JP2005148720A - Photosensitive resin composition for color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition for a color filter, the composition producing no residue on a substrate in an unexposed part or on a light shielding layer after development, providing a developed and post-baked pixel with excellent alkali resistance, and having no aggregated pigment particles. <P>SOLUTION: The photosensitive resin composition for a color filter contains (A) an alkali-soluble resin, (B) a polymerizable compound having an ethylenically unsaturated bond, (C) a photopolymerization initiator, (D) solvent and (E) a colorant. The alkali-soluble resin (A) is obtained by polymerization of a maleic acid anhydride monomer, a carboxyl group-containing unsaturated monomer, and other copolymerizable unsaturated monomers except for the above monomers. The ratio of the content of the structural unit derived from the maleic acid anhydride monomer to the content of the colorant (E) ranges from 0.001 to 0.015. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a photosensitive resin composition for a color filter for forming a color filter used in a liquid crystal display, and in particular, on a substrate and a light-shielding layer in an unexposed part after coating, exposing and developing. The present invention relates to a photosensitive resin composition for a color filter in which a pixel post-baked after development is excellent in heat resistance and alkali resistance without generating a residue, and pigment aggregated particles are not generated.

  Conventionally, color filters formed on glass substrates and the like have been widely used in color liquid crystal display devices, color facsimiles, color video cameras, and the like. In the manufacture of this color filter, the use of color liquid crystal display devices for office automation equipment, etc. and the expansion of the market have led to diversification of technology, and dyeing methods, printing methods, electrodeposition methods and dispersion methods have been proposed. Among them, the dyeing method was mainstream.

  In the dyeing method, a predetermined pattern is formed on a glass substrate using a water-soluble resist agent such as acrylic resin or gelatin imparted with photosensitivity, and then a colored pattern is obtained through dyeing, fixing, and anti-dyeing treatment steps. This process is repeated three times to produce red (R), green (G) and blue (B) colored layers, and a protective film is further applied on the colored layers. The dyeing method is excellent in terms of fineness and spectral characteristics, but has a drawback that the process is complicated as described above and the durability is somewhat inferior.

  In recent years, therefore, the dispersion method has attracted attention. In the dispersion method, a resist agent in which a color pigment is dispersed in advance is applied to a glass substrate, and a predetermined pattern is obtained by exposure and development. This process is repeated three times to produce red (R), green (G) and blue (B) colored layers, and a protective film is applied on the colored layers as necessary. As described above, the dispersion method does not require a dyeing process, a fixing process, and the like, so that productivity can be improved and a protective film is not necessarily provided on the colored layer.

  As an alkali developing photosensitive resin capable of forming a pixel pattern by a dispersion method, an alkali-soluble resin containing a methacrylic acid monomer as a component has been reported. Such documents include Patent Document 1, Patent Document 2, Patent Document 3, and the like.

  However, the dispersion method also has a problem in terms of heat resistance. In particular, the resist agent used for the color filter of the liquid crystal color display device is exposed to the post-baking and the heat treatment process of the transparent conductive film, so that it is required not to be colored by heat of 200 ° C. or higher, but the above-mentioned known photosensitivity. The photosensitive resin has a problem in that pigment aggregated particles having a pixel pattern (generally, the particle diameter of the pigment aggregated particles was 1 to 10 μm) are likely to occur when heated at 180 ° C. for about 1 hour.

  Further, as an alkali developing photosensitive resin capable of forming a pixel pattern by a dispersion method, an alkali-soluble resin containing a carboxyl group-containing unsaturated monomer and another copolymerizable monomer as a component has also been reported. Examples of the carboxyl group-containing unsaturated monomer include (meth) acrylic acid monomer, maleic anhydride monomer, and a combination of (meth) acrylic acid monomer and maleic anhydride monomer. Examples of such documents include Patent Document 4 and Patent Document 5.

  However, in the above-mentioned known patent documents, the specific content of (meth) acrylic acid monomer and maleic anhydride monomer and the ratio of both, the content of constituent units derived from maleic anhydride monomer / the content of colorant It is not suggested at all that the effects such as prevention of pigment aggregated particles of the pixel pattern and improvement of heat resistance can be obtained.

  In addition, as an alkali developing photosensitive resin capable of forming a pixel pattern in a dispersion method, a maleic anhydride monomer and a copolymer composed of one or more monomers copolymerizable with the maleic anhydride monomer are mixed with the anhydride of the copolymer. There is also a report that an unsaturated group-containing polycarboxylic acid resin whose maleic acid moiety is half-esterified with a compound such as polyethylene glycol monomethacrylate is an alkali-soluble resin. Examples of such documents include Patent Document 6 and Patent Document 7.

However, the known photosensitive resin composition has a problem in that the post-baked pixels are poor in heat resistance after being subjected to coating, exposure and development, and pigment aggregated particles are likely to be formed.
Japanese Examined Patent Publication No. 6-95211 JP-A-8-183819 JP 9-311210 A Japanese Patent Laid-Open No. 4-122934 Japanese Patent Laid-Open No. 10-260309 JP-A-6-228239 Japanese Patent Laid-Open No. 9-15858

  The present invention has been made in view of the circumstances as described above, and its problem is that after application, exposure, and development processing, no residue is generated on the substrate and the light-shielding layer in the unexposed area, and after development. An object of the present invention is to provide a photosensitive resin composition for a color filter in which post-baked pixels are excellent in heat resistance and alkali resistance, and no pigment aggregated particles are generated.

