TW201131294A - Colored photosensitive resin composition - Google Patents

Abstract

The present inventions provides a colored photosensitive resin composition, including: a colorant, a resin, a photopolymerizable compound, a photopolymerization initiator, a solvent and a typical metal compound, wherein the colorant contains dye and the typical metal compound contains carbon atoms, the typical metal compound has a smaller maximum molar absorptivity in the visible light region than the dye.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored photosensitive resin composition suitable for forming a colored image constituting a color filter used in a liquid crystal display element or a solid-state image sensor, and a use thereof A color light-emitting sheet of the colored photosensitive resin composition. [Prior Art] The color photosensitive resin composition is used in the production of a color light-emitting sheet used in a display device such as a liquid crystal display panel, an electroluminescence panel, or a plasma 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). [Non-Patent Document 1] Suzuki's eighty-two, "Easy-to-understand LCD display manufacturing process", the first edition, 曰刊工业新闻社, March 2005, P112 [Summary of the Invention] A coloring photosensitive resin composition of a solvent, a resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, but the contrast of the coating film formed using the colored photosensitive resin composition is not very satisfactory. The present invention provides the following [1] to [14]. [1] A colored photosensitive resin composition comprising a colorant, a resin, a photopolymerizable compound, a photopolymerization initiator, a solvent, and a typical metal compound, and the colorant is a dye-containing one, and the typical metal compound contains a carbon atom. 'The maximum value of the Mohr absorbance coefficient in the visible light region is smaller than the maximum value of the Mohr absorbance coefficient of the dye in the visible light region. [2] The colored photosensitive resin composition of the above [i], wherein the maximum value of the molar absorption coefficient of the typical metal compound in the visible light region is not less than 〇 and not more than 1,000. [I] The colored photosensitive resin composition of the above [I] or [2], wherein the typical metal compound is a group containing a group selected from the group consisting of magnesium, aluminum, calcium, zinc, gallium, lanthanum, cerium, indium, planer and cerium. a compound of at least one of them. [4] The colored photosensitive resin composition according to any one of the above (1) to (3) wherein the typical metal compound is a compound containing at least one selected from the group consisting of aluminum, indium indium and cerium. [5] The colored photosensitive resin composition of any one of (1) to [4] wherein the typical metal compound is at least one group selected from the group consisting of (where _c(=s)_ [6] The colored photosensitive resin composition of any one of the above-mentioned items (1) to (5), wherein the typical metal compound is a compound selected from the formula (F1), a compound represented by the formula (), and the At least one of the groups consisting of hydrates

(F1) (F2) [In the formula (F1) and the formula (F2), 妒 and ^ independently represent one of the aliphatic hydrocarbon groups of carbon number 6 or the "valent" aromatic hydrocarbon group of carbon number (d), the aliphatic cigarette and the 3 The hydrogen atom contained in the aromatic hydrocarbon group may be substituted by a hydroxyl group; W and W independently of each other represent a carbon number of 丨~6-valent aliphatic hydrocarbon group. 151490.doc 201131294 A hydrogen atom contained in an aliphatic sulfhydryl group may be halogenated Atom substitution; M1 and M2 represent typical metal atoms; fy represents an integer of 1 to 3, and when 乂 is an integer of 2 or more, plural ^! and w may be the same or different from each other, and when y is an integer of 2 or more, A plurality of W3 and W4 may be the same or different from each other]. [7] The colored photosensitive resin composition according to any one of the above [1] to [6] wherein the content of the typical metal compound is 质量 by mass or more based on 100 parts by mass of the total of the resin and the photopolymerizable compound. 2 parts by mass or less. [8] The colored photosensitive resin composition according to any one of the above [1] to (7) wherein the dye is a compound represented by the formula (1):

[In the formula (1), R1 to R4 each independently represent a hydrogen atom, _R6 or a carbon number 6 to a monovalent aromatic hydrocarbon group, and a hydrogen atom contained in the aromatic hydrocarbon group may pass through a dentate atom, -R6, -OH , -OR6, -S〇3-, _S〇3h, s〇3M, c〇2H '-C02R6, -S〇3r6, _s〇2NH2, -S〇2NhrS or _s〇2Nr8r9 are substituted; R5 means -S03- , -S03H, -S03M, -C02H, -C〇2R6, _s〇3r6, -so2nhr8 or -so2nr8r9; m represents an integer from 0 to 5, and when m is an integer of 2 or more, plural R5s may be the same or different X represents a halogen atom; 151490.doc -5- 201131294 a represents an integer of 0 or 1; R represents a one-value saturated nicotine group of 1 to 1 ,, the hydrogen atom contained in the saturated nicotine group may pass through a halogen atom Alternatively, _Ch2_ contained in the saturated hydrocarbon group may be substituted with -Ο-, -CO- or -NR7-; 7 R represents a one-valent saturated hydrocarbon group having a carbon number of 1 to 1 ,, and hydrogen contained in the saturated hydrocarbon group The atom may be substituted by a halogen atom, and the _Ch2_ contained in the saturated hydrocarbon group may be substituted by -Ο- or -CO-; R and R each independently represent a linear or branched monovalent saturated fat having a carbon number of 1 to 10. Family hydrocarbon group, carbon number 3~30 one-price alicyclic ring a hydrocarbon group or _Q, the saturated aliphatic nicotyl group and a hydrogen atom contained in the alicyclic hydrocarbon group may be substituted by 〇H, a halogen atom, -Q, -CH=CH2 or -CH=CHR6, the saturated aliphatic group The hydrocarbon group and -CH2- contained in the alicyclic hydrocarbon group may be substituted by -〇-, _c〇_, NH- or -NR6-; R8 and R9 may be bonded to each other to form a 3~1 〇 ring a heterocyclic ring of a nitrogen atom, the hydrogen atom contained in the heterocyclic ring may be substituted by R6, _0 or -Q; Q is not a slave 6 to 10 one-valent aromatic hydrocarbon group or a carbon number of 5 to 1 〇 a hetero atom, the aromatic hydrocarbon group and a hydrogen atom contained in the heterocyclic group may be substituted by -OH, R6, -OR6, -N〇2, _CH=CH2, _ch=chr6 or (d) 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]. [9] The colored photosensitive resin composition according to any one of (1) to [8] wherein the coloring agent is a pigment-containing composition. [10] The colored photosensitive resin composition according to [9] above, wherein the pigment is one containing 151490.doc 201131294 C _ I · Pigment Blue 1 5:6. [11] The colored photosensitive resin composition according to the above [10], wherein the mass ratio of the pigment containing the pigment blue 15:6 to the dye containing the compound represented by the formula (1) is from 97:3 to 50:50. [12] A coating film obtained by applying the coloring property of any of the above-mentioned items [u] to [u], and drying the composition. [13] A pattern obtained by applying the colored photosensitive resin composition according to any one of the above [1] to [11] and drying it. And 彩色4] a color filter comprising at least one selected from the group consisting of the coating film of the above [i 2] and the pattern of the above [13]. [Embodiment] Hereinafter, the present invention will be described in detail. The colored photosensitive resin composition of the present invention contains a coloring agent (A). The coloring agent (8) used in the colored curable resin composition of the present invention is a dye-containing coloring agent. The dye contained in the colorant (A) is not particularly limited, and a known dye can be used. For example, an oil-soluble dye, an acid dye, an amine salt of an acid dye or a sulfonamide derivative of an acid dye may, for example, be mentioned. The type of dye can be selected according to the target's spectroscopy. As the dye, for example, a dye classified as a dye in the "Dye Index" (published by Dings and Dyers and Colourists) or a dye known as a dyeing note (color dyeing company) can be cited. Specific examples thereof include CI Solvent Yellow 4 (hereinafter, "c·!. Solvent Yellow" is omitted, and only the number is described), 14, 15, 23, 24, 38, 62, Ο, Μ, Μ, 151490.doc 201131294 94 > 98 '99 ' 162 ; CI solvent red 45, 49, 125, 130; CI solvent lamp 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. In addition, as the CI acid dye, CI Acid Yellow 1, 9, 11, 17, 23, 25, 29, 34, 36, 38 , 40, 42 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 116, 119, 123, 128, 134, 135, 138, 139, 140, 150' 155, 157, 160, 161, 163, 168, 169, 172, 178, 179, 184, 190, 193, 196, 197, 199, 202, 204' 205, 207, 212, 214 '220, 221, 228 '230, 235, 238, 240, 242, 243, 251; CI acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80 88 , 91 , 92 , 94 , 173, 117, 145, 151, 158 , 260 , 261 , 266 ' 268 , 270 ' 274 , 277 , 280 , 195 , 308 , 312 , 315 , 316 , 339 ' 341 , 345 , 346 , 382 ' 383 , 394 , 401 , 412 , 417 , 418 , 422 426; CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; CI Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40 151490.doc 35 and so on. 3, 7, 54, 54, 114, _ 177, 203, ' 232 ', 34, 87, 134, 198, • 257 ' 281, 349, 62, 42, 2011 31294 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;

C-I. Acid Green Dyes such as 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109. Further, as the CI direct dye, CI direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95 , 98, 102, 108, 109, 129, 136, 138, 141; CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221 '222, 232' 233, 234, 241, 243, 246, 250; CI Direct Orange 34, 39, 41 , 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI Direct Blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156 '158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 196 '198 ' 199, 200 ' 207 ' 209 , 210 ' 212 ' 213 ' 214, 222, 228 ' 229 ' 237 , 238 ' 242 , 243 , 244 , 245 , 247 , 248 ' 250 , 251 , 252 , 256 , 257 , 259 , 260 , 268 , 274 , 151490.doc -9- 201131294 275 ' 293 ; CI · Direct purple 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; CI direct green 25, 27, 31, 32, 34, 37, 63, 65, 66 '67, 68, 69, 72, 77, 79, 82 and other dyes. In addition, as the CI mord dye, CI mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; CI 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, 40, 41, 44, 45, 47, 48, 53, 58; CI mord green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53 and other dyes. Further, examples of the dye contained in the coloring agent (A) include an azo dye, a metal-missing salt azo dye, an anthraquinone dye, a triphenylmethane dye, a dibenzopyran dye, a cyanine dye, and naphthalene. Anthraquinone dyes, quinone imine dyes, methine dyes, squaric acid dyes, and phthalocyanine dyes. In the dye contained in the coloring agent (A), a dibenzopyrene dye is preferred, and a dye containing a compound represented by the following formula (1) is more preferred. [Chemical 1]

In the compound represented by the formula (1), r1 to r4 each independently represent a hydrogen atom and an aromatic hydrocarbon group having a carbon number of 6 to 10. The above V represents a one-valent saturated hydrocarbon group of carbon number. In addition, the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom, and _CH2_ may be via _〇_, -CO- or -nr7- (r7 represents a saturated hydrocarbon group of carbon number (7), and the carbon number is 1 The hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom, and the -CH2_ may be substituted by -〇- or -CO-). Examples of -R6' include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, and heptyl groups. ,cycloheptyl, octyl, 2-ethylhexyl, cyclooctyl, decyl, decyl, tricyclodecyl, methoxypropyl, ethoxypropyl, hexyloxypropyl, 2-B Hexyloxypropyl, nonyloxyhexyl, ethoxypropyl, and the like. Examples of the one-valent aromatic hydrocarbon group having 6 to 1 carbon atoms of RtR4 and Q include a phenyl group and a naphthyl group. In addition, the hydrogen atom contained in the one-membered aromatic ketone group having a carbon number of 6 to 1 Å of R to R may pass through a halogen atom, -r6, _〇h, -OR6, _s〇3-, _s〇3h, - So3m, -C02H, -C02R6, _s〇3R6, -S〇2NH2, -so2nhr8 151490.doc -11 · 201131294 or -so2nr8r9 replaced. The above R6 represents the same meaning as described above. The above R8 and R9 each independently represent a direct bond or a bond of a carbon number of 10, a strictly saturated aliphatic hydrocarbon group, a carbon number of 3 to 30, a monovalent alicyclic hydrocarbon group or a _q (1) table: carbon number (d)-valence aromatic The hydrocarbon group or the carbon atom having a carbon number of 3 to 1 Q, the hydrogen atom contained in the group or the like may be substituted by _OH, _R6, _〇R6, _N〇2, "-CH=CHR6 or a halogen atom). 2 The linear or branched-chain-saturated aliphatic group of carbon number in R8 and R9 and the hydrogen atom contained in the alicyclic ketone group having a carbon number of 3 to 30 may be: -0H, a halogen atom, _Q, _CH=CH2 or _ch=chr6 may be substituted by -◦_, _S-, -CO-, -NH- or -NR6-. R and R may be bonded to each other to form a nitrogen-containing heterocyclic ring of a 3 to a member ring. At this time, the hydrogen atom contained in the far heterocyclic ring may be substituted by _R6, _〇11 or. Further, the above Μ represents a sodium atom or a potassium atom. Examples of the functional atom of the hydrogen atom contained in the aromatic smoky group having a carbon number of 6 to 1 (1) which can be substituted for the RLR4 towel include a gas atom, a chlorine atom and an agar atom. As -OR6, for example, methoxy, ethoxy, n-propoxy, isopropanyl, n-butoxy, second butoxy, tert-butoxy, n-decyloxyn-hexyloxy a group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a decyloxy group, a decyloxy group, etc. Examples of the -CChR6 include a decyloxycarbonyl group, an ethoxycarbonyl group, and a propoxy group. , isopropoxy group, butoxy m group, isobutoxy methane, decyloxycarbonyl, isopentyloxycarbonyl, neopentyloxycarbonyl, cyclopentyloxy 151490.doc -12· 201131294 , hexyloxy, cyclohexyloxy, heptyloxy, cycloheptyloxy, octyloxy, -2-hexyloxy (tetra), cyclooctyloxy Keto group, decyloxy group, tricyclodecyloxy group, methoxypropoxy group [oxypropoxycarbonyl group, hexyloxypropoxycarbonyl group, ethylhexyloxypropoxy group , methoxyhexyloxycarbonyl, etc. As -S〇3R6, for example, can be listed as cool. Tian g #廿^ 歹] 曱 曱 曱 碛醯 、, ethoxy sulfonyl, hexyloxy sulfonium Base '癸oxysulfonyl group, etc. -so2nr8r9, as r8^r9

