JP2018120044A - Photosensitive composition for color filter and production method of the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive composition for a color filter excellent in developability and wrinkle resistance, a production method of the composition, and a color filter.SOLUTION: A photosensitive colored composition for a color filter is provided, comprising a photosensitive oligomer, a colorant, a dispersion aid, a binder resin and a solvent. The photosensitive oligomer is a reaction product of a compound (C) having a hydroxyl group and a carboxyl group, which is a reaction product of a polyol (A) having at least three hydroxyl groups and a compound (B) having an acid anhydride group, a diisocyanate (D) and a compound (E) having a hydroxyl group and an ethylenically unsaturated bonding group.SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive coloring composition for a color filter.

  The filter segment of the color filter is generally formed by using a coloring composition in which a colorant containing a pigment is dispersed in a dispersant, a resin, a monomer, an organic solvent, and the like, and developability is required in the manufacturing process. It is done. It is also important that the cured coating does not wrinkle. Regarding improvement of developability, Patent Documents 1 to 6 propose carboxyl group-containing monomers and oligomers, but the problems of developability and wrinkles in color filter applications could not be solved.

Japanese Patent Laid-Open No. 1999-181042 JP 1999-184082 A JP 1999-184083 A Japanese Unexamined Patent Publication No. 1987-502848 JP-A-1990-070716 Japanese Patent Laid-Open No. 1990-210443

  The objective of this invention is providing the photosensitive composition for color filters excellent in developability and wrinkle tolerance, its manufacturing method, and a color filter.

  That is, the present invention is a photosensitive coloring composition for a color filter comprising a photosensitive oligomer, a colorant, a dispersion aid, a binder resin and a solvent, wherein the photosensitive oligomer has a polyol (A) having three or more hydroxyl groups. And a compound (C) having a hydroxyl group and a carboxyl group, a diisocyanate (D), and a compound having a hydroxyl group and an ethylenically unsaturated bond group (E ), A photosensitive coloring composition for a color filter.

  The present invention also provides the above photosensitive coloring composition for color filters, wherein the compound (E) having a hydroxyl group and an ethylenically unsaturated bond group is a compound (E1) having a hydroxyl group and three or more ethylenically unsaturated bond groups. Related to things.

  Moreover, this invention relates to the said photosensitive coloring composition for color filters whose acid value of a photosensitive oligomer is 15 or more and 100 or less (mgKOH / g).

  Moreover, this invention relates to the said photosensitive coloring composition for color filters whose diisocyanate (D) is at least 1 sort (s) chosen from the group which consists of hexamethylene diisocyanate and isophorone diisocyanate.

  In addition, the present invention further includes the above-described photosensitivity for a color filter, which includes one kind selected from the group consisting of a photopolymerization initiator and a photopolymerizable monomer (except for a photo-sensitive oligomer or binder resin). The present invention relates to a coloring composition.

  The present invention also relates to the above photosensitive coloring composition for a color filter, wherein the solvent is at least one selected from the group consisting of propylene glycol monomethyl ether acetate and cyclohexanone.

  The present invention also relates to a color filter comprising a filter segment formed on the substrate from the photosensitive coloring composition for a color filter.

  The present invention also relates to a method for producing a photosensitive coloring composition for a color filter in which a photosensitive oligomer, a colorant, a dispersion aid, a binder resin, and a solvent are mixed, wherein the photosensitive oligomer has three or more hydroxyl groups. After reacting the hydroxyl group of the polyol (A) with the acid anhydride group of the compound (B) having an acid anhydride group to obtain a compound (C) having a hydroxyl group and a carboxyl group, the compound (C) The present invention relates to a method for producing a photosensitive coloring composition for a color filter in which a hydroxyl group, 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 are reacted.

  The photosensitive coloring composition for color filters of the present invention can achieve both excellent developability and suppression of wrinkles by containing a specific photosensitive oligomer.

<Photosensitive oligomer>
The photosensitive oligomer of the present invention is a reaction product of a polyol (A) having three or more hydroxyl groups and a compound (B) having an acid anhydride group, a compound (C) having a hydroxyl group and a carboxyl group, and diisocyanate. (D) and a reaction product of a compound (E) having a hydroxyl group and an ethylenically unsaturated bond group, obtained by two reactions, a reaction between a hydroxyl group and an acid anhydride group, and a reaction between a hydroxyl group and an isocyanate group. Since it has a complicated structure and cannot be represented by a general formula (structure) or is not practical, it is described by a manufacturing method.

  Since the photosensitive oligomer of the present invention introduces a flexible structure by using diisocyanate, it is characterized by suppressing generation of wrinkles in color filter applications. Moreover, since it has a carboxyl group which is a developable site, the development speed is improved as compared with the case where there is no carboxyl group.

  Hereinafter, the present invention will be described in detail. In this specification, “(meth) acryl”, “(meth) acrylate”, “(meth) acryloyl” and the like mean “acryl or methacryl”, “acrylate or methacrylate”, “acryloyl or methacryloyl”, and the like. For example, “(meth) acrylic acid” means “acrylic acid or methacrylic acid”.

