TWI570507B - Colored 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 used for the production of a color filter used in a display device such as a liquid crystal display panel, an electroluminescence panel, or a plasma display panel. As such a color-sensitive photosensitive resin composition, a coloring photosensitive resin composition containing a copolymer of methacrylic acid and 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]nonyl acrylate as a resin is known (JP2010- 211198-A).

When a colored pattern is to be formed using the colored photosensitive resin composition, a photolithography method may be employed, that is, a colored photosensitive resin composition is applied onto a substrate to form a composition layer, and the composition layer is exposed through a photomask and developed. Get the pattern. However, when the coloring photosensitive resin composition proposed above is used, a part of the unexposed portion of the composition layer formed from the colored photosensitive resin composition is peeled off during development, and the release sheet adheres to the colored pattern. The situation of becoming a foreign object.

The invention includes the following invention.

[1] A colored photosensitive resin composition containing a colorant, a resin, a polymerizable compound, and a polymerization initiator; the colorant is a coloring agent containing a dibenzopyran dye and a pigment, and the resin is derived from a structural unit selected from the group consisting of a group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride; a structural unit derived from a monomer having a cyclic ether structure having a carbon number of 2 to 4 and an ethylenically unsaturated bond, and From formula (x) [In the formula (x), R ^a1 represents a hydrogen atom or a methyl group; R ^a2 represents an alkyl group having 1 to 6 carbon atoms; p represents an integer of 0 to 5; and when p is 2 or more, plural R ^a2 may be the same or Copolymers of structural units of different monomers shown.

[2] The colored photosensitive resin composition according to [1], wherein the content of the structural unit derived from the monomer represented by the formula (x) is 1 mol% based on the total amount of the structural unit constituting the copolymer. Above, 80% or less.

[3] The colored photosensitive resin composition according to [1] or [2], wherein the monomer represented by the formula (x) is vinyltoluene.

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

[5] A display device comprising a color filter as in [4].

According to the colored photosensitive resin composition of the present invention, it is possible to prevent a portion of the unexposed portion of the composition layer formed from the colored photosensitive resin composition from being peeled off during development, and to reduce foreign matter on the colored pattern.

The colored photosensitive resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and the colorant (A) contains a dibenzopyran dye ( A1) a coloring agent with a pigment (A2), wherein the resin (B) is a structural unit derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and has a carbon number of 2 to 4 a structural unit of a monomer having a cyclic ether structure and an ethylenically unsaturated bond, and derived from the formula (x) [In the formula (x), R ^a1 represents a hydrogen atom or a methyl group; R ^a2 represents an alkyl group having 1 to 6 carbon atoms; p represents an integer of 0 to 5; and when p is 2 or more, plural R ^a2 may be the same or A resin of a copolymer of structural units different from the monomer shown.

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

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

<Colorant (A)>

The colorant (A) contains a dibenzopyran dye (A1) and a pigment (A2). Further, a dye different from the dibenzopyran dye (A1) (hereinafter sometimes referred to as "dye (A3)") may be contained.

The dibenzopyran dye (A1) is a dye containing a compound having a dibenzopyran skeleton in the molecule. As a dibenzopyran dye (A1), for example, it can be listed Lift: CI Acid Red 51 (hereinafter, the description of CI Acid Red is omitted, only the number is written; the others are the same), 52, 87, 92, 94, 289, 388, CI Acid Violet 9, 30, 102, CI Alkali Red 1 (Rose red 6G), 2, 3, 4, 8, CI alkaline red 10 (Rose red B), 11, CI alkaline purple 10, 11, 25, CI solvent red 218, CI mordant red 27, CI reaction Sexual red 36 (Bengal rose red B), acid rose red G, dibenzopyran dye disclosed in Japanese Patent Laid-Open Publication No. 2010-32999, and dibenzopyran dye disclosed in Japanese Patent No. 4492760 . It is preferably dissolved in an organic solvent.

Among these, the dibenzopyran dye (A1) is preferably a dye containing a compound represented by the formula (1a) (hereinafter sometimes referred to as "compound (1a)"). In the case of using the compound (1a), the content of the compound (1a) in the dibenzopyran dye (A1) is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass. the above. Particularly, as the dibenzopyran dye (A1), it is preferred to use only the compound (1a).

[In the formula (1a), R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁸ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent; and R ¹ and R ² may be bonded to each other. The adjacent nitrogen atoms form a ring together, and R ³ and R ⁴ may be bonded to each other to form a ring together with the adjacent nitrogen atom; R ⁵ represents -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , CO ₂ H, -CO ₂ ^- Z ⁺ , -CO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ ; R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; m represents an integer of 0 to 5; when m is an integer of 2 or more, a plurality of R ^{5 are the} same or different; a represents an integer of 0 or 1, and X represents a halogen atom; and R ⁸ represents a carbon number of 1 to 20. a monovalent saturated hydrocarbon group in which a hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom; Z ⁺ represents ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ ; and R ⁹ and R ¹⁰ each independently represent a hydrogen atom or carbon a saturated hydrocarbon group having a valence of 1 to 20, and R ⁹ and R ¹⁰ may be bonded to each other to form a heterocyclic ring of 3 to 10 member rings together with a neighboring nitrogen atom; and R ¹¹ independently represents a hydrogen atom and a carbon number of 1 to 20; a monovalent saturated hydrocarbon group or an aralkyl group having a carbon number of 7 to 10] as a monovalent aromatic group representing a carbon number of 6 to 10 of R ¹ to R ⁴ Examples of the aromatic hydrocarbon group include a phenyl group, a tolylmethyl group, and a xylyl group. Base, propylphenyl and butylphenyl groups.

And a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms of R ¹ to R ⁴ , wherein the hydrogen atom contained in the aromatic hydrocarbon group may pass through a halogen atom, -R ⁸ , -OH, -OR ⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ R ⁸ , -SR ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ^{10 is} substituted. Among the substituents, at least one selected from the group consisting of -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ and -SO ₂ NR ⁹ R ¹⁰ is preferred, and more preferably selected from the group consisting of At least one of the group consisting of -SO ₃ ^- Z ⁺ and -SO ₂ NR ⁹ R ¹⁰ . As this case, -SO ₃ ^- Z ^{+ is} preferably -SO ₃ ^-+ N(R ¹¹ ) ₄ . When R ¹ to R ^{4 are} these groups, the colored photosensitive resin composition containing the compound (1a) can form a color filter having less generation of foreign matter and further excellent heat resistance.

R ¹ and R ² may be bonded to each other to form a ring together with an adjacent nitrogen atom, and R ³ and R ⁴ may be bonded to each other to form a ring together with the adjacent nitrogen atom. Examples of the ring containing the nitrogen atom include the following.

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

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

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

Examples of -SR ⁸ include a methylthio group, an ethylthio group, a butylthio group, a hexylthio group, an anthracenylthio group, and an eicosylthio group.

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

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

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

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

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

Examples of the alkyl group having 1 to 6 carbon atoms of R ⁶ and R ⁷ include the above-mentioned linear alkyl group and branched alkyl group, and the number of carbon atoms is 1 to 6.

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

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

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

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

The dibenzopyran dye (A1) is more preferably a dye containing a compound represented by the formula (2a) (hereinafter sometimes referred to as "compound (2a)"). When the compound (2a) is used, the content of the compound (2a) in the dibenzopyran dye (A1) is preferably 50% by mass or more, more preferably 70% by mass or more, and furthermore Good is 90% by mass or more.

