TWI578105B - Coloring the photosensitive resin composition - Google Patents

Description

Colored photosensitive resin composition

The present invention relates to a colored photosensitive resin composition.

The colored photosensitive resin composition is 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.

It is known that it is contained in Japanese Patent Laid-Open Publication No. 2010-32999. A coloring photosensitive resin composition containing a dye and a pigment as a coloring agent and containing propylene glycol monomethyl ether acetate and 4-hydroxy-4-methyl-2-pentanone as a solvent.

When the colored photosensitive resin composition is applied onto a substrate and dried under reduced pressure to form a dried coating film, a crater-like defect may occur. An object of the present invention is to provide a colored photosensitive resin composition which is less likely to generate crater-like defects.

The present invention provides the following [1] to [5].

[1] A colored photosensitive resin composition containing a colorant, a resin, a polymerizable compound, a polymerization initiator, and a solvent, and the colorant contains For dyes (xanthenedye) and pigments, the solvent contains dipropylene-glycol monomethylether acetate.

[2] The colored photosensitive resin composition according to [1] above, wherein the dipropylene glycol is mono The content of methyl ether acetate in the solvent is 0.1% by mass or more and 30% by mass or less.

[3] The colored photosensitive resin composition according to the above [1] or [2] wherein the solvent further contains ethyl lactate.

[4] The colored photosensitive resin composition according to [3] above, wherein the solvent further contains propylene glycol monomethyl ether and/or propylene glycol monomethyl ether acetate.

[5] The colored photosensitive resin composition according to any one of [1] to [4] wherein the resin is an alkali-soluble resin.

[6] The colored photosensitive resin composition according to any one of [1] to [5] wherein the polymerizable compound is (meth) acrylate.

[7] A color filter formed by the colored photosensitive resin composition according to any one of the above [1] to [6].

[8] A display device comprising the color filter of [7] above.

Even if the colored photosensitive resin composition of the present invention is applied onto a substrate, dried under reduced pressure, and dried to prepare a coating film, the occurrence of crater-like defects is small.

The colored photosensitive resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E), and the colorant (A) contains a pigment and For dyes, the solvent contains dipropylene glycol monomethyl ether acetate.

The coloring agent (A) used in the colored photosensitive resin composition of the present invention contains a pigment and dye.

Examples of the pigment include organic pigments and inorganic pigments, which can be exemplified in the color index. A compound classified as a pigment in the number (published by The Society of Dyers and Colourists). Among them, organic pigments are preferred.

Specific examples of the organic pigment include CI (Colour Index) pigment yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, Yellow pigments such as 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; CI Pigment Orange 13, 31, 36, Orange pigments such as 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 175, Red pigments such as 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265; CI Pigment Blue 15, 15, 3, 15: 4, 15: 6, 60, 80, etc. Blue pigment; CI pigment purple 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; and CI pigment black 1,7 and other black pigments.

Among them, preferred are CI pigment blue 15, 15:3, 15:4, 15:6, 60, 80 and other blue pigments, CI pigment violet 1, 19, 23, 29, 32, 36, 38 and other purple pigments, More preferably, it is a pigment containing at least one selected from the group consisting of CI Pigment Violet 23, CI Pigment Blue 15:3, and CI Pigment Blue 15:6, and further preferably a pigment containing CI Pigment Blue 15:6. By using these pigments with The dye combination can obtain a color filter excellent in heat resistance and color performance. These pigments may be used alone or in combination of two or more.

The pigment may be subjected to rosin treatment as needed, surface treatment using a pigment derivative or a pigment dispersant into which an acidic group or a basic group is introduced, graft treatment of a pigment surface by a polymer compound or the like, and use of sulfuric acid particles. The micronization treatment such as the chemical method, the cleaning treatment using an organic solvent or water for removing impurities, the removal treatment of the ionic impurities by an ion exchange method, or the like. Further, it is preferred that the particle diameter of the pigment is uniform. By performing a dispersion treatment by containing a pigment dispersant, a pigment dispersion liquid in which the pigment is uniformly dispersed in a solution can be obtained.

As the pigment dispersant, a commercially available surfactant can be used, and examples thereof include polyfluorene-based, fluorine-based, ester-based, cationic, anionic, nonionic, amphoteric, polyester, and polyamine. , surfactants such as acrylics, etc. As the above surfactant, in addition to polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amines In addition to modified polyurethanes and polyethyleneimine, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoei Chemical Co., Ltd.), and Solsperse (manufactured by Zeneca Co., Ltd.) can be used. ), EFKA (manufactured by CIBA Co., Ltd.), Ajisper (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (manufactured by BYK Chemie Co., Ltd.), and the like. These may be used alone or in combination of two or more.

In the case of using a pigment dispersant, the amount thereof is preferably 100 parts by mass or less, more preferably 5 to 50 parts by mass, per 100 parts by mass of the pigment. If the amount of the pigment dispersant used is in the above range, uniform dispersion can be obtained. The tendency of the pigment dispersion in the state.

Dye system contains A dye of a compound of the skeleton.

As Examples of the dye include: CI Acid Red 51, 52, 87, 92, 94, 289, 388, CI Acid Violet 9, 30, 102, CI Basic Red 1 (Rhodamine 6G), 2, 3, 4, 8, CI alkaline purple 10 (Rhodamine B), 11, CI alkaline purple 10, 11, 25, CI solvent red 218, CI medium red 27, CI reactive red 36 (Bangladesh rose red B), sulfo group Rhodamine G, as described in Japanese Patent Laid-Open Publication No. 2010-32999 Dyes and Japanese Patent No. 4492760 Dyes, etc.

Among them, as The dye is preferably a dye containing a compound represented by the formula (1) (hereinafter sometimes referred to as "compound (1)"). Compound (1) may also be a tautomer thereof. When using the compound (1), as opposed to The content of the compound (1) is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more. It is especially preferred that substantially only the compound (1) is used as dye.

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

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

m represents an integer from 0 to 5. When m is 2 or more, a plurality of R ^{5 are the} same or different from each other.

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

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

X represents a halogen atom.

a represents an integer of 0 or 1.

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

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

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

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

The monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ to R ⁴ preferably has a group selected from the group consisting of -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- M ⁺ and -SO ₂ NR ⁹ R ¹⁰ . At least one of the group is a substituent, and more preferably has at least one selected from the group consisting of -SO ₃ ^- M ⁺ and -SO ₂ NR ⁹ R ¹⁰ as a substituent. As this case, -SO ₃ ^- M ^{+ is} preferably -SO ₃ ^-+ N(R ¹¹ ) ₄ . When R ¹ to R ^{4 are} the same, the colored photosensitive resin composition of the present invention containing the compound (1) can form a color filter having less foreign matter generation and excellent heat resistance.

