TW201006884A - Colored hardening composite - Google Patents

Abstract

This invention provides a colored hardening composite that contains dye (A), a polymeric compound (B), and a binder resin (C). The binder resin (C) is a copolymer containing a constitutional unit derived from a compound (C0) which has a carbon-carbon unsaturated double bond and cyclic ether structure, and a constitutional unit derived from at least one kind of compound (C2) chosen from a group of compounds consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride.

Description

201006884 VI. Description of the Invention: [Technical Field to Which the Invention Is Ascribed] The present invention relates to a colored curable composition. [Prior Art] A colored curable composition is used for producing a color filter for use in a display device such as a liquid crystal display panel, an electroluminescence panel, or a plasma display panel. As the coloring curable composition, it is known to use a pigment or a dye as a coloring agent (Non-Patent Document υ. [Previous Technical Literature]

[Non-Patent Document] [Non-Patent Document 1] Easily Understand the Production of Liquid Crystal Display (Refer to Chinese translation) Ρ112 (曰刊工业新闻公司, March 31, 2005, first edition, second brush release) [Invention] The object of the present invention is to provide A color filter colored curable composition excellent in solvent resistance can be formed. The inventors of the present invention have completed the present invention in order to find a color-curable composition capable of solving the above problems. That is, the present invention is the following invention. A colored hardening composition comprising a dye (Α), a polymerizable compound field, and a binder resin (c), the binder resin comprising: a carbon-carbon unsaturated double bond and - _ a compound (c_constituting unit; and a constituent unit derived from at least one of the group consisting of a group of free unsaturated carboxylic acids and unsaturated carboxylic anhydrides. The ring-shaped scale structure is an aliphatic polycyclic type. A color-hardening composition, for example, an epoxy structure, an octa-hardening composition of VIII or 2., wherein 'having a carbon-carbon unsaturated double bond, a ether-ether structure (德) "At least one compound of the group consisting of a compound represented by the formula (C1) and a compound represented by the formula (C1-2). 3 201006884

The two im'R substituted by hydroxy i each independently represent a hydrogen atom or an insoluble group. ] X 'each independently' denotes a single bond or may also contain a carbon atom of a hetero atom, and the dye (A) contains 4. The colored hardening composition of any one of 1. to 3. A dye for a dye of a carboxyl group. The colour-hardening composition according to any one of the preceding claims, which further comprises a pigment. The color-curable composition of any one of h to 6. is formed by a light micro-shirt method or an inkjet method. 8. A color filter containing a pattern such as 7. 9. A liquid crystal display device comprising a color filter such as 8. [Embodiment] The dye (A) is not particularly limited, and a known dye such as an oil-soluble dye, an acid dye, an amine salt of an acid dye or a sulfonamide derivative of an acid dye can be used. The aforementioned dyes are, for example, a color index (a compound classified as a dye in The Society of Dyers and Colourists), or a known dye described in Dyeing Notes (color dyeing company), specifically, for example, CI·Solvent Yellow 4 (hereinafter, omitted CI solvent yellow, only the number is recorded.), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162, CI solvent red 45, 49, 125, 130, CI Solvent Orange 2, 7, η, ^, 26, 56, CI Solvent Blue 35, 37, 59, 67, CI Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc. . Further, CI acid dyes, for example: C, I. Acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 4 201006884 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 25, CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 3, 34, 35, 37, 42, 44, 50, 5, 52, 57 , 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 15 158, 176, 182, 183, 198 , 206, 21 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 26, 266, 268, 270, 274, 277, 280, 28, 195, 308, ® 312, 315, 316, 339, 34, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426, CI, Acid Orange 6, 7, 8, 10, 12, 26, 50, 5 Bu 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173, CI Acid Blue Bu 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 17 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 335, 340, CI·Acid Violet 6B, 7, 9, 17, 19, CI Acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109 and other dyes. Further, CI Φ direct dyes, for example: CI direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 7 and 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141, CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176 ,177,179,181,182,184,204,207,211,213,218,220,221,222,232,233,234,241,243,246,250, CI Direct Orange 34, 39, 4 46, 50, 52, 56, 57, 6 Bu 64, 65, 68, 70, 96, 97, 106, 107, CI Direct Blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94 , 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161 , 162, 163, 164, 166, 167, 170, 17 172, 173, 188, 189, 190, 192, 193, 194, 196, 5 201006884 198, 199, 200, 207, 209, 210, 212, 213 , 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 25 252, 256, 257, 259 260, 268, 274, 275, 293, CI·Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104, CI · Direct green 25, 27, 3 Bu 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and other dyes. Also 'CI mordant dyes, for example: CI mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65, CI mordant red 2, 3 , 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 4, 43, 45, 46, 48 , 53, 56, 63, Ή, 74, 85, 86, 88, 90, 94, 95, CI mordant orange 3, 4, 5, 8, 12, 13, 14, 20, 2, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48, CI mord blue 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84, CI mordant purple 1, 2, 4, 5, 7 , 14, 22, 24, 30, 3, 32, 37, 40, 4, 44, 45, 47, 48, 53, 58, CI mord green, 3, 4, 5, 10, 15, 19, 26, 29 , 33, 34, 35, 41, 43, 53 and other dyes. Further, the dye (A)' is, for example, an amine salt of an acid dye represented by the formulae (i) to (vii), and a conjugated amine derivative of an acid dye represented by the formulas (viii) to (ix). D — (S03 ) m (CnH2 n + 1N+ H3 ) m (i) 〇-(S03-)m {(CnH2n+i)2N+H2} m (ii) 〇-(S03-)m {(CnH2n.i ) 3N+H} m (iii) D—(S03 )m {(CnH2n+1)4N+ } m (iv) D—(S〇3 )m (Ce H2 e + 1 OCf H2 fN+ H3 )m (v) D-(S03- )m {(CnH2n+ i)(PhCH2)2N+ H} m (vi) D-(S〇3-)m {(CnH2n+ i)Py+ } m (vii) D-[ {S02NH(CnH2n+ i )} P][(S〇3L)q] (viii) D-[ {S02NH(CeH2e+ i〇CfH2f)} p][(S03L)q] (ix) [Formula (i)~(ix) in 'D Represents the base derived from the pigment. m represents an integer of 1 or more and 20 or less. 201006884 η represents an integer of 1 or more and 20 or less. e and f are independent, table 1 ^ a-

Ph represents a phenyl group. An integer represented by the formula (I) in which a nitrogen atom is bonded to CnH2n+ } (I) (Ra)n Μ Methyl °ma represents an integer of g or 1. ) ❹ Ο P is not an integer of 1 or more and 8 or less. q Table ^ 0 or more and 8 or less integers. L represents no hydrogen atom or monovalent cation. ]

, η Ϊ田一四签 〇 The following integer 'better is 1 or more and 8 or less I number. m ' is preferably an integer of 1 or more and 10 or less, and η ' is preferably 1 or more and 1 〇. A positive number, more preferably 1 or more and 8 or less | e and [, each of which is independent, more than or equal to -1, 1 or more and 6 or less. In addition to the integer below 8, the better shoulder is better than the formula (j-丨). (M) CH, P, preferably represents 1 or more 6 & integer. The following integer is more preferably: q ′ above 5 or less preferably represents 6 above 6 as an integer. More preferably, the integer is 钾5 or more potassium ions, (c2h5)3hn 201006884 The above azo dyes, for example, the dyes represented by the formulae (1) to (4).

In the formula (1), R1 represents an alkyl group having 2 to 20 carbon atoms, a cyclohexylalkyl group having 2 to 12 carbon atoms in the alkyl chain, and an alkylcyclohexyl group having 1 to 4 carbon atoms in the alkyl chain. An alkyl group having a carbon number of 2 to 12 substituted with an alkoxy group having 2 to 12 carbon atoms, a fluorenyl fluorenyl group represented by the formula (1-1), and an alkyloxycarbonyl group represented by the formula (1-2) An alkyl group, a phenyl group substituted with an alkyl group having a carbon number of 20, or a phenyl group substituted with a phenyl group having 1 to 2 carbon atoms. L - CO - Ο - L2 - (1 - 1) L3 - 0 - CO - L4 - (1 - 2) (In the formula (1 - 1), L1 represents an alkyl group having 2 to 12 carbon atoms. L2 represents a carbon number In the formula (1-2), L3 represents an alkyl group having a carbon number of 2 to 12. L represents a stretching group having a carbon number of 2 to 12.) R to R represents a hydrogen atom and a carbon number of 1. ~4 of the alkyl group, the winding group or the _ atom. a base of 2 to 20, such as ethyl, n-propyl, isopropyl, n-hexyl, n-decyl, n-decyl, n-dodecyl, 2-ethylhexyl, 1,3 - dimethyl butyl, 1 201006884 - methyl butyl, 1,5 - dimethylhexyl and U, 3, 3-tetradecyl butyl and the like. The cycloalkyl chain has a carbon number of 2 to 12, such as cyclohexylethyl, 3-cyclohexylpropyl and 8-cyclohexyloctyl. The alkyl group having a carbon number of the alkyl group is i to 4, for example, 2-ethylcyclohexyl group, 2-propylcyclohexyl group, and 2-(n-butyl)cyclohexyl group. An alkyl group having 2 to 12 carbon atoms substituted by an alkoxy group having 2 to 12 carbon atoms, for example, 3-ethoxy-n-propyl, propoxypropyl, 4-propoxy-n-butyl, 3 - mercapto-n-hexyloxyethyl and 3-(2-ethylhexyloxy)propyl and the like. A phenyl group substituted with an alkyl group of 1 to 20, for example, o-isopropylphenyl group or the like. The alkyl group having 1 to 2 carbon atoms substituted by a phenyl group, for example, DL-1-phenylethyl, benzyl and 3-phenyl-n-butyl. 'Alkyl group having 2 to 12 carbon atoms in L1 and L3, for example: ethyl, propyl, n-hexyl, ^yl, n-decyl, n-dodecyl, 2-ethylhexyl, u-dimethylbutyl Base, 1-methylbutyl, 1,5-dimethylhexyl and U 3,3-tetradecylbutyl and the like. a ^ L2 & L4, an alkylene group having 2 to 12 carbon atoms, for example, a dimethylene group and a hexamethylene group. R2 2 to R5 ' represents a hydrogen atom, a carbon number of 4, a secret or a # atom. Flute-butan pot example ^ chlorine atom,? Base, ethyl, n-propyl, n-butyl, isopropyl, etc., etc., fluorine atom, chlorine atom, atom and moth atom - butyl atom, methyl, ethyl, n-propyl, n-butyl Base, isopropyl, first butyl, second butyl, fluorine atom or chlorine atom. In the case of the transformation of the Ϊ化卿, the preferred secret is, for example, a formula (5) f2 from the dye of the group I, such as the compound represented by the formula (6). The compound "from the dye of the base of the diphenylmethythine dye" is, for example, a compound represented by the formula (7). The substance, etc., is derived from a dye based on 9 money, such as a compound represented by the formula (8), a dye having a base derived from a phthalocyanine dye, for example, a compound represented by the formula 201006884

