TWI733858B - Composition, cured film, infrared transmission filter, solid-state imaging element, and infrared sensor - Google Patents

Abstract

The present invention provides a composition capable of forming a cured film excellent in pattern formation and solvent resistance, and a cured film, infrared transmission filter, solid-state imaging element, and infrared sensor using the composition. A composition comprising a near-infrared permeable black color material, a curable compound, and a solvent, wherein the near-infrared permeable black color material contains a dye compound selected from a dye compound having a crosslinkable group and a dye compound having a structure derived from the dye compound. At least one of the aggregates, the ratio of the minimum value A of the absorbance in the wavelength range of 400 to 700 nm to the maximum value B of the absorbance in the wavelength range of 1100 to 1300 nm of the composition, that is, A/B is 4.5 or more.

Description

Composition, cured film, infrared transmission filter, solid-state imaging element, and infrared sensor

The present invention relates to a composition that can be used in the formation of infrared transmission filters and the like. In addition, it also relates to a cured film, an infrared transmission filter, a solid-state imaging element, and an infrared sensor using a composition.

The solid-state imaging element is used as a light sensor for various purposes. For example, infrared light has a longer wavelength than visible light, so it is difficult to scatter, and can be used in distance measurement or 3-dimensional measurement. In addition, infrared rays are not seen by the eyes of humans and animals. Therefore, even if the subject is illuminated by an infrared light source at night, it will not be detected by the subject. It can also be used to photograph nocturnal wild animals and prevent crimes without irritation. Used for the purpose of shooting by the other party. In this way, a photo sensor (infrared sensor) that perceives infrared rays can be developed for various purposes, and it is expected to develop a film that can be used in an infrared sensor.

Patent Document 1 describes a color filter composition containing a black color material that transmits near infrared rays. In addition, in paragraph 0019 of Patent Document 1, there is a description that a near-infrared permeable black color material-based pigment is preferable.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1]: Japanese Patent Application Laid-Open No. 2014-130173

In recent years, further miniaturization of the pattern size has been desired. A composition using a dye-type near-infrared-transmitting black color material can improve the resolution compared to a composition using a pigment-type near-infrared-transmitting black color material. In addition, when preparing the composition, the dye-type near-infrared transparent black color material has the advantage of being able to omit the troubles such as dispersion. However, the cured film using a composition containing a dye-type near-infrared-transmitting black color material has a tendency that the solvent resistance tends to decrease easily compared to a cured film using a composition containing a pigment-type near-infrared-transmitting black color material. .

Therefore, the object of the present invention is to provide a composition capable of forming a cured film having excellent patterning properties and solvent resistance. In addition, there is provided a cured film, an infrared transmission filter, a solid-state imaging element, and an infrared sensor using the aforementioned composition.

The inventors of the present invention conducted intensive studies and found that as a near-infrared permeable black color material, a dye compound having a crosslinkable group and/or a dye polymer having a structure derived from a dye compound having a crosslinkable group is used As a result, it is possible to form a cured film excellent in pattern formability and solvent resistance, thereby completing the present invention. The present invention provides the following.

<1> A composition comprising a near-infrared permeable black color material, a curable compound and a solvent, wherein the near-infrared permeable black color material contains a dye compound selected from a crosslinkable group and a structure derived from the dye compound At least one of the pigment multimers, the ratio of the minimum absorbance value A in the wavelength range of 400 to 700 nm of the composition to the maximum absorbance value B in the wavelength range of 1100 to 1300 nm, that is, A/B is 4.5 or more .

<2> The composition as shown in <1>, wherein the crosslinkable group possessed by the dye compound is at least one selected from a group having an ethylenically unsaturated bond, an epoxy group and an alkoxysilyl group.

<3> The composition according to <1> or <2>, wherein the dye compound having a crosslinkable group is at least 1 selected from the group consisting of xanthene compounds, perylene compounds, azo compounds, and bisbenzofuranone compounds kind.

<4> The composition according to any one of <1> to <3>, wherein the dye polymer system is formed by bonding two or more dye compound-derived structures to a linking group having a valence of two or more.

<5> The composition according to any one of <1> to <3>, wherein the pigment multimer has a repeating unit containing a structure derived from a dye compound.

<6> The composition according to any one of <1> to <5>, which further contains a coloring agent.

<7> A cured film obtained by curing the composition described in any one of <1> to <6>.

<8> An infrared transmission filter having the cured film described in <7>.

<9> A solid-state imaging device having the cured film described in <7>.

<10> An infrared sensor having the cured film described in <7>.

According to the present invention, it is possible to provide a composition capable of forming a cured film having excellent patterning properties and solvent resistance. In addition, it is possible to provide a cured film, an infrared transmission filter, a solid-state imaging element, and an infrared sensor using the aforementioned composition.

100: infrared sensor

110: solid-state image sensor

111: Infrared cut filter

112: Color filter

113: Infrared transmission filter

114: area (resin layer)

115: Micro lens

116: Planarization layer

hν: incident light

Fig. 1 is a schematic cross-sectional view showing the structure of an embodiment of the infrared sensor of the present invention.

In this specification, the total solid content refers to the total mass of the components in which the solvent is removed from the entire composition.

In the label of the group (atomic group) in this specification, the label which does not describe the substitution and the unsubstituted includes a group having no substituent and a group having a substituent. For example, "alkyl" means not only an unsubstituted alkyl group (unsubstituted alkyl), but also a substituted alkyl group (substituted alkyl).

Unless otherwise specified, "exposure" in this specification includes not only exposure using light, but also drawing using particle beams such as electron beams and ion beams. In addition, as the light used in the exposure, actinic rays or radiation such as the bright-ray spectrum of a mercury lamp, extreme ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams can be cited.

In this specification, "(meth)acrylate" means both or either of acrylate and methyl acrylate, "(meth)acrylic" means both or either of acrylic acid and methacrylic acid, "( "Meth)acryloyl group" means both or either of an acryloyl group and a methacryloyl group.

The term "process" in this specification not only refers to an independent process, but also achieves the expected effect of the process even when it cannot be clearly distinguished from other processes, and is included in this term.

In this specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene conversion values measured by gel permeation chromatography (GPC). In this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) can be used, for example, by using HLC-8220 (manufactured by TOSOH CORPORATION), and using TSKgel Super AWM-H (manufactured by TOSOH CORPORATION, 6.0 mmID (inner diameter) as the column )×15.0cm), use 10mmol/L as eluent NMP (N-methylpyrrolidone) solution of lithium bromide.

In this manual, the numerical range indicated by "~" means the range that includes the numerical value described before and after "~" as the lower limit and the upper limit.

<Composition>

The composition of the present invention is a composition containing a near-infrared permeable black color material, a curable compound, and a solvent, and is characterized by: The near-infrared permeable black color material contains at least one selected from the group consisting of a dye compound having a crosslinkable group and a dye multimer having a structure derived from the dye compound having a crosslinkable group, The ratio of the minimum value A of the absorbance in the wavelength range of 400 to 700 nm to the maximum value B of the absorbance in the wavelength range of 1100 to 1300 nm of the composition, that is, A/B is 4.5 or more.

In the composition of the present invention, a dye compound having a crosslinkable group and/or a dye multimer having a structure derived from a dye compound having a crosslinkable group is used as a near-infrared permeable black color material, thereby being able to form A cured film with excellent solvent resistance. In addition, the ratio of the minimum value A of the absorbance in the wavelength range of 400 to 700 nm to the maximum value B of the absorbance in the wavelength range of 1100 to 1300 nm, that is, A/B, is 4.5 or more. A cured film that transmits infrared rays in a specific wavelength range. Therefore, by using the composition of the present invention, it is possible to form an infrared transmission filter and the like having excellent solvent resistance.

In addition, in the manufacturing process of equipment such as infrared sensors, a color filter or a protective film may be laminated on the infrared transmission filter. If the infrared transmission filter has poor solvent resistance, when these films are laminated on the infrared transmission filter, near-infrared rays may be eluted from the infrared transmission filter to transmit black color materials and the like, and the spectral characteristics of the infrared transmission filter may change. In contrast to this, according to the book The composition of the present invention can form a cured film with excellent solvent resistance. Therefore, even when a color filter or a protective film is formed on the cured film formed by using the composition of the present invention, it can suppress the transmission of near infrared rays from the black color material. The elution of the cured film, etc.

In addition, in the composition of the present invention, a dye compound having a crosslinkable group and/or a dye multimer having a structure derived from a dye compound is used as a near-infrared permeable black color material. Therefore, the pattern forming property is good, and it can Form a more subtle pattern.

In addition, in the near-infrared-transmitting black color material, since the transmittance of i-rays (365nm) and the like is low, as the pattern size becomes high resolution, the rectangularity of the pattern may decrease, or pattern peeling may occur, but it is regarded as near-infrared. Through the black color material, use a dye compound with a crosslinkable group (groups with ethylenic unsaturated bonds are preferred), which can be cured to the lower part of the film with a small amount of exposure, even with high resolution The pattern can also be formed into a pattern with excellent rectangularity and adhesion.

In the composition of the present invention, the above-mentioned absorbance condition can be achieved by any means. For example, by adjusting the type and content of the near-infrared-permeable black color material, or further containing a color colorant and/or infrared absorber, and adjusting the type and content, the above-mentioned absorbance condition can be appropriately achieved. In addition, the infrared absorber has the function of restricting the transmitted light (infrared) to the longer wavelength side.

Regarding the spectral characteristics of the composition of the present invention, the above-mentioned A/B value is preferably 7 or more, more preferably 7.5 or more, more preferably 10 or more, more preferably 15 or more, and more preferably 30 or more good.

The absorbance Aλ at a certain wavelength λ is defined by the following formula (1).

Aλ=-log(Tλ/100)……(1)

Aλ is the absorbance at the wavelength λ, and Tλ is the transmittance (%) at the wavelength λ.

The absorbance value may be a value measured in the state of a solution, or may be a value measured in the state of a film manufactured using the composition. When measuring the absorbance in the state of a film, it is better to use the following film for measurement, that is, apply the composition on the glass substrate so that the thickness of the dried film becomes a predetermined thickness by a method such as spin coating, and use The hot plate was dried at 100°C for 120 seconds to prepare the film. The thickness of the film can be measured using a stylus-type surface profile measuring device (DEKTAK150 manufactured by ULVAC) on a substrate having a film.

The absorbance can be measured using a conventionally known spectrophotometer. The absorbance measurement conditions are not particularly limited, but it is preferable to measure the absorbance maximum value B in the range of 1100 to 1300 nm under the condition that the minimum value A of the absorbance in the adjusted wavelength range of 400 to 700 nm becomes 0.1 to 3.0. . By measuring the absorbance under such conditions, the measurement error can be further reduced. The method of adjusting the minimum value A of the absorbance in the wavelength range of 400 to 700 nm to 0.1 to 3.0 is not particularly limited. For example, when measuring the absorbance in the state of the composition, a method of adjusting the optical path length of the sample tube can be cited. In addition, when the absorbance is measured in the state of the film, a method of adjusting the film thickness and the like can be cited.

A specific example of a method for measuring the spectral characteristics, film thickness, and the like of a film formed from the composition of the present invention is shown below.

The composition of the present invention is coated on a glass substrate by a method such as a spin coating method so that the thickness of the dried film becomes a predetermined thickness, and the composition is dried at 100° C. for 120 seconds using a hot plate. The thickness of the film was measured using a stylus-type surface profile measuring device (DEKTAK150 manufactured by ULVAC) on the dried substrate with the film. For the dried substrate with this film, use UV See a near-infrared spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation), and measure the transmittance at a wavelength of 300 to 1300 nm.

Regarding the composition of the present invention, it is also referred to as an infrared-transmitting composition based on the transmission of infrared rays. Hereinafter, each component that can constitute the composition of the present invention will be described.

<<Near infrared transmission black color material>>

The composition of the present invention contains a near-infrared permeable black color material. The near-infrared permeable black color material in the present invention contains at least one selected from a dye compound having a crosslinkable group and a dye multimer having a structure derived from the dye compound having a crosslinkable group.

Near-infrared light is preferably a material that absorbs light in the wavelength range from violet to red through the black color material. The near-infrared-transmitting black color material is preferably a color material that blocks light in the range of 400 to 700 nm in wavelength. The ratio of the minimum absorbance value A1 in the wavelength range of 400 to 700 nm to the minimum absorbance value B1 in the wavelength range of 900 to 1300 nm, that is, the ratio of A1/B1 to 4.5 or more of the near-infrared permeable black color material is preferable. The near-infrared-transmitting black color material is preferably a color material that transmits at least a part of light in the wavelength range of 800 to 1300 nm.

(Dye compound with crosslinkable group)

The dye compound having a crosslinkable group (also called a crosslinkable dye) is preferably at least one compound selected from the group consisting of xanthene compounds, perylene compounds, azo compounds, and bisbenzofuranone compounds, and xanthene compounds For better.

The crosslinkable dye system preferably dissolves 1 g or more of the compound with respect to 100 g of propylene glycol monomethyl ether acetate at 23° C., and more preferably dissolves 3 g or more of the compound.