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

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ⁸ to R ¹¹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, and a neopentyl group. Alkyl, hexyl, heptyl, octyl, 2-ethylhexyl, decyl, decyl, dodecyl, hexadecyl, eicosyl, etc. alkyl having 1 to 20 carbon atoms, cyclopropyl, An alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as 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. Decaconyloxy and the like.

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, a mercaptothio 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 and the like.

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; and N,N-dimethylamine sulfonyl, N , N-ethylmethylamine sulfonyl, N,N-diethylamine sulfonyl N,N-propylmethylamine sulfonyl, N,N-isopropylmethylamine sulfonyl, N,N-tert-butylmethylamine sulfonyl, N,N-butylethylamine sulfonate An N,N-2 substituted amine sulfonyl group such as an anthracenyl group, an N,N-bis(1-methylpropyl)aminesulfonyl group or an N,N-heptylmethylaminesulfonyl group.

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

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

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

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

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

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

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

As ⁺ 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. In the case where ⁺ N(R ¹¹ ) ₄ is present in the compound (1), if R ^{11 is} such a group, the colored photosensitive resin composition of the present invention containing the compound (1) can be formed into a color filter having less foreign matter. Light film.

The compound (1) is preferably a compound represented by the formula (2) (hereinafter sometimes referred to as "compound (2)")) as The dye is preferably one containing the compound (2). Compound (2) may also be a tautomer thereof. In the case of using the compound (2), The content of the compound (2) in the dye is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more. It is especially preferred to use only compound (2) as dye.

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

X ^a represents a halogen atom.

A1 represents an integer of 0 or 1.

M1 represents an integer from 0 to 5. In the case where m1 is an integer of 2 or more, the plurality of R ^{25 are the} same or different from each other.

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

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

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

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

The monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ²¹ to R ²⁴ may be the same as those exemplified as the aromatic hydrocarbon group in R ¹ to R ⁴ .

In the combination of R ²¹ to R ²⁴ , R ²¹ and R ²³ are preferably a hydrogen atom, and R ²² and R ²⁴ are a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and hydrogen contained in the aromatic hydrocarbon group. The atomic system may be substituted by -SO ₃ ^- , -SO ₃ ^- M ⁺ , -SO ₃ H, -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ . More preferably, R ²¹ and R ²³ are a hydrogen atom, and R ²² and R ²⁴ are a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be -SO ₃ ^- M ⁺ Or -SO ₂ NHR ²⁶ replacement. When R ²¹ to R ^{24 are} these groups, a color filter excellent in heat resistance can be formed from the colored photosensitive resin composition of the present invention containing the compound (2).

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

In the case where R ²¹ to R ²⁴ are -R ^{26 ,} it is preferred that -R ^{26 is} independently a hydrogen atom, a methyl group or an ethyl group.

As a -SO ₃ R ²⁶ and -SO ₂ NHR ²⁶ in the 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 preferably It is 2-ethylhexyl. When R ^{26 is} such a group, the colored photosensitive resin composition containing the compound (2) can form a color filter which generates less foreign matter.

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

As ⁺ 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. In the case where ⁺ N(R ²⁷ ) ₄ is present in the compound (2), the coloring photosensitive resin composition of the present invention containing the compound (2) wherein R ^{27 is} the group (2) forms a color filter which generates less foreign matter. Light film.

The compound (1) is, for example, a compound represented by the formula (1-1) to the formula (1-30). In the following formula, Ra 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 C.I. Acid Red 289, a quaternary ammonium salt of C.I. Acid Red 289, a sulfonamide of C.I. Acid Violet 102 or a quaternary ammonium salt of C.I. Acid Violet 102 is preferred. Examples of such a compound include a compound represented by the formula (1-1) to the formula (1-8), the formula (1-11) or the formula (1-12).

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

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

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

Examples of the alkyl group having 1 to 10 carbon atoms of R ³¹ and R ³² include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a second butyl group, and a third butyl group. Hexyl, 2-ethylhexyl, decyl, decyl and the like. Examples of the alkyl group having 1 to 4 carbon atoms of R ³³ and R ³⁴ include those having a carbon number of up to 4.

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 isopropylsulfonate.醯基等.

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

Preferably, p and q are each independently an integer of 0 to 2, more preferably 1 or 2.

Examples of the compound (3) include a compound represented by the formula (1-31) to the formula (1-43). Among them, from the viewpoint of excellent solubility in an organic solvent, a compound represented by the formula (1-31) to the formula (1-40) is preferred.

As Dyes, available for commercial use Dye (for example, "Chugai Aminol Fast Pink RH/C" manufactured by Sino-foreign Chemicals Co., Ltd., "Rhodamin 6G" manufactured by Takooka Chemical Industry Co., Ltd., etc.). Also, it can be marketed The dye is used as a starting material, and is synthesized by referring to Japanese Patent Laid-Open Publication No. 2010-32999.

Colorant (A) may also contain Dyestuffs with different dyes. Examples of such dyes include azo dyes, metal salt azo dyes, anthraquinone dyes, triphenylmethane dyes, cyanine dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, squaric acid dyes, and hydrazines. Cyanine dye.

The colorant (A) can be selected depending on the color of the desired color filter. A plurality of the above dyes and pigments may also be used in combination.

In the coloring agent (A), The content of the dye is preferably from 1 to 80% by mass, more preferably from 3 to 50% by mass, even more preferably from 3 to 35% by mass, based on the total amount of the coloring agent (A). The content of the pigment is preferably 20 to 99% by mass, more preferably 50 to 97% by mass, still more preferably 65 to 97% by mass based on the coloring agent (A). If When the content of the dye and the pigment is within the above range, a color filter excellent in heat resistance and color performance can be obtained.

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

The colored photosensitive resin composition of the present invention contains a resin (B). The resin (B) is not particularly limited, and is preferably an alkali-soluble resin.

Examples of the resin (B) include the following resins [K1] to [K4].

[K1] a monomer having a cyclic ether structure of 2 to 4 carbon atoms and an ethylenically unsaturated bond (a) (hereinafter sometimes referred to as "(a)"), and an unsaturated carboxylic acid and an unsaturated carboxylic acid selected from the group consisting of A copolymer of at least one of the group consisting of acid anhydrides (b) (hereinafter sometimes referred to as "(b)").

[K2] (a), (b) and a monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter sometimes referred to as "(c)") Copolymer.

[K3] a copolymer of (b) and (c).

[K4] A resin obtained by reacting the copolymer of (b) and (c) with (a).

[K5] A resin obtained by reacting the copolymer of (a) and (c) with (b).

[K6] A resin obtained by reacting the copolymer of (a) and (c) with (b) and further reacting with a carboxylic acid anhydride.

