TWI575312B - Coloring the photosensitive resin composition - Google Patents

Description

Colored photosensitive resin composition

The present invention relates to a colored photosensitive resin composition.

The colored photosensitive resin composition is a color filter used for manufacturing a display device such as a liquid crystal display panel, an electroluminescence panel, or a plasma display panel. Japanese Patent Publication No. Hei 10-31308 discloses a copolymer containing a pigment, an N-substituted maleimide and a monomer having an acid group, a photopolymerizable compound, a photopolymerization initiator, and A colored photosensitive resin composition of a solvent. Further, Japanese Laid-Open Patent Publication No. 2010-32999 discloses that a copolymer containing a xanthene dye and a resin is a copolymer of a monomethyl acrylate and a methacrylic acid having a benzyl methacrylate or a tricyclodecane skeleton. A composition of a resin obtained by adding glycidyl methacrylate.

A photolithography method is known in terms of a method of forming a pattern by using a colored photosensitive resin composition. The photolithography method is a method in which a colored photosensitive resin composition is applied onto a substrate and exposed and developed through a photomask to obtain a pattern. In the photolithography method, a part of the unexposed portion of the colored photosensitive resin composition layer is peeled off during development, and the release sheet is a foreign matter on the pattern.

The present invention provides the following [1] to [11].

[1] A colored photosensitive resin composition, which system contains a colorant, a resin, a photopolymerizable compound and a colorant, the resin-based photopolymerization initiator dye, wherein the xanthene-based colorant (xanthene) having from At least one structural unit selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride and N-cyclohexylmaleimide from N-cyclohexylmaleimide ) of the structural unit of the resulting copolymer.

[2] The colored photosensitive resin composition according to [1], wherein the xanthene dye is a compound represented by the formula (1), In the formula, R ¹ to R ⁴ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and a hydrogen atom contained in the aromatic hydrocarbon group. It may be a halogen atom, -R ⁸ , -OH, -OR ⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- M ⁺ , -CO ₂ H, -CO ₂ ^- M ⁺ , -CO ₂ R ⁸ , -SR ⁸ , -SO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ is substituted. The hydrogen atom contained in the saturated hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 3 carbon atoms. The -CH ₂ - contained in the aforementioned saturated hydrocarbon group may be substituted with -O-, -CO- or -NR ¹¹ -. R ¹ and R ² may together form a ring containing a nitrogen atom, and R ³ and R ⁴ may together form a ring containing a nitrogen atom.

R ⁵ represents -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- M ⁺ , -CO ₂ H, -CO ₂ ^- M ⁺ , -CO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ .

m represents an integer from 0 to 5. When m is 2 or more, plural R ^{5 's} may be the same or different.

R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

M ⁺ represents ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ .

X represents a halogen atom.

a represents an integer of 0 or 1.

R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.

R ¹¹ each independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms.

R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a hydroxyl group or a halogen atom, and the saturated aliphatic hydrocarbon group The -CH ₂ -system may be substituted by -O-, -CO-, -NH- or -NR ⁸ -, and R ⁹ and R ¹⁰ may be bonded to each other to form a heterocyclic ring of 3 to 10 members containing a nitrogen atom. ring. ].

[3] The colored photosensitive resin composition according to [1], wherein the xanthene dye is a compound represented by the formula (2). [wherein R ²¹ to R ²⁴ each independently represent a hydrogen atom, -R ²⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be -SO ₃ ^- , -SO ₃ ^- M ^a+ , -SO ₃ H, -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ is substituted.

X ^a represents a halogen atom.

a ¹ represents an integer of 0 or 1.

M1 represents an integer from 0 to 5. When m1 is 2 or more, the plural R ²⁵ may be the same or different.

M ^a+ represents ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ .

R ²⁵ represents -SO ₃ ^- , -SO ₃ ^- M ^a+ , -SO ₃ H or SO ₂ NHR ²⁶ .

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

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

[4] The colored photosensitive resin composition according to [1], wherein the xanthene dye is a compound represented by the formula (3). In the formula (3), R ³¹ and R ³² each independently represent an alkyl group having 1 to 10 carbon atoms. R ³³ and R ³⁴ each independently represent an alkyl group having 1 to 4 carbon atoms, an alkylsulfonyl group having 1 to 4 carbon atoms or an alkylsulfonyl group having 1 to 4 carbon atoms. R ³¹ and R ³³ may together form a ring containing a nitrogen atom, and R ³² and R ³⁴ may be taken together to form a ring containing a nitrogen atom.

p and q independently represent an integer from 0 to 5. When p is 2 or more, the plural R ³³ may be the same or different, and when q is 2 or more, the plural R ³⁴ may be the same or different. ].

[5] The colored photosensitive resin composition according to [1], wherein the xanthene dye is a mixture of the compounds represented by the formula (A1-1) to the formula (A1-8),

[6] The colored photosensitive resin composition according to any one of [1] to [5] wherein the resin is a structure derived from acrylic acid or methacrylic acid. Unit, a structural unit derived from N-cyclohexylmethyleneimine and a copolymer derived from a structural unit of acrylate or methacrylate.

[7] The colored photosensitive resin composition according to any one of [1], wherein a content ratio of a structural unit derived from N-cyclohexylmethyleneimine in the copolymer is relatively The total structural unit of the copolymer is 35 mol% or more.

[8] The colored photosensitive resin composition according to any one of [1] to [7] wherein the coloring agent is a coloring agent further containing a pigment.

[9] The colored photosensitive resin composition according to any one of [1] to [8] wherein the content of the xanthene dye is 0.1 to 50 with respect to the content of the solid content of the colored photosensitive resin composition. quality%.

[10] A color filter formed by the colored photosensitive resin composition according to any one of [1] to [9].

[11] A display device comprising the color filter according to [10].

When the coloring photosensitive resin composition of the present invention is suitable for use in the photolithography method, it is possible to prevent a part of the unexposed portion of the colored photosensitive resin composition layer from being peeled off during development, so that the formed pattern has less foreign matter. .

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

The coloring photosensitive resin composition of the present invention contains a coloring agent (A), a resin (B), a photopolymerizable compound (C), and a photopolymerization initiator (D), and wherein the coloring agent (A) contains a coloring agent for xanthene dye (A1), the resin (B) having a group selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides a copolymer of at least one structural unit and a structural unit derived from N-cyclohexylmethyleneimine.

The colored photosensitive resin composition of the present invention contains a coloring agent (A), and the coloring agent (A) is a coloring agent containing a xanthene dye (A1).

Xanthene dye (A1) is a dye containing a compound having a xanthene skeleton.

In the case of xanthene dye (A1), it is preferably red or purple xanthene dye, for example, CI acid red 51, 52, 87, 92, 289, 388, CI acid violet 9, 30, CI alkaline red 8 , CI dying red 27, Bengal rose B, sulfonium rhodamine G, rhodamine 6G, Japanese Patent Publication No. 2010-32999, and the xanthene dyes described in Japanese Patent No. 4492760.

Among them, in the case of the xanthene dye (A1), a dye containing a compound represented by the formula (1) (hereinafter referred to as "compound (1)") is preferred. Compound (1) may also be a tautomer thereof. When the compound (1) is used, the content of the compound (1) in the xanthene dye (A1) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more. In particular, in the case of the xanthene dye (A), it is preferred to use only the compound (1).

In the formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and are contained in the aromatic hydrocarbon group. The hydrogen atom may be a halogen atom, -R ⁸ , -OH, -OR ⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- M ⁺ , -CO ₂ H, -CO ₂ ^- M ⁺ , -CO ₂ R ⁸ , -SR ⁸ , -SO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ are substituted. The hydrogen atom contained in the saturated hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 3 carbon atoms. The -CH ₂ - contained in the aforementioned saturated hydrocarbon group may be substituted with -O-, -CO- or -NR ¹¹ -. R ¹ and R ² may together form a ring containing a nitrogen atom, and R ³ and R ⁴ may together form a ring containing a nitrogen atom.

R ⁵ represents -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- M ⁺ , -CO ₂ H, -CO ₂ ^- M ⁺ , -CO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ .

m represents an integer from 0 to 5. When m is 2 or more, plural R ^{5 's} may be the same or different.

R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

M ⁺ represents ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ .

X represents a halogen atom.

a represents an integer of 0 or 1.

R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.

R ¹¹ each independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms.

R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a hydroxyl group or a halogen atom, and the saturated aliphatic hydrocarbon group The -CH ₂ -system may be substituted by -O-, -CO-, -NH- or -NR ⁸ -, and R ⁹ and R ¹⁰ may be bonded to each other to form a heterocyclic ring of 3 to 10 members containing a nitrogen atom. ring. ].

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ to R ⁴ include a phenyl group, a tolyl group, a xylyl group, a trimethylphenyl group, a propylphenyl group, and a butylphenyl group.

The monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ to R ⁴ has a substituent of -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- M ⁺ and -SO ₂ NR ^{9 .} At least one selected from the group consisting of R ¹⁰ is preferable, and at least one selected from the group consisting of -SO ₃ ^- M ⁺ and -SO ₂ NR ⁹ R ¹⁰ is more preferable. In the case of -SO ₃ ^- M ⁺ at this time, -SO ₃ ^-+ N(R ¹¹ ) _{4 is} preferred. When R ¹ to R ^{4 are used} as such a base, the amount of foreign matter generated from the colored photosensitive resin composition of the present invention containing the compound (1) is small, and a coating film or pattern excellent in heat resistance can be formed.

The ring formed by the combination of R ¹ and R ² and the ring formed by R ³ and R ⁴ may, for example, be as follows.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ⁸ to R ¹¹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, and a new one. Alkyl group having 1 to 20 carbon atoms such as pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, decyl, decyl, dodecyl, hexadecanyl, and hexyl; cyclopropyl, cyclo An alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a pentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group or a tricyclic fluorenyl group.

Examples of -OR ⁸ include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy And icosyloxy and the like.

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

Examples of the SR- ⁸ include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and a decylsulfonyl group.

Examples of the -SO ₂ R ⁸ group include a methyl fluorenyl group, an ethyl fluorenyl group, a butyl fluorenyl group, a hexyl fluorenyl group, a fluorenyl fluorenyl group, and a decyl fluorenyl group.

Examples of the -SO ₃ R ⁸ group include a methoxy fluorenyl group, an ethoxylated fluorenyl group, a propoxy fluorenyl group, a tert-butoxy fluorenyl group, a hexyloxy fluorenyl group, and a hexyloxy fluorenyl group. .

