WO2021235373A1 - 樹脂組成物、膜、光学フィルタ、固体撮像素子および画像表示装置 - Google Patents
樹脂組成物、膜、光学フィルタ、固体撮像素子および画像表示装置 Download PDFInfo
- Publication number
- WO2021235373A1 WO2021235373A1 PCT/JP2021/018527 JP2021018527W WO2021235373A1 WO 2021235373 A1 WO2021235373 A1 WO 2021235373A1 JP 2021018527 W JP2021018527 W JP 2021018527W WO 2021235373 A1 WO2021235373 A1 WO 2021235373A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- pigment
- compound
- mass
- resin composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/02—Polyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
- C08K5/3475—Five-membered rings condensed with carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/16—Amino-anthraquinones
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B25/00—Quinophthalones
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B45/00—Complex metal compounds of azo dyes
- C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
- C09B45/04—Azo compounds in general
- C09B45/12—Azo compounds in general other metal compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B48/00—Quinacridones
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B55/00—Azomethine dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/04—Isoindoline dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/02—Polyamines
Definitions
- the present invention relates to a resin composition containing a pigment.
- the present invention also relates to a film, an optical filter, a solid-state image pickup device, and an image display device using a resin composition.
- CCD charge-coupled device
- the color filter is manufactured using a resin composition containing a coloring material. Further, in general, when a pigment is used as a coloring material, the pigment is dispersed in the resin composition by using a pigment derivative, a dispersant, or the like.
- Patent Document 1 describes an invention relating to a coloring composition for a color filter containing a xanthene-based pigment, an organic pigment, polyethyleneimine, and a binder resin.
- Patent Document 2 includes a pigment, a dispersant, a photopolymerizable monomer, and a photopolymerization initiator.
- the dispersant is a linear dispersant and a comb-shaped dispersant, and is photopolymerized.
- the invention relating to a coloring composition for a color filter which comprises a photopolymerizable monomer having 3 or less polymerizable functional groups and a photopolymerizable monomer having 3 or more polymerizable functional groups, is contained in the sex monomer. Have been described.
- a film When forming a film using a resin composition, a film may be formed using a resin composition stored at a low temperature.
- the viscosity of the resin composition tends to increase due to the aggregation of the pigment in the resin composition during storage of the resin composition. rice field.
- the viscosity of the resin composition tends to increase.
- an object of the present invention is to provide a resin composition having excellent storage stability at low temperatures. Another object of the present invention is to provide a film, an optical filter, a solid-state image pickup device, and an image display device using a resin composition.
- the present invention provides the following.
- ⁇ 3> The resin composition according to ⁇ 1> or ⁇ 2>, wherein the amine value of the compound A is 15 mmol / g or more.
- ⁇ 4> The resin composition according to any one of ⁇ 1> to ⁇ 3>, wherein the compound A is a polyalkyleneimine.
- ⁇ 5> The resin composition according to any one of ⁇ 1> to ⁇ 3>, wherein the compound A is polyethyleneimine.
- ⁇ 6> The resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein the compound A has a molecular weight of 2000 or less.
- ⁇ 7> The resin composition according to any one of ⁇ 1> to ⁇ 6>, wherein the pigment contains a chromatic pigment.
- the present invention it is possible to provide a resin composition having excellent storage stability at low temperatures. Further, it is possible to provide a film, an optical filter, a solid-state image pickup device, and an image display device using a resin composition.
- the contents of the present invention will be described in detail.
- "to” is used to mean that the numerical values described before and after it are included as the lower limit value and the upper limit value.
- the notation not describing substitution and non-substitution also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group).
- 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).
- the term "exposure” includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, 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.
- 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 structural formula represents a methyl group
- Et represents an ethyl group
- Bu represents a butyl group
- Pr represents a propyl group
- Ph represents a phenyl group.
- the weight average molecular weight and the number average molecular weight are polystyrene-equivalent values measured by a GPC (gel permeation chromatography) method.
- the near infrared ray means light having a wavelength of 700 to 2500 nm.
- the total solid content means the total mass of all the components of the composition excluding the solvent.
- the pigment means a coloring material that is difficult to dissolve in a solvent.
- the solubility of the pigment in 100 g of water at 23 ° C. and 100 g of propylene glycol monomethyl ether acetate at 23 ° C. is preferably 0.1 g or less, and more preferably 0.01 g or less.
- the dye means a coloring material that is easily dissolved in a solvent.
- the term "process" is included in this term not only as an independent process but also as long as the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. ..
- the resin composition of the present invention comprises a pigment, a compound A containing 3 or more basic groups in one molecule, an amine value of 2.7 mmol / g or more, and a molecular weight of 100 or more, and a resin having an acid group. It is a resin composition containing 40% by mass or more of a pigment in the total solid content of the resin composition.
- the resin composition of the present invention has excellent storage stability even though the pigment content in the total solid content is 40% by mass or more, and the resin composition is stored at a low temperature for a long period of time. Even in this case, the increase in viscosity can be suppressed. It is presumed that the reason why such an effect is obtained is as follows. Since the resin composition of the present invention contains a pigment, the above-mentioned compound A, and a resin having an acid group, respectively, a part of the basic group of the compound A is coordinated to the surface of the pigment in the resin composition. However, among the three or more basic groups of the compound A, the basic group not coordinated with the pigment interacts with the acid group of the resin having the acid group, and the pigment-compound A is contained in the resin composition.
- -It is presumed that a network structure of a resin having an acid group is formed. It is presumed that by forming such a network structure in the resin composition, aggregation of the pigments contained in the resin composition could be effectively suppressed, and excellent storage stability was obtained.
- pigments containing metal atoms such as zinc halide phthalocyanine pigments tend to aggregate and the viscosity of the resin composition tends to increase during storage.
- pigments containing metal atoms such as zinc halide phthalocyanine pigments are included. Even when a pigment is used, a resin composition having excellent storage stability can be obtained. Therefore, the effect of the present invention can be remarkably obtained when a pigment containing a metal atom such as a halogenated zinc phthalocyanine pigment is used. It is presumed that the reason why such an effect is obtained is that the basic group of compound A is easily coordinated with the metal atom of the pigment and the above-mentioned network structure is easily formed.
- the resin composition of the present invention it is possible to form a film in which the generation of foreign substances is suppressed. It is presumed that the above network structure was formed even in the film, and the movement of the pigment in the film could be suppressed, and as a result, the generation of foreign substances could be suppressed.
- the aggregation of the pigment in the film can be suppressed, the fluctuation of the spectral characteristics can be suppressed.
- the resin composition of the present invention is preferably used as a resin composition for an optical filter.
- the optical filter include a color filter, a near-infrared transmission filter, a near-infrared cut filter, and the like, and a color filter is preferable.
- the resin composition of the present invention is preferably used for a solid-state image sensor. More specifically, it is preferably used as a resin composition for an optical filter used for a solid-state image sensor, and more preferably used as a resin composition for forming colored pixels of a color filter used for a solid-state image sensor.
- the color filter examples include a filter having colored pixels that transmit light of a specific wavelength.
- the colored pixel examples include a red pixel, a green pixel, a blue pixel, a magenta color pixel, a cyan color pixel, a yellow pixel and the like, and a green pixel or a cyan color pixel is preferable, and a green pixel is more preferable.
- the colored pixels of the color filter can be formed by using a resin composition containing a chromatic pigment.
- the maximum absorption wavelength of the near-infrared cut filter is preferably in the wavelength range of 700 to 1800 nm, more preferably in the wavelength range of 700 to 1300 nm, and even more preferably in the wavelength range of 700 to 1000 nm. ..
- the transmittance of the near-infrared cut filter in the entire wavelength range of 400 to 650 nm is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more.
- the transmittance at at least one point in the wavelength range of 700 to 1800 nm is preferably 20% or less.
- the ratio of the absorbance Amax at the maximum absorption wavelength of the near-infrared cut filter to the absorbance A550 at a wavelength of 550 nm is preferably 20 to 500, more preferably 50 to 500. , 70 to 450, more preferably 100 to 400, and particularly preferably 100 to 400.
- the near-infrared cut filter can be formed by using a resin composition containing a near-infrared absorbing pigment.
- the near-infrared ray transmission filter is a filter that transmits at least a part of near-infrared rays.
- the near-infrared transmission filter may be a filter (transparent film) that transmits both visible light and near-infrared light, and is a filter that shields at least a part of visible light and transmits at least a part of near-infrared light. May be good.
- the maximum value of the transmittance in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the transmittance in the wavelength range of 1100 to 1300 nm.
- a filter satisfying the spectral characteristics having a minimum value of 70% or more is preferably mentioned.
- the near-infrared transmission filter is preferably a filter that satisfies any of the following spectral characteristics (1) to (5).
- a filter of 70% or more (preferably 75% or more, more preferably 80% or more).
- the maximum value of the transmittance in the wavelength range of 400 to 750 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 900 to 1500 nm is.
- a filter of 70% or more (preferably 75% or more, more preferably 80% or more).
- the maximum value of the transmittance in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 1000 to 1500 nm is.
- a filter of 70% or more preferably 75% or more, more preferably 80% or more).
- the maximum value of the transmittance in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 1100 to 1500 nm is.
- a filter of 70% or more preferably 75% or more, more preferably 80% or more.
- the maximum value of the transmittance in the wavelength range of 400 to 1050 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 1200 to 1500 nm is.
- a filter of 70% or more preferably 75% or more, more preferably 80% or more).
- the resin composition of the present invention can also be used as a light-shielding film or the like.
- the solid content concentration of the resin composition of the present invention is preferably 5 to 30% by mass.
- the lower limit is preferably 7.5% by mass or more, more preferably 10% by mass or more.
- the upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less.
- the resin composition of the present invention contains a pigment.
- the pigment include a white pigment, a black pigment, a chromatic pigment, and a near-infrared absorbing pigment.
- the white pigment includes not only pure white but also light gray (for example, grayish white, light gray, etc.) pigment close to white.
- a chromatic pigment is used as the pigment.
- the chromatic pigment may be only one kind or may contain two or more kinds.
- a near-infrared absorbing pigment is used as the pigment.
- the near-infrared absorbing pigment may be only one kind, or may contain two or more kinds.
- two or more kinds of chromatic pigments are used in combination as pigments, or black pigments are used.
- 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, still more preferably 100 nm or less.
- the average primary particle size of the pigment can be obtained from a 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 average value of the primary particle size for the primary particles of 400 pigments.
- the primary particles of the pigment refer to independent particles without aggregation.
- the pigment used in the present invention is preferably a pigment having a metal atom, and more preferably an organic pigment having a metal atom, because the effect of the present invention is more remarkably exhibited.
- the organic pigment having a metal atom include azomethine metal complex pigments, azometal complex pigments and metal phthalocyanine pigments, preferably azomethine metal complex pigments and metal phthalocyanine pigments, and more preferably metal phthalocyanine pigments. ..
- the pigment having a metal atom is preferably a chromatic pigment. According to this aspect, since the aggregation of the pigment in the film can be further suppressed, fluctuations in the spectral characteristics can also be suppressed.
- CI Color Index
- azo metal complex pigment examples include C.I. I. Pigment Yellow 150 and the like. Further, as the azo metal complex pigment, a nickel azobarbiturate complex pigment having the following structure can also be used.
- the metal phthalocyanine pigment examples include copper phthalocyanine pigments, zinc phthalocyanine pigments and aluminum phthalocyanine pigments, preferably halogenated copper phthalocyanine pigments, halogenated zinc phthalocyanine pigments and halogenated aluminum phthalocyanine pigments, and halogenated zinc phthalocyanine pigments. Is more preferable.
- the halogenated zinc phthalocyanine pigment tends to aggregate in the resin composition, and the storage stability of the resin composition containing the halogenated zinc phthalocyanine pigment tends to be low.
- the resin composition of the present invention Even when a halogenated zinc phthalocyanine pigment is used, it has excellent storage stability. Therefore, the effect of the present invention is particularly remarkable when the halogenated zinc phthalocyanine pigment is used.
- the copper phthalocyanine pigment is a phthalocyanine pigment having a copper atom as a central metal.
- the halogenated copper phthalocyanine pigment is a halogenated phthalocyanine pigment having a copper atom as a central metal.
- the halogenated phthalocyanine pigment is a phthalocyanine pigment having a halogen atom as a substituent.
- the zinc phthalocyanine pigment is a phthalocyanine pigment having a zinc atom as a central metal.
- the halogenated zinc phthalocyanine pigment is a halogenated phthalocyanine pigment having a zinc atom as a central metal.
- the aluminum phthalocyanine pigment is a phthalocyanine pigment having an aluminum atom as a central metal.
- the halogenated aluminum phthalocyanine pigment is a halogenated phthalocyanine pigment having an aluminum atom as a central metal.
- metallic phthalocyanine pigment examples include C.I. I. Pigment Green pigments such as Green7, 36, 58, 59, 62, 63, C.I. I. Examples thereof include blue pigments such as Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6.
- the chromatic pigment is not particularly limited, and a known chromatic pigment can be used.
- the chromatic pigment include pigments having a maximum absorption wavelength in the wavelength range of 400 to 700 nm. For example, yellow pigments, orange pigments, red pigments, green pigments, purple pigments, blue pigments and the like can be mentioned. Specific examples of these include, for example, the following.
- Halogenated zinc phthalocyanine pigments can also be used. Specific examples include the phthalocyanine pigment described in International Publication No. 2015/118720.
- Phthalocyanine compounds, phthalocyanine compounds described in JP-A-2018-180023, compounds described in JP-A-2019-038958, and the like can also be used.
- an aluminum phthalocyanine pigment having a phosphorus atom can also be used. Specific examples thereof include the compounds described in paragraph numbers 0022 to 0030 of JP2012-247591A and paragraph numbers 0047 of JP2011-157478A.
- a nickel azobarbiturate complex pigment having the above-mentioned structure can also be used.
- the yellow pigment 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.
- X 1 to X 16 independently represent a hydrogen atom or a halogen atom, and Z 1 represents an alkylene group having 1 to 3 carbon atoms.
- Specific examples of the compound represented by the formula (QP1) include the compound described in paragraph No. 0016 of Japanese Patent No. 6443711.
- Y 1 ⁇ Y 3 represents a halogen atom independently.
- n and m represent integers of 0 to 6, and p represents an integer of 0 to 5.
- N + m is 1 or more.
- Specific examples of the compound represented by the formula (QP2) include the compounds described in paragraphs 0047 to 0048 of Japanese Patent No. 6432077.
- red pigment a diketopyrrolopyrrole compound in which at least one bromine atom is substituted in the structure described in JP-A-2017-201384, a diketopyrrolopyrrole compound described in paragraphs 0016 to 0022 of Patent No. 6248838, Diketopyrrolopyrrole compound described in WO2012 / 102399, diketopyrrolopyrrole compound described in WO2012 / 117965, naphtholazo compound described in JP2012-229344, patent No. 6516119.
- the red pigment described in Japanese Patent Publication No. 6525101, the red pigment described in Japanese Patent No. 6525101, and the like can also be used.
- red pigment 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 can also be used. can.
- Japanese Patent No. 6561862 Japanese Patent No. 6413872, Japanese Patent No. 6281345, Japanese Patent Application Laid-Open No. 2020-026553, and Japanese Patent Application Laid-Open No. 2020-033526 are described. These contents are incorporated herein by reference.
- Two or more kinds of chromatic pigments may be used in combination.
- a green pigment and a yellow pigment in combination.
- the green pigment include C.I. I. Pigment Green7,36,58,59,63 is preferable, and C.I. I. Pigment Green 58 is more preferable.
- the yellow pigment C.I. I. Pigment Yellow 129,150 is preferable, and C.I. I. Pigment Yellow 150 is more preferable.
- black may be formed by a combination of two or more kinds of chromatic pigments.
- a combination include the following aspects (1) to (7).
- the resin composition of the present invention is used for forming a near-infrared transmission filter. It can be preferably used as a resin composition.
- An embodiment containing a red pigment, a blue pigment, a yellow pigment, a purple pigment, and a green pigment An embodiment containing a red pigment, a blue pigment, a yellow pigment, and a green pigment. (6) An embodiment containing a red pigment, a blue pigment, and a green pigment. (7) An embodiment containing a yellow pigment and a purple pigment.
- White pigments include titanium oxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow. Examples include resin particles and zinc sulfide.
- the white pigment is preferably particles having a titanium atom, and more preferably titanium oxide. Further, the white pigment is preferably particles having a refractive index of 2.10 or more with respect to light having a wavelength of 589 nm. The above-mentioned refractive index is preferably 2.10 to 3.00, and more preferably 2.50 to 2.75.
- titanium oxide described in "Titanium Oxide Physical Properties and Applied Technology, by Manabu Kiyono, pp. 13-45, published on June 25, 1991, published by Gihodo Publishing" can also be used.
- the white pigment is not limited to a single inorganic substance, but particles compounded with other materials may be used. For example, particles having pores or other materials inside, particles in which a large number of inorganic particles are attached to core particles, core particles composed of core particles composed of polymer particles, and core and shell composite particles composed of a shell layer composed of inorganic nanoparticles are used. Is preferable.
- the core and shell composite particles composed of the core particles composed of the polymer particles and the shell layer composed of the inorganic nanoparticles for example, the description in paragraphs 0012 to 0042 of JP2015-047520 can be referred to. This content is incorporated herein.
- Hollow inorganic particles can also be used as the white pigment.
- Hollow inorganic particles are inorganic particles having a structure having cavities inside, and refer to inorganic particles having cavities surrounded by an outer shell.
- Examples of the hollow inorganic particles include the hollow inorganic particles described in JP-A-2011-075786, International Publication No. 2013/06621, JP-A-2015-164881, and the like, and the contents thereof are incorporated in the present specification. Is done.
- the black pigment is not particularly limited, and known ones can be used.
- carbon black, titanium black, graphite and the like can be mentioned, with carbon black and titanium black being preferable, and titanium black being more preferable.
- Titanium black is black particles containing a titanium atom, and low-order titanium oxide or titanium oxynitride is preferable. Titanium black can modify the surface as needed for the purpose of improving dispersibility and suppressing cohesion.
- Titanium black preferably has a small primary particle size and an average primary particle size of each particle. Specifically, it is preferable that the average primary particle size is 10 to 45 nm. Titanium black can also be used as a dispersion. For example, a dispersion containing titanium black particles and silica particles and having a content ratio of Si atoms and Ti atoms in the dispersion adjusted to be in the range of 0.20 to 0.50 can be mentioned. Regarding the above dispersion, the description in paragraphs 0020 to 0105 of JP2012-169556A can be referred to, and the contents thereof are incorporated in the present specification.
- titanium black products examples include titanium black 10S, 12S, 13R, 13M, 13M-C, 13RN, 13M-T (trade name: manufactured by Mitsubishi Materials Corporation), Tilac D (Tilack) D (trade name: manufactured by Mitsubishi Materials Corporation). Product name: Ako Kasei Co., Ltd.) and the like.
- the near-infrared absorbing pigment is preferably an organic pigment. Further, the near-infrared absorbing pigment preferably has a maximum absorption wavelength in a range of more than 700 nm and 1400 nm or less. The maximum absorption wavelength of the near-infrared absorbing pigment is preferably 1200 nm or less, more preferably 1000 nm or less, and further preferably 950 nm or less. Further, the near-infrared absorbing pigment 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 lower limit is not particularly limited, but may be, for example, 0.0001 or more, and may be 0.0005 or more.
- the maximum absorption wavelength of the near-infrared absorbing pigment and the value of the absorbance at each wavelength are values obtained from the absorption spectrum of the film formed by using the resin composition containing the near-infrared absorbing pigment.
