TWI491982B - Coloring the photosensitive resin composition - Google Patents

Description

Colored photosensitive resin composition

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 color filter using the colored photosensitive resin composition.

The coloring photosensitive resin composition is used in the industry to manufacture color filters used in display devices such as liquid crystal display panels, electroluminescence panels, and plasma display panels. It is known that a pigment or a dye is used as a coloring agent in the colored photosensitive resin composition (Non-Patent Document 1).

[Non-Patent Document 1] Suzuki's eighty-two, "Easy-to-understand LCD display manufacturing process", first edition, Nikkan Kogyo Shimbun, March 2005, p. 112

An object of the present invention is to provide a colored photosensitive resin composition which can form a coating film, a pattern, and a color filter which are excellent in heat resistance.

That is, the present invention provides the following [1] to [15].

[1] A colored photosensitive resin composition containing a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E), and a colorant (A) is a coloring agent containing a dye, and the binder resin (B) is a resin containing a polycarboxylic acid resin obtained as follows, that is, one or more epoxy resins (a) having two glycidyl groups, One or more of the dibasic acid (b) represented by the formula (Bb) and one or more ethylenically unsaturated monocarboxylic acids (c) are reacted, and then the obtained polymer and one or more polybasic acid anhydrides (d) are reacted. reaction:

HOOC-R ^a -COOH (Bb)

[In the formula (Bb), R ^a represents ^a divalent aliphatic hydrocarbon group having 2 to 8 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 8 carbon atoms, the aliphatic hydrocarbon group and hydrogen contained in the alicyclic hydrocarbon group. The atom can be substituted by a hydroxyl group].

[2] The colored photosensitive resin composition according to [1], wherein the binder resin (B) is a resin comprising a polycarboxylic acid resin obtained in such a manner that more than one ring having two glycidyl groups is obtained The oxygen resin (a), one or more of the dibasic acid (b) represented by the formula (Bb), and one or more ethylenically unsaturated monocarboxylic acids (c) are reacted, and then the obtained polymer is one or more kinds. The polybasic acid anhydride (d) is reacted, and further reacted with one or more radical polymerizable compounds (e) having one glycidyl group:

HOOC-R ^a -COOH (Bb)

[In the formula (Bb), Ra represents a divalent aliphatic hydrocarbon group having 2 to 8 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 8 carbon atoms, and the aliphatic hydrocarbon group and the hydrogen atom contained in the alicyclic hydrocarbon group. Can be substituted by a hydroxyl group].

[3] The colored photosensitive resin composition according to [2], wherein the amount of addition of the radically polymerizable compound (e) having one glycidyl group is 0.05 to 0.90 with respect to the polybasic acid anhydride (d) 1 molar Moor.

[4] The colored photosensitive resin composition according to any one of [1] to [3] wherein the epoxy resin (a) having two glycidyl groups is an epoxy resin represented by the formula (Ba):

[Chemical 1]

[In the formula (Ba), R ^b , R ^c , R ^d and R ^e represent a hydrogen atom or a methyl group; n represents a number from 0 to 10, and when n is an integer of 2 or more, a plurality of R ^b and R ^c are mutually Can be the same or different].

[5] The colored photosensitive resin composition according to any one of [1] to [4] wherein the ethylenically unsaturated monocarboxylic acid (c) is at least selected from the group consisting of acrylic acid and methacrylic acid. One.

[6] The colored photosensitive resin composition according to [2] or [3], wherein the radically polymerizable compound (e) having one glycidyl group is selected from the group consisting of glycidyl acrylate and glycidyl methacrylate At least one of the group consisting of.

[7] The colored photosensitive resin composition according to any one of [1] to [6] wherein the content of the binder resin (B) is relative to the total amount of the binder resin (B) and the photopolymerizable compound (C) It is 20% by mass or more and 80% by mass or less.

[8] The colored photosensitive resin composition according to any one of [1] to [7] wherein the content of the dye is 0.5% by mass or more and 60% by mass or less based on the solid content of the colored photosensitive resin composition. .

[9] The colored photosensitive resin composition according to any one of [1] to [8] wherein the dye contains a metal complex selected from the group consisting of an azo compound, an azo compound as a ligand, and dibenzo At least one of the group consisting of pyran compounds.

[10] The colored photosensitive resin composition according to any one of [1] to [9] wherein the dye comprises the dye represented by the formula (1):

[Chemical 2]

[In the formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁶ or a carbon number 6 to 10 monovalent aromatic hydrocarbon group, and a hydrogen atom contained in the aromatic hydrocarbon group may pass through a halogen atom, - R ⁶ , -OH, -OR ⁶ , -SO ₃ ^- , -SO ₃ H, SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NH ₂ , -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ^{9 is} substituted; R ⁵ represents -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ ; m represents an integer of 0 to 5; when m is an integer of 2 or more, plural R ^{5 's} may be the same or different; X represents a halogen atom; a represents an integer of 0 or 1. R ⁶ represents a one-valent saturated hydrocarbon group having 1 to 10 carbon atoms, 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 -O-, -CO- Or -NR ⁷ -substituted; R ⁷ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, 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 - O- or -CO-; R ⁸ and R ⁹ each independently represent a carbon number of 1 to 10 linear or branched divalent saturated aliphatic hydrocarbon group having one, one having 3 to 30 carbon atoms, divalent alicyclic hydrocarbon group -Q, of the hydrogen atoms contained in the aliphatic hydrocarbon and the saturated alicyclic hydrocarbon group may be substituted with = CHR ⁶ -OH, a halogen atom, -Q, -CH = CH ₂ or -CH, and the saturated aliphatic hydrocarbon -CH ₂ - contained in the alicyclic hydrocarbon group may be substituted by -O-, -S-, -CO-, -NH- or -NR ⁶ -; R ⁸ and R ⁹ may be bonded to each other to form 3~ a heterocyclic ring containing a nitrogen atom of a 10-member ring, wherein the hydrogen atom contained in the hetero ring may be substituted by R ⁶ , -OH or -Q; Q represents a carbon number of 6 to 10 monovalent aromatic hydrocarbon group or carbon number 3~ a monovalent heterocyclic group, the aromatic hydrocarbon group and a hydrogen atom contained in the heterocyclic group may be via -OH, R ⁶ , -OR ⁶ , -NO ₂ , -CH=CH ₂ , -CH=CHR ⁶ Or a halogen atom; M represents a sodium atom or a potassium atom; wherein the compound of the formula (1) has a + charge number which is the same as the - charge number].

[11] The colored photosensitive resin composition according to any one of [1] to [10] wherein the coloring agent (A) is a coloring agent further comprising a pigment.

[12] The colored photosensitive resin composition according to [11], wherein the pigment comprises a pigment selected from the group consisting of CI Pigment Blue 15:6, CI Pigment Red 254, CI Pigment Red 242, CI Pigment Red 177, CI Pigment Green 58, CI Pigment At least one of the group consisting of yellow 150 and CI pigment yellow 138.

[13] A coating film obtained by applying the colored photosensitive resin composition according to any one of [1] to [12] onto a substrate and drying.

[14] A pattern obtained by applying the colored photosensitive resin composition according to any one of [1] to [12] onto a substrate, drying, exposing, and developing.

[15]. A color filter comprising a coating film of [13], a pattern such as [14], or a coating film such as [13] and a pattern such as [14].

The colored photosensitive resin composition of the present invention contains a coloring agent (A).

The coloring agent (A) used in the colored photosensitive resin composition of the present invention is a coloring agent containing a dye. The dye contained in the colorant (A) is not particularly limited, and a well-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 can be mentioned.

Examples of the dyes include those classified as dyes in the "Dye Index" (published by The Society of Dyers and Colourists), and well-known dyes described in "Staining Notes" (color dyeing company). Specific examples thereof include CI Solvent Yellow 4 (hereinafter, "CI Solvent Yellow" is omitted, and only the number is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162; CI solvent red 45, 49, 125, 130; CI solvent orange 2, 7, 11, 15, 26, 56; CI solvent blue 35, 37, 59, 67; CI solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc. Further, examples of the CI acid dye include CI acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76. , 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169 , 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240 , 242, 243, 251; CI acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426; CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; CI Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51 , 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243 , 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340; CI Acid Violet 6B, 7, 9, 17, 19; CI Acid Green 1, 3, 5, 9 , 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109 and other dyes. 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, 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. Further, as the CI mord dye, CI mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; 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.

In addition, examples of the dye contained in the coloring agent (A) include an amine salt of an acid dye represented by the following formulas (i) to (vii) and a sulphur of an acid dye represented by the formulas (viii) and (ix). Amidoxime derivative.

D-(SO ₃ ^- ) _v (C _w H _2w+1 N ⁺ H ₃ ) _v (i)

D-(SO ₃ ^- ) _v {(C _w H _2w+1 ) ₂ N ⁺ H ₂ } _v (ii)

D-(SO ₃ ^- ) _v {(C _w H _2w+1 ) ₃ N ⁺ H} _v (iii)

D-(SO ₃ ^- ) _v {(C _w H _2w+1 ) ₄ N ⁺ } _v (iv)

D-(SO ₃ ^- ) _v (C _e H _2e+1 OC _f H _2f N ⁺ H ₃ ) _v (v)

D-(SO ₃ ^- ) _v {(C _w H _2w+1 )(PhCH ₂ ) ₂ N ⁺ H} _v (vi)

D-(SO ₃ ^- ) _v {(C _w H _2w+1 )Py ⁺ } _v (vii)

D-[{SO ₂ NH(C _w H _2w+1 )} _p ][(SO ₃ L) _q ] (viii)

D-[{SO ₂ NH(C _e H _2e+1 OC _f H _2f )} _p ][(SO ₃ L) _q ] (ix)

[In the formulae (i) to (ix), D represents a group derived from a pigment.

v represents an integer of 1 or more and 20 or less, and w represents an integer of 1 or more and 20 or less.

e and f each independently represent an integer of 1 or more and 10 or less.

Ph represents a phenyl group, and Py represents a group represented by the formula (x) in which a nitrogen atom is bonded to C _w H _2w+1 .

[Chemical 3]

(In the formula (x), R ^a represents a methyl group. ma represents an integer of 0 or 1.)

p represents an integer of 1 or more and 8 or less.

q represents an integer of 0 or more and 8 or less.

L represents a hydrogen atom or a monovalent cation]

Specific examples of D in the formulae (i) to (ix) include a group derived from an azo dye, an anthraquinone dye, a triphenylmethane dye, a dibenzopyran dye, and a phthalocyanine dye.

m is preferably an integer of 1 or more and 10 or less, and more preferably an integer of 1 or more and 8 or less.

n is preferably an integer of 1 or more and 10 or less, and more preferably an integer of 1 or more and 8 or less.

It is preferable that e and f independently represent an integer of 1 or more and 8 or less, and more preferably an integer of 1 or more and 6 or less.

Py is preferably a group represented by the formula (x1).

[Chemical 4]

p is preferably an integer of 1 or more and 6 or less, and more preferably an integer of 1 or more and 5 or less.

q is preferably an integer of 0 or more and 6 or less, and more preferably an integer of 0 or more and 5 or less.

Examples of the L-valent cation include a lithium ion, a sodium ion, a potassium ion, a quaternary ammonium ion such as (C ₂ H ₅ ) ₃ HN ^{+ ,} and the like, and a sodium ion is preferred.

Examples of the azo dye include dyes represented by the following formulas (a) to (d).

[Chemical 5]

In the formula (a), R ^z1 represents an alkyl group having 2 to 20 carbon atoms, a cyclohexylalkyl group having 2 to 12 carbon atoms in the alkyl chain, an alkylcyclohexyl group having 1 to 4 carbon atoms in the alkyl chain, An alkyl group having 2 to 12 carbon atoms substituted with an alkoxy group having 2 to 12 carbon atoms, an alkylcarboxyalkyl group represented by the formula (a-1), and an alkoxycarbonylalkyl group represented by the formula (a-2) a phenyl group substituted with an alkyl group having 1 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms substituted by a phenyl group.

L ¹ -CO-OL ² - (a-1)

L ³ -O-CO-L ⁴ - (a-2)

In the formula (a-1), L ¹ represents an alkyl group having 2 to 12 carbon atoms. L ² represents an alkylene group having 2 to 12 carbon atoms.

In the formula (a-2), L ³ represents an alkyl group having 2 to 12 carbon atoms. L ⁴ represents an alkylene group having a carbon number of 2 to 12]

In the formula (a), R ^z2 to R ^z5 represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxyl group or a halogen atom.

Examples of the alkyl group having 2 to 20 carbon atoms include ethyl group, n-propyl group, isopropyl group, n-hexyl group, n-decyl group, n-decyl group, n-dodecyl group, 2-ethylhexyl group, and 1, 3-dimethylbutyl, 1-methylbutyl, 1,5-dimethylhexyl and 1,1,3,3-tetramethylbutyl and the like.

Examples of the cyclohexylalkyl group having 2 to 12 carbon atoms in the alkyl chain include a cyclohexylethyl group, a 3-cyclohexylpropyl group, and an 8-cyclohexyloctyl group.

Examples of the alkylcyclohexyl group having 1 to 4 carbon atoms in the alkyl chain include 2-ethylcyclohexyl group, 2-propylcyclohexyl group, and 2-(n-butyl)cyclohexyl group.

Examples of the alkyl group having 2 to 12 carbon atoms which are substituted by an alkoxy group having 2 to 12 carbon atoms include 3-ethoxy-n-propyl group, propoxypropyl group, 4-propoxy-n-butyl group, and 3 - methyl n-hexyloxyethyl and 3-(2-ethylhexyloxy)propyl and the like.

Examples of the phenyl group substituted with an alkyl group having 1 to 20 carbon atoms include o-isopropylphenyl group and the like.

Examples of the alkyl group having 1 to 20 carbon atoms substituted by a phenyl group include a DL-1-phenylethyl group, a benzyl group, and a 3-phenyl-n-butyl group.

Examples of the alkyl group having 2 to 12 carbon atoms of L ¹ and L ³ include an ethyl group, a propyl group, a n-hexyl group, a n-decyl group, a n-decyl group, an n-dodecyl group, a 2-ethylhexyl group, and 1, 3-dimethylbutyl, 1-methylbutyl, 1,5-dimethylhexyl and 1,1,3,3-tetramethylbutyl and the like.

Examples of the alkylene group having 2 to 12 carbon atoms of L ² and L ⁴ include an exoethyl group and a hexyl group.

Examples of R ^z2 to R ^z5 in the formula (a) include a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, a n-butyl group, an isopropyl group, a second butyl group, a third butyl group, a carboxyl group, and a fluorine. Examples of the atom, the chlorine atom, the bromine atom and the iodine atom include a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, a n-butyl group, an isopropyl group, a second butyl group, a third butyl group, and a fluorine atom. Atom or chlorine atom.

Among the dyes represented by the formula (a), specific examples of the dyes include compounds represented by the formula (e).

[Chemical 6]

As the dye having a group derived from an anthraquinone dye, for example, a compound represented by the formula (f) can be mentioned.

As the dye having a group derived from a triphenylmethane dye, for example, a compound represented by the formula (g) can be mentioned.

As the dye having a group derived from a dibenzopyran dye, for example, a compound represented by the formula (h) can be mentioned.

In addition, examples of the dye having a group derived from a phthalocyanine dye include a compound represented by the formula (j).

[Chemistry 7]

The dye is preferably a dye containing at least one selected from the group consisting of an azo compound, a metal complex having an azo compound as a ligand, and a dibenzopyran compound, and more preferably contains A dye of at least one selected from the group consisting of compounds represented by the following formulas (1) to (3) is selected. The dye is preferably a dye which can be dissolved in any of the following solvents used in the colored photosensitive resin composition of the present invention.

As the dye, a dye containing a dibenzopyran compound is preferred, and a dye containing a compound represented by the following formula (1) is more preferred.

[化8]

In the compound represented by the formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁶ or a C 6-10 monovalent aromatic hydrocarbon group.

R ⁶ above represents a one-valent saturated hydrocarbon group having 1 to 10 carbon atoms. The 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 -O-, -CO- or -NR ⁷ - (R ⁷ represents a carbon number of 1 to 10) A monovalent saturated hydrocarbon group in which a hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom, and -CH ₂ - may be substituted by -O- or -CO-.

Examples of -R ⁶ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, and g. Base, cycloheptyl, octyl, 2-ethylhexyl, cyclooctyl, decyl, decyl, tricyclodecyl, methoxypropyl, ethoxypropyl, hexyloxypropyl, 2- Ethylhexyloxypropyl, methoxyhexyl, ethoxypropyl, and the like.

Examples of the one-valent aromatic hydrocarbon group having 6 to 10 carbon atoms of R ¹ to R ⁴ and Q include a phenyl group and a naphthyl group.

Further, the hydrogen atom contained in the one-membered aromatic hydrocarbon group having 6 to 10 carbon atoms of R ¹ to R ⁴ may pass through a halogen atom, -R ⁶ , -OH, -OR ⁶ , -SO ₃ ^- , -SO ₃ H , SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NH ₂ , -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ^{9 is} substituted.

The above R ⁶ represents the same meaning as described above.

The above R ⁸ and R ⁹ each independently represent a linear or branched one-valent saturated aliphatic hydrocarbon group having a carbon number of 1 to 10, a carbon number of 3 to 30 one-valent alicyclic hydrocarbon group or -Q (Q represents a carbon number of 6~). a monovalent aromatic hydrocarbon group or a carbon number of 3 to 10 one-valent heterocyclic group, wherein the hydrogen atom contained in the group may be through -OH, -R ⁶ , -OR ⁶ , -NO ₂ , -CH=CH ₂ , -CH=CHR ⁶ or a halogen atom substitution).

The linear or branched one-valent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms of R ⁸ and R ⁹ and the hydrogen atom contained in the one-carbon alicyclic hydrocarbon group having 3 to 30 carbon atoms may pass through -OH, a halogen atom , -Q, -CH=CH ₂ or -CH=CHR ⁶ substituted, -CH ₂ - may be substituted with -O-, -S-, -CO-, -NH- or -NR ⁶ -.

