JP6870329B2 - Photosensitive oligomers, methods for producing them, and photosensitive coloring compositions for color filters. - Google Patents

Description

The present invention relates to a transparent photosensitive material having photocurability, high pencil hardness, good yellowing resistance, and developability. The photosensitive oligomer of the present invention can be used for lenses, waveguides, optical fibers, interference films alternately laminated with low refractive index layers, optical filters, holograms, color filters, and the like.

A coloring composition in which a colorant containing a pigment is dispersed in a dispersant, a resin, a monomer, an organic solvent, or the like is generally used for forming a filter segment of a color filter, and developability is required in the manufacturing process. Be done. It is also important that the coating film after curing does not wrinkle. Carboxyl group-containing monomers and oligomers are effective in improving developability. Patent Documents 1 to 6 propose carboxyl group-containing monomers and oligomers, but they have not been able to solve the problems of developability and wrinkles in color filter applications.

Japanese Unexamined Patent Publication No. 11-181042 Japanese Unexamined Patent Publication No. 11-184082 Japanese Unexamined Patent Publication No. 11-184083 Japanese Unexamined Patent Publication No. 62-502848 Japanese Unexamined Patent Publication No. 02-070716 Japanese Unexamined Patent Publication No. 02-210443

The present invention aims to provide a current image of, for a color filter excellent in wrinkle resistance coloring composition and a color filter.

That is, the present invention is selected from the group consisting of a thiol group and a hydroxyl group, which is a reaction product of a bifunctional or higher functional polyvalent mercaptan compound (A) which may have a hydroxyl group and a compound (B) having an acid anhydride group. The present invention relates to a photosensitive oligomer which is a reaction product of a mercaptan derivative (C) and a diisocyanate (D) having at least one group and a carboxyl group, and a compound (E) having a hydroxyl group and an ethylenically unsaturated bonding group.

Further, in the present invention, the bifunctional or higher polyvalent mercaptan compound (A) which may have a hydroxyl group is a trifunctional or higher polyvalent mercaptan compound which does not have a hydroxyl group in one molecule and has three or more thiol groups. Regarding the photosensitive oligomer according to A1).

The present invention also relates to the photosensitive oligomer in which a trifunctional or higher functional polyvalent mercaptan compound (A1) having no hydroxyl group in one molecule and having three or more thiol groups is a β-mercaptopropionic acid ester compound.

The present invention also relates to a photosensitive coloring composition for a color filter containing the photosensitive oligomer, a colorant (F), a dispersion aid (G), a binder resin and a solvent.

The present invention further relates to the photosensitive coloring composition for a color filter, which further comprises one selected from the group consisting of a photopolymerization initiator and a photopolymerizable monomer.

Further, in the present invention, the thiol group or hydroxyl group of the bifunctional or higher functional polyvalent mercaptan compound (A) which may have a hydroxyl group is reacted with the acid anhydride group of the compound (B) having an acid anhydride group. After obtaining a mercaptan derivative (C) having at least one group selected from the group consisting of a thiol group and a hydroxyl group and a carboxyl group,
The present invention relates to a method for producing a photosensitive oligomer in which a thiol group or a hydroxyl group of a mercaptan derivative (C) is reacted with an isocyanate group of a diisocyanate (D) and a hydroxyl group of a compound (E) having a hydroxyl group and an ethylenically unsaturated bond group.

The coloring composition for a color filter of the present invention can provide a coloring composition for a color filter that suppresses pigment aggregation, has excellent stability of the dispersion, and is also excellent in heat resistance and resolution.

<Photosensitive oligomer>
The photosensitive oligomer of the present invention comprises a thiol group and a hydroxyl group, which is a reaction product of a bifunctional or higher functional polyvalent mercaptan compound (A) which may have a hydroxyl group and a compound (B) having an acid anhydride group. A mercaptan derivative (C) having at least one group selected from the group and a carboxyl group,
Diisocyanate (D) and
It is a reaction product of compound (E) having a hydroxyl group and an ethylenically unsaturated bond group.
It has a complex structure obtained by three reactions: a reaction between a hydroxyl group or thiol group and an acid anhydride group, a reaction between a hydroxyl group or a thiol group and an isocyanate group, and a reaction between an isocyanate group and a hydroxyl group, and has a general formula ( Since it is impossible or almost unrealistic to express by (structure), it is described by the manufacturing method.

Since the photosensitive oligomer of the present invention has a flexible structure introduced by diisocyanate, it is characterized by suppressing the occurrence of wrinkles in color filter applications. Further, since it has a carboxyl group which is a developable part, the developing speed is improved as compared with the one having no carboxyl group.

Hereinafter, the present invention will be described in detail. In the present specification, "(meth) acrylic", "(meth) acrylate", "(meth) acryloyl" and the like mean "acrylic or methacrylic", "acrylate or methacrylate", "acryloyl or methacryloyl" and the like. For example, "(meth) acrylic acid" shall mean "acrylic acid or methacrylic acid".

<Bifunctional or higher multivalent mercaptan compound (A) that may have a hydroxyl group>
As the bifunctional or higher functional polyvalent mercaptan compound (A) which may have a hydroxyl group, a known compound can be used, and one molecule has at least two or more thiol groups, and the thiol group and the hydroxyl group are present. A polyvalent mercaptan compound having 3 or more in total is preferable, and a trifunctional or higher polyvalent mercaptan compound (A1) having 3 or more thiol groups without a hydroxyl group in one molecule is more preferable, and β-mercaptopropionic acid. It is particularly preferably an ester compound. The molecular weight is preferably 3,000 or less, more preferably 2,000 or less, still more preferably 1,000 or less, and particularly preferably 800 or less. The lower limit of the molecular weight of the multivalent mercaptan compound (A) is not particularly limited, but is preferably 200 or more, more preferably 300 or more, for example.

(A polyvalent mercaptan compound having at least two thiol groups in one molecule and a total of three or more thiol groups and hydroxyl groups)
Examples of the polyvalent mercaptan compound having at least two thiol groups in one molecule and having a total of three or more thiol groups and hydroxyl groups include 1,3-dimercapto-2-propanol and dimercaptopentaerythritol. Examples include trimercaptopentaerythritol.

(Trifunctional or higher multivalent mercaptan compound (A1) having 3 or more thiol groups without a hydroxyl group in one molecule)
Examples of the trifunctional or higher polyvalent mercaptan compound (A1) having no hydroxyl group in one molecule and having three or more thiol groups include tetramercaptopentaerythritol, trimercaptopentaerythritol, trimethylolpropane and thio. Glycolate derivatives can be mentioned. Examples of the thioglycolic acid derivative include trimethylolpropane tristhioglycolate and pentaerythritol tetrakisthioglycolate.

(Β-Mercaptopropionic acid esterified product)
Examples of the bifunctional or higher functional polyvalent mercaptan compound (A) which may have a hydroxyl group include β-mercaptopropionic acid esterified products.
Examples of β-mercaptopropionic acid esterified products having a primary thiol group include trimethylolpropanthris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), and tris-[(3-mercaptopropionyloxy). ) -Ethyl] -isocyanurate, tetraethylene glycol bis (3-mercaptopropionate), and dipentaerythritol hexakis (3-mercaptopropionate).
Examples of the β-mercaptopropionic acid esterified product having a secondary thiol group include pentaerythritol tetrakis (3-mercaptobutylate), ”1,3,5-tris (3-mercaptobutylyloxyethyl) -1,3. , 5-Triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptobutylate), trimethylolethanetri (3-mercaptobutylate). ..

