KR20060128653A - Photosensitive composition - Google Patents

Abstract

Provided is a photosensitive composition which can inhibit a formation of foreign material when applied as substrate, thereby providing a quality of black matrix and color filter. The photosensitive composition comprises (a) coloring agent, (b) photopolymerization initiator, and (c) solvent. The composition further comprises dialkyleneglycol monoalkylether as another solvent(d). The dialkyleneglycol monoalkylether is a solvent represented by formula(1): R^1-O-CnH2n-O-CnH2n-OH(wherein, R^1 is C1-C8 linear, branched or cyclic alkyl group, or aryl group, n is an integer of 2-5). An amount of the solvent represented by formula(1) is 1-50 mass% based on total solvent of the composition. The composition further comprises 3-methoxybutylacetate as the solvent(d). An amount of 3-methoxybutylacetate is 50-85 mass% based on total solvent of the composition.

Description

Photosensitive Composition

1 is a graph showing the film thickness uniformity of the photosensitive compositions of Example 5 and Comparative Example 1. FIG.

The present invention relates to a photosensitive composition suitable for forming a black matrix and / or a color filter for use in displays such as liquid crystal panels.

In liquid crystal panels, particularly TN and STN, liquid crystal panels include a black matrix for enhancing the contrast of an image and a colored layer of RGB generally composed of each of red (R), green (G) and blue (B) colors. The formed color filter is provided. The black matrix and the colored layer are formed by applying a photosensitive composition in which black or each colorant is dispersed to a substrate, drying, exposing and developing the obtained coating film, and repeating forming a desired pattern.

When apply | coating the said photosensitive composition to a board | substrate, the method of using a slit nozzle is used in recent years, and the problem that the aggregate called a foreign material arises on a board | substrate arises. This foreign matter becomes a defect of the black matrix and / or the color filter, making it unusable as a product. In addition, this foreign matter is a significant problem in photosensitive compositions using black pigments such as carbon black.

In order to solve such a problem, for example, Japanese Patent Laid-Open No. 2004-246340 discloses a resin composition using a mixed solvent in which specific physical property values have a specific relationship, but the countermeasure against foreign matter is not sufficient.

This invention is made | formed in view of the said problem, Comprising: It aims at providing the photosensitive composition which can suppress generation | occurrence | production of a foreign material at the time of application | coating to a board | substrate.

The photosensitive composition of this invention is a photosensitive composition containing (a) a coloring agent, (b) photopolymerizable compound, (c) photoinitiator, and (d) solvent, Comprising (d) a dialkylene glycol monoalkyl ether as a solvent It is characterized by.

As said dialkylene glycol monoalkyl ether, the solvent represented by following General formula (1) is preferable.

R ¹ -OC _n H _2n -OC _n H _2n -OH

(Wherein R ¹ represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, or an aryl group, n represents an integer of 2 to 5)

The photosensitive composition of this invention is a photosensitive composition containing (a) a coloring agent, (b) photopolymerizable compound, (c) photoinitiator, and (d) solvent, and (d) solvent contains dialkylene glycol monoalkyl ether. .

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, with respect to a total of 100 weight part of (b) photopolymerizable compound (or a polymeric binder and a photopolymerizable monomer), and (c) photoinitiator, It is preferable to add in the range of 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, ben 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, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate Monomers such as hydrate, dipentaerythritol hexaacrylate (DPHA), dipentaerythritol hexamethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, cardepoxy diacrylate , 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 (2) is also applicable. The compound represented by following formula (2) is a preferable compound in the point which is itself high photocurability.

Wherein m is an integer of 1-20. In addition, it is preferable that X of the compound represented by General formula (2) is a group represented by following General formula (3).

In addition, Y of the compound represented by Formula 2 is, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorine 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 (2) 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, penta Erythritol tetraacrylate, pentaerythritol tetra 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, ethanone, 1 -[9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), 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- Dimethyl No-2-isoamyl benzoic acid, benzyl-β-methoxyethylacetal, benzyldimethyl ketal, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, methyl o-benzoyl benzoate, 2,4-diethyl thioxanthone, 2-chloro thioxanthone, 2,4-dimethyl thioxanthone, 1-chloro-4-propoxy thioxanthone, thioxanthene, 2-chlorothioxanthene, 2 , 4-diethyl thioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthra Quinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl)- 4,5-di (m-methoxyphenyl) -imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone , 4,4'-dichlorobenzophenone, 3,3'-dimethyl-4- Oxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2 Diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloro Loacetophenone, p-tert-butyldichloroacetophenone, α, α-dichloro-4-phenoxycetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosberone ( benzosuberone), 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 (trichloro Lome ) -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-dimethoxyphenol) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-meth 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, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine, etc. Can be 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 said (d) solvent contains dialkylene glycol monoalkyl ether as an essential component. In addition, the isomer shall also be included.

As said dialkylene glycol monoalkyl ether, for example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol Monoisobutyl ether, diethylene glycol mono-n-hexyl ether, diethylene glycol monophenyl ether, diethylene glycol mono2-ethylhexyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono -n-propyl ether, dipropylene glycol monoisobutyl ether, dipropylene glycol mono-n-butyl ether, etc. are mentioned.

