JP2019139250A - Photosensitive resin composition for color filter, and color filter - Google Patents

Abstract

To provide a photosensitive coloring composition for color filter excellent in various patterning characteristics, viscosity stability, dimensional stability and linearity, and a high-quality color filter using the coloring composition.SOLUTION: A photosensitive coloring composition for color filter contains a resin type dispersion agent that is a resin formed by reacting a hydroxyl group of a hydroxyl group-containing polymer obtained by polymerizing ethylenically unsaturated monomers (c) including a hydroxyl group-containing ethylenically unsaturated monomer (b), and an isocyanate group of a compound (d) having one isocyanate group and one or more (meth)acryloyl groups in the presence of a reaction product of a hydroxyl group of a compound (a) having two hydroxyl groups and one thiol group in a molecule and an acid anhydride group of a pyromellitic acid anhydride and/or trimellitic acid anhydride in the molecule, where a content of the hydroxyl group-containing ethylenically unsaturated monomer (b) is 35 mass% or more and 80 mass% or less to the total amount of the ethylenically unsaturated monomer (c).SELECTED DRAWING: None

Description

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

The color filter is formed by arranging two or more kinds of fine band-like filter segments having different hues on a transparent substrate such as a glass substrate so as to be parallel to each other (in a stripe shape) or cross each other, or Two or more kinds of fine filter segments having different values are arranged so as to be sequentially arranged in each of the vertical direction and the horizontal direction. The filter segments have small dimensions of several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue.
At present, as a method for producing a color filter, a method called a pigment dispersion method in which a pigment having excellent various resistances such as light resistance and heat resistance is used as a colorant has become 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 with a pattern corresponding to a filter segment of a certain color. Subsequently, the unexposed part of this coating film is removed by development, and then a treatment such as heating is performed as necessary. Thereby, a filter segment pattern of the first color is obtained. Then, by performing the same operation as this, filter segment patterns of other colors are formed, and the color filter is completed.

  In recent years, high color reproduction of displays has become an important trend. Although high color reproduction of a display is mainly focused on improving the color reproducibility of the backlight, it is necessary to use a very dark color for the color filter in order to improve the color reproducibility. In such a case, in the exposure process for forming the color filter pattern, the amount of light reaching the bottom of the coating film becomes weak, so photocuring tends to be insufficient, and a pattern with a desired shape cannot be obtained. To do.

  Specifically, although the dimension of the pattern obtained in the color filter manufacturing process is required to have a dimensional stability that can be accommodated within a certain variation when the exposure amount in the exposure process is varied, the photosensitive coloring composition is required. In the photosensitive coloring composition that realizes high color reproduction, such dimensional stability tends to deteriorate. Similarly, in the 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 a substrate. In patent document 3, the stability of the pattern dimension in the low exposure amount is implement | achieved by adding the polymer of a specific structure to a photosensitive composition. In Patent Document 4, dimensional stability is achieved by using a polymerization initiator having a specific structure. In patent document 5, the dimensional stability with respect to image development is ensured by using a thiol type compound. However, the high dimensional stability and linearity required for color filters today are not fully achieved, and further improvements are needed.

JP 2013-254047 A JP 2013-073115 A JP 2012-108227 A JP 2011-002796 A JP 2010-039475 A

  The present invention has been made in view of the above circumstances, and various patterning characteristics (resolution, linearity, dimensional stability, development stability) required for a photosensitive coloring composition and a photosensitive coloring composition. It aims at providing the photosensitive coloring composition which can implement | achieve high dimensional stability and linearity, satisfy | filling the viscosity stability of a thing, and the color filter manufactured from the photosensitive coloring composition.

  As a result of intensive studies, the present inventors have found that the hydroxyl group of the compound (a) having two hydroxyl groups and one thiol group in the molecule, pyromellitic anhydride and / or trimellitic anhydride 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 a reaction product of It is a resin obtained by reacting one isocyanate group and an isocyanate group of a 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 that is 35 to 80% by mass with respect to the total amount of the polymerizable unsaturated monomer (c) has high dimensional stability and linearity as described above. I found out that it could be realized.

<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) is a hydroxyl group of the compound (a) having two hydroxyl groups and one thiol group in the molecule, and pyromellitic anhydride and / or trimellitic anhydride acid anhydride. And a hydroxyl group of a hydroxyl group-containing polymer obtained by polymerizing the ethylenically unsaturated monomer (c) including the hydroxyl group-containing ethylenically unsaturated monomer (b) in the presence of the reaction product of A resin obtained by reacting an isocyanate group and an isocyanate group of a compound (d) having one or more (meth) acryloyl groups, and containing a structural unit derived from a hydroxyl group-containing ethylenically unsaturated monomer (b) Amount to ethylenically unsaturated monomer (c) Or less 80 wt% or more 35 wt% relative to the total amount of structural units come for a color filter photosensitive coloring composition.

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

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

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

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

<6> A color filter comprising a filter segment formed on the substrate from the photosensitive coloring composition for a color filter.

  By using the resin-type dispersant having a specific structure of the present invention, photosensitive coloring while satisfying various patterning characteristics (resolution, linearity, dimensional stability, development stability) required for the photosensitive coloring composition. The photosensitive coloring composition for color filters excellent in the viscosity stability as a composition, dimensional stability, and linearity can be provided. Moreover, the high quality color filter using the photosensitive coloring composition for color filters can be provided.

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 filter>
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) is a hydroxyl group of the 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 And an 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 an ethylenically unsaturated monomer. 35 mass% or more based on the total amount of the monomer (c) And characterized in that 0 wt% or less.
Below, the photosensitive coloring composition for color filters of this invention is demonstrated 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 anhydride. A first step of first producing a reaction product, followed by ethylenic unsaturation comprising a hydroxyl group-containing ethylenically unsaturated monomer (b) using the remaining thiol group of the reaction product as a chain transfer agent A second step of producing a hydroxyl group-containing polymer in which a vinyl polymer moiety having a hydroxyl group is introduced by radical polymerization of the monomer (c), and further comprising one isocyanate group and one or more (meth) acryloyl groups. It is obtained by going through a third step which is a reaction with the compound (d) it has. A plurality of carboxyl group portions in the resin-type dispersant (B) of the present invention function as a pigment adsorbing portion, and a 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, and cannot be represented by a general formula (structure) or is not practical, 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 (alias: 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, 3-propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol, and the like.

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

  As the catalyst used for reacting the acid anhydride group and the hydroxyl group of the present invention, a known catalyst can be used. 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.

In the reaction product of the hydroxyl group of the compound (a) having two hydroxyl groups and one thiol group and the acid anhydride group of pyromellitic anhydride and / or trimellitic anhydride obtained in the first step , The number of moles of acid anhydride group in pyromellitic acid anhydride (p), the number of moles of acid anhydride group in trimellitic acid anhydride (t), two hydroxyl groups and one thiol group in the molecule When the number of moles of hydroxyl groups in the compound (a) having the formula (a) is (o), the molar ratio thereof is 0.3 <[(p) + (t)] / (o) <1.0, More preferably, 0.5 <[(p) +
(T)] / (o) <1.0, most preferably 0.6 <[(p) + (t)] / (o) <0.8
It is. If it is 0.3 or less, there may be fewer acid anhydride residues as the pigment adsorbing part, and the acid value of the resin may also be lower. If it is 1.0 or more, unreacted acid anhydride groups 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 anhydride. Hydroxyl group-containing ethylenically unsaturated monomer is introduced by radical polymerization of ethylenically unsaturated monomer (c) containing hydroxyl group-containing ethylenically unsaturated monomer (b) using the existing thiol group as a chain transfer agent The second step for producing the hydroxyl group-containing polymer thus prepared will be described. By copolymerizing the ethylenically unsaturated monomer (b) containing a hydroxyl group in the second step, a hydroxyl group can be introduced into the vinyl polymer portion of the dispersant, and one isocyanate is obtained in the third step. It can be reacted with a compound (d) having a group and one or more (meth) acryloyl groups.

(Hydroxyl-containing ethylenically unsaturated monomer (b))
As the hydroxyl group-containing ethylenically unsaturated monomer (b), any monomer having a hydroxyl group and having an ethylenically unsaturated double bond may be used. (Meth) acrylate monomers having, for example, 2-hydroxyethyl (meth) acrylate, 2 (or 3) -hydroxypropyl (meth) acrylate, 2 (or 3 or 4) -hydroxybutyl (meth) acrylate and Hydroxyalkyl (meth) acrylates such as cyclohexanedimethanol mono (meth) acrylate, and alkyl-α-hydroxyalkyl acrylates such as ethyl-α-hydroxymethyl acrylate, or (meth) acrylamide monomers having a hydroxyl group, for example, N- (2-hydroxyethyl) (meth) acrylamide, N- ( - hydroxypropyl) (meth) acrylamide, N
N- (hydroxyalkyl) (meth) acrylamide such as-(2-hydroxybutyl) (meth) acrylamide, or vinyl ether monomers having a hydroxyl group, such as 2-hydroxyethyl vinyl ether, 2- (or 3-) Hydroxypropyl vinyl ether, hydroxyalkyl vinyl ether such as 2- (or 3- or 4-) hydroxybutyl vinyl ether, or an allyl ether monomer having a hydroxyl group, such as 2-hydroxyethyl allyl ether, 2- (or 3-) Examples include hydroxyalkyl allyl ethers such as hydroxypropyl allyl ether and 2- (or 3- or 4-) hydroxybutyl allyl ether.

  Also obtained by adding alkylene oxide and / or lactone to the above hydroxyalkyl (meth) acrylate, alkyl-α-hydroxyalkyl acrylate, N- (hydroxyalkyl) (meth) acrylamide, hydroxyalkyl vinyl ether or hydroxyalkylallyl 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 thereof are used. When two or more kinds of alkylene oxide are used in combination, the bonding form may be random and / or block. As the lactone to be added, δ-valerolactone, ε-caprolactone, ε-caprolactone substituted with an alkyl group having 1 to 6 carbon atoms, and a combination system of two or more of these are used. What added both alkylene oxide and lactone may be used.

(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, and 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 tetrahydrofurfuryl (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, acryloylmorpholine ( (Meth) acrylamides;
Amino group-containing (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate;
Nitriles such as (meth) acrylonitrile are exemplified.

  As monomers that can be used in combination with the above acrylic monomers, styrenes such as styrene, α-methylstyrene, and indene, and vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether And fatty acid vinyls such as vinyl acetate and vinyl propionate.

  Moreover, a carboxyl group-containing ethylenically unsaturated monomer can be used in combination. As the carboxyl group-containing ethylenically unsaturated monomer, one or more kinds 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 from 35% by weight to 80% by weight, preferably from 38% by weight to 60% by weight, based on the total amount of the ethylenically unsaturated monomer (c). It is not more than mass%, more preferably not less than 40 mass% and not more than 50 mass%.

  In the resin-type dispersant of the present invention, the carboxyl group-containing ethylenically unsaturated monomer is most preferably acrylic acid or methacrylic acid, and the ethylenic group containing the hydroxyl group-containing ethylenically unsaturated monomer (b). 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. It is. When the content is less than 2.5% by mass, patterning suitability such as linearity and dimensional stability during production of the color filter is deteriorated, and when it exceeds 10.0% by mass, the pigment dispersion stability may be deteriorated.

  Next, the third step of reacting the hydroxyl group-containing compound with a compound (d) having one isocyanate group and one or more (meth) acryloyl groups will be described. The dispersant of the present invention is obtained by reacting a hydroxyl group in the hydroxyl group-containing compound with an isocyanate group in the compound (d) having one isocyanate group and one or more (meth) acryloyl groups. Thereby, a (meth) acryloyl group can be arbitrarily introduced mainly into the vinyl polymer portion 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)
The compound (d) having one isocyanate group and one or more (meth) acryloyl groups used in the third step is a compound having one isocyanate group and one or two (meth) acryloyl groups. 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. Any structure is acceptable. 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 1 mol of 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. mol. 0 mol, most preferably 0.8 to 1.0 mol. If the amount is less than 0.2 mol, the amount of (meth) acryloyl groups may be reduced, so that the curability may be insufficient. If the amount exceeds 1.0 mol, unreacted isocyanate groups are present in the resin. It may remain and storage stability may deteriorate. The reaction temperature is 50 ° C to 150 ° C, preferably 70 ° C to 120 ° C. When the reaction temperature is less than 50 ° C., the reaction rate is slow, and when it exceeds 150 ° C., the urethane group produced by the reaction is decomposed.

Mole of (meth) acryloyl group introduced into resin type dispersant (B) obtained by reaction of hydroxyl group in said hydroxyl group-containing compound with one isocyanate group and 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 of double bond equivalent (g / mol) calculated as (total weight of the resin) / (mol number of double bonds contained in the resin weight). It is represented by However, in the present invention, it is not the double bond equivalent of the whole resin, but ((c) the total mass of the ethylenically unsaturated monomer + (d) one isocyanate group and one or more (meth) acryloyl groups. Resin-type dispersant (B) expressed as: (d) (d) mol of (meth) acryloyl group contained in a compound having one isocyanate group and one or more (meth) acryloyl groups) The double bond equivalent (Z) in the side chain of this affects the linearity and dimensional stability when producing a color filter. In the present invention, the value of Z is preferably 300 to 600 g / mol for linearity and dimensional stability when forming a 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. If the weight average molecular weight exceeds 100,000, the interaction between the resins may become strong, and the viscosity of the pigment composition may increase. is there.