[In the formula (2a), R ²¹ to R ²⁴ each independently represent a hydrogen atom, -R ²⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent; and R ²¹ and R ²² may be bonded to each other. The adjacent nitrogen atoms form a ring together, and R ²³ and R ²⁴ may be bonded to each other to form a ring together with the adjacent nitrogen atom; R ²⁵ represents -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Zl ⁺ or -SO ₂ NHR ²⁶ ; m1 represents an integer of 0 to 5; when m1 is an integer of 2 or more, a plurality of R ^{25 are the} same or different; a1 represents an integer of 0 or 1, X1 represents a halogen atom; and R ²⁶ represents a carbon number of 1-20. a monovalent saturated hydrocarbon group; Zl ⁺ represents ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ ; R ²⁷ each independently represents a monovalent saturated hydrocarbon group or a benzyl group having a carbon number of 1 to 20] as R ²¹ to R Examples of the aromatic hydrocarbon group having a carbon number of 6 to 10 and having a carbon number of ²⁴ are the same as those exemplified as the above-mentioned R ¹ to R ⁴ as the aromatic hydrocarbon group. The hydrogen atom contained in the aromatic hydrocarbon group may be substituted with -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Zl ⁺ , -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ .

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

Further, it is preferred that R ²¹ and R ²² are bonded to each other to form an aliphatic heterocyclic ring together with a nitrogen atom, and R ²³ and R ²⁴ are bonded to each other to form an aliphatic heterocyclic ring together with a nitrogen atom.

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

Examples of the aliphatic heterocyclic ring include the following.

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

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

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

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

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

The compound (2a) may, for example, be a compound represented by the formula (1-1) to the formula (1-24). Further, in the formula, R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched alkyl group having 6 to 12 carbon atoms, and more preferably 2-ethylhexyl group. Among these, a sulfonium amidate of CI Acid Red 289, a quaternary ammonium salt of CI Acid Red 289, a sulfonamide of CI Acid Violet 102, or a quaternary ammonium salt of CI Acid Violet 102 is preferred. Examples of such a compound include compounds represented by the formulae (1-1) to (1-8), (1-11) and (1-12).

Further, the dibenzopyran dye (A1) is more preferably a dye containing a compound represented by the formula (3a) (hereinafter sometimes referred to as "compound (3a)"). In the case of using the compound (3a), the content of the compound (3a) in the dibenzopyran dye (A1) is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass. the above.

[In the formula (3a), R ³¹ and R ³² each independently represent an alkyl group having 1 to 4 carbon atoms; and R ³³ and R ³⁴ each independently represent an alkyl group having 1 to 4 carbon atoms and an alkylthio group having 1 to 4 carbon atoms; Or an alkylsulfonyl group having 1 to 4 carbon atoms; R ³¹ and R ³³ may be bonded to each other to form a ring together with an adjacent nitrogen atom and a carbon atom, and R ³² and R ³⁴ may be bonded to each other and to a neighboring nitrogen atom and carbon. The atoms form a ring together; p and q independently represent an integer from 0 to 5; when p is 2 or more, the plurality of R ³³ may be the same or different. When q is 2 or more, a plurality of R ³⁴ may be used. The same or different. As the alkyl group having 1 to 4 carbon atoms representing R ³¹ , R ³² , R ³³ and R ³⁴ , a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group or an isobutyl group may be mentioned. , a second butyl group, a third butyl group, and the like.

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

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

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

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

The compound (3a) may, for example, be a compound represented by the formula (1-25) to the formula (1-31). Among them, a compound represented by the formula (1-25) is preferred from the viewpoint of excellent solubility in an organic solvent.

As the dibenzopyran dye (A1), a commercially available dibenzopyran dye (for example, "Chugai Aminol Fast Pink RH/C" manufactured by Sino-foreign Chemical Co., Ltd., and "Rhodamin" manufactured by Tajika Chemical Industry Co., Ltd. can be used. 6G"). Further, a commercially available dibenzopyran dye can also be used as a starting material, and it can be synthesized with reference to JP2010-32999-A.

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

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

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

As the pigment, preferred are blue pigments such as CI Pigment Blue 15, 15:3, 15:4, 15:6, 60, and purple pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38, and the like. Jia is CI Pigment Blue 15:3, 15:6 and CI Pigment Violet 23, and more preferably CI Pigment Blue 15:6. By containing the above pigment, it is easy to optimize the transmission spectrum, and the light resistance and chemical resistance of the color filter are improved.

The pigment (A2) may be subjected to a rosin treatment, a surface treatment using a pigment derivative introduced with an acidic group or a basic group, a graft treatment of a pigment surface by a polymer compound or the like, a sulfuric acid micronization method, or the like. The micronization treatment or the cleaning treatment by an organic solvent or water for removing impurities, the removal treatment of ionic impurities by an ion exchange method, or the like.

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

Examples of the pigment dispersant include pigment dispersants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic. These pigment dispersants may be used singly or in combination of two or more. Examples of the pigment dispersant include a product name KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by CIBA Co., Ltd.), and Ajisper. (Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (manufactured by BYK-Chemie Co., Ltd.), and the like.

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

The dye (A3) is not particularly limited, and known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, mord dyes, and the like, and dyes which are soluble in an organic solvent are preferable.

Examples of the dye (A3) include a dye classified as a dye (published by The Society of Dyers snd Colourists) or a known dye described in Dyeing Note (color dyeing company). Further, according to the chemical structure, examples thereof include an azo dye, a cyanine dye, a triphenylmethane dye, a phthalocyanine dye, an anthraquinone dye, a naphthoquinone dye, a quinone imine dye, a methine dye, and a methine azo dye. , squaric acid dye, acridine dye, styrene Dyes, coumarin dyes, quinoline dyes, nitro dyes, and the like. Among these, an organic solvent-soluble dye is preferred.

Specifically, CI solvent yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 117, 162, 163, 167, 189; CI solvent red 45 , 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247; CI Solvent Orange 2, 7, 11, 15, 26, 56, 77, 86; CI solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; CI solvent blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59: 1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139; CI solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 and other CI solvent dye; CI acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 57, 66, 73, 76, 80, 88, 97 , 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 182, 183, 195, 198, 206, 211, 215, 216 , 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 308, 312, 315, 316, 339, 341, 345, 346, 349 , 382, 383, 394, 401, 412, 417, 418, 422, 426; CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; CI acid violet 6B, 7, 17, 19, 34; CI acid blue 1, 7, 9, 15, 18, 22, 23, 25, 27, 29, 40, 41, 42, 43, 45, 51, 59, 60, 62, 70, 72, 74, 78, 80, 82, 83, 86, 87, 90, 92, 93, 100, 102, 103, 104, 112, 113, 117, 120, 126, 127, 129, 130, 131, 138, 142, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 184, 187, 192, 199, 210, 229, 234 , 236, 242, 243, 256, 259, 267, 285, 296, 315, 324:1, 335; CI acid green 1, 3, 5, 9, 16, 25, 27, 28, 41, 50, 58, CI acid dyes such as 63, 65, 80, 104, 105, 106, 109, CI direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71 , 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141; CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181 , 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250; CI direct orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84 , 89, 90, 93, 95, 96, 103, 104; CI direct blue 1, 2, 6, 8, 15, 22, 25, 40, 41, 57, 71, 76, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293; CI Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68 , 69, 72, 77, 79, 82 and other CI direct dyes, CI disperse yellow 51, 54, 76; CI disperse violet 26, 27; CI disperse blue 1, 14, 56, 60 and other disperse dyes; CI basic blue 1, 3, 5, 7, 9, 19, 22, 24, 25, 26, 28, 29, 40, 41, 47, 54, 58, 59, 64, 65, 66, 67, 68; CI basic green 1 and other CI basic dyes; CI reactive yellow 2, 76, 116; CI reactive orange 16 and other CI reactive dyes; CI mordant yellow 5 , 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; CI mordant red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95; CI mordant orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37 , 42, 43, 47, 48; CI mordant purple 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58; CI mord blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 26, 30, 31, 39, 40, 41, 43, 44, 49 , 53, 61, 74, 77, 83, 84; CI mord green 1, 3, 4, 5, 10, 15, 26, 29 33,34,35,41,43,53 etc. C.I. mordant dyes;. 1 C. I. Vat Green C.I. vat dyes and the like; and the like.

