JP6915646B2 - Photosensitive compositions for color filters and color filters - Google Patents

Description

The present invention relates to a photosensitive coloring composition for a color filter, and more specifically, for forming red, green, and blue filter segments of a color filter used in a liquid crystal display device, an organic EL display, or the like. It relates to a particularly useful photosensitive coloring composition.

The color filter is formed by arranging two or more kinds of fine band-shaped filter segments having different hues on a transparent substrate such as a glass substrate so as to be parallel (striped) or intersect with each other, or the hue. Two or more kinds of fine filter segments having different values are arranged so as to be arranged in order in each of the vertical direction and the horizontal direction. The filter segments have small dimensions of a few microns to a few hundreds of microns and are neatly arranged in a predetermined arrangement for each hue.
Currently, as a method for manufacturing a color filter, a method called a pigment dispersion method, which uses a pigment having excellent various resistances such as light resistance and heat resistance as a coloring material, is the mainstream. In the pigment dispersion method, a color filter is manufactured by the following method. First, a photosensitive coloring composition (pigment resist) obtained by dispersing a pigment in a photosensitive transparent resin solution is applied to a transparent substrate such as glass. After removing the solvent from the coating by drying, the coating is exposed in a pattern corresponding to a filter segment of a certain color. Next, the unexposed portion of the coating film is removed by development, and then heat treatment or the like is performed as necessary. As a result, the filter segment pattern of the first color is obtained. Then, by performing the same operation as this, a filter segment pattern of another color is formed, and the color filter is completed.

In recent years, high-color reproduction of displays has become an important trend. High-color reproduction of displays has been focused on improving the color reproducibility of backlights, but it is necessary to use very dark colors for color filters in order to improve color reproducibility. In such a case, in the exposure process of forming the pattern of the color filter, the amount of light reaching the bottom of the coating film becomes weak, so that the photocuring tends to be insufficient, and a problem that a pattern having a desired shape cannot be obtained occurs. do.

Specifically, the photosensitive coloring composition is required to have dimensional stability in which the size of the pattern obtained in the color filter manufacturing process is within a certain degree of variation when the exposure amount in the exposure process is varied. In a photosensitive coloring composition that realizes high color reproduction, such dimensional stability tends to deteriorate. Similarly, in a photosensitive coloring composition that realizes high color reproduction, the linearity of the pattern tends to deteriorate.

Various methods have been studied so far to solve these problems. For example, in Patent Document 1, dimensional stability is ensured by adding a polymer having a specific structure to the photosensitive composition. In Patent Document 2, the pattern shape and dimensional stability are realized by providing an anchor layer on the substrate. In Patent Document 3, the stability of the pattern size at a low exposure amount is realized by adding a polymer having a specific structure to the photosensitive composition. In Patent Document 4, dimensional stability is achieved by using a polymerization initiator having a specific structure. In Patent Document 5, dimensional stability with respect to development is ensured by using a thiol compound. However, the high dimensional stability and linearity required for color filters today have not been sufficiently achieved, and further improvement is required.

Japanese Unexamined Patent Publication No. 2013-254047 Japanese Unexamined Patent Publication No. 2013-073115 Japanese Unexamined Patent Publication No. 2012-108227 Japanese Unexamined Patent Publication No. 2011-002796 Japanese Unexamined Patent Publication No. 2010-039475

The present invention has been made in view of the above circumstances, and has various patterning characteristics (resolution, linearity, dimensional stability, development stability) and a photosensitive coloring composition required for a photosensitive coloring composition. It is an object of the present invention to provide a photosensitive coloring composition capable of achieving high dimensional stability and linearity while satisfying the viscosity stability of an object, and a color filter produced from the photosensitive coloring composition.

As a result of diligent studies, the present inventors have made that the hydroxyl group of compound (a) having two hydroxyl groups and one thiol group in the molecule, and acid anhydride of pyromellitic acid anhydride and / or trimellitic acid anhydride. In the presence of the reaction product of the compound group, the hydroxyl group of the hydroxyl group-containing polymer obtained by polymerizing the ethylenically unsaturated monomer (c) containing the hydroxyl group-containing ethylenically unsaturated monomer (b) and 1 It is a resin obtained by reacting one isocyanate group and the isocyanate group of compound (d) having one or more (meth) acryloyl groups, and the content of the hydroxyl group-containing ethylenically unsaturated monomer (b) is ethylene. The photosensitive coloring composition for a color filter containing a resin-type dispersant containing 35 to 80% by mass based on the total amount of the sex unsaturated monomer (c) has high dimensional stability and linearity as described above. I found that it could be achieved.

<1> A photosensitive coloring composition for a color filter containing a colorant (A), a resin-type dispersant (B), a photopolymerization initiator (C), an organic solvent (D), and a polymerizable compound (E). The resin-type dispersant (B) contains the hydroxyl group of the compound (a) having two hydroxyl groups and one thiol group in the molecule, and the acid anhydride of pyromellitic acid anhydride and / or trimellitic acid anhydride. One hydroxyl group of a hydroxyl group-containing polymer obtained by polymerizing an ethylenically unsaturated monomer (c) containing a hydroxyl group-containing ethylenically unsaturated monomer (b) in the presence of a reaction product of the group. A resin obtained by reacting an isocyanate group and an isocyanate group of compound (d) having one or more (meth) acryloyl groups, and containing a structural unit derived from a hydroxyl group-containing ethylenically unsaturated monomer (b). A photosensitive coloring composition for a color filter, wherein the amount is 35% by mass or more and 80% by mass or less with respect to the total amount of the constituent units derived from the ethylenically unsaturated monomer (c).

<2> ((c) Total mass of constituent units derived from ethylenically unsaturated monomers + (d) All constituent units derived from compounds having one isocyanate group and one or more (meth) acryloyl groups Mass) / ((d) Mol number of (meth) acryloyl group contained in a structural unit derived from a compound having one isocyanate group and one or more (meth) acryloyl groups) The photosensitive coloring composition for a color filter, wherein the double bond equivalent (Z) in the side chain of (B) is 300 to 600 g / mol.

<3> The content of the structural unit derived from the hydroxyl group-containing ethylenically unsaturated monomer (b) in the resin-type dispersant (B) is the total amount of the structural unit derived from the ethylenically unsaturated monomer (c). The photosensitive coloring composition for a color filter, which is 38% by mass or more and 60% by mass or less with respect to the above.

<4> The photosensitive coloring composition for a color filter, wherein the content of the colorant (A) is 40% by mass or more with respect to the total solid content of the photosensitive coloring composition for a color filter.

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

<6> A color filter comprising a filter segment formed from the above-mentioned photosensitive coloring composition for a color filter on a base material.

By using the resin type dispersant having the specific structure of the present invention, photosensitive coloring is performed while satisfying various patterning characteristics (resolution, linearity, dimensional stability, development stability) required for the photosensitive coloring composition. It is possible to provide a photosensitive coloring composition for a color filter having excellent viscosity stability, dimensional stability and linearity as a composition. Further, it is possible to provide a high-quality color filter using the photosensitive coloring composition for a color filter.

Hereinafter, embodiments of the present invention will be described in detail. In the present 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 a color filter of the present invention contains a colorant (A), a resin-type dispersant (B), a photopolymerization initiator (C), an organic solvent (D) and a polymerizable compound (E). , The resin-type dispersant (B) has a hydroxyl group of compound (a) having two hydroxyl groups and one thiol group in the molecule, and an acid anhydride group of pyromellitic acid anhydride and / or trimellitic acid anhydride. A hydroxyl group of a hydroxyl group-containing polymer obtained by polymerizing an ethylenically unsaturated monomer (c) containing a hydroxyl group-containing ethylenically unsaturated monomer (b) in the presence of the reaction product of It is a resin obtained by reacting with the isocyanate group of the compound (d) having one or more (meth) acryloyl groups, and the content of the hydroxyl group-containing ethylenically unsaturated monomer (b) is ethylenically unsaturated mono. It is characterized in that it is 35% by mass or more and 80% by mass or less with respect to the total amount of the polymer (c).
Hereinafter, the photosensitive coloring composition for a color filter of the present invention will be described in detail.

<Resin type dispersant (B)>
The resin-type dispersant (B) of the present invention comprises a hydroxyl group of a compound (a) having two hydroxyl groups and one thiol group, and an acid anhydride group of pyromellitic anhydride and / or trimellitic acid anhydride. The first step of first producing the reaction product, followed by ethylenically unsaturated containing the hydroxyl group-containing ethylenically unsaturated monomer (b) using the remaining thiol groups of the reaction product as a chain transfer agent. A second step of producing a hydroxyl group-containing polymer in which a vinyl polymer portion having a hydroxyl group is introduced by radically polymerizing the monomer (c), and further, one isocyanate group and one or more (meth) acryloyl groups are added. It is obtained by going through a third step, which is a reaction with the compound (d) having. The plurality of carboxyl group portions in the resin-type dispersant (B) of the present invention function as a pigment adsorbing portion, and the vinyl polymer portion functions as a solvent affinity portion.

Further, the resin-type dispersant (B) of the present invention has a plurality of reactions such as a 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 has a complicated structure obtained via the above, and it is impossible or almost unrealistic to express it by a general formula (structure), it is described by 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 (also known as 1-thioglycerol), 2-mercapto-1,3-propanediol, 2-mercapto-1,2-propanediol, 2-
Mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1, Examples thereof include 3-propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol, and the like.

In the present specification, the vinyl polymer portion obtained by radical polymerization of the ethylenically unsaturated monomer (c) containing the hydroxyl group-containing ethylenically unsaturated monomer (b) is defined in the structure of the resin-type dispersant B. In the above, it is a continuous portion not containing a polyester moiety having a carboxyl group obtained by reacting a compound (a) having two hydroxyl groups and one thiol group with pyromellitic anhydride and / or trimellitic anhydride. .. One molecule constituting the resin-type dispersant (B) contains one vinyl polymer moiety when only trimellitic anhydride is used, and a plurality of vinyl polymer moieties when pyromellitic anhydride is used. Is done. It is more preferable to use pyromellitic anhydride from the viewpoint of dispersion stability.

A known catalyst can be used as the catalyst used when reacting the acid anhydride group of the present invention with the hydroxyl group. For example, triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0]. -5-Nonene, monobutyltin oxide and the like can be mentioned.

In the reaction product of the hydroxyl group of the compound (a) having two hydroxyl groups and one thiol group obtained in the first step and the acid anhydride group of pyromellitic acid anhydride and / or trimellitic acid anhydride. , The number of moles of the acid anhydride group in the pyromellitic acid anhydride (p), the number of moles of the acid anhydride group in the trimellitic acid anhydride (t), two hydroxyl groups and one thiol group in the molecule. When the number of moles of the hydroxyl group in the compound (a) having and is (o), the molar ratio thereof is 0.3 <[(p) + (t)] / (o) <1.0. Preferably, more preferably 0.5 <[(p) +
(T)] / (o) <1.0, most preferably 0.6 <[(p) + (t)] / (o) <0.8
Is. If it is 0.3 or less, the acid anhydride residue that is the pigment adsorbing part may be reduced, and the acid value of the resin may also be low. If it is 1.0 or more, the unreacted acid anhydride group may be used. May remain, resulting in poor storage stability.

Next, it remains 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 acid anhydride. A hydroxyl group-containing ethylenically unsaturated monomer is introduced by radically polymerizing an ethylenically unsaturated monomer (c) containing a hydroxyl group-containing ethylenically unsaturated monomer (b) using the thiol group as a chain transfer agent. The second step of producing the produced hydroxyl group-containing polymer will be described. By copolymerizing the ethylenically unsaturated monomer (b) containing a hydroxyl group in the second step, the hydroxyl group can be introduced into the vinyl polymer portion of the dispersant, and one isocyanate can be introduced in the third step. It can be reacted with compound (d) having a group and one or more (meth) acryloyl groups.

(Hydroxy group-containing ethylenically unsaturated monomer (b))
The hydroxyl group-containing ethylenically unsaturated monomer (b) may be any monomer having a hydroxyl group and having an ethylenically unsaturated double bond, but specifically, a hydroxyl group. (Meta) acrylate-based monomers having, for example, 2-hydroxyethyl (meth) acrylate, 2 (or 3) -hydroxypropyl (meth) acrylate, 2 (or 3 or 4) -hydroxybutyl (meth) acrylate and A hydroxyalkyl (meth) acrylate such as cyclohexanedimethanol mono (meth) acrylate, an alkyl-α-hydroxyalkyl acrylate such as ethyl-α-hydroxymethyl acrylate, or a (meth) acrylamide-based monomer having a hydroxyl group, for example. N- (2-Hydroxyethyl) (meth) acrylamide, N- (2-hydroxypropyl) (meth) acrylamide, N
N- (hydroxyalkyl) (meth) acrylamide such as-(2-hydroxybutyl) (meth) acrylamide, or vinyl ether-based monomers having a hydroxyl group, such as 2-hydroxyethyl vinyl ether, 2- (or 3-). Hydroxyalkyl vinyl ethers such as hydroxypropyl vinyl ethers, 2- (or 3- or 4-) hydroxybutyl vinyl ethers, or allyl ether-based monomers having hydroxyl groups, such as 2-hydroxyethyl allyl ethers, 2- (or 3-). Examples thereof include hydroxyalkylallyl ethers such as hydroxypropylallyl ethers and 2- (or 3- or 4-) hydroxybutylallyl ethers.

Further, obtained by adding an alkylene oxide and / or a lactone to the above-mentioned hydroxyalkyl (meth) acrylate, alkyl-α-hydroxyalkyl acrylate, N- (hydroxyalkyl) (meth) acrylamide, hydroxyalkyl vinyl ether or hydroxyalkyl allyl ether. The ethylenically unsaturated monomer obtained can also be used as the hydroxyl group-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-, 1,4-, 2,3- or 1,3-butylene oxide and a combination system of two or more of these are used. When two or more kinds of alkylene oxides are used in combination, the binding form may be either 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 system of two or more of these are used. Both alkylene oxide and lactone may be added.

(Other ethylenically unsaturated monomers)
Examples of the ethylenically unsaturated monomer other than the hydroxyl group-containing ethylenically unsaturated monomer (b) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth). Acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2,2,4-trimethylcyclohexyl (meth) acrylate , Alkyl (meth) acrylates such as stearyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate;
Aromatic (meth) acrylates such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, and phenoxydiethylene glycol (meth) acrylate;
Heterocyclic (meth) acrylates such as tetrahydrofurfreel (meth) acrylate; alkoxypolyalkylene glycol (meth) acrylates such as methoxypolypropylene glycol (meth) acrylate and ethoxypolyethylene glycol (meth) acrylate;
(N-substituted) such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, acryloyl morpholine, etc. Meta) Acrylamides;
Amino group-containing (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate;
Examples thereof include nitriles such as (meth) acrylonitrile.

Further, as a monomer that can be used in combination with the above acrylic monomer, styrenes such as styrene, α-methylstyrene and inden, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether and isobutyl vinyl ether. , Vinyl acetate, vinyl propionate and other fatty acid vinyls.

Further, a carboxyl group-containing ethylenically unsaturated monomer can also be used in combination. As the carboxyl group-containing ethylenically unsaturated monomer, one or more can be selected from acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid and the like.

The content of the hydroxyl group-containing ethylenically unsaturated monomer (b) is 35% by mass or more and 80% by mass or less, preferably 38% by mass or more and 60% by mass or less, based on the total amount of the ethylenically unsaturated monomer (c). It is not more than mass%, and more preferably 40% by mass or more and 50% by mass or less.

In the resin-type dispersant of the present invention, acrylic acid or methacrylic acid is most preferably used as the carboxyl group-containing ethylenically unsaturated monomer, and ethylenic acid containing the hydroxyl group-containing ethylenically unsaturated monomer (b) is used. The content of the carboxyl group-containing ethylenically unsaturated monomer in the unsaturated monomer (c) is preferably 2.5 to 10.0% by mass, more preferably 2.5 to 5.0% by mass. Is. If it is less than 2.5% by mass, the patterning suitability such as linearity and dimensional stability at the time of manufacturing a color filter deteriorates, and if it exceeds 10.0% by mass, the pigment dispersion stability may deteriorate.

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

(Compound (d) having one isocyanate group and one or more (meth) acryloyl groups)
Examples of the compound (d) having one isocyanate group and one or more (meth) acryloyl groups used in the third step include a compound having one isocyanate group and one or two (meth) acryloyl groups. Preferably, specifically, 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, and 1,1-bis (acryloyloxymethyl) ethyl isocyanate are preferable.

The compound (d) having one isocyanate group and one or more (meth) acryloyl groups used in the present invention is not limited to the compounds exemplified above, and may have an isocyanate group and one or more (meth) acryloyl groups. It does not matter what kind of structure it has. These may be used alone or in combination.

The molar ratio of the hydroxyl group in the hydroxyl group-containing compound to the isocyanate group in the compound (d) having one isocyanate group and one or more (meth) acryloyl groups is based on 1 mol of the hydroxyl group in the hydroxyl group-containing compound. The isocyanate group in the compound (d) having one isocyanate group and one or more (meth) acryloyl groups is preferably 0.2 to 1.0 mol, more preferably 0.5 to 1. It is 0 mol, most preferably 0.8 to 1.0 mol. If it is less than 0.2 mol, the amount of (meth) acryloyl group is reduced and the curability may be insufficient. If it exceeds 1.0 mol, unreacted isocyanate groups are contained in the resin. It may remain and the storage stability may deteriorate. 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 is slow, and if it exceeds 150 ° C, the urethane groups generated by the reaction are decomposed.

The molar of the (meth) acryloyl group introduced into the resin-type dispersant (B) obtained by the reaction of the hydroxyl group in the hydroxyl group-containing compound with one isocyanate group and a compound having one or more (meth) acryloyl groups. The number is preferably a certain amount. Generally, the amount of double bonds in a resin is a numerical value called double bond equivalent (g / mol) calculated as (total weight of the resin) / (the number of moles of double bonds contained in the weight of the resin). It is represented by. However, in the present invention, it is not the double bond equivalent of the entire resin, but ((c) the total mass of the ethylenically unsaturated monomer + (d) a compound having one isocyanate group and one or more (meth) acryloyl groups. The resin type dispersant (B) represented as ((d) the number of mols of (meth) acryloyl groups contained in the compound having one isocyanate group and one or more (meth) acryloyl groups). The double bond equivalent (Z) in the side chain of Acryloyl affects the linearity and dimensional stability when creating a color filter. In the present invention, it is preferable that the value of Z is 300 to 600 g / mol because of the linearity and dimensional stability at the time of producing the color filter.

The weight average molecular weight of the obtained dispersant of the present invention is preferably 2,000 to 10,000, 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, and if it exceeds 100,000, the interaction between the resins may become strong and the pigment composition may thicken. be.

