KR101900497B1 - Colored photosensitive resin composition, color filter and liquid crystal display - Google Patents

Abstract

Provided is a colored photosensitive resin composition capable of preventing the generation of foreign matter (defects) upon drying under reduced pressure after application of the 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. The (S) solvent contains at least one (R) nonvolatile solvent having a boiling point of 180 ° C or more and 250 ° C or less, and the (D) dispersant contains a compound (D11) satisfying predetermined requirements.

Description

COLORED PHOTOSENSITIVE RESIN COMPOSITION, COLOR FILTER AND LIQUID CRYSTAL DISPLAY,

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

A display body such as a liquid crystal display or the like has a structure in which a liquid crystal layer is sandwiched between two substrates on which electrodes facing each other are formed. A color filter including pixel regions of respective colors of red (R), green (G), and blue (B) is formed on the inner side of one substrate. In this color filter, a black matrix is usually formed so as to partition red, green, and blue pixel regions.

Generally, color filters are produced by lithography. That is, first, a black colored photosensitive resin composition is coated on a substrate, followed by vacuum drying (vacuum drying) using a vacuum drying apparatus (VCD), followed by exposure and development to form a black matrix. Subsequently, coating, drying, exposure, and development are repeated for each colored photosensitive resin composition of each color of red, green, and blue, and a pixel area of each color is formed at a predetermined position to produce a color filter.

The coloring agent which is a component of the colored photosensitive resin composition is generally dispersed in the composition by a dispersant.

Here, Patent Document 1 discloses a pigment-dispersed resist composition for a color filter using a pigment adsorption block containing a basic group as a pigment adsorber and a block copolymer resin comprising a block not containing a pigment adsorber as a dispersant.

[Patent Document 1] JP-A-2004-054213

However, depending on the kind of the dispersing agent and the 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 the product, it is an important task to suppress the generation of foreign matter.

SUMMARY OF THE INVENTION 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 matter (defects) upon drying under reduced pressure after application, a color filter having a pattern formed using the colored photosensitive resin composition, It is an object of the present invention to provide a liquid crystal display having a color filter.

The present inventors have found that a colored photosensitive resin composition containing (A) a photopolymerizable compound, (B) a photopolymerization initiator, (C) a colorant, (D) a dispersant and (S) (D) containing at least one kind of (R) nonvolatile solvent satisfying the condition (D) and containing the compound (D11) satisfying the predetermined requirements in the dispersant (D), the occurrence of defects The present invention has been accomplished on the basis of these findings.

Specifically, the present invention provides the following.

A 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) (D) at least one kind of (R) nonvolatile solvent having a boiling point of 180 ° C or higher and 250 ° C or lower, wherein the dispersant (D) Resin composition.

[Chemical Formula 1]

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

Further, a second aspect of the present invention is a color filter having a pattern formed using the colored photosensitive resin composition of the present invention.

Further, a third aspect of the present invention is a liquid crystal display display having the color filter of the present invention.

According to the present invention, since the (S) solvent contains the (R) nonvolatile solvent and (D) the dispersant contains the predetermined compound (D11), the Generation can be suppressed.

Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments 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 described as "component (A)", "component (B)", "component (C)", "component (D)" and "component (S)".

[(A) Photopolymerizable compound]

The photopolymerizable compound includes a resin having an ethylenic unsaturated group or a monomer. As the photopolymerizable compound, it is more preferable to combine a resin having an ethylenic unsaturated group and a monomer. By combining a resin having an ethylenic unsaturated group and a monomer having an ethylenic unsaturated group, the curability can be improved and pattern formation can be facilitated. In the present specification, those having a mass average molecular weight of 1000 or more in the compounds having an ethylenic unsaturated group are referred to as "resins having an ethylenic unsaturated group" and those having a mass average molecular weight of less than 1000 are referred to as "monomer having an ethylenic unsaturated group" .

(A resin having an ethylenic unsaturated group)

Examples of the resin having an ethylenic unsaturated group include (meth) acrylic acid, maleic acid, fumaric acid monomethyl, fumaric acid monoethyl, 2-hydroxyethyl (meth) acrylate, ethylene glycol monomethyl ether (Meth) acrylates such as ethylene glycol monoethyl ether (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, acrylonitrile, methacrylonitrile, (Meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol diacrylate, triethylene glycol di Acrylates such as ethylene glycol di (meth) acrylate, butylene glycol dimethacrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, , 1,6-hexanediol di (meth) acrylate, and cardo epoxy diacrylate; A polyester (meth) acrylate obtained by reacting (meth) acrylic acid with a polyester prepolymer obtained by condensing a polyhydric alcohol with a monobasic acid or a polybasic acid; A polyurethane (meth) acrylate obtained by reacting a polyol with a compound having two isocyanate groups and then reacting (meth) acrylic acid; Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolak type epoxy resin, resol type epoxy resin, triphenol methane type epoxy resin, polycarboxylic acid polyglycidyl ester, (Meth) acrylate resins obtained by reacting an epoxy resin such as polyglycidyl ester, aliphatic or alicyclic epoxy resin, amine epoxy resin or dihydroxybenzene type epoxy resin with (meth) acrylic acid, and the like. A resin obtained by reacting an epoxy (meth) acrylate resin with a polybasic acid anhydride may be used.