• so2nh(ch2)3och(ch3)2 S03H |u .b (9) a = 2^4 , b = 2 dye (A), from the viewpoint of having a tendency to improve solvent resistance by reacting with a cyclic ether structure, 2010-0684 It is preferred to use a dye containing a m-based dyeing group. (2〇^^^^7_limit 'Korean known substance such as formula (10)~

11 201006884

12 201006884 These dyes may be suitably selected in accordance with the light fading resistance or the spectroscopic spectrum when the solubility of the solvent or the pattern of the color filter comprising the color-curable composition containing the dye is used. The content of the dye (A) is preferably from 5 to 65 mass%, more preferably from 8 to 60 mass%/0, more preferably from 1 to 5% by mass based on the solid content of the colored curable composition. ~55 mass%. When the dye (A) contains a dye having a carboxyl group, the content thereof is preferably from 1 to 100% by mass, more preferably from 5 to 1% by mass, based on the mass fraction of the dye (A). It is especially good for 10~1〇〇% by mass.固体 In this specification, the solid content refers to the total of the components after the solvent is removed by the coloring curable composition. h The colored curable composition of the present invention contains pigments in addition to the dye (A). good. / Pigment' Specifically, for example, a compound classified as a pigment in a color index (published by The Society of Dyers and ^olourists). Specifically, for example, CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 11〇, in, 125, 128 Yellow pigments such as 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; CI pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59 , 6 dips 64, 65, 71, 73 and other orange pigments; CI pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, Red pigments such as 224, 242, 254, 255, 264, and 265; CI·Pigment Blue 15, 15 : 3, 15 : 4, 15 : 6, 60 and other blue pigments; CI Pigment Violet 1, 19, 23, 29, Purple pigments such as 32, 36, 38; CI pigment green 7, 36, 58 and other green pigments; CI pigment brown 23, 25 and other color pigments; CI pigment black 1, 7 and other black pigments. _ where 'CI pigment yellow 138, 139, 15 〇, CI pigment red 177, 209, 242, 254, CI pigment red purple 23, c 丄 pigment blue 15: 3, 15: 6 and 〇 1 pigment green 7, 13 201006884 36 5 8 is preferred. When the coloring curable composition contains the dye (A) and the pigment, the content of the pigment is preferably from 2 to 98 by mass based on the total amount of the dye (A) and the pigment in the coloring curable composition. %, more preferably 5 to 95 mass ° /. , especially good for 1〇~95皙晋%. The above pigment may be used in the form of a pigment dispersion liquid in a state where it is dispersed by a dispersing agent and uniformly dispersed in a solution in the presence of a pigment. The dispersing agent may be used singly or in combination of two or more kinds, such as a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric, a polyester, or a polyamine. Examples of the surfactant, for example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, grade 3 Amine-denatured polyurethanes, polyethyleneimine, etc., brand name, chemical industry (share), POLYFLOW (common company), EFT〇p (T〇kem (10) company), Megafacc Dainippon Ink Chemical Industry Co., Ltd., Friends 3M (_), ASahiGUard, SURFL〇N (above, Asahi' Solsperse^ca (^)%) 'EFKA (EFKA CHEMICALS) and PB821 (supplier), etc. In the case of 4 S, the amount used is 100% by mass based on the pigment, and more preferably 5 G% by mass based on the mass fraction. The use of the dispersing agent is placed in the right center, and there is a tendency to produce a uniform dispersion. The compound (8) can be used for heat or light, or because of its body or oligomer, and can further be hardened. Know the substance early. Take a step and shoot. The flat wire (4) can be used in five cases of male alcohol (four) fine alcohol four (methyl (tetra) _, two pentaerythritol (rothene) propylene vinegar, dipentaerythritol hexa) propylene glycolate, and f pentaerythritol five (meth)acrylic acid vinegar derivative, oxygen: methyl, : ester and oxyethylated trishydroxymethyl, phthalocyanine, methyl (10) bis (methyl) such as (meth) propyl (meth) acrylate ) C-acrylic acid and oxy-propylated glycerol tri-polymeric polymer 'for example: epoxy (methyl) propyl axis, amine acrylic acid vinegar and poly 14 201006884 ester (meth) acrylate vinegar, etc., for example, 帛The current situation and hope of υν·ΕΒhardening technology (CMC it} version) The oligomers described on pages 18 to 20. The content of the polymerizable compound (B) is preferably in the range of 1 to 90% by mass, more preferably 20 to 2 by mass, based on the weight of the coloring curable composition. % ' is preferably 30 to 70% by mass. The exudation and the 'polymerizable compound (9) have a tendency to increase the solvent resistance k by reacting with a cyclic reaction, and the monomer or oligomer containing a mercapto group is more preferable. Examples of secret monomers or silks, such as ······················································ Etc.: a hydroxyl group-containing polyacrylate such as trimethylolpropane di(methyl)propane diacetate di(meth)propacrylate, pentaerythritol tris(methyl)propene^^pentaerythritol (Methyl) acrylate vinegar, etc. The aforementioned polycarboxylic acid, such as phthalic acid, 3,4-dimethyl-terephthalic acid, pyromellitic acid, trimellitic acid, M, 5, 8 —Cai Sizhi acid 3,3,4,4 - two bases, four thieves and other aromatic polyphthalic acid; azelaic acid, adipic acid, W, 3,4 - butyl burning four ships, maleic acid, rich Fatty diversity such as horse lice and itaconic acid Acids; formic acid six ί ϊΐ formic acid, 3,4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, ί: Ί;; acid, 1,2,4-cyclopentanthene tridecanoic acid, 4 - Cyclohexanthene - alicyclic polycarboxylic acid cages such as pentylene sulphate, 1,2,4,5-cyclohexanyltetradecanoate - description of multiple New Zealand livers, such as ortho-benzene Dicarboxylic acid liver, pyromellitic anhydride, partial class of sub-xuan, 3,3',4,4'-diphenyl-tetracarboxylic acid di-hepatic and other aromatic poly-ordinated needles formic acid f?, succinic anhydride , citraconic anhydride, dodecenyl succinic anhydride, C3; - maleic anhydride, 1,2,3,4-butadiene, four thieves, two needles, etc., aliphatic multi-droked anhydride, cyclopentanyl dicarboxylic acid liver, 3 , 4 - dimethyltetrazolylphthalic acid bribe, 1 U, 4 - cyclohexane tris-anhydride, cyclopentanic acid two needles, ' ', jade hexane tetracarboxylic dianhydride, salic anhydride (himic anhydride), that new acid 15 201006884 anhydride (nadic anhydride) and other alicyclic polycarboxylic anhydrides; anhydrides such as benzene, triglycerides, glycerin, silk, bribes, etc. Specific examples of the substance, for example: Sanjing Jiaqi Burn II (A), the neighbor of sour vinegar Phthalate, glycerol II (exhaustive C. ester; ^ acid ^ ^, tetra = di(meth) acrylate phthalate series, pentaerythritol triacrylate vinegar succinyl ester, dipentaerythritol a phthalic acid ester of penta(meth)acrylate, a succinate of ditetraolpenta(methyl)propionate, etc., which is used in the ίίϊ compound (8)' using a silky monomer or oligomer When the content of the compound (9) is divided by mass, it is recorded as Η(8) ❹ is 5~1〇〇% by mass, particularly preferably 1〇~1〇〇% by mass. Further 隹-carbon test solubility is a copolymerization Included in the product, including: (from the carbon), 槿ίί ΐ 之 化合物 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( F epoxy structure, aliphatic monocyclic epoxy structure and 氧 o oxygen structure 'aliphatic polycyclic epoxy structure is especially good.

Q, a compound of the t-ring aliphatic epoxy structure, specifically an acid ester, β ===_, p-methylepoxypropyl (methyl) propylene \ /

(CH2OCH2CH-CH2)n silky listener seed number 1~Η) burned 16 201006884 The compound represented by the above formula, for example: o-ethene-based epipepene, propylene = ketone epoxy _, pair Vinyl-based glycidyl ether, α-methyl-o-mentylbenzyl epoxidized propyl ether, α-methyl-m-vinylbenzyl epoxidized propyl ether, α-fluorenyl-p-vinyl group Epoxy (tetra), 2,3-diepoxypropoxymethyl styrene, 2,4-dipropyleneoxymethyl styrene, 2,5-diepoxypropoxymethyl styrene, 2, 6-diethyleneoxypropenyl styrene, 2,3,4-trisethoxypropoxyphenyl styrene, 2,3,5-trisethoxypropoxymethyl styrene, 2,3, 6-trisethoxypropoxyphenyl styrene, 3,4,5-trisuccinoxypropylmethylstyrene and 2,4,6-trisethoxypropoxymethylstyrene. A compound having a carbon-carbon unsaturated double bond and an aliphatic monocyclic epoxy structure, which is an epoxy group-containing compound on the ring of an aliphatic monocyclic compound. a compound having a carbon-carbon unsaturated double bond and an aliphatic monocyclic epoxy structure, and in the form of, for example, vinylcyclohexene monooxygenated U-epoxy-4-4-ethenylcyclohexane (for example, CELLOXIDE2®) 00 ; Daicel Chemical Industry Co., Ltd., 3,4-epoxycyclohexyl methacrylate (for example, CYCLMER A400; Daicel Chemical K Co., Ltd.), 3,4-epoxycyclohexylmethyl fluorenyl Acrylate (for example, CYCLMER M1 〇〇; manufactured by Daicel Chemical Industry Co., Ltd.). A compound (Cl) having a carbon-carbon unsaturated double bond and an aliphatic polycyclic epoxy structure (hereinafter sometimes referred to as "(ci)")" is an epoxy group having an epoxy group on a ring of an aliphatic polycyclic compound. Compound. An aliphatic polycyclic compound such as dicyclopentanthene or tricyclic tercene. © (C1) 'For example, 3,4_epoxy-decyl acrylate, 3,4-epoxy-decyl acrylate, compound of formula (C1-1) and formula (C1-2) The compound shown is preferably at least one compound selected from the group consisting of a compound represented by the free formula (C1 - 1) and a compound represented by the formula (C1 - 2).

