KR102050684B1 - Photosensitive resin composition, color filter and liquid crystal display - Google Patents

Abstract

The present invention can be obtained using a photosensitive resin composition having a high leveling effect and excellent in flatness even when it contains a colorant and capable of reducing the occurrence of defects and pin marks, and the photosensitive resin composition thereof. It is to provide a manufactured color filter and a liquid crystal display. The photosensitive resin composition which concerns on this invention contains (A) resin component, (B) photosensitive agent, and (C) surfactant. (C) As surfactant, it has a C1-C20 fluorinated alkyl group (however, it may be interrupted by ether bond, ester bond, carbonyl group, urethane bond) and a lipophilic group in a side chain, and a weight average molecular weight is 10,000-50,000. Phosphorus polymer is used.

Description

Photosensitive resin composition, color filter, and liquid crystal display display {PHOTOSENSITIVE RESIN COMPOSITION, COLOR FILTER AND LIQUID CRYSTAL DISPLAY}

This invention relates to the photosensitive resin composition and the color filter and liquid crystal display display manufactured using the photosensitive resin composition.

Since the photosensitive resin composition can obtain the resin pattern of a desired shape by exposure and image development, it is used for various uses, 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 apply | coated to a board | substrate, it is made to dry under reduced pressure (vacuum drying) by a vacuum drying apparatus (VCD), and it exposes and develops and forms a black matrix. Subsequently, application | coating, exposure, and image development are repeated for every photosensitive resin composition of each of R, G, and B colors, a pattern of each color is formed in a predetermined position, and a color filter is manufactured.

In such a use, making the film thickness of the photosensitive resin layer after application | coating uniform is one of the important subjects. In order to make the film thickness of the conventional photosensitive resin layer uniform, it is common to add surfactant which has a leveling effect to the photosensitive resin composition (refer Japanese patent document 1, 2 etc.).

[Patent Document 1] Japanese Patent Application Laid-Open No. 2005-107131 [Patent Document 2] Japanese Patent Application Laid-Open No. 2005-105045

However, especially in the case of the photosensitive resin composition containing a coloring agent, since the structure of the dispersing agent which disperse | distributes a coloring agent is similar to the structure of surfactant, the effect of surfactant is not fully acquired, and the application uniformity and flatness of a photosensitive resin layer worsen. there was. In addition, in recent years, high color density and high OD (Optical Density) values are desired in color filters and black matrices, and therefore, the amount of colorant added tends to increase, which leads to a decrease in fluidity of the photosensitive resin composition. The application uniformity and flatness of the resin layer became a factor worsening.

When the photosensitive resin layer is vacuum-dried, defects (defects) are generated in the photosensitive resin layer or when the heat treatment is applied, the marks (pin marks) of the proxy pins supporting the substrate may remain in the photosensitive resin layer. However, the inventors have investigated and studied that the type and nature of the surfactant is one of these factors.

The present invention has been made in view of such a conventional situation, and it is possible to obtain a photosensitive resin layer having a high leveling effect and excellent coating uniformity and flatness even when it contains a colorant, and also prevents occurrence of defects and pin marks. It aims at providing the photosensitive resin composition which can be reduced, and the color filter and liquid crystal display display manufactured using this photosensitive resin composition.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly researched about various types of surfactant in order to solve the said subject. The silicone-based surfactant has a lower leveling effect than the fluorine-based surfactant, and has a low applicability when the other photosensitive resin composition is applied onto the formed photosensitive resin layer, and there is a possibility that coating unevenness may occur. The review was further focused on. As a result, it has been found that the above problems can be solved by using a specific fluorine-based surfactant, and the present invention has been completed. Specifically, the present invention provides the following.

The 1st aspect of this invention is a photosensitive resin composition containing (A) resin component, (B) photosensitive agent, and (C) surfactant, Comprising: The said (C) surfactant is a C1-C20 fluorinated alkyl group (However, an ether bond. It may be interrupted by an ester bond, a carbonyl group, or a urethane bond.) And a lipophilic group in the side chain, and a photosensitive resin composition which is a polymer of a weight average molecular weight of 10,000-50,000.

The 2nd aspect of this invention is a color filter which has a pattern formed using the photosensitive resin composition which concerns on this invention.

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

<< photosensitive resin composition >>

The photosensitive resin composition which concerns on this invention contains (A) resin component, (B) photosensitive agent, and (C) surfactant. This photosensitive resin composition may be negative or positive type, and in the case of positive type, it may be a non-chemical amplification type or a chemical amplification type. Hereinafter, each component contained in the photosensitive resin composition is explained in full detail.

<(A) Resin Component>

The resin component (A) contained in the photosensitive resin composition according to the present invention differs depending on whether the photosensitive resin composition is negative, positive, or non-chemically amplified or chemically amplified.

When the photosensitive resin composition which concerns on this invention is negative type, alkali-soluble resin is used as (A) resin component, This alkali-soluble resin contains a photopolymerizable resin. As this photopolymerizable resin, resin which has an ethylenically unsaturated group is preferable.

Examples of the resin having an ethylenically unsaturated group include (meth) acrylic acid, fumaric acid, maleic acid, monomethyl fumarate, monoethyl fumarate, 2-hydroxyethyl (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, and 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, tetraethylene glycol Di (meth) acrylate, butylene glycol dimethacrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, te Methylol propane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1, Oligomers in which 6-hexanediol di (meth) acrylate, cardoepoxy diacrylate, and the like are polymerized; After (meth) acrylic acid is reacted with a polyester (meth) acrylate obtained by reacting (meth) acrylic acid to a polyester prepolymer obtained by condensing polyhydric alcohols with monobasic acid or polybasic acid, a compound having a polyol and two isocyanate groups Polyurethane (meth) acrylate obtained by making it react; Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolak type epoxy resin, resol type epoxy resin, triphenol methane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycol Epoxy (meth) acrylate resin etc. which are obtained by making (meth) acrylic acid react with epoxy resins, such as a cydyl ester, an aliphatic or alicyclic epoxy resin, an amine epoxy resin, and a dihydroxy benzene type epoxy resin, are mentioned. Moreover, resin which made polybasic acid anhydride react with epoxy (meth) acrylate resin can be used suitably.