The acid value of the resin-type dispersant of the present invention is preferably 5 to 200 mgKOH / g, more preferably 5 to 150 mgKOH / g, and particularly preferably 5 to 100 mgKOH / g. If the acid value is less than 5 mgKOH / g, the pigment adsorption capacity may decrease and the pigment dispersibility may be problematic. If the acid value exceeds 200 mgKOH / g, the interaction between the resins becomes stronger and the viscosity of the pigment dispersion composition increases. In some cases.

<Colorant (A)>
The photosensitive coloring composition for a color filter of the present invention may contain a pigment or a dye as a colorant. As the pigment, an organic or inorganic pigment can be used alone or in combination of two or more. As the pigment, a pigment having high color development and high heat resistance, particularly a pigment having high heat resistance decomposition property is preferable, and an organic pigment is usually used. Specific examples of organic pigments that can be used in the coloring composition for color filters are shown below by color index numbers.

<Organic pigment>
Examples of the red pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281 And so on. Among these, from the viewpoint of heat resistance, light resistance, and transmittance of the filter segment, C.I. I. Pigment Red 48: 1, 122, 177, 224, 242, 254, more preferably C.I. I. Pigment Red 177, 254.

Further, the red coloring composition includes C.I. I. Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, 73 and other orange pigments and / or the yellow pigments described below may be used in combination.

Examples of the blue pigment include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like can be mentioned. Among these, from the viewpoint of heat resistance, light resistance, and transmittance of the filter segment, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, or 15: 6, more preferably C.I. I. Pigment Blue 15: 6. Further, it is also preferable to use an aluminum phthalocyanine pigment, and the aluminum phthalocyanine pigment and the like described in JP-A-2004-333817, Patent No. 4893859 and the like can also be used. Further, the purple pigment described later may be used in combination with the blue coloring composition.

Examples of the purple pigment include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like can be mentioned. Among these, from the viewpoint of heat resistance, light resistance, and transmittance of the filter segment, C.I. I. Pigment Violet 19 or 23, more preferably C.I. I. Pigment Violet 23.

Examples of the green pigment include C.I. 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, Examples thereof include zinc phthalocyanine pigments described in JP-A-2008-19383, JP-A-2007-320986, JP-A-2004-70342, and aluminum phthalocyanine pigments described in Japanese Patent No. 4893859. , Especially not limited to these. Among these, from the viewpoint of transmittance, C.I. I. Pigment Green 36 or 58.
Further, the yellow pigment described later may be used in combination with the green coloring composition.

For yellow pigments, for example, C.I. I. 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, Examples thereof include, but are not limited to, the quinophthalone compounds described in 192, 193, 194, 196, 198, 199, 213, 214, and 2012-226110. Among these, from the viewpoint of heat resistance, light resistance, and transmittance of the filter segment, C.I. I. Pigment Yellow 138, 139, 150, 185 and at least one selected from the quinophthalone pigments described in JP2012-226110A are preferable. More preferably, C.I. I. Pigment Yellow 139, 150, 185.

Examples of the quinophthalone-based pigment described in JP-A-2012-226110 include compounds represented by the following.

Examples of the cyan coloring composition for forming the cyan filter segment include C.I. I. Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, 81 and other blue pigments can be used alone or in combination.

Magenta coloring compositions for forming magenta filter segments include, for example, C.I. I. Pigment Violet 1, 19, C.I. I. Purple pigments such as Pigment Red 144, 146, 177, 169, 81 and red pigments can be used alone or in combination. A yellow pigment can be used in combination with the magenta color composition.

Inorganic pigments include titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, dark blue, chromium oxide green, cobalt green, and amber. , Synthetic iron black and the like. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability, etc. while balancing saturation and lightness.

(Pigment miniaturization)
The organic pigment is preferably miniaturized by salt milling treatment or the like in order to correspond to high transmittance and high contrast. The primary particle size of the pigment is preferably 10 nm or more because it is well dispersed in the colorant carrier. Further, it is preferably 80 nm or less because a filter segment having high contrast can be formed. A particularly preferable range is the range of 20 to 60 nm.

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

<Dye>
In the coloring composition according to the embodiment of the present invention, a dye can also be used as a coloring agent. As the dye, any of acidic dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, medium dyes, construction dyes, sulfide dyes and the like can be used. Further, these derivatives or a rake pigment obtained by rake-forming the dye may be used.

Further, an acidic dye having an acidic group such as sulfonic acid or carboxylic acid, or in the case of a direct dye form, an inorganic salt of the acidic dye, an acidic dye and a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, Alternatively, a salt-forming compound with a nitrogen-containing compound such as a primary amine compound, or chloride-forming using a resin component having these functional groups and using the salt-forming compound, or sulfonamide formation and use as a sulfonic acid amide compound. In order to obtain excellent resistance, a coloring composition having excellent fastness can be obtained, which is preferable.
Further, a salt-forming compound of an acid dye and a compound having an onium base is also preferable because it has excellent fastness, and more preferably, the compound having an onium base is a resin having a cationic group in the side chain.

In the case of the basic dye form, it can be used by chlorinating with an organic acid, perchloric acid or a metal salt thereof. Salt-forming compounds of basic dyes are preferable because they have excellent resistance and compatibility with pigments, and further, basic dyes and organic sulfonic acid, organic sulfuric acid, and fluorine group-containing phosphorus anion compounds which are counter components that act as counter ions. It is more preferable to use a salt-forming compound obtained by salting a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugated base of an organic acid having a halogenated hydrocarbon group, or an acidic dye. It is a thing.

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

In one embodiment, the chemical structure of the dye includes, for example, an azo dye, an azomethine dye (indaniline dye, indophenol dye, etc.), a dipyrromethene dye, a quinone dye (benzoquinone dye, naphthoquinone dye, etc.). Anthraquinone dyes, anthrapyridone dyes, etc.), Carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acrydin dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azine Dyes, polymethine dyes (oxonol dyes, merocyanine dyes, allylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, Examples thereof include dye structures derived from dyes selected from perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, and their metal complex dyes.

Among these dye structures, from the viewpoint of color characteristics such as hue, color separability, and color unevenness, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and squaryliums. Dye structures derived from dyes selected from dyes selected from dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes are preferable, and xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are preferable. A dye structure derived from a dye selected from the dyes is more preferable. For specific dye compounds that can form a dye structure, see "New Edition Dye Handbook" (Society of Synthetic Organic Chemistry; Maruzen, 1970), "Color Index" (The Society of Dyers and colorists), "Dye Handbook" (Okawara et al.) Edited by Kodansha, 1986).

Examples of the dyes in another embodiment include azo dyes, azo metal complex dyes, anthraquinone dyes, indigo dyes, thioindigo dyes, phthalocyanine dyes, methine dyes, diarylmethane dyes, and triarylmethane dyes. Xanthene dyes, thiazine dyes, cationic dyes, cyanine dyes, nitro dyes, quinoline dyes, naphthoquinone dyes, oxazine dyes, perylene dyes, diketopyrrolopyrrole dyes, quinacridone dyes, anthanthrone dyes. Examples thereof include, but are not limited to, dyes, isoindolinone dyes, isoindrin dyes, indanslon dyes, coumarin dyes, quinacridone dyes, pyranthron dyes, flavanthron dyes, and perinone dyes.

Examples of the organic dye that can be used in still another embodiment include triarylmethane-based, xanthene-based, and anthraquinone-based dyes, and among them, xanthene-based dyes are preferably used.

[Xanthene dyes]
The xanthene-based dye that can be preferably used has a red color or a purple color, and preferably has any form of an oil-soluble dye, an acid dye, a direct dye, and a basic dye. Further, it may be in the form of a rake pigment obtained by rake-forming these dyes.
Among these, it is preferable to use a xanthene-based oil-soluble dye or a xanthene-based acid dye because of its excellent hue.

Those exhibiting red and purple are C.I. I. Solvent Red, C.I. I. Oil-soluble dyes such as solvent violet, C.I. I. Basic Red, C.I. I. Basic dyes such as basic violet, C.I. I. Acid Red, C.I. I. Acid dyes such as acid violet, C.I. I. Direct Red, C.I. I. Examples include those belonging to direct dyes such as direct violet.
Here direct dyes, sulfonic acid group in the structure _{(-SO 3 H, -SO 3 Na} ) has, in the present disclosure, dyes are those regarded as acid dye directly.

[Salt formation and sulfonamide formation of xanthene dyes]
Further, the xanthene-based basic dye is preferably used by chlorinating with an organic acid or perchloric acid. As the organic acid, it is preferable to use an organic sulfonic acid or an organic carboxylic acid. Of these, it is preferable to use naphthalene sulfonic acid such as tobias acid and perchloric acid in terms of resistance.

Further, the xanthene-based acidic dye is used as a salt-forming compound by chloride-forming using a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, a primary amine compound, or a resin component having a functional group thereof. In terms of resistance, it is preferable that the compound is sulfonamided and used as a sulfonic acid amide compound.

Salt-forming compounds of xanthene-based acid dyes and / or sulfonic acid amide compounds of xanthene-based acid dyes are preferable because they have excellent hue and resistance, and quaternary ammonium, which is a counter component that acts as a counter ion, further uses xanthene-based acid dyes. It is more preferable to use a compound obtained by chloride using a salt compound and a sulfonic acid amide compound obtained by sulfonamide-forming a xanthene acid dye.

Further, among xanthene dyes, rhodamine dyes are preferable because they are excellent in color development and resistance.

Hereinafter, the morphology of the xanthene dye will be described in detail.

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

[Xanthene-based basic dye]
Examples of the xanthene-based basic dye include C.I. I. Basic Red 1 (Rhodamine 6 GCP), 8 (Rhodamine G), C.I. I. Examples thereof include Basic Violet 10 (Rhodamine B). Among them, C.I. I. Basic Red 1, C.I. I. It is preferable to use Basic Violet 10.

[Xanthene acid dye]
Examples of xanthene-based acid dyes include C.I. I. Acid Red 51 (erythrosine (edible red No. 3)), C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 87 (Eosin G (Edible Red No. 103)), C.I. I. Acid Red 92 (Acid Phloxine PB (Edible Red No. 104)), C.I. I. Acid Red 289, C.I. I. Acid Red 388, Rose Bengal B (Edible Red No. 5), Acid Rhodamine G, C.I. I. It is preferable to use Acid Violet 9.
Among them, C.I., which is a xanthene-based acid dye, has heat resistance and light resistance. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 388 or C.I., a rhodamine-based acid dye. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 289, Acid Rhodamine G, C.I. I. It is more preferable to use Acid Violet 9.
Among these, C.I., a rhodamine-based acid dye, is particularly excellent in color development, heat resistance, and light resistance. I. Acid Red 52, C.I. I. Most preferably, Acid Red 289 is used.

The acidic dye (not limited to the xanthene type) is preferably a salt-forming compound of the acidic dye and the nitrogen-containing compound, and is a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, a primary amine compound, or the like. It is preferable to form chloride using a resin component having these functional groups to obtain a salt-forming compound of an acidic dye, because high heat resistance, light resistance, and solvent resistance can be imparted. Acid dyes can be imparted with high heat resistance, light resistance, and solvent resistance even by sulfonamide formation.
Further, it may be a salt-forming compound of an acid dye and a compound having an onium base, and among them, the compound having an onium base is a resin having a cationic group in the side chain, so that the brightness and resistance can be improved. It can be an excellent coloring composition.

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

Examples of the secondary amine compound include aliphatic unsaturated secondary amines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine and diallylamine, methylaniline, ethylaniline, dibenzylamine, diphenylamine and dicocoalkyl. Examples include amines, di-cured beef fat alkylamines, distearylamines, etc.

Examples of the tertiary amine compound include trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, dimethylaniline, diethylaniline, tribenzylamine and the like.

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

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

The molecular weight of the counter portion, which is a cationic component of the quaternary ammonium salt compound, is preferably in the range of 190 to 900. Here, the cation portion _{corresponds to the (NR 1} R ₂ R ₃ R ₄ ) ⁺ portion in the following general formula (1). If the molecular weight is smaller than 190, the light resistance and heat resistance may be lowered, and the solubility in a solvent may be further lowered. Further, when the molecular weight becomes larger than 900, the ratio of the color-developing component in the molecule decreases, the color-developing property decreases, and the brightness may also decrease. More preferably, the molecular weight of the counter portion is in the range of 240 to 850. Particularly preferred is the molecular weight of the counter portion in the range of 350-800. Here, the molecular weight was calculated based on the structural formula, and the atomic weight of C was 12, the atomic weight of H was 1, and the atomic weight of N was 14.

As the quaternary ammonium salt compound, 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 independently represent an alkyl group or a benzyl group having 1 to 20 carbon atoms, and at least two or more of _{R 1} , R ₂ , R ₃ , and R _{4 are present.} The number of C is 5 to 20. Y ⁻ represents m inorganic or organic anion.)

By _{setting the number of at least two or more Cs of R 1 to} R ₄ to 5 to 20, the solubility in a solvent becomes good. If the number of C is less than 5, the number of alkyl groups is 3 or more, the solubility in a solvent is deteriorated, and foreign matter in the coating film is likely to be generated. Further, if there is an alkyl group in which the number of C exceeds 20, the color-developing property of the salt-forming compound (a) is impaired.

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

Examples of the quaternary ammonium salt compound include tetramethylammonium chloride, tetraethylammonium chloride, monostearyltrimethylammonium chloride, distearyldimethylammonium chloride, tristearylmonomethylammonium chloride, cetyltrimethylammonium chloride, trioctylmethylammonium chloride, and dioctyldimethylammonium chloride. , Monolauryltrimethylammonium chloride, Dilauryldimethylammonium chloride, Trilaurylmethylammonium chloride, Triamylbenzylammonium chloride, Trihexylbenzylammonium chloride, Trioctylbenzylammonium chloride, Trilaurylbenzylammonium chloride, benzyldimethylstearylammonium chloride, and Examples thereof include benzyldimethyloctylammonium chloride, dialkyl (alkyl is C14 to C18) and dimethylammonium chloride (hardened beef fat).

Specific quaternary ammonium salt compound products include, for example, Kao's Coatamine 24P, Coatamine 86P Conch, Coatamine 60W, Coatamine 86W, Coatamine D86P, Sanizol C, Sanizol B-50, etc. 80E, 2C-75, 2HT-75, 2HT flakes, 2O-75I, 2HP-75, 2HP flakes, etc. C18) Dimethylammonium chloride).

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

When a blue coloring composition for a color filter containing a salt-forming compound (a') is prepared and the characteristics as a color filter are exhibited, a resin of the same type as the binder resin constituting the blue coloring composition for a color filter is used. It is preferable to do so. In one embodiment of the present invention, since an acrylic resin is preferably used as the binder resin in the coloring composition for a color filter, a resin having a cationic group in the side chain for obtaining the salt-forming compound (a') is used. It is preferably an acrylic resin.

As the resin having a cationic group in the side chain, an alkaline 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 of the cationic group in the general formula (2) with the anionic group of the xanthene acid dye.

［一般式（２）中、Ｒ^５１は水素原子、又は置換もしくは無置換のアルキル基を表す。Ｒ^５２〜Ｒ^５４は、それぞれ独立に、水素原子、置換されていてもよいアルキル基、置換されていてもよいアルケニル基、又は置換されていてもよいアリール基を表し、Ｒ^５２〜Ｒ^５４のうち２つが互いに結合して環を形成しても良い。Ｑはアルキレン基、アリーレン基、−ＣＯＮＨ−Ｒ^５５−、−ＣＯＯ−Ｒ^５５−を表し、Ｒ^５５はアルキレン基を表す。Ｙ⁻は無機又は有機のアニオンを表す。］ 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 independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, respectively, of R ^{52 to} R ⁵⁴ . Two of them may be combined with each other to form a ring. Q represents an alkylene group, an arylene ^{group, -CONH-R 55 -, -} COO-R 55 - ^{represents, R 55} represents an alkylene group. Y ⁻ represents an inorganic or organic anion. ]

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

When the ^{alkyl group represented by R 51} has a substituent, examples of the substituent include a hydroxyl group and an alkoxyl group.

Among the above, ^{as R51} , a hydrogen atom or a methyl group is most preferable.

Examples of the alkyl group 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, etc. n-Hexadecyl and n-octadecyl, etc.), branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, 2-ethylhexyl and 1,1,3,3-tetramethyl Butyl, etc.), cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.) and crosslinked cyclic alkyl groups (norbornyl, adamantyl, pinanyl, etc.). As the alkyl group, an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms is more preferable.

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.), cycloalkenyl groups (2-cyclohexenyl, 3-cyclohexenyl, etc.) and the like. As the alkenyl group, an alkenyl group having 2 to 18 carbon atoms is preferable, and an alkenyl group having 2 to 8 carbon atoms is more preferable.

Examples of the aryl group in R ^{52 to} R ⁵⁴ include a monocyclic aryl group (phenyl, etc.), a fused polycyclic aryl group (naphthyl, anthracenyl, phenanthrenyl, anthraquinolyl, fluorenyl, naphthoquinolyl, etc.) and an aromatic heterocyclic hydrocarbon. Groups (thienyl (group derived from thiophene), frill (group derived from furan), pyranyl (group derived from pyran), pyridyl (group derived from pyridine), 9-oxoxanthenyl (from xantone) Induced groups) and 9-oxothioxanthenyl (groups derived from thioxanthone), etc.).

When the ^{alkyl group, alkenyl group, and aryl group represented by R 52 to} R ⁵⁴ have a substituent, the substituent includes, for example, a halogen atom, a hydroxyl group, an alkoxyl group, an aryloxy group, an alkenyl group, an acyl group, and the like. Examples thereof include a substituent selected from an alkoxycarbonyl group, a carboxyl group, a phenyl group and the like. As the substituent, a halogen atom, a hydroxyl group, an alkoxyl group, and a phenyl group are particularly preferable.

As R ^{52 to} R ⁵⁴ , an alkyl group which may be substituted is preferable from the viewpoint of stability, and an unsubstituted alkyl group is more preferable.

Further, two of R ^{52 to} R ⁵⁴ may be bonded to each other to form a ring.

In the general formula (2), Q components is an alkylene group linking vinyl moiety and ammonium salt, an arylene ^{group, -CONH-R 55 -, -} COO-R 55 - ^represents, but ^{R 55} represents an alkylene group, Among them, the polymerizable, for reasons of ^{availability, -CONH-R 55 -, -} COO-R 55 - is preferably. Further, it is more preferable that R ⁵⁵ is a methylene group, an ethylene group, a propylene group, or a butylene group, and it is particularly preferable that it is an ethylene group.