  The present invention includes, as means for solving the problems, (A) an alkali-soluble resin, (B) a polymerizable compound having an ethylenically unsaturated bond, (C) a photopolymerization initiator, (D) a solvent, and (E) a colorant. A photosensitive resin composition for a color filter, wherein the (A) alkali-soluble resin comprises 0.2 to 30 parts by weight of a maleic anhydride monomer (a-1) and a carboxyl group-containing unsaturated monomer (a-2) 3 to 40 30 parts by weight of copolymerizable unsaturated monomer (a-3) other than (a-1) and (a-2) above (a-1), (a-2) and (a- 3) (total amount 100 parts by weight) obtained by polymerizing alkali-soluble resin (A-1) 0.1-100 parts by weight, maleic anhydride monomer (a'-1) 0-0.2 parts by weight (including 0.2 parts by weight) Not) and carboxyl group-containing unsaturated monomer (a'-2) 5 to 50 parts by weight and copolymerizable unsaturated monomer (a'-3) other than (a'-1) and (a'-2) above It is obtained by polymerizing 49.8 to 95 parts by weight (total amount of (a'-1), (a'-2) and (a'-3) 100 parts by weight) It consists of 99.9-0 parts by weight of an alkali-soluble resin (A-2) (total amount of (A-1) and (A-2) 100 parts by weight), and the maleic anhydride monomer (a-1) and (a The present invention provides a photosensitive resin composition for color filters, wherein the ratio of the content of the structural unit derived from '-1) / the content of the colorant (E) is 0.001 to 0.015.

(A) Alkali-soluble resin The alkali-soluble resin (A) in the present invention is an alkali-soluble resin (A-1) 0.1 to 100 parts by weight, and an alkali-soluble resin (A-2) 99.9 to 0 parts blended as necessary. Parts (100 parts by weight of the total amount of (A-1) and (A-2)). The alkali-soluble resin (A-1) is a maleic anhydride monomer (a-1) 0.2 to 30 parts by weight, a carboxyl group-containing unsaturated monomer (a-2) 3 to 40 parts by weight, and the above (a-1) Copolymerizable unsaturated monomer other than (a-2) (a-3) 30-96.8 parts by weight (total amount of (a-1), (a-2) and (a-3) 100 parts by weight) The alkali-soluble resin (A-2) is obtained by polymerization of maleic anhydride monomer (a′-1) 0.2 part by weight or less (excluding 0.2 part by weight), carboxyl group-containing unsaturated monomer (a ′ -2) 5-50 parts by weight, and copolymerizable unsaturated monomer other than (a'-1) and (a'-2) (a'-3) 49.8-95 parts by weight ((a'-1 ), (A'-2) and (a'-3) in a total amount of 100 parts by weight).

  Examples of the carboxyl group-containing unsaturated monomer (a-2) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, ethylacrylic acid and cinnamic acid; fumaric acid, itaconic acid, Examples thereof include unsaturated dicarboxylic acids (anhydrides) such as itaconic anhydride, citraconic acid and citraconic anhydride; and trivalent or higher unsaturated polycarboxylic acids (anhydrides).

  Of these carboxyl group-containing unsaturated monomers, acrylic acid, methacrylic acid and the like are preferable. The carboxyl group-containing unsaturated monomers can be used alone or in admixture of two or more.

  Examples of the carboxyl group-containing unsaturated monomer (a′-2) are the same as those of the carboxyl group-containing unsaturated monomer (a-2) described above.

  As the copolymerizable unsaturated monomer (a-3) other than (a-1) and (a-2), a copolymerizable unsaturated monomer (a-3-1) containing an aromatic functional group, or It is a mixture comprising a copolymerizable unsaturated monomer (a-3-1) containing an aromatic functional group and a copolymerizable unsaturated monomer (a-3-2) containing no aromatic functional group.

  Examples of the copolymerizable unsaturated monomer (a-3-1) containing an aromatic functional group include aromatic vinyl group compounds such as styrene, α-methylstyrene, vinyltoluene, chloroethylene, and methoxystyrene; benzyl acrylate, Unsaturated carboxylic acid esters such as benzyl methacrylate, phenyl acrylate and phenyl methacrylate; N-phenylmaleimide, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-o- Such as methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, N-o-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, Np-methoxyphenylmaleimide, N-cyclohexylmaleimide, etc. Maleimides It is.

  Examples of the copolymerizable unsaturated monomer (a-3-2) not containing an aromatic functional group include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, Isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybuty Acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, Unsaturated carboxylic acid esters such as dodecyl methacrylate, tetradecyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, eicosyl methacrylate, docosyl methacrylate; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-aminopropyl acrylate, 2- Aminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate Unsaturated carboxylic acid aminoalkyl esters such as acrylate; Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate and vinyl butyrate; Vinyl methyl ether and vinyl Unsaturated ethers such as ethyl ether, allyl glycidyl ether, methallyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylidene cyanide; acrylamide, methacrylamide, α-chloroacrylamide, N -Unsaturated amides such as hydroxyethylacrylamide and N-hydroxyethylmethylacrylamide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene It is done.

  Of these copolymerizable unsaturated monomers (a-3), styrene, benzyl acrylate, benzyl methacrylate, N-phenylmaleimide, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and the like are preferable. . The copolymerizable unsaturated monomer (a-3) can be used alone or in admixture of two or more.

  Examples of copolymerizable unsaturated monomers (a'-3) other than (a'-1) and (a'-2) include copolymerizable unsaturated monomers (a'-3-) containing an aromatic functional group. It is a mixture comprising 1) and a copolymerizable unsaturated monomer (a′-3-2) which does not contain an aromatic functional group.

  Examples of the copolymerizable unsaturated monomer (a′-3-1) containing an aromatic functional group and the copolymerizable unsaturated monomer (a′-3-2) containing no aromatic functional group are described above. This is the same as the copolymerizable unsaturated monomer (a-3-1) containing an aromatic functional group and the copolymerizable unsaturated monomer (a-3-2) containing no aromatic functional group.