Moreover, as resin which has an ethylenically unsaturated group, resin obtained by making the reaction material of an epoxy compound and an unsaturated group containing carboxylic acid compound further react with polybasic acid anhydride can be used suitably.

Especially, the compound represented by following formula (a1) is preferable. The compound represented by this formula (a1) is preferable at the point which itself has high photocurability.

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

In said formula (a2), R <^1a> represents a hydrogen atom, a C1-C6 hydrocarbon group, or a halogen atom each independently, R <^2a> represents a hydrogen atom or a methyl group each independently, W is a single bond or a following formula The group represented by (a3) is shown.

In addition, in said formula (a1), Y represents the residue remove | excluding the acid anhydride group (-CO-O-CO-) from dicarboxylic acid anhydride. Examples of the dicarboxylic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chloric anhydride, methyltetrahydrophthalic anhydride, Glutaric anhydride etc. are mentioned.

In addition, in said formula (a1), Z represents the residue remove | excluding two acid anhydride groups from tetracarboxylic dianhydride. Examples of tetracarboxylic dianhydride include pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride and the like.

In addition, in said formula (a1), n represents the integer of 0-20.

It is preferable that it is 10-150 mgKOH / g, and, as for the acid value of resin which has an ethylenically unsaturated group, it is more preferable that it is 70-110 mgKOH / g. By making an acid value 10 mgKOH / g or more, sufficient solubility to a developing solution can be obtained. Moreover, sufficient sclerosis | hardenability can be obtained by setting an acid value to 150 mgKOH / g or less, and surface quality can be made favorable.

Moreover, it is preferable that the weight average molecular weight (Mw: measured value by polystyrene conversion of a gel permeation chromatography (GPC). Same in this specification.) Of resin which has an ethylenically unsaturated group is 1,000-40,000, It is 2,000- It is more preferable that it is 30,000. By setting the weight average molecular weight to 1,000 or more, heat resistance and film strength can be improved. Moreover, sufficient solubility to a developing solution can be obtained by making a weight average molecular weight 40,000 or less.

On the other hand, when the photosensitive resin composition which concerns on this invention is positive type, the non-chemically amplified photosensitive resin composition and the chemically amplified photosensitive resin composition exist.

When the photosensitive resin composition which concerns on this invention is positive type and non-chemically amplified type, alkali-soluble resin is used as (A) resin component. As this alkali-soluble resin, phenols (phenol, m-cresol, p-cresol, xylenol, trimethyl phenol, etc.), and aldehydes (formaldehyde, formaldehyde precursor, propionaldehyde, 2-hydroxybenzaldehyde, 3-hydride) Novolak resin obtained by condensing oxybenzaldehyde, 4-hydroxybenzaldehyde and the like) and / or ketones (methyl ethyl ketone, acetone and the like) in the presence of an acidic catalyst; Acrylic resins obtained by polymerizing (meth) acrylic acid or its derivatives; Homopolymers of hydroxystyrene or copolymers of hydroxystyrene and other styrene monomers; And copolymers of hydroxy styrene with (meth) acrylic acid or derivatives thereof.

Among them, thermal crosslinking such as (meth) acrylic acid derivatives having a hydroxyphenyl group such as p-hydroxyphenyl (meth) acrylate and p-hydroxyphenylethyl (meth) acrylate and glycidyl (meth) acrylate Copolymers of (meth) acrylic acid derivatives having a group are preferred.

It is preferable that it is 2,000-50,000, and, as for the weight average molecular weight of such alkali-soluble resin, it is more preferable that it is 5,000-30,000. By making a weight average molecular weight 2,000 or more, it becomes possible to form easily in a film form. Moreover, sufficient solubility to a developing solution can be obtained by making a weight average molecular weight into 50,000 or less.

Moreover, when the photosensitive resin composition which concerns on this invention is positive type or chemically amplified type, resin which alkali alkali solubility increases by action of an acid is used as (A) resin component. Alkali-soluble resin protected with an acid dissociable, dissolution inhibiting group is used as such resin, and many conventionally known resins are used for resist resins, such as for ArF excimer laser and KrF excimer laser.

It is preferable that the weight average molecular weight of resin which alkali solubility increases by the action of such an acid is 2,000-50,000, It is more preferable that it is 3,000-30,000, It is further more preferable that it is 4,000-20,000, Especially it is 5,000-20,000 desirable. By setting it as said range, when it uses, for example as a resist composition, it can fully acquire solubility with respect to a resist solvent, and dry etching resistance improves and the cross-sectional shape of the resin pattern obtained also becomes favorable.

<(E) Photopolymerizable Monomer>

When the photosensitive resin composition which concerns on this invention is negative type, it is preferable that this photosensitive resin composition contains (E) photopolymerizable monomer in addition to the photopolymerizable resin as (A) resin component. As this (E) photopolymerizable monomer, the monofunctional monomer or polyfunctional monomer which has an ethylenically unsaturated group is preferable.

As a monofunctional monomer, (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymeth Methoxymethyl (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-methylpropanesulfonic acid, tert-butylacrylamidesulfonic 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) acrylic Latex, 2-phenoxy-2-hydroxypropyl (meth) a Relate, 2- (meth) acryloyloxy-2-hydroxypropylphthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidyl ( Meta) acrylates, 2,2,2-trifluoroethyl (meth) acrylates, 2,2,3,3-tetrafluoropropyl (meth) acrylates, and half (meth) acrylates of phthalic acid derivatives; Can be mentioned. These monofunctional monomers may be used independently or may be used in combination of 2 or more type.

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 ( Meta) 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 (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipene Erythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydrate Roxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglyc Cydyl ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (ie tolylene diisocyanate), trimethylhexamethylene diisocyanate and hexamethylene Reactant of diisocyanate and 2-hydroxyethyl (meth) acrylate, methylene bis (meth) acrylamide, (meth) acrylamide methylene ether, the axis of polyhydric alcohol and N-methylol (meth) acrylamide Multi-functional monomers, such as water or the like can be given triacrylate formal. These polyfunctional monomers may be used independently or may be used in combination of 2 or more type.

