KR101517281B1 - Colored photosensitive resin composition, color filter and liquid crystal display - Google Patents

Abstract

assignment
A color filter having a pattern formed by using the colored photosensitive resin composition, and a liquid crystal display display having the color filter, which can effectively suppress surface defects and surface roughening of a coating film when the coating film is dried under reduced pressure do.
Solution
The colored photosensitive resin composition according to the present invention contains a photopolymerizable compound (A), a photopolymerization initiator (B), a colorant (C) and a solvent (S). The solvent (S) comprises at least one low boiling point solvent (L) having a boiling point of less than 170 占 폚 at atmospheric pressure, at least one first high boiling point solvent (H1) having a boiling point of at least 170 占 폚 and less than 180 占 폚 at atmospheric pressure, (H 2) having a boiling point of 180 ° C. or higher, and the ratio of the first high boiling point solvent (H 1) in the solvent (S) is at least 60% by weight.

Description

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

The present invention relates to a colored photosensitive resin composition, a color filter having a pattern formed using the colored photosensitive resin composition, and a liquid crystal display having the color filter.

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 opposed to each other and having paired electrodes formed thereon. On one side of the substrate, a color filter composed of pixel regions of each color such as red (R), green (G), and blue (B) is formed. 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. In this lithography method, first, a black colored photosensitive resin composition is coated on a substrate, the coated film is dried under reduced pressure by a vacuum drying apparatus (VCD), and then exposed and developed 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 to form a pixel region of each color at a predetermined position to produce a color filter.

In recent years, a method of manufacturing a color filter by an ink jet method has been studied in order to improve the productivity of a color filter. In this ink jet method, a black matrix is first formed by a lithography method. Next, a colored photosensitive resin composition of each color of red, green and blue is discharged from an ink jet nozzle in each pixel region partitioned by a black matrix, and the collected colored photosensitive resin composition is cured by heat or light to manufacture a color filter do.

Patent Document 1: Japanese Patent Application Laid-Open No. 2006-349981

However, as described above, after the colored photosensitive resin composition is applied onto the substrate, the coated film is dried under reduced pressure by a vacuum drying apparatus (VCD). However, when the coated film is dried under reduced pressure, There has been a problem that a surface defect or surface roughness occurs in the coating film.

Accordingly, a colored photosensitive resin composition comprising dipropylene glycol dimethyl ether in a proportion of 5 wt% to 40 wt% in the solvent has been disclosed in order to prevent the conventional solvent from being molten (see Patent Document 1).

However, even with the composition of the solvent disclosed in Patent Document 1, surface defects and surface roughening suppressing effects generated in the coating film still remain insufficient. Particularly, when the content of the colorant is large or when the decompression speed is increased for shortening the tact, surface defects and surface roughness of the coating film become conspicuous.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide a colored photosensitive resin composition capable of effectively suppressing surface flaws and surface roughening of a coating film when the coating film is dried under reduced pressure, a color filter having a pattern formed using the colored photosensitive resin composition And a liquid crystal display having the color filter.

The inventors of the present invention have studied hard to solve the above problems. As a result, it has been found that the above problems can be solved by setting the solvent in the colored photosensitive resin composition to a specific composition, and the present invention has been accomplished. Specifically, the present invention provides the following.

A first aspect of the present invention is a colored photosensitive resin composition containing a photopolymerizable compound (A), a photopolymerization initiator (B), a colorant (C) and a solvent (S), wherein the solvent (S) has a boiling point of 170 And at least one first high boiling point solvent (H1) having a boiling point of 170 DEG C or more and less than 180 DEG C at atmospheric pressure; and at least one second boiling point solvent having a boiling point of 180 DEG C or higher at atmospheric pressure (H2), and the ratio of the first high boiling point solvent (H1) in the solvent (S) is not less than 60% by weight.

A second aspect of the present invention is a color filter having a pattern formed using the colored photosensitive resin composition according to the present invention.

A third aspect of the present invention is a liquid crystal display display having a color filter according to the present invention.

According to the present invention, there is provided a colored photosensitive resin composition capable of effectively suppressing surface defects and surface roughening of a coating film when the coating film is dried under reduced pressure, a color filter having a pattern formed using the colored photosensitive resin composition, A liquid crystal display can be provided.

