TW201403234A - Colored photosensitive resin composition - Google Patents

Abstract

The present invention provides a colored photosensitive resin composition comprising a colorant, a resin, a polymerizable compound, a polymerization initiator and a thiol compound, wherein the colorant comprising a xanthene dye and a pigment, and the polymerization initiator comprising a biimidazole compound or an O-acyloxime compound.

Description

Colored photosensitive resin composition

The present invention relates to a coloring photosensitive resin composition.

The colored photosensitive resin composition can be used for producing a color filter used in a display device such as a liquid crystal display device, an electroluminescence display device, and a plasma display device. As such a colored photosensitive resin composition, a colored photosensitive resin composition containing a phthalocyanine dye (JP2011-28236-A) is known.

When a colored pattern is formed by photolithography, during development, When the colored photosensitive resin composition layer on the substrate is removed to the developing solution by peeling, the release sheet may be applied as a foreign matter impurity on the colored pattern, or may block the development of the developed developer. Piping. Conventionally, the above-described colored photosensitive resin composition is as described above, and the above-described developability is not always sufficient.

The present invention includes the following inventions.

[1] A colored photosensitive resin composition containing a colorant, a resin, a polymerizable compound, a polymerization initiator, and a thiol compound, and the colorant is a xanthene dye and a pigment. The toner, the polymerization initiator contains a biimidazole compound or an O-acyloxime compound.

[2] The colored photosensitive resin composition according to [1], wherein the xanthene dye is a dye containing a compound represented by the formula (1a).

[In the formula (1a), R ¹ to R ⁴ are each independently, represent a hydrogen atom, a substituent having a carbon number of 1 to 20 monovalent saturated hydrocarbon group or may have a substituent group of carbon number 6 to 10 is a monovalent The aromatic hydrocarbon group may be substituted by -O-, -CO- or -NR ¹¹ - in the -CH ₂ - contained in the saturated hydrocarbon group. R ¹ and R ² may also form a ring together with an adjacent nitrogen atom, and R ³ and R ⁴ may form a ring together with an adjacent 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 are each independently a hydrogen atom and an alkyl group having 1 to 6 carbon atoms.

m represents an integer from 0 to 5. When m is 2 or more, a plurality of R ⁵ may be the same or different.

a represents an integer of 0 or 1.

X represents a halogen atom.

Z ⁺ represents ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and 4 R ¹¹ may be the same or different.

R ⁸ is a C 1-20 monovalent saturated hydrocarbon group comprising a hydrogen atom of the saturated hydrocarbon group may be substituted with a halogen atom.

R ⁹ and R ¹⁰ are each independently a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and the -CH ₂ - contained in the saturated aliphatic hydrocarbon group may also be -O-, - CO-, -NH- or -NR ⁸ - substitution. R ⁹ and R ¹⁰ may also form a nitrogen-containing heterocyclic ring of 3 to 10 members together with the adjacent nitrogen atom of the bond.

R ¹¹ 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.

[3] The colored photosensitive resin composition according to [1], wherein the polymerization initiator contains a biimidazole compound.

[4] The colored photosensitive resin composition according to [1], wherein the polymerization initiator contains an O-indenyl ruthenium compound.

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

[6] A display device comprising the color filter according to [5].

According to the colored photosensitive resin composition of the present invention, in the developing solution after development, the release sheet which is produced from the coloring photosensitive resin composition is less.

The colored photosensitive resin composition of the present invention contains a coloring agent (A), a resin (B), a polymerizable compound (C), and a polymerization initiator. (D) and a thiol compound (T).

The colored photosensitive resin composition of the present invention preferably further contains a solvent (E) and/or a leveling agent (F).

The colored photosensitive resin composition of the present invention may contain a polymerization initiation aid (D1).

In the present specification, the compounds exemplified as the respective components may be used singly or in combination of plural kinds unless otherwise specified.

<Colorant (A)>

The colorant (A) contains the xanthene dye (A1) and the pigment (A2), and may further contain a dye other than the xanthene dye (A1).

The xanthene dye (A1) is a dye of a compound containing a xanthene skeleton in the molecule. Examples of the xanthene dye (A1) include CI Acid Red 51 (hereinafter, the symbol of CI acid red is omitted, only the number is described. Others are the same), 52, 87, 92, 94, 289, 388; CI acid violet 9, 30, 102; CI basic red (CIBasic Red) 1 (Rhodamine 6G), 2, 3, 4, 8; CI alkaline red 10 (rose red B ); 11; CI alkaline violet 10, 11, 25; CI solvent red 218; CI media red (CI Mordant Red) 27, CI reactive red 36 (Rose bengal B), Sulforhodamine G, a xanthene dye described in JP2010-32999-A, a xanthene dye described in JP4492760-B, and the like. It is preferred to dissolve in an organic solvent.

In the above, the oxanthene dye (A1) contains a compound represented by the formula (1a) (hereinafter, referred to as "the compound (1a)"). Dyes are preferred. The compound (1a) may also be a tautomer thereof. When the compound (1a) is used, the content of the compound (1a) in the xanthene dye (A1) is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more. In particular, as the xanthene dye (A1), it is preferred to use only the compound (1a).

In the formula (1a), when -SO ₃ ^{- is} present, the number thereof is one.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ to R ⁴ include a phenyl group, a toluyl group, a xylyl group, and a 2,4,6-trimethylphenyl group. (mesityl), propylphenyl, butylphenyl and the like.

Examples of the substituent which the aromatic hydrocarbon group may have include 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 ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ . Wherein the substituent again _{^{-SO 3 -, -SO 3 H,}} -SO 3 - Z + and -SO ₂ NR ⁹ R ¹⁰ preferred, and -SO ₃ ^- Z ⁺ and -SO ₂ NR ⁹ R ¹⁰ For better. In this case, as -SO ₃ ^- Z ⁺ , -SO ₃ ^-+ N(R ¹¹ ) _{4 is} preferred. Less impurities present invention the colored photosensitive resin composition of R ¹ to R ⁴ group, etc. For this reason, by containing the compound (1a) to form generated, and excellent heat resistance of the color filter.

In the case of R ¹ to R ⁴ and R ⁸ to R ¹¹ , examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. Octyl, fluorenyl, fluorenyl, dodecyl, hexadecanyl, eicosyl and other linear alkyl groups; isopropyl, isobutyl, isopentyl, neopentyl, 2-ethylhexyl A branched alkyl group; a cyclopropyl 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.

The hydrogen atom contained in the saturated hydrocarbon group in R ¹ to R ⁴ may be substituted, for example, by an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom.

In R ⁸ and R ¹⁰ , the hydrogen atom contained in the saturated hydrocarbon group may be substituted, for example, by a hydroxyl group or a halogen atom.

Examples of the ring formed by R ¹ and R ² together with the adjacent nitrogen atom and the ring formed by R ³ and R ⁴ together with the adjacent nitrogen atom include the following.

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 the like. An icosyloxy group or the like.

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

As -SR ^8, for example, may include: a methyl group, an ethyl group, a butyl group, a hexyl group, a decyl group, a twenty-ylthio and the like.

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 tertiary butoxysulfonyl group, a hexyloxysulfonyl group, and 20 Alkoxysulfonyl and the like.

As -SO ₂ NR ⁹ R ¹⁰ , for example, a sulfamoyl group; N-methylamine sulfonyl group, N-ethylamine sulfonyl group, N-propylamine sulfonyl group, N- Isopropylamine sulfonyl, N-butylamine sulfonyl, N-isobutylamine sulfonyl, N-tertiary butylamine sulfonyl, N-tert-butylamine sulfonyl, N - amylamine sulfonyl, N-(1-ethylpropyl)amine sulfonyl, N-(1,1-dimethylpropyl)amine sulfonyl, N-(1,2-dimethyl Propyl sulfonyl, N-(2,2-dimethylpropyl)amine sulfonyl, N-(1-methylbutyl)amine sulfonyl, N-(2-methylbutyl Aminesulfonyl, N-(3-methylbutyl)aminesulfonyl, N-cyclopentylaminesulfonyl, N-hexylaminesulfonyl, N-(1,3-dimethyl Butyl)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 N-1 substituted amine sulfonyl group such as hexylamine sulfonyl group, N-(1,1,2,2-tetramethylbutyl)amine sulfonyl group; NN-dimethylamine sulfonyl group, N, N-ethylmethylamine sulfonyl, N,N-diethylamine sulfonate N,N-propylmethylamine sulfonyl, N,N-isopropylmethylamine sulfonyl, N,N-tertiary butylmethylamine sulfonyl, N,N-butylethyl An N,N-2 substituted amine sulfonyl group such as an aminesulfonyl group, an N,N-bis(1-methylpropyl)aminesulfonyl group or an N,N-heptylmethylaminesulfonyl group.

