JP2021091770A - Coloring composition, infrared light cut filter, filter for solid-state image sensor, solid-state image sensor, and method for manufacturing filter for solid-state image sensor - Google Patents

Abstract

To provide a coloring composition that enables suppression of decrease in absorbance of infrared light.SOLUTION: A coloring composition includes a coloring agent including an expanded phthalocyanine represented by a formula (3), a curable compound, an organic solvent dissolving the curable compound, and a dispersant including a block copolymer which has: a first block including a functional group having affinity to adsorb the expanded phthalocyanine; and a second block having affinity with the organic solvent or the curable compound.SELECTED DRAWING: None

Description

The present invention relates to a coloring composition, an infrared light cut filter, a filter for a solid-state image sensor including an infrared light cut filter, a solid-state image sensor, and a method for manufacturing a filter for a solid-state image sensor.

A solid-state image sensor such as a CMOS image sensor or a CCD image sensor includes a photoelectric conversion element that converts light intensity into an electric signal. An example of a solid-state image sensor is capable of detecting light for a plurality of colors. The solid-state image sensor includes a color filter for each color and a photoelectric conversion element, and detects light for each color by the photoelectric conversion element for each color (see, for example, Patent Document 1). Another example of the solid-state imaging device includes an organic photoelectric conversion element and an inorganic photoelectric conversion element, and each photoelectric conversion element detects light of each color without using a color filter (see, for example, Patent Document 2).

The solid-state image sensor includes an infrared light cut filter on the photoelectric conversion element. The infrared light cut filter absorbs the infrared light to cut the infrared light that can be detected by each photoelectric conversion element with respect to the photoelectric conversion element. As a result, the detection accuracy of visible light in each photoelectric conversion element is improved. The infrared light cut filter contains, for example, phthalocyanine (see, for example, Patent Document 3).

Japanese Unexamined Patent Publication No. 2003-060176 JP-A-2018-060910 Japanese Unexamined Patent Publication No. 2018-12907

By the way, in the process of manufacturing an infrared light cut filter, phthalocyanines that are aggregated or aggregated without being dispersed in a solvent may form an infrared light cut filter as an aggregate such as an aggregate or an aggregate. Since the absorbance of infrared light contained in phthalocyanine existing as an aggregate is lower than the absorbance of infrared light possessed by dispersed phthalocyanine, it is desired to enhance the dispersibility of phthalocyanine in an infrared light cut filter containing phthalocyanine. ing.

The present invention provides a coloring composition capable of suppressing a decrease in the absorbance of infrared light, an infrared light cut filter, a filter for a solid-state image sensor, a solid-state image sensor, and a method for manufacturing a filter for a solid-state image sensor. With the goal.

The coloring composition for solving the above-mentioned problems includes a colorant, a dispersant, a curable compound, and an organic solvent that dissolves the curable compound. The colorant contains an expanded phthalocyanine represented by the following formula (1), and the dispersant contains a block copolymer having a first block and a second block. The first block contains either an acidic functional group or a basic functional group having an affinity for adsorbing the expanded phthalocyanine, and the second block makes the expanded phthalocyanine insoluble and said. It has an affinity with an organic solvent or the curable compound.

However, in the formula (1), M is molybdenum or tungsten. R1 and R2 are hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocycle. Oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl Sulfonylamino group, arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, aryloxy It contains any one of a carbonyl group, an alkoxycarbonyl group, a carbamoyl group, an arylazo group, a heterocyclic azo group, an imide group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, and a silyl group.

The infrared light cut filter for solving the above problems includes a colorant, a dispersant, and a cured product of a curable compound. The colorant contains an expanded phthalocyanine represented by the following formula (1), and the dispersant contains a block copolymer having a first block and a second block. The first block contains either an acidic functional group or a basic functional group having an affinity for adsorbing the expanded phthalocyanine, and the second block makes the expanded phthalocyanine insoluble and said. It has an affinity with an organic solvent that dissolves a curable compound or the curable compound.

However, in the formula (1), M is molybdenum or tungsten. R1 and R2 are hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocycle. Oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl Sulfonylamino group, arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, aryloxy It contains any one of a carbonyl group, an alkoxycarbonyl group, a carbamoyl group, an arylazo group, a heterocyclic azo group, an imide group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, and a silyl group.

A method for producing a filter for a solid-state image sensor for solving the above problems is a coating film containing a coloring agent, a dispersant, a curable compound, and a coloring composition containing an organic solvent, wherein the coloring agent is as follows. Includes extended phthalocyanine represented by formula (1). The dispersant contains the first block containing either an acidic functional group or a basic functional group having an affinity for adsorbing the expanded phthalocyanine, and the expanded phthalocyanine insoluble and the curable compound. Coloring is performed by forming the coating film containing a block copolymer having a second block having an affinity for an organic solvent that dissolves the substance, and by curing the curable compound to cure the coating film. It includes forming a layer and patterning the colored layer by dry etching.

However, in the formula (1), M is molybdenum or tungsten. R1 and R2 are hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocycle. Oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl Sulfonylamino group, arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, aryloxy It contains any one of a carbonyl group, an alkoxycarbonyl group, a carbamoyl group, an arylazo group, a heterocyclic azo group, an imide group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, and a silyl group.

According to each of the above configurations, the dispersant is located between the dilated phthalocyanine and the other dilated phthalocyanine by adsorbing the first block of the dispersant on the dilated phthalocyanine. Then, a distance is formed between the dilated phthalocyanines to the extent that the association and aggregation of the dilated phthalocyanines are suppressed. As a result, the decrease in absorbance due to the association and aggregation of the expanded phthalocyanine, that is, the decrease in the absorbance at the wavelength at which the monomer is expected to be absorbed by the expanded phthalocyanine is suppressed. As a result, in the infrared light cut filter, it is possible to suppress a decrease in the absorbance of infrared light.

In the coloring composition, the curable compound contains an acrylic polymer, and the acrylic polymer may be an acrylic polymer containing any of an aromatic ring, an alicyclic, and a cyclic ether in a side chain. According to this configuration, when the acrylic polymer contains any of aromatic ring, alicyclic, and cyclic ether, the effect of suppressing the decrease in absorbance at the wavelength expected to be absorbed by the extended phthalocyanine is effective. Can be enhanced.

In the coloring composition, the organic solvent may contain at least one of a ketone solvent, an ether solvent, and an ester solvent. According to this configuration, it is possible to enhance the dispersibility of the expanded phthalocyanine in a dispersion system using at least one of a ketone solvent, an ether solvent, and an ester solvent as an organic solvent.

In the coloring composition, the organic solvent may be propylene glycol monomethyl ether acetate. According to this configuration, since the organic solvent is propylene glycol monomethyl ether acetate, the dispersibility of the expanded phthalocyanine is enhanced, and further, a coating film having a uniform thickness can be formed when an infrared light cut filter is obtained. It's easy.

In the coloring composition, the glass transition temperature of the dispersant may be 30 ° C. or higher. According to this configuration, since the glass transition temperature of the dispersant is 30 ° C. or higher, it is possible to suppress a decrease in the absorbance of infrared light.

In the coloring composition, the glass transition temperature of the curable compound may be 30 ° C. or higher. According to this configuration, since the glass transition temperature of the curable compound is 30 ° C. or higher, it is possible to suppress a decrease in the absorbance of infrared light.

In the coloring composition, the average molecular weight of the curable compound may be 10,000 or more and 150,000 or less. According to this configuration, since the average molecular weight of the curable compound is 10,000 to 150,000 or less, it is possible to sufficiently obtain the mechanical strength and light resistance of the infrared light cut filter.

In the coloring composition, the curable compound contains an acrylic polymer, and the mass of the acrylic monomer (MM) with respect to the sum (MS) of the mass of the acrylic polymer and the mass of the acrylic monomer used to produce the acrylic polymer. ) May be 20% or less (MM / MS × 100).

According to the above configuration, since the amount of the acrylic monomer remaining in the coloring composition is 20% or less, it is possible to suppress the decrease in the absorbance of infrared light in the expanded phthalocyanine due to the residual acrylic monomer.

In the coloring composition, the percentage of the mass of the coloring agent to the mass of the total solid content contained in the coloring composition may be 30% or more.

According to the above configuration, the mass of the colorant with respect to the mass of the total solid content contained in the coloring composition is 30% or more, and the dispersibility of the expanded phthalocyanine is enhanced by the block copolymer. Therefore, for example, 1 μm. It is also possible to increase the absorbance of infrared light even when an infrared light cut filter having the following thickness is formed.

The infrared light cut filter for solving the above problems is an infrared light cut filter formed by using the above coloring composition.
The filter for a solid-state image sensor for solving the above-mentioned problems includes the above-mentioned infrared light cut filter.
The solid-state image sensor for solving the above problems includes a photoelectric conversion element and the filter for the solid-state image sensor.

According to the present invention, in the infrared light cut filter, it is possible to suppress a decrease in the absorbance of infrared light.

The exploded perspective view which shows the layer structure in one Embodiment of a solid-state image sensor.

An embodiment in a method for manufacturing a coloring composition, an infrared light cut filter, a filter for a solid-state image sensor, a solid-state image sensor, and a filter for a solid-state image sensor will be described with reference to FIG. FIG. 1 is a schematic configuration diagram showing each layer of a part of a solid-state image sensor separated. In the present embodiment, the infrared light means light having a wavelength included in the range of 0.7 μm or more and 1 mm or less, and the near infrared light is particularly 700 nm or more and 1100 nm among the infrared light. It means light having a wavelength included in the following range.

[Solid image sensor]
As shown in FIG. 1, the solid-state image sensor 10 includes a filter 10F for a solid-state image sensor and a plurality of photoelectric conversion elements 11. The solid-state image sensor filter 10F includes a plurality of visible light filters 12R, 12G, 12B, an infrared light path filter 12P, an infrared light cut filter 13, a plurality of visible light microlenses 15R, 15G, 15B, and a plurality of visible light filters. , A microlens 15P for infrared light is provided.

The plurality of photoelectric conversion elements 11 include a red photoelectric conversion element 11R, a green photoelectric conversion element 11G, a blue photoelectric conversion element 11B, and an infrared light photoelectric conversion element 11P. The solid-state imaging device 10 includes a plurality of red photoelectric conversion elements 11R, a plurality of green photoelectric conversion elements 11G, a plurality of blue photoelectric conversion elements 11B, and a plurality of infrared light photoelectric conversion elements 11P. The plurality of infrared light photoelectric conversion elements 11P measure the intensity of infrared light. Note that FIG. 1 shows the repeating unit of the photoelectric conversion element 11 in the solid-state image sensor 10 for convenience of illustration.

The color filter for visible light is composed of a red filter 12R, a green filter 12G, and a blue filter 12B. The red filter 12R is located on the incident side of the light with respect to the red photoelectric conversion element 11R. The green filter 12G is located on the incident side of light with respect to the green photoelectric conversion element 11G. The blue filter 12B is located on the incident side of light with respect to the blue photoelectric conversion element 11B.

The solid-state image sensor filter 10F includes an infrared light path filter 12P on the incident side of light with respect to the infrared light photoelectric conversion element 11P. The infrared light path filter 12P cuts visible light that can be detected by the infrared light photoelectric conversion element 11P with respect to the infrared light photoelectric conversion element 11P. As a result, the detection accuracy of infrared light by the infrared light photoelectric conversion element 11P is improved. The infrared light that can be detected by the infrared light photoelectric conversion element 11P is, for example, near-infrared light having a wavelength of 700 nm or more and 1100 nm or less. The infrared light pass filter 12P is formed by forming a coating film containing a black photosensitive resin and patterning the coating film using a photolithography method.

The infrared light cut filter 13 is located on the incident side of light with respect to the filters 12R, 12G, and 12B for each color. The infrared light cut filter 13 includes a through hole 13H, so that the infrared light cut filter 13 is not located on the incident side of light with respect to the infrared light path filter 12P. The infrared light cut filter 13 is common to the red filter 12R, the green filter 12G, and the blue filter 12B. The infrared light cut filter 13 overlaps the color filters 12R, 12G, and 12B when viewed from the direction in which the solid-state image sensor filter 10F and the photoelectric conversion element 11 overlap. The infrared light cut filter 13 can have a thickness of, for example, 300 nm or more and 3 μm or less.

The microlens is composed of a red microlens 15R, a green microlens 15G, a blue microlens 15B, and an infrared light microlens 15P. The red microlens 15R is located on the incident side of the light with respect to the red filter 12R. The green microlens 15G is located on the incident side of the light with respect to the green filter 12G. The blue microlens 15B is located on the incident side of the light with respect to the blue filter 12B. The infrared light microlens 15P is located on the incident side of the light with respect to the infrared light path filter 12P.

Each microlens 15R, 15G, 15B, 15P includes an incident surface 15S which is an outer surface. Each microlens 15R, 15G, 15B, 15P has a refractive index difference with the outside air for collecting light entering the incident surface 15S toward each photoelectric conversion element 11R, 11G, 11B, 11P.

[Infrared light cut filter]
Hereinafter, the infrared light cut filter 13 will be described in more detail.
The infrared light cut filter 13 contains a colorant, a dispersant, and a cured product of a curable compound. The infrared light cut filter 13 is formed by using a coating liquid containing a coloring composition. The coloring composition comprises a colorant, a dispersant, a curable compound, and an organic solvent.

[Colorant]
The colorant contains dilated phthalocyanine represented by the following formula (1).

In the above formula (1), M is molybdenum or tungsten. R1 and R2 are hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocycle. Oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfate Famoylamino group, alkylsulfonylamino group, arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group , Acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, arylazo group, heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, and silyl group. Including either.

The dilated phthalocyanine is a phthalocyanine obtained by extending the π-conjugated system of the phthalocyanine. In the above formula (1), the plurality of R1s may be the same as each other or may be different from each other. The plurality of R2s may be the same as each other or different from each other. Further, two substituents existing on the same benzene ring and selected from R1 and R2 may be linked to each other to form a ring. R1 and R2 are preferably a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, and an arylthio group.

The alkyl group may be linear or branched. Alkyl groups include cycloalkyl groups and bicycloalkyl groups. The number of carbon atoms of the alkyl group may be 1 or more and 20 or less, and preferably 4 or more and 12 or less. The alkyl group includes, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group and an octyl group. , Nonyl group, decyl group, dodecyl group and the like. The hydrogen atom of the alkyl group may be substituted with a halogen atom or the like.