In the formulae (C1-1) and (C1-2), 'R' is independently an alkyl group having 1 to 4 carbon atoms or a hydrogen atom which may be substituted by a hydroxyl group. ' 17 201006884 based. ] X each independently' denotes a single bond or a carbon number of a hetero atom which may be substituted with a carbon number of 1 to 4, specifically: for example, a hydrogen atom, a methicone , isopropyl, n-butyl, t-butyl, tert-butyl, ethyl, 2-ylethyl, propyl-n-propyl, 2-indole and 1-oxa, 3-perylene- N-propyl, propyl-isopropyl, 2-hydroxy-

The second entanglement, ... the sulphur original ====: neutron • oxygen atom, (4) ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί , an oxygen-extended ethyl group, an oxygen-extended propyl group, a thiomethylene group, a sulfur-extended ethyl group, a group or an amine is more preferably a monomethylene group, an ethylene group, a gas methylene group or an oxyethylene group.

A compound represented by the formula (C1 -1), for example, a compound represented by the formula (C1 - i~^~ - i - - is preferably a formula (C1 - i-1), a formula (C1 - i - 3) , a compound of the formula (C1 - i - 5), the formula (C1 - Bu 7), the formula (d - n), the formula (C1 -} - (1) - the formula - i - 15), more preferably (d - 丨一)), a formula (C1 - 丨 - 7), a formula (C1 - 1 - 9) or a compound of the formula (Cl - 1 - 15). 18 201006884

9H3i h2c=ch-co h2c=ch-co-ch2 h2c=ch-c-o-c2h4 Η2〇=ΟΗ—C Ο一C2H4—ο ch3o I II h2c=c—c—o ch3 o I II h2c= C-co-ch2 H2C-C-C-O-C2H4

C2Hs〇 I II h2c=c-c-o CHoOH o I II h2c=c-c-o (Cl-1-13)

H2c=ch-c—〇-C2H4—so II H h2c=ch-c—o—c2h4-n ch3o I II H2C=0—C—O—C2H4—s CH30 I II H Η2〇=0—C—O One C2H4-N

(Cl-1-8)

(Cl-1-10)

Ch3〇 / II H2C=C——C-O-C2H4-O c2h4oh o I 11 h2c=c-c-o

(Cl-1-15)

a compound represented by the formula (Cl-2), for example, a compound represented by the formula (Cl-2-1) to the formula (Cl-2-15), preferably a formula (Cl-2-1), a formula (Cl) —2 —3), Formula (Cl—2 —5), Formula (Cl—2—7), Formula (C1-2—9), Formula (Cl—2—11)~ (C1-2—15) The compound shown is more preferably a compound of the formula (C1 - 2 - 1), the formula (C1 - 2 - 7), the formula (C1 - 2 - 9) or the formula (C1 - 2 - 15). 19 201006884 ?

H2C=CH—0—〇 H2C=CH-C-〇-CH

(Cl-2-5) ?H3i h2c=c一ό-o-c2h4-s h2c=ch-c-〇-c2h4

(Cl-2-8) H2C=CH-C-〇-c2H4-0 CH3 o HgC—C—C_O ch3 o h2c=c—c—〇—ch2 ch3 o I II H2C=C—C-O-C2H4

丨H3 o H2C=C-C~〇-C2H4-N(Cl-2-15) C2H^) h2c=c-c-0 CH2OH 0 h2c==c--c-o

P—q ❹ c2h4oh 0

CH30 I 11 H2C=C-C—〇—C2H4-O

At least one compound selected from the group consisting of the compound represented by the free formula (Cl-1) and the compound represented by the formula (Cl-2) can be used alone. Also, these can be mixed at an arbitrary ratio. When mixing, the mixing ratio is preferably 5: 95 to 95: 5 in terms of the molar ratio of the formula (C1 - 1): formula (C1 - 2). More preferably 10: 90~90: 10, especially good for 20: 80~80: 20. (C2) 'Unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; An acid needle of a dicarboxylic acid; a polybasic acid of 2 or more valences such as succinic acid mono [2-(methyl) propylene oxiranyl], phthalic acid mono[2-(methyl)ethyl] Saturated mono[(methyl) propylene oxide ^ 20 201006884 For example, α-(transmethyl)acrylic acid is an unsaturated acrylate containing a hydroxyl group and a carboxyl group in the same molecule. Among these, acrylic acid, methacrylic acid, and maleic anhydride are suitable for the user from the viewpoints of copolymerization reactivity and solubility in an alkaline aqueous solution. These are used singly or in combination. The binder resin (c) is a copolymer comprising a constituent unit derived from (C1) and a constituent soap from (C2), a constituent unit derived from (C1), and a ratio derived from (C2). Relative to the total number of moles constituting the constituent units of the aforementioned copolymer,

If the fractional meter is as follows, it is preferable that the stability, the resistance, and the mechanical strength of the product are improved. From the constituent unit of (C1); 2 to 98 mol% from the constituent unit of (C2); 2 to 98 moles/〇 and 'if the ratio of the above constituent units is the following range, from the developer property The point of view is better. The constituent unit derived from (C1); 40 to 85 mol% from the constituent unit of (C2); 15 to 60 mol% The above-mentioned binder resin (C) can be referred to, for example, the literature "Experimental method for polymer synthesis" (Otsu The method described in the documentary and the cited documents cited in the document is published in the EI issue of the Chemical Co., Ltd. (i). ^ Body, the quantitative (C1) and (C2), polymerization initiator and solvent are added to the reaction vessel, replacing oxygen with nitrogen, in the absence of oxygen by stirring, heating, temperature, can be obtained Things. Further, the silk product can be directly dissolved or diluted, or a concentrated or diluted solution can be used, or a solid (powder) can be used to form a take-out by a method such as reprecipitation. Further, the 'bonding resin (c) may contain, in addition to the constituent unit derived from (C1) and the constituent unit derived from (C2), a compound which can be copolymerized with (C1) and (C2) (except, without (C) ^) (C3) (hereinafter sometimes referred to as "d) is a constituent unit. The above '(C3), for example: (mercapto) decyl acrylate, ethyl (meth) acrylate, (meth) acrylate Butyl vinegar, (meth)acrylic acid second butyl vinegar, (meth) acrylic acid tert-butyl ester, etc. (mercapto) acrylic acid alkyl ester; 21 201006884 decyl acrylate, isopropyl acrylate, etc. Alkyl acrylates; (methyl-2-yl)cyclohexyl acrylate, 2-mercaptocyclohexyl (meth) acrylate, tricyclo [5.2.1.0''6] fluorenyl 8-(meth) acrylate ( In the technical field, conventionally used (indenyl dicyclopentanyl acrylate), (cyclo)oxyethyl (meth) acrylate, (meth) acrylate, etc. (meth) acrylate ring a succinyl group; a cyclohexyl acrylate, 2-methylcyclohexyl acrylate, a tricyclo[5.2.1.02,6]decane-8 acrylate (in the technical field, the conventional name uses a bicyclic ring of acrylic acid) Amyl ester), propylene Acrylic cyclic alkyl esters such as dicyclopentyloxyethyl ester and isodecyl acrylate; aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate; phenyl acrylate, Aryl phthalate such as benzyl propionate; bis-diester diester of diethyl maleate, diethyl fumarate, diethyl itaconate; 2-hydroxyl (meth) acrylate Ethyl ester, (meth)acrylic acid 2-hydroxypropyl ester and other base-based vinegar; $cyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2J]hept-2-ene, 5- Ethyl ε[2·2.1]hept-2-ene, hydroxybicyclic P.2.1]heptyl-2-ene, 5-nonylbicyclo[2.2.1]g- 2-dilute, 5-hydroxymethylbicyclo[2 2 _-2-ene, 5-(2,-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]gly-2-ene, 5-ethoxy Bicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2]]hept-2-ene, π- Bis(by mercapto)bicycloindole [2.2.1] hept-2-ene, 5,6-bis(2,-hydroxyethyl)bicyclo[2 2 hept-2-ene, 5,6-decyloxy Double loop [2.2.1] 2-ene, 5,6-diethoxybicyclo[22- 2 - dilute, f-trans-yl-5-methylbicyclo[2.2.1]hept-2,5-yl-5-ethyl Bicyclo[2.2.1]hept-2-ene, 5~indolyl-5-indenylbicyclo[2.2.1]hept-2-diluted, fluorenyl-5-ethylbicyclo[2 2 Cong-2-ene, 5-Hydroxymercapto-5-indenyl bis-[2.2.1]hept-2-ene, 5-silyl-6-methylbicyclo[2.2.1]gly-2-ene, 5-sil-6-B Bis-ring [2 2 hept-2-ene, 5 6 - bis-bicyclo[2.2.1] heptane 2-ene anhydrate (heme acid liver), 5 -t-butoxycarbonyl bicyclo [221] = dioxadiylbicyclo[2.2.1]hept-2-ene, 5-phenoxy nitrite double coat [· .1]hept-2-ene, 5,6-di (t-butoxy) Bicyclo [221] G? - 22 201006884 2 - alkene, 5,6-di(cyclohexyloxycarbonyl)bicyclic P.2.1]hepta-2-ene and other bicyclic unsaturated compounds; N-phenylmaleimide , n-cyclohexylmaleimide, n-benzyl maleimide, amber quinone imine-3, maleimide benzoate, N-amber, imino-4-yl醯iminobutyrate, N-succinimide- 6-maleimide caproic acid vinegar, N-succinimide 3- (PEI) a maleic acid ester and n- (9 ° Ah a bite-yl) maleic imides two acyl groups of several brewing imine derivatives;

