KR20090049541A - Colored photosensitive resin composition - Google Patents

Abstract

assignment

The present invention provides a colored photosensitive resin composition and a color filter and a liquid crystal display using the colored photosensitive resin composition.

The coloring photosensitive resin composition of this invention contains (A) photopolymerizable compound, (B) photoinitiator, (C) phosphate ester compound, and (D) coloring agent. As the (C) phosphate ester compound, a compound represented by the general formula (1) or a condensate thereof is preferable.

O = P (OR ¹ ) (OR ² ) (OR ³ ) (1)

[In formula, R <^1> , R <^2> and R <^3> are respectively independently chosen from the group which consists of a C1-C10 alkyl group, a C1-C10 alkoxyalkyl group, and a C6-C20 aryl group.]

Description

Colored photosensitive resin composition {COLORED PHOTOSENSITIVE RESIN COMPOSITION}

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

Display bodies, such as a liquid crystal display, have a structure which sandwiches a liquid crystal layer between two board | substrates with which the paired electrode was mutually opposed. And inside the one board | substrate, the color filter which consists of pixel areas of each color of red (R), green (G), and blue (B) is formed. In this color filter, a black matrix is usually formed so as to partition each pixel area of red, green, and blue.

Generally, a color filter is manufactured by the lithographic method. That is, first, after apply | coating and drying a black coloring photosensitive resin composition on a board | substrate, it exposes and develops and forms a black matrix. Subsequently, application | coating, drying, exposure, and image development are repeated for each coloring photosensitive resin composition of each color of red, green, and blue, a pixel area of each color is formed in a predetermined position, and a color filter is manufactured.

As a material of the said color filter, Patent Documents 1-3, for example, disclose the coloring photosensitive resin composition containing a photopolymerizable compound, a photoinitiator, and a coloring agent. Moreover, in recent years, the improvement of the contrast of a liquid crystal display is desired, and the necessity of improving the OD value of a black matrix is increasing.

Patent Document 1: Japanese Unexamined Patent Publication No. 2004-295084

Patent Document 2: Japanese Unexamined Patent Publication No. 2006-313379

Patent Document 3: Japanese Unexamined Patent Publication No. 2006-350153

However, in order to improve OD value, the addition amount of a pigment must be increased. When the addition amount of the pigment is increased, the flow characteristic in the post bake process is lowered, and the taper angle of the formed pattern is increased. For this reason, in the edge part of the pattern of the formed black matrix, the coloring photosensitive resin composition of each color apply | coated rises, and the polish process is further needed in a post process. Therefore, the coloring photosensitive resin composition which has a high flow characteristic and which can implement | achieve a high OD value without increasing the addition amount of a pigment is preferable. Moreover, the improvement of color density is desired also about the pixel area of each color. Therefore, also in the coloring photosensitive resin composition for forming the pixel area of each color, it is preferable that high flow characteristic and high color density can be made compatible.

This invention is made | formed in view of the above subject, Comprising: It aims at providing the coloring photosensitive resin composition which can implement | achieve a high flow characteristic, a high OD value, or a color density.

MEANS TO SOLVE THE PROBLEM The present inventors discovered that the said subject could be solved by adding a phosphate ester compound to a coloring photosensitive resin composition, and came to complete this invention.

Specifically, the present invention provides the following.

A 1st aspect of this invention is the coloring photosensitive resin composition containing (A) photopolymerizable compound, (B) photoinitiator, (C) phosphate ester compound, and (D) coloring agent.

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

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

According to this invention, since it contains the (C) phosphate ester compound, the flow characteristic, OD value, or color density of a coloring photosensitive resin composition can be improved simultaneously.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail. In addition, this invention is not limited to the following embodiment at all.

[Coloring Photosensitive Resin Composition]

The coloring photosensitive resin composition of this invention contains (A) photopolymerizable compound, (B) photoinitiator, (C) phosphate ester compound, and (D) coloring agent.

[(A) Photopolymerizable Compound]

As a photopolymerizable compound, what contains resin or monomer which has an ethylenically unsaturated group is mentioned. Moreover, as a photopolymerizable compound, it is more preferable to combine resin and monomer which have an ethylenically unsaturated group. By combining the resin which has an ethylenically unsaturated group, and the monomer which has an ethylenically unsaturated group, sclerosis | hardenability can be improved and pattern formation can be made easy. In addition, in this specification, what has a mass mean molecular weight of 1000 or more among the compounds which have an ethylenically unsaturated group is called "resin which has an ethylenically unsaturated group", and what has a mass mean molecular weight of less than 1000 is called "monomer which has an ethylenically unsaturated group" do.