The term -SO ₂ NR ⁹ R ¹⁰ may, for example, be an amine sulfonyl group; and

N-methylamine sulfonyl, N-ethylamine sulfonyl, N-propylamine sulfonyl, N-isopropylamine sulfonyl, N-butylamine sulfonyl, N-isobutyl Amine sulfonyl, N-sec-butylamine sulfonyl, N-tert-butylamine sulfonyl, N-pentylamine sulfonyl, N-(1-ethylpropyl)amine sulfonate , N-(1,1-dimethylpropyl)amine sulfonyl, N-(1,2-dimethylpropyl)amine sulfonyl, N-(2,2-dimethylpropyl Aminesulfonyl, N-(1-methylbutyl)aminesulfonyl, N-(2-methylbutyl)aminesulfonyl, N-(3-methylbutyl)aminesulfonyl , N-cyclopentylamine sulfonyl, N-hexylamine sulfonyl, N-(1,3-dimethylbutyl)amine sulfonyl, N-(3,3-dimethylbutyl) Aminesulfonyl, N-heptylaminesulfonyl, N-(1-methylhexyl)aminesulfonyl, N-(1,4-dimethylpentyl)aminesulfonyl, N-octyl Aminesulfonyl, N-(2-ethylhexyl)aminesulfonyl, N-(1,5-dimethyl)hexylaminesulfonyl, N-(1,1,2,2-tetramethyl N-1 of butyl)amine sulfonyl group N,N-dimethylamine sulfonyl, N,N-ethylmethylamine sulfonyl, N,N-diethylamine sulfonyl, N,N-propyl Amine sulfonyl, N,N-isopropylmethylamine sulfonyl, N,N-tert-butylmethylamine sulfonyl, N,N-butylethylamine sulfonyl, N,N- An N,N-2 substituted amine sulfonyl group such as bis(1-methylpropyl)amine sulfonyl group or N,N-heptylmethylamine sulfonyl group.

Further, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ⁹ and R ¹⁰ may be a hydrogen atom contained in the saturated hydrocarbon group which may be substituted with -OH or a halogen atom, and -CH ₂ contained in the saturated hydrocarbon group The system may be substituted with -O-, -CO-, -NH- or -NR ⁸ -.

R ⁹ and R ¹⁰ may be bonded to each other to form a heterocyclic ring having a 3 to 10 membered ring of a nitrogen atom. Examples of the heterocyclic ring include the following.

R ⁵ is preferably -CO ₂ H, -CO ₂ R ⁸ , -SO ₃ ^- , -SO ₃ ^- M ⁺ , -SO ₃ H or SO ₂ NHR ⁹ , SO ₃ ^- , -SO ₃ ^- M ⁺ , -SO ₃ H or SO ₂ NHR ^{9 is} better.

The m system is preferably 1 to 4, more preferably 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.

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

^{In the case of +} 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. When ⁺ N(R ¹¹ ) ₄ is present in the compound (1), if R ¹¹ is a group such as the above, the colored photosensitive resin composition of the present invention containing the compound (1) can form a coating film or a pattern having a small foreign matter. type.

The compound (1) is preferably a compound represented by the formula (2) (hereinafter referred to as "compound (2)"), and a dye containing the compound (2) is more preferable. Compound (2) may also be a tautomer thereof. When the compound (2) is used, the content of the compound (2) in the xanthene dye (A1) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more. In particular, in the case of the xanthene dye (A1), it is preferred to use only the compound (2).

In the formula (2), R ²¹ to R ²⁴ each independently represent a hydrogen atom, -R ²⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be -SO ₃ ^- , -SO ₃ ^- M ^a+ , -SO ₃ H, -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ are substituted.

X ^a represents a halogen atom.

a ¹ represents an integer of 0 or 1.

M1 represents an integer from 0 to 5. When m1 is 2 or more, the plural R ²⁵ may be the same or different.

M ^a+ represents ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ .

R ²⁵ represents -SO ₃ ^- , -SO ₃ ^- M ^a+ , -SO ₃ H or SO ₂ NHR ²⁶ .

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

R ²⁷ each independently represents a monovalent saturated hydrocarbon group or a benzyl group having 1 to 20 carbon atoms. 〕

^Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ²¹ to R ²⁴ include the same groups as those exemplified as the aromatic hydrocarbon group in R ¹ to R ⁴ .

In the combination of R ²¹ to R ²⁴ , R ²¹ and R ²³ are preferably a hydrogen atom, and R ²² and R ²⁴ are a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the aromatic hydrocarbon group is contained in the aromatic hydrocarbon group. The hydrogen atom contained may also be substituted with -SO ₃ ^- , -SO ₃ ^- M ⁺ , -SO ₃ H, -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ . 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 contained in the aromatic hydrocarbon group may be -SO ₃ ^- M ⁺ or -SO ₂ NHR ²⁶ replaced. When R ²¹ to R ^{24 are used} as such a base, a colored photosensitive resin composition of the present invention containing the compound (2) can form a coating film or a pattern excellent in heat resistance.

^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 of the saturated hydrocarbon group in R ⁸ to R ¹¹ .

When R ²¹ to R ²⁴ are -R ²⁶ , it is preferred that -R ²⁶ each independently represents a hydrogen atom, a methyl group or an ethyl group.

-SO ₃ R ²⁶ and -SO ₂ In the R ²⁶ aspect of NHR ²⁶ , a branched chain alkyl group having 3 to 20 carbon atoms is preferred, and a branched chain alkyl group having 6 to 12 carbon atoms is preferred, 2-B. The base is even better. When R ^{26 is used} as a base, the coloring photosensitive resin composition containing the compound (2) can form a coating film or pattern having little foreign matter.

M ^a+ is ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ²⁷ ) ₄ .

^{In the case of +} N(R ²⁷ ) ₄ , among the four R ²⁷ , at least two monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms are preferred. Further, the total carbon number of the four R ²⁷ is preferably from 20 to 80, more preferably from 20 to 60. When ⁺ N(R ²⁷ ) ₄ is present in the compound (2), the coloring photosensitive resin composition of the present invention containing the compound (2) having R ²⁷ or the like can form a coating film or a pattern with less foreign matter generation. type.

The compound (1) may, for example, be a compound represented by the formula (1-1) to the formula (1-30). Further, in the following formula, Ra represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched chain alkyl group having 6 to 12 carbon atoms, and more preferably 2-ethylhexyl group. Among these, a sulfonated guanamine of CI Acid Red 289, a 4-grade ammonium salt of CI Acid Red 289, a sulfonated sulfonamide of CI Acid Violet 102, or a 4-grade ammonium salt of CI Acid Violet 102 are mentioned. good. Examples of such a compound include a compound represented by the formula (1-1) to the formula (1-8), the formula (1-11) or the formula (1-12).

Further, in the case of the xanthene dye (A1), a dye containing a compound represented by the formula (3) (hereinafter referred to as "compound (3)") is also preferable. Compound (3) may also be a tautomer thereof. When the compound (3) is used, the content of the compound (3) in the xanthene dye (A1) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more.

In the formula (3), R ³¹ and R ³² each independently represent an alkyl group having 1 to 10 carbon atoms. R ³³ and R ³⁴ each independently represent an alkyl group having 1 to 4 carbon atoms, an alkylsulfonyl group having 1 to 4 carbon atoms or an alkylsulfonyl group having 1 to 4 carbon atoms. R ³¹ and R ³³ may together form a ring containing a nitrogen atom, and R ³² and R ³⁴ may be taken together to form a ring containing a nitrogen atom.

p and q independently represent an integer from 0 to 5. When p is 2 or more, the plural R ³³ may be the same or different, and when q is 2 or more, the plural R ³⁴ may be the same or different. 〕

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ³¹ and R ³² include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. , hexyl, 2-ethylhexyl, fluorenyl, fluorenyl and the like. In the case of the alkyl group having 1 to 4 carbon atoms represented by R ³³ and R ³⁴ , among these, a group having a carbon number of 4 can be given.

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

Examples of the alkyl fluorenyl group having 1 to 4 carbon atoms represented by R ³³ and R ³⁴ include a methyl fluorenyl group, an ethyl fluorenyl group, a propyl fluorenyl group, a butyl fluorenyl group, and an isopropyl fluorenyl group.

R ³¹ and R ³² each independently represent a methyl group, an ethyl group, a propyl group or an isopropyl group. R ³³ and R ³⁴ are preferably those having an alkyl group having 1 to 4 carbon atoms, more preferably those having a methyl group.

p and q independently represent each other as an integer of 0 to 2, preferably 1 or 2.

In the case of the compound (3), for example, a compound represented by the formula (1-31) to the formula (1-43) can be used. Among them, a compound represented by the formula (1-31) to the formula (1-40) is preferred because it has excellent solubility in an organic solvent.

For the xanthene dye (A1), a commercially available xanthene dye (for example, "Chugai Aminol Fast Pink RH/C" manufactured by Sino-foreign Chemical Co., Ltd., "Rhodamin 6G" manufactured by Tajika Chemical Industry Co., Ltd., etc.) can be used. . In addition, the commercially available xanthene dye is used as a starting material, and it can be synthesized by referring to Japanese Patent Laid-Open Publication No. 2010-32999.

The content of xanthene dye (A1) is fixed to the coloring photosensitive resin composition The content of the component is preferably 0.1 to 50% by mass, more preferably 0.1 to 30% by mass, still more preferably 0.1 to 20% by mass, particularly preferably 0.1 to 10% by mass. By containing the xanthene dye (A1) in the above-mentioned content, the coloring photosensitive resin composition excellent in developability is obtained. Here, the solid content in the present specification means the total amount of components obtained by removing the solvent from the colored photosensitive resin composition of the present invention. The solid content and the content of each component can be measured, for example, by a known analytical method such as liquid chromatography or gas chromatography.

The coloring agent (A) may contain a dye other than the xanthene dye (A1) (hereinafter referred to as "dye (A3)") and a xanthene dye (A1). Dye (A3) is not particularly limited aspect, known dyes can be used, such as solvent may be for example a dye (solvent dye), an acid dye (acid dye), direct dyes (direct dye), the dye mordant (mordant dye) and the like. Among them, organic solvent-soluble dyes are preferred.

As the dye (A3), for example, a color index (published by The Society of Dyers and Colourists) is classified as a compound having a hue other than a colorant, or a known dye described in a dyeing note (color dyeing company).

Specific examples of the solvent dye include CI Solvent Yellow 4 (hereinafter, the description of CI Solvent Yellow is omitted, only the number thereof is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94. , 98, 99, 162; CI solvent red 45, 49, 125, 130; CI solvent orange 2, 7, 11, 15, 26, 56; CI solvent blue 35, 37, 59, 67; CI solvent green 1, 3 , 4, 5, 7, 28, 29, 32, 33, 34, 35 In terms of acid dyes, CI acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76 , 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169 , 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240 , 242, 243, 251; CI acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 57, 66, 73, 80, 88, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426; CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 10 7, 108, 169, 173; CI Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87 , 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290 , 296, 315, 324: 1, 335, 340; CI Acid Violet 6B, 7, 17, 19; CI Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, etc., direct dyes , can be cited as CI direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141; CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179 ,181,182,184,204,207,211,213,218,220,221,222,232,233,234,241,243,246,250; CI direct orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI Direct Blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97 , 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163 , 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 2 28,229,237,238,242,243,244,245,247,248,250,251,252,256,257,259,260,268,274,275,293; CI Direct Violet 47, 52, 54 , 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; CI direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc., in the mordant dyes, there are CI mordant dyes, such as CI 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; CI mordant red 1, 2, 3, 4, 9, 11, 12 , 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71 , 74, 85, 86, 88, 90, 94, 95; CI mordant orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; CI mordant blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30 , 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84; CI mordant purple 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58; CI mord green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35 , 41, 43, 53 and so on.