Benzene, α-methylstyrene, m-decyl styrene, p-nonylstyrene, ethyl bromide, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, Acrylamide, mercapto acrylamide, vinyl acetate, 1,3-butadiene, isoprene, di-decyl-1,3-butadiene, glycidyl acrylate, methacrylic acid ring Oxypropyl propyl ester, α-ethyl acrylate propyl acrylate, α-n-propyl propylene glycol propyl acrylate, α-n-butyl propylene glycol propyl acrylate, acrylic acid _3, 4 epoxybutyl acrylate , 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 2,7:epoxyheptyl acrylate, α-ethyl acrylate-6,7-epoxy Heptyl ester, hydrazine-vinylbenzyl epoxidized propyl ether, m-vinylbenzyl epoxidized propyl ether and p-vinylbenzyl epoxidized propyl ether. Here, in the present specification, (meth) acrylate means at least one selected from the group consisting of acrylate and acetoacetic acid vinegar. Further, (meth)acrylic acid means at least one selected from the group consisting of acrylic acid and methacrylic acid. Among the classes, benzyl acrylate, styrene, N-phenyl maleimide, N_cyclohexylmaleimine, N-benzyl maleimide, bicyclo [2.2 1] hept-2 _浠 The above (C3) can be used singly or in combination. When (C3) is contained, the ratio of the constituent units derived from (ci) to (C3) to the total number of moles of the constituent units of the copolymer is preferably in the range of the molar fraction. ° Bu from the constituent unit of (C1); 2 to 97 mol% from the constituent unit of (C2); 2 to 97 mol% from the constituent unit of (C3); 1 to % mol% containing the above ( C1)~(C3) a binder resin (〇, which can be produced in the same manner as described above, 23 201006884. Further, the constituent unit in the above-mentioned binder resin (c) is contained in a macromonomer having a monopropylene monomethyl group at the end. The unit represented by the formula (21) and the unit represented by the formula (22) are more preferable from the viewpoints of pattern adhesion and solvent resistance. R8, Re

CO I 0,

HO· (21) R9

CO OH

(22) (In the formulae (21) and (22), R8 and R9 are each independently a hydrogen atom or a carbon group having 1 to 6 carbon atoms.) A binder resin having a constituent unit represented by the formula (21) (C) (), (ci), (C2), and (C3) can be polymerized to obtain a three-component copolymer, and the obtained three-component copolymer, the formula represented by the formula (C2), or a carboxyl group or an acid anhydride group can be reacted. And got it. ’, ^ R9 ❹

(23) A binder resin having a constituent component represented by the formula (22), wherein (3) a copolymer of the three components can be obtained, and the obtained component 3 can be used, for example, with methyl propyl acetoacetate. The method described in JP-A-H05-189574 is carried out in the same manner as in the above. The weight average molecular weight of 1 〇 = tree == benzene is calculated to be 3, _ to 100,000, more preferably 5,000 to 50,000. The above-mentioned range of the weight of the binder resin (C) is eight: the tendency of good coating property, and the film thickness is reduced when developing, and the non-pixel portion has good tendency to be detached during development, and the molecular weight distribution is early. [W the weight average molecular weight (Mw) / number average molecule S (Mn)], preferably U 〜 6 · 〇, more preferably L 2 〜 4 〇. Molecular weight distribution 24 201006884 The above range is preferred because it has a tendency to be excellent in developability. The content of the binder resin (c), based on the mass fraction, is preferably a solid binder resin (c, if the content is in the foregoing range, ^ J 15~mas ❶/, based on the mass fraction, preferably 1 G to 35 f. It is not easy to generate frequency on the substrate of the non-pixel part and the solubility of the liquid is sufficient. 'The pixel part is less likely to reduce the film thickness, and it is better than the direction of the exposure part. It is better.' There is a good guanamine compound in the form of a bird guanamine compound and/or a melamine-containing compound can be used, and it is not particularly limited to use a Japanese sulphate compound, 瘳面-47378, Japanese special-grade - 24^ flat side 4, Japan A well-known substance described in JP-A No. 2007, 169, 607, _ = 巧 = compound, specifically, for example, mono-frost melamine, diso-methane melamine, trimethylol melamine, tetrahydroxy three ^ Mercaptan, hexa(tetra)yl melamine, hexamethylenemethyl cyanoamine, formazan = 6 methoxymethylated compounds or mixtures thereof, hexahydrate trimeric aryl group (4) groups 1 to 6 An ethoxylated methyl compound or a mixture thereof, 1 to 6 propyloxymethylated compounds or Mixing Φ to read 1 to 6 methylated compounds of methylation: diligently, ί ί amine compounds, such as mono (tetra)-based guanamine, di-henry guanamine, bismuth:f-amine, four 1 to 4 carboxy-oxime-sit methylated compounds or mixtures thereof via thiol guanamine, tetramethyl guanine, and methyl ethoxylated oxime of tetramethylol guanamine a compound of a compound or a mixture thereof, tetramethylol guano # I # 4 thiol-methylated compounds or mixtures thereof, and 4 to 4 methyl methacrylates a compound of a butoxy-indenylated compound or a mixture thereof, or a methoxymethyl group of 1 to 3 methoxymethyl groups thereof, which is subjected to butoxymethylation, can be combined with an iron bird fecal amine compound (D). 'Also can be used separately' also 25 201006884 The content of the chemical guano chelates (D), compared to the colored hardening composition of the color hardening composition of the present invention, may further comprise thermal polymerization starting from 2002-348344 '-based, oxidation Bismuth, peroxidation 2,4-—chlorobenzhydrazide © tert-butylperoxychloride, U,3,3,-tetramethylbutyl peroxide to oxidize 2,5 (second butyl peroxidation) Burned, u-double (Third butyl peroxidation ^

酉 酉 ΐ ” ” ” ” ” ” ” ” ” ” ” 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ Isopropyl peroxo hydrogen peroxide, ±3,3,-tetramethylbutyl peroxy 12,5-dimethyl feta 47-butyl =, butyl peroxylated) hexane, dithiol peroxidation , peroxidation, ❹ ” Third butyl acetylation II oxidized acetic acid S day, second butyl peroxide benzoic acid vinegar or 2, 2 - two = more ί is diacetyl peroxide, peroxide II Third hexyl; ί: ίί fr3r di-tert-butyl, p-peroxide, diisopropyl benzoquinone y, 3,3 '-tetradecyl butyl hydroperoxide or hydrazine peroxide. An azo compound such as u, azobiscyclohexanone - ϊίϊΓ-bis, 2,2'-azobis(2,4-dimethylvaleronitrile), '2,2,- (1 even =, ^Methyl·, 2,2,- weaving U,-double 26 201006884 These thermal polymerization initiators (E) may be used singly or in combination of two or more. Using a thermal polymerization initiator (E) The content of the binder resin (c) is preferably in the range of 0.01 to 20% by mass, more preferably in the range of 2 to 1% by mass based on the mass fraction. The colored hardening composition of the present invention Further, the photopolymerization initiator (F) may be further contained, and the photopolymerization initiator may be, for example, a tri-grain-based compound, an acetophenone-based compound, a biimidazole-based compound, an active radical generator, an acid generator, or the like. Three-tillage compounds, such as 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-_1,3,5-three tillage, 2,4-bis(trichloromethyl) )-6-(4-methoxynaphthyl)-_13L5-three-h, 2,4-bis(trichloroindenyl)-6-(4-methoxystyryl)--two tillage, 2 , 4-bis(trimethylsulfonyl)-6-[2-(5-fluorenylfuran-2-yl)vinyl]-1,3,5-two tons, 2 ,4-bis(trichloroindenyl)-6-[2-(indolyl-2-yl)ethenyl]1,3,5-di-spray, 2,4-bis(di-methyl)-6 —[2 —(4—diethylamino-2-indenylphenyl)vinyl]—I,3,5—three tillage, 2,4-bis(trichloromethyl)_6 —[2 — (3 ,4-dimethoxyphenyl)vinyl]-1,3,5-sankun and 2,4-bis(trichloromethyl)-6-/month pepper base-1,3,5-three tillage And, preferably, 2,4-bis(trichloroindenyl)-6-(4-methoxyphenyl)-I,3,5-tri-h,2,4-bis(trichloroindenyl)_6 —(4-methoxynaphthyl)-1,3,5-three tillage, 2,4-bis(trichloroindenyl)-6-(4-methoxyphenylethyl)~1,3, 5 - three tillage or 2,4 - bis (trichloromethyl) - 6 - piperonyl - w, 5 - three call, more ❿ good for 2,4 - bis (three gas methyl) - 6 - pepper base I, 3, 5 - three tillage. The above-mentioned acetophenone-based compound 'e.g. diethoxy acetophenone, 2- fluorenyl-2-indanyl 1-(4-indolyl) phenyl- 1 - Ketone|, 2-yl-2-methyl-1-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-2-methyl-1—[4—(2—hydroxyl Oxy)phenyl] 1-keto, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1 1,4-(4- porphyrin)- 1-ketone, 2-(4-hydrazinobenzyl — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — A propionate of a propyl-1-ketone, etc., preferably 2-mercapto- 2 - porphyrin- 1 - (4-methylthienyl)-propyl-! —ketone, 2__benzyl-2” monoamine-amino-1—(4-flavonyl)butyl-1—anthracene or 2-(4-methyl-benzyl)- 2-dimethylamino-i- (4_porphyrinphenyl) butyl-i-ketone, more preferably benzyl- 2 27 201006884 - dimethylamino-1-(4-porphyrinphenyl) butyl-i