As the resin having an ethylenically unsaturated group, resins obtained by reacting a reaction product of an epoxy compound (a1) and an ethylenically unsaturated group-containing carboxylic acid compound (a2) with a polybasic acid anhydride (a3) can be preferably used.

(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 novolak type and orthocresol type epoxy resins, and the like.

(Carboxylic acid compound (a2) containing an ethylenic unsaturated group)

As the ethylenic unsaturated group-containing carboxylic acid compound (a2), a monocarboxylic acid compound containing a reactive ethylenic double bond such as an acrylic group or a methacrylic group in the molecule is preferable. Examples of such an ethylenically unsaturated group-containing carboxylic acid compound include acrylic acid, methacrylic acid,? -Styryl acrylic acid,? -Furfuryl acrylic acid,? -Cyano cinnamic acid, cinnamic acid and the like. The ethylenic unsaturated group-containing carboxylic acid compound (a2) may be used alone, or two or more kinds thereof may be used in combination.

As a method of reacting the epoxy compound (a1) with the ethylenically unsaturated carboxylic acid compound (a2), a known method can be used. For example, the epoxy compound (a1) and the ethylenically unsaturated carboxylic acid compound (a2) may be reacted with a tertiary amine such as triethylamine or benzylethylamine, dodecyltrimethylammonium chloride, tetramethylammonium chloride, A method in which a quaternary ammonium salt such as chloride or benzyltriethylammonium chloride or a pyridine or triphenylphosphine catalyst is reacted in an organic solvent at a reaction temperature of 50 ° C or higher and 150 ° C or lower for several hours to several hours have.

The ratio of the epoxy compound (a1) to the ethylenic unsaturated group-containing carboxylic acid compound (a2) in the reaction is preferably such that the epoxy equivalence of the epoxy compound (a1) and the carboxyl equivalent of the carboxylic acid compound (a2) Acid ratio is usually 1: 0.5 to 1: 2, preferably 1: 0.8 to 1: 1.25, more preferably 1: 1. In 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, anhydrous trimellitic acid, Methylhexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, -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 amount ratio is usually 1: 1 to 1: 1, preferably 1: 1 to 1: 1, more preferably 1: 1 to 1: 1, more preferably 1: 1 to 1: 1, 1: 0.1, preferably 1: 0.8 to 1: 0.2. When the concentration is in the above range, the solubility in the developer tends to become appropriate.

The acid value of the resin obtained by reacting the reaction product of the epoxy compound (a1) and the ethylenically unsaturated group-containing carboxylic acid compound (a2) with the polybasic acid anhydride (a3) is 10 mgKOH / g or more and 150 mgKOH / g or less, more preferably 70 mgKOH / g or more and 110 mgKOH / g or less. When the acid value of the resin is 10 mgKOH / g or more, sufficient solubility in a developing solution can be obtained. When the acid value is 150 mgKOH / g or less, sufficient curability can be obtained and the surface property can be improved.

The mass average molecular weight (Mw) of the resin is preferably from 1,000 to 40,000, more preferably from 2,000 to 30,000. When the mass average molecular weight is 1000 or more, heat resistance and film strength can be improved. When the weight average molecular weight is 40000 or less, sufficient solubility in a developer can be obtained.

As the resin having an ethylenic unsaturated group, a resin having a cardo structure in the molecule can be preferably used. Since a resin having a cardo structure has high heat resistance and chemical resistance, it can be used in a photopolymerizable compound to improve the heat resistance and chemical resistance of the colored photosensitive resin composition. For example, a resin represented by the following formula (2) can be preferably used.

(2)

In the formula (2), X is a group represented by the following formula (3). n is an integer of 1 or more and 20 or less.

(3)

In formula (2), Y is at least one selected from the group consisting of maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, (-CO-O-CO-) is removed from a dicarboxylic acid anhydride such as anhydrous phthalic acid or anhydrous glutaric acid.

In the formula (2), Z is tetracarboxylic acid dianhydride such as pyromellitic anhydride, benzophenonetetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, biphenyl ether tetracarboxylic acid dianhydride, etc. In which the two carboxylic acid anhydride groups are removed.

(A monomer having an ethylenic unsaturated group)

Monomers having an ethylenic unsaturated group include monofunctional monomers and polyfunctional monomers.

Examples of the monofunctional monomer include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, (Meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (Meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isopropyl (meth) acrylate, (Meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl Phenoxy-2-hydroxypropyl (meth) acrylate (Meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidyl (Meth) acrylate of 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate and phthalic acid derivatives have. These monofunctional monomers may be used alone, or two or more monofunctional monomers may be used in combination.

Examples of the polyfunctional monomer include 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, trimethylolpropane tri (meth) acrylate, glycerin (meth) acrylate, trimethylolpropane tri (meth) (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol (Meth) acryloxypolyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxy diethoxyphenyl) propane, (Meth) acryloyloxypropyl (meth) acrylate, ethyleneglycol diglycidylether di (meth) acrylate, diethyleneglycol diglycidylether di (meth) acrylate, phthalic acid diglycidyl (Meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (i.e., tolylene diisocyanate), trimethylhexamethylene diisocyanate and hexamethylene (Meth) acrylamide, (meth) acrylamide methylene ether, a condensation product of a polyhydric alcohol and N-methylol (meth) acrylamide, a reaction product of triacryl Formal, and the like. These multifunctional monomers may be used alone, or two or more of them may be used in combination.