R ⁵ is preferably -CO ₂ H, -CO ₂ ^- Z ⁺ , -CO ₂ R ⁸ , -SO ₃ ^- , -SO ₃ ^- Z ⁺ , -SO ₃ H, or -SO ₂ NHR ⁹ -SO ₃ ^- , -SO ₃ ^- Z ⁺ , -SO ₃ H, or -SO ₂ NHR ⁹ is more preferred.

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

Examples of the alkyl group having 1 to 6 carbon atoms in R ⁶ and R ⁷ include those having 1 to 6 carbon atoms in the above-exemplified alkyl groups.

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

Z ⁺ is ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and ⁺ N(R ¹¹ ) _{4 is} preferred.

As the above ⁺ N(R ¹¹ ) ₄ , among the four R ¹¹ , at least two monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms are preferred. Further, the total carbon number of the four R ¹¹ is preferably from 20 to 80, more preferably from 20 to 60. In the case of the compound (1a), when R ¹¹ is such a group in the presence of ⁺ N(R ¹¹ ) ₄ , the colored photosensitive resin composition of the present invention containing the compound (1a) can form less impurities. Color filter.

The compound (1a) is preferably a compound represented by the formula (2a) (hereinafter, referred to as "compound (2a)"). Compound (2a) may also be a tautomer thereof.

In the formula (2a), R ²¹ to R ²⁴ are each independently a hydrogen atom, -R ²⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. R ²¹ and R ²² may form a ring together with an adjacent nitrogen atom, and R ²³ and R ²⁴ may form a ring together with an adjacent 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. When m1 is 2 or more, a plurality of R ²⁵ are the same or different.

A1 represents an integer of 0 or 1.

X1 represents a halogen atom.

R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.

Represents Z1 ^{+ _{+ N (R 27) 4,}} Na + or K ^+, 4 th R ²⁷ may be the same or different.

R ²⁷ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or a benzyl group].

The monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ²¹ to R ²⁴ may be the same as those exemplified as the aromatic hydrocarbon group of R ¹ to R ⁴ described above. The hydrogen atom contained in the aromatic hydrocarbon group may be substituted by -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z1 ⁺ , -SO ₃ R ²⁸ or -SO ₂ NHR ²⁸ .

As a combination of R ²¹ to R ²⁴ , R ²¹ and R ²³ are a hydrogen atom, and R ²² and R ²⁴ are a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the aromatic hydrocarbon group contains a hydrogen atom, which is -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z1 ⁺ , -SO ₃ R ²⁸ or -SO ₂ NHR ²⁸ is preferred. More preferably, R ²¹ and R ²³ are a hydrogen atom, and R ²² and R ²⁴ are a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom of the aromatic hydrocarbon group is -SO ₃ ^- Z1 ⁺ , Or -SO ₂ NHR ²⁸ replacement.

When R ²¹ to R ^{24 are} these groups, a color filter which is more excellent in heat resistance can be formed from the colored photosensitive resin composition of the present invention containing the compound (2a).

The ring formed by R ²¹ and R ²² together with the adjacent nitrogen atom and the ring formed by R ²³ and R ²⁴ together with the adjacent nitrogen atom may be the same as those formed by R ¹ and R ² together with the adjacent nitrogen atom. . Among them, aliphatic heterocyclic rings are preferred. Examples of the aliphatic heterocyclic ring include the following.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ²⁶ and R ²⁷ include the same groups as those in the case of R ⁸ to R ¹¹ as a saturated hydrocarbon group.

When R ²¹ to R ²⁴ are -R ²⁶ , -R ²⁶ is each independently, and a methyl group or an ethyl group is preferred. Further, as -SO ₃ R ^26, and in the -SO ₂ NHR ²⁶ R ^26, is a branched chain alkyl group having a carbon number of 3 to 20 is preferred to branched chain alkyl of 6 to 12 carbon atoms, The base is more preferred, and 2-ethylhexyl is more preferred. When R ^{26 is} such a group, a color filter which produces less impurities can be formed from the colored photosensitive resin composition of the present invention containing the compound (2a).

Z1 ⁺ is ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ²⁷ ) ₄ . As the above ⁺ N(R ²⁷ ) ₄ , it is preferred that at least two of the four R ²⁷ are a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. In addition, four of R ²⁷ is the total number of carbon atoms is preferably 20 to 80, more preferably 20 to 60 is a. When ⁺ N(R ²⁷ ) ₄ is present in the compound (2a), when R ²⁷ has such a group, a color filter which produces less impurities can be formed from the colored photosensitive resin composition of the present invention containing the compound (2a). Light film.

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

Further, as the compound (1a), a compound represented by the formula (3a) (hereinafter referred to as "the compound (3a)") is also preferable. Compound (3a) may also be a tautomer thereof.

[In the formula (3a), R ³¹ and R ³² are each independently and represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be an aromatic hydrocarbon group having 6 to 10 carbon atoms or The halogen atom may be substituted, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted by an alkoxy group having 1 to 3 carbon atoms, and the -CH ₂ - contained in the saturated hydrocarbon group may also be -O-, -CO- or -NR ¹¹ - replaced.

R ³³ and R ³⁴ are each independently and represent an alkyl group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms or an alkanesulfonyl group having 1 to 4 carbon atoms.

R ³¹ and R ³³ may form a ring together with an adjacent nitrogen atom, and R ³² and R ³⁴ may form a ring together with an adjacent nitrogen atom.

p and q are integers representing 0 to 5 independently of each other. When p is 2 or more, a plurality of R ³³ may be the same or different, and when q is 2 or more, a plurality of R ³⁴ may be the same or different.

R ¹¹ represents the same meaning as above].

^Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in R ³¹ and R ³³ include a group having 1 to 10 carbon atoms in R ⁸ .

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent include the same groups as those exemplified for R ¹ .

Examples of the alkoxy group having 1 to 3 carbon atoms include a methoxy group, an ethoxy group, a propoxy group and the like.

R ³¹ and R ³³ are each independently a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms.

Examples of the alkyl group having 1 to 4 carbon atoms in R ³³ and R ³⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a secondary butyl group, and a tertiary butyl group. .

Examples of the alkylthio group having 1 to 4 carbon atoms in R ³³ and R ³⁴ include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, and an isopropylthio group.

Examples of the alkylsulfonyl group having 1 to 4 carbon atoms in 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 ³³ and R ³⁴ are preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.

Preferably, p and q are 0 to 2, and more preferably 0 or 1.

The compound (1a) may, for example, be a compound represented by the formula (1-1) to the formula (1-43). Further, in the formula, R ⁴⁰ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched chain alkyl group having 6 to 12 carbon atoms, more preferably 2-ethylhexyl group.

Among the above compounds, the compound represented by the formula (1-1) to the formula (1-23) and the formula (1-37) to the formula (1-43) is equivalent to the compound (2a), the formula (1-24). The compound represented by the formula (1-36) corresponds to the compound (3a).

Among these, a sulfonamide compound of C.I. Acid Red 289, a grade 4 ammonium salt of C.I. Acid Red 289, a sulfonamide compound of C.I. Acid Violet 102, or a quaternary ammonium salt of C.I. Acid Violet 102 is preferred. Examples of such a compound include a compound represented by the formula (1-1) to the formula (1-8), the formula (1-11), and the formula (1-12).

Further, the point of the solubility in the organic solvent is preferably a compound represented by any one of the formulae (1-24) to (1-33).

As the xanthene dye (A1), a commercially available xanthene dye (for example, "Chugai Aminol Fast Pink R-H/C" manufactured by Nakato Chemical Co., Ltd., "Rhodamin 6G" manufactured by Tajika Chemical Industry Co., Ltd.) can be used. Further, a commercially available xanthene dye can be used as a starting material, and it can be synthesized by referring to JP2010-32999-A.

The content of the xanthene dye (A1) is preferably from 0.5 to 50% by mass, more preferably from 0.5 to 40% by mass, still more preferably from 0.5 to 30% by mass, based on the total amount of the coloring agent (A).

The pigment (A2) is not particularly limited, and a known pigment can be used. For example, a pigment classified as a pigment in a color index (COLOR 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, Yellow pigments such as 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43 , 51, 53, 59, 61, 64, 65, 71, 73 and other orange pigments; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209 , red pigments such as 215, 216, 224, 242, 254, 255, 264, 265; blue pigments such as CI Pigment Blue 15, 15:3, 15:4, 15:6, 60; CI Pigment Violet 1, 19, 23, 29, 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.

As the pigment, C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 60 and other blue pigments, C.I. Pigment Violet 1, 19, 23, 29, Purple pigments such as 32, 36, 38; more preferably C.I. Pigment Blue 15:3, 15:6 and C.I. Pigment Violet 23; and more preferably C.I. Pigment Blue 15:6. By containing the above-mentioned pigment, the spectrum of the transmitted light becomes easy to be optimized, and the light resistance and chemical resistance of the color filter become better.

