KR20120102529A - Colored photosensitive resin composition - Google Patents

Abstract

PURPOSE: A colored photosensitive resin composition is provided to form patterns based on the little amount of exposure based on the superior sensitivity of the composition. CONSTITUTION: A colored photosensitive resin composition includes a coloring agent, a binder resin, a polymerizable compound, and a polymerization initiator. The coloring agent includes a dye. The polymerization initiator includes an oxime compound and an alkyl phenone compound. The resin composition further includes a thioxanthone compound. The content of the oxime compound is 20-98 mass% based on the content of the polymerization initiator. A color filter is formed based on the composition. A display device includes the color filter.

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. As this coloring photosensitive resin composition, the coloring photosensitive resin composition containing only N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine as a polymerization initiator is known (patent document 1).

Japanese Patent Publication No. 2010-224204

The coloring photosensitive resin composition conventionally known may not fully satisfy sensitivity. If the sensitivity is low, there is a fear that productivity is lowered because a long time is required for exposure through a photomask.

This invention provides the following [1]-[6].

[1] a colorant, a binder resin, a polymerizable compound and a polymerization initiator,

The colorant is a colorant comprising a dye,

The coloring photosensitive resin composition whose polymerization initiator is a polymerization initiator containing an oxime compound and an alkylphenone compound.

[2] The colored photosensitive resin composition according to [1], further comprising a thioxanthone compound.

[3] The colored photosensitive resin composition according to [1] or [2], wherein the content of the oxime compound is 20% by mass to 98% by mass with respect to the content of the polymerization initiator.

[4] The colored photosensitive resin composition according to any one of [1] to [3], wherein the coloring agent is a coloring agent containing a pigment and a dye.

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

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

(Effects of the Invention)

Since the coloring photosensitive resin composition of this invention has high sensitivity, a pattern can be formed with a small exposure amount.

The coloring photosensitive resin composition of this invention contains a coloring agent (A), binder resin (B), a polymeric compound (C), and a polymerization initiator (D),

The colorant (A) is a colorant containing a dye (A1),

A polymerization initiator (D) is a coloring photosensitive resin composition which is a polymerization initiator containing an oxime compound and an alkylphenone compound.

It is preferable that a coloring agent (A) also contains pigment (A2) with dye (A1).

It is preferable that the coloring photosensitive resin composition of this invention contains at least 1 sort (s) chosen from the group which consists of a polymerization start adjuvant (D1) and a solvent (E).

In addition, the coloring photosensitive resin composition of this invention may contain surfactant (F).

Colorant (A) comprises dye (A1). Examples of the dye (A1) include dyes such as oil-soluble dyes, acid dyes, amine salts of acid dyes, and sulfonamide derivatives of acid dyes. For example, dyes, i.e., pigs, can be obtained from the color index (The Society of Dyers and Colourists). The well-known dye described in the compound classified by the addition to a pigment, and a dyeing note (Shiksen Corporation) is mentioned. Moreover, according to chemical structure, azo dye, anthraquinone dye, triphenylmethane dye, xanthene dye, phthalocyanine dye, etc. are mentioned. These dyes may be used independently or may use 2 or more types together.

Specifically, C.I. solvent yellow 4 (hereinafter, mention of C.I. solvent yellow is omitted and only mentions number), 14, 15, 23, 24, 38, 62, 63, 68, 82 94, 98, 99, 162;

C. I. Solvent Red 45, 49, 125, 130;

C. I. Solvent orange 2, 7, 11, 15, 26, 56;

C. I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;

C. I. Solvent blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59: 1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;

C．I．Solvent green C．I. Solvent dyes such as 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc.

C. I. Acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

C. I. Acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;

C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

C. I. Acid Violet 6B, 7, 9, 17, 19, 30, 34, 102;

C. I. Acid blue 1, 7, 9, 15, 18, 22, 23, 25, 27, 29, 40, 41, 42, 43, 45, 51, 54, 59, 60, 62, 70, 72, 74, 78, 80, 82, 83, 86, 87, 90, 92, 93, 96, 100, 102, 103, 104, 112, 113, 117, 120, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 229, 234, 236, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340;

C. I. Acid dyes such as acid green 1, 3, 5, 9, 16, 25, 27, 28, 41, 50, 58, 63, 65, 80, 104, 105, 106, 109, etc.

C. I. Direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;

C. I. Direct red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

C. I. Direct orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

C. I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

C. I. Direct blue 1, 2, 6, 8, 15, 22, 25, 40, 41, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;

C. I. Direct dyes such as direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc.

C. I. Dispers Yellow 51, 54, 76;

C. I. Disperse violet 26, 27;

C．I．Disperse blue C．I. Disperse dyes such as 1, 14, 56, 60,

C. I. Basic red 1, 10;

C．I． Basic blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68;

C. I. Basic green 1; C. I. Basic dyes such as

C. I. Reactive Yellow 2, 76, 116;

C. I. Reactive orange 16;

C．I．Reactive Red 36; C.I. reactive dyes such as

C. I. Modern Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

C．I．Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38 , 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;

C. I. Modern orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48 ;

C. I. Modern Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;

C．I．Modern Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40 , 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;

C. I. Modern green C, I. Modern dyes such as 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53, etc.

C. I. Bat dyes, such as bat green 1, etc. are mentioned.

As dye (A1), xanthene dye is preferable.

Xanthene dyes are dyes comprising a compound having a xanthene skeleton in its molecule.

As xanthene dye, for example, C.I. Acid red 51, 52, 87, 91, 92, 94, 95, 98, 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, xanthene dyes described in Japanese Patent Laid-Open No. 2010-32999 and Japanese Patent No. 4492760. Xanthene dye etc. are mentioned.

Especially, as xanthene dye, the dye containing the compound represented by Formula (1) (hereinafter may be called "compound (1)") is preferable. Compound (1) may be a tautomer thereof. When using compound (1), content of compound (1) in xanthene dye becomes like this. Preferably it is 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 (1) as xanthene dye.

[In formula (1), R <^1> -R <^4> respectively independently represents a hydrogen atom, a C1-C20 monovalent saturated hydrocarbon group, or a C6-C10 monovalent aromatic hydrocarbon group, and the hydrogen atom contained in the said aromatic hydrocarbon group is 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 ,- 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 a 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 combined to form a ring containing a nitrogen atom, and R ³ and R ⁴ may be combined to form a ring containing a nitrogen atom.