Of these, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), and dipentaerythritol hexakis (3-mercaptopropionate) are preferable, and trimethylolpropane tris (3-Mercaptopropionate) is more preferred.

In addition, examples of the bifunctional thiol compound include ethylene glycol bisthiopropionate, butanjiol bisthiopropionate, butanjiol bisthioglycolate, and hexanedio-rubistioglycolate.

<Compound (B) having an acid anhydride group>
As the compound (B) having an acid anhydride group, known compounds can be used.
For example, succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic acid anhydride, glutaric anhydride, octenyl succinic anhydride, dodecenyl succinic anhydride, Examples thereof include trimellitic acid anhydride and chlorendec acid anhydride. Preferred are succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, octenyl succinic anhydride and trimellitic anhydride, and more preferably phthalic anhydride and tetrahydrophthalate. Acid anhydride, hexahydrophthalic anhydride, octenyl succinic anhydride, trimellitic anhydride, and particularly preferably trimellitic anhydride.

<Mercaptan derivative (C) having at least one group selected from the group consisting of a thiol group and a hydroxyl group and a carboxyl group>
The mercaptan derivative (C) having at least one group selected from the group consisting of a thiol group and a hydroxyl group and a carboxyl group is a thiol group or a hydroxyl group of a bifunctional or higher functional polyvalent mercaptan compound (A) which may have a hydroxyl group. And the compound (B) having an acid anhydride group can be obtained by esterification or thioesteration reaction with the acid anhydride group.

(Esterification, thioesterification reaction solvent)
The esterification and thioesterification reactions can be produced using only the raw materials mentioned above, but it is preferable to use a solvent in order to avoid problems such as high viscosity and non-uniform reaction. The solvent used is not particularly limited, and known solvents can be used. For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, toluene, xylene, acetonitrile, propylene glycol monomethyl ether acetate and the like can be mentioned. After the reaction is completed, the solvent used in the reaction can be removed by an operation such as distillation, or can be used as it is as a solvent in the next step, or can be used as a part of a product.

(Esterification, thioesterification reaction catalyst)
As the catalyst used for the esterification and thioesterification reactions, a known catalyst can be used. The catalyst is preferably a tertiary amine compound, for example, triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1, Examples thereof include 5-diazabicyclo- [4.3.0] -5-nonen.

(Reaction temperature)
The reaction temperature of ester and thioesteration is 50 ° C. to 180 ° C., preferably 80 ° C. to 140 ° C. When the reaction temperature is 50 ° C. or lower, the reaction rate is slow, and when the reaction temperature is 180 ° C. or higher, the carboxyl group and the hydroxyl group undergo an esterification reaction, which may reduce the acid value or cause gelation.

<Diisocyanate (D)>
As the diisocyanate (D) used in the present invention, conventionally known diisocyanates can be used, and examples thereof include aromatic diisocyanates, aliphatic diisocyanates, aromatic aliphatic diisocyanates, and alicyclic diisocyanates.

Examples of aromatic diisocyanates include 1,3-phenylenediocyanate, 4,4'-diphenyldiisocyanate, 1,4-phenylenediocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate. Examples thereof include isocyanate, 4,4'-toluidine diisocyanate, dianisidine diisocyanate, and 4,4'-diphenyl ether diisocyanate.

Examples of the aliphatic diisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, and dodecamethylene diisocyanate. 2,4,4-trimethylhexamethylene diisocyanate and the like can be mentioned.

Examples of the aromatic aliphatic diisocyanate include ω, ω'-diisocyanate 1,3-dimethylbenzene, ω, ω'-diisocyanate 1,4-dimethylbenzene, ω, ω'-diisocyanate 1,4-diethylbenzene, 1,4-tetra. Examples thereof include methylxylylene diisocyanate and 1,3-tetramethylxylylene diisocyanate.

Examples of the alicyclic diisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexylisocyanate (IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexanediisocyanate, 1,4-cyclohexanediisocyanate, and methyl-2. , 4-Cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), 1,4-bis (isocyanatemethyl) cyclohexane and the like.

As the diisocyanate (D) used in the present invention, it is preferable to use a non-yellowing diisocyanate compound such as hexamethylene diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexylisocyanate (isophorone diisocyanate) from the viewpoint of hue. ..

<Compound (E) having a hydroxyl group and an ethylenically unsaturated bond group>
As the compound (E) having a hydroxyl group and an ethylenically unsaturated bond group, known compounds can be used.
Examples of the compound having a hydroxyl group and one ethylenically unsaturated bonding group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl. (Meta) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid, glycerol mono Examples thereof include (meth) acrylate, dihydroxy acrylate, glycerol (meth) acrylate, pentaerythritol mono (meth) acrylate, and dipentaerythritol mono (meth) acrylate.
Examples of the compound having a hydroxyl group and two or more ethylenically unsaturated bond groups include 2-hydroxy3-acryloyloxypropyl methacrylate, pentaerythritol di (meth) acrylate, dipentaerythritol di (meth) acrylate, and penta. Examples thereof include erythritol diacrylate, isocyanuric acid EO-modified diacrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate.

<Synthesis of photosensitive oligomers>
The photosensitive oligomer of the present invention has at least one group selected from the group consisting of a thiol group and a hydroxyl group and at least one group selected from the group consisting of a thiol group and a hydroxyl group of the mercaptan derivative (C) having a carboxyl group. After the urethanization or thiourelation reaction of diisocyanate (D) with the isocyanate group, the reaction of the surplus isocyanate group with the hydroxyl group of the compound (E) having a hydroxyl group and an ethylenically unsaturated bond group is carried out by the urethanization reaction. Obtainable.

(Urethaneization, thiourethaneization reaction solvent)
The urethanization and thiourethanization reactions can be produced using only the raw materials mentioned above, but it is preferable to use a solvent in order to avoid problems such as high viscosity and non-uniform reaction. The solvent used is not particularly limited, and known solvents can be used. For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, toluene, xylene, acetonitrile, propylene glycol monomethyl ether acetate and the like can be mentioned. After the reaction is completed, the solvent used in the reaction can be removed by an operation such as distillation, or can be used as it is as a solvent in the next step, or can be used as a part of a product.

(Urethaneization, thiourethaneization reaction catalyst)
As the catalyst used for the urethanization and thiourethanization reactions, a known catalyst can be used. For example, tertiary amine compounds, organometallic compounds and the like can be mentioned.

Examples of tertiary amine compounds include, for example.
Examples thereof include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, and diazabicycloundecene (DBU).

Examples of the organometallic compound include tin-based compounds and non-tin-based compounds.

Examples of tin compounds include, for example.
Dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyl Examples thereof include tin ethoxide, tributyl tin ethoxide, dioctyl tin oxide, dioctyl tin dilaurate, tributyl tin chloride, tributyl tin trichloroacetate, tin 2-ethylhexanoate and the like.

When a solvent is used, the concentration in the reaction system is preferably 20 to 95% by weight in terms of solid content concentration from the viewpoint of reaction control, and more preferably 30 to 95% by weight from the viewpoint of viscosity control. 90% by weight. If it is less than 30% by weight, the reaction is slowed down and unreacted substances may remain, which is not preferable. If it exceeds 95% by weight, the reaction may partially proceed rapidly, which makes it difficult to control the molecular weight and the like, which is not preferable.