The dyes may be suitable for the spectroscopic spectrum of the desired color filter select. These dyes may be used alone or in combination of two or more.

When the coloring agent (A) contains the dye (A3), the content of the dye (A3) is preferably from 1 to 90% by mass, more preferably from 1 to 50% by mass, based on the total amount of the coloring agent (A).

In the case where the colorant (A) contains the dibenzopyran dye (A1) and the pigment (A2), the content ratio of the dye (A1) to the pigment (A2) is preferably from 1:99 to 90 on a mass basis. : 10, more preferably 2:98~70:30, and even more preferably 2:98~50:50. By setting such a ratio, it is easy to optimize the transmission spectrum, and the obtained color filter tends to be excellent in contrast, brightness, heat resistance, and chemical resistance.

The content of the colorant (A) is preferably from 5 to 60% by mass, more preferably from 8 to 50% by mass, even more preferably from 10 to 40% by mass, based on the total amount of the solid content component. When the content of the coloring agent (A) is in the above range, the color density when the color filter is prepared is sufficient, and the necessary amount of the resin (B) or the polymerizable compound (C) can be contained in the composition, so that it can be formed. A color filter with sufficient mechanical strength.

Here, the "total amount of the solid content component" in the present specification means the amount of the solvent removed from the total amount of the colored photosensitive resin composition. The total amount of the solid content component and the content of each component relative thereto can be measured, for example, by a known analytical method such as liquid chromatography or gas chromatography.

<Resin (B)>

The resin (B) contains a structural unit derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter sometimes referred to as "(a)"), derived from having a carbon number of 2~ a structural unit of a cyclic ether structure of 4 and a monomer having an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b)"), and derived from the formula (x) [In the formula (x), R ^a1 represents a hydrogen atom or a methyl group; R ^a2 represents an alkyl group having 1 to 6 carbon atoms; p represents an integer of 0 to 5; and when p is 2 or more, plural R ^a2 may be the same or A copolymer of a structural unit of a monomer (hereinafter sometimes referred to as "(x)") (hereinafter sometimes referred to as "copolymer (B1)").

From the aspect of the polymerizability of the monomer, R ^{a1 is} preferably a hydrogen atom.

In the formula (x), examples of the alkyl group having 1 to 6 carbon atoms of R ^a2 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, and an isopenic group. Base, neopentyl and so on.

R ^{a2 is} preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group.

p is preferably an integer of 0 to 2, more preferably 1.

Examples of (x) include styrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, α-methylstyrene, and ethylstyrene. Among them, o-vinyltoluene, m-vinyltoluene and p-vinyltoluene are preferred, and p-vinyltoluene is more preferred. When the (x) is vinyl toluene, the film to which the colored photosensitive resin composition is applied is excellent in solubility in an organic solvent, and therefore, for example, precipitation in a pipe or a discharge portion inside the coating device tends to be suppressed.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-p-vinylbenzoic acid, and maleic acid and antibutene. Acid, methyl maleic acid, methyl fumaric acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrogen Unsaturated dicarboxylic acids such as phthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid; methyl-5 -drop Aceene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methyl Bicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2- a bicyclic unsaturated compound containing a carboxyl group such as a olefin or a 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene; maleic anhydride, methyl maleic anhydride, itaconic anhydride, 3 -vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride , an unsaturated dicarboxylic acid anhydride such as dimethyltetrahydrophthalic anhydride or 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (bicycloheptene dicarboxylic anhydride); succinic acid mono[ Unsaturated mono- or more than two or more polycarboxylic acids such as 2-(methyl)propenyloxyethyl]ester and phthalic acid mono[2-(methyl)propenyloxyethyl]ester Alkyloxyalkylene esters; such as α-(hydroxymethyl)acrylic acid, unsaturated acrylates having a hydroxyl group and a carboxyl group in the same molecule.

Among these, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferable from the viewpoint of copolymerization reactivity or solubility in an alkaline aqueous solution.

In the present specification, the term "(meth)acrylinyl" means at least one selected from the group consisting of an acryloyl group and a methacryl group. The expressions "(meth)acrylic acid" and "(meth) acrylate" have the same meaning.

(b) means, for example, a cyclic ether structure having a carbon number of 2 to 4 (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and ethylene are not A polymerizable compound of a saturated bond. (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloxy group.

(b), for example, a monomer (b1) having an oxirane group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), having an oxetane group and an ethyl group a monomer (b2) having an unsaturated bond (hereinafter sometimes referred to as "(b2)"), a monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)"), etc.) .

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

Examples of (b1-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, and glycidyl vinyl ether. , o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-divinyl Benzyl glycidyl ether, a-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidoxymethyl)styrene, 2,4-bis(glycidoxymethyl)benzene Ethylene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4-tris(glycidoxymethyl)styrene, 2,3,5-tris(glycidoxymethyl)styrene, 2,3,6-tris(glycidoxymethyl)styrene, 3,4,5-tris(glycidoxymethyl) ) styrene, 2,4,6-tris(glycidoxymethyl)styrene, and the like.

Examples of (b1-2) include cyclohexene oxide ethylene and 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000; manufactured by Daicel Chemical Industry Co., Ltd.), (methyl). 3,4-epoxycyclohexyl methyl acrylate (for example, Cyclomer A400; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexyl methyl (meth)acrylate (for example, Cyclomer M100; Daicel Chemical Industry) (Production), a compound represented by the formula (I), a compound represented by the formula (II), and the like.

[In the formulae (I) and (II), R ^b1 and R ^b2 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group; X ^b1 and X ^b2 represent a single ^{bond, -R b3 -, * - R} b3 -O -, * - R b3 -S- or * -R ^b3 -NH-; R ^b3 represents alkanediyl group having a carbon number of 1 to 6; and O * represents the Key button]

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

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

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

Examples of the alkanediyl group include a methylene group, an exoethyl group, a propionyl-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a penta-1,5-di group. Base, hex-1,6-diyl, and the like.

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

Examples of the compound represented by the formula (I) include a compound represented by the formula (I-1) to the formula (I-15). Among them, preferred are the formula (I-1), the formula (I-3), the formula (I-5), the formula (I-7), the formula (I-9), and the formula (I-11) to the formula (I). a compound represented by any one of -15), more preferably a compound represented by any one of the formula (I-1), the formula (I-7), the formula (I-9) and the formula (I-15) .

