TWI249552B - Photosensitive resin composition used for color filter - Google Patents

Abstract

This invention relates to a photosensitive resin composition used for color filter, in which after coating, exposure and development, the unexposed portion of the substrate and the black matrix using the disclosed resin composition contains very few quantities of residues; whose heat-resistance and alkaline-resistance on pixel color layer remains excellent after post-bake without pigment particle coagulation. The disclosed composition comprises alkaline soluble resin (A), vinyl unsaturated group containing compound (B), photoinitiator (C), organic solvent (D), and pigment (E), wherein the alkaline soluble resin (A) is composed of 0.1 to 100 weight parts of alkaline soluble resin (A-1) and, if necessary, chosen from another alkaline soluble resin (A-2) in weight parts of 99.9 to 0, in which (A-1) and (A-2) add up to 100 parts; wherein the alkaline soluble resin (A-1) is composed of copolymerized composition of 0.2 to 30 weight parts of maleic anhydride monomer (a-1), 3 to 40 weight parts of carboxylic-group containing unsaturated monomer (a-2), and 30 to 96.8 weight parts of other copolymerisable vinyl monomer (a-3) than monomers (a-1) and (a-2), with (a-1), (a-2), and (a-3) add up to 100 parts; the alkaline soluble resin (A-2) is composed of copolymerized composition of blow 0.2 weight parts of maleic anhydride monomer (a'-1), 5 to 50 weight parts of carboxylic-group containing unsaturated monomer (a'-2), and 49.8 to 95 weight parts of other copolymerisable vinyl monomer (a'-3) than monomers (a'-1) and (a'-2), with (a'-1), (a'-2), and (a'-3) add up to 100 parts; and in the above photosensitive resin composition, the ratio of the total content of repeating units for the maleic anhydride monomers (a-1) and (a'-1) of alkaline soluble resin (A) to the content of pigment (E) is between 0.001 and 0.015.

Description

[Technical Field] The present invention relates to a photosensitive resin composition for a color filter of a liquid crystal display. In particular, it provides a small amount of residue on a portion of the substrate that is not exposed on a substrate and a black matrix after coating, exposure, and development; after baking, the heat resistance of the pixel colored layer is good. Further, a photosensitive resin composition for a color filter containing no pigment agglomerated particles. [Prior Art] Currently, color filters have been widely used in applications such as color liquid crystal displays, color facsimile machines, and color cameras. With the increasing market demand for office equipment such as color liquid crystal displays, the production techniques of color filters are also diversified. Methods such as dyeing, printing, electroplating, and dispersion have been developed successively, with dyeing as the main stream. The dyeing process generally uses a photosensitive water-soluble photoresist (such as acrylic resin, gelatin, etc.) to form a specific pattern on the glass substrate, and then after dyeing, fixing, and anti-pollution treatment. A colored pattern can be produced. This process is repeated three times to obtain a pattern of a pixel colored layer such as red (R), green (G), and blue (B), and a protective film is applied to the pattern of the halogen-colored layer. Although the dyeing method has advantages in terms of fineness and spectral characteristics, its dyeing process is complicated and has disadvantages of poor durability. Therefore, recently, the dispersion method has gradually attracted attention. In the dispersion process, the coloring pigment is first dispersed in a photosensitive resin, and the photosensitive resin is applied onto a glass substrate, and subjected to exposure, development, and the like.

1249552 V. Description of invention (2) Fixed pattern. This operation is repeated three times to obtain a pattern of red (R), green (G) and blue (B) pixel colored layers, and a protective film can be applied to the pattern of the pixel colored layer as needed. Therefore, the dispersing method does not require complicated work such as dyeing and fixing, so the productivity can be relatively improved, and the protective film can be produced as needed, and the waste of materials and engineering can be reduced. In the process of the dispersion method, for example, a copolymer obtained by polymerizing thioglycol as a monomer component is used as a binder of a photosensitive resin. The related documents of the photosensitive resin are disclosed in Japanese Patent Publication No. Hei 6-9 5 2 1 No., Japanese Patent Publication No. Hei. No. Hei. However, in the manufacturing process of the color filter, it is necessary to undergo multiple heat treatment steps, such as red (R), green (G) and blue (B), etc., after the formation of the alizarin colored layer pattern is post-bake. The step and the step of forming a transparent conductive film (IT film), etc., which are generally required to be performed at a high temperature of 200 ° C or higher, but the above-mentioned known photosensitive resin is at about 180 ° C for about 1 hour. The heating under the conditions is prone to problems such as the generation of pigment agglomerated particles in the halogen colored layer (the particle diameter of the pigment agglomerated particles is generally between 1 and 10 // m) and the heat resistance is poor. In general, in the process of the dispersion method, the photosensitive resin composition used may also contain a polymer obtained by polymerizing a carboxyl group-unsaturated monomer and another copolymerizable vinyl monomer as a photosensitive resin. For example, it is mentioned in Japanese Patent Laid-Open No. Hei 4 - 1 2 2 9 3 4, Unexamined 10 0 - 2 6 0 3 0 9 that the carboxyl group-containing unsaturated monomer may be a (fluorenyl)acrylic monomer or a water-free horse. The anhydride monomer or both are used in combination.

1249552 V. INSTRUCTIONS (3) Acid monomer 盥2::f1 optical resin composition, for (meth) propylene rate 'anhydro-manic anhydride monomer, specific use amount and the ratio of use of both and check out* The teaching of the specific ratio of the content of the early polymerization unit to the pigment content: the pigment agglomerated particles and the heat resistance in the plain color layer are not made in any way::: The process of the dispersion T ★ 'The other photosensitive resin used The extremely unsaturated acid monomer and other copolymerizable monomers form an unsaturated beauty--addition of polyethylene-containing (meth)propionate-containing ethylenic groups. After the half esterification reaction, the formed ethylenically unsaturated patent is not used as a binder for the photosensitive resin. The phase of the photosensitive resin is as follows: Japanese Patent Laid-Open No. 6-2 282 39, and JP-A-9-9858.昼 昼 ί ί 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光SUMMARY OF THE INVENTION The purpose of sensitization is to provide a color filter for a liquid crystal display, which is developed and then formed.彳 是 是 是 是 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由It is a photosensitive resin composition for the color-resistant filter of alkali particles. The base material contains: · alkali soluble resin (Α), containing ethylenic unsaturated (Ε); its do not (: 8) L photoinitiator (c), organic solvent (D), and pigment 0 In the 1~u, the alkali-soluble resin (Α) is heavily damaged by the alkali-soluble resin (AM) and is optionally selected from an alkali-soluble resin (A - 2 ) 1249552. V. Invention (4)

99. 9~0 parts by weight combined, 100 parts by weight of the above (A-1) and (A_2); wherein the alkali-soluble resin (A-1) is a maleic anhydride monomer (a-1) 0. 2 to 30 parts by weight, 3 to 40 parts by weight of a carboxyl group-containing unsaturated monomer (a-2), and other copolymerizable vinyl monomers other than the monomers (a-1) and (a-2) (8-3) 30 to 96.8 parts by weight of a total of 100 parts by weight of the above (3-1), (8-2), and (a-3); the alkali-soluble resin (A-2) is a horse 0.2 parts by weight or less (excluding 0.2 parts by weight) of the anhydride monomer (a'-1), 5 to 50 parts by weight of the carboxyl group-containing unsaturated monomer (a'-2), monomer (a'-1), 8 to 95 parts by weight of other copolymerizable vinyl monomer (a'-3) other than (a'-2), (a'-1), (a' -2) (a'-3) is a total of 100 parts by weight; and in the above photosensitive resin composition, the total of the polymerized units of the maleic anhydride monomers (a-1) and (a'-1) of the soluble resin (A) is measured. The ratio of the content to the content of the pigment (E) is between 0. 001 and 0. 015. The following is a detailed description of each component of the present invention: (A) Determination of Soluble Resin The soluble resin (A) of the present invention is determined by examining the soluble resin (A - 1 ) 0.1 to 1.0 parts by weight and optionally From an alkali soluble resin (A-2)

