WO2021171929A1 - Curable composition, film, infrared-transmitting filter, solid imaging element, and infrared sensor - Google Patents
Curable composition, film, infrared-transmitting filter, solid imaging element, and infrared sensor Download PDFInfo
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- WO2021171929A1 WO2021171929A1 PCT/JP2021/003657 JP2021003657W WO2021171929A1 WO 2021171929 A1 WO2021171929 A1 WO 2021171929A1 JP 2021003657 W JP2021003657 W JP 2021003657W WO 2021171929 A1 WO2021171929 A1 WO 2021171929A1
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- curable composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/12—Polymers provided for in subclasses C08C or C08F
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- H10F39/00—Integrated devices, or assemblies of multiple devices, comprising at least one element covered by group H10F30/00, e.g. radiation detectors comprising photodiode arrays
- H10F39/10—Integrated devices
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- H10F39/00—Integrated devices, or assemblies of multiple devices, comprising at least one element covered by group H10F30/00, e.g. radiation detectors comprising photodiode arrays
- H10F39/10—Integrated devices
- H10F39/12—Image sensors
Definitions
- the present invention relates to a curable composition suitable for producing an infrared transmission filter or the like, and a film using the above-mentioned curable composition. It also relates to an infrared transmission filter, a solid-state image sensor, and an infrared sensor.
- the solid-state image sensor is used as an optical sensor in various applications.
- infrared rays have a longer wavelength than visible light, so they are less likely to scatter, and can be used for distance measurement and three-dimensional measurement.
- infrared rays are invisible to humans and animals, even if the subject is illuminated with an infrared light source at night, the subject will not be noticed, and it will not stimulate the other party for shooting nocturnal wild animals or for crime prevention. It can also be used for shooting.
- the optical sensor infrared sensor
- the optical sensor that senses infrared rays can be developed for various purposes, and it is desired to develop a film that can be used for the infrared sensor.
- Patent Document 1 describes a composition containing a coloring material that transmits infrared rays to block visible light, an infrared absorber, and a curable compound, and the infrared absorber has a wavelength in the range of more than 1000 nm and less than 1200 nm.
- a / B is the ratio of the minimum value A of the absorbance of the above composition in the wavelength range of 400 to 1100 nm to the maximum value B of the absorbance in the wavelength range of 1400 to 1500 nm.
- Compositions of 5 or more are described.
- an object of the present invention is to provide a novel curable composition capable of forming a film capable of transmitting infrared rays in a state where there is little noise derived from visible light. It is also an object of the present invention to provide a film, an infrared transmission filter, a solid-state image sensor, and an infrared sensor.
- the present invention provides: ⁇ 1> A curable composition containing quantum dots having a maximum absorption wavelength in the wavelength range of 700 to 2000 nm and a curable compound. A curable composition containing 5% by mass or more of the quantum dots in the total solid content of the curable composition. ⁇ 2> The curable composition according to ⁇ 1>, wherein the quantum dots contain Pb atoms. ⁇ 3> The curable composition according to ⁇ 1> or ⁇ 2>, wherein the average primary particle size of the quantum dots is 1 to 10 nm.
- the above quantum dots are A first quantum dot having a maximum absorption wavelength in the wavelength range of 700 to 2000 nm,
- the curable composition according to ⁇ 4> which contains 10 to 80 parts by mass of the second quantum dot with respect to 100 parts by mass of the first quantum dot.
- ⁇ 6> The curable composition according to ⁇ 4> or ⁇ 5>, wherein the difference between the maximum absorption wavelength of the second quantum dot and the maximum absorption wavelength of the first quantum dot is 30 to 200 nm.
- ⁇ 7> The curable composition according to any one of ⁇ 1> to ⁇ 6>, wherein a ligand is coordinated to the quantum dots.
- a ligand is a carboxylic acid compound.
- the carboxylic acid compound has a molecular weight of 100,000 or less.
- the content of the organic coloring material is 500 parts by mass or less with respect to 100 parts by mass of the quantum dots.
- ⁇ 12> The curable composition according to ⁇ 10> or ⁇ 11>, wherein the organic coloring material is a compound having a maximum absorption wavelength in a wavelength range of more than 700 nm and 1400 nm or less.
- the curable compound contains a resin and contains a resin.
- the curable composition according to any one of ⁇ 1> to ⁇ 13>, wherein the content of the resin having an amine value in the total amount of the resin is 30% by mass or less.
- ⁇ 15> A / B which is the ratio of the minimum absorbance A in the wavelength range of 400 to 650 nm and the absorbance B at the wavelength of 2200 nm, of the curable composition is 4.5 or more
- ⁇ 17> A film obtained from the curable composition according to any one of ⁇ 1> to ⁇ 16>.
- ⁇ 19> A solid-state image sensor having the film according to ⁇ 17>.
- a novel curable composition capable of forming a film capable of transmitting infrared rays in a state where there is little noise derived from visible light. Further, a film, an infrared transmission filter, a solid-state image sensor, and an infrared sensor can be provided.
- the total solid content refers to the total mass of the components of the curable composition excluding the solvent.
- infrared rays refer to light (electromagnetic waves) having a wavelength of 700 to 2500 nm.
- the notation not describing substitution and non-substitution includes a group having a substituent as well as a group having no substituent.
- the "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
- exposure includes not only exposure using light but also drawing using particle beams such as an electron beam and an ion beam, unless otherwise specified.
- the light used for exposure include the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
- EUV light extreme ultraviolet rays
- (meth) acrylate” represents both acrylate and methacrylate, or either
- (meth) acrylic represents both acrylic and methacrylic, or either.
- Acryloyl "represents both acryloyl and / or methacryloyl.
- Me in the chemical formula represents a methyl group
- Et represents an ethyl group
- Pr represents a propyl group
- Bu represents a butyl group
- Ph represents a phenyl group.
- the term "process” is included in this term not only as an independent process but also as long as the desired action of the process is achieved even if it cannot be clearly distinguished from other processes. ..
- the weight average molecular weight and the number average molecular weight are defined as polystyrene-equivalent values in gel permeation chromatography (GPC) measurements.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) for example, HLC-8220 (manufactured by Tosoh Corporation) is used, and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6) is used as a column. It can be determined by using a 0.0 mm ID (inner diameter) x 15.0 cm) and using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.
- Mw weight average molecular weight
- Mn number average molecular weight
- HLC-8220 manufactured by Tosoh Corporation
- TSKgel Super AWM-H manufactured by Tosoh Corporation
- the curable composition of the present invention contains quantum dots having a maximum absorption wavelength in the wavelength range of 700 to 2000 nm and a curable compound, and contains 5% by mass or more of the quantum dots in the total solid content of the curable composition. It is characterized by containing.
- Quantum dots have a discontinuous energy level of quantum effect and a bandgap type continuous energy level.
- the maximum absorption wavelength (absorption peak) of a quantum dot corresponds to a discontinuous energy level expressed by the quantum effect, and the energy level changes depending on the particle size.
- the quantum dots have a light-shielding property due to bandgap type absorption for light having a wavelength shorter than the maximum absorption wavelength of the quantum dots. Therefore, for example, a quantum dot having a maximum absorption wavelength in the wavelength range of 700 to 2000 nm has a high light-shielding property for light in the vicinity of the maximum absorption wavelength and light having a wavelength shorter than that.
- the present inventors By incorporating such quantum dots in the total solid content of the curable composition in an amount of 5% by mass or more, the present inventors have a high light-shielding property in the visible region, which is higher than the maximum absorption wavelength of the quantum dots. It has been found that a film having high transparency to light having a wavelength on the long wavelength side can be formed. Therefore, it has been found that the curable composition of the present invention can form a film capable of transmitting infrared rays in a state where there is little noise derived from visible light. Further, the present inventors have found that the maximum absorption wavelength can be adjusted by adjusting the size of the quantum dot or the like.
- the maximum absorption wavelength can be shifted to the long wave side, and by reducing the size of the quantum dots, the maximum absorption wavelength can be shifted to the short wave side. .. Therefore, it has been found that the spectroscopic design of infrared rays transmitted through the film can be easily changed and adjusted, and the design can be changed according to the purpose.
- the curable composition of the present invention is preferably used as a curable composition for an infrared transmission filter.
- the ratio of the minimum value A of the absorbance of the curable composition of the present invention in the wavelength range of 400 to 650 nm and the absorbance B at the wavelength of 2200 nm is preferably 4.5 or more, and preferably 10 or more. It is preferably 20 or more, more preferably 30 or more, and even more preferably 30 or more.
- the upper limit can be, for example, 90 or less.
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 650 nm is 20% or less, and the light having a wavelength of 2200 nm in the film thickness direction. It is possible to preferably form a film having a spectral characteristic of 70% or more in transmittance.
- composition of the present invention satisfies any of the following spectral characteristics (IR1) to (IR12).
- (IR1) A1 / B1 which is the ratio of the minimum absorbance A1 in the wavelength range of 400 to 830 nm and the maximum absorbance B1 in the wavelength range of 1000 to 2200 nm of the curable composition is 4.5 or more. Is more preferable, 10 or more is more preferable, 20 or more is further preferable, and 30 or more is even more preferable.
- the upper limit can be, for example, 90 or less.
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 830 nm is 20% or less, and the light transmittance in the film thickness direction. It is possible to preferably form a film having a spectral characteristic with a minimum value of 70% or more in the wavelength range of 1000 to 2200 nm.
- the ratio of the minimum absorbance A2 in the wavelength range of 400 to 950 nm and the maximum absorbance B2 in the wavelength range of 1100 to 2200 nm of the curable composition is 4.5 or more. Is more preferable, 10 or more is more preferable, 20 or more is further preferable, and 30 or more is even more preferable.
- the upper limit can be, for example, 90 or less.
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 940 nm is 20% or less, and the light transmittance in the film thickness direction. It is possible to preferably form a film having a spectral characteristic with a minimum value of 70% or more in the wavelength range of 1100 to 2200 nm.
- the ratio of the minimum absorbance A3 in the wavelength range of 400 to 1050 nm and the maximum absorbance B3 in the wavelength range of 1200 to 2200 nm of the curable composition is 4.5 or more. Is more preferable, 10 or more is more preferable, 20 or more is further preferable, and 30 or more is even more preferable.
- the upper limit can be, for example, 90 or less.
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1050 nm is 20% or less, and the light transmittance in the film thickness direction. It is possible to preferably form a film having a spectral characteristic with a minimum value of 70% or more in the wavelength range of 1200 to 2200 nm.
- IR4 A4 / B4 which is the ratio of the minimum absorbance A4 in the wavelength range of 400 to 1150 nm and the maximum absorbance B4 in the wavelength range of 1300 to 2200 nm of the curable composition, is 4.5 or more. Is more preferable, 10 or more is more preferable, 20 or more is further preferable, and 30 or more is even more preferable.
- the upper limit can be, for example, 90 or less.
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1150 nm is 20% or less, and the light transmittance in the film thickness direction. It is possible to preferably form a film having a spectral characteristic with a minimum value of 70% or more in the wavelength range of 1300 to 2200 nm.
- the ratio of the minimum absorbance A5 in the wavelength range of 400 to 1250 nm and the maximum absorbance B5 in the wavelength range of 1400 to 2200 nm of the curable composition is 4.5 or more. Is more preferable, 10 or more is more preferable, 20 or more is further preferable, and 30 or more is even more preferable.
- the upper limit can be, for example, 90 or less.
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1250 nm is 20% or less, and the light transmittance in the film thickness direction. It is possible to preferably form a film having a spectral characteristic with a minimum value of 70% or more in the wavelength range of 1400 to 2200 nm.
- IR6 A6 / B6 which is the ratio of the minimum absorbance A6 in the wavelength range of 400 to 1350 nm and the maximum absorbance B6 in the wavelength range of 1500 to 2200 nm of the curable composition, is 4.5 or more. Is more preferable, 10 or more is more preferable, 20 or more is further preferable, and 30 or more is even more preferable.
- the upper limit can be, for example, 90 or less.
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1350 nm is 20% or less, and the light transmittance in the film thickness direction. It is possible to preferably form a film having a spectral characteristic with a minimum value of 70% or more in the wavelength range of 1500 to 2200 nm.
- the ratio of the minimum absorbance A7 in the wavelength range of 400 to 1450 nm and the maximum absorbance B7 in the wavelength range of 1600 to 2200 nm of the curable composition, A7 / B7, is 4.5 or more. Is more preferable, 10 or more is more preferable, 20 or more is further preferable, and 30 or more is even more preferable.
- the upper limit can be, for example, 90 or less.
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1450 nm is 20% or less, and the light transmittance in the film thickness direction. It is possible to preferably form a film having a spectral characteristic with a minimum value of 70% or more in the wavelength range of 1600 to 2200 nm.
- the ratio of the minimum absorbance A8 in the wavelength range of 400 to 1550 nm and the maximum absorbance B8 in the wavelength range of 1700 to 2200 nm of the curable composition, A8 / B8, is 4.5 or more. Is more preferable, 10 or more is more preferable, 20 or more is further preferable, and 30 or more is even more preferable.
- the upper limit can be, for example, 90 or less.
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1550 nm is 20% or less, and the light transmittance in the film thickness direction. It is possible to preferably form a film having a spectral characteristic with a minimum value of 70% or more in the wavelength range of 1700 to 2200 nm.
- the ratio of the minimum absorbance A9 in the wavelength range of 400 to 1650 nm and the maximum absorbance B9 in the wavelength range of 1800 to 2200 nm of the curable composition is 4.5 or more. Is more preferable, 10 or more is more preferable, 20 or more is further preferable, and 30 or more is even more preferable.
- the upper limit can be, for example, 90 or less.
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1650 nm is 20% or less, and the light transmittance in the film thickness direction. It is possible to preferably form a film having a spectral characteristic with a minimum value of 70% or more in the wavelength range of 1800 to 2200 nm.
- IR10 A10 / B10 which is the ratio of the minimum absorbance A10 in the wavelength range of 400 to 1750 nm and the maximum absorbance B10 in the wavelength range of 1900 to 2200 nm of the curable composition, is 4.5 or more. Is more preferable, 10 or more is more preferable, 20 or more is further preferable, and 30 or more is even more preferable.
- the upper limit can be, for example, 90 or less.
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1750 nm is 20% or less, and the light transmittance in the film thickness direction. It is possible to preferably form a film having a spectral characteristic with a minimum value of 70% or more in the wavelength range of 1900 to 2200 nm.
- IR11 A11 / B11, which is the ratio of the minimum absorbance A11 in the wavelength range of 400 to 1850 nm and the maximum absorbance B11 in the wavelength range of 2000 to 2200 nm of the curable composition, is 4.5 or more. Is more preferable, 10 or more is more preferable, 20 or more is further preferable, and 30 or more is even more preferable.
- the upper limit can be, for example, 90 or less.
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1850 nm is 20% or less, and the light transmittance in the film thickness direction.
- a film having a spectral characteristic with a minimum value of 70% or more in the wavelength range of 2000 to 2200 nm can be preferably formed.
- IR12 A12 / B12 which is the ratio of the minimum absorbance A12 in the wavelength range of 400 to 1950 nm and the maximum absorbance B12 in the wavelength range of 2100 to 2200 nm of the curable composition, is 4.5 or more. Is more preferable, 10 or more is more preferable, 20 or more is further preferable, and 30 or more is even more preferable.
- the upper limit can be, for example, 90 or less.
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1950 nm is 20% or less, and the light transmittance in the film thickness direction. It is possible to preferably form a film having a spectral characteristic with a minimum value of 70% or more in the wavelength range of 2100 to 2200 nm.
- the above absorbance condition can be achieved, for example, by adjusting the type and content of quantum dots having a maximum absorption wavelength in the wavelength range of 700 to 2000 nm.
- the absorbance A ⁇ at a certain wavelength ⁇ is defined by the following equation (1).
- a ⁇ -log (T ⁇ / 100) ...
- a ⁇ is the absorbance at the wavelength ⁇
- T ⁇ is the transmittance (%) at the wavelength ⁇ .
- the absorbance value may be a value measured in a solution state or a value in a film formed by using the curable composition of the present invention.
- a curable composition is applied onto a glass substrate by a method such as spin coating so that the thickness of the film after drying becomes a predetermined thickness, and a hot plate is used. It is preferable to measure using a membrane prepared by drying at 100 ° C. for 120 seconds.
- the thickness of the film can be measured by using a stylus type surface shape measuring device (DEKTAK150 manufactured by ULVAC, Inc.) for the substrate having the film.
- the absorbance can be measured using a conventionally known spectrophotometer.
- the measurement condition of the absorbance is not particularly limited, but the absorbance B at the wavelength of 2200 nm is measured under the condition that the minimum value A of the absorbance in the wavelength range of 400 to 650 nm is adjusted to 0.1 to 3.0. Is preferable. By measuring the absorbance under such conditions, the measurement error can be further reduced.
- the method for adjusting the minimum absorbance A in the wavelength range of 400 to 650 nm to be 0.1 to 3.0 is not particularly limited. For example, when measuring the absorbance in the state of a solution, a method of adjusting the optical path length of the sample cell can be mentioned. Further, when measuring the absorbance in the state of a film, a method of adjusting the film thickness and the like can be mentioned.
- the curable composition of the present invention is applied onto a glass substrate by a method such as spin coating so that the thickness of the film after drying becomes a predetermined thickness, and dried at 100 ° C. for 120 seconds using a hot plate. ..
- the thickness of the film is measured by using a stylus type surface shape measuring device (DEKTAK150 manufactured by ULVAC) on the dried substrate having the film.
- the transmittance of the dried substrate having this film is measured using an ultraviolet-visible near-infrared spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation).
- the total solid content (solid content concentration) of the curable composition of the present invention varies depending on the method of application to the substrate, but is preferably 1 to 50% by mass, for example.
- the lower limit is more preferably 10% by mass or more.
- the upper limit is more preferably 30% by mass or less.
- the curable composition of the present invention is the above-mentioned film when a film having a film thickness of 0.1 to 50 ⁇ m (preferably 0.1 to 20 ⁇ m, more preferably 0.5 to 10 ⁇ m) after drying is formed. At least one of the thicknesses, the maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 650 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the wavelength is 2200 nm. It is preferable that the light transmittance of the light is 70% or more (preferably 75% or more, more preferably 80% or more).
- composition of the present invention satisfies the spectral characteristics of any of the following aspects (1) to (12).
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmittance in the film thickness direction.
- An embodiment in which the minimum value of the rate in the wavelength range of 1000 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 830 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 940 nm.
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmittance in the film thickness direction.
- An embodiment in which the minimum value of the rate in the wavelength range of 1100 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 950 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1040 nm.
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1050 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmittance in the film thickness direction.
- An embodiment in which the minimum value of the rate in the wavelength range of 1200 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, it is possible to obtain a film capable of transmitting infrared rays having a wavelength of more than 1140 nm by blocking light in the wavelength range of 400 to 1050 nm.
- a film having a film thickness of 0.1 to 50 ⁇ m (preferably 0.1 to 20 ⁇ m, more preferably 0.5 to 10 ⁇ m) after drying is formed, at least one of the above-mentioned film thicknesses is used.
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1150 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmittance in the film thickness direction.
- An embodiment in which the minimum value of the rate in the wavelength range of 1300 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1150 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1240 nm.
- a film having a film thickness of 0.1 to 50 ⁇ m (preferably 0.1 to 20 ⁇ m, more preferably 0.5 to 10 ⁇ m) after drying is formed, at least one of the above-mentioned film thicknesses is used.
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1250 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmittance in the film thickness direction.
- An embodiment in which the minimum value of the rate in the wavelength range of 1400 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1250 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1340 nm.
- a film having a film thickness of 0.1 to 50 ⁇ m (preferably 0.1 to 20 ⁇ m, more preferably 0.5 to 10 ⁇ m) after drying is formed, at least one of the above-mentioned film thicknesses is used.
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1350 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmittance in the film thickness direction.
- An embodiment in which the minimum value of the rate in the wavelength range of 1500 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1350 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1440 nm.
- a film having a film thickness of 0.1 to 50 ⁇ m (preferably 0.1 to 20 ⁇ m, more preferably 0.5 to 10 ⁇ m) after drying is formed, at least one of the above-mentioned film thicknesses is used.
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1450 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmittance in the film thickness direction.
- An embodiment in which the minimum value of the rate in the wavelength range of 1600 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1450 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1540 nm.
- a film having a film thickness of 0.1 to 50 ⁇ m (preferably 0.1 to 20 ⁇ m, more preferably 0.5 to 10 ⁇ m) after drying is formed, at least one of the above-mentioned film thicknesses is used.
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1550 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmittance in the film thickness direction.
- An embodiment in which the minimum value of the rate in the wavelength range of 1700 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1550 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1640 nm.
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1650 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmittance in the film thickness direction.
- An embodiment in which the minimum value of the rate in the wavelength range of 1800 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1650 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1740 nm.
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1750 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmittance in the film thickness direction.
- An embodiment in which the minimum value of the rate in the wavelength range of 1900 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1750 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1840 nm.
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1850 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmittance in the film thickness direction.
- An embodiment in which the minimum value of the rate in the wavelength range of 2000 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1850 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1940 nm.
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmittance in the film thickness direction.
- An embodiment in which the minimum value of the rate in the wavelength range of 2100 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1950 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 2040 nm.
- the curable composition of the present invention transmits infrared rays, it can also be said to be an infrared transmissive composition.
- each component that can constitute the curable composition of the present invention will be described.
- Quantum dots The curable composition of the present invention contains quantum dots (hereinafter, also referred to as quantum dot IR) having a maximum absorption wavelength in the wavelength range of 700 to 2000 nm.
- quantum dot IR quantum dots
- the value of the maximum absorption wavelength of a quantum dot is a value in a solution.
- the maximum absorption wavelength of the quantum dots can be determined by preparing a toluene solution of quantum dots of 10 mg / mL and measuring the absorbance of the toluene solution using an ultraviolet-visible near-infrared spectrophotometer.
- the quantum dot IR may be a semiconductor particle.
- Examples of the quantum dot material constituting the quantum dot include general semiconductor crystals [a) group IV semiconductors, b) group IV-IV, group III-V, or group II-VI compound semiconductors, c) group II, and the like. Nanoparticles (particles having a size of 0.5 nm or more and less than 100 nm) of a compound semiconductor composed of a combination of three or more of group III, group IV, group V, and group VI elements can be mentioned.
- the quantum dot IR preferably contains at least one metal atom selected from Pb atom, In atom, Ge atom, Si atom, Cd atom, Zn atom, Hg atom, Al atom, Sn atom and Ga atom. It is more preferable that it contains at least one metal atom selected from Pb atom, In atom, Ge atom and Si atom, and it is further preferable that it contains Pb atom.
- quantum dot material constituting the quantum dot IR, PbS, PbSe, InN, InAs, Ge, InAs, InGaAs, CuInS, CuInSe, CuInGaSe, InSb, HgTe, HgCdTe, Ag 2 S, Ag 2 Se, Ag 2 Te, SnS, SnSe, SnTe , Si, narrow semiconductor material having relatively bandgap such InP can be mentioned, preferably a PbS or PbSe, more preferably PbS.
- the maximum absorption wavelength of the quantum dot IR can be appropriately selected according to the application and purpose. For example, when a quantum dot having a maximum absorption wavelength in the wavelength range of 1000 to 1100 nm is used as the quantum dot IR, a film that blocks light having a wavelength of 400 to 1100 nm and transmits light having a wavelength of 1200 nm or more. Can be formed.
- the average primary particle size of the quantum dot IR is preferably 1 to 10 nm.
- the average primary particle size of the quantum dot IR is an average value of the primary particle size of 10 arbitrarily selected quantum dots.
- a transmission electron microscope may be used to measure the particle size of the quantum dots.
- a ligand is coordinated to the quantum dot IR.
- the quantum dot IR includes the first quantum dot and the second quantum dot described later, it is preferable that the ligand is coordinated to at least one quantum dot, and the ligand is coordinated to both quantum dots. It is more preferable that the position is coordinated. According to this aspect, the dispersibility of the quantum dots in the curable composition is good.
- the ligand include a carboxylic acid compound, an amine compound, a phosphonic acid compound, and a thiol compound, and a carboxylic acid compound is preferable from the viewpoint of dispersibility of the quantum dot IR.
- the molecular weight of the carboxylic acid compound is preferably 100,000 or less, more preferably 60 to 10,000, and even more preferably 100 to 1,000.
- Specific examples of the carboxylic acid compound include oleic acid, 3-mercaptopropionic acid, 4-mercaptobenzoic acid and the like.
- the curable composition of the present invention has a first quantum dot having a maximum absorption wavelength in the wavelength range of 700 to 2000 nm as a quantum dot IR, and a maximum absorption on the wavelength side longer than the maximum absorption wavelength of the first quantum dot. It is also preferable to use a second quantum dot having a wavelength. According to this aspect, it is possible to form a film having a better light-shielding property of light having a wavelength on the short wave side than the maximum absorption wavelength of the second quantum dot. Two or more types of second quantum dots may be included.
- the difference between the maximum absorption wavelength of the second quantum dot and the maximum absorption wavelength of the first quantum dot is preferably 1 to 500 nm because the visible light-shielding property of the obtained film can be further enhanced. It is more preferably 20 to 300 nm, and even more preferably 30 to 200 nm.
- the difference between the maximum absorption wavelength of the second quantum dot having the maximum absorption wavelength on the shortest wavelength side and the maximum absorption wavelength of the first quantum dot is large. It is preferably in the above range.
- the maximum absorption wavelength of the second quantum dot A a where the maximum absorption wavelength exists in a long wavelength side in a th is preferably 1 to 500 nm, more preferably 20 to 300 nm. It is more preferably 30 to 200 nm.
- a represents an integer of 1 to n-1
- n represents an integer of 3 or more.
- the content of the quantum dot IR in the total solid content of the curable composition is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more. It is even more preferably 25% by mass or more, and particularly preferably 30% by mass or more.
- the upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, and further preferably 60% by mass or less.
- the second quantum dots are added to 100 parts by mass of the first quantum dots. It is preferable to contain 100 parts by mass.
- the upper limit is preferably 80 parts by mass or less, and more preferably 50 parts by mass or less.
- the lower limit is preferably 10 parts by mass or more, and more preferably 20 parts by mass or more.
- the curable composition of the present invention may further contain quantum dots having a maximum absorption wavelength in the wavelength range of 400 nm or more and less than 700 nm (hereinafter, also referred to as quantum dots Vl).
- quantum dots Vl quantum dots having a maximum absorption wavelength in the wavelength range of 400 nm or more and less than 700 nm
- Examples of the material of the quantum dot Vl include those explained in the quantum dot IR.
- the maximum absorption wavelength of the quantum dot Vl is preferably in the wavelength range of 450 nm or more and less than 700 nm, more preferably in the wavelength range of 500 nm or more and less than 700 nm, and more preferably in the wavelength range of 600 nm or more and less than 700 nm. More preferred.
- the content of the quantum dot Vl in the total solid content of the curable composition is preferably more than 0% by mass and 10% by mass or less.
- the lower limit is preferably 1% by mass or more, and more preferably 2% by mass or more.
- the upper limit is preferably 8% by mass or less, and more preferably 5% by mass or less.
- the total content of the quantum dot IR and the quantum dot Vl in the total solid content of the curable composition is preferably 5 to 80% by mass.
- the lower limit is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 25% by mass or more, and particularly preferably 30% by mass or more.
- the upper limit is preferably 75% by mass or less, and more preferably 70% by mass or less.
- the curable composition of the present invention can contain an organic coloring material. According to this aspect, it is easy to enhance the light blocking property and form a film capable of selectively transmitting the target light.
- the organic color material include a chromatic color material, a black color material, and a near-infrared absorbing color material.
- the organic color material means a color material composed of an organic compound.
- the organic coloring material in the present specification includes a coloring material composed of an organic compound containing a metal atom such as a metal complex. Examples of the coloring material composed of an organic compound containing a metal atom include a phthalocyanine compound containing a metal atom such as copper, zinc, and aluminum as a central metal.
- the organic coloring material may be a pigment or a dye. Pigments and dyes may be used in combination.
- the organic coloring material preferably contains a compound having a maximum absorption wavelength in the range of more than 700 nm and 1400 nm or less. Examples of such a color material include a near-infrared absorbing color material.
- the average primary particle size of the pigment is preferably 1 to 200 nm.
- the lower limit is preferably 5 nm or more, more preferably 10 nm or more.
- the upper limit is preferably 180 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less.
- the primary particle size of the pigment can be determined from the image photograph obtained by observing the primary particles of the pigment with a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is obtained, and the corresponding circle-equivalent diameter is calculated as the primary particle diameter of the pigment.
- the average primary particle size in the present invention is an arithmetic mean value of the primary particle size for the primary particles of 400 pigments.
- the primary particles of the pigment refer to independent particles without agglomeration.
- chromatic color material examples include a color material having a maximum absorption wavelength in the wavelength range of 400 to 700 nm. For example, a yellow color material, an orange color material, a red color material, a green color material, a purple color material, a blue color material, and the like can be mentioned. Specific examples of the chromatic color material include those shown below.
- a halogenated zinc phthalocyanine having an average of 10 to 14 halogen atoms in one molecule, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms. Pigments can also be used. Specific examples include the compounds described in WO 2015/118720. Further, as a green color material, the compound described in Chinese Patent Application No. 1069009027, the phthalocyanine compound having a phosphate ester described in International Publication No. 2012/10395 as a ligand, and Japanese Patent Application Laid-Open No. 2019-008014. , The phthalocyanine compound described in JP-A-2018-180023, the compound described in JP-A-2019-038958, and the like can also be used.
- an aluminum phthalocyanine compound having a phosphorus atom can also be used. Specific examples include the compounds described in paragraphs 0022 to 0030 of JP2012-247591A and paragraphs 0047 of JP2011-157478A.
- the quinophthalone compound described in Kai 2019-008014 can also be used.
- red color material a diketopyrrolopyrrole pigment in which at least one bromine atom is substituted in the structure described in JP-A-2017-201384, and a diketopyrrolopyrrole pigment described in paragraphs 0016 to 0022 of Patent No. 6248838.
- the red color material described in Japanese Patent No. 6516119, the red color material described in Japanese Patent No. 6525101, and the like can also be used.
- a compound having a structure in which an aromatic ring group having an oxygen atom, a sulfur atom, or a nitrogen atom bonded to the aromatic ring is bonded to a diketopyrrolopyrrole skeleton is used. You can also.
- a dye can be used as a chromatic color material.
- the dye is not particularly limited, and known dyes can be used.
- pyrazole azo compound, anilino azo compound, triarylmethane compound, anthraquinone compound, anthrapyridone compound, benzylidene compound, oxonol compound, pyrazorotriazole azo compound, pyridone azo compound, cyanine compound, phenothiazine compound, pyropyrazole azomethine compound, xanthene compound Examples thereof include phthalocyanine compounds, benzopyran compounds, indigo compounds and pyromethene compounds.
- the thiazole compound described in JP2012-158649A, the azo compound described in JP2011-184493, and the azo compound described in JP2011-145540 can also be used.
- a dye multimer can also be used.
- the dye multimer has two or more dye structures in one molecule, and preferably has three or more dye structures.
- the upper limit is not particularly limited, but may be 100 or less.
- the plurality of dye structures contained in one molecule may have the same dye structure or different dye structures.
- the weight average molecular weight (Mw) of the dye multimer is preferably 2000 to 50,000.
- the lower limit is more preferably 3000 or more, and even more preferably 6000 or more.
- the upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less.
- Dye multimers are available from JP-A-2011-213925, JP-A-2013-041097, JP-A-2015-028144, JP-A-2015-030742, JP-A-2016-102191, International Publication No. 2016 / Compounds described in 031442 and the like can also be used.
- Two or more kinds of chromatic color materials may be used in combination. Further, when two or more kinds of chromatic color materials are used in combination, black may be formed by a combination of two or more kinds of chromatic color materials. Examples of such a combination include the following aspects (1) to (8). (1) An embodiment containing a yellow color material, a blue color material, a purple color material, and a red color material. (2) An embodiment containing a yellow color material, a blue color material, and a red color material. (3) An embodiment containing a yellow color material, a purple color material, and a red color material. (4) An embodiment containing a yellow color material and a purple color material.
- An embodiment containing a green color material, a blue color material, a purple color material, and a red color material An embodiment containing a purple color material and an orange color material.
- An embodiment containing a green color material, a purple color material, and a red color material An embodiment containing a green color material and a red color material.
- the black color material is not particularly limited, and known materials can be used.
- bisbenzofuranone compound, azomethine compound, perylene compound, azo compound and the like can be mentioned, and bisbenzofuranone compound and perylene compound are preferable.
- Examples of the bisbenzofuranone compound are described in JP-A-2010-534726, JP-A-2012-515233, App. Compounds are mentioned and are available, for example, as "Irgaphor Black” manufactured by BASF.
- Examples of the perylene compound include C.I. I. Pigment Black 31, 32 and the like can be mentioned.
- the azomethine compound include the compounds described in JP-A-01-170601 and JP-A-02-0346664, and are available as, for example, "Chromofine Black A1103" manufactured by Dainichiseika.
- the near-infrared absorbing color material is preferably an organic coloring material having a maximum absorption wavelength in the range of more than 700 nm and 1400 nm or less.
- the maximum absorption wavelength of the near-infrared absorbing color material is preferably 1200 nm or less, more preferably 1000 nm or less, and further preferably 950 nm or less.
- the near-infrared absorbing color material preferably has A 550 / A max, which is the ratio of the absorbance A 550 at a wavelength of 550 nm and the absorbance A max at the maximum absorption wavelength, to be 0.1 or less, preferably 0.05 or less.
- the absorbance ratio is in the above range, a near-infrared absorbing color material having excellent visible transparency and near-infrared shielding property can be obtained.
- the near-infrared absorbing color material is preferably a pigment.
- the maximum absorption wavelength of the near-infrared absorbing color material and the value of the absorbance at each wavelength are values obtained from the absorption spectrum of the film formed by using the composition containing the near-infrared absorbing color material.
- the near-infrared absorbing coloring material is not particularly limited, but is pyrolopyrrole compound, cyanine compound, squarylium compound, phthalocyanine compound, naphthalocyanine compound, quaterylene compound, merocyanine compound, croconium compound, oxonor compound, iminium compound, dithiol compound, and tria.
- Examples thereof include a reelmethane compound, a pyromethene compound, an azomethine compound, an anthraquinone compound, a dibenzofuranone compound, and a dithiolene metal complex.
- Examples of the pyrolopyrrole compound include the compounds described in paragraphs 0016 to 0058 of JP2009-263614, the compounds described in paragraphs 0037 to 0052 of JP2011-066731, and International Publication No. 2015/166783. Examples thereof include the compounds described in paragraphs 0010 to 0033.
- Examples of the squarylium compound include the compounds described in paragraphs 0044 to 0049 of JP2011-208101A, the compounds described in paragraphs 0060 to 0061 of Patent No. 6065169, and paragraph numbers 0040 of International Publication No. 2016/181987. , The compound described in JP-A-2015-176046, the compound described in paragraph number 0072 of International Publication No.
- JP2012-077153 the oxytitanium phthalocyanine described in JP2006-343631, and paragraphs 0013 to 0029 of JP2013-195480.
- vanadium phthalocyanine compound described in Japanese Patent No. 6081771.
- examples of the naphthalocyanine compound include the compounds described in paragraph No. 0093 of JP2012-077153.
- Examples of the dithiolene metal complex include the compounds described in Japanese Patent No. 5733804.
- Examples of the near-infrared absorbing coloring material include a squarylium compound described in JP-A-2017-197437, a squarylium compound described in JP-A-2017-025311, a squarylium compound described in International Publication No. 2016/154782, and Patent No. 5884953.
- Squarylium compound described in Japanese Patent Publication No. 60366689 Squalylium compound described in Japanese Patent No. 581604, Squalylium compound described in International Publication No. 2017/213047, paragraph numbers 0090 to 0107, special feature.
- Linked squalylium compound compound having a pyrrolbis-type squalylium skeleton or croconium skeleton described in JP-A-2017-141215, dihydrocarbazolebis-type squalylium compound described in JP-A-2017-082029, JP-A-2017-068120
- the asymmetric compound described in paragraphs 0027 to 0114 of Japanese Patent Application Laid-Open No. 2017, the pyrrole ring-containing compound (carbazole type) described in JP-A-2017-067963, the phthalocyanine compound described in Japanese Patent No. 6251530, and the like are used. You can also do it.
- the content of the organic coloring material is preferably 500 parts by mass or less, preferably 100 parts by mass or less, with respect to 100 parts by mass of the quantum dot IR (quantum dot having a maximum absorption wavelength in the wavelength range of 700 to 2000 nm). More preferably, it is more preferably 50 parts by mass or less.
- the lower limit may be 1 part by mass or more, or 10 parts by mass or more.
- the curable composition of the present invention contains a curable compound.
- the curable compound include polymerizable compounds, resins, and natural polymers such as gelatin and cellulose.
- the gelatin there are acid-treated gelatin and alkali-treated gelatin (lime treatment and the like) depending on the synthesis method, and both of them can be preferably used.
- the molecular weight of gelatin is preferably 10,000 to 1,000,000.
- modified gelatin modified by utilizing an amino group or a carboxyl group of gelatin can also be used (for example, phthalated gelatin).
- the resin may be a non-polymerizable resin (a resin having no polymerizable group) or a polymerizable resin (a resin having a polymerizable group).
- the polymerizable group include an ethylenically unsaturated bond-containing group, an epoxy group, and a methylol group.
- the ethylenically unsaturated bond-containing group include a vinyl group, an allyl group, and a (meth) acryloyl group.
- the polymerizable resin (resin having a polymerizable group) is also a polymerizable compound.
- the curable compound preferably contains at least a resin, more preferably a resin and a monomer-type polymerizable compound, and a monomer-type compound having an ethylenically unsaturated bond with the resin. It is more preferable to use a polymerizable compound.
- the content of the curable compound in the total solid content of the curable composition of the present invention is preferably 0.1 to 80% by mass.
- the lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more, and further preferably 5% by mass or more.
- the upper limit is preferably 70% by mass or less, more preferably 60% by mass or less, further preferably 50% by mass or less, further preferably 40% by mass or less, and particularly preferably 30% by mass or less.
- the curable compound may be only one kind or two or more kinds. In the case of two or more types, the total amount is preferably in the above range.
- polymerizable compound examples include a compound having an ethylenically unsaturated bond-containing group, a compound having an epoxy group, and a compound having a methylol group.
- the polymerizable compound may be a monomer or a resin.
- a monomer-type polymerizable compound having an ethylenically unsaturated bond-containing group can be preferably used as a radically polymerizable compound.
- the compound having an epoxy group can be preferably used as a cationically polymerizable compound.
- the molecular weight of the monomer-type polymerizable compound is preferably less than 2000, more preferably 100 or more and less than 2000, and even more preferably 200 or more and less than 2000.
- the upper limit of the molecular weight of the monomer-type polymerizable compound is preferably 1500 or less.
- the weight average molecular weight (Mw) of the resin-type polymerizable compound is preferably 2000 to 2000000.
- the upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less.
- the lower limit is preferably 3000 or more, and more preferably 5000 or more.
- Examples of the resin type polymerizable compound include an epoxy resin and a resin containing a repeating unit having a polymerizable group.
- Examples of the repeating unit having a polymerizable group include the following formulas (A2-1) to (A2-4).
- R 1 represents a hydrogen atom or an alkyl group.
- the number of carbon atoms of the alkyl group is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1.
- R 1 is preferably a hydrogen atom or a methyl group.
- L 51 represents a single bond or a divalent linking group.
- the divalent linking group includes an alkylene group, an arylene group, -O-, -S-, -CO-, -COO-, -OCO-, -SO 2- , -NR 10- (R 10 is a hydrogen atom or (Representing an alkyl group, preferably a hydrogen atom), or a group consisting of a combination thereof can be mentioned.
- the alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 15 carbon atoms, and even more preferably 1 to 10 carbon atoms.
- the alkylene group may have a substituent, but is preferably unsubstituted.
- the alkylene group may be linear, branched or cyclic. Further, the cyclic alkylene group may be either monocyclic or polycyclic.
- the arylene group preferably has 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, and even more
- P 1 represents a polymerizable group.
- the polymerizable group include an ethylenically unsaturated bond-containing group, an epoxy group, a methylol group, and an alkoxymethyl group.
- the compound having a monomer-type ethylenically unsaturated bond-containing group is preferably a 3- to 15-functional (meth) acrylate compound, and more preferably a 3- to 6-functional (meth) acrylate compound.
- a compound containing a monomer-type ethylenically unsaturated bond-containing group the description in paragraphs 0033 to 0034 of JP2013-253224A can be referred to, and the content thereof is incorporated in the present specification.
- Examples of the compound having a group having a monomer-type ethylenically unsaturated bond include ethylene oxy-modified pentaerythritol tetraacrylate (commercially available NK ester ATM-35E; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and dipentaerythritol tri.
- Acrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (Meta) acrylate (commercially available KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A- DPH-12E; manufactured by Shin-Nakamura Chemical Industry Co., Ltd., and compounds having a structure in which these (meth) acryloyl groups are bonded via ethylene glycol residues and / or propylene glycol residues are preferable.
- oligomer types can be used. Further, the polymerization described in paragraph numbers 0034 to 0038 of JP2013-253224A and paragraph number 0477 of JP2012-208494A (paragraph number 0585 of the corresponding US Patent Application Publication No. 2012/0235099). Sexual monomers and the like can also be used and these contents are incorporated herein.
- Compounds having a monomer-type ethylenically unsaturated bond-containing group include diglycerin EO (ethylene oxide) modified (meth) acrylate (commercially available M-460; manufactured by Toa Synthetic) and pentaerythritol tetraacrylate (Shin-Nakamura).
- the compound containing a monomer-type ethylenically unsaturated bond-containing group may have an acid group such as a carboxyl group, a sulfo group, or a phosphoric acid group.
- an acid group such as a carboxyl group, a sulfo group, or a phosphoric acid group.
- Examples of commercially available products include the Aronix series manufactured by Toagosei Co., Ltd. (for example, M-305, M-510, M-520).
- the compound containing a monomer-type ethylenically unsaturated bond-containing group is preferably a compound having a caprolactone structure.
- the compound having a caprolactone structure the description in paragraphs 0042 to 0045 of JP2013-253224A can be referred to, and the contents thereof are incorporated in the present specification.
- Examples of the compound having a caprolactone structure include DPCA-20, DPCA-30, DPCA-60, DPCA-120, etc., which are commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series.
- a compound having an ethylenically unsaturated bond-containing group and an alkyleneoxy group can also be used.
- the compound having an ethylenically unsaturated bond-containing group and an alkyleneoxy group a compound having an ethylenically unsaturated bond-containing group and an ethyleneoxy group and / or a propyleneoxy group is preferable, and a group having an ethylenically unsaturated bond.
- a compound having an ethyleneoxy group and an ethyleneoxy group is more preferable, and a 3 to 6 functional (meth) acrylate compound having 4 to 20 ethyleneoxy groups is further preferable.
- SR-494 which is a tetrafunctional (meth) acrylate having four ethyleneoxy groups manufactured by Sartomer, and three isobutyleneoxy groups.
- examples thereof include KAYARAD TPA-330, which is a trifunctional (meth) acrylate having.
- Examples of the compound containing an ethylenically unsaturated bond-containing group are described in Japanese Patent Application Laid-Open No. 48-041708, Japanese Patent Application Laid-Open No. 51-0371993, Japanese Patent Application Laid-Open No. 02-032293, and Japanese Patent Application Laid-Open No. 02-0176765.
- Urethane acrylates and urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418. Is also suitable.
- addition-polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238. Can be done.
- Commercially available products include UA-7200 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T- Examples include 600 and AI-600 (Kyoeisha Chemical Co., Ltd.).
- the compound containing an ethylenically unsaturated bond-containing group the compounds described in Japanese Patent Application Laid-Open No. 2017-0438367, Japanese Patent No. 6057891, and Japanese Patent No. 6031807 can also be used. Further, as the compound containing an ethylenically unsaturated bond-containing group, it is also preferable to use 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.), light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), or the like. ..
- the content of the compound containing an ethylenically unsaturated bond-containing group in the total solid content of the curable composition is 0. It is preferably 1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, and particularly preferably 5% by mass or more.
- the upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, further preferably 50% by mass or less, further preferably 40% by mass or less, and particularly preferably 30% by mass or less. preferable.
- Examples of the compound having an epoxy group include a monofunctional or polyfunctional glycidyl ether compound, a polyfunctional aliphatic glycidyl ether compound, and the like. Further, as the epoxy compound, a compound having an alicyclic epoxy group can also be used.
