JP2009222762A - Colored photosensitive resin composition, black matrix, color filter and liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored photosensitive resin composition capable of preventing foreign substances (defects) from occurring when dried under reduced pressure after coating. <P>SOLUTION: The colored photosensitive resin composition comprises (A) a photopolymerizable compound, (B) a photopolymerization initiator, (C) a colorant, (D) a dispersant, and (S) a solvent, wherein the solvent (S) comprises at least one (R) slightly volatile solvent having a boiling point of 180-250°C, and the dispersant (D) comprises a compound (D11) satisfying predetermined requirements. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a colored photosensitive resin composition, a black matrix, a color filter, and a liquid crystal display.

  A display body such as a liquid crystal display has a structure in which a liquid crystal layer is sandwiched between two substrates on which a pair of electrodes facing each other is formed. A color filter made up of pixel regions of each color such as red (R), green (G), and blue (B) is formed inside one substrate. In this color filter, normally, a black matrix is formed so as to partition red, green, and blue pixel regions.

  Generally, a color filter is manufactured by a lithography method. That is, first, a black colored photosensitive resin composition is applied on a substrate, dried under reduced pressure (vacuum drying) with a vacuum drying apparatus (VCD), and then exposed and developed to form a black matrix. Next, for each colored photosensitive resin composition of each color of red, green, and blue, coating, drying, exposure, and development are repeated to form a pixel region of each color at a predetermined position to manufacture a color filter.

  The colorant that is a component of the colored photosensitive resin composition is generally dispersed in the composition by a dispersant.

Here, in Patent Document 1, as a dispersant, pigment dispersion for a color filter using a block copolymer resin comprising a pigment adsorption block containing a basic group that is a pigment adsorption group and a block not containing a pigment adsorption group. A resist composition is disclosed.
Japanese Patent Laid-Open No. 2004-054213

  However, depending on the type of dispersant and solvent used in the colored photosensitive resin composition, there is a problem that foreign matter is generated when drying under reduced pressure. In order to maintain the quality of products, it is an important issue to suppress the generation of foreign substances.

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a colored photosensitive resin composition capable of preventing the occurrence of foreign matters (defects) during drying under reduced pressure after application of the colored photosensitive resin composition. And

  In the colored photosensitive resin composition containing (A) a photopolymerizable compound, (B) a photopolymerization initiator, (C) a colorant, (D) a dispersant, and (S) a solvent, (S) The solvent contains at least one (R) hardly volatile solvent whose boiling point satisfies a predetermined condition, and (D) the dispersant contains a compound (D11) that satisfies the predetermined requirement. In this case, it was found that generation of defects after drying under reduced pressure can be prevented, and the present invention has been completed.

  Specifically, the present invention provides the following.

［式（ｄ−１）中、Ｑ及びＱ’は、それぞれ２価の有機基である。Ａ、Ｂは各骨格の割合（モル比）を示す。］ The first aspect of the present invention is a colored photosensitive resin composition comprising (A) a photopolymerizable compound, (B) a photopolymerization initiator, (C) a colorant, (D) a dispersant, and (S) a solvent. The (S) solvent contains at least one (R) hardly volatile solvent having a boiling point of 180 ° C. or higher and 250 ° C. or lower, and the (D) dispersant is represented by the following formula (d-1): It is a coloring photosensitive resin composition containing the compound (D11) which has each frame | skeleton represented by this.

[In formula (d-1), Q and Q ′ each represents a divalent organic group. A and B show the ratio (molar ratio) of each skeleton. ]

  The second aspect of the present invention is a black matrix and / or a color filter having a pattern formed by using the colored photosensitive resin composition of the present invention.

  Furthermore, a third aspect of the present invention is a liquid crystal display having the black matrix and / or color filter of the present invention.

  According to the present invention, (S) the solvent contains (R) a hardly volatile solvent, and (D) the dispersant contains the predetermined compound (D11). Can be suppressed.

  Hereinafter, embodiments of the present invention will be described in detail. In addition, this invention is not limited to the following embodiment at all.

<Colored photosensitive resin composition>
The colored photosensitive resin composition of the present invention contains (A) a photopolymerizable compound, (B) a photopolymerization initiator, (C) a colorant, (D) a dispersant, and (S) a solvent. (Hereinafter, they may be referred to as “component (A)”, “component (B)”, “component (C)”, “component (D)”, and “component (S)”, respectively).

[(A) Photopolymerizable compound]
The photopolymerizable compound includes a resin or monomer having an ethylenically unsaturated group. Moreover, as a photopolymerizable compound, it is more preferable to combine the resin and monomer which have an ethylenically unsaturated group. By combining a resin having an ethylenically unsaturated group and a monomer having an ethylenically unsaturated group, curability can be improved and pattern formation can be facilitated. In the present specification, among compounds having an ethylenically unsaturated group, those having a mass average molecular weight of 1000 or more are referred to as “resin having an ethylenically unsaturated group”, and those having a mass average molecular weight of less than 1000 are referred to as “ It will be referred to as a “monomer having an ethylenically unsaturated group”.

(Resin having an ethylenically unsaturated group)
As the resin having an ethylenically unsaturated group, (meth) acrylic acid, fumaric acid, maleic acid, monomethyl fumarate, monoethyl fumarate, 2-hydroxyethyl (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, ethylene Glycol monoethyl ether (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, acrylonitrile, methacrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol diacrylate, triethylene glycol di (meth) acrylate, tetrae Lenglycol di (meth) acrylate, butylene glycol dimethacrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra Oligomers in which (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, cardoepoxy diacrylate, etc. are polymerized; polyhydric alcohol Polyester (meth) acrylate obtained by reacting (meth) acrylic acid with a polyester prepolymer obtained by condensation of a monobasic acid with a polybasic acid. Polyurethane (meth) acrylate obtained by reacting a rate, a polyol and a compound having two isocyanate groups and then reacting with (meth) acrylic acid; and bisphenol A type epoxy resin and bisphenol F type epoxy resin Bisphenol S type epoxy resin, phenol or cresol novolak type epoxy resin, resol type epoxy resin, triphenolmethane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ester, aliphatic or cycloaliphatic epoxy resin, amine epoxy Examples thereof include an epoxy (meth) acrylate resin obtained by reacting a resin and an epoxy resin such as a dihydroxybenzene type epoxy resin with (meth) acrylic acid. Furthermore, a resin obtained by reacting an epoxy (meth) acrylate resin with a polybasic acid anhydride can be used.