The pigment may be carried out as needed: rosin treatment, surface treatment using a pigment derivative introduced with an acidic group or a basic group, graft treatment of a pigment surface by a polymer compound, etc., by a sulfuric acid micronization method, or the like The micronization treatment or the treatment of removing the impurities by an organic solvent or water, or the removal of the ionic impurities by an ion exchange method or the like.

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

Examples of the pigment dispersant include pigment dispersants such as cationic, anionic, nonionic, zwitterionic, polyester, polyamine, and acrylic. These pigment dispersing agents may be used singly or in combination of two or more. As a pigment dispersing agent, KP (made by Shin-Etsu Chemical Co., Ltd.), Flowlen (made by Kyoei Chemical Co., Ltd.), Solsperse (made by Zeneca Co., Ltd.), and EFKA (made by CIBA) are mentioned. AJISPER (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (manufactured by BYK Chemical Co., Ltd.), and the like.

When the pigment dispersant is used, the amount thereof is preferably from 1% by mass to 100% by mass, more preferably 5% by mass, based on the total amount of the pigment (A2). Above 50% by mass. When the amount of the pigment dispersant used is within the above range, there is a tendency to obtain a pigment dispersion liquid in a uniformly dispersed state.

The content of the pigment (A2) is preferably from 50 to 99.5% by mass, more preferably from 60 to 99.5% by mass, still more preferably from 70 to 99.5% by mass, based on the total amount of the coloring agent (A).

A dye other than the xanthene dye (A1) (hereinafter referred to as "dye (A3)") is not particularly limited as long as it is different from the xanthene dye (A1), and a known dye can be used, for example. Usa: azo dye, cyanine dye, triphenylmethane dye, anthraquinone dye, anthraquinone dye, naphthoquinone dye, quinone imine dye, methine dye, azo Base dyes, squarylium dyes, acridinine dyes, styryl dyes, coumarin dyes, quinoline dyes, and nitro dyes. Among these, organic solvent-soluble dyes are preferred.

Among them, an anthraquinone dye is preferred, and a compound represented by the formula (4) is more preferred.

[In the formula (4), G ¹ represents an alkanediyl having 2 to 12 carbon atoms, and a hydrogen atom contained in the alkanediyl group may also be substituted with an alkyl group having 1 to 4 carbon atoms, in the alkanediyl group. The -CH ₂ - contained in the group may also be replaced 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 of 1 to 4].

The formula (4) is a group in which p hydrogen atoms contained in the compound represented by the 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 as each other or may be different from each other.

Examples of the alkanediyl group having 2 to 12 carbon atoms include a methylene group, an exoethyl group, a propanediyl group, and a butyl group.

The alkanediyl group having 2 to 12 carbon atoms which is substituted by -O ₂ - is a group represented by the formula (G-1) and a group represented by the formula (G-2).

In the formulae (G-1) and (G-2), G ² to G ⁵ each independently represent an alkanediyl group having 1 to 8 carbon atoms.

n ¹ represents an integer of 1 to 3.

n ² represents an integer of 0 to 3.

However, 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 total number of carbon atoms and oxygen atoms contained in the group represented by the formula (G-2) is 2 to 12.

* is a bond indicating 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, a butyl group and the like.

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

When 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.

When G ¹ is the formula (G-2) the group shown as _{^{-SO 2 -NH-G 1 -J 1}} , for example, include a group represented by the following formula.

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

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

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, a decyl group and the like.

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, an anthracenyl group and the like.

X-CO ₂ ^- is an organic anion containing a CO ₂ ^- group, and Y-SO ₃ ^- is an organic anion containing a SO ₃ ^- group, and examples thereof include an anion represented by the formula (Q-1) to the formula (Q-4) .

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

m represents an integer from 0 to 5.].

As Q ^- who, based on X-CO ₂ ^- and Y-SO ₃ ^- preferably, of formula (Q-4) is more preferably an anion shown. In the case of these anions, the solubility of the compound represented by the formula (2) in a solvent tends to be high.

Examples of the compound represented by the formula (4) include compounds represented by the formula (2-1) to the formula (2-92). In the compound represented by the formula (2-1) to the formula (2-92), when n ^a is an integer of 2 or more, it is preferred that a plurality of -SO ₂ —NH—G ¹ —J ¹ are bonded to each other. Different benzene rings.

For example, the compound represented by formula (2-24) is more specific Examples thereof include compounds represented by the formula (2-24-1) and the formula (2-24-2).

When the colorant (A) contains the dye (A3), the content of the dye (A3) is preferably 0.5% by mass or more and 40% by mass or less, and preferably 0.5% by mass or more and 30% by mass or less based on the total amount of the coloring agent (A). The following is better.

When the colorant (A) is a coloring agent containing the xanthene dye (A1) and the pigment (A2), the content of the coloring agent (A) is preferably a xanthene dye (A1), respectively, based on the total amount of the coloring agent (A). 0.5% by mass or more and 50% by mass or less of the pigment (A2): 50% by mass or more and 99.5% by mass or less, more preferably xanthene dye (A1): 0.5% by mass or more and 40% by mass or less of the pigment (A2): 60% by mass The above 99.5 mass% or less.

When the coloring agent (A) is a coloring agent containing the xanthene dye (A1), the pigment (A2), and the dye (A3), the content of the coloring agent (A) is preferably oxygen mixed with respect to the total amount of the coloring agent (A). Anthraquinone dye (A1): 0.5% by mass or more and 50% by mass or less of pigment (A2): 49.5 mass% or more and 99% by mass or less of dye (A3): 0.5% by mass or more and 40% by mass or less, more preferably xanthene dye (A1) ): 0.5% by mass or more and 40% by mass or less Pigment (A2): 59.5 mass% or more and 99 mass% or less of dye (A3): 0.5 mass% or more and 30 mass% or less.

The content of the colorant (A) is preferably from 5 to 60% by mass, more preferably from 8 to 55% by mass, still more preferably from 10 to 50% by mass, based on the total amount of the solid content. 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 since the necessary amount of the resin (B) or the polymerizable compound (C) can be contained in the composition, A pattern having sufficient mechanical strength is formed. Here, the "total amount of solid content" in the present specification means the amount of the solvent removed by the total amount of the colored photosensitive resin composition. The total amount of the solid fraction and the content of each of the fractions formed thereon can be measured, for example, by a known analytical method such as liquid chromatography or gas chromatography.

<Resin (B)>

The resin (B) is not particularly limited, but an alkali-soluble resin is preferred. Examples of the resin (B) include resins [K1] to [K6].

Resin [K1]: at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (a) (hereinafter referred to as (a)), and a ring having a carbon number of 2 to 4. a copolymer of an ether structure and a monomer having an ethylenically unsaturated bond (b) (hereinafter referred to as a case of (b)); a resin [K2]: (a), (b), and copolymerizable with (a) a monomer (c) (but (a) and (b) are different) (hereinafter referred to as the case of (c)); a resin [K3]: a copolymer of (a) and (c); Resin [K4]: a resin obtained by reacting the copolymer of (a) and (c) with (b); resin [K5]: reacting the copolymer of (b) and (c) with (a) Resin; resin [K6]: reacting the copolymer of (b) and (c) with (a), and then with carboxylic anhydride The resin obtained by the reaction.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid; maleic acid, fumaric acid, and citrine Acid, mesaconic acid, isoconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrogen Unsaturated carboxylic acids such as phthalic acid, dimethyltetrahydrophthalic acid, and 1,4-cyclohexene dicarboxylic acid; methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2,1]hept-2-ene, 5,6-dicarboxybicyclo[2.2,1]hept-2-ene, 5-carboxy-5-methylbicyclo[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-ene, 5-carboxy-6-ethylbicyclo[2.2 , 1] a bicyclic unsaturated compound containing a carboxyl group such as hept-2-ene; maleic anhydride, citraconic anhydride, isaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3, 4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2,1] Unsaturated carboxylic anhydrides such as hept-2-ene anhydrate; succinic acid Unsaturated mono[(methyl) propylene oxime of a divalent or higher polycarboxylic acid such as [2-(methyl) propylene oxime) or phthalic acid mono [2-(methyl) propylene oxime] An oxyalkyl]ester; such as an α-(hydroxymethyl) acrylate having an unsaturated acrylate having a hydroxyl group and a carboxyl group in the same molecule.

Among them, acrylic acid, methacrylic acid, maleic anhydride, etc., in terms of the point of copolymerization reactivity or the solubility of the obtained resin in an aqueous alkali solution It is better.

(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, an oxetane ring, and a tetrahydrofuran ring) and ethylenic unsaturation A polymerizable compound of a bond. (b) It is preferred to use a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloxy group.