There are no particular limitations on the type of crosslinkable group possessed by the crosslinkable dye. Can give A group that can produce cross-linking reaction by the action of heat, light, free radicals, etc. As a specific example of a crosslinkable group, the group which has an ethylenically unsaturated bond, an epoxy group, an alkoxysilyl group, a hydroxymethyl group, etc. are mentioned. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth)allyl group, and a (meth)acryloyl group. Examples of alkoxysilyl groups include monoalkoxysilyl groups, dialkoxysilyl groups, and trialkoxysilyl groups. The carbon number of the alkoxy group in the alkoxysilyl group is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 or 2. As the crosslinkable group, an epoxy group and an alkoxysilyl group are preferable, and an epoxy group is more preferable. According to this aspect, there is no difference in the crosslinking rate in the upper portion (surface side) and the lower portion (support side) of the film, and the entire film can be crosslinked almost uniformly. In addition, the pattern formability is good, and the shape of the obtained pattern is good. Furthermore, pattern peeling can be effectively suppressed.

Regarding the crosslinkable dye, it is preferable to have 1 to 4 crosslinkable groups in one molecule, it is more preferable to have 1 to 3, and it is more preferable to have 1 to 2 groups. According to this state, effects such as improvement of resistance to solvents can be expected.

Crosslinkable dye-based monomer type compounds are preferred. The crosslinkable dye is preferably a compound having one dye skeleton in one molecule. In addition, the molecular weight of the crosslinkable dye is preferably 300 to 3000, and more preferably 500 to 1500. In addition, the value of the molecular weight of the crosslinkable dye is a value calculated based on the structural formula.

As a specific example of a crosslinkable dye, the following compounds can be mentioned. In addition, commercially available products can also be used for crosslinkable dyes. For example, K01 (manufactured by Wako Pure Chemical Industries, Ltd., xanthene compound), R56 (manufactured by Wako Pure Chemical Industries, Ltd., xanthene compound), etc. may be mentioned. In the following structural formulae, Me is a methyl group.

[Chemical formula 1]

(Pigment polymer)

The dye multimer used as a near-infrared permeable black color material is a dye multimer having a structure derived from a dye compound having a crosslinkable group (hereinafter also referred to as dye multimer A).

Regarding the pigment polymer A, it is preferable to dissolve 1 g or more with respect to 100 g of propylene glycol monomethyl ether acetate at 23° C., and it is more preferable to dissolve 3 g or more.

Regarding the dye multimer A, it is preferable to have two or more structures derived from the above-mentioned crosslinkable dye in one molecule, and it is more preferable to have three or more. The upper limit is not particularly limited, but it can also be set to 100 or less.

The dye multimer A is preferably a compound having a structure in which two or more structures derived from a dye compound (crosslinkable dye) are bonded to a bivalent or higher linking group. As the linking group with more than two valences, alkylene, aryl, -O-, -S-, -SO-, -CO-, -COO-, -OCO-, -SO ₂ -, -NR can be mentioned -(R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), or a group containing these combinations.

In addition, the dye multimer A is preferably a compound (polymer) having a repeating unit derived from a dye compound (crosslinkable dye). The pigment multimer A is preferably a polymer containing a repeating unit represented by formula (A). In the dye multimer A, the ratio of the repeating unit represented by the formula (A) is preferably 10 to 100% by mass of the total repeating units constituting the dye multimer A. The lower limit is more preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more. The upper limit is more preferably 95% by mass or less.

In the formula (A), X ¹ represents the main chain of the repeating unit, and L ¹ represents a single bond or a divalent linking group. DyeI represents the pigment structure.

In the formula (A), X ¹ represents the main chain of the repeating unit. The main chain of the repeating unit differs depending on the type of crosslinkable group possessed by the crosslinkable dye. For example, when the cross-linkable dye is a compound having an ethylenically unsaturated bond as a cross-linkable group, as X ¹ , the structure represented by the following (XX-1) to (XX-24) can be exemplified by The structure represented by (XX-1) or (XX-24) is preferred.

[Chemical formula 3]

In the formula, * represents the bond ^{with L 1.} Me represents methyl. In addition, R in (XX-18) and (XX-19) represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.

L ¹ represents a single bond or a divalent linking group. Examples of the divalent linking group include alkylene groups having 1 to 30 carbon atoms, arylene groups having 6 to 30 carbon atoms, heterocyclic linking groups, -CH=CH-, -O-, -S-, -C (=O)-, -COO-, -NR-, -CONR-, -OCO-, -SO-, -SO ₂ -and a linking group formed by linking two or more of these. Here, R each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. The carbon number of the alkylene group is preferably 1 to 30. The upper limit is more preferably 25 or less, and more preferably 20 or less. The lower limit is more preferably 2 or more, and more preferably 3 or more. The alkylene group may be any of linear, branched, and cyclic. The carbon number of the aryl group is more preferably 6-20, and 6-12 is even more preferable. The heterocyclic linking group is preferably a 5-membered ring or a 6-membered ring. The heteroatoms included in the heterocyclic linking group are preferably an oxygen atom, a nitrogen atom, and a sulfur atom. The number of heteroatoms in the heterocyclic linking group is preferably 1 to 3.

The dye structure represented by DyeI is a dye structure derived from a crosslinkable dye. For example, a xanthene dye structure, a perylene dye structure, an azo dye structure, and a bisbenzofuranone dye structure can be mentioned.

The repeating unit represented by the formula (A) is preferably the repeating unit represented by the following formulas (A-1) to (A-3).

In the formula (A-1), R ^1A represents a hydrogen atom or an alkyl group, L ^1A represents a single bond or a divalent linking group, and Dyel represents a dye structure. In the formula (A-2), L ^2A represents a single bond or a divalent linking group, and Dyel represents a dye structure. In the formula (A-3), R ^3A represents an alkyl group or an aryl group, L ^3A represents a single bond or a divalent linking group, a represents 0 or 1, and Dyel represents a dye structure.

^{The definition of the divalent linking group represented by L 1A} to L ^3A in formula (A-1)~(A-3) is the same as the definition of the divalent linking group represented ^{by L 1} in formula (A), and the preferred range is The same is true. The dye structure represented by Dyel in formula (A-1) to (A-3) has the same definition as the dye structure represented by Dyel in formula (A), and the preferred range is also the same.

^{The carbon number system of the alkyl group represented by R 1A} in the formula (A-1) is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1. R ^1A is preferably a hydrogen atom or a methyl group.

The carbon number of the alkyl group in the formula (A-3) is preferably 1-10, more preferably 1-8, and still more preferably 1-6. In addition, the alkyl group may be any of straight chain, branched chain, and cyclic, and straight chain is preferred. The carbon number of the aryl group in the formula (A-3) is preferably 6-20, more preferably 6-14, and still more preferably 6-10.

The dye multimer A may contain other repeating units in addition to the repeating unit represented by formula (A). Other repeating units may contain functional groups such as crosslinkable groups and acid groups. In addition, other repeating units may not include a functional group. As the crosslinkable group, a group having an ethylenically unsaturated bond, an epoxy group, an alkoxysilyl group, a hydroxymethyl group, and the like can be mentioned. As an acid group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, etc. are mentioned.

When the pigment multimer A contains a repeating unit with a crosslinkable group, the proportion of the repeating unit with a crosslinkable group is preferably greater than 0% by mass and 50% by mass or less of the total repeating units constituting the dye multimer A . The lower limit is more preferably 1% by mass or more, and more preferably 3% by mass or more. The upper limit is more preferably 35% by mass or less, and more preferably 30% by mass or less.

When the dye multimer A includes a repeating unit having an acid group, the ratio of the repeating unit having an acid group is preferably greater than 0% by mass and 50% by mass or less of the total repeating units constituting the dye multimer A. The lower limit is more preferably 1% by mass or more, and more preferably 3% by mass or more. Upper limit 35% by mass or less is more preferable, and 30% by mass or less is still more preferable.

In the composition of the present invention, the content of the near-infrared-transmitting black color material is preferably 1 to 60% by mass of the total solid content of the composition. The lower limit is more preferably 5% by mass or more, and more preferably 10% by mass or more. The upper limit is more preferably 50% by mass or less, and more preferably 40% by mass or less.

In the composition of the present invention, when a crosslinkable dye is contained as a near-infrared permeable black color material, the content of the crosslinkable dye is preferably 1 to 60% by mass of the total solid content of the composition. The lower limit is more preferably 5% by mass or more, and more preferably 10% by mass or more. The upper limit is more preferably 50% by mass or less, and more preferably 40% by mass or less. In addition, the content of the crosslinkable dye in the total mass of the near-infrared permeable black color material is preferably 10-100% by mass, more preferably 25-100% by mass, and still more preferably 50-100% by mass. A crosslinkable dye may be used only 1 type, and may use 2 or more types together. When two or more crosslinkable dyes are used at the same time, the total amount is preferably in the above-mentioned range.

In the composition of the present invention, when the pigment multimer A is contained as a near-infrared permeable black color material, the content of the pigment multimer A is preferably 1 to 60% by mass of the total solid content of the composition. The lower limit is more preferably 5% by mass or more, and more preferably 10% by mass or more. The upper limit is more preferably 50% by mass or less, and more preferably 40% by mass or less. In addition, the content of the pigment polymer A in the total mass of the near-infrared permeable black color material is preferably 10-100% by mass, more preferably 25-100% by mass, and still more preferably 50-100% by mass. The pigment multimer A may use only one type or two or more types at the same time. When two or more pigment multimers A are used at the same time, the total amount is preferably within the above-mentioned range.

In the composition of the present invention, it is also preferable to use both the crosslinkable dye and the dye multimer A as the near-infrared permeable black color material. When both are used at the same time, the content of the crosslinkable dye relative to 100 parts by mass of the pigment polymer A is preferably 10~90 parts by mass, more preferably 25~75 parts by mass, and more preferably 40~60 parts by mass .

(Other near infrared rays transmit through black color material)

The composition of the present invention may also contain the above-mentioned crosslinkable dye and the above-mentioned pigment polymer A as a near-infrared permeable black color material (hereinafter, also referred to as other near-infrared permeable black color material). Color material). Other near-infrared-transmitting black color materials are pigment-type near-infrared-transmitting black color materials or dye-type near-infrared-transmitting black color materials, and examples include dye compounds that do not have a crosslinkable group. Examples of other near-infrared permeable black color materials include bisbenzofuranone compounds, azomethine compounds, perylene compounds, azo compounds, and the like. Bisbenzofuranone compounds and perylene compounds are preferred.

Examples of the bisbenzofuranone compound include those described in Japanese Special Publication No. 2010-534726, Japanese Special Publication No. 2012-515233, Japanese Special Publication No. 2012-515234, and the like. For example, they can be manufactured by BASF Corporation. "Irgaphor Black" and acquired.

Examples of the perylene compound include C.I. Pigment Black 31, 32 and the like.

Examples of the azomethine compound include those described in Japanese Patent Laid-Open No. 1-170601, Japanese Patent Laid-Open No. 2-34664 and the like. For example, it can be referred to as "Chromofine manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd. Black A1103" and acquired.

The azo compound is not particularly limited, but a compound represented by the following formula (A-1) and the like can be appropriately mentioned.

The bisbenzofuranone compound is preferably a compound represented by the following general formula and a mixture thereof.

In the formula, R ¹ and R ² each independently represent a hydrogen atom or a substituent, R ³ and R ⁴ each independently represent a substituent, and a and b each independently represent an integer of 0-4. When a is 2 or more, a plurality of R ³ may be the same or different, and a plurality of R ³ may be bonded to form a ring. When b is 2 or more, a plurality of R ⁴ may be the same or different, and a plurality of R ⁴ may be bonded to form a ring.

For the details of the bisbenzofuranone compound, reference can be made to the description of paragraph numbers 0014 to 0037 of JP 2010-534726 A, and this content is incorporated in this specification.

When the composition of the present invention contains other near-infrared permeable black color material, the content of the other near-infrared permeable black color material is preferably 1-60% by mass of the total solid content of the composition, more preferably 1-30% by mass . In addition, the content of the other near-infrared-transmitting black color material in the total amount of the near-infrared-transmitting black color material is preferably 5-50% by mass, and more preferably 5-30% by mass.

In addition, the composition of the present invention can also be substantially free of other near-infrared permeable black color materials. The fact that no other near-infrared-permeable black color material is contained substantially means that the content of other near-infrared-permeable black color materials in the near-infrared-permeable black color material is preferably 3% by mass or less, and more preferably 1% by mass or less. It is more preferable not to contain it.

<<Infrared Absorber>>

The composition of the present invention can contain an infrared absorber. In the infrared transmission filter, the infrared absorber has the function of restricting the transmitted light (near infrared) to the longer wavelength side.

In the present invention, as the infrared absorber, a compound having a maximum absorption wavelength in a wavelength region of the infrared region (a wavelength greater than 700 nm and 1300 nm or less is preferable) can be preferably used. The infrared absorber may be a pigment or a dye.