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 or less, based on the solid content of the colored photosensitive resin composition. When the content is in the above range, there is a tendency to balance the sensitivity, developability and resolution. In addition, the solid content refers to the total of components other than the solvent.

The content of the photopolymerizable compound is preferably 5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 40% by mass or less based on the solids content of the colored photosensitive resin composition. When the content is in the above range, there is a tendency to balance the sensitivity, developability and resolution.

[(B) Photopolymerization initiator]

Examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) Methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy- 2-methylpropane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) (Methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino- 3-yl] -1- (O-acetyloxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl- Dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino -2-isoamylbenzoic acid, Ben benzyl dimethyl ketal, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, methyl O-benzoylbenzoate, 2,4- , 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2-methylthioxanthone, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethyl anthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, Benzoyl peroxide, benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (O- 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, benz Benzoin isopropyl ether, benzoin isobutyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethyl P-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyl acetophenone, p-dimethylaminoacetophenone, 2-methyl thioxanthone, 2-isopropyl thioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) propane, p-methoxy Triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) Furan-2-yl) ethenyl] -4,6-bis (trichloromethane ) -s-triazine, 2- [2- (4-diethylamino) -phenyl] (Trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) Bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis Phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl- 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4- 4-methoxy) styrylphenyl-s-triazine. Among them, it is particularly preferable to use an oxime-based photopolymerization initiator in terms of sensitivity. 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, more preferably 1% by mass or more and 20% by mass or less based on the solid content of the colored photosensitive resin composition. Within the above range, sufficient heat resistance and chemical resistance can be obtained, and the coating film forming ability can be improved and the photo-curing failure can be suppressed.

[(C) Colorant]

The colorant is not particularly limited, but conventionally known pigments can be used. For example, when a black matrix or a black stripe is formed by using the colored photosensitive resin composition of the present invention, it is preferable to use a coloring agent such as carbon black, titanium black, chromium oxide, iron oxide, aniline black, Black pigments can be used. Carbon black coated with an epoxy resin or the like; Inorganic black pigments such as composite oxides such as titanium, manganese, iron, copper and cobalt; A combination of organic pigments shown below; A combination of the organic pigment and the above-described black pigment can also be suitably employed. Depending on the combination, a high resistance value or a color tone may be adjusted. Further, when combining a black pigment and another coloring component, it is preferable to mix other coloring components within a range not lowering the light-shielding performance.

As the inorganic black pigment, carbon black dispersion "CF black" (containing 24% of high-resistance carbon) manufactured by Mikuni Color Co., Ltd. and the like can be mentioned.

Further, a violet dispersion (containing 10% of violet pigment) manufactured by Mikuni Color Co., Ltd., a blue pigment dispersion "CF Blue" (manufactured by Mikuni Color Co., Ltd.) containing blue pigment 20%) may be mixed.

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

Specifically, as a color index number (C. I. No.)

Yellow pigments: C.I. 20, 24, 83, 86, 93, 109, 110, 117, 125, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 168, 180, 185, 195

Color Pigment: C. I. 36, 43, 51, 55, 59, 61

Red pigment: C. I. 9,92,123,149,168,177,180,192,215,216,217,220,223,224,226,227,228,240,254

Purple Pigment: C. I. 19, 23, 29, 30, 37, 40, 50

Blue pigments: C. I. 15, 15: 3, 15: 6, 22, 60, 64

Green pigments: C. I. 7, 36

Brown pigment: C. I. 23, 25, 26

Can be preferably used since it has high transparency and is excellent in heat resistance, weather resistance and chemical resistance.

The pigment is preferably contained in an amount of 1% by mass or more and 70% by mass or less based on the solid content of the colored photosensitive resin composition, more preferably 20% by mass or more and 60% by mass or less. 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 may be lowered and heat resistance and chemical resistance of the coating film after curing may be lowered.

In addition, 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, more preferably 50% by mass or more based on the solid content of the colored photosensitive resin composition. When the content of the pigment is more than 40% by mass, a colored photosensitive resin composition having excellent light shielding properties can be obtained. On the other hand, it is preferable that the content of the black pigment is 70% by mass or less based on the solid content of the colored photosensitive resin composition, because the sensitivity, heat resistance and chemical resistance of the coated film after curing are satisfactorily maintained. The upper limit value is more preferably 60% by mass.

In the colored photosensitive resin composition in which the black pigment is dispersed, a colored photosensitive resin composition having a high light shielding property (optical density, OD value) can be obtained by containing the colorant within the above content range. 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 particularly preferably 4.5 or more.

[(D) Dispersant]

The colored photosensitive resin composition of the present invention contains a dispersing agent for dispersing the pigment in the colored photosensitive resin composition. In the present invention, the dispersant (D) contains a compound (D11) having a skeleton represented by the following general formula (d-1).

