TW201321893A - Colored photosensitive resin composition - Google Patents

Abstract

A colored photosensitive resin composition comprising (A), (B1), (B2), (C) and (D) is provided. (A) coloring matter; (B1) a resin comprising a structural unit derived from a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride and a structural unit derived from a monomer having a C2-4 cyclic ether structure and an ethylenic unsaturated bond; (B2) a resin comprising a structural unit derived from a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride and a structural unit derived from a monomer having an alicyclic hydrocarbon structure, provided that the structural unit derived from a monomer having a C2-4 cyclic ether structure and an ethylenic unsaturated bond is not contained; (C) a polymerizable compound; and (D) a polymerization initiator.

Description

Colored photosensitive resin composition

The present invention relates to a 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. As such a color-sensitive photosensitive resin composition, a color-sensitive photosensitive resin composition containing only a copolymer of methacrylic acid and 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate as a resin is known (JP2010) -211198-A).

When the pattern is formed by the photolithography method, the colored photosensitive resin composition is applied onto the substrate, and the composition layer formed by drying is peeled off during development to flow out into the developer, and the release sheet is attached as a foreign matter. On the pattern, or clogging the piping of the developer waste liquid in the developing machine. The coloring photosensitive resin composition which has been known in the prior art has a case where the developability cannot be sufficiently satisfied as described above.

The invention includes the following inventions.

[1] A colored photosensitive resin composition comprising (A), (B1), (B2), (C), and (D): (A) a colorant; (B1) comprising a source selected from the group consisting of unsaturated carboxylic acids a structural unit of at least one of a group consisting of an acid and an unsaturated carboxylic anhydride; and a resin derived from a structural unit having a cyclic ether structure having a carbon number of 2 to 4 and a monomer having an ethylenically unsaturated bond; (B2) comprising a resin derived from at least one structural unit selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and a structural unit derived from a monomer having an alicyclic hydrocarbon structure (wherein The structural unit derived from a monomer having a cyclic ether structure having a carbon number of 2 to 4 and an ethylenically unsaturated bond; (C) a polymerizable compound; and (D) a polymerization initiator.

[2] The colored photosensitive resin composition according to [1], wherein (B2) further comprises a structural unit derived from a monomer having an aromatic hydrocarbon group.

[3] The colored photosensitive resin composition according to [1] or [2], wherein the content of (B2) is from 10 to 90% by mass based on the total of (B1) and (B2).

[4] A color filter formed of the colored photosensitive resin composition according to any one of [1] to [3].

[5] A display device comprising the color filter of [4].

According to the colored photosensitive resin composition of the present invention, a release sheet derived from the colored photosensitive resin composition is less likely to be produced in the developer after development.

The colored photosensitive resin composition of the present invention comprises the following (A), (B1), (B2), (C) and (D).

(A) a colorant; (B1) comprising at least one structural unit derived from a group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, and a cyclic ether structure derived from a carbon number of 2 to 4. And a resin of a structural unit of a monomer having an ethylenically unsaturated bond (hereinafter sometimes referred to as "resin (B1)"); (B2) comprises a material selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride. a resin having at least one structural unit and a structural unit derived from a monomer having an alicyclic hydrocarbon structure (excluding a cyclic ether structure having a carbon number of 2 to 4 and ethylene) a structural unit of a monomer of a saturated bond (hereinafter, sometimes referred to as "resin (B2)"); (C) a polymerizable compound; and (D) a polymerization initiator.

The colored photosensitive resin composition of the present invention preferably further contains a solvent (E).

Moreover, the colored photosensitive resin composition of the present invention may optionally contain at least one selected from the group consisting of a polymerization starting aid (D1) and a surfactant (F).

In addition, each component may be used alone or in combination of two or more, unless otherwise specified.

<Colorant (A)>

Examples of the colorant (A) include a dye (A1) and a pigment (A2).

The dye (A1) is not particularly limited, and known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, mord dyes, and the like, and dyes which are soluble in an organic solvent are preferable.

Examples of the dye (A1) include a compound classified as a dye in the Colour Index (published by The Society of Dyers and Colourists), or a well-known dye described in Dyeing Note (color dyeing company). Further, examples of the chemical structure include azo dyes, cyanine dyes, triphenylmethane dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, and methine azo dyes. Squaric acid dye, acridine dye Materials, styrene dyes, coumarin dyes, quinoline dyes, nitro dyes, and the like. Among these, an organic solvent-soluble dye is preferred.

Specifically, CI solvent yellow 4 (hereinafter, the description of CI solvent yellow is omitted, only the number is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 117 , 162, 163, 167, 189, CI solvent red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247, CI Solvent Orange 2, 7, 11, 15, 26, 56, 77, 86, CI Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60, CI Solvent Blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59: 1, 63, 67, 68, 69, 70, 78, 79, 83 , 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139, CI solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 and other CI solvent dyes; 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, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76 , 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172 , 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281 , 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 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 Violet 6B, 7, 9, 17, 19, 30 , 34, 102, CI Acid Blue 1, 7, 9, 15, 18, 22, 23, 25, 27, 29, 40, 41, 42, 43, 45, 51, 54, 59, 60, 62, 70, 72, 74, 78, 80, 82, 83, 86, 87, 90, 92, 93, 96, 100, 102, 103, 104, 112, 113, 117, 120, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 229, 234, 236, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340, CI Acid Green 1, 3, 5, 9, 16, 25, 27, 28, 41, 50, 58 CI acid dyes such as 63, 65, 80, 104, 105, 106, 109; 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 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107, CI directly Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104, CI Direct Blue 1, 2, 6, 8, 15, 22, 25, 40, 41, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293, CI directly CI direct dyes such as green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82; CI disperse yellow 51, 54, 76, CI disperse violet 26, 27, CI disperse blue 1, 14, 56, 60 and other CI disperse dyes; CI alkaline red 1, 10, CI alkaline blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, CI basic green 1 and other CI basic dyes; CI reactivity Yellow 2, 76, 116, CI Reactive Orange 16, CI Reactive Red 36 and other CI reactive dyes; 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, 27, 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 purple 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58, 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 mord green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53 and other CI mordant dyes; C.I. Reduction of green 1, etc. C.I. vat dyes and the like.

These dyes may be appropriately selected depending on the spectral spectrum of the desired color filter.

As the dye (A1), it is preferably Dye (Aa).

Dye (Aa) contains intramolecular A dye of a compound of the skeleton. As Examples of the dye (Aa) include CI Acid Red 51 (hereinafter, the description of CI Acid Red is omitted, only the number is described; the others are the same), 52, 87, 92, 94, 289, 388, CI Acid Violet 9, 30 , 102, CI alkaline red 1 (rhodamine 6G), 2, 3, 4, 8, CI alkaline red 10 (rhodamine B), 11, CI alkaline purple 10, 11, 25, CI solvent red 218, CI mordant red 27, CI reactive red 36 (Bengal rose red B), sulfonium rhodamine G, JP2010-32999-A Dyes and materials described in JP4492760-B Dyes, etc. It is preferably one which is soluble in an organic solvent.

Among these, The dye (Aa) is preferably a dye containing a compound represented by the formula (1a) (hereinafter sometimes referred to as "compound (1a)"). In the case of using the compound (1a), The content of the compound (1a) in the dye (Aa) is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more. It is especially preferred to use only compound (1a) as Dye (Aa).

[In the formula (1a), R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁸ or a C 6-10 monovalent aromatic hydrocarbon group which may have a substituent. R ¹ and R ² may form a ring containing a nitrogen atom together with a nitrogen atom, and R ³ and R ⁴ may form a ring containing a nitrogen atom together with a nitrogen atom. R ⁵ represents -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ ^- Z ⁺ , -CO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ . R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. m represents an integer from 0 to 5. In the case where m is an integer of 2 or more, a plurality of R ^{5 may} be the same or different. Wherein, when R ⁵ is -SO ₃ ^- , m is 1. a represents an integer of 0 or 1. X represents a halogen atom. R ⁸ represents a one-valent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom. Z ⁺ represents ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ . R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and R ⁹ and R ¹⁰ may be bonded to each other to form a nitrogen-containing heterocyclic ring having a 3 to 10 member ring together with the nitrogen atom. R ¹¹ each independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms.

Examples of the one-valent aromatic hydrocarbon group having 6 to 10 carbon atoms of R ¹ to R ⁴ include a phenyl group, a tolylmethyl group, and a xylyl group. Base, propyl phenyl and butyl phenyl.

In the one-valent aromatic hydrocarbon group having 6 to 10 carbon atoms of R ¹ to R ⁴ , the hydrogen atom contained in the aromatic hydrocarbon group may also pass through a halogen atom, -R ⁸ , -OH, -OR ⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ R ⁸ , -SR ⁸ , -SO ₃ R ⁸ , -SO ₂ NR ⁹ R ^{10 ,} etc. Among the substituents, at least one selected from the group consisting of -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ and -SO ₂ NR ⁹ R ¹⁰ is preferred, and more preferably At least one selected from the group consisting of -SO ₃ ^- Z ⁺ and -SO ₂ NR ⁹ R ¹⁰ is selected. At this time, -SO ₃ ^- Z ^{+ is} preferably -SO ₃ ^-+ N(R ¹¹ ) ₄ . When R ¹ to R ^{4 are} such a group, the colored photosensitive resin composition containing the compound (1a) can form a color filter which is less likely to generate foreign matter and is excellent in heat resistance.

R ¹ and R ² may form a ring containing a nitrogen atom together with a nitrogen atom, and R ³ and R ⁴ may form a ring containing a nitrogen atom together with a nitrogen atom. Examples of the ring containing a nitrogen atom include the following.

Examples of the one-valent saturated hydrocarbon group having 1 to 20 carbon atoms of R ⁸ to R ¹¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, and a decyl group. a linear alkyl group having 1 to 20 carbon atoms such as dodecyl, hexadecyl or icosyl; carbon such as isopropyl, isobutyl, isopentyl, neopentyl or 2-ethylhexyl a branched alkyl group of 3 to 20; an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group or a tricyclodecyl group.

