JP7163673B2 - Photosensitive coloring composition for color filter and color filter - Google Patents

Description

The present invention relates to a photosensitive coloring composition, particularly in color filters used in liquid crystal display devices and solid-state imaging devices. It relates to a coloring composition. The present invention also relates to a color filter formed using the photosensitive coloring composition.

In order to improve the color reproduction characteristics of the color filter and the light shielding property of the black matrix, it is necessary to increase the pigment content in the photosensitive coloring composition or increase the film thickness. However, in the method of increasing the content of the pigment, problems such as a decrease in sensitivity and deterioration in developability and resolution occur. In the method of increasing the thickness of the film, exposure light does not reach the bottom of the film, resulting in problems such as poor pattern shape.
In order to solve such problems, it is necessary to increase the sensitivity of the photosensitive coloring composition. Selection or increase in amount of sensitizer, (3) selection or increase in amount of monomer, etc. are performed.

Japanese Patent Application Laid-Open No. 2001-264530 JP 2003-156842 A

However, there is a limit to improving the sensitivity only by imparting double bonds to the resin and by selecting photopolymerization initiators, sensitizers and monomers. In particular, when the amount of the photopolymerization initiator is increased, coloring due to the color peculiar to the photopolymerization initiator, deterioration in heat resistance, reduction in light transmittance, deterioration in resolution, and the like occur. Further, when the amount of the monomer is increased, problems such as tackiness arise. Therefore, the embodiments of the present invention have high sensitivity, excellent linearity, pattern shape, resolution, development resistance, chemical resistance, and even excellent heat resistance, even when the pigment content is high or the film thickness is thick. It is an object of the present invention to provide a photosensitive coloring composition and a color filter using the same.

The photosensitive coloring composition according to one embodiment of the present invention is highly sensitive and has excellent linearity, pattern shape, resolution, development resistance, and chemical resistance, so that the following general formula (1) It is characterized by using the represented photoinitiator.

That is, the present invention provides a color polymer containing a photopolymerization initiator (A) represented by the following general formula (1), a urethane-based photopolymerizable monomer (B), a colorant (C), and a binder resin (X). A photosensitive coloring composition for filters.
General formula (1)

[In general formula (1), R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted Alkyl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclicoxy group, substituted Alternatively, it represents an unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group. ] regarding.

The present invention also provides the photosensitive coloring composition for a color filter, wherein the urethane-based photopolymerizable monomer (B) contains a photopolymerizable monomer (B1) having 3 or more urethane bonding sites. Regarding.

Further, in the present invention, the urethane-based photopolymerizable monomer (B) contains at least two types of photopolymerizable monomers (B1) having 3 or more urethane bonding sites. It relates to a coloring composition.

The present invention also relates to the photosensitive coloring composition for color filters, wherein the coloring agent (C) contains a halogenated metal phthalocyanine.

The present invention also provides the photosensitive coloring composition for a color filter, wherein the halogenated metal phthalocyanine comprises an aluminum phthalocyanine pigment (PCY) represented by the following general formula (2).

general formula (2)

[In the general formula (2),
X represents a halogen atom and n represents an integer of 1-16. However, the average number of substituted halogen atoms represented by X is 1 to 15, and the halogen distribution width is 2 or more.
Y represents -OP(=O)R ₁ R ₂ , -OC(=O)R ₃ or -OS(=O) ₂ R ₄ .
R ₁ and R ₂ are each independently a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxyl group, or It represents an aryloxy group which may have a substituent.
R ₃ is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, or an optionally substituted represents a heterocyclic group.
R ₄ represents a hydroxyl group, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted heterocyclic group. ] regarding.

The present invention also relates to the photosensitive coloring composition for color filters, which further contains a resin-type dispersant.

The present invention also relates to the photosensitive coloring composition for color filters, wherein the resin-type dispersant comprises an acidic resin-type dispersant and a basic resin-type dispersant.

The present invention also relates to a color filter comprising a substrate, a filter segment formed using the photosensitive coloring composition for a color filter, and a black matrix.

Furthermore, the present invention relates to a liquid crystal display device comprising the color filter.

The photosensitive coloring composition according to the embodiment of the present invention uses a specific oxime ester compound as a photopolymerization initiator, so that even if the pigment content is high or the film thickness is thick, excellent pattern shape and chemical Each color filter segment can be formed, which can be tolerant. Therefore, a high-quality color filter can be obtained by using the photosensitive coloring composition of the present invention.

FIG. 1 is a schematic cross-sectional view of a liquid crystal display device.

Terms used herein are defined. "(Meth)acryloyl", "(meth)acryl", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" unless otherwise specified , “acryloyl and/or methacryloyl”, “acrylic and/or methacrylic”, “acrylic acid and/or methacrylic acid”, “acrylate and/or methacrylate”, or “acrylamide and/or methacrylamide”. Also, "C.I." represents a color index number.

The photosensitive coloring composition for color filters of the present invention comprises a specific oxime ester photopolymerization initiator (A) represented by the following general formula (1), a urethane photopolymerizable monomer (B), a colorant (C) and resin (X). The photopolymerization initiator (A) represented by the general formula (1) has high sensitivity, and a coating film having a particularly high residual film rate can be obtained. Therefore, a photosensitive coloring composition having excellent production stability of color filters. is obtained. By using a photosensitive coloring composition containing the photopolymerization initiator, it is possible to form a filter segment and a black matrix having excellent linearity, pattern shape, resolution, development resistance and chemical resistance. Moreover, by using other initiators in combination, a better pattern shape can be obtained.

In addition, since the urethane-based photopolymerizable monomer (B) contains the photopolymerizable monomer (B1) having 3 or more urethane bond sites, the chemical resistance after curing is further improved. . Therefore, by using a photosensitive coloring composition containing this structure, the chemical resistance of the filter segment and the black matrix is further improved.

In addition, since the colorant (C) contains the phthalocyanine pigment represented by the general formula (2), the brightness of the filter segment and the black matrix is further improved.

<Photoinitiator (A)>
The photopolymerization initiator (A) contained in the photosensitive coloring composition of the present invention is a compound represented by general formula (1).

General formula (1)

In general formula (1), R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclicoxy group, substituted or unsubstituted It represents an unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group.

The hydrogen atoms of the substituents in R ₁ , R ₂ , R ₃ and R ₄ described above may be further substituted with other substituents.

Examples of such substituents include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, aryl groups such as phenoxy group and p-tolyloxy group. oxy, methoxycarbonyl, butoxycarbonyl, phenoxycarbonyl and other alkoxycarbonyl groups; acetoxy, propionyloxy, benzoyloxy and other acyloxy groups; acetyl, benzoyl, isobutyryl, acryloyl, methacryloyl; acyl groups such as a methoxalyl group, alkylsulfanyl groups such as a methylsulfanyl group and a tert-butylsulfanyl group, arylsulfanyl groups such as a phenylsulfanyl group and a p-tolylsulfanyl group, methylamino groups, alkylamino groups such as a cyclohexylamino group, dialkylamino groups such as dimethylamino group, diethylamino group, morpholino group and piperidino group; arylamino groups such as phenylamino group and p-tolylamino group; alkyl groups such as methyl group, ethyl group, tert-butyl group and dodecyl group; aryl groups such as phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, benzofuranyl group; heterocyclic groups such as furyl group and thienyl group; formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammoniumyl group, dimethylsulfoniumyl group, triphenylphenacylphosphoniumyl group, and the like.

Among them, R ₁ is preferably a substituted or unsubstituted alkyl group, more preferably an unsubstituted alkyl group having 1 to 10 carbon atoms. Also, R ₂ and R ₃ are preferably hydrogen atoms. Also, R ₄ is preferably a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group.

The most preferred structure of the photopolymerization initiator (A) includes compounds represented by the following chemical formulas (2) and (3).

chemical formula (2)

The photopolymerization initiator (A) contained in the photosensitive coloring composition of the present invention is an oxime ester photopolymerization initiator. In oxime ester photopolymerization initiators, the oxime ester moiety decomposes upon absorption of ultraviolet rays to generate iminyl radicals and alkyloxy radicals, and the radicals of the active species generated by further decomposition are thought to cause reactions. However, the photopolymerization initiator (A) contained in the photosensitive coloring composition of the present invention has a structure represented by the general formula (1), so that the decomposition efficiency by ultraviolet irradiation is very high, A pattern can be formed with a small amount of exposure.
It is assumed that the photopolymerization initiator (A) of the present invention has higher sensitivity than conventional initiators for the following two reasons.

The first reason is that the photopolymerization initiator (A) of the present invention has a structure represented by the general formula (1) and has good ultraviolet absorption performance, so that the energy of the given energy ray is extremely absorbed. It should be able to absorb well. Furthermore, it is thought that the efficient use of the obtained energy to decompose the oxime ester moiety makes it possible to rapidly decompose by energy beam irradiation and instantly generate a large amount of radicals.

The second reason is that the photopolymerization initiator (A) of the present invention decomposes from iminyl radicals generated by absorbing ultraviolet rays into radicals of active species, the structure represented by the general formula (1) can be considered to be very fast due to If the iminyl radicals produced are metastable, the decomposition will be slow and the amount of active radicals produced will be small, but this is greatly affected by the chemical structure of the UV-absorbing moiety. Since the photopolymerization initiator (A) of the present invention has the structure represented by the general formula (1), the iminyl radical generated by the decomposition by light irradiation is decomposed very quickly, resulting in the generation of a large amount of radicals. presumably brought about.
In addition, as described above, the photopolymerization initiator (A) of the present invention decomposes iminyl radicals very quickly, so recombination is thought to be suppressed. When there are many recombination, active species generated by decomposition are reduced, so that the function as a radical polymerization initiator is lowered.

The photopolymerization initiator (A) represented by the general formula (1) is preferably 1 to 50 parts by mass, particularly preferably 1 part by mass, with respect to 100 parts by mass of the colorant (C) in the photosensitive coloring composition. It can be used in amounts of up to 30 parts by weight.

<Other Photopolymerization Initiator (Y)>
The photosensitive coloring composition according to the embodiment of the present invention, together with the photopolymerization initiator (A) represented by the general formula (1), it is more preferable to use other photopolymerization initiators (Y) in combination. It is preferable because a pattern shape can be obtained.
Other photopolymerization initiators (Y) include oxime ester compounds other than the photopolymerization initiator (A), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, p-dimethylamino Acetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopro pan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]- Acetophenone compounds such as 1-[4-(4-morpholinyl)phenyl]-1-butanone, benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, benzophenone, benzoylbenzoic acid , methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, etc. benzophenone compounds, thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone and 2,4-diethylthioxanthone, 2,4,6-trichloro-s-triazine , 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)- 4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s- Triazine compounds such as triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, 2,4-trichloromethyl(4′-methoxystyryl)-6-triazine, 1,2- Octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], O-(acetyl)-N-(1-phenyl-2-oxo-2-(4'-methoxy-naphthyl) ) ethylidene) hydroxylamine and other oxime ester compounds, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and other phosphine compounds, -bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(o-methoxyphenyl)-4,4',5,5 imidazole compounds such as '-tetraphenylbiimidazole, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetra(p-methylphenyl)biimidazole, 9,10-phenyl Quinone-based compounds such as nanthrenequinone, camphorquinone, and ethylanthraquinone, borate-based compounds, carbazole-based compounds, titanocene-based compounds, and the like can be used.

Among these, it is more preferable to contain at least one photopolymerization initiator (Y) selected from the group consisting of oxime ester compounds, acetophenone compounds, phosphine compounds, and imidazole compounds.

These other photopolymerization initiators (Y) can be used singly or as a mixture of two or more at an arbitrary ratio, if necessary. The other photopolymerization initiator (Y) can be used in an amount of 1 to 100 parts by weight, preferably 1 to 50 parts by weight, with respect to 100 parts by weight of the coloring agent (C) in the photosensitive coloring composition. .
Moreover, it can be used in an amount of 1 to 3000 parts by mass with respect to 100 parts by mass of the photopolymerization initiator (A). In order to obtain a better pattern shape, the amount is preferably 5 to 2000 parts by mass with respect to 100 parts by mass of the photopolymerization initiator (A).

<Binder resin (X)>
The binder resin (X) disperses or penetrates the pigment, and examples thereof include thermoplastic resins. The binder resin is preferably a transparent resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more, in the entire wavelength range of 400 to 700 nm in the visible light region. When used in the form of an alkali-developable photosensitive coloring composition, it is preferable to use an alkali-soluble vinyl resin obtained by copolymerizing an ethylenically unsaturated monomer containing an acidic substituent. Moreover, in order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.

Examples of thermoplastic resins include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, and polyurethane resins. , polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.

Examples of vinyl alkali-soluble resins obtained by copolymerizing ethylenically unsaturated monomers containing acidic substituents include resins having acidic substituents such as carboxyl groups and sulfone groups. Specific examples of alkali-soluble resins include acrylic resins having acidic substituents, α-olefin/(anhydride) maleic acid copolymers, styrene/styrenesulfonic acid copolymers, ethylene/(meth)acrylic acid copolymers, Alternatively, isobutylene/(anhydrous) maleic acid copolymer and the like can be mentioned. Among them, at least one resin selected from acrylic resins having acidic substituents and styrene/styrene sulfonic acid copolymers, particularly acrylic resins having acidic substituents, is preferably used because of its high heat resistance and transparency. be done.

Examples of active energy ray-curable resins having ethylenically unsaturated double bonds include resins into which ethylenically unsaturated double bonds are introduced by methods (i) and (ii) shown below.

[Method (i)]
As method (i), for example, the side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group and one or more other monomers. , The carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond is added, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to form an ethylenically unsaturated double bond and a carboxyl group. There is a way to introduce

Ethylenically unsaturated monomers having an epoxy group include, for example, glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate. , and 3,4-epoxycyclohexyl (meth)acrylate, which may be used alone or in combination of two or more. Glycidyl (meth)acrylate is preferred from the viewpoint of reactivity with the unsaturated monobasic acid in the next step.

Examples of unsaturated monobasic acids include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted (meth)acrylic acid. Monocarboxylic acids and the like are mentioned, and these may be used alone or in combination of two or more.

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. These may be used alone or in combination of two or more. I don't mind. If necessary, such as increasing the number of carboxyl groups, use a tricarboxylic anhydride such as trimellitic anhydride, or use a tetracarboxylic dianhydride such as pyromellitic dianhydride to remove the remaining anhydride. It is also possible to hydrolyze the group. Moreover, when tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the number of ethylenically unsaturated double bonds can be further increased.

As a method analogous to method (i), for example, a side chain of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and one or more other monomers There is a method in which an ethylenically unsaturated monomer having an epoxy group is added to a part of the carboxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.

[Method (ii)]
As method (ii), an ethylenically unsaturated monomer having a hydroxyl group is used, and another unsaturated monobasic acid monomer having a carboxyl group or another monomer is copolymerized. There is a method of reacting the side chain hydroxyl groups of the resulting copolymer with the isocyanate groups of an ethylenically unsaturated monomer having an isocyanate group.

Ethylenically unsaturated monomers having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate, glycerol (Meth)acrylates and hydroxyalkyl methacrylates such as cyclohexanedimethanol mono(meth)acrylate may be mentioned, and these may be used alone or in combination of two or more. In addition, polyether mono(meth)acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and/or butylene oxide, etc. to the above hydroxyalkyl (meth)acrylate, poly γ-valerolactone, poly ε-caprolactone, and/or Polyester mono(meth)acrylates added with poly-12-hydroxystearic acid or the like can also be used. 2-Hydroxyethyl methacrylate or glycerol methacrylate is preferred from the viewpoint of suppressing coating film foreign matter.

Examples of the ethylenically unsaturated monomer having an isocyanate group include 2-(meth)acryloyloxyethyl isocyanate, 1,1-bis[methacryloyloxy]ethyl isocyanate and the like, but are not limited to these. Two or more types can also be used together.

In order to preferably disperse the pigment, the weight average molecular weight (Mw) of the binder resin (B) is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw/Mn is preferably 10 or less.

In addition, from the viewpoint of pigment dispersibility, stability, developability, and heat resistance, a carboxyl group that acts as a pigment adsorption group and an alkali-soluble group during development, an aliphatic group that acts as an affinity group for the pigment carrier and solvent, and an aromatic group. The balance of group groups is important for pigment dispersibility, developer permeability in the coating film, developer solubility of the uncured portion, and durability. preferable. If the acid value is less than 20 mgKOH/g, the solubility in a developer is poor, making it difficult to form a fine pattern. Moreover, if it exceeds 300 mgKOH/g, a fine pattern may not remain.

Since the binder resin (X) has good film-forming properties and various resistances, it is preferably used in an amount of 30 parts by mass or more with respect to 100 parts by mass of the total mass of the colorant (C). It is preferable to use it in an amount of 500 parts by mass or less because it is high and can express good color characteristics. More preferably 100 to 400 parts by mass. More preferably 160 to 320 parts by mass. The chromaticity range can be widened by such a composition ratio of the coloring agent.

<Urethane-based photopolymerizable monomer (B)>
The photosensitive coloring composition of the present invention contains a urethane-based photopolymerizable monomer (B). Photopolymerizable monomers include monomers or oligomers that are cured by ultraviolet rays, heat, or the like to form transparent resins.
The urethane-based photopolymerizable monomer (B) is a photopolymerizable compound containing at least one ethylenically unsaturated bond and at least one urethane bond. For example, a polyfunctional urethane acrylate obtained by reacting a polyfunctional isocyanate with a (meth)acrylate having a hydroxyl group, or a polyfunctional polyfunctional obtained by reacting a polyfunctional isocyanate with an alcohol and further reacting a (meth)acrylate having a hydroxyl group. urethane acrylate and the like.

(Meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri( meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide-modified penta(meth)acrylate, dipentaerythritol propylene oxide-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol acrylate Examples include methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, reaction products of epoxy group-containing compounds and carboxy(meth)acrylate, and hydroxyl group-containing polyol polyacrylates.

Polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, polyisocyanate and the like.

Although the structure of the alcohol is not limited, it is preferable to use a polyhydric alcohol because the degree of cross-linking of the cured coating increases and the resistance of the coating increases. Polyhydric alcohols include propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol and the like.

These urethane-based photopolymerizable monomers (B) can be used singly or as a mixture of two or more at an arbitrary ratio as required.