These dyes may be appropriately selected in accordance with the spectral spectrum of the desired color filter. These dyes may be used singly or in combination of two or more.

The coloring agent (A) contained in the colored photosensitive resin composition of the present invention may preferably contain the pigment (A2).

In terms of pigment (A2), specifically, a color index (The A compound classified as a colorant in the Society of Dyers and Colourists. Specifically, for example, CI color yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125 Yellow pigments of 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214, etc.; CI color oranges 13, 31, 36, 38, 40, 42, 43, 51 Orange pigments of 55, 59, 61, 64, 65, 71, 73; CI pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, Red pigments of 209, 215, 216, 224, 242, 254, 255, 264, 265, etc.; blue pigments of CI color blue 15, 15:3, 15:4, 15:6, 60, etc.; CI colorant Purple pigments of purple 1, 19, 23, 29, 32, 36, 38; green pigments of CI pigments green 7, 36, 58; brown pigments of CI pigments brown 23, 25, etc.; , 7 black pigments, etc.

Among them, CI color yellow 138, 139, 150, CI color red 177, 209, 242, 254, CI color purple 23, CI color blue 15:3, 15:6 and CI color green 7,36 58 is better. These pigments may be used singly or in combination of two or more.

The above-mentioned pigment is preferably subjected to dispersion treatment in the presence of a dispersing agent, and is preferably used after the pigment dispersion liquid in which the pigment is uniformly dispersed in a solvent. Examples of the dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine. The dispersing agent may be used singly or in combination of two or more.

Examples of the dispersant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, and tertiary amines. Modified polyurethanes, polyethyleneimine, etc., other trade names KP (Shin-Etsu Chemical Co., Ltd.), Floren (Kyoei Chemical Co., Ltd.), Solsperse (Zeneca) )), EFKA (manufactured by CIBA Co., Ltd.), Disperbyk (manufactured by BYK Co., Ltd.), and AJISPER (Ajinomoto Fine-Techno Co., Ltd.).

When the amount of the pigment (A2) is 100 parts by mass, it is preferably 0.1 to 100 parts by mass, more preferably 5 to 50 parts by mass. When the amount of the dispersant used is in the above range, it is preferred because a uniform dispersion liquid tends to be obtained.

When the colorant (A) contains the xanthene dye (A1) and the pigment (A2), the content of the xanthene dye (A1) and the pigment (A2) is preferably in the following range for the colorant (A).

Xanthene dye (A1); 1 to 50% by mass (more preferably 1 to 40% by mass, still more preferably 1 to 30% by mass)

Pigment (A2); 50 to 99% by mass (more preferably 60 to 99% by mass, still more preferably 70 to 99% by mass)

When the content of the xanthene dye (A1) and the pigment (A2) is within the above range, the obtained color filter is excellent in contrast, lightness, heat resistance, and chemical resistance.

Further, when the coloring agent (A) contains a xanthene dye (A1), a dye (A3), and a pigment (A2), the content of the coloring agent (A) is preferably in the following range.

Xanthene dye (A1); 1 to 50% by mass (more preferably 1 to 40% by mass, still more preferably 1 to 30% by mass)

Dye (A3); 1 to 50% by mass (more preferably 1 to 40% by mass, still more preferably 1 to 30% by mass)

Pigment (A2); 50 to 98% by mass (more preferably 60 to 98% by mass, still more preferably 70 to 98% by mass)

When the content of the xanthene dye (A1), the dye (A3), and the pigment (A2) is within the above range, the obtained color filter is excellent in contrast, lightness, heat resistance, and chemical resistance.

The total amount of the coloring agent (A) is preferably from 5 to 65% by mass, more preferably from 8 to 60% by mass, even more preferably from 10 to 55% by mass, based on the solid content of the colored photosensitive resin composition.

The colored photosensitive resin composition of the present invention contains a resin (B). The resin (B) has a copolymer derived from at least one structural unit selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, and a structural unit derived from N-cyclohexylmethyleneimine. The colored photosensitive resin composition contains a resin (B) to suppress partial peeling of a pattern at the time of development.

The content ratio of the structural unit derived from N-cyclohexylmethyleneimine in the copolymer is usually 1 mol% or more, preferably 35 mol%, based on the total structural unit of the copolymer. More preferably, the above is more than 43% by mole. Further, it is usually 90 mol% or less, preferably 85 mol% or less, more preferably 75 mol% or less. When the content of the structural unit derived from N-cyclohexylmethyleneimine is within the above range, in addition to the small amount of foreign matter from the release sheet, a high-density color filter tends to be obtained.

Examples of the resin (B) include the following copolymers [T1] to [T10].

[T1] A copolymer of at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride (hereinafter referred to as "(a)") and N-cyclohexylmethyleneimine.

[T2] (a), a monomer having a cyclic ether structure of 2 to 4 carbon atoms and an ethylenically unsaturated bond (b) (hereinafter referred to as "(b)")) and N-cyclohexylbutylene oxide A copolymer of an imine.

[T3] (a), N-cyclohexylmethyleneimine, and monomer (c) copolymerizable with (a) (only, (a), (b) and N-cyclohexyl-butenylene A copolymer of bismuth imine) (hereinafter referred to as "(c)").

[T4] (a), (b), a copolymer of N-cyclohexylmethyleneimine and (c).

[T5] A resin obtained by reacting (b) with a copolymer [T1] and/or a copolymer [T3].

[T6] A resin obtained by reacting (a) with a copolymer of (b) and N-cyclohexylmethyleneimine.

[T7] A resin obtained by reacting (a) with a copolymer of (b) and (c) with N-cyclohexylmethyleneimine.

[T8] A resin obtained by reacting a carboxylic anhydride with a copolymer [T6].

[T9] A resin obtained by reacting a carboxylic anhydride with a copolymer [T7].

[T10] is derived from the structural unit of acrylic acid or methacrylic acid. A structural unit derived from N-cyclohexylmethyleneimine and a structural unit derived from an acrylate or methacrylate.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid; maleic acid and fubutene; Diacid, methyl maleic acid, methyl fumaric acid, methylene succinic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3, 4, 5, Unsaturated dicarboxylic acid such as 6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid or 1, 4-cyclohexene dicarboxylic acid Acids; methyl-5-nordecene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]heptan-2- Alkene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methyl Bicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene and the like carboxyl group-containing bicyclic unsaturated compounds; anhydrous maleic acid, A Base maleic anhydride, methylene succinic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydroortylene Unsaturated dicarboxylic acid anhydrate of anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydrate, etc.; succinic acid mono[2-( Divalent or higher polycarboxylic acid unsaturated mono[(meth) propylene such as methyl) propylene decyloxyethyl] or phthalic acid mono [2-(methyl) propylene methoxyethyl] Mercaptooxyalkyl]esters; An unsaturated acrylate having a hydroxyl group and a carboxyl group in the same molecule as α-(hydroxymethyl)acrylic acid.

From the viewpoint of the copolymerization reactivity or the solubility in the aqueous alkali solution of the resin, (a) is preferably acrylic acid, methacrylic acid or anhydrous maleic acid.

(b) is, for example, a polymer having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, a propylene oxide ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. Compound. (b) It is preferred to use a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acrylonitrileoxy group.

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

In the case of (b), for example, a monomer (b1) having an oxirane group and an ethylenically unsaturated bond (hereinafter referred to as "(b1)"), and a monomer having an propylene oxide group and an ethylenically unsaturated bond may be mentioned. The body (b2) (hereinafter referred to as "(b2)"), a monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter referred to as "(b3)"), and the like.

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

(b1-1), for example, glycidyl (meth) acrylate, β-methyl glycidyl (meth) acrylate, β-ethyl glycidyl ( Methyl) acrylate, glycidyl vinyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α -methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene , 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-cis (glycidyloxymethyl)styrene, 2,3,5-gin (glycidyloxy) Methyl)styrene, 2,3,6-gin (glycidyloxymethyl)styrene, 3,4,5-glycol (glycidyloxymethyl)styrene and 2,4,6- Ginseng (glycidyloxymethyl) styrene and the like.

(b1-2), for example, vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, CELLOXIDE 2000; manufactured by DAICEL Chemical Industry Co., Ltd.), 3, 4 Epoxycyclohexylmethyl (meth) acrylate (eg CYCLOMER A400; manufactured by DAICEL Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (eg CYCLOMER M100; DAICEL chemistry) Industrial (stock) system, a compound represented by formula (I), a compound represented by formula (II), and the like.

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

X ¹ and X ² each independently represent a single ^{bond, -R c -, * - R} c -O -, * - R c -S -, * - R c -NH-.

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

* indicates the bond key with O. 〕

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

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

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

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

In the case of X ¹ and X ² , a single bond, a methyl group, an ethyl group, a *-CH ₂ -O- (* represents a bond with O) group, and *-CH ₂ CH ₂ -O are preferable. The base is more preferably a single bond or a *-CH ₂ CH ₂ -O- group.

The compound represented by the formula (I) may, for example, be a compound represented by any one of the formulae (I-1) to (I-15), and preferably a formula (I-1) or a formula (I- 3), a compound of the formula (I-5), the formula (I-7), the formula (I-9) or the formula (I-11) to the formula (I-15), more preferably a formula (I-1) a compound represented by 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), and preferably a formula (II-1) or a formula (II-). 3), a compound of the formula (II-5), the formula (II-7), the formula (II-9) or the formula (II-11) to the formula (II-15), more preferably a formula (II-1) a compound represented by 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 mixed individually or in any ratio. When mixing, the mixing ratio is in terms of a molar ratio, preferably from 5:95 to 95:5, more preferably from 10:90 to 90:10, more preferably from the formula (I): formula (II). 20:80~80:20.

The monomer (b2) having an oxypropylene group and an ethylenically unsaturated bond is more preferably a monomer having an oxypropylene group and a (meth) acrylonitrile group. (b2), 3-methyl-3-methylpropenyl methoxymethyl propylene oxide, 3-methyl-3-propenyl methoxymethyl propylene oxide, 3-ethyl -3- Methyl propylene decyloxymethyl propylene oxide, 3-ethyl-3-propenyl methoxymethyl propylene oxide, 3-methyl-3-methyl propylene decyl oxyethyl propylene oxide , 3-methyl-3-propenyloxyethyl propylene oxide, 3-ethyl-3-methylpropenyloxyethyl propylene oxide, 3-ethyl-3-propenyl oxime oxygen Ethyl propylene oxide and the like.

The monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond is more preferably a monomer having a tetrahydrofuranyl group and a (meth)acrylenyloxy group. Specific examples of the (b3) include tetrahydrofurfuryl acrylate (for example, VISCOTE V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

In the case of the (b) of the copolymers [T2] and [T4], it is preferable that the color filter obtained by the obtained color filter has higher reliability such as heat resistance and chemical resistance. . Further, from the viewpoint of excellent storage stability of the colored photosensitive resin composition, it is more preferable that (b1-2) is a compound represented by the formula (I) and a compound represented by the formula (II). At least one of the groups selected is even better.

(C), for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert- Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl methacrylate (meth) acrylate , cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl ( Methyl) acrylate (in the technical field to which the invention pertains, "dicyclopentyl (meth) acrylate" is a conventional name. Also known as "tricyclodecyl (meth) acrylate" Case), dicyclopentaoxyethyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decene-8-yl (meth) acrylate (in the technical field to which the invention pertains, In terms of its customary name, it is called dicyclopentenyl (meth) acrylate), isodecyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, Propargyl (meth) acrylate, phenyl (methyl) propyl (meth) acrylates such as acid esters, naphthyl (meth) acrylates, benzyl (meth) acrylates, etc.; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (A) a hydroxyl group-containing (meth) acrylate such as acrylate; diethyl maleate, diethyl fumarate, diethyl methylene succinate, etc. Carboxylic 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]g 2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]heptan-2- Alkene, 5,6-dimethoxybicyclo[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]hept-2-ene, 5-tert-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(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxy) Bicyclic unsaturated compounds such as bicyclo[2.2.1]hept-2-ene; N-phenyl maleimide, N-benzyl maleimide, N-butyl Diterpenoidimine-3-maleimide imide benzoate, N-butanediamine-4-butyleneimine butyrate, N-butanediamine -6-m-butylenimine hexanoate, N-butylenediamine-3-oxedimide propionate, N-(9-acridinyl)butylene Dicarbonyl quinone imine derivatives such as imine; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, propylene Nitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-di Methyl-1,3-butadiene and the like.

Among these, styrene, benzyl methacrylate, vinyl toluene, 2-hydroxyethyl (meth) acrylate, etc. are preferable from the viewpoint of copolymerization reactivity and development.

In the copolymer [T1], the content ratio of each structural unit is preferably in the range of the following range in the total structural unit constituting the copolymer [T1].

The structural unit from (a): 10 to 60 mol% (more preferably 15 to 57 mol%, and even more preferably 15 to 40 mol%)

a structural unit derived from N-cyclohexylmethyleneimine; 40 to 90 mol% (more preferably 43 to 85 mol%, still more preferably 60 to 85 mol%)

The content ratio of each structural unit of the copolymer [T1] is within the above range , the imaging is good, and one part of the pattern is difficult to peel off during development.

In the copolymer [T2], the content ratio of each structural unit is preferably in the range of the following in the entire structural unit constituting the copolymer [T2].

The structural unit from (a): 4 to 45 mol% (more preferably 10 to 45 mol%, and even more preferably 15 to 40 mol%)

The structural unit from (b): 2 to 95 mol% (more preferably 5 to 80 mol%, and even more preferably 5 to 40 mol%)

a structural unit derived from N-cyclohexylmethyleneimine; 1 to 65 mol% (more preferably 5 to 60 mol%, still more preferably 43 to 60 mol%)

When the content of each structural unit of the copolymer [T2] is within the above range, the developability is good, and it is difficult to peel off one of the patterns at the time of development, and the solvent resistance and heat resistance of the obtained pattern are further improved. Excellent in mechanical and mechanical strength.

The copolymer [T2] is preferably a copolymer of (a) and (b1) with N-cyclohexylmethyleneimine, (a) and (b1-2) and N-cyclohexyl. The copolymer of maleimide is more preferable, and the copolymer of (meth)acrylic acid and (b1-2) and N-cyclohexylmethyleneimine is more preferable.

In the copolymer [T3], the content ratio of each structural unit is preferably in the range of the following range in the total structural unit constituting the copolymer [T3].

The structural unit from (a): 4 to 45 mol% (more preferably 5 to 30 mol%, and even more preferably 10 to 30 mol%)

The structural unit from (c): 1 to 65 mol% (more preferably 5 to 60 mol%, and even more preferably 20 to 50 mol%)

a structural unit derived from N-cyclohexylmethyleneimine; 1 to 65 mol% (more preferably 5 to 60 mol%, still more preferably 20 to 50 mol%)

When the content of each structural unit of the copolymer [T3] is within the above range, the developability is good, and it is difficult to peel off one of the patterns at the time of development, and the solvent resistance and heat resistance of the obtained pattern are further improved. Excellent in mechanical and mechanical strength.

The copolymer [T3] is preferably a copolymer of (meth)acrylic acid and (c) with N-cyclohexylmethyleneimine, and (meth)acrylic acid with styrene and ethylene. Preferably, at least one of the copolymers selected from the group consisting of toluene, 2-hydroxyethyl (meth) acrylate and benzyl methacrylate is copolymerized with N-cyclohexyl maleimide. .

In the copolymer [T4], the content ratio of each structural unit is preferably in the range of the following range in the total structural unit constituting the copolymer [T4].

The structural unit from (a): 4 to 45 mol% (more preferably 10 to 45 mol%, and even more preferably 10 to 40 mol%)

The structural unit from (b): 2 to 94 mol% (more preferably 5 to 80 mol%, and even more preferably 5 to 40 mol%)

The structural unit from (c): 1 to 65 mol% (more preferably 5 to 60 mol%, and even more preferably 5 to 40 mol%)

a structural unit derived from N-cyclohexylmethyleneimine; 1 to 65 mol% (more preferably 5 to 60 mol%, still more preferably 43 to 60 mol%)

When the content of each structural unit of the copolymer [T4] is within the above range, the developability is good, and it is difficult to peel off one of the patterns at the time of development, and the solvent resistance and heat resistance of the obtained pattern are further improved. Excellent in mechanical and mechanical strength.

The copolymers [T1] to [T4] can be referred to, for example, in the literature "Experimental Methods for Polymer Synthesis" (published by Otsuka Ryokan, Ltd., 1st edition, 1st edition, 1st issue, March 1, 1972). Method and the literature Manufactured in the cited documents.

Specifically, the respective amounts of the monomers to be polymerized, the polymerization initiator, the solvent, and the like are placed in the reaction vessel, and the mixture is stirred under a deoxidizing atmosphere, for example, by replacing oxygen with nitrogen. Heating and holding methods. Further, the polymerization initiator, the solvent and the like used herein are not particularly limited, and any of those conventionally used in the art can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or organic In the solvent, if the monomer is dissolved, the solvent (E) or the like described later can be used as the solvent for coloring the photosensitive resin composition.

Further, the obtained copolymer 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, in the case of the polymerization, by using the solvent contained in the colored photosensitive resin composition of the present invention, the solution after the reaction is directly used for the production of the colored photosensitive resin composition. The preparation of the colored photosensitive resin composition of the present invention can be used to simplify the production steps of the colored photosensitive resin composition of the present invention.

The copolymer [T5] is a carboxylic acid and/or a carboxylic anhydride of (a) and (b) having a carbon number of 2 to 4 derived from the copolymer [T1] and/or the copolymer [T3] obtained as described above. The cyclic ether is reacted to produce.

After the production of the copolymer [T1] and/or the copolymer [T3], the reaction atmosphere of (b), a carboxylic acid or a carboxylic acid anhydride and a cyclic ether is continued by replacing the atmosphere in the flask with nitrogen, for example, (dimethylaminomethyl)phenol, etc.) A polymerization inhibitor or the like is placed in a flask, and the copolymer [T5] can be obtained by, for example, reacting at 60 to 130 ° C for 1 to 10 hours. The reaction conditions such as the charging method, the reaction temperature, and the time may be appropriately adjusted in consideration of the production equipment or the calorific value due to polymerization. Further, similarly to the polymerization conditions, the charging method or the reaction temperature can be appropriately adjusted in consideration of the production equipment or the calorific value due to the polymerization.

The amount of (b) used is preferably from 5 to 80 mol, more preferably from 10 to 75, for (a) 100 mol for copolymerization of the copolymer [T1] and/or the copolymer [T3]. Moor. By setting these ranges as such, the storage stability, development and sensitivity of the colored photosensitive resin composition and the balance of solvent resistance, heat resistance and mechanical strength of the color filter are good.

The amount of the reaction catalyst used for the carboxylic acid or the carboxylic acid anhydride and the cyclic ether is 100 parts by mass based on the total amount of the all monomers copolymerized with the copolymer [T1] and/or the copolymer [T3] and (b). In other words, it is preferably 0.001 to 5 parts by mass.

The amount of the polymerization inhibitor is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total monomer copolymerized with the copolymer [T1] and/or the copolymer [T3] and (b).

Since the reactivity of the cyclic ether is high and the unreacted (b) is difficult to remain, the aspect (b) used in the copolymer [T5] is preferably (b1) and more preferably (b1-1).

The copolymer [T6] can be obtained by (b) a copolymer of (b) with N-cyclohexylmethyleneimine, (a) having a carboxylic acid or a carboxylic anhydride and (b) It is produced by partially or completely reacting one of the cyclic ethers.

In the first stage, it is the same as the above-mentioned copolymer [T1]. The sample is carried out to obtain a copolymer of (b) and N-cyclohexylmethyleneimine. As the copolymer, the solution after the reaction may be used as it is, or a solution which is concentrated or diluted may be used, or a solid (powder) may be taken out by reprecipitation or the like.

The content ratio of the structural unit derived from (b) and N-cyclohexylmethyleneimine is the total number of moles constituting the entire structural unit of the copolymer, which are each within the following range. good.

Structural unit from (b): 5 to 95 mol% (more preferably 10 to 90 mol%)

a structural unit derived from N-cyclohexylmethyleneimine; 5 to 95 mol% (more preferably 10 to 90 mol%)

Further, by reacting the carboxylic acid or carboxylic anhydride having (a) with the cyclic ether derived from (b) in the copolymer [T5] under the same conditions as in the method for producing the copolymer [T5], Copolymer [T6].

The amount of (a) used for reacting with the aforementioned copolymer is preferably from 5 to 80 mols for (b) 100 mol. Since the reactivity of the cyclic ether is high and the unreacted (b) is difficult to remain, the aspect (b) used in the copolymer [T6] is preferably (b1) and more preferably (b1-1).

The copolymer [T7] can be obtained by the same method as the copolymer [T6] by obtaining a copolymer of (b) and (c) and N-cyclohexylmethyleneimine. a) Manufactured by reacting a carboxylic acid or a carboxylic anhydride with a part or all of the cyclic ether derived from (b) in the copolymer.

The content ratio of the structural unit derived from (b), (c), and N-cyclohexylmethyleneimine, and the total number of moles of the total structural unit constituting the copolymer In the following range, it is preferred.

