KR20080007209A - Photosensitive composition and color filter formed from this photosensitive composition - Google Patents

Abstract

The present invention provides a photosensitive composition capable of forming a black matrix and / or a colored layer having high adhesion and good quality, and a color filter formed of the photosensitive composition. A colorant-containing photosensitive composition containing (a) a colorant, (b) a photopolymerizable compound, (c) a photopolymerization initiator, and (d) an adhesion enhancer, wherein (d) the adhesion enhancer is a silane compound having a group containing nitrogen. Compounds having one or less hydrogens bonded to nitrogen are used.

Description

Photosensitive Composition and Color Filter Formed from the Same

The present invention relates to a photosensitive composition, a color filter formed of the photosensitive composition, and more particularly, to a photosensitive composition suitable for forming a black matrix and / or a color filter of a liquid crystal panel, and a color filter formed of the photosensitive composition.

Liquid crystal panels, in particular, liquid crystal panels such as TN and STN systems, have a black matrix for enhancing the contrast of an image, or an RGB colored layer generally composed of red (R), green (G), and blue (B) colors. The formed color filter is provided. This black matrix and a colored layer are formed by apply | coating the photosensitive composition which black or the coloring agent of each color disperse | distributed to a board | substrate, drying, exposing and developing the obtained coating film, and repeating forming a desired pattern. In particular, the black matrix and the colored layer are required to have high adhesion with the substrate in order to secure reliability in the liquid crystal panel. In contrast, Japanese Patent Application Laid-Open No. 2000-35670 discloses adding an amine silane coupling agent to a colored photosensitive resin composition. However, the document compares whether there is peeling when the cellophane tape is attached and the cellophane tape is peeled off. This takes into account the curability of the colored photosensitive resin composition, and peeling occurs when the curability is low.

For example, the liquid crystal panel has a structure in which a substrate on which a color filter is formed and an opposing substrate are attached, and a liquid crystal is filled between the two substrates. Therefore, when a color filter is peeled off, the problem that a liquid crystal leaks out from a liquid crystal panel arises. Therefore, PCT (Pressure Cooker Test) is performed as a durability test regarding adhesion. In this PCT, the liquid crystal panel is left for 2 hours under severe conditions such as a temperature of 120 ° C., a humidity of 100% and an air pressure of 2 atm, to check whether there is a leakage of the liquid crystal enclosed between the color filter substrate and the TFT substrate of the liquid crystal panel. As such, in recent years, the demand for adhesion is further advanced. As a result, there is a demand for a black matrix and / or a colored layer having high adhesion even under stringent conditions different from those of the prior art. On the other hand, the peeling test by the cellophane tape like the said document can be said to be inadequate as an adhesive test in the present state. In particular, when forming a black matrix, since the light-shielding agent is contained in the photosensitive composition, there exists a problem that curability becomes low, adhesiveness falls, peeling etc. tend to occur.

The present invention has been made in view of the above problems, and an object thereof is to provide a photosensitive composition capable of forming a black matrix and / or a colored layer having high adhesion and good quality even in PCT, and a color filter formed of the photosensitive composition. .

The photosensitive composition of the present invention is a colorant-containing photosensitive composition containing (a) a colorant, (b) a photopolymerizable compound, (c) a photopolymerization initiator, and (d) an adhesion enhancer, wherein (d) the adhesion enhancer is a group containing nitrogen. It is a silane compound, It is characterized by having one or less hydrogen couple | bonded with the said nitrogen.

The coloring agent containing photosensitive composition of this invention contains (a) a coloring agent, (b) photopolymerizable compound, (c) photoinitiator, and (d) adhesion promoter.

As the (a) coloring agent, for example, a compound classified as a pigment in a color index (CI; issued by The Society of Dyers and Colourists, Inc.), specifically the following color index (CI) number is given. I can hear that.

C.I. Pigment Yellow 1 (hereinafter 'CI Pigment Yellow' is the same and only numbers are listed), 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 only numbers are listed), 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 lists 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.