(Resin having an ethylenically unsaturated group)

Examples of the resin having an ethylenic unsaturated group include (meth) acrylic acid, fumaric acid, maleic acid, monomethyl fumarate, monoethyl fumarate, 2-hydroxyethyl (meth) acrylate, ethylene glycol monomethyl ether 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 Tramethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) Oligomers obtained by polymerization of acrylate, 1,6-hexanediol di (meth) acrylate and cardoepoxy diacrylate; polyester prepolymers obtained by condensation of polyhydric alcohols with monobasic or polybasic acids Polyurethane (meth) acrylate obtained by making (meth) acrylic acid react after making polyester (meth) acrylate and polyol and the compound which has two isocyanate groups react by making (meth) acrylic acid react; And 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, triphenol methane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ester, aliphatic or alicyclic epoxy resin, amine epoxy resin and dihydroxybenzene type epoxy resin Epoxy (meth) acrylate resin etc. which are obtained by making an epoxy resin and (meth) acrylic acid react are mentioned. Moreover, resin which made polybasic acid anhydride react with epoxy (meth) acrylate resin can be used.

Moreover, as resin which has an ethylenically unsaturated group, resin obtained by making the reaction material of an epoxy compound (a1) and an ethylenically unsaturated group containing carboxylic acid compound (a2) react with a polybasic acid anhydride (a3) further can be used preferably. have.

(Epoxy compound (a1))

As an epoxy compound (a1), glycidyl ether type, glycidyl ester type, glycidyl amine type, alicyclic type, bisphenol A type, bisphenol F type, bisphenol S type, biphenyl type, naphthalene type, fluorene type And phenol novolac type and orthocresol type epoxy resins.

(Ethylenically unsaturated group-containing carboxylic acid compound (a2))

As ethylenically unsaturated group containing carboxylic acid compound (a2), the monocarboxylic acid compound containing reactive ethylenic double bonds, such as an acryl group and a methacryl group, is preferable in a molecule | numerator. Examples of such ethylenically unsaturated group-containing carboxylic acid compounds include acrylic acid, methacrylic acid, β-styrylacrylic acid, β-furfuryl acrylic acid, α-cyano cinnamic acid, and cinnamic acid. This ethylenically unsaturated group containing carboxylic acid compound (a2) may be used independently, and may be used in combination of 2 or more type.

As a method for reacting the epoxy compound (a1) with the ethylenically unsaturated carboxylic acid compound (a2), a known method can be used. For example, the epoxy compound (a1) and the ethylenically unsaturated carboxylic acid compound (a2) may be reacted with a tertiary amine such as triethylamine and benzylethylamine, dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethyl Quaternary ammonium salts such as ammonium chloride and benzyltriethylammonium chloride, pyridine and triphenylphosphine as catalysts, and the reaction is carried out in an organic solvent at a reaction temperature of 50 ° C to 150 ° C for several hours to several tens of hours .

The usage-amount ratio in reaction of an epoxy compound (a1) and an ethylenically unsaturated group containing carboxylic acid compound (a2) is a carbon equivalent of the epoxy equivalent of an epoxy compound (a1) and an ethylenically unsaturated group containing carboxylic acid compound (a2). The ratio of acid equivalents is usually 1: 0.5 to 1: 2, preferably 1: 0.8 to 1: 1.25, and more preferably 1: 1. By setting it as said range, there exists a tendency for crosslinking efficiency to improve.

(Polybasic acid anhydride (a3))

As polybasic acid anhydride (a3), for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydro phthalic anhydride, hexahydro phthalic anhydride, methyl hexahydro phthalic anhydride, methyltetrahydro phthalic anhydride, trimelli anhydride Acid, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-ethylhexahydro phthalic anhydride, 4-ethylhexahydro phthalic anhydride, tetrahydro Phthalic anhydride, 3-methyl tetrahydro phthalic anhydride, 4-methyl tetrahydro phthalic anhydride, 3-ethyl tetrahydro phthalic anhydride, and 4-ethyl tetrahydro phthalic anhydride are mentioned. These polybasic acid anhydrides may be used independently and may be used in combination of 2 or more type.

A well-known method can be used as a method of making a polybasic acid anhydride (a3) react after making an epoxy compound (a1) and an ethylenically unsaturated group containing carboxylic acid compound (a2) react. In addition, the usage-amount ratio is an equivalence ratio of the number-of-moles of OH group in the reaction material of an epoxy compound (a1) and an ethylenically unsaturated group containing carboxylic acid compound (a2), and the acid anhydride group of polybasic acid anhydride (a3), and it is 1: 1. 1-1: 0.1, Preferably it is 1: 0.8-1: 0.2. By setting it as said range, there exists a tendency for the solubility to a developing solution to become suitable.

