TW201113303A - Colored photosensitive resin compositions - Google Patents

Abstract

This invention discloses a colored photosensitive resin composition, containing a coloring agent (A), a binding resin (B), a photo polymeric compound (c), a photopolymerizing initiator (D), and a solvent (E). The coloring agent (A) is a coloring agent that contains dyes. The binding resin (B) is a binding resin that contains the resin obtained by means of the following method: reacting the resin obtained by adding monomers (Bb) having carboxyl group and polymeric double bonds to at least one (Ba) selected from the group consisting of bisphenol A type epoxy resin and bisphenol F type epoxy resin, with at least one (Bc) selected from the group consisting of succinic anhydride, maleic anhydride and tetrahydrophthalic anhydride, and further reacting with a multifunctional epoxy compound (Bd) having at least one selected from the group consisting of bisphenol A type epoxy resin and bisphenol F type epoxy resin.

Description

[Technical Field] The present invention relates to a colored photosensitive resin composition and a color filter using the colored photosensitive resin composition. [Prior Art] a The colored photosensitive resin composition is used for producing a color filter used in a display device such as a liquid crystal display panel, an electroluminescence panel, or an electrophoretic display panel. It is known that a pigment or a dye is used as a coloring agent in the colored photosensitive resin composition (Non-Patent Document 1). [Non-Patent Document 1] Suzuki's "Essence of Liquid Crystal Display Manufacturing Process", First Edition, Industrial Press, March 2005, p. 112 [Invention] The subject of the present invention is A colored photosensitive resin composition capable of forming a coating film, a pattern, and a color filter excellent in heat resistance is provided. The present invention provides the following [1] to [12]. 〇 [1] color-sensitive photosensitive resin composition containing a coloring agent (A), a musk tree (B), a photopolymerizable compound (c), a photopolymerization initiator (D), and a solvent 'E The colorant (A) is a dye-containing coloring agent, and the binder resin (b) contains a resin obtained by a resin obtained by selecting a bisphenol A type epoxy resin and a bisphenol. a resin obtained by adding a monomer having a (four) and a polymerizable double bond (4) to at least one of the groups of the F-type epoxy resin (Ba), and a resin selected from the group consisting of oleic acid and succinic acid At least one of the group consisting of liver and tetracarboxylic anhydride (Bc) is reacted, and further comprising at least one selected from the group consisting of bisphenol A type epoxy resin and bisphenol epoxy resin containing 15073I.doc 201113303 The polyfunctional epoxy compound (Bd) is reacted. [2] The colored photosensitive resin composition according to [1], wherein the dye contains a group selected from the group consisting of an azo compound, a metal complex having an azo compound as a ligand, and a dibenzopyran compound. At least one. [3] The colored photosensitive resin composition according to [1] or [2] above, wherein the dye contains a compound represented by the formula (1): [Chemical Formula 1]

[In the formula (1), R1 to R4 each independently represent a monovalent aromatic hydrocarbon group, the aromatic 3 atom, -R6, -OH, -〇R6, _s〇-C02R6'-so3r6 > -so2nh2 > R4 independently represents a hydrogen atom, _R6 or a carbon number of 6~1 fluorenyl. The hydrogen atom contained in the aromatic hydrocarbon group may be halogen-S03-, _s〇3H, so3m, H, -〇R6, -S 〇3_, -so3h, so3m, -co2h, -S〇2NH2, -so2nhr8 or -so2nr8r9 take -co2h, -co2r6, -so3r6, R5 denotes -S〇3·, -S〇3H, S〇3M, - S02NHR8 or -so2nr8r9 ; When m is an integer of 2 or more, the complex number m represents an integer of 〇~5; the R5 may be the same or different in the work; X represents a statin atom; a represents an integer of 0 or 1; .doc -4- 201113303 R represents a carbon number of 1 to ί, a valence saturated hydrocarbon group. The hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom, and the _CIi2_ contained in the saturated hydrocarbon group may be -Ο-, -CO- or -NR7-substituted; 7 R represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the -hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom, and -CH2- contained in the saturated hydrocarbon group may be . Replaced by -〇- or -CO- R8 and R9 each independently represent a linear or branched one-valent saturated aliphatic hydrocarbon group having a carbon number, a carbon number of 3 to 30 one-valent alicyclic hydrocarbon group or _Q, the saturated aliphatic aliphatic hydrocarbon group and the alicyclic ring The hydrogen atom contained in the hydrocarbon group may be substituted by _OH, a functional atom, -Q, -CH=CH2 or -CH=CHR6, and the saturated aliphatic hydrocarbon group and the _CH2_ contained in the alicyclic hydrocarbon group may be S_, _c〇_, -NH- or -NR6-substituted; r8 and r9 may be bonded to each other to form a nitrogen-containing heterocyclic ring of a 3 to 1 member ring, and the hydrogen atom contained in the hetero ring may pass through R6 , _〇h or -Q is substituted; Q represents a carbon number of 6 to 10 one-valent aromatic hydrocarbon group or a carbon number of 3 to 1 fluorene monovalent heterocyclic group, and a hydrogen atom contained in the hydrocarbon group and the heterocyclic group It can be substituted by a halogen atom via _0H, R6, -OR6, _N〇2, -CH=CH2, _ch=chr^; Μ represents a sodium atom or a potassium atom; wherein, the compound of the formula (1) has a charge number and _ The number of charges is the same]. [4] The colored photosensitive resin composition according to the above (1) to (b), wherein the binder resin contains a binder resin of a resin obtained by the following method: ρ, a main group (Bb) having a carboxyl group and a polymerizable double bond 150731.doc 201113303, is added to at least one of the group consisting of ρρ, main 虱 虱 曰 and bisphenol F-type epoxy resin The obtained resin is reacted with at least one selected from the group consisting of succinic anhydride, maleic anhydride, and tetraphthalic anhydride (Bc), and then contains an epoxy resin selected from the group consisting of bisphenol A and The polyfunctional epoxy compound (Bd) of at least one of the group consisting of bisphenol F type epoxy resins is reacted, and the obtained resin is further contained and selected from the group consisting of succinic anhydride, maleic anhydride, and tetrahydroortylene The compound (Be) of at least one of the groups consisting of dicarboxylic anhydride is reacted. [5] The colored photosensitive resin composition according to any one of the above [1] to [4] wherein the monomer (Bb) having a carboxyl group and a polymerizable double bond is selected from the group consisting of acrylic acid and methacrylic acid. At least one of them. [6] The colored photosensitive resin composition according to any one of the above (1) to (5), which is viscous. The total amount of the resin (8) and the photopolymerizable compound (C) is 20% by mass or more and 8% by mass or less. [7] The colored photosensitive resin composition according to any one of the above [1] to (4) wherein the solid content of the dye 3 in the dyed photosensitive resin composition is 5% by mass or more and 6% by mass. the following. [01] The colored photosensitive resin composition according to the above [1] to [7], wherein the coloring agent (A) is a coloring agent containing a pigment. [01] The colored photosensitive resin composition according to the above [8], wherein the pigment contains a color selected from the group consisting of CI Pigment Blue 15:6, c Iη τ , " Yan Yanhong 254 ' c.l_Pigment Red 242, CI Pigment Red 177 At least one of the group consisting of CI phase Yanke green 58, CI pigment yellow 15 〇 and ci pigment yellow 138. [10] A coating film, i is etched, and is formed by using the colored photosensitive resin composition according to any one of the above [1] to [9]. 150731.doc 201113303 [11] A pattern formed by using the colored photosensitive resin composition according to any one of the above π] to [9]. [12] The pattern of [U] above is formed by photolithography. [13] A % color filter comprising at least one selected from the group consisting of the coating film of the above [1〇] and the pattern of [11] and [12]. [Embodiment] The colored photosensitive resin composition of the present invention contains a coloring agent (A). Ο

The coloring agent (A) used in the colored curable resin composition of the present invention is a dye-containing coloring agent. The dye contained in the coloring agent (A) is not particularly limited, and a well-known dye can be used. For example, oil-soluble: dyes, acid dyes, amine salts of acid dyes or acid dyes can be used as the above-mentioned dyes, for example, in "The ocnety of Dyers and Colourists" (The ocnety of Dyers and Colourists The compound which is classified as a dye in the publication, or a well-known dye described in "Staining Notes" (color dyeing company): Specific examples thereof include CI Solvent Yellow 4 (hereinafter, "Γ ' ^ Solvent Yellow is omitted, and only the number is described) , 14, 15, 23, 24, 38, 〇'" 62, 63, 68, 82, 94, 98, 99, 162; CI solvent red 45, 49, 125, 130; CI solvent orange 2, 7, 11, 15, 26, 56; CI solvent blue 35, 37, 59, 67; CI solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 and so on. Also, 'as CI acid dye' can be enumerated: c. I. Acid dragon, steam, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, μ 42 , 54 , 65 , 150731.doc 201113303 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, 251; CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50 , 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143 '145, 150, 151, 158, 176 , 182 , 183 , 198 , 206 ' 211 , 215 , 216 , 217 , 227 , 228 , 249 ' 252 , 257 , 258 , 260 ' 261 , 266 , 268 ' 270 ' 274 , 277 , 280 ' 281 , 1 95, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426; CI·acid dial 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; CI Acid Blue 1, 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 , 171 , 182 , 192 , 210 ' 242 , 243 , 256 , 259 ' 267 , 278 , 280 , 285 , 290 , 296 , 315 , 324 : 1 , 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. In addition, as CI direct dye 150731.doc 201113303 materials, can be cited as: CI direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 1〇8, 1〇9, 129, 136, 138, 141; CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105 , 106 , 1〇7 , 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, 41, 46, 50, 52, 56, 57, 61, 64, 〇65, 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, 171, 172, 173, 188, 189, 190, 192, 193, 194, 196 '198 '199 ' 200 ' 207 ' 209 ' 210 ' 21 2 ' 213 ' 214 ' 222, 228, 229 ' 237, 238, 242, 243, 244 ' 245 ' 247, 〇 248 ' 250 , 251 ' 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; m CI Direct Green 25, 27 , 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and other dyes. Further, as the CI mord dye, CI mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; 150731.doc -9 - 201113303 cl mordant red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39 , 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88 ' 90 ' 94 ' 95 ; CI mordant orange 3, 4, 5, 8, 12, 13, 14 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42 , 43 , 47 , 48 ; CI mordant blue 1, 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, 31, 32, 37, 4, 41, 44, 45, 47, 48, 53 '58; CI · mordant green 1, Dyes such as 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, and 53. In addition, examples of the dye contained in the coloring agent (A) include an amine salt of an acid dye represented by the following formulas (i) to (vii) and a sulphur of an acid dye represented by the formulas (viii) and (ix). Amidoxime derivative. D-(S03)v(CwH2w+1N+H3)v (i) D-(S〇3')v{(CwH2w+1)2N+H2}v (ϋ) D-(S03-)v{(CwH2w +1)3N+H}v (iii) D-(S03-)v{(CwH2w+1)4N+}v (iv) D-(S03')v(CeH2e+ , OCfH2fN+H3) (v) D-( S03-)v{(CwH2w+1)(PhCH2)2N+H}v (vi) D-(S03_)v{(CwH2w+1)Py+}v (vii) D-[{S02NH(CwH2w+ ,)}p ][(S03L)q] (viii) D-[{S02NH(CeH2e+ 10CfH2f)}p][(S03L)q] (ix) 150731.doc -10- 201113303 [Formula (i)~(ix), D Represents the base from the pigment. v represents an integer of 1 or more and 20 or less, and w represents an integer of i or more and 2 〇 or less. e and f each independently represent an integer of 1 or more and 丨〇 below.

Ph represents a phenyl group, and Py represents a group represented by the formula (1) in which a nitrogen atom is bonded to CwH2w+i. [Chemical 2]

(In the formula (I), Ra represents a methyl group. ma represents 〇 or an integer of 1). p represents an integer of 1 or more and 8 or less. q represents an integer of 0 or more and 8 or less. L represents a hydrogen atom or a monovalent cation]. Specific examples of D in the formulae (i) to (ix) include those derived from an azo dye, an enamel dye, a triphenyl decane dye, a dibenzopyran dye, and a phthalocyanine dye. m is preferably an integer of 1 or more and 1 Torr or less, more preferably an integer of the above or more than 8 or less. η is preferably an integer of 1 or more and 1 Å or less, and more preferably an integer of 1 or more and 8 or less. e and f are each independently an integer of 1 or more and 8 or less, and more preferably an integer of 1 or more and 6 or less. 150731.doc -11 - 201113303

Py is preferably a group represented by the formula (1-1). [Chemical 3]

P preferably represents an integer of 1 or more and 6 or less, and more preferably represents an integer of 1 or more and 5 or less. q is preferably an integer representing 〇 or more, and more preferably an integer of 0 or more and 5 or less. Examples of the L-valent cation include lithium ion, sodium ion, potassium ion, and a quaternary ammonium ion such as (C2H5)3HN+. Preferred examples thereof include sodium ion. Examples of the azo dye include dyes represented by the following formulas (a) to (d). [Chemical 4]

150731.doc -12- 201113303 ο rz-hno2s

(C) SOjNH-R2

O

HO

In the formula (a), R represents an alkyl group having 2 to 20 carbon atoms, a cyclohexylalkyl group having 2 to 12 carbon atoms in the alkyl chain, an alkylcyclohexyl group having 1 to 4 carbon atoms in the alkyl chain, An alkyl group having 2 to 12 carbon atoms substituted with an alkoxy group having 2 to 12 carbon atoms, an alkylcarboxyalkyl group represented by the formula (a-fluorene), and an alkoxycarbonylalkyl group represented by the formula (a-2) a base, a phenyl group substituted with a decyl group having 1 to 20 carbon atoms or a carbon group having a carbon number of 20 replaced by a phenyl group. o (a-1) (a-2) represents an alkyl group having a carbon number of 2 to 12, l^co-o-l2, L3-0-C0-L4. L2 represents a carbon number of 2 to 12 [formula (a-) 1), an alkyl group. (Expressing an alkyl group having a carbon number of 2 to 12; L4 represents an alkyl group in the formula (a-2) having a carbon number of 2 to 12.] In the formula (a), p Ζ 2 η Z5 ± p 〜 R represents a ruthenium atom, carbon An alkyl group, a carboxyl group or a halogen atom having a number of 1 to 4. 150731.doc • 13· 201113303 Examples of the alkyl group having 2 to 20 carbon atoms include ethyl group, n-propyl group, isopropyl group, n-hexyl group and fluorene group. Base, n-decyl, n-dodecyl, 2-ethylhexyl, 1,3-dimethylbutyl, 1-methylbutyl, iota, 5-didecylhexyl and 1,1,3, 3-tetramethylbutyl group, etc. Examples of the cyclohexyl group having 2 to 12 carbon atoms as a base bond include cyclohexylethyl group, 3-cyclohexylpropyl group, and 8-cyclohexyloctyl group. The alkyl group of the alkyl group having a hindrance bond of 1 to 4 may be, for example, 2-ethylcyclohexyl group, 2-propylcyclohexyl group, 2-(n-butyl)cyclohexyl group or the like. The alkyl group having a carbon number of 2 to 12 substituted by an alkoxy group of 12 may, for example, be 3-ethoxypropyl, propoxypropyl, 4-propoxy-n-butyl, 3-nonyl-n-hexyloxy And 3-(2-ethylhexyloxy)propyl group, etc. As a phenyl group substituted by the alkyl group of 1-20 of carbon, it is mentioned. Isopropylphenyl group, etc. Examples of the alkyl group having 1 to 2 carbon atoms substituted by a phenyl group include DL-1 phenylethyl group, a benzyl group, a 3-phenyl-n-butyl group, and the like. Examples of the alkyl group having 2 to 12 carbon atoms of L3 include ethyl group, propyl group, n-hexyl group, n-decyl group, n-decyl group, n-dodecyl group, 2-ethylhexyl group, and 1,3-dimethyl group. Butyl, decyl butyl, 15-dimethylhexyl, 1,1,3,3-tetramethylbutyl, etc. As the alkyl groups of L and L having a carbon number of 2 to 12, for example, Ethyl, hexyldiyl, etc. As Rz2 to Rd in the formula (a), a hydrogen atom, a mercapto group, an ethyl group, a n-propyl group, a n-butyl group, an isopropyl group, a second butyl group, and a third group are exemplified. Butyl, carboxyl, fluorine, gas, bromine and iodine atoms, etc., preferably listed in 150731.doc -14- 201113303: hydrogen atom, methyl, ethyl, n-propyl, n-butyl, iso The propyl group, the second butyl group, the third butyl group, the fluorine atom or the gas atom. Among the dyes represented by the formula (a), specific examples of the dyes include compounds of the formula (e). ]

As the dye having a group derived from an anthraquinone dye, for example, a compound represented by the formula (7) can be given. As the dye having a group derived from a triphenylmethane dye, a compound represented by the formula (g) is exemplified. As the dye having a group derived from a dibenzopyran dye, for example, J 1 1J is a compound represented by the formula (h). Further, examples of the dye having a group derived from a phthalocyanine dye include a compound represented by the formula (j). [化6] 〇

(f)

〇CH3 150731.doc -15* 201113303

As the dye, a dye containing at least one selected from the group consisting of an azo compound, a metal complex having an azo compound as a ligand, and a dibenzopyran compound is preferred. A dye containing at least one selected from the group consisting of compounds represented by the following formulas (1) to (7). The dye is preferably a dye which can be dissolved in the following solvents used in the coloring photosensitive resin composition of the present invention. As the dye, it is preferred to contain a dye of the compound of the following formula (1): a dye of the compound of the present invention. 150731.doc • 16 - 201113303

Ra (1) [In the formula, r1 to r4 each independently represent a hydrogen atom, _R6 or a carbon number of 6 to 1 Å; a monovalent aromatic hydrocarbon group, and a hydrogen atom contained in the aromatic hydrocarbon group may pass through a halogen atom, -R6 , -OH, -OR6, _S〇3-, _s〇3h, s〇3M, _c〇2H, _C〇2R6, -S〇3R6, _S〇2NH2, -S02NHR8 or -S02NR8R9 take o. R Table - S〇3., -SC^H, so3m, -co2h, -co2r6, ·8〇3ΐ16, -S02NHR8 or -S〇2NR8R9. Indicates the number of 0 5 . When the melon is an integer of 2 or more, the plural R<5> may be the same or different. x represents a halogen atom, a represents an integer of 〇 or 1. QR represents a one-valent saturated hydrocarbon group having a carbon number of 1 to 10, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted by an atom of an atom. The _CH2_ contained in the saturated hydrocarbon group may be substituted by -0, _CO- or -NR7-. ' &amp; R represents a monovalent saturated hydrocarbon group having a carbon number of 1 to ί, and a hydrogen atom contained in the saturated hydrocarbon group It can be substituted by a dentate atom, and the _0112_ contained in the saturated hydrocarbon group can be substituted by 〇· or -co-, and R9 independently represents a linear or branched one of the carbon number 10 Family smoke base, carbon number 3~3〇 a monovalent alicyclic hydrocarbon group or a gas atom contained in the saturated aliphatic ketone group and the alicyclic hydrocarbon group may be passed through 〇h, a functional element 150731.doc •17·201113303 atom, -Q, -CH=CH2 Or -CH=rHR 6 says that the HR substitution, the saturated aliphatic hydrocarbon group and the τ of the alicyclic hydrocarbon group, _LH2_ may be via -〇-, -s-, -CO-,

-NH- or -NR6- substituted. j A 卜 " R" is a heterocyclic ring containing a nitrogen atom bonded to each other to form a 3 to 10 member ring.