  The alkali-soluble resin (A) in the present invention comprises an alkali-soluble resin (A-1) and an alkali-soluble resin (A-2) blended as necessary. In the alkali-soluble resin (A), the content of the alkali-soluble resin (A-1) is 0.1 to 100 parts by weight, preferably 0.1 to 99.9 parts by weight, more preferably 1 to 90 parts by weight, particularly preferably 2 to The content of the alkali-soluble resin (A-2) is 99.9-0 parts by weight, preferably 99.9-0.1 parts by weight, more preferably 99-10 parts by weight, particularly preferably 98-20 parts by weight. (The total amount of (A-1) and (A-2) is 100 parts by weight). When the content of the alkali-soluble resin (A-1) is less than 0.1 parts by weight or the content of the alkali-soluble resin (A-2) exceeds 99.9 parts by weight, the photosensitive resin composition for the color filter is developed. The post-baked pixels have poor heat resistance, and pigment agglomerated particles are easily generated.

  In the polymerization of the alkali-soluble resin (A-1) in the present invention, the content of each monomer (with respect to the total amount of monomers (a-1), (a-2), and (a-3) of 100 parts by weight) is It is as follows.

  The content of the maleic anhydride monomer (a-1) is 0.2 to 30 parts by weight, preferably 0.5 to 25 parts by weight, and more preferably 1.0 to 20 parts by weight.

  The content of the carboxyl group-containing unsaturated monomer (a-2) is 3 to 40 parts by weight, preferably 5 to 35 parts by weight, and more preferably 8 to 30 parts by weight.

  The content of the copolymerizable unsaturated monomer (a-3) other than (a-1) and (a-2) is 30 to 96.8 parts by weight, preferably 40 to 94.5 parts by weight, more preferably 50 to 91 parts by weight. Part.

  In particular, the content of the copolymerizable unsaturated monomer (a-3-1) containing an aromatic functional group contained in the unsaturated monomer (a-3) is preferably 45 parts by weight or more, more preferably 55 parts by weight. It is 70 parts by weight or more, particularly preferably 70 parts by weight or more.

  In the copolymerization monomer of the alkali-soluble resin (A-1) of the present invention, if the content of the maleic anhydride monomer (a-1) is less than 0.2 parts by weight, the heat resistance of the post-baked pixel after development is increased. It becomes worse and pigment aggregated particles are likely to occur. On the other hand, when the content exceeds 30 parts by weight, after application, exposure, and development treatment, a residue is likely to occur on the unexposed portion of the substrate and on the light shielding layer, and the post-baked post-development pixel becomes alkaline. Deteriorate.

  When the content of the carboxyl group-containing unsaturated monomer (a-2) is less than 3 parts by weight in the copolymerization monomer of the alkali-soluble resin (A-1) of the present invention, coating, exposure, and development are performed. After that, a residue tends to be generated on the unexposed portion of the substrate and the light shielding layer. On the other hand, if the content exceeds 40 parts by weight, the alkali resistance of the post-baked pixels after development deteriorates.

  In the copolymerization monomer of the alkali-soluble resin (A-1) of the present invention, the content of the copolymerizable unsaturated monomer (a-3) other than (a-1) and (a-2) is 30 to 96.8. When it is in parts by weight, there is little residue on the unexposed substrate and the light-shielding layer after coating, exposure, and development, and the post-baked post-development pixels have good heat resistance.

  In the copolymerization monomer of the alkali-soluble resin (A-1) of the present invention, when the content of the copolymerizable unsaturated monomer (a-3-1) containing an aromatic functional group exceeds 45 parts by weight, development is performed. The post-baked pixel has good heat resistance and alkali resistance.

  In the copolymerization monomer of the alkali-soluble resin (A-1) of the present invention, the content ratio of the monomer (a-1) to the monomer (a-2) is 0.01 to 3.0, preferably 0.03 to 2.8, more preferably Is 0.05 to 2.5. When the ratio is 0.01 to 3.0, there is little residue on the unexposed substrate and the light-shielding layer after coating, exposure and development, and the post-baked post-baked pixels are resistant to heat and resistance. The alkalinity is excellent, and pigment aggregated particles are hardly generated.

  The alkali-soluble resin (A-1) of the present invention can be used alone or in admixture of two or more. For example, a copolymer consisting of maleic anhydride monomer / acrylic acid monomer / benzyl methacrylate monomer (monomer ratio 5/15/80) and maleic anhydride monomer / methacrylic acid monomer / benzyl methacrylate monomer The combined use of a copolymer (monomer ratio 10/15/75) can be mentioned.

  In the polymerization of the alkali-soluble resin (A-2) in the present invention, the content of each monomer (based on a total amount of 100 parts by weight of the monomers (a′-1), (a′-2), and (a′-3)) Is as follows.

  The content of the maleic anhydride monomer (a′-1) is less than 0.2 parts by weight, preferably 0 to 0.15 parts by weight, more preferably 0 to 0.1 parts by weight.

  The content of the carboxyl group-containing unsaturated monomer (a′-2) is 5 to 50 parts by weight, preferably 8 to 45 parts by weight, and more preferably 10 to 40 parts by weight.

The content of the copolymerizable unsaturated monomer (a'-3) other than (a'-1) and (a'-2) is 49.8 to 95 parts by weight, preferably 54.85 to 92 parts by weight, more preferably 59.9. ~ 90 parts by weight.
In particular, the alkali-soluble resin (A-2) contains 5 to 50 parts by weight of the carboxyl group-containing unsaturated monomer (a′-2) without adding the maleic anhydride monomer (a′-1), (a′- It can also be formed by polymerizing 50 to 95 parts by weight of copolymerizable unsaturated monomer (a′-3) other than 1) and (a′-2).