R ⁵ is _{-OH, -SO 3 -, -SO 3} H, -SO 3 - M +, -CO2H, -CO 2 - M +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ NR ⁹ R ¹⁰ is represented.

m represents the integer of 0-5. When m is an integer of 2 or more, a plurality of R ⁵ are 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 hydroxy group or a halogen atom and is contained in the saturated aliphatic hydrocarbon group. CH ₂ — may be substituted with —O—, —CO—, —NH— or —NR ⁸ —, or R ⁹ and R ¹⁰ may be bonded to each other to form a 3 to 10 membered heterocycle including a nitrogen atom; good]

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

R ¹ to R ⁴ 6 carbon atoms in a group of 10 monovalent aromatic hydrocarbon substituent _{-SO 3 -??, -SO 3} H, -SO 3 - M + and -SO ₂ selected from the group consisting of NR ⁹ R ¹⁰ preferably has at least one kind, and, -SO ₃ ^- and more preferably that has at least one member selected from the group consisting of M ⁺ and SO 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 these groups, the color filter which has little generation | occurrence | production of a foreign material and is 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 forming R ¹ and R ² together and the ring formed by R ³ and R ⁴ together include the following.

As a C1-C20 monovalent saturated hydrocarbon group in R <^1> -R <^4> , R <^8> -R <^11> , a methyl group, an ethyl group, a propyl group, isopropyl group, a butyl group, isobutyl group, a pentyl group, isopentyl group, Alkyl groups having 1 to 20 carbon atoms such as neopentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group, hexadecyl group and eicosyl group; C3-C20 cycloalkyl 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, an octyloxy group, 2-ethylhexyloxy group, an ecosyloxy group etc. are mentioned, for example. have.

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

Examples of -SR ⁸ include methylsulfanyl group, ethylsulfanyl group, butylsulfanyl group, hexylsulfanyl group, decylsulfanyl group, and eicosylsulfanyl group.

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

Examples of -SO ₃ R ⁸ include a methoxysulfonyl group, ethoxysulfonyl group, propoxysulfonyl group, tert-butoxysulfonyl group, hexyloxysulfonyl group, ecosyloxysulfonyl group and the like.

-SO ₂ NR ⁹ R ^{10 is} , 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 a sulfamoyl group, N- (1,5-dimethyl) hexyl sulfamoyl group, and N- (1,1,2,2- tetramethylbutyl) sulfamoyl group; 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 may be substituted by hydrogen atoms are -OH, or a halogen atom contained to said saturated hydrocarbon, -CH ₂ contained to said saturated hydrocarbon - is -O -, -CO-, -NH-, or -NR ⁸ -may be substituted.

R ⁹ and R ¹⁰ may be bonded to each other to form a 3 to 10 membered heterocycle including 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.

As a C1-C6 alkyl group in R <^6> and R <^7> , a C1-C6 thing is mentioned among the alkyl groups enumerated above.

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

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 s} are preferably 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 <^11> , 20-60 pieces are more preferable. When ⁺ N (R ¹¹ ) ₄ is present in the compound (1), if R ¹¹ is their group, a color filter with less foreign matter can be formed from the colored photosensitive resin composition of the present invention containing the compound (1).

The xanthene dye is more preferably a dye containing a compound represented by the formula (2) (hereinafter may be referred to as "compound (2)"). Compound (2) may be a tautomer thereof. When using compound (2), content of the 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 the equation (2): R ²¹ R ²⁴ are each independently a hydrogen atom, -R ²⁶ or a carbon number of 6 to 10 show 1-valent aromatic hydrocarbon group, hydrogen atoms contained to said aromatic hydrocarbon is -SO ₃ ^-?, -SO ₃ ^- M ^{a +} , -SO ₃ H, -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ may be substituted.

X ^a represents a halogen atom.

a ¹ 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;

As a C6-C10 monovalent aromatic hydrocarbon group in R <^21> -R <^24> , the group similar to what was mentioned as an aromatic hydrocarbon group in R <^1> -R <^4> is mentioned.

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 It is -SO ₃ ^- may be 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 monovalent aromatic hydrocarbon groups 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 these groups, the color filter excellent in heat resistance can be formed from the coloring photosensitive resin composition of this invention containing compound (2).

As a C1-C20 monovalent saturated hydrocarbon group in R <^26> and R <^27> , the group similar to what was mentioned as a saturated hydrocarbon group in R <^8> -R <^11> is mentioned.

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.

-SO ₃ R ^26, and -SO ₂ NHR ²⁶ R ²⁶ as in the carbon number of 3? Are 20 branch chain alkyl group are preferred, and C 6? Are 12 branch chain alkyl group, and more preferably, is more preferably a 2-ethylhexyl group Do. If R <^26> is these groups, the color filter with little generation | occurrence | production of a foreign material can be formed from the coloring photosensitive resin composition of this invention containing compound (2).

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

^{As +} N (R ²⁷ ) ₄ , at least two of four R ²⁷ are preferably a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. Moreover, 20-80 pieces are preferable and, as for the 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 includes the compound (2) as a group thereof.

1-4 are preferable and, as for m1, 1 or 2 is more preferable.

As a preferable xanthene dye, the dye which has a compound represented by a formula (1-1)-a formula (1-29) as a main component is mentioned, for example. In the following formulae, Ra represents a C 1-20 monovalent saturated hydrocarbon group, preferably a C 6-12 branched alkyl group, more preferably 2-ethylhexyl group. Among these, sulfonamides of C.I. acid red 289, quaternary ammonium salts of C.I. acid red 289, sulfonamides of C.I. acid violet 102 or quaternary ammonium salts of C.I. acid violet 102 desirable. As such a compound, the compound etc. which are represented, for example by Formula (1-1)-Formula (1-8), Formula (1-11), and Formula (1-12) are mentioned.

Moreover, as xanthene dye, the dye containing the compound represented by Formula (3) (Hereinafter, it may be called "compound (3)") is more preferable. Compound (3) may be a tautomer thereof. When using compound (3), content of the compound (3) 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 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 combined to form a ring containing a nitrogen atom, and R ³² and R ³⁴ may be combined to form a ring containing a nitrogen atom.

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

As a C1-C10 alkyl group which shows R <^31> and R <^32> , a methyl group, an ethyl group, a propyl group, a butyl group, isopropyl group, isobutyl group, sec-butyl group, tert- butyl group, hexyl group, and 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 up to 4 carbon atoms is mentioned among these.

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 C1-C4 alkyl groups, and it is more preferable that it is a methyl group.

Independently of p and q, the integer of 0-2 is preferable, and 1 or 2 is more preferable.