The acid value of resin obtained by making the reaction material of an epoxy compound (a1) and an ethylenically unsaturated group containing carboxylic acid compound (a2) react with a polybasic acid anhydride (a3) further is 10 mgKOH / g-in resin solid content. It is preferable that it is 150 mgKOH / g, and it is more preferable that it is 70 mgKOH / g-110 mgKOH / g. By making the acid value of resin into 10 mgKOH / g or more, sufficient solubility to a developing solution can be obtained, and by setting it to 150 mgKOH / g or less, sufficient hardenability can be obtained and surface quality can be made favorable.

Moreover, it is preferable that the mass mean molecular weight (Mw) of resin is 1000-400000, More preferably, it is 2000-30000. By setting the mass average molecular weight to 1000 or more, heat resistance and film strength can be improved, and by setting it to 40000 or less, sufficient solubility in a developer can be obtained.

Moreover, as resin which has an ethylenically unsaturated group, resin which has a cardo structure in a molecule | numerator can be used preferably. Since resin which has a cardo structure has high heat resistance and chemical-resistance, it can improve the heat resistance and chemical-resistance of a coloring photosensitive resin composition by using it for a photopolymerizable compound. For example, resin represented by General formula (1) can be used preferably.

In general formula (1), n is an integer of 1-20, X is group represented by General formula (2).

In General Formula (1), Y represents maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylene tetrahydrophthalic anhydride, chloric anhydride, methyltetra. It is the residue which removed carboxylic anhydride group (-CO-O-CO-) from dicarboxylic acid anhydrides, such as hydrophthalic anhydride and glutaric anhydride.

In General Formula (1), Z is tetracarboxylic acid 2 such as pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, and biphenyl ether tetracarboxylic dianhydride. It is the residue which removed two carboxylic acid anhydride groups from an anhydride.

(Monomer having an ethylenically unsaturated group)

The monomer which has an ethylenically unsaturated group has a monofunctional monomer and a polyfunctional monomer.

As the monofunctional monomer, (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxy Methyl (meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, sheet Laconic acid, citraconic anhydride, crotonic acid, 2-acrylamide-2-methylpropanesulfonic 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 Yit, 2- (meth) acryloyloxy-2-hydroxypropylphthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidyl (meth ) Acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, half (meth) acrylate of a phthalic acid derivative, etc. are mentioned. Can be. These monofunctional monomers may be used independently, or may be used in combination of 2 or more type.

On the other hand, as a 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 (meth) acrylate, pentaerythritol tree (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythr Tolhexa (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 digly Cydyl ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (ie tolylene diisocyanate), trimethylhexamethylene diisocyanate and hexa Reactant of 2-hydroxyethyl (meth) acrylate, such as methylene diisocyanate, methylenebis (meth) acrylamide, (meth) acrylamide methylene ether, condensate of polyhydric alcohol and N-methylol (meth) acrylamide, tri Arc It may include formal and more. These polyfunctional monomers may be used independently and may be used in combination of 2 or more type.

It is preferable that content of the monomer which has this ethylenically unsaturated group is 5 mass%-50 mass% with respect to solid content of a coloring photosensitive resin composition, More preferably, it is the range of 10 mass%-40 mass%. By setting it as said range, it exists in the tendency to balance the sensitivity, developability, and resolution. In addition, solid content means the sum total of components other than a solvent.

It is preferable that it is 5 mass%-50 mass% with respect to solid content of a coloring photosensitive resin composition, and, as for content of a photopolymerizable compound, it is more preferable that it is 10 mass%-40 mass%. By setting it as said range, it exists in the tendency to balance the sensitivity, developability, and resolution.

[(B) Photoinitiator]

As a photoinitiator, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 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-dimethyl Amino-2-isoamylbenzoic acid, benzyl-β-meth Cyethylacetal, benzyl dimethyl ketal, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, methyl O-benzoylbenzoate, 2,4-diethyl thioxanthone, 2-chloro Thioxanthone, 2,4-dimethyl thioxanthone, 1-chloro-4-propoxy thioxanthone, thioxanthene, 2-chloro thioxanthene, 2,4-diethyl thioxanthene, 2-methyl thi Oxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, Cumeneperoxide, 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, benzoinmethyl 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-butyltrichloroacetophenone, p-tert-butyldichloroaceto Phenone, α, α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropyl thioxanthone, dibenzosuberon, 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-methoxy) styrylphenyl-s-triazine and 2,4-bis-trichloromethyl-6- ( 2-bromo-4-methoxy) styrylphenyl-s-triazine etc. are mentioned. Among these, using an oxime system photoinitiator is especially preferable at the point of a sensitivity. These photoinitiators may be used independently and may be used in combination of 2 or more type.

It is preferable that it is 0.5 mass%-30 mass% with respect to solid content of a coloring photosensitive resin composition, and, as for content of a photoinitiator, it is more preferable that it is 1 mass%-20 mass%. By setting it as said range, sufficient heat resistance and chemical-resistance can be obtained, a coating film formation ability can be improved, and a photocuring defect can be suppressed.