R ⁸ and R ⁹ may be bonded to each other to form a heterocyclic ring of 3 to 10 membered rings. In this case, the hydrogen atom contained in the hetero ring may be substituted by -R ⁶ , -OH or -Q.

Further, the above M represents a sodium atom or a potassium atom.

Examples of the halogen atom which can replace the hydrogen atom contained in the one-valent aromatic hydrocarbon group having 6 to 10 carbon atoms of R ¹ to R ⁴ include a fluorine atom, a chlorine atom and a bromine atom.

Examples of -OR ⁶ include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a second butoxy group, a third butoxy group, a n-pentyloxy group, and a hexyl group. Oxyl, heptyloxy, octyloxy, 2-ethylhexyloxy, decyloxy, decyloxy and the like.

Examples of -CO ₂ R ⁶ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, a pentyloxycarbonyl group, and an isopenic group. Oxycarbonyl, neopentyloxycarbonyl, cyclopentyloxycarbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, heptyloxycarbonyl, cycloheptyloxycarbonyl, octyloxycarbonyl, 2-ethylhexyloxy Carbonyl, cyclooctyloxycarbonyl, decyloxycarbonyl, decyloxycarbonyl, tricyclodecyloxycarbonyl, methoxypropoxycarbonyl, ethoxypropoxycarbonyl, hexyloxypropoxycarbonyl, 2 Ethylhexyloxypropoxycarbonyl, methoxyhexyloxycarbonyl and the like.

The heterocyclic ring containing a nitrogen atom of a 3 to 10 membered ring formed by bonding R ⁸ and R ^{9 to} each other in -SO ₂ NR ⁸ R ⁹ may, for example, be:

Wait. Further, the above heterocyclic ring is bonded to a sulfur atom by a bond described in the above figure.

As a one-valent heterocyclic group having 3 to 10 carbon atoms of Q, examples thereof include:

Wait. Further, the bond of the heterocyclic group of Q may be any position.

Examples of -SO ₃ R ⁶ include a methoxysulfonyl group, an ethoxysulfonyl group, a hexyloxysulfonyl group, and a decyloxysulfonyl group.

Examples of -SO ₂ NHR ⁸ include N-methylaminesulfonyl, N-ethylaminesulfonyl, N-propylaminesulfonyl, N-isopropylaminesulfonyl, N-butyl Amine sulfonyl, N-isobutylamine sulfonyl, N-pentylamine sulfonyl, N-isoamylamine sulfonyl, N-neopentylamine sulfonyl, N-cyclopentyl Aminesulfonyl, N-hexylaminesulfonyl, N-cyclohexylaminesulfonyl, N-heptylaminesulfonyl, N-cycloheptylaminesulfonyl, N-octylaminesulfonyl, N-(2-ethylhexyl)amine sulfonyl, N-(1,5-dimethylhexyl)amine sulfonyl, N-cyclooctylamine sulfonyl, N-decylamine sulfonyl, N-decylamine sulfonyl, N-tricyclodecylamine sulfonyl, N-methoxypropylamine sulfonyl, N-ethoxypropylamine sulfonyl, N-propoxy Amine sulfonyl, N-isopropoxypropylamine sulfonyl, N-hexyloxypropylamine sulfonyl, N-(2-ethylhexyloxypropyl)amine sulfonyl, N -(Methoxyhexyl)aminesulfonyl, N-(3-phenyl-1-methylpropyl)aminesulfonyl and the like.

Further, examples of -SO ₂ NHR ⁸ include a group represented by the following formula.

[Chemistry 9]

[化10]

[11]

[化12]

In the above formula, X ¹ represents a halogen atom. Examples of the halogen atom of X ¹ include a fluorine atom, a chlorine atom, and a bromine atom.

[Chemistry 13]

[Chemistry 14]

[化15]

[Chemistry 16]

In the above formula, X ³ represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and a hydrogen atom of the alkyl group and the alkoxy group may be substituted by a halogen atom.

Examples of the alkyl group having 1 to 3 carbon atoms which may be substituted by a halogen atom include a methyl group, an ethyl group, a propyl group, an isopropyl group, and 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.

[化17]

[化18]

[Chemistry 19]

[Chemistry 20]

[Chem. 21]

In the above formula, X ³ represents the same meaning as described above.

In the above formula, X ² represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a halogen atom or a nitro group, and the hydrogen atom contained in the alkyl group and the alkoxy group may pass through a halogen atom. Replace.

Examples of the halogen atom of X ² include a fluorine atom, a chlorine atom and a bromine atom.

Examples of the alkyl group having 1 to 3 carbon atoms which may be substituted by a halogen atom include a methyl group, an ethyl group, a propyl group, an isopropyl group, and 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.

[化22]

Among them, as -SO ₂ NHR ⁸ , R ⁸ is 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, a phenyl group, and a carbon number. 8 to 10 aralkyl groups, a saturated aliphatic hydrocarbon group having a hydroxyl group of 2 to 8 and an aryl group or a saturated aliphatic hydrocarbon group or aryl group having an alkoxy group having 2 to 8 carbon atoms, particularly preferably R ⁸ is 2-ethylhexyl.

Examples of -SO ₂ NR ⁸ R ⁹ include a group represented by the following formula.

[化23]

[Chem. 24]

[化25]

[Chem. 26]

In the above formula, X ² represents the same meaning as described above.

[化27]

R ⁸ and R ⁹ contained in -SO ₂ NR ⁸ R ⁹ are preferably a branched saturated aliphatic hydrocarbon group having 6 to 8 carbon atoms, an alicyclic hydrocarbon group having 5 to 7 carbon atoms, and an allyl group. a phenyl group, an aralkyl group having 8 to 10 carbon atoms, a saturated aliphatic hydrocarbon group having a hydroxyl group of 2 to 8 and an aryl group or a saturated aliphatic hydrocarbon group or aryl group having an alkoxy group having 2 to 8 carbon atoms. Particularly preferred is 2-ethylhexyl.

The substituent of the aromatic hydrocarbon group having 6 to 10 carbon atoms of R ¹ to R ⁴ in the formula (1) is preferably ethyl, propyl, phenyl, dimethylphenyl or -SO ₃ R ^{6 .} Or -SO ₂ NHR ⁸ .

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms having a substituent include methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, hexylphenyl, nonylphenyl, and fluorine. Phenyl, chlorophenyl, bromophenyl, hydroxyphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, decyloxyphenyl, trifluoromethyl Phenyl and the like.

In R ¹ to R ⁴ in the formula (1), it is preferred that at least one of R ¹ and R ² or at least one of R ³ and R ⁴ is a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms or The carbon number 6 to 10 monovalent aromatic hydrocarbon group which may be substituted.

Further, it is preferred that at least one of R ¹ and R ² and at least one of R ³ and R ⁴ is one of a carbon number of 1 to 4 saturated hydrocarbon groups or a carbon number of 6 to 10 which may be substituted The valent aromatic hydrocarbon group is more preferably at least one of R ¹ and R ² and at least one of R ³ and R ⁴ is a substitutable carbon number 6 to 10 monovalent aromatic hydrocarbon group.

In the compound represented by the formula (1), R ⁵ represents -SO ₃ -, -SO ₃ H, SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ .

In the formula (1), m represents an integer of 0 to 5, and when m is an integer of 2 or more, a plurality of R ^{5 's} may be the same or different.

Preferred examples of R ⁵ include a carboxyl group, an ethoxycarbonyl group, a sulfo group, N-(2-ethylhexyloxypropyl)aminesulfonyl group, and N-(1,5-dimethylhexyl). Aminesulfonyl, N-(3-phenyl-1-methylpropyl)aminesulfonyl, N-(isopropoxypropyl)aminesulfonyl.

In the formula (1), X represents a halogen atom, and a represents an integer of 0 or 1.

Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, and a bromine atom.

The compound represented by the formula (1) is preferably a compound represented by the following formula (1-1) or (1-2).

[化28]

[In the formula (1-1), R ¹¹ to R ¹⁴ each independently represent a hydrogen atom, -R ⁶ or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and a hydrogen atom contained in the aromatic hydrocarbon group may pass through a halogen atom, - R ⁶ , -OH, -OR ⁶ , -SO ₃ -, -SO ₃ H, -SO ₃ Na, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NH ₂ , -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ substituted.

R ¹⁵ represents a hydrogen atom, -SO ₃ -, -SO ₃ H, -SO ₂ NH ₂ , -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ .

R ¹⁶ represents -SO ₃ -, -SO ₃ H, -SO ₂ NH ₂ , -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ .

R ⁶ , R ⁸ , R ⁹ , m, X and a have the same meanings as described above.

Wherein the compound represented by the formula (1-1) has the same charge number as the - charge number]

[化29]

[In the formula (1-2), R ²¹ to R ²⁴ each independently represent a hydrogen atom, -R ²⁶ or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and a hydrogen atom contained in the aromatic hydrocarbon group may pass through a halogen atom, - R ²⁶ , -OH, -OR ²⁶ , -SO ₃ ^- , -SO ₃ Na, -CO ₂ H, -CO ₂ R ²⁶ , -SO ₃ H, -SO ₃ R ²⁶ or -SO ₂ NHR ^{28 are} substituted.

R ²⁵ represents -SO ₃ ^- , -SO ₃ Na, -CO ₂ H, -CO ₂ R ²⁶ , -SO ₃ H or -SO ₂ NHR ²⁸ .

R ²⁶ 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 -OR ²⁷ or a halogen atom.

R ²⁷ 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 a halogen atom.

R ²⁸ represents a hydrogen atom, -R ²⁶ , -CO ₂ R ²⁶ or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and a hydrogen atom contained in the aromatic hydrocarbon group may be substituted with -R ²⁶ or -OR ²⁶ .

m, X and a represent the same meanings as described above.

Wherein, the compound of the formula (1-2) has the same charge number as the - charge number]

Further, the compound represented by the formula (1) is preferably a compound represented by the following formula (1-3).

[化30]

[In the formula (1-3), R ³¹ and R ³² each independently represent a phenyl group, and a hydrogen atom contained in the phenyl group may pass through a halogen atom, -R ²⁶ , -OR ²⁶ , -CO ₂ R ²⁶ , -SO ₃ R ²⁶ or -SO ₂ NHR ²⁸ substituted.

R ³³ represents -SO ₃ ^- or -SO ₂ NHR ²⁸ .

R ³⁴ represents a hydrogen atom, -SO ₃ ^- or -SO ₂ NHR ²⁸ .

R ²⁶ , R ²⁸ , X and a have the same meanings as described above.

In addition, the compound represented by the formula (1-3) has the same charge number as the -charge number. Further, the compound represented by the formula (1) is more preferably a compound represented by the following formula (1-4).

[化31]

[In the formula (1-4), R ⁴¹ and R ⁴² each independently represent a phenyl group, and a hydrogen atom contained in the phenyl group may be substituted with -R ²⁶ or -SO ₂ NHR ²⁸ .

R ⁴³ represents -SO ₃ ^- or -SO ₂ NHR ²⁸ .

R ²⁶ , R ²⁸ , X and a have the same meanings as described above.

Wherein, the compound of the formula (1-4) has the same charge number as the - charge number]

Examples of the compound represented by the formula (1) include compounds represented by the following formulas (1a) to (f).

[化32]

[In the formula (1a), R ⁵¹ and R ⁵² each independently represent a hydrogen atom, -SO ₃ ^- , -SO ₃ H, -CO ₂ H or -SO ₂ NHR ⁵⁰ . R ⁵⁰ represents 2-ethylhexyl. X and a have the same meanings as described above.

Wherein, the compound of formula (1a) has the same number of + charges as the number of charges -

[化33]

In the formula (1b), R ⁵¹ represents the same meaning as described above. Wherein, the compound of formula (1b) has the same number of + charges as the number of charges -

The compound represented by the formula (1b) is a tautomer of the compound represented by the formula (1b-1).

[化34]

In the formula (1b-1), R ⁵¹ , X and a have the same meanings as described above. Wherein, the compound of the formula (1b-1) has the same charge number as the - charge number]

[化35]

[In the formulae (1c) and (1d), R ⁵³ , R ⁵⁴ and R ⁵⁵ each independently represent -SO ₃ ^- , -SO ₃ Na or -SO ₂ NHR ⁵⁰ . R ⁵⁰ represents 2-ethylhexyl. Wherein, the compound represented by the formula (1c) and the compound represented by the formula (1d) have the same charge number and charge number respectively]

[化36]

In the formulae (1e) and (1f), R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represent a hydrogen atom, -SO ₃ ^- , -SO ₃ H or -SO ₂ NHR ⁵⁰ . R ⁵⁰ represents 2-ethylhexyl. Wherein, the compound represented by the formula (1e) and the compound represented by the formula (1f) have the same charge number and charge number respectively]

Specific examples of the compound represented by the formula (1a) to the formula (1f) include a compound obtained by sulfonylation of sulfonate rose B, sulfonate rose B, and -SO ₃ - or -SO ₃ H, CI Solvent Red 49, Rose Bengal B, CI Acid Violet 102, CI Acid Violet 102 ^- SO ₃ ^- or -SO ₃ H Compound obtained by sulfoximation, CI Acid Red 289, CI Acid Red 289 ^- SO ₃ ^- Or a compound obtained by sulfonylation of -SO ₃ H or the like. In particular, the dye used in the colored photosensitive resin composition of the present invention is preferably a compound represented by the formula (1e) or the formula (1f), and specifically, CI red 289, CI is preferred. The compound obtained by sulfoximation of acid red 289-SO ₃ ^- or -SO ₃ H. Particularly preferred is a compound of the formula (h).

[化37]

The compound represented by the formula (1) can be produced, for example, by chlorinating a dye or a pigment intermediate having -SO ₃ H by a usual method, and obtaining a pigment or pigment having -SO ₂ Cl obtained. The intermediate is reacted with an amine represented by R ⁸ -NH ₂ . In addition, it is also possible to produce a dye produced by the method described in the upper right column to the lower left column of page 3 of Japanese Patent Laid-Open No. Hei 3-78702, and then chlorinated in the same manner as described above to The amine is reacted.

In the case where the coloring agent (A) contains the compound represented by the formula (1), the content of the compound represented by the formula (1) in the coloring agent (A) is preferably from 3 to 80% by mass, more preferably 3 to 70% by mass, and further preferably 3 to 50% by mass.

When the colorant (A) contains a dye different from the compound represented by the formula (1), the mixing ratio of the compound represented by the formula (1) and the dye different from the compound represented by the formula (1) is preferred. It is in the following range.

Compound represented by formula (1): 1 to 99% by mass

Dye different from the compound represented by formula (1): 1 to 99% by mass

When the compounding ratio of the compound represented by the formula (1) and the dye different from the compound represented by the formula (1) is within the above range, the target spectroscopic light can be obtained.

As the dye, a dye containing an azo compound is preferred, and a dye containing a compound represented by the formula (2) is more preferred.

In the formula (2), A ⁰ represents a divalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent.

B ⁰ represents a one-valent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent or a monovalent heterocyclic group having 3 to 14 carbon atoms which may have a substituent.

R ⁵¹ represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent, or a fluorenyl group having 2 to 18 carbon atoms which may have a substituent.

P1 represents 1 or 2. In the case where p1 is 2, the plurality of A ⁰ , B ⁰ , R ⁵¹ and R ⁵² may be the same or different from each other.

In the case where p1 is 1, R ⁵² represents a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a monovalent substituent, and in the case where p1 is 2, R ⁵² represents a carbon which may have a substituent. a divalent aliphatic hydrocarbon group of 1 to 35, and the monovalent aliphatic hydrocarbon group and -CH ₂ - contained in the divalent aliphatic hydrocarbon group may be -O-, -S-, -CO-, and -NR'- Replace.

R' represents a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms]

The compound represented by the formula (2) is preferably a compound represented by the formula (2-1).

[In the formula (2-1), Z ¹ , Z ² and Z ³ each independently represent a divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent, and are contained in Z ¹ , Z ² and Z ³ - CH ₂ - may be substituted by -CO- or -O-.

R ⁵³ and R ⁵⁴ each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent, or a fluorenyl group having 2 to 18 carbon atoms which may have a substituent.

A ¹ and A ² each independently represent a divalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent.

B ¹ and B ² each independently represent a one-valent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent or a 3 to 14 one-valent heterocyclic group having a substituent;

Z ¹ , Z ² and Z ³ each independently represent a divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent. The carbon number of the divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms does not include the carbon number of the substituent, and the amount thereof is preferably 2 to 10, more preferably 2 to 8.

Examples of the divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms include alkanediyl having 1 to 16 carbon atoms, and examples thereof include a methylene group, an ethylidene group, a propylenediyl group, a dibutyl group, a pentanediyl group and a hexamethylene group. Base, heptadienyl, octyldiyl, decyldiyl, tetradecanediyl and hexadecanediyl.

The -CH ₂ - contained in the divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms may be substituted by -CO- or -O-. The hydrogen atom contained in the aliphatic hydrocarbon group having 1 to 16 carbon atoms may be substituted with a halogen atom such as a fluorine atom.

Z ¹ and Z ^{2 are} preferably an alkanediyl group having 1 to 8 carbon atoms which may contain -O-, more preferably an alkanediyl group having 5 to 7 carbon atoms which may contain -O-. As a preferred group, for example, -(CH ₂ ) ₃ -, -(CH ₂ ) ₂ -O-(CH ₂ ) ₂ -, -(CH ₂ ) ₂ -O-(CH ₂ ) ₂ -O -(CH ₂ ) ₂ - or -CH ₂ -CH(CH ₃ )-.

Z ^{3 is} preferably a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms which may contain -C(=C)-, more preferably an unsubstituted alkanediyl group having 1 to 8 carbon atoms, more preferably An unsubstituted alkanediyl group having 4 to 8 carbon atoms. Preferred examples thereof include -(CH ₂ ) ₂ -, -(CH ₂ ) ₄ - or -CH ₂ -C(=CH ₂ )-.