Structural unit from (b): 5 to 95 mol% (more preferably 10 to 90 mol%)

Structural unit from (c): 4 to 94 mol% (more preferably 5 to 85 mol%)

Structural unit derived from N-cyclohexylmethyleneimine; 1 to 91 mol% (more preferably 5 to 85 mol%)

The amount of (a) to be reacted with the copolymer of (b) and (c) and N-cyclohexylmethyleneimine is 5 to 80 for (b) 100 mol. Moor is better. Since the reactivity of the cyclic ether is high and the unreacted (b) is difficult to remain, the aspect (b) used in the copolymer [T7] is preferably (b1) and more preferably (b1-1).

The copolymer [T8] is a resin obtained by further reacting a carboxylic anhydride with a copolymer [T6], and a copolymer [T9], which is a resin obtained by further reacting a carboxylic anhydride with a copolymer [T8]. Both are produced by reacting a carboxylic anhydride with a hydroxyl group produced by the reaction of a cyclic ether with a carboxylic acid or a carboxylic acid anhydride.

Examples of the carboxylic acid anhydride include anhydrous maleic acid, methyl maleic anhydride, methylene succinic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, and 3 , 4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[ 2.2.1] Hept-2-ene anhydrate and the like.

Specific examples of the resin (B) include a copolymer [T1] of a (meth)acrylic acid/N-cyclohexylmethylene iodide copolymer; 3,4-epoxycyclohexylmethyl (Meth)acrylate/(meth)acrylic acid/N-cyclohexylmethyleneimine copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate/(methyl) Copolymer of acrylic acid/N-cyclohexylmethylene iodide copolymer, etc. [T2]; benzyl (meth) acrylate / (meth) acrylate / N-cyclohexyl maleimide Copolymer, copolymer of styrene/(meth)acrylic acid/N-cyclohexylmethyleneimine copolymer, etc. [T3]; glycidyl (meth) acrylate/benzyl (methyl) Acrylate/(meth)acrylic acid/N-cyclohexylmethyleneimine copolymer, glycidyl (meth)acrylate/styrene/(meth)acrylic acid/N-cyclohexylbutene Yttrium imine copolymer, 3-methyl-3-(methyl)propenyl methoxymethyl propylene oxide / (meth) acrylate / styrene / N-cyclohexyl maleimide copolymer Copolymer [T4]; glycidyl (meth) acrylate and (meth) propyl Resin obtained by addition of acid/N-cyclohexylmethyleneimine copolymer, glycidyl (meth) acrylate and benzyl (meth) acrylate / (meth) acrylate / N- A resin obtained by addition of a cyclohexyl maleimide copolymer, a glycidyl (meth) acrylate and a tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid / N- A resin obtained by addition of a cyclohexyl maleimide copolymer, a glycidyl (meth) acrylate and a tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / ( a copolymer of a resin such as a methyl methacrylate/N-cyclohexyl maleimide copolymer; [T5]; a (meth)acrylic acid and a glycidyl (meth) acrylate/N a copolymer of a resin such as cyclohexylmethyleneimine, [T6]; (meth)acrylic acid and dicyclopentanyl (meth) acrylate/glycidyl (A) a resin obtained by reacting a copolymer of acrylate/N-cyclohexylmethyleneimine with (meth)acrylic acid and dicyclopentanyl (meth) acrylate/styrene/glycidyl group ( a copolymer of a resin such as a copolymer of methyl acrylate/N-cyclohexylmethylene iminoimide [T7]; a copolymer of (meth)acrylic acid and glycidyl (meth) acrylate a copolymer of a resin obtained by reacting a copolymer of /N-cyclohexylmethyleneimine, and a resin such as a resin obtained by reacting anhydrous maleic acid with a copolymer [T8]; a resin formed by reacting a copolymer of dicyclopentanyl (meth) acrylate/glycidyl (meth) acrylate/N-cyclohexyl maleimide, and then tetrahydro phthalene a copolymer [T9] or the like of a resin or the like obtained by reacting a form of the anhydride. These resins may be used singly or in combination of two or more.

In the case of the resin (B), the copolymer [T2], the copolymer [T3] and the copolymer [T4] are preferred, and the copolymer [T2] and the copolymer [T3] are more preferred.

The molecular weight (weight average molecular weight Mw) of the resin (B) is preferably from 3,000 to 100,000, more preferably from 4,000 to 50,000. When the weight average molecular weight of the resin (B) is within the above range, the coating property of the colored photosensitive resin composition is improved, and the pixel portion (exposed portion) is less likely to cause film reduction during development, and even the non-pixel portion at the time of development The detachability (solubility in the developing solution) of the (unexposed portion) tends to be improved. Moreover, the hardness of the obtained color filter tends to become high.

The acid value of the resin (B) is preferably from 30 to 150. When the acid value is within the above range, the solubility of the colored photosensitive resin composition in the developing solution is increased upward, and the unexposed portion is easily dissolved, and the residual film ratio of the exposed portion tends to increase due to high sensitivity. .

The content of the resin (B) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, particularly preferably from 17 to 55% by mass, based on the solid content of the colored photosensitive resin composition. When the content of the resin (B) is within the above range, a pattern can be formed, and the resolution and the residual film ratio are improved.

The colored photosensitive resin composition of the present invention contains a photopolymerizable compound (C). The photopolymerizable compound (C) is a compound which can be polymerized by an active radical generated by the photopolymerization initiator (D) or the like, and is not particularly limited. For example, a compound having a polymerizable ethylenically unsaturated bond or the like can be given.

In the photopolymerizable compound (C), a photopolymerizable compound having three or more ethylenically unsaturated bonds is preferred, and examples thereof include trimethylolpropane tri(meth)acrylate and pentaerythritol tris(A). Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol VII (methyl) ) acrylate, pentaerythritol deca (meth) acrylate, pentaerythritol 九 (meth) acrylate, ginseng (2-(methyl) propylene decyl oxyethyl) isocyanurate, ethylene glycol Modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate The caprolactone is modified with pentaerythritol tetra(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, and the like. Among them, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like are preferable.

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

The content of the photopolymerizable compound (C) is preferably 20 to 150 parts by mass based on 100 parts by mass of the resin (B) in the colored photosensitive resin composition.

The colored photosensitive resin composition of the present invention contains a photopolymerization initiator (D). In the case of the photopolymerization initiator (D), a compound which generates an active radical by the action of light and starts polymerization of the photopolymerizable compound (C) is not particularly limited, and a known photopolymerization initiator can be used. . Examples of the photopolymerization initiator (D) include a triazine compound, an alkylphenone compound, a mercaptophosphine oxide compound, an anthracene compound, and a biimidazole compound. Among them, a photopolymerization initiator containing a ruthenium compound is preferred.

The above triazine compound may, for example, be 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine or 2,4-bis(trichloro). Methyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-mallowyl-1,3,5-triazine , 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[ 2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl) Vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]- 1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine Wait.

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

Examples of the compound having a partial structure represented by the formula (d2) include, for example, 2-methyl-2-morpholinyl-1-(4-methylsulfonylphenyl)propan-1-one, 2-di Methylamino-1-(4-morpholinylphenyl)-2-benzylidenebutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl) Methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one and the like. Commercial products such as IRUGACURE (registered trademark) 369, 907, and 379 (manufactured by BASF Corporation) can also be used.

The compound having a partial structure represented by the formula (d3) may, for example, be 2-hydroxy-2-methyl-1-phenylpropan-1-one or 2-hydroxy-2-methyl-1-[4- (2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1- Olefin of ketone, α,α-diethoxyacetophenone, benzyldimethylketal, and the like.

From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (d2), and 2-methyl-2-morpholinyl-1-(4-methylsulfonate). Further, mercaptophenyl)propan-1-one and 2-dimethylamino-1-(4-morpholinylphenyl)-2-benzylidenebutan-1-one are more preferred.

The above-mentioned mercaptophosphine oxide compound may, for example, be 2,4,6-trimethylbenzimidyldiphenylphosphine oxide.

The above hydrazine compound is a compound having a partial structure represented by the formula (d1). Hereinafter, * indicates a keying key.

The above hydrazine compound may, for example, be an O-indenyl hydrazine compound, and specific examples thereof include N-benzimidyloxy-1-(4-phenylsulfonylbenzene). Butane-1-one-2-imine, N-benzylideneoxy-1-(4-phenylsulfonylphenyl)octane-1-one-2-imine, N- Benzamethyleneoxy-1-(4-phenylsulfonylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-ethyloxy-1-[9-B -6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{ 2-methyl-4-(3,3-dimethyl-2,4-dioxolylmethyloxy)benzimidyl}-9H-indazol-3-yl]ethane- 1-Imino, N-acetoxy-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-3-cyclopentylpropane- 1-Imino, N-benzylideneoxy-1-[9-ethyl-6-(2-methylbenzylidenyl)-9H-indazol-3-yl]-3-cyclopentyl Propane-1-keto-2-imine and the like. Commercial products such as IRUGACURE (registered trademark) OXE01, OXE02 (above, BASF), and N-1919 (made by Adeka) can also be used. Among them, N-benzylideneoxy-1-(4-phenylsulfonylphenyl)butan-1-one-2-imine, N-benzylideneoxy-1-(4) -phenylsulfonylphenyl)octane-1-one-2-imine and N-benzylideneoxy-1-(4-phenylsulfonylphenyl)-3-cyclopentylpropane 1-keto-2-imine is preferred. In the case of the above-mentioned compound, in particular, when the colored photosensitive resin composition of the present invention is prepared as a blue colored photosensitive resin composition, a high-density color filter can be obtained.

The biimidazole compound may, for example, be 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, JP-A-6-75372, JP-A-6-75373, etc.), 2, 2'-double (2) -Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxy) Phenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dioxane Oxyphenyl) biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (refer to for example, Gong Gong Zhao 48- An imidazole compound in which a phenyl group at the 4,4'5,5'-position is substituted with a carboxy group (refer to, for example, JP-A-7-10913, etc., for example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. )Wait.

Further, examples of the photopolymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, o- Benzoyl benzoic acid methyl ester, 4-phenyl benzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3', 4,4'-tetra (tert- a benzophenone compound such as butylperoxycarbonyl)benzophenone or 2,4,6-trimethylbenzophenone; an anthracene compound such as 9,10-phenanthrenequinone, 2-ethylhydrazine, camphorquinone or the like ; 10-butyl-2-chloroacridone, benzyl, phenylglyoxylate methyl ester, titanocene compound, and the like. These are preferably used in combination with a photopolymerization initiation auxiliary (D1) (particularly an amine) to be described later.

The colored photosensitive resin composition of the present invention may contain a photopolymerization initiation auxiliary (D1). When the photopolymerization initiation aid (D1) is contained, it can usually be used in combination with the photopolymerization initiator (D). The photopolymerization initiation auxiliary (D1) is a compound or a sensitizer used for the polymerization of the photopolymerizable compound (C) which starts polymerization by the photopolymerization initiator (D).