As this dialkylene glycol monoalkyl ether, the solvent represented by following General formula (1) is preferable.

Formula 1

R ¹ -OC _n H _2n -OC _n H _2n -OH

(Wherein R ¹ represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, or an aryl group, n represents an integer of 2 to 5)

Especially as R <^1> , a C1-C8 linear alkyl group is preferable, and a C1-C4 linear alkyl group is more preferable. Moreover, n is preferably 2 or 3.

Among the above solvents, dipropylene glycol monomethyl ether is particularly preferable.

Moreover, you may mix | blend the solvent of that excepting the above in order to improve applicability | paintability and viscosity adjustment.

As the solvent, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol Monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol monomethyl Ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate Diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monophenyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Propylene glycol monopropyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate (MBA), 4-methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxy Butyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4 -Methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4 Methyl-4-methoxypentyl acetate, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, tetrahydrofuran, cyclohexanone, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, ethyl-3-propionate Foxy propionate, propyl-3-methoxypropionate, isopropyl-3-methoxypropionate, ethyl ethoxy acetate, ethyl oxy acetate, 2-hydroxy-3-methylbutyrate, propyl acetate, Butyl acetate, isoamyl acetate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl lactate, ethyl lactate, butyl lactate Tylhexyl, benzyl methyl ether, benzyl ethyl ether, dihexyl ether, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, benzene, toluene, xylene, cyclohexanone, Butanol, 3-methyl- 3-methoxybutanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, glycerin and the like. Especially, it is preferable to contain 3-methoxybutyl acetate from the point of time stability, especially.

Although the usage-amount of a solvent is not specifically limited, It is set suitably according to the coating film thickness in the density | concentration which can apply a photosensitive composition to a board | substrate. The viscosity of the photosensitive composition in this invention is 1-100cp, Preferably it is 2-50cp, More preferably, it is 2-10cp. Moreover, it is preferable that it is 5-100 mass%, and, as for solid content concentration, it is more preferable that it is 10-40 mass%.

By using dialkylene glycol monoalkyl ether as a solvent as mentioned above, generation | occurrence | production of a foreign material can be suppressed. In particular, when carbon black is used as the colorant, generation of foreign matters can be particularly suppressed. Furthermore, the roughness of the surface of the film formed of the photosensitive composition can be suppressed. And when apply | coating a photosensitive composition using a spin coater, the uniformity of a film thickness can be improved.

Moreover, it is preferable to contain 1-50 mass% of the said dialkylene glycol monoalkyl ether in the whole solvent in the photosensitive composition, It is more preferable that 3-30 mass% is contained, It is further more preferable that it is 5-15 mass%. Do. Moreover, when combining 3-methoxybutyl acetate, it is preferable that 3-methoxybutyl acetate is contained 40-85 mass% in the total solvent in the photosensitive composition.

Moreover, it is preferable that boiling point is 150-210 degreeC among the said dialkylene glycol monoalkyl ether, and it is more preferable that it is 170-190 degreeC. By setting it as this range, the applicability | paintability of the photosensitive composition can improve and dryness can be improved. In particular, in the case of using a non-spin coater coated with a slit nozzle, the photosensitive composition is dried and solidified at the tip of the slit nozzle, thereby suppressing defects, and further, the dryness of the coating film after coating can be improved.

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) colorant, (b) photopolymerizable compound, (c) photopolymerization initiator and (d) solvent and, if necessary, organic additives are added and mixed with stirrers such as three roll mills, ball mills, and sand mills (dispersion and kneading). Then, for example, a 5 μm membrane filter is used to prepare a photosensitive composition.

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

Hereinafter, as an example of the method of forming a light shielding layer using the photosensitive composition of this invention, the example of the method of forming a black matrix is demonstrated.

First, a photosensitive composition using a light-shielding agent as a colorant is coated on a substrate by a contact transfer type coating device such as a roll coater, reverse coater, bar coater, spinner (rotary coating device), catechin flow coater, and slit nozzle. It is applied using a non-contact type coating device such as a North Pin Coater. 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>

With respect to the substrate on which the black matrix is formed, the photosensitive composition is applied, dried, exposed, and developed in the same manner as described above so that a colored layer of a predetermined color is formed at a predetermined position (opening part) of the black matrix to form a pattern (such as a stripe or a dot). do. For example, when manufacturing the RGB color filter of red (R), green (G), and blue (B), the said process is carried out using the photosensitive composition containing the coloring agent of each color of R, G, and B. This is repeated to form three colored layers.

From the above, the color filter can be formed.

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, Compound 1 represented by Chemical Formula 2 was synthesized according to the method described in JP 2001-354735 A.

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. And it cooled to room temperature, and obtained the bisphenol fluorene type | mold epoxy acrylate represented by following General formula (4) of colorless and transparent.

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 (2). Disappearance of the acid anhydride group was confirmed by IR spectrum.

Here, Compound 1 is a compound represented by the formula (2), X is a group represented by the formula (3), 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.