The farmer's corpse scared 3 of the 11 atoms and could be replaced by R6, -OH or -Q. Q represents a carbon number of 6 to Π)-valent aromatic hydrocarbon group or carbon number (tetra) one-valent heterocyclic group 'The hydrogen atom contained in the aromatic hydrocarbon group and the heterocyclic group may pass through -OH, R6, -OR, _N 〇2, _CH=CH2, _Ch=chr6 or dentate atom substitution. Μ represents a sodium atom or a potassium atom. Among them, the compound represented by the formula (1) has the same number of + charges as the number of _ charges. In the compound represented by the formula (1), R1 to R4 each independently represent a hydrogen atom, _R| or a carbon number of 6 to 10 monovalent aromatic hydrocarbon group. The above R6 represents a one-valent saturated hydrocarbon group having a carbon number hiO. The hydrogen atom contained in the saturated hydrocarbon group may be substituted by a functional atom, and _CH2• may be represented by _〇_, _c〇_ or -NR7- (R7 represents a saturated hydrocarbon group of carbon number ～~〇, which is contained in the saturated hydrocarbon group. The hydrogen atom may be substituted by a halogen atom, and the CH2_ may be substituted by _〇 or _c〇_. Examples of -R6 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, a neopentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, and a heptyl group. ,cycloheptyl, octyl, 2-ethylhexyl, cyclooctyl, decyl, decyl, bicyclodecyl, methoxypropyl, ethoxypropyl, hexyloxypropyl, 2-B Hexyloxypropyl, methoxyhexyl, ethoxypropyl and the like. The one-valent aromatic hydrocarbon group having 6 to 1 carbon atoms of R1 to R4 and Q may be, for example, a phenyl group or a naphthyl group, for example, 150731.doc -18-201113303. Further, the hydrogen atom contained in the one-valent aromatic hydrocarbon group having 6 to 1 carbon atoms of R to R 4 may be a halogen atom, _r6, _0H, _〇r6, _s〇3·, _s〇3H, S03M, -C. 〇2h, -c〇2r6, -S03R6, _s〇2nh2, -so2nhr8 - or -so2NR8R9 are substituted. - R above means the same meaning as described above. The above R and R are independently a linear or branched monovalent saturated aliphatic hydrocarbon group having a carbon number of 1 to ίο, a carbon number of 3 to 30, a monovalent alicyclic hydrocarbon group or _Q (Q represents a 〇 carbon number of 6~) a valence aromatic hydrocarbon group or a carbon number of 3 to 10 one-valent heterocyclic group, wherein the hydrogen atom contained in the group may be via 〇H, _r6, _〇r6, _CH=CH2, -CH=CHR6 Or a halogen atom is substituted). The linear or branched one-valent saturated aliphatic hydrocarbon group having a carbon number of 1 to 1 Å of R and R and the hydrogen atom contained in the one-valent alicyclic hydrocarbon group having a carbon number of 3 to 30 may be passed through _H, The prime atom, -Q, _CH=CH2 or -CH=CHR6 is substituted, and _Ch2_ may be substituted by -0, -S-, -CO-, _NH_ or _NR6_. 〇/, R may be bonded to each other to form a heterocyclic ring of 3 to 1 member ring. In this case, the hydrogen atom contained in the heterocyclic ring may be substituted by _R6, _〇H or . Further, the above Μ represents a sodium atom or a potassium atom. Examples of the dentate atom of the gas atom contained in the one-valent aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted for R1 to R4 include a fluorine atom, a gas atom and a specific one. 'As -OR6, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy 'second butoxy, tert-butoxy, n-pentyl, hexyl Oxyl, heptyloxy, octyloxy, 2-ethylhexyloxy, oxime 150731.doc -19 201113303 base, decyloxy and the like. Examples of -C〇2R6 include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, a pentyloxycarbonyl group, and an isopenic group. Oxycarbonyl, neopentyloxycarbonyl, cyclopentyloxycarbyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, heptyloxycarbonyl, cycloheptyloxy, octyloxy, 2-ethyl Oxyl group, cyclooctyloxy decyloxy group, decyloxy group, tricyclodecyloxy group, methoxypropoxycarbonyl group, ethoxypropoxy group, hexyloxy A propyloxycarbonyl group, a 2-ethylhexyloxypropoxycarbonyl group, a methoxyhexyloxycarbonyl group or the like. As the HG ring formed by the bonding of ...r9 in -S02NR8R9

Further, the above heterocyclic ring system utilizes the 0# subbond in the above figure. ° The binding bond and sulfur originally carried as a carbon number of 3 to 10 one-valent heterocyclic group of Q, can be cited as: 15073 丨.d〇c -20- 201113303

Further, the bonding key of the 'Q% miscellaneous base' can be set to any position. Examples of the -S〇3R6' include a methoxy lysyl group, an ethoxy sulphate base, a hexyloxy sulfenyl group, and a decyloxy group. 〇 as _S〇2NHR8, can be exemplified by: N·methylamine phase group, N-ethylamine yellow wine base, N-propyl amine base, N. isopropylamine base, ν·丁Alkaloid yellow base, Ν-isobutylamine oxime, N-pentylamine ketone, ν·isodecylamine hydrazino, Ν·nepentylamine gamma, Ν·(tetra)ylamine Phase group, η-aminosulfonyl, fluorene-cyclohexylamine sulfonyl, heptylamine sulfonyl, cycloheptylamine sulfonyl, fluorenyl-octylamine sulfonyl, Ν_(2_B Aminosulfonyl, N-(l,5-didecylhexyl)amine sulfonyl, fluorene-cyclooctylamine sulfonyl, fluorenyl-hydrazinylsulfonyl, fluorenyl-decylamine sulfonate Indenyl, fluorene-tricyclodecylamine sulfonyl, fluorenyl-methoxypropylamine sulfonyl, hydrazine-ethoxypropyl sulfonyl sulfonyl, hydrazine-propoxypropylamine sulfonyl sulfhydryl -Isopropoxypropylamine sulfonyl, Ν-hexyloxypropylamine hydrazino, Ν-(2-ethylhexyloxypropyl)amine, Ν-(曱, oxyhexyl Amine thiol, Ν-(3-phenyl-1-methylpropyl)amine hydrazino and the like. Further, examples of -SC^NHR8 include a group represented by the following formula. [Chemical 8] ΛΛ ‘γ^. 2 150731.doc •21 - 201113303 [Chemistry 9]

——NHS〇2 ^Jx^NHS〇2

SvX1V/nhso2 )&lt;!^2 NHSO,

Xy NHS〇2 [化10]

[Hist] ll] HO HO* nhso2 hct , ΝΗί , nhso2

HO ^^v^NHSOz HO^^Y^NHSOa

OH

Ms〇2 , OH HO, ^S^〇Vs^V'nhso2 X1 nhs〇2 X1 *^S^vNHS〇2

NHSO,

CF3CH2NHS〇2 CF3(CF2)7CH2NHs〇2 CI 150731.doc • 22- 201113303 In the above formula, X1 represents a halogen atom. The halogen atom of X1 may, for example, be a fluorine atom, a chlorine atom or a bromine atom. [化 12]

Me0-NHS02 ^〇ν-^*ΝΗ502 NHS〇2

〇, NHS〇2

Nhso2 〇 [Chem. 13]

HO .NHi〇2

^\^nhso2 [化14]

150731.doc -23- 201113303 [Chem. 15]

In the above formula, X3 represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and a hydrogen atom of the alkyl group and the alkoxy group may be substituted with an ifi atom. The alkyl group having 1 to 3 carbon atoms which may be substituted by a halogen atom may, for example, be an alkyl group, an ethyl group, a propyl group, an isopropyl group or a perfluoromethyl group. Examples of the alkoxy group having 1 to 3 carbon atoms which may be substituted by a halogen atom include a methoxy group, an ethoxy group, a propoxy group and the like. [Chemistry 16]

150731.doc 24· 201113303

[Chem. 17]

Ν

XT, Ο [化 18] j ^-vn^v.NHS〇2 八晒2 CXT (y^° ,xy nhso2 NHS〇2

Nhso2

Ct

Nhso2 Ο [Chem. 19]

150731.doc -25- 201113303

NH |〇2

At the top of the eight, λ&quot; means the same meaning as above. In the above formula, X2 represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having a carbon number of 1-3, a halogen atom or a nitro group, and the alkyl group and the hydrogen atom halogen atom contained in the alkoxy group are substituted. , σ ^ sub-character atom of Χ 2, can be cited as: fluorine atom, gas atom and (iv) as a carbon atom can be substituted by the atomic number 〜~3 base, ethyl, propyl, isopropyl, Sandon methyl Wait.作为] 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 [Chem. 21]

NHS

J50731.doc -26 - 201113303

Wherein 'as -S02NHR8, preferably R8 is a carbon number Q saturated aliphatic hydrocarbon group, a carbon number 5 to 7 alicyclic hydrocarbon group, an allyl group, a phenyl group, an aralkyl group having a carbon number of 8 to 10, and a carbon number 2 to 8 of a saturated aliphatic hydrocarbon group having a hydroxyl group and an aryl group or a saturated aliphatic aryl group having a carbon number of 2 to 8 and having a methoxy group, particularly preferably an ethylhexyl group. "Or as -S〇2NW, for example [Chem. 22], the base shown in Equation 4.

150731.doc -27- 201113303 1 1 S02 s°2 ,.八/^〇 Eight production, [Chemistry 24]

In the above formula, X2 represents the same meaning as described above. 150731.doc -28- 201113303 [Chem. 26]

\ 〇 as R8 and Μ contained in _S〇2NRR9, preferably carbon number... (4) saturated aliphatic nicotine, alicyclic nicotine with a carbon number of 5 to 7, propyl radical, carbon number 8~ 1 〇 芳 烧 烧 烧 烧 烧 烧 烧 烧 烧 烧 烧 烧 烧 烧 烧 烧 烧 烧 烧 烧 烧 烧 烧 烧 烧 烧 烧 烧 烧 烧 烧 烧 烧 烧2-ethylhexyl. The group of the aromatic hydrocarbon group having 6 to 1 carbon atoms of R to r4 in the formula (1) is preferably an ethyl group, a propyl group, a phenyl group, a dimethylphenyl group, _s〇 or -SO2NHR8. Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms having a substituent include a phenyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a hexyl decyl group, a fluorophenyl group, and the like. Chlorophenyl, bromophenyl, phenyl, methyl J5073l.doc •29- 201113303 phenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, decyloxyphenyl, tri Fluoromethylphenyl and the like. In R1 to R4 in the formula (1), it is preferred that at least one of R丨 and R2 or at least one of Han 3 and R is a carbon number 4 4 or a monovalent saturated hydrocarbon group or may be substituted. A carbon number of 6 to 1 〇 one-valent aromatic hydrocarbon group. Further, it is preferred that at least one of R1 and R2 and at least one of R3 and R4 have an inverse number of 14 or more, or a substituted carbon number of 6 to 丨〇 one-valent aromatic hydrocarbon group, Preferably, at least one of R1 and R2 and at least one of the ruthenium 3 and the ruthenium are substituted carbon number 6 to 1 fluorene monovalent aromatic hydrocarbon groups. R5 in the compound represented by the formula (1) represents -so3., -so3H, so3M, 〇2H, _C〇2R6, _s〇3R6 s〇2Nhr8 or _s〇2Nr8r9. In the formula (1), m represents an integer of 〇~5, and in the case of an integer of 2 or more, a plurality of R5s may be the same or different. Preferred examples of R ' are: a carboxyl group, an ethoxycarbonyl group, a sulfo group, a mercaptoethyl group; hexyl propyl propyl) amine continuation base, and N-(1,5-dimethylhexyl)amine. Amine 醯t 本 小 小 甲基 甲基 甲基 、 、 、 、 、 、 、 、 、 异丙 异丙 异丙 异丙 异丙 异丙 异丙 异丙 异丙 异丙 异丙 异丙 异丙 异丙 异丙 异丙 异丙 异丙 异丙 异丙 异丙 异丙 异丙 异丙 异丙 异丙 异丙 异丙 异丙 异丙A chlorine atom and a compound represented by the compound represented by the formula (1) are preferably the following formula (1-1) or (1_2) 150731.doc -30-201113303

In 6 , Rn to rM each independently represent a hydrogen atom, a -r6 or a carbon number of the aromatic smog group. The hydrogen atom contained in the aromatic hydrocarbon group may pass through a halogen atom, -R6, ^TT 6 '〇H,- 〇R, -S〇3-, -S03H, -S03Na, -C02H, CO 2 R 6 , _ r 6 Ο 3R, -S〇2NH2, -so2nhr8 or -so2nr8r9 are substituted.

Rl5 represents a hydrogen atom or -S02NR8R9. Rl6 represents -S〇3_ or -S02NR8R9. -S〇3-, -S〇3H, -so2nh2, _s〇3H, _so2nh2 -so2nhr8 -so2nhr8

R6, R8, r9, wherein the formula (K m, 1) is the same as x and a represents the same meaning as described above. The number of +charges of the compound and the number of _charges of the compound [Chem. 28]

, -R26 or a carbon number hydrogen atom may be halogenated 150731.doc ' 31. 201113303 Atom, -R26, -〇H, -OR26, -S03·, -S〇3Na, -C02H, -C02R26, -S〇3h , -S03R26 or -so2nhr28 replaced. R25 represents -S〇3., -S03Na, -C02H, -C02R26, -S03H or -so2nhr28 〇R26 represents a saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may pass through -OR27 or a halogen atom. Replace. 2 7 R represents a saturated hydrocarbon group having 1 to 10 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with an i atom. R28 represents a hydrogen atom, _R26, _c〇2R26 or an aromatic hydrocarbon group having 6 to 1 carbon atoms. The hydrogen atom contained in the aromatic smog group may be substituted by _R26 or _〇R26. m, X and a represent the same meanings as described above. In the compound represented by the formula (1-2), the number of charges is the same as the number of charges.] 0 Further, the compound represented by the formula (1) is preferably a compound represented by the following formula (1-3). [化29]

And R32 independently represent a phenyl group, an atom, -R26, _〇R26, I, and -C〇2R26, -S03R26 contained in the phenyl group [in the formula (1-3), and a hydrogen atom of r32 may be passed through Substituted by a prime atom, or -S02NHR28. 150731.doc •32- 201113303 »33 • 28 &gt;28 R33 means that the pin or milk is represented by a = hydrogen atom, s〇3• or _s〇2Nhr2 R , R 8 , x is. The main-pot table does not have the same meaning as above. Wherein the formula shown by the formula (U)]. The number of the first electric charge and the - charge number phase are further referred to as a compound represented by the formula (1). "Good 疋 4 (1-4) Ο [Chem. 30]

H, [In the formula (1-4), R4&gt; R42 independently represents a phenyl group. The hydrogen contained in the phenyl group may be substituted by _r26 or _s〇2Nhr28. The R table is not -8〇3· or -S02NHR28. R26, R28, and a represent the same meaning as described above. Ο Among them, the compound represented by 4 ', (1_4) has the same charge number as the - charge number]. The compound represented by the formula (1) to the formula (1f) is exemplified by the compound represented by the formula (1). [Chem. 3 1]

(1a) 150731.doc -33. 201113303 ' -S〇3* ' -SO3H ' . X and a are the same meanings as in the above [in the formula (la), R51 and independently represent the gas atom _c 〇 2h or - s 〇 2 n hr 5, and r 5 〇 represents 2 ethyl hexyl. Wherein the compound represented by the formula (la) [Chem. 32]

The + charge number of (1b) is the same as the - charge number, and has the same meaning as described above. among them

The compound shown in LiUlb) has the same charge number as the - charge number]. The compound represented by the formula (10) is a formula (a tautomer of the compound shown).

[In the formula (lb-Ι), p51 κ , 乂 and &amp; represent the same meaning as described above. Among them, the type of charge of the compound is the same as the number of charges and the number of charges. 150731.doc -34- 201113303

R53 〇C)

&lt;1d) [In the formula (lc) and the formula (Id), R53, R54 and R55 each independently represent _s〇3_, -S03Na or -S02NHR50. R50 represents 2-ethylhexyl. Here, the compound represented by the formula (lc) and the compound represented by the formula (Id) have the same charge number and charge number, respectively. [化35]

In the formula (le) and the formula (If), R56, R57 and R58 each independently represent a hydrogen atom, -SO, -S03H or -S02NHR5〇. R50 represents 2-ethylhexyl. Here, the compound represented by the formula (le) and the compound represented by the formula (If) have the same charge number and charge number, respectively. Specific examples of the compound represented by the formula (la) to the formula (If) include: sulfonate rose B, sulfonate rose B-SO3- or -SOsH sulfonamide-aminated compound, CI·solvent red 49, rose red B, CI acid purple 102, CI acid purple 102 -S〇3 · or -SOsH compound obtained by sulfoximation, c'I. acid red 289, CI acid red 289 -S (V Or a compound obtained by sulfonylation of -S〇3H, etc., wherein 'the dye used in the color-sensitive photosensitive resin composition of the present invention is 150731.doc-35-201113303, preferably a formula (le) or a formula Specifically, a compound represented by (If) is preferably a compound obtained by subjecting CI Acid Red 289, CI Acid Red 289-SO/ or -S〇3H to amidoximation. ) the compound shown. [Chem. 36]

The compound represented by the formula (?) can be produced, for example, by gasifying a pigment or a pigment intermediate having _S〇3H by a conventional method, and allowing the obtained pigment having -S〇2Cl or The pigment intermediate is reacted with an amine represented by rS_nh2. Further, it is also possible to produce a dye produced by the method described in the upper right column to the lower left barrier of page 3 of the Japanese Patent Laid-Open No. Hei. π (4) in the color of the middle: Α) In the case of the compound represented by the formula (1), the colorant is more preferable: (1) the content of the compound which is not particularly preferably is 3 to 80 mass. 2 疋 3 to 70% by mass, and further preferably 3 to 50% by mass. In the case where H(A) contains a dye different from the compound represented by the formula (1), the ratio of the wood = is preferably in the following range. Compounds indicated by '(): 1~&quot;% by mass &quot;) different dyes of different compounds: 丨~99% by mass 150731.d〇( -36 - 201113303 Right type (1) The compound and the dye of the formula (1) are different in dyeing ratio; the blending ratio is within the above range, and the target spectrophotometry can be obtained. The dye which is preferably dyed is an azo compound-containing dye, and more preferably contains the formula (2). A dye of the compound shown.

[In the formula (7), a divalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent is shown. The valence-free aromatic hydrocarbon group having a carbon number of 6 to 14 which may have a substituent or a monovalent heterocyclic group having 3 to 14 carbon atoms which may have a substituent. R51 represents a hydrogen atom, a carbon number which may have a substituent, a monovalent aliphatic hydrocarbon group, or a fluorenyl group having 2 to 18 carbon atoms which may have a substituent. Pl represents 1 or 2. In the case where pi is 2, the plurality of A〇, B〇, r51 and R52 may be the same or different. In the case where pl is 1, R52 represents a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a monovalent substituent, and in the case of ^, R52 represents a carbon number which may have a substituent a divalent aliphatic hydrocarbon group of ～35, which may be substituted by _〇2, _s-, -C Ο - and -NR ' in the monovalent aliphatic and valence aliphatic hydrocarbon groups. 'is a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms. The compound represented by the formula (2) is preferably a compound represented by the formula (2-1).

(2-1) 150731.doc -37- 201113303 [In the formula (2·Ι), 72, A, Ζ and Ζ3 each independently represent a valence aliphatic hydrocarbon group which may have a substituent of ~% number 1, and 22 The _CH plant contained in the old ten can be replaced by -CO· or _〇_. 5 3 JR 5 4 each independently represents a hydrogen atom, a carbon number 6 aliphatic aliphatic group which may have a substituent, or a fluorenyl group having 2 to 18 carbon atoms which may have a substituent. Α and Α respectively represent a divalent aromatic hydrocarbon group which may have a carbon number of a substituent. B and ^ each independently represent a carbon number of 6 to 14 which may have a substituent, and may have a substituent. The carbon number is 3 to 14-valent heterocyclic group. Z, Z2 and Z3 each independently represent a carbon number which may have a substituent, and the divalent aliphatic group of carbon number The carbon number of the hydrocarbon group does not include the carbon number of the substituent, and the amount thereof is preferably ruthenium, more preferably W. As the divalent aliphatic hydrocarbon group of carbon number 16, a carbon number W of the succinyl group can be cited. Listed: methylene, ethyl, propylenediyl, butyldiyl, pentyldiyl-hexyl, heptyl, octyldiyl, fluorenyldiyltetradecyl and hexadecane The _ch...-(3) substitution in the divalent aliphatic nicotine group of the number W6 may be substituted by a halogen atom such as a fluorine atom in the aliphatic hydrocarbon group of the carbon number H6. Z1 and Z2 are preferably It has a carbon number of ◦乂~8 to find a dibasic group, and a better θ may contain a calcined diyl group having a carbon number of 5 to 7. As a preferred base, for example, -(CH2)3-,- (CH2)2-CKCH2)2 ... ^CH2-CH(CH3)-〇( 2)2'〇'(CH2)2'°-(Ch^- 150731.doc •38- 201113303 z3 is better mc(=c)_ carbon number 8 is a better unsubstituted alkanediyl group having a carbon number of 1 to 8 and an unsubstituted alkyl group of 4 to 8. As a preferred embodiment: -(ch2)2·, _(CH2)4 • or .CH2_c (=ch2). A divalent aliphatic hydrocarbon, more preferably a carbon group, for example, 1 to 4 may represent R5丨, R52, R, and R54, and the carbon number H6-(iv) may be a linear, branched or cyclic type. The carbon number of the aliphatic hydrocarbon group does not include the carbon number of the substituent, and the amount thereof is preferably 6 to ig, more preferably

Examples of the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a second butyl group, and a decyl group. Butyl (^3·tetramethylbutyl, etc.), methylhexyl (1,5-dimethylhexyl, etc.), ethylhexyl (2-ethylhexyl, etc.), cyclopentyl, cyclohexyl, methyl ring Hexyl (2-methylcyclohexyl, etc.) and cyclohexylalkyl group. The hydrogen atom contained in the one-valent aliphatic hydrocarbon group of carbon number 16 may be substituted with an alkoxy group or a carboxyl group having 1 to 8 carbon atoms. Examples of the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which are substituted by the alkoxy group of carbon number 8 include a propoxypropyl group (3-(isopropoxy)propyl group, etc.) and an alkoxypropyl group. (3_(2-ethylhexyloxy)propyl, etc.). Examples of the aliphatic hydrocarbon group having 1 to 16 carbon atoms substituted by a carboxyl group include a 2-(sodium)ethyl group, a 3-(remedial)propyl group, and a 4-(indenyl)butyl group. Examples of the divalent aliphatic hydrocarbon group having a carbon number of 1 to 3 5 which may have a value of R include an alkylene group having a carbon number of 1 to 35, and examples thereof include a methylene group, an ethylidene group, and a propylene group. Butadiyl, pentanediyl, hexamethylene, heptadienyl, octyldiyl, decyldiyl, tetradecanediyl and hexadecandiyl. _(^1^2- can be replaced by -〇_, _; §- 150731.doc -39- 201113303, -co- and -NR,_ contained in the divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms The hydrogen atom contained in the aliphatic hydrocarbon group of the carbon number 35 may be substituted by a halogen atom such as a fluorine atom. The monovalent aliphatic hydrocarbon group having a carbon number of 丨 to 6 representing R| may, for example, be a methyl group or an ethyl group. a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, etc., and a chlorine atom represented by a carbon number of 2 to 18 of π may be substituted by an oxy group of a carbon number of 8. The carbon number of the carbon number of the carbon number (four) is counted by the number of carbon atoms of the substituent, and the number thereof is preferably 〇. As the thiol group which may have a substituent, for example, an ethylenic group, a benzamidine group,曱 苯 苯 苯 醯 ( 对 对 对 对 。 。 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为The fluorenyl group having a number of 2 to 5 is, for example, a hydrogen atom, an ethyl fluorenyl group or a propyl fluorenyl group. Examples of the divalent aromatic smoky group having a carbon number of 6 to 14 representing A and AjA2 are exemplified. Phenyl and naphthalene The preferred one is a phenyl group. As a substituent of a carbon number of 6 to 14: a valent aromatic group, an alkoxy group, a sulfhydryl group, and a decyl group of 8 And a sulfhydryl group, a fluorenyl group, an anthracene group, a fluorene atom, a fluorinated atom, a fluorinated atom, a fluorinated atom, a fluorinated atom, a fluorinated atom Atom or a bromine atom. As a group having a carbon number of 1 to 8, a methyl group, an ethyl group, a propyl group, a hetero group, a butyl group, an isobutyl group, a second butyl group, a tert-butyl group, a pentyl group are exemplified. And a hexyl group or the like is preferably a carbon group having 1 to 4 carbon atoms, more preferably a carbon number of 2, and particularly preferably a methyl group. As the alkoxy group having 1 to 8 carbon atoms, mention may be made of: Methoxy, ethoxy, propyl 15073 ] .doc -40- 201113303 oxy, isopropoxy, butoxy, isobutoxy, second butoxy, tert-butoxy, pentyloxy and The hexyloxy group and the like are preferably a decyloxy group having a carbon number of 4, more preferably an oxy group having a carbon number of 2, particularly preferably a decyloxy group. _s〇2NHR55 and -S〇2N (, with The same as those exemplified as -S〇2NHmS〇2N(R8)R9 in the compound represented by the formula (1), wherein (4) R' and R56 are each independently a carbon number which may have a substituent. The N-substituted amine fluorenyl group of the ketone group having a carbon number of 2 to 18 which may have a substituent. B°, B1 and ¥ each independently represent a carbon number which may have a substituent (2) The aromatic hydrocarbon group or the carbon number (10)-valent heterocyclic group which may have a substituent. Examples of the valent aromatic hydrocarbon group having a carbon number of 6 to 14 include a phenyl group, a naphthyl group, etc. As one of the carbon numbers 3 to 14 Examples of the valent heterocyclic group include the groups shown below.