Examples of the photopolymerization initiation auxiliary (D1) include an amine compound, an alkoxy fluorene compound, a thioxanthone compound, a carboxylic acid compound, and the like. The photopolymerization initiation auxiliary agent may be used singly or in combination of two or more.

The above amine compound may, for example, be triethanolamine or methyldiethanolamine. , triisopropanolamine, 4-dimethylamino benzoic acid methyl ester, 4-dimethylamino benzoic acid ethyl ester, 4-dimethylamino benzoic acid isoamyl ester, benzoic acid 2 -dimethylaminoethyl ester, 2-ethylhexyl benzoic acid 2-ethylhexyl ester, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino) Benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, etc., among which 4,4'-double ( Diethylamino)benzophenone is preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

Examples of the alkoxyfluorene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl. -9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

Examples of the aforementioned thioxanthone-based compound include 2-isopropylthiaxanthone, 4-isopropylthiaxanthone, 2,4-diethylthioxanthone, and 2,4-dichloro. Thioxanthone and 1-chloro-4-propoxythiazinone and the like.

Examples of the carboxylic acid compound include phenylsulfonyl acetic acid, methylphenylsulfonyl acetic acid, ethylphenylsulfonyl acetic acid, methyl ethyl phenylsulfonyl acetic acid, and dimethylphenyl. Sulfhydryl acetic acid, methoxyphenylsulfonyl acetic acid, dimethoxyphenylsulfonyl acetic acid, chlorophenylsulfonyl acetic acid, dichlorophenylsulfonyl acetic acid, N-phenylglycine , phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, and the like.

When the photopolymerization initiation auxiliary (D1) is used, the content thereof is preferably 0.01 to 10 mol, more preferably 0.01 to 5 mol, to the photopolymerization initiator (D) 1 mol. .

The content of the photopolymerization initiator (D) is preferably from 1 to 40 parts by mass, more preferably from 5 to 20 parts by mass, per 100 parts by mass of the photopolymerizable compound (C). When the content of the photopolymerization initiator (D) is within the above range, the sensitivity is shortened and the productivity is improved.

The colored photosensitive resin composition of the present invention is preferably a solvent (E). The solvent (E) is not particularly limited, and a solvent generally used in the field can be used. For example, it may be an ester solvent (a solvent containing a -COO-structure in a molecule and not containing an -O-structure), an ether solvent (a solvent containing a -O-structure in a molecule and not containing a -COO-structure), an ether ester solvent (molecule) a solvent containing a -COO-structure and a -O-structure, a ketone solvent (a solvent containing a -CO-structure in the molecule and not containing a -COO-structure), an alcohol solvent (containing an OH group in the molecule, and containing no -O - Structure, -CO-structure and -COO-structure solvent), aromatic hydrocarbon solvent, guanamine solvent, dimethyl hydrazine, etc. are selected and used.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, and isobutyl acetate. , amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, pyruvate A base ester, an ethyl acetate, an ethyl acetate, an ethyl acetoacetate, a cyclohexanol acetate, and a 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 Ethyl, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl Ether, diethylene glycol dibutyl ether, anisole, phenethyl ether and methyl anisole.

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

The ketone solvent may, for example, be 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone or 4-methyl-2- Pentanone, cyclopentanone, 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 trimethylbenzene.

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

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

Among the above solvents, from the viewpoint of coatability and drying properties, an organic solvent having a boiling point of from 1 ° to 120 ° C to 180 ° C is preferred. Among them, 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, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-di Methylformamide or the like is preferred, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3 More preferably, methoxy-1-butanol or ethyl 3-ethoxypropionate.

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 coloring photosensitive resin composition. In other words, the solid content of the colored photosensitive resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating is good, and the color density at the time of forming the color filter is not insufficient, so that the display characteristics are good.

The colored photosensitive resin composition of the present invention may contain additives such as a filler, other polymer compound, adhesion promoter, leveling agent, antioxidant, ultraviolet absorber, light stabilizer, chain transfer agent, etc. as needed (hereinafter Called "other ingredients").

The coloring photosensitive resin composition of the present invention can be, for example, a mixed coloring agent (A), a resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent which is optionally used. (E), a polymerization starting adjuvant (D1) and other components are prepared.

In the case of containing the pigment (A2), it is preferred to mix the pigment with a part or all of the solvent (E) in advance and to disperse it into a pigment having an average particle diameter of about 0.2 μm or less. In this case, some or all of the pigment dispersant and the resin (B) may be blended as needed. By mixing the remaining components and the like into a predetermined concentration in the obtained pigment dispersion liquid, the desired color-sensitive photosensitive resin composition can be prepared.

Preferably, the xanthene dye (A1) is previously dissolved in part or all of the solvent (E) to prepare a solution. Further, it is preferred that the solution be filtered through a filter having a pore diameter of about 0.01 to 1 μm.

It is preferred that the colored photosensitive resin composition prepared by mixing as described above is filtered by a filter having a pore diameter of about 0.01 to 10 μm.

The colored photosensitive resin composition of the present invention can be suitably used in a photolithography method.

The photolithography method is a method in which a colored photosensitive resin composition is applied onto a substrate, dried, and exposed through a photomask to obtain a pattern by development. The pattern can be used as a color filter, or in the photolithography method, the formed film can be used as a color filter by using no mask and/or no image during exposure.

The colored photosensitive resin composition of the present invention can be suitably used in an inkjet method, a printing method, or the like.

Examples of the substrate include glass, metal, plastic, and the like, and may be in the form of a plate or a film. Further, on such a substrate, a structure such as a color filter, various insulating or conductive films, and a driving circuit may be formed.

For coating the substrate, for example, a spin coater, a slit & spin coater, a slit coater (also referred to as a die coater, or a die coater) can be used. A coating device such as a curtain flow coater, a spinless coater, or an inkjet.

Examples of the method for drying the film coated on the substrate include heat drying (prebaking), natural drying, air drying, and reduced pressure drying. It is also possible to combine the plural methods. The drying temperature is preferably from 10 to 120 ° C and more preferably from 25 to 100 ° C. Further, the heating time is preferably from 10 seconds to 60 minutes, and more preferably from 30 seconds to 30 minutes. The vacuum drying is preferably carried out at a pressure of 50 to 150 Pa and a temperature range of 20 to 25 °C.

The film thickness of the coating film after drying is not particularly limited, and can be appropriately adjusted depending on the material to be used, the use, and the like, and is, for example, 0.1 to 20 μm, preferably 1 to 6 μm.

The dried coating film can be exposed through a photomask for forming a target pattern. At this time, the shape of the pattern on the photomask is not particularly limited, and the shape of the pattern for the intended purpose can be used.

The light source used in the exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light of less than 350 nm can be sheared by using a filter that shears the wavelength region, or light of a vicinity of 436 nm, around 408 nm, and around 365 nm can be used with a band pass filter that can take out such wavelength regions. Selectively removed. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned.

In order to uniformly illuminate the entire exposed surface with parallel light, or to perform a proper positional matching of the mask and the substrate, it is preferable to use a mask to align the exposure machine, the stepper, or the like.

After the exposure, by bringing it into contact with the developing solution, a predetermined portion such as an unexposed portion is dissolved and developed to obtain a pattern. In terms of imaging liquid, although it is also Although an organic solvent is used, it is difficult to dissolve or swell the exposed portion of the coating film by the developing solution, and a pattern having a good shape can be obtained, and an aqueous solution of a basic compound is preferred.

The development method may be any of a paddle stirring method, a dipping method, a spray method, and the like. The substrate can be tilted at any angle even during development.

It is better to perform water washing after development.

Examples of the basic compound include sodium hydroxide, potassium hydroxide, disodium hydrogen citrate, sodium dihydrogen citrate, diammonium hydrogen citrate, ammonium dihydrogen citrate, potassium dihydrogen citrate, sodium citrate, potassium citrate, Inorganic basic compound of sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, ammonia, etc.; tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, single An organic basic compound such as methylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine or ethanolamine. Among them, potassium hydroxide, sodium hydrogencarbonate and tetramethylammonium hydroxide are preferred.

The concentration in the aqueous solution of the inorganic or organic basic compound is preferably from 0.01 to 10% by mass, more preferably from 0.03 to 5% by mass.

The aqueous solution of the aforementioned basic compound may contain a surfactant.

Examples of the surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene/oxypropylene block copolymer, and sorbitol. Nonionics such as alcoholic anhydride fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, glycerol fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, etc. System surfactant; An anionic surfactant such as sodium lauryl sulfate, sodium oleyl sulfate, sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate or sodium dodecylnaphthalenesulfonate; A cationic surfactant such as an amine hydrochloride or a lauryl trimethylammonium chloride.

The concentration of the surfactant in the aqueous solution of the basic compound is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, particularly preferably 0.1 to 5% by mass.

Further post-baking can be carried out as needed. Post-baking is preferably carried out, for example, in the range of 150 to 250 ° C for 1 to 240 minutes.

The color filter obtained by the coloring photosensitive resin composition of the present invention can be suitably used as a display device (for example, a liquid crystal display device, an organic EL device, etc.) or an electronic paper because the amount of foreign matter is small. A color filter provided in a machine for various color images, such as a solid-state imaging device. In these machines, it can be utilized in a known manner.

Example

Next, the present invention will be specifically described by way of examples. In the examples, "%" and "parts" are % by mass and parts by mass unless otherwise stated.

Synthesis Example 1

In the flask with the cooling tube and the stirring device, the input type (A0-1) 15 parts of a mixture of the compound represented by the formula (A0-2) (manufactured by the method of chemical conversion), 150 parts of chloroform and 8.9 parts of N,N-dimethylformamide, and maintained at 20 ° C or lower while stirring. Then, 10.9 parts of thidium chloride was added dropwise. After completion of the dropwise addition, the temperature was raised to 50 ° C, and the reaction was carried out for 5 hours while maintaining the same temperature, followed by cooling to 20 ° C. After the cooled reaction solution was maintained at 20 ° C or lower while stirring, a mixture of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise. Thereafter, the mixture was stirred at the same temperature for 5 hours to cause a reaction. Next, the obtained reaction mixture was distilled off by a rotary evaporator, and then methanol was added in a small amount, followed by vigorous stirring. This mixture was added to a mixed solution of 375 parts of ion-exchanged water while stirring to precipitate crystals. The precipitated crystals were filtered, washed thoroughly with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain 11.3 parts of a dye A1 (a mixture of compounds represented by formula (A1-1) to formula (A1-8)).

The dye was dissolved in A1 0.35g ethyl lactate manipulation volume of 250cm ^3, which will be diluted to 100cm ³ 2cm ³ to ethyl lactate, adjusted to a concentration of 0.028g / L of solution. With respect to this solution, an ultraviolet absorption spectrophotometer (V-650DS; manufactured by JASCO Corporation) (quartz tube, optical path length; 1 cm) was used, and the maximum absorption wavelength (λ _max ) was measured, and as a result, it was 525 nm.