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 according to the present invention contains a photopolymerizable compound (A), a photopolymerization initiator (B), a colorant (C) and a solvent (S). Hereinafter, each component contained in the colored photosensitive resin composition will be described in detail.

[(A) Photopolymerization  compound]

As the photopolymerizable compound (A), resins or monomers having an ethylenic unsaturated group are preferable, and it is more preferable to combine them. 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 weight average molecular weight of 1,000 or more among the ethylenically unsaturated group-containing compounds are referred to as "resins having an ethylenic unsaturated group" and those having a weight average molecular weight of less than 1,000 will be referred to as "monomer having an ethylenic unsaturated group" .

( Ethylenic Unsaturated group  Resin)

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, diethyleneglycol di (meth) acrylate, triethyleneglycol di (meth) acrylate, tetra (meth) (Meth) acrylates such as ethylene glycol di (meth) acrylate, butylene glycol dimethacrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meta) acrylate, ) Acrylates, oligomers obtained by polymerizing 1,6-hexanediol di (meth) acrylate, cardo epoxy diacrylate and the like; (Meth) acrylate obtained by reacting a polyester prepolymer obtained by condensing a polyhydric alcohol with a monobasic acid or a polybasic acid with (meth) acrylic acid, a compound obtained by reacting a polyol with a compound having two isocyanate groups, (Meth) acrylate; 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 ether, (Meth) acrylate resins obtained by reacting an epoxy resin such as a cydyl ester, an aliphatic or alicyclic epoxy resin, an amine epoxy resin or a dihydroxybenzene type epoxy resin with (meth) acrylic acid. A resin obtained by reacting an epoxy (meth) acrylate resin with a polybasic acid anhydride can be suitably used.

As the resin having an ethylenic unsaturated group, a resin obtained by further reacting a reaction product of an epoxy compound and an unsaturated group-containing carboxylic acid compound with a polybasic acid anhydride can be suitably used.

Among them, a compound represented by the following formula (a1) is preferable. The compound represented by the formula (a1) is preferable in view of its high photocurability.

In the formula (a1), X represents a group represented by the following formula (a2).

( ^2a ), R ^1a independently represents a hydrogen atom, a hydrocarbon group of 1 to 6 carbon atoms or a halogen atom, R ^2a independently represents a hydrogen atom or a methyl group, W represents a single bond or a group represented by the following formula a3).

In the formula (a1), Y represents a residue obtained by removing an acid anhydride group (-CO-O-CO-) from a dicarboxylic acid anhydride. Examples of the dicarboxylic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylene tetrahydrophthalic anhydride, chlorenedic anhydride, methyltetrahydrophthalic anhydride, And glutaric acid.

In the above formula (a1), Z represents a residue obtained by subtracting two acid anhydride groups from a tetracarboxylic acid dianhydride. Examples of the tetracarboxylic acid dianhydride include pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, and the like.

In the above formula (a1), m represents an integer of 0 to 20.

The acid value of the resin having an ethylenic unsaturated group is preferably 10 to 150 mgKOH / g, more preferably 70 to 110 mgKOH / g, in terms of resin solid content. When the acid value 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 weight average molecular weight of the resin having an ethylenic unsaturated group is preferably 1,000 to 40,000, more preferably 2,000 to 30,000. When the weight average molecular weight is 1,000 or more, heat resistance and film strength can be improved. When the weight average molecular weight is 40,000 or less, sufficient solubility in a developer can be obtained.

( Ethylenic Unsaturated group  Branch Monomer )

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, butoxymethoxy (Meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, maleic anhydride, maleic anhydride, Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, (Meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl ) Acrylate, 2-phenoxy-2-hydroxypropyl (meth) (Meth) acrylate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidyl (Meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, and half . These monofunctional monomers may be used alone or in combination of two or more.

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 di (meth) acrylate, butyleneglycol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (Meth) acryloxypolyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxy diethoxyphenyl) propane, (Meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (Meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (i.e., tolylene diisocyanate), trimethylhexamethylene diisocyanate, A reaction product of methylene diisocyanate and 2-hydroxyethyl (meth) acrylate, a reaction product of methylene bis (meth) acrylamide, (meth) acrylamide methylene ether, polyhydric alcohol and N-methylol Multi-functional monomers, such as water or the like can be given triacrylate formal. These multifunctional monomers may be used alone or in combination of two or more.