Although the addition amount of (a) coloring agent can be suitably changed according to the target color tone, Generally, (b) 100 weight part of photopolymerizable compounds (or a polymeric binder and a photopolymerizable monomer), and (c) a photoinitiator total. It is preferable to add in 5-250 mass parts, and a more preferable range is about 10-200 mass parts.

In addition, when forming a black mask, a light-shielding agent is used as a coloring agent. The light shielding agent is not particularly limited as long as it has a sufficient light shielding ratio when used as the light shielding layer, and examples thereof include black pigments. Carbon black, titanium black, perylene black, etc. are mentioned as this black pigment. Furthermore, in order to reduce color tone or obtain a higher resistance value, the coloring agent may be added within a range not to impair the light shielding performance.

In addition, in order to maintain an image with high contrast, the black matrix formed by coating the photosensitive composition using the light-shielding agent as a colorant generally has an OD value of 1.5 or more, preferably 3.0 or more, and more preferably 4.0 or more. It is good.

The amount of the light-shielding agent added to the photosensitive composition of the present invention is 20 to 150 parts by weight, preferably 100 parts by weight of the total of (b) the photopolymerizable compound (or the polymer binder and the photopolymerizable monomer) and (c) the photopolymerization initiator. Is in the range of 25 to 100 parts by weight, more preferably 30 to 80 parts by weight. By making the said range 20 weight part or more, the black matrix which has sufficient light-shielding property can be provided. Moreover, by making the said range into 150 weight part or less, a hardening failure can be prevented and a favorable black matrix can be formed.

Moreover, the said (a) coloring agent can be mixed with another component as a solution disperse | distributed to a suitable density | concentration (for example, 10 to 20%) using a dispersing agent. Although the said dispersing agent is not specifically limited, For example, the polymer dispersing agent of a polyethyleneimine system, a urethane resin system, and an acrylic resin system is used preferably.

Said (b) photopolymerizable compound is a substance which superposes | polymerizes and hardens | cures by irradiation of light, such as an ultraviolet-ray. As the photopolymerizable compound, a compound having an ethylenic double bond is preferable, and specifically, acrylic acid, methacrylic acid, fumaric acid, maleic acid, monomethyl fumarate, monoethyl fumarate, 2-hydroxyethyl acrylate, 2-hydroxyethyl Methacrylate, ethylene glycol monomethyl ether acrylate, ethylene glycol monomethyl ether methacrylate, ethylene glycol monoethyl ether acrylate, ethylene glycol monoethyl ether methacrylate, glycerol acrylate, glycerol methacrylate, acrylic acid amide, Methacrylate amide, acrylonitrile, methacrylonitrile, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, benzyl acrylate, benzyl Methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol di Methacrylate, butylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolpropane tetraacrylate, tetramethyl Roll propane tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate (DPTA), pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate Relate, dipentaerythritol hexaacrylate (DPHA), dipentaerythritol hexamethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, cardepoxy diacrylate, and the like Monomers and oligomers; 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 group and two isocyanate groups Polyurethane (meth) acrylate obtained by reacting; 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 reacting (meth) acrylic acid 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, the resin which made polybasic acid anhydride react with the said epoxy (meth) acrylate resin can also be used preferably.

Moreover, as a photopolymerizable compound, the compound represented by following formula (1) is also applicable. The compound represented by this general formula (1) is a preferable compound by the point that itself is highly photocurable.

Here, n is an integer of 1-20. In addition, it is preferable that X of the compound represented by General formula (1) is group represented by following General formula (2).

In addition, Y of the compound represented by Formula 1 is, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chloride anhydride, for example. It is the residue which removed carboxylic anhydride group (-CO-O-CO-) from dicarboxylic anhydrides, such as an acid (chlorendic acid), methyltetrahydro phthalic anhydride, and glutaric anhydride.