[(C) phosphate ester compound]

As the phosphate ester compound, any conventionally known phosphate ester compound can be used. By containing a phosphate ester compound, the flow characteristic at the time of baking of a coloring photosensitive resin composition improves, and a coloring photosensitive resin composition film (or pattern) is shrunk at the time of post-baking. As a result, the OD value increases when a black matrix is formed, and when the pixel areas of each color such as red, green, and blue are formed, the color density increases. In addition, good substrate adhesion can be maintained.

In the present invention, in particular, general formula (3)

O = P (OR ¹ ) (OR ² ) (OR ³ ) (3)

In formula, R <^1> , R <^2> and R <^3> are respectively independently chosen from the group which consists of a C1-C10 alkyl group, a C1-C10 alkoxyalkyl group, and a C6-C20 aryl group, or its Condensates are preferred.

The alkyl group includes a substituted or unsubstituted linear, branched, or cyclic alkyl group. The alkoxyalkyl group includes a substituted or unsubstituted linear, branched, or cyclic alkyl group substituted with one or more alkoxy groups.

An alkoxy group includes what the linear, branched, or cyclic alkyl group couple | bonded with the oxygen atom in the range which the sum total of carbon number of the alkyl group which the said alkoxy group couple | bonds with the alkoxy group becomes 2-9.

The aryl group contains substituted or unsubstituted monocyclic rings and condensed ring aromatic hydrocarbons. When the alkyl group, alkoxyalkyl group and aryl group are substituted, the substituent may be optionally selected from the group consisting of a hydrocarbon group such as an alkyl group and an aryl group, an alkoxy group, a phenoxy group, an alkoxyalkyl group, a hydroxyl group and a halogen-containing group. Preferred substituents are alkyl groups, aryl groups, alkoxy groups, phenoxy groups and alkoxyalkyl groups, with alkyl groups and aryl groups being particularly preferred.

In addition, R ¹ , R ² And R ³ is preferably an unsubstituted alkyl group or an alkyl group substituted aryl group or an unsubstituted aryl group.

Specifically, there may be mentioned trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris (2-ethylhexyl) phosphate, tris (butoxyethyl) phosphate, triphenyl fauate, tricresyl phosphate, trixylenyl phosphate, Tris (dibromopropyl) phosphate, tris (tribromoneopentyl) phosphate, condensates thereof, and the like can be used in the present invention. Examples of the phosphoric acid ester compound include phenyl phosphate, 2-ethylhexyldiphenyl phosphate, cresyldi 2,6-xylenyl phosphate, tris (chloropropyl) And 1, 3- phenylene bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), and 1, 3- phenylene bis (di2, 6- xylenyl phosphate) can be used. Among these, triphenylphosphate, 2-ethylhexyl diphenyl phosphate, or bisphenol A bis (diphenyl phosphate) is preferable, and triphenylphosphate or 2-ethylhexyl diphenyl phosphate is more preferable.

It is preferable that content of a phosphate ester compound is 0.1 mass%-20 mass% with respect to solid content of a coloring photosensitive resin composition, 1 mass%-15 mass% are more preferable, It is still more preferable that they are 3 mass%-10 mass%. Do. By setting it as said range, favorable flow characteristics and the outstanding shrink ratio are shown.

[(D) Colorant]

Although it does not specifically limit as a coloring agent, A conventionally well-known pigment or dye can be used. For example, when forming a black matrix and a black stripe using the coloring photosensitive resin composition of this invention, carbon black, titanium black, chromium oxide, iron oxide, aniline black, a perylene type pigment, CI solvent black 123, etc. are used. Can be used. Moreover, carbon black coated with epoxy resin etc .; inorganic black pigments, such as complex oxides, such as titanium, manganese, iron, copper, and cobalt; The combination of the organic pigment shown below; And the organic pigment and the black pigment mentioned above Combinations may also be appropriately employed.

In addition, in the colored photosensitive resin composition which concerns on this invention, black pigment can also be disperse | distributed using a black pigment dispersion liquid, and "Carbon dispersion liquid CF black (20% of carbon concentration containing 20%) by Mikuni dye company" which is an inorganic black pigment dispersion liquid. And "carbon dispersion liquid CF black (containing 24% of high resistance carbon)" manufactured by Mikuni dye company, "titanium black dispersion liquid CF black (containing 20% black titanium pigment)" manufactured by Mikuni dyeing company can be used. Moreover, you may use "violet dispersion liquid (containing 10% of violet pigments)" by Mikuni dye company, and "blue pigment dispersion CF blue (containing 20% of blue pigments)" by Mikuni dye company.

In addition, in the case of chromatic colors, such as red, green, blue, cyan, magenta, and yellow, the pigment or dye of Unexamined-Japanese-Patent No. 60-237403 and Unexamined-Japanese-Patent No. 4-310901 is used, for example. Can be mentioned.