<Polyol (A) having three or more hydroxyl groups>
A well-known thing can be used as a polyol (A) which has a 3 or more hydroxyl group. For example, aliphatic polyhydric alcohols such as glycerin, trimethylolethane, trimethylolpropane, trimethylolalkane, 1,2,6-hexanetriol, pentaerythritol, sorbitol, tris (2-hydroxyethyl) isocyanurate, Examples thereof include cyclic polyhydric alcohols such as inositol and cellulose. Furthermore, the compound etc. which were obtained by reaction of a polyhydric alcohol compound and alkylene oxides, such as ethylene oxide and a propylene oxide, are illustrated. From the molecular weight and melting point, glycerin, trimethylolpropane, and 1,2,6-hexanetriol are preferable.

<Compound (B) having an acid anhydride group>
A well-known thing can be used as a compound (B) which has an acid anhydride group.
For example, succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, glutaric anhydride, octenyl succinic anhydride, dodecenyl succinic anhydride, Examples include trimellitic acid anhydride and chlorendec acid anhydride. Preferred are succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, octenyl succinic anhydride, trimellitic anhydride, and more preferred are phthalic anhydride, tetrahydrophthalic anhydride. An acid anhydride, hexahydrophthalic anhydride, octenyl succinic anhydride, and trimellitic anhydride are preferable, and trimellitic anhydride is particularly preferable.

<Compound (C) having a hydroxyl group and a carboxyl group, which is a reaction product of a polyol (A) having three or more hydroxyl groups and a compound (B) having an acid anhydride group>
The compound (C) having a hydroxyl group and a carboxyl group is obtained by an esterification reaction between the hydroxyl group of the polyol (A) having three or more hydroxyl groups and the acid anhydride group of the compound (B) having an acid anhydride group. Can do.

(Esterification reaction solvent)
The esterification reaction can be produced using only the raw materials mentioned so far, but it is preferable to use a solvent in order to avoid problems such as high viscosity and non-uniform reaction. There is no limitation in particular as a solvent used, A well-known thing can be used. Examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, toluene, xylene, acetonitrile, propylene glycol monomethyl ether acetate and the like. After completion of the reaction, 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 for the next step or as part of a product.

(Esterification reaction catalyst)
As the catalyst used in the esterification reaction, a known catalyst can be used. The catalyst is preferably a tertiary amine compound such as triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1, 5-diazabicyclo- [4.3.0] -5-nonene and the like.

(Reaction temperature)
The reaction temperature for esterification 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 may undergo an esterification reaction, resulting in a decrease in acid value or gelation.

<Diisocyanate (D)>
A conventionally well-known thing can be used as diisocyanate (D) used for this invention, For example, aromatic diisocyanate, aliphatic diisocyanate, araliphatic diisocyanate, alicyclic diisocyanate, etc. are mentioned.

   As aromatic diisocyanates, 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate Examples thereof include isocyanate, 4,4′-toluidine diisocyanate, dianisidine diisocyanate, and 4,4′-diphenyl ether diisocyanate.

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

   Examples of the araliphatic diisocyanate include ω, ω′-diisocyanate 1,3-dimethylbenzene, ω, ω′-diisocyanate 1,4-dimethylbenzene, ω, ω′-diisocyanate 1,4-diethylbenzene, 1,4-tetrabenzene. Examples thereof include methylxylylene diisocyanate and 1,3-tetramethylxylylene diisocyanate.

   As alicyclic diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2 , 4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylene bis (cyclohexyl isocyanate), 1,4-bis (isocyanate methyl) cyclohexane and the like.

  The diisocyanate (D) used in the present invention is preferably a non-yellowing diisocyanate compound such as hexamethylene diisocyanate or 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate) from the viewpoint of hue.

<Compound (E) having a hydroxyl group and an ethylenically unsaturated bond group>
A well-known thing can be used as a compound (E) which has a hydroxyl group and an ethylenically unsaturated bond group.
Examples of the compound having a hydroxyl group and one ethylenically unsaturated bond group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl. (Meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid, glycerol mono (Meth) acrylate, dihydroxy acrylate, glycerol (meth) acrylate, pentaerythritol mono (meth) acrylate, dipentaerythritol mono (meth) acrylate and the like.
Examples of the compound having a hydroxyl group and two or more ethylenically unsaturated bond groups include 2-hydroxy-3-acryloyloxypropyl methacrylate, pentaerythritol di (meth) acrylate, dipentaerythritol di (meth) acrylate, penta Examples 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 oligomer>
The photosensitive oligomer of the present invention comprises an excess isocyanate group, a hydroxyl group and an ethylenically unsaturated bond group after the urethanization reaction between the hydroxyl group of the compound (C) having a hydroxyl group and a carboxyl group and the isocyanate group of the diisocyanate (D). The reaction of the compound (E) having a hydroxyl group can be obtained by a urethanization reaction.