(Reaction temperature)
The reaction temperature for urethanization and thiourethaneization is 50 ° C. to 130 ° C., preferably 80 ° C. to 120 ° C. When the reaction temperature is 50 ° C. or lower, the reaction rate is slow, and when the reaction temperature is 130 ° C. or higher, the isocyanate group and the urethane group react with each other, which may cause gelation.

A mercaptan derivative (C) having at least one group selected from the group consisting of a thiol group and a hydroxyl group of the present invention and a carboxyl group, and a diisocyanate capable of reacting with the thiol group and / or the hydroxyl group of the compound (C). The weight average molecular weight (Mw) of the resin composition, which comprises reacting (D) with the compound (E) having a hydroxyl group and an ethylenically unsaturated bond group, is 1,000 to 100,000. Is preferable, more preferably 1,500 to 50,000, and particularly preferably 1,500 to 20,000. If the weight average molecular weight is less than 1,000, the stability of the pigment composition may decrease, and if it exceeds 100,000, the interaction between the resins may become strong and the pigment composition may thicken. is there. The acid value of the obtained photosensitive composition is preferably 1 to 300 mgKOH / g, more preferably 2 to 200 mgKOH / g. If the acid value is less than 1 mgKOH / g, the developability of the resist is insufficient, and if it exceeds 300 mgKOH / g, the double bond equivalent is insufficient and sufficient hardness may not be obtained. The double bond equivalent of the photosensitive composition is preferably 100 g / mol to 1,000 g / mol, more preferably 150 g / mol to 300 g / mol. If the double bond equivalent is 300 g / mol or more, the curability of the resist is insufficient, and if it is less than 100 g / mol, the acid value is insufficient and sufficient developability may not be obtained.

<Colorant (F)>
The colorant (F) that can be used in the coloring composition of the present invention can be arbitrarily selected from various conventionally known pigments and dyes. Hereinafter, typical pigments and dyes that can be used in the present invention are listed.

The red pigments that can be used in the present invention include, for example, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 221 224, 226, 242, 246, 254, 255, 264, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, Examples thereof include, but are not limited to, 284, 285, 286, 287, or the diketopyrrolopyrrole pigments described in JP-A-2011-523433. Further, red dyes such as xanthene-based, azo-based, disazo-based, and anthraquinone-based dyes can also be used. Specifically, C.I. I. Examples thereof include salt-forming compounds of xanthene-based acid dyes such as Acid Red 52, 87, 92, 289, and 338.

The orange pigments that can be used in the present invention include, for example, C.I. I. Pigment Orange 38, 43, 71, 73 and the like, but are not particularly limited thereto.

Yellow dyes include azo dyes, azo metal complex salt dyes, anthraquinone dyes, indigo dyes, thioindigo dyes, phthalocyanine dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, thiazine dyes, cationic dyes, cyanine dyes, nitro dyes, and quinoline dyes. , Naftquinone dyes, oxazine dyes and the like.

Therefore, specific examples of the yellow dye include C.I. I. Acid Yellow 2,3,4,5,6,7,8,9,9: 1,10,11,11: 1,12,13,14,15,16,17,17: 1,18,20, 21, 22, 23, 25, 26, 27, 29, 30, 31, 33, 34, 36, 38, 39, 40, 40: 1, 41, 42, 42: 1, 43, 44, 46, 48, 51, 53, 55, 56, 60, 63, 65, 66, 67, 68, 69, 72, 76, 82, 83, 84, 86, 87, 90, 94, 105, 115, 117, 122, 127, 131, 132, 136, 141, 142, 143, 144, 145, 146, 149, 153, 159, 166, 168, 169, 172, 174, 175, 178, 180, 183, 187, 188, 189, 190, 191 and 192, 199 and the like can be mentioned.

In addition, C.I. I. Direct Yellow 1, 2, 4, 5, 12, 13, 15, 20, 24, 25, 26, 32, 33, 34, 35, 41, 42, 44, 44: 1, 45, 46, 48, 49, 50, 51, 61, 66, 67, 69, 70, 71, 72, 73, 74, 81, 84, 86, 90, 91, 92, 95, 107, 110, 117, 118, 119, 120, 121, 126, 127, 129, 132, 133, 134 and the like can also be mentioned.

In addition, C.I. I. Basic Yellow 1, 2, 5, 11, 13, 14, 15, 19, 21, 24, 25, 28, 29, 37, 40, 45, 49, 51, 57, 79, 87, 90, 96, 103, Examples include 105 and 106.

In addition, C.I. I. Solvent Yellow 2, 3, 4, 7, 8, 10, 11, 12, 13, 14, 15, 16, 18, 19, 21, 22, 25, 27, 28, 29, 30, 32, 33, 34, 40, 42, 43, 44, 45, 47, 48, 56, 62, 64, 68, 69, 71, 72, 73, 77, 79, 81, 82, 83, 85, 88, 89, 90, 93, 94, 98, 104, 107, 114, 116, 117, 124, 130, 131, 133, 135, 138, 141, 143, 145, 146, 147, 157, 160, 162, 163, 167, 172, 174, 175, 176, 177, 179, 181, 182, 183, 184, 185, 186, 187, 188, 190, 191, 192, 194, 195 and the like can also be mentioned.

In addition, C.I. I. Disperse Yellow 1, 2, 3, 5, 7, 8, 10, 11, 13, 13, 23, 27, 33, 34, 42, 45, 48, 51, 54, 56, 59, 60, 63, 64 , 67, 70, 77, 79, 82, 85, 88, 93, 99, 114, 118, 119, 122, 123, 124, 126, 163, 184, 184: 1, 202, 211, 229, 231, 232 , 233, 241, 245, 246, 247, 248, 249, 250, 251 and the like.

As the yellow pigment, an organic or inorganic pigment can be used alone or in combination of two or more, and a pigment having high color development and high heat resistance, particularly a pigment having high heat resistance decomposition property is preferable, and usually Organic pigments are used. As the organic pigment, a commercially available pigment can be used, and a natural pigment or an inorganic pigment can be used in combination depending on the desired hue of the filter segment.

Specific examples of the yellow organic pigment that can be used in the coloring composition are shown below. Examples of the yellow pigment include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 1
5, 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, Use yellow pigments such as 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214. Can be done. In particular, from the viewpoint of heat resistance, light resistance, and brightness of the filter segment, C.I. I. Pigment Yellow 138, 139, 150 and 185 are preferred.
These yellow pigments can be used alone or in admixture of two or more, depending on the desired color characteristics.

The green pigments that can be used in the present invention include, for example, C.I. I. Pigment Green 7, 10, 36, 37, 58, 62, 63 and the like, but are not particularly limited thereto.

The blue pigments that can be used in the present invention include, for example, C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, JP-A-2004-333817, Examples thereof include aluminum phthalocyanine pigments described in Japanese Patent No. 4893859, but the present invention is not particularly limited thereto.

The content of the colorant preferable in all the non-volatile components of the coloring composition according to the present invention is 10 to 90% by weight, more preferably 15 to 85% by weight from the viewpoint of sufficient color reproducibility and stability. Most preferably, it is 20 to 80% by weight.