  In addition, as the resin having an ethylenically unsaturated group, a reaction product of the epoxy compound (a1) and the ethylenically unsaturated group-containing carboxylic acid compound (a2) is further reacted with the polybasic acid anhydride (a3). The resin obtained by this can be used preferably.

(Epoxy compound (a1))
Examples of the epoxy compound (a1) include glycidyl ether type, glycidyl ester type, glycidyl amine type, alicyclic type, bisphenol A type, bisphenol F type, bisphenol S type, biphenyl type, naphthalene type, fluorene type, phenol novolac type, and An ortho-cresol type epoxy resin etc. are mentioned.

(Ethylenically unsaturated group-containing carboxylic acid compound (a2))
The ethylenically unsaturated group-containing carboxylic acid compound (a2) is preferably a monocarboxylic acid compound containing a reactive ethylenic double bond such as an acryl group or a methacryl group in the molecule. Examples of such ethylenically unsaturated group-containing carboxylic acid compounds include acrylic acid, methacrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, α-cyanocinnamic acid, and cinnamic acid. This ethylenically unsaturated group-containing carboxylic acid compound (a2) may be used alone or in combination of two or more.

  As a method of reacting the epoxy compound (a1) with the ethylenically unsaturated group-containing carboxylic acid compound (a2), a known method can be used. For example, an epoxy compound (a1) and an ethylenically unsaturated group-containing carboxylic acid compound (a2) are converted into a tertiary amine such as triethylamine and benzylethylamine, dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, and benzyl. Examples thereof include a method of reacting in an organic solvent at a reaction temperature of 50 ° C. or more and 150 ° C. or less for several hours to several tens of hours using a quaternary ammonium salt such as triethylammonium chloride, pyridine, triphenylphosphine, or the like as a catalyst.

  The use amount ratio in the reaction between the epoxy compound (a1) and the ethylenically unsaturated group-containing carboxylic acid compound (a2) is the same as the epoxy equivalent of the epoxy compound (a1) and the carboxyl of the ethylenically unsaturated group-containing carboxylic acid compound (a2). The ratio to the acid equivalent is usually 1: 0.5 to 1: 2, preferably 1: 0.8 to 1: 1.25, more preferably 1: 1. By setting it as the above range, the crosslinking efficiency tends to be improved.

(Polybasic acid anhydride (a3))
Examples of the polybasic acid anhydride (a3) include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride. Acid, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4- Examples include ethylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-ethyltetrahydrophthalic anhydride, and 4-ethyltetrahydrophthalic anhydride. These polybasic acid anhydrides may be used alone or in combination of two or more.

  As a method for reacting the epoxy compound (a1) with the ethylenically unsaturated group-containing carboxylic acid compound (a2) and further reacting the polybasic acid anhydride (a3), a known method can be used. The ratio of the amounts used is the number of moles of OH groups in the reaction product of the epoxy compound (a1) and the ethylenically unsaturated group-containing carboxylic acid compound (a2) and the acid anhydride of the polybasic acid anhydride (a3). The equivalent ratio of groups is usually from 1: 1 to 1: 0.1, preferably from 1: 0.8 to 1: 0.2. By making it into said range, there exists a tendency for the solubility to a developing solution to become moderate.

  The acid value of the resin obtained by further reacting the reaction product of the epoxy compound (a1) with the ethylenically unsaturated group-containing carboxylic acid compound (a2) with the polybasic acid anhydride (a3) is the resin solid content. It is preferably 10 mgKOH / g or more and 150 mgKOH / g or less, and more preferably 70 mgKOH / g or more and 110 mgKOH / g or less. By setting the acid value of the resin to 10 mgKOH / g or more, sufficient solubility in the developer can be obtained, and by setting it to 150 mgKOH / g or less, sufficient curability can be obtained and the surface property should be improved. Can do.

  Further, the mass average molecular weight (Mw) of the resin is preferably 1000 or more and 40000 or less, and more preferably 2000 or more and 30000 or less. By making the mass average molecular weight 1000 or more, heat resistance and film strength can be improved, and by making it 40000 or less, sufficient solubility in a developer can be obtained.

  Moreover, as resin which has an ethylenically unsaturated group, resin which has a cardo structure in a molecule | numerator can be used preferably. Since the resin having a cardo structure has high heat resistance and chemical resistance, the heat resistance and chemical resistance of the colored photosensitive resin composition can be improved by using it as a photopolymerizable compound. For example, a resin represented by the following formula (2) can be preferably used.

In formula (2), X is a group represented by the following formula (3). n is 1-20.

  In the formula (2), Y is maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyl It is a residue obtained by removing a carboxylic anhydride group (—CO—O—CO—) from a dicarboxylic anhydride such as tetrahydrophthalic anhydride and glutaric anhydride.

  In the formula (2), Z is 2 from tetracarboxylic dianhydrides such as pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, and biphenyl ether tetracarboxylic dianhydride. This residue is obtained by removing one carboxylic anhydride group.

(Monomer having an ethylenically unsaturated group)
Monomers having an ethylenically unsaturated group include monofunctional monomers and polyfunctional monomers.

  Monofunctional monomers include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-methylol ( (Meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide- 2-methylpropane sulfonic acid, tert-butylacrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate Cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (Meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl ( And (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, and phthalic acid derivative half (meth) acrylate. These monofunctional monomers may be used alone or in combination of two or more.

  On the other hand, as the polyfunctional monomer, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol Tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meta Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxydi Ethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) Acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (Meth) acrylate, urethane (meth) acrylate (ie, tolylene diisocyanate), reaction product of trimethylhexamethylene diisocyanate and hexamethylene diisocyanate and 2-bidoxyethyl (meth) acrylate, methylenebis (meth) acrylamide, (meth) acrylamide methylene Examples include ethers, condensates of polyhydric alcohols and N-methylol (meth) acrylamide, and triacryl formal. These polyfunctional monomers may be used alone or in combination of two or more.