The 3~10 member ring of the 3 3 ring atom formed by the mutual exchange of the gas eyebrows „ ” can be cited as:

Q I The binding bond and sulfur atom in the above figure

As a carbon number of Q 3 to 10, a heterocyclic group can be enumerated: 151490.doc -13- 201131294

Further, the bond of the heterocyclic group of Q may be any position. Examples of -SOzNHR8 include N-methylamine sulfonyl group, N-ethylamine stone aryl group, N-propyl amine powder base, N-isopropylamine continuation base, and ST-butyl group. Aminestone, N-isobutylamine sulfonyl, N-pentylamine sulfonyl, N-isoamylamine, N-neopentylamine sulfonyl, N-cyclopentylamine sulfonate Sulfhydryl, N-hexylamine sulfonyl, N-cyclohexylamine sulfonyl, N-heptylamine sulfonyl, N-cycloheptylamine sulfonyl, N-octylamine sulfonyl, N-( 2-ethylhexyl)amine sulfonyl, NK1,5-dimethylhexylamine sulfonyl, N-cyclooctylamine sulfonyl, N-decylamine sulfonyl, N-decylamine Sulfhydryl, mutricyclodecylamine sulfonyl, N-methoxypropylamine sulfonyl, N-ethoxypropylamine sulfonyl, n-propoxypropylamine sulfonyl, N -isopropoxypropylamine sulfonate, N-hexyloxy

Further, examples of -SC^NHR8 include a group represented by the following formula. [Chemical 2]

[Chemical 3] 151490.doc •14- 201131294 NHSO- NHSO2 ,2 ^jws〇2 NHS〇2 'NHS〇a [Chemical 4] «〇2 NHSO, Ιη^2

❹ 〇2?hn OzSHN^ OjSHN- , N. nhso2 NHS〇2 I 2 i [Chemical 5] S〇i HO~NH; ΗΟ-^-^ΝΗέΟ, NHSOj

OH NHSO: 2 Ο NHSOj xi-^\^nhso2 χΐ*Λνν^'ΝΗ3〇2 CF3CH2NHS〇2 CF3(CF2)7CH2NHS〇2 Cfv^^^Js^NHSOj In the above formula, X1 represents a halogen atom. The halogen atom of X1 is a fluorine atom, a chlorine atom or a bromine atom. [Chem. 6] can be listed

MeO-NHi 'NHSOz /0 ^0'^n'NHSO2 >|^〇'NHS02 ^νη4〇2 , 〇丄 νη^ο2 〇Ν NHS〇2 O'

151490.doc 15- 201131294 [Chem. 7]

HO

, NHS〇2 /N, ^^nhso2 [化*8]

Η Λ NHS〇2 Λ

ο ci^A

".2 NC J o NHS〇2 MeO^^NHS02

O

Nhso2 NHS〇2

hhL2 ^Λνη i〇3 [化9]

NHi〇2 ".2 NH^〇2 NHS〇2 ό ό-χ3 0~F4 丄2 NHS〇2 NHS〇2 ό-- 0"ci2 0~Br2 In the above formula, X3 represents a carbon number of 1 to 3 Alkoxy group having 1 to 3 carbon atoms; the hydrogen atom of the alkyl group and the alkoxy group may be substituted by a halogen atom. -16- 151490.doc 201131294 As an alkyl group having 1 to 3 carbon atoms which may be substituted by a halogen atom, A group, an ethyl group, a propyl group, an isopropyl group, a trifluoromethyl group, etc., an alkoxymethoxy group having 1 to 3 carbon atoms which may be substituted by a halogen atom, an ethoxy group, a propoxy group or the like. ] Can be listed: A, can be listed:

[化11]

[化 12]

151490.doc -17- 201131294 [Chem. 13]

In the above formula, X3 represents the same meaning as described above. In the above formula, X2 represents an alkyl group having a carbon number of 3, a carbon atom of a carbon number of 3 or a Schiffky group, and the hydrogen group contained in the alkyl group and the alkoxy group is substituted with a halogen atom. Examples of the halogen atom of X2 include a single atom, a chlorine atom, and an atom. Examples of the alkyl group which may be substituted with an i atom are a methyl group, an ethyl group, a propyl group, an isopropyl group or a trifluoromethyl 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. 151490.doc -18· 201131294 [Chem. 15] NHSOj

OX" 03⁄4 〇> 二仏Ο, wherein, as -S02NHR8', R8 is a branched saturated aliphatic hydrocarbon group having 6 to 8 carbon atoms, an alicyclic hydrocarbon group having 5 to 7 carbon atoms, an allyl group, a phenyl group having an anionic number of 8 to 10, a saturated aliphatic group having an alkyl group having 2 to 8 carbon atoms and an aryl group or a saturated aliphatic hydrocarbon group having an alkoxy group having 2 to 8 carbon atoms Particularly preferred is that R8 is 2-ethylhexyl. 5 Examples of -S〇2NR8R9 include a group represented by the following formula. [Chemistry 16]

[Chem. 17]

Fh

151490.doc -19- 201131294 S〇2 S02 [Chem. 18]

[Chem. 19]

151490.doc -20- 201131294 [Chem. 20] Ο

,. 1>again

R8 and R9 contained in 4 sS 2Nr8r9 are preferably a branched saturated aliphatic hydrocarbon group having 6 to 8 carbon atoms, an alicyclic hydrocarbon group having 5 to 7 carbon atoms, an allyl group, and a ninth number. 8 10 of the aromatic base, the number of 2 to 8 containing saturated amino acid

The hydrocarbon group and the aryl group or the alkoxy-containing saturated aliphatic hydrocarbon group or aryl group having a carbon number of 2 to 8 are particularly preferably 2-ethylhexyl. The substituent of the aromatic hydrocarbon group having a carbon number of 6 to r of r to R4 in the formula (1) is preferably ethyl, propyl, phenyl, dimethylphenyl, _s〇3r6 or -so2nhr8. . Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms having a substituent include methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, hexylphenyl, nonylphenyl, &; phenyl, phenyl, bromophenyl, phenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, decyloxyphenyl, trifluoro Methyl phenyl and the like. 151490.doc -21· 201131294 In R to R4 in the formula (1), it is preferred that at least one of the ruler and R2, or at least one of R and R is a carbon number of 丨~4 The saturated hydrocarbon group may have a carbon number of 6 to 10 monovalent aromatic hydrocarbon groups. Further, it is preferred that at least one of R1 and R2, and the eve of R3 and R4 are a carbon number of 1 to 4 one-valent saturated hydrocarbon group or a substituted carbon number of 6 to (7) * aromatic hydrocarbon group Particularly preferred is at least one of the ruler and the ruler 2, and at least one of r3 and R is a carbon number 6 to 10 one-valent aromatic hydrocarbon which can be substituted ^ = 'in the compound represented by the formula (1) R5 represents _s〇3·, _s〇3H, C02H > -C02R6 . -S〇3r6 . -so2nhr8^-so2nr8r9 In the formula (1), m represents an integer of 0 to 5, when 〇1 is 2 In the above integer, a plurality of R5s may be the same or different. Preferred examples of R5 include a carboxyl group, an ethoxycarbonyl group, a sulfo group, an N-(2-ethylhexyloxypropyl)amine fluorenyl group, and a dimethylhexylamine stone xanthine (3phenyl-1). -Methylpropyl)aminesulfonyl, N-isopropoxypropylsulfonyl. In the formula (1), X represents a halogen atom, and a represents an integer of ruthenium or osmium. Examples of the atom of X which is not represented by X include a gas atom, a chlorine atom atom and the like. - a compound of the formula (preferably, a compound represented by the following formula (b) or (1-2). 151490.doc -22- 201131294 [Chem. 21]

[Aroma of u 6 to 10 in the formula (1-1) _ its ~" independently represents a hydrogen atom, -R6 or a carbon number atom, and also a hydrogen atom contained in the aromatic hydrocarbon group. Rn UK, -S〇3-, -S03H, -S03Na, -C02H, -CU2K ' -S〇3j^6 generation. , -S〇2NH2, -so2nhr8 or -S02NR8R9 Take R15 for hydrogen or -s〇2nr0 atom, _S〇3_, -s〇3H, -s〇2NH2, -s〇2NHR8 R16 for -S〇3_, R6, r8 , r9, 's〇3H, _s〇2NH2, -so2NHR8 or -so2nr8r9. J: Φ , , 111, x&a denote the same meaning as described above. , A-type household /f - 〇 [Chem. 22] The juice does not have a compound + charge number is the same as - charge number]

»22 R

(1-2) [In the formula (1-2), the aromatic oxime to R of R2 4 6 to 10 independently represent a hydrogen atom, -R26 or a carbon number atom, and R^ group h in the aromatic smog group. Containing hydrogen atoms can pass through South-S03' '-S03Na ' -C02H '

'〇H > -〇R 26 151490.doc •23- 201131294 -C02R26, -S03H, -S03R26 or -so2nhr28 replaced. 2 5 R represents -S〇3-, _S〇3Na, _C〇2h, _c〇2R26, -so3h or -so2nhr28. 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 -OR27 or a halogen atom. R represents a saturated hydrocarbon group having 1 to 10 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group may be substituted by a fang 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 hydrocarbon group may be substituted by _R26 or -OR26. m, X and a represent the same meanings as described above. Among them, the compound of the formula (1-2) has the same number of + charges as the number of _ charges. Further, the compound represented by the formula (1) is preferably a compound represented by the following formula (1-3). [Chem. 23]

Η U

The hydrogen atom may be substituted with a (tetra) atom, ·r26, only 26, _co2r26, -so3R26 or -so2nhr28. R33 represents -so3. or -S〇2nhr28. R represents no hydrogen atom, -S〇3- or _s〇2NHR28. 151490.doc -24· 201131294 R26, r28, γ, and a represent the same meaning as above. Among them, the number of + charges of the compound represented by the formula (1-3) is further the same as the number of electric charges. ] 卞 is a compound represented by the formula (1), more preferably a compound shown. The following formula (1-4)

[Chem. 24]

(1-4) In the formula [1-4], R4 and R42 each independently represent that the hydrogen atom of the phenyl group may be substituted by -R26 or -sc^NHR28. R represents ·s〇3· or -so2nhr28. 〇 26 ^28 , K , x and a represent the same meaning as above. The compound represented by the formula (1_4) has the same number of + charges as the number of charges. ]

Examples of the compound represented by the formula (1) include compounds represented by the following formulas (ia) to (9). [Chem. 25]