  In particular, the content of the copolymerizable unsaturated monomer (a′-3-1) containing an aromatic functional group contained in the unsaturated monomer (a-3) is preferably 45 parts by weight or more, more preferably It is 55 parts by weight or more, particularly preferably 70 parts by weight or more.

  In the copolymerization monomer of the alkali-soluble resin (A-2) of the present invention, the content of the maleic anhydride monomer (a′-1) is less than 0.2 parts by weight (excluding 0.2 parts by weight), Residues are less likely to occur on the unexposed portions of the substrate and the light shielding layer after exposure and development.

  In the copolymerization monomer of the alkali-soluble resin (A-2) of the present invention, if the content of the carboxyl group-containing unsaturated monomer (a′-2) is less than 5 parts by weight, coating, exposure, and development treatment are performed. After this is done, residues are likely to occur on the unexposed substrate and the light shielding layer. On the other hand, if the content exceeds 50 parts by weight, the alkali resistance of the post-baked pixels after development deteriorates.

  In the copolymerization monomer of the alkali-soluble resin (A-2) of the present invention, the content of the copolymerizable unsaturated monomer (a'-3) other than (a'-1) and (a'-2) is When the amount is 49.8 to 95 parts by weight, there is little residue on the unexposed part of the substrate and the light-shielding layer after coating, exposure and development, and the post-baked post-development pixels have good heat resistance. is there.

  In the copolymerization monomer of the alkali-soluble resin (A-2) of the present invention, when the content of the copolymerizable unsaturated monomer (a′-3-1) containing an aromatic functional group exceeds 45 parts by weight, The heat resistance and alkali resistance of the post-baked pixel after development are good.

  Solvents used in the production of alkali-soluble resins (A-1) and (A-2) include ethylene glycol monomethyl ether, ethylene glycol monoethyl 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, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono n- Propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol (Poly) alkylene glycol monoalkyl ethers such as methyl ether and tripropylene glycol monoethyl ether; (poly) alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate ) Alkylene glycol monoalkyl ether acetates; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; 2-hydroxy Methyl propionate, 2-hydroxypropionic acid Lactic acid alkyl esters such as chill; methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate , Ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate , N-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate , Ethyl pyruvate, n-propyl pyruvate, Other esters such as methyl acetate, ethyl acetoacetate and ethyl 2-oxobutyrate; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and the like And carboxylic acid amides. These solvents can be used alone or in admixture of two or more. Of these solvents, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate and the like are preferable.

  The polymerization initiator used for the production of the alkali-soluble resins (A-1) and (A-2) is a general radical polymerization initiator, 2,2′-azobisisobutyronitrile, 2,2 ′. -Azo such as azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis-2-methylbutyronitrile System compounds; peroxides such as benzoyl peroxide.

(B) Polymerizable compound having an ethylenically unsaturated bond The content of the polymerizable compound (B) having an ethylenically unsaturated bond in the present invention is preferably 5 to 100 parts by weight (A) of the alkali-soluble resin. 220 parts by weight, more preferably 50 to 160 parts by weight.

  The polymerizable compound (B) having an ethylenically unsaturated bond in the present invention comprises a monomer having one or more polymerizable ethylenically unsaturated bonds.

  Examples of ethylenically unsaturated compounds having one ethylenically unsaturated group include acrylamide, (meth) acryloylmorpholine, 7-amino-3,7-dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) acrylamide, Nyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyldiethylene glycol (meth) acrylate, t-octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate , Dodecyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, N, N-dimethyl (meth) acrylamide, tetrachlorophenyl (meth) a Relate, 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetrabromophenyl (meth) acrylate, 2-tetrabromophenoxyethyl (meth) acrylate, 2-trichlorophenoxyethyl (meth) acrylate, Tribromophenyl (meth) acrylate, 2-tribromophenoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, vinylcaprolactam, N-vinylpyrrolidone, phenoxyethyl (meth) Acrylate, pentachlorophenyl (meth) acrylate, pentabromophenyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) Acrylate, bornyl (meth) acrylate.

  Examples of the ethylenically unsaturated compound having two or more ethylenically unsaturated groups include ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di ( (Meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone-modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate , Trimethylolpropane tri (meth) acrylate, ethylene oxide (hereinafter abbreviated as “EO”) modified trimethylolpropane tri (meth) acrylate, propylene oxide (hereinafter abbreviated as “PO”) Limethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate , Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol tetra (meth) acrylate, caprolaclone modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol penta (Meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, PO-modified bisphenol A di (meth) acrylate, EO-modified hydrogenated bisphenol A di (meth) acrylate, PO-modified hydrogenated bisphenol A di (meth) acrylate, PO-modified glycerol tri (meth) acrylate, EO-modified bisphenol F di (meth) acrylate, (meth) acrylate of phenol novolac polyglycidyl ether, and the like.

  Among the polymerizable compounds having an ethylenically unsaturated bond, particularly preferred are trimethylolpropane triacrylate, EO-modified trimethylolpropane triacrylate, PO-modified trimethylolpropane triacrylate, pentaerythritol triacrylate, and pentaerythritol tetraacrylate. Dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetra (meth) acrylate, caprolaclone-modified dipentaerythritol hexaacrylate, ditrimethylolpropane tetraacrylate, PO-modified glycerol triacrylate.

(C) Photopolymerization initiator The content of the photopolymerization initiator (C) in the present invention is preferably 20 to 120 parts by weight with respect to 100 parts by weight of the polymerizable compound (B) having an ethylenically unsaturated bond, and The amount is preferably 30 to 100 parts by weight.

  Examples of the photopolymerization initiator (C) include acetophenone compounds and biimidazole compounds.