- the near-infrared absorbing pigment is not particularly limited, but is a pyrolopyrrole compound, a lilene compound, an oxonol compound, a squarylium compound, a cyanine compound, a croconium compound, a phthalocyanine compound, a naphthalocyanine compound, a pyrylium compound, an azurenium compound, an indigo compound and a pyrromethene compound.
- a pyrolopyrrole compound is at least one selected from a pyrolopyrrole compound, a squarylium compound, a cyanine compound, a phthalocyanine compound and a naphthalocyanine compound, and more preferably a pyrolopyrrole compound or a squarylium compound, which is a pyrolopyrrole compound.
- a pyrolopyrrole compound a squarylium compound, a cyanine compound, a phthalocyanine compound and a naphthalocyanine compound
- a pyrolopyrrole compound or a squarylium compound which is a pyrolopyrrole compound.
- Specific examples of the near-infrared absorbing pigment include the compounds described in Examples described later.
- the content of the pigment in the total solid content of the resin composition is 40% by mass or more, preferably 45% by mass or more, more preferably 50% by mass or more, and preferably 55% by mass or more. It is even more preferably 60% by mass or more, and even more preferably 60% by mass or more.
- the upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and further preferably 70% by mass or less.
- the content of the pigment containing a metal atom in the pigment is preferably 30% by mass or more, more preferably 40% by mass or more, and further preferably 50% by mass or more.
- the upper limit may be 100% by mass or less, 90% by mass or less, or 80% by mass or less.
- the content of the chromatic color pigment in the pigment is preferably 30 to 100% by mass, more preferably 40 to 100% by mass, and further preferably 50 to 100% by mass.
- the content of the halogenated zinc phthalocyanine pigment in the pigment is preferably 30% by mass or more, more preferably 40% by mass or more, and further preferably 50% by mass.
- the upper limit may be 100% by mass or less, 90% by mass or less, or 80% by mass or less.
- the resin composition of the present invention may contain a dye.
- the dye is not particularly limited, and known dyes can be used. Examples of the dye include chromatic dyes, black dyes, and near-infrared absorbing dyes.
- a known dye can be used.
- the methine dye described in JP-A-2019-073695, the methine dye described in JP-A-2019-073696, the methine dye described in JP-A-2019-073697, and JP-A-2019-073698 are described. It is also possible to use a methine dye or the like. 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 may have 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.
- the compounds described in 031442 and the like can also be used.
- the content of the dye in the total solid content of the resin composition is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less.
- the content of the dye in the resin composition is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, and further preferably 60 parts by mass or less with respect to 100 parts by mass of the pigment. preferable.
- the resin composition of the present invention contains substantially no dye.
- the ratio of the pigment in the resin composition can be increased, and the effect of suppressing the aggregation of the pigment can be obtained more remarkably.
- the case where the dye is substantially not contained means that the content of the dye in the total solid content of the resin composition is 0.1% by mass or less, and is 0.01% by mass. The following is preferable, and it is more preferable that the dye is not contained.
- the resin composition of the present invention contains a resin.
- the resin is blended, for example, for the purpose of dispersing the pigment in the resin composition or for the purpose of a binder.
- the resin mainly used for dispersing the pigment is also referred to as a dispersant.
- such use of the resin is an example, and it can be used for purposes other than such use.
- the weight average molecular weight (Mw) of the resin is preferably 3000 to 2000000.
- the upper limit is more preferably 1,000,000 or less, and particularly preferably 500,000 or less.
- the lower limit is more preferably 4000 or more, and particularly preferably 5000 or more.
- the resin examples include (meth) acrylic resin, en-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, and polyamideimide resin. , Polyolefin resin, cyclic olefin resin, polyester resin, styrene resin and the like. One of these resins may be used alone, or two or more thereof may be mixed and used.
- the resin described in JP-A-2017-032685, the resin described in JP-A-2017-075248, and the resin described in JP-A-2017-066240 can also be used.
- a resin having an acid group is used as the resin.
- the resin composition of the present invention preferably contains a resin having an acid group as a dispersant. According to this aspect, the above-mentioned network structure is easily formed between the pigment, the compound A, and the resin having an acid group, and the storage stability of the resin composition can be more effectively improved.
- the resin having an acid group may be contained as a binder.
- the resin having an acid group can be used, for example, as an alkali-soluble resin.
- Examples of the type of acid group contained in the resin having an acid group include a carboxyl group, a phosphoric acid group, a sulfo group, and a phenolic hydroxy group, and a carboxyl group is preferable.
- the resin having an acid group preferably contains a repeating unit having an acid group in the side chain, and more preferably contains 5 to 70 mol% of the repeating unit having an acid group in the side chain in all the repeating units of the resin.
- the upper limit of the content of the repeating unit having an acid group in the side chain is preferably 50 mol% or less, more preferably 30 mol% or less.
- the lower limit of the content of the repeating unit having an acid group in the side chain is preferably 10 mol% or more, more preferably 20 mol% or more.
- the acid value of the resin having an acid group is preferably 30 to 500 mgKOH / g.
- the lower limit is more preferably 40 mgKOH / g or more, and particularly preferably 50 mgKOH / g or more.
- the upper limit is more preferably 400 mgKOH / g or less, further preferably 300 mgKOH / g or less, and particularly preferably 200 mgKOH / g or less.
- the weight average molecular weight (Mw) of the resin having an acid group is preferably 5000 to 100,000, more preferably 5000 to 50000.
- the number average molecular weight (Mn) of the resin having an acid group is preferably 1000 to 20000.
- 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 to include repeating units derived from the components.
- R 1 and R 2 each independently represent a hydrocarbon group having 1 to 25 carbon atoms which may have a hydrogen atom or a substituent.
- R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
- the resin having an acid group also preferably contains 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 and may contain 1 to 20 carbon atoms.
- n represents an integer from 1 to 15.
- the resin having an acid group contains a repeating unit having a polymerizable group.
- the polymerizable group include an ethylenically unsaturated bond-containing group and a cyclic ether group, and an ethylenically unsaturated bond-containing group is preferable.
- the ethylenically unsaturated bond-containing group include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
- the cyclic ether group include an epoxy group and an oxetanyl group.
- the resin having an acid group is also preferably a graft resin having an acid group (hereinafter, also referred to as an acidic graft resin).
- an acidic graft resin can be preferably used as a dispersant.
- the graft resin means a resin containing a repeating unit having a graft chain.
- the graft chain means a polymer chain that branches and extends from the main chain of a repeating unit.
- the number of atoms excluding hydrogen atoms is preferably 40 to 10,000, the number of atoms excluding hydrogen atoms is more preferably 50 to 2000, and the number of atoms excluding hydrogen atoms is 60 to. It is more preferably 500.
- the graft chain preferably contains at least one structure selected from polyester chains, polyether chains, poly (meth) acrylic chains, polyurethane chains, polyurea chains and polyamide chains, preferably polyester chains, polyether chains and poly (meth) chains. ) It is more preferable to include at least one structure selected from acrylic chains.
- the terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent.
- substituents include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, a hydroxy group, an amino group and the like.
- a group having a steric repulsion effect is preferable, and an alkyl group or an alkoxy group having 5 to 24 carbon atoms is preferable, from the viewpoint of improving the dispersibility of pigments and the like.
- the alkyl group and the alkoxy group may be linear, branched, or cyclic, and linear or branched is preferable.
- the weight average molecular weight of the graft chain is preferably 500 to 10000.
- the upper limit is preferably 8000 or less, and more preferably 6000 or less.
- the lower limit is preferably 1000 or more, and more preferably 1500 or more.
- the weight average molecular weight of the graft chain is a value calculated from the weight average molecular weight of the raw material monomer used for the polymerization of the repeating unit having the graft chain.
- repeating units with graft chains can be formed by polymerizing macromonomers.
- the macromonomer means a polymer compound having a polymerizable group introduced at the end of the polymer.
- the value of the weight average molecular weight of the raw material monomer the polystyrene-equivalent value measured by the GPC (gel permeation chromatography) method is used.
- Examples of the acid group contained in the acidic graft resin include a carboxyl group, a sulfo group, and a phosphoric acid group, and the carboxyl group is preferable from the viewpoint of dispersibility of the pigment.
- the acid value of the acidic graft resin is preferably 20 to 150 mgKOH / g.
- the upper limit is preferably 130 mgKOH / g or less, and more preferably 110 mgKOH / g or less.
- the lower limit is preferably 30 mgKOH / g or more, and more preferably 40 mgKOH / g or more.
- the weight average molecular weight of the acidic graft resin is preferably 5000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 10,000 to 30,000.
- the number average molecular weight (Mn) of the acidic graft resin is preferably 2500 to 50000, more preferably 5000 to 30000, and even more preferably 5000 to 15000.
- the acidic graft resin is preferably a resin containing a repeating unit having a graft chain and a repeating unit having an acid group. Further, the acidic graft resin preferably contains 1 mol% or more of the repeating units having a graft chain, more preferably 2 mol% or more, and 3 mol% or more of the repeating units of the acidic graft resin. Is more preferable.
- the upper limit can be 90 mol%, 80 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less. can.
- the acidic graft resin preferably contains 1 mol% or more of the repeating units having an acid group, more preferably 2 mol% or more, and 3 mol% or more of the repeating units of the acidic graft resin. Is more preferable.
- the upper limit can be 90 mol%, 80 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less. can.
- the acidic graft resin may further contain other repeating units other than the above.
- other repeating units include repeating units having a polymerizable group.
- the polymerizable group include an ethylenically unsaturated bond-containing group and a cyclic ether group.
- acidic graft resin examples include the resins described in paragraphs 0025 to 0094 of JP-A-2012-255128 and the resins having the structures described in Examples described later.
- the resin composition of the present invention preferably contains a resin having an aromatic carboxyl group (hereinafter, also referred to as resin Ac) as the resin having an acid group.
- resin Ac the aromatic carboxyl group may be contained in the main chain of the repeating unit or may be contained in the side chain of the repeating unit.
- the aromatic carboxyl group is preferably contained in the main chain of the repeating unit.
- an aromatic carboxyl group is a group having a structure in which one or more carboxyl groups are bonded to an aromatic ring.
- the number of carboxyl groups bonded to the aromatic ring is preferably 1 to 4, and more preferably 1 to 2.
- the resin Ac is preferably a resin containing at least one repeating unit selected from the repeating unit represented by the formula (Ac-1) and the repeating unit represented by the formula (Ac-2).
- Ar 1 represents a group containing an aromatic carboxyl group
- L 1 represents -COO- or -CONH-
- L 2 represents a divalent linking group
- Ar 10 represents a group containing an aromatic carboxyl group
- L 11 represents -COO- or -CONH-
- L 12 represents a trivalent linking group
- P 10 represents a polymer. Represents a chain.
- Examples of the group containing an aromatic carboxyl group represented by Ar 1 in the formula (Ac-1) include a structure derived from an aromatic tricarboxylic acid anhydride, a structure derived from an aromatic tetracarboxylic acid anhydride, and the like.
- Examples of the aromatic tricarboxylic acid anhydride and the aromatic tetracarboxylic acid anhydride include compounds having the following structures.
- Q 1 is represented by a single bond, -O-, -CO-, -COOCH 2 CH 2 OCO-, -SO 2- , -C (CF 3 ) 2- , and the following formula (Q-1). Represents a group to be used or a group represented by the following formula (Q-2).
- the group containing an aromatic carboxyl group represented by Ar 1 may have a polymerizable group.
- the polymerizable group include an ethylenically unsaturated bond-containing group and a cyclic ether group, and an ethylenically unsaturated bond-containing group is preferable.
- Specific examples of the group containing an aromatic carboxyl group represented by Ar 1 include a group represented by the formula (Ar-11), a group represented by the formula (Ar-12), and a group represented by the formula (Ar-13). Examples include the base.
- n1 represents an integer of 1 to 4, preferably 1 or 2, and more preferably 2.
- n2 represents an integer of 1 to 8, preferably an integer of 1 to 4, more preferably 1 or 2, and even more preferably 2.
- n3 and n4 each independently represent an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 1 or 2, and preferably 1. More preferred. However, at least one of n3 and n4 is an integer of 1 or more.
- Q 1 is a single bond, -O-, -CO-, -COOCH 2 CH 2 OCO-, -SO 2- , -C (CF 3 ) 2- , the above formula (Q-). It represents a group represented by 1) or a group represented by the above formula (Q-2).
- L 1 represents -COO- or -CONH-, and preferably -COO-.
- the divalent linking group represented by L 2 in the formula (Ac-1) includes an alkylene group, an arylene group, -O-, -CO-, -COO-, -OCO-, -NH-, -S- and these.
- a group that combines two or more of the above can be mentioned.
- the alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and even more preferably 1 to 15 carbon atoms.
- the alkylene group may be linear, branched or cyclic.
- the arylene group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 10 carbon atoms.
- the alkylene group and the arylene group may have a substituent.
- the substituent include a hydroxy group and the like.
- the divalent linking group L 2 represents is preferably a group represented by -L 2a -O-.
- L 2a is an alkylene group; an arylene group; a group in which an alkylene group and an arylene group are combined; at least one selected from an alkylene group and an arylene group, and —O—, —CO—, —COO—, —OCO—, Examples thereof include a group in which at least one selected from —NH— and —S— is combined, and an alkylene group is preferable.
- the alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and even more preferably 1 to 15 carbon atoms.
- the alkylene group may be linear, branched or cyclic.
- the alkylene group and the arylene group may have a substituent. Examples of the substituent include a hydroxy group and the like.
- the group containing the aromatic carboxyl group represented by Ar 10 in the formula (Ac-2) has the same meaning as Ar 1 in the formula (Ac-1), and the preferred range is also the same.
- L 11 represents -COO- or -CONH-, and preferably -COO-.
- the trivalent linking group represented by L 12 in the formula (Ac-2) includes a hydrocarbon group, -O-, -CO-, -COO-, -OCO-, -NH-, -S- and two of these.
- a group that combines species or more can be mentioned.
- the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group.
- the number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15.
- the aliphatic hydrocarbon group may be linear, branched or cyclic.
- the number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 10.
- the hydrocarbon group may have a substituent.
- substituent include a hydroxy group and the like.
- the trivalent linking group represented by L 12 is preferably a group represented by the formula (L12-1), and more preferably a group represented by the formula (L12-2).
- L 12b represents a trivalent linking group
- X 1 represents S
- * 1 represents the bonding position with L 11 in the formula (Ac-2)
- * 2 represents the bonding position with L 11 in the formula (Ac-2). It represents a bonding position to P 10 of the Ac-2).
- the trivalent linking group represented by L 12b is a hydrocarbon group; a hydrocarbon group and at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S-. Examples thereof include a group in which the above is combined with, and a hydrocarbon group or a group in which a hydrocarbon group and —O— are combined is preferable.
- L 12c represents a trivalent linking group
- X 1 represents S
- * 1 represents the bonding position with L 11 of the formula (Ac-2)
- * 2 represents the binding position of the formula (L12-2). It represents a bonding position to P 10 of the Ac-2).
- the trivalent linking group represented by L 12c is a hydrocarbon group; a hydrocarbon group and at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S-. Examples thereof include a group in which the above is combined, and a hydrocarbon group is preferable.
- P 10 represents a polymer chain.
- the polymer chain represented by P 10 preferably has at least one repeating unit selected from poly (meth) acrylic repeating units, polyether repeating units, polyester repeating units and polyol repeating units.
- the weight average molecular weight of the polymer chain P 10 is preferably 500 to 20000.
- the lower limit is preferably 1000 or more.
- the upper limit is preferably 10,000 or less, more preferably 5000 or less, and even more preferably 3000 or less.
- the weight average molecular weight of P 10 is in the above range, the dispersibility of the pigment in the composition is good.
- the resin having an aromatic carboxyl group is a resin having a repeating unit represented by the formula (Ac-2), this resin is preferably used as a dispersant.
- the polymer chain represented by P 10 may contain a polymerizable group.
- the polymerizable group include an ethylenically unsaturated bond-containing group and a cyclic ether group, and an ethylenically unsaturated bond-containing group is preferable.
- the polymer chain represented by P 10 is preferably a polymer chain containing a repeating unit represented by the following formulas (P-1) to (P-5), and is preferably (P-5). More preferably, it is a polymer chain containing a repeating unit represented by.
- RP1 and RP2 each represent an alkylene group.
- the alkylene group represented by RP1 and RP2 a linear or branched alkylene group having 1 to 20 carbon atoms is preferable, and a linear or branched alkylene group having 2 to 16 carbon atoms is more preferable. , A linear or branched alkylene group having 3 to 12 carbon atoms is more preferable.
- RP3 represents a hydrogen atom or a methyl group.
- L P1 represents a single bond or an arylene group
- L P2 represents a single bond or a divalent linking group.
- L P1 is preferably a single bond.
- Examples of the divalent linking group L P2 represents an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), - NH -, - SO-, -SO 2 -, - CO -, - O -, - COO -, - OCO -, - S -, - NHCO -, - CONH-, and include a group formed by combining two or more of these.
- RP4 represents a hydrogen atom or a substituent.
- Substituents include hydroxy group, carboxyl group, alkyl group, aryl group, heteroaryl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthioether group, arylthioether group, heteroarylthioether group, and (meth) acryloyl.
- Examples include a group, an oxetanyl group, a blocked isocyanate group and the like.
- the blocked isocyanate group in the present specification is a group capable of generating an isocyanate group by heat, and for example, a group in which a blocking agent and an isocyanate group are reacted to protect the isocyanate group can be preferably exemplified.
- the blocking agent examples include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, imide compounds and the like.
- the blocking agent examples include the compounds described in paragraphs 0115 to 0117 of JP-A-2017-06793, the contents of which are incorporated herein by reference.
- the blocked isocyanate group is preferably a group capable of generating an isocyanate group by heat of 90 ° C to 260 ° C.
- the polymer chain represented by P 10 has at least one group (hereinafter, also referred to as “functional group A”) selected from the group consisting of a (meth) acryloyl group, an oxetanyl group, a blocked isocyanate group and a t-butyl group. Is preferable. It is more preferable that the functional group A is at least one selected from the group consisting of a (meth) acryloyl group, an oxetanyl group and a blocked isocyanate group.
- the polymer chain contains a functional group A, it is easy to form a film having excellent solvent resistance.
- the above effect is remarkable when at least one group selected from a (meth) acryloyl group, an oxetanyl group and a blocked isocyanate group is contained.
- the functional group A has a t-butyl group, it is preferable that the resin composition contains a compound having an epoxy group or an oxetanyl group.
- the functional group A has a blocked isocyanate group, it is preferable to include a compound having a hydroxy group in the resin composition.
- the polymer chain represented by P 10 is more preferably a polymer chain having a repeating unit containing the functional group A in the side chain.
- the proportion of the repeating unit containing the functional group A in the whole repeating units constituting the P 10 in a side chain is preferably 5 mass% or more, more preferably 10 mass% or more, 20 mass % Or more is more preferable.
- the upper limit can be 100% by mass, preferably 90% by mass or less, and more preferably 60% by mass or less.
- the polymer chain represented by P 10 has a repeating unit containing an acid group.
- the acid group include a carboxyl group, a phosphoric acid group, a sulfo group, and a phenolic hydroxy group.
- the ratio of the repeating unit containing an acid group in all the repeating units constituting P 10 is preferably 1 to 30% by mass, more preferably 2% by mass to 20% by mass, and 3 to 10% by mass. Is more preferable.
