KR20120090840A - Colored photosensitive resin composition - Google Patents

Abstract

PURPOSE: A colored photo-sensitive resin composition is provided to prepare a film by applying the composition on a substrate and preparing the film after the decompression-drying the composition on the substrate. CONSTITUTION: A colored photo-sensitive resin composition includes a coloring agent, a resin, a polymeric compound, a polymerization initiator, and a solvent. The coloring agent includes a xanthene dye and a xanthene pigment. The solvent includes dipropylene glycol monomethyl ether acetate. The content of the dipropylene glycol monomethyl ether acetate in the solvent is 0.1 to 30 mass%. The solvent further includes ethyl acetate and further includes glycol monomethyl ether and/or propylene glycol monomethyl ether acetate. The resin is an alkali soluble resin. The polymeric compound is a (meta)acrylic acid ester.

Description

Colored photosensitive resin composition {COLORED PHOTOSENSITIVE RESIN COMPOSITION}

The present invention relates to a colored photosensitive resin composition.

The coloring photosensitive resin composition is used for manufacture of the color filter used for display apparatuses, such as a liquid crystal display panel, an electroluminescent panel, and a plasma display panel.

Japanese Patent Application Laid-Open No. 2010-32999 discloses a coloring photosensitive agent comprising xanthene dye and pigment as a colorant and propylene glycol monomethyl ether acetate and 4-hydroxy-4-methyl-2-pentanone as a solvent. Resin compositions are known.

When apply | coating a coloring photosensitive resin composition to a board | substrate, and drying under reduced pressure and producing a coating film after drying, a crater type defect may generate | occur | produce. An object of the present invention is to provide a colored photosensitive resin composition with less occurrence of crater-shaped defects.

This invention provides the following [1]-[i].

[1] A colorant comprising a colorant, a resin, a polymerizable compound, a polymerization initiator, and a solvent, wherein the colorant is a colorant comprising xanthene dye and a pigment, and the solvent is dipropylene-glycol monomethylether. Colored photosensitive resin composition which is a solvent containing acetate).

[2] The coloring photosensitive resin composition as described in [1] whose content of dipropylene glycol monomethyl ether acetate is 0.1 mass% or more and 30 mass% or less in a solvent.

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

[4] The colored photosensitive resin composition according to [3], in which the solvent further comprises 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 a (meth) acrylic acid ester.

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

[Iii] A display device comprising the color filter according to [7].

The colored photosensitive resin composition of this invention applied to a board | substrate, dried under reduced pressure, and dried, and even if it produced a coating film, there existed little generation | occurrence | production of a crater-shaped defect.

The coloring photosensitive resin composition of this invention contains a coloring agent (A), resin (i), a polymeric compound (C), a polymerization initiator (D), and a solvent (E), and a coloring agent (A) uses a pigment and xanthene dye. It is a coloring agent to contain, and is a coloring photosensitive resin composition whose solvent is a solvent containing dipropylene glycol monomethyl ether acetate.

The coloring agent (A) used for the coloring photosensitive resin composition of this invention contains a pigment and xanthene dye.

Examples of the pigment include organic pigments and inorganic pigments, and examples include compounds classified as pigments in the Color Index (Published by The Society of Dyers and Colourists). Among these, organic pigments are preferable.

Specific examples of the organic pigments include C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139 Yellow pigments such as, 147, 148, 150, 153, 154, 166, 173, 194, and 214;

C.I. Pigment oranges such as pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and the like;

C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 175, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc. Red pigment;

C.I. Blue pigments such as Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60, and 80;

C.I. Violet pigments such as pigment violet 1, 19, 23, 29, 32, 36 and 38;

C.I. Green pigments such as pigment green 7, 36 and 58;

C.I. Brown pigments such as Pigment Brown 23 and 25; And

C.I. Black pigments, such as pigment black 1 and 7, are mentioned.

Among these, C.I. Blue pigments such as Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60, and 80; C.I. Pigment violet 1, 19, 23, 29, 32, 36, 38, etc. Violet pigments are preferable, C.I. Pigment Violet 23, C.I. Pigment Blue 15: 3 and C.I. Pigment Blue 15: 6 is more preferably a pigment containing at least one selected from the group consisting of C.I. Even more preferred is a pigment comprising Pigment Blue 15: 6. By combining such a pigment and xanthene dye, a color filter excellent in heat resistance and color performance can be obtained. You may use these pigments individually or in mixture of 2 or more types.

The pigment may be rosin-treated, surface-treated with a pigment derivative or a pigment dispersant incorporating an acidic group or a basic group, graft treatment on the surface of the pigment with a polymer compound, atomization by a sulfuric acid atomization method, or the like, if necessary. For example, a washing treatment with an organic solvent, water, or the like, a removal treatment by an ion exchange method of ionic impurities, or the like may be performed. Moreover, it is preferable that a pigment is uniform particle diameter. By carrying out a dispersion process by containing a pigment dispersant, the pigment dispersion liquid of the form which the pigment disperse | distributed uniformly in the solution can be obtained.

Commercially available surfactants can be used as the pigment dispersant, and examples thereof include surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic, amphoteric, polyester, polyamine, acrylic, and the like. Can be. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines. , KP [made by Shin-Etsu Chemical Co., Ltd.], Floren [made by Kyoeisha Chemical Co., Ltd.], Solz Purse [Geneca Co., Ltd.], EFKA (made by CIBA Corporation), Ajisper [Ajinomoto Fine Techno Co., Ltd.] ), Disperbyk (manufactured by Beek Chemical Co., Ltd.), etc. are mentioned. These can be used individually or in combination of 2 types or more, respectively.

When using a pigment dispersant, its usage-amount is preferably 100 mass parts or less with respect to 100 mass parts of pigments, More preferably, it is 5-50 mass parts. When the usage-amount of a pigment dispersant exists in said range, there exists a tendency for the pigment dispersion liquid of a uniform dispersion state to be obtained.

The xanthene dye is a dye containing a compound having a xanthene skeleton.

As xanthene dye, it is C.I. Acid red 51, 52, 87, 92, 94, 289, 388, C.I. Acid violet 9, 30, 102, C.I. Basic Red 1 (Rhodamine 6G), 2, 3, 4, 8, C.I. Basic Red 10 (Rhodamine B), 11, C.I. Basic Violet 10, 11, 25, C.I. Solvent Red 218, C.I. Modern Red 27, C.I. Reactive red 36 (rose bengal B), sulforhodamine G, the xanthene dye of Unexamined-Japanese-Patent No. 2010-32999, the xanthene dye of patent 4449760, etc. are mentioned.

Among these, as xanthene dye, the dye containing the compound represented by Formula (1) (henceforth "compound (1)") is preferable. Compound (1) may be a tautomer thereof. When using compound (1), 50 mass% or more of content of compound (1) with respect to the total amount of xanthene dye is preferable, More preferably, it is 70 mass% or more, More preferably, it is 90 mass% or more. In particular, it is preferable to use only compound (1) substantially as xanthene dye.

[In formula (1), R <^1> -R <^4> represents a hydrogen atom, a C1-C20 monovalent saturated hydrocarbon group, or a C6-C10 monovalent aromatic hydrocarbon group each independently, and is a hydrogen atom contained in the said aromatic hydrocarbon group are halogen ^{atoms, -R 8, -OH, -OR 8} , -SO 3 -, -SO 3 H, -SO 3 - M +, -CO 2 H, -CO 2 - M +, -CO 2 R 8, It may be substituted by -SR ⁸ , -SO ₂ R ⁸ , -SO ₃ R ^8, or -SO ₂ NR ⁹ R ¹⁰ . The hydrogen atom contained in the said saturated hydrocarbon group may be substituted by the C6-C10 aromatic hydrocarbon group or the halogen atom, and the hydrogen atom contained in the said aromatic hydrocarbon group may be substituted by the C1-C3 alkoxy group, and the said saturated hydrocarbon group -CH ₂ -to be included may be substituted with -O-, -CO-, or -NR ^11- . R ¹ and R ² may be bonded to each other to form a ring containing a nitrogen atom, and R ³ and R ⁴ may be bonded to each other to form a ring containing a nitrogen atom.

R ⁵ is _{^{-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 is shown.

m represents the integer of 0-5. When m is two or more, some R <^5> is the same or different.

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

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

X represents a halogen atom.

a represents the integer of 0 or 1.

R <^8> represents a C1-C20 monovalent saturated hydrocarbon group, and the hydrogen atom contained in the said saturated hydrocarbon group may be substituted by the halogen atom.