As compound (3), the compound represented, for example by Formula (1-30)-Formula (1-42) is mentioned, respectively. Especially, the compound represented by Formula (1-30)-Formula (1-39) is preferable at the point which is excellent in the solubility to an organic solvent.

As xanthene dye, you may use commercially available xanthene dye (for example, "Chugai Aminol Fast Pink RH / C" by Chugai Kasei Co., Ltd., "Rhodamin6G" by Taoka Kagaku Kogyo Co., Ltd.). have. Moreover, a commercially available xanthene dye can also be synthesized with reference to Japanese Patent Laid-Open No. 2010-32999 as a starting material.

The pigment (A2) is not particularly limited, and known pigments can be used, and compounds classified as pigments in the color index (Published by The Society of Dyers and Colourists), for example, 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, 147, 148, 150 Yellow pigments such as, 153, 154, 166, 173, 194, and 214;

C. I. Pigment Orange Pigment of orange color, such as 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

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 Red pigments such as 265;

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

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

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

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

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

Among them, C.I. Pigment Yellow 138, 139, 150, C. I. Pigment Red 177, 209, 242, 254, C. I. Pigment Violet 23, C. I. Pigment Blue 15: 3, 15: 6 and C. I. Pigment Green 7, 36 and 58 are preferable. As a pigment used for the coloring photosensitive resin composition of this invention, C.I. pigment blue 15: 6, C.I. pigment red 254, C.I. pigment red 242, C.I. pigment red 177, Pigment containing at least 1 sort (s) chosen from the group which consists of C. I. Pigment Green 58, C. I. Pigment Yellow 150, and C. I. Pigment Yellow 138 is more preferable. By including the pigment, optimization of the transmission spectrum is easy, and chemical resistance becomes good.

These pigments may be used independently or may use 2 or more types together.

Pigments may be rosin-treated, surface-treated with pigment derivatives having acidic or basic groups introduced therein, graft treatment to the surface of the pigments with high molecular compounds, etc., microorganisms such as sulfuric acid atomization, or organic solvents to remove impurities. A washing treatment with water or the like, a removal treatment by an ion exchange method of ionic impurities, or the like may be performed.

It is preferable that a pigment is uniform particle size. The pigment dispersion liquid of the state in which the pigment was disperse | distributed uniformly in the solution can be obtained by containing a pigment dispersing agent and performing a dispersion process.

Examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic. You may use these pigment dispersants individually or in combination of 2 or more types. As a pigment dispersant, it is KP (made by Shin-Etsu Kagaku Kogyo Co., Ltd.), Floren (made by Kyoeisha Kagaku Co., Ltd.), Solsperth (made by Geneca Co., Ltd.), EFKA (made by CIBA company), Aji spa ( Ajinomoto Fine Techno Co., Ltd., Disperbyk (made by BICKEM Corporation), etc. are mentioned.

When using a pigment dispersant, the usage-amount is 100 mass parts or less with respect to 100 mass parts of pigments (A2), More preferably, they are 5 mass parts or more and 50 mass parts or less. When the usage-amount of a pigment dispersant exists in the said range, there exists a tendency for the pigment dispersion liquid of a uniform dispersion state to be obtained.

When the pigment (A2) is included, the content ratio ((A1) :( A2)) of the dye (A1) and the pigment (A2) is preferably 1:99 to 99: 1 by mass, and 3:97 to 90: 10 is more preferable. By setting it as such a ratio, the optimization of a transmission spectrum becomes easy, and the color filter obtained tends to be excellent in contrast, brightness, heat resistance, and chemical resistance.

In particular, when preparing the colored photosensitive resin composition of this invention as a blue coloring photosensitive resin composition, as a coloring agent (A), the coloring agent containing a xanthene dye and a blue pigment is preferable, and xanthene dye and C. I. pigment blue 15 The coloring agent containing: 6 is more preferable. The mass ratio of xanthene dye and blue pigment is preferably 3:97 to 90:10, more preferably 3:97 to 70:30, and even more preferably 3:97 to 50:50.

Content of a coloring agent (A) becomes like this. Preferably it is 5-60 mass% with respect to solid content in a coloring photosensitive resin composition, More preferably, it is 8-55 mass%, More preferably, it is 10-50 mass%. Solid content means the sum total of the component except the solvent in a coloring photosensitive resin composition here. When the content of the colorant (A) is in the above range, desired spectroscopic or color concentration can be obtained when the color filter is used, and a necessary amount of binder resin or polymerizable compound can be contained in the composition, thereby forming a pattern having sufficient mechanical strength. Can be.

Although binder resin (B) is not specifically limited, It is preferable that it is alkali-soluble resin. As binder resin (B), the following resin [K1]-[K6] etc. are mentioned, for example.

[K1] at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter may be referred to as "(a)"), a cyclic ether structure having 2 to 4 carbon atoms, and ethylene Copolymer of the monomer (b) (Hereinafter, it may be called "(b)") which has a sex unsaturated bond.

[K2] The air of monomers (c) copolymerizable with (a) and (b) and (a) (wherein (a) and (b) are different) (hereinafter may be referred to as "(c)") coalescence

[K3] Copolymer of (a) and (c)

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

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

Resin obtained by making (a) react with the copolymer of (b) and (c), and making carboxylic anhydride further react.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic 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, Unsaturated dicarboxylic acids such as dimethyltetrahydrophthalic 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 (hymic acid anhydride);

Unsaturated mono [(meth) acryloyloxy alkyl of a bivalent or more polyvalent carboxylic acid, such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic mono [2- (meth) acryloyloxyethyl] ] Esters;

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

Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferable from the point of copolymerization reactivity or the solubility of the resin obtained to aqueous alkali solution.

(b) is a polymerizable polymer having an ethylenically unsaturated bond with, for example, a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) Say a compound. As for (b), the monomer which has a C2-C4 cyclic ether and a (meth) acryloyloxy group is preferable.

In addition, in this specification, "(meth) acrylic acid" shows at least 1 sort (s) chosen from the group which consists of acrylic acid and methacrylic acid. Notation, such as "(meth) acryloyl" and "(meth) acrylate", also has the same meaning.

As (b), for example, a monomer (a1) (hereinafter may be referred to as "(b1)") having an oxiranyl group and an ethylenically unsaturated bond, and a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter "(B2)" may be mentioned, the monomer (b3) (henceforth "(b3)" hereafter) which has a tetrahydrofuryl group and ethylenically unsaturated bond, etc. are mentioned.