- a polyimine-based dispersant containing a nitrogen atom in at least one of a main chain and a side chain can also be used.
- the polyimine-based dispersant has a main chain having a partial structure having a functional group of pKa14 or less, a side chain having 40 to 10,000 atoms, and a basic nitrogen atom in at least one of the main chain and the side chain.
- the resin to have 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 0166 of JP2012-255128A can be referred to, and the content thereof is incorporated in the present specification.
- a resin having an acid group a resin having a structure in which a plurality of polymer chains are bonded to a core portion can also be used.
- resins include dendrimers (including star-shaped polymers).
- specific examples of the dendrimer include the polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP2013-043962.
- a commercially available acidic dispersant can also be used as the resin having an acid group.
- Specific examples thereof include DISPERBYK series manufactured by BYK Chemie (for example, DISPERBYK-111 etc.), Solsparse series manufactured by Japan Lubrizol K.K., and the like.
- the pigment dispersants described in paragraphs 0041 to 0130 of JP2014-130338A can also be used, and the contents thereof are incorporated in the present specification.
- the resin composition of the present invention can further contain a resin containing no acid group.
- resins are not particularly limited, and are (meth) acrylic resin, en-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide. Examples thereof include resins, polyimide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, and styrene resins.
- a resin having a basic group can also be used as the resin containing no acid group.
- the resin having a basic group is preferably a resin containing a repeating unit having a basic group in the side chain, and has both a repeating unit having a basic group in the side chain and a repeating unit not containing a basic group.
- a polymer is more preferable, and a block copolymer having a repeating unit having a basic group in the side chain and a repeating unit not containing a basic group is further preferable.
- a resin having a basic group can also be used as a dispersant.
- the amine value of the resin having a basic group is preferably 5 to 300 mgKOH / g.
- the lower limit is preferably 10 mgKOH / g or more, and more preferably 20 mgKOH / g or more.
- the upper limit is preferably 200 mgKOH / g or less, and more preferably 100 mgKOH / g or less.
- Examples of the resin having a basic group are described in the block copolymers (B) described in paragraphs 0063 to 0112 of JP2014-219665A and paragraphs 0046 to 0076 of JP-A-2018-156021.
- the block copolymer A1 can be mentioned.
- the content of the resin in the total solid content of the resin composition is preferably 5 to 40% by mass.
- the lower limit is preferably 10% by mass or more.
- the upper limit is preferably 30% by mass or less, more preferably 25% by mass or less.
- the content of the resin having an acid group in the total solid content of the resin composition is preferably 5 to 40% by mass.
- the lower limit is preferably 10% by mass or more.
- the upper limit is preferably 30% by mass or less, more preferably 25% by mass or less.
- the content of the resin having an acid group is preferably 20 to 120 parts by mass with respect to 100 parts by mass of the pigment.
- the lower limit is preferably 25 parts by mass or more, more preferably 30 parts by mass or more.
- the upper limit is preferably 110 parts by mass or less, more preferably 100 parts by mass or less.
- the content of the resin having an acid group as a dispersant is preferably 10 to 60 parts by mass with respect to 100 parts by mass of the pigment.
- the lower limit is preferably 15 parts by mass or more, more preferably 20 parts by mass or more.
- the upper limit is preferably 50 parts by mass or less, more preferably 40 parts by mass or less.
- the resin composition of the present invention contains a compound A having 3 or more basic groups in one molecule, an amine value of 2.7 mmol / g or more, and a molecular weight of 100 or more.
- the molecular weight of compound A is 100 or more, preferably 200 or more, and more preferably 250 or more.
- the upper limit is preferably 100,000 or less, more preferably 50,000 or less, further preferably 10,000 or less, and particularly preferably 2000 or less.
- the molecular weight of compound A is the value calculated from the structural formula.
- the molecular weight of compound A cannot be calculated from the structural formula or is difficult to calculate, the value of the number average molecular weight measured by the boiling point elevation method is used. If the measurement cannot be performed by the boiling point elevation method or is difficult to measure, the value of the number average molecular weight measured by the viscosity method is used.
- the value of the number average molecular weight in the polystyrene conversion value measured by the GPC (gel permeation chromatography) method is used.
- the amine value of compound A is 2.7 mmol / g or more, preferably 5 mmol / g or more, more preferably 10 mmol / g or more, and even more preferably 15 mmol / g or more.
- the amine value of compound A was calculated by the method described in Examples described later.
- the number of basic groups contained in compound A is 3 or more, preferably 4 or more, more preferably 6 or more, still more preferably 10 or more.
- the basic group of compound A is preferably an amino group. Further, the compound A is preferably a compound having a primary amino group, more preferably a compound containing a primary amino group and a tertiary amino group, respectively, and a primary amino group and a secondary amino group. It is more preferable that the compound contains a tertiary amino group and a tertiary amino group, respectively.
- the amino group of compound A may be a cyclic amino group.
- the cyclic amino group may be an aliphatic cyclic amino group such as a piperidino group or an aromatic cyclic amino group such as a pyridyl group.
- the cyclic amino group is preferably a cyclic amino group having a 5-membered ring or a 6-membered ring structure, more preferably a cyclic amino group having a 6-membered ring structure, and an aliphatic cyclic amino having a 6-membered ring structure. It is more preferably a group.
- the cyclic amino group preferably has a hindered amine structure, and particularly preferably has a 6-membered ring hindered amine structure.
- the two carbon atoms in the ring structure adjacent to the nitrogen atom of the cyclic amino group have a substituent such as an alkyl group.
- the cyclic amino group having a hindered amine structure include 1,2,2,6,6-pentamethylpiperidyl group, 2,2,6,6-tetramethylpiperidyl group and 1,2,6,6-trimethylpiperidyl.
- 2,6-dimethylpiperidyl group 1-methyl-2,6-di (t-butyl) piperidyl group, 2,6-di (t-butyl) piperidyl group, 1,2,2,5,5- Examples thereof include a pentamethylpyrrolidyl group and a 2,2,5,5-tetramethylpyrrolidyl group.
- 1,2,2,6,6-pentamethylpiperidyl group or the 2,2,6,6-tetramethylpiperidyl group is preferable, and the 1,2,2,6,6-pentamethylpiperidyl group is preferable. More preferred.
- the compound A is preferably polyalkyleneimine because the storage stability of the resin composition can be further improved.
- Polyalkyleneimine is a polymer obtained by ring-opening polymerization of alkyleneimine.
- the polyalkyleneimine is preferably a polymer having a branched structure containing a primary amino group, a secondary amino group, and a tertiary amino group, respectively.
- the number of carbon atoms of the alkyleneimine is preferably 2 to 6, more preferably 2 to 4, further preferably 2 or 3, and particularly preferably 2.
- alkyleneimine examples include ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, and the like, preferably ethyleneimine or propyleneimine, and more preferably ethyleneimine. preferable.
- the polyalkyleneimine is particularly preferably polyethyleneimine.
- polyethyleneimine preferably contains a primary amino group in an amount of 10 mol% or more, more preferably 20 mol% or more, based on the total of the primary amino group, the secondary amino group and the tertiary amino group. , 30 mol% or more is more preferable.
- Examples of commercially available polyethyleneimine products include Epomin SP-003, SP-006, SP-012, SP-018, SP-200, and P-1000 (all manufactured by Nippon Shokubai Co., Ltd.).
- a compound having a cyclic amino group can also be used.
- examples of such a compound include compounds having the following structures. Examples of commercially available products include ADEKA STAB LA-52, LA-57, LA-63P, LA-68 (all manufactured by ADEKA Corporation) and the like.
- a resin having an amino group in the side chain can also be used.
- a compound having the following structure can also be used.
- the content of compound A in the total solid content of the resin composition is preferably 0.1 to 5% by mass.
- the lower limit is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass or more.
- the upper limit is preferably 4.5% by mass or less, more preferably 4% by mass or less, and further preferably 3% by mass or less.
- the content of compound A is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the pigment.
- the lower limit is preferably 0.6 parts by mass or more, more preferably 1 part by mass or more, and further preferably 2 parts by mass or more.
- the upper limit is preferably 8 parts by mass or less, more preferably 7% by mass or less, and further preferably 5 parts by mass or less.
- the content of the compound A is preferably 0.5 to 50 parts by mass with respect to 100 parts by mass of the resin having an acid group.
- the lower limit is preferably 0.6 parts by mass or more, more preferably 1 part by mass or more, and further preferably 3 parts by mass or more.
- the upper limit is preferably 45 parts by mass or less, more preferably 40% by mass or less, and further preferably 30 parts by mass or less.
- the content of the compound A is preferably 1 to 70 parts by mass with respect to 100 parts by mass of the resin having an acid group as a dispersant.
- the lower limit is preferably 2 parts by mass or more, more preferably 3 parts by mass or more, and further preferably 5 parts by mass or more.
- the upper limit is preferably 65 parts by mass or less, more preferably 60 parts by mass or less, and further preferably 50 parts by mass or less.
- the resin composition of the present invention can contain a pigment derivative.
- the storage stability of the resin composition can be further improved.
- the pigment derivative include compounds having a structure in which an acid group or a basic group is bonded to a pigment skeleton.
- the pigment skeletons constituting the pigment derivatives include quinoline pigment skeleton, benzoimidazolone pigment skeleton, benzoisoindole pigment skeleton, benzothiazole pigment skeleton, iminium pigment skeleton, squarylium pigment skeleton, croconium pigment skeleton, oxonol pigment skeleton, and pyrolopyrrole pigment.
- Examples of the acid group include a sulfo group, a carboxyl group, a phosphoric acid group and salts thereof.
- 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 ion.
- Examples of the basic group include an amino group, a pyridinyl group and a salt thereof, a salt of an ammonium group, and a phthalimidemethyl 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.
- a pigment derivative having excellent visible transparency (hereinafter, also referred to as a transparent pigment derivative) can be used.
- the maximum value of the molar extinction coefficient in the wavelength region of 400 ⁇ 700 nm of the transparent pigment derivative (.epsilon.max) is that it is preferable, 1000L ⁇ mol -1 ⁇ cm -1 or less is not more than 3000L ⁇ mol -1 ⁇ cm -1 Is more preferable, and 100 L ⁇ mol -1 ⁇ cm -1 or less is further preferable.
- the lower limit of ⁇ max is, for example, 1 L ⁇ mol -1 ⁇ cm -1 or more, and may be 10 L ⁇ mol -1 ⁇ cm -1 or more.
- pigment derivative examples include the compounds described in Examples described later, JP-A-56-118462, JP-A-63-246674, JP-A-01-217077, and JP-A-03-009961.
- Japanese Patent Laid-Open No. 03-026767 Japanese Patent Application Laid-Open No. 03-153780
- Japanese Patent Application Laid-Open No. 03-045662 Japanese Patent Application Laid-Open No. 04-285669
- Japanese Patent Application Laid-Open No. 06-145546 Japanese Patent Application Laid-Open No. 06-212088, Kaihei 06-240158
- Japanese Patent Laid-Open No. 10-030063 Japanese Patent Application Laid-Open No. 10-195326
- Paragraph Nos Japanese Patent Laid-Open No.
- the content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass with respect to 100 parts by mass of the pigment.
- the pigment derivative only one kind may be used, or two or more kinds may be used in combination. When two or more kinds are used in combination, the total amount thereof is preferably in the above range.
- the content of the pigment derivative is preferably 300 parts by mass or less, more preferably 200 parts by mass or less, and further preferably 100 parts by mass or less with respect to 100 parts by mass of compound A.
- the total content of the pigment derivative and the compound A is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the pigment.
- the resin composition of the present invention preferably contains a polymerizable compound.
- a polymerizable compound a known compound that can be crosslinked by radicals, acids or heat can be used.
- the polymerizable compound is preferably, for example, a compound having an ethylenically unsaturated bond-containing group.
- the ethylenically unsaturated bond-containing group include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
- the polymerizable compound used in the present invention is preferably a radically polymerizable compound.
- the polymerizable compound may be in any chemical form such as a monomer, a prepolymer or an oligomer, but a monomer is preferable.
- the molecular weight of the polymerizable compound is preferably 100 to 3000.
- the upper limit is more preferably 2000 or less, and even more preferably 1500 or less.
- the lower limit is more preferably 150 or more, and even more preferably 250 or more.
- the polymerizable compound is preferably a compound containing 3 or more ethylenically unsaturated bond-containing groups, more preferably a compound containing 3 to 15 ethylenically unsaturated bond-containing groups, and more preferably an ethylenically unsaturated bond. It is more preferable that the compound contains 3 to 6 containing groups. Further, the polymerizable compound is preferably a (meth) acrylate compound having 3 to 15 functionalities, and more preferably a (meth) acrylate compound having 3 to 6 functionalities.
- polymerizable compound examples include paragraph numbers 0995 to 0108 of JP2009-288705, paragraphs 0227 of JP2013-029760, paragraphs 0254 to 0257 of JP2008-292970, and JP-A.
- the compounds described in paragraph numbers 0034 to 0038 of Japanese Patent Application Laid-Open No. 2013-253224, paragraph numbers 0477 of Japanese Patent Application Laid-Open No. 2012-208494, Japanese Patent Application Laid-Open No. 2017-048637, Japanese Patent No. 6057891 and Japanese Patent Application Laid-Open No. 6031807 are These contents are incorporated herein by reference.
- dipentaerythritol tri (meth) acrylate commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.
- dipentaerythritol tetra (meth) acrylate commercially available KAYARAD D-320.
- diglycerin EO ethylene oxide modified (meth) acrylate
- pentaerythritol tetraacrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd., NK ester A
- 1,6-hexanediol diacrylate manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA
- RP-1040 manufactured by Nippon Kayaku Co., Ltd.
- Aronix TO-2349 manufactured by Toa Synthetic Co., Ltd.
- NK Oligo UA-7200 manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
- DPHA-40H manufactured by Nippon Kayaku Co., Ltd.
- Examples of the polymerizable compound include trimethylolpropane tri (meth) acrylate, trimethylolpropane propylene oxide modified tri (meth) acrylate, trimethylolpropane ethylene oxide modified tri (meth) acrylate, and isocyanuric acid ethylene oxide modified tri (meth) acrylate.
- Trifunctional (meth) acrylate compounds such as pentaerythritol tri (meth) acrylate can also be used.
- Commercially available trifunctional (meth) acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305.
- M-303, M-452, M-450 manufactured by Toa Synthetic Co., Ltd.
- NK ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT manufactured by Shin Nakamura Chemical Industry Co., Ltd.
- KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) And so on.
- a compound having an acid group can also be used as the polymerizable compound.
- the polymerizable compound having an acid group By using a polymerizable compound having an acid group, the polymerizable compound in the unexposed portion can be easily removed during development, and the generation of development residue can be suppressed.
- the acid group include a carboxyl group, a sulfo group, a phosphoric acid group and the like, and a carboxyl group is preferable.
- the polymerizable compound having an acid group include succinic acid-modified dipentaerythritol penta (meth) acrylate.
- Examples of commercially available products of the polymerizable compound having an acid group include Aronix M-510, M-520, and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.).
- the preferable acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, and more preferably 5 to 30 mgKOH / g.
- the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the solubility in a developing solution is good, and when the acid value is 40 mgKOH / g or less, it is advantageous in production and handling.
- a compound having a caprolactone structure can also be used.
- examples of commercially available products of the polymerizable compound having a caprolactone structure include KAYARAD DPCA-20, DPCA-30, DPCA-60, DPCA-120 (all manufactured by Nippon Kayaku Co., Ltd.) and the like.
- a polymerizable compound having an alkyleneoxy group can also be used.
- a polymerizable compound having an ethyleneoxy group and / or a propyleneoxy group is preferable, a polymerizable compound having an ethyleneoxy group is more preferable, and 3 to 3 having 4 to 20 ethyleneoxy groups.
- a hexafunctional (meth) acrylate compound is more preferred.
- Commercially available products of the polymerizable compound having an alkyleneoxy group include SR-494, which is a tetrafunctional (meth) acrylate having four ethyleneoxy groups manufactured by Sartmer, and a trifunctional (meth) having three isobutyleneoxy groups. ) KAYARAD TPA-330, which is an acrylate, and the like.
- a polymerizable compound having a fluorene skeleton can also be used.
- examples of commercially available products of the polymerizable compound having a fluorene skeleton include Ogsol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemical Co., Ltd., a (meth) acrylate monomer having a fluorene skeleton).
- the polymerizable compound it is also preferable to use a compound that does not substantially contain an environmentally regulatory substance such as toluene.
- an environmentally regulatory substance such as toluene.
- commercially available products of such compounds include KAYARAD DPHA LT and KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.).
- the content of the polymerizable compound in the total solid content of the resin composition is preferably 0.1 to 50% by mass.
- the lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more, and further preferably 3% by mass or more.
- the upper limit is preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less.
- the polymerizable compound may be used alone or in combination of two or more. When two or more kinds are used in combination, it is preferable that the total of them is in the above range.
- the resin composition of the present invention preferably contains a 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.
- the photopolymerization initiator is preferably a photoradical polymerization initiator.
- photopolymerization initiator examples include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazoles, oxime compounds, organic peroxides, and thio compounds. , Ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds and the like.
- the photopolymerization initiator is a trihalomethyltriazine compound, a benzyldimethylketal 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 halomethyloxadiazole compound and a 3-aryl substituted coumarin compound, preferably an oxime compound and an ⁇ -hydroxyketone compound.
- ⁇ -Aminoketone compound, and a compound selected from an acylphosphine compound are more preferable, and an oxime compound is further preferable.
- the photopolymerization initiator the compound 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, JP-A-2019-043864. Examples thereof include the photopolymerization initiator described in JP-A-2019-044030, the photopolymerization initiator described in JP-A-2019-167313, and the contents thereof are described in the present invention. Incorporated in the specification.
- ⁇ -hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (above, IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure27, 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), Irgacure 907, Irgacure 369, Irgacure 369, Irger 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 compound described in JP-A-2001-233842, the compound described in JP-A-2000-080068, the compound described in JP-A-2006-342166, and J. Am. 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 Photopolisr Science and Technology (1995, pp. 202-232), the compound described in JP-A-2000-066385, the compound described in JP-A-2000-066385.
- oxime compound examples include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminovtan-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyimiminopentane-3-one, and the like.
- an oxime compound having a fluorene ring can also be used.
- Specific examples of the oxime compound having a fluorene ring include the compound described in JP-A-2014-137466 and the compound described in Japanese Patent No. 06636081.
- 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 photopolymerization 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 can be mentioned.
- an oxime compound having a nitro group can be used as the photopolymerization 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 JP-A-2014-137466. Examples thereof include the compound described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, ADEKA ARCULDS 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.
- an oxime compound having an aromatic ring group Ar OX1 having an electron-attracting group introduced into the aromatic ring (hereinafter, also referred to as oxime compound OX) can also be used.
- the electron-attracting group of the aromatic ring group Ar OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group and a cyano group.
- the benzoyl group may have a substituent.
- the substituent include a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group and an arylsulfanyl group.
- an acyl group or an amino group more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group or an amino group, and more preferably an alkoxy group or an alkyl group. It is more preferably a sulfanyl group or an amino group.
- the oxime compound OX is preferably at least one selected from the compound represented by the formula (OX1) and the compound represented by the formula (OX2), and more preferably the compound represented by the formula (OX2). preferable.
- RX1 is an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group.
- RX2 contains an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group and an aryl.
- R X3 ⁇ R X14 represents a hydrogen atom or a substituent independently; Provided that at least one of R X10 ⁇ R X14 is an electron withdrawing group.