(E) When it contains a photopolymerizable monomer, it is preferable that it is 5-50 weight% with respect to solid content of the photosensitive resin composition, and it is more preferable that it is 10-40 weight%. By setting it as said range, there exists a tendency which is easy to obtain the balance of sensitivity, developability, and resolution.

<(B) Photosensitive Agent>

The photosensitive agent (B) contained in the photosensitive resin composition which concerns on this invention differs depending on whether this photosensitive resin composition is negative type | mold, positive type, or non-chemically amplified type, or chemically amplified type.

When the photosensitive resin composition which concerns on this invention is negative type, a photoinitiator is used as (B) photosensitive agent.

Examples of the photopolymerization initiator include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy Hydroxy-2-methyl-1-propane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2- Hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-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-trimethylbenzoyldiphenylphosphineoxide, 4-benzoyl-4 ' -Methyldimethylsulfide, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid methyl, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid butyl, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2 Isoamylbenzoic acid, benzyl-β-methoxyethyl Cetal, benzyldimethyl ketal, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2,4-diethyl thioxanthone, 2-chlorothioke Santone, 2,4-dimethyl thioxanthone, 1-chloro-4-propoxy thioxanthone, thioxanthene, 2-chloro thioxanthene, 2,4-diethyl thioxanthene, 2-methyl thioxanthene , 2-isopropyl thioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene perox Seed, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -imida Zolyl dimer, benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl 4-methoxy benzophenone, benzyl, benzoin, benzoin methyl ether, ben Inethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylamino Propiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α, α -Dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberon, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis- (9-acridyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) propane, p-methoxytri Azine, 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 (trichloro) Rhomethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-di Ethylamino-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-trichloro Methyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-tri Azine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine and 2,4-bis-trichloromethyl-6- (2-bro Mother-4-methoxy) styrylphenyl-s-triazine, etc. are mentioned. Especially, it is especially preferable to use an oxime system photoinitiator from a viewpoint of a sensitivity. These photoinitiators may be used individually or may be used in combination of 2 or more type.

It is preferable that content of this photoinitiator is 0.1-50 weight% with respect to solid content of the photosensitive resin composition. By setting it as the said range, sufficient heat resistance and chemical-resistance can be obtained, and a film formation ability can be improved and a photocuring defect can be suppressed.

On the other hand, when the photosensitive resin composition which concerns on this invention is a positive type and a non-chemically amplified type, the quinonediazide group containing compound is used as a photosensitive agent (B).

Examples of the quinone diazide group-containing compound include phenol compounds such as 2,3,4-trihydroxybenzophenone and 2,3,4,4'-tetrahydroxybenzophenone, and naphthoquinone-1,2-diazide. Fully esterified or partially esterified products of naphthoquinone diazide sulfonic acid compounds such as -5-sulfonic acid and naphthoquinone-1,2-diazide-4-sulfonic acid; These nucleosubstituted derivatives such as orthobenzoquinone diazide, orthonaphthoquinone diazide or orthoanthraquinone diazide, or orthonaphthoquinone diazide sulfonic acid esters; Orthoquinonediazide sulfonyl chloride and a compound having a hydroxyl group or an amino group, for example, phenol, p-methoxyphenol, dimethylphenol, hydroquinone, bisphenol A, naphthol, pyrocatechol, pyrogarol, pyrogarol monomethyl ether And pyrogarol-1,3-dimethylether, a molar asset, a molar esterified or etherified leaving some hydroxyl groups, and reaction products such as aniline and p-aminodiphenylamine. These quinonediazide group containing compounds may be used independently, or may be used in combination of 2 or more type.

It is preferable that content of this quinone diazide group containing compound is 5-50 weight part with respect to 100 weight part of (A) resin components. By setting it as said range, it becomes possible to reduce the film | membrane reduction amount after forming a resin pattern by improving resolution, and it becomes possible to provide a suitable sensitivity and transmittance | permeability.

Moreover, when the photosensitive resin composition which concerns on this invention is a positive type and a chemical amplification type, the photoacid generator is used as (B) photosensitive agent.

As a photo-acid generator, many things conventionally known are used for resin for resists, such as for ArF excimer laser and KrF excimer laser. For example, onium salt acid generators, such as an iodine salt and a sulfonium salt, an oxime sulfonate acid generator, bisalkyl or bisaryl sulfonyl diazomethanes, poly (bissulfonyl) diazomethanes, etc. Many kinds of diazomethane-based acid generators, nitrobenzylsulfonate-based acid generators, iminosulfonate-based acid generators, disulfone-based acid generators and the like can be used.

It is preferable that it is 0.5-30 weight part with respect to 100 weight part of (A) resin components, and, as for content of this photo-acid generator, it is more preferable that it is 1-20 weight part. Pattern formation is fully performed by setting it as said range. Moreover, since a uniform solution is obtained and storage stability becomes favorable, it is preferable.

<(C) surfactant>

(C) surfactant contained in the photosensitive resin composition which concerns on this invention has a C1-C20 fluorinated alkyl group (however, it may be interrupted by ether bond, ester bond, carbonyl group, urethane bond) and a lipophilic group in a side chain. Polymer.

The fluorinated alkyl group is not particularly limited as long as it is 1 to 20 carbon atoms, and includes an ether bond (-O-), an ester bond (-CO-O-), a carbonyl group (-CO-), and a urethane bond (-NH-CO-O-). Although not interrupted by these groups, i.e., -C _k H _l F _m (k represents an integer of 1 to 20, l represents an integer of 0 to 40, and m represents an integer of 1 to 41). And l + m = 2k + 1.).

Here, recently, compounds having a perfluoroalkyl group having a fluorinated carbon number of 7 or more have been reported to have ecological effects such as carcinogenicity, and thus may be subject to the important New Use Rule (SNUR), which is a US ecological impact rule. have. Therefore, it is preferable that a fluorinated alkyl group contains the C1-C5 perfluoroalkyl group, and the remaining carbon atoms are not fluorinated. As for carbon number of a perfluoroalkyl group, it is more preferable that it is 3-5.