The alkenyl group may include a cycloalkenyl group and a bicycloalkenyl group. The alkenyl group may be, for example, a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, a hexenyl group, a cyclohexenyl group, an octenyl group and the like.

The aryl group may be monocyclic or polycyclic. Further, the aryl group may be a group in which two or more benzene rings are bonded via a single bond or a divalent organic group. Further, the aryl group may be a group in which two or more fused rings are bonded via a single bond or a divalent organic group. The divalent organic group may be an alkenylene group such as a vinylene group. The aryl group may be a heteroaryl group. The number of carbon atoms of the aryl group may be 6 or more and 20 or less, and preferably 6 or more and 14 or less. Aryl groups include, for example, phenyl group, alkylphenyl group, alkoxyphenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthrasenyl group, 2-anthracenyl group, 9-anthrasenyl group, 2-biphenyl group, 3-biphenyl group. The group may be a 4-biphenyl group, a thienyl group, a pyridyl group, an indrill group, or the like. The hydrogen atom of the aryl group may be substituted with a halogen atom or the like.

The alkylphenyl group may be one in which the hydrogen atom of the phenyl group is replaced with an alkyl group. The alkylphenyl group includes, for example, methylphenyl group, ethylphenyl group, dimethylphenyl group, propylphenyl group, mesityl group, methylethylphenyl group, isopropylphenyl group, n-butylphenyl group, isobutylphenyl group, and t-butyl. It may be a phenyl group or the like.

The alkoxyphenyl group may be one in which the hydrogen atom of the phenyl group is replaced with an alkoxy group. The alkoxyphenyl group includes, for example, a methoxyphenyl group, an ethoxyphenyl group, a propyloxyphenyl group, an isopropyloxyphenyl group, an n-butoxyphenyl group, an isobutoxyphenyl group, an s-butoxyphenyl group, a t-butoxyphenyl group, and the like. May be.

The alkoxy group may be linear or branched. The alkoxy group may be, for example, a cycloalkyloxy group. The number of carbon atoms of the alkoxy group may be 1 or more and 20 or less, and preferably 4 or more and 12 or less. The alkoxy group includes, for example, a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, an n-butoxy group, an isobutoxy group, an s-butoxy group, a t-butoxy group, a pentyloxy group, a hexyloxy group, a cyclohexyloxy group, and the like. It may be a heptyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group, a dodecyloxy group and the like. The hydrogen atom of the alkoxy group may be substituted with a halogen atom or the like.

The aryloxy group may have 6 or more and 20 or less carbon atoms. The aryloxy group may be, for example, a phenoxy group, an alkylphenoxy group, an alkoxyphenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group and the like. The hydrogen atom of the aryloxy group may be substituted with a halogen atom or the like.

The alkylphenoxy group may be one in which the hydrogen atom of the phenoxy group is substituted with an alkyl group. The alkoxyphenoxy group may be one in which the hydrogen atom of the phenoxy group is substituted with an alkoxy group.

The alkylthio group may be linear or branched. The alkylthio group may be, for example, a cycloalkylthio group. The number of carbon atoms of the alkylthio group may be 1 or more and 20 or less, and preferably 4 or more and 12 or less. The alkylthio group includes, for example, a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, an n-butylthio group, an isobutylthio group, an s-butylthio group, a t-butylthio group, a pentylthio group, a hexylthio group, a cyclohexylthio group and a heptylthio group. , Octylthio group, nonylthio group, decylthio group, dodecylthio group and the like. The hydrogen atom of the alkylthio group may be substituted with a halogen atom or the like.

The number of carbon atoms of the arylthio group may be 6 or more and 20 or less. The arylthio group may be a phenylthio group, an alkylphenylthio group, an alkoxyphenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, or the like. The hydrogen atom of the arylthio group may be substituted with a halogen atom or the like.

The alkylphenylthio group may be one in which the hydrogen atom of the phenylthio group is substituted with an alkyl group. The alkoxyphenylthio group may be one in which the hydrogen atom of the phenylthio group is substituted with an alkoxy group.

The dilated phthalocyanine may have a structure represented by the following formula (2).

In the above formula (2), M is molybdenum or tungsten. R3 is a monovalent alkoxy group having 1 or more and 20 or less carbon atoms, which is independent of each other.
The dilated phthalocyanine may have a structure represented by the following formula (3).

The dilated phthalocyanine has the maximum value in the absorbance of infrared light at any wavelength contained in 700 nm or more and 1100 nm or less. Therefore, according to the infrared light cut filter 13, it is possible to reliably absorb the near infrared light passing through the infrared light cut filter 13. As a result, the near-infrared light that can be detected by the photoelectric conversion element 11 for each color is sufficiently cut by the infrared light cut filter 13.

The absorbance Aλ at the wavelength λ is calculated by the following formula.
Aλ = -log ₁₀ (% T / 100)
The transmittance T depends on the ratio (TL / IL) of the transmitted light intensity (TL) to the incident light intensity (IL) when the infrared light cut filter 13 having the extended phthalocyanine is transmitted through the infrared light. expressed. In the infrared light cut filter 13, the intensity of transmitted light when the intensity of incident light is 1, is the transmittance T, and the value obtained by multiplying the transmittance T by 100 is the transmittance %% T.

In the coloring composition, the content of the coloring agent with respect to the total solid content in the coloring composition is preferably 10% or more and 70% or less, and more preferably 20% or more and 50% or less.

The percentage of the mass of the colorant to the mass of the total solid content contained in the coloring composition is preferably 30% or more. As a result, the mass of the colorant with respect to the total mass of the total solid content contained in the coloring composition is 30% or more, and the dispersibility of the expanded phthalocyanine is enhanced by the block copolymer, for example, 1 μm or less. It is also possible to increase the absorbance of infrared light in the infrared light cut filter 13 having the thickness of.

[Dispersant]
The dispersant comprises a block copolymer having a first block and a second block. The first block contains either an acidic functional group or a basic functional group having an affinity for adsorbing dilated phthalocyanine. The second block has an affinity for an organic solvent or a curable compound that insolubilizes the expanded phthalocyanine and dissolves the curable compound. Insoluble means that the solubility of the solute in the organic solvent is less than 0.01 to 30 mg / L, and dissolution means that the solubility of the solute in the organic solvent is 10 g / L or more. The dispersant has a plurality of block copolymers, and it is preferable that each block copolymer has one first block and one second block.

Each block of the block copolymer can constitute a monomer as follows.
The monomers constituting the first block having an acidic functional group include, for example, (meth) acrylic acid, phthalic acid, isophthalic acid, adipic acid, maleic acid, itaconic acid, succinic acid, terephthalic acid, azelaic acid, malonic acid, and fumar. Acids, high mitta acids, het acids, trimellitic acids, aconitic acids, butane tricarboxylic acids, 6-carboxy-3-methyl-1,2,3,6-hexahydrophthalic acid, dimer acid, pyromellitic acid, sorbic acid, Butane tetracarboxylic acid, tetrahydrophthalic anhydride, trimellitic anhydride, phthalic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride and the like may be used.

The monomer constituting the first block having a basic functional group is, for example, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl. It may be (meth) acrylate, diethylaminobutyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide and the like.

The first block may contain two or more kinds of monomers different from each other. The monomer contained in the first block may be a group that adsorbs to the expanded phthalocyanine, and may be, for example, a quaternary amine. Further, in the first block, a plurality of block copolymers having different groups adsorbed on the expanded phthalocyanine may be used. If the groups adsorbed on the expanded phthalocyanine are basic, groups having different amine values may be introduced. When the first block has either an acidic functional group or a basic functional group, the dispersion stability of the coloring composition becomes good, and a coloring composition having a low viscosity and an excellent viscosity stability can be obtained.

The first block preferably has a polar group. The first block is adsorbed on the dilated phthalocyanine by an acid-base reaction between the colorant and the dispersant. Therefore, it is preferable that the first block of the dispersant has a polar group having a polarity different from that of the colorant. The first block preferably has, for example, an amine structure. The amine value in the first block is preferably 10 mgKOH / g or more and 200 mgKOH / g or less.

The monomer constituting the second block is preferably a (meth) acrylic vinyl monomer. The (meth) acrylic vinyl monomer constituting the second block may have only one type or two or more types. By using a structural unit derived from a (meth) acrylic vinyl monomer, a high affinity between the second block and an organic solvent or a curable compound can be maintained.

The (meth) acrylic vinyl monomer has a (meth) acrylate having a chain alkyl group such as a linear alkyl group or a branched alkyl group, a (meth) acrylate having a cyclic alkyl group, and a (meth) having a polycyclic structure. Acrylate, (meth) acrylate having an aromatic group, (meth) acrylate having a polyalkylene glycol structural unit, (meth) acrylate having a hydroxy group, (meth) acrylate having a lactone-modified hydroxy group, and (meth) having an alkoxy group. ) Acrylate, (meth) acrylate having an oxygen-containing heterocyclic group, (meth) acrylate having an acidic group, (meth) acrylic acid and the like may be used. As the (meth) acrylic vinyl monomer, one type may be used alone, or two or more types may be used in combination.

The (meth) acrylate having a linear alkyl group is preferably a (meth) acrylate having a linear alkyl group having 1 or more and 20 or less carbon atoms, and the linear alkyl group has a carbon number of 20 or less. More preferably, it is a (meth) acrylate having a linear alkyl group of 1 or more and 10 or less. The (meth) acrylate having a linear alkyl group includes methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, n-hexyl (meth) acrylate, and n-. It may be octyl (meth) acrylate, n-nonyl (meth) acrylate, decyl (meth) acrylate, n-lauryl (meth) acrylate, n-stearyl (meth) acrylate and the like.

The (meth) acrylate having a branched chain alkyl group is preferably a (meth) acrylate having a branched chain alkyl group having 1 or more and 20 or less carbon atoms, and the branched chain alkyl group has a carbon number of carbon. It is preferably a (meth) acrylate having a branched alkyl group of 1 or more and 10 or less. The (meth) acrylate having a branched chain alkyl group includes isopropyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isooctyl (meth) acrylate, and 2-ethylhexyl (2-ethylhexyl). It may be a meta) acrylate, an isononyl (meth) acrylate, an isodecyl (meth) acrylate or the like.

The (meth) acrylate having a cyclic alkyl group is preferably a (meth) acrylate having a cyclic alkyl group having 6 or more and 12 or less carbon atoms. The cyclic alkyl group may be a cyclic alkyl group having a monocyclic structure such as a cycloalkyl group. The (meth) acrylate having a cyclic alkyl group having a monocyclic structure may be, for example, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, or the like.

The (meth) acrylate having a polycyclic structure is preferably a (meth) acrylate having a polycyclic structure having 6 or more and 12 or less carbon atoms. The polycyclic structure may be, for example, a cyclic alkyl group having a bridging ring structure such as an adamantyl group, a norbornyl group, and an isobornyl group. Examples of the (meth) acrylate having a polycyclic structure include isobornyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and dicyclopentanyloxyethyl (meth) acrylate, 2-methyl-2-adamantyl (meth). ) Acrylate, 2-ethyl-2-adamantyl (meth) acrylate and the like.

The (meth) acrylate having an aromatic group is preferably a (meth) acrylate having an aromatic group having 6 or more and 12 or less carbon atoms. The aromatic group may be an aryl group, an alkylaryl group, an aralkyl group, an aryloxy group, an aryloxyalkyl group, an alkylaryloxy group, an aralkyloxy group or the like. The aromatic group is preferably a phenyl group, a benzyl group, a tolyl group, a phenoxyethyl group or the like. The (meth) acrylate having an aromatic group may be, for example, benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate and the like.

The (meth) acrylate having a polyalkylene glycol structural unit is polyethylene glycol (polymerization degree 2 or more and 10 or less) methyl ether (meth) acrylate, polyethylene glycol (polymerization degree 2 or more and 10 or less) ethyl ether (meth) acrylate, polyethylene glycol (polymerization degree 2 or more and 10 or less). Polymerization degree 2 or more and 10 or less) Polyethylene glycol having a polyethylene glycol structural unit such as propyl ether (meth) acrylate (meth) acrylate, polypropylene glycol (polymerization degree 2 or more and 10 or less) Methyl ether (meth) acrylate, polypropylene glycol (polymerization degree 2 or more) It may be (meth) acrylate having a polypropylene glycol structural unit such as ethyl ether (meth) acrylate, polypropylene glycol (polymerization degree 2 or more and 10 or less) propyl ether (meth) acrylate.

(Meta) acrylates having a hydroxy group are 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl. It may be (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate and the like.

The (meth) acrylate having a lactone-modified hydroxy group may be a (meth) acrylate having a hydroxy group with lactone added, and is preferably caprolactone. The amount of caprolactone added is preferably 1 mol or more and 10 mol or less, and more preferably 1 mol or more and 5 mol or less. The (meth) acrylate having a lactone-modified hydroxy group is a caprolactone 1 mol adduct of 2-hydroxyethyl (meth) acrylate, a caprolactone 2 mol adduct of 2-hydroxyethyl (meth) acrylate, and a caprolactone of 2-hydroxyethyl (meth) acrylate. 3 mol adduct, caprolactone 4 mol adduct of 2-hydroxyethyl (meth) acrylate, caprolactone 5 mol adduct of 2-hydroxyethyl (meth) acrylate, caprolactone 10 mol adduct of 2-hydroxyethyl (meth) acrylate, etc. It's okay.

The (meth) acrylate having an alkoxy group may be methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, or the like.

The (meth) acrylate having an oxygen-containing heterocyclic group is preferably a (meth) acrylate having a 4-membered ring, a 5-membered ring, and a 6-membered heterocyclic group. (Meta) acrylates having an oxygen-containing heterocyclic group include, for example, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (3-ethyloxetane-3-yl) methyl (meth) acrylate, and (2-methyl-). 2-Ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, cyclic trimethylolpropane formal (meth) acrylate, 2-[(2-tetrahydropyranyl) oxy] ethyl (meth) acrylate, and It may be 1,3-dioxane- (meth) acrylate or the like.

The acidic groups are carboxy group (-COOH), sulfonic acid group (-SO ₃ H), phosphoric acid group (-OPO ₃ H ₂ ), phosphonic acid group (-PO ₃ H ₂ ), and phosphinic acid group (-). It may be PO ₂ H ₂ ) or the like. The (meth) acrylate having an acidic group has a carboxy group (meth) such as a monomer obtained by reacting a hydroxyalkyl (meth) acrylate with an acid anhydride such as maleic anhydride, succinic anhydride, and phthalic anhydride. ) Acrylate, (meth) acrylate having a sulfonic acid group such as ethyl sulfonate (meth) acrylate, and (meth) acrylate having a phosphoric acid group such as 2- (phosphonooxy) ethyl (meth) acrylate. Often, it is more preferably a (meth) acrylate having a carboxy group.