- Examples of the electron-attracting group include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group and a cyano group, preferably an acyl group and a nitro group, and lightfast resistance.
- An acyl group is more preferable, and a benzoyl group is further preferable, because it is easy to form a film having excellent properties.
- R X12 is an electron withdrawing group, it is preferred that R X10, R X11, R X13 , R X14 is a hydrogen atom.
- oxime compound OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600.
- 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, still more 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 photoradical polymerization initiator may be used as the photopolymerization 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 resin composition with time can be improved.
- Specific examples of the bifunctional or trifunctional or higher functional photo-radical polymerization initiators include Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No.
- the content of the photopolymerization initiator in the total solid content of the resin composition is preferably 0.1 to 20% by mass.
- the lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more.
- the upper limit is preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 6% by mass or less.
- the photopolymerization initiator may be used alone or in combination of two or more. When two or more kinds are used in combination, it is preferable that the total of them is in the above range.
- the resin composition of the present invention can contain a compound having a cyclic ether group.
- the cyclic ether group include an epoxy group and an oxetanyl group.
- the compound having a cyclic ether group is preferably a compound having an epoxy group (hereinafter, also referred to as an epoxy compound).
- the epoxy compound include compounds having one or more epoxy groups in one molecule, and compounds having two or more epoxy groups are preferable.
- the epoxy compound is preferably a compound having 1 to 100 epoxy groups in one molecule.
- the upper limit of the epoxy group contained in the epoxy compound may be, for example, 10 or less, or 5 or less.
- the lower limit of the epoxy group contained in the epoxy compound is preferably two or more.
- the epoxy compound may be a low molecular weight compound (for example, a molecular weight of less than 2000, further, a molecular weight of less than 1000), or a polymer compound (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). But it may be.
- the weight average molecular weight of the compound having an epoxy group is preferably 200 to 100,000, more preferably 500 to 50,000.
- the upper limit of the weight average molecular weight is more preferably 10,000 or less, particularly preferably 5000 or less, and even more preferably 3000 or less.
- an epoxy resin can be preferably used as the epoxy compound.
- the epoxy resin include an epoxy resin which is a glycidyl etherified product of a phenol compound, an epoxy resin which is a glycidyl etherified product of various novolak resins, an alicyclic epoxy resin, an aliphatic epoxy resin, a heterocyclic epoxy resin, and a glycidyl ester.
- Examples thereof include a copolymer with another polymerizable unsaturated compound.
- the epoxy equivalent of the epoxy resin is preferably 310 to 3300 g / eq, more preferably 310 to 1700 g / eq, and even more preferably 310 to 1000 g / eq.
- EHPE3150 manufactured by Daicel Corporation
- EPICLON N-695 manufactured by DIC Corporation
- Marproof G-0150M G-0105SA, G-0130SP, G. -0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (all manufactured by NOF CORPORATION, epoxy group-containing polymer) and the like can be mentioned.
- the content of the compound having a cyclic ether group in the total solid content of the resin composition is preferably 0.1 to 20% by mass.
- the lower limit is, for example, more preferably 0.5% by mass or more, further preferably 1% by mass or more.
- the upper limit is, for example, more preferably 15% by mass or less, further preferably 10% by mass or less.
- the compound having a cyclic ether group only one kind may be used, or two or more kinds may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.
- the resin composition of the present invention may contain a curing accelerator.
- the curing accelerator include thiol compounds, methylol compounds, amine compounds, phosphonium salt compounds, amidin salt compounds, amide compounds, base generators, isocyanate compounds, alkoxysilane compounds, onium salt compounds and the like.
- Specific examples of the curing accelerator include the compound described in paragraph Nos. 0094 to 0097 of International Publication No. 2018/056189, the compound described in paragraph numbers 0246 to 0253 of JP-A-2015-034963, and JP-A-2013-041165. Compounds described in Japanese Patent Laid-Open No.
- the content of the curing accelerator in the total solid content of the resin composition is preferably 0.3 to 8.9% by mass, more preferably 0.8 to 6.4% by mass.
- the resin 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 silicone-based surfactant can be used.
- the surfactant the surfactant described in paragraph Nos. 0238 to 0245 of International Publication No. 2015/166779 is mentioned, and the content thereof is incorporated in the present specification.
- the surfactant is preferably a fluorine-based surfactant.
- a fluorine-based surfactant in the resin composition, the liquid characteristics (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 in the thickness of the coating film and liquid saving, and has good solubility in the resin composition.
- fluorine-based surfactant examples include the surfactants described in paragraphs 0060 to 0064 of Japanese Patent Laid-Open No. 2014-041318 (paragraphs 0060 to 0064 of International Publication No. 2014/017669) and the like, Japanese Patent Application Laid-Open No. 2011-.
- the surfactants described in paragraphs 0117 to 0132 of Japanese Patent Application Laid-Open No. 132503 and the surfactants described in JP-A-2020-008634 are mentioned, and the contents thereof are incorporated in the present specification.
- fluorine-based surfactants include, for example, Megafuck F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144. , F-437, F-475, F-477, F-479, F-482, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560.
- the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which a portion of the functional group containing a fluorine atom is cut off and the fluorine atom volatilizes when heat is applied.
- a fluorine-based surfactant 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.
- the fluorine-based surfactant a block polymer can also be used.
- 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 to 50,000, 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. Specific examples thereof include the compounds described in paragraphs 0050 to 0090 and 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 JP-A-2015-117327 can also be used.
- Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ethers, polyoxyethylene stearyl ethers, etc.
- silicone-based surfactant examples include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400 (all, Toray Dow Corning Co., Ltd.). ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, manufactured by Momentive Performance Materials), KP-341, KF-6001, KF-6002 (above, (Made by Shin-Etsu Chemical Industry Co., Ltd.), BYK307, BYK323, BYK330 (all manufactured by Big Chemie) and the like.
- the content of the surfactant in the total solid content of the resin composition is preferably 0.001% by mass to 5.0% by mass, more preferably 0.005 to 3.0% by mass. Only one type of surfactant may be used, or two or more types may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.
- the resin composition of the present invention can contain a solvent.
- the type of solvent is basically not particularly limited as long as it satisfies the solubility of each component and the coatability of the composition.
- the solvent is preferably an organic solvent.
- the organic solvent include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, hydrocarbon-based solvents and the like.
- paragraph No. 0223 of International Publication No. 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.
- organic solvent examples include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2 -Heptanone, cyclohexanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N , N-Dimethylpropanamide, propylene glycol diacetate, 3-methoxybutanol and the like.
- aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents may need to be reduced for environmental reasons (for example, 50 parts by mass (parts) with respect to the total amount of organic solvent. Per millision) or less, 10 mass ppm or less, or 1 mass ppm or less).
- an organic solvent having a low metal content it is preferable to use an organic solvent having a low metal content, and the metal content of the organic solvent is preferably, for example, 10 mass ppb (parts per parts) or less. If necessary, an organic solvent at the mass ppt (parts per trillion) level may be used, and such an organic 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 organic 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 organic 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 content of peroxide in the organic solvent is preferably 0.8 mmol / L or less, and more preferably substantially free of peroxide.
- the content of the solvent in the resin composition is preferably 10 to 95% by mass.
- the upper limit is preferably 92.5% by mass or less, and more preferably 90% by mass or less.
- the lower limit is preferably 20% by mass or more, more preferably 50% by mass or more, further preferably 70% by mass or more, and further preferably 75% by mass or more. It is preferably 80% by mass or more, and even more preferably.
- the resin composition of the present invention does not substantially contain an environmentally regulated substance from the viewpoint of environmental regulations.
- substantially free of the environmentally regulated substance means that the content of the environmentally regulated substance in the resin composition is 50 mass ppm or less, and preferably 30 mass ppm or less. It is more preferably 10 mass ppm or less, and particularly preferably 1 mass ppm or less.
- the environmentally regulated substance include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene.
- REACH Registration Evolution Analysis and Restriction of Chemicals
- PRTR Policy Release and Transfer Register
- VOC Volatile and Transfer Registor
- VOC Volatile Organic Compounds
- VOC Volatile Organic Compounds
- VOC Volatile Organic Compounds
- VOC Volatile Organic Compounds
- a method for reducing the environmentally regulated substance there is a method of heating or depressurizing the inside of the system to raise the boiling point of the environmentally regulated substance or higher and distilling off the environmentally regulated substance from the system to reduce the amount. Further, when distilling off a small amount of an environmentally regulated substance, it is also useful to azeotrope with a solvent having a boiling point equivalent to that of the corresponding solvent in order to improve efficiency.
- a polymerization inhibitor or the like is added and the mixture is distilled off under reduced pressure in order to prevent the radical polymerization reaction from proceeding and cross-linking between molecules during distillation under reduced pressure. May be.
- distillation methods are a stage of a raw material, a stage of a product obtained by reacting the raw materials (for example, a resin solution after polymerization or a polyfunctional monomer solution), or a stage of a resin composition prepared by mixing these compounds. It is possible at any stage such as.
- the resin 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.
- 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) allyl group, a (meth) acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group and an isocyanate group.
- a phenyl group and the like preferably an amino group, a (meth) acryloyl group and an epoxy group.
- silane coupling agent examples include N- ⁇ -aminoethyl- ⁇ -aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-602), N- ⁇ -aminoethyl- ⁇ -amino.
- Propyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-603), N- ⁇ -aminoethyl- ⁇ -aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-602), ⁇ -Aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-903), ⁇ -aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-903), 3-methacryloxy There are propylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-502), 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co
- silane coupling agent examples include the compounds described in paragraphs 0018 to 0036 of JP2009-288703 and the compounds described in paragraphs 0056 to 0066 of JP2009-242604A. , These contents are incorporated herein.
- the content of the silane coupling agent in the total solid content of the resin composition is preferably 0.1 to 5% by mass.
- the upper limit is more preferably 3% by mass or less, further preferably 2% by mass or less.
- the lower limit is more preferably 0.5% by mass or more, further preferably 1% by mass or more. Only one kind of silane coupling agent may be used, or two or more kinds may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.
- the resin 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 indole 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 JP2013-066814.
- the compounds described in paragraphs 0061 to 0080 of JP 2016-162946 are mentioned, the contents of which are incorporated herein by reference.
- 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 of Miyoshi Oil & Fat (The Chemical Daily, February 1, 2016).
- 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 resin 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 kinds are used, it is preferable that the total amount thereof is within the above range.
- the resin composition of the present invention can contain an antioxidant.
- the antioxidant include a phenol compound, a phosphite ester compound, a thioether compound 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. Further, as the antioxidant, a phosphorus-based antioxidant can also be preferably used. Further, as the antioxidant, the compound described in Korean Patent Publication No. 10-2019-0059371 can also be used.
- the content of the antioxidant in the total solid content of the resin composition is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass. Only one kind of antioxidant may be used, or two or more kinds may be used. When two or more kinds are used, it is preferable that the total amount is within the above range.
- the resin 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 resin composition is preferably 0.0001 to 5% by mass.
- the polymerization inhibitor may be only one kind or two or more kinds. In the case of two or more types, it is preferable that the total amount is within the above range.
- the resin composition is, if necessary, 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). , Flame retardant, leveling agent, peeling accelerator, fragrance, surface tension modifier, chain transfer agent, etc.) may be contained.
- auxiliary agents for example, conductive particles, a filler, a defoaming agent.
- the resin 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. This includes compounds in which the protecting group is desorbed and functions as an antioxidant.
- 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 of latent antioxidants include ADEKA ARKULS GPA-5001 (manufactured by ADEKA Corporation).
- the resin composition of the present invention may contain a light resistance improving agent.
- the light resistance improving agent include the compounds described in paragraphs 0036 to 0037 of JP-A-2017-198787, the compounds described in paragraphs 0029 to 0034 of JP-A-2017-146350, and JP-A-2017-129774.
- the resin composition of the present invention preferably has a free metal content of 100 ppm or less, more preferably 50 ppm or less, still more preferably 10 ppm or less, which is not bonded or coordinated with a pigment or the like. , It is particularly preferable that it is not substantially contained. According to this aspect, stabilization of pigment dispersibility (suppression of aggregation), improvement of spectral characteristics due to improvement of dispersibility, stabilization of curable components, suppression of conductivity fluctuation due to elution of metal atoms / metal ions, Effects such as improvement of display characteristics can be expected.
- the types of free metals include Na, K, Ca, Sc, Ti, Mn, Cu, Zn, Fe, Cr, Co, Mg, Al, Sn, Zr, Ga, Ge, Ag, Au, Pt, and the like.
- the resin composition of the present invention preferably has a content of free halogen not bonded or coordinated with a pigment or the like of 100 ppm or less, more preferably 50 ppm or less, and more preferably 10 ppm or less. It is more preferable, and it is particularly preferable that it is not substantially contained.
- the halogen include F, Cl, Br, I and their anions.
- the method for reducing free metals and halogens in the resin composition include washing with ion-exchanged water, filtration, ultrafiltration, and purification with an ion-exchange resin.
- the resin composition of the present invention does not substantially contain a terephthalic acid ester.
- substantially free means that the content of the terephthalic acid ester is 1000 mass ppb or less in the total amount of the resin composition, and more preferably 100 mass ppb or less. Zero is particularly preferred.
- perfluoroalkyl sulfonic acid and its salt and perfluoroalkyl carboxylic acid and its salt may be restricted.
- the perfluoroalkyl sulfonic acid particularly the perfluoroalkyl sulfonic acid having 6 to 8 carbon atoms in the perfluoroalkyl group
- a salt thereof and a per.
- the content of the fluoroalkylcarboxylic acid (particularly the perfluoroalkylcarboxylic acid having 6 to 8 carbon atoms in the perfluoroalkyl group) and its salt is 0.01 ppb to 1,000 ppb with respect to the total solid content of the resin composition. It is preferably in the range of 0.05 ppb to 500 ppb, and even more preferably in the range of 0.1 ppb to 300 ppb.
- the resin composition of the present invention may be substantially free of perfluoroalkyl sulfonic acid and salts thereof, as well as perfluoroalkyl carboxylic acid and salts thereof.
- a compound that can substitute for perfluoroalkyl sulfonic acid and its salt and a compound that can substitute for perfluoroalkyl carboxylic acid and its salt, perfluoroalkyl sulfonic acid and its salt, and perfluoroalkyl carboxylic acid can be used.
- a resin composition that is substantially free of salts thereof may be selected.
- compounds that can substitute for the regulated compound include compounds excluded from the regulation due to the difference in the number of carbon atoms of the perfluoroalkyl group.
- the above-mentioned contents do not prevent the use of perfluoroalkyl sulfonic acid and its salt, and perfluoroalkyl carboxylic acid and its salt.
- the resin composition of the present invention may contain a perfluoroalkyl sulfonic acid and a salt thereof, and a perfluoroalkyl carboxylic acid and a salt thereof within the maximum allowable range.
- the storage container for the resin composition is not particularly limited, and a known storage container can be used.
- a storage container for the purpose of suppressing impurities from being mixed into raw materials and resin compositions, a multi-layer bottle having a container inner wall composed of 6 types and 6 layers of resin and a bottle having 6 types of resin having a 7-layer structure. It is also preferable to use. 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, improving the storage stability of the resin composition, and suppressing the deterioration of the components.
- the resin composition of the present invention can be prepared by mixing the above-mentioned components.
- all the components may be dissolved and / or dispersed in a solvent at the same time to prepare a resin composition, or each component may be appropriately used as two or more solutions or dispersions, if necessary. Then, these may be mixed at the time of use (at the time of application) to prepare a resin composition.
- 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.
- JP-A-2015-157893 "Comprehensive Data Collection, Published by Management Development Center Publishing Department, October 10, 1978" can be preferably used.
- the particles 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.
- fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF)
- polyamide resins such as nylon (eg, nylon-6, nylon-6,6)
- polyolefin resins such as polyethylene and polypropylene (PP).
- filters using materials such as (including high-density, ultra-high molecular weight polyolefin resin).
- polypropylene (including high-density polypropylene) and nylon are preferable.
- the pore diameter 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 diameter 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. DFA4201NXEY, DFA4201NAEY, DFA4201J006P, etc.
- KITZ Microfilter Co., Ltd., etc. can be used. ..
- a fiber-like filter medium As the filter.
- the fiber-like 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.
- 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 resin composition of the present invention.
- the film thickness of the film of the present invention can be appropriately adjusted depending on the intended purpose.
- the film thickness is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less.
- the lower limit of the film thickness is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, still more preferably 0.3 ⁇ m or more.
- the film of the present invention can be used as a color filter, a near-infrared transmission filter, a near-infrared cut filter, a black matrix, a light-shielding film, and the like.
- the film of the present invention can be preferably used as a colored pixel of a color filter.
- the colored pixel include a red pixel, a green pixel, a blue pixel, a magenta color pixel, a cyan color pixel, a yellow pixel and the like, and a green pixel or a cyan color pixel is preferable, and a green pixel is more preferable.
- the wavelength at which the light transmittance of the film of the present invention is 50% preferably exists in the wavelength range of 470 to 520 nm, and is preferably in the wavelength range of 475 to 520 nm. It is more preferably present, and even more preferably in the wavelength range of 480 to 520 nm. Above all, it is preferable that the wavelength at which the light transmittance is 50% exists in each of the wavelength range of 470 to 520 nm and the wavelength range of 575 to 625 nm.
- the wavelength on the short wavelength side where the light transmittance is 50% preferably exists in the wavelength range of 475 to 520 nm, and more preferably exists in the wavelength range of 480 to 520 nm. Further, the wavelength on the long wavelength side where the light transmittance is 50% preferably exists in the wavelength range of 580 to 620 nm, and more preferably exists in the wavelength range of 585 to 615 nm. A film having such spectral characteristics is preferably used as a green pixel.
- the maximum absorption wavelength of the film of the present invention preferably exists in the wavelength range of 700 to 1800 nm, more preferably in the wavelength range of 700 to 1300 nm. It is more preferably present in the wavelength range of 700 to 1100 nm.
- the transmittance of the film in the entire wavelength range of 400 to 650 nm is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more. Further, the transmittance at at least one point in the wavelength range of 700 to 1800 nm of the film is preferably 20% or less.
- the ratio of the absorbance Amax at the maximum absorption wavelength to the absorbance A550 at a wavelength of 550 nm is preferably 20 to 500, more preferably 50 to 500, and 70 to 450. It is more preferably present, and particularly preferably 100 to 400.
- the film of the present invention preferably has any of the following spectral characteristics (i1) to (i5).
- (I1) The maximum value of the transmittance in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 800 to 1500 nm is.
- a film having such spectral characteristics can block light in the wavelength range of 400 to 640 nm and transmit light having a wavelength of more than 750 nm.
- the maximum value of the transmittance in the wavelength range of 400 to 750 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 900 to 1500 nm is.
- a film having such spectral characteristics can block light in the wavelength range of 400 to 750 nm and transmit light having a wavelength of more than 850 nm.
- the maximum value of the transmittance in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 1000 to 1500 nm is.
- a film having such spectral characteristics can block light in the wavelength range of 400 to 830 nm and transmit light having a wavelength exceeding 950 nm.
- the maximum value of the transmittance in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 1100 to 1500 nm is.
- a film having such spectral characteristics can block light in the wavelength range of 400 to 950 nm and transmit light having a wavelength exceeding 1050 nm.
- the maximum value of the transmittance in the wavelength range of 400 to 1050 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 1200 to 1500 nm is.
- a film having such spectral characteristics can block light in the wavelength range of 400 to 1050 nm and transmit light having a wavelength exceeding 1150 nm.