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

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

(a), for example, a monomer (a1) having an oxirane group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(a1)"), having an oxetanyl group and an ethylenic group are not mentioned. A monomer (a2) having a saturated bond (hereinafter sometimes referred to as "(a2)"), a monomer (a3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(a3)").

(a1), for example, a monomer (a1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized and an ethylenically unsaturated bond (hereinafter sometimes referred to as " (a1-1)"), and a monomer (a1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(a1-2)" ).

Examples of (a1-1) 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, α-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)benzene Ethylene, 2,3,5-tris(glycidoxymethyl)styrene, 2,3,6-tris(glycidoxymethyl)styrene, 3,4,5-tris(glycidyloxy) Methyl)styrene, 2,4,6-tris(glycidoxymethyl)styrene, and the like.

As (a1-2), vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000, Daicel Chemical Industry) Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer A400, manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexyl (meth)acrylate An ester (for example, Cyclomer M100, manufactured by Daicel Chemical Industry Co., Ltd.), a compound represented by the formula (I), a compound represented by the formula (II), and the like.

In the formulae (I) and (II), R ^a and R ^b each independently 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 ¹ and X ² each independently represent a single bond, -R ^c -, ^* -R ^c -O-, ^* -R ^c -S-, ^* -R ^c -NH-.

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

^* indicates the key with O.].

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

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

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

As the alkanediyl group, a methylene group, an ethylidene group, and a propane-1,2-di are mentioned. Base, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl and the like.

As X ¹ and X ² , a single bond, a methylene group, an ethyl group, a ^* CH ₂ -O- ( ^* represents a bond bond with O), and ^* -CH ₂ CH ₂ - are preferable. More preferably, the O-group is a single bond or a ^* CH ₂ CH ₂ -O- group.

The compound represented by the formula (I) includes a compound represented by the formula (I-1) to the formula (I-15). Preferably, it is a formula (I-1), a formula (I-3), a formula (I-5), a formula (I-7), a formula (I-9) or a formula (I-11) to a formula (I). -15) The compound represented. More preferably, it is a compound represented by the formula (I-1), the formula (I-7), the formula (I-9) or the formula (I-15).

The compound represented by the formula (II) includes a compound represented by the formula (II-1) to the formula (II-15). Preferably, it is a formula (II-1), a formula (II-3), a formula (II-5), a formula (II-7), a formula (II-9) or a formula (II-11) to a formula (II). -15) The compound represented. More preferably, it is a compound represented by the formula (II-1), the formula (II-7), the formula (II-9) or the formula (II-15).

The compound represented by the formula (I) and the compound represented by the formula (II) can be used alone. Also, these can be mixed in any ratio. In the case of mixing, the mixing ratio is in molar ratio, and formula (I): formula (II) is preferably 5:95 to 95:5, more preferably 10:90 to 90:10, and particularly preferably 20:80~80:20.

The monomer (a2) having an oxetanyl group and an ethylenically unsaturated bond is more preferably a monomer having an oxetanyl group and a (meth)acryloxy group. Examples of (a2) include 3-methyl-3-methylpropenyloxymethyloxetane, 3-methyl-3-propenyloxymethyloxetane, and 3-ethyl b. 3-methylpropenyloxymethyloxetane, 3-ethyl-3-propenyloxymethyloxetane, 3-methyl-3-methylpropenyloxy Ethyloxetane, 3-methyl-3-propenyloxyethyloxetane, 3-ethyl-3-methylpropenyloxyethyloxetane, 3- Ethyl-3-propenyloxyethyloxetane and the like.

The monomer (a3) 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 (a3) include tetrahydrofurfuryl acrylate (for example, Viscoat V #150, manufactured by Osaka Organic Chemical Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

(a) is preferably (a1) from the viewpoint of higher reliability such as heat resistance and chemical resistance of the obtained color filter. Further, from the viewpoint of excellent storage stability of the colored photosensitive resin composition, (a1-2) is more preferable.

Specific examples of (b) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid; and Diacid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydroortene Unsaturated dicarboxylic acid such as phthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid or 1,4-cyclohexene dicarboxylic acid; 5-nor Ethylene-2,3-dicarboxylic acid methyl ester, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5- Methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]heptane- 2-olefin, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene and other carboxyl-containing bicyclic unsaturated compounds; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-ethylene Phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, two Unsaturated dicarboxylic acid anhydride such as methyltetrahydrophthalic anhydride or 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride; succinic acid mono[2-(methyl)propene oxime Unsaturated mono[(meth)acryloxyalkyl] of a divalent or higher polycarboxylic acid such as a phenylethyl ester or a mono[2-(methyl) propylene oxyethyl] phthalate An ester; and an unsaturated acrylate having a hydroxyl group and a carboxyl group in the same molecule as the α-(hydroxymethyl)acrylate.

Among these, from the viewpoint of the copolymerization reactivity or the solubility of the obtained resin to the alkaline aqueous solution, acrylic acid, methacrylic acid, maleic anhydride or the like is preferable.

Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, and (meth)acrylic acid. Tributyl ester, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylic acid ring Amyl ester, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate art, and referred to as the common name (meth) acrylate, dicyclopentanyl acrylate), (meth) acrylate, dicyclopentanyl oxyethyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decene - 8-based ester (referred to as dicyclopentenyl (meth) acrylate in the technical field as a conventional name), (meth)acrylic acid Ester, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, (meth)acrylic acid (meth) acrylates such as benzyl ester; (hydroxy) (meth) acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; maleic acid a dicarboxylic acid diester such as ethyl ester, diethyl fumarate or diethyl itaconate; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]heptane-2 - alkene, 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-diethoxy Bicyclo[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- Alkene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]heptane-2 - alkene, 5-tributoxycarbonylbicyclo[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] bicyclic unsaturated compounds such as hept-2-ene; N-phenyl maleimide, N-cyclohexyl maleimide, N-benzyl maleimide , N-butyl quinone imino-3-butyl quinone imide benzoate, N-butyl quinone imido-4-butylene imidate butyrate, N-butyl醯imino-6-m-butyleneimine hexanoate, N-butyl succinimide-3-synylene diimide propionate, N-(9-acridinyl) cis Dicarbonyl quinone imine derivatives such as butylene diimide; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, propylene Nitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene and 2,3-dimethyl- 1,3-butadiene and the like.

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

In the resin [K1], the ratio of the structural unit of each source to the total structural unit constituting the resin [K1] is preferably in the following range.

The structural unit from (a), 50~98 mol% (more preferably 60-90 mol%)

The structural unit from (b), 2 to 50 mol% (more preferably 10 to 40 mol%)

When the ratio of the structural unit of the resin [K1] is within the above range, the storage stability and developability of the colored photosensitive resin composition and the solvent resistance of the color filter tend to be good.