Examples of infrared absorbers include pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, diimine compounds, transition metal oxides, square ylide (Squarylium) compounds, naphthalocyanine Compounds, quatratene compounds, dithiol metal complexes, crotonic acid compounds, etc. As the pyrrolopyrrole compound, for example, the compound described in paragraph numbers 0016 to 0058 of JP 2009-263614 A, the compound described in paragraph numbers 0037 to 0052 of JP 2011-68731 A, etc. can be cited. These contents are incorporated into this manual. As the squaraine ylide compound, for example, the compounds described in paragraphs 0044 to 0049 of JP 2011-208101 A are included, and this content is incorporated in this specification. As the cyanine compound, for example, the compounds described in paragraphs 0044 to 0045 of JP 2009-108267 A, the compounds described in paragraphs 0026 to 0030 of JP 2002-194040, and these The content is incorporated into this manual. As the diimine compound, for example, Japanese special table The compound described in the 2008-528706 publication is incorporated in this specification. As the phthalocyanine compound, for example, the compound described in paragraph 0093 of JP 2012-77153 A, the oxytitanium phthalocyanine described in JP 2006-343631, and JP 2013- The compounds described in paragraph numbers 0013 to 0029 of the 195480 publication are incorporated in this specification. As the naphthalocyanine compound, for example, the compound described in Paragraph No. 0093 of JP 2012-77153 A is incorporated, and this content is incorporated in this specification. In addition, as the cyanine compound, phthalocyanine compound, diimine compound, squaraine ylide compound, and crotonic acid compound, the compounds described in paragraph numbers 0010 to 0081 of JP 2010-111750 A can be used. Included in this manual. In addition, the cyanine-based compound can be referred to, for example, "functional dyes, Ogawara Shinshi/Matsuoka Ken/Kitao Tejiro/Hirashima Hiraki, Kodansha Scientific Ltd.", and this content is incorporated in this specification.

In the present invention, as the infrared absorber, the compound described in paragraph numbers 0004 to 0016 of JP-A-H07-164729 or the compound described in paragraph numbers 0027 to 0062 of JP-A 2002-146254 can also be used. , Japanese Patent Laid-Open No. 2011-164583, paragraph numbers 0034 to 0067, composed of microcrystals containing Cu and/or P oxides, and having a number average aggregate particle size of 5 to 200 nm near infrared absorbing particles. These contents are incorporated into this manual. In addition, FD-25 (manufactured by YAMADA CHEMICAL CO., LTD.), IRA842 (naphthalocyanine compound, manufactured by Exiton), etc. can also be used.

As the infrared absorber, inorganic fine particles can also be used. In terms of more excellent infrared shielding properties, inorganic microparticle-based metal oxide microparticles or metal microparticles are preferable. Examples of metal oxide particles include indium tin oxide (ITO) particles, antimony tin oxide (ATO) particles, zinc oxide (ZnO) particles, Al-doped zinc oxide (Al-doped ZnO) particles, fluorine Doped tin dioxide (F doped SnO ₂ ) particles, niobium doped titanium dioxide (Nb doped TiO ₂ ) particles, etc. Examples of metal fine particles include silver (Ag) particles, gold (Au) particles, copper (Cu) particles, nickel (Ni) particles, and the like. In addition, a tungsten oxide-based compound can be used as the inorganic fine particles. The tungsten oxide compound type cesium tungsten oxide is preferred. For the details of the tungsten oxide-based compound, refer to Paragraph No. 0080 of JP 2016-006476 A, which is incorporated in this specification. The shape of the inorganic fine particles is not particularly limited, and it may be spherical, non-spherical, sheet-like, linear, or tubular.

When the composition of the present invention contains an infrared absorber, the content of the infrared absorber is preferably 1 to 60% by mass of the total solid content of the composition, and more preferably 10 to 40% by mass. In addition, the content of the infrared absorber is preferably 10 to 200 parts by mass, more preferably 20 to 150 parts by mass, and more preferably 30 to 80 parts by mass relative to 100 parts by mass of the near-infrared permeable black color material. An infrared absorber may be used individually by 1 type, and may use 2 or more types together. When two or more kinds of infrared absorbers are used at the same time, it is preferable that the total thereof is in the above-mentioned range.

<<Color Colorant>>

The composition of the present invention preferably contains a coloring agent. In addition, in this specification, the color colorant means a coloring agent other than a white coloring agent and a black coloring agent. The coloring agent is preferably a coloring agent having a maximum absorption wavelength in the range of 400 to 650 nm.

The coloring agent may be a pigment or a dye. Dyes are preferred. In addition, the color colorant is preferably a compound having a crosslinkable group.

Pigment-based organic pigments are preferable, and the following can be mentioned. But the present invention is not limited to That's it.

Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137,138,139,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214 etc. (above, yellow pigment), CIPigment Orange 2, 5, 13, 16, 17:1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73 etc. (above, orange pigment), CIPigment 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, 270, 272, 279 etc. (above, red pigment), CIPigment Green 7, 10, 36, 37, 58, 59 etc. (above, green pigment), CIPigment Violet 1, 19, 23, 27, 32, 37, 42 etc. (above, purple pigment), CIPigment Blue 1, 2, 15, 15:1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80, etc. (above, blue pigment) .

These organic pigments can be used alone or in various combinations.

The dye is not particularly limited, and known dyes can be used. As the chemical structure, pyrazole azo series, aniline azo series, triarylmethane series, anthraquinone series, anthrapyridone series, benzylidene series, oxacyanine series, pyrazolotriazole azo series can be used , Pyridone azo series, cyanine series, phenanthrazine series, pyrrolopyrazole azomethine series, xanthene series, phthalocyanine series, benzopyran series, indigo series, pyrromethene series And other dyes.

As the coloring agent, a pigment multimer can be used. Dyes used for the pigment polymer system dissolved in a solvent are preferred, but they can form particles. When the dye multimer is a particle, the dye multimer is dispersed in a solvent or the like for use. The pigment multimer in the particle state can be obtained, for example, by emulsion polymerization. For example, as a specific example, the compound and the production method described in JP 2015-214682 A can be cited. In addition, as the dye multimer, compounds described in Japanese Patent Application Publication No. 2011-213925, Japanese Patent Application Publication No. 2013-041097, Japanese Patent Application Publication No. 2015-028144, Japanese Patent Application Publication No. 2015-030742, and the like can also be used.

Examples of the color colorant having a crosslinkable group include the following compounds. The compound is a red dye.

In the composition of the present invention, it is preferable to contain at least one coloring agent selected from the group consisting of a red coloring agent, a blue coloring agent and a purple coloring agent as a color coloring agent, and it is more preferable to contain a red coloring agent and/or a blue coloring agent. good. According to this state, the light shielding of the visible area can be improved more effectively.

When the composition of the present invention contains a color colorant, the content of the color colorant is preferably 0.1 to 60% by mass in the total solid content of the composition of the present invention. The lower limit is more preferably 0.5% by mass or more, and more preferably 1.0% by mass or more. The upper limit is more preferably 50% by mass or less, and more preferably 40% by mass or less.

The content of the color colorant is preferably 1-100 parts by mass, and more preferably 30-100 parts by mass relative to 100 parts by mass of the near-infrared permeable black color material. In addition, the content of the color colorant is preferably 1-100 parts by mass, and more preferably 30-100 parts by mass relative to the total of 100 parts by mass of the above-mentioned crosslinkable dye and the above-mentioned pigment polymer A.

The coloring agent may be used singly, or two or more of them may be used at the same time. When two or more color colorants are used at the same time, the total amount thereof is preferably within the above-mentioned range.

<<hardening compound>>

The composition of the present invention contains a curable compound. Examples of the curable compound include polymerizable compounds, resins, and the like. The resin may be a non-crosslinkable resin (resin without a crosslinkable group) or a crosslinkable resin (resin with a crosslinkable group). As a crosslinkable group, the group which has an ethylenically unsaturated bond, an epoxy group, an alkoxysilyl group, etc. are mentioned. In the present invention, it is preferable to use both a polymerizable compound (a radical polymerizable compound is preferable) and a resin as the curable compound. In addition, the resin preferably contains an alkali-soluble resin described later. In addition, in the present invention, the curable compound is a component other than the near-infrared permeable black color material.

In the composition of the present invention, the content of the curable compound relative to the total solid content of the composition is preferably 1% by mass or more, more preferably 5% by mass or more, more preferably 10% by mass or more, and 15% by mass or more Especially good. The upper limit is preferably 90% by mass or less, more preferably 80% by mass or less, and more preferably 75% by mass or less.

<<<Polymerizable compound>>>

The polymerizable compound may be in any form of a monomer or a polymer, but a monomer is preferred. Among the monomer-type polymerizable compounds, a molecular weight of 100 to 3000 is preferred. The upper limit is preferably 2000 or less, and more preferably 1500 or less. The lower limit is preferably 150 or more, and more preferably 250 or more. In addition, the polymerizable compound is preferably a compound that does not substantially have a molecular weight distribution. Here, the fact that it has substantially no molecular weight distribution means that the dispersion of the compound (weight average molecular weight (Mw)/number average molecular weight (Mn)) is preferably 1.0 to 1.5, and more preferably 1.0 to 1.3. The polymerizable compound is preferably a compound that can be polymerized by the action of free radicals. That is, the polymerizable compound is preferably a radical polymerizable compound. The polymerizable compound is preferably a compound having at least one ethylenically unsaturated bond-containing group, and a compound having two or more ethylenically unsaturated bond-containing groups is more preferable, with 3 or more Compounds of ethylenically unsaturated bond groups are further preferred. The upper limit of the number of groups having ethylenically unsaturated bonds is preferably 15 or less, and more preferably 6 or less. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a styryl group, a (meth)allyl group, a (meth)acryloyl group, and the like, and a (meth)acryloyl group is preferred. The polymerizable compound is preferably a 3- to 15-functional (meth)acrylate compound, and a 3- to 6-functional (meth)acrylate compound is more preferable.

As an example of a polymerizable compound, refer to JP 2013-253224 A The contents of paragraph numbers 0033~0034 are incorporated into this manual. As the above-mentioned compound, ethyleneoxy-modified neopentyl erythritol tetraacrylate (as a commercial product, NK ester ATM-35E; manufactured by Shin Nakamura Chemical Co., Ltd.), dineopentaerythritol triacrylate (as a commercial product) Commercial product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dineopentol tetraacrylate (as a commercial product, KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dinepentyl Tetraol penta(meth)acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dineopentol hexa(meth)acrylate (as a commercial product, KAYARAD DPHA ; Nippon Kayaku Co., Ltd., A-DPH-12E; Shin Nakamura Chemical Co., Ltd.), and the structure in which these (meth)acrylic groups are bonded via ethylene glycol and propylene glycol residues is Better. And these oligomer types can also be used. In addition, the description of the polymerizable compound in paragraph numbers 0034 to 0038 of JP 2013-253224 A can be referred to, and this content is incorporated in this specification. In addition, the polymerizable monomers described in paragraph 0477 of JP 2012-208494 A (corresponding to U.S. Patent Application Publication No. 2012/0235099 Paragraph No. 0585) can be cited, and these contents are incorporated in this specification. middle.

In addition, diglycerin EO (ethylene oxide) modified (meth)acrylate (as a commercial product, M-460; manufactured by TOAGOSEI CO., LTD.) is preferred. Neopentyl erythritol tetraacrylate (manufactured by Shin Nakamura Chemical Co., Ltd., A-TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA) is also preferred . These oligomer types can also be used. For example, RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) etc. are mentioned.

The polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Regarding polymerizable compounds with acid groups, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred. The aromatic carboxylic acid anhydride reacts with the unreacted hydroxyl group of the aliphatic polyhydroxy compound to add an acid group to the polymerizable compound. Among the above esters, the aliphatic polyhydroxy compound is neopentylerythritol and dineopentaerythritol The compound of at least one of them is more preferable. Examples of commercially available products include ARONIX M-510, M-520 (manufactured by TOAGOSEI CO., LTD.), CBX-0, CBX-1 (manufactured by Shin Nakamura Chemical Co., Ltd.), and the like. The acid value of the polymerizable compound having an acid group is preferably 0.1 to 40 mgKOH/g. The lower limit is more preferably 5 mgKOH/g or more. The upper limit is more preferably 30 mgKOH/g or less. If the acid value of the polymerizable compound is 0.1 mgKOH/g or more, the development dissolution characteristics are good, and if it is 40 mgKOH/g or less, it is advantageous in terms of production or handling. Furthermore, it is excellent in curability.

Among the polymerizable compounds, compounds having a caprolactone structure are also preferred.

The compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule. For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, Ditrimethylolpropane, neopentylerythritol, dineopentylerythritol, trineopentitol, glycerol, diglycerol, trimethylolmelamine and other polyols, and by combining (meth)acrylic acid and ε- The ε-caprolactone obtained by esterification of caprolactone is modified as a multifunctional (meth)acrylate. For compounds having a caprolactone structure, reference can be made to the description of paragraph numbers 0153 to 0170 of International Publication WO2015/166779, which content is incorporated in this specification. As a commercially available product, for example, SR-494, which is a tetrafunctional acrylate having 4 vinyloxy chains, manufactured by Sartomer, and a product manufactured by Nippon Kayaku Co., Ltd., which has 6 pentyloxy chains, can be cited. DPCA-60 as a 6-functional acrylate, TPA-330 as a tri-functional acrylate with 3 isobutoxy chains, etc.

It is also preferable that the polymerizable compound is a (meth)acrylate modified by isocyanuric acid ethylene oxide. Examples of commercially available products include ARONIX M-315 and M-313 (TOAGOSEI CO.,LTD. Manufactured), NK ester A-9300 (manufactured by Shin Nakamura Chemical Co., Ltd.), SR368 (manufactured by Sartomer), and the like. As the polymerizable compound used in combination with the oxytitanium cyanine pigment, from the viewpoint of heat resistance, the higher the SP value (Solubility Parameter), the better. Examples of polymerizable compounds with high SP values include ARONIX M-315 and M-313 (manufactured by TOAGOSEI CO., LTD.).