On the other hand, although a lipophilic group contains what is contained in a conventionally well-known nonionic surfactant, it is preferable to include the alkylene group interrupted by the ether bond, ester bond, or carbonyl group. Especially, it is preferable that polyalkyleneoxy group (polyethyleneoxy group, polypropyleneoxy group, polybutyleneoxy group etc.) is included.

Although the molar ratio of a fluorinated alkyl group and a lipophilic group changes also with the composition of the photosensitive resin composition, it is preferable that it is 4: 6-9: 1, It is more preferable that it is 4: 6-8: 2, It is more preferable that it is 5: 5-7: It is more preferable that it is three.

Such a surfactant can be obtained by polymerizing at least the monomer which has the said fluorinated alkyl group, and the monomer which has the said lipophilic group. As a monomer which has a fluorinated alkyl group and a monomer which has a lipophilic group, the monomer represented by following formula (c1) and (c2) is preferable, respectively.

In the formula (c1), R ^1c represents a hydrogen atom or a methyl group, R ^2c represents a linear, branched, or cyclic alkylene group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, and Rf represents carbon number 1-5, Preferably it is a C3-C5 perfluoroalkyl group.

In the formula (c2), R ^3c represents a hydrogen atom or a methyl group, R ^4c represents an alkylene group having 2 to 4 carbon atoms, R ^5c represents a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms. Indicates.

In addition, in said formula (c2), p represents the integer of 1-50.

Specific examples of the monomer represented by the 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, etc. are mentioned.

Moreover, as a specific example of the monomer represented by said formula (c2), (meth) acrylic-acid methoxy polyethyleneglycol ester [for example, the number (r) of ethylene glycol repeating units is 1-50], (meth) Acrylic methoxy polypropylene glycol ester [For example, the number (r) of a propylene glycol repeating unit is 1-50], (meth) acrylic-acid methoxy poly (ethylene-propylene) glycol ester [For example, ethylene glycol Total sum of the number of repeating units and the number of propylene 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 sum total (r) of the number of the tetramethylene glycol repeating units is 2-50], (meth) acrylic-acid butoxy poly (ethylene-propylene) glycol ester [For example, the number of ethylene glycol repeating units and a propylene glycol repeat Sum of the number of units (r) is 2-50], (meth) acrylic acid octoxy poly (ethylene-propylene) glycol ester [For example, the sum (r) of the number of ethylene glycol repeating units and the number of propylene glycol repeating units is 2 -50], (meth) acrylic-acid lauoxy polyethyleneglycol ester [For example, the number (r) of ethylene glycol repeating units is 2-50], (meth) acrylic-acid lauxy poly (ethylene propylene) glycol Ester [for example, the sum (r) of the number of ethylene glycol repeating units and the number of propylene glycol repeating units is 2-50], polyethyleneglycol (meth) acrylate, polypropylene glycol (meth) acrylate, polyethylene To glycol ester polypropylene glycol (meth) acrylate, polyethylene glycol polybutylene glycol (meth) acrylate, polystyrylethyl (meth) acrylate, or light ester HOA-MS, the Kyoeisha Chemical company Ster HOMS etc. are mentioned.

It is preferable that it is 4: 6-9: 1, and, as for the molar ratio at the time of superposing | polymerizing the monomer represented by said formula (c1) and the monomer represented by said formula (c2), it is more preferable that it is 4: 6-8: 2. , 5: 5-7: 3 are more preferable.

In addition to the monomer represented by the said Formula (c1) and the monomer represented by the said Formula (c2), (C) surfactant has superposed | polymerized the (meth) acrylic-acid alkylester in the range which does not impair the effect of this invention. You can do it. As a specific example of the (meth) acrylic-acid alkylester, 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, and the like.

The surfactant may be any of a random polymer and a graft polymer, but is preferably a graft polymer. By setting it as a graft polymer, a leveling effect can be heightened more, maintaining compatibility with alkali-soluble resin (A). Moreover, in the case of a graft polymer, there is little possibility that it will become cloudy even if it increases content.

It is preferable that the sp value of surfactant is 8.0-9.5 (cal / cm <3>) ^1/2 . By setting it as said range, the compatibility of 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.

Moreover, the weight average molecular weights of resin contained in surfactant are 10,000-50,000, and it is preferable that it is 10,000-30,000. In general, surfactants made of a compound having a low carbon number of a fluorinated alkyl group have a low leveling effect. However, when the weight average molecular weight is in the above range, a sufficient leveling effect can be obtained even when the carbon number of the fluorinated alkyl group is less than 5, for example. have. Moreover, the photosensitive resin layer excellent in coating uniformity and flatness can be obtained by making a weight average molecular weight into the said range.

That is, in general, the surfactant exhibits the surfactant effect by having an insoluble site and a soluble site for the solvent. However, in the low molecular weight surfactant, when the carbon number fluorinated alkyl group was used as an insoluble site, the effect as an insoluble site was too small to obtain a sufficient surfactant effect. In addition, when the ratio of insoluble sites was increased, sufficient soluble sites could not be obtained because fewer soluble sites were obtained. On the other hand, when the fluorinated alkyl group having a low carbon number is used, the amount of the insoluble moiety (fluorinated alkyl group) in one molecule of the surfactant can be increased by setting the weight average molecular weight of the surfactant to 10,000 or more, so that the solubility in the solvent It can be dropped and the surfactant activity can be secured. Moreover, since the ratio of a soluble site | part can be taken large, the density | concentration of an alkyl fluoride group can be prevented by 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 make it hard to become cloudy.

Moreover, when spin-coating a photosensitive resin composition, a photosensitive resin composition is dripped at a board | substrate, and a board | substrate is rotated and apply | coated. In the case of using a conventional low molecular weight surfactant, it is possible to erase the streaks, but since liquid pooling of the photosensitive resin composition occurs at the end of the substrate, a protruding portion of the photosensitive resin composition is finally formed at the end. .

That is, application | coating uniformity and flatness will become inferior. On the other hand, in the photosensitive resin composition which concerns on this invention, since the weight average molecular weight uses surfactant more than 10,000, the protruding of an edge part can also be eliminated also in spin coating. In particular, when the solid content concentration in the photosensitive resin composition is 30 weight% or more, there exists a big effect in eliminating the protruding edge part.