For example, the resin [K1] can be referred to in the literature "Experimental Method for Polymer Synthesis". (The method described in the document, and the cited documents in the literature, manufactured by Otsuka, Ltd., the company, the chemical company, the first edition of the first edition, issued on March 1, 1972).

Specifically, a method in which a specific amount of (a) and (b), a polymerization initiator, a solvent, and the like are introduced into a reaction vessel, for example, by replacing oxygen with nitrogen to form a deoxidizing environment, and heating and keeping warm while stirring . In addition, the polymerization initiator, solvent, and the like used herein are not particularly limited, and any of those generally used in the field can be used. Examples of the polymerization initiator include an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or organic Oxide (benzaldehyde peroxide, etc.). The solvent can be used as the solvent (E) of the colored photosensitive resin composition of the present invention as long as it can dissolve each monomer.

Further, the obtained copolymer may be directly used as a solution after the reaction, or a solution which is concentrated or diluted, or may be extracted in the form of a solid (powder) by a method such as reprecipitation. In particular, in the polymerization, the solvent contained in the colored photosensitive resin composition of the present invention is used as a solvent, and the colored photosensitive resin composition of the present invention can be directly used as the solution after the reaction, so that the present invention can be used. The manufacturing steps of the colored photosensitive resin composition are simple.

In the resin [K2], the ratio of the structural unit of each source to the total structural unit constituting the resin [K2] is preferably in the following range.

The structural unit from (a), 2 to 95 mol% (more preferably 5 to 80 mol%)

The structural unit from (b), 4 to 45 mol% (more preferably 10 to 30 mol%)

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

When the ratio of the structural unit of the resin [K2] is within the above range, the storage stability and developability of the colored photosensitive resin composition, and the solvent resistance, heat resistance and mechanical strength of the color filter become good. tendency.

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

Specifically, a specific amount of (a), (b), and (c), a polymerization initiator, and a solvent are put into a reaction container, and for example, oxygen is replaced with nitrogen to form a deoxidizing environment, and the mixture is heated while stirring. The method of insulation. The obtained copolymer may be directly used as a solution after the reaction, or may be a solution which is concentrated or diluted, or may be extracted as a solid (powder) by a method such as reprecipitation.

In the resin [K3], the ratio of the structural unit of each source to the total structural unit constituting the resin [K3] is preferably in the following range.

(b) 2 to 50% by mole, more preferably 5 to 40% by mole

(c) 50 to 98% by mole, more preferably 60 to 95% by mole

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

The resin [K4] can be obtained by obtaining a copolymer of (b) and (c), and (a) having a cyclic ether having 2 to 4 carbon atoms and (b) having a carboxyl group or The carboxylic anhydride is added.

First, the copolymers of (b) and (c) are produced in the same manner as those described for the production method of [K1]. In this case, the ratio of the structural unit of each source to the total structural unit of the copolymer constituting (b) and (c) is preferably in the following range.

(b) 5 to 50 mol%, more preferably 10 to 45 mol%

(c) 50 to 95% by mole, more preferably 55 to 90% by mole

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

After the copolymer of (b) and (c) is produced, the environment in the flask is then replaced with air from nitrogen, and the reaction catalyst of (a), a carboxyl group and a cyclic ether is introduced into the flask, for example, at 60 to 130 ° C. The reaction was carried out for 1 to 10 hours, whereby a resin [K4] was obtained. Examples of the reaction catalyst include tris(dimethylaminomethyl)phenol and the like. The amount of the above-mentioned reaction catalyst used is preferably 0.001 to 5% by mass based on the total amount of (a) to (c). Examples of the polymerization inhibitor include hydroquinone and the like. The amount of the polymerization inhibitor to be used is preferably 0.001 to 5% by mass based on the total amount of (a) to (c). The reaction conditions such as the charging 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 charging method or the reaction temperature can be appropriately adjusted in consideration of the production equipment or the amount of heat generated by the polymerization.

In this case, the amount of use of (a) is preferably from 5 to 80 moles, more preferably from 10 to 75 moles, and even more preferably from 15 to 70 moles, relative to (b) 100 moles. When it is in this range, the storage stability, developability, and sensitivity of the colored photosensitive resin composition tend to be good, and the balance of solvent resistance, heat resistance, and mechanical strength of the color filter tends to be good.

Regarding the resin [K5], as a first stage, a copolymer of (a) and (c) was obtained in the same manner as in the production method of the above-mentioned resin [K1]. As in the above, the obtained copolymer can be directly used as a solution after the reaction, or can be used as a concentrated solution. The diluted or diluted solution may also be extracted as a solid (powder) by reprecipitation or the like.

Preferably, the ratio of the structural units derived from (a) and (c) to the total number of moles of the total structural unit constituting the copolymer is in the following range.

The structural unit from (a), 5 to 95 mol% (more preferably 10 to 90 mol%)

The structural unit from (c), 5 to 95 mol% (more preferably 10 to 90 mol%)

Further, the copolymer of (a) and (c) may have a cyclic ether derived from (a) and (b) a carboxylic acid or a carboxy group, under the same conditions as in the production method of the resin [K4]. The acid anhydride is reacted, whereby the resin [K5] is obtained.

The amount of (b) used for the reaction with the above copolymer is preferably from 5 to 80 moles per 100 moles of (a). The (a), preferably (a1), and more preferably (a1) used as the resin [K5], from the viewpoint that the reactivity of the cyclic ether is high and the unreacted (a) is not easily left. 1).

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

Examples of the carboxylic anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, and 3,4,5,6-tetrahydrogen. Phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene Anhydride, etc.

Specific examples of the resin (B) include (meth)acrylic acid 3,4-epoxycyclohexylmethyl ester/(meth)acrylic acid copolymer, and acrylic 3,4-epoxytricyclo[5.2.1.0 ^2.6 Resin such as oxime ester/(meth)acrylic copolymer [K1]; glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, glycidyl (meth)acrylate /styrene/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate/(meth)acrylic acid/N-cyclohexylmethylene iodide copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate/(meth)acrylic acid/vinyltoluene copolymer, 3-methyl-3-(methyl)acrylic acid oxiranyloxymethyl epoxide Resin such as butane/(meth)acrylic acid/styrene copolymer [K2]; benzyl (meth)acrylate/(meth)acrylic acid copolymer, styrene/(meth)acrylic acid copolymer, etc. [K3] a resin formed by adding a benzyl (meth) acrylate/(meth)acrylic acid copolymer and a glycidyl (meth) acrylate to make tricyclodecyl (meth) acrylate/styrene/(A) Acrylic copolymer and glycidyl (meth)acrylate a resin formed by addition, a resin formed by adding a tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer and glycidyl (meth)acrylate Resin [K4]; a resin formed by reacting a copolymer of dicyclopentyl (meth)acrylate/glycidyl (meth)acrylate with (meth)acrylic acid to make dicyclopentanyl (meth)acrylate/ a resin such as a resin obtained by reacting a copolymer of styrene/glycidyl (meth)acrylate with (meth)acrylic acid [K5]; a dicyclopentanyl (meth)acrylate/glycidyl (meth)acrylate The resin formed by the reaction of the copolymer with (meth)acrylic acid and further reacted with tetrahydrophthalic anhydride to form a resin such as a resin [K6]. Among them, the resin [K1] and the resin [K2] are preferable, and the resin [K1] is more preferable, and further, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]nonyl acrylate/(meth)acrylic acid is preferred. Copolymer. When the resin (B) contains the structural unit derived from (a), the reliability of the heat resistance and chemical resistance of the obtained color filter can be further improved.