- Examples of the epoxy compound include compounds having one or more epoxy groups in one molecule.
- the epoxy compound is preferably a compound having 1 to 100 epoxy groups in one molecule.
- the upper limit of the number of epoxy groups may be, for example, 10 or less, or 5 or less.
- the lower limit of the epoxy group is preferably two or more.
- the epoxy compound may be either a small molecule compound (for example, a molecular weight of less than 1000) or a high molecular compound (macromolecule) (for example, a molecular weight of 1000 or more, and in the case of a polymer, a weight average molecular weight of 1000 or more).
- the weight average molecular weight of the epoxy compound is preferably 2000 to 100,000.
- the upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5000 or less, and even more preferably 3000 or less.
- epoxy compounds include EHPE3150 (manufactured by Daicel Co., Ltd.), EPICLON N-695 (manufactured by DIC Corporation), ADEKA Glycyrrol ED-505 (manufactured by ADEKA Co., Ltd., epoxy group-containing monomer), and marproof.
- the content of the epoxy compound in the total solid content of the curable composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more. 1, 1% by mass or more is more preferable, and 5% by mass or more is particularly preferable.
- the upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, further preferably 50% by mass or less, further preferably 40% by mass or less, and particularly preferably 30% by mass or less. preferable.
- Examples of the compound having a methylol group include a compound in which the methylol group is bonded to a nitrogen atom or a carbon atom forming an aromatic ring.
- Compounds in which the methylol group is bonded to a nitrogen atom include alkoxymethylated melamine, methylolated melamine, alkoxymethylated benzoguanamine, methylated benzoguanamine, alkoxymethylated glycol uryl, methylated glycol uryl, alkoxymethylated urea and methylol.
- Urea compound and the like are preferable. Further, the description of paragraphs 0134 to 0147 of JP-A-2004-295116 and paragraphs 095 to 0126 of JP-A-2014-089408 can be referred to, and these contents are incorporated in the present specification.
- the content of the methylol compound in the total solid content of the curable composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more. 1, 1% by mass or more is more preferable, and 5% by mass or more is particularly preferable.
- the upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, further preferably 50% by mass or less, further preferably 40% by mass or less, and particularly preferably 30% by mass or less. preferable.
- a resin in the curable composition of the present invention, can be used as the curable compound. It is preferable to use a curable compound containing at least a resin.
- the resin can also be used as a dispersant.
- the resin used to disperse pigments and the like is also referred to as a dispersant.
- such an application of the resin is an example, and the resin can be used for a purpose other than such an application.
- the resin having a polymerizable group also corresponds to a polymerizable compound.
- the weight average molecular weight (Mw) of the resin is preferably 2000 to 2000000.
- the upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less.
- the lower limit is preferably 3000 or more, and more preferably 5000 or more.
- Examples of the resin include (meth) acrylic resin, epoxy resin, en-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, and polyimide resin.
- Examples thereof include polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, and styrene resin.
- Examples of the epoxy resin include polymer-type compounds among the compounds exemplified as the epoxy compounds described in the above-mentioned section of polymerizable compounds.
- Examples of commercially available cyclic olefin resins include ARTON F4520 (manufactured by JSR Corporation).
- the resin described in Japanese Patent Application Laid-Open No. 2017-066240 can also be used, and the contents thereof are incorporated in the present specification. Further, a resin having a fluorene skeleton can also be used.
- the resin used in the present invention may have an acid group.
- the acid group include a carboxyl group, a phosphoric acid group, a sulfo group, a phenolic hydroxy group and the like, and a carboxyl group is preferable. These acid groups may be only one kind or two or more kinds.
- the resin having an acid group can also be used as an alkali-soluble resin.
- a polymer having a carboxyl group in the side chain is preferable.
- Specific examples include alkali-soluble methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and novolak resins.
- examples thereof include phenol resins, acidic cellulose derivatives having a carboxyl group in the side chain, and resins obtained by adding an acid anhydride to a polymer having a hydroxy group.
- a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin.
- Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, vinyl compounds and the like.
- alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and pentyl (meth) acrylate.
- Examples thereof include ⁇ -methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethylmethacrylate macromonomer and the like.
- N-substituted maleimide monomers described in JP-A-10-300922 for example, N-phenylmaleimide, N-cyclohexylmaleimide and the like can also be used.
- the other monomers copolymerizable with these (meth) acrylic acids may be only one kind or two or more kinds.
- the resin having an acid group may further contain a repeating unit having a polymerizable group.
- the content of the repeating unit having a polymerizable group in all the repeating units is preferably 10 to 90 mol%, and 20 to 20 to 90 mol%. It is more preferably 90 mol%, further preferably 20 to 85 mol%.
- the content of the repeating unit having an acid group in all the repeating units is preferably 1 to 50 mol%, more preferably 5 to 40 mol%, and preferably 5 to 30 mol%. More preferred.
- the resin having an acid group is a monomer containing a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as "ether dimer"). It is also preferable that the polymer contains repeating units derived from the components.
- R 1 and R 2 represent hydrocarbon groups having 1 to 25 carbon atoms, which may each independently have a hydrogen atom or a substituent.
- R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
- the description of JP-A-2010-168539 can be referred to.
- ether dimer for example, paragraph number 0317 of JP2013-209760A can be referred to, and this content is incorporated in the present specification.
- the ether dimer may be of only one type or of two or more types.
- the resin having an acid group may contain a repeating unit derived from the compound represented by the following formula (X).
- R 1 represents a hydrogen atom or a methyl group
- R 2 represents an alkylene group having 2 to 10 carbon atoms
- R 3 represents a hydrogen atom or a benzene ring having 1 to 20 carbon atoms.
- n represents an integer from 1 to 15.
- the acid value of the resin having an acid group is preferably 30 to 200 mgKOH / g.
- the lower limit is preferably 50 mgKOH / g or more, and more preferably 70 mgKOH / g or more.
- the upper limit is preferably 150 mgKOH / g or less, and more preferably 120 mgKOH / g or less.
- Examples of the resin having an acid group include a resin having the following structure.
- Me represents a methyl group.
- the composition of the present invention may also contain a resin as a dispersant.
- the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin).
- the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is larger than the amount of basic groups.
- the acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups accounts for 70 mol% or more when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%, and is substantially an acid. A resin consisting only of groups is more preferable.
- the acid group of the acidic dispersant (acidic resin) is preferably a carboxyl group.
- the acid value of the acidic dispersant (acidic resin) is preferably 40 to 105 mgKOH / g, more preferably 50 to 105 mgKOH / g, and even more preferably 60 to 105 mgKOH / g.
- the basic dispersant (basic resin) represents a resin in which the amount of basic groups is larger than the amount of acid groups.
- the basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol% when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%.
- the basic group contained in the basic dispersant is preferably an amino group.
- the dispersant is preferably an acidic dispersant (acidic resin).
- the resin used as the dispersant is also preferably a graft copolymer. Since the graft copolymer has an affinity with a solvent due to the graft chain, it is excellent in the dispersibility of the pigment and the dispersion stability after aging.
- the description in paragraphs 0025 to 0094 of JP2012-255128A can be referred to, and the content thereof is incorporated in the present specification.
- the resin used as the dispersant is an oligoimine-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain.
- the oligoimine-based dispersant has a structural unit having a partial structure X having a functional group of pKa14 or less, a side chain containing a side chain Y having 40 to 10,000 atoms, and a main chain and a side chain.
- a resin having a basic nitrogen atom on at least one of them is preferable.
- the basic nitrogen atom is not particularly limited as long as it is a nitrogen atom exhibiting basicity.
- the description in paragraphs 0102 to 0174 of JP2012-255128A can be referred to, and this content is incorporated in the present specification.
- the dispersant is also available as a commercially available product, and specific examples thereof include BYK2000 (manufactured by Big Chemie Japan Co., Ltd.). Further, the pigment dispersants described in paragraphs 0041 to 0130 of JP-A-2014-130338 can also be used, and the contents thereof are incorporated in the present specification. Further, the above-mentioned resin having an acid group or the like can also be used as a dispersant.
- the content of the resin having an amine value in the total amount of the resin contained in the curable composition is 30% by mass from the viewpoint of storage stability of the curable composition. It is preferably 20% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, and further preferably 1% by mass or less. It is more preferably 0.1% by mass or less, and particularly preferably 0.1% by mass or less.
- the content of the resin in the total solid content of the curable composition is preferably 0.1 to 50% by mass.
- the lower limit is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, and particularly preferably 10% by mass or more.
- the upper limit is more preferably 40% by mass or less, further preferably 30% by mass or less.
- the content of the resin having an amine value in the total solid content of the curable composition is preferably 30% by mass or less, preferably 20% by mass or less. Is more preferable, and 10% by mass or less is further preferable.
- the curable composition of the present invention contains substantially no resin having an amine value.
- the content of the resin having an amine value in the total solid content of the curable composition is 0.05% by mass or less. It is preferably 0.01% by mass or less, and particularly preferably does not contain a resin having an amine value.
- the curable composition of the present invention may contain only one type of resin, or may contain two or more types of resin. When two or more kinds are contained, it is preferable that the total amount thereof is within the above range.
- the mass ratio of the polymerizable compound to the resin is polymerizable.
- the compound / resin is preferably 0.4 to 1.4.
- the lower limit of the mass ratio is preferably 0.5 or more, more preferably 0.6 or more.
- the upper limit of the mass ratio is preferably 1.3 or less, more preferably 1.2 or less.
- the curable composition of the present invention can contain a photopolymerization initiator.
- the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator. It is preferable to select and use it according to the type of the polymerizable compound. When a radically polymerizable compound such as a compound having an ethylenically unsaturated bond-containing group is used as the polymerizable compound, it is preferable to use a photoradical polymerization initiator as the photopolymerization initiator.
- a photocationic polymerization initiator is not particularly limited and may be appropriately selected from known photopolymerization initiators.
- a compound having photosensitivity to light rays in the ultraviolet region to the visible region is preferable.
- the content of the photopolymerization initiator in the total solid content of the curable composition is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, still more preferably 1 to 20% by mass.
- the curable composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types of photopolymerization initiators. When two or more types of photopolymerization initiators are contained, the total amount thereof is preferably in the above range.
- Photoradical polymerization initiator examples include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole, oxime compounds, organic peroxides, and thio. Examples thereof include compounds, ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, and ⁇ -aminoketone compounds.
- halogenated hydrocarbon derivatives for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.
- acylphosphine compounds examples include hexaarylbiimidazole, oxime compounds, organic peroxides, and thio. Examples thereof include compounds, ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, and ⁇ -aminoketone compounds.
- the photopolymerization initiator is a trihalomethyltriazine compound, a benzyl dimethyl ketal compound, an ⁇ -hydroxyketone compound, an ⁇ -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, or a triarylimidazole.
- It is preferably a dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxaziazole compound and a 3-aryl substituted coumarin compound, and an oxime compound and an ⁇ -hydroxyketone compound.
- ⁇ -Aminoketone compound, and an acylphosphine compound are more preferable, and an oxime compound is further preferable.
- the photoradical polymerization initiator the compounds described in paragraphs 0065 to 0111 of JP-A-2014-130173 and JP-A-6301489, MATERIAL STAGE 37-60p, vol.
- ⁇ -hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), Irgacure 184, Irgacure 1173, Irgacare 1173, Irgacure29. (Manufactured by the company) and the like.
- Commercially available ⁇ -aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (above, IGM Resins BV), Irgacare 907, Irgacare 369, Irgacure 369, Irgacure 369, Irgar (Made) and so on.
- acylphosphine compounds examples include Omnirad 819, Omnirad TPO (above, manufactured by IGM Resins BV), Irgacure 819, and Irgacure TPO (above, manufactured by BASF).
- Examples of the oxime compound include the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-080068, and the compounds described in JP-A-2006-342166.
- oxime compound examples include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-Acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxycarbonyloxy Examples thereof include imino-1-phenylpropane-1-one.
- an oxime compound having a fluorene ring can also be used.
- Specific examples of the oxime compound having a fluorene ring include the compounds described in JP-A-2014-137466.
- an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used.
- Specific examples of such an oxime compound include the compounds described in International Publication No. 2013/083505.
- an oxime compound having a fluorine atom can also be used as the photoradical polymerization initiator.
- Specific examples of the oxime compound having a fluorine atom are described in the compounds described in JP-A-2010-262028, compounds 24, 36-40 described in JP-A-2014-500852, and JP-A-2013-164471. Compound (C-3) and the like.
- an oxime compound having a nitro group can be used as the photoradical polymerization initiator.
- the oxime compound having a nitro group is also preferably a dimer.
- Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP2013-114249A and paragraphs 0008-0012 and 0070-0079 of JP2014-137466. Examples thereof include the compound described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, ADEKA ARKULS NCI-831 (manufactured by ADEKA Corporation).
- an oxime compound having a benzofuran skeleton can also be used.
- Specific examples include OE-01 to OE-75 described in International Publication No. 2015/036910.
- an oxime compound in which a substituent having a hydroxy group is bonded to the carbazole skeleton can also be used.
- Examples of such a photopolymerization initiator include the compounds described in International Publication No. 2019/088055.
- the oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, and more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm.
- the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or a wavelength of 405 nm is preferably high, more preferably 1000 to 300,000, further preferably 2000 to 300,000, and more preferably 5000 to 200,000. It is particularly preferable to have.
- the molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).
- a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used as the photoradical polymerization initiator.
- two or more radicals are generated from one molecule of the photoradical polymerization initiator, so that good sensitivity can be obtained.
- the crystallinity is lowered, the solubility in a solvent or the like is improved, the precipitation is less likely to occur with time, and the stability of the curable composition with time is improved.
- Specific examples of the bifunctional or trifunctional or higher functional photo-radical polymerization initiators include JP-A-2010-527339, JP-A-2011-524436, International Publication No.
- the photoradical polymerization initiator contains an oxime compound and an ⁇ -aminoketone compound.
- the developability is improved and it is easy to form a pattern having excellent rectangularity.
- the ⁇ -aminoketone compound is preferably 50 to 600 parts by mass, more preferably 150 to 400 parts by mass with respect to 100 parts by mass of the oxime compound.
- the content of the photoradical polymerization initiator in the total solid content of the curable composition is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, still more preferably 1 to 20% by mass.
- the curable composition of the present invention may contain only one kind of photoradical polymerization initiator, or may contain two or more kinds of photoradical polymerization initiators. When two or more kinds of photoradical polymerization initiators are contained, the total amount thereof is preferably in the above range.
- Photocationic polymerization initiator examples include a photoacid generator.
- the photoacid generator include onium salt compounds such as diazonium salt, phosphonium salt, sulfonium salt, and iodonium salt, which are decomposed by light irradiation to generate acid, imide sulfonate, oxime sulfonate, diazodisulfone, disulfone, and o-nitrobenzyl.
- sulfonate compounds such as sulfonate.
- the content of the photocationic polymerization initiator in the total solid content of the curable composition is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, still more preferably 1 to 20% by mass.
- the curable composition of the present invention may contain only one type of photocationic polymerization initiator, or may contain two or more types of photocationic polymerization initiators. When two or more types of photocationic polymerization initiators are contained, the total amount thereof is preferably in the above range.
- the curable composition of the present invention can contain a polyfunctional thiol.
- a polyfunctional thiol is a compound having two or more thiol (SH) groups.
- the polyfunctional thiol acts as a chain transfer agent in the radical polymerization process after light irradiation and generates chile radicals that are less susceptible to polymerization inhibition by oxygen.
- the sensitivity can be increased.
- a polyfunctional aliphatic thiol in which the SH group is bonded to an aliphatic group such as methylene or ethylene group is preferable.
- polyfunctional thiol examples include hexanedithiol, decandithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropio.
- the content of polyfunctional thiol in the total solid content of the curable composition is preferably 0.1 to 20% by mass, more preferably 0.1 to 15% by mass, still more preferably 0.1 to 10% by mass.
- the curable composition of the present invention may contain only one type of polyfunctional thiol, or may contain two or more types of polyfunctional thiols. When two or more kinds are contained, it is preferable that the total amount thereof is within the above range.
- Epoxy resin curing agent When the curable composition of the present invention contains an epoxy resin, it is preferable that the curable composition further contains an epoxy resin curing agent.
- the epoxy resin curing agent include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and polyvalent carboxylic acids.
- a polyvalent carboxylic acid is preferable from the viewpoint of heat resistance and transparency of the cured product, and a compound having two or more carboxylic acid anhydride groups in the molecule is most preferable.
- Specific examples of the epoxy resin curing agent include butane diic acid.
- the content of the epoxy resin curing agent is preferably 0.01 to 20 parts by mass, more preferably 0.01 to 10 parts by mass, still more preferably 0.1 to 6.0 parts by mass with respect to 100 parts by mass of the epoxy resin. ..
- the curable composition of the present invention can further contain a pigment derivative.
- the pigment derivative include compounds having a structure in which an acid group or a basic group is bonded to the pigment skeleton.
- the pigment skeletons constituting the pigment derivatives include quinoline pigment skeleton, benzoimidazolone pigment skeleton, benzoisoindole pigment skeleton, benzothiazole pigment skeleton, inimium pigment skeleton, squarylium pigment skeleton, croconium pigment skeleton, oxonor pigment skeleton, and pyrolopyrrolop pigment.
- Examples of the acid group include a carboxyl group, a sulfo group, a carboxylic acid amide group, a sulfonic acid amide group, an imic acid group and salts thereof.
- a carboxylic acid amide group a group represented by -NHCOR X1 is preferable.
- the sulfonic acid amide group preferably a group represented by -NHSO 2 R X2.
- a group represented by -SO 2 NHSO 2 R X3 , -CONHSO 2 R X4 , -CONHCOR X5 or -SO 2 NHCOR X6 is preferable.
- RX1 to RX6 independently represent a hydrocarbon group or a heterocyclic group.
- Hydrocarbon or heterocyclic group R X1 ⁇ R X6 represents may further have a substituent.
- alkali metal ions Li + , Na + , K +, etc.
- alkaline earth metal ions Ca 2+ , Mg 2+, etc.
- ammonium ions imidazolium ions, pyridinium ions, etc.
- Examples include phosphonium ions.
- the basic group include an amino group, a pyridinyl group and a salt thereof, a salt of an ammonium group, and a phthalimide methyl group.
- the atom or atomic group constituting the salt include hydroxide ion, halogen ion, carboxylic acid ion, sulfonic acid ion, and phenoxide ion.
- pigment derivative examples include Japanese Patent Application Laid-Open No. 56-118462, Japanese Patent Application Laid-Open No. 63-264674, Japanese Patent Application Laid-Open No. 01-2170777, Japanese Patent Application Laid-Open No. 03-009961, and Japanese Patent Application Laid-Open No. 03-026767.
- the content of the pigment derivative is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the pigment.
- the lower limit is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more.
- the upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less.
- the curable composition of the present invention can contain a solvent.
- the solvent include organic solvents.
- the solvent is basically not particularly limited as long as it satisfies the solubility of each component and the coatability of the curable composition.
- organic solvents include, for example, esters, ethers, ketones, aromatic hydrocarbons, hydrocarbons and the like.
- paragraph No. 0223 of WO 2015/166779 can be referred to, the contents of which are incorporated herein by reference.
- an ester solvent substituted with a cyclic alkyl group and a ketone solvent substituted with a cyclic alkyl group can also be preferably used.
- hydrocarbon solvent having 5 to 30 carbon atoms can be preferably used.
- the hydrocarbon solvent may be a mixture of a linear compound and a branched compound, or may be a mixture of two or more compounds having different carbon atoms.
- Specific examples of the organic solvent include dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, and the like.
- Examples thereof include cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate, pentane, hexane, heptane, octane, nonane, decane, cyclopentane, cyclohexane and the like.
- the organic solvent may be used alone or in combination of two or more.
- 3-methoxy-N, N-dimethylpropanamide and 3-butoxy-N, N-dimethylpropanamide are also preferable from the viewpoint of improving solubility.
- aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as a solvent may need to be reduced for environmental reasons (for example, 50 mass ppm (parts per) with respect to the total amount of the organic solvent. Million) or less, 10 mass ppm or less, or 1 mass ppm or less).
- a solvent having a low metal content it is preferable to use a solvent having a low metal content, and the metal content of the solvent is preferably, for example, 10 mass ppb (parts per parts) or less. If necessary, a solvent of mass ppt (parts per parts) level may be used, and such a high-purity solvent is provided by, for example, Toyo Synthetic Co., Ltd. (The Chemical Daily, November 13, 2015).
- Examples of the method for removing impurities such as metals from the solvent include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter.
- the filter pore diameter of the filter used for filtration is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and even more preferably 3 ⁇ m or less.
- the filter material is preferably polytetrafluoroethylene, polyethylene or nylon.
- the solvent may contain isomers (compounds having the same number of atoms but different structures). Further, only one kind of isomer may be contained, or a plurality of kinds may be contained.
- the organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide.
- the content of the solvent is preferably 10 to 99% by mass with respect to the total amount of the curable composition of the present invention.
- the upper limit is preferably 95% by mass or less, more preferably 90% by mass or less.
- the lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, further preferably 60% by mass or more, and particularly preferably 70% by mass or more.
- the curable composition of the present invention can contain a polymerization inhibitor.
- the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), and the like. Examples thereof include 2,2'-methylenebis (4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxyamine salts (ammonium salt, first cerium salt, etc.). Of these, p-methoxyphenol is preferable.
- the content of the polymerization inhibitor in the total solid content of the curable composition is preferably 0.0001 to 5% by mass.
- the curable composition of the present invention can contain a silane coupling agent.
- the silane coupling agent means a silane compound having a hydrolyzable group and other functional groups.
- the hydrolyzable group refers to a substituent that is directly linked to a silicon atom and can form a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction.
- Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group and the like, and an alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group.
- Examples of the functional group other than the hydrolyzable group include a vinyl group, a (meth) acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group, an isocyanate group and a phenyl group.
- the (meth) acryloyl group and the epoxy group are preferable.
- Examples of the silane coupling agent include the compounds described in paragraphs 0018 to 0036 of JP2009-288703A and the compounds described in paragraphs 0056 to 0066 of JP2009-242604A. Incorporated into the specification.
- the content of the silane coupling agent in the total solid content of the curable composition is preferably 0.01 to 15.0% by mass, more preferably 0.05 to 10.0% by mass.
- the silane coupling agent may be only one type or two or more types. In the case of two or more types, the total amount is preferably in the above range.
- the curable composition of the present invention can contain a surfactant.
- a surfactant various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicon-based surfactant can be used.
- the surfactant include the surfactants described in paragraphs 0238 to 0245 of WO2015 / 166779, the contents of which are incorporated herein by reference.
- the surfactant is preferably a fluorine-based surfactant.
- a fluorine-based surfactant in the curable composition, the liquid properties (particularly, fluidity) can be further improved, and the liquid saving property can be further improved. It is also possible to form a film having a small thickness unevenness.
- the fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass.
- a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid saving property, and has good solubility in a curable composition.
- fluorine-based surfactant examples include the surfactants described in paragraphs 0060 to 0064 of Japanese Patent Application Laid-Open No. 2014-041318 (paragraphs 0060 to 0064 of the corresponding international publication No. 2014/017669), and Japanese Patent Application Laid-Open No. 2011-.
- the surfactants described in paragraphs 0117 to 0132 of JP 132503 are mentioned and their contents are incorporated herein by reference.
- Commercially available products of fluorine-based surfactants include, for example, Megafuck F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, MFS.
- the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and when heat is applied, the portion of the functional group containing the fluorine atom is cut and the fluorine atom is volatilized.
- fluorine-based surfactants include the Megafuck DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Megafuck. DS-21 can be mentioned.
- fluorine-based surfactant it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.
- a fluorine-based surfactant include the fluorine-based surfactants described in JP-A-2016-216602, the contents of which are incorporated in the present specification.
- a block polymer can also be used as the fluorine-based surfactant.
- the fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meth).
- a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used.
- the fluorine-containing surfactants described in paragraphs 0016 to 0037 of JP-A-2010-032698 and the following compounds are also exemplified as the fluorine-based surfactants used in the present invention.
- the weight average molecular weight of the above compounds is preferably 3000-50000, for example 14000.
- % indicating the ratio of the repeating unit is mol%.
- a fluorine-based surfactant a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used.
- the compounds described in paragraphs 0050 to 0090 and paragraph numbers 0289 to 0295 of JP2010-164965, Megafuck RS-101, RS-102, RS-718K manufactured by DIC Corporation, RS-72-K and the like can be mentioned.
- the fluorine-based surfactant the compounds described in paragraphs 0015 to 0158 of JP2015-117327A can also be used.
- Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, etc.
- the content of the surfactant in the total solid content of the curable composition is preferably 0.001% by mass to 5.0% by mass, more preferably 0.005 to 3.0% by mass.
- the surfactant may be only one kind or two or more kinds. In the case of two or more types, the total amount is preferably in the above range.
- the curable composition of the present invention can contain an ultraviolet absorber.
- an ultraviolet absorber a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, an indol compound, a triazine compound and the like can be used. Examples of such compounds include paragraph numbers 0038 to 0052 of JP2009-217221A, paragraph numbers 0052 to 0072 of JP2012-208374A, and paragraph numbers 0317 to 0334 of JP2013-068814.
- Examples include the compounds described in paragraphs 0061 to 0080 of JP 2016-162946, the contents of which are incorporated herein.
- Specific examples of the ultraviolet absorber include compounds having the following structures. Examples of commercially available ultraviolet absorbers include UV-503 (manufactured by Daito Kagaku Co., Ltd.). Examples of the benzotriazole compound include the MYUA series made by Miyoshi Oil & Fat Co., Ltd. (The Chemical Daily, February 1, 2016). Further, as the ultraviolet absorber, the compounds described in paragraphs 0049 to 0059 of Japanese Patent No. 6268967 can also be used.
- the content of the ultraviolet absorber in the total solid content of the curable composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass. Only one kind of ultraviolet absorber may be used, or two or more kinds may be used. When two or more types are used, the total amount is preferably in the above range.
- the curable composition of the present invention can contain an antioxidant.
- the antioxidant include phenol compounds, phosphite ester compounds, thioether compounds and the like.
- the phenol compound any phenol compound known as a phenolic antioxidant can be used.
- Preferred phenolic compounds include hindered phenolic compounds.
- a compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxy group is preferable.
- a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable.
- the antioxidant a compound having a phenol group and a phosphite ester group in the same molecule is also preferable.
- a phosphorus-based antioxidant can also be preferably used.
- a phosphorus-based antioxidant tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosfepine-6 -Il] Oxy] Ethyl] amine, Tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosfepin-2-yl] ) Oxy] ethyl] amine, ethylbis phosphite (2,4-di-tert-butyl-6-methylphenyl) and the like.
- antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (above, manufactured by ADEKA Corporation) and the like. Further, as the antioxidant, the polyfunctional hindered amine antioxidant described in International Publication No. 2017/006600 can also be used.
- the content of the antioxidant in the total solid content of the curable composition is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, the total amount is preferably in the above range.
- the curable composition of the present invention can be used as a sensitizer, a curing accelerator, a filler, a thermosetting accelerator, a plasticizer and other auxiliary agents (for example, conductive particles, a filler, a defoaming agent), if necessary. , Flame retardant, leveling agent, peeling accelerator, fragrance, surface tension modifier, chain transfer agent, etc.) may be contained. By appropriately containing these components, properties such as film physical characteristics can be adjusted. These components are described in, for example, paragraph No. 0183 and subsequent paragraphs of JP2012-003225A (paragraph number 0237 of the corresponding US Patent Application Publication No. 2013/0034812), paragraphs of JP-A-2008-250074.
- the curable composition of the present invention may contain a latent antioxidant, if necessary.
- the latent antioxidant is a compound in which the site that functions as an antioxidant is protected by a protecting group, and is heated at 100 to 250 ° C. or at 80 to 200 ° C. in the presence of an acid / base catalyst.
- Examples of the latent antioxidant include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219.
- Examples of commercially available products include ADEKA ARKULS GPA-5001 (manufactured by ADEKA Corporation) and the like.
- the storage container for the curable composition of the present invention is not particularly limited, and a known storage container can be used.
- a storage container a multi-layer bottle composed of 6 types and 6 layers of resin and 6 types of resin have a 7-layer structure for the purpose of suppressing impurities from being mixed into raw materials and curable compositions. It is also preferable to use a bottle. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.
- the inner wall of the container is preferably made of glass or stainless steel for the purpose of preventing metal elution from the inner wall of the container, enhancing the storage stability of the curable composition, and suppressing deterioration of components.
- the curable composition of the present invention can be prepared by mixing the above-mentioned components.
- all the components may be dissolved or dispersed in a solvent at the same time to prepare a curable composition, or if necessary, two or more solutions in which each component is appropriately blended or
- the dispersion may be prepared in advance and mixed at the time of use (at the time of application) to prepare a curable composition.
- the curable composition of the present invention contains a pigment
- the mechanical force used for dispersing the pigment includes compression, squeezing, impact, shearing, cavitation and the like. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high speed impellers, sand grinders, flow jet mixers, high pressure wet atomization, ultrasonic dispersion and the like.
- the process and disperser for dispersing pigments are "Dispersion Technology Complete Works, Published by Information Organization Co., Ltd., July 15, 2005" and "Dispersion technology centered on suspension (solid / liquid dispersion system) and industrial. Practical application The process and disperser described in Paragraph No.
- the pigment may be miniaturized in the salt milling step.
- the materials, equipment, processing conditions, etc. used in the salt milling step for example, the descriptions in JP-A-2015-194521 and JP-A-2012-046629 can be referred to.
- any filter that has been conventionally used for filtration or the like can be used without particular limitation.
- a fluororesin such as polytetrafluoroethylene (PTFE), a polyamide resin such as nylon (for example, nylon-6, nylon-6,6), and a polyolefin resin such as polyethylene and polypropylene (PP) (high density, ultrahigh molecular weight).
- PP polypropylene
- a filter using a material such as (including the polyolefin resin of) is mentioned.
- polypropylene (including high-density polypropylene) and nylon are preferable.
- the pore size of the filter is preferably 0.01 to 7.0 ⁇ m, more preferably 0.01 to 3.0 ⁇ m, and even more preferably 0.05 to 0.5 ⁇ m. If the pore size of the filter is within the above range, fine foreign matter can be removed more reliably.
- the nominal value of the filter manufacturer can be referred to.
- various filters provided by Nippon Pole Co., Ltd. (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), KITZ Microfilter Co., Ltd., etc. can be used.
- fibrous filter medium examples include polypropylene fiber, nylon fiber, glass fiber and the like.
- examples of commercially available products include SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.) and SHPX type series (SHPX003, etc.) manufactured by Roki Techno Co., Ltd.
- filters for example, a first filter and a second filter
- the filtration with each filter may be performed only once or twice or more.
- filters having different pore diameters may be combined within the above-mentioned range.
- the filtration with the first filter may be performed only on the dispersion liquid, and after mixing the other components, the filtration may be performed with the second filter.
- the film of the present invention is a film obtained from the above-mentioned composition of the present invention.
- the film of the present invention can be preferably used as an infrared transmission filter.
- the film thickness of the film of the present invention is not particularly limited, but is preferably 0.1 to 50 ⁇ m, more preferably 0.1 to 20 ⁇ m, and even more preferably 0.5 to 10 ⁇ m.
- the film of the present invention preferably has the spectral characteristics of any of the following aspects (1) to (12).
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction.
- the minimum value of the transmittance in the wavelength range of 1000 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 830 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 940 nm.
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction.
- the minimum value of the transmittance in the wavelength range of 1100 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 950 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1040 nm.
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1050 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction.
- the minimum value of the transmittance in the wavelength range of 1200 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, it is possible to obtain a film capable of transmitting infrared rays having a wavelength of more than 1140 nm by blocking light in the wavelength range of 400 to 1050 nm.
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1150 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction.
- the minimum value of the transmittance in the wavelength range of 1300 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1150 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1240 nm.
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1250 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction.
- the minimum value of the transmittance in the wavelength range of 1400 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1250 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1340 nm.
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1350 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction.
- the minimum value of the transmittance in the wavelength range of 1500 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1350 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1440 nm.
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1450 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction.
- the minimum value of the transmittance in the wavelength range of 1600 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1450 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1540 nm.
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1550 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction.
- the minimum value of the transmittance in the wavelength range of 1700 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1550 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1640 nm.
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1650 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction.
- the minimum value of the transmittance in the wavelength range of 1800 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1650 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1740 nm.
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1750 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction.
- the minimum value of the transmittance in the wavelength range of 1900 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1750 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1840 nm.
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1850 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction.
- the minimum value of the transmittance in the wavelength range of 2000 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1850 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1940 nm.
- the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction.
- the minimum value of the transmittance in the wavelength range of 2100 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1950 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 2040 nm.
- the film of the present invention can be produced through a step of applying the curable composition of the present invention.
- the curable composition is applied onto a support.
- the support include a substrate made of a material such as silicon, non-alkali glass, soda glass, Pyrex (registered trademark) glass, and quartz glass.
- An organic film, an inorganic film, or the like may be formed on these substrates.
- the material of the organic film include the resin described in the section of the curable composition described above.
- a substrate made of resin can also be used as the support.
- the support may be formed with a charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like.
- the support may be formed with a black matrix that separates each pixel.
- the support may be provided with a base layer for improving the adhesion with the upper layer, preventing the diffusion of substances, or flattening the surface of the substrate.
- the surface contact angle of the base layer is preferably 20 to 70 ° when measured with diiodomethane. Further, it is preferably 30 to 80 ° when measured with water. When the surface contact angle of the base layer is within the above range, the curable composition has good coatability.
- the surface contact angle of the base layer can be adjusted by, for example, adding a surfactant.
- a known method can be used as a method for applying the curable composition.
- a dropping method drop casting
- a slit coating method for example, a spray method; a roll coating method; a rotary coating method (spin coating method); a casting coating method; a slit and spin method; a pre-wet method (for example, JP-A-2009-145395).
- Inkjet for example, on-demand method, piezo method, thermal method
- ejection system printing such as nozzle jet, flexo printing, screen printing, gravure printing, reverse offset printing, metal mask printing, etc.
- Various printing methods transfer method using a mold or the like; nano-imprint method and the like.
- the method of application to inkjet is not particularly limited, and is, for example, the method shown in "Expandable and usable inkjet-infinite possibilities seen in patents-, published in February 2005, Sumi Betechno Research" (especially from page 115). (Page 133), and the methods described in JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, JP-A-2006-169325, and the like. Can be mentioned. Further, the application by the spin coating method is preferably performed at a rotation speed of 1000 to 2000 rpm.
- the curable composition layer formed by applying the curable composition may be dried (prebaked). Prebaking may not be required if the pattern is formed by a low temperature process.
- the prebaking temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and even more preferably 110 ° C. or lower.
- the lower limit can be, for example, 50 ° C. or higher, or 80 ° C. or higher.
- the prebaking time is preferably 10 seconds to 3000 seconds, more preferably 40 to 2500 seconds, and even more preferably 80 to 220 seconds. Drying can be performed on a hot plate, an oven, or the like.
- the film manufacturing method further includes a step of forming a pattern.
- the pattern forming method include a pattern forming method using a photolithography method and a pattern forming method using a dry etching method, and a pattern forming method using a photolithography method is preferable.
- the film of the present invention is used as a flat film, it is not necessary to perform the step of forming the pattern.
- the process of forming the pattern will be described in detail.
- the pattern forming method in the photolithography method includes a step of exposing the curable composition layer formed by applying the curable composition of the present invention in a pattern (exposure step) and a curable composition of an unexposed portion. It is preferable to include a step of developing and removing the layer to form a pattern (development step). If necessary, a step of baking the developed pattern (post-baking step) may be provided. Hereinafter, each step will be described.
- the curable composition layer is exposed in a pattern.
- a pattern exposure can be performed by exposing the curable composition layer through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like.
- the exposed portion can be cured.
- radiation (light) that can be used for exposure include g-line and i-line.
- light having a wavelength of 300 nm or less preferably light having a wavelength of 180 to 300 nm
- Examples of the light having a wavelength of 300 nm or less include KrF line (wavelength 248 nm) and ArF line (wavelength 193 nm), and KrF line (wavelength 248 nm) is preferable.
- pulse exposure is an exposure method of a method of repeatedly irradiating and pausing light in a cycle of a short time (for example, a millisecond level or less).
- Irradiation dose for example, preferably 0.03 ⁇ 2.5J / cm 2, more preferably 0.05 ⁇ 1.0J / cm 2, most preferably 0.08 ⁇ 0.5J / cm 2 ..
- the oxygen concentration at the time of exposure can be appropriately selected. For example, it may be exposed in the atmosphere, or it may be exposed in a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, substantially anoxic), and the oxygen concentration is high. Exposure may be carried out in a high oxygen atmosphere exceeding 21% by volume (for example, 22% by volume, 30% by volume, 50% by volume). Further, the exposure illuminance can be appropriately set and is preferably selected from the range of 1000 to 100,000 W / m 2. Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10000 W / m 2 at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20000W / m 2.
- the curable composition layer in the unexposed portion of the curable composition layer after exposure is developed and removed to form a pattern.
- Development and removal of the curable composition layer in the unexposed portion can be performed using a developing solution.
- the curable composition layer of the unexposed portion in the exposure step is eluted in the developer, and only the photocured portion remains on the support.
- the temperature of the developing solution is preferably, for example, 20 to 30 ° C.
- the development time is preferably 20 to 180 seconds. Further, in order to improve the residue removability, the steps of shaking off the developing solution every 60 seconds and further supplying a new developing solution may be repeated several times.
- Examples of the developing solution include organic solvents and alkaline developing solutions, and alkaline developing solutions are preferably used.
- the alkaline developer an alkaline aqueous solution (alkaline developer) obtained by diluting an alkaline agent with pure water is preferable.
- the alkaline agent include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide.
- Ethyltrimethylammonium hydroxide Ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene and other organic substances.
- alkaline compounds examples include alkaline compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate and sodium metasilicate.
- the alkaline agent a compound having a large molecular weight is preferable in terms of environment and safety.
- the concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass.
- the developer may further contain a surfactant.
- the surfactant include the above-mentioned surfactants, and nonionic surfactants are preferable.
- the developer may be once produced as a concentrated solution and diluted to a concentration required for use from the viewpoint of convenience of transfer and storage.
- the dilution ratio is not particularly limited, but can be set in the range of, for example, 1.5 to 100 times.
- the rinsing is performed by supplying the rinsing liquid to the developed curable composition layer while rotating the support on which the developed curable composition layer is formed. It is also preferable to move the nozzle for discharging the rinse liquid from the central portion of the support to the peripheral edge of the support. At this time, when moving the nozzle from the central portion of the support to the peripheral portion, the nozzle may be moved while gradually reducing the moving speed. By rinsing in this way, in-plane variation of rinsing can be suppressed. Further, the same effect can be obtained by gradually reducing the rotation speed of the support while moving the nozzle from the center to the peripheral edge of the support.
- Additional exposure treatment and post-baking are post-development curing treatments to complete the curing.
- the heating temperature in the post-baking is, for example, preferably 100 to 240 ° C, more preferably 200 to 240 ° C.
- Post-baking can be performed on the developed film in a continuous or batch manner using a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater so as to meet the above conditions. ..
- the light used for the exposure is preferably light having a wavelength of 400 nm or less. Further, the additional exposure process may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.
- the curable composition layer formed by applying the curable composition of the present invention on a support is cured to form a cured product layer, and then on the cured product layer.
- a patterned resist layer is formed, and then the cured product layer is dry-etched with an etching gas using the patterned resist layer as a mask.
- the description in paragraphs 0010 to 0067 of JP2013-064993A can be referred to, and this content is incorporated in the present specification.
- the infrared transmission filter of the present invention has the above-mentioned film of the present invention.
- the infrared transmission filter of the present invention can also be used in combination with a color filter containing a chromatic colorant.
- the color filter can be produced by using a coloring composition containing a chromatic colorant.
- the infrared transmission filter of the present invention has pixels of the film of the present invention and pixels selected from red, green, blue, magenta, yellow, cyan, black and colorless.
- the solid-state image sensor of the present invention includes the above-mentioned film of the present invention.
- the configuration of the solid-state image sensor is not particularly limited as long as it has the film of the present invention and functions as a solid-state image sensor. For example, the following configuration can be mentioned.
- a transfer electrode formed of a plurality of photodiodes forming the light receiving area of the solid-state image sensor and polysilicon or the like is provided, and from tungsten or the like in which only the light receiving portion of the photodiode is opened on the photodiode and the transfer electrode.
- the present invention has a light-shielding film to be formed, a device protective film formed of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and a photodiode light receiving portion, and the present invention is provided on the device protective film. It is a configuration having a membrane in.
- a configuration having a condensing means for example, a microlens or the like; the same applies hereinafter
- the color filter may have a structure in which a film forming each pixel is embedded in a space partitioned by a partition wall, for example, in a grid pattern.
- the partition wall in this case preferably has a lower refractive index than each pixel. Examples of the image pickup apparatus having such a structure include the apparatus described in JP-A-2012-227478 and JP-A-2014-179757.
- the infrared sensor of the present invention includes the above-mentioned film of the present invention.
- the configuration of the infrared sensor is not particularly limited as long as it functions as an infrared sensor.
- an embodiment of the infrared sensor of the present invention will be described with reference to the drawings.
- reference numeral 110 is a solid-state image sensor.
- the image pickup region provided on the solid-state image sensor 110 includes an infrared cut filter 111 and an infrared transmission filter 114. Further, a color filter 112 is laminated on the infrared cut filter 111.
- a microlens 115 is arranged on the incident light h ⁇ side of the color filter 112 and the infrared transmission filter 114.
- the flattening layer 116 is formed so as to cover the microlens 115.
- the infrared cut filter 111 is a filter that transmits light in the visible light region (for example, light having a wavelength of 400 to 700 nm) and shields light in the infrared region.
- the color filter 112 is a color filter on which pixels that transmit and absorb light of a specific wavelength in the visible region are formed, and is not particularly limited, and a conventionally known color filter for pixel formation can be used. For example, a color filter in which red (R), green (G), and blue (B) pixels are formed is used. For example, the description in paragraphs 0214 to 0263 of JP2014-043556 can be referred to, and this content is incorporated in the present specification.
- the infrared transmission filter 114 is a filter that has visible light shielding properties and transmits infrared rays of a specific wavelength.
- an infrared cut filter (another infrared cut filter) different from the infrared cut filter 111 may be further arranged on the flattening layer 116.
- Other infrared cut filters include those having a copper-containing layer and / or a dielectric multilayer film. These details include those mentioned above. Further, as another infrared cut filter, a dual bandpass filter may be used.
- the color filter 112 is provided on the incident light h ⁇ side of the infrared cut filter 111, but the order of the infrared cut filter 111 and the color filter 112 is changed to cut infrared rays.
- the filter 111 may be provided on the incident light h ⁇ side of the color filter 112.
- the infrared cut filter 111 and the color filter 112 are laminated adjacent to each other, but both filters do not necessarily have to be adjacent to each other, and another layer is provided between them. Is also good.
- another infrared transmission filter having a spectral characteristic different from that of the infrared transmission filter 114 may be further provided.
- the film of the present invention can also be used in an image display device such as a liquid crystal display device or an organic electroluminescence (organic EL) display device.
- an image display device such as a liquid crystal display device or an organic electroluminescence (organic EL) display device.
- an image display device such as a liquid crystal display device or an organic electroluminescence (organic EL) display device.
- an image display device such as a liquid crystal display device or an organic electroluminescence (organic EL) display device.
- electroluminescence (organic EL) display device for details on the definition of display devices and the details of each display device, see, for example, “Electronic Display Device (Akio Sasaki, Kogyo Chosakai Co., Ltd., 1990)", “Display Device (Junaki Ibuki, Sangyo Tosho Co., Ltd.)” (Issued in the first year) ”and so on.
- the liquid crystal display device is described in, for example, “Next
- the image display device may be an image display device having a white organic EL element as the display element.
- the white organic EL element preferably has a tandem structure.
- Japanese Patent Application Laid-Open No. 2003-045676 supervised by Akiyoshi Mikami, "Frontiers of Organic EL Technology Development-High Brightness, High Precision, Long Life, Know-how Collection-", Technical Information Association, It is described on pages 326-328, 2008 and the like.
- the spectrum of white light emitted by the organic EL device preferably has strong maximum emission peaks in the blue region (430 nm-485 nm), the green region (530 nm-580 nm), and the yellow region (580 nm-620 nm). In addition to these emission peaks, it is more preferable to have a maximum emission peak in the red region (650 nm-700 nm).