[Photopolymerizable Monomer (B1) Having Three or More Urethane Bonding Sites]
The number of urethane bonds in the urethane-based photopolymerizable monomer (B) is preferably 3 or more. When the number of urethane bonds is 3 or more, it is possible to form hydrogen bonds at multiple points. It is possible to suppress the occurrence of wrinkles on the skin.
In addition, by containing the photopolymerizable monomer (B1) having 3 or more urethane bond sites, it is possible to obtain a uniform and appropriate curing effect in the exposure and post-baking steps. It is possible to prevent the photocuring degree decrease phenomenon, and it is possible to obtain a photosensitive coloring composition excellent in NMP (N-methyl-2-pyrrolidone) resistance and shape.
The photopolymerizable monomer (B1) having 3 or more urethane bonding sites can be obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate.

(Meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri( meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide-modified penta(meth)acrylate, dipentaerythritol propylene oxide-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol acrylate Examples include methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, reaction products of epoxy group-containing compounds and carboxy(meth)acrylate, and hydroxyl group-containing polyol polyacrylates.

Polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, polyisocyanate and the like.

The photopolymerizable monomer (B1) having 3 or more urethane bonding sites that can be used in the coloring composition of the present invention includes, in addition to the polyfunctional urethane acrylate described above, a (meth)acrylate having a hydroxyl group. may contain a component having a double bond group that was not obtained as a polyfunctional urethane acrylate having a (meth)acryloyl group as another monomer when the polyfunctional isocyanate is reacted with the polyfunctional isocyanate.

The number of urethane groups in the photopolymerizable monomer (B1) having 3 or more urethane bonding sites provides sufficient NMP resistance in the coating film after curing, and the colorant ( It is preferably 0.9×10 ⁻³ mol/g or more from the viewpoint of suppressing the elution of A) and preventing display unevenness due to pixel surface defects and chromaticity changes, alignment defects, and the like. More preferably 0.95×10 ⁻³ mol/g to 2.2×10 ⁻³ mol/g.
Within this range, the coloring property in the heating step is low, which is preferable from the viewpoint of heat resistance.

Further, the number of double bond groups is preferably 6.0×10 ⁻³ mol/g or more from the viewpoint of high exposure sensitivity and excellent shape in the development process. More preferably 8.0×10 ⁻³ mol/g to 10.0×10 −3 mol/g. Within this range, the cure shrinkage is low, which is preferable from the viewpoint of the residual film rate.

The content of the photopolymerizable monomer (B1) having 3 or more urethane bond sites is preferably 40% by mass to 90% by mass, more preferably 50% by mass in the photopolymerizable monomer (B). % to 90% by mass, more preferably 60% to 80% by mass.

In addition, in order to suppress the elution of the colorant (C) by NMP, the content of the photopolymerizable monomer (B1) having 3 or more urethane bond sites is adjusted to 100 parts by mass of the colorant (A). It is preferably 30 to 250 parts by mass, more preferably 50 to 230 parts by mass. In particular, when the content of the photopolymerizable monomer is 150 parts by mass or more with respect to 100 parts by mass of the colorant (C), the color difference before and after immersion in NMP is favorable, which is preferable.

[Other photopolymerizable monomers]
The colored composition of the present invention may contain a photopolymerizable monomer other than the urethane-based photopolymerizable monomer (B).
Other monomers include ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolactone monomethacrylate, 2-acryloyloxyethylsuccinic acid, 2-methacryloyloxyethylsuccinic acid, 2-acryloyloxypropylsuccinic acid, 2-methacryloyloxypropyl succinic acid, methoxyethylene glycol acrylate, methoxyethylene glycol methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydiethylene glycol acrylate Propylene glycol acrylate, methoxydipropylene glycol methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate and commercially available 2-acryloyloxyethyl succinic acid, polyethylene glycol di(meth) Acrylate, epoxy (meth)acrylate, EO-modified bisphenol A di(meth)acrylate, 1,4-butanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neo Pentyl glycol di(meth)acrylate, polyester (meth)acrylate, dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol hexaacrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, trimethylol Propane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, etc. Monomers having acidic groups such as acrylic acid esters and methacrylic acid esters, or photopolymerizable monomers in which polymerization is partially induced by radicals can be used.

Moreover, the colored composition of the present invention preferably contains two or more photopolymerizable monomers (B1) having different numbers of urethane bond sites. The photopolymerizable monomers (B1) having different numbers of urethane bond sites preferably have three or more urethane bond sites.

The urethane bond sites of the photopolymerizable monomer (B1) can form hydrogen bonds, so that the crosslink density and glass transition temperature (Tg) of the film are improved, and curing shrinkage due to photocuring and heat curing can be suppressed. In addition, by containing two or more photopolymerizable monomers (B1) having different numbers of urethane bonds, surface wrinkles of the cured film can be further suppressed. In addition, when other photopolymerizable monomers are used in combination, the hardness of the film can be easily adjusted.

The content of the urethane-based polymerizable monomer (B) is 30 to 100% by mass based on the total amount of the photopolymerizable monomers of 100% by mass, whereby wrinkle suppression and development residue are improved, and 45 to 55% by mass is more preferable. .

The content of the photopolymerizable monomer of the present invention is preferably 30% by mass to 70% by mass based on 100% by mass of the solid content of the coloring composition.

<Colorant (C)>
As the colorant (C), organic or inorganic pigments can be used singly or in combination of two or more. Among pigments, pigments having high color developability and high heat resistance are preferred, and organic pigments are usually used. Specific examples of organic pigments that can be used in the photosensitive coloring composition according to the embodiment of the present invention are shown below by color index numbers.
Further, the coloring agent (C) may contain a dye (Cx) or a dye derivative described later within a range that does not lower the heat resistance.

[Pigment]
Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81: 3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276 and the like. Among these, azo pigments, diketopyrrolopyrrole-based, anthraquinone-based, quinophthalone-based, isoindoline-based, perinone-based, perylene-based, and benzimidazolone-based dyes are exemplified from the viewpoint of brightness and tinting strength. Specifically, C.I. I. Pigment Red 176, 177, 179, 254, 242 and naphthol azo pigments represented by the following general formula (4) are preferred.

general formula (4)

[In general formula (4), A represents a hydrogen atom, a benzimidazolone group, a phenyl group optionally having a substituent, or a heterocyclic group optionally having a substituent. R1 represents a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, ^-OR7 or ^COOR8 . R ² to R ⁶ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁹ , —COOR ¹⁰ , —CONHR ¹¹ , —NHCOR ¹² or SO2NHR ¹³ ; R ⁷ to R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
with the proviso that R ⁴ is —NHCOR ¹² , A, R ² , R ³ , R ⁵ and R ⁶ are hydrogen atoms, and R ¹ is a halogen atom. ]

Examples of blue pigments include C.I. I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like. Among these, from the viewpoint of brightness and coloring strength, C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, or 15:6, more preferably C.I. I. Pigment Blue 15:6. In addition, aluminum phthalocyanine pigments and the like described in JP-A-2004-333817, Japanese Patent No. 4893859, etc. can also be used, but are not particularly limited to these.

Examples of green pigments include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63 can be mentioned. Among these, from the viewpoint of brightness and coloring strength, C.I. I. Pigment Green 7, 36, 58, 59, 62, 63. In addition, zinc phthalocyanine pigments and the like described in JP-A-2008-19383, JP-A-2007-320986, JP-A-2004-70342, etc. can also be used, but are not particularly limited to these.

Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95,97,100,101,104,105,108,109,110,111,116,117,119,120,126,127,127:1,128,129,133,134,136,138,139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, 231 and the like. Among these, from the viewpoint of brightness and coloring strength, C.I. I. Pigment Yellow 138, 139, 150, 185, 231.

Examples of purple pigments include C.I. I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like. Among these, from the viewpoint of brightness and coloring strength, C.I. I. Pigment Violet 19 or 23, more preferably C.I. I. Pigment Violet 23.

Examples of orange pigments include C.I. I. Pigment Orange 38, 43, 64, 71, or 73 and the like. Among them, C.I. I. Pigment Orange 38, 43 and 64 are preferred.

Black photosensitive coloring compositions for forming a black matrix include, for example, carbon black, aniline black, anthraquinone black pigments, perylene black pigments, specifically C.I. I. Pigment Black 1, 6, 7, 12, 20, 31, etc. can be used. A mixture of a red pigment, a blue pigment and a green pigment can also be used in the black photosensitive coloring composition. As the black pigment, carbon black is preferable because of its price and high light-shielding properties, and the carbon black may be surface-treated with a resin or the like. Moreover, in order to adjust the color tone, a blue pigment or a purple pigment can be used in combination with the black photosensitive coloring composition.

Inorganic pigments include barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron oxide (III)), cadmium red, ultramarine blue, Prussian blue, chromium oxide green, cobalt green, amber, and titanium black. , synthetic iron black, titanium oxide, metal oxide powder such as iron tetroxide, metal sulfide powder, metal powder, and the like. Inorganic pigments can be used in combination with organic pigments in order to ensure good applicability, sensitivity, developability, etc. while balancing chroma and lightness.

<Halogenated metal phthalocyanine>
The colorant (C) preferably contains a halogenated metal phthalocyanine. Ordinary metal phthalocyanines have 16 hydrogen atoms in one molecule, and halogenated metal phthalocyanines are obtained by replacing these hydrogen atoms with bromine atoms or chlorine atoms. As the central metal of the metal phthalocyanine halide, copper, zinc or aluminum is preferred.
Preferred halogenated metal phthalocyanines are brominated copper phthalocyanine, brominated zinc phthalocyanine, and aluminum phthalocyanine (PCY) represented by the following general formula (2), more preferably C.I. I. Pigment Green 36, C.I. I. Pigment Green 58 or an aluminum phthalocyanine pigment (PCY) represented by the following general formula (2), particularly preferably an aluminum phthalocyanine pigment represented by the following general formula (2).

[Phthalocyanine Pigment (PCY) Represented by Formula (2)]
general formula (2)

[In the general formula (2),
X represents a halogen atom and n represents an integer of 1-16. However, the average number of substituted halogen atoms represented by X is 1 to 15, and the halogen distribution width is 2 or more.
Y represents -OP(=O)R ₁ R ₂ , -OC(=O)R ₃ or -OS(=O) ₂ R ₄ .
R ₁ and R ₂ are each independently a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxyl group, or It represents an aryloxy group which may have a substituent.
R ₃ is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, or an optionally substituted represents a heterocyclic group.
R ₄ represents a hydroxyl group, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted heterocyclic group. ]

"Halogen" in formula (2) includes fluorine, bromine, chlorine and iodine, with bromine and chlorine being preferred. Two or more types of halogen atoms may be used in combination as long as they are within the range of the above-mentioned average value and distribution width of the number of substitutions. In particular, it is preferable to use bromine and chlorine together.

The average number of substituted halogen atoms represented by X in the general formula (2) is 1 to 15, preferably 2 to 12, more preferably 1 to less than 6 from the viewpoint of hue and fastness. , particularly preferably 1 to 4. The halogen distribution width is 2 or more, preferably 4 or more and 10 or less. When the halogen distribution width is 4 or more and 10 or less, the association between phthalocyanine molecules can be significantly suppressed, which greatly contributes to suppressing an increase in particle size and a decrease in contrast due to association between molecules, and improves transmittance. do.

Here, the "halogen distribution width" is the distribution of the number of halogens substituted in the phthalocyanine pigment represented by general formula (2). Halogen distribution width is obtained by calculating the signal intensity of the molecular ion peak corresponding to each component (each peak value) and the integrated value of each peak value (total peak value) in the mass spectrum obtained by mass spectrometry, The number of peaks in which the ratio of each peak value to the total peak value was 1% or more was counted and used as the halogen distribution width.

In general formula (2), the alkyl group for R ₁ and R ₂ includes methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, neopentyl group, n-hexyl group, Linear or branched alkyl groups such as n-octyl group, stearyl group and 2-ethylhexyl group can be mentioned, and alkyl groups having 1 to 6 carbon atoms are preferred.
Examples of substituents of the substituted alkyl group include halogen atoms such as chlorine, fluorine and bromine, alkoxyl groups such as methoxy, aryl groups such as phenyl and tolyl, and nitro groups. Also, there may be a plurality of substituents. Accordingly, examples of substituted alkyl groups include trichloromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2-dibromoethyl group, 2-ethoxyethyl group, 2-butoxy ethyl group, 2-nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl group and the like.

In general formula (2), the aryl group for R ₁ and R ₂ includes monocyclic aromatic hydrocarbon groups such as phenyl group and p-tolyl group, and condensed aromatic hydrocarbon groups such as naphthyl group and anthryl group. and monocyclic aromatic hydrocarbon groups are preferred. Also, an aryl group having 6 to 12 carbon atoms is preferable.
Examples of substituents of the aryl group having a substituent include halogen atoms such as chlorine, fluorine and bromine, alkoxyl groups, amino groups and nitro groups. Also, there may be a plurality of substituents. Therefore, aryl groups having substituents include, for example, p-bromophenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-dimethylaminophenyl group, 2-methyl-4-chlorophenyl group, 4-methoxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group and the like.

In general formula (2), the alkoxyl groups for R ₁ and R ₂ include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, neopentyloxy, 2 , 3-dimethyl-3-pentyloxy group, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2-ethylhexyloxy group and other linear or branched alkoxyl groups having 1 to 6 carbon atoms. is preferred.
Examples of substituents of the alkoxyl group having a substituent include halogen atoms such as chlorine, fluorine and bromine, aryl groups such as alkoxyl groups, phenyl groups and tolyl groups, and nitro groups. Also, there may be a plurality of substituents. Therefore, examples of substituted alkoxyl groups include a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, a 2,2- ditrifluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, benzyloxy group and the like.

In general formula (2), the aryloxy group for R ₁ and R ₂ includes an aryloxy group consisting of a monocyclic aromatic hydrocarbon group such as a phenoxy group and a p-methylphenoxy group, a naphthaloxy group, and an anthryloxy group. An aryloxy group consisting of a condensed aromatic hydrocarbon group such as is preferred, and an aryloxy group consisting of a monocyclic aromatic hydrocarbon group is preferred. Also, an aryloxy group having 6 to 12 carbon atoms is preferred.
Examples of substituents of the aryloxy group having a substituent include halogen atoms such as chlorine, fluorine and bromine, alkyl groups, alkoxyl groups, amino groups and nitro groups. Also, there may be a plurality of substituents. Therefore, the aryloxy group having a substituent includes, for example, p-nitrophenoxy group, p-methoxyphenoxy group, 2,4-dichlorophenoxy group, pentafluorophenoxy group, 2-methyl-4-chlorophenoxy group and the like. mentioned.

In general formula (2), the alkyl group and aryl group for R ₃ are synonymous with the alkyl group and aryl group for R ₁ and R ₂ in general formula (2).
In general formula (2), the cycloalkyl group for R ₃ includes monocyclic aliphatic hydrocarbon groups such as cyclopentyl group, cyclohexyl group, 2,5-dimethylcyclopentyl group, and 4-tert-butylcyclohexyl group, Condensed aliphatic hydrocarbon groups such as bornyl group and adamantyl group are included. A cycloalkyl group having 5 to 12 carbon atoms is also preferred.
Examples of substituents of a cycloalkyl group having a substituent include halogen atoms such as chlorine, fluorine, and bromine, alkyl groups, alkoxyl groups, hydroxyl groups, amino groups, nitro groups, and the like. Also, there may be a plurality of substituents. Examples of substituted cycloalkyl groups include a 2,5-dichlorocyclopentyl group and a 4-hydroxycyclohexyl group.
In general formula (2), examples of the heterocyclic group for R ₃ include aliphatic heterocyclic groups and aromatic heterocyclic groups such as pyridyl group, pyrazyl group, piperidino group, pyranyl group, morpholino group and acridinyl group. A heterocyclic group having 4 to 12 carbon atoms is preferred, and a heterocyclic group having 5 to 13 ring members is preferred.
Examples of substituents of the heterocyclic group having a substituent include halogen atoms such as chlorine, fluorine and bromine, alkyl groups, alkoxyl groups, hydroxyl groups, amino groups and nitro groups. Also, there may be a plurality of substituents. A heterocyclic group having a substituent includes a 3-methylpyridyl group, an N-methylpiperidyl group, an N-methylpyrrolyl group, and the like.

In general formula (2), the alkyl group, aryl group and heterocyclic group for R ₄ include the alkyl group and aryl group for R ₁ and R ₂ in general formula (2), and R ₃ in general formula (2) It is synonymous with heterocyclic group.

In the phthalocyanine compound represented by the general formula (2), at least one of R ₁ and R ₂ has an optionally substituted aryl group or a substituent from the viewpoint of dispersibility and color characteristics. is preferably an aryloxy group that may be substituted, more preferably both R ₁ and R ₂ are an aryl group or an aryloxy group, and both R ₁ and R ₂ are a phenyl group or a phenoxy group is more preferred. Also, R ₃ and R ₄ are preferably an aryl group which may have a substituent or a heterocyclic group which may have a substituent.

In the present invention, the phthalocyanine compound represented by the general formula (2) is [AlPc(Y)]Xn (4 ≤ n ≤ 16) (where Pc is a phthalocyanine ring, X is a halogen atom, and n is 4 to 16 representative examples of general formula (2) are [AlPc(Y)] Brn (4 ≤ n ≤ 16), [AlPc(Y)] Cln (4 ≤ n ≤ 16), [AlPc(Y)]In (4 ≤ n ≤ 16), [AlPc(Y)]Fn (4 ≤ n ≤ 16), etc., but the present invention is not limited to these. do not have. Cyclized isomers of the exemplified compounds are also included as preferred examples of the present invention.

Representative examples of Y in the general formula (2) include the structures shown below (* represents the bonding position of the substituent with Al in the general formula (2)). is not limited to Cyclized isomers of the exemplified compounds are also included as preferred examples of the present invention.

[Quinophthalone compound represented by general formula (20)]
As the yellow pigment, a quinophthalone compound represented by the general formula (20) can be preferably used from the viewpoint of brightness and tinting strength.

general formula (20)

[In the general formula (20), X1 to X13 are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxyl group, a substituted aryl group, —SO ₃ H group, —COOH group, metal salt of —SO ₃ H group or —COOH group, alkylammonium salt of —SO ₃ H group or —COOH group, substituent It represents a phthalimidomethyl group which is good, or a sulfamoyl group which may have a substituent. Adjacent groups of X1 to X4 and/or X10 to X13 together form an aromatic ring which may have a substituent. ]

Here, halogen atoms include fluorine, chlorine, bromine and iodine.