[Chemical Formula 4]

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

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

In the formula (d-1), A and B represent the ratio (molar ratio) of each skeleton. The preferred range is A: B = 1:99 to 99: 1, more preferably 1:99 to 20:80, and even more preferably 2:98 to 10:90. The compound (D11) having a skeleton represented by the formula (d-1) may contain plural kinds of skeletons (different Q and / or Q ') when A and B are within the above ranges, In embodiments, it is preferred that Q and / or Q 'be present in a form having different linking groups.

The ratio (molar ratio) of the skeleton represented by the formula (d-1) when the total amount of the compound (D11) is 100 is preferably 70 or more, more preferably 80 or more, and even more preferably 90 or more.

Among these compounds (D11), compounds (D12) each having a skeleton represented by the following general formula (d-2) are preferably exemplified.

[Chemical Formula 5]

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

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

Specific examples of the skeleton having Ph include the following examples.

[Chemical Formula 6]

(7)

In formula (d-2), A and B are the same as in the case of (d-1). The compound (D12) having the skeleton of the formula (d-2) may contain plural kinds of skeletons (different from Ph and / or x), when A and B are within the above- It is preferred that Ph and / or x are present in a form having different substituents and / or linking groups. When x contains a different one, the average value of x is preferably 0 or more and 6 or less, more preferably 0 or more and 3 or less.

The ratio (molar ratio) of the skeleton represented by the formula (d-2) when the total amount of the compound (D12) is 100 is preferably 70 or more, more preferably 80 or more, and even more preferably 90 or more. It is particularly preferable that the compound (D12) has a skeleton represented by the general formula (d-2) by removing terminal residues.

The compound (D11) may contain a skeleton (d-3) represented by the following general formula (d-3) within the range not impairing the effect of the present invention.

[Chemical Formula 8]

[In the formula (d-3), Q "is a divalent organic group.]

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

When the compound (D11) contains a skeleton represented by the formula (d-3), the ratio (d-1) :( d-3) = 99 : 1 to 85:15, more preferably in the range of 99: 1 to 90:10, and still more preferably in the range of 99: 1 to 95: 5. Within the above range, the skeleton (d-3) may contain plural kinds of Q ''.

The skeleton (d-3) is preferably a skeleton (d-3 ') represented by the following general formula (d-3').

[Chemical Formula 9]

In the formula (d-3 '), y is an integer of 0 or more and 20 or less.

In the formula (d-3 '), y is an integer of 0 or more and 20 or less, preferably 0 or more and 15 or less, and more preferably 1 or more and 10 or less. When the compound (D11) contains the skeleton (d-3 '), the preferable range of the content of the compound (D11) is the same as that in the skeleton (d-3). Within this range, the skeleton (d-3 ') represented by the formula (d-3') may contain plural kinds of skeletons (the y may be different). When y contains a different one, the average value of y is preferably 0 or more and 15 or less, more preferably 1 or more and 10 or less. The sum of the ratios (molar ratios) of the respective skeletons represented by the formulas (d-1) and (d-3) when the total amount of the compound (D11) is 100 is preferably 70 or more, more preferably 80 or more , And 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 weight average molecular weight (Mw) of the compound (D11) is preferably 1,000 or more and 100,000 or less, and more preferably 2,000 or more and 50,000 or less.

In the present invention, it is preferable that the turbidity of the compound (D11) represented by the following formula (1) is 16% or less at 400 nm when the compound (D11) is mixed into an egg volatile solvent so as to be 30 mass%.

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

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

The compound (D11) preferably has a turbidity measured under the above conditions of 16% or less. There is no particular lower limit, and a smaller turbidity is preferable because the effect of the present invention is excellent. , More preferably not more than 13%, even more preferably not more than 11%, and particularly preferably not more than 6%. By combining the volatile solvent (R) and the compound (D11) so that the turbidity is lowered, the generation of foreign matter in the reduced-pressure drying step can be effectively suppressed.

The method for producing the compound (D11) is not particularly limited, but can be generally obtained by reacting (i) a polyisocyanate compound having two isocyanate groups bonded to a divalent organic group and (ii) a polyester polyol. (Iii) a compound selected from the group consisting of a polyol and / or a polythiol, (iv) a polyol having a tertiary amino group or a heterocyclic nitrogen atom, a polythiol and an amine, and (v) ) Chain terminator may be reacted together. Further, for example, a method may be used in which the urethane prepolymer (terminal isocyanate compound) is obtained by reacting the above (i) and the above (ii), and then further reacting the above (ii) to (iv) (I) and the above-mentioned (ii) until the unreacted isocyanate group disappears to obtain an intermediate product, then reacting the intermediate product with the above-mentioned (ii), and further reacting with the above (i) do.

The reaction conditions may be arbitrarily set by conventionally known methods. In general, the reaction may be carried out in an inert atmosphere, preferably in a nitrogen gas, using a catalyst or a solvent as required. The reaction temperature may be in the range of 0 占 폚 to 140 占 폚, preferably 20 占 폚 to 120 占 폚. Examples of the catalyst include dibutyltin dilaurate, stannous octoate, triethylenediamine, diethylenediamine, triethylamine, naphthenic acid metal salt, and the like. Examples of the solvent include acetone, methyl ethyl ketone, dimethyl formamide, dimethylacetamide, N-methylpyrrolidone, ethyl acetates, ethylene acetate, butyl acetate, methoxypropyl acetate, propylene glycol, toluene, xylene , t-butyl alcohol, and the like.