(Urethane reaction solvent)
The urethanization reaction can be produced using only the raw materials mentioned so far, but it is preferable to use a solvent in order to avoid problems such as high viscosity and non-uniform reaction. There is no limitation in particular as a solvent used, A well-known thing can be used. Examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, toluene, xylene, acetonitrile, propylene glycol monomethyl ether acetate and the like. After completion of the reaction, 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 for the next step or as part of a product.

(Urethanization reaction catalyst)
As the catalyst used for the urethanization reaction, a known catalyst can be used. For example, a tertiary amine compound, an organometallic compound, etc. can be mentioned.

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

  Examples of organometallic compounds include tin compounds and non-tin compounds.

Examples of tin compounds include:
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, and tin 2-ethylhexanoate.

  Further, the concentration in the reaction system when using a solvent is preferably 20 to 95% by weight from the viewpoint of reaction control in terms of solid content concentration, and more preferably 30 to 95% from the viewpoint of viscosity control. 90% by weight. If it is less than 30% by weight, the reaction becomes slow and unreacted substances may remain. If it exceeds 95% by weight, the reaction may partially proceed abruptly, and it is difficult to control the molecular weight or the like, which is not preferable.

(Reaction temperature)
The reaction temperature for urethanization is 50 ° C to 130 ° C, preferably 80 ° C to 120 ° C. If the reaction temperature is 50 ° C. or lower, the reaction rate is slow, and if it is 130 ° C. or higher, the isocyanate group and the urethane group may react to cause gelation.

  In addition to the compound (C) having a hydroxyl group and a carboxyl group of the present invention, a compound (E) having a diisocyanate (D) capable of reacting with the hydroxyl group of the compound (C), a hydroxyl group, and an ethylenically unsaturated bond group; The weight average molecular weight (Mw) of the resin composition characterized by reacting is preferably 1,000 to 100,000, more preferably 1,500 to 50,000, and particularly preferably 1,500. ~ 20,000. If the weight average molecular weight is less than 1,000, the stability of the pigment composition may decrease. If the weight average molecular weight exceeds 100,000, the interaction between the resins becomes strong and the pigment composition may increase in viscosity. is there.

  The acid value of the obtained photosensitive oligomer is preferably 1 to 300 mgKOH / g, more preferably 5 to 200 mgKOH / g, and still more preferably 15 to 100 mgKOH / g. If the acid value is less than 1 mgKOH / g, the developability when resist is made 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 oligomer is preferably 100 g / mol to 1,000 g / mol, and more preferably 150 g / mol to 300 g / mol. If the double bond equivalent is 300 g / mol or more, the curability when resist is made is insufficient, and if it is less than 100 g / mol, the acid value is insufficient and sufficient developability may not be obtained.

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

  Examples of red pigments that can be used in the present invention include 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, 208,209,210,216,220,221,224,226,242,246,254,255,264,270,272,273,274,276,277,278,279,280,281,2 2,283,284,285,286,287 or diketopyrrolopyrrole pigment described in JP-T 2011-523433 discloses the like, but not particularly limited thereto. Also, red dyes such as xanthene, azo, disazo, and anthraquinone can be used. Specifically, C.I. I. Examples thereof include salt-forming compounds of xanthene acid dyes such as Acid Red 52, 87, 92, 289 and 338.

  Examples of the orange pigment that can be used in the present invention include C.I. I. Pigment Orange 38, 43, 71, 73, etc. are mentioned, but it is not particularly limited to these.

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

  Therefore, specific examples of yellow dyes 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, 192, 199 Etc.

  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 etc. are also 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, 105, 106 and the like.

  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 are also included.

  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, organic or inorganic pigments can be used alone or in admixture of two or more, and pigments having high color development properties and high heat resistance, particularly pigments having high heat decomposition resistance are preferred. Organic pigments are used. As the organic pigment, commercially available ones can be used, and natural pigments and inorganic pigments can be used in combination according to the desired hue of the filter segment.

Below, the specific example of the yellow organic pigment which can be used for the said coloring composition is shown. Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, Yellow pigments such as 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214 can be used. 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 preferable.
These yellow pigments can be used alone or in combination of two or more depending on the desired color characteristics.

  Examples of the green pigment that can be used in the present invention include C.I. I. Pigment Green 7, 10, 36, 37, 58, 62, 63, and the like are exemplified, but not limited thereto.

  Examples of blue pigments that can be used in the present invention include 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 2004-333817, Examples include aluminum phthalocyanine pigments described in Japanese Patent No. 4893859, but are not limited thereto.

  The preferred colorant content in all the non-volatile components of the colored 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.

(Miniaturization of pigment)
When the colorant used in the coloring composition of the present invention is a pigment, it can be refined by a salt milling process or the like. It is preferable that the average primary particle diameter calculated | required by TEM (transmission electron microscope) of a pigment is the range of 5-90 nm. When the thickness is smaller than 5 nm, dispersion in an organic solvent becomes difficult. When the thickness is larger than 90 nm, a sufficient contrast ratio cannot be obtained. For these reasons, a more preferable average primary particle size is in the range of 10 to 70 nm.