R ¹¹ each independently represents a hydrogen atom, a C 1-20 monovalent saturated hydrocarbon group or a C 7-10 aralkyl group.

R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a hydroxyl group or a halogen atom, and the saturated aliphatic hydrocarbon group -CH ₂ -to be included may be substituted with -O-, -CO-, -NH- or -NR ^8- , and R ⁹ and R ¹⁰ are bonded to each other to form a 3 to 10 membered heterocycle containing a nitrogen atom; May be formed]

As a C6-C10 monovalent aromatic hydrocarbon group in R <^1> -R <^4> , a phenyl group, tolyl group, xylyl group, mesityl group, a propylphenyl group, a butylphenyl group, etc. are mentioned, for example.

In R ^1, R ⁴ as C 6 10 1-valent aromatic hydrocarbon group is a substituent _{^{-SO 3 -??, -SO 3}} H, -SO 3 - M + and -SO ₂ NR ⁹ R ¹⁰ is selected from the group consisting of 1 desirable to have a more thereof and, -SO ₃ ^- and more preferably having a M ⁺ 1 and -SO or more selected from the group consisting of ₂ NR ⁹ R ^10. In this case, -SO ₃ ^- M ⁺ as -SO ₃ ^- is N ⁺ (R ¹¹⁾ ₄ are preferred. If R <^1> -R <^4> is such a group, the color filter which is little in generation of a foreign material and excellent in heat resistance can be formed from the coloring photosensitive resin composition of this invention containing compound (1).

Examples of the ring formed by bonding of R ¹ and R ² to the ring formed by bonding of R ³ and R ⁴ include the following ones.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ^{8 to} R ¹¹ are methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, Alkyl groups having 1 to 20 carbon atoms such as heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group, hexadecyl group and icosyl group; C3-C20 alicyclic saturated hydrocarbon groups, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecyl group, are mentioned.

As -OR <^8> , a methoxy group, an ethoxy group, a propoxy group, butoxy group, a pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, an icosyloxy group, etc. are mentioned, for example. Can be.

Examples of -CO ₂ R ^8, for example, and the like can be mentioned methoxy group, an ethoxy group, a propoxy group, a tert- butoxy group, a hexyloxy group and an oxycarbonyl group Aiko chamber.

Examples of -SR ⁸ include methylsulfanyl group, ethylsulfanyl group, butylsulfanyl group, hexylsulfanyl group, decylsulfanyl group, icosylsulfanyl group and the like.

Examples of -SO ₂ R ^8, and examples thereof include a methyl sulfonyl group, ethyl sulfonyl, butyl sulfonyl group, hexyl sulfonyl group, sulfonyl group and decyl Aiko room sulfonyl group.

Examples of -SO ₃ R ^8, and examples thereof include a methoxy group, etc. Four treatment groups, ethoxy procedure Four group, propoxy procedure Four group, tert- butoxy procedure Four group, hexyloxy group and PO procedure Aiko -1,3 procedure Four groups.

As —SO ₂ NR ⁹ R ¹⁰ , for example, a sulfamoyl group;

N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N-sec-butylsulf Pamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) sulfamoyl group, N- (1, 2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (2-methylbutyl) sulfamoyl group, N- ( 3-methylbutyl) sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexyl sulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamo Diary, N-heptyl sulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octyl sulfamoyl group, N- (2-ethylhexyl) N-1 substituted sulfamoyl groups such as sulfamoyl group, N- (1,5-dimethyl) hexyl sulfamoyl group, N- (1,1,2,2-tetramethylbutyl) sulfamoyl group; And

N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-isopropylmethylsulfamoyl group, N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N, N-heptylmethylsulfamoyl group, etc. N-2 substituted sulfamoyl group etc. are mentioned.

In addition, R ⁹ and the carbon number of 1 to 20 monovalent saturated hydrocarbon group representing the R ¹⁰ group is optionally substituted hydrogen atoms are -OH, or a halogen atom contained to said saturated hydrocarbon, -CH ₂ contained to said saturated hydrocarbon - is -O It may be substituted with-, -CO-, -NH- or -NR ^8- .

R ⁹ and R ¹⁰ may be bonded to each other to form a 3 to 10 membered heterocycle containing a nitrogen atom. As said heterocycle, the following are mentioned, for example.

R ⁵ is ^{_{-CO 2 H, -CO 2 R 8}} , -SO 3 -, -SO 3 - M +, -SO 3 H or -SO ₂ NHR ⁹ are _{^{preferred, -SO 3 -, -SO 3 -}} M More preferred is ⁺ , -SO ₃ H or -SO ₂ NHR ⁹ .

1-4 are preferable and, as for m, 1 or 2 is more preferable.

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 among the alkyl groups mentioned above.

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 .

⁺ N (R ¹¹ ) ₄ is ₄ R ¹¹ It is preferable that two or more are a C5-C20 monovalent saturated hydrocarbon group in it. Moreover, 20-80 pieces are preferable and, as for the sum total carbon number of four R <^11> , 20-60 pieces are more preferable. Compound (1) from the ⁺ N (R ¹¹⁾ is _4, if there are R ¹¹ such the group, it is possible to form a small foreign body color filter from the colored photosensitive resin composition of the present invention comprising the compound (1).

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

? In the equation (2), R ²¹ R ²⁴ each independently represents a hydrogen atom, or -R ²⁶ C 6 10 1-valent aromatic hydrocarbon group, hydrogen atoms contained to said aromatic hydrocarbon is -SO ₃ ^{-?, -} SO ₃ ^- may be substituted by _{^{M a +, -SO 3 H,}} -SO 3 R 26 or -SO ₂ NHR ^26.

X ^a represents a halogen atom.

a1 represents the integer of 0 or 1.

m1 represents the integer of 0-5. When m1 is an integer of 2 or more, some R <^25> is the same or different.

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

R ²⁵ is -SO ₃ ^- shows a M ^{a +,} -SO ₃ H or _{^{-SO 2 NHR 26 -, -SO 3}} .

R ²⁶ represents a C 1-20 monovalent saturated hydrocarbon group.

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

Examples of the C 6-10 monovalent aromatic hydrocarbon group for R ^{21 to} R ²⁴ include the same groups as those listed as the aromatic hydrocarbon group for R ^{1 to} R ⁴ .

Especially, as a combination of R <^21> -R <^24> , Preferably, R <^21> and R <^23> is a hydrogen atom, R <^22> and R <^24> is a C6-C10 monovalent aromatic hydrocarbon group, The hydrogen atom contained in the said aromatic hydrocarbon group is -SO ₃ ^- is optionally substituted by _{^{M +, -SO 3 H, -SO}} 3 R 26 or _{^{-SO 2 NHR 26 -, -SO 3}} . More preferably, R ²¹ and R ²³ are hydrogen atoms, 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 is -SO ₃ ^- M ⁺ or- It may be substituted by SO ₂ NHR ²⁶ . If R <^21> -R <^24> is such a group, the color filter excellent in heat resistance can be formed from the coloring photosensitive resin composition of this invention containing compound (2).

Examples of the C 1-20 monovalent saturated hydrocarbon group for R ²⁶ and R ²⁷ include the same groups as those listed as the saturated hydrocarbon group for R ⁸ -R ¹¹ .

When R <^21> -R <^24> is -R <^26> , it is preferable that -R <^26> is a hydrogen atom, a methyl group, or an ethyl group each independently.

In —SO ₃ R ²⁶ and —SO ₂ NHR ²⁶ , R ²⁶ is preferably a C 3-20 branched alkyl group, more preferably a C 6-12 branched alkyl group, even more preferably a 2-ethylhexyl group. . If R <^26> is such a group, the coloring photosensitive resin composition containing a compound (2) can form the color filter with little generation | occurrence | production of a foreign material.

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

^{As +} N (R ²⁷ ) _4, it is preferable that two or more of the four R ²⁷ be a C 5-20 monovalent saturated hydrocarbon group. Moreover, 20-80 pieces are preferable and, as for the sum total carbon number of four R <^27> , 20-60 pieces are more preferable. When ⁺ N (R ²⁷ ) ₄ is present in the compound (2), a color filter with less generation of foreign matters can be formed from the colored photosensitive resin composition of the present invention in which R ²⁷ contains the compound (2).