Examples of -OR ⁸ include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, and two. Decaconoxy.

Examples of the -CO ₂ R ⁸ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a third butoxycarbonyl group, a hexyloxycarbonyl group, and an eicosyloxycarbonyl group.

Examples of -SR ⁸ include a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a mercaptosulfanyl group, and a decylsulfanyl group.

Examples of -SO ₂ R ⁸ include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and a decylsulfonyl group.

Examples of -SO ₃ R ⁸ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a third butoxysulfonyl group, a hexyloxysulfonyl group, and Alkoxysulfonyl.

Examples of -SO ₂ NR ⁹ R ¹⁰ include an aminesulfonyl group; N-methylaminesulfonyl group, N-ethylaminesulfonyl group, N-propylaminesulfonyl group, and N-isopropyl group; Aminesulfonyl, N-butylamine sulfonyl, N-isobutylamine sulfonyl, N-tert-butylamine sulfonyl, N-tert-butylamine sulfonyl, N-pentyl Aminesulfonyl, N-(1-ethylpropyl)aminesulfonyl, N-(1,1-dimethylpropyl)aminesulfonyl, N-(1,2-dimethylpropyl Aminesulfonyl, N-(2,2-dimethylpropyl)aminesulfonyl, N-(1-methylbutyl)aminesulfonyl, N-(2-methylbutyl)amine Sulfonyl, N-(3-methylbutyl)amine sulfonyl, N-cyclopentylamine sulfonyl, N-hexylamine sulfonyl, N-(1,3-dimethylbutyl) Aminesulfonyl, N-(3,3-dimethylbutyl)aminesulfonyl, N-heptylaminesulfonyl, N-(1-methylhexyl)aminesulfonyl, N-(1 ,4-dimethylpentyl)amine sulfonyl, N-octylamine sulfonyl, N-(2-ethylhexyl)amine sulfonyl, N-(1,5-dimethyl)hexylamine N-1 substituted amine sulfonyl group such as sulfonyl, N-(1,1,2,2-tetramethylbutyl)amine sulfonyl; N,N-dimethylamine sulfonyl, N,N -ethylmethylamine sulfonyl, N,N-diethylamine sulfonyl, N,N- Propylmethylamine sulfonyl, N,N-isopropylmethylamine sulfonyl, N,N-t-butylmethylamine sulfonyl, N,N-butylethylamine sulfonyl, N An N, N-2 substituted amine sulfonyl group such as N-bis(1-methylpropyl)amine sulfonyl group or N,N-heptylmethylamine sulfonyl group.

Further, in the one-valent saturated hydrocarbon group having 1 to 20 carbon atoms of R ⁹ and R ¹⁰ , the hydrogen atom contained in the saturated hydrocarbon group may be substituted by -OH or a halogen atom, and the -CH ₂ - contained in the saturated hydrocarbon group is also It may be replaced by -O-, -CO-, -NH- or -NR ⁸ -.

R ⁹ and R ¹⁰ may be bonded to each other to form a nitrogen-containing heterocyclic ring of 3 to 10 membered rings together with a nitrogen atom. Examples of the hetero ring include the following.

Examples of the alkyl group having 1 to 6 carbon atoms of R ⁶ and R ⁷ include those having 1 to 6 carbon atoms in the linear alkyl group and the branched alkyl group described above.

Examples of the aralkyl group having 7 to 10 carbon atoms of R ¹¹ include a benzyl group, a phenylethyl group, and a phenylbutyl group.

Z ⁺ is ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ¹¹ ) ₄ .

As the above ⁺ N(R ¹¹ ) ₄ , at least two of the four R ¹¹ are preferably a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. Further, the total carbon number of the four R ¹¹ is preferably from 20 to 80, more preferably from 20 to 60. When R ^{11 is} such a group, the colored photosensitive resin composition containing the compound (1a) can form a color filter having less foreign matter.

m is preferably from 1 to 4, more preferably 1 or 2.

As The dye (Aa) is more preferably a dye containing a compound represented by the formula (2a) (hereinafter sometimes referred to as "compound (2a)"). In the case of using the compound (2a), The content of the compound (2a) in the dye (Aa) is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more.

[In the formula (2a), R ²¹ to R ²⁴ each independently represent a hydrogen atom, -R ²⁶ or a monovalent aromatic hydrocarbon group having a carbon number of 6 to 10 which may have a substituent. R ²¹ and R ²² may form a ring containing a nitrogen atom together with a nitrogen atom, and R ²³ and R ²⁴ may form a ring containing a nitrogen atom together with a nitrogen atom. R ²⁵ represents -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z1 ⁺ or -SO ₂ NHR ²⁶ . M1 represents an integer from 0 to 5. In the case where m1 is an integer of 2 or more, the plurality of R ^{25 may} be the same or different. Wherein, in the case where R ²⁵ is -SO ₃ ^- , m1 is 1. A1 represents an integer of 0 or 1. X1 represents a halogen atom. R ²⁶ represents a one-valent saturated hydrocarbon group having 1 to 20 carbon atoms. Z1 ⁺ represents ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ . R ²⁷ independently represents a monovalent saturated hydrocarbon group or a benzyl group having 1 to 20 carbon atoms.

Examples of the one-valent aromatic hydrocarbon group having 6 to 10 carbon atoms of R ²¹ to R ²⁴ include the same groups as those exemplified as the aromatic hydrocarbon group in the above R ¹ to R ⁴ . The hydrogen atom contained in the aromatic hydrocarbon group may be substituted by -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z1 ⁺ , -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ .

As a combination of R ²¹ to R ²⁴ , R ²¹ and R ²³ are preferably a hydrogen atom, and R ²² and R ²⁴ are a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and a hydrogen atom contained in the aromatic hydrocarbon group. Substituted by -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z1 ⁺ , -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ . Further preferably, R ²¹ and R ²³ are a hydrogen atom, R ²² and R ²⁴ are a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and a hydrogen atom contained in the aromatic hydrocarbon group is via -SO ₃ ^- Z1 ⁺ Or -SO ₂ NHR ²⁶ replacement.

Further, it is preferred that R ²¹ and R ²² together with a nitrogen atom form an aliphatic heterocyclic ring containing a nitrogen atom, and R ²³ and R ²⁴ together with a nitrogen atom form an aliphatic heterocyclic ring containing a nitrogen atom.

When R ²¹ to R ^{24 are} these groups, the colored photosensitive resin composition containing the compound (2a) can form a color filter excellent in heat resistance.

Examples of the aliphatic heterocyclic ring include the following.

Examples of the one-valent saturated hydrocarbon group having 1 to 20 carbon atoms of R ²⁶ and R ²⁷ include the same groups as those exemplified as the saturated hydrocarbon group in R ⁸ to R ¹¹ .

R ²¹ ~ R -R is preferably in the ^{24 26} are each independently a hydrogen atom, methyl or ethyl. Further, and as -SO ₃ R ²⁶ in the -SO ₂ NHR ²⁶ R ^26, preferred is a branched alkyl group having a carbon number of 3 to 20, more preferably 6 to 12 carbon atoms of the branched chain alkyl group, and further It is preferably 2-ethylhexyl. When R ^{26 is} such a group, the colored photosensitive resin composition containing the compound (2a) can form a color filter which generates less foreign matter.

Z1 ⁺ is ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ²⁷ ) ₄ .

As the above ⁺ N(R ²⁷ ) ₄ , at least two of the four R ²⁷ are preferably a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. Further, the total carbon number of the four R ²⁷ is preferably from 20 to 80, more preferably from 20 to 60. When R ^{27 is} such a group, the colored photosensitive resin composition containing the compound (2a) can form a color filter which generates less foreign matter.

M1 is preferably from 1 to 4, more preferably 1 or 2.

The compound (2a) is, for example, a compound represented by the formula (1-1) to the formula (1-25). Further, in the formula, R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched alkyl group having 6 to 12 carbon atoms, and further preferably 2-ethylhexyl group. Among these, a sulfonium amidate of CI Acid Red 289, a quaternary ammonium salt of CI Acid Red 289, a sulfonamide of CI Acid Violet 102, or a quaternary ammonium salt of CI Acid Violet 102 is preferred. Examples of such a compound include compounds represented by formula (1-1) to formula (1-8), formula (1-11), and formula (1-12).

Again, as The dye (Aa), which contains a compound represented by the formula (3a) (hereinafter sometimes referred to as "compound (3a)"), is also more preferable. In the case of using the compound (3a), The content of the compound (3a) in the dye (Aa) is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more.

[In the formula (3a), R ³¹ and R ³² each independently represent an alkyl group having 1 to 4 carbon atoms. R ³³ and R ³⁴ each independently represent an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms or an alkylsulfonyl group having 1 to 4 carbon atoms. R ³¹ and R ³³ may form a ring containing a nitrogen atom together with a nitrogen atom, and R ³² and R ³⁴ may form a ring containing a nitrogen atom together with a nitrogen atom. p and q independently represent an integer from 0 to 5. When p is 2 or more, the plurality of R ^{33 may} be the same or different. When q is 2 or more, the plurality of R ^{34 may} be the same or different.

Examples of the alkyl group having 1 to 4 carbon atoms of R ³¹ , R ³² , R ³³ and R ³⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group and a second butyl group. , third butyl, and the like.

Examples of the alkylsulfanyl group having 1 to 4 carbon atoms of R ³³ and R ³⁴ include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a butylsulfanyl group, and an isopropyl group. Sulfuryl group and the like.

Examples of the alkylsulfonyl group having 1 to 4 carbon atoms of R ³³ and R ³⁴ include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, and an isopropyl group. Sulfonyl and the like.