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

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

The monomer (b2) having an oxetane group and an ethylenically unsaturated bond is more preferably a monomer having an oxetane group and a (meth) acryloxy group. Examples of (b2) include 3-methyl-3-methylpropenyloxymethyloxetane, 3-methyl-3-propenyloxymethyloxetane, and 3- Ethyl-3-methyl Propylene methoxymethyl oxetane, 3-ethyl-3-propenyloxymethyl oxetane, 3-methyl-3-methylpropenyloxyethyl oxetane Alkane, 3-methyl-3-propenyloxyethyloxetane, 3-ethyl-3-methylpropenyloxyethyloxetane, 3-ethyl-3-propene Alkoxyethyloxetane 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)acryloxy group. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

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

Further, the copolymer (B1) may have a structural unit derived from a monomer which is different from (a), (b) and (x) and which may be copolymerized with the above (hereinafter sometimes referred to as "(c)").

Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, and (meth)acrylic acid. (meth) acrylates such as tributyl acrylate, allyl (meth) acrylate, propargyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxy propyl (meth) acrylate a (meth) acrylate containing a hydroxyl group such as an ester; a dicarboxylic acid diester such as diethyl maleate, diethyl fumarate or diethyl itaconate; Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2 .1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5- Methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6 -dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1 Hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-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(t-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]g Bicyclic unsaturated compounds such as 2-ene; N-phenyl maleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N- Diterpenoidimine-3-maleimide imide benzoate, N-butanediamine-4-butyleneimine butyrate, N-butanediamine -6-m-butylenediamine hexanoate, N-butyl succinimide-3-synylene diimide propionate and N-(9-acridinyl) maleic acid Dicarbonyl ruthenium derivatives such as imine; p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1 , 3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

Among these, from the aspects of copolymerization reactivity and heat resistance, it is preferably N-phenyl maleimide, N-cyclohexyl maleimide, N-benzyl maleimide, and bicyclo [2.2.1] hept-2-ene.

When the copolymer (B1) is a copolymer containing a structural unit derived from (x), a structural unit derived from (a), and a structural unit derived from (b), respectively, derived from (x), (a) And the content ratio of the structural unit of (b) is preferably a structural unit derived from (x): 1 to 80 mol% with respect to the total amount of structural units constituting the copolymer.

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

The structural unit derived from (b): 2 to 95 mol%, more preferably the structural unit derived from (x): 1 to 65 mol%

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

The structural unit derived from (b): 5 to 80 mol%.

When the ratio of the respective structural units is in the above range, the peeling of the unexposed portion during development from the composition layer formed of the colored photosensitive resin composition tends to be suppressed, so that the generation of foreign matter tends to be further reduced.

When the copolymer (B1) is a copolymer containing a structural unit derived from (x), a structural unit derived from (a), a structural unit derived from (b), and a structural unit derived from (c), The content ratio of the structural unit derived from (x), (a), (b), and (c), respectively, is preferably a structural unit derived from (x) with respect to the total amount of structural units constituting the copolymer: ~80 mole%

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

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

Structural unit derived from (c): 2~80 mol%, More preferably from (x) structural unit: 1~65 mol%

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

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

The structural unit derived from (c): 2 to 65 mol%.

When the ratio of the respective structural units is in the above range, the peeling of the unexposed portion during development from the composition layer formed of the colored photosensitive resin composition tends to be suppressed, so that the generation of foreign matter tends to be further reduced.

The copolymer (B1) is preferably a copolymer containing a structural unit derived from (x), a structural unit derived from (a), and a structural unit derived from (b).

The copolymer (B1) can be, for example, the method described in the "Experimental Method for Polymer Synthesis" (the first printing of the first edition of the Otsuka Ryokan Institute of Chemicals, the first printing of March 1, 1972) and the document. The cited documents are produced by reference.

Specifically, a specific amount of (x), (a), (b), and optionally (c), a polymerization initiator, a solvent, and the like are introduced into a reaction container, for example, by replacing oxygen with nitrogen. Deoxidation environment, heating and heat preservation while stirring. In addition, the polymerization initiator, the solvent, and the like used herein are not particularly limited, and a general user in the field can be used. For example, examples of the polymerization initiator include an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or organic. A peroxide (such as benzamidine peroxide) may be used as a solvent to dissolve each monomer, and a solvent (E) or the like which will be described later may be used as a solvent for coloring the photosensitive resin composition.

Furthermore, the obtained copolymer can be directly used as a solution after the reaction, and can also be used. The concentrated or diluted solution can also be used as a solid (powder) acquirer by a method such as reprecipitation. In particular, since the solvent (E) described later is used as a solvent in the polymerization, the solution after the reaction can be used as it is, thereby simplifying the production steps.

The polystyrene-equivalent weight average molecular weight of the copolymer (B1) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000. When the molecular weight is in the above range, the hardness of the color filter is improved, the residual film ratio is also high, the solubility of the unexposed portion to the developer is good, and the resolution is further improved.

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

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

The resin (B) may contain a resin different from the copolymer (B1) (hereinafter sometimes referred to as "resin (B2)"). The resin (B2) is not particularly limited, and is preferably an alkali-soluble resin. Examples of the resin (B2) include the following resins [K1] to [K6].

Resin [K1]: copolymer of (a) and (b); resin [K2]: copolymer of (a) and (b) and (c); resin [K3]: (a) and (a) a copolymer of a monomer which is copolymerized and different from (a) and (b) (hereinafter sometimes referred to as "(c')"); a resin [K4]: a copolymer of (a) and (c') (b) the tree obtained by the reaction Fatty resin [K5]: a resin obtained by reacting the copolymer of (b) and (c') with (a); resin [K6]: copolymer of (b) and (c') with (a) The reaction is further carried out by reacting a carboxylic anhydride with a resin. Here, examples of (c') include the monomers exemplified in the above (x) and (c). In the resin [K1], the ratio of the structural units derived from (a) and (b), respectively, is preferably a structural unit derived from (a) with respect to the total structural unit constituting the resin [K1]: 2 to 60. Moer%

The structural unit derived from (b): 40 to 98 mol%, more preferably the structural unit derived from (a): 10 to 50 mol%

The structural unit derived from (b): 50 to 90 mol%.

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

The resin [K1] can be produced, for example, in the same manner as the method disclosed as the method for producing the copolymer (B1).

In the resin [K2], the ratio of the structural units derived from (a), (b) and (c), respectively, in the total structural unit constituting the resin [K2], preferably the structural unit derived from (a) : 2~45mol%

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

Structural unit derived from (c): 1 to 65 mol%, more preferably Structural unit derived from (a): 5~40 mol%

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

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

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

The resin [K2] can be produced, for example, in the same manner as the method disclosed as the method for producing the copolymer (B1).

In the resin [K3], the ratio of the structural units derived from (a) and (c'), respectively, in the total structural unit constituting the resin [K3], preferably the structural unit derived from (a): 2~ 60% by mole

The structural unit derived from (c'): 40 to 98 mol%, more preferably the structural unit derived from (a): 10 to 50 mol%

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

The resin [K3] can be produced, for example, in the same manner as the method disclosed as the method for producing the copolymer (B1).