In addition, the alkyl group which may have a substituent includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, an n-hexyl group and an n-octyl group. linear or branched alkyl groups such as groups, stearyl groups, 2-ethylhexyl groups, trichloromethyl groups, trifluoromethyl groups, 2,2,2-trifluoroethyl groups, 2,2-dibromoethyl groups, 2,2,3,3-tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, pentyl group, 4-methylpentyl group, 4-tert-butylbenzyl group, 4-methoxy Alkyl groups having substituents such as a pentyl group, a 4-nitrobenzyl group and a 2,4-dichlorobenzyl group can be mentioned.

Examples of the alkoxyl group which may have a substituent include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isoptyloxy, tert-butyloxy, neopentyloxy, 2, In addition to linear or branched alkoxyl groups such as 3-dimethyl-3-pentoxy, n-hexyloxy, n-octyloxy, stearyloxy, and 2-ethylhexyloxy, trichloromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropyloxy group, 2,2-ditrifluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitro An alkoxyl group having a substituent such as a propoxy group and a benzyloxy group can be mentioned.

In addition, the aryl group which may have a substituent includes a phenyl group, a naphthyl group, an anthranyl group and the like, as well as a p-methylphenyl group, a p-bromophenyl group, a p-nitrophenyl group, a p- methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4 , 5,8-trichloro-2-naphthyl group, anthraquinonyl group and 2-aminoanthraquinonyl group.

The acidic group includes -SO ₃ H and -COOH, and the monovalent to trivalent metal salts of these acidic groups include sodium salt, potassium salt, magnesium salt, calcium salt, iron salt and aluminum salt. etc. Examples of alkylammonium salts of acidic groups include ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine and stearylamine; quaternary alkyl salts such as palmityltrimethylammonium, dilauryldimethylammonium and distearyldimethylammonium salts; Ammonium salts are mentioned.

_{The " substituent _ _ _} "" includes the above halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxyl group, an optionally substituted aryl group, and the like.

Adjacent groups of X1 to X4 and/or X10 to X13 in general formula (2) together form an aromatic ring which may have a substituent. The aromatic ring referred to herein includes aromatic hydrocarbon rings and heteroaromatic rings. Examples of aromatic hydrocarbon rings include benzene, naphthalene, anthracene, and phenanthrene rings. Examples of heteroaromatic rings include pyridine ring, pyrazine ring, pyrrole ring, quinoline ring, quinoxaline ring, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, oxazole ring, thiazole ring, imidazole ring, pyrazole ring, indole ring, carbazole ring and the like.

The quinophthalone compound represented by general formula (20) is preferably any one of general formulas (20A) to (20C) below.

General formula (20A)

General formula (20C)

[In the general formulas (20A) to (20C), X14 to X28, X29 to X43, and X44 to X60 are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group, or a an alkoxyl group which may be substituted, an aryl group which may have a substituent, a -SO ₃ H group, a -COOH group, a metal salt of a -SO ₃ HH group or a -COOH group, a -SO ₃ H group or a -COOH group , an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group. ]

Furthermore, X14 to X28, X29 to X43, and X44 to X60 in general formulas (20A) to (20C) are more preferably hydrogen atoms or halogen atoms.

Specific examples of the quinophthalone compound represented by formula (20) include quinophthalone compounds (a) to (p) shown below, but the present invention is not limited thereto.

When a yellow pigment is used in combination with the phthalocyanine pigment represented by general formula (2), the mass ratio of yellow pigment/phthalocyanine pigment represented by general formula (2) is in the range of 40/60 to 90/10. , brightness and color reproducibility are more preferable.

The content of the coloring agent (C) is preferably 20% by mass or more, more preferably 30% by mass, and particularly preferably 35% by mass in 100% by mass of the solid content of the photosensitive coloring composition for color filters according to the embodiment of the present invention. If it is more than mass %, sufficient color reproducibility can be obtained and the film thickness can be reduced. In addition, if it is preferably 60% by mass or less, more preferably 50% by mass or less, and particularly preferably 45% by mass or less, the content of the resin as the curing material and the photopolymerizable monomer will be appropriate and sufficient. A cured coating film can be obtained.

[Refinement of pigment]
When the coloring agent used in the photosensitive coloring composition of the present invention is a pigment, it can be made finer by salt milling or the like. The average primary particle size of the pigment determined by TEM (transmission electron microscope) is preferably in the range of 5 to 90 nm. If it is smaller than 5 nm, it becomes difficult to disperse in an organic solvent, and if it is larger than 90 nm, a sufficient contrast ratio cannot be obtained. For these reasons, the average primary particle size is more preferably in the range of 10 to 70 nm.

The salt milling process involves milling a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent while heating using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, and sand mill. This is a treatment in which water-soluble inorganic salts and water-soluble organic solvents are removed by washing with water after kneading to a certain extent. The water-soluble inorganic salt functions as a crushing aid, and the high hardness of the inorganic salt is used to crush the pigment during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate, etc. can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2,000 parts by mass, most preferably 300 to 1,000 parts by mass, based on 100 parts by mass of the pigment, from the viewpoint of both processing efficiency and production efficiency.

The water-soluble organic solvent has the function of moistening the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (miscible in) water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point solvent having a boiling point of 120° C. or higher is preferable from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1,000 parts by mass, most preferably 50 to 500 parts by mass, per 100 parts by mass of the pigment.

When salt milling the pigment, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resins used are preferably solid at room temperature, water-insoluble, and more preferably partially soluble in the above organic solvents. The amount of the resin used is preferably in the range of 5 to 200 parts by mass with respect to 100 parts by mass of the pigment.

[Dye (Cx)]
A coloring composition according to an embodiment of the present invention can also use a dye as a coloring agent. Any of acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, and the like can be used as dyes. Moreover, it may be in the form of a derivative of these or a lake pigment obtained by turning a dye into a lake.

Furthermore, in the case of acid dyes having an acidic group such as sulfonic acid or carboxylic acid, or in the form of direct dyes, inorganic salts of acid dyes, acid dyes and quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, Alternatively, a salt-forming compound with a nitrogen-containing compound such as a primary amine compound, or a salt-forming compound using a resin component having these functional groups, or a sulfonamidation and use as a sulfonic acid amide compound. In order to be excellent in resistance, it is possible to make a coloring composition excellent in fastness, which is preferable.
In addition, a salt-forming compound of an acid dye and a compound having an onium base is also preferable because of excellent fastness, and more preferably, the compound having an onium base is a resin having a cationic group in its side chain.

In the case of the form of a basic dye, it can be used by forming a salt using an organic acid, perchloric acid, or a metal salt thereof. A salt-forming compound of a basic dye is preferable because of its excellent resistance and compatibility with pigments. Further, the basic dye and the organic sulfonic acid, organic sulfuric acid, and fluorine group-containing phosphorus anion compound, which are counter components acting as counter ions, are preferably used. , a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or an acid dye. It is.

Further, when the dye skeleton has a polymerizable unsaturated group, the dye can be excellent in resistance, which is preferable.
Moreover, when the dye has an oxetane group, the coloring composition containing the dye has excellent heat resistance after curing. A dye having an oxetane group can be achieved, for example, by using an ethylenically unsaturated monomer having an oxetane structure in a resin constituting a salt-forming compound containing a dye. By having an oxetane group, the coloring composition containing the coloring agent has excellent heat resistance after curing.

In one embodiment, the chemical structure of the dye includes, for example, azo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinone imine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes, polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, A dye structure derived from a dye selected from perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, metal complex dyes thereof, and the like can be mentioned.

Among these dye structures, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium Xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanines. A dye structure derived from a dye selected from the group of dyes is more preferable. Specific dye compounds capable of forming a dye structure are described in "Shinban Dye Handbook" (edited by the Society of Synthetic Organic Chemistry; Maruzen, 1970), "Color Index" (The Society of Dyers and Colorists), "Dye Handbook" (Ogawara et al.). Ed.; Kodansha, 1986).

Dyes in another embodiment include azo dyes, azo metal complex dyes, anthraquinone dyes, indigo dyes, thioindigo dyes, phthalocyanine dyes, methine dyes, diarylmethane dyes, triarylmethane dyes, Xanthene dyes, thiazine dyes, cationic dyes, cyanine dyes, nitro dyes, quinoline dyes, naphthoquinone dyes, oxazine dyes, perylene dyes, diketopyrrolopyrrole dyes, quinacridone dyes, anthanthrone dyes Examples include, but are not limited to, dyes, isoindolinone dyes, isoindoline dyes, indanthrone dyes, coumarin dyes, quinacridone dyes, pyranthrone dyes, flavanthrone dyes, and perinone dyes.

Organic dyes that can be used in still another embodiment include triarylmethane-based, xanthene-based, and anthraquinone-based dyes, with xanthene-based dyes being preferred.

[Xanthene dye]
Xanthene dyes that can be preferably used exhibit red or purple color, and are preferably in the form of oil-soluble dyes, acid dyes, direct dyes, or basic dyes. Alternatively, it may be in the form of a lake pigment obtained by converting these dyes into a lake.
Among these, the use of xanthene-based oil-soluble dyes and xanthene-based acid dyes is preferable because of their excellent hue.

Examples of those exhibiting red and purple colors include C.I. I. solvent red, C.I. I. oil-soluble dyes such as solvent violet, C.I. I. basic red, C.I. I. basic dyes such as basic violet, C.I. I. Acid Red, C.I. I. Acid dyes such as Acid Violet, C.I. I. direct red, C.I. I. and direct dyes such as direct violet.
Here, the direct dye has a sulfonic acid group (-SO3H, -SO3Na) in its structure, and in the present disclosure, the direct dye is regarded as an acid dye.

Moreover, it is preferable to use the xanthene-based basic dye after salt formation using an organic acid or perchloric acid. As the organic acid, it is preferable to use an organic sulfonic acid or an organic carboxylic acid. Among them, it is preferable to use naphthalenesulfonic acid such as Tobias acid and perchloric acid in terms of resistance.

In addition, the xanthene-based acid dye is used as a salt-forming compound by salting using a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, a primary amine compound, etc., or a resin component having these functional groups. or sulfonamidated to be used as a sulfonic acid amide compound is preferred from the standpoint of resistance.

Salt-forming compounds of xanthene-based acid dyes and/or sulfonic acid amide compounds of xanthene-based acid dyes are preferable because they are excellent in hue and resistance. It is more preferable to use a compound prepared using a salt compound and a sulfonic acid amide compound obtained by sulfonamidating a xanthene acid dye.

Among xanthene dyes, rhodamine dyes are preferable because they are excellent in color developability and durability.
The form of the xanthene dye will be specifically described below.

[Xanthene oil-soluble dye]
Examples of xanthene-based oil-soluble dyes include C.I. I. Solvent Red 35, C.I. I. Solvent Red 36, C.I. I. Solvent Red 42, C.I. I. Solvent Red 43, C.I. I. Solvent Red 44, C.I. I. Solvent Red 45, C.I. I. Solvent Red 46, C.I. I. Solvent Red 47, C.I. I. Solvent Red 48, C.I. I. Solvent Red 49, C.I. I. Solvent Red 72, C.I. I. Solven Red 73, C.I. I. Solvent Red 109, C.I. I. Solvent Red 140, C.I. I. Solvent Red 141, C.I. I. Solvent Red 237, C.I. I. Solvent Red 246, C.I. I. solvent violet 2, C.I. I. and Solvent Violet 10.
Among them, C.I. I. Solvent Red 35, C.I. I. Solvent Red 36, C.I. I. Solvent Red 49, C.I. I. Solvent Red 109, C.I. I. Solvent Red 237, C.I. I. Solvent Red 246, C.I. I. Solvent Violet 2 is more preferred.

[Xanthene-based basic dye]
Examples of xanthene-based basic dyes include C.I. I. Basic Red 1 (Rhodamine 6GCP), 8 (Rhodamine G), C.I. I. Basic Violet 10 (Rhodamine B) and the like. Among them, C.I. I. Basic Red 1, C.I. I. Basic Violet 10 is preferably used.

[Xanthene acid dye]
Examples of xanthene-based acid dyes include C.I. I. Acid Red 51 (erythrosine (food red No. 3)), C.I. I. Acid Red 52 (acid rhodamine), C.I. I. Acid Red 87 (Eosin G (Edible Red No. 103)), C.I. I. Acid Red 92 (Acid Phloxine PB (Edible Red No. 104)), C.I. I. Acid Red 289, C.I. I. Acid Red 388, Rose Bengal B (Edible Red No. 5), Acid Rhodamine G, C.I. I. It is preferred to use Acid Violet 9.
Among them, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 388, or C.I., which is a rhodamine acid dye. I. Acid Red 52 (acid rhodamine), C.I. I. Acid Red 289, Acid Rhodamine G, C.I. I. More preferably, Acid Violet 9 is used.
Among these, C.I. I. Acid Red 52, C.I. I. Most preferably, Acid Red 289 is used.

Further, as xanthene dyes, JP-A-2010-032999, JP-A-2011-138094, JP-A-2011-227313, JP-A-2011-242752, JP-A-2012-107192, JP-A-2012-107192, 2013-033194, Japanese Patent Application No. 2011-71888, Japanese Patent Application No. 2013-72263, Japanese Patent Application No. 2013-81209, Japanese Patent Application No. 2014-173064, Japanese Patent Application No. 2013-53028, Japanese Patent Application No. 2013- 52186, JP 2014-196392, JP 2014-196393, JP 2014-201714, JP 2014-201715, JP 2013-050693, JP 2013-178478 Publicly known techniques described in Japanese Patent Laid-Open No. 2013-203956, International Publication No. 2013/011687, etc. can be used.

[Dipyrromethene dye]
The dipyrromethene-based dye is a dye that has a partial structure derived from a dipyrromethene dye as a partial structure of the dye site, and is preferably a dipyrromethene compound and a dipyrromethene metal complex compound obtained from a dipyrromethene compound and a metal or a metal compound, especially A metal complex compound in which the structure represented by the general formula (6) is coordinated to a metal atom or a metal compound (hereinafter referred to as "dipyrromethene metal complex compound" as appropriate) is preferred.

[Dipyrromethene metal complex compound]
A metal complex compound (dipyrromethene metal complex compound) in which the structure represented by the general formula (6) is coordinated to a metal atom or a metal compound will be described.

general formula (6)

In general formula (6), R ¹ to R ⁶ each independently represent a hydrogen atom or a monovalent substituent, and R ⁷ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. represents
The metal or metal compound may be any metal atom or metal compound capable of forming a complex, such as a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or a divalent metal compound. valence metal chlorides. Examples of metals or metal compounds include Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, B, etc., as well as AlCl ₃ , InCl ₃ , FeCl ₃ , TiCl ₂ , SnCl ₂ , SiCl ₂ , GeCl ₂ and other metal chlorides, TiO, VO and other metal oxides, and Si(OH) ₂ and other metal hydroxides.
Among these, as metals or metal compounds, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B or VO is preferred, Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B or VO is more preferred, Fe, Zn, Cu, Co, B or VO is most preferred.

Such dipyrromethene dyes include JP-A-2008-292970, JP-A-2010-85758, JP-A-2010-84009, JP-A-2010-43530, JP-A-2013-080010, Known techniques described in JP-A-2013-210596, International Publication No. 2013/141156, etc. can be used.

[Triphenylmethane dye]
Examples of the triphenylmethane dye skeleton include a diaminotriphenylmethane dye skeleton, a triaminotriphenylmethane dye skeleton, and a rosolic acid dye skeleton having an OH group. A triaminotriphenylmethane-based dye skeleton is preferable in terms of excellent color tone and superior lightfastness to other dyes. Among these, a diphenylnaphthylmethane dye skeleton, which is a basic dye, is particularly preferred.

[Triphenylmethane-based basic dye]
A triphenylmethane-based basic dye develops color when an NH2 or OH group positioned para to the central carbon is oxidized to form a quinone structure. They are classified into the following three types depending on the number of NH ₂ and OH groups. Among them, triaminoarylmethane-based basic dyes are preferable in terms of developing good blue, red and green colors.
a) diaminotriphenylmethane-based basic dyes b) triaminotriphenylmethane-based basic dyes c) rosolic acid-based basic dyes having an OH group triaminotriphenylmethane-based basic dyes, diaminotriphenylmethane-based basic dyes Dyes are preferred because they are vivid in color and have better lightfastness than others.

Blue-based triphenylmethane-based basic dyes have spectral characteristics with high transmittance in the range of 400 to 440 nm, so that high brightness can be obtained particularly when used for forming blue filter segments. It is preferable because it can

Specific examples of triphenylmethane-based basic dyes include C.I. I. Basic Violet 1 (Methyl Violet), Basic Violet 3 (Crystal Violet), Basic Violet 14 (Magenta), C.I. I. Basic Blue 1 (Basic Cyanine 6G), Basic Cyanine 5 (Basic Cyanine EX), Basic Blue 7 (Victoria Pure Blue BO), Basic Blue 26 (Victoria Blue B conc.), C.I. I. Examples include Basic Green 1 (Brilliant Green GX) and Basic Green 4 (Malachite Green).
Among them, C.I. I. It is preferred to use Basic Blue 7.

Examples of such triphenylmethane-based dyes include JP-A-2002-014222, JP-A-2003-246935, JP-A-2003-246935, JP-A-2008-304766, and JP-A-2010-256598. , JP 2011-200560, JP 2011-186043, JP 2012-173399, JP 2012-233033, JP 2012-098522, JP 2012-288970, JP Application No. 2012-200469, JP 2014-196262, International Publication No. 2010/123071, International Publication No. 2011/162217, International Publication No. 2013/108591, etc. can be used.

In one embodiment, the triphenylmethane dye includes C.I. I. Acid Violet 15, C.I. I. Acid Violet 17, C.I. I. Acid Violet 19, C.I. I. Acid Violet 21, C.I. I. Acid Violet 24, C.I. I. Acid Violet 25, C.I. I. Acid Violet 38, C.I. I. Acid Violet 49, C.I. I. Acid Blue 1, C.I. I. Acid Blue 3, C.I. I. Acid Blue 5, C.I. I. Acid Blue 7, C.I. I. Acid Blue 9, C.I. I. Acid Blue 11, C.I. I. Acid Blue 13, C.I. I. Acid Blue 15, C.I. I. Acid Blue 17, C.I. I. Acid Blue 22, C.I. I. Acid Blue 24, C.I. I. Acid Blue 26, C.I. I. Acid Blue 75, C.I. I. Acid Blue 83, C.I. I. Acid Blue 90, C.I. I. Acid Blue 93, C.I. I. Acid Blue 100, C.I. I. Basic Blue 81, C.I. I. Basic Blue 83 is preferably used.

