TW200839444A - Radiation sensitive composition, color filter, black matrix and liquid crystal display device - Google Patents

Abstract

There is provided a radiation sensitive composition comprising: (A) a colorant, (B) an alkali soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator, wherein the alkali soluble resin (B) having a structure represented by the following formula (B-1): (wherein R1, R2 and R3 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, X represents a monovalent organic group having an acryloyl group or methacryloyl group, a vinyl group or a l-methylvinyl group, Y represents a divalent organic group, and h is an integer of 1 to 5), and the composition is used for formation of a colored layer.

Description

200839444 IX. INSTRUCTIONS OF THE INVENTION [Technical Field] The present invention relates to a radiation-sensitive composition for forming a coloring layer for use in a color liquid crystal display, a camera tube device, and the like, and also relates to a color filter, Black matrix and liquid crystal display device. In particular, it relates to a radiation-sensitive composition for forming a coloring layer which can easily produce a coloring layer which is excellent in various properties including coating film properties and has excellent developability, and has a composition from the composition. A color filter of a colored layer, a black matrix containing a coloring layer formed from the composition, and a liquid crystal display device including the color filter or the black matrix. The base of the tool is black or the pre-color of the precursor has been filtered or formed into a super-shaped plate. The group is added to the group and the sensory substance is formed into a group. The spoke m' is used to sense the sensitivity. [On the substrate with the desired pattern of the light-shielding layer, the solvent is removed, and the resulting coating film is exposed and developed into a desired pattern to obtain a coloring layer comprising a pixel array of each color or a black matrix. The coloring layer formed has a colored layer which is easy to have an unexposed area of the substrate during development or has residue or scum on the light blocking layer, and the adhesion of the colored layer formed in the exposed area to the substrate or the light blocking layer is insufficient and developed Post-color layer post-baking shows the disadvantage of poor film properties. The present patent application publication No. 1 1 〇 5 7 7/1 9 9 5 discloses a photopolymerizable composition containing (1) a photopolymerization initiator, and (2) an ethylenically unsaturated double bond. a polymerizable monomer and (3) an alkali-soluble resin which is reacted with a styrene or a cyclic substituted derivative thereof and a maleic anhydride -6 - 200839444 copolymer with an arylalkylamine having a primary amine group Further, it is produced that the resin has alkali solubility and can form a color filter excellent in developer resistance, alkali resistance, substrate adhesion, and the like. However, in recent years, it has become necessary to increase the concentration of the pigment in the composition because of the need to form a radiation-sensitive composition having a color filter having high color purity and a black matrix having high light-shielding ability. As a result, there is a problem that the residue remains in the residue during development of the composition and the adhesion between the substrate and the colored layer is insufficient, and it is desired to solve such problems. In addition, in recent years, in the field of color filters, pixels and black substrates formed with low exposure amount are mainly shortened by reducing the exposure amount, and the size of the substrate for forming a color filter is increased. The shape of the pattern and the adhesion to the substrate are extremely excellent. However, it is difficult to obtain a pixel and a black matrix having a good pattern shape while using a conventional color-sensitive radiation-sensitive composition, because when a low exposure amount condition is used, defects are easily generated in the pattern, and side defects or patterns are easily caused. The substrate has insufficient adhesion and is detached from the substrate. It is known that none of the radiation-sensitive compositions can form a color filter having high color purity and a black matrix having high light-shielding ability without causing the aforementioned problems. SUMMARY OF THE INVENTION The present invention has been conceived based on the foregoing circumstances. SUMMARY OF THE INVENTION It is an object of the present invention to provide a radiation-sensitive composition for forming a coloring layer exhibiting excellent developability. In particular, a novel radiation-sensitive composition for forming a colored layer, even at low exposure levels There will be no pattern edge defects or side etching, which can form a fine pattern during development without having undissolved material 200839444 material and scum at the edge of the pattern, and can form a color filter with high color purity and black with high light blocking ability. Matrix. Another object of the present invention is to provide a color filter having a coloring layer formed from the above radiation-sensitive composition and a black matrix formed from the radiation-sensitive composition, and a liquid crystal display device comprising the color filter or the black matrix. Other objects and advantages of the invention will be apparent from the description.

According to the present invention, the above objects and advantages of the present invention are first achieved by a radiation-sensitive composition comprising: (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, And (D) a photopolymerization initiator,

The alkali-soluble resin (B) has a structure represented by the following formula (B-1):

(wherein R1, r2 and R3 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms' X represents a unit price having an acrylonitrile group or a methacryl group, a vinyl group or a 1-methyl group The organic group, γ represents a divalent organic group 'and h is an integer from 1 to 5) and the composition is used to form a colored layer. • 8-200839444 Next, the objects and advantages of the present invention are achieved by a color filter having a layer formed from the aforementioned radiation-sensitive composition or a coloring layer formed from the aforementioned radical. Third, the above objects and advantages are achieved by a liquid crystal display device including the aforementioned black matrix. In the present invention, "radiation" includes visible light, ultraviolet ultraviolet radiation, electron beam, and X-ray, and the "colored layer" includes a layer of a pixel array constituting the color filter or is itself a black matrix: Further, the present invention "filters" The color filter includes at least one substrate and a pixel array having various colors (colored layers) on the substrate, and is also a matrix, a transparent conductive film, a thin film transistor, a protective film, and the like. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention is described in detail below. The radiation-sensitive composition of the present invention comprises (A) a colorant, a soluble resin, (C) a polyfunctional monomer, and (D) a photosensitive poly(A) colorant. The coloring agent contained in the radiation-sensitive composition of the present invention ( The color is not limited and is appropriately selected according to the application of the target colored layer, and may be an organic colorant or an inorganic colorant. Illustrative examples of the organic colorant include organic pigments and natural pigments, including inorganic pigments and constitutions. Pigment. The colored black matrix reaches the color filter or the radiation, and the far surface is 7K package: layer. The formation of the black separator and the (B) alkali start initiator A) is not particularly selected. This material. Inorganic 200839444 The illustrative examples of the aforementioned organic pigments include compounds classified as "pigments" in the Color Index (CI; published by The Society of Dyers and Colourists), in particular, having the following color index (CI) ) Numbered compound: CI·Pigment Yellow 12, CI·Pig Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 17, CI·Pig Yellow 20, CI·Pig Yellow 24, CI Pigment Yellow 31, (:·Ι·Pigment Huang 55, CI·Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 109, CI·Pig Yellow 110, CI·Pig Yellow 138, CI·Pig Yellow 139, CI·Pig Yellow 150, CI·Pig Yellow 153, CI · Pigment Yellow 154, CI Pigment Yellow 166, CI Pigment Yellow 168 and CI·Pigment Yellow ci Pigment Yellow 180; CI Pigment Orange 36, CI·Pigment Orange 43 and CI·Pigment Orange 51; CI·Pigment Red 9, CI·Pigment Red 97, CI·Pigment Red 122, CI Pigment Red 123, CI·Pigment Red 149, CI·Pigment Red 176, CI Pigment Red 177, CI·Pigment Red 180, CI·Pigment Red 215, CI Pigment Red 242, and CI Pigment Red 254; CI·Pigment Violet 19, CI Pigment Violet 23 and CI·Pigment Violet 29; CI Material Blue 15, CI Pigment Blue 15:3, CI·Pigment Blue 15:6; CI·Pigment Green 7, CI·Pigment Green 36 and CI·Pig Green 58; CI·Pigment Brown 23 and CI Pigment Brown 25; and CI · Pigment black! and cj. Pigment black 7. Examples of the aforementioned inorganic pigments include lead sulfate, yellow lead, zinc yellow, rouge (red iron oxide (III)), cadmium red, ultramarine blue, iron blue, chromium oxide green, cobalt Recording, amber, titanium black, synthetic iron black and carbon black. The above-mentioned constitutional pigments -10- 200839444 illustrative examples include titanium oxide, barium sulfate, zinc oxide and calcium carbonate. Examples of the aforementioned carbon black include furnace black, hot carbon Black and acetylene black. Specific examples of furnace black include SAF, SAF-HS, ISAF, ISAF-LS, ISAF-HS, HAF, HAF-LS, HAF-HS, MAF, FEF, FEF-HS, SRF, SRF- LM, SRF-LS, GPF, ECF, N-3 3 9 and N-35 1. Specific examples of thermal carbon black include FT and MT.

Illustrative examples of the commercially available products include DIABLACK A of SAF type (product of Mitsubishi Chemical Corporation) and SEAST 9 (product of Tokai Carbon Co., Ltd.); DIABLACK SA of SAF-HS type (product of Mitsubishi Chemical Corporation) And SEAST 9Η (product of Tokai Carbon Co., Ltd.); ISAF type DIABLACK I (product of Mitsubishi Chemical Corporation) and SEAST 6 (Tokai Carbon Co.,

Ltd.'s product); ISABL-LS type DIABLACK LI (product of Mitsubishi Chemical Corporation) and SEAST 600 (Tokai

Carbon Co·, Ltd.); ISABL-HS type DIABLACK N 2 3 4 (product of Mitsubishi Chemical Corporation) and SEAST 7HM (product of Tokai Carbon Co·, L td ·); DIABLACK H of H AF type ( Products of Mitsubishi Chemical Corporation) and SEAST 3 (products of Tokai Carbon Co., Ltd.); DIABLACK LH (product of Mitsubishi Chemical Corporation) of HAF-LS type and SEAST 300 (Tokai Carbon Co.,

Ltd.'s product); HAF-HS type DIABLACK SH (product of Mitsubishi Chemical Corporation) and SEAST KH ( Tokai -11 - 200839444

Product of Carbon Co., Ltd.; DIABLACK N5 50M of MAF type (product of Mitsubishi Chemical Corporation) and SEAST 116 (product of Tokai Carbon Co., Ltd.); DIABLACK E of FEF type (product of Mitsubishi Chemical Corporation) And SEAST SO, SEAST F and SEAST FM (products of Tokai Carbon Co., Ltd.); DIABLACK N760M of SRF-LM type (