2-Dimethylamino-bu(4-indolylphenyl)-di-platinum (4 methyl meridyl K compound, for example: 2,2, fluorenylphenyl)-4,4,5,5' a tetraphenyl-imidazole, 2,2, a double, a 4,4,5,5'-tetra(m-methoxyphenyl)biimidazole, 2,2,__-di'^ thiophene group, Sit, clever, - bis (2_ sure phenyl) - 4, 4, 5, 5, one, 2, 2'-bis (2-methylphenyl) - 4, 4,, 5, 5,-Tetraphenyl-linked Mimi =: bis(2-chlorophenyl)-4,4,,5,5,_tetraphenyl-linked saliva or 2,2,-double on j stupid)-4 , 4', 5, 5, tetraphenylbiimidazole. One gas The active radical generates fibers to generate active radicals by irradiating light. The above-mentioned radical generating agent 'e.g., a benzoin-based compound, a diphenyl-based compound-based compound, an anthraquinone-based compound, and the like. ^ The aforementioned benzoin compounds, such as benzoin, benzoin ether, benzoin shrine, benzoin isopropyl mystery, and benzoin acetoin. The aforementioned diphenyl ketone compound, for example, diphenyl ketone, o-benzoinylacetoic acid methyl vinegar, 4-phenyldiphenyl fluorene, 4-benzylidene-4, methyl diphenyl sulphide, 3, 3,4 4, ◎~tetrakis(t-butylperoxycarbonyl)diphenyl ketone and 2,4,6-trimethyldiphenyl _ and the like: the aforementioned thioxanthone-based compound, such as 2-isopropyl A thioxanthone, a 4-isopropyl thiophene ketone, a 2,4-diethyl π syringone, a 2,4-dichloropyridinone, and a 1-chloro-4-pyrene thioxanthone. A compound of the earthworms, such as a ruthenium-based compound, and a specific example thereof, for example, .1 - (4 - thiol-phenyl-phenyl)-butyl 1,2 - bis-2 - 躬 - 0—stupic acid @曰,1—(4-phenylthiononyl-phenyl)-octyl-1,2-di- 2-fat-p-formate, 1-(4-phenylsulfane) Base-phenyl)-octyl-1-ketooxime-oxime-acetate and 1-(4-nylthioalkyl-phenyl)-buty-1-net will be a hydrazine-acetic acid vinegar. 28 201006884 An active radical generator other than the foregoing examples, such as 2,4,6-trimercaptophenylphosphonium diphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthracene Benzyl, 9,10-phenanthrene, camphor, phenylethyl ruthenium, ferrocene compound, and the like. The foregoing acid generator, for example, 4-hydroxyphenyldimethylhydrazine p-toluenesulfonate, 4-hydroxyphenyldifluorenylphosphonium hexafluoroantimonate, 4-ethoxylated phenyldifluorenylphosphonium - p-benzoic acid salt, 4-ethoxylated phenyl benzyl hydrazine hexafluoroantimonate, triphenyl sulfonium phthalate, triphenyl sulfonium hexafluoroantimonate, diphenyl A sulfonium salt such as p-toluene acid salt or diphenyl sulfonium hexafluoride, or a nitrobenzyl benzoate acid ester or a benzoin tosylate. Further, the above-mentioned living radical generating agent is also a compound which generates an acid simultaneously with a living radical among the above compounds, and for example, a three-till photopolymerization initiator can be used as an acid generator. When the photopolymerization initiator (F) is used, the content thereof is based on the total amount of the polymerizable compound (b) and the binder resin (C), preferably ο 〜 25% by mass, more preferably 1 to 20% by mass. The color hardening composition of the present invention may further comprise a photopolymerization start aid (G). The photopolymerization initiation aid (G)' is usually used in combination with a photopolymerization initiator (F) to promote polymerization of a photopolymerizable compound which starts polymerization by a photopolymerization initiator (F). Lu Guang polymerization start aid (G), for example, an amine compound, an alkoxy oxime compound, and a thioxanthone compound. The aforementioned amine compound 'e.g.: triethanolamine, methyldiethanolamine, triisopropanolamine, 4-diamylphosphonium phthalate, ethyl 4-diguanyl benzoate, 4-dimethylamine Isoamyl benzoate, 2-nonylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4' Bis(diamine-amino)diphenyl ketone, 4,4'-di(diethylamino)diphenyl ketone, and 4,4'-bis(ethylamidino)diphenyl ketone, etc., 4, 4'-bis(diethylamino)diphenyl ketone is preferred. The alkoxy fluorene-based compound, for example, 9,10-dimethoxyanthracene, 2-ethyl-n- 9,10-dimethoxy fluorene, 9,10-diethoxy fluorene, and 2-ethyl- 9 , 10 - diethoxy hydrazine and the like. 29 201006884 The aforementioned thioxanthone compounds, such as 2-isopropylthioxanthene, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dithioxanthone and anthracene ~Chloro_4_propoxy thioxanthone and the like. The soil photopolymerization start aid (G) ' can be used singly or in combination of two or more. In addition, as a photopolymerization start aid (G), a commercially available product, a commercially available photopolymerization start aid (G), and an organic amine compound such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can be used. Wait. In the present invention, when a photopolymerization initiation aid (G) is used, a combination of a photopolymerization initiator (g)/photopolymerization initiation aid (G) is used, for example, 2,4-bis(trichloroindenyl)-6-piperidin —I,3,5 —Sanwei M,4′-di(diethylamino)diphenyl ketone, diethoxyacetophenone/4,4,bis(diethylamino)diphenyl ketone, 2—曱基一二—咮淋一 1-(4-methylmethoxyphenyl)® propan-1-ketone M,4′-bis(diethylamino)diphenyl ketone, 2-hydroxy-2— Mercapto-p-phenylpropan-1-one/4,4'-bis(diethylamino)diphenyl ketone, benzyldidecyl ketal/4,4'-di(diethylamino) Phenyl ketone, 2-hydroxy-2-methyl-[4-(2-carbylethoxy)phenyl]propan-1-one/4,4'-bis(diethylamino)diphenyl Ketone, 1-cyclohexyl phenyl ketone / 4, 4, mono-(diethylamino) diphenyl ketone, 2-hydroxy-2-indolyl — 1 — [4 — (1 - methyl vinyl Oligomer of phenyl]propan-1-one/4,4'-bis(diethylamino)diphenyl ketone, 2-benzyl-2-diguanidinyl-1 - (4 - 咮Phenyl) butyl-1-ketone/4,4'-di(diethylamino)diphenyl ketone, 2-benzyl- 2 Dimethylamino-1 - (4- porphyrin phenyl) butan-1-one / 4,4'-bis(diethylamino)diphenyl ketone and 2-(4- benzyl benzyl) 2-diaminol-l-(4-indolyl)butan-1-one/4,4, bis(diethylamino)diphenyl ketone, etc., preferably 2-benzyl- 2 - Diammonium-l-(4-carboline)-butyl-1-ketone/4,4'-bis(diethylamino)diphenyl ketone, 2,4-bis(tris) a 6 - pepper base - 1, 3, 5 - three tillage / 4, 4, a pair of (diethylamino) diphenyl ketone or 2 (4 fluorenyl fluorenyl) a 2 - a 'methylamino 1 — (4 — Wei Lin Phenyl) Ding Yi 1 — Mesh / 4,4′-double (diethylamino) diphenyl ketone. When the photopolymerization start assistant (G) is used, the amount thereof is preferably 〇.〇ι 10 parts by mass, more preferably 〇.〇1, based on 1 part by mass of the photopolymerization initiator (F). ~ 5 parts by mass. The color hardening composition of the present invention may further contain a solvent (H). Solvent (H) such as ether 30 201006884 class, ^ aroma hydrocarbons, _, alcohols, _: 1 _ member, tetrahydrogen, tetrahydropyranamine mouth diethylene glycol monobutyl ether monomethyl ether, Ethylene glycol monoethyl ether, ethylene two systems, si - 1 > 兀, ethylene glycol monomethyl sulphate, diethylene glycol mono acesulfame, . , ethylene glycol monobutyl ether, diethylene glycol diethylene glycol diethylene glycol, diethylene glycol di-propyl ether -, = Ding shout, diethylene glycol dimethyl ether, decyl ether acetic acid g, propylene glycol single B Rainbow-Dibutyl Ether, Propylene Glycol Single Sacrificial Acetate, Ethyl sulphate Acetate Monopropyl Ether Acetate, Mercaptoacetic Acid M Alcohol (IV) B _ _ _ carbitol Ethyl, butyl Kaki acetic acid vinegar, benzoic acid, phenylethyl _, f yl group, methoxy pentene ❹ 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族Ketones; Ben and Stupid 4-ketones, 4-MtL ketone 2-heptanone, 3-heptanone, 4-heptane=_pentane (tetra)fluorenone, cyclohexanone and 4-alkyl-4-methyl- 2 ^ For example, f alcohol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethyl alcohol, diacetone alcohol, and glycerin.酸酸异丁§, _ alone, butyric acid isopropyl vinegar, butyric acid Γ Γ s s, lactic acid methyl vinegar, lactic acid ethyl acetate, methyl methacrylate, butyl hydroxyacetate, methyl decyl oxyacetate , methoxyethyl oxime oxonate acetic acid butyl g, ethoxy acetoxy hydrazine ethoxylate, ethoxyacetic acid ethyl vinegar, 3 j propyl propionate methyl ester, 3- propyl propyl acetonate, 3-methoxy Methyl propyl propyl acrylate, ethyl methoxyacetate, ethyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl acetoacetate, 2-propionic acid Ethyl ester, 2-propyl propyl propionate, decyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionic acid propyl vinegar, 2-ethoxypropionic acid曱0曰, 2-ethoxyethyl propionate, 2-oxo-2-methylpropanoate, 2-oxo-2-ethylpropionate, 2_methoxy_2_ Methyl methacrylate, ethyl 2-ethoxymethylpropionate, decyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetonate, ethyl acetate, vinegar, 2- Oxygenated butyric acid methyl vinegar, 2-oxobutyric acid ethyl vinegar, 3-methoxybutyl acetate vinegar, 3-methyl-3-methoxybutyl acetate and γ- Lactone. 31 201006884 The aforementioned guanamines are, for example, N,N-di-f-carbamamine and N,N-didecylacetamide. Other solvents (H)' such as N-methylpyrrolidone and dimethyl hydrazine. f The solvent (H) may be used alone or in combination of two or more. The solvent (H) ' is preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, lactic acid ethyl acetate or dipropylene alcohol. The content of the granules (H) is preferably from 70 to 90% by mass, more preferably from 75 to 88% by mass, based on the mass fraction of the coloring curable composition. Further, the color hardening composition of the present invention may contain the surfactant 1. The surfactant (I)' is, for example, an anthrone-based surfactant, a fluorine-based surfactant, and a dreamone-based surfactant having a fluorine atom. The above-mentioned alkaloid surfactant is, for example, a surfactant having a zephyroxygen bond. Specifically, the trade name is Toray SiliconeDC3PA, the same SH7PA, the same DC11PA, the same SH21PA, the same SH28PA, the same 29SHPA, the same SH30PA, the polyether modified eucalyptus SH8400 (manufactured by TORAY SILICONE), KP32, KP322, KP323, KP324, KP326 KP340, KP341 (manufactured by Shin-Etsuketone), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (GE Toshiba Ketone). The fluorine-based surfactant is, for example, a surfactant having a fluorocarbon chain. Specifically, the trade name is FLUORADFC430, the same as FC431 (Sumitomo 3M (share) system), MEGAFACF142D, the same F171, the same F172, the same F173, the same F177, the same F183, the same F470, the same F475, the same R30 (大曰本墨化学Industrial (stock) system, EFTOPEF301, EF303, EF351, EF352 (new Akita Chemicals Co., Ltd.), SURFLONS381, S382, SC101, SC105 (Asahi Glass Co., Ltd.), E5844 (Daikin Fine Chemical) (share) research institute), BM-1000, BM-1100 (manufactured by BM Chemie Co., Ltd.). The above-mentioned fluorenone-based surfactant having a fluorine atom is, for example, a surfactant having a siloxane chain and a fluorocarbon chain. Specifically, the trade name is MEGAFAC R08, the same BL20, the same F4?5, the same F477, and the same F443 (manufactured by Otsuka Ink Chemical Industry Co., Ltd.). 201006884, and other surfactants may be used singly or in combination of two or more. The colored hardening composition of the present invention may contain a molecular weight of ~5~343631: Kang-stupid: A (2) Kang ^ 4' grass: horse macaic acid and thiopropyl propylene (4), which may further contain a filler, The binder resin (c) is a filler such as fine particles such as glass and alumina. The polymer compound other than the above-mentioned binder resin (C) is, for example, polyvinyl olefinic acid, polyethylene glycol monoalkyl ether or polyfluoroalkyl acrylate. The aforementioned adhesion promoter, such as vinyl trimethoxy decane, vinyl triethyl decane, vinyl ginseng (2-methoxyethoxy) oxalate, N-(2-aminoethyl)-3 :amine, propylmethyltrimethoxyxanthene L (2-aminoerythridyl)-3-aminopropyldimethoxydecane, 3-aminopropyltriethoxydecane, 3-epoxypropoxylate Propyldimethoxycarbazide, 3-glycidoxymethyldimethoxycarbazide, 2-(3,4-epoxycyclohexyl)ethyldimethoxyoxime, 3-chloro Propylmethyldimethoxycarbazide, 3-chloropropyltrimethoxyoxydecane, 3-methylpropenyloxypropyltrimethoxyindol, and 3-mercaptopropyltrimethoxydecane.前述 The aforementioned antioxidants, for example: 4,4'-sulfur mono-bis(6-t-butyl-3-methylbenzene), triethylene glycol-double [3-(3-t-butyl-5-) Methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-mono-μ-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], pentaerythritol [肆-[3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) Propionate, 1,3,5-trimethyl- 2,4,6-parade (3,5-di-t-butyl- 4-hydroxybenzyl) benzene, 2,6-di-second butyl 4- 4-Methylbenzene, 2,6-di-t-butyl-4-ethylbenzene, 2,2'-methylenebis(4-methyl-6-t-butylphenylene), 4,4,-sulfur-bis(3-methyl-6-t-butylphenol), 4,4'-butylidene-double (3-methyl-6-third 33 201006884 butyl benzene), 1,1,3 - ginseng (2-methyl-4, 4-hydroxy-5-t-butadiene, 1; 3,5-para (4-)-based benzene and hydrazine [indolyl- 3_(( 3,5'-1, butyl- 4'- phenyl phenylpropionic acid g)] A burn, etc. a line absorber, for example, 2-(2-amino-3-3-t-butyl-5-phenyl)-5-gas benzotrisene, etc. benzotrizene; 2-hydroxy-4-octyloxy a diphenyl ketone such as diphenyl ketone; a benzoate such as W2 Tian 4^ dif-tributyl phenyl~3,5-di-t-butyl butyl- 4- benzoic acid ester; 2, r; (4, 6r diphenyl-u, 5-tris- 2 -yl)-5-hexyloxy, etc., such as agglomeration inhibitors, such as sodium polyacrylate, etc. ^The aforementioned organic amine compound, for example N-propylamine, isopropylamine, n-butylamine, isobutylamine, second butylamine, tert-butylamine, n-amylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-nonylamine, n-decylamine a monoalkylamine such as n-dodecylamine; a monocyclic ring: methyl ethylamine such as 2-nonylcyclohexylamine, 3-hexylamine or 4-methylcyclohexylamine, diethylamine, methyl-n-propylamine, a dialkylamine such as ethyl n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-second-butylamine, di-third-butylamine, di-n-pentylamine or di-n-hexylamine;单 monoalkylmonocycloalkylamines such as methylcyclohexylamine and ethylcyclohexylamine; dicyclohexylamine, etc. Dicycloalkylamines; dimercaptoethylamine, mercapto diethylamine, triethylamine, dimethyl-n-propylamine, diethyl-n-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, three-positive Trialkylamines such as propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-tert-butylamine, tri-tert-butylamine, tri-n-amine, tri-n-hexylamine; dimethylcyclohexylamine, two a dialkyl monocycloalkylamine such as ethylcyclohexylamine; a monoalkyl bicyclic product such as methyl dicyclohexylamine, ethyl dicyclohexylamine or tricyclohexylamine; a decylamine 2~amino group Ethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol Monobutanol 34 201006884 Amines; 4 - Alkyl mono-1 -cyclohexanol and other monocyclic alcohols; diethanolamine, di-n-propanolamine, diiso-lactamamine, di-n-butanolamine, di-n-pentane a dialkanolamine such as an alkanolamine or a di-n-hexanolamine; a dicycloalkanolamine such as a pro-isobutyl bis(4-cyclohexanol)amine; 'triethanolamine, tri-n-propanolamine, triisopropanol Amine, tri-n-butanolamine, tri-n-pentanolamine, tri-n-hexanol a trialkanolamine such as an amine; a tricyclic anthracylamine such as a tris(4-cyclohexanol)amine; e ❿ 3-amino-1,2-propanediol, 2-amino-ubutanediol , 4-amino-u-butylene glycol, 3-dimethyl alcohol, 3-polyethylamino-1,2-propanediol, 2-dimethylamino-u-propanediol, 2-diethylamine 1, 3-propanediol and other amine-based glycerols; burnt di-alcohol amine-U-cyclohexanediol, 4-amino-U-cyclohexanediol and other amine rings