As the polymerizable compound, for example, urethane acrylic acid described in Japanese Patent Publication No. 48-41708, Japanese Patent Application Publication No. 51-37193, Japanese Patent Publication No. 2-32293, Japanese Patent Publication No. 2-16765 Esters, or those having an ethylene oxide skeleton described in Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 Urethane compounds are preferred. Use the addition polymerizable compounds described in JP 63-277653, JP 63-260909, and Hei 1-105238 that have an amine structure or a sulfide structure in the molecule Therefore, it is possible to obtain a composition having a very excellent photosensitive speed.

Commercial products include urethane oligomer UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin Nakamura Chemical Co., Ltd.), and DPHA -40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by KYOEISHA CHEMICAL Co., Ltd.), etc.

The content of the polymerizable compound in the composition is preferably 0.1 to 50% by mass relative to the total solid content of the composition. For example, the lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is, for example, more preferably 45% by mass or less, and more preferably 40% by mass or less. The polymerizable compound may be used alone or in combination of two or more kinds. When two or more types are used at the same time, it is preferable that the total amount falls within the above-mentioned range.

<<<Resin>>>

The composition of the present invention may contain a resin as a curable compound. Examples of resins include alkali-soluble resins and the like. The weight average molecular weight (Mw) of the resin is preferably 2,000-2,000,000. The upper limit is more preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit is more preferably 3,000 or more, and more preferably 5,000 or more. The content of the resin is preferably 10 to 80% by mass of the total solid content of the composition, and more preferably 20 to 60% by mass. The composition may include only one type of resin, or may include two or more types. When two or more kinds of resins are contained, the total amount thereof is preferably within the above-mentioned range.

(Alkali-soluble resin)

In the composition of the present invention, it is preferable to contain an alkali-soluble resin as the resin. By containing alkali-soluble resin, developability and pattern formability are improved.

The molecular weight of the alkali-soluble resin is not particularly limited, but the weight average molecular weight (Mw) is preferably 5,000 to 100,000. The number average molecular weight (Mn) is preferably 1,000 to 20,000.

As an alkali-soluble resin, it can select suitably from the resin which has the group which promotes alkali dissolution. As the group that promotes alkali dissolution (hereinafter, also referred to as acid group), for example, a carboxyl group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxyl group, etc. can be mentioned, and a carboxyl group is preferred. These acid groups may be only one type or two or more types.

As the alkali-soluble resin, from the viewpoint of heat resistance, polyhydroxystyrene-based resins, polysiloxane-based resins, acrylic resins, acrylamide-based resins, and acrylic/acrylamide copolymer resins are preferred. From the viewpoint of controlling developability, acrylic resins, acrylamide resins, and acrylic/acrylamide copolymer resins are preferred.

Alkali-soluble resins are preferably polymers having a carboxyl group in the side chain. Specific examples include methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and novolac resins. Alkali-soluble phenolic resins, acidic cellulose derivatives with carboxyl groups in the side chains, and resins in which acid anhydrides are added to polymers with hydroxyl groups. In particular, a copolymer of (meth)acrylic acid and other monomers copolymerizable therewith is preferable as the alkali-soluble resin. Examples of other monomers that can be copolymerized with (meth)acrylic acid include alkyl (meth)acrylates, aryl (meth)acrylates, vinyl compounds, and the like. Examples of alkyl (meth)acrylates and aryl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (meth)acrylate. Butyl acrylate, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate Base) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, etc.; examples of the vinyl compound include styrene and α-methyl styrene , Vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofuran methyl methacrylate, polystyrene macromonomers, polymethyl methacrylate macromolecules Monomers and so on. Other monomers can also use the N-substituted maleimide monomers described in JP 10-300922 A, for example, N-phenyl maleimide, N-cyclohexyl maleimide Endiimines and others. In addition, the other monomers that can be copolymerized with these (meth)acrylic acids may be only one type or two or more types.

In order to improve the crosslinking efficiency of the film, an alkali-soluble resin having polymerizable groups can be used. As a polymerizable group, a (meth)allyl group, a (meth)acryloyl group, etc. are mentioned. Polymeric base Among the alkali-soluble resins, alkali-soluble resins containing polymerizable groups in the side chain are useful. Examples of alkali-soluble resins containing polymerizable groups include DIANALNR series (manufactured by MITSUBISHI RAYON CO., LTD.), Photomer6173 (containing COOH polyurethane acrylic oligomer, manufactured by Diamond Shamrock Co., Ltd.), Viscoat R-264, KS Photoresist 106 (all manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.), CYCLOMER P series (for example, ACA230AA), PLACCEL CF200 series (all manufactured by Daicel Corporation), Ebecry13800 (manufactured by Daicel-UCB Co., Ltd.), Akurikiyua -RD-F8 (manufactured by NIPPON SHOKUBAI CO., LTD.), etc.

Alkali-soluble resins can preferably be used containing benzyl (meth)acrylate/(meth)acrylic acid copolymer, benzyl (meth)acrylate/(meth)acrylic acid/2-hydroxy(meth)acrylic acid Ester copolymer, multi-element copolymer of benzyl (meth)acrylate/(meth)acrylic acid/other monomers. It is also possible to preferably use 2-hydroxy(meth)acrylate copolymerized with ethyl 2-hydroxy(meth)acrylate, as described in Japanese Patent Laid-Open No. 7-140654, 2-hydroxy(meth)acrylate/polystyrene macro Molecular monomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxy-3-phenoxy propyl acrylate/polymethyl methacrylate macromonomer/benzyl methacrylate/methacrylic acid copolymer Compounds, 2-hydroxyethyl methacrylate/polystyrene macromonomer/methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/methyl Benzyl acrylate/methacrylic acid copolymer, etc.

The alkali-soluble resin contains a single compound that contains 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") Polymers formed by polymerization of body components are also preferred.

[Chemical formula 8]

In formula (ED1), 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.

In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the formula (ED2), refer to the description in JP 2010-168539 A.

In the formula (ED1), ^{the hydrocarbon group having 1 to 25 carbon atoms which may have substituents represented by R 1} and R ² is not particularly limited, for example, methyl, ethyl, n-propyl, isopropyl Straight-chain or branched alkyl groups such as butyl, n-butyl, isobutyl, tertiary butyl, tertiary pentyl, stearyl, lauryl, 2-ethylhexyl, etc.; aryl groups such as phenyl; Cyclohexyl, tertiary butylcyclohexyl, dicyclopentadienyl, tricyclodecyl, isobornyl, adamantyl, 2-methyl-2-adamantyl and other alicyclic groups; by 1- Alkyl substituted with alkoxy such as methoxyethyl and 1-ethoxyethyl; alkyl substituted with aryl such as benzyl; etc. Among these, from the viewpoint of heat resistance, particularly preferred are substituents of primary or secondary carbon, such as methyl, ethyl, cyclohexyl, and benzyl, which are difficult to be removed by acid or heat.

As a specific example of the ether dimer, paragraph number 0317 of JP 2013-29760 A can be referred to, and this content is incorporated in this specification. The ether dimer may be only one type or two or more types.

The alkali-soluble resin may contain a structural unit derived from a compound represented by the following formula (X).

In the formula (X), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 10 carbon atoms, and R ₃ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms that may contain a benzene ring. n represents an integer of 1-15.

In the formula (X), the carbon number system of the alkylene group of _{R 2 is preferably 2 to 3.} The carbon number of the alkyl group of R ₃ is 1-20, but 1-10 is more preferable, and _{the alkyl group of R 3} may contain a benzene ring. Examples of the benzene ring-containing alkyl group represented by R ₃ include benzyl, 2-phenyl(iso)propyl and the like.

As a specific example of alkali-soluble resin, the following can be mentioned. In the following resins, the values attached to the main chain are molar ratios.

Alkali-soluble resins can refer to paragraph numbers 0558-0571 of JP 2012-208494 A (corresponding to 0685-0700 of the specification of U.S. Patent Application Publication No. 2012/0255099) The contents are incorporated into this manual. Furthermore, the copolymer (B) described in paragraph numbers 0029 to 0063 of JP 2012-32767 A and the alkali-soluble resin used in the examples, and paragraph numbers 0088 to 0098 of JP 2012-208474 A can also be used. The adhesive resins described in and the adhesive resins used in the examples, the adhesive resins described in paragraph numbers 0022 to 0032 of JP 2012-137531 A, and the adhesive resins used in the examples, JP 2013 The binder resin described in paragraph numbers 0132 to 0143 of 024934 and the binder resin used in the examples, and the binder resin described in paragraph numbers 0092 to 0098 of JP 2011-242752 and the examples The binder resin used is the binder resin described in paragraph numbers 0030 to 0072 of JP 2012-032770 A. These contents are incorporated into this manual.

The acid value of the alkali-soluble resin is preferably 30 to 500 mgKOH/g. The lower limit is more preferably 50 mgKOH/g or more, and more preferably 70 mgKOH/g or more. The upper limit is more preferably 400 mgKOH/g or less, more preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less, and particularly preferably 120 mgKOH/g or less.

The content of the alkali-soluble resin is preferably 0.1 to 20% by mass relative to the total solid content of the composition. The lower limit is more preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, and particularly preferably 3% by mass or more. The upper limit is more preferably 12% by mass or less, and more preferably 10% by mass or less. The composition of the present invention may contain only one kind of alkali-soluble resin, or may contain two or more kinds. When two or more types are contained, it is preferable that the total amount thereof falls within the above-mentioned range.

(Other resins)

The composition of the present invention can contain other than the above-mentioned alkali-soluble resin (also referred to as other resin). As other resins, for example, (meth)acrylic resins, (meth)acrylamide resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polyether resins, and polyether resins can be cited. Aluminium resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, silicon Oxyane resin, epoxy resin, etc. As the cyclic olefin resin, a norbornene resin can be preferably used from the viewpoint of improving heat resistance. Examples of commercially available products of norbornene resins include ARTON series manufactured by JSR Corporation (for example, ARTON F4520).

Examples of epoxy resins include epoxy resins which are glycidyl ether compounds of phenolic compounds, epoxy resins which are glycidyl ether compounds of various novolak resins, alicyclic epoxy resins, and aliphatic epoxy resins. , Heterocyclic epoxy resins, glycidyl ester epoxy resins, glycidylamine epoxy resins, epoxy resins glycidylated with halogenated phenols, silicon compounds with epoxy groups and other silicon compounds Condensates of, copolymers of polymerizable unsaturated compounds with epoxy groups and other polymerizable unsaturated compounds, etc. As a copolymer of a polymerizable unsaturated compound having an epoxy group and other polymerizable unsaturated compounds, among the products available on the market, MARPROOF G-0150M, G-0105SA, G-0130SP, G -0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (manufactured by NOF CORPORATION), etc.

The epoxy equivalent of the epoxy resin is preferably 310~3300g/eq, more preferably 310~1700g/eq, and still more preferably 310~1000g/eq. One type or two or more types of epoxy resins can be mixed and used.

Commercially available epoxy resins can also be used. As a commercially available product, the following epoxy resins can be mentioned, for example. Examples of bisphenol A epoxy resins include JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (above , DIC Corporation) and so on. Bisphenol F type epoxy resins include JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON830, EPICLON835 (above, manufactured by DIC Corporation), LCE-21, RE-602S ( The above, manufactured by Nippon Kayaku Co., Ltd.), etc. Examples of phenol novolak type epoxy resins include JER152, JER154, JER157S70, JER157S65 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N-770, and EPICLON N-775 (above, manufactured by DIC Corporation) Wait. Examples of cresol novolac type epoxy resins include EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above, DIC Corporation (manufactured by DIC Corporation), EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.), etc. Examples of aliphatic epoxy resins include ADEKA RESIN EP-4080S, ADEKA RESIN EP-4085S, ADEKA RESIN EP-4088S (above, manufactured by ADEKA Corporation), CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2083, CELLOXIDE 2085, EHPE3150, EPOLEAD PB 3600, EPOLEAD PB4700 (above, manufactured by Daicel Corporation), DENACOL EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above, manufactured by Nagase ChemteX Corporation), and the like. In addition, ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, ADEKA RESIN EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), JER1031S ( Mitsubishi Chemical Corporation.), etc.

The content of the epoxy resin is preferably 1 to 30% by mass relative to the total solid content of the composition. The lower limit is more preferably 2% by mass or more, and more preferably 3% by mass or more. The upper limit is more preferably 25% by mass or less, and more preferably 20% by mass or less. The composition of the present invention may include only one type of epoxy resin, or may include two or more types. When two or more types are contained, it is preferable that the total amount thereof falls within the above-mentioned range.

Also, when the composition contains epoxy resin and polymerizable compound, the mass ratio of polymerizable compound to epoxy resin is polymerizable compound: epoxy resin=100:1~100:400 is preferably, 100:1~100 : 100 is better.

<<<Multifunctional thiol compound>>>

The composition of the present invention is for the purpose of accelerating the reaction of the polymerizable compound and the like, and may contain a multifunctional thiol compound having two or more mercapto groups in the molecule. The polyfunctional thiol compound is preferably a secondary alkane thiol, and particularly preferably a compound having a structure represented by the following general formula (T1).

(In formula (T1), n represents an integer of 2 to 4, and L represents a linking group of 2 to 4 valences.)