In the present specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The expressions of "(meth)acrylonitrile" and "(meth)acrylate" have the same meaning.

(b), for example, a monomer (b1) having an oxirane group and an ethylenically unsaturated bond (hereinafter referred to as "(b1)"), an oxetane group and ethylene a monomer (b2) having an unsaturated bond (hereinafter referred to as "(b2)"), a monomer having a tetrahydrofuranyl group and an ethylenically unsaturated bond (b3) (hereinafter referred to as "(b3)") Situation) and so on.

(b1), for example, a monomer (b1-1) having a structure in which a linear or branched chain aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as "(b1-1)" In the case of the case, the monomer (b1-2) having a structure in which the alicyclic unsaturated hydrocarbon is epoxidized (hereinafter referred to as "(b1-2)").

Examples of (b1-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, and glycidylethylene. Ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzene Methyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxy) Styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl) Styrene, 2,3,4-glycol (glycidyloxymethyl)styrene, 2,3,5-gin (glycidyloxymethyl)styrene, 2,3,6-gin (glycidyl) Oxymethyl)styrene, 3,4,5-gin (glycidyloxymethyl)styrene, 2,4,6-gin (glycidyloxymethyl)styrene, and the like.

(b1-2), for example, vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, CELLOXIDE 2000; manufactured by Daicel Co., Ltd.), 3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, CYCLOMER A-400; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, CYCLOMER M-100; manufactured by Daicel Co., Ltd.), a compound represented by the formula (I), a compound represented by the formula (II), and the like.

In the formulae (I) and (II), R ^a and R ^{b each} 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 ^a and X ^b represents a single ^{bond, -R C -, * - R} C -O -, * - R C -S-, or * -R ^C -NH-.

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

* indicates a bond 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 secondary butyl group, and a tertiary butyl group.

Examples of the alkyl group in which the hydrogen atom is substituted by 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.

Examples of R ^a and R ^b include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, and more preferred examples thereof include a hydrogen atom and 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.

As X ^a and X ^b are, may preferably include: a single bond, methylene, ethyl stretch, * - CH ₂ -O-, and * -CH ₂ CH ₂ -O-, more preferably may include: Single bond, *-CH ₂ CH ₂ -O- (* indicates a bond with O).

The compound represented by the formula (1) may, for example, be a compound represented by any one of the formulae (I-1) to (I-15). Wherein, the formula (I-1), the formula (I-3), the formula (I-5), the formula (I-7), the formula (I-9) or the formula (I-11) to the formula (I-15) The compound shown is preferably a compound represented by the formula (I-1), the formula (I-7), the formula (I-9), or 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). Wherein, using formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11) to formula (II-15) The compound shown is 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 alone or in combination of two or more. When a compound represented by the formula (I) and a compound represented by the formula (II) are used in combination, the content ratio of the compound [the compound represented by the formula (I): the compound represented by the formula (II)] is based on the molar basis. It is preferably 5:95 to 95:5, more preferably 20:80 to 80:20.

As (b2), with oxetane and (methyl) propyl A monomer having an oxiranyloxy group is preferred. Examples of (b2) include 3-methyl-3-methylpropenyloxymethyloxetane, 3-methyl-3-propenyloxymethyloxetane, and 3- Ethyl-3-methylpropenyloxymethyloxetane, 3-ethyl-3-propenyloxymethyloxetane, 3-methyl-3-methylpropene oxime Ethyloxyoxetane, 3-methyl-3-propenyloxyethyloxetane, 3-ethyl-3-methylpropenyloxyethyloxetane, 3 Ethyl-3-propenyloxyethyloxetane and the like.

As (b3), a monomer having a tetrahydrofuranyl group and a (meth)acryloxy group is preferred. Specific examples of (b3) include tetrahydrofuran acrylate (for example, Biscoat v #150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofuranylmethyl acrylate, and the like.

In view of the fact that the reliability of heat resistance and chemical resistance of the color filter can be further improved, (b) is preferably (b1). Further, in terms of excellent storage stability of the colored photosensitive resin composition, (b1-2) is preferred.

Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, n-butyl (meth)acrylate, and (meth)acrylic acid III. Butyl methacrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2.6 ] decane-8-yl (meth) acrylate (a common name in the art, There is a case called "dicyclopentanyl (meth)acrylate", or a case called "tricyclodecyl (meth)acrylate), tricyclo[methyl]acrylic acid [5.2.1.0 ^2.6 ]nonene- 8-Base ester (a commonly used name in the art is referred to as "dicyclopentyl (meth)acrylate)", dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate , adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, (meth) acrylate (meth)acrylates such as esters; (meth)acrylic acid 2 a hydroxyl group-containing (meth) acrylate such as hydroxyethyl ester or 2-hydroxypropyl (meth)acrylate; dicarboxylate such as diethyl maleate, diethyl fumarate or diethyl itaconate; Acid diester; 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- Alkene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]heptane- 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-dimethoxyhydroxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methyl Bicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]heptane- 2-ene, 5-tris-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(tertiary butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis ( Bicyclic unsaturated compounds such as hexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaline Yttrium imine, N-succinimide-3-maleimide benzoate, N-amber succinimide-4-maleimide butyrate, N-succinimide -6-maleimide caproate, N-succinimide-3-maleimide propionate, N-(9-acridinyl)maleimide (N-(9) -Acridinyl)maleimide) and other dicarbonyl ruthenium derivatives; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile , methacrylonitrile, ethylene chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 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-cyclohexylmaleimide, N-benzoic acid are used. Preferably, carbamazepine, bicyclo[2.2.1]hept-2-ene, and the like.

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

When the structural unit ratio of the resin [K1] is in 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 color filter tend to be excellent.

Resin [K1], for example, can be referred to the method described in the "Experimental Method for Polymer Synthesis" (Otsuya Ryokan, Chemicals Co., Ltd., 1st Edition, 1st, 1st, 1972, March 1st). Manufactured by references cited in the literature.

Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, and for example, a deoxidizing gas atmosphere is set by substituting nitrogen gas for oxygen, and stirring is performed while stirring. One method of heating and keeping warm. Moreover, the polymerization initiator, the solvent, and the like used herein are not particularly limited, and those skilled in the art 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 solvent (E) which is a composition of the colored photosensitive resin of the present invention is a solvent (E), and a solvent to be described later.

Further, the copolymer obtained may be used as it is, or a solution obtained by concentration or dilution may be used, or a solid (powder) may be taken out by reprecipitation or the like. In particular, since the solvent used in the polymerization is a solvent contained in the composition of the colored photosensitive resin of the present invention, the solution after the reaction can be directly used for preparing the colored photosensitive resin composition of the present invention. The manufacturing steps of the colored photosensitive resin composition of the present invention can be simplified.

In the resin [K2], in all the structural units constituting the resin [K2], the ratio of the structural units of each source is preferably a structural unit derived from (a): 2 to 45 mol% derived from (b) Structural unit: 2 to 95 mol% of structural unit derived from (c): 1 to 65 mol%, more preferably structural unit derived from (a): 5 to 40 mol% derived from the structure of (b) Unit: 5 to 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 when forming a colored pattern, and the solvent resistance, heat resistance and mechanical properties of the obtained color filter The strength has an excellent tendency.

The resin [K2] can be produced, for example, in the same manner as the method described in the production method of the resin [K1].

In the resin [K3], in all the structural units constituting the resin [K3], the ratio of the structural units of each source is preferably a structural unit derived from (a): 2 to 60 mol% derived from (c) The structural unit: 40 to 98 mol%, and more preferably the structural unit derived from (a): 10 to 50 mol% of the structural unit derived from (c): 50 to 90 mol%.

The resin [K3] can be produced, for example, in the same manner as the method described in the production method of the resin [K1].

Resin [K4], after obtaining the copolymer of (a) and (c), by adding the carboxylic acid and/or carboxylic anhydride having (a) to a cyclic ether having a carbon number of 2 to 4 ( b) can be manufactured.

First, the copolymers of (a) and (c) were produced in the same manner as described in the method for producing the resin [K1]. At this time, the ratio of the structural units of each source is preferably the same ratio as the ratio exemplified by the resin [K3].

Next, the cyclic ether having a carbon number of 2 to 4 in (b) is reacted with a part of the carboxylic acid and/or carboxylic anhydride derived from (a) in the above copolymer.

After the copolymer of (a) and (c) is produced, the gas atmosphere in the flask is Substituting nitrogen for air, reacting (b), a carboxylic acid or a reaction agent of a carboxylic anhydride with a cyclic ether (for example, phenol (phenol), etc.) and a polymerization inhibitor (such as hydroquinone) The resin [K4] can be produced by, for example, being placed in a flask, for example, by reacting at 60 to 130 ° C for 1 to 10 hours.

