TWI820050B - Photosensitive coloring composition for color filter, and color filter - Google Patents

Abstract

An object of the present invention is to provide a photosensitive coloring composition for color filters and a color filter. A photosensitive coloring composition for color filters, which contains a resin-type dispersant composed of a hydroxyl group of a compound (a) having two hydroxyl groups and a thiol group in the molecule, and a benzene-type dispersant. Ethylenically unsaturated monomer (c) containing an ethylenically unsaturated monomer (b) containing a hydroxyl group is polymerized in the presence of a reaction product of an acid anhydride group of tetracarboxylic anhydride and/or trimellitic anhydride. Resin obtained by reacting the hydroxyl group of a hydroxyl-containing polymer with the isocyanate group of the compound (d) having one isocyanate group and one or more (meth)acrylyl groups, and an ethylenically unsaturated monomer containing a hydroxyl group The content of (b) is 35 mass% or more and 80 mass% or less based on the total amount of ethylenically unsaturated monomer (c).

Description

Photosensitive coloring composition for color filter, and color filter

The present invention relates to a photosensitive coloring composition that can be used in the formation of color filters used in liquid crystal display devices or organic electroluminescence (EL) displays.

Color filters are made by arranging two or more fine strip-shaped filter segments of different hues parallel to each other (in a stripe shape) or crossing each other on a transparent substrate such as a glass substrate. It is formed by, or by arranging two or more fine filter segments with different hues in order in the longitudinal and transverse directions. The filter segments have a small size ranging from several microns to hundreds of microns, and are neatly arranged in a prescribed arrangement for each hue.

Currently, the mainstream method for manufacturing color filters is a method called a pigment dispersion method, which uses a pigment with excellent light resistance, heat resistance, etc. as a coloring material. In addition, in the pigment dispersion method, the following method is used to manufacture a color filter. First, a photosensitive coloring composition (pigment resist) in which a pigment is dispersed in a photosensitive transparent resin solution is applied to a transparent substrate such as glass. After the solvent is removed from the coating film by drying, the coating film is exposed using a pattern corresponding to a filter segment of a certain color. Then, the unexposed portion of the coating film is removed by development, and the Heating and other processing may be required later. Thereby, a filter segment pattern of the first color is obtained. Furthermore, filter segment patterns of other colors are formed by performing the same operation as described above, thereby completing the color filter.

In recent years, high color reproduction of displays has become an important trend. High color reproducibility of displays is centered on research to improve the color reproducibility of backlights. However, in order to improve color reproducibility of color filters, very dense colors must be used. In this case, in the exposure step of forming the pattern of the color filter, the amount of light reaching the bottom of the coating film is weak, so photohardening often becomes insufficient, resulting in problems such as failure to obtain a pattern of a desired shape.

Specifically, the photosensitive colored composition is required to have dimensional stability such that the size of the pattern obtained in the color filter manufacturing step is limited to a certain degree of variation when the exposure amount in the exposure step is varied. , but there is a tendency for such dimensional stability to deteriorate in photosensitive colored compositions that achieve high color reproduction. Similarly, in photosensitive colored compositions that achieve high color reproduction, the linearity of patterns tends to deteriorate.

Therefore, Patent Document 1 discloses a composition using a polymer with a specific structure. Patent Document 2 discloses a method of providing an anchor layer on a substrate. Patent Document 3 discloses a composition using a polymer with a specific structure. Patent Document 4 discloses a composition using a polymerization initiator with a specific structure. Patent Document 5 discloses a composition using a thiol-based compound.

[Prior art documents]

[Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2013-254047

[Patent Document 2] Japanese Patent Application Publication No. 2013-073115

[Patent Document 3] Japanese Patent Application Laid-Open No. 2012-108227

[Patent Document 4] Japanese Patent Application Publication No. 2011-002796

[Patent Document 5] Japanese Patent Application Publication No. 2010-039475

However, there is a problem that existing compositions cannot fully improve the pattern shape, dimensional stability, and pattern linearity after development.

An object of the present invention is to provide a photosensitive coloring composition that has good viscosity stability, has good patterning properties (resolution, linearity, dimensional stability, development stability) when forming a film, and can form dimensional stability. and photosensitive coloring compositions for resist patterns with good linearity, and color filters.

The photosensitive coloring composition for color filters of the present invention is <1> a photosensitive coloring composition for color filters, which contains a colorant (A), a resin dispersant (B), and a photopolymerization initiator (C), organic solvent (D) and polymerizable compound (E). Resin-type dispersant (B) is composed of the hydroxyl group of the compound (a) having two hydroxyl groups and one thiol group in the molecule, and pyromellitic acid. Ethylenically unsaturated monomer (c) containing an ethylenically unsaturated monomer (b) containing a hydroxyl group is polymerized in the presence of a reaction product of an acid anhydride group of formic anhydride and/or trimellitic anhydride. The hydroxyl group of a hydroxyl polymer has one isocyanate group and one or more (meth)acrylyl groups. A resin obtained by reacting the isocyanate group of substance (d), and the content of the structural units derived from the ethylenically unsaturated monomer (b) containing a hydroxyl group is relative to the content of the structural units derived from the ethylenically unsaturated monomer (c). The total amount of structural units is 35 mass% or more and 80 mass% or less.

<2> The photosensitive coloring composition for color filters, wherein (the total mass of the structural units derived from (c) ethylenically unsaturated monomer + derived from (d) has one isocyanate group and more than one The total mass of the structural units of the (meth)acrylyl compound)/((meth)acrylyl group derived from (d) contained in the structural units of the compound having one isocyanate group and more than one (meth)acrylyl group The double bond equivalent (Z) in the side chain of the resin-type dispersant (B) represented by the molar (mol) number of the acrylic group) is 300g/mol to 600g/mol.

<3> The photosensitive colored composition for color filters, wherein the content of the structural unit derived from the hydroxyl-containing ethylenically unsaturated monomer (b) in the resin-type dispersant (B) is relative to the source. It is 38 mass % or more and 60 mass % or less based on the total amount of the structural units of the ethylenically unsaturated monomer (c).

<4> The photosensitive coloring composition for color filters, wherein the content of the colorant (A) is 40 mass % or more based on the total amount of non-volatile components of the photosensitive coloring composition for color filters.

<5> The photosensitive colored composition for color filters, wherein the photopolymerization initiator (C) contains an oxime ester compound.

<6> A color filter including a filter segment formed of the photosensitive colored composition for the color filter on a base material.

According to the present invention, it is possible to provide a photosensitive coloring composition that has good viscosity stability, has good patterning properties (resolution, linearity, dimensional stability, development stability) when forming a film, and can form dimensional A photosensitive coloring composition for a resist pattern with excellent stability and linearity, and a color filter.

Hereinafter, embodiments of the present invention will be described in detail. In addition, in this specification, (meth)acrylate means acrylate and/or methacrylate, and (meth)acrylic acid means acrylic acid and/or methacrylic acid.

<Photosensitive coloring composition for color filters>

The photosensitive coloring composition for color filters of the present invention contains a colorant (A), a resin dispersant (B), a photopolymerization initiator (C), an organic solvent (D) and a polymerizable compound (E), And it is characterized in that the resin dispersant (B) is composed of the hydroxyl group of the compound (a) having two hydroxyl groups and one thiol group in the molecule, and the acid anhydride group of pyromellitic anhydride and/or trimellitic anhydride. In the presence of the reaction product, the hydroxyl group of the hydroxyl-containing polymer obtained by polymerizing the ethylenically unsaturated monomer (c) containing the hydroxyl-containing ethylenically unsaturated monomer (b) and having one isocyanate group A resin formed by reacting one or more isocyanate groups of a (meth)acrylyl compound (d), and the content of the hydroxyl-containing ethylenically unsaturated monomer (b) is relative to the ethylenically unsaturated monomer The total amount of body (c) is 35 mass% or more and 80 mass% or less.

Hereinafter, the photosensitive colored composition for color filters of the present invention will be described in detail.

<Resin type dispersant (B)>

The resin-type dispersant (B) of the present invention can be obtained by initially producing a hydroxyl group of a compound (a) having two hydroxyl groups and one thiol group, and mixing it with pyromellitic anhydride and/or trimellitic anhydride. the first step of producing a reaction product of an acid anhydride group; then, using the remaining thiol group of the reaction product as a chain transfer agent to make the ethylenically unsaturated monomer containing the hydroxyl-containing ethylenically unsaturated monomer (b) The second step of producing a hydroxyl-containing polymer into which a vinyl polymer moiety having a hydroxyl group is introduced by radical polymerization of the mass (c); and further as having one isocyanate group and one or more (meth)acrylic The third step of the reaction of the acyl compound (d). The plurality of carboxyl moieties in the resin-type dispersant (B) of the present invention function as a pigment adsorption section, and the vinyl polymer moiety functions as a solvent affinity section.

In addition, the resin-type dispersant (B) of the present invention is obtained through a plurality of reactions such as the reaction between a hydroxyl group and an acid anhydride group, a radical polymerization reaction using a residual thiol group as a chain transfer agent, and a reaction between a residual hydroxyl group and an isocyanate group. Since it is impossible or basically impractical to express a complex structure using a general formula (structure), it is described using a manufacturing method.

(Compound (a) having two hydroxyl groups and one thiol group in the molecule)

Examples of the compound (a) having two hydroxyl groups and one thiol group in the molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, and 3-mercapto- 1,2-propanediol (alias: 1-thioglycerol), 2-mercapto-1,3-propanediol, 2-mercapto-1,2-propane Diol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2 -Mercaptoethyl-2-methyl-1,3-propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol, etc.

In this specification, the vinyl polymer part containing the ethylenically unsaturated monomer (b) containing a hydroxyl group and obtained by radical polymerization of the ethylenically unsaturated monomer (c) refers to a resin-type dispersed In the structure of Agent B, the compound (a) having two hydroxyl groups and one thiol group is reacted with pyromellitic anhydride and/or trimellitic anhydride and is a continuous polyester part that does not contain a carboxyl group. part. One molecule constituting the resin-type dispersant (B) contains one vinyl polymer part when only trimellitic anhydride is used, and a plurality of vinyl polymer parts when pyromellitic anhydride is used. object part. From the viewpoint of dispersion stability, it is more preferable to use pyromellitic anhydride.

As the catalyst used when reacting an acid anhydride group and a hydroxyl group in the present invention, a known catalyst can be used. Examples include: triethylamine, triethylenediamine, N,N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo-[5.4.0]-7-eleven Alkene, 1,5-diazabicyclo-[4.3.0]-5-nonene, monobutyltin oxide, etc.

In the reaction product of the hydroxyl group of the compound (a) having two hydroxyl groups and one thiol group and the acid anhydride group of pyromellitic anhydride and/or trimellitic anhydride obtained in the first step, the pyromellitic acid anhydride is Let the mole number of the acid anhydride group in the acid anhydride be (p), let the mole number of the acid anhydride group in trimellitic anhydride be (t), and let the compound having two hydroxyl groups and one thiol group in the molecule ( When the molar number of the hydroxyl group in a) is (o), the molar ratio of these is preferably 0.3<[(p)+(t)]/(o)<1.0, and further Preferably, it is 0.5<[(p)+(t)]/(o)<1.0, and most preferably, it is 0.6<[(p)+(t)]/(o)<0.8. If it is 0.3 or less, the acid anhydride residues that serve as pigment adsorption sites may decrease, and the acid value of the resin may also become low. If it is 1.0 or more, unreacted acid anhydride groups remain and storage stability exists. Sexual deterioration.

Next, the second step is described. The second step is to combine the hydroxyl group of the compound (a) having two hydroxyl groups and one thiol group with the acid anhydride group of pyromellitic anhydride and/or trimellitic anhydride. The thiol group remaining in the reaction product serves as a chain transfer agent, and the ethylenically unsaturated monomer (c) containing the hydroxyl-containing ethylenically unsaturated monomer (b) is radically polymerized to produce a hydroxyl-containing ethylenic unsaturated monomer. A hydroxyl-containing polymer of ethylenically unsaturated monomers. In the second step, a hydroxyl group can be introduced into the vinyl polymer part of the dispersant by copolymerizing the ethylenic unsaturated polymer (b) containing a hydroxyl group, and in the third step, it is possible to combine one isocyanate group with one or more The (meth)acrylyl compound (d) reacts.

(hydroxyl-containing ethylenically unsaturated monomer (b))

The hydroxyl-containing ethylenically unsaturated monomer (b) may be any monomer as long as it is a monomer having a hydroxyl group and an ethylenically unsaturated double bond. Specific examples include (meth)acrylate monomers having a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate or 3-hydroxypropyl (meth)acrylate. ester, 2-hydroxybutyl (meth)acrylate or 3-hydroxybutyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate and cyclohexanedimethanol mono(meth)acrylate, etc. hydroxyalkyl acrylate, and alkyl-α-hydroxyalkyl acrylate such as ethyl-α-hydroxymethyl acrylate; or (meth)acrylamide-based monomers with hydroxyl groups, such as N-( 2-Hydroxyethyl N-(hydroxyalkyl) (meth)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide, N-(2-hydroxybutyl)(meth)acrylamide, etc. ) (meth)acrylamide; or vinyl ether monomers with hydroxyl groups, such as 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether or 3-hydroxypropyl vinyl ether, 2 -Hydroxyalkyl vinyl ethers such as hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether or 4-hydroxybutyl vinyl ether; or allyl ether monomers with hydroxyl groups, such as 2-hydroxyl Ethyl allyl ether, 2-hydroxypropyl allyl ether or 3-hydroxypropyl allyl ether, 2-hydroxybutyl allyl ether or 3-hydroxybutyl allyl ether or 4-hydroxy Butyl allyl ether and other hydroxyalkyl allyl ethers.

In addition, for the hydroxyalkyl (meth)acrylate, alkyl-α-hydroxyalkyl acrylate, N-(hydroxyalkyl)(meth)acrylamide, hydroxyalkyl vinyl ether or hydroxyalkyl An ethylenically unsaturated monomer obtained by adding an alkylene oxide and/or a lactone to an allyl ether can also be used as the hydroxyl-containing ethylenically unsaturated monomer (b) in the method of the present invention. As the alkylene oxide to be added, ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,4-butylene oxide, 2,3-butylene oxide or 1,3 -Butylene oxide and combinations of two or more of these. When two or more alkylene oxides are used in combination, the bonding form may be random and/or block. As the lactone to be added, δ-valerolactone, ε-caprolactone, ε-caprolactone substituted with an alkyl group having 1 to 6 carbon atoms, and a combination of two or more of these can be used. Both alkylene oxide and lactone can also be added together.

(Other ethylenically unsaturated monomers)

Examples of the ethylenically unsaturated monomer other than the hydroxyl-containing ethylenically unsaturated monomer (b) include: (meth)methyl acrylate, (meth)ethyl acrylate, and (meth)n-propyl acrylate. , Isopropyl (meth)acrylate, n-Butyl (meth)acrylate, (Methyl) Isobutyl acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2,2,4-trimethyl (meth)acrylate Alkyl (meth)acrylates such as cyclohexyl, stearyl (meth)acrylate, lauryl (meth)acrylate, isobornyl (meth)acrylate, etc.; phenyl (meth)acrylate Aromatic (meth)acrylates such as ester, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate; (meth) Heterocyclic (meth)acrylates such as tetrahydrofurfuryl acrylate; alkoxy polyalkylene glycols such as methoxy polypropylene glycol (meth)acrylate and ethoxy polyethylene glycol (meth)acrylate. Alcohol (meth)acrylates; (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-iso Propyl(meth)acrylamide, diacetone(meth)acrylamide, acrylmorpholine and other (N-substituted) (meth)acrylamides; (meth)acrylic acid N,N- Amino-containing (meth)acrylates such as dimethylaminoethyl ester and N,N-diethylaminoethyl (meth)acrylate; nitriles such as (meth)acrylonitrile.

Examples of monomers that can be used in combination with the acrylic monomer include styrenes such as styrene, α-methylstyrene, and indene, ethyl vinyl ether, n-propyl vinyl ether, and isopropyl vinyl ether. Vinyl ethers such as propyl vinyl ether, n-butyl vinyl ether and isobutyl vinyl ether; fatty acid vinyl esters such as vinyl acetate and vinyl propionate.

In addition, a carboxyl group-containing ethylenically unsaturated monomer may be used together. as The ethylenically unsaturated monomer containing a carboxyl group may be one or more selected from acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, and the like.

The content of the hydroxyl-containing ethylenically unsaturated monomer (b) is 35 mass% or more and 80 mass% or less, preferably 38 mass% or more and 60 mass% with respect to the total amount of the ethylenically unsaturated monomer (c). mass% or less, more preferably 40 mass% or more and 50 mass% or less.

In the resin-type dispersant of the present invention, the carboxyl group-containing ethylenically unsaturated monomer is most preferably an ethylenically-containing ethylenically unsaturated monomer (b) containing a hydroxyl group using acrylic acid or methacrylic acid. The content of the carboxyl group-containing ethylenically unsaturated monomer in the unsaturated monomer (c) is preferably 2.5 to 10.0 mass%, and more preferably 2.5 to 5.0 mass%. If it is less than 2.5% by mass, the patterning suitability such as linearity and dimensional stability during the production of the color filter may be deteriorated. If it exceeds 10.0% by mass, the pigment dispersion stability may be deteriorated.

Next, the third step of reacting the hydroxyl-containing compound with the compound (d) having one isocyanate group and one or more (meth)acrylyl groups will be described. The dispersant of the present invention can be obtained by reacting a hydroxyl group in the hydroxyl-containing compound and an isocyanate group in the compound (d) having one isocyanate group and one or more (meth)acrylyl groups. Thereby, a (meth)acryl group can be arbitrarily introduced into the main vinyl polymer part in the dispersant, and a curable dispersant having curability in the solvent-affinity portion can be obtained.

(Compound (d) having one isocyanate group and one or more (meth)acrylyl groups)

The compound (d) having one isocyanate group and one or more (meth)acrylyl groups used in the third step is preferably a compound having one isocyanate group and one or two (meth)acrylyl groups, Specifically preferred are: 2-methacryloxyethyl isocyanate, 2-acryloxyethyl isocyanate, and 1,1-bis(acryloxymethyl)ethyl isocyanate.

The compound (d) having one isocyanate group and one or more (meth)acrylyl groups used in the present invention is not limited to the illustrated compounds, as long as it has an isocyanate group and one or more (meth)acrylyl groups. , it can be set to any structure. These can be used alone or in combination.

The molar ratio of the hydroxyl group in the hydroxyl-containing compound and the isocyanate group in the compound (d) having one isocyanate group and one or more (meth)acrylyl groups is preferably relative to the molar ratio of the hydroxyl group-containing compound. The isocyanate group in the compound (d) in which the hydroxyl group is 1 mole and has one isocyanate group and one or more (meth)acrylyl groups is 0.2 mole to 1.0 mole, and more preferably 0.5 mole to 1.0 mole, The most preferred range is 0.8 mole to 1.0 mole. If it is less than 0.2 mol, the amount of (meth)acrylyl groups may be reduced and the curability may be insufficient. If it exceeds 1.0 mol, unreacted isocyanate groups may remain in the resin, resulting in poor storage stability. condition. The reaction temperature is in the range of 50°C to 150°C, preferably 70°C to 120°C. If the reaction temperature is less than 50°C, the reaction rate will be slow. If it exceeds 150°C, the urethane group generated by the reaction will be decomposed.

Ideally, it is produced by the reaction of a hydroxyl group in the hydroxyl-containing compound and a compound having one isocyanate group and one or more (meth)acrylyl groups. The molar number of (meth)acrylyl groups introduced into the obtained resin-type dispersant (B) is a certain fixed amount. Generally, the amount of double bonds in a resin is the double bond equivalent (g/mol) calculated as (total weight of the resin)/(moles of double bonds contained in the weight of the resin) express. However, in the present invention, it is not the double bond equivalent of the entire resin but ((c) the total mass of ethylenically unsaturated monomers + (d) those having one isocyanate group and one or more (meth)acrylyl groups. Resin-type dispersant represented by the total mass of the compound)/((d) the number of moles of (meth)acrylyl groups contained in the compound having one isocyanate group and one or more (meth)acrylyl groups) The double bond equivalent (Z) in the side chain of (B) affects the linearity or dimensional stability when forming a color filter. In the present invention, the value of Z is preferably 300 g/mol to 600 g/mol because of linearity or dimensional stability when forming a color filter.

The weight average molecular weight of the dispersant obtained in the present invention is preferably 2,000 to 100,000, and more preferably 5,000 to 30,000. If the weight average molecular weight is less than 2,000, the stability of the pigment composition may decrease. If it exceeds 100,000, the interaction between resins may become stronger and thickening of the pigment composition may occur.

The acid value of the resin dispersant of the present invention is preferably 5 mgKOH/g to 200 mgKOH/g, more preferably 5 mgKOH/g to 150 mgKOH/g, and particularly preferably 5 mgKOH/g to 100 mgKOH/g. If the acid value is less than 5 mgKOH/g, the pigment adsorption capacity decreases and pigment dispersion problems may occur. If it exceeds 200 mgKOH/g, the interaction between resins becomes stronger and the viscosity of the pigment dispersion composition may increase.

<Color(A)>

The photosensitive coloring composition for color filters of the present invention may contain a pigment or dye as a coloring agent. As a pigment, an organic or inorganic pigment can be used individually or in mixture of 2 or more types. The pigment is preferably a pigment with high color development and high heat resistance, especially a pigment with high thermal decomposition resistance. Generally, organic pigments can be used. Hereinafter, specific examples of organic pigments that can be used in the coloring composition for color filters are shown with dye index (Colour Index) numbers.

<Organic Pigments>

Examples of red pigments include: C.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, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, the diketopyrrolopyrrole pigment described in Japanese Patent Publication No. 2011-523433, Or the azo pigment described in Japanese Patent Publication No. 2014-112527, the azo pigment described in Japanese Patent Publication No. 2013-161026, etc. Among these, from the viewpoint of the heat resistance, light resistance, and transmittance of the filter segment, C.I. Pigment Red 48:1, 122, 177, 224, 242, and 254 are preferred, and C.I. Pigment Red 177 and 254 are more preferred. .

In addition, orange pigments such as C.I. Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, or 73 and/or yellow pigments described below may be used together in the red coloring composition.

Examples of blue pigments include: C.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, etc. Among these, from the viewpoint of the heat resistance, light resistance, and transmittance of the filter segment, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, or 15:6 is preferred. Furthermore, C.I. Pigment Blue 15:6 is preferred. In addition, aluminum phthalocyanine pigments are also preferably used, and aluminum phthalocyanine pigments described in Japanese Patent Laid-Open No. 2004-333817, Japanese Patent No. 4893859, etc. may also be used.

In addition, a purple pigment described below may be used together in the blue coloring composition.

