JP5507938B2 - Photosensitive resin composition for color filter, color filter, and liquid crystal display - Google Patents

Description

The present invention relates to a photosensitive resin composition for a color filter, and a color filter and a liquid crystal display manufactured using the photosensitive resin composition.

  Since the photosensitive resin composition can obtain a resin pattern having a desired shape by exposure and development, it is used for various applications such as a color filter and a spacer in a printing plate, a photoresist, or a liquid crystal display. For example, when manufacturing a color filter, first, a black photosensitive resin composition is applied to a substrate, dried under reduced pressure (vacuum drying) with a vacuum drying apparatus (VCD), exposed to light, developed, and black matrix. Form. Next, coating, exposure, and development are repeated for each of the R, G, and B photosensitive resin compositions, thereby forming a pattern of each color at a predetermined position to manufacture a color filter.

  In such applications, it is one of the important issues to make the film thickness of the photosensitive resin layer after coating uniform. Conventionally, in order to make the film thickness of the photosensitive resin layer uniform, it is common to add a surfactant having a leveling effect to the photosensitive resin composition (see Patent Documents 1 and 2, etc.).

JP-A-2005-107131 JP 2005-105045 A

  However, particularly in the case of a photosensitive resin composition containing a colorant, since the structure of the dispersant for dispersing the colorant is similar to the structure of the surfactant, the effect of the surfactant cannot be sufficiently obtained. The coating uniformity and flatness of the photosensitive resin layer were poor. In recent years, as a result of the desire for high color density and high OD (Optical Density) value in color filters and black matrices, the amount of colorant added tends to increase. This has led to a decrease in the coating property and the coating uniformity and flatness of the photosensitive resin layer become worse.

  Furthermore, when the photosensitive resin layer is vacuum-dried, defects (defects) occur in the photosensitive resin layer, or when the heat treatment is performed, the traces of proxy pins (pin marks) that support the substrate are photosensitive. Although it may remain in the resin layer, the present inventors investigated and studied, and it was found that the type and property of the surfactant is one of these factors.

  The present invention has been made in view of such a conventional situation, and obtains a photosensitive resin layer having a high leveling effect and excellent coating uniformity and flatness even when a colorant is contained. A photosensitive resin composition capable of reducing the occurrence of defects and pin marks, and a color filter and a liquid crystal display manufactured using the photosensitive resin composition are provided. Objective.

  In order to solve the above-mentioned problems, the present inventors have conducted extensive research on various types of surfactants. And, the silicone-based surfactant has a lower leveling effect than the fluorine-based surfactant, and the coating property when applying another photosensitive resin composition on the formed photosensitive resin layer is low, Since there is a risk of uneven coating, further investigations were repeated with a focus on fluorine-based surfactants. As a result, the inventors have found that the above problem can be solved by using a specific fluorine-based surfactant, and have completed the present invention. Specifically, the present invention provides the following.

  A first aspect of the present invention is a photosensitive resin composition containing (A) a resin component, (B) a photosensitive agent, and (C) a surfactant, wherein the (C) surfactant is carbon. It has a fluorinated alkyl group of 1 to 20 (but may be interrupted by an ether bond, an ester bond, a carbonyl group or a urethane bond) and a philic group in the side chain, and has a mass average molecular weight. It is the photosensitive resin composition which is a 10000-50000 polymer.

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

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

  Since the photosensitive resin composition according to the present invention has a high leveling property, a photosensitive resin layer excellent in coating uniformity and flatness can be obtained even when it contains a colorant. Further, when manufacturing a color filter for a liquid crystal display, it is possible to reduce the occurrence of defects and pin marks in the photosensitive resin layer.

It is a figure for demonstrating the nonuniformity width | variety in the Example of this invention.

≪Photosensitive resin composition≫
The photosensitive resin composition according to the present invention contains (A) a resin component, (B) a photosensitive agent, and (C) a surfactant. This photosensitive resin composition may be a negative type or a positive type, and in the case of a positive type, it may be a non-chemical amplification type or a chemical amplification type. Hereinafter, each component contained in the photosensitive resin composition will be described in detail.

<(A) Resin component>
The resin component (A) contained in the photosensitive resin composition according to the present invention is a negative or positive type, a non-chemically amplified type or a chemically amplified type. It depends on whether there is.