As compound (1), the compound represented, for example by Formula (1-1)-Formula (1-3) is mentioned. Moreover, in the following formula, Ra represents a C1-20 monovalent saturated hydrocarbon group, preferably a C6-12 branched alkyl group, even more preferably 2-ethylhexyl group. Among these, C.I. Sulfonamides of acid red 289, C.I. Quaternary ammonium salt of acid red 289, C.I. Sulfonamides of acid violet 102 or C.I. Preference is given to quaternary ammonium salts of acid violet 102. As such a compound, the compound etc. which are represented, for example by Formula (1-1)-Formula (1-1), Formula (1-11), or Formula (1-1) are mentioned.

Moreover, as xanthene dye, the dye containing the compound represented by Formula (3) (henceforth "compound (3)") is also more preferable. Compound (3) may be a tautomer thereof. In the case of using compound (3), the content of compound (3) in xanthene dye is preferably at least 50 mass%, more preferably at least 70 mass%, even more preferably at least 90 mass%.

In formula (3), R <^31> and R <^32> represents a C1-C10 alkyl group mutually independently. R ³³ and R ³⁴ independently of each other represent an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms. R ³¹ and R ³³ may be bonded to each other to form a ring containing a nitrogen atom, and R ³² and R ³⁴ may be bonded to each other to form a ring containing a nitrogen atom.

p and q represent 0-5 integers independently of each other. when p is 2 or more, a plurality of R ³³ may be the same or different, and when q is 2 or more, a plurality of R ³⁴ may be the same or different.]

R ³¹ and R ³² represents the number of carbon atoms 1? 10 As the alkyl group a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, sec- butyl group, tert- butyl group, a hexyl group, a 2-ethylhexyl group , Nonyl group, decyl group, etc. are mentioned. As a C1-C4 alkyl group which shows R <^33> and R <^34> , the group of C4 up to these is mentioned.

R having a carbon number of 1? ³³ and R ³⁴ represents a and the like can be given four alkyl sulfanyl group as methyl sulfanyl group, ethyl sulfanyl group, a propyl sulfanyl group, a butyl sulfanyl group, and an isopropyl sulfanyl group.

As a C1-C4 alkylsulfonyl group which shows R <^33> and R <^34> , a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, an isopropylsulfonyl group, etc. are mentioned.

R ³¹ and R ³² are preferably each independently a methyl group, an ethyl group, a propyl group or an isopropyl group. It is preferable that R <^33> and R <^34> are a C1-C4 alkyl group, and it is more preferable that it is a methyl group.

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

As compound (3), the compound represented by Formula (1-3)-Formula (1-4), respectively is mentioned, for example. Among these, the compound represented by Formula (1-3)-Formula (1-4) is preferable at the point which is excellent in solubility with respect to an organic solvent.

As xanthene dyes, commercially available xanthene dyes (for example, "Chugai Aminol Fast Pink RH / C" manufactured by Chugaikasei Co., Ltd., "Rhodamin 6G" manufactured by Taoka Chemical Co., Ltd.), etc., can be used. Can be. Commercially available xanthene dyes can also be synthesized with reference to Japanese Patent Application Laid-Open No. 2010-32999 as a starting material.

The coloring agent (A) may contain a dye different from the xanthene dye. Examples of such dyes include azo dyes, metal complex salt azo dyes, anthraquinone dyes, triphenylmethane dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, squarylium dyes and phthalocyanine dyes. .

The colorant (A) is selected according to the color of the desired color filter. You may use said dye and pigment in combination of multiple types.

1-80 mass% is preferable with respect to the total amount of a coloring agent (A), as for content of a xanthene dye in a coloring agent (A), 3-50 mass% is more preferable, and its 3-35 mass% is still more preferable. As for content of a pigment, 20-99 mass% is preferable with respect to a coloring agent (A), 50-97 mass% is more preferable, 65-97 mass% is still more preferable. When content of xanthene dye and a pigment is in the said range, the color filter excellent in heat resistance and color performance can be obtained.

As for content of a coloring agent (A), 5-60 mass% is preferable with respect to solid content in the coloring photosensitive resin composition of this invention, 8-55 mass% is more preferable, 10-50 mass% is further more preferable. When content of a coloring agent (A) exists in said range, since the color density at the time of setting it as a color filter is sufficient, resin in a composition can be contained in a required amount, and there exists a tendency which can form a pattern with sufficient mechanical strength, it is preferable. Do. Here, solid content means the quantity remove | excluding the solvent from the total amount of the coloring photosensitive resin composition of this invention. The total amount of solids and the content of each component thereof can be measured by known analytical means, such as liquid chromatography or gas chromatography, for example.

The coloring photosensitive resin composition of this invention contains resin. Although it does not specifically limit as resin (B), It is preferable that it is alkali-soluble resin.

As resin (B), the following resin [K1], [K6] etc. are mentioned, for example.

[X1] Selected from the group consisting of a monomer having an ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter referred to as "a"), and an unsaturated carboxylic acid and an unsaturated carboxylic anhydride. Copolymer with at least 1 sort (s) (hereinafter, referred to as "(vi)").

[B2] A copolymer of monomers (c) copolymerizable with (a), (iii) and (a), but different from (a) and (iii) (hereinafter referred to as "(c)").

[3] A copolymer of (iii) and (c).

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

[V5] Resin obtained by reacting (b) with the copolymer of (a) and (c).

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

(a) is an ethylenically unsaturated bond, for example with a C2-C4 cyclic ether structure (e.g., at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) Eggplant refers to a polymerizable compound. As for (a), the monomer which has a C2-C4 cyclic ether and a (meth) acryloyloxy group is preferable.

Moreover, in this specification, "(meth) acrylic acid" represents 1 or more types chosen from the group which consists of acrylic acid and methacrylic acid. Notations such as "(meth) acryloyl" and "(meth) acrylate" have the same meaning.

As (a), for example, a monomer (a1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter referred to as "(a1)") and a monomer (a2) having an oxetanyl group and an ethylenically unsaturated bond [hereinafter, "(A2)"], the monomer (a3) which has a tetrahydrofuryl group and ethylenically unsaturated bond (henceforth "(a3)"), etc. are mentioned.

(a1) is a monomer (a1-1) (henceforth "(a1-1)") and alicyclic which have a structure in which a linear or branched aliphatic unsaturated hydrocarbon has epoxidized, and ethylenically unsaturated bond, for example. The monomer (a1-2) (henceforth "(a1-2)") which has a structure in which an unsaturated hydrocarbon group epoxidized, and ethylenically unsaturated bond is mentioned.

As (a1.1), glycidyl (meth) acrylate, (beta) -methyl glycidyl (meth) acrylate, (beta) -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinyl benzyl glyco Cylyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycidyl ether, α- Methyl-p-vinylbenzylglycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl ) Styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2 , 3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) styrene, and the like. have.

As (a1-2), vinylcyclohexene monooxide and 1,2-epoxy-4-vinylcyclohexane [for example, ceroxide 2000; Daicel Chemical Industries, Ltd.], 3, 4- epoxycyclohexylmethyl (meth) acrylate [for example, cyclomer A400; Daicel Chemical Industries, Ltd.], 3, 4- epoxycyclohexyl methyl (meth) acrylate [for example, cyclomer M100; Daicel Chemical Industry Co., Ltd.], the compound represented by Formula (I), the compound represented by Formula (II), etc. are mentioned.

[Formula (I) and Formula (II), R ^<a> and R <^b> represent a hydrogen atom or a C1-C4 alkyl group independently of each other, and the hydrogen atom contained in the said alkyl group may be substituted by hydroxy.

X ¹ and X ² 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.

* Represents a bond with O]

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

As an alkyl group in which a hydrogen atom was substituted by hydroxy, it is a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy The -1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, etc. are mentioned.

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

Examples of the alkanediyl group are methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1, 6-diyl group etc. are mentioned.

There may be mentioned (* denotes a bond with O hand) group, * -CH ₂ CH ₂ -O- group, - X ¹ and X ² as preferably a single bond, methylene group, ethylene group, * -CH ₂ -O more preferably, there may be mentioned a single bond, * -CH ₂ CH ₂ -O- group.

As a compound represented by Formula (I), the compound etc. which are represented by Formula (II-1) Formula (II-15) are mentioned. Preferably, Formula (II), Formula (II-3), Formula (II-5), Formula (II-7), Formula (II) or Formula (II-1) -Formula (II-15) The compound represented by) is mentioned. More preferably, the compound shown by Formula (II), Formula (II), Formula (II), or Formula (II-15) is mentioned.