Specifically, in the color index number (C. I. No.),

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

Orange pigment: C. I. 36, 43, 51, 55, 59, 61

Red pigment: C. I. 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254

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

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

Green pigment: C. I. 7, 36

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

Since what is shown as high transparency and excellent heat resistance, weather resistance, and chemical-resistance can be used preferably.

Moreover, as a dye, it is specifically C.I. in

Yellow dye: C. I. Direct Yellow 1, CI Direct Yellow 11, CI Direct Yellow 12, CI Direct Yellow 28, CI Ex Yellow 1, CI Ex Yellow 3, CI Ex Yellow 11, CI Ex Yellow 17, CI Ex Yellow 23, CI Ex Yellow 38, CI Excid Yellow 40, CI Excid Yellow 42, CI Exid Yellow 76, CI Exid Yellow 98, CI Basic Yellow 1, CI Disperse Yellow 3, CI Disperse Yellow 4, CI Disperse Yellow 7, CI Disperse Yellow 31 , CI Disperse Yellow 61, CI Solvent Yellow 2, CI Solvent Yellow 14, CI Solvent Yellow 15, CI Solvent Yellow 16, CI Solvent Yellow 21, CI Solvent Yellow 33, CI Solvent Yellow 56

CI Excess Orange 1, CI Exed Orange 7, CI Exed Orange 8, CI Exed Orange 10, CI Exed Orange 20, CI Exed Orange 24, CI Exed Orange 28, CI Exed Orange 33, CI Exed Orange 56, Orange 74, CI Direct Orange 1, CI Disperse Orange 5, CI Solvent Orange 1, CI Solvent Orange 2, CI Solvent Orange 5, CI Solvent Orange 6, CI Solvent Orange 45

Red dye: C. I. Direct Red 20, CI Direct Red 37, CI Direct Red 39, CI Direct Red 44, CI Exid Red 6, CI Exid Red 8, CI Ex Red 9, CI Ex Red 13, CI Ex Red 14, CI Ex Red 18 , CI EXID Red 26, CI EX EX RED 27, CI EX EX RED 51, CI EX EX RED 52, CI EX EX RED 87, CI EX EX RED 88, CI EX RED 89, CI EX RED 92, CI EX RED 94, CI EX RED 97 , CI Exed Red 111, CI Exed Red 114, CI Exed Red 115, CI Exed Red 134, CI Exed Red 145, CI Exed Red 154, CI Exed Red 180, CI Exed Red 183, CI Exed Red 184, CI Exed Red 186 , CI Exid Red 198, CI Basic Red 12, CI Basic Red 13, CI Disperse 5, CI Disperse 7, CI Disperse 13, CI Disperse 17, C I. Dispers 58, CI Solvent Red 1, CI Solvent Red 3, CI Solvent Red 8, CI Solvent Red 23, CI Solvent Red 24, CI Solvent Red 25, CI Solvent Red 27, CI Solvent Red 30, CI Solvent Red 49, CI Solvent Red 100

Purple dyes: C. I. direct violet 22, C. I. seed violet 49, C. I. basic violet 2, C. I. basic violet 7, C. I. basic violet 10, C. I. disperse violet 24

Blue dye: C. I. Direct Blue 25, CI Direct Blue 86, CI Direct Blue 90, CI Direct Blue 108, CI Extract Blue 1, CI Extract Blue 7, CI Extract Blue 9, CI Extract Blue 15, CI Extract Blue 103, CI Extract Blue 104 CI CI Blue 158, CI Blue 161, CI Basic Blue 1, CI Basic Blue 3, CI Basic Blue 9, CI Basic Blue 25

Green dye: C. I. EXID GREEN 3, C. I. EXID GREEN 9, C. I. EXID GREEN 16, C. I. BASIC GREEN 1, C. I. BASIC GREEN 4

Brown dye: C. I. Direct Brown 6, C. I. Direct Brown 58, C. I. Direct Brown 95, C. I. Direct Brown 101, C. I. Direct Brown 173, C. I. Acid Brown 14

Etc. are used preferably.

It is preferable to contain the said pigment and / or dye in the range of 1 mass%-70 mass% with respect to solid content of a coloring photosensitive resin composition, and it is more preferable to contain in 20 mass%-60 mass%. When it is less than 1 mass%, it is difficult to function as a color filter, On the other hand, when it exceeds 70 mass%, a sensitivity may fall and the heat resistance and chemical-resistance of the coating film after hardening may fall.