Moreover, when apply | coating with a slit coater, there exists a tendency to lower solid content concentration of the photosensitive resin composition generally. When the solid content concentration of the photosensitive resin composition is made low, since the fluidity | liquidity of the photosensitive resin composition becomes large, the film thickness of the apply | coated photosensitive resin composition tends to become nonuniform. Moreover, although there exists a process of drying the apply | coated photosensitive resin composition, liquid return to the center part from the edge part of a board | substrate at the time of a drying process is influenced by the influence of surface tension, temperature, and density change at the time of drying which apply | coated the photosensitive resin composition apply | coated once. It arises, and the uniformity of a film thickness becomes easy to worsen. In particular, when a large substrate was used, the uniformity of the film thickness was largely affected. On the other hand, since the photosensitive resin composition which concerns on this invention uses surfactant whose weight average molecular weight is 10,000 or more, film thickness uniformity can be improved.

It is preferable that content of this (C) surfactant is 0.005-1 weight% with respect to whole quantity of the photosensitive resin composition, It is more preferable that it is 0.01-0.5 weight%, More preferably, 0.05-0.2 weight%. By setting it as said range, the photosensitive resin layer excellent in coating uniformity and flatness can be obtained. In addition, even when producing a color filter, the occurrence of defects and pin marks can be reduced.

Moreover, the photosensitive resin composition which concerns on this invention may contain the other conventionally well-known surfactant in the range which does not impair the effect of this invention.

<(D) Colorant>

The photosensitive resin composition which concerns on this invention may contain the (D) coloring agent. As this (D) coloring agent, the compound classified as pigment in the color index (CI; The Society of Dyers and Colourists, for example), specifically the following color index (CI) number And the like are mentioned. This coloring agent may be used independently and may be used in combination of 2 or more type in order to adjust color tone.

C.I. Pigment Yellow 1 (hereinafter, "CI Pigment Yellow" is the same and only numbers are written.), 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 numbers are listed.), 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 the same and lists only the numbers), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50;

C.I. Pigment Red 1 (hereinafter, "CI Pigment Red" is the same and writes the number only), 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, 179, 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, "C.I. Pigment Blue" is the same and describes only the numbers.), 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.

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

It is preferable to use carbon black or titanium black as a black pigment. 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, complex oxides, metal emulsions, metal lactates, metal carbonates, and the like can also be used.

As carbon black, well-known carbon black, such as channel black, furnace black, thermal black, and lamp black, can be used, but channel black can be suitably used because of its excellent light shielding properties. Moreover, resin coated carbon black can also be used. Specifically, a resin-coated carbon black obtained by mixing a carbon black with a resin having reactivity with a carboxyl group, a hydroxyl group, a carbonyl group present on the surface of the carbon black, and heating at 50 to 380 ° C, or a water-organic solvent mixture system or water- The resin coating carbon black etc. which were obtained by disperse | distributing an ethylenic monomer to surfactant mixed system and carrying out radical polymerization or radical copolymerization in presence of a radical polymerization initiator are mentioned. Since the resin-coated carbon black has lower conductivity than carbon black without resin coating, when used as a color filter such as a liquid crystal display, there is less leakage of current and a highly reliable display of low power consumption is formed. can do.

Moreover, you may add an organic pigment as said auxiliary pigment to said inorganic black pigment. The following effects can be acquired by suitably selecting and adding the organic pigment which has a complementary color of an inorganic black pigment. For example, carbon black has a reddish black color. Therefore, by adding a blue-colored organic pigment that is a red complementary color to the carbon black, the reddish color of the carbon black disappears to give a more preferable black color as a whole. The organic pigment is preferably 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 black pigment and the organic pigment.

As said inorganic black pigment and organic pigment, the solution which disperse | distributed the pigment to appropriate density | concentration normally using a dispersing agent is used. For example, as the inorganic black pigment, carbon dispersion CF black (containing 20% carbon concentration) manufactured by Mikuni Dyestuffs Co., carbon dispersion CF black (containing 24% high resistance carbon) manufactured by Mikuni Dyestuffs Co., Ltd. and titanium black dispersion CF manufactured by Mikuni Dyestuff Co., Ltd. And black (containing 20% black titanium pigment). Moreover, as an organic pigment, blue pigment dispersion liquid CF blue (20% of blue pigment containing) made by Mikuni dye company, violet pigment dispersion liquid (containing 10% of violet pigment) made by Mikuni dye company, etc. are mentioned, for example. Moreover, a urethane resin type polymeric dispersant can be used suitably as a dispersing agent.

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

Moreover, when using a black pigment as (D) coloring agent, it is preferable to adjust so that the OD value per film thickness of 1 micrometer of the film | membrane formed may be 3.5 or more, Preferably it is 4.0 or more. When the OD value per film thickness of 1 micrometer is 3.5 or more, sufficient display contrast can be obtained when it is used for the black matrix of a liquid crystal display, and the required performance can be obtained.

Conventionally, in the photosensitive resin composition containing such a coloring agent, since the dispersing agent which has a structure similar to surfactant is contained, even if surfactant was added by the influence of a dispersing agent, sufficient leveling effect was not acquired. On the other hand, since the said (C) surfactant has a high leveling effect, even if the photosensitive resin composition contains a coloring agent, the photosensitive resin layer excellent in application | coating uniformity and flatness can be obtained.

<(S) solvent>

It is preferable that the photosensitive resin composition which concerns on this invention contains the (S) solvent for dilution. As this (S) solvent, 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, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tri (Poly) alkylene glycol monoalkyl such as propylene glycol monomethyl ether and tripropylene glycol monoethyl ether Ethers; (Poly) alkylenes such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate Glycol monoalkyl ether acetates; Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; Lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2 -Hydroxy-3-methyl butyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 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, methyl pyruvate, ethyl pyruvate, Other esters such as n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutyrate; Aromatic hydrocarbons such as benzene, toluene and xylene; Amides such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and the like. Especially, it is preferable to use at least 1 sort (s) of cyclohexanone and propylene glycol monomethyl ether acetate. These solvents may be used alone or in combination of two or more thereof.