The one-valent aliphatic hydrocarbon group having 1 to 16 carbon atoms of R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ may be linear, branched or cyclic. The carbon number of the aliphatic hydrocarbon group does not include the carbon number of the substituent, and the amount thereof is preferably from 6 to 10, more preferably from 1 to 4.

Examples of the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, second butyl group, and third butyl group. Butyl (1,1,3,3-tetramethylbutyl, etc.), methylhexyl (1,5-dimethylhexyl, etc.), ethylhexyl (2-ethylhexyl, etc.), cyclopentyl , cyclohexyl, methylcyclohexyl (2-methylcyclohexyl, etc.) and cyclohexylalkyl.

The hydrogen atom contained in the one-valent aliphatic hydrocarbon group having 1 to 16 carbon atoms may be substituted with an alkoxy group having 1 to 8 carbon atoms or a carboxyl group. Examples of the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which are substituted by an alkoxy group having 1 to 8 carbon atoms include propoxypropyl (3-(isopropoxy)propyl group, etc.) and alkoxy group. Propyl (3-(2-ethylhexyloxy)propyl, etc.). Examples of the aliphatic hydrocarbon group having 1 to 16 carbon atoms substituted by a carboxyl group include a 2-carboxyethyl group, a 3-carboxypropyl group, and a 4-carboxybutyl group.

The divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent of R ⁵² may, for example, be an alkylene group having 1 to 35 carbon atoms, and examples thereof include a methylene group, an ethylidene group, a propylenediyl group and a butyl group. Dikito, pentanediyl, hexamethylene, heptadienyl, octyldiyl, decyldiyl, tetradecanediyl and hexadecandiyl.

The -CH ₂ - contained in the divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms may be substituted by -O-, -S-, -CO- and -NR'-. The hydrogen atom contained in the aliphatic hydrocarbon group having 1 to 35 carbon atoms may be substituted with a halogen atom such as a fluorine atom.

Examples of the one-valent aliphatic hydrocarbon group having 1 to 6 carbon atoms of R' include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a cyclohexyl group.

The hydrogen atom contained in the fluorenyl group having 2 to 18 carbon atoms of R ⁵¹ , R ⁵³ and R ⁵⁴ may be substituted by an alkoxy group having 1 to 8 carbon atoms. The carbon number of the fluorenyl group having 2 to 18 carbon atoms which may have a substituent is counted by the number of carbon atoms of the substituent, and the number thereof is preferably 6 to 10. Examples of the fluorenyl group which may have a substituent include an ethenyl group, a benzamidine group, a methoxybenzylidene group (p-methoxybenzylidene group, etc.).

R ⁵³ and R ^{54 are} preferably a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 4 carbon atoms, and a mercapto group having 2 to 5 carbon atoms. As a preferable group, a hydrogen atom, an ethyl fluorenyl group, or a propyl fluorenyl group is mentioned, for example.

Examples of the divalent aromatic hydrocarbon group having 6 to 14 carbon atoms of A ⁰ , A ¹ and A ² include a phenylene group and a naphthalene diyl group. Among them, a phenyl group is preferred.

Examples of the substituent of the divalent aromatic hydrocarbon group having 6 to 14 carbon atoms include a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a nitro group, a sulfo group, and an amine sulfonamide. And N-substituted amine sulfonyl groups and the like.

The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and is preferably a fluorine atom, a chlorine atom or a bromine atom.

Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, second butyl group, tert-butyl group, pentyl group and hexyl group. Preferably, it is an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, and particularly preferably a methyl group.

Examples of the alkoxy group having 1 to 8 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a second butoxy group, and a third butoxy group. The base, pentyloxy group, hexyloxy group and the like are preferably an alkoxy group having 1 to 4 carbon atoms, more preferably an alkoxy group having 1 to 2 carbon atoms, particularly preferably a methoxy group.

Examples of the N-substituted amine sulfonyl group include -SO ₂ NHR ⁵⁵ and -SO ₂ N(R ⁵⁵ )R ⁵⁶ , and specific examples thereof include -SO ₂ NHR ⁸ in the compound represented by the formula (1). -SO ₂ N(R ⁸ )R ⁹ and the same groups are listed. Among them, it is preferred that R ⁵⁵ and R ⁵⁶ are each independently an aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent or an N-substituted amine sulfonyl group having a carbon number of 2 to 18 which may have a substituent. .

B ⁰ , B ¹ and B ² each independently represent a one-valent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent or a monovalent heterocyclic group having 3 to 14 carbon atoms which may have a substituent.

Examples of the one-valent aromatic hydrocarbon group having 6 to 14 carbon atoms include a phenyl group and a naphthyl group.

Examples of the monovalent heterocyclic group having 3 to 14 carbon atoms include the groups shown below.

[R represents a hydrogen atom or an organic group]

Examples of the organic group include the same groups as the following R ⁵⁹ .

The hydrogen atom contained in the one-valent aromatic hydrocarbon group having 6 to 14 carbon atoms and the one-valent heterocyclic group having 3 to 14 carbon atoms may be a hydroxyl group, a pendant oxy group, a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms, and cyanogen. Substituted by an amino group, an amine group or an N-substituted amine group.

As the N-substituted amine group, a -NHR ⁵⁷ group or a -NR ⁵⁷ R ⁵⁸ group is preferred. Wherein R ⁵⁷ and R ⁵⁸ each independently represent a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent or a monovalent heterocyclic group having 3 to 14 carbon atoms which may have a substituent. Examples of the one-valent aliphatic hydrocarbon group having 1 to 16 carbon atoms and the one-valent heterocyclic group having 3 to 14 carbon atoms include the same groups as described above.

B ⁰ , B ¹ and B ^{2 are} preferably each independently a group represented by the formula (2-1a).

[In the formula (2-1a), R ⁵⁹ represents a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent. R ⁶⁰ represents a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent]

The pyridone ring of the group represented by the formula (2-1a) may be a ketone type or an enol type.

Examples of the one-valent aliphatic hydrocarbon group having 1 to 16 carbon atoms include the same as those described above, and R ^{59 is} preferably methylbutyl (1,1,3,3-tetramethylbutyl or the like) or methylhexyl. (1,5-dimethylhexyl, etc.), ethylhexyl (2-ethylhexyl, etc.), methylcyclohexyl (2-methylcyclohexyl, etc.) and alkoxypropyl (3-(2-B) A branched aliphatic hydrocarbon group such as a hexyloxy)propyl group.

Examples of the substituent of R ⁵⁹ and R ⁶⁰ include a hydroxyl group, a halogen atom, an alkoxy group having 1 to 8 carbon atoms, and a decyloxy group having 1 to 8 carbon atoms. Examples of the alkoxy group having 1 to 8 carbon atoms are the same as those described above. Examples of the decyloxy group having 1 to 8 carbon atoms include an ethoxycarbonyl group, a propenyloxy group, a hexylcarbonyloxy group, an octylcarbonyloxy group, and a benzhydryloxy group.

R ^{60 is} preferably a methyl group.

The compound represented by the formula (2) includes a compound represented by the formula (I-1) to the formula (I-18). The bond on the right side of A ¹ , A ² , Z ¹ and Z ^{2 in} the table indicates a bond bond near the Z ³ side.

It is preferred that B ¹ and B ² are the same type of base, and more preferably, A ¹ and A ² , R ⁵³ and R ⁵⁴ , and Z ¹ and Z ² are each a group of the same kind. When it is such a base, the compound represented by Formula (2-1) is easy to manufacture.

The compound represented by the formula (2-1) can be obtained by reacting a compound represented by the formula (IA) and a compound represented by the formula (I-A') with a compound represented by the formula (IB) in a solvent. Manufactured by reaction at ~150 °C.

[Formula (IA), Formula (I-A') and Formula (IB), Z ¹ , Z ² , Z ³ , R ⁵³ , R ⁵⁴ , A ¹ , A ² , B ¹ and B ² represent the same as above The meaning.

R ⁶⁷ and R ⁶⁸ each independently represent -OR ⁶⁹ or a halogen atom. R ⁶⁹ represents a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms].

Examples of the compound represented by the formula (IB) include dimethyl malonate, isobutyl succinate, dimethyl adipate and diethyl suberate, propional chloride, amber, and chlorine. Dichloro, octane dichloride and the like.

The compound of the formula (IB) is used in an amount of 1 mol, preferably 0.5 to 3 mol, based on the total amount of the compound represented by the formula (IA) and the compound represented by the formula (I-A'). . Further, when water is contained in the solvent, it is preferred to use the compound represented by the formula (I-B) in excess of the above amount.

In the case where R ⁶⁷ and R ⁶⁸ of the compound of the formula (IB) are -OR ^69, it is preferred to add a well-known acid catalyst. Examples of the acid catalyst include sulfuric acid and p-toluenesulfonic acid. The acid catalyst is used in an amount of 1 mol based on the total amount of the compound represented by the formula (IA) and the compound represented by the formula (I-A'), and is preferably, for example, 0.01 to 2 mol.

The reaction of the compound represented by the formula (I-A) and the compound represented by the formula (I-A') with the compound represented by the formula (I-B) is carried out in a solvent. As the solvent, for example, water; ethers such as 1,4-dioxane (especially cyclic ethers); chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane are preferred. a halogenated hydrocarbon such as dichloroethylene, trichloroethylene, perchloroethylene, dichloropropane, chloropentane or 1,2-dibromoethane; a ketone such as acetone, methyl isobutyl ketone or cyclohexanone; Carbon aromatics such as benzene, toluene and xylene; N,N-dimethylformamide, N,N-dibutylformamide, N,N-dimethylacetamide, N-methylpyrrolidine Alkyl amide such as a ketone or the like may be used in combination of two or more kinds of solvents. The amount of the solvent to be used is, for example, 1 to 20 parts by mass, more preferably 2 parts by mass, based on the total amount of the compound represented by the formula (IA) and the compound represented by the formula (I-A'). ~10 parts by mass.

The reaction of the compound represented by the formula (IA) and the compound represented by the formula (I-A') with the compound represented by the formula (IB) is preferably carried out under a nitrogen atmosphere or an argon atmosphere, or The reaction is carried out under air dried by using calcium chloride or the like.

The reaction temperature is, for example, preferably from 0 to 150 ° C, more preferably from 10 to 130 ° C. The reaction time is, for example, preferably from 1 to 25 hours, more preferably from 3 to 15 hours.

The order of addition of the compound represented by the formula (IA), the compound represented by the formula (I-A'), the compound represented by the formula (IB) and the solvent is not particularly limited, and it is preferred to contain the formula (IA). A compound represented by the formula (IB) is added (dropwise) to a solution of the compound shown, the compound of the formula (I-A') and a solvent. In the case of using an acid catalyst, it is preferred to add (drop) to a solution containing a compound represented by the formula (IA), a compound represented by the formula (I-A'), an acid catalyst, and a solvent. The compound shown in (IB).

The method for obtaining the target compound, that is, the compound represented by the formula (2-1), in the reaction mixture obtained by the above method is not particularly limited, and various well-known methods can be employed, for example, by extracting the reaction mixture by using an organic solvent. purification. Further, it may be further purified by a known method such as washing or recrystallization using an aqueous alkaline solution or an acidic aqueous solution, if necessary.

Further, the compound represented by the formula (2-1) can be subjected to a coupling reaction with a compound represented by the formula (IC), a compound represented by the formula (ID) and a compound represented by the formula (I-D'). Manufacturing. It can be produced by reacting a salt of a compound represented by the formula (IC) with a compound represented by the formula (ID) and a compound represented by the formula (I-D') in, for example, an aqueous solvent at 20 to 60 ° C. a compound represented by the formula (2-1).

(In the formula (IC) and the formula (ID), Z ¹ , Z ² , Z ³ , R ⁵³ , R ⁵⁴ , A ¹ , A ² , B ¹ and B ^{2 have} the same meanings as described above.

X ^- indicates inorganic or organic anion)

Examples of the inorganic or organic anion of the compound represented by the formula (IC) include fluoride ion, chloride ion, bromide ion, iodide ion, perchlorate ion, hypochlorous acid ion, CH ₃ -COO ^- , Ph-COO- ^, etc., preferably, chloride ion, bromide ion, CH ₃ -COO ^- .

As the dye, a dye containing a metal complex of an azo compound as a ligand is preferable, and a dye containing a compound represented by the formula (3) is more preferable. The compound represented by the formula (3) is a chromium-substituted anion or a salt of a cobalt-substituted anion and a cation.

[In the formula (3), R ^a1 to R ^a18 each independently represent a hydrogen atom, a halogen atom, a carbon number of 1 to 8 monovalent aliphatic hydrocarbon group, a nitro group, a phenyl group, -SO ₂ NHR ^a30 , -SO ₃ ^- , -COOR ^a30 or -SO ₂ R ^a30 .

R ^a19 and R ^a20 each independently represent a hydrogen atom, a methyl group, an ethyl group or an amine group.

R ^a30 independently represents a hydrogen atom and a one-valent hydrocarbon group having 1 to 10 carbon atoms, and -CH ₂ - contained in the hydrocarbon group may be substituted by -O- or -CO-.

M ¹ represents Cr or Co.

n ¹ represents an integer from 1 to 5.

D ¹ represents a hydrogen cation, a monovalent metal cation or a valent cation derived from a compound having a dibenzopyran skeleton]

Examples of the one-valent aliphatic hydrocarbon group having 1 to 8 carbon atoms of R ^a1 to R ^a18 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, second butyl group and t-butyl group. , n-pentyl, n-hexyl, n-heptyl, n-octyl, decyl, 1-methylbutyl, 1,1,3,3-tetramethylbutyl, 1,5-dimethylhexyl, 1 , 6-dimethylheptyl, 2-ethylhexyl and 1,1,5,5-tetramethylhexyl and the like.

Examples of the one-valent hydrocarbon group having 1 to 10 carbon atoms of R ^a30 include a carbon number of 1 to 10 one-valent aliphatic hydrocarbon group, a carbon number of 3 to 10 one-valent alicyclic hydrocarbon group, and one of carbon numbers 6 to 10. A valence aromatic hydrocarbon group, and a combination of these groups, having a carbon number of 4 to 10. Examples of the one-valent aliphatic hydrocarbon group having 1 to 10 carbon atoms include the same groups as described above, and the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms is the same as the Q of the compound represented by the formula (1). The basis. Examples of the one-valent alicyclic hydrocarbon group having 3 to 10 carbon atoms include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a cyclodecyl group.

Examples of the above hydrocarbon group in which -CH ₂ - is substituted with -O- or -CO- include -R ^a32 -OR ^a33 , -R ^a32 -CO-OR ^a33 , and -R ^a32 -O-CO-R ^a33 . R ^a32 is a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, and R ^a33 is a one-valent aliphatic hydrocarbon group having 1 to 8 carbon atoms.

Examples of the divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms of R ^a32 include a methylene group, an ethyl group, a propane-1,3-diyl group, a propane-1,2-diyl group, and a butane-1. ,4-diyl, butane-1,3-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1 , 8-diyl, etc.

Examples of -R ^a32 -OR ^a33 include methoxymethyl, ethoxymethyl, propoxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxy. Propyl, ethoxypropyl, propoxypropyl, 2-oxo-4-methoxybutyl, octyloxypropyl, 3-ethoxypropyl, 3-(2-ethyl Hexyloxy)propyl and the like.

Examples of -R ^a32 -CO-OR ^a33 include methoxycarbonylmethyl, methoxycarbonylethyl, ethoxycarbonylmethyl, ethoxycarbonylethyl, propoxycarbonylmethyl, and propoxy. Alkylcarbonylethyl, butoxycarbonylmethyl, butoxycarbonylethyl and the like.

Examples of -R ^a32 -O-CO-R ^a33 include ethoxymethyloxymethyl, ethoxylated ethyl, ethylcarbonyloxymethyl, ethylcarbonyloxyethyl, propylcarbonyloxy. Methyl, propylcarbonyloxyethyl, butylcarbonyloxymethyl, butylcarbonyloxyethyl and the like.

As -SO ₂ NHR ^a30 , there may be mentioned: an amine sulfonyl group; N-methylamine sulfonyl group, N-ethylamine sulfonyl group, N-propylamine sulfonyl group, N-isopropylamine sulfonate , N-butylamine sulfonyl, N-isobutylamine sulfonyl, N-tert-butylamine sulfonyl, N-tert-butylamine sulfonyl, N-pentylamine sulfonate Base, N-(1-ethylpropyl)amine sulfonyl, N-(1,1-dimethylpropyl)amine sulfonyl, N-(1,2-dimethylpropyl)amine sulfonate Indenyl, N-(2,2-dimethylpropyl)aminesulfonyl, N-(1-methylbutyl)aminesulfonyl, N-(2-methylbutyl)aminesulfonyl , N-(3-methylbutyl)amine sulfonyl, N-cyclopentylamine sulfonyl, N-hexylamine sulfonyl, N-(1,3-dimethylbutyl)amine sulfonate , N-(3,3-dimethylbutyl)amine sulfonyl, N-heptylamine sulfonyl, N-(1-methylhexyl)amine sulfonyl, N-(1,4- Dimethylpentyl)aminesulfonyl, N-octylaminesulfonyl, N-(2-ethylhexyl)aminesulfonyl, N-(1,5-dimethyl)hexylaminesulfonyl , N-(1,1,2,2-tetramethylbutyl)amine sulfonyl, N-allylamine sulfonyl, etc., substituted with an aliphatic hydrocarbon group; N-(2-A Oxyethyl)amine sulfonyl, N-(2-ethoxyethyl Aminesulfonyl, N-(1-methoxypropyl)aminesulfonyl, N-(3-methoxypropyl)aminesulfonyl, N-(3-ethoxypropyl)amine Sulfonyl, N-(3-propoxypropyl)amine sulfonyl, N-(3-isopropoxypropyl)amine sulfonyl, N-(3-hexyloxypropyl)amine sulfonate Mercapto, N-(2-ethylhexyloxypropyl)amine sulfonyl, N-(3-tert-butoxypropyl)amine sulfonyl, N-(4-octyloxybutyl) Aminesulfonyl group substituted with -R ³¹ -OR ³² such as amidoxime; N-(methoxycarbonylmethyl)aminesulfonyl, N-(methoxycarbonylethyl)aminesulfonyl, N -(ethoxycarbonylmethyl)amine sulfonyl, N-(ethoxycarbonylethyl)amine sulfonyl, N-(propoxycarbonylmethyl)amine sulfonyl, N-(propoxy Carbonylethyl)amine sulfonyl, N-(butoxycarbonylmethyl)amine sulfonyl, N-(butoxycarbonylethyl)amine sulfonyl, etc., substituted by -R ³¹ -CO-OR ³² Aminesulfonyl; N-(ethoxymethyl)amine sulfonyl, N-(ethyloxyethyl)amine sulfonyl, N-(ethylcarbonyloxy)amine sulfonyl , N-(ethylcarbonyloxyethyl)amine sulfonyl, N-(propylcarbonyloxymethyl)amine sulfonyl, N-(propylcarbonyloxyethyl)amine sulfonyl, N -(butyl Oxymethyl) acyl amine sulfonamide, N- (butylcarbonyloxy) amine and the like by sulfo acyl -R ³¹ -O-CO-R ³² of the amine sulfonamide substituted acyl; sulfo N-cyclohexylamine Sulfhydryl, N-(2-methylcyclohexyl)amine sulfonyl, N-(3-methylcyclohexyl)amine sulfonyl, N-(4-methylcyclohexyl)amine sulfonyl, N- (4-butylcyclohexyl)amine sulfonyl sulfonyl group substituted with a cyclohexyl group having a substituent; a N-benzylamine sulfonyl group, N-(1-phenylethyl)amine sulfonyl group , N-(2-phenylethyl)amine sulfonyl, N-(3-phenylpropyl)amine sulfonyl, N-(4-phenylbutyl)amine sulfonyl, N-[2 -(2-naphthyl)ethyl]amine sulfonyl, N-[2-(4-methylphenyl)ethyl]amine sulfonyl, N-(3-phenyl-1-propyl)amine An sulfonyl group substituted with an aralkyl group such as a sulfonyl group or an N-(3-phenyl-1-methylpropyl)amine sulfonyl group.