- ⁇ Measurement of maximum absorption wavelength of quantum dots For the measurement of the maximum absorption wavelength of the quantum dots, a toluene solution of 10 mg / mL of the quantum dots was prepared, and the absorbance of this solution was measured using an ultraviolet-visible-near-infrared spectrophotometer.
- Quantum dot dispersion liquid [Quantum dot dispersion having a maximum absorption wavelength in the wavelength range of 700 to 2000 nm]
- QD-900 PbS quantum dot dispersion liquid (octane solution having a PbS quantum dot concentration of 10% by mass) in which oleic acid is coordinated as a ligand on the surface of PbS quantum dots having an average primary particle diameter of 3.2 nm.
- the maximum absorption wavelength of the PbS quantum dots was 900 nm.
- QD-1000 PbS quantum dot dispersion liquid (octane solution having a PbS quantum dot concentration of 10% by mass) in which oleic acid is coordinated as a ligand on the surface of PbS quantum dots having an average primary particle diameter of 3.5 nm.
- the maximum absorption wavelength of the PbS quantum dots was 1000 nm.
- QD-1100 PbS quantum dot dispersion liquid (octane solution having a PbS quantum dot concentration of 10% by mass) in which oleic acid is coordinated as a ligand on the surface of PbS quantum dots having an average primary particle diameter of 4.0 nm.
- the maximum absorption wavelength of the PbS quantum dots was 1100 nm.
- QD-1200 PbS quantum dot dispersion liquid (octane solution having a PbS quantum dot concentration of 10% by mass) in which oleic acid is coordinated as a ligand on the surface of PbS quantum dots having an average primary particle diameter of 4.5 nm.
- the maximum absorption wavelength of the PbS quantum dots was 1200 nm.
- QD-1300 PbS quantum dot dispersion liquid (octane solution having a PbS quantum dot concentration of 10% by mass) in which oleic acid is coordinated as a ligand on the surface of PbS quantum dots having an average primary particle diameter of 5.0 nm.
- the maximum absorption wavelength of the PbS quantum dots was 1300 nm.
- QD-1400 PbS quantum dot dispersion liquid (octane solution having a PbS quantum dot concentration of 10% by mass) in which oleic acid is coordinated as a ligand on the surface of PbS quantum dots having an average primary particle diameter of 5.5 nm.
- the maximum absorption wavelength of the PbS quantum dots was 1400 nm.
- QD-1500 PbS quantum dot dispersion liquid (octane solution having a PbS quantum dot concentration of 10% by mass) in which oleic acid is coordinated as a ligand on the surface of PbS quantum dots having an average primary particle diameter of 6.0 nm.
- the maximum absorption wavelength of the PbS quantum dots was 1500 nm.
- QD-1600 PbS quantum dot dispersion liquid (octane solution having a PbS quantum dot concentration of 10% by mass) in which oleic acid is coordinated as a ligand on the surface of PbS quantum dots having an average primary particle diameter of 6.5 nm.
- the maximum absorption wavelength of the PbS quantum dots was 1600 nm.
- QD-1700 PbS quantum dot dispersion liquid (octane solution having a PbS quantum dot concentration of 10% by mass) in which oleic acid is coordinated as a ligand on the surface of PbS quantum dots having an average primary particle diameter of 7.0 nm.
- the maximum absorption wavelength of the PbS quantum dots was 1700 nm.
- QD-1800 PbS quantum dot dispersion liquid (octane solution having a PbS quantum dot concentration of 10% by mass) in which oleic acid is coordinated as a ligand on the surface of PbS quantum dots having an average primary particle diameter of 8.0 nm.
- the maximum absorption wavelength of the PbS quantum dots was 1800 nm.
- QD-1900 PbS quantum dot dispersion liquid (octane solution having a PbS quantum dot concentration of 10% by mass) in which oleic acid is coordinated as a ligand on the surface of PbS quantum dots having an average primary particle diameter of 8.5 nm.
- the maximum absorption wavelength of the PbS quantum dots was 1900 nm.
- QD-2000 PbS quantum dot dispersion liquid (octane solution having a PbS quantum dot concentration of 10% by mass) in which oleic acid is coordinated as a ligand on the surface of PbS quantum dots having an average primary particle diameter of 9.0 nm.
- the maximum absorption wavelength of PbS quantum dots was 2000 nm.
- QD-450 PbS quantum dot dispersion liquid (PbS quantum dot concentration 10% by mass) in which oleic acid is coordinated as a ligand on the surface of perovskite (CsPb (Cl / Br) 3) quantum dots with an average primary particle diameter of 7 nm. solution).
- the maximum absorption wavelength of perovskite quantum dots was 450 nm.
- C-1 A compound having the following structure (organic coloring material having a maximum absorption wavelength in the range of wavelengths exceeding 700 nm and 1400 nm or less)
- C-2 A compound having the following structure (organic coloring material having a maximum absorption wavelength in the range of wavelengths exceeding 700 nm and 1400 nm or less)
- I-1 Irgacure OXE01 (manufactured by BASF)
- I-2 Compound with the following structure
- I-3 Omnirad 907 (manufactured by IGM Resins BV)
- Each curable composition was spin-coated on a glass substrate so that the film thickness after post-baking was 1.0 ⁇ m. Then, using a hot plate, it was heated at 100 ° C. for 120 seconds. Next, a film was formed by heat treatment (post-baking) at 200 ° C. for 300 seconds using a hot plate. Place the obtained film on a piece of paper on which characters (character "A") with a font size of 9 to 20 points (pt) are written, observe the characters from above the film, and visually identify the characters. The visible shading property was evaluated by. In addition, the spectrum of the obtained film was measured using an ultraviolet-visible near-infrared spectrophotometer to evaluate the infrared transparency.
- Unidentifiable 3 Characters on the back side of the film can be identified when the font size of the characters is 15 pt, but characters on the back side of the film cannot be identified when the font size of the characters is 10 pt 2: Membrane when the font size of the characters is 10 pt Characters on the back side can be identified, but characters on the back side of the film cannot be identified when the font size of the characters is 9pt 1: Characters on the back side of the film can be identified even if the font size of the characters is 9pt.
- Transmittance at 2200 nm is 70% or more 4: Transmittance at 2200 nm is 65% or more and less than 70% 3: Transmittance at 2200 nm is 60% or more and less than 65% 2: Transmittance at 2200 nm is 50% or more and less than 60% 1 : Transmittance at 2200 nm is 0% or more and less than 50%
- the curable composition of the example had high visible light-shielding property and excellent infrared transparency. Further, the same effect can be obtained by mixing the solvent S-1 and the solvent S-2. Further, the curable compositions of Examples 1 to 54 were spin-coated on a glass substrate so that the film thickness after post-baking was 1.0 ⁇ m. Then, using a hot plate, it was heated at 100 ° C. for 120 seconds. Next, a film was formed by heat treatment (post-baking) at 200 ° C. for 300 seconds using a hot plate.
- the minimum absorbance A in the wavelength range of 400 to 650 nm and the absorbance B in the wavelength 2200 nm were measured, respectively, and the minimum absorbance A in the wavelength range of 400 to 650 nm and the absorbance B in the wavelength 2200 nm were measured.
- the ratio A / B minimum value of absorbance A in the wavelength range of 400 to 650 nm / absorbance B in the wavelength range of 2200 nm
- the film obtained by using the curable compositions of Examples 1, 14, 15, 28 to 36, 38, 40 to 42, 53 and 54 shields light having a wavelength of 400 to 1000 nm and has a wavelength of 1100 nm or more. It was intended to transmit light of the same wavelength. Further, the film obtained by using the curable compositions of Examples 2, 12, 16 and 43 shields light having a wavelength of 400 to 1100 nm and transmits light having a wavelength of 1200 nm or more. Further, the film obtained by using the curable compositions of Examples 3, 17, and 44 shields light having a wavelength of 400 to 1200 nm and transmits light having a wavelength of 1300 nm or more.
- the films obtained by using the curable compositions of Examples 4, 18 and 45 shielded light having a wavelength of 400 to 1300 nm and transmitted light having a wavelength of 1400 nm or more. Further, the film obtained by using the curable composition of Examples 5, 13, 19, 26, 27, 37, 39, 46 blocks light having a wavelength of 400 to 1400 nm, and light having a wavelength of 1500 nm or more. Was to be transmitted. Further, the film obtained by using the curable compositions of Examples 6, 20 and 47 shields light having a wavelength of 400 to 1500 nm and transmits light having a wavelength of 1600 nm or more.
- the film obtained by using the curable compositions of Examples 7, 21, and 48 shields light having a wavelength of 400 to 1600 nm and transmits light having a wavelength of 1700 nm or more. Further, the film obtained by using the curable compositions of Examples 8, 22, and 49 shields light having a wavelength of 400 to 1700 nm and transmits light having a wavelength of 1800 nm or more. Further, the film obtained by using the curable compositions of Examples 9, 23 and 50 shields light having a wavelength of 400 to 1800 nm and transmits light having a wavelength of 1900 nm or more.
- the film obtained by using the curable compositions of Examples 10, 24 and 51 shields light having a wavelength of 400 to 1900 nm and transmits light having a wavelength of 2000 nm or more. Further, the films obtained by using the curable compositions of Examples 11, 25 and 52 shielded light having a wavelength of 400 to 2000 nm and transmitted light having a wavelength of 2100 nm or more.
- 110 Solid-state image sensor
- 111 Infrared cut filter
- 112 Color filter
- 114 Infrared transmission filter
- 115 Microlens
- 116 Flattening layer
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Abstract
Description
本発明は、赤外線透過フィルタなどの製造に適した硬化性組成物および、前述の硬化性組成物を用いた膜に関する。また、赤外線透過フィルタ、固体撮像素子および赤外線センサに関する。 The present invention relates to a curable composition suitable for producing an infrared transmission filter or the like, and a film using the above-mentioned curable composition. It also relates to an infrared transmission filter, a solid-state image sensor, and an infrared sensor.
固体撮像素子は、様々な用途で光センサとして活用されている。例えば、赤外線は可視光線に比べて波長が長いので散乱しにくく、距離計測や、3次元計測などにも活用可能である。また、赤外線は人間、動物などの目に見えないので、夜間に被写体を赤外線光源で照らしても被写体に気付かれることなく、夜行性の野生動物を撮影する用途、防犯用途として相手を刺激せずに撮影することにも使用可能である。このように、赤外線に感知する光センサ(赤外線センサ)は、様々な用途に展開が可能であり、赤外線センサに用いることができる膜の開発が望まれている。 The solid-state image sensor is used as an optical sensor in various applications. For example, infrared rays have a longer wavelength than visible light, so they are less likely to scatter, and can be used for distance measurement and three-dimensional measurement. In addition, since infrared rays are invisible to humans and animals, even if the subject is illuminated with an infrared light source at night, the subject will not be noticed, and it will not stimulate the other party for shooting nocturnal wild animals or for crime prevention. It can also be used for shooting. As described above, the optical sensor (infrared sensor) that senses infrared rays can be developed for various purposes, and it is desired to develop a film that can be used for the infrared sensor.
特許文献1には、赤外線を透過させて可視光を遮光する色材と、赤外線吸収剤と、硬化性化合物とを含む組成物であって、赤外線吸収剤は、波長1000nmを超え1200nm以下の範囲の光を遮光する材料を含み、上記組成物の波長400~1100nmの範囲における吸光度の最小値Aと、波長1400~1500nmの範囲における吸光度の最大値Bとの比であるA/Bが4.5以上である、組成物が記載されている。 Patent Document 1 describes a composition containing a coloring material that transmits infrared rays to block visible light, an infrared absorber, and a curable compound, and the infrared absorber has a wavelength in the range of more than 1000 nm and less than 1200 nm. A / B is the ratio of the minimum value A of the absorbance of the above composition in the wavelength range of 400 to 1100 nm to the maximum value B of the absorbance in the wavelength range of 1400 to 1500 nm. Compositions of 5 or more are described.
このように、近年においては、可視光を遮光して、赤外線を透過させる膜について種々の検討が進められている。 As described above, in recent years, various studies have been conducted on a film that blocks visible light and transmits infrared rays.
よって、本発明の目的は、可視光由来のノイズが少ない状態で赤外線を透過可能な膜を形成できる新規な硬化性組成物を提供することを目的とする。また、膜、赤外線透過フィルタ、固体撮像素子および赤外線センサを提供することを目的とする。 Therefore, an object of the present invention is to provide a novel curable composition capable of forming a film capable of transmitting infrared rays in a state where there is little noise derived from visible light. It is also an object of the present invention to provide a film, an infrared transmission filter, a solid-state image sensor, and an infrared sensor.
本発明は、以下を提供する。
<1> 波長700~2000nmの範囲に極大吸収波長を有する量子ドットと、硬化性化合物とを含む硬化性組成物であって、
上記硬化性組成物の全固形分中に上記量子ドットを5質量%以上含有する、硬化性組成物。
<2> 上記量子ドットがPb原子を含む、<1>に記載の硬化性組成物。
<3> 上記量子ドットの平均一次粒子径が1~10nmである、<1>または<2>に記載の硬化性組成物。
<4> 上記量子ドットが、
波長700~2000nmの範囲に極大吸収波長を有する第1の量子ドットと、
上記第1の量子ドットの極大吸収波長よりも長波長側に極大吸収波長を有する第2の量子ドットと、を含む、<1>~<3>のいずれか1つに記載の硬化性組成物。
<5> 上記第1の量子ドットの100質量部に対し、上記第2の量子ドットを10~80質量部含む、<4>に記載の硬化性組成物。
<6> 上記第2の量子ドットの極大吸収波長と上記第1の量子ドットの極大吸収波長との差が30~200nmである、<4>または<5>に記載の硬化性組成物。
<7> 上記量子ドットには配位子が配位している、<1>~<6>のいずれか1つに記載の硬化性組成物。
<8> 上記配位子がカルボン酸化合物である、<7>に記載の硬化性組成物。
<9> 上記カルボン酸化合物の分子量が100000以下である、<8>に記載の硬化性組成物。
<10> 更に、有機色材を含む、<1>~<9>のいずれか1つに記載の硬化性組成物。
<11> 上記量子ドットの100質量部に対して、上記有機色材の含有量が500質量部以下である、<10>に記載の硬化性組成物。
<12> 上記有機色材が、波長700nmを超え1400nm以下の範囲に極大吸収波長を有する化合物である、<10>または<11>に記載の硬化性組成物。
<13> 上記硬化性化合物が、樹脂および重合性化合物から選ばれる少なくとも1種を含む、<1>~<12>のいずれか1つに記載の硬化性組成物。
<14> 上記硬化性化合物が樹脂を含み、
上記樹脂の全量中における、アミン価を有する樹脂の含有量が30質量%以下である、<1>~<13>のいずれか1つに記載の硬化性組成物。
<15> 上記硬化性組成物の波長400~650nmの範囲における吸光度の最小値Aと、波長2200nmでの吸光度Bとの比であるA/Bが4.5以上である、<1>~<14>のいずれか1つに記載の硬化性組成物。
<16> 赤外線透過フィルタ用である、<1>~<15>のいずれか1つに記載の硬化性組成物。
<17> <1>~<16>のいずれか1つに記載の硬化性組成物から得られる膜。
<18> <17>に記載の膜を有する赤外線透過フィルタ。
<19> <17>に記載の膜を有する固体撮像素子。
<20> <17>に記載の膜を有する赤外線センサ。
The present invention provides:
<1> A curable composition containing quantum dots having a maximum absorption wavelength in the wavelength range of 700 to 2000 nm and a curable compound.
A curable composition containing 5% by mass or more of the quantum dots in the total solid content of the curable composition.
<2> The curable composition according to <1>, wherein the quantum dots contain Pb atoms.
<3> The curable composition according to <1> or <2>, wherein the average primary particle size of the quantum dots is 1 to 10 nm.
<4> The above quantum dots are
A first quantum dot having a maximum absorption wavelength in the wavelength range of 700 to 2000 nm,
The curable composition according to any one of <1> to <3>, which comprises a second quantum dot having a maximum absorption wavelength on a wavelength side longer than the maximum absorption wavelength of the first quantum dot. ..
<5> The curable composition according to <4>, which contains 10 to 80 parts by mass of the second quantum dot with respect to 100 parts by mass of the first quantum dot.
<6> The curable composition according to <4> or <5>, wherein the difference between the maximum absorption wavelength of the second quantum dot and the maximum absorption wavelength of the first quantum dot is 30 to 200 nm.
<7> The curable composition according to any one of <1> to <6>, wherein a ligand is coordinated to the quantum dots.
<8> The curable composition according to <7>, wherein the ligand is a carboxylic acid compound.
<9> The curable composition according to <8>, wherein the carboxylic acid compound has a molecular weight of 100,000 or less.
<10> The curable composition according to any one of <1> to <9>, further comprising an organic coloring material.
<11> The curable composition according to <10>, wherein the content of the organic coloring material is 500 parts by mass or less with respect to 100 parts by mass of the quantum dots.
<12> The curable composition according to <10> or <11>, wherein the organic coloring material is a compound having a maximum absorption wavelength in a wavelength range of more than 700 nm and 1400 nm or less.
<13> The curable composition according to any one of <1> to <12>, wherein the curable compound contains at least one selected from a resin and a polymerizable compound.
<14> The curable compound contains a resin and contains a resin.
The curable composition according to any one of <1> to <13>, wherein the content of the resin having an amine value in the total amount of the resin is 30% by mass or less.
<15> A / B, which is the ratio of the minimum absorbance A in the wavelength range of 400 to 650 nm and the absorbance B at the wavelength of 2200 nm, of the curable composition is 4.5 or more, <1> to <14> The curable composition according to any one of.
<16> The curable composition according to any one of <1> to <15>, which is used for an infrared transmission filter.
<17> A film obtained from the curable composition according to any one of <1> to <16>.
<18> An infrared transmission filter having the film according to <17>.
<19> A solid-state image sensor having the film according to <17>.
<20> An infrared sensor having the film according to <17>.
本発明によれば、可視光由来のノイズが少ない状態で赤外線を透過可能な膜を形成できる新規な硬化性組成物を提供することができる。また、膜、赤外線透過フィルタ、固体撮像素子および赤外線センサを提供することができる。 According to the present invention, it is possible to provide a novel curable composition capable of forming a film capable of transmitting infrared rays in a state where there is little noise derived from visible light. Further, a film, an infrared transmission filter, a solid-state image sensor, and an infrared sensor can be provided.
本明細書において、全固形分とは、硬化性組成物の全体から溶剤を除いた成分の合計質量をいう。
本明細書において、赤外線とは、波長700~2500nmの光(電磁波)をいう。
本明細書における基(原子団)の表記において、置換および無置換を記していない表記は、置換基を有さない基と共に置換基を有する基を包含する。例えば、「アルキル基」とは、置換基を有さないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)を包含する。
本明細書において「露光」とは、特に断らない限り、光を用いた露光のみならず、電子線、イオンビーム等の粒子線を用いた描画も露光に含める。また、露光に用いられる光としては、水銀灯の輝線スペクトル、エキシマレーザに代表される遠紫外線、極紫外線(EUV光)、X線、電子線等の活性光線または放射線が挙げられる。
本明細書において、「(メタ)アクリレート」は、アクリレートおよびメタクリレートの双方、または、いずれかを表し、「(メタ)アクリル」は、アクリルおよびメタクリルの双方、または、いずれかを表し、「(メタ)アクリロイル」は、アクリロイルおよびメタクリロイルの双方、または、いずれかを表す。
本明細書において、化学式中のMeはメチル基を、Etはエチル基を、Prはプロピル基を、Buはブチル基を、Phはフェニル基をそれぞれ示す。
本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。
本明細書において、重量平均分子量および数平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)測定でのポリスチレン換算値として定義される。本明細書において、重量平均分子量(Mw)及び数平均分子量(Mn)は、例えば、HLC-8220(東ソー(株)製)を用い、カラムとしてTSKgel Super AWM―H(東ソー(株)製、6.0mmID(内径)×15.0cm)を用い、溶離液として10mmol/L リチウムブロミドNMP(N-メチルピロリジノン)溶液を用いることによって求めることができる。
As used herein, the total solid content refers to the total mass of the components of the curable composition excluding the solvent.
In the present specification, infrared rays refer to light (electromagnetic waves) having a wavelength of 700 to 2500 nm.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substitution includes a group having a substituent as well as a group having no substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, "exposure" includes not only exposure using light but also drawing using particle beams such as an electron beam and an ion beam, unless otherwise specified. Examples of the light used for exposure include the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
As used herein, "(meth) acrylate" represents both acrylate and methacrylate, or either, and "(meth) acrylic" represents both acrylic and methacrylic, or either. ) Acryloyl "represents both acryloyl and / or methacryloyl.
In the present specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In the present specification, the term "process" is included in this term not only as an independent process but also as long as the desired action of the process is achieved even if it cannot be clearly distinguished from other processes. ..
In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene-equivalent values in gel permeation chromatography (GPC) measurements. In the present specification, for the weight average molecular weight (Mw) and the number average molecular weight (Mn), for example, HLC-8220 (manufactured by Tosoh Corporation) is used, and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6) is used as a column. It can be determined by using a 0.0 mm ID (inner diameter) x 15.0 cm) and using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.
<硬化性組成物>
本発明の硬化性組成物は、波長700~2000nmの範囲に極大吸収波長を有する量子ドットと、硬化性化合物とを含み、硬化性組成物の全固形分中に上記量子ドットを5質量%以上含有することを特徴とする。
<Curable composition>
The curable composition of the present invention contains quantum dots having a maximum absorption wavelength in the wavelength range of 700 to 2000 nm and a curable compound, and contains 5% by mass or more of the quantum dots in the total solid content of the curable composition. It is characterized by containing.
量子ドットは、量子効果の非連続的なエネルギー準位とバンドギャップ型の連続的なエネルギー準位を有している。量子ドットの極大吸収波長(吸収ピーク)は、量子効果で発現した非連続的なエネルギー準位に相当し、粒径によりそのエネルギー準位が変化する。また、量子ドットは、量子ドットの極大吸収波長よりも短波長側の波長の光に関しては、バンドギャップ型の吸収により遮光性を有している。このため、例えば、波長700~2000nmの範囲に極大吸収波長を有する量子ドットにおいては、極大吸収波長近傍の光と、それよりも短波長の光に対して高い遮光性を有している。
本発明者らは、このような量子ドットを、硬化性組成物の全固形分中に5質量%以上含有させることにより、可視領域の光の遮光性が高く、量子ドットの極大吸収波長よりも長波長側の波長の光に対する透過性の高い膜を形成することができることを見出した。
このため、本発明の硬化性組成物によれば、可視光由来のノイズが少ない状態で赤外線を透過可能な膜を形成することができることを見出した。
また、本発明者らは、量子ドットのサイズなどを調整することで、その極大吸収波長を調整することができることを見出した。例えば、量子ドットのサイズを大きくすることで、極大吸収波長を長波側にシフトさせることができ、量子ドットのサイズを小さくすることで、極大吸収波長を短波側にシフトさせることができることを見出した。このため、膜を透過させる赤外線の分光設計の変更や調整などを容易に行うことができ、目的に応じた設計変更が可能であることを見出した。
Quantum dots have a discontinuous energy level of quantum effect and a bandgap type continuous energy level. The maximum absorption wavelength (absorption peak) of a quantum dot corresponds to a discontinuous energy level expressed by the quantum effect, and the energy level changes depending on the particle size. Further, the quantum dots have a light-shielding property due to bandgap type absorption for light having a wavelength shorter than the maximum absorption wavelength of the quantum dots. Therefore, for example, a quantum dot having a maximum absorption wavelength in the wavelength range of 700 to 2000 nm has a high light-shielding property for light in the vicinity of the maximum absorption wavelength and light having a wavelength shorter than that.
By incorporating such quantum dots in the total solid content of the curable composition in an amount of 5% by mass or more, the present inventors have a high light-shielding property in the visible region, which is higher than the maximum absorption wavelength of the quantum dots. It has been found that a film having high transparency to light having a wavelength on the long wavelength side can be formed.
Therefore, it has been found that the curable composition of the present invention can form a film capable of transmitting infrared rays in a state where there is little noise derived from visible light.
Further, the present inventors have found that the maximum absorption wavelength can be adjusted by adjusting the size of the quantum dot or the like. For example, we found that by increasing the size of the quantum dots, the maximum absorption wavelength can be shifted to the long wave side, and by reducing the size of the quantum dots, the maximum absorption wavelength can be shifted to the short wave side. .. Therefore, it has been found that the spectroscopic design of infrared rays transmitted through the film can be easily changed and adjusted, and the design can be changed according to the purpose.
本発明の硬化性組成物は、赤外線透過フィルタ用の硬化性組成物として好ましく用いられる。 The curable composition of the present invention is preferably used as a curable composition for an infrared transmission filter.
本発明の硬化性組成物の波長400~650nmの範囲における吸光度の最小値Aと、波長2200nmでの吸光度Bとの比であるA/Bが4.5以上であることが好ましく、10以上であることが好ましく、20以上であることがより好ましく、30以上であることが更に好ましい。上限は、例えば、90以下とすることができる。 The ratio of the minimum value A of the absorbance of the curable composition of the present invention in the wavelength range of 400 to 650 nm and the absorbance B at the wavelength of 2200 nm is preferably 4.5 or more, and preferably 10 or more. It is preferably 20 or more, more preferably 30 or more, and even more preferably 30 or more. The upper limit can be, for example, 90 or less.
このような分光特性を有する硬化性組成物によれば、膜の厚み方向における光の透過率の、波長400~650nmの範囲における最大値が20%以下で、膜の厚み方向における波長2200nmの光の透過率が70%以上の分光特性を有する膜を好適に形成することができる。 According to the curable composition having such spectral characteristics, the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 650 nm is 20% or less, and the light having a wavelength of 2200 nm in the film thickness direction. It is possible to preferably form a film having a spectral characteristic of 70% or more in transmittance.
また、本発明の組成物は、以下の(IR1)~(IR12)のいずれかの分光特性を満たしていることが好ましい。 Further, it is preferable that the composition of the present invention satisfies any of the following spectral characteristics (IR1) to (IR12).
(IR1)硬化性組成物の波長400~830nmの範囲における吸光度の最小値A1と、波長1000~2200nmの範囲における吸光度の最大値B1との比であるA1/B1が4.5以上であることが好ましく、10以上であることがより好ましく、20以上であることが更に好ましく、30以上であることが更により好ましい。上限は、例えば、90以下とすることができる。このような分光特性を有する硬化性組成物によれば、膜の厚み方向における光の透過率の、波長400~830nmの範囲における最大値が20%以下で、膜の厚み方向における光の透過率の、波長1000~2200nmの範囲における最小値が70%以上の分光特性を有する膜を好適に形成することができる。 (IR1) A1 / B1 which is the ratio of the minimum absorbance A1 in the wavelength range of 400 to 830 nm and the maximum absorbance B1 in the wavelength range of 1000 to 2200 nm of the curable composition is 4.5 or more. Is more preferable, 10 or more is more preferable, 20 or more is further preferable, and 30 or more is even more preferable. The upper limit can be, for example, 90 or less. According to the curable composition having such spectral characteristics, the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 830 nm is 20% or less, and the light transmittance in the film thickness direction. It is possible to preferably form a film having a spectral characteristic with a minimum value of 70% or more in the wavelength range of 1000 to 2200 nm.
(IR2)硬化性組成物の波長400~950nmの範囲における吸光度の最小値A2と、波長1100~2200nmの範囲における吸光度の最大値B2との比であるA2/B2が4.5以上であることが好ましく、10以上であることがより好ましく、20以上であることが更に好ましく、30以上であることが更により好ましい。上限は、例えば、90以下とすることができる。このような分光特性を有する硬化性組成物によれば、膜の厚み方向における光の透過率の、波長400~940nmの範囲における最大値が20%以下で、膜の厚み方向における光の透過率の、波長1100~2200nmの範囲における最小値が70%以上の分光特性を有する膜を好適に形成することができる。 (IR2) The ratio of the minimum absorbance A2 in the wavelength range of 400 to 950 nm and the maximum absorbance B2 in the wavelength range of 1100 to 2200 nm of the curable composition is 4.5 or more. Is more preferable, 10 or more is more preferable, 20 or more is further preferable, and 30 or more is even more preferable. The upper limit can be, for example, 90 or less. According to the curable composition having such spectral characteristics, the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 940 nm is 20% or less, and the light transmittance in the film thickness direction. It is possible to preferably form a film having a spectral characteristic with a minimum value of 70% or more in the wavelength range of 1100 to 2200 nm.
(IR3)硬化性組成物の波長400~1050nmの範囲における吸光度の最小値A3と、波長1200~2200nmの範囲における吸光度の最大値B3との比であるA3/B3が4.5以上であることが好ましく、10以上であることがより好ましく、20以上であることが更に好ましく、30以上であることが更により好ましい。上限は、例えば、90以下とすることができる。このような分光特性を有する硬化性組成物によれば、膜の厚み方向における光の透過率の、波長400~1050nmの範囲における最大値が20%以下で、膜の厚み方向における光の透過率の、波長1200~2200nmの範囲における最小値が70%以上の分光特性を有する膜を好適に形成することができる。 (IR3) The ratio of the minimum absorbance A3 in the wavelength range of 400 to 1050 nm and the maximum absorbance B3 in the wavelength range of 1200 to 2200 nm of the curable composition is 4.5 or more. Is more preferable, 10 or more is more preferable, 20 or more is further preferable, and 30 or more is even more preferable. The upper limit can be, for example, 90 or less. According to the curable composition having such spectral characteristics, the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1050 nm is 20% or less, and the light transmittance in the film thickness direction. It is possible to preferably form a film having a spectral characteristic with a minimum value of 70% or more in the wavelength range of 1200 to 2200 nm.
(IR4)硬化性組成物の波長400~1150nmの範囲における吸光度の最小値A4と、波長1300~2200nmの範囲における吸光度の最大値B4との比であるA4/B4が4.5以上であることが好ましく、10以上であることがより好ましく、20以上であることが更に好ましく、30以上であることが更により好ましい。上限は、例えば、90以下とすることができる。このような分光特性を有する硬化性組成物によれば、膜の厚み方向における光の透過率の、波長400~1150nmの範囲における最大値が20%以下で、膜の厚み方向における光の透過率の、波長1300~2200nmの範囲における最小値が70%以上の分光特性を有する膜を好適に形成することができる。 (IR4) A4 / B4, which is the ratio of the minimum absorbance A4 in the wavelength range of 400 to 1150 nm and the maximum absorbance B4 in the wavelength range of 1300 to 2200 nm of the curable composition, is 4.5 or more. Is more preferable, 10 or more is more preferable, 20 or more is further preferable, and 30 or more is even more preferable. The upper limit can be, for example, 90 or less. According to the curable composition having such spectral characteristics, the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1150 nm is 20% or less, and the light transmittance in the film thickness direction. It is possible to preferably form a film having a spectral characteristic with a minimum value of 70% or more in the wavelength range of 1300 to 2200 nm.
(IR5)硬化性組成物の波長400~1250nmの範囲における吸光度の最小値A5と、波長1400~2200nmの範囲における吸光度の最大値B5との比であるA5/B5が4.5以上であることが好ましく、10以上であることがより好ましく、20以上であることが更に好ましく、30以上であることが更により好ましい。上限は、例えば、90以下とすることができる。このような分光特性を有する硬化性組成物によれば、膜の厚み方向における光の透過率の、波長400~1250nmの範囲における最大値が20%以下で、膜の厚み方向における光の透過率の、波長1400~2200nmの範囲における最小値が70%以上の分光特性を有する膜を好適に形成することができる。 (IR5) The ratio of the minimum absorbance A5 in the wavelength range of 400 to 1250 nm and the maximum absorbance B5 in the wavelength range of 1400 to 2200 nm of the curable composition is 4.5 or more. Is more preferable, 10 or more is more preferable, 20 or more is further preferable, and 30 or more is even more preferable. The upper limit can be, for example, 90 or less. According to the curable composition having such spectral characteristics, the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1250 nm is 20% or less, and the light transmittance in the film thickness direction. It is possible to preferably form a film having a spectral characteristic with a minimum value of 70% or more in the wavelength range of 1400 to 2200 nm.
(IR6)硬化性組成物の波長400~1350nmの範囲における吸光度の最小値A6と、波長1500~2200nmの範囲における吸光度の最大値B6との比であるA6/B6が4.5以上であることが好ましく、10以上であることがより好ましく、20以上であることが更に好ましく、30以上であることが更により好ましい。上限は、例えば、90以下とすることができる。このような分光特性を有する硬化性組成物によれば、膜の厚み方向における光の透過率の、波長400~1350nmの範囲における最大値が20%以下で、膜の厚み方向における光の透過率の、波長1500~2200nmの範囲における最小値が70%以上の分光特性を有する膜を好適に形成することができる。 (IR6) A6 / B6, which is the ratio of the minimum absorbance A6 in the wavelength range of 400 to 1350 nm and the maximum absorbance B6 in the wavelength range of 1500 to 2200 nm of the curable composition, is 4.5 or more. Is more preferable, 10 or more is more preferable, 20 or more is further preferable, and 30 or more is even more preferable. The upper limit can be, for example, 90 or less. According to the curable composition having such spectral characteristics, the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1350 nm is 20% or less, and the light transmittance in the film thickness direction. It is possible to preferably form a film having a spectral characteristic with a minimum value of 70% or more in the wavelength range of 1500 to 2200 nm.
(IR7)硬化性組成物の波長400~1450nmの範囲における吸光度の最小値A7と、波長1600~2200nmの範囲における吸光度の最大値B7との比であるA7/B7が4.5以上であることが好ましく、10以上であることがより好ましく、20以上であることが更に好ましく、30以上であることが更により好ましい。上限は、例えば、90以下とすることができる。このような分光特性を有する硬化性組成物によれば、膜の厚み方向における光の透過率の、波長400~1450nmの範囲における最大値が20%以下で、膜の厚み方向における光の透過率の、波長1600~2200nmの範囲における最小値が70%以上の分光特性を有する膜を好適に形成することができる。 (IR7) The ratio of the minimum absorbance A7 in the wavelength range of 400 to 1450 nm and the maximum absorbance B7 in the wavelength range of 1600 to 2200 nm of the curable composition, A7 / B7, is 4.5 or more. Is more preferable, 10 or more is more preferable, 20 or more is further preferable, and 30 or more is even more preferable. The upper limit can be, for example, 90 or less. According to the curable composition having such spectral characteristics, the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1450 nm is 20% or less, and the light transmittance in the film thickness direction. It is possible to preferably form a film having a spectral characteristic with a minimum value of 70% or more in the wavelength range of 1600 to 2200 nm.
(IR8)硬化性組成物の波長400~1550nmの範囲における吸光度の最小値A8と、波長1700~2200nmの範囲における吸光度の最大値B8との比であるA8/B8が4.5以上であることが好ましく、10以上であることがより好ましく、20以上であることが更に好ましく、30以上であることが更により好ましい。上限は、例えば、90以下とすることができる。このような分光特性を有する硬化性組成物によれば、膜の厚み方向における光の透過率の、波長400~1550nmの範囲における最大値が20%以下で、膜の厚み方向における光の透過率の、波長1700~2200nmの範囲における最小値が70%以上の分光特性を有する膜を好適に形成することができる。 (IR8) The ratio of the minimum absorbance A8 in the wavelength range of 400 to 1550 nm and the maximum absorbance B8 in the wavelength range of 1700 to 2200 nm of the curable composition, A8 / B8, is 4.5 or more. Is more preferable, 10 or more is more preferable, 20 or more is further preferable, and 30 or more is even more preferable. The upper limit can be, for example, 90 or less. According to the curable composition having such spectral characteristics, the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1550 nm is 20% or less, and the light transmittance in the film thickness direction. It is possible to preferably form a film having a spectral characteristic with a minimum value of 70% or more in the wavelength range of 1700 to 2200 nm.
(IR9)硬化性組成物の波長400~1650nmの範囲における吸光度の最小値A9と、波長1800~2200nmの範囲における吸光度の最大値B9との比であるA9/B9が4.5以上であることが好ましく、10以上であることがより好ましく、20以上であることが更に好ましく、30以上であることが更により好ましい。上限は、例えば、90以下とすることができる。このような分光特性を有する硬化性組成物によれば、膜の厚み方向における光の透過率の、波長400~1650nmの範囲における最大値が20%以下で、膜の厚み方向における光の透過率の、波長1800~2200nmの範囲における最小値が70%以上の分光特性を有する膜を好適に形成することができる。 (IR9) The ratio of the minimum absorbance A9 in the wavelength range of 400 to 1650 nm and the maximum absorbance B9 in the wavelength range of 1800 to 2200 nm of the curable composition is 4.5 or more. Is more preferable, 10 or more is more preferable, 20 or more is further preferable, and 30 or more is even more preferable. The upper limit can be, for example, 90 or less. According to the curable composition having such spectral characteristics, the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1650 nm is 20% or less, and the light transmittance in the film thickness direction. It is possible to preferably form a film having a spectral characteristic with a minimum value of 70% or more in the wavelength range of 1800 to 2200 nm.
(IR10)硬化性組成物の波長400~1750nmの範囲における吸光度の最小値A10と、波長1900~2200nmの範囲における吸光度の最大値B10との比であるA10/B10が4.5以上であることが好ましく、10以上であることがより好ましく、20以上であることが更に好ましく、30以上であることが更により好ましい。上限は、例えば、90以下とすることができる。このような分光特性を有する硬化性組成物によれば、膜の厚み方向における光の透過率の、波長400~1750nmの範囲における最大値が20%以下で、膜の厚み方向における光の透過率の、波長1900~2200nmの範囲における最小値が70%以上の分光特性を有する膜を好適に形成することができる。 (IR10) A10 / B10, which is the ratio of the minimum absorbance A10 in the wavelength range of 400 to 1750 nm and the maximum absorbance B10 in the wavelength range of 1900 to 2200 nm of the curable composition, is 4.5 or more. Is more preferable, 10 or more is more preferable, 20 or more is further preferable, and 30 or more is even more preferable. The upper limit can be, for example, 90 or less. According to the curable composition having such spectral characteristics, the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1750 nm is 20% or less, and the light transmittance in the film thickness direction. It is possible to preferably form a film having a spectral characteristic with a minimum value of 70% or more in the wavelength range of 1900 to 2200 nm.
(IR11)硬化性組成物の波長400~1850nmの範囲における吸光度の最小値A11と、波長2000~2200nmの範囲における吸光度の最大値B11との比であるA11/B11が4.5以上であることが好ましく、10以上であることがより好ましく、20以上であることが更に好ましく、30以上であることが更により好ましい。上限は、例えば、90以下とすることができる。このような分光特性を有する硬化性組成物によれば、膜の厚み方向における光の透過率の、波長400~1850nmの範囲における最大値が20%以下で、膜の厚み方向における光の透過率の、波長2000~2200nmの範囲における最小値が70%以上の分光特性を有する膜を好適に形成することができる。 (IR11) A11 / B11, which is the ratio of the minimum absorbance A11 in the wavelength range of 400 to 1850 nm and the maximum absorbance B11 in the wavelength range of 2000 to 2200 nm of the curable composition, is 4.5 or more. Is more preferable, 10 or more is more preferable, 20 or more is further preferable, and 30 or more is even more preferable. The upper limit can be, for example, 90 or less. According to the curable composition having such spectral characteristics, the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1850 nm is 20% or less, and the light transmittance in the film thickness direction. A film having a spectral characteristic with a minimum value of 70% or more in the wavelength range of 2000 to 2200 nm can be preferably formed.
(IR12)硬化性組成物の波長400~1950nmの範囲における吸光度の最小値A12と、波長2100~2200nmの範囲における吸光度の最大値B12との比であるA12/B12が4.5以上であることが好ましく、10以上であることがより好ましく、20以上であることが更に好ましく、30以上であることが更により好ましい。上限は、例えば、90以下とすることができる。このような分光特性を有する硬化性組成物によれば、膜の厚み方向における光の透過率の、波長400~1950nmの範囲における最大値が20%以下で、膜の厚み方向における光の透過率の、波長2100~2200nmの範囲における最小値が70%以上の分光特性を有する膜を好適に形成することができる。 (IR12) A12 / B12, which is the ratio of the minimum absorbance A12 in the wavelength range of 400 to 1950 nm and the maximum absorbance B12 in the wavelength range of 2100 to 2200 nm of the curable composition, is 4.5 or more. Is more preferable, 10 or more is more preferable, 20 or more is further preferable, and 30 or more is even more preferable. The upper limit can be, for example, 90 or less. According to the curable composition having such spectral characteristics, the maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1950 nm is 20% or less, and the light transmittance in the film thickness direction. It is possible to preferably form a film having a spectral characteristic with a minimum value of 70% or more in the wavelength range of 2100 to 2200 nm.
上記吸光度の条件は、例えば、波長700~2000nmの範囲に極大吸収波長を有する量子ドットの種類及び含有量を調整することにより達成することができる。 The above absorbance condition can be achieved, for example, by adjusting the type and content of quantum dots having a maximum absorption wavelength in the wavelength range of 700 to 2000 nm.
ある波長λにおける吸光度Aλは、以下の式(1)により定義される。
Aλ=-log(Tλ/100) ・・・(1)
Aλは、波長λにおける吸光度であり、Tλは、波長λにおける透過率(%)である。
本発明において、吸光度の値は、溶液の状態で測定した値であってもよく、本発明の硬化性組成物を用いて製膜した膜での値であってもよい。膜の状態で吸光度を測定する場合は、ガラス基板上にスピンコート等の方法により、乾燥後の膜の厚さが所定の厚さとなるように硬化性組成物を塗布し、ホットプレートを用いて100℃、120秒間乾燥して調製した膜を用いて測定することが好ましい。膜の厚さは、膜を有する基板について、触針式表面形状測定器(ULVAC社製 DEKTAK150)を用いて測定することができる。
The absorbance Aλ at a certain wavelength λ is defined by the following equation (1).
Aλ = -log (Tλ / 100) ... (1)
Aλ is the absorbance at the wavelength λ, and Tλ is the transmittance (%) at the wavelength λ.
In the present invention, the absorbance value may be a value measured in a solution state or a value in a film formed by using the curable composition of the present invention. When measuring the absorbance in the state of a film, a curable composition is applied onto a glass substrate by a method such as spin coating so that the thickness of the film after drying becomes a predetermined thickness, and a hot plate is used. It is preferable to measure using a membrane prepared by drying at 100 ° C. for 120 seconds. The thickness of the film can be measured by using a stylus type surface shape measuring device (DEKTAK150 manufactured by ULVAC, Inc.) for the substrate having the film.
また、吸光度は、従来公知の分光光度計を用いて測定できる。吸光度の測定条件は特に限定はないが、波長400~650nmの範囲における吸光度の最小値Aが、0.1~3.0になるように調整した条件で、波長2200nmでの吸光度Bを測定することが好ましい。このような条件で吸光度を測定することで、測定誤差をより小さくできる。波長400~650nmの範囲における吸光度の最小値Aが、0.1~3.0になるように調整する方法としては、特に限定はない。例えば、溶液の状態で吸光度を測定する場合は、試料セルの光路長を調整する方法が挙げられる。また、膜の状態で吸光度を測定する場合は、膜厚を調整する方法などが挙げられる。 Further, the absorbance can be measured using a conventionally known spectrophotometer. The measurement condition of the absorbance is not particularly limited, but the absorbance B at the wavelength of 2200 nm is measured under the condition that the minimum value A of the absorbance in the wavelength range of 400 to 650 nm is adjusted to 0.1 to 3.0. Is preferable. By measuring the absorbance under such conditions, the measurement error can be further reduced. The method for adjusting the minimum absorbance A in the wavelength range of 400 to 650 nm to be 0.1 to 3.0 is not particularly limited. For example, when measuring the absorbance in the state of a solution, a method of adjusting the optical path length of the sample cell can be mentioned. Further, when measuring the absorbance in the state of a film, a method of adjusting the film thickness and the like can be mentioned.
本発明の硬化性組成物により形成される膜の分光特性、膜厚等の具体的な測定方法を以下に示す。
本発明の硬化性組成物を、ガラス基板上にスピンコート等の方法により、乾燥後の膜の厚さが所定の厚さとなるように塗布し、ホットプレートを用いて100℃、120秒間乾燥する。膜の厚さは、膜を有する乾燥後の基板を、触針式表面形状測定器(ULVAC社製 DEKTAK150)を用いて測定する。この膜を有する乾燥後の基板について、紫外可視近赤外分光光度計(日立ハイテクノロジーズ社製 U-4100)を用いて透過率を測定する。
Specific measurement methods for the spectral characteristics, film thickness, etc. of the film formed by the curable composition of the present invention are shown below.