- the film of the present invention can be produced through a step of applying the resin composition of the present invention.
- the film manufacturing method preferably further includes a step of forming a pattern (pixel). Examples of the pattern (pixel) forming method include a photolithography method and a dry etching method, and the photolithography method is preferable.
- the pattern formation by the photolithography method includes a step of forming a resin composition layer on a support using the resin composition of the present invention, a step of exposing the resin composition layer in a pattern, and a step of exposing the resin composition layer in a pattern. It is preferable to include a step of developing and removing the exposed portion to form a pattern (pixel). If necessary, a step of baking the resin composition layer (pre-baking step) and a step of baking the developed pattern (pixels) (post-baking step) may be provided.
- the resin composition layer of the present invention is used to form the resin composition layer on the support.
- the support is not particularly limited and may be appropriately selected depending on the intended use. Examples thereof include a glass substrate and a silicon substrate, and a silicon substrate is preferable. Further, a charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like may be formed on the silicon substrate. Further, a black matrix that separates each pixel may be formed on the silicon substrate. Further, the silicon substrate 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 coating property of the resin composition is good.
- 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 resin composition.
- a drop method drop cast
- a slit coat method a spray method
- a roll coat method a rotary coating method
- spin coating a cast coating method
- a slit and spin method a pre-wet method (for example, JP-A-2009-145395).
- Methods described in the publication Inkjet (for example, on-demand method, piezo method, thermal method), ejection system printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc.
- Various printing methods; transfer method using a mold or the like; nanoinprint method and the like can be mentioned.
- the method of application in inkjet is not particularly limited, and is, for example, the method shown in "Expandable / usable inkjet-infinite possibilities seen in patents-, published in February 2005, Sumi Betechno Research" (especially from page 115). Page 133), 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, regarding the method of applying the resin composition, the description of International Publication No. 2017/030174 and International Publication No. 2017/018419 can be referred to, and these contents are incorporated in the present specification.
- the resin composition layer formed on the support may be dried (prebaked).
- prebaking may not be performed.
- the prebake temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, still more preferably 110 ° C. or lower.
- the lower limit can be, for example, 50 ° C. or higher, or 80 ° C. or higher.
- the prebake time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, still more preferably 80 to 220 seconds. Pre-baking can be performed on a hot plate, an oven, or the like.
- the resin composition layer is exposed in a pattern (exposure step).
- the resin composition layer can be exposed in a pattern by exposing the resin 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), ArF line (wavelength 193 nm) and the like, and KrF line (wavelength 248 nm) is preferable. Further, a long wave light source having a diameter of 300 nm or more can also be used.
- pulse exposure is an exposure method of a method in which light irradiation and pause are repeated 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.
- the oxygen concentration at the time of exposure can be appropriately selected, and in addition to the operation in the atmosphere, for example, in a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially). It may be exposed in an oxygen-free environment (for example, 22% by volume, 30% by volume, or 50% by volume) in a high oxygen atmosphere having an oxygen concentration of more than 21% by volume.
- the exposure illuminance can be set as appropriate, and is usually selected from the range of 1000 W / m 2 to 100,000 W / m 2 (for example, 5000 W / m 2 , 15,000 W / m 2 , or 35,000 W / m 2). Can be done.
- the oxygen concentration and the exposure illuminance may be appropriately combined with each other.
- the oxygen concentration may be 10% by volume and the illuminance may be 10,000 W / m 2
- the oxygen concentration may be 35% by volume and the illuminance may be 20000 W / m 2 .
- the unexposed portion of the resin composition layer is developed and removed to form a pattern (pixel).
- the unexposed portion of the resin composition layer can be developed and removed using a developing solution.
- the resin composition layer in the unexposed portion in the exposure step is eluted in the developer, and only the photocured portion remains.
- the temperature of the developer 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 developer every 60 seconds and supplying a new developer 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, etc.
- examples thereof include organic 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. From the viewpoint of convenience of transfer and storage, the developer may be once produced as a concentrated solution and diluted to a concentration required for use.
- the dilution ratio is not particularly limited, but can be set in the range of, for example, 1.5 to 100 times. It is also 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 resin composition layer while rotating the support on which the developed resin composition layer is formed.
- the nozzle for discharging the rinse liquid from the central portion of the support 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.
- the nozzle may be moved while gradually reducing the moving speed. By rinsing in this way, in-plane variation of the rinse 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 central portion of the support to the peripheral portion.
- Additional exposure processing and post-baking are post-development curing treatments to complete the curing.
- the heating temperature in the post-bake 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 type 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 pattern formation by the dry etching method includes a step of forming a resin composition layer on a support using the resin composition of the present invention and curing the entire resin composition layer to form a cured product layer.
- the optical filter of the present invention has the above-mentioned film of the present invention.
- the type of the optical filter include a color filter, a near-infrared cut filter, a near-infrared transmission filter, and the like, and a color filter is preferable.
- the color filter preferably has the film of the present invention as its pixel, more preferably has the film of the present invention as a colored pixel, and further preferably has the film of the present invention as a green pixel.
- the film thickness of the film of the present invention can be appropriately adjusted according to the purpose.
- the film thickness is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less.
- the lower limit of the film thickness is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, still more preferably 0.3 ⁇ m or more.
- the width of the pixels included in the optical filter is preferably 0.4 to 10.0 ⁇ m.
- the lower limit is preferably 0.4 ⁇ m or more, more preferably 0.5 ⁇ m or more, and further preferably 0.6 ⁇ m or more.
- the upper limit is preferably 5.0 ⁇ m or less, more preferably 2.0 ⁇ m or less, further preferably 1.0 ⁇ m or less, and even more preferably 0.8 ⁇ m or less.
- the Young's modulus of the pixel is preferably 0.5 to 20 GPa, more preferably 2.5 to 15 GPa.
- each pixel included in the optical filter has high flatness.
- the surface roughness Ra of the pixel is preferably 100 nm or less, more preferably 40 nm or less, and further preferably 15 nm or less.
- the lower limit is not specified, but it is preferably 0.1 nm or more, for example.
- the surface roughness of the pixel can be measured using, for example, an AFM (atomic force microscope) Measurement 3100 manufactured by Veeco.
- the contact angle of water on the pixel can be appropriately set to a preferable value, but is typically in the range of 50 to 110 °.
- the contact angle can be measured using, for example, a contact angle meter CV-DT ⁇ A type (manufactured by Kyowa Interface Science Co., Ltd.). Further, it is preferable that the volume resistance value of the pixel is high. Specifically, it is preferred that the volume resistivity value of the pixel is 10 9 ⁇ ⁇ cm or more, and more preferably 10 11 ⁇ ⁇ cm or more. The upper limit is not specified, but it is preferably 10 14 ⁇ ⁇ cm or less, for example.
- the volume resistance value of the pixel can be measured using an ultra-high resistance meter 5410 (manufactured by Advantest).
- a protective layer may be provided on the surface of the film of the present invention.
- various functions such as oxygen blocking, low reflection, prohydrophobicization, and shielding of light of a specific wavelength (ultraviolet rays, near infrared rays, etc.) can be imparted.
- the thickness of the protective layer is preferably 0.01 to 10 ⁇ m, more preferably 0.1 to 5 ⁇ m.
- Examples of the method for forming the protective layer include a method of applying a resin composition for forming a protective layer to form the protective layer, a chemical vapor deposition method, and a method of attaching a molded resin with an adhesive.
- the components constituting the protective layer include (meth) acrylic resin, en-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, and polyimide.
- Resin polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, melamine resin, urethane resin, aramid resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluorine Examples thereof include resins, polycarbonate resins, polyacrylonitrile resins, cellulose resins, Si, C, W, Al 2 O 3 , Mo, SiO 2 , Si 2 N 4, and the like, and two or more of these components may be contained.
- the protective layer for the purpose of blocking oxygen, it is preferable that the protective layer contains a polyol resin, SiO 2 , and Si 2 N 4. Further, in the case of a protective layer for the purpose of reducing reflection, it is preferable that the protective layer contains a (meth) acrylic resin and a fluororesin.
- the protective layer may be an additive such as organic / inorganic fine particles, an absorber for light of a specific wavelength (for example, ultraviolet rays, near infrared rays, etc.), a refractive index adjusting agent, an antioxidant, an adhesive, and a surfactant, if necessary. May be contained.
- organic / inorganic fine particles include polymer fine particles (for example, silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, and titanium oxynitride. , Magnesium fluoride, hollow silica, silica, calcium carbonate, barium sulfate and the like.
- the absorber of light having a specific wavelength a known absorber can be used.
- the content of these additives can be adjusted as appropriate, but is preferably 0.1 to 70% by mass, more preferably 1 to 60% by mass, based on the total mass of the protective layer.
- the protective layer described in paragraphs 0073 to 0092 of JP-A-2017-151176 can also be used.
- the optical filter may have a structure in which each pixel is embedded in a space partitioned by a partition wall, for example, in a grid pattern.
- the solid-state image sensor of the present invention has the above-mentioned film of the present invention.
- the configuration of the solid-state image pickup device of the present invention is not particularly limited as long as it includes the film of the present invention and functions as a solid-state image pickup device, and examples thereof include the following configurations.
- a solid-state image sensor charge coupling element
- CMOS complementary metal oxide semiconductor
- a transfer electrode made of polysilicon or the like.
- the configuration has a color filter on the device protective film.
- the color filter may have a structure in which each pixel is embedded in a space partitioned by a partition wall, for example, in a grid pattern.
- the partition wall preferably has a low refractive index for each pixel. Examples of the image pickup apparatus having such a structure include the apparatus described in Japanese Patent Application Laid-Open No. 2012-227478, Japanese Patent Application Laid-Open No. 2014-179757, and International Publication No. 2018/043654.
- an ultraviolet absorbing layer may be provided in the structure of the solid-state image sensor to improve the light resistance.
- the image pickup device provided with the solid-state image pickup device of the present invention can be used not only for digital cameras and electronic devices having an image pickup function (mobile phones and the like), but also for in-vehicle cameras and surveillance cameras.
- the image display device of the present invention has the above-mentioned film of the present invention.
- the image display device include a liquid crystal display device and an organic electroluminescence display device.
- the liquid crystal display device is described in, for example, “Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, Kogyo Chosakai Co., Ltd., published in 1994)”.
- the liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the above-mentioned "next-generation liquid crystal display technology".
- ⁇ Measuring method of amine value> The amine value was calculated by the following method. The measurement sample was dissolved in acetic acid, and the obtained solution was neutralized and titrated with a 0.1 mol / L perchloric acid / acetic acid solution using a potentiometric titrator (trade name: AT-510, manufactured by Kyoto Denshi Kogyo). The amine value was calculated by the following formula with the inflection point of the titration pH curve as the titration end point.
- Vs Vs ⁇ 0.1 ⁇ f / w
- Amine value (mmol / g)
- Vs Amount of 0.1 mol / L perchloric acid / acetic acid solution required for titration (mL)
- f Titer of 0.1M perchloric acid / acetic acid solution
- w Weight of measurement sample (g) (in terms of solid content)
- Dispersion prescription 1 A mixed solution of 14 parts by mass of the pigment, 3.5 parts by mass of the specific compound, the pigment derivative and the resin in total in terms of solid content, and 82.5 parts by mass of the solvent was mixed with a bead mill (zirconia beads 0.1 mm diameter). ) was mixed and dispersed for 3 hours to prepare a dispersion. Then, a dispersion treatment was performed using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism under the conditions of a pressure of 2000 kg / cm 2 and a flow rate of 500 g / min.
- NANO-3000-10 manufactured by Nippon BEE Co., Ltd.
- This dispersion treatment was repeated up to a total of 10 times to obtain a dispersion liquid.
- the materials shown in the table below were used for the pigments, pigment derivatives, resins, specific compounds and solvents.
- the mixing ratio of the pigment derivative, the resin, and the specific compound in the table below is a value in terms of solid content.
- P-1 C.I. I. Pigment Green7 (Halogenated copper phthalocyanine pigment, green pigment)
- P-2 C.I. I. Pigment Green36 (Halogenated copper phthalocyanine pigment, green pigment)
- P-3 C.I. I. Pigment Green58 (Halogenated Zinc Phthalocyanine Pigment, Green Pigment)
- P-4 C.I. I. Pigment Green59 (Halogenated Zinc Phthalocyanine Pigment, Green Pigment)
- P-5 C.I. I. Pigment Green63 (Halogenated aluminum phthalocyanine pigment, green pigment)
- P-6 C.I. I. Pigment Yellow 129 (azomethine copper complex pigment, yellow pigment)
- P-7 C.I. I.
- Pigment Violet23 (purple pigment)
- P-24 TiO 2 (pigment containing titanium atom, white pigment)
- P-25 TiON (pigment containing titanium atom, black pigment)
- P-26 Compound with the following structure (near infrared absorber pigment)
- P-27 Compound with the following structure (near infrared absorber pigment)
- A-1 Polyethyleneimine (Epomin SP-003, manufactured by Nippon Shokubai Co., Ltd.)
- A-2 Polyethyleneimine (Epomin SP-006, manufactured by Nippon Shokubai Co., Ltd.)
- A-3 Polyethyleneimine (Epomin SP-012, manufactured by Nippon Shokubai Co., Ltd.)
- A-4 Polyethyleneimine (Epomin SP-018, manufactured by Nippon Shokubai Co., Ltd.)
- A-5 Polyethyleneimine (Epomin SP-200, manufactured by Nippon Shokubai Co., Ltd.)
- A-6 Polyethyleneimine (Epomin P-1000, manufactured by Nippon Shokubai Co., Ltd.)
- A-7 Compounds with the following structure (hindered amine compound, ADEKA STAB LA-52, manufactured by ADEKA Corporation)
- A-8 Compounds with the following structure (hindered amine compound, ADEKA STAB LA-57, manufactured by ADEKA Corporation)
- A-9 Compounds with
- the following table shows the physical property values of the specific compounds A-1 to A-14 and AN-1 to AN-3.
- the physical characteristic values of the specific compounds A-1 to A-6 are catalog values.
- the molecular weight values of the specific compounds A-1 to A-5 are the values of the number average molecular weight measured by the boiling point elevation method (catalog values).
- the molecular weight value of the specific compound A-6 is the value of the number average molecular weight measured by the viscosity method (catalog value).
- the molecular weight values of the specific compounds A-9, A-10, A-14, and AN-3 are the values of the number average molecular weight measured by the GPC method.
- the molecular weight values of the specific compounds A-7, A-8, A-11, A-12, A-13, AN-1, and AN-2 are calculated values from the structural formula.
- (resin) B-1 A 30% by mass PGMEA solution of resin B-1 synthesized by the following method. 50 parts by mass of methyl methacrylate, 30 parts by mass of n-butyl methacrylate, 20 parts by mass of t-butyl methacrylate and 45.4 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) were charged in a reaction vessel, and the atmosphere gas was replaced with nitrogen gas. The inside of the reaction vessel is heated to 70 ° C., 6 parts by mass of 3-mercapto-1,2-propanediol is added, and 0.12 parts by mass of AIBN (azobisisobutyronitrile) is further added, and the reaction is carried out for 12 hours. I let you.
- AIBN azobisisobutyronitrile
- B-2 A 30% by mass PGMEA solution of resin B-2 synthesized by the following method. 3-Mercapto-1,2-propanediol 6.0 parts by mass, pyromellitic anhydride 9.5 parts by mass, PGMEA 62 parts by mass, 1,8-diazabicyclo- [5.4.0] -7-undecene 0. Two parts by mass were charged in a reaction vessel, and the atmosphere gas was replaced with nitrogen gas. The inside of the reaction vessel was heated to 100 ° C. and reacted for 7 hours.
- the temperature in the system was cooled to 70 ° C., and 65 parts by mass of methyl methacrylate, 5.0 parts by mass of ethyl acrylate, and t. -Add 53.5 parts by mass of PGMEA solution in which 15 parts by mass of butyl acrylate, 5.0 parts by mass of methacrylic acid, 10 parts by mass of hydroxyethyl methacrylate and 0.1 parts by mass of 2,2'-azobisisobutyronitrile are dissolved. Then, it was reacted for 10 hours.
- the compound obtained in the first step is 160 parts by mass in terms of solid content, 200 parts by mass of 2-hydroxypropyl methacrylate, 200 parts by mass of ethyl acrylate, 150 parts by mass of t-butyl acrylate, and 200 parts by mass of 2-methoxyethyl acrylate.
- 200 parts by mass of methyl acrylate, 50 parts by mass of methacrylic acid, and 663 parts by mass of PGMEA are charged in a reaction vessel, and the inside of the reaction vessel is heated to 80 ° C. to 2,2'-azobis (2,4-dimethylvaleronitrile) 1 .2 parts by mass was added and reacted for 12 hours (second step).
- Resin having the following structure (the numerical value added to the main chain is the molar ratio, and the numerical value added to the side chain is the number of repeating units. Resin having an acid group, weight average molecular weight 16000, acid value 67 mgKOH / g) 30% by mass PGMEA solution
- Resin having the following structure (the numerical value added to the main chain is the molar ratio, and the numerical value added to the side chain is the number of repeating units. Resin having an acid group, weight average molecular weight 24000, acid value 52. 5 mgKOH / g) 30 mass% PGMEA solution
- Resin having the following structure (the numerical value added to the main chain is the molar ratio, and the numerical value added to the side chain is the number of repeating units. Resin having an acid group, weight average molecular weight 18000, acid value 82. 1 mgKOH / g) 30 mass% PGMEA solution
- B-8 A solution in which PGMEA is added to DISPERBYK-111 (manufactured by BYK Chemie, a resin having an acid group) to adjust the non-volatile content (solid content concentration) to 30% by mass.
- the details other than the dispersion liquid are as follows.
- the above-mentioned dispersion was used as the dispersion.
- M-1 Compound with the following structure
- M-2 Compound with the following structure
- M-3 KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
- M-4 Compound with the following structure
- I-1 Irgure OXE01 (Oxime compound manufactured by BASF)
- I-2 Irgure OXE02 (Oxime compound manufactured by BASF)
- I-3 Irgure OXE02 (Oxime compound manufactured by BASF)
- I-3 Irgure OXE02 (Oxime compound manufactured by BASF)
- I-3 I-4: Compounds with the following structure
- I-5 Omnirad 379 ( ⁇ -aminoketone compound manufactured by IGM Resins B.V.)
- (resin) B-1 to B-8 Resins B-1 to B-8 (30% by mass PGMEA solution) described above.
- B-10 30% by mass PGMEA solution of a resin having the following structure (the numerical value added to the main chain is a molar ratio.
- (Surfactant) W-1 A compound having the following structure (weight average molecular weight 14000). In the following formula,% indicating the ratio of the repeating unit is mol%.
- Viscosity volatility (%) ((Viscosity after standing (V1) -Initial viscosity (V0)) / Initial viscosity (V0)) x 100 5: Viscosity volatility is less than 5% 4: Viscosity volatility is 5% or more and less than 10% 3: Viscosity volatility is 10% or more and less than 30% 2: Viscosity volatility is 30% or more and 100% Less than 1: Viscosity volatility is 100% or more
- the composition for an underlayer is applied by a spin coating method, then heated at 100 ° C. for 2 minutes using a hot plate, and then 230 using a hot plate.
- a base layer having a film thickness of 10 nm was formed by heating at ° C. for 2 minutes.
- the composition for the underlayer will be described later.
- the resin compositions of Examples 1 to 128 and Comparative Examples 1 to 3 were applied onto the silicon wafer on which the base layer was formed by a spin coating method so that the film thickness after film formation was 0.4 ⁇ m. Then, it was heated at 100 ° C. for 2 minutes using a hot plate.