Examples of the -COOR ^a30 include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a cyclohexyloxycarbonyl group, and a decyloxycarbonyl group.

As -SO ₂ R ^a30 , a methylsulfonyl group, an ethylsulfonyl group, a propyl sulfonyl group, an isopropyl sulfonyl group, a n-butyl sulfonyl group, a second butyl sulfonyl group, and a third butyl sulfonyl group are mentioned. , pentamsulfonyl, hexylsulfonyl, heptylsulfonyl, octylsulfonyl, 1-methylbutsulfonyl, 1,1,3,3-tetramethylbutsulfonyl, 1,5- Dimethylhexylsulfonyl, 1,6-dimethylheptylsulfonyl, 2-ethylhexylsulfonyl and 1,1,5,5-tetramethylhexulenyl.

It is preferred that at least one of R ^a1 to R ^a18 is a nitro group because of the tendency to have high heat resistance.

As R ^a30 , a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a cyclohexyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, -R ^a32 -OR ^a33 , and -R ^a32 -CO-OR ^{a33 are preferred.} And -R ^a32 -O-CO-R ^a33 .

Preferable examples of the pyrazole azo compound which is a ligand which is a complex anion in the compound represented by the formula (3) include a compound represented by the formula (1-a1) to the formula (1-a64). .

Preferable examples of the complex anion in the compound represented by the formula (3) include an anion represented by the formula (1-b1) to the formula (1-b60).

D ¹ is a hydrogen cation, a monovalent metal cation or a valent cation derived from a compound having a dibenzopyran skeleton. Among them, in view of the higher brightness of the obtained color filter, a valent cation derived from a compound having a dibenzopyran skeleton is preferred. The compound represented by the formula (1) is exemplified as the compound having a dibenzopyran skeleton.

The compound represented by the formula (3) is preferably a compound represented by the formula (3-1) in terms of solubility in an organic solvent.

[In the formula (3-1), R ^a41 to R ^a58 independently of each other represent a hydrogen atom, a halogen atom, a carbon number of 1 to 8 monovalent aliphatic hydrocarbon group, a nitro group, a sulfo group, -SO ₂ R ^a33 or -SO ₂ NHR ^a34 .

R ^a34 represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a cyclohexyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, -R ^a32 -OR ^a33 , -R ^a32 -CO-OR ^a33 , R ^a32 -O-CO-R ^a33 or an aralkyl group having 7 to 10 carbon atoms.

R ^a32 represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.

R ^a33 represents a one-valent aliphatic hydrocarbon group having 1 to 8 carbon atoms.

R ^a59 and R ^a60 independently of each other represent a hydrogen atom, a methyl group, an ethyl group or an amine group.

M ² represents Cr or Co.

R ^a21 to R ^a24 independently of each other represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the aliphatic hydrocarbon group and a hydrogen atom contained in the aromatic hydrocarbon group It may be substituted with a hydroxyl group, -OR ³² , a sulfo group, -SO ₃ Na, -SO ₃ K or a halogen atom.

R ^a25 and R ^a26 are each independently a hydrogen atom or a methyl group.

R ^a27 represents an ethyl group, a propane-1,3-diyl group or a propane-1,2-diyl group.

R ^a28 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

n represents an integer from 1 to 4. In the case where n is an integer of 2 or more, the plurality of R ²⁷ may be the same or different from each other]

Examples of the one-valent aliphatic hydrocarbon group having 1 to 8 carbon atoms include the same groups as those of the above R ^a1 to R ^a18 .

Examples of the divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms include the same groups as those of the above R ^a32 .

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, and a third butyl group.

Examples of the one-valent aromatic hydrocarbon group having 6 to 10 carbon atoms include a phenyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a propylphenyl group, and a butylphenyl group. An aryl group such as a naphthyl group; an aralkyl group such as a benzyl group, a diphenylmethyl group, a phenylethyl group or a 3-phenylpropyl group.

Examples of the cyclohexyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms include 2-methylcyclohexyl group, 2-ethylcyclohexyl group, 2-propylcyclohexyl group, 2-isopropylcyclohexyl group, and 2- Butylcyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-propylcyclohexyl, 4-isopropylcyclohexyl, 4-butylcyclohexyl, and the like.

It is preferred that at least one of R ^a41 to R ^a58 is a nitro group because of the tendency to have high heat resistance.

Further, it is preferred that at least one of R ^a41 to R ^a45 and at least one of R ^a46 to R ^a50 are a sulfo group, -SO ₂ NHR ^a34 or -SO ₂ R ^a33 , more preferably -SO ₂ R ^A33 , and further preferably -SO ₂ CH ₃ .

R ^a21 to R ^{a24 are} preferably a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, more preferably a hydrogen atom or an ethyl group because of a high color density.

As R ^a27 , an ethyl group and a propane-1,2-diyl group are preferred, and an ethyl group is more preferred.

As R ^a28 , a hydrogen atom is preferred.

n is an integer of 1 to 4, preferably an integer of 2 to 4, more preferably 3 or 4, and further preferably 3.

As ^{- (R a27 -O) nR a28} , it is in terms of solubility in an organic solvent, preferred is 2- (2-hydroxyethoxy) ethyl and 2- [2- (2-hydroxyethane Oxy)ethoxy]ethyl, more preferably 2-[2-(2-hydroxyethoxy)ethoxy]ethyl.

Preferable examples of the cation derived from the dibenzopyran compound in the compound represented by the formula (3-1) include a cation represented by the formula (1-c1) to the formula (1-c48).

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

In the specific examples of the compound represented by the formula (3-1), in terms of solubility in an organic solvent, the formula (3a-1), the formula (3a-3) to the formula (3a-5) are preferred. ), Equation (3a-7)~Formula (3a-9), Formula (3a-11)~Formula (3a-16), Formula (3a-18)~Formula (3a-21), and Formula (3a-23) The compound represented by the formula (3a-26) is more preferably a compound represented by the formula (3a-1), a compound represented by the formula (3a-3), and a compound represented by the formula (3a-23).

When the compound of the formula (3) is produced, it can be produced by using a compound represented by the formula (3d) and a chromium compound to form a chromium-substituted salt, or using a compound represented by the formula (3d) and a cobalt compound. wrong form cobalt salts, and thereafter, if necessary so that the misfit salt with a salt of D ¹ having a salt exchange reaction.

[In the formula (3d), R ^a1 to R ^a5 , R ^a11 to R ^a14 and R ^a19 represent the same meanings as in the formula (3)]

The compound represented by the formula (3d) can be produced by a method of diazo coupling of a diazonium salt and a pyrazole compound well known in the field of dyes.

The compound represented by the formula (3-1) can be produced by subjecting the above-mentioned mixed salt to a salt exchange reaction with the dibenzopyran compound represented by the formula (b).

[In the formula (bx), R ^a21 to R ^a28 and n represent the same meanings as in the formula (3-1). A ^- represents a monovalent anion]

Examples of the monovalent anion include Cl ^- , Br ^- , I ^- , ClO ₄ ^- , PF ₆ ^- or BF ₄ ^- .

The dibenzopyran compound represented by the formula (bx) can be produced by reacting a compound represented by the formula (b0) with a compound represented by the formula (b1) in an organic solvent.

[In the formula (b0) and the formula (b1), R ^a21 to R ^a28 and n represent the same meanings as in the formula (3-1). A ^- indicates the same meaning as in the formula (bx)]

In the above reaction, the reaction temperature is preferably from 15 ° C to 60 ° C, and the reaction time is preferably from 1 hour to 12 hours. Further, in terms of shortening the reaction time or increasing the yield, it is preferred to use an acid catalyst and/or a dehydrating agent.

Examples of the acid catalyst include sulfuric acid and p-toluenesulfonic acid.

Examples of the dehydrating agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide salt. Carboxylides such as acid salts; 1-alkyl-2-halopyridinium salts; 1,1'-carbonyldiimidazole; bis(2-oxo-3-oxozolidine) Phosphonium chloride; di-2-pyridyl carbonate and the like. Among them, as the dehydrating agent, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride is preferred because of ease of workup and purification.

The organic solvent used in the above reaction may, for example, be dichloromethane, chloroform, tetrahydrofuran, toluene or acetonitrile.

The compound represented by the formula (3-1) can be produced by subjecting the above-mentioned complex salt to a salt exchange reaction with a dibenzopyran compound represented by the formula (bx) in a solvent. Preferably, the cobalt complex salt is reacted with the dibenzopyran compound (bx) at a molar ratio of 1:1 to 1:4.

These dyes are appropriately selected depending on the solubility in a solvent or the light fading resistance or the spectroscopic spectrum when a pattern of a color filter is formed using the photosensitive resin composition containing the dye.

Further, the content of the dye is preferably from 0.5 to 60% by mass, more preferably from 0.7 to 50% by mass, even more preferably from 1 to 40% by mass, based on the solid content of the colored photosensitive resin composition. Here, the solid content component refers to the total amount of components after removing the solvent from the colored photosensitive resin composition.

Further, the colorant (A) preferably contains a pigment in addition to the dye.

Examples of the pigment include organic pigments and inorganic pigments, and examples thereof include compounds classified as pigments in the "Dye Index" (published by The Society of Dyers and Colourists).

Specific examples of the organic pigment include, for example, CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117. Yellow pigments such as 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, Orange pigments such as 55, 59, 61, 64, 65, 71, 73; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, Red pigments such as 216, 224, 242, 254, 255, 264, 265; blue pigments such as CI Pigment Blue 15, 15:3, 15:4, 15:6, 60; CI Pigment Violet 1, 19, 23, 29 , purple pigments such as 32, 36, 38; CI pigment green 7, 36, 58 and other green pigments; CI pigment brown 23, 25 and other brown pigments; CI pigment black 1, 7 and other black pigments.

Among them, preferred are CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Red 177, CI Pigment Red 209, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red Violet 23, CI Pigment Blue 15 : 3, CI Pigment Blue 15:6 and CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58. The pigment used in the colored photosensitive resin composition of the present invention preferably contains a color selected from the group consisting of CI Pigment Blue 15:6, CI Pigment Red 254, CI Pigment Red 242, CI Pigment Red 177, and CI Pigment Green 58, A pigment of at least one of the group consisting of CI Pigment Yellow 150 and CI Pigment Yellow 138.

The above-mentioned pigment may be subjected to rosin treatment, surface treatment using a pigment derivative or a pigment dispersant into which an acidic group or a basic group is introduced, graft treatment of a pigment surface by a polymer compound or the like, and use of a sulfuric acid micronization method. The micronization treatment, the washing treatment using an organic solvent or water to remove impurities, the treatment for removing ionic impurities by an ion exchange method, or the like. Further, the pigment preferably has a uniform particle size. 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, ester-based, cationic, anionic, nonionic, amphoteric, polyester-based, and polyamine-based. A surfactant such as an acrylic or the like may be used alone or in combination of two or more. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, and tertiary grades. Amine-modified polyurethanes, polyethyleneimine, and the like, in addition to the product name KP (manufactured by Shin-Etsu Chemical Co., Ltd.) and Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), Eftop (Mitsubishi Materials Electronic Chemicals Co., Ltd.), Megaface (manufactured by DIC Corporation), Fluorad (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard (manufactured by Asahi Glass Co., Ltd.), Surflon (manufactured by AGC Seimi Chemical Co., Ltd.) Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by CIBA Co., Ltd.), Ajisper (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (manufactured by BYK-Chemie Co., Ltd.), and the like.

In the case of using a pigment dispersant, the amount thereof is preferably 1 part by mass or less, more preferably 0.05 part by mass or more and 0.5 part by mass or less per 1 part by mass of the pigment. When the amount of the pigment dispersant used is in the above range, there is a tendency to obtain a pigment dispersion liquid in a uniformly dispersed state, which is preferable.

These dyes and pigments may be used alone or in combination of two or more. Further, the dye and the pigment may be used in combination at any ratio.

The content of the dye in the colorant (A) is from 3 to 100% by mass, preferably from 5 to 95% by mass, more preferably from 5 to 80% by mass.

The content of the pigment in the colorant (A) is from 0 to 97% by mass, preferably from 5 to 95% by mass, more preferably from 20 to 95% by mass.

When the content of the dye and the pigment is within the above range, the target spectroscopicity can be obtained, and excellent heat resistance and light resistance tend to be combined, which is preferable.

When a coating film and/or a pattern formed using a colored photosensitive resin composition is used for a color filter provided in a liquid crystal display device or the like, the colored photosensitive resin composition is prepared by separately preparing a blue photosensitive resin composition. A green photosensitive resin composition and a red photosensitive resin composition.

The blue photosensitive resin composition preferably contains a compound represented by the formula (1) as a dye. Further, as the pigment, it is preferred to contain at least one pigment selected from the group consisting of C.I. Pigment Red Violet 23, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:6, and more preferably C.I. Pigment Blue 15:6.

In the case where the pigment is C.I. Pigment Blue 15:6, the mass of the compound represented by C.I. Pigment Blue 15:6 and Formula (1) is preferably 97:3 to 50:50.

The green photosensitive resin composition preferably contains a compound represented by the formula (2) as a dye. Further, it is preferred to contain at least one selected from the group consisting of C.I. Pigment Green 36, C.I. Pigment Green 58, C.I. Pigment Yellow 138, and C.I. Pigment Yellow 150 as a pigment.

The red photosensitive resin composition preferably contains a compound represented by the formula (3) as a dye. Further, it is preferred to contain at least one selected from the group consisting of C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Red 177, C.I. Pigment Red 242, C.I. Pigment Red 254 as a pigment.

The content of the colorant (A) is preferably from 5 to 60% by mass, more preferably from 8 to 55% by mass, more preferably from 8 to 55% by mass, based on the solid content of the colored photosensitive resin composition. 10~50% by mass. Here, the solid content component refers to the total amount of components after removing the solvent from the colored photosensitive resin composition. When the content of the coloring agent (A) is within the above range, the color density when the color filter is formed is sufficient, and the binder resin can be contained in the composition, so that a pattern having a sufficient mechanical strength can be formed. Therefore, it is better.

The colored photosensitive resin composition of the present invention contains a binder resin (B).

The binder resin (B) contained in the colored photosensitive resin composition of the present invention comprises a resin obtained by a polycarboxylic acid resin obtained in such a manner that more than one epoxy resin having two glycidyl groups is used ( a) one or more kinds of the dibasic acid (b) represented by the following formula (Bb) and one or more ethylenically unsaturated monocarboxylic acids (c) are reacted, and then the obtained polymer and one or more The polybasic acid anhydride (d) is reacted.

HOOC-R ^a -COOH (Bb)

[In the formula (Bb), R ^a represents ^a divalent aliphatic hydrocarbon group having 2 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 8 carbon atoms, and the aliphatic hydrocarbon group and the hydrogen atom contained in the alicyclic hydrocarbon group may be Substituted by a hydroxyl group].

Further, the binder resin (B) contained in the colored photosensitive resin composition of the present invention comprises a resin obtained by a polycarboxylic acid resin obtained in such a manner that more than one epoxy having two glycidyl groups is used. Resin (a), one or more dibasic acids (b) represented by the following formula (Bb), and one or more ethylenically unsaturated monocarboxylic acids (c) are reacted, and then the obtained polymer and one kind are obtained. The above polybasic acid anhydride (d) is reacted with one or more radically polymerizable compounds (e) having one glycidyl group.