1-aminoalkyl cyclomethoxide, 4-aminocyclopentanone f-alcohol and the like containing methanol; J 1 monoaminocyclohexane methanol, 4-aminocyclohexane methanol, 4-dimethylaminocyclopentane An amine group-containing ring-burning methanol such as phytosterol, 4-diethylaminocyclopentanol methanol, 4-dimethylaminocyclohexane-methanol, 4-ethylaminocyclohexanol; β-propylamine Acid, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisoacetic acid, 3-aminoisoacetic acid, 2-aminopentanoic acid, 5-aminopentanoic acid , 6-aminocaproic acid, 1-aminocyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid, and the like; aniline, o-methylaniline, m. Aniline, p-methylaniline, p-ethylaniline, n-propylamine, p-isopropylamine, p-n-butylaniline, p-tert-butylaniline, 1-naphthylamine, 2-naphthylamine, anthracene, Aromatic amines such as fluorene-dimethylaniline, hydrazine, hydrazine-diethylaniline, p-methyl fluorene, fluorenyl-diphenyl phenylamine; o-amino sterols, m-amino sterols Amines such as alcohol, p-dimethylamino sterol, p-diethylaminobenzyl alcohol Alcohols; o-amino phenyl age, m-aminophenyl hydrazine, p-amino phenyl expectation, p-dimethylamino benzene and 35 201006884 p-diethylaminophenol and other amino phenols; m-aminobenzoic acid, An aminobenzoic acid such as an aminobenzoic acid or a p-dimethylaminoanilinobenzoic acid; and the like. The above-mentioned hardener is a binder, for example, by heating to bond a resin (a compound obtained in the combination of Q, etc., the aforementioned compound 'for example, a multi-wei type and a multi-needle type, etc. - the aforementioned polycarboxylic acid, such as phthalic acid Capric acid, 3,4-dimethyl benzyl stearic acid, p-dicarboxylic acid, pyromellitic acid, trimellitic acid, ^ 4 5 carboxylic acid, 3, 3', 4, 4' one two Aromatic polycarboxylic acid such as phenyl ketone tetracarboxylic acid ^ · ', not © caffeic acid, glutaric acid, adipic acid, U, 3, 4 - butyl sulphate, maleic acid, itaconic acid, etc. Aliphatic polybasic acid; hexahydrophthalic acid, 3,4 dimethyl tetrahydrophthalic acid, montic acid, hexahydroterephthalic acid, U, 4 -cyclopentanyl three, acid , the four sisters of the ring sister, U, 4, 5-cyclohexanone, etc., and other alicyclic complexes, etc. One of the aforementioned ugly _, such as phthalic acid, pyromellitic acid, partial, trianhydride, 3,3,,4,4,-diphenyl ketone, four Wei, traitors, etc. (4) group of poly-acid-lowering liver; itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl galax, propylene triterpenoid 曱Acid liver, maleic acid Sf, 1, 2, 3, 4 - Ding Shao four Liver of the liver and other thieves; hexamethylene phthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 24 - cyclopentan-di-anhydride, 1,2,4-ring烧三纽轩, 环戊烧叫酸针, 环己细剑二轩, 海魏醛, the new acid alicyclic multi-doleic acid anhydride; alcohol bis-p-benzoic acid, glycerol ginseng A _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ , RIKASID HH and Yingyi 700 (both New Japan Physical and Chemical Co., Ltd.), etc. 36 201006884 The hardeners can be used alone or in combination of two or more. iff f-step heating, forming a pattern, so-called Photolithography: or ϊΐίίίΐ)=coating the ink device on a substrate or other resin layer, removing the germanium into a color layer' by heating or exposing at least its t _ 1Γ5& /!_ τγ* Tty 1 , "τ» Use this side of the color hardening composition of the lion into the color of the county of the pattern of the pattern = = this hair-shaped hard-casting city, (four) secret reduction of other resin layers such as the formation of the substrate Other colored hard female silk layers, etc.): The volatile component of #1 is removed to form a coloring layer, and the colored layer is exposed through a photomask: an inkjet method such as hardening to form a pattern, etc. The color filter contains _, and the color filter of the above-mentioned color can serve an ideal liquid crystal display device. Color extinction = color hardening domain of the present invention, which can form a color excellent in durability. EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples. Synthesis Example 1 <Synthesis of Dye (Α-2)> After 25 parts of water was added to 4 parts of 4 diamine f benzoic acid under cold, 7.6 parts of sodium nitrite was added to ice 5 and stirred for 30 minutes. Add a small amount of 3 = 22.8 parts of acid, make brown, Xuanzang, twist 9 ίη Gu Shao set I to add 35 / 0 salt after the skin 6Q color solution and stir for hours. The 6.9 parts of the guanamine sulfuric acid solution is used to recognize the reaction waste, and the 含有« contains the diazonium salt suspension.