  Examples of acetophenone compounds include p-dimethylaminoacetophenone, α, α′-dimethoxyazoxyacetophenone, 2,2′-dimethyl-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl- (4-methylthiophenol) − 2-morpholino-1-propanone, 2-benzyl-2-N, N-dimethylamino-1- (4-morpholinophenyl) -1-butanone.

  Examples of the biimidazole compound include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-fluorophenyl) -4,5, -diphenylimidazole dimer, 2- (o -Methylphenyl) -4,5, -diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole Dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, 2- (2-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2,4- And dichlorophenyl) -4,5-diphenylimidazole dimer.

  Among them, 2-benzyl-2-N, N-dimethylamino-1- (4-morpholinophenyl) -1-butanone and 2- (2-chlorophenyl) -4,5-diphenylimidazole dimer were used in combination. Photoinitiators are preferred.

  The photosensitive resin composition of the present invention may further contain a benzophenone compound photopolymerization initiator, and examples of the benzophenone compound photopolymerization initiator include thioxanthone, 2,4-diethylthioxanthone, and thioxanthone-4. -Sulfone, benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone and the like.

  Other α-diketones such as benzyl and acetyl; acyloins such as benzoin; acyloin ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; 2,4,6-trimethyl-benzoyldiphenylphosphine oxide; Acylphosphine oxides such as bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylbenzylphosphine oxide; quinones such as anthraquinone and 1,4-naphthoquinone; phenacyl chloride, tribromomethylphenylsulfone And halogen compounds such as tris (trichloromethyl) -s-triazine; peroxides such as di-t-butyl peroxide.

  Of these, benzophenone compounds are preferred, and 4,4′-bis (diethylamino) benzophenone is most preferred.

(D) Solvent The photosensitive composition of the present invention contains the alkali-soluble resin (A), a polymerizable compound (B) having an ethylenically unsaturated bond, and a photopolymerization initiator (C), and is added as necessary. Ingredients are added, but are usually prepared as a liquid composition in which components other than the colorant (E) are dissolved in a suitable solvent (D).

  As the solvent (D), an alkali-soluble resin (A), a polymerizable compound (B) having an ethylenically unsaturated bond, and a photopolymerization initiator (C) are dissolved, and it does not substantially react with these components and is moderate. As long as it has volatility, it can be appropriately selected and used.

  The content of the solvent (D) in the present invention is preferably 300 to 2,500 parts by weight, more preferably 500 to 2,000 parts by weight with respect to 100 parts by weight of the alkali-soluble resin (A). Examples of the solvent (D) are the same as those described in the case of the polymerization of the alkali-soluble resin (A).

  The amount of the solvent (D) of the present invention is preferably 300 to 2500 parts by weight, more preferably 500 to 2000 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A).

  Of these solvents, propylene glycol methyl ether acetate, ethyl 3-ethoxypropionate and the like are preferable. These solvents can be used alone or in admixture of two or more.

(E) Colorant The content of the colorant (E) in the present invention is preferably 20 to 500 parts by weight, more preferably 50 to 400 parts by weight with respect to 100 parts by weight of the alkali-soluble resin (A).

  As the colorant (E) of the present invention, conventionally known various inorganic pigments or organic pigments can be used. Inorganic pigments are metal compounds such as metal oxides and metal complex salts, specifically, metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, And composite oxides of the above metals.

Examples of the organic pigment include the following.
CI Pigment Yellow 1, 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95 , 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152 , 153, 154, 155, 156, 166, 167, 168, 175.

  C.I. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73.

  CI Pigment Red 1, 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, 193, 194, 202, 206, 207, 208, 209, 215, 216, 220, 224, 226, 242, 243, 245, 254, 255, 264, 265.

  C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38, 39.

  C.I. Pigment Blue1, 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 66.

  C.I. Pigment Green 7, 36, 37.

  C.I. Pigment Palm 23, 25, 28.

  C.I. Pigment Black 1, 7.

  The colorant (E) can be used alone or in admixture of two or more.

  In the photosensitive resin composition of the present invention, the average particle size of the organic pigment is preferably 0.03 to 0.5 μm, more preferably 0.04 to 0.4 μm, and particularly preferably 0.05 to 0.3 μm.

  In the photosensitive resin composition of the present invention, “(content of structural unit derived from maleic anhydride monomers (a-1) and (a′-1)) / (content of colorant (E)) Is 0.001 to 0.015, preferably 0.002 to 0.012, and more preferably 0.003 to 0.010.

  When this ratio is less than 0.001, the heat resistance of the post-baked pixels after development is deteriorated and pigment aggregated particles are likely to be generated. On the other hand, if this ratio exceeds 0.015, after application, exposure, and development processing, residues are likely to occur on the unexposed substrate and the light shielding layer, and the alkali resistance of the post-baked pixels after development deteriorates. .

  The colorant (E) in the present invention can be used together with a dispersant as desired. Examples of such a dispersant include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants.

  Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and other polyoxyethylene alkyl ethers. Oxyethylene alkyl phenyl ethers; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters; tertiary amine-modified polyurethanes; polyethyleneimines; , KP (manufactured by Shin-Etsu Chemical), SF-8427 (Toray Dow Corning Silicone), Polyflow (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), Ftop (Manufactured by Tochem Products), Mega Fuck (manufactured by Dainippon Ink and Chemicals), Florard (manufactured by Sumitomo 3M), Asahi Guard, Surflon (manufactured by Asahi Glass) and the like. These surfactants can be used alone or in admixture of two or more.

  In the photosensitive resin composition of the present invention, a surfactant can be used to enhance the coating performance. The compounding amount of the surfactant is preferably 0 to 6 parts by weight, more preferably 0 to 3 parts by weight with respect to 100 parts by weight of the alkali-soluble resin (A). Examples of the surfactant are the same as those described in the section of the colorant.