HOOC-R ^a -COOH (Bb)

[In the formula (Bb), R ^a represents ^a divalent aliphatic hydrocarbon group having 2 to 8 carbon atoms or an alicyclic hydrocarbon group having 3 to 8 carbon atoms, and the aliphatic hydrocarbon group and the hydrogen atom contained in the alicyclic hydrocarbon group may be Substituted by hydroxy]

The epoxy resin (a) having two glycidyl groups (hereinafter sometimes referred to as "epoxy resin (a)") is not particularly limited as long as it has two glycidyl groups in one molecule. Specific examples of such an epoxy resin (a) include a bisphenol type epoxy resin as a glycidyl ether type, and examples thereof include bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A, and double a resin obtained by reacting a bisphenol such as phenol with epichlorohydrin and/or methyl epichlorohydrin, or a condensate of bisphenol A and a condensate of the above phenol with epichlorohydrin and/or methyl a resin obtained by reacting epichlorohydrin, a resin obtained by reacting bisphenol with epichlorohydrin and/or methyl epichlorohydrin (for example, EPIKOTE YX-4000; manufactured by Nippon Epoxy Co., Ltd.); A resin obtained by reacting hydroxynaphthalene with epichlorohydrin and/or methyl epichlorohydrin (for example, EPICLON HP-4032; manufactured by DIC Corporation); from alkyl diphenols to epichlorohydrin and/or methyl a resin obtained by reacting chlorohydrin (for example, EPICLON EXA-7120; manufactured by DIC Corporation); etc.; as a glycidyl ester type, dimer acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester Etc.; as a glycidylamine type, diglycidyl aniline, diglycidyl group An amine or the like; as the alicyclic type, an alicyclic diepoxy carboxylic acid ester, a resin having a oxazolidinone ring obtained by reacting the above epoxy resin with a diisocyanate (for example, ARALDITE AER4152: Asahi Kasei) Epoxy Co., Ltd.) and so on.

These epoxy resins (a) may be used alone or in combination of two or more.

In particular, the epoxy resin (a) is preferably an epoxy resin represented by the following formula (Ba) because it is linearly polymerized in the reaction for forming a polymer without causing gelation. There is a tendency that the obtained polycarboxylic acid resin is excellent in heat resistance and chemical resistance.

[化38]

[In the formula (Ba), R ^b , R ^c , R ^d and R ^e represent a hydrogen atom or a methyl group; n represents a number from 0 to 10, and when n is an integer of 2 or more, a plurality of R ^b and R ^c are mutually Can be the same or different]

Examples of the epoxy resin (a) represented by the formula (Ba) include a bisphenol A epoxy resin and a bisphenol F epoxy resin. Among them, a bisphenol A epoxy resin is preferred.

The dibasic acid (b) used in the present invention is a compound represented by the following formula (Bb).

HOOC-R ^a -COOH (Bb)

[In the formula (Bb), R ^a represents ^a divalent aliphatic hydrocarbon group having 2 to 8 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 8 carbon atoms, the aliphatic hydrocarbon group and hydrogen contained in the alicyclic hydrocarbon group. Atoms can be substituted by hydroxyl groups]

As the dibasic acid (b), the carbon number of R ^a in the formula (Bb) is 2 to 8, preferably 2 to 7 carbon atoms, more preferably 3 to 6 carbon atoms, because of the presence of epoxy. The hydroxyl group formed by the reaction of the glycidyl group of the resin (a) and the carboxyl group of the dibasic acid (b) increases in the proportion of the repeating unit of the polymer which is polymerized, and exhibits a tendency to rapidly dissolve alkali. .

Examples of such a dibasic acid (b) include succinic acid, fumaric acid, maleic acid, glutaric acid, itaconic acid, adipic acid, tetrahydrophthalic acid, and hexahydrogen. Phthalic acid, ethylene glycol 2 molar maleic anhydride adduct, and the like.

Among them, adipic acid is preferred. A composition containing a polycarboxylic acid resin produced using adipic acid tends to have good heat resistance when forming a coating film, and is therefore preferred.

These dibasic acids (b) may be used alone or in combination of two or more.

Further, as the dibasic acid (b), an aliphatic hydrocarbon group of R ^a in the formula (Bb) and ^a hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with a hydroxyl group. Examples of such a dibasic acid (b) include malic acid, tartaric acid, and munic acid. When such a dibasic acid is used, in addition to the hydroxyl group formed by the reaction of the glycidyl group of the epoxy resin (a) and the carboxyl group of the dibasic acid (b), a hydroxyl group derived from the dibasic acid is also present in the polymer. Therefore, the developability and the substrate adhesion tend to be good, which is useful.

Examples of the ethylenically unsaturated monocarboxylic acid (c) include acrylic acid, methacrylic acid, crotonic acid, and cinnamic acid. Further, a reaction product of a polyfunctional (meth) acrylate having one hydroxyl group and two or more (meth) acrylonitrile groups and a polybasic acid anhydride can also be used. Among them, the ethylenically unsaturated monocarboxylic acid (c) is preferably at least one selected from the group consisting of acrylic acid and methacrylic acid because of the tendency that the sensitivity and the chemical resistance of the coating film become good. . These may be used singly or in combination of two or more. In the present specification, the term "(meth) acrylate" means at least one selected from the group consisting of acrylates and methacrylates. In addition, "(meth)acrylic acid" or the like also means the same meaning.

The ethylenically unsaturated monocarboxylic acid (c) exhibits a function of introducing an ethylenically unsaturated group as a photosensitive group to the terminal of the polycarboxylic acid resin and controlling the molecular weight of the polymer.

Examples of the polybasic acid anhydride (d) include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylhexahydrogen. Phthalic anhydride, endomethylene tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, and the like. Among them, tetrahydrophthalic anhydride is preferred because of the tendency for developability to be good. These may be used alone or in combination of two or more.

The radically polymerizable compound (e) having one glycidyl group (hereinafter referred to as "radical polymerizable compound (e)") may, for example, be glycidyl acrylate or glycidyl methacrylate. , β-methyl glycidyl acrylate, β-methyl glycidyl methacrylate, β-ethyl glycidyl acrylate, β-ethyl glycidyl methacrylate, glycidyl vinyl ether , o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, o-isopropenylbenzyl glycidyl ether, m-isopropenylbenzyl glycidyl ether, dimorphism Propylene benzyl glycidyl ether and the like. In particular, the radical polymerizable compound (e) is preferably at least one selected from the group consisting of glycidyl acrylate and glycidyl methacrylate, because the sensitivity tends to increase.

The method for synthesizing the polycarboxylic acid resin is not particularly limited, and it can be obtained by the same reaction as the conventional method for synthesizing a polycarboxylic acid. For example, it can be produced by the method described in JP-A-2004-67814. That is, for example, it can be obtained by first using an esterification catalyst to make a specific amount of the dibasic acid (b) and the ethylenically unsaturated monocarboxylic acid (c) and the epoxy having 2 glycidyl groups. Resin (a) is reacted; then, a polynuclear acid anhydride (d) is subjected to ring-opening addition to one of the above-mentioned polymers and/or secondary hydroxyl groups formed therefrom using a catalyst.

Further, the polycarboxylic acid resin can also be obtained by first using an esterification catalyst to give a specific amount of the dibasic acid (b) and the ethylenically unsaturated monocarboxylic acid (c) with 2 glycidol. The epoxy resin (a) is reacted, and then a catalyst is used for ring-opening addition of a polybasic acid anhydride (d) on one or more secondary hydroxyl groups of the above-mentioned polymer to be synthesized, and then The carboxyl group formed by the addition of the polybasic acid anhydride (d) is reacted with a glycidyl group contained in the radically polymerizable compound (e) having one glycidyl group.

Further, the reaction end point of the epoxy resin (a), the dibasic acid (b) and the ethylenically unsaturated monocarboxylic acid (c) can be observed by the acid value reduction or the absorption peak of the epoxy group by infrared spectrum (910 cm). ^-1 ) Confirmed disappearing.

When the above polymer is formed, the reaction ratio (b) of the dibasic acid (b) to the ethylenically unsaturated monocarboxylic acid (c): (c) is preferably from 1:20 to 5:1 in terms of molar ratio. In the range, it is better in the range of 1:5 to 1:1. When the molar ratio of the dibasic acid (b) to the ethylenically unsaturated monocarboxylic acid (c) is in the above range, the sensitivity and developability tend to be good, and the development residue tends to be suppressed. .

Further, when the above polymer is produced, the reaction ratio of the epoxy resin (a) to the dibasic acid (b) and the ethylenically unsaturated monocarboxylic acid (c) is preferably a ring with respect to the epoxy resin (a). The sum of the oxy groups of 1 equivalent, the dibasic acid (b) and the ethyl carboxyl group of the ethylenically unsaturated monocarboxylic acid (c) is in the range of 0.9 to 1.1 equivalents, more preferably in the range of 0.95 to 1.05 equivalents. When the reaction ratio is within the above range, the sensitivity and developability tend to be good, and the development residue tends to be suppressed, which is preferable.

The molecular weight of the polymer produced is preferably in the range of 800 to 12,000, more preferably in the range of 1200 to 8,000, in terms of polystyrene-equivalent number average molecular weight. When the molecular weight of the linear addition polymer is within the above range, the developability tends to be good, which is preferable.

Further, the amount of the polybasic acid anhydride (d) to be reacted with the obtained polymer may be appropriately selected depending on the acid value of the target polycarboxylic acid resin.

Further, the radically polymerizable compound (e) having one glycidyl group is preferably 0.05 to 0.90 moles, more preferably 0.1 to 0.8 moles, per mole of the polybasic acid anhydride (d). Especially good is the addition of 0.3~0.75 moles.

By the addition reaction of the polybasic acid anhydride (d) and the radically polymerizable compound (e), the amount of the photosensitive group increases. At the same time, a secondary hydroxyl group is formed during the addition reaction, so that the adhesion to the substrate, particularly to the glass, is enhanced, and the effect of developing the developed image to form a property of dissolution development is imparted. Here, the development is a dissolution type development, which means that the unexposed portion of the film obtained by applying the composition is not removed by peeling but is dissolved in the developer to be removed, and if it is dissolved, the pattern end can be suppressed. The tendency of the department to be rough. When the amount of addition of the radically polymerizable compound (e) is less than 0.05 mol per mol of the polybasic acid anhydride (d), the sensitivity, solubility, and adhesion tend to be deteriorated, and if When it exceeds 0.90 mol, the unreacted radical polymerizable compound (e) increases, and the outgassing occurs at the time of post-baking. Therefore, the addition amount of the radically polymerizable compound (e) is preferably in the range of 0.05 to 0.90 mol per mol of the polybasic acid anhydride (d).

The acid value of the polycarboxylic acid resin is usually 10 to 200 KOHmg/g, preferably 10 to 180 KOHmg/g, particularly preferably 20 to 150 KOHmg/g. When the acid value is in the above range, the developability tends to be good, which is preferable.

The weight average molecular weight of the polycarboxylic acid resin determined by gel permeation chromatography using polystyrene resin is preferably from 1,000 to 100,000, more preferably from 1,000 to 50,000, particularly preferably from 2,000 to 25,000. When the weight average molecular weight is within the above range, the developability tends to be good, which is preferable.

The content of the polycarboxylic acid resin is preferably from 10 to 100% by mass, more preferably from 20 to 80% by mass, particularly preferably from 25 to 75% by mass, based on the binder resin (B). When the content of the polycarboxylic acid resin is within the above range, the sensitivity and the heat resistance of the coating film tend to be good, which is preferable.

In the binder resin (B), in addition to the polycarboxylic acid resin, a known resin may be used in combination.

The resin used as the binder resin (B) is preferably not particularly limited as long as it is soluble in the developer used in the development treatment step, particularly the alkali developer, and examples thereof include a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group. A copolymer (BB) (hereinafter sometimes referred to as "resin (BB)") of the compound (B1) (hereinafter sometimes referred to as "(B1)")) which is an acidic functional group, and another copolymerizable compound. Among them, (B1) is preferably an unsaturated compound having a carboxyl group.

(B1) may be used singly or in combination of two or more.

Examples of the unsaturated compound having a carboxyl group include an unsaturated carboxylic acid having one or a plurality of carboxyl groups in a molecule such as an unsaturated monocarboxylic acid or an unsaturated dicarboxylic acid. Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, and cinnamic acid. Succinic acid mono [2-(methyl) propylene oxiranyl ethyl] ester, ω-carboxy polycaprolactone mono (meth) acrylate, 5-carboxy-5-methyl bicyclo [2.2.1] g- 2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6- Ethylbicyclo[2.2.1]hept-2-ene and the like. Among them, acrylic acid and methacrylic acid are preferred.

Among the compounds which can be copolymerized with (B1) as the binder resin (BB), it is particularly preferable to contain a structural unit derived from an unsaturated compound (B0) having a curable group (hereinafter, sometimes referred to as "(B0")). The reason for the resin is that the reliability (heat resistance, light resistance, solvent resistance, mechanical properties, and the like) of the colored pattern formed by the colored photosensitive resin composition is improved.

The unsaturated compound (B0) having a curable group is, for example, preferably a compound having a carbon-carbon unsaturated double bond and a cyclic ether structure. Examples of the cyclic ether structure include an epoxy structure (i.e., an ethylene oxide structure), a propylene oxide structure, and a tetrahydrofuran structure. Particularly preferred are an epoxy structure and a propylene oxide structure.

The epoxy structure can be classified into a structure in which an olefin is epoxidized (hereinafter referred to as "aliphatic epoxy structure"), and a structure in which a cyclic olefin is epoxidized (hereinafter simply referred to as "alicyclic epoxy structure"). Further, the alicyclic epoxy structure can be classified into a cycloolefin having a single ring (hereinafter referred to as "aliphatic monocyclic epoxy structure"), and a cyclic olefin is a polycyclic ring (hereinafter referred to as "aliphatic polycyclic". Epoxy structure"). Among these, an alicyclic epoxy structure is preferred, and an aliphatic polycyclic epoxy structure is more preferred. Examples of the monocyclic cycloolefin include cyclopentene, cyclohexene, and cycloheptene. As the cyclic olefin of the above crosslinked ring, for example, a drop can be mentioned. Alkene, dicyclopentene and tricyclodecene.

(B0) may be used singly or in combination of two or more.

Specific examples of the compound having a carbon-carbon unsaturated double bond and an aliphatic epoxy structure include glycidyl (meth)acrylate and β-methylglycidyl (meth)acrylate. The compound represented by the following formula, which is described in JP-A-H07-248625, is exemplified by acryl-β-ethyl glycidyl ester, glycidyl vinyl ether, and the like.

Here, the (meth) acrylate in the present specification means at least one selected from the group consisting of acrylates and methacrylates.

(wherein, R ^x1 to R ^x3 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and mx is an integer of 1 to 5)

Examples of the compound represented by the above formula include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and α-methyl-o-vinylbenzyl group. Glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidoxymethyl)styrene, 2, 4-bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3, 4-tris(glycidoxymethyl)styrene, 2,3,5-tris(glycidoxymethyl)styrene, 2,3,6-tris(glycidoxymethyl)styrene, 3,4,5-tris(glycidoxymethyl)styrene and 2,4,6-tris(glycidoxymethyl)styrene.

The compound having a carbon-carbon unsaturated double bond and an aliphatic monocyclic epoxy structure is a compound having an epoxy group on the ring of the aliphatic monocyclic compound.

Specific examples of the compound having a carbon-carbon unsaturated double bond and an aliphatic monocyclic epoxy structure include, for example, vinylcyclohexene oxide and 1,2-epoxy-4-vinylcyclohexane. An alkane (for example, Celloxide 2000; manufactured by Daicel Chemical Industry Co., Ltd.), 2,3-epoxycyclohexylmethyl (meth)acrylate, and 3,4-epoxycyclohexylmethyl (meth)acrylate (for example) Cyclomer A400; manufactured by Daicel Chemical Industry Co., Ltd.), methacrylate-3,4-epoxycyclohexylmethyl ester (for example, Cyclomer M100; manufactured by Daicel Chemical Industry Co., Ltd.), and the like.

The compound having a carbon-carbon unsaturated double bond and an aliphatic polycyclic epoxy structure is a compound having an epoxy group on the ring of the aliphatic polycyclic compound. As an aliphatic polycyclic compound, it can be mentioned that: Alkene, dicyclopentane, tricyclodecane, and the like.

Specific examples of the compound having a carbon-carbon unsaturated double bond and an aliphatic polycyclic epoxy structure include a 3,4-epoxy group of acrylic acid. Ester, methacrylic acid-3,4-epoxy group The ester, the compound represented by the formula (B0-1) and the compound represented by the formula (B0-2) are preferably selected from the group consisting of the compound represented by the formula (B0-1) and the formula (B0-2). At least one compound of the group consisting of the compounds.

In the formula (B0-1) and the formula (B0-2), R ^y1 and R ^y2 each independently represent an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and a hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.

X ^y1 and X ^y2 each independently represent a single bond or an alkyl group having a carbon number of 1 to 6 which may contain a hetero atom]

Specific examples of the alkyl group having 1 to 4 carbon atoms which may be substituted by a hydroxyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, second butyl group, tert-butyl group and hydroxyl group. Methyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxy-n-propyl, 2-hydroxy-n-propyl, 3-hydroxy-n-propyl, 1-hydroxy-isopropyl, 2-hydroxyl 1-isopropyl, 1-hydroxy-n-butyl, 2-hydroxy-n-butyl, 3-hydroxy-n-butyl, 4-hydroxy-n-butyl and the like. Among them, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group are preferable, and a methyl group is more preferable.

Examples of R ^y1 and R ^y2 include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group. More preferably, a hydrogen atom or a methyl group is used.

Examples of the hetero atom in the alkylene group having 1 to 6 carbon atoms which may contain a hetero atom include an oxygen atom, a sulfur atom and a nitrogen atom. Furthermore, the number of heteroatoms is not included in the carbon number.

Examples of the alkylene group having 1 to 6 carbon atoms which may contain a hetero atom include a methylene group, an exoethyl group, a propylidene group, an oxymethylene group (i.e., -O-CH ₂ -), and an oxy-ethyl group. Oxypropyl propyl, sulfoalkylmethylene (ie, -S-CH ₂ -), thioalkyl-extended ethyl, thioalkyl-propyl, iminomethylene (ie, -NH-CH ₂ -), sub The amine group and the imido group are preferably a methyl group, an ethyl group, an oxymethylene group or an oxyethyl group. More preferably, the oxy group is an ethyl group.

Examples of X ^y1 and X ^y2 include a single bond, a methylene group, an ethylidene group, an oxymethylene group or an oxyethyl group. More preferably, a single bond or an oxyethyl group is exemplified.