Synthesis Example 2

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 a light-shielding condition, and the resulting solution was stirred at 110 ° C for 6 hours. The resulting reaction solution is cooled to room temperature Thereafter, the mixture was added to a mixed liquid of 800 parts of water and 50 parts of 35% hydrochloric acid, and after stirring at room temperature for 1 hour, crystals were precipitated. The precipitated crystals were obtained in the form of a vacuum-filtered residue, and dried to obtain 24 parts of the compound of the formula (1-31). The yield was 80%.

The compound of the formula (1-31) was identified by mass analysis (LC; Model 1200, manufactured by Agilent, MASS; LC/MSD type manufactured by Agilent).

(mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ 603.4

Exact Mass: 602.2

The maximum absorption wavelength (λ _max ) was measured in the same manner as in Synthesis Example 1. As a result, it was 548 nm.

Synthesis Example 3

The compound represented by the formula (1-39) was obtained in the same manner as in Synthesis Example 1 except that N-propyl-2,6-dimethylaniline was used instead of N-ethyl-o-toluidine. .

The compound represented by the formula (1-39) was identified by mass analysis (LC; Model 1200, manufactured by Agilent, MASS; LC/MSD type manufactured by Agilent).

(mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ 659.9

Exact Mass: 658.9

The maximum absorption wavelength (λ _max ) was measured in the same manner as in Synthesis Example 1. As a result, it was 548 nm.

Synthesis Example 4

Into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a gas introduction tube, 250 parts of propylene glycol monomethyl ether acetate was introduced. Thereafter, nitrogen gas was introduced into the flask using a gas introduction tube, and the atmosphere in the flask was replaced with nitrogen. Thereafter, after raising the temperature of the solution in the flask to 100 ° C, 56.9 parts of benzyl methacrylate, 96.5 parts of N-cyclohexylmethyleneimine, 41.7 parts of methacrylic acid, and azobisisobutyronitrile were used. A mixture of 1.5 parts and 150 parts of propylene glycol monomethyl ether acetate was dropped into the flask using a dropping funnel for 2 hours. After the completion of the dropwise addition, stirring was continued at 100 ° C for 2.5 hours to obtain a solid content of 34% and a solution acid value. 47 mg-KOH/g of the resin B1 solution. The weight average molecular weight in terms of polystyrene measured by GPC was 2.3 × 10 ⁴ . The solid content acid value is calculated from the above solid content and the acid value of the solution, and is 138 mg-KOH/g. Resin B1 has the following structural unit.

Synthesis Example 5

Into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a gas introduction tube, 250 parts of propylene glycol monomethyl ether acetate was introduced. Thereafter, nitrogen gas was introduced into the flask using a gas introduction tube, and the atmosphere in the flask was replaced with nitrogen. Thereafter, after raising the temperature of the solution in the flask to 100 ° C, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ] mercapto acrylate (the compound represented by the formula (I-1) and the formula (II-1) ) the compound shown is 56.9 parts mixed with a molar ratio of 50:50, 96.5 parts of N-cyclohexylmethyleneimine, 41.7 parts of methacrylic acid, 3.6 parts of azobisisobutyronitrile and propylene glycol. A mixture of 150 parts of methyl ether acetate was dropped into the flask over a period of 2 hours using a dropping funnel. After the completion of the dropwise addition, stirring was continued at 100 ° C for 2.5 hours to obtain a solid content of 34% and a solution acid value of 47 mg-KOH/g. Resin B2 solution. The weight average molecular weight in terms of polystyrene measured by GPC was 9.6 × 10 ³ . The solid content acid value is calculated from the above solid content and the acid value of the solution, and is 138 mg-KOH/g.

Resin B2 has the following structural unit.

Synthesis Example 6

In a flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a nitrogen introduction tube, 210 g of propylene glycol monomethyl ether acetate was introduced, and the atmosphere in the flask was changed from air to nitrogen, and then the temperature was raised to 100 ° C. It will be a monomethacrylate of 70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, and a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) a mixture of 22.0 g (0.10 mol) and propylene glycol monomethyl ether acetate (215 g) was added with a solution of 3.6 g of 2,2'-azobisisobutyronitrile, and the solution was continued at 100 ° C. Stir under. Next, the atmosphere in the flask was changed from nitrogen to air, and glycidyl methacrylate was 35.5 g [0.25 mol, (50 mol% for the carboxyl group of methacrylic acid used in the reaction)] 0.9 g of dimethylaminomethylphenol and 0.145 g of hydroquinone were placed in a flask, and the reaction was continued at 110 ° C to obtain a resin B3 solution having a solid content of 79 mgKOH/g and a solid content of 29%.

Synthesis Example 7

In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, nitrogen gas was introduced at 0.02 L/min to create a nitrogen atmosphere, and 268 parts of ethyl lactate was placed, and the mixture was heated to 70 ° C while stirring. Next, 55 parts of acrylic acid, 81 parts of N-cyclohexylmethyleneimine, and 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate (shown by the formula (I-1)) The compound and the compound of the formula (II-1) are obtained by mixing a molar ratio of 50:50, 224 parts, and a tricyclo [5.2.1.0 ^2.6 ] terpene-8-yl acrylate (the formula (c-1) The compound shown by the formula (c-2) and the compound of the formula (c-2) are mixed at a molar ratio of 50:50. 7 parts are dissolved in 140 parts of ethyl lactate to prepare a solution, and it takes 4 hours to use a dropping funnel. The solution was dropped into a flask maintained at 70 °C.

In addition, 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in a solution of 225 parts of ethyl lactate, and another dropping funnel was used. Drop into the flask every hour. The solution of the polymerization initiator was kept at 70 ° C for 4 hours after the completion of the dropwise addition, and then cooled to room temperature to obtain a polystyrene-equivalent weight average molecular weight of 1.12 × 10 ⁴ , a solid content of 37.0%, and a solid component acid value of 119 mg - KOH/g resin B4 solution. Resin B4 has the following structural unit.

Synthesis Example 8

In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, nitrogen gas was introduced at 0.02 L/min to create a nitrogen atmosphere, and 268 parts of ethyl lactate was placed, and the mixture was heated to 70 ° C while stirring. Next, 55 parts of acrylic acid, 203 parts of N-cyclohexylmethyleneimine, and 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate (shown by the formula (I-1)) The compound and the compound of the formula (II-1) are obtained by mixing a molar ratio of 50:50, 101 parts, and tricyclo [5.2.1.0 ^2.6 ] terpene-8-yl acrylate (the formula (c-1) The compound shown by the formula (c-2) and the compound of the formula (c-2) are mixed at a molar ratio of 50:50. 7 parts are dissolved in 538 parts of ethyl lactate to prepare a solution, and the dropping funnel is used for 4 hours. The solution was dropped into a flask maintained at 70 °C. In addition, 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in a solution of 225 parts of ethyl lactate, and another dropping funnel was used. Drop into the flask every hour. The solution of the polymerization initiator was kept at 70 ° C for 4 hours after the completion of the dropwise addition, and then cooled to room temperature to obtain a polystyrene-equivalent weight average molecular weight of 6.5 × 10 ³ , a solid content of 26.2%, and a solid component acid value of 121 mg. - KOH / g of resin B5 solution. Resin B5 has the following structural unit.

Synthesis Example 9

In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, nitrogen gas was introduced at 0.02 L/min to create a nitrogen atmosphere, and 268 parts of ethyl lactate was placed, and the mixture was heated to 70 ° C while stirring. Next, 55 parts of acrylic acid, 258 parts of N-cyclohexylmethyleneimine, and 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate (shown by the formula (I-1)) The compound and the compound of the formula (II-1) are obtained by mixing a molar ratio of 50:50, 36 parts, and a tricyclo[5.2.1.0 ^2.6 ]nonene-8-yl acrylate (the formula (c-1) The compound shown by the formula (c-2) and the compound of the formula (c-2) are mixed at a molar ratio of 50:50. 18 parts are dissolved in 619 parts of ethyl lactate to prepare a solution, and the dropping funnel is used for 4 hours. The solution was dropped into a flask maintained at 70 °C. In addition, 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in a solution of 225 parts of ethyl lactate, and another dropping funnel was used. Drop into the flask every hour. The solution of the polymerization initiator was kept at 70 ° C for 4 hours after the completion of the dropwise addition, and then cooled to room temperature to obtain a polystyrene-equivalent weight average molecular weight of 7.2 × 10 ³ , a solid content of 24.8%, and a solid component acid value of 112 mg. - KOH / g of resin B6 solution. Resin B6 has the following structural unit.

Synthesis Example 10

In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, nitrogen gas was introduced at 0.02 L/min to create a nitrogen atmosphere, and 268 parts of ethyl lactate was placed, and the mixture was heated to 70 ° C while stirring. Next, 55 parts of acrylic acid, 203 parts of N-cyclohexylmethyleneimine, and 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate (shown by the formula (I-1)) The compound and the compound of the formula (II-1) are mixed at a molar ratio of 50:50 to obtain 73 parts of a tricyclo[5.2.1.0 ^2.6 ]nonene-8-yl acrylate (the formula (c-1) The compound shown by the formula (c-2) and the compound of the formula (c-2) are mixed at a molar ratio of 50:50. 35 parts are dissolved in 517 parts of ethyl lactate to prepare a solution, and the dropping funnel is used for 4 hours. The solution was dropped into a flask maintained at 70 °C. In addition, 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in a solution of 225 parts of ethyl lactate, and another dropping funnel was used. Drop into the flask every hour. The solution of the polymerization initiator was kept at 70 ° C for 4 hours after completion of the dropwise addition, and then cooled to room temperature to obtain a polystyrene-equivalent weight average molecular weight of 6.8 × 10 ³ , a solid content of 26.6%, and a solid component acid value of 114 mg. - KOH / g of resin B7 solution. Resin B7 has the following structural unit.

Synthesis Example 11

In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, nitrogen gas was introduced at 0.02 L/min to create a nitrogen atmosphere, and 268 parts of propylene glycol monomethyl ether acetate was placed, and heated to 70 ° C while stirring. until. Next, 55 parts of acrylic acid, 203 parts of N-cyclohexylmethyleneimine, and 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate (shown by the formula (I-1)) The compound and the compound of the formula (II-1) are mixed at a molar ratio of 50:50 to obtain 73 parts of a tricyclo[5.2.1.0 ^2.6 ]nonene-8-yl acrylate (the formula (c-1) The compound shown by the formula (c-2) and the compound of the formula (c-2) are mixed at a molar ratio of 50:50. 35 parts of propylene glycol monomethyl ether acetate are dissolved in 517 parts to prepare a solution, and the dropping funnel is used. The solution was dropped into a flask kept at 70 ° C for 4 hours. Further, 30 parts of a polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in a solution of 225 parts of propylene glycol monomethyl ether acetate, and another drop was used. The funnel was dropped into the flask over 4 hours. The solution of the polymerization initiator was kept at 70 ° C for 4 hours after the completion of the dropwise addition, and then cooled to room temperature to obtain a weight average molecular weight Mw of 1.1 × 10 ⁴ , a solid content of 26.6%, and a solid component acid value of 81 mg - KOH / g resin B8 solution. Resin B8 has the following structural unit.