^{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, known ones can be adopted without limitation, and specifically, hydroxide ion; halogen ion such as chloride ion, bromide ion and iodide ion; carboxylic acid ion such as formate ion and acetate ion; Like carbonate ion, bicarbonate ion, nitrate ion, sulfate ion, sulfite ion, chromate ion, dichromate ion, phosphate ion, cyanide ion, permanganate ion, and even hexacyanoferrate (III) acid ion. Examples include complex ions. From the viewpoint of synthetic suitability and stability, halogen ions and carboxylic acid ions are preferable, and halogen ions are most preferable. When the counter anion is an organic acid ion such as a carboxylic acid ion, the organic acid ion may be covalently bonded to 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 corresponds to an ethylenically unsaturated monomer containing an oxetane structure corresponding to the cationic group represented by the general formula (2). This is a method of copolymerizing with an ethylenically unsaturated monomer.
Examples of the ethylenically unsaturated monomer having an oxetane group include (3-methyl-3-oxetanyl) methyl (meth) acrylate, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, and (3-butyl-3). -Oxetanyl) methyl (meth) acrylate, (3-hexyltyl-3-oxetanyl) methyl (meth) acrylate and the like can be mentioned.
Examples of commercially available products include ETERNAL COLL OXMA (manufactured by Ube Industries, Ltd.), OXE-10, OXE-30 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.) and the like.

(Salt formation)
The salt-forming compound of the acid dye and the nitrogen-containing compound or the resin having a cationic group in the side chain can be produced by a conventionally known method. A specific method is disclosed in JP-A-11-72969.
To give an example using a xanthene-based acid dye, after dissolving the xanthene-based acid dye in water, a quaternary ammonium salt compound may be added and the chloride-forming treatment may be performed while stirring. Here, the sulfonic acid group (-SO ₃ H) and sodium sulfonate group (-SO ₃ Na) in the xanthene acid dye and the ammonium group (NH ₄ ⁺ ) in the quaternary ammonium salt compound are bonded. A salt compound is obtained. In addition, instead of water, methanol and ethanol are also solvents that can be used during chloride formation.

Further, the salt-forming compound is represented by stirring or vibrating an aqueous solution in which a resin having a cationic group in the side chain represented by the general formula (2) and an acid dye are dissolved, or by the general formula (2). It can be easily obtained by mixing an aqueous solution of a resin having a cationic group in the side chain and an aqueous solution of an acid dye under stirring or vibration. 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 ion-bonded portion becomes water-insoluble and precipitates. On the contrary, since the salt composed of the counter anion of the resin and the counter cation of the acid dye is water-soluble, it can be removed by washing with water or the like. As the resin having a cationic group in the side chain to be used and the acid dye, only one type may be used, or a plurality of types having different structures may be used.
As for other acid dyes, a nitrogen-containing compound or a salt-forming compound with a resin having a cationic group in the side chain can be obtained by the same method as that for xanthene dyes.

(Sulfonic acid amide compound)
The acid dye may be a sulfonic acid amide compound obtained by reacting a sulfonic acid amide compound with an anionic dye.
The sulfonic acid amide compound of an acid dye that can be preferably used as an acid dye is obtained by chlorinating _{an acid dye having -SO 3} H and -SO ₃ Na by a conventional method to convert -SO ₃ H to -SO ₂ Cl. The compound can be produced by reacting with an amine having _{two -NH groups.}
Specific examples of the amine compound that can be preferably used in sulfonamide formation include 2-ethylhexylamine, dodecylamine, 3-decyloxypropylamine, 3- (2-ethylhexyloxy) propylamine, and 3-ethoxypropyl. It is preferable to use amine, cyclohexylamine and the like.
To give an example using a xanthene-based acid dye, C.I. I. When a sulfonic acid amide compound obtained by modifying Acid Red 289 with 3- (2-ethylhexyloxy) propylamine is obtained, C.I. I. Acid Red 289 was sulfonyl chlorided and then reacted with a theoretical equivalent of 3- (2-ethylhexyloxy) propylamine in dioxane to give C.I. I. The sulfonic acid amide compound of Acid Red 289 may be obtained.
In addition, C.I. I. When a sulfonic acid amide compound obtained by modifying Acid Red 52 with 3- (2-ethylhexyloxy) propylamine is also obtained, C.I. I. Acid Red 52 was sulfonyl chlorided and then reacted with a theoretical equivalent of 3- (2-ethylhexyloxy) propylamine in dioxane to give C.I. I. The sulfonic acid amide compound of Acid Red 52 may be obtained.
Further, for other acid dyes, a sulfonic acid amide compound can be obtained by the same method as that for xanthene dyes.

Examples of the xanthene dye include JP-A-2010-03299, JP-A-2011-13894, JP-A-2011-227313, JP-A-2011-242752, JP-A-2012-107192, and JP-A-2013. 033194, 2011-71888, 2013-72263, 2013-81209, 2014-173064, 2013-53028, 2013-52186 JP-A-2014-196392, JP-A-2014-196393, JP-A-2014-201714, JP-A-2014-201715, JP-A-2013-050693, JP-A-2013-178478, Known techniques described in Japanese Patent Application Laid-Open No. 2013-203056, International Publication No. 2013/0116887, and the like can be used.

In one embodiment, the xanthene dye is C.I. I. Acid Red 51, C.I. I. Acid Red 52, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 289, C.I. I. Acid Red 388, Rose Bengal B, Acid Rhodamine G, C.I. I. Acid Violet 9, C.I. I. Acid Violet 9, C.I. I. It is preferable to use Acid Violet 30. Above all, C.I. I. Acid Red 52, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 289, C.I. I. It is preferable to use Acid Red 388.

[Dipyrromethene dye]
The dipyrromethene dye is a dye having a partial structure derived from the dipyrromethene dye as a partial structure of the dye portion, and a dipyrromethene compound and a dipyrromethene metal complex compound obtained from the dipyrromethene compound and a metal or a metal compound are preferable. , A metal complex compound in which the structure represented by the general formula (3) is coordinated with a metal atom or a metal compound (hereinafter, appropriately referred to as “dipyrromethene metal complex compound”) is preferable.

[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 is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Represents.
The metal or the metal compound may be any metal atom or metal compound capable of forming a complex, and is a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or 2 Valuable metal chlorides are included. Examples of the metal or metal compound include Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, B, and the like, as well as AlCl ₃ , InCl ₃ , and FeCl. ₃ , _{Metal chlorides such as TiCl 2} , SnCl ₂ , SiCl ₂ and GeCl ₂ , metal oxides such as TiO and VO, and metal hydroxides such as _{Si (OH) 2 are also included.}
Among these, as the metal or the metal compound, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, and C are used from the viewpoints of complex stability, spectral characteristics, heat resistance, light resistance, manufacturing suitability, and the like.
u, Ni, Co, TiO, B, or VO is preferable, Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO is more preferable, and Fe, Zn, Cu, Co, B is more preferable. , Or VO is most preferable.

Examples of such dipyrromethene dyes include JP-A-2008-292970, JP-A-2010-85758, JP-A-2010-84009, JP-A-2010-43530, JP-A-2013-08010, and JP-A-2013-08010. Known techniques described in Kai 2013-210596, International Publication No. 2013/141156, etc. can be used.

[Triphenylmethane dye]
Examples of the triphenylmethane dye skeleton include a diaminotriphenylmethane dye skeleton, a triaminotriphenylmethane dye skeleton, and a rosolic acid dye skeleton having an OH group.
The triaminotriphenylmethane dye skeleton is preferable in that it has excellent color tone and is superior in sunlight fastness to others. Among them, the diphenylnaphthylmethane dye skeleton, which is a basic dye, is particularly preferable.

[Triphenylmethane basic dye]
_{The triphenylmethane-based basic dye develops a color when the NH 2} or OH group located at the para position with respect to the central carbon takes a quinone structure by oxidation.
It _{is classified into the following three types according to the number of NH 2} and OH groups, and among them, the form of a triaminoarylmethane-based basic dye is preferable in that it develops good blue, red, and green colors.
a) Diaminotriphenylmethane-based basic dye b) Triaminotriphenylmethane-based basic dye c) Rozolic acid-based basic dye having an OH group Triaminotriphenylmethane-based basic dye, diaminotriphenylmethane-based basic dye Dyes are preferable because they have a clear color tone and are superior in sunlight fastness to other dyes.

Since blue triphenylmethane basic dyes have spectral characteristics with high transmittance at 400 to 440 nm, they can be made highly bright, especially when used for forming blue filter segments. It is preferable because it can be done.

Specifically, as a triphenylmethane-based basic dye, C.I. I. Basic Violet 1 (Methyl Violet), 3 (Crystal Violet), 14 (Magenta), C.I. I. Basic Blue 1 (Basic Cyanine 6G), 5 (Basic Cyanine EX), 7 (Victoria Pure Blue BO), 26 (Victoria Blue B)
conc. ), C.I. I. Basic Green 1 (Brilliant Green GX), 4 (Malachite Green), etc. can be mentioned.
Above all, from the point of view of brightness, C.I. I. It is preferable to use Basic Blue 7.

Further, in the case of a triphenyl-based basic dye, it can be used by chlorinating with an organic acid, perchloric acid or a metal salt thereof. Among them, the salt-forming compound of the basic dye is preferable because it has excellent resistance and compatibility with the pigment, and further, the basic dye and organic sulfonic acid, organic sulfuric acid, and fluorine group-containing phosphorus, which are counter components that act as counter ions, are preferable. It is possible to use a salt-forming compound obtained by salting an anion compound, a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugated base of an organic acid having a halogenated hydrocarbon group, or an acidic dye. It is more preferable.

Specifically, heteropolyacids, organic sulfonic acids such as aliphatic sulfonic acids and aromatic sulfonic acids, organic sulfuric acids such as aliphatic sulfuric acid and aromatic sulfuric acid, organic carboxylic acids such as aromatic carboxylic acids and fatty acids, and organic acids such as fatty acids, Alternatively, it has the form of an acidic dye. Alternatively, it may be a metal salt thereof. Further, a salt-forming compound with a resin having an acid group is also preferable.

(Salt formation)
Salt-forming compounds of these basic dyes and anionic counters can be synthesized by conventionally known methods. A specific method is disclosed in Japanese Patent Application Laid-Open No. 2003-215850.
As an example, after dissolving a triarylmethane-based basic dye in water, an organic sulfonic acid or a (sodium organic sulfonate) solution may be added, and the chloride-forming treatment may be performed while stirring. Here, a salt-forming compound in which the amino group (-NHC ₂ H ₅ ) portion of the triarylmethane basic dye and the sulfonic acid group (-SO _{3 H) portion of the organic sulfonic acid are bonded is obtained.}
Here, the organic sulfonic acid can be dissolved in an alkaline solution such as sodium hydroxide and used in _{the form of sodium sulfonate (-SO 3 Na) before the salt-forming treatment.} In the present disclosure, the sulfonic acid group (-SO ₃ H) and the functional group (-SO ₃ Na) which is sodium sulfonate can be referred to without distinction.

Examples of such triphenylmethane dyes include JP-A-2002-014222, JP-A-2003-246935, JP-A-2003-246935, JP-A-2008-304766, and JP-A-2010-256598. , Japanese Patent Application Laid-Open No. 2011-200560, Japanese Patent Application Laid-Open No. 2011-186043, Japanese Patent Application Laid-Open No. 2012-173399, Japanese Patent Application Laid-Open No. 2012-233033, Japanese Patent Application Laid-Open No. 2012-098522, Japanese Patent Application Laid-Open No. 2012-288970, The publicly known techniques described in Japanese Patent Application Laid-Open No. 2012-200469, Japanese Patent Application Laid-Open No. 2014-196262, International Publication No. 2010/123071, International Publication No. 2011/162217, International Publication No. 2013/108591, etc. Can be used.

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

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

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

[Anthraquinone dye]
Anthraquinone dyes are dyes that have an anthraquinone skeleton in the molecule.
Examples of the anthraquinone dye include C.I. I. Solvent Yellow 117, 163, 167, 189, C.I. I. Solvent Orange 77, 86, C.I. I. Solvent Red 111, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247, C.I. I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60, C.I. I. Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139, C.I. I. Solvent Green 3, 28, 29, 32, 33, C.I. I. Acid Red 80, C.I. I. Acid Green 25, 27, 28, 41, C.I. I. Acid Violet 34, C.I. I. Acid Blue 25, 27, 40, 45, 78, 80, 112, C.I. I. Disperse Yellow 51, C.I. I. Disperse Violet 26, 27, C.I. I. Disperse Blue 1, 14, 56, 60, C.I. I. Direct Blue 40, C.I. I. Modant Red 3, 11, C.I. I. Modant Blue 8 and the like can be mentioned. In addition, the anthraquinone dyes described in JP-A-9-291237, International Publication No. 2003/08734, International Publication No. 2006/024617, Japanese Patent Application Laid-Open No. 2011-174987, Japanese Patent Application Laid-Open No. 2013-53273, etc. It can be used as a known technique. The anthraquinone dye is preferably one that dissolves in an organic solvent, and more preferably a blue, violet or red anthraquinone dye. Examples of the anthraquinone dye include C.I. I. Solvent Blue 35, C.I. I. Solvent Blue 45, C.I. I. Acid Blue 80, C.I. I. Solvent Blue 104, and C.I. I. Solvent blue 122 is preferable from the viewpoint of brightness and contrast.

In one embodiment, as an anthraquinone dye, C.I. I. Acid Violet 29, C.I. I. Acid Violet 31, C.I. I. Acid Violet 33, C.I. I. Acid Violet 34, C.I. I. Acid Violet 36, C.I. I. Acid Violet 39, C.I. I. Acid Violet 43, C.I. I. Acid Violet 48, C.I. I. Acid Violet 63, C.I. I. Acid Violet 109, C.I. I. Acid Blue 25, C.I. I. Acid Blue 27, C.I. I. Acid Blue 41, C.I. I. Acid Blue 45, C.I. I. Acid Blue 62, C.I. I. Acid Blue 80, C.I. I. Acid Blue 127, C.I. I. Acid Blue 129, C.I. I. Acid Blue 145, C.I. I. Acid Blue 225, C.I. I. Acid Blue 230, C.I. I. Acid Blue 260, C.I. I. Acid Blue 264, C.I. I. Acid Blue 277, C.I. I. Acid Blue 281, C.I. I. Acid Blue 324, or C.I. I. It is preferable to use 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% by mass or more, more preferably 40% by mass or more, based on 100 parts by mass of the solid content of the photosensitive coloring composition for a color filter according to the embodiment of the present invention. It is preferable to obtain a good color reproducibility and reduce the film thickness. Further, if it is preferably 65% by mass or less, more preferably 60% by mass or less, the content of the resin or the photopolymerizable compound as a curing material becomes appropriate, and a sufficient cured coating film can be obtained. Generally, when the content of the colorant is high, the patterning characteristics of the photosensitive coloring composition tend to deteriorate. According to the present invention, not only in the photosensitive coloring composition in which the content of the colorant required for general high color reproduction is 30% by mass to less than 40% by mass, but also the content of the more difficult colorant is 40% by mass. Sufficient patterning characteristics can be obtained even with a photosensitive coloring composition of% or more.

<Photopolymerization initiator (C)>
To the photosensitive composition of the present invention, a photopolymerization initiator (C) is added in order to cure the composition by ultraviolet irradiation and form a filter segment by a photolithography method, and solvent-developed or alkali-developed photosensitive. It is essential to prepare in the form of a sex composition. From the viewpoint of practical ultraviolet sensitivity, the blending amount of the photopolymerization initiator is more preferably 0.3 to 8.0% by mass based on the total solid content of the photosensitive coloring composition.

Examples of the photopolymerization initiator (C) include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one. , 1-Hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl] -1-butanone, or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one and other acetophenone compounds; Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylicized benzophenone, 4-benzoyl Benzopenone compounds such as -4'-methyldiphenylsulfide or 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, isopropylthioxanthone, Thioxanthone compounds such as 2,4-diisopropylthioxanthone or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4 , 6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -S-triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2 , 4-Trichloromethyl- (4'-methoxystyryl) -6-triazine and other triazine compounds; 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-ben) Oxime ester compounds such as zoyloxime)] or etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime); bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, or phosphine compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrene quinone, camphorquinone, and ethylanthraquinone. Examples thereof include a compound; a borate compound; a carbazole compound; an imidazole compound; or a titanosen compound.
These photopolymerization initiators can be used alone or in admixture of two or more at any ratio as required.
As commercially available products, all of the acetophenone compounds are manufactured by BASF, "IRGACURE 907" (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-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-morpholinophenyl) -butane-1-one, as phosphine compounds, all manufactured by BASF, "IRGACURE 819" (bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide), "IRGACURE TPO" (2,4,6-
Trimethylbenzoyldiphenylphosphine oxide), and the like.

In the present invention, among these, it is preferable to contain an oxime ester compound.

[Oxime ester compound]
When an oxime ester compound absorbs ultraviolet rays, the NO bond of the oxime is cleaved to generate an iminyl radical and an alkyroxy radical. Since these radicals are further decomposed to generate highly active radicals, a pattern can be formed with a small amount of exposure. The oxime ester-based compound is preferably an oxime ester-based photopolymerization initiator represented by the general formula (4). By using the above-mentioned initiator, the resin-type dispersant (B) can be efficiently polymerized.

(Oxime ester-based photopolymerization initiator represented by the general formula (4))
General formula (4)

In the general formula (4)
Y ¹ may have a hydrogen atom or a substituent, an alkenyl group, an alkyl group, an alkyloxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group. , Alkyl sulfinyl group, aryl sulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, acyloxy group, amino group, phosphinoyl group, carbamoyl group, or sulfamoyl group.
Y ² may have a hydrogen atom or a substituent, an alkenyl group, an alkyl group, an alkyloxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group. , Alkyl sulfinyl group, aryl sulfinyl group, alkylsulfonyl group, arylsulfonyl group acyloxy group, or amino group.
Z is a direct bond or -CO- group and
Y ³ is a monovalent organic group containing a good carbazole group which may have a substituent, Ph-S-Ph- group (Ph may have a substituent, a phenyl group or represents a phenylene group) Is preferable.

Examples of the ^{alkenyl group which may have a substituent at Y 1} include a linear, branched, monocyclic or condensed polycyclic alkenyl group having 1 to 18 carbon atoms, which have a plurality of carbon atoms in the structure. -It may have a carbon double bond, and specific examples thereof include a vinyl group, a 1-propenyl group, an allyl group, a 2-butenyl group, a 3-butenyl group, an isopropenyl group, an isobutenyl group, and a 1-pentenyl group. , 2-Pentenyl group, 3-Pentenyl group, 4-Pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, cyclopentenyl group, cyclohexenyl group, 1 , 3-Butadienyl group, cyclohexadienyl group, cyclopentadienyl group and the like, but are not limited thereto.

The alkyl group which may have a substituent in Y ¹ is a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms, or 2 to 18 carbon atoms, and optionally 1 Examples include linear, branched, monocyclic or condensed polycyclic alkyl groups 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 group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group and octyl group. Group, nonyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, isopentyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group , Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group and the like, but are not limited thereto. Specific examples of linear and branched alkyl groups having 2 to 18 carbon atoms and being interrupted by one or more of -O- include -CH ₂ -O-CH ₃ and -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 (where n is 1 from a _{8), -} (CH 2 is _{-CH 2 -CH 2 -O) m -CH} 3 ( wherein m is 5 _{1), - CH 2 -CH (} CH 3) -O-CH 2 - CH _3- , -CH _2- CH- (OCH ₃ ) _2, etc. can be mentioned, but the present invention is not limited thereto.