  The content of the monomer having an ethylenically unsaturated group is preferably 5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 40% by mass with respect to the solid content of the colored photosensitive resin composition. The range is as follows. By setting it as the above range, it tends to be easy to balance sensitivity, developability, and resolution. In addition, solid content means the sum total of components other than a solvent.

  The content of the photopolymerizable compound is preferably 5% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 40% by mass or less with respect to the solid content of the colored photosensitive resin composition. By setting it as the above range, it tends to be easy to balance sensitivity, developability, and resolution.

[(B) Photopolymerization initiator]
As photopolymerization initiators, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2 -Methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropane -1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpho Linopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, ethanone-1- [ -Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyl Dimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino- 2-isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, methyl O-benzoylbenzoate, 2,4- Diethylthioxanthone, 2-chlorothioxanthone, 2 4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2, -(O-chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, 4,4 ' Bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin Butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloro Acetophenone, p-tert-butyldichloroacetophenone, α, α-dichloro-4-phenoxyace Tophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) propane, p-methoxytriazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (Trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2) -Yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino) -2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s -Triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4- Butoxy) styryl phenyl -s- triazine, and 2,4-bis - trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl -s- triazine. Among these, it is particularly preferable in terms of sensitivity to use an oxime-based photopolymerization initiator. These photopolymerization initiators may be used alone or in combination of two or more.

  The content of the photopolymerization initiator is preferably 0.5% by mass or more and 30% by mass or less, and more preferably 1% by mass or more and 20% by mass or less with respect to the solid content of the colored photosensitive resin composition. preferable. By setting it within the above range, sufficient heat resistance and chemical resistance can be obtained, coating film forming ability can be improved, and photocuring failure can be suppressed.

[(C) Colorant]
Although it does not specifically limit as a coloring agent, A conventionally well-known pigment can be used. For example, when a black matrix or black stripe is formed using the colored photosensitive resin composition of the present invention, carbon black, titanium black, chromium oxide, iron oxide, aniline black, perylene pigment, and C.I. I. A black pigment such as Solvent Black 123 can be used. Also, carbon black coated with epoxy resin, etc .; inorganic black pigments such as composite oxides such as titanium, manganese, iron, copper, and cobalt; combinations of organic pigments shown below; Combinations with pigments can also be employed as appropriate. Depending on the combination, it is possible to increase the resistance value and adjust the color tone. In addition, when combining a black pigment and another coloring component, it is preferable to mix another coloring component in the range which does not reduce light-shielding performance.

  Examples of the inorganic black pigment include carbon black dispersion “CF black” (containing 24% high-resistance carbon) manufactured by Mikuni Dye.

  In addition, in order to suppress the reddish color tone of carbon black and make it more preferable black as a whole, a violet dispersion liquid (containing 10% violet pigment) manufactured by Mikuni Color Co., Ltd., a blue pigment dispersion liquid “CF Blue” manufactured by Mikuni Color Co., Ltd. ( Blue pigment (containing 20%)) can also be mixed.

  In the case of chromatic colors such as red, green, blue, cyan, magenta, and yellow, for example, pigments described in JP-A-60-237403 and JP-A-4-310901 can be exemplified.

Specifically, the color index number (C.I.No.)
Yellow pigment: C.I. I. 20, 24, 83, 86, 93, 109, 110, 117, 125, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 168, 180, 185, 195
Orange pigment: C.I. I. 36, 43, 51, 55, 59, 61
Red pigment: C.I. I. 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254
Purple pigment: C.I. I. 19, 23, 29, 30, 37, 40, 50
Blue pigment: C.I. I. 15, 15: 3, 15: 6, 22, 60, 64
Green pigment: C.I. I. 7, 36
Brown pigment: C.I. I. 23, 25, 26
Can be suitably used because of its high transparency and excellent heat resistance, weather resistance, and chemical resistance.

  The pigment is preferably contained in the range of 1% by mass to 70% by mass and more preferably in the range of 20% by mass to 60% by mass with respect to the solid content of the colored photosensitive resin composition. . If it is less than 1% by mass, it is difficult to function as a color filter. On the other hand, if it exceeds 70% by mass, the sensitivity is lowered, and the heat resistance and chemical resistance of the cured coating film may be lowered.

  In the colored photosensitive resin composition in which the black pigment is dispersed, the content of the pigment is preferably more than 40% by mass with respect to the solid content of the colored photosensitive resin composition, and is 50% by mass or more. More preferably it is. By making the content of the pigment more than 40% by mass, a colored photosensitive resin composition having excellent light shielding properties can be obtained. On the other hand, when the content of the black pigment is 70% by mass or less based on the solid content of the colored photosensitive resin composition, the sensitivity, the heat resistance of the cured coating film, and the chemical resistance are kept good. Therefore, it is preferable. As an upper limit, 60 mass% is more preferable.

  In a colored photosensitive resin composition in which a black pigment is dispersed, a colored photosensitive resin composition having a high light-shielding property (optical density, OD value) is obtained by containing a colorant within the above-mentioned content range. Can do. In the colored photosensitive resin composition of the present invention, the optical density is preferably 3.8 or more, more preferably 4.0 or more, still more preferably 4.3 or more, and 4.5 The above is particularly preferable.

［式（ｄ−１）中、Ｑ及びＱ’は、それぞれ２価の有機基である。Ａ、Ｂは各骨格の割合を示す。］ [(D) Dispersant]
The colored photosensitive resin composition of the present invention contains a dispersant in order to disperse the pigment in the colored photosensitive resin composition. In the present invention, the dispersant (D) contains a compound (D11) having each skeleton represented by the following general formula (d-1).

[In formula (d-1), Q and Q ′ each represents a divalent organic group. A and B show the ratio of each skeleton. ]

  In formula (d-1), Q and Q ′ are divalent organic groups. Specifically, it is a linear, branched, or cyclic hydrocarbon group having 1 to 20 carbon atoms that may have a substituent, and the hydrocarbon group may be an aliphatic hydrocarbon group. It may be an aromatic hydrocarbon group. Q is preferably an aromatic hydrocarbon group-containing group having 1 to 20 carbon atoms, more preferably a group having 1 to 10 carbon atoms, and among them, a phenylene group is preferable. Q ′ is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and among them, a linear alkylene group having 1 to 15 carbon atoms is preferable.