The resin [K4] can be obtained by adding the copolymer of (a) and (c'), and adding the cyclic ether having 2 to 4 carbon atoms of (b) to the carboxylic acid (a) and/or Manufactured on the carboxylic acid anhydride.

First, a copolymer of (a) and (c') is produced in the same manner as the method disclosed as a method for producing the copolymer (B1). In this case, the structural unit ratios derived from (a) and (c'), respectively, are preferably listed with the resin [K3]. The same ratio.

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

After the copolymer of (a) and (c') is produced, the environment inside the flask is replaced by nitrogen to air, and the reaction catalyst of (b), a carboxylic acid or a carboxylic anhydride and a cyclic ether (for example, tris(dimethylamine) A resin [K4] can be obtained by charging a reaction such as a methyl group (such as a phenol) and a polymerization inhibitor (for example, hydroquinone) into the flask at a temperature of, for example, 60 to 130 ° C for 1 to 10 hours.

The amount of use of (b) is preferably from 5 to 80 moles, more preferably from 10 to 75 moles, relative to (a) 100 moles. When it is in this range, the storage stability of the colored photosensitive resin composition, the developability in forming a colored pattern, and the balance of solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained colored pattern become good. tendency. Since the reactivity of the cyclic ether is high and the unreacted (b) is hard to remain, it is preferably (b1), more preferably (b1-1), as the resin (K4).

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

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

Resin [K5], as the first stage, by using the copolymer (B1) The copolymer of (b) and (c') is obtained in the same manner as the method disclosed. Similarly to the above, the obtained copolymer may be directly used as a solution after the reaction, or may be a solution obtained by concentration or dilution, or may be obtained as a solid (powder) by a method such as reprecipitation.

The ratio of the structural units derived from (b) and (c') is preferably in the following range with respect to the total number of moles of the total structural unit constituting the above copolymer.

Structural unit derived from (b): 5~95 mol%

The structural unit derived from (c'): 5 to 95 mol%, more preferably the structural unit derived from (b): 10 to 90 mol%

The structural unit derived from (c'): 10 to 90 mol%.

Further, under the same conditions as in the production method of the resin [K4], the cyclic ether derived from (b) and the carboxylic acid (a) having the copolymer of (b) and (c') are obtained. The reaction is carried out with a carboxylic acid anhydride, whereby the resin [K5] can be produced.

The amount of (a) used in the reaction with the above copolymer is preferably from 5 to 80 moles per 100 moles of (b). Since the reactivity of the cyclic ether is high and the unreacted (b) is hard to remain, it is preferably (b1), more preferably (b1-1), as the resin (K5).

The resin [K6] is a resin in which the resin [K5] is further reacted with a carboxylic acid anhydride. The hydroxyl group produced by the reaction of a cyclic ether with a carboxylic acid or a carboxylic anhydride is reacted with a carboxylic anhydride.

Examples of the carboxylic acid anhydride include maleic anhydride, methyl maleic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, and 3,4,5. ,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydroortylene Formic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (bicycloheptene dicarboxylic anhydride), and the like. The amount of the carboxylic anhydride used is 1 mole, preferably 0.5 to 1 mole, relative to the amount used in (a).

Specific examples of the resin (B2) include 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer and 3,4-epoxytricycloacrylate [5.2.1.0]. ^2.6 ] resin such as oxime ester/(meth)acrylic acid copolymer [K1]; glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxy acrylate Tricyclo [5.2.1.0 ^2.6 ] decyl ester / (meth) acrylate / N-cyclohexyl maleimide copolymer, 3-methyl-3-(methyl) propylene methoxymethyl oxalate Resin such as cyclobutane/(meth)acrylic acid/N-cyclohexylmethyleneimine copolymer [K2]; benzyl (meth)acrylate/(meth)acrylic acid copolymer, styrene/(A) a resin such as an acrylic copolymer [K3]; a resin obtained by adding a glycidyl (meth)acrylate to a benzyl (meth)acrylate/(meth)acrylic acid copolymer, and a tricyclic fluorene (meth)acrylate Addition of a resin of glycidyl (meth)acrylate to an ester/styrene/(meth)acrylic acid copolymer, tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid Addition of a resin of glycidyl (meth)acrylate to the copolymer Resin [K4]; a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate with (meth)acrylic acid, and tricyclodecyl (meth)acrylate/styrene a resin such as a resin of glycidyl (meth)acrylate and a resin reactive with (meth)acrylic acid [K5]; a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate A resin such as a resin which reacts with (meth)acrylic acid and further reacts with tetrahydrophthalic anhydride, such as a resin [K6].

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

Among them, as the resin (B2), a resin [K1], a resin [K2], and a resin [K3] are preferable.

The polystyrene-equivalent weight average molecular weight of the resin (B2) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000. When the molecular weight is in the above range, the hardness of the color filter is improved, the residual film ratio is also high, and the solubility of the unexposed portion to the developer is good, and the resolution tends to be improved.

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

The acid value of the resin (B2) is preferably 50 to 170 mg-KOH/g, more preferably 60 to 150, and still more preferably 70 to 135 mg-KOH/g.

The resin (B) may be only the copolymer (B1), and in the case of containing the resin (B2), the content thereof is preferably from 1 to 95% by mass, more preferably from 5 to 90, based on the total amount of the resin (B). quality%.

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

<Polymerizable compound (C)>

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

Among them, as the polymerizable compound (C), it is preferred to have three or more ethylene groups. A polymerizable compound of a sexually unsaturated bond. Examples of such a polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylic acid. Ester, dipentaerythritol hexa(meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, pentaerythritol deca (meth) acrylate, pentaerythritol nin (meth) acrylate Ester, tris(2-(meth)acryloxyethyl)isocyanurate, ethylene glycol modified pentaerythritol tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate Ester, propylene glycol modified pentaerythritol tetra(meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth) acrylate, caprolactone modified pentaerythritol tetra(meth) acrylate, caprolactone modified dipentaerythritol hexa Methyl) acrylate or the like. The photopolymerizable compound (C) may be used singly or in combination of two or more.

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

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

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

<Polymerization initiator (D)>

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

As the polymerization initiator (D), it is preferred to contain a compound selected from the group consisting of alkyl benzophenones, and The polymerization initiator of at least one of the compound, the fluorenylphosphine oxide compound, the O-mercapto fluorene compound, and the biimidazole compound is more preferably a polymerization initiator containing an O-fluorenyl hydrazine compound.

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

As the O-indenyl ruthenium compound, for example, N-benzylideneoxy-1-(4-phenylthiophenyl)butan-1-one-2-imine, N-benzylideneoxy group- 1-(4-Phenylthiophenyl)oct-1-one-2-imine, N-benzylideneoxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1 -keto-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethane-1- Imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxocyclopentylmethoxy) Benzamethylene}-9H-indazol-3-yl]ethane-1-imine, N-ethyloxy-1-[9-ethyl-6-(2-methylbenzhydryl) -9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzylideneoxy-1-[9-ethyl-6-(2-methylbenzhydryl) )-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as Irgacure OXE01, OXE02 (above, manufactured by BASF Corporation), and N-1919 (made by ADEKA Co., Ltd.) can also be used.

The alkylphenone compound is a compound having a partial structure represented by the formula (d2) or a partial structure represented by the formula (d3). In this part of the structure, the benzene ring may have a Daiji.