  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. When the acid value is less than 5 mgKOH / g, the pigment adsorbing ability may be lowered and there may be a problem in pigment dispersibility. There is a case.

<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, organic or inorganic pigments can be used alone or in admixture of two or more. The pigment is preferably a pigment having a high color developability and a high heat resistance, particularly a pigment having a high heat decomposition resistance, and an organic pigment is usually used. Below, the specific example of the organic pigment which can be used for the coloring composition for color filters is shown by a color index number.

<Organic pigment>
Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, described in JP 2011-523433. Of diketopyrrolopyrrole pigments or described in publication 2014-112527 Zone pigments, mention may be made of the azo pigments such as described in published 2013-161026. 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, and more preferably C.I. I. Pigment red 177 and 254.

  The red coloring composition includes C.I. I. You may use together orange pigments, such as pigment orange 36, 38, 43, 51, 55, 59, 61, 71, or 73, and / or the yellow pigment mentioned later.

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

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like. Among these, from the viewpoint of 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, and JP-A-2004-70342, and aluminum phthalocyanine pigments described in JP-A-4893859. However, it is not particularly 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.

  Examples of yellow pigments include 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, 82,185,187,188,192,193,194,196,198,199,213,214, although such quinophthalone compounds described in the open 2012-226110 include, but are not particularly limited thereto. Among these, from the viewpoint of heat resistance, light resistance, and transmittance of the filter segment, examples of yellow pigments include C.I. I. Pigment Yellow 138, 139, 150, 185 and at least one selected from quinophthalone pigments described in JP 2012-226110 A are preferable. More preferably, C.I. I. Pigment yellow 139, 150, and 185.

  Examples of the quinophthalone pigment described in JP2012-226110A include compounds represented by the following.

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

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

Inorganic pigments include titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine, bitumen, chromium oxide green, cobalt green, amber And synthetic iron black. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability and the like while maintaining a balance between saturation and lightness.

(Miniaturization of pigment)
The organic pigment is preferably refined by a salt milling process or the like in order to correspond to high transmittance and high contrast. The primary particle diameter of the pigment is preferably 10 nm or more because of good dispersion in the colorant carrier. Moreover, since a filter segment with high contrast can be formed, it is preferable that it is 80 nm or less. A particularly preferred range is 20 to 60 nm.

  When the salt is milled, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. The amount of 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>
The coloring composition by embodiment of this invention can also use dye as a coloring agent. As the dye, any of acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes and the like can be used. Moreover, it may be in the form of lake pigments obtained by rake-forming these derivatives or dyes.

Furthermore, in the case of an acid dye having an acid group such as sulfonic acid or carboxylic acid, or in the form of a direct dye, an inorganic salt of an acid dye, an acid dye and a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, Alternatively, use a salt-forming compound with a nitrogen-containing compound such as a primary amine compound, or salt formation using a resin component having these functional groups, or use as a salt-forming compound after sulfonamidation. Therefore, it is possible to obtain a colored composition having excellent fastness, which is preferable.
A salt-forming compound of an acid dye and a compound having an onium base is also preferable because of excellent fastness. More preferably, the compound having an onium base is a resin having a cationic group in the side chain.

  In the case of a basic dye, it can be used after salt formation using an organic acid, perchloric acid or a metal salt thereof. A salt forming compound of a basic dye is preferable because of its excellent resistance and compatibility with a pigment, and further, a basic dye and an organic sulfonic acid, an organic sulfuric acid, a fluorine group-containing phosphorus anion compound that is a counter component that works as a counter ion 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 conjugate base of an organic acid having a halogenated hydrocarbon group, or an acidic dye. Is.

Moreover, when it has a polymerizable unsaturated group in a pigment | dye frame | skeleton, it can be set as the dye excellent in tolerance, and it is preferable.
Moreover, when a dye has an oxetane group, the coloring composition containing this dye is excellent in the heat resistance after hardening. The dye having an oxetane group can be achieved, for example, by using an ethylenically unsaturated monomer having an oxetane structure in a resin constituting a salt-forming compound containing the dye.

  In one embodiment, the chemical structure of the dye includes, for example, azo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, Anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azines Dyes, polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes Fee, perinone dyes, indigo dyes, mention may be made thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, and a dye structure derived from a dye selected from those metal complex dyes.

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

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

  Further, examples of the organic dye that can be used in another embodiment include triarylmethane, xanthene, and anthraquinone, and it is preferable to use xanthene.

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

Examples of red and purple colors include C.I. I. Solvent Red, C.I. I. Oil-soluble dyes such as solvent violet, C.I. I. Basic Red, C.I. I. Basic dyes such as basic violet, C.I. I. Acid Red, C.I. I. Acid dyes such as Acid Violet, C.I. I. Direct Red, C.I. I. Examples include those belonging to direct dyes such as direct violet.
Here, the direct dye has a sulfonic acid group (—SO ₃ H, —SO ₃ Na) in the structure, and in the present disclosure, the direct dye is regarded as an acid dye.

[Salt formation of xanthene dyes, sulfonamidation]
The xanthene-based basic dye is preferably used after being salted using an organic acid or perchloric acid. As the organic acid, organic sulfonic acid or organic carboxylic acid is preferably used. Of these, naphthalenesulfonic acid such as tobias acid and perchloric acid are preferably used in terms of resistance.

  In addition, xanthene-based acid dyes are used as salt-forming compounds by chlorination using quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, primary amine compounds, etc., or resin components having these functional groups. In view of resistance, it is preferable to use it as a sulfonamide compound after sulfonamidation.

  Salt forming compounds of xanthene acid dyes and / or sulfonic acid amide compounds of xanthene acid dyes are preferred because of their excellent hue and resistance, and quaternary ammonium which is a counter component that works as counter ions. It is more preferable to use a compound prepared by using a salt compound and a sulfonic acid amide compound obtained by sulfonamidating a xanthene acid dye.

  Among xanthene dyes, rhodamine dyes are preferable because they are excellent in color developability and resistance.

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

[Xanthene oil-soluble dye]
Examples of xanthene oil-soluble dyes include C.I. I. Solvent Red 35, C.I. I. Solvent Red 36, C.I. I. Solvent Red 42, C.I. I. Solvent Red 43, C.I. I. Solvent Red 44, C.I. I. Solvent Red 45, C.I. I. Solvent Red 46, C.I. I. Solvent Red 47, C.I. I. Solvent Red 48, C.I. I. Solvent Red 49, C.I. I. Solvent Red 72, C.I. I. Solven Red 73, C.I. I. Solvent Red 109, C.I. I. Solvent Red 140, C.I. I. Solvent Red 141, C.I. I. Solvent Red 237, C.I. I. Solvent Red 246, C.I. I. Solvent Violet 2, C.I. I. Solvent violet 10 and the like.
Among them, C.I., which is a rhodamine-based oil-soluble dye having high color developability. 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 preferable.

[Xanthene basic dye]
Examples of xanthene basic dyes 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 these, C.I. I. Basic Red 1, C.I. I. It is preferable to use basic violet 10.

[Xanthene acid dyes]
Examples of xanthene acid dyes include C.I. I. Acid Red 51 (erythrosin (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 Phloxin 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 these, in terms of heat resistance and light resistance, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 388 or rhodamine acid dye C.I. 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, in particular, C.I., which is a rhodamine acid dye, is excellent in color developability, heat resistance and light resistance. I. Acid Red 52, C.I. I. Most preferably, Acid Red 289 is used.

The acid dye (not limited to xanthene) is preferably a salt-forming compound of an acid dye and a nitrogen-containing compound, such as 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 a salt 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 impart high heat resistance, light resistance, and solvent resistance by sulfonamidation.
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, thereby reducing the lightness and resistance. It can be set as the outstanding coloring composition.

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

  Secondary amine compounds include aliphatic unsaturated secondary amines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, diallylamine, methylaniline, ethylaniline, dibenzylamine, diphenylamine, dicocoalkyl. Amine, di-cured tallow alkylamine, distearylamine, 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 a salt-forming compound (a) comprising an acid dye and a quaternary ammonium salt compound.
The quaternary ammonium salt compound as the counter component of the acid dye will be described. A quaternary ammonium salt compound becomes an acid dye counter by having an amino group.

  A preferable form of the quaternary ammonium salt compound which is a 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. Is. That is, it is preferably one that does not inhibit the color development of the dye component and does not cause a color change.

It is preferable that the molecular weight of the counter part which is a cation component of a quaternary ammonium salt compound is in the range of 190-900. Here, the cation moiety corresponds to the (NR ₁ R ₂ R ₃ R ₄ ) ⁺ moiety in the following general formula (1). If the molecular weight is smaller than 190, light resistance and heat resistance may be lowered, and further solubility in a solvent may be lowered. On the other hand, when the molecular weight is larger than 900, the ratio of the color forming component in the molecule is lowered, the color developability is lowered, and the lightness can be lowered. More preferably, the molecular weight of the counter portion is in the range of 240-850. Particularly preferred is a counter portion with a molecular weight in the range of 350-800. Here, the molecular weight was calculated based on the structural formula. 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, those represented by the following general formula (1) can be used.

General formula (1)

(In General Formula (1), R _{1 to} R ₄ each independently represents an alkyl group having 1 to 20 carbon atoms or a benzyl group, and at least two of R ₁ , R ₂ , R ₃ , and R ₄ are present. C number of 5 to 20 amino .Y ^- represents an anion of m inorganic or organic).

R ₁ to R ₄ in by the a 5 to 20 the number of at least two and C, solubility in solvents is improved. When the number of alkyl groups having a C number of less than 5 is 3 or more, solubility in a solvent is deteriorated, and coating film foreign matter is likely to be generated. Moreover, when the alkyl group in which the number of C exceeds 20 exists, the color development property of a salt-forming compound (a) will be impaired.

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

  The quaternary ammonium salt compounds include tetramethylammonium chloride, tetraethylammonium chloride, monostearyltrimethylammonium chloride, distearyldimethylammonium chloride, tristearylmonomethylammonium chloride, cetyltrimethylammonium chloride, trioctylmethylammonium chloride, dioctyldimethylammonium chloride. , Monolauryltrimethylammonium chloride, dilauryldimethylammonium chloride, trilaurylmethylammonium chloride, triamylbenzylammonium chloride, trihexylbenzylammonium chloride, trioctylbenzylammonium chloride, trilaurylbenzylammonium chloride Id, benzyl dimethyl stearyl ammonium chloride, and benzyl dimethyl octyl ammonium chloride, dialkyl (alkyl C14 -C18) dimethyl ammonium chloride (hydrogenated tallow), and the like.

  Specific examples of the quaternary ammonium salt compound products include, for example, Cotamin 24P, Cotamin 86P Conk, Cotamin 60W, Cotamin 86W, Cotamin D86P, Sanizole C, Sanizole B-50 manufactured by Kao Corporation, and Lion Corporation's Arcade 210- 80E, 2C-75, 2HT-75, 2HT flakes, 2O-75I, 2HP-75, 2HP flakes, and the like. Among them, Cotamine D86P (distearyldimethylammonium chloride), Arcard 2HT-75 (dialkyl (alkyl is C14- C18) dimethylammonium chloride).

(Resin having a cationic group in the side chain)
When the organic dye used in the embodiment of the present invention is an acid dye, it is also preferably used as a salt-forming compound (a ′) comprising an acid dye and a resin having a cationic group in the side chain. The 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 a 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 salts, iodonium salts, sulfonium salts, diazonium salts, and phosphonium salts are preferable, and in consideration of storage stability (thermal stability), they are ammonium salts, iodonium salts, and sulfonium salts. It is more preferable. More preferred is an ammonium salt.

  When preparing a blue coloring composition for a color filter containing a salt-forming compound (a ′) and exhibiting the characteristics as a color filter, the same kind of resin as the binder resin constituting the blue coloring composition for the color filter is used. It is preferable to do. In one embodiment of the present invention, an acrylic resin is preferably used as the binder resin in the color filter coloring composition, and therefore, the resin having a cationic group in the side chain for obtaining the salt-forming compound (a ′) is An acrylic resin is preferred.

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

General formula (2)

[In General Formula (2), R ⁵¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ^{52 to} R ⁵⁴ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, and R ^{52 to} R ⁵⁴ Two of them may be bonded to each other to form a ring. Q represents an alkylene group, an arylene group, —CONH—R ⁵⁵ —, —COO—R ⁵⁵ —, and R ⁵⁵ represents an alkylene group. Y ^- is an anion of an inorganic or organic. ]

Examples of the alkyl group for 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 this alkyl group, a C1-C12 alkyl group is preferable, a C1-C8 alkyl group is more preferable, and a C1-C4 alkyl group is especially preferable.

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

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

Examples of the alkyl group in R ^{52 to} R ⁵⁴ include a linear alkyl group (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, 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), cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.) and bridged cyclic alkyl groups (norbornyl, adamantyl, pinanyl, etc.). As this alkyl group, a C1-C18 alkyl group is preferable, More preferably, it is a C1-C8 alkyl group.