The amount of (b) used is preferably from 5 to 80 moles, more preferably from 10 to 75 moles, relative to (a) 100 moles. By setting it as the range, the storage stability of the colored photosensitive resin composition, the developability at the time of pattern formation, and the balance of solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained pattern tend to be improved. . Since the reactivity of the cyclic ether is high and the unreacted (b) does not easily remain, the (b) used in the resin [K4] is preferably (b1), more preferably (b1-1).

The amount of the above-mentioned reaction catalyst used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total of (a), (b) and (c). The amount of the polymerization inhibitor to be used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total of (a), (b) and (c).

The reaction conditions such as the method, the reaction temperature, and the time can be appropriately adjusted in consideration of the amount of heat generated by the production equipment or the polymerization. Moreover, the charging method and the reaction temperature can be appropriately adjusted in consideration of the heat generation amount by the production equipment or the polymerization in the same manner as the polymerization conditions.

In the first step of the resin [K5], the same operation as the above-described method for producing the resin [K1] was carried out to obtain a copolymer of (b) and (c). In the same manner as described above, the obtained copolymer may be used as it is, or a concentrated or diluted solution may be used, or a solid (powder) taken out by a method such as reprecipitation may be used.

The ratio of the structural units derived from (b) and (c) with respect to the total number of moles of all the structural units constituting the aforementioned copolymer is preferably a structural unit derived from (b): 5 to 95 The ear % is derived from the structural unit of (c): 5 to 95 mol%, and the structural unit derived from (b): 10 to 90 mol% of the structural unit derived from (c): 10 to 90 mol% For better.

Further, under the same conditions as the method for producing the resin [K4], the cyclic ether derived from (b) and the carboxylic acid (a) possessed by the copolymers (b) and (c) may be used. The carboxylic anhydride is reacted to obtain a resin [K5].

The amount of (a) to be reacted with the aforementioned copolymer is preferably from 5 to 80 moles relative to (b) 100 moles. Since the cyclic ether has high reactivity and does not easily remain unreacted (b), (b) used in the resin [K5] is preferably (b1), more preferably (b1-1).

The resin [K6] is a resin which further reacts the carboxylic anhydride with the resin [K5].

The hydroxyl group produced by the reaction of a cyclic ether with a carboxylic acid or a carboxylic anhydride is reacted with a carboxylic acid anhydride.

Examples of the carboxylic anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, and 3,4,5,6-tetrahydrophthalic acid. Anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarbonylbicyclo[2.2.1]hept-2-ene anhydrate, and the like. The amount of the carboxylic anhydride used is preferably from 0.5 to 1 mol per mol of the amount of (a) used.

Specific examples of the resin (B) include (meth)acrylic acid 3,4-epoxycyclohexylmethyl ester/(meth)acrylic acid copolymer, and acrylic 3,4-epoxytricyclo[5.2. .1.0 ^2.6 ] Resin of oxime ester/(meth)acrylic acid copolymer [K1]; glycidyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymer, (methyl Glycidyl acrylate/styrene/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate/(meth)acrylic acid/N-cyclohexylmalazone Amine copolymer, resin such as 3-methyl-3-(meth)acryloxymethyloxybutane/(meth)acrylic acid/styrene copolymer [K2]; benzene (meth)acrylate a resin such as a methyl ester/(meth)acrylic acid copolymer or a styrene/(meth)acrylic acid copolymer [K3]; a copolymer of benzyl (meth)acrylate/(meth)acrylic acid (methyl) a resin of glycidyl acrylate, a resin obtained by adding glycidyl (meth)acrylate to a tricyclodecyl (meth) acrylate/styrene/(meth)acrylic acid copolymer, in (meth)acrylic acid Cyclodecyl ester / benzyl (meth) acrylate / (A a resin obtained by adding a resin such as glycidyl (meth)acrylate to an acrylic copolymer [K4]; a (meth)acrylic acid to tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate a resin which reacts with a copolymer, a resin which reacts a copolymer of (meth)acrylic acid with tricyclodecyl (meth)acrylate/styrene/glycidyl (meth)acrylate, and the like [K5]; A resin obtained by reacting a copolymer of acrylic acid with tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate, a resin such as a resin which is reacted with tetrahydrophthalic anhydride, or the like [K6].

Among them, the resin (B) is preferably a copolymer containing a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, and derived from a carbon number. 2 to 4 ring A structural unit of a monomer having an ether structure and an ethylenically unsaturated bond; that is, a resin [K1] and a resin [K2] are preferred.

The polystyrene-equivalent weight average molecular weight of the resin (B) 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, particularly preferably from 5,000 to 12,000. When the molecular weight is within the above range, the hardness of the color filter is improved, and the solubility in the developer in the unexposed portion is good, and in the developer after development, the generation of the release sheet derived from the colored photosensitive resin composition is changed. Less tendency.

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

The acid value of the resin (B) 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 for measuring the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be obtained, for example, by titration with an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably from 7 to 65 mass%, more preferably from 13 to 60 mass%, still more preferably from 17 to 55 mass%, based on the total amount of the solids. When the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution of the colored pattern and the residual film ratio tend to be improved.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound which can be polymerized by living radicals and/or oxygen generated by the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenically unsaturated bond. Preferably, it is 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 dinoxin. Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentenol octa (meth) acrylate, tripentanisitol hepta (meth) acrylate, Tetrakis pentaerythritol deca (meth) acrylate, tetrapentaerythritol 九 (meth) acrylate, ginseng (2-(methyl) propylene methoxyethyl) isocyanate, ethylene glycol modified pentylene Tetraol tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth) acrylate, propylene glycol modified pentaerythritol tetra(meth) acrylate, propylene glycol modified dipentaerythritol Alcohol hexa (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dine pentaerythritol hexa (meth) acrylate, and the like.

Among them, dipentaerythritol penta (meth) acrylate and dine pentaerythritol hexa (meth) acrylate are preferred.

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 mass%, more preferably from 13 to 60 mass%, still more preferably from 17 to 55 mass%, based on the total amount of the solid component. When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of forming the colored pattern and the chemical resistance of the color filter tend to be improved.

<Polymerization initiator (D)>

The polymerization initiator (D) is free to generate activity by the action of light or heat. The compound which starts polymerization by a base, oxygen, etc., and the polymerization initiator (D) contains a biimidazole compound or an O-indenyl hydrazine compound.

The biimidazole compound is a dimer of an imidazole compound, and a compound represented by the formula (d6) is preferred.

[In the formula (d6), R ³ to R ⁸ represents a substituent having a carbon number of the aromatic group having 6 to 10].

Examples of the aromatic group having 6 to 10 carbon atoms include a phenyl group, a tolylmethyl group, a xylyl group, an ethylphenyl group, and a naphthyl group, and a phenyl group is preferred.

Examples of the substituent include a halogen atom and an alkoxy group having 1 to 4 carbon atoms. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and is preferably a chlorine atom. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like, and a methoxy group is preferred.

As the biimidazole compound, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 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-chloro Phenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxybenzene) Bismuthimide, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkyloxy) Phenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, see JPS 48-38403- B, JPS62-174204-A, etc.), an imidazole compound in which a phenyl group at the 4,4', 5, 5'-position is substituted with an alkoxycarbonyl group (for example, refer to JPH07-10913-A, etc.) and the like. Among them, a compound represented by the following formula or a mixture of the above is preferred.

The above O-indenyl ruthenium compound is a compound having a partial structure represented by the formula (d1), and is preferably a compound represented by the formula (d2).

[In the formula (d1), * represents a bond].

[In the formula (d2), R ^d1 represents a saturated hydrocarbon group having 1 to 12 carbon atoms.

R ^d2 represents a methyl group, a phenyl group or a benzyl group.

L ^d1 , indicating a single bond or -CO-.

R ^d3 represents a phenylthiophenyl group which may have a substituent, or a carbazolyl group which may have a substituent.

The saturated hydrocarbon group may, for example, be an alkyl group, an alicyclic saturated hydrocarbon group or a combination thereof.

Examples of the alkyl group include a linear alkyl group such as 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, a decyl group or a dodecyl group; and an isopropyl group; a branched chain alkyl group such as isobutyl, isopentyl, neopentyl or 2-ethylhexyl.

Examples of the alicyclic saturated hydrocarbon group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a tricyclodecyl group, an adamantyl group and the like.

Examples of the group to be combined include a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexylmethyl group, a cyclohexylethyl group, a methylcyclohexyl group, and the like.

Examples of the substituent which may have a phenylthiophenyl group and a carbazolyl group include an alkyl group having 1 to 6 carbon atoms, a benzamyl group having a saturated hydrocarbon group having 1 to 10 carbon atoms, and the alkyl group and The hydrogen atom contained in the saturated hydrocarbon group may also be substituted with a hydroxyl group, and the alkyl group and the methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom.