  Moreover, in Formula (d-1), A and B show the ratio (molar ratio) of each skeleton. A preferable range is A: B = 1: 99 to 99: 1, more preferably 1:99 to 20:80, and still more preferably 2:98 to 10:90. If A and B are within the above ranges, the compound (D11) having each skeleton represented by the formula (d-1) includes a plurality of types of skeletons (those having different Q and / or Q ′). In the embodiment of the present invention, Q and / or Q ′ are preferably present in a form having different linking groups.

  Further, when the total amount of the compound (D11) is 100, the ratio (molar ratio) of the skeleton represented by the formula (d-1) is preferably 70 or more, more preferably 80 or more, and 90 It is still more preferable that it is above.

［式（ｄ−２）中、Ｐｈは置換基を有していてもよいフェニレン基を示す。ｘは０以上１０以下である。Ａ、Ｂは各骨格の割合を示し、Ａ：Ｂ＝１：９９から９９：１である。］ Of the compounds (D11), a compound (D12) having each skeleton represented by the following general formula (d-2) is preferable.

[In the formula (d-2), Ph represents a phenylene group which may have a substituent. x is 0 or more and 10 or less. A and B indicate the ratio of each skeleton, and A: B = 1: 99 to 99: 1. ]

  In formula (d-2), Ph represents a phenylene group which may have a substituent. x is 0 or more and 10 or less, preferably 0 or more and 8 or less, more preferably 0 or more and 6 or less.

Specifically, preferred examples of the skeleton having Ph include the following.

  In the formula (d-2), A and B are the same as those in the above (d-1). As long as A and B are within the above ranges, the compound (D12) having a skeleton of the formula (d-2) may contain a plurality of types of skeletons (one having different Ph and / or x). In the embodiment, it is preferable that Ph and / or x exist in a form having different substituents and / or linking groups. When x is different, the average value of x is preferably 0 or more and 6 or less, more preferably 0 or more and 3 or less.

  Further, the ratio (molar ratio) of the skeleton represented by the formula (d-2) when the total compound (D12) is 100 is preferably 70 or more, more preferably 80 or more, More preferably, it is 90 or more. The compound (D12) is particularly preferably composed of each skeleton represented by the general formula (d-2) except for a terminal residue.

［式（ｄ−３）中、Ｑ’’は２価の有機基である。］ Moreover, the said compound (D11) may contain the frame | skeleton (d-3) represented by the following general formula (d-3) in the range which does not impair the effect of this invention.

[In formula (d-3), Q ″ represents a divalent organic group. ]

  In formula (d-3), Q ″ is a divalent organic group, specifically the same as in the case of Q or Q ′. Q ″ is preferably an aliphatic hydrocarbon group having 1 to 30 carbon atoms, and among them, a linear alkylene group having 1 to 25 carbon atoms is preferable.

  When the compound (D11) contains a skeleton represented by the formula (d-3), the ratio (molar ratio) to the skeleton in the formula (d-1) is (d-1) :( d- 3) = 99: 1 to 85:15 is preferable, 99: 1 to 90:10 is more preferable, and 99: 1 to 95: 5 is more preferable. Within the above range, the skeleton (d-3) may include a plurality of types of Q ″.

［式（ｄ−３’）中、ｙは０以上２０以下である。］ The skeleton (d-3) is preferably a skeleton (d-3 ′) represented by the following general formula (d-3 ′).

[In Formula (d-3 ′), y is 0 or more and 20 or less. ]

  In the formula (d-3 ′), y is 0 or more and 20 or less, preferably 0 or more and 15 or less, more preferably 1 or more and 10 or less. Moreover, when the said compound (D11) contains frame | skeleton (d-3 '), the preferable range of the content rate is the same as that of the case in the said frame | skeleton (d-3). Within the above range, the skeleton (d-3 ′) represented by the formula (d-3 ′) may include a plurality of types of skeletons (one having different y). In the case where y is different, the average value of y is preferably 0 or more and 15 or less, more preferably 1 or more and 10 or less. Moreover, when the total amount of the compound (D11) is 100, the sum of the ratios (molar ratios) of the skeletons represented by the formulas (d-1) and (d-3) is preferably 70 or more. More preferably, it is 80 or more, and still more preferably 90 or more.

  In the present invention, it is preferable that the compound (D11) does not contain a skeleton represented by the formulas (d-3) and (d-3 ′).

  The compound (D11) has a mass average molecular weight (Mw) of preferably from 1,000 to 100,000, and more preferably from 2,000 to 50,000.

［式（１）中、Ｔは測定試料の透過率値を示し、Ｔ_０は難揮発性溶剤単独での透過率値を示す。］ In the present invention, when the compound (D11) is mixed in a hardly volatile solvent so as to be 30% by mass, the turbidity represented by the following formula (1) is preferably 16% or less at 400 nm. .

[In formula (1), T represents the transmittance value of the measurement sample, and T ₀ represents the transmittance value of the hardly volatile solvent alone. ]

The transmittance T in a mixed liquid (measurement sample) of 30% by mass of the dispersant with a hardly volatile solvent and the transmittance T ₀ of the volatile solvent alone can be measured with a spectrophotometer.

  The compound (D11) preferably has a turbidity of 16% or less measured under the above conditions. There is no lower limit in particular, and the one where turbidity is small is excellent in the effect of this invention, and preferable. More preferably, it is 13% or less, still more preferably 11% or less, and particularly preferably 6% or less. By combining the hardly volatile solvent (R) and the compound (D11) so that the turbidity becomes lower, the generation of foreign matters in the reduced-pressure drying step can be effectively suppressed.

  Although it does not specifically limit as a manufacturing method of the said compound (D11), Generally, (i) the polyisocyanate compound which two isocyanate groups couple | bonded with the bivalent organic group, and (ii) the polyester polyol are made to react. Can be obtained. Furthermore, if necessary, a compound selected from the group consisting of (iii) polyol and / or polythiol, (iv) a polyol having a tertiary amino group or heterocyclic nitrogen atom, polythiol, and amines, and (v) a chain An extender or (vi) a chain terminator may be reacted together. Further, for example, a method may be employed in which (i) and (ii) are reacted to obtain a urethane prepolymer (terminal isocyanate compound), and then (ii) to (iv) are further reacted. For example, the above (i) and the above (ii) are reacted until there is no unreacted isocyanate group to obtain an intermediate product, and then the above (ii) and the above intermediate product are reacted, and the above (i) ).