Products of Mitsubishi Chemical Corporation) and HTC#SL (products of Nippon Steel Chemical Co., Ltd.); and DIABLACK G (product of Mitsubishi Chemical Corporation) and SEASTV (product of Tokai Car bonCo., Ltd.) of GPF type. These colorants can be used to modify the surface of the particles with a polymer as desired. A method of coating a carbon black surface with a polymer is disclosed in, for example, Japanese Patent Application Laid-Open No. 7 1 73 3/1 997, 95625/1 997, and 1 24969/1 997. The foregoing colorants may be used singly or in combination of two or more. When the color filter is formed using the radiation-sensitive composition of the present invention, the colorant (A) is preferably a coloring agent having high color rendering property and high heat resistance, especially a coloring agent having high heat decomposition resistance, Organic colorants are preferred, especially organic pigments, because color filters exhibit high definition color rendering and heat resistance. Meanwhile, when a black matrix is formed using the radiation-sensitive composition of the present invention, it is preferred to use an organic pigment or carbon black as a colorant (.A) because the black matrix is required to have a high light-shielding ability. The coloring agent of the present invention may optionally be used in combination with a dispersing agent or a dispersing aid. -12-200839444 As the aforementioned dispersing agent, various surfactants such as cationic, anionic, nonionic and amphoteric surfactants may be used, or suitable A dispersant such as a polymeric dispersant. Among them, a polymer dispersant is preferred. Specific examples thereof include an acrylic copolymer, a modified acrylic copolymer, a polyurethane polyester, an alkylammonium salt of a copolymer or a phosphate, and a cationic comb-graft polymer. The cationic comb-like graft polymer is a structure having a branched polymer in which two or more molecules are grafted onto one molecule of a backbone polymer having a plurality of basic groups (cationic functional groups) The polymer. An example of such a polymer is a polymer comprising a polyethylenimine as a main polymer portion and a ring-opening polymer of ε-caprolactone as a branched polymer portion. Among these dispersants, modified acrylic copolymers, polyurethanes and cationic comb-like graft polymers are preferred. These dispersants are commercially available products. Commercial examples of modified acrylic copolymers include Disperbyk-2000 and Disperbyk-200 1 (products of BYK Japan KK). Descriptions of commercially available products of polyurethanes include Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-1 67, Disperbyk-1 70 and Disperbyk-1 82 (products of BYK Japan KK). An illustrative example of a commercially available product of a cationic comb-like graft polymer includes Solsperse 24000 (product of Lubrizol Japan L td). These dispersants may be used singly or in combination of two or more. The dispersant is preferably used in an amount of not more than 50 parts by weight, more preferably not more than 30 parts by weight, based on 100 parts by weight of the coloring agent (A). Illustrative examples of the aforementioned dispersing aids include blue pigment derivatives and yellow-13-200839444 pigment derivatives. A specific example thereof includes a copper phthalocyanine derivative. (B) Alkali-soluble resin The alkali-soluble resin (B) contained in the radiation-sensitive composition of the present invention has a structure represented by the above formula (B-1). In the above formula (B-1), R1 and R2 are preferably a hydrogen atom. R3 is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom. Preferably, h is 1. In the above formula (B-1), X is preferably a monovalent group represented by the following formula (X-1): ch2=c-^-0 ten ch2·)^- (x-1) (wherein R represents A hydrogen atom or a methyl group, i is an integer of 2 to 5, and j is an integer of 〇 to 10). In the above formula (X-1), i is preferably 2 or 5, and j is preferably an integer of 〇 to 4. In the above formula (X-1), Y is preferably a methylene group, an alkyl group having 2 to 6 carbon atoms or an alkenyl group (such an alkyl group or an alkenyl group intermediate hetero atom); a hexanediyl group, a cyclohexenediyl group or a aryl group having 6 to 12 carbon atoms (the aryl group may have a carboxyl group or an acid anhydride group), more preferably a methylene group, an ethyl group, or a 1,3-ethyl group. Propyl, 1,2-vinyl, 1,2-extenylene, 1,3-propenyl, 2,3-extenylene, cyclohexane-1,2-diyl, 4-ring Hexene-1,2.diyl, 1,2-phenylene, biphenyl-2,2'-diyl or a divalent group of the formula -CH2-0-CH2-.

The alkali-soluble resin (B-14-200839444) contained in the radiation-sensitive composition of the present invention, in addition to the structure represented by the former formula (B-1), preferably has at least one structure selected from the group consisting of (B-2) structure shown:

(wherein R4 represents an aryl group having 6 to 10 carbon atoms or an alicyclic group having 3 to 10 carbon atoms), and a structure represented by the following formula (B-3):

Illustrative examples of the aryl group having 6 to 10 carbon atoms as R4 in the above formula (B-2) include a phenyl group, an o-hydroxyphenyl group, a m-hydroxyphenyl group, a p-hydroxy group. Phenyl, o-tolyl, m-tolyl, p-tolyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl and naphthyl. An illustrative example of an alicyclic group having 3 to 1 carbon atoms of R4 in the above formula (B-2) includes a cyclohexyl group. As R4 in the above formula (B_2), a phenyl group is preferred. The illustrative examples of the halogen atom of R5 to RiQ in the above formula (B-3) include a chlorine atom, a bromine atom and an iodine atom. It is preferred to use a chlorine atom. -15- 200839444 In the above formula (B-3), preferably all of R5 to R1G are a hydrogen atom or R7 is a chlorine atom, a hydroxyl group or a hydroxymethyl group, and all of R5, R6 and R8 to R1G are a hydrogen atom. More preferably, all of R5 to R1G are hydrogen atoms or R7 is a hydroxyl group, and all of R5, R6 and R8 to R1G are hydrogen atoms. In the alkali-soluble resin (B) contained in the radiation-sensitive composition of the present invention, the structure represented by the former formula (B-1) is preferably from 5 to 80% by weight based on the total amount of the soluble resin (B). More preferably, it is from 10 to 60 weights / 〇. When the content of the structure represented by the formula (Β-1) in the alkali-soluble resin (Β) is within the above range, the developability of the radiation-sensitive composition containing the alkali-soluble resin (Β) is improved' The suppression of residue generated during development becomes more effective. The alkali-soluble resin (Β) contained in the radiation-sensitive composition of the present invention has preferably not more than 50% by weight, more preferably 5 to 45% by weight, based on the total amount of the alkali-soluble resin (Β). - 2) The structure shown. Further, the alkali-soluble resin (Β) has a structure represented by the formula (Β-3) which is preferably not more than 60% by weight, more preferably 5 to 40% by weight based on the total of the alkali-soluble resin (Β). Further, the alkali-soluble resin (Β) may have both a structure represented by the former formula (Β-2) and a structure represented by the former formula (Β·3). In this case, the total content of such structures is preferably a base. The total amount of the soluble resin (Β) is not more than 80% by weight, more preferably 1% to 70% by weight. In this case, the individual contents of the structure represented by the former formula ((-2) and the structure of the former formula (Β3) are preferably within the above range. When the content of the structure represented by the present formula (Β-2) and the structure represented by the former formula (Β**3) in the alkali-soluble resin (Β) is within the above range, it is further improved to be formed by the benefit of -16-394444. Adhesion of the color layer to the substrate The alkali solubility contained in the radiation-sensitive composition of the present invention is measured by gel permeation chromatography (GPC) with respect to polystyrene of 2,000 to 100, and the weight average molecular weight of ruthenium Mw, better 50,000. The weight average molecular weight of the alkali-soluble resin (B): When it is enclosed, the advantage that the alkali-soluble resin is improved in one step in a solvent or a developer is obtained. The weight Mw of the alkali-soluble resin (B) is a number average molecular weight (measured by Gp c with respect to the poly ratio Mw/Mn, preferably from 1 to 4.0 to 4.0, more preferably from 1.0 to 3, Mw/Mn of the soluble resin (B)) In the above range, the resolution of the radiation-sensitive composition to be prepared and the adhesiveness to be formed on the substrate are obtained. The alkali-soluble resin (B) can be, for example, a compound (hereinafter referred to as " Unsaturated monocarboxylic acid (a 1 )": the advantage of X-COOH (a1). The resin (B) preferably has a solubility of 3,0 0 to an amount corresponding to the average molecular weight of styrene. ο. When the base can be further changed into the color layer a)

(where X is as defined in the former formula (B-1)) is referred to as "benzene added to a resin having the structure shown by the following formula (Β-Γ) (with ethylene epoxy resin):

(wherein R1, R2, R3 and h are as defined in the above formula (B-1) -17-), and 200839444 preferably has a structure represented by the former formula (B-Ρ) and at least one selected from the former formula ( a resin represented by the structure represented by B-2) and a group represented by the structure represented by the above formula (B_3), and then a compound represented by the following formula (a2) (hereinafter referred to as "polybasic acid anhydride (a2)") : 0 I!

A \/〇 (a2)

C

II

0 (wherein γ is as defined in the above formula (B-1)) is added to a reaction product of an unsaturated monocarboxylic acid (a 1 ) and a styrene epoxy resin (B·1 f). The styrene epoxy resin is preferably a compound represented by the following formula (b 1 ) (hereinafter referred to as "compound (b 1 )"):

(a polymer in which R1, R2, R3 and h are as defined in the above formula (B-1)) or a copolymer of the compound (b1) and another radical polymerizable compound. Specific examples of the compound (b 1 ) include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o- Vinylbenzyl glycidyl ether, -18- 200839444 α-methyl-m-ethyl benzyl glycidyl ether, α-methyl-p-ethylsulfonyl benzyl glycidyl ether, 2, 3-diglycidoxymethylstyrene, 2,4-diglycidoxymethylstyrene, 2,5-diglycidoxymethylstyrene, 2,6-diglycidyloxy Styrene, 2,3,4-triglycidoxymethylstyrene '2,3,5-triglycidoxymethylstyrene, 2,3,6-triglycidoxymethylbenzene B, 2,4,5-triglycidoxymethylstyrene and 2,4,6-triglycidoxymethylstyrene. Among them, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether are preferred. These compounds may be used in combination of two or more. The above-mentioned other examples of the radical polymerizable compound include a compound represented by the following formula (b2) (hereinafter referred to as "compound (b2)"):

(wherein R4 is as defined in the above formula (B-2)), a compound represented by the following formula (b3) (hereinafter referred to as "compound (b3)")