Alternatively, C.I. I. Basic Violet 1, C.I. I. Basic Violet 2, C.I. I. Basic Violet 3, C.I. I. Basic Violet 4, C.I. I. Basic Violet 14, C.I. I. Basic Blue 1, C.I. I. Basic Blue 5, C.I. I. Basic Blue 7, C.I. I. Basic Blue 11, C.I. I. Basic Blue 26 can be preferably used.

[Cyanine dye]
As the cyanine dye, any compound having a dye moiety containing a cyanine skeleton in the molecule can be used without limitation.
Examples of cyanine dyes include C.I. I. Basic Yellow 11, 12, 13, 14, 21, 22, 23, 24, 28, 29, 33, 35, 40, 43, 44, 45, 48, 49, 51, 52, 53, C.I. I. Basic Red 12, 13, 14, 15, 27, 35, 36, 37, 45, 48, 49, 52, 53, 66, 68, C.I. I. Basic Violet 7, 15, 16, 20, 21, 39, 40, C.I. I. Basic Orange 27, 42, 44, 46, C.I. I. Basic Blue 62, 63 and the like.
In addition, cyanine dyes described in JP-A-2014-224970, JP-A-2013-261614, etc. can also be used.

[Anthraquinone Dyes]
Anthraquinone dyes are dyes having an anthraquinone skeleton in the molecule.
Examples of anthraquinone dyes include C.I. I. Solvent Yellow 117, 163, 167, 189, C.I. I. Solvent Orange 77, 86, C.I. I. Solvent Red 111, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247, C.I. I. solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60, C.I. I. Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59:1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139, C.I. I. Solvent Green 3, 28, 29, 32, 33, C.I. I. Acid Red 80, C.I. I. Acid Green 25, 27, 28, 41, C.I. I. Acid Violet 34, C.I. I. Acid Blue 25, 27, 40, 45, 78, 80, 112, C.I. I. Disperse Yellow 51, C.I. I. Disperse Violet 26, 27, C.I. I. Disperse Blue 1, 14, 56, 60, C.I. I. Direct Blue 40, C.I. I. Mordan Tread 3, 11, C.I. I. Mordant Blue 8 and the like can be mentioned. In addition, the anthraquinone dyes described in JP-A-9-291237, WO 2003/080734, WO 2006/024617, 2011-174987, 2013-53273, etc. It can be used as a known technique. The anthraquinone dye preferably dissolves in an organic solvent, more preferably a blue, violet or red anthraquinone dye. Examples of anthraquinone dyes include C.I. I. Solvent Blue 35, C.I. I. Solvent Blue 45, C.I. I. Acid Blue 80, C.I. I. Solvent Blue 104, and C.I. I. Solvent Blue 122 is preferable from the viewpoint of brightness and contrast.

In one embodiment, the anthraquinone dye is C.I. I. Acid Violet 29, C.I. I. Acid Violet 31, C.I. I. Acid Violet 33, C.I. I. Acid Violet 34, C.I. I. Acid Violet 36, C.I. I. Acid Violet 39, C.I. I. Acid Violet 43, C.I. I. Acid Violet 48, C.I. I. Acid Violet 63, C.I. I. Acid Violet 109, C.I. I. Acid Blue 25, C.I. I. Acid Blue 27, C.I. I. Acid Blue 41, C.I. I. Acid Blue 45, C.I. I. Acid Blue 62, C.I. I. Acid Blue 80, C.I. I. Acid Blue 127, C.I. I. Acid Blue 129, C.I. I. Acid Blue 145, C.I. I. Acid Blue 225, C.I. I. Acid Blue 230, C.I. I. Acid Blue 260, C.I. I. Acid Blue 264, C.I. I. Acid Blue 277, C.I. I. Acid Blue 281, C.I. I. Acid Blue 324 or C.I. I. Preferably, Acid Blue 350 is used.

[Salt dye]
(acidic dyes and salt-forming compounds of cationic counters)
Acid dyes (not limited to xanthene) are preferably salt-forming compounds (hereinafter also referred to as salt-forming dyes) of acid dyes and nitrogen-containing compounds, and include quaternary ammonium salt compounds, tertiary amine compounds, secondary High heat resistance, light resistance, and solvent resistance can be imparted by salt formation using an amine compound, primary amine compound, etc., or a resin component having these functional groups to form a salt-forming compound for an acid dye. preferred because it can Acid dyes can be imparted with high heat resistance, light resistance and solvent resistance by sulfonamidation.
Moreover, it may be a salt-forming compound of an acid dye and a compound having an onium base. An excellent coloring composition can be obtained.

Primary amine compounds include methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine (laurylamine), tridodecylamine, tetra decylamine (myristylamine), pentadecylamine, cetylamine, stearylamine, oleylamine, cocoalkylamine, beef tallow alkylamine, hardened beef tallow alkylamine, aliphatic unsaturated primary amines such as allylamine, aniline, benzylamine, and the like. .

Secondary amine compounds include aliphatic unsaturated secondary amines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine and diallylamine, methylaniline, ethylaniline, dibenzylamine, diphenylamine, dicocoalkyl amines, di-cured beef tallow alkylamines, distearylamines, etc.

Tertiary amine compounds include trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, dimethylaniline, diethylaniline, tribenzylamine and the like.

(Quaternary ammonium salt compound)
When the organic dye used in the embodiment of the present invention is an acid dye, it is preferably used as a salt-forming compound (a) comprising an acid dye and a quaternary ammonium salt compound. A quaternary ammonium salt compound as a counter component of an acid dye will be described. A quaternary ammonium salt compound has an amino group and thus serves as a counter for an acid dye.

A preferred form of the quaternary ammonium salt compound, which is the counter component of the salt-forming compound (a), is colorless or white. Here, colorless or white means a so-called transparent state, and is defined as a state in which the transmittance is 95% or more, preferably 98% or more in the entire wavelength region of 400 to 700 nm in the visible light region. It is. That is, it is preferable that it does not interfere with the color development of the dye component and does not cause color change.

The molecular weight of the counter portion, which is the cationic component of the quaternary ammonium salt compound, is preferably in the range of 190-900. Here, the cationic portion corresponds to the (NR ₁ R ₂ R ₃ R ₄ )+ portion in the following general formula (3). If the molecular weight is less than 190, the light resistance and heat resistance may be lowered, and the solubility in solvents may be lowered. On the other hand, if the molecular weight exceeds 900, the proportion of the coloring component in the molecule will decrease, resulting in a decrease in color developability and brightness. More preferably, the molecular weight of the counter moiety is in the range of 240-850. Particularly preferred are counter moieties with molecular weights in the range of 350-800. Here, the molecular weight was calculated based on the structural formula, and the atomic weight of C was 12, the atomic weight of H was 1, and the atomic weight of N was 14.

As the quaternary ammonium salt compound, one represented by the following general formula (3) can be used.

General formula (3)

(In general formula (3), R ₁ to R ₄ each independently represent an alkyl group having 1 to 20 carbon atoms or a benzyl group, and at least two or more of R ₁ , R ₂ , R ₃ and R ₄ are It has 5 to 20 carbon atoms, and ^Y- represents an inorganic or organic anion.)

When at least two or more of R ₁ to R ₄ have 5 to 20 carbon atoms, good solubility in solvents can be obtained. If there are three or more alkyl groups having a carbon number of less than 5, the solubility in a solvent is deteriorated, and foreign matter is likely to occur in the coating film. In addition, the presence of an alkyl group having more than 20 carbon atoms impairs the color-developing property of the salt-forming compound.

The Y 1 ^- component that constitutes the anion may be an inorganic or organic anion, preferably a halogen, usually chlorine.

Quaternary ammonium salt compounds include tetramethylammonium chloride, tetraethylammonium chloride, monostearyltrimethylammonium chloride, distearyldimethylammonium chloride, tristearylmonomethylammonium chloride, cetyltrimethylammonium chloride, trioctylmethylammonium chloride, and dioctyldimethylammonium chloride. , monolauryltrimethylammonium chloride, dilauryldimethylammonium chloride, trilaurylmethylammonium chloride, triamylbenzylammonium chloride, trihexylbenzylammonium chloride, trioctylbenzylammonium chloride, trilaurylbenzylammonium chloride, benzyldimethylstearylammonium chloride, and Examples include benzyldimethyloctylammonium chloride, dialkyl (alkyl is C14 to C18) dimethylammonium chloride (cured beef tallow), and the like.

Specific products of quaternary ammonium salt compounds include, for example, Kotamine 24P, Kotamine 86P Conc, Kotamine 60W, Kotamine 86W, Kotamine D86P, Sansol C, Sansol B-50 manufactured by Kao Corporation, and Arcade 210- manufactured by Lion Corporation. 80E, 2C-75, 2HT-75, 2HT flakes, 2O-75I, 2HP-75, 2HP flakes, among others, Cortamine D86P (distearyldimethylammonium chloride), Arcade 2HT-75 (dialkyl (alkyl is C14- C18) dimethylammonium chloride).

(Resin having a cationic group in the side chain)
When the organic dye used in the embodiment of the present invention is an acid dye, it is also preferably used as a salt-forming compound (a') comprising an acid dye and a resin having a cationic group in its side chain. A resin having a cationic group in the side chain for obtaining the salt-forming compound (a') used in the embodiment of the present invention will be described.
The resin having a cationic group in the side chain for obtaining the salt-forming compound is not particularly limited as long as it has at least one onium base in the side chain. From the viewpoint of the above, ammonium salts, iodonium salts, sulfonium salts, diazonium salts, and phosphonium salts are preferable, and considering storage stability (thermal stability), ammonium salts, iodonium salts, and sulfonium salts are preferred. is more preferable. Ammonium salts are more preferred.

When preparing a blue colored composition for color filters containing a salt-forming compound (a') and exhibiting properties as a color filter, the same resin as the binder resin constituting the blue colored composition for color filters is used. is preferred. In one embodiment of the present invention, since an acrylic resin is preferably used as a binder resin in a photosensitive coloring composition for color filters, the side chain for obtaining the salt-forming compound (a′) has a cationic group. The resin is preferably an acrylic resin.

As the resin having a cationic group in its side chain, an alkali resin containing a structural unit represented by the following general formula (5) can be used. A salt-forming compound can be obtained by forming a salt between the cationic group in the general formula (5) and the anionic group of the xanthene-based acid dye.

General formula (5)

[In general formula (5), R ⁵¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ⁵² to R ⁵⁴ each independently represent a hydrogen atom, an optionally substituted alkyl group, an ^optionally substituted alkenyl group, or an ^optionally substituted aryl group; Two of them may combine with each other to form a ring. Q represents an alkylene group, an arylene group, --CONH--R ⁵⁵ --, --COO--R ⁵⁵ --, and R ⁵⁵ represents an alkylene group. Y- represents an inorganic or organic anion. ]

Examples of the alkyl group for R ⁵¹ include methyl group, ethyl group, propyl group, n-butyl group, i-butyl group, t-butyl group, n-hexyl group and cyclohexyl group. As the alkyl group, an alkyl group having 1 to 12 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.

When the alkyl group represented by R ⁵¹ has a substituent, examples of the substituent include a hydroxyl group and an alkoxyl group. Among the above, R ⁵¹ is most preferably a hydrogen atom or a methyl group.

In general formula (5), each of R ⁵² to R ⁵⁴ independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group. mentioned.

Here, the alkyl groups for R ⁵² to R ⁵⁴ include, for example, linear alkyl groups (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl, n -tetradecyl, n-hexadecyl and n-octadecyl), branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, 2-ethylhexyl and 1,1,3,3 -tetramethylbutyl, etc.), cycloalkyl groups (such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl) and bridged cyclic alkyl groups (such as norbornyl, adamantyl and pinanyl). The alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms.

Examples of alkenyl groups for R ⁵² to R ⁵⁴ include linear or branched alkenyl groups (vinyl, allyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1 -propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl and 2-methyl-2-propenyl, etc.), cycloalkenyl groups (2-cyclohexenyl, 3-cyclohexenyl, etc.). The alkenyl group is preferably an alkenyl group having 2 to 18 carbon atoms, more preferably an alkenyl group having 2 to 8 carbon atoms.

Examples of aryl groups for R ⁵² to R ⁵⁴ include monocyclic aryl groups (phenyl etc.), condensed polycyclic aryl groups (naphthyl, anthracenyl, phenanthrenyl, anthraquinolyl, fluorenyl and naphthoquinolyl etc.) and aromatic heterocyclic hydrocarbons. Groups (thienyl (group derived from thiophene), furyl (group derived from furan), pyranyl (group derived from pyran), pyridyl (group derived from pyridine), 9-oxoxanthenyl (group derived from xanthone derived groups) and 9-oxothioxanthenyl (groups derived from thioxanthone), etc.).

When the alkyl group, alkenyl group or aryl group represented by R ⁵² to R ⁵⁴ has a substituent, examples of the substituent include a halogen atom, a hydroxyl group, an alkoxyl group, an aryloxy group, an alkenyl group, an acyl group, A substituent selected from an alkoxycarbonyl group, a carboxyl group, a phenyl group, and the like can be mentioned. Among these substituents, halogen atoms, hydroxyl groups, alkoxyl groups, and phenyl groups are particularly preferred.

From the viewpoint of stability, R ⁵² to R ⁵⁴ are preferably optionally substituted alkyl groups, more preferably unsubstituted alkyl groups.

Also, two of R ⁵² to R ⁵⁴ may combine with each other to form a ring.

In the general formula (5), the component of Q connecting the vinyl moiety and the ammonium base represents an alkylene group, an arylene group, -CONH-R ⁵⁵ -, and -COO-R ⁵⁵ -, and R ⁵⁵ represents an alkylene group, Of these, -CONH-R ⁵⁵ - and -COO-R ⁵⁵ - are preferred from the viewpoint of polymerizability and availability. Further, ^R55 is more preferably a methylene group, an ethylene group, a propylene group or a butylene group, and particularly preferably an ethylene group.

The Y component in general formula (5) constituting the counter anion of the resin may be an inorganic or organic anion. As the counter anion, known ones can be employed without limitation, and specific examples include hydroxide ions; halide ions such as chloride ions, bromide ions and iodide ions; carboxylate ions such as formate ions and acetate ions; such as carbonate, bicarbonate, nitrate, sulfate, sulfite, chromate, dichromate, phosphate, cyanide, permanganate and also hexacyanoferrate(III) complex ions and the like. Halogen ions and carboxylate ions are preferred, and halogen ions are most preferred, from the viewpoints of suitability for synthesis and stability. When the counter anion is an organic acid ion such as carboxylate ion, the organic acid ion may be covalently bonded to the resin to form an inner salt.

One method of introducing an oxetane group into a resin having a cationic group in its side chain is to convert an ethylenically unsaturated monomer containing an oxetane structure to a cationic group represented by general formula (5). It is a method of copolymerizing with an ethylenically unsaturated monomer.
Ethylenically unsaturated monomers having an oxetane group include (3-methyl-3-oxetanyl)methyl (meth)acrylate, (3-ethyl-3-oxetanyl)methyl (meth)acrylate, (3-butyl-3 -oxetanyl)methyl (meth)acrylate, (3-hexyltyl-3-oxetanyl)methyl (meth)acrylate and the like.
Examples of commercially available products include ETERNACOLL OXMA (manufactured by Ube Industries, Ltd.), OXE-10, and OXE-30 (manufactured by Osaka Organic Chemical Industry Co., Ltd.).

(salt formation)
A salt-forming compound of an acid dye and a nitrogen-containing compound or a resin having a cationic group in a side chain can be produced by a conventionally known method. A specific method is disclosed in Japanese Patent Application Laid-Open No. 11-72969.
As an example using a xanthene-based acid dye, after dissolving the xanthene-based acid dye in water, a quaternary ammonium salt compound may be added, and the solution may be subjected to chlorination while stirring. Here, a salt-forming compound in which the sulfonic acid group (--SO ₃ H) or sodium sulfonate group (--SO ₃ Na) in the xanthene acid dye and the ammonium group (NH4+) in the quaternary ammonium salt compound are combined. is obtained. In place of water, methanol and ethanol are also usable solvents for chlorination.

Further, the salt-forming compound is obtained by stirring or vibrating an aqueous solution in which a resin having a cationic group in the side chain represented by the general formula (5) and an acid dye are dissolved, or It can be easily obtained by mixing an aqueous solution of a resin having a cationic group in its side chain and an aqueous solution of an acid dye under stirring or shaking. In an aqueous solution, the ammonium group of the resin and the anionic group of the acid dye are ionized, and they form an ionic bond, and the ion-bonded portion becomes water-insoluble and precipitates. On the contrary, since the salt composed of the counter anion of the resin and the counter cation of the acid dye is water-soluble, it can be removed by washing with water or the like. The resin having a cationic group in the side chain and the acid dye to be used may be of a single type, or may be of a plurality of types having different structures.
Also, with other acid dyes, a salt-forming compound with a nitrogen-containing compound or a resin having a cationic group in the side chain can be obtained in the same manner as for xanthene dyes.

(sulfonic acid amide compound)
The acid dye may be a sulfonic acid amide compound obtained by reacting a sulfonic acid amide compound with an anionic dye.
Sulfonic acid amide compounds of acid dyes that can be preferably used for acid dyes are obtained by chlorinating acid dyes having —SO ₃ H and —SO ₃ Na by a conventional method to convert —SO ₃ H to —SO ₂ Cl. Compounds can be prepared by reacting with an amine having a —NH ₂ group.
Amine compounds that can be preferably used in sulfonamidation include, specifically, 2-ethylhexylamine, dodecylamine, 3-decyloxypropylamine, 3-(2-ethylhexyloxy)propylamine, and 3-ethoxypropyl. Amines, cyclohexylamines and the like are preferably used.
As an example of xanthene-based acid dyes, C.I. I. When obtaining a sulfonic acid amide compound obtained by modifying Acid Red 289 with 3-(2-ethylhexyloxy)propylamine, C.I. I. Acid Red 289 is sulfonyl chlorided and then reacted with the theoretical equivalent of 3-(2-ethylhexyloxy)propylamine in dioxane to give C.I. I. A sulfonic acid amide compound of Acid Red 289 may be obtained.
Also, C.I. I. In the case of obtaining a sulfonic acid amide compound by modifying Acid Red 52 with 3-(2-ethylhexyloxy)propylamine, C.I. I. Acid Red 52 is sulfonyl chlorided and then reacted with the theoretical equivalent of 3-(2-ethylhexyloxy)propylamine in dioxane to give C.I. I. A sulfonic acid amide compound of Acid Red 52 may be obtained.
Also, with other acid dyes, sulfonic acid amide compounds can be obtained in the same manner as with xanthene dyes.