The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 35,000, particularly preferably 6,000 to 30,000, and particularly preferably 7,000 to 28,000. When the molecular weight is in the above range, the coating film hardness is improved, and the residual film ratio is also high, and the solubility of the unexposed portion in 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 (B) is preferably from 1.1 to 6, more preferably from 1.2 to 4.

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

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

The colored photosensitive resin composition of the present invention contains a polymerizable compound (C). The polymerizable compound (C) is a compound which can be polymerized by an active radical derived from a polymerization initiator (D), an acid or the like, and examples thereof include a compound having a polymerizable ethylenically unsaturated bond, and the like. The (meth) acrylate compound is mentioned.

Among these, as the polymerizable compound (C), it is preferred to have three or more ethylenically unsaturated bonds. As such a polymerizable compound, for example, season: Pentaerythritol tetra(meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate , pentaerythritol deca (meth) acrylate, pentaerythritol 九 (meth) acrylate, tris(2-(methyl) propylene methoxyethyl) isocyanurate, ethylene glycol modified pentaerythritol tetra (a) Acrylate, ethylene glycol modified dipentaerythritol hexa(meth) acrylate, propylene glycol modified pentaerythritol tetra(meth) acrylate, propylene glycol modified dipentaerythritol hexa(meth) acrylate, caprolactone modification Pentaerythritol tetra(meth)acrylate and caprolactone-modified dipentaerythritol hexa(meth)acrylate. Among them, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like are preferable. The polymerizable compounds may be used singly or in combination of two or more.

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 solid content of the colored photosensitive resin composition of the present invention. %. When the content of the polymerizable compound (C) is within the above range, the curing is sufficiently performed, the residual film ratio during development is improved, and undercut is less likely to occur in the colored pattern, and the adhesion tends to be good. .

The colored photosensitive resin composition of the present invention contains a polymerization initiator (D).

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

As the polymerization initiator (D), it is preferred to generate an active radical by the action of light, more preferably an alkylphenone compound, or three. The compound, a mercaptophosphine oxide compound, an anthracene compound, and a biimidazole compound are further preferably an anthracene compound.

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

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

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

From the viewpoint of sensitivity, as the alkylphenone compound, a compound having a partial structure represented by the formula (d2) is preferred, and 2-methyl-2-morpholinyl-1-(4-) is more preferred. Methylthiophenyl)propan-1-one and 2-dimethylamino-1-(4-? Polinylphenyl)-2-benzylbutan-1-one.

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

The above fluorenylphosphine oxide compound may, for example, be 2,4,6-trimethylbenzimidyldiphenylphosphine oxide. Commercial products such as Irgacure (registered trademark) 819 (manufactured by BASF Corporation) can also be used.

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

The above hydrazine compound may, for example, be N-benzylideneoxy-1-(4-phenylthiophenyl)butan-1-one-2-imine or N-benzylideneoxy-1- (4-phenylthiophenyl)octane-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-di Cyclopentylmethoxy)benzylidene}-9H-indazol-3-yl]ethane-1-imine, N-ethyloxy-1-[9-ethyl-6-(2- Methylbenzylidene)-9H-indazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzylidene-1-(9-ethyl-6-(2) -Methylbenzylidene)-9H-indazol-3-yl]-3-cyclopentylpropan-1-one-2-imine. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF Corporation), and N-1919 (made by ADEKA Co., Ltd.) can also be used. In the case where the colored photosensitive resin composition of the present invention is a blue colored photosensitive resin composition, since the brightness of the obtained color filter becomes high, it is preferred to use a material selected from N-benzonitrile. Oxy-1-(4-phenylthiophenyl)butan-1-one-2-imine, N-benzylideneoxy-1-(4-phenylthiophenyl)octane- a group consisting of 1-keto-2-imine and N-benzylideneoxy-1-(4-phenylthiophenyl)-3-cyclopentylpropan-1-one-2-imine One is used as the above hydrazine compound.

As the biimidazole compound, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-di) Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, see Japanese Patent Laid-Open No. Hei 6-75372, Japanese Patent Application Laid-Open No. Hei 6-75373, etc.), 2, 2' - bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'- Tetrakis(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2 '-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, refer to Japanese Patent Publication No. Sho 48-38403 and Japanese Patent Laid-Open Japanese Patent Publication No. Sho 62-174204, etc., and an imidazole compound in which a phenyl group at the 4,4'5,5'-position is substituted with an alkoxycarbonyl group (for example, refer to JP-A-7-10913, etc.). Preferred examples are: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorobenzene) base)- 4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole.

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'-tetrakis(t-butylperoxycarbonyl)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, benzophenone, phenyl methyl glyoxylate, titanocene compound, and the like. It is preferred to use these in combination with the following polymerization starting assistant (D1) (especially an amine).

Examples of the acid generator which generates an acid by light include 4-hydroxyphenyldimethylhydrazine p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-ethylhydrazine. Oxyphenyl dimethyl quinone p-toluene sulfonate, 4-ethoxy phenyl phenyl-methyl-benzyl hexafluoroantimonate, triphenyl sulfonium p-toluene sulfonate, triphenyl sulfonium An antimony salt such as fluoroantimonate, diphenylphosphonium p-toluenesulfonate or diphenylphosphonium hexafluoroantimonate, or nitrobenzyl tosylate or 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 photopolymerization initiator is within the above range, the sensitivity is improved and the exposure time is shortened, thereby improving productivity.

The colored photosensitive resin composition of the present invention may further contain a polymerization initiation aid (D1). A polymerization initiator (D1) is used to promote polymerization initiators The compound which initiates polymerization of the polymerizable compound to be polymerized, or a sensitizer, is usually used in combination with the polymerization initiator (D).

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

The amine compound may, for example, be triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate or 4-dimethylaminobenzene. Isoamyl formate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-double (two Methylamino)benzophenone (commonly known as miconesone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone Etc., among them, 4,4'-bis(diethylamino)benzophenone is preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

As the alkoxy ruthenium compound, 9,10-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 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 A. Oxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid , N-naphthylglycine, naphthyloxyacetic acid, and the like.