(wherein R5 to rig are as defined in the above formula (B-3)), -19- 200839444 and a radical polymerizable compound other than the compounds (b 1 ), (b2) and (b3) (hereinafter referred to as "compounds" (b 4 )"). The compound (b2) described above introduces the structure represented by the above formula (B-2) into the alkali-soluble resin (B). Specific examples of the compound (b2) include N-phenyl maleimide, N-o-hydroxyphenyl maleimide, N-meta-phenyl-phenyl-butane Amine, N · p-paraphenyl cis-butadiene diimide, N-o-methylphenyl maleimide, N-m-methylphenyl succinimide , N-p-methylphenyl cis-butane diimine, N-o-methoxyphenyl maleimide, N-m-methoxyphenyl cis-butane diimine , N-p-methoxyphenyl cis-butyl bis-imide and N-cyclohexyl maleimide. Among them, N-phenyl maleimide is preferred. The above compound (b3) is introduced into the test soluble resin (B) by the structure represented by the above formula (B-3). Specific examples of the compound (.b3) include hydrazine, 5-chloro-risk, 5-aminomethyl-containing methyl group and 5-amino group. It is preferable to endanger the 5 - basis. • An illustrative example of the aforementioned compound (b4) includes an aromatic ethyl storage compound such as the present invention, α-methylphenylethyl, o-ethyl-toluene, m-ethyl-toluene, p-vinyltoluene, p-Chlorobenzopyrene, o-methoxyphenethyl, ^-methoxystyrene, p-methoxystyrene, hydrazine and p-ethane hydroxy benzyl methyl ether; unsaturated carboxylic acid Ester, such as methyl acrylate, methyl propyl methacrylate, ethyl acetoacetate, methyl propyl acetonate, n-propyl propyl acrylate, n-propyl methacrylate, isopropyl acrylate, methyl Isopropyl acrylate, n-butyl propyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, second butyl acrylate, second butyl methacrylate, propionate - 20- 200839444 Tert-butyl acid ester, tert-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, acrylic acid 3-hydroxypropyl ester, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxy acrylate Butyl ester, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, Phenyl acrylate, phenyl methacrylate, methoxy triethylene glycol acrylate, methoxy triethylene glycol methacrylate and glycerol monomethacrylate; unsaturated carboxylic acid aminoalkyl ester, such as 2-Aminoethyl acrylate, 2-Aminoethyl methacrylate, 2-Aminopropyl acrylate, 2-Aminopropyl methacrylate, 3-Aminopropyl acrylate and 3-amine methacrylate Propyl acrylate; vinyl acetate such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl shrinkage Glycidyl ether and methallyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and vinylidene cyanide; unsaturated decylamines such as acrylamide, methyl Propylene amide, α-chloropropanol, hydrazine-ylethyl acrylamide and hydrazine - phenylethyl methacrylamide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; and polymer molecular chain ends having a mono propylene group or Monomethicone-based macromonomers such as polystyrene, polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, and polyfluorenone. B4) may be used alone or in combination of two or more. -200839444 When a styrene epoxy resin is a copolymer of a compound (bl) and another radical polymerizable compound, the synthesis of the alkali-soluble resin (B) In terms of simplicity, the ratio of the compound (b 1 ) to the other radical polymerizable compound to be copolymerized may be according to the structure of the formula (B-1) required in the alkali-soluble resin (B), and the former formula (B-2) The ratio of the structure shown and the structure shown in the former formula (B-3) is appropriately set. For example, the proportion of the compound (b 1 ) to be copolymerized is preferably from 5 to 80% by weight, more preferably from 1 to 80% by weight. When the proportion of the compound ( bl ) to be copolymerized is more than 80% by weight, it is easy to gel in a non-monocarboxy ( al ) addition reaction described below, and in some cases, it may be difficult to obtain an alkali-soluble resin (B). . Meanwhile, when the ratio of the compound (b 1 ) to be copolymerized is less than 5% by weight, a base of a resin formed by an addition reaction of a styrene epoxy resin, an unsaturated monocarboxylic acid (al ), and a polybasic acid anhydride (a2 ) Solubility is unsatisfactory, so when a colored layer is formed using a radiation-sensitive composition containing the resin, residue or scum may be generated on the unexposed or exposed portion of the substrate. The proportion of the compound (b2) to be copolymerized is preferably not more than 50% by weight, more preferably 5 to 45% by weight. The proportion of the compound (b3) to be copolymerized is preferably not more than 60% by weight, more preferably 5 to 40% by weight. The compounds (b2) and (b3) may be used together for copolymerization, in which case they may be copolymerized in an amount of preferably not more than 80% by weight based on the total amount of the compounds (b2) and (b3), more preferably 5 to 70. weight%. When the compounds (b2) and (b3) are used in combination, the amount thereof is preferably within the aforementioned individual ranges. A styrene epoxy resin is preferably a copolymer of the following compounds: -22- 200839444 (1) Compound (b 1 ) ' (2) at least one of compounds (b2) and (b3), and (3) compound (b4) . In this case, the amount of the compound (b 1 ) in the copolymer is preferably from 1 to 60% by weight, and the amount of at least one of the compounds (b2) and (b; 3) in the copolymer (or when used in combination) The amount of the compound (b 2 ) and (b 3 ) is preferably from 5 to 60% by weight, and the amount of the compound (b4) in the copolymer is preferably not more than 50% by weight. The weight average molecular weight Mw of the styrene epoxy resin and the ratio of the weight average molecular weight to the number average molecular weight Mw/Mn can be appropriately set depending on the Mw and Mw/Mn required for the alkali-soluble resin (B). The styrene epoxy resin can be obtained by polymerizing a mixture of the above compound or the above compound in a suitable solvent in the presence of a suitable radical polymerization initiator. As the solvent which can be used for the production of the styrene epoxy resin, for example, the same solvent as that used hereinafter as the radiation-sensitive composition of the present invention can be used. Illustrative examples of the radical polymerization initiator include 2,2'-azoisobutyronitrile, 2,2'-azobis(2,4.dimethylpentanenitrile), and 2,2'-couple. Nitrogen bis(4-methoxy-2,4-dimethylvaleronitrile). The aforementioned unsaturated residual acid (al) can be appropriately selected depending on the type of X required in the above formula (B-i). Preferred examples of the unsaturated carboxylic acid (al) include acrylic acid, methacrylic acid, carboxy-polycaprolactone monopropionate, ω·carboxy-polycaprolactone monomethacrylate, 2-propene oxime Ethyl succinic acid and 2-methylpropenyl oxyethyl succinic acid. In the aforementioned ω-carboxy-polycaprolactone monoacrylic acid ester and ω-mercapto-polycaprolactone monomethyl propyl acrylate, the number of reproducing units of polycaprolactone is preferably from 10 to 10, More preferably 2 to 4. -23-200839444 Among the unsaturated carboxylic acids (al), acrylic acid and methacrylic acid are particularly preferred because of their high reactivity. These compounds may be used singly or in combination of two or more. The addition reaction of the unsaturated monocarboxylic acid (al) with the aforementioned styrene epoxy resin can be carried out according to a known method. For example, the addition reaction may preferably be carried out at a temperature of from 50 to 150 ° C for 6 to 24 hours in the presence of a solvent and an esterification catalyst. Illustrative examples of the solvent which can be used as a solvent include propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and diethylene glycol. Alcohol dimethyl ether, bisethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl 2-hydroxypropionate, ethyl 3-methoxypropionate, 3- Methyl ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, isobutyl acetate, n-amyl formate, acetic acid Amyl ester, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate and ethyl pyruvate. As the esterification catalyst, for example, tertiary amines such as triethylamine, trimethylamine, benzylmethylamine and benzyldiethylamine; and quaternary ammonium salts such as tetramethylammonium chloride can be used. , tetraethylammonium chloride, benzyltriethylammonium chloride, dodecyltrimethylammonium chloride and tetrabutylammonium bromide. If necessary, a polymerization inhibitor such as p-methoxyphenol or methylhydroquinone can be used. The amount of the esterification catalyst is preferably not more than 〇·5 equivalent, more preferably 0.01 to 0.1 equivalent, based on the epoxy group contained in the styrene epoxy resin. The polymerization inhibitor is preferably used in an amount of not more than 5,000 ppm, more preferably from 50,000 to 3,000 ppm, based on the total amount of the reaction solution. The amount of the unsaturated monocarboxylic acid (al ) is preferably from 0.7 to 1.3 equivalents per equivalent of the epoxy group in the styrene epoxy resin, more preferably from 9 to 1.2 equivalents from 24 to 200839444. ) It can be appropriately selected according to the type required in the former formula (Β·1). Preferred examples of the polybasic acid anhydride (a2) are dianhydride, maleic anhydride, citraconic anhydride, succinic anhydride, pentane, glutaconic anhydride, itaconic anhydride, diglycolic anhydride, phthalic anhydride ketone -1,2-Dicarboxylic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride and biphenyl acid, of which succinic anhydride, glutaric anhydride, phthalic anhydride and 4-cyclohexene dicarboxylic anhydride are particularly preferred. Because of its high reactivity. The addition reaction of the polybasic acid anhydride (a2) to the styrene epoxy resin can be carried out under the conditions of addition of the above unsaturated monocarboxylic acid (al) to styrene epoxy resin. Further, after the addition reaction of the unsaturated monocarboxylic acid (a 1 ) to the styrene resin, the polybasic acid anhydride (a2) may be added to the reactant and the addition reaction may be continued. The amount of the polybasic acid anhydride (a2) is preferably from 0.2 to 1.0 equivalent per equivalent of the oxyethylene oxide epoxy resin, more preferably from 44 to 〇·9 equivalent. The radiation-sensitive composition of the present invention contains the aforementioned alkali-soluble fat (Β) in an amount of preferably 10 to 200 parts by weight based on 100 parts by weight, more preferably 20 to 150% by weight. Number of copies. When the enthalpy is less than the number of parts, the coloring layer to be formed may be insufficient due to insufficient sensitivity, and when it is more than 20 G parts by weight, the color purity of the obtained color filter or the shading ability of the obtained black matrix may be obtained. It may be insufficient. (C) Polyfunctional monomer The Y of the polyfunctional monomer (C) in the radiation-sensitive composition of the present invention includes propionic anhydride and cyclic anhydride. -1,2- In the case of a reaction-epoxy compounding amount of a 10-color hardener, -25-200839444 The example includes an alkanediol, such as ethylene glycol and propylene glycol diacrylate methacrylate Polyalkylene glycols such as polyethylene glycol and polypropylene glycol acrylate or dimethacrylate; having three or more functional hydroxyl alcohols such as glycerol, trimethylolpropane, pentaerythritol and diisoamyl Polyacrylate or polymethacrylate; polyacrylate or polymethyl propyl ester having three or more dicarboxylic acid modified polyhydric alcohols; polyester, epoxy resin, urethane An ester resin, an alkyd resin, a ketone resin, a spiro resin, and the like, an oligoacrylate or oligoenoate; a polymer which is hydroxylated at both ends, such as a hydroxyl terminated polybutadiene at both ends, and hydroxylated at both ends a polyisoprene or a di-capped polycaprolactone diacrylate or dimethacrylate; and a tri-acryloxyethyl ester and a tri-methyl propylene methoxyethyl phosphate . In the above polyfunctional monomer, "polyacrylate or polymethacrylic acid having three or more functional dicarboxylic acid-modified polyhydric alcohols is represented by addition of one dicarboxylic acid to have three or more a polyacrylate or polymethyl propyl ester of a monoester compound formed by a functional hydroxy alcohol. Among these polyfunctional monomers, a polyacrylate or polymethyl group having a base alcohol having three or more functional groups A polyacrylate or polymethacrylate of an acrylate and a dicarboxylic acid-modified polyhydric alcohol having three or more energy groups is preferred. Specific examples thereof include trimethylolpropane trimethylolpropane triacrylate. Methacrylate, pentaerythritol triacrylate pentaerythritol trimethacrylate, succinic acid-modified pentaerythritol triester, succinic acid-modified pentaerythritol trimethacrylate, different Or two or more of the tetradecyl olefinic acid polydecyl propylated hydroxyphosphoric acid esters of polyhydroxyl sulphate, isopropenyl pentylene -26-200839444 alcohol tetraacrylate , pentaerythritol tetramethacrylate, diisoamyl Tetraol hexaacrylate and diisopentaerythritol hexamethacrylate. Among the above compounds, succinic acid-modified isovaerythritol triacrylate and succinic acid-modified pentaerythritol trimethacrylate are compounds represented by the following formula:

(wherein R represents a hydrogen atom or a methyl group). φ Among these polyfunctional monomers, trimethylolpropane triacrylate, pentaerythritol triacrylate and diisopentaerythritol hexaacrylate are particularly preferable because of high strength and excellent surface smoothness. The colored layer and the scum and film residue are generated in a region other than the region where the colored layer pattern is formed. The foregoing polyfunctional monomer may be used singly or in combination of two or more, using the fluorene-sensitive monomer (C) in the radiation-sensitive composition of the present invention in an amount of 1 part by weight based on the alkali-soluble resin ( B) is preferably from 5 to 500 parts by weight, more preferably from 2 to 300 parts by weight. When the amount of the poly--27-200839444 functional monomer (c) is less than 5 parts by weight, the strength and surface smoothness of the colored layer may be lowered, and when the amount is more than 500 parts by weight, the alkali development is performed. The developability of the agent may be insufficient or scum and film residue may be generated in a region other than the region where the pattern of the color layer may be easily formed. In the radiation-sensitive composition of the present invention, the aforementioned polyfunctional monomer may be partially substituted by a monofunctional monomer. Specific examples of such monofunctional monomers include ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolactone monomethacrylate, methoxytriethylene glycol acrylate, methoxy Triethylene glycol methacrylate, methoxybispropanediol acrylate, methoxybispropanediol methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-methacrylate Phenoxypropyl ester, 2-propenyloxyethyl monosuccinate and 2-methylpropenyloxyethyl monosuccinate. Examples of commercially available products include Μ-5 3 00 (TOAGOSEI CO·, LTD.). These monofunctional monomers may be used singly or in combination of two or more. The amount of the aforementioned monofunctional monomer is preferably not more than 30% of the total of the polyfunctional monomer and the monofunctional monomer. More than 90% by weight, more preferably no more than 50% by weight. (D) Photosensitive polymerization initiator The photopolymerization initiator contained in the radiation-sensitive composition of the present invention can be produced by exposure to radiation such as visible light, ultraviolet radiation, far ultraviolet radiation, electron beam or X-ray. Free radical compound, this freedom -28- 200839444

The base may initiate the polymerization of the aforementioned polyfunctional monomer (C) with the monofunctional monomer used in some cases. As the photopolymerization initiator, a ruthenium compound, a biimidazole compound, a benzoin compound, an ethoxybenzene compound, a diphenyl ketone compound, an α-diketone compound, a polycyclic guanidine compound, a xanthone compound, or the like can be suitably used. A phosphine compound, a triazine compound, a diazonium compound, a key salt, a quinone sulfinate compound or the like. The aforementioned hydrazine compounds include carbazole compounds and other bladder compounds. Examples of the oxazole compound are compounds of the formula (D_n:

(wherein R represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms or a phenyl group, and R12 and R13 each independently form a JLL surface having no hydrogen atom and having from -20 to 20 carbon atoms. An alkyl group, a cycloalkyl group having 3 to 8 carbon atoms, a phenyl group which may be substituted or a monovalent alicyclic group having 7 to 20 carbon atoms (excluding the aforementioned ring-based group), and R14 is represented by 1 An alkyl group of 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or a cycloalkoxy group having 3 to 8 carbon atoms, when plural When rM, -29-200839444 may be the same or different from each other, and R15 represents a monovalent oxygen-containing heterocyclic group having 4 to 20 carbon atoms, a monovalent nitrogen-containing heterocyclic group having 4 to 20 carbon atoms or A monovalent sulfur-containing heterocyclic group of 4 to 20 carbon atoms. When a plurality of R15 are present, they may be the same or different from each other, P is an integer from 〇 to 6, and q is 〇 or l, n is m is an integer from 0 to 5, and the constraint is (n + m ) $ 5 ) 〇 as an alkyl group having 1 to 20 carbon atoms of R11 in the formula (D-1) Description Including methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n- Base, n-decyl and n-dodecyl. Illustrative examples of the cycloalkyl group having 3 to 8 carbon atoms as R11 include a cyclopentyl group and a cyclohexyl group. Preferred examples of R11 in the formula (D-1) include a methyl group and an ethyl group. Illustrative examples of the alkyl group having 1 to 20 carbon atoms of R12 and R13 in the formula (D-1) include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, and Tributyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, n-undecyl and n-dodecyl. Illustrative examples of the cycloalkyl group having 3 to 8 carbon atoms of R12 and R13 include a cyclopentyl group and a cyclohexyl group. Illustrative examples of the substituent of the phenyl group of R12 and R13 include an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, a third butyl group, a n-pentyl group and a n-hexyl group; a cycloalkyl group having 3 to 6 carbon atoms, such as a cyclopentyl group and a cyclohexyl group; an alkoxy group having 1 to 6 carbon atoms, such as a methoxy group, B -30- 200839444 oxy, n-propoxy, isopropoxy, n-butoxy and tert-butoxy; cycloalkoxy having 3 to 6 carbon atoms, such as cyclopentyloxy and cyclohexyloxy a phenyl group; and a halogen atom such as a fluorine atom and a chlorine atom. The number of substituents as the phenyl group of R12 and R13 is preferably from 4 to 1, more preferably 0 or 1. Further, illustrative examples of the monovalent alicyclic group having 7 to 20 carbon atoms of R12 and R13 (excluding the aforementioned cycloalkyl group) include a group having a 1-alkylcycloalkane structure and having a tricycloalkane. a group of a structure, a group having a spiro structure, a group having an olefin structure, and a group having an adamantane structure. As R12 and R13 in the formula (D-1), a hydrogen atom, a methyl group and an ethyl group are preferred. Illustrative examples of the alkyl group having 1 to 12 carbon atoms of R14 in the formula (D-1) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, second butyl group, and third group. Butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, n-undecyl and n-dodecyl. Illustrative examples of the cycloalkyl group having 3 to 8 carbon atoms as R14 include a cyclopentyl group and a cyclohexyl group. Illustrative examples of the alkoxy group having 1 to 12 carbon atoms as R14 include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a third butoxy group, and a n-pentyl group. Oxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-decyloxy, n-decyloxy, n-undecyloxy and n-dodecyloxy. The illustrative examples of the cycloalkoxy group having 3 to 8 carbon atoms of R14 include a cyclopentyloxy group and a cyclohexyloxy group. As R14 in the formula (D-1), methyl, ethyl, n-propyl, isopropyl, n-butyl, methoxy and ethoxy groups are preferred. Monovalent having 4 to 20 carbon atoms as R15 in the formula (D-1) -31 - 200839444 oxygen-containing heterocyclic group, monovalent nitrogen-containing heterocyclic group having 4 to 20 carbon atoms, and having 4 to 20 carbons Illustrative examples of monovalent sulfur-containing heterocyclic groups of atoms include thioindolyl, azirretyl, dihydroazetyl, dioxolanyl, triamyl, oxathiocyclohexane, thiazolyl, dioxadiazine , oxahydroindenyl, dithylnaphthyl, furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyrazolyl, furazolyl, piperazine Base, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, pyrrolinyl, morphonyl, piperazinyl, quinacridyl, fluorenyl, isodecyl, benzofuranyl, benzene幷Thienyl, pyridazinyl, chromenyl, quinolyl, isoquinolyl, fluorenyl, quinazolinyl, porphyrinyl, pyridazinyl, acridinyl, oxazolyl, anthracene Base, phenanthrene D, thioxanthyl, phenazinyl, phenothiaphthyl, oxathiazide, phenoxazinyl, thioxyl, tetrahydrofuranyl and tetrahydropyranyl. As the Ri5, dioxolane group, tetrahydrofuranyl group and tetrahydropyranyl group in the formula (D-1), it is preferred. The p in the formula (D-1) is preferably 〇, 1 or 2, especially 1. n in the formula (D-1) is preferably 〇, 1 or 2, especially, and m in the formula (D-1) is preferably 〇 or i. In the compound of the formula (D · 1 ), the compound wherein q is ruthenium (hereinafter referred to as "carbazole compound (1)") and the compound wherein 4 is 1 and (5) is 1 (hereinafter referred to as "carbazole" Compound (2)") is preferred. Specific examples of the aforementioned carbazole compound (1) include b [% ethyl·6_benzamide-9·η·-carbazole-3·yl]-U2-decane-2-肟-◦~benzol Acid ester, 1-[9.ethyl-6-benzhydryl-911-oxazol-3-yl]-1,2-decane-2_肟-〇_-32- 200839444 acetate, 1- [9-ethyl-6-benzamide-9.11.-n-oxazol-3-yl]-1,2-pentane-2-indole-0-acetate, 1-[9-ethyl-6- Benzamidine·9·Η._oxazol-3-yl]-octane-1-one oxime-0-acetate, 1-[9-ethyl-6-(2-methylbenzamide) -9.11.-Acoxazol-3-yl]-ethane-1-one oxime-indole-benzoate, 1-[9-ethyl-6-(2-methylbenzamide)-9.11.- Oxazol-3-yl]-ethane-1-one oxime-indole-acetate, 1-[9-n-butyl-6-(2-ethylbenzylformamidine)-9.Η.-isoxazole 3-yl]-ethane-1-one oxime-indole-benzoate, ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylbenzophenone)-9 ·Η·-oxazol-3-yl]-1-(Ο-acetamidine), Ethyl-1-(9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzene)醯)-9·Η·- oxazol-3-yl]-1-(Ο-acetamidine), ethyl ketone-1-[ 9-ethyl-6-( 2-methyl-5-tetrahydrofuranylbenzene Hyperthyroidism)-9·Η ·- oxazol-3-yl]-1-( 〇-acetamidine), ethyl ketone-1-[ 9-ethyl-6- ( 2-methyl-5-tetrahydropyranyl benzamidine) -9·Η·-oxazol-3-yl]-1-(Ο-acetamidine), and 乙--1-[9-ethyl-6- { 2 -methyl-4- ( 2,2 - monomethyl-1,3-mono-oxopentyl)benzamide}-9.Η·-oxazol-3-yl]-1-(0-acetamidine). Specific examples of the aforementioned carbazole compound (2) include ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzylammonium)-9.Η.-carbazole 3-yl]-1-(0-acetamidine), -33- 200839444 ethyl ketone-1-[9-ethyl-6-(2-methyl-4_tetrahydropyranyl methoxybenzene Formamidine)-9.11.-carbazol-3-yl]-1-(0-acetamidine), ethyl ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylmethoxy) Benzobenzidine··9·Η·-carbazol-3-yl]-1-(0-acetamidine), ethyl ketone-1-[9-ethyl-6- (2-methyl-5_ Tetrahydropyranomethoxybenzyl hydrazide)-9·Η·-oxazol-3-yl]-1-(0-acetamidine), and ethyl ketone-1-[9-ethyl-6- { 2-Methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzimid}-9-Η--oxazol-3-yl]-1- (0-acetamidine) wherein 1-[9-ethyl-6-(2-methylbenzimidoxime)oxazol-3-yl]-ethane-1 is used in the carbazole compound (1) -Ketone oxime-0-acetate and the hexa-(9-ethyl-6-(2-methyl-4-tetramethylenefuranyl methoxybenzoate) in the compound (2)醯)carbazol-3-yl]-1-(0-acetamidine) and ethene-1-[9-ethyl-6- {2-A -4- ( 2,2 - _^methyl-1,3 -monooxypenta) methoxybenzimid} oxazol-3-yl]-1-(0-acetamidine) is preferred . Ethyl ketone-1-[ 9-ethyl-6-{ 2-methyl-4-( 2,2-dimethyl-1,3-dioxolanyl) in the carbazole compound (2) ) methoxybenzimid} -9.H--oxazol-3-yl]-1-(0-acetamidine). The above-mentioned other examples of the ruthenium compound include 1,2-anthracene-l-[4-(phenylthio)benyl]-2·(0-pretylated carbenazole) 1,2-butanedione-1 -[4-(phenylthio)phenyl]-2-(0-benzylidenehydrazide) 1,2-butanedione-1-[4-(phenylthio)phenyl]-2- (0 - 乙醯基肟), -34- 200839444 1,2· octodione-1-[ 4-(methylthio)phenyl]-2-( 0-benzylidene fluorenyl), and 1,2 - Octapressin-1-[4-(phenylthio)phenyl]-2-(0-(4-methylbenzhydrylhydrazine)). Among them, 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(indenyl-benzhydrylhydrazine) is particularly preferred. Illustrative examples of the biimidazole compound include 2,2'-bis(2.chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2. Imidazole, 2,2'-bis(2-bromophenyl)-4,4,5,5'-tetrakis(4ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-double (2-Chlorophenyl)-4,4f,5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4' ,5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl -1,2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetraphenyl-1,2.biimidazole, 2,2'-double (2,4-dibromophenyl)-4,4\5,5'-tetraphenyl-1,2'biimidazole, and 2,2'-bis(2,4,6-tribromophenyl) -4,4',5,5'-tetraphenyl-1,2'-biimidazole. When the biimidazole compound is used as the photosensitive polymerization initiator (D) in the radiation-sensitive composition of the present invention, it is preferably used in combination with a hydrogen donor because the sensitivity can be further improved. "Hydrogen donor" means a compound which provides a hydrogen atom to a radical which is exposed from a biimidazole compound. Preferred as the hydrogen donor 'thiol compound, amine compound and the like. The aforementioned thiol compound is a compound having a benzene ring or a heterocyclic ring and one or more (preferably one to three, more preferably one or two) groups bonded directly to the fluorenyl group of the ring. Specific examples of the thiol compound include 2-mercaptobenzothiazole, -35-200839444 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2,5-dimercapto-1,3,4- Thiadiazole and 2-mercapto-2,5-dimethylaminopyridine. The above amine compound is a compound having a benzene ring or a heterocyclic ring and one or more (preferably one to three 'more preferably one or two) amine groups directly bonded to the ring. Specific examples of the amine compound include 4,4'-bis(dimethylamino)diphenyl ketone, 4,4'-bis(diethylamino)diphenyl ketone, 4-diethyl Aminoethyl phenyl benzene, 4-dimethylamino propyl phenyl benzene, ethyl 4-dimethylamino benzoate, isoamyl 4-dimethylaminobenzoate, 4-dimethylamine Benzoic acid and 4-dimethylaminobenzonitrile. When a bisimidazole compound is used as the photopolymerization initiator (D) in the radiation-sensitive composition of the present invention, it is preferred to use both a thiol compound and an amine compound as a hydrogen donor because of sensitivity of the radiation-sensitive composition. The color is high, and the formed color layer hardly falls off from the substrate during development, and the strength of the colored layer is also high. Illustrative examples of the aforementioned benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, and methyl 2-benzoin benzoate. Illustrative examples of the aforementioned acetylated benzene compound include 2,2-dimethoxyacetamidine, 2,2-diethoxyethyl benzene, and 2,2-dimethoxy-2-phenyl acetylene. Benzene, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-methyl Base-(4-methylthiophenyl-2-morpholine-1-propan-1-one, 4-(2-hydroxyethoxy)phenyl-2-(hydroxy-2-propyl)one, 2 -benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one, 1-hydroxycyclohexyl phenyl ketone and 2,2-dimethoxy-1,2- Diphenylethan-1-one. -36- 200839444 Methotone benzoquinone and phosphinated bis) oxazine A-S - The illustrative examples of the aforementioned diphenyl ketone compound include 4,4'-bis (two Illustrative examples of the aforementioned α-diketone compounds of the above-mentioned α-diketone compounds include bis-indenyl, dimethylhydrazine and benzene. Methyl carbazate. Illustrative examples of the aforementioned polycyclic guanidine compound include hydrazine, 2-ethyl hydrazine, 2-tert-butyl fluorene, and 1,4-naphthoquinone. Illustrative examples of the aforementioned xanthone compounds include xanthone and thioxanthone 2-chloroxanthone. Illustrative examples of the aforementioned phosphine compound include bis(2,4,6-trimethylmethylindenyl)phenylphosphine oxide and oxidized 2,4,6-trimethylbenzimidyldiphenylphosphonium. Illustrative examples include triazine compounds having a halomethyl group such as 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-(trichloromethyl)- S-triazine, 2-[2((furan-2-yl)vinyl] 4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2) -ylvinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)vinyl]-4,6 - bis(trichloromethyl)-s-tris(2-(2-(3,4-dimethoxyphenyl)vinyl]_4,6-bis(trichloro)-s-triazine, 2 - (4-methoxyphenyl)-4,6-bis(trichloromethyl)triazine, 2-(4-ethoxystyryl)_4,6-bis(trichloromethyl)-S · azine and 2-(4-n-butoxyphenyl)_4,6-bis(trichloromethyl)-s-triazine These photopolymerization initiators can be used alone or in combination of two or more. Wherein the amount of the photopolymerization initiator (D) is from 1 to 30 - 200839444 parts of the polyfunctional monomer C) The total amount of the monofunctional monomer is preferably from 0.01 to 500 parts by weight, more preferably from 1 to 300 parts by weight, especially from 10 to 200 parts by weight. When the photosensitive polymerization initiator (D) is used When the amount is less than 0.01 part by weight, the curing by exposure is insufficient, and it may become difficult to obtain a pattern array having a coloring layer pattern arranged according to a predetermined arrangement, and when the amount is more than 500 parts by weight, the formation is performed. The dyed layer is easily detached from the substrate during development, and is easy to form scum and is liable to remain in the unexposed area of the substrate or on the light-shielding layer. The photosensitive polymerization initiator contained in the radiation-sensitive composition of the present invention (D) It is preferred to contain a ruthenium compound, and more preferably a compound represented by the above formula (D-1). When the photopolymerization initiator (D) contains a ruthenium compound and other photopolymerization initiator, it is combined with the ruthenium compound. Other photosensitive polymerization initiators used are preferably a biimidazole compound, an ethenylbenzene compound, a triazine compound, a benzoin compound, a diphenyl ketone compound, an α-diketone compound, a polycyclic guanidine compound, and a xanthone. Compound The diazonium compound, the key salt and the sulfhydryl sulfonate compound, and the ethoxylated benzene compound is particularly preferred. In the present invention, the cerium compound is preferably used in an amount of at least 20% by weight based on the total amount of the photosensitive polymerization initiator (D). %, more preferably at least 50% by weight. Other additives In addition to the aforementioned coloring agent (A), alkali-soluble resin (Β), polyfunctional monomer (C), and photopolymerization initiator (D), the radiation of the present invention The sensitive composition may contain various other additives as needed. Examples of such other additives include chelating agents, surfactants 38·200839444, adhesion promoters, antioxidants, ultraviolet absorbers, coagulation inhibitors, and developability modifiers. . Specific examples of the aforementioned chelating agents include glass and alumina. Specific examples of the aforementioned surfactant include nonionic surfactants, cationic surfactants, and anionic surfactants. Specific examples of the aforementioned adhesion promoter include vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, N-(2-aminoethyl)- 3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyltrimethoxydecane, 3-aminopropylpropyltriethoxydecane , 3-glycidyltrimethoxydecane, 3-glycidylpropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropane Methyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, and 3-mercaptopropyltrimethoxydecane. Specific examples of the aforementioned antioxidant include 2,2-thiobis(4-methyl-6-tert-butylphenol) and 2,6-di-t-butylphenol. Specific examples of the aforementioned ultraviolet absorber include 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole and alkoxydiphenylmethanone. Specific examples of the aforementioned coagulation inhibitors include sodium polyacrylate. The aforementioned developability adjuster may be added to further improve the solubility of the coating film formed from the radiation-sensitive composition of the present invention in an alkali developer, and further suppress the residue of undissolved substances after development. An example of the developability modifier is an organic acid. As such an organic acid, an aliphatic carboxylic acid or a benzene-containing carboxylic acid having a molecular weight of not more than 1,000 is preferred. Specific examples of the aforementioned aliphatic carboxylic acid include monocarboxylic acids such as formic acid, -39 - 200839444 acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, heptanoic acid, and octanoic acid; Carboxylic acids, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, basal acid, methylmalonic acid, ethyl Malonic acid, dimethylmalonic acid, methyl succinic acid, tetramethyl carboxylic acid, cyclohexan dicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid and medium Kang acid, and tricarboxylic acids such as glycerol tricarboxylic acid, aconitic acid and camphorone acid. φ The above-mentioned illustrative examples of the benzene-containing carboxylic acid include an aromatic carboxylic acid in which a carboxyl group is directly bonded to a phenyl group, and a carboxylic acid in which a carboxyl group is bonded to a phenyl group via a carbon chain. Specific examples thereof include aromatic monocarboxylic acids such as benzoic acid, toluic acid, lauric acid, benzotricarboxylic acid and linonic acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid An aromatic polycarboxylic acid having three or more functional groups, such as trimellitic acid, trimellitic acid, pyromellitic acid, and pyromellitic acid; and phenylacetic acid, hydrogenated atropic acid, hydrogenated cinnamic acid, almond Acid, phenyl succinic acid, atropine, cinnamic acid, cinnamic acid, coumaric acid and chelating acid. • Among these organic acids, aliphatic dicarboxylic acids and aromatics are used in view of alkali solubility, solvent of the solvent described below, and scum and film residues in areas other than the formation of the coloring layer portion. Dicarboxylic acids such as malonic acid, hexanedioic acid, itaconic acid, citraconic acid, maleic acid, mesaconic acid and phthalic acid are preferred. The aforementioned organic acids may be used singly or in combination of two or more. In the present invention, the developer adjuster is preferably used in an amount of not more than 10% by weight, more preferably 0.001 to 10% by weight, still more preferably 0.01 to 1% by weight based on the total radiation-sensitive composition. When the amount of the developability adjuster is more than 10% -40 - 200839444% by mass, the adhesion of the formed color layer to the substrate may be insufficient in some cases. Solvent The radiation-sensitive composition of the present invention comprises the above-mentioned coloring agent (A), alkali-soluble resin (B), polyfunctional monomer (C), and photopolymerization initiator (D) as essential components and, if necessary, the aforementioned Other additives. However, the radiation-sensitive composition is preferably prepared as a liquid composition in which components other than the colorant (A) are dissolved in a suitable solvent and the colorant (A) is uniformly dispersed. As the solvent, any solvent may be selected and suitably used, which is limited to dispersing or dissolving the colorant (A), the alkali-soluble resin (B), the polyfunctional monomer (C), and the photopolymerization initiator (D). And other additives' do not react with these components and have appropriate volatility. Illustrative examples of the solvent include (poly)alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, bisethylene glycol monomethyl ether, and diethylene glycol monoethyl ether. , bisethylene 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 brewing, dipropylene glycol monomethyl ether and tripropylene glycol monoethyl ether; (poly) hospital II Alcohol monoether ether acetates, such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl acetate; 3-methoxybutyl acetate; other ethers such as bisethylene glycol dimethyl-41 - 200839444 ether, bisethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran; ketones , such as methyl ethyl ketone, cyclohexanone, 2 - heptanone and 3-heptanone; alkyl lactate, such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; other esters , such as methyl 2-hydroxy-2-methylpropanoate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3_ Methyl ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl acetate, 2-methyl-methyl 3-methylbutanoate, 3-methyl acetate -3-methoxybutyl ester, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, N-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, acetone N-propyl acrylate, methyl acetoxyacetate, ethyl acetoxyacetate and ethyl 2- oxybutyrate; aromatic hydrocarbons such as toluene and xylene; and decylamines such as N-methyl hydrazine Slightly ketone, hydrazine, hydrazine dimethylformamide and n,N-dimethylacetamide. • These solvents may be used alone or in combination of two or more. In addition, such solvents may be combined with high boiling solvents such as benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, acetic acid. Benzyl ester, ethyl benzoate, diethyl oxalate, diethyl maleate, butyrolactone, ethylene glycol carbonate, propylene glycol carbonate or ethylene glycol monophenyl ether acetate are used together. These high boiling solvents may be used singly or in combination of two or more. Among the foregoing solvents, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether-42 - 200839444 acetate, propylene glycol monoethyl ether B, in terms of solubility, pigment dispersibility, coatability, and the like Acid ester, 3-methoxybutyl acetate, ethyl alcohol monomethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 2-hydroxyethyl vinegar, 3-methylmethoxybutyl propionate, Ethyl 3-methoxypropionate methyl ethoxy propionate, ethyl 3-ethoxypropionate, n-butyl acetate 'isobutyl vinegar, n-amyl acetate, isoamyl acetate, n-butyl propionate Esters, butyl vinegar, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate and the like are preferred. As a high-boiling solvent, 7-butyrolactone and the like, dissolved, [[The amount of the radiation-sensitive composition of the present invention (the total amount of the solvent boiling solvent) is i 00 parts by weight of the alkali-soluble resin (B) It is preferably 100 to 1 Torr, 〇〇〇 part by weight, more preferably 5 〇〇 to 5, 〇〇〇 part. When a high boiling point solvent is used together with a solvent in the radiation sensitive composition of the present invention, the amount thereof is used. Not more than 20% by weight, based on the total amount of the solvent, is not more than 10% by weight. Method of forming a coloring layer Next, a method of forming a radiation-sensitive composition using the present invention will be described. First, the coloring layer is described as comprising In the case of the image column of the color filter, the case where the colored layer is a black matrix will be described. [Method for forming a coloring layer including a pixel array] First, a light shielding layer (black matrix) is formed to be divided into pixels on the surface of the substrate. a liquid radiation sensitive composition in which, for example, a pigment is dispersed, and the substrate is subjected to heat treatment (pre-, dipropionic acid > 3-acetic acid, B is preferred and high) weight sensitivity Better color layer matrix array red baking -43- 200839444 ) The solvent is removed by evaporation to form a coating film. Thereafter, after irradiating the radiation to a region of the coating film, the coating film is developed with an alkali developer, and the coating film of the unexposed region is dissolved and removed, followed by heat treatment (post-baking) to form a red color having a predetermined pattern A pixel array of pixels. Then 'applying a liquid radiation-sensitive composition in which individual green pigments and blue pigments are dispersed, pre-baked, exposed to radiation, developed as described above. _, forming a green pixel array and blue on the same substrate in sequence Pixel Φ array. Thus, a color filter having red, green, and blue pixel arrays (colored layers) arranged on the substrate can be obtained. However, in the present invention, the order in which the pixel array of the above three colors is formed is not particularly limited. Illustrative examples of the substrate used to form the colored layer include glass, ruthenium, poly 9 carbonate, polyester, aromatic polyamine, polyamidimide, and polyimine. Such substrates may be suitably pretreated as desired, such as by chemical treatment, plasma treatment, ion plating, sputtering, gas phase reaction methods or vacuum deposition using a decane coupling agent or the like. φ The method of applying the radiation-sensitive composition to the substrate is not particularly limited. The illustrative examples of the method include a method of using a slit nozzle (hereinafter referred to as p "slit nozzle coating method") such as a slit-and-spin coating method and a slit coating method. The coating conditions in the slit nozzle coating method are different in the slit-and-spin coating method than in the slit molding method, and vary depending on the size of the substrate to be coated or the like. For example, when a fifth-generation glass substrate (1,100 mm x 1,250 mm) is applied by a slit molding method, the amount of the radiation-sensitive composition sent from the slit nozzle is preferably 500 to 2,000 μm. l / sec, more -44 - 200839444 better than 800 to 1,500 liters / sec, coating speed is preferably 500 to 1,500 mm / sec, more preferably 700 to 1,200 mm / sec . The solid content of the radiation-sensitive composition used in the slit nozzle coating method (the ratio of the total weight of the components other than the solvent in the composition to the total weight of the composition) is preferably from 1 Torr to 20% by weight. %, more preferably from 1 3 to 18% by weight. When the slit nozzle coating method is employed, the prebaking is preferably "vacuum baking" under reduced pressure. As for the vacuum baking condition, the degree of vacuum is preferably from about 1 Torr to 150 Å, more preferably from about 25 to 7 5 P a, and the temperature is preferably from about 60 to 120 ° C, more preferably about The baking time is preferably from about 1 to 5 minutes, more preferably from about 2 to 4 minutes, from 70 to 110 °C. The thickness of the coating film formed after removing the solvent is preferably from 0.1 to 10 μm, more preferably from 0.2 to 8.0 μm, particularly preferably from 0.2 to 6.0 μm. Thereafter, at least a part of the formed coating film is exposed. This can be achieved by irradiating radiation through a reticle having a suitable pattern. As the radiation to be used for exposure, for example, visible light radiation, ultraviolet radiation, far ultraviolet radiation, electron beam, X-ray or the like can be used. Among them, radiation having a wavelength of 190 to 450 nm is preferred. The radiation exposure is, for example, about 10 to 10,0 0 joules per square meter. Thereafter, the coating film is developed with a developer to dissolve and remove the unexposed areas of the coating film. As the developer, it is preferred to contain sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5·4·〇]-7- An alkali developer of an undecene, 1,5-diazabicyclo-[4.3.0]-5-decene or -45-200839444 aqueous solution such as those. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, an surfactant or the like may be added to the aforementioned alkali developer. The developed coating film is preferably rinsed with water. As the developing method, for example, spray development, spray development, immersion development, smelting development or the like can be employed. Development is preferably carried out at room temperature for about 5 to 300 seconds. Thereafter, the developed coating film is post-baked to form a colored layer on the substrate. The post-baking is preferably carried out at 180 to 23 ° C for about 20 to 40 minutes. By repeating the foregoing steps in a coloring layer forming composition in which red, green, and blue pigments are individually dispersed in the order shown, a red pixel array, a green pixel array, and a blue pixel array (colored layer) formed on the same substrate can be obtained. Color filter. [Method for forming a coloring layer as a black matrix] In the above "method for forming a coloring layer including a pixel array", by using radiation in which a black pigment or a mixture of red, yellow, and blue pigments is dispersed The sensitive composition is sequentially subjected to the foregoing steps, and a substrate having a black matrix pattern arranged in a predetermined configuration can be obtained. The color filter formed with a colored layer or a black matrix containing a colored layer is extremely suitable for use in, for example, a color liquid crystal display, a color camera tube device, a color sensor, and the like. -46- 200839444 Liquid Crystal Display Device The liquid crystal display device of the present invention comprises a color filter having a coloring layer formed from the radiation-sensitive composition of the present invention or a black matrix comprising a coloring layer formed from the radiation-sensitive composition of the present invention. The liquid crystal display device of the present invention can have any suitable structure. For example, it may have a color filter formed on a substrate different from a driving substrate on which a thin film transistor (TFT) is formed on the surface, and the substrate for driving and the substrate having the filter chrominator face each other with a space therebetween a structure of a liquid crystal layer, or a color filter formed on a surface of a driving substrate on which a thin film transistor (TFT) is disposed on a surface layer, and a substrate on which an electrode made of ITO (indium oxide doped with tin) is formed on the substrate and the surface layer A structure in which a liquid crystal layer is placed facing each other. The latter structure has the advantage of greatly improving the aperture ratio and producing a bright, high-definition color liquid crystal display device. Those skilled in the art should be able to clarify other specific embodiments of the foregoing liquid crystal display device. # The liquid crystal display device of the present invention is excellent in color purity. [Embodiment] 实施 Embodiments The present invention will be further described below with reference to examples. However, the invention should not be limited to the following examples. In the following examples, the weight average molecular weight (Mw) in terms of polystyrene was determined by gel permeation chromatography (GPC) using a GPC column from Tosoh Corporation (including two G2000HXL, one G3000HXL, and -47-200839444 in series). G4 00 0HXL) was measured using tetrahydrofuran as the dissolution solvent at a flow rate of 〇.〇ml/min and a column temperature of 40 °C using monodisperse polystyrene as a standard. <Synthesis Example of Styrene Epoxy Resin> Synthesis Example 1 In a flask equipped with a condenser and an agitator, 4 g of p-vinylbenzyl glycidyl ether and 27.0 g of N- Phenyl maleimide, 17.0 g of styrene and 16.0 g of benzyl methacrylate were dissolved in 300 g of propylene glycol monomethyl ether acetate. Thereafter, 4.0 g of 2,2'-azobisisobutyronitrile and 6.0 g of α-methylphenethyl dimer were added to the mixture, followed by rinsing with nitrogen for 15 minutes. Thereafter, the reactor was heated to 8 ° C under agitation, and the mixture was reacted for 5 hours to obtain a solution containing 25 wt% of styrene epoxy resin [A-1]. The weight average molecular weight (Mw) of the phenylethylene storage epoxy resin [A-1] based on polystyrene was 6,000. Synthesis Examples 2 to 8 A solution containing 25 wt% of styrene epoxy resins [A-2] to [A-8] was obtained in the same manner as in the above Synthesis Example 1, except that the monomer type and amount were 2, The amounts of 2'-azobisisobutyronitrile and methylphenidene dimer were changed as shown in Table 1. The amounts of the components in Table 1 are expressed by weight (grams). The weight average molecular weight (Mw) of the styrene epoxy resin obtained in these synthesis examples in terms of polystyrene is shown in Table 1. -48- 200839444 £ S.Ex.8 1 A-8 | 34.0 1 43.0 | 1 〇16.0 | 1 〇00 〇〇6 5,500 1 S.Ex.7 A-7 40.0 1 1 40.0 | 1 20.0 1 P 〇VO ο 1 S.Ex.6 A-6 1 44.0 40.0 1 16.0 1 1 I 1 P inch p ο ο οο" S.Ex.5 < 40.0 | 27.0 1 1 L祉―丨〇10.0 〇in ο vd 5,000 S .Ex.4 A-4 1 44.0 1 40.0 | 1 1 1 16.0 | IP ο ν〇6?000 S.Ex.3 _ Μ" 50.0 1 27.0 | 1 "―17·0-1 〇νο 1 ο rn ο ¥ 15,000 S.Ex.2 A-2 ο | 38.0 1 1 1 28.0 1 30.0 1 Ο rn ο to ο ο ri S.Ex.l Al 40.0 | 27.0 | 1 丨17·0 I 16.0 1 Ο — Ο ο I Resin name _ 1 p-vinylbenzyl glycidyl ether | Ν-phenyl maleimide amide I styrene 1 benzyl methacrylate | 2-hydroxyethyl methacrylate 1 2, 2' ·Azobisisobutyronitrile 1 α-methylstyrene dimer 1 Weight average molecular weight (Mw) Frequently weird 4Π: .xws