In addition, Z of the compound represented by General formula (1) is two from tetracarboxylic dianhydrides, such as pyromellitic anhydride, a benzophenone tetracarboxylic dianhydride, a biphenyl tetracarboxylic dianhydride, and a biphenyl ether tetracarboxylic dianhydride, for example. It is the residue remove | excluding the carboxylic anhydride group.

These photopolymerizable compounds may be used alone or in combination of two or more thereof.

In the above, although the molecule | numerator itself was mentioned as a photopolymerizable compound, in this invention, the mixture of (b-1) polymeric binder and (b-2) photopolymerizable monomer shall also be included in (b) photopolymerizable compound.

As said (b-1) polymeric binder, the binder which is easy to develop and which can develop alkali is preferable.

Specifically, monomers having a carboxyl group such as acrylic acid and methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2 Hydroxypropyl methacrylate, N-butyl acrylate, N-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, benzyl acrylate, benzyl methacrylate, phenoxy acrylate, phenoxy methacrylate Copolymers of latex, isobornyl acrylate, isobornyl methacrylate, glycidyl methacrylate, styrene, acrylamide, acrylonitrile and the like, and phenol novolak type epoxy acrylate polymer, phenol novolak type epoxy Methacrylate polymers, cresol novolac type epoxy acrylate polymers, cresol novolac type epoxy methacrylate polymers, 'S phenol A epoxy acrylate polymers, it may be mentioned resins such as bisphenol S-type epoxy acrylate polymer. Acryloyl group or methacryloyl group is introduce | transduced into the said resin, crosslinking efficiency becomes high, and it is excellent in the light resistance and chemical-resistance of a coating film. Content of the monomer component which has carboxyl groups, such as acrylic acid and methacrylic acid which comprise the said resin, has a range of 5-40 mass%. The preferable range of the weight average molecular weight of this polymeric binder is 1,000-100,000. By making a weight average molecular weight 1,000 or more, a coating film can be made uniform. Moreover, developability can be made favorable by setting it as 100,000 or less.

As the photopolymerizable monomer (b-2), methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and ethylene glycol diacryl Ethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacryl Rate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetra Acrylate, Pentaerythritol Tet Methacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 1,6-hexanediol diacrylate, benzyl acrylate, benzyl methacrylate Although acrylate, cardepoxy diacrylate, acrylic acid, methacrylic acid, etc. are mentioned, It is not limited to these.

When the component (b) consists of the component (b-1) and the component (b-2), the component (b-1) is the sum of the component (b-1), the component (b-2) and the photopolymerization initiator (c). It is good to mix | blend in the range of 10-60 weight part among 100 weight part. By making the said compounding quantity 10 weight part or more, a film | membrane can be easily formed at the time of application | coating and drying, and the film strength after hardening can fully be raised. Moreover, developability can be made favorable by making a compounding quantity 60 weight part or less. Furthermore, it is preferable that (b-2) component is mix | blended in the range of 15-50 weight part per 100 weight part of components of (b-1) component, (b-2) component, and (c) photoinitiator in total. By making the said compounding quantity 15 weight part or more, the photocuring defect can be prevented and sufficient heat resistance and chemical-resistance can be obtained. Moreover, coating film formation ability can be made favorable by using 50 weight part or less.

What is necessary is just to select the said (c) photoinitiator according to the kind of said (b) photopolymerizable compound. You may use this photoinitiator 1 type or in combination of 2 or more types. As this photoinitiator, for example, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] 2-hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-ddecylphenyl ) -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-monopolynopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-monopolynophenyl) -butan-1-one, 2,4, 6-trimethylbenzoyldiphenylphosphineoxide, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylamino benzoic acid, 4-dimethylamino benzoic acid methyl, 4-dimethylamino benzoic acid ethyl, 4-dimethylamino benzoic acid butyl, 4- Dimethylamino-2-ethylhexyl benzoic acid, 4-dimethylamino-2-isoamyl benzoic acid, benzyl-β-methoxyethylacetal, benzyldimethyl ketal, 1 -Phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, o-benzoyl methyl benzoate, 2,4-diethyl thioxanthone, 2-chlorothioxanthone, 2,4- Dimethyl thioxanthone, 1-chloro-4-propoxy thioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethyl thioxanthene, 2-methylthioxanthene, 2-isopropylthione Oxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercapto Benzoimidazole, 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-methoxy Benzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, Join 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-butyldichloroacetophenone, α, α-dichloro-4 Phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1 , 7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) heptane, 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- Lyazine, 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-dimethoxyphenol) ethenyl] -4,6-bis (trichloromethyl)- s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloro Methyl) -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, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy ) Styrylphenyl-s-triazine etc. are mentioned.