When the photosensitive resin composition according to the present invention is a negative type, (A) an alkali-soluble resin is used as the resin component, and the alkali-soluble resin contains a photopolymerizable resin. As this photopolymerizable resin, a resin having an ethylenically unsaturated group is preferred.
As the resin having an ethylenically unsaturated group, (meth) acrylic acid, fumaric acid, maleic acid, monomethyl fumarate, monoethyl fumarate, 2-hydroxyethyl (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, ethylene Glycol monoethyl ether (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, acrylonitrile, methacrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol diacrylate, triethylene glycol di (meth) acrylate, tetrae Lenglycol di (meth) acrylate, butylene glycol dimethacrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra Oligomers in which (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, cardoepoxy diacrylate, etc. are polymerized; polyhydric alcohols (Meth) acrylate obtained by reacting (meth) acrylic acid with polyester prepolymer obtained by condensing monobasic acid or polybasic acid with And polyurethane (meth) acrylate obtained by reacting a polyol and a compound having two isocyanate groups and then reacting with (meth) acrylic acid; bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S Type epoxy resin, phenol or cresol novolac type epoxy resin, resol type epoxy resin, triphenolmethane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ester, aliphatic or cycloaliphatic epoxy resin, amine epoxy resin, dihydroxy Examples include epoxy (meth) acrylate resins obtained by reacting an epoxy resin such as a benzene type epoxy resin with (meth) acrylic acid. Furthermore, a resin obtained by reacting an epoxy (meth) acrylate resin with a polybasic acid anhydride can be suitably used.

As the resin having an ethylenically 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 preferably used. .
Among these, the compound represented by the following formula (a1) is preferable. The compound represented by the formula (a1) itself is preferable in terms of high photocurability.

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

In the above formula (a2), R ^1a independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, R ^2a independently represents a hydrogen atom or a methyl group, and 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 the acid anhydride group (—CO—O—CO—) from the dicarboxylic acid anhydride. Examples of dicarboxylic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydro Examples thereof include phthalic anhydride and glutaric anhydride.

In the formula (a1), Z represents a residue obtained by removing two acid anhydride groups from tetracarboxylic dianhydride. Examples of tetracarboxylic dianhydrides include pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, and the like.
Moreover, in said formula (a1), n shows the integer of 0-20.

  The acid value of the resin having an ethylenically unsaturated group is preferably 10 to 150 mgKOH / g, and more preferably 70 to 110 mgKOH / g, in terms of resin solids. By setting the acid value to 10 mgKOH / g or more, sufficient solubility in the developer can be obtained. Moreover, by making an acid value into 150 mgKOH / g or less, sufficient sclerosis | hardenability can be obtained and surface property can be made favorable.

  The mass average molecular weight of the resin having an ethylenically unsaturated group (Mw: measured value in terms of polystyrene in gel permeation chromatography (GPC). Same in this specification) is preferably 1000 to 40000, 2000 More preferably, it is ˜30000. By setting the mass average molecular weight to 1000 or more, heat resistance and film strength can be improved. Moreover, sufficient solubility with respect to a developing solution can be acquired by making a mass mean molecular weight into 40000 or less.

  On the other hand, when the photosensitive resin composition according to the present invention is a positive type, there are a non-chemically amplified photosensitive resin composition and a chemically amplified photosensitive resin composition.

When the photosensitive resin composition according to the present invention is positive and non-chemically amplified, an alkali-soluble resin is used as the resin component (A). Examples of the alkali-soluble resin include phenols (phenol, m-cresol, p-cresol, xylenol, trimethylphenol, etc.) and aldehydes (formaldehyde, formaldehyde precursor, propionaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, etc.) and / or ketones (methyl ethyl ketone, acetone, etc.) in the presence of an acidic catalyst, a novolak resin; an acrylic resin obtained by polymerizing (meth) acrylic acid or its derivative A homopolymer of hydroxystyrene or a copolymer of hydroxystyrene and another styrene-based monomer; a copolymer of hydroxystyrene and (meth) acrylic acid or a derivative thereof;
Among them, (meth) acrylic acid derivatives having a hydroxyphenyl group such as p-hydroxylphenyl (meth) acrylate and p-hydroxyphenylethyl (meth) acrylate, and thermally crosslinkable groups such as glycidyl (meth) acrylate ( A copolymer with a (meth) acrylic acid derivative is preferred.

  The mass average molecular weight of such an alkali-soluble resin is preferably 2000 to 50000, and more preferably 5000 to 30000. By setting the mass average molecular weight to 2000 or more, it can be easily formed into a film. Moreover, sufficient solubility with respect to a developing solution can be acquired by making a mass mean molecular weight into 50000 or less.

  When the photosensitive resin composition according to the present invention is positive and chemically amplified, (A) a resin whose alkali solubility is increased by the action of an acid is used as the resin component. As such a resin, an alkali-soluble resin protected with an acid dissociable, dissolution inhibiting group is used, and there are many known hitherto used as resist resins for ArF excimer laser, KrF excimer laser, etc. Can be used.

  The mass average molecular weight of the resin whose alkali solubility is increased by the action of such an acid is preferably 2000 to 50000, more preferably 3000 to 30000, still more preferably 4000 to 20000, and 5000. It is especially preferable that it is -20,000. By using the above range, for example, when used as a resist composition, sufficient solubility with respect to a resist solvent is obtained, dry etching resistance is improved, and the resulting resin pattern has a good cross-sectional shape. It becomes.

<(E) Photopolymerizable monomer>
When the photosensitive resin composition according to the present invention is a negative type, the photosensitive resin composition may contain (E) a photopolymerizable monomer in addition to (A) a photopolymerizable resin as a resin component. preferable. As this (E) photopolymerizable monomer, the monofunctional monomer or polyfunctional monomer which has an ethylenically unsaturated group is preferable.