9 9. 9 to 0 parts by weight, a total of 100 parts by weight of the above (A-1) and (A-2); wherein the alkali-soluble resin (A-1) is a maleic anhydride monomer (a-1) 0. 2 to 30 parts by weight, carboxyl group-containing unsaturated monomer (a-2) 3 to 40 parts by weight, other monomers (a-Ι), (a-2) other than copolymerizable The vinyl monomer (a-3) 30 to 9 is a total of 100 parts by weight of the above (a-1), (a-2), and (a-3); the alkali-soluble resin (A-2) is a maleic anhydride monomer (a'-1) 0.2 parts by weight or less (excluding 0.2 parts by weight), containing a carboxyl group

Page 8 1249552 V. Inventive Note (5) 5 to 50 parts by weight of unsaturated monomer (a'-2), copolymerizable other than monomers (a'-1), (a'-2) The ethylene monomer (a'-3) is obtained by copolymerization of 49.8 to 95 parts by weight, and the total of (a'-1), (a'-2), and (a'-3) is 100 parts by weight. The above carboxyl group-containing unsaturated monomer (a-2) is, for example, an unsaturated monocarboxylic acid such as acrylic acid, mercaptoacrylic acid, crotonic acid, α-chloroacrylic acid, ethacrylic acid or cinnamic acid; fumaric acid and clothing Unsaturated dicarboxylic acids (anhydrides) such as tonic acid, itaconic anhydride, tococanic acid, and tococanic anhydride; unsaturated polyvalent carboxylic acids (anhydrides) having a valence of three or more, and the like. Among them, acrylic acid and methacrylic acid are preferred. These carboxyl group-containing unsaturated monomers may be used singly or in combination of plural kinds. The type of the above-mentioned carboxyl group-containing unsaturated monomer (a'-2) is the same as that of the above-mentioned carboxyl group-containing unsaturated monomer (a-2), and will not be described herein. The copolymerizable vinyl monomer (a-3) other than the above monomers (a-1) and (a-2) is, for example, a copolymerizable vinyl monomer containing an aromatic functional group (a- 3-1), such as: aromatic vinyl compounds such as styrene, α-mercaptostyrene, vinyl anthracene, vinyl, methoxystyrene; benzyl acrylate, benzyl methacrylate, An unsaturated carboxylic acid ester such as phenyl acrylate or phenyl methacrylate; Ν-phenyl maleimide, Ν-o-hydroxyphenyl maleimide, Ν-m-hydroxyphenyl malay醯iamine, Ν-p-hydroxyphenylmaleimide, Ν-o-nonylphenylmaleimide, Ν-m-nonylphenylmaleimide, Ν-p-a Stupid base maleimide, Ν-o-methoxyphenyl maleimide, Ν-m-methoxyphenyl maleimide, Ν-p-methoxyphenyl Malay马imine, Ν-cyclohexylmaleimide, etc.

1249552

5. Description of the invention (6) Anthraquinones; and a copolymerizable ethylenic monomer (a-3-2) which does not contain an aromatic functional group, such as decyl acrylate or methacrylate. Ethyl acrylate, ethyl methacrylate, n-propyl acrylate, propyl acrylate, isopropyl acrylate, isopropyl acrylate, butyl acrylate, methyl acrylate, Acetate, butyl acrylate, butyl acrylate, second butyl acrylate, second butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-hydroxyethyl acrylate, Mercaptopropane acid 2 is based on the group B, acrylic acid 2 - propyl propyl, methacrylic acid 2 - propyl acetoacetate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, acrylic acid Butyl ester, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 4-propyl hydroxybutyl acrylate, acryl allyl Ester, allyl methacrylate, methoxy triethylene glycol acrylate , meth〇Xy triethyiene glycol methacrylate, lauryl methacrylate, tetradecyl methacrylate, methacrylic acid Cetyl methacrylate, methacrylic acid decyl methacrylate, eicosyl methacrylate, dodecyl decanoate (docosyl) Unsaturated carboxylic acid esters such as methacrylate; acrylic acid 2_aminoacetic acid, 2-aminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 3-aminopropyl acrylate, Unsaturated carboxylic acid aminoalkyl esters such as 3-aminopropyl methacrylate; cyclopropyl acrylate, methacrylic acid ring

1249552 V. INSTRUCTIONS (7) Epoxypropyl esters of unsaturated carboxylic acids such as oxypropyl ester; vinyl carboxylates such as vinyl acetate, vinyl propionate and vinyl butyrate; vinyl methyl ether; An unsaturated ether such as vinyl ether, allyl epoxypropyl ether or decyl allyl epoxypropyl ether; cyanide such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile or vinyl cyanide Vinyl compound; unsaturated decylamine such as acrylamide, methacrylamide, α-chloropropenylamine, hydrazine-hydroxyethyl acrylamide, hydrazine-hydroxyethyl methacrylamide; 3 - an aliphatic conjugated diene such as butadiene, isopropylene or chloropropene.

Among them, styrene, benzyl acrylate, phenyl decyl methacrylate, fluorenyl-phenylmaleimide, decyl acrylate, decyl methacrylate, 2-hydroxyethyl acrylate, fluorenyl group 2-Hydroxyethyl acrylate is preferred. The other copolymerizable vinyl monomers other than the monomers (a-1) and (a-2) may be used singly or in combination of plural kinds. The copolymerizable vinyl monomer (a '-3) other than the above monomers (a'-1) and (a'-2) is, for example, a copolymerizable vinyl monomer containing an aromatic functional group. The copolymer (a ' - 3 - 1 ) and the copolymerizable vinyl monomer (a'-3-2) which does not contain an aromatic functional group.

The above-mentioned aromatic functional group-containing copolymerizable vinyl monomer (a'-3-1) and the aromatic functional group-free copolymerizable vinyl monomer (a'-3-2) An example of a copolymerizable vinyl monomer (a-3-1) and an aromatic functional group-free copolymerizable vinyl monomer (a-3-2) The same, will not be described here. The soluble resin (A) of the present invention is composed of a combination of a soluble resin (A-1) and, if necessary, an alkali-soluble resin (A-2).

Page 11 1249552 V. Description of the invention (8), the content of the soluble resin (A - 1 ) is preferably from 0.1 to 1 0 0 parts by weight, more preferably from 1 to 90 parts by weight, most preferably 2~ 80 parts by weight; and the content of the soluble resin (A-2) is preferably 99.9 to 0 parts by weight, more preferably 99 to 10 parts by weight, most preferably 98 to 20 parts by weight. If the content of the soluble resin (A - 1 ) is less than 0.1 part by weight, or the content of the soluble resin (A - 2 ) is more than 9.9 parts by weight, the photosensitive resin composition is developed, After baking, the heat-staining layer of the alizarin is not good, and pigment agglomerated particles are easily generated. The alkali-soluble resin (A-1) of the present invention, the amount of the monomer for copolymerization, based on 100 parts by weight of the total of the monomers for copolymerization, is as follows: Maleic anhydride monomer (a-1) The amount of use is preferably from 0.2 to 3 parts by weight, more preferably from 0.5 to 25 parts by weight, most preferably from 1.0 to 20 parts by weight. The carboxyl group-containing unsaturated monomer (a-2) is preferably used in an amount of from 3 to 40 parts by weight, more preferably from 5 to 35 parts by weight, most preferably from 8 to 30 parts by weight. 5重量份,更优选为40〜94。 The monomer (a - 1), (a - 2) other than the copolymerizable vinyl monomer (a-3) is preferably used in an amount of 30 to 96. 8 parts by weight, more preferably 40 to 94. 5 parts by weight, preferably 50 to 91 parts by weight. Further, the above-mentioned aromatic functional group-containing copolymerizable vinyl monomer (a-3-l) is preferably used in an amount of 45 parts by weight or more, more preferably 55 parts by weight or more, most preferably 70% by weight. More than one. In the monomer for copolymerization of the alkali-soluble resin (A-1) of the present invention, if the amount of the maleic acid Sf monomer (a-1) is less than 0.2 part by weight, the photosensitive resin composition is developed. After baking, the color of the alizarin colored layer is not good, and it is easy to produce pigment agglomerated particles; if the amount is more than 30 parts by weight, the photosensitive tree