  Salt milling is a process in which 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, 2-roll mill, 3-roll mill, ball mill, attritor, or sand mill. 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 serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions at the time of subjecting the pigment to salt milling, a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range can be obtained.

  The water-soluble organic solvent functions to wet 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 to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. 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, and most preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment.

  When the salt is milled, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. The amount of 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 one that disperses, dyes, or penetrates a colorant, and includes a thermoplastic resin. Moreover, when using with the form of an alkali image development type colored resist material, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can be used.

  In particular, when an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain is used for an alkali development type colored resist material, the resin is 3 when exposed to active energy rays to form a coating film. By dimensional crosslinking, the colorant is fixed, heat resistance is improved, and color fading (deterioration of spectral characteristics) due to heat of the colorant can be suppressed. In addition, there is also an effect of suppressing aggregation and precipitation of the colorant component in the development 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 disperse the colorant preferably. 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 colorant adsorbing group and a carboxyl group that acts as an alkali-soluble group during development, an aliphatic group that acts as an affinity group for the colorant carrier and solvent, and The balance of the aromatic group is important for the dispersibility, penetrability, developability and durability of the colorant, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developer is poor, and it may be difficult to form a fine pattern. When it exceeds 300 mgKOH / g, a fine pattern may not remain.

  The binder resin is preferably used in an amount of 20 parts by weight or more based on 100 parts by weight of the total weight of the colorant because the film formability and various resistances are good, 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, poly Vinyl acetate, polyurethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, cellulose, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resin Etc. Among them, it is preferable to use an acrylic resin.

Examples of the vinyl-based alkali-soluble resin copolymerized with an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group or a sulfone group.
Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and 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 resins having an ethylenically unsaturated double bond introduced by the following methods (i) and (ii).

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

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

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

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can also be hydrolyzed. Moreover, when an etrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bonds 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 and one or more other monomers. There is a method in which an unsaturated ethylenic monomer having an epoxy group is added to a part of a carboxyl group to introduce an 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 a monomer of an unsaturated monobasic acid having another carboxyl group or another monomer is copolymerized. There is a method of reacting an isocyanate group of an unsaturated ethylenic monomer having an isocyanate group with a side chain hydroxyl group of the obtained copolymer.

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

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

(Thermosetting compound)
In the present invention, a thermosetting compound may be further contained in combination with the thermoplastic resin which is a binder resin. Examples of the thermosetting compound include 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 urea compounds and / or resins, phenol compounds and / or resins, but the present invention is not limited thereto.

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

  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, 2 -Methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1, 3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butyl Benzene, 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 monotert-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 Monoethyl 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, di Propylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol mono Chill 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, isoamyl acetate , Isobutyl acetate, vinegar Propyl, dibasic acid esters and the like. These solvents can be used alone or in admixture of two or more at any ratio as required.

  Among them, the dispersibility of the coloring agent, the penetrability, and the coating property of the coloring composition are good, so that ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl It is preferable to use glycol acetates such as ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone, which are selected from the group consisting of propylene glycol monomethyl ether acetate and clohexanone. The inclusion of at least one kind is particularly preferable from the viewpoint of wrinkle suppression.

  In addition, 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 colored composition can be adjusted to an appropriate viscosity to form a desired colored film having a uniform thickness. Is preferred.

<Photopolymerizable monomer>
Photopolymerizable monomers that may be added to the colored composition of the present invention include monomers or oligomers that are cured by ultraviolet rays or heat 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-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy Luether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylic acid ester, epoxy (meth) acrylate, urethane acrylate and other acrylic acid esters and methacrylic acid esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, ru (meth) acrylamide, N-vinylformamide, acrylonitrile and the like. These photopolymerizable compounds can be used singly or in combination 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. It is more preferable that

<Photopolymerization initiator>
In the colored composition of the present invention, the composition is cured by ultraviolet irradiation, and a photopolymerization initiator is added to form a filter segment by photolithography, and a solvent development type or alkali development type photosensitive coloring composition is added. It can be prepared in the form of a product. Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or Benzoin compounds such as dimethyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3 ' , 4,4'-tetra (t-butylperoxycarbonyl) benzophenone and the like; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethyl Thioxanthone compounds such as thioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxy) Enyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- Triazine compounds such as (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime) Or an oxime ester compound such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethylbenzoyl) ) Phosphine compounds such as phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphor-quinone and ethylanthraquinone; borate compounds; A carbazole compound; an imidazole compound; or a titanocene compound is used. These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

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

<Sensitizer>
Furthermore, the coloring composition of the present invention can contain a sensitizer. Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphor-quinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinones Derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene Derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal allene complexes, organoruthenium complexes, or Mihira-ketone derivatives, biimidazole derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9, 10-phenanthrenequinone, camphor-quinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', or 4,4'-tetra (t-butylperoxyca Rubonyl) benzophenone, 4,4′-diethylaminobenzophenone and the like. These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

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

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

<Multifunctional thiol>
The coloring composition of the present invention can contain a polyfunctional thiol that functions as a chain transfer agent. The polyfunctional thiol may be a compound having two or more thiol groups, such as hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate. , Ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate) Pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionate tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercap -s- triazine, 2- (N, N- dibutylamino) -4,6-dimercapto -s- triazine. These polyfunctional thiols can be used singly or in combination of two or more in any ratio as necessary.