Specific examples of the monocyclic or condensed polycyclic alkyl group having 2 to 18 carbon atoms and optionally interrupted by one or more of -O- include, but are limited to: It is not something that is done.

The ^{alkyloxy group which may have a substituent in Y 1} is a linear, branched chain, monocyclic or condensed polycyclic alkyloxy group having 1 to 18 carbon atoms, or 2 to 18 carbon atoms. In some cases, linear, branched chain, monocyclic or condensed polycyclic alkyloxy groups interrupted by one or more —O—s can be mentioned. Specific examples of linear, branched, monocyclic or condensed polycyclic alkyloxy groups having 1 to 18 carbon atoms include methyloxy group, ethyloxy group, propyloxy group, butyloxy group, pentyloxy group and hexyloxy group. Group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropyloxy group, isobutyloxy group, isopentyloxy group, sec-butyloxy group, tert-butyloxy group, sec-pentyl Oxy group, tert-pentyloxy group, tert-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group, boronyloxy group , 4-Decilcyclohexyloxy group and the like, but are not limited thereto. Specific examples of linear and branched alkyloxy groups having 2 to 18 carbon atoms and optionally interrupted by one or more -O- are -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 (where n is 1 to 8), -O- (CH _2- CH _2- CH ₂ -O) _m- CH ₃ (where m is 1 to 5), -O-CH _{2 -CH (CH 3) -O-} CH 2 -CH 3 -, - OCH 2 -CH- (OCH 3) can be cited _2, etc., but is not limited thereto.

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

Examples of the aryl group which may have a substituent in Y ¹ include a monocyclic or condensed polycyclic aryl group having 6 to 24 carbon atoms, and specific examples thereof include a phenyl group, a 1-naphthyl group and a 2-naphthyl group. Group, 1-anthrill group, 9-anthrill group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthril group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azulenyl group, 1-acenaphthyl Group, 2-fluorenyl group, 9-fluorenyl group, 3-perylenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-kisilyl group, 2,5-kissyl group, mesityl group, p. -Cumenyl group, p-dodecylphenyl group, p-cyclohexylphenyl group, 4-biphenyl group, o-fluorophenyl group, m-chlorophenyl group, p-bromophenyl group, p-hydroxyphenyl group, m-carboxyphenyl group, Examples thereof include, but are not limited to, an o-mercaptophenyl group, a p-cyanophenyl group, an m-nitrophenyl group, and an m-azidophenyl group.

Examples of the aryloxy group which may have a substituent in Y ¹ include a monocyclic or condensed polycyclic aryloxy group having 4 to 18 carbon atoms, and specific examples thereof include a phenoxy group, a naphthyloxy group, and 2-. Naftyloxy group, 9-anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azulenyloxy group, 1-acenaphthyloxy group , 9-Fluorenyloxy group and the like, but are not limited thereto.

Examples of the heterocyclic group which may have a substituent in Y ¹ include aromatic or aliphatic heterocyclic groups having 4 to 24 carbon atoms including a nitrogen atom, an oxygen atom, a sulfur atom and a phosphorus atom. , 2-thienyl group, 2-benzothienyl group, naphtho [2,3-b] thienyl group, 3-thianthrenyl group, 2-thianthrenyl group, 2-furyl group, 2-benzofuryl group, pyranyl group, isobenzofuranyl Group, chromenyl group, xanthenyl group, phenoxatyynyl group, 2H-pyrrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridadinyl group, indridinyl group, isoindryl group, 3H-indrill group , 2-indrill group, 3-indrill group, 1H-indazolyl group, prynyl group, 4H-quinolinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyldinyl group, quinoxaniryl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH- Carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, β-carbazoleyl group, phenanthridinyl group, 2-acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group , Isoxazolyl group, Frazanyl group, 3-Phenixazinyl group, Isochromanyl group, Chromanyl group, Pyrrolidinyl group, Pyrrolinyl group, Imidazolydinyl group, Imidazolinyl group, Pyrazolydinyl group, Pyrazolinyl group, Piperidyl group, Piperazinyl group, Indolinyl group, Isoindrinyl group. , Morphorinyl group, thioxanthril group, 4-quinolinyl group, 4-isoquinolyl group, 3-phenothiazine group, 2-phenoxatyynyl group, 3-cummarinyl group and the like, but are limited thereto. It's not a thing.

Examples of the ^{heterocyclic oxy group which may have a substituent at Y 1} include a monocyclic or condensed polycyclic heterocyclic oxy group having 4 to 18 carbon atoms including a nitrogen atom, an oxygen atom, a sulfur atom and a phosphorus atom. Specific examples thereof include 2-furanyloxy group, 2-thienyloxy group, 2-indrilloxy group, 3-indrilloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group and 2-carbazoli. Luoxy group, 3-carbazolyloxy group, 4-carbazolyloxy group, 9-acridinyloxy group and the like can be mentioned, but the present invention is not limited thereto.

A good alkylsulfanyl group optionally having a substituent in Y ^1, number 1 to 18 linear, branched, monocyclic or fused polycyclic alkylthio group, and specific examples include a methylthio group , Ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, octylthio group, decylthio group, dodecylthio group, octadecylthio group and the like, but are not limited thereto.

Examples of the arylsulfanyl group which may have a substituent in Y ¹ include a monocyclic or condensed polycyclic arylthio group having 6 to 18 carbon atoms, and specific examples thereof include a phenylthio group, a 1-naphthylthio group and a 2-. Examples thereof include, but are not limited to, a naphthylthio group, a 9-anthrylthio group, a 9-phenanthrylthio group and the like.

As the ^{alkylsulfinyl group which may have a substituent in Y 1} , an alkylsulfinyl group having 1 to 20 carbon atoms is preferable, and specific examples thereof include a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, and an isopropylsulfinyl group. Butylsulfinyl group, hexylsulfinyl group, cyclohexylsulfinyl group, octylsulfinyl group, 2-ethylhexylsulfinyl group, decanoylsulfinyl group, dodecanoylsulfinyl group, octadecanoylsulfinyl group, cyanomethylsulfinyl group, methyloxymethylsulfinyl group, etc. However, it is not limited to these.

A good arylsulfinyl group optionally having a substituent in Y ^1, carbon atoms 6 to 30
, And specific examples thereof include phenylsulfinyl group, 1-naphthylsulfinyl group, 2-naphthylsulfinyl group, 2-chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methyloxyphenylsulfinyl group, 2 -Butyloxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, Examples thereof include, but are not limited to, 4-methyloxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanylphenylsulfinyl group, 4-dimethylaminophenylsulfinyl group and the like.

As ^{the alkylsulfonyl group which may have a substituent in Y 1,} an alkylsulfonyl group having 1 to 20 carbon atoms is preferable, and specific examples thereof include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, and an isopropylsulfonyl group. Butylsulfonyl group, hexylsulfonyl group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methyloxymethylsulfonyl group, etc. These are, but are not limited to.

The arylsulfonyl group which may have a substituent in Y ^1, preferably an arylsulfonyl group having 6 to 30 carbon atoms, and specific examples include a phenylsulfonyl group, a 1-naphthylsulfonyl group, 2-naphthylsulfonyl group, 2-Chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methyloxyphenylsulfonyl group, 2-butyloxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group , 3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methyloxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group, 4-dimethylamino Examples thereof include, but are not limited to, phenylsulfonyl groups.

Examples of the acyl group which may have a substituent in Y ¹ include a hydrogen atom, a carbonyl group in which a linear, branched, monocyclic or condensed polycyclic aliphatic having 1 to 18 carbon atoms is bonded, and a carbon number of carbon atoms. A carbonyl group substituted with 2 to 20 alkyloxy groups, a carbonyl group to which a monocyclic or condensed polycyclic aryl group having 6 to 18 carbon atoms is bonded, and a monocyclic or condensed polycyclic aryloxy group having 6 to 18 carbon atoms Examples thereof include a carbonyl group in which a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms including a substituted carbonyl group, a nitrogen atom, an oxygen atom, a sulfur atom and a phosphorus atom is bonded, and specific examples thereof include formyl. Group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl group, stearoyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, crotonoyl Group, isocrotonoyl group, oleoil group, cinnamoyl group, benzoyl group, methyloxycarbonyl group, ethyloxycarbonyl group, propyloxycarbonyl group, butyloxycarbonyl group, hexyloxycarbonyl group, octyloxycarbonyl group, decyloxycarbonyl group, octadecyl Oxycarbonyl group, trifluoromethyloxycarbonyl group, benzoyl group, toluoil group, 1-naphthoyl group, 2-naphthoyl group, 9-anthrylcarbonyl group, phenyloxycarbonyl group, 4-methylphenyloxycarbonyl group, 3-nitro Phenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 2-methylsulfanylphenyloxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 9-anthrryloxycarbonyl group, 3-fluoroyl Groups, 2-tenoyl groups, nicotinoyyl groups, isonicotinoyl groups and the like can be mentioned, but are not limited thereto.

Examples of the acyloxy group which may have a substituent in Y ¹ include an acyloxy group having 2 to 20 carbon atoms, and specific examples thereof include an acetyloxy group, a propanoyloxy group, a butanoyloxy group, and a pentanoyloxy group. Examples thereof include a group, a trifluoromethylcarbonyloxy group, a benzoyloxy group, a 1-naphthylcarbonyloxy group, a 2-naphthylcarbonyloxy group and the like.

Examples ^{of the amino group which may have a substituent in Y 1} include an amino group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, an alkylarylamino group, a benzylamino group, a dibenzylamino group and the like. Can be mentioned.

Here, as the alkylamino group, a methylamino group, an ethylamino group, a propylamino group, a butylamino group, a pentylamino group, a hexylamino group, a heptylamino group, an octylamino group, a nonylamino group, a decylamino group and a dodecylamino group. , Octadecylamino group, isopropylamino group, isobutylamino group, isopentylamino group, sec-butylamino group, tert-butylamino group, sec-pentylamino group, tert-pentylamino group, tert-octylamino group, neopentyl Examples thereof include amino groups, cyclopropylamino groups, cyclobutylamino groups, cyclopentylamino groups, cyclohexylamino groups, cycloheptylamino groups, cyclooctylamino groups, cyclododecylamino groups, 1-adamantamino groups, 2-adamantamino groups and the like. , Not limited to these.

Examples of the dialkylamino group include dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, diheptylamino group, dioctylamino group, dinonylamino group, didecylamino group and didodecylamino group. Dioctadecylamino group, diisopropylamino group, diisobutylamino group, diisopentylamino group, methylethylamino group, methylpropylamino group, methylbutylamino group, methylisobutylamino group, cyclopropylamino group, pyrrolidino group, piperidino group, Examples thereof include, but are not limited to, piperadino groups.

Examples of the arylamino group include anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p-toluidino group, 2-biphenylamino group, 3-biphenylamino group and 4- Examples thereof include, but are not limited to, a biphenylamino group, a 1-fluoreneamino group, a 2-fluoreneamino group, a 2-thiazoleamino group, and a p-terphenylamino group.

Examples of the diarylamino group include, but are not limited to, a diphenylamino group, a ditrilamino group, an N-phenyl-1-naphthylamino group, and an N-phenyl-2-naphthylamino group.

Examples of the alkylarylamino group include N-methylanilino group, N-methyl-2-pyridino group, N-ethylanilino group, N-propylanilino group, N-butylanilino group, N-isopropyl, N-pentylanilino group and N. Examples thereof include, but are not limited to, an ethylanilino group and an N-methyl-1-naphthylamino group.

Examples of the phosphinoyl group which may have a substituent in Y ¹ include a phosphinoyl group having 2 to 50 carbon atoms, and specific examples thereof include a dimethylphosphinoyl group, a diethylphosphinoyl group, and a dipropylphosphinoyl. Examples include, but are limited to, groups, diphenylphosphinoyl groups, dimethoxyphosphinoyl groups, diethoxyphosphinoyl groups, dibenzoylphosphinoyl groups, bis (2,4,6-trimethylphenyl) phosphinoyl groups and the like. It is not something that is done.

Examples of the carbamoyl group which may have a substituent in Y ¹ include a carbamoyl group having 1 to 30 carbon atoms, and specific examples thereof include an N-methylcarbamoyl group, an N-ethylcarbamoyl group, and an N-propylcarbamoyl group. , N-butylcarbamoyl group, N-hexylcarbamoyl group, N-cyclohexylcarbamoyl group, N-octylcarbamoyl group, N-decylcarbamoyl group, N-octadecylcarbamoyl group, N-phenylcarbamoyl group, N-2-methylphenylcarbamoyl group. Group, N-2-chlorophenylcarbamoyl group, N-2-isopropoxyphenylcarbamoyl group, N-2- (2-ethylhexyl) phenylcarbamoyl group, N-3-chlorophenylcarbamoyl group, N-3-nitrophenylcarbamoyl group, N-3-cyanophenylcarbamoyl group, N-4-methoxyphenylcarbamoyl group, N-4-cyanophenylcarbamoyl group, N-4-methylsulfanylphenylcarbamoyl group, N-4-phenylsulfanylphenylcarbamoyl group, N-methyl Examples thereof include, but are not limited to, -N-phenylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-dibutylcarbamoyl group, N, N-diphenylcarbamoyl group and the like.

Examples of the sulfamoyl group which may have a substituent in Y ¹ include a sulfamoyl group having 0 to 30 carbon atoms, and specific examples thereof include a sulfamoyl group, an N-alkyl sulfamoyl group, and an N-aryl sulfamoyl. Examples include groups, N, N-dialkylsulfamoyl groups, N, N-diarylsulfamoyl groups, N-alkyl-N-arylsulfamooil groups and the like. More specifically, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsul. Famoyl group, N-octyl sulfamoyl group, N-2-ethylhexyl sulfamoyl group, N-decyl sulfamoyl group, N-octadecyl sulfamoyl group, N-phenyl sulfamoyl group, N-2- Methylphenyl sulfamoyl group, N-2-chlorophenyl sulfamoyl group, N-2-methoxyphenyl sulfamoyl group, N-2-isopropoxyphenyl sulfamoyl group, N-3-chlorophenyl sulfamoyl group, N-3-nitrophenyl sulfamoyl group, N-3-cyanophenyl sulfamoyl group, N-4-methoxyphenyl sulfamoyl group, N-4-cyanophenyl sulfamoyl group, N-4-dimethylamino Phenylsulfamoyl group, N-4-methylsulfanylphenylsulfamoyl group, N-4-phenylsulfanylphenylsulfamoyl group, N-methyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl Groups, N, N-dibutylsulfamoyl groups, N, N-diphenylsulfamoyl groups and the like can be mentioned, but are not limited thereto.

An alkenyl group, an alkyl group, an alkyloxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, which may have a substituent at ^{Y 2.} As the arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyloxy group, and amino group, the above-mentioned alkenyl group which may have a substituent in R1, an alkyl group which may have a substituent, and a substituent may be used. It has an alkyloxy group which may have, an aryl group which may have a substituent, an aryloxy group which may have a substituent, a heterocyclic group which may have a substituent, and a substituent. Also good heterocyclic oxy group, alkylsulfanyl group which may have a substituent, arylsulfanyl group which may have a substituent, alkylsulfinyl group which may have a substituent, may have a substituent. It may have a good arylsulfinyl group, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, an acyloxy group which may have a substituent, and a substituent. Synonymous with amino group.

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, phenoxy group and p-tolyloxy. Aryloxy groups such as groups, methoxycarbonyl groups, butoxycarbonyl groups, alkoxycarbonyl groups such as phenoxycarbonyl groups, acyloxy groups such as acetoxy groups, propionyloxy groups and benzoyloxy groups, acetyl groups, benzoyl groups, isobutyryl groups and acryloyl groups. , Acyl group such as methacryloyl group, metoxalyl group, alkylsulfanyl group such as methylsulfanyl group, tert-butylsulfanyl group, arylsulfanyl group such as phenylsulfanyl group, p-tolylsulfanyl group, methylamino group, cyclohexylamino group and the like. Dialkylamino groups such as alkylamino group, dimethylamino group, diethylamino group, morpholino group, piperidino group, arylamino group 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, cycloheptyl group, cyclooctyl group, cyclooctadecyl group and other alkyl groups, phenyl group, p-tolyl group, xsilyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl In addition to aryl groups such as groups, heterocyclic groups such as frill groups and thienyl groups, hydroxy groups, carboxy groups, formyl groups, mercapto groups, sulfo groups, mesyl groups, p-toluenesulfonyl groups, amino groups and nitro groups, Examples thereof include a cyano group, a trifluoromethyl group, a trichloromethyl group, a trimethylsilyl group, a phosphinico group, a phosphono group, a trimethylammoniumyl group, a dimethylsulfoniumyl group, and a triphenylphenacylphosphoniumyl group.
Further, one or more or one or more of these substituents may be present, and the hydrogen atom of these substituents may be further substituted with another substituent.

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 (6), particularly the carbazole moiety represented by (6) is used. The oxime ester-based photopolymerization initiator contained in the molecule is used as the photopolymerization initiator (C) in the present invention in combination with the resin-type dispersant (B) in order to obtain good patterning properties. It is even more preferable among the initiators.

(Oxime ester-based photopolymerization initiator represented by the general formula (5))
General formula (5)

The general formula (5) corresponds to the case where Z is a -CO- group and Y ³ is a Ph-S-Ph- group in the ^{general formula (4), and Y 4 to Y 6} are hydrogen atoms or substituents. An alkyl group or an aryl group which may have an alkyl group is preferable. The alkyl group which may have a substituent or the aryl group which may have a substituent in ^{Y 4 to Y 6} is synonymous with the alkyl group or the aryl group in ^{Y 1} and Y ^2.

Further, Y ¹ may have an aryl group having a substituent, Y ² may have an alkyl group having 1 to 20 carbon atoms, and Y ⁴ and Y ⁶ have a hydrogen atom. It is preferable that Y ⁵ is a hydrogen atom or a Y ^7- CO- group.

As Y ⁷ , for example, a halogen group such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom,
Alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, aryloxy groups such as phenoxy group and p-tolyloxy group, alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group, acetoxy group and propionyloxy. Aryloxy groups such as groups and benzoyloxy groups, acetyl groups, benzoyl groups, isobutyryl groups, acryloyl groups, methacryloyl groups, acyl groups such as methoxalyl groups, alkylsulfanyl groups such as methylsulfanyl groups and tert-butylsulfanyl groups, and phenylsulfanyl groups. , P-tolylsulfonyl group such as arylsulfanyl group, methylamino group, cyclohexylamino group and other alkylamino group, dimethylamino group, diethylamino group, morpholino group, piperidino group and other dialkylamino group, phenylamino group, p-tolylamino Alrylamino group such as arylamino group, methyl group, ethyl group, tert-butyl group, dodecyl group and other alkyl group, phenyl group, p-tolyl group, xsilyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, benzofuranyl group. In addition to aryl groups such as aryl groups, frill groups, heterocyclic groups such as thienyl groups, etc., hydroxy groups, carboxy groups, formyl groups, mercapto groups, sulfo groups, mesyl groups, p-toluenesulfonyl groups, amino groups, nitro groups, cyano groups, etc. Examples thereof include a group, a trifluoromethyl group, a trichloromethyl group, a trimethylsilyl group, a phosphinico group, a phosphono group, a trimethylammoniumyl group, a dimethylsulfoniumyl group, a triphenylphenacylphosphoniumyl group and the like.