The measurement of the polystyrene-equivalent weight average molecular weight of the resin obtained in the above synthesis example was carried out under the following conditions using a GPC method.

Device; HLC-8120GPC (TOSOH system)

Pipe string; TSK-GELG2000HXL

Column temperature; 40 ° C

Solvent; THF

Flow rate; 1.0mL/min

Solid concentration of the liquid to be tested; 0.001~0.01% by mass

Injection volume; 50μL

Detector; RI

Standard material for calibration; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by TOSOH)

Example 1 [Preparation of coloring photosensitive resin composition]

Mix the following ingredients: And use a bead mill to fully disperse the pigment, then mix the following ingredients: A colored photosensitive resin composition was obtained.

[Production of pattern and observation of peeling sheet]

The colored photosensitive resin composition was applied by a spin coating method on a square glass substrate (EAGLE 2000; manufactured by Corning Co., Ltd.), and then prebaked at 100 ° C for 3 minutes. After cooling, the interval between the substrate coated with the colored photosensitive resin composition and the mask made of quartz glass having a pattern was 100 μm, and an exposure machine (TME-150RSK; TOPCON) was used in an atmosphere. Light irradiation was performed at an exposure amount of 150 mJ/cm ² (365 nm basis). After the light irradiation, the coating film was immersed in a water-based developing solution containing 0.12% of a nonionic surfactant and 2% of sodium carbonate at 28 ° C for 80 seconds, and was subjected to water washing. The substrate after the water washing was observed with a microscope (magnification: 500 times; VF-7510; manufactured by KEYENCE), and the foreign matter from the release sheet was observed on the portion corresponding to the unexposed portion of the colored photosensitive resin composition layer. When there is no foreign matter, it is marked as ○, and when there is foreign matter, it is marked as ×, which is shown in Table 1.

Thereafter, post-baking at 230 ° C for 30 minutes in an oven gave a pattern.

[Measurement of film thickness]

With respect to the obtained pattern, the film thickness was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 1.

[Chroma evaluation]

For the obtained pattern, the color separation was measured using a color measuring machine (OSP-SP-200; OLYMPUS), and the xy chromaticity coordinate in the XYZ color system of the CIE was measured using the characteristic function 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 1.

Example 2

The coloring photosensitive resin composition was obtained in the same manner as in Example 1 except that the resin B1 solution was changed to the resin B2 solution. Further, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

Comparative example [Preparation of coloring photosensitive resin composition]

Mix the following ingredients: And use a bead mill to fully disperse the pigment, then mix the following ingredients: Thus, a photosensitive resin composition is colored. The obtained colored photosensitive resin composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 3 [Preparation of coloring photosensitive resin composition]

Mix the following ingredients: And use a bead mill to fully disperse the pigment, then mix the following ingredients: A colored photosensitive resin composition was obtained.

[Production of pattern and observation of peeling sheet]

The colored photosensitive resin composition was applied by a spin coating method on a square glass substrate (EAGLE 2000; manufactured by Corning Co., Ltd.), and then prebaked at 100 ° C for 3 minutes. After cooling, the interval between the substrate coated with the colored photosensitive resin composition and the mask made of quartz glass having a pattern was 100 μm, and an exposure machine (TME-150RSK; TOPCON) was used in an atmosphere. Light irradiation was performed at an exposure amount of 150 mJ/cm ² (365 nm basis). After the light irradiation, the coating film was immersed in a water-based developing solution containing 0.12% of a nonionic surfactant and 2% of sodium carbonate at 28 ° C for 80 seconds, and was subjected to water washing. The substrate after the water washing was observed with a microscope (magnification: 500 times; VF-7510; manufactured by KEYENCE), and the foreign matter from the release sheet was observed on the portion corresponding to the unexposed portion of the colored photosensitive resin composition layer. When there is no foreign matter, it is marked as ○, and when there is foreign matter, it is marked as ×, which is shown in Table 1.

Thereafter, post-baking was carried out at 230 ° C for 180 minutes in an oven to obtain a pattern. The obtained pattern was evaluated in the same manner as in Example 1. The results are shown in Table 2.

Example 4 [Preparation of coloring photosensitive resin composition]

Mix the following ingredients: And use a bead mill to fully disperse the pigment, then mix the following ingredients: Thus, a photosensitive resin composition is colored. Further, evaluation was carried out in the same manner as in Example 3. The results are shown in Table 2.

Example 5 [Preparation of coloring photosensitive resin composition]

Mix the following ingredients: And use a bead mill to fully disperse the pigment, then mix the following ingredients: Thus, a photosensitive resin composition is colored. Further, evaluation was carried out in the same manner as in Example 3. The results are shown in Table 2.

Example 6 [Preparation of coloring photosensitive resin composition]

Mix the following ingredients: Pigment: CI color blue 15:6 32 parts And use a bead mill to fully disperse the pigment, then mix the following ingredients: Thus, a photosensitive resin composition is colored. Further, evaluation was carried out in the same manner as in Example 3. The results are shown in Table 2.

Example 7 [Preparation of coloring photosensitive resin composition]

Mix the following ingredients: And use a bead mill to fully disperse the pigment, then mix the following ingredients: Thus, a photosensitive resin composition is colored. Further, evaluation was carried out in the same manner as in Example 3. The results are shown in Table 2.

Comparative example 2 [Preparation of coloring photosensitive resin composition]

Mix the following ingredients: And use a bead mill to fully disperse the pigment, then mix the following ingredients: Thus, a photosensitive resin composition is colored. Further, evaluation was carried out in the same manner as in Example 3. The results are shown in Table 2.

Example 8

In the same manner as in Example 7, except that the compound represented by the formula (1-39) was replaced by the compound represented by the formula (1-31), a colored photosensitive resin composition was obtained. The same evaluation as in Example 3 was carried out, and it was confirmed that there was no foreign matter from the release sheet.

Industrial availability

According to the colored photosensitive resin composition of the present invention, since a part of the unexposed portion of the colored photosensitive resin composition layer can be prevented from being peeled off during development, the foreign matter formed on the pattern is small.

Claims (10)

A colored photosensitive resin composition containing a colorant, a resin, a photopolymerizable compound, and a photopolymerization initiator, wherein the colorant is a xanthene dye-containing coloring agent, and the resin is derived from an unsaturated carboxylic acid a copolymer of at least one structural unit selected from the group consisting of an acid and an unsaturated carboxylic anhydride and a structural unit derived from N-cyclohexylmethyleneimine, the aforementioned N-cyclohexyl-butenylene The content of the structural unit of the quinone is 35 mol% or more based on the total structural unit of the copolymer. The coloring photosensitive resin composition of claim 1, wherein the xanthene dye is a compound represented by the formula (1), In the formula, R ¹ to R ⁴ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and a hydrogen atom contained in the aromatic hydrocarbon group. It may be a halogen atom, -R ⁸ , -OH, -OR ⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- M ⁺ , -CO ₂ H, -CO ₂ ^- M ⁺ , -CO ₂ R ⁸ , -SR ⁸ , -SO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ is substituted; the hydrogen atom contained in the saturated hydrocarbon group may be an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom. And the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 3 carbon atoms; the -CH ₂ - contained in the above saturated hydrocarbon group may be -O-, -CO- or - NR ¹¹ -substituted; R ¹ and R ² may together form a ring containing a nitrogen atom, R ³ and R ⁴ may together form a ring containing a nitrogen atom, and R ⁵ represents -OH, -SO ₃ ^- , - SO ₃ H, -SO ₃ ^- M ⁺ , -CO ₂ H, -CO ₂ ^- M ⁺ , -CO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ , m represents an integer of 0-5 . When m is 2 or more, plural R ^{5 's} may be the same or different, and R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and M ⁺ represents ⁺ N(R ¹¹ ) ₄ , Na ^{+ .} Or K ⁺ , X represents a halogen atom, a represents an integer of 0 or 1, 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 ¹¹ Each independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, and R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturation having a carbon number of 1 to 20. a hydrocarbon group, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a hydroxyl group or a halogen atom, and the -CH ₂ - contained in the saturated aliphatic hydrocarbon group may be -O-, -CO-, -NH- or -NR ⁸ - is substituted, and R ⁹ and R ¹⁰ may be bonded to each other to form a heterocyclic ring of a 3 to 10 membered ring containing a nitrogen atom]. The coloring photosensitive resin composition of claim 1, wherein the xanthene dye is a compound represented by the formula (2), [wherein R ²¹ to R ²⁴ each independently represent a hydrogen atom, -R ²⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be -SO ₃ ^- , -SO ₃ ^- M ^a+ , -SO ₃ H, -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ is substituted, X ^a represents a halogen atom, a ¹ represents an integer of 0 or 1, m1 represents an integer of 0-5, m1 When it is 2 or more, the plural R ²⁵ may be the same or different, and M ^a+ represents ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ , and R ²⁵ represents -SO ₃ ^- , -SO ₃ ^- M ^a+ , -SO ₃ H or SO ₂ NHR ²⁶ , R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and R ²⁷ each independently represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group. The colored photosensitive resin composition of claim 1, wherein the xanthene dye is a compound represented by the formula (3), [In the formula (3), R ³¹ and R ³² each independently represent an alkyl group having 1 to 10 carbon atoms, and R ³³ and R ³⁴ each independently represent an alkyl group having 1 to 4 carbon atoms and an alkyl group having 1 to 4 carbon atoms. a sulfonyl group or an alkyl fluorenyl group having 1 to 4 carbon atoms, R ³¹ and R ³³ may be taken together to form a ring containing a nitrogen atom, and R ³² and R ³⁴ may be taken together to form a ring containing a nitrogen atom, p and q independently represents an integer of 0 to 5, and when p is 2 or more, the plural R ³³ may be the same or different, and when q is 2 or more, the plural R ³⁴ may be the same or different. The coloring photosensitive resin composition of claim 1, wherein the xanthene dye is a mixture of compounds represented by the formula (A1-1) to the formula (A1-8), The colored photosensitive resin composition of claim 1, wherein the aforementioned The resin is a copolymer composed of a structural unit derived from acrylic acid or methacrylic acid, a structural unit derived from N-cyclohexylmethyleneimine, and a structural unit derived from acrylate or methacrylate. The colored photosensitive resin composition of claim 1, wherein the colorant is a pigment-containing coloring agent. The colored photosensitive resin composition of claim 1, wherein the content of the xanthene dye is 0.1 to 50% by mass based on the content of the solid content of the colored photosensitive resin composition. A color filter formed by the colored photosensitive resin composition of claim 1. A display device comprising the color filter as recited in claim 9.