The second block may contain a plurality of block copolymers having different molecular weights from each other. In addition, the second block may contain two or more kinds of monomers. When two or more kinds of monomers are contained, various monomers contained in the second block may have any structure such as random copolymerization and block copolymerization in the second block, and random copolymerization may occur. Is preferable. The monomer contained in the second block includes a monomer having a high affinity with a curable compound and an organic solvent, a monomer having a high affinity with other coloring compositions other than a colorant, and a monomer having a polar group. At least one of them may be included. The second block may contain two or more types of monomers having a polar group.

The content of the dispersant in the coloring composition is preferably 5% or more and 70% or less, and more preferably 10% or more and 30% or less with respect to the total solid content of the coloring composition. The content of the dispersant is preferably 5 parts by weight or more and 200 parts by weight or less, and more preferably 10 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the expanded phthalocyanine. The dispersant may contain one kind alone or two or more kinds in the coloring composition.

The dispersant is preferably a resin-type dispersant from the viewpoint of compatibility in the coloring composition. Resin-type dispersants include, for example, polyurethane and polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid esters and their modifications, amides formed by the reaction of poly (lower alkyleneimine) with polyesters having free carboxyl groups, salts thereof, etc. Oil-based dispersant, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, water-soluble resin such as polyvinylpyrrolidone It may be a water-soluble polymer compound, a polyester type, a modified polyacrylate type, an ethylene oxide / propylene oxide addition compound, a phosphoric acid ester type, or the like. One of these may be used alone, or two or more thereof may be mixed and used.

Resin-type dispersants having an acidic functional group include, for example, Disperbyk-101, 110, 111, 130, 140, 170, 171, 174, 180, 2001, 2020, 2025, 2070 or BYK-P104, P104S, 220S (Big Chemie). -It may be manufactured by Japan Co., Ltd. (Disperbyk is a registered trademark). Resin-type dispersants having acidic functional groups are SOLPERSE-3000, 13240, 13650, 13940, 16000, 17000, 18000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 32600, 34750, 35100. , 36600, 38500, 41000, 41090, 53095, 55000 (manufactured by Nippon Lubrizol Co., Ltd.) and the like (SOLSPERSE is a registered trademark). Resin-type dispersants having an acidic functional group may be EFKA-4008, 4009, 4010, 4406, 5010, 5065, 5066, 5070 (manufactured by BASF) and the like (EFKA is a registered trademark). The resin-type dispersant having an acidic functional group may be Ajispar PA111, PB821, PB822 (manufactured by Ajinomoto Fine-Techno Co., Ltd.) or the like (Ajisper is a registered trademark).

Resin-type dispersants having a basic functional group include, for example, Disperbyk-101, 108, 116, 130, 140, 161, 162, 163, 164, 165, 166, 180, 182, 183, 184, 185, 2000, It may be 2001, 2020, 2025, 2050, 2070, 2150 or BYK-6919 (manufactured by Big Chemie Japan Co., Ltd.). Resin-type dispersants having a basic functional group include SOLSPERSE-13240, 13650, 13940, 20000, 24000, 26000, 31845, 32000, 32500, 32550, 34750, 35100 (manufactured by Nippon Lubrizol Co., Ltd.). Good. Resin-type dispersants having basic functional groups include EFKA-4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4300, 4330, 4500, It may be 4510, 4530, 4550, 4560, 4800 (manufactured by BASF) or the like. The resin-type dispersant having a basic functional group may be Azisper PB711, PB821, PB822 (manufactured by Ajinomoto Fine-Techno Co., Ltd.) or the like.

The amount of the resin-type dispersant used is preferably 5% or more and 200% or less, and more preferably 10% or more and 40% or less from the viewpoint of film forming property.

The dispersant having a basic functional group may be, for example, a nitrogen atom-containing graft copolymer, a nitrogen atom-containing acrylic block copolymer, a urethane-based polymer dispersant, or the like. The nitrogen atom-containing acrylic block copolymer preferably has a functional group containing a tertiary amino group, a quaternary ammonium base, a nitrogen-containing heterocycle, and the like in the side chain.

The dispersant having an acidic functional group preferably has a functional group containing, for example, a carboxylic acid group, a phosphoric acid group, a sulfonic acid group, and the like. The dispersant having an acidic functional group may be, for example, an acrylic ester copolymer, an acrylic block copolymer, a urethane polymer dispersant, or the like.

The glass transition temperature of the dispersant is preferably 30 ° C. or higher. When the glass transition temperature of the dispersant is 30 ° C. or higher, it is possible to suppress a decrease in the absorbance of infrared light in the infrared light cut filter.

The dispersant having an acidic functional group preferably has a moiety formed by polymerizing an ethylenically unsaturated monomer containing (meth) acrylate. The glass transition temperature of the site is preferably 30 ° C. or higher, and more preferably 80 ° C. or higher. When the glass transition temperature is 80 ° C. or higher, the resistance of the infrared light cut filter 13 to the stripping liquid is improved in the manufacturing process of the infrared light cut filter 13.

The dispersant having an acidic functional group may be a dispersant having an aromatic carboxyl group in the molecule. It is preferable to use a dispersant having an aromatic carboxyl group because the resistance to the stripping liquid in the manufacturing process of the infrared light cut filter 13 is increased. The dispersant having an aromatic carboxyl group is preferably a dispersant obtained by reacting a polymer having a hydroxyl group with at least one of an aromatic tricarboxylic acid anhydride and an aromatic tetracarboxylic dianhydride.

As the dispersant having an aromatic carboxyl group, it is preferable that the polymer having a hydroxyl group is a polymer having a hydroxyl group at one end. The dispersant having an aromatic carboxyl group is more preferably a polymer having a hydroxyl group at one end and a polymer having two hydroxyl groups at one end. By using a dispersant having an aromatic carboxyl group, the stability of the infrared light cut filter 13 can be made excellent.

The polymer having a hydroxyl group at one end may be at least one of a polyester and a polyether polymer having a hydroxyl group at one end, or a vinyl polymer having a hydroxyl group at one end. It is more preferable to use a vinyl polymer having a hydroxyl group at one end because the dispersion stability is improved.

At least one of the aromatic tricarboxylic acid anhydride and the aromatic tetracarboxylic dianhydride is preferably an aromatic tetracarboxylic dianhydride. Aromatic tetracarboxylic dianhydride is preferable because it is superior to aromatic tricarboxylic acid anhydride in terms of storage stability of the coloring composition.

The method for obtaining a dispersant having an aromatic carboxyl group is to radically polymerize an ethylenically unsaturated monomer with a compound having two hydroxyl groups and one thiol group in the molecule, and vinyl having two hydroxyl groups at one end. The hydroxyl group in the polyol containing at least the polymer may be reacted with the acid anhydride group in the polycarboxylic acid anhydride containing at least the aromatic tetracarboxylic acid dianhydride.

Among such dispersants having an aromatic carboxyl group, it is preferable to contain methyl methacrylate as a constituent monomer of the vinyl polymer moiety. By containing methyl methacrylate, the resistance of the infrared light cut filter 13 containing the dispersant to the stripping solution is increased. The content of methyl methacrylate is preferably 30% or more, more preferably 50% or more, and even more preferably 65% or more in terms of mass ratio in the polymer.

By adsorbing the first block of the dispersant to the dilated phthalocyanine, the dispersant is located between the dilated phthalocyanine and the other dilated phthalocyanines. Then, a distance is formed between the dilated phthalocyanines to the extent that the association and aggregation of the dilated phthalocyanines are suppressed. As a result, the decrease in absorbance due to the association and aggregation of the expanded phthalocyanine, that is, the decrease in the absorbance at the wavelength at which the monomer is expected to be absorbed by the expanded phthalocyanine is suppressed. As a result, in the infrared light cut filter 13, it is possible to suppress a decrease in the absorbance of infrared light. The above-mentioned dispersant may be used alone or in combination of two or more.

[Curable compound]
As the curable compound, a compound that can be cured by radicals, acids, and heat can be used. The curable compound may be a thermosetting resin, an ultraviolet curable resin, or the like. In the curable compound, a polymer compound constituting a thermosetting resin or an ultraviolet curable resin is crosslinked with another polymer compound by a side chain or the like of the polymer compound to form a three-dimensional network structure. Form. This cures the curable compound. A cured product is a cured compound. The curable compound contains a polymer as a main component, and may contain a monomer and an oligomer in addition to the polymer. The monomer contained in the curable compound preferably has a molecular weight of 100 or more and 3000 or less, more preferably 150 or more and 2000 or less, and further preferably 250 or more and 1500 or less.

The curable compound may be a compound having an epoxy group, a compound having a methylol group, a compound having an alkoxysilyl group, or the like. The curable compound may contain two or more of these compounds. The curable compound may be an acrylic polymer. The acrylic polymer may contain, for example, any of aromatic rings, alicyclics, and cyclic ethers in the side chains.

The acrylic polymer containing an aromatic ring in the side chain is represented by the following formula (4).

In the formula (4), R4 is a hydrogen atom or a methyl group, and R5 is a single bond, a linear alkylene group having 1 or more carbon atoms, or a branched chain alkylene group having 3 or more carbon atoms. R5 may be, for example, a methylene group, an ethylene group, a trimethylene group, a propylene group, a butylene group, or the like. In acrylic polymers, R6 is a hydrogen atom or a given substituent. When R6 is a substituent, m is an integer of 1 to 5. When m is 2 or more, R6 may contain only one kind of substituent or may contain two or more kinds of substituents.

R6 may form a fused ring by binding to an aromatic ring located between R5 and R6. R6 may be, for example, an alkyl group containing a benzene ring. The alkyl group containing a benzene ring may be a benzyl group, a 2-phenyl (iso) propyl group, or the like. R6 is, for example, an alkyl group, a haloalkyl group, an alkoxy group, a hydroxyalkyl group, an alkylthio group, an alkylamino group, a dialkylamino group, a cyclic amino group, a halogen atom, an acyl group, an alkoxycarbonyl group, a ureido group, a sulfamoyl group and a carbamoyl group. It may be a group, an alkylcarbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxysulfonyl group, an aryloxysulfonyl group, a cyano group, a nitro group and the like.

Monomer of an acrylic polymer containing an aromatic ring, for example, phenyl methacrylate represented by the following formula (5), methacrylic acid biphenyl represented by the following formula (6), and, benzyl methacrylate (C ₁₁ H ₁₂ O ₂ ) And so on.

Further, the monomer of the acrylic polymer containing an aromatic ring includes, for example, benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, and the like. Phenoxypolypropylene glycol (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropylphthalate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl hydrogenphthalate, 2-( Meta) acryloyloxypropyl hydrogen phthalate, ethoxylated ortho-phenylphenol (meth) acrylate, o-phenylphenoxyethyl (meth) acrylate, 3-phenoxybenzyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, 2-naphthol (Meta) acrylate, 4-biphenyl (meth) acrylate, 9-anthrylmethyl (meth) acrylate, 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl] ethyl (meth) acrylate, It may be phenolethylene oxide (EO) modified acrylate, nonylphenol EO modified acrylate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid and the like.

The acrylic polymer is represented by the following formula (7). The alicyclic structure includes a monocyclic or a polycyclic aromatic ring-free structure such as a fused ring and a bridging ring.

In the formula (7), R7 is a hydrogen atom or a methyl group, and R8 is a single bond, a linear alkylene group having 1 or more carbon atoms, or a branched chain alkylene group having 3 or more carbon atoms. R8 may be, for example, a methylene group, an ethylene group, a trimethylene group, a propylene group, a butylene group, or the like. In the acrylic polymer, R9 has an alicyclic structure having 3 or more carbon atoms. The alicyclic structure may be a saturated alicyclic structure containing only a single bond, or an unsaturated alicyclic structure containing at least one of a double bond and a triple bond.

The alicyclic structure includes, for example, cyclohexyl skeleton, dicyclopentadiene skeleton, adamantane skeleton, norbornane skeleton, isobornane skeleton, cycloalkane skeleton, cycloalkene skeleton, norbornene skeleton, norbornadiene skeleton, tricycloalkane skeleton, tetracycloalkane skeleton, and many. It may include a cyclic skeleton and a spiro skeleton.

The cycloalkane skeleton may be, for example, a cyclopropane skeleton, a cyclobutane skeleton, a cyclopentane skeleton, a cyclohexane skeleton, a cycloheptane skeleton, a cyclooctane skeleton, a cyclononane skeleton, a cyclodecane skeleton, a cycloundecane skeleton, a cyclododecane skeleton, or the like. The cycloalkene skeleton may be, for example, a cyclopropene skeleton, a cyclobutene skeleton, a cyclopentene skeleton, a cyclohexene skeleton, a cycloheptene skeleton, a cyclooctene skeleton, or the like. The tricycloalkane skeleton may be, for example, a tricyclodecane skeleton. The tetracycloalkane skeleton may be, for example, a tetracyclododecane skeleton. The polycyclic skeleton may be, for example, a cubane skeleton, a basketane skeleton, a housane skeleton, or the like.

Acrylic polymer monomers containing an alicyclic structure include, for example, isobornyl acrylate (C ₁₃ H ₂₀ O ₂ ) represented by the following formula (8) and dicyclopentanyl methacrylate represented by the following formula (9). It may be (C ₁₄ H ₂₀ O ₂ ) or the like.

Further, acrylic polymer monomers containing an alicyclic structure include, for example, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-t-cyclohexyl (meth) acrylate, isobornyl methacrylate, dicyclopentanyl acrylate, and dicyclopentanyl acrylate. Cyclopentenyl (meth) acrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, and tetracyclododecyl (meth) acrylate. You can.

The acrylic polymer forming the infrared light cut filter 13 together with the expanded phthalocyanine contains an aromatic ring or an alicyclic structure in the side chain. Therefore, by locating the aromatic ring or alicyclic structure of the acrylic polymer between the expanded phthalocyanine and other expanded phthalocyanines located in the vicinity of the expanded phthalocyanine, aggregation between the expanded phthalocyanines is performed. Is unlikely to occur. Therefore, the aggregation of the expanded phthalocyanine suppresses the decrease in the absorbance of infrared light expected for the expanded phthalocyanine, and as a result, the decrease in the absorbance of infrared light in the infrared light cut filter is suppressed. ..