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

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

From the viewpoint of sensitivity, as the alkylphenone compound, a compound having a partial structure represented by the formula (d2) is preferred.

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

The fluorenylphosphine oxide compound may, for example, be 2,4,6-trimethylbenzimidyldiphenylphosphine oxide or the like. Commercial products such as Irgacure 819 (manufactured by Ciba Japan Co., Ltd.) can also be used.

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

Further, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl phthalate; 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(t-butylcarbonyl peroxide) benzophenone a benzophenone compound such as 2,4,6-trimethylbenzophenone; an anthracene compound such as 9,10-phenanthrenequinone, 2-ethylhydrazine, camphorquinone; 10-butyl-2-chloropurine Pyridone, benzoin, methyl phenylglyoxylate, titanocene compound, and the like. These are preferably used in combination with a polymerization initiation aid (D1) (especially an amine) to be described later.

Examples of the acid generator include 4-hydroxyphenyldimethylhydrazine p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-ethyloxyphenylene. Methyl hydrazine p-toluene sulfonate, 4-ethyl methoxy phenyl. methyl. Benzyl hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenylphosphonium p-toluenesulfonate, diphenylphosphonium hexafluorophosphate An onium salt such as a citrate or a nitrobenzyl tosylate or a benzoin tosylate.

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

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

Examples of the polymerization initiation assistant (D1) include an amine compound, an alkoxy fluorene compound, and 9-oxosulfuric acid. a compound, a carboxylic acid compound or the like.

The amine compound may, for example, be triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate or 4-dimethyl group. Isoamyl benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4 '-Bis(dimethylamino)benzophenone (commonly known as Michlerone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethyl Methylamino)benzophenone or the like, of which 4,4'-bis(diethylamino)benzophenone is preferred. It can also be marketed using EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.). Product.

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

9-oxosulfur Compounds can be exemplified by 2-isopropyl 9-oxosulfur 4-isopropyl 9-oxosulfur 2,4-diethyl 9-oxosulfur 2,4-dichloro 9-oxosulfur And 1-chloro-4-propoxy 9-oxosulfur Wait.

Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, and methoxyphenylthio group. Acetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine , naphthoxyacetic acid, and the like.

The polymerization initiation aid (D1) may be used singly or in combination of two or more.

When the polymerization initiator (D1) is used, the amount thereof is preferably 0.1 to 30 parts by mass, based on 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). Good is 1~20 parts by mass. When the amount of the polymerization initiation aid (D1) is in this range, the coloring pattern can be formed with a further high sensitivity, and the productivity of the color filter tends to be improved.

<Solvent (E)>

The solvent (E) is not particularly limited, and a solvent generally used in the field can be used. For example, it can be derived from an ester solvent (a solvent containing -COO- in the molecule, a solvent containing no -O-), an ether solvent (a solvent containing -O- in the molecule, a solvent containing no -COO-), an ether ester solvent (containing -COO in the molecule). - a solvent with -O-), a ketone solvent (a solvent containing -CO- in the molecule, a solvent containing no -COO-), an alcohol solvent, an aromatic hydrocarbon solvent, hydrazine It is selected for use as an amine solvent, dimethyl hydrazine or the like.

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

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

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

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

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

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

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

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

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

The content of the solvent (E) is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass based on the total amount of the colored photosensitive resin composition. In other words, the solid content of the colored photosensitive resin composition is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass. When the content of the solvent (E) is in the above range, the flatness at the time of coating becomes good, and the color filter is not formed. Since the color density is insufficient, the display characteristics tend to be good.

<Interacting Agent (F)>

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

Examples of the polyoxymethylene-based surfactant include a surfactant having a ruthenium oxygen bond. Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (manufactured by TORAY.DOWCORNING), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, SF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Momentive) Performance Materials Japan LLC))).

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

The polyfluorene-based surfactant having a fluorine atom may, for example, be a surfactant having a ruthenium oxygen bond or a fluorocarbon chain. Specific examples include Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, and Megafac F443 (manufactured by DIC).

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

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

<Other ingredients>

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

<Method for Producing Colored Photosensitive Resin Composition>

The colored photosensitive resin composition of the present invention can be, for example, a resin (B), a polymerizable compound (C), a polymerization initiator (D), and optionally a polymerization initiator (D1), a surfactant. (F) and other ingredients are prepared by mixing with the solvent (E).

In the case of containing the pigment (A2), it is preferred to preliminarily dissolve the pigment (A2). The agent (E) is mixed and dispersed using a bead mill or the like until the average particle diameter of the pigment is 0.2 μm or less. At this time, part or all of the above-mentioned pigment dispersant and resin (B) may be blended as needed. In the obtained pigment dispersion liquid, the dibenzopyran dye (A1), the remainder of the resin (B), and the polymerizable compound (C) and the polymerization initiator (D) used as needed are mixed at a specific concentration. The target coloring photosensitive resin composition can be prepared by remaining the solvent (E), the surfactant (F), and other components.

The dibenzopyran dye (A1) and the dye (A3) in the case of containing the dye (A3) may be previously dissolved in the solvent (E). The solution is preferably filtered by a filter having a pore diameter of about 0.01 to 1 μm.

The colored photosensitive resin composition after mixing is preferably filtered by a filter having a pore diameter of about 0.01 to 10 μm.

<Method of Manufacturing Color Filter>

The method of producing the colored pattern of the color filter from the colored photosensitive resin composition of the present invention includes a photolithography method, an inkjet method, a printing method, and the like. Among them, photolithography is preferred. The photolithography method is a method in which the colored photosensitive resin composition is applied onto a substrate, dried to form a composition layer, and the composition layer is exposed and developed through a photomask. In the photolithography method, a colored coating film as a cured product of the above composition layer can be formed by not using a photomask and/or not developing during exposure.

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

As the substrate, quartz glass, borosilicate glass, aluminosilicate glass can be used. a glass plate such as a soda-lime glass coated with cerium oxide on the surface, or a resin plate such as polycarbonate, polymethyl methacrylate or polyethylene terephthalate, and aluminum is formed on the substrate. Silver, silver/copper/palladium alloy films, etc. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on the substrates.

The formation of the pixels of the respective colors by the photolithography method can be carried out by known or conventional devices or conditions. For example, it can be produced by the following method.

First, the colored photosensitive resin composition is applied onto a substrate, and a volatile component such as a solvent is removed by heat drying (prebaking) and/or drying under reduced pressure, followed by drying to obtain a smooth composition layer.

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

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

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

The film thickness of the composition layer is not particularly limited, and can be appropriately adjusted depending on the materials to be used, the use, and the like. The thickness of the obtained colored pattern or the colored coating film is, for example, preferably 0.1 to 20 μm, more preferably 0.5 to 6 μm.

Next, the composition layer is exposed through a photomask used to form the target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern corresponding to the intended use can be used.

As the light source used in the exposure, a light source that generates light of a wavelength of 250 to 450 nm is preferable. For example, a light that is less than 350 nm can be cut off by a filter that cuts off the band, or a light band near the 436 nm, near 408 nm, and around 365 nm can be selectively extracted by extracting the band pass filters of the bands. Specifically, a mercury lamp, a light-emitting diode, a halide lamp, a halogen lamp, etc. are mentioned.

The entire surface of the exposure surface can be uniformly irradiated with parallel rays, or the reticle can be properly aligned with the substrate. Therefore, it is preferable to use an exposure device such as a reticle alignment machine and a stepper.