As a compound represented by Formula (II), the compound etc. which are represented by Formula (II-1)-Formula (II-15) are mentioned. Preferably Formula (II-1), Formula (II-3), Formula (II-5), Formula (II-7), Formula (II-1) or Formula (II-1) -Formula (II-15). The compound represented by) is mentioned. More preferably, the compound represented by Formula (II-1), Formula (II-7), Formula (IIIX), or Formula (II-15) is mentioned.

The compound represented by Formula (I) and the compound represented by Formula (II) can be used independently, respectively. In addition, they can be mixed in any ratio. When mixing, the mixing ratio thereof is in a molar ratio, preferably as formula (I): formula (II), 5:95 to 95: 5, more preferably 10:90 to 90:10, and even more preferably Is 20: 80? 80: 20.

As a monomer (a2) which has an oxetanyl group and ethylenically unsaturated bond, the monomer which has an oxetanyl group and a (meth) acryloyloxy group is more preferable. Examples of (a2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, and 3- Ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacrylo Iloxy ethyl oxetane, 3-ethyl-3- acryloyloxy ethyl oxetane, etc. are mentioned.

As a monomer (a3) which has a tetrahydrofuryl group and ethylenically unsaturated bond, the monomer which has a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable.

Specific examples of (a3) include tetrahydrofurfuryl acrylate (for example, biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

As (a), it is preferable that it is (a1) from a viewpoint which can further improve reliability, such as heat resistance and chemical-resistance of the color filter obtained. Moreover, (a1-2) is more preferable at the point which is excellent in the storage stability of a coloring photosensitive resin composition.

Specific examples of (iii) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m- and p-vinyl benzoic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hepto-2-ene, 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-6-methylbicyclo [ Bicyclo unsaturated compounds containing carboxyl groups such as 2.2.1] hepto-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hepto-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, Unsaturated dicarboxylic anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene anhydride;

Unsaturated mono [(meth) acryloyloxyalkyl] of divalent or higher polyhydric carboxylic acid such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Esters; And

and unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule as?-(hydroxymethyl) acrylic acid.

Among them, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity or the solubility of the obtained resin in the aqueous alkali solution.

As (c), for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert- butyl (meth) acrylate, 2 Ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2 Methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate [in the art known as dicyclopentanyl (meth) acrylate], Dicyclopentanyloxyethyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate [in the art, it is commonly known as dicyclopentenyl (meth) acrylate. ], Isobornyl (meth) acrylic Yate, adamantyl (meth) acrylate, aryl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, etc. (Meth) acrylic acid esters;

Hydroxyl group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconic acid;

Bicyclo [2.2.1] hepto-2-ene, 5-methylbicyclo [2.2.1] hepto-2-ene, 5-ethylbicyclo [2.2.1] hepto-2-ene, 5-hydroxybi Cyclo [2.2.1] hepto-2-ene, 5-hydroxymethylbicyclo [2.2.1] hepto-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hepto-2 -Ene, 5-methoxybicyclo [2.2.1] hepto-2-ene, 5-ethoxybicyclo [2.2.1] hepto-2-ene, 5,6-dihydroxybicyclo [2.2.1 ] Hepto-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hepto-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] Hepto-2-ene, 5,6-dimethoxybicyclo [2.2.1] hepto-2-ene, 5,6-diethoxybicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5 -Methylbicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2. 1] hepto-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5- Cyclohexyloxycarbonylbicyclo [2.2.1] hepto-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5,6-bis (tert-butoxycarbonyl Bicyclo unsaturated compounds, such as) bicyclo [2.2.1] hepto-2-ene and 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hepto-2-ene;

N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl- Dicarbonylimide derivatives such as 6-maleimide caproate, N-succinimidyl-3-maleimide propionate and N- (9-acridinyl) maleimide;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, acetic acid Vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

Among them, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hepto-2-ene and the like are preferable from the viewpoint of copolymerization reactivity and heat resistance. Do.

In resin [K1], it is preferable that the ratio of the structural unit derived from each exists in the following ranges among all the structural units which comprise resin [K1].

structural units derived from (a); 50-98 mol% (more preferably 60-90 mol%)

structural units derived from (iii); 2-50 mol% (more preferably 10-40 mol%)

When the ratio of the structural unit of resin [k1] exists in the said range, there exists a tendency for the storage stability of a coloring photosensitive resin composition, developability, and the solvent resistance of a color filter to become favorable.

Resin B1 is, for example, the method described in the document "Experimental method of polymer synthesis" [Osaka Chemicals Co., Ltd. First Edition First Edition March 1, 1972] and the citation described in the document. It can be manufactured with reference to the literature.

Specifically, the method of heating and keeping warm while stirring in a deoxygen atmosphere by putting predetermined amounts of (a) and (iii), a polymerization initiator, a solvent, and the like into a reaction vessel and replacing oxygen with nitrogen, for example, Can be mentioned. Moreover, the polymerization initiator, the solvent, etc. which are used here are not specifically limited, Any conventionally used in the said field | area can be used. As a polymerization initiator, For example, an azo compound [2,2'- azobisisobutyronitrile, 2,2'- azobis (2, 4- dimethylvaleronitrile), etc.] and an organic peroxide (benzoyl peroxide etc.) Can be mentioned. What is necessary is just to melt | dissolve each monomer as a solvent, The solvent etc. which are mentioned later as a solvent (E) of the coloring photosensitive resin composition of this invention can be used.

Moreover, the obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and may use what extracted as solid (powder) by methods, such as reprecipitation. In particular, by using the solvent contained in the coloring photosensitive resin composition of this invention as a solvent at the time of this superposition | polymerization, since the solution after reaction can be used for preparation of the coloring photosensitive resin composition of this invention, the coloring photosensitive resin of this invention The manufacturing process of the composition can be simplified.

In resin [K2], it is preferable that the ratio of the structural unit derived from each exists in the following ranges among all the structural units which comprise resin [K2].

structural units derived from (a); 2 to 95 mol% (more preferably 5 to 80 mol%)

structural units derived from (iii); 4 to 45 mol% (more preferably 10 to 30 mol%)

structural units derived from (c); 1-65 mol% (more preferably 5-60 mol%)

When the ratio of the structural unit of resin [2] is in the said range, there exists a tendency for the storage stability of a coloring photosensitive resin composition, developability, and the solvent resistance, heat resistance, and mechanical strength of a color filter to become favorable.

Resin [K2] can be manufactured similarly to the method described as a manufacturing method of resin [K1], for example.

Specifically, a predetermined amount of (a), (iii) and (c), a polymerization initiator and a solvent are placed in a reaction vessel, and, for example, by replacing with oxygen by nitrogen, heating and warming while stirring in a deoxygenated atmosphere. How to do this. The obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and may use what extracted as solid (powder) by methods, such as reprecipitation.

In resin [K3], it is preferable that the ratio of the structural unit derived from each exists in the following ranges among all the structural units which comprise resin [K3].

(iii) 2 to 50 mol%, more preferably 5 to 40 mol%

(c) 50-98 mol%, More preferably, 60-95 mol%

Resin [K3] can be manufactured similarly to the method described as a manufacturing method of resin [K1], for example.

Resin [4] can obtain the copolymer of (i) and (c), and can be obtained by adding the C2-C4 cyclic ether which (a) has to the carboxy group or carboxylic anhydride which (iii) has.

First, the copolymer of (b) and (c) is manufactured similarly to the method described as a manufacturing method of [b1]. In this case, it is preferable that the ratio of the structural unit derived from each exists in the following ranges in all the structural units which comprise the copolymer of (i) and (c).

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

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

Next, the C2-C4 cyclic ether which (a) has is made to react with a part of carboxyl group and / or carboxylic anhydride contained in the structural unit derived from (i) in the said copolymer.

Subsequent to the production of the copolymers of (iii) and (c), the atmosphere in the flask was replaced with nitrogen from air, and (a), a reaction catalyst of the carboxyl group and the cyclic ether and a polymerization inhibitor were placed in the flask. For example, resin [K4] can be obtained by making it react at 60-130 degreeC for 1 to 10 hours. As said reaction catalyst, tris (dimethylaminomethyl) phenol etc. are mentioned, for example. The usage-amount of the said reaction catalyst is preferably 0.001-5 mass% with respect to the total amount of (a)-(c). As said polymerization inhibitor, hydroquinone etc. are mentioned, for example. The usage-amount of the said polymerization inhibitor is preferably 0.001-5 mass% with respect to the total amount of (a)-(c). Reaction conditions, such as a compounding method, reaction temperature, and time, can be suitably adjusted in consideration of the amount of heat generated by a manufacturing facility, polymerization, etc. In addition, the mixing method and the reaction temperature can be appropriately adjusted in consideration of the amount of heat generated by the production equipment, polymerization, and the like in the same manner as the polymerization conditions.