Further, the acrylic polymer is represented by the following formula (10).

In the formula (10), R10 is a hydrogen atom or a methyl group, and R11 is a single bond, a linear alkylene group having 1 or more carbon atoms, or a branched chain alkylene group having 3 or more carbon atoms. R11 may be, for example, a methylene group, an ethylene group, a trimethylene group, a propylene group, a butylene group, or the like. In acrylic polymers, R12 is a cyclic ether group containing an oxygen atom and two or more carbon atoms. The cyclic ether group has an ether bond in the ring formed by containing a plurality of carbon atoms. The cyclic ether group may be, for example, an epoxy group, an oxetanyl group, a tetrahydrofuranyl group, a tetrahydropyranyl group, or the like.

The monomer of the acrylic polymer containing a cyclic ether group may be, for example, glycidyl methacrylate represented by the following formula (11).

Further, the monomer of the acrylic polymer containing the cyclic ether group is, for example, glycidyl acrylate, 2-methylglycidyl (meth) acrylate, 2-ethylglycidyl (meth) acrylate, 2-oxylanylethyl (meth) acrylate, 2-glycidyl. Oxyethyl (meth) acrylate, 3-glycidyloxypropyl (meth) acrylate, glycidyloxyphenyl (meth) acrylate, oxetanyl (meth) acrylate, 3-methyl-3-oxetanyl (meth) acrylate, 3-ethyl-3-oxetanyl (Meta) Acrylate, (3-Methyl-3-oxetanyl) Methyl (Meta) Acrylate, (3-Ethyl-3-oxetanyl) Methyl (Meta) Acrylate, 2- (3-Methyl-3-oxetanyl) Ethyl (Meta) Acrylate 2- (3-ethyl-3-oxetanyl) ethyl (meth) acrylate, 2-[(3-methyl-3-oxetanyl) methyloxy] ethyl (meth) acrylate, 2-[(3-ethyl-3--) Oxetanyl) methyloxy] ethyl (meth) acrylate 3-[(3-methyl-3-oxetanyl) methyloxy] propyl (meth) acrylate 3-[(3-ethyl-3-oxetanyl) methyloxy] propyl (meth) ) Acrylate, tetrahydrofurfuryl (meth) acrylate and the like may be used.

Since the acrylic polymer contains a cyclic ether group in the side chain, the absorbance of infrared light in the infrared light cut filter 13 after heating is lower than the absorbance of infrared light in the infrared light cut filter 13 before heating. Is suppressed. The solid-state image sensor 10 is mounted on a mounting substrate by soldering by a reflow method. At this time, the solid-state image sensor 10 is heated to a temperature at which the solder can be melted. The solid-state image sensor 10 is heated to, for example, 250 ° C. Therefore, the infrared light cut filter 13 forming the solid-state image sensor 10 is required not to change its absorption characteristics with respect to infrared light due to the heat applied to the infrared light cut filter 13 at the time of soldering. In particular, the infrared light cut filter 13 is required not to reduce the absorbance of infrared light contained in the infrared light cut filter 13 by heating the infrared light cut filter 13. If the acrylic polymer contained in the infrared light cut filter 13 contains a cyclic ether group in the side chain, even if the infrared light cut filter 13 undergoes a soldering step by a reflow method, the infrared light cut filter 13 can be used. The decrease in the absorbance of infrared light is suppressed.

The acrylic polymer may be a polymer formed by polymerizing only one of the above-mentioned acrylic monomers, or a copolymer obtained by polymerizing two or more kinds of acrylic monomers.

The acrylic polymer may contain a monomer other than the above-mentioned acrylic monomer.
The monomer other than the above-mentioned acrylic monomer may be, for example, a styrene-based monomer, a (meth) acrylic monomer, a vinyl ester-based monomer, a vinyl ether-based monomer, a halogen element-containing vinyl-based monomer, a diene-based monomer, or the like. Styrene-based monomers include, for example, styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, p-methoxystyrene, p-hydroxystyrene, p-acetoxystyrene, vinyltoluene, ethylstyrene, phenylstyrene, and. It may be benzyl styrene or the like. The (meth) acrylic monomer may be, for example, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate and the like. The vinyl ester-based monomer may be, for example, vinyl acetate. The vinyl ether-based monomer may be, for example, vinyl methyl ether. The halogen element-containing vinyl-based monomer may be, for example, vinyl chloride. The diene-based monomer may be, for example, butadiene, isobutylene, or the like. The acrylic polymer may contain only one kind of monomer other than the above-mentioned acrylic monomer, or may contain two or more kinds of monomers.

Further, the acrylic polymer may contain a monomer for adjusting the polarity of the acrylic polymer. The monomer for adjusting the polarity adds an acid group or a hydroxyl group to the acrylic polymer. Such monomers may be, for example, acrylic acid, methacrylic acid, maleic anhydride, maleic acid half ester, acrylic acid-2 hydroxyethyl, and (meth) acrylic acid-4-hydroxyphenyl.

When the acrylic polymer is a copolymer obtained by polymerizing two or more kinds of acrylic monomers, the acrylic polymer is a random copolymer, an alternating copolymer, a block copolymer, and a graft copolymer. It may have any structure. If the structure of the acrylic polymer is a random copolymer, the manufacturing process and preparation with expanded phthalocyanine are easy. Therefore, the random copolymer is preferable to other copolymers.

The polymerization method for obtaining the acrylic polymer may be, for example, radical polymerization, cationic polymerization, anionic polymerization, living radical polymerization, living cationic polymerization, living anionic polymerization and the like. Radical polymerization is preferably selected as the polymerization method for obtaining the acrylic polymer because it is industrially easy to produce. The radical polymerization may be a solution polymerization method, an emulsion polymerization method, a lump polymerization method, a suspension polymerization method or the like. For radical polymerization, it is preferable to use a solution polymerization method. By using the solution polymerization method, it is easy to control the molecular weight of the acrylic polymer. Further, after the polymerization of the acrylic monomer, the solution containing the acrylic polymer can be used in the state of the solution for manufacturing the filter 10F for a solid-state image sensor.

In radical polymerization, the above-mentioned acrylic monomer may be diluted with a polymerization solvent, and then a radical polymerization initiator may be added to polymerize the acrylic monomer.

The polymerization solvent may be an ester solvent, an alcohol ether solvent, a ketone solvent, an aromatic solvent, an amide solvent, an alcohol solvent, or the like. The ester solvent may be, for example, methyl acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, t-butyl acetate, methyl lactate, ethyl lactate and the like. Alcohol ether solvents include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 3-methoxy-1-butanol, and 3-methoxy-3-methyl-1-. It may be butanol or the like. The ketone solvent may be, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone or the like. The aromatic solvent may be, for example, benzene, toluene, xylene or the like. The alcohol solvent may be, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, s-butanol, t-butanol, diacetone alcohol, 2-methyl-2-butanol and the like. .. Of these, the ketone solvent and the ester solvent are preferable because they can be used in the production of the filter 10F for a solid-state image sensor. In the above-mentioned polymerization solvent, one type may be used alone, or two or more types may be used in combination.

In the infrared light cut filter 13 containing an acrylic polymer produced by using formamide and an amide-based solvent containing a nitrogen compound such as dimethylformamide, if the nitrogen compound remains, the nitrogen compound is expanded phthalocyanine. The infrared light cut filter 13 may fade in color. Therefore, it is preferable not to use an amide solvent as the polymerization solvent when producing the acrylic polymer.

In radical polymerization, the amount of the polymerization solvent used is not particularly limited, but when the total amount of the acrylic monomers is set to 100 parts by weight, the amount of the polymerization solvent used may be 1 part by weight or more and 1000 parts by weight or less. It is preferably 10 parts by weight or more and 500 parts by weight or less.

The radical polymerization initiator may be, for example, a peroxide and an azo compound. Peroxides may be, for example, benzoyl peroxide, t-butylperoxyacetate, t-butylperoxybenzoate, di-t-butyl peroxide and the like. Azo compounds include, for example, azobisisobutyronitrile, azobisamidinopropane salt, azobiscyanovaleric acid (salt), and 2,2'-azobis [2-methyl-N- (2-hydroxyethyl)). Propion amide] and the like.

If the azo compound remains in the solution containing the acrylic polymer, the azo compound may fade the expanded phthalocyanine when the acrylic polymer and the expanded phthalocyanine are mixed. Therefore, it is preferable to use a peroxide as the radical polymerization agent.

The amount of the radical polymerization initiator used is preferably 0.0001 parts by weight or more and 20 parts by weight or less, preferably 0.001 parts by weight or more and 15 parts by weight or less when the total amount of the acrylic monomers is set to 100 parts by weight. It is more preferable that the amount is 0.005 parts by weight or more and 10 parts by weight or less. The radical polymerization initiator may be added to the acrylic monomer and the polymerization solvent before the initiation of the polymerization, or may be added dropwise to the polymerization reaction system. It is preferable to add the radical polymerization initiator to the acrylic monomer and the polymerization solvent in the polymerization reaction system because the heat generation due to the polymerization can be suppressed.

The reaction temperature of radical polymerization is appropriately selected depending on the type of radical polymerization initiator and polymerization solvent. The reaction temperature is preferably 60 ° C. or higher and 110 ° C. or lower from the viewpoint of ease of production and reaction controllability.

The glass transition temperature of the curable compound is preferably 30 ° C. or higher, more preferably 75 ° C. or higher. When the glass transition temperature is 30 ° C. or higher, it is possible to suppress a decrease in the absorbance of infrared light in the infrared light cut filter.

The average molecular weight of the curable compound is preferably 10,000 or more and 150,000 or less, and more preferably 30,000 or more and 150,000 or less. When the average molecular weight of the curable compound is included in this range, it is possible to sufficiently obtain the mechanical strength and light resistance of the infrared light cut filter 13. A curable compound having a molecular weight of more than 150,000 is difficult to be coated together with expanded phthalocyanine due to an increase in viscosity during polymerization. Therefore, when the molecular weight of the curable compound exceeds 150,000, it is not easy to form the infrared light cut filter 13. On the other hand, if the molecular weight of the curable compound is 150,000 or less, it is possible to form a coating liquid containing the curable compound and the expanded phthalocyanine, so that the infrared light cut filter 13 can be more easily formed. Is.

The average molecular weight of the curable compound is a weight average molecular weight. The weight average molecular weight of the curable compound can be measured, for example, by gel permeation chromatography. For example, in the radical polymerization reaction, the molecular weight of the curable compound can be controlled by changing the concentrations of the acrylic monomer and the radical polymerization initiator in the solution.

When the curable compound is an acrylic polymer, the percentage (MM / MS) of the mass (MM) of the acrylic monomer to the sum (MS) of the mass of the acrylic polymer and the mass of the acrylic monomer used to produce the acrylic polymer. X100) is preferably 20% or less. Since the amount of the acrylic monomer remaining in the infrared light cut filter 13 is 20% or less, it is possible to suppress a decrease in the absorbance of infrared light in the expanded phthalocyanine due to the residual acrylic monomer.

The percentage (MM / MS × 100) of the mass of the acrylic monomer (MM) with respect to the sum (MS) of the mass of the acrylic polymer and the mass of the acrylic monomer is more preferably 10% or less, and more preferably 3% or less. Is more preferable. The mass of the acrylic polymer and the mass of the acrylic monomer can be quantified based on the analysis result of the mixture containing the acrylic polymer and the acrylic monomer. The method for analyzing the mixture may be, for example, gas chromatography-mass spectrometry (GC-MS), nuclear magnetic resonance spectroscopy (NMR), infrared spectroscopy (IR), or the like.

The method of changing the ratio of the mass of the acrylic monomer to the sum of the mass of the acrylic polymer and the mass of the acrylic monomer may be, for example, a method of changing the polymerization time, a method of changing the polymerization temperature, or the like. Further, the method of changing the ratio of the mass of the acrylic monomer to the sum of the mass of the acrylic polymer and the mass of the acrylic monomer is a method of changing the concentrations of the acrylic monomer and the radical polymerization initiator at the start of the polymerization reaction. Good. The method of changing the ratio of the mass of the acrylic monomer to the sum of the mass of the acrylic polymer and the mass of the acrylic monomer may be a method of changing the purification conditions after the polymerization reaction. Of these, the method of changing the polymerization time is preferable because the control for changing the mass ratio of the acrylic monomer is highly accurate.

Further, the curable compound is preferably a compound having substantially no molecular weight distribution. A compound having substantially no molecular weight distribution is a compound having a compound dispersion degree (weight average molecular weight (Mw) / number average molecular weight (Mn)) of 1.0 or more and 1.5 or less. It is more preferable that the curable compound has a dispersity of 1.0 or more and 1.3 or less.
As described above, it is preferable that the curable compound after formation does not contain a nitrogen compound.

[Compound with epoxy group]
The curable compound may be a compound having an epoxy group. The compound having an epoxy group may be a monofunctional or polyfunctional glycidyl ether compound, a polyfunctional aliphatic glycidyl ether compound, or the like. The compound having an epoxy group is a compound having a glycidyl group such as glycidyl acrylate having a cyclic ether group in the side chain of the above-mentioned curable compound, allyl glycidyl ether, and a compound having an alicyclic epoxy group. May be good.

The compound having an epoxy group may be a compound having one or more epoxy groups in one molecule, and is preferably a compound having two or more epoxy groups. The number of epoxy groups is preferably 1 or more and 100 or less in one molecule. The number of epoxy groups is more preferably 2 or more and 10 or less, and further preferably 2 or more and 5 or less.

Among the compounds having an epoxy group, the epoxy equivalent represented by the molecular weight of the compound having an epoxy group / the number of epoxy groups is preferably 500 g / eq or less. The epoxy equivalent is more preferably 100 g / eq or more and 400 g / eq or less, and further preferably 100 g / eq or more and 300 g / eq or less.

The compound having an epoxy group may be a low molecular weight compound or a high molecular weight compound. In the present embodiment, the low molecular weight compound means a compound having a molecular weight of less than 2000, and the high molecular weight compound means a compound having a molecular weight of 1000 or more. When the compound is a polymer, the polymer compound has a weight average molecular weight of 1000 or more. The weight average molecular weight of the compound having an epoxy group is preferably 200 or more and 100,000 or less, and more preferably 500 or more and 50,000 or less. The weight average molecular weight is more preferably 500 or more and 10000 or less, and further preferably 500 or more and 5000 or less.

The compound having an epoxy group may be, for example, a bisphenol A type epoxy resin, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, an aliphatic epoxy resin, or the like.