Page 12 1249552 V. Description of the invention (9) After the development of the lipid composition, the unexposed portion of the substrate and the light-shielding layer (b丨ack nmtnx) are liable to generate residue, and after baking, the base of the halogen-colored layer Poor sex. In the monomer for copolymerization of the alkali-soluble resin (A-ruthenium) of the present invention, if the amount of the Wei group-containing unsaturated monomer (a-2) is less than 3 parts by weight, the photosensitive resin composition is developed. The unexposed portion of the substrate and the black matnx are liable to generate residue; if the amount is more than 4 parts by weight, the photosensitive resin composition is developed, post-baked, and the alizarin-colored layer is alkali-resistant. Not good. In the monomer for copolymerization of the soluble resin (A-1), the use of the copolymerizable vinyl monomer (a-3) other than the monomer (a_W, U-2) is right between 3 0 to 9 6 · 8 parts by weight, the photosensitive resin composition is less likely to be generated on the unexposed portion of the substrate and the black matrix after development, and is checked and then baked, and the pixel colored layer is Heat resistance is preferred. The monomer for copolymerization of the soluble resin (A to 1) of the present invention contains an aromatic f-group functional group, and the amount of the copolymerizable vinyl monomer (aU) used is 45 parts by weight. After the resin composition is developed and post-baked, the heat-sensitive and economical properties of the halogen colored layer are preferred. In the monomer for copolymerization of the soluble resin (A-1), the ratio of the amount of the monomer (a-1) to the amount of the monomer (a_2) used is preferably 〇, 〇1 〜3·0. Between the 'better between 〇 · 〇 3 ~ 2. 8 , the best between 〇 · 〇 5 ~ 2.5; if the ratio of the use of monomer / monomer (a_2) is between 0 · 0 1~3 · Between the 〇, the photosensitive resin composition is developed, and the unexposed part of the substrate and the black matrix are less likely to be produced.

Page 13 1249552 V. INSTRUCTIONS (10) After the residue is produced, and after baking, the colored layer of the pixel is more economical and has better heat and is less likely to produce pigment agglomerated particles. The alkali-soluble resin (A-1) of the present invention may be an alkali-soluble resin of a single composition, or may be used together with two or more different compositions of soluble resins, for example, anhydrous maleic anhydride monomer/acrylic monomer/ Copolymer of abbreviated methacrylate monomer (monomer usage: 5 / 15 / 80) and copolymer of anhydrous maleic anhydride monomer / mercapto acrylate monomer / benzyl methacrylate monomer (Monomer usage: 10/15/75).

The alkali-soluble resin (A-2) of the present invention, the amount of the monomer for copolymerization, is 100 parts by weight based on the total amount of the monomers for copolymerization, as shown below: Maleic anhydride monomer (a ' - The amount of use of 1) is preferably 0. 2 parts by weight or less (excluding 0.2 parts by weight), more preferably 0 to 0.15 parts by weight, most preferably 0 to 0.1 part by weight. The carboxyl group-containing unsaturated monomer (a' - 2 ) is preferably used in an amount of 5 to 50 parts by weight, more preferably 8 to 45 parts by weight, most preferably 10 to 40 parts by weight.

The amount of the copolymerizable vinyl monomer (a'-3) other than the monomers (a '-1" and (a'-2) is preferably 49. 8 to 95 parts by weight, more preferably 54. 85〜92重量份。 The best is 55.9 to 90 parts by weight. Further, the above-mentioned aromatic functional group-containing copolymerizable vinyl monomer (a'-3-1) is preferably used in an amount of 45 parts by weight or more, more preferably 55 parts by weight or more, most preferably 7 0. More than the weight. The weight of the monomer is less than 0.2 parts by weight, and the amount of the maleic anhydride monomer (a' -1 ) is less than 0.2 parts by weight (excluding 0.2 weight).

Page 14 1249552 V. INSTRUCTION OF THE INVENTION (n) Parts) ′ After the photosensitive resin composition is developed, residues are less likely to be generated on the unexposed portions of the substrate and the light-shielding layer (black mat r 1 x ). In the present invention, the monomer for copolymerization of the soluble resin (A~^^-% 甘σ Τ ^ ^ Ζ , , , , , , 含有 含有 含有 含有 含有 曰 曰 曰 曰 曰 曰 曰 1 1 If the amount of history is less than 5 parts by weight, the photosensitive resin composition is developed, and the base is v ^ ^ /u, 1. , the unexposed portion of the electric plate and the black matriX are easily generated. When the amount used is higher than "parts by weight", the photosensitive resin composition is developed and then baked, and the color of the halogen pigment is not good. In the monomer for copolymerization of the alkali-soluble resin (m^β A , , ιλ , , 曰) of the present invention, the monomers (a-1) and (a-2) may be shamelessly < When the copolymerized vinyl monomer (a, -3) is used in the range of 49.8 to 八, 彳 77 ', the photosensitive resin composition is developed, the unexposed portion of the substrate and the light shielding layer (Mack matrix) It is less prone to residue; it is checked, and after development and post-baking, the color resistance of the halogen colored layer is better. 'The copolymerization monomer of the alkali-soluble resin (A-2) of the present invention contains aromatic When the amount of the copolymerizable vinyl monomer (1), -3_1 ) is between 45 and 5 parts by weight, the photosensitive resin composition is developed and baked, and the heat resistance and resistance of the halogen colored layer are Basicity is preferred. The solvent used in the production of the alkali-soluble resins (A-1) and (A-2) of the present invention is generally ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol oxime ether, diethylene glycol. Ether, diethylene glycol n-propyl ether, diethylene glycol n-butyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether, propylene glycol oxime ether, propylene glycol ethyl ether, dipropylene glycol methyl ether, dipropylene glycol diethyl ether, dipropylene glycol Dipropyl ether, dipropylene glycol n-butyl ether, tripropylene glycol oxime ether (

Page 15

1249552 V. Description of invention (12)

Tripropylene glycol mono methyl ether), (poly)alkylene glycol monoalkyl ethers such as tripropylene glycol mono ethyl ether; ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate Ester, propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, etc. (poly) alkylene glycol monoalkyl ether acetate; diglyme, diethylene glycol methyl ether, diethylene glycol diethyl ether, tetrahydroanthracene Other ethers such as ketone; ketones such as acetophenone, cyclohexanone, 2-heptanone, and 3-heptanone; alkyl lactate such as 2-hydroxypropionic acid methyl vinegar or 2-hydroxypropionic acid ethyl ester; Methyl hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-mercaptopropionate, decyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropane Oxalate ester, ethyl 3-ethoxypropionate, ethoxyacetic acid ethyl acetate, ethyl hydroxyacetate, 2-hydroxy-3-indolyl decanoate, 3-methyl-3-decyloxybutyrate Acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-butyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, N-amyl acetate, isoamyl acetate, N-butyl acrylate, ethyl butyrate, n-propyl butyrate, isopropyl acetonate, n-butyl butyrate, methyl acetonate, ethyl pyruvate, propyl acetonate, acetic acid vinegar, Other esters such as ethyl acetate and ethyl 2-oxybutyrate; aromatic hydrocarbons such as toluene and diphenyl; N-methylpyrrolidone, N,N-dimethylformamide, A carboxylic acid amide such as N,N-dimercaptoacetamide or the like. These solvents may be used singly or in combination of two or more. Among the above solvents, propylene glycol oxime ether acetate and ethyl 3-ethoxypropionate are preferred. The initiator used in the manufacture of the alkali-soluble resins (A-1) and (A-2) is generally a radical-type polymerization initiator such as 2, 2'-azobisisobutyronitrile (2, 2' -azobisisobutyronitrile), 2,2'-azobis(2,4-dimethyl)