Ο [R represents a hydrogen atom or an organic group]. Examples of the organic group include the same groups as the following r59. a carbon atom having a carbon number of from 6 to 14 and a valence of a heterocyclic group having a carbon number of from 3 to 14 and a valence of a heterocyclic group of 2 to 14 may be a group of a hydroxyl group having a hydroxyl group of 1 to 16 and a valence aliphatic group. , earthy, cyano, amine or N substituted amine substituted. As the hydrazine-substituted amino group, a -NHR57 group or a fluorene W8 group is preferred. R and 尺' are each independently represented by a carbon number which may have a substituent - 16731.doc -41. 201113303 A valence of a hydrocarbon group or a carbon number of 4 one-valent heterocyclic group which may have a substituent. Examples of the one-valent aliphatic hydrocarbon group having a carbon number of 1 to 16 and the one-valent heterocyclic group having a carbon number of 3 to 14 are the same as those described above. Preferably, Β, Β1 and Β2 are each independently a group represented by the formula (27). HO R» ~O=0 (2-1a)

R6. CN

[In the formula (2 U), R represents a hydrogen atom or a sulfonium-containing aliphatic hydrocarbon group having a carbon number of 1 to 16 which may have a substituent. R6Q represents a valence aliphatic hydrocarbon group having a carbon number of 丨~16 which may have a substituent. The pyridine ring of the group represented by the formula (2 1 a) may be a ketone type or an enol type. The one-numbered aliphatic hydrocarbon group having an inverse number of 1 to 16 is preferably the same as the above, and preferably R is methylbutyl (1,1,3,3-tetramethylbutyl or the like) or methylhexyl ( 1,5--methylhexyl, etc.), ethylhexyl (2·ethylhexyl, etc.), methylcyclohexyl (2-nonylcyclohexyl, etc.) and methoxypropyl (3-(2-ethyl) Hexyloxy) propyl, etc.) is a branched aliphatic hydrocarbon group. Examples of the substituent of R59 and R6 are those of a transradical group, a dentate atom, an alkoxy group having a carbon number of 1 to 8, and a carbon number of 8 carbon. Examples of the oxygen-burning group of the carbon number 8 are the same as those described above. The decyloxy group having a carbon number of 丨8 may, for example, be an ethoxycarbonyl group, a propenyloxy group, a hexyloxy group, an octyloxy group or a benzyloxy group. R6Q is preferably a methyl group. Examples of the compound represented by the formula (2) include those represented by the formula (^) to the formula (6) 8). The binding bond on the right side of A1, A2, Z1 and Z2 in the table indicates a bond close to 150731.doc -42 - 201113303 z3.

[Table 1] 1-1 A1 A2 Z 1 z2 ο- R59 R59, R60 R60' -c2h5 -c2h5 —ch3 —ch3 R 5 3 R54 z3 —Η —H —(CH2)2 — z2 side z1 side

[Table 2] 1-2 A1 A2 Z 1 z2 h3c - ύ- h3c R59 R59, R60 R6. , -c4h9 -c4h9 —ch3 —ch3 R53 R54 z3 —H —H —(CH2)2 — z2 side z1 side 150731.doc 43- 201113303 [Table 3] 1-3 A1 A2 z 1 z2 h3c R59 R59, R60 R60, -c4h9 -c4h9 —ch3 —ch3 R53 R54 z3 VH3 0 0 ——(CH2)8 — Z1 side z1 side [Table 4] 1—4 A1 A2 Z 1 z 2 CH3 ch3 4 R 5 9 R59, R60 R60' -C4H9 -c4h9 —ch3 —ch3 R53 R54 z3 —H —H —(CH2)8 — z2 side z1 side [Table 5] A1 A2 Z 1 Z 2 ch3 ch3 ch3 ch3 R59 RS9' R60 R60' -c4h9 - C4h9 —CH3 —ch3 R 5 3 R54 z 3 —H —H —(CH2)4—z2 side z1 side】5073 l.doc -44- 201113303 [Table 6] 1 to 6 A1 A2 Z 1 z2 ch3 ch3 4 ch3 Ch3 R59 R59, R60 R60, , ch3 , ch3 —ch3 --ch3 R53 R 54 z3 —H —H —(CH2)8—z2 side z1 side 〇[Table 7] 1-7 A1 A2 z 1 z2 ch3 ch3 Ch3 ch3 R 5 9 R59' R60 R60, XH3, ch3 —ch3 —ch3 r 53 R54 z3 —H —H —(CH2)4 — Z2 side ZM

[Table 8] 1-8 A1 A2 Z 1 z2 ch3 ch3 ch3 R59 R59, R60 R60, CH3 CH3 - C2H5 - C2H5 R53 R54 Z3 - H - H - (CH2) 8 - z2 side z1 side - 45 - 150731.doc 201113303 [Table 9] 1-9 A1 A2 Z 1 z2 ch3 ch3 ch3 ch3 R 5 9 R59' R60 R60' ^CH3 0 r〇H3 CH 3 0 —ch3 —ch3 R53 R 54 z3 —H ——H —(CH2 ) 4 — z2 side z1 side [Table i〇]

I - 1 0 A1 A2 Z 3 z 2 ch3 ch3 ch3 ch3 R59 R59' R60 R60' rCH3 CH 3 0 ^ch3 CH; 0 —ch3 —ch3 R53 R54 z3 —H —H ——(CH2)8 — z2 side z ] Side -46- 150731.doc 201113303 [Table η] 1-11 A1 A2 Z 1 z2 Let R 6 1 R6 1, R62 R62. —ch3 ~ch3 —ch3 —ch3 R53 R54 z3 —Η —H —(CH2) 2—z2 side z1 side

[Table 12] 1 - 12 A1 A2 Z 1 z2 h3c H3C R 6 1 R61, R62 R62' —^^-och3 -~^^och3 -C4H9 -c4h9 R53 R54 z3 —H —H —(CH2)4— z2 Side z1 side [Table 13] 1-13 A1 A2 z 1 z2 h3c H3CO R 6 1 R61' R62 R62' —^^-C〇2C2H5 -c3h7 -C4H9 R53 R54 z3 ,xh3 VH3 ——(CH2)8— 0 0 z2 side z1 side -47- 150731.doc 201113303 [Table 14] 1-14 A1 A2 z 1 z2 ch3 Capture ch3 4 R6 1 R6 R62 R62' -^^-〇ch3 —^^och3 - c4h9 -c4h9 R53 R54 Z3 Υ&quot;〇Η3 0 丫ch3 0 ch2 Z2 side z1 side [Table 15] 1-15 A5 A2 z 3 z2 ch3 ch3 R6 1 R61, R62 R62' —^^och3 - c4h9 - C4H9 R53 R54 z3 V&quot;ch3 0 Vch3 〇ch2 z2 side z1 side [Table 16] 1-16 A1 A2 z 1 z2 ch3 ch3 ch3 R6 1 R6], R62 R62' -〇-〇ch3 —^^*och3 -C4H9 -C4H9 R 53 R 54 z 3 ——H—H—(CHja—z2 side z3 side 150731.doc 201113303

[Table 17]

R65h 1-17 A1 A2 Z 1 z2 Cl Cl &lt;K R53 R54 R63 R63' —H —H —ch3 —ch3 Z 3 —(CH2)2 — z2 side z1 side [Table 18] —18 A1 A2 Z 1 z 2 ch3 奋ch3 R64 R64, R65 R65' O) ~QH〇R53 R54 z3 —H ——H ——(CH^a— .z2 side z1 side Ο ~N—22~〇^(ϋ—Z3—&amp; —0—Z1—ή—^—A1—N==N—R66 〇H HO Corpse 49-150731.doc 201113303 [Table 19]

1 — 19 A1 A2 z 1 Zz ~〇~ ~Q~ R53 R 54 R66 R 6 6, —Η —H ——H —H ζ3 —(CH2)8 — Z2 side Ζ1 side [Table 20] 1-20 A1 A2 Z 1 z2 points R53 R54 Z 3 —H —H ——(CH^q – z2 side z1 side

150731.doc 50- 201113303 [Table 21]

Preferably, Β1 and B2A; te Flai Ο 冋 type base, and, more preferably, eight and A, R and R54, 71 and 72. If it is such a base, the compound represented by the formula (2-1) can be easily produced. The compound of the formula (2-indole) can be represented by the formula (I-A) in a solvent, and the compound represented by the formula (I-A) and the compound represented by the formula G-B) in the range of 0 to 150. (: Manufactured under the reaction. R«〇一》iS—II 0f 9 A1—N==N—B1 (IA) ο (IB) [Formula (IA), Formula (Ι·Α'), and Formula (IB) In the above, Z1, Z2, Z3, r53, R54, A, A'B1 and B2 have the same meanings as described above. R and R8 each independently represent _〇R69 or a halogen atom, and R69 represents a monovalent carbon number of 1 to 16 An aliphatic hydrocarbon group]. Examples of the compound represented by the formula (IB) include dinonyl malonate, isobutyl succinate, dimethyl adipate, diethyl suberate, and propylene dichloride. 150731.doc -51- 201113303 Broken straw, hexamethylene chloride and octane dichloride. The compound of formula (IB) is used in comparison with the compound and formula (I-A) shown in formula (I_A). The total amount of the compound shown by ') is 1 mole, for example, preferably 0.5 to 3 moles. Further, when water is contained in the solvent, it is preferred to use the formula (I_B) in excess of the above amount. In the case where the compound represented by the formula (IB) has r3! and the size 32 is _〇1133, a well-known acid catalyst is preferably added as the acid catalyst. A stupid sulfonic acid and the like. The amount of the catalyst used is a total amount of the compound represented by the formula (I_A) and the compound represented by the formula (Ι-A,)! Mo, for example, preferably 0.01 to 2 mol. The reaction of the compound represented by A) and the compound represented by the formula with a compound of the formula (i-b) is carried out in a solvent. As the solvent, for example, water or an ether such as 1,4-dioxane is preferred. Especially cyclic ethers); gas imitation, di-methane, tetra-carbonized carbon, antimony, 2-dichloroethane, dichloroethylene, trichloroethylene, dilute ethylene, ethylene, propylene, sulphur, 1 , halogenated hydrocarbons such as 2-dioxacin; ketones such as acetone, mercaptoisobutyl ketone and cyclohexanone; carbon aromatics such as stupid, toluene and xylene; N,N-dimethylhydrazine Amine, N, N_: alkyl decylamine such as butyl decylamine, N,N-dimethylacetamide or N-methylpyrrolidone, or two or more solvents may be used in combination. The amount used is 1 part by mass based on the total of the compound represented by the formula (Ι-A) and the compound represented by the formula (I_A), and is preferably, for example, a mass fraction of Buchuan, more preferably 2 to 1 Torr. Mass portion. · The compound shown by the formula and the compound of the formula (Ι-A,) and the compound of the formula (I_B) are preferably reacted under a nitrogen atmosphere or an argon atmosphere 150731.doc -52 - 201113303 The reaction may be carried out under air dried by using calcium chloride or the like. The reaction temperature is, for example, preferably 〇 150 ° C, more preferably 1 Torr to 130 ° C. The reaction time is preferably, for example. 1 to 2 5 hours, more preferably 3 to 15 hours. The order of addition of the compound of the formula (Ι-A), the compound of the formula (I_A'), the compound of the formula (I_B) and the solvent is It is not particularly limited, and it is preferred to contain a compound represented by the formula (I_A), a compound represented by the formula (Ι-A), and a solvent; and a solution of the formula (I_B) is added (dropped) to the solution. Compound. In the case of using an acid catalyst, it is preferred to add (drop) to a solution containing a compound represented by the formula (I-A), a compound of the formula (1-8), an acid catalyst, and a solvent. a compound of the formula (IB). The method for obtaining the target compound, that is, the compound of the formula (2-1), in the reaction mixture obtained by the above method is not particularly limited, and various well-known methods can be employed, for example, by extracting the reaction mixture by using an organic solvent. purification. Further, it may be further purified by a well-known method such as washing or recrystallization using an alkaline aqueous solution or an acidic aqueous solution, if necessary.

Further, the compound represented by the formula (2_1) can be produced by coupling a compound represented by the formula (IC) with a compound represented by the formula (Ι-D) and a compound represented by the formula (I_D). . The formula can be produced by reacting a salt of the compound represented by the formula (I-C) with a compound represented by the formula (D-D) and a compound represented by the formula (I-D), for example, in an aqueous solvent at 20 to 6 Torr. Compound represented by 2·1} ΝΞΝ—A2—S—λ ^ 9 ^53 9 φ π 2 -0-C—Z»-C-0-Z1-N~S-A1-N=NX' ( } (id) H—B2 (I-〇r) 150731.doc -53· 201113303 A1, a:

R 54

B (in the formula (ί-C) and the formula (J_D), zi, y, r53 and B2 have the same meanings as described above. X represents an inorganic or organic anion). As a compound of the formula (Ι-C) and an inorganic or organic anion of the first element, a mouse element ion, a chloride ion, a π Μ π private shoulder ion, an iodide ion, a milk S ion, a second The chloric acid ion and the above-mentioned LH3-COO &gt; Ph-COO M are preferably chlorinated as the amide ion and CH3-COO-. As the dip, it is preferred that the quinone I 3 has a dye of a metal complex having an azo compound as a ligand, more preferably 3 Å, and the ruthenium contains a compound represented by the formula (3). Completed. The compound represented by the formula (3) is a salt of chromium ' and a cation. 4 material secrets anion and

Knife independently indicates gas atom, dentate atom, carbon number [in formula (3), Ral~Rai8 is divided into 1~8 one-price aliphatic nicotine group, Shifenqi-based, base, _S〇2NHRa30, s

, -COORU. Or ·s〇2Ra3. . W

Ral9 and Ra20 are independent tables

Da3〇 v represents an atom, a methyl group, an ethyl group or an amine group. R is independently represented by a hydrogen atom, an early atomic, an atomic anomaly of 1 to fluorene, and a -CH2· contained in the hydrocarbon group may be substituted by VII or _c〇. 150731.doc -54· 201113303 Μ1 indicates Cr or Co. N1 represents an integer of 1 to 5. D represents no hydrogen cation (hydr〇n), a monovalent metal cation or a valent cation derived from a compound having a benzopyran skeleton. Ο

G is a one-valent aliphatic hydrocarbon group which represents a carbon number of Ral to RaU, and examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, and a third butyl group. N-pentyl, n-hexyl, n-heptyl, n-octyl, decyl, methylbutyl, U,3,3·tetramethylbutyl, 1,5-dimethylhexyl, anthracene, 6-dimethyl Heptyl, 2-ethylhexyl and ^'^^tetramethylhexyl. The monovalent hydrocarbon group represented by the carbon number is a valence aliphatic hydrocarbon group having a carbon number of 1 to 10, a monovalent alicyclic hydrocarbon group having a carbon number of 3 to 10, and a carbon number of 6 to H. An aromatic hydrocarbon group and a group having a carbon number of 4, which are combined. Examples of the monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms include the same groups as described above, and the valent aromatic hydrocarbon group having a carbon number of 6 to 1 () is the same as the Q of the compound represented by the formula (1). base. Examples of the carbon number [Μ Μ alicyclic hydrocarbon group include a propyl group, a cyclopentyl group, a cyclohexyl group, a cyclodecyl group and the like. As the above hydrocarbon group in which -CH2- is substituted into 〇_ or _c〇_, it can be listed as ^3; ^32·0-^33 ' -Ra32-C〇-〇-Ra33 . .Ra32.〇.c〇_ Ra33 〇