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, 2-methyl-2-propenyl and the like) and cycloalkenyl groups (such as 2-cyclohexenyl and 3-cyclohexenyl). As this alkenyl group, a C2-C18 alkenyl group is preferable, More preferably, it is a C2-C8 alkenyl group.

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

When the alkyl group, alkenyl group, or aryl group represented by R ^{52 to} R ⁵⁴ has a substituent, examples of the substituent include a halogen atom, a hydroxyl group, an alkoxyl group, an aryloxy group, an alkenyl group, an acyl group, Examples include a substituent selected from an alkoxycarbonyl group, a carboxyl group, a phenyl group, and the like. Among these substituents, a halogen atom, a hydroxyl group, an alkoxyl group, and a phenyl group are particularly preferable.

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

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

In general formula (2), the component of Q connecting the vinyl moiety and the ammonium base represents an alkylene group, an arylene group, —CONH—R ⁵⁵ —, —COO—R ⁵⁵ —, and R ⁵⁵ represents an alkylene group, Among these, —CONH—R ⁵⁵ — and —COO—R ⁵⁵ — are preferable because of polymerizability and availability. R ⁵⁵ is more preferably a methylene group, an ethylene group, a propylene group, or a butylene group, and particularly preferably an ethylene group.

The component of Y ⁻ 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 used without limitation. Specifically, hydroxide ions; halogen ions such as chloride ions, bromide ions, and iodide ions; carboxylate ions such as formate ions and acetate ions; Carbonate ions, bicarbonate ions, nitrate ions, sulfate ions, sulfite ions, chromate ions, dichromate ions, phosphate ions, cyanide ions, permanganate ions, and even hexacyanoferrate (III) ions And complex ions. From the viewpoint of synthesis suitability and stability, halogen ions and carboxylate ions are preferable, and halogen ions are most preferable. When the counter anion is an organic acid ion such as a carboxylate ion, the organic acid ion may be covalently bonded in the resin to form an inner salt.

One method for introducing an oxetane group into a resin having a cationic group in the side chain is that the ethylenically unsaturated monomer containing an oxetane structure corresponds 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.
Examples of commercially available products include ETERNACOLL OXMA (manufactured by Ube Industries), OXE-10, and OXE-30 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.).

(Salt formation)
A salt-forming compound of an acid dye and a nitrogen-containing compound or a resin having a cationic group in the side chain can be produced by a conventionally known method. A specific method is disclosed in Japanese Patent Laid-Open No. 11-72969.
For example, a xanthene acid dye may be used, and after the xanthene acid dye is dissolved in water, a quaternary ammonium salt compound may be added and subjected to chlorination 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 ⁺ ) part of the quaternary ammonium salt compound are combined. A salt compound is obtained. In addition, instead of water, methanol and ethanol are also solvents that can be used for the chlorination.

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

(Sulphonic acid amide compound)
The acidic dye may be a sulfonic acid amide compound obtained by reacting a sulfonic acid amide compound with an anionic dye.
A sulfonic acid amide compound of an acid dye that can be preferably used for 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. Compounds can be prepared by reacting with amines having —NH ₂ groups.
Specific examples of amine compounds that can be preferably used in sulfonamidation include 2-ethylhexylamine, dodecylamine, 3-decyloxypropylamine, 3- (2-ethylhexyloxy) propylamine, and 3-ethoxypropyl. It is preferable to use amine, cyclohexylamine or the like.
An example using a xanthene acid dye is C.I. I. In the case of obtaining a sulfonic acid amide compound obtained by modifying Acid Red 289 with 3- (2-ethylhexyloxy) propylamine, C.I. I. Acid Red 289 was converted to a sulfonyl chloride and reacted with a theoretical equivalent of 3- (2-ethylhexyloxy) propylamine in dioxane to give C.I. I. What is necessary is just to obtain the sulfonic acid amide compound of Acid Red 289.
In addition, C.I. I. In the case of obtaining a sulfonic acid amide compound obtained by modifying Acid Red 52 with 3- (2-ethylhexyloxy) propylamine, C.I. I. Acid Red 52 was converted to a sulfonyl chloride and reacted with a theoretical equivalent of 3- (2-ethylhexyloxy) propylamine in dioxane to give C.I. I. What is necessary is just to obtain the sulfonic acid amide compound of Acid Red 52.
Moreover, also in other acidic dyes, a sulfonic acid amide compound can be obtained in the same manner as xanthene dyes.

  As the xanthene-based dyes, JP2010-032999A, JP2011-138094A, JP2011-227313A, JP2011-242752A, JP2012-107192A, JP2013-103A. No. 033194, Japanese Patent Application No. 2011-71888, Japanese Patent Application No. 2013-72263, Japanese Patent Application No. 2013-81209, Japanese Patent Application Laid-Open No. 2014-173064, Japanese Patent Application No. 2013-53028, Japanese Patent Application No. 2013-52186 JP, 2014-196392, JP 2014-196393, JP 2014-201714, JP 2014-201715, JP 2013-050693, JP 2013-178478, JP2013-203156A, International It may be a known technique described in Hirakidai 2013/011687 pamphlet or the like.

In one embodiment, xanthene dyes include 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. Among them, 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 a dipyrromethene dye as a partial structure of the dye part, and preferably a dipyrromethene compound and a dipyrromethene metal complex compound obtained from a dipyrromethene compound and a metal or a metal compound. A metal complex compound in which the structure represented by the general formula (3) is coordinated to a metal atom or a metal compound (hereinafter, appropriately referred to as “dipyrromethene metal complex compound”) is preferable.

[Dipyrromethene metal complex compound]
The 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 General Formula (3), R ^{1 to} R ⁶ each independently represent a hydrogen atom or a monovalent substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Represents.
The metal or metal compound may be any metal atom or metal compound capable of forming a complex, and may be any divalent metal atom, divalent metal oxide, divalent metal hydroxide, or 2 Valent metal chlorides are included. Examples of the metal or metal compound include ZnCl, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, and B, 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 a metal or a metal compound, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, and C are used from the viewpoint of the stability of the complex, spectral characteristics, heat resistance, light resistance, and production suitability.
u, Ni, Co, TiO, B, or VO are preferred, Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO are more preferred, and Fe, Zn, Cu, Co, B Or VO is most preferred.

  Examples of such dipyrromethene dyes include JP-A-2008-292970, JP-A-2010-85758, JP-A-2010-84009, Japanese Patent Application No. 2010-43530, JP-A-2013-080010, Known techniques described in Japanese Unexamined Patent Publication No. 2013-210596 and International Publication No. 2013/141156 can be used.

[Triphenylmethane dye]
Examples of the triphenylmethane dye skeleton include a diaminotriphenylmethane dye skeleton, a triaminotriphenylmethane dye skeleton, and a rosic acid dye skeleton having an OH group.
Triaminotriphenylmethane-based dye skeletons are preferable in that they are excellent in color tone and more excellent in fastness to sunlight than others. Among them, a diphenylnaphthylmethane dye skeleton that is a basic dye is particularly preferable.

[Triphenylmethane basic dye]
The triphenylmethane-based basic dye develops color when the NH ₂ or OH group located in the para position with respect to the central carbon takes a quinone structure by oxidation.
Depending on the number of NH ₂ and OH groups, it can be divided into the following three types. Among them, a triaminoarylmethane-based basic dye is preferable in terms of good blue, red and green coloring.
a) Diaminotriphenylmethane basic dye b) Triaminotriphenylmethane basic dye c) Rosolic acid basic dye having OH group Triaminotriphenylmethane basic dye, diaminotriphenylmethane basic dye The dye has a vivid color tone and is preferable because it is more excellent in fastness to sunlight than other dyes.

  Since the blue triphenylmethane basic dye has a spectral characteristic having a high transmittance at 400 to 440 nm, it can have high brightness, particularly when used for forming a blue filter segment. This is preferable because it is possible.

Specific examples of triphenylmethane basic dyes include 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. Examples include Basic Green 1 (Brilliant Green GX) and 4 (Malachite Green).
Above all, from the point of brightness, C.I. I. It is preferable to use Basic Blue 7.

  Further, in the case of a triphenyl basic dye, it can be used after being salted using an organic acid, perchloric acid or a metal salt thereof. Among them, a salt forming compound of a basic dye is preferable because of its resistance and excellent compatibility with pigments, and further, a basic dye and organic sulfonic acid, organic sulfuric acid, fluorine group-containing phosphorus, which are counter components that function as counter ions. 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 conjugate base of an organic acid having a halogenated hydrocarbon group, or an acidic dye. It is more preferable.

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

(Salt formation)
These salt forming compounds of a basic dye and an anionic counter can be synthesized by a conventionally known method. A specific method is disclosed in Japanese Patent Laid-Open No. 2003-215850.
For example, after the triarylmethane basic dye is dissolved in water, an organic sulfonic acid or (sodium organic sulfonate) solution may be added and subjected to chlorination treatment while stirring. Here, a salt-forming compound in which the amino group (—NHC ₂ H ₅ ) portion in the triarylmethane-based 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 alkali solution such as sodium hydroxide before the salt-forming treatment and used as a form of sodium sulfonate (—SO ₃ Na). In the present disclosure, a sulfonic acid group (—SO ₃ H) and a functional group (—SO ₃ Na) that is sodium sulfonate may be referred to without distinction.

  Examples of such triphenylmethane dyes include JP-A No. 2002-014222, JP-A No. 2003-246935, JP-A No. 2003-246935, JP-A No. 2008-304766, and JP-A No. 2010-256598. Japanese Patent Application No. 2011-200560, Japanese Unexamined Patent Application Publication No. 2011-186043, Japanese Unexamined Patent Application Publication No. 2012-173399, Japanese Unexamined Patent Application Publication No. 2012-233303, Japanese Unexamined Patent Application Publication No. 2012-098522, Japanese Patent Application No. 2012-288970, Known techniques described in Japanese Patent Application No. 2012-200469, Japanese Patent Application Laid-Open No. 2014-196262, International Publication No. 2010/123071, Pamphlet of International Publication No. 2011/162217, International Publication No. 2013/108591, etc. Use It can be.

  In one embodiment, the triphenylmethane dye includes C.I. I. Acid Violet 15, C.I. I. Acid Violet 17, C.I. I. Acid Violet 19, C.I. I. Acid Violet 21, C.I. I. Acid Violet 24, C.I. I. Acid Violet 25, C.I. I. Acid Violet 38, C.I. I. Acid Violet 49, C.I. I. Acid Blue 1, C.I. I. Acid Blue 3, C.I. I. Acid Blue 5, C.I. I. Acid Blue 7, C.I. I. Acid Blue 9, C.I. I. Acid Blue 11, C.I. I. Acid Blue 13, C.I. I. Acid Blue 15, C.I. I. Acid Blue 17, C.I. I. Acid Blue 22, C.I. I. Acid Blue 24, C.I. I. Acid Blue 26, C.I. I. Acid Blue 75, C.I. I. Acid Blue 83, C.I. I. Acid Blue 90, C.I. I. Acid Blue 93, C.I. I. Acid Blue 100, C.I. I. Basic Blue 81, C.I. I. 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 dyes]
Any cyanine dye can be used without limitation as long as it is a compound having a dye moiety containing a cyanine skeleton in the molecule.
Examples of cyanine dyes include C.I. I. Basic yellow 11, 12, 13, 14, 21, 22, 23, 24, 28, 29, 33, 35, 40, 43, 44, 45, 48, 49, 51, 52, 53, C.I. I. Basic Red 12, 13, 14, 15, 27, 35, 36, 37, 45, 48, 49, 52, 53, 66, 68, C.I. I. Basic violet 7, 15, 16, 20, 21, 39, 40, C.I. I. Basic orange 27, 42, 44, 46, C.I. I. Basic blue 62, 63, etc. may be mentioned.
In addition, cyanine dyes described in JP2014-224970A, JP2013-261614A, and the like can also be used.

[Anthraquinone dyes]
An anthraquinone dye is a dye having 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. Modern Red 3, 11, C.I. I. Modern Blue 8 etc. are mentioned. Further, anthraquinone dyes described in JP-A-9-291237, WO2003 / 080734, WO2006 / 024617, JP2011-174987, JP2013-53273, and the like are used. It can be used as a known technique. The anthraquinone dye is preferably soluble in an organic solvent, and more preferably a blue, violet or red anthraquinone dye. As an anthraquinone dye, 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, it is necessary to increase the content of the colorant in the photosensitive coloring composition in order to improve the color reproduction characteristics and reduce the thickness of the color filter. The content of the colorant (A) is preferably 30% by mass or more, and more preferably 40% by mass or more, in 100 parts by mass of the solid content of the photosensitive coloring composition for color filter according to the embodiment of the present invention. It is preferable for obtaining a good color reproducibility and reducing the film thickness. Moreover, if it is 65 mass% or less, More preferably, it is 60 mass% or less, content of resin which is a hardening material, or a photopolymerizable compound will become appropriate, and sufficient cured coating film can be obtained. Generally, when the content of the colorant increases, the patterning characteristics of the photosensitive coloring composition tend to deteriorate. According to the present invention, the content of the colorant required for general high color reproduction is of course 30 wt% to less than 40 wt%, and of course, the more difficult colorant content is 40 wt%. Sufficient patterning characteristics can be obtained even with a photosensitive coloring composition of at least%.