The polymerization initiation aids 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, more preferably 1 to 30 parts by mass, based on 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). ~20 parts by mass. When the amount of the polymerization initiation aid (D1) is within this range, the pattern can be further formed with high sensitivity, and the productivity of the pattern tends to be improved.

The colored photosensitive resin composition of the present invention contains a solvent (E). The solvent (E) is one containing dipropylene glycol monomethyl ether acetate.

The content of the dipropylene glycol monomethyl ether acetate is preferably 0.1% by mass or more and 30% by mass or less, more preferably 1% by mass or more and 20% by mass or less, and further preferably 2% by mass based on the total amount of the solvent (E). % or more and 15% by mass or less.

The solvent (E) may also contain a solvent other than dipropylene glycol monomethyl ether acetate. The solvent is not particularly limited, and a solvent which is generally used in the field can be used. For example, an ester solvent (a solvent containing a -COO- structure in a molecule and not containing an -O- structure), an ether solvent (a solvent containing a -O- structure in a molecule and not containing a -COO-structure), Ether ester solvent (solvent containing -COO-structure and -O-structure in the molecule), ketone solvent (solvent containing -CO- structure in the molecule, without -COO-structure), alcohol solvent (in the molecule) An OH group containing no -O-structure, a -CO-structure and a solvent of a -COO-structure, an aromatic hydrocarbon solvent, a guanamine solvent, and dimethyl hydrazine.

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, pyruvic acid Propyl ester, ethyl acetate methyl acetate, ethyl acetate ethyl acetate, cyclohexanol acetate, γ-butyrolactone and the like.

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

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

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

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

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

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

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

Among the above solvents, from the viewpoint of coatability and drying property, an organic solvent having a boiling point of from 120 ° C to 180 ° C at 1 standard atmosphere (1 atm) is preferred. Among them, preferred are propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether. , diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, N-methylpyrrolidone, etc., more preferably propylene glycol monomethyl ether acetate , propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, and the like.

Preferably, the solvent (E) contains dipropylene glycol monomethyl ether acetate and ethyl lactate. In this case, the content of the ethyl lactate is preferably 5% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 80% by mass or less, and still more preferably 40% by mass or more based on the total amount of the solvent (E). 70% by mass or less.

Further, the solvent (E) is preferably a mixed solvent of three or more kinds of dipropylene glycol monomethyl ether acetate, and more preferably a mixed solvent of four or more kinds.

When the solvent (E) is a mixed solvent containing three or more kinds of dipropylene glycol monomethyl ether acetate, it is preferred that the solvent (E) contains dipropylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol single Methyl ether and / or propylene glycol monomethyl ether B The acid ester is more preferably a dipropylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether or propylene glycol monomethyl ether acetate. Furthermore, it is preferable to contain the above, and the total content of dipropylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate is 90 mass with respect to the total amount of the solvent (E). More than %, more preferably 95% by mass or more.

When the solvent (E) contains propylene glycol monomethyl ether, the content thereof is preferably 1% by mass or more and 40% by mass or less, and more preferably 5% by mass or more and 30% by mass or less based on the total amount of the solvent (E).

When the solvent (E) contains propylene glycol monomethyl ether acetate, the content thereof is preferably 1% by mass or more and 40% by mass or less, more preferably 5% by mass or more and 30% by mass based on the total amount of the solvent (E). %the following.

When the solvent (E) is the above solvent, the film produced by drying under reduced pressure is less likely to generate crater-like defects, and the occurrence of unevenness can be suppressed.

The content of the solvent (E) is preferably from 70 to 95% by mass, more preferably from 75 to 92% by mass, based on the total amount of the colored photosensitive resin composition of the present invention. In other words, the solid content component of the colored photosensitive resin composition of the present invention is preferably from 5 to 30% by mass, more preferably from 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating becomes good, and the color density is sufficient when the color filter is formed, so that the display characteristics tend to be good.

The colored photosensitive resin composition of the present invention may further contain a surfactant (G). Examples of the surfactant (G) include a polyfluorene-based surfactant, a fluorine-based surfactant, and a polyfluorene-based surfactant having a fluorine atom. These may also have a polymerizable group on the branch.

As the polyoxymethylene surfactant, an interface having a decane bond can be cited. Active agent, etc. Specifically, Toray Silicone (trade name) DC3PA, Toray Silicone SH7PA, Toray Silicone DCllPA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone 8400 (Manufactured by Toray Dow Corning Co., Ltd.) ), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Momentive Performance Materials Japan Manufacturing) and so on.

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 Co., Ltd.), MEGAFAC (registered trademark) F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, and MEGAFAC F554. MEGAFAC R30, MEGAFAC RS-718-K (manufactured by DIC Corporation), Eftop (registered trademark) EF301, EftopEF303, Eftop EF351, Eftop EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Co., Ltd.), and the like.

Examples of the polyfluorene-based surfactant having a fluorine atom include A surfactant having a siloxane chain and a fluorocarbon chain. Specifically, MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477, MEGAFAC F443 (manufactured by DIC Corporation), and the like are mentioned.

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

The content of the surfactant (G) 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, more preferably 0.002% by mass or more, based on the total amount of the coloring photosensitive resin composition of the present invention. 0.01% by mass or more and 0.05% by mass or less. When the content of the surfactant (F) is in the above range, the flatness of the coating film can be improved.

The colored photosensitive resin composition of the present invention may contain various additives such as a filler, another polymer compound, an adhesion promoter, an antioxidant, an ultraviolet inhibitor, a light stabilizer, and a chain transfer agent as occasion demands (hereinafter sometimes referred to as As "other ingredients").

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

It is preferred to previously mix the pigment with a part or all of the solvent (E) and to disperse it by using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. At this time, part or all of the above-mentioned pigment dispersant and resin (B) may be blended as needed. The target coloring photosensitive resin composition can be prepared by mixing the remaining components and the like into the obtained pigment dispersion liquid to have a specific concentration.

Preferably pre- The solution is prepared by dissolving the dye in part or all of the solvent (E). Preferably, the solution is filtered using a filter having a pore diameter of about 0.01 to 1 μm.

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

The method of forming the colored pattern of the color filter using the colored photosensitive resin composition of the present invention includes, for example, a lithography method and a method using an inkjet device. The lithography method is a method of forming a pattern by applying the colored photosensitive resin composition of the present invention to a substrate or another resin layer (for example, another colored photosensitive resin composition layer formed on the substrate, etc.) The volatile component such as a solvent is removed/dried to form a dried coating film, and the dried coating film is exposed and developed by a mask. In the lithography method, a color filter film may be formed without using a photomask at the time of exposure, and/or development may be performed without using development.