The content of the photopolymerizable compound (A) is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, based on the solid content of the colored photosensitive resin composition. When the amount is in the above-mentioned range, there is a tendency that a balance of sensitivity, developability and resolution tends to be achieved.

[ Light curing  Initiator (B)]

Examples of the photopolymerization initiator (B) 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-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis (4-dimethylaminophenyl) 2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, ethanone-1 - [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (o- acetyloxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4- Benzyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4- Dimethylamino-2-isoamylbenzoic acid, benzyl- beta -methoxy Ethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2,4- 2-methylthioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthone, 2-chlorothioxanthogen, Tetraethyl orthoquinone, 2-ethyl anthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazole, 2-mercaptobenzothiazole, Benzoquephenone, 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-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, alpha, alpha -dichloroacetophenone, p-tert- Phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) propane, p-methoxytriazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -Yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine (Trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) 2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, (Trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) bis (trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo) 4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- Trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine and 2,4-bis- trichloromethyl-6- S-triazine and the like can be used. Among them, it is particularly preferable to use a photopolymerization initiator of oxime type in terms of sensitivity. These photopolymerization initiators may be used alone or in combination of two or more.

The content of the photopolymerization initiator (B) is preferably 0.5 to 30% by weight, more preferably 1 to 20% by weight based on the solid content of the colored photosensitive resin composition. When the content is in 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.

[Colorant (C)]

As the colorant (C), for example, a compound classified as a pigment in the color index (CI, published by The Society of Dyers and Colourists), specifically, a color index (CI) number And the like can be used. These coloring agents may be used alone or in combination of two or more in order to prepare a color tone.

C.I. Pigment Yellow 1 (hereinafter, "CI Pigment Yellow" will be similarly described only), 3,11,12,13,14,15,16,17,20,24,31,35,55,60,61 , 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, , 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180, 185;

C.I. Pigment Orange 1 (hereinafter, " CI Pigment Orange " is similarly described only), 5,13,14,16,17,24,34,36,38,40,43,46,49,51,55 , 59, 61, 63, 64, 71, 73;

C.I. Pigment Violet 1 (hereinafter, "C.I. Pigment Violet" is similarly numbered), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50;

C.I. Pigment Red 1 (hereinafter, "CI Pigment Red" will be similarly described only), 2,3,4,5,6,7,8,9,10,11,12,14,15,16,17 48: 3, 48: 4, 49: 1, 49: 2, 48, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 81: 1, 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170 , 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, , 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, 265;

C.I. Pigment Blue 1 (hereinafter, "C.I. Pigment Blue" is similarly described only), 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66;

C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 37;

C.I. Pigment Brown 23, C.I. Pigment Brown 25, C.I. Pigment Brown 26, C.I. Pigment Brown 28;

C.I. Pigment Black 1, C.I. Pigment Black 7.

In the case of forming a black matrix in the color filter, a black pigment is used as the colorant (C).

As the black pigment, it is preferable to use carbon black or titanium black. In addition, Cu, Fe, Mn, Cr, Co, Ni, V, Zn, Se, Mg, Ca, Sr, Ba, Pd, Ag, Cd, In, Sn, Sb, Hg, Pb, And inorganic pigments such as various metal oxides, complex oxides, metal sulfides, metal sulfates, and metal carbonates can also be used.

As the carbon black, known carbon blacks such as channel black, furnace black, thermal black and lamp black can be used, but channel black can be suitably used because it has excellent light shielding properties. Resin-coated carbon black may also be used. Specifically, resin-coated carbon black obtained by mixing carbon black and a resin having reactivity with a carboxyl group, a hydroxyl group and a carbonyl group present on the surface of the carbon black, and heating at 50 to 380 ° C, or a water- Or resin-coated carbon black obtained by dispersing an ethylenic monomer in a water-surfactant mixed system and radical polymerization or radical copolymerization in the presence of a polymerization initiator. This resin-coated carbon black has a lower conductivity than carbon black having no resin coating, so that leakage of current when used in a color filter is small, and a liquid crystal display with low power consumption and high reliability can be formed.

An organic pigment may be added to the inorganic pigment as an auxiliary pigment. The following effects can be obtained by appropriately selecting and adding the complementary color of the inorganic pigment to the organic pigment. For example, carbon black is reddish black. Therefore, by adding an organic pigment having a blue color which is a complementary color of red as an auxiliary pigment to carbon black, the red light of the carbon black disappears and the black color is more preferable as a whole. The organic pigment is preferably used in an amount of 10 to 80 parts by weight, more preferably 20 to 60 parts by weight, and most preferably 20 to 40 parts by weight, based on 100 parts by weight of the total amount of the inorganic pigment and the organic pigment.