The compound having an epoxy group may have a glycidyl group as an epoxy group such as glycidyl (meth) acrylate and allyl glycidyl ether, or may be an unsaturated compound having an alicyclic epoxy group.

[Compound having an alkoxysilyl group]
The curable compound may be a compound having an alkoxysilyl group. The alkoxysilyl group may be, for example, a monoalkoxysilyl group, a dialkoxysilyl group, a trialkoxysilyl group, or the like. The alkoxysilyl group is preferably a dialkoxysilyl group and a trialkoxysilyl group. Further, the number of carbon atoms of the alkoxy group in the alkoxysilyl group is preferably 1 or more and 5 or less, more preferably 1 or more and 3 or less, and further preferably 1 or 2. It is preferable to have two or more alkoxysilyl groups in one molecule, and it is more preferable to have two or three alkoxysilyl groups.

The monomers of compounds having an alkoxysilyl group include, for example, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-. Propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis (trimethoxysilyl) hexane, trifluoropropyltrimethoxysilane, hexamethyldisilazane, vinyl Trimethoxysilane, vinyl triethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl Methyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-Methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxy Silane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, tris- (trimethoxysilylpropyl) isocyanurate, 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, It may be 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanuppropyltriethoxysilane and the like. In addition to the above, an alkoxy oligomer can be used. The compound having an alkoxysilyl group may be a polymer having an alkoxysilyl group in the side chain.

[Compound having a methylol group]
The curable compound may be a compound having a methylol group. The compound having a methylol group may be a compound in which the methylol group is bonded to a nitrogen atom or a carbon atom forming an aromatic ring.

Compounds in which the methylol group is bonded to a nitrogen atom include, for example, alkoxymethylated melamine, methylolated melamine, alkoxymethylated benzoguanamine, methylolated benzoguanamine, alkoxymethylated glycoluryl, methylolated glycoluryl, 1,3,4. , 6-Tetramethoxymethyl glycol uryl, alkoxymethylated urea, methylolated urea and the like.

[Organic solvent]
The organic solvent is used in a coating liquid for producing the infrared light cut filter 13 together with each component such as a colorant, a dispersant, and a curable compound. When the infrared light cut filter 13 is formed on the substrate using a coating liquid containing a coloring composition, the organic solvent is applied so that the film thickness of the dried coating film is 0.2 μm or more and 10 μm or less. To facilitate. The film thickness of the dried coating film is preferably 1 μm or less.

The organic solvent does not dissolve the dilated phthalocyanine contained in the colorant, and also dissolves the dispersant and the curable compound. The carbon number of the organic solvent is preferably 3 or more and 10 or less. Further, the organic solvent preferably has low polarity, and more preferably non-polarity. The organic solvent preferably has a boiling point of 100 ° C. or higher and 200 ° C. or lower. Such an organic solvent is preferable because it facilitates the formation of a uniform coating film on the substrate.

The organic solvent is preferably an organic solvent containing at least one of a ketone solvent, an ether solvent, and an ester solvent. In a dispersion system using at least one of a ketone solvent, an ether solvent, and an ester solvent as an organic solvent, the dispersibility of the expanded phthalocyanine can be enhanced. The organic solvent may be, for example, propylene glycol monomethyl ether acetate. Since the organic solvent is propylene glycol monomethyl ether acetate, it is easy to enhance the dispersibility of the expanded phthalocyanine and to form a coating film having a uniform thickness when obtaining an infrared light cut filter.

Organic solvents include, for example, ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, and the like. 2-Heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexene-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl -1,3-butanoldiol, 3-methoxy-3-methyl-1-butanol, 3-toxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m -Diethyl benzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene , O-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol Monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotersial butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl Ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone , Dipropylene glycol dimethyl ether, Dipropylene glycol methyl ether acetate, Dipropylene glycol Noethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether , Propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone , Methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters. One of these organic solvents may be used alone, or two or more of these organic solvents may be mixed and used in an arbitrary ratio as required.

The organic solvent is preferably added so that the solid content of the coloring composition is 5% or more and 50% or less, and more preferably 10% or more and 30% or less.

[Dispersion aid]
In addition to the above-mentioned colorants, dispersants, curable compounds, and organic solvents, the coloring composition may contain dye derivatives and dispersion aids such as surfactants. The dispersion aid improves the dispersibility of the colorant and prevents the colorant from associating and agglomerating over time after being dispersed in an organic solvent.

[Dye derivative]
The coloring composition may contain a dye derivative. The dye derivative is a dispersion aid for facilitating the adsorption of the dispersant on the surface of the colorant, and suppresses the colorant from associating and aggregating over time after being dispersed in an organic solvent. By using the dye derivative in the coloring composition, the spectral characteristics and the viscosity stability are improved. The dye derivative has an effect of protecting the surface of a pigment having a weak solvent resistance. Therefore, the chemical resistance of the pigment is improved when the infrared light cut filter 13 is formed.

The dye in the dye derivative can be appropriately selected from organic pigments and dyes. The dye derivative preferably has a structure similar to that of the dye contained in the colorant and has a polar group. The dye derivative may have, for example, a phthalocyanine skeleton. The dye derivative may be a dye derivative having an acidic group, a basic group, a neutral group, or the like in the organic dye residue. For example, compounds having acidic functional groups such as sulfo group, carboxy group and phosphoric acid group and amine salts thereof, compounds having basic functional groups such as sulfonamide group and tertiary amino group at the terminal, phenyl group and phthalimide. It may be a compound having a neutral functional group such as an alkyl group. Further, these may be used alone or in combination of two or more.

From the viewpoint of improving the dispersibility of the colorant, the amount of the dye derivative to be blended is preferably 0.5 parts by weight or more, and preferably 1 part by weight or more when the colorant is set to 100 parts by weight. More preferably, it is 3 parts by weight or more. Further, from the viewpoint of heat resistance and light resistance, the blending amount of the dye derivative is preferably 40 parts by weight or less, preferably 35 parts by weight or less when the colorant is set to 100 parts by weight. Is more preferable.

The coloring composition for forming the infrared light cut filter 13 may contain a surfactant, an antioxidant, an ultraviolet absorber, a polymerization inhibitor, a storage stabilizer, a leveling agent, and the like.

[Manufacturing method of filter for solid-state image sensor]
The method for producing the filter 10F for a solid-state image sensor is to form a coating film containing a coloring composition containing a colorant, a dispersant, a curable compound, and an organic solvent, and to cure the curable compound to cure the coating film. This includes forming a colored layer and patterning the colored layer by dry etching. By forming a coating film, a colorant containing expanded phthalocyanine, and a first block containing either an acidic functional group or a basic functional group having an affinity for adsorbing to expanded phthalocyanine, and an expanded type A coating film is formed using an organic solvent that insolubles phthalocyanine and dissolves a curable compound, or a dispersant containing a second block having an affinity for the curable compound and a block copolymer having. To do. Hereinafter, a method for manufacturing the filter 10F for a solid-state image sensor will be described in more detail.

The color filters 12R, 12G, 12B, and the infrared light pass filter 12P are formed by forming a coating film containing a colored photosensitive resin and patterning the coating film using a photolithography method. For example, a coating film containing a red photosensitive resin is formed by applying a coating liquid containing a red photosensitive resin and drying the coating film. The red filter 12R is formed by exposing and developing a coating film containing a red photosensitive resin, which corresponds to a region of the red filter 12R. The green filter 12G, the blue filter 12B, and the infrared light pass filter 12P are also formed by the same method as the red filter 12R.

As the pigment contained in the coloring composition of the red filter 12R, the green filter 12G, and the blue filter 12B, an organic or inorganic pigment can be used alone or in combination of two or more. The pigment is preferably a pigment having high color development and high heat resistance, particularly a pigment having high heat resistance decomposition property, and preferably an organic pigment. Organic pigments include, for example, phthalocyanine, azo, anthraquinone, quinacridone, dioxazine, anthraslon, indanthrone, perylene, thioindigo, isoindoline, quinophthalone, and diketopyrrolopyrrole. And so on. Further, a black dye or a black dye can be used as the coloring component contained in the infrared light pass filter 12P. The black pigment may be a single pigment having a black color, or a mixture having a black color due to two or more kinds of pigments. The black dye may be, for example, an azo dye, an anthraquinone dye, an azine dye, a quinoline dye, a perinone dye, a perylene dye, and a methine dye. The photosensitive coloring composition of each color further includes a binder resin, a photopolymerization initiator, a polymerizable monomer, an organic solvent, a leveling agent, and the like.

Forming a colored layer includes forming a coating film containing a coloring composition and obtaining a colored layer by curing the coating film. The coating film is produced by dispersing a colorant, a dispersant, and a curable compound in an organic solvent.

A kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annual bead mill, an attritor, or the like may be used to disperse the colorant. At this time, two or more kinds of colorants may be dispersed in an organic solvent, or those dispersed separately in an organic solvent may be mixed. The colorant may be dispersed in an organic solvent together with a dye derivative and a dispersion aid such as a surfactant.

The above-mentioned colorant containing the expanded phthalocyanine, the dispersant, the curable compound, and the coating liquid containing the organic solvent are applied to the transparent substrate, and the coating film is dried. The dried coating is then cured by cross-linking the curable compound by heating. As a result, a colored layer is formed.

The through hole 13H included in the infrared light cut filter 13 is formed by dry etching the colored layer. Thereby, the colored layer can be patterned.
Patterning the colored layer by dry etching means forming a photoresist layer on the colored layer, forming a resist mask by patterning the photoresist layer, and using the resist mask to form a colored pattern on the colored layer. Includes forming a resist mask and removing the resist mask from the colored layer.

First, a photoresist layer is formed on the colored layer. By exposing and developing the photoresist layer, the photoresist layer is patterned to form a resist mask. The colored layer is patterned by dry etching using a resist mask. As a result, a colored pattern is formed on the colored layer, and the stripping liquid is brought into contact with the resist mask to remove the resist mask from the colored layer. As a result, the infrared light cut filter 13 having a colored pattern formed by patterning the colored layer by dry etching is formed.

Each of the microlenses 15R, 15G, 15B, and 15P is formed by forming a coating film containing a transparent resin, patterning the coating film using a photolithography method, and reflowing by heat treatment. The transparent resin is, for example, an acrylic resin, a polyamide resin, a polyimide resin, a polyurethane resin, a polyester resin, a polyether resin, a polyolefin resin, a polycarbonate resin, a polystyrene resin, a norbornene resin, or the like. is there.

The solid-state image sensor is manufactured by combining the solid-state image sensor filter 10F formed by the above method with a plurality of photoelectric conversion elements 11.

[Production example of acrylic polymer]
By using an acrylic monomer, a polymerization solvent, and a radical polymerization initiator as shown in Table 1 below, the acrylic polymers of Production Examples 1-1 to 1-3 and Production Example 2 were obtained. In addition, the extrapolated glass transition start temperature of the acrylic polymer was measured. In the produced acrylic copolymer, the weight ratio in the repeating unit derived from the acrylic monomer is equal to the weight ratio of the acrylic monomer at the time of producing the acrylic copolymer.

<Manufacturing Example 1-1>
60 parts by weight of propylene glycol monomethyl ether acetate and (PGMAc) was prepared as a polymerization solvent, 40 parts by weight of phenyl methacrylate and _{(C 10 H 10 O 2)} was prepared as an acrylic monomer, 0.60 parts by weight of benzoyl peroxide ( BPO) was prepared as a radical polymerization initiator. These were placed in a reaction vessel equipped with a stirrer and a reflux tube, and the mixture was stirred and refluxed for 8 hours while being heated to 80 ° C. while introducing nitrogen gas into the reaction vessel. As a result, a homopolymer solution of phenyl methacrylate was obtained. When the extrapolation glass transition start temperature of the formed polymer was measured by a method conforming to JIS K7121, it was confirmed that the extrapolation glass transition start temperature was 113 ° C.

<Manufacturing Example 1-2>
40 parts by weight of methacrylic acid dicyclopentanyl of the _{(C 14 H} 20 _{O 2)} was prepared as an acrylic monomer was prepared BPO of 0.44 parts by weight as a radical polymerization initiator. A homopolymer solution of dicyclopentanyl methacrylate was obtained by the same method as in Production Example 1-1 except for the above. When the extrapolation glass transition start temperature of the formed polymer was measured by a method conforming to JIS K7121, it was confirmed that the extrapolation glass transition start temperature was 175 ° C.

<Manufacturing Example 1-3>
28 parts by weight of phenyl methacrylate, 6 parts by weight of 4-hydroxyphenyl methacrylate _{(C 10 H 10 O 3)} , and were prepared 6 parts by weight of glycidyl methacrylate and _{(C 7 H} 10 _{O 3)} as an acrylic monomer .. A polymer solution containing a copolymer of phenyl methacrylate, -4-hydroxyphenyl methacrylate, and glycidyl methacrylate was obtained by the same method as in Production Example 1-1 except for the above. When the extrapolation glass transition start temperature of the formed polymer was measured by a method conforming to JIS K7121, it was confirmed that the extrapolation glass transition start temperature was 101 ° C.

<Manufacturing example 2>
The PGMAc 80 parts by weight was prepared as a polymerization solvent, except that the 20 parts by weight of methyl methacrylate and _{(C 5} H 8 _{O 2)} was prepared as an acrylic monomer was prepared BPO of 0.48 parts by weight as a radical polymerization initiator Obtained a homopolymer solution of methyl methacrylate by the same method as in Production Example 1-1. When the extrapolation glass transition start temperature of the formed polymer was measured by a method conforming to JIS K7121, it was confirmed that the extrapolation glass transition start temperature was 105 ° C.

<Manufacturing example 3>
In Production Example 1-1, the acrylic monomer, the polymerization solvent, and the radical polymerization initiator were changed as shown in Table 2 below to obtain the acrylic polymer of Production Example 3-9 from Production Example 3-1. In addition, the extrapolated glass transition start temperature of the acrylic polymer was measured.

<Manufacturing Example 3-1>
A polymer solution containing a copolymer of phenyl methacrylate, -4-hydroxyphenyl methacrylate, and glycidyl methacrylate was obtained by the same method as in Production Example 1-3.