Moreover, you may combine photoinitiator with the said photoinitiator.

As this photoinitiation adjuvant, for example, triethanolamine, methyl diethanolamine, triisopropanolamine, 4-dimethylamino benzoate, 4-dimethylamino benzoate, 4-dimethylamino benzoate isoamyl, 4-dimethylamino benzoic acid 2- Ethylhexyl, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (collectively, Michler's Ketone), 4,4'-bis (di Ethylamino) benzophenone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. . You may use this photoinitiator, 1 type, or in combination of 2 or more types.

The (d) adhesion promoter in the photosensitive composition of the present invention is a silane compound having a group containing nitrogen, and a compound having one or less hydrogens bonded to the nitrogen.

As this compound, the amine silane compound which is a secondary or tertiary amine, an isocyanate silane compound, a ketimine silane compound is mentioned, for example. By using these compounds, adhesiveness can be improved.

As said amine silane compound, the compound represented by following formula (3) is mentioned, for example.

(Wherein, R ¹ and R ² represents hydrogen or an organic (provided that at least one of R ¹ and R ² is an organic group), R ^3, R ^4, and R ⁵ are each other independently of 1 to 6 carbon atoms An alkoxy group or an organic group (wherein at least one of R ³ , R ⁴ , and R ⁵ is an alkoxy group), and n represents an integer of 1 to 6)

As an organic group which concerns on said R <^1> and R <^2> , For example, a C1-C10 primary or secondary alkyl group, a C3-C7 cycloalkyl group, a C6-C10 aryl group, a C7-C10 aralkyl group Etc. can be mentioned. Specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, isobutyl group, 2-methylbutyl group, isopentyl group, isohexyl group, iso Propyl group, sec-butyl group, 2-pentyl group, 3-pentyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, phenyl group, trilyl group, xylyl group, mesityl group, 1-naphthyl group, 2-naphthyl group, benzyl group, (alpha)-phenethyl group, (beta) -phenethyl group, etc. are mentioned. It is preferable that it is an electron-donating group among these, and it is especially preferable that it is a phenyl group.

As said isocyanate type silane compound, the compound represented by following formula (4) is mentioned, for example.

* (In formula, R <^3> , R <^4> and R <^5> are the same as the above. Moreover, n represents the integer of 1-6.)

As said ketimine silane compound, the compound represented by following formula (5) is mentioned, for example.

(In formula, R <^6> and R <^7> represents hydrogen or an organic group, and R <^3> , R <^4> and R <^5> are the same as the above. Moreover, n represents the integer of 1-6.

As an organic group which concerns on said R <^6> and R <^7> , For example, a C1-C10 primary or secondary alkyl group, a C3-C7 cycloalkyl group, a C6-C10 aryl group, a C7-C10 aralkyl group Etc. can be mentioned. Specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, isobutyl group, 2-methylbutyl group, isopentyl group, isohexyl group, iso Propyl group, sec-butyl group, 2-pentyl group, 3-pentyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, phenyl group, trilyl group, xylyl group, mesityl group, 1-naphthyl group, 2-naphthyl group, benzyl group, (alpha)-phenethyl group, (beta) -phenethyl group, etc. are mentioned.

The adhesion enhancer is preferably blended in the range of 10 to 10000 ppm, more preferably in the range of 5000 to 9000 ppm, based on the total weight of the photosensitive composition. By setting it as this range, adhesiveness can be improved further.