Examples of purple pigments include: C.I. Pigment Violet (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, etc. Among these, from the viewpoint of the heat resistance, light resistance, and transmittance of the filter segment, C.I. Pigment Violet 19 or 23 is preferred, and C.I. Pigment Violet 23 is further preferred.

Examples of green pigments include C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 62, 63, zinc phthalocyanine pigments described in Japanese Patent Application Publication No. 2008-19383, Japanese Patent Application Publication No. 2007-320986, Japanese Patent Application Publication No. 2004-70342, etc., Japanese Patent Applications Aluminum phthalocyanine pigments, etc. described in Publication No. 4893859, etc. Among these, C.I. Pigment Green 36 or 58 is preferred from the viewpoint of transmittance.

In addition, a yellow pigment described below may be used together in the green coloring composition.

Examples of yellow pigments include: C.I. pigment yellow (pigment yellow) 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35 ,35:1,36,36:1,37,37:1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,93,94 ,95,97,98,100,101,104,106,108,109,110,113,114,115,116,117,118,119,120,123,126,127,128,129,138,139 ,147,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179,180 , 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, quinoline yellow compounds described in Japanese Patent Laid-Open No. 2012-226110, etc., are not particularly limited to these. . Among these, from the viewpoint of heat resistance, light resistance, and transmittance of the filter segment, the yellow pigment is preferably selected from C.I. Pigment Yellow 138, 139, 150, 185 and Japanese Patent Laid-Open No. 2012-226110 At least one of the described quinoline yellow pigments. C.I. Pigment Yellow 139, 150, and 185 are more preferred.

Examples of the quinoline yellow pigment described in Japanese Patent Application Laid-Open No. 2012-226110 include compounds shown below.

[Chemicalization 2]

C.I. pigment blue 15:1, 15:2, 15:4, 15:3, 15:6, 16, etc. can be used alone or in mixture in the cyan coloring composition used to form the cyan filter segment. 81 and other blue pigments.

Purple pigments or red pigments such as C.I. Pigment Violet 1 and 19, C.I. Pigment Red 144, 146, 177, 169, and 81 can be used alone or in mixture in the magenta coloring composition used to form the magenta filter segment. A yellow pigment may be used together with the magenta composition.

In addition, examples of inorganic pigments include titanium oxide, barium sulfate, zinc white, lead sulfate, chrome yellow, zinc yellow, iron lead (red iron (III) oxide), cadmium red, ultramarine blue, Prussian blue, chromium oxide green, Cobalt green, umber, synthetic iron black, etc. In order to achieve a balance between chroma and brightness and ensure good coating properties, sensitivity, developability, etc., inorganic pigments can be used in combination with organic pigments.

(Miniaturization of pigments)

In order to cope with high transmittance and high contrast, the organic pigment is preferably finely divided by salt milling treatment or the like. The primary particle diameter of the pigment is preferably 10 nm or more in terms of good dispersion in the colorant carrier. In addition, in terms of forming a filter segment with high contrast, the thickness is preferably 80 nm or less. A particularly preferred range is from 20 nm to 60 nm.

When salt milling the pigment, resin can be added if necessary. The type of resin used is not particularly limited, and natural resin, modified natural resin, synthetic resin, synthetic resin modified by natural resin, etc. can be used. The resin used is preferably solid at room temperature and water-insoluble, and further preferably is partially soluble in the organic solvent. The usage amount of the resin is preferably in the range of 5 to 200 mass % based on the total weight of the pigment (100 mass %).

<Dye>

The colored composition according to the embodiment of the present invention may also use a dye as a colorant. As the dye, any of acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, etc. can be used. In addition, these derivatives or the form of a lake pigment obtained by lake-forming a dye may also be used.

Furthermore, in the case of an acid dye or a direct dye having an acidic group such as a sulfonic acid group or a carboxylic acid group, an inorganic salt of an acid dye, or an acid dye and a quaternary ammonium salt compound, a tertiary amine compound, or a diamine compound is used. A primary amine compound, a salt-forming compound of a nitrogen-containing compound such as a primary amine compound, or a resin component having these functional groups can be used as a salt-forming compound by salifying it, or a sulfonamide compound can be used as a sulfonamide compound. It is preferred because it has excellent durability and can be used to prepare a colored composition with excellent fastness.

In addition, a salt-forming compound of an acid dye and a compound having an onium salt group is also preferred because of its excellent fastness, and more preferably, the compound having an onium salt group is a resin having a cationic group in a side chain.

When it is in the form of a basic dye, it can be salified using an organic acid, perchloric acid, or a metal salt thereof and used. Salt-forming compounds of basic dyes are preferred because of their excellent resistance and compatibility with pigments, and it is more preferred to use organic sulfonic acids and organic sulfuric acids, which are counter components that function as counter ions for basic dyes. , a phosphorus anion compound containing a fluorine group, a boron anion compound containing a fluorine group, a nitrogen anion compound containing a cyano group, an anion compound containing the conjugate base of an organic acid having a halogenated hydrocarbon group, or an acid dye that is salted salt compound.

In addition, it is preferable to have a polymerizable unsaturated group in the dye skeleton because a dye having excellent resistance can be produced.

In addition, when the dye has an oxetanyl group, the colored composition containing the dye has excellent heat resistance after curing. The dye having an oxetane group can be obtained, for example, by using an ethylenically unsaturated monomer containing an oxetane structure in a resin constituting a salt-forming compound containing the dye.

In one embodiment, the chemical structure of the dye may be derived from azo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrrole dyes, etc. Methyl (dipyrromethene) dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium (carbonium) dyes (diphenylmethane dyes, Triphenylmethane-based dyes, xanthene-based dyes, acridine-based dyes, etc.), quinoneimine-based dyes (oxazine-based dyes, thiazine-based dyes, etc.), azine-based dyes, polymethine-based dyes ( Oxocyanine-based dyes, merocyanine-based dyes, arylidene-based dyes, styrene-based dyes, cyanine-based dyes, squarylium-based dyes, croconium-based dyes, etc.), Quinoline dyes, phthalocyanine dyes, subphthalocyanine dyes, ionone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes , and the pigment structure of dyes in these metal complex dyes and the like.

Among these dye structures, from the viewpoint of color characteristics such as hue, color separability, and color unevenness, those derived from azo dyes, xanthene dyes, Cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrrromethylene dyes, squarylide dyes, quinoline yellow dyes, phthalocyanine dyes, and subphthalocyanine dyes The pigment structure of the dye is more preferably derived from a dye selected from the group consisting of xanthene-based dyes, cyanine-based dyes, triphenylmethane-based dyes, anthraquinone-based dyes, dipyrromethene-based dyes, and phthalocyanine-based dyes. pigment structure. Regarding specific pigment compounds that can form pigment structures, see "New Edition of Dyes Handbook" (edited by the Society of Organic Chemistry; Maruzen, 1970), "Dye Index" (The Society of Dyers and colourists), "Pigments "Handbook" (edited by Ohgawara; Kodansha, 1986), etc.

Examples of dyes in other embodiments include azo dyes, azo metal complex dyes, anthraquinone dyes, indigo dyes, thioindigo dyes, phthalocyanine dyes, and methine dyes. Diarylmethane dyes, triarylmethane dyes, xanthene dyes, thiazine dyes, cationic dyes, cyanine dyes, nitro dyes, quinoline dyes, naphthoquinone dyes, oxazines Dyes, perylene dyes, diketopyrrolopyrrole dyes, quinacridone dyes, anthranthrone dyes, isoindolinone dyes, isoindoline dyes, indanthrine (indanthrone)-based dyes, coumarin-based dyes, pyranthrone-based dyes, flavoxone-based dyes, elastrone-based dyes, etc., but are not limited to these.

Furthermore, examples of organic dyes that can be used in other embodiments include triarylmethane-based dyes, xanthene-based dyes, and anthraquinone-based dyes. Among them, xanthene-based dyes are preferably used.

[Xanthene dyes]

The xanthene-based dye that can be preferably used preferably exhibits red or purple color and has an oily Dyes in any form including soluble dyes, acid dyes, direct dyes, and basic dyes. In addition, these dyes may also be in the form of lake pigments obtained by lake-forming these dyes.

Among these, the use of xanthene-based oil-soluble dyes and xanthene-based acid dyes is preferred because of their excellent hue.

Examples of dyes that exhibit red or purple include oil-soluble dyes such as C.I. solvent red (solvent red) and C.I. solvent violet (solvent violet), and bases such as C.I. basic red (basic red) and C.I. basic violet (basic violet) Dyes such as acid dyes, acid dyes such as C.I. acid red and C.I. acid violet, and direct dyes such as C.I. direct red and C.I. direct violet.

Here, the direct dye has a sulfonic acid group (-SO ₃ H, -SO ₃ Na) in the structure, and the direct dye is regarded as an acid dye in this disclosure.

[Salt formation and sulfonyl amination of xanthene dyes]

In addition, it is preferable to use an xanthene-based basic dye by salting it using an organic acid or perchloric acid. As the organic acid, organic sulfonic acid and organic carboxylic acid are preferably used. Among them, naphthalenesulfonic acid such as Tobias acid and perchloric acid are preferably used in terms of resistance.

In addition, in terms of resistance, the xanthene-based acid dye is preferably formed 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. It can be salified and used as a salt-forming compound, or it can be sulfonamided and used as a sulfonamide compound.

The salt-forming compound of the xanthene-based acid dye and/or the sulfonamide compound of the xanthene-based acid dye is preferred because of its excellent hue and resistance, and it is more preferred to use, for example, The following compound: a compound in which a xanthene-based acid dye is salified using a quaternary ammonium salt compound that is a counter component that functions as a counterion; and a compound in which a xanthene-based acid dye is sulfonated of sulfonamide compounds.

Moreover, among the xanthene-based dyes, rhodamine-based dyes are preferred because they also have excellent color development properties and tolerance.

Hereinafter, the form of the xanthene-based dye will be specifically described in detail.

[Xanthene-based oil-soluble dyes]

Examples of xanthene-based oil-soluble dyes include: C.I. Solvent Red 35, C.I. Solvent Red 36, C.I. Solvent Red 42, C.I. Solvent Red 43, C.I. Solvent Red 44, C.I. Solvent Red 45, C.I. Solvent Red 46, C.I. Solvent Red 47. C.I. Solvent Red 48, C.I. Solvent Red 49, C.I. Solvent Red 72, C.I. Solvent Red 73, C.I. Solvent Red 109, C.I. Solvent Red 140, C.I. Solvent Red 141, C.I. Solvent Red 237, C.I. Solvent Red 246, C.I. Solvent Violet 2. C.I. Solvent Violet 10, etc.

Among them, C.I. Solvent Red 35, C.I. Solvent Red 36, C.I. Solvent Red 49, C.I. Solvent Red 109, C.I. Solvent Red 237, C.I. Solvent Red 246, and C.I. Solvent which are rhodamine-based oil-soluble dyes with high color development properties are more preferred. Purple 2.

[Xanthene-based basic dye]

Examples of xanthene-based basic dyes include C.I. Basic Red 1 (Rhodamine 6GCP), 8 (Rhodamine G), C.I. Basic Violet 10 (Rhodamine B), and the like. Among them, C.I. Basic Red 1 and C.I. Basic Violet 10 are preferably used in terms of excellent color development properties.

[Xanthene acid dye]

As the xanthene-based acid dye, C.I. acid red 51 (erythrosine (erythrosine) (edible red No. 3)), C.I. acid red 52 (acid rhodamine), C.I. acid red 87 (eosin (eosin) G (edible red No. 103)), C.I. acid red 92 (acid fluorescent pink (acid) phloxine) PB (edible red No. 104)), C.I. acid red 289, C.I. acid red 388, rose-bengal B (edible red No. 5), acid rhodamine G, C.I. acid violet 9.

Among them, in terms of heat resistance and light resistance, it is more preferable to use C.I. Acid Red 87, C.I. Acid Red 92, C.I. Acid Red 388, which are xanthene-based acid dyes, or C.I. Acid Red, which is a rhodamine-based acid dye. 52 (acid rhodamine), C.I. acid red 289, acid rhodamine G, C.I. acid violet 9.

Among them, C.I. Acid Red 52 and C.I. Acid Red 289, which are rhodamine-based acid dyes, are most preferably used in terms of excellent color development properties, heat resistance, and light resistance.

The acid dye (not limited to the xanthene type) is preferably a salt-forming compound of an acid dye and a nitrogen-containing compound, and a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, a primary amine compound, etc., or a compound having these is used. It is preferable to salify the resin component of the functional group to form a salt-forming compound of the acid dye, since this can provide high heat resistance, light resistance, and solvent resistance. Acid dyes can also be given high heat resistance, light resistance, and solvent resistance through sulfonamide.

Alternatively, a salt-forming compound of an acidic dye and a compound having an onium salt group may be used. In particular, when the compound having an onium salt group is a resin having a cationic group in a side chain, a colored composition excellent in brightness and durability can be produced. .

Examples of primary amine compounds include: methylamine, ethylamine, propylamine, isopropylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, Decylamine, undecylamine, dodecylamine (laurylamine), tridecylamine, tetradecylamine (myristylamine), pentadecylamine, cetylamine, stearylamine, Aliphatic unsaturated primary amines such as oleyl amine, coconut oil alkylamine (cocoalkylamine), tallow alkylamine, hardened tallow alkylamine, allylamine, aniline, benzylamine, etc.

Examples of secondary amine compounds include aliphatic unsaturated compounds such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, dipentylamine, and diallylamine. Secondary amines, methylaniline, ethylaniline, dibenzylamine, diphenylamine, dicocoalkylamine, dishardened tallow alkylamine, distearylamine, etc.

Examples of tertiary amine compounds include trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, dimethylaniline, diethylaniline, and tribenzylamine.

(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) containing an acid dye and a quaternary ammonium salt compound.

The quaternary ammonium salt compound which is a counter component of an acid dye is demonstrated. The quaternary ammonium salt compound becomes a compound that competes with acidic dyes by having an amino group.

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

The molecular weight of the counter portion of the cationic component of the quaternary ammonium salt compound is preferably in the range of 190 to 900. Here, the counterbalancing part corresponds to the (NR ₁ R ₂ R ₃ R ₄ ) ⁺ part in the following general formula (1). If the molecular weight is less than 190, the light resistance and heat resistance will be reduced, and the solubility in the solvent will also be reduced. In addition, if the molecular weight exceeds 900, the proportion of color-developing components in the molecule decreases, the color development property decreases, and the brightness also decreases. More preferably, the molecular weight of the counter part is in the range of 240 to 850. Particularly preferably, the molecular weight of the counter part is in the range of 350 to 800. Here, the molecular weight is calculated based on the structural formula, and the atomic weight of C is 12, the atomic weight of H is 1, and the atomic weight of N is 14.

As the quaternary ammonium salt compound, a compound represented by the following general formula (1) can be used.

General formula (1)

(In the general formula (1), R ₁ to R ₄ each independently represent an alkyl group or benzyl group having 1 to 20 carbon atoms, and the number of at least two or more Cs in R ₁ , R ₂ , R ₃ , and R ₄ is 5~20; Y ^- represents inorganic or organic anions)

By setting the number of at least two C's in R ₁ to R ₄ to 5 to 20, the solubility in the solvent becomes good. If the alkyl group with the number of C's less than 5 is 3 or more, the solubility in the solvent becomes poor, and foreign matter in the coating film is likely to be generated. In addition, if there is an alkyl group in which the number of C exceeds 20, the color development property of the salt-forming compound (a) will be impaired.

The Y ^- component constituting the anion may be an inorganic or organic anion, and is preferably a halogen, usually chlorine.

Examples of quaternary ammonium salt compounds include tetramethylammonium chloride, tetraethylammonium chloride, monostearyltrimethylammonium chloride, distearyldimethylammonium chloride, and tristearyl ammonium chloride. Monomethylammonium chloride, cetyltrimethylammonium chloride, trioctylmethylammonium chloride, dioctyldimethylammonium chloride, monolauryltrimethylammonium chloride, dilauryldimethylammonium chloride Methyl ammonium chloride, trilauryl methyl ammonium chloride, tripentyl benzyl ammonium chloride, trihexyl benzyl ammonium chloride, trioctyl benzyl ammonium chloride, trilauryl benzyl ammonium chloride, Benzyl dimethyl stearyl ammonium chloride, benzyl dimethyl octyl ammonium chloride, dialkyl (alkyl group is C14~C18) dimethyl ammonium chloride (hardened tallow), etc.

Examples of specific products of quaternary ammonium salt compounds include Quartamin 24P, Quartamin 86P CONC, Quartamin 60W and Quartamin 86W manufactured by Kao Corporation. Quartamin D86P, Sanisol C, Sanisol B-50, etc., Arquad 210-80E, 2C-75 manufactured by Lion Company , 2HT-75, 2HT flakes (FLAKE), 2O-75I, 2HP-75, 2HP flakes (FLAKE), etc., among which Quartamin (Quartamin) D86P (distearyl dimethyl ammonium chloride), moxa Arquad (Arquad) 2HT-75 (dialkyl (alkyl group is C14~C18) dimethyl ammonium 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′) containing an acid dye and a resin having a cationic group in a side chain. The resin for obtaining the salt-forming compound (a′) used in the embodiment of the present invention having a cationic group in the side chain 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 salt group in the side chain. As a suitable onium salt structure, from the viewpoint of availability, etc., Ammonium salts, iodonium salts, sulfonium salts, diazonium salts, and phosphonium salts are preferred, and in consideration of storage stability (thermal stability), ammonium salts, iodonium salts, and sulfonium salts are more preferred. Ammonium salts are further preferred.

When preparing a blue coloring composition for color filters containing a salt-forming compound (a') and expressing the characteristics of a color filter, it is preferable to use an adhesive with a blue coloring composition constituting a color filter. The agent resin is the same type of resin. In one embodiment of the present invention, the coloring composition for color filters preferably uses an acrylic resin as a binder resin. Therefore, the resin having a cationic group in the side chain for obtaining the salt-forming compound (a') is preferably Acrylic resin.

As a resin having a cationic group in a side chain, an alkali resin containing a structural unit represented by the following general formula (2) can be used. A salt-forming compound can be obtained by forming a salt between the cationic group in the general formula (2) and the anionic group of the xanthene-based acid dye.

General formula (2)

[In the general formula (2), 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, or an optionally substituted alkenyl group. , or an aryl group that may be substituted, two of R ⁵² ~ R ⁵⁴ may be bonded to each other to form a ring; Q represents an alkylene group, an aryl group, -CONH-R ⁵⁵ -, -COO-R ⁵⁵ - , R ⁵⁵ represents an alkylene group; Y ^- represents an inorganic or organic anion]

Examples of the alkyl group in R ⁵¹ include methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, n-hexyl, and cyclohexyl. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.

When the alkyl group represented by R ⁵¹ has a substituent, examples of the substituent include a hydroxyl group, an alkoxy group, and the like.

Among the above, R ⁵¹ is most preferably a hydrogen atom or a methyl group.

Examples of alkyl groups in R ⁵² to R ⁵⁴ include: linear alkyl groups (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl, n- Tetradecyl, n-hexadecyl and n-octadecyl, etc.), branched alkyl (isopropyl, isobutyl, second butyl, third butyl, isopentyl, neopentyl, third pentyl , isohexyl, 2-ethylhexyl and 1,1,3,3-tetramethylbutyl, etc.), cycloalkyl (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.) and cross-linked rings Formula alkyl (norbornyl, adamantyl and pinanyl (pinanyl), etc.). The alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms.

Examples of the alkenyl group in 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.), cycloalkene base (2-cyclohexenyl and 3-cyclohexenyl, etc.). The alkenyl group is preferably an alkenyl group having 2 to 18 carbon atoms, and more preferably an alkenyl group having 2 to 8 carbon atoms.

Examples of the aryl group in R ⁵² to R ⁵⁴ include monocyclic aryl groups (phenyl, etc.), condensed polycyclic aryl groups (naphthyl, anthracenyl, phenanthrenyl, anthraquinone, fluorenyl and naphthoquinone). etc.) and aromatic heterocyclic hydrocarbon 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) and 9-oxoxanthenyl (group derived from thioxanthone), etc.).

When the alkyl group, alkenyl group, or aryl group represented by R ⁵² to R ⁵⁴ has a substituent, the substituent may be selected from a halogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, an alkenyl group, Substituents in acyl group, alkoxycarbonyl group, carboxyl group, phenyl group, etc. As the substituent, a halogen atom, a hydroxyl group, an alkoxy group, and a phenyl group are particularly preferred.

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

In addition, two of R ⁵² to R ⁵⁴ may be bonded to each other to form a ring.

In the general formula (2), the Q component connecting the vinyl moiety and the ammonium salt group represents an alkylene group, an aryl group, -CONH-R ⁵⁵ -, -COO-R ⁵⁵ -, and R ⁵⁵ represents an alkylene group, where , in terms of polymerizability and availability, -CONH-R ⁵⁵ - and -COO-R ⁵⁵ - are preferred. In addition, R ⁵⁵ is more preferably methylene, ethylene, propylene, or butylene, and particularly preferably ethylene.

The Y ^- component in the general formula (2) constituting the counter anion of the resin may be an inorganic or organic anion. As the counter anion, well-known ions can be used without limitation, and specific examples include: hydroxide ions; halogen ions such as chloride ions, bromide ions, and iodide ions; carboxylate ions such as formate ions and acetate ions; and carbonic acid ions. ion, bicarbonate ion, nitrate ion, sulfate ion, sulfite ion, chromate ion, dichromate ion, phosphate ion, cyanide ion, permanganate ion, and then ferricyanate(III) Complex ions such as radical ions, etc. In terms of synthesis suitability and stability, halide ions and carboxylate ions are preferred, and halide ions are most preferred. When the counter anion is an organic acid ion such as a carboxylate ion, the organic acid ion can be covalently bonded in the resin to form an intramolecular salt.

One method of introducing an oxetane group into a resin having a cationic group in the side chain is to combine an ethylenically unsaturated monomer containing an oxetane structure with a general A method of copolymerizing ethylenically unsaturated monomers corresponding to the cationic groups represented by formula (2).

Examples of the ethylenically unsaturated monomer having an oxetanyl group include (meth)acrylic acid (3-methyl-3-oxetanyl)methyl ester, (meth)acrylic acid (3- Ethyl-3-oxetanyl)methyl ester, (meth)acrylic acid (3-butyl-3-oxetanyl)methyl ester, (meth)acrylic acid (3-hexyl-3-oxa) cyclobutyl) methyl ester, etc.

Examples of commercially available products include: ETERNACOLL OXMA (manufactured by Ube Kosan Co., Ltd.), OXE-10, OXE-30 (the above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), and the like.

(Salt Formation) A acid dye and a salt-forming compound with a nitrogen-containing compound or a resin having a cationic group in a side chain can be produced by a conventionally known method. Specific methods are disclosed in Japanese Patent Application Laid-Open No. 11-72969 and the like.