  Moreover, what is necessary is just to set arbitrarily as reaction conditions from a conventionally well-known method. In general, the reaction may be performed in an inert atmosphere, preferably in nitrogen gas, using a catalyst or a solvent as necessary. The reaction temperature may be in the range of 0 ° C to 140 ° C, preferably 20 ° C to 120 ° C. Examples of the catalyst include dibutyltin dilaurate, stannous octoate, triethylenediamine, diethylenediamine, triethylamine, and naphthenic acid metal salts. Examples of the solvent include acetone, methyl ethyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethyl acetate, ethylene acetate, butyl acetate, methoxypropyl acetate, propylene glycol, toluene, xylene, and t-butyl alcohol. be able to.

  Moreover, as a range of the compounding amount at the time of making the said compound react, (i) is 5 mass% or more and 50 mass% or less with respect to the total weight of said (D1), (ii) is 10 mass% or more and 95 mass% or less. , (Iii) is 0% by mass to 30% by mass, (iv) is 0% by mass to 25% by mass, and (v) is 0% by mass to 50% by mass. The equivalent ratio (NCO / OH) of the isocyanate (NCO) group in (i) to the hydroxyl group (OH) in (ii) is preferably 1.1 to 10.0, and 1.1 to 5 0.0 is more preferable, and 1.2 to 3.0 is still more preferable.

  Examples of the compound (i) include dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, 1 , 5-diisocyanate-2-methylpentane, 2,2-dimethylpentane-1,5-diisocyanate, 2,5-dimethylhexane-1,6-diisocyanate, 2,2,4-trimethylpentane-1,5-diisocyanate And a linear or branched alkylene diisocyanate compound such as 2,2,4-trimethylhexane diisocyanate; Cyclic alkylene diisocyanate compounds such as 1,4-cyclohexylene diisocyanate, isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), and 1,3-bis (isocyanatomethyl) cyclohexane; 1,4-phenylene diisocyanate, 1,3- Phenylene diisocyanate, tolylene-α, 4-diisocyanate, tolylene-2,5-diisocyanate, 1,3-bis (1-isocyanate-1-methylethyl) benzene, 4,4′-methylenebis (phenylisocyanate), 3,3 '-Dimethylphenylmethane-4,4-diisocyanate, 4,4'-methylenebis (2,6-diethylphenylisocyanate), m-xylene diisocyanate, and naphthalene-1,5-diisocyanate Examples thereof include diisocyanate compounds having an aromatic group such as nate. These compounds may be used as one kind or a mixture of two or more, and it is particularly preferable to use a diisocyanate compound having an aromatic group as one kind or a mixture of two or more.

  In the compound (ii), examples of the polyester polyol include compounds obtained by reacting a hydroxycarboxylic acid with a hydroxy group-containing compound or a carboxyl group-containing compound, such as 3-hydroxybutyric acid, 4-hydroxybutyric acid, 3-hydroxyvaleric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, glycolic acid, dimethylglycolic acid, β-hydroxypropanoic acid, α-hydroxybutyric acid, γ-hydroxybutyric acid, α-hydroxycaproic acid, β-hydroxy Caproic acid, γ-hydroxycaproic acid, δ-hydroxycaproic acid, δ-hydroxymethylcaproic acid, ε-hydroxycaproic acid, ε-hydroxymethylcaproic acid, lactic acid, ricinoleic acid, 12-hydroxystearic acid, 12-hydroxydodecane Acid, 4-hydro Hydroxycarboxylic acids such as sideroic acid and 5-hydroxydecanoic acid, glycolide, β-propiolactone, δ-valerolactone, γ-valerolactone, γ-undecalactone, ε-caprolactone, β-methyl-δ- Valerolactone, 2-methyl-ε-caprolactone, 3-methyl-ε-caprolactone, 4-methyl-ε-caprolactone, 5-t-butyl-ε-caprolactone, 7-methyl-4,4,6-trimethyl-ε -It may be selected from cyclic esters such as caprolactone, 4,4,6-trimethyl-ε-caprolactone, and lactide.

  You may use these compounds as 1 type, or 2 or more types of mixtures.

  In the compound (iii), the polyol includes ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polypropylene glycol, butylene glycol, trimethylol propane, trimethylol ethane, polymethylol ethane, trimethylol propane, polytrimethylol propane. , Pentaerythritol, polypentaerythritol, sorbitol, mannitol, arabitol, xylitol, galactitol, glycerin, polyglycerin, polytetramethylene glycol, 1,3-butanediol, 1,4-butanediol, polybutylene glycol, 3-methyl -1,5-pentadiol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,9-no Njioru, 1,2-dodecanediol, 2-phenyl-1,2-propanediol, may be mentioned 1,4-benzene dimethanol, and neopentyl glycol.

  In the present invention, a polyether diol compound such as polyalkylene glycol may be used as the polyol, but it is preferable not to use it.

  Examples of polythiol include ethylene glycol such as ethylene glycol dithioglycolate, ethylene glycol dithiopropionate, 1,4-butanediol dithioglycolate, and 1,4-butanediol dithiopropionate, and 1,4-butanediol. Diesters of such diols and carboxyl-containing mercaptans; Triols such as trimethylolpropane such as trimethylolpropane trithioglycolate and trimethylolpropane trithiopropinate; Triesters of carboxyl-containing mercaptans; pentaerythritol tetrakis Compounds having four hydroxyl groups such as thioglycolate and pentaerythritol tetrakisthiopropionate, and carboxyl group-containing mercapts Polyesters such as dipentaerythritol hexakisthioglycolate and dipentaerythritol hexakisthiopropionate, and the like. Polyester compounds of 6-hydroxyl groups such as dipentaerythritol hexakisthiopropionate and carboxyl groups-containing mercaptans; A compound having three or more and a carboxyl group-containing mercaptan polyester compound; a compound having three or more mercapto groups such as trithioglycerin; 2-di-n-butylamino-4,6-dimercapto-S-triazine, and Triazine polyvalent thiols such as 2,4,6-trimercapto-S-triazine; compounds obtained by introducing a plurality of mercapto groups by adding hydrogen sulfide to a plurality of epoxy groups of a polyvalent epoxy compound; Multiple carboxyl groups of carboxylic acid It can be exemplified formed by esterification of mercaptoethanol ester compound. These may be used alone or in combination of two or more. Here, the carboxyl group-containing mercaptans refer to compounds having one mercapto group and one carboxyl group, such as thioglycols, mercaptopropionic acid, and thiosalicylic acid.