The content of the multifunctional thiol compound is 0.3 to 8.9 relative to the total solid content of the composition The mass% is more preferable, and 0.8 to 6.4 mass% is more preferable. A polyfunctional thiol compound can be added for the purpose of improving stability, odor, resolution, developability, adhesion, and the like.

<<Photopolymerization initiator>>

In the composition of the present invention, when a polymerizable compound is used as the curable compound, it is preferable to contain a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and it can be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light from the ultraviolet region to the visible region is preferable. The photopolymerization initiator is preferably a photoradical polymerization initiator.

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), phosphine compounds such as phosphine oxides, and hexaarylbisimidazole , Oxime derivatives and other oxime compounds, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, amine acetophenone compounds, hydroxyacetophenone, etc. Examples of halogenated hydrocarbon compounds having a triazine skeleton include compounds described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), compounds described in British Patent No. 1388492, and Japanese Patent Application Publication No. 53 -133428, the compound described in German Patent No. 3337024, the compound described in the specification of German Patent No. 3337024, the compound described in J. Org. Chem.; 29, 1527 (1964) based on FC Schaefer et al., Japanese Patent Laid-Open No. 62-58241 The compound described in JP 5-281728 A, the compound described in JP 5-34920 A, the compound described in the specification of U.S. Patent No. 4,212,976, and the like.

From the viewpoint of exposure sensitivity, the photopolymerization initiator is selected from the group consisting of trihalomethyl triazine compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, and acetone compounds. Phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium compounds, benzothiazole compounds, diphenyl ketone compounds, acetophenone compounds, cyclopentadiene-benzene-iron compound Compounds, halomethyl oxadiazole compounds, and 3-aryl-substituted coumarin compounds are preferred. In particular, when the composition of the present invention is used in a solid-state imaging element, in order to form a fine pattern in a sharp shape, it is important to develop the composition without leaving any residue in the unexposed part along with the curability. From this viewpoint, it is particularly preferable to use an oxime compound as the photopolymerization initiator. In particular, when forming a fine pattern in a solid-state imaging element, a stepper exposure machine is used for exposure for hardening. However, the exposure machine may be damaged by halogens, and the addition amount of the photopolymerization initiator needs to be kept low. Therefore, considering these points, it is particularly preferable to use an oxime compound as a photopolymerization initiator. As a specific example of the photopolymerization initiator, paragraph numbers 0265 to 0268 of JP 2013-29760 A can be referred to, and this content is incorporated in this specification.

As the photopolymerization initiator, an α-hydroxyketone compound, an α-aminoketone compound, and an acylphosphine compound can also be suitably used. For example, the α-amine ketone compound described in Japanese Patent Application Laid-Open No. 10-291969 and the phosphine compound described in Patent No. 4225898 can also be used. As the α-hydroxy ketone compound, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (above, manufactured by BASF Corporation) can be used. As the α-amine ketone compound, IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (above, manufactured by BASF Corporation) can be used. As the α-amine ketone compound, the compounds described in JP 2009-191179 A can be used. As the phosphine compound, commercially available IRGACURE-819 or DAROCUR-TPO (above, manufactured by BASF Corporation) can be used.

It is preferable to use an oxime compound as a photoinitiator. Specific examples of the oxime compound include compounds described in Japanese Patent Application Publication No. 2001-233842, Japanese Patent Application Publication No. 2000-80068, Japanese Patent Application Publication No. 2006-342166, and Japanese Patent Application Publication No. 2016-21012, etc. . As an oxime compound that can be suitably used in the present invention, for example, 3-benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3 -Propyloxyiminobutan-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one , 2-benzyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyl Oxyimino-1-phenylpropan-1-one and the like. Can also cite JCSPerkin II (1979, pp.1653-1660), JCSPerkin II (1979, pp.156-162), Journal of Photopolymer Science and Technology (1995, pp.202-232), Japan Compounds described in JP 2000-66385, JP 2000-80068, JP 2004-534797, JP 2006-342166, etc.

Among the commercially available products, IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, and IRGACURE-OXE04 (above, manufactured by BASF Corporation) are also suitably used. You can also use TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD), ADEKA ARKLS NCI-831 (manufactured by ADEKA Corporation), ADEKA ARKLS NCI-930 (manufactured by ADEKA Corporation), ADEKAOPTOMER N-1919 (manufactured by ADEKA Corporation) Production, Photopolymerization initiator described in JP 2012-14052 A) 2).

As an oxime compound other than the above, the compound described in Japanese Patent Application Publication No. 2009-519904 in which an oxime is linked to the N position of the wisazole ring, and US Pat. No. 7,626,957 in which a heterosubstituent is introduced at the diphenyl ketone site can also be used. The compounds described in the bulletin are introduced into the pigment site with The nitro compound described in Japanese Patent Laid-Open No. 2010-15025 and U.S. Patent Publication No. 2009-292039, and the ketoxime compound described in International Publication No. WO2009/131189, containing a triazine skeleton and an oxime skeleton in the same molecule The compound described in U.S. Patent No. 7556910, and the compound described in Japanese Patent Application Laid-Open No. 2009-221114, which has an absorption maximum at 405 nm and has good sensitivity to g-ray light sources, and the like.

The oxime compound is preferably a compound represented by the following formula (OX-1). In addition, the N-O bond of the oxime may be an oxime compound of the (E) body, or an oxime compound of the (Z) body, or a mixture of the (E) body and the (Z) body.

In formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. For details of the formula (OX-1), reference can be made to the description of paragraph numbers 0276 to 0304 of JP 2013-029760 A, and this content is incorporated in this specification.

As the photopolymerization initiator, an oxime compound having a fluorine atom can also be used. Specific examples of the oxime compound having a fluorine atom include the compounds described in JP 2010-262028 A, the compounds 24, 36 to 40 described in JP 2014-500852 A, and JP 2013- Compound (C-3) described in 164471 Bulletin, etc. This content is incorporated in this manual.

As the photopolymerization initiator, an oxime initiator having a nitro group can also be used. The oxime compound having a nitro group is also preferably used as a dimer. As a specific example of the oxime compound having a nitro group, there can be mentioned Paragraph Nos. 0031 to 0047 of JP 2013-114249, Paragraph Nos. 0008 to 0012 and 0070 to 0079 of JP 2014-137466, Compounds described in Paragraph Nos. 0007 to 0025 of Japanese Patent No. 4223071 The described compound, ADEKA ARKLS NCI-831 (manufactured by ADEKA Corporation).

As the photopolymerization initiator, an oxime compound having a sulphur ring can also be used. As a specific example of the oxime compound which has a sulphur ring, the compound described in Unexamined-Japanese-Patent No. 2014-137466 can be mentioned. This content is incorporated in this manual.

As the photopolymerization initiator, an oxime compound having a benzofuran skeleton can also be used. As a specific example, the compounds OE-01 to OE-75 described in International Publication WO2015/036910 can be cited.

Preferred specific examples of the oxime compound are shown below, but the present invention is not limited to these.

[Chemical formula 14]

[Chemical formula 15]

The oxime compound is preferably a compound having an absorption maximum in the wavelength region of 350 nm to 500 nm, and a compound having an absorption maximum in the wavelength region of 360 nm to 480 nm is more preferred. The oxime compound is preferably a compound having a relatively high absorbance at 365 nm and 405 nm.

From the viewpoint of sensitivity, the molar absorption coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and even more preferably 5,000 to 200,000.

The molar absorption coefficient of the compound can be measured using a known method. For example, an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian), an ethyl acetate solvent, and a concentration of 0.01 g/L are preferably used for measurement.

It is also preferable that the photopolymerization initiator contains an oxime compound and an α-amine ketone compound. By simultaneously using By using both, developability is improved, and it is easy to form a pattern with excellent rectangularity. When the oxime compound and the α-amine ketone compound are used at the same time, relative to 100 parts by mass of the oxime compound, the α-amine ketone compound is preferably 50 to 600 parts by mass, and more preferably 150 to 400 parts by mass.

With respect to the total solid content of the composition, the content of the photopolymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and still more preferably 1 to 20% by mass. If the content of the photopolymerization initiator is within the above range, better sensitivity and pattern formation can be obtained. The composition of the present invention may include only one type of photopolymerization initiator, or may include two or more types. When two or more types are contained, it is preferable that the total amount thereof falls within the above-mentioned range.

<<Solvent>>

The composition of the present invention can contain a solvent. Examples of the solvent include organic solvents. The solvent is basically not particularly limited as long as it satisfies the solubility of each component or the coatability of the composition, but it is preferably selected in consideration of coatability and safety of the composition.

Examples of organic solvents include esters, ethers, ketones, and aromatic hydrocarbons. As specific examples, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl serosol acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate Ester, 3-methoxymethyl propionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol monomethyl ether ethyl Acid esters and so on. For the details of the organic solvent, refer to the description of paragraph No. 0223 of International Publication WO2015/166779, which is incorporated in this specification.

However, it is better to reduce the aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) used as solvents for environmental reasons, for example, 50 mass ppm (parts per million) relative to the total amount of organic solvents. The following is better, 10 mass ppm or less is more preferable, and 1 mass ppm or less is advanced One step is better.

An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more types. When two or more organic solvents are used in combination, they are selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl serosol acetate, ethyl lactate, diethylene glycol Dimethyl ether, butyl acetate, 3-methoxymethyl propionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether A mixed solution composed of two or more of propylene glycol methyl ether acetate and propylene glycol methyl ether acetate is preferable.

It is better to use a solvent with a lower metal content, and the metal content of the solvent is preferably 10 parts per billion (parts per billion) or less by mass. A solvent of quality ppt (parts per trillion) grade can be used according to needs, such a high-purity solvent is provided by Toyo Gosei Co., Ltd (The Chemical Daily Co., Ltd., November 13, 2015), for example.

As a method of removing impurities such as metals from the solvent, for example, distillation (molecular distillation, thin film distillation, etc.) or filtration using a filter can be cited. As the filter pore size of the filter used for filtration, 10 nm or less is preferable, 5 nm or less is more preferable, and 3 nm or less is more preferable. The material of the filter is preferably polytetrachloroethylene, polyethylene or nylon.

The solvent may contain isomers (compounds with the same number of atoms and different structures). The isomer may contain only one type, or may contain a plurality of types.

In the organic solvent, the peroxide content is preferably 0.8 mmol/L or less, and it is more preferred that the peroxide content is not substantially contained.

The content of the solvent relative to the total amount of the composition is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and more preferably 25 to 75% by mass.

<<Polymerization inhibitor>>

The composition of the present invention may contain a polymerization inhibitor. Examples of polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tertiary butyl-p-cresol, gallic phenol, tertiary butyl catechol, benzoquinone, 4,4'-sulfur Substituted bis(3-methyl-6-tertiary butylphenol), 2,2'-methylene bis(4-methyl-6-tertiary butylphenol), N-nitrosophenylhydroxylamine The first cerium salt and so on. Among them, p-methoxyphenol is preferred.

The content of the polymerization inhibitor is preferably 0.01 to 5% by mass relative to the total solid content of the composition.

<<Silane Coupling Agent>>

The composition of the present invention can further contain a silane coupling agent. In addition, the silane coupling agent in the present invention has a different component from the above-mentioned near-infrared transparent black color material.

In this specification, the silane coupling agent refers to a silane compound having a hydrolyzable group and other functional groups. The hydrolyzable group refers to a substituent that is directly connected to a silicon atom and can generate a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. As a hydrolyzable group, a halogen atom, an alkoxy group, an acyloxy group, etc. are mentioned, for example, and an alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. The functional group other than the hydrolyzable group is preferably a group that interacts with the resin or forms a bond to show affinity. For example, vinyl groups, styryl groups, (meth)acrylic groups, mercapto groups, epoxy groups, oxetanyl groups, amino groups, ureido groups, sulfide groups, isocyanate groups, etc. can be mentioned, (methyl) Propylene groups and epoxy groups are preferred.

Specific examples of the silane coupling agent include vinyl trimethoxy silane, vinyl triethoxy silane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidol Ether propyl methyl dimethoxy silane, 3-glycidyl ether propyl trimethoxy silane, 3-glycidyl ether propyl methyl diethoxy silane, 3-glycidyl ether propyl triethoxy silane , P-styryl trimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyl Trimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane Silane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyl Trimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyl Trimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyl trimethoxysilane hydrochloride, tris-(trimethoxysilylpropyl) isocyanuric acid Ester, 3-ureapropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl) tetrasulfide , 3-isocyanate propyl triethoxysilane, etc. Alkoxy oligomers can be used in addition to the above. The following compounds can also be used.

Commercial products include KBM-13, KBM-22, KBM-103, KBE-13, KBE-22, KBE-103, KBM-3033, and KBE-3033 manufactured by Shin-Etsu Chemical Co., Ltd. , KBM-3063, KBM-3066, KBM-3086, KBE-3063, KBE-3083, KBM-3103, KBM-3066, KBM-7103, SZ-31, KPN-3504, KBM-1003, KBE-1003, KBM - 303, KBM-402, KBM-403, KBE-402, KBM-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, KBE-9103, KBM-573, KBM-575, KBM-9659, KBE-585, KBM-802, KBM-803, KBE-846, KBE-9007, X-40-1053, X-41-1059A, X-41-1056, X-41-1805, X-41-1818, X-41-1810, X-40-2651, X-40-2655A, KR-513, KC-89S, KR-500, X-40-9225, X-40-9246, X-40-9250, KR-401N, X-40-9227, X-40-9247, KR-510, KR-9218, KR-213, X-40-2308, X-40-9238, etc. Examples of the silane coupling agent include the compounds described in paragraphs 0018 to 0036 of JP 2009-288703, the compounds described in paragraphs 0056 to 0066 of JP 2009-242604, and International Publication WO2015/ The compounds described in paragraph numbers 0229 to 0236 of 166779 are incorporated in this specification.