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

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

  (E) When it contains a photopolymerizable monomer, the content thereof is preferably 5 to 50% by mass, more preferably 10 to 40% by mass with respect to the solid content of the photosensitive resin composition. . By setting it as the above range, it tends to be easy to balance sensitivity, developability, and resolution.

<(B) Photosensitive agent>
The photosensitive agent (B) contained in the photosensitive resin composition according to the present invention may be a negative type or a positive type, or a non-chemically amplified type or a chemically amplified type. It depends on whether there is.

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

  The content of the photopolymerization initiator is preferably 0.1 to 50% by mass with respect to the solid content of the photosensitive resin composition. By setting it as said range, sufficient heat resistance and chemical-resistance can be acquired, a coating-film formation ability can be improved, and photocuring failure can be suppressed.

On the other hand, when the photosensitive resin composition according to the present invention is positive and non-chemically amplified, a quinonediazide group-containing compound is used as the photosensitive agent (B).
Examples of the quinonediazide group-containing compound include phenol compounds such as 2,3,4-trihydroxybenzophenone and 2,3,4,4′-tetrahydroxybenzophenone, naphthoquinone-1,2-diazide-5-sulfonic acid, and naphthoquinone- Completely esterified products and partially esterified products with naphthoquinone diazide sulfonic acid compounds such as 1,2-diazide-4-sulfonic acid; orthobenzoquinone diazide, orthonaphthoquinone diazide, or orthoanthraquinone diazide, or orthonaphthoquinone diazide sulfonic acid esters, etc. Of these compounds: orthoquinonediazidesulfonyl chloride and a compound having a hydroxyl group or an amino group, such as phenol, p-methoxyphenol, dimethylphenol, hydroquinone, bisphenol A, naphtho Toll, pyrocatechol, pyrogallol, pyrogallol monomethyl ether, pyrogallol-1,3-dimethyl ether, gallic acid, reaction products with gallic acid, aniline, p-aminodiphenylamine, etc. that are esterified or etherified leaving some hydroxyl groups Thing etc. are mentioned. These quinonediazide group-containing compounds may be used alone or in combination of two or more.

  It is preferable that content of this quinonediazide group containing compound is 5-50 mass parts with respect to 100 mass parts of (A) resin component. By setting it as said range, it becomes possible to improve the resolution, to reduce the amount of film loss after forming the resin pattern, and to impart appropriate sensitivity and transmittance.

When the photosensitive resin composition according to the present invention is positive and chemically amplified, a photoacid generator is used as the photosensitive agent (B).
As the photoacid generator, a number of conventionally known photoacid generators that can be used for resist resins such as for ArF excimer laser and KrF excimer laser can be used. For example, onium salt acid generators such as iodonium salts and sulfonium salts, oxime sulfonate acid generators, bisalkyl or bisarylsulfonyldiazomethanes, diazomethane acid generators such as poly (bissulfonyl) diazomethanes, nitrobenzyl sulfonates A variety of acid generators such as acid generators, iminosulfonate acid generators and disulfone acid generators can be used.

  The content of the photoacid generator is preferably 0.5 to 30 parts by mass and more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the resin component (A). By setting it as the above range, pattern formation is sufficiently performed. Moreover, since a uniform solution is obtained and storage stability becomes favorable, it is preferable.

<(C) Surfactant>
The surfactant (C) contained in the photosensitive resin composition according to the present invention is a fluorinated alkyl group having 1 to 20 carbon atoms (provided that it is interrupted by an ether bond, an ester bond, a carbonyl group, or a urethane bond). And a polymer having a philic group in the side chain.

The fluorinated alkyl group is not particularly limited as long as it has 1 to 20 carbon atoms, and is an ether bond (—O—), an ester bond (—CO—O—), a carbonyl group (—CO—), a urethane bond (— NH-CO-O-) may be interrupted by, but shall not be interrupted by these groups, i.e. _-C k _H l _F m (k is an integer of from 1 to 20, l is 0 to 40 In which m represents an integer of 1 to 41, and 1 + m = 2k + 1.

  Here, in recent years, it has been reported that compounds having a perfluoroalkyl group having 7 or more fluorinated carbon atoms have ecological effects such as carcinogenicity. It can also be subject to rules (SNUR). Therefore, as a fluorinated alkyl group, a C1-C5 perfluoroalkyl group is preferable, and the remaining carbon atoms are not fluorinated. More preferably, the perfluoroalkyl group has 3 to 5 carbon atoms.

  On the other hand, examples of the amphiphilic group include those contained in conventionally known nonionic surfactants, and those containing an alkylene group interrupted by an ether bond, an ester bond, or a carbonyl group are preferable. Among these, those containing a polyalkyleneoxy group (polyethyleneoxy group, polypropyleneoxy group, polybutyleneoxy group, etc.) are preferable.