If a xanthene-based acid dye is used as an example, the xanthene-based acid dye may be dissolved in water, and then a quaternary ammonium salt compound may be added and stirred to perform a salification treatment. Here, a combination of a part of the sulfonic acid group (-SO ₃ H) and the sodium sulfonate group (-SO ₃ Na) in the xanthene-based acid dye and the ammonium group (NH ₄ ⁺ ) of the quaternary ammonium salt compound can be obtained. A partially bonded salt-forming compound. In addition, instead of water, methanol and ethanol are also solvents that can be used for salinization.

In addition, the salt-forming compound can be easily obtained by stirring or vibrating an aqueous solution in which the resin having a cationic group in the side chain represented by the general formula (2) and the acid dye are dissolved, or by stirring Or the aqueous solution of the resin represented by the general formula (2) having a cationic group in the side chain and the acid dye water are vibrated. The solution is mixed. In the aqueous solution, the ammonium group of the resin and the anionic group of the acid dye are ionized, and these are ionically bonded, and the ionically bonded portion becomes water-insoluble and precipitates. On the contrary, the salt containing the counter anion of the resin and the counter cation of the acid dye is water-soluble and can be removed by washing with water or the like. A single type of resin and acid dye having a cationic group in a side chain may be used, or a plurality of types having different structures may be used.

In addition, among other acidic dyes, a salt-forming compound with a nitrogen-containing compound or a resin having a cationic group in the side chain can also be obtained by the same method as the xanthene-based dye.

(Sulfonamide compound)

The acid dye may be a sulfonamide compound obtained by reacting a sulfonamide compound with an anionic dye.

A sulfonamide compound of an acid dye that can be preferably used among acid dyes can be produced by chlorinating an acid dye having -SO ₃ H and -SO ₃ Na using a conventional method to convert -SO ₃ H into -SO ₂ Cl and react the compound with an amine having a -NH ₂ group.

In addition, as the amine compound that can be preferably used for sulfonamide formation, specifically, 2-ethylhexylamine, dodecylamine, 3-decyloxypropylamine, 3-(2-ethylhexylamine) is preferably used. Oxy)propylamine, 3-ethoxypropylamine, cyclohexylamine, etc.

If a xanthene-based acid dye is used as an example, when a sulfonamide compound modified with C.I. Acid Red 289 using 3-(2-ethylhexyloxy)propylamine is obtained, as long as After chlorinating C.I. Acid Red 289 sulfonyl, it was dissolved in dioxane. Just react with equivalent amounts of 3-(2-ethylhexyloxy)propylamine to obtain the sulfonamide compound of C.I. Acid Red 289.

In addition, when obtaining a sulfonamide compound in which C.I. Acid Red 52 is modified using 3-(2-ethylhexyloxy)propylamine, it is only necessary to chlorinate C.I. Acid Red 52 sulfonamide. , react with a theoretical equivalent of 3-(2-ethylhexyloxy)propylamine in dioxane to obtain a sulfonamide compound of C.I. Acid Red 52.

In addition, among other acid dyes, sulfonamide compounds can also be obtained by the same method as xanthene-based dyes.

As the xanthene-based dye, Japanese Patent Laid-Open No. 2010-032999, Japanese Patent Laid-Open No. 2011-138094, Japanese Patent Laid-Open No. 2011-227313, Japanese Patent Laid-Open No. 2011-242752, Japan Japanese Patent Application Publication No. 2012-107192, Japanese Patent Application Publication No. 2013-033194, Japanese Patent Application Publication No. 2011-71888, Japanese Patent Application Publication No. 2013-72263, Japanese Patent Application Publication No. 2013-81209, Japan Japanese Patent Application Publication No. 2014-173064, Japanese Patent Application Publication No. 2013-53028, Japanese Patent Application Publication No. 2013-52186, Japanese Patent Application Publication No. 2014-196392, Japanese Patent Application Publication No. 2014-196393, Japan Japanese Patent Laid-Open No. 2014-201714, Japanese Patent Laid-Open No. 2014-201715, Japanese Patent Laid-Open No. 2013-050693, Japanese Patent Laid-Open No. 2013-178478, Japanese Patent Laid-Open No. 2013-203956, International Publicly known technologies described in Manual No. 2013/011687 etc. are disclosed.

In one embodiment, the xanthene-based dyes are preferably C.I. Acid Red 51, C.I. Acid Red 52, C.I. Acid Red 87, C.I. Acid Red 92, C.I. Acid Red 289, C.I. Acid Red 388, Rose Red B, Acid Rhodamine G, C.I. Acid Violet 9, C.I. Acid Violet 30. Among them, C.I. Acid Red 52, C.I. Acid Red 87, C.I. Acid Red 92, C.I. Acid Red 289, and C.I. Acid Red 388 are more preferred.

[Dipyrromethene dye]

The dipyrromethene dye is a dye having a partial structure derived from a dipyrromethene dye as a dye moiety, and is preferably a dipyrromethene compound, a dipyrromethene compound and a metal or a metal The dipyrromethene metal complex compound obtained by the compound is preferably a metal complex compound in which the structure represented by the general formula (3) is coordinated to a metal atom or a metal compound (hereinafter, suitably referred to as "dipyrromethene metal complex compound"). Pyrromethene metal complex compound").

[Dipyrromethene metal complex compound]

A metal complex compound (dipyrromethene metal complex compound) in which the structure represented by the general formula (3) is coordinated to a metal atom or a metal compound will be described.

General formula (3)

In the general formula (3), R ¹ to R ⁶ each independently represent a hydrogen atom or a monovalent substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group.

The metal or metal compound may be any metal atom or metal compound that can form a complex, and may include a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or a divalent metal chloride. Metals or metal compounds include, for example, AlCl ₃ , InCl ₃ , FeCl ₃ in addition to Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, B, etc. , TiCl ₂ , SnCl ₂ , SiCl ₂ , GeCl ₂ and other metal chlorides, TiO, VO and other metal oxides, Si(OH) ₂ and other metal hydroxides.

Among these, as the metal or metal compound, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn are preferred from the viewpoints of stability, spectral characteristics, heat resistance, light resistance, and manufacturing suitability of the complex. , Cu, Ni, Co, TiO, B, or VO, more preferably Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO, most preferably Fe, Zn, Cu, Co , B, or VO.

As such a dipyrromethene-based dye, Japanese Patent Application Publication No. 2008-292970, Japanese Patent Application Publication No. 2010-85758, Japanese Patent Application Publication No. 2010-84009, and Japanese Patent Application Publication No. 2010-43530 can be used. Publication No. 2013-080010, Japanese Patent Application Laid-Open No. 2013-210596, International Publication No. 2013/141156, etc.

[Triphenylmethane dye]

Examples of the triphenylmethane dye skeleton include a diaminotriphenylmethane dye skeleton, a triaminotriphenylmethane dye skeleton, a rosolic acid dye skeleton having an OH group, and the like.

The trisaminotriphenylmethane dye skeleton is preferred in terms of excellent color tone and excellent light fastness compared to other skeletons. Among them, as an alkaline dye, it is particularly preferred The diphenylnaphthylmethane dye backbone of the material.

[Triphenylmethane basic dye]

Triphenylmethane-based basic dyes develop color by oxidizing the NH ₂ or OH gene at the para position with respect to the central carbon to obtain a quinone structure.

It is classified into the following three types according to the number of NH ₂ and OH groups. Among them, the triaminoarylmethane-based basic dye is preferred in terms of emitting good blue, red, and green colors.

a) Diaminotriphenylmethane basic dye

b)Triaminotriphenylmethane basic dye

c) Rose acid basic dye with OH group

Triaminotriphenylmethane-based basic dyes and diaminotriphenylmethane-based basic dyes have bright color tones and are excellent in light fastness compared to other dyes, and are therefore preferred.

The blue (blue) triphenylmethane-based basic dye has spectral characteristics with high transmittance in 400nm~440nm, so it can be produced especially when used for forming blue filter segments. Because of its high brightness, it is preferred.

Specific examples of triphenylmethane-based basic dyes include: C.I. Basic Violet 1 (Methyl Violet), C.I. Basic Violet 3 (Crystal Violet), C.I. Basic Violet 14 (Magenta), C.I. Alkali Basic blue 1 (basic cyanine 6G), C.I. basic blue 5 (basic cyanine EX), C.I. basic blue 7 (Victoria pure blue (Victoria pure blue) BO), C.I. basic blue 26 (Victoria blue (Victoria blue) Bconc.), C.I. basic green (basic green) 1 (brilliant green (brilliant green) GX), C.I. basic green 4 (malachite green), etc.

Among them, C.I. Basic Blue 7 is preferably used in terms of brightness.

In the case of a triphenyl-based basic dye, an organic acid, perchloric acid, or a metal salt thereof can be used to form a salt. Among them, salt-forming compounds of basic dyes are preferable because of their excellent resistance and compatibility with pigments. More preferably, organic sulfonic acid, organic sulfuric acid, and organic sulfuric acid, which are countercomponents that act as counterions to basic dyes, are used. A phosphorus anion compound containing a fluorine group, a boron anion compound containing a fluorine group, a nitrogen anion compound containing a cyano group, an anion compound containing a conjugate base of an organic acid having a halogenated hydrocarbon group, or a salt-forming compound obtained by salting an acidic dye .

Specifically, they are organic acids such as heteropoly acids, organic sulfonic acids such as aliphatic sulfonic acid and aromatic sulfonic acid, organic sulfuric acids such as aliphatic sulfuric acid and aromatic sulfuric acid, aromatic carboxylic acids, organic carboxylic acids such as fatty acids, or Those with the form of acid dye. Alternatively, these metal salts may be used. In addition, a salt-forming compound with a resin having an acid group is also preferred.

(salt formation)

These salt-forming compounds of basic dyes and anionic counter components can be synthesized using conventionally known methods. Specific methods are disclosed in Japanese Patent Application Laid-Open No. 2003-215850 and the like.

To give an example, after dissolving the triarylmethane-based basic dye in water, an organic sulfonic acid or (sodium organic sulfonate) solution may be added and stirred to perform a salification treatment. Here, a salt-forming compound in which part of the amino group (-NHC ₂ H ₅ ) in the triarylmethane-based basic dye is bonded to part of the sulfonic acid group (-SO ₃ H) of the organic sulfonic acid can be obtained.

Here, the organic sulfonic acid may be dissolved in an alkaline solution such as sodium hydroxide and used in the form of sodium sulfonate (-SO ₃ Na) before performing a salt-forming treatment. In the present disclosure, the sulfonic acid group (-SO ₃ H) and the functional group (-SO ₃ Na) as sodium sulfonate may be mentioned without distinction.

As such a triphenylmethane-based dye, Japanese Patent Laid-Open No. 2002-014222, Japanese Patent Laid-Open No. 2003-246935, Japanese Patent Laid-Open No. 2008-304766, and Japanese Patent Laid-Open No. 2010-256598 can be used. Gazette, Japanese Patent Application Publication No. 2011-200560, Japanese Patent Application Publication No. 2011-186043, Japanese Patent Application Publication No. 2012-173399, Japanese Patent Application Publication No. 2012-233033, Japanese Patent Application Publication No. 2012-098522 Gazette, Japanese Patent Application Publication No. 2012-288970, Japanese Patent Application Publication No. 2012-200469, Japanese Patent Application Publication No. 2014-196262, International Publication No. 2010/123071 Manual, International Publication No. 2011/162217 Manual, Publicly known technology described in International Publication No. 2013/108591.

In one embodiment, as the triphenylmethane-based dye, C.I. Acid Violet 15, C.I. Acid Violet 17, C.I. Acid Violet 19, C.I. Acid Violet 21, C.I. Acid Violet 24, C.I. Acid Violet 25, C.I. Acid Violet 38, C.I. acid violet 49, C.I. acid blue (acid blue) 1, C.I. acid blue 3, C.I. acid blue 5, C.I. acid blue 7, C.I. acid blue 9, C.I. acid blue 11, C.I. acid blue 13, C.I. acid blue 15, C.I. Acid Blue 17, C.I. Acid Blue 22, C.I. Acid Blue 24, C.I. Acid Blue 26, C.I. Acid Blue 75, C.I. Acid Blue 83, C.I. Acid Blue 90, C.I. Acid Blue 93, C.I. Acid Blue 100, C.I. Basic Blue 81. C.I. Basic blue 83.

Alternatively, as the triarylmethane dye, C.I. Basic Violet 1, C.I. Basic Violet 2, C.I. Basic Violet 3, C.I. Basic Violet 4, C.I. Basic Violet 14, C.I. Basic Blue 1, C.I. Alkali can be preferably used. C.I. basic blue 5, C.I. basic blue 7, C.I. basic blue 11, C.I. basic blue 26.

[Cyanine dye]

As the cyanine-based dye, any compound having a pigment moiety including a cyanine skeleton in the molecule can be used without limitation.

Examples of cyanine dyes include: C.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. basic red 12, 13, 14, 15, 27, 35, 36, 37, 45, 48, 49, 52, 53, 66, 68, C.I. basic violet 7, 15, 16, 20, 21, 39, 40, C.I. basic orange (basic orange) 27, 42, 44, 46, C.I. basic blue 62, 63, etc.

In addition, cyanine-based dyes described in Japanese Patent Laid-Open No. 2014-224970, Japanese Patent Laid-Open No. 2013-261614, etc. can also be used.

[Anthraquinone dye]

The anthraquinone dye is a dye having an anthraquinone skeleton in the molecule.

Examples of anthraquinone dyes include: C.I. solvent yellow (solvent yellow) 117, 163, 167, 189, C.I. solvent orange (solvent orange) 77, 86, C.I. solvent red 111, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247, C.I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59 , 60, C.I. solvent blue (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. solvent green (solvent green) 3, 28, 29, 32, 33, C.I. acid red 80, C.I. acid green (acid green) 25, 27, 28, 41, C.I. acid violet 34, C.I. Acid blue 25, 27, 40, 45, 78, 80, 112, C.I. Disperse yellow (disperse yellow) 51, C.I. Disperse violet (disperse violet) 26, 27, C.I. Disperse blue (disperse blue) 1, 14, 56, 60. C.I. direct blue (direct blue) 40, C.I. mordant red (mordant red) 3, 11, C.I. mordant blue (mordant blue) 8, etc. In addition, Japanese Patent Application Laid-Open No. 9-291237, International Publication No. 2003/080734 Manual, International Publication No. 2006/024617 Manual, Japanese Patent Application Publication No. 2011-174987, Japanese Patent Application Publication No. 2013-53273 can be used Anthraquinone dyes described in gazettes and the like are known technologies. The anthraquinone dye is preferably dissolved in an organic solvent, and is more preferably a blue, purple or red anthraquinone dye. As an anthraquinone dye, from the viewpoint of brightness or contrast, C.I. Solvent Blue 35, C.I. Solvent Blue 45, C.I. Acid Blue 80, C.I. Solvent Blue 104, and C.I. Solvent Blue 122 are preferred.

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

In recent years, in order to improve the color reproduction characteristics and reduce the thickness of color filters, it is necessary to increase the content of the colorant in the photosensitive coloring composition. The content of the colorant (A) is preferably 30 mass % or more, and more preferably 40 mass % or more in 100 mass parts of non-volatile components of the photosensitive coloring composition for color filters according to the embodiment of the present invention. This case is preferable because sufficient color reproducibility is obtained and the film thickness is reduced. In addition, if it is preferably 65 mass % or less, more preferably 60 mass % or less, the content of the resin or photopolymerizable compound as the curing material is appropriate and a sufficient cured coating film can be obtained. Generally, when the content of the colorant becomes high, the patterning properties of the photosensitive coloring composition tend to deteriorate. According to the present invention, sufficient patterning characteristics can be obtained in a photosensitive coloring composition in which the colorant content required for normal high color reproduction is 30 mass % to less than 40 mass %. Of course, in more difficult coloring Sufficient patterning properties can also be obtained in a photosensitive coloring composition whose content of the agent is 40% by mass or more.

<Photopolymerization initiator (C)>

In order to harden the composition by ultraviolet irradiation and form a filter segment by photodevelopment, the photosensitive composition of the present invention must add a photopolymerization initiator (C) and use a solvent-developing type or an alkali-developing type photosensitive composition. The form of the composition is prepared. From the viewpoint of practical ultraviolet sensitivity, it is more preferable that the compounding amount of the photopolymerization initiator is 0.3% by mass to 8.0% by mass in the total nonvolatile components of the photosensitive coloring composition.

Examples of the photopolymerization initiator (C) include: 4-phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4- Isopropylphenyl)-2- Hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one , 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, or 2-benzyl Acetophenone compounds such as -2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzene Benzoin compounds such as dimethyl ketal; benzophenone, benzoyl benzoic acid, methyl benzoate, 4-phenyl benzophenone, hydroxybenzophenone, acrylation Benzophenone, 4-benzyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone etc. Benzophenone compounds; thioxanthone, 2-chlorothioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diisopropyl thioxanthone, or Thiaxanthone compounds such as 2,4-diethylthiaxantone; 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-(naphthyl-1-yl) -4,6-bis(trichloromethyl)s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)s-triazine, 2,4 -Trichloromethyl-(piperonyl)-6-triazine, or triazine compounds such as 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; 1, 2-Octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyloxime)], or ethyl ketone, 1-[9-ethyl-6-(2- Methyl)-9H-triazol-3-yl]-,1-(O-acetyl oxime) and other oxime ester compounds; bis(2,4,6-trimethylbenzoyl) ) Phosphine compounds such as phenylphosphine oxide or 2,4,6-trimethylbenzyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethyl anthraquinone ; Boric acid ester compounds; benzazole compounds; imidazole compounds; or titanocene compounds, etc. These photopolymerization initiators can Used alone or in combination of two or more.

Examples of commercially available acetophenone compounds include "IRGACURE 907" (2-methyl-1-[4-(methylthio)phenyl]- manufactured by BASF Corporation). 2-morpholinylpropan-1-one), "IRGACURE 369" (2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4 -(4-morpholinyl)phenyl]-1-butanone), "IRGACURE 379" (2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl )-butane-1-one), all examples of phosphine compounds include "IRGACURE 819" (bis(2,4,6-trimethylbenzoyl)benzene manufactured by BASF) phosphine oxide), "IRGACURE TPO" (2,4,6-trimethylbenzyldiphenylphosphine oxide), etc. Among these, oxime ester compounds are preferred.

[Oxime ester compounds]

The oxime ester compound absorbs ultraviolet rays and causes the cleavage of the N-O bond of the oxime, thereby generating iminyl radicals and alkyloxy radicals. These radicals are further decomposed to generate highly active radicals, so patterns can be formed with a small amount of exposure. As the oxime ester-based compound, an oxime ester-based photopolymerization initiator represented by the general formula (4) is preferred. By using this initiator, the resin-type dispersant (B) can be efficiently polymerized.

(Oxime ester photopolymerization initiator represented by general formula (4))

General formula (4) [Chemical formula 7]

In the general formula (4), it is preferable that Y ¹ is a hydrogen atom, or an alkenyl group, an alkyl group, an alkyloxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, or an alkyl group which may have a substituent. Alkylthio, arylthio, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acyl, acyloxy, amino, phosphinyl ( phosphinoyl), carbamate group, or sulfamate group, Y ² is a hydrogen atom, or an alkenyl group, alkyl group, alkyloxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic group which may have a substituent Epoxy group, alkylthio group, arylthio group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyloxy group, or amino group; Z is Direct bonding or -CO- group, Y ³ is a monovalent organic group containing a benzazole group which may have a substituent, or a Ph-S-Ph- group (Ph represents a phenyl group or a phenylene group which may have a substituent).

Examples of the optionally substituted alkenyl group in Y ¹ include linear, branched, monocyclic or condensed polycyclic alkenyl groups having 1 to 18 carbon atoms. These may also have multiple carbon atoms in the structure. - Carbon double bond, specific examples include vinyl, 1-propenyl, allyl, 2-butenyl, 3-butenyl, isopropenyl, isobutenyl, 1-pentenyl, 2 -Pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, cyclopentenyl base, cyclohexenyl, 1,3-butadienyl, cyclohexadienyl, cyclopentadienyl, etc.

Examples of the alkyl group in Y ¹ that may have a substituent include a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms, or an alkyl group having 2 to 18 carbon atoms, as appropriate. A linear, branched chain, monocyclic or condensed polycyclic alkyl group interrupted by more than one -O-. Specific examples of linear, branched, monocyclic or condensed polycyclic alkyl groups having 1 to 18 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl Base, octyl, nonyl, decyl, dodecyl, octadecyl, isopropyl, isobutyl, isopentyl, second butyl, third butyl, second pentyl, third pentyl , tertiary octyl, neopentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, boronyl, 4-decylcyclohexyl, etc. In addition, specific examples of a linear or branched chain alkyl group having a carbon number of 2 to 18 and optionally interrupted by one or more -O- include: -CH ₂ -O-CH ₃ , -CH ₂ - CH ₂ -O-CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -O-CH ₂ -CH ₃ , -(CH ₂ -CH ₂ -O) _n -CH ₃ (here, n is 1 to 8), -(CH ₂ -CH ₂ -CH ₂ -O) _m -CH ₃ (here, m is 1 to 5), -CH ₂ -CH(CH ₃ )-O-CH ₂ -CH ₃ - , -CH ₂ -CH-(OCH ₃ ) ₂ , etc.

Specific examples of the monocyclic or condensed polycyclic alkyl group having 2 to 18 carbon atoms and optionally interrupted by one or more -O- include the following groups, but are not limited thereto.

[Chemical 8]

Examples of the alkyloxy group in Y ¹ which may have a substituent include a linear, branched chain, monocyclic or condensed polycyclic alkyloxy group having 1 to 18 carbon atoms, or an alkyloxy group having 2 carbon atoms. to 18 and optionally a linear, branched chain, monocyclic or condensed polycyclic alkyloxy group interrupted by more than one -O-. Specific examples of linear, branched chain, monocyclic or condensed polycyclic alkyloxy groups having 1 to 18 carbon atoms include: methyloxy group, ethyloxy group, propyloxy group, Butyloxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, dodecyloxy, octadecyloxy, isopropyloxy base, isobutyloxy, isopentyloxy, second butyloxy, third butyloxy, second pentyloxy, third pentyloxy, third octyloxy, new Pentyloxy, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, adamantyloxy, norbornyloxy, boronyloxy, 4-decyl ring Hexyloxy etc. In addition, specific examples of linear or branched chain alkyloxy groups having 2 to 18 carbon atoms and optionally interrupted by one or more -O- include: -O-CH ₂ -O-CH ₃ , -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₃ , -O-CH ₂ -CH ₂ -CH ₂ -O-CH ₂ -CH ₃ , -O-(CH ₂ -CH ₂ -O) _n -CH ₃ (here, n is 1 to 8), -O-(CH ₂ -CH ₂ -CH ₂ -O) _m -CH ₃ (here, m is 1 to 5), -O-CH ₂ - CH(CH ₃ )-O-CH ₂ -CH ₃ -, -O-CH ₂ -CH-(OCH ₃ ) ₂ , etc.