  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 (100% by weight) of the total solid content of the color filter coloring composition. . When the polyfunctional thiol content is less than 0.1% by weight, the effect of adding the polyfunctional thiol is insufficient, and when it exceeds 30% by weight, the sensitivity is too high and the resolution may be lowered.

<Antioxidant>
The coloring composition of the present invention can contain an antioxidant. The antioxidant prevents the photopolymerization initiator and thermosetting compound contained in the coloring composition from being oxidized and yellowed by the thermal process during thermal 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 coating film transmittance can be obtained.

  The “antioxidant” in the present invention may be a compound having an ultraviolet absorption function, a radical scavenging function, or a peroxide decomposition function. Specifically, as an antioxidant, a hindered phenol, a hinder -Doamine-based, phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet absorbers and antioxidants can be used. Among these antioxidants, from the viewpoint of achieving both transmittance and sensitivity of the coating film, preferred are hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur. And system antioxidants. More preferably, it is a hindered phenol antioxidant, a hindered amine antioxidant, or a phosphorus antioxidant. These antioxidants can be used singly or in combination 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 color filter coloring composition (100% by weight) because the brightness and sensitivity are good.

<Amine compound>
Moreover, the coloring composition of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen. Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

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

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, 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 end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of the linear block copolymer types which are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, Examples thereof include, but are not limited to, FZ-2207.

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

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added as an auxiliary to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate. And amphoteric surfactants such as alkylbetaines such as alkyldimethylaminoacetic acid betaines and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Of these, compounds having two or more phenolic hydroxyl groups in one molecule and amine curing agents are preferred. 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 amidine compounds and salts thereof ( For example, imidazole, 2-methyl imidazole, 2-ethyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 4-phenyl imidazole, 1-cyanoethyl-2 -Phenylimidazole, 1- (2-cyanoethyl) -2-e Ru-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, 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. As content of the said hardening accelerator, 0.01-15 weight part is preferable with respect to 100 weight part of thermosetting resins.

<Other additive components>
The coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity with time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained. 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 methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. 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.

  Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and 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, with respect to 100 parts by weight of the colorant in the coloring composition.

<Method for producing colored composition>
The coloring composition of the present invention contains a colorant in a colorant carrier such as a binder resin, a photosensitive oligomer and / or a solvent, preferably together with a dispersion aid, a kneader, a two-roll mill, a three-roll mill, -It can be produced by finely dispersing using various dispersing means such as a rumill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor (colorant dispersion). The binder resin and the photosensitive oligomer may be added after obtaining the colorant dispersant. At this time, two or more kinds of colorants or the like may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the colorant carrier may be mixed. When the solubility of the colorant such as a dye is high, specifically, it is highly soluble in the solvent to be used, and if it is dissolved and no foreign matter is confirmed by stirring, it is finely dispersed as described above. There is no need.

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

<Dispersing aid>
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, or a surfactant may be appropriately contained. Since the dispersion aid has a great effect of preventing reaggregation of the colorant after dispersion, the color composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has lightness and viscosity stability. Become good. The dye derivative is as described above.

[Dye derivative]
As the dye derivative, various conventionally known dye derivatives can be arbitrarily selected and contained, and the organic pigment, anthraquinone, acridone or triazine has a basic substituent, an acidic substituent, or a substituent. Examples thereof include compounds in which a phthalimidomethyl group may be introduced. For example, JP-A 63-305173, JP-B 57-15620, JP-B 59-40172, JP-B 63-17102, Japanese Patent Publication Nos. 5-9469, 2001-335717, 2003-128669, 2003-167112, 2004-091497, 2004-307854, 2007 -156395, JP2008-094773, JP2008-094986 , JP 2008-095007, JP 2008-195916, JP-those described in Patent No. 4,585,781 discloses the like can be used.

Examples of the pigment derivative having a basic group of the present invention are shown below, but are not limited thereto.

Compound 1:

Compound 2:

Compound 3:

Compound 4:

Compound 5:

[Resin dispersant]
The resin-type dispersant has a colorant-affinity part that has the property of adsorbing to the additive colorant and a part that is compatible with the colorant carrier, and is adsorbed to the additive colorant and dispersed in the colorant carrier. It works to stabilize. Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-based dispersants such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Water-soluble resin, water-soluble polymer compound, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide adduct, phosphoric ester or the like is used, they may be used alone or in combination, it is not necessarily limited thereto.

