KR20240089673A - Pigment dispersion compositions, photosensitive coloring compositions and color filters - Google Patents

Abstract

A pigment dispersion composition having good pigment dispersibility and storage stability is provided. Furthermore, by using the pigment dispersion composition in a photosensitive coloring composition, curing proceeds at low temperature, and a cured product having excellent solvent resistance and good developability is obtained. Additionally, a color filter comprising a cured product of the photosensitive coloring composition and an image display element comprising the same are provided. The pigment dispersion composition of the present invention contains a binder resin (A-1), a pigment (B), a polymer dispersant (C), and a solvent (D-1). The binder resin (A-1) has a functional group (X), and the polymer dispersant (C) has a functional group (Y) that is reactive with the functional group (X).

Description

Pigment dispersion compositions, photosensitive coloring compositions and color filters

The present invention relates to pigment dispersion compositions, photosensitive coloring compositions and color filters.

This application claims priority based on Japanese Patent Application No. 2021-209989, filed in Japan on December 23, 2021, and uses the content here.

Currently, from the viewpoint of resource conservation and energy conservation, photosensitive resin compositions that can be cured by active energy rays such as ultraviolet rays and electron beams are widely used in various fields such as coatings, printing, paints, and adhesives. Photosensitive resin compositions are used in the field of electronic materials, such as solder resists for printed wiring boards and other resists for color filters in displays such as liquid crystal and organic EL.

A color filter generally consists of a transparent substrate such as a glass substrate, red, green, and blue pixels formed on the transparent substrate, a black matrix formed at the boundary of the pixel, and a protective film formed on the pixel and the black matrix. do. A color filter having such a structure is usually manufactured by sequentially forming a colored pattern such as a black matrix or pixel, or a pattern such as a protective film on a transparent substrate. As a method of forming various patterns, various methods have been proposed. Among them, color filters manufactured using a photosensitive resin composition in which pigments/dyes are dispersed as a resist and using a photolithography method that repeats application, exposure, development, and baking have excellent durability and fewer defects such as pinholes. Gives a coloring pattern. For that reason, the photolithography method is currently mainstream.

Generally, the photosensitive resin composition used in the photolithography method contains an alkali-soluble binder resin, a reactive diluent, a photopolymerization initiator, a pigment/dye (also called a colorant), and a solvent. In the method of producing a color filter using this photosensitive resin composition, a black matrix and a pattern of red, green, and blue are formed repeatedly, and the cured product of the photosensitive resin composition has resistance to various solvents exposed during the manufacturing process. This is required.

In addition, the organic EL light-emitting layer often uses members that are weak to heat, and a color filter that cures at a low curing temperature is required.

In recent years, displays such as liquid crystal and organic EL have been required to have higher image quality and higher precision, and color filters have also been required to be designed to achieve higher brightness and an expanded color reproduction range. In order to achieve higher brightness or expand the color reproduction range, there are examples of using only dye as a colorant, but dyes have lower heat resistance and solvent resistance than pigments, and the rate and type of use are limited, so in many cases, pigments are added to the colorant. there is. When forming a color filter using a pigment, uniform micronization of the pigment is essential. By refining the pigment, scattering of light passing through the color filter by the pigment particles is reduced, contributing to the transmittance is high, and high brightness is achieved.

However, micronized pigment particles are prone to aggregation, and there is a problem that the dispersibility of the pigment and the storage stability of the pigment dispersion composition tend to deteriorate. As a method of improving the dispersibility of micronized pigment in a pigment dispersion composition, it is effective to use a pigment and a dispersant in combination.

Additionally, in order to expand the color reproduction range, efforts are being made to blend colorants in high concentrations. As the concentration of the colorant increases, the concentration of the dispersant and other compositions relatively decreases, so even with a smaller amount of the dispersant, the pigment dispersibility, storage stability, heat resistance, solvent resistance, and pattern adhesion of the pigment dispersion composition are affected. It is required to exhibit resist characteristics.

Generally, a dispersant has a site that is adsorbed to a pigment and a site that has high affinity with a solvent or other resin composition. The optimal structure of the site adsorbed to the pigment changes depending on the surface condition of the pigment. For example, a dispersant having a basic adsorption site is used for a pigment having a surface biased toward acidity, and in many cases, an amino group is used for the basic adsorption site as in Patent Document 1.

In addition, in recent years, as in Patent Documents 1 to 3, dispersants excellent in solvent resistance have been developed by introducing an ethylenically unsaturated group, which is a photosensitive group, into the dispersant, imparting a curing function, and improving photocuring.

Japanese Patent Publication No. 2008-542523 International Publication No. 2006/075754 International Publication No. 2013/175978

However, when the dispersant disclosed in Patent Documents 1 to 3 is used, a cured product with good solvent resistance is obtained, but the pigment dispersibility is insufficient and use alone is difficult, and the storage stability of the pigment dispersion composition also needs to be improved. did. In addition, since the curable group being introduced is an ethylenically unsaturated group, a high curing temperature is required, and it cannot be used in combination with materials vulnerable to heat, etc., so improvements have been required.

The present invention was made to solve the problems described above, and its purpose is to provide a pigment dispersion composition with good pigment dispersibility and good storage stability. Another object of the present invention is to provide a photosensitive coloring composition that cures at a low temperature when using the present pigment dispersion composition and gives a cured product with excellent solvent resistance and good developability, and a color filter having the cured product. The purpose is to provide an image display element having this.

The present invention includes the following aspects.

[1] Binder resin (A-1),

Pigment (B),

A polymer dispersant (C),

Solvent (D-1)

It is a pigment dispersion composition containing,

The binder resin (A-1) has at least one selected from amino groups and quaternary ammonium cation groups, and has a functional group (X),

A pigment dispersion composition characterized in that the polymer dispersant (C) has a functional group (Y) that is reactive with the functional group (X).

[2] The pigment dispersion composition according to [1], wherein the polymer dispersant (C) is a reaction product of the amino group-containing polymer compound (c-1) and the halogen compound (c-2) having the functional group (Y).

[3] The pigment dispersion composition according to [2], wherein the amino group of the amino group-containing polymer compound (c-1) is a tertiary amino group.

[4] The functional group (X) of the binder resin (A-1) is at least one selected from hydroxy groups and mercapto groups,

The pigment dispersion composition according to any one of [1] to [3], wherein the functional group (Y) of the polymer dispersant (C) is at least one selected from the group consisting of a block isocyanato group and an alkyl ester.

[5] [1] wherein the functional group (X) of the binder resin (A-1) is a carboxyl group, and the functional group (Y) of the polymer dispersant (C) is at least one selected from epoxy groups and oxetanyl groups. The pigment dispersion composition according to any one of [3] to [3].

[6] The functional group (X) of the binder resin (A-1) is at least one selected from the group consisting of a block isocyanato group and an alkyl ester,

The pigment dispersion composition according to any one of [1] to [3], wherein the functional group (Y) of the polymer dispersant (C) is at least one selected from a hydroxy group and a mercapto group.

[7] The functional group (X) of the binder resin (A-1) is at least one selected from an epoxy group and an oxetanyl group,

The pigment dispersion composition according to any one of [1] to [3], wherein the functional group (Y) of the polymer dispersant (C) is a carboxyl group.

[8] The pigment dispersion composition according to any one of [1] to [7], wherein the pigment (B) contains a pigment having a halogenated phthalocyanine skeleton.

[9] For 100 parts by mass of the above pigment (B),

Containing 10 to 80 parts by mass of the binder resin (A-1),

The pigment dispersion composition according to any one of [1] to [8], containing 10 to 80 parts by mass of the polymer dispersant (C).

[10] The pigment dispersion composition according to any one of [1] to [9],

Binder resin (A-2),

a reactive diluent (E),

Photopolymerization initiator (F)

A photosensitive coloring composition comprising:

[11] For 100 parts by mass of the above pigment (B),

Containing 10 to 80 parts by mass of the binder resin (A-1),

Containing 10 to 80 parts by mass of the polymer dispersant (C),

Containing 50 to 280 parts by mass of the binder resin (A-2),

Containing 40 to 200 parts by mass of the reactive diluent (E),

Containing 0.1 to 10 parts by mass of the photopolymerization initiator (F)

The photosensitive coloring composition according to [10].

[12] A resin cured film obtained by curing the photosensitive coloring composition according to [10] or [11].

[13] A color filter having a cured product of the photosensitive coloring composition according to [10] or [11].

[14] An image display element including the color filter according to claim 13.

According to the present invention, it is possible to provide a pigment dispersion composition with good pigment dispersibility and good storage stability. Furthermore, by using the pigment dispersion composition in a photosensitive coloring composition, curing proceeds at low temperature, and a cured product having excellent solvent resistance and good developability is obtained. Additionally, a color filter containing a cured product of the photosensitive coloring composition and an image display element containing the same can be provided.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the embodiments described below.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the embodiments described below. In addition, in this specification, “(meth)acryloyloxy group” refers to one or more types selected from methacryloyloxy group and acryloyloxy group. The same applies to “(meth)acrylic acid.”

<Pigment dispersion composition>

The pigment dispersion composition of this embodiment contains binder resin (A-1), pigment (B), polymer dispersant (C), and solvent (D-1).

[Binder Resin (A-1)]

The binder resin (A-1) of this embodiment does not have an amino group or a quaternary ammonium structure, but has a functional group (X). By using the binder resin (A-1), the functional group (X) is crosslinked with the functional group (Y) that is reactive with the functional group (X) contained in the polymer dispersant (C) described later, so it can be used as a photosensitive coloring composition. It exhibits excellent low-temperature curing properties. In addition, even when cured at low temperature, the obtained resin cured film exhibits excellent solvent resistance.

The functional group (X) possessed by the binder resin (A-1) is a group that does not have an amino group or a quaternary ammonium structure and can be crosslinked by heating with the functional group (Y) possessed by the polymer dispersant (C) described later. There is no particular limitation. Examples of the functional group (X) include a hydroxy group, a carboxyl group, a block isocyanato group, an epoxy group, an oxetanyl group, an alkyl ester group (preferably an alkyl ester group having 1 to 3 carbon atoms), and a mercapto group. . Among these, a hydroxy group and a block isocyanato group are preferable because they have high reactivity and from the viewpoint of stability when used as a mill base. These functional groups (X) may be included individually or in combination of two or more.

The type of binder resin (A-1) is not particularly limited as long as it is a binder resin generally used in negative resists. For example, (meth)acrylic resin, vinyl ester resin, etc. can be mentioned. Among them, (meth)acrylic resin is preferable because it has excellent developability as a photosensitive coloring composition.