As the inorganic pigments and organic pigments, a solution in which the pigment is dispersed at an appropriate concentration using a dispersant can be used. For example, as the inorganic pigment, a carbon dispersion CF black (containing 20% of carbon concentration) manufactured by Mikuni Color, a carbon dispersion CF black (containing 24% of high resistance carbon) manufactured by Mikuni Color Co., Ltd., a titanium black dispersion CF black Containing 20% of titanium pigment). Examples of the organic pigment include blue pigment dispersion CF blue (containing 20% of blue pigment) manufactured by Mikuni Color Co., and violet pigment dispersion (containing 10% of violet pigment) manufactured by Mikuni Color. As the dispersing agent, a polyethyleneimine-based, urethane resin-based, acrylic resin-based polymeric dispersing agent is preferably used.

The content of the colorant (C) is preferably 1 to 70% by weight, more preferably 20 to 60% by weight, based on the solid content of the colored photosensitive resin composition. By setting the content in the above range, it is possible to improve the coloring performance while suppressing the occurrence of hardening defects.

When a black pigment is used as the colorant (C), it is preferable to adjust the OD (Optical Density) value to be 3.5 or more, preferably 4.0 or more per 1 m of the film thickness of the formed film. When the OD value per 1 탆 of the film thickness is 3.5 or more, a sufficient display contrast can be obtained and a required performance can be obtained when used as a black matrix of a color filter.

[Solvent (S)]

At least one low boiling point solvent (L) having a boiling point of less than 170 DEG C, at least one first high boiling point solvent (H1) having a boiling point of 170 DEG C or more and less than 180 DEG C, 2 high boiling point solvent (H2) is used. In addition, the boiling point referred to herein is a value at atmospheric pressure. When the solvent (S) has such a composition, surface defects and surface roughness of the coating film when the coated film of the colored photosensitive resin composition is dried under reduced pressure can be effectively suppressed.

The boiling point of the low boiling point solvent (L) is less than 170 캜, preferably 160 캜 or lower. The boiling point is preferably 130 ° C or higher, and more preferably 140 ° C or higher. Concretely, such low boiling point solvent (L) is preferably at least one selected from cyclohexanone (AN) and propylene glycol monomethyl ether acetate (PGMEA). Of these, propylene glycol monomethyl ether acetate (PGMEA) is more preferable.

The content of the low boiling point solvent (L) is preferably less than 35 wt%, more preferably not more than 30 wt% with respect to the total amount of the solvent (S). The content is preferably 5% by weight or more, more preferably 10% by weight or more, and still more preferably 15% by weight or more. Since the low-boiling point solvent (L) is volatilized for the first time when the colored photosensitive resin composition is applied, the low boiling point solvent (L) can be contained in such a content so that the efficiency of drying the coated film of the colored photosensitive resin composition under reduced pressure can be increased.

The boiling point of the first high boiling point solvent (H1) is 170 占 폚 or higher and lower than 180 占 폚. Specific examples of the first high boiling point solvent (H1) include at least one selected from 3-methoxybutyl acetate (MA), dipropylene glycol dimethyl ether (DMM) and cyclohexanol acetate (CHXA) . Among them, 3-methoxybutyl acetate (MA) and cyclohexanol acetate (CHXA) are more preferable, and 3-methoxybutyl acetate (MA) is particularly preferable.

The content of the first high boiling point solvent (H1) is preferably 60% by weight or more, more preferably 63% by weight or more, and still more preferably 65% by weight or more based on the total amount of the solvent (S). The content is preferably 90% by weight or less, and more preferably 85% by weight or less.

The boiling point of the second high boiling point solvent (H2) is 180 ° C or higher, preferably 190 ° C or higher, and more preferably 200 ° C or higher. The boiling point is preferably 250 ° C or lower. Specific examples of the second high boiling point solvent H2 include propylene glycol diacetate (PGDA), gamma butyrolactone (GBL), dipropylene glycol methyl ether acetate (DPMA), diethylene glycol monoethyl ether acetate (EDGAC ), 1,3-butylene glycol diacetate (BGDA), and diethylene glycol monobutyl ether acetate (BDGAC). Among these, 1,3-butylene glycol diacetate (BGDA) and diethylene glycol monobutyl ether acetate (BDGAC) are particularly preferable.