Page 16 1249552 V. Description of the invention (13) pentylene) [2, 2, a azobis — (2, 4 — dimethylvaleronitrile)], 2, 2, — 1 bis (4-methoxy 2,4 - Dimethylpentanium)[2,2-82〇1313-(4-methoxy-2, 4-dimethylvaleronitri le)], 2, 2'-azobis-2-methylbutanine (2,2' An azo compound such as azobis-2-methyl butyronitrile; a peroxy compound such as benzoylperoxide. (B) The compound containing an ethylenically unsaturated group is based on 100 parts by weight of the soluble resin (A), and the compound (B) containing the ethylenically unsaturated group of the invention is preferably used in an amount of 5 to 2 2 0 by weight. More preferably, it is 50-160 parts by weight. The above ethylenically unsaturated group-containing compound (B) is an ethylenically unsaturated compound having at least one ethylenically unsaturated group. Specific examples of the compound having an ethylenically unsaturated group in f are propylamine, (meth)acryloquinone morpholine, (mercapto)acrylic acid-7-amino-3,7-diisobutoxymethyl Base (meth) acrylamide, (mercapto) diethyl oxime ethyl acrylate, isobornyl (meth) acrylate, (meth) propylene methyl) diethyl diglycol ( Methyl) acrylate, a third octyl group (dimethylammonamine, diacetone (decyl) acrylamide, cyclopentene (meth) acrylate ^ ^ : (decyl) decyl acrylate, (Mercapto) dimethyl methacrylate acrylonitrile dicyclopentenyl (meth) acrylate, N,N-dimethyl (2~ tetrachloro oxyamino (meth) acrylate tetrachloro ester, (methyl) Acrylic acid tetraterpene ester t ethyl sulfonate, (meth)acrylic acid tetrahydrofurfuryl ester, (fluorenyl) acrylic acid acrylate 2~曰:j:yl)acrylic acid-2-pyromyloxyethyl ester, (曱基) gas oxyethyl ester, (bromo)tribromophenyl acrylate, (A)

1249552 V. INSTRUCTIONS (14) Base) acrylic acid-2-trisphenoxy Ethyl, (mercapto)acrylic acid-2 - acetonitrile, (meth)acrylic acid-2-hydroxypropyl vinegar , vinyl caprolactam, N-vinyl tyrosinone, phenoxyethyl (meth) acrylate, pentaphenyl (meth) acrylate, pentabromophenyl (meth) acrylate, poly (fluorenyl) ethylene glycol acrylate, poly(mono(meth)acrylic acid propylene glycol ester, borneyl (meth)acrylate. Specific examples of the ethylenically unsaturated compound having two or more ethylenically unsaturated groups include ethylene glycol bis(indenyl)acrylate, di(indenyl)dicyclopentenyl acrylate, and triethylene glycol Acrylate, tetraethylene glycol di(meth) acrylate, tris(2-hydroxyethyl)isocyanate bis(indenyl) acrylate, tris(2-hydroxyethyl)isocyanate tri(meth) acrylate, Caprolactone modified tris(2-hydroxyethyl)isocyanate tris(indenyl)acrylate, tris(hydroxy)propyl tris(decyl)acrylate, ethylene oxide (hereinafter referred to as E0) modified by three (hereinafter referred to as E0) Trimethylol propyl acrylate, propylene oxide (hereinafter referred to as P0) modified tris(meth)acrylic acid trishydroxypropyl propyl ester, triethylene glycol bis(indenyl) acrylate, neopentyl glycol Di(indenyl) acrylate, 1,4-butanediol di(meth) acrylate, 1,6-hexanediol di(meth) acrylate, pentaerythritol tris(decyl) acrylate, pentaerythritol tetra ( Methyl) acrylate, polyester bis(indenyl) acrylate, polyethylene glycol bis(indenyl) acrylate Ester, dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta(indenyl) acrylate, dipentaerythritol tetra(meth) acrylate, caprolactone modified dipentaerythritol hexa(meth) acrylate, Ester-modified dipentaerythritol penta(indenyl) acrylate, tetrakis(hydroxy)propyl tetra(decyl)acrylate, E 0 modified bisphenol A di(meth) acrylate, P0 modified bisphenol A di(meth)acrylate, E0 modified hydrogenated bisphenol A bis(indenyl) acrylate, P0 modified hydrogenated bisphenol A di(indenyl)

Page 18 1249552 V. INSTRUCTIONS (15) Acrylate, P 0 modified triglyceride, E 0 modified bisphenol F di(meth)acrylate, phenolic acid polyglycidyl ether (methyl ) Acrylate and so on. Among the above ethylenically unsaturated compounds, preferred is trimethylolpropyl triacrylate, E 0 modified trimethylolpropyl acrylate, p 〇 modified tripropionate trihydroxy decyl propyl Ester, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, caprolactone modified dipentaerythritol hexaacrylate, ditrihydroxymethyl propyl tetraacrylate Ester, P 〇 modified glycerol propionate S. (C) The photoinitiator Lu is preferably used in an amount of from 20 to 120 parts by weight based on 100 parts by weight of the ethylenically unsaturated group-containing compound (B). More preferably, it is from 3 0 to 1 0 0 parts by weight. The photoinitiator (C) may be selected from the group consisting of an acetophenone compound or a biimidazole compound. Among them, an acetophenone-based compound such as: p-dimethylamino acetophenone, a, α'-dimethoxy azo acetophenone (α, α'-dimethoxyazoxyacetophenone), 2, 2 '2,2' ~dimethyl-2-phenylacet〇phenone ^ ), p-oxoylacetophenone (?_11167)1〇乂;^〇61:〇 0]1611〇116), 2-methyl-1 -(4-mercaptothiophenyl)-2-morpholine-1-propanone (2-methyl-l-(4-methylthio pheny1)-2) M〇rph〇1ino propane-1-on ), 2 — T base — 2- N,N-diguanamine-1-(4-morpholino)-1-butanone [2-benzyl · -2 -N, N-dimethy lamino-l-( 4-morphol inopheny 1 )-1-

Page 19 1249552 V. Description of invention (16) butanone] 〇

The di-salt compound (biimida ζ ο 1 e ) such as · 2,2 '-bis(o-o-phenyl)-4,4',5,5'-tetraphenyldiimidazole [2,2' -1^3(〇-chlorophenyl)-4, 41, 5, 55-tetraphenyl-biimidazole], 2, 2'-bis(o-fluorophenyl)_4, 4',5, 5'-tetraphenyl Imidazole [2, 2'-bis (〇-fluorophenyl)-4,4,,5,5,-tetraphenylbiimidazole], 2, 2'-bis(o-methylphenyl)-4, 4', 5, 5 '-, 2'-bis(o-methyl phenyl)-4,4',5,5'-tetraphenyl biimidazole], 2, 2'-bis(o-methoxyphenyl) -4, 4',5,5'-tetraphenyldi^[2,2'-bis(o-methoxyphenyl)-4,4',5,5'-tetraphenylbiimidazole], 2, 2'-double ( P-methoxyphenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(p-methoxyphenyl)-4,4',5,5'-tetraphenylbiimidazole 2,2'-bis(2,2,4,4,4-tetramethoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole [2,2,-1^3 ( 2, 2,,4,4J -tetramethoxyphenyl)-4,4y ,5, -tetraphenyl-13^11^(132〇16], 2,2'-bis(2-phenylphenyl)- 4,4',5,5'-tetraphenyldiimidazole [2,2'-bis(2-chlorophenyl)-4, 4,5,5,-tetraphenylbiimidazole], 2, 2, - double (2, 4-dichlorophenyl)-4,

4',5,5'-tetraphenyldiimidazole [2,2'-1^3(2,4-(11(:}11〇1'〇01161^1)-4, 4',5, 5 '-tetraphenylbiimidazole], such as 2-benzyl-2-N,N-diguanamine-1-(4-morpholinophenyl)-butanone, 2,2-bis(o-chlorophenyl) The photoinitiator is preferably used in combination with -4,4',5,5'-tetraphenyl dimethane. The photosensitive resin composition for color and light-proof sheets of the present invention can be further improved.