-49- 200839444 <Synthesis of alkali-soluble resin represented by formula (1)> Synthesis Example 9 200 g of the styrene epoxy resin [A-1] obtained in the above Synthesis Example 1 and 10.0 g as an unsaturated A solution of monocarboxylic acid methacrylic acid, 0.2 gram of p-methoxyphenol, 〇 2 g of tetrabutylammonium bromide and 300 g of propylene glycol monomethyl ether acetate was placed in a flask at 120 ° The reaction was carried out at C temperature for 9 hours. The reaction is carried out in the case where the equivalent epoxy group of the styrene epoxy resin has 1 equivalent of φ of acrylic acid. Separately, 16.0 g of 4-cyclohexene-1,2-dicarboxylic anhydride as a polybasic acid anhydride was added, and the mixture was reacted at 80 ° C for 6 hours. The reaction mixture was rinsed twice with water and concentrated under vacuum at a solution temperature of 80 °C. As a result, a solution containing 20% by weight of the alkali-soluble resin [B-1] was obtained. The alkali-soluble resin [B-1] had a weight average molecular weight (Mw) of 7,800 in terms of polystyrene. Synthesis Example 1 〇 to 18 8 A solution containing 20% by weight of an alkali-soluble resin [B-2] to [B-10] was obtained in the same manner as in the above Synthesis Example 9, except that a styrene epoxy resin solution was used. The type and amount of the unsaturated monocarboxylic acid and the type and amount of the polybasic acid anhydride are as shown in Table 2. The weight average molecular weight (Mw) of the alkali-soluble resin obtained by these synthesis examples in terms of polystyrene is shown in Table 2. -50- 200839444