The weight change ratio of the second high boiling point solvent (H2) at 100 캜 is preferably 15 TG% or less, more preferably 10 TG% or less, and even more preferably 8 TG% or less. The weight change rate is preferably 2 TG% or more, more preferably 4 TG% or more. Here, the " weight change rate at 100 占 폚 " indicates a change in weight 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 weight change amount of the solvent in the air.

It is preferable that the dissolution parameter of the second high boiling point solvent (H2) is 8.7 (cal / cm < 3 >) ^1/2 or more. Since the second high boiling point solvent H2 is hardly volatilized most in the solvent S, when the coating film of the colored photosensitive resin composition is dried under reduced pressure using a vacuum drying apparatus (VCD) or the like, the solvent remains in the coating film until the last. At this time, if the dissolution parameter of the second high boiling point solvent (H2) is 8.7 (cal / cm3) ^1/2 or more, the dispersibility of the colorant (C) is maintained well until the end of the decompression drying and surface roughening or surface roughening . The dissolution parameter is preferably 11 (cal / cm3) ^1/2 or less, more preferably 10 (cal / cm3) ^1/2 or less.

The content of the second high boiling point solvent (H2) is preferably 0.1 to 10 wt%, more preferably 1 to 8 wt% with respect to the total amount of the solvent (S).

The solvent (S) preferably has an average boiling point of 165 DEG C or higher, more preferably 167 DEG C or higher, and still more preferably 168 DEG C or higher. The average boiling point is preferably 200 占 폚 or lower, more preferably 185 占 폚 or lower, even more preferably 180 占 폚 or lower, and particularly preferably 175 占 폚 or lower. Here, the " average boiling point " is obtained by multiplying the boiling point of each solvent by the content ratio of the solvent to the total amount of the solvent (S) and averaging the boiling points.

The content of the solvent (S) is preferably such that the solid concentration of the colored photosensitive resin composition is 1 to 50% by weight, more preferably 5 to 30% by weight. When the amount is in the above range, the film-forming ability and the coating property in the colored photosensitive resin composition can be satisfactorily maintained.

[Other components]

The colored photosensitive resin composition of the present invention may contain additives as required. Examples of the additives include a thermal polymerization inhibitor, a defoaming agent, a surfactant, a sensitizer, a curing accelerator, a photo-crosslinking agent, a dispersant, a dispersing aid, a filler, an adhesion promoter, an antioxidant, an ultraviolet absorber and an antiflocculating agent.

[Method of preparing colored photosensitive resin composition]

The colored photosensitive resin composition according to the present invention can be obtained by mixing all of the above components with a stirrer. The filtration may be performed using a filter so that the resulting mixture becomes uniform.

According to the colored photosensitive resin composition of the present invention, it is possible to effectively suppress surface defects and surface roughening of the coating film upon drying under reduced pressure. Among them, it is particularly effective when a black pigment is used as the colorant (C). The colored photosensitive resin composition containing a black pigment preferably has a high OD value as described above. However, even if the content of the black pigment is increased for high OD by the solvent (S) satisfying the above conditions It is possible to effectively suppress the risk of occurrence of surface defects and surface roughening.

<Color filter>

The color filter according to the present invention has a pattern formed by using the colored photosensitive resin composition according to the present invention. This color filter can be manufactured, for example, as follows.

First, the colored photosensitive resin composition according to the present invention is coated on a substrate (substrate) using a non-contact type coating device such as a contact transfer type coating device such as a roll coater, a reverse coater, or a bar coater or a spinner (rotary coating device), a slit coater, Lt; / RTI &gt; Examples of the material of the substrate include glass, polyethylene terephthalate, acrylic resin, polycarbonate and the like.

Subsequently, the coating film of the colored photosensitive resin composition is dried. The drying method is not particularly limited. For example, it is dried under reduced pressure at room temperature using a vacuum drying apparatus (VCD), and then dried in a hot plate at a temperature of 80 to 120 DEG C, preferably 90 to 100 DEG C for 60 to 120 seconds Followed by drying. According to the colored photosensitive resin composition of the present invention, even when the coating film is dried under reduced pressure, surface defects and surface roughness of the coating film can be effectively suppressed.