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

In the salt milling treatment, a mixture of a pigment, a water-soluble inorganic salt and a water-soluble organic solvent is heated using a kneader such as a kneader, a 2-roll mill, a 3-roll mill, a ball mill, an attritor, or a sand mill. However, after mechanically kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

The water-soluble organic solvent has a function of wetting the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, most preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment.

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

<Binder resin>
The binder resin used in the coloring composition of the present invention is for dispersing, dyeing, or permeating a coloring agent, and examples thereof include thermoplastic resins. When used in the form of an alkali-developable colored resist material, it is preferable to use an alkali-soluble vinyl-based resin copolymerized with an acidic group-containing ethylenically unsaturated monomer. Further, in order to further improve the photosensitivity, an active energy-ray curable resin having an ethylenically unsaturated double bond can also be used.

In particular, by using an active energy-ray curable resin having an ethylenically unsaturated double bond in the side chain as an alkali-developable colored resist material, the resin becomes 3 when exposed to active energy rays to form a coating film. By dimensionally cross-linking, the colorant is fixed, the heat resistance is improved, and fading (deterioration of spectral characteristics) due to the heat of the colorant can be suppressed. It also has the effect of suppressing aggregation and precipitation of colorant components in the developing process.

The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region.

The weight average molecular weight (Mw) of the binder resin is preferably in the range of 5,000 to 100,000, more preferably in the range of 7,000 to 80,000 in order to preferably disperse the colorant. The number average molecular weight (Mn) is preferably in the range of 2,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

When the binder resin is used as a photosensitive coloring composition for a color filter, a carboxyl group that acts as a colorant adsorbent group and an alkali-soluble group during development, an aliphatic group that acts as an affinity group for a colorant carrier and a solvent, and an aliphatic group. The balance of aromatic groups is important for the dispersibility, permeability, developability, and durability of the colorant, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. If the acid value is less than 20 mgKOH / g, the solubility in a developing solution is poor, and it may be difficult to form a fine pattern. If it exceeds 300 mgKOH / g, fine patterns may not remain.

Since the binder resin has good film forming properties and various resistances, it is preferable to use the binder resin in an amount of 20 parts by weight or more with respect to 100 parts by weight of the total weight of the colorant, and the colorant concentration is high and good color characteristics are obtained. Since it can be expressed, it is preferably used in an amount of 1000 parts by weight or less.

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

Examples of the vinyl-based alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer include a resin having an acidic group such as a carboxyl group and a sulfone group.
Specifically, the alkali-soluble resin includes an acrylic resin having an acidic group, an α-olefin / (maleic anhydride) maleic anhydride copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Isobutylene / (maleic anhydride) maleic anhydride copolymer and the like can be mentioned. Among them, an acrylic resin having an acidic group and at least one resin selected from a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

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

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

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

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

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

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

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

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

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

(Thermosetting compound)
In the present invention, a thermosetting compound may be further contained in combination with a thermoplastic resin which is a binder resin. Thermosetting compounds include, for example, epoxy compounds and / or resins, benzoguanamine compounds and / or resins, rosin-modified maleic acid compounds and / or resins, rosin-modified fumaric acid compounds and / or resins, melamine compounds and / or resins. Examples include, but are not limited to, urea compounds and / or resins, phenolic compounds and / or resins.

<Solvent>
In the coloring composition of the present invention, the coloring agent is sufficiently dispersed and permeated into the coloring agent carrier, and applied onto a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm to form a coloring film. An organic solvent is included to facilitate the formation. The organic solvent is selected in consideration of the solubility of each component of the coloring composition and the safety in addition to the good coatability of the coloring composition.

Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, and 2, -Methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexene-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1, 3-Butanjiol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene , N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-diethylbenzene, 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 monother share. Butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether , Diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene Glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol mono Methyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether , Propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, acetate Examples thereof include isoamyl, isobutyl acetate, propyl acetate, dibasic acid ester and the like. These solvents can be used alone or in admixture of two or more in any ratio as required.

Among them, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl are good because of the good dispersibility and permeability of the colorant and the applicability of the coloring composition. It is preferable to use glycol acetates such as ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone.

Further, the organic solvent can be used in an amount of 500 to 4000 parts by weight with respect to 100 parts by weight of the colorant because the coloring composition can be adjusted to an appropriate viscosity and a colored film having a desired uniform film thickness can be formed. Is preferable.

<Photopolymerizable monomer>
The photopolymerizable monomer that may be added to the coloring composition of the present invention includes a monomer or an oligomer that is cured by ultraviolet rays, heat, or the like to produce 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-hexanedioldi (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( Meta) Acrylate, Trimethylol Propanetri (Meta) Acrylate, Pentaerythritol Tri (Meta) Acrylate, Pentaerythritol Tetra (Meta) Acrylate, 1,6-Hexane Dioldiglycidyl Acrylate Di (Meta) Acrylate, Bisphenol A Diglycidyl Acrylate (Meta) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated melamine (Meta) acrylic acid ester, epoxy (meth) acrylate, various acrylic acid esters such as urethane acrylate and methacrylic acid ester, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol tri Examples thereof include, but are not limited to, vinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, and acrylonitrile. These photopolymerizable compounds may be used alone or in admixture of two or more at any ratio as required.

The blending amount of the photopolymerizable monomer is preferably 5 to 400 parts by weight based on the total weight of the colorant (100 parts by weight), and 10 to 300 parts by weight from the viewpoint of photocurability and developability. Is more preferable.

<Photopolymerization initiator>
To the coloring composition of the present invention, a photopolymerization initiator is added to cure the composition by ultraviolet irradiation and to form a filter segment by a photolithography method, and a solvent-developed or alkali-developed photosensitive coloring composition is added. It can be prepared in the form of an object. Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-. Hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 -[4- (4-morpholinyl) phenyl] -1-butanone, or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one and other acetophenone compounds; benzophenone, benzoin Benzophenones such as methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylicized benzophenone, 4-benzoyl- Benzophenone compounds such as 4'-methyldiphenylsulfide or 3,3', 4,4'-tetra (t-butylpa-oxycarbonyl) benzophenone; thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2 , 4-Diisopropylthioxanthone, or thioxanthone compounds such as 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2, -(P-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4, 6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) -4,6-bis (trichloromethyl)- s-triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2, Triazine compounds such as 4-trichloromethyl- (4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoy) Luoxime)], or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4'-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6) -Trimethylbenzoyl) phenylphosphine oxide, or phosphine compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrene quinone, camphorquinone, ethylanthraquinone; borate A system compound; a carbazoyl compound; an imidazole compound; or a titanosen compound or the like is used. These photopolymerization initiators can be used alone or in admixture of two or more at any ratio, if necessary.

The content of the photopolymerization initiator is preferably 2 to 200 parts by weight, and more preferably 3 to 150 parts by weight from the viewpoint of photocurability and developability with respect to 100 parts by weight of the colorant.

<Sensitizer>
Further, the coloring composition of the present invention may contain a sensitizer. Examples of the sensitizer include chalcone derivatives, unsaturated ketones typified by dibenzalacetone, 1,2-diketone derivatives typified by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone. Polymethine dyes such as derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, acrydin derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indolin derivatives, azulene Derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triallylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, Naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrilium derivative, tetraphyllin derivative, anurene derivative, spiropyrane derivative, spiroxazine derivative, thiospiropyrane derivative, metal allene complex, organic ruthenium complex, or Mihira-ketone derivative, bimidazo- Derivatives, α-acyloxyester, acylphosphine oxide, methylphenylglycolate, benzyl, 9,10-phenanthrene quinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalofenone , 3,3', or 4,4'-tetra (t-butylpa-oxycarbonyl) benzophenone, 4,4'-diethylaminobenzophenone and the like. These sensitizers can be used alone or in admixture of two or more at any ratio as required.