- i-line stepper exposure apparatus FPA-3000i5 + manufactured by Canon Inc.
- exposure was performed at an exposure amount of 150 mJ / cm 2 through a mask having an island pattern of 1.0 ⁇ m.
- paddle development was performed at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH).
- TMAH tetramethylammonium hydroxide
- the composition for an underlayer is applied by a spin coating method, then heated at 100 ° C. for 2 minutes using a hot plate, and then 230 using a hot plate. A base layer having a film thickness of 10 nm was formed by heating at ° C. for 2 minutes. The composition for the underlayer will be described later.
- the resin compositions of Examples 1 to 23, 28 to 85, 88 to 128, and Comparative Examples 1 to 3 are placed on a glass wafer on which a base layer is formed, and the film thickness after film formation becomes 0.4 ⁇ m. It was applied by the spin coating method as described above, and then heated at 100 ° C.
- TMAH tetramethylammonium hydroxide
- the fluctuation rate of the transmittance of light having a wavelength of 400 to 700 nm was determined before and after the constant temperature test (holding for 2000 hours in an environment of a temperature of 150 ° C.).
- Variable rate of transmittance (%) (
- T1 is an integrated value of the transmittance of light having a wavelength of 400 to 700 nm before the constant temperature test
- T2 is an integrated value of the transmittance of light having a wavelength of 400 to 700 nm after the constant temperature test.
- Transmittance volatility is less than 3% 4: Transmittance volatility is 3% or more and less than 5% 3: Transmittance volatility is 5% or more and less than 10% 2: Transmittance volatility is 10% or more Less than 20% 1: Transmittance fluctuation rate is 20% or more
- composition for base layer The composition for the underlayer was produced by mixing the following raw materials.
- Resin A 0.7 parts by mass
- Surfactant A 0.8 parts by mass
- the resin composition of the example had good storage stability. Furthermore, it was possible to form a film in which the generation of foreign substances was suppressed. Further, in Examples 1 to 23, 28 to 85, and 88 to 128, it was possible to form a film in which fluctuations in spectral characteristics were suppressed.
- Example 1001 The composition for the underlayer is applied onto the silicon wafer by the spin coating method, then heated at 100 ° C. for 2 minutes using a hot plate, and then heated at 230 ° C. for 2 minutes using a hot plate to form a film thickness. An underlayer of 10 nm was formed. The composition for the underlayer is the same as the composition for the underlayer used in the evaluation of foreign matter. Next, the green resin composition was applied onto the silicon wafer on which the base layer was formed by a spin coating method so that the film thickness after film formation was 1.0 ⁇ m. Then, using a hot plate, it was heated at 100 ° C. for 2 minutes.
- i-line stepper exposure apparatus FPA-3000i5 + manufactured by Canon Inc.
- exposure was performed with an exposure amount of 1000 mJ / cm 2 via a mask of a 2 ⁇ m square dot pattern.
- paddle development was performed at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH).
- TMAH tetramethylammonium hydroxide
- the green resin composition was patterned to form green pixels by heating at 200 ° C. for 5 minutes using a hot plate.
- the red resin composition and the blue resin composition were patterned by the same process to sequentially form red pixels and blue pixels to form a color filter having green pixels, red pixels and blue pixels.
- green pixels are formed by a Bayer pattern
- red pixels and blue pixels are formed by an island pattern in an adjacent region thereof.
- the obtained color filter was incorporated into a solid-state image sensor according to a known method. This solid-state image sensor had suitable image recognition ability.
- the green resin composition the resin composition of Example 99 was used.
- the red resin composition the resin composition of Example 79 was used.
- the blue resin composition the resin composition of Example 84 was used.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Optical Filters (AREA)
- Materials For Photolithography (AREA)
Abstract
Description
<1> 顔料と、
1分子中に塩基性基を3個以上含み、アミン価が2.7mmol/g以上で、分子量が100以上の化合物Aと、
酸基を有する樹脂とを含む樹脂組成物であり、
上記樹脂組成物の全固形分中に上記顔料を40質量%以上含む樹脂組成物。
<2> 化合物Aが有する塩基性基がアミノ基である、<1>に記載の樹脂組成物。
<3> 上記化合物Aのアミン価が15mmol/g以上である、<1>または<2>に記載の樹脂組成物。
<4> 上記化合物Aがポリアルキレンイミンである、<1>~<3>のいずれか1つに記載の樹脂組成物。
<5> 上記化合物Aがポリエチレンイミンである、<1>~<3>のいずれか1つに記載の樹脂組成物。
<6> 上記化合物Aの分子量が2000以下である、<1>~<5>のいずれか1つに記載の樹脂組成物。
<7> 上記顔料は有彩色顔料を含む、<1>~<6>のいずれか1つに記載の樹脂組成物。
<8> 上記顔料は金属原子を含む顔料を含む、<1>~<7>のいずれか1つに記載の樹脂組成物。
<9> 上記顔料はハロゲン化亜鉛フタロシアニン顔料を含む、<1>~<8>のいずれか1つに記載の樹脂組成物。
<10> 上記樹脂組成物の全固形分中に上記顔料を60質量%以上含む、<1>~<9>のいずれか1つに記載の樹脂組成物。
<11> 更に顔料誘導体を含む、<1>~<10>のいずれか1つに記載の樹脂組成物。
<12> <1>~<11>のいずれか1つに記載の樹脂組成物を用いて得られる膜。
<13> <12>に記載の膜を有する光学フィルタ。
<14> <12>に記載の膜を有する固体撮像素子。
<15> <12>に記載の膜を有する画像表示装置。
本明細書において、「~」とはその前後に記載される数値を下限値および上限値として含む意味で使用される。
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(原子団)と共に置換基を有する基(原子団)をも包含する。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)をも包含する。
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、構造式中のMeはメチル基を表し、Etはエチル基を表し、Buはブチル基を表し、Prはプロピル基を表し、Phはフェニル基を表す。
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、GPC(ゲルパーミエーションクロマトグラフィ)法により測定したポリスチレン換算値である。
本明細書において、近赤外線とは、波長700~2500nmの光をいう。
本明細書において、全固形分とは、組成物の全成分から溶剤を除いた成分の総質量をいう。
本明細書において、顔料とは、溶剤に対して溶解しにくい色材を意味する。例えば、顔料は、23℃の水100gおよび23℃のプロピレングリコールモノメチルエーテルアセテート100gに対する溶解度がいずれも0.1g以下であることが好ましく、0.01g以下であることがより好ましい。
本明細書において、染料とは、溶剤に対して溶解しやすい色材を意味する。
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。
本発明の樹脂組成物は、顔料と、1分子中に塩基性基を3個以上含み、アミン価が2.7mmol/g以上で、分子量が100以上の化合物Aと、酸基を有する樹脂とを含む樹脂組成物であり、樹脂組成物の全固形分中に顔料を40質量%以上含むことを特徴とする。
(1):波長400~640nmの範囲における透過率の最大値が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800~1500nmの範囲における透過率の最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)であるフィルタ。
(2):波長400~750nmの範囲における透過率の最大値が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900~1500nmの範囲における透過率の最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)であるフィルタ。
(3):波長400~830nmの範囲における透過率の最大値が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1000~1500nmの範囲における透過率の最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)であるフィルタ。
(4):波長400~950nmの範囲における透過率の最大値が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1100~1500nmの範囲における透過率の最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)であるフィルタ。
(5):波長400~1050nmの範囲における透過率の最大値が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1200~1500nmの範囲における透過率の最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)であるフィルタ。
本発明の樹脂組成物は顔料を含む。顔料としては、白色顔料、黒色顔料、有彩色顔料、近赤外線吸収顔料が挙げられる。なお、本明細書において、白色顔料には純白色のみならず、白に近い明るい灰色(例えば灰白色、薄灰色など)の顔料などが含まれる。
また、亜鉛フタロシアニン顔料とは、亜鉛原子を中心金属として有するフタロシアニン顔料のことである。また、ハロゲン化亜鉛フタロシアニン顔料とは、亜鉛原子を中心金属として有するハロゲン化フタロシアニン顔料のことである。
また、アルミニウムフタロシアニン顔料とは、アルミニウム原子を中心金属として有するフタロシアニン顔料のことである。また、ハロゲン化アルミニウムフタロシアニン顔料とは、アルミニウム原子を中心金属として有するハロゲン化フタロシアニン顔料のことである。
有彩色顔料としては、特に限定されず、公知の有彩色顔料を用いることができる。有彩色顔料としては、波長400~700nmの範囲に極大吸収波長を有する顔料が挙げられる。例えば、黄色顔料、オレンジ色顔料、赤色顔料、緑色顔料、紫色顔料、青色顔料などが挙げられる。これらの具体例としては、例えば、以下が挙げられる。
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)。
(1)赤色顔料と青色顔料とを含有する態様。
(2)赤色顔料と青色顔料と黄色顔料とを含有する態様。
(3)赤色顔料と青色顔料と黄色顔料と紫色顔料とを含有する態様。
(4)赤色顔料と青色顔料と黄色顔料と紫色顔料と緑色顔料とを含有する態様。
(5)赤色顔料と青色顔料と黄色顔料と緑色顔料とを含有する態様。
(6)赤色顔料と青色顔料と緑色顔料とを含有する態様。
(7)黄色顔料と紫色顔料とを含有する態様。
白色顔料としては、酸化チタン、チタン酸ストロンチウム、チタン酸バリウム、酸化亜鉛、酸化マグネシウム、酸化ジルコニウム、酸化アルミニウム、硫酸バリウム、シリカ、タルク、マイカ、水酸化アルミニウム、ケイ酸カルシウム、ケイ酸アルミニウム、中空樹脂粒子、硫化亜鉛などが挙げられる。白色顔料は、チタン原子を有する粒子が好ましく、酸化チタンがより好ましい。また、白色顔料は、波長589nmの光に対する屈折率が2.10以上の粒子であることが好ましい。前述の屈折率は、2.10~3.00であることが好ましく、2.50~2.75であることがより好ましい。
黒色顔料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、カーボンブラック、チタンブラック、グラファイト等が挙げられ、カーボンブラック、チタンブラックが好ましく、チタンブラックがより好ましい。チタンブラックとは、チタン原子を含有する黒色粒子であり、低次酸化チタンや酸窒化チタンが好ましい。チタンブラックは、分散性向上、凝集性抑制などの目的で必要に応じ、表面を修飾することが可能である。例えば、酸化珪素、酸化チタン、酸化ゲルマニウム、酸化アルミニウム、酸化マグネシウム、又は、酸化ジルコニウムでチタンブラックの表面を被覆することが可能である。また、特開2007-302836号公報に表されるような撥水性物質での処理も可能である。黒色顔料として、C.I.Pigment Black 1,7等が挙げられる。チタンブラックは、個々の粒子の一次粒子径及び平均一次粒子径のいずれもが小さいことが好ましい。具体的には、平均一次粒子径が10~45nmであることが好ましい。チタンブラックは、分散物として用いることもできる。例えば、チタンブラック粒子とシリカ粒子とを含み、分散物中のSi原子とTi原子との含有比が0.20~0.50の範囲に調整された分散物などが挙げられる。上記分散物については、特開2012-169556号公報の段落0020~0105の記載を参酌でき、この内容は本明細書に組み込まれる。チタンブラックの市販品の例としては、チタンブラック10S、12S、13R、13M、13M-C、13R-N、13M-T(商品名:三菱マテリアル(株)製)、ティラック(Tilack)D(商品名:赤穂化成(株)製)などが挙げられる。
近赤外線吸収顔料は、有機顔料であることが好ましい。また、近赤外線吸収顔料は、波長700nmを超え1400nm以下の範囲に極大吸収波長を有することが好ましい。また、近赤外線吸収顔料の極大吸収波長は、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、近赤外線吸収顔料は、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顔料とすることができる。なお、本発明において、近赤外線吸収顔料の極大吸収波長および各波長における吸光度の値は、近赤外線吸収顔料を含む樹脂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。
本発明の樹脂組成物は染料を含んでいてもよい。染料としては特に制限はなく、公知の染料が使用できる。染料としては、有彩色染料、黒色染料、近赤外線吸収染料などが挙げられる。染料としては、公知の染料を用いることができる。また、特開2019-073695号公報に記載のメチン染料、特開2019-073696号公報に記載のメチン染料、特開2019-073697号公報に記載のメチン染料、特開2019-073698号公報に記載のメチン染料等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。
本発明の樹脂組成物は、樹脂を含有する。樹脂は、例えば、顔料を樹脂組成物中で分散させる用途やバインダーの用途で配合される。なお、主に顔料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使用することもできる。
本発明の樹脂組成物において、樹脂としては、酸基を有する樹脂が用いられる。本発明の樹脂組成物は、分散剤として酸基を有する樹脂を含むことが好ましい。この態様によれば、顔料と化合物Aと酸基を有する樹脂との間で上述したネットワーク構造が形成されやすく、樹脂組成物の保存安定性をより効果的に向上できる。なお、酸基を有する樹脂はバインダーとして含まれていてもよい。酸基を有する樹脂は、例えば、アルカリ可溶性樹脂として用いることができる。
式(Ac-2)中、Ar10は芳香族カルボキシル基を含む基を表し、L11は、-COO-または-CONH-を表し、L12は3価の連結基を表し、P10はポリマー鎖を表す。
式(Ar-12)中、n2は1~8の整数を表し、1~4の整数であることが好ましく、1または2であることがより好ましく、2であることが更に好ましい。
式(Ar-13)中、n3およびn4はそれぞれ独立して0~4の整数を表し、0~2の整数であることが好ましく、1または2であることがより好ましく、1であることが更に好ましい。ただし、n3およびn4の少なくとも一方は1以上の整数である。
式(Ar-13)中、Q1は、単結合、-O-、-CO-、-COOCH2CH2OCO-、-SO2-、-C(CF3)2-、上記式(Q-1)で表される基または上記式(Q-2)で表される基を表す。
式(Ar-11)~(Ar-13)中、*1はL1との結合位置を表す。
上記式において、RP3は、水素原子またはメチル基を表す。
上記式において、LP1は、単結合またはアリーレン基を表し、LP2は、単結合または2価の連結基を表す。LP1は、単結合であることが好ましい。LP2が表す2価の連結基としては、アルキレン基(好ましくは炭素数1~12のアルキレン基)、アリーレン基(好ましくは炭素数6~20のアリーレン基)、-NH-、-SO-、-SO2-、-CO-、-O-、-COO-、-OCO-、-S-、-NHCO-、-CONH-、およびこれらの2以上を組み合わせてなる基が挙げられる。
RP4は、水素原子又は置換基を表す。置換基としては、ヒドロキシ基、カルボキシル基、アルキル基、アリール基、ヘテロアリール基、アルコキシ基、アリールオキシ基、ヘテロアリールオキシ基、アルキルチオエーテル基、アリールチオエーテル基、ヘテロアリールチオエーテル基、(メタ)アクリロイル基、オキセタニル基、ブロックイソシアネート基等が挙げられる。なお、本明細書におけるブロックイソシアネート基とは、熱によりイソシアネート基を生成することが可能な基であり、例えば、ブロック剤とイソシアネート基とを反応させイソシアネート基を保護した基が好ましく例示できる。ブロック剤としては、オキシム化合物、ラクタム化合物、フェノール化合物、アルコール化合物、アミン化合物、活性メチレン化合物、ピラゾール化合物、メルカプタン化合物、イミダゾール系化合物、イミド系化合物等を挙げることができる。ブロック剤については、特開2017-067930号公報の段落0115~0117に記載された化合物が挙げられ、この内容は本明細書に組み込まれる。また、ブロックイソシアネート基は、90℃~260℃の熱によりイソシアネート基を生成することが可能な基であることが好ましい。
本発明の樹脂組成物は、酸基を含まない樹脂を更に含有することができる。このような樹脂としては、特に限定はなく、(メタ)アクリル樹脂、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。
本発明の樹脂組成物は、1分子中に塩基性基を3個以上含み、アミン価が2.7mmol/g以上で、分子量が100以上の化合物Aを含む。
本発明の樹脂組成物は、顔料誘導体を含有することができる。この態様によれば、樹脂組成物の保存安定性をより向上させることができる。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、イミニウム色素骨格、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、スルホ基、カルボキシル基、リン酸基及びこれらの塩が挙げられる。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。
本発明の樹脂組成物は、重合性化合物を含有することが好ましい。重合性化合物としては、ラジカル、酸または熱により架橋可能な公知の化合物を用いることができる。本発明において、重合性化合物は、例えば、エチレン性不飽和結合含有基を有する化合物であることが好ましい。エチレン性不飽和結合含有基としては、ビニル基、(メタ)アリル基、(メタ)アクリロイル基などが挙げられる。本発明で用いられる重合性化合物は、ラジカル重合性化合物であることが好ましい。