Specific examples of the monocyclic or condensed polycyclic alkyloxy group having 2 to 18 carbon atoms and optionally interrupted by one or more -O- include the following groups, but are not limited thereto.

Examples of the optionally substituted aryl group in Y ¹ include monocyclic or condensed polycyclic aryl groups having 6 to 24 carbon atoms. Specific examples include: phenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 9-anthracenyl, 2-phenanthrenyl, 3-phenanthrenyl, 9-phenanthrenyl, 1-pyrenyl, 5-tetraphenyl, 1-indenyl, 2-acenaphthyl, 1-acenaphthene base, 2-benzyl, 9-benzyl, 3-perylene, o-tolyl, m-tolyl, p-tolyl, 2,3-xylyl, 2,5-xylyl, mesityl, p-cumenyl, p-dodecylphenyl, p-cyclohexylphenyl, 4-biphenyl, o-fluorophenyl, m-chlorophenyl, p-bromophenyl, p-hydroxyphenyl, m-carboxyphenyl, o- Mercaptophenyl, p-cyanophenyl, m-nitrophenyl, m-azidophenyl, etc.

Examples of the optionally substituted aryloxy group in Y ¹ include monocyclic or condensed polycyclic aryloxy groups having 4 to 18 carbon atoms. Specific examples include: phenoxy group and 1-naphthyloxy group. base, 2-naphthyloxy, 9-anthracenyloxy, 9-phenanthrenyloxy, 1-pyrenyloxy, 5-tetraphenyloxy, 1-indenyloxy, 2-azulenyl Oxygen group, 1-acenaphthyloxy group, 9-benzoyloxy group, etc.

啉基(quinoxalinylgroup)、喹唑啉基(quinazolinyl group)、噌啉基(cinnolinyl group)、蝶啶基(pteridinyl group)、4aH-哢唑基、2-哢唑基、3-哢唑基、β-哢啉基(β-carbolinyl group)、啡啶基(phenanthridinyl group)、2-吖啶基、萘嵌間二氮雜苯基(perimidinyl group)、啡啉基(phenanthrolinyl group)、啡(口井)基、啡呻嗪基(phenarsazinyl group)、異噻唑基、酚噻(口井)基、異噁唑基、呋呫基(furazanyl group)、3-啡

(口井)基(3-phenoxazinyl group)、異苯並二氫吡喃基(isochromanyl group)、苯並二氫吡喃基、吡咯烷基(pyrrolidinyl group)、吡咯啉基(pyrrolinyl group)、咪唑烷基(imidazolidinyl group)、咪唑啉基(imidazolinyl group)、吡唑烷基(pyrazolidinyl group)、吡唑啉基(pyrazolinyl group)、呱啶基、呱嗪基、吲哚啉基(indolinyl group)、異吲哚啉基、奎寧環基(quinuclidinyl group)、嗎啉基、硫雜蒽酮基(thioxantholyl group)、4-喹啉基、4-異喹啉基、3-酚噻(口井)基、2-吩噁噻基、3- 香豆素基(3-coumarinyl)等。 Examples of the heterocyclic group in Y ¹ that may have a substituent include an aromatic or aliphatic heterocyclic group with 4 to 24 carbon atoms containing a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Examples include: 2 -Thienyl, 2-benzothienyl, naphtho[2,3-b]thienyl, 3-thienthyl, 2-thienthyl, 2-furyl, 2-benzofuranyl, pyranyl , isobenzofuranyl, chromenyl group, xanthranyl, phenoxathiinyl group, 2H-pyrrolyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyridyl Azinyl, pyrimidinyl, pyridazinyl, indolizinyl group, isoindolyl, 3H-indolyl, 2-indolyl, 3-indolyl, 1H-indazolyl, purinyl ( purinyl group), 4H-quinolizinyl group, isoquinolinyl, quinolinyl, phthalazinyl, naphthyridinyl, quinolinyl

Quinoxalinyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-conazolyl group, 2-conazolyl group, 3-conazolyl group, β -β-carbolinyl group, phenanthridinyl group, 2-acridinyl, perimidinyl group, phenanthrolinyl group, phenanthrolinyl group ) group, phenarsazinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazinyl group, 3-phenanthrene group

(3-phenoxazinyl group), isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazole Alkyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, pyridinyl group, pyrazinyl group, indolinyl group, Isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxantholyl group, 4-quinolinyl group, 4-isoquinolinyl group, 3-phenothiol (guchi) base, 2-phenoxathiyl, 3-coumarinyl (3-coumarinyl), etc.

Examples of the heterocyclic oxy group in Y ¹ which may have a substituent include a monocyclic or condensed polycyclic heterocyclic oxy group having 4 to 18 carbon atoms containing a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples include: 2-furyloxy, 2-thienyloxy, 2-indolyloxy, 3-indolyloxy, 2-benzofuryloxy, and 2-benzothiophene baseoxy group, 2-conazolyloxy group, 3-conazolyloxy group, 4-conazolyloxy group, 9-acridinyloxy group, etc.

Examples of the optionally substituted alkylthio group in Y ¹ include linear, branched, monocyclic or condensed polycyclic alkylthio groups having 1 to 18 carbon atoms. Specific examples include: Methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, octylthio, decylthio, dodecylthio, octadecylthio, etc.

Examples of the optionally substituted arylthio group in Y ¹ include monocyclic or condensed polycyclic arylthio groups having 6 to 18 carbon atoms. Specific examples include phenylthio group and 1-naphthylthio group. base, 2-naphthylthio group, 9-anthracenethio group, 9-phenanthrenethio group, etc.

The alkylsulfinyl group in Y ¹ which may have a substituent is preferably an alkylsulfinyl group having 1 to 20 carbon atoms. Specific examples include: methylsulfinyl group and ethylsulfinyl group. acyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl, hexylsulfinyl, cyclohexylsulfinyl, octylsulfinyl, 2-ethylhexyl Sulfinyl group, decanoyl sulfenyl group, dodecyl sulfenyl group, octadecyl sulfenyl group, cyanomethyl sulfenyl group, methyloxymethyl sulfenyl group wait.

The arylsulfinyl group in Y ¹ which may have a substituent is preferably an arylsulfinyl group having 6 to 30 carbon atoms. Specific examples include: phenylsulfinyl group and 1-naphthyl group. Sulfenyl group, 2-naphthylsulfenyl group, 2-chlorophenylsulfenyl group, 2-methylphenylsulfenyl group, 2-methyloxyphenylsulfinyl group, 2- Butyloxyphenylsulfinyl, 3-chlorophenylsulfinyl, 3-trifluoromethylphenylsulfinyl, 3-cyanophenylsulfinyl, 3-nitrobenzene Sulfenyl group, 4-fluorophenylsulfenyl group, 4-cyanophenylsulfenyl group, 4-methyloxyphenylsulfenyl group, 4-methylthiophenylsulfenyl group acyl group, 4-phenylthiophenyl sulfenyl group, 4-dimethylaminophenyl sulfenyl group, etc.

The alkylsulfonyl group in Y ¹ which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms. Specific examples include: methylsulfonyl group, ethylsulfonyl group, propyl group Sulfonyl group, isopropylsulfonyl group, butylsulfonyl group, hexylsulfonyl group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decylsulfonyl group , dodecanoyl sulfonyl, octadecanoyl sulfonyl, cyanomethylsulfonyl, methyloxymethylsulfonyl, etc.

The arylsulfonyl group in Y ¹ which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms. Specific examples include phenylsulfonyl group and 1-naphthylsulfonyl group. , 2-naphthylsulfonyl, 2-chlorophenylsulfonyl, 2-methylphenylsulfonyl, 2-methoxyphenylsulfonyl, 2-butyloxyphenylsulfonyl base, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group base, 4-cyanophenylsulfonyl group, 4-methyloxyphenylsulfonyl group, 4-methylthiophenylsulfonyl group, 4-phenylthiophenylsulfonyl group, 4- Dimethylaminophenylsulfonyl, etc.

Examples of the acyl group in Y ¹ which may have a substituent include a hydrogen atom or a carbonyl group bonded to a linear, branched, monocyclic or condensed polycyclic aliphatic having 1 to 18 carbon atoms, and a carbonyl group. A carbonyl group substituted by an alkyloxy group having 2 to 20 carbon atoms, a carbonyl group bonded to a monocyclic or condensed polycyclic aryl group having 6 to 18 carbon atoms, a monocyclic or condensed polycyclic group having 6 to 18 carbon atoms A carbonyl group substituted by an aryloxy group, a carbonyl group bonded to a C4-18 monocyclic or condensed polycyclic heterocyclic group containing a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom, as specific examples, Examples include: formyl, acetyl, propyl, butyl, isobutyl, pentyl, isopentyl, trimethylacetyl, lauryl, myristyl, palmityl, hard Aliphatyl, cyclopentylcarbonyl, cyclohexylcarbonyl, acrylyl, methacrylyl, butenyl, isobutenyl, oleyl, cinnamyl, benzyl, methyloxycarbonyl , ethyloxycarbonyl, propyloxycarbonyl, butyloxycarbonyl, hexyloxycarbonyl, octyloxycarbonyl, decyloxycarbonyl, octadecyloxycarbonyl, trifluoromethyloxycarbonyl , Toluyl, 1-naphthoyl, 2-naphthoyl, 9-anthracenylcarbonyl, phenyloxycarbonyl, 4-methylphenyloxycarbonyl, 3-nitrophenyloxycarbonyl , 4-dimethylaminophenyloxycarbonyl, 2-methylthiophenyloxycarbonyl, 1-naphthyloxycarbonyl, 2-naphthyloxycarbonyl, 9-anthracenyloxy Carbonyl group, 3-furyl carboxyl group, 2-thenoyl group (2-thenoyl), nicotinoyl group (nicotinoyl), isonicotinoyl group, etc.

Examples of the acyloxy group in Y ¹ which may have a substituent include a acyloxy group having 2 to 20 carbon atoms. Specific examples include an acetyloxy group, a propionyloxy group, and a butyloxy group. , pentyloxy, trifluoromethylcarbonyloxy, benzyloxy, 1-naphthylcarbonyloxy, 2-naphthylcarbonyloxy, etc.

Examples of the optionally substituted amino group in Y ¹ include amino group, alkylamino group, dialkylamino group, arylamino group, diarylamino group, alkylarylamino group, benzylamino group, dibenzylamino group, etc. .

Here, examples of the alkylamino group include methylamino, ethylamino, propylamino, butylamino, pentylamino, hexylamino, heptylamino, octylamino, nonylamino, decylamino, Dodecyl amino, octadecyl amino, isopropylamino, isobutylamino, isopentylamino, second butylamino, third butylamino, second pentylamino, third pentylamino, third Trioctylamino, neopentylamino, cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, cycloheptylamino, cyclooctylamino, cyclododecylamino, 1-adamantanamino , 2-adamantane amino, etc.

Examples of the dialkylamino group include: dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, diheptylamino group, dioctyl amino group, dinonyl group amino group, didecyl amino group, di-dodecyl amino group, di-octadecyl amino group, diisopropylamino group, diisobutylamino group, diisopentylamino group, methylethylamino group, methylpropyl group Amino, methylbutylamino, methylisobutylamino, cyclopropylamino, pyrrolidinyl, pyridinyl, pyridinyl, etc.

Examples of the arylamino group include anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidine group, m-toluidine group, p-toluidine group, 2-biphenylamino group, and 3-biphenyl group. Amino, 4-biphenylamino, 1-hydroxylamino, 2-hydroxylamino, 2-thiazoleamino, p-terphenylamino, etc.

Examples of diarylamino groups include diphenylamino, ditolylamino, N-phenyl-1-naphthylamino, N-phenyl-2-naphthylamino, and the like.

Examples of the alkylaryl amino group include: N-methylanilino group, N-methyl-2-pyridinyl group, N-ethylanilino group, N-propylanilino group, N-butylanilino group, N- Isopropyl base, N-pentylanilino group, N-ethylanilino group, N-methyl-1-naphthylamino group, etc.

Examples of the phosphinyl group in Y ¹ which may have a substituent include a phosphinyl group having 2 to 50 carbon atoms. Specific examples include: dimethylphosphinyl group and diethylphosphinyl group. , Dipropylphosphinyl, diphenylphosphenyl, dimethoxyphosphenyl, diethoxyphosphenyl, diphenylphosphenyl, bis(2,4 , 6-trimethylphenyl) phosphinyl, etc.

Examples of the optionally substituted aminoformyl group in Y ¹ include aminoformyl groups having 1 to 30 carbon atoms. Specific examples include: N-methylcarbamoformyl group and N-ethylcarbamoformyl group. Cyl, N-propylcarbamacyl, N-butylcarbamacyl, N-hexylcarbamacyl, N-cyclohexylcarbamacyl, N-octylcarbamacyl, N-decyl N-methylcarbamocarbonyl, N-octadecylcarbamocarbamate, N-phenylcarbamocarbamate, N-2-methylphenylcarbamocarbamate, N-2-chlorophenylcarbamocarbamate, N-2-isopropoxyphenylcarbamacyl, N-2-(2-ethylhexyl)phenylcarbamacyl, N-3-chlorophenylcarbamacyl, N-3-nitro phenylcarbamate, N-3-cyanophenylcarbamate, N-4-methoxyphenylcarbamate, N-4-cyanophenylcarbamate, N- 4-Methylthiophenylcarbamacyl, N-4-phenylthiophenylcarbamacyl, N-methyl-N-phenylcarbamacyl, N,N-dimethylamine Formyl, N,N-dibutylcarbamacyl, N,N-diphenylcarbamyl, etc.

Examples of the optionally substituted sulfamic acid group in Y ¹ include a sulfamic acid group having 0 to 30 carbon atoms. Specific examples include: sulfamic acid group, N-alkyl sulfamic acid group, N -Aryl sulfamate group, N,N-dialkyl sulfamate group, N,N-diaryl sulfamate group, N-alkyl-N-aryl sulfamate group, etc. More specific examples include: N-methylsulfamate group, N-ethylsulfamate group, N-propylsulfamate group, N-butylsulfamate group, N-hexylsulfamate group, N -Cyclohexylsulfamate, N-octylsulfamate, N-2-ethylhexylsulfamate, N-decylsulfamate, N-octadecylsulfamate, N- Phenylsulfamate group, N-2-methylphenylsulfamate group, N-2-chlorophenylsulfamate group, N-2-methoxyphenylsulfamate group, N-2- Isopropoxyphenyl sulfamate, N-3-chlorophenyl sulfamate, N-3-nitrophenyl sulfamate, N-3-cyanophenylsulfamate, N -4-Methoxyphenylsulfamate, N-4-cyanophenylsulfamate, N-4-dimethylaminophenylsulfamate, N-4-methylthiobenzene sulfamate group, N-4-phenylthiophenylsulfamate group, N-methyl-N-phenylsulfamate group, N,N-dimethylsulfamate group, N,N -Dibutylsulfamate, N,N-diphenylsulfamate, etc.

Alkenyl group, alkyl group, alkyloxy group, aryl group, aryloxy group, heterocyclic group, heterocyclicoxy group, alkylthio group, arylthio group, alkyl group which may have a substituent in Y ² Sulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyloxy group, and amino group, and the alkenyl group in Y ¹ which may have a substituent, may have a substitution Alkyl group of the base, alkyloxy group which may have a substituent, aryl group which may have a substituent, aryloxy group which may have a substituent, heterocyclic group which may have a substituent, heterocyclic oxy which may have a substituent group, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, an alkylsulfinyl group which may have a substituent, an arylthio group which may have a substituent, an arylthio group which may have a substituent The alkylsulfonyl group, the arylsulfonyl group which may have a substituent, the acyloxy group which may have a substituent, and the amino group which may have a substituent have the same meaning.

Examples of these substituents in Y ¹ and Y ² 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; and phenoxy group , p-tolyloxy and other aryloxy groups; methoxycarbonyl, butoxycarbonyl, phenoxycarbonyl and other alkoxycarbonyl groups; acetyloxy, propyloxy, benzyloxy, etc. Cyloxy; acetyl, benzyl, isobutyl, acryl, methacryl, methoxalyl and other acyl groups; methylthio, tert-butylthio Alkylthio groups; arylthio groups such as phenylthio group and p-tolylthio group; alkylamino groups such as methylamino group and cyclohexylamino group; dimethylamino group, diethylamino group, morpholinyl group, and pyridine group dialkylamino groups such as phenylamino group; arylamino groups such as phenylamino group and p-tolylamino group; methyl group, ethyl group, tert-butyl group, dodecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, Alkyl groups such as cycloheptyl, cyclooctyl and cyclooctadecyl; aryl groups such as phenyl, p-tolyl, xylyl, cumenyl, naphthyl, anthracenyl and phenanthryl; heterogeneous groups such as furyl and thienyl Ring groups, etc., in addition: hydroxyl group, carboxyl group, formyl group, mercapto group, sulfo group, methanesulfonyl group (mesyl), p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trifluoromethyl group, etc. Chloromethyl, trimethylsilyl, phosphinico group, phosphono group, trimethylammonium group, dimethylsulfonyl group, triphenylbenzoylmethylphosphonium group, etc.

In addition, one or more types of these substituents may be present, and the hydrogen atoms of these substituents may be substituted with other substituents.

Among the oxime ester-based photopolymerization initiators represented by the general formula (4), the oxime ester-based photopolymerization initiator represented by the following general formula (5) or the general formula (6), especially the general formula (6) ), an oxime ester-based photopolymerization initiator having a benzole moiety in the molecule is used as the photopolymerization initiator (C) used in the present invention in combination with the resin-type dispersant (B) to obtain good patterning properties. , so it is more preferred among oxime ester photopolymerization initiators.

(Oxime ester photopolymerization initiator represented by general formula (5))

General formula (5)

General formula (5) corresponds to the case where Z in general formula (4) is a -CO- group and Y ³ is a Ph-S-Ph- group. Y ⁴ to Y ⁶ are preferably hydrogen atoms or may have substituents. Alkyl or aryl. The optionally substituted alkyl group or the optionally substituted aryl group in Y ⁴ to Y ⁶ has the same meaning as the alkyl group or aryl group in Y ¹ and Y ² .

Furthermore, Y ¹ is more preferably an aryl group which may have a substituent, Y ² is more preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent, Y ⁴ and Y ⁶ are more preferably a hydrogen atom, and Y ⁵ is more preferably Hydrogen atom, or Y ⁷ -CO- group.

Examples of Y ⁷ 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; and aromatic groups such as phenoxy group and p-tolyloxy group. baseoxy; alkoxycarbonyl such as methoxycarbonyl, butoxycarbonyl, phenoxycarbonyl; acetyloxy, propyloxy, benzoyloxy and other acetyloxy; acetyloxy , benzoyl, isobutyl, acryl, methacryl, methoxyl and other acyl groups; methylthio, tert-butylthio and other alkylthio groups; phenylthio, Arylthio groups such as p-tolylthio group; alkylamino groups such as methylamino and cyclohexylamino groups; dialkylamino groups such as dimethylamino, diethylamino, morpholinyl and piridinyl groups; phenylamino, Arylamino groups such as p-tolylamino; alkyl groups such as methyl, ethyl, tert-butyl, and dodecyl; phenyl, p-tolyl, xylyl, cumenyl, naphthyl, anthracenyl, and phenanthryl , aryl groups such as benzofuranyl; heterocyclic groups such as furyl and thienyl, etc. In addition, hydroxyl, carboxyl, formyl, mercapto, sulfo, methanesulfonyl, p-toluenesulfonyl, amino , nitro, cyano, trifluoromethyl, trichloromethyl, trimethylsilyl, phosphate subunit, phosphonium, trimethylammonium, dimethylsulfonyl, triphenylbenzoyl Phosphonium base et al.

As the substituent of Y ² , cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclooctadecyl are further preferred.

Specific examples of the oxime ester-based photopolymerization initiator represented by the general formula (5) include photopolymerization initiators represented by the following chemical formulas (5-1) to (5-4).

(Oxime ester photopolymerization initiator represented by general formula (6))

General formula (6)

General formula (6) corresponds to the case where Y ³ in general formula (4) is a monovalent organic group containing a benzazole group which may have a substituent, and the substituents in Y ⁷ to Y ¹⁴ and Y ¹ and Y ² are Same meaning.

Furthermore, Y ¹ is preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent, Y ² is preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent, and Y ⁷ ~ Y ¹⁴ is preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent.

When Z in the general formula (6) represents a direct bond, it is preferably the following general formula: An oxime ester photopolymerization initiator represented by formula (6a).

(Oxime ester photopolymerization initiator represented by general formula (6a))

General formula (6a)

General formula (6a) corresponds to the case where Z in general formula (6) is directly bonded, and Y ⁷ to Y ¹⁰ and Y ¹² to Y ¹³ in general formula (6) are hydrogen atoms.

In addition, Y ¹¹ is preferably a Y ¹⁵ -CO- group or a nitro group. Y ¹⁵ has the same meaning as the substituent in Y ¹ and Y ² , and is preferably an aryl group which may have a substituent. The Y ¹⁵ -CO- group is further preferably an acetyl group, a benzyl group, an isobutyl group, an acryl group, a methacryl group, a methoxyl group or the like which may have a substituent. More preferred is a benzyl group or nitro group which may have a substituent. R ¹⁴ is preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent.

In addition, the substituent in the benzyl group which may have a substituent is preferably an alkyl group having 1 to 20 carbon atoms or an alkyloxy group. Furthermore, the alkyl group is preferably a methyl group or an ethyl group, and among the alkyloxy groups, a straight chain, a branched chain, or a monocyclic chain having a carbon number of 2 to 18 and optionally interrupted by one or more -O- is preferable. Or a condensed polycyclic alkyloxy group, and a linear, branched chain, monocyclic or condensed polycyclic alkane with a carbon number of 2 to 18 in Y ¹ and optionally interrupted by more than one -O- The baseoxy group has the same meaning.

Y ² is preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent. The substituent is preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, or a cyclooctadecyl group. base and other cycloalkyl groups. In addition, an aryl group which may have a substituent is preferred, and the substituent is preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an alkyl group such as a methoxy group, an ethoxy group, or a tert-butoxy group. Oxygen group is preferred.

Specific examples of the oxime ester-based photopolymerization initiator represented by the general formula (6a) include photopolymerization initiators represented by the following chemical formulas (6a-1) to (6a-6).

(Oxime ester photopolymerization initiator represented by general formula (6b))

When Z in the general formula (6) is a -CO- group, it is preferably an oxime ester-based photopolymerization initiator represented by the following general formula (6b).