HOOC <y NH2 (24) is represented by the formula (25): 1-(2-ethylhexyl)_3___氦美hydroxypyridine~~2-ketone 1〇5 ΡΛπλ Μ ® ^ 甲基methyl~6 — , Yu, Yongk, methyl, each bite _ 105 parts and 53 parts of water 'under ice, adjusted to pH 8~9 with 30% sodium hydroxide solution. 37 201006884

CN & The following operations were carried out under ice cooling. The aqueous solution of the pyridone was stirred to obtain a colorless liquid, and then adjusted to pH Η8 to 9 with a 30% aqueous sodium hydroxide solution, and it took 2 hours to pump a suspension containing a diazonium salt. After the end of the addition, stir for an additional 2 hours, = to a brown suspension. After filtration, the obtained yellow solid was dried under reduced pressure at EtOAc (yield: 73%).

The structure of the azo compound (10) was determined by N]V [R, I3c-NMR, and mass analysis. The NMR apparatus used was ECA-500 (manufactured by JASCO Corporation), and the mass spectrometer was Agilentl 100 HP LC/MSD (manufactured by Agilent Technology Co., Ltd.). : iH-NMR (500 MHz, δ 値 (ppm, TMS basis), DMSO); 13C-NMR (125 MHz, δ 値 (ppm, TMS basis), DMSO). Mass analysis: ' ❹ TIC=ESI+ > Fr=50V :[M+H] m/z=411 TIC=ESI- 'Fr=50V:[MH] m/z=409 The obtained azo compound (l〇) 〇.35g is dissolved in ethyl lactate to a volume of 25 〇 cm3, in which W is diluted with ethyl lactate to make the volume 1 〇 'degree: 0.028 g / L), and the absorption spectrum is measured using a spectrophotometer [quartz colorimetric suit and colorimetric length 丨. This compound showed an absorbance 丨97 (anything w position) at >umax = 431 nm. ~ 'Flat Synthesis Example 2 To a solution of 5.0 parts of 4-aminobenzoic acid represented by the formula (24), 25 parts of water was added, followed by cooling, and the mixture was adjusted to pH 7 to 8 with a 30% aqueous sodium hydroxide solution. The following operations were performed on icy ^ 38 201006884 φ. Add 7.6 parts of sodium nitrite and mix for 3 minutes. After less,, and after making a brown solution, _ 2 hours. The guanamine sulfur: rinsing. - Floating

The following operation is carried out under ice cooling, and the pre-lighted aqueous solution is made into a colorless solution, and adjusted to a positive 8 to 9 with a 30% aqueous sodium hydroxide solution, and the suspension containing heavy gas salt is added to the liquid salt! t·, 2 hours to pump drops plus. After the completion of the dropwise addition, the cake was further baked for 2 hours to obtain a brown suspension. The obtained yellow solid was dried under reduced pressure at 6G 〇C to give 12.5 parts (yield: 73%) of azo compound of formula (12).

HOOC -CVn=

The structure of the azo compound (12) is determined by mass analysis. Mass analysis device use

Agilent 1100 HP LC/MSD (manufactured by Agilent Technology). : Mass analysis: TIC=ESI+ ' Fr=50V:[M+H] m/z=469 TIC=ESI- ' Fr=50V:[MH] m/z=467 The azo compound (12) will be obtained. 35 g dissolved in ethyl lactate to make a volume of 39 201006884 250 cm 3 'Diluted 2 cm 3 of the lactic acid to make the volume 1 〇〇 cm 3 (concentration: 0.028 g / L) 'Using a spectrophotometer [quartz cuvette _ The length of the colorimetric phoenix is 丨 (4) The absorption spectrum is measured. The compound showed an absorbance of 1.89 (arbitrary units) at Ajnax = 431 nm. Synthesis Example 3 <Synthesis of Resin (C-1)> In a 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen gas was passed at 0.02 L/min to form a nitrogen atmosphere, and 3_methoxy group was added.丨-butanol ❹ quality. A portion and a mass fraction of 3-methoxybutyl acetate were heated to 70 C while stirring. Next, 54 parts by mass of methacrylic acid, 3,4-epoxytricyclo[5.2.1.02 6]decyl acrylate (compound represented by formula (ci-1 1-1) and formula (C1-2) The compound shown is mixed at a molar ratio of 50:50.) 180 parts by weight and 67 parts by mass of N-cyclohexylmaleimine dissolved in 14 parts by mass of 3-methoxy-i-butanol to prepare a solution. The solution was added to the chestnut solution for 4 hours, and added dropwise to the flask which was kept in the flask. On the other hand, the polymerization initiator 2,2,-azobis (2,4-dimethyl methine, in a solution of 3-methoxybutylacetic acid vinegar 24 〇# parts, using another drop Pump flower » 4 small coffee was added to the burnt. The initial polymerization wire was added for 4 hours, 70 ° C ', and then cooled to room temperature to obtain a solid content of 32 6 mass %, acid value of 34.3 mg-KOH / g. The copolymer of the copolymer (resin c-1) has a weight average molecular weight Mw of 9 _ and a degree of dispersion of 丨 9. Η之树月曰 Synthesis Example 4 &lt;Synthesis of Resin (C-2)&gt;

In a 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen gas was passed at 0.02 L/min to form a nitrogen atmosphere, and a 3-methoxy-J was added. The parts and 3-methoxybutyl acetoacetate 1 part by mass were heated to 70 C while being disturbed. Next, '68 parts by mass of methyl acrylate, 3,4_epoxytridecyl acrylate (the compound represented by formula (C1~1-1)) and the formula-e compound are mixed at a molar ratio of 50:5G. .) 15G f parts and benzene to U solution in 3-foxy-1 -butanol 14 〇 parts by mass, prepared as a solution, the solution was added to the insulation using a drop pump for 4 hours. 7〇. Internal = surface, polymerization initiator 2, r-azobis(2,4-dimethylvaleronitrile) fQ g internal portion 40 201006884 methoxybutyl acetate 240 parts by mass, using another A drop of pumping costs 4 small. Add dropwise to the flask. After the completion of the dropwise addition of the solution of the polymerization initiator, the mixture was kept for 4 hours and 7 ° C, and then cooled to room temperature to obtain a solution of a copolymer (resin C to 2) having a solid content of 271 mass% and an acid value of 44 2 η. The weight of the obtained resin c-2 was 7000, and the degree of dispersion was L7. Synthesis Example 5 <Synthesis of Resin (C-3)> In a 1 L flask without a flow cooler, a dropping funnel, and a stirrer, a nitrogen gas atmosphere was added to a dilute dish/knife/cucumber Alcohol methyl ether 3 〇〇 mass ❹ 参 - 面 面 面 面 面 面 面 面 。 。 。 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其84 parts by mass == agent 2,2'-azobis(2,4-dimethylvaleronitrile) 37 parts by mass solution = 225 parts by mass, prepared as a solution, the solution is spent on the &gt; In the flask of the machine, after the completion of the dropwise addition, the solution was kept for 4 hours, 70/ ϊίΐΐϊ, and a solution of octapolymer (resin C-3) having a sputum content of 4% and an acid value of 39. heart-KOH/g was obtained. Resin A-3