(I) is not less than 5% by mass and not more than 50% by mass, (ii) is not less than 10% by mass and not more than 95% by mass based on the total mass of the compound (D1) (Iii) is 0 mass% or more and 30 mass% or less, (iv) is 0 mass% or more and 25 mass% or less, and (v) is 0 mass% or more and 50 mass% or less. The equivalent ratio (NCO / OH) of the isocyanate (NCO) group of (i) and the hydroxyl group (OH) of (ii) is preferably 1.1 to 10.0, more preferably 1.1 to 5.0, desirable.

Examples of the compound (i) include, but are not limited to, 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, 2,2,4-trimethylhexane diisocyanate, and other straight chain or branched chain alkylene diisocyanate compounds; cyclic alkylene diisocyanate compounds such as trans-1,4-cyclohexylene diisocyanate, isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), and 1,3-bis (isocyanate methyl) cyclohexane; 1,4-phenylene diisocyanate, 1,3-phenylene diisocyanate, tolylene- ?, 4-diisocyanate, tolylene-2,5-diisocyanate, 1,3-bis (1-isocyanate- ) Benzene, 4,4'-methylenebis (phenylisocyanate), 3,3'-dimethylphenylmethane-4,4-diisocyanate, 4,4'-methylenebis (2,6-diethylphenylisocyanate), m Diisocyanate compounds having an aromatic group such as xylene diisocyanate and naphthalene-1,5-diisocyanate, and the like. These compounds may be used singly or as a mixture of two or more kinds, and it is particularly preferable to use one diisocyanate compound having an aromatic group or a mixture of two or more kinds thereof.

Examples of the polyester polyol in the compound of the above (ii) include a compound obtained by reacting a hydroxycarboxylic acid with a hydroxy group-containing compound or a carboxyl group-containing compound, and examples thereof include 3-hydroxybutyric acid, 4-hydroxybutyric acid Hydroxystearic acid,? -Hydroxybutyric acid,? -Hydroxy valeric acid,? -Hydroxy valeric acid,? -Hydroxy valeric acid,? -Hydroxy valeric acid, Hydroxycaproic acid,? -Hydroxycaproic acid,? -Hydroxycaproic acid,? -Hydroxycaproic acid,? -Hydroxycaproic acid,? -Hydroxycaproic acid,? -Hydroxymethylcaproic acid, , Hydroxycarboxylic acids such as ricinolic acid, 12-hydroxystearic acid, 12-hydroxydodecanoic acid, 4-hydroxydecanoic acid, and 5-hydroxydecanoic acid, glycolide,? -Propiolactone, ? -valerolactone,? -valerolactone,? -valerate Caprolactone,? -Caprolactone,? -Caprolactone,? -Caprolactone,? -Caprolactone,? -Caprolactone,? -Caprolactone,? -Methyl-δ-valerolactone, -caprolactone,? -caprolactone, 7-methyl-4,4,6-trimethyl-epsilon -caprolactone, 4,4,6-trimethyl-epsilon -caprolactone, and lactide.

These compounds may be used alone or as a mixture of two or more thereof.

In the compound (iii), examples of the polyol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polypropylene glycol, butylene glycol, trimethylolpropane, trimethylolethane, , Polytrimethylol propane, pentaerythritol, polypentaerythritol, sorbitol, mannitol, arabitol, xylitol, galactitol, glycerin, polyglycerin, polytetramethylene glycol, 1,3-butanediol, Methylene-1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,9-nonanediol, 1,2-dodecanediol, 1,2-propanediol, 1,4-benzenedimethanol, neopentyl glycol, and the like.

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

Examples of the polythiol include ethylene glycol or 1,4-butanediol such as ethylene glycol dithioglycolate, ethylene glycol dithiophosphate, 1,4-butanediol dithioglycolate and 1,4-butanediol dithiophosphate, Diesters of the same diols and carboxyl group-containing mercaptans; Triesters of a triol such as trimethylol propane, such as trimethylolpropane trithioglycolate and trimethylolpropane trithiopropanate, and mercaptans containing a carboxyl group; Pentaerythritol such as pentaerythritol tetrakisthioglycolate and pentaerythritol tetrakisthiopropionate; and polyesters of carboxyl group-containing mercaptans; compounds having four hydroxyl groups such as pentaerythritol, A polyester compound of a compound having 6 hydroxyl groups such as dipentaerythritol such as dipentaerythritol hexa chitioglycolate and dipentaerythritol hexa chitiopropionate and a carboxyl group-containing mercaptan; A polyester compound of a compound having three or more hydroxyl groups and a carboxyl group-containing mercaptan; Compounds having three or more mercapto groups such as trithioglycerin; Di-n-butylamino-4,6-dimercapto-S-triazine, and 2,4,6-trimercapto-S-triazine; A compound obtained by adding hydrogen sulfide to a plurality of epoxy groups of a polyvalent epoxy compound and introducing a plurality of mercapto groups; And an ester compound obtained by esterifying a plurality of carboxyl groups of a polycarboxylic acid with mercaptoethanol. These may be used alone, or two or more of them may be used in combination. Here, the carboxyl group-containing mercaptans are compounds having one mercapto group and one carboxyl group such as thioglycols, mercaptopropionic acid and thiosalicylic acid.