R ³¹ and R ^{32 are} preferably each independently a methyl group and an ethyl group. R ³³ and R ^{34 are} preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.

m and n are preferably an integer of 0 to 2, more preferably 0 or 1.

The compound (3a) is, for example, a compound represented by the formula (1-26) to the formula (1-32). Among them, the compound represented by the formula (1-26) is preferred from the viewpoint of excellent solubility in an organic solvent.

Dye (Aa) can be used commercially Dye (for example, "Chugai Aminol Fast Pink RH/C" manufactured by Sino-foreign Chemical Co., Ltd., "Rhodamin 6G" manufactured by Tajika Chemical Industry Co., Ltd.). Also, it is also available for sale. The dye was used as a starting material and synthesized by referring to JP2010-32999-A.

As the dye (A1), a phthalocyanine dye (Ab) is also preferred. The phthalocyanine dye (Ab) is preferably a compound represented by the formula (4).

[In the formula (4), G ¹ represents an alkanediyl group having 2 to 16 carbon atoms, and -CH ₂ - contained in the alkanediyl group may be substituted by -O-. J ¹ represents a hydrogen atom, -NR ^a R ^b or -NR ^a R ^b H ⁺ Q ^- . R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Q ^- represents a halide ion, BF ₄ ^- , PF ₆ ^- , ClO ₄ ^- , X-CO ₂ ^- or Y-SO ₃ ^- . X and Y each independently represent a monovalent organic group. p represents an integer from 1 to 4].

Formula (4) represents that p hydrogen atoms contained in the compound represented by formula (4-0) are substituted with -SO ₂ -NH-G ¹ -J ¹ . When p is 2 or more, a plurality of -SO ₂ -NH-G ¹ -J ^{1 may} be the same or different from each other.

Examples of the alkanediyl group having 2 to 12 carbon atoms include a methylene group, an ethylidene group, a propylenediyl group, and a butyldiyl group.

Examples of the alkanediyl group having 2 to 12 carbon atoms which are substituted by -CH ₂ -O-O are a group represented by the formula (G-1) and a group represented by the formula (G-2).

[In the formula (G-1) and the formula (G-2), G ² to G ⁵ each independently represent an alkanediyl group having 1 to 8 carbon atoms. N1 represents an integer from 1 to 3. N2 represents an integer from 0 to 3. Wherein the total number of carbon atoms and oxygen atoms contained in the group represented by the formula (G-1) is 3 to 12, and the carbon atom and oxygen atom contained in the group represented by the formula (G-2) The total count is 2~12. * indicates a bond with -NH-].

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

Examples of -SO ₂ -NH-G ¹ -J ¹ include a group represented by the following formula.

In the case where G ¹ is a group represented by the formula (G-1), examples of the -SO ₂ -NH-G ¹ -J ¹ include a group represented by the following formula.

In the case where G ¹ is a group represented by the formula (G-2), examples of the -SO ₂ -NH-G ¹ -J ¹ include a group represented by the following formula.

In the case where J ¹ is -NR ^a R ^b , examples of -SO ₂ -NH-G ¹ -J ¹ include a group represented by the following formula.

In the case where J ¹ is -NR ^a R ^b H ⁺ Q ^- , examples of -SO ₂ -NH-G ¹ -NR ^a R ^b H ⁺ include a group represented by the following formula.

Q ^- represents a halide ion, BF ₄ ^- , PF ₆ ^- , ClO ₄ ^- , X-CO ₂ ^- or Y-SO ₃ ^- .

X and Y represent a monovalent organic group. Examples of the monovalent organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a group in which these groups are combined.

Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a decyl group.

Examples of the cycloalkyl group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclodecyl group.

Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, and an anthracenyl group.

X-CO ₂ ^- is an organic anion containing a CO ₂ ^- group, and Y-SO ₃ ^- is an organic anion containing an SO ₃ ^- group, and is represented by, for example, a formula (Q-1) to a formula (Q-4). Anion.

[R ^y represents an alkyl group having 1 to 20 carbon atoms.

N3 represents an integer from 0 to 5.].

As Q ^- , X-CO ₂ ^- and Y-SO ₃ ^{- are} preferable, and an anion represented by the formula (Q-4) is more preferable. In the case of these anions, the solubility of the compound represented by the formula (2) in a solvent tends to be improved.

The compound represented by the formula (4) is, for example, a compound disclosed in JP2011-28236-A. Among them, a compound represented by the formula (4-1) to the formula (4-5) is preferred, and a compound represented by the formula (4-2) and a compound represented by the formula (4-5) are more preferred. .

As the pigment (A2), for example, a compound classified as a pigment in the Colour Index (published by The Society of Dyers and Colourists) can be cited.

As the pigment, for example, CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128 can be cited. Yellow pigments such as 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180, 185, 194, 214, 219; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43 , 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 175, 176, 177, 180, 192 209, 215, 216, 224, Red pigments such as 242, 254, 255, 264, and 265; blue pigments such as CI Pigment Blue 15, 15:3, 15:4, 15:6, 60, 80; CI Pigment Violet 1, 19, 23, 29, 32 , 36, 38 and other purple pigments; CI pigment green 7, 36, 58 and other green pigments; CI pigment brown 23, 25 and other brown pigments; CI pigment black 1, 7 and other black pigments.

When the colored photosensitive resin composition of the present invention is prepared as a blue colored photosensitive resin composition, it is preferably a pigment such as CI Pigment Blue 15, 15:3, 15:4, 15:6, 60, etc. as a pigment. Color pigment and CI pigment purple, purple pigments such as 19, 23, 29, 32, 36, 38, etc., more preferably CI pigment blue 15:3, 15:6 and CI pigment violet 23, and further preferably CI pigment blue 15 :6.

When the colored photosensitive resin composition of the present invention is prepared as a green colored photosensitive resin composition, the pigment is preferably a green pigment such as CI Pigment Green 7, 36, and 58 and a yellow pigment such as CI Pigment Yellow 138, 139, and 150. .

When the colored photosensitive resin composition of the present invention is prepared as a red colored photosensitive resin composition, the pigment is preferably a red pigment such as CI Pigment Red 177, 209, 242, 254, 255, CI Pigment Orange 38, 43, 71 and other orange pigments and CI pigment yellow 138, 139, 150 and other yellow pigments.

By including the above pigment, the transmission spectrum is easily optimized, and the light resistance and chemical resistance of the color filter are improved.

The pigment (A2) may also be subjected to the following treatments as needed: rosin treatment; surface treatment using a pigment derivative or the like into which an acidic group or a basic group is introduced; graft treatment of a pigment surface by using a polymer compound or the like; A micronization treatment such as a chemical method, or a treatment for removing impurities, an organic solvent or water, or the like, and an ion exchange method or the like for removing ionic impurities.

The pigment (A2) preferably has a uniform particle size. By performing a dispersion treatment by containing a pigment dispersant, a pigment dispersion liquid in a state in which the pigment is uniformly dispersed in a solution can be obtained.

Examples of the pigment dispersant include pigment dispersants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic. These pigment dispersants may be used singly or in combination of two or more. Examples of the pigment dispersant include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoei Chemical Co., Ltd.), Solsperse (manufactured by Zeneca), EFKA (manufactured by CIBA), and Ajisper ( 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 to be used is preferably 1% by mass or more and 100% by mass or less, more preferably 5% by mass or more and 50% by mass or less based on the pigment (A2). When the amount of the pigment dispersant used is within the above range, there is a tendency that a pigment dispersion liquid having a uniform dispersion state can be obtained.

The colorant (A) preferably contains the dye (A1). The transmission spectrum is easily optimized by including the dye (A1).

Further, the colorant (A) more preferably contains the dye (A1) and the pigment (A2). In this case, the content ratio of the dye (A1) to the pigment (A2) is preferably from 1:99 to 99:1, more preferably from 3:97 to 90:10, on a mass basis. By setting this ratio, it is easy to optimize the transmission spectrum, and the obtained color filter exists. The tendency to be excellent in contrast, brightness, heat resistance and chemical resistance.

The dye (A1) preferably contains Dye (Aa) dye, more preferably Dye of dye (Aa) and phthalocyanine dye (Ab). In this case, The content ratio of the dye (Aa) to the phthalocyanine dye (Ab) is preferably 5:95 to 95:5, more preferably 20:80 to 80:20, and still more preferably 40:60 to 65:35 on a mass basis. .

In particular, the colorant (A) preferably comprises a coloring agent for dye (Aa) and blue pigment, preferably containing Dye (Aa) and CI Pigment Blue 15:6 colorant. The content ratio of the dye (Aa) to the blue pigment is preferably from 1:99 to 90:10, more preferably from 2:98 to 70:30, still more preferably from 2:98 to 50:50, on a mass basis.

The content of the colorant (A) is preferably from 5 to 60% by mass, more preferably from 8 to 50% by mass, even more preferably from 10 to 40% by mass, based on the total amount of the solid content component. 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 necessary amount of the resin or the polymerizable compound (C) can be contained in the composition, so that mechanical strength can be formed. A full color filter.

Here, the term "the total amount of the solid content component" in the present specification means the amount obtained by subtracting the content of the solvent from the total amount of the colored photosensitive resin composition of the present invention. The total amount of the solid content component and the content of each component with respect to the total amount can be measured by a well-known analytical method such as liquid chromatography or gas chromatography.

<Resin (B1)>

The resin (B1) contains a structure derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter, sometimes referred to as "(a)"). The unit and the resin derived from a structural unit having a monomer having a carbon number of 2 to 4 and a monomer having an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b)"). The resin (B1) may further have a structural unit derived from a monomer which is different from (a) and (b) and which is copolymerizable with the above (hereinafter, sometimes referred to as "(c)").

The resin (B1) is exemplified by the following resin [K1] and resin [K2].

Resin [K1]: a copolymer of (a) and (b); a resin [K2]: a copolymer of (a), (b) and (c).