<Photopolymerization initiator (C)>
In the photosensitive composition of the present invention, the composition is cured by ultraviolet irradiation, and a photopolymerization initiator (C) is added to form a filter segment by photolithography. It is essential to prepare it in the form of a sex composition. The blending amount of the photopolymerization initiator is more preferably 0.3 to 8.0% by mass in the total solid content of the photosensitive coloring composition from the viewpoint of practical ultraviolet sensitivity.

As photopolymerization initiator (C), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl Acetophenone compounds such as 1- [4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether Or benzoin compounds such as benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3 Benzophenone compounds such as', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4- Thioxanthone compounds such as diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-me Xylphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- Triazine compounds such as (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoy Oxime)], or oxime ester compounds such as ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime); Phosphine compounds such as 2,4,6-trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone A borate compound; a carbazole compound; an imidazole compound; or a titanocene compound.
These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.
Commercially available acetophenone compounds are all manufactured by BASF Corporation, “IRGACURE 907” (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one), “IRGACURE 369”. (2- (dimethylamino) -2
-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone), “IRGACURE 379” 2-benzyl-2-dimethylamino-1
As-(4-morpholinophenyl) -butan-1-one and 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 this invention, it is preferable to contain an oxime ester type compound among these.

[Oxime ester compounds]
The oxime ester-based compound absorbs ultraviolet rays to cleave the N—O bond of the oxime to generate an iminyl radical and an alkyloxy radical. Since these radicals are further decomposed to generate radicals with high activity, a pattern can be formed with a small exposure amount. The oxime ester compound is preferably an oxime ester photopolymerization initiator represented by the general formula (4). By using the initiator, the resin type dispersant (B) can be efficiently polymerized.

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

In general formula (4),
Y ¹ is a hydrogen atom or an optionally substituted alkenyl group, alkyl group, alkyloxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group An alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group, or a sulfamoyl group,
Y ² is a hydrogen atom or an optionally substituted alkenyl group, alkyl group, alkyloxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group , An alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group, or an amino group.
Z is a direct bond or a -CO- group;
Y ³ is a monovalent organic group including a carbazole group which may have a substituent, a Ph-S-Ph- group (Ph represents a phenyl group or a phenylene group which may have a substituent). It is preferable that

Examples of the alkenyl group which may have a substituent in Y ¹ include a linear, branched, monocyclic or condensed polycyclic alkenyl group having 1 to 18 carbon atoms, and these include a plurality of carbon atoms in the structure. -It may have a carbon double bond, and specific examples include vinyl group, 1-propenyl group, allyl group, 2-butenyl group, 3-butenyl group, isopropenyl group, isobutenyl group, 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 one or more —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, 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 the linear or branched alkyl group having 2 to 18 carbon atoms and optionally interrupted by one or more of —O— include —CH ₂ —O—CH ₃ , —CH _2. —CH ₂ —O—CH ₂ —CH ₃ , —CH ₂ —CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , — (CH ₂ —CH ₂ —O) _n —CH ₃ (where n is 1) To 8), — (CH ₂ —CH ₂ —CH ₂ —O) _m —CH ₃ (where m is 1 to 5), —CH ₂ —CH (CH ₃ ) —O—CH ₂ —. _{CH 3 -, - CH 2 -CH-} (OCH 3) but ₂ and the like, but 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 the following, but are not limited thereto. Is not to be done.

The alkyloxy group which may have a substituent in Y ¹ is a linear, branched, monocyclic or condensed polycyclic alkyloxy group having 1 to 18 carbon atoms, or 2 to 18 carbon atoms. Examples include linear, branched, monocyclic or condensed polycyclic alkyloxy groups optionally interrupted by one or more —O—. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyloxy group having 1 to 18 carbon atoms include methyloxy group, ethyloxy group, propyloxy group, butyloxy group, pentyloxy group, hexyloxy 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, boronyl Alkoxy group, may be mentioned 4-decyl cyclohexyl group and the like, but is not limited thereto. Specific examples of the linear or branched alkyloxy group having 2 to 18 carbon atoms and optionally interrupted by one or more —O— include —O—CH ₂ —O—CH ₃ , _{-O-CH 2 -CH 2 -O-} CH 2 -CH 3, -O-CH 2 -CH 2 -CH 2 -O-CH 2 -CH 3, -O- (CH 2 -CH 2 -O) n -CH ₃ (wherein n is 1 to _{8), - O- (CH 2} -CH 2 -CH 2 -O) m -CH 3 ( here m is 5 1), - 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 that 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 2-naphthyl. Group, 1-anthryl group, 9-anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 1-acenaphthyl group Group, 2-fluorenyl group, 9-fluorenyl group, 3-perylenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl group, 2,5-xylyl 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, o-mercaptophenyl group, p-cyanophenyl group, m-nitrophenyl group, m-azidophenyl group, and the like, but are not limited thereto. It is not a thing.

Examples of the aryloxy group which may have a substituent for Y ¹ include a monocyclic or condensed polycyclic aryloxy group having 4 to 18 carbon atoms. Specific examples include a phenoxy group, a 1-naphthyloxy group, 2- Naphtyloxy group, 9-anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy 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 for 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, phenoxathiinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group 2-indolyl group, 3-indolyl group, 1H-indazolyl group, purinyl group, 4H-quinolidinyl group, isoquino Lyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, β-carbolinyl group, phenanthridinyl group, 2-acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, 3-phenixazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, Imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthryl group 4-quinolinyl group, 4-isoquinolyl group, 3-phenothiazinyl group, 2-phenoxathiinyl group, 3-coumarinyl of the group and the like, but is not limited thereto.

Examples of the heterocyclic oxy group that may have a substituent for 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 include 2-furanyloxy group, 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 2-carbazolyl. Examples thereof include, but are not limited to, a ruoxy group, a 3-carbazolyloxy group, a 4-carbazolyloxy group, and a 9-acridinyloxy group.

Examples of the alkylsulfanyl group which may have a substituent for Y ¹ include a linear, branched, monocyclic or condensed polycyclic alkylthio group having 1 to 18 carbon atoms. 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 for 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, 2- A naphthylthio group, a 9-anthrylthio group, a 9-phenanthrylthio group and the like are exemplified, but the invention is not limited thereto.

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 include a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, 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. Although it is mentioned, it is not limited to these.

The arylsulfinyl group which may have a substituent for Y ¹ has 6 to 30 carbon atoms.
The arylsulfinyl group is preferably a 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, 4-methyloxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanylphenylsulfinyl group, 4-dimethylaminophenylsulfinyl group Le group and the like, but not limited thereto.

The alkylsulfonyl group which may have a substituent in Y ¹ is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, and specific examples include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, 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. Although it is mentioned, it is not limited to these.

The arylsulfonyl group which may have a substituent for Y ¹ is preferably an arylsulfonyl group having 6 to 30 carbon atoms, and specific examples include a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 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-phenylsulfanylphenylsulfo Examples thereof include, but are not limited to, a nyl group and a 4-dimethylaminophenylsulfonyl group.

Examples of the acyl group that may have a substituent in Y ¹ include a hydrogen atom or a carbonyl group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded. A carbonyl group substituted by an alkyloxy group having 2 to 20 carbon atoms, a carbonyl group to which a monocyclic or condensed polycyclic aryl group having 6 to 18 carbon atoms is bonded, or a monocyclic or condensed polycyclic aryloxy group having 6 to 18 carbon atoms. Examples include a substituted carbonyl group, a carbonyl group having a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples include formyl Group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl group, Thearoyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, crotonoyl group, isocrotonoyl group, oleoyl group, cinnamoyl group benzoyl group, methyloxycarbonyl group, ethyloxycarbonyl group, propyloxycarbonyl group, butyloxycarbonyl Group, hexyloxycarbonyl group, octyloxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, trifluoromethyloxycarbonyl group, benzoyl group, toluoyl group, 1-naphthoyl group, 2-naphthoyl group, 9-anthrylcarbonyl Group, phenyloxycarbonyl group, 4-methylphenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-dimethylaminophenyloxy group Carbonyl group, 2-methylsulfanylphenyloxycarbonyl group, 1-naphthoyloxycarbonyl group, 2-naphthoyloxycarbonyl group, 9-anthrylyloxycarbonyl group, 3-furoyl group, 2-thenoyl group, nicotinoyl group, isonicotinoyl Although groups etc. can be mentioned, it is not limited to these.

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 include an acetyloxy group, a propanoyloxy group, a butanoyloxy group, and a pentanoyloxy group. Group, trifluoromethylcarbonyloxy group, benzoyloxy group, 1-naphthylcarbonyloxy group, 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, and a dibenzylamino group. Can be mentioned.

  Here, as the alkylamino group, methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group, decylamino group, 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 Amino group, cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, cyclohexylamino group, cycloheptylamino group, cyclooctylamino group, cyclododecylamino group, 1-adamantamino group, 2-adamantami Group, and the like, but not limited thereto.

  Dialkylamino group includes dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, diheptylamino group, dioctylamino group, dinonylamino group, didecylamino group, 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 include, but are not limited to, piperazino groups.

  As an arylamino group, an anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p-toluidino group, 2-biphenylamino group, 3-biphenylamino group, 4- A biphenylamino group, a 1-fluoreneamino group, a 2-fluoreneamino group, a 2-thiazoleamino group, a p-terphenylamino group, and the like are exemplified, but the invention is not limited thereto.

  Examples of the diarylamino group include, but are not limited to, a diphenylamino group, a ditolylamino 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, N -Ethylanilino group, N-methyl-1-naphthylamino group and the like are exemplified, but not limited thereto.

Examples of the phosphinoyl group which may have a substituent in Y ¹ include phosphinoyl groups having 2 to 50 carbon atoms, and specific examples thereof include dimethylphosphinoyl group, diethylphosphinoyl group, dipropylphosphinoyl group. Group, diphenylphosphinoyl group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, bis (2,4,6-trimethylphenyl) phosphinoyl group, etc. Is not to be done.

Examples of the carbamoyl group which may have a substituent for Y ¹ include carbamoyl groups 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-cyanoph Enylcarbamoyl group, N-4-methoxyphenylcarbamoyl group, N-4-cyanophenylcarbamoyl group, N-4-methylsulfanylphenylcarbamoyl group, N-4-phenylsulfanylphenylcarbamoyl group, N-methyl-N-phenylcarbamoyl Group, N, N-dimethylcarbamoyl group, N, N-dibutylcarbamoyl group, N, N-diphenylcarbamoyl group, and the like, but are not limited thereto.

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-alkylsulfamoyl group, and an N-arylsulfamoyl group. Group, N, N-dialkylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group and the like. More specifically, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsulfur group. Famoyl group, N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group, N-octadecylsulfamoyl group, N-phenylsulfamoyl group, N-2- Methylphenylsulfamoyl group, N-2-chlorophenylsulfamoyl group, N-2-methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N-3-chlorophenylsulfamoyl group, N-3-nitrophenylsulfamoyl group, N-3-cyanophenylsulfamoyl group, N-4-methoxyphenyl Nylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4-dimethylaminophenylsulfamoyl group, N-4-methylsulfanylphenylsulfamoyl group, N-4-phenylsulfanylphenylsulfamoyl Group, N-methyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N-diphenylsulfamoyl group and the like. It is not limited to.

Y ² may have 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, an alkylsulfinyl group, As the arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyloxy group, and amino group, the aforementioned alkenyl group that may have a substituent in R1, an alkyl group that may have a substituent, and a substituent An alkyloxy group that may have, an aryl group that may have a substituent, an aryloxy group that may have a substituent, a heterocyclic group that may have a substituent, and a substituent A good heterocyclic oxy group, an optionally substituted alkylsulfanyl group, an optionally substituted arylsulfanyl group, and a substituent. Alkylsulfinyl group which may have, arylsulfinyl group which may have substituent, alkylsulfonyl group which may have substituent, arylsulfonyl group which may have substituent, and substituent It is synonymous with the acyloxy group which may be sufficient, and the amino group which may have a substituent.

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 methoxycarbonyl groups, butoxycarbonyl groups, alkoxycarbonyl groups such as phenoxycarbonyl groups, acyloxy groups such as acetoxy groups, propionyloxy groups, benzoyloxy groups, acetyl groups, benzoyl groups, isobutyryl groups, acryloyl groups , Acyl groups such as methacryloyl group and methoxalyl group, alkylsulfanyl groups such as methylsulfanyl group and tert-butylsulfanyl group, arylsulfanyl groups such as phenylsulfanyl group and p-tolylsulfanyl group, methylamino group Alkylamino group such as cyclohexylamino group, dialkylamino group such as dimethylamino group, diethylamino group, morpholino group, piperidino group, arylamino group such as phenylamino group, 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, xylyl group, cumenyl group, naphthyl group In addition to aryl groups such as anthryl group and phenanthryl group, heterocyclic groups such as furyl group and thienyl group, etc., hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group Group, nitro group, cyano group, trif Examples thereof include a fluoromethyl group, a trichloromethyl group, a trimethylsilyl group, a phosphinico group, a phosphono group, a trimethylammoniumyl group, a dimethylsulfoniumum group, and a triphenylphenacylphosphoniumyl group.
One or more of these substituents may be present, 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 photopolymerization initiators represented by the general formula (4), an oxime ester photopolymerization initiator represented by the following general formula (5) or (6), particularly a carbazole moiety represented by (6) The oxime ester photopolymerization initiator in the molecule is an oxime ester photopolymerization photopolymerization initiator (C) used in the present invention in combination with the resin type dispersant (B) to obtain good patterning characteristics. Among initiators, it is more preferable.