  The photosensitive resin composition of the present invention contains various additives as necessary, for example, a filler, a polymer compound other than the alkali-soluble resin (A), an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor and the like. Can be blended. The amount of these additives in the present invention is 0 to 10 parts by weight, preferably 0 to 6 parts by weight, more preferably 0 to 3 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A).

  Specific examples of additives include fillers such as glass and alumina; polymer compounds other than carboxyl group-containing alkali-soluble resin (A) such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate; Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltri Methoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropyl Methyldimethoxysilane, 3-chloropropyltrimeth Adhesion promoters such as xylsilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol Antioxidants such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone and other UV absorbers; anti-aggregation agents such as sodium polyacrylate Can be mentioned.

  The photosensitive resin composition of the present invention is a mixture of the above components (A) to (E), other surfactants used as necessary, adhesion promoters and the like with the solvent (D), and various It can be prepared by mixing and dispersing using a mixer and a disperser.

  The photosensitive resin composition of the present invention is applied to a substrate by using a coating method such as a spin coating method, a casting coating method or a roll coating method, and the solvent is removed by pre-baking to form a coating film of the photosensitive resin composition. It is formed.

  As the substrate, for example, non-alkaline glass, soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal displays and the like, and a transparent conductive film attached thereto, or a photoelectric conversion element substrate used for a solid-state imaging device, etc. Examples thereof include a silicon substrate. A black matrix for isolating each pixel is generally formed on these substrates.

  The pre-baking conditions vary depending on the type of each component and the blending ratio, but are usually about 70 to 90 ° C. for about 1 to 15 minutes. After pre-baking, the coating film of the photosensitive resin composition is exposed through a predetermined pattern mask, and unnecessary portions are removed by developing with, for example, a developer at 23 ± 2 ° C. for 30 seconds to 5 minutes. Form a pattern. The light rays used at this time are preferably ultraviolet rays such as g-line, h-line and i-line. As the ultraviolet irradiation device, a high-pressure mercury lamp or a metal halide lamp can be used.

  Examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxy Concentrations of alkaline compounds such as copper, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene are 0.001 to 10% by mass, preferably 0.01 to 1% by mass An alkaline aqueous solution dissolved so as to be used is used.

  When a developer composed of such an alkaline aqueous solution is used, the pattern is generally formed by washing with water after development and then air-drying with compressed air or compressed nitrogen.

  The pattern is then heated by a heating device such as a hot plate or oven at a predetermined temperature, for example, 150 ° C. to 250 ° C. for a predetermined time, for example, 5 minutes to 60 minutes on the hot plate, and 30 to 90 minutes in the oven (post By baking, a target pixel pattern can be obtained.

  By repeating this process for each color (mainly three colors of red, green, and blue), a color filter can be prepared. Then, an indium tin oxide (ITO) vapor deposition film is applied thereon under a vacuum of about 220 to 250 ° C., and the ITO film is etched and formed as necessary, and then a polyimide varnish for liquid crystal alignment film is applied and baked. Thus, it is provided as a color filter for a liquid crystal display.

  Hereinafter, embodiments of the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples.

<Synthesis example of alkali-soluble resin (A-1)>
"Synthesis Example A-1-1"
Under a nitrogen gas atmosphere, in a 1000 ml four-necked flask equipped with a nitrogen gas inlet, stirrer, heater, condenser and thermometer, 1 part by weight of maleic anhydride monomer (hereinafter referred to as MAn), methacrylic 14 parts by weight of acid monomer (hereinafter referred to as MAA), 75 parts by weight of benzyl methacrylate monomer (hereinafter referred to as BzMA), 10 parts by weight of methyl acrylate (hereinafter referred to as MA), and ethyl 3-ethoxypropionate as a solvent 200 parts by weight (hereinafter referred to as EEP) were fed. The feed system for each monomer was batch addition.

  While the contents of the four-necked flask are being stirred, the temperature of the oil bath is raised to 100 ° C., and then the polymerization initiator 2,2′-azobis-2-methylbutyronitrile (hereinafter referred to as AMBN) is used. 4 parts by weight were dissolved in the solvent EEP, and an equal amount of 5 parts of the solution was added into the four-necked flask every hour.

  The temperature of the solution was maintained at 100 ° C., and this temperature was maintained for 6 hours. After completion of the polymerization, the polymer solution was taken out from the four-necked flask, and the solvent was evaporated to obtain an alkali-soluble resin A-1-1.

`` Synthesis example A-1-2 to A-1-8 ''
Resins A-1-2 to A-1-8 were obtained in the same manner as in Synthesis Example A-1-1 except that the type and amount of the monomer were changed. Table 1 shows the types of monomers used, the mixing ratio, and the reaction conditions.

Synthesis Example A-1-9
Under a nitrogen gas atmosphere, a 1000 ml four-necked flask equipped with a nitrogen gas inlet, a stirrer, a heater, a condenser tube and a thermometer was added to a styrene-maleic anhydride copolymer (copolymerization ratio 1: 1, After dissolving 500 parts by weight of molecular weight 10000) in 1300 parts by weight of ethyl cellosolve acetate at room temperature, 10 parts by weight of triethylamine, 2 parts by weight of hydroquinone monomethyl ether, polyethylene glycol monomethacrylate (trade name Blemmer PE-350) 109 manufactured by NOF Corporation A part by weight was added at room temperature and reacted at 90 to 95 ° C. for 3 hours.

  After cooling the reaction solution to 80 ° C., add 250 parts by weight of hydroxyethyl acrylate, react again at 90-95 ° C. for 3 hours, take out the polymer solution from the 4-neck flask, and volatilize the solvent. Alkali-soluble resin A-1-9 was obtained.