In this case, as for the usage-amount of (a), 5-80 mol is preferable with respect to 100 mol of (iii), More preferably, it is 10-75 mol, More preferably, it is 15-70 mol. By setting it as this range, there exists a tendency for the balance of the storage stability, developability, and the sensitivity of a coloring photosensitive resin composition, and the solvent resistance, heat resistance, and mechanical strength of a color filter to become favorable.

Resin [K5] is carried out similarly to the manufacturing method of resin [K1] mentioned above as a 1st step, and obtains the copolymer of (a) and (c). In the same manner as described above, the obtained copolymer may be used as it is, the concentrated or diluted solution may be used, or the extracted copolymer may be used as a solid (powder) by reprecipitation or the like.

It is preferable that the ratio of the structural unit derived from (a) and (c) exists in the following ranges with respect to the total number-of-moles of all the structural units which comprise the said copolymer, respectively.

structural units derived from (a); 5 to 95 mol% (more preferably 10 to 90 mol%)

structural units derived from (c); 5 to 95 mol% (more preferably 10 to 90 mol%)

Furthermore, the carboxylic acid or carboxylic anhydride which (b) has reacts with the cyclic ether derived from (a) which the copolymer of (a) and (c) has on the same conditions as the manufacturing method of resin [4]. By doing so, resin [K5] can be obtained.

As for the usage-amount of (b) which reacted with the said copolymer, 5-80 mol is preferable with respect to 100 mol of (a). Since the reactivity of a cyclic ether is high and it is hard to remain unreacted (a), as (a) used for resin [K5], (a1) is preferable and (a1-1) is more preferable.

Resin [6] is resin which made carboxylic anhydride further react with resin [5]. The carboxylic anhydride is reacted with a hydroxy group generated by the reaction of the cyclic ether with carboxylic acid or carboxylic anhydride.

As the carboxylic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetra Hydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene anhydride, and the like.

Specific examples of the resin include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer and 3,4-epoxycyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid air. Resins such as coalescing [X1]; Glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxy cicyclo [5.2 .1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid / vinyltoluene copolymer, 3 Resins such as -methyl-3- (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer; Resins such as benzyl (meth) acrylate / (meth) acrylic acid copolymer and styrene / (meth) acrylic acid copolymer; Resin tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer which added glycidyl (meth) acrylate to the benzyl (meth) acrylate / (meth) acrylic acid copolymer glycidyl (meth) Resins such as resin to which acrylate is added and resin to which glycidyl (meth) acrylate is added to tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer; Of resins obtained by reacting (meth) acrylic acid with a copolymer of dicyclopentanyl (meth) acrylate / glycidyl (meth) acrylate and dicyclopentanyl (meth) acrylate / styrene / glycidyl (meth) acrylate Resins such as resins in which (meth) acrylic acid is reacted with a copolymer; Resins, such as resin which further made tetrahydrophthalic anhydride react with resin which (meth) acrylic acid made to react the copolymer of dicyclopentanyl (meth) acrylate / glycidyl (meth) acrylate, etc. are mentioned. . Among these, Resin [K1] and Resin [K2] are preferable, Resin [K1] is more preferable, A 3, 4- epoxy cyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid copolymer is still more preferable. desirable. If resin (b) is resin containing the structural unit derived from (a), reliability, such as heat resistance and chemical-resistance, of a color filter obtained can be made higher.

Preferably the weight average molecular weight of polystyrene conversion of resin is 3,000-100,000, More preferably, it is 5,000-50,000, More preferably, it is 5,000-35,000, Especially preferably, it is 6,000-30,000, Among these, Preferably Is 7,000-28,000. When the molecular weight is in the above range, the coating film hardness is improved, the residual film ratio is also high, and the solubility in the developer of the unexposed part is good, so that the resolution tends to be improved.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of resin (B) becomes like this. Preferably it is 1.1-6, More preferably, it is 1.2-4.

The acid value of the resin is preferably 50 to 150 mg-KOH / g, more preferably 60 to 135 mg-KOH / g, 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 determined by titration using, for example, an aqueous potassium hydroxide solution.

The content of the resin is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, still more preferably 17 to 55% by mass relative to the solid content of the colored photosensitive resin composition of the present invention. . When content of resin exists in the said range, a coloring pattern can be formed and there exists a tendency for the resolution and a residual film rate to improve.

The coloring photosensitive resin composition of this invention contains a polymeric compound (C). The polymerizable compound (C) is a compound which can be polymerized by an active radical generated 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. ) Acrylic acid ester compound.

Especially, as a polymeric compound (C), it is preferable that it is a polymeric compound which has three or more ethylenically unsaturated bonds. As such a polymeric compound, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and tripentaerythritol octa (meth) acrylate, for example. , Tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylene Glycol-modified pentaerythritol tetra (meth) acrylate, ethylene glycol-modified dipentaerythritol hexa (meth) acrylate, propylene glycol-modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, capro Lactone-modified pentaerythritol tetra (meth) acrylate and caprolactone-modified And the like can be mentioned pentaerythritol hexa (meth) acrylate. Among these, Preferably, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned. You may use a polymeric compound individually or in combination of 2 or more types.

Preferably the weight average molecular weight of a polymeric compound (C) is 150 or more and 2,900 or less, More preferably, it is 250-1,500 or less.

It is preferable that content of a polymeric compound (C) is 7-65 mass% with respect to solid content of the coloring photosensitive resin composition of this invention, More preferably, it is 13-60 mass%, More preferably, it is 17-55 mass %to be. When content of the said polymeric compound (C) exists in the said range, hardening arises enough, the residual film rate in image development improves, it becomes difficult to undercut in a coloring pattern, and adhesiveness tends to become favorable. desirable.

The coloring photosensitive resin composition of this invention contains a polymerization initiator (D).

As said polymerization initiator (D), if it is a compound which generate | occur | produces an active radical, an acid, etc. by the action of light or heat, and can start superposition | polymerization, it will not specifically limit, A well-known polymerization initiator can be used.

As the polymerization initiator (D), compounds which generate active radicals by the action of light are preferable, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, oxime compounds and biimidazole compounds are more preferable, and oxime compounds are Even more preferred.

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

As a compound which has a partial structure represented by a formula (d2), for example, 2-methyl- 2-portolino- 1- (4-methylsulfanylphenyl) propane- 1-one, 2-dimethylamino-1- ( 4-morpholinophenyl) -2-benzylbutan-1-one, and 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] Butan-1-one etc. are mentioned. You may use commercially available products, such as Ilgacure (trademark) 369, 907, and 379 (above, BASF Corporation make).

As a compound which has a partial structure represented by a formula (d3), for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1- [4- (2 Oligomers of -hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, (alpha), (alpha)-diethoxy acetophenone, benzyl dimethyl ketal, etc. are mentioned.

From the viewpoint of sensitivity, as the alkylphenone compound, a compound having a partial structure represented by formula (d2) is preferable, and 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and More preferred is 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- ( 4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloro Rhomethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) Ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2 , 4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl)- 6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

2,4,6-trimethylbenzoyl diphenylphosphine oxide etc. are mentioned as said acylphosphine oxide compound. You may use commercially available products, such as Monocure (registered trademark) 819 (made by BASF Corporation).

The oxime compound is a compound having a partial structure represented by formula (d1). Hereinafter, * represents a bonding hand.

Examples of the oxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one- 2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2, 4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H- Carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3 -Cyclopentyl propane-1-one-2-imine, etc. are mentioned. You may use commercially available products, such as Ilgacure (trademark) OXE01, OXE02 (above, BASF Corporation), and N-1919 (ADEKA Corporation). Among these, when the colored photosensitive resin composition of this invention is a blue colored photosensitive resin composition, since the brightness of the color filter obtained becomes high, it is N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane- as said oxime compound. 1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3 Preference is given to using at least one member selected from the group consisting of -cyclopentylpropane-1-one-2-imine.