Examples of the compound represented by the formula (B0-1) include a compound represented by the formula (B0-1-1) to the formula (B0-1-15), and a formula (B0-1-1) is preferred. , formula (B0-1-3), formula (B0-1-5), formula (B0-1-7), formula (B0-1-9), formula (B0-1-11)~ formula (B0- 1-15) The compound shown by the formula (B0-1-1), the formula (B0-1-7), the formula (B0-1-9) or the formula (B0-1-15) The compound shown.

Examples of the compound represented by the formula (B0-2) include a compound represented by the formula (B0-2-1) to the formula (B0-2-15), and a formula (B0-2-1) is preferred. , formula (B0-2-3), formula (B0-2-5), formula (B0-2-7), formula (B0-2-9), formula (B0-2-11)~ formula (B0- 2-15) The compound shown by the formula (B0-2-1), the formula (B0-2-7), the formula (B0-2-9) or the formula (B0-2-15) The compound shown.

At least one compound selected from the group consisting of a compound represented by the formula (B0-1) and a compound represented by the formula (B0-2) can be used alone. Alternatively, they may be mixed at any ratio. In the case of mixing, the mixing ratio is preferably 5:95 to 95:5, more preferably 10:90 to 90:10, in the molar ratio of the formula (B0-1): formula (B0-2). Especially good is 20:80~80:20.

Specific examples of the compound having a carbon-carbon unsaturated double bond and a propylene oxide structure include 3-(meth)acryloxymethyl propylene oxide and 3-methyl-3-(methyl) group. Propylene methoxymethyl propylene oxide, 3-ethyl-3-(methyl) propylene methoxymethyl propylene oxide, 3-methyl-3-[1-(methyl) propylene oxime] Methyl propylene oxide, 3-ethyl-3-[1-(methyl) propylene decyloxy] methyl propylene oxide, 3-methyl-3-[1-(methyl) propylene decyloxy] Ethyl propylene oxide, 3-ethyl-3-[1-(meth)acryloxy)ethyl propylene oxide, 2-phenyl-3-(methyl) propylene methoxymethyl epoxy Propane, 2-trifluoromethyl-3-(methyl)propenyloxymethyl propylene oxide, 2-pentafluoroethyl-3-(methyl) propylene decyloxymethyl propylene oxide, 3- Methyl-3-(methyl)propenyloxyethyl propylene oxide, 3-methyl-3-(methyl)propenyloxyethyl propylene oxide, 2-phenyl-3-(methyl Ethylene oxyethyl propylene oxide, 2-trifluoromethyl-3-(methyl) propylene oxiranyl ethyl propylene oxide or 2-pentafluoroethyl-3-(methyl) propylene oxime Ethyl propylene oxide, 3-methyl propylene oxy propylene oxide, and the like. Among these, 3-ethyl-3-(meth)acryloxymethyl propylene oxide is preferred.

Specific examples of the compound having a carbon-carbon unsaturated double bond and a tetrahydrofuran structure include tetrahydrofurfuryl (meth)acrylate, tetrahydrofuranylmethoxyethyl (meth)acrylate, and tetrahydrofuran (meth)acrylate. Methoxypropyl propyl ester and the like.

In the case where the binder resin (BB) is a copolymer of (B1) and (B0), if it is a total number of moles relative to the structural unit constituting the copolymer, the structural unit derived from (B1) and from (B0) When the ratio of the structural unit is within the following range in terms of the molar fraction, storage stability, heat resistance, and mechanical strength tend to be good, which is preferable.

Structural unit from (B1): 2~98 mol%

Structural unit from (B0): 2~98 mol%

Further, when the ratio of the above structural unit is within the following range, it is more preferable in terms of developability, residual film ratio, and solvent resistance.

Structural unit from (B1): 15~60 mol%

Structural unit from (B0): 40~85 mol%

For example, the method of the above-mentioned adhesive resin (BB) can be referred to in the document "Experimental method for polymer synthesis" (Dazu Takashi, Chemical Co., Ltd., First Edition, First Printing, March 1, 1972). It is manufactured by reference to the documents described in the literature.

Specifically, a compound such as (B1) and (B0), a polymerization initiator, and a solvent can be introduced into a reaction vessel, and the mixture can be stirred, heated, and insulated by replacing oxygen with nitrogen in the absence of oxygen. The copolymer is obtained. Further, the obtained copolymer may be directly used as a solution after the reaction, or a solution obtained by concentration or dilution, or a solid (powder) taken out by a method such as reprecipitation.

The binder resin (BB) may further contain, in addition to (B1) or (B1) and (B0), a compound (B2) (excluding (B1) and (B0)) which may be copolymerized with (B1) ( Hereinafter, it may be referred to as a structural unit of "(B2)"). (B2), for example, a carboxylic acid ester having an olefinic double bond, a guanamine compound having an olefinic double bond, an aromatic compound having a polymerizable carbon-carbon unsaturated bond, a substituted ethylene compound, and a diene , N-substituted maleimide compounds, polycyclic unsaturated compounds, and the like.

Specific examples of (B2) include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and (methyl). Benzyl acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, (meth) acrylate Esters, tricyclo[5.1.02 ^2,6 ]decane-8-yl (meth)acrylate (in the technical field, the conventional name is called "dicyclopentyl (meth)acrylate"), ( Dicyclopentyloxyethyl methacrylate, phenyl (meth) acrylate, aminoethyl (meth) acrylate, diethyl maleate, diethyl fumarate, Yikang Unsaturated carboxylic acid esters such as diethyl acid acetate; vinyl carboxylates such as vinyl acetate or vinyl propionate; polymerization of dimethyl (meth) acrylamide, isopropyl (meth) acrylamide Amidoxime; a polymerizable aromatic such as styrene, α-methylstyrene or vinyltoluene; a nitrileated vinyl such as acrylonitrile, methacrylonitrile or α-chloro(meth)acrylonitrile; N- Methyl maleimide, N-ethyl maleimide, N-butyl maleimide, N-cyclohexyl maleimide, N-benzyl cis N-substituted maleimide, such as enediamine, N-phenyl maleimide, styrene, α-methylstyrene, m-methylstyrene, p-methylbenzene a polymerizable aromatic compound such as ethylene, vinyl toluene or p-methoxystyrene; Halogenated vinyls such as vinyl chloride, dichloroethylene, trichloroethylene, vinyl fluoride, difluoroethylene, trifluoroethylene, tetrafluoroethylene; 1,3-butadiene, isoprene, 2,3-dimethyl -diene such as 1,3-butadiene; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1 Hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-di Hydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[ 2.2.1] hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methyl Bicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5 a polycyclic unsaturated compound such as 6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene.

Among these, preferred are benzyl (meth) acrylate, styrene, N-phenyl maleimide, N-cyclohexyl maleimide, N-benzyl butene Diimine, bicyclo [2.2.1] hept-2-ene, and the like.

The above (B2) may be used singly or in combination of two or more.

In the case where the binder resin (BB) is a copolymer of (B1) and (B2), the structural unit derived from (B1) and from (B2) are relative to the total number of moles of the structural unit constituting the copolymer. When the ratio of the structural unit is in the range of the following by the molar fraction, the storage stability and the heat resistance tend to be good, which is preferable.

Structural unit from (B1): 2~98 mol%

Structural unit from (B2): 2~9.8 mol%

Further, when the ratio of the above structural unit is within the following range, it is more preferable in terms of developability and residual film ratio.

Structural unit from (B1): 15~60 mol%

Structural unit from (B2): 40~85 mol%

In the case where the binder resin (BB) is a copolymer of (B1), (B0) and (B2), if it is a total number of moles relative to the structural unit constituting the copolymer, it is derived from (B0) to (B2). When the ratio of the structural unit is within the following range in terms of the molar fraction, storage stability, heat resistance, and mechanical strength tend to be good, which is preferable.

Structural unit from (B0): 2~97 mol%

Structural unit from (B1): 2~97 mol%

Structural unit from (B2): 1~96 mol%

Further, when the ratio of the above structural unit is within the following range, it is more preferable in terms of developability, residual film ratio, and solvent resistance.

Structural unit from (B0): 20~80 mol%

Structural unit from (B1): 10~50 mol%

Structural unit from (B2): 10~70 mol%

The above-mentioned binder resin (BB) containing the structural unit derived from (B0) to (B2) can be produced by the same method as the above-mentioned resin containing the structural units derived from (B1) and (B0).

As the binder resin (BB) containing the structural unit derived from (B2), a copolymer of (B1), (B0) and (B2) is preferred because of the colored pattern formed by the colored photosensitive resin composition. Heat resistance, light resistance, solvent resistance, and mechanical properties are improved.

Further, as a structural unit in the above-mentioned binder resin (BB), a macromonomer having a monopropenyl group or a monomethacrylinyl group at the terminal, a unit represented by the following formula (21), and a formula (22) are contained. The unit or the like shown is more excellent in terms of pattern adhesion, solvent resistance, and sensitivity.

[化43]

[In the formulae (21) and (22), R ^y3 , R ^y4 , R ^y5 and R ^y6 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms]

The binder resin (BB) containing the structural unit represented by the formula (21) can be obtained by obtaining a structural unit (B1a) containing an unsaturated compound derived from a carboxyl group or an unsaturated compound having a carboxylic acid anhydride (hereinafter, a resin sometimes referred to as "(B1a)"), for example, a copolymer of (B1a) and (B0), a copolymer of (B1a) and (B2), a copolymer of (B1a) and (B0) and (B2) Then, the obtained copolymer is reacted with a compound represented by the following formula (23) in a carboxylic acid moiety or a carboxylic anhydride moiety contained in (B1a).

Examples of the unsaturated compound having a carboxyl group in (B1a) include a compound exemplified as a specific example of (B1), and specific examples of the unsaturated compound having a carboxylic acid anhydride include maleic anhydride and 5,6. - Dicarboxybicyclo[2.2.1]hept-2-ene anhydride (bicycloheptene dicarboxylic anhydride) or the like. Among them, preferred is (meth)acrylic acid.

[化44]

[In the formula (23), R ^y4 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms]

The binder resin (BB) having the structural unit represented by the formula (22) can be obtained in the same manner as described above, and then obtained in the same manner as the method described in, for example, JP-A-2005-189574. The copolymer is obtained by reacting a compound represented by the formula (24).

[化45]

[In the formula (24), R ^y6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms]

The acid value of the resin (BB) is usually 50 to 150, preferably 60 to 135, particularly preferably 70 to 135. When the acid value is in the above range, the solubility in the developer is improved, and the unexposed portion is easily dissolved, which is preferable.

The weight average molecular weight of the resin (BB) determined by gel permeation chromatography on the basis of polystyrene is preferably 2,000 to 100,000, more preferably 2,000 to 50,000, particularly preferably 3,000 to 30,000. When the weight average molecular weight is within the above range, the coating property tends to be good, and the residual film ratio at the time of development can be maintained, and a high development speed tends to be obtained, which is preferable.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (BB) is preferably from 1.1 to 6.0, more preferably from 1.2 to 4.0. When the molecular weight distribution is within the above range, the developability tends to be excellent, which is preferable.

When the binder resin (B) contains a polycarboxylic acid resin and a resin (BB), the polycarboxylic acid resin and the resin (BB) may be used in combination at any ratio. At this time, the mixing ratio of the polycarboxylic acid resin to the resin (BB) is preferably in the following range in terms of a mass ratio.

Polycarboxylic acid resin: 10 to 90% by mass

Resin (BB): 90~10% by mass

The content of the binder resin (B) is preferably from 10 to 35% by mass, more preferably from 15 to 30% by mass, based on the mass fraction of the coloring photosensitive resin composition.

In addition, the content of the binder resin (B) is preferably from 20 to 80% by mass, particularly preferably from 30 to 70% by mass, based on the total amount of the binder resin (B) and the photopolymerizable compound (C). It is 40 to 65 mass%. When the content of the binder resin (B) is within the above range, the solubility in the developer is sufficient, development residue is not easily generated on the substrate of the non-pixel portion, and the pixel portion of the exposed portion is less likely to cause film reduction during development, and the non-pixel The partial peeling property tends to be good, so it is preferable. Further, there is a tendency that the resolution and the residual film ratio are increased, which is preferable.

The colored photosensitive resin composition of the present invention contains a photopolymerizable compound (C). The photopolymerizable compound (C) is a compound which is polymerized by an active radical, an acid or the like which is produced by photopolymerization initiator (D) by light irradiation, and examples thereof include carbon-carbon which is not polymerizable. A compound such as a saturated bond.

The photopolymerizable compound (C) is preferably a photopolymerizable compound having a trifunctional or higher carbon-carbon unsaturated bond. Examples of the trifunctional or higher polyfunctional photopolymerizable compound include pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol. Penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. The 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, more preferably from 13 to 60% by mass, more preferably from 13 to 60% by mass, based on the solid content of the colored photosensitive resin composition. It is 17 to 55 mass%. When the content of the photopolymerizable compound (C) is within the above range, the curing can be sufficiently performed, and the film thickness ratio before and after the development is increased, the undercut is less likely to occur in the pattern, and the adhesion tends to be good. it is good.

The colored photosensitive resin composition of the present invention contains a photopolymerization initiator (D). Examples of the photopolymerization initiator (D) include an active radical generator, an acid generator, and the like.

The living radical generator generates active radicals by light irradiation. Examples of the living radical generating agent include an alkylphenone compound, a benzoin compound, a benzophenone compound, and 9-oxosulfuric acid. Compound, three Compounds, hydrazine compounds, and the like.

Examples of the alkylphenone compound include diethoxyacetophenone and 2-methyl-2- Lolinyl-1-(4-methylthiophenyl)propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzoin dimethyl ketal, 2- Hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-[ An oligomer of 4-(1-methylvinyl)phenyl]propan-1-one or the like.

Preferred is 2-methyl-2- Orolinyl-1-(4-methylthiophenyl)propan-1-one and the like.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the benzophenone compound include benzophenone, methyl ortho-benzoylbenzoate, 4-phenylbenzophenone, and 4-benzylidene-4'-methyldiphenyl. Thioether, 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, and the like.

9-oxosulfur For the compound, for example, 2-isopropyl-9-oxysulfide 4-isopropyl-9-oxosulfur 2,4-diethyl-9-oxosulfur 2,4-dichloro-9-oxosulfur 1-chloro-4-propoxy-9-oxosulfur Wait.

As three The compound may, for example, be 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tri , 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-three 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-three Wait.

Examples of the ruthenium compound include an O-indenyl ruthenium compound, and specific examples thereof include N-benzylideneoxy-1-(4-phenylsulfanylphenyl)butan-1-one. -2-imine, N-benzylideneoxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-ethyloxy-1-[9 -ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethane-1-imine, N-ethyloxy-1-[9-ethyl-6 -{2-Methyl-4-(3,3-dimethyl-2,4-dioxolanylmethoxy)benzylidenyl}-9H-indazol-3-yl]ethane- 1-Imino and the like. Commercial products such as Irgacure OXE-01, Irgacure OXE-02 (manufactured by Ciba Japan Co., Ltd.), and N-1919 (manufactured by ADEKA Co., Ltd.) can also be used.

As the living radical generator other than the above-exemplified ones, for example, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide or 2,2'-bis(o-chlorophenyl)-4 can also be used. , 4',5,5'-tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylhydrazine, benzoin, 9,10-phenanthrenequinone , camphorquinone, methyl phenylglyoxylate, titanium titanate compound, and the like.

As the acid generator, for example, p-toluenesulfonic acid 4-hydroxyphenyldimethylhydrazine, hexafluorodecanoic acid-4-hydroxyphenyldimethylhydrazine, p-toluenesulfonic acid-4-ethenyloxy group can be mentioned. Phenyldimethylhydrazine, hexafluoroantimonic acid-4-ethenyloxyphenyl ‧methyl‧benzyl hydrazine, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, p-toluenesulfonic acid An anthracene salt such as diphenylanthracene or diphenylphosphonium hexafluoroantimonate, or a nitrobenzyl tosylate or ester, a benzoin tosylate or the like.

Further, among the compounds described above as the active radical generator, there are also compounds which generate an acid while generating an active radical, for example, three. The compound can also be used as an acid generator.

The content of the photopolymerization initiator (D) is preferably from 0.1 to 30 parts by mass, more preferably from 1 to 20 parts by mass, per 100 parts by mass of the total of the resin (B) and the photopolymerizable compound (C). When the content of the photopolymerization initiator is within the above range, the sensitivity is improved, the exposure time is shortened, and the productivity is improved, which is preferable.

The colored photosensitive resin composition of the present invention contains a solvent (E). Examples of the solvent (E) include ethers, aromatic hydrocarbons, ketones other than the above, alcohols, esters, guanamines, N-methylpyrrolidone, and dimethyl hydrazine.

Examples of the ethers include tetrahydrofuran, tetrahydropyran, 1,4-didecane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether. , diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene Alcohol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monomethyl ether, methyl cyproterone acetate, Ethyl cyproterone acetate, ethyl carbitol acetate, butyl carbitol acetate, anisole, phenethyl ether, methyl anisole, and the like.

Examples of the aromatic hydrocarbons include benzene, toluene, xylene, and mesitylene.

Examples of the ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, and 4-hydroxy-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 esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, and butyrate B. Ester, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxy Ethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 2-hydroxypropionic acid Methyl ester, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionic acid Ethyl ester, methyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, acetamidine Methyl acetate, ethyl acetate ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxy Butyl acetate, γ-butyrolactone, and the like.

Examples of the guanamines include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

Among these, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and 4-hydroxy-4-methyl-2-pentanone are preferred, and it is more preferred to use them in combination.

Further, the solvent (E) may be used singly or in combination of two or more.

The content of the solvent (E) in the colored photosensitive resin composition is preferably from 70 to 95% by mass, more preferably from 75 to 90% by mass, based on the mass fraction of the photosensitive resin composition. When the content of the solvent (E) is within the above range, the flatness at the time of coating is good, and the color density is not insufficient when the color filter is formed, so that the display characteristics tend to be good, which is preferable.

Further, the coloring photosensitive resin composition of the present invention may further contain a photopolymerization initiation aid (F). The photopolymerization initiation aid (F) is a compound or a sensitizer which is usually used in combination with a photopolymerization initiator (D) to promote polymerization of a photopolymerizable compound which starts polymerization by a photopolymerization initiator.