(S) When it contains a solvent, the content of the content of solid content concentration of the photosensitive resin composition becomes like this. 1-50 weight% is preferable, and the amount which becomes 5-30 weight% is more preferable.

<Preparation method of the photosensitive resin composition>

The photosensitive resin composition which concerns on this invention can be obtained by mixing all the above components and an additive with a stirrer as needed. You may filter using a filter so that the obtained mixture may be uniform.

≪Pattern formation method≫

When forming a resin pattern using the photosensitive resin composition which concerns on this invention, first, non-contacts, such as a contact transfer type | mold coating apparatus, such as a roll coater, a reverse coater, and a bar coater, or a spinner (rotary coating apparatus), a slit coater, a curtain flow coater, etc. The photosensitive resin composition which concerns on this invention is apply | coated on the board | substrate which consists of glass, a polyethylene terephthalate, an acrylic resin, polycarbonate, etc. using a type | mold coating apparatus.

Next, the applied photosensitive resin composition is dried to form a photosensitive resin layer. As a drying method, it vacuum-dried at room temperature using a vacuum drying apparatus (VCD), for example, and after that, it heats for 60 to 120 second on 80-120 degreeC, Preferably it is 90-100 degreeC on a hotplate. Etc. can be mentioned.

Subsequently, this 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 irradiate changes also with the composition of the photosensitive resin composition, it is preferable that it is 30-2,000mJ / cm <2>.

Next, the photosensitive resin layer after exposure is developed with a developing solution, and a resin pattern of a desired shape is obtained. The developing method may be an immersion method or a spray method. Examples of the developing solution include organic compounds such as monoethanolamine, diethanolamine and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salts.

Then, the resin pattern after image development is heated (post-baked), for example at 220-250 degreeC. When the apply | coated photosensitive resin composition is a negative type, it is preferable to fully expose the resin pattern formed at this time. The resin pattern of a predetermined shape can be obtained by the above.

≪Color filter≫

The color filter which concerns on this invention has a pattern formed using the photosensitive resin composition which concerns on this invention. In order to manufacture this color filter, first, a resin pattern is formed according to the said pattern formation method using the photosensitive resin composition in which black pigment was disperse | distributed. This resin pattern turns into a black matrix. Next, pattern formation is performed similarly to the photosensitive resin composition in which the red, green, and blue coloring agent was disperse | distributed, and the pixel pattern of each color is formed. Thereby, a color filter is manufactured.

In the manufacture of a color filter, ink of red, green, and blue colors may be discharged from an inkjet nozzle in each area partitioned by a black matrix, and the accumulated ink may be cured with heat or light to produce a color filter. have.

When manufacturing a color filter using the photosensitive resin composition containing a conventional coloring agent, the flat photosensitive resin layer was not obtained by the dispersing agent contained in the photosensitive resin composition. In particular, when there was much content of a coloring agent, the fluidity | liquidity of the photosensitive resin composition fell and the coating uniformity and flatness of the photosensitive resin layer worsened. In the case of manufacturing a color filter, defects (defects) are generated in the photosensitive resin layer when the photosensitive resin layer is vacuum dried, or the marks (pin marks) of the proxy pins supporting the substrate when the heat treatment is applied may be photosensitive. There was something left in the strata. On the other hand, according to the photosensitive resin composition of this invention, even if it contains a coloring agent, the photosensitive resin layer excellent in application | coating uniformity and flatness can be obtained, and generation | occurrence | production of a defect and a pin mark can be reduced.

≪Liquid crystal display display≫

The liquid crystal display display which concerns on this invention has a color filter which concerns on this invention. In order to manufacture this liquid crystal display, the said color filter is first formed on one board | substrate, and then an electrode, a spacer, etc. are formed sequentially. Then, an electrode or the like is formed on the other substrate, and both are bonded together, and then a predetermined amount of liquid crystal is injected and sealed. Thereby, a liquid crystal display is manufactured.

Since the photosensitive resin composition which concerns on this invention has high leveling property, even if it contains a coloring agent, the photosensitive resin layer excellent in coating uniformity and flatness can be obtained. Moreover, also when manufacturing the color filter of a liquid crystal display display, generation | occurrence | production of the defect in a photosensitive resin layer and a pin mark can be reduced.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure for demonstrating the width | variety of the stain in the Example of this invention.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail with reference to an Example. In addition, this invention is not limited to a following example at all.

<Examples 1-7, Comparative Examples 1-10>

[(A) Synthesis of alkali-soluble resin]

First, 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 were put into a 500 ml four-neck flask. It heated and melt | dissolved at 90-100 degreeC, blowing air into this at a rate of 25 ml / min. Next, the solution was gradually warmed up to a cloudy state, heated to 120 ° C, and completely dissolved. At this time, the solution gradually became transparent viscous, but continued stirring as it was. The acid value was measured during this time, and heating and stirring were continued until it became less than 1.0 mgKOH / g. It took 12 hours for the acid value to reach the target value. Then, it cooled to room temperature and obtained the bisphenol fluorene type epoxy acrylate which is colorless and transparent and a solid phase is represented by following formula (a4).

[Tue 5]

Then, 600 g of 3-methoxybutyl acetate is added to and dissolved in 307.0 g of the bisphenol fluorene type epoxy acrylate thus obtained, and then 80.5 g of benzophenone tetracarboxylic dianhydride and 1 g of tetraethylammonium bromide are mixed. It heated up gradually and made it react at 110-115 degreeC for 4 hours. After confirming the 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 a resin (A-1). Disappearance of the acid anhydride group was confirmed by IR spectrum. The weight average molecular weight was 3,400.

[Preparation of Photosensitive Resin Composition]

As shown in Table 1 below, (S) solvent was added to (A) alkali-soluble resin, (E) photopolymerizable monomer, (C) surfactant, and (D) coloring agent, and solid content concentration was 15 weight% or After adjusting to 17 weight% and mixing in a stirrer for 2 hours, it filtered by the 5 micrometer membrane filter, and prepared the photosensitive resin composition. In addition, the compounding quantity of each component of Table 1 is "weight part".