As a biimidazole compound, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenylbiimidazole and 2,2'-bis (2,3-dichlorophenyl) -4 , 4'5,5'-tetraphenylbiimidazole (see, eg, JP-A 6-75372, JP-A 6-75373, etc.), 2,2'-bis (2-chlorophenyl) -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'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (trialkoxyphenyl) biimidazole (see, eg, JP-A-48-38403 and JP-A 62-174204, etc.), 4,4 ', 5,5'-position The imidazole compound (For example, refer Unexamined-Japanese-Patent No. 7-10913 etc.) in which the phenyl group of is substituted by the carboalkoxy group is mentioned. Preferably 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole.

Furthermore, as a polymerization initiator (D), Benzoin compounds, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone and camphor quinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compound and the like. It is preferable to use these in combination with the polymerization initiator adjuvant (D1) [in particular, amines] mentioned later.

As an acid generator which generate | occur | produces an acid by light, 4-hydroxyphenyl dimethyl sulfonium p-toluene sulfonate, 4-hydroxyphenyl dimethyl sulfonium hexafluoro antimonate, 4-acetoxy phenyl dimethyl, for example. Sulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodine Onium salts such as nium p-toluenesulfonate and diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylates and benzointosylates;

Content of a polymerization initiator (D) becomes like this. Preferably it is 0.1-30 mass parts with respect to 100 mass parts of total amounts of resin (K) and a polymeric compound (C), More preferably, it is 1-20 mass parts. When content of a photoinitiator exists in the said range, it will become high sensitivity, shortening an exposure time, and improving productivity.

The coloring photosensitive resin composition of this invention may contain the polymerization initiator adjuvant (D1) further. The polymerization initiator (D1) is a compound or sensitizer used to promote the polymerization of the polymerizable compound in which polymerization is initiated by the polymerization initiator, and is usually used in combination with the polymerization initiator (D).

As polymerization initiator (D1), an amine compound, an alkoxy anthracene compound, a thioxanthone compound, a carboxylic acid compound, etc. are mentioned.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid isoamyl, 2-dimethylaminoethyl benzoic acid and 4-dimethylaminobenzoic acid 2 -Ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone [commonly known as Michler's ketone], 4,4'-bis (diethylamino) benzophenone, 4,4 ' -Bis (ethylmethylamino) benzophenone etc. are mentioned, Among these, 4,4'-bis (diethylamino) benzophenone is preferable. You may use commercial items, such as EAB-F (made by Hodogaya Chemical Co., Ltd.).

Examples of the alkoxy anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxy Anthracene, 2-ethyl-9, 10-dibutoxy anthracene, etc. are mentioned.

As a thioxanthone compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy city oxane Tone, etc. can be mentioned.

As the carboxylic acid compound, phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenyl sulfone Panyl acetic acid, dichlorophenylsulfanyl acetic acid, N-phenylglycine, phenoxy acetic acid, naphthyl thioacetic acid, N-naphthyl glycine, naphthoxy acetic acid, etc. are mentioned.

You may use a polymerization initiator independently or in combination of 2 or more types.

When using a polymerization initiator (D1), its usage-amount is preferably 0.1-30 mass parts with respect to 100 mass parts of total amounts of resin (K) and a polymeric compound (C), More preferably, it is 1-20. It is a mass part. When the amount of the polymerization initiator (D1) is within this range, the pattern can be formed even more sensitively, and the productivity of the pattern tends to be improved.

The coloring photosensitive resin composition of this invention contains a solvent (E). Solvent (E) is a solvent containing dipropylene glycol monomethyl ether acetate.

As for content of dipropylene glycol monomethyl ether acetate, 0.1 mass% or more and 30 mass% or less are preferable with respect to the total amount of a solvent (E), 1 mass% or more and 20 mass% or less are more preferable, 2 mass% or more and 15 mass% Even more preferred is% or less.

The solvent (E) may contain a solvent other than dipropylene glycol monomethyl ether acetate. It does not specifically limit as such a solvent, The solvent normally used in the said field can be used. For example, an ester solvent (a solvent containing a -COO-structure in a molecule and no -O-structure), an ether solvent (a solvent containing a -O-structure in a molecule and no -COO-structure) ), Ether ester solvent (solvent containing -COO-structure and -O-structure in the molecule), ketone solvent (solvent containing -CO-structure in the molecule and not containing -COO-structure), alcohol solvent ( The solvent which contains an OH group in a molecule | numerator, and does not contain -O-structure, -CO-structure, and -COO-structure), an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide, etc. are mentioned.

As the ester solvent, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyric acid Butyl, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, gamma -butyrolactone, and the like.

As the ether solvent, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol Monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1 , 4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methylethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phentol, methyl anisole, etc. Can be mentioned.

As an ether ester solvent, methyl methoxy acetate, ethyl methoxy acetate, methoxy acetate butyl, ethoxy acetate methyl, ethoxy acetate ethyl, 3-methoxy propionate methyl, 3-methoxy propionate ethyl, 3-ethoxy propionate methyl, Ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionic acid, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2-methyl Methyl propionate, 2-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 mono Ether and the like can be mentioned acetate, diethylene glycol monobutyl ether acetate.

As the ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentane Warm, cyclohexanone, isophorone and the like.

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

Benzene, toluene, xylene, mesitylene etc. are mentioned as an aromatic hydrocarbon solvent.

Examples of the amide solvents include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

You may use these solvents individually or in combination of 2 or more types.

Among the solvents described above, organic solvents having a boiling point of 120 ° C. or higher and 180 ° C. or lower at 1 atm are preferable from the viewpoint of applicability and drying properties. Among these, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, 3-ethoxy propionate ethyl, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4 -Hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide, N-methylpyrrolidone and the like are preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, 3- Ethoxy propionate ethyl etc. are more preferable.

It is preferable that a solvent (E) contains ethyl lactate with dipropylene glycol monomethyl ether acetate. In this case, as for content of ethyl lactate, 5 mass% or more and 90 mass% or less are preferable with respect to the total amount of a solvent (E), 20 mass% or more and 80 mass% or less are more preferable, 40 mass% or more and 70 mass% or less Even more preferred.

Moreover, it is preferable that a solvent (E) is three or more types of mixed solvents including dipropylene glycol monomethyl ether acetate, and it is more preferable that it is four or more types of mixed solvents.

When the solvent (E) is three or more mixed solvents including dipropylene glycol monomethyl ether acetate, the solvent (E) is dipropylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether and / or propylene. A solvent containing glycol monomethyl ether acetate is preferable, and a solvent containing dipropylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate is more preferable. Furthermore, it is preferable that the total content of these including dipropylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate is 90 mass% or more with respect to the total amount of the solvent (E), 95 mass% or more is more preferable.

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, more preferably 5% by mass or more and 30% by mass or less with respect to 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 or less with respect to the total amount of the solvent (E). Do.

When solvent (E) is said solvent, the film | membrane produced by drying under reduced pressure has little generation | occurrence | production of a crater-shaped defect, and can also suppress generation | occurrence | production of a stain.

Content of a solvent (E) becomes like this. Preferably it is 70-95 mass% with respect to the total amount of the coloring photosensitive resin composition of this invention, More preferably, it is 75-92 mass%. In other words, solid content of the coloring photosensitive resin composition of this invention becomes like this. Preferably it is 5-30 mass%, More preferably, it is 8-25 mass%. When content of a solvent (E) exists in the said range, flatness at the time of application | coating will become favorable, and since a color density does not run short when forming a color filter, there exists a tendency for display characteristics to become favorable.

The coloring photosensitive resin composition of this invention may further contain surfactant. As surfactant, silicone type surfactant, a fluorine-type surfactant, the silicone type surfactant which has a fluorine atom, etc. are mentioned. These may have a polymeric group in a side chain.

As silicone type surfactant, surfactant etc. which have a siloxane bond are mentioned. Specifically, Torre silicon (brand name) DC3PA, Torre silicon SH7PA, Torre silicon DC11PA, Torre silicon SH21PA, Torre silicon SH28PA, Torre silicon SH29PA, Torre silicon SH30PA, Torre silicon 8400 (made by Torre Downing 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 joint company] etc. are mentioned.