Examples of the photopolymerization initiation assistant (F) include an amine compound, an alkoxy fluorene compound, and 9-oxosulfuric acid. Compounds, etc.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethyl Isoamyl benzoate benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as micbutone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis ( Ethylmethylamino)benzophenone or the like, among them, 4,4'-bis(diethylamino)benzophenone is preferred.

As the alkoxy ruthenium compound, for example, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl -9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

9-oxosulfur For the compound, for example, 2-isopropyl-9-oxysulfide 4-isopropyl-9-oxosulfur 2,4-diethyl-9-oxosulfur 2,4-dichloro-9-oxosulfur 1-chloro-4-propoxy-9-oxosulfur Wait.

The photopolymerization initiation aid (F) may be used singly or in combination of two or more. In addition, as a photopolymerization initiation aid (F), for example, a commercial item such as "EAB-F" (manufactured by Hodogaya Chemical Industry Co., Ltd.) can be used.

The combination of the photopolymerization initiator (D) and the photopolymerization initiation assistant (F) in the coloring photosensitive resin composition of the present invention may, for example, be diethoxyacetophenone/4,4'- Bis(diethylamino)benzophenone, 2-methyl-2- Lolinyl-1-(4-methylthiophenyl)propan-1-one/4,4'-bis(diethylamino)benzophenone, 2-hydroxy-2-methyl-1-benzene Propane-1-one/4,4'-bis(diethylamino)benzophenone, benzoin dimethyl ketal/4,4'-bis(diethylamino)benzol Ketone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one/4,4'-bis(diethylamino)benzophenone , 1-hydroxycyclohexyl phenyl ketone / 4,4'-bis(diethylamino)benzophenone, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl) Oligomer of phenyl]propan-1-one/4,4'-bis(diethylamino)benzophenone, 2-benzyl-2-dimethylamino-1-(4- Polinylphenyl)butan-1-one/4,4'-bis(diethylamino)benzophenone, etc., preferably 2-methyl-2- Lolinyl-1-(4-methylthiophenyl)propan-1-one / 4,4'-bis(diethylamino)benzophenone.

When the photopolymerization initiation assistant (F) is used, the amount thereof is preferably 0.01 to 10 mol, more preferably 0.01 to 5 mol, based on the photopolymerization initiator (D). ear.

The coloring photosensitive resin composition of the present invention may further contain a surfactant (G). The surfactant (G) is at least one selected from the group consisting of a polyfluorene-based surfactant, a fluorine-based surfactant, and a polyfluorene-based surfactant having a fluorine atom.

The polyoxosiloxane surfactant may, for example, be a surfactant having a decane bond. Specifically, DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, 29SHPA, SH30PA, SH8400 (trade name, manufactured by Dow Corning Toray Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (Shin-Etsu Chemical) Industrial Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, manufactured by a subsidiary of TSF4460 (Momentive Performance Materials Japan), etc.

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain. Specifically, Fluorad (trade name) FC430, Fluorad FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megaface (trade name) F142D, Megaface F171, Megaface F172, Megaface F173, Megaface F177, Megaface F183, Megaface R30 (DIC) Co., Ltd.), 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 SC101, Surflon SC105 (Asahi Glass Co., Ltd.) Co., Ltd.), E5844 (manufactured by Daikin Precision Chemical Research Co., Ltd.), BM-1000, BM-1100 (all trade names, manufactured by BM Chemie).

Examples of the polyfluorene-based surfactant having a fluorine atom include a surfactant having a decane bond and a fluorocarbon chain. Specific examples include Megaface (registered trademark) R08, Megaface BL20, Megaface F475, Megaface F477, Megaface F443 (manufactured by DIC Corporation), and the like.

These surfactants may be used singly or in combination of two or more.

The content of the surfactant (G) is preferably 0.00001 to 0.1% by mass, more preferably 0.00005 to 0.01% by mass, based on the coloring photosensitive resin composition. When the content of the surfactant (G) 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 using the colored photosensitive resin composition of the present invention, for example, the colored photosensitive resin composition of the present invention is applied to a substrate or another resin layer (for example, previously formed on a substrate) a method of removing a volatile component such as a solvent to form a colored layer, and then exposing and developing the colored layer via a photomask (ie, photolithography); and using no light on the other colored photosensitive resin composition layer or the like The method of the lithography inkjet machine, and the like.

In the pattern forming method described above, the coating film of the present invention can be obtained by using no mask and/or without developing.

Specifically, a plurality of TFTs 22 are formed on the glass substrate 21 for each pixel by a known method such as photolithography (see FIG. 1). TFT 22 comprises: for example by molybdenum (Mo) is formed on the glass substrate 21 on the shutter gate line and constitute a part of the source electrode 22a, are formed on the gate electrode 22a, for example, on the nitride film (SiN _x) and a gate insulating film 22b composed of a laminated film of an oxide film (SiO ₂ ), a polysilicon film 22c formed on the gate insulating film 22b, and a layer of, for example, an oxide film (SiO ₂ ) and a nitride film (SiN _x ) A protective film 22d formed of a film. A region of the polysilicon film 22c opposed to the gate electrode 22a serves as a channel region of the TFT 22, and a region on both sides of the channel region serves as a source region or a drain region. The source region of the polysilicon film 22c is electrically connected to a signal line 27 formed of, for example, aluminum (Al) via a connection hole (contact hole) provided in the protective film 22d. Further, the drain region of the polysilicon film 22c is electrically connected to the pixel electrode 24 via a connection hole (contact hole) 201 as described below.

When a plurality of TFTs 22 are formed on each of the pixels on the glass substrate 21, alignment marks (not shown) are formed while the TFTs 22 are formed on the glass substrate 21. This alignment mark serves as a position alignment reference in the formation step of the color filter layer 23 as described below. Further, the alignment marks may also serve as marks for bonding the drive substrate and the counter substrate. The alignment mark can be formed in the same step by at least one of the layers when a metal layer such as a wiring or a polysilicon layer is formed in the manufacturing process of the TFT 22.

Next, on the glass substrate 21 on which the TFT 22 and the alignment mark are formed, a colored photosensitive resin composition layer 23A having a film thickness of 0.5 to 5.0 μm, for example, 1.0 μm, is formed by a spin coating method or another method. The colored photosensitive resin composition layer 23A corresponds to the color filter of the present invention.

Then, heat treatment is performed at a temperature in the range of 30 to 120 ° C, for example, 60 to 110 ° C, whereby the colored photosensitive resin composition layer 23A is dried. To dry and color the photosensitive composition layer 23A, it can carry out by combining a vacuum drying and heat drying. Then, the colored photosensitive resin composition layer 23A is irradiated with ultraviolet rays through a mask (not shown), and the excess portion (unexposed portion) is selectively removed by the developer, thereby forming a drain reaching the polysilicon film 22c. The connection hole (contact hole) 201 of the area is then washed with water. After that, the colored photosensitive resin composition layer 23A is reflowed (reflowed), and the curable component contained in the colored photosensitive composition layer 23A is cured to be in a temperature range of 100 to 300 ° C. For example, heating at 150~230 °C.

Thereby, the colored photosensitive resin composition layer 23A is formed as a color filter layer 23 including the red color filter 23a, the green color filter 23b, and the blue color filter 23c for each pixel row (refer to FIG. 2). . The region between the filters of the color filter layer 23 serves as a mixed region of adjacent colors. However, since this region is opposed to the light-shielding region 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 film 29 as a protective film having a film thickness of 0.3 to 2.0 μm is formed by, for example, a spin coating method to cover the color filter layer 23. Then, the photosensitive resin film 29 is irradiated with ultraviolet rays through a photomask (not shown), and the region corresponding to the connection hole 201 and the excess portion are selectively removed by the developer, thereby forming a drain region reaching the polysilicon film 22c. The connection hole (contact hole) 202 is then washed with water. Thereafter, the photosensitive resin film 29 is reflowed (remelted), and heated at a temperature in the range of 100 to 300 ° C, for example, 200 ° C. Then, in order to remove the residue such as a dye deposited in the contact hole 202 and the organic substance, etching is performed by oxygen plasma, and further, etching is performed by dilute hydrofluoric acid to remove the oxide film formed of the oxygen plasma.

Next, a transparent conductive material such as ITO (Indium-Tin Oxide: indium-tin oxide mixed film) is formed on the photosensitive resin film 29 by, for example, a sputtering method, and then the photolithography technique and etching are used. The ITO film is patterned to form a transparent pixel electrode 24 (see FIG. 3). Further, depending on the device to be fabricated, the pixel electrode 24 may be formed of a metal such as aluminum (Al) or silver (Ag). Thereafter, an alignment film is formed 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 heat resistance can be obtained.

Example

Hereinafter, the present invention will be described in more detail by way of examples. Unless otherwise stated, the "%" and "parts" in the examples are % by mass and parts by mass.

[Synthesis Example 0]

In a four-necked flask equipped with a stirrer, a thermometer, an air-sealed tube, and a reflux condenser, a bisphenol A type epoxy resin [ARALDITE AER2603, manufactured by Asahi Kasei Epoxy Co., Ltd., having an epoxy equivalent of 186 was charged. 186 parts, 40 parts of adipic acid, 31 parts of acrylic acid, 420 parts of propylene glycol monomethyl ether acetate, 0.8 parts of triphenylphosphine and 0.2 parts of hydroquinone were heated to 120 ° C while blowing air. The reaction was carried out for about 20 hours to obtain a reactant having an acid value of 0.5 KOHmg/g. Then, 22 parts of tetrahydrophthalic anhydride was added, and further reacted at 100 ° C for 6 hours to obtain an acid value of a solid content of 29 KOH mg / g, a solid content concentration of 40%, and a weight average molecular weight in terms of polystyrene. It is a resin solution 0 of a 4.0 × 10 ³ polycarboxylic acid resin (B0).

[Synthesis Example 1]

In a four-necked flask equipped with a stirrer, a thermometer, an air-sealed tube, and a reflux condenser, a bisphenol A type epoxy resin [ARALDITE AER2603, manufactured by Asahi Kasei Epoxy Co., Ltd., having an epoxy equivalent of 189 was charged. 189 parts by weight, 40.2 parts by weight of adipic acid, 31.0 parts by weight of acrylic acid, 208.2 parts by weight of propylene glycol monomethyl ether acetate, 0.8 parts by weight of triphenylphosphine, and 0.2 parts by weight of methyl hydroquinone, while blowing air. The mixture was heated to 120 ° C for about 20 hours to obtain a reactant having an acid value of 0.5 KOH mg / g.

Then, 126.6 parts by weight of tetrahydrophthalic anhydride was charged, and further reacted at 100 ° C for 6 hours. Then, 88.5 parts by weight of glycidyl methacrylate was added, and the mixture was reacted at 120 ° C for 10 hours, and then 504.6 parts by weight of propylene glycol monomethyl ether acetate was added to obtain an acid value of the solid content of 30.0 KOH mg / g, and the solid content concentration was obtained. A resin solution 1 of a polycarboxylic acid resin (B1) having a weight average molecular weight of 7.0 × 10 ^{3 in terms} of polystyrene of 40%.

[Synthesis Example 2]

In a four-necked flask equipped with a stirrer, a thermometer, an air-sealed tube, and a reflux condenser, a bisphenol A type epoxy resin [ARALDITE AER2603, manufactured by Asahi Kasei Epoxy Co., Ltd., having an epoxy equivalent of 189 was charged. 189 parts by weight, 7.3 parts by weight of adipic acid, 63.4 parts by weight of acrylic acid, 189.0 parts by weight of propylene glycol monomethyl ether acetate, 0.8 parts by weight of triphenylphosphine, and 0.2 parts by weight of hydroquinone, while blowing air, The mixture was heated to 120 ° C for about 20 hours to obtain a reactant having an acid value of 0.5 KOH mg / g.

Then, 133.8 parts by weight of tetrahydrophthalic anhydride was charged, and further reacted at 100 ° C for 6 hours. Then, 112.2 parts by weight of glycidyl methacrylate was added, and the mixture was reacted at 120 ° C for 10 hours, and then 546.6 parts by weight of propylene glycol monomethyl ether acetate was added to obtain an acid value of a solid content of 15.5 KOH mg / g, and a solid content concentration. 40%, polystyrene-converted resin solution 2 of a polycarboxylic acid resin (B2) having a weight average molecular weight of 4.0 × 10 ³ .

[Comparative Synthesis Example]

Nitrogen gas was introduced into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer at 0.02 L/min to form a nitrogen atmosphere, and 200 parts by mass of 3-methoxy-1-butanol and 3-methoxybutyl group were added. 105 parts by mass of the base acetate was heated to 70 ° C while stirring. Then, it was dissolved in 60 parts by mass of methacrylic acid, and 3,4-epoxytricyclo[5.2.1.0 ^2.6 ] decyl acrylate (the compound represented by the following formula (B0-1-1)) A solution was prepared by dissolving 240 parts by mass of a compound represented by (B0-2-1) in a molar ratio of 50:50 and 140 parts by mass of 3-methoxybutyl acetate, using a dropping funnel for 4 hours. The dissolved droplets were added to the flask kept at 70 ° C for an hour. On the other hand, 30 parts by mass of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 225 parts by mass of 3-methoxybutyl acetate, and another The dropping funnel was added dropwise to the flask over 4 hours. After the dropwise addition of the solution of the polymerization initiator, the mixture 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 × 10 ⁴ , a molecular weight distribution of 2.5, and a solid content of 33% by mass. A resin solution H1 of a resin (H1) having an acid value of 34 mg-KOH/g.

[Chem. 46]

The measurement of the polystyrene-equivalent weight average molecular weight (Mw) of the obtained resins B1, B2, B0, and H1 was carried out under the following conditions using a GPC method.

Device: HLC-8120GPC (manufactured by Tosoh Co., Ltd.)

Column: TSK-GELG2000HXL

Column temperature: 40 ° C

Solvent: THF (tetrahydrofuran, tetrahydrofuran)

Flow rate: 1.0 mL/min

The concentration of the solid content of the test liquid: 0.001~0.01% by mass

Injection volume: 50 μL

Detector: RI

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

[Synthesis Example 3] (Synthesis Example of Compound of Formula (1))

In a flask equipped with a cooling tube and a stirring device, 15 parts of a mixture of a compound represented by the formula (A0-1) and a compound represented by the formula (A0-2) (manufactured by external production), 15 parts of chloroform, and N, N were charged. 8.9 parts of dimethylformamide was maintained at 20 ° C or lower while stirring, and 10.9 parts of sulfite chloride was added dropwise. 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 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise. Thereafter, the mixture was stirred at the same temperature for 5 hours to cause a reaction. After the solvent of the obtained reaction mixture was distilled off by a rotary evaporator, a small amount of methanol was added and stirred vigorously. The mixture was added to a mixed solution 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 (A1-a) and the compound of the formula (A1-b) (dye). A1) (a mixture of the compounds represented by the formula (A1-1) to the formula (A1-8)) 11.3 parts.

[化47]

[In the formula (A1-a) and the formula (A1-b), R ^g , R ^h and R ⁱ each independently represent a hydrogen atom, -SO ₃ ^- , -SO ₃ H or 2-ethylhexylsulfanyl]

[48]

[Example 1] (Preparation of Colored Photosensitive Resin Composition 1)

The colored photosensitive resin composition 1 was obtained.

The obtained colored photosensitive resin composition 1 was evaluated by the following method. The results are shown in Table 1.

<Formation of pattern>

The colored photosensitive resin composition 1 was applied by a spin coating method on a glass substrate (Eagle 2000; manufactured by Corning) of 2 inches square, and then prebaked at 100 ° C for 3 minutes. After cooling, the interval between the substrate coated with the colored photosensitive resin composition and the patterned quartz glass mask was 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used in an atmosphere. The light was irradiated with an exposure amount of 150 mJ/cm ² (based on 365 nm). After the light irradiation, the coating film was immersed and developed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 28 ° C for 80 seconds, washed with water, and then placed in an oven at 220 ° C. Bake after 20 minutes. After leaving to stand for cooling, the film thickness of the obtained hardened pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.) and found to be 2.2 μm.

<heat resistance evaluation>

The pattern on the obtained glass substrate was measured for spectroscopic using a color measuring machine (OSP-SP-200; manufactured by Olympus Co., Ltd.), and CIE (Commission International de I) was measured using a color matching function of a C light source. XY chromaticity coordinates (Bx, By) and brightness BY in the XYZ color system of 'Eclairage, International Commission on Illumination. The above pattern was heated in an oven at 230 ° C for 2 hours. After heating, the chromaticity coordinates were measured again, and the color difference ΔEab* before and after heating was calculated. The results are shown in Table 22.

The smaller the color difference ΔEab*, the better the heat resistance. Moreover, when the heat resistance of the pattern is good, the coating film also exhibits good heat resistance similarly to the pattern.

[Examples 2 to 4]

A colored photosensitive resin composition and a pattern were obtained in the same manner as in Example 1 except that the resin was changed or a plurality of resins were combined so as to have the composition shown in Table 22. This was evaluated in the same manner as in Example 1. The results are shown in Table 22.

[Comparative Example 1] (Preparation of coloring photosensitive resin composition)

A colored photosensitive resin composition was obtained. With respect to the obtained colored photosensitive resin composition, a pattern was obtained in the same manner as in Example 1, and it was evaluated in the same manner as in Example 1. The results are shown in Table 22.

[Synthesis Example 4] (Synthesis Example of Compound of Formula (2))

After adding 200 parts of water to 10.0 parts of toluidine-4-sulfonic acid represented by the formula (a-2), the pH was adjusted to 7 to 8 with a 30% aqueous sodium hydroxide solution under ice cooling. The following operations were carried out under ice bath cooling. 11.1 parts of sodium nitrite was added and stirred for 30 minutes. 39.0 parts of 35% hydrochloric acid was added in small portions to prepare a brown solution, followed by stirring for 2 hours. An aqueous solution obtained by dissolving 10.1 parts of aminosulfuric acid in 101 parts of water was added to the reaction solution and stirred to obtain a suspension containing a diazonium salt.