Specific examples of (a) include acrylic acid, methacrylic acid, crotonic acid, unsaturated monocarboxylic acids such as o-, m-, p-vinylbenzoic acid, and maleic acid and fumaric acid. , methyl maleic acid, methyl fumaric acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydroortene Unsaturated dicarboxylic acids such as phthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid; methyl-5- drop Alkene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-A Bicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2 - a bicyclic unsaturated compound containing a carboxyl group such as a olefin or a 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene; maleic anhydride, methyl maleic anhydride, and itaconic anhydride; 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic acid Acid anhydride, dimethyltetrahydrophthalic anhydride, acid anhydride of unsaturated dicarboxylic acid such as 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride; succinic acid mono[2-(methyl) Unsaturated mono[(methyl)acryloxyloxy group of divalent or higher polycarboxylic acid such as propylene methoxyethyl ester, phthalic acid mono [2-(methyl) propylene oxyethyl] ester An alkyl group ester; an unsaturated acrylate having a hydroxyl group and a carboxyl group in the same molecule such as α-(hydroxymethyl)acrylic acid.

Among these, in terms of copolymerization reactivity or solubility in an aqueous alkali solution, (meth)acrylic acid, maleic anhydride, etc. are preferable, and (meth)acrylic acid is more preferable.

In the present specification, the "(meth)acryl fluorenyl group" means at least one selected from the group consisting of an acryloyl group and a methacryl group. The notation such as "(meth)acrylic acid" and "(meth)acrylate" has the same meaning.

(b) means, for example, a cyclic ether structure having a carbon number of 2 to 4 (for example, at least one selected from the group consisting of an oxirane ring, a propylene oxide ring, and a tetrahydrofuran ring) and ethylenic unsaturation A polymerizable compound of a bond. (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloxy group.

(b), for example, a monomer (b1) having an oxirane group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), having an oxypropylene group and an ethylenic unsaturated group The monomer (b2) of the bond (hereinafter sometimes referred to as "(b2)"), the monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "(b3)")) .

(b1), for example, a monomer (b1-1) having a structure in which a linear or branched unsaturated aliphatic hydrocarbon is epoxidized (hereinafter, sometimes referred to as "(b1-) 1)"), and a monomer (b1-2) having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized (hereinafter, sometimes referred to as "(b1-2)").

Examples of (b1-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, and glycidyl group. Vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-inter 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 (glycidol) Oxymethyl)styrene and 2,4,6-tris(glycidoxymethyl)styrene.

(b1-2), vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000; manufactured by Daicel Chemical Industries), (A) 3,4-epoxycyclohexylmethyl acrylate (for example, Cyclomer A400; manufactured by Daicel Chemical Industries), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer M100) ; manufactured by Daicel Chemical Industries, a compound represented by the formula (I), a compound represented by the formula (II), and the like.

[In the formula (I) and the formula (II), R ^b1 and R ^b2 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.

X ^b1 and X ^b2 represents a single ^{bond, -R b3 -, * - R} b3 -O -, * - R b3 -S- or * -R ^b3 -NH-.

R ^b3 represents an alkanediyl group having 1 to 6 carbon atoms.

* indicates the key with O.].

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 alkyl group in which a hydrogen atom is substituted with a hydroxyl group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, and a 1-hydroxy group. 1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like.

The R ^b1 and R ^{b2 are} preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.

Examples of the alkanediyl group include a methylene group, an ethylidene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1,5. - Diyl, hexane-1,6-diyl and the like.

Preferred examples of X ^b1 and X ^b2 include a single bond, a methylene group, an exoethyl group, *-CH ₂ -O-, and *-CH ₂ CH ₂ -O-, and more preferably a single bond or *-CH. ₂ CH ₂ -O- (* indicates the bond with O).

The compound represented by the formula (I) may, for example, be a compound represented by any one of the formulae (I-1) to (I-15). Among them, preferred are formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) and formula (I-11)-form ( The compound represented by any one of I-15) is more preferably of the formula (I-1), the formula (I-7), and the formula (I-9). Or a compound represented by the formula (I-15).

The compound represented by the formula (II) may, for example, be a compound represented by any one of the formulae (II-1) to (II-15). Among them, preferred are formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9), and formula (II-11)-form ( The compound represented by any one of II-15) is more preferably a compound represented by the formula (II-1), the formula (II-7), the formula (II-9) or the formula (II-15).

The compound represented by the formula (I) and the compound represented by the formula (II) may be used singly or in combination at any ratio. In the case of mixed use, the content ratio of the compound represented by the formula (I) to the compound represented by the formula (II) is preferably from 5:95 to 95:5, more preferably 10:90 on a molar basis. ~90:10, and further preferably 20:80~80:20.

The monomer (b2) having an oxypropylene group and an ethylenically unsaturated bond is more preferably a monomer having an oxypropylene group and a (meth)acryloxy group. As (b2), exemplified by 3-methyl-3-methylpropenyloxymethyl propylene oxide, 3-methyl-3-propenyloxymethyl propylene oxide, 3-ethyl-3- Methyl propylene methoxymethyl propylene oxide, 3-ethyl-3-propenyl methoxymethyl propylene oxide, 3-methyl-3-methyl propylene methoxyethyl propylene oxide, 3- Methyl-3-propenyloxyethyl propylene oxide, 3-ethyl-3-methylpropenyloxyethyl propylene oxide, 3-ethyl-3-propenyloxyethyl propylene oxide Wait.

The monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond is more preferably a monomer having a tetrahydrofuranyl group and a (meth)acryloxy group.

Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.

(b) is preferably (b1) in terms of further improving the reliability of heat resistance and chemical resistance of the obtained color filter. Further, in terms of excellent storage stability of the colored photosensitive resin composition, (b1-2) is more preferable.

Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, and (meth)acrylic acid. Tributyl ester, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, (methyl) Cyclopentyl acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] 癸-8-yl (meth) acrylate ( In the technical field, the conventional name is called "dicyclopentanyl (meth) acrylate." Further, it is sometimes called "tricyclodecyl (meth) acrylate"), tricyclo(meth) acrylate [ 5.2.1.0 ^2,6 ]decene-8-yl ester (in the technical field, the conventional name is called "dicyclopentenyl (meth) acrylate)", dicyclopentyloxy (meth) acrylate Ethyl ethyl ester, (meth)acrylic acid Ester, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, (methyl) a (meth) acrylate such as benzyl acrylate; a hydroxyl group-containing (meth) acrylate such as 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate; Dicarboxylic acid diesters such as diethyl diacid, diethyl fumarate, diethyl iconate; bicyclo [2.2.1] hept-2-ene, 5-methyl bicyclo [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]heptane- 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-dihydroxybicyclo[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-di Ethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]g 2-ene, 5-hydroxymethyl- 5-methylbicyclo[2.2.1]hept-2-ene, 5-t-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]g 2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(t-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5, a bicyclic unsaturated compound such as 6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-phenyl maleimide, N-cyclohexylbutylene Amine, N-benzyl maleimide, N-butylenediamine-3-butyleneimine benzoate, N-butylenediamine-4-cis Acetylimine butyrate, N-butylenediamine-6-methyleneimide hexanoate, N-butylenediamine-3-oxenimide Dicarbonyl ruthenium derivatives such as acid esters, N-(9-acridinyl) maleimide, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, Vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene Diene, 2,3-dimethyl-1,3-butadiene, and the like.

Among these, in terms of copolymerization reactivity and heat resistance, styrene, vinyl toluene, N-phenyl maleimide, N-cyclohexylbutylene oxide are preferred. Amine, N-benzyl maleimide and bicyclo [2.2.1] hept-2-ene.

In the resin [K1], the ratio of the structural unit derived from each monomer is preferably relative to the entire structural unit constituting the resin [K1]: the structural unit derived from (a): 2 to 60 mol% is derived from ( b) The structural unit: 40 to 98 mol%, more preferably: the structural unit derived from (a): 10 to 50 mol% derived from the structural unit of (b): 50 to 90 mol%.

When the ratio of the structural unit constituting the resin [K1] is within the above range, the storage stability of the colored photosensitive resin composition, the developability in forming a colored pattern, and the solvent resistance of the obtained colored pattern tend to be excellent.

For example, the resin [K1] can be referred to the "Experimental Method for Polymer Synthesis" (Dazu Takashi, Chemical Tongren (Public) Press, 1st Edition, 1st Printing, published on March 1, 1972). Manufactured by reference to the literature disclosed in this document.

Specifically, a method in which a specific amount of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction container, for example, by dissolving oxygen with nitrogen to form a deoxidizing environment, stirring Heating and keeping warm on one side. Further, the polymerization initiator, the solvent and the like used herein are not particularly limited, and a general user in the field can be used. For example, examples of the polymerization initiator include an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or organic The oxide (such as benzamidine peroxide) may be used as a solvent, and the solvent (E) described later may be mentioned as a solvent for the colored photosensitive resin composition.

Further, the obtained resin may be used as it is, or a solution obtained by concentration or dilution may be used, or a solid (powder) may be formed by a method such as reprecipitation. In particular, since the solvent (E) described later is used as a solvent in the polymerization, the solution after the reaction can be directly used for producing a colored photosensitive resin composition, so that the production steps of the colored photosensitive resin composition can be simplified.

In the resin [K2], the ratio of the structural units derived from each of them is preferably among all the structural units constituting the resin [K2]:

Structural unit derived from (a): 2~45mol%

Structural unit derived from (b): 2~95 mol%

Structural unit derived from (c): 1 to 65 mol%,

More preferably:

Structural unit derived from (a): 5~40 mol%

Structural unit derived from (b): 5~80 mol%

The structural unit derived from (c): 5 to 60 mol%.

When the ratio of the structural unit of the resin [K2] is within the above range, the storage stability of the colored photosensitive resin composition, the developability in forming a colored pattern, and the solvent resistance and heat resistance of the obtained colored pattern and The tendency to have excellent mechanical strength.