Page 20 1249552 V. Description of the invention (17) Step by adding a benzophenone (be η ζ 〇phe η ο ne ) compound as a photoinitiator, such as thi嘲xanth〇ne, 2,4 -2,4-diethylthioxanthanone, D Sekouton, the same 4 - fil wind (thioxanthone - 4 -su 1 f one ), benzophenone, 4, 4' - Bis(diamine) benzophenone [4, 4'-bis(dimethylamino)benzophen〇ne], 4, 4'-bis(diethylamine)dibenzophenone [4,4'-bis(diethylamin〇 ) benzophenone] # 0

Others include benzoic acid (benzil), acetyl (acetyl) and the like α-: _ (a-diketone), benzoin (benzoin) and other keto alcohols (acyl 〇in); diphenylethanol Benzoin methylether,

Benzene ethylether, benzoin isopropyl ether, etc., acyloin ether; 2, 4, 6-trimethylbenzoquinone Phenylphosphine oxide (2,4,6-trime thy 1-benzoyl diphenylphosphineoxide), bis-(2,6-dimethoxybenzoquinone)-2,4,4-tridecylphenylphosphine oxide Bis-(2,6-dimethoxy- benzoyl)-2,4, 4-trimethylbenzyl phosphineoxide] acylphosphine oxide; anthraquinone, 1,4-naphthoquinone (1,4 -naphthoquinone) quinone class; phenacyl chloride, tribromomethyl phenylsulfone, tris(trichloromethyl)-s-triazine [tris(trichloromethyl) a halide such as -s-triazine or a peroxide such as di-tertbutylperoxide. Among them, benzophenone is the best compound, especially

Page 21 1249552

4, 4'-bis(diethylamine) benzophenone works best. (D) Organic solvent The photosensitive resin group for the color filter of the present invention, the hexagram Η匕ΓA, and the 八 乂 系 系 以 以 以 述 述 述 述 述 述 生 〖 The compound of the unsaturated group (the starting component (C) and the pigment (E) described later are essential components, and the additive component is added. The meaning of the compound can be added as described below, and usually, the components other than the pigment (8) are dissolved in an appropriate amount. Organic ί K): "/ week to make a liquid composition. The solvent (D) is selected as the above-mentioned solvent and the alkali-soluble resin (A) and the ethylenic unsaturated group are added.

And (B) ' and the photoinitiator (6), and do not react with the components, and have appropriate volatility. The organic solvent of the present invention is preferably used in an amount of from 300 to 2,500 parts by weight, more preferably from 5 to 2 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A). The above solvent (D) may be selected from the solvents used in the polymerization of the aforementioned alkali-soluble resin (A), and will not be described herein. The above solvents may be used singly or in combination of two or more. Among the solvents (D) described in the month, propylene glycol methyl ether acetate and ethyl 3-ethoxypropionate are also preferred. (Ε) Pigment The pigment (Ε) of the present invention is preferably used in an amount of 20 to 500 parts by weight, preferably 50 to 4,000 parts by weight, based on the parts by weight of the alkali-soluble resin (Α). The pigment (Ε) of the present invention can be used for various inorganic pigments known as the right-weight β ± a-city pigment. The inorganic pigment is composed of a metal oxide, a metal salt, or the like.

1249552 V. INSTRUCTIONS (19) Metal compounds 'specifically, metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, stellite, lanthanum, ytterbium, ytterbium, etc., and composite oxidation of the aforementioned metals For example, the object. Examples of branched pigments are as follows: CI·Pigment Yellow 1, 3, 11, 12, 13, 14, 15, 16, 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, 16 6, 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 〇CI headstock red 1, 2, 3, 4, 5, 6, 7, 8,9, 10, 11, 12, 14,1 5, 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, 5 3 : 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 , 16 6, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 2 0 2, 2 0 6, 2 0 7, 2 0 8, 2 0 9, 215, 216, 2 20, 2 24, 2 2 6, 2 42 243, 2 45, 2 5 4, 2 5 5, 2 64, 265 〇CI Pigment Violet 1, 19, 23, 29, 32, 36, 38, 39 〇 Page 23 1249552 V. INSTRUCTIONS (20) CI Pigment Blue 1, 2, 15, 15:3, 15:4, 15:6, 16, 22, 60, 66. C. I. Pigment Green 7, 3 6, 3 7. C. I. Pigment brown 2 3, 2 5, 2 8 . C. I. Pigment Black 1, 7. The above pigments may be used singly or in combination of two or more kinds. In the photosensitive resin composition for a color filter of the present invention, the average particle diameter of the organic pigment is preferably 〇. 〇3 to 0. 5 // m, more preferably 0. 0 4 to 0. 4 //m , the best is 0.05 ~ 0.3 / / m. In the photosensitive resin composition for a color filter of the present invention, the total content of the polymerized units of the maleic anhydride monomers (a-1) and (a'-1) of the alkali-soluble resin (A) and the content of the pigment (E) are The ratio is preferably between 0. 0 0 1~0 . 0 1 5 , more preferably between 0.0 0 2 and 0.012, and most preferably between 0.0 0 3 and 0.010. If the ratio is less than 0. 0 01, the photosensitive resin composition is developed, and then baked, the heat resistance of the pigmented layer is not good, and pigment agglomerated particles are easily generated; if the ratio is higher than 0. 0 1 5 After the development of the photosensitive resin composition, residues are easily generated on the unexposed portions of the substrate and the black matrix, and the cured color of the halogen colored layer is not good after the baking. In the present invention, the coloring agent (E) may be accompanied by a dispersing agent depending on the intended purpose. Examples of such a dispersing agent include surfactants such as a cationic system, an anionic system, a nonionic system, an amphoteric group, a polyoxo system, and a fluorine system. Wherein, the surfactant is exemplified by polyethylene oxide alkyl ethers such as polyepoxybutane 12-ether ether, polyethylene oxide stearyl ether, polyethylene oxide oleyl ether; Polyethylene oxide octyl phenyl ether, polyethylene oxide nonyl phenyl ether

1249552

Etc. xK epoxy b-alkyl benzoic acid; polyethylene glycol dilaurate, polyethylene glycol distearate and other polyethylene glycol diesters; sorbitan fatty acid vinegar; fatty acid Polyester type; grade 3 amine modified polyamino carboxylic acid vinegar, the following trade names: ΚΡ (Shin-Etsu Chemical Co., Ltd.), sf-8427 (toray Dow Corning Silicon), Pfillon (polyfl〇) w, Kyoeisha Oil Chemical Industry Co., Ltd.), Evdopp [F_T〇p, Tochem Products Co., Ltd.], Megafac (Majorak) Ink Chemical Industry), Frodo (Flu〇rade, Sumitomo 3M), Asahi Guard, Surflon, Asahi Glass, etc. These surfactants may be used singly or in combination of plural kinds or more. In the photosensitive resin composition of the present invention, the coating property is improved, and a surfactant can be used concomitantly. The amount of the surfactant used in the present invention is generally from 〇 to 6 parts by weight based on 1 part by weight of the alkali-soluble resin (A), preferably from 〇 to 3 parts by weight, and the above-mentioned surfactant is exemplified as described above. A surfactant used in pigments. Further, in the photosensitive resin composition of the present invention, various additives may be blended as necessary, such as a filler, a polymer compound other than the alkali-soluble resin (A), an adhesion promoter, an antioxidant, an ultraviolet absorber, and an anti-defense agent. Aggregating agent, etc. The amount of the additive of the present invention is generally 〇1 to 1 part by weight, more preferably 〇6 parts by weight, and most preferably 0 to 3 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A).