TABLE 1

The detail about (A) alkali-soluble resin, (B) photosensitive agent, (D) coloring agent, and (S) organic solvent which were used in Table 1 is as follows.

(A) -1: Preparation liquid which 3-methoxybutyl acetate was added to resin (A-1), and adjusted to 50 weight% of solid content concentration.

(E) -1: dipentaerythritol hexaacrylate

(B) -1: IRGACURE OXE 02 (product of Chiba specialty chemicals company)

(B) -2: IRGACURE 369 (product of Chiba specialty chemicals company)

(D) -1: Carbon black (manufactured by Mikuni Dyestuffs Co., Ltd., carbon concentration: 55%, solvent: 3-methoxybutyl acetate)

(S) -1: 3-methoxybutyl acetate / cyclohexanone / propylene glycol monomethyl ether acetate = 60/20/20 (weight ratio)

In addition, the detail about the (C) surfactant used in Table 1 is as showing in following Table 2. In Table 2, the number in parentheses in the copolymer of (C4) -1-(C4) -9 shows the ratio of the supply amount of each monomer when the monomer total amount at the time of synthesize | combining a copolymer is 100 weight part. In addition, (C8) -1 and Si-1 are manufactured by Kyoisha Chemical Co., Ltd.

TABLE 2

<Evaluation>

[Stain width evaluation]

After apply | coating the photosensitive resin composition of Examples 1-7 and Comparative Examples 1-10 which were obtained above on the glass substrate (1737 glass) of 100 mm x 100 mm using a spin coater (made by MIKASA Corporation), respectively, on a hotplate It mounted on the 5 mm width glass piece which installed, and prebaked at 90 degreeC for 120 second. The stain width at that time was measured using the surface roughness measuring instrument Surfcoder SE-2300 (manufactured by Kosaka Research Institute). The results are written together in Table 1.

In addition, the width | variety of a stain | membrane is made into the spot width (nm) by measuring the location shown in FIG. Since only heat is transmitted from the glass piece to the glass substrate, convection occurs from the heated place, causing the photosensitive resin composition to bounce off, and this bounce becomes the bead. The less the sticking out, that is, the less the portion where the film thickness is extremely thin, the better the coating uniformity and flatness.

[Pin mark evaluation]

Hot plate after apply | coating the photosensitive resin composition of Examples 1-7 and Comparative Examples 1-10 obtained above which were respectively applied to the glass substrate of 680 mm x 880 mm using spin-coating apparatus TR-45310 (made by Tokyo-Oka Industry Co., Ltd.). It mounted on the lift pin provided on the surface, and prebaked at 120 degreeC for 100 second, and obtained the photosensitive resin layer which has a film thickness of 1.3 micrometers. About this photosensitive resin layer, the pin trace of the surface of the photosensitive resin layer was evaluated using "AOI" (made by TAKANO). Evaluation criteria are as follows and the result is written together in Table 1.

◎ ： There is no pin mark

○: Thin pin marks are visible, but no problem

△ ： Small amount of pin mark is shown

×: Many pin marks are shown

As Table 1 shows, in Examples 1-7 using a specific surfactant, even if it contained a coloring agent, the photosensitive resin layer excellent in coating uniformity and flatness was obtained. Moreover, the pin trace was not confirmed on the surface. On the other hand, in Comparative Examples 1 to 10 using other surfactants, the stain width was large, and coating uniformity and flatness were bad. In addition, pin marks remained on the surface.

[High speed applicability evaluation]

In the photosensitive resin composition A (solid content concentration 15 weight%) similar to the comparative example 1, and the photosensitive resin composition B which changed solid content concentration from 15 weight% to 12 weight% in Comparative Example 1, the photosensitive resin composition of Example 2, (A) The compounding quantity of alkali-soluble resin is changed into 20 weight part, (E) The compounding quantity of a photopolymerizable monomer is changed into 8 weight part, (B) The photosensitizer is changed into 10 weight part only by (B) -1, (D ) The amount of the coloring agent was changed to 120 parts by weight, the organic solvent was changed to 3-methoxybutyl acetate / cyclohexanone / propylene glycol monomethyl ether acetate = 65/25/10 (weight ratio), and the solid content concentration was 12% by weight. The photosensitive resin composition C adjusted by the above was prepared, respectively. High-speed coating (coating rate: 250 nm / sec, application | coating GAP) on this 2160 mm x 2460 mm glass substrate (thickness 0.7 mm) using this non-spin type coating apparatus TR130200FC (made by Tokyo-Oka Industry Co., Ltd.) : 130 µm), followed by drying under reduced pressure at 13 Pa for 10 seconds to obtain a photosensitive resin layer. As a result, liquid breakup generate | occur | produced in the photosensitive resin composition A, and high speed application | coating could not be performed. In the photosensitive resin composition B, although high speed application was possible, liquid return generate | occur | produced immediately after application | coating, and the photosensitive resin layer waved (liquid return width 3-4 mm). On the other hand, in the photosensitive resin composition C, there was no liquid return after high speed application | coating, and applicability | paintability was favorable.

[Film Thickness Uniformity Evaluation]

The film thickness uniformity of the board | substrate after application | coating was evaluated using the film thickness measuring apparatus MCPD (made by Otsuka Electronics Co., Ltd.). In addition, since the photosensitive resin composition A could not be apply | coated at high speed, it could not be evaluated. Moreover, liquid return was intense and the photosensitive resin composition B could not be evaluated. On the other hand, the photosensitive resin composition C had little in-plane film thickness nonuniformity, and was a favorable result.