[In the formula (la), R5i and R52 each independently represent a hydrogen atom, _s〇3H, -c〇2H or -S〇2Nhr5G. R5. Represents 2 ethyl hexyl. M a represents the same meaning as described above. 151490.doc •25· 201131294 where the compound of formula (la) has the same charge number as the charge number [Chem. 26]

(1b) [In the formula (lb), R5i - R is not the same as the above-mentioned compound + 荇 1 盥 + 3 sense. Wherein, the number of equations (lb) is the same as the number of _charges. The compound of the formula (lb) is a compound. Tautomerization of non-compounds [Chem. 27]

(1M) [In the formula (lb-Ι), r5i, in and a are not related to the above, and the compound represented by the formula (lb-Ι) is 3 sense. Its [Chemical 28] sentence + electric number and - charge number are the same. ]

Rs* (1C)

R^S

(1d), ^^ respectively indicate that 151490.doc -26 - 201131294, -S03Na or -SO2NHR50 are in the formula (lc) and formula (id). R5° represents 2-ethylhexyl. Here, the compound represented by the formula (1c) and the compound represented by the formula (1d) have the same charge number and charge number. ] [Chem. 29]

(1e) 〇0 [In the formula (le) and the formula (If), R56, R57 and R58 each independently represent a hydrogen atom, -S03-, -S03H or -S02NHR50. R50 represents 2-ethylhexyl. The + charge number and the charge number of the compound represented by the formula (Ie) and the compound represented by the formula (If) are respectively the same. Specific examples of the compound represented by the formula (1 a) to the formula (1 f) include a compound obtained by hydrating amygdalin B, a red rose b-S03- or -S03H, and a hydrazine amination. CI Solvent Red 49, Rose Bengal B, CI Acid Violet 102, CI Acid Violet 102-S〇3_ or -S〇3H Compound obtained by sulfoximation, c_I. Acid Red 289, CI Acid Red 289 S〇3_ or _s〇3H is obtained by sulfoximation and the like. Among them, the dye used in the colored photosensitive resin composition of the present invention is preferably a compound represented by the formula (le) or the formula (If), and specifically 5' is preferably a CI acid red 289, ci. Acid red 289-S〇3_ or -S〇3H is obtained by sulfoximation. Particularly preferred are the compounds of the formula (A-Ι). [化30] 151490.doc -27- 201131294

The compound represented by the formula (1) can be produced, for example, by chlorinating the pigment or pigment intermediate having the same color as in the conventional method, and obtaining the pigment or the pigmented interdental body having the mother C1 and the r8 The amine shown is reacted. In addition, it is also possible to produce a dye produced by the method described in the above-mentioned upper right column to the lower left of the 31st of Japanese Patent Laid-Open No. Hei. No. 3,787,2, in the same manner as described above, and then The amine is reacted. As the coloring agent (4), a dye can be selected according to the color of the target color filter, and a plurality of dyes can be used in combination. When the heart coloring agent (4) contains the compound represented by the formula (1), the compound represented by the formula (1) of the coloring agent (A) t is preferably contained in the phase 3 of the compound such as the sizing agent 3 with respect to the coloring agent (A). It is 3 to 80 baht % 'extra good is %.疋J 7 〇Berry%, more preferably 3 to 50 mass: when the coloring agent (4) contains a compound represented by the formula (1) and a dye different from the hydration compound of the formula (1), - fly (1) The mixing of the different compounds and the dyes different from the compound of the formula (1) is within the following range. "A compound having a higher U ratio than the compound of the formula (1): 1 to 99% by mass to 99% by mass. A spectroscopic target having a different target of the compound. A dye different from the compound of the formula (1). When the compound represented by the formula (1) and the formula (1) are in the above range, the content of the dye can be obtained from the solid content of the colored photosensitive resin composition. Preferably, the knives are 〇5 to 6 〇 mass%, more preferably 〇7 to 5 〇 mass%, and even more preferably 1 to 40 mass. Here, the solid content component means The coloring agent (A) may contain a pigment in addition to the dye. The pigment may, for example, be an organic pigment or an inorganic pigment, and may be exemplified by the "dye 4 index". (Compounds classified as pigments in The Society of Dyers and Colourists). Specific examples of the organic pigment include: CI Pigment Yellow 1, 3 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86 93, 94, 1〇9, 11〇 Yellow pigments such as 117, 125, 128, 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, 160, 168, 176, 177 ' 18 〇, 192, 2〇9, 215, 2ΐ6, 224, μ, 254, 255, 264, 265 and other red pigments; CI pigment blue 15, 15:3, 15:4, 15:6, 60 and other blue pigments; c·; • 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, etc. Among them, CI Pigment Yellow 138, CI Pigment Yellow 139, c丄 151490.doc -29- 201131294 Yellow 150, CU•Pigment Red C.1·Pigment Red 209, CI Pigment Red 242, CI Pigment Red are preferred. 254 .. 颜枓,,工糸23, CI Pigment Blue 15:3, C, I. Pigment Blue 15:6 and CI Yan Xi Lu 7 n τ c〇〃,, Pro 7, CI Pigment Green 36, CI · Pigment Green 58. These pigments may be used singly or in combination of two or more.

The above-mentioned pigments may also be treated by the yoke of the yoke, the surface treatment of the pigment derivative or the pigment dispersion, or the like, and the grafting treatment of the surface of the pigment by using a sub-compound or the like. The use of the sulfuric acid micronization method for the micronization treatment of the niobium, or the cleaning treatment by the organic solvent or water, etc., and the removal of the ionic impurities by the ion exchange method, etc. #x, the pigment is preferably a pellet. The diameter is even. The pigment dispersion liquid in a state in which the pigment is uniformly dispersed in the solution can be obtained by dispersion treatment with a pigment dispersant. As the pigment dispersant, a commercially available surfactant can be used, and examples thereof include polyfluorene-based, fluorine-based, I-based, cationic, anionic, nonionic, amphoteric, polyester, and polyamine. A surfactant such as an acrylic acid or the like may be used alone or in combination of two or more. As the above-mentioned interface-active sword, it is possible to use 丨·················································· , fatty acid modified polyacetate, tertiary amine modified polyamino carboxylic acid vinegar, polyethylenimine, etc., in addition, may also be listed under the trade name KP (Shin-Etsu Chemical Industry Co., Ltd.) Polyfl()w (manufactured by Kyoeisha Chemical Co., Ltd.), Eftop (Mitsubishi Gentleman (5), (4) Co., Ltd.), Megaface (made by mc Co., Ltd.), ^(10)d (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard (Asahi Glass Co., Ltd. has 151490.doc -30·201131294 limited company manufacturing), Surflon (AGC Seimi Chemical Co., Ltd.)

Manufactured, manufactured by 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 5 parts by mass or more and 0.5 part by mass or less. If the amount of the pigment dispersant is in the above range

Internally, there is a tendency to obtain a pigment dispersion liquid in a uniformly dispersed state, which is preferable. The dye and the pigment may be used alone or in combination of two or more. In addition, dyes and pigments can be used in any ratio. The content of the dye in the colorant (A) is usually from 1 to 100% by mass, preferably from 3 to 95% by mass, more preferably from 5 to 80% by mass. The content of the pigment in the colorant (A) is usually from 〇 to 99% by mass, preferably from 5 to 97% by mass. /. More preferably, the content of the dye and the pigment is within the above range, and the knives X which can be obtained are excellent in heat resistance and lightness. The mass ratio of the compound shown is, in particular, the case where the pigment is CI pigment blue ruthenium is preferably CI·Pigment Blue 15:6 and formula 〇) 97:3 to 50:50 ° with respect to coloring sensitivity The content of the solid content in the resin composition, the content of the colorant (4) is preferably 5, % by weight, more preferably 8 and more preferably 1 Torr to 5% by mass. When the content of the coloring agent (4) is in the above range of 151490.doc * 31 - 201131294, the color density at the time of forming the color filter is sufficient, and the necessary amount of the resin can be contained in the composition, so that the mechanical strength can be sufficiently formed. The tendency of Figure = is better. The colored photosensitive resin composition of the present invention contains a resin (B). The resin (B) is preferably a resin which is soluble in a developing solution (especially an alkali developing solution) used in the photolithography method, and more preferably has an acidic functional group such as a carboxyl group, a phenolic hydroxyl group or a sulfo group (and furthermore Good is the resin of carboxyl). The preferred resin (B) is at least one monomer (4) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and monomer (8) different from the monomer (4) having an ethylenically unsaturated bond ( Hereinafter, it is simply referred to as a "monomer (χ)") copolymer. ^ The body (4) and the monomer (8) may be used alone or in combination of two or more. Examples of the monomer (a) include (meth)acrylic acid, crotonic acid, cinnamic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, and succinic acid mono [2_(methyl). ) propylene methoxyethyl] phthalate mono [2_(methyl) propylene oxyethyl] phthalate, ω-carboxy polycaprolactone mono (meth) acrylate, 5-carboxyl_5 _Methylbicyclo[2.2.1]hept-2-ene, 5-sided _5-ethylbicyclo[221]hept-2-ene, 5-carboxy-6-methylbicyclo[2·2.__2_ene , cumyl ethyl bicyclo [22"] hept-2-saturated monounsaturated monocarboxylic acid; butyl succinyl g anti-succinic acid, citraconic acid, mesaconic acid, itaconic acid, 3_vinyl Phthalic acid, 4_vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 152,3,6-tetrahydroortylene dicarboxylic acid, dimethyltetrachloro-o-phenyl Formic acid '1,4-cyclohexene dibasic acid, methyl _5_norfosene bismuth subacid, etc. 151490.doc -32· 201131294 Unsaturated dicarboxylic acid; maleic anhydride, citraconic anhydride, clothing Tonic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic acid 1,2,3,6-tetrahydrophthalic anhydride, dimercaptotetrahydrophthalic acid needle, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (bicycloheptane Alkene phthalic anhydride) 'isounsaturated dicarboxylic anhydrides; Among these, '(meth)acrylic acid is preferred, and mercaptoacrylic acid is more preferred. Further, in the present specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The expressions "(meth)acryloyl" and "(meth)acrylate" have the same meaning. The monomer (X) preferably contains a monomer having an ethylenically unsaturated bond and a hardenable group, and more preferably a monomer having an ethylenically unsaturated bond and a ring number of 2 to 4 (b) ) (hereinafter referred to as "monomer (b)"). When a resin containing a monomer having a Q-hardenable group is used as the resin (B), the reliability (heat resistance, light resistance, solvent resistance, mechanical properties, etc.) of the obtained coloring pattern tends to increase. Preferably, the monomer (b) having an ethylenically unsaturated bond and a cyclic ether having 2 to 4 carbon atoms may be used singly or in combination of two or more. Examples of the monomer (8) include a monomer having an ethylenically unsaturated bond and an ethylene oxide ring, a monomer having an ethylenically unsaturated bond and a propylene oxide ring, and an ethylene group. An unsaturated bond and a monomer (10) of a tetrahydroanthracene ring. Among these, a monomer having an ethylenically unsaturated bond and an ethylene oxide ring, and a monomer having an ethylenically unsaturated bond and a propylene oxide ring of 151490.doc -33 - 201131294 are preferred. (b2), more preferably a monomer having an ethylenically unsaturated bond and an oxirane ring (Μ). VIII as a monomer having an ethylenically unsaturated bond and an oxirane ring, and a single structure having an ethylenically unsaturated bond and an epoxidized structure of an olefin (ie, a monocyclic epoxy ring) The body (bl_1) (hereinafter referred to as "monomer") and the structure of an epoxidized ring having an ethylenically unsaturated bond and a cyclic olefin (ie, a structure in which a ring of an aliphatic hydrocarbon is condensed with an epoxy ring) single. The body is called -2) (hereinafter referred to as "monomer (μ_2)"). In the middle, it is better to single = (bl-2). As the above cyclic olefin, fluorene is exemplified by a cyclic olefin of a monocyclic ring such as cyclopentene or cyclohexylene; a cyclic olefin of a crosslinked ring of a distillate, a dicyclopentene and a tricyclic ruthenium. The ethylenically unsaturated bond is preferably acetoxycarbonyl, methyl(tetra)decyloxy, ethoxylated, allyloxy, or vinyl, more preferably propylene oxide. Base, benzyloxy group. Examples of the monomer (bU) include (meth)acrylic acid glycidol vinegar, (meth)acrylic acid ♦ methyl glycidol vinegar, and (meth)acrylic acid ethyl glycidyl ester. A compound represented by the formula (bi_3) described in Japanese Laid-Open Patent Publication No. Hei 7-248625. [化31]