An organic solvent can be mix | blended with the photosensitive composition of this invention for the improvement of applicability | paintability, and viscosity adjustment. Organic solvents include benzene, toluene, xylene, methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, glycerin, ethylene glycol Monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 3 Methoxybutyl acetate (MBA), 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, methyl carbonate And ethyl carbonate, propyl carbonate, butyl carbonate and the like. Especially, 3-methoxybutyl acetate is preferable at the point which shows not only the outstanding solubility with respect to the soluble component in a photosensitive composition, but also makes the dispersibility of insoluble components, such as a pigment, favorable.

Although the usage-amount of an organic solvent is not specifically limited, It is suitably set according to the coating film thickness in the density | concentration which can be apply | coated to a board | substrate. The viscosity of the photosensitive composition in this invention is 5-100cp, Preferably it is 10-50cp, More preferably, it is 20-30cp. Moreover, solid content concentration is 5-100 mass%, Preferably it is the range of 20-50 mass%.

Moreover, you may add a thermal polymerization inhibitor, an antifoamer, surfactant, etc. to the photosensitive composition of this invention. These can also be used individually or in combination.

As said thermal polymerization inhibitor, a conventionally well-known thing may be sufficient, hydroquinone, hydroquinone monoethyl ether, etc. are mentioned.

As said antifoamer, a conventionally well-known thing may be sufficient, and a silicone type and a fluorine-type compound are mentioned.

As said surfactant, a conventionally well-known thing may be sufficient, and compounds, such as an anionic type, a cation type, and a nonionic type, are mentioned.

<Method of Preparing Photosensitive Composition>

The photosensitive composition of this invention can be prepared by the following method.

(a) a colorant, (b) a photopolymerizable compound, (c) a photopolymerization initiator, (d) an adhesion enhancer, and an organic additive, if necessary, mixed with three roll mills, ball mills, sand mills, etc. Kneading), for example, by filtration with a 5 μm membrane filter to prepare a photosensitive composition.

<Forming method of light shielding layer (black matrix)>

Hereinafter, as an embodiment of the method of forming the light shielding layer using the photosensitive composition of the present invention, an example of a method of forming a black matrix will be described.

First, a photosensitive composition using a light shielding agent as a colorant is coated on a substrate, such as a contact transfer type coating device such as a roll coater, a reverse coater, a bar coater, a spinner (rotary coating device), a kate flow coater, or the like. Apply using a mold coating device. As the substrate, a substrate having light transparency is used, for example, a glass substrate.

After application of the photosensitive composition, the solvent is dried to remove the solvent.

Next, active energy rays, such as an ultraviolet-ray and an excimer laser beam, are irradiated and partially exposed through a negative mask. A light source that emits ultraviolet rays such as a high pressure mercury lamp, an ultra high pressure mercury lamp, a xenon lamp, and a carbon arc can be used for the exposure. Although the energy dose to irradiate changes with the composition of the photosensitive composition, about 30-2000mJ / cm <^2> is preferable, for example.

The black matrix is formed by developing the film | membrane after exposure using a developing solution. The image development method is not specifically limited, For example, an immersion method, a spray method, etc. can be used. In addition, pre-wet may be employed. After image formation, post-bake, post-curing, or the like may be employed for the purpose of increasing the drying of the developer and curing of the resist film. Specific 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.

<Formation method of color filter>

A photosensitive resin composition is applied, dried, exposed to light, and developed on the substrate on which the black matrix is formed, and a pattern (such as a stripe or a dot) is formed at a predetermined position (opening) of a predetermined color on a black layer. Be sure to For example, when manufacturing the RGB color filter of red (R), green (G), and blue (B), using the photosensitive resin composition containing the coloring agent of each color of R, G, and B, the said The process is repeated to form three colored layers.

From the above, the color filter can be formed.

According to the above configuration, it is possible to provide a black matrix and / or a colored layer which hardly peels even under strict conditions such as PCT, and to provide a high quality color filter, and thus a high quality liquid crystal panel.