Ra32 is a divalent aliphatic nicotinyl group of the carbon number i to 8 'Ra33 is a carbon number Η one-valent aliphatic hydrocarbon group. Examples of the divalent aliphatic nicotyl group which represents the carbon number of Ra32 include a methylene group, an exoethyl group, an alkyl group, a 3-diyl group, a propanol group, a 2-diyl group, a butyl group, and a m- group. Butane-1,3-diyl, pentane deca-5-diyl, hexane], 6-diyl, g-150731.doc 55- 201113303 Burning _1,7-diyl, octane-1,8-two Base. Examples of -Ra32-〇-Ra33 ': methoxymethyl, ethoxymethyl, propoxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxy Propyl, ethoxypropyl, propoxypropyl, 2-hydroxyl-4-ylmethoxy, octyloxypropyl, 3-ethoxypropyl, 3-(2-ethylhexyl) Oxy)propyl and the like. Examples of -Ra32-C0-0-Ra33 include a methoxycarbonylmethyl group, a methoxycarbonylethyl group, an ethoxycarbonylcarbonyl group, an ethoxycarbonylethyl group, a propoxycarbonylmethyl group, and a propoxy group. Alkylcarbonylethyl, butoxycarbonylmethyl, butoxycarbonylethyl and the like. Examples of -Ra32-0-C0-Ra33 include ethoxymethyloxymethyl, ethoxylated ethyl, ethylcarbonyloxymethyl, ethylcarbonyloxyethyl, propylcarbonyloxyfluorenyl. And propylcarbonyloxyethyl, butylcarbonyloxyindenyl, butylcarbonyloxyethyl and the like. As -S02NHRa3G, there may be mentioned: an amine sulfonyl group; N-methylamine sulfonyl group, N-ethylamine sulfonyl group, N-propylamine sulfonyl group, N-isopropylamine sulfhydryl group, N -butylamine hydrazino, N-isobutylamine sulfhydryl, N-second butylamine sulfonyl, N-tert-butylamine sulfonyl, N-pentylamine sulfonyl, N -(l-ethylpropyl)aminesulfonyl, N-(l,l-dimethylpropyl)aminesulfonyl, N-(l,2-dimercaptopropyl)aminesulfonyl, N-(2,2-dimethylpropyl)amine sulfonyl, N-(l-decylbutyl)amine sulfonyl, N-(2-mercaptobutyl)amine sulfonyl, N- (3-methylbutyl)amine sulfonyl, N-cyclopentylamine sulfonyl, N-hexylamine sulfonyl, N-(l,3-didecylbutyl)amine sulfonyl, N -(3,3-dimercaptobutyl)amine sulfonyl, N-heptylamine sulfonyl, N-(l-曱150731.doc -56- 201113303 hexyl)amine sulfonyl, N-( l,4-Dimethylpentyl)amine sulfonyl, N-octylamine (tetra)decyl, fluorenyl-(2-ethylhexyl)amine, n-(i,5-dimethyl)hexylamine An aliphatic hydrocarbon group such as a sulfonyl group, an N-(l,l,2,2-tetramethylbutyl)amine sulfonyl group, or an N-allylamine fluorenyl group Substituted amine fluorenyl; N-(2-decyloxyethyl)amine sulfonyl, N-(2-ethoxyethyl)amine sulfonyl, N-(1-methoxypropyl)amine Sulfonyl, N_(3-methoxypropyl)amine sulfonyl, N-(3-ethoxypropyl)amine sulfonyl, N-(3-propoxypropyl)amine sulfonyl, N-(3-Isopropoxypropyl)amine sulfonyl, n-(3-hexyloxypropyl)amine sulfonyl, N-(2-ethylhexyloxypropyl)amine sulfonyl , N_(3_2nd-butoxypropyl)amine, N-(4-octyloxybutyl)amine, and the aminesulfonyl group substituted by -R31-0-R32; N- (methoxycarbonyl fluorenyl) amine sulfonyl, N-(methoxycarbonylethyl)amine sulfonyl, N-(ethoxycarbonylmethyl)amine sulfonyl, N-(ethoxy Alkyl sulfonyl, N-(propoxycarbonylindenyl)amine sulfonyl, n-(propoxycarbonylethyl)amine sulfonyl, N-(butoxycarbonylmethyl)amine Amine substituted by -R31-CO-0-R32 such as sulfonyl, N-(butoxycarbonylethyl)aminesulfonyl; N-(ethyloxymethyl)amine hydrazino, N -(Ethyloxyethyl)amine, N-(ethylcarbonyloxymethyl)amine sulfonate , N-(ethylcarbonyloxyethyl)amine hydrazino, N-(propylcarbonyloxymethyl)amine decyl, N-(propylcarbonyloxyethyl)amine sulfonyl, N -(butylcarbonyloxymethyl)amine sulfonic acid, N-(butylcarbonyloxyethyl)amine sulfonyl group, etc. substituted with -R3]-0-C0-R32; Cyclohexylamine continuation base, N-(2-decyl ruthenyl) amine base, 150731.doc -57· 201113303 decylcyclohexyl)amine sulfonyl, N-(4-decylcyclohexyl) Aminesulfonyl group substituted with a cyclohexyl group having a substituent such as a sulfonyl group or an N-(4-butylcyclohexyl)amine sulfonyl group; N-benzylaminesulfonyl group, N-(l-phenyl group) Ethyl)sulfonyl, n-(2-phenylethyl)aminesulfonyl, N-(3-phenylpropyl)aminesulfonyl, n-(4-phenylbutyl)amine Indenyl, N-[2-(2-naphthyl)ethyl;j-aminosulfonyl, N-[2-(4-methylphenyl)ethyl]aminesulfonyl, N-(3-styl) An arylsulfonyl group substituted with an aralkyl group such as a 1-propyl)aminesulfonyl group or an N-(3-phenyl-1-methylpropyl)aminesulfonyl group. Examples of the -COORa30 include a decyloxycarbonyl group, an ethoxycarbonyl group, a propyloxycarbonyl group, a butoxycarbonyl group, a cyclohexyloxycarbonyl group, and a decyloxycarbonyl group. Examples of the -S〇2Ra30 include a sulfonyl group, an ethylsulfonyl group, a propyl sulfonyl group, an isopropyl sulfonyl group, a n-butyl sulfonyl group, a second butyl sulfonyl group, and a third butyl sulfonyl group. Ethylsulfonyl, hexylsulfonyl, heptylsulfonyl, octylsulfonyl, methylbutasulfonyl, 1,1,3,3-tetradecylsulfonyl, anthracene, 5_didecyl Sulfhydryl group, 1,6-dimethylheptanesulfonyl group, 2-ethylhexylsulfonyl group, 115,5 tetramethylhexanyl group, and the like. It is preferred that at least one of 疋R 1 to Ra 8 is a nitro group because of the tendency to have high heat resistance. As R, a one-valent aliphatic nicotinyl group having 1 to 8 carbon atoms, a cyclohexyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, -Ra32-0-Ra33, and -Ra32-C0-0-Ra33 are preferred. And -Ra32-〇_C〇_Ra33. A preferred example of the azo compound which becomes a ligand of a miscellaneous anion in the compound represented by the formula (3) is exemplified by the formula (l-al) to (l_a64) 150731.doc -58- 201113303 shows compounds and the like.

(1-a3)

(1-a2)

(1-34) (1-36) (1-a8)

(1-a10) (1-a12)

(1-a14)

(1-a16)

(1-a18) (1-a20) 150731.doc -59- 201113303

(1-a21) (1-a23) (1^a25)

〇H Hd N=/ (1-a22) so2nh2 卞 S02NH2_ 02N ^ OH HO0^ν=νΆ ο2νλ^ oh ho so2nh2 (1-a26)

(1-a27&gt; (1-a29)

(1-a28) (1-a30) TN=N_^no2 {1'a31) h2no2s/w OH ho o2n n=/ HsNOaS^^ 〇H HO O2N /=^\^〇Η3 ^Ynt N=N' H2N02S ^ OH HO 〇2N N=^ /=\vCI t N=N^ HaNOaS^^ OH H〇

(1^a33) (1-a35) (1-a37)

S02NH2 (1a-32)

N02 N-N—4 ^ (1-934) )—^so2nh2

〇H HO

〇H HO fe^N=N I,,^

〇H HO 150731.doc -60- 201113303 Ο

(1-a39) {1-a41) (1-a43) (1-a45) (1-a47) (1a-49) (1-a51) (1-a53) (1-a65)

(l-a40) (1-842) (1-a44)

(1-a46) (1-a46)

(1-a50)

(1-a52) (1-a54) (1-a56) 150731.doc -61 - 201113303

(1-a58) (1-a60) &lt;1-a62)

(1-a64) A preferred example of the complex anion in the compound represented by the formula (3) is an anion represented by the formula (Ι-bl) to the formula (1-b60).

150731.doc -62- 201113303 o

(1-t&gt;7) &lt;1-b9)

Θ •b MW· ja1

H^S λρ- P〆 \ o jcr Θ (1-b8) 02N&quot; ,N〇2 Θ HO3Sςτ * 〇2N^ , so3h

S02NH2 Θ (1 7 12)

Θ 3) Θ

XQ a

\CXN·'

,0

N pf 5 i o

150731.doc -63· 201113303

150731.doc -64- 201113303

-65 - 201113303

150731.doc -66- 201113303

θ (1·Μ8) (1-b50)

θ &lt;1«b62) Θ (1-b54) Θ (1-b56) 150731.doc -67- 201113303

(1 cut 7) &lt;1*b59) Ν«\ , 〇r'

Nr?

Ν〇2 &gt;s〇2〇h4 θ 0-b58) Π2 S〇jCH3, ο °^Ν^ΝΝ^ e d-beo)

Dl is a monovalent cation of a hydrogen cation monovalent metal cation or a compound of a skeleton. Potted one" with dibenzopyran

The brightness of the film is higher, and t is better. The color light obtained by the film is good. It is also derived from a cation having a bis-x compound. The compound represented by the formula (1): a compound having a surface of the formula (1), which is not a compound of the formula (3), is soluble in an organic solvent. Preferred are the compounds represented by the formula (IV). square

(3-1) Ra28 [Formula (3-1) allows R to Ra58 of carbon number 1 to 8 to independently represent a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group, a nitro group, a sulfo group, _s〇2Ra33 15073i.doc -68- 201113303 or -S02NHRa34 〇

Ra34 represents a hydrogen atom, a valent aliphatic hydrocarbon group of a carbon number, a cyclohexyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, Κ&amp;32_〇·κ&amp;33, _Ra32_c〇_〇Ra33, -Ra32 -0-C0-Ra33 or an aralkyl group having a carbon number of 7 to 1 Å.

Ra32 represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.

Ra33 represents a one-valent aliphatic hydrocarbon group having 1 to 8 carbon atoms.

Ra59 and Ra0〇 independently of each other represent a hydrogen atom, a thiol group, an ethyl group or an amine group. M2 represents Cr or Co.

Ra21 to Ra24 independently of each other represent a hydrogen atom, a carbon number, a monovalent aliphatic hydrocarbon group or a carbon number of 6 to 10, a monovalent aromatic hydrocarbon group, and the aliphatic hydrocarbon group and the hydrogen atom contained in the aromatic hydrocarbon group may pass through a hydroxyl group. , _ 〇 R32, contiguous, -S03Na, -S03K or halogen atom substitution.

Ra25 and Ra26 are each independently an atom or a methyl group.

Ra27 represents an ethyl group, a propane-1,3-diyl group or a propanediyl group.

Ra28 represents a hydrogen atom or a carbon group having 1 to 4 carbon atoms. η represents an integer of 1 to 4. In the case where η is an integer of 2 or more, a plurality of R27s may be the same or different from each other]. Examples of the one-valent aliphatic hydrocarbon group having 1 to 8 carbon atoms include the same groups as those of Ral to Ral8. Examples of the divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms include the same groups as those of the above Ra32. Examples of the alkyl group having 1 to 4 carbon atoms include a mercapto group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, and a third butyl group. Examples of the one-valent aromatic hydrocarbon group having 6 to 10 carbon atoms include a phenyl group and a methyl group 150731.doc • 69·201113303 phenyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, and propyl group. An aryl group such as a phenyl group, a butylphenyl group or a naphthyl group; an aralkyl group such as a benzyl group, a diphenylmethyl group, a phenylethyl group or a 3-phenylpropyl group; and the like. Examples of the cyclohexyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms include 2-methylcyclohexyl group, 2-ethylcyclohexyl group, 2-propylcyclohexyl group, 2-isopropylcyclohexyl group, and 2-butyl group. Alkylcyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-propylcyclohexyl, 4-isopropylcyclohexyl, 4-butylcyclohexyl, and the like. It is preferred that at least one of Ra41 to Ra58 is a nitro group because of the tendency to have high heat resistance. Further, it is preferred that at least one of Ra41 to Ra45 and at least one of Ra46 to RaSO are a sulfo group, _S〇2NHRa34 or _s〇2Ra33, more preferably _s〇2Ra33, and further preferably -so2ch3 . R is R to R, preferably a hydrogen atom or a valent aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, more preferably a hydrogen atom or an ethyl group, because the color density is high. As an extension of Ra27 ethyl. It is preferred to extend ethyl and propane q, 2 - diyl, more preferably hydrazine... preferably a hydrogen atom. Further preferably, the number of 'supplements' is preferably 2 or 4, and more preferably 3 or 琨, and preferably 3. ~ as -(R_a27_〇, n Ra28, K, solubility in organic solvents, ethoxylate) ethyl p-hydroxyethyl) ethyl and 2_[2-(2. ethoxylated) More preferably, ruthenyl ethoxy) ethoxy 15 3l.d〇c • 70- 201113303 is preferred as the cation of the dibenzopipen compound in the compound of formula (3-1). Examples thereof include a cation represented by the formula (Ι-cl) to the formula (1-C48). ο

201113303

150731.doc -72- 201113303

150731.doc ·73· 201113303

(1-C37)

(1-〇40)

(1-C46)

Specific examples of the compound represented by the formula (3-1) include a compound represented by the formula (3a-1) to the formula (3a-26). 150731.doc -74- 201113303

150731.doc -75 201113303

HsN02S

I

N〇2

o

N Λ 〇2N~\ // so2nh2

N-^ I Θ

(3a-6)

NO, e H2NO2S ^Cr 0

〇2N

\ fy so2w2 °-

0

Cr

(3a-7), . ~OH

J〇^ \ H2N〇2S ^br-^° 0^- (\ /&gt;-N^ J^^-^^so2nh2

y^N Θ

(3a-8), . ~OH N-

λ &quot;N

θ , N, H2NO2S r p

So2nh2

0

S- (3a-9)

H2N02S

N

_0

Xr&quot;

γ ~so2nh2 I N Θ

(3a-10) .Os 150731.doc -76- 201113303

(3a-15) 150731.doc -77· 201113303 Η〇3$

Π© so3h

*πθ

H2NO2S

150731.doc &gt;78- 201113303

150731.doc -79- 201113303

The octagonal order of the compound represented by the formula (3-1) is in terms of solubility in an organic solvent, preferably g, a good formula (3, formula (3a-3) to (3a_5) And the compound of the formula 3 7) (Μ, (3a_U) to (h-16), (3a-18) to 2) and the formula (3a-23) to (3a-26), more preferably The compound represented by the formula (3a-l), the compound of the formula (3), and the compound of the formula (3a-23)-w / (iv) the compound of the formula (3) can be used as follows And the manufacture: '(10) The compound and the chromium compound form a chromium-mismatched salt, and the compound represented by the formula (IV) and the compound compound-shaped wire are used, and the salt of the wrong salt is exchanged as needed.

(3d) The same as in the formula (3), [in the formula (3d), the meaning of Ral to Ra5].

Ran~Ra&quot; and R(1) are produced by the method of diazo coupling of L-azole compounds in the field of H. The compound represented by the formula (3_1) can be produced by subjecting the above-mentioned mixed salt to a salt exchange reaction with a benzoquinone compound of the formula: 150731.doc •80·201113303.

A Θ (b) [In the formula (8), W8 and η represent a formula (3_ represents a monovalent anion). Examples of the monovalent anion include .C1·BF4·, etc. The compound of the formula (8) and the compound of the formula (8) can be used. The compound of the formula (10) is produced by reacting a compound represented by the formula with an organic solvent. The same meaning is used in the oxime.

Bre, CKV, PF6. or combination

A Θ (b0) (bl) Ο , Ra21^ U. A represents the same meaning as in the formula (8)]. In the reaction described above, the reaction temperature is preferably 15. . ~60. . The reaction time is better for 1 hour ~]? /丨 _ 』, hour. Also, it is in terms of shortening the reaction time or increasing the yield. It is preferred to use an acid catalyst and/or a dehydrating agent. As an acid catalyst, Kelio #J enumerates sulfuric acid, p-toluenesulfonic acid, and the like. As a dehydrating agent, it can be used as a dehydrating agent. Dicyclohexylcarbodiimide, diisopropyl rabbit-imine, "卩|^土-(3-dimethylaminopropyl)carbon dioxime Imine salt 150731.doc 201113303 Carboxylides such as acid salts; 丨-alkyl 2 代 pyridinium salts; hydrazine, 1, carbonyl monoimidazole, bis (2- oxo-3- oxime) Oxazinyl)phosphinium sulfonate; di-2-pyridyl carbonate, etc. Among them, as the dehydrating agent, u-Z Z 3 -(3-monodecylaminopropyl)carbodiimide hydrochloride is preferred. The salt is easily post-treated and purified. Examples of the organic solvent used in the above reaction include dichlorosilane, chloroform, tetrahydrofuran, toluene, acetonitrile, etc. The compound represented by the formula (3-1) can be used. It is produced by subjecting the above-mentioned mixed salt to a salt exchange reaction with a dibenzopyran compound represented by the formula in a solvent. Preferably, the cobalt is miscible with a molar ratio of 1:1 to 1:4. The benzopyrazole compound (b) is reacted. The dyes are formed according to the solubility in a solvent or by using a photosensitive resin composition containing the dye to form a color filter. The content of the dye is preferably 0.5 to 60% by mass relative to the solid content of the colored photosensitive resin composition. The better is 〇7~5. 〇% by mass, and further preferably 疋1 to 40% by mass. Here, the solid content component refers to the total amount of components after removing the solvent from the colored photosensitive resin composition. Further, the colorant (Α) is preferred. In addition to the dye, the pigment is also contained. The pigment may, for example, be an organic pigment or an inorganic pigment, and may be exemplified by a compound classified as a pigment in "The Society 〇f Dyers" (The Society 〇f Dyers _~1〇山山出版). Specific examples of the organic pigment' include, for example. Pigment Astragalus, 3, 12, 13, 14, 15, 16, 17, 2, 24, 31, 53, %, J50731.doc -82· 201113303 93, 94, 109, 110, 117, 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 , 61, 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, 224 , red pigments such as 242, 254, 255, 264, 265; CI pigment blue 15, 15:3, 15·_4 '15:6, 60 and other blue pigments; CI·Pigment Violet 1, 19, 23, 29, 32 , 36, 38 and other purple pigments; CI pigment green 7, 36, 58 and other green pigments; CI pigment brown 23, 25 and other brown pigments; CI · pigment black 1, 7 and other black pigments. Among them, preferred are ci·pigment yellow 138, cj pigment yellow 139, c] pigment κ 150, CI pigment red 177, CI pigment red 2〇9, cj pigment red 242, CI pigment red 254, c〗. Pigment red purple 23, c丨·Pigment Blue 15:3, CI Pigment Blue 15:6 and c.] [Pigment Green 7, CI. Pigment Green %, 匚丄 Pigment Green 58. The pigment used in the coloring photosensitive resin composition of the present invention is more preferably selected from the group consisting of „. Pigment Blue 15:6, ct Pigment Red 254, C丄 Pigment Red 242, „Pigment Red m, ci Pigment Green. 58. A pigment of at least one of the group consisting of Pigment Yellow 15〇 and C丄 Pigment Yellow 138. The above pigment may also be subjected to a rosin treatment, a surface treatment using a pigment derivative or a pigment dispersant having an acidic group or an experimental group, and a pure treatment of the surface of the compound material by using 150731.doc •83-201113303 It is preferable to use a sulfuric acid atomization treatment, a cleaning treatment using an organic solvent to remove impurities, a ionic waste material to be removed by an ion exchange method, etc., and the pigment preferably has a uniform particle diameter. The pigment dispersion liquid in a state in which the pigment is uniformly dispersed in the solution can be obtained by dispersing the film containing the enamel. As the pigment dispersant, a commercially available surfactant can be used, and examples thereof include polyfluorene, fluorine, hydrazine, cation, anionic, nonionic, amphoteric, polyester, and polyamine. A surfactant such as an acrylic or the like may be used alone or in combination of two or more. Examples of the above-mentioned surfactant include polyoxyethylene alkyl mystery polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, montmorillonic acid modified polyesters, and the like. In addition to the above, the product name is κρ (manufactured by Shin-Etsu Chemical Co., Ltd.) and P〇ly fl〇w (Kyoeisha Chemical Co., Ltd.). Co., Ltd.), Eftop (Mitsubishi Materials Electronic Chemicals Co., Ltd.), Megaface (manufactured by DIC Corporation), Fluorad (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard (made by Asahi Co., Ltd.), Surflon ( Manufactured by AGC Seimi Chemical Co., Ltd., Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by CIBA Co., Ltd.), Ajisper (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (manufactured by BYK-Chemie Co., Ltd.), and the like. In the case of using a pigment dispersant, the amount thereof is preferably 1 part by mass or less per 1 part by mass of the pigment, more preferably 0.05 part by mass to 150731.doc -84 - 201113303 3 if the pigment is dispersed The amount of the agent to be used is in the range of the above-described range of the pigment dispersion liquid in the state of the knives. Therefore, the dyes and the pigments may be used alone or in combination of two or more. In addition, the dye and the sister-in-law, Shiyan and Yan Yan can be mixed at any ratio. The amount of Α i dyed 4 in the colorant (A) is 3 to 100% by mass, preferably 5% by weight, more preferably 5 to 80% by mass.