Page 25 1249552 V. Description of invention (22)

A polymer compound other than the alkali-soluble resin (A); vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) oxime, N-(2-amino group B -3 -aminopropyl decyl decyl oxycarbazide, N-(2-aminoethyl)-3~ sulfopropyltrimethoxy oxalate, 3-aminopropyltriethoxy decane, 3--glycidylpropyltrimethoxydecane, 3-glycidylpropylmercaptodimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltridecyloxydecane, 3 - chloropropylmethyldimethoxydecane, 3-apropylpropyltrimethoxydecane, 3-methylpropoxypropyltrimethoxydecane, 3-thiolpropyltrimethoxydecane, etc. Promoter; 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, etc.; 2 - (3 - tert-butyl An ultraviolet absorber such as -5-mercapto-2-hydroxyphenyl)-5-chlorophenyl azide or alkoxyphenone; and an anti-agglomerating agent such as sodium polyacrylate. In the photosensitive resin composition for a color filter of the present invention, the above components (A) to (E) are uniformly mixed into a solution state in a stirrer, and if necessary, other additives such as a surfactant and an adhesion aid may be added.

The photosensitive resin composition of the present invention is coated on a substrate by a coating method such as rotary coating, cast coating or roll coating. After coating, the solvent was removed by pre-baking (p r e b a k e ) to form a photosensitive resin composition layer. The substrate according to the present invention may be, for example, an alkali-free glass, a soda-lime glass, a hard glass (Pyrus glass), a quartz glass, or a transparent conductive film attached to the glass, or the like. A photoelectric conversion device substrate (such as a germanium substrate) of a solid-state imaging device or the like. These substrates generally form a black release film that separates the pixels.

Page 26 1249552 V. INSTRUCTIONS (23) The conditions for pre-baking vary depending on the type and blending ratio of each component, and are usually carried out at a temperature of 70 to 90 ° C for 1 minute to 15 minutes. After pre-baking, the photosensitive resin composition layer is exposed between the designated masks, and is immersed in the developing solution at a temperature of 23 ° C for 30 seconds to 5 minutes for development, and is not partially removed. Form a pattern. For the light used for exposure, ultraviolet rays such as g-line, h-line, and i-line are preferable, and the ultraviolet device may be a (super) high mercury lamp and a metal halogen lamp. Further, the developing solution is used, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, sodium citrate, sodium decyl citrate, aqueous ammonia, ethylamine, diethylamine, and Basicity of methylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo-(5,4,0)-7-undecene The concentration of the compound and the developer is preferably from 0. 0 0 to 1% by weight, most preferably from 0 to 1% by weight. When a developer composed of such an alkaline aqueous solution is used, it is usually washed with water after development. Next, the pattern is air-dried with compressed air or compressed nitrogen, and then heated by a heating device such as a hot plate or an oven. The heating temperature is set to 150 to 250 ° C, the heating time is 5 minutes to 60 minutes when using a hot plate, and the heating time is 30 minutes to 90 minutes when heated in an oven. By repeating the above steps for each color (mainly including red, green, and blue colors), a color filter layer of a color filter or a light sheet can be produced. Next, an I TO vapor deposited film is formed on the halogen colored layer at a temperature of 2 2 0 ° C to 250 ° C, and if necessary, after etching and wiring the I TO film, the liquid crystal alignment film is coated. Jujua

Page 27 1249552 V. INSTRUCTIONS (24) Amine, and then fired [Embodiment]

It can be used as a color filter for liquid crystal display. The above-mentioned and other techniques of the present invention are described above, and the descriptions of the examples and comparative examples of the above-mentioned examples and comparative examples will be Γ ^ ^ ,. .... ^ A clear understanding. In the four-necked flask of a volume of 100 cc in a synthesis example of a soluble resin (synthesis of sulphur-1), a helium gas inlet, a stirrer, a heater, a condenser, and a thermometer were introduced and introduced. Nitrogen gas was added to the feed composition in an amount shown in Table 1. The above feed composition comprises: 1 part by weight of a maleic anhydride monomer (hereinafter referred to as MAn), and 14 parts by weight of a methyl methic acid monomer (hereinafter abbreviated as maa). 75 parts by weight of benzyl methacrylate monomer (hereinafter referred to as βζΜΑ), 10 parts by weight of methyl acrylate monomer (hereinafter referred to as MA), and solvent 3-ethoxypropionate (hereinafter referred to as EEP) 2 0 0 parts by weight, wherein the monomer mixture is fed in one time. When the contents of the four-necked flask are stirred, the temperature of the oil bath is raised to 100 ° C, and then polymerized as shown in Table 1. 4 parts by weight of the initiator 2, 2,-azobis-2-mercaptobutyronitrile (hereinafter abbreviated as AMBN) was dissolved in the organic solvent EEp, and added to the four-necked cone at intervals of five aliquots at one hour intervals. In the bottle, the reaction temperature of the polymerization process is maintained at 100 ° C for 6 hours. The polymerized product is taken out from the four-necked flask, and the lyophilized solution is devolatilized to obtain an alkali-soluble resin A-Bu. 1. Synthesis Example A_l-2~A-1-8 Synthetic Example A-: l-1 The operation method differs in changing the type and mixing amount of the monomer for polymerization, and the formulation and reaction conditions are as shown in Table 1.

1249552 V. INSTRUCTIONS (25) Synthesis Example A - 1 - 9

At room temperature, a styrene-maleic anhydride copolymer (copolymerization ratio 1:1, molecular weight 10,0 0) 500 parts by weight is dissolved in 135 parts by weight of ethoxyethyl acetate, and added to three 10 parts by weight of ethylamine, 2 parts by weight of argon helium, and 109 parts by weight of polyethylene glycol monomethacrylate (trade name: Blemmer-PE-350) manufactured by Sakamoto Oil Co., Ltd. at 90 to 95° The reaction was carried out for 3 hours at a temperature of C. Further, the reaction solution was cooled to 80 ° C, and 250 parts by weight of hydroxyethyl acrylate was added thereto, and the mixture was reacted at a temperature of 90 to 95 ° C for 3 hours. After the completion of the polymerization, the polymerization product was taken out from the four-necked flask, and the solvent was devolatilized to obtain the soluble resin A - 1 - 9. Synthesis Example A-1-1 0 A nitrogen inlet, a stirrer, a heater, a condenser, and a thermometer were placed on a four-necked flask having a volume of 1 000 ml, and nitrogen gas was introduced. 50 parts by weight of MAn monomer, 50 parts by weight of styrene monomer (hereinafter abbreviated as SM), solvent methyl isobutyl ketone (hereinafter abbreviated as B I BK ) 200 parts by weight, and initiator double peroxide 2 parts by weight of phenylisopropyl (hereinafter abbreviated as DCP) was simultaneously added to a four-necked flask.