(b1) is a monomer (b1-1) (hereinafter sometimes referred to as "(b1-1)") having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized, and the alicyclic unsaturated hydrocarbon is epoxy. The monomer (b1-2) which has a ized structure (henceforth "(b1-2)") is mentioned.

As (b1-1), glycidyl (meth) acrylate, (beta) -methyl glycidyl (meth) acrylate, (beta) -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, and 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 (b1-2), vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, ceoxide 2000; made by Daicel Kagaku Kogyo Co., Ltd.), 3,4-epoxycyclohexyl Methyl (meth) acrylate (for example, cyclomer A400; manufactured by Daicel Kagaku Kogyo Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, cyclomer M100; dicel) Kagaku Kogyo Co., Ltd.), the compound represented by Formula (I), the compound represented by Formula (II), etc. are mentioned.

[In formula (I) and (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 the hydroxy group.

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

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

＊ represents the number of bonds 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 -1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, etc. are mentioned.

As R ^<a> and R <^b>, Preferably, a hydrogen atom, a methyl group, a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group are mentioned, More preferably, a hydrogen atom and a methyl group are mentioned.

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.

X ¹ and X ² as preferably a single bond, methylene group, ethylene group, * -CH ₂ -O - include (* indicates the number of engagement with the O) group, * -CH ₂ CH ₂ -O- group and , and 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 (I-1)-Formula (I-15) are mentioned. Preferably formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) or formula (I-11)? The compound represented by) is mentioned. More preferably, the compound represented by Formula (I-1), Formula (I-7), Formula (I-9), or Formula (I-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-9) or formula (II-11)? The compound represented by) is mentioned. More preferably, the compound represented by Formula (II-1), Formula (II-7), Formula (II-9), 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 is preferably in the molar ratio of 5:95 to 95: 5, more preferably 10:90 to 90:10, and more preferably 20:80 to the formula (I): formula (II). 80:20.

As a monomer (b2) 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 (b2) 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 (b3) 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 (b3) include tetrahydrofurfuryl acrylate (for example, bis coat V # 150, manufactured by Osaka Organic Chemical Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

As (b), it is preferable that it is (b1) from the point which can make high reliability, such as heat resistance and chemical-resistance, of a color filter obtained. Moreover, (b1-2) is more preferable at the point that the storage stability of a coloring photosensitive resin composition is good.

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 technical field referred to as dicyclopentanyl (meth) acrylate as a conventional name), Dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate , Naphthyl (meth) acrylate, benzyl (meth) Such as a relay agent (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-methyl Bicyclo [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-phenoxy Cycarbonylbicyclo [2.2.1] hepto-2-ene, 5,6-bi Ratios of s (tert-butoxycarbonyl) bicyclo [2.2.1] hepto-2-ene and 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hepto-2-ene Cyclo unsaturated compounds;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinitrile-3-maleimidebenzoate, N-succinitrile-4-maleimidebutyrate, N-succinitrile Dicarbonylimide derivatives, such as -6-maleimide caproate, N-succinimid-3-maleimide propionate, and N- (9-acridinyl) maleimide;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxy styrene, 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 these, styrene, N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, bicyclo [2.2.1] hepto-2-ene, etc. are preferable from the point of copolymerization reactivity and heat resistance.

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

structural units derived from (a); 2-50 mol% (more preferably 10-45 mol%)

structural units derived from (b); 50-98 mol% (more preferably 55-90 mol%)

When the ratio of the structural unit of resin [K1] is in the said range, it exists in the tendency which is excellent in the storage stability of a coloring photosensitive resin composition, developability, and the solvent resistance of the pattern obtained.

Resin [K1] is, for example, the method described in the document "Experimental method of polymer synthesis" (the first edition of March 1, 1972, first edition of Oka Takayuki Co., Ltd.), and the cited document described in the above document. It can be prepared with reference to.

Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, and the method of heating and warming while stirring as a deoxygen atmosphere by replacing oxygen in the atmosphere with nitrogen, for example, Can be mentioned. In addition, the polymerization initiator, solvent, etc. which are used here are not specifically limited, Although it is normally used in the said field | area, any can be used. For example, as a polymerization initiator, an azo compound (2,2'- azobisisobutyronitrile, 2,2'- azobis (2, 4- dimethylvaleronitrile), etc.) and an organic peroxide (benzoyl peroxide etc.) As a solvent, what is necessary is just to melt | dissolve each monomer, and the solvent etc. which are mentioned later as a solvent (E) of the coloring photosensitive resin composition of this invention can be used.

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

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

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

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

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

When the ratio of the structural unit of resin [K2] is in the said range, there exists a tendency which is excellent in the storage stability, developability, and the solvent resistance, heat resistance, and mechanical strength of a coloring photosensitive resin composition.

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

Specifically, the predetermined amount of (a), (b) and (c), a polymerization initiator and a solvent are put into a reaction container, and it heats and keeps warm, stirring, for example as a deoxidation atmosphere by replacing oxygen in air with nitrogen. How to do this. The obtained copolymer may use the solution after reaction as it is, the solution which concentrated or diluted may be used, and what was taken out as solid (powder) by methods, such as reprecipitation, may be used.

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

(a) 2-55 mol%, More preferably, it is 10-50 mol%

(c) 45-98 mol%, More preferably, it is 50-90 mol%

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

Resin [K4] can be manufactured by obtaining the copolymer of (a) and (c), and adding the C2-C4 cyclic ether which (b) has to the carboxyl group and / or carboxylic anhydride which (A) has have.

First, the copolymer of (a) and (c) is manufactured similarly to the method described as a manufacturing method of [K1]. In this case, 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 the copolymer of (a) and (c).

(a) 5-50 mol%, More preferably, it is 10-45 mol%

(c) 50-95 mol%, More preferably, 55-90 mol%

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

Subsequent to the preparation of the copolymers of (a) and (c), the atmosphere in the flask was replaced with nitrogen from air, and 5 to 80 mole% of (b), carboxylic acid or carboxylic anhydride based on the number of moles of (a) 0.001-5 mass% and a polymerization inhibitor (for example, tris (dimethylaminomethyl) phenol, etc.) with respect to the total amount of (a), (b), and (c) Hydroquinone) and the like, in an amount of 0.001 to 5% by mass in a flask based on the total amount of (a), (b) and (c), for example, the resin [K4] by reacting at 60 to 130 ° C for 1 to 10 hours. You can get it. The reaction conditions such as the injection method, the reaction temperature and the time can be appropriately adjusted in consideration of the amount of heat generated by the production equipment, polymerization, and the like. In addition, similarly to the polymerization conditions, the injection 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 this case, as for the usage-amount of (b), 5-80 mol is preferable with respect to 100 mol of (a), More preferably, it is 10-75 mol. By setting it as this range, there exists a tendency for the balance of the storage stability, developability, and the solvent resistance, heat resistance, mechanical strength, and the sensitivity of a colored photosensitive resin composition to become favorable.