The content of the silane coupling agent relative to the total solid content of the composition is preferably 0.1-30% by mass, more preferably 0.5-20% by mass, and still more preferably 1-10% by mass.

<<<Surface Active Agent>>>

From the viewpoint of further improving coatability, the composition of the present invention may contain various surfactants. As the surfactant, various surfactants such as fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used. Surfactants can refer to paragraph numbers 0238 to 0245 of International Publication WO2015/166779, which are incorporated in this specification.

By containing a fluorine-based surfactant in the composition of the present invention, the liquid properties (especially fluidity) during the preparation of the coating liquid are further improved, and the uniformity of the coating thickness can be further improved Sexual or liquid-saving. When a coating liquid applied with a composition containing a fluorine-based surfactant is used for film formation, the interfacial tension between the coated surface and the coating liquid decreases, thereby improving the wettability of the coated surface and The coatability of the coated surface is improved. Therefore, it is possible to more appropriately form a uniform thickness film with less uneven thickness.

The fluorine content in the fluorine-based surfactant is preferably 3-40% by mass, more preferably 5-30% by mass, and even more preferably 7-25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective from the viewpoint of uniformity of the thickness of the coating film and liquid-saving properties, and the solubility in the composition is also good.

As a fluorine-based surfactant, specifically, the interface described in paragraph numbers 0060 to 0064 of JP 2014-41318 (corresponding to paragraph numbers 0060 to 0064 of International Publication No. 2014/17669) etc. can be cited. The active agent, the surfactant described in paragraph numbers 0117 to 0132 of JP 2011-132503 A, these contents are incorporated in this specification. Commercial products of fluorine-based surfactants include, for example, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F176, MEGAFAC F177, MEGAFAC F141, MEGAFAC F142, MEGAFAC F143, MEGAFAC F144, MEGAFAC R30, MEGAFAC F437, MEGAFAC F437, F475, MEGAFAC F479, MEGAFAC F482, MEGAFAC F554, MEGAFAC F780 (above, manufactured by DIC Corporation), Fluorado FC430, Fluorado FC431, Fluorado FC171 (above, manufactured by Sumitomo 3M Limited), SURFLON S-382, SURFLON SC-101, SURFLON SC -103, SURFLON SC-104, SURFLON SC-105, SURFLON SC-1068, SURFLON SC-381, SURFLON SC-383, SURFLON S-393, SURFLON KH-40 (above, ASAHI GLASS CO., LTD. (Manufactured by OMNOVA), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (above, manufactured by OMNOVA), etc.

In addition, fluorine-based surfactants can also appropriately use acrylic compounds. The acrylic compound has a molecular structure containing a fluorine atom-containing functional group, and when heated, the portion of the functional group containing the fluorine atom is cut and the fluorine atom Volatile. Examples of such fluorine-based surfactants include MEGAFAC DS series manufactured by DIC Corporation (The Chemical Daily Co., Ltd., February 22, 2016) (Nikkei Sangyo Shimbun, February 23, 2016), For example, MEGAFAC DS-21, and it can be used.

Block polymers can also be used as fluorine-based surfactants. For example, the compound described in JP 2011-89090 A can be mentioned. Fluorine-based surfactants can also be preferably used containing repeating units derived from (meth)acrylate compounds having fluorine atoms and derived from alkoxyl groups having 2 or more (5 or more are preferred). Ethoxy group and propyleneoxy group are preferred) fluorine-containing polymer compound which is the repeating unit of the (meth)acrylate compound. The following compounds are also exemplified as fluorine-based surfactants used in the present invention.

The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000. In the above compound, the% representing the proportion of the repeating unit is mole %.

Fluorine-based surfactants can also be used with fluorine-containing ethylenically unsaturated groups in the side chain Polymer. As a specific example, the compounds described in paragraph numbers 0050 to 0090 and paragraph numbers 0289 to 0295 of JP 2010-164965 A, such as MEGAFAC RS-101, RS-102, RS-718K, manufactured by DIC Corporation, RS-72-K and so on. As the fluorine-based surfactant, the compounds described in paragraph numbers 0015 to 0158 of JP 2015-117327 A can also be used.

Examples of nonionic surfactants include glycerin, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol ethoxylate). Compounds, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurel Ester, polyethylene glycol distearate, sorbitan fatty acid ester, PLURONIC L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), TETRONIC 304, 701, 704, 901, 904 , 150R1 (manufactured by BASF Corporation), SOLSPERSE 20000 (manufactured by The Lubrizol Corporation), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), PIONIN D-6112, D-6112-W, D-6315 (manufactured by TAKEMOTO OIL & FATCO., LTD.), OLFINE E1010, SURFYNOL 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.), and the like.

The content of the surfactant relative to the total solid content of the composition is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass. Surfactant may use only 1 type, and may combine 2 or more types. When two or more types are used, it is preferable that the total amount thereof falls within the above-mentioned range.

<<Other ingredients>>

The composition of the present invention can contain thermal polymerization initiators, thermal polymerization components, ultraviolet absorbers, antioxidants, plasticizers, low-molecular-weight organic carboxylic acids, etc. developability enhancing agents, other fillers, antioxidants Various additives such as chemical agents and anti-aggregation agents. As the ultraviolet absorber, ultraviolet absorbers such as amine diene compounds, salicylic acid compounds, diphenyl ketone compounds, benzotriazole compounds, acrylonitrile compounds, and triazine compounds can be used. Specific examples include Japanese Patent Application Publication No. 2013 -The compound described in No. 68814. As the benzotriazole compound, the MYUA series manufactured by MIYOSHI OIL & FAT CO., LTD. (The Chemical Daily Co., Ltd., February 1, 2016) can be used. As the antioxidant, for example, a phenol compound, a phosphorus compound (for example, the compound described in paragraph 0042 of JP 2011-90147 A), a thioether compound, and the like can be used. As commercially available products, for example, ADKSTAB series manufactured by ADEKA Corporation (AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60, AO-60G, AO-80, AO- 330 etc.).

Metal elements are sometimes included in the composition due to the raw materials used, but from the viewpoint of suppressing the occurrence of defects, etc., the content of the group 2 elements (calcium, magnesium, etc.) in the composition is less than 50 mass ppm. Better, 0.01-10 mass ppm is more preferable. The total amount of the inorganic metal salt in the composition is preferably 100 mass ppm or less, and more preferably 0.5 to 50 mass ppm.

<Preparation method of composition>

The composition of the present invention can be prepared by mixing the aforementioned components.

When preparing the composition, each component may be blended at once, or each component may be dissolved or dispersed in a solvent and then blended one by one. The input sequence and operating conditions during cooperation are not particularly restricted. For example, a composition can be prepared by dissolving or dispersing all the components in a solvent at the same time, or if necessary, two or more solutions or dispersions in which the components are appropriately blended can be prepared in advance, and they can be mixed during use (during coating) It is prepared as a composition.

When the composition of the present invention contains particles such as pigments, the process of dispersing the particles is relatively good. In the process of dispersing particles, the mechanical force used for dispersing particles includes compression, squeezing, impact, shearing, pitting, etc. Specific examples of these processes include bead milling, sand milling, roller milling, ball milling, paint mixing, micro jets, high-speed impellers, sand mixing, jet mixing, high-pressure wet micronization, ultrasonic dispersion, and the like. In the pulverization of particles in a sand mill (bead mill), it is preferable to perform the treatment under conditions that increase the pulverization efficiency by using beads with a smaller diameter and increasing the filling rate of the beads. It is preferable to remove coarse particles by filtration, centrifugal separation, etc. after the pulverization treatment. The process of particle dispersion and the dispersing machine can appropriately use "Dispersion Technology Encyclopedia, issued by JOHOKIKO CO., LTD., July 15, 2005" or "Dispersion technology and industry centered on suspension (solid/liquid dispersion system)" The actual integrated data collection used, issued by the Publishing Department of the Business Development Center, October 10, 1978", the process and dispersion machine described in paragraph number 0022 of Japanese Patent Application Publication No. 2015-157893. In the process of dispersing particles, a salt milling process can be used to refine the particles. The materials, equipment, processing conditions, etc. used in the salt milling process can be referred to, for example, Japanese Patent Application Publication No. 2015-194521 and Japanese Patent Application Publication No. 2012-046629.

When preparing the composition, it is preferable to filter the composition with a filter for the purpose of removing foreign matter or reducing defects. As the filter, as long as it is a filter conventionally used for filtering purposes, etc., it can be used without particular limitation. For example, fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (for example, nylon-6, nylon-6, 6), and polyolefin resins such as polyethylene and polypropylene (PP) are used. (Containing high-density, ultra-high molecular weight polyolefin resin) and other materials. Among these materials, polypropylene (including high-density polypropylene) and nylon are preferred.

The pore size of the filter is preferably about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, and more preferably about 0.05 to 0.5 μm. If the pore size of the filter is in the above range, it can be reliably removed Fine foreign matter. It is also preferable to use a fibrous filter material. Examples of fibrous filter materials include polypropylene fibers, nylon fibers, and glass fibers. Specifically, ROKI TECHNO CO., LTD. SBP type series (SBP008 etc.), TPR type series (TPR002, TPR005 etc.), SHPX type series (SHPX003 etc.) filter cartridges can be mentioned.

When a filter is used, different filters (for example, the first filter and the second filter, etc.) can be combined. At this time, the filtration by each filter may be performed only once, or it may be performed more than twice.

Filters with different pore sizes within the above range can be combined. The pore size here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, Nihon Pall Ltd. (DFA4201NXEY, etc.), Advantec Toyo Kaisha, Ltd., Entegris Japan Co., Ltd. (formerly Japan Microlis Co., Ltd.), or KITZ MICRO FILTER CORPORATION, etc. can be obtained. Choose from various filters provided.

The second filter can be formed of the same material as the first filter.

Filtration with the first filter can filter only the dispersion, and after mixing other components, filter with the second filter.

The total solid content (solid content concentration) of the composition can be changed depending on the applicable method, for example, 1-50% by mass is preferable. More preferably, the lower limit is 10% by mass or more. The upper limit is more preferably 30% by mass or less.

With regard to the composition of the present invention, when a film with a film thickness of 1 μm, 2 μm, 3 μm, 4 μm, or 5 μm after drying is produced, it satisfies the maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 700 nm 20% or less, and the transmittance of light in the thickness direction of the film is at the wavelength The spectroscopic characteristic in the range of 1100 to 1300 nm is preferably 70% or more. The maximum value in the wavelength range of 400 to 700 nm is preferably 15% or less, and more preferably 10% or less. The minimum value in the wavelength range of 1100 to 1300 nm is more preferably 75% or more, and more preferably 80% or more.

It is more preferable that the composition of the present invention satisfies any of the following (1) to (3) spectral characteristics.

(1): When a film with a film thickness of 1 μm, 2 μm, 3 μm, 4 μm, or 5 μm after drying is manufactured, the maximum transmittance of light in the thickness direction of the film in the wavelength range of 400 to 750 nm is 20% or less ( 15% or less is preferable, 10% or less is more preferable), and the light transmittance in the thickness direction of the film has a minimum value of 70% or more in the wavelength range of 900 to 1300 nm (75% or more is preferable, 80 Above% is better).

(2): When a film with a film thickness of 1 μm, 2 μm, 3 μm, 4 μm, or 5 μm after drying is manufactured, the maximum transmittance of light in the thickness direction of the film in the wavelength range of 400 to 830 nm is 20% or less ( 15% or less is preferable, 10% or less is more preferable), and the light transmittance in the thickness direction of the film has a minimum value of 70% or more in the wavelength range of 1000 to 1300 nm (75% or more is preferable, 80 Above% is better).

(3): When a film with a film thickness of 1 μm, 2 μm, 3 μm, 4 μm, or 5 μm after drying is manufactured, the maximum transmittance of light in the thickness direction of the film in the wavelength range of 400 to 950 nm is 20% or less ( 15% or less is preferable, 10% or less is more preferable), and the light transmittance in the thickness direction of the film has a minimum value of 70% or more in the wavelength range of 1100 to 1300 nm (75% or more is preferable, 80 Above% is better).

<Pattern Formation Method>

Next, a pattern formation method using the composition of the present invention will be described. The pattern forming method includes a process of forming a composition layer on a support using the composition of the present invention and a process of patterning the composition layer by photolithography or dry etching.

The pattern formation using the photolithography method includes a process of forming a composition layer on a support using the composition of the present invention, a process of exposing the composition layer in a pattern, and a process of developing and removing unexposed parts to form a pattern. Better.

Pattern formation by dry etching includes a process of forming a composition layer on a support using the composition of the present invention and curing to form a hardened layer, and a process of forming a photoresist layer on the hardened layer. The process of patterning the photoresist layer by exposure and development to obtain a photoresist pattern, and the process of dry etching the hardened layer using the photoresist pattern as an etching mask to form a pattern are preferable. Hereinafter, each manufacturing process will be described.

<<The process of forming the composition layer>>

In the process of forming the composition layer, the composition of the present invention is used to form the composition layer on the support.