(b1-1a) The formula (bl-la) cards 'R to R62' each independently represent a hydrogen atom or a carbon number of 1 to 1. Ml represents an integer from 1 to 5. 151490.doc -34- 201131294 As a monomer (Μ七), for example, a ruthenium, a methylene-based sulfhydryl group, a glycidyl ether, a 1-methyl-o-vinyl group Glycidyl ruthenyl group shrinks to ethyl bromide 雔 u ^ u to vinyl nodal glycidyl ether, 2,3- bis (glycidoxy fluorenyl 7 ~ Luo D this ethylene, 2, 4- Bis(glycidoxymethyl) Benzoethylene, 2,5-bis (glycidol 4, its pore-based methyl group), ethylene, 2,6-bis(glycidoxyfluorenyl)styrene, 23 ^, 3 , 4-di(glycidyloxyindenyl)phenidinium quinone 2,3,5-di (glycidol gas, its 7 7 & methyl group), ethylene, 2,3,6-three (shrinkage) Glyceryloxymethyl)styrene, 3 4 ς wi ^ 3,4,5-di(glycidoxymethyl)styrene, and 2,4,6-tris(glycidoxymethyl) Examples of the monomer (bl-2) include ls2_epoxy-4-ethylidenecyclohexane (for example, Celloxide (registered trademark) 2〇〇〇; manufactured by Daicei Chemical Industry Co., Ltd. ), (fluorenyl)acrylic acid _2,3_epoxycyclohexyl Ester, 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer (registered trademark) A400; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl methacrylate ( For example, cyci〇mer Ml00; manufactured by Daicei Chemical Industry Co., Ltd., etc. Further, in the monomer (b 1 - 2), a monomer which is epoxidized as a cyclic olefin having an ethylenically unsaturated bond and a crosslinked ring (bl-3) (hereinafter referred to as "monomer (bl-3)")", for example, (meth)acrylic acid epoxy-decyl ester (for example, (meth)acrylic acid-3,4-epoxy group) a compound represented by the formula (bl-3 a) and a compound represented by the formula (bl-3b). 151490.doc •35· 201131294 [Chem. 32]

In the formula (bl-3a) and the formula (bl-3b), Rb1 represents a hydrogen atom or a monovalent saturated aliphatic hydrocarbon group having a carbon number of 丨~4, and a hydrogen atom contained in the saturated aliphatic hydrocarbon group may be substituted with a hydroxyl group. L represents a single bond or a divalent saturated aliphatic hydrocarbon group having a carbon number i to 6, and the saturated aliphatic hydrocarbon group -CH2. may be substituted with -?, -S- or -NRb2-, and the above Rb2 represents a hydrogen atom or A carbon number of 1 to 1 〇 one-valent saturated aliphatic hydrocarbon group. Examples of the saturated aliphatic hydrocarbon group which may be substituted with a hydroxyl group as Rbd include methyl group, ethyl group, propyl group, isopropyl group, butyl group, second butyl group, tert-butyl group, hydroxymethyl group, and hydrazine-hydroxy group. Ethyl, 2-hydroxyethyl, hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, hydrazine-hydroxy-hydrazine-methylethyl, 2-hydroxy-1-methylethyl, 1- Hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl and the like. Ri is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a hydroxyethyl group or a 2-hydroxyethyl group, more preferably a hydrogen atom or a methyl group. Examples of the divalent saturated aliphatic hydrocarbon group which may be substituted by -〇_, -S_ or _NRb2_, etc. of L1 include an anthracenylene group, an ethylidene group, a propylenediyl group, and an anthranylene group (-CH2). -0-), stretch {-(ch2)3-o_, etc., ethyloxy{-(CH2)2_〇-}, propylenedioxymethylenethio (_ch2-s_), extension B Alkylthio {-(CH2)2_S-}, propylenedithiochab (CH2)3_S_, etc., methyleneimido (-CH2_NH-), exoethylenimine (CH2)2_NH_} 'Pro-diimido group {-(CH2)3_NH-etc. etc.). L is preferably a single bond, anthracene extended ethyl, 151490.doc • 36- 201131294 methyleneoxy, ethyl ethoxy, ethylthio, or ethyl imino, preferably It is a single bond or an ethyloxy group. The compound represented by the formula (bl-3a) and the compound represented by the formula (bl-3b) may be used singly or in combination of two or more. Further, a mixture of a compound represented by the formula (bl_3a) and a compound represented by the formula (Μ#) can also be used. In the case of using a mixture of the materials, the compound represented by the formula (8) VII: the molar compound of the formula (bl-3b) is preferably 5:95 to 95:5, more preferably 1G: 9G. ~9G: 1G, and thus better is 2 please ~ 8〇: 2〇. Among the compounds represented by the formula (bl_3a), the formula (bl-1-l) to the formula (bl_^15) are preferred. Among these, 'better is monomer (bH-1), monomer (bUl_3), monomer (bl-1-5), monomer (bl small 7), monomer (Μ_ΐ9), and monomer (8)- 1_11)~monomer (bl]-15), and more preferably monomer (bl-1-l), monomer (bi-1-7), monomer (8)], and monomer (bi Small 15). 〇0 H2C=CH-i-0 丫Ο η H2C=CH-C-0-CH2 (bM-3) Ο H2C==CH-C-0-C2H4 (b1-1-5) Ο II H2C =C HC -O -C2H4O -(M-1-7) 0 HaCssC-CO-

CHs H2C=CH-d-0-C2H4S (M-1-2) 0 h2c=ch-c -0-C2H4NH (b1-1-4) 0 H2C=GC-0-C2H4S CH3 (bi-1-Q 0 II H2C=CC-〇-C2H*NH- △h3 (b1-1-B) 0 II H2C=CC-0-C2H5 (b1-1-1〇)

151490.doc -37- 201131294

0 HjC^C~C—〇 CHzOH

{b1-1 -12)

Ο CHs

0 H2C=C-C-0 C2H40H

O =<:-δ«2ιν·^^0 (iiHs (b1-1-13)^^ η^^^-〇^2Η4〇-^Ττ^° CH3 (bl-1-15) A ^ (bl The compound represented by the formula (bl-3b) is preferably a formula (bp2J)-3), 15). Among the above, 'better is monomer (bl-2-ι), monoterpene (b^^(bl. monomer(bl-2-5), monomer (bl-2_7), monomer (bl_2_9) ), as well as car grass mixed 2-11) ~ monomer (b 2 2-15), and more preferably monomer (b 卜 2 〇 (bl-2-7), monomer (b 卜 2-9 ) and monomer (bl-2-15).

HzC=CH-i 0)1-2-1)

—0— (b1-2-5) §

H2C=C"』-〇-C2H4S

0 i-0-C2H4NH-^J〇>< (b1-2-4) Ό H2C—C—i~0—C2H4S CH3 (b1-2-Q 〇

(b1-2-7)

(b1-2-1〇)

O H2C=C-C-0 ch3 (b1-2-9) H2C=C-C-0-CH2 CH3 (bl-2-11)

O h2c=c-c-o C2Hs

CH2 (V port) 151490.doc 38- 201131294

ο HaC^C-C-O-C^ CHt (b1-2»13) O

O Ο

G As the monomer (b2) having an ethylenically unsaturated bond and a propylene oxide ring, for example, 3-(meth)acryloxycarbonyl propylene oxide and 3 fluorenyl _3_(methyl) Propylene methoxymethyl propylene oxide, 3-ethyl_3_(methyl) propylene methoxymethyl epoxide, 3 mercapto-3-[b (meth) propylene oxime] Propylene oxide, 3-ethyl-3-[1-(indolyl)propenyloxy]methyl propylene oxide, 3-methyl-3-[1-(methyl) propylene oxy) Propylene oxide, 3-ethyl-3-[1-(indolyl)propenyloxy]ethyl propylene oxide, 2-phenyl-3-(methyl) propylene methoxymethyl propylene oxide , 2-trifluoromethyl-3-(methyl)propenyloxymethyl propylene oxide, 2-pentafluoroethyl-3-(methyl) propylene methoxymethyl propylene oxide, 3-methyl 3-(meth)acryloyloxyethyl propylene oxide, 3-mercapto-3-(methyl) propylene oxiranyl ethyl epoxide, 2 phenyl _3_(methyl) propylene Ethoxyethyl propylene oxide, 2-trifluoromethyl 3-(indenyl) propylene methoxyethyl propylene oxide or 2-pentafluoroethyl 3-(methyl) propylene oxyethyl Ethylene-acrylic, 3-(A Base) propylene oxy propylene bromide and the like. Of these, 3-ethyl-3-(indenyl) propylene fluorenyl decyl propylene oxide is preferred. As the monomer (10) having a ethyl (10) unsaturated bond and a tetrahydrocyclic ring, (meth)acrylic acid tetrahydrosaccharide and (meth)acrylic acid tetrahydroanthracene are exemplified. Methane (m), tetrahydro-w-methoxypropyl vinegar, etc. The monomer (8) may also contain a monomer (4) different from the monomer (4) and the monomer (b). 151490.doc • 39- 201131294 is a monomer (c), for example, a carboxylic acid ester having an ethylenically unsaturated bond, an oxime amine having an ethylenically unsaturated bond, and a side chain having a polymerizable unsaturated bond ( In particular, an aromatic compound, a substituted ethylene compound, an N-substituted maleimide, a diene, a polycyclic unsaturated compound, or the like, which is an ethylenically unsaturated bond. The monomer (c) may be used singly or in combination of two or more. More specifically, as the monomer (c)', methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate are mentioned. , (fluorenyl) benzyl acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, isodecyl (meth) acrylate, tricyclo(methyl) acrylate [5.2 ·! 〇2,6]decane _8•yl ester (in the field, sometimes also known as the "dicyclopentyl (meth) acrylate), (mercapto) acrylic-4-tricyclic [5.2.1.02'6] terpene _8_yl ester, (fluorenyl) acrylate-5-dioxime [5.2.1 · 〇2'6] decene-8-yl ester, benzene (meth) acrylate a carboxylic acid ester having an ethylenically unsaturated bond, such as anthracene, fluorenylaminoethyl acrylate, maleic acid diethylene glycol, diethyl fumarate, diethyl itaconate ; decylamines having ethylenic unsaturated bonds such as dimethyl(fluorenyl) acrylamide, isopropyl (meth) acrylamide; styrene, α-methyl styrene, vinyl Methoxystyrene is equal to the side chain An aromatic compound having a polymerizable unsaturated bond; a nitrileated vinyl compound such as acrylonitrile, methyl acrylonitrile or α-gas (fluorenyl) acrylonitrile; a mouse, a lacto-diethyl, a di-thirsty ethylene, Ethylene, ethylene, ethylene, ethylene, ethylene, tetrafluoroethylene N-substituted cis such as amine, butyl maleimide, N_cyclohexyl maleimide, N-benzyl maleimide, N-phenyl maleimide Butylene diimide; 1,3-butadiene, isoprene, 2,3-didecyl q, % butadiene and other dienes; bicyclo [2·2.1] hept-2-ene ,5-fluorenylbicyclo[2.2.1]heptane-2_dilute,5·ethylbicyclo[2.2.1]hept-2-ene,5-trans-bicyclo[221]hept-2-d,5_jing Methylbicyclo[2.2.1]hept-2-ene, 5-(2,-transethylethyl)bicyclo[2.21]hept-2-ene, 5-nonyloxybicyclo[2.2.1]hept-2- Alkene, 5-ethoxybicyclo[2 2 1;|hept-2-ene, 5,6-dihydroxybicyclo[22^heptene], 56_bis(hydroxyindenyl)biguanide [2.2_1]g 2-ene, 5,6_ di(2·-hydroxyethyl Bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2 2^heptene-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene 5-Hydroxy-5-indenylbicyclo[221]hept-2-ene, 5-hydroxyl yl-5-ethylbicyclo[2·2·1]hept-2-ene, 5-hydroxymethyl-5- Indenylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenyloxycarbonylbicyclo[2.2. a polycyclic unsaturated compound such as 5,6-di(cyclohexyloxycarbonyl)bicyclo-[2.2.1]hept-2-ene. Among the monomers (c), preferred are benzyl (meth)acrylate, bicyclo[5.2.1.〇2'6]decane-8-yl ester, styrene, N_ Cyclohexyl maleimide, N-benzyl maleimide, N-phenyl maleimide, bicyclo [2.2.1] hept-2-ene. As the monomer (X), only one of the monomer (b) or the monomer (c) may be used, or both of them may be used by 151490.doc -41 - 201131294. The monomer (4) is preferably only a single impurity (9). If using a copolymer containing a single Zhao (9), the reference to heat, light resistance, solvent resistance, and mechanical properties: when it is a single copolymer... =::: In the unit: from Zhao The structural unit of (4) is better than (4) is that the unit is preferably 2~=::~: mole %' from the monomer (b) (four) = the ratio of the early body (seven) is within the above preferred range, then there is = heat resistance Sexual and mechanical strength tends to be good. If it is within the scope of the above, the target is better.