The alkyl group and the saturated hydrocarbon group may be the same as described above.

As such a substituent, the above alkyl group; 2-hydroxyethyl group, 2-hydroxyethoxy group, ethoxyethyl group; benzylidene group, 2-methylbenzylidene group, (3, 3-Dimethyl-2,4-dioxolylmethyloxy)benzhydryl group and the like.

The compound represented by the formula (d2) is preferably a compound represented by the formula (d3) or the formula (d4), more preferably a compound represented by the formula (d3).

In the formulae (d3) and (d4), R ^d1 and R ^{d2 have} the same meanings as described above.

R ^d4 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, the hydrogen atoms contained in the alkyl group may also be substituted by a hydroxyl group, the alkyl group may contain a methylene replaced by an oxygen atom.

R ^d5 represents a benzamyl group which may have a saturated hydrocarbon group of 1 to 10 carbon atoms, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and a hydrogen atom contained in the alkyl group and the saturated hydrocarbon group may also pass through a hydroxyl group. Alternatively, the alkyl group and the methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom.

R ^d5 represents an alkyl group having 1 to 6 carbon atoms].

The alkyl group and the saturated hydrocarbon group are the same as those described above.

Examples of the O-indenyl ruthenium compound include N-benzylideneoxy-1-(4-phenylthiophenyl)butan-1-one-2-imide and N-benzamide. Oxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzylideneoxy-1-(4-phenylthiophenyl)-3- Cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzylidene)-9H-indazol-3-yl Ethyl-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxa) Cyclopentyl methoxy)benzylidene}-9H-indazol-3-yl]ethane-1-imine, N-ethyloxy-1-[9-ethyl-6-(2 -Methylbenzylidene)-9H-indazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzylideneoxy-1-[9-ethyl-6-( 2-methylbenzhydryl)-9H-indazol-3-yl]-3-cyclopentylpropane An alkane-1-one-2-imine or the like; an O-mercaptopurine compound or the like described in JP2001-233842-A, JP2004-534797-A, or JP2011-132215-A. Commercial products such as Irgacure OXE 01, OXE02 (above, BASF) and N-1919 (made by Adeka) can also be used. Wherein the O-indenyl hydrazine compound is selected from the group consisting of N-benzylideneoxy-1-(4-phenylthiophenyl)butan-1-one-2-imine, N-benzyl hydrazine 1-(4-phenylthiophenyl)octane-1-one-2-imine and N-benzylideneoxy-1-(4-phenylthiophenyl)-3-cyclo Preferably, at least one of the group of pentylpropan-1-one-2-imine is N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one- 2-Amine is more preferred.

The polymerization initiator (D) may also contain a polymerization initiator other than the biimidazole compound or the O-mercaptopurine compound, as needed. Further, the sensitizer may be used together with the polymerization initiator (D) as needed.

The content of the polymerization initiator (D) is preferably from 0.1 to 30 parts by mass, more preferably from 1 to 20 parts by mass, per 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is within the above range, the generation of the release sheet in the developer after the formation of the colored pattern is small.

<thiol compound (T)>

The thiol compound (T) is a compound having -SH in the molecule.

Examples of the compound having one -SH in the molecule include, for example, a 2-fluorenyl group. Oxazole, 2-mercaptothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoene Azole, 2-mercaptonicotinic acid, 2-mercaptopyridine, 2-mercaptopyridine-3-ol, 2-mercaptopyridine-N-oxide, 4-amino-6-hydroxy-2-mercaptopyrimidine, 4-amine 6-hydroxy-2-mercaptopyrimidine, 4-amino-6-hydroxy-2-mercaptopyrimidine, 4-amino-2-mercaptopyrimidine, 6-amino-5-nitroso-2-thiourea Pyrimidine, 4,5-diamino-6-hydroxy-2-mercaptopyrimidine, 4,6-diamino-2-mercaptopyrimidine, 2,4-diamino-6-mercaptopyrimidine, 4,6-di Hydroxy-2-mercaptopyrimidine, 4,6-dimethyl-2-mercaptopyrimidine, 4-hydroxy-2-indolyl-6-methylpyrimidine, 4-hydroxy-2-indolyl-6-propylpyrimidine, 2- Mercapto-4-methylpyrimidine, 2-mercaptopyrimidine, 2-thiouracil, 3,4,5,6-tetrahydropyrimidin-2-thiol, 4,5-diphenylimidazole-2-thiol, 2-mercaptoimidazole, 2-mercapto-1-methylimidazole, 4-amino-3-indolyl-5-mercapto-1,2,4-triazole, 3-amino-5-mercapto-1,2 , 4-triazole, 2-methyl-4H-1,2,4-triazole-3-thiol, 4-methyl-4H-1,2,4-triazole-3-thiol, 3- Mercapto-1H-1,2,4-triazole-3-thiol, 2-amino-5-mercapto-1,3,4-thiadiazole, 5-amino-1,3,4-thiadi Oxazole-2-thiol, 2,5-dimercapto-1,3,4-thiadiazole, (furan-2-yl)methanethiol, 2-mercapto-5-thiazole , 2-mercaptothiazoline, 2-mercapto-4(3H)-quinazolinone, 1-phenyl-1H-tetrazole-5-thiol, 2-quinolinyl mercaptan, 2-mercapto-5-methyl Benzimidazole, 2-mercapto-5-nitrobenzimidazole, 6-amino-2-mercaptobenzothiazole, 5-chloro-2-mercaptobenzothiazole, 6-ethoxy-2-mercaptobenzene Thiazole, 6-nitro-2-mercaptobenzothiazole, 2-mercaptophthalimidazole, 2-nonylnaphthyl Oxazole, 3-mercapto-1,2,4-triazole, 4-amino-6-mercaptopyrazolo[2,4-d]pyridine, 2-amino-6-anthracenethiol, 6-mercaptopurine , 4-mercapto-1H-pyrazole [2,4-d]pyrimidine, and the like.

Examples of the compound having two or more -SH in the molecule include hexanedithiol, decanedithiol, 1,4-bis(methylindenyl)benzene, and butanediol bis(3-mercaptopropionic acid). Ester), butanediol bis(3-mercaptoacetate), ethylene glycol bis(3-mercaptoacetate), trimethylolpropane ginseng (3-mercaptoacetate), butanediol bis (3) - mercaptopropionate), trimethylolpropane ginseng (3-mercaptopropionate), trimethylolpropane ginseng (3-mercaptoacetate), pentaerythritol bismuth (3-mercaptopropionic acid) Ester), neopentyl quinone oxime (3-mercaptoacetate), hydroxyethyl ginseng (3-mercaptopropionate), neopentyl quinone oxime (3-mercaptobutyrate), 1,4-double (3-mercaptobutoxy)butane and the like.

As the thiol compound (T), a compound having one -SH in the molecule is preferred.

The content of the thiol compound (T) is preferably from 1 to 150 parts by mass, more preferably from 5 to 100 parts by mass, still more preferably from 8 to 70 parts by mass, per 100 parts by mass of the polymerization initiator (D). When the content of the thiol compound (T) is within this range, the sensitivity is high and the developability tends to be good.

<Solvent (E)>

The solvent (E) is not particularly limited, and a solvent generally used in the art can be used. For example, an ester solvent (a solvent containing -COO- in the molecule and a solvent containing no -O-), an ether solvent (a solvent containing -O- in the molecule, and a solvent containing no -COO-), an ether ester solvent (in the molecule) a solvent containing -COO- and -O-), a ketone solvent (a solvent containing -CO- in the molecule, a solvent containing no -COO-), an alcohol solvent (containing OH in the molecule, and containing no -O-, -CO) - and -COO-solvent), aromatic hydrocarbon solvent, 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 and γ-butyrolactone.

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, and diethyl ether. Glycol monoethyl ether, diethylene 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 ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, benzo Anisole, phenetole and methylanisole.

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- Methyl ethoxy-2-methylpropanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol Monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate And 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- Heptone, cycloheptanone, cyclohexanone, and isophorone.

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,N-methylpyrrolidone.

Among the above solvents, in terms of coatability and dryness, an organic solvent having a boiling point of 1 atm of 120 ° C or more and 180 ° C or less is preferred. As a solvent, 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, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone and N,N-dimethylformamide are preferred as propylene glycol monomethyl ether acetate Further, propylene glycol monomethyl ether, ethyl lactate and ethyl 3-ethoxypropionate are more preferred.

The content of the solvent (E) is preferably from 70 to 95% by mass, more preferably from 75 to 92% by mass, based on the total amount of the colored photosensitive resin composition of the present invention. In other words, the total amount of 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 in the above range, the flatness at the time of coating is improved, and the color density is not insufficient when the color filter is formed, so that the display characteristics tend to be good.

<Leveling agent (F)>

Examples of the leveling agent (F) include a silicone-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.