<Manufacturing Example 3-2>
28 parts by weight of phenyl methacrylate, 8 parts by weight of 4-hydroxyphenyl methacrylate, and 4 parts by weight of glycidyl methacrylate were prepared as acrylic monomers. A polymer solution containing a copolymer of phenyl methacrylate, 4-hydroxyphenyl methacrylate, and glycidyl methacrylate was obtained by the same method as in Production Example 3-1 except for the above. When the extrapolation glass transition start temperature of the formed copolymer was calculated by a method based on JIS K7121, it was found that the extrapolation glass transition start temperature was 104 ° C.

<Manufacturing example 3-3>
0.69 parts by weight of BPO was prepared as a radical polymerization initiator. A polymer solution containing a copolymer of phenyl methacrylate, methacrylic acid, and glycidyl methacrylate was obtained by the same method as in Production Example 3-1 except for the above. When the extrapolation glass transition start temperature of the formed copolymer was calculated by a method based on JIS K7121, it was found that the extrapolation glass transition start temperature was 106 ° C.

<Manufacturing example 3-4>
A homopolymer solution of phenyl methacrylate was obtained by the same method as in Production Example 1-1.

<Manufacturing example 3-5>
The PGMAc 80 parts by weight was prepared as a polymerization solvent, 10 parts by weight of phenyl methacrylate, and 10 parts by weight of methyl methacrylate and _{(C 5} H 8 _{O 2)} was prepared as an acrylic monomer, 0.39 parts by weight BPO was prepared as a radical polymerization initiator. A polymer solution containing a copolymer of phenyl methacrylate and methyl methacrylate was obtained by the same method as in Production Example 1-1 except for the above. When the extrapolation glass transition start temperature of the formed copolymer was calculated by a method based on JIS K7121, it was found that the extrapolation glass transition start temperature was 109 ° C.

<Manufacturing example 3-6>
The PGMAc 80 parts by weight was prepared as a polymerization solvent, 10 parts by weight of methacrylic acid 2- [3- (2H- benzotriazol-2-yl) -4-hydroxyphenyl] ethyl _{(C 18 H 17 N 3 O} 3) , And 10 parts by weight of methyl methacrylate were prepared as an acrylic monomer, and 0.32 parts by weight of BPO was prepared as a radical polymerization initiator. Other than that, a copolymer of 2- [3- (2H-benzotriazole-2-yl) -4-hydroxyphenyl] ethyl methacrylate and methyl methacrylate was prepared by the same method as in Production Example 1-1. A polymer solution containing the mixture was obtained. When the extrapolation glass transition start temperature of the formed copolymer was calculated by a method based on JIS K7121, it was found that the extrapolation glass transition start temperature was 85 ° C.

<Manufacturing example 3-7>
A homopolymer solution of dicyclopentanyl methacrylate was obtained by the same method as in Production Example 1-2.

<Manufacturing example 3-8>
The PGMAc 80 parts by weight was prepared as a polymerization solvent, acrylic acid 2-phenoxyethyl of 14 parts by weight _{(C 11 H 12 O 3)} , methacrylic acid 2.4 parts by weight, and 3.6 parts by weight of methacrylic acid Glycidyl was prepared as an acrylic monomer, and 0.31 parts by weight of BPO was prepared as a radical polymerization initiator. A polymer solution containing a copolymer of 2-phenoxyethyl acrylate, methacrylic acid, and glycidyl methacrylate was obtained by the same method as in Production Example 1-1 except for the above. When the extrapolation glass transition start temperature of the formed copolymer was calculated by a method based on JIS K7121, it was found that the extrapolation glass transition start temperature was 4 ° C.

<Manufacturing example 3-9>
80 parts by weight of PGMAc was prepared as a polymerization solvent, 10 parts by weight of acrylic acid-3-phenoxybenzyl _{(C 16 H 14 O 3)} , and, to prepare the 10 weight parts of methyl methacrylate as an acrylic monomer, 0. 34 parts by weight of BPO was prepared as a radical polymerization initiator. A polymer solution containing a copolymer of -3-phenoxybenzyl acrylate and methyl methacrylate was obtained by the same method as in Production Example 1-1 except for the above. When the extrapolation glass transition start temperature of the formed polymer was calculated by a method based on JIS K7121, it was found that the extrapolation glass transition start temperature was 19 ° C.

<Manufacturing example 4>
In Production Example 1, the amounts of the acrylic monomer, radical polymerization initiator, and polymerization solvent used, and the polymerization time were changed as shown in Table 3 below, and the acrylic polymers of Production Examples 4-1 to 4-6 were changed. Got Further, by analyzing the acrylic polymer using 1H-NMR (400 MHz), the residual amount (RM) of the acrylic monomer represented by the following formula was calculated.
RM = MM / MS x 100
In the above formula, MM is the area ratio of the peak of the acrylic monomer in the NMR spectrum of the acrylic polymer, and MS is the sum of the area ratio of the peak of the acrylic polymer and the area ratio of the peak of the acrylic monomer in the NMR spectrum of the acrylic polymer. Is.

<Manufacturing Example 4-1>
A polymer solution containing a copolymer of phenyl methacrylate, 4-hydroxyphenyl methacrylate, and glycidyl methacrylate was obtained by the same method as in Production Example 1-3. When the residual amount of monomer in the polymer solution was calculated by analysis using 1H-NMR (400 MHz), it was found that the residual amount of monomer (RM) was 3%.

<Manufacturing Example 4-2>
A polymer solution containing a copolymer of phenyl methacrylate, 4-hydroxyphenyl methacrylate, and glycidyl methacrylate was obtained by the same method as in Production Example 4-1 except that the polymerization time was changed to 6 hours. When the residual amount of monomer in the polymer solution was calculated by analysis using 1H-NMR (400 MHz), it was found that the residual amount of monomer (RM) was 10%.

<Manufacturing Example 4-3>
A polymer solution containing a copolymer of phenyl methacrylate, 4-hydroxyphenyl methacrylate, and glycidyl methacrylate was obtained by the same method as in Production Example 4-1 except that the polymerization time was changed to 4 hours. When the residual amount of monomer in the polymer solution was calculated by analysis using 1H-NMR (400 MHz), it was found that the residual amount of monomer (RM) was 20%.

<Manufacturing example 4-4>
80 parts by weight of PGMAc was prepared as a polymerization solvent, 14 parts by weight of phenyl methacrylate, 3 parts by weight of 4-hydroxyphenyl methacrylate, and 3 parts by weight of glycidyl methacrylate were prepared as an acrylic monomer, and 0.30. A weight portion of BPO was prepared as a radical polymerization initiator. A polymer solution containing a copolymer of phenyl methacrylate, 4-hydroxyphenyl methacrylate, and glycidyl methacrylate was obtained by the same method as in Production Example 4-1 except for the above. When the residual amount of monomer in the polymer solution was calculated by analysis using 1H-NMR (400 MHz), it was found that the residual amount of monomer (RM) was 25%.

<Manufacturing example 4-5>
A polymer solution containing a copolymer of phenyl methacrylate, 4-hydroxyphenyl methacrylate, and glycidyl methacrylate was obtained by the same method as in Production Example 4-4 except that the polymerization time was changed to 6 hours. When the residual amount of monomer in the polymer solution was calculated by analysis using 1H-NMR (400 MHz), it was found that the residual amount of monomer (RM) was 30%.

<Manufacturing example 4-6>
A polymer solution containing a copolymer of phenyl methacrylate, 4-hydroxyphenyl methacrylate, and glycidyl methacrylate was obtained by the same method as in Production Example 4-4 except that the polymerization time was changed to 4 hours. When the residual amount of monomer in the polymer solution was calculated by analysis using 1H-NMR (400 MHz), it was found that the residual amount of monomer (RM) was 45%.

<Manufacturing example 5>
In Production Example 1, the amounts of the acrylic monomer, the polymerization solvent, and the radical polymerization initiator used were changed as shown in Table 4 below, and the acrylic copolymers of Production Examples 5-1 to 5-5 were obtained. Obtained. In addition, the weight average molecular weight of the acrylic copolymer was calculated by analysis using a gel permeation chromatography method.

<Manufacturing Example 5-1>
80 parts by weight of PGMAc was prepared as a polymerization solvent, 14 parts by weight of phenyl methacrylate, 3 parts by weight of 4-hydroxyphenyl methacrylate, and 3 parts by weight of glycidyl methacrylate were prepared as an acrylic monomer, 1.50 parts by weight. A weight portion of BPO was prepared as a radical polymerization initiator. A polymer solution containing a copolymer of phenyl methacrylate, 4-hydroxyphenyl methacrylate, and glycidyl methacrylate was obtained by the same method as in Production Example 1-1 except for the above. When the weight average molecular weight of the acrylic copolymer was calculated by analysis using a gel permeation chromatography method, it was found that the weight average molecular weight of the acrylic copolymer was 5000.

<Manufacturing example 5-2>
A copolymer of phenyl methacrylate, 4-hydroxyphenyl methacrylate, and glycidyl methacrylate was prepared by the same method as in Production Example 5-1 except that 1.00 parts by weight of BPO was prepared as a radical polymerization initiator. A polymer solution containing the mixture was obtained. When the weight average molecular weight of the acrylic copolymer was calculated by analysis using a gel permeation chromatography method, it was found that the weight average molecular weight of the acrylic copolymer was 10,000.

<Manufacturing example 5-3>
60 parts by weight of PGMAc was prepared as a polymerization solvent, 28 parts by weight of phenyl methacrylate, 6 parts by weight of 4-hydroxyphenyl methacrylate, and 6 parts by weight of glycidyl methacrylate were prepared as an acrylic monomer, and 1.00. A weight portion of BPO was prepared as a radical polymerization initiator. A polymer solution containing a copolymer of phenyl methacrylate, 4-hydroxyphenyl methacrylate, and glycidyl methacrylate was obtained by the same method as in Production Example 5-1 except for the above. When the weight average molecular weight of the acrylic copolymer was calculated by analysis using a gel permeation chromatography method, it was found that the weight average molecular weight of the acrylic copolymer was 30,000.

<Manufacturing example 5-4>
A copolymer of phenyl methacrylate, 4-hydroxyphenyl methacrylate, and glycidyl methacrylate was prepared by the same method as in Production Example 5-3, except that 0.60 parts by weight of BPO was prepared as a radical polymerization initiator. A polymer solution containing the mixture was obtained. When the weight average molecular weight of the acrylic copolymer was calculated by analysis using a gel permeation chromatography method, it was found that the weight average molecular weight of the acrylic copolymer was 50,000.

<Manufacturing example 5-5>
A copolymer of phenyl methacrylate, 4-hydroxyphenyl methacrylate, and glycidyl methacrylate was prepared by the same method as in Production Example 5-3, except that 0.20 parts by weight of BPO was prepared as a radical polymerization initiator. A polymer solution containing the mixture was obtained. When the weight average molecular weight of the acrylic copolymer was calculated by analysis using a gel permeation chromatography method, it was found that the weight average molecular weight of the acrylic copolymer was 100,000.

[Production example of dispersant]
<Manufacturing example 1>
1.9 parts by mass of azobisisobutynitrile (AIBN) was prepared as a radical polymerization initiator, and 186 parts by mass of propylene glycol monomethyl ether acetate (PGMAc) was prepared as a polymerization solvent. These were charged into a reactor equipped with a gas inlet tube, a condenser, a stirrer, and a thermometer. Next, 27 parts by mass of methyl methacrylate, 27 parts by mass of butyl methacrylate, 21 parts by mass of 2-ethylhexyl methacrylate, and 18 parts by mass of benzyl methacrylate were prepared as monomers constituting the second block, and 3.6 parts by mass were prepared. Kumildithiobenzoate was prepared as a chain transfer agent. These were charged into a reactor and replaced with nitrogen for 30 minutes. Then, the mixture was gently stirred and the reaction solution was reacted at 60 ° C. for 24 hours. As a result, a solution containing the second block was prepared. In addition, the polymerization rate of the second block was calculated by analyzing the second block using 1H-NMR (400 MHz). The polymerization rate of the second block represented by the area ratio of the monomer peak in the NMR spectrum of the second block to the sum of the area ratio of the polymer peak and the area ratio of the monomer peak in the NMR spectrum of the second block is 98. It was 0%.

1.0 part by mass of AIBN substituted with argon was prepared as a radical polymerization initiator, 35 parts by mass of dimethylaminoethyl methacrylate was prepared as a monomer constituting the first block, 70 parts by mass of PGMAc was prepared, and the PGMac was prepared. A solution in which AIBN and dimethylaminoethyl methacrylate were dissolved and replaced with nitrogen for 30 minutes was added to the solution containing the second block, and the mixture was reacted at 60 ° C. for 24 hours. In addition, the polymerization rate of the first block was calculated by analyzing the first block using 1H-NMR (400 MHz). The polymerization rate of the first block represented by the area ratio of the monomer peak in the NMR spectrum of the first block to the sum of the area ratio of the polymer peak and the area ratio of the monomer peak in the NMR spectrum of the first block is 99. It was 3%.

After completion of the reaction, 50 parts by mass of PGMAc was added to the reaction solution, and the reaction solution was poured into 800 mL of n-heptane being stirred. The precipitated polymer was suction-filtered and dried to obtain a copolymer. Then, PGMAc was added so that the non-volatile content was 40% by weight. As a result, a resin-type dispersant solution of Production Example 1 having a tertiary amino group having an amine value per solid content of 71.4 mgKOH / g, a weight average molecular weight of 9900 (Mw), and a non-volatile content of 40% by weight was obtained. ..

<Manufacturing example 2>
22.74 parts by mass of methyl methacrylate was prepared as a monomer constituting the second block, 0.328 parts by mass of AIBN was prepared as a radical polymerization initiator, and 22.74 parts by mass of PGM Ac was prepared as a polymerization solvent. .. These were charged into a reactor equipped with a gas inlet tube, a condenser, a stirrer, and a thermometer. After argon substitution, 3.00 parts by mass of ethyl-2-methyl-2-n-butylteranyl-propionate and 1.116 parts by mass of dibutylditerlide were added as chain transfer agents and reacted at 60 ° C. for 20 hours. It was. In addition, the polymerization rate of the second block was calculated by analyzing the second block using 1H-NMR (400 MHz). The polymerization rate of the second block represented by the area ratio of the monomer peak in the NMR spectrum of the second block to the sum of the area ratio of the polymer peak and the area ratio of the monomer peak in the NMR spectrum of the second block is 98. It was 0%.