(B1) is preferable and (b1-1) is more preferable as (b) used for resin [K4] from the point that reactivity of cyclic ether is high and unreacted (b) is hard to remain | survive.

Resin [K5] is obtained similarly to the manufacturing method of resin [K1] mentioned above as a 1st step, and obtains the copolymer of (b) and (c). The copolymer obtained as mentioned above may use the solution after reaction as it is, the concentrated or diluted solution may be used, and the thing extracted as solid (powder) by methods, such as reprecipitation, may be used.

It is preferable that the ratio of the structural unit derived from (b) 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 (b); 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%)

Moreover, the carboxylic acid or carboxylic anhydride which (a) has is made to react with the cyclic ether derived from (b) which the copolymer of (b) and (c) has on conditions similar to the manufacturing method of resin [K4]. The resin [K5] can be obtained by doing this.

As for the usage-amount of (a) made to react with the said copolymer, 5-80 mol is preferable with respect to 100 mol of (b). (B1) is preferable and (b1-1) is preferable as (b) used for resin [K5] from the point that reactivity of cyclic ether is high and unreacted (b) is hard to remain.

Resin [K6] is resin which made carboxylic anhydride further react with resin [K5]. The carboxylic acid anhydride is reacted with the hydroxy group generated by the reaction of the cyclic ether with the carboxylic acid or the carboxylic anhydride.

As carboxylic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6 -Tetrahydrophthalic anhydride, dimethyl tetrahydrophthalic anhydride, 5, 6- dicarboxybicyclo [2.2.1] hepto-2-ene anhydride (hymic acid anhydride), etc. are mentioned.

Specific examples of the binder resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid Resins such as copolymers [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) resins such as acrylic acid / N- cyclohexyl maleimide copolymer, 3-methyl-3- (meth) acryloyloxyethyl-methyl oxetane / (meth) acrylic acid / styrene copolymer [K2]; Resins such as benzyl (meth) acrylate / (meth) acrylic acid copolymer and styrene / (meth) acrylic acid copolymer; Resin which glycidyl (meth) acrylate was added to the benzyl (meth) acrylate / (meth) acrylic acid copolymer, and glycidyl (meth) to the tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer Resin [K4], such as resin which added the acrylate, resin which added glycidyl (meth) acrylate to the tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer; Of a resin obtained by reacting (meth) acrylic acid to a copolymer of dicyclopentanyl (meth) acrylate / glycidyl (meth) acrylate, and dicyclopentanyl (meth) acrylate / styrene / glycidyl (meth) acrylate Resins [K5], such as resin which made (meth) acrylic acid react with the copolymer; [K6] etc., such as resin which further made tetrahydrophthalic anhydride react with resin which (meth) acrylic acid reacted with the copolymer of dicyclopentanyl (meth) acrylate / glycidyl (meth) acrylate, is mentioned. .

These resin may be used independently or may use 2 or more types together.

Especially, as binder resin (B), resin [K1] and resin [K2] are preferable, resin [K1] is more preferable, 3, 4- epoxy cyclocyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) Acrylic acid copolymers are more preferred.

The weight average molecular weight of polystyrene conversion of binder resin (B) becomes like this. Preferably it is 3,000-100,000, More preferably, it is 5,000-50,000, More preferably, it is 5,000-30,000. When molecular weight exists in the said range, there exists a tendency for the solubility with respect to the developing solution of an unexposed part to be high, and the residual film ratio and hardness of the pattern obtained are also high.

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

The acid value of binder resin (B) becomes like this. Preferably it is 50-180 mg-KOH / g, More preferably, it is 60-170 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 by, for example, titration using an aqueous potassium hydroxide solution.

Content of binder resin (B) becomes like this. Preferably it is 7-65 mass% with respect to solid content of a coloring photosensitive resin composition, More preferably, it is 13-55 mass%, More preferably, it is 17-50 mass%. When content of binder resin (B) exists in the said range, there exists a tendency for the solubility to the developing solution of an unexposed part to be high.

The polymerizable compound (C) is a compound which can be polymerized by active radicals and / or acids generated from the polymerization initiator (D) by the action of light, and examples thereof include a compound having a polymerizable ethylenically unsaturated bond, and the like. Preferably, a (meth) acrylic acid ester compound is mentioned.

Especially, it is preferable that a polymeric compound (C) is a polymeric compound which has 3 or more of ethylenically unsaturated bonds. Examples of such a polymerizable compound include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and tripentaerythritol. Octa (meth) acrylate, 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 ( Meta) acrylate, caprolactone-modified pentaerythritol La (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate. Especially, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable. These polymeric compounds may be used independently or may use 2 or more types together.

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 a coloring photosensitive resin composition, More preferably, it is 13-60 mass%, More preferably, it is 17-55 mass%. When content of the said polymeric compound (C) exists in the said range, since hardening arises sufficiently and the film thickness ratio before and behind image development improves, it becomes difficult to undercut into a pattern, and adhesiveness tends to become favorable, and it is preferable.

The polymerization initiator (D) includes an oxime compound and an alkylphenone compound.

An O-acyl oxime compound is mentioned as an oxime compound, and an O-acyl oxime compound is a compound which has the partial structure represented by Formula (d1). Hereinafter, * represents a coupling | bonding number.

Specifically N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, 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-carbox Bazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3- And cyclopentylpropane-1-one-2-imine. You may use commercially available products, such as Irgacure (trademark) OXE01, OXE02 (above, BASF Corporation), and N-1919 (ADEKA Corporation). Among them, the oxime compound is N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one At least one selected from the group consisting of 2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine is preferable, and N-benzoyloxy -1- (4-phenylsulfanylphenyl) octan-1-one-2-imine is more preferred. If it is these oxime compounds, there exists a tendency for the high brightness color filter to be obtained.

As an alkyl phenone compound, the (alpha)-aminoalkyl phenone compound, the (alpha)-alkoxy alkyl phenone compound, the (alpha)-hydroxyalkyl phenone compound, etc. are mentioned.

α-aminoalkylphenone compound is represented by formula (d2)

It is a compound having a partial structure represented by, specifically 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-mor Polynophenyl) -2-benzylbutan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2- (4-methylphenylmethyl) butan-1-one, and the like. As a commercial item, Irgacure (trademark) 369, 379, 907 (above, BASF Corporation make), etc. are mentioned.