  In the compound (iv), a compound selected from the group consisting of a polyol having a tertiary amino group or heterocyclic nitrogen atom, polythiol, and amines, N-methyldiethanolamine, N-phenyldiethanolamine, and N, N -Bis (2-hydroxyethyl) isonicotinamide and the like can be mentioned.

  Moreover, the dispersing agent (D) used by this invention may contain other dispersing agents other than the said compound (D11) in the range which does not impair the effect of this invention. The ratio of the compound (D11) in the dispersant (D) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and most preferably 100% by mass. It is.

  The amount of the dispersant (D) used in the colored photosensitive resin composition of the present invention is appropriately set according to the type and content of the colorant used in the colored photosensitive resin composition of the present invention. Is preferred. The content of the dispersant in the colored photosensitive resin composition is preferably 0.5% by mass or more and 40% by mass or less, and preferably 1% by mass or more and 30% by mass or less with respect to the total amount of the colored photosensitive resin composition. It is more preferable that By making content of a dispersing agent into the said range, the photosensitivity fall of a coloring photosensitive resin composition can be prevented, maintaining the dispersibility of a coloring agent favorable.

  Further, when the solid content of the colored photosensitive resin composition is 100, the content of the colorant with respect to the content of the dispersant (D) is preferably 1.5 times or more and 25 times or less, preferably 2 times. More preferably, it is 20 times or less and more preferably 2.5 times or more and 15 times or less. By making the content of the colorant relative to the content of the dispersant within the above range, the dispersibility of the added dispersant in the colored photosensitive resin composition can be kept good, and the colored photosensitive resin Good photosensitivity of the composition can be obtained.

[(S) solvent]
The (S) solvent in the present invention contains at least one (R) hardly volatile solvent.

((R) hardly volatile solvent)
(R) The hardly volatile solvent has a boiling point of 180 ° C or higher and 250 ° C or lower. The solubility parameter of the hardly volatile solvent is preferably 8.7 (cal / cm ³ ) ^1/2 or more. Generation | occurrence | production of the foreign material at the time of reduced pressure drying can be prevented because the solubility parameter of a hardly volatile solvent is 8.7 (cal / cm < ³ >) ^<1/2 > or more. Further, it is more preferable that the hardly volatile solvent has a solubility parameter of 11 (cal / cm ³ ) ^1/2 or less. When the solubility parameter is 11 (cal / cm ³ ) ^1/2 or less, the compatibility between the hardly volatile solvent and the solid component contained in the colored photosensitive resin composition is maintained, and the generation of foreign matters is further suppressed. be able to.

  The hardly volatile solvent has a boiling point under atmospheric pressure of 180 ° C. or higher and 250 ° C. or lower, and preferably 190 ° C. or higher and 240 ° C. or lower. When the boiling point is 180 ° C. or higher, surface roughness and drying unevenness of the coating film after drying under reduced pressure can be prevented. Moreover, the said hardly volatile solvent is easily removed in the post-baking after pattern formation of a colored photosensitive resin composition because the boiling point is 250 degrees C or less. Therefore, it is possible to prevent the solvent from remaining in the color filter formed from the colored photosensitive resin composition of the present invention.

  The hardly volatile solvent preferably has a weight change rate at 100 ° C. of 10 TG% or less. By setting the weight change rate of the hardly volatile solvent to 10 TG% or less, it is possible to further prevent the generation of foreign matters after drying under reduced pressure in the coating film formed from the colored photosensitive resin composition of the present invention. In addition, surface roughness and drying unevenness in the dried coating film can be prevented. The weight change rate is more preferably 1 TG% or more and 9 TG% or less.

  Here, “weight change rate at 100 ° C.” refers to a change in the weight of the solvent per unit time. In the present specification, the measurement is performed by adding a solvent to a thermobalance kept at 100 ° C. and determining the amount of change in the weight of the solvent in the atmosphere.

  The content of the hardly volatile solvent is preferably 0.1% by mass or more based on the total amount of the solvent. When the content of the hardly volatile solvent is 0.1% by mass or more, generation of foreign matters in the coating film formed from the colored photosensitive resin composition can be further suppressed, and surface roughness and drying unevenness can be suppressed. Can also be prevented. Moreover, it is preferable that content of a hardly volatile solvent is 10 mass% or less with respect to the whole quantity of a solvent. When the content of the hardly volatile solvent is 10% by mass or less, the coating property and the film forming ability of the colored photosensitive resin composition can be kept good, and the removal of the hardly volatile solvent at the time of post-baking can be performed. It is easy to prevent the solvent from remaining in the formed color filter. The content is more preferably 1% by mass or more and 8% by mass or less, and further preferably 3% by mass or more and 7% by mass or less.

  Specific examples of the hardly volatile solvent include gamma butyrolactone (GBL), 1,3-butylene glycol diacetate (1,3-BGA), diethylene glycol monoethyl ether acetate (EDGAC), and diethylene glycol monobutyl ether acetate (BDGAC). , Dipropylene glycol methyl ether acetate (DPMA), or propylene glycol diacetate (PGDA). Among these, 1,3-BGA, EDGAC, BDGAC, DPMA and PGDA are preferable, and 1,3-BGA and BDGAC are more preferable.