Synthesis Example A-1-10
Under a nitrogen gas atmosphere, in a 1000 ml 4-neck flask equipped with a nitrogen gas inlet, a stirrer, a heater, a condenser tube and a thermometer, 50 parts by weight of MAn and 50 parts by weight of styrene monomer (hereinafter referred to as SM) In addition, 200 parts by weight of methyl isobutyl ketone (hereinafter referred to as MIBK) as a solvent and 2 parts by weight of dicumyl peroxide (hereinafter referred to as DCP) as a polymerization initiator were fed. The feed system for each monomer was batch addition.

Man 無水マレイン酸
AA アクリル酸
MAA メタクリル酸
BzMA ベンジルメタクリレート
SM スチレン
HEMA 2-ヒドロキシエチルメタクリレート
MA メチルアクリレート
AMBN 2,2’-アゾビス-2-メチルブチロニトリル
EEP 3-エトキシプロピオン酸エチル The temperature of the solution was maintained at 130 ° C., and this temperature was maintained for 4 hours. After completion of the polymerization, the polymer solution was taken out from the four-necked flask, and the solvent was evaporated to obtain an alkali-soluble resin A-1-10.

Man maleic anhydride
AA acrylic acid
MAA methacrylic acid
BzMA benzyl methacrylate
SM Styrene
HEMA 2-hydroxyethyl methacrylate
MA methyl acrylate
AMBN 2,2'-azobis-2-methylbutyronitrile
EEP Ethyl 3-ethoxypropionate

<Synthesis example of alkali-soluble resin (A-2)>
"Synthesis Example A-2-1"
Under a nitrogen gas atmosphere, in a 1000 ml four-necked flask equipped with a nitrogen gas inlet, a stirrer, a heater, a condenser tube and a thermometer, 5 parts by weight of acrylic acid monomer (hereinafter referred to as AA), MAA 15 Part by weight, 60 parts by weight of SM, 10 parts by weight of MA, and 200 parts by weight of EEP as a solvent were fed. The feed system for each monomer was batch addition.

  While the contents of the four-necked flask are being stirred, the temperature of the oil bath is raised to 100 ° C., and then 4 parts by weight of the polymerization initiator AMBN is dissolved in the solvent EEP, and the solution is divided into five equal parts. The amount was batch-added into the four-necked flask every hour.

  The temperature of the solution was maintained at 100 ° C., and this temperature was maintained for 6 hours. After completion of the polymerization, the polymer solution was taken out from the four-necked flask, and the solvent was evaporated to obtain an alkali-soluble resin A-2-1.

MAn 無水マレイン酸
AA アクリル酸
MAA メタクリル酸
BzMA ベンジルメタクリレート
SM スチレン
MA メチルアクリレート
AMBN 2,2’-アゾビス-2-メチルブチロニトリル
EEP 3-エトキシプロピオン酸エチル `` Synthesis examples A-2-2 to A-2-4 ''
Resins A-2-2 to A-2-4 were obtained by the same operation method as in Synthesis Example A-2-1 except that the type and amount of the monomer were changed. Table 2 shows the types of monomers used, the mixing ratio, and the reaction conditions.

MAn maleic anhydride
AA acrylic acid
MAA methacrylic acid
BzMA benzyl methacrylate
SM Styrene
MA methyl acrylate
AMBN 2,2'-azobis-2-methylbutyronitrile
EEP Ethyl 3-ethoxypropionate

<Examples and Comparative Examples of Photosensitive Resin Composition>
`` Example 1 ''
(A) 100 parts by weight (solid content) of the alkali-soluble resin (A-1-1) obtained in Synthesis Example, (B) a polymerizable compound having an ethylenically unsaturated bond, (C) a photopolymerization initiator, Each component shown in Table 3 (numerical values are parts by weight) as a solvent and (E) colorant was dissolved and mixed with a vibration stirrer, and then a photosensitive resin composition was prepared. Using the obtained photosensitive resin composition, the following measurement items were evaluated. The results are shown in Table 3.

<Measurement item>

"Content of constituent units derived from maleic anhydride monomers (a-1) and (a'-1)"
This content was determined by the following calculation method. The unit of content obtained by the following calculation is% by weight.
(Constituent unit derived from maleic anhydride monomers (a-1) and (a′-1) / content of alkali-soluble resin (A)) × 100% by weight.
Among them, for structural units derived from maleic anhydride monomers (a-1) and (a'-1), the raw material charge during the polymerization reaction of alkali-soluble resins (A-1) and (A-2), Calculation is based on the conversion rate of each monomer and the recovered volatile components.

`` Colorant (E) content ''
This content was calculated | required from the following formula. The unit of content obtained by the following calculation is% by weight.
(Amount of colorant used / content of alkali-soluble resin (A)) x 100% by weight

“Ratio of content of structural units derived from maleic anhydride monomers (a-1) and (a′-1) / content of colorant (E)”
This ratio value was obtained from the following calculation formula.
Content of structural units derived from maleic anhydride monomers (a-1) and (a'-1) / colorant (E) content

"Heat-resistant"
Using a photosensitive resin composition, a coating film having a thickness of 8 μm was applied to a 10 cm × 10 cm glass substrate by spin coating, and after prebaking at 85 ° C. for 5 minutes, a coating film of the photosensitive resin composition was obtained. . The coating film of the photosensitive resin composition was irradiated with 200 mJ / cm ² of ultraviolet rays (exposure machine Canon PLA-501F), immersed in a developer at 23 ° C. for 2 minutes, and rinsed with pure water. Further, post-baking was performed at 200 ° C. for 40 minutes to obtain a photosensitive resin layer on the glass substrate.