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

The general formula (5) corresponds to the case where Z in the general formula (4) is a —CO— group and Y ³ is a Ph—S—Ph— group, and Y ⁴ to Y ^{6 each} represents a hydrogen atom or a substituent. An alkyl group or an aryl group which may be contained is preferable. The alkyl group that may have a substituent or the aryl group that may have a substituent in Y ^{4 to} Y ⁶ has the same meaning as the alkyl group or the aryl group in Y ¹ and Y ² .

Further, Y ¹ may be an aryl group that may have a substituent, Y ² may be an optionally substituted alkyl group having 1 to 20 carbon atoms, and Y ⁴ and Y ⁶ may further be a hydrogen atom. Y ⁵ is more preferably 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, an iodine atom,
Alkoxy groups such as methoxy group, ethoxy group, tert-butoxy group, aryloxy groups such as phenoxy group, p-tolyloxy group, alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group, phenoxycarbonyl group, acetoxy group, propionyloxy Group, acyloxy group such as benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, methoxalyl group and other acyl groups, methylsulfanyl group, tert-butylsulfanyl group and other alkylsulfanyl groups, phenylsulfanyl group , Arylsulfanyl groups such as p-tolylsulfanyl group, alkylamino groups such as methylamino group and cyclohexylamino group, dimethylamino group, diethylamino group, morpholino group, piperidino group Dialkylamino group, phenylamino group, arylamino group such as p-tolylamino group, alkyl group such as methyl group, ethyl group, tert-butyl group, dodecyl group, phenyl group, p-tolyl group, xylyl group, cumenyl group , Naphthyl group, anthryl group, phenanthryl group, benzofuranyl group and other aryl groups, furyl group, thienyl group and other heterocyclic groups, hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p -Toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammonium group, dimethylsulfonyl group, triphenylphenacylphosphoniumyl group Groups and the like.

More preferable examples of the substituent for Y ² include cycloalkyl groups 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 photopolymerization initiator represented by the general formula (5) include photopolymerization initiators represented by the following chemical formulas (5-1) to (5-4).

(Oxime ester photopolymerization initiator represented by 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 including 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 .

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

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

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

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

Moreover, as a substituent in the benzoyl group which may have a substituent, a C1-C20 alkyl group or an alkyloxy group is preferable. Further, the alkyl group is preferably a methyl group or an ethyl group, 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 condensed polycyclic alkyloxy groups are preferred, linear, branched, monocyclic or condensed polycyclic having 2 to 18 carbon atoms in Y ¹ and optionally interrupted by one or more —O— Synonymous with alkyloxy group.

Y ² is preferably an alkyl group having 1 to 20 carbon atoms that may have a substituent, and the substituent is preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, A cycloalkyl group such as a cyclooctadecyl group; In addition, an aryl group which may have a substituent is preferable, and as the substituent, an alkyl group having 1 to 20 carbon atoms which may further have a substituent, a methoxy group, an ethoxy group, or a tert-butoxy group Etc. are preferred.

As the oxime ester photopolymerization initiator represented by the general formula (6a), specifically,
And photopolymerization initiators represented by the following chemical formulas (6a-1) to (6a-6).

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

General formula (6b)

The general formula (6b) corresponds to the case where Z in the general formula (6) is a -CO- group and Y ³ is a monovalent organic group including a carbazole group which may have a substituent. Is an oxime ester photopolymerization initiator.
Y ^{7 to} Y ¹³ are preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent, and Y ¹⁴ may have a substituent. A good aryl group is preferred.
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 methoxalyl group is preferable, and a benzoyl group is more preferable.

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

Commercially available products of these oxime ester compounds include 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)] (IR from BASF
GACURE OXE-01), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (IRGACURE OXE 02), N- 1919 (made by ADEKA), TRONLYTR-P
BG-304, TRONLY TR-PBG-305, TRONLY TR-PBG-309 (all of which are manufactured by Changzhou Strong New Materials Co., Ltd.) are commercially available. In addition to these, oximes described in JP2007-210991A, JP2009-179619A, JP2010-037223A, JP2010-215575A, JP2011-020998A, and the like. It is also possible to use an ester photopolymerization initiator.

<Organic solvent (D)>
The photosensitive coloring composition of this invention contains the organic solvent (D). The colorant is sufficiently dispersed and infiltrated into the colorant carrier with the organic solvent (D), and applied to a glass substrate or the like so as to have a dry film thickness of 0.2 to 5 μm to form a filter segment. Can make it easier.
An organic solvent can be used individually by 1 type or in mixture of 2 or more types. Moreover, since the solvent can adjust the coloring composition to an appropriate viscosity and can form a filter segment with a desired uniform film thickness, the total weight of the colorant is 100% by mass (500% to 4000% by mass). It is preferable to use it in the quantity.

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 diester. Acetate, 1,4-butanediol diacetate, 1,
4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m -Xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenze , P-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether , Ethylene glycol monoethyl ether acetate, ethylene glycol mono tertiary 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 Ke T, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol Methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetate , 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 esters. These solvents can be used alone or in admixture of two or more at any ratio as required.

  Among them, the dispersibility of the colorant, the penetrability, and the coating property of the photosensitive composition are good, so that ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol diacetate, ethylene glycol monomethyl ether 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 a polymerizable compound (E). The polymerizable compound (E) includes monomers and oligomers that are cured by ultraviolet rays or heat to generate 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, trimethylolpropane tri (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, trimethylol Ropan PO modified tri (meth) acrylate, trimethylolpropane EO modified tri (meth) acrylate, isocyanuric acid EO modified di (meth) acrylate, isocyanuric acid EO modified tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, penta Erythritol 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, tricyclodecanyl (meth) acrylate , Ester acrylate, methylolated melamine (meth) acrylic acid ester, epoxy (meth) acrylate, urethane acrylate and other acrylic acid esters and methacrylic acid esters, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, Examples include, but are not necessarily limited to, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.
These polymerizable compounds can be used singly or as a mixture of two or more at any ratio as required.

These commercially available products include KAYARAD R-128H, KAYARAD R526, KAYARAD PEG400DA, KAYARADMAND, 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 Toa Gosei 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 BISCOAT # 310HP, BISCOAT # 335HP, BISCOAT # 700, BISCOAT # 295, BISCOAT # 330, biscoat # 360, biscoat #GPT, biscoat # 400, biscoat # 405, A-9300 manufactured by Shin-Nakamura Chemical Co., etc. can be suitably 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. When the amount is less than the above, the tapered portion of the photosensitive coloring composition pattern is elongated and it becomes difficult to form a high-definition fine pixel pattern. If it is more than the above, problems such as resolution and deterioration of the 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 esterified products of poly (meth) acrylates containing a free hydroxyl group of polyhydric alcohol and (meth) acrylic acid and dicarboxylic acids; polyhydric carboxylic acid and monohydroxyalkyl Examples include esterified products with (meth) acrylates. Specific examples include monohydroxy oligoacrylates or monohydroxy oligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, etc. And a monoesterified product of free carboxyl group with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, 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 monohydroxy monoacrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, or monohydroxy monomethacrylates containing free carboxyl group-containing oligoesters and the like. However, the effects of the present invention are not limited to these.

As these commercially available products, Biscoat _# 2500P manufactured by Osaka Organic Chemical Co., Ltd., M-5300, M-5400, M-5700, M-510, M-520 manufactured by Toa Gosei Co., Ltd., and the like can be suitably used.

  These polymerizable compounds having an acid group can be used singly or as a mixture of two or more at any ratio as required.

(Polymerizable compound having 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 obtained by reacting a polyfunctional isocyanate with an alcohol and further reacting a (meth) acrylate having a hydroxyl group. Examples thereof include urethane acrylate.

As the (meth) acrylate having a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri ( (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol ethylene oxide modified penta (meth) acrylate, dipentaerythritol propylene oxide modified penta (meth) acrylate, dipentaerythritol caprolactone modified penta (meth) acrylate, glycerol acrylate Methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, containing epoxy groups The reaction product of compound and the carboxy (meth) acrylate, hydroxyl group-containing polyol polyacrylate, and the like.

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

  Moreover, although there is no restriction | limiting in the structure of alcohol, when a polyhydric alcohol is used, since the crosslinking degree of a cured coating film becomes high and coating-film resistance goes up, it is preferable. Examples of the polyhydric alcohol include propylene glycol, ethylene glycol, glycerin, trimethylolpropane, and pentaerythritol.

  As these commercial products, AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, DAUA-167, manufactured by Kyoeisha Chemical Co., Ltd., manufactured by Shin-Nakamura Chemical Co., Ltd. UA-160TM, UV-4108F manufactured by Osaka Organic Chemical Industry Co., Ltd., UV-4117F, and the like can be suitably used.

  These photopolymerizable monomers having a urethane bond can be used singly or in combination of two or more at any 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 a thermoplastic resin and a thermosetting resin.

(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, polyvinyl acetate. , Polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. . Among them, it is preferable to use an acrylic resin.

(Thermosetting resin)
Examples of the thermosetting resin used for the binder resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, cardo resins, and phenol resins.

  The thermosetting resin may be, for example, a low-molecular 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 at the time of firing the filter segment, the cross-linking density of the coating film is increased, the heat resistance is improved, and the effect of suppressing pigment aggregation at the time of firing the filter segment is obtained. It is done. Among these, an epoxy resin, a cardo resin, or a melamine resin is preferable.

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

  Since the binder resin has good film formability and various resistances, it is preferably used 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 expressed, the resin solid content is preferably used 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 development type colored resist material, an alkali-soluble vinyl resin prepared using an acidic group-containing ethylenically unsaturated monomer from the viewpoint of developability. Is preferably used as a binder resin. In another embodiment, a photosensitive coloring composition may be configured for the purpose of improving photosensitivity and 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 more specifically.

  As the vinyl-based alkali-soluble resin that can be suitably used as a binder, for example, a homopolymer or copolymer prepared using an ethylenically unsaturated monomer having an acidic group such as a carboxyl group, a hydroxyl group, or a sulfone group Is 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. Among these, 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 of its high heat resistance and transparency.

  As the acidic group in the acidic group-containing ethylenically unsaturated monomer used for preparing the resin, those having a carboxylic acid or a hydroxyl group are preferable. Examples of the ethylenically unsaturated monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid. Examples of the ethylenically unsaturated monomer having a hydroxyl group include, for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 4 -Hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl acrylate, or caprolactone adducts of these monomers (additional mole number is preferably 1 to 5).

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

  From the above viewpoint, the vinyl 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 10,000 to 80000. It 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 constituting a photosensitive coloring composition as an alkali development type color 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, no coating film foreign matter is generated after the resist is applied, and the stability of the colorant in the resist material is improved. Tend. When the above-mentioned linear resin that does not have an ethylenically unsaturated double bond in the side chain is used, the colorant is not easily trapped by the resin and has a degree of freedom in a mixture of resin and colorant. As a result, the colorant component easily aggregates and precipitates. In contrast, when an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain is used, the colorant is easily trapped in the resin in a mixture of the resin and the colorant. For this reason, in the solvent resistance test, it is difficult for the pigment to elute and the colorant component does not easily aggregate and precipitate. In addition, when the film is formed by exposure with active energy rays, the colorant molecules are fixed by the three-dimensional crosslinking of the resin, and the colorant component aggregates and precipitates even if the solvent is removed in the subsequent development process. It is estimated that it becomes difficult to do.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins having an unsaturated ethylenic double bond introduced by the following methods (a) and (b).

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

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

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. Remaining by using a tricarboxylic anhydride such as trimellitic anhydride or using a tetracarboxylic dianhydride such as pyromellitic dianhydride, if necessary, such as increasing the number of carboxyl groups An anhydride group can also be hydrolyzed. Moreover, when an etrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be 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 and one or more other monomers. There is a method in which an unsaturated ethylenic monomer having an epoxy group is added to a part of a carboxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.

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

  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 or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Further, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) 12-hydroxystearic acid added (poly) ester mono (meth) acrylate can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable.

  Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like. In addition, two or more types can be used in combination.

<Sensitizer>
A sensitizer can be contained in the photosensitive composition of the present invention.
Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 'or 4,4'-tetra (t-butylperoxycarbonyl) benzophenone 4,4′-bis (diethylamino) benzophenone and the like.
Specific examples include Okawara Nobu et al., “Dye Handbook” (1986, Kodansha), Okawara Nobu et al., “Functional Dye Chemistry” (1981, CMC), Ikemori Chusaburo et al., “Special Examples include, but are not limited to, sensitizers described in “Functional Materials” (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.
Among the sensitizers, sensitizers that can be sensitized particularly preferably include thioxanthone derivatives, Michler ketone derivatives, and carbazole derivatives. 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 singly or in combination of two or more at any ratio as required.
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 Co., Ltd.). It is done.