The curable composition of the present invention is applied onto a glass substrate by a method such as spin coating so that the thickness of the film after drying becomes a predetermined thickness, and dried at 100 ° C. for 120 seconds using a hot plate. .. The thickness of the film is measured by using a stylus type surface shape measuring device (DEKTAK150 manufactured by ULVAC) on the dried substrate having the film. The transmittance of the dried substrate having this film is measured using an ultraviolet-visible near-infrared spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation).
本発明の硬化性組成物の全固形分(固形分濃度)は、基板への適用方法により変更するが、例えば、1~50質量%であることが好ましい。下限は10質量%以上がより好ましい。上限は30質量%以下がより好ましい。 The total solid content (solid content concentration) of the curable composition of the present invention varies depending on the method of application to the substrate, but is preferably 1 to 50% by mass, for example. The lower limit is more preferably 10% by mass or more. The upper limit is more preferably 30% by mass or less.
本発明の硬化性組成物は、乾燥後の膜厚が0.1~50μm(好ましくは0.1~20μm、より好ましくは0.5~10μm)の膜を製膜した際に、前述の膜厚の少なくとも1つにおいて、膜の厚み方向における光の透過率の、波長400~650nmの範囲における最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、波長2200nmの光の透過率が70%以上(好ましくは75%以上、より好ましくは80%以上)である分光特性を満たしていることが好ましい。 The curable composition of the present invention is the above-mentioned film when a film having a film thickness of 0.1 to 50 μm (preferably 0.1 to 20 μm, more preferably 0.5 to 10 μm) after drying is formed. At least one of the thicknesses, the maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 650 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the wavelength is 2200 nm. It is preferable that the light transmittance of the light is 70% or more (preferably 75% or more, more preferably 80% or more).
また、本発明の組成物は、以下の(1)~(12)のいずれかの態様の分光特性を満たしていることが好ましい。 Further, it is preferable that the composition of the present invention satisfies the spectral characteristics of any of the following aspects (1) to (12).
(1)乾燥後の膜厚が0.1~50μm(好ましくは0.1~20μm、より好ましくは0.5~10μm)の膜を製膜した際に、前述の膜厚の少なくとも1つにおいて、膜の厚み方向における光の透過率の、波長400~830nmの範囲における最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、膜の厚み方向における光の透過率の、波長1000~2200nmの範囲における最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である態様。この態様によれば、波長400~830nmの範囲の光を遮光して、波長940nmを超える赤外線が透過可能な膜とすることができる。 (1) When a film having a film thickness of 0.1 to 50 μm (preferably 0.1 to 20 μm, more preferably 0.5 to 10 μm) after drying is formed, at least one of the above-mentioned film thicknesses is used. The maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmittance in the film thickness direction. An embodiment in which the minimum value of the rate in the wavelength range of 1000 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 830 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 940 nm.
(2)乾燥後の膜厚が0.1~50μm(好ましくは0.1~20μm、より好ましくは0.5~10μm)の膜を製膜した際に、前述の膜厚の少なくとも1つにおいて、膜の厚み方向における光の透過率の、波長400~950nmの範囲における最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、膜の厚み方向における光の透過率の、波長1100~2200nmの範囲における最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である態様。この態様によれば、波長400~950nmの範囲の光を遮光して、波長1040nmを超える赤外線が透過可能な膜とすることができる。 (2) When a film having a film thickness of 0.1 to 50 μm (preferably 0.1 to 20 μm, more preferably 0.5 to 10 μm) after drying is formed, at least one of the above-mentioned film thicknesses is used. The maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmittance in the film thickness direction. An embodiment in which the minimum value of the rate in the wavelength range of 1100 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 950 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1040 nm.
(3)乾燥後の膜厚が0.1~50μm(好ましくは0.1~20μm、より好ましくは0.5~10μm)の膜を製膜した際に、前述の膜厚の少なくとも1つにおいて、膜の厚み方向における光の透過率の、波長400~1050nmの範囲における最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、膜の厚み方向における光の透過率の、波長1200~2200nmの範囲における最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である態様。この態様によれば、波長400~1050nmの範囲の光を遮光して、波長1140nmを超える赤外線が透過可能な膜とすることができる。 (3) When a film having a film thickness of 0.1 to 50 μm (preferably 0.1 to 20 μm, more preferably 0.5 to 10 μm) after drying is formed, at least one of the above-mentioned film thicknesses is used. The maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1050 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmittance in the film thickness direction. An embodiment in which the minimum value of the rate in the wavelength range of 1200 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, it is possible to obtain a film capable of transmitting infrared rays having a wavelength of more than 1140 nm by blocking light in the wavelength range of 400 to 1050 nm.
(4)乾燥後の膜厚が0.1~50μm(好ましくは0.1~20μm、より好ましくは0.5~10μm)の膜を製膜した際に、前述の膜厚の少なくとも1つにおいて、膜の厚み方向における光の透過率の、波長400~1150nmの範囲における最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、膜の厚み方向における光の透過率の、波長1300~2200nmの範囲における最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である態様。この態様によれば、波長400~1150nmの範囲の光を遮光して、波長1240nmを超える赤外線が透過可能な膜とすることができる。 (4) When a film having a film thickness of 0.1 to 50 μm (preferably 0.1 to 20 μm, more preferably 0.5 to 10 μm) after drying is formed, at least one of the above-mentioned film thicknesses is used. The maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1150 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmittance in the film thickness direction. An embodiment in which the minimum value of the rate in the wavelength range of 1300 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1150 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1240 nm.
(5)乾燥後の膜厚が0.1~50μm(好ましくは0.1~20μm、より好ましくは0.5~10μm)の膜を製膜した際に、前述の膜厚の少なくとも1つにおいて、膜の厚み方向における光の透過率の、波長400~1250nmの範囲における最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、膜の厚み方向における光の透過率の、波長1400~2200nmの範囲における最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である態様。この態様によれば、波長400~1250nmの範囲の光を遮光して、波長1340nmを超える赤外線が透過可能な膜とすることができる。 (5) When a film having a film thickness of 0.1 to 50 μm (preferably 0.1 to 20 μm, more preferably 0.5 to 10 μm) after drying is formed, at least one of the above-mentioned film thicknesses is used. The maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1250 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmittance in the film thickness direction. An embodiment in which the minimum value of the rate in the wavelength range of 1400 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1250 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1340 nm.
(6)乾燥後の膜厚が0.1~50μm(好ましくは0.1~20μm、より好ましくは0.5~10μm)の膜を製膜した際に、前述の膜厚の少なくとも1つにおいて、膜の厚み方向における光の透過率の、波長400~1350nmの範囲における最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、膜の厚み方向における光の透過率の、波長1500~2200nmの範囲における最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である態様。この態様によれば、波長400~1350nmの範囲の光を遮光して、波長1440nmを超える赤外線が透過可能な膜とすることができる。 (6) When a film having a film thickness of 0.1 to 50 μm (preferably 0.1 to 20 μm, more preferably 0.5 to 10 μm) after drying is formed, at least one of the above-mentioned film thicknesses is used. The maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1350 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmittance in the film thickness direction. An embodiment in which the minimum value of the rate in the wavelength range of 1500 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1350 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1440 nm.
(7)乾燥後の膜厚が0.1~50μm(好ましくは0.1~20μm、より好ましくは0.5~10μm)の膜を製膜した際に、前述の膜厚の少なくとも1つにおいて、膜の厚み方向における光の透過率の、波長400~1450nmの範囲における最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、膜の厚み方向における光の透過率の、波長1600~2200nmの範囲における最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である態様。この態様によれば、波長400~1450nmの範囲の光を遮光して、波長1540nmを超える赤外線が透過可能な膜とすることができる。 (7) When a film having a film thickness of 0.1 to 50 μm (preferably 0.1 to 20 μm, more preferably 0.5 to 10 μm) after drying is formed, at least one of the above-mentioned film thicknesses is used. The maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1450 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmittance in the film thickness direction. An embodiment in which the minimum value of the rate in the wavelength range of 1600 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1450 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1540 nm.
(8)乾燥後の膜厚が0.1~50μm(好ましくは0.1~20μm、より好ましくは0.5~10μm)の膜を製膜した際に、前述の膜厚の少なくとも1つにおいて、膜の厚み方向における光の透過率の、波長400~1550nmの範囲における最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、膜の厚み方向における光の透過率の、波長1700~2200nmの範囲における最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である態様。この態様によれば、波長400~1550nmの範囲の光を遮光して、波長1640nmを超える赤外線が透過可能な膜とすることができる。 (8) When a film having a film thickness of 0.1 to 50 μm (preferably 0.1 to 20 μm, more preferably 0.5 to 10 μm) after drying is formed, at least one of the above-mentioned film thicknesses is used. The maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1550 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmittance in the film thickness direction. An embodiment in which the minimum value of the rate in the wavelength range of 1700 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1550 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1640 nm.
(9)乾燥後の膜厚が0.1~50μm(好ましくは0.1~20μm、より好ましくは0.5~10μm)の膜を製膜した際に、前述の膜厚の少なくとも1つにおいて、膜の厚み方向における光の透過率の、波長400~1650nmの範囲における最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、膜の厚み方向における光の透過率の、波長1800~2200nmの範囲における最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である態様。この態様によれば、波長400~1650nmの範囲の光を遮光して、波長1740nmを超える赤外線が透過可能な膜とすることができる。 (9) When a film having a film thickness of 0.1 to 50 μm (preferably 0.1 to 20 μm, more preferably 0.5 to 10 μm) after drying is formed, at least one of the above-mentioned film thicknesses is used. The maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1650 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmittance in the film thickness direction. An embodiment in which the minimum value of the rate in the wavelength range of 1800 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1650 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1740 nm.
(10)乾燥後の膜厚が0.1~50μm(好ましくは0.1~20μm、より好ましくは0.5~10μm)の膜を製膜した際に、前述の膜厚の少なくとも1つにおいて、膜の厚み方向における光の透過率の、波長400~1750nmの範囲における最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、膜の厚み方向における光の透過率の、波長1900~2200nmの範囲における最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である態様。この態様によれば、波長400~1750nmの範囲の光を遮光して、波長1840nmを超える赤外線が透過可能な膜とすることができる。 (10) When a film having a film thickness of 0.1 to 50 μm (preferably 0.1 to 20 μm, more preferably 0.5 to 10 μm) after drying is formed, at least one of the above-mentioned film thicknesses is used. The maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1750 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmittance in the film thickness direction. An embodiment in which the minimum value of the rate in the wavelength range of 1900 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1750 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1840 nm.
(11)乾燥後の膜厚が0.1~50μm(好ましくは0.1~20μm、より好ましくは0.5~10μm)の膜を製膜した際に、前述の膜厚の少なくとも1つにおいて、膜の厚み方向における光の透過率の、波長400~1850nmの範囲における最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、膜の厚み方向における光の透過率の、波長2000~2200nmの範囲における最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である態様。この態様によれば、波長400~1850nmの範囲の光を遮光して、波長1940nmを超える赤外線が透過可能な膜とすることができる。 (11) When a film having a film thickness of 0.1 to 50 μm (preferably 0.1 to 20 μm, more preferably 0.5 to 10 μm) after drying is formed, at least one of the above-mentioned film thicknesses is used. The maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1850 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmittance in the film thickness direction. An embodiment in which the minimum value of the rate in the wavelength range of 2000 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1850 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1940 nm.
(12)乾燥後の膜厚が0.1~50μm(好ましくは0.1~20μm、より好ましくは0.5~10μm)の膜を製膜した際に、前述の膜厚の少なくとも1つにおいて、膜の厚み方向における光の透過率の、波長400~1950nmの範囲における最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、膜の厚み方向における光の透過率の、波長2100~2200nmの範囲における最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である態様。この態様によれば、波長400~1950nmの範囲の光を遮光して、波長2040nmを超える赤外線が透過可能な膜とすることができる。 (12) When a film having a film thickness of 0.1 to 50 μm (preferably 0.1 to 20 μm, more preferably 0.5 to 10 μm) after drying is formed, at least one of the above-mentioned film thicknesses is used. The maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmittance in the film thickness direction. An embodiment in which the minimum value of the rate in the wavelength range of 2100 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1950 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 2040 nm.
本発明の硬化性組成物は、赤外線を透過させることから、赤外線透過性組成物ということもできる。以下に、本発明の硬化性組成物を構成し得る各成分について説明する。 Since the curable composition of the present invention transmits infrared rays, it can also be said to be an infrared transmissive composition. Hereinafter, each component that can constitute the curable composition of the present invention will be described.
<<量子ドット>>
本発明の硬化性組成物は、波長700~2000nmの範囲に極大吸収波長を有する量子ドット(以下、量子ドットIRともいう)を含む。なお、本明細書において、量子ドットの極大吸収波長の値は、溶液中での値である。量子ドットの極大吸収波長は、量子ドット10mg/mLのトルエン溶液を調製し、このトルエン溶液の吸光度を紫外可視近赤外分光光度計を用いて測定して求めることができる。
<< Quantum dots >>
The curable composition of the present invention contains quantum dots (hereinafter, also referred to as quantum dot IR) having a maximum absorption wavelength in the wavelength range of 700 to 2000 nm. In addition, in this specification, the value of the maximum absorption wavelength of a quantum dot is a value in a solution. The maximum absorption wavelength of the quantum dots can be determined by preparing a toluene solution of quantum dots of 10 mg / mL and measuring the absorbance of the toluene solution using an ultraviolet-visible near-infrared spectrophotometer.
量子ドットIRは、半導体粒子であってもよい。本発明における「半導体」とは、比抵抗値が10-2Ωcm以上108Ωcm以下である物質を意味する。量子ドットを構成する量子ドット材料としては、例えば一般的な半導体結晶〔a)IV族半導体、b)IV-IV族、III-V族、またはII-VI族の化合物半導体、c)II族、III族、IV族、V族、および、VI族元素の内3つ以上の組み合わせからなる化合物半導体〕のナノ粒子(0.5nm以上100nm未満の大きさの粒子)が挙げられる。 The quantum dot IR may be a semiconductor particle. The "semiconductor" in the present invention, specific resistance means a material is 10 -2 [Omega] cm or more 10 8 [Omega] cm or less. Examples of the quantum dot material constituting the quantum dot include general semiconductor crystals [a) group IV semiconductors, b) group IV-IV, group III-V, or group II-VI compound semiconductors, c) group II, and the like. Nanoparticles (particles having a size of 0.5 nm or more and less than 100 nm) of a compound semiconductor composed of a combination of three or more of group III, group IV, group V, and group VI elements can be mentioned.
量子ドットIRは、Pb原子、In原子、Ge原子、Si原子、Cd原子、Zn原子、Hg原子、Al原子、Sn原子およびGa原子から選ばれる少なくとも1種の金属原子を含むものであることが好ましく、Pb原子、In原子、Ge原子およびSi原子から選ばれる少なくとも1種の金属原子を含むものであることがより好ましく、Pb原子を含むものであることが更に好ましい。 The quantum dot IR preferably contains at least one metal atom selected from Pb atom, In atom, Ge atom, Si atom, Cd atom, Zn atom, Hg atom, Al atom, Sn atom and Ga atom. It is more preferable that it contains at least one metal atom selected from Pb atom, In atom, Ge atom and Si atom, and it is further preferable that it contains Pb atom.
量子ドットIRを構成する量子ドット材料の具体例としては、PbS、PbSe、InN、InAs、Ge、InAs、InGaAs、CuInS、CuInSe、CuInGaSe、InSb、HgTe、HgCdTe、Ag2S、Ag2Se、Ag2Te、SnS、SnSe、SnTe、Si、InP等の比較的バンドギャップの狭い半導体材料が挙げられ、PbSまたはPbSeであることが好ましく、PbSであることがより好ましい。 Specific examples of the quantum dot material constituting the quantum dot IR, PbS, PbSe, InN, InAs, Ge, InAs, InGaAs, CuInS, CuInSe, CuInGaSe, InSb, HgTe, HgCdTe, Ag 2 S, Ag 2 Se, Ag 2 Te, SnS, SnSe, SnTe , Si, narrow semiconductor material having relatively bandgap such InP can be mentioned, preferably a PbS or PbSe, more preferably PbS.
量子ドットIRの極大吸収波長は、用途や目的に応じて適宜選択することができる。例えば、量子ドットIRとして、波長1000~1100nmの範囲に極大吸収波長を有する量子ドットを用いた場合は、波長400~1100nmの波長の光を遮光し、波長1200nm以上の波長の光を透過させる膜を形成することができる。 The maximum absorption wavelength of the quantum dot IR can be appropriately selected according to the application and purpose. For example, when a quantum dot having a maximum absorption wavelength in the wavelength range of 1000 to 1100 nm is used as the quantum dot IR, a film that blocks light having a wavelength of 400 to 1100 nm and transmits light having a wavelength of 1200 nm or more. Can be formed.
量子ドットIRの平均一次粒子径は、1~10nmであることが好ましい。なお、量子ドットIRの平均一次粒子径は、任意に選択された10個の量子ドットの一次粒子径の平均値である。量子ドットの粒径の測定には、透過型電子顕微鏡を用いればよい。 The average primary particle size of the quantum dot IR is preferably 1 to 10 nm. The average primary particle size of the quantum dot IR is an average value of the primary particle size of 10 arbitrarily selected quantum dots. A transmission electron microscope may be used to measure the particle size of the quantum dots.
量子ドットIRには配位子が配位していることも好ましい。ここで、量子ドットIRが後述の第1の量子ドットと第2の量子ドットとを含む場合、少なくとも一方の量子ドットに配位子が配位していることが好ましく、両方の量子ドットに配位子が配位していることがより好ましい。この態様によれば、硬化性組成物中における量子ドットの分散性が良好である。配位子としては、カルボン酸化合物、アミン化合物、ホスホン酸化合物、チオール化合物が挙げられ、量子ドットIRの分散性の観点からカルボン酸化合物であることが好ましい。また、カルボン酸化合物の分子量は、100000以下であることが好ましく、60~10000であることがより好ましく、100~1000であることが更に好ましい。カルボン酸化合物の具体例としては、オレイン酸、3-メルカプトプロピオン酸、4-メルカプト安息香酸などが挙げられる。 It is also preferable that a ligand is coordinated to the quantum dot IR. Here, when the quantum dot IR includes the first quantum dot and the second quantum dot described later, it is preferable that the ligand is coordinated to at least one quantum dot, and the ligand is coordinated to both quantum dots. It is more preferable that the position is coordinated. According to this aspect, the dispersibility of the quantum dots in the curable composition is good. Examples of the ligand include a carboxylic acid compound, an amine compound, a phosphonic acid compound, and a thiol compound, and a carboxylic acid compound is preferable from the viewpoint of dispersibility of the quantum dot IR. The molecular weight of the carboxylic acid compound is preferably 100,000 or less, more preferably 60 to 10,000, and even more preferably 100 to 1,000. Specific examples of the carboxylic acid compound include oleic acid, 3-mercaptopropionic acid, 4-mercaptobenzoic acid and the like.
本発明の硬化性組成物は、量子ドットIRとして、波長700~2000nmの範囲に極大吸収波長を有する第1の量子ドットと、第1の量子ドットの極大吸収波長よりも長波長側に極大吸収波長を有する第2の量子ドットとを用いることも好ましい。この態様によれば、第2の量子ドットの極大吸収波長よりも短波側の波長の光の遮光性により優れた膜を形成することができる。第2の量子ドットは2種以上含まれていてもよい。
例えば、第1の量子ドットとして波長900nm近傍に極大吸収波長を有するものを用い、第2の量子ドットとして波長1000nm近傍に極大吸収波長を有するものを用いた場合、1000nm以下の波長の光の遮光性に優れた膜を形成することができる。
The curable composition of the present invention has a first quantum dot having a maximum absorption wavelength in the wavelength range of 700 to 2000 nm as a quantum dot IR, and a maximum absorption on the wavelength side longer than the maximum absorption wavelength of the first quantum dot. It is also preferable to use a second quantum dot having a wavelength. According to this aspect, it is possible to form a film having a better light-shielding property of light having a wavelength on the short wave side than the maximum absorption wavelength of the second quantum dot. Two or more types of second quantum dots may be included.
For example, when a first quantum dot having a maximum absorption wavelength near 900 nm is used and a second quantum dot having a maximum absorption wavelength near 1000 nm is used, light with a wavelength of 1000 nm or less is blocked. It is possible to form a film having excellent properties.
第2の量子ドットの極大吸収波長と第1の量子ドットの極大吸収波長との差は、得られる膜の可視遮光性をより高めることができるという理由から、1~500nmであることが好ましく、20~300nmであることがより好ましく、30~200nmであることが更に好ましい。
また、第2の量子ドットを2種以上含む場合は、最も短波長側に極大吸収波長が存在する第2の量子ドットの極大吸収波長と、第1の量子ドットの極大吸収波長との差が上記範囲であることが好ましい。
また、第2の量子ドットを2種以上含む場合は、n個の第2の量子ドットのうち、極大吸収波長がa番目に長波長側に存在する第2の量子ドットAaの極大吸収波長と、極大吸収波長が(a+1)番目に長波長側に存在する第2の量子ドットAa+1の極大吸収波長の差が1~500nmであることが好ましく、20~300nmであることがより好ましく、30~200nmであることが更に好ましい。ここで、aは1~n-1の整数を表し、nは3以上の整数を表す。
The difference between the maximum absorption wavelength of the second quantum dot and the maximum absorption wavelength of the first quantum dot is preferably 1 to 500 nm because the visible light-shielding property of the obtained film can be further enhanced. It is more preferably 20 to 300 nm, and even more preferably 30 to 200 nm.
When two or more types of second quantum dots are included, the difference between the maximum absorption wavelength of the second quantum dot having the maximum absorption wavelength on the shortest wavelength side and the maximum absorption wavelength of the first quantum dot is large. It is preferably in the above range.
Furthermore, if containing a second quantum dot 2 or more, among the n second quantum dot, the maximum absorption wavelength of the second quantum dot A a where the maximum absorption wavelength exists in a long wavelength side in a th The difference in the maximum absorption wavelength of the second quantum dot Aa + 1 , which has the maximum absorption wavelength on the (a + 1) th longest wavelength side, is preferably 1 to 500 nm, more preferably 20 to 300 nm. It is more preferably 30 to 200 nm. Here, a represents an integer of 1 to n-1, and n represents an integer of 3 or more.
硬化性組成物の全固形分中における量子ドットIRの含有量は、5質量%以上であることが好ましく、10質量%以上であることがより好ましく、20質量%以上であることが更に好ましく、25質量%以上であることがより一層好ましく、30質量%以上であることが特に好ましい。上限は、80質量%以下であることが好ましく、70質量%以下であることがより好ましく、60質量%以下であることが更に好ましい。 The content of the quantum dot IR in the total solid content of the curable composition is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more. It is even more preferably 25% by mass or more, and particularly preferably 30% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, and further preferably 60% by mass or less.
また、本発明の硬化性組成物が上記第1の量子ドットと上記第2の量子ドットとを含む場合、上記第1の量子ドットの100質量部に対して上記第2の量子ドットを1~100質量部含むことが好ましい。上限は80質量部以下であることが好ましく、50質量部以下であることがより好ましい。下限は10質量部以上であることが好ましく、20質量部以上であることがより好ましい。 When the curable composition of the present invention contains the first quantum dots and the second quantum dots, the second quantum dots are added to 100 parts by mass of the first quantum dots. It is preferable to contain 100 parts by mass. The upper limit is preferably 80 parts by mass or less, and more preferably 50 parts by mass or less. The lower limit is preferably 10 parts by mass or more, and more preferably 20 parts by mass or more.
本発明の硬化性組成物は、更に、波長400nm以上700nm未満の範囲に極大吸収波長を有する量子ドット(以下、量子ドットVlともいう)を含んでいてもよい。量子ドットVlをさらに含むことで、可視領域の波長の光の遮光性により優れた膜を形成することができる。 The curable composition of the present invention may further contain quantum dots having a maximum absorption wavelength in the wavelength range of 400 nm or more and less than 700 nm (hereinafter, also referred to as quantum dots Vl). By further including the quantum dots Vl, it is possible to form a film having a better light-shielding property of light having a wavelength in the visible region.
量子ドットVlの材質としては、量子ドットIRで説明したものが挙げられる。 Examples of the material of the quantum dot Vl include those explained in the quantum dot IR.
量子ドットVlの極大吸収波長は、波長450nm以上700nm未満の範囲に存在することが好ましく、波長500nm以上700nm未満の範囲に存在することがより好ましく、波長600nm以上700nm未満の範囲に存在することが更に好ましい。 The maximum absorption wavelength of the quantum dot Vl is preferably in the wavelength range of 450 nm or more and less than 700 nm, more preferably in the wavelength range of 500 nm or more and less than 700 nm, and more preferably in the wavelength range of 600 nm or more and less than 700 nm. More preferred.
本発明の硬化性組成物が量子ドットVlを含む場合、硬化性組成物の全固形分中における量子ドットVlの含有量は、0質量%を超え10質量%以下であることが好ましい。下限は、1質量%以上であることが好ましく、2質量%以上であることがより好ましい。上限は、8質量%以下であることが好ましく、5質量%以下であることがより好ましい。
また、硬化性組成物の全固形分中における量子ドットIRと量子ドットVlとの合計の含有量は、5~80質量%であることが好ましい。下限は、10質量%以上であることが好ましく、20質量%以上であることがより好ましく、25質量%以上であることが更に好ましく、30質量%以上であることが特に好ましい。上限は、75質量%以下であることが好ましく、70質量%以下であることがより好ましい。
When the curable composition of the present invention contains quantum dot Vl, the content of the quantum dot Vl in the total solid content of the curable composition is preferably more than 0% by mass and 10% by mass or less. The lower limit is preferably 1% by mass or more, and more preferably 2% by mass or more. The upper limit is preferably 8% by mass or less, and more preferably 5% by mass or less.
Further, the total content of the quantum dot IR and the quantum dot Vl in the total solid content of the curable composition is preferably 5 to 80% by mass. The lower limit is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 25% by mass or more, and particularly preferably 30% by mass or more. The upper limit is preferably 75% by mass or less, and more preferably 70% by mass or less.
<<有機色材>>
本発明の硬化性組成物は有機色材を含有することができる。この態様によれば、光の遮光性を高めて、目的の光を選択的に透過させることができる膜を形成しやすい。有機色材としては、有彩色色材、黒色色材、近赤外線吸収色材が挙げられる。なお、有機色材とは有機化合物で構成された色材のことを意味する。なお、本明細書における有機色材には、金属錯体などの金属原子を含む有機化合物で構成された色材が含まれる。金属原子を含む有機化合物で構成された色材としては、例えば、銅、亜鉛、アルミニウムなどの金属原子を中心金属として含むフタロシアニン化合物などが挙げられる。
<< Organic Color Material >>
The curable composition of the present invention can contain an organic coloring material. According to this aspect, it is easy to enhance the light blocking property and form a film capable of selectively transmitting the target light. Examples of the organic color material include a chromatic color material, a black color material, and a near-infrared absorbing color material. The organic color material means a color material composed of an organic compound. The organic coloring material in the present specification includes a coloring material composed of an organic compound containing a metal atom such as a metal complex. Examples of the coloring material composed of an organic compound containing a metal atom include a phthalocyanine compound containing a metal atom such as copper, zinc, and aluminum as a central metal.
有機色材は、顔料であってもよく、染料であってもよい。顔料と染料とを併用してもよい。有機色材は、波長700nmを超え1400nm以下の範囲に極大吸収波長を有する化合物を含むことが好ましい。このような色材としては、近赤外線吸収色材が挙げられる。 The organic coloring material may be a pigment or a dye. Pigments and dyes may be used in combination. The organic coloring material preferably contains a compound having a maximum absorption wavelength in the range of more than 700 nm and 1400 nm or less. Examples of such a color material include a near-infrared absorbing color material.
顔料の平均一次粒子径は、1~200nmが好ましい。下限は5nm以上が好ましく、10nm以上がより好ましい。上限は、180nm以下が好ましく、150nm以下がより好ましく、100nm以下が更に好ましい。顔料の平均一次粒子径が上記範囲であれば、硬化性組成物中における顔料の分散安定性を良好にすることができる。なお、本発明において、顔料の一次粒子径は、顔料の一次粒子を透過型電子顕微鏡により観察し、得られた画像写真から求めることができる。具体的には、顔料の一次粒子の投影面積を求め、それに対応する円相当径を顔料の一次粒子径として算出する。また、本発明における平均一次粒子径は、400個の顔料の一次粒子についての一次粒子径の算術平均値とする。また、顔料の一次粒子とは、凝集のない独立した粒子をいう。 The average primary particle size of the pigment is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, more preferably 10 nm or more. The upper limit is preferably 180 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less. When the average primary particle size of the pigment is in the above range, the dispersion stability of the pigment in the curable composition can be improved. In the present invention, the primary particle size of the pigment can be determined from the image photograph obtained by observing the primary particles of the pigment with a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is obtained, and the corresponding circle-equivalent diameter is calculated as the primary particle diameter of the pigment. Further, the average primary particle size in the present invention is an arithmetic mean value of the primary particle size for the primary particles of 400 pigments. Further, the primary particles of the pigment refer to independent particles without agglomeration.
(有彩色色材)
有彩色色材としては、波長400~700nmの範囲に極大吸収波長を有する色材が挙げられる。例えば、黄色色材、オレンジ色色材、赤色色材、緑色色材、紫色色材、青色色材などが挙げられる。有彩色色材の具体例としては、例えば、以下に示すものが挙げられる。
(Coloring material)
Examples of the chromatic color material include a color material having a maximum absorption wavelength in the wavelength range of 400 to 700 nm. For example, a yellow color material, an orange color material, a red color material, a green color material, a purple color material, a blue color material, and the like can be mentioned. Specific examples of the chromatic color material include those shown below.
カラーインデックス(C.I.)Pigment Yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34,35,35:1,36,36:1,37,37:1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,86,93,94,95,97,98,100,101,104,106,108,109,110,113,114,115,116,117,118,119,120,123,125,126,127,128,129,137,138,139,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214,215,228,231,232(メチン系),233(キノリン系),234(アミノケトン系),235(アミノケトン系),236(アミノケトン系)等(以上、黄色顔料)、
C.I.Pigment Orange 2,5,13,16,17:1,31,34,36,38,43,46,48,49,51,52,55,59,60,61,62,64,71,73等(以上、オレンジ色顔料)、
C.I.Pigment Red 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48:1,48:2,48:3,48:4,49,49:1,49:2,52:1,52:2,53:1,57:1,60:1,63:1,66,67,81:1,81:2,81:3,83,88,90,105,112,119,122,123,144,146,149,150,155,166,168,169,170,171,172,175,176,177,178,179,184,185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,269,270,272,279,291,294(キサンテン系、Organo Ultramarine、Bluish Red),295(モノアゾ系),296(ジアゾ系),297(アミノケトン系)等(以上、赤色顔料)、
C.I.Pigment Green 7,10,36,37,58,59,62,63,64(フタロシアニン系),65(フタロシアニン系),66(フタロシアニン系)等(以上、緑色顔料)、
C.I.Pigment Violet 1,19,23,27,32,37,42,60(トリアリールメタン系),61(キサンテン系)等(以上、紫色顔料)、
C.I.Pigment Blue 1,2,15,15:1,15:2,15:3,15:4,15:6,16,22,29,60,64,66,79,80,87(モノアゾ系),88(メチン系)等(以上、青色顔料)。
Color Index (CI) Pigment Yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34, 35,35: 1,36,36: 1,37,37: 1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,86, 93,94,95,97,98,100,101,104,106,108,109,110,113,114,115,116,117,118,119,120,123,125,126,127,128, 129,137,138,139,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174 175,176,177,179,180,181,182,185,187,188,193,194,199,213,214,215,228,231,232 (methine type), 233 (quinoline type), 234 ( Amino ketone type), 235 (amino ketone type), 236 (amino ketone type), etc. (above, yellow pigment),
C. I. Pigment Orange 2,5,13,16,17: 1,31,34,36,38,43,46,48,49,51,52,55,59,60,61,62,64,71,73, etc. (The above is orange pigment),
C. I. Pigment Red 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48: 1,48: 2,48: 3,48: 4, 49,49: 1,49: 2,52: 1,52: 2,53: 1,57: 1,60: 1,63: 1,66,67,81: 1,81: 2,81: 3, 83,88,90,105,112,119,122,123,144,146,149,150,155,166,168,169,170,171,172,175,176,177,178,179,184 185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,269,270,272,279,291 294 (xanthene type, Organo Ultramarine, Bluish Red), 295 (monoazo type), 296 (diazo type), 297 (aminoketone type), etc. (above, red pigment),
C. I. Pigment Green 7,10,36,37,58,59,62,63,64 (phthalocyanine type), 65 (phthalocyanine type), 66 (phthalocyanine type), etc. (above, green pigment),
C. I. Pigment Violet 1,19,23,27,32,37,42,60 (triarylmethane type), 61 (xanthene type), etc. (above, purple pigment),
C. I. Pigment Blue 1,2,15,15: 1,15: 2,15: 3,15: 4,15: 6,16,22,29,60,64,66,79,80,87 (monoazo system), 88 (methine-based) and the like (above, blue pigment).
また、緑色色材として、1分子中のハロゲン原子数が平均10~14個であり、臭素原子数が平均8~12個であり、塩素原子数が平均2~5個であるハロゲン化亜鉛フタロシアニン顔料を用いることもできる。具体例としては、国際公開第2015/118720号に記載の化合物が挙げられる。また、緑色色材として中国特許出願第106909027号明細書に記載の化合物、国際公開第2012/102395号に記載のリン酸エステルを配位子として有するフタロシアニン化合物、特開2019-008014号公報に記載のフタロシアニン化合物、特開2018-180023号公報に記載のフタロシアニン化合物、特開2019-038958号公報に記載の化合物などを用いることもできる。 Further, as a green color material, a halogenated zinc phthalocyanine having an average of 10 to 14 halogen atoms in one molecule, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms. Pigments can also be used. Specific examples include the compounds described in WO 2015/118720. Further, as a green color material, the compound described in Chinese Patent Application No. 1069009027, the phthalocyanine compound having a phosphate ester described in International Publication No. 2012/10395 as a ligand, and Japanese Patent Application Laid-Open No. 2019-008014. , The phthalocyanine compound described in JP-A-2018-180023, the compound described in JP-A-2019-038958, and the like can also be used.
また、青色色材として、リン原子を有するアルミニウムフタロシアニン化合物を用いることもできる。具体例としては、特開2012-247591号公報の段落0022~0030、特開2011-157478号公報の段落0047に記載の化合物が挙げられる。 Further, as the blue color material, an aluminum phthalocyanine compound having a phosphorus atom can also be used. Specific examples include the compounds described in paragraphs 0022 to 0030 of JP2012-247591A and paragraphs 0047 of JP2011-157478A.
また、黄色色材として、特開2017-201003号公報に記載の化合物、特開2017-197719号公報に記載の化合物、特開2017-171912号公報の段落番号0011~0062、0137~0276に記載の化合物、特開2017-171913号公報の段落番号0010~0062、0138~0295に記載の化合物、特開2017-171914号公報の段落番号0011~0062、0139~0190に記載の化合物、特開2017-171915号公報の段落番号0010~0065、0142~0222に記載の化合物、特開2013-054339号公報の段落番号0011~0034に記載のキノフタロン化合物、特開2014-026228号公報の段落番号0013~0058に記載のキノフタロン化合物、特開2018-062644号公報に記載のイソインドリン化合物、特開218-203798号公報に記載のキノフタロン化合物、特開2018-062578号公報に記載のキノフタロン化合物、特許第6432077号公報に記載のキノフタロン化合物、特許第6432076号公報に記載のキノフタロン化合物、特開2018-155881号公報に記載のキノフタロン化合物、特開2018-111757号公報に記載のキノフタロン化合物、特開2018-040835号公報に記載のキノフタロン化合物、特開2017-197640号公報に記載のキノフタロン化合物、特開2016-145282号公報に記載のキノフタロン化合物、特開2014-085565号公報に記載のキノフタロン化合物、特開2014-021139号公報に記載のキノフタロン化合物、特開2013-209614号公報に記載のキノフタロン化合物、特開2013-209435号公報に記載のキノフタロン化合物、特開2013-181015号公報に記載のキノフタロン化合物、特開2013-061622号公報に記載のキノフタロン化合物、特開2013-054339号公報に記載のキノフタロン化合物、特開2013-032486号公報に記載のキノフタロン化合物、特開2012-226110号公報に記載のキノフタロン化合物、特開2008-074987号公報に記載のキノフタロン化合物、特開2008-081565号公報に記載のキノフタロン化合物、特開2008-074986号公報に記載のキノフタロン化合物、特開2008-074985号公報に記載のキノフタロン化合物、特開2008-050420号公報に記載のキノフタロン化合物、特開2008-031281号公報に記載のキノフタロン化合物、特公昭48-032765号公報に記載のキノフタロン化合物、特開2019-008014号公報に記載のキノフタロン化合物を用いることもできる。 Further, as the yellow color material, the compounds described in JP-A-2017-201003, the compounds described in JP-A-2017-197719, and paragraph numbers 0011 to 0062 and 0137-0276 of JP-A-2017-171912 are described. , Compounds described in paragraphs 0010 to 0062, 0138 to 0295 of JP-A-2017-171913, compounds described in paragraphs 0011 to 0062, 0139-0190 of JP-A-2017-171914, JP-A-2017. The compounds described in paragraphs 0010 to 0065 and 0142 to 0222 of JP-A-171915, the quinophthalone compounds described in paragraphs 0011 to 0034 of JP2013-054339, paragraph numbers 0013 to JP-A-2014-0226228. The quinophthalone compound described in 0058, the isoindolin compound described in JP-A-2018-062644, the quinophthalone compound described in JP-A-218-203798, the quinophthalone compound described in JP-A-2018-062578, Patent No. 6432077. The quinophthalone compound described in Japanese Patent Application Laid-Open No. 6432076, the quinophthalone compound described in JP-A-2018-155881, the quinophthalone compound described in JP-A-2018-11175, the quinophthalone compound described in JP-A-2018-1040835 The quinophthalone compound described in JP-A-2017-197640, the quinophthalone compound described in JP-A-2016-145282, the quinophthalone compound described in JP-A-2014-0855565, the quinophthalone compound described in JP-A-2014-085565, JP-A-2014. The quinophthalone compound described in JP-A-201139, the quinophthalone compound described in JP2013-209614, the quinophthalone compound described in JP2013-209435, the quinophthalone compound described in JP2013-181015, and the present invention. The quinophthalone compound described in JP2013-061622, the quinophthalone compound described in JP2013-054339, the quinophthalone compound described in JP2013-032486, and the quinophthalone compound described in JP2012-226110. , A quinophthalone compound described in JP-A-2008-074987, a quinophthalone compound described in JP-A-2008-081565, a quinophthalone compound described in JP-A-2008-074986, a quinophthalone compound described in JP-A-2008-074986, JP-A-2008. The quinophthalone compound described in JP-A-074985, the quinophthalone compound described in JP-A-2008-050420, the quinophthalone compound described in JP-A-2008-031281, the quinophthalone compound described in JP-A-48-032765, and the special publication. The quinophthalone compound described in Kai 2019-008014 can also be used.
赤色色材として、特開2017-201384号公報に記載の構造中に少なくとも1つ臭素原子が置換したジケトピロロピロール顔料、特許第6248838号の段落番号0016~0022に記載のジケトピロロピロール顔料、特許6516119号公報に記載の赤色色材、特許6525101号公報に記載の赤色色材などを用いることもできる。また、赤色色材として、芳香族環に対して、酸素原子、硫黄原子または窒素原子が結合した基が導入された芳香族環基がジケトピロロピロール骨格に結合した構造を有する化合物を用いることもできる。 As a red color material, a diketopyrrolopyrrole pigment in which at least one bromine atom is substituted in the structure described in JP-A-2017-201384, and a diketopyrrolopyrrole pigment described in paragraphs 0016 to 0022 of Patent No. 6248838. , The red color material described in Japanese Patent No. 6516119, the red color material described in Japanese Patent No. 6525101, and the like can also be used. Further, as the red color material, a compound having a structure in which an aromatic ring group having an oxygen atom, a sulfur atom, or a nitrogen atom bonded to the aromatic ring is bonded to a diketopyrrolopyrrole skeleton is used. You can also.
また、有彩色色材として、染料を用いることもできる。染料としては特に制限はなく、公知の染料が使用できる。例えば、ピラゾールアゾ化合物、アニリノアゾ化合物、トリアリールメタン化合物、アントラキノン化合物、アントラピリドン化合物、ベンジリデン化合物、オキソノール化合物、ピラゾロトリアゾールアゾ化合物、ピリドンアゾ化合物、シアニン化合物、フェノチアジン化合物、ピロロピラゾールアゾメチン化合物、キサンテン化合物、フタロシアニン化合物、ベンゾピラン化合物、インジゴ化合物、ピロメテン化合物が挙げられる。また、特開2012-158649号公報に記載のチアゾール化合物、特開2011-184493号公報に記載のアゾ化合物、特開2011-145540号公報に記載のアゾ化合物を用いることもできる。また、染料としては、色素多量体を用いることもできる。色素多量体は、一分子中に、色素構造を2以上有するものであり、色素構造を3以上有することが好ましい。上限は、特に限定はないが、100以下とすることもできる。一分子中に有する複数の色素構造は、同一の色素構造であってもよく、異なる色素構造であってもよい。色素多量体の重量平均分子量(Mw)は、2000~50000が好ましい。下限は、3000以上がより好ましく、6000以上がさらに好ましい。上限は、30000以下がより好ましく、20000以下がさらに好ましい。色素多量体は、特開2011-213925号公報、特開2013-041097号公報、特開2015-028144号公報、特開2015-030742号公報、特開2016-102191号公報、国際公開第2016/031442号等に記載されている化合物を用いることもできる。 Also, a dye can be used as a chromatic color material. The dye is not particularly limited, and known dyes can be used. For example, pyrazole azo compound, anilino azo compound, triarylmethane compound, anthraquinone compound, anthrapyridone compound, benzylidene compound, oxonol compound, pyrazorotriazole azo compound, pyridone azo compound, cyanine compound, phenothiazine compound, pyropyrazole azomethine compound, xanthene compound, Examples thereof include phthalocyanine compounds, benzopyran compounds, indigo compounds and pyromethene compounds. Further, the thiazole compound described in JP2012-158649A, the azo compound described in JP2011-184493, and the azo compound described in JP2011-145540 can also be used. Further, as the dye, a dye multimer can also be used. The dye multimer has two or more dye structures in one molecule, and preferably has three or more dye structures. The upper limit is not particularly limited, but may be 100 or less. The plurality of dye structures contained in one molecule may have the same dye structure or different dye structures. The weight average molecular weight (Mw) of the dye multimer is preferably 2000 to 50,000. The lower limit is more preferably 3000 or more, and even more preferably 6000 or more. The upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less. Dye multimers are available from JP-A-2011-213925, JP-A-2013-041097, JP-A-2015-028144, JP-A-2015-030742, JP-A-2016-102191, International Publication No. 2016 / Compounds described in 031442 and the like can also be used.
有彩色色材は、2種以上組み合わせて用いてもよい。また、有彩色色材を2種以上組み合わせて用いる場合、2種以上の有彩色色材の組み合わせで黒色を形成していてもよい。そのような組み合わせとしては、例えば以下の(1)~(8)の態様が挙げられる。
(1)黄色色材、青色色材、紫色色材および赤色色材を含有する態様。
(2)黄色色材、青色色材および赤色色材を含有する態様。
(3)黄色色材、紫色色材および赤色色材を含有する態様。
(4)黄色色材および紫色色材を含有する態様。
(5)緑色色材、青色色材、紫色色材および赤色色材を含有する態様。
(6)紫色色材およびオレンジ色色材を含有する態様。
(7)緑色色材、紫色色材および赤色色材を含有する態様。
(8)緑色色材および赤色色材を含有する態様。
Two or more kinds of chromatic color materials may be used in combination. Further, when two or more kinds of chromatic color materials are used in combination, black may be formed by a combination of two or more kinds of chromatic color materials. Examples of such a combination include the following aspects (1) to (8).
(1) An embodiment containing a yellow color material, a blue color material, a purple color material, and a red color material.
(2) An embodiment containing a yellow color material, a blue color material, and a red color material.