Development is carried out by bringing the exposed composition layer into contact with the developer to form a colored pattern on the substrate. By development, the unexposed portion of the composition layer is dissolved in the developer to be removed. As the developer, for example, an aqueous solution of a basic compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate or tetramethylammonium hydroxide is preferred. The concentration in the aqueous solution of the basic compound is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant.

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

It is preferred to carry out water washing after development.

Further, the obtained colored pattern is preferably post-baked. The post-baking temperature is preferably from 150 to 250 ° C, more preferably from 160 to 235 ° C. The post-baking time is preferably from 0.5 to 10 minutes, more preferably from 1 to 5 minutes.

The colored pattern and the colored coating film thus obtained are useful as a color filter.

According to the colored photosensitive resin composition of the present invention, a color filter excellent in brightness can be produced. The color filter is useful as a color filter used in a display device (for example, a liquid crystal display device or an organic EL device), an electronic paper, a solid-state imaging device, or the like.

Example

Next, the embodiments will be described, and the present invention will be specifically described. In the examples, % and parts of the content or the amount used are indicated, and unless otherwise specified, the mass basis is indicated.

Synthesis Example 1

In a flask equipped with a cooling tube and a stirring device, a mixture of a compound represented by the formula (A1-1a) and a compound represented by the formula (A1-1b) (trade name: Chugai Aminol Fast Pink R; manufactured by Sinotrans) was used. There were 150 parts of chloroform and 8.9 parts of N,N-dimethylformamide, and 10.9 parts of sulfite chloride was added dropwise while maintaining the temperature below 20 ° C under stirring. After completion of the dropwise addition, the temperature was raised to 50 ° C, and the mixture was allowed to react at the same temperature for 5 hours, and then cooled to 20 ° C. The reaction solution after cooling was maintained at 20 ° C or lower while stirring, and a mixture of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise. Thereafter, the mixture was stirred at the same temperature for 5 hours to cause a reaction. Then, the obtained reaction mixture was distilled off by a rotary evaporator to remove the solvent, and a small amount of methanol was added and stirred vigorously. The mixture was added to a mixed solution of 375 parts of ion-exchanged water while stirring to precipitate crystals. The precipitated crystals were separated by filtration, carefully washed with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain a dye (A1-1) (a compound of the formula (A1-1-1) to the formula (A2-2-8). A mixture of 11.3 parts.

Synthesis Example 2

40.5 parts of the compound of the formula (A1-2a) and 64.4 parts of 2-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.), and further N-methylpyridone (Kantong Chemical Co., Ltd.) (manufactured by) ()) 263 parts, stirred at 120 ° C for 8 hours. After the obtained reaction liquid was cooled to room temperature, it was added to a mixed liquid of 1200 parts of water and 75 parts of 35% hydrochloric acid, and the mixture was stirred at room temperature for 1 hour to precipitate crystals. The precipitated crystals were obtained as a residue obtained by suction filtration, and washed with 50 parts of tetrahydrofuran and 200 parts of water, and then dried under reduced pressure at 60 ° C for one night to obtain 49 parts of the compound of the formula (A1-2b). The yield was 89%.

Then, 20.1 parts of the compound of the formula (A1-2b), 28.7 parts of iodoethanol (manufactured by Tokyo Chemical Industry Co., Ltd.), 25.4 parts of potassium carbonate, and N-methylpyrrolidone (manufactured by Kanto Chemical Co., Ltd.) 130.7 The mixture was stirred at 80 ° C for 4 hours under light-shielding conditions. The obtained reaction liquid was cooled to room temperature, concentrated, added to 460 parts of water, and stirred at 10 to 15 ° C for 1 hour to precipitate crystals. After the obtained crystal was obtained as a residue for suction filtration, it was washed with 500 parts of 20% methanol water and 1000 parts of ion-exchanged water, and then dried under reduced pressure at 60 ° C for 1 night to obtain a formula (A1-2). Compound 20.6 parts. The yield was 93%.

Identification of the compound represented by formula (A1-2) (mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ 603.3 Exact Mass: 602.2

Synthesis Example 3

40.5 parts of the compound of the formula (A1-3a) and 60.5 parts of 2,6-diphenylmethylamine (manufactured by Tokyo Chemical Co., Ltd.) were mixed under light-shielding conditions, and 200 parts of N-methylpyridone was added. Stir at 150 ° C for 8 hours. After the obtained reaction liquid was cooled to room temperature, it was added to a mixed liquid of 1200 parts of water and 75 parts of 35% hydrochloric acid, and the mixture was stirred at room temperature for 1 hour to precipitate crystals. The precipitated crystals were obtained as a residue obtained by suction filtration, washed with 100 parts of methanol, and then dried under reduced pressure at 60 ° C for one night to obtain 49 parts of the compound of the formula (A1-3b). The yield was 85%.

Then, 28.8 parts of the compound represented by the formula (A1-3b), 21.6 parts of 1-bromopropane and 24.2 parts of potassium carbonate were added to 144 parts of N-methylpyridone, and the mixture was stirred at 90 ° C for 4 hours. The obtained reaction liquid was cooled to room temperature, concentrated, added to 560 parts of water, and stirred at 10 to 15 ° C for 1 hour to precipitate crystals. The obtained crystal was obtained as a residue obtained by suction filtration, dried, washed with 1000 parts of ion-exchanged water, and then dried under reduced pressure at 60 ° C for 1 night to obtain 30.0 parts of a compound represented by the formula (A1-3). The yield was 91%.

Identification of the compound represented by formula (A1-3) (mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ 659.3 Exact Mass: 658.3

Synthesis Example 4

Nitrogen was passed through a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel at 0.02 L/min to obtain a nitrogen atmosphere, and 257 parts by mass of propylene glycol monomethyl ether acetate was added thereto, and the mixture was heated to 70 ° C while stirring. Then, 68 parts by mass of methacrylic acid, 83 parts of vinyltoluene, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate (the compound represented by formula (I-1) and formula (II-) 1) The compound shown is mixed with 227 parts by mass of a molar ratio of 50:50, dissolved in 140 parts by mass of propylene glycol monomethyl ether acetate, and the solution is added dropwise to the solution by using a dropping funnel for 4 hours. In a 70 ° C flask.

On the other hand, 30 parts by mass of a polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) is dissolved in 225 parts by mass of propylene glycol monomethyl ether acetate, and other solutions are used. The dropping funnel was added dropwise to the flask over 4 hours. After completion of the dropwise addition of the solution of the polymerization initiator, it was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a weight average molecular weight (Mw) of 8.1 × 10 ³ and a solid content of 37.8% by mass. A resin B1 solution having a component acid value of 106 mg-KOH/g. The resin B1 has the following structural unit.

Synthesis Example 5

Nitrogen was passed through a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel at 0.02 L/min to obtain a nitrogen atmosphere, and 257 parts by mass of propylene glycol monomethyl ether acetate was added thereto, and the mixture was heated to 70 ° C while stirring. Then, 57 parts by mass of acrylic acid, 83 parts of vinyltoluene, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate (the compound represented by formula (I-1) and formula (II-1)) The compound shown was mixed with 238 parts by mass of a molar ratio of 50:50, dissolved in 140 parts by mass of propylene glycol monomethyl ether acetate, and the solution was added dropwise to a temperature of 70 ° C using a dropping funnel over 4 hours. Inside the flask. On the other hand, 30 parts by mass of a polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) is dissolved in 225 parts by mass of propylene glycol monomethyl ether acetate, and other solutions are used. The dropping funnel was added dropwise to the flask over 4 hours. After completion of the dropwise addition of the solution of the polymerization initiator, it was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a weight average molecular weight (Mw) of 1.04 × 10 ⁴ and a solid content of 37.4% by mass. A resin B2 solution having a component acid value of 112 mg-KOH/g. The resin B2 has the following structural unit.