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

The content of the sensitizer is preferably 3 to 60 parts by weight, and 5 to 50 parts by weight from the viewpoint of photocurability and developability, with respect to 100 parts by weight of the photopolymerization initiator contained in the coloring composition. Is more preferable.

<Multifunctional thiol>
The coloring composition of the present invention can contain a polyfunctional thiol that acts as a chain transfer agent. The polyfunctional thiol may be a compound having two or more thiol groups, for example, hexanedithiol, decandithiol, 1,4-butandiol bisthiopropionate, 1,4-butanjiol bisthioglycolate. , Ethylene Glycol Bisthioglycolate, Ethylene Glycol Bisthiopropionate, Trimethylol Propane Tristhioglycolate, Trimethylol Propane Tristhiopropionate, Trimethylol Propantris (3-Mercapto Butyrate) , Pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, tris (2-hydroxyethyl) trimercaptopropionate, isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto- Examples thereof include s-triazine and 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine. These polyfunctional thiols can be used alone or in admixture of two or more at any ratio as required.

The content of the polyfunctional thiol is preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight, based on the weight of the total solid content of the coloring composition for a color filter (100% by weight). .. If the content of the polyfunctional thiol is less than 0.1% by weight, the effect of adding the polyfunctional thiol is insufficient, and if it exceeds 30% by weight, the sensitivity may be too high and the resolution may be lowered.

<Antioxidant>
The coloring composition of the present invention can contain an antioxidant. The antioxidant is used to reduce the transmittance of the coating film in order to prevent the photopolymerization initiator and thermosetting compound contained in the coloring composition from being oxidized and yellowed by the thermal process during heat curing or ITO annealing. Can be high. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high transmittance of the coating film can be obtained.

The "antioxidant" in the present invention may be a compound having an ultraviolet absorption function, a radical capture function, or a peroxide decomposition function. Specifically, the antioxidant is a hydride phenolic compound or a hinda. -Doamine-based, phosphorus-based, sulfur-based, benzotriazol-based, benzophenone-based, hydroxylamine-based, sartylate ester-based, and triazine-based compounds can be mentioned, and known ultraviolet absorbers, antioxidants, and the like can be used. Among these antioxidants, from the viewpoint of achieving both the transmittance and the sensitivity of the coating film, the preferred ones are hydride-based phenol-based antioxidants, hydride-based amine-based antioxidants, phosphorus-based antioxidants or sulfur. Examples include system antioxidants. Further, more preferably, it is a hydride-based phenol-based antioxidant, a hydride-based amine-based antioxidant, or a phosphorus-based antioxidant. These antioxidants can be used alone or in admixture of two or more at any ratio as required.

The content of the antioxidant is more preferably 0.5 to 5.0% by weight based on the solid content weight of the coloring composition for a color filter because the brightness and sensitivity are good.

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

<Leveling agent>
It is preferable to add a leveling agent to the coloring composition of the present invention in order to improve the leveling property of the composition on the transparent substrate. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of the dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Doukoning Co., Ltd. and BYK-333 manufactured by Big Chemi Co., Ltd. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by Big Chemi. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can also be used in combination. The content of the leveling agent is usually preferably 0.003 to 0.5% by weight based on the total weight of the coloring composition (100% by weight).

A particularly preferable leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a hydrophilic group but has low solubility in water, and when added to a coloring composition, the same. It is useful to have a feature of low surface tension lowering ability and good wettability to the glass plate despite low surface tension lowering ability, and the amount of addition does not cause defects in the coating film due to foaming. Those capable of sufficiently suppressing chargeability can be preferably used. As a leveling agent having such preferable properties, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. The polyalkylene oxide unit includes a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

The bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the polyalkylene oxide unit is bonded to the terminal of dimethylpolysiloxane, and dimethylpolysiloxane. It may be any of linear block copolymer types that are alternately and repeatedly bonded. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Doukoning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, Examples include, but are not limited to, FZ-2207.

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

Examples of the chaotic surfactant added as a supplement to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. Nonionic surfactants to be added as a supplement to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, and polyoxyethylene sorbitan monosteare. Examples include alkyl betaines such as alkyldimethylaminoacetic acid betaine, amphoteric surfactants such as alkylimidazoline, and fluorine-based and silicone-based surfactants, such as polyethylene glycol monolaurate.

<Curing agent, curing accelerator>
Further, the coloring composition of the present invention may contain a curing agent, a curing accelerator, or the like, if necessary, in order to assist the curing of the thermosetting resin. Phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective as the curing agent, but the curing agent is not particularly limited to these, and is a thermosetting resin. Any curing agent may be used as long as it can react with. Further, among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine-based curing agent are preferably mentioned. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (eg, dimethylamine, etc.), imidazole derivative bicyclic amidin compounds and salts thereof (eg, dimethylamine) For example, imidazole, 2-methylimidazole, 2-ethyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 4-phenyl imidazole, 1-cyanoethyl-2. -Phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetguanamine, etc.) Benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino -S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15 parts by weight with respect to 100 parts by weight of the thermosetting resin.

<Other additive ingredients>
The coloring composition of the present invention may contain a storage stabilizer to stabilize the viscosity over time. Further, an adhesion improver such as a silane coupling agent can be contained in order to improve the adhesion with the transparent substrate. Examples of the storage stabilizer include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine. Examples thereof include organic phosphine and phosphite. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the colorant.

Adhesion improvers include vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, and β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino) Ethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysisilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-amino Examples thereof include aminosilanes such as propyltrimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane, and silane coupling agents such as thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the colorant in the coloring composition.

<Manufacturing method of coloring composition>
In the coloring composition of the present invention, a colorant is placed in a colorant carrier such as a binder resin and / or a solvent, preferably with a dispersion aid, in a kneader, a two-roll mill, a three-roll mill, a ball mill, and a horizontal type. It can be produced by finely dispersing it using various dispersion means such as a sand mill, a vertical sand mill, an annular bead mill, or an attritor (colorant dispersion). At this time, two or more kinds of colorants and the like may be dispersed in the colorant carrier at the same time, or those dispersed separately in the colorant carrier may be mixed. If the colorant such as a dye is highly soluble, specifically, if it is highly soluble in the solvent used, dissolved by stirring, and no foreign matter is confirmed, it is manufactured by finely dispersing as described above. No need.

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

<Dispersion aid (G)>
When the colorant is dispersed in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, or a surfactant may be appropriately contained. Since the dispersion aid has a great effect of preventing the reaggregation of the colorant after dispersion, the coloring composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has high lightness and viscosity stability. Become good.