As the (meth)acrylic resin, a copolymer of an ethylenically unsaturated group-containing compound having a functional group (X) and a (meth)acrylate monomer is preferable. An ethylenically unsaturated group-containing compound having a functional group (X) is a compound having a functional group (X) and an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include vinyl group, allyl group, and (meth)acryloyl group.

When the functional group (X) is a hydroxy group, examples of the ethylenically unsaturated group-containing compound having the functional group (X) include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1, and ethylenically unsaturated group-containing compounds having a hydroxy group, such as 6-hexanediol (meth)acrylate and 3-methylpentanediol (meth)acrylate.

When the functional group (X) is a carboxyl group, examples of the ethylenically unsaturated group-containing compound having the functional group (X) include (meth)acrylic acid, itaconic acid, crotonic acid, cinnamic acid, and 2-(meth)acryloyloxyethyl. Succinic acid, 2-(meth)acryloyloxyethylphthalic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, α-bromo(meth)acrylic acid, β-furyl(meth)acrylic acid, crotonic acid, propiolic acid , unsaturated monobasic acids such as cinnamic acid, α-cyanocinnamic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, monomethyl fumarate, monoethyl itaconate, monomethyl maleate, monoethyl maleate , unsaturated dibasic acid monoesters such as monoisopropyl maleate, monomethyl fumarate, and monoethyl itaconate, or compounds containing an ethylenically unsaturated group having a carboxyl group.

When the functional group (X) is a block isocyanato group, examples of the ethylenically unsaturated group-containing compound having the functional group ( ) Acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, Compounds containing an ethylenically unsaturated group having a blocked isocyanato group, such as compounds obtained by blocking the isocyanato group in isocyanate compounds such as 4-isocyanatocyclohexyl (meth)acrylate and methacryloyl isocyanate with a blocking agent. can be mentioned.

When the functional group (X) is an epoxy group, examples of ethylenically unsaturated group-containing compounds having the functional group (X) include glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and alicyclic (meth)acrylate having an epoxy group and its lactone adduct, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, epoxide of dicyclopentenyl (meth)acrylate, And ethylenically unsaturated group-containing compounds having an epoxy group, such as epoxy group-containing (meth)acrylate, such as an epoxidized product of dicyclopentenyloxyethyl (meth)acrylate.

When the functional group (X) is an oxetanyl group, examples of the ethylenically unsaturated group-containing compound having the functional group (X) include (3-ethyloxetan-3-yl)methyl (meth)acrylate, 4-[3 -(3-ethyloxetan-3-ylmethoxy)propoxy]styrene, 4-[6-(3-ethyloxetan-3-ylmethoxy)hexyloxy]styrene, 4-[5-(3-ethyl and ethylenically unsaturated group-containing compounds having an oxetanyl group, such as oxetan-3-ylmethoxy)pentyloxy]styrene and 2-vinyl-2-methyloxetane.

When the functional group ( and ethylenically unsaturated group-containing compounds having an alkyl ester group having 1 to 3 carbon atoms, such as diethyl fumarate and diethyl itaconate.

When the functional group (X) is a mercapto group, examples of the ethylenically unsaturated group-containing compound having the functional group ( -Ethylenically unsaturated group-containing compounds having a mercapto group such as sulfanylbutyl (meth)acrylate, 2-vinylbenzenethiol, and 11-bromo-1-undecanethiol can be mentioned.

Examples of the blocking agent that blocks the isocyanate compound include lactams such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam; Alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol, and cyclohexanol; Phenol, cresol, xylenol, ethyl phenol, o-isopropyl phenol, butyl phenol such as p-tert-butyl phenol, p-tert-octyl phenol, nonyl phenol, dinonyl phenol, styrenated phenol, oxybenzoic acid ester, phenols such as thymol, p-naphthol, p-nitrophenol, and p-chlorophenol; Active methylene series such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone; mercaptans such as butyl mercaptan, thiophenol, and tert-dodecyl mercaptan; Amines such as diphenylamine, phenylnaphthylamine, aniline, and carbazole; Acid amide series such as acetanilide, acetanisidide, acetic acid amide, and benzamide; Acid imide series such as succinimide and maleimide; Imidazole series such as imidazole, 2-methylimidazole, and 2-ethylimidazole; Urea systems such as urea, thiourea, and ethylene urea; Carbamate series such as phenyl N-phenylcarbamate and 2-oxazolidone; Imine series such as ethyleneimine and polyethyleneimine; oximes such as formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, and cyclohexanone oxime; Bisulfite-based salts such as sodium bisulfite and potassium bisulfite can be mentioned. Among these, from the viewpoint of good low-temperature curing properties as a photosensitive coloring composition, diethyl malonate, 3,5-dimethylpyrazole, and methylethylketoxime are preferable as the blocking agent, and 3,5-dimethylpyrazole and methylethylketoxime are more preferable. desirable.

Among the ethylenically unsaturated group-containing compounds having the above-mentioned functional group ( Unsaturated group-containing compounds and ethylenically unsaturated group-containing compounds having an epoxy group are preferred; Hydroxyalkyl (meth)acrylates, (meth)acrylic acid, (meth)acrylates containing a block isocyanato group, and (meth)acrylates containing an epoxy group are more preferable; Block isocyanato group-containing (meth)acrylates are more preferred. These compounds may be used individually or in combination of two or more.

As a (meth)acrylate monomer that is copolymerized with an ethylenically unsaturated group-containing compound having the above-mentioned functional group ( There is no particular limitation as long as it is a (meth)acrylate monomer that can be copolymerized with an ethylenically unsaturated group-containing compound. Examples of the (meth)acrylate monomer include alkyl (meth)acrylate having 4 or more carbon atoms, alicyclic alkyl (meth)acrylate, and aromatic-containing (meth)acrylate.

Examples of the alkyl (meth)acrylate having 4 or more carbon atoms include tert-butyl (meth)acrylate, pentyl (meth)acrylate, neopentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, iso Amyl (meth)acrylate, dodecyl (meth)acrylate, etc. are mentioned.

Examples of the alicyclic alkyl (meth)acrylate include cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, ethylcyclohexyl (meth)acrylate, norbornyl (meth)acrylate, and dicyclo. Fentanyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, etc. can be mentioned.

Examples of the aromatic-containing (meth)acrylate include benzyl (meth)acrylate, triphenylmethyl (meth)acrylate, cumyl (meth)acrylate, naphthalene (meth)acrylate, anthracene (meth)acrylate, etc. can be mentioned.

Among these, from the viewpoint of dispersion stability when used as a mill base, alkyl (meth)acrylates having 6 or more carbon atoms (for example, 2-ethylhexyl (meth)acrylate), dicyclofentanyl (meth)acrylate, Benzyl (meth)acrylate is preferred. These compounds may be used individually or in combination of two or more.

When the binder resin (A-1) is a (meth)acrylic resin, in addition to the ethylenically unsaturated group-containing compound having a functional group (X) and the (meth)acrylate monomer, other ethylenically unsaturated group-containing monomers may be copolymerized. . Other ethylenically unsaturated group-containing monomers include styrenes such as styrene and α-, o-, m-, and p-alkyl derivatives of styrene, norbornene (bicyclo[2.2.1]hept-2-ene), 5 -methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, tetracyclo[4.4.0.12,5.17,10]dodeca-3-ene, 8 -Methyltetracyclo[4.4.0.12,5.17,10]dodeca-3-ene, 8-ethyltetracyclo[4.4.0.12,5.17,10]dodeca-3-ene, dicyclopentadiene, tricyclo[5.2 .1.02,6]dec-8-ene, tricyclo[5.2.1.02,6]dec-3-ene, tricyclo[4.4.0.12,5]undeca-3-ene, tricyclo[6.2.1.01,8 ]undeca-9-ene, tricyclo[6.2.1.01,8]undeca-4-ene, tetracyclo[4.4.0.12,5.17,10.01,6]dodeca-3-ene, 8-methyltetracyclo[ 4.4.0.12,5.17,10.01,6]dodeca-3-ene, 8-ethylidenetetracyclo[4.4.0.12,5.17,12]dodeca-3-ene, 8-ethylidenetetracyclo[4.4.0.12, 5.17,10.01,6]dodeca-3-ene, pentacyclo[6.5.1.13,6.02,7.09,13]pentadec-4-ene, pentacyclo[7.4.0.12,5.19,12.08,13]pentadec-3 Vinyl compounds such as -ene, vinyl acetate, and vinyl toluene can be mentioned.

When using a vinyl ester resin as the binder resin (A-1), in the process of synthesizing a vinyl ester resin by reacting an epoxy resin with (meth)acrylic acid, the epoxy group is ring-opened to generate a hydroxy group, thereby forming a hydroxy group as the functional group (X) is introduced.

When introducing a carboxyl group as the functional group (X), the carboxyl group can be introduced by adding a polybasic acid anhydride such as succinic anhydride or maleic anhydride to the hydroxy group of the vinyl ester resin.

When introducing an epoxy group as the functional group (X), a part of the epoxy group of the raw material epoxy resin may be left unreacted in the process of synthesizing the vinyl ester resin.

When it is desired to introduce a block isocyanato group, an alkyl ester group, a mercapto group, an oxetanyl group, etc. as a functional group (X), for example, a compound having these functional groups and a carboxyl group is added to the hydroxy group of the vinyl ester resin. Methods of introducing it by ordering it are included.

The binder resin (A-1) may have an ethylenically unsaturated group introduced from the viewpoint of excellent developing properties when exposing and developing the photosensitive coloring composition and improving the adhesion of the resin cured film to the substrate. For example, by adding a compound having a functional group (Y) reactive with the functional group (X) and an ethylenically unsaturated group to a portion of the functional group (X) of the binder resin (A-1), the binder resin (A-1) ) can be given a stand-alone hardening function. Examples of the compound having a functional group (Y) and an ethylenically unsaturated group include, for example, a block isocyanato group and an alkyl binder resin (A-1) having at least one selected from the group consisting of a hydroxy group and a mercapto group as the functional group (X). One or more types selected from groups having an ester and a compound having an ethylenically unsaturated group can be mentioned.

Furthermore, with respect to the binder resin (A-1) having a carboxyl group as the functional group (X), a compound having at least one type selected from an epoxy group and an oxetanyl group and an ethylenically unsaturated group can be mentioned.