, 颏 性, residual film rate and solvent resistance become H::: (8) is the case of the copolymer of monomer (4) and monomer (4):: the king of the structural unit of the polymer, come... 2, Mo Ear %, more () - structure read well is the unit compared to ... Moer%, from the structure of the monomer (4) read well 疋 2~98 mol%, more preferably 4 (:: monomer (4) The ratio is in the above-mentioned preferred range, and the storage property and the heat resistance tend to be good. If the above-mentioned better is true, the developability and the residual film ratio become good. In the case of a monomer (a), a single monomer, a copolymer of all C and an early hetero (4) copolymer is preferably 2 to 97 mol mr / the structural unit derived from the monomer (4) is better than the structural unit. ~97 Mo::: Moer: 'From monomer (b) From the monomer (4) structural unit (four) ° is 丨 = 7~5G mol%, 10~70 mol%. If monomer (a) ~ The ratio of the monomer (4) / /0, more preferably the ratio of () in the above preferred range I5I490.doc -42 - 201131294, the storage stability, .. heat resistance and mechanical strength become good. Tendency, if better in the above In the dry circumference, the developability and the residual solvent ratio are also good. The thousand and the resin-resistant (B), for example, the spring method can be used in the test of molecular synthesis. The method described in the publication of the second edition of the BiL 仏 仃 仃 股份有限公司 股份有限公司 股份有限公司 3 3 3 3 3 3 3 3 3 3 3 3 3 袢 袢 袢 Bi Bi Bi Bi Bi Bi Bi Bi Bi Bi Bi Bi Bi Bi Bi Bi Bi Yang Yanhua. More specifically, by

The monomer (4), the monomer (b) and/or the monomer (4), the polymerization initiator and the solvent are put into a reaction vessel, and are stirred, heated, and kept in an atmosphere in which oxygen is replaced by nitrogen to produce copolymerization. Things. The method of the copolymerization or the reaction temperature may be adjusted as long as the surface of the production equipment and the heat generated by the polymerization are considered. The obtained copolymer can be directly used as a solution after the reaction. In particular, when a solvent (G) to be described later is used as the polymerization solvent, the solvent can be used as a resin composition without removing the solvent from the copolymer solution after polymerization, and the production step can be simplified. Alternatively, the copolymer solution can be concentrated or diluted. Further, a solid (powder) copolymer taken out by a method such as reprecipitation may also be used. The resin (B) may further contain a structural unit represented by the formula (d1) or the formula (d2). When the resin (B) containing a structural unit is used, pattern adhesion, solvent resistance, and sensitivity can be improved. 151490.doc -43- 201131294 [Chem. 35] R84

(d1)

In the formula (4)) and the formula (d2), ... and ^ each independently represent a hydrogen atom or an alkyl group having 6 carbon atoms (preferably a hydrogen atom or a mercapto group).

The structural unit represented by the formula (6) can be formed by copolymerizing the monomer (4) and the monomer (8) and/or the monomer (4), for example, in the same manner as described in Japanese Laid-Open Patent Publication No. 2005-189574. In the method, the hair is derived from the monomer of the monomer (4) or the oxo group (10) anhydride structure) and the monomer represented by 3 (M-4) is added. Further, the structural unit represented by the formula (4)) can be formed in the same manner as described above using the monomer represented by the formula (M-5). [化36]

(b1-5)

[In the formula (bi·4) or (bl-5), the meaning of R65 is the same as above] The acid value of the resin (8) is preferably (9) ~ ΐ 5 () ηι_Η / §, better 6 〇 ~ 135 呵Lihua 'into * is better 70~135 mgKOH / g. If the solubility of the 贞m developer is increased, the unexposed portion is easily dissolved. Here, the acid value is a value obtained by measuring the amount (mg) of the desired amount of hydrogenation of the polymer having an acidic group such as a carboxyl group, 151490.doc -44 - 201131294, usually by using an aqueous solution of potassium oxychloride. Determined by titration. The weight average molecular weight of the resin (B) is preferably 〇〇, deleted (more preferably 2, qing ~ 5G, _ ' and more preferably 3, _~%, coffee). If it is within this range, the coating property of the composition is good, and the residual film ratio at the time of development can be maintained and a high developing speed tends to be obtained. Further, the weight average molecular weight can be determined by gel permeation chromatography using polystyrene as a standard.分子量 分子量 The molecular weight distribution of the resin (B) {i.e., the weight average molecular weight pottery/number average molecular weight (Mn) m is preferably η, (more preferably 丨2 to 4 〇). If it is in this range, the developability tends to be excellent. The content of the resin (B) is preferably ～35 mass% (more preferably 15 to 3 Qf4%) with respect to the solid content of the composition, and is preferably in combination with the photopolymerizable compound (6). It is 3 () ~ 85 mass% (better... 5 mass and further preferably 4 〇 ~ 65 mass%). If the content of the resin w is within the above range, the solubility in the positive (4) is sufficient, and the tendency of the non-exposed portion (non-pixel portion) is not likely to occur. Further, there is a tendency that the exposed portion (pixel portion) is less likely to cause film reduction during development, and the non-exposed portion (non-pixel portion) is excellent in peeling property, and the resolution and the residual film ratio tend to increase. In the present specification, the "solid content component of the composition" is referred to as "the total of the components of the composition after the solvent is removed". The solid content can be measured by a method known in the art of gas chromatography or liquid chromatography. The colored photosensitive resin composition of the present invention contains a photopolymerizable compound (c). The photopolymerizable compound (c)' is a compound which can be enumerated by a photopolymerization initiator (D) by 151490.doc -45-201131294 photopolymerization initiator (D) by a light irradiation, for example, It has a reverse-slave unsaturated bond that is incorporated into the mountain as a compound for the polymerization of soil. In the above, the photopolymerizable compound (6) is preferably a compound having a (meth)propenyl group, more preferably a compound having three or more (fluorenyl) acrylonitrile groups. The photopolymerizable compound (c) is preferably a photopolymerizable compound having a polymerizable group of _ or more. Examples of the photopolymerizable compound having three or more polymerizable groups include pentaerythritol tris(meth)acrylic acid vinegar, trimethyl:propyl k-(meth)acrylic acid, and pentaerythritol tetrakis(methyl)propionic acid. Dipentaerythritol penta (meth)acrylic gambling, dipentaerythritol hexa(meth)acrylic acid, etc., compared with the cup-counter-Yong, > Photopolymerizable Compound (c) may be used singly or in combination of two or more. The content of the photopolymerizable compound (C) is preferably from 7 to 65% by mass based on the solid content of the photosensitive resin composition of the color, and more preferably (9) quality: and further preferably 17 ~55 mass%. When 3 of the photopolymerizable compound (6) is in the above range, the curing is sufficiently performed, and the film thickness ratio before and after the development is improved, and the undercut (und(10)t) is less likely to occur, and the adhesion is better. it is good. The coloring photosensitive resin composition of the present invention contains a photopolymerization initiator (D) as a photopolymerization initiator (D), and examples thereof include an active radical generator and an acid generator. The living radical generating agent generates active radicals by light irradiation. As the living radical generating agent, for example, an alkyl ketone compound, a scented compound, a benzophenone compound, a sulfonium phthalocyanine compound, a tritonic 151490.doc • 46 - 201131294 compound, an anthraquinone compound, and the like can be exemplified. Among them, in terms of sensitivity, a ruthenium compound is preferred. Examples of the alkyl ketone ketone compound include diethoxyacetophenone, 2-methyl-2-naphthyl-1-(4-sulfonylphenyl)propane oxime ketone, and 2-hydroxyl group. _2_mercapto-1-phenylpropan-1-one, pheno-indolyl ketal, 2-hydroxy-2-indole-1- 1-[4-(2-hydroxyethoxy)phenyl] An oligomer of propane ketone, hydrazine-hydroxycyclohexyl phenyl ketone, 2-yl-2-mercaptomethylvinyl) phenyl] propanone acetonone or the like. 0 The car can be exemplified by 2_methyl-2·weilinjixiao(4)methylthiophenyl)propanone-ketone. Examples of the benzoin compound include, for example, benzoin g, wensijin, feminine, benzoin, benzoin isopropyl, benzoin isobutyl ether, etc.::: dimethyl 'compounds', for example, benzene (tetra), O-benzhydrazyl radical methyl formate, 4-phenylene _ ^ χ - benzophenone, 4-phenylmercapto-4,-mercaptodiyl thioether, 3,3,,4,4,_four 〇 2A6-trimethyl benzophenone, etc. - thiol-based thiophene _, as a 9-oxo sulphate mountain compound, dichloro 9-oxo sulphur ... - chlorodiethyl _9 _ oxy sulphur ♦ star, 2, heart as a three-hook compound, for example Milk base _9 · gas sulfur coffee star and so on. Methoxyphenyl)-1,3,5_三哜^ 举.2,4_bis(trichloromethyl)-6-(4-yl)-U-2,: bis (two 4 2 1 , 3,5-three tillage, 2,4_bis (trichloro, tau)-6-(4-methoxystyryl)-yl]_1,3,5_three_, 2,4^: X'6_[2_(5-methyl. fumarantyl) ethylene monooxymethyl)_6-[2_(furan-2-yl)ethylene I51490.doc -47- 201131294 base]-1,3,5- Trihalo, 2,4-bis(trichloroindenyl)_6_[2_(4diethylamino-2-phenylphenyl)vinyl]-1,3,5-three tillage, 2,4-double ( Trichloroindolyl)_6_[2_(3,4-monomethoxyphenyl)ethenyl]-1,3,5-three wells, and the like. Examples of the ruthenium compound include a ruthenium ruthenium ruthenium compound, and specific examples thereof include N-abidomethyl oxy-("4-phenylthioalkylphenyl)butane-1-ketone-2 -imine, N-benzofluorenylphenylsulfanylphenyl)octanophenone-2-imine, N-acetoxy-^, ethyl-6 (2-methylbenzhydryl) _ 9H-carbazol-3-yl]ethane_ι_imine, n_6-methoxyethyl-6_2]methyl-4·(3,3-dimercapto-2,4-dioxacyclohexane Pentyl decyloxy) benzhydryl quinone 9 Η-oxazol-3-yl] ethane 丨 亚 imine, etc. 〇χΕ _ 〇 1 11 " Lv 8 (: 111 ^ 〇 and £ - 〇 2 can also be used (The above is a commercial product such as (^3)3卩&11 company), >) [-1 91 9 (manufactured by Adeka Co., Ltd.). The active radical generator other than the above-exemplified ones can be used, for example. 2,4,6-Dimethylbenzimidyldiphenylphosphine oxide, 2,2,_bis(o-chlorophenyl)-4,4',5,5'-tetraphenylisineimide, 1〇_butyl_2_chloroacridone, 2-ethyl hydrazine, octopus, 9, phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound, etc. For the acid generator, for example, Toluenesulfonic acid _4-hydroxyphenyl dimethyl hydrazine, hexafluoroantimonic acid _4 hydroxyphenyl dimethyl hydrazine, p-toluene sulfonic acid _4_ ethoxylated phenyl dimethyl hydrazine, hexafluoroantimony Acid-4-ethoxylated phenyl group. The methyl group is a p-toluene triphenyl sulfonate, triphenyl sulfonium hexafluoroantimonate, diphenyl sulfonate p-toluenesulfonate, hexafluoroantimonate An anthracene salt such as phenylhydrazine, or a nitrobenzyl tosylate or a benzoin tosylate, etc. Among the compounds described as active radical generators, 151490.doc •48· 201131294 A compound that produces acid at the same time as a free radical, for example, a compound can also be used as an acid generator. - Well (t) two (D) - content relative to resin (Β) The photopolymerizable compound is preferably 0.1 to 30 parts by mass, more preferably 1 to 2 parts by mass, if the content of the photopolymerization initiator is within the above range, and there is a salty light. In the target area of the Λ丨 上 , , , ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' Incorporation of starting auxiliaries (8). 弁平人^3 has a prepolymerization (the first polymerization initiation aid (Ε) is usually used in combination with photopolymerization initiation (10)) to promote photopolymerization initiators. A compound or a sensitizer for polymerizing a photopolymerizable compound to be polymerized. The 'photopolymerization initiation assistant (8) may, for example, be an amine compound, an alkoxy onion compound or a 9-oxothione compound. Examples of the amine compound include triethanolamine, methyldiethanolamine: triisopropanolamine, 4-dimethylaminobenzoic acid methyl ketone, heart dimethylamine oxime basic ethyl formate, and 4-dimethylamine. Isoamyl benzoate, didecylaminoethyl benzoate, 2-ethylhexyl 4-methylaminobenzoate, hydrazine, hydrazinyl-p-toluidine, 4,4,- Bis(dimethylamino)benzamide (commonly known as mazinone) 4,4_bis(monoethylamino)benzophenone, 4,4,-bis(ethyldecylamino) Among them, benzophenone or the like is preferably 4,4,-bis(diethylamino)benzhydryl. As the alkoxy hydrazine compound, for example, 9, i Q. dimethoxy bromo, 2 ethyl-9,10-methoxy fluorene, 9,1 fluorene diethoxy fluorene, 2 - B may be mentioned. Base _9,1〇_diethoxy onion, 9,1 〇-dibutoxy fluorene, hydrazine ethyl -9,1 〇 _ dibutoxy 蒽 151490.doc • 49· 201131294 and so on. As 9-oxo-sulfur, a mountain Pf compound, such as, for example, a star, a heart isopropyl-9-oxo-sulfur such as a star, 24] its isopropyl 9-oxosulfuryl lactate ^Mountain m4_propoxy_9_ Oxygen sulfur _ and so on. The photopolymerization initiation aid (E) can be used alone or in combination of two or more. In addition, as a photopolymerization start aid, rFAR. (), for example, a commercial product such as the trade name EAB-F" (made by Gutani Chemical Industry Co., Ltd., Guyang, Koujiu Co., Ltd.) can be used. The combination of the photopolymerization initiator (9) and the photopolymerization initiation aid (8) in the color sensitization of the cockroach cockroach and the photopolymerization initiation aid (8) is exemplified by the following: diethoxy acetophenone / 4,4,·bis(diethylamino)benzophenone, 2·methyl I-saltyl-bis(4-methylthiophenyl)propylamine small copper/4,4,•double (two Ethylamino)benzophenone, 2-hydroxy-2-methyl-i-phenylpropane·buxone/, bis(diethylamino)benzophenone, benzoin dimethyl嗣/4'4, · bis(diethylamino)benzophenone, 2-starting-2-mercapto-l-[4-(2-carbylethoxy)phenyl]propane嗣/44,_bis(diethylamino)benzophenone, hydrazine-hydroxycyclohexyl phenyl ketone/44,-bis(diethylamino)benzophenone, 2-hydroxy-2-methyl base-. ['(丨-Methylvinyl)phenyl]propan-1-one oligomer/4,4,-bis(diethylamino)dibenzophenone, 2-benzyl-2-indenyl Amino-1-(4-imidylphenyl) butyring_ι_ketone/4,4,_bis(diethylamino)benzophenone, etc. 'Better is 2_methyl· 2_ sulphonyl d-(4-methylthiophenyl)propan-1-one / 4,4,-bis(diethylamino)benzophenone. When such photopolymerization initiation aids (Ε) are used, the amount thereof is preferably 〇.1~1〇莫耳, more preferably 〇〇, relative to the photopolymerization initiator (D). 1~5 Moer. 151490.doc -50- 201131294 The colored photosensitive resin composition shown herein contains a typical metal compound (F). As a typical metal compound (F), a typical metal compound (1?) containing a carbon atom and having a maximum molar absorption coefficient in a visible light region is smaller than a maximum value of a molar absorption coefficient of a dye in a visible light region. By containing the typical metal compound, the contrast, heat resistance and light resistance of the coating film can be improved. As the typical metal compound (F), a typical metal complex, a typical metal salt or the like can be mentioned. It is preferred that it is dissolved in an organic solvent. The maximum value of the molar absorption coefficient in the visible light region (wavelength 3 80 nm to 780 nm) is prepared by diluting a typical metal compound (F) 〇ig with ethyl lactate %% L to prepare a solution using ultraviolet visible spectrophotometry. The absorption spectrum of the solution in the visible light region was measured and calculated by the Law of Lamben_Beer. The maximum value of the molar absorption coefficient of the typical metal compound (F) in the visible light region is smaller than the maximum value of the molar absorption coefficient of the dye contained in the visible light region of the colored photosensitive resin composition of the present invention, preferably 〇. More preferably, it is 1000 or more, more preferably 〇 or more, 500 or less, further preferably 〇 or more, 100 or less, and more preferably 20 or more, and 8 〇 or less is preferably 30 or more and 60 or less. When the maximum value of the molar absorption coefficient in the visible light region is 1 Å or less, the brightness of the coating film tends to increase, which is preferable. As a typical metal contained in the typical metal compound (F), for example, Group 1A (alkali metal), Group 2A (alkaline earth metal), Group 23 (Zinc group), Group 3B (side group), 4B of the periodic table can be cited. Metals contained in the family (carbon family) and 5B group (nitrogen group) 151490.doc -51 - 201131294 Element. Specific examples of the typical metal contained in the typical metal compound (F) include bismuth (Be), magnesium (Mg), aluminum (A1), calcium (Ca), bis (Zn), and gallium (Ga).铷(Rb), strontium (Sr), cadmium (Cd), indium (In), tin (Sn), absolute (Cs), barium (Ba), mercury (Hg), strontium (T1), lead (Pb),铋 (Bi), 鲂 (Fr), radium (Ra), and the like. Among them, 'preferably magnesium (Mg), aluminum (A1), calcium (Ca), zinc (Zn), gallium (Ga), antimony (Rb), antimony (Sr), indium (In), planer (Cs) More preferably, it is aluminum (A1), zinc (Zn), indium (In), and barium (Ba), and more preferably aluminum (A1), zinc (Zn), or indium (In). In the case where the compound containing the above-mentioned typical metal is used for coloring the photosensitive resin, the coating film obtained from the colored photosensitive resin composition tends to have a higher contrast ratio, heat resistance and light resistance. Further, as the typical metal compound (F), it is preferred to contain a carbon atom, and more preferably a compound selected from at least one group selected from the group consisting of 4 (where _c(=s)_, typically The metal compound is preferably a compound represented by the formula (F1), a compound represented by the formula (F2), and at least one compound of the group consisting of the hydrates. In the case of the above compound, the solubility in the organic solvent tends to increase, which is preferable.