(3) An embodiment containing a yellow color material, a purple color material, and a red color material.
(4) An embodiment containing a yellow color material and a purple color material.
(5) An embodiment containing a green color material, a blue color material, a purple color material, and a red color material.
(6) An embodiment containing a purple color material and an orange color material.
(7) An embodiment containing a green color material, a purple color material, and a red color material.
(8) An embodiment containing a green color material and a red color material.
(黒色色材)
黒色色材としては特に限定されず、公知のものを用いることができる。例えば、ビスベンゾフラノン化合物、アゾメチン化合物、ペリレン化合物、アゾ化合物などが挙げられ、ビスベンゾフラノン化合物、ペリレン化合物が好ましい。ビスベンゾフラノン化合物としては、特表2010-534726号公報、特表2012-515233号公報、特表2012-515234号公報、国際公開第2014/208348号、特表2015-525260号公報などに記載の化合物が挙げられ、例えば、BASF社製の「Irgaphor Black」として入手可能である。ペリレン化合物としては、C.I.Pigment Black 31、32などが挙げられる。アゾメチン化合物としては、特開平01-170601号公報、特開平02-034664号公報などに記載の化合物が挙げられ、例えば、大日精化社製の「クロモファインブラックA1103」として入手できる。
(Black color material)
The black color material is not particularly limited, and known materials can be used. For example, bisbenzofuranone compound, azomethine compound, perylene compound, azo compound and the like can be mentioned, and bisbenzofuranone compound and perylene compound are preferable. Examples of the bisbenzofuranone compound are described in JP-A-2010-534726, JP-A-2012-515233, App. Compounds are mentioned and are available, for example, as "Irgaphor Black" manufactured by BASF. Examples of the perylene compound include C.I. I. Pigment Black 31, 32 and the like can be mentioned. Examples of the azomethine compound include the compounds described in JP-A-01-170601 and JP-A-02-0346664, and are available as, for example, "Chromofine Black A1103" manufactured by Dainichiseika.
(近赤外線吸収色材)
近赤外線吸収色材は、波長700nmを超え1400nm以下の範囲に極大吸収波長を有する有機色材であることが好ましい。また、近赤外線吸収色材の極大吸収波長は、1200nm以下であることが好ましく、1000nm以下であることがより好ましく、950nm以下であることが更に好ましい。また、近赤外線吸収色材は、波長550nmにおける吸光度A550と極大吸収波長における吸光度Amaxとの比であるA550/Amaxが0.1以下であることが好ましく、0.05以下であることがより好ましく、0.03以下であることが更に好ましく、0.02以下であることが特に好ましい。下限は、特に限定はないが、例えば、0.0001以上とすることができ、0.0005以上とすることもできる。上述の吸光度の比が上記範囲であれば、可視透明性および近赤外線遮蔽性に優れた近赤外線吸収色材とすることができる。また、近赤外線吸収色材は、顔料であることが好ましい。なお、本発明において、近赤外線吸収色材の極大吸収波長および各波長における吸光度の値は、近赤外線吸収色材を含む組成物を用いて形成した膜の吸収スペクトルから求めた値である。
(Near infrared absorbing color material)
The near-infrared absorbing color material is preferably an organic coloring material having a maximum absorption wavelength in the range of more than 700 nm and 1400 nm or less. The maximum absorption wavelength of the near-infrared absorbing color material is preferably 1200 nm or less, more preferably 1000 nm or less, and further preferably 950 nm or less. Further, the near-infrared absorbing color material preferably has A 550 / A max, which is the ratio of the absorbance A 550 at a wavelength of 550 nm and the absorbance A max at the maximum absorption wavelength, to be 0.1 or less, preferably 0.05 or less. More preferably, it is more preferably 0.03 or less, and particularly preferably 0.02 or less. The lower limit is not particularly limited, but can be, for example, 0.0001 or more, or 0.0005 or more. When the above-mentioned absorbance ratio is in the above range, a near-infrared absorbing color material having excellent visible transparency and near-infrared shielding property can be obtained. Further, the near-infrared absorbing color material is preferably a pigment. In the present invention, the maximum absorption wavelength of the near-infrared absorbing color material and the value of the absorbance at each wavelength are values obtained from the absorption spectrum of the film formed by using the composition containing the near-infrared absorbing color material.
近赤外線吸収色材としては、特に限定はないが、ピロロピロール化合物、シアニン化合物、スクアリリウム化合物、フタロシアニン化合物、ナフタロシアニン化合物、クアテリレン化合物、メロシアニン化合物、クロコニウム化合物、オキソノール化合物、イミニウム化合物、ジチオール化合物、トリアリールメタン化合物、ピロメテン化合物、アゾメチン化合物、アントラキノン化合物、ジベンゾフラノン化合物、ジチオレン金属錯体等が挙げられる。ピロロピロール化合物としては、特開2009-263614号公報の段落番号0016~0058に記載の化合物、特開2011-068731号公報の段落番号0037~0052に記載の化合物、国際公開第2015/166873号の段落番号0010~0033に記載の化合物などが挙げられる。スクアリリウム化合物としては、特開2011-208101号公報の段落番号0044~0049に記載の化合物、特許第6065169号公報の段落番号0060~0061に記載の化合物、国際公開第2016/181987号の段落番号0040に記載の化合物、特開2015-176046号公報に記載の化合物、国際公開第2016/190162号の段落番号0072に記載の化合物、特開2016-074649号公報の段落番号0196~0228に記載の化合物、特開2017-067963号公報の段落番号0124に記載の化合物、国際公開第2017/135359号に記載の化合物、特開2017-114956号公報に記載の化合物、特許6197940号公報に記載の化合物、国際公開第2016/120166号に記載の化合物などが挙げられる。シアニン化合物としては、特開2009-108267号公報の段落番号0044~0045に記載の化合物、特開2002-194040号公報の段落番号0026~0030に記載の化合物、特開2015-172004号公報に記載の化合物、特開2015-172102号公報に記載の化合物、特開2008-088426号公報に記載の化合物、国際公開第2016/190162号の段落番号0090に記載の化合物、特開2017-031394号公報に記載の化合物などが挙げられる。クロコニウム化合物としては、特開2017-082029号公報に記載の化合物が挙げられる。イミニウム化合物としては、例えば、特表2008-528706号公報に記載の化合物、特開2012-012399号公報に記載の化合物、特開2007-092060号公報に記載の化合物、国際公開第2018/043564号の段落番号0048~0063に記載の化合物が挙げられる。フタロシアニン化合物としては、特開2012-077153号公報の段落番号0093に記載の化合物、特開2006-343631号公報に記載のオキシチタニウムフタロシアニン、特開2013-195480号公報の段落番号0013~0029に記載の化合物、特許第6081771号公報に記載のバナジウムフタロシアニン化合物が挙げられる。ナフタロシアニン化合物としては、特開2012-077153号公報の段落番号0093に記載の化合物が挙げられる。ジチオレン金属錯体としては、特許第5733804号公報に記載の化合物が挙げられる。 The near-infrared absorbing coloring material is not particularly limited, but is pyrolopyrrole compound, cyanine compound, squarylium compound, phthalocyanine compound, naphthalocyanine compound, quaterylene compound, merocyanine compound, croconium compound, oxonor compound, iminium compound, dithiol compound, and tria. Examples thereof include a reelmethane compound, a pyromethene compound, an azomethine compound, an anthraquinone compound, a dibenzofuranone compound, and a dithiolene metal complex. Examples of the pyrolopyrrole compound include the compounds described in paragraphs 0016 to 0058 of JP2009-263614, the compounds described in paragraphs 0037 to 0052 of JP2011-066731, and International Publication No. 2015/166783. Examples thereof include the compounds described in paragraphs 0010 to 0033. Examples of the squarylium compound include the compounds described in paragraphs 0044 to 0049 of JP2011-208101A, the compounds described in paragraphs 0060 to 0061 of Patent No. 6065169, and paragraph numbers 0040 of International Publication No. 2016/181987. , The compound described in JP-A-2015-176046, the compound described in paragraph number 0072 of International Publication No. 2016/190162, the compound described in paragraph number 0196-0228 of JP-A-2016-074649. , The compound described in paragraph No. 0124 of JP-A-2017-067963, the compound described in International Publication No. 2017/135359, the compound described in JP-A-2017-114956, the compound described in Patent No. 61979940, Examples thereof include the compounds described in International Publication No. 2016/120166. Examples of the cyanine compound include the compounds described in paragraphs 0044 to 0045 of JP2009-108267A, the compounds described in paragraphs 0026 to 0030 of JP2002-194040, and the compounds described in JP2015-172004. , The compound described in JP-A-2015-172102, the compound described in JP-A-2008-088426, the compound described in paragraph No. 0090 of International Publication No. 2016/190162, JP-A-2017-031394. Examples thereof include the compounds described in. Examples of the croconium compound include the compounds described in JP-A-2017-082029. Examples of the iminium compound include the compounds described in JP-A-2008-528706, the compounds described in JP-A-2012-012399, the compounds described in JP-A-2007-092060, and International Publication No. 2018/043564. Examples thereof include the compounds described in paragraphs 0048 to 0063 of. Examples of the phthalocyanine compound include the compound described in paragraph No. 0093 of JP2012-077153, the oxytitanium phthalocyanine described in JP2006-343631, and paragraphs 0013 to 0029 of JP2013-195480. , And the vanadium phthalocyanine compound described in Japanese Patent No. 6081771. Examples of the naphthalocyanine compound include the compounds described in paragraph No. 0093 of JP2012-077153. Examples of the dithiolene metal complex include the compounds described in Japanese Patent No. 5733804.
近赤外線吸収色材としては、特開2017-197437号公報に記載のスクアリリウム化合物、特開2017-025311号公報に記載のスクアリリウム化合物、国際公開第2016/154782号に記載のスクアリリウム化合物、特許第5884953号公報に記載のスクアリリウム化合物、特許第6036689号公報に記載のスクアリリウム化合物、特許第5810604号公報に記載のスクアリリウム化合物、国際公開第2017/213047号の段落番号0090~0107に記載のスクアリリウム化合物、特開2018-054760号公報の段落番号0019~0075に記載のピロール環含有化合物、特開2018-040955号公報の段落番号0078~0082に記載のピロール環含有化合物、特開2018-002773号公報の段落番号0043~0069に記載のピロール環含有化合物、特開2018-041047号公報の段落番号0024~0086に記載のアミドα位に芳香環を有するスクアリリウム化合物、特開2017-179131号公報に記載のアミド連結型スクアリリウム化合物、特開2017-141215号公報に記載のピロールビス型スクアリリウム骨格又はクロコニウム骨格を有する化合物、特開2017-082029号公報に記載されたジヒドロカルバゾールビス型のスクアリリウム化合物、特開2017-068120号公報の段落番号0027~0114に記載の非対称型の化合物、特開2017-067963号公報に記載されたピロール環含有化合物(カルバゾール型)、特許第6251530号公報に記載されたフタロシアニン化合物などを用いることもできる。 Examples of the near-infrared absorbing coloring material include a squarylium compound described in JP-A-2017-197437, a squarylium compound described in JP-A-2017-025311, a squarylium compound described in International Publication No. 2016/154782, and Patent No. 5884953. Squarylium compound described in Japanese Patent Publication No. 60366689, Squalylium compound described in Japanese Patent No. 581604, Squalylium compound described in International Publication No. 2017/213047, paragraph numbers 0090 to 0107, special feature. Pyrrole ring-containing compounds described in paragraphs 0019 to 0075 of Japanese Patent Application Laid-Open No. 2018-054760, pyrrole ring-containing compounds described in paragraph numbers 0078 to 0082 of JP-A-2018-040955, paragraphs of JP-A-2018-002773. Pyrrole ring-containing compounds described in Nos. 0043 to 0069, squarylium compounds having an aromatic ring at the amide α position described in paragraphs 0024 to 0086 of JP-A-2018-041047, amides described in JP-A-2017-179131. Linked squalylium compound, compound having a pyrrolbis-type squalylium skeleton or croconium skeleton described in JP-A-2017-141215, dihydrocarbazolebis-type squalylium compound described in JP-A-2017-082029, JP-A-2017-068120 The asymmetric compound described in paragraphs 0027 to 0114 of Japanese Patent Application Laid-Open No. 2017, the pyrrole ring-containing compound (carbazole type) described in JP-A-2017-067963, the phthalocyanine compound described in Japanese Patent No. 6251530, and the like are used. You can also do it.
有機色材の含有量は、量子ドットIR(波長700~2000nmの範囲に極大吸収波長を有する量子ドット)の100質量部に対して500質量部以下であることが好ましく、100質量部以下であることがより好ましく、50質量部以下であることが更に好ましい。下限は、1質量部以上とすることもでき、10質量部以上とすることもできる。 The content of the organic coloring material is preferably 500 parts by mass or less, preferably 100 parts by mass or less, with respect to 100 parts by mass of the quantum dot IR (quantum dot having a maximum absorption wavelength in the wavelength range of 700 to 2000 nm). More preferably, it is more preferably 50 parts by mass or less. The lower limit may be 1 part by mass or more, or 10 parts by mass or more.
<<硬化性化合物>>
本発明の硬化性組成物は、硬化性化合物を含有する。硬化性化合物としては、重合性化合物、樹脂、ゼラチンやセルロース等の天然高分子等が挙げられる。ゼラチンとしては、その合成方法によって、酸処理ゼラチンおよびアルカリ処理ゼラチン(石灰処理など)があり、いずれも好ましく用いることができる。ゼラチンの分子量は、10000~1000000であることが好ましい。また、ゼラチンのアミノ基やカルボキシル基を利用して変性処理した変性ゼラチンも用いることができる(例えば、フタル化ゼラチンなど)。ゼラチンとしては、イナートゼラチン(例えば、新田ゼラチン750)、フタル化ゼラチン(例えば、新田ゼラチン801)などを用いることができる。樹脂は、非重合性の樹脂(重合性基を有さない樹脂)であってもよく、重合性の樹脂(重合性基を有する樹脂)であってもよい。重合性基としては、エチレン性不飽和結合含有基、エポキシ基、メチロール基などが挙げられる。エチレン性不飽和結合含有基としては、ビニル基、アリル基、(メタ)アクリロイル基などが挙げられる。なお、重合性の樹脂(重合性基を有する樹脂)は、重合性化合物でもある。
<< Curable compound >>
The curable composition of the present invention contains a curable compound. Examples of the curable compound include polymerizable compounds, resins, and natural polymers such as gelatin and cellulose. As the gelatin, there are acid-treated gelatin and alkali-treated gelatin (lime treatment and the like) depending on the synthesis method, and both of them can be preferably used. The molecular weight of gelatin is preferably 10,000 to 1,000,000. Further, modified gelatin modified by utilizing an amino group or a carboxyl group of gelatin can also be used (for example, phthalated gelatin). As the gelatin, inert gelatin (for example, Nitta Gelatin 750), phthalated gelatin (for example, Nitta Gelatin 801) and the like can be used. The resin may be a non-polymerizable resin (a resin having no polymerizable group) or a polymerizable resin (a resin having a polymerizable group). Examples of the polymerizable group include an ethylenically unsaturated bond-containing group, an epoxy group, and a methylol group. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, an allyl group, and a (meth) acryloyl group. The polymerizable resin (resin having a polymerizable group) is also a polymerizable compound.
本発明において、硬化性化合物としては、樹脂を少なくとも含むものを用いることが好ましく、樹脂とモノマータイプの重合性化合物とを用いることがより好ましく、樹脂と、エチレン性不飽和結合を有するモノマータイプの重合性化合物とを用いることが更に好ましい。 In the present invention, the curable compound preferably contains at least a resin, more preferably a resin and a monomer-type polymerizable compound, and a monomer-type compound having an ethylenically unsaturated bond with the resin. It is more preferable to use a polymerizable compound.
本発明の硬化性組成物の全固形分中における硬化性化合物の含有量は、0.1~80質量%であることが好ましい。下限は、0.5質量%以上が好ましく、1質量%以上がより好ましく、5質量%以上が更に好ましい。上限は、70質量%以下が好ましく、60質量%以下がより好ましく、50質量%以下が更に好ましく、40質量%以下がより一層好ましく、30質量%以下が特に好ましい。硬化性化合物は、1種類のみでもよく、2種類以上でもよい。2種類以上の場合は、合計量が上記範囲となることが好ましい。 The content of the curable compound in the total solid content of the curable composition of the present invention is preferably 0.1 to 80% by mass. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more, and further preferably 5% by mass or more. The upper limit is preferably 70% by mass or less, more preferably 60% by mass or less, further preferably 50% by mass or less, further preferably 40% by mass or less, and particularly preferably 30% by mass or less. The curable compound may be only one kind or two or more kinds. In the case of two or more types, the total amount is preferably in the above range.
(重合性化合物)
重合性化合物としては、エチレン性不飽和結合含有基を有する化合物、エポキシ基を有する化合物、メチロール基を有する化合物等が挙げられる。重合性化合物は、モノマーであってもよく、樹脂であってもよい。エチレン性不飽和結合含有基を有するモノマータイプの重合性化合物は、ラジカル重合性化合物として好ましく用いることができる。また、エポキシ基を有する化合物はカチオン重合性化合物として好ましく用いることができる。
(Polymerizable compound)
Examples of the polymerizable compound include a compound having an ethylenically unsaturated bond-containing group, a compound having an epoxy group, and a compound having a methylol group. The polymerizable compound may be a monomer or a resin. A monomer-type polymerizable compound having an ethylenically unsaturated bond-containing group can be preferably used as a radically polymerizable compound. Moreover, the compound having an epoxy group can be preferably used as a cationically polymerizable compound.
モノマータイプの重合性化合物の分子量は、2000未満であることが好ましく、100以上2000未満であることがより好ましく、200以上2000未満であることがさらに好ましい。モノマータイプの重合性化合物の分子量の上限は、1500以下であることが好ましい。樹脂タイプの重合性化合物の重量平均分子量(Mw)は、2000~2000000であることが好ましい。上限は、1000000以下であることが好ましく、500000以下であることがより好ましい。下限は、3000以上であることが好ましく、5000以上であることがより好ましい。 The molecular weight of the monomer-type polymerizable compound is preferably less than 2000, more preferably 100 or more and less than 2000, and even more preferably 200 or more and less than 2000. The upper limit of the molecular weight of the monomer-type polymerizable compound is preferably 1500 or less. The weight average molecular weight (Mw) of the resin-type polymerizable compound is preferably 2000 to 2000000. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit is preferably 3000 or more, and more preferably 5000 or more.
樹脂タイプの重合性化合物としては、エポキシ樹脂や、重合性基を有する繰り返し単位を含む樹脂などが挙げられる。重合性基を有する繰り返し単位としては、下記式(A2-1)~(A2-4)などが挙げられる。
式中、R1は、水素原子またはアルキル基を表す。アルキル基の炭素数は、1~5が好ましく、1~3がさらに好ましく、1が特に好ましい。R1は、水素原子またはメチル基が好ましい。 In the formula, R 1 represents a hydrogen atom or an alkyl group. The number of carbon atoms of the alkyl group is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1. R 1 is preferably a hydrogen atom or a methyl group.
L51は、単結合または2価の連結基を表す。2価の連結基としては、アルキレン基、アリーレン基、-O-、-S-、-CO-、-COO-、-OCO-、-SO2-、-NR10-(R10は水素原子あるいはアルキル基を表し、水素原子が好ましい)、または、これらの組み合わせからなる基が挙げられる。アルキレン基の炭素数は、1~30が好ましく、1~15がより好ましく、1~10がさらに好ましい。アルキレン基は、置換基を有していてもよいが、無置換が好ましい。アルキレン基は、直鎖、分岐、環状のいずれであってもよい。また、環状のアルキレン基は、単環、多環のいずれであってもよい。アリーレン基の炭素数は、6~18が好ましく、6~14がより好ましく、6~10がさらに好ましい。 L 51 represents a single bond or a divalent linking group. The divalent linking group includes an alkylene group, an arylene group, -O-, -S-, -CO-, -COO-, -OCO-, -SO 2- , -NR 10- (R 10 is a hydrogen atom or (Representing an alkyl group, preferably a hydrogen atom), or a group consisting of a combination thereof can be mentioned. The alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 15 carbon atoms, and even more preferably 1 to 10 carbon atoms. The alkylene group may have a substituent, but is preferably unsubstituted. The alkylene group may be linear, branched or cyclic. Further, the cyclic alkylene group may be either monocyclic or polycyclic. The arylene group preferably has 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, and even more preferably 6 to 10 carbon atoms.
P1は、重合性基を表す。重合性基としては、エチレン性不飽和結合含有基、エポキシ基、メチロール基、アルコキシメチル基などが挙げられる。 P 1 represents a polymerizable group. Examples of the polymerizable group include an ethylenically unsaturated bond-containing group, an epoxy group, a methylol group, and an alkoxymethyl group.
モノマータイプのエチレン性不飽和結合含有基を有する化合物としては、3~15官能の(メタ)アクリレート化合物であることが好ましく、3~6官能の(メタ)アクリレート化合物であることがより好ましい。モノマータイプのエチレン性不飽和結合含有基を含む化合物の例としては、特開2013-253224号公報の段落番号0033~0034の記載を参酌することができ、この内容は本明細書に組み込まれる。モノマータイプのエチレン性不飽和結合を有する基を有する化合物としては、エチレンオキシ変性ペンタエリスリトールテトラアクリレート(市販品としては、NKエステルATM-35E;新中村化学工業(株)製)、ジペンタエリスリトールトリアクリレート(市販品としては、KAYARAD D-330;日本化薬(株)製)、ジペンタエリスリトールテトラアクリレート(市販品としては、KAYARAD D-320;日本化薬(株)製)、ジペンタエリスリトールペンタ(メタ)アクリレート(市販品としては KAYARAD D-310;日本化薬(株)製)、ジペンタエリスリトールヘキサ(メタ)アクリレート(市販品としては、KAYARAD DPHA;日本化薬(株)製、A-DPH-12E;新中村化学工業(株)製)、およびこれらの(メタ)アクリロイル基が、エチレングリコール残基および/またはプロピレングリコール残基を介して結合している構造の化合物が好ましい。またこれらのオリゴマータイプも使用できる。また、特開2013-253224号公報の段落番号0034~0038、特開2012-208494号公報の段落番号0477(対応する米国特許出願公開第2012/0235099号明細書の段落番号0585)に記載の重合性モノマー等を用いることもでき、これらの内容は本明細書に組み込まれる。また、モノマータイプのエチレン性不飽和結合含有基を有する化合物としては、ジグリセリンEO(エチレンオキシド)変性(メタ)アクリレート(市販品としてはM-460;東亞合成製)、ペンタエリスリトールテトラアクリレート(新中村化学工業(株)製、A-TMMT)、1,6-ヘキサンジオールジアクリレート(日本化薬(株)製、KAYARAD HDDA)、RP-1040(日本化薬(株)製)、アロニックス M-350、TO-2349(東亞合成製)を使用することもできる。 The compound having a monomer-type ethylenically unsaturated bond-containing group is preferably a 3- to 15-functional (meth) acrylate compound, and more preferably a 3- to 6-functional (meth) acrylate compound. As an example of a compound containing a monomer-type ethylenically unsaturated bond-containing group, the description in paragraphs 0033 to 0034 of JP2013-253224A can be referred to, and the content thereof is incorporated in the present specification. Examples of the compound having a group having a monomer-type ethylenically unsaturated bond include ethylene oxy-modified pentaerythritol tetraacrylate (commercially available NK ester ATM-35E; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and dipentaerythritol tri. Acrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (Meta) acrylate (commercially available KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A- DPH-12E; manufactured by Shin-Nakamura Chemical Industry Co., Ltd., and compounds having a structure in which these (meth) acryloyl groups are bonded via ethylene glycol residues and / or propylene glycol residues are preferable. Also, these oligomer types can be used. Further, the polymerization described in paragraph numbers 0034 to 0038 of JP2013-253224A and paragraph number 0477 of JP2012-208494A (paragraph number 0585 of the corresponding US Patent Application Publication No. 2012/0235099). Sexual monomers and the like can also be used and these contents are incorporated herein. Compounds having a monomer-type ethylenically unsaturated bond-containing group include diglycerin EO (ethylene oxide) modified (meth) acrylate (commercially available M-460; manufactured by Toa Synthetic) and pentaerythritol tetraacrylate (Shin-Nakamura). Chemical Industry Co., Ltd., A-TMMT), 1,6-hexanediol diacrylate (Nippon Kayaku Co., Ltd., KAYARAD HDDA), RP-1040 (Nippon Kayaku Co., Ltd.), Aronix M-350 , TO-2349 (manufactured by Toa Synthetic) can also be used.
モノマータイプのエチレン性不飽和結合含有基を含む化合物は、カルボキシル基、スルホ基、リン酸基等の酸基を有していてもよい。市販品としては、例えば、東亞合成株式会社製のアロニックスシリーズ(例えば、M-305、M-510、M-520)などが挙げられる。 The compound containing a monomer-type ethylenically unsaturated bond-containing group may have an acid group such as a carboxyl group, a sulfo group, or a phosphoric acid group. Examples of commercially available products include the Aronix series manufactured by Toagosei Co., Ltd. (for example, M-305, M-510, M-520).
モノマータイプのエチレン性不飽和結合含有基を含む化合物は、カプロラクトン構造を有する化合物であることも好ましい。カプロラクトン構造を有する化合物としては、特開2013-253224号公報の段落0042~0045の記載を参酌することができ、この内容は本明細書に組み込まれる。カプロラクトン構造を有する化合物は、例えば、日本化薬(株)からKAYARAD DPCAシリーズとして市販されている、DPCA-20、DPCA-30、DPCA-60、DPCA-120等が挙げられる。 The compound containing a monomer-type ethylenically unsaturated bond-containing group is preferably a compound having a caprolactone structure. As the compound having a caprolactone structure, the description in paragraphs 0042 to 0045 of JP2013-253224A can be referred to, and the contents thereof are incorporated in the present specification. Examples of the compound having a caprolactone structure include DPCA-20, DPCA-30, DPCA-60, DPCA-120, etc., which are commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series.
モノマータイプのエチレン性不飽和結合を有する基を含む化合物として、エチレン性不飽和結合含有基とアルキレンオキシ基を有する化合物を用いることもできる。エチレン性不飽和結合含有基とアルキレンオキシ基を有する化合物としては、エチレン性不飽和結合含有基と、エチレンオキシ基および/またはプロピレンオキシ基とを有する化合物が好ましく、エチレン性不飽和結合を有する基とエチレンオキシ基とを有する化合物がより好ましく、エチレンオキシ基を4~20個有する3~6官能(メタ)アクリレート化合物がさらに好ましい。エチレン性不飽和結合含有基とアルキレンオキシ基を有する化合物の市販品としては、例えばサートマー社製のエチレンオキシ基を4個有する4官能(メタ)アクリレートであるSR-494、イソブチレンオキシ基を3個有する3官能(メタ)アクリレートであるKAYARAD TPA-330などが挙げられる。 As a compound containing a group having a monomer-type ethylenically unsaturated bond, a compound having an ethylenically unsaturated bond-containing group and an alkyleneoxy group can also be used. As the compound having an ethylenically unsaturated bond-containing group and an alkyleneoxy group, a compound having an ethylenically unsaturated bond-containing group and an ethyleneoxy group and / or a propyleneoxy group is preferable, and a group having an ethylenically unsaturated bond. A compound having an ethyleneoxy group and an ethyleneoxy group is more preferable, and a 3 to 6 functional (meth) acrylate compound having 4 to 20 ethyleneoxy groups is further preferable. Commercially available products of compounds having an ethylenically unsaturated bond-containing group and an alkyleneoxy group include SR-494, which is a tetrafunctional (meth) acrylate having four ethyleneoxy groups manufactured by Sartomer, and three isobutyleneoxy groups. Examples thereof include KAYARAD TPA-330, which is a trifunctional (meth) acrylate having.
エチレン性不飽和結合含有基を含む化合物としては、特公昭48-041708号公報、特開昭51-037193号公報、特公平02-032293号公報、特公平02-016765号公報に記載されているウレタンアクリレート類や、特公昭58-049860号公報、特公昭56-017654号公報、特公昭62-039417号公報、特公昭62-039418号公報に記載されているエチレンオキサイド系骨格を有するウレタン化合物類も好適である。また、特開昭63-277653号公報、特開昭63-260909号公報、特開平01-105238号公報に記載されている分子内にアミノ構造やスルフィド構造を有する付加重合性化合物類を用いることができる。市販品としては、UA-7200(新中村化学工業(株)製)、DPHA-40H(日本化薬(株)製)、UA-306H、UA-306T、UA-306I、AH-600、T-600、AI-600(共栄社化学(株))製などが挙げられる。また、エチレン性不飽和結合含有基を含む化合物としては、特開2017-048367号公報、特許第6057891号公報、特許第6031807号公報に記載されている化合物を用いることもできる。また、エチレン性不飽和結合含有基を含む化合物としては、8UH-1006、8UH-1012(大成ファインケミカル(株)製)、ライトアクリレートPOB-A0(共栄社化学(株)製)などを用いることも好ましい。 Examples of the compound containing an ethylenically unsaturated bond-containing group are described in Japanese Patent Application Laid-Open No. 48-041708, Japanese Patent Application Laid-Open No. 51-0371993, Japanese Patent Application Laid-Open No. 02-032293, and Japanese Patent Application Laid-Open No. 02-0176765. Urethane acrylates and urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418. Is also suitable. Further, use of addition-polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238. Can be done. Commercially available products include UA-7200 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T- Examples include 600 and AI-600 (Kyoeisha Chemical Co., Ltd.). Further, as the compound containing an ethylenically unsaturated bond-containing group, the compounds described in Japanese Patent Application Laid-Open No. 2017-0438367, Japanese Patent No. 6057891, and Japanese Patent No. 6031807 can also be used. Further, as the compound containing an ethylenically unsaturated bond-containing group, it is also preferable to use 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.), light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), or the like. ..
本発明の硬化性組成物がエチレン性不飽和結合含有基を含む化合物を含有する場合、硬化性組成物の全固形分中におけるエチレン性不飽和結合含有基を含む化合物の含有量は、0.1質量%以上であることが好ましく、0.5質量%以上がより好ましく、1質量%以上が更に好ましく、5質量%以上が特に好ましい。上限は、80質量%以下が好ましく、70質量%以下がより好ましく、60質量%以下が更に好ましく、50質量%以下がより一層好ましく、40質量%以下が更に一層好ましく、30質量%以下が特に好ましい。 When the curable composition of the present invention contains a compound containing an ethylenically unsaturated bond-containing group, the content of the compound containing an ethylenically unsaturated bond-containing group in the total solid content of the curable composition is 0. It is preferably 1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, and particularly preferably 5% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, further preferably 50% by mass or less, further preferably 40% by mass or less, and particularly preferably 30% by mass or less. preferable.
エポキシ基を有する化合物(以下、エポキシ化合物ともいう)としては、単官能または多官能グリシジルエーテル化合物や、多官能脂肪族グリシジルエーテル化合物などが挙げられる。また、エポキシ化合物としては、脂環式エポキシ基を有する化合物を用いることもできる。 Examples of the compound having an epoxy group (hereinafter, also referred to as an epoxy compound) include a monofunctional or polyfunctional glycidyl ether compound, a polyfunctional aliphatic glycidyl ether compound, and the like. Further, as the epoxy compound, a compound having an alicyclic epoxy group can also be used.
エポキシ化合物としては、1分子にエポキシ基を1つ以上有する化合物が挙げられる。エポキシ化合物はエポキシ基を1分子に1~100個有する化合物が好ましい。エポキシ基の数の上限は、例えば、10個以下とすることもでき、5個以下とすることもできる。エポキシ基の下限は2個以上が好ましい。 Examples of the epoxy compound include compounds having one or more epoxy groups in one molecule. The epoxy compound is preferably a compound having 1 to 100 epoxy groups in one molecule. The upper limit of the number of epoxy groups may be, for example, 10 or less, or 5 or less. The lower limit of the epoxy group is preferably two or more.
エポキシ化合物は、低分子化合物(例えば、分子量1000未満)でもよいし、高分子化合物(macromolecule)(例えば、分子量1000以上、ポリマーの場合は、重量平均分子量が1000以上)のいずれでもよい。エポキシ化合物の重量平均分子量は、2000~100000が好ましい。重量平均分子量の上限は、10000以下が好ましく、5000以下がより好ましく、3000以下が更に好ましい。 The epoxy compound may be either a small molecule compound (for example, a molecular weight of less than 1000) or a high molecular compound (macromolecule) (for example, a molecular weight of 1000 or more, and in the case of a polymer, a weight average molecular weight of 1000 or more). The weight average molecular weight of the epoxy compound is preferably 2000 to 100,000. The upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5000 or less, and even more preferably 3000 or less.
エポキシ化合物の市販品としては、EHPE3150((株)ダイセル製)、EPICLON N-695(DIC(株)製)、アデカグリシロール ED-505((株)ADEKA製、エポキシ基含有モノマー)、マープルーフG-0150M、G-0105SA、G-0130SP、G-0250SP、G-1005S、G-1005SA、G-1010S、G-2050M、G-01100、G-01758(日油(株)製、エポキシ基含有ポリマー)などが挙げられる。また、エポキシ化合物としては、特開2013-011869号公報の段落番号0034~0036、特開2014-043556号公報の段落番号0147~0156、特開2014-089408号公報の段落番号0085~0092に記載された化合物を用いることもできる。これらの内容は、本明細書に組み込まれる。 Commercially available epoxy compounds include EHPE3150 (manufactured by Daicel Co., Ltd.), EPICLON N-695 (manufactured by DIC Corporation), ADEKA Glycyrrol ED-505 (manufactured by ADEKA Co., Ltd., epoxy group-containing monomer), and marproof. G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (manufactured by Nichiyu Co., Ltd., containing epoxy group) Polymer) and the like. Further, as the epoxy compound, it is described in paragraph numbers 0034 to 0036 of JP2013-011869A, paragraph numbers 0147 to 0156 of JP-A-2014-0435556, and paragraph numbers 0085-0092 of JP-A-2014-089408. It is also possible to use the compound. These contents are incorporated herein by reference.
本発明の硬化性組成物がエポキシ化合物を含有する場合、硬化性組成物の全固形分中におけるエポキシ化合物の含有量は、0.1質量%以上が好ましく、0.5質量%以上がより好ましく、1質量%以上が更に好ましく、5質量%以上が特に好ましい。上限は、80質量%以下が好ましく、70質量%以下がより好ましく、60質量%以下が更に好ましく、50質量%以下がより一層好ましく、40質量%以下が更に一層好ましく、30質量%以下が特に好ましい。 When the curable composition of the present invention contains an epoxy compound, the content of the epoxy compound in the total solid content of the curable composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more. 1, 1% by mass or more is more preferable, and 5% by mass or more is particularly preferable. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, further preferably 50% by mass or less, further preferably 40% by mass or less, and particularly preferably 30% by mass or less. preferable.
メチロール基を有する化合物(以下、メチロール化合物ともいう)としては、メチロール基が、窒素原子または芳香族環を形成する炭素原子に結合している化合物が挙げられる。メチロール基が、窒素原子に結合している化合物としては、アルコキシメチル化メラミン、メチロール化メラミン、アルコキシメチル化ベンゾグアナミン、メチロール化ベンゾグアナミン、アルコキシメチル化グリコールウリル、メチロール化グリコールウリル、アルコキシメチル化尿素およびメチロール化尿素等が好ましい。また、特開2004-295116号公報の段落0134~0147、特開2014-089408号公報の段落0095~0126の記載を参酌でき、これらの内容は本明細書に組み込まれる。 Examples of the compound having a methylol group (hereinafter, also referred to as a methylol compound) include a compound in which the methylol group is bonded to a nitrogen atom or a carbon atom forming an aromatic ring. Compounds in which the methylol group is bonded to a nitrogen atom include alkoxymethylated melamine, methylolated melamine, alkoxymethylated benzoguanamine, methylated benzoguanamine, alkoxymethylated glycol uryl, methylated glycol uryl, alkoxymethylated urea and methylol. Urea compound and the like are preferable. Further, the description of paragraphs 0134 to 0147 of JP-A-2004-295116 and paragraphs 095 to 0126 of JP-A-2014-089408 can be referred to, and these contents are incorporated in the present specification.
本発明の硬化性組成物がメチロール化合物を含有する場合、硬化性組成物の全固形分中におけるメチロール化合物の含有量は、0.1質量%以上が好ましく、0.5質量%以上がより好ましく、1質量%以上が更に好ましく、5質量%以上が特に好ましい。上限は、80質量%以下が好ましく、70質量%以下がより好ましく、60質量%以下が更に好ましく、50質量%以下がより一層好ましく、40質量%以下が更に一層好ましく、30質量%以下が特に好ましい。 When the curable composition of the present invention contains a methylol compound, the content of the methylol compound in the total solid content of the curable composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more. 1, 1% by mass or more is more preferable, and 5% by mass or more is particularly preferable. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, further preferably 50% by mass or less, further preferably 40% by mass or less, and particularly preferably 30% by mass or less. preferable.
(樹脂)
本発明の硬化性組成物は、硬化性化合物として樹脂を用いることができる。硬化性化合物は、樹脂を少なくとも含むものを用いることが好ましい。樹脂は分散剤として用いることもできる。なお、顔料などを分散させるために用いられる樹脂を分散剤ともいう。ただし、樹脂のこのような用途は一例であって、このような用途以外の目的で樹脂を使用することもできる。なお、重合性基を有する樹脂は、重合性化合物にも該当する。
(resin)
In the curable composition of the present invention, a resin can be used as the curable compound. It is preferable to use a curable compound containing at least a resin. The resin can also be used as a dispersant. The resin used to disperse pigments and the like is also referred to as a dispersant. However, such an application of the resin is an example, and the resin can be used for a purpose other than such an application. The resin having a polymerizable group also corresponds to a polymerizable compound.
樹脂の重量平均分子量(Mw)は、2000~2000000が好ましい。上限は、1000000以下が好ましく、500000以下がより好ましい。下限は、3000以上が好ましく、5000以上がより好ましい。 The weight average molecular weight (Mw) of the resin is preferably 2000 to 2000000. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit is preferably 3000 or more, and more preferably 5000 or more.
樹脂としては、(メタ)アクリル樹脂、エポキシ樹脂、エン・チオール樹脂、ポリカーボネート樹脂、ポリエーテル樹脂、ポリアリレート樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、ポリフェニレン樹脂、ポリアリーレンエーテルホスフィンオキシド樹脂、ポリイミド樹脂、ポリアミドイミド樹脂、ポリオレフィン樹脂、環状オレフィン樹脂、ポリエステル樹脂、スチレン樹脂などが挙げられる。エポキシ樹脂としては、上述した重合性化合物の欄で説明したエポキシ化合物として例示した化合物のうちポリマータイプの化合物が挙げられる。環状オレフィン樹脂の市販品としては、ARTON F4520(JSR(株)製)などが挙げられる。また、国際公開第2016/088645号の実施例に記載された樹脂、特開2017-057265号公報に記載された樹脂、特開2017-032685号公報に記載された樹脂、特開2017-075248号公報に記載された樹脂、特開2017-066240号公報に記載された樹脂を用いることもでき、これらの内容は本明細書に組み込まれる。また、フルオレン骨格を有する樹脂を用いることもできる。 Examples of the resin include (meth) acrylic resin, epoxy resin, en-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, and polyimide resin. Examples thereof include polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, and styrene resin. Examples of the epoxy resin include polymer-type compounds among the compounds exemplified as the epoxy compounds described in the above-mentioned section of polymerizable compounds. Examples of commercially available cyclic olefin resins include ARTON F4520 (manufactured by JSR Corporation). Further, the resin described in Examples of International Publication No. 2016/088645, the resin described in JP-A-2017-057256, the resin described in JP-A-2017-032685, JP-A-2017-075248. The resin described in Japanese Patent Application Laid-Open No. 2017-066240 can also be used, and the contents thereof are incorporated in the present specification. Further, a resin having a fluorene skeleton can also be used.
本発明で用いる樹脂は、酸基を有していてもよい。酸基としては、例えば、カルボキシル基、リン酸基、スルホ基、フェノール性ヒドロキシ基などが挙げられ、カルボキシル基が好ましい。これら酸基は、1種のみであってもよいし、2種以上であってもよい。酸基を有する樹脂はアルカリ可溶性樹脂として用いることもできる。 The resin used in the present invention may have an acid group. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfo group, a phenolic hydroxy group and the like, and a carboxyl group is preferable. These acid groups may be only one kind or two or more kinds. The resin having an acid group can also be used as an alkali-soluble resin.
酸基を有する樹脂としては、側鎖にカルボキシル基を有するポリマーが好ましい。具体例としては、メタクリル酸共重合体、アクリル酸共重合体、イタコン酸共重合体、クロトン酸共重合体、マレイン酸共重合体、部分エステル化マレイン酸共重合体、ノボラック樹脂などのアルカリ可溶性フェノール樹脂、側鎖にカルボキシル基を有する酸性セルロース誘導体、ヒドロキシ基を有するポリマーに酸無水物を付加させた樹脂が挙げられる。特に、(メタ)アクリル酸と、これと共重合可能な他のモノマーとの共重合体が、アルカリ可溶性樹脂として好適である。(メタ)アクリル酸と共重合可能な他のモノマーとしては、アルキル(メタ)アクリレート、アリール(メタ)アクリレート、ビニル化合物などが挙げられる。アルキル(メタ)アクリレートおよびアリール(メタ)アクリレートとしては、メチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、ペンチル(メタ)アクリレート、ヘキシル(メタ)アクリレート、オクチル(メタ)アクリレート、フェニル(メタ)アクリレート、ベンジル(メタ)アクリレート、トリル(メタ)アクリレート、ナフチル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート等、ビニル化合物としては、スチレン、α-メチルスチレン、ビニルトルエン、グリシジルメタクリレート、アクリロニトリル、ビニルアセテート、N-ビニルピロリドン、テトラヒドロフルフリルメタクリレート、ポリスチレンマクロモノマー、ポリメチルメタクリレートマクロモノマー等が挙げられる。また他のモノマーは、特開平10-300922号公報に記載のN位置換マレイミドモノマー、例えば、N-フェニルマレイミド、N-シクロヘキシルマレイミド等を用いることもできる。なお、これらの(メタ)アクリル酸と共重合可能な他のモノマーは1種のみであってもよいし、2種以上であってもよい。 As the resin having an acid group, a polymer having a carboxyl group in the side chain is preferable. Specific examples include alkali-soluble methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and novolak resins. Examples thereof include phenol resins, acidic cellulose derivatives having a carboxyl group in the side chain, and resins obtained by adding an acid anhydride to a polymer having a hydroxy group. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, vinyl compounds and the like. Examples of alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and pentyl (meth) acrylate. Hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, trill (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, etc. Examples thereof include α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethylmethacrylate macromonomer and the like. As the other monomer, N-substituted maleimide monomers described in JP-A-10-300922, for example, N-phenylmaleimide, N-cyclohexylmaleimide and the like can also be used. The other monomers copolymerizable with these (meth) acrylic acids may be only one kind or two or more kinds.
酸基を有する樹脂は、更に重合性基を有する繰り返し単位を含有していてもよい。酸基を有する樹脂が、更に重合性基を有する繰り返し単位を含有する場合、全繰り返し単位中における重合性基を有する繰り返し単位の含有量は、10~90モル%であることが好ましく、20~90モル%であることがより好ましく、20~85モル%であることがさらに好ましい。また、全繰り返し単位中における酸基を有する繰り返し単位の含有量は、1~50モル%であることが好ましく、5~40モル%であることがより好ましく、5~30モル%であることがさらに好ましい。 The resin having an acid group may further contain a repeating unit having a polymerizable group. When the resin having an acid group further contains a repeating unit having a polymerizable group, the content of the repeating unit having a polymerizable group in all the repeating units is preferably 10 to 90 mol%, and 20 to 20 to 90 mol%. It is more preferably 90 mol%, further preferably 20 to 85 mol%. The content of the repeating unit having an acid group in all the repeating units is preferably 1 to 50 mol%, more preferably 5 to 40 mol%, and preferably 5 to 30 mol%. More preferred.
酸基を有する樹脂は、下記式(ED1)で示される化合物および/または下記式(ED2)で表される化合物(以下、これらの化合物を「エーテルダイマー」と称することもある。)を含むモノマー成分に由来する繰り返し単位を含むポリマーであることも好ましい。 The resin having an acid group is a monomer containing a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as "ether dimer"). It is also preferable that the polymer contains repeating units derived from the components.