  The solvent may contain a solvent other than the hardly volatile solvent (other solvents). The other solvent is not particularly limited, and a solvent usually used for the colored photosensitive resin composition can be used. Specific examples of other solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono- n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n -Butyl ether, dipropylene glycol monomethyl ether (Poly) alkylene glycol monoalkyl such as dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether Ethers; (poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; diethylene glycol dimethyl ether; Diethylene glycol Other ethers such as ruethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate Lactic acid alkyl esters; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, hydroxyacetic acid Ethyl, 2-hydroxy-3-methylbutanoic acid methyl, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate N-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate , Other esters such as n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate; aromatic carbonization such as toluene and xylene Hydrogen; and amides such as N-methylpyrrolidone, N, N-dimethylformamide, and N, N-dimethylacetamide. Among these, 3-methoxybutyl acetate is preferable because it exhibits excellent solubility in a photopolymerizable compound and a photopolymerization initiator and improves dispersibility of insoluble components such as a colorant. Also preferred are propylene glycol monomethyl ether acetate and cyclohexanone. As other solvent combinations, it is preferable to include three kinds of 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, and cyclohexanone.

  The solvent in the colored photosensitive resin composition of the present invention is preferably in an amount such that the solid content concentration is 1% by mass or more and 50% by mass or less, and is an amount that provides 5% by mass or more and 30% by mass or less. It is more preferable. When the amount of the solvent is within the above range, the film forming ability and the coating property in the colored photosensitive resin composition can be kept good.

[Other ingredients]
The colored photosensitive resin composition of the present invention may contain an additive as necessary. Additives include thermal polymerization inhibitors, antifoaming agents, surfactants, sensitizers, curing accelerators, photocrosslinking agents, photosensitizers, dispersants, dispersion aids, fillers, adhesion promoters, oxidation Examples thereof include an inhibitor, an ultraviolet absorber, and an aggregation inhibitor.

[Method for preparing colored photosensitive resin composition]
The colored photosensitive resin composition of the present invention can be obtained by mixing all the above components with a stirrer. In addition, you may filter using a filter so that the obtained mixture may become uniform.

<Color filter>
The color filter is formed using the colored photosensitive resin composition of the present invention. That is, a colored photosensitive resin composition in which a black colorant is dispersed on a substrate made of glass, polyethylene terephthalate, acrylic resin, polycarbonate, or the like is applied to a contact transfer type coating apparatus such as a roll coater, reverse coater, or bar coater. Coating is performed on the substrate using a non-contact coating apparatus such as a spinner (rotary coating apparatus), a slit coater, and a curtain flow coater.

  Next, the applied colored photosensitive resin composition is dried to form a coating film. The drying method is not particularly limited, and for example, vacuum drying is performed at room temperature using a vacuum drying apparatus, and then, at a temperature of 80 ° C. to 120 ° C., preferably 90 ° C. to 100 ° C. for 60 seconds on a hot plate The method of drying for 120 seconds or less can be mentioned.

Next, this coating film is partially exposed by irradiating active energy rays such as ultraviolet rays and excimer laser light through a negative mask. Energy dose to be irradiated also differ depending on the composition of the colored photosensitive resin composition is preferably, for example, 30 mJ / cm ² or more 2000 mJ / cm ² or less.

  Next, the exposed coating film is developed into a desired shape by developing with a developer. The development method is not particularly limited, and for example, an immersion method, a spray method, or the like can be used. Examples of the developer include organic ones such as monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.

  Next, the pattern after development is post-baked at about 220 ° C. to 250 ° C. At this time, it is preferable to expose the entire surface of the formed pattern. As described above, a black matrix having a predetermined pattern shape can be formed.

  The above operation is performed on the colored photosensitive resin composition in which red, green, and blue pigments are dispersed to form pixel patterns of each color. Thereby, a color filter is formed.

  In the production of the color filter of the present invention, the ink of each color of red, green, and blue is ejected from the inkjet nozzles in each region partitioned by the black matrix, and the stored ink is cured by heat or light, Color filters can also be manufactured.

  The colored photosensitive resin composition of the present invention can maintain good dispersibility of the colorant even when it is applied to a substrate and then dried under reduced pressure using a vacuum dryer. Therefore, the generation of foreign matters after drying under reduced pressure can be prevented.

<Liquid crystal display>
The liquid crystal display of the present invention includes the color filter of the present invention. In manufacturing the liquid crystal display of the present invention, the color filter is formed on a substrate, and then electrodes, spacers, and the like are sequentially formed. Then, an electrode or the like is formed on another substrate, the two are bonded together, and a predetermined amount of liquid crystal is injected and sealed.

表１に示すｘ及びｙの値は平均値である。Ａ、Ｂ、Ｃは各骨格のモル比である。 [(D) Dispersant]
Dispersants 1 to 4... Random copolymers having skeletons represented by the following formula (5) were obtained by a known method. Table 1 shows the values of x, y, A, B, and C of each dispersant.

The values of x and y shown in Table 1 are average values. A, B, and C are molar ratios of each skeleton.

[Turbidity of dispersants 1 to 4]
The turbidity of dispersants 1 to 4 with respect to the solvents listed in Table 2 was measured. Table 2 shows the boiling point of each solvent under atmospheric pressure, the weight change rate at 100 ° C., and the values of the solubility parameters. Moreover, the weight change rate in Table 2 is obtained by adding a thermobalance ("TG / DTA6200", manufactured by SII Nanotechnology Co., Ltd.) kept at 100 ° C to the solvent and determining the change in the weight of the solvent under atmospheric pressure. It was measured.

［式（１）中、Ｔは測定試料の透過率値を示し、Ｔ_０は表２の溶剤単独での透過率値を示す。］ [Turbidity evaluation method]
The dispersant of Table 2 was mixed with a dispersant at 30% by mass, and turbidity at 400 nm was measured with a spectrophotometer “UV-3600 (device name)” (manufactured by Shimadzu Corporation). In Table 2, there are some solvents that do not meet the requirements for the (R) hardly volatile solvent used in the present invention, but turbidity was measured for reference. In calculating the turbidity, the following formula (1) was used. The results are shown in Table 3.