As a method of applying to the composition of the support, a known method can be used. For example, the drop method (drop casting); slit coating method; spray method; roll coating method; spin coating method (spin coating method); cast coating method; slit spin coating method; pre-wet method (For example, the method described in Japanese Patent Application Publication No. 2009-145395); inkjet (for example, on-demand method, piezoelectric method, thermal method), nozzle jet and other ejection printing, flexographic printing, screen printing, gravure printing , Reverse offset printing, metal mask printing and other printing methods; transfer methods using molds, etc.; nanoimprinting, etc. There is no particular limitation on the applicable method of using inkjet. For example, "Extension‧ Usable Inkjet-Patented Unlimited Possibilities to See -, issued in February 2005, the method described in the Japanese Patent Publication of SBRESEARCH CO., LTD. (especially pages 115 to 133), or Japanese Patent Application Publication No. 2003-262716 , Japanese Patent Application Publication No. 2003-185831, Japanese Patent Application Publication No. 2003-261827, Japanese Patent Application Publication No. 2012-126830, Japanese Patent Application Publication No. 2006-169325, etc.

The composition layer formed on the support can be dried (pre-baked). When the pattern is formed by a low-temperature process, pre-bake is not necessary. When pre-baking is performed, the pre-baking temperature is preferably 150°C or lower, more preferably 120°C or lower, and even more preferably 110°C or lower. The lower limit can be set to 50°C or higher, or 80°C or higher, for example. The pre-bake time is preferably from 10 to 3000 seconds, more preferably from 40 to 2500 seconds, and even more preferably from 80 to 2200 seconds. Drying can be performed using a hot plate, an oven, or the like.

(When using photolithography to form patterns)

<<Exposure Process>>

Next, the composition layer is exposed in a pattern (exposure process). For example, by exposing the composition layer through an exposure device such as a stepper through a mask having a predetermined mask pattern, pattern exposure can be performed. Thereby, the exposed part can be cured.

As the radiation (light) that can be used for exposure, ultraviolet rays such as g-rays and i-rays are preferably used (i-rays are particularly preferred). Irradiation amount (exposure amount) based, for example, 0.03 ~ 2.5J / cm ² is preferred, 0.05 ~ 1.0J / cm ² is more preferably, 0.08 ~ 0.5J / cm ² is further preferred.

Regarding the oxygen concentration during exposure, it can be appropriately selected. In addition to performing under high pressure, for example, it can be performed in a low-oxygen atmosphere with an oxygen concentration of 19% by volume or less (15% by volume or less is preferable, and 5% by volume or less is more preferable. Substantially oxygen-free is further preferred.) Exposure can also be carried out under a high oxygen atmosphere with an oxygen concentration greater than 21% by volume (22% by volume or more is preferred, 30% by volume or more is more preferred, and 50% by volume or more is more preferred. Best) Exposure. Exposure illuminance can be appropriately set generally possible (as preferred, 15000W / m ² or more is more preferably 5000W / m ² or more, 35000W / m ² or more is further preferred) from ^{1000W / m 2 ~ 100000W / m} 2 range Make a selection. Oxygen concentration may be appropriately combined exposure illuminance condition, for example, can be set / m, an oxygen concentration of 35 volume% ^CO2 illuminance 20000W / m% at an oxygen concentration of 10 vol illuminance 10000W ² and the like.

<<Development process>>

Next, the unexposed portion is removed by development to form a pattern. The development and removal of the unexposed part can be performed with a developer. Thereby, the composition layer of the unexposed part is eluted by the developing solution during the exposure process, and only the light-hardened part remains on the support.

As the developer, an alkaline developer that does not cause damage to the solid-state imaging element or circuit of the substrate is preferable.

The temperature of the developer is preferably 20 to 30°C, for example. The development time is preferably 20 to 180 seconds. In addition, in order to improve the residue removal, the following process can be repeated several times: every 60 seconds, the developer is thrown off, and then a new developer is supplied.

As the alkali agent used in the developer, for example, ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethyl hydroxide Ammonium, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole, Organic basic compounds such as piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, or sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, Inorganic alkaline compounds such as sodium silicate and sodium metasilicate. The developer preferably uses an alkaline aqueous solution diluted with pure water. The concentration of the alkali agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass. Surfactants can be used in the developer. As an example of the surfactant, the surfactant described in the above-mentioned composition can be mentioned, and a nonionic surfactant is preferred. When a developer containing such an alkaline aqueous solution is used, it is better to wash (rinse) with pure water after development.

After the development process, after drying, a curing process of curing by heat treatment (post-baking) or post-exposure can be performed.

Post-baking is the heat treatment after development for complete hardening. The heating temperature in the post-baking is, for example, preferably 100 to 240°C, more preferably 200 to 240°C. When an organic electroluminescence (organic EL) element is used as the light source, or when the photoelectric conversion film of an image sensor is made of organic materials, the heating temperature is preferably 150°C or less, more preferably 120°C or less, 100°C The following are further preferred, and the temperature below 90°C is particularly preferred. The lower limit can be set to 50°C or higher, for example. Post-baking can be carried out in a continuous or batch type using a heating mechanism such as a heating plate, a flow oven (hot air circulation type dryer), or a high-frequency heater so as to meet the above-mentioned conditions on the developed film.

Post-exposure can be performed by g-ray, h-ray, i-ray, KrF or ArF and other excimer lasers, electron beams, X-rays, etc., but the original high-pressure mercury lamp is used at a low temperature of about 20-50 ℃. Better. The irradiation time is preferably from 10 seconds to 180 seconds, and more preferably from 30 seconds to 60 seconds. When using post-exposure and post-heating at the same time, it is better to perform post-exposure first.

(When patterning by dry etching method)

Regarding pattern formation by dry etching, the composition layer formed on the support is performed Curing to form a cured product layer, and then, the obtained cured product layer can be performed using an etching gas using the patterned photoresist layer as a mask. In the formation of the photoresist layer, it is preferable to further perform a pre-baking treatment. In particular, as a photoresist forming process, a form of performing a heat treatment after exposure and a heat treatment (post-baking treatment) after development is preferable. Regarding the pattern formation by the dry etching method, reference can be made to the description of paragraph numbers 0010 to 0067 of JP 2013-064993 A, which are incorporated in this specification.

By performing the processes described above, it is possible to form a pattern of pixels having the specific spectral characteristics of the present invention. The infrared transmission filter can be composed of only the pixels having the specific spectral characteristics of the present invention, or it can be combined with the pixels having the specific spectral characteristics of the present invention with red, green, blue, magenta, yellow, cyan, black, colorless, etc. Other pixels constitute an infrared transmission filter. When combining pixels with the specific spectral characteristics of the present invention and pixels of other colors to form an infrared transmission filter, the pattern of pixels having the specific spectral characteristics of the present invention may be formed first, or the pattern of other pixels described above may be formed. After that, a pattern of pixels having the specific spectral characteristics of the present invention is formed.

<Cured film>

Next, the cured film in the present invention will be described. The film of the present invention is formed by curing the above-mentioned composition of the present invention. The cured film of the present invention can be suitably used as an infrared transmission filter.

Regarding the cured film of the present invention, the maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 700 nm is 20% or less (15% or less is preferable, and 10% or less is more preferable), and the film The light transmittance in the thickness direction is the minimum value in the wavelength range of 1100~1300nm It is preferably 70% or more (75% or more is preferable, 80% or more is more preferable). According to this aspect, it can be set as a film that can transmit infrared rays while shielding light in the range of 400 to 700 nm in wavelength and having less interference from visible rays.

The cured film of the present invention preferably has any one of the following (1) to (3) spectral characteristics. In this specification, the spectral characteristics of the cured film indicate the value of the transmittance measured in a wavelength range of 300 to 1300 nm using an ultraviolet-visible-near-infrared spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation).

(1): The maximum value of the transmittance of light in the thickness direction of the film in the wavelength range of 400 to 750 nm is 20% or less (15% or less is preferable, and 10% or less is more preferable), and the film thickness direction The minimum value of the transmittance of the upper light in the wavelength range of 900 to 1300 nm is 70% or more (75% or more is preferable, and 80% or more is more preferable). According to this aspect, it can be set as a film that can transmit infrared rays having a wavelength of 900 nm or more while shielding light in the range of 400 to 750 nm in wavelength, while having less interference from visible light.

(2): The maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 830 nm is 20% or less (15% or less is preferable, 10% or less is more preferable), and the film thickness direction The minimum value of the transmittance of the upper light in the wavelength range of 1000 to 1300 nm is 70% or more (75% or more is preferable, and 80% or more is more preferable). According to this aspect, it can be set as a film that can transmit infrared rays having a wavelength of 1000 nm or more while shielding light in the range of 400 to 830 nm in wavelength, while having less interference from visible light.

(3): The maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 950 nm is 20% or less (15% or less is preferable, 10% or less is more preferable), and the film thickness direction superior The minimum value of the light transmittance in the wavelength range of 1100 to 1300 nm is 70% or more (75% or more is preferable, 80% or more is more preferable). According to this aspect, it can be set as a film which can transmit infrared rays with a wavelength of 1100 nm or more while shielding light in the range of 400 to 950 nm in wavelength and with little interference from visible light.

The cured film having the spectroscopic characteristics of (1) above can be formed using the composition of the present invention containing a near-infrared transparent black color material. By further containing a coloring agent, it is easy to adjust the above-mentioned (1) spectroscopy to a preferable range.

The cured film having the spectroscopic properties of (2) above can be formed using the composition of the present invention that contains an infrared absorber in addition to the near-infrared permeable black color material. The infrared absorber is preferably a compound having a maximum absorption wavelength in the range of 800 nm or more and less than 900 nm. Furthermore, by further containing a coloring agent, it is easy to adjust the above-mentioned (2) spectroscopy to a preferable range.

The cured film having the spectral characteristics of (3) above can be formed using the composition of the present invention containing an infrared absorber in addition to the near-infrared permeable black color material. The infrared absorber is preferably a compound having a maximum absorption wavelength in the range of 900 nm or more and less than 1000 nm. In addition, by further containing a coloring agent and/or a compound having a maximum absorption wavelength in the range of 800 nm or more and less than 900 nm, it is easy to adjust the spectroscopy of the above (3) to a preferable range.

The film thickness of the cured film of the present invention is not particularly limited, but is preferably 0.1 to 20 μm, and more preferably 0.5 to 10 μm.

<Infrared transmission filter>

Next, the infrared transmission filter of the present invention will be described. The infrared transmission filter of the present invention has the cured film of the present invention.

The infrared transmission filter of the present invention is preferably used by being laminated on a support. Examples of the support include a substrate made of materials such as silicon, alkali-free glass, soda glass, PYREX (registered trademark) glass, and quartz glass. A charge coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, etc. may be formed on the support. Sometimes a black matrix is formed on the support to isolate each pixel. If necessary, in order to improve the adhesion with the upper layer, prevent the diffusion of substances, or flatten the surface of the substrate, an undercoat layer may be provided on the support.

The infrared transmission filter of the present invention can also be used in combination with a color filter containing a color colorant. The color filter can be manufactured using a coloring composition containing a coloring agent. As the color coloring agent, the color coloring agent described in the above composition can be exemplified. The coloring composition can also contain resins, polymerizable compounds, photopolymerization initiators, surfactants, solvents, polymerization inhibitors, ultraviolet absorbers, and the like. Regarding these details, the materials described in the above-mentioned composition can be cited, and these can be used.

It is also preferable that the infrared transmission filter of the present invention has pixels of the film or laminate of the present invention and pixels selected from red, green, blue, magenta, yellow, cyan, black, and colorless.

<Solid-state imaging device>

The solid-state imaging element of the present invention has the cured film of the present invention. The structure of the solid-state imaging element of the present invention is not particularly limited as long as it has the cured film body of the present invention and functions as a solid-state imaging element. For example, the following structures can be mentioned.

The structure is as follows: on the support, there are a plurality of photodiodes that constitute the light receiving area of the solid-state image sensor (CCD image sensor, CMOS image sensor, etc.) and transfer electrodes including polysilicon, etc., in the photodiode The polar body and the transfer electrode have a light-receiving part with only a photodiode The opening includes a light-shielding film containing tungsten, etc., on the light-shielding film, there is a device protection film including silicon nitride and the like formed to cover the entire surface of the light-shielding film and the photodiode light-receiving part. On the device protection film, the present invention is provided The hardened film. Furthermore, it may be on the device protective film and under the hardened film of the present invention (close to the side of the support) with a light-concentrating mechanism (for example, microlens, etc.), or may be used in the hardened film of the present invention. The film has the structure of the light-concentrating mechanism and so on.

<Infrared Sensor>

The infrared sensor of the present invention has the cured film of the present invention. The structure of the infrared sensor of the present invention is not particularly limited as long as it has the cured film of the present invention and functions as an infrared sensor.

Hereinafter, an embodiment of the infrared sensor of the present invention will be described using FIG. 1.

In the infrared sensor 100 shown in FIG. 1, the symbol 110 is a solid-state imaging device.

The imaging area provided on the solid-state imaging element 110 has an infrared cut filter 111 and a color filter 112.

The infrared cut filter 111 transmits light in the visible light region (for example, light with a wavelength of 400 to 700 nm) and shields light in the infrared region (for example, at least a part of light with a wavelength of 800 to 1300 nm, and light with a wavelength of 900 to 1200 nm. At least a part is preferable, and at least part of light with a wavelength of 900 to 1000 nm is more preferable).