  More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

  The content when using the sensitizer is preferably 3 to 60 parts by mass with respect to 100 parts by mass of the radical photopolymerization initiator contained in the colored composition, from the viewpoint of photocurability and developability. It is more preferable that it is 5-50 mass parts.

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

Epoxy compounds include phenol novolac type epoxy resin, cresol novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, biphenol type epoxy. Examples thereof include resins, bisphenol-A novolac 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 improvement of water spots or heat resistance and chemical resistance.

  Specific examples of the phenol novolac type epoxy resin include, for example, Epicron N-740, Epicron N-770, Epicron N-775 manufactured by DIC Corporation, and D.C. E. N438, Nippon Kayaku Co., Ltd. RE-306, Mitsubishi Chemical Corporation jER152, jER154, etc. are mentioned.

  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. EXP, Epicron N-672-EXP, Nippon Kayaku Co., Ltd. EOCN-102S, EOCN-103S, EOCN-104S, Union Carbide Corporation UVR-6650, Sumitomo Chemical Co., Ltd. ESCN-195 etc. are mentioned.

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

  Specific examples of the dicyclopentadiene phenol type epoxy resin include Epicron EXA-7200 manufactured by DIC Corporation, and TACTIX-556 manufactured by Dow Chemical Co., Ltd.

  Specific examples of the bisphenol type epoxy resin include jER828 and jER1001 manufactured by Mitsubishi Chemical Corporation, UVR-6410 manufactured by Union Carbide Corporation, and D.C. E. Bisphenol-A type epoxy resin such as R-331, YC-8125 manufactured by Nippon Kayaku Manufacturing Co., Ltd., UVR-6490 manufactured by Union Carbide Co., Ltd., YDF-8170 manufactured by Nippon Kayaku Manufacturing Co., Ltd. An epoxy resin etc. are 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 Co., Ltd., jERY manufactured by Mitsubishi Chemical Corporation.
Examples thereof include xylenol type epoxy resins such as X-4000 and jER YL-6121.

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

  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 Seikeside 2021P, 2081, 2000, Epolide PB3600, PB4700, GT401, EHPE-3150, and Cyclomer M100 manufactured by Daicel Corporation.

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

  These epoxy compounds can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

  Content of the epoxy compound used for the photosensitive coloring composition of this invention is 0.5-50 mass% normally in 100 mass% of solid content of a coloring composition, Preferably it is 1-40 mass%. When the content of the epoxy compound is in the above range, heat resistance is high and an excellent coating film is 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 is not particularly limited and can be used. 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 more.

Examples of monofunctional oxetane groups include (3-ethyloxetane-3-yl) methyl acrylate, (3-ethyloxetane-3-yl) methyl methacrylate, 3-ethyl-3
-Hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-methacryloxymethyl) oxetane, 3- And ethyl-3-{[3- (triethoxysilyl) propoxy] methyl} oxetane.
Specific examples include OXE-10 manufactured by Osaka Organic Chemical Industry Co., Ltd., OXE-30 manufactured by Toagosei Co., Ltd., OXT-101, 212, and the like.

Examples of the bifunctional oxetane group include 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl), 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl]. Benzene, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, 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- Oxetanyl) -5-oxa-nonane, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3- Til-3-oxetanylmethoxy) methyl] propane, ethyleneglycose bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethyleneglycolbis (3-ethyl) -3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl) -3-Oxetanylmethoxy) hexane, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO) modified bis Enol 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.
Specific examples include Ube Industries, Ltd., OXBP, OXTP, Toagosei Co., Ltd., OXT-121, OXT-221, and the like.

  Examples of the oxetane group having two or more functional groups include pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, 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-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis (3- (Ru-3-oxetanylmethyl) ether, a resin containing an oxetane group (for example, an oxetane-modified phenol novolak resin described in Japanese Patent No. 3784462) or a (meth) acrylic monomer such as the aforementioned OXE-30 is radically polymerized. The obtained polymer is mentioned. Such a polymer can be obtained using a known polymerization method.

  Content of the oxetane compound used for the photosensitive composition of this invention is 0.5-50 mass% normally in 100 mass% of solid content of a coloring composition, Preferably it is 1-40 mass%. It is preferable for the content of the oxetane compound to be in the above range since an excellent coating film having good water spots and high chemical resistance can be obtained.

<Thiol chain transfer agent>
The photosensitive composition of the present invention can contain a thiol chain transfer agent as a chain transfer agent. By using thiol together with a photopolymerization initiator, a thiyl radical that acts as a chain transfer agent and is less susceptible to polymerization inhibition by oxygen is generated in the radical polymerization process after light irradiation, so that the resulting colored composition has high sensitivity. .

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, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropioate. , Trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid Tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibu Tilamino) -4,6-dimercapto-s-triazine and the like, preferably ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate.

  These thiol chain transfer agents can be used singly or in combination of two or more.

Moreover, it is preferable that content of a thiol type | system | group chain transfer agent is 1-10% in the total solid of a coloring composition, More preferably, it is 2.0-8.0%. In this range, the effect of the chain transfer agent is increased, and the sensitivity, taper shape, wrinkle, film shrinkage ratio and the like are improved.

<Ultraviolet absorber>
The photosensitive composition of the present invention can 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 organic compounds, triazine organic compounds, benzophenone organic compounds, cyanoacrylate organic compounds, and salicylate organic compounds. .

  As for content of a ultraviolet absorber, 5-70 mass% is preferable in a total of 100 mass% of a photoinitiator and a ultraviolet absorber. When 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. When the content is more than the above, the sensitivity is low and the pixel peeling or the hole diameter is larger than the design value. In some cases, such a problem may occur.

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

  Further, the total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass in 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 deteriorate.

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

Examples of the benzotriazole-based organic compound include 2- (5 methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, and octyl-3 [3-tert-butyl. -4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H) -Benzotriazol-2-yl) phenyl] propionate, 2- [2-hydroxy-
3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (
3-tbutyl-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, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) pheno Le, and the like.

More specifically, “TINUVIN P”, “TINUVIN PS”, “TINUVIN 109”, “TINUVIN 234”, “TINUVIN 326” manufactured by BASF
, “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 and the like.

  Examples of triazine organic compounds include 2- [4,6-di (2,4-xylyl) -1,3,5-triazin-2-yl] -5-octyloxyphenol, 2- [4,6-bis. (2,4-Dimethylphenyl) -1,3,5-triazin-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropoxy] phenol, 2- (2,4-dihydroxyphenyl)- Reaction product of 4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl-glycidic acid ester, 2,4-bis “2-hydroxy-4-butoxyphenyl” And -6- (2,4-dibutoxyphenyl) -1,3-5-triazine.

More specifically, “KEMISORB 102” manufactured by Chemipro Kasei 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 Co., Ltd., and the like.

  Examples of benzophenone-based organic compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3 water temperature, 2-hydroxy-4-n- Examples 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 "," SEESORB 101 "," SEESORB 10 "manufactured by Sipro Kasei Co., Ltd.
7 ”,“ Adeka Stub 1413 ”manufactured by ADEKA, and the like.

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

  As polymerization inhibitors, catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert- Alkyl catechol compounds such as butyl catechol and 3,5-di-tert-butyl catechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresor Alkyl resorcinol compounds such as sinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, 4-tert-butylresorcinol, methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, Alkylhydroquinone compounds such as 2,5-di-tert-butylhydroquinone, phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine, trioctylphosphine oxide, triphenylphosphine oxide, etc. Phosphites such as phosphine oxide compounds, triphenyl phosphite, trisnonylphenyl phosphite Compounds, pyrogallol, and the like phloroglucinol. As for content of a polymerization inhibitor, 0.01-0.4 mass part is preferable with respect to 100 mass parts of weight except the solvent of the coloring composition. In this range, the effect of the polymerization inhibitor is increased, and the taper linearity, the wrinkle of the coating film, the pattern resolution, etc. are improved.

<Antioxidant>
The photosensitive composition of the present invention can contain an antioxidant. Antioxidant (The photopolymerization initiator and thermosetting compound contained in the red photosensitive composition are oxidized to prevent yellowing due to thermal process during thermal curing or ITO annealing. In particular, when the colorant concentration of the coloring composition is high, the amount of the coating film crosslinking component decreases, so the use of a highly sensitive crosslinking component and the increase in the amount of the photopolymerization initiator are taken into account in the thermal process. There is a phenomenon that the yellowing of
Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high coating film transmittance can be obtained.

  The “antioxidant” in the present invention may be a compound having an ultraviolet absorption function, a radical scavenging function, or a peroxide decomposition function. Specifically, as an antioxidant, a hindered phenol type, a hindered amine type are used. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used. In addition, the antioxidant used in the present invention preferably does not contain a halogen atom.

  Among these antioxidants, a hindered phenol antioxidant, a hindered amine antioxidant, a phosphorus antioxidant, or a sulfur antioxidant is preferable from the viewpoint of achieving both transmittance and sensitivity of the coating film. Agents.

As the hindered phenol-based antioxidant, 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), 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-tert-butyl-5-methylphenol), 2,2'-thio- Su- (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 Cinnamamide) 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 ADK STAB AO-20, AO-30, AO-40,
AO50, AO60, AO80, AO320, Kemipro Corporation KEMINOX 101, 179, 76, 9425, BASF Corporation IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057 565, Cyanox CY-1790, CY-2777, manufactured by Sun Chemical Co., Ltd., and the like.

Examples of hindered amine-based antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 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-triazine-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)- Polycondensate with 4-hydroxy-2,2,6,6-tetramethylpiperidine, N, N′-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2 , 6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, etc. Other oligomer type having a hindered amine structure And poly Mer type compounds can also be used.
Specific examples include Adeka Stab LA-52, LA-57, LA-63 manufactured by ADEKA Corporation.
P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, LA-502XP, KAMISTAB 29, 62, 77, 29 manufactured by Chemipro Kasei Co., Ltd. 94, Tinuvin 249, TINUVIN111FDL, 123, 144, 292, 5100 manufactured by BASF Corporation, Siasorb UV-3346, UV-3529, UV-3385 manufactured by Sun Chemical Co., Ltd., and the like.

Phosphorous antioxidants include tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl Phosphite, diphenyltridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, 4,4 ′ isopropylidenediphenol phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris (2 , 4-di-t-butylphenyl) phosphite, tris (biphenyl) phosphite, distearyl pentaerythritol diphosphite, di (2 , 4-di-t-butylphenyl) pentaerythritol diphosphite, di (nonylphenyl) 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) butane triphosphite, 3,5-di-t-butyl -4-hydroxybenzyl phosphite diethyl ester, sodium bis (4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3 -Bis (diphenoxyphosphonoxy) -ben Zen, ethylbisphosphite (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.
Specific examples include Adeka Stab PEP-36, PEP-8, and HP-1 manufactured by ADEKA Corporation.
0, ADK STAB 2112, 1178, 1500, C, 3013, TPP, IRGAFOS168 manufactured by BASF Corporation, HostanoxP-EPQ manufactured by Clariant Chemicals Corporation, and the like.

As sulfur-based antioxidants, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 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 Stub AO-412S and AO-503 manufactured by ADEKA Corporation, and KEMINOXPLS manufactured by Chemipro Kasei Corporation.

As the benzotriazole-based antioxidant, oligomer-type and polymer-type compounds having a benzotriazole structure can be used.
Specific examples include Adeka Stab LA-29, LA-31RG, LA- manufactured by ADEKA Corporation.
32, LA-36, -412S, Chemipro Chemical Co., Ltd. KEMISORB 71, 73, 74, 79, 279, BASF Corporation TINUVIN PS, 99-2, 384-2, 900, 928, 1130 and the like.

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

Examples of the triazine 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 Stab LA-46 and F70 manufactured by ADEKA Co., Ltd., KEMISORB102 manufactured by Chemipro Kasei Co., Ltd., TINUVIN400, 405, 460, 477 and 479 manufactured by BASF Co., Ltd., and Siasorb UV-1164 manufactured by Sun Chemical Co., Ltd. .

  Examples of the salicylate ester antioxidant include phenyl salicylate, p-octylphenyl salicylate, p-tertbutylphenyl salicylate, and the like. In addition, oligomer-type and polymer-type compounds having a salicylate structure can also be used.

  These antioxidants can be used singly or as a mixture of two or more at any ratio as required.

  Further, the content of the antioxidant is more preferably 0.5 to 5.0% by mass in 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 can contain an adhesion improving agent such as a silane coupling agent in order to improve the adhesion to the substrate. By improving the adhesion with the adhesion improver, the reproducibility of fine lines is improved and the resolution is improved.

  Examples of the adhesion improver include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3- (Meth) acrylsilanes such as methacryloxypropyltriethoxysilane and 3-acryloxypropyltrimethoxysilane 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3- Epoxysilanes such as glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylme Rudimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3- Aminosilanes such as dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-mercaptopropyl Mercaptos such as methyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, styryls such as p-styryltrimethoxysilane, ureides such as 3-ureidopropyltriethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, etc. Sulfides Silane coupling agent of isocyanates such as 3-isocyanate propyl triethoxysilane and the like. 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. Within this range, the effect becomes large, and the balance between adhesion, resolution, and sensitivity is good, which is more preferable.