EXAMPLE

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

(Resin Synthesis Example 1)

First, the compound 1 represented by General formula (1) was synthesize | combined according to the method of Unexamined-Japanese-Patent No. 2001-354735.

That is, 235 g (epoxy equivalent 235) of bisphenol fluorene-type epoxy resin, 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tertbutyl-4-methylphenol, and 72.0 g of acrylic acid were placed in a 500 ml inlet flask. It melted by heating at 90-100 degreeC, blowing in air at a rate of 25 ml / min. Subsequently, the solution was gradually warmed as it was in a cloudy state, heated to 120 ° C, and completely dissolved. Here, although the solution became transparent viscous one by one, stirring was continued as it was. In the meantime, heating stirring was continued until the acid value was measured and it became less than 1.0 mgKOH / g. Twelve hours were required until the acid value reached the goal. Then, it cooled to room temperature and obtained the bisphenol fluorene type epoxy acrylate represented by following formula (6) of colorless and transparent solid.

Subsequently, 600 g of propylene glycol monomethyl ether acetate (PGMEA) was added to 307.0 g of the bisphenol fluorene type epoxy acrylate obtained as described above, and dissolved therein, and then 80.5 g of benzophenonetetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were 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 Compound 1 represented by the above formula (1). Disappearance of the acid anhydride group was confirmed by IR spectrum.

Here, Compound 1 is a compound represented by the formula (1), X is a group represented by the formula (2), Y is an acid anhydride group from 1,2,3,6-tetrahydrophthalic anhydride dianhydride (-CO-O-CO The residue from which-) is removed, Z is a residue from which an acid anhydride is removed from 3,3 ', 4,4'-benzophenone tetracarboxylic acid anhydride, and the Y / Z molar ratio is 50.0 / 50.0.

The photosensitive composition of this invention was prepared using this compound 1 as a main photopolymerizable compound.

Example  One

A photosensitive composition was prepared by the composition shown in Table 1 below.

* 1 20% carbon concentration, manufactured by Mikuni Color, Japan

* 2 adjusted to 55% solids

* 3 Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), from Chiba Specialty Chemicals Co., Ltd.

* 4 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1one manufactured by Chiba-Geigi Co., Ltd.

About Examples 1-4 and Comparative Examples 1-5, the mixture which consists of the said component was mixed with the stirrer for 2 hours, and it filtered with the 5 micrometer membrane filter, and obtained the photosensitive composition.

The obtained photosensitive composition was applied onto a glass substrate having a clean surface having a thickness of 1 mm using a spin coater (TR 25000 (manufactured by Tokyooka Co., Ltd.)) so as to have a dry film thickness of 1.2 μm, and dried at 90 ° C. for 2 minutes to dry the photosensitive composition. Film (photosensitive layer) was formed. This film was then selectively irradiated with ultraviolet light through a negative mask. The exposure amount was 50 mJ. Thereafter, spray development at 25 ° C. for 60 seconds with a 0.5 wt% sodium carbonate aqueous solution was performed to form a black matrix including a line having a line width of 10 μm. Thereafter, it was post-baked in a 220 ° C -30 min circulation oven. The film thickness of each created black matrix was 1.0 micrometer.

In addition, when the produced black matrix was measured with OD measuring apparatus D-200II (made by Gretag Macbeth), OD value was 3.5.

The black matrices of Examples 1 to 4 and Comparative Examples 1 to 5 obtained as described above were left to stand for 2 hours under conditions of a temperature of 120 ° C., a humidity of 100%, and an atmospheric pressure of 2 atm, and the presence or absence of peeling of the black matrix was evaluated. The results are shown in Table 1.

As mentioned above, even in the severe conditions of temperature 120 degreeC, humidity 100%, and atmospheric pressure 2atm, peeling did not generate | occur | produce and adhesiveness was favorable. On the other hand, peeling occurred in the comparative example. In addition, the development residue was not confirmed also in each Example and the comparative example.