式(ED1)中、R1およびR2は、各々独立に水素原子または置換基を有していてもよい炭素数1~25の炭化水素基を表す。
エーテルダイマーの具体例としては、例えば、特開2013-029760号公報の段落番号0317を参酌することができ、この内容は本明細書に組み込まれる。エーテルダイマーは、1種のみであってもよいし、2種以上であってもよい。 As a specific example of the ether dimer, for example, paragraph number 0317 of JP2013-209760A can be referred to, and this content is incorporated in the present specification. The ether dimer may be of only one type or of two or more types.
酸基を有する樹脂は、下記式(X)で示される化合物に由来する繰り返し単位を含んでいてもよい。
酸基を有する樹脂については、特開2012-208494号公報の段落番号0558~0571(対応する米国特許出願公開第2012/0235099号明細書の段落番号0685~0700)の記載、特開2012-198408号公報の段落番号0076~0099の記載を参酌でき、これらの内容は本明細書に組み込まれる。また、酸基を有する樹脂は市販品を用いることもできる。例えば、アクリベースFF-426(藤倉化成(株)製)などが挙げられる。 Regarding the resin having an acid group, the description in paragraph numbers 0558 to 0571 of JP2012-208494A (paragraph numbers 0685 to 0700 of the corresponding US Patent Application Publication No. 2012/0235099), JP2012-198408 The description of paragraphs 0076 to 09999 of the publication can be taken into consideration, and these contents are incorporated in the present specification. Further, as the resin having an acid group, a commercially available product can also be used. For example, Acrybase FF-426 (manufactured by Fujikura Kasei Co., Ltd.) and the like can be mentioned.
酸基を有する樹脂の酸価は、30~200mgKOH/gが好ましい。下限は、50mgKOH/g以上が好ましく、70mgKOH/g以上がより好ましい。上限は、150mgKOH/g以下が好ましく、120mgKOH/g以下がより好ましい。 The acid value of the resin having an acid group is preferably 30 to 200 mgKOH / g. The lower limit is preferably 50 mgKOH / g or more, and more preferably 70 mgKOH / g or more. The upper limit is preferably 150 mgKOH / g or less, and more preferably 120 mgKOH / g or less.
酸基を有する樹脂としては、例えば下記構造の樹脂などが挙げられる。以下の式中、Meはメチル基を表す。
本発明の組成物は、分散剤としての樹脂を含むこともできる。分散剤は、酸性分散剤(酸性樹脂)、塩基性分散剤(塩基性樹脂)が挙げられる。ここで、酸性分散剤(酸性樹脂)とは、酸基の量が塩基性基の量よりも多い樹脂を表す。酸性分散剤(酸性樹脂)は、酸基の量と塩基性基の量の合計量を100モル%としたときに、酸基の量が70モル%以上を占める樹脂が好ましく、実質的に酸基のみからなる樹脂がより好ましい。酸性分散剤(酸性樹脂)が有する酸基は、カルボキシル基が好ましい。酸性分散剤(酸性樹脂)の酸価は、40~105mgKOH/gが好ましく、50~105mgKOH/gがより好ましく、60~105mgKOH/gがさらに好ましい。また、塩基性分散剤(塩基性樹脂)とは、塩基性基の量が酸基の量よりも多い樹脂を表す。塩基性分散剤(塩基性樹脂)は、酸基の量と塩基性基の量の合計量を100モル%としたときに、塩基性基の量が50モル%を超える樹脂が好ましい。塩基性分散剤が有する塩基性基は、アミノ基であることが好ましい。分散剤は、酸性分散剤(酸性樹脂)であることが好ましい。 The composition of the present invention may also contain a resin as a dispersant. Examples of the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin). Here, the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is larger than the amount of basic groups. The acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups accounts for 70 mol% or more when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%, and is substantially an acid. A resin consisting only of groups is more preferable. The acid group of the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 40 to 105 mgKOH / g, more preferably 50 to 105 mgKOH / g, and even more preferably 60 to 105 mgKOH / g. Further, the basic dispersant (basic resin) represents a resin in which the amount of basic groups is larger than the amount of acid groups. The basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol% when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%. The basic group contained in the basic dispersant is preferably an amino group. The dispersant is preferably an acidic dispersant (acidic resin).
分散剤として用いる樹脂は、グラフト共重合体であることも好ましい。グラフト共重合体は、グラフト鎖によって溶剤との親和性を有するために、顔料の分散性、及び、経時後の分散安定性に優れる。グラフト共重合体の詳細は、特開2012-255128号公報の段落番号0025~0094の記載を参酌でき、この内容は本明細書に組み込まれる。 The resin used as the dispersant is also preferably a graft copolymer. Since the graft copolymer has an affinity with a solvent due to the graft chain, it is excellent in the dispersibility of the pigment and the dispersion stability after aging. For details of the graft copolymer, the description in paragraphs 0025 to 0094 of JP2012-255128A can be referred to, and the content thereof is incorporated in the present specification.
分散剤として用いる樹脂は、主鎖及び側鎖の少なくとも一方に窒素原子を含むオリゴイミン系分散剤であることも好ましい。オリゴイミン系分散剤としては、pKa14以下の官能基を有する部分構造Xを有する構造単位と、原子数40~10,000の側鎖Yを含む側鎖とを有し、かつ主鎖及び側鎖の少なくとも一方に塩基性窒素原子を有する樹脂が好ましい。塩基性窒素原子とは、塩基性を呈する窒素原子であれば特に制限はない。オリゴイミン系分散剤については、特開2012-255128号公報の段落番号0102~0174の記載を参酌でき、この内容は本明細書に組み込まれる。 It is also preferable that the resin used as the dispersant is an oligoimine-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain. The oligoimine-based dispersant has a structural unit having a partial structure X having a functional group of pKa14 or less, a side chain containing a side chain Y having 40 to 10,000 atoms, and a main chain and a side chain. A resin having a basic nitrogen atom on at least one of them is preferable. The basic nitrogen atom is not particularly limited as long as it is a nitrogen atom exhibiting basicity. Regarding the oligoimine-based dispersant, the description in paragraphs 0102 to 0174 of JP2012-255128A can be referred to, and this content is incorporated in the present specification.
分散剤は、市販品としても入手可能であり、そのような具体例としては、BYK2000(ビックケミージャパン(株)製)などが挙げられる。また、特開2014-130338号公報の段落番号0041~0130に記載された顔料分散剤を用いることもでき、この内容は本明細書に組み込まれる。また、上述した酸基を有する樹脂などを分散剤として用いることもできる。 The dispersant is also available as a commercially available product, and specific examples thereof include BYK2000 (manufactured by Big Chemie Japan Co., Ltd.). Further, the pigment dispersants described in paragraphs 0041 to 0130 of JP-A-2014-130338 can also be used, and the contents thereof are incorporated in the present specification. Further, the above-mentioned resin having an acid group or the like can also be used as a dispersant.
本発明の硬化性組成物が樹脂を含む場合、硬化性組成物に含まれる樹脂の全量中における、アミン価を有する樹脂の含有量は、硬化性組成物の保存安定性の観点から30質量%以下であることが好ましく、20質量%以下であることがより好ましく、10質量%以下であることが更に好ましく、5質量%以下であることがより一層好ましく、1質量%以下であることが更に一層好ましく、0.1質量%以下であることが特に好ましい。 When the curable composition of the present invention contains a resin, the content of the resin having an amine value in the total amount of the resin contained in the curable composition is 30% by mass from the viewpoint of storage stability of the curable composition. It is preferably 20% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, and further preferably 1% by mass or less. It is more preferably 0.1% by mass or less, and particularly preferably 0.1% by mass or less.
本発明の硬化性組成物が樹脂を含有する場合、硬化性組成物の全固形分中における樹脂の含有量は、0.1~50質量%が好ましい。下限は、1質量%以上が好ましく、3質量%以上がより好ましく、5質量%以上が更に好ましく、10質量%以上が特に好ましい。上限は、40質量%以下がより好ましく、30質量%以下が更に好ましい。
また、硬化性組成物の保存安定性の観点から、硬化性組成物の全固形分中におけるアミン価を有する樹脂の含有量は30質量%以下であることが好ましく、20質量%以下であることがより好ましく、10質量%以下であることが更に好ましい。本発明の硬化性組成物は、アミン価を有する樹脂を実質的に含有しないことが特に好ましい。本発明の硬化性組成物が、アミン価を有する樹脂を実質的に含有しない場合とは、硬化性組成物の全固形分中におけるアミン価を有する樹脂の含有量が、0.05質量%以下であることを意味し、0.01質量%以下であることが好ましく、アミン価を有する樹脂を含有しないことが特に好ましい。
本発明の硬化性組成物は、樹脂を、1種のみを含んでいてもよいし、2種以上含んでいてもよい。2種以上含む場合は、それらの合計量が上記範囲となることが好ましい。
When the curable composition of the present invention contains a resin, the content of the resin in the total solid content of the curable composition is preferably 0.1 to 50% by mass. The lower limit is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, and particularly preferably 10% by mass or more. The upper limit is more preferably 40% by mass or less, further preferably 30% by mass or less.
Further, from the viewpoint of storage stability of the curable composition, the content of the resin having an amine value in the total solid content of the curable composition is preferably 30% by mass or less, preferably 20% by mass or less. Is more preferable, and 10% by mass or less is further preferable. It is particularly preferable that the curable composition of the present invention contains substantially no resin having an amine value. When the curable composition of the present invention does not substantially contain a resin having an amine value, the content of the resin having an amine value in the total solid content of the curable composition is 0.05% by mass or less. It is preferably 0.01% by mass or less, and particularly preferably does not contain a resin having an amine value.
The curable composition of the present invention may contain only one type of resin, or may contain two or more types of resin. When two or more kinds are contained, it is preferable that the total amount thereof is within the above range.
本発明の硬化性組成物が重合性化合物(好ましくはエチレン性不飽和結合含有基を有するモノマータイプの重合性化合物)と樹脂とを含む場合、重合性化合物と樹脂との質量比は、重合性化合物/樹脂=0.4~1.4であることが好ましい。上記質量比の下限は0.5以上が好ましく、0.6以上がより好ましい。上記質量比の上限は1.3以下が好ましく、1.2以下がより好ましい。上記質量比が、上記範囲であれば、より矩形性に優れた画素(膜)を形成することができる。 When the curable composition of the present invention contains a polymerizable compound (preferably a monomer-type polymerizable compound having an ethylenically unsaturated bond-containing group) and a resin, the mass ratio of the polymerizable compound to the resin is polymerizable. The compound / resin is preferably 0.4 to 1.4. The lower limit of the mass ratio is preferably 0.5 or more, more preferably 0.6 or more. The upper limit of the mass ratio is preferably 1.3 or less, more preferably 1.2 or less. When the mass ratio is in the above range, pixels (films) having more rectangular properties can be formed.
<<光重合開始剤>>
本発明の硬化性組成物は、光重合開始剤を含有することができる。光重合開始剤としては、光ラジカル重合開始剤、光カチオン重合開始剤などが挙げられる。重合性化合物の種類に応じて選択して用いることが好ましい。重合性化合物として、エチレン性不飽和結合含有基を有する化合物などのラジカル重合性化合物を用いた場合においては、光重合開始剤として光ラジカル重合開始剤を用いることが好ましい。また、重合性化合物としてカチオン重合性化合物を用いた場合においては、光重合開始剤として光カチオン重合開始剤を用いることが好ましい。光重合開始剤としては、特に制限はなく、公知の光重合開始剤の中から適宜選択することができる。例えば、紫外領域から可視領域の光線に対して感光性を有する化合物が好ましい。
<< Photopolymerization Initiator >>
The curable composition of the present invention can contain a photopolymerization initiator. Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator. It is preferable to select and use it according to the type of the polymerizable compound. When a radically polymerizable compound such as a compound having an ethylenically unsaturated bond-containing group is used as the polymerizable compound, it is preferable to use a photoradical polymerization initiator as the photopolymerization initiator. When a cationically polymerizable compound is used as the polymerizable compound, it is preferable to use a photocationic polymerization initiator as the photopolymerization initiator. The photopolymerization initiator is not particularly limited and may be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light rays in the ultraviolet region to the visible region is preferable.
硬化性組成物の全固形分中における光重合開始剤の含有量は、0.1~50質量%が好ましく、0.5~30質量%がより好ましく、1~20質量%が更に好ましい。光重合開始剤の含有量が上記範囲であれば、より良好な感度とパターン形成性を有する膜が得られる。本発明の硬化性組成物は、光重合開始剤を1種類のみ含んでいてもよいし、2種類以上含んでいてもよい。光重合開始剤を2種類以上含む場合は、それらの合計量が上記範囲となることが好ましい。 The content of the photopolymerization initiator in the total solid content of the curable composition is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, still more preferably 1 to 20% by mass. When the content of the photopolymerization initiator is in the above range, a film having better sensitivity and pattern forming property can be obtained. The curable composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types of photopolymerization initiators. When two or more types of photopolymerization initiators are contained, the total amount thereof is preferably in the above range.
(光ラジカル重合開始剤)
光ラジカル重合開始剤としては、ハロゲン化炭化水素誘導体(例えば、トリアジン骨格を有する化合物、オキサジアゾール骨格を有する化合物など)、アシルホスフィン化合物、ヘキサアリールビイミダゾール、オキシム化合物、有機過酸化物、チオ化合物、ケトン化合物、芳香族オニウム塩、α-ヒドロキシケトン化合物、α-アミノケトン化合物などが挙げられる。光重合開始剤は、露光感度の観点から、トリハロメチルトリアジン化合物、ベンジルジメチルケタール化合物、α-ヒドロキシケトン化合物、α-アミノケトン化合物、アシルホスフィン化合物、ホスフィンオキサイド化合物、メタロセン化合物、オキシム化合物、トリアリールイミダゾールダイマー、オニウム化合物、ベンゾチアゾール化合物、ベンゾフェノン化合物、アセトフェノン化合物、シクロペンタジエン-ベンゼン-鉄錯体、ハロメチルオキサジアゾール化合物および3-アリール置換クマリン化合物であることが好ましく、オキシム化合物、α-ヒドロキシケトン化合物、α-アミノケトン化合物、および、アシルホスフィン化合物から選ばれる化合物であることがより好ましく、オキシム化合物であることが更に好ましい。また、光ラジカル重合開始剤としては、特開2014-130173号公報の段落0065~0111、特許第6301489号公報に記載された化合物、MATERIAL STAGE 37~60p,vol.19,No.3,2019に記載されたパーオキサイド系光重合開始剤、国際公開第2018/221177号に記載の光重合開始剤、国際公開第2018/110179号に記載の光重合開始剤、特開2019-043864号公報に記載の光重合開始剤、特開2019-044030号公報に記載の光重合開始剤が挙げられ、これらの内容は本明細書に組み込まれる。
(Photoradical polymerization initiator)
Examples of the photoradical polymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole, oxime compounds, organic peroxides, and thio. Examples thereof include compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, and α-aminoketone compounds. From the viewpoint of exposure sensitivity, the photopolymerization initiator is a trihalomethyltriazine compound, a benzyl dimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, or a triarylimidazole. It is preferably a dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxaziazole compound and a 3-aryl substituted coumarin compound, and an oxime compound and an α-hydroxyketone compound. , Α-Aminoketone compound, and an acylphosphine compound are more preferable, and an oxime compound is further preferable. Further, as the photoradical polymerization initiator, the compounds described in paragraphs 0065 to 0111 of JP-A-2014-130173 and JP-A-6301489, MATERIAL STAGE 37-60p, vol. 19, No. 3, 2019 Peroxide-based Photopolymerization Initiator, International Publication No. 2018/221177, Photopolymerization Initiator, International Publication No. 2018/110179, Photopolymerization Initiator, Japanese Patent Application Laid-Open No. 2019-043864 Examples thereof include the photopolymerization initiator described in JP-A-2019-044030 and the photopolymerization initiator described in JP-A-2019-044030, the contents of which are incorporated in the present specification.
α-ヒドロキシケトン化合物の市販品としては、Omnirad 184、Omnirad 1173、Omnirad 2959、Omnirad 127(以上、IGM Resins B.V.社製)、Irgacure 184、Irgacure 1173、Irgacure 2959、Irgacure 127(以上、BASF社製)などが挙げられる。α-アミノケトン化合物の市販品としては、Omnirad 907、Omnirad 369、Omnirad 369E、Omnirad 379EG(以上、IGM Resins B.V.社製)、Irgacure 907、Irgacure 369、Irgacure 369E、Irgacure 379EG(以上、BASF社製)などが挙げられる。アシルホスフィン化合物の市販品としては、Omnirad 819、Omnirad TPO(以上、IGM Resins B.V.社製)、Irgacure 819、Irgacure TPO(以上、BASF社製)などが挙げられる。 Commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), Irgacure 184, Irgacure 1173, Irgacare 1173, Irgacure29. (Manufactured by the company) and the like. Commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (above, IGM Resins BV), Irgacare 907, Irgacare 369, Irgacure 369, Irgacure 369, Irgar (Made) and so on. Examples of commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (above, manufactured by IGM Resins BV), Irgacure 819, and Irgacure TPO (above, manufactured by BASF).
オキシム化合物としては、特開2001-233842号公報に記載の化合物、特開2000-080068号公報に記載の化合物、特開2006-342166号公報に記載の化合物、J.C.S.Perkin II(1979年、pp.1653-1660)に記載の化合物、J.C.S.Perkin II(1979年、pp.156-162)に記載の化合物、Journal of Photopolymer Science and Technology(1995年、pp.202-232)に記載の化合物、特開2000-066385号公報に記載の化合物、特表2004-534797号公報に記載の化合物、特開2017-019766号公報に記載の化合物、特許第6065596号公報に記載の化合物、国際公開第2015/152153号に記載の化合物、国際公開第2017/051680号に記載の化合物、特開2017-198865号公報に記載の化合物、国際公開第2017/164127号の段落番号0025~0038に記載の化合物、国際公開第2013/167515号に記載の化合物などが挙げられる。オキシム化合物の具体例としては、3-ベンゾイルオキシイミノブタン-2-オン、3-アセトキシイミノブタン-2-オン、3-プロピオニルオキシイミノブタン-2-オン、2-アセトキシイミノペンタン-3-オン、2-アセトキシイミノ-1-フェニルプロパン-1-オン、2-ベンゾイルオキシイミノ-1-フェニルプロパン-1-オン、3-(4-トルエンスルホニルオキシ)イミノブタン-2-オン、及び2-エトキシカルボニルオキシイミノ-1-フェニルプロパン-1-オンなどが挙げられる。市販品としては、Irgacure OXE01、Irgacure OXE02、Irgacure OXE03、Irgacure OXE04(以上、BASF社製)、TR-PBG-304(常州強力電子新材料有限公司製)、アデカオプトマーN-1919((株)ADEKA製、特開2012-014052号公報に記載の光重合開始剤2)が挙げられる。また、オキシム化合物としては、着色性が無い化合物や、透明性が高く変色し難い化合物を用いることも好ましい。市販品としては、アデカアークルズNCI-730、NCI-831、NCI-930(以上、(株)ADEKA製)などが挙げられる。 Examples of the oxime compound include the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-080068, and the compounds described in JP-A-2006-342166. C. S. The compound according to Perkin II (1979, pp. 1653-1660), J. Mol. C. S. The compound described in Perkin II (1979, pp. 156-162), the compound described in Journal of Photopolymer Science and Technology (1995, pp. 202-232), the compound described in JP-A-2000-066385, the compound described in JP-A-2000-066385. Compounds described in Japanese Patent Application Laid-Open No. 2004-534977, compounds described in JP-A-2017-109766, compounds described in Japanese Patent Application Laid-Open No. 6065596, compounds described in International Publication No. 2015/152153, International Publication No. 2017 / 051680, compounds described in JP-A-2017-198865, compounds described in paragraphs 0025 to 0038 of International Publication No. 2017/164127, compounds described in International Publication No. 2013/167515, etc. Can be mentioned. Specific examples of the oxime compound include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-Acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxycarbonyloxy Examples thereof include imino-1-phenylpropane-1-one. Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04 (above, manufactured by BASF), TR-PBG-304 (manufactured by Joshu Powerful Electronic New Materials Co., Ltd.), ADEKA PTOMER N-1919 (Co., Ltd.). Examples thereof include a photopolymerization initiator 2) manufactured by ADEKA and described in Japanese Patent Application Laid-Open No. 2012-014052. Further, as the oxime compound, it is also preferable to use a compound having no coloring property or a compound having high transparency and difficult to discolor. Examples of commercially available products include ADEKA ARKULS NCI-730, NCI-831, and NCI-930 (all manufactured by ADEKA Corporation).
光ラジカル重合開始剤としては、フルオレン環を有するオキシム化合物を用いることもできる。フルオレン環を有するオキシム化合物の具体例としては、特開2014-137466号公報に記載の化合物が挙げられる。 As the photoradical polymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include the compounds described in JP-A-2014-137466.
光ラジカル重合開始剤としては、カルバゾール環の少なくとも1つのベンゼン環がナフタレン環となった骨格を有するオキシム化合物を用いることもできる。そのようなオキシム化合物の具体例としては、国際公開第2013/083505号に記載の化合物が挙げられる。 As the photoradical polymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used. Specific examples of such an oxime compound include the compounds described in International Publication No. 2013/083505.
光ラジカル重合開始剤としては、フッ素原子を有するオキシム化合物を用いることもできる。フッ素原子を有するオキシム化合物の具体例としては、特開2010-262028号公報に記載の化合物、特表2014-500852号公報に記載の化合物24、36~40、特開2013-164471号公報に記載の化合物(C-3)などが挙げられる。 As the photoradical polymerization initiator, an oxime compound having a fluorine atom can also be used. Specific examples of the oxime compound having a fluorine atom are described in the compounds described in JP-A-2010-262028, compounds 24, 36-40 described in JP-A-2014-500852, and JP-A-2013-164471. Compound (C-3) and the like.
光ラジカル重合開始剤としては、ニトロ基を有するオキシム化合物を用いることができる。ニトロ基を有するオキシム化合物は、二量体とすることも好ましい。ニトロ基を有するオキシム化合物の具体例としては、特開2013-114249号公報の段落番号0031~0047、特開2014-137466号公報の段落番号0008~0012、0070~0079に記載されている化合物、特許4223071号公報の段落番号0007~0025に記載されている化合物、アデカアークルズNCI-831((株)ADEKA製)が挙げられる。 As the photoradical polymerization initiator, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is also preferably a dimer. Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP2013-114249A and paragraphs 0008-0012 and 0070-0079 of JP2014-137466. Examples thereof include the compound described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, ADEKA ARKULS NCI-831 (manufactured by ADEKA Corporation).
光ラジカル重合開始剤としては、ベンゾフラン骨格を有するオキシム化合物を用いることもできる。具体例としては、国際公開第2015/036910号に記載されているOE-01~OE-75が挙げられる。 As the photoradical polymerization initiator, an oxime compound having a benzofuran skeleton can also be used. Specific examples include OE-01 to OE-75 described in International Publication No. 2015/036910.
光ラジカル重合開始剤としては、カルバゾール骨格にヒドロキシ基を有する置換基が結合したオキシム化合物を用いることもできる。このような光重合開始剤としては国際公開第2019/088055号に記載された化合物などが挙げられる。 As the photoradical polymerization initiator, an oxime compound in which a substituent having a hydroxy group is bonded to the carbazole skeleton can also be used. Examples of such a photopolymerization initiator include the compounds described in International Publication No. 2019/088055.
本発明において好ましく使用されるオキシム化合物の具体例を以下に示すが、本発明はこれらに限定されるものではない。 Specific examples of the oxime compound preferably used in the present invention are shown below, but the present invention is not limited thereto.
オキシム化合物は、波長350~500nmの範囲に極大吸収波長を有する化合物が好ましく、波長360~480nmの範囲に極大吸収波長を有する化合物がより好ましい。また、オキシム化合物の波長365nm又は波長405nmにおけるモル吸光係数は、感度の観点から、高いことが好ましく、1000~300000であることがより好ましく、2000~300000であることが更に好ましく、5000~200000であることが特に好ましい。化合物のモル吸光係数は、公知の方法を用いて測定することができる。例えば、分光光度計(Varian社製Cary-5 spectrophotometer)にて、酢酸エチル溶媒を用い、0.01g/Lの濃度で測定することが好ましい。 The oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, and more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm. The molar extinction coefficient of the oxime compound at a wavelength of 365 nm or a wavelength of 405 nm is preferably high, more preferably 1000 to 300,000, further preferably 2000 to 300,000, and more preferably 5000 to 200,000. It is particularly preferable to have. The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).
光ラジカル重合開始剤としては、2官能あるいは3官能以上の光ラジカル重合開始剤を用いてもよい。そのような光ラジカル重合開始剤を用いることにより、光ラジカル重合開始剤の1分子から2つ以上のラジカルが発生するため、良好な感度が得られる。また、非対称構造の化合物を用いた場合においては、結晶性が低下して溶剤などへの溶解性が向上して、経時で析出しにくくなり、硬化性組成物の経時安定性を向上させることができる。2官能あるいは3官能以上の光ラジカル重合開始剤の具体例としては、特表2010-527339号公報、特表2011-524436号公報、国際公開第2015/004565号、特表2016-532675号公報の段落番号0407~0412、国際公開第2017/033680号の段落番号0039~0055に記載されているオキシム化合物の2量体、特表2013-522445号公報に記載されている化合物(E)および化合物(G)、国際公開第2016/034963号に記載されているCmpd1~7、特表2017-523465号公報の段落番号0007に記載されているオキシムエステル類光開始剤、特開2017-167399号公報の段落番号0020~0033に記載されている光開始剤、特開2017-151342号公報の段落番号0017~0026に記載されている光重合開始剤(A)、特許第6469669号公報に記載されているオキシムエステル光開始剤などが挙げられる。 As the photoradical polymerization initiator, a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, so that good sensitivity can be obtained. Further, when a compound having an asymmetric structure is used, the crystallinity is lowered, the solubility in a solvent or the like is improved, the precipitation is less likely to occur with time, and the stability of the curable composition with time is improved. can. Specific examples of the bifunctional or trifunctional or higher functional photo-radical polymerization initiators include JP-A-2010-527339, JP-A-2011-524436, International Publication No. 2015/004565, and JP-A-2016-532675. Dimerics of oxime compounds described in paragraphs 0407 to 0412, paragraphs 0039 to 0055 of International Publication No. 2017/033680, compounds (E) and compounds described in JP2013-522445. G), Cmpd1 to 7 described in International Publication No. 2016/034963, Oxime Esters Photoinitiator described in paragraph No. 0007 of Japanese Patent Application Laid-Open No. 2017-523465, JP-A-2017-167399. The photoinitiator described in paragraphs 0020 to 0033, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of JP-A-2017-151342, described in Japanese Patent No. 6469669. Examples include oxime ester photoinitiators.
光ラジカル重合開始剤は、オキシム化合物とα-アミノケトン化合物とを含むことも好ましい。両者を併用することで、現像性が向上し、矩形性に優れたパターンを形成しやすい。オキシム化合物とα-アミノケトン化合物とを併用する場合、オキシム化合物100質量部に対して、α-アミノケトン化合物が50~600質量部が好ましく、150~400質量部がより好ましい。 It is also preferable that the photoradical polymerization initiator contains an oxime compound and an α-aminoketone compound. By using both in combination, the developability is improved and it is easy to form a pattern having excellent rectangularity. When the oxime compound and the α-aminoketone compound are used in combination, the α-aminoketone compound is preferably 50 to 600 parts by mass, more preferably 150 to 400 parts by mass with respect to 100 parts by mass of the oxime compound.
硬化性組成物の全固形分中における光ラジカル重合開始剤の含有量は、0.1~50質量%が好ましく、0.5~30質量%がより好ましく、1~20質量%が更に好ましい。光ラジカル重合開始剤の含有量が上記範囲であれば、より良好な感度とパターン形成性が得られる。本発明の硬化性組成物は、光ラジカル重合開始剤を1種類のみ含んでいてもよいし、2種類以上含んでいてもよい。光ラジカル重合開始剤を2種類以上含む場合は、それらの合計量が上記範囲となることが好ましい。 The content of the photoradical polymerization initiator in the total solid content of the curable composition is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, still more preferably 1 to 20% by mass. When the content of the photoradical polymerization initiator is in the above range, better sensitivity and pattern forming property can be obtained. The curable composition of the present invention may contain only one kind of photoradical polymerization initiator, or may contain two or more kinds of photoradical polymerization initiators. When two or more kinds of photoradical polymerization initiators are contained, the total amount thereof is preferably in the above range.
(光カチオン重合開始剤)
光カチオン重合開始剤としては、光酸発生剤が挙げられる。光酸発生剤としては、光照射により分解して酸を発生する、ジアゾニウム塩、ホスホニウム塩、スルホニウム塩、ヨードニウム塩などのオニウム塩化合物、イミドスルホネート、オキシムスルホネート、ジアゾジスルホン、ジスルホン、o-ニトロベンジルスルホネート等のスルホネート化合物などを挙げることができる。光カチオン重合開始剤の詳細については特開2009-258603号公報の段落番号0139~0214の記載を参酌でき、この内容は本明細書に組み込まれる。
(Photocationic polymerization initiator)
Examples of the photocationic polymerization initiator include a photoacid generator. Examples of the photoacid generator include onium salt compounds such as diazonium salt, phosphonium salt, sulfonium salt, and iodonium salt, which are decomposed by light irradiation to generate acid, imide sulfonate, oxime sulfonate, diazodisulfone, disulfone, and o-nitrobenzyl. Examples thereof include sulfonate compounds such as sulfonate. For details of the photocationic polymerization initiator, the description in paragraphs 0139 to 0214 of JP2009-258603A can be referred to, and the contents thereof are incorporated in the present specification.
硬化性組成物の全固形分中における光カチオン重合開始剤の含有量は0.1~50質量%が好ましく、0.5~30質量%がより好ましく、1~20質量%が更に好ましい。光カチオン重合開始剤の含有量が上記範囲であれば、より良好な感度とパターン形成性が得られる。本発明の硬化性組成物は、光カチオン重合開始剤を1種類のみ含んでいてもよいし、2種類以上含んでいてもよい。光カチオン重合開始剤を2種類以上含む場合は、それらの合計量が上記範囲となることが好ましい。 The content of the photocationic polymerization initiator in the total solid content of the curable composition is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, still more preferably 1 to 20% by mass. When the content of the photocationic polymerization initiator is in the above range, better sensitivity and pattern forming property can be obtained. The curable composition of the present invention may contain only one type of photocationic polymerization initiator, or may contain two or more types of photocationic polymerization initiators. When two or more types of photocationic polymerization initiators are contained, the total amount thereof is preferably in the above range.
<<多官能チオール>>
本発明の硬化性組成物は多官能チオールを含有することができる。多官能チオールは、チオール(SH)基を2個以上有する化合物である。多官能チオールは上述の光ラジカル重合開始剤とともに使用することにより、光照射後のラジカル重合過程において、連鎖移動剤として働き、酸素による重合阻害を受けにくいチイルラジカルが発生するので、硬化性組成物の感度を高めることができる。特にSH基がメチレン、エチレン基等の脂肪族基に結合した多官能脂肪族チオールが好ましい。
<< Polyfunctional Thiol >>
The curable composition of the present invention can contain a polyfunctional thiol. A polyfunctional thiol is a compound having two or more thiol (SH) groups. When the polyfunctional thiol is used together with the above-mentioned photoradical polymerization initiator, it acts as a chain transfer agent in the radical polymerization process after light irradiation and generates chile radicals that are less susceptible to polymerization inhibition by oxygen. The sensitivity can be increased. In particular, a polyfunctional aliphatic thiol in which the SH group is bonded to an aliphatic group such as methylene or ethylene group is preferable.
多官能チオールとしては、例えば、ヘキサンジチオール、デカンジチオール、1,4-ブタンジオールビスチオプロピオネート、1,4-ブタンジオールビスチオグリコレート、エチレングリコールビスチオグリコレート、エチレングリコールビスチオプロピオネート、トリメチロールプロパントリスチオグリコレート、トリメチロールプロパントリスチオプロピオネート、トリメチロールエタントリス(3-メルカプトブチレート)、トリメチロールプロパントリス(3-メルカプトブチレート)、トリメチロールプロパントリス(3-メルカプトプロピオネート)、ペンタエリスリトールテトラキスチオグリコレート、ペンタエリスリトールテトラキスチオプロピオネート、ペンタエリスリトールテトラキス(3-メルカプトプロピオネート)、ジペンタエリスリトールヘキサキス(3-メルカプトプロピオネート)、トリメルカプトプロピオン酸トリス(2-ヒドロキシエチル)イソシアヌレート、1,4-ジメチルメルカプトベンゼン、2、4、6-トリメルカプト-s-トリアジン、2-(N,N-ジブチルアミノ)-4,6-ジメルカプト-s-トリアジンなどが挙げられる。また、下記構造の化合物も挙げられる。 Examples of the polyfunctional thiol include hexanedithiol, decandithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropio. Nate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolethanetris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate) Mercaptopropionate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetraxthiopropionate, pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), trimethylolpropane propion Tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s -Triazine, etc. can be mentioned. Further, a compound having the following structure can also be mentioned.
硬化性組成物の全固形分中における多官能チオールの含有量は、0.1~20質量%が好ましく、0.1~15質量%がより好ましく、0.1~10質量%が更に好ましい。本発明の硬化性組成物は、多官能チオールを、1種のみを含んでいてもよいし、2種以上含んでいてもよい。2種以上含む場合は、それらの合計量が上記範囲となることが好ましい。 The content of polyfunctional thiol in the total solid content of the curable composition is preferably 0.1 to 20% by mass, more preferably 0.1 to 15% by mass, still more preferably 0.1 to 10% by mass. The curable composition of the present invention may contain only one type of polyfunctional thiol, or may contain two or more types of polyfunctional thiols. When two or more kinds are contained, it is preferable that the total amount thereof is within the above range.
<<エポキシ樹脂硬化剤>>
本発明の硬化性組成物がエポキシ樹脂を含む場合、エポキシ樹脂硬化剤をさらに含むことが好ましい。エポキシ樹脂硬化剤としては、例えばアミン化合物、酸無水物化合物、アミド化合物、フェノール化合物、多価カルボン酸などが挙げられる。エポキシ樹脂硬化剤としては耐熱性、硬化物の透明性という観点から多価カルボン酸が好ましく、分子内に二つ以上のカルボン酸無水物基を有する化合物が最も好ましい。エポキシ樹脂硬化剤の具体例としては、ブタン二酸などが挙げられる。
<< Epoxy resin curing agent >>
When the curable composition of the present invention contains an epoxy resin, it is preferable that the curable composition further contains an epoxy resin curing agent. Examples of the epoxy resin curing agent include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and polyvalent carboxylic acids. As the epoxy resin curing agent, a polyvalent carboxylic acid is preferable from the viewpoint of heat resistance and transparency of the cured product, and a compound having two or more carboxylic acid anhydride groups in the molecule is most preferable. Specific examples of the epoxy resin curing agent include butane diic acid.
エポキシ樹脂硬化剤の含有量は、エポキシ樹脂100質量部に対し、0.01~20質量部が好ましく、0.01~10質量部がより好ましく、0.1~6.0質量部がさらに好ましい。 The content of the epoxy resin curing agent is preferably 0.01 to 20 parts by mass, more preferably 0.01 to 10 parts by mass, still more preferably 0.1 to 6.0 parts by mass with respect to 100 parts by mass of the epoxy resin. ..
<<顔料誘導体>>
本発明の硬化性組成物は、更に顔料誘導体を含有することができる。顔料誘導体としては、色素骨格に酸基または塩基性基が結合した構造を有する化合物が挙げられる。顔料誘導体を構成する色素骨格としては、キノリン色素骨格、ベンゾイミダゾロン色素骨格、ベンゾイソインドール色素骨格、ベンゾチアゾール色素骨格、イニミウム色素骨格、スクアリリウム色素骨格、クロコニウム色素骨格、オキソノール色素骨格、ピロロピロール色素骨格、ジケトピロロピロール色素骨格、アゾ色素骨格、アゾメチン色素骨格、フタロシアニン色素骨格、ナフタロシアニン色素骨格、アントラキノン色素骨格、キナクリドン色素骨格、ジオキサジン色素骨格、ペリノン色素骨格、ペリレン色素骨格、チオインジゴ色素骨格、イソインドリン色素骨格、イソインドリノン色素骨格、キノフタロン色素骨格、イミニウム色素骨格、ジチオール色素骨格、トリアリールメタン色素骨格、ピロメテン色素骨格等が挙げられる。酸基としては、カルボキシル基、スルホ基、カルボン酸アミド基、スルホン酸アミド基、イミド酸基及びこれらの塩が挙げられる。カルボン酸アミド基としては、-NHCORX1で表される基が好ましい。スルホン酸アミド基としては、-NHSO2RX2で表される基が好ましい。イミド酸基としては、-SO2NHSO2RX3、-CONHSO2RX4、-CONHCORX5または-SO2NHCORX6で表される基が好ましい。RX1~RX6は、それぞれ独立に、炭化水素基または複素環基を表す。RX1~RX6が表す炭化水素基および複素環基は、さらに置換基を有してもよい。
塩を構成する原子または原子団としては、アルカリ金属イオン(Li+、Na+、K+など)、アルカリ土類金属イオン(Ca2+、Mg2+など)、アンモニウムイオン、イミダゾリウムイオン、ピリジニウムイオン、ホスホニウムイオンなどが挙げられる。塩基性基としては、アミノ基、ピリジニル基およびその塩、アンモニウム基の塩、並びにフタルイミドメチル基が挙げられる。塩を構成する原子または原子団としては、水酸化物イオン、ハロゲンイオン、カルボン酸イオン、スルホン酸イオン、フェノキシドイオンなどが挙げられる。
<< Pigment derivative >>
The curable composition of the present invention can further contain a pigment derivative. Examples of the pigment derivative include compounds having a structure in which an acid group or a basic group is bonded to the pigment skeleton. The pigment skeletons constituting the pigment derivatives include quinoline pigment skeleton, benzoimidazolone pigment skeleton, benzoisoindole pigment skeleton, benzothiazole pigment skeleton, inimium pigment skeleton, squarylium pigment skeleton, croconium pigment skeleton, oxonor pigment skeleton, and pyrolopyrrolop pigment. Skeleton, diketopyrrolopyrrole pigment skeleton, azo pigment skeleton, azomethine pigment skeleton, phthalocyanine pigment skeleton, naphthalocyanine pigment skeleton, anthraquinone pigment skeleton, quinacridone pigment skeleton, dioxazine pigment skeleton, perinone pigment skeleton, perylene pigment skeleton, thioindigo pigment skeleton, Examples thereof include an isoindrin pigment skeleton, an isoindolinone pigment skeleton, a quinophthalone pigment skeleton, an iminium pigment skeleton, a dithiol pigment skeleton, a triarylmethane pigment skeleton, and a pyromethene pigment skeleton. Examples of the acid group include a carboxyl group, a sulfo group, a carboxylic acid amide group, a sulfonic acid amide group, an imic acid group and salts thereof. As the carboxylic acid amide group, a group represented by -NHCOR X1 is preferable. The sulfonic acid amide group, preferably a group represented by -NHSO 2 R X2. As the imidic acid group, a group represented by -SO 2 NHSO 2 R X3 , -CONHSO 2 R X4 , -CONHCOR X5 or -SO 2 NHCOR X6 is preferable. RX1 to RX6 independently represent a hydrocarbon group or a heterocyclic group. Hydrocarbon or heterocyclic group R X1 ~ R X6 represents may further have a substituent.
As atoms or groups of atoms constituting the salt, alkali metal ions (Li + , Na + , K +, etc.), alkaline earth metal ions (Ca 2+ , Mg 2+, etc.), ammonium ions, imidazolium ions, pyridinium ions, etc. Examples include phosphonium ions. Examples of the basic group include an amino group, a pyridinyl group and a salt thereof, a salt of an ammonium group, and a phthalimide methyl group. Examples of the atom or atomic group constituting the salt include hydroxide ion, halogen ion, carboxylic acid ion, sulfonic acid ion, and phenoxide ion.
顔料誘導体の具体例としては、特開昭56-118462号公報、特開昭63-264674号公報、特開平01-217077号公報、特開平03-009961号公報、特開平03-026767号公報、特開平03-153780号公報、特開平03-045662号公報、特開平04-285669号公報、特開平06-145546号公報、特開平06-212088号公報、特開平06-240158号公報、特開平10-030063号公報、特開平10-195326号公報、国際公開第2011/024896号の段落番号0086~0098、国際公開第2012/102399号の段落番号0063~0094、国際公開第2017/038252号の段落番号0082、国際公開第2017/146092号の段落番号0052、特開2015-151530号公報の段落番号0171、特開2011-252065号公報の段落番号0162~0183、特開2003-081972号公報、特許第5299151号公報、特開2015-172732号公報、特開2014-199308号公報、特開2014-085562号公報、特開2014-035351号公報、特開2008-081565号公報に記載の化合物が挙げられる。 Specific examples of the pigment derivative include Japanese Patent Application Laid-Open No. 56-118462, Japanese Patent Application Laid-Open No. 63-264674, Japanese Patent Application Laid-Open No. 01-2170777, Japanese Patent Application Laid-Open No. 03-009961, and Japanese Patent Application Laid-Open No. 03-026767. Japanese Patent Application Laid-Open No. 03-153780, Japanese Patent Application Laid-Open No. 03-405662, Japanese Patent Application Laid-Open No. 04-285669, Japanese Patent Application Laid-Open No. 06-145546, Japanese Patent Application Laid-Open No. 06-212088, Japanese Patent Application Laid-Open No. 06-240158, Japanese Patent Application Laid-Open No. 10-030063, Japanese Patent Application Laid-Open No. 10-195326, International Publication No. 2011/024896, paragraph numbers 0083-0998, International Publication No. 2012/102399, paragraph numbers 0063-0094, International Publication No. 2017/038252 Paragraph No. 1982, Paragraph No. 0052 of International Publication No. 2017/146092, Paragraph No. 0171 of JP-A-2015-151530, Paragraph Nos. 0162-0183 of JP-A-2011-52065, JP-A-2003-081972, The compounds described in Japanese Patent No. 5299151, Japanese Patent Application Laid-Open No. 2015-172732, Japanese Patent Application Laid-Open No. 2014-199308, Japanese Patent Application Laid-Open No. 2014-0855662, Japanese Patent Application Laid-Open No. 2014-055351, and Japanese Patent Application Laid-Open No. 2008-081565 Can be mentioned.
本発明の硬化性組成物が顔料誘導体を含有する場合、顔料誘導体の含有量は、顔料100質量部に対し、1~50質量部が好ましい。下限値は、3質量部以上が好ましく、5質量部以上がより好ましい。上限値は、40質量部以下が好ましく、30質量部以下がより好ましい。顔料誘導体の含有量が上記範囲であれば、顔料の分散性を高めて、顔料の凝集を効率よく抑制できる。顔料誘導体は1種のみを用いてもよく、2種以上を用いてもよい。2種以上を用いる場合は、合計量が上記範囲となることが好ましい。 When the curable composition of the present invention contains a pigment derivative, the content of the pigment derivative is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the pigment. The lower limit is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less. When the content of the pigment derivative is within the above range, the dispersibility of the pigment can be enhanced and the aggregation of the pigment can be efficiently suppressed. Only one kind of pigment derivative may be used, or two or more kinds may be used. When two or more types are used, the total amount is preferably in the above range.