  Among the above-mentioned dispersants, a polymer dispersant having a basic functional group is preferable because the viscosity of the dispersion is lowered and a high contrast is exhibited with a small addition amount, and a nitrogen atom-containing graft copolymer or side chain is preferable. Nitrogen atom-containing acrylic block copolymers and urethane polymer dispersants having functional groups containing tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles, and the like are preferred. The resin type dispersant is preferably used in an amount of about 5 to 200% by weight based on the total amount of the colorant, and more preferably about 10 to 100% by weight from the viewpoint of film formability.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, manufactured by Big Chemi Japan. 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, or LACTIMON, LACTIMON-WS or BYKUMEN, etc., SOLPERSE-3000, 9000, manufactured by Nippon Lubrizol, Inc. 3000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc., BASF EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4 00,5010,5065,5066,5070,7500,7554,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of Ajisupa -PA111, PB711, PB821, PB822, PB824, and the like.

Moreover, as a resin type dispersing agent used by this invention, the following (S1) or (S2) resin can be contained as a dispersing agent which has a carboxyl group.
(S1) A resin which is a reaction product of the hydroxyl group of the polymer (S1) having a hydroxyl group and the acid anhydride group of tricarboxylic anhydride and / or tetracarboxylic dianhydride.
(S2) In the presence of the reaction product of the hydroxyl group of the compound (S2) having a hydroxyl group and the acid anhydride group of tricarboxylic anhydride and / or tetracarboxylic dianhydride, an ethylenically unsaturated monomer is used. A resin that is a polymerized polymer.

[Resin (S1)]
Resin (S1) can be manufactured by well-known methods, such as WO2008 / 007776, Unexamined-Japanese-Patent No. 2008-029901. 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. The compound (b) having a hydroxyl group is preferably a compound having a hydroxyl group and a thiol group in the molecule as described later. Since the terminal hydroxyl group is preferably plural, among them, the compound (b1) having two hydroxyl groups and one thiol group in the molecule is preferably used.

  That is, a polymer having two hydroxyl groups at one end, which is a more preferable example, includes the monomer (c1) in the presence of the 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). The hydroxyl group of the polymer (a) having a hydroxyl group reacts with an acid anhydride group of a tricarboxylic anhydride and / or tetracarboxylic dianhydride to form an ester bond, while the anhydrous ring is opened to give a carboxylic acid Produce.

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

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

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

  When the surfactant is added, the amount is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the colorant. When the blending amount of the surfactant is less than 0.1 parts by weight, it is difficult to obtain the added effect. When the content is more than 55 parts by weight, the dispersion may be affected by an excessive dispersant. .

<Removal of coarse particles>
The colored composition of the present invention is a coarse particle having a size of 5 μm or more, preferably a coarse particle having a size of 1 μm or more, more preferably a coarse particle having a size of 0.5 μm or more. It is preferable to remove the mixed dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less.

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

  As the transparent substrate, glass plates such as soda-lime glass, low alkali borosilicate glass, non-alkali aluminoborosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate are used. . In addition, 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 in order to drive the liquid crystal after forming the panel.

  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.

  Formation of each color filter segment and black matrix by the photolithography method is performed by the following method. That is, a photosensitive coloring composition prepared as a solvent developing type or alkali developing type colored resist material is dried on a transparent substrate by a coating method such as spray coating, spin coating, slit coating or roll coating. It is applied so that the thickness is 0.2 to 10 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film.

  Thereafter, the filter segment and the black matrix can be formed by immersing in a solvent or an alkaline developer, or spraying the developer by spraying or the like to remove uncured portions and forming a desired pattern. Furthermore, in order to accelerate the polymerization of the filter segment and the black matrix formed by development, heating can be performed as necessary. According to the photolithography method, it is possible to form a filter segment and a black matrix with higher accuracy than the printing method.

  In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution. As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.

  In order to increase the UV exposure sensitivity, the photosensitive coloring composition is applied and dried, and then water-soluble or alkali-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to prevent polymerization inhibition due to oxygen. After the film to be formed is formed, ultraviolet exposure can be performed.

  EXAMPLES The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In Examples and Comparative Examples, “part” and “%” mean “part by mass” and “% by mass”, respectively.

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

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

(Production of refined pigment (Y-1))
100 parts of quinophthalone yellow pigment PY138 (“Pariol Yellow K0961HD” manufactured by BASF), 3 parts of a pigment derivative (the above-mentioned compound 1), 800 parts of crushed salt, and 180 parts of diethylene glycol are made of 1 gallon kneader made of stainless steel (Inoue Seisakusho). And kneaded at 70 ° C. for 4 hours. The mixture was poured into 3000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 24 ° C. for 24 hours. It was dried for a period of time to obtain 98 parts of refined pigment (Y-1).

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

(Production of refined pigment (R-1))
100 parts of diketopyrrolopyrrole-based red pigment PR254 ("Irgafore Red B-CF" manufactured by BASF), 10 parts of a pigment derivative (previously compound 2), 1000 parts of crushed salt, and 120 parts of diethylene glycol, 1 gallon made of stainless steel The mixture was charged into a kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 8 hours. The mixture was poured into 2000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 24 ° C. for 24 hours. After drying for 100 hours, 100 parts of a refined pigment (R-1) was obtained.