More preferably, the substituent of Y ² is a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and a cyclooctadecyl group.

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

(Oxime ester-based photopolymerization initiator represented by the general formula (6))
General formula (6)

^{The general formula (6) corresponds to the case where Y 3} in the general formula (4) is a monovalent organic group containing a carbazole group which may have a substituent, and Y ^{7 to Y 14} are Y ¹ and Y. It is synonymous with the substituent in ^2.

Further, the alkyl group having 1 to 20 carbon atoms which may have a substituent as ^{Y 1} may have an alkyl group or an alkyl group having 1 to 20 carbon atoms which may have a substituent as ^{Y 2.} A good aryl group is preferably an alkyl group having 1 to 20 carbon atoms which may have a hydrogen atom or a substituent as ^{Y 7 to Y 14, or an aryl group which may have a substituent.}

When Z in the general formula (6) is a direct bond, an oxime ester-based photopolymerization initiator represented by the following general formula (6a) is preferable.

(Oxime ester-based photopolymerization initiator represented by the general formula (6a))
General formula (6a)

The general formula (6a) corresponds to the case where Z in the general formula (6) is a direct bond, and Y ^{7 to Y 10 and Y 12 to Y 13} in the general formula (6) are hydrogen atoms.
Further, Y ¹¹ is ^{preferably a Y 15-} CO- group or a nitro group. Y ¹⁵ is ^{synonymous with the substituents in Y 1} and Y ² , and is preferably an aryl group which may have a substituent. The Y ^15- CO- group is preferably an acyl group such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group, or a metoxalyl group which may further have a substituent. More preferably, it is a benzoyl group or a nitro group which may have a substituent. As Y ¹⁴ , an alkyl group having 1 to 20 carbon atoms which may have a substituent or an aryl group which may have a substituent is preferable.

Further, as the substituent in the benzoyl group which may have a substituent, an alkyl group having 1 to 20 carbon atoms or an alkyloxy group is preferable. Further, as the alkyl group, a methyl group and an ethyl group are preferable, and among the alkyloxy groups, a linear or branched chain having 2 to 18 carbon atoms and optionally interrupted by one or more −O−. monocyclic or fused polycyclic alkyl group is preferable, if a carbon number of 2 in the Y ¹ 18 by linear interrupted by one or more -O-, branched, monocyclic or fused polycyclic Synonymous with alkyloxy group.

Y ² is preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent, and is preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like. It is a cycloalkyl group such as a cyclooctadecyl group. Further, an aryl group which may have a substituent is preferable, and an alkyl group having 1 to 20 carbon atoms which may further have a substituent, or a methoxy group, an ethoxy group, or a tert-butoxy group is preferable as the substituent. Alkoxy groups such as are preferable.

Specifically, as the oxime ester-based photopolymerization initiator represented by the general formula (6a),
These are photopolymerization initiators represented by the following chemical formulas (6a-1) to (6a-6).

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

General formula (6b)

Formula (6b) is, Z in the general formula (6) is -CO- group, Y ³ corresponds to the case of the monovalent organic group containing a good carbazole group which may have a substituent group, the keto form carbazole group It is an oxime ester-based photopolymerization initiator having the above.
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} may have a substituent. It is preferably a good aryl group.
As the substituent of the aryl group which may have a substituent, an acyl group such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group and a metoxalyl group is preferable, and a benzoyl group is more preferable.

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

Commercially available products of these oxime ester compounds are from BASF, 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)] (IR).
GACURE OXE-01), Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) (IRGACURE OXE 02), N- 1919 (manufactured by ADEKA), TRONLYTR-P
BG-304, TRONLY TR-PBG-305, TRONLY TR-PBG-309 (all manufactured by Changzhou Strong New Materials Co., Ltd.) and the like are commercially available. In addition, the oximes described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-0372223, JP-A-2010-215575, JP-A-2011-02998, etc. It is also possible to use an ester-based photopolymerization initiator.

<Organic solvent (D)>
The photosensitive coloring composition of the present invention contains an organic solvent (D). The colorant is sufficiently dispersed and permeated into the colorant carrier with the organic solvent (D), and is applied onto a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm to form a filter segment. Can be facilitated.
As the organic solvent, one type can be used alone, or two or more types can be mixed and used. Further, since the solvent can adjust the coloring composition to an appropriate viscosity and form a filter segment having a desired uniform film thickness, 500 to 4000% by mass is based on the total weight of the coloring agent (100% by mass). It is preferable to use the amount of.

Examples of the organic solvent (D) include 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, and 1,3-butylene glycol di. Acetate, 1,4-butanediol diacetate, 1,
4-Dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexene-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate , 3-Methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m -Xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol di Butyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotersial butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether , Ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclo Hexanol 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, triase Chin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol Monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid Examples include ester. These solvents can be used alone or in admixture of two or more in any ratio as required.

Among them, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol diacetate, and ethylene glycol monomethyl ether have good dispersibility, permeability, and coating property of the photosensitive composition. Acetates such as acetate, ethylene glycol monoethyl ether acetate, 1,3-butylene glycol diacetate, cyclohexanol acetate, 1,4-butanediol diacetate, butanediol diacetate, benzyl alcohol, diacetone alcohol, 1-methoxy It is preferable to use alcohols such as -2-propanol and 3-methoxybutanol, ketones such as cyclohexanone, ethyl 3-ethoxypropionate, and the like.

<Polymerizable compound (E)>
The photosensitive coloring composition of the present invention contains the polymerizable compound (E). The polymerizable compound (E) contains monomers and oligomers that are cured by ultraviolet rays, heat, or the like to form a transparent resin.

Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , 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 ) Acrylate, Trimethylol Propane Tri (meth) Acrylate, Phenoxytetraethylene Glycol (Meta) Acrylate, Phenoxy Hexaethylene Glycol (Meta) Acrylate, Trimethylol Propane PO Modified Tri (Meta) Acrylate, Trimethylol Propane EO Modified Tri (Meta) Acrylate, EO-modified di (meth) acrylate of isocyanuric acid, EO-modified tri (meth) acrylate of isocyanuric acid, ditrimethylol propanetetra (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 ) Acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, various acrylic acid esters such as methylolated melamine (meth) acrylic acid ester, epoxy (meth) acrylate, urethane acrylate, and methacrylate ester, (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. It is not something that is done.
These polymerizable compounds may be used alone or in admixture of two or more at any ratio as required.

These commercially available products include KAYARAD R-128H, KAYARAD R526, KAYARAD PEG400DA, KAYARADMAND, and KAY manufactured by Nippon Kayaku Co., Ltd.
ARD NPGDA, KAYARAD R-167, KAYARAD HX-220, KAYARAD R-551, KAYARAD R712, KAYARADR-604, KA
YARAD R-684, KAYARAD GPO-303, KAYARAD TMPTA
, KAYARAD DPHA, KAYARAD DPEA-12, KAYARAD DPH
A-2C, KAYARAD D-310, KAYARAD D-330, KAYARAD
DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, and M-303, M-305, M-3 manufactured by Toagosei Co., Ltd.
06, 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, Osaka Organic Co., Ltd. Viscort # 310HP, Viscort # 335HP, Viscort # 700, Viscort # 295, Viscort # 330, biscoat # 360, biscoat #GPT, biscoat # 400, biscoat # 405, A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd. and the like can be preferably used.

The content of the polymerizable compound (E) with respect to the total solid content is preferably 15 to 45% by mass. More preferably, the content is 20 to 35% by mass. If it is less than the above, the tapered portion of the photosensitive coloring composition pattern is elongated for a long time, and it becomes difficult to form a high-definition fine pixel pattern. If the amount is more than the above, problems such as deterioration of resolution and residue may occur.

(Polymerizable compound having an acid 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, and a phosphoric acid group.

Examples of the polymerizable compound having an acid group include an esterified product of a free hydroxyl group-containing poly (meth) acrylate of a polyhydric alcohol and (meth) acrylic acid and a dicarboxylic acid; a polyvalent carboxylic acid and a monohydroxyalkyl. Examples thereof include esterified products with (meth) acrylates. Specific examples include monohydroxyoligoacrylates such as trimethylolpropane diacrylate, trimethylolpropanedimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate, or monohydroxyoligomethacrylates. Free carboxyl group-containing monoesteride with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarbaryl acid), butane-1,2,4 -Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, and 2-hydroxyethyl acrylate, 2- Examples thereof include monohydroxymonoacrylates such as hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, and oligoesterides containing a free carboxyl group with monohydroxymonomethacrylates, but the effects of the present invention are limited thereto. It is not something that is done.

_{As these commercially available products, Viscoat #} 2500P manufactured by Osaka Organic Co., Ltd., M-5300, M-5400, M-5700, M-510, M-520 manufactured by Toagosei Co., Ltd. and the like can be preferably used.

These polymerizable compounds having an acid group can be used alone or in admixture of two or more at any ratio, if necessary.

(Polymerizable compound with urethane bond)
The polymerizable compound in the present invention may contain a polymerizable compound containing at least one ethylenically unsaturated bond and one urethane bond. For example, a polyfunctional urethane acrylate obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate, or a polyfunctional urethane acrylate obtained by reacting an alcohol with a polyfunctional isocyanate and further reacting with a (meth) acrylate having a hydroxyl group. Urethane acrylate and the like can be mentioned.

Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trimethylolpropandi (meth) acrylate, pentaerythritol tri (meth) acrylate, and ditrimethylol propanetri (meth). Meta) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol ethylene oxide-modified penta (meth) acrylate, dipentaerythritol propylene oxide-modified penta (meth) acrylate, dipentaerythritol caprolactone-modified penta (meth) acrylate, glycerol acrylate Examples thereof include methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and carboxy (meth) acrylate, and a hydroxyl group-containing polyol polyacrylate.

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

Further, although the structure of the alcohol is not limited, it is preferable to use a polyhydric alcohol because the degree of cross-linking of the cured coating film is increased and the coating film resistance is increased. Examples of the polyhydric alcohol include propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol and the like.

These commercially available products include AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, DAUA-167, manufactured by Kyoeisha Chemical Co., Ltd. UA-160TM, UV-4108F, UV-4117F manufactured by Osaka Organic Chemical Industry Co., Ltd., and the like can be preferably used.

As these photopolymerizable monomers having a urethane bond, one type can be used alone, or two or more types can be mixed at an arbitrary ratio as required.

<Binder resin>
The photosensitive coloring composition of the present invention can contain a binder resin. Specific examples of the binder resin include thermoplastic resins and thermosetting resins.

(Thermoplastic resin)
Examples of the thermoplastic resin used for the binder resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, and polyvinyl acetate. , Polyurethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resin and the like. .. Above all, it is preferable to use an acrylic resin.

(Thermosetting resin)
Examples of the thermosetting resin used for 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.

The thermosetting resin may be a low molecular weight compound such as an epoxy compound, a benzoguanamine compound, a rosin-modified maleic acid compound, a rosin-modified fumaric acid compound, a melamine compound, a urea compound, a cardo compound, and a phenol compound. It is not limited to this. By including such a thermosetting resin, the resin reacts when the filter segment is fired, the crosslink density of the coating film is increased, the heat resistance is improved, and the pigment aggregation during the firing of the filter segment is suppressed. Be done. Among these, epoxy resin, cardo resin, or melamine resin is preferable.

When a color filter is produced using the photosensitive coloring composition, the binder resin is a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Is preferable.
The weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000 in order to preferably disperse the colorant. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the Mw / Mn value is preferably 10 or less.

Since the binder resin has good film-forming properties and various resistances, it is preferable to use the binder resin in an amount of 10 parts by mass or more in terms of resin solid content with respect to 100 parts by mass of the total mass of the colorant, and the colorant concentration is high. Since good color characteristics can be exhibited, it is preferable to use the resin solid content in an amount of 500 parts by mass or less.

In one embodiment, when the coloring composition is used in the form of an alkali-developing colored resist material, an alkali-soluble vinyl-based resin prepared by using an acidic group-containing ethylenically unsaturated monomer from the viewpoint of developability. Is preferably used as the binder resin. Further, in another embodiment, a photosensitive coloring composition may be formed for the purpose of improving the light sensitivity and the solvent resistance. In this case, an active energy ray-curable resin having an ethylenically unsaturated double bond can be used as the binder resin. Hereinafter, these embodiments will be described in more detail.

As the vinyl-based alkali-soluble resin that can be suitably used as a binder, for example, a homopolymer or a copolymer prepared by using an ethylenically unsaturated monomer having an acidic group such as a carboxyl group, a hydroxyl group, or a sulfone group. Can be mentioned. Specific examples of the vinyl-based alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, and an ethylene / (meth) acrylic acid copolymer. , Or isobutylene / (anhydrous) maleic acid copolymer and the like. Among them, at least one resin selected from a (meth) acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer is preferable. In particular, a (meth) acrylic resin having an acidic group is preferably used because it has high heat resistance and transparency.

The acidic group in the acidic group-containing ethylenically unsaturated monomer used for preparing the resin is preferably a carboxylic acid or a hydroxyl group. Examples of ethylenically unsaturated monomers having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid and the like. Examples of ethylenically unsaturated monomers having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 4 Examples thereof include −hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl acrylate, and caprolactone adducts of these monomers (the number of addition moles is preferably 1 to 5).

In one embodiment, when a photosensitive coloring composition for a color filter is formed, the binder resin is a colorant adsorbing group and an alkali during development from the viewpoints of pigment dispersibility, permeability, developability, and heat resistance. The balance between the carboxyl group acting as a soluble group and the aliphatic group and the aromatic group acting as an affinity group for the colorant carrier and the solvent is the weight. In one embodiment, from the viewpoint of pigment dispersibility, permeability, developability, and durability, it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g as the binder resin. By using a resin having an acid value within the above range, appropriate solubility in a developing solution can be obtained, and it becomes easy to form a fine pattern.

From the above viewpoint, the vinyl-based alkali-soluble resin obtained by polymerizing the acidic group-containing ethylenically unsaturated monomer has an acid value of 20 to 300 mgKOH / g and a weight average molecular weight (Mw) of 1000 to 80,000. Is preferable. In one embodiment, the resin may be a copolymer of methacrylic acid, 2-hydroxyethyl (meth) acrylate, and other monomers such as n-butyl methacrylate.

As another embodiment, when a photosensitive coloring composition is formed as an alkali-developable coloring resist for a color filter, it is preferable to use an active energy ray-curable resin having an ethylenically unsaturated double bond as a binder resin. In particular, it is preferable to use an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain. When the above resin having an ethylenically unsaturated double bond in the side chain is used as the binder resin, foreign matter in the coating film is not generated after the resist is applied, and the stability of the colorant in the resist material is improved. Tend. When the linear resin having no ethylenically unsaturated double bond in the side chain is used, the colorant is less likely to be trapped by the resin in the liquid in which the resin and the colorant are mixed, and has a degree of freedom. As a result, the colorant component is likely to aggregate and precipitate. On the other hand, when an active energy ray-curable resin having an ethylenically unsaturated double bond is used in the side chain, the colorant is likely to be trapped in the resin in a liquid in which the resin and the colorant are mixed. Therefore, in the solvent resistance test, the dye is less likely to elute, and the colorant component is less likely to aggregate and precipitate. Further, when the resin is three-dimensionally crosslinked to form a film by exposure with active energy rays, the colorant molecules are fixed, and even if the solvent is removed in the subsequent developing step, the colorant components are aggregated and precipitated. It is estimated that it will be difficult to do.

Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include a resin in which an unsaturated ethylenically double bond is introduced by the methods (a) and (b) shown below.

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

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

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

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like, and these may be used alone or in combination of two or more. It doesn't matter. It remained by using a tricarboxylic acid anhydride such as trimellitic acid anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride as needed, such as by increasing the number of carboxyl groups. It is also possible to hydrolyze the anhydride group. Further, when etrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenically double bond is used as the polybasic acid anhydride, the unsaturated ethylenically double bond can be further increased.

As a method similar to the method (a), for example, a side chain of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group with one or more other monomers. There is a method of introducing an unsaturated ethylenically double bond and a carboxyl group by adding an unsaturated ethylenic monomer having an epoxy group to a part of the carboxyl groups.

[Method (b)]
As the method (b), an unsaturated ethylenic monomer having a hydroxyl group is used, and by copolymerizing with an unsaturated monobasic acid monomer having another carboxyl group or another monomer. There is a method of reacting the side chain hydroxyl group of the obtained copolymer with the isocyanate group of an unsaturated ethylenic monomer having an isocyanate group.

Examples of the unsaturated ethylenic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol. Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate and cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Further, a polyether mono (meth) acrylate obtained by addition-polymerizing the above hydroxyalkyl (meth) acrylate with ethylene oxide, propylene oxide, and / or butylene oxide, (poly) γ-valerolactone, and (poly) ε-caprolactone. , And / or (poly) ester mono (meth) acrylate to which (poly) 12-hydroxystearic acid or the like is added can also be used. 2-Hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable from the viewpoint of suppressing foreign matter in the coating film.

Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate and 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, but the present invention is limited thereto. However, two or more types can be used together.

<Sensitizer>
The photosensitive composition of the present invention may contain a sensitizer.
Examples of the sensitizer include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone derivatives. , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonoal derivatives and other polymethine dyes, acrydin derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indolin derivatives, Azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative , Naphthalocyanine derivative, Subphthalocyanine derivative, Pyrylium derivative, Thiopyrylium derivative, Tetraphyllin derivative, Anuren derivative, Spiropyran derivative, Spiroxazine derivative, Thiospiropirane derivative, Metal allene complex, Organic ruthenium complex, or Michler ketone derivative, α-Acyloxy ester , Acylphosphine oxide, methylphenylglioxylate, benzyl, 9,10-phenanthrene quinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalofenone, 3,3'or 4,4'- Examples thereof include tetra (t-butylperoxycarbonyl) benzophenone and 4,4'-bis (diethylamino) benzophenone.
More specific examples include Nobu Ogawara et al., "Dye Handbook" (1986, Kodansha), Nobu Ogawara et al., "Chemistry of Functional Dyes" (1981, CMC), Chuzaburo Ikemori et al., "Special". The sensitizers described in "Functional Materials" (1986, CMC) can be mentioned, but are not limited thereto. In addition, a sensitizer that absorbs light from the ultraviolet to the near infrared region can also be contained.
Among the above sensitizers, examples of the sensitizer that can be particularly preferably sensitized include a thioxanthone derivative, a Michler ketone derivative, and a carbazole derivative. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis (Dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (ethylmethylamino) benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- N-ethylcarbazole or the like is used.
These sensitizers can be used alone or in admixture of two or more at any ratio, if necessary.
Examples of commercially available products include "KAYACURE DETX-S" (2,3-diethylthioxanthone manufactured by Nippon Kayaku Co., Ltd.) and "EAB-F"(4,4'-bis (diethylamino) benzophenone manufactured by Hodogaya Chemical Industry Co., Ltd.). Be done.