  The molar ratio between the fluorinated alkyl group and the amphiphilic group varies depending on the composition of the photosensitive resin composition, but is preferably 4: 6 to 9: 1, and is 4: 6 to 8: 2. Is more preferable, and 5: 5 to 7: 3 is more preferable.

Such a surfactant can be obtained by polymerizing at least the monomer having the fluorinated alkyl group and the monomer having the philic group. As the monomer having a fluorinated alkyl group and the monomer having an amphiphilic group, monomers represented by the following formulas (c1) and (c2) are preferable.

In the above formula (c1), R ^1c represents a hydrogen atom or a methyl group, and R ^2c represents a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms. Rf represents a perfluoroalkyl group having 1 to 5 carbon atoms, preferably 3 to 5 carbon atoms.

In the above formula (c2), R ^3c represents a hydrogen atom or a methyl group, R ^4c represents an alkylene group having 2 to 4 carbon atoms, and R ^5c represents a hydrogen atom or 1 to 15 carbon atoms, preferably carbon. The alkyl group of number 1-10 is shown.
Moreover, in said formula (c2), p shows the integer of 1-50.

  Specific examples of the monomer represented by the above formula (c1) include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2- (Perfluorobutyl) ethyl (meth) acrylate, 2- (perfluoro-3-methylbutyl) ethyl (meth) acrylate and the like.

  Specific examples of the monomer represented by the formula (c2) include (meth) acrylic acid methoxypolyethylene glycol ester [for example, those having 1 to 50 ethylene glycol repeating units (r)], (meth) Acrylic acid methoxypolypropylene glycol ester [for example, one having 1 to 50 propylene glycol repeating units (r)], (meth) acrylic acid methoxypoly (ethylene-propylene) glycol ester [for example, ethylene glycol repeating unit number and propylene The total number of glycol repeating units (r) is 2 to 50], (meth) acrylic acid methoxy poly (ethylene-tetramethylene) glycol ester [for example, the number of ethylene glycol repeating units and the number of tetramethylene glycol repeating units And the sum (r) is ˜50], (meth) acrylic acid butoxy poly (ethylene-propylene) glycol ester [for example, the sum of the number of ethylene glycol repeating units and the number of propylene glycol repeating units (r) is 2 to 50], ( (Meth) acrylic acid octoxy poly (ethylene-propylene) glycol ester [for example, one having a total (r) of 2 to 50 ethylene glycol repeating units and propylene glycol repeating units), (meth) acrylic acid lauroxy polyethylene Glycol esters [for example, those having 2 to 50 ethylene glycol repeating units (r)], (meth) acrylic acid lauroxy poly (ethylene-propylene) glycol esters [for example, the number of ethylene glycol repeating units and propylene glycol repeating units number In which the total (r) is 2 to 50], polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polyethylene glycol-polybutylene glycol (meth) acrylate, polystyryl Examples include ethyl (meth) acrylate, Kyoeisha Chemical Co., Ltd. light ester HOA-MS, light ester HOMS, and the like.

  The molar ratio when the monomer represented by the above formula (c1) and the monomer represented by the above formula (c2) are polymerized is preferably 4: 6 to 9: 1. 2 is more preferable, and 5: 5 to 7: 3 is more preferable.

  (C) In addition to the monomer represented by the formula (c1) and the monomer represented by the formula (c2), the surfactant is an alkyl (meth) acrylate as long as the effects of the present invention are not impaired. It may be a polymerized ester. Specific examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i -Butyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, i-nonyl (meth) acrylate, lauryl (meth) acrylate, hexadecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (Meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, etc. are mentioned.

  The surfactant may be either a random polymer or a graft polymer, but is preferably a graft polymer. By using a graft polymer, the leveling effect can be further enhanced while maintaining compatibility with the (A) alkali-soluble resin. Moreover, in the case of a graft polymer, there is little possibility of becoming cloudy even if content is increased.

The sp value of the surfactant is preferably 8.0 to 9.5 (cal / cm ³ ) ^1/2 . By setting it as said range, compatibility with a resin component and a solvent can be improved and the effect as surfactant can be improved. In addition, sp value can be measured by the method of Unexamined-Japanese-Patent No. 2005-290128, for example.

  The mass average molecular weight of the resin contained in the surfactant is 10,000 to 50,000, and preferably 10,000 to 30,000. In general, a surfactant made of a compound having a small number of carbon atoms in the fluorinated alkyl group has a low leveling effect. Even if it exists, sufficient leveling effect can be acquired. Moreover, the photosensitive resin layer excellent in application | coating uniformity and flatness can be obtained by making a mass mean molecular weight into said range.