(Production of refined pigment (R-2))
100 parts of anthraquinone red pigment PR177 (“chromophthaled red A2B” manufactured by BASF), 5 parts of a pigment derivative (the above-mentioned compound 3), 800 parts of crushed salt and 180 parts of diethylene glycol are made of 1 gallon kneader made of stainless steel (manufactured by Inoue Seisakusho). And kneaded at 70 ° C. for 5 hours. The mixture was added to 4000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 24 ° C. for 24 hours. After drying for 100 hours, 100 parts of a refined pigment (R-2) was obtained.

(Production of refined pigment (B-1))
100 parts of copper phthalocyanine-based blue pigment PB15: 6 (“Lionol Blue ES” manufactured by Toyocolor Co., Ltd.), 5 parts of a pigment derivative (the above-mentioned compound 4), 1000 parts of crushed salt, and 100 parts of diethylene glycol, 1 gallon kneader made of stainless steel (Made by Inoue Seisakusho) and kneaded at 50 ° C. for 12 hours. The mixture was poured into 3000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 24 ° C. for 24 hours. After drying for 98 hours, 98 parts of a fine pigment (B-1) was obtained.

(Production of refined pigment (V-1))
300 parts of dioxazine-based purple pigment PV23 (“Rionogen Violet RL” manufactured by Toyocolor Co., Ltd.) was added to 3000 parts of 96% sulfuric acid, and the mixture was stirred for 1 hour and poured into 5 ° C. water. After stirring for 1 hour, it was filtered, washed with warm water until the washing solution became neutral, and dried at 70 ° C. 120 parts of the obtained acid pasting pigment, 5 parts of a dye derivative (compound 5 described above), 1500 parts of pulverized sodium chloride and 100 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) at 20 ° C. Kneaded for hours. The mixture was poured into 5000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 24 ° C. for 24 hours. It dried for a time and obtained 115 parts of micronized pigment (V-1).

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

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

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

<Manufacture of binder resin solution>
370 parts of propylene glycol monomethyl ether acetate (PGMAc) is put 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 dropped 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 parts

  After completion of the dropwise addition, the mixture was further reacted 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. The reaction was continued for a time to obtain a copolymer solution. After cooling to room temperature, about 2 g of the alkali-soluble resin solution is sampled and heated and dried 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 32,000 and an acid value of 78.

<Manufacture of dispersant>
(Production 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 reaction vessel was heated to 80 ° C., and 5.7 parts of 3-mercapto-1,2-propanediol and 0.1 part of 2,2′-azobisisobutyronitrile were added to propylene glycol monomethyl ether acetate. The solution dissolved in 45.4 parts was added and reacted for 10 hours. It was confirmed that 95% had reacted by solid content measurement. At this time, the weight average molecular weight was 4000. Next, 9.2 parts of pyromellitic dianhydride, 31.7 parts of propylene glycol monomethyl ether acetate and 0.2 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added. And reacted at 120 ° C. for 7 hours. The reaction was completed after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. After completion of the reaction, propylene glycol monomethyl ether acetate was added so as to have a nonvolatile content of 60% by weight to obtain a solution of dispersant (X) having an acid value of 70 mgKOH / g and a weight average molecular weight of 9,500.

<Production of photosensitive oligomer>
(Production example of photosensitive oligomer 1)
In a four-necked flask equipped with a stirrer, reflux condenser, dry air introduction pipe, thermometer, 10.0 g of trimethylolpropane, 11.3 g of 1,2,3,6-tetrahydrophthalic anhydride, 0.1 g of DBU, 21.3 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, 0.05 g of p-methoxyphenol, 25.1 g of hexamethylene diisocyanate, 68.4 g of pentaerythritol triacrylate, and 93.5 g of propylene glycol monomethyl ether acetate were added, and then 0.23 g of dioctyltin was added as a catalyst until the temperature reached 100 ° C. The temperature rose. After reacting at 100 ° C. for 3 hours and confirming the disappearance of the isocyanate peak 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 a weight average molecular weight of MW 7,200.

(Production example of photosensitive oligomers 2 to 10)
Synthesis was performed in the same manner as the photosensitive oligomer 1 solution except that the raw materials and preparation amounts shown in Table 1 were used, and photosensitive oligomer 2 to 10 solutions were obtained.

(Production example of photosensitive oligomer 11)
In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, 5.0 g trimethylolpropane, 18.8 g hexamethylene diisocyanate, 51.3 g pentaerythritol triacrylate, propylene glycol monomethyl ether acetate 75. 1 g, 0.02 g of p-methoxyphenol, and then 0.12 g of dioctyltin as a catalyst were added, and the temperature was raised to 100 ° C. After reacting at 100 ° C. for 3 hours and confirming the disappearance of the isocyanate peak by IR, the reaction was terminated by cooling to room temperature to obtain a photosensitive oligomer 11 solution. This reaction solution was colorless and transparent, had a solid content of 50%, and a weight average molecular weight of MW 7,600.