As said fluorine-type surfactant, surfactant etc. which have a fluorocarbon chain | strand are mentioned. Specifically, Floroid (registered trademark) FC430, Floride FC431 (manufactured by Sumitomo 3M Co., Ltd.), Mega Pack (registered trademark) F142D, Mega Pack F171, Mega Pack F172, Mega Pack F173, Mega Pack F177, Mega Pack F183, Megapack F554, Megapack R30, Megapack RS-718-K (manufactured by DIC Corporation), FTOP® EF301, FTop EF303, Ftop EF351, Ftop EF352 [Mitsubishi Electronic Materials Hwasung Co., Ltd.], Saffron (registered trademark) S381, Saffron S382, Saffron SC101, Saffron SC105 (manufactured by Asahi Co., Ltd.), E5844 [manufactured by Daikin Fine Chemical Research Institute Co., Ltd.]. have.

As silicone type surfactant which has the said fluorine atom, surfactant etc. which have a siloxane bond and a fluorocarbon chain | strand are mentioned. Specifically, Mega Pack (R) R08, Mega Pack BL20, Mega Pack F475, Mega Pack F477, Mega Pack F443 (manufactured by DIC Corporation), and the like.

You may use these surfactant individually or in combination of 2 or more types.

Content of surfactant is preferably 0.001 mass% or more and 0.2 mass% or less with respect to the total amount of the coloring photosensitive resin composition of this invention, Preferably it is 0.002 mass% or more and 0.1 mass% or less, More preferably, 0.01 It is mass% or more and 0.05 mass% or less. If content of surfactant is in the said range, flatness of a coating film can be made favorable.

The colored photosensitive resin composition of the present invention may contain various additives (hereinafter referred to as "other components"), such as fillers, other polymer compounds, adhesion promoters, antioxidants, ultraviolet light inhibitors, light stabilizers, and chain transfer agents, as necessary. You may include it.

The coloring photosensitive resin composition of this invention is a coloring agent (A), resin (B), a polymeric compound (C), a polymerization initiator (D), a solvent (E), and the polymerization initiator (D1) used as needed, for example. ), Surfactant, and other components can be prepared by mixing.

It is preferable to mix a pigment previously with one part or all part of solvent (E), and to disperse | distribute using BeadsMill etc. until the average particle diameter of a pigment becomes about 0.2 micrometer or less. Under the present circumstances, you may mix | blend a part or all of the said pigment dispersant and resin as needed. The target coloring photosensitive resin composition can be prepared by mixing components etc. which remain in the obtained pigment dispersion liquid so that it may become a predetermined density | concentration.

It is preferable to dissolve xanthene dye beforehand in one part or all part of solvent (E), and to prepare a solution. It is preferable to filter the said solution with the filter of about 0.01-1 micrometer of pore diameters.

It is preferable to filter the coloring photosensitive resin composition manufactured by mixing as mentioned above with the filter of about 0.01-10 micrometers of pore diameters.

As a method of forming the coloring pattern of a color filter using the coloring photosensitive resin composition of this invention, the photolithographic method, the method of using an inkjet apparatus, etc. are mentioned, for example. The photolithography method applies the colored photosensitive resin composition of the present invention onto a substrate or another resin layer (e.g., a separate colored photosensitive resin composition layer formed on the substrate first), and removes / drys volatile components such as a solvent. To form a coating film after drying, and then to form a pattern by exposing and developing the coating film after drying through a photomask. In this photolithography method, a coloring coating film may be formed by not using a photomask and / or developing at the time of exposure, and may be set as a color filter.

The film thickness of the color filter to manufacture is not specifically limited, It can adjust suitably according to the material, a use, etc. to use, For example, it is 0.1-30 micrometers, Preferably it is 1-20 micrometers, More preferably, it is 1? 6 μm.

A coloring photosensitive resin composition is apply | coated on a board | substrate, a solvent is removed by heat-drying (pre-bake) and / or drying under reduced pressure, and the coating film after smooth drying is obtained.

Examples of the substrate include glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and soda-lime glass coated with silica on the surface, resin plates such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, and the substrate. What formed aluminum, silver, silver / copper / palladium alloy thin film, etc. on the above is used.

As a coating method, the spin coat method, the slit coat method, the slit n spin coat method, etc. are mentioned.

30-120 degreeC is preferable and 40-100 degreeC of heat drying is more preferable. The heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.

It is preferable to perform drying under reduced pressure at the temperature range of 20-25 degreeC under the pressure of 50-150 Pa. The colored photosensitive resin composition of this invention shows the effect that generation | occurrence | production of a crater-shaped defect is few, even when drying under reduced pressure on such conditions.

The film thickness of the coating film after drying is not specifically limited, It can adjust suitably according to the material, a use, etc. to be used.

The coating film after drying is exposed through a photomask for forming a target pattern. At this time, the pattern on a photomask is not specifically limited, The thing according to the intended use is used.

As a light source used for exposure, the light source which produces the light of 250-450 nm wavelength is preferable. For example, light below 350 nm can be cut using a filter that cuts its wavelength range, or light around 436 nm, near 408 nm, and 365 nm can be selectively selected using a bandpass filter to extract their wavelength range. May be extracted. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp etc. are mentioned.

Since it is possible to irradiate parallel light uniformly to the entire exposure surface or to align the exact position of the mask and the substrate on which the coating film after drying is formed, it is preferable to use a device such as a mask aligner or a stepper.

After exposure, a coloring pattern can be obtained by contacting a developing solution and dissolving and removing an unexposed part (that is, developing). As a developing solution, the aqueous solution of alkaline compounds, such as potassium hydroxide, sodium hydrogencarbonate, tetramethylammonium hydroxide, etc., is preferable, for example. The density | concentration in the aqueous solution of such an alkaline compound becomes like this. Preferably it is 0.01-10 mass%, More preferably, it is 0.03-5 mass%. The developing solution may further contain surfactant.

The developing method may be any of paddle method, dipping method, spray method and the like. Further, the substrate may be tilted at any angle during development.

It is preferable to wash with water after image development.

Furthermore, you may post-bake as needed. 150-250 degreeC is preferable and 160-220 degreeC of post-baking temperature is more preferable. The post-baking time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

According to the coloring photosensitive resin composition of this invention, the color filter with few bonds can be produced especially. The said color filter is useful as a color filter used for a display apparatus (for example, a liquid crystal display device, an organic electroluminescent apparatus, and an electronic paper), and a solid-state image sensor.

Example

Hereinafter, the coloring photosensitive resin composition of this invention is demonstrated in detail by an Example. "%" And "part" in an Example are mass% and a mass part, unless there is particular notice.

Synthesis Example 1

In a flask equipped with a cooling tube and a stirring device, 15 parts of a compound represented by Formula (A0-1) and a compound (manufactured by Chugai Kasei) represented by Formula (A0-2), 150 parts of chloroform, and N, N-dimethylform 8.9 parts of amides were added and 10.9 parts of thionyl chlorides were added dropwise while maintaining 20 ° C or less under stirring. After completion of the dropwise addition, the temperature was raised to 50 ° C, held at the same temperature for 5 hours for reaction, and then cooled to 20 ° C. The mixed solution of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was dripped, and added, maintaining the reaction solution after cooling at 20 degrees C or less under stirring. Thereafter, the reaction was stirred at the same temperature for 5 hours. Subsequently, the obtained reaction mixture was removed by evaporating the solvent with a rotary evaporator, and then a small amount of methanol was added thereto, followed by vigorous stirring. This mixture was added to the liquid mixture of 375 parts of ion-exchange water, stirring, and the crystal | crystallization was deposited. Precipitated crystals were separated by filtration, washed further with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain 11.3 parts of dye A1 (a mixture of compounds (1-1) and (1)).

Synthesis Example 2

20 parts of compounds represented by Formula (1) and 200 parts of N-ethyl-o-toluidine (made by Wako Pure Chemical Industries, Ltd.) were mixed under light-shielding conditions, and the obtained solution was stirred at 110 degreeC for 6 hours. After cooling the obtained reaction liquid to room temperature, it added in 800 parts of water and 50 parts of 35% hydrochloric acid, and the crystal | crystallization precipitated when it stirred at room temperature for 1 hour. The precipitated crystals were obtained as a residue of suction filtration and dried to obtain 24 parts of the compound represented by the formula (1-3). Yield 80%.

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

Exact Mass: 602.2

Synthesis Example 3

Except having used N-propyl-2,6-dimethylaniline instead of N-ethyl-o-toluidine, it carried out similarly to the synthesis example 1, and obtained the compound shown by Formula (1-393).