<<溶剤>>
本発明の硬化性組成物は、溶剤を含有することができる。溶剤としては、有機溶剤が挙げられる。溶剤は、各成分の溶解性や硬化性組成物の塗布性を満足すれば基本的には特に制限はない。有機溶剤の例としては、例えば、エステル類、エーテル類、ケトン類、芳香族炭化水素類、炭化水素類などが挙げられる。これらの詳細については、国際公開第2015/166779号の段落番号0223を参酌でき、この内容は本明細書に組み込まれる。また、環状アルキル基が置換したエステル系溶剤、環状アルキル基が置換したケトン系溶剤を好ましく用いることもできる。また、炭化水素類として、炭素数5~30の炭化水素系溶剤を好ましく用いることもできる。炭化水素系溶剤は直鎖と分岐の化合物が混合していてもよく、炭素数が異なる2種以上の化合物の混合物でもよい。有機溶剤の具体例としては、ジクロロメタン、3-エトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル、エチルセロソルブアセテート、乳酸エチル、ジエチレングリコールジメチルエーテル、酢酸ブチル、3-メトキシプロピオン酸メチル、2-ヘプタノン、シクロヘキサノン、酢酸シクロヘキシル、シクロペンタノン、エチルカルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールモノメチルエーテル、及びプロピレングリコールモノメチルエーテルアセテート、ペンタン、ヘキサン、ヘプタン、オクタン、ノナン、デカン、シクロペンタン、シクロヘキサンなどが挙げられる。本発明において有機溶剤は、1種単独で用いてもよく、2種以上を組み合わせて用いてもよい。また、3-メトキシ-N,N-ジメチルプロパンアミド、3-ブトキシ-N,N-ジメチルプロパンアミドも溶解性向上の観点から好ましい。ただし溶剤としての芳香族炭化水素類(ベンゼン、トルエン、キシレン、エチルベンゼン等)は、環境面等の理由により低減したほうがよい場合がある(例えば、有機溶剤全量に対して、50質量ppm(parts per million)以下とすることもでき、10質量ppm以下とすることもでき、1質量ppm以下とすることもできる)。
<< Solvent >>
The curable composition of the present invention can contain a solvent. Examples of the solvent include organic solvents. The solvent is basically not particularly limited as long as it satisfies the solubility of each component and the coatability of the curable composition. Examples of organic solvents include, for example, esters, ethers, ketones, aromatic hydrocarbons, hydrocarbons and the like. For these details, paragraph No. 0223 of WO 2015/166779 can be referred to, the contents of which are incorporated herein by reference. Further, an ester solvent substituted with a cyclic alkyl group and a ketone solvent substituted with a cyclic alkyl group can also be preferably used. Further, as the hydrocarbons, a hydrocarbon solvent having 5 to 30 carbon atoms can be preferably used. The hydrocarbon solvent may be a mixture of a linear compound and a branched compound, or may be a mixture of two or more compounds having different carbon atoms. Specific examples of the organic solvent include dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, and the like. Examples thereof include cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate, pentane, hexane, heptane, octane, nonane, decane, cyclopentane, cyclohexane and the like. In the present invention, the organic solvent may be used alone or in combination of two or more. Further, 3-methoxy-N, N-dimethylpropanamide and 3-butoxy-N, N-dimethylpropanamide are also preferable from the viewpoint of improving solubility. However, aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as a solvent may need to be reduced for environmental reasons (for example, 50 mass ppm (parts per) with respect to the total amount of the organic solvent. Million) or less, 10 mass ppm or less, or 1 mass ppm or less).
本発明においては、金属含有量の少ない溶剤を用いることが好ましく、溶剤の金属含有量は、例えば10質量ppb(parts per billion)以下であることが好ましい。必要に応じて質量ppt(parts per trillion)レベルの溶剤を用いてもよく、そのような高純度溶剤は例えば東洋合成社が提供している(化学工業日報、2015年11月13日)。 In the present invention, it is preferable to use a solvent having a low metal content, and the metal content of the solvent is preferably, for example, 10 mass ppb (parts per parts) or less. If necessary, a solvent of mass ppt (parts per parts) level may be used, and such a high-purity solvent is provided by, for example, Toyo Synthetic Co., Ltd. (The Chemical Daily, November 13, 2015).
溶剤から金属等の不純物を除去する方法としては、例えば、蒸留(分子蒸留や薄膜蒸留等)やフィルタを用いたろ過を挙げることができる。ろ過に用いるフィルタのフィルタ孔径としては、10μm以下が好ましく、5μm以下がより好ましく、3μm以下が更に好ましい。フィルタの材質は、ポリテトラフルオロエチレン、ポリエチレンまたはナイロンが好ましい。 Examples of the method for removing impurities such as metals from the solvent include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter. The filter pore diameter of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene or nylon.
溶剤は、異性体(原子数が同じであるが構造が異なる化合物)が含まれていてもよい。また、異性体は、1種のみが含まれていてもよいし、複数種含まれていてもよい。 The solvent may contain isomers (compounds having the same number of atoms but different structures). Further, only one kind of isomer may be contained, or a plurality of kinds may be contained.
本発明において、有機溶剤は、過酸化物の含有率が0.8mmol/L以下であることが好ましく、過酸化物を実質的に含まないことがより好ましい。 In the present invention, the organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide.
溶剤の含有量は、本発明の硬化性組成物の全量に対し、10~99質量%であることが好ましい。上限は、95質量%以下が好ましく、90質量%以下がより好ましい。下限は、30質量%以上が好ましく、40質量%以上がより好ましく、50質量%以上が更に好ましく、60質量%以上がより一層好ましく、70質量%以上が特に好ましい。 The content of the solvent is preferably 10 to 99% by mass with respect to the total amount of the curable composition of the present invention. The upper limit is preferably 95% by mass or less, more preferably 90% by mass or less. The lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, further preferably 60% by mass or more, and particularly preferably 70% by mass or more.
<<重合禁止剤>>
本発明の硬化性組成物は、重合禁止剤を含有することができる。重合禁止剤としては、ハイドロキノン、p-メトキシフェノール、ジ-tert-ブチル-p-クレゾール、ピロガロール、tert-ブチルカテコール、ベンゾキノン、4,4’-チオビス(3-メチル-6-tert-ブチルフェノール)、2,2’-メチレンビス(4-メチル-6-t-ブチルフェノール)、N-ニトロソフェニルヒドロキシアミン塩(アンモニウム塩、第一セリウム塩等)が挙げられる。中でも、p-メトキシフェノールが好ましい。硬化性組成物の全固形分中における重合禁止剤の含有量は、0.0001~5質量%が好ましい。
<< Polymerization inhibitor >>
The curable composition of the present invention can contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), and the like. Examples thereof include 2,2'-methylenebis (4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxyamine salts (ammonium salt, first cerium salt, etc.). Of these, p-methoxyphenol is preferable. The content of the polymerization inhibitor in the total solid content of the curable composition is preferably 0.0001 to 5% by mass.
<<シランカップリング剤>>
本発明の硬化性組成物は、シランカップリング剤を含有することができる。本発明において、シランカップリング剤は、加水分解性基とそれ以外の官能基とを有するシラン化合物を意味する。また、加水分解性基とは、ケイ素原子に直結し、加水分解反応及び縮合反応の少なくともいずれかによってシロキサン結合を生じ得る置換基をいう。加水分解性基としては、例えば、ハロゲン原子、アルコキシ基、アシルオキシ基などが挙げられ、アルコキシ基が好ましい。すなわち、シランカップリング剤は、アルコキシシリル基を有する化合物が好ましい。また、加水分解性基以外の官能基としては、例えば、ビニル基、(メタ)アクリロイル基、メルカプト基、エポキシ基、オキセタニル基、アミノ基、ウレイド基、スルフィド基、イソシアネート基、フェニル基などが挙げられ、(メタ)アクリロイル基およびエポキシ基が好ましい。シランカップリング剤は、特開2009-288703号公報の段落番号0018~0036に記載の化合物、特開2009-242604号公報の段落番号0056~0066に記載の化合物が挙げられ、これらの内容は本明細書に組み込まれる。
<< Silane Coupling Agent >>
The curable composition of the present invention can contain a silane coupling agent. In the present invention, the silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. The hydrolyzable group refers to a substituent that is directly linked to a silicon atom and can form a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group and the like, and an alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of the functional group other than the hydrolyzable group include a vinyl group, a (meth) acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group, an isocyanate group and a phenyl group. The (meth) acryloyl group and the epoxy group are preferable. Examples of the silane coupling agent include the compounds described in paragraphs 0018 to 0036 of JP2009-288703A and the compounds described in paragraphs 0056 to 0066 of JP2009-242604A. Incorporated into the specification.
硬化性組成物の全固形分中におけるシランカップリング剤の含有量は、0.01~15.0質量%が好ましく、0.05~10.0質量%がより好ましい。シランカップリング剤は、1種類のみでもよく、2種類以上でもよい。2種類以上の場合は、合計量が上記範囲となることが好ましい。 The content of the silane coupling agent in the total solid content of the curable composition is preferably 0.01 to 15.0% by mass, more preferably 0.05 to 10.0% by mass. The silane coupling agent may be only one type or two or more types. In the case of two or more types, the total amount is preferably in the above range.
<<界面活性剤>>
本発明の硬化性組成物は、界面活性剤を含有することができる。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコン系界面活性剤などの各種界面活性剤を使用することができる。界面活性剤としては、国際公開第2015/166779号の段落番号0238~0245に記載された界面活性剤が挙げられ、この内容は本明細書に組み込まれる。
<< Surfactant >>
The curable composition of the present invention can contain a surfactant. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicon-based surfactant can be used. Examples of the surfactant include the surfactants described in paragraphs 0238 to 0245 of WO2015 / 166779, the contents of which are incorporated herein by reference.
界面活性剤はフッ素系界面活性剤であることが好ましい。硬化性組成物にフッ素系界面活性剤を含有させることで液特性(特に、流動性)がより向上し、省液性をより改善することができる。また、厚みムラの小さい膜を形成することもできる。 The surfactant is preferably a fluorine-based surfactant. By containing a fluorine-based surfactant in the curable composition, the liquid properties (particularly, fluidity) can be further improved, and the liquid saving property can be further improved. It is also possible to form a film having a small thickness unevenness.
フッ素系界面活性剤中のフッ素含有率は、3~40質量%が好適であり、より好ましくは5~30質量%であり、特に好ましくは7~25質量%である。フッ素含有率がこの範囲内であるフッ素系界面活性剤は、塗布膜の厚さの均一性や省液性の点で効果的であり、硬化性組成物中における溶解性も良好である。 The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid saving property, and has good solubility in a curable composition.
フッ素系界面活性剤としては、特開2014-041318号公報の段落番号0060~0064(対応する国際公開第2014/017669号の段落番号0060~0064)等に記載の界面活性剤、特開2011-132503号公報の段落番号0117~0132に記載の界面活性剤が挙げられ、これらの内容は本明細書に組み込まれる。フッ素系界面活性剤の市販品としては、例えば、メガファックF171、F172、F173、F176、F177、F141、F142、F143、F144、R30、F437、F475、F479、F482、F554、F780、EXP、MFS-330(以上、DIC(株)製)、フロラードFC430、FC431、FC171(以上、住友スリーエム(株)製)、サーフロンS-382、SC-101、SC-103、SC-104、SC-105、SC-1068、SC-381、SC-383、S-393、KH-40(以上、AGC(株)製)、PolyFox PF636、PF656、PF6320、PF6520、PF7002(以上、OMNOVA社製)等が挙げられる。 Examples of the fluorine-based surfactant include the surfactants described in paragraphs 0060 to 0064 of Japanese Patent Application Laid-Open No. 2014-041318 (paragraphs 0060 to 0064 of the corresponding international publication No. 2014/017669), and Japanese Patent Application Laid-Open No. 2011-. The surfactants described in paragraphs 0117 to 0132 of JP 132503 are mentioned and their contents are incorporated herein by reference. Commercially available products of fluorine-based surfactants include, for example, Megafuck F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, MFS. -330 (above, manufactured by DIC Co., Ltd.), Florard FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Ltd.), Surfron S-382, SC-101, SC-103, SC-104, SC-105, Examples thereof include SC-1068, SC-381, SC-383, S-393, KH-40 (above, manufactured by AGC Inc.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (above, manufactured by OMNOVA) and the like. ..
また、フッ素系界面活性剤は、フッ素原子を含有する官能基を持つ分子構造を有し、熱を加えるとフッ素原子を含有する官能基の部分が切断されてフッ素原子が揮発するアクリル系化合物も好適に使用できる。このようなフッ素系界面活性剤としては、DIC(株)製のメガファックDSシリーズ(化学工業日報(2016年2月22日)、日経産業新聞(2016年2月23日))、例えばメガファックDS-21が挙げられる。 In addition, the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and when heat is applied, the portion of the functional group containing the fluorine atom is cut and the fluorine atom is volatilized. Can be preferably used. Examples of such fluorine-based surfactants include the Megafuck DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Megafuck. DS-21 can be mentioned.
また、フッ素系界面活性剤は、フッ素化アルキル基またはフッ素化アルキレンエーテル基を有するフッ素原子含有ビニルエーテル化合物と、親水性のビニルエーテル化合物との重合体を用いることも好ましい。このようなフッ素系界面活性剤は、特開2016-216602号公報に記載されたフッ素系界面活性剤が挙げられ、この内容は本明細書に組み込まれる。 Further, as the fluorine-based surfactant, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound. Examples of such a fluorine-based surfactant include the fluorine-based surfactants described in JP-A-2016-216602, the contents of which are incorporated in the present specification.
フッ素系界面活性剤は、ブロックポリマーを用いることもできる。フッ素系界面活性剤は、フッ素原子を有する(メタ)アクリレート化合物に由来する繰り返し単位と、アルキレンオキシ基(好ましくはエチレンオキシ基、プロピレンオキシ基)を2以上(好ましくは5以上)有する(メタ)アクリレート化合物に由来する繰り返し単位と、を含む含フッ素高分子化合物も好ましく用いることができる。また、特開2010-032698号公報の段落番号0016~0037に記載されたフッ素含有界面活性剤や、下記化合物も本発明で用いられるフッ素系界面活性剤として例示される。
また、フッ素系界面活性剤は、エチレン性不飽和結合含有基を側鎖に有する含フッ素重合体を用いることもできる。具体例としては、特開2010-164965号公報の段落番号0050~0090および段落番号0289~0295に記載された化合物、DIC(株)製のメガファックRS-101、RS-102、RS-718K、RS-72-K等が挙げられる。また、フッ素系界面活性剤は、特開2015-117327号公報の段落番号0015~0158に記載の化合物を用いることもできる。 Further, as the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used. As specific examples, the compounds described in paragraphs 0050 to 0090 and paragraph numbers 0289 to 0295 of JP2010-164965, Megafuck RS-101, RS-102, RS-718K manufactured by DIC Corporation, RS-72-K and the like can be mentioned. Further, as the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP2015-117327A can also be used.
ノニオン系界面活性剤としては、グリセロール、トリメチロールプロパン、トリメチロールエタン並びにそれらのエトキシレート及びプロポキシレート(例えば、グリセロールプロポキシレート、グリセロールエトキシレート等)、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート、ソルビタン脂肪酸エステル、プルロニックL10、L31、L61、L62、10R5、17R2、25R2(BASF社製)、テトロニック304、701、704、901、904、150R1(BASF社製)、ソルスパース20000(日本ルーブリゾール(株)製)、NCW-101、NCW-1001、NCW-1002(和光純薬工業(株)製)、パイオニンD-6112、D-6112-W、D-6315(竹本油脂(株)製)、オルフィンE1010、サーフィノール104、400、440(日信化学工業(株)製)などが挙げられる。 Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, etc. Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF) , Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solspers 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Wako Pure Chemical Industries, Ltd.) (Manufactured by Kogyo Co., Ltd.), Pionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Yushi Co., Ltd.), Orphine E1010, Surfinol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.) And so on.
硬化性組成物の全固形分中における界面活性剤の含有量は、0.001質量%~5.0質量%が好ましく、0.005~3.0質量%がより好ましい。界面活性剤は、1種類のみでもよく、2種類以上でもよい。2種類以上の場合は、合計量が上記範囲となることが好ましい。 The content of the surfactant in the total solid content of the curable composition is preferably 0.001% by mass to 5.0% by mass, more preferably 0.005 to 3.0% by mass. The surfactant may be only one kind or two or more kinds. In the case of two or more types, the total amount is preferably in the above range.
<<紫外線吸収剤>>
本発明の硬化性組成物は、紫外線吸収剤を含有することができる。紫外線吸収剤は、共役ジエン化合物、アミノジエン化合物、サリシレート化合物、ベンゾフェノン化合物、ベンゾトリアゾール化合物、アクリロニトリル化合物、ヒドロキシフェニルトリアジン化合物、インドール化合物、トリアジン化合物などを用いることができる。このような化合物としては、特開2009-217221号公報の段落番号0038~0052、特開2012-208374号公報の段落番号0052~0072、特開2013-068814号公報の段落番号0317~0334、特開2016-162946号公報の段落番号0061~0080に記載された化合物が挙げられ、これらの内容は本明細書に組み込まれる。紫外線吸収剤の具体例としては、下記構造の化合物などが挙げられる。紫外線吸収剤の市販品としては、例えば、UV-503(大東化学(株)製)などが挙げられる。また、ベンゾトリアゾール化合物としては、ミヨシ油脂製のMYUAシリーズ(化学工業日報、2016年2月1日)が挙げられる。また、紫外線吸収剤は、特許第6268967号公報の段落番号0049~0059に記載された化合物を用いることもできる。
The curable composition of the present invention can contain an ultraviolet absorber. As the ultraviolet absorber, a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, an indol compound, a triazine compound and the like can be used. Examples of such compounds include paragraph numbers 0038 to 0052 of JP2009-217221A, paragraph numbers 0052 to 0072 of JP2012-208374A, and paragraph numbers 0317 to 0334 of JP2013-068814. Examples include the compounds described in paragraphs 0061 to 0080 of JP 2016-162946, the contents of which are incorporated herein. Specific examples of the ultraviolet absorber include compounds having the following structures. Examples of commercially available ultraviolet absorbers include UV-503 (manufactured by Daito Kagaku Co., Ltd.). Examples of the benzotriazole compound include the MYUA series made by Miyoshi Oil & Fat Co., Ltd. (The Chemical Daily, February 1, 2016). Further, as the ultraviolet absorber, the compounds described in paragraphs 0049 to 0059 of Japanese Patent No. 6268967 can also be used.
硬化性組成物の全固形分中における紫外線吸収剤の含有量は、0.01~10質量%が好ましく、0.01~5質量%がより好ましい。紫外線吸収剤は1種のみを用いてもよく、2種以上を用いてもよい。2種以上を用いる場合は、合計量が上記範囲となることが好ましい。 The content of the ultraviolet absorber in the total solid content of the curable composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass. Only one kind of ultraviolet absorber may be used, or two or more kinds may be used. When two or more types are used, the total amount is preferably in the above range.
<<酸化防止剤>>
本発明の硬化性組成物は、酸化防止剤を含有することができる。酸化防止剤としては、フェノール化合物、亜リン酸エステル化合物、チオエーテル化合物などが挙げられる。フェノール化合物としては、フェノール系酸化防止剤として知られる任意のフェノール化合物を使用することができる。好ましいフェノール化合物としては、ヒンダードフェノール化合物が挙げられる。フェノール性ヒドロキシ基に隣接する部位(オルト位)に置換基を有する化合物が好ましい。前述の置換基としては炭素数1~22の置換又は無置換のアルキル基が好ましい。また、酸化防止剤は、同一分子内にフェノール基と亜リン酸エステル基を有する化合物も好ましい。また、酸化防止剤は、リン系酸化防止剤も好適に使用することができる。リン系酸化防止剤としてはトリス[2-[[2,4,8,10-テトラキス(1,1-ジメチルエチル)ジベンゾ[d,f][1,3,2]ジオキサホスフェピン-6-イル]オキシ]エチル]アミン、トリス[2-[(4,6,9,11-テトラ-tert-ブチルジベンゾ[d,f][1,3,2]ジオキサホスフェピン-2-イル)オキシ]エチル]アミン、亜リン酸エチルビス(2,4-ジ-tert-ブチル-6-メチルフェニル)などが挙げられる。酸化防止剤の市販品としては、例えば、アデカスタブ AO-20、アデカスタブ AO-30、アデカスタブ AO-40、アデカスタブ AO-50、アデカスタブ AO-50F、アデカスタブ AO-60、アデカスタブ AO-60G、アデカスタブ AO-80、アデカスタブ AO-330(以上、(株)ADEKA製)などが挙げられる。また、酸化防止剤として、国際公開第2017/006600号に記載された多官能ヒンダードアミン酸化防止剤を用いることもできる。
<< Antioxidant >>
The curable composition of the present invention can contain an antioxidant. Examples of the antioxidant include phenol compounds, phosphite ester compounds, thioether compounds and the like. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. Preferred phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxy group is preferable. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. Further, as the antioxidant, a compound having a phenol group and a phosphite ester group in the same molecule is also preferable. Further, as the antioxidant, a phosphorus-based antioxidant can also be preferably used. As a phosphorus-based antioxidant, tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosfepine-6 -Il] Oxy] Ethyl] amine, Tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosfepin-2-yl] ) Oxy] ethyl] amine, ethylbis phosphite (2,4-di-tert-butyl-6-methylphenyl) and the like. Commercially available products of antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (above, manufactured by ADEKA Corporation) and the like. Further, as the antioxidant, the polyfunctional hindered amine antioxidant described in International Publication No. 2017/006600 can also be used.
硬化性組成物の全固形分中における酸化防止剤の含有量は、0.01~20質量%であることが好ましく、0.3~15質量%であることがより好ましい。酸化防止剤は1種のみを用いてもよく、2種以上を用いてもよい。2種以上を用いる場合は、合計量が上記範囲となることが好ましい。 The content of the antioxidant in the total solid content of the curable composition is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, the total amount is preferably in the above range.
<<その他成分>>
本発明の硬化性組成物は、必要に応じて、増感剤、硬化促進剤、フィラー、熱硬化促進剤、可塑剤及びその他の助剤類(例えば、導電性粒子、充填剤、消泡剤、難燃剤、レベリング剤、剥離促進剤、香料、表面張力調整剤、連鎖移動剤など)を含有してもよい。これらの成分を適宜含有させることにより、膜物性などの性質を調整することができる。これらの成分は、例えば、特開2012-003225号公報の段落番号0183以降(対応する米国特許出願公開第2013/0034812号明細書の段落番号0237)の記載、特開2008-250074号公報の段落番号0101~0104、0107~0109等の記載を参酌でき、これらの内容は本明細書に組み込まれる。
また、本発明の硬化性組成物は、必要に応じて、潜在酸化防止剤を含有してもよい。潜在酸化防止剤としては、酸化防止剤として機能する部位が保護基で保護された化合物であって、100~250℃で加熱するか、又は酸/塩基触媒存在下で80~200℃で加熱することにより保護基が脱離して酸化防止剤として機能する化合物が挙げられる。潜在酸化防止剤としては、国際公開第2014/021023号、国際公開第2017/030005号、特開2017-008219号公報に記載された化合物が挙げられる。市販品としては、アデカアークルズGPA-5001((株)ADEKA製)等が挙げられる。
<< Other ingredients >>
The curable composition of the present invention can be used as a sensitizer, a curing accelerator, a filler, a thermosetting accelerator, a plasticizer and other auxiliary agents (for example, conductive particles, a filler, a defoaming agent), if necessary. , Flame retardant, leveling agent, peeling accelerator, fragrance, surface tension modifier, chain transfer agent, etc.) may be contained. By appropriately containing these components, properties such as film physical characteristics can be adjusted. These components are described in, for example, paragraph No. 0183 and subsequent paragraphs of JP2012-003225A (paragraph number 0237 of the corresponding US Patent Application Publication No. 2013/0034812), paragraphs of JP-A-2008-250074. The descriptions of Nos. 0101 to 0104, 0107 to 0109, etc. can be taken into consideration, and these contents are incorporated in the present specification.
In addition, the curable composition of the present invention may contain a latent antioxidant, if necessary. The latent antioxidant is a compound in which the site that functions as an antioxidant is protected by a protecting group, and is heated at 100 to 250 ° C. or at 80 to 200 ° C. in the presence of an acid / base catalyst. As a result, a compound in which the protecting group is eliminated and functions as an antioxidant can be mentioned. Examples of the latent antioxidant include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219. Examples of commercially available products include ADEKA ARKULS GPA-5001 (manufactured by ADEKA Corporation) and the like.
<収容容器>
本発明の硬化性組成物の収容容器としては、特に限定はなく、公知の収容容器を用いることができる。また、収容容器として、原材料や硬化性組成物中への不純物混入を抑制することを目的に、容器内壁を6種6層の樹脂で構成する多層ボトルや6種の樹脂を7層構造にしたボトルを使用することも好ましい。このような容器としては例えば特開2015-123351号公報に記載の容器が挙げられる。また、容器内壁は、容器内壁からの金属溶出を防ぎ、硬化性組成物の保存安定性を高めたり、成分変質を抑制するなど目的で、ガラス製やステンレス製などにすることも好ましい。
<Container>
The storage container for the curable composition of the present invention is not particularly limited, and a known storage container can be used. In addition, as a storage container, a multi-layer bottle composed of 6 types and 6 layers of resin and 6 types of resin have a 7-layer structure for the purpose of suppressing impurities from being mixed into raw materials and curable compositions. It is also preferable to use a bottle. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351. Further, the inner wall of the container is preferably made of glass or stainless steel for the purpose of preventing metal elution from the inner wall of the container, enhancing the storage stability of the curable composition, and suppressing deterioration of components.
<硬化性組成物の調製方法>
本発明の硬化性組成物は、前述の成分を混合して調製できる。硬化性組成物の調製に際しては、全成分を同時に溶剤に溶解または分散して硬化性組成物を調製してもよいし、必要に応じては、各成分を適宜配合した2つ以上の溶液または分散液をあらかじめ調製し、使用時(塗布時)にこれらを混合して硬化性組成物として調製してもよい。
<Method for preparing curable composition>
The curable composition of the present invention can be prepared by mixing the above-mentioned components. In preparing the curable composition, all the components may be dissolved or dispersed in a solvent at the same time to prepare a curable composition, or if necessary, two or more solutions in which each component is appropriately blended or The dispersion may be prepared in advance and mixed at the time of use (at the time of application) to prepare a curable composition.
また、本発明の硬化性組成物が顔料を含む場合は、顔料を分散させるプロセスを含むことが好ましい。顔料を分散させるプロセスにおいて、顔料の分散に用いる機械力としては、圧縮、圧搾、衝撃、剪断、キャビテーションなどが挙げられる。これらプロセスの具体例としては、ビーズミル、サンドミル、ロールミル、ボールミル、ペイントシェーカー、マイクロフルイダイザー、高速インペラー、サンドグラインダー、フロージェットミキサー、高圧湿式微粒化、超音波分散などが挙げられる。またサンドミル(ビーズミル)における粒子の粉砕においては、径の小さいビーズを使用する、ビーズの充填率を大きくする事等により粉砕効率を高めた条件で処理することが好ましい。また、粉砕処理後にろ過、遠心分離などで粗粒子を除去することが好ましい。また、顔料を分散させるプロセスおよび分散機は、「分散技術大全集、株式会社情報機構発行、2005年7月15日」や「サスペンション(固/液分散系)を中心とした分散技術と工業的応用の実際 総合資料集、経営開発センター出版部発行、1978年10月10日」、特開2015-157893号公報の段落番号0022に記載のプロセス及び分散機を好適に使用出来る。また顔料を分散させるプロセスにおいては、ソルトミリング工程にて顔料の微細化処理を行ってもよい。ソルトミリング工程に用いられる素材、機器、処理条件等は、例えば特開2015-194521号公報、特開2012-046629号公報の記載を参酌できる。 Further, when the curable composition of the present invention contains a pigment, it is preferable to include a process of dispersing the pigment. In the process of dispersing the pigment, the mechanical force used for dispersing the pigment includes compression, squeezing, impact, shearing, cavitation and the like. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high speed impellers, sand grinders, flow jet mixers, high pressure wet atomization, ultrasonic dispersion and the like. Further, in the pulverization of particles in a sand mill (bead mill), it is preferable to use beads having a small diameter and to process the particles under conditions in which the pulverization efficiency is increased by increasing the filling rate of the beads. Further, it is preferable to remove coarse particles by filtration, centrifugation or the like after the pulverization treatment. In addition, the process and disperser for dispersing pigments are "Dispersion Technology Complete Works, Published by Information Organization Co., Ltd., July 15, 2005" and "Dispersion technology centered on suspension (solid / liquid dispersion system) and industrial. Practical application The process and disperser described in Paragraph No. 0022 of JP-A-2015-157893, "Comprehensive Data Collection, Published by Management Development Center Publishing Department, October 10, 1978" can be preferably used. Further, in the process of dispersing the pigment, the pigment may be miniaturized in the salt milling step. For the materials, equipment, processing conditions, etc. used in the salt milling step, for example, the descriptions in JP-A-2015-194521 and JP-A-2012-046629 can be referred to.
硬化性組成物の調製にあたり、異物の除去や欠陥の低減などの目的で、硬化性組成物をフィルタでろ過することが好ましい。フィルタとしては、従来からろ過用途等に用いられているフィルタであれば特に限定されることなく用いることができる。例えば、ポリテトラフルオロエチレン(PTFE)等のフッ素樹脂、ナイロン(例えばナイロン-6、ナイロン-6,6)等のポリアミド系樹脂、ポリエチレン、ポリプロピレン(PP)等のポリオレフィン樹脂(高密度、超高分子量のポリオレフィン樹脂を含む)等の素材を用いたフィルタが挙げられる。これら素材の中でもポリプロピレン(高密度ポリプロピレンを含む)およびナイロンが好ましい。 In preparing the curable composition, it is preferable to filter the curable composition with a filter for the purpose of removing foreign substances and reducing defects. As the filter, any filter that has been conventionally used for filtration or the like can be used without particular limitation. For example, a fluororesin such as polytetrafluoroethylene (PTFE), a polyamide resin such as nylon (for example, nylon-6, nylon-6,6), and a polyolefin resin such as polyethylene and polypropylene (PP) (high density, ultrahigh molecular weight). A filter using a material such as (including the polyolefin resin of) is mentioned. Among these materials, polypropylene (including high-density polypropylene) and nylon are preferable.
フィルタの孔径は、0.01~7.0μmが好ましく、0.01~3.0μmがより好ましく、0.05~0.5μmが更に好ましい。フィルタの孔径が上記範囲であれば、微細な異物をより確実に除去できる。フィルタの孔径値については、フィルタメーカーの公称値を参照することができる。フィルタは、日本ポール株式会社(DFA4201NIEYなど)、アドバンテック東洋株式会社、日本インテグリス株式会社(旧日本マイクロリス株式会社)および株式会社キッツマイクロフィルタ等が提供する各種フィルタを用いることができる。 The pore size of the filter is preferably 0.01 to 7.0 μm, more preferably 0.01 to 3.0 μm, and even more preferably 0.05 to 0.5 μm. If the pore size of the filter is within the above range, fine foreign matter can be removed more reliably. For the pore size value of the filter, the nominal value of the filter manufacturer can be referred to. As the filter, various filters provided by Nippon Pole Co., Ltd. (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), KITZ Microfilter Co., Ltd., etc. can be used.
また、フィルタとしてファイバ状のろ材を用いることも好ましい。ファイバ状のろ材としては、例えばポリプロピレンファイバ、ナイロンファイバ、グラスファイバ等が挙げられる。市販品としては、ロキテクノ社製のSBPタイプシリーズ(SBP008など)、TPRタイプシリーズ(TPR002、TPR005など)、SHPXタイプシリーズ(SHPX003など)が挙げられる。 It is also preferable to use a fibrous filter medium as the filter. Examples of the fibrous filter medium include polypropylene fiber, nylon fiber, glass fiber and the like. Examples of commercially available products include SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.) and SHPX type series (SHPX003, etc.) manufactured by Roki Techno Co., Ltd.
フィルタを使用する際、異なるフィルタ(例えば、第1のフィルタと第2のフィルタなど)を組み合わせてもよい。その際、各フィルタでのろ過は、1回のみでもよいし、2回以上行ってもよい。また、上述した範囲内で異なる孔径のフィルタを組み合わせてもよい。また、第1のフィルタでのろ過は、分散液のみに対して行い、他の成分を混合した後で、第2のフィルタでろ過を行ってもよい。 When using a filter, different filters (for example, a first filter and a second filter) may be combined. At that time, the filtration with each filter may be performed only once or twice or more. Further, filters having different pore diameters may be combined within the above-mentioned range. Further, the filtration with the first filter may be performed only on the dispersion liquid, and after mixing the other components, the filtration may be performed with the second filter.
<膜>
次に、本発明の膜について説明する。
本発明の膜は、上述した本発明の組成物から得られる膜である。本発明の膜は、赤外線透過フィルタとして好ましく用いることができる。
<Membrane>
Next, the film of the present invention will be described.
The film of the present invention is a film obtained from the above-mentioned composition of the present invention. The film of the present invention can be preferably used as an infrared transmission filter.
本発明の膜の膜厚は、特に限定はないが、0.1~50μmが好ましく、0.1~20μmがより好ましく、0.5~10μmが更に好ましい。 The film thickness of the film of the present invention is not particularly limited, but is preferably 0.1 to 50 μm, more preferably 0.1 to 20 μm, and even more preferably 0.5 to 10 μm.
本発明の膜は、以下の(1)~(12)のいずれかの態様の分光特性を有することが好ましい。 The film of the present invention preferably has the spectral characteristics of any of the following aspects (1) to (12).
(1)膜の厚み方向における光の透過率の、波長400~830nmの範囲における最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、膜の厚み方向における光の透過率の、波長1000~2200nmの範囲における最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である態様。この態様によれば、波長400~830nmの範囲の光を遮光して、波長940nmを超える赤外線が透過可能な膜とすることができる。 (1) The maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction. The minimum value of the transmittance in the wavelength range of 1000 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 830 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 940 nm.
(2)膜の厚み方向における光の透過率の、波長400~950nmの範囲における最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、膜の厚み方向における光の透過率の、波長1100~2200nmの範囲における最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である態様。この態様によれば、波長400~950nmの範囲の光を遮光して、波長1040nmを超える赤外線が透過可能な膜とすることができる。 (2) The maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction. The minimum value of the transmittance in the wavelength range of 1100 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 950 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1040 nm.
(3)膜の厚み方向における光の透過率の、波長400~1050nmの範囲における最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、膜の厚み方向における光の透過率の、波長1200~2200nmの範囲における最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である態様。この態様によれば、波長400~1050nmの範囲の光を遮光して、波長1140nmを超える赤外線が透過可能な膜とすることができる。 (3) The maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1050 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction. The minimum value of the transmittance in the wavelength range of 1200 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, it is possible to obtain a film capable of transmitting infrared rays having a wavelength of more than 1140 nm by blocking light in the wavelength range of 400 to 1050 nm.
(4)膜の厚み方向における光の透過率の、波長400~1150nmの範囲における最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、膜の厚み方向における光の透過率の、波長1300~2200nmの範囲における最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である態様。この態様によれば、波長400~1150nmの範囲の光を遮光して、波長1240nmを超える赤外線が透過可能な膜とすることができる。 (4) The maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1150 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction. The minimum value of the transmittance in the wavelength range of 1300 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1150 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1240 nm.
(5)膜の厚み方向における光の透過率の、波長400~1250nmの範囲における最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、膜の厚み方向における光の透過率の、波長1400~2200nmの範囲における最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である態様。この態様によれば、波長400~1250nmの範囲の光を遮光して、波長1340nmを超える赤外線が透過可能な膜とすることができる。 (5) The maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1250 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction. The minimum value of the transmittance in the wavelength range of 1400 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1250 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1340 nm.
(6)膜の厚み方向における光の透過率の、波長400~1350nmの範囲における最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、膜の厚み方向における光の透過率の、波長1500~2200nmの範囲における最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である態様。この態様によれば、波長400~1350nmの範囲の光を遮光して、波長1440nmを超える赤外線が透過可能な膜とすることができる。 (6) The maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1350 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction. The minimum value of the transmittance in the wavelength range of 1500 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1350 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1440 nm.
(7)膜の厚み方向における光の透過率の、波長400~1450nmの範囲における最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、膜の厚み方向における光の透過率の、波長1600~2200nmの範囲における最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である態様。この態様によれば、波長400~1450nmの範囲の光を遮光して、波長1540nmを超える赤外線が透過可能な膜とすることができる。 (7) The maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1450 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction. The minimum value of the transmittance in the wavelength range of 1600 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1450 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1540 nm.
(8)膜の厚み方向における光の透過率の、波長400~1550nmの範囲における最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、膜の厚み方向における光の透過率の、波長1700~2200nmの範囲における最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である態様。この態様によれば、波長400~1550nmの範囲の光を遮光して、波長1640nmを超える赤外線が透過可能な膜とすることができる。 (8) The maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1550 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction. The minimum value of the transmittance in the wavelength range of 1700 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1550 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1640 nm.
(9)膜の厚み方向における光の透過率の、波長400~1650nmの範囲における最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、膜の厚み方向における光の透過率の、波長1800~2200nmの範囲における最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である態様。この態様によれば、波長400~1650nmの範囲の光を遮光して、波長1740nmを超える赤外線が透過可能な膜とすることができる。 (9) The maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1650 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction. The minimum value of the transmittance in the wavelength range of 1800 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1650 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1740 nm.
(10)膜の厚み方向における光の透過率の、波長400~1750nmの範囲における最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、膜の厚み方向における光の透過率の、波長1900~2200nmの範囲における最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である態様。この態様によれば、波長400~1750nmの範囲の光を遮光して、波長1840nmを超える赤外線が透過可能な膜とすることができる。 (10) The maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1750 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction. The minimum value of the transmittance in the wavelength range of 1900 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1750 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1840 nm.
(11)膜の厚み方向における光の透過率の、波長400~1850nmの範囲における最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、膜の厚み方向における光の透過率の、波長2000~2200nmの範囲における最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である態様。この態様によれば、波長400~1850nmの範囲の光を遮光して、波長1940nmを超える赤外線が透過可能な膜とすることができる。 (11) The maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1850 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction. The minimum value of the transmittance in the wavelength range of 2000 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1850 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 1940 nm.
(12)膜の厚み方向における光の透過率の、波長400~1950nmの範囲における最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、膜の厚み方向における光の透過率の、波長2100~2200nmの範囲における最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である態様。この態様によれば、波長400~1950nmの範囲の光を遮光して、波長2040nmを超える赤外線が透過可能な膜とすることができる。 (12) The maximum value of the light transmittance in the film thickness direction in the wavelength range of 400 to 1950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light in the film thickness direction. The minimum value of the transmittance in the wavelength range of 2100 to 2200 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, light in the wavelength range of 400 to 1950 nm can be shielded to form a film capable of transmitting infrared rays having a wavelength of more than 2040 nm.
<膜の製造方法>
次に、本発明の膜の製造方法について説明する。本発明の膜は、本発明の硬化性組成物を塗布する工程を経て製造できる。
<Membrane manufacturing method>
Next, the method for producing the film of the present invention will be described. The film of the present invention can be produced through a step of applying the curable composition of the present invention.
本発明の膜の製造方法において、硬化性組成物は支持体上に塗布することが好ましい。支持体としては、例えば、シリコン、無アルカリガラス、ソーダガラス、パイレックス(登録商標)ガラス、石英ガラスなどの材質で構成された基板が挙げられる。これらの基板には、有機膜や無機膜などが形成されていてもよい。有機膜の材料としては、例えば上述した硬化性組成物の欄で説明した樹脂が挙げられる。また、支持体としては、樹脂で構成された基板を用いることもできる。また、支持体には、電荷結合素子(CCD)、相補型金属酸化膜半導体(CMOS)、透明導電膜などが形成されていてもよい。また、支持体には、各画素を隔離するブラックマトリクスが形成されている場合もある。また、支持体には、上部の層との密着性改良、物質の拡散防止或いは基板表面の平坦化のために下地層が設けられていてもよい。下地層の表面接触角は、ジヨードメタンで測定した際に20~70°であることが好ましい。また、水で測定した際に30~80°であることが好ましい。下地層の表面接触角が上記範囲であれば、硬化性組成物の塗れ性が良好である。下地層の表面接触角の調整は、たとえば、界面活性剤の添加などの方法で行うことができる。 In the method for producing a film of the present invention, it is preferable that the curable composition is applied onto a support. Examples of the support include a substrate made of a material such as silicon, non-alkali glass, soda glass, Pyrex (registered trademark) glass, and quartz glass. An organic film, an inorganic film, or the like may be formed on these substrates. Examples of the material of the organic film include the resin described in the section of the curable composition described above. Further, as the support, a substrate made of resin can also be used. Further, the support may be formed with a charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like. Further, the support may be formed with a black matrix that separates each pixel. Further, the support may be provided with a base layer for improving the adhesion with the upper layer, preventing the diffusion of substances, or flattening the surface of the substrate. The surface contact angle of the base layer is preferably 20 to 70 ° when measured with diiodomethane. Further, it is preferably 30 to 80 ° when measured with water. When the surface contact angle of the base layer is within the above range, the curable composition has good coatability. The surface contact angle of the base layer can be adjusted by, for example, adding a surfactant.
硬化性組成物の塗布方法としては、公知の方法を用いることができる。例えば、滴下法(ドロップキャスト);スリットコート法;スプレー法;ロールコート法;回転塗布法(スピンコート法);流延塗布法;スリットアンドスピン法;プリウェット法(たとえば、特開2009-145395号公報に記載されている方法);インクジェット(例えばオンデマンド方式、ピエゾ方式、サーマル方式)、ノズルジェット等の吐出系印刷、フレキソ印刷、スクリーン印刷、グラビア印刷、反転オフセット印刷、メタルマスク印刷法などの各種印刷法;金型等を用いた転写法;ナノインプリント法などが挙げられる。インクジェットでの適用方法としては、特に限定されず、例えば「広がる・使えるインクジェット-特許に見る無限の可能性-、2005年2月発行、住ベテクノリサーチ」に示された方法(特に115ページ~133ページ)や、特開2003-262716号公報、特開2003-185831号公報、特開2003-261827号公報、特開2012-126830号公報、特開2006-169325号公報などに記載の方法が挙げられる。また、スピンコート法での塗布は、1000~2000rpmの回転数で行うことが好ましい。また、スピンコート法での塗布は、特開平10-142603号公報、特開平11-302413号公報、特開2000-157922号公報に記載されているように、回転速度を塗布中に高めても良い。また「最先端カラーフィルターのプロセス技術とケミカルス」2006年1月31日、シーエムシー出版記載のスピンコートプロセスも好適に使用することができる。 As a method for applying the curable composition, a known method can be used. For example, a dropping method (drop casting); a slit coating method; a spray method; a roll coating method; a rotary coating method (spin coating method); a casting coating method; a slit and spin method; a pre-wet method (for example, JP-A-2009-145395). (Methods described in the Gazette); Inkjet (for example, on-demand method, piezo method, thermal method), ejection system printing such as nozzle jet, flexo printing, screen printing, gravure printing, reverse offset printing, metal mask printing, etc. Various printing methods; transfer method using a mold or the like; nano-imprint method and the like. The method of application to inkjet is not particularly limited, and is, for example, the method shown in "Expandable and usable inkjet-infinite possibilities seen in patents-, published in February 2005, Sumi Betechno Research" (especially from page 115). (Page 133), and the methods described in JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, JP-A-2006-169325, and the like. Can be mentioned. Further, the application by the spin coating method is preferably performed at a rotation speed of 1000 to 2000 rpm. Further, in the coating by the spin coating method, as described in JP-A-10-142603, JP-A-11-302413, and JP-A-2000-157922, even if the rotation speed is increased during coating. good. In addition, the spin coating process described in "State-of-the-art color filter process technology and chemicals", January 31, 2006, CMC Publishing, can also be preferably used.
硬化性組成物を塗布して形成した硬化性組成物層は、乾燥(プリベーク)してもよい。低温プロセスによりパターンを形成する場合は、プリベークを行わなくてもよい。プリベークを行う場合、プリベーク温度は、150℃以下が好ましく、120℃以下がより好ましく、110℃以下が更に好ましい。下限は、例えば、50℃以上とすることができ、80℃以上とすることもできる。プリベーク温度を150℃以下で行うことにより、例えば、イメージセンサの光電変換膜を有機素材で構成した場合において、これらの特性をより効果的に維持することができる。
プリベーク時間は、10秒~3000秒が好ましく、40~2500秒がより好ましく、80~220秒がさらに好ましい。乾燥は、ホットプレート、オーブン等で行うことができる。
The curable composition layer formed by applying the curable composition may be dried (prebaked). Prebaking may not be required if the pattern is formed by a low temperature process. When prebaking is performed, the prebaking temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and even more preferably 110 ° C. or lower. The lower limit can be, for example, 50 ° C. or higher, or 80 ° C. or higher. By performing the prebaking temperature at 150 ° C. or lower, for example, when the photoelectric conversion film of the image sensor is made of an organic material, these characteristics can be maintained more effectively.
The prebaking time is preferably 10 seconds to 3000 seconds, more preferably 40 to 2500 seconds, and even more preferably 80 to 220 seconds. Drying can be performed on a hot plate, an oven, or the like.