When a liquid crystal panel is produced using the color filter in which this black matrix was formed, there is little peeling of a black matrix even under severe conditions, and liquid crystal leakage can be prevented. Therefore, a highly reliable liquid crystal panel can be provided.

In addition, instead of the black pigment, a red, green, or blue colorant is used. A photosensitive composition can be used to form a color filter. Thus, when a red, green, or blue coloring agent is used, photosensitivity is improved compared with the black coloring agent with high light-shielding rate. Therefore, adhesiveness becomes higher than using the black coloring agent. Therefore, by using this photosensitive composition, a color filter with high adhesiveness can be formed and a highly reliable liquid crystal panel can be provided.

Claims (7)

A colorant-containing photosensitive composition containing (a) a colorant, (b) a photopolymerizable compound, (c) a photopolymerization initiator, and (d) an adhesion enhancer, (b) The photopolymerizable compound is acrylic acid, methacrylic acid, fumaric acid, maleic acid, monomethyl fumaric acid, monoethyl fumarate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, ethylene glycol monomethyl ether acryl Ethylene glycol monomethyl ether methacrylate, ethylene glycol monoethyl ether acrylate, ethylene glycol monoethyl ether methacrylate, glycerol acrylate, glycerol methacrylate, acrylic acid amide, methacrylic acid amide, acrylonitrile, meta Chrylonitrile, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, benzyl acryl Latex, benzyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimeth Acrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, butylene glycol dimethacrylate, propylene glycol Diacrylate, propylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, pentaerythritol triacrylate, penta Erythritol trimethacrylate, pentaerythritol tetraacrylate (DPTA), pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate (DPHA), dipenta Eris Lititol hexamethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, cardepoxydiacrylate; Oligomers of the compounds; Polyester (meth) acrylate obtained by reacting (meth) acrylic acid with a polyester prepolymer obtained by condensing polyhydric alcohols with monobasic acid or polybasic acid; Polyurethane (meth) acrylates obtained by reacting a compound having a polyol group and two isocyanate groups and then reacting (meth) acrylic acid; Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolak type epoxy resin, resol type epoxy resin, triphenol methane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycol Epoxy (meth) acrylate resins obtained by reacting a cydyl ester, an aliphatic or alicyclic epoxy resin, an amine epoxy resin or a dihydroxybenzene type epoxy resin with (meth) acrylic acid; Resin which made polybasic acid anhydride react with the said epoxy (meth) acrylate resin; And at least one kind selected from compounds represented by the following formula (1), [Formula 1]

(Wherein n is an integer of 1 to 20, X is a group represented by the following formula (2), Y is a residue obtained by removing a carboxylic anhydride group (-CO-O-CO-) from a dicarboxylic anhydride, Z is a tetracarboxylic dianhydride) Residues removed from the two carboxylic acid anhydride groups) [Formula 2]

 (d) the adhesion enhancer, [Formula 3]

Wherein R ¹ and R ² represent hydrogen or an organic group, provided that R ¹ and R ² At least one is an organic group), R ³ , R ⁴ , and R ⁵ independently of each other represent an alkoxy group or organic group having 1 to 6 carbon atoms, provided that at least one of R ³ , R ⁴ , and R ⁵ is alkoxy Group, and n represents an integer of 1-6).) The photosensitive composition characterized by the above-mentioned. The method of claim 1, Said photopolymerizable compound (b) contains the compound represented by General formula (1), The photosensitive composition characterized by the above-mentioned. The method of claim 1, R ¹ and R ² is an organic group, characterized in that. The method according to claim 1 or 3, At least one of the R ¹ and R ² is an electron donating group, characterized in that the photosensitive composition. The method of claim 1. At least one of the R ¹ and R ² is a phenyl group, characterized in that. The method of claim 1, Said (a) colorant is a light-shielding agent, The photosensitive composition characterized by the above-mentioned. It has a colored layer formed from the photosensitive composition of Claim 1, The color filter characterized by the above-mentioned.