The photosensitive resin layer was measured for transmittance at a wavelength of 400 to 700 nm using a microanalyzer (“TC-1800M” manufactured by Tokyo Denshoku Co., Ltd.), and then baked at 250 ° C. for 60 minutes in a clean oven. Carried out. After the additional baking, the transmittance was measured again, and the change rate of the transmittance before and after the additional baking was calculated. The results were evaluated according to the following criteria.
○: Less than 5%.
Δ: 5 to 10%.
×: Over 10%.

"Alkali resistance"
After measuring the transmittance at a wavelength of 400 to 700 nm using a microanalyzer (“TC-1800M” manufactured by Tokyo Denshoku Co., Ltd.) for the photosensitive resin layer formed in the same manner as the heat resistance measurement, 2% hydroxylation Immersion was carried out for 10 minutes in an aqueous sodium solution. After the additional immersion, the transmittance was measured again, and the change rate of the transmittance before and after the additional immersion was calculated. The results were evaluated according to the following criteria.
○: Less than 5%.
Δ: 5 to 10%.
×: Over 10%.

"Pigment aggregated particles"
About the photosensitive resin layer formed similarly to the heat resistance measurement, the presence or absence of pigment aggregated particles was observed with a microscope and evaluated according to the following criteria (the particle diameter of general pigment aggregated particles is 1 to 10 μm).
○: No pigment aggregated particles.
Δ: Little pigment aggregated particles.
X: There are many pigment aggregation particles.

"Residue"
Using this photosensitive resin composition, a coating film having a thickness of 8 μm was applied to a 10 cm × 10 cm glass substrate by spin coating, and after prebaking at 85 ° C. for 5 minutes, a coating film of the photosensitive resin composition was obtained. It was.
Then, this photosensitive resin composition coating film was irradiated with ultraviolet rays (exposure device Canon PLA-501F) 300 mJ / cm ² through a predetermined pattern mask, immersed in a developer at 23 ° C. for 2 minutes, and then purified water Rinse with.
Unnecessary portions were removed by these operations, and further post-baked at 200 ° C. for 40 minutes to obtain a pixel pattern on the glass substrate. This pixel pattern was observed with an electron microscope, and the presence or absence of surface residue was observed and evaluated according to the following criteria.
○: No residue.
Δ: There is a little residue.
X: There are many residues.

`` Examples 2 to 4 ''
A photosensitive resin composition was obtained by the same operation method as in Example 1, except that the type and content of the alkali-soluble resin (A) were changed. Table 3 shows the types of ingredients used, the blending ratio, and the evaluation results.

`` Examples 5 to 7 ''
A photosensitive resin composition was obtained by the same operation method as in Example 1, except that the types and contents of the alkali-soluble resin (A) and the colorant (E) were changed. Table 3 shows the types of ingredients used, the blending ratio, and the evaluation results.

`` Comparative Examples 1-9 ''
A photosensitive resin composition was obtained by the same operation method as in Example 1, except that the type and content of the alkali-soluble resin (A) were changed. Table 3 shows the types of ingredients used, the blending ratio, and the evaluation results.

B-1 ジペンタエリスリトールヘキサアクリレート
C-1 2-ベンジル-2-N,N-ジメチルアミノ-1-(4-モルホリノフェニル)-1-ブタノン
C-2 4,4’- ビス(ジエチルアミノ)ベンゾフェノン
C-3 2,-(2-クロロフェニル)-4,5-テトラフェニルビイミダゾール二量体
D-1 3-エトキシプロピオン酸エチル
D-2 プロピレングリコールメチルエーテルアセテート
E-1 顔料 CI254
E-2 顔料 G36
E-3 顔料 B15:6 `` Comparative example 10 ''
A photosensitive resin composition was obtained by the same operation method as in Example 1, except that the contents of the alkali-soluble resin (A) and the colorant (E) were changed. Table 3 shows the types of ingredients used, the blending ratio, and the evaluation results.

B-1 Dipentaerythritol hexaacrylate
C-1 2-Benzyl-2-N, N-dimethylamino-1- (4-morpholinophenyl) -1-butanone
C-2 4,4'-bis (diethylamino) benzophenone
C-3 2,-(2-Chlorophenyl) -4,5-tetraphenylbiimidazole dimer
D-1 Ethyl 3-ethoxypropionate
D-2 Propylene glycol methyl ether acetate
E-1 Pigment CI254
E-2 Pigment G36
E-3 Pigment B15: 6

Claims (1)

A photosensitive resin composition for a color filter comprising (A) an alkali-soluble resin, (B) a polymerizable compound having an ethylenically unsaturated bond, (C) a photopolymerization initiator, (D) a solvent, and (E) a colorant. The (A) alkali-soluble resin is
Maleic anhydride monomer (a-1) 0.2-30 parts by weight, carboxyl group-containing unsaturated monomer (a-2) 3-40 parts by weight, copolymer other than (a-1) and (a-2) above Alkali-soluble resin obtained by polymerizing 30-96.8 parts by weight of possible unsaturated monomer (a-3) (total amount of (a-1) and (a-2) and (a-3) of 100 parts by weight) ( A-1) 0.1 to 100 parts by weight,
Maleic anhydride monomer (a′-1) 0 to 0.2 parts by weight (excluding 0.2 parts by weight), carboxyl group-containing unsaturated monomer (a′-2) 5 to 50 parts by weight, and (a′-1 ), Copolymerizable unsaturated monomers other than (a'-2) (a'-3) 49.8 to 95 parts by weight (of (a'-1), (a'-2) and (a'-3) (9-2 to 99.9 parts by weight) obtained by polymerizing (total amount 100 parts by weight) (total amount of (A-1) and (A-2) 100 parts by weight), and For color filters, wherein the ratio of the content of structural units derived from maleic anhydride monomers (a-1) and (a'-1) / colorant (E) is 0.001 to 0.015 Photosensitive resin composition.