[In Formula (1), T shows the transmittance value of the measurement sample, and T ₀ shows the transmittance value of the solvent alone in Table 2. ]

<Examples 1 to 4 and Comparative Examples 1 to 28>
[(A) Synthesis of photopolymerizable compound]
First, in a 500 ml four-necked flask, 235 g of bisphenolfluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72. 0 g was charged, and heated and dissolved at 90 to 100 ° C. while blowing air at a rate of 25 ml / min. Next, the temperature was gradually raised while the solution was clouded, and the solution was heated to 120 ° C. to be completely dissolved. Here, the solution gradually became transparent and viscous, but stirring was continued as it was. During this time, the acid value was measured, and heating and stirring were continued until the acid value was less than 1.0 mgKOH / g. It took 12 hours for the acid value to reach the target. And it cooled to room temperature and obtained the bisphenol fluorene type epoxy acrylate.

  Next, after adding 600 g of 3-methoxybutyl acetate to 307.0 g of the bisphenolfluorene type epoxy acrylate thus obtained and dissolving, 80.5 g of benzophenone tetracarboxylic dianhydride and 1 g of tetraethylammonium bromide Were mixed, gradually heated, and reacted at 110 to 115 ° C. for 4 hours. After confirming the disappearance of the acid anhydride, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to obtain a photopolymerizable compound 1. The disappearance of the acid anhydride was confirmed by IR spectrum. The weight average molecular weight was 3400.

[Preparation of colored photosensitive resin composition]
The following (A), (B), (C), (D) components were prepared with the (S) component;
((A) component)
・ Preparation solution of photopolymerizable compound obtained by adding 10.6 parts by mass of 3-methoxybutyl acetate to 13.0 parts by mass of photopolymerizable compound 1 ・ 4.8 parts by mass of dipentaerythritol hexaacrylate ((B) component)
・ 1.4 parts by mass of photopolymerization initiator (“IRGACURE OXE 02”, manufactured by Ciba Specialty Chemicals)
((C) and (D) component)
The present invention shown below with respect to a carbon dispersion obtained by adding 74.0 parts by weight of 3-methoxybutyl acetate to 24.0 parts by weight of carbon black (high resistance carbon) and 5 parts by weight of the dispersant 1 The (S) component was added to prepare 138 parts by mass to obtain a colored photosensitive resin composition 1 (solid content concentration: 18% by mass).
((S) component)
A mixed solvent consisting of MA, AN, PGMEA, and [Solvents listed in Table 2]. The mass ratio is MA / AN / PGMEA / [Solvents listed in Table 2] = 65/15/15/5.

  In the colored photosensitive resin composition 1, the component (S) was MA / AN / PGMEA / 1,3-BGA = 65/15/15/5.

  The colored photosensitive resin compositions 2 to 32 were prepared in the same manner as the colored photosensitive resin composition 1 except that the combination of the dispersant and the component (S) was changed as shown in Table 4.

[Formation of coating film]
The colored photosensitive resin compositions 1 to 32 obtained above were coated on a 680 mm × 880 mm glass substrate, dried under reduced pressure at 60 Pa for 30 seconds, and then pre-baked at 110 ° C. for 120 seconds to obtain about 1.0 μm. A coating film having a film thickness was obtained. Moreover, the foreign material and surface roughness were evaluated.

[Evaluation of foreign matter]
Using “AOI” (manufactured by TAKANO), defects on the coating film surface were inspected and the number of defects was measured. The results are shown in Table 4.

[Evaluation of surface roughness]
Surface roughness (Ra) was evaluated using an atomic force microscope (“AFM”, manufactured by SII Nanotechnology Co., Ltd.) with respect to the coating films of the colored photosensitive resin compositions 1 to 4. The results are shown in Table 4. In addition, about the colored photosensitive resin compositions 5 to 32, since there were too many foreign materials, it was not necessary to evaluate.

  As can be seen from Table 4, in Examples 1 to 14 to which a dispersant having a turbidity of 16% or less when dissolved in the hardly volatile solvent (R) was added, the generation of foreign matters in the coating film was small, and the surface The roughness was found to be good at 15 nm or less. On the other hand, in Comparative Examples 1 to 28, it was found that 2000 or more foreign substances exceeding the limit of the measured value were generated.

Claims (10)

A colored photosensitive resin composition comprising (A) a photopolymerizable compound, (B) a photopolymerization initiator, (C) a colorant, (D) a dispersant, and (S) a solvent,
The (S) solvent contains at least one (R) hardly volatile solvent having a boiling point of 180 ° C. or higher and 250 ° C. or lower,
The (D) dispersant is a colored photosensitive resin composition containing a compound (D11) having each skeleton represented by the following formula (d-1).

[In formula (d-1), Q and Q ′ each represents a divalent organic group. A and B show the ratio (molar ratio) of each skeleton. ] The colored photosensitive resin composition according to claim 1, wherein the compound (D11) is a compound (D12) represented by the following formula (d-2).

[In the formula (d-2), Ph represents a phenylene group which may have a substituent. x is 0 or more and 8 or less. A and B show the ratio (molar ratio) of each skeleton. ]   The colored photosensitive resin composition according to claim 1 or 2, wherein in formula (d-1), the molar ratio of A and B is A: B = 1: 99 to 99: 1.   The colored photosensitive resin composition according to any one of claims 1 to 3, wherein a weight change rate at 100 ° C of the (R) hardly volatile solvent is 10 TG% or less. The colored photosensitive resin composition according to any one of claims 1 to 4, wherein a solubility parameter of the (R) hardly volatile solvent is 8.7 (cal / cm ³ ) ^1/2 or more.   The colored photosensitive resin composition according to any one of claims 1 to 5, wherein a content of the (R) hardly volatile solvent is 0.1% by mass or more based on a total amount of the (S) solvent.   The (R) hardly volatile solvent is gamma butyrolactone (GBL), 1,3-butylene glycol diacetate (1,3-BGA), diethylene glycol monoethyl ether acetate (EDGAC), diethylene glycol monobutyl ether acetate (BDGAC), di The colored photosensitive resin composition according to any one of claims 1 to 6, which is propylene glycol methyl ether acetate (DPMA) or propylene glycol diacetate (PGDA).   The colored photosensitive resin composition according to claim 1, wherein the (C) colorant contains a black pigment.   A color filter having a pattern formed by using the colored photosensitive resin composition according to claim 1.   A liquid crystal display comprising the color filter according to claim 9.