In addition, for the binder resin (A-1) having at least one selected from the group having a block isocyanato group and an alkyl ester as the functional group (X), one or more types selected from the group consisting of a hydroxy group and a mercapto group, and an ethylenic group. Compounds having an unsaturated group can be mentioned.

Moreover, with respect to the binder resin (A-1) which has at least one type selected from an epoxy group and an oxetanyl group as a functional group (X), a compound which has a carboxyl group and an ethylenically unsaturated group can be mentioned.

Specifically, in the case where the above-mentioned binder resin (A-1) is a (meth)acrylic resin, compounds containing an ethylenically unsaturated group having a functional group (X) and compounds similar to those listed as specific examples can be appropriately selected. .

The solid acid value of the binder resin (A-1) is preferably 10 to 300 mgKOH/g, and more preferably 20 to 200 mgKOH/g, from the viewpoint of improving developability when exposing and developing the photosensitive coloring composition. , more preferably 30 to 150 mgKOH/g. When the acid value is 10 or more, the developability improvement effect of the photosensitive coloring composition is sufficiently exhibited. If the acid value is 300 or less, the stability as a pigment dispersion composition is good.

In addition, the acid value of the binder resin (A-1) is a value measured using a mixed indicator of bromothymol blue and phenol red according to JIS K6901 5.3. The acid value of binder resin (A-1) means the number of mg of potassium hydroxide required to neutralize the acidic component contained in 1 g of binder resin (A-1).

The acid value of the binder resin (A-1) is determined by using an ethylenically unsaturated group-containing compound having a carboxyl group as an ethylenically unsaturated group-containing compound having a functional group (X) during copolymerization of the binder resin (A-1). It can be adjusted depending on the mixing amount. Additionally, when the binder resin (A-1) has a hydroxy group, the acid value can be adjusted by adding a polybasic acid anhydride to introduce a carboxyl group. Polybasic acid anhydrides include 1,2,3,6-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, and methyl ratio. Cyclo[2.2.1]heptane-2,3-dicarboxylic acid anhydride, succinic anhydride, octenylsuccinic anhydride, etc. are mentioned.

Methods for making the binder resin (A-1) contain a hydroxy group include the following methods (1) to (3).

Method (1): A method of copolymerizing a binder resin (A-1) using an ethylenically unsaturated group-containing compound having a hydroxy group as an ethylenically unsaturated group-containing compound having a functional group (X).

Method (2): As the ethylenically unsaturated group-containing compound having a functional group (X), an ethylenically unsaturated group-containing compound having a carboxyl group is used, and the precursor of the binder resin (A-1) is copolymerized; Thereafter, an ethylenically unsaturated group-containing compound having an epoxy group, as a compound having a functional group (Y) and an ethylenically unsaturated group, is added to the carboxyl group of the precursor to introduce an ethylenically unsaturated group; Along with that, a method of introducing a hydroxy group by ring opening of an epoxy group.

Method (3): As the ethylenically unsaturated group-containing compound having a functional group (X), an ethylenically unsaturated group-containing compound having an epoxy group is used, and the precursor of the binder resin (A-1) is copolymerized; Thereafter, an ethylenically unsaturated group-containing compound having a carboxyl group, as a compound having a functional group (Y) and an ethylenically unsaturated group, is added to the epoxy group of the precursor to introduce an ethylenically unsaturated group; Along with that, a method of introducing a hydroxy group by ring opening of an epoxy group.

The weight average molecular weight of the binder resin (A-1) is preferably 1,000 to 50,000, more preferably 3,000 to 30,000, and even more preferably 5,000 to 20,000. If the weight average molecular weight is 5000 or more and 20000 or less, good dispersion stability is obtained when used as a mill base.

The amount of functional group (X) contained in 1 g of solid binder resin (A-1) is preferably 100 to 3000 μmol/g, more preferably 300 to 2500 μmol/g, and 500 to 2000 μmol/g. It is more preferable that it is g. If the amount of functional group (X) is 100 μmol/g or more, a mill base with good solvent resistance when formed into a coating film can be produced. If the amount of functional group (X) is 3000 μmol/g or less, good dispersion stability can be obtained when used as a mill base.

[Composition of binder resin (A-1)]

When the binder resin (A-1) is a (meth)acrylic resin, the content of the ethylenically unsaturated group-containing compound having a functional group (X) is preferably 10 to 75 mol%, with the copolymerization monomer being 100 mol%, 20 to 80 mol% is more preferable, and 30 to 70 mol% is still more preferable. If the content is 10 mol% or more, a sufficient amount of crosslinking with the functional group (Y) of the polymer dispersant (C) described later can be secured, and a photosensitive coloring composition with good low-temperature curability can be obtained. If the content is 75 mol% or less, the pigment dispersion composition has good storage stability.

In addition, when a compound having a functional group (Y) and an ethylenically unsaturated group is added to the functional group (X) and an ethylenically unsaturated group is introduced into the binder resin (A-1), the addition rate is the total number of moles of the functional group (X) It is preferably 10 to 80 mol%, and more preferably 20 to 70 mol%. If the addition ratio is 10 mol% or more, solvent resistance is improved when using the mill base as a coating film, and if the addition ratio is 80 mol% or less, good dispersion stability is obtained when using the mill base as a coating film.

The content of the (meth)acrylate monomer is preferably 25 to 90 mol%, preferably 30 to 70 mol%, and preferably 35 to 60 mol%, based on 100 mol% of the copolymerized monomer.

[Method for producing binder resin (A-1)]

When the binder resin (A-1) is a (meth)acrylic resin, it can be manufactured using, for example, the manufacturing method shown below. That is, a compound containing an ethylenically unsaturated group having a functional group ( are mixed and radically polymerized under nitrogen atmosphere, usually under conditions of 70°C to 130°C, to obtain a (meth)acrylic resin that is the binder resin (A-1). The solvent for polymerization may be any solvent that is inert to the copolymerization reaction of the raw material monomer and is not particularly limited. The solvent may be partially or entirely different from the solvent contained in solvent (D-1) described later. When the solvent for polymerization is partly or entirely the same as the solvent contained in solvent (D-1) contained in the pigment dispersion composition, the solvent for polymerization is not separated or removed from the reaction liquid after completion of the copolymerization reaction, and the solvent (D It is preferable because it can be used as part of -1).

Examples of the solvent for polymerization include those exemplified as solvents that may be contained in the solvent (D-1) described later. Among these, from the viewpoint of handling, it is preferable to use (poly)alkylene glycol monoalkyl ether acetates, and it is especially preferable to use propylene glycol monomethyl ether acetate.

The amount of the solvent for polymerization is not particularly limited, but is preferably 30 parts by mass to 1000 parts by mass, more preferably 50 parts by mass to 800 parts by mass, based on 100 parts by mass of the raw material monomer. If the amount of the solvent for polymerization is 30 parts by mass or more, the copolymerization reaction of the raw material monomer can be performed stably, and coloring and gelation of the functional group-containing resin precursor (a) can be prevented. If the amount of the polymerization solvent used is 1000 parts by mass or less, a decrease in the molecular weight of the functional group-containing resin precursor (a) due to chain transfer action can be suppressed, and the viscosity of the reaction solution can be controlled to an appropriate range.

(polymerization initiator)

The polymerization initiator that can be used in the copolymerization reaction of the raw material monomer is not particularly limited, but examples include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvalene) Ronitrile), 2,2'-azobis(isobutyric acid)dimethyl, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, etc. These polymerization initiators may be used individually by 1 type, or may be used in combination of 2 or more types.

The amount of the polymerization initiator used is not particularly limited, but is preferably 0.1 parts by mass to 20 parts by mass, more preferably 0.5 parts by mass to 16 parts by mass, based on 100 parts by mass of the raw material monomer.

When introducing an ethylenically unsaturated group into the binder resin (A-1), a polymerization inhibitor or catalyst is added as necessary, a compound having a functional group (Y) and an ethylenically unsaturated group is added, and the mixture is incubated under conditions of 50 to 150°C. , react for 1 to 10 hours.

[Pigment (B)]

The pigment (B) in this embodiment is not particularly limited as long as it can be uniformly dispersed with other compositions to form a pixel of a color filter. Pigments of each color can be used, including pigments of the three primary colors of light such as red, green, and blue, pigments such as yellow, orange, and purple that can be used as complementary colors, and pigments such as black and brown used in the black matrix. In addition, the chemical structure of the pigment (B) includes isoindolinone, isoindoline, azomethine, anthraquinone, anthrone, xanthene, diketopyrrolopyrrole, perylene, perinone, quinacridone, indigoid, These include all organic pigments such as dioxazine, indigoid, phthalocyanine, anthocyanin, and azo, and inorganic pigments such as carbon black, titanium black, and titanium dioxide.

Especially, it is preferable that the pigment (B) in this embodiment contains a green pigment which has a halogenated phthalocyanine skeleton represented by the following formula (1).

In formula (1), M represents a divalent or tetravalent metal atom. From the viewpoint of color reproducibility, zinc or copper is preferable, and zinc is especially preferable. X represents any one of a hydrogen atom, a chlorine atom, and a bromine atom, and contains at least one chlorine atom or a bromine atom. The addition ratio of chlorine atoms and bromine atoms changes depending on brightness or color reproducibility. The more chlorine atoms and fewer bromine atoms, the higher the brightness. Conversely, the more bromine atoms and fewer chlorine atoms, the better the color reproducibility. The number of chlorine atoms is preferably 1 to 10, and more preferably 1.5 to 8. The number of bromine atoms is preferably 5 to 15, and more preferably 7 to 14.

By using a green pigment having a halogenated phthalocyanine skeleton and the polymer dispersant (C), sufficient pigment dispersibility and storage stability of the pigment dispersion composition are obtained, and a color filter with high brightness and a wide color reproduction range can be provided. It can provide heat resistance, solvent resistance, and pattern adhesion to the colored pattern.

As the halogenated phthalocyanine pigment, you may use a commercially available product or prepare it yourself. As an example of a commercially available product, C.I. Pigment Green 7, 36, 58, 59, etc. are included, and among them, C.I. is superior in terms of high brightness and color reproducibility. The use of pigment greens 58 and 59 is preferred.

When preparing it yourself, use known preparation methods. For example, a method of forming a phthalocyanine skeleton under a catalyst such as ammonium molybdate using phthalocyanine or phthalonitrile in which some or all of the hydrogen atoms of the aromatic ring are replaced with halogen atoms as a starting material, or phthalocyanine is converted into chlorine gas. One example is halogenation using bromine gas. The desired green pigment can be obtained by dry grinding the crude pigment obtained by these methods in a grinder such as a ball mill or vibrating mill and treating it by a known solvent salt milling method or the like.