Using the compound 1 as the main photopolymerizable compound, the photosensitive composition of the present invention was prepared.

(Examples 1-5 and Comparative Examples 1-4)

As the component (a),

(a-1) Carbon dispersion CF black EX-1455 (24% high resistance carbon, 5% dispersant, 29% nonvolatile component, solvent: 3-methoxybutyl acetate, manufactured by Mikuni Color Co., Ltd.)

(b) as a component,

(b-1) 40 parts by mass of compound 1 (55% solids, solvent: 3-methoxybutyl acetate (MBA), molecular weight 3400)

(b-2) 10 parts by mass of dipentaerythritol tetraacrylate

(c) as a component,

(c-1) ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), (CGI242: chiba specialty chemical 2 parts by mass)

(c-2) 1 part by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1one (Igure Cure 369:

Was used.

And (d) component

(d-1) dipropylene glycol monomethyl ether (DPM)

(d-2) 3-methoxybutyl acetate (MA)

(d-3) cyclohexanone

(d-4) Propylene Glycol Monomethyl Ether Acetate

The solvent was prepared so that solid content concentration might be 16 mass% and the ratio with respect to the whole solvent in the photosensitive composition became the ratio shown in Table 1.

Solvent (mass%)  Number of foreign bodies (d-1) (d-2) (d-3) (d-4) Example 1 30 60 10 - 2 Example 2 20 80 - - 2 Example 3 20 70 10 - 3 Example 4 10 80 10 - 3 Example 5 10 90 - - 3 Comparative Example 1 - 100 - - 31 Comparative Example 2 - 90 10 - 13 Comparative Example 3 - 80 20 - 12 Comparative Example 4 - 60 20 20 9

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

A non-spin coater (TR 45410: manufactured by Tokyo Okaka Co., Ltd.), which applies the obtained photosensitive composition with a slit nozzle onto a glass substrate (680 mm x 880 mm x 0.7 mm), having a clean surface, is applied so as to have a dry film thickness of 1.4 µm. It dried at 90 degreeC for 2 minutes, and formed the film (photosensitive layer) of the photosensitive composition. Then, the number of foreign matter in the photosensitive layer on the glass substrate was counted by naked eye and metal microscope using a Na lamp. The results are shown in Table 1. This foreign material can be considered to be an aggregate of (a) component.

As mentioned above, although the number of foreign matters was five or less in the Example, it was a level which is hardly a problem practically, In the comparative example, the number of foreign matters exceeded five and became a level which is problematic in practical use.

(Evaluation of surface roughness)

In addition, the surface roughness (Ra) was measured with the atomic force microscope (AFM) about the film | membrane after apply | coating and drying the photosensitive composition of Example 3 and Comparative Examples 2 and 4 above. The results are shown in Table 2.

Surface Roughness Ra (Å) Example 3 13.2 Comparative Example 2 15.9 Comparative Example 4 15.1

In Example 3 using a dialkylene glycol monoalkyl ether as described above, the surface roughness was good.

(Evaluation of Film Thickness Uniformity)

Furthermore, the photosensitive compositions of Example 5 and Comparative Example 1 were applied by spin coating onto a glass substrate of 550 mm x 650 mm, and the film thickness at the distance from the edge of the substrate was measured.

The result is shown in FIG. As can be seen from FIG. 1, it was evident that the film thickness uniformity was improved by using dialkylene glycol monoalkyl ether.

According to the said structure, generation | occurrence | production of a foreign material can be suppressed at the time of application | coating of the photosensitive composition to a board | substrate, especially at the time of application | coating by the apply | coating method using a slit nozzle. As a result, a high quality black matrix and color filter can be provided, and further, a high quality liquid crystal panel can be provided.

Claims (9)

As a photosensitive composition containing (a) a coloring agent, (b) photopolymerizable compound, (c) photoinitiator, and (d) solvent, (d) Dialkylene glycol monoalkyl ether as a solvent, The photosensitive composition characterized by the above-mentioned. The method of claim 1, The dialkylene glycol monoalkyl ether is a photosensitive composition, characterized in that the solvent represented by the following formula (1): Formula 1 R ¹ -OC _n H _2n -OC _n H _2n -OH (In the above formula, R ¹ represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, or an aryl group, and n represents an integer of 2 to 5). The method of claim 2, R ¹ is a C1-C4 linear alkyl, characterized in that the photosensitive composition. The method of claim 2 or 3, n is 2 or 3, the photosensitive composition. The method of claim 1, The solvent represented by the formula (1) is a dipropylene glycol monomethyl ether, characterized in that the photosensitive composition. The method of claim 1, Content of the solvent represented by the said Formula (1) is 1 mass%-50 mass% in the whole solvent in the photosensitive composition, The photosensitive composition characterized by the above-mentioned. The method of claim 1, The photosensitive composition further comprises 3-methoxybutyl acetate as said (d) solvent. The method of claim 7, wherein Content of the said 3-methoxy butyl acetate is 50 mass%-85 mass% in the whole solvent in the photosensitive composition, The photosensitive composition characterized by the above-mentioned. The method of claim 1, (A) the colorant comprises a carbon black photosensitive composition.

Images