α-alkoxyalkylphenone compound is represented by formula (d3)

R < ^z represents an alkyl group in Formula (d3)], It is a compound which has a partial structure shown, Specifically, diethoxy acetophenone, benzyl dimethyl ketal, etc. are mentioned.

As (alpha)-hydroxyalkyl phenone compound, it is a formula (d4)

It is a compound having a partial structure represented by, specifically 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxy Oligomers of ethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, etc. Can be mentioned.

As the alkylphenone compound, an α-aminoalkylphenone compound is preferable, and 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4- Morpholinophenyl) -2-benzylbutan-1-one is more preferable.

Although the polymerization initiator (D) may contain the polymerization initiator of that excepting the above, it is preferable not to contain substantially from the point of a sensitivity. As a polymerization initiator of that excepting the above, if it is a compound which can start superposition | polymerization of a polymeric compound (C), a well-known polymerization initiator can be used without a limitation. As a polymerization initiator of that excepting the above, a triazine compound, an acyl phosphine oxide compound, a biimidazole compound, etc. are mentioned, for example.

As the triazine compound, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4- Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl ) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) 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, etc. are mentioned.

2,4,6-trimethyl benzoyl diphenyl phosphine oxide etc. are mentioned as an acyl phosphine oxide compound. You may use a commercial item, such as Irgacure (trademark) 819 (made by BASF Corporation).

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, for example, Japanese Patent Application 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'-tetra (alkoxyphenyl) ratio Imidazole, 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, for example, Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 62-174204, etc.), 4,4' The imidazole compound (for example, Unexamined-Japanese-Patent No. 7-10913 etc.) in which the phenyl group of a 5,5'-position 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.

Moreover, as a polymerization initiator (D), Benzoin compounds, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, 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 start adjuvant (D1) (especially amines) mentioned later.

Content of an oxime compound in a polymerization initiator (D) becomes like this. Preferably it is 20-98 mass%, More preferably, it is 40-95 mass%, More preferably, it is 60-95 mass%.

Moreover, content of an alkyl phenone compound in a polymerization initiator (D) becomes like this. Preferably it is 2-80 mass%, More preferably, it is 5-60 mass%, More preferably, it is 5-40 mass%.

The mass ratio (oxime compound: alkylphenone compound) of the oxime compound and the alkylphenone compound in the polymerization initiator (D) is preferably 30:70 to 95: 5, more preferably 40:60 to 90:10, still more preferably 50: 50? 85: 15.

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 binder resin (B) and a polymeric compound (C), More preferably, it is 1-20 mass parts. When content of a polymerization initiator (D) exists in the said range, a pattern can be formed with high sensitivity, and there exists a tendency for the color filter which is further high brightness to be obtained.

A polymerization start adjuvant (D1) is a compound or a sensitizer used in order to accelerate superposition | polymerization of the polymeric compound in which superposition | polymerization was started with a polymerization initiator. When including a polymerization start adjuvant (D1), it is normally used in combination with a polymerization initiator (D).

As polymerization start adjuvant (D1), an amine compound, an alkoxy anthracene compound, a thioxanthone compound, a carboxylic acid compound, etc. are mentioned, Preferably it is a thioxanthone compound.

As the thioxanthone compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro-4-propoxythioke Santon etc. can be mentioned.

As the amine compound, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid isoamyl, benzoic acid 2-dimethylaminoethyl, 4-dimethylaminobenzoic acid 2 -Ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (collectively Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4,4'- Bis (ethylmethylamino) benzophenone etc. are mentioned, Especially, 4,4'-bis (diethylamino) benzophenone is preferable. You may use commercial items, such as EAB-F (made by Hodogaya Kagaku Kogyo KK).

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 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 Sulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N-phenylglycine, phenoxy acetic acid, naphthylthioacetic acid, N-naphthyl glycine, naphthoxy acetic acid, and the like.

These polymerization start adjuvant may be used independently or may use 2 or more types together.

Moreover, when using a polymerization start adjuvant (D1), the usage-amount becomes like this. Preferably it is 0.1-30 mass parts with respect to 100 mass parts of total amounts of binder resin (B) and a polymeric compound (C), More preferably, it is 1-20 mass It is wealth. Moreover, Preferably it is 20-100 mass parts, More preferably, it is 30-80 mass parts with respect to 100 mass parts of content of a polymerization initiator (D). If the amount of the polymerization initiation assistant (D1) is within this range, the pattern can be formed with high sensitivity, and there is a tendency for a color filter with higher brightness to be obtained.

Solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. For example, an ester solvent (a solvent containing -COO- in a molecule and not containing -O-), an ether solvent (a solvent containing -O- in a molecule and not containing -COO-) and an ether ester Solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule and no -COO-), alcoholic solvents (containing OH in the molecule,- Solvents not containing O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide and the like.

As ester solvent, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxy isobutane, 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, γ-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 methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisol, phentol, methyl anisol, 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 To ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl And the like Le 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, cyclopenta Paddy fields, cyclohexanone, isophorone, etc. are mentioned.

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.

These solvents may be used independently or may use 2 or more types together.

The organic solvent whose boiling point in 1 atm is 120 degreeC or more and 180 degrees C or less from the point of applicability | paintability and dryness in the said solvent is preferable. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxypropionate ethyl, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl Acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide, and the like are preferable, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, Dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 3-ethoxypropionate, and the like are more preferable.

Content of the solvent (E) in a coloring photosensitive resin composition 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 a coloring photosensitive resin composition 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 of a coloring photosensitive resin composition becomes favorable, and since a color concentration does not run short when a color filter is formed, there exists a tendency for display characteristics to become favorable.

As surfactant (F), 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, Toray silicon DC3PA, copper SH7PA, copper DC11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30 ', copper SH8400 (brand name: Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326 , KP340, KP341 (manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (manufactured by Momentive Performance Materials Japan Japan) Can be mentioned.

As said fluorine-type surfactant, surfactant etc. which have a fluorocarbon chain | strand are mentioned. Specifically, fluoride (trademark) FC430, copper FC431 (manufactured by Sumitomo Industries Co., Ltd.), mega pack (registered trademark) F142D, copper F171, copper F172, copper F173, copper F177, copper F183, copper R30, copper RS-718-K (product made by DIC Corporation), F-top (registered trademark) EF301, copper EF303, copper EF351, copper EF352 (made by Mitsubishi Material Denshi Kasei Co., Ltd.), Supron (registered trademark) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemicals Co., Ltd.), and the like.