Adding 125 parts of water and N-methyl group to 14.0 parts of 1-(2-ethylhexyl)-3-cyano-4-methyl-6-hydroxypyridin-2-one represented by formula (c-2) After 25.0 parts of pyrrolidone, the pH was adjusted to 8-9 using a 30% aqueous sodium hydroxide solution under ice cooling.

The following operations were carried out under ice bath cooling. After stirring the above aqueous solution of pyridone to form a colorless solution, the pH was adjusted to 8 to 9 with a 30% aqueous sodium hydroxide solution, and a suspension containing a diazonium salt was added dropwise by a pump for 2 hours. After completion of the dropwise addition, the mixture was further stirred for 2 hours, whereby a yellow suspension was obtained. The yellow solid obtained by filtration was dried under reduced pressure at 60 ° C to obtain 21.4 parts of the compound of formula (d-3) (yield: 87%).

0.35 g of the compound (d-3) was dissolved in N,N-dimethylformamide to a volume of 250 cm ³ , and 2 cm ^{3 of the solution was} diluted with water to a volume of 100 cm ³ (concentration: 0.028 g) /L), the absorption spectrum was measured using a spectrophotometer [quartz cell, the length of the groove was 1 cm]. The compound showed an absorbance of 2.9 (arbitrary unit) at λ max = 433 nm.

5.0 parts of the compound (d-3), 35 parts of acetonitrile, and 1.6 parts of N,N-dimethylformamide were placed in a flask equipped with a cooling tube and a stirring device, and the mixture was maintained at 20 ° C or lower while stirring. 2.4 parts of thioindigo chloride. After completion of the dropwise addition, the temperature was raised to 40 ° C, and the mixture was allowed to react at the same temperature for 2 hours, and then cooled to 20 ° C. The cooled reaction solution was poured into 150 parts of ice water while stirring, and stirred for 30 minutes. The precipitated yellow crystals were separated by filtration, washed thoroughly with tap water, and dried at room temperature for 1 hour. Further, a flask equipped with a cooling tube and a stirring device was prepared, and 2.0 parts of 1-amino-2-propanol and 20 parts of N-methylpyrrolidone were placed, and the mixture was maintained at 20 ° C or lower under stirring, and was allowed to stand for 1 hour. Preparation of yellow crystals. After the yellow solid was charged, the temperature of the solution was raised to room temperature, and the reaction solution was stirred for 30 minutes. After 40 parts of methanol was added to the reaction solution and stirred, the mixed solution was added to a mixed liquid of 29 parts of acetic acid and 300 parts of ion-exchanged water while stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed thoroughly with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain 3.9 parts of a compound of formula (III-3) (yield: 69%).

0.35 g of the compound (III-3) was dissolved in ethyl lactate to a volume of 250 cm ³ , and 2 cm ^{3 of the} solution was diluted with ion-exchanged water to a volume of 100 cm ³ (concentration: 0.028 g/L). The absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). The compound showed an absorbance of 2.3 (arbitrary unit) at λ max = 431 nm.

The following reaction was carried out under a nitrogen atmosphere. After 4.0 parts of N-methylpyrrolidone was added to 2.0 parts of the compound (III-3), the mixture was stirred for 30 minutes to prepare a reaction solution. The reaction solution was stirred while stirring at room temperature, and 0.1 part of ruthenium dichloride was added dropwise. After the completion of the dropwise addition, the mixture was further stirred for 8 hours. After the reaction solution was poured into 300 parts of water, 80 parts of ethyl acetate was added thereto, and the mixture was stirred for 30 minutes. The organic phase was separated by using a separatory funnel, and further washed with 500 parts of water, 500 parts of a 10% sodium carbonate aqueous solution, 500 parts of a 10% aqueous acetic acid solution, and 500 parts of ion-exchanged water. The solvent of the organic phase of the partition was distilled off to obtain 2.0 parts of the compound (dye A2) represented by the formula (I-6). The yield was 85%.

The structure of the compound (I-6) was determined by mass spectrometry. The mass spectrometer was JMS-700 (manufactured by JEOL Ltd.).

Mass spectrometry: ionization mode = FD +: m / z = 1200

0.35 g of the compound (I-6) was dissolved in ethyl lactate to a volume of 250 cm ³ , and 2 cm ^{3 of the} solution was diluted with ion-exchanged water to a volume of 100 cm ³ (concentration: 0.028 g/L). The absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). The compound showed an absorbance of 2.2 (arbitrary unit) at λ max = 431 nm.

[Synthesis Example 8] (Synthesis Example of Compound of Formula (3))

After adding 65 parts of water to 7.5 parts of 2-amino-4-methylsulfonyl-6-nitrophenol (CAS No. 101861-04-5), 1.3 parts of sodium hydroxide was added and dissolved. Under ice cooling, 6.1 parts of an aqueous solution of 35% sodium nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and then 19.4 parts of 35% hydrochloric acid was added in a small amount to be dissolved, and stirred for 2 hours. A suspension containing a diazonium salt. Then, an aqueous solution obtained by dissolving 5.6 parts of an aminosulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.) in 26 parts of water was slowly added, and excess sodium nitrite was quenched.

Then, 5.6 parts of 3-methyl-1-phenyl-5-pyrazolone (manufactured by Wako Pure Chemical Industries, Ltd.) was suspended in 70 parts of water, and the pH was adjusted to 8.0 using sodium hydroxide. At this time, the suspension was added dropwise over 15 minutes while appropriately adding a 10% sodium hydroxide solution to the suspension containing the diazonium salt to control the pH in the range of 7 to 7.5. After completion of the dropwise addition, the mixture was further stirred for 30 minutes, whereby a yellow suspension was obtained. Stir for 1 hour. The yellow solid obtained by filtration was dried under reduced pressure at 60 ° C to obtain 11.7 parts of the compound of formula (p-1) (yield: 87%).

Add 10 parts of the compound of the formula (p-1) to 100 parts of dimethylformamide (manufactured by Tokyo Chemical Industry Co., Ltd.) and dissolve it, and add ammonium sulfate (III) ammonium sulfate dodecahydrate (Wako Pure Chemical Industries Co., Ltd.) After making 1.1 parts of sodium acetate (manufactured by Wako Pure Chemical Industries Co., Ltd.), the mixture was heated and refluxed for 4 and a half hours. After cooling to room temperature, the reaction solution was poured into 1500 parts of 20% saline solution, and the red-orange solid obtained after filtration was dried at 60 ° C to obtain 13.6 parts of the compound represented by the formula (z-1). %).

The structure of the compound represented by the formula (z-1) was identified using a mass spectrometer JMS-700 (manufactured by JEOL Ltd.).

Identification of compounds represented by formula (z-1)

(mass spectrometry) ionization mode = ESI-: m/z = 882.1 [M-Na ⁺ ] ^-

Exact Mass: 905.1

170 parts of anhydrous chloroform (manufactured by Kanto Chemical Co., Ltd.), camphorsulfonic acid (manufactured by Aldrich Co., Ltd.), 1.0 part, 4-(N, N-) were added to 18 parts of Rose Red B (manufactured by Tokyo Chemical Industry Co., Ltd.). 1.4 parts of dimethylamino)pyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 18 parts of triethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) were stirred for about 30 minutes. Then, slowly added to 10.5 parts of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.), and added anhydrous chloroform (47 parts). After pre-dissolving the resulting solution, it was stirred at room temperature for about 2 hours. After two times of liquid separation operation with 150 parts of 1 N aqueous hydrochloric acid solution, the organic layer was washed twice with 150 parts of 10% saline. Then, after adding 43 parts of anhydrous magnesium sulfate and stirring for about 30 minutes, the desiccant was filtered and the solvent was distilled off, thereby obtaining 20.6 parts of the compound represented by the formula (g-1) (yield 90%).

Identification of compounds represented by formula (g-1)

(mass spectrometry) ionization mode = ESI +: m / z = 575.3 [M-Cl ^- ] ⁺

Accurate mass: 610.3

A solution (s3) was prepared by adding 4030 parts of methanol to 253 parts of the compound represented by the formula (z-1). Further, 1080 parts of methanol was added to 153 parts of the compound represented by (g-1) to prepare a solution (t3). Thereafter, the solution (s3) and the solution (t3) were mixed at room temperature and stirred for about 1 hour. The resulting red solid was dried under reduced pressure at 60 ° C, washed with 3,500 parts of water, filtered, and dried under reduced pressure at 60 ° C to obtain a compound of formula (3a-23) (dye A3) 263 parts (yield 65%).

The structure of the compound represented by the formula (3a-23) is determined by elemental analysis. The analytical equipment was an ICP (Inductively Coupled Plasma) luminescence analyzer (ICPS-8100; manufactured by Shimadzu Corporation).

C: 55.6; H: 5.1; N: 11.9; Cr: 3.71

[Example 5] (Preparation of coloring photosensitive resin composition)

A colored photosensitive resin composition was obtained.

A pattern was obtained in the same manner as in Example 1 and evaluated. The results are shown in Table 23.

[Examples 6 to 8]

A colored photosensitive resin composition was obtained in the same manner as in Example 5 except that the resin was changed or a plurality of resins were combined so as to have the composition shown in Table 23. Further, a pattern was obtained in the same manner as in Example 1 and evaluated. The results are shown in Table 23.

[Embodiment 9] (Preparation of coloring photosensitive resin composition)

A colored photosensitive resin composition was obtained.

A pattern was obtained in the same manner as in Example 1 and evaluated. The results are shown in Table 24.

[Examples 10 to 12]

A colored photosensitive resin composition was obtained in the same manner as in Example 9 except that the resin was changed or a plurality of resins were combined so as to have the composition shown in Table 24. Further, a pattern was obtained in the same manner as in Example 1 and evaluated. The results are shown in Table 24.

[Example 13] (Preparation of colored photosensitive resin composition 0)

The colored photosensitive resin composition 0 was obtained.

The obtained colored photosensitive resin composition 0 was evaluated by the above method. The results are shown in Table 25.

[Embodiment 14]

A colored photosensitive resin composition and a pattern were obtained in the same manner as in Example 13 except that a plurality of resins were combined so as to have the composition shown in Table 25. The evaluation was carried out in the same manner as in Example 13. The results are shown in Table 25.

[Example 15] (Preparation of coloring photosensitive resin composition)

A colored photosensitive resin composition was obtained.

A pattern was obtained in the same manner as in Example 13 and evaluated. The results are shown in Table 26.

[Example 16]

A colored photosensitive resin composition was obtained in the same manner as in Example 15 except that the resin was changed to a composition shown in Table 26 or a plurality of resins were combined. Further, a pattern was obtained in the same manner as in Example 13 and evaluated. The results are shown in Table 26.

[Example 17] (Preparation of coloring photosensitive resin composition)

A colored photosensitive resin composition was obtained.

A pattern was obtained in the same manner as in Example 13 and evaluated. The results are shown in Table 27.

[Embodiment 18]

A colored photosensitive resin composition was obtained in the same manner as in Example 17 except that the resin was changed to a composition shown in Table 27 or a plurality of resins were combined. Further, a pattern was obtained in the same manner as in Example 13 and evaluated. The results are shown in Table 27.

In the pattern formed by using the colored photosensitive resin composition of the present invention, ΔEab* showed a small value, and it was confirmed that the heat resistance was high.

[Industrial availability]

According to the present invention, a coating film, a pattern, and a color filter having high heat resistance can be obtained.

twenty one. . . glass substrate

twenty two. . . TFT (switching element)

22a. . . Gate electrode

22b. . . Gate insulating film

22c. . . Polycrystalline germanium film

22d. . . Protective film

twenty three. . . Color filter layer

23A. . . Coloring photosensitive resin composition layer (film for color filter)

23a. . . Red filter

23b. . . Green filter

23c. . . Blue filter

twenty four. . . Pixel electrode

27. . . Signal line

29. . . Photosensitive resin film (protective film)

201, 202. . . Connection hole

1 is a schematic view showing a method of manufacturing a color filter of the present invention;

2 is a schematic view showing a method of manufacturing the color filter of the present invention; and

Fig. 3 is a schematic view showing a method of manufacturing the color filter of the present invention.

Claims (15)

A colored photosensitive resin composition containing a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E), and the colorant (A) is a coloring agent containing a dye, and the binder resin (B) is a resin containing a polycarboxylic acid resin obtained in such a manner that one or more epoxy resins (a) having two glycidyl groups, one or more types The dibasic acid (b) shown in (Bb) and one or more ethylenically unsaturated monocarboxylic acids (c) are reacted, and then the obtained polymer is reacted with one or more polybasic acid anhydrides (d): HOOC- R ^a -COOH (Bb) In the formula (Bb), R ^a represents ^a divalent aliphatic hydrocarbon group having 2 to 8 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 8 carbon atoms, the aliphatic hydrocarbon group and the alicyclic group. The hydrogen atom contained in the hydrocarbon group may be substituted with a hydroxyl group. The colored photosensitive resin composition of claim 1, wherein the binder resin (B) is a resin comprising a polycarboxylic acid resin obtained in such a manner that more than one epoxy resin having two glycidyl groups (a) And reacting the dibasic acid (b) represented by the above formula (Bb) and one or more ethylenically unsaturated monocarboxylic acids (c), and then the obtained polymer and one or more polybasic acid anhydrides ( d) reacting with one or more radically polymerizable compounds (e) having one glycidyl group: HOOC-R ^a -COOH (Bb) In the formula (Bb), R ^a represents a carbon number of 2-8 The divalent aliphatic hydrocarbon group or the divalent alicyclic hydrocarbon group having 3 to 8 carbon atoms, and the aliphatic hydrocarbon group and the hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with a hydroxyl group. The colored photosensitive resin composition of claim 2, wherein the amount of the radically polymerizable compound (e) having one glycidyl group is 0.05 to 0.90 moles per mole of the polybasic acid anhydride (d). The colored photosensitive resin composition according to claim 1 or 2, wherein the epoxy resin (a) having two glycidyl groups is an epoxy resin represented by the formula (Ba): In the formula (Ba), R ^b , R ^c , R ^d and R ^e represent a hydrogen atom or a methyl group; n represents a number from 0 to 10, and when n is an integer of 2 or more, a plurality of R ^b and R ^c are mutually compatible. The same can be different. The colored photosensitive resin composition of claim 1 or 2, wherein the ethylenically unsaturated monocarboxylic acid (c) is at least one selected from the group consisting of acrylic acid and methacrylic acid. The colored photosensitive resin composition of claim 2 or 3, wherein the radically polymerizable compound (e) having one glycidyl group is selected from the group consisting of glycidyl acrylate and glycidyl methacrylate. At least one. The colored photosensitive resin composition of claim 1 or 2, wherein the content of the binder resin (B) is 20% by mass or more and 80% by mass or less based on the total amount of the binder resin (B) and the photopolymerizable compound (C). . The colored photosensitive resin composition of claim 1 or 2, wherein the dye is contained The amount is 0.5% by mass or more and 60% by mass or less based on the solid content of the colored photosensitive resin composition. The colored photosensitive resin composition of claim 1 or 2, wherein the dye contains at least one selected from the group consisting of an azo compound, a metal complex having an azo compound as a ligand, and a dibenzopyran compound. One. The colored photosensitive resin composition of claim 1 or 2, wherein the dye comprises the dye of the formula (1): In the formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁶ or a carbon number 6 to 10 monovalent aromatic hydrocarbon group, and the hydrogen atom contained in the aromatic hydrocarbon group may pass through a halogen atom, -R ⁶ , -OH, -OR ⁶ , -SO ₃ ^- , -SO ₃ H, SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NH ₂ , -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ substituted; R ⁵ represents -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NHR ⁸ or -SO ₂ NR ⁸ R ⁹ ; m represents an integer of 0 to 5; when m is an integer of 2 or more, a plurality of R ⁵ may be the same or different; X represents a halogen atom; a represents an integer of 0 or 1; R ⁶ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, 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 -O-, -CO- or -NR ⁷ -substituted; R ⁷ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, 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 -O - or -CO-substituted; R ⁸ and R ⁹ each independently represent a linear or branched monovalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, a carbon number of 3 to 30 one-valent alicyclic hydrocarbon group or -Q, the saturated aliphatic hydrocarbon group and the hydrogen atom contained in the alicyclic hydrocarbon group may be substituted by -OH, a halogen atom, -Q, -CH=CH ₂ or -CH=CHR ⁶ , the saturated aliphatic hydrocarbon group and -CH ₂ - contained in the alicyclic hydrocarbon group may be substituted by -O-, -S-, -CO-, -NH- or -NR ⁶ -; R ⁸ and R ⁹ may be bonded to each other to form 3~ a heterocyclic ring containing a nitrogen atom of a 10-member ring, wherein the hydrogen atom contained in the hetero ring may be substituted by R ⁶ , -OH or -Q; Q represents a carbon number of 6 to 10 monovalent aromatic hydrocarbon group or carbon number 3~ a monovalent heterocyclic group, the aromatic hydrocarbon group and a hydrogen atom contained in the heterocyclic group may be via -OH, R ⁶ , -OR ⁶ , -NO ₂ , -CH=CH ₂ , -CH=CHR ⁶ Or a halogen atom; M represents a sodium atom or a potassium atom; wherein the compound of the formula (1) has the same number of + charges as the number of charges. The colored photosensitive resin composition of claim 1 or 2, wherein the colorant (A) is a coloring agent further comprising a pigment. The colored photosensitive resin composition of claim 11, wherein the pigment comprises a color selected from the group consisting of CI Pigment Blue 15:6, CI Pigment Red 254, CI Pigment Red 242, CI Pigment Red 177, CI Pigment Green 58, CI Pigment Yellow 150, and CI pigment At least one of the group consisting of yellow 138. A coating film formed by applying a colored photosensitive resin composition according to claim 1 or 2 to a substrate and drying it. A pattern obtained by applying the colored photosensitive resin composition of claim 1 or 2 onto a substrate, drying, exposing, and developing. A color filter comprising the coating film of claim 13, the pattern of claim 14, or the coating film of claim 13 and the pattern of claim 14.