Claims (20)

As a photosensitive resin composition for color filter formation containing (A) resin component, (B) photosensitive agent, and (C) surfactant,
The said (C) surfactant has a C3-C20 fluorinated alkyl group (however, it may be interrupted by an ether bond, an ester bond, a carbonyl group, a urethane bond), and a lipophilic group in a side chain, and the said fluorinated alkyl group has C3-C5 A perfluoroalkyl group, the molar ratio of the fluorinated alkyl group to the lipophilic group is 5: 5 to 7: 3, a weight average molecular weight of 10,000 to 50,000 polymer, and the sp value is 8.0 to 9.5 (cal / Cm 3) Photosensitive resin composition, which is ^1/2 . As a photosensitive resin composition containing (A) resin component, (B) photosensitive agent, and (C) surfactant,
The said (C) surfactant has a C3-C20 fluorinated alkyl group (however, it may be interrupted by an ether bond, an ester bond, a carbonyl group, a urethane bond), and a lipophilic group in a side chain, and the said fluorinated alkyl group has C3-C5 A perfluoroalkyl group, the molar ratio of the fluorinated alkyl group to the lipophilic group is 5: 5 to 7: 3, and a weight average molecular weight is 10,000 to 50,000 polymer,
The said photosensitive resin composition is a negative photosensitive resin composition for color filter formation,
Said (B) photosensitive agent is an oxime ester type photoinitiator, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino propane-1-one, or 2-benzyl-2- dimethylamino-1- The photosensitive resin composition containing (4-morpholinophenyl) -butan-1-one. The method according to claim 2,
The photosensitive agent (B) is ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (o-acetyloxime), 1-phenyl-1, 2-propanedione-2- (o-ethoxycarbonyl) oxime, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, or 2-benzyl-2- The photosensitive resin composition which is dimethylamino-1- (4-morpholinophenyl) -butan-1-one. The method according to claim 1 or 2,
The photosensitive resin composition in which the said (A) resin component contains a photopolymerizable resin and the said photopolymerizable resin contains the compound represented by following formula (a1).

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

(In formula (a2), R <^1a> represents a hydrogen atom, a C1-C6 hydrocarbon group, or a halogen atom each independently, R <^2a> represents a hydrogen atom or a methyl group each independently, W represents a single bond or the following The group represented by formula (a3) is represented.)

(In addition, in said Formula (a1), Y represents the residue remove | excluding the acid anhydride group (-CO-O-CO-) from dicarboxylic acid anhydride. In said Formula (a1), Z represents from tetracarboxylic dianhydride. The residue except two acid anhydride groups is shown, n shows the integer of 0-20 in said Formula (a1).) The method according to claim 1 or 2,
The fluorinated alkyl group is represented by -C _k H _l F _m (k represents an integer of 3 to 20, l represents an integer of 0 to 34, m represents an integer of 7 to 41, and l + m = 2k + 1). Photosensitive resin composition. delete The method according to claim 1 or 2,
The photosensitive resin composition in which the said lipophilic group contains the alkylene group interrupted by the ether bond, the ester bond, or the carbonyl group. The method according to claim 1 or 2,
The photosensitive resin composition in which the said lipophilic group contains a polyalkyleneoxy group. delete The method according to claim 1 or 2,
The photosensitive resin composition whose said (C) surfactant is a polymer which polymerized the monomer which has the said fluorinated alkyl group, and the monomer which has the said lipophilic group at least. The method according to claim 10,
The photosensitive resin composition whose monomer which has the said fluorinated alkyl group is a monomer represented by following formula (c1), and the monomer which has the said lipophilic group is a monomer represented by following formula (c2).

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 an alkylene having 2 to 4 carbon atoms. Group, R ^5c represents a hydrogen atom or an alkyl group of 1 to 5 carbon atoms, Rf represents a perfluoroalkyl group of 3 to 5 carbon atoms, p represents an integer of 1 to 50.) The method according to claim 2,
The said (C) surfactant is a photosensitive resin composition whose sp value is 8.7-9.5 (cal / cm <3>) ^1/2 . The method according to claim 1 or 2,
The photosensitive resin composition in which said (A) resin component contains photopolymerizable resin, and said (B) photosensitive agent is a photoinitiator. The method according to claim 1 or 2,
Furthermore, (D) Photosensitive resin composition containing colorant. The method according to claim 14,
The photosensitive resin composition in which the said (D) coloring agent contains a black pigment. The color filter which has a pattern formed using the photosensitive resin composition of Claim 14. A liquid crystal display display having the color filter of claim 16. As a manufacturing method of the color filter containing the process of forming a pattern using the photosensitive resin composition containing (A) resin component, (B) photosensitive agent, and (C) surfactant,
The said (C) surfactant has a C3-C20 fluorinated alkyl group (however, it may be interrupted by an ether bond, an ester bond, a carbonyl group, a urethane bond), and a lipophilic group in a side chain, and the said fluorinated alkyl group has C3-C5 A perfluoroalkyl group, the molar ratio of the fluorinated alkyl group to the lipophilic group is 5: 5 to 7: 3, a weight average molecular weight of 10,000 to 50,000 polymer, and the sp value is 8.0 to 9.5 (cal / Cm 3) A method for producing a color filter which is ^1/2 . As a manufacturing method of the color filter containing the process of forming a pattern using the photosensitive resin composition containing (A) resin component, (B) photosensitive agent, and (C) surfactant,
The said (C) surfactant has a C3-C20 fluorinated alkyl group (however, it may be interrupted by an ether bond, an ester bond, a carbonyl group, a urethane bond), and a lipophilic group in a side chain, and the said fluorinated alkyl group has C3-C5 A perfluoroalkyl group, the molar ratio of the fluorinated alkyl group to the lipophilic group is 5: 5 to 7: 3, and a weight average molecular weight is 10,000 to 50,000 polymer,
Said (B) photosensitive agent is an oxime ester type photoinitiator, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino propane-1-one, or 2-benzyl-2- dimethylamino-1- The manufacturing method of a color filter containing (4-morpholinophenyl) -butan-1-one. The method according to claim 18 or 19,
The manufacturing method of the color filter in which said (A) resin component contains photopolymerizable resin and the said photopolymerizable resin contains the compound represented by following formula (a1).

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

(In formula (a2), R <^1a> represents a hydrogen atom, a C1-C6 hydrocarbon group, or a halogen atom each independently, R <^2a> represents a hydrogen atom or a methyl group each independently, W represents a single bond or the following The group represented by formula (a3) is represented.)

(In addition, in said Formula (a1), Y represents the residue remove | excluding the acid anhydride group (-CO-O-CO-) from dicarboxylic acid anhydride. In said Formula (a1), Z represents from tetracarboxylic dianhydride. The residue except two acid anhydride groups is shown, n shows the integer of 0-20 in said Formula (a1).)

Images