45.48 parts of n-butyl methacrylate previously substituted with argon are prepared as a monomer constituting the second block, 0.328 parts of AIBN is prepared as a radical polymerization initiator, and 45.48 parts of PGMAc is used as a polymerization solvent. Got ready. These were added to the above-mentioned solutions and reacted at 60 ° C. for 20 hours. In addition, the polymerization rate of the second block was calculated by analyzing the second block using 1H-NMR (400 MHz). The polymerization rate of the second block represented by the area ratio of the monomer peak in the NMR spectrum of the second block to the sum of the area ratio of the polymer peak and the area ratio of the monomer peak in the NMR spectrum of the second block is 99. It was 2%.

The first block is composed of 22.92 parts of 4-methacryloxyethyl trimellitic acid previously substituted with argon, 22.74 parts of n-butyl methacrylate, and 6.13 parts of methacrylic acid in the obtained solution. Prepared as a monomer, 0.328 parts of AIBN was prepared as a radical polymerization initiator, and 51.79 parts of PGMAc was prepared as a polymerization solvent. These were added to the mixed solution and reacted at 60 ° C. for 20 hours. In addition, the polymerization rate of the first block was calculated by analyzing the first block using 1H-NMR (400 MHz). The polymerization rate of the first block represented by the area ratio of the monomer peak in the NMR spectrum of the first block to the sum of the area ratio of the polymer peak and the area ratio of the monomer peak in the NMR spectrum of the first block is 98. It was 3%.

After completion of the reaction, 50.00 parts of PGMAc was added to the reaction solution and poured into 800 mL of n-heptane being stirred. The precipitated polymer was suction-filtered and dried to obtain a copolymer. Then, PGMAc was added so that the non-volatile content was 40% by weight. As a result, a resin-type dispersant solution of Production Example 2 having an acid value of 105 mgKOH / g per solid content, a weight average molecular weight of 8300 (Mw), and a non-volatile content of 40% by weight was obtained.

[Test example]
[Expanded phthalocyanine]
[Test Example 1]
The mixture having the following composition was uniformly stirred and mixed, dispersed with an Eiger mill for 10 hours using zirconia beads having a diameter of 0.5 mm, and then filtered through a 1.0 μm filtration filter to prepare a colored composition. The prepared dispersion was applied onto a transparent substrate and dried. Then, the coating film was thermoset by post-baking at 230 ° C. to obtain an infrared light cut filter of Test Example 1 having a thickness of 1 μm. In preparing the coloring composition, it was confirmed that the dilated phthalocyanine dye was insoluble in propylene glycol monomethyl ether acetate, which is an organic solvent.

Expanded phthalocyanine formula (3) 15.0 parts Pigment derivative (phthalocyanine derivative having a sulfonic acid group) 1.0 part Resin type dispersant (Production example 1) (Solid content 40%) 12.5 parts Acrylic polymer (Production example) 1-1) 25.0 parts propylene glycol monomethyl ether acetate 96.5 parts

[Test Example 2]
Using a mixture having the following composition, a coloring composition was prepared in the same manner as the coloring composition of Test Example 1. Using the prepared dispersion, an infrared light cut filter of Test Example 2 was obtained by the same method as in Test Example 1.

Expanded phthalocyanine formula (3) 15.0 parts Dye derivative (dialkylaminomethylene phthalocyanine derivative) 1.0 part Resin type dispersant (Production example 2) (Solid content 40%) 12.5 parts Acrylic polymer (Production example 1- 1) 25.0 parts Propylene glycol monomethyl ether acetate 96.5 parts

[Test Example 3]
In Test Example 1, a coloring composition was prepared in the same manner as in Test Example 1 except that the resin-type dispersant of Production Example 1 was removed. Using the prepared dispersion, an infrared light cut filter of Test Example 3 was obtained by the same method as in Test Example 1.

[Test Example 4]
In Test Example 2, a coloring composition was prepared in the same manner as in Test Example 2 except that the resin-type dispersant of Production Example 2 was removed. Using the prepared dispersion, an infrared light cut filter of Test Example 4 was obtained by the same method as in Test Example 1.

[Evaluation method]
Using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation), the transmittance of the infrared light cut filter of each test example for light having each wavelength of 350 nm to 1150 nm was measured. Then, the absorbance was calculated from the measurement result of the transmittance. As a result, the absorbance spectrum was obtained for each infrared light cut filter. The spectrum of absorbance of the dilated phthalocyanine represented by the above formula (3) has a peak at 930 nm. Therefore, it was evaluated whether or not the absorbance at 930 nm of each infrared light cut filter was 0.8 or more. An infrared light cut filter having an absorbance at 930 nm of 0.8 or more has an infrared light absorbing ability suitable for application to a solid-state image sensor.

[Evaluation results]
The absorbance at 930 nm in the infrared light cut filter of Test Example 1 was 1.00, which was found to exceed 0.8. The absorbance of Test Example 2 with the infrared light cut filter was 0.98, which was found to exceed 0.8. On the other hand, the absorbance of the infrared light cut filter of Test Example 3 was 0.35, which was found to be less than 0.8. The absorbance of Test Example 4 with the infrared light cut filter was 0.30, which was found to be less than 0.8.

As described above, as in Test Example 1 and Test Example 2, the solution containing the expanded phthalocyanine, which is insoluble in the organic solvent, contains the dispersant, so that the spectral characteristics derived from the pigment are exhibited by the uniform dispersion state. Obtained. On the other hand, when the solution containing the expanded phthalocyanine insoluble in the organic solvent, as in Test Example 3 and Test Example 4, does not contain a dispersant, the expanded phthalocyanine dye forms aggregates and aggregates. It's easy to do. Therefore, the spectral characteristics are deteriorated. In the infrared light cut filters of Test Examples 1 and 2, the dispersant is located between the expanded phthalocyanines by adsorbing them on the expanded phthalocyanines, so that these expanded phthalocyanines do not associate with each other. It is considered that the distance was formed between the dilated phthalocyanine pigments.

[Acrylic polymer side chain]
[Test Example 5]
25.0 g of the acrylic polymer according to Production Examples 1-1 to 1-3, 15.0 g of extended phthalocyanine, 1.0 g of dye derivative, 12.5 g of resin-type dispersant, 96.5 g of organic A solvent was prepared, and the colored compositions of Test Examples 5-1 to 5-3 were prepared by the same method as in Test Example 1. Further, 66.5 g of the acrylic polymer according to Production Example 2, 15.0 g of expanded phthalocyanine, 1.0 g of a dye derivative, 12.5 g of a resin-type dispersant, and 55.0 g of an organic solvent were prepared and tested. The coloring composition of Example 5-4 was prepared. Using each coloring composition, an infrared light cut filter was formed by the same method as in Test Example 1. As a result, infrared light cut filters of Test Examples 5-1 to 5-4 were obtained.

[Evaluation method]
The absorbance of infrared light in the infrared light cut filters of Test Examples 5-1 to 5-4 was evaluated by the same evaluation method as that of the infrared light cut filter of Test Example 1.

[Evaluation results]
In the infrared light cut filters of Test Examples 5-1 to 5-4, the absorbance at 930 nm was found to be as shown in Table 5 below.

As shown in Table 5, the absorbance at 930 nm of the infrared light cut filter of Test Example 5-1 is 1.00, and the absorbance of the infrared light cut filter of Test Example 5-2 is 0.91. It was confirmed that the absorbance of Test Example 5-3 with the infrared light cut filter was 0.95. Further, it was confirmed that the absorbance at 930 nm in the infrared light cut filter of Test Example 4 was 0.70.
As described above, when the absorbance at 930 nm was calculated for each infrared light cut filter, it was confirmed that the absorbance of the infrared light cut filters of Test Examples 5-1 to 5-3 was 0.8 or more. It was. On the other hand, it was confirmed that the absorbance of the infrared light cut filter of Test Example 5-4 was less than 0.8.
As described above, from the comparison between the infrared light cut filter of Test Examples 5-1 to 5-3 and the infrared light cut filter of Test Example 5-4, the coloring composition for forming the infrared light cut filter is obtained. It was found that the side chain structure of the acrylic polymer contained therein had an aromatic ring or an alicyclic structure, so that the decrease in absorbance in the infrared light cut filter was suppressed. In the infrared light cut filters of Test Examples 5-1 to 5-3, the aromatic ring or alicyclic structure located in the side chain of the acrylic polymer is located between the expanded phthalocyanine and the other expanded phthalocyanine. Therefore, it is considered that the distance between the expanded phthalocyanines was formed so that these expanded phthalocyanines did not associate with each other.

[Organic solvent]
[Test Example 6]
Propylene glycol monomethyl ether acetate was used as the organic solvent of Test Example 6-1 and propylene glycol monomethyl ether was used as the organic solvent of Test Example 6-2. Cyclohexanone was used as the organic solvent of Test Example 6-3, 2-propanol was used as the organic solvent of Test Example 6-4, and toluene was used as the organic solvent of Test Example 6-5. Other than that, as in Test Example 1, 25.0 g of the acrylic polymer according to Production Example 1, 15.0 g of expanded phthalocyanine, 1.0 g of a dye derivative, 12.5 g of a resin-type dispersant, and 96.5 g of an organic solvent was prepared, and the colored compositions of Test Examples 6-1 to 6-5 were prepared by the same method as in Test Example 1. Then, using each coloring composition, an infrared light cut filter was formed by the same method as in Test Example 1. As a result, infrared light cut filters of Test Examples 6-1 to 6-5 were obtained.

[Evaluation method]
The absorbance of infrared light in the infrared light cut filters of Test Examples 6-1 to 6-5 was evaluated by the same evaluation method as the infrared light cut filter of Test Example 1.

[Evaluation results]
In the infrared light cut filters of Test Examples 6-1 to 6-5, the absorbance at 930 nm was found to be as shown in Table 6 below.

As shown in Table 6, the absorbance of Test Example 6-1 is 1.00, the absorbance of Test Example 6-2 is 0.88, and the absorbance of Test Example 6-3 is 0.94. Admitted. Further, it was confirmed that the absorbance of Test Example 6-4 was 0.32 and the absorbance of Test Example 6-5 was 0.31.

As described above, when the absorbance at 930 nm was calculated for each infrared light cut filter, it was confirmed that the absorbance of the infrared light cut filters of Test Examples 6-1 to 6-3 was 0.8 or more. Was done. On the other hand, it was confirmed that the absorbance of the infrared light cut filters of Test Examples 6-4 to 6-5 was less than 0.8. From these results, it can be said that the organic solvent contained in the infrared light cut filter is preferably a ketone solvent, an ether solvent, and an ester solvent. Test Example 5-1 using propylene glycol monomethyl ether acetate as the organic solvent does not show a decrease in absorbance and can be said to be particularly preferable.

[Glass transition temperature of acrylic polymer]
[Test Example 7]
The acrylic polymers described in Production Examples 3-1 to 3-9 were prepared, and a colored composition was prepared in the same manner as in Test Example 1. By forming an infrared light cut filter by the same method as in Test Example 1, infrared light cut filters of Test Examples 7-1 to 7-9 were obtained.

[Evaluation method]
The absorbance of infrared light in the infrared light cut filters of Test Examples 7-1 to 7-9 was evaluated by the same evaluation method as that of the infrared light cut filter of Test Example 1.

[Evaluation results]
In the infrared light cut filters of Test Examples 7-1 to 7-9, the absorbance at 930 nm was found to be as shown in Table 7 below.

As shown in Table 7, the absorbance at 930 nm of the infrared light cut filter of Test Example 7-1 is 0.95, and the absorbance of the infrared light cut filter of Test Example 7-2 is 0.97. It was confirmed that the absorbance of Test Example 7-3 with the infrared light cut filter was 0.95. Further, the absorbance of the infrared light cut filter of Test Example 7-4 at 930 nm was 0.95, and the absorbance of the infrared light cut filter of Test Example 7-5 was 0.92. The absorbance of the 7-6 infrared cut filter was found to be 1.10. The absorbance of the infrared light cut filter of Test Example 7-7 at 930 nm was 0.91, and the absorbance of the infrared light cut filter of Test Example 7-8 was 0.65. The absorbance of the 7-9 infrared cut filter was found to be 0.77.

As described above, it was confirmed that the absorbances of Test Examples 7-1 to 7-7 were 0.8 or more. On the other hand, it was confirmed that the absorbance of the infrared light cut filters of Test Examples 7-8 to 7-9 was less than 0.8. From these results, it can be said that the glass transition temperature of the acrylic polymer contained in the infrared light cut filter is preferably 30 ° C. or higher.

[Residual amount of acrylic monomer]
[Test Example 8]
The acrylic polymers described in Production Examples 4-1 to 4-6 were prepared, and a colored composition was prepared in the same manner as in Test Example 1. By forming the infrared light cut filter by the same method as in Test Example 1, the infrared light cut filters of Test Examples 8-1 to 8-6 were obtained.

[Evaluation method]
The absorbance of infrared light in the infrared light cut filters of Test Examples 8-1 to 8-6 was evaluated by the same evaluation method as that of the infrared light cut filter of Test Example 1.

[Evaluation results]
In the infrared light cut filters of Test Examples 8-1 to 8-6, the absorbance at 930 nm was found to be as shown in Table 8 below.

As shown in Table 8, the absorbance at 930 nm of the infrared light cut filter of Test Example 8-1 is 0.95, and the absorbance of the infrared light cut filter of Test Example 8-2 is 0.95. It was confirmed that the absorbance of Test Example 8-3 with the infrared light cut filter was 0.95. Further, the absorbance at 930 nm of the infrared light cut filter of Test Example 8-4 was 0.79, and the absorbance of the infrared light cut filter of Test Example 8-5 was 0.78. The absorbance of the 7-6 infrared cut filter was found to be 0.78.

As described above, it was confirmed that the infrared light cut filters of Test Examples 8-1 to 8-3 had an absorbance of 0.8 or more at 930 nm. On the other hand, in the infrared light cut filters of Test Examples 8-4 to 8-6, it was found that the absorbance at 930 nm was less than 0.8. From these results, it can be said that the amount of residual monomer in the acrylic polymer in the infrared light cut filter is preferably 20% or less.

[Average molecular weight of acrylic polymer]
[Test Example 9]
The acrylic polymers described in Production Examples 5-1 to 5-5 were prepared, and a colored composition was prepared in the same manner as in Test Example 1. By forming an infrared light cut filter by the same method as in Test Example 1, infrared light cut filters of Test Examples 9-1 to 9-5 were obtained.

[Evaluation method]
The absorbance of infrared light in the infrared light cut filters of Test Examples 9-1 to 9-5 was evaluated by the same evaluation method as that of the infrared light cut filter of Test Example 1.