As a polyoxo-based surfactant, it can be mentioned that it has a ruthenium in a molecule. Surfactant such as oxyalkylene bond. Specifically, Toray Silicone DC3PA, the same series of SH7PA, the same series of DC11PA, the same series of SH21PA, the same series of SH28PA, the same series of SH29PA, the same series of SH30PA, the same series of SH8400 (trade name: East KL321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 ( Momentive Performance Materials Japan contract company) and so on.

The fluorine-based surfactant may, for example, be a surfactant having a fluorocarbon bond in a molecule. Specifically, Fluorad (registered trademark) FC430, FC431 of the same series (manufactured by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) F142D, F171 of the same series, F172 of the same series, F173 of the same series, and the same Series F177, F183 of the same series, F554 of the same series, R30 of the same series, RS-718-K of the same series (made by DIC Corporation); Eftop (registered trademark) EF301, EF303 of the same series, the same series EF351, the same series of EF352 (Mitsubishi Materials Electronics Co., Ltd.); Surflon (registered trademark) S381, the same series of S382, the same series of SC101, the same series of SC105 (made by Asahi Glass Co., Ltd.); and E5844 ( Daikin Fine Chemical Research Institute Co., Ltd.) and the like.

Examples of the polyfluorene-based surfactant having a fluorine atom include a surfactant having a decane bond and a fluorocarbon bond in the molecule. Specifically, it can be enumerated: Megafac (registered trademark) R08, the same Series BL20, F475 of the same series, F477 of the same series, and 443 of the same series (made by DIC Corporation).

The content of the leveling agent (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 still more preferably 0.01% by mass based on the total amount of the coloring photosensitive resin composition. % or more and 0.05% by mass or less. Further, the content of the above-mentioned pigment dispersant is not included in this content. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be good.

<Other ingredients>

The colored photosensitive resin composition of the present invention may contain a filler, another polymer compound, an adhesion promoter, an antioxidant, a photosetter, a chain transfer agent, etc., as needed, and is a well-known additive in this technical field.

<Method for Producing Colored Photosensitive Resin Composition>

The colored photosensitive resin composition of the present invention can be, for example, a mixed coloring agent (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E) which are used as needed. , a leveling agent (F), a polymerization initiator (D1), and other components are prepared.

The xanthene dye (A1) and the dye (A3) may be dissolved in a part or all of the solvent (E) in advance to prepare a solution. Preferably, the solution is preferably filtered through a filter having a pore diameter of about 0.01 to 1 μm.

The pigment (A2) is preferably partially or wholly mixed with one of the solvent (E) and dispersed in a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. At this time, part or all of the above-mentioned pigment dispersant and resin (B) may be blended as needed. In this way In the dispersion liquid, the remaining components are mixed so as to have a predetermined concentration, whereby the intended color-sensitive photosensitive resin composition can be prepared.

It is preferred to filter the mixed color-sensitive photosensitive resin composition with a filter having a pore diameter of about 0.01 to 10 μm.

<Method of Manufacturing Color Filter>

Examples of the method for producing a colored pattern from the colored photosensitive resin composition of the present invention include photolithography, a spray method, a printing method, and the like. Among them, photolithography is preferred. The photolithography method is a method in which the colored photosensitive resin composition is applied onto a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask to develop the composition. In the photolithography method, the colored coating film of the cured product of the colored composition layer can be formed without using a photomask during exposure and/or without development. The colored pattern or colored coating film formed in this manner is the color filter of the present invention.

The film thickness of the produced color filter is not particularly limited, and can be appropriately adjusted depending on the purpose and use, 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 alkali glass coated with ruthenium may be used; or polycarbonate, polymethyl methacrylate or polyparaphenylene A resin plate such as ethylene formate; a film of aluminum, silver, a silver/copper/palladium alloy, or the like formed on the substrate. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on the substrates.

By the formation of various color pixels by photolithography, it can be used Known or customary devices and conditions can be made, for example, in the following manner.

First, a colored photosensitive resin composition is applied onto a substrate, and dried by heating (prebaking) and/or drying under reduced pressure to remove volatile components such as a solvent and drying them to obtain a smooth colored resin composition layer. .

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

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

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

The film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected in accordance with the film thickness of the intended color filter.

Next, the colored composition layer is exposed through the photomask in order to form the intended color pattern. The pattern on the photomask is not particularly limited, and a pattern corresponding to the intended use is used.

The light source used for the exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light having a wavelength of less than 350 nm is blocked by a filter that blocks the wavelength band, and a band pass filter that emits light in a wavelength band of around 436 nm, around 408 nm, and around 365 nm may be used. Light of the same wavelength band is selectively released. Specifically, a mercury lamp, a light-emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned.

Because the entire surface of the exposure surface can be uniformly illuminated with parallel rays, and the light can be made Since the cover and the substrate on which the colored composition layer are formed are correctly aligned, it is preferable to use an exposure apparatus such as a mask-aligner and a stepper.

A colored pattern is formed on the substrate by bringing the exposed coloring composition layer into contact with the developing solution and developing it. By development, the unexposed portion of the colored composition layer is dissolved in the developer and 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 these basic compounds 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 contain a surfactant.

The developing method may be any one of a paddle immersion method, a dipping method, and a spray method. Moreover, the substrate can be tilted at an arbitrary angle during development.

After development, it is preferred to perform water washing.

Further, it is preferred to perform post-baking on the obtained colored pattern. The post-baking temperature is preferably 150 to 250 ° C, more preferably 160 to 235 ° C. The post-baking time is preferably from 1 to 120 minutes, more preferably from 10 to 60 minutes.

According to the colored photosensitive resin composition of the present invention, since the color filter can have a high yield particularly in the production of a color filter, the color filter is used as a display device (for example, a liquid crystal display device, an organic EL device, or an electron). Books, etc.) and color filters used in solid-state imaging devices.

(Example)

Hereinafter, the colored photosensitive resin composition of the present invention will be described in more detail based on examples.

In the example, "%" and "parts" are mass% and mass parts unless otherwise specified.

In the following synthesis examples, the compounds were identified by mass analysis (LC: Model 1200, manufactured by Agilent, Mass; LC/MSD type manufactured by Agilent).

[Synthesis Example 1]

20 parts of the compound of the formula (1x) and 200 parts of N-ethyl-o-toluidine (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed under light-shielding conditions, and the resulting solution was stirred at 110 ° C for 6 hours. After cooling the obtained reaction liquid to room temperature, it was added to a mixed liquid of 800 parts of water and 50 parts of 35% hydrochloric acid, and the mixture was stirred at room temperature for 1 hour to precipitate crystals. The precipitated crystal was taken as a residue for suction filtration, and dried to obtain 24 parts of the compound represented by the formula (1-24). The yield was 80%.

The same formula of the compound represented by formula (1-24): (mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ 603.4

Exact Mass: 602.2

[Synthesis Example 2]

In addition to using N-propyl-2,6-dimethylaniline instead of N-ethyl-ne-methyl Except for aniline, the same operation as in Synthesis Example 1 was carried out to obtain a compound represented by the formula (1-32).

Identification of the compound of formula (1-32): (mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ 659.9

Exact quality: 658.9

[Synthesis Example 3]

In a flask equipped with a cooling tube and a stirring device, a mixture of a compound represented by the formula (A0-1) and a compound represented by the formula (A0-2) (trade name: Chugai Aminol Fast Pink R; manufactured by a Chinese company) 15 A portion, chloroform (150 parts) and N,N-diethylformamide (8.9 parts) were added dropwise to a solution of 10.9 parts of sulfinium chloride while maintaining the temperature at 20 ° C or lower while stirring. After the completion of the dropwise addition, the temperature was raised to 50 ° C, and the reaction was maintained at the same temperature for 5 hours, followed by cooling to 20 ° C. The cooled reaction solution was stirred and maintained at 20 ° C or lower, and a mixture of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise. Thereafter, the mixture was stirred at the same temperature for 5 hours to cause a reaction. Thereafter, the obtained reaction mixture was distilled off with a rotary evaporator, and then a small amount of methanol was added and stirred vigorously. This mixture was added to a mixed liquid of 375 parts of ion-exchanged water while stirring to precipitate crystals. The precipitated crystal was filtered, washed thoroughly with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain 11.3 parts of xanthene dye 1 [formula (Aa-1-1) to formula (Aa-1-8) Show a mixture of compounds].

[Synthesis Example 4]

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen was introduced in an appropriate amount to replace nitrogen gas, and 371 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 85 ° C while stirring. Next, 54 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]癸-8-yl acrylate and 3,4-epoxytricyclo[?.1.0 ^2.6 ]癸-9- a mixture of base esters (containing a molar ratio of 50:50) of 225 parts, and it takes 4 hours to prepare a solution of 81 parts of vinyl toluene (isomer mixture) dissolved in 80 parts of propylene glycol monomethyl ether acetate. The mixed solution was dropped into the flask.