Oo τ-Η >< ω ζ/i B-10 | Α-8 1 00 1 1 〇\ 1 (N 〇(N 〇7,200 | S.Ex.17 B-9 Α-7 1 inch οό 1 fog 1 12.0 1 (N &(N c> 〇S.Ex.16 B-8 Α-6 11.0 I 1 12.8 1 1 1 (N 〇(N 〇〇tH S.Ex.15 —Bi; Α-5 10.0 I 16.0 1 1 (N 〇CN 〇 7,000 S.Ex.l4| B-6 Α-4 ρ r—Η rH 1 λ rH 1 1 ( 1 〇(N 〇〇〇〇〇S.Ex.13 B-5 Α -1 10.0 1 I 1 〇\ <0 (N 〇〇〇ϊ> S.Ex.12 B-4 Α-3 1 20.0 1 1 (N 〇<N Ο 17,000 S.Ex.l! cn ώ Α -2 O rmmmi I ΓΠ τ—Η 1 1 (N 〇Ο ο ο inch. rmmi S.Ex.10 B-2 1—( < 1 inch οό ΟΟ inch · 1 I (N 〇(N Ο ο S. Ex.9 r—4 ώ τ—Η < 10.0 1 16.0 1 1 (N 〇CN Ο 7,800 1 Name of alkali-soluble resin 1 Type of styrene epoxy resin I methacrylic acid (g) 1 Acrylic acid (g) 1 4-cyclohexene-1,2-dicarboxylic anhydride (g) 1 succinic anhydride (g) 1 glutaric anhydride (g) I p-methylphenol (g) l tetrabutylammonium bromide (g) 1 weight Average molecular weight (Mw) 匡 chain: .xars -51 - 200839444 <alkali soluble resin Comparative Synthesis Example> Comparative Synthesis Example 1 In a flask equipped with a condenser and an agitator, 30.0 g of styrene, 45.0 g of benzyl methacrylate, and 15.0 g of methacrylic acid were dissolved in 200 g of propylene glycol monomethyl ether. In the acetate, 4,0 g of 2,2'-azobisisobutyronitrile and 6.0 g of α-methylstyrene dimer were added to the mixture, followed by nitrogen purge for 15 minutes. Thereafter, the reactor was heated to 80 ° C under agitation, and the mixture was reacted for 5 hours to obtain a solution containing 33% by weight of a styrene epoxy resin [R-1]. The alkali-soluble resin [:^-1] was polyphenylene. The weight average molecular weight (Mw) of ethylene was 6,000. Comparative Synthesis Example 2 In a flask equipped with a condenser and an agitator, 30.0 g of N-phenyl maleimide, 20.0 g of styrene, 35.0 was used. Benzyl methacrylate and 15.0 g of methacrylic acid were dissolved in 200 g of propylene glycol monomethyl ether acetate. Thereafter, 3.0 g of 2,2'-azobisisobutyronitrile and 5.0 g of α-methylstyrene dimer were added to the mixture, followed by rinsing with nitrogen for 15 minutes. Thereafter, the reactor was heated to 80 ° C under agitation, and the mixture was reacted for 5 hours to obtain a solution containing 33% by weight of a styrene epoxy resin [R-2]. The alkali-soluble resin [R-2] had a weight average molecular weight (Mw) of 12,000 in terms of polystyrene. <Preparation and evaluation of radiation-sensitive composition> Example 1 - 52 - 200839444 1 5 parts by weight including 80% by weight C. I. Pigment red 2 5 4 and 20% by weight CI Pigment Red 177 Mixture of colorant (Α), 4 parts by weight - based on solid content (by weight other than solvent) - Disperbyk-2000 (trademark, product of BYK-Chemie GmbH) and 81 parts by weight as pigment A pigment dispersion liquid was prepared by a propylene glycol monomethyl ether acetate system in a dispersion medium and processed by a bead mill.

Then, 100 parts by weight of the pigment dispersion prepared above, and 65 parts by weight of the alkali-soluble resin (B) containing the alkali-soluble resin [B-1] (resin concentration: 20% by weight), 13 parts by weight a number of diisopentyl alcohol hexaacrylate as a polyfunctional monomer (C), and 4.3 parts by weight of 2-methyl-(4-methylthienyl)-2- as a photopolymerization initiator (D)琳琳-1_丙院-1-嗣 and 63 parts by weight as a solvent for the 3-ethoxypropionic acid evaluation method. The object-forming group is formed into a group forming layer. The layer 3 color setting table is formed on the soda glass substrate by using a spin coater to evaluate the composition of the radiation sensitive composition. A SiO 2 film for preventing sodium ions from being dissolved is formed on the substrate, and the substrate is prebaked on a 90 ° C hot plate for 2 minutes to form a coating film having a thickness of 0.7 μm. After the substrate with the coating film is cooled to room temperature, the coating film is exposed by a high pressure mercury lamp at a exposure angle of 1,000 J/m 2 via a mask having slits having different widths of 5 to 50 μm. 65 nm, 405 nm and 436-53-200839444 Ultraviolet radiation at nanometer wavelengths. Thereafter, the substrate having the exposed coating film was used 23. (: 〇. 〇 4% by weight aqueous potassium hydroxide solution for 1 minute, rinsed with ultrapure water and air dried. In addition, the substrate was baked in a dust-free oven at 220 ° C for 30 minutes to obtain A pixel array of red stripe pixel patterns arranged on the substrate. The surface of the substrate is formed with a pixel array, and the edge of the pixel pattern is evaluated according to the following three-level rating, and whether the pigment remains in the non-pixel pattern area on the substrate Residues [Defects in Pixel Patterns] 〇: No defects were found in the pixel pattern of width 30 μm. △: Some defects were found in the pixel pattern of width 3 〇 micron. X: Many defects were found in the pixel pattern of width of 30 μm. Pigment residue in areas other than the pixel pattern 〇: No residue found △: Some residue X was found: Many residues were found. In addition, the minimum pixel pattern width which did not fall off completely and remained intact was evaluated as being formed. The minimum pattern width (micrometer). The results are shown in Table 3. Example 2 and Comparative Example 1 - 54 - 200839444 Prepared in the same manner as in Example 1. The pigment dispersion liquid, the coloring agent (A) at different points, the dispersing agent, and the dispersion medium for the pigment were changed as shown in Table 3. The composition for forming a colored layer was prepared and evaluated in the same manner as in Example 1, and the difference was obtained. The pigment dispersion liquid prepared as described above and the type and amount of the alkali-soluble resin (B), the photosensitive polymerization initiator (D) and the solvent, and the amount of diisoprolol hexaacrylate as the polyfunctional monomer are as follows. The changes are shown in Table 3. The results are shown in Table 3.