General formula (6b)

General formula (6b) corresponds to the case where Z in general formula (6) is a -CO- group and Y ³ is a monovalent organic group containing a benzazolyl group which may have a substituent, and is a ketone type having a benzazolyl group. Oxime ester is a photopolymerization initiator.

Y ⁷ to Y ¹³ are preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent, and Y ¹⁴ is preferably an aryl group which may have a substituent.

As a substituent of the aryl group which may have a substituent, an acetyl group and a benzyl group are preferable. A acyl group such as an isobutyl group, an acryl group, a methacryl group, a methoxychloryl group, and the like, and a benzyl group is more preferred.

Specific examples of the oxime ester-based photopolymerization initiator represented by the general formula (6b) include photopolymerization initiators represented by the following chemical formulas (6b-1) to (6b-4).

Commercially available products of these oxime ester compounds include BASF's 1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzyl) Benzyl oxime)] (IRGACURE OXE-01), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-triazol-3-yl] -,1-(O-acetyl oxime) (IRGACURE OXE 02), N-1919 (manufactured by ADEKA), TRONLY TR-PBG-304, TRONLY TR-PBG-305, TRONLY TR-PBG-309 (both manufactured by Changzhou Qianli New Materials Co., Ltd.), etc. In addition, Japanese Patent Laid-Open No. 2007-210991, Japanese Patent Laid-Open No. 2009-179619, Japanese Patent Laid-Open No. 2010-037223, Japanese Patent Laid-Open No. 2010-215575, Japanese Patent Laid-Open No. 2010-215575, and Japanese Patent Laid-Open No. 2010-215575 may also be used. The oxime ester-based photopolymerization initiator described in Publication No. 2011-020998 and others was developed.

<Organic solvent (D)>

The photosensitive coloring composition of the present invention contains an organic solvent (D). Using the organic solvent (D), the colorant can be easily dispersed and infiltrated into the colorant carrier, and then coated on a substrate such as a glass substrate with a dry film thickness of 0.2 μm to 5 μm to form a filter segment.

An organic solvent can be used individually by 1 type, or in mixture of 2 or more types. In addition, the solvent can adjust the coloring composition to an appropriate viscosity and form a filter segment with a target uniform film thickness. Therefore, it is preferable to use the total weight of the coloring agent as the basis (100 mass%) and 500 mass% to Used in an amount of 4000% by mass.

Examples of the organic solvent (D) include 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1 ,3-butylene glycol (1,3-butylene glycol), 1,3-butylene glycol diacetate, 1,4-butylene glycol diacetate, 1,4-dioxane, 2-heptane Ketone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, 3-ethoxy Ethyl propionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutylacetate , 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, 2nd butylbenzene, 3rd butylbenzene, γ-butyrolactone, isobutyl alcohol , isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol 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, di Isobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol Alcohol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene 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 , methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid esters, etc.

These solvents can be used individually or in combination of 2 or more types.

Among them, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol diethyl acetate are preferably used in terms of good dispersibility and penetrability of the colorant and good coating properties of the photosensitive composition. Acid ester, ethylene glycol monomethyl ether acetic acid Ester, ethylene glycol monoethyl ether acetate, 1,3-butanediol diacetate, cyclohexanol acetate, 1,4-butanediol diacetate, butanediol diacetate, etc. Alcohols such as acetate, benzyl alcohol, diacetone alcohol, 1-methoxy-2-propanol, 3-methoxybutanol, ketones such as cyclohexanone, ethyl 3-ethoxypropionate, etc. .

<Polymerizable compound (E)>

The photosensitive coloring composition of the present invention contains a polymerizable compound (E). The polymerizable compound (E) contains a monomer or oligomer that is cured by ultraviolet rays, heat, or the like to form a transparent resin.

Examples of monomers and oligomers that are cured by ultraviolet light or heat to form a transparent resin include: (meth)acrylic acid methyl ester, (meth)ethyl acrylate, (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid ethyl ester, (meth)acrylic acid ethyl ester 2-hydroxypropyl methacrylate, cyclohexyl (meth)acrylate, β -carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di (meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol ( Meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane propylene oxide (PO) modified tri(meth)acrylate, trimethylolpropane ring Ethylene oxide (EO) modified tri(meth)acrylate, isocyanuric acid EO modified di(meth)acrylate, isocyanuric acid EO modified tri(meth)acrylate, di(meth)acrylate -Trimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate , bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate Various acrylates and Methacrylate; (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N- Hydroxymethyl (meth)acrylamide, N-vinylformamide, acrylonitrile, etc., but are not necessarily limited to these.

These polymerizable compounds can be used alone or in combination of two or more types.

Examples of these commercial products include: KAYARAD R-128H, KAYARAD R526, KAYARAD PEG400DA, KAYARAD ( KAYARAD)MAND, KAYARAD NPGDA, KAYARAD R-167, KAYARAD HX-220, KAYARAD R-551, KAYARAD (KAYARAD) R712, KAYARAD (KAYARAD) R-604, KAYARAD (KAYARAD) R-684, KAYARAD (KAYARAD) GPO-303, KAYARAD (KAYARAD) TMPTA, KAYARAD KAYARAD DPHA, KAYARAD DPEA-12, KAYARAD DPHA-2C, KAYARAD D-310, KAYARAD D-330, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, and Toa Gosei Co., Ltd. M-303, M-305, M-306, M-309, M-310, M-321, M-325, M-350, M-360, M-313, M-315, M-400, M- 402, M-403, M-404, M-405, M-406, M-450, M-452, M-408, M-211B, M-101A, Viscoat #310HP, Viscoat #335HP, Viscoat #700, Viscoat #295, Viscoat manufactured by Osaka Organic Co., Ltd. #330, Viscoat #360, Viscoat #GPT, Viscoat #400, Viscoat #405, A-9300 manufactured by Shin Nakamura Chemical Company, etc.

The content of the polymerizable compound (E) relative to all nonvolatile components is preferably 15% by mass to 45% by mass. Furthermore, it is preferable that the content is 20% by mass to 35% by mass. When the amount is less than the above, the taper of the photosensitive colored composition pattern becomes long and extended, making it difficult to form a high-definition fine pixel pattern. When the amount is greater than the above, problems such as deterioration of analytical properties and residues may occur.

(Polymerizable compound with acidic group)

The polymerizable compound in the present invention may contain a polymerizable compound having an acid group. Examples of the acid group include a sulfonic acid group, a carboxyl group, a phosphate group, and the like.

Examples of the polymerizable compound having an acid group include free hydroxyl-containing poly(meth)acrylates of polyhydric alcohols and (meth)acrylic acid, and esterified products of dicarboxylic acids; polycarboxylic acids, and (meth)acrylic acid. Esterates of monohydroxyalkyl esters, etc. Specific examples include trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate. Monohydroxyl oligoacrylates such as acrylates or monohydroxyl oligomethacrylates, and monoesters containing free carboxyl groups with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and terephthalic acid; propane -1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4-tricarboxylic acid acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid and other tricarboxylic acids, and 2-hydroxyethyl acrylate, Monoacrylic acid monohydroxy esters such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate, or oligomeric esters of monomethacrylic acid monohydroxy esters containing free carboxyl groups, etc.

As these commercial products, Viscoat #2500P manufactured by Osaka Organic Co., Ltd., M-5300, M-5400, M-5700, M-510, M-520, etc. manufactured by Toagosei Co., Ltd. can be suitably used.

These polymerizable compounds having an acid group can be used alone or in combination of two or more.

(Polymerizable compound having urethane bond)

The polymerizable compound in the present invention may contain a polymerizable compound containing at least one each of an ethylenically unsaturated bond and a urethane bond. For example, polyfunctional urethane acrylate obtained by reacting a polyfunctional isocyanate and a (meth)acrylate having a hydroxyl group, or a polyfunctional isocyanate reacting with an alcohol to further react a (meth)acrylate having a hydroxyl group. Polyfunctional urethane acrylate obtained by reacting with acrylic acid ester.

Examples of the (meth)acrylate having a hydroxyl group include: (2-hydroxyethylmeth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, and pentaerythritol. Tri(meth)acrylate, di-trimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide modified penta(meth)acrylate, dipentaerythritol ethylene oxide modified penta(meth)acrylate, Pentaerythritol propylene oxide modified penta(meth)acrylate, dipentaerythritol caprolactone modified penta(meth)acrylate, glyceryl acrylate methyl Acrylate, glyceryl dimethacrylate, 2-hydroxy-3-acrylylpropyl methacrylate, reaction product of epoxy group-containing compound and (meth)acrylic acid carboxyl ester, hydroxyl-containing polyol polyacrylic acid Ester etc.

Examples of the polyfunctional isocyanate include toluene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, polyisocyanate, and the like.

In addition, the structure of the alcohol is not limited, but when using a polyhydric alcohol, it is preferable because the crosslinking degree of the cured coating film becomes high and the coating film resistance is improved. Examples of the polyhydric alcohol include propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, and the like.

As these commercially available products, AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, DAUA-167, and Shin UA-160TM manufactured by Nakamura Chemical Industry Co., Ltd., UV-4108F, UV-4117F manufactured by Osaka Organic Chemical Industry Co., Ltd., etc.

These photopolymerizable monomers having a urethane bond can be used alone or in combination of two or more types.

<Binder resin>

The photosensitive coloring composition of the present invention may contain a binder resin. Specific examples of the binder resin include thermoplastic resin, thermosetting resin, and the like.

(Thermoplastic resin)

Examples of thermoplastic resins used in binder resins include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, and vinyl chloride-vinyl acetate copolymer. material, polyvinyl acetate, polyamine Formate resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, cellulose, polyethylene (high density polyethylene (High Density Polyethylene, HDPE), low density polyethylene (Low Density Polyethylene, LDPE)), polybutadiene, and polyimide resin, etc. Among them, acrylic resin is preferably used.

(thermosetting resin)

Examples of the thermosetting resin used in the binder resin include epoxy resin, benzoguanamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine resin, urea resin, Cardo ) resin, and phenol resin, etc.

Examples of the thermosetting resin include low molecular compounds such as epoxy compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, cardo compounds, and phenol compounds. , the present invention is not limited thereto. By including such a thermosetting resin, the following effects can be obtained: the resin reacts during the firing of the filter segment to increase the cross-linking density of the coating film, the heat resistance is improved, and the aggregation of pigments during the firing of the filter segment is suppressed. Among these, epoxy resin, cardo resin, or melamine resin is preferred.

When producing a color filter using a photosensitive colored composition, the binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in all wavelength regions of the visible light region from 400 nm to 700 nm. .

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

The binder resin is preferably used in an amount of 10 parts by mass or more in non-volatile components of the resin with respect to 100 parts by mass of the total mass of the colorant in terms of good film-forming properties and good resistance. It is preferable to use it in an amount of 500 parts by mass or less in the resin non-volatile components in order to achieve a high concentration and develop good color characteristics.

In one embodiment, when the colored composition is used in the form of an alkali-developable colored resist material, from the viewpoint of developability, it is preferable to use an ethylenically unsaturated monomer containing an acidic group. The prepared alkali-soluble vinyl-based resin was used as a binder resin. In addition, in other embodiments, a photosensitive colored composition may be constituted for the purpose of improving photosensitivity and solvent resistance. In this case, as the binder resin, an active energy ray-curable resin having an ethylenically unsaturated double bond can be used. Hereinafter, these embodiments are described in more detail.

Examples of vinyl-based alkali-soluble resins that can be suitably used as binder resins include homopolymers or copolymers prepared using ethylenically unsaturated monomers having acidic groups such as carboxyl groups, hydroxyl groups, and sulfonic acid groups. Specific examples of the vinyl-based alkali-soluble resin include acrylic resin having an acidic group, α-olefin/maleic acid (anhydride) copolymer, styrene/styrenesulfonic acid copolymer, ethylene/(methane base) acrylic copolymer, or isobutylene/maleic acid (anhydride) copolymer, etc. Among these, at least one resin selected from the group consisting of (meth)acrylic resin having an acidic group and styrene/styrenesulfonic acid copolymer is preferred. In particular, (meth)acrylic resins having an acidic group are suitably used because they have high heat resistance and transparency.

The acidic group in the acidic group-containing ethylenically unsaturated monomer used to prepare the resin preferably has a carboxylic acid group or a hydroxyl group. Examples of the ethylenically unsaturated monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid. Examples of the ethylenically unsaturated monomer having a hydroxyl group include: (2-hydroxyethylmeth)acrylate, 3-hydroxypropyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, Glyceryl mono(meth)acrylate, 4-hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl acrylate, or caprolactone adducts of these monomers (the molar addition number is preferably 1 to 5) etc.

As one embodiment, when constituting a photosensitive colored composition for a color filter, it is important that the binder resin is A balance between the colorant adsorbing group and the carboxyl group that functions as an alkali-soluble group during development, and the aliphatic and aromatic groups that function as affinity groups for the colorant carrier and solvent. In one embodiment, from the viewpoint of pigment dispersion, penetrability, developability, and durability, it is preferable to use a resin with an acid value of 20 mgKOH/g to 300 mgKOH/g as the binder resin. By using a resin having an acid value within the above range, it is easy to obtain appropriate solubility in a developer and form a fine pattern.

From this viewpoint, the vinyl-based alkali-soluble resin obtained by polymerizing the acidic group-containing ethylenically unsaturated monomer preferably has an acid value of 20 mgKOH/g to 300 mgKOH/g and a weight average molecular weight (Mw) of 10000~80000. In one embodiment, the resin may be a copolymer of methacrylic acid and other monomers such as 2-hydroxyethyl (meth)acrylate and n-butyl methacrylate.

As another embodiment, when the photosensitive colored composition is constituted in the form of an alkali-developable colored resist for color filters, it is preferable to use an active energy ray having an ethylenically unsaturated double bond as the binder resin. As the curable resin, it is particularly preferable to use an active energy ray curable resin having an ethylenically unsaturated double bond in the side chain. When the above-mentioned resin having an ethylenically unsaturated double bond in the side chain is used as the binder resin, there is a tendency to improve the coloring in the resist material without generating foreign matter in the coating film after the resist is applied. agent stability. When the straight-chain resin is used and does not have an ethylenically unsaturated double bond in the side chain, in a liquid in which the resin and the colorant are mixed, the colorant is less likely to be captured by the resin and has a degree of freedom. Colorant components tend to aggregate and precipitate. On the other hand, when an active energy ray-curable resin having an ethylenically unsaturated double bond in a side chain is used, in a liquid in which the resin and the colorant are mixed, the colorant is easily captured by the resin. Therefore, in the solvent resistance test, the pigment is difficult to dissolve, and the colorant component is difficult to aggregate and precipitate. In addition, it is inferred that when a film is formed by exposure to active energy rays, the resin is three-dimensionally cross-linked and the colorant molecules are fixed. Even if the solvent is removed in the subsequent development step, the colorant components are unlikely to agglomerate and precipitate.

Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include a resin into which an unsaturated ethylenically double bond has been introduced by the method (a) or (b) shown below.

[Method(a)]

Method (a) includes, for example, a method of copolymerizing an unsaturated ethylenic monomer having an epoxy group and one or more other monomers. The side chain epoxy group is added to the carboxyl group of an unsaturated monobasic acid having an unsaturated ethylenic double bond, and the polybasic acid anhydride is reacted with the generated hydroxyl group to introduce the unsaturated ethylenic double bond and carboxyl group.

Examples of the unsaturated ethylenic monomer having an epoxy group include: (glycidylmeth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate and 3,4-epoxycyclohexyl (meth)acrylate may be used alone or two or more types may be used in combination. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth)acrylate is preferred.

Examples of the unsaturated monobasic acid include: (meth)acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, α-halogenated alkyl group of (meth)acrylic acid, alkoxy group, halogen, nitro, cyano substituents and other monocarboxylic acids, etc. These may be used alone or two or more types may be used in combination.

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc. These may be used alone or two or more types may be used in combination. By increasing the number of carboxyl groups and using tricarboxylic anhydrides such as trimellitic anhydride or tetracarboxylic dianhydrides such as pyromellitic dianhydride as necessary, the remaining anhydride groups can be hydrolyzed. In addition, if tetrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as the polybasic acid anhydride, the unsaturated ethylenic double bonds can be further increased.

A method similar to method (a) includes, for example, a method of co-binding an unsaturated ethylenic monomer having a carboxyl group with one or more other monomers. A part of the side chain carboxyl groups of the obtained copolymer is added to an unsaturated ethylenic monomer having an epoxy group, thereby introducing unsaturated ethylenic double bonds and carboxyl groups.

[Method (b)]

As the method (b), there is a method of using an isocyanate group of an unsaturated ethylenic monomer having an isocyanate group, and a monomer using an unsaturated ethylenic monomer having a hydroxyl group and another unsaturated monobasic acid having a carboxyl group. The side chain hydroxyl groups of the copolymer obtained by copolymerizing monomers or other monomers are reacted.

Examples of the unsaturated ethylenic monomer having a hydroxyl group include: (meth)acrylic acid 2-hydroxyethyl ester, (meth)acrylic acid 2-hydroxypropyl ester or (meth)acrylic acid 3-hydroxypropyl ester, (meth)acrylic acid 3-hydroxypropyl ester, (meth)acrylic acid 3-hydroxypropyl 2-hydroxybutyl acrylate or 3-hydroxybutyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate, glyceryl (meth)acrylate, or cyclohexanedimethanol mono(methyl) (meth)acrylic acid hydroxyalkyl esters such as acrylic acid esters. These may be used alone or two or more types may be used in combination. In addition, polyether mono(meth)acrylate obtained by addition-polymerizing ethylene oxide, propylene oxide, and/or butylene oxide, etc. to the hydroxyalkyl (meth)acrylate may also be used. Or (poly)ester mono(meth)acrylate obtained by adding (poly)γ-valerolactone, (poly)ε-caprolactone, and/or (poly)12-hydroxystearic acid, or the like. From the viewpoint of suppressing foreign matter in the coating film, 2-hydroxyethyl (meth)acrylate or glyceryl (meth)acrylate is preferred.

Examples of the unsaturated ethylenic monomer having an isocyanate group include 2-(meth)acryloxyethyl isocyanate or 1,1-bis[(meth)acryloxy]ethyl isocyanate. etc., are not limited to these, and two or more types may be used in combination.

<sensitizer>

The photosensitive composition of the present invention may contain a sensitizer.

啉並紫菜嗪衍生物、萘酞菁衍生物、亞酞菁衍生物、吡喃鎓衍生物、噻喃鎓(thiopyrylium)衍生物、四菲林(tetraphyrin)衍生物、輪烯(annulene)衍生物、螺吡喃衍生物、螺噁嗪衍生物、硫代螺吡喃衍生物、金屬芳烴錯合物、有機釕錯合物、或米氏酮(Michler's ketone)衍生物、α-醯氧基酯、醯基膦氧化物、苯甲醯甲酸甲酯、9,10-菲醌、乙基蒽醌、4,4'-二乙基間二苯代酚酞(4,4'-diethyl isophthalophenone)、3,3'-四(第三丁基過氧化羰基)二苯甲酮或4,4'-四(第三丁基過氧化羰基)二苯甲酮、4,4'-雙(二乙基氨基)二苯甲酮等。 Examples of sensitizers include unsaturated ketones represented by chalcone derivatives and dibenzalacetone, and 1,2-diketones represented by benzoyl and camphorquinone. Derivatives, benzoin derivatives, benzoin derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin Derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxocyanine derivatives and other polymethine pigments, acridine derivatives, azine derivatives, thiazine derivatives, oxanine derivatives Azine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetraphenyl Porphyrazine derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquine

Porphyrin derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyranium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, Spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal aromatic hydrocarbon complexes, organic ruthenium complexes, or Michler's ketone derivatives, α-carboxylic acid esters, Phosphine oxide, methyl benzoate, 9,10-phenanthrenequinone, ethyl anthraquinone, 4,4'-diethyl isophthalophenone, 3, 3'-Tetrakis(tert-butylperoxycarbonyl)benzophenone or 4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino) Benzophenone etc.

Furthermore, specific examples include "Handbook of Pigments" compiled by Nobu Okawara et al. (1986 Sensitizers described in "Chemistry of Functional Pigments" (1981, CMC) by Nobu Ohgawara and others, and "Special Functional Materials" (1986, CMC) by Chusanro Ikemori and others, But it is not limited to these. In addition, a sensitizer that absorbs light in the ultraviolet to near-infrared range may be included.

Among the sensitizers, examples of sensitizers that can be particularly suitably sensitized include thioxanthone derivatives, Michler's ketone derivatives, and benzazole derivatives. Furthermore, specific examples include: 2,4-diethyl thioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropyl thioxanthone, 4-isopropylthioxanthone, Propylthiaxantrone, 1-chloro-4-propoxythiaxantrone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino) Benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethyltriazole, 3-benzoyl-N-ethyltriazole, 3,6-diphenyl Formyl-N-ethyltriazole, etc. Examples of commercially available products include "KAYACURE DETX-S" (manufactured by 2,3-diethylthiaxantrone Nippon Chemical Co., Ltd.), "EAB-F" (4,4'-bis (diethylamino)benzophenone (manufactured by Hodogaya Chemical Industry Co., Ltd.), etc.

These sensitizers can be used individually or in combination of 2 or more types.

Furthermore, specific examples include "Handbook of Pigments" edited by Nobu Okawara et al. (1986, Kodansha), "Chemistry of Functional Pigments" edited by Nobu Okawara et al. (1981, CMC), and "Handbook of Pigments" edited by Tasanro Ikemori et al. Sensitizers described in "Special Functional Materials" (1986, CMC), but are not limited to these. In addition, a sensitizer that absorbs light in the ultraviolet to near-infrared range may be included.

When using a sensitizer, the content is preferably 3 to 60 parts by mass relative to 100 parts by mass of the photoradical polymerization initiator contained in the coloring composition. From the viewpoint of chemical properties and developability, it is more preferably 5 to 50 parts by mass.

<Epoxy compound>

The photosensitive composition of the present invention may contain an epoxy compound. As the epoxy compound used, a known compound having an epoxy group can be used without particular limitation.

Examples of the epoxy compound include: phenol novolak type epoxy resin, cresol novolak type epoxy resin, trihydroxyphenylmethane type epoxy resin, dicyclopentadienol type epoxy resin, and bisphenol-A. epoxy resin, bisphenol-F epoxy resin, bisphenol epoxy resin, bisphenol-A novolac epoxy resin, epoxy resin containing naphthalene skeleton, alicyclic epoxy resin, heterocyclic epoxy resin Epoxy resin, etc.

Among these, it is preferable that the epoxy compound is an alicyclic epoxy resin from the viewpoint of improvement of water stains or heat resistance or chemical resistance.

Specific examples of the phenol novolak type epoxy resin include: Epiclon N-740, Epiclon N-770, and Epiclon manufactured by DIC Co., Ltd. (Epiclon) N-775, D.E.N438 manufactured by Dow Chemical Co., Ltd., RE-306 manufactured by Nippon Kayaku Co., Ltd., jER152, jER154 manufactured by Mitsubishi Chemical Co., Ltd., etc.