More specifically, Ogawara Nobu et al., "Dye Handbook" (1986, Kodansha), Ogawara Nobu et al., "Functional Dye Chemistry" (1981, CMC), Ikemori Chuzaburo et al., And " The sensitizers described in "Special Functional Materials" (1986, CMC) can be mentioned, but are not limited thereto. In addition, a sensitizer that absorbs light from the ultraviolet to the near infrared region can also be contained.

The content of the sensitizer when used is preferably 3 to 60 parts by mass with respect to 100 parts by mass of the photoradical polymerization initiator contained in the coloring composition, from the viewpoint of photocurability and developability. More preferably, it is 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 novolac type epoxy resin, cresol novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, dicyclopentadienephenol type epoxy resin, bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, and biphenol type epoxy. Examples thereof include resins, bisphenol-A novolak type epoxy resins, naphthalene skeleton-containing epoxy resins, alicyclic epoxy resins, and heterocyclic epoxy resins.
Among these, it is preferable that the epoxy compound is an alicyclic epoxy resin from the viewpoint of improving water stains, heat resistance and chemical resistance.

Specific examples of the phenol novolac type epoxy resin include Epicron N-740, Epicron N-770, Epicron N-775 manufactured by DIC Corporation, and D.D. E. Examples thereof include N438, RE-306 manufactured by Nippon Kayaku Corporation, jER152 and jER154 manufactured by Mitsubishi Chemical Corporation.

Specific examples of the cresol novolac type epoxy resin include Epicron N-660, Epicron N-665, Epicron N-670, Epicron N-673, Epicron N-680, Epicron N-695, and Epicron N-665 manufactured by DIC Corporation. Examples thereof include EXP, Epicron N-672-EXP, EOCN-102S manufactured by Nippon Kayaku Co., Ltd., EOCN-103S, EOCN-104S, UVR-6650 manufactured by Union Carbide Co., Ltd., ESCN-195 manufactured by Sumitomo Chemical Industries, Ltd. and the like.

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

Specific examples of the dicyclopentadienephenol type epoxy resin include Epicron EXA-7200 manufactured by DIC Corporation and TACTIX-556 manufactured by Dow Chemical Corporation.

Specific examples of the bisphenol type epoxy resin include jER828 and jER1001 manufactured by Mitsubishi Chemical Co., Ltd., UVR-6410 manufactured by Union Carbide Co., Ltd., and D.D. E. R-331, bisphenol-A type epoxy resin such as YD-8125 manufactured by Shin Nikka Epoxy Manufacturing Co., Ltd., UVR-6490 manufactured by Union Carbide Co., Ltd., bisphenol-F type such as YDF-8170 manufactured by Shin Nikka Epoxy Manufacturing Co., Ltd. Epoxy resin and the like can be mentioned.

Specific examples of the biphenol type epoxy resin include biphenol type epoxy resins such as NC-3000 and NC-3000H manufactured by Nippon Kayaku Corporation, and jERY manufactured by Mitsubishi Chemical Corporation.
Examples thereof include bixylenol type epoxy resins such as X-4000 and jER YL-6121.

Specific examples of the bisphenol A novolak type epoxy resin include Epicron N-880 manufactured by DIC Corporation and jER E157S75 manufactured by Mitsubishi Chemical Corporation.

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

Specific examples of the alicyclic epoxy resin include Seikiside 2021P, 2081, 2000 manufactured by Daicel Corporation, Epolide PB3600, PB4700, GT401, EHPE-3150, Cyclomer M100 and the like.

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

These epoxy compounds may be used alone or in admixture of two or more at any ratio as required.

The content of the epoxy compound used in the photosensitive coloring composition of the present invention is usually 0.5 to 50% by mass, preferably 1 to 40% by mass, based on 100% by mass of the solid content of the coloring composition. When the content of the epoxy compound is in the above range, the heat resistance is high and an excellent coating film 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 oxetane group can be used without particular limitation. Examples of the oxetane compound include those in which the oxetane group is monofunctional, those in which the oxetane group is bifunctional, and those in which the oxetane group is bifunctional or higher.

Examples of monofunctional oxetane groups include (3-ethyloxetane-3-yl) methyl acrylate, (3-ethyloxetane-3-yl) methyl methacrylate, and 3-ethyl-3.
-Hydroxymethyl oxetane, 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 and the like can be mentioned.
Specific examples include OXE-10 manufactured by Osaka Organic Chemical Industry Co., Ltd., OXT-101 and 212 manufactured by Toagosei Co., Ltd., and the like.

Examples of bifunctional oxetane groups include 4,4'-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl) and 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl]. Benzene, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, di [1-ethyl (3-oxetanyl)] methyl ether, di [1-ethyl (3-oxetanyl)] methyl Ether-3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (2-phenoxymethyl) oxetane, 3,7-bis (3-bis) Oxetanyl) -5-oxa-nonane, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene Glycosbis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (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-oxetanylmethoxy) 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) ether, PO-modified hydrogenated bisphenol A-bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl-3) -Oxetanylmethyl) ether and the like can be mentioned.
Specific examples include OXBP and OXTP manufactured by Ube Industries, Ltd., OXT-121 and OXT-221 manufactured by Toagosei Co., Ltd.

Examples of those having a bifunctional or higher oxetane group include pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, and dipentaerythritol hexa (3-ethyl). -3-oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa (3-ethyl) Ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis (3-ethyl-3-oxetanylmethyl) ether, resin containing an oxetane group (For example, the oxetane-modified phenol novolac resin described in Patent No. 3783462) and the polymer obtained by radically polymerizing a (meth) acrylic monomer such as OXE-30 described above can be mentioned. Such a polymer can be obtained by using a known polymerization method.

The content of the oxetane compound used in the photosensitive composition of the present invention is usually 0.5 to 50% by mass, preferably 1 to 40% by mass, based on 100% by mass of the solid content of the coloring composition. When the content of the oxetane compound is within the above range, it is preferable because an excellent coating film having good water stains and high chemical resistance can be obtained.

<Thiol chain transfer agent>
The photosensitive composition of the present invention may contain a thiol-based chain transfer agent as the chain transfer agent. By using thiol together with a photopolymerization initiator, in the radical polymerization process after light irradiation, a chile radical that acts as a chain transfer agent and is less susceptible to polymerization inhibition by oxygen is generated, so that the obtained coloring composition becomes highly sensitive. ..

Further, a polyfunctional aliphatic thiol bonded to an aliphatic group such as methylene or ethylene group having two or more SH groups is preferable. More preferably, it is a polyfunctional aliphatic thiol having 4 or more SH groups. By increasing the number of functional groups, the polymerization initiation function is improved, and the pattern can be cured from the surface to the vicinity of the substrate.

Examples of the polyfunctional thiol include hexanedithiol, decandithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropio. Nate, Trimethylol Propanetristhioglycolate, Trimethylol Propanetristhiopropionate, Trimethylol Propantris (3-mercaptobutyrate), Pentaerythritol Tetrakissthioglycolate, Pentaerythritol Tetraxthiopropionate, Trimercaptopropionic Acid Tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s- Examples thereof include triazine, and preferred examples include ethylene glycol bisthiopropionate, trimethylpropantristhiopropionate, and pentaerythritol tetrakisthiopropionate.

These thiol-based chain transfer agents may be used alone or in admixture of two or more.

The content of the thiol chain transfer agent is preferably 1 to 10%, more preferably 2.0 to 8.0% of the total solid content of the coloring composition. In this range, the effect of the chain transfer agent is increased, and the sensitivity, taper shape, wrinkles, film shrinkage rate, etc. are improved.

<UV absorber>
The photosensitive composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorber in the present invention is an organic compound having an ultraviolet absorbing function, and examples thereof include benzotriazole-based organic compounds, triazine-based organic compounds, benzophenone-based organic compounds, cyanoacrylate-based organic compounds, and salicylate-based organic compounds. ..

The content of the ultraviolet absorber is preferably 5 to 70% by mass based on 100% by mass of the total of the photopolymerization initiator and the ultraviolet absorber. If the content of the UV absorber is less than the above, the effect of the UV absorber is small and the resolution cannot be ensured, and if it is more than the above, the sensitivity is low and the pixel peeling and hole diameter are larger than the design value. There may be a problem such as becoming.

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

The total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass based on 100% by mass of the solid content of the photosensitive coloring composition. If the total content of the photopolymerization initiator and the ultraviolet absorber is less than the above, the adhesion is weakened and pixel peeling occurs, and if it is more than the above, the sensitivity may be too high and the resolution may be deteriorated.

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-t-butylphenyl) -2H-benzotriazole, and octyl-3 [3-tert-butyl. -4-Hydroxy-5- (5-chloro-2H-benzotriazole-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H) -Benzotriazole-2-yl) phenyl] propionate mixture, 2- [2-hydroxy-
3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (
3-t butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy- 5'-t-octylphenyl) benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3- (2H-benzotriazol-2-yl)-(1,1-dimethyl) Ethyl) -4-hydroxy, C7-9 side chain and linear alkyl ester compounds, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, Examples thereof include 2- (2H-benzotriazole-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol.

More specifically, BASF's "TINUVIN P", "TINUVIN PS", "TINUVIN 109", "TINUVIN 234", "TINUVIN 326"
, "TINUVIN 328", "TINUVIN 329", "TINUVIN 360"
, "TINUVIN 384-2", "TINUVIN 900", "TINUVIN"
928 ”,“ TINUVIN 99-2 ”,“ TINUVIN 1130 ”,“ ADEKA STAB LA-29 ”manufactured by ADEKA,“ RUNA-93 ”manufactured by Otsuka Chemical Co., Ltd., and the like.

Examples of the triazine-based organic compound include 2- [4,6-di (2,4-kisilyl) -1,3,5-triazine-2-yl] -5-octyloxyphenol, 2- [4,6-bis. (2,4-Dimethylphenyl) -1,3,5-triazine-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropoxy] phenol, 2- (2,4-dihydroxyphenyl)- Reaction product of 4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl-glycidate ester, 2,4-bis "2-hydroxy-4-butoxyphenyl" -6- (2,4-dibutoxyphenyl) -1,3-5-triazine and the like can be mentioned.

More specifically, "KEMISORB 102" manufactured by Chemipro Kasei Co., Ltd. and "KEMISORB 102" manufactured by BASF Co., Ltd.
"TINUVIN 400", "TINUVIN 405", "TINUVIN 460",
"TINUVIN 477-DW", "TINUVIN 479", "TINUVIN 1"
577 ”,“ ADEKA STAB LA-46 ”manufactured by ADEKA,“ ADEKA STAB LA-F70 ”,“ CYASORB UV-1164 ”manufactured by Sun Chemical, and the like.

Examples of benzophenone-based organic compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulphonic acid-3 water temperature, and 2-hydroxy-4-n-. Examples thereof include octoxybenzophenone and 2,2-di-hydroxy-4-methoxybenzophenone.

More specifically, "KEMISORB 10" and "KEMISOR" manufactured by Chemipro Kasei Co., Ltd.
B 11 ”,“ KEMISORB 11S ”,“ KEMISORB 12 ”,“ KEMIS
ORB 111 ", Cipro Kasei Co., Ltd." SEESORB 101 "," SEESORB 10 "
7 ”,“ ADEKA STAB 1413 ”manufactured by ADEKA, etc. can be mentioned.

<Polymerization inhibitor>
The photosensitive composition of the present invention may contain a polymerization inhibitor in order to prevent the mask from being exposed to light by diffracted light during exposure. By adding a polymerization inhibitor, it is possible to obtain the effect of preventing the curing from proceeding outside the desired pattern by chain polymerization by photosensitization.

Examples of the polymerization inhibitor include catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, and 2-propylcatechol. , 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-tert-butyl catechol, 3-tert-butyl catechol, 4-tert- Alkyl catechol compounds such as butyl catechol, 3,5-di-tert-butyl catechol, 2-methyl resorcinol, 4-methyl resorcinol, 2-ethyl resorcinol, 4-ethyl resorcinol, 2-propyl resorcinol, 4-propyl resorcinol, Alkyl resorcinol compounds such as 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, 4-tert-butylresorcinol, methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, 2, Alkylhydroquinone compounds such as 5-di-tert-butylhydroquinone, phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine, phosphines such as trioctylphosphine oxide and triphenylphosphine oxide. Examples thereof include phosphite compounds such as oxide compounds, triphenylphosphite and trisnonylphenylphosphite, pyrogallol and fluoroglucin. The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass with respect to 100 parts by mass by weight of the coloring composition excluding the solvent. In this range, the effect of the polymerization inhibitor is increased, and the linearity of the taper, wrinkles of the coating film, pattern resolution and the like are improved.

<Antioxidant>
The photosensitive composition of the present invention may contain an antioxidant. The antioxidant is (to prevent the photopolymerization initiator and thermosetting compound contained in the red photosensitive composition from being oxidized and yellowed by the thermal process during thermosetting or ITO annealing, the transmittance of the coating film is high. In particular, when the colorant concentration of the coloring composition is high, the amount of the coating film cross-linking component is small, so that a high-sensitivity cross-linking component is used and the amount of the photopolymerization initiator is increased in order to take measures such as a thermal step. There is a phenomenon that the yellowing of the light becomes stronger.
Therefore, by including 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 catching function, or a peroxide decomposition function. Specifically, the antioxidant is a hindered phenol-based or a hindered amine-based compound. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, sulcylic acid ester-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used. Further, the antioxidant used in the present invention preferably does not contain a halogen atom.

Among these antioxidants, from the viewpoint of achieving both the transmittance and the sensitivity of the coating film, the ones preferable are hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Agents can be mentioned.

Examples of the hindered phenolic antioxidant include 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), and the like. 1,3,5-Tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di) -T-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-t-butyl-4- Nonylphenol, 2,2'-isobutylidene-bis- (4,6-dimethyl-phenol), 4,4'-butylidene-bis- (2-t-butyl-5-methylphenol), 2,2'-thio- Bis- (6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,2'thiodiethylbis- (3,5-di-t-butyl-4-hydroxyphenyl) )-Propionate, 1,1,3-tris- (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -butane, 2,2'-methylene-bis- (6- (1-methyl) -Cyclohexyl) -p-cresol), 2,4-dimethyl-6- (1-methyl-cyclohexyl) -phenol, N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydro) Phenol) and the like. In addition, oligomer-type and polymer-type compounds having a hindered phenol structure can also be used.
Specific examples include ADEKA Corporation's ADEKA STAB AO-20, AO-30, AO-40,
AO50, AO60, AO80, AO320, KEMINOX101 179, 76, 9425 manufactured by Chemipro Co., Ltd., IRGANOX1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057 manufactured by BASF Corporation. , 565, Sianox CY-1790, CY-2777 manufactured by Sun Chemical Co., Ltd. and the like.

Examples of hindered amine antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate. N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4) -Piperidyl) Amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (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-piperidyl) imino} Hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazin-2,4) -Diyl) {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-Hydroxyethyl) -4-hydroxy-2,2,6,6-polycondensate with tetramethylpiperidine, N, N'-4,7-tetrakis [4,6-bis {N-butyl-N -(1,2,2,6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazine-2-yl] -4,7-diazadecan-1,10-diamine and the like. In addition, oligomer-type and polymer-type compounds having a hindered amine structure can also be used.
As a specific example, ADEKA Corporation LA-52, LA-57, LA-63
P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, LA-502XP, KAMISTAB29, 62, 77, 29 manufactured by ChemiPro Kasei Co., Ltd. , 94, Tinuvin249 manufactured by BASF Co., Ltd., TINUVIN111FDL, 123, 144, 292, 5100, Siasorb UV-3346, UV-3259, UV-3853 manufactured by Sun Chemical Co., Ltd. and the like.

Phenyl antioxidants include tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenylisooctylphosphite, phenylisodecylphosphite, phenyldi (tridecyl) phosphite, diphenylisooctylphosphite, diphenylisodecyl. Phosphite, Diphenyltridecylphosphite, Triphenylphosphite, Tris (nonylphenyl) phosphite, 4,4'isopropyridene diphenolalkylphosphite, trisnonylphenylphosphite, trisdinonylphenylphosphite, tris (2) , 4-di-t-butylphenyl) phosphite, tris (biphenyl) phosphite, distearyl pentaerythritol diphosphite, di (2,4-di-t-butylphenyl) pentaerythritol diphosphite, di (nonyl) Phenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis (3-methyl-6-t-butylphenol) diphosphite, hexatridecyl 1,1,3- Tris (2-methyl-4-hydroxy-5-t-butylphenyl) butanetriphosphite, 3,5-di-t-butyl-4-hydroxybenzylphosphite diethyl ester, sodium bis (4-t-butylphenyl) Phosphite, Sodium-2,2-Methylene-bis (4,6-di-t-butylphenyl) -Phosphite, 1,3-bis (diphenoxyphosphonyloxy) -benzene, ethylbis phosphite (2, 4-Ditert-butyl-6-methylphenyl) and the like. In addition, oligomer-type and polymer-type compounds having a phosphite structure can also be used.
As a specific example, ADEKA Corporation ADEKA STAB PEP-36, PEP-8, HP-1
0, Adecastab 2112, 1178, 1500, C, 3013, TPP, IRGAFOS168 manufactured by BASF Corporation, HostanoxP-EPQ manufactured by Clariant Chemicals Co., Ltd. and the like.

Examples of sulfur-based antioxidants include 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and 2,4-bis [(octylthio) methyl]-. o-cresol, 2,4-bis [(laurylthio) methyl] -o-cresol, 2,2-bis {[3- (dodecylthio) -1-oxopropoxy] methyl} propane-1,3-diylbis [3- (Dodecylthio) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and the like. In addition, oligomer-type and polymer-type compounds having a thioether structure can also be used.
Specific examples include ADEKA STAB AO-412S and AO-503 manufactured by ADEKA Corporation, and KEMINOXPLS manufactured by Chemipro Kasei Co., Ltd.

As the benzotriazole-based antioxidant, oligomer-type and polymer-type compounds having a benzotriazole structure can be used.
As a specific example, ADEKA Corporation LA-29, LA-31RG, LA-
32, LA-36, -412S, KEMIPRO B71, 73, 74, 79, 279 manufactured by Chemipro Kasei Co., Ltd., TINUVIN PS manufactured by BASF Co., Ltd., 99-2, 384-2, 900, 928, 1130 and the like.