Specific examples of the resin (B1) include a resin [K1], a (meth)acrylic acid-3,4-epoxycyclohexylmethyl ester/(meth)acrylic acid copolymer, and an acrylic-3,4-epoxy resin. Tricyclo [5.2.1.0 ^2.6 ] decyl ester / (meth)acrylic acid copolymer; resin [K2], glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylate copolymer, (meth)acrylic acid glycidyl ester / styrene / (meth) acrylic acid copolymer, acrylic acid -3,4-epoxytricyclo[5.2.1.0 ^2.6 ] decyl ester / (meth)acrylic acid / N-cyclohexyl cis maleic copolymer (PEI), 3,4-epoxy acrylate, tricyclo [5.2.1.0 ^2.6] decyl acrylate / (meth) acrylic acid / vinyl toluene copolymer, 3-methyl-3- (methyl Propylene methoxymethyl propylene oxide / (meth) acrylic acid / N-cyclohexyl maleimide copolymer.

The resin [K2] can be produced, for example, in the same manner as the method disclosed in the method for producing the resin [K1].

The polystyrene-equivalent weight average molecular weight of the resin (B1) is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000, still more preferably from 5,000 to 30,000. When the molecular weight is within the above range, the hardness of the color filter is increased, the residual film ratio is also high, and the solubility of the unexposed portion to the developer is good. Ok, the tendency to improve resolution.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B1) is preferably from 1.1 to 6, more preferably from 1.2 to 4.

The acid value of the resin (B1) is preferably from 50 to 170 mg-KOH/g, more preferably from 60 to 150 mg-KOH/g, still more preferably from 70 to 135 mg-KOH/g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be obtained, for example, by titration using an aqueous potassium hydroxide solution.

The content of the resin (B1) is preferably from 10 to 90% by mass, more preferably from 25 to 85% by mass, even more preferably from 50 to 80% by mass, based on the total amount of the resin (B1) and the resin (B2).

<Resin (B2)>

The resin (B2) is a resin containing (a) and a structural unit derived from a monomer having an alicyclic hydrocarbon structure (hereinafter sometimes referred to as "(x)"). Here, the resin (B2) does not contain the structural unit (b) derived from a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond. The resin (B2) may further have a structural unit derived from a monomer which is different from (a), (b), and (x) and which is copolymerizable with the above (hereinafter, sometimes referred to as "(d)"). .

The resin (B2) is exemplified by the following resin [K3] and resin [K4].

Resin [K3]: a copolymer of (a) and (x); a resin [K4]: a copolymer of (a), (x) and (d).

(a) is the same as (a) of the resin (B1). Among these, (meth)acrylic acid and maleic anhydride are more preferable in terms of the aspect of copolymerization reactivity or the solubility in an aqueous alkali solution, more preferably (meth) acrylic acid.

Examples of (x) include a monocyclic alicyclic hydrocarbon structure such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, or 2-methylcyclohexyl (meth)acrylate. (meth) acrylates; trimethyl [meth) acrylate [5.2.1.0 ^2,6 ] 癸-8-yl ester, trimethyl [meth) acrylate [5.2.1.0 ^2,6 ] decene-8 -yl ester, dicyclopentyloxyethyl (meth)acrylate, (meth)acrylic acid a (meth) acrylate having a polycyclic alicyclic hydrocarbon structure such as an ester or an adamantyl (meth) acrylate; 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-ethoxyl Bicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2- Alkene, 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-methylbicyclo[2.2.1]hept-2-ene, 5-t-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5 -cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(t-butoxycarbonyl)bicyclo [2.2.1] Bicyclic unsaturated compounds such as hept-2-ene and 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene N- cyclohexyl-maleic N- acyl imine having the alicyclic hydrocarbon structure substituted maleic acyl imines.

Wherein (x) is preferably selected from (meth) propylene having an alicyclic hydrocarbon structure At least one of the group consisting of an acid ester and a bicyclic unsaturated compound is more preferably a (meth) acrylate having an alicyclic hydrocarbon structure, and further preferably a polycyclic alicyclic hydrocarbon structure. (meth) acrylates. When (x) is such a monomer, when a colored pattern is produced from the colored photosensitive resin composition of the present invention containing the resin (B2), the release sheet derived from the colored photosensitive resin composition in the developing solution after development Reduced production. Further, it is possible to suppress foreign matter caused by adhesion of the release sheets to the colored pattern.

Examples of (d) include those excluding monomers corresponding to (x) in (c) of the resin (B1).

Examples of (d) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, and (meth)acrylic acid. Tributyl ester, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, (methyl) (meth)acrylates such as allyl acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate; (methyl) a hydroxyl group-containing (meth) acrylate such as 2-hydroxyethyl acrylate or 2-hydroxypropyl (meth) acrylate; diethyl maleate, diethyl fumarate, and y Dicarboxylic acid diester such as diethyl benzoate; N-phenyl maleimide, N-benzyl maleimide, N-butyl quinone imin-3-butene Diterpene imide benzoate, N-butanediamine-4-butyleneimine butyrate, N-butanediamine-6-m-butyleneimine Acid ester, N-butyl diimide imino-3-butane diimide Dicarbonyl quinone imine derivatives such as acid esters and N-(9-acridinyl) maleimide; styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, Vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene Diene, 2,3-dimethyl-1,3-butadiene, and the like.

Among them, preferred are styrene, vinyl toluene, N-phenyl maleimide, N-benzyl maleimide, and benzyl (meth)acrylate having an aromatic hydrocarbon structure. The monomer is more preferably styrene, vinyl toluene or benzyl (meth)acrylate. When (d) is such a monomer, the viscosity of the resin (B2) solution during or after the polymerization is not excessively high, so that it tends to be easy to handle. In addition, when the resin (B2) containing the structural unit derived from the monomers is used in the colored photosensitive resin composition, the occurrence of the release sheet during development can be further suppressed.

In the resin [K3], the ratio of the structural unit derived from each monomer is preferably relative to the entire structural unit constituting the resin [K3]: the structural unit derived from (a): 2 to 60 mol%

Structural unit derived from (x): 40 to 98% by mole, more preferably: structural unit derived from (a): 10 to 50% by mole

Structural unit derived from (x): 50 to 90 mol%.

When the ratio of the structural unit of the resin [K3] is within the above range, there is a tendency that a colored pattern having a good shape can be obtained.

The resin [K3] can be produced, for example, in the same manner as the method disclosed in the method for producing the resin [K1].

In the resin [K4], the ratio of the structural unit derived from each monomer to all the structural units constituting the resin [K4] is preferably: structural unit derived from (a): 2 to 45 mol%

Structural unit derived from (x): 2~95 mol%

The structural unit derived from (d): 1 to 65 mol%, more preferably: structural unit derived from (a): 5 to 40 mol%

Structural unit derived from (x): 5~80 mol%

The structural unit derived from (d): 5 to 60 mol%.

When the ratio of the structural unit of the resin [K4] is within the above range, there is a tendency that a colored pattern having a good shape can be obtained.

In the case of a structural unit containing a monomer derived from an aromatic hydrocarbon structure (hereinafter referred to as "(d')") as the resin (K4) (d), it is preferred that the structure derived from (a) Unit: 5~45mol%

Structural unit derived from (x): 5~80 mol%

Structural unit derived from (d'): 30 to 65 mol%, more preferably: structural unit derived from (a): 10 to 40 mol%

Structural unit derived from (x): 5~40 mol%

The structural unit derived from (d'): 40 to 65 mol%.

When the resin [K4] is such a resin, the occurrence of the release sheet due to development is further reduced, and a color pattern having a good shape tends to be obtained.

The resin [K4] can be produced, for example, in the same manner as the method disclosed in the method for producing the resin [K1].

Specific examples of the resin (B2) include a resin [K3], a cyclohexyl (meth)acrylate/(meth)acrylic acid copolymer, and a tricyclodecyl (meth)acrylate/(meth)acrylic acid copolymer. , bicyclo[2.2.1]hept-2-ene/(meth)acrylic acid copolymer, etc.; resin [K4], cyclohexyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid Copolymer, tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, tricyclodecyl (meth)acrylate/styrene/(meth)acrylic acid copolymer, Tricyclodecyl (meth)acrylate/vinyltoluene/(meth)acrylic acid copolymer, bicyclo[2.2.1]hept-2-ene/styrene/(meth)acrylic acid copolymer, and the like.

Among them, as the resin (B2), a resin [K4] is preferred.

The polystyrene-equivalent weight average molecular weight of the resin (B2) is preferably from 3,000 to 100,000, more preferably from 3,000 to 30,000, still more preferably from 4,000 to 15,000. When the molecular weight is within the above range, the hardness of the color filter is improved, the residual film ratio is also high, the solubility of the unexposed portion to the developer is good, and the resolution tends to be improved.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B2) is preferably from 1.1 to 6, more preferably from 1.2 to 4.

The acid value of the resin (B2) is preferably from 50 to 170 mg-KOH/g, more preferably from 60 to 150 mg-KOH/g, still more preferably from 70 to 135 mg-KOH/g. When the acid value is within the above range, there is a tendency that a colored pattern having a good shape can be obtained. When the acid value is higher than the above range, the colored pattern is likely to be undercut, which causes the pattern to peel off. Again, in acid When the value is lower than the above range, there is a problem that development residue is generated. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be obtained, for example, by titration using an aqueous potassium hydroxide solution.

The content of the resin (B2) is preferably from 10 to 90% by mass, more preferably from 15 to 75% by mass, even more preferably from 50 to 80% by mass, based on the total amount of the resin (B1) and the resin (B2).