About the pigment (B) in this embodiment, the green pigment which has a halogenated phthalocyanine skeleton may be used individually, or may be used in combination of 2 or more types. Additionally, pigments other than the green pigment having a halogenated phthalocyanine skeleton may be used together.

Specific examples of other pigments include C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139 , 147, 148, 150, 153, 154, 166, 173, 194, 214, etc.; C.I. Orange pigments such as Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, and 73; C.I. Red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 ; C.I. Blue pigments such as Pigment Blue 15, 15: 3, 15: 4, 15: 6, and 60; C.I. Purple pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, and 38; C.I. Brown pigments such as Pigment Brown 23 and 25; C.I. Black pigments such as pigment black 1 and 7, carbon black, titanium black, and iron oxide can be mentioned. These pigments may be used individually or in combination of two or more types, depending on the color of the target pixel.

Additionally, with respect to the pigment (B) in this embodiment, not only the pigment but also the dye may be used in combination. When a dye is used in combination, higher brightness, an expansion of the color reproduction range, and good developability can be expected compared to when a pigment is used. On the other hand, when a pigment is used together, heat resistance is excellent compared to dye, and color change after forming a colored pattern is small. Depending on the required performance or the target pixel color, dye and pigment may be used together.

As dyes, from the viewpoint of solubility in solvent (D) or alkaline developer, interaction with other components in the resin composition, heat resistance, etc., acid dyes with acidic groups such as carboxyl groups, salts of acid dyes with nitrogen compounds, and acid dyes It is preferable to use a sulfonamide form, etc. Specific examples of such dyes include Acid Alizarin Violet N; Acid Black 1, 2, 24, 48; Acid Blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; Acid Chrome Violet K; Acid Fuzz; Acid Green 1, 3, 5, 25, 27, 50; Acid Orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; Acid Violet 6B, 7, 9, 17, 19; Acid Yellow 1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; Food Yellow 3 and derivatives thereof may be included. Among these, azo-based, xanthene-based, anthraquinone-based or phthalocyanine-based acid dyes are preferable. These dyes may be used individually, or may be used in combination of two or more types. When using a dye, the amount is preferably 20 to 80 parts by mass with respect to 100 parts by mass of the pigment (B).

[Polymer dispersant (C)]

The polymer dispersant (C) of the present embodiment has at least one selected from amino groups and quaternary ammonium cation groups, and has a functional group (Y) that is reactive with the functional group (X) possessed by the binder resin (A-1). There is no particular limitation as long as it is. A polymer dispersant having at least one substituent selected from the group consisting of a tertiary amino group and a quaternary ammonium cation group is more preferable. Since the polymer dispersant (C) has a functional group (Y), it can react with the functional group (X) of the binder resin (A-1) to crosslink it. Therefore, even when the photosensitive coloring composition is cured at low temperature, a cured resin film with excellent solvent resistance is obtained. In addition, when the polymer dispersant (C) has at least one selected from amino groups and quaternary ammonium cation groups, the dispersibility of the pigment in the pigment dispersion composition is improved and the developability when used as a photosensitive coloring composition is good. .

In this specification, a quaternary ammonium cation group refers to a group in which four carbon atoms are bonded to a nitrogen atom, and does not include an amide bond or a urea bond.

The functional group (Y) reactive with the functional group (X) is not particularly limited as long as it is a functional group reactive with the functional group (X) contained in the binder resin (A). Specifically, from the viewpoint of reactivity with the functional group ( A carboxyl group, etc. can be mentioned.

Examples of the amino group that the polymer dispersant (C) may have include primary, secondary, and tertiary amino groups. Respectively, a primary amino group refers to a group in which one carbon atom is bonded to a nitrogen atom, a secondary amino group refers to a group in which two carbon atoms are bonded to a nitrogen atom, and a tertiary amino group refers to a group in which three carbon atoms are bonded to a nitrogen atom. .

Among amino groups and quaternary ammonium cation groups, those containing at least a tertiary amino group are preferred from the viewpoint of dispersibility and storage stability of the pigment dispersion composition.

The polymer dispersant (C) is preferably a reaction product of an amino group-containing polymer compound (c-1) and a halogen compound (c-2) having the functional group (Y). Halogen compounds refer to organic chemical substances in which halogen atoms such as chlorine, bromine, and iodine are bonded.

When the amino group-containing polymer compound (c-1) reacts with the halogen compound (c-2) having the functional group (Y), the residue from which the halogen atom of the halogen compound (c-2) has been removed becomes the amino group-containing polymer compound (c-2). -1) Coordinates to the amino group. Among them, a polymer containing an amino group (c-1) containing a tertiary amino group is reacted with a halogen compound (c-2) having the functional group (Y) to form a polymer in which the tertiary amino group is a quaternary ammonium cation group. Dispersant (C) is preferred.

“Amino group-containing polymer compound (c-1)”

Examples of the amino group-containing polymer compound (c-1) include polyamine obtained by homopolymerizing a monomer having an amino group and an ethylenically unsaturated group or copolymerizing it with another monomer having an ethylenically unsaturated group. Examples of such high molecular compounds include polyamines, which are polymers of vinylamine or polymers of allylamine; or polyamine copolymerized with vinylamine or allylamine and a monomer having another ethylenically unsaturated group; Polymers obtained by ring-opening polymerization of 1-substituted aziridines, 2-oxazolines, etc.; Examples include polyalkyleneimines obtained by polycondensation of polyfunctional amine compounds such as ethylenediamine and hexamethylenediamine and haloalkanes. In addition to the amino group, the polymer compound (c-1) may contain amide, imide, urea, urethane, etc. as long as the effect is not impaired, and the halogen compound (c-2) having the above functional group (Y) does not prevent addition. As described above, since it is the amine structure that greatly contributes to pigment dispersibility, it is preferable that amide, imide, urea, and urethane bonds are substantially not included. Among them, polyamines obtained by block polymerization of a monomer having an amino group and an ethylenically unsaturated group and a monomer having another ethylenically unsaturated group are preferred, and polyamines obtained by block polymerization of a monomer having a tertiary amino group and an ethylenically unsaturated group and a monomer having another ethylenically unsaturated group are preferred. This is more preferable. By using block-polymerized polyamine as the polymer dispersant (C), amino groups are localized in the partial terminal region, and affinity with the pigment (B) is improved. In addition, the other end region increases the affinity with other pigment dispersion compositions, specifically binder resin (A-1) and the solvent (D-1) described later, thereby improving the pigment dispersibility and the pigment dispersion composition. Storage stability can be dramatically improved.

Specific examples of monomers having an amino group and an ethylenically unsaturated group include dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, dimethylaminobutyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and dimethylaminoethyl (meth)acrylate. Ethylaminopropyl (meth)acrylate, diethylaminobutyl (meth)acrylate, pentamethylpiperidyl (meth)acrylate, tetramethylpiperidyl (meth)acrylate, N, N-dimethyl (meth)acrylate Amide, N,N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, dimethylaminoethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, diacetone (meth)acrylamide, or (meth)acrylamides such as acryloylmorpholine. These monomers may be used individually, or two or more types may be used. Among them, monomers having a tertiary amino group and an ethylenically unsaturated group are preferable, and dimethylaminoethyl (meth)acrylate is more preferable because it greatly contributes to improving the dispersibility and storage stability of the pigment dispersion composition. In addition, a monomer having a tertiary amino group and an ethylenically unsaturated group is used to prepare an amino group-containing polymer compound (c-1) having a tertiary amino group, and a halogen compound (c) having the above functional group (Y) in part of the tertiary amino group. When -2) is reacted to form a quaternary ammonium cation, hydrophilicity is improved and developability as a photosensitive coloring composition is improved.

Examples of monomers having other ethylenically unsaturated groups include (meth)acrylates having an alkyl group, aryl group, aralkyl group, cycloalkyl group, (poly)oxyalkylene skeleton, etc., but they have compatibility with other pigment dispersion compositions. There are no particular restrictions as long as it does not cause damage. Specific examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate. , t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate ) Acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene (meth)acrylates such as glycol (meth)acrylate or ethoxypolyethylene glycol (meth)acrylate, styrenes such as styrene or α-methylstyrene, ethyl vinyl ether, n-propyl vinyl ether, and isopropyl vinyl. Examples include vinyl ethers such as ether, n-butyl vinyl ether, or isobutyl vinyl ether, and fatty acid vinyls such as vinyl acetate or vinyl propionate. These monomers may be used individually, or two or more types may be used.

The amino group-containing polymer compound (c-1) may be a commercially available product or may be prepared yourself. When using a commercial product, examples of suitable amino group-containing polymer compounds (c-1) include the DISPERBYK series manufactured by Big Chemistry, the Solsperse series manufactured by Lubrizol, and the EFKA-PX series manufactured by BASF. When preparing yourself, use known polymer preparation methods. These amino group-containing polymer compounds (c-1) may be used individually, or in combination of two or more, as needed.

“Halogen compound (c-2)”

The halogen compound (c-2) is not particularly limited as long as it is a monohalogen compound having the above functional group (Y). The number of functional groups (Y) is not particularly limited. For example, bromides, chlorides, iodides, etc. of compounds having one or more types selected from the group consisting of block isocyanato groups, alkyl ester groups, epoxy groups, oxetanyl groups, hydroxy groups, mercapto groups, and carboxyl groups. You can. Specifically, 2-bromoethanol, epibromohydrin, etc. can be mentioned. These compounds may be used individually, or two or more types may be used. Among them, bromide is preferable from the viewpoint of reactivity.

The addition ratio of the halogen compound (c-2) relative to the total amount of amino groups in the amino group-containing polymer compound (c-1) is preferably 5 to 80%, more preferably 10 to 60%, and 15 to 40%. It is more preferable that it is %. If the addition ratio of the halogen compound (c-2) is 5% or more, a sufficient amount of functional group (Y) is introduced into the polymer dispersant (C). Therefore, a sufficient amount of crosslinking with the functional group (X) of the binder resin (A-1) can be secured. As a result, a resin cured film having good low-temperature curability as a photosensitive coloring composition and excellent solvent resistance is obtained. If the addition ratio of the halogen compound (c-2) is 80% or less, the polymer dispersant (C) can be easily manufactured without gelation during synthesis, and good dispersion stability can be maintained when used as a mill base. In particular, when the amino group of the amino group-containing polymer compound (c-1) is a tertiary amino group, if the addition ratio of the halogen compound (c-2) is 80% or less, the amount of remaining tertiary amino group can be sufficiently secured. Therefore, the dispersibility and storage stability as a pigment dispersion composition are sufficient.