W2

JX (F1)

(F2) 151490.doc •52- 201131294 [In the formula (4) and (4), _ and Jia 2 are independent of each other and represent a carbon number of 6 one-valent aliphatic hydrocarbon group or a carbon number of 6 to 10 one-valent aromatic hydrocarbon group, the fat The hydrocarbon group and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted by (d). W and W independently of each other represent a carbon number of 6 valence aliphatic group, and a hydrogen atom contained in the aliphatic hydrocarbon group may be substituted by a fang atom. Μ1 and Μ2 represent typical metal atoms. And the y table is not an integer of 1 to 3, when χ is an integer of 2 or more Ο Ο

And w2 may be the same or different from each other. When y^2 is an integer of 2 or more, and a plurality of W and w4 may be the same or different. W1 and W2 are carbon atoms which can be substituted by a carbon number, and are substituted with a valence aliphatic hydrocarbon group or a hydrogen atom which can be substituted with a carbon number of 6 to a valence aromatic furnace 0 'work 1 - via base 3 The hydroxypropyl 1-carbobutyl group is preferably a carbon number which may be substituted by a radical as a hydrogen atom, and a monovalent aliphatic nicotyl group, for example, a mercapto group, an ethyl group, an isopropyl group, Butyl, first butyl, second butyl, pentyl, hexyl, hydroxymethyl, 2-hydroxyethyl, hydrazine-hydroxypropyl, 2-hydroxypropyl 1 hydroxy-1-methylethyl 2, hydroxy-丨-methylethyl 2 hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl and the like ethyl, butyl, 2-hydroxyethyl. Examples of the monovalent aromatic hydrocarbon having 6 to 10 carbon atoms which may be substituted by a hydroxyl group as a hydrogen atom include a phenyl group, a tolylhydryl group, a xylyl group, a benzyl group, a propyl group, a butyl group, and a phenyl group. The group, the transmethyl group, and the like are preferably a phenyl group or a benzyl group. ,