<Leveling agent>
A leveling agent is preferably added to the photosensitive composition of the present invention for the purpose of improving the coating property of the composition on the transparent substrate and the drying property of the colored film. As the leveling agent, various surfactants such as silicone surfactants, fluorine surfactants, nonionic surfactants, and cationic surfactants (surfactants and anionic surfactants) can be used.
Examples of silicone surfactants include linear polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups are introduced into side chains and terminals.
Specific examples include BYK-300, BYK-306, BYK-310, BYK-313, BYK-315N, BYK-320, BYK-322, BYK-323, BYK-330, BYK-331, BYK-manufactured by BYK-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-22-2 4272, X-22-6266, KF-351A, K354L, KF-3 5A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, etc. KF-6004 and the like.

Examples of the fluorosurfactant 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, DIC Corporation MegaFuck F-253, F-477, F-551, F-552, F-555, F-558, F-560, F-570, F-575, F-576, R-40-LM, R-41, RS-72-K, DS-21, Sumitomo 3M Limited FC-4430, FC-4432, Mitsubishi Materials Electronics Chemical Co., Ltd. Examples thereof include EF-PP31N09, EF-PP33G1, EF-PP32C1, and Neos Corporation's Footgent 602A.

Nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristol ether, polyoxyethylene octyldodecyl Ether, polyoxyalkylene alkyl ether, polyoxyphenylene distyrenated phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyethylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl Ether phosphate, sorbitan monolaurate, sorbitan monopalmitate, sol Tan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan monolaurate, sorbitan esquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, Polyoxyethylene orbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbite tetraoleate, glycerol monostearate, glycerol monooleate Ate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol di Teareto, polyethylene glycol monomethyl oleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl amines, alkyl alkanol amides, alkyl betaine such as alkyl imidazoline and alkyl dimethyl amino acetic acid betaine.
Specific examples include Emulgen 103, Emulgen 104P, Emulgen 106, Emulgen 108, Emulgen 109P, Emulgen 120, and Emulgen 123 manufactured by Kao Corporation.
P, Emulgen 130K, Emulgen 147, Emulgen 150, Emulgen 210P, Emulgen 220, Emulgen 306P, Emulgen 320P, Emulgen 350, Emulgen 404, Emulgen 408, Emulgen 409PV, Emulgen 420, Emulgen 430, Emulgen 705, Emulgen 707, Emulgen 709, Emulgen 1108, Emulgen 1118S-70, Emulgen 1135S-70, Emulgen 1150S-60, Emulgen 2020G-HA, Emulgen 2025G, Emulgen LS-106, Emulgen LS-110, Emulgen LS-114, Emulgen MS-110, Emulgen A-60 , Emulgen A-90, Emulgen B-66, Emulgen PP-290, Latemul PD-420, Latem PD-430, LATEMUL PD-430S, LATEMUL PD450, RHEODOL SP-L10, LEODOL SP-P10, LEODOL SP-S10V, LEODOL SP-S20, LEODOL SP-S30V, LEODOL SP-O10V, LEODOL SP-O30V, LEODOL SUPER SP-L1, Rheodor AS-10V, Rheodor AO-10V, Rheodor AO-15V, Rheodor TW-L120, Rheodor TW-L106, Rheodor TW-P120, Rheodor TW-S120V, Rheodor TW-L106V, Rheodor TW-S320V, Rheodor TW-O120V, Rheodor TW-O106V, Rheodor TW-IS399C, Rheodor Super TW-L120, Rheodor 430V, Rheodor 440V, Rheodo 460V, Rheodor MS-50, Rheidol MS-60, Rheodor MO-60, Rheodor MS-165V, Emanon 1112, Emanon 3199V, Emanon 3299V, Emanon 3299RV, Emanon 4110, Emanon CH-25, Emanon CH-40, Emanon CH -60 (K), Amite 102, Amite 105, Amite 105A, Amite 302, Amite 320, Aminone PK-02S, Aminone L-02, Homogenol L-95, Adeka Pluronic L-23, 31, 44 61, 62, 64, 71, 72, 101, 121, Adeka Pluronic TR-701, 702, 704, 913R, and the like.

Examples of cationic surfactants include alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, and their ethylene oxide adducts.
As specific examples, Acetamine 24, 26, Cotamin 24P, 86P Conch manufactured by Kao Corporation, KP341 manufactured by Shin-Etsu Chemical Co., Ltd., (meth) acrylic acid (co) polymer polyflow No. manufactured by Kyoeisha Chemical Co., Ltd. 75, no. 90, no. 95 etc. are mentioned.

Anionic surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, lauryl sulfate monoethanolamine , Lauryl sulfate triethanolamine, 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 Neos Inc.'s Footgent 100, 150, Adeka Corporation Adeka Hope YES-25, Adeka Coal 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 addition amount of the surfactant is preferably 0.001 to 2.0% by mass with respect to the total solid content of the composition of the present invention. Preferably it is 0.005-1.0 mass%. By being in this range, the balance between the coating property of the colored composition, the pattern adhesion, and the transmittance is improved.
The photosensitive composition of the present invention may contain only one type of surfactant or two or more types of surfactant. When two or more types are included, the total amount is preferably within the above range.

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

<Method for producing colored dispersion>
The photosensitive coloring composition included in the present invention comprises a kneader, a two-roll mill, a three-coloring agent in a coloring agent carrier such as a dispersing agent, a binder resin, and / or a solvent, preferably together with a dispersing aid. It can be produced based on a colored dispersion produced by fine dispersion using various dispersing means such as a roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor. At this time, two or more kinds of colorants or the like may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the colorant carrier may be mixed. When the solubility of the colorant such as a dye is high, specifically, it is not necessary to carry out fine dispersion as long as the solubility in the solvent to be used is high and dissolution and foreign matter are not confirmed by stirring. In the present invention, it is preferable to disperse the colorant (A) using the resin-type dispersant (B) when producing the colored dispersion.

  Moreover, when using as a photosensitive coloring composition (resist material) for color filters, it can prepare as a solvent developing type or an alkali developing type coloring composition. The solvent development type or alkali development type coloring composition comprises 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 colored composition, or may be added later to the prepared colored composition.

<Dispersing aid>
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, and a surfactant can be appropriately contained. Since the dispersion aid has a great effect of preventing re-aggregation of the colorant after dispersion, the color composition formed by dispersing the colorant in the colorant carrier using the dispersion aid has brightness, contrast, and storage stability. Property is improved.

[Resin dispersant]
Although the photosensitive composition of this invention contains the above-mentioned resin type dispersing agent (B), you may contain a conventionally well-known resin type dispersing agent as others.
The resin-type dispersant has a colorant-affinity part that has the property of adsorbing to the additive colorant and a part that is compatible with the colorant carrier, and is adsorbed to the additive colorant and dispersed in the colorant carrier. It works to stabilize. Specific examples of resin-type dispersants include 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 thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-based 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 resin, water-soluble polymer compound, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide adduct, phosphoric ester or the like is used, they may be used alone or in combination, it is not necessarily limited thereto.

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

  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 Chemi 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 or Bykumen, etc. 3000, 13240, 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., BASF EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4 00,5010,5065,5066,5070,7500,7554,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of Ajisupa -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 suitably used. The resin-type dispersant used in the present invention preferably contains the following (S1) or (S2) as a resin-type dispersant having a carboxyl group.
(S1) A resin-type dispersant that is a reaction product of a hydroxyl group of a polymer having a hydroxyl group and an acid anhydride group of a tricarboxylic anhydride and / or a tetracarboxylic dianhydride.
(S2) A polymer obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product of a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of a tricarboxylic anhydride and / or a tetracarboxylic dianhydride. A resinous 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, JP2008-029901A, or JP2009-155406A. 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 it is preferable that there are a plurality of terminal hydroxyl groups, a compound (q1) having two hydroxyl groups and one thiol group in the molecule is preferably used.

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

≪Resin type dispersant (S2) ≫
The resin-type dispersant (S2) can be produced by a known method such as JP2009-155406A, JP2010-185934A, JP2011-157416A, 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 of (q) and the acid anhydride group of tricarboxylic anhydride and / or tetracarboxylic dianhydride. can get. In particular, 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 anhydride and / or tetracarboxylic dianhydride. And a polymer obtained by polymerizing the ethylenically unsaturated monomer (r) containing the monomer (r1).

The difference between (S1) and (S2) is whether the polymer site obtained by polymerizing the ethylenically unsaturated monomer (r) is introduced first or later. The molecular weight and the like may be slightly different depending on various conditions, but theoretically the same can be obtained if the raw materials and reaction conditions are the same.

[Dye derivative]
As the dye derivative used in the present invention, a known dye derivative having an organic group, an acidic group, a basic group, a neutral group or the like 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. JP-A 63-305173, JP-B 57-15620, JP-B 59-40172, JP-B 63-17102, JP-B 5-9469, JP-A 2001-335717, JP JP 2003-128669, JP 2004-091497, JP 2007-156395, JP 2008-094773, JP 2008-094986, JP 2008-095007, JP 2008. JP-A-195916, JP-B-45855781, JP-A-2006-291194, JP-A-2007-226161, JP-A-2007-314681, JP-A-2007-314785, JP-A-2012-226110 JP-A-2017-165820, JP-A-2005-2005 81383 JP, include known dye derivative according to such. In these documents, the dye derivative may be described as a derivative, a pigment derivative, a pigment dispersant, or simply a compound. However, an acidic group, a basic group, a neutral group, or the like may be added to the organic dye residue. The compound having the functional group is synonymous with the pigment derivative. Moreover, these can be used individually or in mixture of 2 or more types.

  The content of the pigment derivative is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and most preferably 3 parts by mass or more with respect to 100 parts by mass of the colorant from the viewpoint of improving dispersibility. 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 pigment derivative to the pigment and performing a dispersion treatment such as wet dispersion using two rolls, three rolls, or beads, the pigment derivative is adsorbed on the pigment surface and the pigment surface has polarity, and the resin type dispersant is adsorbed. And improved compatibility with pigments, dye derivatives, resin-type dispersants, solvents, and other additives, and improved dispersion stability and viscosity stability over time when used as a colored composition or colored curable composition To do. In addition, the compatibility improves so that the coating aging stability is excellent when the colored curable composition is applied to glass, and the waiting time from application of the colored curable composition to exposure (PCD: Post Coating Delay). In addition, stability and characteristic dependency such as pattern shape with respect to a waiting time from exposure to heat treatment (PED: Post Exposure Delay) and line width sensitivity stability are improved. Furthermore, development time variations and development residues are also suppressed.

[Surfactant]
Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these may be used alone or in admixture of two or more, but are not necessarily limited thereto.

  When adding a surfactant, 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. When the content of the surfactant is less than 0.1 parts by mass, it is difficult to obtain the added effect. When the content is more than 55 parts by mass, the dispersion may be affected by an excessive dispersant. .

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

Any filter can be used without particular limitation as long as it has been conventionally used for filtration. For example, fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg nylon-6, nylon-6,6), polyolefin resins such as polyethylene and polypropylene (PP) (high density, ultra high molecular weight) Etc.) and the like. Among these materials, polypropylene (including high density polypropylene) and nylon are preferable.
The filter has a pore diameter of 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. By setting it as this range, it becomes possible to remove a fine foreign material reliably. It is also preferable to use a fiber-shaped filter medium. Examples of the fiber-shaped filter medium include polypropylene fiber, nylon fiber, glass fiber, and the like. Specifically, SBP type series (SBP008 etc.), TPR type series (TPR002, TPR005 etc.), SHPX type series manufactured by Loki 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 may be performed twice or more.
Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above. The pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, selected from various filters provided by Nippon Pole Co., Ltd. (DFA4201NXEY, etc.), Advantech Toyo Co., Ltd., Japan Integris Co., Ltd. (formerly Nihon Microlith Co., Ltd.) or KITZ Micro Filter Co., Ltd. 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. The color filter may further include a magenta filter segment, a cyan filter segment, and a yellow filter segment. The color filter of the present invention preferably has a red filter segment formed from the red photosensitive composition of the present invention.

<Color filter manufacturing method>
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 simply by repeating the printing and drying of the coloring composition prepared as the printing ink. Therefore, the color filter manufacturing method is low in cost and excellent in mass productivity. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

  When the filter segment is formed by photolithography, the colored composition prepared as a solvent developing type or alkali developing type colored resist material is applied on a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. By a method, it applies so that a dry film thickness may be set to 0.2-5 micrometers. If necessary, the dried film is exposed (irradiation with radiation) through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate | stimulate superposition | polymerization of a colored resist material, it can also heat at 80 to 250 degreeC as needed. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
In order to increase exposure sensitivity, after coating and drying the colored resist, 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 that prevents polymerization inhibition due to oxygen. The exposure can also be performed.

The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an ink jet method or the like in addition to the above method, but the colored composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . 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 this filter segment is transferred to a desired substrate.

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

  The color filter of the present invention is bonded to a counter substrate using a sealant, and after injecting liquid crystal from an injection port provided in a seal portion, the injection port is sealed, and a polarizing film or a retardation film is formed on the substrate as necessary. A color liquid crystal display device is manufactured by pasting to the outside. This color liquid crystal display device includes Twisted Nematic (TN), Super Twisted Nematic (STN), In-Plane Switching (IPS), Vertical Alignment (VA), Optically Convencend Bend (OCB). ) Etc., and can be used in a liquid crystal display mode in which colorization is performed.