When the polymer dispersant (C) has one or more types selected from amino groups and quaternary ammonium cation groups, the amine content (the total amount of primary amine, secondary amine, and tertiary amine) is determined by the amine value (standards shown in JIS K7237, etc. By measuring the measured value according to , the amount can be quantitatively determined. The amine content of the polymer compound (c-1) of the present embodiment is not particularly limited, but is preferably 10 mgKOH/g to 400 mgKOH/g, more preferably 20 mgKOH/g to 200 mgKOH/g, and even more preferably 30 mgKOH/g. to 100mgKOH/g. If the amine value is 10 mgKOH/g or more, the pigment dispersion composition will have sufficient dispersibility and storage stability.

When the polymer dispersant (C) has an amino group, the contribution rate of the tertiary amino group is particularly large to the improvement of the dispersibility and storage stability of the pigment dispersion composition. Therefore, it is desirable to ensure a sufficient tertiary amine content of the polymer dispersant (C). From that viewpoint, the tertiary amine value of the polymer dispersant (C) is preferably 10 mgKOH/g to 400 mgKOH/g, more preferably 30 mgKOH/g to 200 mgKOH/g, and still more preferably 40 mgKOH/g to 100 mgKOH/g. .

The tertiary amine titer is a value calculated based on the amine titer V ₀ (value measured according to the standards shown in JIS K7237, etc.) and the amount of amino group-containing monomer and halogen compound (c-2) used.

The amount of functional group (Y) contained in 1g of solid polymer dispersant (C) is preferably 50 to 5000 μmol/g, more preferably 100 to 3000 μmol/g, and 150 to 1000 μmol/g. It is more desirable. When the amount of the functional group (X) is 50 μmol/g or more, a resin cured film with excellent developability and low-temperature curing properties as a photosensitive coloring composition and good solvent resistance is obtained. If the amount of functional group (X) is 5000 μmol/g or less, good dispersion stability can be obtained when used as a mill base.

The weight average molecular weight of the polymer dispersant (C) of this embodiment is preferably 1,000 to 40,000, more preferably 1,000 to 30,000. In addition, the molecular weight distribution (value obtained by dividing the weight average molecular weight in terms of polystyrene by the number average molecular weight) of the polymer dispersant (C) is preferably in the range of 1.0 to 3.0, more preferably in the range of 1.0 to 2.0. If the molecular weight or molecular weight distribution of the polymer dispersant (C) is within the above range, the viscosity of the pigment dispersion composition can be controlled to an appropriate range. As a result, sufficient pigment dispersibility and storage stability of the pigment dispersion composition are obtained, and excellent heat resistance, solvent resistance, pattern adhesion, developability, etc. can be secured.

[Preferable combination of functional group (X) and functional group (Y)]

As a preferable combination of the functional group (X) possessed by the binder resin (A-1) and the functional group (Y) possessed by the polymer dispersant (C), from the viewpoint of improving low-temperature curability as a photosensitive coloring composition, the following combinations (1) to ( 4) can be mentioned.

Combination (1): A combination of at least one type selected from a hydroxy group and a mercapto group as the functional group (X), and a group having a block isocyanato group and an alkyl ester as the functional group (Y).

Combination (2): A combination of one or more types selected from a carboxyl group as the functional group (X), an epoxy group, and an oxetanyl group as the functional group (Y).

Combination (3): A combination of at least one type selected from groups having a block isocyanato group and an alkyl ester as the functional group (X), and at least one type selected from a hydroxy group and a mercapto group as the functional group (Y).

Combination (4): A combination of at least one selected from epoxy group and oxetanyl group as the functional group (X) and a carboxyl group as the functional group (Y).

Additionally, functional groups other than the above combination may be used together. For example, as the functional group (X) of the binder resin (A-1), it is preferable that a carboxyl group is used together in any combination from the viewpoint of improving developability as a photosensitive coloring composition.

<Method for producing polymer dispersant (C)>

The polymer dispersant (C) can be produced, for example, by the following method. That is, it can be produced by adding the halogen compound (c-2) having the above functional group (Y) to the amino group of the amino group-containing polymer compound (c-1). As a method of adding the halogen compound (c-2) having the functional group (Y) to the amino group of the polymer compound (c-1), it is preferable to use a bromo chlorination reaction. Specifically, the polymer compound (c-1), the halogen compound (c-2) having the functional group (Y), and the solution are mixed in an arbitrary ratio, and the temperature is room temperature to 150°C, preferably 30°C to 130°C. By reacting under the conditions, a polymer dispersant (C), which is a reaction product of the polymer compound (c-1) and the halogen compound (c-2) having the functional group (Y), is obtained.

[Solvent (D-1)]

The solvent (D-1) is not particularly limited as long as it is a solvent that does not react with each component contained in the pigment dispersion composition of the present embodiment or the photosensitive coloring composition and is capable of dissolving or dispersing them. As the solvent (D-1), the same solvent as the solvent used when producing the binder resin (A-1) or the polymer dispersant (C) can be used, and the solvent contained after the reaction can be used as is, or more can be added. there is. Additionally, when adding other components, they may coexist there. Specific examples of the solvent (D-1) include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, isopropyl acetate, propylene glycol monomethyl ether, and dipropylene glycol. Monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethylene glycol monoethyl ether acetate, diethylene glycol ethyl ether acetate. etc. can be mentioned. These may be used individually, or may be used in combination of two or more types. Moreover, among these, glycol ether-based solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, which are preferably used when manufacturing color filters, are preferable.

<Method for producing pigment dispersion composition>

The pigment dispersion composition of the present embodiment is prepared by weighing a predetermined amount of binder resin (A-1), polymer dispersant (C), pigment (B), and solvent (C-1), and dispersing the pigment (C-1) using a known dispersion treatment process. B) is micronized and dispersed. In this dispersion treatment process, various devices such as paint shakers, bead mills, ball mills, roll mills, stone mills, jet mills, homogenizers, planetary mixers, and rotation/revolution mixers are used. Additionally, in this dispersion treatment step, if beads with a diameter of 0.01 to 10 mm are used, the pigment (B) can be uniformly refined efficiently. There are no restrictions on the material of the beads, but considering hardness and contamination of the pigment dispersion composition, it is preferable to use glass beads or zirconia beads. The appropriate time, temperature, bead diameter, and usage amount for the dispersion treatment may be adjusted appropriately because the appropriate conditions vary depending on the composition of the pigment dispersion composition, the size of the device, etc.

Finally, for the purpose of removing fine dust and particles or aggregates of the pigment (B) from the pigment dispersion composition, it is preferable to filter the pigment dispersion composition through a glass filter or the like.

[Mixing ratio of pigment dispersion composition]

The content of the binder resin (A-1) is preferably 10 to 80 parts by mass, more preferably 15 to 50 parts by mass, and still more preferably 20 to 40 parts by mass, based on 100 parts by mass of the pigment (B). When the content of binder resin (A-1) is 10 parts by mass or more, sufficient developability is obtained. If the content of the binder resin (A-1) is 80 parts by mass or less, good dispersion stability can be obtained when used as a mill base.

The content of the polymer dispersant (C) is preferably 10 to 80 parts by mass, more preferably 15 to 50 parts by mass, and still more preferably 20 to 40 parts by mass, based on 100 parts by mass of the pigment (B). If the content of the polymer dispersant (C) is 10 parts by mass or more, good dispersion stability is obtained when used as a mill base. If the content of the polymer dispersant (C) is 80 parts by mass or less, sufficient developability is obtained.

The compounding amount of solvent (D-1) is preferably 100 to 900 parts, more preferably 120 to 600 parts, and still more preferably 100 parts by mass of the total components of the pigment dispersion composition excluding solvent (D-1). Typically, it is 150 to 400 copies. If the content of the solvent (D-1) is within the above range, a pigment dispersion composition having an appropriate viscosity is obtained.

<Photosensitive coloring composition>

The content of the polymer dispersant (C) is preferably 10 to 80 parts by mass, more preferably 15 to 50 parts by mass, and still more preferably 20 to 40 parts by mass, based on 100 parts by mass of the pigment (B). If the content of the polymer dispersant (C) is 10 parts by mass or more, good dispersion stability is obtained when used as a mill base. If the content of the polymer dispersant (C) is 80 parts by mass or less, sufficient developability is obtained.

The photosensitive coloring composition of this embodiment contains the pigment dispersion composition, binder resin (A-2), reactive diluent (E), and photopolymerization initiator (F). The photosensitive coloring composition of this embodiment may contain a solvent (D-2).

In the photosensitive coloring composition of the present embodiment, the total binder resin (A) of the binder resin (A-1) and (A-2) is 50 to 280 parts by mass, with respect to 100 parts by mass of the pigment (B), and the polymer. It is preferable to contain 10 to 80 parts by mass of the dispersant (C), 40 to 200 parts by mass of the reactive diluent (E), and 0.1 to 10 parts by mass of the photopolymerization initiator (F).

The solvent (D-2) may be the same as the solvent (D-1) contained in the pigment dispersion composition, or another solvent may be added.

[Binder Resin (A-2)]

As the binder resin (A-2), conventionally known resins that can be used as photosensitive coloring compositions can be used without particular restrictions, and those common to the binder resin (A-1) contained in the pigment dispersion composition may be used. , it can be anything else. In addition, binder resin (A-1) may be used as (A-2) instead of adding it as binder resin (A-2).

The total binder resin (A) content of the binder resin (A-1) and (A-2) is preferably 50 to 280 parts by mass, and 75 to 230 parts by mass, based on 100 parts by mass of the pigment (B). It is more preferable that it is 100 to 200 parts by mass.

[Reactive diluent (E)]

The reactive diluent (E) is not particularly limited as long as it is a low molecular weight compound containing an ethylenically unsaturated double bond such as a vinyl group or (meth)acryloyloxy group. Specific examples of the reactive diluent (C) include aromatic vinyl monomers such as styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, divinylbenzene, diallyl phthalate, and diallylbenzenephosphonate; polycarboxylic acid monomers such as vinyl acetate and vinyl adipic acid; Methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, β-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, ethylene glycol Di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri( (meth)acrylic monomers such as meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tri(meth)acrylate of tris(hydroxyethyl)isocyanurate. ; Triallyl cyanurate, etc. can be mentioned. These may be used individually, or may be used in combination of two or more types. Among these, compounds having multiple (meth)acryloyloxy groups are preferable, such as trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tris Compounds having three or more (meth)acryloyloxy groups, such as tri(meth)acrylate of (hydroxyethyl)isocyanurate, are more preferable.