Synthesis Example 6

Nitrogen was passed through a flask equipped with a reflux condenser, a dropping funnel and a stirrer at 0.02 L/min to obtain a nitrogen atmosphere, and 220 parts of ethyl lactate was added thereto, and the mixture was heated to 70 ° C while stirring. Then, 84 parts of methacrylic acid and 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate of the compound (the compound represented by the formula (I-1) and the compound represented by the formula (II-1) are A mixture of 336 parts of molar ratio of 50:50 was dissolved in 140 parts of ethyl lactate to prepare a solution, and the solution was added dropwise to a flask kept at 70 ° C for 4 hours using a dropping funnel. On the other hand, 30 parts by mass of a polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in a solution of 95 parts of ethyl lactate, and other dropping funnels were used. It was added dropwise to the flask over 4 hours. After completion of the dropwise addition of the solution of the polymerization initiator, it was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a weight average molecular weight (Mw) of 8.0 × 10 ³ , a molecular weight distribution of 2.5, and a solid content of 48. %, a resin B3 solution having a solution acid value of 50 mg-KOH/g (acid value of solid content of 104 mgKOH/g). Resin B3 has the following structural unit.

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

Device: K2479 (manufactured by Shimadzu Corporation)

Column: SHIMADZU Shim-pack GPC-80 M

Column temperature: 40 ° C

Solvent: THF (tetrahydrofuran)

Flow rate: 1.0 mL/min

Detector: RI

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh)

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

Examples 1, 2 and Comparative Example 1 [Preparation of Pigment Dispersion 1]

The pigment was sufficiently dispersed using a bead mill, whereby the pigment dispersion 1 was obtained.

[Preparation of Pigment Dispersion 2]

The pigment was sufficiently dispersed using a bead mill, whereby the pigment dispersion 2 was obtained.

[Preparation of Colored Photosensitive Resin Composition]

The components described in Table 1 were mixed to obtain a colored photosensitive resin composition.

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

Colorant (A); (A1-1); dye (A1-1)

Colorant (A); (A2-1); Pigment Dispersion 1

Colorant (A); (A2-2); Pigment Dispersion 2

Resin (B); (B-1); resin B1 solution

Resin (B); (B-2); resin B2 solution

Resin (B); (B-3); Resin B3 solution

Polymerizable compound (C); (C-1); dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Chemical Co., Ltd.)

Polymerization initiator (D); (D-1); N-benzylideneoxy-1-(4-phenylthiophenyl)oct-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF; O-mercaptopurine compound)

Polymerization initiator (D); (D-2); 2-methyl-2- Orolinyl-1-(4-methylthiophenyl)propan-1-one (Irgacure (registered trademark) 907; manufactured by BASF Corporation; alkylphenone compound)

Polymerization initiation aid (D1); (D1-1); 2,4-ethyl 9-oxosulfur (KAYACURE (registered trademark) DETX; manufactured by Nippon Chemical Co., Ltd.; 9-oxygen sulfur Compound)

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

Solvent (E); (E-2); ethyl lactate

Solvent (E); (E-3); propylene glycol monomethyl ether

Surfactant (F); (F-1); polyether modified eucalyptus oil (Toray Silicone SH8400; manufactured by TORAY.DOWCORNING)

[Solubility evaluation]

The colored photosensitive resin composition was applied by a spin coating method on a glass substrate (Eagle XG; manufactured by Corning Co., Ltd.) of 2 inches square, and then dried by a vacuum dryer (VCD; manufactured by MICROTEK Co., Ltd.). Dry at 50 Pa for 2 seconds under reduced pressure. The dried film was immersed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 2% of sodium carbonate at 23 ° C for 20 seconds, and washed with water. Using a microscope (magnification: 250 times; VF-7510; manufactured by KEYENCE), the substrate after washing was observed, and the case where no foreign matter was confirmed on the substrate after washing was set to ○, and the foreign matter was confirmed on the substrate after washing with water. Set to ×, shown in the table 3. If it is confirmed by the test that there is no foreign matter on the substrate, it means that when the colored pattern is formed on the substrate by photolithography, there is no foreign matter on the substrate and the colored pattern.

[Production of coloring patterns]

The colored photosensitive resin composition was applied by a spin coating method on a glass substrate (Eagle XG; manufactured by Corning) of 2 inches square, and then prebaked at 100 ° C for 3 minutes. After cooling, the interval between the substrate coated with the colored photosensitive resin composition and the patterned quartz glass mask was set to 100 μm, and an exposure machine (TME-150RSK; TOPCON) was used in the atmosphere. Next, light irradiation was performed at an exposure amount of 150 mJ/cm ² (365 nm reference). Further, as the photomask, a photomask capable of forming a line pattern of 100 μm lines and gaps was used. After the light irradiation, the coating film was immersed and developed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 2% of sodium carbonate at 24 ° C for 60 seconds, washed with water, and then dried in an oven at 230 ° C. Bake after 30 minutes to obtain a colored pattern.

[Measurement of film thickness]

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

[Color Evaluation]

The coloring pattern on the obtained glass substrate was measured for spectroscopic using a color measuring machine (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the xy chromaticity coordinate in the XYZ color system of CIE was measured using the characteristic function of the C light source (x). , y) and brightness Y. The results are shown in Table 2.

Example 3, 4 [Preparation of Colored Photosensitive Resin Composition]

The components described in Table 3 were mixed to obtain a colored photosensitive resin composition. Further, evaluation was carried out in the same manner as in Example 1. The results are shown in Table 4.

In the colored photosensitive resin composition of the example, it was confirmed that peeling due to development was suppressed during the formation of the colored pattern, and no foreign matter was present on the substrate after the formation of the colored pattern. Thus, by using the colored pattern obtained from the colored photosensitive resin composition of the present invention as a color filter, the display device can be manufactured at a high yield.

According to the colored photosensitive resin composition of the present invention, it is possible to prevent a portion of the unexposed portion of the composition layer formed from the colored photosensitive resin composition from being peeled off during development, and to reduce foreign matter on the colored pattern.

Claims (4)

A colored photosensitive resin composition containing a colorant, a resin, a polymerizable compound, and a polymerization initiator; the colorant is a coloring agent containing a xanthene dye and a pigment, and the resin is derived from a structural unit selected from the group consisting of a group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride; a structural unit derived from a monomer having a cyclic ether structure having a carbon number of 2 to 4 and an ethylenically unsaturated bond, and A copolymer derived from a structural unit of vinyl toluene. The colored photosensitive resin composition of claim 1, wherein the content of the structural unit derived from vinyl toluene is 1 mol% or more and 80 mol% or less based on the total amount of the structural unit constituting the copolymer. A color filter formed by the colored photosensitive resin composition of claim 1 or 2. A display device comprising a color filter as claimed in claim 3.