The total amount of the resin (B1) and the resin (B2) is preferably 7 to 65 mass%, more preferably 13 to 60 mass%, still more preferably 17 to 55 mass%, based on the total amount of the solid content component. When the total amount is within the above range, the resolution of the colored pattern and the residual film ratio tend to increase.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound which can be polymerized by heat or an active radical and/or an acid produced by the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenically unsaturated bond. And the like, preferably a (meth) acrylate compound.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such a polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylic acid. Ester, dipentaerythritol hexa(meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, pentaerythritol deca (meth) acrylate, pentaerythritol nin (meth) acrylate Ester, tris(2-(meth)acryloxyethyl)isocyanurate, B Glycol modified pentaerythritol tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth) acrylate, propylene glycol modified pentaerythritol tetra(meth) acrylate, propylene glycol modified dipentaerythritol hexa(methyl) Acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and the like.

Among them, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, more preferably 250 to 1,500 or less.

The content of the polymerizable compound (C) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, even more preferably from 17 to 55% by mass, based on the total amount of the solid content component. When the content of the polymerizable compound (C) is within the above range, the residual film ratio and chemical resistance of the colored pattern tend to be improved.

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound which can initiate polymerization by the action of light or heat to generate an active radical, an acid or the like, and a known polymerization initiator can be used.

As the polymerization initiator (D), an alkylphenone compound, three a compound, a mercaptophosphine oxide compound, an O-mercaptopurine compound, a biimidazole compound, and the like. Among them, a polymerization initiator containing an O-fluorenyl ruthenium compound is preferable, and a polymerization initiator containing an O-fluorenyl ruthenium compound and an alkyl phenone compound is more preferable.

The O-indenyl compound is a compound having a partial structure represented by the formula (d1).

Hereinafter, * indicates a keying key.

Examples of the O-indenyl hydrazine compound include N-benzylideneoxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine and N-benzidine. Oxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-benzylideneoxy-1-(4-phenylsulfanylphenyl)- 3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazole-3 -yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-di Oxearylmethoxy)benzhydryl}-9H-indazol-3-yl]ethane-1-imine, N-ethyloxy-1-[9-ethyl-6-( 2-methylbenzimidyl)-9H-indazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzylideneoxy-1-[9-ethyl-6- (2-Methylbenzylidene)-9H-oxazol-3-yl]-3-cyclopentylpropan-1-one-2-imine. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF Corporation), and N-1919 (manufactured by ADEKA Co., Ltd.) can also be used.

The alkylphenone compound is a compound having a partial structure represented by the formula (d2) or a partial structure represented by the formula (d3). In these partial structures, the benzene ring may also have a substituent.

As the compound having a partial structure represented by the formula (d2), for example, 2-methyl-2- Lolinyl-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4- Phenylphenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4- Morpholinyl)phenyl]butan-1-one and the like. Commercial products such as Irgacure (registered trademark) 369, 907, and 379 (above, manufactured by BASF Corporation) can also be used.

Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1-[ 4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane - 1-ketone oligomer, α,α-diethoxyacetophenone, benzoin dimethyl ketal, and the like.

The alkylphenone compound is preferably a compound having a partial structure represented by the formula (d2) in terms of sensitivity.

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-sunflower-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.

The fluorenylphosphine oxide compound may, for example, be 2,4,6-trimethylbenzimidyldiphenylphosphine oxide. Irgacure (registered trademark) 819 (BASF) Commercial products such as the company's manufacturing).

Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, and 2,2'-bis(2,3- Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, refer to JPH06-75372-A, JPH06-75373-A, etc.), 2,2'-bis(2-chlorobenzene) -4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl) Biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chloro Phenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, refer to JPS48-38403-B, JPS62-174204-A, etc.), 4, 4', 5, An imidazole compound in which a phenyl group at the 5'-position is substituted with an alkoxycarbonyl group (for example, refer to JPH07-10913-A, etc.) and the like.

Further, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone and methyl benzoyl benzoate; , 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis(t-butylperoxycarbonylcarbonyl)diphenyl a benzophenone compound such as ketone or 2,4,6-trimethylbenzophenone; an anthracene compound such as 9,10-phenanthrenequinone, 2-ethylhydrazine or camphorquinone; 10-butyl-2- Chloramphenicone, benzoin, methyl phenylglyoxylate, titanocene compound, and the like. These are preferably used in combination with the polymerization starting assistant (D1) (especially an amine) described below.

Examples of the acid generator include 4-hydroxyphenyldimethylhydrazine p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-ethenoxyphenyldimethylate.鋶p-toluenesulfonate, 4-acetoxyphenyl-methyl-benzylphosphonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate An acid salt, a diphenylsulfonium p-toluenesulfonate, a phosphonium salt such as diphenylsulfonium hexafluoroantimonate, or a nitrobenzyl tosylate/salt, a benzoin tosylate/salt or the like.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass based on 100 parts by mass of the total of the resin (B1), the resin (B2) and the polymerizable compound (C). Share. When the content of the polymerization initiator (D) is within the above range, the sensitivity is improved and the exposure time tends to be shortened, so that productivity is improved.

Further, together with the polymerization initiator (D), a polymerization initiation aid (D1) may be further contained. The polymerization initiation aid (D1) is a compound or a sensitizer for promoting polymerization of a photopolymerizable compound which starts polymerization by a polymerization initiator.

As the polymerization initiation aid (D1), an amine compound, an alkoxy oxime compound, and 9-oxosulfuric acid can be cited. a compound, a carboxylic acid compound or the like, preferably 9-oxosulfur Compound.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylamine. Isoamyl benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4, 4'-bis(dimethylamino)benzophenone (commonly known as mickleone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethyl Methylamino)benzophenone or the like, of which 4,4'-bis(diethylamino)benzophenone is preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

As the alkoxy ruthenium compound, 9,10-dimethoxy oxime, 2-B Base-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-B Base-9,10-dibutoxyanthracene, and the like.

9-oxosulfur The compound may, for example, be 2-isopropyl-9-oxosulfur 4-isopropyl-9-oxosulfur 2,4-diethyl-9-oxosulfur 2,4-dichloro-9-oxosulfur 1-chloro-4-propoxy-9-oxosulfur Wait.

Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, and dimethylphenylsulfide. Alkylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, Phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, and the like.

When the polymerization initiator (D1) is used, the amount thereof is 100 parts by mass, preferably 0.1 to 30, based on the total amount of the resin (B1), the resin (B2), and the polymerizable compound (C). The mass part is more preferably 1 to 20 parts by mass. When the amount of the polymerization initiation aid (D1) is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.

<Solvent (E)>

The solvent (E) is not particularly limited, and a solvent which is usually used in the field can be used. For example, it can be selected from the following solvents: an ester solvent (a solvent containing -COO- in the molecule and containing no -O-), an ether solvent (a solvent containing -O- in the molecule and containing no -COO-) , an ether ester solvent (a solvent containing -COO- and -O- in the molecule), a ketone solvent (a solvent containing -CO- in the molecule and containing no -COO-), an alcohol solvent, an aromatic hydrocarbon solvent, a guanamine Solvent, dimethyl hydrazine, and the like.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and isoamyl acetate. , butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, ring Hexanol acetate, γ-butyrolactone, and the like.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and two. Ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, Tetrahydrofuran, tetrahydropyran, 1,4-two Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyl ether, methyl Anisole and the like.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxypropionic acid. Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionic acid Ethyl ester, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2- Ethyl ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol Ethyl acetate, propylene glycol monopropyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate Ester, diethylene glycol monobutyl ether acetate, and the like.

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, and 4-methyl-2- Pentanone, cyclopentanone, cyclohexanone, isophorone and the like.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

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

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

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

Among the above solvents, an organic solvent having a boiling point of from 120 ° C to 180 ° C at 1 atm is preferred in terms of coatability and drying property. As the solvent (E), preferred is propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether. , diethylene glycol monoethyl ether and 4-hydroxy-4-methyl-2-pentanone, more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate and 3-ethoxypropionic acid ester.

The content of the solvent (E) is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass based on the total amount of the colored photosensitive resin composition. In other words, the solid content of the colored photosensitive resin composition is preferably from 5 to 30% by mass, more preferably from 8 to 25% by mass.

When the content of the solvent (E) is within the above range, the flatness at the time of coating becomes good, and the color density is not insufficient when the color filter is formed. Therefore, the tendency to display characteristics is good.

<Interacting Agent (F)>

Examples of the surfactant (F) include a polyfluorene-based surfactant, a fluorine-based surfactant, and a polyfluorene-based surfactant having a fluorine atom. These may also have a polymerizable group in the side chain.

Examples of the polyoxymethylene-based surfactant include a surfactant having a decane bond in the molecule. Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (trade name: manufactured by Dow Corning Toray); KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan) )Wait.

The fluorine-based surfactant may, for example, be a surfactant having a fluorocarbon chain in the molecule. Specifically, Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M), Megafac (registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac R30, Megafac RS-718-K (manufactured by DIC), Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (Mitsubishi Materials Electronic) (manufactured by Chemicals), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Co., Ltd.) .

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

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

The content of the surfactant (F) is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.1% by mass or less, and further preferably 0.01% by mass or less based on the total amount of the coloring photosensitive resin composition. The above 0.05% by mass or less. Further, the content of the above pigment dispersant is not included in the content. When the content of the surfactant (F) is within the above range, the flatness of the color filter can be improved.

<Other ingredients>

The colored photosensitive resin composition of the present invention may optionally contain additives such as a filler, another polymer compound, an adhesion promoter, an antioxidant, a light stabilizer, and a chain transfer agent, which are well known in the art.

<Method for Producing Colored Photosensitive Resin Composition>

The colored photosensitive resin composition of the present invention can be started, for example, by coloring agent (A), resin (B1), resin (B2), polymerizable compound (C), and polymerization. The agent (D) and, if necessary, a polymerization starting aid (D1), a solvent (E), a surfactant (F), and other components are mixed and prepared.