本発明の樹脂組成物は光重合開始剤を含むことが好ましい。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、紫外線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。光重合開始剤は、光ラジカル重合開始剤であることが好ましい。
RX2は、アルキル基、アルケニル基、アルコキシ基、アリール基、アリールオキシ基、複素環基、複素環オキシ基、アルキルスルファニル基、アリールスルファニル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、アシルオキシ基またはアミノ基を表し、
RX3~RX14は、それぞれ独立して水素原子または置換基を表す;
ただし、RX10~RX14のうち少なくとも一つは、電子求引性基である。
本発明の樹脂組成物は、環状エーテル基を有する化合物を含有することができる。環状エーテル基としては、エポキシ基、オキセタニル基などが挙げられる。環状エーテル基を有する化合物は、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)であることが好ましい。エポキシ化合物としては、1分子内にエポキシ基を1つ以上有する化合物が挙げられ、エポキシ基を2つ以上有する化合物が好ましい。エポキシ化合物はエポキシ基を1分子内に1~100個有する化合物であることが好ましい。エポキシ化合物に含まれるエポキシ基の上限は、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。エポキシ化合物に含まれるエポキシ基の下限は、2個以上が好ましい。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、特開2017-179172号公報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。
本発明の樹脂組成物は、硬化促進剤を含んでもよい。硬化促進剤としては、チオール化合物、メチロール化合物、アミン化合物、ホスホニウム塩化合物、アミジン塩化合物、アミド化合物、塩基発生剤、イソシアネート化合物、アルコキシシラン化合物、オニウム塩化合物などが挙げられる。硬化促進剤の具体例としては、国際公開第2018/056189号の段落番号0094~0097に記載の化合物、特開2015-034963号公報の段落番号0246~0253に記載の化合物、特開2013-041165号公報の段落番号0186~0251に記載の化合物、特開2014-055114号公報に記載のイオン性化合物、特開2012-150180号公報の段落番号0071~0080に記載の化合物、特開2011-253054号公報に記載のアルコキシシラン化合物、特許第5765059号公報の段落番号0085~0092に記載の化合物、特開2017-036379号公報に記載のカルボキシル基含有エポキシ硬化剤などが挙げられる。樹脂組成物の全固形分中における硬化促進剤の含有量は0.3~8.9質量%が好ましく、0.8~6.4質量%がより好ましい。
本発明の樹脂組成物は、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、シリコー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。界面活性剤については、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。
本発明の樹脂組成物は、溶剤を含有することができる。溶剤の種類は、各成分の溶解性や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。溶剤は、有機溶剤であることが好ましい。有機溶剤としては、エステル系溶剤、ケトン系溶剤、アルコール系溶剤、アミド系溶剤、エーテル系溶剤、炭化水素系溶剤などが挙げられる。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も好ましく用いることもできる。有機溶剤の具体例としては、ポリエチレングリコールモノメチルエーテル、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、プロピレングリコールモノメチルエーテルアセテート、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、プロピレングリコールジアセテート、3-メトキシブタノールなどが挙げられる。ただし有機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)。
本発明の樹脂組成物は、シランカップリング剤を含有することができる。本明細書において、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)アリル基、(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、アミノ基、(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の具体例としては、N-β-アミノエチル-γ-アミノプロピルメチルジメトキシシラン(信越化学工業(株)製、商品名 KBM-602)、N-β-アミノエチル-γ-アミノプロピルトリメトキシシラン(信越化学工業(株)製、商品名 KBM-603)、N-β-アミノエチル-γ-アミノプロピルトリエトキシシラン(信越化学工業(株)製、商品名 KBE-602)、γ-アミノプロピルトリメトキシシラン(信越化学工業(株)製、商品名 KBM-903)、γ-アミノプロピルトリエトキシシラン(信越化学工業(株)製、商品名 KBE-903)、3-メタクリロキシプロピルメチルジメトキシシラン(信越化学工業(株)製、商品名 KBM-502)、3-メタクリロキシプロピルトリメトキシシラン(信越化学工業(株)製、商品名 KBM-503)等がある。また、シランカップリング剤の具体例については、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。
本発明の樹脂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。樹脂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、それらの合計量が上記範囲となることが好ましい。
本発明の樹脂組成物は、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。また、酸化防止剤は、韓国公開特許第10-2019-0059371号公報に記載の化合物を用いることもできる。樹脂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。
本発明の樹脂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。樹脂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。重合禁止剤は、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。
本発明において、樹脂組成物は、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、本発明の樹脂組成物は、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。潜在酸化防止剤の市販品としては、アデカアークルズGPA-5001((株)ADEKA製)等が挙げられる。
樹脂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、原材料や樹脂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、樹脂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。
本発明の樹脂組成物は、前述の成分を混合して調製できる。樹脂組成物の調製に際しては、全成分を同時に溶剤に溶解および/または分散して樹脂組成物を調製してもよいし、必要に応じて、各成分を適宜2つ以上の溶液または分散液としておいて、使用時(塗布時)にこれらを混合して樹脂組成物を調製してもよい。
本発明の膜は、上述した本発明の樹脂組成物から得られる膜である。本発明の膜の膜厚は、目的に応じて適宜調整できる。例えば、膜厚は、20μm以下が好ましく、10μm以下がより好ましく、5μm以下がさらに好ましい。膜厚の下限は、0.1μm以上が好ましく、0.2μm以上がより好ましく、0.3μm以上がさらに好ましい。
(i1):波長400~640nmの範囲における透過率の最大値が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800~1500nmの範囲における透過率の最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である膜。このような分光特性を有する膜は、波長400~640nmの範囲の光を遮光して、波長750nmを超える光を透過させることができる。
(i2):波長400~750nmの範囲における透過率の最大値が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900~1500nmの範囲における透過率の最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である膜。このような分光特性を有する膜は、波長400~750nmの範囲の光を遮光して、波長850nmを超える光を透過させることができる。
(i3):波長400~830nmの範囲における透過率の最大値が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1000~1500nmの範囲における透過率の最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である膜。このような分光特性を有する膜は、波長400~830nmの範囲の光を遮光して、波長950nmを超える光を透過させることができる。
(i4):波長400~950nmの範囲における透過率の最大値が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1100~1500nmの範囲における透過率の最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である膜。このような分光特性を有する膜は、波長400~950nmの範囲の光を遮光して、波長1050nmを超える光を透過させることができる。
(i5):波長400~1050nmの範囲における透過率の最大値が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1200~1500nmの範囲における透過率の最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である膜。このような分光特性を有する膜は、波長400~1050nmの範囲の光を遮光して、波長1150nmを超える光を透過させることができる。
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、本発明の樹脂組成物を塗布する工程を経て製造できる。膜の製造方法においては、更にパターン(画素)を形成する工程を含むことが好ましい。パターン(画素)の形成方法としては、フォトリソグラフィ法、ドライエッチング法が挙げられ、フォトリソグラフィ法が好ましい。
本発明の光学フィルタは、上述した本発明の膜を有する。光学フィルタの種類としては、カラーフィルタ、近赤外線カットフィルタおよび近赤外線透過フィルタなどが挙げられ、カラーフィルタであることが好ましい。カラーフィルタは、その画素として本発明の膜を有することが好ましく、着色画素として本発明の膜を有することがより好ましく、緑色画素として本発明の膜を有することが更に好ましい。
本発明の固体撮像素子は、上述した本発明の膜を有する。本発明の固体撮像素子の構成としては、本発明の膜を備え、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が、例えば、以下のような構成が挙げられる。
本発明の画像表示装置は、上述した本発明の膜を有する。画像表示装置としては、液晶表示装置や有機エレクトロルミネッセンス表示装置などが挙げられる。画像表示装置の定義や各画像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に特に制限はなく、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。
カラムの種類:TOSOH TSKgel Super HZM-Hと、TOSOH TSKgel Super HZ4000と、TOSOH TSKgel Super HZ2000とを連結したカラム
展開溶媒:テトラヒドロフラン
カラム温度:40℃
流量(サンプル注入量):1.0μL(サンプル濃度:0.1質量%)
装置名:東ソー製 HLC-8220GPC
検出器:RI(屈折率)検出器
検量線ベース樹脂:ポリスチレン樹脂
アミン価は、以下の方法で算出した。
測定サンプルを酢酸に溶解し、電位差滴定装置(商品名:AT-510、京都電子工業製)を用いて、得られた溶液を0.1mol/L過塩素酸/酢酸溶液で中和滴定した。滴定pH曲線の変曲点を滴定終点として、以下の式によりアミン価を算出した。
B=Vs×0.1×f/w
B:アミン価(mmol/g)
Vs:滴定に要した0.1mol/L過塩素酸/酢酸溶液の使用量(mL)
f:0.1M過塩素酸/酢酸溶液の力価
w:測定サンプルの重量(g)(固形分換算)
(分散液処方1)
顔料を14質量部と、特定化合物と顔料誘導体と樹脂とを固形分換算で合計で3.5質量部と、溶剤を82.5質量部との混合液を、ビーズミル(ジルコニアビーズ0.1mm径)を用いて3時間混合および分散して、分散液を調製した。その後、減圧機構付き高圧分散機NANO-3000-10(日本ビーイーイー(株)製)を用いて、圧力2000kg/cm2および流量500g/minの条件の下、分散処理を行なった。この分散処理を全10回まで繰り返して、分散液を得た。なお、顔料、顔料誘導体、樹脂、特定化合物および溶剤はそれぞれ下記表に示す素材を用いた。また、下記表中における顔料誘導体、樹脂、特定化合物の混合比率は固形分換算での値である。
顔料を14質量部と、特定化合物と顔料誘導体と樹脂とを固形分換算で合計で4.9質量部と、溶剤を81.1質量部との混合液を、ビーズミル(ジルコニアビーズ0.1mm径)を用いて3時間混合および分散して、分散液を調製した。その後、減圧機構付き高圧分散機NANO-3000-10(日本ビーイーイー(株)製)を用いて、圧力2000kg/cm2および流量500g/minの条件の下、分散処理を行なった。この分散処理を全10回まで繰り返して、分散液を得た。なお、顔料、顔料誘導体、樹脂、特定化合物および溶剤はそれぞれ下記表に示す素材を用いた。また、下記表中における顔料誘導体、樹脂、特定化合物の混合比率は固形分換算での値である。
P-1: C.I.Pigment Green7(ハロゲン化銅フタロシアニン顔料、緑色顔料)
P-2: C.I.Pigment Green36(ハロゲン化銅フタロシアニン顔料、緑色顔料)
P-3: C.I.Pigment Green58(ハロゲン化亜鉛フタロシアニン顔料、緑色顔料)
P-4: C.I.Pigment Green59(ハロゲン化亜鉛フタロシアニン顔料、緑色顔料)
P-5: C.I.Pigment Green63(ハロゲン化アルミニウムフタロシアニン顔料、緑色顔料)
P-6: C.I.Pigment Yellow129(アゾメチン銅錯体顔料、黄色顔料)
P-7: C.I.Pigment Yellow138(黄色顔料)
P-8: C.I.Pigment Yellow139(黄色顔料)
P-9: C.I.Pigment Yellow150(アゾニッケル金属錯体顔料、黄色顔料)
P-10: C.I.Pigment Yellow185(黄色顔料)
P-11: C.I.Pigment Yellow215(黄色顔料)
P-12: C.I.Pigment Yellow231(黄色顔料)
P-13: C.I.Pigment Yellow233(黄色顔料)
P-14: C.I.Pigment Red122(赤色顔料)
P-15: C.I.Pigment Red177(赤色顔料)
P-16: C.I.Pigment Red254(赤色顔料)
P-17: C.I.Pigment Red264(赤色顔料)
P-18: C.I.Pigment Red269(赤色顔料)
P-19: C.I.Pigment Red272(赤色顔料)
P-20: C.I.Pigment Blue15:4(銅フタロシアニン顔料、青色顔料)
P-21: C.I.Pigment Blue15:6(銅フタロシアニン顔料、青色顔料)
P-22: C.I.Pigment Blue16(青色顔料)
P-23: C.I.Pigment Violet23(紫色顔料)
P-24: TiO2(チタン原子を含む顔料、白色顔料)
P-25: TiON(チタン原子を含む顔料、黒色顔料)
P-26: 下記構造の化合物(近赤外線吸収顔料)
A-1: ポリエチレンイミン(エポミンSP-003、(株)日本触媒製)
A-2: ポリエチレンイミン(エポミンSP-006、(株)日本触媒製)
A-3: ポリエチレンイミン(エポミンSP-012、(株)日本触媒製)
A-4: ポリエチレンイミン(エポミンSP-018、(株)日本触媒製)
A-5: ポリエチレンイミン(エポミンSP-200、(株)日本触媒製)
A-6: ポリエチレンイミン(エポミンP-1000、(株)日本触媒製)
A-7: 下記構造の化合物(ヒンダードアミン化合物、アデカスタブLA-52、(株)ADEKA製)
A-8: 下記構造の化合物(ヒンダードアミン化合物、アデカスタブLA-57、(株)ADEKA製)
A-9: 下記構造の化合物(ヒンダードアミン化合物、アデカスタブLA-63P、(株)ADEKA製)
A-10: 下記構造の化合物(ヒンダードアミン化合物、アデカスタブLA-68、(株)ADEKA製)
A-11: 下記構造の化合物
A-12: 下記構造の化合物
A-13: 下記構造の化合物
A-14: 下記構造の化合物
AN-1: 下記構造の化合物
AN-2: 下記構造の化合物
AN-3: 下記構造の樹脂(主鎖に付記した数値は質量比である)
Syn-1:下記構造の化合物(アミン価2.2mmol/g、アミノ基を2個有する化合物)
B-1:以下の方法で合成した樹脂B-1の30質量%PGMEA溶液。
メチルメタクリレート50質量部、n-ブチルメタクリレート30質量部、t-ブチルメタクリレート20質量部、プロピレングリコールモノメチルエーテルアセテート(PGMEA)45.4質量部を反応容器に仕込み、雰囲気ガスを窒素ガスで置換した。反応容器内を70℃に加熱して、3-メルカプト-1,2-プロパンジオール6質量部を添加して、さらにAIBN(アゾビスイソブチロニトリル)0.12質量部を加え、12時間反応させた。固形分測定により95%が反応したことを確認した。次に、ピロメリット酸無水物9.7質量部、PGMEA70.3質量部、触媒としてDBU(1,8-ジアザビシクロ-[5.4.0]-7-ウンデセン)0.20質量部を追加し、120℃で7時間反応させた。酸価の測定で98%以上の酸無水物がハーフエステル化していることを確認し反応を終了して、酸価43mgKOH/g、重量平均分子量9000の下記構造の樹脂B-1(酸基を有する樹脂)を得た。
3-メルカプト-1,2-プロパンジオール6.0質量部、ピロメリット酸無水物9.5質量部、PGMEA62質量部、1,8-ジアザビシクロ-[5.4.0]-7-ウンデセン0.2質量部を反応容器に仕込み、雰囲気ガスを窒素ガスで置換した。反応容器内を100℃に加熱して、7時間反応させた。酸価の測定で98%以上の酸無水物がハーフエステル化していることを確認した後、系内の温度を70℃に冷却し、メチルメタクリレート65質量部、エチルアクリレート5.0質量部、t-ブチルアクリレート15質量部、メタクリル酸5.0質量部、ヒドロキシエチルメタクリレート10質量部、2,2’-アゾビスイソブチロニトリル0.1質量部を溶解したPGMEA溶液53.5質量部を添加して、10時間反応させた。固形分測定により重合が95%進行したことを確認し反応を終了して、酸価70.5mgKOH/g、重量平均分子量10000の下記構造の樹脂B-2(酸基を有する樹脂)を得た。
樹脂B-1の合成において、t-ブチルメタクリレート20質量部を、(3-エチルオキセタン-3-イル)メチルメタクリレート20質量部に変更した以外は同様にして、酸価43mgKOH/g、重量平均分子量9000の下記構造の樹脂B-3(酸基を有する樹脂)を得た。
1-チオグリセロール108質量部、ピロメリット酸無水物174質量部、メトキシプロピルアセテート650質量部、触媒としてモノブチルスズオキシド0.2質量部を反応容器に仕込み、雰囲気ガスを窒素ガスで置換した後、120℃で5時間反応させた(第一工程)。酸価の測定で95%以上の酸無水物がハーフエステル化していることを確認した。次に、第一工程で得られた化合物を固形分換算で160質量部、2-ヒドロキシプロピルメタクリレート200質量部、エチルアクリレート200質量部、t-ブチルアクリレート150質量部、2-メトキシエチルアクリレート200質量部、メチルアクリレート200質量部、メタクリル酸50質量部、PGMEA663質量部を反応容器に仕込み、反応容器内を80℃に加熱して、2,2’-アゾビス(2,4-ジメチルバレロニトリル)1.2質量部を添加し、12時間反応させた(第二工程)。固形分測定により95%が反応したことを確認した。最後に、第二工程で得られた化合物の50質量%PGMEA溶液500質量部、2-メタクリロイルオキシエチルイソシアネート(MOI)27.0質量部、ヒドロキノン0.1質量部を反応容器に仕込み、イソシアネート基に基づく2270cm-1のピークの消失を確認するまで反応を行った(第三工程)。ピーク消失の確認後、反応溶液を冷却して、酸価68mgKOH/g、エチレン性不飽和結合基価0.62mmol/g、重量平均分子量13000の下記構造の樹脂B-4(酸基を有する樹脂)を得た。
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(PGMEA)
S-2:プロピレングリコールモノメチルエーテル(PGME)
S-3:シクロヘキサノン
S-4:シクロペンタノン
S-5:2-ヘプタノン
S-6:ガンマブチロラクトン
各素材を、以下に示す処方1~5の割合で混合し、孔径0.45μmのナイロン製フィルタ(日本ポール(株)製)でろ過して各樹脂組成物を製造した。下記表において、樹脂組成物の全固形分中における顔料の含有量の値を「顔料濃度」の欄に記載する。
下記表に記載の分散液 ・・・51.4質量部
下記表に記載の重合性モノマー ・・・3.6質量部
下記表に記載の樹脂 ・・・12.5質量部(30質量%PGMEA溶液での配合量)
下記表に記載の光重合開始剤 ・・・0.9質量部
下記表に記載の界面活性剤 ・・・0.02質量部
下記表に記載の重合禁止剤 ・・・0.0002質量部
下記表に記載の溶剤 ・・・31.5質量部
下記表に記載の分散液 ・・・64.3質量部
下記表に記載の重合性モノマー ・・・2.7質量部
下記表に記載の樹脂 ・・・7.4質量部(30質量%PGMEA溶液での配合量)
下記表に記載の光重合開始剤 ・・・0.9質量部
下記表に記載の界面活性剤 ・・・0.02質量部
下記表に記載の重合禁止剤 ・・・0.0002質量部
下記表に記載の溶剤 ・・・24.7質量部
下記表に記載の分散液 ・・・77.1質量部
下記表に記載の重合性モノマー ・・・0.9質量部
下記表に記載の樹脂 ・・・6.5質量部(30質量%PGMEA溶液での配合量)
下記表に記載の光重合開始剤 ・・・0.5質量部
下記表に記載の界面活性剤 ・・・0.02質量部
下記表に記載の重合禁止剤 ・・・0.0002質量部
下記表に記載の溶剤 ・・・14.9質量部
下記表に記載の分散液 ・・・83.6質量部
下記表に記載の重合性モノマー ・・・0.9質量部
下記表に記載の樹脂 ・・・5.2質量部(30質量%PGMEA溶液での配合量)
下記表に記載の光重合開始剤 ・・・0.5質量部
下記表に記載の界面活性剤 ・・・0.02質量部
下記表に記載の重合禁止剤 ・・・0.0002質量部
下記表に記載の溶剤 ・・・9.8質量部
下記表に記載の分散液 ・・・77.1質量部
下記表に記載の重合性モノマー ・・・0.9質量部
下記表に記載の樹脂 ・・・5.3質量部(30質量%PGMEA溶液での配合量)
下記表に記載の光重合開始剤 ・・・0.5質量部
下記表に記載の特定化合物の30質量%シクロペンタノン溶液 ・・・1.2質量部
下記表に記載の界面活性剤 ・・・0.02質量部
下記表に記載の重合禁止剤 ・・・0.0002質量部
下記表に記載の溶剤 ・・・14.9質量部
I-1:Irgacure OXE01(BASF社製、オキシム化合物)
I-2:Irgacure OXE02(BASF社製、オキシム化合物)
I-3、I-4:下記構造の化合物
B-1~B-8:上述した樹脂B-1~B-8(30質量%PGMEA溶液)
A-2:上述した特定化合物A-2