(Salt-forming compounds of basic dyes and anionic counters)
Moreover, in the case of a basic dye, it can be used by forming a salt using an organic acid, perchloric acid, or a metal salt thereof. Among them, salt-forming compounds of basic dyes are preferable because of their excellent resistance and compatibility with pigments. An anion compound, a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or a salt-forming compound obtained by forming a salt with an acid dye can be used. It is more preferable.

Specifically, organic acids such as heteropoly acids, organic sulfonic acids such as aliphatic sulfonic acids and aromatic sulfonic acids, organic sulfuric acids such as aliphatic sulfuric acids and aromatic sulfuric acids, aromatic carboxylic acids, organic carboxylic acids such as fatty acids, Or it has the form of an acid dye. Or they may be metal salts thereof. Salt-forming compounds with resins having acid groups are also preferred.

(salt formation)
Salt-forming compounds of these basic dyes and anionic counters can be synthesized by conventionally known methods. A specific technique is disclosed in Japanese Unexamined Patent Application Publication No. 2003-215850.
For example, after dissolving a triarylmethane-based basic dye in water, an organic sulfonic acid or (organic sodium sulfonate) solution may be added, and chloride-forming treatment may be performed while stirring. Here, a salt-forming compound is obtained in which the amino group (--NHC ₂ H ₅ ) portion of the triarylmethane-based basic dye and the sulfonic acid group (--SO ₃ H) portion of the organic sulfonic acid are combined.
Here, the organic sulfonic acid can also be dissolved in an alkaline solution such as sodium hydroxide and used in the form of sodium sulfonate (--SO ₃ Na) before salt formation. In the present disclosure, the sulfonic acid group (--SO ₃ H) and the functional group being sodium sulfonate (--SO ₃ Na) may be referred to interchangeably.

<Solvent>
The photosensitive coloring composition is prepared by sufficiently dispersing the coloring agent (C) in a dye carrier such as the resin (X) or the urethane-based photopolymerizable monomer (B), and forming a dry film on a transparent substrate such as a glass substrate. A solvent can be contained in order to facilitate the formation of filter segments and black matrices by coating to a thickness of 0.2 to 10 μm. Examples of solvents include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl -1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol , 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene , N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o- Dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono Ethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate , diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, di Propylene Glycol Methyl Ether Acetate, Dipropylene Glycol Monoethyl Ether, Dipropylene Glycol Monobutyl Ether, Dipropylene Glycol Monopropyl Ether, Dipropylene Glycol Monomethyl Ether, Diacetone Alcohol, Triacetin, Tripropylene Glycol Monobutyl Ether, Tripropylene Glycol Monomethyl Ether, Propylene Glycol Diacetate, Propylene Glycol Phenyl Ether, Propylene Glycol Monoethyl Ether , propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, acetic acid Examples include n-amyl, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid esters and the like, and these are used alone or in combination.
The solvent can be used in an amount of 100 to 10,000 parts by weight, preferably 500 to 5,000 parts by weight, per 100 parts by weight of the coloring agent (C) in the photosensitive coloring composition.

<Other ingredients>
<Sensitizer>
Additionally, the photosensitive coloring composition according to embodiments of the present invention may contain a sensitizer. The content of the sensitizer can be used in an amount of 1 to 200 parts by mass with respect to 100 parts by mass of the photopolymerization initiator (A) in the photosensitive coloring composition.

Sensitizers include unsaturated ketones such as chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives and anthraquinone derivatives. , xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives .

Further specific examples include Shin Okawara et al., "Dye Handbook" (1986, Kodansha), Shin Okawara et al., "Chemistry of Functional Dyes" (1981, CMC), Chuzaburo Ikemori et al., "Special functional materials '' (1986, CMC). In addition, a sensitizer that absorbs light in the ultraviolet to near-infrared region can also be included.

Among the above sensitizers, thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives can be mentioned as sensitizers that can particularly favorably sensitize the compound represented by formula (1). More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4′-bis (Dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- N-ethylcarbazole and the like can be used.
The sensitizer may contain two or more sensitizers in any ratio.

<Silane coupling agent>
The photosensitive coloring composition can contain an adhesion improver such as a silane coupling agent in order to improve adhesion to the transparent substrate. By improving the adhesion due to the silane coupling agent, the reproducibility of fine lines is improved and the resolution is improved.
Examples of the silane coupling agent include vinylsilanes such as vinyltris(β-methoxyethoxy)silane, vinylethoxysilane and vinyltrimethoxysilane, (meth)acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β-( 3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)methyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxy Epoxysilanes such as cyclohexyl)methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ -aminopropyltrimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

The silane coupling agent can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, per 100 parts by weight of the coloring agent (C) in the photosensitive coloring composition.

<Polyfunctional thiol>
A photosensitive coloring composition can contain a polyfunctional thiol. Polyfunctional thiols are compounds having two or more thiol (SH) groups.
By using the polyfunctional thiol together with the photopolymerization initiator (A) described above, in the radical polymerization process after light irradiation, it acts as a chain transfer agent and generates thiyl radicals that are less susceptible to polymerization inhibition by oxygen. The sensitive coloring composition becomes highly sensitive. Polyfunctional aliphatic thiols in which SH groups are bonded to aliphatic groups such as methylene and ethylene groups are particularly preferred.
For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tris. thioglycolate, trimethylolpropane tristhiopropionate, trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptopropionate), Pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), trimercaptopropionate tris(2-hydroxy ethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine and the like. . These polyfunctional thiols can be used singly or in combination of two or more.

The content of the polyfunctional thiol is preferably 0.05 to 100 parts by mass, more preferably 1.0 to 50.0 parts by mass, per 100 parts by mass of the colorant (C).
Better development resistance can be obtained by using 0.05 parts by mass or more of the polyfunctional thiol. When a monofunctional thiol having one thiol (SH) group is used, such an improvement in development resistance cannot be obtained.

<Antioxidant>
The photosensitive coloring composition can contain an antioxidant. Antioxidants are used to prevent photopolymerization initiators and thermosetting compounds contained in the photosensitive coloring composition for color filters from oxidizing and yellowing due to thermal curing and thermal processes during ITO annealing. Transmittance can be increased. Therefore, by including an antioxidant, it is possible to prevent yellowing due to oxidation during the heating process and obtain a high transmittance of the coating film.

The "antioxidant" may be a compound having an ultraviolet absorption function, a radical scavenging function, or a peroxide decomposition function. , sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylic acid ester-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used.

Among these antioxidants, from the viewpoint of achieving both transmittance and sensitivity of the coating film, preferred are hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. agents. More preferably, it is a hindered phenol-based antioxidant, a hindered amine-based antioxidant, or a phosphorus-based antioxidant.
These antioxidants can be used singly or as a mixture of two or more at any ratio as required.

The content of the antioxidant is more preferably 0.5 to 5.0% by mass based on the solid content of the photosensitive coloring composition (100% by mass), because the brightness and sensitivity are good.

<Ultraviolet absorber, polymerization inhibitor>
The photosensitive coloring composition can contain an ultraviolet absorber or a polymerization inhibitor. By containing an ultraviolet absorber or a polymerization inhibitor, the shape and resolution of the pattern can be controlled. UV absorbers include, for example, 2-[4-[(2-hydroxy-3-(dodecyl and tridecyl)oxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl) -1,3,5-triazine, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, etc. hydroxyphenyltriazine series, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, Benzotriazoles such as 2-(3-tbutyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2' , 4,4′-tetrahydroxybenzophenone and other benzophenones, phenyl salicylate, p-tert-butylphenyl salicylate and other salicylates, ethyl-2-cyano-3,3′-diphenyl acrylate and other cyanoacrylates system, 2,2,6,6-tetramethylpiperidine-1-oxyl (triacetone-amine-N-oxyl), bis(2,2,6,6-tetramethyl-4-piperidyl)-sebacate, poly[ [6-[(1,1,3,3-tetrabutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino ] and the like, and these are used singly or in combination. Examples of polymerization inhibitors include methylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, 4-benzoquinone, 4-methoxyphenol, 4-methoxy-1-naphthol and t-butylcatechol. , amine compounds such as phenothiazine, bis-(1-dimethylbenzyl)phenothiazine, 3,7-dioctylphenothiazine, copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, manganese diphenyldithiocarbamate, etc. copper and manganese salt compounds, 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, N-nitrosocyclohexylhydroxylamine, N-nitrosophenylhydroxylamine and other nitroso compounds and their ammonium salts or aluminum salts. Alternatively, they are mixed and used.

The ultraviolet absorber and the polymerization inhibitor can be used in an amount of 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, with respect to 100 parts by weight of the coloring agent (C) in the coloring composition. .
Better resolution can be obtained by using 0.01 parts by mass or more of the ultraviolet absorber or the polymerization inhibitor.

<Storage stabilizer>
The photosensitive coloring composition can contain a storage stabilizer. By containing a storage stabilizer, the viscosity of the composition over time can be stabilized. Storage stabilizers include, for example, 2,6-bis(1,1-dimethylethyl)-4-methylphenol, pentaerythyryl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate], hindered phenols such as 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino) 1,3,5-triazine, tetraethylphosphine, tri Organic phosphines such as phenylphosphine and tetraphenylphosphine; phosphites such as zinc dimethyldithiophosphate, zinc dipropyldithiophosphate and molybdenum dibutyldithiophosphate; sulfur compounds such as dodecyl sulfide and benzothiophene; Examples include quaternary ammonium chlorides such as diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, methyl ethers thereof, and the like, and these may be used alone or in combination.

The storage stabilizer can be used in an amount of 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the colorant (C) in the coloring composition.
By using 0.01 parts by mass or more of the storage stabilizer, the stability over time of the photosensitive coloring composition is improved.

In addition, the photosensitive coloring composition can contain an amine-based compound that acts to reduce dissolved oxygen.
Examples of such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylamino benzoate. ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl p-toluidine and the like.

<Leveling agent>
The photosensitive coloring composition may contain a leveling agent to improve the leveling properties of the composition on the transparent substrate. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in its main chain is preferred. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Dow Corning Toray Co., Ltd. and BYK-333 manufactured by BYK Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK-Chemie. A dimethylsiloxane having a polyether structure in its main chain and a dimethylsiloxane having a polyester structure in its main chain can be used in combination. The content of the leveling agent is usually preferably from 0.003 to 1.0 parts by weight per 100 parts by weight of the total weight of the coloring composition.

Especially preferred as a leveling agent is a type of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a hydrophilic group but has low solubility in water, and when added to the coloring composition, its It is useful that it has the characteristic of low surface tension lowering ability and good wettability to the glass plate despite the low surface tension lowering ability, and it is added in an amount that does not cause defects in the coating film due to bubbling. A substance capable of sufficiently suppressing chargeability can be preferably used. A dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used as a leveling agent having such preferred properties. Polyalkylene oxide units include polyethylene oxide units and polypropylene oxide units, and dimethylpolysiloxane may have both polyethylene oxide units and polypropylene oxide units.

In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane is a pendant type in which the polyalkylene oxide unit is bonded to the repeating unit of dimethylpolysiloxane, a terminal modified type in which the terminal is bonded to the terminal of dimethylpolysiloxane, and a dimethylpolysiloxane. It may be of any linear block copolymer type with alternating repeating bonds. Dimethylpolysiloxanes having polyalkylene oxide units are commercially available from Dow Corning Toray Co., Ltd., such as FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ -2207, but not limited to.

Anionic, cationic, nonionic or amphoteric surfactants can be added to the leveling agent as auxiliaries. Two or more kinds of surfactants may be mixed and used.
Examples of anionic surfactants added to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, and alkyldiphenyl ether disulfonic acid. Sodium, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate and esters.

Cationic surfactants added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate. , polyethylene glycol monolaurate; alkylbetaines such as alkyldimethylaminoacetic acid betaine; amphoteric surfactants such as alkylimidazoline; and fluorine-based and silicone-based surfactants.

Cationic surfactants added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate. , polyethylene glycol monolaurate; alkylbetaines such as alkyldimethylaminoacetic acid betaine; amphoteric surfactants such as alkylimidazoline; and fluorine-based and silicone-based surfactants.

<Method for producing photosensitive coloring composition for color filter>
The photosensitive coloring composition for a color filter of the present invention is prepared by dispersing a coloring agent using a dispersing aid in a coloring agent carrier such as a binder resin and/or a solvent, if necessary, using a kneader, a two-roll mill, or a three-roll mill. , a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor. At this time, two or more kinds of colorants, etc. may be dispersed in the colorant carrier at the same time, or may be mixed separately dispersed in the colorant carrier.
The active energy ray-curable resin having an ethylenically unsaturated double bond may be added at the stage of preparing the colorant dispersion, or may be added later to the prepared colorant dispersion to obtain the same effect. From the viewpoint of the stability of the coloring composition, it is preferably added at the stage of preparing the photosensitive coloring composition.
If the colorant such as dye has high solubility, specifically, if it has high solubility in the solvent to be used, and if it is dissolved by stirring and no foreign matter is confirmed, it is manufactured by finely dispersing as described above. No need. In this case, the dispersing aid can also be used by simply adding to and mixing with a colorant solution in which dyes and the like are dissolved.

When used as a photosensitive coloring composition (resist material) for color filters, it can be prepared as a solvent-developing or alkali-developing coloring composition. The solvent-developable or alkali-developable coloring composition comprises the above-mentioned colorant dispersion, a photopolymerizable monomer and/or a photopolymerization initiator, and optionally a solvent, other pigment dispersants, and additives. etc. can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added later to the prepared coloring composition.

<Dispersing aid>
When dispersing the colorant in the colorant carrier, a dispersing aid such as a resin-type dispersant, a dye derivative, or a surfactant may be contained as appropriate. Since the dispersing aid has a great effect of preventing the reaggregation of the colorant after dispersion, the coloring composition obtained by dispersing the colorant in the colorant carrier using the dispersing aid has good brightness and viscosity stability. get better.

[Resin Dispersant]
The resin-type dispersant has a colorant affinity site having a property of adsorbing to the added colorant and a site compatible with the colorant carrier, and adsorbs to the added colorant to disperse in the colorant carrier. It works to stabilize the Specific examples of resin-type dispersants include polyurethanes, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, amides formed by the reaction of poly(lower alkyleneimine) with polyesters having free carboxyl groups, and salts thereof oily dispersants such as (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Water-soluble resins, water-soluble polymer compounds, polyesters, modified polyacrylates, ethylene oxide/propylene oxide addition compounds, phosphoric acid esters, etc. are used, and these can be used alone or in combination of two or more. However, it is not necessarily limited to these.

(Basic resin type dispersant)
As the dispersant used in the present invention, a basic resin-type dispersant having a basic functional group is preferable, and a nitrogen atom-containing graft copolymer, a tertiary amino group in the side chain, a quaternary ammonium base, a nitrogen-containing heterogeneous Nitrogen atom-containing acrylic block copolymers and urethane polymer dispersants having functional groups containing rings are preferred. The resin-type dispersant is preferably used in an amount of about 5 to 200% by mass, more preferably in an amount of about 10 to 100% by mass, based on the total amount of the coloring agent.

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166 manufactured by BYK-Japan. or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, SOLSPERSE-3000, 9000, 13000, 13240 manufactured by Nippon Lubrizol, １３６５０、１３９４０、１６０００、１７０００、１８０００、２００００、２１０００、２４０００、２６０００、２７０００、２８０００、３１８４５、３２０００、３２５００、３２５５０、３３５００、３２６００、３４７５０、３５１００、３６６００、３８５００、４１０００、４１０９０、５３０９５、５５０００、 EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408 manufactured by BASF, such as 56000, 76500 , 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., Ajinomoto Fine-Techno Co., Ltd. Ajisper-PA111, PB711, PB821, PB822, PB824 and the like are preferable.

(Acidic resin-type dispersant)
Moreover, as the resin-type dispersant used in the present invention, an acidic resin-type dispersant can also be suitably used. The resin-type dispersant used in the present invention preferably contains the following (S1) or (S2) as a resin-type dispersant having a carboxyl group.
(S1) A resin type dispersant which is a reaction product of a hydroxyl group of a polymer having a hydroxyl group and an acid anhydride group of a tricarboxylic anhydride and/or a tetracarboxylic dianhydride.
(S2) a polymer obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product of a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of a tricarboxylic anhydride and/or a tetracarboxylic dianhydride; A resin-type dispersant that is a coalesce.

<<Resin Dispersant (S1)>>
The resin-type dispersant (S1) can be produced by known methods such as those disclosed in WO2008/007776, JP-A-2008-029901, JP-A-2009-155406, and the like. The polymer (p) having a hydroxyl group is preferably a polymer having a terminal hydroxyl group. For example, an ethylenically unsaturated monomer (r) is polymerized in the presence of a compound (q) having a hydroxyl group. It can be obtained as a polymer. The compound (q) having a hydroxyl group is preferably a compound having a hydroxyl group and a thiol group in the molecule. Since it is preferable to have a plurality of hydroxyl groups at the terminals, the compound (q1) having two hydroxyl groups and one thiol group in the molecule is preferably used.

That is, a polymer having two hydroxyl groups at one end, which is a more preferable example, is obtained by adding a monomer (r1) in the presence of a compound (q1) having two hydroxyl groups and one thiol group in the molecule. It can be obtained as a polymer (p1) by polymerizing the ethylenically unsaturated monomer (r) contained. The hydroxyl group of the polymer (p) having a hydroxyl group reacts with the acid anhydride group of the tricarboxylic anhydride and/or the tetracarboxylic dianhydride to form an ester bond, while the anhydride ring is opened to form a carboxylic acid. produces

<<Resin Dispersant (S2)>>
The resin-type dispersant (S2) can be produced by known methods such as JP-A-2009-155406, JP-A-2010-185934, and JP-A-2011-157416. By polymerizing an ethylenically unsaturated monomer (r) in the presence of a reaction product between a hydroxyl group of (q) and an acid anhydride group of a tricarboxylic anhydride and/or a tetracarboxylic dianhydride. can get. Above all, in the presence of a reaction product of a hydroxyl group of a compound (q1) having two hydroxyl groups and one thiol group in the molecule and an acid anhydride group of a tricarboxylic anhydride and/or a tetracarboxylic dianhydride. Furthermore, it is preferably a polymer obtained by polymerizing an ethylenically unsaturated monomer (r) containing a monomer (r1).