The film thickness of the produced color filter is not particularly limited, and can be appropriately adjusted depending on the material to be used, the use, and the like, and is, for example, 0.1 to 30 μm, preferably 1 to 20 μm, and more preferably 1 to 6 μm. .

The colored photosensitive resin composition is applied onto a substrate, and the solvent is removed by heat drying (pre-baking) and/or drying under reduced pressure to obtain a smooth dried coating film.

As the substrate, a glass plate such as quartz glass, borosilicate glass, aluminum bismuth glass, or soda lime glass coated with cerium oxide, or polycarbonate, polymethyl methacrylate or polyethylene terephthalate may be used. A resin plate such as an ester is formed on the substrate, and an aluminum, silver, silver/copper/palladium alloy film or the like is formed on the substrate.

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

The heat drying is preferably from 30 to 120 ° C, more preferably from 40 to 100 ° C. Further, the heating time is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 30 minutes.

Preferably, it is dried under reduced pressure at a pressure of 50 to 150 Pa at a temperature ranging from 20 to 25 °C. When the colored photosensitive resin composition of the present invention is dried under reduced pressure under such conditions, the effect of generating a crater-like defect may be less.

The film thickness of the coating film after drying is not particularly limited, and can be appropriately adjusted depending on the materials to be used, the use, and the like.

After drying, the coating film is exposed through a reticle that forms a target pattern. At this time, the pattern on the photomask is not particularly limited, and those corresponding to the intended use can be used.

As the light source used for the exposure, it is preferred to generate light having a wavelength of 250 to 450 nm. For example, a filter that cuts off this band can be used for light that is less than 350 nm, and a bandpass filter that can extract the bands can be used for light around 436 nm, around 408 nm, and around 365 nm. Ground extraction. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned.

Since the entire exposed surface can be uniformly irradiated with parallel rays, or the position of the mask and the substrate on which the dried coating film is formed can be prepared, it is preferable to use a mask alignment exposure machine, a stepper, or the like. .

After the exposure, the unexposed portion can be dissolved and removed (i.e., developed) by bringing it into contact with the developer to obtain a colored pattern. As the developer, for example, preferably It is an aqueous solution of a basic compound such as potassium hydroxide, sodium hydrogencarbonate or tetramethylammonium hydroxide. The concentration of the basic compound in the aqueous solution is preferably from 0.01 to 10% by mass, more preferably from 0.03 to 5% by mass. Further, the developer may also contain a surfactant.

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

It is preferred to carry out water washing after development.

Further, post-baking can be performed as needed. The post-baking temperature is preferably from 150 to 250 ° C, more preferably from 160 to 220 ° C. The post-baking time is preferably from 1 to 120 minutes, more preferably from 10 to 60 minutes.

According to the colored photosensitive resin composition of the present invention, a color filter having particularly few defects can be produced. The color filter is used as a display device (for example, a liquid crystal display device, an organic EL (Electro luminescent) device, and an electronic paper) or a color filter used for a solid-state imaging device.

Example

Hereinafter, the colored photosensitive resin composition of the present invention will be described in more detail by way of examples. In the examples, "%" and "parts" are % by mass and parts by mass unless otherwise stated.

Synthesis Example 1

Into a flask equipped with a cooling tube and a stirring device, 15 parts of a compound represented by the formula (A0-1) and a compound represented by the formula (A0-2) (manufactured by a method of external chemical conversion), 15 parts of chloroform, and N, N were charged. - 8.9 parts of dimethylformamide, while stirring and maintaining at 20 ° C or lower, 10.9 parts of sulfite chloride was added dropwise. After the completion of the dropwise addition, the temperature was raised to 50 ° C, and maintained at this temperature for 5 hours, after which Cool to 20 °C. The reaction solution after cooling was stirred and maintained at 20 ° C or lower, and a mixture of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise. Thereafter, the mixture was stirred and reacted at 20 ° C for 5 hours. Then, after the obtained reaction mixture was subjected to solvent distillation in a rotary evaporator, a small amount of methanol was added and vigorously stirred. The mixture was added to a mixed solution of 375 parts of ion-exchanged water while stirring to precipitate crystals. The precipitated crystals were filtered, washed thoroughly with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain 11.3 parts of the dye A1 (mixture of the compound (1-1) to the compound (1-8)).

Synthesis Example 2

20 parts of the compound represented by the formula (1x) and 200 parts of N-ethyl-o-toluidine (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed under a light-shielding condition, and the obtained solution was stirred at 110 ° C for 6 hours. . After the obtained reaction liquid was cooled to room temperature, it was added to a mixed liquid of 800 parts of water and 50 parts of 35% hydrochloric acid, and the mixture was stirred at room temperature for 1 hour, and then crystals were precipitated. The precipitated crystals were suction-filtered to obtain a residue, followed by drying to obtain 24 parts of the compound represented by the formula (1-31). The yield was 80%.

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

Exact mass: 602.2

Synthesis Example 3

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

Identification of compounds represented by formula (1-39)

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

Exact quality: 658.9

Synthesis Example 4

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen gas was introduced at 0.02 L/min to form a nitrogen atmosphere, and 305 parts by mass of ethyl lactate was placed, and the mixture was heated to 70 ° C while stirring. Then, 60 parts by mass 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)) A solution was prepared by dissolving 240 parts by mass and 140 parts by mass of ethyl lactate in a molar ratio of 50:50, and the solution was dropped into a flask kept at 70 ° C for 4 hours using a dropping funnel.

On the other hand, using a separate dropping funnel, 30 parts by mass of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 225 parts by mass of ethyl lactate. The resulting solution was dropped into the flask. After the completion of the dropwise addition of the polymerization initiator solution, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a weight average molecular weight Mw of 9.1 × 10 ³ , a molecular weight distribution of 2.5, and a solid content of 33% by mass. A solution of the resin B1 having a solution acid value of 34 mg-KOH/g. Based on the above solid content and the acid value of the solution, the acid content of the solid content of the resin B1 was 100 mg-KOH/g. The resin B1 has the structural unit shown below.

Synthesis Example 4

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a nitrogen introduction tube, and the temperature in the flask was changed from air to nitrogen, and then the temperature was raised to 100 ° C. Containing 70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, and dicyclopentanyl methacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) 22.0 g (0.10 m) A solution of 3.6 g of 2,2'-azobisisobutyronitrile was added to a mixture of 136 g of propylene glycol monomethyl ether acetate, and the mixture was continuously stirred at 100 °C. Then, the environment inside the flask was changed from nitrogen to air, and glycidyl methacrylate was 35.5 g [0.25 mol, (50 mol% relative to the carboxyl group of methacrylic acid used in the reaction)], three (two) 0.9 g of methylamino)methylphenol and 0.145 g of hydroquinone were placed in a flask, and the reaction was continued at 110 ° C to obtain a resin B2 solution having a solid content of 32% and a solid content of 79 mgKOH/g. Polystyrene-converted by GPC (gel permeation chromatography) The weight average molecular weight was 30,000.