[(S) solvent]

The coloring photosensitive resin composition which concerns on this invention can contain a solvent in addition to each component mentioned above. It does not specifically limit as such a solvent, The solvent normally used for a coloring photosensitive resin composition can be used. Specific examples of the other solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl 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, (Poly) alcohols such as tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether Ethylene glycol monoalkyl ethers; (poly) alkylenes such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate Glycol monoalkyl ether acetates; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; methyl ethyl ketone, cyclohexanone, 2-heptanone, and the like; Ketones such as 3-heptanone; lactic acid alkyl esters such as 2-hydroxypropionate methyl and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, 3-methoxy Ethyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethoxya Ethyl acetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate , Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-butyric acid Other esters such as propyl, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; and Amides such as N-methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide. Among these, 3-methoxybutyl acetate is preferable at the point which shows the outstanding solubility with respect to a photopolymerizable compound and a photoinitiator, and makes dispersibility of insoluble components, such as a black pigment, favorable. Moreover, propylene glycol monomethyl ether acetate and cyclohexanone are also preferable. Other solvents may be used alone or in combination of two or more thereof.

As a combination, it is preferable to contain 3 types of 3-methoxybutyl acetate, a propylene glycol monomethyl ether acetate, and cyclohexanone.

Moreover, it is preferable that it is an amount which solid content concentration becomes 1 mass% or more and 50 mass% or less, and, as for the solvent in the coloring photosensitive resin composition of this invention, it is more preferable that it is an amount which will be 5 mass% or more and 30 mass% or less. When the quantity of a solvent exists in the said range, the film formation ability and applicability | paintability in a coloring photosensitive resin composition can be kept favorable.

[Other ingredients]

The coloring photosensitive resin composition of this invention can be made to contain an additive as needed. Examples of the additive include a thermal polymerization inhibitor, an antifoaming agent, a surfactant, a sensitizer, a curing accelerator, a photocrosslinker, a photosensitizer, a dispersant, a dispersion aid, a filler, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an anti-agglomerating agent. As the dispersant, polymer dispersants such as urethane resin dispersants are preferably used.

[Preparation method of colored photosensitive resin composition]

The coloring photosensitive resin composition of this invention is obtained by mixing each said component with a stirrer. In addition, you may filter using a filter so that the obtained mixture may be uniform.

[Color filter]

A color filter is formed using the coloring photosensitive resin composition of this invention. That is, the photosensitive resin composition in which black colorant was disperse | distributed to the board | substrate which consists of glass, polyethylene terephthalate, an acrylic resin, polycarbonate, etc., and a contact transfer type | mold coating apparatus, such as a roll coater, a reverse coater, a bar coater, and a spinner (rotary coating device) ) And a non-contact type coating device such as a slit coater and a curtain flow coater.

Next, the applied coloring photosensitive resin composition is dried to form a coating film. Although a drying method is not specifically limited, For example, it is made to dry under reduced pressure at room temperature using a vacuum drying apparatus, and then 60 seconds-at a temperature of 80 degreeC-120 degreeC, Preferably it is 90 degreeC-100 degreeC in a hotplate- The method of drying for 120 second is mentioned.

Subsequently, active energy rays, such as an ultraviolet-ray and an excimer laser beam, are irradiated and partially exposed through a negative mask to this coating film. Although the amount of energy to irradiate changes also with the composition of the photosensitive resin composition, it is preferable that they are 30mJ / cm <2> -2000mJ / cm <2>, for example.

Subsequently, the coating film after exposure is developed with a developing solution, and is patterned in a desired shape. The image development method is not specifically limited, For example, an immersion method, a spray method, etc. can be used. Examples of the developer 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.

Next, post-baking is performed at 220 degreeC-250 degreeC, Preferably it is 230 degreeC-240 degreeC about the pattern after image development. At this time, it is preferable to expose the formed pattern to the whole surface. By the above, the black matrix which has a predetermined pattern shape can be formed.

It is preferable that it is 87% or less, and, as for the shrinkage rate of the film thickness by post-baking, it is more preferable that it is 85% or less.

Moreover, in the cross-sectional shape of the formed black matrix pattern, it is preferable that the taper angle (the angle which forms the surface which contacts the board | substrate of a pattern, and the board | substrate surface) is 75 degrees or less, It is more preferable if it is 70 degrees or less, If it is 65 degrees or less More preferred. It is preferable that the lower limit of a taper angle is 30 degrees or more, and it is more preferable if it is 35 degrees or more.

In this invention, flow characteristic can be improved by containing (C) component, and the taper angle can obtain the black matrix pattern in the said range.

Moreover, in this invention, it is preferable that the OD value of a black matrix pattern is more than 4.4, It is more preferable that it is 4.5 or more, It is further more preferable that it is 4.6 or more.

 The above operation is performed with respect to the coloring photosensitive resin composition in which the pigment of red, green, and blue was disperse | distributed, and the pixel pattern of each color is formed. As a result, a color filter is formed. Also about red, green, and blue coloring photosensitive resin composition, since containing this application (C) component can improve a color density, a shrink ratio, and a flow characteristic, the part which a colored layer overlaps on a black matrix can be made smooth. have.