Examples of the compound selected from the group consisting of a polyol having a tertiary amino group or a heterocyclic nitrogen atom, a polythiol and an amine in the compound (iv) include N-methyldiethanolamine, N-phenyldiethanolamine, N , N-bis (2-hydroxyethyl) isonicotinamide, and the like.

The dispersant (D) to be used in the present invention may contain a dispersant other than the compound (D11) within a range not to impair the effect of the present invention. The proportion of the compound (D11) in the dispersant (D) is preferably 50 mass% or more, more preferably 70 mass% or more, further preferably 90 mass% or more, and most preferably 100 mass% % to be.

The amount of the dispersant (D) used in the colored photosensitive resin composition of the present invention is preferably set appropriately in accordance with the type and content of the colorant used in the colored photosensitive resin composition of the present invention. The content of the dispersing agent in the colored photosensitive resin composition is preferably 0.5% by mass or more and 40% by mass or less, more preferably 1% by mass or more and 30% by mass or less based on the total amount of the colored photosensitive resin composition. When the content of the dispersing agent is within the above range, deterioration of the photosensitivity of the colored photosensitive resin composition can be prevented while favorably maintaining the dispersibility of the coloring agent.

When the solid content of the colored photosensitive resin composition is 100, the content of the colorant relative to the content of the dispersant (D) is preferably 1.5 times or more and 25 times or less, more preferably 2 times or more and 20 times or less , And more preferably 2.5 times or more and 15 times or less. When the content of the coloring agent relative to the content of the dispersing agent is within the above range, the dispersibility of the added dispersing agent in the colored photosensitive resin composition can be satisfactorily maintained and good photosensitivity of the colored photosensitive resin composition can be obtained.

[(S) Solvent]

The (S) solvent in the present invention contains at least one (R) nonvolatile solvent.

((R) nonvolatile solvent)

(R) volatile solvent has a boiling point of 180 ° C or more and 250 ° C or less. The dissolution parameter of the volatile solvent is preferably 8.7 (cal / cm 3) ^1/2 or more. Since the dissolution parameter of the volatile solvent is 8.7 (cal / cm < 3 >) ^1/2 or more, generation of foreign matter at the time of reduced pressure drying can be prevented. It is more preferable that the volatile solvent has a dissolution parameter of 11 (cal / cm 3) ^1/2 or less. The solubility parameter by 11 (cal / ㎤) less than or equal to ^1/2, i compatibility of the solid content contained in the volatile solvent and the colored photosensitive resin composition is maintained, it is possible to suppress the occurrence of more debris.

The volatile solvent preferably has a boiling point of 180 占 폚 or higher and 250 占 폚 or lower at atmospheric pressure and 190 占 폚 or higher and 240 占 폚 or lower. When the boiling point is 180 占 폚 or higher, it is possible to prevent the surface roughness and drying unevenness of the coated film after reduced pressure drying. Further, the nonvolatile solvent has a boiling point of 250 캜 or lower, whereby the coloring photosensitive resin composition is easily removed in the post-baking after pattern formation. Therefore, it is possible to prevent the solvent from remaining in the color filter formed of the colored photosensitive resin composition of the present invention.

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

Here, the " weight change rate at 100 deg. C " indicates a weight change of the solvent per unit time. In the present specification, the solvent is measured by adding a solvent to a thermal balance kept at 100 캜 and determining the amount of change in the weight of the solvent in the atmosphere.

The content of the volatile solvent is preferably 0.1% by mass or more with respect to the total amount of the solvent. When the content of the volatile solvent is 0.1 mass% or more, generation of foreign matter in the coating film formed of the colored photosensitive resin composition can be further suppressed, and surface roughness and drying unevenness can be prevented. The content of the volatile solvent is preferably 10% by mass or less based on the total amount of the solvent. When the content of the volatile solvent is 10 mass% or less, it is possible to satisfactorily maintain the coating property and the film forming ability of the colored photosensitive resin composition, and to easily remove the oily volatile solvent during post-baking, It is possible to prevent the solvent from remaining in the reaction chamber. The content is more preferably 1% by mass or more and 8% by mass or less, and still more preferably 3% by mass or more and 7% by mass or less.