膜の製造方法において、更にパターンを形成する工程を含むことも好ましい。パターン形成方法としては、フォトリソグラフィ法を用いたパターン形成方法、ドライエッチング法を用いたパターン形成方法が挙げられ、フォトリソグラフィ法を用いたパターン形成方法が好ましい。なお、本発明の膜を平坦膜として用いる場合には、パターンを形成する工程を行わなくてもよい。以下、パターンを形成する工程について詳細に説明する。 It is also preferable that the film manufacturing method further includes a step of forming a pattern. Examples of the pattern forming method include a pattern forming method using a photolithography method and a pattern forming method using a dry etching method, and a pattern forming method using a photolithography method is preferable. When the film of the present invention is used as a flat film, it is not necessary to perform the step of forming the pattern. Hereinafter, the process of forming the pattern will be described in detail.
(フォトリソグラフィ法でパターン形成する場合)
フォトリソグラフィ法でのパターン形成方法は、本発明の硬化性組成物を塗布して形成した硬化性組成物層に対しパターン状に露光する工程(露光工程)と、未露光部の硬化性組成物層を現像除去してパターンを形成する工程(現像工程)と、を含むことが好ましい。必要に応じて、現像されたパターンをベークする工程(ポストベーク工程)を設けてもよい。以下、各工程について説明する。
(When forming a pattern by photolithography)
The pattern forming method in the photolithography method includes a step of exposing the curable composition layer formed by applying the curable composition of the present invention in a pattern (exposure step) and a curable composition of an unexposed portion. It is preferable to include a step of developing and removing the layer to form a pattern (development step). If necessary, a step of baking the developed pattern (post-baking step) may be provided. Hereinafter, each step will be described.
<<露光工程>>
露光工程では硬化性組成物層をパターン状に露光する。例えば、硬化性組成物層に対し、ステッパー露光機やスキャナ露光機などを用いて、所定のマスクパターンを有するマスクを介して露光することで、パターン露光することができる。これにより、露光部分を硬化することができる。露光に際して用いることができる放射線(光)としては、g線、i線等が挙げられる。また、波長300nm以下の光(好ましくは波長180~300nmの光)を用いることもできる。波長300nm以下の光としては、KrF線(波長248nm)、ArF線(波長193nm)などが挙げられ、KrF線(波長248nm)が好ましい。
<< Exposure process >>
In the exposure step, the curable composition layer is exposed in a pattern. For example, a pattern exposure can be performed by exposing the curable composition layer through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. As a result, the exposed portion can be cured. Examples of radiation (light) that can be used for exposure include g-line and i-line. Further, light having a wavelength of 300 nm or less (preferably light having a wavelength of 180 to 300 nm) can also be used. Examples of the light having a wavelength of 300 nm or less include KrF line (wavelength 248 nm) and ArF line (wavelength 193 nm), and KrF line (wavelength 248 nm) is preferable.
また、露光に際して、光を連続的に照射して露光してもよく、パルス的に照射して露光(パルス露光)してもよい。なお、パルス露光とは、短時間(例えば、ミリ秒レベル以下)のサイクルで光の照射と休止を繰り返して露光する方式の露光方法のことである。 Further, at the time of exposure, light may be continuously irradiated for exposure, or pulsed irradiation may be performed for exposure (pulse exposure). The pulse exposure is an exposure method of a method of repeatedly irradiating and pausing light in a cycle of a short time (for example, a millisecond level or less).
照射量(露光量)は、例えば、0.03~2.5J/cm2が好ましく、0.05~1.0J/cm2がより好ましく、0.08~0.5J/cm2が最も好ましい。露光時における酸素濃度については適宜選択することができる。例えば、大気下で露光してもよく、酸素濃度が19体積%以下の低酸素雰囲気下(例えば、15体積%、5体積%、実質的に無酸素)で露光してもよく、酸素濃度が21体積%を超える高酸素雰囲気下(例えば、22体積%、30体積%、50体積%)で露光してもよい。また、露光照度は適宜設定することができ、1000~100000W/m2の範囲から選択することが好ましい。酸素濃度と露光照度は適宜条件を組み合わせてよく、例えば、酸素濃度10体積%で照度10000W/m2、酸素濃度35体積%で照度20000W/m2などとすることができる。 Irradiation dose (exposure dose), for example, preferably 0.03 ~ 2.5J / cm 2, more preferably 0.05 ~ 1.0J / cm 2, most preferably 0.08 ~ 0.5J / cm 2 .. The oxygen concentration at the time of exposure can be appropriately selected. For example, it may be exposed in the atmosphere, or it may be exposed in a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, substantially anoxic), and the oxygen concentration is high. Exposure may be carried out in a high oxygen atmosphere exceeding 21% by volume (for example, 22% by volume, 30% by volume, 50% by volume). Further, the exposure illuminance can be appropriately set and is preferably selected from the range of 1000 to 100,000 W / m 2. Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10000 W / m 2 at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20000W / m 2.
<<現像工程>>
次に、露光後の硬化性組成物層における未露光部の硬化性組成物層を現像除去してパターンを形成する。未露光部の硬化性組成物層の現像除去は、現像液を用いて行うことができる。これにより、露光工程における未露光部の硬化性組成物層が現像液に溶出し、光硬化した部分だけが支持体上に残る。現像液の温度は、例えば、20~30℃が好ましい。現像時間は、20~180秒が好ましい。また、残渣除去性を向上させるため、現像液を60秒ごとに振り切り、さらに新たに現像液を供給する工程を数回繰り返してもよい。
<< Development process >>
Next, the curable composition layer in the unexposed portion of the curable composition layer after exposure is developed and removed to form a pattern. Development and removal of the curable composition layer in the unexposed portion can be performed using a developing solution. As a result, the curable composition layer of the unexposed portion in the exposure step is eluted in the developer, and only the photocured portion remains on the support. The temperature of the developing solution is preferably, for example, 20 to 30 ° C. The development time is preferably 20 to 180 seconds. Further, in order to improve the residue removability, the steps of shaking off the developing solution every 60 seconds and further supplying a new developing solution may be repeated several times.
現像液は、有機溶剤、アルカリ現像液などが挙げられ、アルカリ現像液が好ましく用いられる。アルカリ現像液としては、アルカリ剤を純水で希釈したアルカリ性水溶液(アルカリ現像液)が好ましい。アルカリ剤としては、例えば、アンモニア、エチルアミン、ジエチルアミン、ジメチルエタノールアミン、ジグリコールアミン、ジエタノールアミン、ヒドロキシアミン、エチレンジアミン、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、エチルトリメチルアンモニウムヒドロキシド、ベンジルトリメチルアンモニウムヒドロキシド、ジメチルビス(2-ヒドロキシエチル)アンモニウムヒドロキシド、コリン、ピロール、ピペリジン、1,8-ジアザビシクロ[5.4.0]-7-ウンデセンなどの有機アルカリ性化合物や、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸水素ナトリウム、ケイ酸ナトリウム、メタケイ酸ナトリウムなどの無機アルカリ性化合物が挙げられる。アルカリ剤は、分子量が大きい化合物の方が環境面および安全面で好ましい。アルカリ性水溶液のアルカリ剤の濃度は、0.001~10質量%が好ましく、0.01~1質量%がより好ましい。また、現像液は、さらに界面活性剤を含有していてもよい。界面活性剤としては、上述した界面活性剤が挙げられ、ノニオン系界面活性剤が好ましい。現像液は、移送や保管の便宜などの観点より、一旦濃縮液として製造し、使用時に必要な濃度に希釈してもよい。希釈倍率は特に限定されないが、例えば1.5~100倍の範囲に設定することができる。なお、アルカリ性水溶液を現像液として使用した場合には、現像後純水で洗浄(リンス)することが好ましい。また、リンスは、現像後の硬化性組成物層が形成された支持体を回転させつつ、現像後の硬化性組成物層へリンス液を供給して行うことが好ましい。また、リンス液を吐出させるノズルを支持体の中心部から支持体の周縁部に移動させて行うことも好ましい。この際、ノズルの支持体中心部から周縁部へ移動させるにあたり、ノズルの移動速度を徐々に低下させながら移動させてもよい。このようにしてリンスを行うことで、リンスの面内ばらつきを抑制できる。また、ノズルの支持体中心部から周縁部へ移動させつつ、支持体の回転速度を徐々に低下させても同様の効果が得られる。 Examples of the developing solution include organic solvents and alkaline developing solutions, and alkaline developing solutions are preferably used. As the alkaline developer, an alkaline aqueous solution (alkaline developer) obtained by diluting an alkaline agent with pure water is preferable. Examples of the alkaline agent include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. , Ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene and other organic substances. Examples thereof include alkaline compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate and sodium metasilicate. As the alkaline agent, a compound having a large molecular weight is preferable in terms of environment and safety. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. In addition, the developer may further contain a surfactant. Examples of the surfactant include the above-mentioned surfactants, and nonionic surfactants are preferable. The developer may be once produced as a concentrated solution and diluted to a concentration required for use from the viewpoint of convenience of transfer and storage. The dilution ratio is not particularly limited, but can be set in the range of, for example, 1.5 to 100 times. When an alkaline aqueous solution is used as a developing solution, it is preferable to wash (rinse) with pure water after development. Further, it is preferable that the rinsing is performed by supplying the rinsing liquid to the developed curable composition layer while rotating the support on which the developed curable composition layer is formed. It is also preferable to move the nozzle for discharging the rinse liquid from the central portion of the support to the peripheral edge of the support. At this time, when moving the nozzle from the central portion of the support to the peripheral portion, the nozzle may be moved while gradually reducing the moving speed. By rinsing in this way, in-plane variation of rinsing can be suppressed. Further, the same effect can be obtained by gradually reducing the rotation speed of the support while moving the nozzle from the center to the peripheral edge of the support.
現像後、乾燥を施した後に追加露光処理や加熱処理(ポストベーク)を行うことが好ましい。追加露光処理やポストベークは、硬化を完全なものとするための現像後の硬化処理である。ポストベークにおける加熱温度は、例えば100~240℃が好ましく、200~240℃がより好ましい。ポストベークは、現像後の膜を、上記条件になるようにホットプレートやコンベクションオーブン(熱風循環式乾燥機)、高周波加熱機等の加熱手段を用いて、連続式あるいはバッチ式で行うことができる。追加露光処理を行う場合、露光に用いられる光は、波長400nm以下の光であることが好ましい。また、追加露光処理は、韓国公開特許第10-2017-0122130号公報に記載の方法で行ってもよい。 It is preferable to perform additional exposure treatment or heat treatment (post-baking) after development and drying. Additional exposure treatment and post-baking are post-development curing treatments to complete the curing. The heating temperature in the post-baking is, for example, preferably 100 to 240 ° C, more preferably 200 to 240 ° C. Post-baking can be performed on the developed film in a continuous or batch manner using a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater so as to meet the above conditions. .. When the additional exposure process is performed, the light used for the exposure is preferably light having a wavelength of 400 nm or less. Further, the additional exposure process may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.
(ドライエッチング法でパターン形成する場合)
ドライエッチング法でのパターン形成は、本発明の硬化性組成物を支持体上に塗布して形成した硬化性組成物層を硬化して硬化物層を形成し、次いで、この硬化物層上にパターニングされたレジスト層を形成し、次いで、パターニングされたレジスト層をマスクとして硬化物層に対してエッチングガスを用いてドライエッチングするなどの方法で行うことができる。ドライエッチング法でのパターン形成については、特開2013-064993号公報の段落番号0010~0067の記載を参酌でき、この内容は本明細書に組み込まれる。
(When forming a pattern by dry etching method)
In the pattern formation by the dry etching method, the curable composition layer formed by applying the curable composition of the present invention on a support is cured to form a cured product layer, and then on the cured product layer. A patterned resist layer is formed, and then the cured product layer is dry-etched with an etching gas using the patterned resist layer as a mask. Regarding the pattern formation by the dry etching method, the description in paragraphs 0010 to 0067 of JP2013-064993A can be referred to, and this content is incorporated in the present specification.
<赤外線透過フィルタ>
次に、本発明の赤外線透過フィルタについて説明する。本発明の赤外線透過フィルタは、上述した本発明の膜を有する。
<Infrared transmission filter>
Next, the infrared transmission filter of the present invention will be described. The infrared transmission filter of the present invention has the above-mentioned film of the present invention.
本発明の赤外線透過フィルタは、有彩色着色剤を含むカラーフィルタと組み合わせて用いることもできる。カラーフィルタは、有彩色着色剤を含む着色組成物を用いて製造できる。 The infrared transmission filter of the present invention can also be used in combination with a color filter containing a chromatic colorant. The color filter can be produced by using a coloring composition containing a chromatic colorant.
また、本発明の赤外線透過フィルタは、本発明の膜の画素と、赤、緑、青、マゼンタ、黄、シアン、黒および無色から選ばれる画素とを有する態様も好ましい態様である。 It is also preferable that the infrared transmission filter of the present invention has pixels of the film of the present invention and pixels selected from red, green, blue, magenta, yellow, cyan, black and colorless.
<固体撮像素子>
本発明の固体撮像素子は、上述した本発明の膜を含む。固体撮像素子の構成としては、本発明の膜を有する構成であり、固体撮像素子として機能する構成であれば特に限定はない。例えば、以下のような構成が挙げられる。
<Solid image sensor>
The solid-state image sensor of the present invention includes the above-mentioned film of the present invention. The configuration of the solid-state image sensor is not particularly limited as long as it has the film of the present invention and functions as a solid-state image sensor. For example, the following configuration can be mentioned.
支持体上に、固体撮像素子の受光エリアを構成する複数のフォトダイオードおよびポリシリコン等から形成される転送電極を有し、フォトダイオードおよび転送電極上にフォトダイオードの受光部のみ開口したタングステン等から形成される遮光膜を有し、遮光膜上に遮光膜全面およびフォトダイオード受光部を覆うように形成された窒化シリコン等から形成されるデバイス保護膜を有し、デバイス保護膜上に、本発明における膜を有する構成である。さらに、デバイス保護膜上であって、本発明における膜の下(支持体に近い側)に集光手段(例えば、マイクロレンズ等。以下同じ)を有する構成や、本発明における膜上に集光手段を有する構成等であってもよい。また、カラーフィルタは、隔壁により例えば格子状に仕切られた空間に、各画素を形成する膜が埋め込まれた構造を有していてもよい。この場合の隔壁は各画素よりも低屈折率であることが好ましい。このような構造を有する撮像装置の例としては、特開2012-227478号公報、特開2014-179577号公報に記載の装置が挙げられる。 On the support, a transfer electrode formed of a plurality of photodiodes forming the light receiving area of the solid-state image sensor and polysilicon or the like is provided, and from tungsten or the like in which only the light receiving portion of the photodiode is opened on the photodiode and the transfer electrode. The present invention has a light-shielding film to be formed, a device protective film formed of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and a photodiode light receiving portion, and the present invention is provided on the device protective film. It is a configuration having a membrane in. Further, a configuration having a condensing means (for example, a microlens or the like; the same applies hereinafter) on the device protective film under the film (closer to the support) in the present invention, or condensing on the film in the present invention. It may be a configuration having means or the like. Further, the color filter may have a structure in which a film forming each pixel is embedded in a space partitioned by a partition wall, for example, in a grid pattern. The partition wall in this case preferably has a lower refractive index than each pixel. Examples of the image pickup apparatus having such a structure include the apparatus described in JP-A-2012-227478 and JP-A-2014-179757.
<赤外線センサ>
本発明の赤外線センサは、上述した本発明の膜を含む。赤外線センサの構成としては、赤外線センサとして機能する構成であれば特に限定はない。以下、本発明の赤外線センサの一実施形態について、図面を用いて説明する。
<Infrared sensor>
The infrared sensor of the present invention includes the above-mentioned film of the present invention. The configuration of the infrared sensor is not particularly limited as long as it functions as an infrared sensor. Hereinafter, an embodiment of the infrared sensor of the present invention will be described with reference to the drawings.
図1において、符号110は、固体撮像素子である。固体撮像素子110上に設けられている撮像領域は、赤外線カットフィルタ111と、赤外線透過フィルタ114とを有する。また、赤外線カットフィルタ111上には、カラーフィルタ112が積層している。カラーフィルタ112および赤外線透過フィルタ114の入射光hν側には、マイクロレンズ115が配置されている。マイクロレンズ115を覆うように平坦化層116が形成されている。
In FIG. 1,
赤外線カットフィルタ111は、可視光線領域の光(例えば、波長400~700nmの光)を透過し、赤外領域の光を遮蔽するフィルタである。カラーフィルタ112は、可視領域における特定波長の光を透過及び吸収する画素が形成されたカラーフィルタであって、特に限定はなく、従来公知の画素形成用のカラーフィルタを用いることができる。例えば、赤色(R)、緑色(G)、青色(B)の画素が形成されたカラーフィルタなどが用いられる。例えば、特開2014-043556号公報の段落番号0214~0263の記載を参酌することができ、この内容は本明細書に組み込まれる。赤外線透過フィルタ114は、可視光線遮蔽性を有し、かつ、特定波長の赤外線を透過させるフィルタである。
The
図1に示す赤外線センサにおいて、平坦化層116上には、赤外線カットフィルタ111とは別の赤外線カットフィルタ(他の赤外線カットフィルタ)がさらに配置されていてもよい。他の赤外線カットフィルタとしては、銅を含有する層および/または誘電体多層膜を有するものなどが挙げられる。これらの詳細については、上述したものが挙げられる。また、他の赤外線カットフィルタとしては、デュアルバンドパスフィルタを用いてもよい。
In the infrared sensor shown in FIG. 1, an infrared cut filter (another infrared cut filter) different from the
また、図1に示す実施形態では、カラーフィルタ112が、赤外線カットフィルタ111よりも入射光hν側に設けられているが、赤外線カットフィルタ111と、カラーフィルタ112との順序を入れ替えて、赤外線カットフィルタ111を、カラーフィルタ112よりも入射光hν側に設けてもよい。
Further, in the embodiment shown in FIG. 1, the
また、図1に示す実施形態では、赤外線カットフィルタ111とカラーフィルタ112は隣接して積層しているが、両フィルタは必ずしも隣接している必要はなく、間に他の層が設けられていても良い。
Further, in the embodiment shown in FIG. 1, the
また、図1に示す実施形態において、赤外線透過フィルタ114とは異なる分光特性を有する他の赤外線透過フィルタを更に有していてもよい。
Further, in the embodiment shown in FIG. 1, another infrared transmission filter having a spectral characteristic different from that of the
<画像表示装置>
本発明の膜は、液晶表示装置や有機エレクトロルミネッセンス(有機EL)表示装置などの画像表示装置に用いることもできる。表示装置の定義や各表示装置の詳細については、例えば「電子ディスプレイデバイス(佐々木 昭夫著、(株)工業調査会 1990年発行)」、「ディスプレイデバイス(伊吹 順章著、産業図書(株)平成元年発行)」などに記載されている。また、液晶表示装置については、例えば「次世代液晶ディスプレイ技術(内田 龍男編集、(株)工業調査会 1994年発行)」に記載されている。本発明が適用できる液晶表示装置のタイプは特に制限はなく、例えば、上記の「次世代液晶ディスプレイ技術」に記載されている色々な方式の液晶表示装置に適用できる。
<Image display device>
The film of the present invention can also be used in an image display device such as a liquid crystal display device or an organic electroluminescence (organic EL) display device. For details on the definition of display devices and the details of each display device, see, for example, "Electronic Display Device (Akio Sasaki, Kogyo Chosakai Co., Ltd., 1990)", "Display Device (Junaki Ibuki, Sangyo Tosho Co., Ltd.)" (Issued in the first year) ”and so on. The liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994)". The type of liquid crystal display device to which the present invention can be applied is not particularly limited, and for example, it can be applied to various types of liquid crystal display devices described in the above-mentioned "next-generation liquid crystal display technology".
画像表示装置は、表示素子として白色有機EL素子を有する画像表示装置であってもよい。白色有機EL素子としては、タンデム構造であることが好ましい。有機EL素子のタンデム構造については、特開2003-045676号公報、三上明義監修、「有機EL技術開発の最前線-高輝度・高精度・長寿命化・ノウハウ集-」、技術情報協会、326-328ページ、2008年などに記載されている。有機EL素子が発光する白色光のスペクトルは、青色領域(430nm-485nm)、緑色領域(530nm-580nm)及び黄色領域(580nm-620nm)に強い極大発光ピークを有することが好ましい。これらの発光ピークに加え更に赤色領域(650nm-700nm)に極大発光ピークを有することがより好ましい。 The image display device may be an image display device having a white organic EL element as the display element. The white organic EL element preferably has a tandem structure. Regarding the tandem structure of organic EL elements, Japanese Patent Application Laid-Open No. 2003-045676, supervised by Akiyoshi Mikami, "Frontiers of Organic EL Technology Development-High Brightness, High Precision, Long Life, Know-how Collection-", Technical Information Association, It is described on pages 326-328, 2008 and the like. The spectrum of white light emitted by the organic EL device preferably has strong maximum emission peaks in the blue region (430 nm-485 nm), the green region (530 nm-580 nm), and the yellow region (580 nm-620 nm). In addition to these emission peaks, it is more preferable to have a maximum emission peak in the red region (650 nm-700 nm).
以下、本発明を実施例により更に具体的に説明するが、本発明はその主旨を越えない限り、以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded.
<量子ドットの極大吸収波長の測定>
量子ドットの極大吸収波長の測定は、量子ドットの10mg/mLのトルエン溶液を調製し、この溶液の吸光度を紫外可視近赤外分光光度計を用いて測定した。
<Measurement of maximum absorption wavelength of quantum dots>
For the measurement of the maximum absorption wavelength of the quantum dots, a toluene solution of 10 mg / mL of the quantum dots was prepared, and the absorbance of this solution was measured using an ultraviolet-visible-near-infrared spectrophotometer.
<硬化性組成物の調製>
下記表に記載の原料を、下記表に記載の割合で混合して硬化性組成物を調製した。
<Preparation of curable composition>
The raw materials listed in the table below were mixed at the ratios listed in the table below to prepare a curable composition.
上記表に記載の略語で記載した原料は以下の通りである。 The raw materials described by the abbreviations in the above table are as follows.
(量子ドット分散液)
[波長700~2000nmの範囲に極大吸収波長を有する量子ドットの分散液]
QD-900:平均一次粒子径3.2nmのPbS量子ドットの表面にオレイン酸が配位子として配位したPbS量子ドット分散液(PbS量子ドット濃度10質量%のオクタン溶液)。PbS量子ドットの極大吸収波長は900nmであった。
QD-1000:平均一次粒子径3.5nmのPbS量子ドットの表面にオレイン酸が配位子として配位したPbS量子ドット分散液(PbS量子ドット濃度10質量%のオクタン溶液)。PbS量子ドットの極大吸収波長は1000nmであった。
QD-1100:平均一次粒子径4.0nmのPbS量子ドットの表面にオレイン酸が配位子として配位したPbS量子ドット分散液(PbS量子ドット濃度10質量%のオクタン溶液)。PbS量子ドットの極大吸収波長は1100nmであった。
QD-1200:平均一次粒子径4.5nmのPbS量子ドットの表面にオレイン酸が配位子として配位したPbS量子ドット分散液(PbS量子ドット濃度10質量%のオクタン溶液)。PbS量子ドットの極大吸収波長は1200nmであった。
QD-1300:平均一次粒子径5.0nmのPbS量子ドットの表面にオレイン酸が配位子として配位したPbS量子ドット分散液(PbS量子ドット濃度10質量%のオクタン溶液)。PbS量子ドットの極大吸収波長は1300nmであった。
QD-1400:平均一次粒子径5.5nmのPbS量子ドットの表面にオレイン酸が配位子として配位したPbS量子ドット分散液(PbS量子ドット濃度10質量%のオクタン溶液)。PbS量子ドットの極大吸収波長は1400nmであった。
QD-1500:平均一次粒子径6.0nmのPbS量子ドットの表面にオレイン酸が配位子として配位したPbS量子ドット分散液(PbS量子ドット濃度10質量%のオクタン溶液)。PbS量子ドットの極大吸収波長は1500nmであった。
QD-1600:平均一次粒子径6.5nmのPbS量子ドットの表面にオレイン酸が配位子として配位したPbS量子ドット分散液(PbS量子ドット濃度10質量%のオクタン溶液)。PbS量子ドットの極大吸収波長は1600nmであった。
QD-1700:平均一次粒子径7.0nmのPbS量子ドットの表面にオレイン酸が配位子として配位したPbS量子ドット分散液(PbS量子ドット濃度10質量%のオクタン溶液)。PbS量子ドットの極大吸収波長は1700nmであった。
QD-1800:平均一次粒子径8.0nmのPbS量子ドットの表面にオレイン酸が配位子として配位したPbS量子ドット分散液(PbS量子ドット濃度10質量%のオクタン溶液)。PbS量子ドットの極大吸収波長は1800nmであった。
QD-1900:平均一次粒子径8.5nmのPbS量子ドットの表面にオレイン酸が配位子として配位したPbS量子ドット分散液(PbS量子ドット濃度10質量%のオクタン溶液)。PbS量子ドットの極大吸収波長は1900nmであった。
QD-2000:平均一次粒子径9.0nmのPbS量子ドットの表面にオレイン酸が配位子として配位したPbS量子ドット分散液(PbS量子ドット濃度10質量%のオクタン溶液)。PbS量子ドットの極大吸収波長は2000nmであった。
(Quantum dot dispersion liquid)
[Quantum dot dispersion having a maximum absorption wavelength in the wavelength range of 700 to 2000 nm]
QD-900: PbS quantum dot dispersion liquid (octane solution having a PbS quantum dot concentration of 10% by mass) in which oleic acid is coordinated as a ligand on the surface of PbS quantum dots having an average primary particle diameter of 3.2 nm. The maximum absorption wavelength of the PbS quantum dots was 900 nm.
QD-1000: PbS quantum dot dispersion liquid (octane solution having a PbS quantum dot concentration of 10% by mass) in which oleic acid is coordinated as a ligand on the surface of PbS quantum dots having an average primary particle diameter of 3.5 nm. The maximum absorption wavelength of the PbS quantum dots was 1000 nm.
QD-1100: PbS quantum dot dispersion liquid (octane solution having a PbS quantum dot concentration of 10% by mass) in which oleic acid is coordinated as a ligand on the surface of PbS quantum dots having an average primary particle diameter of 4.0 nm. The maximum absorption wavelength of the PbS quantum dots was 1100 nm.
QD-1200: PbS quantum dot dispersion liquid (octane solution having a PbS quantum dot concentration of 10% by mass) in which oleic acid is coordinated as a ligand on the surface of PbS quantum dots having an average primary particle diameter of 4.5 nm. The maximum absorption wavelength of the PbS quantum dots was 1200 nm.
QD-1300: PbS quantum dot dispersion liquid (octane solution having a PbS quantum dot concentration of 10% by mass) in which oleic acid is coordinated as a ligand on the surface of PbS quantum dots having an average primary particle diameter of 5.0 nm. The maximum absorption wavelength of the PbS quantum dots was 1300 nm.
QD-1400: PbS quantum dot dispersion liquid (octane solution having a PbS quantum dot concentration of 10% by mass) in which oleic acid is coordinated as a ligand on the surface of PbS quantum dots having an average primary particle diameter of 5.5 nm. The maximum absorption wavelength of the PbS quantum dots was 1400 nm.
QD-1500: PbS quantum dot dispersion liquid (octane solution having a PbS quantum dot concentration of 10% by mass) in which oleic acid is coordinated as a ligand on the surface of PbS quantum dots having an average primary particle diameter of 6.0 nm. The maximum absorption wavelength of the PbS quantum dots was 1500 nm.
QD-1600: PbS quantum dot dispersion liquid (octane solution having a PbS quantum dot concentration of 10% by mass) in which oleic acid is coordinated as a ligand on the surface of PbS quantum dots having an average primary particle diameter of 6.5 nm. The maximum absorption wavelength of the PbS quantum dots was 1600 nm.
QD-1700: PbS quantum dot dispersion liquid (octane solution having a PbS quantum dot concentration of 10% by mass) in which oleic acid is coordinated as a ligand on the surface of PbS quantum dots having an average primary particle diameter of 7.0 nm. The maximum absorption wavelength of the PbS quantum dots was 1700 nm.
QD-1800: PbS quantum dot dispersion liquid (octane solution having a PbS quantum dot concentration of 10% by mass) in which oleic acid is coordinated as a ligand on the surface of PbS quantum dots having an average primary particle diameter of 8.0 nm. The maximum absorption wavelength of the PbS quantum dots was 1800 nm.
QD-1900: PbS quantum dot dispersion liquid (octane solution having a PbS quantum dot concentration of 10% by mass) in which oleic acid is coordinated as a ligand on the surface of PbS quantum dots having an average primary particle diameter of 8.5 nm. The maximum absorption wavelength of the PbS quantum dots was 1900 nm.
QD-2000: PbS quantum dot dispersion liquid (octane solution having a PbS quantum dot concentration of 10% by mass) in which oleic acid is coordinated as a ligand on the surface of PbS quantum dots having an average primary particle diameter of 9.0 nm. The maximum absorption wavelength of PbS quantum dots was 2000 nm.
[波長700nm未満に極大吸収波長を有する量子ドットの分散液]
QD-450:平均一次粒子径7nmのペロブスカイト(CsPb(Cl/Br)3)量子ドットの表面にオレイン酸が配位子として配位したPbS量子ドット分散液(PbS量子ドット濃度10質量%のオクタン溶液)。ペロブスカイト量子ドットの極大吸収波長は450nmであった。
[Quantum dot dispersion having a maximum absorption wavelength below 700 nm]
QD-450: PbS quantum dot dispersion liquid (PbS quantum dot concentration 10% by mass) in which oleic acid is coordinated as a ligand on the surface of perovskite (CsPb (Cl / Br) 3) quantum dots with an average primary particle diameter of 7 nm. solution). The maximum absorption wavelength of perovskite quantum dots was 450 nm.
(有機色材)
C-1:下記構造の化合物(波長700nmを超え1400nm以下の範囲に極大吸収波長を有する有機色材)
C-2:下記構造の化合物(波長700nmを超え1400nm以下の範囲に極大吸収波長を有する有機色材)
C-1: A compound having the following structure (organic coloring material having a maximum absorption wavelength in the range of wavelengths exceeding 700 nm and 1400 nm or less)
C-2: A compound having the following structure (organic coloring material having a maximum absorption wavelength in the range of wavelengths exceeding 700 nm and 1400 nm or less)
(樹脂)
P-1:下記構造の樹脂(主鎖に付記した数値はモル比である。重量平均分子量=40000)
P-2:下記構造の樹脂(主鎖に付記した数値はモル比である。重量平均分子量=11000)
P-3:下記構造の樹脂(主鎖に付記した数値はモル比である。重量平均分子量=33000)
P-1: Resin having the following structure (the numerical value added to the main chain is the molar ratio. Weight average molecular weight = 40,000)
P-2: Resin having the following structure (the numerical value added to the main chain is the molar ratio. Weight average molecular weight = 11000)
P-3: Resin having the following structure (the numerical value added to the main chain is the molar ratio. Weight average molecular weight = 33000)
(重合性化合物)
M-1:ジペンタエリスリトールヘキサアクリレート
M-2:ペンタエリスリトールテトラアクリレート
(Polymerizable compound)
M-1: Dipentaerythritol hexaacrylate M-2: Pentaerythritol tetraacrylate
(光重合開始剤)
I-1:Irgacure OXE01(BASF社製)
I-2:下記構造の化合物
I-1: Irgacure OXE01 (manufactured by BASF)
I-2: Compound with the following structure
(界面活性剤)
W-1:下記混合物(重量平均分子量=14000)。下記の式中、繰り返し単位の割合を示す%はモル%である。
W-1: The following mixture (weight average molecular weight = 14000). In the formula below,% indicating the ratio of the repeating unit is mol%.
(重合禁止剤)
G-1:p-メトキシフェノール
(Polymerization inhibitor)
G-1: p-methoxyphenol
(溶剤)
S-1:プロピレングリコールモノメチルエーテルアセテート
S-2:シクロペンタノン
(solvent)
S-1: Propylene glycol monomethyl ether acetate S-2: Cyclopentanone
<評価>
各硬化性組成物をポストベーク後の膜厚が1.0μmとなるようにガラス基板上にスピンコートした。次いで、ホットプレートを用いて、100℃、120秒間加熱した。次いで、ホットプレートを用いて200℃、300秒間加熱処理(ポストベーク)を行い、膜を形成した。得られた膜を、フォントサイズが9~20ポイント(pt)の文字(「A」という文字)を記載した紙の上に置き、膜の上から文字を観察し、目視での文字の識別度合いによって可視遮光性を評価した。また、得られた膜の分光について、紫外可視近赤外分光光度計を用いて測定して赤外透過性を評価した。
<Evaluation>
Each curable composition was spin-coated on a glass substrate so that the film thickness after post-baking was 1.0 μm. Then, using a hot plate, it was heated at 100 ° C. for 120 seconds. Next, a film was formed by heat treatment (post-baking) at 200 ° C. for 300 seconds using a hot plate. Place the obtained film on a piece of paper on which characters (character "A") with a font size of 9 to 20 points (pt) are written, observe the characters from above the film, and visually identify the characters. The visible shading property was evaluated by. In addition, the spectrum of the obtained film was measured using an ultraviolet-visible near-infrared spectrophotometer to evaluate the infrared transparency.
(可視遮光性の評価基準)
5:文字のフォントサイズが20ptでも膜裏面の文字を識別できない
4:文字のフォントサイズが20ptの場合は膜裏面の文字を識別できるが、文字のフォントサイズが15ptの場合は膜裏面の文字を識別できない
3:文字のフォントサイズが15ptの場合は膜裏面の文字を識別できるが、文字のフォントサイズが10ptの場合は膜裏面の文字を識別できない
2:文字のフォントサイズが10ptの場合は膜裏面の文字を識別できるが、文字のフォントサイズが9ptの場合は膜裏面の文字を識別できない
1:文字のフォントサイズが9ptでも膜裏面の文字を識別できる
(Evaluation criteria for visible shading)
5: Characters on the back surface of the film cannot be identified even if the font size of the characters is 20 pt 4: Characters on the back surface of the film can be identified when the font size of the characters is 20 pt, but characters on the back surface of the film can be identified when the font size of the characters is 15 pt. Unidentifiable 3: Characters on the back side of the film can be identified when the font size of the characters is 15 pt, but characters on the back side of the film cannot be identified when the font size of the characters is 10 pt 2: Membrane when the font size of the characters is 10 pt Characters on the back side can be identified, but characters on the back side of the film cannot be identified when the font size of the characters is 9pt 1: Characters on the back side of the film can be identified even if the font size of the characters is 9pt.
(赤外透過性の評価基準)
5:2200nmにおける透過率が70%以上
4:2200nmにおける透過率が65%以上70%未満
3:2200nmにおける透過率が60%以上65%未満
2:2200nmにおける透過率が50%以上60%未満
1:2200nmにおける透過率が0%以上50%未満
(Evaluation criteria for infrared transparency)
5: Transmittance at 2200 nm is 70% or more 4: Transmittance at 2200 nm is 65% or more and less than 70% 3: Transmittance at 2200 nm is 60% or more and less than 65% 2: Transmittance at 2200 nm is 50% or more and less than 60% 1 : Transmittance at 2200 nm is 0% or more and less than 50%
上記表に示すように、実施例の硬化性組成物は、可視遮光性が高く、かつ、赤外透過性に優れていた。また、溶剤S-1と溶剤S-2を混合しても同様の効果が得られる。また、実施例1~54の硬化性組成物をポストベーク後の膜厚が1.0μmとなるようにガラス基板上にスピンコートした。次いで、ホットプレートを用いて、100℃、120秒間加熱した。次いで、ホットプレートを用いて200℃、300秒間加熱処理(ポストベーク)を行い、膜を形成した。得られた膜について、波長400~650nmの範囲における吸光度の最小値Aと、波長2200nmでの吸光度Bをそれぞれ測定し、波長400~650nmの範囲における吸光度の最小値Aと波長2200nmでの吸光度Bとの比A/B(波長400~650nmの範囲における吸光度の最小値A/波長2200nmでの吸光度B)を測定したところ、いずれも前述の比は4.5以上であった。 As shown in the above table, the curable composition of the example had high visible light-shielding property and excellent infrared transparency. Further, the same effect can be obtained by mixing the solvent S-1 and the solvent S-2. Further, the curable compositions of Examples 1 to 54 were spin-coated on a glass substrate so that the film thickness after post-baking was 1.0 μm. Then, using a hot plate, it was heated at 100 ° C. for 120 seconds. Next, a film was formed by heat treatment (post-baking) at 200 ° C. for 300 seconds using a hot plate. For the obtained film, the minimum absorbance A in the wavelength range of 400 to 650 nm and the absorbance B in the wavelength 2200 nm were measured, respectively, and the minimum absorbance A in the wavelength range of 400 to 650 nm and the absorbance B in the wavelength 2200 nm were measured. When the ratio A / B (minimum value of absorbance A in the wavelength range of 400 to 650 nm / absorbance B in the wavelength range of 2200 nm) was measured, the above-mentioned ratio was 4.5 or more.
また、実施例1、14、15、28~36、38、40~42、53、54の硬化性組成物を用いて得られた膜は、波長400~1000nmの光を遮光し、波長1100nm以上の波長の光を透過させるものであった。
また、実施例2、12、16、43の硬化性組成物を用いて得られた膜は、波長400~1100nmの光を遮光し、波長1200nm以上の波長の光を透過させるものであった。
また、実施例3、17、44の硬化性組成物を用いて得られた膜は、波長400~1200nmの光を遮光し、波長1300nm以上の波長の光を透過させるものであった。
また、実施例4、18、45の硬化性組成物を用いて得られた膜は、波長400~1300nmの光を遮光し、波長1400nm以上の波長の光を透過させるものであった。
また、実施例5、13、19、26、27、37、39、46の硬化性組成物を用いて得られた膜は、波長400~1400nmの光を遮光し、波長1500nm以上の波長の光を透過させるものであった。
また、実施例6、20、47の硬化性組成物を用いて得られた膜は、波長400~1500nmの光を遮光し、波長1600nm以上の波長の光を透過させるものであった。
また、実施例7、21、48の硬化性組成物を用いて得られた膜は、波長400~1600nmの光を遮光し、波長1700nm以上の波長の光を透過させるものであった。
また、実施例8、22、49の硬化性組成物を用いて得られた膜は、波長400~1700nmの光を遮光し、波長1800nm以上の波長の光を透過させるものであった。
また、実施例9、23、50の硬化性組成物を用いて得られた膜は、波長400~1800nmの光を遮光し、波長1900nm以上の波長の光を透過させるものであった。
また、実施例10、24、51の硬化性組成物を用いて得られた膜は、波長400~1900nmの光を遮光し、波長2000nm以上の波長の光を透過させるものであった。
また、実施例11、25、52の硬化性組成物を用いて得られた膜は、波長400~2000nmの光を遮光し、波長2100nm以上の波長の光を透過させるものであった。
Further, the film obtained by using the curable compositions of Examples 1, 14, 15, 28 to 36, 38, 40 to 42, 53 and 54 shields light having a wavelength of 400 to 1000 nm and has a wavelength of 1100 nm or more. It was intended to transmit light of the same wavelength.
Further, the film obtained by using the curable compositions of Examples 2, 12, 16 and 43 shields light having a wavelength of 400 to 1100 nm and transmits light having a wavelength of 1200 nm or more.
Further, the film obtained by using the curable compositions of Examples 3, 17, and 44 shields light having a wavelength of 400 to 1200 nm and transmits light having a wavelength of 1300 nm or more.
Further, the films obtained by using the curable compositions of Examples 4, 18 and 45 shielded light having a wavelength of 400 to 1300 nm and transmitted light having a wavelength of 1400 nm or more.
Further, the film obtained by using the curable composition of Examples 5, 13, 19, 26, 27, 37, 39, 46 blocks light having a wavelength of 400 to 1400 nm, and light having a wavelength of 1500 nm or more. Was to be transmitted.
Further, the film obtained by using the curable compositions of Examples 6, 20 and 47 shields light having a wavelength of 400 to 1500 nm and transmits light having a wavelength of 1600 nm or more.
Further, the film obtained by using the curable compositions of Examples 7, 21, and 48 shields light having a wavelength of 400 to 1600 nm and transmits light having a wavelength of 1700 nm or more.
Further, the film obtained by using the curable compositions of Examples 8, 22, and 49 shields light having a wavelength of 400 to 1700 nm and transmits light having a wavelength of 1800 nm or more.
Further, the film obtained by using the curable compositions of Examples 9, 23 and 50 shields light having a wavelength of 400 to 1800 nm and transmits light having a wavelength of 1900 nm or more.
Further, the film obtained by using the curable compositions of Examples 10, 24 and 51 shields light having a wavelength of 400 to 1900 nm and transmits light having a wavelength of 2000 nm or more.
Further, the films obtained by using the curable compositions of Examples 11, 25 and 52 shielded light having a wavelength of 400 to 2000 nm and transmitted light having a wavelength of 2100 nm or more.
110:固体撮像素子、111:赤外線カットフィルタ、112:カラーフィルタ、114:赤外線透過フィルタ、115:マイクロレンズ、116:平坦化層 110: Solid-state image sensor, 111: Infrared cut filter, 112: Color filter, 114: Infrared transmission filter, 115: Microlens, 116: Flattening layer
Claims (20)
前記硬化性組成物の全固形分中に前記量子ドットを5質量%以上含有する、硬化性組成物。 A curable composition containing quantum dots having a maximum absorption wavelength in the wavelength range of 700 to 2000 nm and a curable compound.
A curable composition containing 5% by mass or more of the quantum dots in the total solid content of the curable composition.
波長700~2000nmの範囲に極大吸収波長を有する第1の量子ドットと、
前記第1の量子ドットの極大吸収波長よりも長波長側に極大吸収波長を有する第2の量子ドットと、を含む、請求項1~3のいずれか1項に記載の硬化性組成物。 The quantum dots
A first quantum dot having a maximum absorption wavelength in the wavelength range of 700 to 2000 nm,
The curable composition according to any one of claims 1 to 3, further comprising a second quantum dot having a maximum absorption wavelength on a wavelength side longer than the maximum absorption wavelength of the first quantum dot.
前記樹脂の全量中における、アミン価を有する樹脂の含有量が30質量%以下である、請求項1~13のいずれか1項に記載の硬化性組成物。 The curable compound contains a resin and contains
The curable composition according to any one of claims 1 to 13, wherein the content of the resin having an amine value in the total amount of the resin is 30% by mass or less.
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| JP2014058036A (en) * | 2012-09-17 | 2014-04-03 | Boeing Co | Ir absorbing coatings comprising fluorinated nanoparticles |
| WO2014084353A1 (en) * | 2012-11-30 | 2014-06-05 | 住友金属鉱山株式会社 | Near-infrared absorption filter and image pickup element |
| WO2019054281A1 (en) * | 2017-09-15 | 2019-03-21 | 富士フイルム株式会社 | Composition, film, laminate, infrared transmission filter, solid-state imaging device and infrared sensor |
| CN110784312A (en) * | 2019-09-25 | 2020-02-11 | 宁波大学 | Preparation method of PUF device and key generation method thereof |
| WO2020059509A1 (en) * | 2018-09-20 | 2020-03-26 | 富士フイルム株式会社 | Curable composition, cured film, infrared transmission filter, laminate, solid-state imaging element, sensor, and pattern formation method |
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| JP2017147324A (en) * | 2016-02-17 | 2017-08-24 | 日本電気株式会社 | Infrared detector and manufacturing method thereof |
| JP2018100959A (en) * | 2016-12-16 | 2018-06-28 | シャープ株式会社 | Detector, detector calibration method, correction method, and detection apparatus |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2014058036A (en) * | 2012-09-17 | 2014-04-03 | Boeing Co | Ir absorbing coatings comprising fluorinated nanoparticles |
| WO2014084353A1 (en) * | 2012-11-30 | 2014-06-05 | 住友金属鉱山株式会社 | Near-infrared absorption filter and image pickup element |
| WO2019054281A1 (en) * | 2017-09-15 | 2019-03-21 | 富士フイルム株式会社 | Composition, film, laminate, infrared transmission filter, solid-state imaging device and infrared sensor |
| WO2020059509A1 (en) * | 2018-09-20 | 2020-03-26 | 富士フイルム株式会社 | Curable composition, cured film, infrared transmission filter, laminate, solid-state imaging element, sensor, and pattern formation method |
| CN110784312A (en) * | 2019-09-25 | 2020-02-11 | 宁波大学 | Preparation method of PUF device and key generation method thereof |
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| WO2023120215A1 (en) * | 2021-12-24 | 2023-06-29 | 住友化学株式会社 | Composition, film and display device |
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