In the case of 0.5 parts by mass or less, it is preferable to obtain uniformity. The content of the pigment in the colorant (Α) is from 〇 to 97% by mass, preferably from 5% to 95% by weight, more preferably from 2 to 95% by mass. When the content of the dye and the pigment is within the above range, the target knives may be obtained, and excellent heat resistance and light resistance may be obtained. Therefore, it is preferred to use a coating film formed by using the colored photosensitive resin composition and In the case of a color filter provided in a liquid crystal display device or the like, the colored photosensitive resin composition is prepared by preparing a blue photosensitive resin composition, a green photosensitive resin composition, and Red photosensitive resin composition. The blue photosensitive resin composition preferably contains a compound represented by the formula (1) as a dye. X ' as a pigment' preferably contains at least one pigment selected from the group consisting of ci·pigment red violet 23, C.I. pigment blue 15:3, C.I. pigment blue 15:6, and more preferably contains C.I. Pigment Blue 15:6. In the case where the pigment is C.I. Pigment Blue 15:6, the mass of the compound represented by C.I. Pigment Blue 15:6 and Formula U) is preferably 97:3 to 50:50. The green photosensitive resin composition preferably contains a compound represented by the formula (2) as a dye. Further, it is preferred to contain at least one selected from the group consisting of C I. Pigment Green 36, c I 颜 150731.doc -85 - 201113303 Green 58, 58. C. 1. Pigment Yellow 138, C.I. Pigment Yellow 150 as a pigment. The red photosensitive resin composition preferably contains a compound represented by the formula (3) as a dye. Further, it is preferred to contain at least one selected from the group consisting of C.I. Pigment Yellow 138, C丄 Pigment Yellow 139, C.I. Pigment Yellow 15〇, c.I. Pigment Red 177, C.I. Pigment Red 242, C_I. Pigment Red 254 as a pigment. The content of the coloring agent (A) is preferably from 5 to 60% by mass, more preferably from 8 to 55% by mass, even more preferably from 10 to 50% by mass, based on the solid content of the colored photosensitive resin composition. When the content of the coloring agent (A) is within the above range, the color density when the color filter is formed is sufficient, and the composition may contain a desired amount of the binder resin, so that a pattern having a sufficient mechanical strength can be formed. It tends to be better. The colored photosensitive resin composition of the present invention contains a binder resin (B). The binder resin (7) contained in the colored photosensitive resin composition of the present invention contains a binder resin (BA) (hereinafter sometimes referred to as "Architecture (BA)") obtained by the following method: a monomer (Bb) having a carboxyl group and a polymerizable double bond, and at least one selected from the group consisting of a free bisphenol a type epoxy resin and a bisphenol F type epoxy resin (Ba) At least one of the group consisting of sour liver, maleic anhydride, and tetrahydrophthalic anhydride (Be) is reacted, and further contains an epoxy resin selected from the group consisting of a double-type epoxy resin and a bisphenol F-type epoxy resin. The polyfunctional epoxy compound (Bd) of at least one of the groups is reacted. At least one type (Ba) (hereinafter sometimes referred to as "epoxy resin (four)") selected from the group consisting of bisphenol A type epoxy resin and bisphenol F type epoxy resin is 150731.doc -86 - 201113303 A compound represented by the following formula (Ba-1). [化37]

OH In the formula (Ba-1), R represents a hydrogen atom or a methyl group. n represents the average value of the degree of polymerization, and is 0 to 20 Å, preferably 〇 2, and further preferably 〇 〜 ι. Specific examples of the monomer (Bb) having a carboxyl group and a polymerizable double bond (hereinafter sometimes referred to as "monomer (Bb)") include acrylic acid, mercaptoacrylic acid, crotonic acid, itaconic acid, and butylene. Diacid, fumaric acid, citraconic acid, mesaconic acid, cinnamic acid, succinic acid mono [2-(methyl) propylene methoxyethyl] ester, 'carboxypolycaprolactone mono(indenyl) ) Acrylate and the like. Among them, acrylic acid and methacrylic acid are preferred, and acrylic acid is particularly preferred because of the tendency of high light polymerizability and high sensitivity. In the present specification, the "(meth)acryl fluorenyl group" means at least one selected from the group consisting of an acryloyl group and a fluorenyl fluorenyl group. Moreover, "(meth)propionic acid" and the like also mean the same meaning. At least one selected from the group consisting of succinic anhydride, maleic anhydride, and tetrahydrophthalic anhydride (Bc) (hereinafter sometimes referred to as "anhydride (Be)") can be used alone. Succinic anhydride, maleic acid, and tetrachlorophthalic anhydride may be used in combination of two or more kinds. Among them, preferred is succinic anhydride. Further, an acid anhydride different from the acid anhydride (Be) (hereinafter sometimes referred to as "anhydride (Be)) may be used in combination. As the acid anhydride (Bcl), a glutaric acid needle can be cited, and it falls 150731.doc • 87- 201113303 Tonic anhydride, itaconic anhydride, _ phthalic anhydride, 5,6-dicarboxybicyclo[2.2.1] ng 2 training (bicycloheptene dicarboxylic acid Xuan) and so on. As a polyfunctional epoxy compound (Bd) containing 5 φ &amp; 至 夕 选自 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( It is called "multifunctional fg &amp; mannitol oxide 5 (Bd)"), and bisphenol A type epoxy resin and double type F type 虱 虱 resin can be used separately, or two or more types can be combined. The use of the compound can be enumerated and the like. Further, as a polyfunctional epoxidized bisphenol S-type epoxy resin containing a resin, a bisphenol quinone type epoxy resin starting material, an oxygen resin (Ba), and a reaction after reacting with an acid Sf (Be) The epoxy compound (Bd) may be the same or different. The resin (BA) can be obtained by a reaction as described below. First, the monomer _ is reacted with an epoxy group (Ba); a fluorenyloxy group is introduced to conduct a fluorenyl group, and a reactant obtained by adding a monomer (Bb) to the epoxy resin (Ba) is obtained. . Then, 'the acid needle (b... is bonded to the base formed by ring opening of the epoxy group in the obtained anti-deer), thereby introducing a slow group. The product obtained by (4) is further combined with a polyfunctional epoxy compound. (10)) The reaction is carried out, whereby a resin (BA) can be obtained. The reaction between the epoxy resin (Ba) and the monomer (Bb) is preferably substantially the same equivalent as the retardation in the epoxy group 1 〇 chemical equivalent monomer (10) in the epoxy resin (Ba). In the same manner, a reaction of 〇.8~U chemical equivalent is carried out. Further, the reaction between the epoxy resin (Ba) and the monomer (Bb) can be, for example, a polymerization inhibitor such as a phenanthrene, a monomethyl ether, a benzoic acid, or an oxygen, and a tertiary amine, a tri-phosphine, a lithium hydride, or the like. The reaction catalysts such as quaternary ammonium salts and quaternary scale salts are coexisted at 150731.doc -88-201113303 80~130 C. The reaction of the reactant obtained by the reaction of the epoxy resin (Ba) with the monomer (Bb) with the acid anhydride (Be) is preferably carried out with respect to the epoxy resin (Ba) and the monomer (Bb). The hydroxyl group formed by the reaction of 1 〇 is chemically equivalent, and 9 chemical equivalents of the anhydride (Be) are reacted therewith. When the acid anhydride (Bc) is in the above range, the developability tends to be good, which is preferable. When the acid anhydride (Be') is used in combination, it is preferred that the total amount of the acid anhydride (Bc) and the acid anhydride (Bc) is within the above range. The δHel reaction can be carried out, for example, in the presence of a polymerization inhibitor such as hydroquinone, monomethyl ether, benzophenone or oxygen, in the absence of a catalyst or a tertiary amine, a tertiary phosphine, a lithium chloride, a quaternary ammonium salt, The coexistence of four grades of scale salts, etc., is carried out at 5〇~13〇t. In the reaction of the resin obtained by the above reaction with the polyfunctional epoxy compound (Bd), it is preferred to use a carboxyl group equivalent to a carboxyl group in the resin obtained by the reaction with the acid anhydride (Bc). The epoxy group in the polyfunctional epoxy compound (Bd) is reacted in a G.1 to G.8 chemical equivalent. When the epoxy group of the polyfunctional epoxy compound (Bd) is in the above-mentioned position, the developability mechanical strength tends to be good, which is preferable. The reaction can be carried out, for example, in the presence of a polymerization inhibitor such as hydroquinone, monomethyl ether hydroquinone or oxygen; in a tertiary amine, a tertiary phosphine, a lithium chloride, a quaternary: a salt, a quaternary phosphonium salt, etc. Under the coexistence of reaction catalysts, Yu Chuan ~ 丨 艽 进行. The binder resin (BA) is preferably a compound (Be) containing at least one acid anhydride selected from the group consisting of succinic anhydride, maleic anhydride, and tetrahydrophthalic anhydride (hereinafter sometimes referred to as The resin obtained by the reaction of the resin obtained by the reaction described in the above-mentioned reaction of 150731.doc-89-201113303 is used for the reaction of the acid needle (4). The coughing reaction tends to improve the developability, which is preferable. The lyophilized reaction towel, the acid liver (8) which can be used, is the same compound as the above-mentioned acid anhydride (Be). X, the reaction conditions are the same as those of the reactant obtained by the reaction of the epoxy resin (tetra) with the monomer (10)) and the acid anhydride (Bc). The acid value of the resin (BA) is preferably 2 〇 15 15 Torr, more preferably 25 〜 13 〇, especially preferably 疋 3G 〜 110 。. When the acid value is in the above range, the solubility of the resin (BA) in the developer is improved, and the unexposed portion is easily dissolved, which is preferable. Here, the value obtained by measuring the amount of chlorine oxidative removal (mg) required for the i g-pro-glycolic acid polymer in the acid value is usually determined by titration using an aqueous potassium hydroxide solution. The weight average molecular weight of the resin (BA) determined by gel permeation chromatography ((4) permeati〇n chromatography, GPC) based on polystyrene: preferably 2,000 to 1 〇〇, 000, more preferably It is 2〇〇〇~5〇〇〇〇, especially good is 3,000~30,0〇〇. When the weight average molecular weight is within the above range, coating properties tend to be good, and there is a tendency that the residual film ratio at the time of development can be maintained and a high developing speed is obtained, which is preferable. The molecular weight distribution of the resin (BA) [weight average molecular weight (Mw) / number average molecular weight (?η)] is preferably 1.1 to 6. 〇, more preferably 12 to 4 〇. When the molecular weight distribution is within the above range, the developability tends to be excellent, which is preferable. The content of the resin (ΒΑ) relative to the binder resin is preferably 30 to 100% by mass, more preferably 4 to 1% by mass, particularly preferably 50 to 1%. quality%. When the content of the resin (ΒΑ) is within the above range, it is preferable that the solubility in the sputum sputum is sufficient to produce a developing residue on the substrate of the non-pixel portion. Further, in addition to the resin (BA), the binder resin (B) may be used in combination with a well-known resin. The resin which can be used in combination as the binder resin (B) is preferably not particularly limited as long as it is a developer which is used in the development treatment v, and particularly preferably, the developer solution is soluble, and examples thereof include, for example, a copolymer (BB) of a compound (B1) (hereinafter sometimes referred to as (B1)) having an acidic functional group such as a fluorinated group or a sulfonic acid group and another copolymerizable compound (hereinafter, sometimes It is called "resin (BB)"). Among them, (B1) is preferably an unsaturated compound having a carboxyl group. (B1) may be used singly or in combination of two or more. The unsaturated compound having a carboxyl group may, for example, be an unsaturated carboxylic acid having a singular or plural number of carboxyl groups in the molecule, such as an unsaturated monocarboxylic acid or an unsaturated dicarboxylic acid. Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, cinnamic acid, and dibutyl Acid mono[2_(methyl)acryloxyethyl)ester, ω-carboxypolycaprolactone mono(meth)acrylate, 5-carboxy-5-fluorenylbicyclo[2.2.1]heptan-2- Alkene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]heptene, 5-carboxy-6-ethylbicyclo[2.2 .1] Geng-2 - Rare. Among them, preferred are acrylic acid and methyl acrylate. For the binder resin (ΒΒ), a compound which can be copolymerized with (Β1), particularly preferably contains an unsaturated compound (Β〇) derived from a curable group (hereinafter, 150731.doc •91 · 201113303 sometimes called The structure of "(BO)") is more than a resin of 7 ° soap, because it can improve the reliability of the color pattern (resistant to light, solvent resistance, mechanical properties, etc.). And, as a hardening group, the chemical substance 5 (B0), for example, preferably has carbon-carbon unsaturated β-butyl

m A compound having a bond and a cyclic ether structure. The structure of the A-like ether ether can be exemplified by a gas-type m-coating structure (i.e., an ethylene oxide structure), an oxa%-butane structure, and a tetrahydrofurandu #) fluorene-butane structure. As a % oxygen structure, for example, it can be listed as a single-ring aliphatic epoxy structure, an aliphatic early-coating type, a oxidized oxygen, a 纟0 structure, and an aliphatic polymorphous & erotic milk structure, especially good Group polycyclic epoxy structure.疋月曰 (Β〇) can be used alone or in combination of two or more. The so-called aliphatic epoxy structure means that the fumed epoxy monocyclic epoxy structure refers to a monocyclic cycloolefin ring; (hri, a A . x coating % oxygen structure means a bridged ring (bndged nng) Cycloolefin epoxidation 乂 结构 structure. Examples of the monoterpene olefins include cyclopentene 3 decene % hexene and cycloheptene, etc. Cyclosporin, hydrazine, and decene oxime, for example, and tricyclic terpenes, etc. berberene, monopentene, as a carbon-carbon unsaturated double and &quot;heart fork and moon 曰 aliphatic ring Specific examples of the compound having an oxygen structure include, for example, glycerol, 1 T丞) glycidyl acrylate, (meth)acrylic acid-β-methylglycidol^ μ, 1 fluorenyl)acrylic acid-β-ethyl The shrinkage 'θ, glycidyl vinyl ether, t K -FH in the publication, and the compound shown by the formula 4 in the above-mentioned Japanese Patent Laid-Open No. Hei 7-248625. 150731.doc -92- 201113303 Here, the (meth) acrylate in the present specification means at least one selected from the group consisting of acrylates and methacrylates. R X J ' O /fnx (wherein RX1 to Rx3 are each independently a hydrogen atom or a carbon atom, and mx is an integer of 1 to 5). 〇 As the compound represented by the above formula, for example, o-vinylbenzyl glycidol, m-vinyl glycidyl glycidyl bond, p-vinyl phenyl glycidyl ether, α-methyl-o-vinyl benzyl bromide Glycidyl ether, cardiomethyl-m-vinylgangyl glycidyl ether, α-methyl-p-vinylbenzyl glycidol, 2,3-bis(glycidoxymethyl)styrene, 2 , 4_bis(glycidyloxyindenyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3 , 4_3 (glycidoxymethyl) stupid ethylene, 2,3,5-di(glycidyloxyindenyl)styrene, 2,3,6-nonyl(glycidoxymethyl)styrene 3,4,5-tris(glycidoxymethyl)styrene and 2,4,6-tris(glycidoxyfluorenyl)styrene. • Specific examples of the compound having a carbon-carbon unsaturated double bond and an aliphatic monocyclic epoxy structure include, for example, vinylCyCl〇hexene monoxide, i,2-epoxy 4_ vinylcyclohexane (for example, Celloxide 2000; manufactured by Daicel Chemical Industry Co., Ltd.), 2,3-epoxycyclohexylmethyl (meth)acrylate, and (meth)acrylic acid-3,4- Epoxy cyclohexyl hydrazine vinegar (for example, Cyclomer A400; Daicel Chemical 150731.doc -93-201113303 Industrial Co., Ltd.), methacrylic acid _3,4-epoxycyclohexylmethyl s (for example, Cyclomer M100; Daicel Chemical Industry Co., Ltd.) and so on. Specific examples of the compound having a carbon-carbon unsaturated double bond and an aliphatic polycyclic epoxy oxime structure include acrylonitrile-3,4-epoxynorbornyl ester and methacrylic acid-3,4-epoxy. The compound represented by the formula (B0-1) and the compound represented by the formula (B〇_2) are preferably a compound selected from the formula: @〇_1} and a formula (B0). -2) at least one compound of the group consisting of the compounds shown. [化39]

[Formula (B0-D and formula (B0_2)_, Ryl&amp;Ry2 each independently represents an alkyl group or a hydrogen atom of a carbon number, and a hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.

Xyl and χβ each independently represent a single bond or a carbon number which may contain a hetero atom 丨 ~ stone alkyl group]. Specific examples of the alkyl group having a carbon number of 丨~4 which may be substituted by a hydroxyl group include an anthracenyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, a tert-butyl group, and a hydroxy fluorenyl group. , i-hydroxyethyl, 2-hydroxyethyl, hydroxy-n-propyl, 2-hydroxyl-propyl, 3-amino-propyl &amp; , isopropyl, 2, isopropyl, 1-hydroxy-n-butyl, 2-hydroxy-n-butyl, 3-hydroxy-n-butyl, 4, 150,731.doc -94-

201113303 Benzyl butyl and so on. It is preferred to be a base, a hydrazine ethyl group, a better one can be a base group, a base group, and a B group: R, preferably a chlorine atom 1 group, "yi η via an ethyl group, The hydrogen atom and the methyl group are listed as hydrogen atoms and sulfur atoms, and the oxygen atoms and sulfur hetero atoms in the exudyl group having a carbon number of 1 to 6 which may contain a hetero atom may not be contained in the atom. Furthermore, the number of heteroatoms and the number of carbon atoms which may contain a hetero atom are as follows: methylene chloride, ethylidene, propylidene, oxymethylene (ie, _〇_) Ch^, oxy: oxypropyl, sulfoalkylmethylene (ie, -S_CH2_), sulfane (tetra)ethyl, sulfanylpropyl, imino subf (ie _nh_cH2_), imine The alkyl group and the imino group extending propyl group and the like are preferably those of a methylene group, an ethyloxymethylene group or an oxy group. Further, an alkyl group of ethyl group 0 is used as xyl and xy2. Preferable examples thereof include a single bond, a methylene group, an ethylidene group, an oxymethylene group or an oxyethyl group. More preferably, it is a single bond or an oxyethyl group. Compounds shown can be enumerated (BOH)~ a compound represented by the formula (B〇_ 1-15), etc., preferably a formula (Βο·^), a formula (B(M_3), a formula (B0-1-5), a formula (B0) -1-7), a compound of the formula (B0-1-9), a formula (B〇-l-ll)~ (B0-1-15), more preferably a formula (Bn-i), a formula (B0_ 1-7), a compound of the formula (B0-1-9) or a formula (B0-1-15). [Chem. 40] 150731.doc •95· 201113303

S 0 II h2c=ch«一 ch2 ?i h2c=ch-c-o h2c=ch-c~o-czh4 H2C=CH - C - o-c# 广〇

H2C*CH-C-〇—C2H4-S H2C=CH_C—O—C2H4—N CH3〇 H2C—C—C—O—CjH^—S

(BO-1-6) (BO-1-7) Household 0 HjC—C—C—0—C2H4-*ίΐ&quot; ch3o I II H2C*C—c—0 h2c=Ho- 〇43 ο H2Ci=C— S-ο-C^i4

(B(M-8) (B0-l-t3) QiH4〇H o , I II H2C»c-c-o ch30 ^ ^ I II (^C test ό-ό-〇-C points (

(BO-1-15) The compound represented by the formula (B〇-2) may, for example, be a compound represented by the formula (BO-2-1) to the formula (BO-2 15), and preferably, Formula (BO-2-1), formula (B0-2-3), formula (B0-2-5), formula (B0-2-7), formula (B0_2_9), formula (b〇_2_11)~ The compound represented by the formula (B0-2-15) is preferably a formula (b〇_2_1), a formula (B0-2-7), a formula (B0-2-9) or a formula (B0-). 2-15) Compounds shown. [化41] 0

(B0-2-2) H2C*CH-C~〇~CjHii_s H2C=CH-C-〇 〜

-96- 150731.doc 201113303

ο ο H2C=CH-C-〇-C2H4-〇

?h30 heart 1 tl H2c=c~—C-0-CH2 〇~-CjH4

(B0-2-5)

(BO-2-7) CH3 CH3o H2c =C —C—Ο—〇2Η4 ch3o

(BO-2-6) H2〇=C—C—O—C2H4~s HjC^C—C—O— ch3〇 H2C«C--C_〇_CjHj|_〇

The compound of the formula _) and the compound represented by the formula (b〇-2) may be used alone. In addition, these can also be mixed at any rate. In the case of mixing, it is mixed

The ratio of the molar ratio of the formula (B0-Iv + 9, ## | L )·(B0-2) is preferably 5:95 to 95.5 5 ® JtL PL· 〇• 子10:90 ~90:10, especially good 2〇: 8〇~

G 80:20. Specific examples of the compound having a carbon-carbon unsaturated double bond and an oxetane structure include 3-(meth)acryloxymethyloxybutane, 3-methyl-3- (Meth) propylene fluorenyl fluorenyl oxetane, 3-ethyl 3-(methyl) propylene decyl oxetane oxetane, 3- fluorenyl (fluorenyl) propylene oxide Methyloxetane, 3-ethyl-3-[1-(methyl)propenyloxy]methyloxetane, 3-methyl-3-[1-(methyl) Propylene oxime]ethyloxetane, 3-ethyl-3-[1-(methyl)propenyloxy]ethyloxetane, 2-phenyl-3-(methyl Acetyleneoxymethyloxetane, 150731.doc •97· 201113303 2-trifluoromethyl_3_(methyl)propenyloxymethyloxetane, pentafluoroethyl_3 -(Meth)acryloxymethyloxybutane, 3-methyl-3-(methyl)propenyloxyethyloxeane, 3-methyl-3-(methyl)propene Thin oxyethyloxetane, 2-phenyl-3-(methyl)propenyloxyethyloxetane, 2-difluoroindolyl_3_(methyl) propylene oxide Ethyl oxetane or 2- _3_ fluoroethyl (meth) Bing Xixi oxyethyl oxetane, methyl acrylic acyl group 3_ oxetane. Among these, 3 - ethyl-3-(methyl) propylene fluorenyl fluorenyl oxetane is preferred. Specific examples of the compound having a carbon-carbon unsaturated double bond and a tetrahydrofuran structure include (mercapto) tetrahydrofurfuryl acrylate, tetrahydrofuranyl methoxyethyl (meth)acrylate, and (meth) propylene. Acid tetrahydrofuranyl methoxypropyl ester and the like. In the case where the binder resin (BB) is a copolymer of (B1) and (B0), the structural unit derived from (B1) and from (B〇) are relative to the total number of moles of the structural unit constituting the copolymer. When the ratio of the structural unit is in the following range, storage stability, heat resistance, and mechanical strength tend to be good, which is preferable. Structural unit derived from (B1): 2 to 98 mol% Structural unit derived from (B0): 2 to 98 mol% Further 'If the ratio of the above structural unit is within the following range, then developability, residual film ratio or Better solvent resistance. Structural unit derived from (B1): is~6〇mol% % Structural unit derived from (B0): 40 to 85 mol% The above-mentioned adhesive resin (BB) can be referred to, for example, the experiment of polymer synthesis 150731.doc-98 · The 201113303 Act (the method described in the first print of the Chemicals Incident Publishing Co., Ltd., issued on March 1, 1972) and the references cited in the literature were produced. Specifically, a compound such as (B1) or (B0), a polymerization initiator, and a solvent can be introduced into a reaction vessel, and oxygen can be replaced with nitrogen gas to stir, heat, and heat in the presence of oxygen. A copolymer is obtained. Further, the copolymer to be used may be used as it is, or a concentrated or diluted solution may be used. Further, a solid body (powder) which is taken out by a method such as reprecipitation may be used. The binder resin (BB) may further contain, in addition to (B 1) or (B 1) and (B0), a compound (B2) derived from (B1) copolymerizable (excluding (B1) and (B〇)) (hereinafter sometimes referred to as "(B2)")). (B2), for example, a taurine compound having an olefinic double bond, a guanamine compound having a dilute hydrocarbon double bond, an aromatic compound having a polymerizable carbon-carbon unsaturated bond, and a substituted vinyl compound , a diene, an N-substituted maleimide compound, a polycyclic unsaturated compound, and the like. ❹ Specific examples of (B2) include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate; Benzyl (meth) acrylate, cyclohexyl (meth) acrylate, -2-methylcyclohexyl (meth) acrylate, iso- keto (meth) acrylate, tricyclo (meth) acrylate [ 5.2.1.02 '6] decane-8-yl ester (common name in the art is called dicyclopentyl (meth) acrylate), dicyclopentyloxyethyl (meth) acrylate, (fluorenyl) phenyl acrylate, aminoethyl (meth) acrylate, diethyl maleate, diethyl fumarate, diethyl itaconate, etc., unsaturated 150731.doc -99 - 201113303 phthalic acid esters; vinyl carboxylic acid esters such as vinyl acetate vinegar or vinyl propionate; polymeric phthalamides such as dimethyl (methyl methacrylate) acrylamide and isopropyl (meth) acrylamide; Polymeric aromatics such as styrene, α-methylstyrene or vinyl toluene; propylene such as acrylonitrile, methacrylonitrile or α-chloro(fluorenyl)acrylonitrile Nitrile; N-methyl maleimide ' N_ethyl maleimide butyl butyl succinimide, N-cyclohexyl succinimide ' 沁 基 顺Terbium-substituted quinone imines such as butylene diimine and N-phenyl maleimide; styrene, α-methylstyrene, m-decyl styrene, p-methyl Polymeric aromatics such as ethylene, vinyl toluene, p-nonyloxy styrene; halogenated ethylene such as ethylene, ethylene, trichloroethylene, vinyl fluoride, difluoroethylene, trifluoroethylene, tetrakis Rare; I'3 butadiene, isoprene '2,3-monodecyl_ι, 3_ butadiene and other dienes; bicyclo [2.2.1] hept-2-ene, 5-fluorenyl Bicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxyindolebicyclo[ 2.2.1] hept-2-indole, 5-(2'-hydroxyethyl)bicyclo[2.2_1]hept-2-ene, 5-nonyloxybicyclo[2.2.1]hept-2-ene, 5- Ethoxybicyclo[2.2.1]hept-2-ene, 5,6-di-propylbicyclo[2.2.1]hept-2-ene, 5,6-di(methyl)bicyclo[2.2_1]g 2-ene, 5,6-bis(2,-hydroxyethyl)bicyclo[2·2·1]hept-2-ene , 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-fluorenylbicyclo [2.2.1] Hept-2-ene, 5-hydroxy-5-ethylbicyclo[2·2·1]hept-2-ene, 5-methyl-5-fluorenylbicyclo[22.1]heptane- 2-Diluted, 5-150731.doc •100- 201113303 Cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycyclobicyclo[2.2.1]hept-2-ene, 5 a polycyclic unsaturated compound such as 6-bis(cyclohexyloxycarbonyl)bicyclo[2.21]hept-2-ene. Among these, preferred are (benzyl) benzyl acrylate, stupid ethylene, phenyl phenyl succinimide, Ν-cyclohexyl succinimide, Ν 节 顺 顺Equinone imine, bicyclo [2.2.1] hept-2-ene, and the like. The above (Β2) may be used singly or in combination of two or more.