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 R08, BL20, F475, F477, F443 (manufactured by DIC Corporation), and the like can be given.

These surfactant may be used independently or may use 2 or more types together.

Content of surfactant (F) becomes like this. Preferably it is 0.001 mass% or more and 0.2 mass% or less with respect to a coloring photosensitive resin composition, Preferably it is 0.002 mass% or more and 0.1 mass% or less, More preferably, 0.01 mass% or more and 0.05 mass% It is as follows. In addition, content of the said pigment dispersant is not contained in this content. If content of surfactant (F) exists in the said range, flatness of a color filter can be made favorable.

The colored photosensitive resin composition of this invention may also contain various additives well-known in the said technical field, such as a filler, another high molecular compound, an adhesion promoter, antioxidant, a ultraviolet absorber, a light stabilizer, a chain transfer agent, as needed.

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

In the case of including the pigment (A2), it is preferable to mix the pigment (A2) with some or all of the solvent (E) in advance, and disperse it using a bead mill or the like until the average particle diameter of the pigment is about 0.2 µm or less. Do. At this time, you may mix | blend a part or all of the said pigment dispersant and resin (B) as needed. The remainder of the dye (A1), the resin (B), the polymerizable compound (C) and the polymerization initiator (D), and the polymerization start aid (D1) and the solvent (E) used in the obtained pigment dispersion, and the surfactant. The desired colored photosensitive resin composition can be prepared by mixing (F) and other components to a predetermined concentration.

It is preferable to dissolve the dye (A1) in part or all of the solvent (E) in advance to prepare a solution. Moreover, 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 colored photosensitive resin composition mixed and prepared as mentioned above with the filter of about 0.01-10 micrometers of pore diameters.

As a method of forming the pattern of a color filter using the coloring photosensitive resin composition of this invention, the photolithographic method, the inkjet method, etc. are mentioned, for example. In order to form a pattern by the photolithography method, it is apply | coated on a board | substrate or another resin layer (for example, the other coloring photosensitive resin composition layer formed on a board | substrate etc.), and removes (dry) a volatile component, such as a solvent, and forms a colored layer. What is necessary is just to form and to expose and develop the said colored layer through a photomask. In the photolithography method, a coating film having no pattern can be formed by not using a photomask and / or not developing at the time of exposure.

The film thickness of the pattern to produce is not specifically limited, It can adjust suitably according to the material used, a use, etc., for example, 0.1-30 micrometers, Preferably it is 1-20 micrometers, More preferably, it is 1-6 micrometers.

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 and polyethylene terephthalate, silicon, and aluminum on the substrate. , Silver / copper / palladium alloy thin film or the like is used. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates.

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

As a method of forming each color pixel by the photolithographic method, a well-known or a conventional method can be used. For example, it can produce as follows.

A colored photosensitive resin composition is apply | coated on a board | substrate, and volatile components, such as a solvent, are removed by heat-drying (prebaking) and / or drying under reduced pressure, and a smooth colored layer is obtained.

30-120 degreeC is preferable and, as for the temperature at the time of heat-drying, 50-110 degreeC is more preferable. Moreover, as heating time, it is preferable for 10 seconds-60 minutes, and it is more preferable for 30 seconds-30 minutes.

When drying under reduced pressure, it is preferable to carry out in the temperature range of 20-25 degreeC under the pressure of 50-150 Pa.

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

After drying, the coating film is exposed through a photomask for forming a desired pattern. The pattern shape on the photomask at this time is not specifically limited, The pattern shape 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 of less than 350 nm may be cut using a filter that cuts this wavelength range, or light of around 436 nm, 408 nm, or 365 nm wavelengths may be selectively selected using a bandpass filter that extracts their wavelength range. May be withdrawn. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp etc. are mentioned.

It is preferable to use apparatuses, such as a mask aligner and a stepper, in order to irradiate a parallel light beam uniformly to the whole exposure surface or to perform the exact alignment of a mask and the said colored layer.

A pattern can be obtained by making a predetermined part, for example, an unexposed part, melt | dissolve and develop by making it contact with a developing solution after exposure. 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 these alkaline compounds becomes like this. Preferably it is 0.01-10 mass%, More preferably, it is 0.03-5 mass%. In addition, the developing solution may contain surfactant.

The developing method may be any of a paddle method, an immersion method, and a spray method. In addition, you may incline a board | substrate at arbitrary angles at the time of image development.

It is preferable to wash with water after image development.

In addition, you may post-bake as needed. 150-250 degreeC is preferable and 160-235 degreeC of postbaking temperature is more preferable. The postbaking time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

According to the coloring photosensitive resin composition of this invention, a color filter can be manufactured especially with high sensitivity. 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, etc.) and a solid-state image sensor.

Example

Next, an Example is given and this invention is demonstrated further more concretely. "%" And "part" in an example are the 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 mixture of the compound represented by formula (A0-1) and a compound represented by formula (A0-2) (made by Chugai Kasei), 150 parts of chloroform and N, N -8.9 parts of dimethylformamides were added, and 10.9 parts of thionyl chlorides were added dropwise, keeping 20 degrees C or less under stirring. It heated up at 50 degreeC after completion | finish of dripping, it hold | maintained for 5 hours and made it react at the same temperature, and it cooled at 20 degreeC after that. A mixture of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise while maintaining the reaction solution after cooling at 20 ° C. or less under stirring. Then, it stirred and reacted for 5 hours at the same temperature. Subsequently, the solvent was distilled off from the obtained reaction mixture with a rotary evaporator, and 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. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, and dried under reduced pressure at 60 ° C. to give 11.3 parts of dye A1 (dye A1) (a mixture of compounds represented by formulas (A1-1) to (A1-8)). Got it.

[Synthesis Example 2]

20 parts of compounds represented by formula (1a) and 200 parts of N-ethyl-o-toluidine (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed under light shielding conditions, and the resulting solution was stirred at 110 ° C for 6 hours. After cooling the obtained reaction liquid to room temperature, it added to the liquid mixture of 800 parts of water and 50 parts of 35% hydrochloric acid, and stirred at room temperature for 1 hour, and the crystal | crystallization precipitated. The precipitated crystals were obtained as a residue of suction filtration and dried to obtain 24 parts of the compound represented by the formula (1-30). Yield 80%.

Identification of the compound represented by formula (1-30)

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

                       Exact Mass: 602.2

[Synthesis Example 3]

A compound represented by the formula (1-34) was obtained in the same manner as in Synthesis Example 2 except that N-ethyl-o-toluidine was changed to N-ethyl-2,6-dimethylaniline.