The content of the reactive diluent (E) is preferably 40 to 200 parts by mass, more preferably 60 to 180 parts by mass, and still more preferably 80 to 160 parts by mass, based on 100 parts by mass of the pigment (B).

[Photopolymerization initiator (F)]

The photopolymerization initiator (F) is preferably a photo radical generator, and specific examples thereof include benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether; Acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and 4-(1-t-butyldioxy-1-methylethyl)acetophenone; Anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; Thioxanthone such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenone, such as benzophenone, 4-(1-t-butyldioxy-1-methylethyl)benzophenone, and 3,3',4,4'-tetrakis(t-butyldioxycarbonyl)benzophenone. ; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one; 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1; Acylphosphine oxides; and xanthons. These may be used individually, or may be used in combination of two or more types.

The content of the photopolymerization initiator (F) is preferably 0.1 to 10 parts by mass, more preferably 1 to 9 parts by mass, and even more preferably 2 to 8 parts by mass, based on 100 parts by mass of the pigment (B).

[Other ingredients]

In addition to the above components, the photosensitive coloring composition of the present embodiment may contain known additives such as a photoacid generator, a photobase generator, a coupling agent, and a leveling agent, fillers, etc., in order to impart desired properties. . The mixing amount of these components is not particularly limited as long as it is within a range that does not impair the effect of the present invention.

<Method for producing photosensitive coloring composition>

The photosensitive coloring composition of this embodiment can be manufactured by mixing each of the above components using a known mixing device. For example, it can be prepared by first adjusting the pigment dispersion composition, and then sequentially mixing the binder resin (A-2), the reactive diluent (E), the photopolymerization initiator (F), etc. Additionally, if necessary, solvent (D-2) may be added in addition to solvent (D-1) contained in the pigment dispersion composition. In that case, the solvent (D) contained in the photosensitive coloring composition includes solvent (D-1) and solvent (D-2). In addition, the solvent (D-2) may be the same as the solvent (D-1), or may be different.

The photosensitive coloring composition obtained as described above has sufficient pigment dispersibility and storage stability of the pigment dispersion composition, can achieve high brightness, and suppresses bleed-out of the dispersant and colorant, and has excellent heat resistance, solvent resistance, and pattern adhesion. , various resist characteristics such as developability can be expressed. As a result, a highly reliable coloring pattern can be formed. That is, by using the photosensitive coloring composition, a highly reliable color filter can be provided.

<Resin cured film>

The resin cured film of this embodiment can be produced, for example, by the following method.

The photosensitive coloring composition of the present embodiment is coated on a substrate such as glass so that the average thickness of the final cured film is a predetermined value depending on the purpose, and then heated at, for example, 50 to 150°C for 1 to 50 minutes. Volatilize the solvent. Next, the entire surface of the coating film is exposed (for example, using USH-250BY manufactured by Ushio Denki Co., Ltd. as a lamp, exposure amount of 40 mJ/cm2), and then baked at, for example, 50 to 200°C for 10 to 180 minutes. By doing this, a cured coating film is obtained. Additionally, by exposing the coating film through a photomask and developing it with an alkaline developer, a cured coating film with a predetermined coloring pattern is obtained.

<Color Filter>

Next, a color filter having a coloring pattern containing a cured product of the photosensitive coloring composition of the present invention will be described. The color filter of the present invention has a coloring pattern formed using the photosensitive coloring composition described above. A color filter usually consists of a substrate, RGB pixels formed thereon, a black matrix formed at the boundary of each pixel, and a protective film formed on the pixels and the black matrix. In this configuration, except that the pixels and the black matrix (coloring pattern) are formed using the above-mentioned photosensitive coloring composition, other known configurations can be adopted.

Next, one embodiment of a method for manufacturing a color filter will be described. First, a colored pattern is formed on the substrate. Specifically, a black matrix and RGB pixels are sequentially formed on the substrate. The material of the substrate is not particularly limited and includes glass substrate, silicon substrate, polycarbonate substrate, polyester substrate, polyamide substrate, polyamideimide substrate, polyimide substrate, aluminum substrate, printed wiring substrate, array substrate, etc. can be used appropriately.

The colored pattern can be formed by photolithography. Specifically, the above photosensitive coloring composition is applied on a substrate to form a coating film, and then the coating film is exposed through a photomask with a predetermined pattern to photocure the exposed portion. Then, a predetermined colored pattern can be formed by developing the unexposed portion with an aqueous alkaline solution and then baking it.

The application method of the photosensitive coloring composition is not particularly limited, and screen printing, roll coating, curtain coating, spray coating, spin coating, etc. can be used. Additionally, after application of the photosensitive coloring composition, if necessary, the solvent (D) may be volatilized by heating using a heating means such as a circulation oven, an infrared heater, or a hot plate. Heating conditions are not particularly limited and may be set appropriately depending on the type of photosensitive coloring composition to be used. In general, heating may be performed at a temperature of 50°C to 120°C for 30 seconds to 30 minutes.

Next, the formed coating film is partially exposed by irradiating active energy rays such as ultraviolet rays or excimer laser light through a negative mask. The energy dose to be irradiated may be appropriately selected depending on the composition of the photosensitive coloring composition, and is preferably, for example, 30 to 2000 mJ/cm2. The light source used for exposure is not particularly limited, and a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, etc. can be used.

The alkaline aqueous solution used for development is not particularly limited, but includes aqueous solutions such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, and potassium hydroxide; Aqueous solutions of amino compounds such as ethyl amino group, diethylamino group, and dimethylethanolamino group; Tetramethylammonium, 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N -P-phenyl such as ethyl-N-β-methanesulfonamideethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfate, hydrochloride or p-toluenesulfonate salts. An aqueous solution of a lendiamino compound may be used. Additionally, an antifoaming agent or surfactant may be added to these aqueous solutions as needed. In addition, after developing with the aqueous alkaline solution described above, it is preferable to wash with water and dry.

In addition, the baking conditions are not particularly limited, and heat treatment may be performed depending on the type of photosensitive coloring composition to be used. In general, heating at 80 to 250°C for 10 to 60 minutes is sufficient.

By sequentially repeating the above application, exposure, development and baking using the photosensitive coloring composition for the black matrix and the photosensitive coloring composition for red, green, and blue pixels, a desired coloring pattern can be formed. After that, a protective film is formed on the colored pattern (each pixel of RGB and the black matrix). The protective film is not particularly limited and may be formed using a known protective film.

The color filter manufactured in this way has excellent pigment dispersibility by realizing uniform micronization of the pigment, achieves high brightness, has excellent heat resistance, solvent resistance, and adhesion, and can be expected to suppress bleed out of dispersants and colorants. there is.

<Image display element>

The image display element of this embodiment is an image display element provided with the color filter described above, and specific examples thereof include solid-state imaging elements such as liquid crystal display elements, organic EL display elements, CCD elements and CMOS elements. . Manufacturing of the image display element of this embodiment may be performed according to conventional methods other than using the color filter described above. For example, when manufacturing a liquid crystal display element, the color filter is formed on a substrate, and then electrodes, spacers, etc. are sequentially formed. Then, an electrode or the like is formed on another substrate, the two are placed against each other, and a predetermined amount of liquid crystal is injected and sealed.

Example

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. Additionally, in this example, parts and percentages are all based on mass, unless otherwise specified.

<Content of functional group (X) in binder resin (A-1)>

It is the number of moles of functional group (X) per mass of binder resin (A-1), and is a calculated value calculated based on the amount of raw material monomer used.

<Amount of compound containing functional group (X)>

The amount of the functional group (X)-containing compound is the amount (mol%) of the functional group (X)-containing compound used relative to 100 mol% of all monomers as the raw material for the binder resin (A-1). This is a calculated value calculated based on the amount of total monomers and the amount of the functional group (X)-containing compound contained in the actual raw materials of the binder resin (A-1).

<Amount of unreacted functional group (X)>

The amount of unreacted functional group (X) is the amount after subtracting the amount of functional group (X) consumed in the addition reaction from the amount of the compound containing the functional group (X). This is a calculated value based on the amount of the functional group (X)-containing compound calculated above and the actual amount of monomer added for the addition reaction to the binder resin (A-1).

<Addition rate (C=C introduction rate) relative to the total amount of functional group (X) of binder resin (A-1)>

When a compound having a functional group (Y) and an ethylenically unsaturated group is added to the functional group (X) and an ethylenically unsaturated group is introduced into the binder resin (A-1), the addition rate is 100 moles of the total number of moles of the functional group (X). % is the molar ratio (mol%) of the compound. It was calculated based on the actual amount of functional group (X)-containing monomer used and the amount of the compound used for the addition reaction.

<Solid content concentration>

It is the ratio of the total components excluding the solvent in the solution after the binder resin (A-1) synthesis.

<Solid content acid value>

The acid value was measured using a mixed indicator of bromothymol blue and phenol red according to JIS K6901 5.3.

<Method for measuring weight average molecular weight and number average molecular weight>

The weight average molecular weight and number average molecular weight mean the standard polystyrene conversion weight average molecular weight and number average molecular weight measured under the following conditions using gel permeation chromatography (GPC).

Column: Showex (registered trademark) LF-804+LF-804 (made by Showa Denko Co., Ltd.)

Column temperature: 40℃

Sample: 0.2% tetrahydrofuran solution of the measurement object

Development solvent: tetrahydrofuran

Detector: Differential refractometer (Shodex RI-71S) (made by Showa Denko Co., Ltd.)

Flow rate: 1mL/min

<Addition rate of halogen compound (c-2) relative to the total amount of amino groups possessed by amino group-containing polymer compound (c-1)>

The addition ratio of the halogen compound (c-2) relative to the total amount of amino groups in the amino group-containing polymer compound (c-1) is the difference between the actual polymer compound (c-1) and the halogen compound (c-) having the functional group (Y). It is a calculated value calculated based on the usage amount of 2), the amount of functional group (Y) of the polymer dispersant (C), the amine value of the polymer dispersant (C), and the tertiary amine value of the polymer dispersant (C).