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

  EXAMPLES The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. 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 TPCgel column (manufactured by Tosoh Corporation), GPC equipped with RI detector (manufactured by Tosoh Corporation, HLC-8320GPC), and measured in terms of polystyrene measured using THF as a developing solvent. It is a weight average molecular weight (Mw).

(Resin acid value)
The resin acid value is a value obtained by converting the measured acid value (mgKOH / g) into a solid content according to the potentiometric titration method of JIS K0070.

<Production of resin-type dispersant (B)>
(Resin type dispersant (B-1))
In a reaction vessel equipped with a gas inlet 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), catalyst After adding 0.2 parts of monobutyltin oxide and replacing with nitrogen gas, the mixture was reacted at 120 ° C. for 5 hours (first step). It was confirmed by acid value measurement that 95% or more of the acid anhydride was half-esterified. Next, 30 parts methyl methacrylate (MMA), 10 parts t-butyl acrylate (tBA), 10 parts ethyl acrylate (EA), 5 parts methacrylic acid (MAA), 10 parts benzyl methacrylate (BzMA), 2-hydroxyethyl methacrylate (HEMA) 35 parts, the inside of the reaction vessel was heated to 80 ° C., 1 part of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and reacted for 12 hours (second step). . It was confirmed that 95% had reacted by solid content measurement. Next, the inside of the flask was purged with air, charged with 38.0 parts of 2-methacryloyloxyethyl isocyanate (MOI) and 0.1 part of hydroquinone, and reacted at 70 ° C. for 4 hours (third step). After confirming the disappearance of the peak at 2270 cm-1 based on the isocyanate group by IR, the reaction solution was cooled and the solid content was adjusted with PGMAc to obtain a solution of the resin type dispersant (B-1) having a solid content of 40%. Obtained. The resulting 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))
The synthesis was performed in the same manner as the resin type dispersant (B-1) except that the raw materials and preparation amounts shown in Table 1 and Table 2 were used, and the resin type dispersants (B-2) to (B-2) to (solid content 40%)-( A solution of B-22) was obtained.

BTDA: 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride MMA: methyl methacrylate tBA: t-butyl acrylate EA: ethyl acrylate MAA: methacrylic acid BzMA: benzyl methacrylate HEMA: 2-hydroxyethyl methacrylate HPMA: 2-hydroxypropyl methacrylate FM-3: terminal hydroxyl group polycaprolactone-modified methacrylate (manufactured by Daicel Chemical Industries: Plaxel FM-3)
MOI: 2-methacryloyloxyethyl isocyanate (manufactured by Showa Denko: Karenz MOI)
AOI: 2-acryloyloxyethyl isocyanate (produced by Showa Denko: Karenz AOI) BEI: 1,1-bis (acryloyloxymethyl) ethyl isocyanate (produced by Showa Denko: Karenz BEI)

<Manufacture of binder resin>
(Acrylic resin solution 1)
Place 100 parts of propylene glycol monomethyl ether acetate in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas inlet tube and stirrer in a separable four-necked flask, and heat to 120 ° C while injecting nitrogen gas into the vessel. 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 dropped over 2.5 hours from the dropping tube at a temperature to polymerize. Reaction was performed.
Next, the inside of the flask was purged with air, and 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. The reaction was terminated when the value 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 part of triethylamine were added and reacted at 120 ° C. for 4 hours, and propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 40% to prepare an acrylic resin solution 1. .

<Production of colorant (A)>
<Production of refined red pigment (PR254-1)>
Diketopyrrolopyrrole red pigment C.I. I. 200 parts of Pigment Red 254 ("Irgajin RedL 3630" manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. Diketopyrrolopyrrole-based fine red pigment (PR254-1) was obtained.

<Production of fine yellow pigment (PY 139-1)>
Yellow pigment C.I. I. 200 parts of Pigment Yellow 139 (“Pariotor Yellow D1819” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A fine yellow pigment (PY139-1) was obtained.

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

<Production of refined purple pigment (PV23-1)>
Dioxazine-based purple pigment C.I. I. 200 parts of Pigment Violet 23 (“LIONOGEN VIOLET RL” manufactured by Toyocolor Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A dioxazine-based purple refined purple pigment (PV23-1) was obtained.

<Production of refined green pigment (PG58-1)>
Phthalocyanine green pigment C.I. I. 200 parts of Pigment Green 58 (“FASTOGEN GREEN A110” manufactured by DIC Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A phthalocyanine-based fine green pigment (PG58-1) was obtained.

<Production of refined yellow pigment (PY150-1)>
Nickel complex yellow pigment C.I. I. 200 parts of Pigment Yellow 150 (“E-4GN” manufactured by LANXESS), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A nickel complex-based fine yellow pigment (PY150-1) was obtained.

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

<Method for Producing Salt-Forming Compound (V)>
In the following procedure, 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. In order to obtain a 5% aqueous solution, C.I. I. Acid Red 289 10 parts dissolved in 200 parts water, heated to 30-50 ° C., then dissolved 5.5 parts tristearyl monomethyl ammonium chloride to a 5% solution in methanol / water = 20/80 solution Then, it was dripped little by little. After dropwise addition of the tristearyl monomethyl ammonium chloride solution, the mixture was stirred at 30 to 50 ° C. for 3 hours. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer. I. Salt Formation Compound of Acid Red 289 and Tristearyl Monomethyl Ammonium Chloride (V)
8 parts were obtained.

<Method for producing 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-forming 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
<Production of colored dispersion>
(Coloring composition D-1)
After the following mixture was stirred and mixed so as to be uniform, it was dispersed for 5 hours with an Eiger mill (“Mini Model M-250MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm Filtration through a filter produced a colored composition (D-1).
Refined 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 parts

(Coloring composition D-2 to 65)
(Coloring compositions D-2 to 65) were produced 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.

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

  Abbreviations in Table 10 are shown below.

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

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

[Viscosity and viscosity stability of photosensitive coloring composition]
Regarding the obtained photosensitive coloring composition, the initial viscosity at 25 ° C. was measured using a viscometer TV22 manufactured by Toki Sangyo Co., Ltd. Moreover, the viscosity after acceleration at 40 ° C. for one month was measured, and the rate of increase in viscosity was calculated. Evaluation was performed according to the following criteria.
A: Initial viscosity is 10.0 Pa · s or less and increase in viscosity with time is less than 40% O: Initial viscosity is 10.0 Pa · s or less and increase in viscosity with time is 40% or more ×: Initial viscosity is 10. 0 Pa · s or more,

[Filter segment pattern formation]
The obtained photosensitive coloring composition was applied to a 10 cm × 10 cm glass substrate by spin coating, and then the solvent was removed by heating in a clean oven at 70 ° C. for 5 minutes 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 through a photomask having a stripe pattern of 100 μm width (pitch 200 μm) and 25 μm width (pitch 50 μm) at 50 mJ / cm ² . Thereafter, this substrate was spray-developed using a sodium carbonate aqueous solution at 23 ° C., washed with ion-exchanged water, air-dried, and heated at 230 ° C. for 20 minutes in a clean oven. The spray development was performed in the shortest time during which a pattern can be formed without any development remaining on the coating film of each photosensitive coloring composition, and this was set as an appropriate development time.
The film thickness of the coating film was determined using Dektak 3030 (manufactured by Nippon Vacuum Technology Co., Ltd.).

[Measurement of film thickness at specified chromaticity]
When the filter segment was formed by the above method, the number of spin coat rotations 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 is x = 0.655 in the case of the red photosensitive coloring composition, the film thickness is y = 0.614 in the case of the green photosensitive coloring composition, and the blue color sensitivity. In the case of the coloring composition, the film thickness at which y = 0.049 was obtained by calculation. Evaluation was performed according to the following criteria using the calculated film thickness.
A: Film thickness is 1.2 μm or more and less than 1.8 μm O: Film thickness is 1.8 μm or more and less than 2.2 μm X: Film thickness is 2.2 μm or more

[Resolution evaluation]
About the pattern in the 25 micrometer photomask part of the filter segment formed by the said method, the resolution was visually evaluated using the optical microscope. The poor resolution means that adjacent stripe patterns are connected or chipped. The rank of evaluation is as follows.
◎: Stripe pattern is completely independent, and no residue is observed between lines. ○: Stripe pattern is completely independent, but residue is observed between lines. △: Adjacent stripe patterns are partially connected. Yes: Adjacent stripe pattern is connected

[Linearity evaluation]
The pattern in the 100 μm photomask portion of the filter segment formed by the above method was evaluated by observing with an optical microscope. The rank of evaluation is as follows. C and D are difficult to use.
S: Linearity is very good A: Linearity is good B: Linearity is generally good and usable level C: Partially poor linearity and difficult to use D: Linearity poor

[Dimensional stability evaluation]
The line width was measured using an optical microscope for the pattern in the 100 μm photomask portion of the substrate subjected to patterning with exposure amounts of 30 mJ / cm ² and 50 mJ / cm ² . It 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 increase, the better the dimensional stability. If the increase was less than 3 μm, it was evaluated as a usable level. That is, C and D are difficult to use.
S: Increase 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 thicknesses of the filter segments formed by developing twice the appropriate time were compared with reference to the pattern film thickness formed by developing with the appropriate development time. The ranks of evaluation are as follows, and those having a difference in film thickness within 25% were regarded as usable levels.
◎: Film thickness difference within 15% ○: Film thickness difference over 15%, within 25%
Δ: Film thickness difference exceeds 25% and within 40% ×: Film thickness difference exceeds 40% Or chipping or peeling occurs.

As shown in Table 11, the filter segments formed using the photosensitive colored compositions of Examples 101 to 121, 201 to 209, and 301 to 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 better, and the pattern shape shows better characteristics. It was.
Further, the ratio 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 revealed that the pattern shape can be formed. Moreover, the photosensitive coloring composition manufactured using resin type dispersing agent B-22 had a high viscosity and was difficult to use. In addition, those using resin type dispersants B-14, B-15, B-16, and B-22 had good initial viscosity and were practical, but increased in viscosity over time.
Moreover, the double bond equivalent Z of the side chain of the resin-type dispersant (B) calculated as ((c) weight + (d) weight) / ((meth) acryloyl group mol number in (d)) is 300 to 300. Resins (B-1) to (B-7) and (B-10) to (B-19) at 600 g / mol exhibited excellent characteristics in a good pattern shape as compared with those not. 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%. Excellent resolution was shown. It has also been clarified 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 this patent.
Further, in RR-20, which is a comparative example having a high colorant content of 40% or more, the patterning characteristics are further deteriorated compared to RR-25 having a low colorant content, making 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

<Production of color filter>
A black matrix is patterned on a glass substrate, and the red photosensitive coloring composition (RR-3) of the present invention is applied to the substrate with a spin coater at x = 0.655, y = 0.
The coating was applied to 325 to form a colored film. The film was irradiated with ultraviolet rays of 50 mJ / cm ² using a super high pressure mercury lamp through a photomask.
Next, spray development was performed with an alkali developer composed of a 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, followed by washing with ion-exchanged water. Formed. In the same manner, the blue photosensitive coloring composition (RB- 1) of the present invention is adjusted so that 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, and a color filter was obtained.

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

Claims (6)

  A photosensitive coloring composition for a color filter comprising a colorant (A), a resin-type dispersant (B), a photopolymerization initiator (C), an organic solvent (D), and a polymerizable compound (E), wherein the resin The type dispersant (B) has a hydroxyl group of the compound (a) having two hydroxyl groups and one thiol group in the molecule, an acid anhydride group of pyromellitic acid anhydride and / or trimellitic acid anhydride, In the presence of the reaction product, 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), one isocyanate group, and It is a resin obtained by reacting an isocyanate group of the compound (d) having one or more (meth) acryloyl groups, and the content of the structural unit derived from the hydroxyl group-containing ethylenically unsaturated monomer (b) is Derived from ethylenically unsaturated monomer (c) Or less 80 wt% or more 35 wt% relative to the total amount of the structural units, for a color filter photosensitive coloring composition.   ((C) Total mass of structural units derived from ethylenically unsaturated monomer + (d) Total mass of structural units derived from a compound having one isocyanate group and one or more (meth) acryloyl groups) / (D) Resin-type dispersant (B) expressed as (m) (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 according to claim 1, wherein the double bond equivalent (Z) in the side chain is 300 to 600 g / mol.   Content of the structural unit derived from the hydroxyl group-containing ethylenically unsaturated monomer (b) in the resin-type dispersant (B) is based on the total amount of the structural unit derived from the ethylenically unsaturated monomer (c). The photosensitive coloring composition for color filters of Claim 1 or 2 which is 38 mass% or more and 60 mass% or less.   The photosensitive coloring composition for color filters according to any one of claims 1 to 3, wherein the content of the colorant (A) is 40% by mass or more based on the total solid content of the photosensitive coloring composition for color filters. object.   The photosensitive coloring composition for color filters of any one of Claims 1-4 in which a photoinitiator (C) contains an oxime ester type compound.   The color filter which comprises the filter segment formed from the photosensitive coloring composition for color filters of any one of Claims 1-5 on a base material.