^ M TEL is a valence of 1 to 6 carbon atoms which can be substituted by a halogen atom. 151490.doc -53- 201131294 Aromatic hydrocarbon group. The halogen atom, and the atom, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like is preferably a gas atom. The valence aliphatic radical group having a carbon number of 1 to 6 which may be substituted by a self atomic atom is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group, and a second group.丁其,士故^一" butylpentyl, hexyl, fluoromethyl, difluoromethyl, gas fluorenyl-fluoroethyl, chloromethyl, chloroethyl, dichloroethyl, chloropropyl, A gas butyl group, a butyl group, a fluorenyl group or the like is preferably a methyl group, a third butyl group or a trifluoromethyl group. Specific examples of the preferred metal compound (7) include, for example, tris(2,4-pentanedioic acid) succinium (tetra), tris(trioxane-2,4 oxalic acid), (πι), and one (2 I). Aluminum compound such as aluminum, bis(2-ethylhexanoic acid) hydroxy aluminum: bis(2-sulfanyl-N-oxidized pyridine) zinc, bis-"_bis(2-hydroxyethyl) Thioamine decanoic acid]zinc, bis(N-dimethyldithiocarbamic acid), bis(N,N-diethyldithiocarbamic acid), double (n,n_: Butyl bisdithiocarbamic acid) zinc, bis(N-ethyl·Ν_styldithiocarbamic acid), bis(Ν'Ν-dibenzyldithiocarbamic acid) zinc, Zinc compounds such as bis(thiocyanate)zinc and bis(2-hydroxypropionate)zinc: tris(2,4-pentanedioic acid) indium (III), tris(2 2,6,6-tetramethyl·3 5_pimelic acid) Indium compounds such as indium (III) and di(difluoro 2,4-pentanoic acid) indium (III): bis(2,4-pentanedioic acid) bismuth, bis(hexafluoro_2) , 4_glutaric acid) bismuth, bis(2,2,6,6-tetramethyl-3,5-pimelic acid) hydrazine, bis(2-hydroxypropionic acid) hydrazine, bis(thiocyanate) hydrazine, Bis(stearic acid) bismuth, tartaric acid An anthracene compound such as cerium oxalate: a hydrate of the above compound, etc.; preferably, it is a double (Ν, Ν_二丁151490.doc -54-201131294 thiodithiocarbamic acid) word, double "Ν Ν别其田秘 - ·, bis(2, ylethyl) dithiocarbazone, bis(2,4-pentanedioic acid) indium (111), or hydrates of the above - (2, 4-Pentaic acid) _ If a feed metal compound is used, the solubility of the material in the organic solvent and the contrast of the coating film tend to be high. Therefore, the content of the dimetallic compound (F) is relatively high. In the case of resin (Β) and photopolymerization, it is preferably a mass part or more, a mass ratio of 20 parts or less, more preferably 20 parts by mass or less. The content is less than or equal to 1 part by mass and 10 parts by mass. θ ^. If the content of the typical metal compound is within the above range, the contrast of the deposited film tends to be high, so that the film is preferred. Further, the coating agent Γ:: the coloring photosensitive resin composition contains a solvent (6). As a solution, for example, J: a bond, an aromatic smog, a ketone other than the above, an alcohol , esters, decylamines, Ν _ _ 垃 丞 疋 疋 疋 疋 同 同 同 同 同 二 二 二 二 二 二 二 二 二 二 二 二 二 / / / / / / / / / / / / / / / / / / / , Ethyl alcohol monomethyl ether 'ethylene glycol mono-flat G ether, ethylene glycol monopropyl ether, B: Succinium, diethylene glycol monomethyl shrine, diethylene glycol monoethyl bond, diethylene glycol early Dibutyl ether, diethylene glycol dimethyl ether, diyiping monoethyl ether, diethylene glycol methyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl acetate, propylene glycol Ethyl acetate vinegar, propylene glycol monopropyl ether acetate vinegar, propylene glycol Cuijiajun, methyl sagitar acetate vinegar, ethyl seisu acetic acid vinegar: ethyl carbitol acetate vinegar, butyl carbitol acetate vinegar, benzene A mystery, benzene, methine, methylbenzene, etc. 151490.doc -55· 201131294 As an aromatic smoke _ dimethyl poor Chu a T winter search. For example, benzene, toluene, diterpene benzene, and ketone oxime may, for example, be propylene, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-reviewed i, T 1 . -2-pentanone, 4-cysyl-4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and the like. Examples of the alcohols include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin. Examples of the self-quinones include ethyl acetate, n-butyl acetate, isobutyl hydrazine, amyl phthalate, isoamyl acetate, isobutyl acetate, butyl butyl acrylate, and butyric acid. Ethyl ester, butyl butyrate, alkyl ester, lactic acid, ethyl acetoate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, decyl ethoxylate, Ethyl ethoxylate, 3-decyloxypropane sulphate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 2_ Ethyl hydroxypropionate, oxazepine 2 - methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2 - ethoxy propyl oxime I 曰, 2 -ethyl ethoxypropionate, methyl 2-methoxy-2-propenylpropionate, ethyl 2-ethoxy-2-methylpropionate, decyl pyruvate, ethyl pyruvate, acetone Acid propyl ester, decyl pyruvate, ethyl acetate ethyl acetate, methyl 2-oxetoxybutyrate, ethyl 2-oxooxybutyrate, 3-methoxybutyl acetate, % methyl _ 3_ methyl lactyl butyl acetate, γ_ butane vinegar, and the like. Examples of the guanamines include ν, ν-dimethylformamide, ν, ν_χmethylacetamide, Ν-methylpyrrolidone, and the like. Among these, preferred are propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and 4-hydroxy-4-methyl-2-pentanone, and more preferably 151490.doc-56 - 201131294 These. Further, the solvent (-τ may be used singly or in combination of two or more. I & * light; the content of the solvent (G) in the raw resin composition is preferably higher than that of the coloring photosensitive tree compound. It is 70 to 95% by mass, more preferably 75 to 90 f 3: °/« ° The content of the agent (G) is within the above range, and there is + ia '14 @ & In the coloring photosensitive resin composition of the present invention, the coloring photosensitive resin composition may further contain a surfactant (H). As the surfactant (H), the color density of the filter is not insufficient, and the characteristic is good. 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 is exemplified. A surfactant having a siloxane coupling, etc. Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA 'Toray Silicone SH28PA ' Toray Silicone 29SHPA, Toray Silicone SH30PA, polyether modified eucalyptus oil S H8400 (trade name: manufactured by Toray Silicone Co., Ltd.), KP321, KP322, KP323, KP324, KP326 'KP340, KP341 (manufactured by Shin-Etsu Silicone)' TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, manufactured by a subsidiary of TSF4460 (Momentive Performance Materials Japan), etc. The fluorine-based surfactant can be exemplified by a surfactant having a fluorocarbon chain. Specifically, Fluorad (trade name) FC430, Fluorad-57-151490.doc 201131294 FC43 1 (manufactured by Sumitomo 3M Co., Ltd.), Megaface (trade name) F142D, Megaface F171, Megaface F172, Megafaee F173, Megaface F177 , Megaface F183, Megaface R30 (manufactured by DIC Corporation), Eftop (trade name) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (trade name) S381, Surflon S382 ' Surflon SC 101 ' Surflon SC 105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Precision Chemical Research Co., Ltd.), BM-1000, BM-1100 (all trade names: manufactured by BM Chemie Co., Ltd.). The polyfluorene-based surfactant having a fluorine atom may, for example, be a surfactant having a ceramide bond and a fluorocarbon chain. Specifically, it can be enumerated:

Megaface (registered trademark) r〇8, 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 (H), kJ, based on the coloring photosensitive resin composition is preferably 〇1 to 〇1 by mass. /. It is better that 0.00005~〇.〇1% by mass. When the content of the surfactant is within the above range, flatness tends to be good, which is preferable. Here, the content of the surfactant (G) does not include the content of the above-mentioned pigment dispersant. As a method of forming a pattern of a color filter ruthenium using the colored photosensitive resin composition of the present invention, for example, the colored photosensitive dendritic composition of the present invention is applied to a substrate or another resin layer (for example, before A method of forming a coloring layer by removing a solvent or the like to form a coloring layer, and then exposing and developing the colored layer via a photomask, is formed on a layer of 151490.doc-58-201131294 other colored photosensitive resin composition layer. (ie, photolithography); and a method of using an inkjet machine that does not require photolithography. In the photolithography method described above, the coating film of the present invention can be obtained by using no mask and/or not developing during exposure. Specifically, a plurality of TFTs 22 are formed on each of the pixels on the glass substrate 21 by a known method such as photolithography (see Fig. 1). The TFT 22 includes, for example, a gate electrode 22a formed on the glass substrate 2A by molybdenum (Mo) and constituting a part of the gate line 、, and a nitride film (SiNx) formed on the gate electrode 22& a gate insulating film 22b' formed of a build-up film of an oxide film (Si〇2), a polysilicon film 22, formed on the gate insulating layer 22b, and, for example, an oxide film (sioj and a nitride film (SiNx)i The protective film 22d formed by the laminated film, the region of the polysilicon film 22c opposed to the gate electrode 22a serves as a channel region of the TFT 22, and the region on both sides of the channel region becomes a source region or a drain region. The source region of 22c is electrically connected to a signal line 27 formed, for example, by aluminum, via a connection hole (contact hole) provided in the film 22d. Further, the drain region of the polysilicon film 22c is as follows Generally, it is electrically connected to the pixel electrode 24 via a connection hole (contact hole) 2〇1. When a plurality of TFTs 22 are formed on each of the pixels on the glass substrate 21, alignment is formed while forming the TFT 22 on the glass substrate 21. Mark (not shown). The alignment mark is as follows The alignment index in the forming step of the color filter layer 23 is used as described above. Further, the alignment marks may also serve as a mark for bonding the driving substrate and the opposite substrate. When a metal layer or a polysilicon layer such as a wiring is formed in the manufacturing process of the TFT 22, 151490.doc -59-201131294 is formed in the same step by using at least one of the layers. Next, the glass substrate 21 on which the TFT 22 and the alignment mark are formed is formed. The colored photosensitive resin composition layer 23 having a film thickness of 〇5 to 5_〇μηι, for example, 丨.0 μηι, is formed by a spin coating method or another method. The colored photosensitive resin composition layer 23 corresponds to the color of the present invention. Then, the coloring photosensitive resin composition layer 23 A is dried at a temperature of 30 to 12 (the temperature in the range of TC, for example, 60 to 11 (r), and the coloring photosensitive composition layer 23 is dried. A can be combined with drying under reduced pressure and heat drying. Next, the colored photosensitive resin composition layer 23 A is irradiated with ultraviolet rays through a mask (not shown), and the excess portion is selectively removed by the developer. (unexposed portion), thereby forming a connection hole (contact hole) 201 reaching the drain region of the polysilicon film 22C, and then performing water washing. Thereafter, the coloring photosensitive sapphire composition layer 23 A is reflowed. (Reflow) The hardening component contained in the colored photosensitive composition layer 23A is cured, and is heated at a temperature in the range of 100 to 300 ° C, for example, i5 〇 23 23 ° C. Thus, the colored photosensitive resin composition layer 23 A is formed to include a red color filter 23a, a green color filter 23b, and a blue color filter 23 (for example, the color filter layer 23 for each pixel row). 2). The area between the respective filters of the color filter layer 23 serves as a mixed area of adjacent colors. However, since this area is opposed to the light-shielding area of the signal line 27, the quality is not particularly affected. Furthermore, the area between the respective filters may not be colored. Then, for example, a photosensitive resin layer 29 (see Fig. 3) as a protective film having a thickness of 0.3 to 2 Å is formed by a spin coating method so as to cover the color filter layer 23. Then, the photosensitive resin film μ 151490.doc 201131294 is irradiated with ultraviolet rays through a mask (not shown), and the area and the excess portion of the developer are selected by the developer, and the release and connection holes 201 are released. The connection hole (contact hole) of the opposite pole region reaches the non-photosensitive tree of the polycrystalline stone 臈 22c. "29 (4) "Then, for the purpose of assigning the degree, for example: in the range of 100 to continuation The temperature lr is selected and heated. Then, the residual edge and the organic matter in the dye are collected by oxygen electricity: the contact hole 202 is used to remove the oxygen formed by the oxygen, and the column is further ordered, for example, by dilute hydrogen fluoride. Acid etching

W is formed by forming a transparent conductive material on the photosensitive resin film 29 by sputtering [eg, ndium_Tin: a mixed film of indium and tin oxide)" and then by photolithography and then (10) The film is patterned to form a transparent pixel electrode 24 (see Fig. 2, which can be made of a metal such as Ming (4)) or silver (Ag) depending on the device to be fabricated (deVlee). form. Thereafter, % is formed into a alignment film by a known method, and then the drive substrate is bonded to the counter substrate, whereby a liquid crystal display device can be manufactured. According to the colored photosensitive resin composition of the present invention, a coating film, a pattern, and a color filter excellent in contrast can be obtained. EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples. Unless otherwise specified, 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, δ490 and Doc. Mixture of the compound shown in A0-2) (manufactured by Chinese and foreign products) 15 parts, 15 parts by air, and 8 parts of N,N-dimethylformamide, while stirring - the surface is maintained below 2G °C'- Add 9 parts of sulphite chloride 1G. After completion of the dropwise addition, the temperature was raised to 50 ° C, 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 12 parts of 2 ethylhexylamine and 22 parts of triethylamine 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, thoroughly washed with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain a mixture of the compound of the formula (Al-a) and the compound of the formula (Ai-b) (dye A1). (a mixture of the compounds represented by the formula (A1_1} to the formula (A1_8)) 11.3 parts.

[In the formula (Al-a) and the formula (Al-b), Rg and RlRi each independently represent 氡原^/子, -S〇3X^-S〇3H or N-(2-ethylhexyl)amine sulfonium sulfonate. Base] 151490.doc -62· 201131294

(A1-1)

(A1-7)

(A1-8) [Synthesis Example 2] (Synthesis of Resin) A nitrogen atmosphere was introduced into a QL flask equipped with a reflux condenser, a dropping funnel and a stirrer at 0.02 L/min to form a nitrogen atmosphere, and a 3-methoxy group was added thereto. -1 - 200 parts by mass of butanol and 105 parts by mass of 3-methoxybutyl acetate, and heated to 70 ° C while stirring. Then, it was dissolved in 60 parts by mass of methacrylic acid, and 3,4-epoxytricyclo[5.2.1.02·6]decyl acrylate (the compound represented by the following formula (B1-1-1) was A solution prepared by formula (B 1-2-1) was mixed with 240 parts by mass of a molar ratio of 50:50 and 140 parts by mass of 3-decyloxybutyl acetate, and a dropping funnel was used. The dissolved droplets were added to a flask maintained at 70 ° C for 4 hours. On the other hand, 30 parts by mass of the polymerization initiator 2,2'-151490.doc -63- 201131294 azobis(2,4-dimethylvaleronitrile) is dissolved in 3-methoxybutyl acetate. Of the 225 parts by mass, the obtained solution was added dropwise to the flask over 4 hours using another dropping funnel. After completion of dropwise addition of the solution of the polymerization initiator, it was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a weight average molecular weight Mw of 1.3 χΙΟ 4, a molecular weight distribution of 2.5, a solid content of 33% by mass, and a solution acid. A resin solution 1 having a value of 34 mg-KOH/g. [化37]

(B1-1-1) 〇 II h2c=ch-c-o

The measurement of the polystyrene-equivalent weight average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) of the resin obtained in Synthesis Example 2 was carried out under the following conditions using a GPC method. Device: HLC-8120GPC (manufactured by Tosoh Co., Ltd.)