Examples of benzophenone-based antioxidants include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, and 2-hydroxy-4. -Octadecyloxybenzophenone, 2,2'dihydroxy-4-methoxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4 Examples thereof include −methoxy-5 sulfobenzophenone and 2-hydroxy-4-methoxy-2'-carboxybenzophenone. In addition, oligomer-type and polymer-type compounds having a benzophenone structure can also be used.
Specific examples include ADEKA Corporation's ADEKA STAB 1413 and Chemipro Kasei Co., Ltd.'s K.
EMISORB10, 11, 11S, 12, 111, UV-12 manufactured by Sun Chemical Co., Ltd., UV-329 and the like can be mentioned.

Examples of the triazine-based antioxidant include 2,4-bis (allyl) -6- (2-hydroxyphenyl) 1,3,5-triazine. In addition, oligomer-type and polymer-type compounds having a triazine structure can also be used.
Specific examples include ADEKA Corporation LA-46 and F70, KEMIPRO B102 manufactured by Chemipro Kasei Co., Ltd., TINUVIN400, 405, 460, 477, 479 manufactured by BASF Co., Ltd., and Siasorb UV-1164 manufactured by Sun Chemical Co., Ltd. ..

Examples of the salicylic acid ester-based antioxidant include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butyl phenyl salicylate. In addition, oligomer-type and polymer-type compounds having a sulcylic acid ester structure can also be used.

These antioxidants may be used alone or in admixture of two or more at any ratio as required.

The content of the antioxidant is more preferably 0.5 to 5.0% by mass based on 100% by mass of the solid content of the coloring composition because the transmittance, spectral characteristics, and sensitivity are good.

<Adhesion improver>
The photosensitive composition of the present invention may contain an adhesion improver such as a silane coupling agent in order to enhance the adhesion to the substrate. By improving the adhesion by the adhesion improver, the reproducibility of fine lines is improved and the resolution is improved.

Adhesion improvers include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-. (Meta) acrylic silanes such as methacryloxypropyltriethoxysilane and 3-acryloxipropyltrimethoxysilane 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3- Epoxysilanes such as glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane , N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) ) Aminosilanes such as propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-mercaptopropylmethyldimethoxysilane , Mercapts such as 3-mercaptopropyltrimethoxysilane, styryls such as p-styryltrimethoxysilane, ureids such as 3-ureidopropyltriethoxysilane, sulfides such as bis (triethoxysilylpropyl) tetrasulfide, Examples thereof include silane coupling agents such as isocyanates such as 3-isocyanoxide propyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the colorant in the coloring composition. It is more preferable because the effect is large within this range and the balance between adhesion, resolution and sensitivity is good.

<Leveling agent>
It is preferable to add a leveling agent to the photosensitive composition of the present invention for the purpose of improving the coatability of the composition on the transparent substrate and the drying property of the colored film. As the leveling agent, various surfactants such as silicone-based surfactants, fluorine-based surfactants, nonionic surfactants, and cationic surfactants (surfactants, anionic surfactants, etc.) can be used.
Examples of the silicone-based surfactant include a linear polymer composed of a siloxane bond and a modified siloxane polymer in which an organic group is introduced into a side chain or a terminal.
Specific examples include BYK-300, BYK-306, BYK-310, BYK-313, BYK-315N, BYK-320, BYK-322, BYK-323, BYK-330, BYK-331, BYK- made by Big Chemie. 333, BYK-342, BYK-345 / 346, BYK-347, BYK-348, BYK-349, BYK-370, BYK-377, BYK-378, BYK-3455, BYK-UV3510, BYK-3570, Toray. Dow Corning Co., Ltd., FZ-7001, FZ-7002, FZ-2110, FZ-2122, FZ-2123, FZ-2191, FZ-5609, Shin-Etsu Chemical Co., Ltd. X-22-4952, X-22- 4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, etc. Can be mentioned.

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain.
Specific examples include Surflon S-242 and S-243 manufactured by AGC Seimi Chemical Co., Ltd.
S-420, S-611, S-651, S-386, Megafuck F-253, F-477, F-551, F-552, F-555, F-558, F-560, manufactured by DIC Corporation. F-570, F-575, F-576, R-40-LM, R-41, RS-72-K, DS-21, Sumitomo 3M Ltd. FC-4430, FC-4432, Mitsubishi Materials Electronics Chemical Co., Ltd. Examples thereof include EF-PP31N09 manufactured by a company, EF-PP33G1, EF-PP32C1, and Futergent 602A manufactured by Neos Co., Ltd.

Nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristel ether, and polyoxyethylene octyldodecyl. Ether, polyoxyalkylene alkyl ether, polyoxyphenylenedistyrene phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyethylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl Ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan monolaurate, sorbitan esquioleate, poly Oxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene orbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, tetra Polyoxyethylene sorbit oleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol mooleate, polyoxyethylene hydrogenated castor oil, polyoxy Examples thereof include ethylene alkylamine, alkyl alkanolamide, alkyl betaine such as alkyl imidazoline and alkyl dimethylamino acetate betaine.
Specific examples include Kao Corporation's Emargen 103, Emargen 104P, Emargen 106, Emargen 108, Emargen 109P, Emargen 120, and Emargen 123.
P, Emargen 130K, Emargen 147, Emargen 150, Emargen 210P, Emargen 220, Emargen 306P, Emargen 320P, Emargen 350, Emargen 404, Emargen 408, Emargen 409PV, Emargen 420, Emargen 430, Emargen 705, Emargen 707 Emargen 1108, Emargen 1118S-70, Emargen 1135S-70, Emargen 1150S-60, Emargen 2020G-HA, Emargen 2025G, Emargen LS-106, Emargen LS-110, Emargen LS-114, Emargen MS-110, Emargen A-60 , Emargen A-90, Emargen B-66, Emargen PP-290, Latemuru PD-420, Latemuru PD-430, Latemuru PD-430S, Latemuru PD450, Leodor SP-L10, Leodor SP-P10, Leodor SP-S10V, Leodor SP-S20, Leodor SP-S30V, Leodor SP-O10V, Leodor SP-O30V, Leodor Super SP-L1, Leodor AS-10V, Leodor AO-10V, Leodor AO-15V, Leodor TW-L120, Leodor TW-L106 , Leo Doll TW-P120, Leo Doll TW-S120V, Leo Doll TW-L106V, Leo Doll TW-S320V, Leo Doll TW-O120V, Leo Doll TW-O106V, Leo Doll TW-IS399C, Leo Doll Super TW-L120, Leo Doll 430V, Leo Doll 440V, Leo Doll 460V, Leodor MS-50, Leodor MS-60, Leodor MO-60, Leodor MS-165V, Emanon 1112, Emanon 3199V, Emanon 3299V, Emanon 3299RV, Emanon 4110, Emanon CH-25, Emanon CH-40, Emanon CH- 60 (K), Amit 102, Amit 105, Amit 105A, Amit 302, Amit 320, Aminone PK-02S, Aminone L-02, Homogenol L-95, ADEKA Corporation ADEKA PLRONIC L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, ADEKA PLRONIC TR-701, 702, 704, 913R and the like can be mentioned.

Examples of the cationic surfactant include alkylquaternary ammonium salts such as alkylamine salts, lauryltrimethylammonium chlorides, stearyltrimethylammonium chlorides, and cetyltrimethylammonium chlorides, and ethylene oxide adducts thereof.
Specific examples include Acetamine 24, 26 manufactured by Kao Corporation, Cotamine 24P, 86P Conch, KP341 manufactured by Shin-Etsu Chemical Co., Ltd., and (meth) acrylic acid-based (co) polymer Polyflow No. manufactured by Kyoeisha Chemical Co., Ltd. 75, No. 90, No. 95 and the like can be mentioned.

Examples of anionic surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalin sulfonate, sodium alkyldiphenyl ether disulfonate, and monoethanolamine lauryl sulfate. , Triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate and the like.
Specific examples include Futergent 100 and 150 manufactured by Neos Co., Ltd., Adeka Hope YES-25 manufactured by ADEKA Corporation, Adeka Call TS-230E, PS-440E, EC-8600 and the like.

As the surfactant used in the leveling agent, only one type 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 based on the total solid content of the composition of the present invention. It is preferably 0.005 to 1.0% by mass. Within this range, the balance between the coatability of the coloring composition, the pattern adhesion, and the transmittance is good.
The photosensitive composition of the present invention may contain only one type of surfactant, or may contain two or more types of surfactants. When two or more types are included, the total amount is preferably in the above range.

<Amine compounds>
Further, the photosensitive composition of the present invention may contain an amine compound having a function of reducing dissolved oxygen. Examples of such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminobenzoate. Examples thereof include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

<Manufacturing method of colored dispersion>
In the photosensitive coloring composition contained in the present invention, a colorant is placed in a colorant carrier such as a dispersant or a binder resin and / or a solvent, preferably with a dispersion aid, in a kneader, two roll mills, or three. It can be produced based on a colored dispersion produced by finely dispersing using various dispersion means such as a roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annual bead mill, or an attritor. At this time, two or more kinds of colorants and the like may be dispersed in the colorant carrier at the same time, or those dispersed separately in the colorant carrier may be mixed. If the colorant such as a dye has high solubility, specifically, if the colorant has high solubility in the solvent to be used, is dissolved by stirring, and no foreign matter is confirmed, fine dispersion may not be performed. In the present invention, it is preferable to disperse the colorant (A) by using the resin type dispersant (B) when producing the colorant dispersion.

When used as a photosensitive coloring composition (resist material) for a color filter, it can be prepared as a solvent-developing type or alkali-developing type coloring composition. The solvent-developed or alkaline-developed coloring composition includes the colorant dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and if necessary, a solvent, other dispersion aids, and additives. Etc. can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added later to the prepared coloring composition.

<Dispersion aid>
When the colorant is dispersed in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, or a surfactant can be appropriately contained. Since the dispersion aid has a great effect of preventing the reaggregation of the colorant after dispersion, the coloring composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has lightness, contrast, and storage stability. The sex becomes good.

[Resin type dispersant]
The photosensitive composition of the present invention contains the above-mentioned resin type dispersant (B), but may also contain a conventionally known resin type dispersant.
The resin-type dispersant has a colorant-affinitive portion having a property of adsorbing to the additive colorant and a portion compatible with the colorant carrier, and is adsorbed on the additive colorant and dispersed on the colorant carrier. It works to stabilize. Specifically, as the resin type dispersant, polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products of these, amides and salts thereof formed by the reaction of poly (lower alkyleneimine) with polyester having a free carboxyl group. Oily dispersants such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Water-soluble resins, water-soluble polymer compounds, polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide-added compounds, phosphate esters, etc. are used, and these can be used alone or in admixture of two or more. However, it is not necessarily limited to these.

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

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, manufactured by Big Chemie Japan. 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, Bykuman, etc. 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, manufactured by BASF. 4,300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. Ajinomoto Fine-Techno's Ajispa-PA111, PB711, PB821, PB822, PB824 and the like are preferable.

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

≪Resin type dispersant (S1) ≫
The resin-type dispersant (S1) can be produced by a known method such as WO2008 / 007776, Japanese Patent Application Laid-Open No. 2008-029901, and Japanese Patent Application Laid-Open No. 2009-155406. The polymer (p) having a hydroxyl group is preferably a polymer having a hydroxyl group at the terminal. For example, the ethylenically unsaturated monomer (r) is polymerized in the presence of the compound (q) having a hydroxyl group. It can be obtained as a polymer. The compound (q) having a hydroxyl group is preferably a compound having a hydroxyl group and a thiol group in the molecule. Since the number of terminal hydroxyl groups is preferably plural, a compound (q1) having two hydroxyl groups and one thiol group in the molecule is preferably used.

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

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

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

[Dye derivative]
As the dye derivative used in the present invention, a known dye derivative having an acidic group, a basic group, a neutral group or the like in the organic dye residue can be used. For example, compounds having acidic functional groups such as sulfo group, carboxy group and phosphoric acid group and amine salts thereof, compounds having basic functional groups such as sulfonamide group and tertiary amino group at the terminal, phenyl group and phthalimide. Examples thereof include compounds having a neutral functional group such as an alkyl group. Japanese Patent Application Laid-Open No. 63-305173, Japanese Patent Application Laid-Open No. 57-15620, Japanese Patent Application Laid-Open No. 59-40172, Japanese Patent Application Laid-Open No. 63-17102, Japanese Patent Application Laid-Open No. 5-9469, Japanese Patent Application Laid-Open No. 2001-335717, Japanese Patent Application Laid-Open No. 63-305173 Kai 2003-128669, JP2004-091497, 2007-156395, 2008-094873, 2008-094986, 2008-095007, 2008 -195916, Japanese Patent No. 4585781, Japanese Patent Application Laid-Open No. 2006-291194, Japanese Patent Application Laid-Open No. 2007-226161, Japanese Patent Application Laid-Open No. 2007-314681, Japanese Patent Application Laid-Open No. 2007-314785, Japanese Patent Application Laid-Open No. 2012-226110. , Japanese Patent Application Laid-Open No. 2017-165820, Japanese Patent Application Laid-Open No. 2005-181383, and the like. In these documents, the dye derivative may be described as a derivative, a pigment derivative, a pigment dispersant, or simply a compound, but the above-mentioned organic dye residue includes an acidic group, a basic group, a neutral group, or the like. A compound having a functional group of is synonymous with a dye derivative. In addition, these can be used alone or in combination of two or more.

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

By adding a dye derivative to the pigment and performing dispersion treatment such as wet dispersion using two rolls, three rolls, and beads, the dye derivative is adsorbed on the pigment surface and the pigment surface is polar, and the resin type dispersant is adsorbed. Is promoted, compatibility with pigments, pigment derivatives, resin-type dispersants, solvents, and other additives is improved, and dispersion stability and viscosity stability over time when made into a coloring composition or a coloring curable composition are improved. do. Further, by improving the compatibility, the coating film is excellent in stability over time when the color-curable composition is applied to glass, and the waiting time from application to exposure of the color-curable composition (PCD: Post Coating Delay). The stability and characteristic dependence of the pattern shape and the like with respect to the waiting time (PED: Post Exposure Day) from exposure to heat treatment and the line width sensitivity stability are improved. Furthermore, variations in development time and development residues are suppressed.

[Surfactant]
Examples of the surfactant include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalin sulfonate, sodium alkyldiphenyl ether disulfonate. , Monoethanolamine lauryl sulfate, Triethanolamine lauryl sulfate, Ammonium lauryl sulfate, Monoethanolamine stearate, Monoethanolamine styrene-acrylic acid copolymer, Anionic surfactants such as polyoxyethylene alkyl ether phosphate; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; alkyl Chaotic surfactants such as quaternary ammonium salts and their ethylene oxide adducts; alkyl betaines such as alkyldimethylaminoacetic acid betaine and amphoteric surfactants such as alkylimidazoline, which may be used alone or in combination of two or more. They can be mixed and used, but are not necessarily limited to these.

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

<Removal of coarse particles>
The colored dispersion or photosensitive composition of the present invention has coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm, by means such as centrifugation, filtration with a sintering filter or a membrane filter. It is preferable to remove the above coarse particles and mixed dust. As described above, it is preferable that the coloring composition does not substantially contain particles having a size of 0.5 μm or more. More preferably, it is 0.3 μm or less.

The filter can be used without particular limitation as long as it has been conventionally used for filtration purposes and the like. For example, fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg, nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP) (high density, ultrahigh molecular weight). (Including those) and the like. Among these materials, polypropylene (including high-density polypropylene) and nylon are preferable.
The pore size of the filter is preferably about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, and more preferably about 0.05 to 0.5 μm. Within this range, fine foreign matter can be reliably removed. It is also preferable to use a fibrous filter medium. Examples of the fibrous filter medium include polypropylene fiber, nylon fiber, glass fiber and the like. Specifically, SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.) and SHPX type series manufactured by Roki Techno Co., Ltd. A filter cartridge (such as SHPX003) can be used.

When using filters, different filters may be combined. At that time, the filtration with the first filter may be performed only once or twice or more.
Further, first filters having different pore diameters within the above-mentioned range may be combined. For the hole diameter here, the nominal value of the filter manufacturer can be referred to. As a commercially available filter, for example, select from various filters provided by Nippon Pole Co., Ltd. (DFA4201NXEY, etc.), Advantech Toyo Co., Ltd., Nippon Integris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), KITZ Micro Filter Co., Ltd., etc. can do.

<Color filter>
Next, the color filter of the present invention will be described.
The color filter of the present invention includes a red filter segment, a green filter segment, and a blue filter segment. Further, the color filter may further include a magenta color filter segment, a cyan color 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>
The color filter can be manufactured by a printing method or a photolithography method.
The formation of the filter segment by the printing method can be patterned only by repeating printing and drying of the coloring composition prepared as the printing ink, and therefore, as a manufacturing method of the color filter, it is excellent in mass productivity at low cost. Further, with the development of printing technology, it is possible to print a fine pattern having high dimensional accuracy and smoothness. In order to perform printing, it is preferable that the composition is such that the ink does not dry or solidify on the printing plate or on the blanket. It is also important to control the fluidity of the ink on the printing machine, and the viscosity of the ink can be adjusted with a dispersant or an extender pigment.

When the filter segment is formed by the photolithography method, the coloring composition prepared as the solvent-developing type or alkali-developing type colored resist material is applied onto a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. By the method, the coating is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed (irradiated with radiation) through a mask having a predetermined pattern provided in contact with or without contact with the film. Then, after immersing in a solvent or an alkaline developer or spraying the developer with a spray or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to manufacture a color filter. be able to. Further, in order to promote the polymerization of the colored resist material, heating at 80 ° C. to 250 ° C. can be applied as needed. According to the photolithography method, a color filter having higher accuracy than the above printing method can be manufactured.

At the time of development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as the alkaline developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant can be added to the developing solution.
In order to increase the exposure sensitivity, the colored resist is applied and dried, and then a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film for preventing polymerization inhibition by oxygen. , Exposure can also be performed.

The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an inkjet method or the like in addition to the above methods, and the coloring composition of the present invention can be used in any of the methods. The electrodeposition method is a method of manufacturing a color filter by electrodepositing each color filter segment on the transparent conductive film by electrophoresis of colloidal particles using the transparent conductive film formed on the substrate. .. Further, the transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and the filter segment is transferred to a desired substrate.

A black matrix can be formed in advance before each color filter segment is formed on the transparent substrate or the 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 is used, but the black matrix is not limited thereto. It is also possible to form a thin film transistor (TFT) on the transparent substrate or the reflective substrate in advance, and then form each color filter segment. Further, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention, if necessary.