Mwl070G, dispersion 2.74. Synthetic Example 6 in the Knife Knife <Synthesis of Resin (C-4)> With a reflux condenser, a dropping funnel, and a mixer, the nitrogen is distributed to make a nitrogen atmosphere, and 3-methoxyx is added. 0217 3-methoxybutyl acetic acid g 105 parts, - surface - ^ 勒, 〇〇 parts and, acid, a compound of the formula i- υ and a solution of the formula (C1 - shows), dissolved The liquid is added to the flask of the funnel, which is a mixture of the funnel and the squid. In another aspect, the polymerization is carried out by adding 2, 24, _== of the carboxylic acid to 30 parts of the methoxy-i- A solution of 9 parts of butanol and 135 parts of 3-acetate is used within 4 bases of other dropping funnels. After the addition of the solution of the polymerization initiator is completed, it is kept, small ^ &amp; burned at 201006884 - The mixture was cooled to room temperature to obtain a solution of a copolymer (resin C-4) having a weight average molecular weight of Mw 7.5×10 3 , a degree of dispersion of 2.5, a solid content of 33%, and an acid value of 34 mg—KOH/g. About the weight average molecular weight of the above-mentioned binder resin ( Mw) and the number average molecular weight (Μη) were measured by the following conditions using the GPC method. Apparatus; Κ2479 (manufactured by Shimadzu Corporation); column; SHIMAD ZU Shim- pack GPO80M column temperature; 40 ° C solvent; THF (tetrahydrofuran)

Flow rate; l.OmL/min detector; RI is the dispersion ratio (Mw/Mn) of the weight average molecular weight and the number average of the polystyrene conversion obtained in the above-mentioned polystyrene. (A-1) Dye: Compound represented by formula (5) (Neptun Yellow 075: manufactured by BASF Corporation) (A-2) Dyes: Compound (A-3) represented by formula (1) obtained in Synthesis Example 1. Dye: Compound pigment dispersion liquid of the formula (12) obtained in Synthesis Example 2: 14 parts of CI Pigment Green 58 parts and 3.4 parts of acrylic pigment dispersant and 82.6 parts of propylene glycol monoterpene ether acetate were mixed, and a bead mill was used. A pigment dispersion liquid (B-1) obtained by sufficiently dispersing a pigment (B-1) photopolymerizable compound: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.: ◎ a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylic acid) (B-2) light Polymeric compound: TO-2349 (manufactured by Shin-Nakamura Chemical Co., Ltd.): a mixture of pentaerythritol hexaacrylate vinegar and dipentaerythritol pentaacrylate, and a mixture of dipentaerythritol pentaacrylate succinic acid derivative, acid value 67.8 mg K 〇 H/g) (C-1) Adhesive resin: Resin (c-1) obtained in Synthesis Example 3 (solid content 32 6 mass ° / c 〇 (C - 2) binder resin: resin obtained in Synthesis Example 4 ( C-2) (solid component 27.1 mass' (C~3) binder resin: tree obtained in synthesis example 5 (C-3) (solid content: 〇.〇% by mass) * 42 201006884 (C-4) Adhesive resin: Resin (c_4) obtained in Synthesis Example 6 (solid content % by mass) '(F-1) light Polymerization initiator: 2-benzyl- 2-dimethylamino- 1 - (4 - cough phenyl) butyl-1-one-one (F-2) photopolymerization initiator: 2,4-double ( Trichloroindenyl)-6_piperidinyl-^5—three clocks, (G-1) photopolymerization start aid··4,4, bis(diethylamino)diphenyl ketone (Η-1) Solvent: propylene glycol monoterpene (H-2) solvent: 3-ethoxypropionate ethyl ester 。 (b) 1 surfactant: MEGAFACF475 (manufactured by Dainippon Ink Chemicals Co., Ltd.) Example 1 [Color hardening Preparation of the composition 1] (A-1) 40.6 parts by mass (B-1) 21.8 parts by mass (C-1) 83.4 parts by mass (converted solid content: 27.2 parts by mass) (F-1) 8.9 parts by mass (G-1) 1.5 parts by mass (Η-1) 334.8 parts by mass (H-2) 16.7 parts by mass (1-1) 0.004 parts by mass to obtain a colored curable composition 1. [Formation of coating film 1] Secondly, 'on glass (#1737; manufactured by Corning Co., Ltd.) was applied by spin coating to obtain the color hardening obtained above. After the composition 1 'to 100. (: 3 minutes to volatilize volatile components, to form a colored curable composition of the film after cooling, for which the colored curable composition film is irradiated with i-line [a wavelength of 365 nm] exposed. The light source of the i-line is illuminated by parallel light using an ultra-high pressure mercury lamp. The amount of illumination light was set to 500 mJ/cm2. Next, a color-curable composition film having a film thickness of 2 μm was obtained by baking at 22 TC for 20 minutes. • [Evaluation 1] Evaluation of solvent resistance 1 43 201006884 Using a color measuring machine (OSP-SP-200; 0LYMPUS metric coloring hardening composition film chromaticity. AJ policy Ml 疋 到 到 接着 , , , , , 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 = The chromaticity of the cured film, the color difference before and after the immersion is obtained, and the ship's *=炱18 colorization is less than 5', then the hue is almost unchanged, and the color filter has good characteristics, if it is more than 5, 10 The following is the case where the color is 10 or more, and it is confirmed that there is a problem as a color filter. ❹ [Evaluation 2] Evaluation of the solvent property 2, using the same measurement as described above The machine 'measured the chromaticity of the color-curable composition film obtained. Then, the film obtained by the color-hardening composition is immersed in methyl-2 for _〇 minutes, and the smear-hardening group of money after the sample The color of the film, the color difference before and after the isthmus, she ^ = 6.5. [Formation of coating film 2] The colored hardening composition 1 obtained above was applied by spin coating to a glass (#1737; manufactured by Corning Co., Ltd.) at 100. (: The volatile component was volatilized in 3 minutes to form a color hardening composition. After the film was cooled, the film of the colored curable composition was irradiated with one line [wavelength 365 nm] through a mask, and exposed. The light source of the i line was irradiated with parallel light using an ultrahigh pressure mercury lamp. The amount of the light was set to 5 〇〇mJ. /cm2. Photomask, used to form line masks of line color 3μιη, 4μιη, 5μιη, 6μιη, 7μιη, 8μιη, 9μιη, ΙΟμιη, 2〇μηη, 30μιη, 40μιη, 50μιη, and ΙΟΟμπι. The aqueous developing solution containing the nonionic surfactant 〇12% and potassium hydroxide 〇〇4% was immersed at 25 ° C for 60 seconds and developed, and then washed with pure water to obtain a patterned wired and spacer pattern glass substrate. /' [Evaluation 3] Evaluation of development residue The line obtained by the above operation and the line spectrum of the non-exposed portion of the glass substrate were measured using the same color measuring machine as described above. As a result, the wavelength was 55 〇 nm. The transmittance of the light is 99.98%. In terms of the evaluation criteria of the development residue, if the transmittance of light having a wavelength of 55 〇 nm is = 9 =0 / or more, it is considered that there is almost no development residue, and it is presented as a color filter. The characteristics of the light sheet, if the transmittance of light having a wavelength of 550 nm is less than 99.9%, is a problem as a color light-receiving sheet. Examples 2 to 6 The composition of the constituent components of the colored curable composition is changed to The colored curable compositions 2 to 6 were obtained in the same manner as in Example 1 except that the results were evaluated in the same manner as in Example 1 in the obtained color-curable compositions 2 to 6. Show. [Table 1] 着色 Colored hardening j Raw composition 1 40.6 A-2 40.6

C-1 Solid component only C-2 Solid component only 27.2 C~3 Solid component only C-4 Solid component only

Example 2 27.2 Example 3 Example 4 Example 5 Example 6 Coloring hardening coloring hardening coloring hardening composition 3 composition 4 composition 5 composition 6 4 — — 9.1 A 40.6 — _ 40.6 I—208.5 — 21.8 27.1 21.8 21.8 — I— 27.2 I — 27.2 — A 27.2 — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — 0.004 0.036 45 201006884 [Table 2] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Coloring hardening coloring hardening coloring hardening coloring coloring hardening coloring curable composition physical property composition physical property composition physical property composition physical composition ____ _ 2 3 4 5 6 Solvent resistance evaluation 1 1.8 1.5 0.5 0.1 0.9 ,— Solvent resistance evaluation 2 6.5 4.6 1.3 0.2 1.6 1.1 Development residue evaluation 99.98 100.00 99.99 100.00 99.99 99.98 &lt;Industry utilization|Health&gt; According to the present invention, it is possible to provide a coloring f group capable of forming a color filter excellent in solvent resistance. Adult. The color light-receiving sheet can be used for a display device such as a liquid crystal display panel, an electroluminescence panel, or a plasma display panel. [Simple description of the figure] Helmet [Description of main component symbols]

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Claims (1)

.201006884 VII. Patent application scope: 1. A color-hardening composition containing dye (A), polymerizable compound, binder resin (C), f-bonding resin (C)-based copolymer, containing derived carbon- A constituent unit of a carbon unsaturated double bond, a cyclic _ structure compound (co), and a constituent unit derived from at least one compound (C2) selected from the group consisting of unsaturated tickic acid and unsaturated carboxylic anhydride. 2. The colored hardening composition of claim 1, wherein the annular riding structure is an aliphatic polycyclic epoxy structure. ❹ 3. The color-hardening composition of claim 1 or 2, wherein the compound (c〇) having a carbon-carbon unsaturated double bond and a cyclic ether structure having a carbon number of 2 to 4 is selected from At least one compound of the group consisting of the compound represented by the formula (C1 - 1) and the compound represented by the formula (C1 - 2); [In the formula (Cl-1) and the formula (C1-2), R each independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom which may be substituted with a trans group; 毳 X is independent of each other and represents a single bond or a carbon number i to 6 of a hetero atom. The colored hardening composition according to any one of claims 1 to 3, wherein the dye (A) contains a dye having a retinal dye. The colored hardening composition according to any one of claims 1 to 4, wherein the polymerizable compound (B) is a monomer or oligomer having a carboxyl group. 6. The colored hardening composition according to any one of claims 1 to 5, which further comprises a pigment. The pattern is formed by photolithography or inkjet method using the color hardening composition of any one of claims 1 to 6. 8. 8. A color filter 'includes the pattern of claim 7 of the scope of the patent. 47 201006884 9. A liquid crystal display device having a color filter of the eighth application patent, Fig. 48