Ο In the case where the binder resin (ΒΒ) is a copolymer of (Β1) and (Β2), the structural unit derived from (βι) and from (Β2) with respect to the total number of moles of the structural unit constituting the above copolymer When the ratio of the structural unit is in the following range, storage stability and heat resistance tend to be good, which is preferable. Structural unit derived from (Β 1): 2 to 98 mol% Structural unit derived from (Β2): 2 to 98 mol% Further 'If the ratio of the above structural unit is within the following range, the developability or residual film ratio The aspect is better. Structural unit derived from (Β1): 15~6〇mol% Structural unit derived from (Β2): 40-85 mol% Copolymer of (Bl), (Β0) and (Β2) in the adhesive resin (ΒΒ) When the ratio of the structural unit derived from (Β0) to (Β2) is within the following range with respect to the total number of moles of the structural unit constituting the copolymer, storage stability, heat resistance, and mechanical strength become Good tendencies, so do it well. Structural unit from (Β0): 2 to 97 mol% Structural unit from (Β1): 2 to 97 mol% 150731.doc 101 · 201113303 Structural unit from (B2): 1 to 96 mol% and ' When the ratio of the above structural unit is in the following range, it is more preferable in terms of developability, residual film ratio, or solvent property. Structural unit from (B0): 20~80mol% Structural unit from (B1): 1〇~50mol% % Structural unit from (B2): 1〇~70mol% Contains the above from (B0) The binder resin (BB) of the structural unit of (B2) can be produced by the same method as the above-mentioned resin containing the structural units derived from (B1) and (B0). Among the binder resins (BB) containing the structural unit derived from (B2), copolymers of (B1), (B0) and (B2) are preferred because the coloring formed by the colored photosensitive resin composition can be improved. Heat resistance, light resistance, solvent resistance and mechanical properties of the pattern. In addition, as a structural unit in the above-mentioned binder resin (BB), a macromonomer having a monopropenyl group or a monomethacrylinyl group at the terminal, a unit represented by the following formula (21), and a formula (22) The unit or the like shown is more excellent in pattern adhesion, solvent resistance, and sensitivity. [化42]

[In the formulae (21) and (22), RW, Ry4, Ry5 and Ry6 each independently represent a hydrogen atom 150731.doc -102-201113303 or an alkyl group having a carbon number of 1-6. The binder resin (bb) containing the structural unit represented by the formula (21) can be obtained by obtaining a structural unit (Bla) containing an unsaturated compound having a carboxyl group or an unsaturated compound having a carboxylic acid anhydride (hereinafter) a resin referred to as "(Bla)j), such as a copolymer of (Bla) and (B0), a copolymer of (Bla) and (B2), a copolymer of (Bla) and (B0) and (B2), Then, the obtained copolymer is reacted with a compound represented by the following formula (23) in a carboxylic acid moiety or a carboxylic anhydride moiety contained in (B丨a). Ο As an unsaturated compound having a carboxyl group in (Bla), Examples of the compound exemplified as the specific example of (7) i), and specific examples of the unsaturated compound having a carboxylic acid anhydride include maleic anhydride and 5,6-dicarboxybicyclo[2.2.1]g·2·lean. (Bicycloheptene: f anhydride), etc. Among them, (meth)acrylic acid is preferred.

0 〇 [In the formula (23), Ry4 represents a hydrogen atom or a carbon number. The adhesive resin (bb) having the formula (2 2) shown in the formula (2 2) can be obtained in the same manner as described above, and is lacking in the design of No. J ^ 2〇05', which is described in the pure towel, is obtained by reacting the obtained mound with a compound of the formula (5) (IV). ^ [化44] 150731.doc •103· (24) 201113303

[In the formula (24), Ry6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms]. The acid value of the resin (BB) is usually 5 Å to 15 Å, preferably 6 Å to 5 Å, particularly preferably 70 135 Å. When the acid value is in the above range, the solubility in the developer is improved, and the unexposed portion is easily dissolved, which is preferable. The weight average molecular weight of the resin (BB) determined by the gel permeation chromatography based on polystyrene is preferably 2 〇〇〇 to 1 〇〇〇〇〇, more preferably 2,000 to 50 Å. 0〇〇, especially good is 3〇〇〇~3〇〇〇〇. When the average weight of the octagonal amount is within the above range, the coating property tends to be good and i tends to maintain the residual film ratio at the time of development and to obtain a higher development speed. The molecular weight distribution of the resin (BB) [weight average molecular weight (Mw) / number average molecular weight (?η)] is preferably ^^^, more preferably 丨2 to 4 〇. If the molecular weight distribution is within the above range, the developability tends to be excellent, which is preferable. In the case where the binder resin (B) contains the resin (BA) and the resin (BB), the resin (BA) and the resin (BB) may be used in combination at any ratio. In this case, the mixing ratio of the resin (BA) to the resin (BB) is preferably in the following range in terms of the mass ratio j. Resin (BA): 1 〇 to 90% by mass Resin (BB): 90 〜1 〇% by mass The content of the bonded tree 曰 (B) is calculated by mass fraction with respect to the solid content in the colored photosensitive resin composition. The good is 丨〇 ~ 3 5 mass%, better 150731.doc -104- 201113303 is 15~30% by mass. The content of the binder (MB) is preferably 2 〇 to 8 〇 mass%, particularly preferably 30 to 7 〇 mass%, based on the total amount of the binder resin (8) and the photopolymerizable compound (6). &amp; f amount %. The silk-containing resin (8) contains yttrium in the above range H 丨 面 树 ) ) ) _ 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 + + 易于 易于 易于 易于 易于 易于 易于 易于 易于 易于 易于 易于 易于 易于 易于 易于 易于 易于 易于 易于 易于 易于 易于 易于 易于When the non-pixel portion is reduced, the detachment property tends to be good. Therefore, it is preferable that the resolution and the residual film ratio tend to increase. The colored photosensitive resin composition of the present invention contains a photopolymerizable compound (C). The photopolymerizable compound (6)' refers to a compound which can be polymerized by using an active radical, an acid or the like generated from a photopolymerization initiator (D) by irradiation with light, and examples thereof include a polymerizable carbon-carbon unsaturated bond. Compounds and the like. &quot; The photopolymerizable compound (C) is preferably a photopolymerizable compound having three or more carbon-carbon unsaturated bonds. Examples of the trifunctional or higher polyfunctional photopolymerizable compound include pentaerythritol tris(meth)acrylic acid vinegar, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol. Four yeast five (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. The photopolymerizable compound may be used singly or in combination of two or more. The content of the photopolymerizable compound (C) is preferably from 7 to 65 mass%, more preferably from 13 to 60 mass%, more preferably from 13 to 60 mass%, based on the solid content of the coloring photosensitive resin composition. 17 to 55 mass. /. . When the content of the photopolymerizable property 150731.doc -105· 201113303 is within the above range, the curing can be sufficiently performed, and the film thickness ratio before and after the development is improved, and the pattern is less likely to be undercut, and the adhesion is changed. It is better to have a good tendency. The colored photosensitive resin composition of the present invention contains a photopolymerization initiator (9) m polymerization initiator (9), and examples thereof include an active radical generator, an acid generator, and the like. The living radical generator generates active radicals by irradiating light. Examples of the living radical generating agent' include, for example, a compound, an aroma compound, a dibenzoyl compound, an oxysulfuric-star compound, a triazine compound, a fat compound, and the like. Examples of the acetophenone compound include diethoxyacetophenone, 2-methyl-2-carbolinyl o-methylthiophenyl)propane ketone, and 2-hydroxyl-methyl-1-benzene. Propane small _ 'stupid 醯 dimethyl condensate, 2 hydroxy I methyl 1-l-[4-(2-hydroxyethoxy) benzene 1 soil] propan-1-one, 1-hydroxycyclohexyl Phenyl ketone, 2-hydroxy-2-methyl field * (-methylvinyl) phenyl] propane - ketone - ketone oligomers, etc. 'better can be listed" Tian * @ 2_ methyl ~ 2. Weilinji-ι-(4-indolethiophenyl)propan-1-one and the like. As a benzoin compound, for example, w j illusion, feminine, benzoin

Ether, benzoin, benzoin π D, isopropyl ether, benzoin isobutyl ether, etc. As a formazan compound, for example - * can be exemplified by: benzamidine, o-benzazole-based methyl formate, 4-phenyl-bi-cage, -4-, 4-benzylidene- 4, _methyl Benyl sulfide, 3,3',4,4'-tetra (p-τ w 24, φ ^ butyl peroxycarbonyl) diphenylmethyl, 2,4,6-trimethylbenzophenone Wait. As the 9-oxosulfur ρ Yamaguchi star compound, / for example, 2·isopropyl_9_oxime 150731.doc •106-201113303 咄蠖, 4-isopropyl-9-oxosulfonium, 2 4_Diethyl_9_oxysulfide p ant, 2,4-chloro-9-oxothioxanthine, Buqi·'propoxy- 9-oxopurine and the like. Examples of the second-till compound include 2,4-bis(trichloroindenyl)·6·(4-methoxyphenyl)-1,3,5-tri-u well, and 2,4-bis (trichloro). Methyl)_6_(4•methoxy-based)-1,3,5-three-spray, 2,4-bis(trimethyl)methyl-6-(4-methoxystyryl)-1'3, 5-three tillage, 2,4_bis (trioxanyl)_6_[2_(5_f-based furanyl)ethidyl]-1,3,5-three-spray, 2,4·bis(trichloromethyl) )_6·[2 十夫喃_2_基) Ethyl]_1,3,5-three-spray, 2,4-bis(trichloroindenyl)-6-[2-(4-diethylamine) Benzyl-2-methylphenyl)diyl]·1,3,5_three IJ well, 2,4_bis(trichloromethyl)-6-[2-(3,4-didecyloxy) Phenyl)vinyl]_丨, 3,5-three tillage, etc. Examples of the ruthenium compound include a ruthenium ruthenium ruthenium compound, and specific examples thereof include N-benzyl methoxy 丨 ( ( (4-phenylthioalkylphenyl) butan-1-one- 2-imine, N_benzylideneoxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N_acetoxyl-l-[9_ Ethyl·6_(2_mercaptobenzylidene)-9H-carbazole·3_yl]ethaneimine, N_acetoxyl “seven ethyl heart Q {2_methyl_4_(3 , 3_Dimethyl-2,4·dioxalanylmethoxy)benzimidyl}-911-oxazol-3-yl]ethane·imide-imine, etc. Irgaeure OXE can also be used. -01, lrgacure OXE_02 (the above is manufactured by Ciba Chemicals Co., Ltd.), and 'N-1919 (made by ADEKA Co., Ltd.), etc. 'As an active radical generator other than the above-exemplified ones, for example, 2 may be used. 4,6-trimethylbenzimidyldiphenylphosphine oxide, 2,2,_bis(o-indolyl)-4,4,5,5'-tetraphenylbiimidazole, 1〇_丁Base 2_chloroacridine_, ethyl hydrazine, benzophenone, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound, etc. I50731.doc •107· 201113303 As an acid generator' For example, p-toluenesulfonic acid _4-hydroxyphenyl dimethyl hydrazine, hexafluoroantimonic acid-4-hydroxyphenyl dimethyl hydrazine, p-toluenesulfonic acid ethoxylated phenyl dimethyl hydrazine, six Fluoric acid _4_acetoxyphenyl methyl sulfonium hydrazide, diphenyl sulfonium p-toluenesulfonate, triphenyl sulfonium hexafluoroantimonate, diphenyl quinone p-toluenesulfonate, hexafluoroantimonic acid An anthracene salt such as phenylhydrazine, or a nitrobenzyl tosylate or a benzoin tosylate, etc. Further, the above-mentioned compound which is described as an active radical generating agent is also present in A compound which generates an acid while generating an active radical, for example, a three-till compound can also be used as an acid generator. As the photopolymerization initiator (D), it is more preferable to contain at least one selected from the group consisting of stupid substances. The photopolymerization of the ruthenium-containing compound can form a pattern of sensitivity, preferably a living radical generator, a ketone compound, a tri-farming compound, and a photopolymerization initiator of a ruthenium compound, and further preferably a starter. In the case of the photopolymerization initiators, the total amount of #...&amp; resin (8) and the photopolymerizable compound (c) is photopolymerized. The content of the agent (9) is preferably .1 to 3. parts by mass, and the inner diterpene is 2 to 2 parts by mass. If the content of the photopolymerization initiator is in the above-mentioned range, the sensitivity is increased and the exposure time is shortened, and the production is shortened. If you improve your sexuality, you will be better at the same time. Agent: The color-sensitive resin composition contains (4), etc. 曰, 醯 amine, N-methyl pyrrolidine, dimethyl sulfoxide as ether Examples thereof include tetrahydrofuran, tetrahydropyran, 1,4-two 150731.doc 201113303 alcohol monoethyl ether, ethylene glycol monopropyl ether, ethyl chloride, ethylene glycol monomethyl ether, and ethyl acetate. ~ 13⁄43⁄4 m 3.1, alcohol early methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl hydrazine - alcohol monoethyl ether, diethylene glycol methyl ether, diethylene Alcohol dioxime, monoethylene glycol dibutyl sulphate, propylene glycol monoterpene acetate vinegar, propylene glycol mono &amp; early ether ether acetate, propylene glycol monopropyl ether acetate vinegar, propylene glycol early 曱 、, A 丞金丞赛路Acetate, ethyl sirolimus acetate, ethyl carbitol acetic acid s, butyl carbamide acetate, anisole, benzene, Anisole and the like.

Examples of the aromatic smog include benzene, toluene, diphenylbenzene, and 1,3,5-trisylbenzene. Examples of the ketones include propanone, 4-heptanone, 4-methyl-2-pentanone, pentyl, cyclohexyl and the like. _, 2-butanone, 2-heptanone, 3-heptan-4-yl-4-mercapto-2-pentanyl, ring as an alcohol, for example, can be listed with · wp J. methanol, ethanol, propanol , butanol, hexanol 'cyclohexanol, ethylene _. One%, glycerol, etc. Ο As a broad class, for example, ethyl acetate, n-butyl acetate, acetic acid: amyl succinate, isoamyl acetate, isobutyl acetate, butyl acetobutyrate, butyric acid Ethyl vinegar, butyric acid butyrate, alkyl vinegar, lactic acid: ester, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, methyl acetonitrile, _ 曰 ethoxy ethoxyacetate Ethyl ethoxyacetate, ethyl 3-methoxypropionate methyl methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxypropionate, bismuth 2-hydroxypropionate Ester, ethyl 2-methoxymethoxypropionate, propyl 2-methoxypropionate, methyl acetoacetate, ethyl lactyl propionate, 2-decyloxy Ethyl -2-methylpropionate, 15073l.doc 201113303 Ethyl 2-ethoxy-2-methylpropionate Methyl pyruvate, ethyl pyruvate, propyl acrylate, acetonitrile acetate Ethyl acetate, ethyl acetate, 2, methyl acetobutanoate, ethyl 2-oxetoxybutyrate, 3-methoxybutyl acetate, 3-mercapto-3-methoxybutyl Alkyl acetate, γ·butyrolactone, and the like. Examples of the brewed amines include hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine dimethylacetamide, hydrazine-methylpyrrolidone, and the like. Among the above, etc., preferred are propylene glycol monomethyl ether acetate, propylene glycol monomethyl sulfonate, and 4' base methyl &amp; 173⁄4 ig # u m g. Further, the solvent (8) may be used singly or in combination of two or more. The content of the solvent (E) in the colored photosensitive resin composition is preferably 7 () to 95% by mass, more preferably 75 to 90% by mass, based on the mass fraction. When the content of the solvent (8) is within the above range, the flatness at the time of coating becomes good, and (4) the color shading is not insufficient when the color filter is formed. Therefore, the display characteristics tend to be good, which is preferable. The photopolymerization starter (F) may also be included in the «u kiss~alumina resin composition. The photopolymerization start-up aid system is used in combination with a photopolymerization initiator to promote the polymerization of the light-emitting compound by the extraction of the initiator. The sensitizer. Examples of the photopolymerization initiation aid (F) include an amine compound, a 4-oxo oxime compound, and a 9-oxothione compound. Examples of the amine compound include &gt;

^ 平.Diethanolamine, methyldiethyl S fee, diisopropanolamine, 4_dimethyl~benzic acid formic acid, 4-dimethyl sequence 15073],doe-110- 201113303 benzoic acid ethyl , 4-dimethylamino-based benzoic acid, isoamyl vinegar, benzoic acid, 2-dimethylaminoethyl acetonate, 4-dimethylamino benzoic acid, 2-ethylhexyl phthalate, dimethyl-methyl Aniline, 4,4'-bis(dimethylamino)benzhydryl network (commonly known as rice basin (4), hydrazine, -bis(di 6-amino) benzophenone, 4,4, • double (B More preferably, 4,4 or bis(diethylamino)benzhydrazide is used as the alkoxypurine compound, and for example, 9,1 〇 is exemplified. Dimethoxy depleted, ethyl-9,10-di(tetra) onion, 9,1 〇•diethoxy f, 2 ethane oxime diethoxy oxime, 9,10-dibutoxy onion, 2 _Ethyl_9,1〇-dibutoxy onion, etc. As the 9-oxo-sulfur such as a star compound, for example, 2-isopropyl-5-oxathione, 4-isopropyl-7-- Oxygen sulfur ♦ star, 2,4_diethyl_9_oxysulfur such as star, 2,4·dichloro_9_oxysulfide, hawthorn, 丨_chloro·4_propoxy oxysulfonium, and the like. Photopolymerization start aid (F) In the case of the photopolymerization initiation aid (F), for example, a commercial product such as the trade name AB F" (manufactured by Hodogaya Chemical Industry Co., Ltd.) can be used as the present invention. The combination of the photopolymerization initiator (:) and the photopolymerization initiation assistant (F) in the coloring photosensitive resin composition of the invention may, for example, be diethoxyacetophenone / 4,4 -bis (two Ethylamino)dimercaptoketone, 2-methyl-2-yl-morpholinyl](4-methylthiophenyl)propanone]-ketone/4,4,_bis(diethylamino) Dimethyl ketone, 2-hydroxy-2-methyl-hydrazine-phenylpropane, bis(diethylamino), benzamidine, benzoin dimethyl ketal / 4,4, _ double ( Diethylamino)benzophenone, 2-carbyl-2-methyl-W4_(2-diethoxyethoxy)phenyl]propanone/150731.doc -111 - 201113303 4,4- Bis(ethylethylamino)benzophenone, hydroxycyclohexyl phenyl ketone bis(diethylamino)benzophenone, 2-hydroxy-2-methylnonylvinyl)phenyl]propane 1-ketone oligomer/4,4,_bis(diethylamino)benzophenone, 2-benzyl-2-butan-1-one/dimethylamino- 1-(4-morpholinylphenyl) 4,4'-bis(diethylamino)benzophenone, etc., preferably, methyl-2-tyrosolinyl-K4-methylthio Phenyl)propanone/4,4,_bis(diethylamino)dibenzophenone. In the case of using the photopolymerization initiation assistant (F), it is preferably used in an amount of from 1 to 1 mol per mol of the photopolymerization initiator (D) per i mole. Good is 0.01~5 m. The colored photosensitive resin composition of the present invention may further contain an interface active agent (G). The surfactant (G) is at least one selected from the group consisting of a polyfluorene-based surfactant, a fluorine-based surfactant, and a polyfluorene-based surfactant having a fluorine atom. The polyoxo-based surfactant may, for example, be an interfacial surfactant having a decane bond. Specific examples include: T〇ray SUic〇ne DC3pA, D. ^^