In-1:p-メトキシフェノール
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(PGMEA)
製造直後の樹脂組成物の初期粘度(V0)を、東機産業(株)製「RE-85L」にて測定した。初期粘度(V0)を測定後、樹脂組成物を4℃の温度にて、6か月静置したのち、静置後の粘度(V1)を測定した。下記式から静置後の樹脂組成物の粘度変動率(%)を算出し、以下の基準により保存安定性を評価した。樹脂組成物の粘度は25℃に温度調整を施した状態で測定した。
粘度変動率(%)=((静置後の粘度(V1)-初期粘度(V0))/初期粘度(V0))×100
5:粘度変動率が5%未満である
4:粘度変動率が5%以上10%未満である
3:粘度変動率が10%以上30%未満である
2:粘度変動率が30%以上100%未満である
1:粘度変動率が100%以上である
直径8インチ(20.32cm)のシリコンウエハ上に、下地層用組成物をスピンコート法で塗布し、次いでホットプレートを用いて、100℃で2分間加熱し、次いで、ホットプレートを用いて230℃で2分間加熱して膜厚10nmの下地層を形成した。下地層用組成物については後述する。
次に、下地層を形成したシリコンウエハ上に、実施例1~128、比較例1~3の樹脂組成物を、製膜後の膜厚が0.4μmになるようにスピンコート法で塗布し、次いで、ホットプレートを用いて100℃で2分間加熱した。次いで、i線ステッパー露光装置FPA-3000i5+(Canon(株)製)を用い、1.0μmのアイランドパターンを有するマスクを介して、150mJ/cm2の露光量で露光した。次いで、温度23℃、湿度50%の環境下にて、30分間保管した後、水酸化テトラメチルアンモニウム(TMAH)0.3質量%水溶液を用い、23℃で60秒間パドル現像を行った。その後、スピンシャワーにてリンスを行い、さらに純水にて水洗した後に、ホットプレートを用いて220℃で5分間加熱してアイランドパターンの画素を形成した。
アイランドパターンが形成されたシリコンウエハについて、恒温試験(温度150℃の環境下での2000時間の保持)を実施した後に、シリコンウエハ面内の30点を光学顕微鏡で観察し、膜中の異物の発生の有無を確認した。評価結果を下記表に示す。
5: 恒温試験後に異物が観察された箇所が0箇所
4: 恒温試験後に異物が観察された箇所が1~3箇所
3: 恒温試験後に異物が観察された箇所が4~10箇所
2: 恒温試験後に異物が観察された箇所が11~20箇所
1: 恒温試験後に異物が観察された箇所が21~30箇所
直径8インチ(20.32cm)のガラスウエハ上に、下地層用組成物をスピンコート法で塗布し、次いでホットプレートを用いて、100℃で2分間加熱し、次いで、ホットプレートを用いて230℃で2分間加熱して膜厚10nmの下地層を形成した。下地層用組成物については後述する。
次に、下地層を形成したガラスウエハ上に、実施例1~23、28~85、88~128、比較例1~3の樹脂組成物を、製膜後の膜厚が0.4μmになるようにスピンコート法で塗布し、次いで、ホットプレートを用いて100℃で2分間加熱した。次いで、i線ステッパー露光装置FPA-3000i5+(Canon(株)製)を用い、2cmのアイランドパターンを有するマスクを介して、150mJ/cm2の露光量で露光した。次いで、ガラスウエハを温度23℃、湿度50%の環境下にて30分間保管した後、水酸化テトラメチルアンモニウム(TMAH)0.3質量%水溶液を用い、23℃で60秒間パドル現像を行った。その後、スピンシャワーにてリンスを行い、さらに純水にて水洗した後に、ホットプレートを用いて220℃で5分間加熱して分光評価用のパターンを形成した。
分光測定用パターンが形成されたガラスウエハについて、恒温試験(温度150℃の環境下での2000時間の保持)を実施した前後での波長400~700nmの光の透過率の変動率を求めた。
透過率の変動率(%)=(|T2-T1|/T1)×100
T1は恒温試験前の波長400~700nmの光の透過率の積分値であり、T2は恒温試験後の波長400~700nmの光の透過率の積分値である。
5: 透過率の変動率が3%未満
4: 透過率の変動率が3%以上5%未満
3: 透過率の変動率が5%以上10%未満
2: 透過率の変動率が10%以上20%未満
1: 透過率の変動率が20%以上
下地層用組成物は、下記原料を混合して製造した。
樹脂A ・・・0.7質量部
界面活性剤A ・・・0.8質量部
プロピレングリコールモノメチルエーテルアセテート(PGMEA) ・・・98.5質量部
・樹脂A:サイクロマーP(ACA)230AA ((株)ダイセル製、酸価=30mgKOH/g、Mw=15000、54質量%PGME溶液)
・界面活性剤A:下記構造の化合物(Mw=14000、繰り返し単位の割合を示す%の数値はモル%である、フッ素系界面活性剤)の0.2質量%PGMEA溶液
シリコンウエハ上に、下地層用組成物をスピンコート法で塗布し、次いでホットプレートを用いて、100℃で2分間加熱し、次いで、ホットプレートを用いて230℃で2分間加熱して膜厚10nmの下地層を形成した。下地層用組成物については異物評価で用いた下地層用組成物と同様である。
次に、下地層を形成したシリコンウエハ上に、緑色樹脂組成物を製膜後の膜厚が1.0μmになるようにスピンコート法で塗布した。次いで、ホットプレートを用いて、100℃で2分間加熱した。次いで、i線ステッパー露光装置FPA-3000i5+(キヤノン(株)製)を用い、1000mJ/cm2の露光量で2μm四方のドットパターンのマスクを介して露光した。次いで、水酸化テトラメチルアンモニウム(TMAH)0.3質量%水溶液を用い、23℃で60秒間パドル現像を行った。その後、スピンシャワーにてリンスを行い、更に純水にて水洗した。次いで、ホットプレートを用いて、200℃で5分間加熱することで、緑色樹脂組成物をパターニングして緑色画素を形成した。同様に赤色樹脂組成物、青色樹脂組成物を同様のプロセスでパターニングして、赤色画素、青色画素を順次形成して、緑色画素、赤色画素および青色画素を有するカラーフィルタを形成した。このカラーフィルタにおいては、緑色画素がベイヤーパターンで形成されており、その隣接する領域に、赤色画素、青色画素がアイランドパターンで形成されている。得られたカラーフィルタを公知の方法に従い固体撮像素子に組み込んだ。この固体撮像素子は好適な画像認識能を有していた。なお、緑色樹脂組成物は実施例99の樹脂組成物を用いた。赤色樹脂組成物は実施例79の樹脂組成物を用いた。青色樹脂組成物は実施例84の樹脂組成物を用いた。
Claims (15)
- 顔料と、
1分子中に塩基性基を3個以上含み、アミン価が2.7mmol/g以上で、分子量が100以上の化合物Aと、
酸基を有する樹脂とを含む樹脂組成物であり、
前記樹脂組成物の全固形分中に前記顔料を40質量%以上含む樹脂組成物。 - 化合物Aが有する塩基性基がアミノ基である、請求項1に記載の樹脂組成物。
- 前記化合物Aのアミン価が15mmol/g以上である、請求項1または2に記載の樹脂組成物。
- 前記化合物Aがポリアルキレンイミンである、請求項1~3のいずれか1項に記載の樹脂組成物。
- 前記化合物Aがポリエチレンイミンである、請求項1~3のいずれか1項に記載の樹脂組成物。
- 前記化合物Aの分子量が2000以下である、請求項1~5のいずれか1項に記載の樹脂組成物。
- 前記顔料は有彩色顔料を含む、請求項1~6のいずれか1項に記載の樹脂組成物。
- 前記顔料は金属原子を含む顔料を含む、請求項1~7のいずれか1項に記載の樹脂組成物。
- 前記顔料はハロゲン化亜鉛フタロシアニン顔料を含む、請求項1~8のいずれか1項に記載の樹脂組成物。
- 前記樹脂組成物の全固形分中に前記顔料を60質量%以上含む、請求項1~9のいずれか1項に記載の樹脂組成物。
- 更に顔料誘導体を含む、請求項1~10のいずれか1項に記載の樹脂組成物。
- 請求項1~11のいずれか1項に記載の樹脂組成物を用いて得られる膜。
- 請求項12に記載の膜を有する光学フィルタ。
- 請求項12に記載の膜を有する固体撮像素子。
- 請求項12に記載の膜を有する画像表示装置。
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020227039514A KR102869416B1 (ko) | 2020-05-22 | 2021-05-17 | 수지 조성물, 막, 광학 필터, 고체 촬상 소자 및 화상 표시 장치 |
| CN202180032489.9A CN115516039B (zh) | 2020-05-22 | 2021-05-17 | 树脂组合物、膜、滤光器、固体摄像元件及图像显示装置 |
| JP2022524452A JP7344379B2 (ja) | 2020-05-22 | 2021-05-17 | 樹脂組成物、膜、光学フィルタ、固体撮像素子および画像表示装置 |
| US18/057,349 US20230159752A1 (en) | 2020-05-22 | 2022-11-21 | Resin composition, film, optical filter, solid-state imaging element, and image display device |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020089720 | 2020-05-22 | ||
| JP2020-089720 | 2020-05-22 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US18/057,349 Continuation US20230159752A1 (en) | 2020-05-22 | 2022-11-21 | Resin composition, film, optical filter, solid-state imaging element, and image display device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2021235373A1 true WO2021235373A1 (ja) | 2021-11-25 |
Family
ID=78708440
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2021/018527 Ceased WO2021235373A1 (ja) | 2020-05-22 | 2021-05-17 | 樹脂組成物、膜、光学フィルタ、固体撮像素子および画像表示装置 |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20230159752A1 (ja) |
| JP (1) | JP7344379B2 (ja) |
| KR (1) | KR102869416B1 (ja) |
| CN (1) | CN115516039B (ja) |
| TW (1) | TWI881123B (ja) |
| WO (1) | WO2021235373A1 (ja) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2025041642A1 (ja) * | 2023-08-23 | 2025-02-27 | 富士フイルム株式会社 | 組成物、膜、光学フィルタ、固体撮像素子および画像表示装置 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI889415B (zh) * | 2024-06-25 | 2025-07-01 | 台虹應用材料股份有限公司 | 暫時接著層、多層結構、暫時接著用組成物及裝置的封裝方法 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1036648A (ja) * | 1996-07-25 | 1998-02-10 | Konica Corp | 固体分散組成物、感光性組成物及びカラープルーフ用感光材料 |
| JP2010084119A (ja) * | 2008-09-02 | 2010-04-15 | Fujifilm Corp | 加工顔料、顔料分散組成物、光硬化性組成物、カラーフィルタ、及びカラーフィルタの製造方法 |
| JP2012053278A (ja) * | 2010-09-01 | 2012-03-15 | Fujifilm Corp | 着色感光性組成物、カラーフィルタの製造方法、カラーフィルタ、および液晶表示装置 |
| JP2014191102A (ja) * | 2013-03-26 | 2014-10-06 | Fuji Xerox Co Ltd | 液体現像剤、画像形成装置、画像形成方法、プロセスカートリッジ、及び液体現像剤カートリッジ |
| JP2017187765A (ja) * | 2016-03-31 | 2017-10-12 | 東友ファインケム株式会社Dongwoo Fine−Chem Co., Ltd. | 青色感光性樹脂組成物、これを含む青色カラーフィルタおよびディスプレイ素子 |
| JP2019174673A (ja) * | 2018-03-28 | 2019-10-10 | 花王株式会社 | 静電荷像現像用トナー |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5371449B2 (ja) * | 2008-01-31 | 2013-12-18 | 富士フイルム株式会社 | 樹脂、顔料分散液、着色硬化性組成物、これを用いたカラーフィルタ及びその製造方法 |
| CN101978004B (zh) * | 2008-03-17 | 2013-11-06 | 富士胶片株式会社 | 颜料分散组合物、着色感光性组合物、光固化性组合物、滤色器、液晶显示元件及固体摄像元件 |
| JP5224936B2 (ja) * | 2008-06-26 | 2013-07-03 | 富士フイルム株式会社 | 分散液、黒色硬化性組成物、製造方法、固体撮像素子用の遮光膜または反射防止膜の製造方法、および固体撮像素子 |
| KR101511202B1 (ko) * | 2008-09-02 | 2015-04-10 | 후지필름 가부시키가이샤 | 가공 안료, 안료 분산 조성물, 광경화성 조성물, 컬러 필터, 및 컬러 필터의 제조방법 |
| WO2011030726A1 (ja) * | 2009-09-09 | 2011-03-17 | Dic株式会社 | カラーフィルター用顔料分散組成物及びカラーフィルター |
| JP2013041145A (ja) | 2011-08-17 | 2013-02-28 | Toyo Ink Sc Holdings Co Ltd | カラーフィルタ用着色組成物、およびカラーフィルタ |
| WO2014069544A1 (ja) * | 2012-11-01 | 2014-05-08 | 富士フイルム株式会社 | 感光性組成物、これを用いた灰色硬化膜、灰色画素及び固体撮像素子 |
| JP6481479B2 (ja) * | 2014-04-24 | 2019-03-13 | Jsr株式会社 | 着色剤、硬化性組成物、硬化膜、並びに表示素子及び固体撮像素子 |
| CN106488941B (zh) * | 2014-07-04 | 2019-12-10 | 三菱化学株式会社 | 树脂、感光性树脂组合物、固化物、滤色片及图像显示装置 |
| KR102491715B1 (ko) * | 2015-03-27 | 2023-01-25 | 미쯔비시 케미컬 주식회사 | 착색 수지 조성물, 컬러 필터, 및 화상 표시 장치 |
| JP6733280B2 (ja) * | 2015-04-28 | 2020-07-29 | Jsr株式会社 | 着色剤分散液及びその製造方法、着色組成物及びその製造方法、着色硬化膜、表示素子並びに固体撮像素子 |
| JP2017171711A (ja) * | 2016-03-18 | 2017-09-28 | 味の素株式会社 | ポリアリルアミン誘導体及びポリエチレンイミン誘導体 |
| JP7037568B2 (ja) * | 2017-08-31 | 2022-03-16 | 富士フイルム株式会社 | 樹脂組成物、膜、近赤外線カットフィルタ、赤外線透過フィルタ、固体撮像素子、画像表示装置、赤外線センサおよびカメラモジュール |
| JP7010119B2 (ja) | 2018-04-06 | 2022-01-26 | 東洋インキScホールディングス株式会社 | カラーフィルタ用着色組成物、フィルタセグメント、およびカラーフィルタ |
-
2021
- 2021-05-17 CN CN202180032489.9A patent/CN115516039B/zh active Active
- 2021-05-17 KR KR1020227039514A patent/KR102869416B1/ko active Active
- 2021-05-17 TW TW110117614A patent/TWI881123B/zh active
- 2021-05-17 JP JP2022524452A patent/JP7344379B2/ja active Active
- 2021-05-17 WO PCT/JP2021/018527 patent/WO2021235373A1/ja not_active Ceased
-
2022
- 2022-11-21 US US18/057,349 patent/US20230159752A1/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1036648A (ja) * | 1996-07-25 | 1998-02-10 | Konica Corp | 固体分散組成物、感光性組成物及びカラープルーフ用感光材料 |
| JP2010084119A (ja) * | 2008-09-02 | 2010-04-15 | Fujifilm Corp | 加工顔料、顔料分散組成物、光硬化性組成物、カラーフィルタ、及びカラーフィルタの製造方法 |
| JP2012053278A (ja) * | 2010-09-01 | 2012-03-15 | Fujifilm Corp | 着色感光性組成物、カラーフィルタの製造方法、カラーフィルタ、および液晶表示装置 |
| JP2014191102A (ja) * | 2013-03-26 | 2014-10-06 | Fuji Xerox Co Ltd | 液体現像剤、画像形成装置、画像形成方法、プロセスカートリッジ、及び液体現像剤カートリッジ |
| JP2017187765A (ja) * | 2016-03-31 | 2017-10-12 | 東友ファインケム株式会社Dongwoo Fine−Chem Co., Ltd. | 青色感光性樹脂組成物、これを含む青色カラーフィルタおよびディスプレイ素子 |
| JP2019174673A (ja) * | 2018-03-28 | 2019-10-10 | 花王株式会社 | 静電荷像現像用トナー |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2025041642A1 (ja) * | 2023-08-23 | 2025-02-27 | 富士フイルム株式会社 | 組成物、膜、光学フィルタ、固体撮像素子および画像表示装置 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2021235373A1 (ja) | 2021-11-25 |
| KR20230002664A (ko) | 2023-01-05 |
| CN115516039B (zh) | 2023-09-15 |
| KR102869416B1 (ko) | 2025-10-14 |
| TW202146379A (zh) | 2021-12-16 |
| US20230159752A1 (en) | 2023-05-25 |
| JP7344379B2 (ja) | 2023-09-13 |
| CN115516039A (zh) | 2022-12-23 |
| TWI881123B (zh) | 2025-04-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7113899B2 (ja) | 着色組成物、硬化膜、パターン形成方法、カラーフィルタ、固体撮像素子および画像表示装置 | |
| WO2021215133A1 (ja) | 着色組成物、膜、光学フィルタ、固体撮像素子及び画像表示装置 | |
| JP7717204B2 (ja) | 着色組成物、膜、光学フィルタ、固体撮像素子及び画像表示装置 | |
| JPWO2020044720A1 (ja) | 着色組成物、膜、カラーフィルタ、カラーフィルタの製造方法、固体撮像素子及び画像表示装置 | |
| WO2020241537A1 (ja) | 樹脂組成物、膜、カラーフィルタ、固体撮像素子および画像表示装置 | |
| WO2022059394A1 (ja) | 硬化性組成物、硬化物、カラーフィルタ、固体撮像素子、画像表示装置、及び、高分子化合物 | |
| JP2024014989A (ja) | 着色感光性組成物、硬化物、カラーフィルタ、固体撮像素子、及び、画像表示装置 | |
| WO2021166855A1 (ja) | 着色組成物、膜、赤色画素、カラーフィルタ、固体撮像素子、画像表示装置およびキット | |
| JP2025063188A (ja) | 着色感光性組成物、硬化物、カラーフィルタ、固体撮像素子、画像表示装置、及び、非対称ジケトピロロピロール化合物 | |
| WO2022044650A1 (ja) | 着色組成物、光学フィルタの製造方法および固体撮像素子の製造方法 | |
| WO2022202204A1 (ja) | 着色組成物、膜、光学フィルタ、固体撮像素子および画像表示装置 | |
| WO2022085485A1 (ja) | 樹脂組成物、樹脂組成物の製造方法、膜の製造方法、光学フィルタの製造方法、固体撮像素子の製造方法および画像表示装置の製造方法 | |
| WO2021166859A1 (ja) | 着色組成物、膜、赤色画素、カラーフィルタ、固体撮像素子、画像表示装置およびキット | |
| JP7344379B2 (ja) | 樹脂組成物、膜、光学フィルタ、固体撮像素子および画像表示装置 | |
| JPWO2020166510A1 (ja) | 硬化性組成物、膜、カラーフィルタ、カラーフィルタの製造方法、固体撮像素子、画像表示装置、及び、高分子化合物 | |
| JPWO2020022248A1 (ja) | 硬化性組成物、膜、カラーフィルタ、カラーフィルタの製造方法、固体撮像素子および画像表示装置 | |
| JPWO2020022247A1 (ja) | 硬化性組成物、硬化性組成物の製造方法、膜、カラーフィルタ、カラーフィルタの製造方法、固体撮像素子および画像表示装置 | |
| WO2021166856A1 (ja) | 着色組成物、膜、赤色画素、カラーフィルタ、固体撮像素子、画像表示装置およびキット | |
| WO2021002237A1 (ja) | 着色組成物、膜、カラーフィルタおよび固体撮像素子 | |
| WO2022230625A1 (ja) | 着色組成物、膜、光学フィルタ、固体撮像素子、画像表示装置および化合物 | |
| WO2022085496A1 (ja) | 樹脂組成物、膜の製造方法、光学フィルタの製造方法、固体撮像素子の製造方法および画像表示装置の製造方法 | |
| WO2021256361A1 (ja) | 着色組成物、膜、カラーフィルタ、固体撮像素子及び画像表示装置 | |
| JP2022119701A (ja) | 感光性組成物、感光性組成物の製造方法、膜、光学フィルタ、固体撮像素子および画像表示装置 | |
| WO2021166858A1 (ja) | 着色組成物、膜、赤色画素、カラーフィルタ、固体撮像素子、画像表示装置およびキット | |
| WO2022024554A1 (ja) | 着色組成物、硬化物、カラーフィルタ、固体撮像素子、画像表示装置、並びに、樹脂及びその製造方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21808578 Country of ref document: EP Kind code of ref document: A1 |
|
| ENP | Entry into the national phase |
Ref document number: 2022524452 Country of ref document: JP Kind code of ref document: A |
|
| ENP | Entry into the national phase |
Ref document number: 20227039514 Country of ref document: KR Kind code of ref document: A |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 21808578 Country of ref document: EP Kind code of ref document: A1 |