Specific examples of the volatile solvent include gamma butyrolactone (GBL), 1,3-butylene glycol diacetate (1,3-BGA), diethylene glycol monoethyl ether acetate (EDGAC), diethylene glycol monobutyl ether Acetate (BDGAC), dipropylene glycol methyl ether acetate (DPMA) and propylene glycol diacetate (PGDA). Of 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 solvent). The other solvent is not particularly limited, and a solvent usually used in the colored photosensitive resin composition can be used. Specific examples of the other solvent 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 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, dipropylene glycol mono-n-butyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono- (Poly) alkyl (meth) acrylate such as tripropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, Glycol monomethyl ether; (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; Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; Lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, Butyl acetate, n-butyl acetate, n-butyl acetate, n-propyl acetate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate , Ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate; Aromatic hydrocarbons such as toluene and xylene; And amides such as N-methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide. Among them, 3-methoxybutylacetate is preferable in that it exhibits excellent solubility in a photopolymerizable compound and a photopolymerization initiator, and improves the dispersibility of an insoluble component such as a colorant. Propylene glycol monomethyl ether acetate and cyclohexanone are also preferable. As the combination of other solvents, it is preferable to contain 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 such that the concentration of the solid content is 1% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 30% by mass or less. 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 well maintained.

[Other components]

The colored photosensitive resin composition of the present invention may contain additives as required. Examples of the additives include heat polymerization inhibitors, defoaming agents, surfactants, sensitizers, curing accelerators, photo-crosslinking agents, photosensitizers, dispersants, dispersion aids, fillers, adhesion promoters, antioxidants, ultraviolet absorbers and antiflocculants.

[Method of preparing colored photosensitive resin composition]

The colored photosensitive resin composition of the present invention is obtained by mixing all of the above components with a stirrer. Further, the mixture may be filtered using a filter so as to be uniform.

<Color filter>

A 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 coloring agent is dispersed is applied to a substrate made of glass, polyethylene terephthalate, acrylic resin, polycarbonate or the like by a contact transfer type application device such as a roll coater, a reverse coater, a bar coater, ), A slit coater, a curtain flow coater, or the like.

Subsequently, the applied colored photosensitive resin composition is dried to form a coating film. The drying method is not particularly limited. For example, a vacuum drying apparatus is used for drying under reduced pressure at room temperature. Thereafter, the substrate is heated at a temperature of 80 ° C or more and 120 ° C or less, preferably 90 ° C or more and 100 ° C or less, Followed by drying for 120 seconds or less.

Subsequently, the coating film is irradiated with active energy rays such as ultraviolet rays and excimer laser rays through a negative mask to partially expose the coating film. The energy dose to be irradiated varies depending on the composition of the colored photosensitive resin composition but is preferably 30 mJ / cm 2 to 2000 mJ / cm 2, for example.

Subsequently, the coated film after exposure is developed with a developing solution to be patterned into a desired shape. The developing method is not particularly limited, and for example, a dipping method, a spraying method, or the like can be used. Examples of the developing solution 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.

Subsequently, post-baking is performed at 220 to 250 DEG C on the developed pattern. At this time, it is preferable that the formed pattern is entirely exposed. Thus, a black matrix having a predetermined pattern shape can be formed.

The above operation is carried out for a colored photosensitive resin composition in which red, green or blue pigment is dispersed to form a pixel pattern of each color. As a result, a color filter is formed.

In manufacturing the color filter of the present invention, inks of respective colors of red, green, and blue are ejected from the inkjet nozzles in the respective regions partitioned by the black matrix, and the collected ink is cured by heat or light, May be produced.

The colored photosensitive resin composition of the present invention can satisfactorily maintain the dispersibility of the coloring agent even when subjected to vacuum drying after application on a substrate and using a vacuum drying apparatus. Therefore, it is possible to prevent the generation of foreign matter after the reduced-pressure drying.

&Lt; 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 an electrode, a spacer, and the like are sequentially formed. Then, an electrode or the like is formed on another substrate, and a predetermined amount of liquid crystal is poured and sealed together so as to be manufactured by a conventional method.

Example

[(D) for dispersant]

Dispersants 1 to 4 ... A random copolymer having each skeleton represented by the following formula (5) was obtained by a known method. The values of x, y, A, B, and C of each dispersant are shown in Table 1.

[Chemical formula 10]

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

[About turbidity of dispersants 1 to 4]

The turbidity of dispersants 1 to 4 for the solvents exemplified in Table 2 was measured. Table 2 shows the boiling points of the respective solvents at atmospheric pressure, the weight change rate at 100 캜, and the values of the dissolution parameters. The weight change ratio in Table 2 was measured by adding a thermal balance (&quot; TG / DTA6200 &quot;, manufactured by SII Nanotechnology) warmed at 100 占 폚 to a solvent and determining the change in weight of the solvent under atmospheric pressure.

[Evaluation method of turbidity]

The dispersant was mixed with the solvent of Table 2 in an amount of 30% by mass, and the turbidity at 400 nm was measured by a spectrophotometer "UV-3600 (apparatus name)" (manufactured by Shimadzu Corporation). In Table 2, there are solvents which do not meet the requirements of the (R) nonvolatile solvent used in the present invention, but the turbidity was measured for reference. At the time of turbidity calculation, the following formula (1) was used. The results are shown in Table 3.

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

&Lt; Examples 1 to 4 and Comparative Examples 1 to 28 &gt;

[(A) Synthesis of photopolymerizable compound]

First, in a 500 ml four-necked flask, 235 g of bisphenol fluorene epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, And the mixture was heated and dissolved at 90 to 100 占 폚 while blowing air at a rate of 25 ml / min. Then, the solution was gradually heated with the solution in a cloudy state, and completely dissolved by heating to 120 ° C. The solution gradually became a clear viscous solution, but stirring was continued as it was. During this period, the acid value was measured, and heating and stirring were continued until it was less than 1.0 mg KOH / g. It took 12 hours for the mountain to reach its goal. The mixture was then cooled to room temperature to obtain a bisphenol fluorene-type epoxy acrylate.