Silicone SH7PA ^ Toray Silicone DCllPA^ T〇ray Silicone SH21PA &gt; Toray Silicone SH28PA ^ Toray Silicone 29SHPA, Toray Silicone SH30PA, Polycrystalline Shishi Oil SH8400 (named by Toray Silicone Co., Ltd.), κρ32ΐ, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Silicone), TSF4〇〇, TSF401, TSF41〇, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Sakamoto Moto High-Tech Materials Co., Ltd. ( M〇mentive perf〇rmance 150731.doc •112- 201113303

Materials Japan) manufactured by a subsidiary). The fluorine-based surfactant may, for example, be a surfactant having a fluorocarbon chain. Specific examples include: Fluorad (trade name) FC430, Fluorad FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megaface (trade name) F142D, Megaface F171, Megaface F172, Megaface F173, Megaface F177 ' Megaface F183, Megaface R30 (DIC shares limited) Manufactured by the company, Eftop (trade name) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (manufactured by New Akita Chemical Co., Ltd.), Surflon (trade name) S381, Surflon S382, Surflon SC101, Surflon SCIO5 (manufactured by Asahi Glass Co., Ltd.) ), E5 844 (manufactured by Daikin Precision Chemical Research Co., Ltd.), bm-1000, ΒΜ-11〇〇 (all trade names, manufactured by bm Chemie). The polyfluorene-based surfactant having a fluorine atom may, for example, be a surfactant having an anthracycline bond or a fluorocarbon chain. Specific examples are:

Megaface (registered trademark) R08, Megaface BL20, Megaface F475, Megaface F477, Megaface F443 (manufactured by DIC Corporation), and the like. These surfactants may be used singly or in combination of two or more. The content of the surfactant (G) is preferably from 〇〇〇〇〇1 to 〇丨% by mass, more preferably from 0.00005 to 0.01% by mass based on the mass fraction of the coloring photosensitive resin composition. . When the content of the surfactant (6) is within the above range, the flatness tends to be good, and it is preferable. Here, the content of the surfactant (G) does not include the content of the above pigment dispersant. As a method of forming a pattern of color filter 150731.doc • 113·201113303 using the colored photosensitive resin composition of the present invention, for example, the colored photosensitive resin composition of the present invention is applied to a substrate or another resin layer. (for example, a layer of another colored photosensitive resin composition previously formed on a substrate, etc.), a method of forming a colored layer by removing a volatile component such as a solvent, and then exposing and developing the colored layer via a photomask (ie, photolithography) Method); and a method of using an inkjet machine that does not require photolithography. The coating film of the present invention can be obtained by the use of the mask 'and/or no development' during exposure in the above pattern forming method. A plurality of TFTs 22 are formed on each of the pixels on the glass substrate 21 by a well-known method such as photolithography (see FIG. TFT. The TFT 22 includes, for example, molybdenum (Mo) formed on the glass substrate 21 a gate electrode 22a constituting one of the gate lines, and a gate insulating film 22b formed of a laminated film of a nitride film (SiNx) and an oxide film (Si〇2) formed on the gate electrode 22a, a polysilicon film 22c formed on the gate insulating film 22b, and a protective film 22d formed of, for example, a laminated film of an oxide film (Si〇2) and a nitride film (SiNx), and a gate electrode 22a of the polysilicon film 22c. The opposite region becomes the channel region of the TFT 22 and the region on both sides of the channel region becomes the source region or the drain region. The source region of the polysilicon film 22c passes through the connection hole (contact hole) provided in the protective film 22d. Further, the signal line 27 formed by, for example, aluminum (A1) is electrically connected. Further, the drain region of the polysilicon film 22c is electrically connected to the pixel electrode 24 via a connection hole (contact hole) 201 as described below. Forming each pixel on the glass substrate 21 When a plurality of TFTs 22 are formed, alignment marks are formed while forming the TFTs 22 on the glass substrate 21. (not shown in Fig. 150731.doc • 114-201113303). The alignment marks are formed as a color light-receiving sheet layer 23 as described below. Further, the alignment marks may also serve as a mark for bonding the drive substrate and the counter substrate. The material mark may form a metal layer or a polysilicon layer such as a wiring in the manufacturing process of the TFT 22. When at least one of the layers is used, it is formed in the same step.

Next, on the glass substrate on which the TFT 22 and the alignment mark are formed, a photosensitive resin composition layer 23 of a film thickness of 〇 5 to 5 Å μηι, for example, i 〇 μ μηι, is formed by spin coating or the like. The colored photosensitive resin composition layer 23 A corresponds to the color filter of the present invention.

Then, the colored photosensitive resin composition layer 23A is dried by heat treatment at a temperature in the range of 30 to 120 t, for example, 6 〇 to U (rc). The dried coloring photosensitive composition layer 23 A can be decompressed. Drying is combined with heat drying. Next, the colored photosensitive resin composition layer 23A is irradiated with ultraviolet rays through a mask (not shown), and the excess portion (unexposed portion) is selectively removed by the developer. A connection hole (contact hole) 201 reaching the drain region of the polysilicon film 22c is formed, and then washed with water. Thereafter, the coloring photosensitive sapling composition layer 23 A is reflowed (re-dissolved) And curing the curable component contained in the colored photosensitive composition layer 23A, and heating at a temperature in the range of 100 to 300 ° C, for example, 15 Torr to 23 ° C. Thereby, the colored photosensitive resin composition is colored. The layer 23 A is formed as a color filter layer 23 (see FIG. 2) including a red color filter 23a, a green color filter 23b, and a blue color filter 23c corresponding to each pixel row. The color filter layer 23 The area between the filters becomes a mixture of adjacent colors The area is combined, but since the area is opposite to the light-shielding area of the signal line 27, it does not particularly affect the quality of the product. Further, the area between the filters may not be colored. Then, for example, a photosensitive resin film as a protective film having a film thickness of 0.3 to 2.Q μΓη is formed by a spin coating method so as to cover the color filter layer 23, and is formed by a photomask (not shown). The photosensitive resin film 29', the line, and the line are selectively removed by the developer to the pair of connection holes 20 1 . The product region and the evening # &amp; ' thereby forming a connection hole (contact hole) 2G2 reaching the non-polar region of the polycrystalline film 22c, and then performing water washing. Thereafter, in order to reflow (rejugate) the photosensitive resin film 29, it is heated at a fox degree of, for example, 2 GG C in the range of 10 G to 30 Gt. Then, in order to remove the residual fish and organic matter deposited in the contact hole 202, the oxide film formed by the oxygen destruction is removed by etching, for example, by dilute hydrofluoric acid. The two persons form a transparent human material such as IT〇 (Indium_Tin: an oxide of indium and tin) on the photosensitive resin film 29 by sputtering, for example, and then pattern the ITO film by photolithography and surname. Thereby, the transparent pixel electrode 24 is formed (refer to FIG. 4). Further, depending on the material to be fabricated, the pixel electrode 24 may be formed of a metal such as Ai or Ag (Ag). Thereafter, the alignment film is formed by a known method - and then the drive substrate is bonded to the opposite substrate, whereby the liquid crystal display can be manufactured. According to the light sheet of the present invention, a bulk imaging element is obtained. The color film of the coating film 'pattern and color tear which is excellent in heat resistance can be suitably used for a liquid crystal display element or a solid example 150731.doc-116-201113303 Hereinafter, the present invention will be described in more detail by way of examples. Unless otherwise stated, the "%" and "parts" in the examples are % by mass and parts by mass. [Synthesis Example 1] (Synthesis Example of Compound of Formula (1)) In a flask equipped with a cooling tube and a stirring device, 15 parts of a compound represented by the formula (AO-1) and a formula (A0-2) are charged. A mixture of the compounds (manufactured by Chinese and foreign chemical production), 150 parts of chloroform and 8.9 parts of N,N-dimercaptocarbamide were maintained at 20 ° C or lower while stirring, and 10.9 parts of sulfoxide gas was added dropwise thereto. After the completion of the dropwise addition, the temperature was raised to 5 CTC, and the mixture was allowed to react at the same temperature for 5 hours, and then cooled to 20 °C. While the cooled reaction solution was maintained at 20 ° C or lower under stirring, a mixture of 125 parts of 2-ethylhexylamine and triethylamine as a mixture was added dropwise. Thereafter, the mixture was stirred at the same temperature for 5 hours to cause a reaction. Then, the solvent of the obtained reaction mixture was distilled off by a rotary evaporator, and a small amount of methanol was added thereto and stirred vigorously. The mixture was added to a mixed liquid of 375 parts of ion-exchanged water while stirring to precipitate crystals. The precipitated crystals are separated by filtration, and the mixture of the compound represented by the formula (A1_a) and the compound of the formula (4)-oxime (A1) is obtained by sufficiently washing with a water-exchanged water at 60 C under reduced pressure (A1) (Formula (4)" A mixture of the compounds of the formula (Ai 8)) 11 &gt; 3 parts. [化45]

150731.doc •117 201113303

[In the formula (Al-a) and the formula (Al-b), Rg, Rh and t each independently represent a hydrogen atom, -S03-, -S03H or 2-ethylhexylsulfanyl group]. [Chem. 46]

Ra-HNC^S

Ra-rt^OjS

[Synthesis Example 2] 350 parts of a bisphenol A type epoxy resin (epoxy equivalent weight: 1 87 150731.doc -118 - 201113303 g/eq) was added to the reaction tank, and a p-methoxy group as a polymerization inhibitor was added. 1 part of phenol, one side of a mixture of nitrogen and oxygen (oxygen concentration of 5%) foaming side 2 heat to 115C, then add 138 parts of acrylic acid, propylene glycol monomethyl ether acetate vinegar (hereinafter referred to as PGMEA) 135 parts, 32 parts of triethylamine, reaction * hour. The reaction was cooled to 105 ° C, and 187 parts of succinic anhydride and pGMEA 2 were added for a reaction for 7 hours. Then, 233 parts of a bisphenol A type epoxy resin (epoxy equivalent: 187 g/eq), 1000 parts of PGMEA, and 1 part of a polymerization inhibitor methoxy phenol were added, and the reaction was carried out at 115 t: for 12 hours, and then cooled to a chamber. The resin solution 1 was obtained by heating. The obtained resin solution 1 was measured for various physical properties, and as a result, the weight average molecular weight was 1.2×104, and the solid content concentration obtained after drying at 16 (vacuum under vacuum was 40% by weight, per unit amount determined by titration) The acid value of the solid content was 49 mgKOH/g. [Synthesis Example 3] A bisphenol fluorene type A epoxy resin (epoxy equivalent weight: 187 g/eq) was added to a separable flask equipped with a cooling tube as a reaction vessel. 35 parts, and added as a poly &amp; inhibitor of p-oxybenzene to 1 part of 'on one side, a mixture of nitrogen and oxygen (oxygen concentration of 5%) foaming while heating to 115. (:, then add Acetone. 138 parts of acid, 135 parts of PGMEA, and 3.2 parts of dimethylbenzylamine were reacted for 4 hours. The reaction was cooled to 1 〇〇t: 87 parts of succinic anhydride ι and 221 parts of PGMEA were added and reacted for 5 hours. Then, 262 parts of a bisphenol A type epoxy resin (epoxy equivalent: 187 g/eq), 1040 parts of PGMEA, and 1 part of p-methoxyphenol as a polymerization inhibitor were added at 115. (: 1 hour reaction) Further, 9 parts by weight of succinic anhydride was added, and after reacting for 3 hours at u 〇 °c, cold 150731.doc -119-2011 13303 was obtained at room temperature, thereby obtaining a resin solution 2. The obtained resin solution 2 was measured for various physical properties in the same manner as in the resin solution 1, and as a result, the weight average molecular weight was 2.36 X 104 and the solid content concentration was 41.4 ° / °. The acid value per unit amount of the solid content was 44 mgKOH/g. [Synthesis Example 4] A double-aged type A epoxy resin (epoxy equivalent weight: 187 g/) was added as a reaction tank "separable flask with cooling f". Eq) 35 parts and adding p-methoxyphenol as a polymerization inhibitor i part while foaming a mixed gas of nitrogen and oxygen (oxygen concentration of 7%), heating to 115 art, and then adding 138 parts of acrylic acid, 135 parts of PGMEA and 3·2 parts of triethylamine were reacted for 4 hours. The reaction was cooled to 100 ° C, 187 parts of succinic anhydride and 220 parts were added, and reacted for 3 hours, followed by addition of bisphenol A type epoxy resin ( 653 parts of epoxy equivalent (467 g / eq), 1500 parts of PGMEA, 1.3 parts of p-methoxyphenol as a polymerization inhibitor, reacted for 1 hour at U5t: further added 9 parts by weight of succinic anhydride at 11 ( After reacting for 3 hours at rc, cool to room temperature and borrow

This obtained resin solution 3 D was measured for various physical properties of the obtained resin solution 3 in the same manner as the resin solution 1 'Results The weight average molecular weight was i 82 xi 04, the solid content concentration was 40% by weight, and the solid content per unit amount was The acid value is 50 mgKOH/g. [Synthesis Example 5] A bisphenol A type epoxy resin (epoxy equivalent weight: 187 g/eq) 34 parts and pGMEa 42 parts ' was added to a separable flask equipped with a cooling tube as a reaction tank and added as One part of the polymerization inhibitor p-methoxyphenol was heated to 150731.doc •120·201113303 115°C while foaming a mixture of nitrogen and oxygen (oxygen concentration of 7%), then adding 135 parts of acrylic acid, PGMEA 135 parts, two 7-C»amines 3.2 parts 'reaction for 8 hours. The reaction was cooled to 1 Torr (Tc, 160 parts of _*_Ifc anhydride was added, and reacted for 3 hours. Then, 2l3 parts of bisphenol a type epoxy resin (epoxy equivalent of I87 g/eq) and 700 parts of PGMEA were added. 1 part of p-methoxyphenol as a polymerization inhibitor, at 115. (: After 10 hours of reaction, it was cooled to room temperature, thereby obtaining a resin solution 4. The obtained was obtained in the same manner as the resin solution 1. The resin solution 4 was measured for various physical properties, and as a result, the weight average molecular weight was 9 〇 x 103, and the solid content concentration was 40.0 ° /. 'The acid value per unit amount of the solid content was 33 mg KOH / g. [Synthesis Example 6] In a 1 L flask of a reflux condenser, a dropping funnel and a stirrer, a nitrogen gas was introduced at 0.02 L/min to form a nitrogen atmosphere, and 200 parts by mass of 3-methoxy-1-butanol and 3-methoxybutylethyl group were added. 1 〇 5 parts by mass of the acid ester, heated to 70 while stirring on the surface. (:. Further, dissolved in 6 parts by mass of methacrylic acid, 3,4-epoxytricyclo[5.2.1.02'6] decyl acrylate (The compound represented by the following formula (B 1-1-1) and the compound represented by the formula (B1-2-1)) are mixed in a molar ratio of 5 〇:5 240, and 240 parts by mass and 3 A solution was prepared in 140 parts by mass of methoxybutyl acetate, and the dropping solution was added to a flask maintained at 7 ° C for 4 hours using a dropping funnel. On the other hand, another drop was used. The funnel was added to the flask over 30 hours, and 30 parts by mass of the polymerization initiator 2,2,-azobis(2,4-dimethylvaleronitrile) was dissolved in 3-methoxybutyl acetate. The solution obtained in 225 parts by mass. After the dropwise addition of the solution of the polymerization initiator, it was kept at 7 (rc for 4 hours) and then cooled to room temperature to obtain a weight average molecular weight Mw of 1.3×10 4 and a degree of dispersion (Mw/Mn). The resin solution HI having a solid content of 33% by mass and 150731.doc -121 - 201113303 having an acid value of 34 mg-KOH/g.

〇II H2C=CH-C—0 0 » h2c=ch-c~-o· About the obtained polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Μη) of the above resins 1 to 4 and HI The measurement was carried out under the following conditions using a GPC method.

Device: HLC-8120GPC (manufactured by Tosoh Co., Ltd.) Column: TSK-GELG2000HXL Column temperature: 40 ° C Solvent: THF (tetrahydrofuran, tetrahydrofuran) Flow rate: 1.0 mL/min Test liquid Solid content concentration: 0.001~0.01% by mass

Injection amount: 50 pL Detector: Standard material for RI calibration: TSK STANDARD POLYSTYRENE F-40, F-4, Fl, A-2500, A-500 (manufactured by Tosoh Corporation) [Example 1] (Coloring sensitivity) Preparation of Resin Composition 1) (A) Colorant: CI Pigment Blue 15:6 (Pig: PB 15:6) 33 parts 150731.doc -122- 201113303 Acrylic pigment dispersant 5 parts propylene glycol monomethyl ether B 137 parts of the acid ester are mixed, and the pigment is sufficiently dispersed using a bead mill, followed by mixing (A) Colorant: Dye A1 5 parts (B) Resin. Resin solution 1 1 5 parts '(C) Photopolymerizable compound: II Pentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Sakamoto Chemical Co., Ltd.) 50 parts (D) Photopolymerization initiator: N-benzylideneoxy 4-(4-phenylsulfanylphenyl) Xinyuan-1-en-2-amine (irgacure OXE 01; manufactured by Ciba Japan Co., Ltd.) 15 parts (E) Solvent: 289 parts of ethyl lactate to obtain a colored photosensitive resin composition 1. The colored photosensitive resin composition 1 obtained was evaluated by the following method. The results are shown in Table 1. &lt;Formation of Patterns&gt; The colored photosensitive resin composition 1 was applied by spin coating on a glass substrate (Eagle 2000; manufactured by Corning Co., Ltd.) of 2 inches square, and then at 100 ° C Pre-bake for 3 minutes. After cooling, the distance between the substrate coated with the colored photosensitive resin composition and the patterned quartz glass mask was 100 μm. Using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) under atmospheric conditions The light was irradiated with an exposure amount of 15 〇mj/cm 2 (based on 365 nm). After the light irradiation, the coating film was immersed and developed in an aqueous developing solution containing a nonionic surfactant 〇·12% and potassium hydroxide 0.04% at 23° C. for 80 seconds, washed with water, and then placed in an oven. After 20 minutes, it was baked at 150731.doc -123- 201113303 220 C. After leaving to cool, the film thickness of the obtained hardened pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.), and as a result, it was 2.2 μηι 〇 &lt;heat resistance evaluation&gt; The upper pattern is measured by a color measuring machine (OSP Sp_2〇〇; manufactured by Olympus Co., Ltd.) and measured by a color matching function of the C light source (CIEmmission Internati〇nai de rEclairage, International Commission on Illumination) The xy chromaticity coordinates (X, y) and the luminance Y in the XYZ color system. The above pattern was heated in an oven of 23 (rc for 2 hours. After heating, the chromaticity coordinates were measured again, and the color difference Δ Eab* before and after heating was calculated. The results are shown in Table 22. The smaller the color difference AEab*, the better the heat resistance. When the heat resistance of the pattern is good, the coating film also exhibits good heat resistance similarly to the pattern. [Examples 2 to 5] In addition to changing the resin or combining a plurality of resins in such a manner as to have the composition shown in Table 22 The colored photosensitive resin composition and the pattern were obtained in the same manner as in Example 1. The evaluation was carried out in the same manner as in Example 1. The results are shown in Table 22. [Comparative Example 1] (Coloring photosensitive resin composition) Preparation) 33 parts 5 parts 5 parts 137 parts (A) Colorant: CI Pigment Blue 15: 6 (Pigment: pBi5: 6) Colorant: CI Pigment Violet 23 (Pigment: pV23) Acrylic Pigment Dispersant Propylene Glycol Single Methyl ether acetate 150731.doc • 124· 201113303 Mix, use a bead mill to fully disperse the pigment, and then mix (B) Resin: Resin solution H1 150 parts (C) Photopolymerizable compound: dipentaerythritol hexaacrylate ( KAYARADDPHA; capitalization 50 parts (D) Photopolymerization initiator: Irgacure OXEO1 • (manufactured by Ciba Japan Co., Ltd.) 15 parts (E) Solvent: 289 parts of ethyl lactate to obtain a colored photosensitive resin composition. The photosensitive resin composition was obtained in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The results are shown in Table 22. [Table 22] Example Comparative Example 1 2 3 4 5 1 Colorant (A) PB15: 6 (parts) 1) 33 33 33 33 33 33 PV23 (parts) 1 - - - - - 5 A1 (parts) 5 5 5 5 5 - Adhesive resin (B) Resin solution 1 ( Parts) 150 • Resin solution 2 (parts) - 148 - - - Resin solution 3 (parts) - 150 - - - Resin solution 4 (parts) - - - 150 75 - &amp; Lipid solution H1 (parts) - - - - 78 150 Photopolymerizable compound (C) Dipentaerythritol hexa-propionate (part) 50 50 50 50 50 50 Photopolymerization initiator (D) OXE-01 (part) 15 15 15 15 15 15 Solvent (F) Acid Ethyl ester (parts) 289 289 289 289 289 289 △ Eab* 4.8 4.3 4.5 3.6 3.9 8.7 1) PB15: 6 is mixed and dispersed with an acrylic dispersant (5 parts) and PGMEA (137 parts). 150731.doc • 125- 1 PV23 is mixed with PB15:6 (33 parts) with acrylic dispersant (5 parts) and PGMEA (137 parts). 201113303 [Synthesis Example 7] (Synthesis Example of Compound of Formula (2)) After adding 200 parts of water to 10.0 parts of toluidine-4-sulfonic acid represented by formula (a-2), it was cooled in an ice bath. Next, the pH was adjusted to 7 to 8 using a 30% aqueous sodium hydroxide solution. The following operations were carried out under ice bath cooling. 11 1 part of sodium nitrite was added and stirred for 30 minutes. 39.0 parts of 35% hydrochloric acid was added in a small amount in a small amount to prepare a brown solution, and the mixture was mixed for 2 hours. To the reaction solution, an aqueous solution obtained by dissolving 10.1 parts of aminosulfuric acid in 1 part of water was added and stirred to obtain a suspension containing a diazonium salt.