On the other hand, a solution in which 30 parts of the polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) was dissolved in 160 parts of propylene glycol monomethyl ether acetate was dropped over 5 hours. After completion of the dropwise addition of the polymerization initiator solution, the mixture was kept at 85 ° C for 4 hours, and then cooled to room temperature to obtain a resin B1 (copolymer) solution. The solid content of the resin B1 solution was 37.5%, and the viscosity measured by the B type viscosity meter (23 ° C) was 246 mPa. s. The weight average molecular weight of the resin B1 was 1.06 × 10 ⁴ , the molecular weight distribution was 2.01, and the acid value in terms of solid content was 115 mg-KOH/g. The resin B1 has the following structural unit.

[Synthesis Example 5]

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was introduced at 0.02 L/min to replace the nitrogen atmosphere, and 200 parts of 3-methoxy-1-butanol and 3-methoxyacetic acid were charged. 105 parts of butyl ester was heated to 70 ° C while stirring. Next, 60 parts of methacrylic acid and 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate, ie, acrylic acid 3, 4, are dissolved in 140 parts of 3-methoxybutyl acetate. a mixture of epoxycyclotricyclo[5.2.1.0 ^2.6 ]decane-8-yl ester and 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decane-9-yl acrylate (containing molar ratio) 50:50) 240 parts, to prepare a solution, and the solution was dropped into a flask kept at 70 ° C for 4 hours using a dropping funnel.

On the other hand, a solution of 30 parts of a polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 225 parts of 3-methoxybutyl acetate, and other solutions were used. The funnel took 4 hours to drip into the flask. 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 resin B 2 (copolymer) solution having a solid content of 33% by mass. The weight average molecular weight of the resin B2 was 1.3 × 10 ⁴ , the molecular weight distribution was 2.5, and the acid value in terms of solid content was 103 mg-KOH/g. The resin B2 has the following structural unit.

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in the synthesis example was carried out under the following conditions using a GPC method.

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 materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by TOSOH Co., Ltd.)

The ratio (Mw/Mn) of the weight average molecular weight and the number average molecular weight of the converted polystyrene obtained above was defined as a molecular weight distribution.

Examples 1 to 8 and Comparative Example 1

(Modulation of coloring photosensitive resin composition)

The components of the composition shown in Tables 1 and 2 were mixed to obtain a colored photosensitive resin composition.

In Tables 1 and 2, "A2-1" is described in the column of "propylene glycol monomethyl ether acetate and "E-2 ²⁾ " in the column of "acrylic pigment dispersant and "E-1 ²⁾ ". The amount of propylene glycol monomethyl ether is mixed and pre-dispersed.

The column "E-1 ¹⁾ " indicates the total content of propylene glycol monomethyl ether acetate, and the column "E-2 ¹⁾ indicates the total amount of propylene glycol monomethyl ether.

In Tables 1 and 2, each component represents the following. The resin (B) is a content (parts) indicating a solid content conversion.

Colorant (A): A1-1; a compound represented by formula (1-32)

Colorant (A): A1-2; xanthene dye 1

Colorant (A): A2-1; C.I. Pigment Blue 15:6 (pigment)

Coloring agent (A): A3-1; C.I. direct blue (C.I. direct blue) 264 and dodecylbenzenesulfonic acid salt (Orient Chemical Industry Co., Ltd.) (anthraquinone dye)

Resin (B): B-1; Resin B1

Resin (B): B-2; Resin B2

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

Polymerization initiator (D): D-1; a mixture of compounds represented by the following formula (CHEMCURE-TCDM; manufactured by Cambridge; biimidazole compound)

Polymerization initiator (D): D-2; N-benzylideneoxy-1-(4-phenylmercaptophenyl)octane-1-one-2-imine (IRGACURE (registered trademark) OXE01; BASF company)

Thiol compound (T): 2-mercaptobenzothiazole (Sanceler (registered trademark) M; Sanshin Chemical Industry Co., Ltd.)

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

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

Solvent (E): E-3; ethyl lactate

Solvent (E): E-4; 3-methoxy-1-butanol

Solvent (E): E-5; 3-methoxybutyl acetate

Leveling agent (F): Polyether modified polyoxygenated oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)

<Production of Coloring Patterns>

The colored photosensitive resin composition was applied by a spin coating method on a glass substrate (Eagle 2000; manufactured by Corning Incorporated) of 5 cm square, and then prebaked at 100 ° C for 3 minutes to form a colored composition layer. After cooling, the distance between the substrate on which the colored composition layer was formed and the mask made of quartz glass was set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcone Co., Ltd.) was used, and in an atmosphere, 60 mJ/cm. The exposure amount of ² (365 nm reference) was illuminated. As the reticle, a line and space pattern in which 100 μm is formed is used. The colored composition layer after the light irradiation was immersed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 26 ° C for 60 seconds to be developed, and after washing with water, it was baked. Post-baking at 230 ° C for 20 minutes in the oven gave a colored pattern.

<Thickness evaluation>

The film thickness of the obtained coloring pattern was measured using a film thickness measuring device (DEKTAK 3; manufactured by Nippon Vacuum Technology Co., Ltd.).

<Color Evaluation>

Regarding the obtained color pattern, the spectroscopic measurement was performed using a color measuring machine (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the xy chromaticity coordinate in the XYZ color system of CIE was measured using the characteristic coefficient of the C light source. (x, y) and tristimulus value Y. The larger the value of Y, the higher the brightness. The results are shown in Table 2.

<Observation of peeling sheet>

The developed developer was visually observed for the colored pattern produced. In the developing solution, the peeling sheet derived from the coloring photosensitive resin composition was confirmed to be ○ when it was not confirmed, and the case where the peeling sheet was confirmed was regarded as X. When it is confirmed that the release sheet derived from the coloring photosensitive resin composition is present in the developer, the impurities adhering to the pattern may cause defects in the pattern, which is not preferable. The results are shown in Table 3.

Example 9

The same procedure as in Example 1 was carried out except that the compound of the formula (1-24) was used instead of the compound of the formula (1-3) to obtain a colored photosensitive resin composition, and the same operation as above was carried out. It is possible to obtain a high-brightness coloring pattern in which a peeling sheet does not occur in the developer.

Example 10

The same procedure as in Example 6 was carried out except that the compound of the formula (1-24) was used instead of the compound of the formula (1-3), and a colored photosensitive resin composition was obtained, which was carried out in the same manner as above. In the operation, a release sheet is not generated in the developer, and a high-brightness coloring pattern can be obtained.

From the above results, it is understood that, in the case of the colored photosensitive resin composition of the present invention, it is confirmed that the release sheet is not formed in the developer after development. Moreover, it was confirmed that the color pattern produced by the colored photosensitive resin composition of the present invention has high brightness. Thus, according to the colored photosensitive resin composition of the present invention, a color filter excellent in brightness can be produced 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.

Claims (6)

A colored photosensitive resin composition containing a colorant, a resin, a polymerizable compound, a polymerization initiator, and a thiol compound; the colorant contains a xanthene dye and a pigment, and the polymerization initiator contains a biimidazole compound Or an O-indenyl compound. The colored photosensitive resin composition according to claim 1, wherein the xanthene dye contains a compound represented by the formula (1a), [In the formula (1a), R ¹ to R ⁴ are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a carbon number 6 to 10 which may have a substituent. a valent aromatic hydrocarbon group, the -CH ₂ - contained in the saturated hydrocarbon group may also be substituted by -O-, -CO- or -NR ¹¹ -; R ¹ and R ² may also form a ring together with the adjacent nitrogen atom, and R ³ and R ⁴ may form a ring together with an adjacent nitrogen atom, and 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 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; m represents 0 to An integer of 5, when m is 2 or more, a plurality of R ⁵ may be the same or different, a represents an integer of 0 or 1, X represents a halogen atom, and Z ⁺ represents ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ , 4 R ¹¹ may be the same or different; R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom; R ⁹ and R ¹⁰ Is a self-independent, representing a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, The -CH ₂ - contained in the saturated aliphatic hydrocarbon group may also be substituted by -O-, -CO-, -NH- or -NR ⁸ -; R ⁹ and R ¹⁰ may also form together with the bonded adjacent nitrogen atom. A nitrogen-containing heterocyclic ring to 10 members; R ¹¹ 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. The colored photosensitive resin composition according to claim 1 or 2, wherein the polymerization initiator contains a biimidazole compound. The colored photosensitive resin composition according to claim 1 or 2, wherein the polymerization initiator contains an O-mercaptopurine compound. A color filter formed of the colored photosensitive resin composition according to any one of claims 1 to 4. A display device comprising the color filter of claim 5 of the patent application.