Identification of the compound represented by formula (1-39)

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

Exact Mass: 658.9

Synthesis Example 4

In a flask equipped with a reflux condenser, a dropping rod, and a stirrer, nitrogen was flowed at 0.02 L / min to a nitrogen atmosphere, and 305 parts by mass of ethyl lactate was heated to 70 ° C while stirring. Subsequently, 60 parts by mass of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate [a compound represented by the formula (1-1) and a compound represented by the formula (II-1) in a molar ratio of 50: Mixed with 50] A solution was prepared by dissolving 240 parts by mass and 140 parts by mass of ethyl lactate, and the solution was added dropwise into a flask kept at 70 ° C. over 4 hours using a dropping rod.

On the other hand, the solution which melt | dissolved 30 mass parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) at 225 mass parts of ethyl lactate was dripped in the flask over 4 hours using the other dropping rod. After the dropwise addition of the solution of the polymerization initiator was completed, the solution was maintained 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, a solid content of 33 mass%, and a solution acid value. A resin # 1 solution of 34 mg-KOH / g was obtained. Calculated from said solid content and solution acid value, solid content acid value of resin # 1 is 100 mg-KOH / g. Resin B1 has the structural unit shown below.

Synthesis Example 5

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping rod, and a nitrogen inlet tube, the atmosphere was changed to nitrogen from air, and then heated to 100 ° C. 70.5 g (0.40 mol) of methacrylate, 43.0 g (0.5 mol) of methacrylic acid, 22.0 g (0.10 mol) of dicyclopentanyl methacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.), and propylene glycol monomethyl ether acetate 136 The solution which added 3.6 g of 2,2'- azobisisobutyronitrile was dripped at the mixture which consists of g, and stirring was further continued at 100 degreeC. Subsequently, the atmosphere in the flask was nitrogen to air, and 35.5 g [0.25 mol of glycidyl methacrylate ((50 mol% based on the carboxyl group of methacrylic acid used in this reaction)], 0.9 g of trisdimethylaminomethylphenol and hydro 0.145 g of quinone was charged into a flask, and the reaction was continued at 110 ° C. to obtain a resin # 2 solution having a solid content of 32% and a solid acid value of 79 mgKOH / g.The weight average molecular weight of polystyrene measured by GPC was 30,000.

The measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of resin obtained by the synthesis example was performed on condition of the following using GPC method.

Device; K2479 [product made by Shimadzu Corporation]

column; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ℃

menstruum; Tetrahydrofuran (THF)

Flow rate; 1.0 mL / min

Detectors; RI

Calibration standards; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 [product of Tosoh Corporation]

The ratio (Mw / Mn) of the weight average molecular weight and number average molecular weight of polystyrene conversion obtained above was made into molecular weight distribution.

Examples 1-12 and Comparative Example 1

Each component was mixed like the composition shown in Table 1 and Table 2, and the coloring photosensitive resin composition was obtained.

In Table 1 and Table 2, (A-1) ¹⁾ was mixed with the acrylic dispersant and the total amount of propylene glycol monomethyl ether acetate, and used beforehand to disperse. However, (A-1) in the comparative example 1 was mixed with 137 parts of an acryl-type dispersing agent and propylene glycol monomethyl ether acetate, and used previously, disperse | distributing.

Moreover, in Table 1 and Table 2, each component shows the following.

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

Colorant (A); (A? 2); Dye A1 (Xanthene Dye)

Colorant (A); (A? 3); Compound (Xanthene Dye) Represented by Formula (1-9)

Resin; (Ｂ? 1); Resin X1 table shows the mass part of solid content conversion.

Resin; (2); Resin X2 table shows the mass part of solid content conversion.

Polymeric compound (C); (C? 1); Dipentaerythritol hexaacrylate [KAYARAD DPHA; Nippon Gunpowder Co., Ltd.]

Polymerization initiator (D); (D? 1); N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (monocure OXE 01; made by BASF Japan)

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

Surfactants; (Ｇ? 1); Polyether modified silicone oils [Torre Silicone SH8400; Torre Downing Co., Ltd.]

<Production of colored pattern>

After apply | coating the coloring photosensitive resin composition on the 2-inch square glass substrate (Eagle 2000; the product made by Corning Corporation) by the spin coat method, it pre-baked at 100 degreeC for 3 hours, it dried, and formed the coating film. After cooling, the gap between the substrate on which the coating film after drying was formed and a photomask made of quartz glass having a pattern (100 µm line-and-space pattern) was set to 100 µm, and the exposure machine [TME-150RSK; Topcon Co., Ltd.] was used and light irradiation was carried out at an exposure amount (365 nm standard) of 150 mJ / cm 2 under an atmospheric atmosphere. After light irradiation, the coating film was deposited and developed at 23 ° C. for 80 seconds in an aqueous developer containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide, washed with water, and post-baked at 220 ° C. for 20 minutes in an oven. It carried out and obtained the coloring pattern. After cooling, the film thickness of the obtained colored pattern was measured by a film thickness measuring apparatus [DEKTAK3; It was 2.2 micrometers when it measured using Nippon Vacuum Technology Co., Ltd. product.

<Color evaluation>

Regarding the obtained colored pattern, a colorimeter [OSP-SP-200; Spectrophotometry was measured using Olympus Co., Ltd., and the xy chromaticity coordinates (Bx, By) and tristimulus values Y in the XYZ colorimeter of CIE were measured using the characteristic coefficient of the C light source. The larger the value of Y, the higher the brightness. The results are shown in Tables 3 and 4.

<Defect Evaluation>

The colored photosensitive resin composition was apply | coated by the spin coat method on the 3-inch-angle glass substrate (Eagle 2000; the product made by Corning Corporation), and it dried by the pressure reduction dryer (made by VCD Microtech Co., Ltd.) until the pressure reduction degree reached 0.5 torr. . Subsequently, it prebaked at 100 degreeC for 3 hours in a clean oven, and the dried coating film was formed on the board | substrate. The dried coating film was subjected to a surface optical microscope [magnification of 250 times; VF-7510; Made by Keyence Co., Ltd. and counted the number of defects having the same shape as the crater existing in the entire substrate except for the range of 1 cm at the substrate end. The results are shown in Tables 3 and 4.

<Heat resistance evaluation>

A colored coating film was produced in the same manner as the preparation of the pattern except that no photomask was used at the time of exposure. The colored coating film was heated in an oven at 230 ° C. for 2 hours, and chromaticity and tristimulus values Y were measured in the same manner as above. Color difference (DELTA) Eab * was computed from the chromaticity and tristimulus value Y before and behind heating. The smaller the color difference ΔEab * is, the less the color change before and after heating, indicating that the heat resistance is good. The value of calculated color difference (DELTA) Eab * was shown in the "heat resistance" column of Table 3 and Table 4.

Examples 13-18

Each colored photosensitive resin composition was obtained like Example 1-6 except having used the compound shown by Formula (1-3) instead of dye A1. The same operation as above was performed and the coating film after drying with few defects was obtained. Furthermore, the coloring pattern excellent in the brightness and heat resistance was obtained.

From the said result, it turned out that the coloring photosensitive resin composition of Examples 1-12 does not reduce the brightness and heat resistance of the color filter obtained, and can obtain the coating film after drying with few defects.

By forming the coating film after drying from the coloring photosensitive resin composition of such this invention, and making the color pattern obtained from the coating film after the drying into a color filter, it becomes possible to manufacture a display apparatus with a high yield.

The colored photosensitive resin composition of this invention is dried under reduced pressure after a coating film to a board | substrate, and generation | occurrence | production of the crater-shaped defect is few in the coating film after drying which was produced.

Claims (8)

The coloring photosensitive resin composition containing a coloring agent, resin, a polymeric compound, a polymerization initiator, and a solvent, the said coloring agent is a coloring agent containing a xanthene dye and a pigment, and the said solvent is a solvent containing dipropylene glycol monomethyl ether acetate. The method of claim 1,
The coloring photosensitive resin composition whose content of the said dipropylene glycol monomethyl ether acetate is 0.1 mass% or more and 30 mass% or less in a solvent. The method according to claim 1 or 2,
The coloring photosensitive resin composition whose said solvent is a solvent containing ethyl lactate further. The method of claim 3, wherein
The coloring photosensitive resin composition whose said solvent is a solvent which further contains a propylene glycol monomethyl ether and / or a propylene glycol monomethyl ether acetate. The method of claim 1,
The coloring photosensitive resin composition whose said resin is alkali-soluble resin. The method of claim 1,
The coloring photosensitive resin composition whose said polymeric compound is (meth) acrylic acid ester. The color filter formed with the coloring photosensitive resin composition of Claim 1. The display device containing the color filter of Claim 7.