The abbreviations in Table 1 are shown below.
DBU: 1,8-diazabicyclo- [5.4.0] -7-undecene PGMAc: propylene glycol monomethyl ether acetate M-306: pentaerythritol tri and tetraacrylate (manufactured by Toagosei Co., Ltd.)
M-403: dipentaerythritol penta and hexaacrylate (manufactured by Toagosei Co., Ltd.)

<Adjustment of photosensitive coloring composition for color filter>
[Example 1]
(Adjustment of photosensitive coloring composition (C1))
A 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 colored 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- Morpholinopropan-1-one)
: 1.8 parts Sensitizer (4,4'-bis (diethylamino) benzophenone)
: 0.2 part PGMAc: 34.0 parts

[Examples 2 to 30, Comparative Examples 1 to 6]
(Adjustment of photosensitive coloring composition (C2 to C36))
A photosensitive colored composition (C2 to C36) was obtained in the same manner as in Example 1 except that the photosensitive oligomer described in Table 2 was 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)
About the obtained photosensitive coloring composition (C1-36), a photosensitive coloring composition is apply | coated so that it may become a film thickness of 3.4 micrometers on a 100 mm x 100 mm and 0.7 mm glass substrate, and it has a predetermined pattern. UV exposure was performed under the condition of 40 mJ / cm ² through a mask. Thereafter, an alkali developer was sprayed by spraying to remove the uncured portion and form a desired pattern. About the obtained coating film, the heat processing (post-baking) were performed for 20 minutes in 230 degreeC oven, and the presence or absence of wrinkles was confirmed with the microscope (OLYMPUS Optical Co., Ltd. "BX-51"). Evaluation was made by observing a square pixel of 400 μm × 400 μm 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.).
◎: Wrinkle does not occur ○: Wrinkle occurs in a part of the pattern ×: It occurs in the entire pattern

(Developability (pattern residue evaluation))
About the obtained photosensitive coloring composition (C1-36), a photosensitive coloring composition is apply | coated so that it may become a film thickness of 3.4 micrometers on a 100 mm x 100 mm and 0.7 mm glass substrate, and it has a predetermined pattern. UV exposure was performed under the condition of 40 mJ / cm ² through a mask. Thereafter, an alkali developer was sprayed by spraying to remove the uncured portion and form a desired pattern. About the obtained coating film, the heat processing (post-baking) were performed for 20 minutes in 230 degreeC oven, and the presence or absence of the residue was confirmed with the microscope (OLYMPUS Optical Co., Ltd. "BX-51"). In 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 ○: Less than 50 μm ² ×: 50 μm ² or more

Claims (8)

A photosensitive coloring composition for a color filter comprising a photosensitive oligomer, a colorant, a dispersion aid, a binder resin and a solvent,
Compound (C) having a hydroxyl group and a carboxyl group, wherein the photosensitive oligomer is a reaction product of a polyol (A) having three or more hydroxyl groups and a compound (B) having an acid anhydride group,
Diisocyanate (D) and
A photosensitive coloring composition for a color filter, which is a reaction product of a compound (E) having a hydroxyl group and an ethylenically unsaturated bond group.   The photosensitive coloring composition for a color filter according to claim 1, wherein the compound (E) having a hydroxyl group and an ethylenically unsaturated bond group is a compound (E1) having a hydroxyl group and three or more ethylenically unsaturated bond groups. object.   The photosensitive coloring composition for color filters according to claim 1 or 2, wherein the photosensitive oligomer has an acid value of 15 or more and 100 or less (mgKOH / g).   The photosensitive coloring composition for color filters according to any one of claims 1 to 3, wherein the diisocyanate (D) is at least one selected from the group consisting of hexamethylene diisocyanate and isophorone diisocyanate.   Furthermore, 1 type chosen from the group which consists of a photoinitiator and a photopolymerizable monomer (however, it is a photosensitive oligomer or binder resin) is contained as described in any one of Claims 1-4. The photosensitive coloring composition for color filters.   The photosensitive coloring composition for color filters according to any one of claims 1 to 5, wherein the solvent is at least one selected from the group consisting of propylene glycol monomethyl ether acetate and cyclohexanone.   A color filter comprising a filter segment formed on the substrate from the photosensitive coloring composition for a color filter according to any one of claims 1 to 6. A method for producing a photosensitive coloring composition for a color filter comprising mixing a photosensitive oligomer, a colorant, a dispersion aid, a binder resin and a solvent,
The photosensitive oligomer
The compound (C) having a hydroxyl group and a carboxyl group was obtained by reacting the hydroxyl group of the polyol (A) having three or more hydroxyl groups with the acid anhydride group of the compound (B) having an acid anhydride group. rear,
The manufacturing method of the photosensitive coloring composition for color filters which makes the hydroxyl group of the compound (E) which has the hydroxyl group of a compound (C), the isocyanate group of a diisocyanate (D), and a hydroxyl group and an ethylenically unsaturated bond group react.