In the manufacture of the color filter of the present invention, the ink of each color of red, green, and blue is discharged from the inkjet nozzle in each area partitioned by the black matrix, and the deceased ink is cured by heat or light, and the color filter It may be prepared.

[Liquid crystal display display]

The liquid crystal display of this invention is equipped with the color filter of this invention. When manufacturing the liquid crystal display of this invention, the said color filter is formed on a board | substrate, and then an electrode, a spacer, etc. are formed one by one. Then, an electrode or the like is formed on another substrate, and both are attached to each other, and a predetermined amount of liquid crystal is injected and sealed to manufacture by a conventional method.

Example

EXAMPLE 1

Synthesis of Photopolymerizable Compound

First, in a 500 ml four-necked flask, 235 g of bisphenol fluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methyl phenol and 72.0 g of acrylic acid Was melt | dissolved by heating at 90 degreeC-100 degreeC, blowing air into this at a rate of 25 ml / min. Next, the solution was gradually heated up in a cloudy state, heated to 120 ° C, and completely dissolved. The solution gradually became transparent and viscous, but stirring continued as it was. In the meantime, heating and stirring were continued until the acid value was measured and it became less than 1.0 mgKOH / g. It took 12 hours to reach the goal. And it cooled to room temperature and obtained bisphenol fluorene type epoxy acrylate.

Subsequently, 600 g of 3-methoxybutyl acetate is added to and dissolved in 307.0 g of the bisphenol fluorene type epoxy acrylate obtained as described above, 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 degreeC-115 degreeC for 4 hours. After disappearance of the acid anhydride was confirmed, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 DEG C for 6 hours to obtain a photopolymerizable compound 1. Loss of acid anhydride was confirmed by IR spectrum.

[Preparation of a colored photosensitive resin composition]

(A) component (photopolymerizable compound): Photopolymerizable compound 1 (mass average molecular weight 3400, solid content: 55%, solvent: 3-methoxybutyl acetate) ... 23.6 parts by mass and

Dipentaerythritol hexaacrylate... 4.8 parts by mass

(B) component (photoinitiator): "IRGACURE OXE 02" (brand name, Chiba Specialty Chemicals Corporation make)…. 1.4 parts by mass

(C) component (phosphate ester compound): 2-ethylhexyl diphenyl phosphate ... 3 parts by mass

(D) component (coloring agent): Carbon dispersion liquid "CF black EX-1455" (brand name, Mikuni dye company make, high resistance carbon: 24%, dispersing agent: 5%, solvent: 3-methoxybutyl acetate)…. 100 parts by mass

It adjusted with the following mixed solvents so that solid content concentration of the said component might be 18 mass%.

(S) Component (solvent): 3-methoxybutyl acetate / cyclohexanone / propylene glycol monomethyl ether acetate = 55/30/15 (mass ratio))

After mixing these mixtures for 2 hours in the stirrer, it filtered by the 5 micrometer membrane filter, and obtained the coloring photosensitive resin composition.

(Cured resin pattern forming method)

After apply | coating the said colored photosensitive resin composition on the glass substrate (680 mm x 880 mm) with the slit coater, it prebaked at 110 degreeC for 120 second, and formed the resin composition film of 1 micrometer in film thickness. Subsequently, this coating film was exposed (brand name: MPA6000CF, Canon Co., Ltd., energy dose 50mJ / cm <2>), image development was performed at 25 degreeC with 0.04 mass% KOH aqueous solution for 50 second, and post-baking was performed at 230 degreeC, and pattern size 10 A cured resin pattern of 탆 was formed.

EXAMPLE 2

A cured resin pattern was formed in the same manner as in Example 1 except that the component (C) was replaced by the following.

(C) component (phosphate ester compound): 2-ethylhexyl diphenyl phosphate ... 5 parts by mass

EXAMPLE 3

A cured resin pattern was formed in the same manner as in Example 1 except that the component (C) was replaced by the following.

(C) component (phosphate ester compound): 2-ethylhexyl diphenyl phosphate ... 10 parts by mass

EXAMPLE 4

A cured resin pattern was formed in the same manner as in Example 1 except that the component (C) was replaced by the following.

(C) component (phosphate ester compound): Triphenylphosphate ... 5 parts by mass

[Comparative Example 1]

A cured resin pattern was formed in the same manner as in Example 1 except that the component (C) was not contained.

[Comparative Examples 2-1 and 2-2]

A cured resin pattern was formed in the same manner as in Example 1 except that the component (C) was replaced by the following.

Phthalic acid ester compound: Phthalic acid diisodecyl ester

Comparative Example 2-1 5 parts by mass

Comparative Example 2-2 10 parts by mass

[Comparative Examples 3-1 and 3-2]

A cured resin pattern was formed in the same manner as in Example 1 except that the component (C) was replaced by the following.