When the pigment (A2) is contained as the coloring agent (A), it is preferred to mix the pigment (A2) with the solvent (E) in advance, and to use a bead mill or the like to disperse until the average particle diameter of the pigment is 0.2 μm or less. The extent of it. At this time, a part or all of the above-mentioned pigment dispersant, one part or all of the resin (B1) or one part of the resin (B2) may be blended as needed. To the obtained pigment dispersion, the remainder of the resin (B1), the remainder of the resin (B2), and the polymerizable compound (C), and optionally the dye (A1), polymerization initiator (D) The remaining portion of the solvent (E), the surfactant (F), and other components are mixed so as to have a specific concentration, whereby the intended colored photosensitive resin composition can be prepared.

The dye (A1) in the case where the dye (A1) is contained may also be separately dissolved in the solvent (E) in advance. The solution is preferably filtered using a filter having a pore size of about 0.01 to 1 μm.

The colored photosensitive resin composition after mixing is preferably filtered using a filter having a pore diameter of about 0.1 to 10 μm.

<Color filter and method of manufacturing liquid crystal display device>

A method of producing a color-patterned coating film (hereinafter, a "coloring pattern coating film" is simply referred to as a "coloring pattern") for producing a color filter from the colored photosensitive resin composition of the present invention includes a photolithography method and a spray method. Ink method, printing method, etc. Among them, photolithography is preferred. In the photolithography method, the colored photosensitive resin composition of the present invention is applied onto a substrate, and dried by removing a volatile component such as a solvent to form a composition layer, and then, via a photomask The composition layer is exposed and developed. After development, heating is performed as needed, whereby a colored pattern can be formed. In the method of forming the colored pattern described above, a colored coating film which is a cured product of the composition layer can be formed without using a photomask and/or without developing at the time of exposure. The colored patterned coating film and the colored coating film thus obtained can be used as a color filter.

The film thickness of the produced color filter is not particularly limited, and can be appropriately adjusted depending on the purpose, use, and the like, and is, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

As the substrate, a glass plate such as quartz glass, borosilicate glass, aluminosilicate glass, or soda lime glass coated with cerium oxide, or polycarbonate, polymethyl methacrylate or polyparaphenyl may be used. A resin plate such as ethylene formate is formed on the substrate, and an aluminum, silver, silver/copper/palladium alloy film or the like is formed on the substrate. Another color filter layer, a resin layer, a transistor, a circuit, or the like may be formed on the substrates.

Hereinafter, a method of forming a pattern on a glass substrate on which a thin film transistor (hereinafter referred to as "TFT") is formed will be described.

Specifically, a plurality of TFTs 22 are formed on the glass substrate 21 for each pixel by a well-known method such as photolithography (see FIG. 1). The TFT 22 includes a gate electrode 22a which is formed on the glass substrate 21 by, for example, molybdenum (Mo), and constitutes a part of the gate line, and a gate insulating film 22b which is formed on the gate electrode 22a and includes For example, a laminated film of a nitride film (SiN _x ) and an oxide film (SiO ₂ ); a polycrystalline germanium film 22c formed on the gate insulating film 22b; and a protective film 22d made of, for example, an oxide film (SiO ₂ ) and A laminated film of a nitride film (SiN _x ) is formed. 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 becomes 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 will be described later.

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

Next, the colored photosensitive resin composition of the present invention is applied onto the glass substrate 21 on which the TFT 22 and the alignment mark are formed, and dried by heating (prebaking) and/or drying under reduced pressure to remove volatile components such as a solvent. It is dried to form a composition layer having a film thickness of 0.5 to 5.0 μm, for example, 1.0 μm.

Examples of the coating method include a spin coating method, a slit coating method, and a slit-spin coating method.

The temperature at the time of heat drying is preferably from 30 to 120 ° C, more preferably from 50 to 110 ° C. Further, the heating time is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 30 minutes.

In the case of drying under reduced pressure, it is preferably carried out at a temperature of from 20 to 25 ° C under a pressure of 50 to 150 Pa.

Then, the composition layer is irradiated with ultraviolet rays through a photomask (not shown), and the unnecessary portion (unexposed portion) is selectively removed by the developer, whereby the connection to the drain region reaching the polysilicon film 22c is obtained. The layer of the composition of the hole (contact hole) 201 formed on the pixel is then washed with water.

By developing, the unexposed portion of the composition layer is dissolved in the developer to be removed. As the developer, for example, an aqueous solution of a basic compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate or tetramethylammonium hydroxide is preferred. The concentration of the basic compound in the aqueous solution is preferably from 0.01 to 10% by mass, more preferably from 0.03 to 5% by mass. Further, the developer may also contain a surfactant.

The developing method may be any one of a puddle method, a dipping method, and a spray method. Further, the substrate can be inclined at an arbitrary angle during development.

Thereafter, in order to reflow (reflow) and/or harden the composition layer in which the connection holes (contact holes) 201 are formed, it is, for example, in the range of 150 to 250 ° C, preferably 160 to 235 ° C. The temperature is heated for 10 to 60 minutes, preferably 1 to 120 minutes. Thus, the colored photosensitive resin composition layer 23A was formed. The colored photosensitive resin composition layer 23A corresponds to the color filter of the present invention.

By repeating this operation, the colored photosensitive resin composition layer 23A is formed of the red colored photosensitive resin composition, the green colored photosensitive resin composition, and the blue colored photosensitive resin composition, respectively, thereby forming inclusions corresponding to the respective pixel columns. The color filter layer 23 of the red color filter 23a, the green color filter 23b, and the blue color filter 23c (refer FIG. 2). The region between the filters of the color filter layer 23 is a mixed region of adjacent colors. However, since this region is a light-blocking region facing the signal line 27, there is no particular disadvantage in quality. Furthermore, the area between the 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 so as 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 unnecessary portion are selectively removed by the developer, thereby forming a drain reaching the polysilicon film 22c. The connection hole (contact hole) 202 of the area is then washed with water. Thereafter, in order to reflow (reflow) the photosensitive resin film 29, it is heated at a temperature in the range of 100 to 300 ° C, for example, 200 ° C. Then, in order to remove residues and organic substances such as dyes deposited in the contact holes 202, etching is performed by oxygen plasma, and further, etching is performed by using, for example, dilute hydrofluoric acid to remove the oxide film formed of the oxygen plasma.

Next, a transparent conductive material such as ITO (Indium-Tin Oxide: mixed film of indium and tin oxide) is formed on the photosensitive resin film 29 by, for example, a sputtering method, and the ITO film is formed by photolithography and etching. The pattern is formed to form a transparent pixel electrode 24 (see Fig. 3). Furthermore, the pixel electrode 24 may be formed of a metal such as aluminum (Al) or silver (Ag) depending on the device to be fabricated. Thereafter, the alignment film is formed by a known method, and then the driving substrate and the counter substrate are bonded together, whereby a liquid crystal display device can be manufactured.

According to the colored photosensitive resin composition of the present invention, a high-performance color filter having less surface foreign matter can be produced with good yield, and thus the color filter can be used as a display device (for example, a liquid crystal display device, organic A color filter used in an EL (electroluminescence) device, an electronic paper, a solid-state imaging device, or the like.

Example

Next, the present invention will be more specifically described by way of examples. The % and the parts indicating the content or the amount used in the examples are based on mass unless otherwise specified.

[Synthesis Example 1]

In a flask including a cooling tube and a stirring device, a mixture of a compound represented by the formula (A1-1a) and a compound represented by the formula (A1-1b) (trade name: Chugai Aminol Fast Pink R; manufactured by Sinotrans) 15 parts, 150 parts of chloroform, and 8.9 parts of N,N-dimethylformamide were maintained at 20 ° C or less while stirring, and 10.9 parts of sulfite chloride was added dropwise thereto. After completion of the dropwise addition, the temperature was raised to 50 ° C, and the reaction was maintained at this temperature for 5 hours, and then cooled to 20 ° C. The reaction solution after cooling was maintained at 20 ° C or lower while stirring, and a mixed liquid of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise. Thereafter, the reaction was carried out by stirring at this temperature for 5 hours. Then, after 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 were separated by filtration, thoroughly washed with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain a dye (A1-1) (from the formula (A1-1-1) to the formula (A1-1- 8) A mixture of the indicated compounds) 11.3 parts.

[Synthesis Example 2]

Nitrogen gas was introduced into a flask including a reflux condenser, a dropping funnel and a stirrer at 0.02 L/min to adjust to a nitrogen atmosphere, and 305 parts by mass of ethyl lactate was added thereto, and the mixture was heated to 70 ° C while stirring.

Then, 60 parts by mass of acrylic acid and 3,4-epoxytricyclo[5.2.1.0 ^2.6 ] decyl acrylate (the compound represented by the formula (I-1) and the compound represented by the formula (II-1) A solution was prepared by dissolving 240 parts by mass of ethyl lactate in an amount of 240 parts by mass in a molar ratio of 50:50, and the solution was added dropwise to a flask maintained at 70 ° C for 4 hours using a dropping funnel.

On the other hand, a solution obtained by dissolving 30 parts by mass of a polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) in 225 parts by mass of ethyl lactate, using another dropping funnel It was added dropwise to the flask over 4 hours. After completion of 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 9.1 × 10 ³ , a molecular weight distribution of 2.1, and a solid content of 26% by mass. A solution of a resin (B1-1) having a solid content of 120 mg-KOH/g.

The resin (B1-1) has the following structural unit.