The reaction temperature in the polymerization process was maintained at 130 ° C, and the polymerization time was 4 hours. After the polymerization was completed, the polymerization product was taken out from the four-necked flask, and the solvent was devolatilized to obtain an alkali-soluble resin A-1-1 0. [Synthesis Example of Alkali-Soluble Resin (A-2)] Synthesis Example A-2-1 A nitrogen inlet, a stirrer, a heater, a condenser, and a thermometer were placed on a four-necked flask having a volume of 1 000 ml, and Nitrogen gas was introduced and the feed composition was added in an amount shown in Table 1. The above feed composition included: acrylic monomer

Page 29 1249552 V. Description of invention (26) (hereinafter referred to as AA) 5 parts by weight, MAA strictly! r to -a 0 八μλ ® η tongue μ8 15 parts by weight of the original body, 60 parts by weight of the SM monomer, 1 part by weight of the sputum, 1 part by weight, and the solvent, parts by weight. The feeding method of the body mixture is all added at one time. , A, as early as the contents of the four-necked cone bottle was surnamed 1ΠΠ 〇r,,,, ^, Μ ^ arrogant mix, the temperature of the oil bath was raised to 1〇0 C, and then according to the table - The initiator for the polymerization should be in the organic solvent mash, and in a five-necked cone bottle of five equals. The reaction temperature of the polymerization process is maintained at 10 rc for one hour interval, and the polymerization time is "after the completion of the mixing", the polymerization product is obtained from four, and the alkali soluble resin Α-2-1 is obtained. w脱禅' Synthesis Example A-2-2~A-2-4 The same operation method as the synthesis example ^2_1, the difference is to change the type and mixing amount of the early body for the use of the compound, the formulation and reaction conditions are —° [Examples and Comparative Examples of Photosensitive Resin Composition] and Yiyi. Example 1 The alkali-soluble resin fraction (solid fraction) obtained in the above Synthesis Example was used, and the dipentazone shown in Table 3 was used. 〇 weight is abbreviated as B-1) 120 parts by weight, 2-benzyl-2-N,N-dimethylamine y or lower phenyl)-butanone (hereinafter referred to as c-) 22 parts by weight, 4, 4,雔~morpholino)benzophenone (hereinafter referred to as C-2) 22 parts by weight, 2,2,: double and j = ethylamine 4,4,5,5,-tetraphenyldiimidazole (hereinafter referred to as C—3) 22=dano-oxyphenyl)-CI 2 54 (hereinafter referred to as E-1) a mixture of 13 parts by weight, plus = two added pigment oxypropionate (hereinafter referred to as D-丨) 83 〇 weight And C2' After the solvent 3~ethyl ester (hereinafter referred to as D-2) is 170 parts by weight, it is shake-dried, and the solution is dissolved in a dry state, and then dissolved in 12,495,525, and the invention (27) is unmixed, and the color filter can be modulated. The photosensitive resin composition for a sheet is evaluated by the measurement evaluation method of the photosensitive resin composition below, and the result is shown in Table 3. [Evaluation method] (1) Maleic anhydride single sheet of alkali-soluble resin (A) Total content of polymerized units of the bodies (a-Ι) and (a' -1 ) (unit: % by weight) The content can be determined by the following formula: Maleic anhydride monomer (a-Ι) and (a' -1) The total content of the polymerization unit / the total content of the photosensitive resin composition X 1 0 0% by weight

Wherein, the content of the polymerized units of the maleic anhydride monomers (a-Ι) and (a'-1) can be respectively from the raw materials in the polymerization reaction of the alkali-soluble resins (A-1) and (A-2), The conversion rate of each monomer and the volatile components recovered were calculated. (2) Pigment (E) content (unit: % by weight) The content can be obtained by the following calculation formula. The amount of the pigment used / the total content of the photosensitive resin composition X 1 0 0% by weight (III) The total of the polymerized units of the maleic anhydride monomer (a-1) and (a'-1) of the alkali-soluble resin (A) Ratio of content to pigment (E) content

This ratio can be obtained by the following calculation formula. Total content of polymerized units of maleic anhydride monomer (a-1) and (a' -1 ) of alkali-soluble resin (A) / pigment (E) content (IV) Heat resistance The photosensitive resin composition prepared by the heat-resistant property Coated on a 10 cm X 10 cm glass substrate by spin coating to obtain a coating of about 8 // m at 8 5

Page 31 1249552 V. INSTRUCTIONS (28) Pre-bake for 5 minutes at °C. Then, the coating film was irradiated with ultraviolet light (exposure machine Cano η PLA-501F) 200 mJ/cm 2 , and then developed by dip in a developer solution at 23 ° C for 2 minutes, washed with pure water, and then at 200 °. After b baking for 40 minutes, a photosensitive resin layer can be formed on the glass substrate. The photosensitive resin layer on the prepared glass substrate was measured for light transmittance change at a wavelength of 4 〇〇 to 700 nm, and then placed in a 25 〇 art for 6 〇 minutes, and then at 4 0 Light having a wavelength of 0 to 7 0 nm was measured for change in transmittance, and was evaluated based on the change ratio based on the following criteria.

〇: The transmittance changes by 5% or less △: The transmittance changes by 5 to 1 〇% X: The transmittance changes by 10% or more. (5) The testability is obtained, and the photosensitive resin layer on the obtained glass substrate is 4 〇. 〇~7 〇〇1 ^ The light is measured for its light transmittance change' and then placed in 2% Na0H, and then the transmittance change is measured at a wavelength of 4 0 0 to 70 nm, and according to the change ratio It is evaluated on the basis of the following. 〇: The transmittance changes by 5% or less Δ: The transmittance changes by 5 to 10%. X: The transmittance changes by 1% or more. (6) The pigment agglomerated particles, the photosensitive resin layer on the glass substrate to be produced, and the microscope The appearance of pigment agglomerated particles (the particle size of the general agglomerated particles is 1 V m ) is evaluated on the basis of the following. 〇 : no pigment agglomerated particles

1249552 V. INSTRUCTIONS (29) ^ Life pigment agglomerated particles X: multi-pigment agglomerated particles (7) residue, the above-prepared photosensitive resin composition is spin-coated, =1 at a knife X 1 0 cm On the glass substrate, a coating film of about 8 // m was obtained, and it was pre-baked at C for 5 minutes. Then, the coating film is irradiated to the specified mask pattern, the external light (exposure machine Can〇n PLA - 5〇1F) 3 0 0 mJ/cm 2 , ^ , ^ Ϊ 23 2 developer 2 Minute development, removal on the unexposed part 2 of the substrate, washing with pure water, and baking at 200 ° C for 40 minutes, the desired photosensitive resin pattern can be formed in the broken: ΐ t ,, observed by a microscope Whether there is any residue in the unexposed part. 〇: No residue △: a little residue X: Residue reported many examples 2~4 Π Μ Example 1 operation method 'The difference is to change the type and amount of soluble fat (Α), its formula and evaluation results In Table 3. s, Example 5~7 The method of operation of the first example is the change of the soluble fat (A) and the type and amount of the pigment (E). The formulation and evaluation results are shown in the comparison table of Table 3. 1~9 Method of operation of mussels Example 1 The difference is the change in the type and amount of soluble fat (A). The formulation and evaluation results are shown in Table 3.

1249552 V. INSTRUCTION DESCRIPTION (30) Comparative Example 1 0 The same procedure as in Example 1 was carried out except that the amounts of the alkali-soluble resin (A) and the pigment (E) were changed. The formulation and evaluation results are shown in Table 3. The above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, that is, the simple equivalent changes and modifications made by the scope of the invention and the description of the invention are All should remain within the scope of the invention patent. [Note to the attached table]

Table 1: Composition ratio of each synthesis example of the alkali-soluble resin (A-1) of the present invention. Table 2: The composition ratio of each synthesis example of the soluble resin (A-2) of the present invention. Table 3: Composition ratios and evaluation results of the respective examples and comparative examples of the resin composition of the present invention.