That is, in general, a surfactant exhibits a surface active effect by having an insoluble part and a soluble part in a solvent. However, in a low molecular weight surfactant, when a fluorinated alkyl group having a small number of carbon atoms is used as an insoluble site, the effect as an insoluble site is too small, so that a sufficient surfactant effect cannot be obtained. Further, when the proportion of the insoluble part is increased, the soluble part is decreased, so that sufficient solubility cannot be obtained. In contrast, when a fluorinated alkyl group having a small number of carbon atoms is used, by setting the mass average molecular weight of the surfactant to 10,000 or more, the insoluble portion (fluorinated alkyl group) in one molecule of the surfactant is reduced. Since the amount can be increased, the solubility in a solvent can be lowered, and the surface active effect can be ensured. Moreover, since the ratio of a soluble site | part can also be taken large, crowding of a fluorinated alkyl group can be prevented by the steric hindrance by this soluble site | part. Moreover, since the solubility with respect to a solvent can be ensured, even if it increases the addition amount of surfactant, it can become difficult to become cloudy.
Moreover, when spin-coating the photosensitive resin composition, the photosensitive resin composition is dropped on the substrate, and the substrate is rotated for coating. When a conventional low molecular weight surfactant is used, striation can be eliminated, but a liquid puddle of the photosensitive resin composition is generated at the edge of the substrate. A raised part of the resin composition is formed. That is, the coating uniformity and flatness are poor. On the other hand, since the photosensitive resin composition according to the present invention uses a surfactant having a mass average molecular weight of 10,000 or more, the bulge of the end can be eliminated even in spin coating. In particular, when the solid content concentration in the photosensitive resin composition is 30% by mass or more, there is a great effect in eliminating the rising of the end portion.
Furthermore, when apply | coating with a slit coater, it exists in the tendency which makes the solid content concentration of the photosensitive resin composition low generally. When the solid content concentration of the photosensitive resin composition is lowered, the flowability of the photosensitive resin composition increases, so that the applied photosensitive resin composition tends to have a non-uniform film thickness. In addition, there is a step of drying the applied photosensitive resin composition, but due to the effects of surface tension, temperature, concentration change during drying, etc. once applied to the photosensitive resin composition, from the edge of the substrate during the drying step The liquid returns to the center, and the uniformity of the film thickness tends to become worse. In particular, when a large substrate was used, the film thickness uniformity was greatly affected. On the other hand, since the photosensitive resin composition according to the present invention uses a surfactant having a mass average molecular weight of 10,000 or more, the film thickness uniformity can be improved.

  The content of the surfactant (C) is preferably 0.005 to 1% by mass and more preferably 0.01 to 0.5% by mass with respect to the total amount of the photosensitive resin composition. 0.05 to 0.2% by mass is more preferable. By setting it as said range, the photosensitive resin layer excellent in application | coating uniformity and flatness can be obtained. Also, when producing a color filter, the occurrence of defects and pin marks can be reduced.

  The photosensitive resin composition according to the present invention may contain other conventionally known surfactants as long as the effects of the present invention are not impaired.

<(D) Colorant>
The photosensitive resin composition according to the present invention may contain (D) a colorant. Examples of the colorant (D) include, for example, compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), specifically, the following color Examples are those with index (CI) numbers. These colorants may be used alone or in combination of two or more in order to adjust the color tone.

C. I. Pigment Yellow 1 (hereinafter, “CI Pigment Yellow” is the same and only the number is described) 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 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 the same, and only the number is described) 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, “CI Pigment Violet” is the same and only the numbers are described), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50;
C. I. Pigment Red 1 (hereinafter, “CI Pigment Red” is the same and only the number is described) 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 81: 1, 83, 88, 90: 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, 79, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, 265;
C. I. Pigment Blue 1 (hereinafter, “CI Pigment Blue” is the same and only the numbers are described), 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 37;
C. I. Pigment brown 23, C.I. I. Pigment brown 25, C.I. I. Pigment brown 26, C.I. I. Pigment brown 28;
C. I. Pigment black 1, C.I. I. Pigment Black 7.

  Moreover, when using it when forming the black matrix in a liquid crystal display, a black pigment is used as (D) coloring agent.

  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, Bi, Si, Al Inorganic pigments such as various metal oxides, composite oxides, metal sulfides, metal sulfates, metal carbonates, and the like can also be used.

  As the carbon black, known carbon blacks such as channel black, furnace black, thermal black, lamp black and the like can be used. In particular, channel black can be preferably used because of its excellent light shielding properties. Resin-coated carbon black can also be used. Specifically, carbon black and a resin-coated carbon black obtained by mixing 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., Examples thereof include resin-coated carbon black obtained by dispersing an ethylenic monomer in a water-organic solvent mixed system or water-surfactant mixed system and performing radical polymerization or radical copolymerization in the presence of a radical polymerization initiator. This resin-coated carbon black has low conductivity compared to carbon black without resin coating, so there is little current leakage when used as a color filter for liquid crystal display displays, etc., and a highly reliable display with low power consumption Can be formed.

  Moreover, you may add an organic pigment as an auxiliary pigment to said inorganic black pigment. By appropriately selecting and adding an organic pigment that exhibits a complementary color of an inorganic black pigment, the following effects can be obtained. For example, carbon black exhibits a reddish black color. Therefore, by adding an organic pigment exhibiting a blue color that is a complementary color of red as an auxiliary pigment to the carbon black, the redness of the carbon black disappears and a more preferable black color as a whole is exhibited. The organic pigment is preferably 10 to 80 parts by mass, more preferably 20 to 60 parts by mass, and more preferably 20 to 40 parts by mass with respect to 100 parts by mass of the sum of the inorganic black pigment and the organic pigment. Is most preferred.