(Dye derivative)
The coloring composition of the present invention can arbitrarily select and contain various conventionally known dye derivatives. Examples of the dye derivative include compounds in which an organic pigment, anthraquinone, acridone or triazine is introduced with a basic substituent, an acidic substituent, or a phthalimide methyl group which may have a substituent. No. 63-305173, No. 57-15620, No. 59-40172, No. 63-17102, No. 5-9469, No. 2001-335717, No. 2003-2003. 128669, 2003-167112, 2004-091497, 2004-307854, 2007-156395, 2008-094873, 2008-094986. Those described in Japanese Patent Application Laid-Open No. 2008-905007, Japanese Patent Application Laid-Open No. 2008-195916, Japanese Patent Application Laid-Open No. 4585781, and the like can be used.

The following is an example of a dye derivative having a basic group of the present invention, but the present invention is not limited thereto.

Compound 1:

Compound 2:

Compound 3:

Compound 4:

Compound 5:

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

A polymer dispersant having a basic functional group is preferable because the viscosity of the dispersion becomes low and a high contrast is exhibited with a small amount of the dispersant added, and it is preferable for a nitrogen atom-containing graft copolymer or a side chain. Nitrogen atom-containing acrylic block copolymers and urethane polymer dispersants having a functional group containing a tertiary amino group, a quaternary ammonium base, a nitrogen-containing heterocycle and the like are preferable. The resin type dispersant is preferably used in an amount of about 5 to 200% by weight, more preferably about 10 to 100% by weight, based on the total amount of the colorant.

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

Further, as the resin type dispersant used in the present invention, the following resin (S1) or (S2) can be contained as the dispersant having a carboxyl group.
(S1) A resin which is a reaction product of a hydroxyl group of a polymer (S1) having a hydroxyl group and an acid anhydride group of a tricarboxylic acid anhydride and / or a tetracarboxylic dianhydride.
(S2) An ethylenically unsaturated monomer is added in the presence of a reaction product of the hydroxyl group of the compound (S2) having a hydroxyl group and the acid anhydride group of a tricarboxylic acid anhydride and / or a tetracarboxylic acid dianhydride. A resin that is a polymerized polymer.

[Resin (S1)]
The resin (S1) can be produced by a known method such as WO2008 / 007776, Japanese Patent Application Laid-Open No. 2008-029901 and the like. The polymer (a) having a hydroxyl group is preferably a polymer having a hydroxyl group at the terminal. For example, the ethylenically unsaturated monomer (c) is polymerized in the presence of the compound (b) having a hydroxyl group. It can be obtained as a polymer. As the compound (b) having a hydroxyl group, as described later, a compound having a hydroxyl group and a thiol group in the molecule is preferable. Since the number of terminal hydroxyl groups is preferably plural, the compound (b1) having two hydroxyl groups and one thiol group in the molecule is preferably used.

That is, a more preferable example, a polymer having two hydroxyl groups at one end contains a monomer (c1) in the presence of a compound (b1) having two hydroxyl groups and one thiol group in the molecule. It can be obtained as a polymer (a1) obtained by polymerizing the ethylenically unsaturated monomer (c) contained therein. The hydroxyl group of the polymer (a) having a hydroxyl group reacts with the acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride to form an ester bond, while the anhydrous ring is opened and the carboxylic acid. Produces.

[Resin (S2)]
The resin (S2) can be produced by a known method such as JP-A-2010-185934. For example, the hydroxyl group of the compound (b) having a hydroxyl group, a tricarboxylic acid anhydride and / or a tetracarboxylic acid dianhydride can be produced. It is obtained by polymerizing the ethylenically unsaturated monomer (c) in the presence of a reaction product with an acid anhydride group of a compound. Above all, in the presence of a reaction product of the hydroxyl group of the compound (b1) having two hydroxyl groups and one thiol group in the molecule and the acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride. It is preferably a polymer obtained by polymerizing an ethylenically unsaturated monomer (c) containing the monomer (c1).

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

<Surfactant>
Examples of the surfactant include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalin sulfonate, sodium alkyldiphenyl ether disulfonate. , Monoethanolamine lauryl sulfate, Triethanolamine lauryl sulfate, Ammonium lauryl sulfate, Monoethanolamine stearate, Monoethanolamine styrene-acrylic acid copolymer, Anionic surfactants such as polyoxyethylene alkyl ether phosphate; Nonionic interfaces such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate. Activators; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyl betaines such as alkyldimethylaminoacetic acid betaine, amphoteric surfactants such as alkyl imidazoline, these alone or Two or more types can be mixed and used, but the present invention is not necessarily limited to these.

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

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

<Color filter>
Next, the color filter of the present invention will be described. The color filter of the present invention comprises a filter segment or a black matrix formed from the coloring composition of the present invention on a transparent substrate, and a general color filter has at least one red filter segment and at least one. It comprises a green filter segment and at least one blue filter segment, or at least one magenta color filter segment, at least one cyan color filter segment, and at least one yellow color filter segment.

As the transparent substrate, glass plates such as soda-lime glass, low-alkali borosilicate glass, and non-alkali aluminoborosilicate glass, and resin plates such as polycarbonate, polymethylmethacrylate, and polyethylene terephthalate are used. .. Further, a transparent electrode made of indium oxide, tin oxide or the like may be formed on the surface of the glass plate or the resin plate for driving the liquid crystal after the panelization.

The dry film thickness of the filter segment and the black matrix is preferably 0.2 to 10 μm, more preferably 0.2 to 5 μm. When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate or the like may be used.

Each color filter segment and black matrix are formed by the photolithography method by the following method. That is, a photosensitive coloring composition prepared as a solvent-developable or alkali-developable colored resist material is applied onto a transparent substrate by a method of applying a spray coat, a spin coat, a slit coat, a roll coat, or the like to a dry film. Apply so that the thickness is 0.2 to 10 μm. If necessary, the dried film is exposed to ultraviolet rays through a mask having a predetermined pattern provided in contact with or without contact with the film.

After that, the filter segment and the black matrix can be formed by immersing in a solvent or an alkaline developer, or spraying the developer with a spray or the like to remove the uncured portion and form a desired pattern. Further, in order to promote the polymerization of the filter segment and the black matrix formed by the development, heating can be applied if necessary. According to the photolithography method, a filter segment and a black matrix with higher accuracy than the printing method can be formed.

At the time of development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as the alkaline developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant can be added to the developing solution. As the developing method, a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (liquid filling) developing method and the like can be applied.

In order to increase the UV exposure sensitivity, the photosensitive coloring composition is applied and dried, and then a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to prevent polymerization inhibition by oxygen. It is also possible to perform ultraviolet exposure after forming the film.

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

(Weight average molecular weight (Mw))
The weight average molecular weight (Mw) was measured by using a TSKgel column (manufactured by Toso Co., Ltd.) and a GPC (manufactured by Toso Co., Ltd., HLC-8320 GPC) equipped with an RI detector, and using THF as a developing solvent. It is the converted weight average molecular weight (Mw).

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

(Manufacturing of refined pigment (Y-1))
100 parts of quinophthalone yellow pigment PY138 (BASF's "Pariotol Yellow K0961HD"), 3 parts of dye derivative (compound 1 mentioned above), 800 parts of crushed salt, and 180 parts of diethylene glycol are made of stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho). ), And kneaded at 70 ° C. for 4 hours. This mixture is poured into 3000 parts of warm water, stirred with a high speed mixer for about 1 hour while heating at about 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then 24 at 80 ° C. The mixture was dried for a time to obtain 98 parts of a finely divided pigment (Y-1).