<Amine value of polymer dispersant (C)>

The amine titer of the polymer dispersant (C) was measured based on the method described above (JIS K7237). Additionally, the tertiary amine number was calculated using the calculation method described herein. Each result is shown in Table 1a and Table 1b.

<Amount of functional group (Y) of polymer dispersant (C)>

It is the number of moles of the functional group (Y) per mass of the polymer dispersant (C), and is a calculated value calculated based on the actual usage amount of the polymer compound (c-1) and the halogen compound (c-2) having the functional group (Y). am.

A production example of binder resin (A-1) is shown below.

“Synthesis of binder resin (Synthesis Examples a1 to a12, Comparative Synthesis Examples a’1 to a’3)”

<Synthesis example a1>

73.7 g of propylene glycol monomethyl ether acetate was added to a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, and the mixture was stirred while being replaced with nitrogen gas, and the temperature was raised to 120°C. Next, 15.5 g of as a polymerization initiator was added to the monomer mixture containing 27.5 g of tricyclodecanyl methacrylate, 66.0 g of benzyl methacrylate, 45.0 g of acrylic acid, and 16.3 g of ethylene glycol methacrylate (HEMA). t-Butylperoxy-2-ethylhexanoate was added dropwise into the flask from a dropping funnel. After completion of the dropwise addition, the mixture was stirred at 120°C for 2 hours to perform a copolymerization reaction.

Next, after replacing the flask with dry air, 26.6 g of glycidyl methacrylate, 0.5 g of triphenylphosphine as a catalyst, and 0.4 g of hydroquinone monomethyl ether as a polymerization inhibitor were added, and the mixture was heated at 120°C. After conducting the reaction for 5 hours, 132 g of propylene glycol monomethyl ether acetate was added as a solvent to adjust the solid content to 40%, and a binder resin (A-1) having a hydroxyl group as a functional group (Y) and a carboxylic acid as an alkali soluble Alternatively, sample PR1 was obtained as (A-2).

<Synthesis Examples a2 to a12, Comparative Synthesis Examples a'1 to a'3>

Using the monomers shown in Tables 2a and 2b, samples PR2 to PR12 and cPR1 were prepared as binder resins (A-1) or (A-2) in the same manner as in Synthesis Example a1, except for polymerization temperature and monomer ratio. to obtain cPR3.

[Table 1a]

[Table 1b]

The description of the notation in Table 1a and Table 1b is as follows.

TCDMA: Tricyclodecanyl methacrylate

BZMA: Benzyl methacrylate

2EHA: 2-ethylhexyl acrylate

HEMA: Hydroxyethyl methacrylate

4HBA: 4-hydroxybutylacrylate

MAA: methacrylic acid

AA: Acrylic acid

MOI-DEM: malonic acid-2-[[[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3 diethyl ester

MOI-BP: 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate

MOI-BM: 2-[0-(1'-methylpropylidene amino)carboxyamino]ethyl methacrylate

GMA: Glycidyl methacrylate

3EOXMA: (3-ethyloxetan-3-yl)methyl methacrylate

A production example of the polymer dispersant (C) is shown below.

“Synthesis of amino group-containing polymer compound (c-1) (Synthesis examples b1 to b2)”

<Synthesis example b1>

In a flask equipped with a stirring device, dropping funnel, condenser, thermometer, and gas introduction tube, 133 g of propylene glycol monomethyl ether acetate, 80.5 g of isobornyl methacrylate, and 13.2 g of tetramethylethylenediamine as a catalyst were added, The flask was stirred at 50°C for 1 hour while purging with nitrogen. After that, 9.3 g of ethyl bromoisobutyrate and 5.6 g of cuprous chloride were added as catalysts, the flask was heated to 110°C, and a polymerization reaction was performed for 4 hours. After the reaction, the solution was sampled to measure the non-volatile content, and after confirming that the polymerization conversion rate was 98% or more in terms of the non-volatile content, 61 g of propylene glycol monomethyl ether acetate and 19.5 g of dimethylaminoethyl as a monomer having a tertiary amino group were added. Methacrylate was added, and reaction was performed at 110°C for 2 hours. After the reaction, the solution was sampled again to measure the non-volatile content, and after confirming that the polymerization conversion ratio was 98% or more in conversion from the non-volatile content, the solution was cooled. Finally, propylene glycol monomethyl ether acetate was added as a solvent so that the solid content was 40.0%, and bPD1 (amine value 70 mgKOH/g, weight average molecular weight 5500) was obtained as a polymer compound (c-1) containing a tertiary amino group.

<Synthesis example b2>

As a polymer compound (c-1) containing a tertiary amino group, bPD2 (amine value 160 mgKOH/g, weight Average molecular weight 5500) was obtained.

“Synthesis of polymer dispersant (Synthesis Examples c1 to c11, Comparative Synthesis Examples c’1 to c’2)”

<Synthesis Example c1>

35 g (converted to solid content excluding solvent) of bPD1 obtained in Synthesis Example b1 as polymer compound (c-1), and 3-bromo-2-methylpropanol-2 as halogen compound (c-2) having the above functional group (Y). 2.87 g of -[(3,5-dimethylpyrazolyl)carbonylamino]-ethyl ester (20 mol% based on the total amount of amino groups in polymer compound (c-1)) and propylene glycol monomethyl ether acetate as a solvent. It was added so that the non-volatile matter calculated from 30% was stirred while replacing the inside of the flask with nitrogen gas, and the temperature was raised from room temperature to 100°C. After stirring until the peak shift of 3-bromo-2-methylpropanol-2-[(3,5-dimethylpyrazolyl)carbonylamino]-ethyl ester was confirmed in the NMR spectrum, the temperature was lowered to room temperature, and the amino group was added. A polymer dispersant (PD1) was obtained as a reaction product of the containing polymer compound (c-1) and the halogen compound (c-2) having the above functional group (Y).

<Synthesis examples c2 to c8, c10>

Except for changing the type and amount of the amino group-containing polymer compound (c-1) and the type and amount of the halogen compound (c-2) having the functional group (Y), the same procedure as in Synthesis Example 1 was used as the polymer dispersant (C). , samples PD2 to PD8 and PD10 were obtained. The amount of functional group (Y) of the polymer dispersant (C) is shown in Tables 2a and 2b.

<Synthesis example c9>

Sample PD9 was prepared in the same manner as in Synthesis Example c5, except that tertiary amine dispersant EFKA-PX4300 (manufactured by BASF, solid content 30%, amine value 57 mgKOH/g, weight average molecular weight 25000) was used as the amino group-containing polymer compound (c-1). got it The amount of functional group (Y) of the functional group (Y)-containing polymer dispersant is shown in Table 2b.

<Synthesis example c11>

Sample PD11 was prepared in the same manner as in Synthesis Example c3, except that Polyment NK-380 (manufactured by Nippon Shokubai, solid content 30%, amine value 56 mgKOH/g, weight average molecular weight 100000) was used as the amino group-containing polymer compound (c-1). got it The amount of functional group (Y) of the functional group (Y)-containing polymer dispersant is shown in Table 2b.

<Comparative synthesis examples c'1 to c'2>

Dispersant synthesis example except that a halogen compound not containing the functional group (Y) shown in Tables 1a and 1b is used instead of the halogen compound (c-2) having the above functional group (Y), and the reaction temperature is set to 40°C. In the same manner as 1, samples cPD1 to cPD2 were obtained as a polymer dispersant not containing a functional group (Y). The amount of functional group (Y) in the polymer dispersant without functional group (Y) is shown in Table 2b.

[Table 2a]

[Table 2b]

The description of the notation in Table 2a and Table 2b is as follows.

EFKA-PX4300: BASF product, solid content 30%, tertiary amine dispersant, amine value 57mgKOH/g, weight average molecular weight 25000

bPD1: Amino group-containing polymer compound (c-1) obtained in Synthesis Example b1, amine value 70 mgKOH/g

bPD2: Amino group-containing polymer compound (c-1) obtained in Synthesis Example b2, amine value 160 mgKOH/g

Polyment NK-380: manufactured by Nippon Shokubai, solid content 30%, primary and secondary amine dispersant, amine value 56 mgKOH/g, weight average molecular weight 100000)

Brominated MOI-BP: 2-bromo-2-methylpropionic acid, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl ester

Brominated MOI-DEM: malonic acid-2-[[[2-bromo-2-methyl-1-oxo-2-propanyl]oxy]ethyl]amino]carbonyl]-1,3diethyl ester epibro Mohydrin: 3-bromopropylene oxide

Brominated EVMO: 3-ethyl-3-[2-bromoethoxymethyl]-oxetane

EBr: Ethylene bromohydrin:

3BrP: 3-Bromo-1,2-propanediol:

11BrUn: 11-bromo-1-undecanthiol:

BrAc: bromoacetic acid

BrE: Bromoethylene

ABr: Allyl bromide

A production example of the pigment dispersion composition is shown below.

<Examples a1 to a19>

C.I. was added as a pigment (B) to a SUS container (inner diameter 50 mm 7.5 g (100 parts by mass) of Pigment Green 58 (Fastogen Green A110 manufactured by DIC), any of the samples PD1 to PD11 obtained in Synthesis Examples c1 to c11 as the polymer dispersant (C), and Synthesis Example a1 as the binder resin (A). Samples PR1 to PR11 obtained in to a11 were mixed with the composition shown in Tables 3a and 3b, propylene glycol monomethyl ether acetate was added as a solvent (D-1), and the solid content excluding zirconia beads was adjusted to 24%. After mixing and dispersing for 2 hours at room temperature with a paint shaker (Red Devil 5400 manufactured by Red Devil Equipment), the contents were suction filtered through a glass filter to obtain pigment dispersion compositions MB1 to MB19.

<Comparative examples a'1 to a'6>

C.I. was added as a pigment (B) to a SUS container (inner diameter 50 mm 7.5 g (100 parts by mass) of Pigment Green 58 (Fastogen Green A110 manufactured by DIC) as a polymer dispersant, any of the samples cPD1 to cPD2 obtained in Comparative Synthesis Examples c'1 and c'2, and Synthesis Examples a1 to cPD2 as a binder resin. a11, Comparative Synthesis Examples The samples obtained in a'1 to a'3 were mixed with the composition shown in Table 3b, propylene glycol monomethyl ether acetate was added as a solvent (D-1), and the solid content excluding zirconia beads was 24%. After mixing and dispersing for 2 hours at room temperature with a paint shaker (Red Devil 5400 manufactured by Red Devil Equipment), the contents were suction filtered through a glass filter to obtain pigment dispersion compositions cMB1 to cMB6.