  As said inorganic black pigment and organic pigment, the solution which disperse | distributed the pigment at a suitable density | concentration using a dispersing agent is used normally. For example, as the inorganic black pigment, carbon dispersion CF black (containing 20% carbon concentration) manufactured by Mikuni Color Co., Ltd., carbon dispersion CF black (containing high resistance carbon 24%) manufactured by Mikuni Color Co., Ltd. Examples thereof include titanium black dispersion CF black (containing 20% black titanium pigment). Examples of the organic pigment include Blue pigment dispersion CF blue (containing 20% blue pigment) manufactured by Mikuni Dye, and Violet pigment dispersion (containing 10% violet pigment) manufactured by Mikuni Dye. As the dispersant, a urethane resin-based polymer dispersant can be suitably used.

  (D) When it contains a coloring agent, it is preferable that the content is 1-70 mass parts with respect to 100 mass parts of solid content of the photosensitive resin composition, and it is more preferable that it is 20-60 mass parts. preferable. By setting it as said range, the coloring performance of the coloring pattern formed can be improved, and pattern formation ability can be improved.

  Further, when a black pigment is used as the colorant (D), it is preferable to adjust the OD value per 1 μm of the film to be formed to 3.5 or more, preferably 4.0 or more. If the OD value per film thickness of 1 μm is 3.5 or more, sufficient display contrast can be obtained when used in a black matrix of a liquid crystal display, and necessary performance can be obtained.

  Conventionally, a photosensitive resin composition containing such a colorant contains a dispersant having a structure similar to that of a surfactant. Therefore, a surfactant is added under the influence of the dispersant. However, a sufficient leveling effect could not be obtained. On the other hand, since the surfactant (C) has a high leveling effect, the photosensitive resin composition is excellent in coating uniformity and flatness even when a colorant is contained in the photosensitive resin composition. A layer can be obtained.

<(S) Solvent>
The photosensitive resin composition according to the present invention preferably contains a (S) solvent for dilution. Examples of the solvent (S) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n- Propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether , Dipropylene glycol monomethyl ether, di (Poly) alkylene glycol monoalkyl ethers such as propylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; ethylene (Poly) alkylene glycol monoalkyl ether acetates such as glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; diethylene glycol dimethyl Other ethers such as ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, etc. Lactic acid alkyl esters; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, hydroxyacetic acid Ethyl, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate Lopionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate , Other esters such as methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate; aromatic hydrocarbons such as benzene, toluene and xylene; N- Examples include amides such as methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and the like. Among these, it is preferable to use at least one of cyclohexanone and propylene glycol monomethyl ether acetate. These solvents may be used alone or in combination of two or more.

  (S) When a solvent is contained, the content is preferably such that the solid content concentration of the photosensitive resin composition is 1 to 50% by mass, and more preferably 5 to 30% by mass.

<Method for preparing photosensitive resin composition>
The photosensitive resin composition according to the present invention is obtained by mixing all of the above components and, if necessary, all the additives with a stirrer. You may filter using a filter so that the obtained mixture may become uniform.

≪Pattern formation method≫
When forming a resin pattern using the photosensitive resin composition according to the present invention, first, a contact transfer type coating device such as a roll coater, a reverse coater, a bar coater, or a spinner (rotary coating device), a slit coater. The photosensitive resin composition according to the present invention is applied on a substrate made of glass, polyethylene terephthalate, acrylic resin, polycarbonate, or the like using a non-contact type coating apparatus such as a curtain flow coater.

  Next, the applied photosensitive resin composition is dried to form a photosensitive resin layer. As a drying method, for example, vacuum drying at room temperature using a vacuum drying apparatus (VCD), followed by drying on a hot plate at 80 to 120 ° C., preferably 90 to 100 ° C. for 60 to 120 seconds, etc. Is mentioned.

Next, the photosensitive resin layer is partially exposed by irradiating active energy rays such as ultraviolet rays and excimer laser light through a mask. Although the energy dose to be irradiated varies depending on the composition of the photosensitive resin composition, it is preferably 30 to 2000 mJ / cm ² .

  Next, the exposed photosensitive resin layer is developed with a developer to obtain a resin pattern having a desired shape. Examples of the developing method include an immersion method and a spray method. Examples of the developer include organic ones such as monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.

  Next, the developed resin pattern is heated (post-baked) at 220 to 250 ° C., for example. When the applied photosensitive resin composition is a negative type, it is preferable to expose the formed resin pattern on the entire surface. As described above, a resin pattern having a predetermined shape can be obtained.