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 (made by Shimadzu Corporation)

Column: SHIMADZU Shim-pack GPC-80M

Column temperature: 40 ° C

Solvent: THF (Tetrahydrofuran, tetrahydrofuran)

Flow rate: 1.0 mL/min

Detector: RI

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

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

Examples 1 to 12 and Comparative Example 1

The components were mixed so as to have the compositions shown in Tables 1 and 2 to obtain a colored photosensitive resin composition.

In Tables 1 and 2, (A-1) ¹⁾ is obtained by mixing an acrylic dispersant and a total amount of propylene glycol monomethyl ether acetate, and dispersing them in advance. In (A-1) of Comparative Example 1, acrylic dispersant and 137 parts of propylene glycol monomethyl ether acetate were mixed and dispersed in advance.

In addition, in Table 1 and Table 2, each component is shown below.

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

Colorant (A), (A-2): Dye A1 ( dye)

Colorant (A), (A-3): a compound represented by formula (1-39) ( dye)

Resin (B), (B-1): Resin B1, which shows the parts by mass in terms of solid content.

Resin (B), (B-2): Resin B2, which shows the parts by mass in terms of solid content.

Polymerizable compound (C), (C-1): dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)

Polymerization initiator (D), (D-1): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure OXE 01, BASF JAPAN company)

Solvent (E), (E-1): Dipropylene glycol monomethyl ether acetate

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

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

Solvent (E), (E-4): Propylene glycol monomethyl ether acetate

Solvent (E), (E-5): 4-hydroxy-4-methyl-2-pentanone

Surfactant (G), (G-1): Polyether modified polyoxyxide oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.)

<Production of coloring pattern>

The colored photosensitive resin composition was applied onto a 2 inch square glass substrate (Eagle 2000, manufactured by Corning) by a spin coating method, and then prebaked at 100 ° C for 3 minutes to form a dried coating film. After standing to cool, the interval between the substrate on which the dried coating film was formed and the quartz glass reticle having the pattern (100 μm line and gap pattern) was set to 100 μm, and an exposure machine (TME-150RSK, TOPCON) was used. The company manufactures light exposure at an exposure of 150 mJ/cm ² (365 nm basis) in an atmospheric environment. After the light irradiation, the coating film was immersed and developed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C for 80 seconds, washed with water, and then placed in an oven at 220 ° C. After 20 minutes of baking at ° C, a colored pattern was obtained. After the film was allowed to stand for cooling, the film thickness of the obtained coloring pattern was measured by a film thickness measuring device (DEKTAK3, manufactured by Nippon Vacuum Technology Co., Ltd.) to be 2.2 μm.

<Color Evaluation>

For the obtained color pattern, the color measurement was measured 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 ( Bx, By) and tristimulus value Y. A larger Y value indicates a higher brightness. The results are shown in Tables 3 and 4.

<Defect evaluation>

The colored photosensitive resin composition was applied to a 3 inch square glass substrate (Eagle 2000, manufactured by Corning Incorporated) by a spin coating method, and dried to a reduced pressure in a vacuum dryer (manufactured by VCD MICROTEK Co., Ltd.). The degree reaches 0.5 torr. Then, in a dust-free oven, pre-baked at 100 ° C for 3 minutes to form a dried coating film on the substrate. The dry-coated film was observed by a surface-shaped optical microscope (magnification: 250 times, VF-7510, manufactured by KEYENCE Co., Ltd.), and a volcano existing on the entire substrate except for a range of 1 cm from the end of the substrate was counted. The number of defects in the shape of the mouth. The results are shown in Tables 3 and 4.

<heat resistance evaluation>

A colored coating film was produced in the same manner as the patterning except that the mask was not used at the time of exposure. The colored coating film was heated in an oven at 230 ° C for 2 hours, and the color and tristimulus value Y were measured in the same manner as above. The color difference ΔEab* is calculated from the chromaticity before and after heating and the tristimulus value Y. The smaller the color difference ΔEab*, the smaller the color change before and after heating, and the better the heat resistance. The value of the obtained color difference ΔEab* is shown in the column of "heat resistance" in Tables 3 and 4.

Example 13~18

A colored photosensitive resin composition was obtained in the same manner as in Examples 1 to 6, except that the compound represented by the formula (1-31) was used instead of the dye A1. Perform the same operation as above to obtain a dry coating after less defects membrane. Further, a coloring pattern excellent in brightness or heat resistance is obtained.

According to the above results, it is understood that the colored photosensitive resin compositions of Examples 1 to 12 can obtain a post-drying coating film having few defects without lowering the brightness or heat resistance of the obtained color filter.

By forming the dried coating film from the colored photosensitive resin composition of the present invention and forming the colored pattern obtained from the dried coating film into a color filter, the display device can be manufactured with high yield.

Industrial availability

The colored photosensitive resin composition of the present invention is applied to a substrate and then dried under reduced pressure, and the occurrence of crater-like defects on the coating film after drying is small.

Claims (7)

A colored photosensitive resin composition containing a colorant, a resin, a polymerizable compound, a polymerization initiator, and a solvent, and the colorant contains Dyes and pigments, The dye contains a compound represented by the formula (3), and the solvent contains dipropylene glycol monomethyl ether acetate, and the content of the dipropylene glycol monomethyl ether acetate in the solvent is 0.1% by mass or more and 30% by mass or less. In the formula (3), R ³¹ and R ³² each independently represent an alkyl group having 1 to 10 carbon atoms, and R ³³ and R ³⁴ each independently represent an alkyl group having 1 to 4 carbon atoms and an alkyl group having 1 to 4 carbon atoms. a sulfur group or an alkylsulfonyl group having 1 to 4 carbon atoms, R ³¹ and R ³³ may together form a ring containing a nitrogen atom, and R ³² and R ³⁴ may together form a ring containing a nitrogen atom, and p and q are independent of each other. The ground represents an integer of 0 to 5. When p is 2 or more, the plurality of R ³³ may be the same or different. When q is 2 or more, the plurality of R ³⁴ may be the same or different. The colored photosensitive resin composition of claim 1, wherein the solvent further contains ethyl lactate. The colored photosensitive resin composition of claim 2, wherein the solvent further contains propylene glycol monomethyl ether and/or propylene glycol monomethyl ether acetate. The colored photosensitive resin composition of claim 1, wherein the resin is an alkali-soluble resin. The colored photosensitive resin composition of claim 1, wherein the polymerizable compound is (meth) acrylate. A color filter formed of the colored photosensitive resin composition of claim 1. A display device comprising the color filter of claim 6.