Phthalic acid ester compound: Phthalic acid bis (2-ethylhexyl) ester

Comparative Example 3-1 5 parts by mass

Comparative Example 3-2 10 parts by mass

[Comparative example 4]

A cured resin pattern was formed in the same manner as in Example 1 except that the component (C) was replaced by the following.

Phthalic acid ester compound: Dimethyl phthalate ester…. 5 parts by mass

[Comparative Example 5]

A cured resin pattern was formed in the same manner as in Example 1 except that the component (C) was replaced by the following.

Phthalic acid ester compound: Phthalic acid diethyl ester. 5 parts by mass

[Comparative Example 6]

A cured resin pattern was formed in the same manner as in Example 1 except that the component (C) was replaced by the following.

Phthalic acid ester compound: Phthalic acid butyl benzylster… 5 parts by mass

[evaluation]

The OD value of the cured resin pattern formed by the said Example and the comparative example, the taper angle (the surface which contact | connects the board | substrate of a pattern, the angle which a board | substrate surface forms), and the shrinkage rate were evaluated. The results are shown in Table 1. In addition, OD value was measured using "Gretag Machbeth D-200-2" (brand name, Machbeth company make), and made the film thickness of cured resin pattern into 1 micrometer.

The taper angle was measured from the cross-sectional photograph of the formed pattern.

In addition, a shrink ratio shows the ratio of the film thickness of the cured resin pattern after post-baking with respect to the film thickness of the resin composition film after exposure.

OD / μm Taper angle Shrink Rate Example 1 4.5 74 degrees 87% Example 2 4.6 52 degrees 84% Example 3 4.7 39 degrees 80% Example 4 4.6 65 degrees 86% Comparative Example 1 4.4 84 degrees 90% Comparative Example 2-1 4.4 75 degrees 88% Comparative Example 2-2 Not measurable No pattern Not measurable Comparative Example 3-1 4.4 76 degrees 88% Comparative Example 3-2 Not measurable No pattern Not measurable Comparative Example 4 Not measurable No pattern Not measurable Comparative Example 5 Not measurable No pattern Not measurable Comparative Example 6 Not measurable No pattern Not measurable

In Table 1, since the resin composition film peeled off from the board | substrate after the image development process in the said resin composition hardening pattern formation method, and the pattern was not formed, in the comparative example 2-2, 3-2, and 4-6, an OD value The value of the shrink rate could not be measured.

From Table 1, in Examples 1-4 which added (C) component, the system which added the phthalic ester instead of the system (Comparative Example 1) and (C) component which did not add (C) component (Comparative Example 2- 1, 3-1), the value of the shrink rate becomes smaller (i.e., the film thickness after postbaking is significantly contracted), so that the OD value increases and the taper angle decreases (i.e., the flow characteristics are improved). It turned out to be. Therefore, it turns out that the increase of an OD value and the improvement of a flow characteristic were simultaneously achieved by adding (C) component.

Moreover, in Examples 1-4, the board | substrate adhesiveness was also favorable, but in Comparative Examples 2-2, 3-2, and 4-6, a pattern is peeled off from a board | substrate after image development, board | substrate adhesiveness is bad, and it is inappropriate as a coloring photosensitive resin composition. I could see that.

Moreover, from the result of Examples 1-3, it turns out that OD value and a flow characteristic improved as the addition amount of (C) component increased. At the same time, even if the addition amount of the component (C) is increased, the substrate adhesion is good, whereas in the case of other than the component (C), as shown in the results of Comparative Examples 2-1 to 3-2, the addition amount is shown. It was found that when the was increased, the substrate adhesiveness could not be achieved at the same time, and it did not lead to the improvement of the OD value and the flow characteristics.

Claims (6)

Colored photosensitive resin composition containing (A) photopolymerizable compound, (B) photoinitiator, (C) phosphate ester compound, and (D) coloring agent. The method of claim 1, Colored photosensitive resin composition whose said (C) phosphate ester compound is a compound represented by General formula (1), or its condensate. O = P (OR ¹ ) (OR ² ) (OR ³ ) (1) [In formula, R <^1> , R <^2> and R <^3> are respectively independently chosen from the group which consists of a C1-C10 alkyl group, a C1-C10 alkoxyalkyl group, and a C6-C20 aryl group.] The method of claim 1, The coloring photosensitive resin composition containing 0.1 mass%-20 mass% of said (C) phosphate ester compound with respect to solid content. The method of claim 1, The coloring photosensitive resin composition whose said (D) coloring agent is a black pigment. The color filter which has a pattern formed using the coloring photosensitive resin composition of any one of Claims 1-4. The liquid crystal display which has the color filter of Claim 5.