Specific examples of the cresol novolak type epoxy resin include: Epiclon N-660, Epiclon N-665, Epiclon manufactured by DIC Co., Ltd. Epiclon N-670, Epiclon N-673, Epiclon N-680, Epiclon N-695, Epiclon N -665-EXP, Epiclon N-672-EXP, EOCN-102S, EOCN-103S manufactured by Nippon Kayaku Co., Ltd. EOCN-104S, UVR-6650 manufactured by Union Carbide Co., Ltd., ESCN-195 manufactured by Sumitomo Chemical Industries, Ltd., etc.

Specific examples of the trihydroxyphenylmethane type epoxy resin include EPPN-503, EPPN-502H, and EPPN-501H manufactured by Nippon Kayaku Co., Ltd., and TACTIX manufactured by Dow Chemical Co., Ltd. -742, jER E1032H60 manufactured by Mitsubishi Chemical Co., Ltd., etc.

Specific examples of the dicyclopentadienol-type epoxy resin include Epiclon EXA-7200 manufactured by DIC Co., Ltd. and Dow Chemical Co., Ltd. TACTIX-556 et al.

Specific examples of bisphenol-type epoxy resins include jER828 and jER1001 manufactured by Mitsubishi Chemical Co., Ltd., UVR-6410 manufactured by Union Carbide Co., Ltd., and Dow Chemical Co., Ltd. D.E.R-331 manufactured by the company, YD-8125 and other bisphenol-A epoxy resins manufactured by Shinnikka Epoxy Manufacturing Co., Ltd., UVR-6490 manufactured by Union Carbide Co., Ltd., Shinnikka Bisphenol-F epoxy resins such as YDF-8170 manufactured by Epoxy Manufacturing Co., Ltd.

Specific examples of biphenol-type epoxy resins include biphenol-type epoxy resins such as NC-3000 and NC-3000H manufactured by Nippon Kayaku Co., Ltd., jER YX-4000 and jER manufactured by Mitsubishi Chemical Co., Ltd. YL-6121 and other xylenol type epoxy resins, etc.

Specific examples of the bisphenol A novolak type epoxy resin include Epiclon N-880 manufactured by DIC Co., Ltd. jER E157S75 manufactured by Ryo Chemical Co., Ltd., etc.

Specific examples of the epoxy resin containing a naphthalene skeleton include NC-7000 and NC-7300 manufactured by Nippon Kayaku Co., Ltd., EXA-4750 manufactured by DIC Co., Ltd., and the like.

Specific examples of alicyclic epoxy resins include Celloxide 2021P, 2081, and 2000 manufactured by Daicel Co., Ltd., Epolead PB3600, PB4700, and GT401. EHPE-3150, Cyclomer M100, etc.

Specific examples of heterocyclic epoxy resins include TEPIC-L, TEPIC-H, TEPIC-S manufactured by Nissan Chemical Industries, Ltd., and the like.

These epoxy compounds can be used individually or in combination of 2 or more types.

The content of the epoxy compound used in the photosensitive coloring composition of the present invention is usually 0.5 to 50 mass%, preferably 1 to 40 mass%, based on 100 mass% of non-volatile components of the coloring composition. When the content of the epoxy compound is within the above range, a coating film having high heat resistance and excellent performance can be obtained, which is preferable.

<Oxetane compound>

An oxetane compound can be added to the photosensitive composition of the present invention. As the oxetane compound, a known compound having an oxetanyl group can be used without particular limitation. Examples of the oxetane compound include compounds in which the oxetanyl group is monofunctional, compounds in which the oxetanyl group is bifunctional, and compounds in which the oxetanyl group is bifunctional or higher.

Examples of compounds having a monofunctional oxetanyl group include: acrylic acid (3- Ethyloxetan-3-yl)methyl ester, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane alkane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl -3-(2-Methacryloxymethyl)oxetane, 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane Butane etc. Specific examples include OXE-10 and OXE-30 manufactured by Osaka Organic Chemical Industry Co., Ltd., OXT-101 and 212 manufactured by Toagosei Co., Ltd., and the like.

Examples of compounds in which the oxetanyl group is bifunctional include: 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 1,4 -Bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy] Methyl}benzene, bis[1-ethyl(3-oxetanyl)]methyl ether, bis[1-ethyl(3-oxetanyl)]methylether-3-ethyl- 3-Hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl) )oxetane, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy) )methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl) ) ether, dicyclopentenyl bis(3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol Bis(3-ethyl-3-oxetanylmethyl)ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl) -3-oxetanylmethoxy)hexane, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, ethylene oxide (EO) modified bisphenol A bis(3- Ethyl-3-oxetanylmethyl) ether, propylene oxide (PO) modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO modified hydrogenated bisphenol A bis( 3-ethyl-3-oxetanylmethyl base) ether, PO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether, etc. . Specific examples include OXBP and OXTP manufactured by Ube Kosan Co., Ltd., OXT-121 and OXT-221 manufactured by Toa Gosei Co., Ltd., and the like.

Examples of compounds in which the oxetanyl group is bifunctional or higher include: pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ) ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol penta(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl- 3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol penta(3-ethyl-3- Oxetanyl methyl) ether, di-trimethylolpropane tetrakis (3-ethyl-3-oxetanyl methyl) ether, and resins containing oxetanyl groups (for example, Japanese Patent No. 3783462 A polymer obtained by radical polymerization of a (meth)acrylic monomer such as the described oxetane-modified phenol novolac resin, etc.) or the above-mentioned OXE-30. Such polymers can be obtained using known polymerization methods.

The content of the oxetane compound used in the photosensitive composition of the present invention is usually 0.5% to 50% by mass, and preferably 1% to 40% by mass in 100% by mass of non-volatile components of the coloring composition. %. When the content of the oxetane compound is within the above range, an excellent coating film with good water staining and high chemical resistance can be obtained, which is preferable.

<Mercaptan chain transfer agent>

The photosensitive composition of the present invention may contain a thiol chain transfer agent as a chain transfer agent. agent. By using a thiol together with a photopolymerization initiator, thiyl radicals are generated during the radical polymerization process after light irradiation, which function as a chain transfer agent and are less susceptible to polymerization inhibition by oxygen. The obtained colored composition has high sensitivity.

In addition, a polyfunctional aliphatic thiol in which two or more SH groups are bonded to an aliphatic group such as a methylene group or an ethylidene group is preferred. More preferred are polyfunctional aliphatic thiols having four or more SH groups. By increasing the number of functional groups, the polymerization initiating function is increased and can be hardened from the surface in the pattern to the vicinity of the substrate.

Examples of polyfunctional thiols include hexanedithiol, decanedithiol, 1,4-butanediol dithiopropionate, 1,4-butanediol dithioglycolate, and ethylene glycol dithiol. Thioglycolate, ethylene glycol dithiopropionate, trimethylolpropane trithioglycolate, trimethylolpropane trithiopropionate, trimethylolpropane tris(3-mercapto) Butyrate), pentaerythritol tetrathioglycolate, pentaerythritol tetrathiopropionate, trimercaptopropionate tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2 , 4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, etc. Preferred examples include: ethylene glycol dithiopropionic acid Ester, trimethylolpropane trithiopropionate, pentaerythritol tetrathiopropionate.

These thiol chain transfer agents can be used individually by 1 type, or in mixture of 2 or more types.

In addition, the content of the thiol chain transfer agent is preferably 1% to 10%, and more preferably 2.0% to 8.0% of the total non-volatile components of the coloring composition. Within the above range, the effect of the chain transfer agent becomes greater, and the sensitivity, taper shape, wrinkles, film shrinkage, etc. become favorable.

<UV absorber>

The photosensitive composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorber in the present invention refers to an organic compound with an ultraviolet absorbing function. Examples thereof include: benzotriazole-based organic compounds, triazine-based organic compounds, benzophenone-based organic compounds, and cyanoacrylate-based organic compounds. compounds, and salicylate (salicylate) organic compounds, etc.

The content of the ultraviolet absorber is preferably 5 to 70 mass % in the total of 100 mass % of the photopolymerization initiator and the ultraviolet absorber. When the content of the ultraviolet absorber is less than the above, the effect of the ultraviolet absorber is small and resolution cannot be ensured. When the content is more than the above, the sensitivity becomes low and pixel peeling may occur or the aperture may be larger than the designed value. Undesirable situations such as enlarging the size.

At this time, when the photosensitive coloring composition contains a sensitizer, the content of the photopolymerization initiator includes the content of the sensitizer.

In addition, the total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20 mass% in 100 mass% of non-volatile components of the photosensitive coloring composition. When the total content of the photopolymerization initiator and ultraviolet absorber is less than the above, the adhesion is weak and pixel peeling occurs. When it is more than the above, the sensitivity may be too high and resolution may become poor.

At this time, when the photosensitive composition contains a sensitizer, the content of the photopolymerization initiator includes the content of the sensitizer.

Examples of benzotriazole-based organic compounds include: 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)-2H- Benzotriazole, Octyl -3[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate and 2-ethylhexyl-3-[3- Mixture of tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-[2-hydroxy-3,5-bis(α , α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-Di-tertiary pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tertiary octylphenyl)benzotriazole, 5% 2-Methoxy-1-methylethyl acetate with 95% phenylpropionic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl) -4-Hydroxy, C7-9 side chain and linear alkyl ester compounds, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl) yl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutanyl) base) phenol.

Furthermore, specific examples include: "TINUVIN P", "TINUVIN PS", "TINUVIN 109" and "TINUVIN" manufactured by BASF. 234", "TINUVIN(TINUVIN)326", "TINUVIN(TINUVIN)328", "TINUVIN(TINUVIN)329", "TINUVIN(TINUVIN)360", "TINUVIN(TINUVIN) 384-2", "TINUVIN (TINUVIN) 900", "TINUVIN (TINUVIN) 928", "TINUVIN (TINUVIN) 99-2", "TINUVIN (TINUVIN) 1130", Ediko "Adekastab LA-29" manufactured by ADEKA, "RUNA-93" manufactured by Otsuka Chemical Company, etc.

Examples of triazine-based organic compounds include: 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-octyloxyphenol, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxy Propoxy]phenol, 2-(2,4- Reaction product of dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-ethylhexyl-glycidyl ester, 2,4- Bis "2-hydroxy-4-butoxyphenyl"-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, etc.

Furthermore, specific examples include: "KEMISORB 102" manufactured by Chemipro Kasei, "TINUVIN 400" and "TINUVIN" manufactured by BASF (TINUVIN)405", "TINUVIN(TINUVIN)460", "TINUVIN(TINUVIN)477-DW", "TINUVIN(TINUVIN)479", "TINUVIN(TINUVIN)1577", Eddie "Adekastab LA-46" and "Adekastab LA-F70" manufactured by ADEKA, and "Saiya Sobu" manufactured by sun-chemical (CYASORB)UV-1164" etc.

Examples of benzophenone-based organic compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-hydroxy-4-methoxybenzophenone. Keto-5-sulfonic acid-3 water temperature, 2-hydroxy-4-n-octyloxybenzophenone, 2,2-di-hydroxy-4-methoxybenzophenone, etc.

Furthermore, specific examples include: "KEMISORB 10", "KEMISORB 11", and "KEMISORB 11S" manufactured by Chemipro Kasei Co., Ltd. , "KEMISORB (KEMISORB) 12", "KEMISORB (KEMISORB) 111", "SEESORB (SEESORB) 101", "SEESORB (SEESORB)" manufactured by Shipro Kasei Company )107", "Adekastab 1413" manufactured by ADEKA, etc.

<Polymerization inhibitor>

In order to prevent photosensitization due to diffracted light from the mask during exposure, the photosensitive composition of the present invention may contain a polymerization inhibitor. By adding a polymerization inhibitor, it is possible to obtain the effect of preventing hardening from proceeding beyond a desired pattern by utilizing photosensitive chain polymerization.

Examples of polymerization inhibitors include catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, and 4-methylo-catechol. Diphenol, 2-ethyl catechol, 3-ethyl catechol, 4-ethyl catechol, 2-propyl catechol, 3-propyl catechol, 4 -Propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-tert-butyl catechol, 3 - Alkyl catechol compounds such as tert-butyl catechol, 4-tert-butyl catechol, 3,5-di-tert-butyl catechol, and 2-methyl m-catechol Resorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2 - Alkyl resorcin compounds such as n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, and 4-tert-butylresorcinol; Methyl hydroquinone, ethyl hydroquinone, propyl hydroquinone, tert-butyl hydroquinone, 2,5-di-tert-butyl hydroquinone and other alkyl hydroquinones Phenolic compounds; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, and tribenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide ; Phosphite compounds such as triphenyl phosphite and trinonylphenyl phosphite; pyrogallol, phloroglucin, etc. The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass relative to 100 parts by mass of the coloring composition excluding the solvent. In the above range, the effect of the polymerization inhibitor becomes greater, and the linearity of the taper, the wrinkles of the coating film, the pattern resolution, etc. become improved. good.

<Antioxidant>

The photosensitive composition of the present invention may contain an antioxidant. Antioxidants prevent the photopolymerization initiator or thermosetting compound contained in the red photosensitive composition from oxidizing and yellowing due to thermal hardening or the thermal step during annealing of indium tin oxide (ITO), thereby improving the The transmittance of the coating film. Especially when the colorant concentration of the coloring composition is high, the amount of the cross-linking component in the coating film is reduced and countermeasures such as the use of a highly sensitive cross-linking component or the increase of the photopolymerization initiator are adopted, so the thermal step occurs. The phenomenon of yellowing becoming stronger.

Therefore, by containing an antioxidant, yellowing due to oxidation during the heating step can be prevented and a high transmittance of the coating film can be obtained.

The "antioxidant" in the present invention may be a compound having an ultraviolet absorbing function, a radical capturing function, or a peroxide decomposing function. Specifically, examples of antioxidants include hindered phenol-based and hindered amine-based antioxidants. , phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, well-known ultraviolet absorbers, antioxidants, etc. can be used. In addition, the antioxidant used in the present invention preferably does not contain halogen atoms.

Among these antioxidants, from the viewpoint of both transmittance and sensitivity of the coating film, preferred antioxidants include hindered phenol antioxidants, hindered amine antioxidants, phosphorus antioxidants, and sulfur antioxidants.

Examples of hindered phenol-based antioxidants include: 2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-tert-butyl-4 -hydroxybenzyl), 1,3,5-tris(4- tert-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butyl) anilinyl)-1,3,5-triazine, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,6-di-tert-butyl Base-4-nonylphenol, 2,2'-isobutylene-bis-(4,6-dimethyl-phenol), 4,4'-butylene-bis-(2-tert-butyl- 5-methylphenol), 2,2'-thio-bis-(6-tert-butyl-4-methylphenol), 2,5-di-tertiary amyl-hydroquinone, 2, 2'-Thiodiethylbis-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate, 1,1,3-tris-(2'-methyl-4' -Hydroxy-5'-tert-butylphenyl)-butane, 2,2'-methylene-bis-(6-(1-methyl-cyclohexyl)-p-cresol), 2,4- Dimethyl-6-(1-methyl-cyclohexyl)-phenol, N,N-hexamethylene bis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), etc. Oligomer-type and polymer-type compounds having other hindered phenol structures may also be used. Specific examples include: Adekastab AO-20, AO-30, AO-40, AO50, AO60, AO80, AO320 manufactured by ADEKA Co., Ltd., Kemibro KEMINOX 101, 179, 76, 9425 manufactured by Chemipro Kasei Co., Ltd., IRGANOX 1010, 1035, 1076, 1098, 1135 manufactured by BASF Co., Ltd. , 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565, CYANOX CY-1790, CY-2777, etc. manufactured by Sun-Chemical Co., Ltd.

Examples of hindered amine antioxidants include bis(2,2,6,6-tetramethyl-4-piridinyl) sebacate and bis(N-methyl-2,2,6,6- Tetramethyl-4-piridyl) sebacate, N,N'-bis(2,2,6,6-tetramethyl-4-piridinyl)-1,6-hexamethylenebis Amine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piridyl)amino-N-(2,2,6,6-tetramethyl-4-piridyl) )Bingxi Amine, tetrakis(2,2,6,6-tetramethyl-4-piridinyl)-1,2,3,4-butanetetracarboxylate, poly[{6-(1,1,3, 3-Tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-pyridinyl)imino} Hexamethyl{(2,2,6,6-tetramethyl-4-pyridinyl)imino}], poly[(6-morpholinyl-1,3,5-triazine-2,4- Diyl){(2,2,6,6-tetramethyl-4-piridinyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piridinyl) Imino}], condensation polymer of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiridine, N,N'-4,7 -Tetrakis[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piridinyl)amino}-1,3,5-triazine-2 -base]-4,7-diazadecane-1,10-diamine, etc. Oligomer-type and polymer-type compounds having other hindered amine structures may also be used. Specific examples include: Adekastab LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, manufactured by ADEKA Co., Ltd. LA-77G, LA-81, LA-82, LA-87, LA-402F, LA-502XP, KAMISTAB 29, 62, manufactured by Chemipro Kasei Co., Ltd. 77, 29, 94, Tinuvin 249, Tinuvin 111FDL, 123, 144, 292, 5100, manufactured by BASF Co., Ltd., manufactured by Sun-Chemical Co., Ltd. CYASORB UV-3346, UV-3529, UV-3853, etc.

Examples of phosphorus-based antioxidants include tris(isodecyl)phosphite, tris(tridecyl)phosphite, phenylisooctylphosphite, phenylisodecylphosphite, and phenyldiphosphate. (Tridecyl)phosphite, diphenylisooctylphosphite, diphenylisodecylphosphite, diphenyltridecylphosphite, triphenylphosphite, tris(nonyl) Phenyl) phosphite, 4,4'-isopropylidenephenolalkyl phosphite, trinonylphenyl phosphite Esters, tris-dinonylphenyl phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(biphenyl)phosphite, distearyl pentaerythritol diphosphite Esters, di(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetrakis-tris Decyl 4,4'-butylene bis(3-methyl-6-tert-butylphenol) diphosphite, hexa-tridecyl 1,1,3-tris(2-methyl-4-hydroxy) -5-tert-butylphenyl)butane triphosphite, 3,5-di-tert-butyl-4-hydroxybenzylphosphite diethyl ester, sodium bis(4-tert-butylphenyl) base) phosphite, sodium-2,2-methylene-bis(4,6-di-tert-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy) )-benzene, ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite, etc. Oligomer-type and polymer-type compounds having other phosphite structures may also be used. Specific examples include: Adekastab PEP-36, PEP-8, HP-10, Adekastab 2112, 1178, manufactured by ADEKA Co., Ltd. 1500, C, 3013, TPP, IRGAFOS 168 manufactured by BASF Co., Ltd., Hostanox P-EPQ manufactured by Clariant Chemicals Co., Ltd., etc.

Examples of sulfur-based antioxidants include: 2,2-thio-diethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4 -Bis[(octylthio)methyl]-o-cresol, 2,4-bis[(laurylthio)methyl]-o-cresol, 2,2-bis{[3-(dodecyl Thio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], 2,2-thio-diethylene Bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] etc. Oligomer types and polymer types with other thioether structures can also be used compounds, etc.

Specific examples include: Adekastab AO-412S and AO-503 manufactured by ADEKA Co., Ltd., Chemipro Kasei Co., Ltd. North (KEMINOX) PLS, etc.

As the benzotriazole-based antioxidant, oligomer-type and polymer-type compounds having a benzotriazole structure, etc. can be used.

Specific examples include: Adekastab LA-29, LA-31RG, LA-32, LA-36, -412S manufactured by ADEKA Co., Ltd., Kemibro Chemical Co., Ltd. KEMISORB 71, 73, 74, 79, 279 manufactured by Chemipro Kasei Co., Ltd., TINUVIN PS, 99-2, 384-2 manufactured by BASF Co., Ltd. ,900,928,1130, etc.

Examples of benzophenone-based antioxidants include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-n-octoxybenzophenone. Ketone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-5 -Sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, etc. Oligomer-type and polymer-type compounds having other benzophenone structures may also be used. Specific examples include: Adekastab 1413 manufactured by ADEKA Co., Ltd., Chemipro Kasei Co., Ltd. KEMISORB 10, 11, 11S, 12, 111, UV-12, UV-329 manufactured by Sun-Chemical Co., Ltd., etc.

Examples of triazine-based antioxidants include 2,4-bis(allyl)-6-(2-hydroxyphenyl)-1,3,5-triazine and the like. Oligomer-type and polymer-type compounds having other triazine structures may also be used. Specific examples include: LA-46 and F70 manufactured by ADEKA Co., Ltd., KEMISORB 102 manufactured by Chemipro Kasei Co., Ltd., BASF TINUVIN 400, 405, 460, 477, 479 manufactured by Sun-Chemical Co., Ltd., CYASORB UV-1164 manufactured by Sun-Chemical Co., Ltd., etc.

Examples of salicylate-based antioxidants include phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, and the like. Oligomer-type and polymer-type compounds having other salicylate structures may also be used.

These antioxidants can be used individually or in combination of 2 or more types.

In addition, the content of the antioxidant is more preferably 0.5% by mass to 5.0% by mass in 100% by mass of non-volatile components of the coloring composition because the transmittance, spectral characteristics, and sensitivity are good.

<Adhesion improver>

In order to improve the adhesiveness with the base material, the photosensitive composition of the present invention may contain an adhesive improving agent such as a silane coupling agent. By improving the adhesion using the adhesion improving agent, the reproducibility of the thin wire becomes good and the resolution is improved.

Examples of adhesion improving agents include: vinyltrimethoxysilane, ethylene Triethoxysilane and other vinyl silanes; 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methylpropene (Meth)acrylic silanes such as hydroxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane ;2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3 -Epoxysilanes such as glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane; N-2-(aminoethyl)-3-aminopropylmethyl dimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- Triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2 -Aminosilanes such as the hydrochloride of aminoethyl-3-aminopropyltrimethoxysilane; thiols such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; Styryl compounds such as styryltrimethoxysilane; ureido compounds such as 3-ureidopropyltriethoxysilane; sulfide compounds such as bis(triethoxysilylpropyl)tetrasulfide; 3- Silane coupling agents such as isocyanate propyltriethoxysilane and other isocyanates. The adhesion improving agent can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass relative to 100 parts by mass of the colorant in the coloring composition. Within the above range, the effect becomes larger and the balance between adhesion, resolution, and sensitivity is good, so it is more preferable.

<Leveling agent>

In order to improve the coating properties of the composition on the transparent substrate and the drying properties of the colored film, it is preferable to add a leveling agent to the photosensitive composition of the present invention. as leveling Various surfactants such as silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants can be used.