String: TSK-GELG2000HXL

Column temperature: 40 ° C Solvent: THF (tetrahydrofuran, tetrahydrofuran) Flow rate: 1 · 0 mL / min The concentration of the solid content of the test liquid: 0.001 to 0.01% by mass Injection amount: 50 μ! > 151490.doc -64- 201131294

Detector : RI

Standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, Fl, A-2500, A-500 (manufactured by Tosoh Corporation) Examples 1 to 4 (Preparation of colored photosensitive resin composition 1) (A) Colorant: CI Pigment Blue 15 : 6 33 parts, acrylic pigment dispersant 5 parts, and

137 parts of propylene glycol monomethyl ether acetate were mixed, and the pigment was sufficiently dispersed using a bead mill, followed by mixing (A) coloring agent: dye A1 5 parts, (B) resin: resin solution 1 150 parts, (C) light Polymerizable compound: dipentaerythritol hexaacrylate ((KAYARAD DPHA; manufactured by Sakamoto Chemical Co., Ltd.) 50 parts, (D) Photopolymerization initiator: N-benzylideneoxy-1-(4-phenyl Sulfur-alkylbenzene I ) Ning; % -丄-03⁄4® (丄rgacure ΟΧϋ 0丄, made by ciDa Japans 5J %) 15 parts, (E) Solvent: 289 parts of ethyl lactate, (F) equivalent to dye A1 A typical metal compound having a mass fraction of 1.5 moles: a typical metal compound described in Table 2, a colored photosensitive resin composition is obtained. Further, as the molecular weight of the dye A1, the molecular weight of the formula (A1-1) is used. [Calculation of Molar Absorption Coefficient] 151490.doc -65- 201131294 The compounds shown in Table 1 were separately weighed in 1 μg in a quantitative flask, followed by dilution with ethyl lactate to reach 0.250 L. UV-visible spectrophotometry Meter (V-650DS; manufactured by JASCO Corporation) (quartz tank, long optical path length Degree: 1 cm) The absorption spectrum of the solution was measured, and the maximum value of the Mohr absorption coefficient ε from the visible light region (380 nm to 780 nm) was calculated using the Lambert-Beer rule. The results are shown in Table 1. [Table 1] Maximum value of Mohr absorbance coefficient (Lmol^cm-1) Dye A1 8031 Bis(dibutyldithiocarbamic acid) zinc 55 bis[bis(2-hydroxyethyl)dithiocarbamic acid] 49 49 (2,4-glutaric acid) indium (III) 35 tris(2,4-pentanedioic acid) aluminum (III) 35 It can be seen that the maximum value of the molar absorption coefficient of any typical metal compound is smaller than that of the dye. The maximum value of the Mohr absorption coefficient. [Formation of the pattern] On a glass substrate of 5 cm square (Eagle 2000; manufactured by Corning), the spin coating method was used to make the chromaticity By after baking to be 0.085. After the coloring photosensitive resin composition was applied, it was prebaked in a clean oven at 100 ° C for 3 minutes, and after standing to cool, an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used in the atmosphere. The substrate coated with the colored photosensitive resin composition 1 was exposed to an exposure amount of 150 mJ/cm 2 (based on 365 nm). After the light irradiation, the coating film was immersed and developed at 23 ° C for 80 seconds in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide of hydrogen 151490.doc -66 - 201131294. After washing with water, it was baked in an oven at 220 ° C for 20 minutes to obtain a pattern. [Colorimetric evaluation] The obtained pattern was measured for spectroscopic using a color measuring machine (OSP-SP-200; manufactured by Olympus Co., Ltd.), and CIE (Commission International de I'Eclairage, χ γ chromaticity coordinates (Βχ, By) and brightness in the XYZ color system of the International Commission on Illumination.

If the brightness is 9.2 or more, it can be judged to be good. The results are shown in Table 2. [Contrast evaluation] The same operation as described above was carried out except that the photomask was not used in the light irradiation, and a coating film was produced in such a manner that the chromaticity By after the post-baking was 〇85. For the obtained coating film, a contrast ratio was measured using a contrast meter (color difference meter BM_5A; Topcon & = clothes, light source. F-10, polarizing film: manufactured by Kesaka Electric Co., Ltd.), and the blank value was set to 30,000. If the contrast is 17_ or more, it can be judged to be good. The results are shown in Table 2. [Heat resistance evaluation] The coating film obtained in 2 was measured by heating in a clean oven for 2 hours, coordinates (Bx, By) and brightness, and calculating the color difference before and after heating. When UAE was 5 or less, it was judged that the heat resistance was good. As a result, in addition, if the heat resistance of the coating film is good, the sample shows good heat resistance. _The case is also the same as the film

[Light resistance evaluation J for the coating film of Toyo Seiki Co., Ltd., measured by Light Resistance Test Co., Ltd.) (Suntest CPS+; I51490.doc •67-201131294 xy chromaticity coordinates before and after treatment for 48 hours ( Bx, By) and brightness, calculate the color difference AEab* before and after the treatment. If AEab* is 5 or less, Beij can judge that the light resistance is good. The results are shown in Table 2. In addition, if the light resistance of the coating film is good, the pattern is also The coating film similarly showed good optical properties. [Table 2] Example 1 2 3 4 Colorant (A) PB15: 6 (parts) υ 33 33 33 33 Dyes Α 1 (parts) 5 5 5 5 Resin (B) Resin solution 1 (part) 150 150 150 150 Photopolymerizable compound (C) Dipentaerythritol hexaacrylate (part) 50 50 50 50 Photopolymerization initiator (D) ΟΧΕ01 (part) 12 12 12 12 Solvent (G) Lactic acid Ethyl ester (parts) 289 289 289 289 Typical metal compound (F) bis(dibutyldithiocarbamic acid) zinc 5.8 - bis bis[bis(2-hydroxyethyl)dithiocarbamic acid] zinc - 4.5 - - Tris(2,4-pentanedioic acid) indium (III) 4.3 - Tris(2,4-glutaric acid) aluminum (III) - _ - 3.4 Contrast 18050 17650 18250 17900 Degree Βχ 0.142 0.142 0.142 0.142 By 0.085 0.085 0.085 0.085 Brightness 9.6 9.6 9.6 9.7 Heat resistance AEab* 4 5 5 4 Visibility AEab* 0.8 1 1 1 Coating formed using the colored photosensitive resin compositions of Examples 1 to 4 In the film, high contrast was observed, and since the brightness was high and the AEab* was 5 or less, it was confirmed that the heat resistance and the light resistance were good. [Industrial Applicability] The colored photosensitive resin composition of the present invention A coating film having a high contrast ratio of 151490.doc -68 to 201131294 can be obtained. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a method of manufacturing a color filter of the present invention. Fig. 2 is a view showing 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. [Description of main components] 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 纟 and compound layer (color film) 23a red filter 23b green filter 23c blue 24 filters the signal line 27 pixel electrode 29 of the photosensitive resin film (protective film) 201, a color filter hole 202 is connected Ο Ο 151490.doc -69 ·

Claims (1)

201131294 VII. Patent Application Range·· 1 · A coloring photosensitive resin composition containing a coloring agent, a resin, a photopolymerizable compound, a photopolymerization initiator, a solvent, and a typical metal compound, and the coloring agent is a dye-containing one The typical metal compound is a carbon atom containing 'the maximum value of the molar absorption coefficient in the visible light region is smaller than the maximum value of the molar absorption coefficient of the dye in the visible light region. 2. A coloring photosensitive resin composition according to the item 1, wherein the maximum value of the molar absorption coefficient of the typical metal compound in the visible light region is 〇 or more Ο 100% or less. 3. The colored photosensitive resin composition of claim 1, wherein the typical metal compound is at least one selected from the group consisting of strontium free magnesium, aluminum, calcium, zinc, gallium, antimony, bismuth, indium, planer and bismuth. Compound. The photosensitive resin composition of the first aspect of the invention, wherein the typical metallized α is a compound containing at least one selected from the group consisting of aluminum, rhodium, indium and ruthenium. 〇 5. The colored photosensitive resin composition of claim 1, which is typically metallized. The substance is selected from the group consisting of _. (=〇)_ and _c(=s)_ are at least a group of compounds. 6. A colored photosensitive resin composition wherein typical metallization :: is selected from the group consisting of a compound represented by the formula (IV) and represented by the formula (F2) (F2) At least one of the group of hydrates of these hydrates: X (F1) 151490.doc 201131294 [In formula (F1) and (F2), wi and w2 are independent of each other and represent carbon number. — a valent aliphatic hydrocarbon group or a carbon number 6 to 1 fluorene monovalent aromatic hydrocarbon group. The aliphatic hydrocarbon group and a hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a hydroxyl group; W and W independently of each other represent a carbon number of 6 6 6 a monovalent aliphatic hydrocarbon group in which a hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with a _ atom; M1 and M2 represent a typical metal atom; ^ and y represent an integer of 1 to 3, and when 乂 is an integer of 2 or more, The plurality of W1 and W2 may be the same or different from each other. When y is an integer of 2 or more, the plurality of W and W4 may be the same or different from each other]. 7. The coloring photosensitive resin composition of the present invention, wherein the content of the typical metal compound is 0.1 part by mass or more and 2 parts by mass or less based on the total amount of the resin and the photopolymerizable compound. 8. The colored photosensitive resin composition according to item 1, wherein the dye is a compound represented by the formula (1): The hydrogen atom contained in the 5 aromatic hydrocarbon group may be independently H, -〇R6, -so3·, -so3h, so3m, -S〇3R6, and -Sn»XTUr.8 [in the formula (1), respectively, R1 to R4 are independent a monovalent aromatic hydrocarbon group, the aromatic; dentate atom, -R6, -0Η, -co2h, _C〇2R6, _s〇r6-S02NR8r9 substituted; hydrogen atom, -R6 or carbon number 6~i〇-S 〇3 ' -SO3H ' S〇3M ' -S02NH2 ' -S02NHR8 or means -S03_, -S〇3H, -S〇3M, -C02H, -C02R6, 151490.doc 201131294 -S03R6, -S02NHR8 or -S02NR8R9 ; m An integer representing 〇~5; when m is an integer of 2 or more, the plurality of feet 5 may be the same or different; X represents a fang atom; a represents an integer of 〇 or 1; and R represents one of carbon numbers 1 to 1 〇 a valence saturated hydrocarbon group 'the remainder and a hydrogen atom contained in the hydrocarbon group may be substituted by a halogen atom', and the _ch2_ contained in the saturated hydrocarbon group may be substituted with -Ο-, -CO- or -NR7-; R represents a number 1 to 1 〇 one-valent saturated hydrocarbon group, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom, and _CH 2 — contained in the saturated hydrocarbon group may be substituted by -Ο- or -CO-; R8 And R9 independently represent a carbon number 〇~〗 直 a linear or branched one-valent saturated aliphatic hydrocarbon group, a carbon number of 3 to 30 one-valent alicyclic hydrocarbon group or _q 'the saturated aliphatic hydrocarbon group and the alicyclic ring The hydrogen atom contained in the hydrocarbon group may be substituted by _, a halogen atom, -Q, _CH=CHCH=CHR6, and the saturated aliphatic hydrocarbon group and the _CH2_ contained in the alicyclic hydrocarbon group may be via _〇_, _s_ , -CO-, -ΝΗ· or _NR, substituted; and the ulnar 9 may be bonded to each other to form a nitrogen atom-containing heterocyclic ring of a 3 to 1 member ring, and the hydrogen atom contained in the hetero ring may pass through R6 , -OH or -Q is substituted; (10) shows a carbon number of 6 to 1 G-valent aryl (tetra)hydrocarbyl group or a carbon number of 5 to 10 -4 ', " earthy aromatic hydrocarbon group and hydrogen contained in the heterocyclic group Atomic 矣OR > -n〇2 . -CH=CH2 > -CH=CHR6^ Substituent; Μ represents a sodium atom or a potassium atom, 151490.doc 201131294 where the + charge of the compound of the formula (1) Number and charge 9. 10. 11. 12. The phase out seeking entry of the colored photosensitive resin composition 1, wherein the colorant's pigment. The colored photosensitive resin composition of claim 9, wherein the pigment is a pigment having a c.i. pigment blue of 15:6. The colored photosensitive resin composition of claim 1 is contained therein. The mass ratio of the pigment of the pigment blue 15.6 to the dye containing the compound of the formula (1) is 97:3 to 50:50. A coating film which is coated with the colored photosensitive resin composition of claim 1 and dried to form By. 13. A pattern formed by coating a material as claimed and drying. A color-sensitive resin combination 14. A color filter comprising at least one selected from the group consisting of the coating of claim 12 and the coating film of claim 12. 151490.doc