Then, this coating film is irradiated with active energy rays such as ultraviolet rays and excimer laser beams through a negative-type mask to selectively expose it. The energy dose to be irradiated varies depending on the composition of the colored photosensitive resin composition, but is preferably 30 to 2,000 mJ / cm &lt; 2 &gt;.

Subsequently, the coated film after exposure is patterned into a desired shape by developing with a developing solution. 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 on the developed pattern at about 220 to 250 캜, preferably about 230 to 240 캜. 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 on the colored photosensitive resin composition of each color of red, green and blue to form a pixel pattern of each color. As a result, a color filter is formed.

Further, when manufacturing a color filter, it is also possible to eject ink of each color of red, green, and blue from the ink jet nozzles in each pixel region partitioned by the black matrix, and cure the collected ink with heat or light.

&Lt; Liquid crystal display &

The liquid crystal display according to the present invention has a color filter according to the present invention. In order to manufacture the liquid crystal display, first, the color filter is formed on one of the substrates, and then an electrode, a spacer, and the like are sequentially formed. Then, an electrode or the like is formed on the other substrate, and a predetermined amount of liquid crystal is injected and sealed by adhering them together.

Example

EXAMPLES Hereinafter, examples of the present invention will be described, but the scope of the present invention is not limited to these examples.

&Lt; Example 1 &gt;

[ Photopolymerization  Synthesis of Compound]

First, in a 500 ml four-necked flask, 235 g of bisphenol fluorene 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 of acrylic acid , And the mixture was heated and dissolved at 90 ° C to 100 ° C while blowing air at a rate of 25 ml / min. Then, the solution was gradually warmed to a cloudy state and heated to 120 DEG C to dissolve completely. Here, the solution gradually became transparent (viscous), but stirring was continued. During this time, the acid value was measured, and the heating and stirring were continued until the concentration was less than 1.0 mgKOH / g. The acid value required 12 hours to reach the target. Then, the mixture was 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 benzophenonetetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed, And the reaction was allowed to proceed at 110 ° C to 115 ° C for 4 hours. After confirming disappearance of the acid anhydride, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 DEG C for 6 hours to obtain Resin A-1 (weight average molecular weight: 3,400). The disappearance of the acid anhydride was confirmed by IR spectrum.

[Preparation of colored photosensitive resin composition]

The following components were mixed to a solid content concentration of 18% by weight, stirred with a stirrer for 2 hours, and filtered through a 5 탆 membrane filter to obtain a colored photosensitive resin composition. The boiling point, the dissolution parameter and the weight change ratio at 100 캜 of each solvent used for preparing the colored photosensitive resin composition under atmospheric pressure are shown in Table 1.

(A): Resin A-1 (solid content: 55%, solvent: 3-methoxybutyl acetate) 23.6 parts by weight

Dipentaerythritol hexaacrylate ... 4.8 parts by weight

(B): IRGACURE OXE 02 (manufactured by Ciba Specialty Chemicals) ... 1.4 parts by weight

(C): Carbon dispersion ("CF Black EX-1455" manufactured by Mikuni Color Co., Ltd., high resistance carbon: 24%, dispersant: 5%, solvent: 3-methoxybutyl acetate) 100 parts by weight

(S): 3-methoxybutyl acetate / cyclohexanone / propylene glycol monomethyl ether acetate / 1,3-butylene glycol diacetate = 65: 15: 13:

&Lt; Examples 2 to 12 and Comparative Examples 1 to 11 &gt;

A colored photosensitive resin composition was prepared in the same manner as in Example 1 except that the composition of the solvent (S) was changed as shown in Tables 2 and 3. The OD value of the colored photosensitive resin composition used in Examples and Comparative Examples was 4.5. The boiling point, the dissolution parameter and the weight change ratio at 100 캜 of each solvent used for preparing the colored photosensitive resin composition under atmospheric pressure are shown in Table 1.

Here, the weight change rate was measured by adding a solvent to a thermal balance (&quot; TG / DTA6200 (trade name) &quot;, manufactured by SII Nanotechnology) kept at 100 캜 and calculating the weight change amount of the solvent in the atmosphere.

<Evaluation>

The colored photosensitive resin compositions prepared in Examples 1 to 12 and Comparative Examples 1 to 11 were applied on a glass substrate having a size of 680 mm x 880 mm and then dried under reduced pressure at 66 Pa for 30 seconds and then prebaked at 110 캜 for 120 seconds To obtain a coating film having a film thickness of about 1.0 mu m. The coating film was evaluated for surface defects and surface roughness as follows.