(Manufacturing of refined pigment (Y-2))
500 parts of the metal complex yellow pigment PY150 (“E4GN” manufactured by LANXESS), 2500 parts of sodium chloride, and 250 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 100 ° C. for 6 hours. Next, this kneaded product was put into 5 liters of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then at 80 ° C. for 24 hours. The mixture was dried to obtain 98 parts of a finely divided pigment (Y-2).

(Manufacturing of refined pigment (R-1))
Diketopyrrolopyrrole red pigment PR254 (BASF's "Irgafore Red B-CF") 100 parts, dye derivative (compound 2 mentioned above) 10 parts, crushed salt 1000 parts, diethylene glycol 120 parts 1 gallon made of stainless steel It was charged in a kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 8 hours. This mixture is poured into 2000 parts of warm water, stirred with a high speed mixer for about 1 hour while heating at about 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then 24 at 80 ° C. It was dried for a time to obtain 100 parts of a finely divided pigment (R-1).

(Manufacturing of refined pigment (R-2))
100 parts of anthraquinone red pigment PR177 (BASF's "Chromophthalred A2B"), 5 parts of dye derivative (compound 3 mentioned above), 800 parts of crushed salt, and 180 parts of diethylene glycol are made of stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho). ), And kneaded at 70 ° C. for 5 hours. This mixture is poured into 4000 parts of warm water, stirred with a high speed mixer for about 1 hour while heating at about 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then 24 at 80 ° C. It was dried for a time to obtain 100 parts of a finely divided pigment (R-2).

(Manufacturing of refined pigment (B-1))
100 parts of copper phthalocyanine blue pigment PB15: 6 (“Lionol Blue ES” manufactured by Toyo Color Co., Ltd.), 5 parts of dye derivative (compound 4 mentioned above), 1000 parts of crushed salt, and 100 parts of diethylene glycol are made of stainless steel 1 gallon kneader. It was charged in (manufactured by Inoue Seisakusho) and kneaded at 50 ° C. for 12 hours. This mixture is poured into 3000 parts of warm water, stirred with a high speed mixer for about 1 hour while heating at about 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then 24 at 80 ° C. It was dried for a time to obtain 98 parts of a finely divided pigment (B-1).

(Manufacturing of refined pigment (V-1))
300 parts of the dioxazine-based purple pigment PV23 (“Rionogen Violet RL” manufactured by Toyo Color Co., Ltd.) was put into 3000 parts of 96% sulfuric acid, stirred for 1 hour, and then injected into water at 5 ° C. After stirring for 1 hour, the mixture was filtered, washed with warm water until the washing liquid became neutral, and dried at 70 ° C. 120 parts of the obtained acid pasting-treated pigment, 5 parts of the dye derivative (compound 5 described above), 1500 parts of crushed salt, and 100 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and 20 at 70 ° C. Time kneaded. This mixture is poured into 5000 parts of warm water, stirred with a high speed mixer for about 1 hour while heating at about 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then 24 at 80 ° C. It was dried for a time to obtain 115 parts of a finely divided pigment (V-1).

<Adjustment of pigment dispersion>
(Adjustment of green pigment dispersion (D1))
The mixture having the following composition is uniformly stirred and mixed, dispersed with an Eiger mill (“Mini model M-250 MKII” manufactured by Eiger Japan) for 2 hours using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. , A green pigment dispersion (D1) was prepared.
Fine pigment (G-1): 8.0 parts Fine pigment (Y-1): 6.0 parts Dispersant (X) solution: 6.0 parts Binder resin solution: 16.0 parts PGMAC: 64.0 parts Department

(Adjustment of red pigment dispersion (D2))
The mixture having the following composition is uniformly stirred and mixed, dispersed with an Eiger mill (“Mini model M-250 MKII” manufactured by Eiger Japan) for 2 hours using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. , A red pigment dispersion (D2) was prepared.
Fine pigment (R-1): 5.0 parts Fine pigment (R-2): 4.0 parts Fine pigment (Y-2): 2.0 parts Dispersant (X) solution: 5.0 parts Binder resin solution: 28.0 parts PGMac: 55.0 parts

(Adjustment of blue pigment dispersion (D3))
The mixture having the following composition is uniformly stirred and mixed, dispersed with an Eiger mill (“Mini model M-250 MKII” manufactured by Eiger Japan) for 2 hours using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. , A blue pigment dispersion (D3) was prepared.
Fine pigment (B-1): 13.0 parts Fine pigment (V-1): 1.0 part Dispersant (X) solution: 6.0 parts Binder resin solution: 16.0 parts PGMAc: 64.0 Department

<Manufacturing of binder resin solution>
370 parts of propylene glycol monomethyl ether acetate (PGMAc) is placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomer and thermal polymerization initiator is added dropwise at the same temperature over 1 hour. The polymerization reaction was carried out.
Methacrylic acid: 13.0 parts 2-Hydroxyethyl methacrylate: 14.0 parts Glycerol monomethacrylate: 25.0 parts Benzyl methacrylate: 25.0 parts Butyl methacrylate: 23.0 parts 2,2'-azobisisobutyronitrile : 4.0 copies

After completion of the dropping, the reaction was further carried out at 80 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of propylene glycol monomethyl ether acetate (PGMAc) was added, and further 1 at 80 ° C. The reaction for a time was continued to obtain a copolymer solution. After cooling to room temperature, about 2 g of the alkali-soluble resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, so that the non-volatile content is 20% by weight in the previously synthesized alkali-soluble resin solution. Propylene glycol monomethyl ether acetate (PGMAc) was added to obtain a binder resin solution. The obtained non-photosensitive transparent resin had a weight average molecular weight of 32000 and an acid value of 78.

<Manufacturing of dispersant>
(Manufacturing of dispersant (X))
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 65.0 parts of methyl methacrylate, 30.0 parts of ethyl acrylate, and 5.0 parts of methacrylic acid, and replaced with nitrogen gas. The inside of the reaction vessel is heated to 80 ° C., and 5.7 parts of 3-mercapto-1,2-propanediol and 0.1 part of 2,2'-azobisisobutyronitrile are added to propylene glycol monomethyl ether acetate. The dissolved solution was added to 45.4 parts and reacted for 10 hours. It was confirmed by solid content measurement that 95% had reacted. At this time, the weight average molecular weight was 4000. Next, 9.2 parts of pyromellitic acid dianhydride, 31.7 parts of propylene glycol monomethyl ether acetate, and 0.2 parts of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added. Then, the reaction was carried out at 120 ° C. for 7 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was harf esterified, and the reaction was terminated. After completion of the reaction, propylene glycol monomethyl ether acetate was added so as to have a non-volatile content of 60% by weight, and a solution of a dispersant (X) having an acid value of 70 mgKOH / g and a weight average molecular weight of 9500 was obtained.

<Manufacturing of photosensitive oligomer>
[Example 1] (Production of photosensitive oligomer 1)
Pentaerythritol tetrakis (3-mercaptopropionate) 15.0 g, trimellitic anhydride 5.9 g, DBU 0.1 g, in a 4-neck flask equipped with a stirrer, reflux condenser, dry air-introduction tube, and thermometer. 20.8 g of propylene glycol monomethyl ether acetate was charged and the temperature was raised to 120 ° C. The mixture was stirred at 120 ° C. for 2 hours and cooled to 80 ° C. Next, 0.04 g of p-methoxyphenol, 15.5 g of hexamethylene isocyanate, 50.4 g of pentaerythritol triacrylate, and 65.9 g of propylene glycol monomethyl ether acetate were charged, and then 0.18 g of dioctyl tin as a catalyst was charged, up to 100 ° C. The temperature was raised. The reaction was carried out at 100 ° C. for 3 hours, and after confirming that the peak of isocyanate had disappeared by IR, the reaction was terminated by cooling to room temperature to obtain a photosensitive oligomer 1 solution. This reaction solution was colorless and transparent, had a solid content of 50%, and had a weight average molecular weight of MW 7,100.