Page 34 1249552 V. Description of invention (31)

MAn AA MAA BzMA SM HEMA MA AMBN EEP

碯^^ 骒 骒+3⁄43⁄4 -84.13⁄43⁄4骒舛1 温驷鹞^sds -3⁄43⁄43⁄43⁄4骒24iic^sm(T .3⁄43⁄4缪f龉相鹞2, 2'3«'iL«—21-φ^τφ3—dLia^c ^sIDfT batch cold 桊maleic anhydride acrylic acid methacrylic acid benzyl methacrylar-he styrenemonomer [No-h^drox^ethy 1 (meth )acry 1 ate methyl acrylate 2k-azobislKD-meth^l butyroni tri le ethylGOlrDr+^r〇xypJ- 〇pl〇D^<-frD Al-8 Al-7 1 1 CD > 1 1 cn Al-4 > I 1 GO A-1-2 Al-1 Synthesis Example 〇◦ CO Ol ◦ DO 〇CD cn A MAn (a-1) monomer composition for copolymerization (parts by weight) ΟΊ >· (a-2) CJl INO cn ΟΊ CT) 1~ί o MAA ΟΊ s cn <〇cn —J Cn BzMA ( A-3-1) (a-3) 1-4 CJl HEMA (a-3-2) 〇n CO - CJl A a AMBN Starter oo CD C=5 IND ◦ CD IND ◦ ◦ CsD ◦ iND ◦ CD Ro o CD IND 〇o ro o -d >丨' 露^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ ΕΕΡ ,0-sss ^ 缪 缪 鹞 -3⁄43⁄43⁄4 鹞 -^3⁄43⁄4 缪舛 缪舛 lie lie Ss0as 2, 2ι ^ ιιΛ-2-ψ ^ τ ^

Medicin anhydride acrylic acid methacrylic acid benzyl me1:hacrylai:e styrene monomer-methyl acrylate 2,2' laz〇bis-2-methyl butyronitrile ethyloolCDth〇xypropi〇natrD A-2-4 A-2-3 > 1 IND ώ A-2-1 Synthesis Example CD CD o H—^ P il·—1 Monomer composition for copolymerization (parts by weight) ΟΊ /^NA 1 DO w/ CJ1 Ol CO IND CD h—^ CJ1 > CD BzMA (a -3-1) s Cn IND IND CO (a' -3-2) Private AMBN Starter IND CD 〇〇CD 〇) > Bu ' Emotion ^^ii#smfr(A-2) Xu Xuan Page 36 1249552 V. Description of Invention (33) E-3 D—一〒2 .=-^^:33⁄4^.3⁄4 Curtain Festival 2—Light^12-Λ, τ'ρ·-«Port- 1Λ4-; wife^沭 furnace rl-Tl 4,4·1 stagnation (Bu (^zhong) Bu 舛诮1 2,2·嵴(卷-笋舛_r4,4-,5,5- -S 舛&amp ;卜# 异3丨(^|1妒^琛^器^卜众-«1众众启湓韦Π254 Wen Wei (;36 湓 Ξ 5:6 CLipentaerythritol hexaacryiatc 2lbcnzyT2IN, N-dimethyliino-l-(4lnlorphol inopheny lTl-butanonc 4, 4- lbis(diethylamino)benz〇phen〇nc 2,N-bis(o-chorophenylr4, 4-,5,5' tetraphenylbi imidazole Ethyl 3— Cthoxypropionate propylenecrqlycol methyl, ether acetate o: > 14s "ST 寒一丨.^ ^ Ί®° II H δΚ级_ H Hi VTM CT s tu)> Curtain•Μλ h 1 nU ^ W «2 _ ° 5"& Mai: Secret ^ p? A Bu tw id : Pull o ^ 3 Hu ° £ Cold: Prayer l^f Radical: ί ΐ ϊ ά x ^ m Two tm (2) 1 tN〇CJ1 y ro 〒 o 1 CO 1 ro 1 CO > 1 ro 1 >- oo t oo > 1 1 tND > 1 [NO 1 > 1 1 Q > 1 ! CO >- 1 oo > i II > 1 1 cr- > 1 1 cn > 1 1 >- 1 oo > 1 1 ro > 1 1 [> 〇〇〇〇◦ 〇GO ◦ ~j Q oo CO 〇to ΓΌ tND tND tND tND g A ioo OO CO o IND ΓΌ t^O ro ro ΓΌ s CO -4 o VO 〇〇〇〇〇g OJ 〇〇<〇〇oo CO o ro ro ro rD to tND <〇so oo 〇〇〇〇〇CD s oo 〇〇◦ <=> oo oo ,<=? ro ΓΟ CND CsD ro ro ◦ 1 ◦ Private CD g CO OO oo CO o Ro ro IN D INO tND tND ro ◦ CO αι O” CJ-t D> 〇〇〇〇g CJI 〇g oo CO o ro tND ΓΟ C\〇ro ro CD OO ro cn 〇〇〇〇O g ro CsD ◦ oo 岂tsD Ro ΓΌ ro ro ro IND CD oo CJI -<1 〇X 〇X o § g CO ο OO GO o ro ND ro tsD ro ro oo ◦ s 〇X 〇X ogg oo CO o tND ro ro tND ro ΓΝ3 Oo iJ X 〇X 〇P CD CO CJt OO CO ot\D CN〇tsD ro IND tND CND O CD CT1 Ot OJ X 〇[> 〇o CJI 仏CO ◦ ◦ oo CO o C\D ΓΟ to tND ro tND CsD ◦ g t> 〇X > CD o CO CD <Z^ oo CO CD ro ro ro ro ro CO ◦ s ro U\ 〇X 〇X ' CO ◦ -J C3> CO CO o IND t\D Ro t^o ro tND tND ◦ ◦ o 〇. 〇X 〇X og -J oo CO Q to ΓΟ tsD ro tND ro 〇CO oo OO -JX 〇〇〇Q <〇~J oo CO CI5 ro ro ro ro Ro ro CO 〇〇X [> CD O 3 ~J oo C O cr> ro NO ro ΓΌ tN〇OO ro 〇CD 〇X 〇X o ◦ C3 <33 ro tND CZ3 -J cz> CO NO IND ro tND ΓΌ ro tND 〇oo CJi o衅麦衮tb荩支第37页1249552 Schematic description page 38

Claims (1)

1249552 VI. Patent Application Range 1. A photosensitive resin composition for a color filter, the composition comprising: (A) a soluble resin; (B) a compound containing an ethylenically unsaturated group; (C) light-emitting a starting agent; (D) an organic solvent; and (E) a pigment; wherein the soluble resin (A) is an alkali-soluble resin (A-1) 0. 1 to 1 0 parts by weight and optionally selected from the group consisting of an alkali-soluble resin (A-2) 99.9 to 0 parts by weight, and the above (A-1) and (A-2) are 100 parts by weight in total. The alkali-soluble resin (A-1) is from 0.2 to 30 parts by weight of the maleic anhydride monomer (a-1), and the carboxyl group-containing unsaturated monomer (a-2) is from 3 to 40 parts by weight. 30 to 96.8 parts by weight of other copolymerizable vinyl monomers (a-3) other than the monomers (a-1) and (a-2), and the above (a-Ι), (a - 2重量份以下(2重量份), 2,0 parts by weight of the maleic anhydride monomer (a'-1), the content of the soluble resin (A - 2) is less than 0.2 parts by weight (excluding 0.2 parts by weight), 5 to 50 parts by weight of a carboxyl group-containing unsaturated monomer (a' -2), monomer (a' -1), 49.8 to 95 parts by weight of other copolymerizable vinyl monomer (a'-3) other than (a'-2) are copolymerized to form 'above (a'-1), (a'-2), ( A'-3) a total of 100 parts by weight; and the above-mentioned photosensitive resin composition, the total of the polymerized units of the maleic anhydride monomer (a-Ι) and (a'-1) of the alkali-soluble resin (A) The ratio of the content to the content of the pigment (E) is between 0.001 and 0. 015. Page 39