[Evaluation results]
In the infrared light cut filters of Test Examples 9-1 to 9-5, the absorbance at 930 nm was found to be as shown in Table 9 below.

As shown in Table 9, the absorbance at 930 nm of the infrared light cut filter of Test Example 9-1 is 0.79, and the absorbance of the infrared light cut filter of Test Example 9-2 is 0.92. It was confirmed that the absorbance of Test Example 9-3 with the infrared light cut filter was 0.95. Further, it was confirmed that the absorbance at 930 nm of the infrared light cut filter of Test Example 9-4 was 0.95, and the absorbance of the infrared light cut filter of Test Example 9-5 was 0.99. Was done.

As described above, it was confirmed that the infrared light cut filters of Test Examples 9-2 to 9-5 had an absorbance of 0.8 or more at 930 nm. On the other hand, in the infrared light cut filter of Test Example 9-1, it was found that the absorbance at 930 nm was less than 0.8. It can be said that the average molecular weight of the acrylic polymer in the infrared light cut filter is preferably 10,000 or more.

As described above, according to one embodiment of the method for manufacturing a coloring composition, an infrared light cut filter, a filter for a solid-state image sensor, a solid-state image sensor, and a filter for a solid-state image sensor, the effects described below can be obtained. Obtainable.

(1) When the first block of the dispersant is adsorbed on the dilated phthalocyanine, the dispersant is located between the dilated phthalocyanine and another dilated phthalocyanine. Then, a distance is formed between the dilated phthalocyanines to the extent that the association and aggregation of the dilated phthalocyanines are suppressed. As a result, the decrease in absorbance due to the association and aggregation of the expanded phthalocyanine, that is, the decrease in the absorbance at the wavelength at which the monomer is expected to be absorbed by the expanded phthalocyanine is suppressed. As a result, in the infrared light cut filter 13, it is possible to suppress a decrease in the absorbance of infrared light.

(2) Since there is an acrylic polymer containing any of aromatic rings, alicyclics, and cyclic ethers, the effectiveness of the effect of suppressing the decrease in absorbance at wavelengths where absorption by extended phthalocyanine is expected is enhanced.

(3) In a dispersion system using at least one of a ketone solvent, an ether solvent, and an ester solvent as an organic solvent, the dispersibility of the expanded phthalocyanine can be enhanced.
(4) Since the organic solvent is propylene glycol monomethyl ether acetate, it is easy to enhance the dispersibility of the expanded phthalocyanine and to form a coating film having a uniform thickness when obtaining the infrared light cut filter 13. is there.

(5) Since the glass transition temperature of the dispersant is 30 ° C. or higher, it is possible to suppress a decrease in the absorbance of infrared light.

(6) Since the glass transition temperature of the curable compound is 30 ° C. or higher, it is possible to maintain the mechanical strength of the infrared light cut filter 13 at room temperature near 20 ° C.
(7) Since the average molecular weight of the curable compound is 10,000 to 150,000 or less, it is possible to sufficiently obtain the mechanical strength and light resistance of the infrared light cut filter 13.

(8) Since the amount of the acrylic monomer remaining in the infrared light cut filter 13 is 20% or less, it is possible to suppress a decrease in the absorbance of infrared light in the expanded phthalocyanine due to the residual acrylic monomer.

(9) The mass of the colorant with respect to the total mass of the coloring composition in the infrared light cut filter 13 having a thickness of 1 μm or less is 30% or more, and the dispersibility of the expanded phthalocyanine is determined by the block copolymer. Since it is enhanced, it is also possible to enhance the absorbance of infrared light.

[Change example]
The above-described embodiment can be modified and implemented as follows.
[Dispersant]
-The glass transition temperature of the dispersant may be lower than 30 ° C. Even in this case, if the infrared light cut filter 13 contains an extended phthalocyanine and a dispersant containing a block copolymer having a first block and a second block, the above-mentioned (1) It is possible to obtain not a little effect according to.

[Curable compound]
-When the curable compound is an acrylic polymer, the side chain may contain a structure other than an aromatic ring, an alicyclic, and a cyclic ether. Even in this case, if the infrared light cut filter 13 contains an extended phthalocyanine and a dispersant containing a block copolymer having a first block and a second block, the above-mentioned (1) It is possible to obtain not a little effect according to.

The glass transition temperature of the curable compound may be lower than 30 ° C. Even in this case, if the infrared light cut filter 13 contains an extended phthalocyanine and a dispersant containing a block copolymer having a first block and a second block, the above-mentioned (1) It is possible to obtain not a little effect according to.

-The average molecular weight of the curable compound may be 10,000 or less, or may be 150,000 or more. Even in this case, if the infrared light cut filter 13 contains an extended phthalocyanine and a dispersant containing a block copolymer having a first block and a second block, the above-mentioned (1) It is possible to obtain not a little effect according to.

-The residual monomer contained in the curable compound may be more than 20%. Even in this case, if the infrared light cut filter 13 contains an extended phthalocyanine and a dispersant containing a block copolymer having a first block and a second block, the above-mentioned (1) It is possible to obtain not a little effect according to.

[Organic solvent]
-The organic solvent may be an organic solvent other than the ketone solvent, the ether solvent, and the ester solvent as long as the following requirements are satisfied. That is, any organic solvent may be used as long as it satisfies that the expanded phthalocyanine, which is a colorant, is insoluble and that the curable compound is dissolved.

[Barrier layer]
The solid-state image sensor filter 10F may include a barrier layer between the infrared light cut filter 13 and each microlens. The barrier layer suppresses the transmission of the oxidation source of the infrared light cut filter 13. Oxidation sources include oxygen and water. The oxygen permeability of the barrier layer is ^{preferably 5.0 cc / m 2} / day / atom or less, for example. The oxygen permeability is a value based on JIS K7126: 2006. Since the oxygen transmittance is set to 5.0 cc / m ² / day / atom or less, the barrier layer suppresses the oxidation source from reaching the infrared light cut filter 13, so that the infrared light cut filter 13 is oxidized. It is less likely to be oxidized by the source. Therefore, the light resistance of the infrared light cut filter 13 can be improved.

The material forming the barrier layer is an inorganic compound, preferably a silicon compound. The material forming the barrier layer is, for example, at least one selected from the group consisting of silicon nitride, silicon oxide, and silicon oxynitride. The layer structure of the barrier layer may be a single layer structure composed of a single compound, a laminated structure of layers composed of a single compound, or a laminated structure of layers composed of different compounds. May be good.

The infrared light cut filter 13 in the above-described embodiment contains expanded phthalocyanine. Dilated phthalocyanines contain cyclic conjugated double bonds. Cyclic conjugated double bonds are more robust and light resistant than chain conjugated double bonds. Therefore, the infrared light cut filter 13 has light resistance even when it does not pass through the barrier layer. As a result, the thickness of the solid-state image sensor filter 10F can be suppressed from increasing because the solid-state image sensor filter 10F does not need to be provided with a barrier layer.

-The barrier layer can be arranged not only between the infrared light cut filter 13 and each microlens but also on the outer surface of each microlens. At this time, the outer surface of the barrier layer functions as an incident surface for incident light on the solid-state image sensor 10. In short, the position of the barrier layer may be on the incident side of light with respect to the infrared light cut filter 13. According to this configuration, the barrier layer is located on the optical surface of each microlens.

[Anchor layer]
When the solid-state image sensor filter 10F includes a barrier layer, the solid-state image sensor 10 includes an anchor layer between the barrier layer and the lower layer of the barrier layer, and the barrier layer and the lower layer of the barrier layer are in close contact with each other. It is also possible to change the configuration so that the anchor layer enhances the sex. Further, the solid-state image sensor 10 is provided with an anchor layer between the barrier layer and the upper layer of the barrier layer, and the structure can be changed so that the anchor layer enhances the adhesion between the barrier layer and the upper layer of the barrier layer.

The material forming the anchor layer is, for example, a polyfunctional acrylic resin, a silane coupling agent, or the like. The thickness of the anchor layer is, for example, 50 nm or more and 1 μm or less, and if it is 50 nm or more, it is easy to obtain adhesion between layers, and if it is 1 μm or less, it is easy to absorb light in the anchor layer. It can be suppressed.

[Color filter]
-The color filter can be changed to a three-color filter consisting of a cyan filter, a yellow filter, and a magenta filter. Further, the color filter can be changed to a four-color filter composed of a cyan filter, a yellow filter, a magenta filter, and a black filter. Further, the color filter can be changed to a four-color filter composed of a transparent filter, a yellow filter, a red filter, and a black filter.

[Other]
The solid-state image sensor 10 has a configuration in which the barrier layer is omitted, and has an oxygen transmittance of 5.0 cc / m ^{2 in a laminated structure located on the incident surface 15S side with respect to the infrared light cut filter 13.} The configuration may be less than / day / atom. For example, the laminated structure may be another functional layer such as a flattening layer or an adhesion layer, and the oxygen transmittance of each microlens may be 5.0 cc / m ² / day / atom or less.

-The infrared light cut filter may be a microlens. In this case, since the microlens having a function of capturing light toward the photoelectric conversion element also has a function of cutting infrared light, the layer structure of the solid-state image sensor filter can be simplified.

-The material forming the infrared light pass filter 12P and the infrared light cut filter 13 is an additive for having other functions such as a light stabilizer, an antioxidant, a heat stabilizer, and an antistatic agent. Can be included.

The solid-state image sensor 10 may be provided with a bandpass filter on the incident surface side of light for a plurality of microlenses. The bandpass filter is a filter that transmits only light having a specific wavelength of visible light and near infrared light, and has a function similar to that of the infrared light cut filter 13. That is, the bandpass filter can cut unnecessary infrared light that can be detected by the photoelectric conversion elements 11R, 11G, and 11B for each color. As a result, the detection accuracy of visible light by the photoelectric conversion elements 11R, 11G, and 11B for each color and the detection of near-infrared light having a wavelength in the 850 nm or 940 nm band, which is the detection target of the photoelectric conversion element 11P for infrared light, are detected. The accuracy can be improved.

10 ... Solid imaging element, 10F ... Solid imaging element filter, 11 ... Photoelectric conversion element, 11R ... Red photoelectric conversion element, 11G ... Green photoelectric conversion element, 11B ... Blue photoelectric conversion element, 11P ... Infrared light Photoelectric conversion element, 12R ... Red filter, 12G ... Green filter, 12B ... Blue filter, 12P ... Infrared light path filter, 13 ... Infrared light cut filter, 13H ... Through hole, 15R ... Red microlens, 15G ... Green microlens, 15B ... Blue microlens, 15P ... Infrared light microlens, 15S ... Incident surface.

Claims (14)

Contains colorants, dispersants, curable compounds, and organic solvents that dissolve the curable compounds.
The colorant contains dilated phthalocyanine represented by the following formula (1).
The dispersant comprises a block copolymer having a first block and a second block.
The first block contains either an acidic functional group or a basic functional group having an affinity for adsorbing the expanded phthalocyanine.
The second block is a coloring composition in which the expanded phthalocyanine is insoluble and has an affinity for the organic solvent or the curable compound.

However, in the formula (1), M is molybdenum or tungsten. R1 and R2 are hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocycle. Oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl Sulfonylamino group, arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, aryloxy It contains any one of a carbonyl group, an alkoxycarbonyl group, a carbamoyl group, an arylazo group, a heterocyclic azo group, an imide group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, and a silyl group. The curable compound contains an acrylic polymer and contains
The coloring composition according to claim 1, wherein the acrylic polymer is an acrylic polymer containing any of an aromatic ring, an alicyclic ring, and a cyclic ether in a side chain. The coloring composition according to claim 1 or 2, wherein the organic solvent contains at least one of a ketone solvent, an ether solvent, and an ester solvent. The coloring composition according to claim 3, wherein the organic solvent is propylene glycol monomethyl ether acetate. The coloring composition according to any one of claims 1 to 4, wherein the glass transition temperature of the dispersant is 30 ° C. or higher. The coloring composition according to any one of claims 1 to 5, wherein the glass transition temperature of the curable compound is 30 ° C. or higher. The coloring composition according to any one of claims 1 to 6, wherein the average molecular weight of the curable compound is 10,000 or more and 150,000 or less. The curable compound contains an acrylic polymer and contains
The percentage (MM / MS × 100) of the mass (MM) of the acrylic monomer to the sum (MS) of the mass of the acrylic polymer and the mass of the acrylic monomer used for producing the acrylic polymer is 20% or less. The coloring composition according to claim 1. The coloring composition according to any one of claims 1 to 8, wherein the percentage of the mass of the coloring agent to the mass of the total solid content contained in the coloring composition is 30% or more. An infrared light cut filter formed by the coloring composition according to any one of claims 1 to 9. A filter for a solid-state image sensor including the infrared light cut filter according to claim 10. Photoelectric conversion element and
A solid-state image sensor comprising the filter for a solid-state image sensor according to claim 11. Contains colorants, dispersants, and cured products of curable compounds
The colorant contains dilated phthalocyanine represented by the following formula (1).
The dispersant comprises a block copolymer having a first block and a second block.
The first block contains either an acidic functional group or a basic functional group having an affinity for adsorbing the expanded phthalocyanine.
The second block is an organic solvent that insolubilizes the expanded phthalocyanine and makes the curable compound soluble, or an infrared light cut filter having an affinity for the curable compound.

However, in the formula (1), M is molybdenum or tungsten. R1 and R2 are hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocycle. Oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl Sulfonylamino group, arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, aryloxy It contains any one of a carbonyl group, an alkoxycarbonyl group, a carbamoyl group, an arylazo group, a heterocyclic azo group, an imide group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, and a silyl group. A coating film containing a coloring composition containing a colorant, a dispersant, a curable compound, and an organic solvent, wherein the colorant contains an expanded phthalocyanine represented by the following formula (1), and the dispersant. Dissolves the first block containing either an acidic functional group or a basic functional group having an affinity for adsorbing the expanded phthalocyanine, and the expanded phthalocyanine insoluble and the curable compound. To form the coating film containing a block copolymer having an organic solvent or a second block having an affinity for the curable compound.
To form a colored layer by curing the curable compound and curing the coating film,
A method for manufacturing a filter for a solid-state image sensor, which comprises patterning the colored layer by dry etching.

However, in the formula (1), M is molybdenum or tungsten. R1 and R2 are hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocycle. Oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl Sulfonylamino group, arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, aryloxy It contains any one of a carbonyl group, an alkoxycarbonyl group, a carbamoyl group, an arylazo group, a heterocyclic azo group, an imide group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, and a silyl group.

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