-55- 200839444 e漱C.Ex.l | Red Pigment 1 BYK-2000 | PGMEA | rH ώ 〇 Starter A 1 inch 3MBA 1 00 00 XX Ex.2 Green Pigment BYK-2001 3MBA Β-4 〇 inch r —ί Initiator B 〇r4 3EPE On 〇〇Ex.l Red pigment BYK-2000 PGMEA ι-Ή ώ yn vo cn Η Starting agent A cn 3EPE cn Ό 〇<] 00 Colorant (A) type dispersion Type of liquid Type of dispersing medium used for pigments Types Dosage Type Dosage Type Dosage Residues Presence or absence of edge defects Exist or absence of formable size (micron) Alkali soluble tree S (Β) Polyfunctional Monomer (C) Photopolymerization Initiator (D) Solvent Pigment Dispersion Radiation Sensitive Composition Evaluation Results -56- 200839444 The abbreviations of the components in Table 3 indicate the following. (A) Colorant: Red pigment: 8 〇 wt% CI·Pigment red 254 and 20% by weight CI Pigment red 177 mixture Green pigment: 60% by weight CI pigment green 36 and 40% by weight CI Pigment yellow 1 50 mixture Dispersant: BYK-2000 : Disperbyk-2000 (trademark of BYK-Chemie GmbH) BYK-200 1 : Disperbyk-2001 (trademark of BYK-Chemie GmbH) Dispersion medium for pigments: PGMEA : propylene glycol monomethyl ether B Acid ester 3MBA: 3-methoxybutyl acetate (D) photopolymerization initiator: initiator A: 2-methyl-(4-methylthienyl)-2-morpholine-11-propyl- 1 -嗣 starter B · acetam-1 -[ 9 -ethyl-6 -[ 2 -methyl-4 - ( 2,2 - monomethyl-1,3-dioxolan) methoxy Benzobenzyl]-9.H--oxazol-3-yl]-1-(anthracene-ethene) Solvent = 3EPE: 3-Ethyloxypropanoate 3MBA: 3-methoxyacetic acid The amount of the components in the butyl ester table 3 is expressed in parts by weight. -57- 200839444 The dispersant for preparing the pigment dispersion is added as a solution, and the amount of the dispersant in Table 3 is expressed as a solid content (weight other than the solvent). The alkali-soluble resin (B) was added as a solution containing the alkali-soluble resin prepared in the above Synthesis Example, and the amount of the alkali-soluble resin in Table 3 was the amount of the solution. Example 3 φ 20 parts by weight as carbon black of the colorant (A) '4 parts by weight Disperbyk-167 (trademark, product of BYK-Chemie Gmb®) and 76 parts by weight as a dispersing agent as a dispersion medium for pigments The 3-methoxybutyl acetate was processed by a bead mill to prepare a pigment dispersion. Then, '100 parts by weight of the pigment dispersion prepared above, 52.5 parts by weight as a solution of the alkali-soluble resin (Β) containing the soluble resin [Β · 2] (resin concentration: 20% by weight), as a polyfunctional 5.6 parts by weight of the monomer (C), isopentitol tetrapropionate, 2.4 parts by weight, diisopentaerythritol hexaacrylate, and 3.7 parts by weight as the photopolymerization initiator (D) Revenue-1-[9-ethyl-6-[6-methyl·4-(2,2-dimethyl-l-1,3-dioxolan)methoxybenzylidene]-9. Η·-carbazol-3-yl]-b-(0-acetamidine) and 76 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a composition for forming a colored layer. The obtained composition for forming a color layer was evaluated by the method of Example 1, and the thickness of the coating film formed at different points was 1. 〇 micrometer. The results of the evaluation are shown in Table 4. -58- 200839444 Examples 4 to 10 and Comparative Example 2 In Examples 4 to 6, 8 to 10 and Comparative Example 2, a pigment dispersion liquid was prepared in the same manner as in Example 1. In Example 7, a pigment dispersion liquid was prepared in the same manner as in Example 3, except that propylene glycol monomethyl ether acetate was used as a dispersion medium for the pigment. The composition for forming a colored layer was prepared and evaluated in the same manner as in Example 3, except that the pigment dispersion prepared above was used, and the type and amount of the alkali-soluble resin (B) and the solvent were changed as shown in Table 4 and used. The polyfunctional monomer and the photopolymerization initiator shown in Table 4 in the amounts shown in Table 4 were used as the polyfunctional monomer (C) and the photopolymerization initiator (D). The results are shown in Table 4.

-59- 200839444 inch 撇 1 C.Ex.2 1 | 32.0 | inch (N 1 卜 3EPE j <] X Ex. 10 B-10 61.7 CN 1 1 ΓΠ 3MBA 68.6 〇〇Ex.9 B-3 1 52,5 j inches (N VO in 1 〇rn 3MBA 〇<1 Ex. 8 B-9 52.5 inches (N 1 卜 3MBA 〇〇Ex.7 B-8 52.5 1 Ο 00 face rn 3MBA VO 〇 〇Ex. 6 1 B^7 inch (N VO 〇r—Η <Ν 3EPE VO 〇〇Ex.5 B-6 |46·5” m cK 1 1 卜 rn 1 3MBA 1 T—Η 00 〇〇Εχ · 4 _1 ώ 1 52.5 1 inch ri Ό ... 1 ΓΛ Imba 1_ VO 〇〇 | | Ex.3 1 B-2 ] 1 52.5 1 inch (N νο 1 rb 1 3MBA 1 vo 〇〇 type usage polyfunctionality Monomer (c) Amount of diisopentyltetraol hexaacrylate! Amount of pentaerythritol hexaacrylate photosensitive polymerization initiator (D) Starting agent Α amount of initiator B amount 丨 type amount residue Presence or absence ί Edge defect presence or absence of pattern size that can be formed (micron) Alkali-soluble resin (B) Solvent radiation sensitivity composition evaluation result f-yi 1 : ΘΗϋ II (4) *..·Χ3 -60 - 200839444 Photosensitive polymerization in Table 4 The abbreviations of the initiator (D) and the solvent are shown in Table 3. In addition, the amounts of the components in Table 4 are expressed in parts by weight. The alkali-soluble resin (B) is prepared by the above-mentioned synthesis example. In the form of a solution of an alkali-soluble resin, the amount of the alkali-soluble resin in Table 4 is the amount of the solution. As described above, the radiation-sensitive composition of the present invention can form a pattern edge without defects and no side even under low exposure. a fine pattern of etching, and is applicable to forming a coloring layer containing a pixel constituting a color filter or a coloring layer which is a black matrix because no insoluble matter remains during development and no scum is formed at the edge of the pattern.

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Claims (1)

200839444 X. Patent application 1 · A radiation-sensitive composition comprising: (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator , wherein the alkali-soluble resin (B) has a structure represented by the following formula (B-i) The "X" system of a carbon atom represents a monovalent organic group having a propylidene group or a methyl propyl sulfhydryl group, an ethyl group or a 1-methylethyl group, and the γ system represents a divalent organic group' h is an integer from 1 to 5) and the composition is used to form a colored layer. 2) The radiation-sensitive composition of the patent application scope, wherein X in the formula (B-1) represents a monovalent group represented by the following formula (χ): -62- 200839444 (x-1) (wherein R represents a hydrogen atom or a methyl group, i is an integer of 2 to 5, and j is an integer of 〇 to 10), and the radiation-sensitive composition of claim 1 Wherein Y is a methylene group, an alkyl group having 2 to 6 carbon atoms or an alkenyl group (such an alkyl group or an alkenyl group intermediate hetero atom), a cyclohexanediyl group, a cyclohexene group A diyl group or a aryl group having 6 to 12 carbon atoms (this aryl group may have a carboxyl group or an acid anhydride group). 3. The radiation-sensitive composition according to claim 1 or 2, wherein the alkali-soluble resin (B) has, in addition to the structure represented by the formula (1), at least one structure selected from the group consisting of: B-2) Structure: (wherein R4 represents an aryl group having 6 to 10 carbon atoms or an alicyclic group having 3 to 10 carbon atoms), and a structure represented by the following formula (B-3): -63- 200839444 (B-3) (wherein R5 to R1g each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a hydroxymethyl group or a carboxyl group). 4. The radiation-sensitive composition according to claim 1 or 2, wherein the photosensitive polymerization initiator (D) comprises a compound represented by the following formula (D-): (wherein R11 represents an alkyl group having from 1 to 2 carbon atoms, a cycloalkyl group having from 3 to 8 carbon atoms or a phenyl group, and R12 and R13 each independently represent a hydrogen atom and have 1 to 20 carbon atoms. An alkyl group, a cycloalkyl group having 3 to 8 carbon atoms, a phenyl group which may be substituted or a monovalent alicyclic group having 7 to 20 carbon atoms (excluding cycloalkyl 64-200839444 R14 is represented by 1) An alkyl group of 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or a cycloalkoxy group having 3 to 8 carbon atoms, when plural When R14, which may be the same or different from each other, R15 represents a monovalent oxygen-containing heterocyclic group having 4 to 20 carbon atoms, a monovalent nitrogen-containing heterocyclic group having 4 to 20 carbon atoms or 4 to 20 The monovalent sulfur-containing heterocyclic group of a carbon atom, when a plurality of R15 are present, may be the same or different from each other, p is an integer of 〇 to 6, q is 0 or 1, and η is an integer of 0 to 5. m is an integer from 0 to 5, and the constraint is (n + m ) S 5 ). 5. A color filter having radiation sensitivity as claimed in claim 1 or 2 A coloring layer formed by a composition. 6. A liquid crystal display device comprising the color filter of item 5 of the patent application. 7. A black matrix comprising the radiation sensitivity of claim 1 or 2 of the patent application scope A coloring layer formed by the composition. A liquid crystal display device comprising the black matrix as in the seventh aspect of the patent application. 9. A method for producing an alkali-soluble resin having a structure represented by the formula (B-1), It comprises a compound represented by the following formula (al): X—COOH (a1 ) (wherein X is as defined by the formula (B-1)) is added to a polymer having a structure represented by the following formula: Β-Γ: -65- 200839444 (wherein R1, R2, R3 and h are as defined in formula (B-l)), and thereafter a compound of the following formula (a2): 0 II A Y\/0 (a2) c II ο (wherein γ is as defined by formula (B-l)) is added to the polymer. -66- 200839444 VII. (1) The representative representative of the case is: None (2), the representative symbol of the representative figure is a simple description: 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none -5-