[Table 3a]

[Table 3b]

<Evaluation of pigment dispersibility>

The viscosity of the pigment dispersion composition immediately after preparation was evaluated by measuring it with an E-type viscometer (RE-80L manufactured by Toki Sangyo Co., Ltd., cone size 4.8 cm, rotation speed 20 rpm, measurement temperature 25°C). In addition, from the viscosity measurement results, the pigment dispersibility was evaluated on a 5-level scale from 1 to 5 according to the following criteria, and 3 or more were considered passing. The evaluation results are shown in Tables 3a and 3b above.

「5」: Less than 6.0mPa·s

“4”: 6.0 mPa·s or more and less than 8.0 mPa·s

“3”: 8.0 mPa·s or more but less than 10.0 mPa·s

「2」: 10.0 mPa·s or more

「1」: No liquidity

<Evaluation of storage stability of pigment dispersion composition>

The viscosity of the prepared pigment dispersion composition after being stored at room temperature for 1 month was evaluated by measuring it with an E-type viscometer (RE-80L manufactured by Toki Sangyo Co., Ltd., measurement temperature 25°C). The viscosity increase rate of the pigment dispersion composition after storage at room temperature for 1 month "(viscosity after storage - viscosity after adjustment) did. The evaluation results are shown in Tables 3a and 3b above.

「5」: Less than 5%

“4”: 5% or more and less than 10%

「3」: 10% or more and less than 20%

「2」: 20% or more but less than 40%

「1」: Liquidity is lost within 14 days

A production example of the photosensitive coloring composition (CR) is shown below.

<Examples b1 to b19, Comparative Examples b'1 to b'6>

When the solid content (total amount of components other than the solvent) of the pigment dispersion compositions MB1 to MB19 obtained in Examples a1 to a19 and the pigment dispersion compositions cMB1 to cMB4 obtained in Comparative Examples a'1 to a'6 is 100 parts by mass, the binder As the resin (A-2), 80 parts by mass of sample PR10 obtained in Resin Synthesis Example a10 was used as a solid content, 80 parts by mass of dipentaerythritol hexaacrylate as a reactive diluent (E), and 1-[9 as a photopolymerization initiator (F). -Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl-]-, -1-(O-acetyloxime) were mixed and 4 parts by mass were mixed with propylene glycol mono as solvent (D-2). Photosensitive coloring compositions CR1 to 19 and cCR1 to cCR6 were prepared by adding methyl ether acetate and mixing so that the total solid content was 30%. In addition, the mixing amount of each component with respect to 100 parts by mass of the pigment (B) is 128 parts by mass for the binder resin (A-2), 128 parts by mass of the reactive diluent (E), and 6.4 parts by mass of the photopolymerization initiator (F). Table 4a and Table 4b show the number of copies of various materials used.

[Table 4a]

[Table 4b]

<Production of green resist (1) for solvent testing>

The obtained photosensitive coloring compositions CR1 to CR19 and cCR1 to cCR6 were spin-coated on a square glass substrate (alkali-free glass substrate) with a side of 5 cm so that the average thickness of the final cured film was 1.5 ㎛, and then 3 times at 100°C. The solvent was volatilized by heating for a minute. Next, the entire surface of the coating film was exposed (using USH-250BY manufactured by Ushio Denki Co., Ltd. as a lamp, exposure dose 40 mJ/cm2), and then baked at 100°C for 30 minutes to obtain a cured coating film, green resist (1). .

<Production of green resist (2) for developability test>

The obtained photosensitive coloring compositions CR1 to 19 and cCR1 to cCR6 were spin-coated on a square glass substrate (alkali-free glass substrate) with a side of 5 cm so that the average thickness of the final cured film was 1.5 μm, and then applied at 100°C for 3 hours. The solvent was volatilized by heating for a minute. Next, a photomask with a line and space or dot pattern was installed on the substrate, the coating film was exposed (as a lamp, USH-250BY manufactured by Ushio Denki Co., Ltd. was used, exposure dose was 40 mJ/cm2), and photocured, then 0.2 mass % potassium hydroxide aqueous solution and baking at 100°C for 30 minutes to obtain a green color resist (2) as a cured film.

<Solvent resistance test>

The entire surface of the green resist was immersed in propylene glycol monomethyl ether acetate at 25°C for 15 minutes. Afterwards, the green resist was taken out and air dried. The solvent resistance of the photosensitive coloring composition was evaluated by confirming the residual film rate of the green resist. From the measurement results, the solvent resistance of the photosensitive coloring composition was evaluated on a 5-grade scale from 1 to 5 according to the following criteria, and 3 or more were considered passing. The evaluation results are shown in Tables 4a and 4b above.

「5」: Remaining film rate of 95% or more

“4”: Residual film rate 90% or more but less than 95%

“3”: Residual film rate 85% or more but less than 90%

“2”: Residual film rate 80% or more but less than 85%

「1」: Remaining film rate less than 80%

<Development test>

The developability test evaluated the development speed. Regarding the development speed, in the development process of the green color resist (2), the time taken until the pattern is fully visible during development in a 0.2% by mass potassium hydroxide aqueous solution is measured, and the time taken for the pattern to be fully visible is measured, and the time taken for the pattern to be fully visible is measured, and the time taken for the pattern to be fully visible is measured, and the time taken for the pattern to be fully visible is measured according to the following criteria. Evaluation was made on a 5-level scale, and a score of 3 or higher was considered passing. The evaluation results are shown in Tables 4a and 4b above.

「5」: Less than 40 seconds

「4」: More than 40 seconds but less than 50 seconds

「3」: More than 50 seconds but less than 60 seconds

「2」: More than 60 seconds but less than 70 seconds

「1」: 70 seconds or more

As can be seen from the results of Tables 3a and 3b, Tables 4a and 4b, in Examples a1 to a19 and Examples b1 to b19, excellent pigment dispersibility and storage stability of the pigment dispersion composition were obtained. Additionally, the photosensitive coloring composition produced using the pigment dispersion composition obtained in Examples a1 to a19 was cured at a low temperature of 100°C through the reaction of functional group X and functional group Y, and excellent solvent resistance and excellent developability were obtained. .

In contrast, in Comparative Example a'4 and Comparative Example b'4, the pigment dispersibility of the pigment dispersion composition was significantly poor, it was difficult to use it as a pigment dispersion composition, and the curing property when used as a photosensitive coloring composition was insufficient; The solvent resistance was poor, making it difficult to use it as a photosensitive coloring composition. In addition, in Comparative Examples a'1, a'5, and a'6 and Comparative Examples b'1, b'5, and b'6, the pigment dispersibility and storage stability of the pigment dispersion composition and the developability of the photosensitive coloring composition were good. , the solvent resistance of the photosensitive coloring composition was poor.

From the above, according to the present invention, a pigment dispersion composition excellent in pigment dispersibility and storage stability, a photosensitive coloring composition containing the pigment dispersion composition, and the photosensitive coloring composition are excellent in solvent resistance and developability, A color filter expected to suppress elution and bleed-out of dispersants and pigments can be provided.

According to the present invention, it is possible to provide a pigment dispersion composition with good pigment dispersibility and good storage stability. Furthermore, by using the pigment dispersion composition, it is possible to provide a photosensitive coloring composition from which a cured product having excellent solvent resistance and developability can be obtained. Additionally, a color filter containing a cured product of the photosensitive coloring composition and an image display element containing the same can be provided.

Claims (14)

Binder resin (A-1),
Pigment (B),
A polymer dispersant (C),
Solvent (D-1)
It is a pigment dispersion composition containing,
The binder resin (A-1) has a functional group (X),
A pigment dispersion composition characterized in that the polymer dispersant (C) has at least one selected from amino groups and quaternary ammonium cation groups, and has a functional group (Y) reactive with the functional group (X). The pigment dispersion composition according to claim 1, wherein the polymer dispersant (C) is a reaction product of an amino group-containing polymer compound (c-1) and a halogen compound (c-2) having the functional group (Y). The pigment dispersion composition according to claim 2, wherein the amino group of the amino group-containing polymer compound (c-1) is a tertiary amino group. The functional group (X) of the binder resin (A-1) according to any one of claims 1 to 3 is at least one selected from a hydroxy group and a mercapto group,
A pigment dispersion composition, wherein the functional group (Y) of the polymer dispersant (C) is at least one selected from a group having a block isocyanato group and an alkyl ester. The functional group (X) of the binder resin (A-1) is a carboxyl group according to any one of claims 1 to 3,
A pigment dispersion composition in which the functional group (Y) of the polymer dispersant (C) is at least one selected from an epoxy group and an oxetanyl group. The functional group (X) of the binder resin (A-1) according to any one of claims 1 to 3 is at least one selected from a block isocyanato group and an alkyl ester group,
A pigment dispersion composition, wherein the functional group (Y) of the polymer dispersant (C) is at least one selected from a hydroxy group and a mercapto group. The functional group (X) of the binder resin (A-1) according to any one of claims 1 to 3 is at least one selected from an epoxy group and an oxetanyl group,
A pigment dispersion composition wherein the functional group (Y) of the polymer dispersant (C) is a carboxyl group. The pigment dispersion composition according to any one of claims 1 to 3, wherein the pigment (B) contains a pigment having a halogenated phthalocyanine skeleton. The method according to any one of claims 1 to 3, with respect to 100 parts by mass of the pigment (B),
Containing 10 to 80 parts by mass of the binder resin (A-1),
A pigment dispersion composition containing 10 to 80 parts by mass of the polymer dispersant (C). The pigment dispersion composition according to any one of claims 1 to 3,
Binder resin (A-2),
a reactive diluent (E),
Photopolymerization initiator (F)
A photosensitive coloring composition comprising: The method of claim 10, wherein for 100 parts by mass of the pigment (B),
Containing 10 to 80 parts by mass of the binder resin (A-1),
Containing 10 to 80 parts by mass of the polymer dispersant (C),
Containing 50 to 280 parts by mass of the binder resin (A-2),
Containing 40 to 200 parts by mass of the reactive diluent (E),
Containing 0.1 to 10 parts by mass of the photopolymerization initiator (F),
Photosensitive coloring composition. A resin cured film formed by curing the photosensitive coloring composition according to claim 10. A color filter comprising a cured product of the photosensitive coloring composition according to claim 10. An image display element comprising the color filter according to claim 13.