[Examples 2 to 8] (Production of photosensitive oligomers 2 to 8)
Synthesis was carried out in the same manner as in Example 1 except that the raw materials and the charged amounts shown in Table 1 were used to obtain a photosensitive oligomer solution 2-8.

[Comparative Example 1] (Production of Photosensitive Oligomer 9)
Trimethylolpropane 5.0 g, hexamethylene diisocyanate 18.8 g, pentaerythritol triacrylate 51.3 g, propylene glycol monomethyl ether acetate 75. 1 g, 0.02 g of p-methoxyphenol, and then 0.12 g of dioctyl tin as a catalyst were charged, and the temperature was raised to 100 ° C. The reaction was carried out at 100 ° C. for 3 hours, and after confirming that the peak of isocyanate had disappeared by IR, the reaction was terminated by cooling to room temperature to obtain a photosensitive oligomer 9 solution. This reaction solution was colorless and transparent, had a solid content of 50%, and had a weight average molecular weight of MW 7,600.

The abbreviations in Table 1 are shown below.
・ PEMP: Pentaerythritol Tetrakis (3-mercaptopropionate)
-TMMP: Trimethylolpropane Tris (3-mercaptopropionate)
-TEMPIC: Tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate-EGFP-4: tetraethylene glycol bis (3-mercaptopropionate)
・ DPMP: Dipentaerythritol Hexakis (3-mercaptopropionate)
-DBU: 1,8-diazabicyclo- [5.4.0] -7-undecene-PGMAc: Propylene glycol monomethyl ether acetate

<Adjustment of photosensitive coloring composition>
[Example 1]
(Adjustment of photosensitive coloring composition (C1))
The mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a photosensitive coloring composition (C1) for a green color filter.
Green pigment dispersion (D1): 54.0 parts Binder resin solution: 6.0 parts Photosensitive oligomer 1 solution: 4.0 parts Photopolymerization initiator (2-methyl-1- (4-methylthiophenyl) -2- Morphorinopropan-1-on)
1.8 parts sensitizer (4,5'-bis (diethylamino) benzophenone)
: 0.2 copies PGMAc: 34.0 copies

[Examples 2 to 24, Comparative Examples 1 to 6]
(Adjustment of photosensitive coloring composition (C2 to C30))
A photosensitive coloring composition (C2 to C30) was obtained in the same manner as in Example 1 except that the photosensitive oligomers shown in Table 2 were used.

The abbreviations in Table 2 are shown below.
-M-402: Dipentaerythritol penta and hexaacrylate (manufactured by Toagosei Co., Ltd.)

<Evaluation of photosensitive coloring composition>
(Wrinkle evaluation)
The obtained photosensitive coloring composition (C1 to 30) is coated on a glass substrate of 100 mm × 100 mm and 0.7 mm so as to have a film thickness of 3.4 μm, and has a predetermined pattern. Ultraviolet exposure was performed under the condition of 40 mJ / cm ^{2 through a mask.} Then, the alkaline developer was sprayed by spraying to remove the uncured portion to form a desired pattern. The obtained coating film was heat-treated (post-baked) in an oven at 230 ° C. for 20 minutes, and the presence or absence of wrinkles was confirmed with a microscope (“BX-51” manufactured by Olympus Optical Co., Ltd.). The evaluation was made by observing 400 μm × 400 μm square pixels with a microscope and judging according to the following criteria. The film thickness of the coating film was measured using Dektak 8 (manufactured by Nippon Vacuum Technology Co., Ltd.).
⊚: No wrinkles ○: Wrinkles occur in a part of the pattern ×: Wrinkles occur in the entire pattern

(Developability (evaluation of pattern residue))
The obtained photosensitive coloring composition (C1 to 30) is coated on a glass substrate of 100 mm × 100 mm and 0.7 mm so as to have a film thickness of 3.4 μm, and has a predetermined pattern. Ultraviolet exposure was performed under the condition of 40 mJ / cm ^{2 through a mask.} Then, the alkaline developer was sprayed by spraying to remove the uncured portion to form a desired pattern. The obtained coating film was heat-treated (post-baked) in an oven at 230 ° C. for 20 minutes, and the presence or absence of residue was confirmed with a microscope (“BX-51” manufactured by Olympus Optical Co., Ltd.). For the evaluation, the remaining area of the residue in the TH pattern having a radius of 15 μm was calculated and judged according to the following criteria. The film thickness of the coating film was measured using Dektak 8 (manufactured by Nippon Vacuum Technology Co., Ltd.).
⊚: No residue ○: 50 μm ^{less than 2} ×: 50 μm ² or more

Claims (5)

At least one selected from the group consisting of a thiol group and a hydroxyl group, which is a reaction product of a bifunctional or higher functional polyvalent mercaptan compound (A) which may have a hydroxyl group and a compound (B) having an acid anhydride group. A mercaptan derivative (C) having a group and a carboxyl group,
Diisocyanate (D) and
It contains a photosensitive oligomer, a colorant (F), a dispersion aid (G), a binder resin and a solvent, which are reactants of the compound (E) having a hydroxyl group and an ethylenically unsaturated bond group.
A photosensitive coloring composition for a color filter containing 26 to 112 parts by mass of the photosensitive oligomer with respect to 100 parts by mass of the colorant (F). Hydroxyl may also be difunctional or higher-that have value mercaptan compound (A) is a trifunctional or higher-valent mercaptan compounds hydroxyl group having a thiol group three or more no in one molecule (A1) a photosensitive The photosensitive coloring composition for a color filter according to claim 1, which contains a sex oligomer . The color according to claim 2, wherein the trifunctional or higher functional polyvalent mercaptan compound (A1) having three or more thiol groups without a hydroxyl group in one molecule contains a photosensitive oligomer which is a β-mercaptopropionic acid ester compound. Photosensitive coloring composition for filters . The photosensitive coloring composition for a color filter according to any one of claims 1 to 3, further comprising one selected from the group consisting of a photopolymerization initiator and a photopolymerizable monomer. The thiol group or hydroxyl group of the bifunctional or higher functional polyvalent mercaptan compound (A) which may have a hydroxyl group is reacted with the acid anhydride group of the compound (B) having an acid anhydride group to react the thiol group and the hydroxyl group. After obtaining a mercaptan derivative (C) having at least one group and a carboxyl group selected from the group consisting of
A photosensitive oligomer or colorant (F ) that reacts a thiol group or hydroxyl group of a mercaptan derivative (C) with an isocyanate group of a diisocyanate (D) and a hydroxyl group of a compound (E) having a hydroxyl group and an ethylenically unsaturated bond group. ), Dispersion aid (G), binder resin and solvent,
A method for producing a photosensitive coloring composition for a color filter, which contains 26 to 112 parts by mass of the photosensitive oligomer with respect to 100 parts by mass of the colorant (F).