[Synthesis Example 3]

Nitrogen gas was introduced into a flask including a stirrer, a thermometer, a reflux condenser, and a dropping funnel at 0.02 L/min to adjust to a nitrogen atmosphere, and 257 parts by mass of propylene glycol monomethyl ether acetate was added thereto, and the mixture was heated to 70 ° C while stirring. until. Then, 57 parts by mass of acrylic acid, 83 parts of vinyltoluene, and 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate (the compound represented by the formula (I-1) and the formula (II-) 1) The compound represented by dissolving 140 parts by mass of propylene glycol monomethyl ether acetate in 238 parts by mass of a molar ratio of 50:50 was prepared, and the solution was added dropwise to a heat retention rate of 70 using a dropping funnel over 4 hours. In a °C flask. On the other hand, a solution obtained by dissolving 30 parts by mass of a polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) in 225 parts by mass of propylene glycol monomethyl ether acetate is used. Another dropping funnel was added dropwise to the flask over 4 hours. After completion of 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 9.9 × 10 ³ , a solid content of 37.5%, and a solid component acid value of 112. A solution of mg-KOH/g of resin (B1-2). The resin (B1-2) has the following structural unit.

[Synthesis Example 4]

The flask including a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a nitrogen introduction tube was adjusted to a nitrogen atmosphere, and 210 parts of propylene glycol monomethyl ether acetate was added thereto, and the mixture was heated to 100 ° C while stirring. Then, 22 parts of benzyl methacrylate, 22 parts of acrylic acid, and dicyclopentyl methacrylate (manufactured by Hitachi Chemical Co., Ltd.) were dissolved in 215 parts of propylene glycol monomethyl ether acetate, and dissolved. A solution prepared by dissolving 3.6 parts of 2,2'-azobisisobutyronitrile was added dropwise to the flask, and stirring was continued at 100 ° C for 5 hours, whereby a weight average molecular weight Mw of 1.00 × 10 ⁴ and a solid content of 34.1% were obtained. A resin (B2-1) solution having a solid content of 109 mgKOH/g. The resin (B2-1) has the following structural unit.

[Synthesis Example 5]

Nitrogen gas was introduced into a flask including a reflux condenser, a dropping funnel and a stirrer at 0.02 L/min to adjust to a nitrogen atmosphere, and 220 parts of ethyl lactate was added thereto, and the mixture was heated to 70 ° C while stirring. Then, 84 parts of methacrylic acid and 3,4-epoxytricyclo[5.2.1.0 ^2.6 ] decyl acrylate (the compound represented by the formula (I-1) and the compound represented by the formula (II-1) A solution was prepared by dissolving 336 parts of the compound in a molar ratio of 50:50, 140 parts of ethyl lactate, and the solution was added dropwise to a flask maintained at 70 ° C for 4 hours using a dropping funnel. On the other hand, a solution obtained by dissolving 30 parts of a polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) in 95 parts of ethyl lactate, and using another dropping funnel for 4 Add dropwise to the flask in an hour. After completion of 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 8.0 × 10 ³ , a molecular weight distribution of 2.5, and a solid content of 48%. A solution of a resin (B1-3) having a solution acid value of 50 mg-KOH/g (acid value of solid content of 104 mgKOH/g). The resin (B1-3) has the following structural unit.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in the synthesis example were measured by GPC method (Gel Permeation Chromatography) under the following conditions.

Device: K2479 (made by Shimadzu Corporation)

Column: SHIMADZU Shim-pack GPC-80M

Column temperature: 40 ° C

Solvent: THF (tetrahydrofuran)

Flow rate: 1.0 mL/min

Detector: RI

Standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh) to convert the weight of polystyrene obtained in the above The ratio of the average molecular weight to the number average molecular weight (Mw/Mn) is taken as the molecular weight distribution.

Examples 1 to 6 and Comparative Example 1 [Preparation of Colored Photosensitive Resin Composition]

The components of the amounts shown in Table 1 were mixed to obtain a colored photosensitive resin composition.

In addition, in Table 1, each component shows the following.

Coloring Agent (A) (A1-1): Dye (A1-1)

(A1-2) of coloring agent (A): C.I. salt of direct blue 264 and dodecylbenzenesulfonic acid (manufactured by Orient Chemical Industry Co., Ltd.) (dye)

Coloring Agent (A) (A2-1): C.I. Pigment Blue 15:6 (Pigment)

Resin (B1) (B1-1): Resin (B1-1)

Resin (B1) (B1-2): Resin (B1-2)

Resin (B1) (B1-3): Resin (B1-3)

Resin (B2) (B2-1): Resin (B2-1)

Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

(D-1) of polymerization initiator (D): N-benzylideneoxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine (Irgacure (registered) Trademark) OXE 01; manufactured by BASF; O-mercaptopurine compound)

(D-2) of polymerization initiator (D): 2-methyl-2- Orolinyl-1-(4-methylsulfanylphenyl)propan-1-one (Irgacure (registered trademark) 907; manufactured by BASF Corporation; alkylphenone compound)

Polymerization start aid (D1): 2,4-diethyl-9-oxosulfur KAYACURE (registered trademark) DETX-S; manufactured by Nippon Chemical Co., Ltd.; 9-oxygen sulfur Compound)

Solvent (E) (E-1): propylene glycol monomethyl ether acetate

Solvent (E) (E-2): propylene glycol monomethyl ether

Solvent (E) (E-3): ethyl lactate

Surfactant (F) (F-1): Polyether modified polyoxyxide oil (Toray Silicone SH8400; manufactured by Dow Corning Toray)

[Developability evaluation]

After coating the colored photosensitive resin composition by a spin coating method on a glass substrate (Eagle XG; manufactured by Corning Co., Ltd.) of 2 inches square, The composition layer was formed by prebaking at 100 ° C for 3 minutes. The substrate on which the above composition layer was formed was immersed at 25 ° C for 120 seconds in a petri dish containing 10 ml of a water-based developer containing 0.12% of a nonionic surfactant and 2% of sodium carbonate, and visually observed after immersion. Developer solution. When the peeling sheet from the coloring photosensitive resin composition was not confirmed in the developing solution, the developability was judged to be good and evaluated as ○, and when the peeling sheet was confirmed, it was evaluated as ×. When the release sheet from the colored photosensitive resin composition is confirmed in the developer, the release sheet adheres to the color filter as a foreign matter, which causes a defect, which is not preferable. The results are shown in Table 2.

[Production of color filter]

The colored photosensitive resin composition was applied by a spin coating method on a glass substrate (Eagle XG; manufactured by Corning) of 2 inches square, and then prebaked at 100 ° C for 3 minutes to form a composition layer. After cooling, the interval between the substrate on which the composition layer was formed and the patterned quartz glass mask was set to 200 μm, and an exposure machine (TME-150RSK; TOPCON) was used in an atmosphere to Light exposure was performed at an exposure of 40 mJ/cm ² (365 nm reference). Further, the light irradiation at this time is performed by passing the emitted light from the ultrahigh pressure mercury lamp through a filter (UV-35; manufactured by Asahi Separation Co., Ltd.). Further, the light irradiation is performed by forming a mask (a light-shielding portion having a square of 30 μm on one side and a square interval of 100 μm) on the same plane (hereinafter, the light shield is transparent to light). A portion that is irradiated with light correspondingly is referred to as an "exposure portion", and a portion of the photomask that is not irradiated with light corresponding to the light shielding portion is referred to as an "unexposed portion". After the light irradiation, the coating film was immersed and developed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 2% of sodium carbonate at 25 ° C for 60 seconds, washed with water, and then placed in an oven at 230 ° C. Baking was carried out for 20 minutes, whereby a color filter having a hole of 30 μm square formed in the unexposed portion was obtained.

[Measurement of film thickness]

The film thickness of the obtained color filter was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 2.

[Color Evaluation]

The spectrophotometer (OSP-SP-200; manufactured by Olympus Co., Ltd.) was used to measure the spectroscopic portion of the obtained color filter, and the color matching function of the C light source was used to measure the XYZ of the CIE. The xy chromaticity coordinates (x, y) and the tristimulus value Y in the color system. The larger the Y value, the higher the brightness. The results are shown in Table 2.

It has been confirmed that the colored photosensitive resin composition of the embodiment forms color filter At the time of filming, the occurrence of the peeling sheet by the development was not confirmed. Thus, the color filter produced by the colored photosensitive resin composition of the present invention can be used to manufacture a display device at a high yield.

According to the colored photosensitive resin composition of the present invention, a release sheet derived from the colored photosensitive resin composition is less likely to be produced in the developer after development.

21‧‧‧ glass substrate

22‧‧‧TFT (switching element)

22a‧‧‧Gate electrode

22b‧‧‧gate insulating film

22c‧‧‧ Polysilicon film

22d‧‧‧Protective film

23‧‧‧Color filter layer

23A‧‧‧Colored photosensitive resin composition layer (color filter)

23a‧‧‧Red Filter

23b‧‧‧Green Filter

23c‧‧‧Blue filter

24‧‧‧pixel electrode

27‧‧‧ signal line

29‧‧‧Photosensitive resin film (protective film)

201, 202‧‧‧ connection holes

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a method of producing a color filter of the present invention.

Fig. 2 is a schematic view showing a method of manufacturing the color filter of the present invention.

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

Claims (5)

A colored photosensitive resin composition comprising (A), (B1), (B2), (C) and (D): (A) a colorant; (B1) comprising a source selected from the group consisting of unsaturated carboxylic acids and not a structural unit of at least one of a group consisting of a saturated carboxylic anhydride; and a resin derived from a structural unit having a cyclic ether structure having a carbon number of 2 to 4 and a monomer having an ethylenically unsaturated bond; (B2) comprising a source a resin derived from at least one structural unit selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and a structural unit derived from a monomer having an alicyclic hydrocarbon structure (wherein a structural unit of a cyclic ether structure having 2 to 4 carbon atoms and a monomer having an ethylenically unsaturated bond; (C) a polymerizable compound; and (D) a polymerization initiator. The colored photosensitive resin composition of claim 1, wherein (B2) further comprises a structural unit derived from a monomer having an aromatic hydrocarbon group. The colored photosensitive resin composition of claim 1 or 2, wherein the content of (B2) is from 10 to 90% by mass based on the total of (B1) and (B2). A color filter formed of the colored photosensitive resin composition according to any one of claims 1 to 3. A display device comprising a color filter as in claim 4.