Subsequently, 600 g of 3-methoxybutyl acetate was added to 307.0 g of the bisphenol fluorene type epoxy acrylate thus obtained and dissolved. Then, 80.5 g of benzophenone tetracarboxylic acid dianhydride and 1 g of tetraethylammonium bromide were mixed , The temperature was gradually raised, and the reaction was carried out at 110 ° C to 115 ° C for 4 hours. After disappearance of the acid anhydride was confirmed, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 DEG C for 6 hours to obtain a photopolymerizable compound 1. [ The disappearance of the acid anhydride was confirmed by IR spectrum. The mass average molecular weight was 3,400.

[Preparation of colored photosensitive resin composition]

The colored photosensitive resin composition 1 was prepared by dissolving the following components (A), (B), (C) and (D) in the component (S). In other words,

(Component (A))

. 13.0 parts by mass of the photopolymerizable compound 1 To 10.6 parts by mass of 3-methoxybutyl acetate was added to the solution of the photopolymerizable compound

4.8 parts by mass of dipentaerythritol hexaacrylate

(Component (B)).

1.4 parts by mass of a photopolymerization initiator (&quot; IRGACURE OXE 02 &quot;, manufactured by Ciba Specialty Chemicals)

(Components (C) and (D)).

24.0 parts by mass of carbon black (high-resistance carbon), 5 parts by mass of the above-mentioned dispersant 1, 71.0 parts by mass of 3-methoxybutyl acetate,

, 138 parts by mass of the following component (S) was added to obtain a colored photosensitive resin composition 1 (solid content concentration: 18% by mass).

((S) component)

- Mixed solvent consisting of MA, AN, PGMEA, and [solvent exemplified in Table 2]. The mass ratio is MA / AN / PGMEA / [solvent exemplified 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 preparation of the colored photosensitive resin compositions 2 to 32 was carried out 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 applied on a glass substrate having a size of 680 mm x 880 mm, followed by drying under reduced pressure at 60 Pa for 30 seconds, followed by pre-baking at 110 캜 for 120 seconds, &Lt; / RTI &gt; Further, evaluation of foreign matter and surface roughness was carried out.

[Evaluation of foreign matter]

"AOI" (manufactured by TAKANO) was used to inspect defects on the surface of the coating film and measure the number of defects. The results are shown in Table 4.

[Evaluation of surface roughness]

The surface roughness (Ra) of the coating film of the colored photosensitive resin compositions 1 to 4 was evaluated by using an atomic force microscope ("AFM", manufactured by SII Nanotechnology Co., Ltd.). The results are shown in Table 4. Further, the colored photosensitive resin compositions 5 to 32 did not need to be evaluated because too much foreign matter was present.

As can be seen from Table 4, in Examples 1 to 14 in which a dispersant having a turbidity of not more than 16% when dissolved in the volatile solvent (R) was added, the generation of foreign matter in the coating film was small and the surface roughness 15 nm or less. On the other hand, in Comparative Examples 1 to 28, it was found that more than 2,000 foreign substances exceeding the limits of the measurement 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) The (S) solvent contains at least one (R) nonvolatile solvent having a boiling point of 180 ° C or more and 250 ° C or less, The dispersant (D) contains a compound (D12) having a skeleton represented by the following formula (d-2) and a skeleton represented by the formula (d-2) (Molar ratio) of 90 or more.

[In the formula (d-2), Ph represents a phenylene group which may have a substituent. x is an integer of 0 to 8 inclusive. A and B represent the ratio (molar ratio) of each skeleton. Polyurethane skeleton and polyester skeleton (except the terminal polyester chain) in the main chain.] delete The method according to claim 1, Wherein the molar ratio of A to B in the formula (d-2) is A: B = 1: 99 to 99: 1. The method according to claim 1, And the weight change ratio of the (R) nonvolatile solvent at 100 캜 is 10 TG% or less. The method according to claim 1, Wherein the dissolution parameter of the (R) nonvolatile solvent is 8.7 (cal / cm 3) ^1/2 or more. The method according to claim 1, Wherein the content of the (R) nonvolatile solvent is 0.1% by mass or more based on the total amount of the (S) solvent. The method according to claim 1, Wherein the (R) nonvolatile solvent is selected from the group consisting of gamma butyrolactone (GBL), 1,3-butylene glycol diacetate (1,3-BGA), diethylene glycol monoethyl ether acetate (EDGAC), diethylene glycol monobutyl ether Acetate (BDGAC), dipropylene glycol methyl ether acetate (DPMA), or propylene glycol diacetate (PGDA). The method according to claim 1, The colored photosensitive resin composition of (C) wherein the colorant contains a black pigment. A color filter having a pattern formed by using the colored photosensitive resin composition according to any one of claims 1 to 8. A liquid crystal display having the color filter according to claim 9.