[Evaluation of surface defects]

The number of defects on the surface of the coating film was measured using a surface defect measuring apparatus (product name: "KLA-213X", manufactured by KLA-Tencor Corporation). The results are shown in Tables 2 and 3.

[Evaluation of Surface Roughness]

The surface roughness (Ra) of the coating film was evaluated using an atomic force microscope (manufactured by SII Nanotechnology). The results are shown in Tables 2 and 3. In Comparative Examples 3 to 11, the surface roughness was not evaluated because the number of defects on the surface of the coating film was remarkably large.

As can be seen from Tables 2 and 3, at least one low boiling point solvent (L) having a boiling point of less than 170 占 폚, at least one first high boiling point solvent (H1) having a boiling point of 170 占 폚 or more and less than 180 占 폚, (S) containing at least one kind of second high boiling point solvent (H2) and a ratio of the first high boiling point solvent (H1) of 60% by weight or more to the coloring photosensitive resin composition of Examples 1 to 12 , Surface defects and surface roughening of the coating film when the coating film was dried under reduced pressure could be effectively suppressed. In particular, by increasing the ratio of the second high boiling point solvent (H2), the effect of suppressing surface defects and surface roughness was improved (Examples 1 to 4 and Examples 5 to 7).

On the other hand, when the colored photosensitive resin compositions of Comparative Examples 1 to 5 and 10 which did not contain the second high boiling point solvent (H2) were used, surface defects and surface roughness of the coating film were remarkably generated Respectively. Even when the second high boiling point solvent (H2) was contained, when the colored photosensitive resin compositions of Comparative Examples 6 to 9 in which the ratio of the first high boiling point solvent (H1) was 55% by weight were used, , Surface defects of the coating film remarkably occurred. In the colored photosensitive resin compositions of Comparative Examples 8 and 9, for example, the solvent (S) has a higher average boiling point than those of Examples 1 and 5. However, even when the average boiling point is high, the ratio of the first high boiling point solvent When the content is less than 10% by weight, surface defects and surface roughness of the coating film can not be suppressed. Further, even when the colored photosensitive resin composition of Comparative Example 11, which does not contain the first high boiling point solvent (H1) and the ratio of the low boiling point solvent (L) was 95 wt%, was used, The defects were remarkable.

Claims (8)

1. A colored photosensitive resin composition comprising a photopolymerizable compound (A), a photopolymerization initiator (B), a colorant (C) and a solvent (S)
The solvent (S)
At least one low boiling point solvent (L) having a boiling point at atmospheric pressure of less than 170 占 폚,
At least one first high boiling point solvent (H1) having a boiling point at atmospheric pressure of 170 DEG C or more and less than 180 DEG C,
And at least one second high boiling point solvent (H2) having a boiling point of 180 DEG C or higher at atmospheric pressure,
Wherein the ratio of the first high boiling point solvent (H1) in the solvent (S) is 60 wt% or more and 90 wt%
, The ratio of the second high boiling point solvent (H2) in the solvent (S) is 0.1 to 8 wt%
Wherein the second high boiling point solvent H2 is selected from the group consisting of propylene glycol diacetate (PGDA), gamma butyrolactone (GBL), dipropylene glycol methyl ether acetate (DPMA), diethylene glycol monoethyl ether acetate (EDGAC) -Butylene glycol diacetate (BGDA) and diethylene glycol monobutyl ether acetate (BDGAC). The method according to claim 1,
And the dissolution parameter of the second high boiling point solvent (H2) is 8.7 (cal / cm &lt; 3 &gt;) ^1/2 or more. The method according to claim 1,
Wherein the solvent (S) has an average boiling point of 165 DEG C or more. The method according to claim 1,
Wherein the first high boiling point solvent (H1) is at least one selected from 3-methoxybutyl acetate (MA), dipropylene glycol dimethyl ether (DMM) and cyclohexanol acetate (CHXA). The method according to claim 1,
Wherein the low boiling point solvent (L) is at least one selected from cyclohexanone (AN) and propylene glycol monomethyl ether acetate (PGMEA). The method according to claim 1,
Wherein the colorant (C) 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 6. A liquid crystal display having the color filter according to claim 7.