(S1) and (S2) are the difference in whether the introduction of the polymer moiety obtained by polymerizing the ethylenically unsaturated monomer (r) is performed first or later. Although the molecular weight and the like may differ slightly depending on various conditions, theoretically the same product can be obtained if the raw materials and reaction conditions are the same.

The coloring composition of the present invention preferably contains a basic resin-type dispersant and an acidic resin-type dispersant.

[Dye derivative]
Examples of dye derivatives include compounds obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group optionally having a substituent into an organic pigment, anthraquinone, acridone or triazine. 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-2001-335717, JP-A-2003- 128669, JP 2004-091497, JP 2007-156395, JP 2008-094873, JP 2008-094986, JP 2008-095007, JP 2008-195916 Those described in publications, Japanese Patent No. 4585781 and the like can be used, and these can be used alone or in combination of two or more.

The content of the pigment derivative is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and most preferably 3 parts by mass or more with respect to 100 parts by mass of the colorant, from the viewpoint of improving dispersibility. From the viewpoint of heat resistance and light resistance, the amount is preferably 40 parts by mass or less, more preferably 35 parts by mass or less.

[Surfactant]
Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalenesulfonate, sodium alkyldiphenylether disulfonate. , monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, anionic surfactants such as polyoxyethylene alkyl ether phosphate; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; cationic surfactants such as quaternary ammonium salts and their ethylene oxide adducts; alkylbetaines such as alkyldimethylaminoacetic acid betaine; amphoteric surfactants such as alkylimidazoline; Although they can be mixed and used, they are not necessarily limited to these.

When a surfactant is added, it is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 45 parts by mass, per 100 parts by mass of the colorant. If the content of the surfactant is less than 0.1 parts by mass, it is difficult to obtain the effect of addition, and if the content is more than 55 parts by mass, the excess dispersant may affect dispersion. .

<Removal of coarse particles>
The colored composition of the present invention is separated by means of centrifugation, filtration with a sintered filter, membrane filter, or the like, and the coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more of coarse particles and It is preferable to remove mixed dust. Thus, the coloring composition preferably does not substantially contain particles of 0.5 μm or larger. More preferably, it is 0.3 μm or less.

<Manufacturing method of color filter>
The color filter of the present invention comprises a substrate (hereinafter also referred to as a transparent substrate), filter segments formed using a photosensitive coloring composition for color filters, and a black matrix.
A color filter comprises a filter segment or a black matrix formed from the photosensitive coloring composition of the present invention on a transparent substrate, and a typical color filter comprises at least one red filter segment, at least one green and at least one blue filter segment, or at least one magenta filter segment, at least one cyan filter segment, and at least one yellow filter segment.

As the transparent substrate, a glass plate of soda lime glass, low-alkali borosilicate glass, alkali-free aluminoborosilicate glass, or the like, or a resin plate of polycarbonate, polymethyl methacrylate, polyethylene terephthalate, or the like can be used. A transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate for driving the liquid crystal after panelization. The dry film thickness of the filter segment and black matrix is preferably 0.2-10 μm, more preferably 0.2-5 μm. A vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used to dry the coating film.

The formation of each color filter segment and black matrix by photolithography can be performed by the following method. That is, a photosensitive colored composition prepared as a solvent-developable or alkali-developable colored resist material is coated on a transparent substrate by a coating method such as spray coating, spin coating, slit coating, roll coating, or the like, to give a dry film thickness of 0.00. It is applied so that it becomes 2 to 10 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact or non-contact with this film.

After that, it is immersed in a solvent or an alkaline developer, or the developer is sprayed by spraying or the like to remove the uncured portion, and a desired pattern is formed to form the filter segment and the black matrix. Furthermore, in order to promote polymerization of the filter segments and black matrix formed by development, heating may be applied as necessary. The photolithography method can form the filter segments and black matrix with higher precision than the printing method.

At the time of development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkaline developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoaming agent or a surfactant can be added to the developer. As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a puddle (liquid puddle) development method, or the like can be applied.
In order to increase the UV exposure sensitivity, after coating and drying the photosensitive coloring composition, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is coated and dried to form a film that prevents polymerization inhibition by oxygen. UV exposure can also be performed after forming the .

<Liquid crystal display device>
The liquid crystal display device of the present specification preferably has a color filter. Further, it is more preferable that the liquid crystal display device includes a color filter and a light source. As a light source, a cold cathode fluorescent lamp (CCFL) and a white LED can be used. In the present invention, it is preferable to use a white LED in terms of widening the reproduction range of red. An example of the liquid crystal display device will be described below with reference to FIG. The liquid crystal display device 10 comprises a pair of transparent substrates 11 and 21 arranged facing each other with a gap therebetween, and a liquid crystal LC is enclosed between them.

The liquid crystal LC is aligned according to a drive mode such as TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane switching), VA (Vertical Alignment), OCB (Optically Compensated Birefringence). A TFT (thin film transistor) array 12 is formed on the inner surface of the first transparent substrate 11, and a transparent electrode layer 13 made of ITO, for example, is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13 . A polarizing plate 15 is formed on the outer surface of the transparent substrate 11 .

On the other hand, the color filter 22 of the present invention is formed on the inner surface of the second transparent substrate 21 . The red, green and blue filter segments that make up color filter 22 are separated by a black matrix (not shown).

A transparent protective film (not shown) is formed as necessary to cover the color filters 22, and a transparent electrode layer 23 made of, for example, ITO is formed thereon. is provided.

A polarizing plate 25 is formed on the outer surface of the transparent substrate 21 . A backlight unit 30 is provided below the polarizing plate 15 .

White LED light sources include those in which a fluorescent filter is formed on the surface of a blue LED and those in which a phosphor is contained in a resin package of a blue LED. λ3), has a wavelength (λ4) at which the emission intensity is maximum within the range of 530 nm to 580 nm, has a wavelength (λ5) at which the emission intensity is maximum within the range of 600 nm to 650 nm, and has a wavelength The ratio (I4/I3) of the emission intensity I3 at λ3 to the emission intensity I4 at wavelength λ4 is 0.2 or more and 0.4 or less, and the ratio of the emission intensity I3 at wavelength λ3 to the emission intensity I5 at wavelength λ5 (I5/I3 ) has a spectral characteristic of 0.1 to 1.3, and a wavelength (λ1) at which the emission intensity is maximized in the range of 430 nm to 485 nm, and the range of 530 nm to 580 nm has a second emission intensity peak wavelength (λ2) within, and the ratio (I2/I1) of the emission intensity I1 at the wavelength λ1 to the emission intensity I2 at the wavelength λ2 is 0.2 or more and 0.7 or less A white LED light source (LED2) with a is preferred.

Specific examples of the LED 1 include NSSW306D-HG-V1 (manufactured by Nichia Corporation), NSSW304D-HG-V1 (manufactured by Nichia Corporation), and the like.

Specific examples of the LED 2 include NSSW440 (manufactured by Nichia Corporation) and NSSW304D (manufactured by Nichia Corporation).

The following examples illustrate the invention. "Parts" and "%" in the examples represent "parts by mass" and "% by mass", respectively. "PGMAc" means propylene glycol monomethyl ether acetate.

(Resin mass average molecular weight (Mw))
The mass-average molecular weight (Mw) of the resin was measured using HLC-8220GPC (manufactured by Tosoh Corporation) as an apparatus, TSK-GEL SUPER HZM-N as a column, and THF as a solvent. It is a polystyrene equivalent molecular weight.

(Ammonium salt value of resin)
The ammonium salt value of the resin is obtained by titration with a 0.1N silver nitrate aqueous solution using a 5% potassium chromate aqueous solution as an indicator, and then converted to the equivalent of potassium hydroxide. represents

(Identification of phthalocyanine)
Identification of phthalocyanine is performed by matching the molecular ion peak of the mass spectrum obtained using a time-of-flight mass spectrometer (autoflex III (TOF-MS), manufactured by Bruker Daltonics) with the mass number obtained by calculation, and , the ratio of carbon, hydrogen and nitrogen obtained using an elemental analyzer (2400CHN elemental analyzer, manufactured by Perkin-Elmer) and the theoretical values.

(Average number of substituted halogen atoms)
The average value of the number of substituted halogen atoms is obtained by burning the pigment by the oxygen combustion flask method, and analyzing the liquid obtained by absorbing the burned product in water by ion chromatography (ICS-2000 ion chromatography, manufactured by DIONEX). It was obtained by quantifying the amount of halogen by the method and converting it into the average value of the number of substituted halogen atoms.

(Halogen distribution width in pigment)
The halogen distribution width is determined by the signal intensity of the molecular ion peak corresponding to each component (each peak value ) and a value obtained by integrating each peak value (total peak value), and the number of peaks having a ratio of each peak value to the total peak value of 1% or more was counted to obtain the halogen distribution width.

(Volume average primary particle size (MV))
The volume average primary particle size (MV) was obtained by using a transmission electron microscope (TEM) "H-7650" manufactured by Hitachi High-Technologies Corporation and the following formula. First, the colorant particles were photographed by TEM. From the obtained image, 100 pigment or colorant particles were arbitrarily selected, and the average value of the short axis diameter and long axis diameter of the primary particles was taken as the particle size (d) of the colorant particles. Next, each pigment or colorant was regarded as a sphere having the particle size (d) previously determined, and the volume (V) of each particle was determined. This operation was carried out for 100 pigment or colorant particles, and calculated using the following formula (1).

Formula (1) MV=Σ(V・d)/Σ(V)

EXAMPLES The embodiments of the present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.

<Production of aluminum phthalocyanine pigment precursor>
(Production of phthalocyanine pigment precursor (P-1))
In a reactor, 225 parts of phthalodinitrile and 78 parts of anhydrous aluminum chloride were mixed and stirred with 1250 parts of n-amyl alcohol. To this, 266 parts of DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene) was added, and the mixture was heated and refluxed at 136° C. for 5 hours. The reaction solution cooled to 30° C. with stirring was poured into a mixed solvent consisting of 5000 parts of methanol and 10000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine (P-1).
Elemental analysis of the obtained chloroaluminum phthalocyanine revealed that the calculated values (C) were 66.85%, (H) was 2.80%, and (N) was 19.49%, while the actual value (C) was 66.85%. 7%, (H) 3.0%, (N) 19.2% and identified as the desired compound.

(Production of phthalocyanine pigment precursor (P-2))
In a reaction vessel, 100 parts of chloroaluminum phthalocyanine (P-1) was slowly added to 1200 parts of concentrated sulfuric acid at room temperature. After stirring at 40°C for 3 hours, the sulfuric acid solution was poured into 24000 parts of cold water at 3°C. A blue precipitate was filtered, washed with water and dried to obtain 92 parts of hydroxyaluminum phthalocyanine (P-2).

(Production of phthalocyanine pigment precursor (CP-1))
In a reaction vessel, 100 parts of chloroaluminum phthalocyanine (P-1) was added to 1500 parts of concentrated sulfuric acid under an ice bath. After that, 40 parts of 1,3-dibromo-5,5-dimethylhydantoin (DBDMH) was gradually added and stirred at 25° C. for 6 hours. Subsequently, this sulfuric acid solution is poured into 9,000 parts of cold water at 3° C., and the precipitate formed is filtered, washed with water, washed with a 1% sodium hydroxide aqueous solution, and washed with water in that order. A pigment (CP-1) was obtained.
When the number of bromine substitutions was calculated for the obtained phthalocyanine pigment (CP-1), it was found to be 1.8 on average. A peak corresponding to the same molecular weight was also confirmed from the mass spectrum, and it was identified as the target compound. did. The halogen distribution width was 3.

(Production of phthalocyanine pigment precursor (CP-2))
In the production of the phthalocyanine pigment (CP-1), except that 40 parts of 1,3-dibromo-5,5-dimethylhydantoin (DBDMH) was changed to 80 parts of N-bromosuccinimide (NBS), 143 parts of phthalocyanine pigment (CP-2) were prepared in the same manner as in Table 1 shows the average value of the substitution number of halogen atoms represented by X and the halogen distribution width.

(Production of phthalocyanine pigment precursors (CP-3, CP-4))
In the production of the phthalocyanine pigment (CP-1), 143 parts of each phthalocyanine pigment (CP-3, CP -4) was obtained. Table 1 shows the average value of the substitution number of halogen atoms represented by X and the halogen distribution width.

(Production of phthalocyanine pigment precursor (CP-5))
In a reactor, 406 parts of aluminum chloride, 94 parts of sodium chloride and 10 parts of ferric chloride were heated and melted, and 100 parts of chloroaluminum phthalocyanine (P-1) was added at 140°C. The temperature was raised to 160° C. and 20 parts of chlorine was blown thereinto. The above reaction solution is poured into 5000 parts of water, filtered, washed with warm water, washed with a 1% hydrochloric acid aqueous solution, washed with warm water, washed with a 1% sodium hydroxide aqueous solution, and washed with warm water in this order, and then dried for crude chlorination. 160 parts of aluminum phthalocyanine were obtained.
The obtained crude chlorinated aluminum phthalocyanine was dissolved in 1200 parts of concentrated sulfuric acid and stirred at 50° C. for 3 hours. Next, the solution is poured into 7200 parts of water with stirring, heated to 70° C., filtered, washed with warm water, washed with a 1% sodium hydroxide aqueous solution, washed with warm water, dried, and dried to give 152 parts of a phthalocyanine pigment (CP-5). ). Table 1 shows the average value of the substitution number of halogen atoms represented by X and the halogen distribution width.

(Production of phthalocyanine pigment precursors (CP-6, CP-7))
In the production of the phthalocyanine pigment (CP-5), 168 parts of each phthalocyanine pigment (CP-6, CP -7) was obtained. Table 1 shows the average value of the substitution number of halogen atoms represented by X and the halogen distribution width.

(Production of phthalocyanine pigment precursor (CP-8))
In the production of the phthalocyanine pigment (CP-1), 40 parts of 1,3-dibromo-5,5-dimethylhydantoin (DBDMH) was added to 45 parts of 1,3-dibromo-5,5-dimethylhydantoin (DBDMH) and N- 141 parts of phthalocyanine pigment (CP-8) was obtained in the same manner as (CP-1) except that 45 parts of chlorosuccinimide (NCS) was used. Table 1 shows the average value of the substitution number of halogen atoms represented by X and the halogen distribution width.

(Production of phthalocyanine pigment precursor (CP-9))
In the production of the phthalocyanine pigment (CP-1), 40 parts of 1,3-dibromo-5,5-dimethylhydantoin (DBDMH) was changed to 120 parts of 1,3-diiodo-5,5-dimethylhydantoin (DIDMH). Except for this, 135 parts of a phthalocyanine pigment (CP-9) was obtained in the same manner as (CP-1). Table 1 shows the average value of the substitution number of halogen atoms represented by X and the halogen distribution width.

(Production of phthalocyanine pigment precursor (CP-10))
500 parts of concentrated sulfuric acid, 50 parts of hydroxyaluminum phthalocyanine (P-2), and 99.1 parts of N-bromosuccinimide (NBS) were added to a reaction vessel, stirred, and reacted at 20° C. for 3 hours. Thereafter, the reaction mixture was poured into 5000 parts of ice water at 3°C, and the precipitated solid was collected by filtration and washed with water. 500 parts of a 2.5% aqueous sodium hydroxide solution and the filtered residue were added to a beaker and stirred at 80° C. for 1 hour. Thereafter, this mixture was collected by filtration, washed with water and dried to obtain a phthalocyanine pigment (CP-10). Table 2 shows the yield, the yield, the average number of substituted halogen atoms represented by X, and the halogen distribution width.

(Production of phthalocyanine pigment precursor (CP-11))
In the production of the above phthalocyanine pigment (CP-10), 50 parts of hydroxyaluminum phthalocyanine (P-2) was added to 50 parts of chloroaluminum phthalocyanine (P-1), and 99.1 parts of NBS was added to 1,3-dibromo-5,5- A phthalocyanine compound (CP-11) was obtained in the same manner as for (CP-10) except that 104.4 parts of dimethylhydantoin (DBDMH) was used and the reaction time was changed from 3 hours to 4 hours. Table 2 shows the yield, the yield, the average number of substituted halogen atoms represented by X, and the halogen distribution width.

(Production of phthalocyanine pigment precursor (CP-12))
A phthalocyanine compound (CP-12) was obtained in the same manner as (CP-11) except that the amount of DBDMH was changed to the conditions shown in Table 2 in the production of the phthalocyanine pigment (CP-11). Table 2 shows the yield, the yield, the average number of substituted halogen atoms represented by X, and the halogen distribution width.

(Production of phthalocyanine pigment precursor (CP-13))
In a reactor, 203 parts of aluminum bromide, 47 parts of sodium bromide and 5 parts of ferric bromide were heated and melted, and 50 parts of hydroxyaluminum phthalocyanine (P-2) was added at 140°C. While the temperature was raised to 160° C. and 173.7 parts of bromine was blown thereinto, the mixture was reacted at 160° C. for 6 hours. The above reaction mixture was poured into 2500 parts of ice water at 3°C, and the precipitated solid was collected by filtration and washed with water. The residue was washed with a 1% hydrochloric acid aqueous solution, warm water, a 1% sodium hydroxide aqueous solution, and warm water in this order, and then dried to obtain 98 parts of brominated aluminum phthalocyanine. The obtained crude brominated aluminum phthalocyanine was dissolved in 980 parts of concentrated sulfuric acid and stirred at 50° C. for 3 hours. After that, the above sulfuric acid solution was poured into 9800 parts of ice water at 3° C., and the precipitated solid was collected by filtration, washed with water and dried. Then, 500 parts of a 2.5% aqueous sodium hydroxide solution and the filtered residue were added to a beaker and stirred at 80° C. for 1 hour. Thereafter, this mixture was collected by filtration, washed with water and dried to obtain a phthalocyanine pigment (CP-13). Table 2 shows the yield, the yield, the average number of substituted halogen atoms represented by X, and the halogen distribution width.