In the color filter of the present invention, a sealant is used to bond the liquid crystal to the opposing substrate, liquid crystal is injected from the injection port provided in the seal portion, the injection port is sealed, and a polarizing film or a retardation film is attached to the substrate as necessary. A color liquid crystal display device is manufactured by sticking it on the outside of the surface. This color liquid crystal display device is twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), optical convensend bend (OCB). It can be used in the liquid crystal display mode in which colorization is performed using a color filter such as).

In addition to the color liquid crystal display device, the color filter of the present invention can also be used for manufacturing a color solid-state image sensor, an organic EL display device, a quantum dot display device, electronic paper, and the like.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded. In the examples and comparative examples, "parts" and "%" mean "parts by mass" and "% by mass".

(Weight average molecular weight of resin)
The weight average molecular weight (Mw) of the resin is polystyrene-equivalent measured using a TSKgel column (manufactured by Tosoh Corporation) and a GPC (manufactured by Tosoh Corporation, HLC-8320 GPC) equipped with an RI detector and using THF as a developing solvent. Weight average molecular weight (Mw).

(Acid value of resin)
The resin acid value is a value obtained by converting the measured acid value (mgKOH / g) into a solid content in accordance with the potentiometric titration method of JIS K 0070.

<Manufacturing of resin type dispersant (B)>
(Resin type dispersant (B-1))
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 8 parts of 3-mercapto-1,2-propanediol, 12 parts of pyromellitic anhydride, 80 parts of propylene glycol monomethyl ether acetate (PGMAc), and a catalyst. As a result, 0.2 part of monobutyltin oxide was charged, replaced with nitrogen gas, and then reacted at 120 ° C. for 5 hours (first step). It was confirmed by measuring the acid value that 95% or more of the acid anhydride was half-esterified. Next, 30 parts of methyl methacrylate (MMA), 10 parts of t-butyl acrylate (tBA), 10 parts of ethyl acrylate (EA), 5 parts of methacrylic acid (MAA), 10 parts of benzyl methacrylate (BzMA), 2-hydroxyethyl methacrylate. 35 parts of (HEMA) was charged, the inside of the reaction vessel was heated to 80 ° C., 1 part of 2,2'-azobis (2,4-dimethylvaleronitrile) was added, and the reaction was carried out for 12 hours (second step). .. It was confirmed by solid content measurement that 95% had reacted. Then, the inside of the flask was replaced with air, 38.0 parts of 2-methacryloyloxyethyl isocyanate (MOI) and 0.1 part of hydroquinone were charged, and the reaction was carried out at 70 ° C. for 4 hours (third step). After confirming the disappearance of the peak of 2270 cm-1 based on the isocyanate group by IR, the reaction solution is cooled and the solid content is adjusted with PGMAc to prepare a solution of the resin type dispersant (B-1) having a solid content of 40%. Obtained. 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 to B-23))
Synthesis was carried out in the same manner as the resin-type dispersant (B-1) except that the raw materials and the charged amounts shown in Tables 1 and 2 were used, and the resin-type dispersants (B-2) to (B-2) having a solid content of 40% ( A solution of B-22) was obtained.

BTDA: 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride MMA: methyl methacrylate tBA: t-butyl acrylate EA: ethyl acrylate MAA: BzMA methacrylate: benzyl methacrylate HEMA: 2-hydroxyethyl methacrylate HPMA: 2-Hydroxypropyl Methacrylate FM-3: Terminal Hydroxy Group Polycaprolactone Modified Methacrylate (Dycel Chemical Co., Ltd .: Praxel FM-3)
MOI: 2-methacryloyloxyethyl isocyanate (Showa Denko: Calends MOI)
AOI: 2-acryloyloxyethyl isocyanate (Showa Denko: Karenz AOI) BEI: 1,1-bis (acryloyloxymethyl) ethyl isocyanate (Showa Denko: Karenz BEI)

<Manufacturing of binder resin>
(Acrylic resin solution 1)
100 parts of propylene glycol monomethyl ether acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer in a separable 4-neck flask, and heated to 120 ° C. while injecting nitrogen gas into the vessel. At temperature, a mixture of 5.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 41.0 parts of dicyclopentanyl methacrylate and 1.0 part of azobisisobutyronitrile was added dropwise from a dropping tube over 2.5 hours for polymerization. The reaction was carried out.
Next, the inside of the flask was replaced with air, 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 17.0 parts of acrylic acid, and the reaction was continued at 120 ° C. for 5 hours, and the solid content acid value = 0. The reaction was terminated when the temperature reached 0.8, and a resin solution having a weight average molecular weight of about 12,000 (measured by GPC) was obtained.
Further, 30.4 parts of tetrahydrophthalic anhydride and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 4 hours, and propylene glycol monomethyl ether acetate was added so that the non-volatile content became 40% to prepare an acrylic resin solution 1. ..

<Manufacturing of colorant (A)>
<Manufacturing of refined red pigment (PR254-1)>
Diketopyrrolopyrrole red pigment C.I. I. Pigment Red 254 (BASF's "Irgajin RedL 3630"), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8000 parts of warm water, stirred for 2 hours while heating at 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours. , Diketopyrrolopyrrole-based finely divided red pigment (PR254-1) was obtained.

<Manufacturing of refined yellow pigment (PY139-1)>
Yellow pigment C.I. I. Pigment Yellow 139 (BASF's "Pariotol Yellow D1819"), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8000 parts of warm water, stirred for 2 hours while heating at 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours. , A finely divided yellow pigment (PY139-1) was obtained.

<Manufacturing of refined blue pigment (PB15: 6-1))>
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (“LIONOL BLUE ES” manufactured by Toyo Color Co., Ltd., specific surface area 60 m2 / g) 200 parts, sodium chloride 1400 parts, and diethylene glycol 360 parts were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), 80 parts. Kneaded at ° C for 6 hours. Next, this kneaded product was put into 8000 parts of warm water, stirred for 2 hours while heating at 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours. , Phthalocyanine-based finely divided blue pigment (PB15: 6-1) was obtained.

<Manufacturing of finely divided purple pigment (PV23-1)>
Dioxazine-based purple pigment C.I. I. Pigment Violet 23 (“LIONOGEN VIOLET RL” manufactured by Toyo Color Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8000 parts of warm water, stirred for 2 hours while heating at 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours. , Dioxazine-based purple finely divided purple pigment (PV23-1) was obtained.

<Manufacturing of refined green pigment (PG58-1)>
Phthalocyanine-based green pigment C.I. I. Pigment Green 58 (“FASTOGEN GREEN A110” manufactured by DIC Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8000 parts of warm water, stirred for 2 hours while heating at 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours. , Phthalocyanine-based finely divided green pigment (PG58-1) was obtained.

<Manufacturing of refined yellow pigment (PY150-1))>
Nickel complex yellow pigment C.I. I. Pigment Yellow 150 (“E-4GN” manufactured by LANXESS), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8000 parts of warm water, stirred for 2 hours while heating at 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours. , A nickel complex-based finely divided yellow pigment (PY150-1) was obtained.

<Manufacturing of refined yellow pigment (PY185-1))>
As a yellow colorant, C.I. I. 200 parts of Pigment Yellow 185 (BASF "Pariotor Yellow L 1155"), 1000 parts of sodium chloride, and 100 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 100 ° C. for 6 hours. Next, this kneaded product was put into 5 liters of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. , Obtained a yellow colorant (PY185-1)

<Manufacturing method of salt-forming compound (V)>
Follow the procedure below to C.I. I. A salt-forming compound (V) composed of Acid Red 289 and tristearyl monomethylammonium chloride, which is a quaternary ammonium salt compound, was prepared. To make a 5% aqueous solution, C.I. I. Dissolve 10 parts of Acid Red 289 in 200 parts of water, heat to 30-50 ° C, and then dissolve 5.5 parts of tristearyl monomethylammonium chloride in a 5% solution of methanol / water = 20/80. Then, it was dropped little by little. After dropping the tristearyl monomethylammonium chloride solution, the mixture was stirred at 30 to 50 ° C. for 3 hours. After allowing to cool to room temperature with stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing water with a dryer. I. Salt-forming compound (V) of acid red 289 and tristearyl monomethylammonium chloride
I got 8 copies.

<Manufacturing method of salt-forming compound-containing resin solution (SV)>
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 5.0 μm filter to prepare a salt-forming compound-containing resin solution (SV).
Salt compound (V): 8.0 parts Cyclohexanone: 92.0 parts

<Dye derivative>
Dye derivative A ... Compound C described in JP-A-2007-314681.
Dye derivative B ... General formula 31 described in JP-A-2006-291194.
Dye derivative C ... Compound iii described in JP-A-2017-165820
Dye Derivative D ... Derivative 51 described in JP-A-2005-181383.
<Manufacturing of colored dispersion>
(Coloring Composition D-1)
The following mixture is stirred and mixed so as to be uniform, and then dispersed for 5 hours with an Eiger mill (“Mini model M-250MKII” manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The colored composition (D-1) was prepared by filtering with a filter.
Micronized pigment (PR254-1): 13.3 parts Dye derivative A: 0.7 parts Dye derivative B: 0.7 parts Resin type dispersant (B-1) solution: 13.0 parts Propylene glycol monomethyl ether acetate ( PGMAC): 72.2 copies

(Coloring Compositions D-2 to 65)
(Coloring compositions D-2 to 65) were prepared in the same manner as the coloring composition D-1 except that the colorant, the dye derivative, and the resin-type dispersant solution were changed to the compositions shown in Tables 3 to 9.

<Manufacturing of photosensitive coloring compositions for color filters>
[Examples 101-121, 201-209, 301-306 and Comparative Examples 101-104, 201-206, 301-304] (RR-1-26, RG-1-15, RB-1-10)
Each material was mixed and stirred at the formulation ratios shown in Table 10 and filtered through a 1 μm filter to obtain a photosensitive coloring composition of each color.

The abbreviations in Table 10 are shown below.

Photopolymerization Initiator C1: 2-Methyl-1- [4- (Methylthio) Phenyl] -2-morpholinopropan-1-one (BASF's "Irgacure 907")
-Photopolymerization initiator C2: (oxime ester type): ethane-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl], 1- (O-acetyl) Oxime) (BASF "Irgacure OXE02")
-Photopolymerizable compound E1: Dipentaerythritol hexaacrylate ("Aronix M-402" manufactured by Toagosei Co., Ltd.)
-Organic solvent: Propylene glycol monomethyl ether acetate

<Evaluation of photosensitive coloring composition for color filters>
The obtained photosensitive coloring composition was evaluated by the following method. The results are shown in Table 11.

[Viscosity and Viscosity Stability of Photosensitive Coloring Composition]
The initial viscosity of the obtained photosensitive coloring composition at 25 ° C. was measured using a viscometer TV22 manufactured by Toki Sangyo Co., Ltd. In addition, the viscosity after accelerating at 40 ° C. for 1 month was measured to calculate the viscosity increase rate. The evaluation was made according to the following criteria.
⊚: Initial viscosity is 10.0 Pa · s or less and viscosity increase with time is less than 40% 〇: Initial viscosity is 10.0 Pa · s or less and viscosity increase with time is 40% or more ×: Initial viscosity is 10. 0 Pa · s or more,

[Pattern formation of filter segment]
The obtained photosensitive coloring composition was applied to a glass substrate of 10 cm × 10 cm by a spin coating method, and then heated in a clean oven at 70 ° C. for 5 minutes to remove the solvent to obtain a coating film of about 2 μm. .. Next, the substrate was cooled to room temperature, and then exposed using an ultra-high pressure mercury lamp at an exposure amount of 50 mJ / cm ² through a photomask having a stripe pattern having a width of 100 μm (pitch 200 μm) and a width of 25 μm (pitch 50 μm). Then, this substrate was spray-developed with an aqueous sodium carbonate solution at 23 ° C., washed with ion-exchanged water, air-dried, and heated in a clean oven at 230 ° C. for 20 minutes. The spray development was carried out for the coating film with each photosensitive coloring composition in the shortest time during which a pattern could be formed without any development residue, and this was set as the 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 a predetermined chromaticity]
When forming the filter segments by the above method, the rotation speed of the spin coat was appropriately changed to form a plurality of filter segments having different film thicknesses. The chromaticity was measured with a microspectrophotometer (“OSP-SP100” C light source manufactured by Olympus Optical Co., Ltd.). From the measured values, the film thickness of the red photosensitive coloring composition is x = 0.655, the film thickness of the green photosensitive coloring composition is y = 0.614, and the blue photosensitive. In the case of the coloring composition, the film thickness at which y = 0.049 was calculated. The calculated film thickness was used for evaluation according to the following criteria.
⊚: Film thickness is 1.2 μm or more and less than 1.8 μm 〇: Film thickness is 1.8 μm or more and less than 2.2 μm ×: Film thickness is 2.2 μm or more

[Resolution evaluation]
The resolvability of the pattern of the filter segment formed by the above method at the 25 μm photomask portion was visually evaluated using an optical microscope. Poor resolution means that adjacent stripe patterns are connected or chipped. The evaluation ranks are as follows.
◎: Stripe pattern is completely independent and no residue is seen between lines 〇: Stripe pattern is completely independent, but residue is seen between lines △: Adjacent stripe pattern is partially connected ×: Adjacent stripe patterns are connected

[Linearity evaluation]
The pattern of the filter segment formed by the above method at the 100 μm photomask portion was observed and evaluated using an optical microscope. The evaluation ranks are as follows. Note that C and D are levels that are difficult to use.
S: Very good linearity A: Good linearity B: Generally good linearity and usable level C: Partially poor linearity and difficult to use D: Poor linearity

[Dimensional stability evaluation]
The line width of the pattern on the 100 μm photomask portion of the substrate patterned with the exposure amounts of 30 ^{mJ / cm 2} and 50 mJ / cm ^{2 was measured using an optical microscope.} Was calculated the increase in line width when the exposure 50 mJ / cm ² with respect to the line width when the exposure 30 mJ / cm ^2. The smaller the amount of increase, the better the dimensional stability, and if the amount of increase was less than 3 μm, it was evaluated as a usable level. That is, C and D are difficult to use.
S: Increase amount is less than 1 μm
A: Increase amount is 1 μm or more and less than 2 μm
B: Increase amount is 2 μm or more and less than 3 μm
C: Increase amount is 3 μm or more and less than 5 μm
D: Increase amount is 5 μm or more

[Development stability evaluation]
At the time of spray development, the pattern film thickness of the filter segments formed by developing at twice the appropriate time was compared with the pattern film thickness formed by developing at the appropriate development time as a reference. The evaluation ranks are as follows, and those having a film thickness difference of 25% or less were regarded as usable levels.
⊚: Film thickness difference within 15% ○: Film thickness difference exceeds 15% and within 25%
Δ: Film thickness difference exceeds 25% and is within 40% ×: Film thickness difference exceeds 40%. Or, chipping or peeling has occurred.

As shown in Table 11, the filter segments formed by using the photosensitive coloring compositions of Examples 101-121, 201-209, and 301-306 using the resin-type dispersant (B) of the present application are Comparative Examples. Compared with the filter segments formed using 101-104, 201-206, 301-304, the resolution, development stability, linearity and dimensional stability are good, and the pattern shape shows better characteristics. rice field.
Further, it is more excellent that the proportion of one or more ethylenically unsaturated monomers selected from the ethylenically unsaturated monomer (c) having a hydroxyl group is 35% to 100%, more preferably 38% to 60%. It was clarified that the pattern shape can be formed. Further, the photosensitive coloring composition produced by using the resin type dispersant B-22 has a high viscosity and is difficult to use. Further, those using the resin type dispersants B-14, B-15, B-16, and B-22 had good initial viscosities and were practical, but thickening with time was observed.
Further, the double bond equivalent Z of the side chain of the resin type dispersant (B) calculated as ((c) weight + (d) weight) / (number of moles of (meth) acryloyl group in (d)) is 300 to The resins (B-1) to (B-7) and (B-10) to (B-19) at 600 g / mol showed excellent properties in a good pattern shape as compared with those that did not. Further, the content of the carboxyl group-containing ethylenically unsaturated monomer in the ethylenically unsaturated monomer (c) is 2.5 to 10.0% by mass, more preferably 2.5% to 5%. It showed excellent resolution. It was also revealed that the photosensitive coloring composition in which the photopolymerization initiator (C) is C2 exhibits excellent dimensional stability in combination with the resin-type dispersant (B) described in the present patent.
Further, in RR-20, which is a comparative example in which the content of the colorant is as high as 40% or more, the patterning characteristics are further deteriorated as compared with RR-25 in which the content of the colorant is low, which makes it more difficult to use. However, as confirmed by RR-3 and the like, even in the photosensitive coloring composition having a high colorant content of 40% or more according to the present invention, the photosensitive coloring composition RR-24 having a low colorant content. It was revealed that the patterning characteristics were as good as those of the above.

<Making 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 onto the substrate with a spin coater at x = 0.655 and y = 0.
It was applied so as to be 325 to form a colored film. The coating film was irradiated with ultraviolet rays of ^{50 mJ / cm 2} using an ultra-high pressure mercury lamp via a photomask.
Next, the unexposed portion was removed by spray development with an alkaline developer consisting of a 0.2 mass% sodium carbonate aqueous solution, washed with ion-exchanged water, and the substrate was heated at 220 ° C. for 20 minutes to obtain a red filter segment. Was formed. By the same method, the blue photosensitive coloring composition (RB-1) of the present invention is adjusted so that the green photosensitive coloring composition (RG-1) of the present invention has x = 0.327 and y = 0.614. Using 1), a green filter segment and a blue filter segment were formed so that 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 could be produced.

Claims (3)

A photosensitive coloring composition for a color filter containing a colorant (A), a resin-type dispersant (B), a photopolymerization initiator (C), an organic solvent (D), and a polymerizable compound (E).
The resin-type dispersant (B) contains 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 acid anhydride and / or trimellitic acid anhydride. In the presence of the reaction product of, the hydroxyl group of the hydroxyl group-containing polymer obtained by polymerizing the ethylenically unsaturated monomer (c) containing the hydroxyl group-containing ethylenically unsaturated monomer (b) and one isocyanate group. A resin obtained by reacting with an isocyanate group of compound (d) having one or more (meth) acryloyl groups.
The content of the structural unit derived from the hydroxyl group-containing ethylenically unsaturated monomer (b) is 35% by mass or more and 80% by mass or less with respect to the total amount of the structural unit derived from the ethylenically unsaturated monomer (c). And
The content of the colorant (A) is 40% by mass or more with respect to the total solid content of the photosensitive coloring composition for a color filter.
A photosensitive coloring composition for a color filter, wherein the photopolymerization initiator (C) contains an oxime ester compound. The content of the structural unit derived from the hydroxyl group-containing ethylenically unsaturated monomer (b) in the resin type dispersant (B) is relative to the total amount of the structural unit derived from the ethylenically unsaturated monomer (c). The photosensitive coloring composition for a color filter according to claim 1, which is 38% by mass or more and 60% by mass or less. A color filter comprising a filter segment formed from the photosensitive coloring composition for a color filter according to claim 1 or 2 on a substrate.