The color filter 112 is a color filter formed with pixels that transmit and absorb light of a specific wavelength in the visible light region. For example, a filter using pixels formed with red (R), green (G), and blue (B) Color device and so on.

Between the infrared transmission filter 113 and the solid-state imaging element 110, an unformed infrared The area 114 of the line cut filter 111. In the area 114, a resin layer (for example, a transparent resin layer, etc.) through which light of the wavelength of the infrared transmission filter 113 can be transmitted is arranged.

The infrared transmission filter 113 is a filter that has visible light shielding properties and transmits infrared light of a specific wavelength, and is composed of the cured film of the present invention.

A microlens 115 is arranged on the incident light hν side of the color filter 112 and the infrared transmission filter 113. A planarization layer 116 is formed to cover the microlens 115.

In the embodiment shown in FIG. 1, the resin layer is arranged in the area 114, but the infrared transmission filter 113 may be formed in the area 114. That is, the infrared transmission filter 113 may be formed on the solid-state imaging element 110.

In the embodiment shown in FIG. 1, the film thickness of the color filter 112 and the film thickness of the infrared transmission filter 113 are the same, but the film thickness of the two may be different.

In the embodiment shown in FIG. 1, the color filter 112 is arranged closer to the incident light hν side than the infrared cut filter 111. However, the order of the infrared cut filter 111 and the color filter 112 may be replaced to make the infrared cut filter 111 The color filter 112 is arranged on the hν side of the incident light.

In the embodiment shown in FIG. 1, the infrared cut filter 111 and the color filter 112 are stacked adjacent to each other, but the two filters need not necessarily be adjacent, and other layers may be provided between the two.

According to the infrared sensor, the image information can be read in real time, so the motion sensing of the object of the recognition and detection motion can be performed. Furthermore, distance information can be obtained, so that it is possible to take pictures of images containing 3D information, etc.

[Example]

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not In violation of its purpose, it is not limited to the following examples. In addition, unless otherwise specified, "part" and "%" are quality standards.

<Preparation of composition>

(Composition 1; Example 1)

Mix 9.0 parts by mass of resin A1, 2.0 parts by mass of color material D1, 1.5 parts by mass of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as a polymerizable compound, 1.5 parts by mass of photopolymerization initiator, and 86.0 parts by mass After stirring the propylene glycol monomethyl ether acetate (PGMEA) as a solvent, it was filtered with a nylon filter (manufactured by NIHON PALL LTD.) with a pore size of 0.5 μm, and a composition 1 was obtained.

(Composition 2; Example 2)

Except that the color material D2 was used instead of the color material D1, in the same manner as the composition 1, a composition 2 was obtained.

(Composition 3; Example 3)

Except that the color material D3 was used instead of the color material D1, in the same manner as the composition 1, a composition 3 was obtained.

(Composition 4; Example 4)

Mix 9.0 parts by mass of resin A2, 2.0 parts by mass of color material D4, 1.5 parts by mass of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as a polymerizable compound, 1.5 parts by mass of photopolymerization initiator, and 86.0 parts by mass After stirring the PGMEA as a solvent, it was filtered with a nylon filter (manufactured by NIHON PALL ITD.) with a pore size of 0.5 μm to obtain a composition 4.

(Composition 5; Example 5)

Mix 9.0 parts by mass of resin A2, 0.5 parts by mass of color material D5, 1.5 parts by mass of color material D3, 1.5 parts by mass of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as a polymerizable compound, and 1.5 parts by mass After stirring a photopolymerization initiator and 86.0 parts by mass of PGMEA as a solvent, it was filtered with a nylon filter (manufactured by NIHON PALL LTD.) with a pore diameter of 0.5 μm, and a composition 5 was obtained.

(Composition 6; Example 6)

Mix 8.0 parts by mass of resin A1, 1.0 parts by mass of resin A3, 2.0 parts by mass of color material D1, 1.5 parts by mass of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as a polymerizable compound, 1.5 parts by mass of light After stirring the polymerization initiator, 70.0 parts by mass of PGMEA, and 16.0 parts by mass of dichloromethane, it was filtered with a nylon filter (manufactured by NIHON PALL LTD.) with a pore diameter of 0.5 μm, and a composition 6 was obtained.

(Composition 7; Example 7)

8.0 parts by mass of resin A1, 1.0 parts by mass of resin A4, 2.0 parts by mass of color material D3, 0.2 parts by mass of color material D7, and 1.5 parts by mass of KAYARAD DPHA (Nippon Kayaku Co., Ltd. as a polymerizable compound) were mixed. (Product), 1.5 parts by mass of a photopolymerization initiator, and 86.0 parts by mass of PGMEA, and stirred, and then filtered with a nylon filter (manufactured by NIHON PALL LTD.) with a pore diameter of 0.5 μm to obtain a composition 7.

(Composition 8; Comparative Example 1)

Except that the color material D6 was used instead of the color material D1, a composition 8 was obtained in the same manner as the composition 1 except that the color material D6 was used.

(Composition 9; Comparative Example 2)

Except having changed the content of the color material D6 to 0.5 parts by mass, in the same manner as in the composition 8, a composition 9 was obtained.

(Composition 10; Comparative Example 3)

600.0g of black pigment (Irgaphor Black S0100CF manufactured by BASF), 321.4g of acrylic resin A (methyl methacrylate/methacrylic acid/styrene copolymer (mass ratio 30/40/30, Mw=10,000, acid Value=110mgKOH/g)) 35% by mass solution of propylene glycol monomethyl ether acetate, 93.8g of dispersant (BYK21116; manufactured by BYK Chemie GmbH), and 1984.8g of propylene glycol monoethyl ether acetate (PGMEA) were added to the tank In this, it was stirred with a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) for 1 hour to obtain a preliminary dispersion liquid 1. After that, the preliminary dispersion 1 was supplied to a nanomill (Ultra Apex Mill) (Kotobuki Industrial Co.) equipped with a centrifugal separator filled with 70% zirconia beads (manufactured by TORAY INDUSTRIES, INC.) with a diameter of 0.10 mm. , Ltd.), dispersion was performed at a rotation speed of 8 m/s for 2 hours to obtain a black pigment dispersion liquid 1 having a solid content concentration of 25% by mass and a pigment/resin (mass ratio)=80/20.

0.38 g of ADEKA ARKLS (registered trademark) NCI-831 as a photopolymerization initiator was added to 29.52 g of PGMEA, and the mixture was stirred until the solid content was dissolved. Furthermore, 16.03 g of a 35% by mass solution of PGMEA of acrylic resin A, 3.38 g of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) as a polymerizable compound, and 0.24 g of a silicone-based surfactant BYK333 as a surfactant were added. A 10% by mass solution of propylene glycol monomethyl ether acetate (PMA) was stirred at room temperature for 1 hour to obtain a photosensitive resist. Add 10.46g to the photosensitive photoresist The black pigment dispersion 1 of, thus the composition 10 was prepared.

Color materials D1~D7: compounds with the following structures. D1, D3, and D4 are near-infrared permeable black color materials containing a dye compound having a crosslinkable group. D2 is a dye multimer formed by polymerizing D1 (where n is 5 and Mw=3000). D5 is a red colorant containing a dye compound having a crosslinkable group. D6 is a near-infrared permeable black color material containing a dye compound that does not have a crosslinkable group. Color materials D1~D7 are compounds that dissolve more than 3g in 100g of propylene glycol monomethyl ether acetate at 23°C.

[Chemical formula 18]

Resin A1: Resin of the following structure (Mw=40,000). The values attached to the main chain are molar ratios.

Resin A2: Resin of the following structure (Mw=14,000). The values attached to the main chain are molar ratios.

Resin A3: ARTON F4520 (manufactured by JSR Corporation, norbornene resin)

Resin A4: MARPROOF G-0150M (manufactured by NOF CORPORATION, glycidyl methacrylate backbone random polymer)

[Chemical formula 19]

Photopolymerization initiator: a compound of the following structure

[Absorbance measurement]

Each composition was spin-coated on a glass substrate so that the film thickness after baking became 1.1 micrometers, and it heated at 100 degreeC with a hotplate for 120 seconds, and it dried. After drying, it was further heated (post-baked) at 220°C for 300 seconds on a hot plate to form a cured film. The glass substrate on which the cured film was formed was measured with an ultraviolet-visible-near-infrared spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation) to measure the transmittance in the wavelength range of 300 to 1300 nm, and the transmittance in the wavelength range of 400 to 700 nm. The minimum value A of absorbance and the maximum value B of absorbance in the wavelength range of 1100 to 1300 nm. The following table shows the value of the spectral characteristic A/B of each composition.

[Pattern Formation]

Each composition was spin-coated on a silicon wafer so that the film thickness after baking became 1.1 μm, and was dried by heating at 100° C. for 120 seconds on a hot plate. Next, use the i-ray stepper exposure device FPA-3000i5+ (manufactured by Canon Inc.), and use a mask formed with a 1.1 μm square pixel pattern to ^{rise from 50 to 750 mJ/cm 2} every 50 mJ/cm ² to determine Analyze the optimal exposure of the above-mentioned square pixel pattern, and perform exposure with the optimal exposure. After that, the silicon wafer with the exposed coating film is placed on the horizontal rotating table of a rotary/spray developing machine (Model DW-30, manufactured by CHEMITRONICS CO., LTD.), and CD-2060 (hydroxide) is used. Tetramethylammonium aqueous solution (manufactured by FUJIFILM Electronic Materials Co., Ltd.) was subjected to spin immersion development at 23°C for 60 seconds to form a pattern on the silicon wafer. The patterned silicon wafer was rinsed with pure water, and then spin-dried. Next, heat treatment (post-baking) was performed for 300 seconds using a heating plate at 220°C to obtain a patterned silicon wafer (infrared transmission filter).

<Solvent resistance evaluation>

The infrared transmission filter was immersed in PGMEA for 300 seconds, and the transmittance (unit %) of light with a wavelength of 400 to 700 nm before and after the immersion in PGMEA was measured, and the change in transmittance was determined by the following formula. In addition, the change in transmittance was evaluated by the transmittance at the wavelength where the change in transmittance before and after immersion in PGMEA is the largest.

Transmittance change=|(Transmittance after immersion in PGMEA (%)-Transmittance before immersion in PGMEA (%))|

The solvent resistance was evaluated based on the following standards.

3: The transmittance change before and after immersion is less than 3%

2: The change in transmittance before and after immersion is 3% or more and less than 5%

1: The change in transmittance before and after immersion is 5% or more

<Pattern Resolution (Pattern Formability)>

The shape of the obtained pattern was evaluated according to the following criteria.

3: The square shape can be clearly recognized.

2: Able to recognize square shapes

1: Shape deformation

<Spectroscopic Recognition>

The obtained infrared transmission filter is assembled in a solid-state imaging device according to a known method. The obtained solid-state imaging device was used to irradiate a near-infrared LED (Light Emitting Diode) light source with an emission wavelength of 940 nm in a low-illuminance environment (0.001 Lux), and image capture was performed, and the image performance was compared and evaluated.

The spectroscopic recognition was evaluated according to the following criteria.

3: Good The subject can be clearly identified on the image.

2: Slightly good The subject can be recognized on the image.

1: Insufficient The subject cannot be recognized on the image.

As shown in the above table, the examples have excellent pattern resolution and solvent resistance. In addition, the infrared transmission filter formed using the composition of the example has good spectroscopic recognition. In contrast, the comparative example was inferior in at least one of solvent resistance and pattern resolution.

In Example 1, instead of the color material D1, the crosslinkable dye of the pigment skeleton of a perylene compound, an azo compound, or a bisbenzofuranone compound was used, and the same effect was also obtained.

100‧‧‧Infrared sensor

110‧‧‧Solid-state image sensor

111‧‧‧Infrared cut filter

112‧‧‧Color filter

113‧‧‧Infrared transmission filter

114‧‧‧area (resin layer)

115‧‧‧Micro lens

116‧‧‧Planarization layer

hν‧‧‧incident light

Claims (9)

A composition comprising a near-infrared permeable black color material, a curable compound, and a solvent, wherein the near-infrared permeable black color material contains a dye having at least one crosslinkable group selected from epoxy groups and alkoxysilyl groups For the compound, the ratio of the minimum value A of the absorbance in the wavelength range of 400 to 700 nm and the maximum value B of the absorbance in the wavelength range of 1100 to 1300 nm of the composition, that is, A/B is 4.5 or more. The composition described in item 1 of the scope of patent application, wherein the crosslinkable group possessed by the aforementioned dye compound is an epoxy group. The composition described in item 1 or item 2 of the scope of patent application, wherein the dye compound having a crosslinkable group is at least one selected from the group consisting of xanthene compounds, perylene compounds, azo compounds, and bisbenzofuranone compounds 1 kind. The composition described in item 1 or item 2 of the scope of patent application, wherein the aforementioned dye compound having a crosslinkable group is a xanthene compound. The composition described in item 1 or item 2 of the scope of the patent application further contains a coloring agent. A cured film formed by curing the composition described in any one of items 1 to 5 in the scope of the patent application. An infrared transmission filter having the cured film described in item 6 of the scope of patent application. A solid-state imaging element having the cured film described in item 6 of the scope of patent application. An infrared sensor with the cured film described in item 6 of the scope of patent application.

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