Examples of silicone-based surfactants include linear polymers containing siloxane bonds or modified siloxane polymers in which organic groups are introduced into side chains or terminals.

Specific examples include: BYK-300, BYK-306, BYK-310, BYK-313, BYK-315N, BYK-320, BYK-322, BYK-323 manufactured by BYK-Chemie, BYK-330, BYK-331, BYK-333, BYK-342, BYK-345/346, BYK-347, BYK-348, BYK-349, BYK-370, BYK-377, BYK-378, BYK-3455, BYK-UV3510, BYK-3570, FZ-7001, FZ-7002, FZ-2110, FZ-2122, FZ-2123, FZ-2191, FZ-5609 manufactured by Toray Dow Corning Co., Ltd., Shin-Etsu X-22-4952, , X-22-6191, X-22-4515, KF-6004, etc.

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain.

Specific examples include Surflon S-242, S-243, S-420, S-611, S-651, and S-386 manufactured by AGC Seimi Chemical Co., Ltd. Megafac F-253, F-477, F-551, F-552, F-555, F-558, F-560, F-570, F-575 manufactured by DIC Co., Ltd. , F-576, R-40-LM, R-41, RS-72-K, DS-21, manufactured by Sumitomo 3M Co., Ltd. FC-4430, FC-4432, manufactured by Mitsubishi Materials Electronics Co., Ltd. EF-PP31N09, EF-PP33G1, EF-PP32C1, Ftergent 602A manufactured by NEOS Co., Ltd., etc.

Examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl ether, Oxyethylene myristyl ether, polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylene distyrenated phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene tribenzylphenyl ether, Oxyethylene polyoxypropylene glycol, polyoxyethylene alkenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate, sorbitan monolaurate, sorbitan monopalmitate , Sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, dehydration Sorbitan monolaurate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monooleate Stearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene tetraoleate Sorbitol, glyceryl monostearate, glyceryl monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol Alkyl betaines such as monooleate, polyoxyethylene hardened castor oil, polyoxyethylene alkylamine, alkyl alkanolamide, alkyl imidazoline or alkyl dimethyl aminoacetate betaine, etc.

Specific examples include Emulgen 103, Emulgen 104P, Emulgen 106, Emulgen 108, Emulgen 109P and Emulgen manufactured by Kao Co., Ltd. (Emulgen) 120. Emulgen 123P, Emulgen 130K, Emulgen 147, Emulgen 150, Emulgen 210P, Emulgen 220, Emulgen 306P , Emulgen 320P, Emulgen 350, Emulgen 404, Emulgen 408, Emulgen 409PV, Emulgen 420, Emulgen 430, Emulgen 705, Emulgen 707, Emulgen 709, Emulgen 1108, Emulgen 1118S-70, Emulgen 1135S-70, Emulgen )1150S-60, Emulgen 2020G-HA, Emulgen 2025G, Emulgen LS-106, Emulgen LS-110, Emulgen LS-114, Emulgen (Emulgen) MS-110, Emulgen A-60, Emulgen A-90, Emulgen B-66, Emulgen PP-290, Latemul PD-420, Latemul PD-430, Latemul PD-430S, Latemul PD450, Rheodol SP-L10, Rheodol (Rheodol)SP-P10, Rheodol (Rheodol) SP-S10V, Rheodol (Rheodol) SP-S20, Rheodol (Rheodol) SP-S30V, Rheodol (Rheodol) SP-O10V , Rheodol SP-O30V, Rheodol super SP-L1, Rheodol AS-10V, Rheodol AO-10V, Rheodol (Rheodol)AO-15V, Rheodol (Rheodol) TW-L120, Rheodol (Rheodol) TW-L106, Rheodol (Rheodol) TW-P120, Rheodol (Rheodol) TW-S120V , Rheodol (Rheodol) TW-L106V, Rheodol Rheodol TW-S320V, Rheodol TW-O120V, Rheodol TW-0106V, Rheodol TW-IS399C, Rheodol super TW -L120, Rheodol 430V, Rheodol 440V, Rheodol 460V, Rheodol MS-50, Rheodol MS- 60. Rheodol MO-60, Rheodol MS-165V, Emanon 1112, Emanon 3199V, Emanon 3299V, Emanon 3299RV, Emanon 4110, Emanon CH-25, Emanon CH-40, Emanon CH-60(K), Amiet 102, Amiet (Amiet) 105, Amiet (Amiet) 105A, Amiet (Amiet) 302, Amiet (Amiet) 320, Aminon (Aminon) PK-02S, Aminon (Aminon) L-02, Fire Homogenol L-95, Adeka Pluronic L-23, 31, 44, 61, 62, 64, 71, 72, 101, manufactured by ADEKA Co., Ltd. 121. Adeka Pluronic TR-701, 702, 704, 913R, etc.

Examples of cationic surfactants include alkyl amine salts or alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride. or ethylene oxide adducts of these.

Specific examples include: Acetamin 24, 26, Quartamin 24P, 86P CONC manufactured by Kao Co., Ltd., KP341 manufactured by Shin-Etsu Chemical Industry Co., Ltd., Kyoeisha Chemical Co., Ltd. (Meth)acrylic (co)polymer Polyflow No. 75 manufactured by Co., Ltd. No.90, No.95, etc.

Examples of the anionic surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, and alkyl diphenyl ether. Sodium disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene Vinyl alkyl ether phosphate, etc.

Specific examples include: Ftergent 100 and 150 manufactured by NEOS Co., Ltd., and ADEKA HOPE YES- manufactured by ADEKA Co., Ltd. 25. ADEKA COL TS-230E, PS-440E, EC-8600, etc.

Only one type of surfactant used in the leveling agent may be used, or two or more types may be combined.

When the photosensitive composition of the present invention contains a surfactant, the amount of the surfactant added is preferably 0.001% to 2.0% by mass, and more preferably 0.005% based on all non-volatile components of the composition of the present invention. Mass%~1.0 mass%. When the content is within the above range, the balance between the coatability, pattern adhesion and transmittance of the colored composition becomes good.

The photosensitive composition of the present invention may contain only one kind of surfactant, or may contain two or more kinds. When two or more types are included, it is preferable that the total amount is within the above range.

<Amine compound>

In addition, the photosensitive composition of the present invention may contain an amine compound having an action of reducing dissolved oxygen. Examples of such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethyl Isoamyl aminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, and N,N-dimethyl-p-toluidine, etc.

<Production method of colored dispersion>

The photosensitive coloring composition contained in the present invention can be produced based on a coloring dispersion using a kneader, a two-roller mill, a three-roller mill, a ball mill, a horizontal sand mill, Various dispersion mechanisms such as a vertical sand mill, a ring bead mill, or an attritor are preferably used to finely disperse the colorant in a colorant carrier such as a dispersant, a binder resin, and/or a dispersion aid. Made with medium solvent. At this time, two or more colorants may be dispersed simultaneously in the colorant carrier, or those dispersed separately in the colorant carrier may be mixed. In the case where the solubility of a dye or colorant is high, fine dispersion does not need to be performed if the solubility in the specifically used solvent is high and dissolution or foreign matter is not confirmed by stirring. In the present invention, it is preferable to use a resin-type dispersant (B) to disperse the colorant (A) when producing the colored dispersion.

In addition, when used in the form of a photosensitive colored composition (resist material) for color filters, it can be prepared as a solvent-developable or alkali-developable coloring composition. The solvent-developable or alkali-developable coloring composition can be made by combining the colorant dispersion with a photopolymerizable monomer and/or a photopolymerization initiator, and optionally a solvent. It is prepared by mixing other dispersing aids and additives. The photopolymerization initiator can be added at the stage of preparing the colored composition, or can be added to the prepared colored composition later.

<Dispersion aid>

When dispersing the colorant in the colorant carrier, dispersion aids such as pigment derivatives, resin-type dispersants, and surfactants may be appropriately contained. The dispersion aid has a large effect of preventing the re-aggregation of the dispersed colorant. Therefore, the brightness, contrast, and storage stability of the colored composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid are improved.

[Resin type dispersant]

The photosensitive composition of the present invention contains the resin-type dispersant (B), and may also contain a conventionally known resin-type dispersant.

The resin-type dispersant includes a colorant-affinitive part that has the property of adsorbing the added colorant and a part that is compatible with the colorant carrier, and exerts the ability to adsorb the added colorant and stabilize the dispersion with respect to the colorant carrier. effect. As the resin-type dispersant, polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid ammonium salt, polycarboxylic acid ammonium salt, etc. can be used. Carboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylates, or modified products of these, through poly(lower alkylene imine) and free carboxyl groups Oily dispersants such as amide or its salt formed by the reaction of polyester, (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone and other water-soluble resins or Water-soluble polymer compounds, polyester systems, modified polyacrylate systems, ethylene oxide/propylene oxide addition compounds, phosphate ester systems, etc. can be used alone or in combination of two or more, and are not necessarily limited to these. .

(Basic resin dispersant)

The dispersant used in the present invention is preferably a basic resin-type dispersant having a basic functional group, preferably a graft copolymer containing a nitrogen atom, or a tertiary amino group or a quaternary ammonium salt group in the side chain. A nitrogen atom-containing acrylic block copolymer and a urethane polymer dispersant containing a functional group such as a nitrogen-containing heterocyclic ring. The resin dispersant is preferably used in an amount of about 5% to 200% by weight based on the total amount of the colorant, and from the viewpoint of film-forming properties, it is more preferably used in an amount of about 10% to 100% by weight.

As a commercially available resin dispersant, preferred are: Disperbyk-101, 103, 107, 108, 110, 111, 116, 130 manufactured by BYK-Chemie Japan, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, or Lactimon , Lactimon-WS or Bykumen, etc.; SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000 manufactured by Japan's Lubrizol Company , 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc.; EFKA-46, 47, 48, 452, 4008, 4009, 4010 manufactured by BASF , 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 480 0 , 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc.; Ajisper-PA111, manufactured by Ajinomoto Fine-Techno Company PB711, PB821, PB822, PB824, etc.

(acidic resin dispersant)

In addition, as the resin-type dispersant used in the present invention, an acidic resin-type dispersant can also be suitably used. It is also preferable that the resin dispersant used in the present invention contains the following (S1) or (S2) as a resin dispersant having a carboxyl group.

(S1) A resin-type dispersant that 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 resin-type dispersant for a polymer in which ethylenic properties are obtained in the presence of a reaction product between a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of a tricarboxylic anhydride and/or a tetracarboxylic dianhydride. It is formed by polymerizing unsaturated monomers.

"Resin type dispersant (S1)"

The resin dispersant (S1) can be produced by a known method such as WO2008/007776, Japanese Patent Application Laid-Open No. 2008-029901, Japanese Patent Application Laid-Open No. 2009-155406, and the like. The polymer (p) having a hydroxyl group is preferably a polymer having a hydroxyl group at the terminal. For example, the polymer (p) having a hydroxyl group can be obtained by A polymer obtained by polymerizing ethylenically unsaturated monomer (r). The compound (q) having a hydroxyl group is preferably a compound having a hydroxyl group and a thiol group in the molecule. It is preferable to have a plurality of terminal hydroxyl groups. Therefore, a compound (q1) having two hydroxyl groups and one thiol group in the molecule can be suitably used.

That is, as a more preferred example, a polymer having two hydroxyl groups at one end can be obtained as a polymer (p1) having two hydroxyl groups and one thiol group in the molecule It is formed by polymerizing the ethylenically unsaturated monomer (r) including the monomer (r1) in the presence of the compound (q1). 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 anhydrous ring opens to generate a carboxylic acid.

《Resin type dispersant (S2)》

The resin-type dispersant (S2) can be produced by a known method such as Japanese Patent Laid-Open No. 2009-155406, Japanese Patent Laid-Open No. 2010-185934, Japanese Patent Laid-Open No. 2011-157416, etc., for example, it can be produced as follows. Obtained by polymerizing the ethylenically unsaturated monomer (r) in the presence of a reaction product between the hydroxyl group of the compound (q) having a hydroxyl group and the acid anhydride group of the tricarboxylic anhydride and/or tetracarboxylic dianhydride. Among them, it is preferable that the compound (q1) containing two hydroxyl groups and one thiol group in the molecule contains a reaction product of a hydroxyl group and an acid anhydride group of a tricarboxylic anhydride and/or a tetracarboxylic dianhydride. A polymer obtained by polymerizing the ethylenically unsaturated monomer (r) of the monomer (r1).

The difference between (S1) and (S2) lies in whether the polymer moiety obtained by polymerizing the ethylenically unsaturated monomer (r) is introduced first or later. Although due to various There are some differences in molecular weight, etc., but as long as the raw materials and reaction conditions are the same, they can be the same in theory.

[Pigment Derivatives]

As the dye derivative used in the present invention, known dye derivatives having an acidic group, a basic group, a neutral group, etc. in the organic dye residue can be used. Examples include compounds having acidic functional groups such as sulfonyl group, carboxyl group, and phosphate group, and amine salts thereof; compounds having a sulfonamide group or a basic functional group such as a tertiary amino group at the terminal; compounds having a phenyl group or o-phenyl group; Compounds with neutral functional groups such as dimethylimide alkyl groups. Examples include Japanese Patent Publication No. 63-305173, Japanese Patent Publication No. 57-15620, Japanese Patent Publication No. 59-40172, Japanese Patent Publication No. 63-17102, and Japanese Patent Publication No. 5-9469. No. 2001-335717, 2003-128669, 2004-091497, 2007-156395, 2008-094873 Publication No., Japanese Patent Publication No. 2008-094986, Japanese Patent Publication No. 2008-095007, Japanese Patent Publication No. 2008-195916, Japanese Patent Publication No. 4585781, Japanese Patent Publication No. 2006-291194, Japanese Patent Laid-Open No. 2007-226161, Japanese Patent Laid-Open No. 2007-314681, Japanese Patent Laid-Open No. 2007-314785, Japanese Patent Laid-Open No. 2012-226110, Japanese Patent Laid-Open No. 2017-165820, Known pigment derivatives described in Japanese Patent Application Laid-Open No. 2005-181383 and the like. Furthermore, in these documents, the pigment derivative may be described as a derivative, a pigment derivative, a pigment dispersant, or simply as a compound, etc., and the organic color Compounds having functional groups such as acidic groups, basic groups, and neutral groups in the pigment residues have the same meaning as pigment derivatives. In addition, these can be used individually or in mixture of 2 or more types.

From the viewpoint of improving dispersibility, 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 based on 100 parts by mass of the colorant. In addition, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by mass or less, and further preferably 35 parts by mass or less.

By adding pigment derivatives to pigments and performing dispersion processes such as wet dispersion using two rollers, three rollers, and beads, the pigment derivatives are adsorbed on the pigment surface and the pigment surface is polar, thereby promoting the adsorption of the resin dispersant. , the compatibility with pigments, pigment derivatives, resin dispersants, solvents, and other additives is improved, and the dispersion stability or viscosity stability over time when made into a colored composition or a colored curable composition is improved. In addition, when the colored curable composition is applied to glass, the coating film has excellent stability over time due to improved compatibility. Regarding the waiting time from application of the colored curable composition to exposure (post-coating delay (PCD): The stability of the pattern shape, characteristic dependence, or line width sensitivity stability of the Post Coating Delay) or the waiting time from exposure to heat treatment (Post Exposure Delay (PED: Post Exposure Delay)) are improved. Furthermore, variation in development time and development residue are also suppressed.

[Surfactant]

Examples of surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salts of styrene-acrylic acid copolymer, sodium stearate, and alkyl naphthalene sulfonic acid. Sodium, sodium alkyl diphenyl ether disulfonate, lauryl sulfate monoethanol Amine, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate and other anionic surfactants; polyoxyethylene oleyl Ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate and other non- Ionic surfactants; cationic surfactants such as alkyl quaternary ammonium salts or their ethylene oxide adducts; alkyl betaines such as alkyldimethylaminoacetic acid betaine, alkyl imidazolines, etc. The surfactant may be used alone or in mixture of two or more types, and is not necessarily limited to these.

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

<Removal of coarse particles>

The colored dispersion or photosensitive composition of the present invention preferably has coarse particles of 5 μm or more, preferably 1 μm or more, and further preferably 0.5 μm or more by centrifugal separation, filtration with a sintered filter or a membrane filter, etc. Removal of coarse particles and mixed dust. In this way, it is preferable that the colored composition does not substantially contain particles of 0.5 μm or more. More preferably, it is 0.3 micrometer or less.

As the filter, if it is a filter which has been used for filtration purposes etc. in the past, it can be used without particular limitation. For example, the use of fluororesins such as polytetrafluoroethylene (PTFE), nylon (such as nylon-6, Filters for polyamide-based resins such as nylon-6,6), polyolefin resins (including those with high density and ultra-high molecular weight) such as polyethylene and polypropylene (PP). Among these raw materials, polypropylene (including high-density polypropylene) and nylon are preferred.

The pore size of the filter is suitably about 0.01 μm to 7.0 μm, preferably about 0.01 μm to 3.0 μm, and more preferably about 0.05 μm to 0.5 μm. By setting it within the above range, fine foreign matter can be reliably removed. In addition, it is also preferable to use a fibrous filter material. Examples of fibrous filter materials include polypropylene fiber, nylon fiber, glass fiber, etc. Specifically, SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.), and SHPX type manufactured by Rokitechno can be used. Series (SHPX003, etc.) filter cartridges.

When using filters you can combine different filters. At this time, filtration by the first filter may be performed only once, or may be performed two or more times.

In addition, first filters with different pore sizes may be combined within the above range. The pore size here can refer to the filter manufacturer's nominal value. Commercially available filters can be purchased from, for example, Nihon Pall Co., Ltd. (DFA4201NXEY, etc.), Advantec Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Nihon Mico) Choose from various filters provided by Mykrolis Co., Ltd. or Kitz Micro Filter Co., Ltd.

<Color filter>

Next, the color filter of the present invention will be described.

The color filter of the present invention has a red filter segment, a green filter segment, and a blue filter segment. filter section. In addition, the color filter may further include a magenta filter segment, a cyan filter segment, and a yellow filter segment. The color filter of the present invention preferably has a red filter segment formed from the red photosensitive composition of the present invention.

<Manufacturing method of color filter>

Color filters can be produced by printing or photodevelopment.

Regarding the formation of filter segments using the printing method, patterning can be achieved by simply repeating printing and drying of a colored composition prepared as a printing ink, so it is low-cost and mass-producible as a manufacturing method for color filters. Excellent. Furthermore, the development of printing technology has made it possible to print fine patterns with high dimensional accuracy and smoothness. For printing, it is preferable to have a composition such that the ink does not dry or solidify on the printing plate or blanket. In addition, it is also important to control the fluidity of the ink on the printing press. Dispersants or extender pigments can also be used to adjust the viscosity of the ink.

When the filter segment is formed by a photodevelopment method, a coating method such as spray coating, spin coating, slit coating, roll coating, etc. is used to prepare the solvent-developing type or alkali-developing type colored resist material. The colored composition is applied on the transparent substrate so that the dry film thickness becomes 0.2 μm to 5 μm.

The film that has been dried as necessary is exposed (irradiated with radiation) through a mask having a predetermined pattern that is provided in a state of being in contact with or not in contact with the film. Thereafter, the film is immersed in a solvent or an alkali developer, or the developer is sprayed with a spray or the like, and the unhardened portion is removed to form a desired pattern. The same operation is repeated for other colors to produce a color filter. Furthermore, in order to promote the polymerization of colored resist materials, If necessary, heating at 80℃~250℃ can also be implemented. According to the photodevelopment method, a color filter with higher precision than the above-mentioned printing method can be produced.

During development, an aqueous solution such as sodium carbonate or sodium hydroxide may be used as an alkali developer, or an organic base such as dimethylbenzylamine or triethanolamine may be used. In addition, defoaming agents or surfactants can also be added to the developer.

Furthermore, in order to improve the exposure sensitivity, after the colored resist is coated and dried, a water-soluble or alkali-water-soluble resin, such as polyvinyl alcohol or a water-soluble acrylic resin, may be coated and dried to form a protective layer that prevents damage caused by oxygen. After causing polymerization to hinder the film, exposure is performed.

In addition to the above-mentioned methods, the color filter of the present invention can be produced by an electrodeposition method, a transfer method, an inkjet method, etc., and the colored composition of the present invention can also be used in any method. Furthermore, the electrodeposition method is a method of manufacturing a color filter by utilizing a transparent conductive film formed on a substrate and electrophoresis of colloidal particles to form filter segments of various colors on the transparent conductive film. In addition, the transfer method is a method of forming a filter segment in advance on the surface of a peelable transfer base sheet and transferring the filter segment to a desired substrate.

A black matrix can be formed in advance before forming filter segments of various colors on the transparent substrate or reflective substrate. As the black matrix, a multilayer film of chromium or chromium/chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed can be used, but it is not limited to these. In addition, a thin film transistor (TFT) may be preformed on the transparent substrate or reflective substrate, and then filter segments of various colors may be formed. In addition, on the color filter of the present invention, if necessary, an overcoat film, a transparent conductive film, or the like is formed.

The color filter of the present invention is bonded to an opposing substrate using a sealant, and liquid crystal is injected from an injection port provided in the sealing portion. The injection port is then sealed, and a polarizing film or a retardation film is bonded to the outside of the substrate if necessary. This is used to manufacture color liquid crystal display devices. The color liquid crystal display device can be configured in Twisted Nematic (TN), Super Twisted Nematic (STN), In-Plane Switching (IPS), Vertically Alignment (VA) , Optically Compensated Bend (OCB) and other liquid crystal display modes that use color filters to perform colorization.

In addition to color liquid crystal display devices, the color filter of the present invention can also be used in the production of color solid-state imaging elements, organic EL display devices, quantum dot display devices, electronic paper, and the like.

[Example]

Hereinafter, the present invention will be specifically described using examples. However, the present invention is not limited to the following examples unless the gist thereof is exceeded. In addition, in the examples and comparative examples, "parts" and "%" mean "mass parts" and "mass %".

(weight average molecular weight of resin)

The weight average molecular weight (Mw) of the resin was measured using a Gel Permeation Chromatograph (GPC) equipped with an RI detector using a TSKgel column (manufactured by Tosoh Co., Ltd.) and equipped with an RI detector (manufactured by Tosoh Co., Ltd. , HLC-8320GPC), and the weight average molecular weight (Mw) measured in terms of polystyrene using tetrahydrofuran (THF) as a developing solvent.

(acid value of resin)

The acid value of the resin is a value obtained by converting the measured acid value (mgKOH/g) into non-volatile content by the potentiometric titration method in accordance with Japanese Industrial Standards (JIS) K 0070.