(Production of phthalocyanine pigment precursors (CP-14, CP-15))
In the production of the phthalocyanine pigment (CP-13), each phthalocyanine pigment (CP-14, CP-15) was prepared in the same manner as (CP-13), except that the amount of bromine was changed to the conditions shown in Table 2. ). Table 2 shows the yield, the yield, the average number of substituted halogen atoms represented by X, and the halogen distribution width.

(Production of phthalocyanine pigment precursor (CP-16))
In the production of the phthalocyanine pigment (CP-10), except that 99.1 parts of NBS were replaced with 74.4 parts of N-chlorosuccinimide (NCS) and the reaction time was changed from 3 hours to 4 hours, (CP-10) and A phthalocyanine pigment (CP-16) was obtained in the same manner. Table 2 shows the yield, the yield, the average number of substituted halogen atoms represented by X, and the halogen distribution width.

(Production of phthalocyanine pigment precursor (CP-17))
250 parts of aluminum chloride, 60 parts of sodium chloride and 2.25 parts of iodine were added to a reactor and stirred at 150° C. for 30 minutes. 50 parts of hydroxyaluminum phthalocyanine (P-2) was added thereto and dissolved by stirring at 155° C. for 30 minutes. Further, 58.5 parts of trichloroisocyanuric acid was added, and the mixture was stirred at 190°C for 5 hours. Thereafter, the reaction mixture was poured into 5000 parts of ice water at 3°C, and the precipitated solid was collected by filtration and washed with water. 500 parts of a 2.5% aqueous sodium hydroxide solution and the filtered residue were added to a beaker and stirred at 80° C. for 1 hour. Thereafter, this mixture was collected by filtration, washed with water and dried to obtain a phthalocyanine pigment (CP-17). Table 2 shows the yield, the yield, the average number of substituted halogen atoms represented by X, and the halogen distribution width.

(Production of phthalocyanine pigment precursors (CP-18 to CP-21))
In the production of the phthalocyanine pigment (CP-17), each phthalocyanine pigment (CP-18 to CP -21) was obtained. Table 2 shows the yield, the yield, the average number of substituted halogen atoms represented by X, and the halogen distribution width.

(Production of phthalocyanine pigment precursor (CP-22))
In a reaction vessel, 100 parts of chloroaluminum phthalocyanine (P-1) was added to 1500 parts of concentrated sulfuric acid under an ice bath. After that, 45.0 parts of trichloroisocyanuric acid was gradually added, and the mixture was stirred at 25°C for 3 hours. After that, 210.0 parts of 1,3-dibromo-5,5-dimethylhydantoin (DBDMH) was gradually added and stirred at 25° C. for 5 hours. Subsequently, this sulfuric acid solution is poured into 9,000 parts of cold water at 3°C, and the precipitate formed is filtered, washed with water, washed with a 1% aqueous sodium hydroxide solution, washed with water in that order, and dried to obtain 165.7 parts. of the phthalocyanine pigment (CP-22) was obtained. Table 2 shows the yield, the yield, the average number of substituted halogen atoms represented by X, and the halogen distribution width.

(Production of phthalocyanine pigment precursor (CP-23))
In a reaction vessel, 100 parts of chloroaluminum phthalocyanine (P-1) was added to 1500 parts of concentrated sulfuric acid under an ice bath. Then, 125.0 parts of trichloroisocyanuric acid was gradually added, and the mixture was stirred at 25°C for 3 hours. After that, 155.0 parts of 1,3-dibromo-5,5-dimethylhydantoin (DBDMH) was gradually added and stirred at 25° C. for 5 hours. Subsequently, this sulfuric acid solution is poured into 9000 parts of cold water at 3° C., and the precipitate formed is filtered, washed with water, washed with a 1% sodium hydroxide aqueous solution, washed with water in that order, dried, and dried to 157.1 parts. of the phthalocyanine pigment (CP-23) was obtained. Table 2 shows the yield, the yield, the average number of substituted halogen atoms represented by X, and the halogen distribution width.

(Production of phthalocyanine pigment precursor (CP-24))
In a reaction vessel, 100 parts of chloroaluminum phthalocyanine (P-1) was added to 1500 parts of concentrated sulfuric acid under an ice bath. After that, 45.0 parts of trichloroisocyanuric acid was gradually added, and the mixture was stirred at 25°C for 3 hours. After that, 205.0 parts of 1,3-diiodo-5,5-dimethylhydantoin (DIDMH) was gradually added and stirred at 25° C. for 5 hours. Subsequently, this sulfuric acid solution is poured into 9000 parts of cold water at 3° C., and the precipitate formed is filtered, washed with water, washed with a 1% sodium hydroxide aqueous solution, washed with water in that order, dried, and dried to 145.3 parts. of the phthalocyanine pigment (CP-24) was obtained. Table 2 shows the yield, the yield, the average number of substituted halogen atoms represented by X, and the halogen distribution width.

Structural formulas of the phthalocyanine pigments (CP-1) to (CP-24) are shown below. In the structural formula, the number of halogen atoms bonded to the phthalocyanine ring is the average number of substituted halogen atoms.

<Production of aluminum phthalocyanine pigment (PCY)>
(Production of phthalocyanine pigment (PCY-1))
1000 parts of 1-methyl-2-pyrrolidinone, 100 parts of phthalocyanine pigment (CP-1) and 40 parts of diphenylphosphinic acid were added to a reactor. After reacting at 85° C. for 3 hours, this solution was poured into 5000 parts of water. The reaction product was filtered, washed with 12,000 parts of water, and dried at 60° C. under reduced pressure for one day to obtain 124 parts of a phthalocyanine pigment (PCY-1).
When the number of bromine substitutions was calculated for the obtained phthalocyanine pigment (PCY-1), it was found to be 1.7 on average, and a peak corresponding to the same molecular weight was also confirmed from the mass spectrum, identifying it as the target compound. did. The halogen distribution width was 3.

(Production of phthalocyanine pigments (PCY-2 to CP-19))
In the production of the phthalocyanine pigment (PCY-1), the same operation as in (PCY-1) was performed except that the phthalocyanine pigment and the acidic compound used as raw materials were changed to the conditions shown in Table 3, respectively. PCY-2 to PCY-19) were obtained. Table 4 shows the average number of substituted halogen atoms represented by X and the halogen distribution width.

(Production of phthalocyanine pigment (PCY-20))
500 parts of N-methylpyrrolidone, 50 parts of phthalocyanine pigment (CP-10) and 18.2 parts of diphenyl phosphate were added to a reactor, heated to 90° C., and reacted for 8 hours. After cooling this to room temperature, this reaction liquid was poured into 4000 parts of water. The product was filtered, washed with methanol, and dried to obtain a phthalocyanine pigment (PCY-20). Table 6 shows the yield, the yield, the average number of substituted halogen atoms represented by X, and the halogen distribution width.

(Production of phthalocyanine pigments (PCY-21 to PCY-42))
In the production of the phthalocyanine pigment (PCY-20), the same operation as in (PCY-20) was performed except that the phthalocyanine pigment and the acidic compound used as raw materials were changed to the conditions described in Table 5, respectively. PCY-21 to PCY-42) were obtained. Table 6 shows the yield, the yield, the average number of substituted halogen atoms represented by X, and the halogen distribution width.

Structural formulas of the phthalocyanine pigments (PCY-1 to PCY-42) are shown below. In the structural formula, the number of halogen atoms bonded to the phthalocyanine ring is the average number of substituted halogen atoms.

<Manufacture of other pigments>
[Production of micronized green pigment (C-G1)]
C. I. 100 parts of Pigment Green 58 ("FASTOGEN Green A110" manufactured by DIC), 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70°C for 6 hours. This kneaded product is put into 3000 parts of hot water and stirred for 1 hour while heating to 70°C to form a slurry, which is repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, then dried at 80°C for a day and night to give a green color. 97 parts of a coloring agent (G-1) were obtained. The average primary particle size was 28.2 nm.

[Yellow colorant (CY1)]
Compound (1) was obtained according to the synthesis method described in JP-A-2008-81566.

100 parts of compound (1), 108 parts of tetrachlorophthalic anhydride, and 143 parts of benzoic acid were added to 300 parts of methyl benzoate, and the mixture was heated to 180° C. and reacted for 4 hours. Formation of the quinophthalone compound (b) and disappearance of the raw material compound (1) were confirmed by TOF-MS. After cooling to room temperature, the reaction mixture was poured into 3510 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol, and dried to obtain 120 parts of quinophthalone compound (b). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (b) described above.

Subsequently, 100 parts of the obtained quinophthalone compound (b), 1200 parts of sodium chloride and 120 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 60° C. for 8 hours. Next, this kneaded product is put into hot water and stirred for 1 hour while heating to about 70°C to form a slurry, which is repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80°C for a day and night. 98 parts of a yellow coloring agent (CY1) were obtained. The average primary particle size was 31.1 nm.

[Yellow colorant (CY2)]
Compound (2) was obtained according to the synthesis method described in JP-A-2008-81566.

100 parts of compound (2), 70 parts of 2,3-naphthalenedicarboxylic anhydride and 143 parts of benzoic acid were added to 300 parts of methyl benzoate, and the mixture was heated to 180° C. and reacted for 4 hours. Formation of the quinophthalone compound (a) and disappearance of the raw material compound (2) were confirmed by TOF-MS. After cooling to room temperature, the reaction mixture was poured into 3130 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol and dried to obtain 120 parts of quinophthalone compound (a). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (a) described above.

Next, 100 parts of the quinophthalone compound (a), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60° C. for 6 hours, and subjected to salt milling. The resulting kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70°C to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80°C for a day and night. , to give 98 parts of yellow colorant 2 (CY2). The average primary particle size was 31.3 nm.

[Yellow colorant (CY3)]
40 parts of 8-aminoquinaldine, 150 parts of 2,3-naphthalenedicarboxylic anhydride and 154 parts of benzoic acid were added to 200 parts of methyl benzoate, heated to 180° C., and stirred for 4 hours. After cooling to room temperature, the reaction mixture was poured into 5440 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol, and dried to obtain 116 parts of quinophthalone compound (c). As a result of mass spectrometry by TOF-MS, it was identified to be the aforementioned quinophthalone compound (c).

Subsequently, 100 parts of the obtained quinophthalone compound (c), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 60° C. for 8 hours. Next, this kneaded product is put into hot water and stirred for 1 hour while heating to about 70°C to form a slurry, which is repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80°C for a day and night. 97 parts of yellow colorant 3 (CY3) were obtained. The average primary particle size was 34.1 nm.

[Yellow colorant (CY4)]
C. I. Pigment Yellow 138 (PY138) (BASF "Pariotol Yellow K0960-HD") 100 parts, sodium chloride 700 parts, and diethylene glycol 180 parts are charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and heated at 80 ° C. for 6 hours. Kneaded. This mixture was poured into 2000 parts of hot water and stirred for 1 hour while heating to 80°C to form a slurry, which was repeatedly filtered and washed with water to remove salt and solvent. A colorant (CY4) was obtained. The average primary particle size was 40.2 nm.

[Yellow colorant (CY5)]
C. I. Pigment Yellow 138, C.I. I. A yellow coloring agent (CY5) was obtained in the same manner as the yellow coloring agent (CY4) except that Pigment Yellow 150 (“E4GN” manufactured by LANXESS) was used. The average primary particle size was 40.2 nm.

<Method for producing dye salt-forming compound>
[Salt-forming compound (Cx-1)]
A four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube and a condenser was charged with 80.0 parts of isopropyl alcohol and heated to 75° C. under a nitrogen stream. Separately, 25.0 parts of methyl methacrylate, 25.0 parts of n-butyl methacrylate, 30.0 parts of 2-ethylhexyl methacrylate, 20.0 parts of methacryloylaminopropyltrimethylammonium chloride, 47.0 parts of isopropyl alcohol, 2,2'- After 5.0 parts of azobis(2,4-dimethylvaleronitrile) and 18.0 parts of methyl ethyl ketone were homogenized, they were placed in a dropping funnel, attached to a four-necked separable flask, and added dropwise over 2 hours. After 2 hours from the completion of dropping, it was confirmed from the solid content that the polymerization yield was 98% or more and the mass average molecular weight (Mw) was 9000, and the mixture was cooled to 50°C. Thereafter, isopropyl alcohol was added for adjustment to obtain Resin 1 having a nonvolatile content of 40% by mass and having a cationic group in a side chain. The ammonium salt value of the obtained resin was 54 mgKOH/g.
Subsequently, the C.I. I. A salt-forming compound was prepared from Acid Red 289 and Resin 1 having a cationic group in the side chain obtained above.
To 2000 parts of water was added 30 parts of Resin 1 having a cationic group on its side chain in terms of solid content, and the mixture was sufficiently stirred and mixed, and then heated to 60°C. On the other hand, 10 parts of C.I. I. An aqueous solution was prepared by dissolving Acid Red 289, and was added dropwise to the previous resin solution. After dropping, the mixture was stirred at 60° C. for 120 minutes to sufficiently react. To confirm the end point of the reaction, the reaction solution was added dropwise to a filter paper, and the point at which no bleeding occurred was regarded as the end point, and it was determined that a salt-forming compound was obtained. After allowing to cool to room temperature while stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing moisture with a dryer. I. A salt-forming compound (Cx-1) of Acid Red 289 and resin 1 having a cationic group in the side chain was obtained. At this time, C.I. I. The content of the active coloring component derived from Acid Red 289 was 60% by mass.

<Dye derivative (Cy)>
(Dye derivative (Cy-1))
A diketopyrrolopyrrole pigment derivative represented by formula (9) was used as the dye derivative (Cy-1).

formula (9)

(Dye derivative (Cy-2))
A dye derivative (Cy-2) was obtained according to the synthesis method described in JP-A-2004-067715.
Dye derivative (Cy-2)

<Production of resin-type acidic dispersant (Xa)>
[Resin type acidic dispersant (Xa-1)]
50 parts of methyl methacrylate, 50 parts of n-butyl methacrylate and 45.4 parts of PGMAc were introduced into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser and a stirrer, and the contents were purged with nitrogen gas. The inside of the reaction vessel was heated to 70° C., 6 parts of 3-mercapto-1,2-propanediol was added, and 0.12 part of AIBN (azobisisobutyronitrile) was further added and reacted for 12 hours. Solid content measurement confirmed that 95% had reacted. Next, add 9.7 parts of pyromellitic anhydride, 70.3 parts of PGMAc, and 0.20 parts of DBU (1,8-diazabicyclo-[5.4.0]-7-undecene) as a catalyst, and heat at 120°C. was reacted for 7 hours. It was confirmed by acid value measurement that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. PGMAc was added to adjust the non-volatile content to 30% to obtain a dispersant (Xa-1) having an acid value of 43 and a weight average molecular weight of 9,000.

[Resin type acidic dispersant (Xa-2)]
A resin-type acidic dispersant (Xa-2) was prepared in the same manner as the resin-type acidic dispersant (Xa-1), except that the amount (parts by mass) of each component added was changed as shown in Table 7.

Abbreviations in Table 7 are shown below.
MMA: methyl methacrylate n-BA: n-butyl acrylate AIBN: 2,2'-azobisisobutyronitrile TMA: trimellitic anhydride (Mitsubishi Gas Chemical Co., Ltd.)
PMA: pyromellitic dianhydride (manufactured by Daicel Chemical Industries, Ltd.)
DBU: 1,8-diazabicyclo-[5.4.0]-7-undecene (manufactured by San-Apro Co., Ltd.)

<Production of resin-type basic dispersant (Xb)>
[Resin type basic dispersant (Xb-1)]
133 parts of PGMAc was charged into a reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, and the temperature was raised to 100° C. while purging with nitrogen. 85 parts of N,N-dimethylaminoethyl methacrylate, 40 parts of 3-(methacryloyloxymethyl) 3-ethyloxetane, 45 parts of methyl acrylate, 35 parts of methyl methacrylate, 63 parts of PGMAc, and 2,2'-azobis (2 ,4-dimethylvaleronitrile) was charged, stirred until uniform, added dropwise to the reactor over 2 hours, and then the reaction was continued at the same temperature for 3 hours. Thus, a vinyl dispersant (Xb-1) having an amine value per solid content of 146 mgKOH/g and a number average molecular weight of 5,000 (Mn) and having an amino group and a crosslinkable functional group was obtained.

[Resin type basic dispersant (Xb-2 to 3)]
A vinyl resin having an amino group and a crosslinkable functional group (Xb- 2-3) were obtained.

<Production of Binder Resin Solution (Xc)>
[Binder resin solution (Xc-1)]
200 parts of propylene glycol monomethyl ether acetate (PGMAc) was placed in a reaction vessel equipped with a separable 4-necked flask, a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer, and heated to 120°C while introducing nitrogen gas into the vessel. At the same temperature, a mixture of 60 parts of cyclohexyl methacrylate, 20 parts of styrene, 58 parts of glycidyl methacrylate, and 8 parts of azobisisobutyronitrile as a catalyst required for the reaction of the precursor in this stage was added from a dropping tube over 2.5 hours. was added dropwise to carry out a polymerization reaction.
Next, the inside of the flask was replaced with air, and 29 parts of acrylic acid and 0.6 parts of trisdimethylaminomethylphenol and 0.6 parts of hydroquinone as catalysts required for the reaction of the precursor at this stage were added, and the mixture was heated at 120°C for 5 hours. reacted. Since the acrylic acid introduced is ester-bonded to the epoxy group terminal of the glycidyl methacrylate constitutional unit, it does not generate a carboxyl group in the resin structure.
Further, 33 parts of tetrahydrophthalic anhydride and 1 part of triethylamine as a catalyst required for the reaction of the precursor at this stage were added and reacted at 120° C. for 4 hours. In the added tetrahydrophthalic anhydride, one of the two carboxyl groups produced by cleavage of the carboxylic anhydride moiety is ester-bonded to the hydroxyl group in the resin structure, and the other produces a terminal carboxyl group.
Propylene glycol monomethyl ether acetate was added so that the non-volatile content was 30% to obtain a resin solution (Xc-1).

[Binder resin solution (Xc-2, 3)]
Binder resin solutions (Xc-2, 3) were prepared in the same manner as the binder resin solution (Xc-1), except that the materials and amounts charged were changed as shown in Table 9-1.