Adding 125 parts of water and N-methyl to 14.0 parts of 1-(2-ethylhexyl)-3-cyano-4-indolyl-6-hydroxypyridin-2-copper represented by formula (c-2) After 25.0 parts of pyrrolidone, the pH was adjusted to 8~9 by using a 3 〇% aqueous sodium hydroxide solution under ice cooling.

The following operation is carried out under ice-cooling to form a colorless solution. The above aqueous solution of pyridone is stirred.

Thereby, the yellow suspension is obtained into 8~9, liquid. Drop addition knot 150731.doc -126- 201113303 liquid. The yellow solid obtained by filtration was dried under reduced pressure at 60 ° C to give 21.4 parts of the compound of formula (d-3) (yield: 87%).

HO^S -4 Vn=n Dissolve compound (d-3) 0.35 g in N,N-didecylguanamine to make the volume reach 250 cm3, and dilute 2 cm3 of it with water to make the volume reach 1〇. 〇cm (concentration: 0.028 g/L), the absorption spectrum was measured using a spectrophotometer [quartz tank, length of the groove 1 cm]. The compound showed an absorbance of 2.9 (arbitrary unit) at ληΐ3χ = 433 ηιη. 5 parts of the compound (d-3), 35 parts of acetonitrile, and 6 parts of N,N-dimethylguanamine ι·6 were placed in a flask equipped with a cooling tube and a stirring device, and maintained at 20 ° C or lower while stirring. Add 24 parts of sulfoxide to the side. After completion of the dropwise addition, the temperature was raised to 40 ° C, and the mixture was allowed to react at the same temperature for 2 hours, and then cooled to 20 C. The cooled reaction solution was poured into 15 parts of ice water while stirring for 3 minutes. The precipitated yellow crystals were separated by 充分 "cleaned thoroughly with tap water" and dried at room temperature for several hours. In addition, a flask equipped with a cooling tube and a mixing device was prepared, and 2 parts of chloramine 2 -propanol and 2 parts of N-methylpyrrolidone were administered, and the mixture was kept under the stirring for 1 hour. The yellow crystals prepared by the present invention were introduced. After the yellow solid was charged, the temperature of the liquid was raised to the temperature of the liquid, and the mixture was stirred until the coffee was finished: the reaction solution was stirred for 30 minutes. To the reaction solution, 40 parts of a solution and 40 parts of a dry solution were added and stirred, and the mixed solution was added to a mixture of 29 parts of acetic acid and 300 parts of ion-exchanged water while stirring, 150731.doc • 127-201113303. The crystals are precipitated. The precipitated crystals were separated by filtration, washed thoroughly with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain 3.9 parts of a compound of the formula (m.sub.3) (yield: 69%).

0.35 g of the compound (111-3) was dissolved in ethyl lactate to a volume of 250 cm3, and 2 cm3 of the compound was diluted with ion-exchanged water to a volume of 100 cm3 (concentration: 0.028 g/L) using spectrophotometry. The absorption spectrum was measured (quartz cell, optical path length: 1 cm). The compound showed an absorbance of 2·3 (arbitrary unit) at Xmax = 431. The following reaction was carried out under a nitrogen atmosphere. After the hydrazine-hydrazinopyrrolidone was added to the compound (ΙΠ_3) 2 parts, the mixture was stirred for 3 minutes to prepare a reaction solution. The reaction solution was stirred while stirring at room temperature, and 0.1 part of ruthenium dichloride was added dropwise. After the completion of the dropwise addition, the mixture was further stirred for 8 hours. After the reaction solution was poured into 300 parts of water, 8 parts of ethyl acetate was added and stirred for 3 minutes. The organic phase was separated by using a separatory funnel, and further washed with 5 parts of water, 5 parts of a 1% by weight aqueous sodium carbonate solution, 5 parts of a 10% aqueous acetic acid solution, and 5 parts of ion-exchanged water. The solvent of the organic phase of the partition was distilled off to obtain a compound (yield A2) of the formula (i_q). The yield was μ%. 150731.doc 128·201113303

The structure of the compound (1-6) was determined by mass spectrometry. The mass spectrometry apparatus was JMS-700 (manufactured by JEOL Ltd.). ' Mass spectrometry: ionization mode = FD+ : m/z = l200 0.35 g of compound (1-6) was dissolved in ethyl lactate to a volume of 25 〇 Q Cm '2 cm3 of which was diluted with ion-exchanged water. The volume was made up to 100 cm (/time.0.028 g/L), and the absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length 1 Cm). The compound showed an absorbance of 2.2 (arbitrary unit) at xmax = 43 1 nm. [Synthesis Example 8] (Synthesis example of the compound represented by the formula (3)) 7.5 parts of 2-amino group 4-methylsulfonyl-6-nitrophenol (CAS No. 101861-〇4·5) After adding 65 parts of water, 13 parts of sodium hydroxide was added and the mixture was decomposed and combined. After cooling in an ice bath, 6.1 parts of an aqueous solution of 35% sodium nitrite (manufactured by Wako Pure Chemical Industries Co., Ltd.) was added, and then 19.4 parts of 35% hydrochloric acid was added in a form of a human-to-human amount to dissolve and stir. A suspension containing the diazonium salt was obtained in 2 hours. Then, the water/liquid solution obtained by dissolving 5.6 parts of the aminosulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.) in 26 parts of water was slowly added to quench the excess sodium nitrite. Then, 5.6 parts of sulphonic acid (made by Wako Pure Chemical Industries Co., Ltd.) was suspended in 70 parts of water. 'Use sodium hydroxide to adjust the pH value to 8.0. At this time, a l〇% sodium hydroxide solution is appropriately added to the suspension containing the diazo rust salt 150731.doc • 129-201113303 to control the value of 151^ in the range of 7 to 7 5 for 15 minutes. The suspension was added dropwise. After the completion of the dropwise addition, the mixture was further stirred for 30 minutes, whereby a yellow suspension was obtained. Stir for 丨 hours. The nucleation solid obtained by filtration was dried under reduced pressure at 60 ° C to obtain 11.7 parts of the compound of formula (p-1) (yield: 87.%).

(P-1) 10 parts of the compound of the formula (p-2) was added to a hydrazine group (manufactured by Tokyo Chemical Industry Co., Ltd.) and dissolved, and a sulfate chain of 12 hydrate was added (111). 31 parts (manufactured by Wako Pure Chemical Industries Co., Ltd.) and 1.1 parts of sodium acetate (manufactured by Wako Pure Chemical Industries, Ltd.) were heated and refluxed for 4 and a half hours. After cooling to room temperature, the reaction solution was poured into 1500 parts of 2% saline solution. The reddish-orange solid obtained after filtration was dried under 6 Torr to obtain the compound 13.6 represented by the formula (Ζ·Π). Share (63. / 〇).

The JMS-700 of the formula (z-1) was identified by using a mass spectrometer (manufactured by the Electronics Co., Ltd.). 150731.doc •130- 201113303 Identification of compounds of formula (zl) (mass spectrometry) Ionization mode=ESI- : m/z=882.1[M-Na+r Exact Mass: 905.1 in rose red B (manufactured by Tokyo Chemical Industry Co., Ltd.) 无水8 parts were added with anhydrous gas imitation (manufactured by Kanto Chemical Co., Ltd.) 170 parts, camphorsulfonic acid, (made by Aldrich Co., Ltd. 0 parts, 4_(N, N_) 14 parts of dimethylamino)pyridine (manufactured by Tokyo Chemical Industry Co., Ltd.), 13 parts of triethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), and stirred for about 3 〇 minutes. Butyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.) 1 part of 5 parts, a solution of 47 parts of anhydrous chloroform and pre-dissolved After that, the mixture was stirred at room temperature for about 2 hours. After two times of liquid separation operation with 150 parts of 1 N aqueous hydrochloric acid solution, the organic layer was washed twice with 150 parts of 1% saline, followed by the addition of anhydrous magnesium sulfate. After stirring for about 30 minutes, the desiccant is filtered and the solvent is distilled off, thereby obtaining 20.6 parts of the compound (g-1) (yield 90%). Determination of the compound of the formula (g-1) (mass spectrometry) ionization mode = ESi+ : ^/2 = 575.3 [ M-Cr] + exact quality: 610.3

To a solution of 253 parts of the compound represented by the formula (z-I), 4? 3 parts of methanol was added to prepare 150731.doc -131 - 201113303; a solution (S3). Further, a solution (t3) was prepared by adding 8 parts of methanol ι〇 to 153 parts of the compound represented by (g_i). Thereafter, the solution (s3) and the solution (t3) were mixed at room temperature, and stirred for about 1 hour. The resulting red solid was dried under reduced pressure at 60 ° C, washed with 35 parts of water, filtered, and dried under reduced pressure at 6 〇t to obtain a compound of formula (3a-23). A3) 263 parts (yield 65%). The structure of the compound represented by the formula (3a-23) is determined by elemental analysis. The analytical equipment was an ICP (inductively coupled plasma) luminescence analyzer (ICPS_8100; manufactured by Shimadzu Corporation).

[Example 6] (Preparation of colored photosensitive resin composition) 45 parts 10 parts 5 parts 155 parts (A) Colorant: cI Pigment Green 58 (Pigment: PG58) (A) Colorant: C_I. Pigment Yellow 138 (Pigment: PY138) Acrylic pigment dispersant propylene glycol monomethyl ether acetate was mixed. 'The beads were thoroughly dispersed using a bead mill, and then mixed 150731.doc •132· 201113303 (A) Colorant: Dye A2 10 parts (B Resin: Resin solution 1 150 parts (C) Photopolymerizable compound: dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Sakamoto Chemical Co., Ltd.) 50 parts (D) Photopolymerization initiator: N-benzoquinone醯oxy-1-(4-phenylsulfanylphenyl) octyl-1-ketone-2-imine (Irgacure OXE-01; manufactured by Ciba Japan Co., Ltd.) 15 parts (E) Solvent: ethyl lactate A coloring photosensitive resin composition was obtained in 250 parts of hydrazine. A pattern was obtained in the same manner as in Example 1 and evaluated. The results are shown in Table 23. [Examples 7 to 10] A colored photosensitive resin composition was obtained in the same manner as in Example 6 except that the resin was changed or a plurality of resins were combined so as to have the composition shown in Table 23. Further, a pattern was obtained in the same manner as in Example 1 and evaluated. The results are shown in Table 23. 〇150731.doc 133- 201113303 [Table 23] Example 6 7 8 9 10 Colorant (A) PG58 (part) υ 45 45 45 45 45 RY138 (parts) 1) 10 10 10 10 10 A2 (parts) 10 10 10 10 10 Resin solution 1 (parts) 150 - - - - Resin solution 2 (parts) - 148 - - - Adhesive resin (B) Resin solution 3 (parts) - - 150 - - Resin solution 4 (parts) - - - 150 75 Resin solution H1 (parts) - - - - 78 Photopolymerizable compound (C) Dipentaerythritol hexaacrylic acid S (part) 50 50 50 50 50 Photopolymerization initiator (D) OXE-01 (part) 15 15 15 15 15 Solvent (F) Ethyl lactate (parts) 250 250 250 250 250 △ Eab* 2.2 3.0 3.3 2.9 3.1 1) PG58 and PY138 together with acrylic dispersant (5 parts) and propylene glycol monomethyl ether The acetate (155 parts) was mixed and dispersed. [Example 11] (Preparation of colored photosensitive resin composition) (A) Colorant: CI Pigment Red 254 (Pigment: PR254) 40 parts (A) Colorant: CI Pigment Red 177 (Pigment: PR177) 17 parts Acrylic pigment dispersant 146 parts of propylene glycol monomethyl ether acetate was mixed, and the pigment was sufficiently dispersed using a bead mill, followed by mixing 150731.doc -134- 201113303 (A) Colorant: Dye A3 10 parts (B) Resin: Resin solution 1 150 parts (C) Photopolymerizable compound: dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Sakamoto Chemical Co., Ltd.) 50 parts (D) Photopolymerization initiator: N-benzonitrile 1-(4-phenylsulfanylbenzene, phenyl)octane-1-one-2-imine (Irgacure OXE-01; manufactured by Ciba Japan Co., Ltd.) 15 parts (E) Solvent: 250 parts of ethyl lactate着色 A colored photosensitive resin composition was obtained. A pattern was obtained in the same manner as in Example 1 and evaluated. The results are shown in Table 24. [Examples 12 to 15] A colored photosensitive resin composition was obtained in the same manner as in Example 11 except that the resin was changed or a plurality of resins were combined so as to have the composition shown in Table 24. Further, a pattern was obtained in the same manner as in Example 1 and evaluated. The results are shown in Table 24. 〇150731.doc 135 - 201113303 [Table 24] Example 11 12 13 14 15 Colorant (8) PR254 (parts) 1) 40 40 40 40 40 RP177 (parts) 17 17 17 17 17 A3 (parts) 10 10 10 10 10 Adhesive resin (B) Resin solution 1 (parts) 150 - - - Resin solution 2 (parts) - 148 - - - Resin solution 3 (parts) - - 150 - - Resin solution 4 (parts) - - - 150 75 Resin Solution H1 (parts) - - - - 78 Photopolymerizable compound (C) Dipentaerythritol hexaacrylate (parts) 50 50 50 50 50 Photopolymerization initiator (D) OXE-01 (parts) 15 15 15 15 15 Solvent (F) Ethyl lactate (parts) 250 250 250 250 250 △ Eab* 2.5 2.9 2.6 2.2 2.5 1) PR254 and PR177 together with acrylic dispersant (6 parts) and propylene glycol monomethyl ether acetate (148 parts) In the pattern formed by the coloring photosensitive resin composition of the example, Δ Eab* shows a small value, and it is confirmed that it is highly heat-sensitive. Industrial Applicability According to the present invention, high heat resistance can be obtained. Coating film, pattern and color filter [Simplified illustration of the drawing] Fig. 1 is a view showing a method of manufacturing the color filter of the present invention BRIEF DESCRIPTION OF THE DRAWINGS Fig. 2 is a schematic view showing a method of manufacturing a color filter of the present invention. Fig. 3 is a schematic view showing a method of manufacturing a color filter of the present invention. A schematic view of a method of producing a color filter of the present invention. [Description of main component symbols] Ο

21 Glass substrate 22 TFT (switching element) 22a Gate electrode 22b Gate insulating film 22c Polycrystalline film 22d Protective film 23 Color filter layer 23A Colored photosensitive resin group 1 23a Red filter 23b Green filter 23c Blue filter 24 pixel electrode 27 signal line 29 photosensitive resin film (protection 201 '202 connection hole 150731.doc -137-

Claims (1)

201113303 VII. Application for Patent Park: 1. A colored photosensitive resin composition containing a coloring agent (A), a binder resin (B), a photopolymerizable compound (c), a photopolymerization initiator (d), and In the solvent (E), the colorant (A) is a dye-containing coloring agent, and the binder resin (b) is a binder resin containing a resin obtained by a bisphenol A type epoxy resin and a resin obtained by adding a monomer (Bb) having a carboxyl group and a polymerizable double bond to at least one of (Ba) composed of a bisphenol F-type epoxy resin, and a resin selected from the group consisting of broken tetra( IV) if, cis T succinic anhydride And reacting with at least one of (4) of the group consisting of tetrahydrophthalic anhydride, and further comprising at least one selected from the group consisting of bisphenol A type epoxy resin and bisphenol F type epoxy resin The functional epoxy compound (Bd) is reacted. 2. 3. The color-sensitive photosensitive resin composition of the epoch of item 1, wherein the dye contains a group selected from the group consisting of an azo compound, a metal compound having an azo compound as a ligand, and a dibenzopyran compound. At least one of them.著 The colored photosensitive resin composition of the long-term item 1, wherein the dye contains a dye of the compound represented by the formula (1): [Chemical Formula 1] (1) [In the formula (1), R to R4 independently represent a chlorine atom, · r6 or a carbon number of 150731.doc 201113303 6 to 10 a monovalent aromatic hydrocarbon group, and a hydrogen atom contained in the aromatic hydrocarbon group may pass through a halogen atom , -R6, -OH ' _ 〇 R6, _s 〇 3 · sc > 3H, so3m, -co2h, -C〇2r6, -sow, _s〇2NH2, s〇2Nhr8 or -so2nr8r9 substituted; R5 represents -S〇3 , -S03H, SO3M, -C〇2H, -C02R6, _s〇3R6, -so2nhr8 or -so2nr8r9; m represents an integer from 0 to 5; when m is an integer of 2 or more, plural R5s may be the same or Different; X represents a halogen atom; a represents an integer of 0 or 1; R6 represents a monovalent saturated hydrocarbon group of 1 to 10, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom, which is contained in the saturated tobacco group _ch2_ may be substituted by -Ο-, -CO- or -nr7-; R represents a monovalent saturated hydrocarbon group having a carbon number of 1 to 1 ,, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom, the saturated hydrocarbon group _Ch2_ may be substituted by -Ο- or -CO-; R and R each independently represent a linear or branched one-valent saturated aliphatic hydrocarbon group having a carbon number of 丨~(7), and a carbon number of 3 to 3 a valence alicyclic hydrocarbon group or _Q, the saturated samarium aliphatic group and the hydrogen atom contained in the alicyclic hydrocarbon group may be via 〇H, a spectrin atom, -Q, _CH=CH2 or -CH=CHR6 Substituting, the saturated alicyclic group and the _CH2_ contained in the alicyclic hydrocarbon group may be substituted by _〇_, -s-, -CO-, -NH- or -NR6-; R8 and R9 may mutually Bonding to form a nitrogen-containing heterocyclic ring of 3 to 10 membered rings, the hydrogen atom contained in the heterocyclic ring may be substituted by R, -OH or -Q; 150731.doc 201113303 Q represents a carbon number of 6 to Η) a monovalent aromatic group or a monovalent heterocyclic group having a carbon number of 3 to ι, wherein the aromatic hydrocarbon group and the heterocyclic group are substituted by 2 LH to CH2, -CH=CHR6 or a halogen atom; Μ represents a sodium atom or a potassium atom. ; , wherein the compound represented by the formula (1) has the same charge number as the - charge number]. 4. The colored photosensitive resin composition of claim 1, wherein the binder resin (8) contains an adhesive resin of a resin obtained by a bisphenol quinone type epoxy resin and a bisphenol F type ring a resin obtained by adding a monomer (Bb) having a rebel and a polymerizable double bond to a group of Ba (E) in a group consisting of an oxyresin, and a resin selected from the group consisting of succinic acid anhydride and maleic acid At least one of the group consisting of tetrahydrophthalic acid livers (four) is reacted, and then with a polyfunctional group containing at least one selected from the group consisting of bisphenol quinone type epoxy resins and bisphenol F type epoxy resins The epoxy compound 〇 is subjected to ruthenium to make the obtained resin $ and a compound (Be) containing at least one selected from the group consisting of acethanide anhydride, maleic anhydride, and tetrahydrophthalic anhydride. Carry out the reaction. 5. The colored photosensitive resin composition of claim 1, wherein the monomer (Bb) having a carboxyl group and a poly-sigma double bond is at least one selected from the group consisting of acrylic acid and methacrylic acid. 6. The colored photosensitive resin composition of claim 1, wherein the amount of the binder resin (b) is 20 mass based on the total amount of the binder resin (B) and the photopolymerizable compound (c). /. Above, 8〇% by mass or less. 150731.doc 201113303 7. 8. 9. 10. 11. 12. 13. The colored photosensitive resin composition of claim 1, wherein the content of the dye is 0.5% by mass based on the solid content of the colored photosensitive resin composition. Above 60% by mass. The coloring photosensitive resin composition according to item 1, wherein the coloring agent further contains a pigment coloring agent. The colored photosensitive resin composition according to Item 8, wherein the pigment contains a color selected from C.1·Pigment Blue 15:6, CI Pigment Red 254, CI Pigment Red 242, CI Pigment Red 177, CI Pigment Green 58, CI· At least one of the group consisting of Pigment Yellow 150 and C.I_Pigment η 13 8 . A coating film formed by using the colored photosensitive resin composition as claimed in the claims. A pattern formed by using the colored photosensitive resin composition as claimed in the claims. For example, the pattern of the item 11 is formed by photolithography. A color filter comprising at least one selected from the group consisting of a coating film as claimed in claim 0 and a pattern such as β-terms 11 and 12. 150731.doc