<Manufacture of resin dispersant (B)>

(Resin dispersant (B-1))

Put 8 parts of 3-mercapto-1,2-propanediol, 12 parts of pyromellitic anhydride, and 80 parts of propylene glycol monomethyl ether acetate (PGMAc) into a reaction vessel equipped with a gas introduction pipe, a thermometer, a condenser, and a stirrer. 0.2 parts of monobutyltin oxide as a catalyst was replaced with nitrogen gas, and then reacted at 120° C. for 5 hours (first step). By measuring the acid value, it was confirmed that more than 95% of the acid anhydride was half-esterified. Next, add 30 parts of methyl methacrylate (MMA), 10 parts of tert-butyl acrylate (tBA), 10 parts of ethyl acrylate (EA), 5 parts of methacrylic acid (MAA), and benzyl methacrylate ( BzMA) 10 parts, 35 parts 2-hydroxyethyl methacrylate (HEMA), heat the reaction vessel to 80°C, and add 2,2'-azobis(2,4-dimethylvaleronitrile) 1 portion, react for 12 hours (second step). Measurement of non-volatile components confirmed that 95% of the reaction was completed. Next, the air in the flask was replaced, 38.0 parts of 2-methacryloxyethyl isocyanate (MOI) and 0.1 part of hydroquinone were put in, and the reaction was carried out at 70° C. for 4 hours (third step) . After confirming the disappearance of the peak at 2270 cm ^-1 based on the isocyanate group by IR, the reaction solution was cooled and the non-volatile content was adjusted using PGMAc to obtain a resin-type dispersant (B-1) with 40% non-volatile content. solution. The obtained resin-type dispersant had an acid value of 40 and a weight-average molecular weight of 12,000.

(Resin type dispersant (B-2~B-23))

Except using the raw materials and input amounts described in Table 1 and Table 2, the synthesis was carried out in the same manner as the resin dispersant (B-1) to obtain a resin dispersant (B-2) ~ resin type with a non-volatile content of 40%. Solution of dispersant (B-22).

[Table 1]

BTDA: 3,3',4,4'-benzophenone tetracarboxylic dianhydride

MMA: methyl methacrylate

tBA: tert-butyl acrylate

EA: Ethyl acrylate

MAA: methacrylic acid

BzMA: Benzyl methacrylate

HEMA: 2-hydroxyethyl methacrylate

HPMA: 2-hydroxypropyl methacrylate

FM-3: Terminal hydroxyl polycaprolactone modified methacrylate (produced by Daicel Chemical: Placcel FM-3)

MOI: 2-methacryloxyethyl isocyanate (manufactured by Showa Denko: Karenz MOI)

AOI: 2-acryloxyethyl isocyanate (manufactured by Showa Denko: Karenz AOI)

BEI: 1,1-bis(acryloxymethyl)ethyl isocyanate (manufactured by Showa Denko: Karenz BEI)

<Manufacture of adhesive resin>

(Acrylic resin solution 1)

Add 100 parts of propylene glycol monomethyl ether acetate to a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirring device in a detachable four-necked flask, and heat to 120°C while injecting nitrogen gas into the vessel. Use drops at the same temperature A mixture of 5.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 41.0 parts of dicyclopentyl methacrylate, and 1.0 part of azobisisobutyronitrile was added dropwise over 2.5 hours, and the polymerization reaction was performed.

Next, the air in the flask was replaced, and 0.3 parts of tris-dimethylaminomethylphenol and 0.3 parts of hydroquinone were added to 17.0 parts of acrylic acid, and the reaction was continued at 120°C for 5 hours and the acid value of the non-volatile component was maintained =0.8, the reaction was completed, and a resin solution with a weight average molecular weight of approximately 12,000 (measured by GPC) was obtained.

Furthermore, 30.4 parts of tetrahydrophthalic anhydride and 0.5 part of triethylamine were added, and the mixture was reacted at 120°C for 4 hours, and propylene glycol monomethyl ether acetate was added so that the non-volatile content was 40% to prepare acrylic acid. Resin solution 1.

<Manufacture of Coloring Agent (A)>

<Manufacture of micronized red pigment (PR254-1)>

Mix 200 parts of diketopyrrolopyrrole red pigment C.I. Pigment Red 254 ("Irgajin Red L 3630" manufactured by BASF), 1,400 parts of sodium chloride, and 360 parts of diethylene glycol A portion was put into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), and kneaded at 80° C. for 6 hours. Next, the kneaded product was put into 8,000 parts of warm water and stirred for 2 hours while heating to 80° C. to form a slurry. Filtration and water washing were repeated to remove sodium chloride and diethylene glycol. After drying at 85°C for one day and night, a diketopyrrolopyrrole-based fine red pigment (PR254-1) was obtained.

<Manufacture of finely divided yellow pigment (PY139-1)>

The yellow pigment C.I. Pigment Yellow 139 (PASF manufactured by BASF 200 parts of Paliotol Yellow (D1819"), 1,400 parts of sodium chloride, and 360 parts of diethylene glycol were put into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), and kneaded at 80°C for 6 hours . Next, the kneaded product was put into 8,000 parts of warm water and stirred for 2 hours while heating to 80° C. to form a slurry. Filtration and water washing were repeated to remove sodium chloride and diethylene glycol. After drying at 85°C for one day and night, a finely divided yellow pigment (PY139-1) was obtained.

<Manufacture of finely divided blue pigment (PB15:6-1)>

Mix 200 parts of phthalocyanine blue pigment CI Pigment Blue 15:6 ("LIONOL BLUE ES" manufactured by Toyo-Color Co., Ltd., specific surface area ^60m2 /g) and sodium chloride 1,400 parts and 360 parts of diethylene glycol were put into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), and kneaded at 80° C. for 6 hours. Next, the kneaded product was put into 8,000 parts of warm water and stirred for 2 hours while heating to 80° C. to form a slurry. Filtration and water washing were repeated to remove sodium chloride and diethylene glycol. It was dried at 85°C for one day and night to obtain a phthalocyanine-based micron blue pigment (PB15: 6-1).

<Manufacture of finely divided purple pigment (PV23-1)>

Mix 200 parts of dioxazine-based purple pigment C.I. Pigment Violet 23 ("LIONOGEN VIOLET RL" manufactured by Toyo-Color Co., Ltd.), 1,400 parts of sodium chloride, and 360 parts of diethylene glycol A portion was put into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), and kneaded at 80° C. for 6 hours. Next, the kneaded product was put into 8,000 parts of warm water and stirred for 2 hours while heating to 80° C. to form a slurry. Filtration and water washing were repeated to remove sodium chloride and diethylene glycol. After removal, it was dried at 85° C. for one day and night to obtain a dioxazine-based purple micronized purple pigment (PY23-1).

<Manufacture of micronized green pigment (PG58-1)>

Mix 200 parts of phthalocyanine green pigment C.I. Pigment Green 58 ("Fastogen Green A110" manufactured by DIC Co., Ltd.), 1,400 parts of sodium chloride, and 360 parts of diethylene glycol It was put into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), and kneaded at 80°C for 6 hours. Next, the kneaded product was put into 8,000 parts of warm water and stirred for 2 hours while heating to 80° C. to form a slurry. Filtration and water washing were repeated to remove sodium chloride and diethylene glycol. It was dried at 85°C for one day and night to obtain a phthalocyanine-based micronized green pigment (PG58-1).

<Manufacture of finely divided yellow pigment (PY150-1)>

Add 200 parts of nickel complex-based yellow pigment C.I. Pigment Yellow 150 ("E-4GN" manufactured by Lanxess), 1,400 parts of sodium chloride, and 360 parts of diethylene glycol into a stainless steel 1-gallon kneader. machine (manufactured by Inoue Seisakusho), and kneaded at 80°C for 6 hours. Next, the kneaded product was put into 8,000 parts of warm water and stirred for 2 hours while heating to 80° C. to form a slurry. Filtration and water washing were repeated to remove sodium chloride and diethylene glycol. It was dried at 85°C for one day and night to obtain a nickel complex-based fine yellow pigment (PY150-1).

<Manufacturing of micronized yellow pigment (PY185-1)>

As a yellow colorant, 200 parts of C.I. Pigment Yellow 185 ("Paliotol Yellow L 1155" manufactured by BASF), 1,000 parts of sodium chloride, and 100 parts of diethylene glycol were put into stainless steel Make a 1-gallon kneader (Made by Inoue (manufactured) and kneaded at 100°C for 6 hours. Next, the kneaded product was put into 5 liters of warm water and stirred for 1 hour while heating to 70° C. to form a slurry. Filtration and water washing were repeated to remove sodium chloride and diethylene glycol. After drying at 80°C for one day and night, a yellow colorant (PY185-1) was obtained.

<Production method of salt-forming compound (V)>

A salt-forming compound (V) containing C.I. Acid Red 289 and tristearylmonomethylammonium chloride as a quaternary ammonium salt compound was prepared according to the following procedure. Dissolve 10 parts of C.I. Acid Red 289 in 200 parts of water to form a 5% aqueous solution. After heating to 30°C to 50°C, dissolve 5.5% of the methanol/water = 20/80 solution to form a 5% solution. of tristearylmonomethylammonium chloride and add it dropwise little by little. After adding the tristearylmonomethylammonium chloride solution dropwise, stir at 30°C to 50°C for 3 hours. While stirring, let it cool to room temperature, perform suction filtration, and after washing with water, use a dryer to remove the water from the salt-forming compound remaining on the filter paper and dry it to obtain C.I. Acid Red 289 and tristearyl monomethyl. 8 parts of salt-forming compound (V) of ammonium chloride.

<Method for producing a resin solution (SV) containing a salt-forming compound>

The following mixture was stirred and mixed to become uniform, and then filtered through a 5.0 μm filter to prepare a resin solution (SV) containing a salt-forming compound.

Salt-forming compound (V): 8.0 parts

Cyclohexanone: 92.0 parts

<Pigment Derivatives>

Pigment derivative A…a compound described in Japanese Patent Application Laid-Open No. 2007-314681 Object C

Pigment derivative B…General formula 31 described in Japanese Patent Application Laid-Open No. 2006-291194

Pigment derivative C...Compound iii described in Japanese Patent Application Laid-Open No. 2017-165820

Pigment derivative D…derivative 51 described in Japanese Patent Application Laid-Open No. 2005-181383

<Manufacture of Colored Dispersion>

(Coloring composition D-1)

After stirring and mixing the following mixture to become uniform, use an eiger mill (mini model M manufactured by eiger Japan) using zirconia beads with a diameter of 0.5 mm. -250MKII") was dispersed for 5 hours, and then filtered with a 5.0 μm filter to prepare a colored composition (D-1).

Micronized pigment (PR254-1): 13.3 parts

Pigment derivative A: 0.7 parts

Pigment derivative B: 0.7 parts

Resin type dispersant (B-1) solution: 13.0 parts

Propylene glycol monomethyl ether acetate (PGMAC): 72.2 parts

(Coloring composition D-2~Coloring composition D-65)

(Coloring composition D-2 to Coloring composition D- were produced in the same manner as Colored Composition D-1 except that the colorant, pigment derivative, and resin dispersant solution were changed to the compositions shown in Table 3 to Table 9. 65).

<Manufacture of photosensitive coloring composition for color filters>

[Example 101~Example 121, Example 201~Example 209, Example 301~Example 306 and Comparative Example 101~Comparative Example 104, Comparative Example 201~Comparative Example 206, Comparative Example 301~Comparative Example 304] ( RR-1~RR-26, RG-1~RG-15, RB-1~RB-10)

Each material was mixed and stirred at the formula ratio shown in Table 10, and filtered with a 1 μm filter to obtain photosensitive coloring compositions of each color.

[Table 10]

The abbreviations in Table 10 are shown below.

． Photopolymerization initiator C1: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one (IRGACURE manufactured by BASF) )907》)

． Photopolymerization initiator C2: (oxime ester): ethane-1-one, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-oxazol-3-yl] , 1-(O-acetyl oxime) ("IRGACURE OXE02" manufactured by BASF)

． Photopolymerizable compound E1: dipentaerythritol hexaacrylate ("Aronix M-402" manufactured by Toagosei Co., Ltd.)

． Organic solvent: propylene glycol monomethyl ether acetate

<Evaluation of photosensitive coloring compositions for color filters>

The obtained photosensitive colored composition was evaluated by the following method. The results are shown in Table 11.

[Viscosity and viscosity stability of photosensitive coloring compositions]

About the obtained photosensitive coloring composition, the initial viscosity at 25 degreeC was measured using viscometer TV22 manufactured by Toki Sangyo Co., Ltd. In addition, the viscosity after promotion during one menstrual period was measured at 40° C. and the viscosity increase rate was calculated. Evaluation is based on the following criteria.

◎: Initial viscosity is 10.0Pa. s or less, and the viscosity increase over time is less than 40%

○: Initial viscosity is 10.0Pa. s or less, and the viscosity increase over time is more than 40%

×: Initial viscosity is 10.0Pa. s or above

[Pattern formation of filter segments]

The obtained photosensitive coloring composition was applied to a 10 cm × 10 cm glass substrate by spin coating, and then heated at 70° C. for 5 minutes in a clean oven to remove the solvent, thereby obtaining a coating film of approximately 2 μm. Then, after the substrate was cooled to room temperature, an ultrahigh-pressure mercury lamp was used to expose the photoresist with a stripe pattern of 100 μm wide (pitch 200 μm) and 25 μm wide (pitch 50 μm) at an exposure dose of 50 mJ/cm ² . Thereafter, the substrate was spray developed using a sodium carbonate aqueous solution at 23° C., then washed with ion-exchange water, air-dried, and heated at 230° C. for 20 minutes in a clean oven. Spray development is performed for the shortest time that can form a pattern without development residue on the coating film using each photosensitive coloring composition, and this is set as an appropriate development time.

The film thickness of the coating film was measured using Dektak 3030 (manufactured by Nippon Vacuum Technology Co., Ltd.).

[Measurement of film thickness at specified color]

When using the above method to form a filter segment, the number of revolutions of spin coating is appropriately changed to form a plurality of filter segments with different film thicknesses. The chromaticity was measured using a microspectrophotometer ("OSP-SP100" C light source manufactured by Olympus Optical Co., Ltd.). Based on the measured values, the film thickness of x=0.655 in the case of the red photosensitive coloring composition, y=0.614 in the case of the green photosensitive coloring composition, and the film thickness of y=0.614 in the case of the blue photosensitive coloring composition were calculated by calculation. In the case of a color photosensitive coloring composition, the film thickness is y=0.049. The calculated film thickness was used and evaluated based on the following criteria.

◎: Film thickness is 1.2μm or more and less than 1.8μm

○: Film thickness is 1.8 μm or more and less than 2.2 μm

×: Film thickness is 2.2 μm

[Analytical evaluation]

Regarding the pattern in the 25 μm photoresist portion of the filter segment formed by the above method, the resolution was visually evaluated using an optical microscope. Poor resolution means that adjacent stripe patterns are connected or have defects. The levels of evaluation are as follows.

◎: The stripe pattern is completely independent and no residue is found between the lines.

○: The stripe pattern is completely independent, but residue is found between the lines

△: Adjacent stripe patterns are partially connected.

×: Adjacent stripe patterns are connected.

[Linearity evaluation]

The pattern in the 100 μm photoresist portion of the filter segment formed by the above method was observed and evaluated using an optical microscope. The levels of evaluation are as follows. Furthermore, C and D are levels that are difficult to use.

S: Very good linearity

A: Good linearity

B: Straightness is generally good and usable.

C: The linearity is partially defective and the level is difficult to use.

D: Poor linearity

[Dimensional stability evaluation]

Regarding the pattern in the 100 μm photoresist portion of the substrate patterned with exposure amounts of 30 mJ/cm ² and 50 mJ/cm ² , the line width was measured using an optical microscope. The increase in line width when the exposure amount is 50 mJ/cm ² is calculated relative to the line width when the exposure amount is 30 mJ/cm ² . The smaller the increase, the better the dimensional stability. If the increase is less than 3 μm, it is evaluated as a usable level. That is, C and D are levels that are difficult to use.

S: The increase is less than 1μm

A: The increase is more than 1μm and less than 2μm

B: The increase is more than 2μm and less than 3μm

C: The increase is 3 μm or more and less than 5 μm

D: The increase is 5μm or more

[Evaluation of development stability]

During spray development, the pattern film thickness formed by developing at an appropriate development time is used as a standard, and the pattern film thickness of a filter segment formed by developing at twice the appropriate development time is compared. The evaluation level is as follows, and the case where the film thickness difference is within 25% is considered a usable level.

◎: Film thickness difference is within 15%

○: Film thickness difference exceeds 15% and is within 25%

△: Film thickness difference exceeds 25% and is within 40%

×: The film thickness difference exceeds 40%. Or become chipped or peeled off

[Table 11]

As shown in Table 11, it was formed using the photosensitive coloring compositions of Examples 101 to 121, 201 to 209, and 301 to 306 of the present application using the resin-type dispersant (B). Compared with the filter segments formed using Comparative Examples 101 to 104, Comparative Examples 201 to 206, and Comparative Examples 301 to 304, the resolution, development stability, linearity, and dimensional stability of the filter segments are stable The properties are good, and the pattern shape shows more excellent characteristics.

Furthermore, it is clear that by setting the ratio of one or more ethylenically unsaturated monomers selected from the ethylenically unsaturated monomers (c) having a hydroxyl group to 35% to 100%, and more preferably to 38% to 60% , can form a better pattern shape. In addition, the photosensitive coloring composition produced using the resin-type dispersant B-22 has a high viscosity and is difficult to use. In addition, the initial viscosity of the photosensitive coloring composition using the resin-type dispersants B-14, B-15, B-16, and B-22 was good and practical, but thickening with time was confirmed.

In addition, the double bond equivalent Z of the side chain of the resin-type dispersant (B) calculated as ((c) weight + (d) weight)/((meth)acrylyl mole number in (d)) Resin (B-1) ~ Resin (B-7), Resin (B-10) ~ Resin (B-19), which are 300g/mol ~ 600g/mol, have good pattern shapes compared with resins that are not. Shows excellent characteristics. In addition, if the content of the carboxyl group-containing ethylenically unsaturated monomer in the ethylenically unsaturated monomer (c) is 2.5 mass% to 10.0 mass%, and more preferably 2.5 mass% to 5 mass%, it is shown Excellent resolution. In addition, it was also found that the photosensitive coloring composition in which the photopolymerization initiator (C) is C2 shows excellent dimensional stability in combination with the resin-type dispersant (B) described in this patent.

In addition, comparative examples with a colorant content of more than 40%, namely RR-20 and coloring Compared with RR-25 with a low content of additives, the patterning characteristics are further deteriorated and it is difficult to use. However, as confirmed in RR-3 and the like, it is clear that according to the present invention, even in a photosensitive coloring composition with a colorant content of 40% or more, it is better than the photosensitive coloring composition RR with a low colorant content. Compared with -24, it also has equally good patterning properties.

<Production of color filters>

A black matrix is patterned on a glass substrate, and the red photosensitive coloring composition (RR-3) of the present invention is applied to the substrate using a spin coater so that x=0.655 and y=0.325 in a C light source. and form a colored film. The film was irradiated with ultraviolet light of 50 mJ/cm ² using an ultrahigh-pressure mercury lamp through a photoresist.

Next, spray development was performed using an alkaline developer containing 0.2 mass % sodium carbonate aqueous solution to remove the unexposed portion, and then the substrate was washed with ion-exchanged water and heated at 220° C. for 20 minutes to form a red filter. part. Using the same method, the green photosensitive coloring composition (RG-1) of the present invention is used to form a green filter segment such that x=0.327, y=0.614, and the blue photosensitive coloring composition of the present invention is used (RB-1) forms a blue filter segment with x=0.147 and y=0.049 to obtain a color filter.

By using the photosensitive coloring composition of the present invention, a high-quality color filter can be produced.

Claims (9)

A photosensitive coloring composition for color filters, containing a colorant A, a resin dispersant B, a photopolymerization initiator C, an organic solvent D and a polymerizable compound E, wherein the resin dispersant B is in the molecule An ethylenically unsaturated monomer containing a hydroxyl group in the presence of a reaction product of a hydroxyl group of a compound a having two hydroxyl groups and a thiol group, and an acid anhydride group of pyromellitic anhydride and/or trimellitic anhydride It is formed by reacting the hydroxyl group of the hydroxyl group-containing polymer obtained by polymerizing the ethylenically unsaturated monomer c of b and the isocyanate group of the compound d having one isocyanate group and one or more (meth)acrylyl groups. Resin in which the content of the structural units derived from the hydroxyl-containing ethylenically unsaturated monomer b is 35 mass % or more and 80 mass % or less with respect to the total amount of structural units derived from the ethylenically unsaturated monomer c. , the content of the carboxyl group-containing ethylenically unsaturated monomer in the ethylenically unsaturated monomer (c) of the hydroxyl-containing ethylenically unsaturated monomer (b) is 2.5 mass% to 10.0 mass%, The molar ratio of the hydroxyl group in the hydroxyl-containing compound and the isocyanate group in the compound (d) having one isocyanate group and more than one (meth)acrylyl group is relative to the hydroxyl-containing compound. The hydroxyl group in the compound (d) having one isocyanate group and one or more (meth)acrylyl groups is 0.2 mole to 1.0 mole, and the resin dispersant B is The weight average molecular weight is 2,000~100,000, and the acid value of the resin dispersant B is 5 mgKOH/g~200 mgKOH/g. The photosensitive coloring composition for color filters described in claim 1, wherein (the total mass of the structural units derived from c ethylenically unsaturated monomer + derived from d has one isocyanate group and one The total mass of the structural units of the above (meth)acrylyl compound)/((Methyl group derived from d) contained in the structural units of the compound having one isocyanate group and more than one (meth)acrylyl group ) The double bond equivalent Z in the side chain of the resin-type dispersant B represented by ) is 300 g/mol to 600 g/mol. The photosensitive coloring composition for color filters according to claim 1 or 2, wherein the resin dispersant B contains a structural unit derived from an ethylenically unsaturated monomer b containing a hydroxyl group. The content of is 38 mass% or more and 60 mass% or less with respect to the total amount of structural units derived from the ethylenically unsaturated monomer c. The photosensitive coloring composition for color filters according to claim 1 or 2, wherein the content of colorant A is relative to the total non-volatile content of the photosensitive coloring composition for color filters. And it is 40 mass % or more. The photosensitive coloring composition for color filters according to claim 3, wherein the content of colorant A is 40 mass based on the total amount of non-volatile components of the photosensitive coloring composition for color filters. %above. The photosensitive coloring composition for color filters according to claim 1 or 2, wherein the photopolymerization initiator C contains an oxime ester compound. The photosensitive coloring composition for color filters according to claim 3, wherein the photopolymerization initiator C contains an oxime ester compound. The photosensitive coloring composition for color filters according to claim 4, wherein the photopolymerization initiator C contains an oxime ester compound. A color filter includes: a filter segment formed on a substrate by the photosensitive coloring composition for color filters described in any one of items 1 to 8 of the patent application scope.