≪Color filter≫
The color filter according to the present invention has a pattern formed using the photosensitive resin composition according to the present invention. In order to produce this color filter, first, a resin pattern is formed using the photosensitive resin composition in which a black pigment is dispersed according to the above-described pattern forming method. This resin pattern becomes a black matrix. Next, pattern formation is performed in the same manner for the photosensitive resin composition in which red, green, and blue colorants are dispersed to form pixel patterns of respective colors. Thereby, a color filter is manufactured.

  In manufacturing the color filter, the ink of each color of red, green, and blue is ejected from the inkjet nozzles to each area partitioned by the black matrix, and the stored ink is cured by heat or light, and the color filter is It can also be manufactured.

  Conventionally, when a color filter is produced using a photosensitive resin composition containing a colorant, a flat photosensitive resin layer is obtained using a dispersant that is contained in the photosensitive resin composition. I could not. In particular, when the content of the colorant is large, the fluidity of the photosensitive resin composition is lowered, and the coating uniformity and flatness of the photosensitive resin layer are worsened. Furthermore, when manufacturing a color filter, when the photosensitive resin layer is vacuum-dried, defects (defects) occur in the photosensitive resin layer, or when the heat treatment is performed, the proxy pins that support the substrate In some cases, traces of pins (pin traces) may remain in the photosensitive resin layer. On the other hand, according to the photosensitive resin composition of the present invention, a photosensitive resin layer excellent in coating uniformity and flatness can be obtained even when a colorant is contained, and defects and The occurrence of pin marks can be reduced.

≪LCD display≫
The liquid crystal display according to the present invention has the color filter according to the present invention. In order to manufacture this liquid crystal display, first, the color filter is formed on one substrate, and then electrodes, spacers, and the like are sequentially formed. Then, after an electrode or the like is formed on the other substrate and bonded together, a predetermined amount of liquid crystal is injected and sealed. Thereby, a liquid crystal display is manufactured.

  Hereinafter, the present invention will be described in detail with reference to examples. In addition, this invention is not limited to the following Example at all.

<Examples 1-7, Comparative Examples 1-10>
[(A) Synthesis of alkali-soluble resin]
First, in a 500 ml four-necked flask, 235 g of bisphenolfluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0 g of acrylic acid Was heated and dissolved at 90 to 100 ° C. while blowing air at a rate of 25 ml / min. Next, the temperature was gradually raised while the solution was clouded, and the solution was heated to 120 ° C. to be completely dissolved. At this time, the solution gradually became transparent and viscous, but stirring was continued as it was. During this time, the acid value was measured, and heating and stirring were continued until the acid value was less than 1.0 mgKOH / g. It took 12 hours for the acid value to reach the target value. And it cooled to room temperature and obtained the bisphenol fluorene type epoxy acrylate represented by the following formula (a4) of colorless and transparent solid.

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

[Preparation of photosensitive resin composition]
As shown in Table 1 below, (S) a solvent is added to (A) an alkali-soluble resin, (E) a photopolymerizable monomer, (C) a surfactant, and (D) a colorant to obtain a solid concentration of 15 It adjusted to the mass% or 17 mass%, and after mixing for 2 hours with the stirrer, it filtered with a 5 micrometer membrane filter, and prepared the photosensitive resin composition. In addition, the compounding quantity of each component in Table 1 is a "mass part".

The details of (A) alkali-soluble resin, (B) photosensitizer, (D) colorant, and (S) organic solvent used in Table 1 are as follows.
(A) -1: Preparation liquid (E) -1: dipentaerythritol hexaacrylate (B) -1: IRGACURE prepared by adding 3-methoxybutyl acetate to resin (A-1) to adjust the solid content concentration to 50% by mass OXE 02 (Ciba Specialty Chemicals)
(B) -2: IRGACURE 369 (Ciba Specialty Chemicals)
(D) -1: Carbon black (manufactured by Mikuni Color Co., Ltd., carbon concentration: 55%, solvent: 3-methoxybutyl acetate)
(S) -1: 3-methoxybutyl acetate / cyclohexanone / propylene glycol monomethyl ether acetate = 60/20/20 (mass ratio)

  The details of the (C) surfactant used in Table 1 are as shown in Table 2 below. In Table 2, the numbers in parentheses in the copolymers of (C4) -1 to (C4) -9 are the charged amounts of each monomer when the total monomer amount when synthesizing the copolymer is 100 parts by mass. Indicates the percentage. (C8) -1 and Si-1 are manufactured by Kyoeisha Chemical Co., Ltd.

<Evaluation>
[Evaluation of uneven width]
The photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 10 obtained above were applied onto a 100 mm × 100 mm glass substrate (1737 glass) using a spin coater (manufactured by MIKASA). Then, it mounted on the glass piece of 5 mm width installed on the hotplate, and prebaked at 90 degreeC for 120 second. The unevenness width at that time was measured using a surface roughness measuring machine Surfcorder SE-2300 (manufactured by Kosaka Laboratory Ltd.). The results are also shown in Table 1.
The unevenness width is the unevenness width (nm) measured at the location shown in FIG. Since heat is transmitted only to the glass substrate from the glass substrate, convection occurs from the heated place and the photosensitive resin composition is repelled, and this repelling becomes a bead. The smaller the repelling, that is, the smaller the portion where the film thickness is extremely thin, the better the coating uniformity and flatness.