[Binder resin solution (Xc-4)]
200 parts of propylene glycol monomethyl ether acetate (PGMAc) was placed in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube, and the mixture was stirred while being replaced with nitrogen and heated to 120°C. A monomer mixture consisting of 10 parts of cyclohexyl methacrylate, 20 parts of styrene, 41 parts of methacrylic acid, and 60 parts of methyl methacrylate to which 4 parts of azobisisobutyronitrile was added was added dropwise from the dropping funnel to the flask over 2 hours. Stirring was continued for 2 hours at 120° C. for aging. Next, the inside of the flask was replaced with air, and 0.6 parts of trisdimethylaminomethylphenol and 0.1 parts of hydroquinone were added to 69 parts of glycidyl methacrylate, and the mixture was reacted and stirred at 120° C. for 6 hours. Propylene glycol monomethyl ether acetate was added so that the non-volatile content was 30% to obtain a resin solution (Xc-4).

[Binder resin solution (Xc-5)]
200 parts of propylene glycol monomethyl ether acetate (PGMAc) was charged into a reaction vessel equipped with a separable 4-necked flask, a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube and a stirring device, heated to 80° C., and placed in the reaction vessel. After replacing with nitrogen, from the dropping tube, 50 parts of benzyl methacrylate, 30 parts of 2-hydroxyethyl methacrylate, 20 parts of methacrylic acid, 40 parts of methyl methacrylate, paracumylphenol ethylene oxide modified acrylate (manufactured by Toagosei Co., Ltd. "Aronix M110" ) and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropwise addition was completed, the reaction was continued for an additional 3 hours. Propylene glycol monomethyl ether acetate was added so that the non-volatile content was 30% to obtain a resin solution (Xc-5).

[Binder resin solution (Xc-6)]
A binder resin solution (Xc-6) was prepared in the same manner as the binder resin solution (Xc-5), except that the materials and amounts charged were changed as shown in Table 9-1.

[Binder resin solution (Xc-7)]
200 parts of cyclohexanone was charged into a reaction vessel equipped with a separable 4-necked flask, a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube and a stirring device, heated to 80 ° C., and after replacing the inside of the reaction vessel with nitrogen, dropping From a tube, 28 parts of methacrylic acid, 30 parts of paracumylphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 28 parts of benzyl methacrylate, 48 parts of glycerin monomethacrylate, and 1 part of 2,2'-azobisisobutyronitrile .3 parts of the mixture was added dropwise over 2 hours. After completion of dropping, the reaction was continued for 3 hours to obtain a resin solution. Next, the nitrogen gas was stopped and dry air was introduced into the entire amount of the resin solution obtained while stirring for 1 hour. A mixture of 66 parts, 0.1 part of dibutyl tin laurate and 26 parts of cyclohexanone was added dropwise at 70° C. over 3 hours. After the dropwise addition was completed, the reaction was continued for an additional hour to obtain an acrylic resin solution. Cooled to room temperature. Propylene glycol monomethyl ether acetate was added so that the non-volatile content was 30% to obtain a resin solution (Xc-7).

Table 9-2 shows the composition ratios and molecular weights of the prepared binder resin solutions (Xc-1 to 7).

Abbreviations in Tables 9-1 and 9-2 are shown below.
St: Styrene BzMA: Benzyl methacrylate M110: Paracumylphenoxyethyl acrylate CHMA: Cyclohexyl methacrylate BMA: Butyl methacrylate MAA: Methacrylic acid MMA: Methyl methacrylate GMA: Glycidyl methacrylate AA: Acrylic acid THPA: Tetrahydrophthalic anhydride SucAA: Succinic anhydride GMA-AA: AA (acrylic acid) is added and bonded to the epoxy site of the structural unit (glycidyl methacrylate) GMA-AA-THPA: Acrylic acid is added and bonded to the structural unit glycidyl methacrylate, resulting in GMA-AA-SucAA in which tetrahydrophthalic anhydride is esterified and bonded to the OH group: acrylic acid is added and bonded to the structural unit glycidyl methacrylate, and the OH group generated at that time is esterified with succinic anhydride. Bound GLM: glycerol monomethacrylate MOI: 2-methacryloyloxyethyl isocyanate GLM-MOI: reactant of 2-methacryloyloxyethyl isocyanate to glycerol monomethacrylate HEMA: hydroxyethyl methacrylate

<Production of photopolymerizable monomer>
[Urethane-based photopolymerizable monomer 1 (B-1)]
18.8 g of hexyl isocyanate, 51.3 g of pentaerythritol triacrylate, 75.1 g of propylene glycol monomethyl ether acetate, and 0.02 g of methylhydroquinone were placed in a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, and thermometer. Then, 0.12 g of dioctyltin was added as a catalyst, and the temperature was raised to 100°C. After reacting at 100° C. for 3 hours and confirming disappearance of the isocyanate peak by IR, the reaction was terminated by cooling to room temperature. Thereafter, the solvent was removed from this reaction solution under reduced pressure using an evaporator to obtain a colorless and transparent urethane-based photopolymerizable monomer 1 (B-1) having a mass average molecular weight of MW 4,800.

[Urethane-based photopolymerizable monomer 2 (B-2)]
8.8 g of 2-ethyl-2-methyl-1,3-propanediol, 11.3 g of tetrahydrophthalic anhydride, and dimethylbenzylamine were placed in a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, and thermometer. 0.1 g (manufactured by Wako Pure Chemical Industries, Ltd.) and 21.3 g of propylene glycol monomethyl ether acetate were added and the temperature was raised to 120°C. The mixture was stirred at 120°C for 2 hours and cooled to 80°C. Next, 0.05 g of methylhydroquinone, 21.3 g of hexamethylene diisocyanate, 68.4 g of pentaerythritol triacrylate, and 93.5 g of propylene glycol monomethyl ether acetate were charged, and then 0.23 g of dioctyltin as a catalyst was charged, and the temperature was raised to 100°C. did. After reacting at 100° C. for 3 hours and confirming disappearance of the isocyanate peak by IR, the reaction was terminated by cooling to room temperature. Thereafter, the solvent was removed from this reaction solution under reduced pressure using an evaporator to obtain a colorless transparent urethane-based photopolymerizable monomer 2 (B-2) having a mass average molecular weight of MW 7,200 and having an acid group.

[Urethane-based photopolymerizable monomer 3 (B1-1)]
A four-necked flask equipped with a stirrer, a reflux condenser, a dry air inlet tube and a thermometer was charged with 5.0 g of trimethylolpropane, 18.8 g of hexamethylene diisocyanate, 51.3 g of pentaerythritol triacrylate, and 75 g of propylene glycol monomethyl ether acetate. 1 g of methylhydroquinone, 0.02 g of methylhydroquinone, and then 0.12 g of dioctyltin as a catalyst were charged, and the temperature was raised to 100.degree. After reacting at 100° C. for 3 hours and confirming disappearance of the isocyanate peak by IR, the reaction was terminated by cooling to room temperature. Thereafter, the solvent was removed from this reaction solution under reduced pressure using an evaporator to obtain a colorless and transparent urethane-based photopolymerizable monomer 3 (B1-1) having a mass average molecular weight of MW 7,600.

[Urethane-based photopolymerizable monomer 4 (B1-2)]
10.0 g of trimethylolpropane, 11.3 g of tetrahydrophthalic anhydride, and 0.1 g of dimethylbenzylamine (manufactured by Wako Pure Chemical Industries, Ltd.) were placed in a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, and thermometer. , and 21.3 g of propylene glycol monomethyl ether acetate were charged, and the temperature was raised to 120°C. The mixture was stirred at 120°C for 2 hours and cooled to 80°C. Next, 0.05 g of methylhydroquinone, 12.5 g of hexamethylene diisocyanate, 34.2 g of pentaerythritol triacrylate, and 93.5 g of propylene glycol monomethyl ether acetate were charged, and then 0.23 g of dioctyltin as a catalyst was charged, and the temperature was raised to 100°C. did. After reacting at 100° C. for 3 hours and confirming disappearance of the isocyanate peak by IR, the reaction was terminated by cooling to room temperature. Thereafter, the solvent was removed from this reaction solution under reduced pressure using an evaporator to obtain a colorless transparent urethane-based photopolymerizable monomer 4 (B1-2) having a mass average molecular weight of MW 7,200 and having an acid group (B1-2).

The resulting photopolymerizable monomer and photopolymerizable compound nB-1: number of urethane bonds of dipentaerythritol hexaacrylate (“Aronix M-402” manufactured by Toagosei Co., Ltd.), presence or absence of acid groups, and unsaturated Table 10 shows the number of functional groups.

<Production of pigment dispersion>
[Red Pigment Dispersion (PR-1)]
After uniformly stirring and mixing a mixture having the following composition, using zirconia beads with a diameter of 1 mm, the mixture was dispersed for 5 hours with an Eiger mill (manufactured by Eiger Japan Co., Ltd. "Mini Model M-250 MKII"), and then filtered through a 5 μm filter. A red pigment dispersion (PR-1) was prepared.
Anthraquinone pigment (CI Pigment Red 177): 10.0 parts ("Chromophthal Red A2B" manufactured by BASF)
Diketopyrrolopyrrole pigment derivative Cy-1 represented by formula (9): 2.0 parts Resin type acidic dispersant solution (Xa-1): 8.0 parts Binder resin solution (Xc-5): 12. 0 parts Binder resin solution (Xc-1): 6.7 parts Propylene glycol monomethyl ether acetate: 61.3 parts

[Preparation of pigment dispersions (PR-2, PB-1, PG-1 to 43, PY-1 to 5]
Pigment dispersions PR-2, PB-1, PG-1 to 43, and PY-1 to 5 were prepared in the same manner as the red pigment dispersions using mixtures of the compositions shown in Table 11.

<Preparation of coloring composition>
[Adjustment of colored compositions (P-1) to (P-55)]
The resulting pigment dispersion and salt-forming compound are mixed under C light source so that the chromaticities are red: x = 0.600, blue: y = 0.080, and yellowish green: y = 0.600. Colored compositions (P-1) to (P-55) were obtained by adjusting with a solvent so that the part was 20%. P-1, 2, 4, 6 to 48 were used as they were without mixing the pigment dispersion.

<Preparation of photosensitive coloring composition>
Each material was mixed and stirred at the prescription ratio shown in Tables 14 and 15, and filtered through a 1 μm filter to obtain a photosensitive coloring composition of each color.

Abbreviations in Tables 14 and 15 are shown below.
- Photopolymerization initiator A1: a compound represented by the following formula (2) Formula (2)

- Photopolymerization initiator Y1: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (manufactured by BASF "Irgacure 907")
Photopolymerization initiator Y2: 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (manufactured by BASF "Irgacure 379" )
- Photopolymerization initiator Y3: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (manufactured by BASF "Lucirin TPO")
- Photopolymerization initiator Y4: 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole (manufactured by Kurogane Kasei Co., Ltd. "Biimidazole")
- Photoinitiator Y5: ethan-1-one, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl], 1-(O-acetyloxime)
(“Irgacure OXE02” manufactured by BASF)
・ Leveling agent: “BYK-330” manufactured by BYK
(Solution obtained by diluting 1 part of non-volatile content of 100% by mass with 99 parts of cyclohexanone)

・PGMAc: propylene glycol monomethyl ether acetate ・EEP: ethyl 3-ethoxypropionate

<Other additives>
・ Sensitizer E1: 2,4-diethylthioxanthone (“Kayacure DETX-S” manufactured by Nippon Kayaku Co., Ltd.)
- Sensitizer E2: 4,4'-bis (diethylamino) benzophenone ("EAB-F" manufactured by Hodogaya Chemical Industry Co., Ltd.)
・ Silane coupling agent S1: 3-glycidoxypropylmethyldimethoxysilane (“Z-6044” manufactured by Dow Corning Toray Co., Ltd.)
・ Silane coupling agent S2: 3-methacryloxypropyltriethoxysilane (“KBE-503” manufactured by Shin-Etsu Chemical Co., Ltd.)
・ Silane coupling agent S3: 3-acryloxypropyltrimethoxysilane ("KBM-5103" manufactured by Shin-Etsu Chemical Co., Ltd.)
- Polyfunctional thiol F1: trimethylolpropane tri(3-mercaptobutyrate) (manufactured by Showa Denko "TPMB")
- Polyfunctional thiol F2: pentaerythritol tetrakis (3-mercaptopropionate) ("PEMP" manufactured by Sakai Chemical Industry Co., Ltd.)
· Antioxidant G1: 2 pentaerythrityl-tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate]
("IRGANOX1010" manufactured by BASF)
- Polymerization inhibitor H1: methyl hydroquinone (manufactured by Seiko Chemical Co., Ltd. "MH")

<Evaluation of photosensitive coloring composition>
A filter segment pattern was formed on the obtained photosensitive colored composition by the following method.

[Filter segment pattern formation]
After applying the obtained photosensitive coloring composition to a glass substrate of 10 cm × 10 cm by spin coating, the solvent was removed by heating at 70 ° C. for 15 minutes in a clean oven to obtain a coating film of about 2 μm. . Then, after cooling the substrate to room temperature, it was exposed to ultraviolet light through a photomask having a stripe pattern of 100 μm width (pitch: 200 μm) and 25 μm width (pitch: 50 μm) using an extra-high pressure mercury lamp. Thereafter, the substrate was developed by spraying with an aqueous solution of sodium carbonate at 23° C., washed with deionized water, air-dried, and heated at 230° C. for 30 minutes in a clean oven. The spray development was carried out for the shortest time in which the coating film with each photosensitive coloring composition could be patterned without development residue, and this was defined as the proper development time. Dektak 3030 (manufactured by Japan Vacuum Engineering Co., Ltd.) was used to determine the film thickness of the coating film.

The patterns obtained were evaluated for pattern shape and chemical resistance by the following methods. Further, for Examples 6 to 48 using a blue-green pigment dispersion mixture, brightness was evaluated by the following method. The results are shown in Table 16.

[Chemical resistance evaluation]
For the filter segment formed by the above method,
Chromaticity ([L*(1), a*(1), b*(1)]) under C light source was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). Furthermore, after that, the coating film obtained as a chemical resistance test was immersed in 1-methyl-2-pyrrolidone for 30 minutes, then the 1-methyl-2-pyrrolidone was washed with pure water, air-dried, and then the color was measured with a C light source. The degree ([L*(2), a*(2), b*(2)]) was measured, and the color difference ΔE*ab was determined by the following formula.
ΔE*ab = [[L*(2)-L*(1)]2+[a*(2)-a*(1)]2+[b*(2)-b*(1)]2] 1/2
Furthermore, the pattern on the 100 μm photomask portion after the chemical immersion was visually observed with an optical microscope and evaluated. Evaluation criteria are as follows.
◎: No change in appearance, color difference (ΔE*ab) less than 3.0 ○: Wrinkles occur in part of appearance, but color difference (ΔE*ab) is less than 3.0 △: Wrinkles in part of appearance etc., but the color difference (ΔE*ab) is 3.0 or more and less than 5.0 ×: peeling occurs, or the color difference (ΔE*ab) is 5.0 or more

[Pattern shape evaluation]
The section of the pattern in the 100 μm photomask portion of the filter segment formed by the above method was observed and evaluated using an electron microscope. The cross section of the pattern has a favorable forward taper. Evaluation criteria are as follows.
◎: Smooth forward tapered cross section ○: Forward tapered cross section ×: Reverse tapered cross section

As shown in Table 16, the filter segments and black matrices formed using the photosensitive coloring compositions of Examples 1 to 78 had good pattern shape and chemical resistance. In addition, Examples 43 to 46 containing a polyfunctional thiol (F) were excellent in sensitivity. In addition, Examples 33, 35, 47 and 48 containing an antioxidant (G) or a polymerization inhibitor (H) were excellent in resolution. When other oxime ester photopolymerization initiators were used as in Comparative Example 1, even though the shape was good, the brightness and chemical resistance were poor, and all the evaluation items were not good. . In addition, when the photopolymerizable monomer (B) was not present as in Comparative Example 2, the shape and chemical resistance were poor, and all the evaluation items were not satisfactory.

10 liquid crystal display device 11 transparent substrate 12 TFT array 13 transparent electrode layer 14 alignment layer 15 polarizing plate 21 transparent substrate 22 color filter 23 transparent electrode layer 24 alignment layer 25 polarizing plate 30 backlight unit 31 white LED light source LC liquid crystal

Claims (9)

A photopolymerization initiator (A) represented by the following general formula (1), a urethane-based photopolymerizable monomer (B), a colorant (C), and a binder resin (X), wherein the urethane-based photopolymerization A photosensitive coloring composition for a color filter, wherein the photopolymerizable monomer (B) contains two or more photopolymerizable monomers having different numbers of urethane bonding sites.

General formula (1)

[In general formula (1), R ₁ represents an alkyl group, R ₂ and R ₃ represent a hydrogen atom, and R ₄ represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. ] The photopolymerization initiator (A) represented by the general formula (1) contains a photopolymerization initiator represented by the following chemical formula (2) or (3), the photosensitive for color filters according to claim 1 coloring composition.

chemical formula (2)

3. The photosensitive material for a color filter according to claim 1, wherein the urethane-based photopolymerizable monomer (B) comprises a photopolymerizable monomer (B1) having 3 or more urethane bonding sites. coloring composition. The photosensitive coloring composition for color filters according to any one of claims 1 to 3, wherein the coloring agent (C) contains a halogenated metal phthalocyanine. 5. The photosensitive coloring composition for color filters according to claim 4, wherein the halogenated metal phthalocyanine contains an aluminum phthalocyanine pigment (PCY) represented by the following general formula (2).
general formula (2)

[In the general formula (2),
X represents a halogen atom and n represents an integer of 1-16. However, the average number of substituted halogen atoms represented by X is 1 to 15, and the halogen distribution width is 2 or more.
Y represents -OP(=O)R ₁ R ₂ , -OC(=O)R ₃ or -OS(=O) ₂ R ₄ .
R ₁ and R ₂ are each independently a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxyl group, or It represents an aryloxy group which may have a substituent.
R ₃ is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, or an optionally substituted represents a heterocyclic group.
R ₄ represents a hydroxyl group, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted heterocyclic group. ] The photosensitive coloring composition for color filters according to any one of claims 1 to 5, further comprising a resin type dispersant. 7. The photosensitive coloring composition for color filters according to claim 6, wherein the resin type dispersant comprises an acidic resin type dispersant and a basic resin type dispersant. A color filter comprising a substrate, a filter segment formed using the photosensitive coloring composition for a color filter according to any one of claims 1 to 7, and a black matrix. A liquid crystal display device comprising the color filter according to claim 8 .

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