[Pin mark evaluation]
Using the spin coating apparatus TR-45310 (manufactured by Tokyo Ohka Kogyo Co., Ltd.), the photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 10 obtained above were each formed on a glass substrate of 680 mm × 880 mm. After the coating, it was placed on a lift pin installed on a hot plate and prebaked at 120 ° C. for 100 seconds to obtain a photosensitive resin layer having a thickness of 1.3 μm. About this photosensitive resin layer, the pin mark on the surface of the photosensitive resin layer was evaluated using “AOI” (manufactured by TAKANO). The evaluation criteria are as follows, and the results are also shown in Table 1.
◎: No pin traces ○: Thin pin traces are visible, but no problem level △: A small amount of pin traces are observed ×: Many pin traces are observed

  As can be seen from Table 1, in Examples 1 to 7 using a specific surfactant, a photosensitive resin layer excellent in coating uniformity and flatness can be obtained even when a colorant is contained. did it. Moreover, no pin trace was confirmed on the surface. On the other hand, in Comparative Examples 1 to 10 using other surfactants, the unevenness width was large, and the coating uniformity and flatness were poor. Also, pin marks remained on the surface.

[High-speed applicability evaluation]
The same photosensitive resin composition A as in Comparative Example 1 (solid content concentration of 15% by mass), the photosensitive resin composition B in which the solid content concentration was changed from 15% by mass to 12% by mass in Comparative Example 1, and the photosensitivity of Example 2 In the photosensitive resin composition, the blending amount of (A) the alkali-soluble resin is changed to 20 parts by mass, the blending amount of the (E) photopolymerizable monomer is changed to 8 parts by mass, and (B) the photosensitive agent is (B). -1 alone is changed to 10 parts by mass, the blending amount of (D) colorant is changed to 120 parts by mass, and the organic solvent is 3-methoxybutyl acetate / cyclohexanone / propylene glycol monomethyl ether acetate / = 65/25/10 It changed into (mass ratio), and each photosensitive resin composition C which adjusted solid content concentration to 12 mass% was prepared. The photosensitive resin compositions A to C are applied at a high speed (application speed: 250 nm / second) on a 2160 mm × 2460 mm glass substrate (thickness 0.7 mm) using a non-spin type application apparatus TR130200FC (manufactured by Tokyo Ohka Kogyo Co., Ltd.). sec., coating GAP: 130 μm) and then dried under reduced pressure at 13 Pa for 10 seconds to obtain a photosensitive resin layer. As a result, the photosensitive resin composition A was out of liquid and could not be applied at high speed. Although the photosensitive resin composition B was able to be applied at high speed, liquid return occurred immediately after the application, and the photosensitive resin layer was wavy (liquid return width 3 to 4 mm). On the other hand, with the photosensitive resin composition C, there was no liquid return after high-speed application, and the applicability was good.

[Evaluation of film thickness uniformity]
The film thickness uniformity of the substrate after coating was evaluated using a film thickness measuring device MCPD (manufactured by Otsuka Electronics Co., Ltd.). The photosensitive resin composition A could not be evaluated because it could not be applied at high speed. Moreover, the photosensitive resin composition B had a severe liquid return and could not be evaluated. On the other hand, the photosensitive resin composition C had a good result with little in-plane film thickness variation.

Claims (6)

A photosensitive resin composition for a color filter containing (A) a resin component, (B) a photosensitive agent , ( C) a surfactant , and (D) a colorant ,
The weight obtained by polymerizing at least a monomer represented by the following formula (c1) and a monomer represented by the following formula (c2) in a molar ratio of 4: 6 to 9: 1. a coalescing, the polymer of the mass average molecular weight of the color filter for the photosensitive resin composition is from 10,000 to 5000 0.

(In formulas (c1) and (c2), R ^1c and R ^3c each independently represent a hydrogen atom or a methyl group, R ^2c represents an alkylene group having 1 to 15 carbon atoms, and R ^4c represents 2 to 4 carbon atoms. R ^5c represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, Rf represents a perfluoroalkyl group having 1 to 5 carbon atoms, and p represents an integer of 1 to 50.) The surfactant (C) is, sp value 8.0~9.5 (cal ^/ cm ^{3) 1/2} in a claim 1 Symbol placement color filter photosensitive resin composition. The photosensitive resin composition for a color filter according to claim 1 or 2, wherein the (A) resin component contains a photopolymerizable resin, and the (B) photosensitive agent is a photopolymerization initiator. Wherein (D) any one color filter photosensitive resin composition according to claims 1-3 in which the coloring agent contains a black pigment. The color filter which has a pattern formed using the photosensitive resin composition for color filters of any one of Claim 1 to 4 . A liquid crystal display having the color filter according to claim 5 .

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