Identification of the compound represented by formula (1-34)

(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 630.3

                       Exact Mass: 630.3

[Synthesis Example 4]

A compound represented by the formula (1-35) was obtained in the same manner as in Synthesis example 2 except that N-ethyl-o-toluidine was changed to N-isopropyl-o-toluidine.

Identification of the compound represented by formula (1-35)

(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 630.3

                       Exact Mass: 630.3

Synthesis Example 5

A compound represented by the formula (1-38) was obtained in the same manner as in Synthesis example 2 except that N-ethyl-o-toluidine was changed to N-propyl-2,6-dimethylaniline.

Identification of the compound represented by formula (1-38)

(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 659.4

                       Exact Mass: 658.9

[Synthesis Example 6]

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

On the other hand, the solution which melt | dissolved 30 mass parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 225 mass parts of ethyl lactate was dripped in the flask over 4 hours using the other dropping funnel. After dripping of the solution of a polymerization initiator is complete | finished, it hold | maintains at 70 degreeC, and after that, it cools to room temperature, the weight average molecular weight Mw is 9.1 * 10 <^3> , molecular weight distribution is 2.1, 26 mass% of solid content, and solid content acid value 120 mg-. A resin B1 solution of KOH / g was obtained. Resin B1 has a structural unit shown below.

[Synthesis Example 7]

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to a nitrogen atmosphere, and 220 parts of ethyl lactate was added thereto and heated to 70 ° C while stirring. Subsequently, 84 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (compound represented by formula (I-1) and compound represented by formula (II-1) are molar ratios 50 336 parts were melt | dissolved in 140 parts of ethyl lactates, the solution was prepared, and this solution was dripped at the flask kept at 70 degreeC over 4 hours using the dropping funnel. On the other hand, the solution which melt | dissolved 30 parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 95 parts of ethyl lactate was dripped in the flask over 4 hours using the other dropping funnel. After dripping of the solution of a polymerization initiator is complete | finished, it hold | maintains at 70 degreeC for 4 hours, and it cools to room temperature after that, The weight average molecular weight Mw is 8.0x10 <^3> , molecular weight distribution is 2.5, solid content is 48%, and solution acid value is 50 mg. A resin B2 solution of -KOH / g was obtained. When the solid acid value is calculated from the solid content and the acid value of the solution, it is 104 mg-KOH / g. Resin B2 has a structural unit shown below.

[Synthesis Example 8]

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to make a nitrogen atmosphere, and 305 parts by mass of ethyl lactate was added thereto and heated to 100 ° C while stirring. Subsequently, it melt | dissolves in 90 mass parts of methacrylic acid, 210 mass parts of benzyl methacrylates, and 140 mass parts of ethyl lactate, and prepares a solution, and the said liquid solution is dripped in the flask kept warm at 100 degreeC over 4 hours using the dropping funnel. did. On the other hand, the solution which melt | dissolved 30 mass parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 225 mass parts of ethyl lactate was dripped in the flask over 4 hours using the other dropping funnel. After the dropping of the polymerization initiator solution is completed for 4 hours, held at 100 ℃, and cooled to room temperature and then the weight average molecular weight Mw of 1.2 × 10 ^4, a molecular weight distribution of 2.2, a solid content of 30% by weight and a solid content acid value 154㎎- A resin B3 solution of KOH / g was obtained. Resin B3 has a structural unit shown below.

Synthesis Example 9

133 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube, and the atmosphere in the flask was changed from air to nitrogen. It heated up at 100 degreeC, 82.0 g (0.47 mol) of benzyl methacrylate, 37.0 g (0.43 mol) of methacrylic acid, monomethacrylate (FA-513M by Hitachikasei Co., Ltd.) of tricyclodecane skeleton (22.0 g) 0.10 mol) and the solution which added 3.6 g of 2,2'- azobisisobutylonitrile to the mixture which consists of 164g of propylene glycol monomethyl ether acetates were dripped, and it stirred further at 100 degreeC. Subsequently, the atmosphere in the flask was changed from nitrogen to air, 21.5 g [0.15 mol of glycidyl methacrylate ((50 mol% of the carboxyl groups of methacrylic acid used in this reaction)]], 0.9 g of trisdimethylaminomethylphenol, and 0.145 g of hydroquinone was charged into a flask, and the reaction was continued at 110 ° C to obtain a resin B4 solution (solid content: 38%) having a solid acid value of 97 mgKOH / g. Resin B4 has a structural unit shown below.

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

Device; K2479 (shimashima seisakusho festival)

column; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ℃

menstruum; THF (tetrahydrofuran)

Flow rate; 1.0 mL / min

Detectors; RI

Calibration standard material; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by 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 1-8 and Comparative Example 1

Each component was mixed so that it might become the composition shown in Table 1, and the coloring photosensitive resin composition was obtained.

In addition, each component in Table 1 shows the following. In addition, binder resin (B) showed the mass part of solid content conversion.

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

Colorant (A); (A-2); Dye A1

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

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

Binder resin (B); (B-3); Resin B3

Binder resin (B); (B-4); Resin B4

Polymerizable compound (C); (C-1); Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nihon Kayaku Co., Ltd.)

Polymerization initiator (D); (D-1); N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (irgacure® OXE 01; manufactured by BASF; oxime compound)

Polymerization initiator (D); (D-2); 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one (irgacure®907; manufactured by BASF; alkylphenone compound)

Polymerization initiator (D); (D-3); 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one (irgacure® 369; manufactured by BASF; alkylphenone compound)

Polymerization initiation aid (D1); (D1-1); 2,4-diethyl thioxanthone (KAYACURE® DETX-S; Nihon Kayaku Co., Ltd .; thioxanthone compound)

Solvent (E); (E-1); Propylene Glycol Monomethyl Ether Acetate

Solvent (E); (E-2); Propylene Glycol Monomethyl Ether

Solvent (E); (E-3); Ethyl lactate

Surfactant (F); (F-1); Polyether modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)

Example 9

Colorant (A); C. I. Pigment blue 15: 6 (pigment) 16 copies,

6.2 parts of an acrylic pigment dispersant,

Solvent (E); 85 parts of propylene glycol monomethyl ether acetate and

Solvent (E); 25 parts ethyl lactate

A pigment dispersion liquid in which the pigments are sufficiently mixed with the

Colorant (A); 4.5 parts of the compound represented by the formula (1-30),

Binder resin (B); 40 parts of Resin B1,

Polymerizable compound (C): 60 parts of dipentaerythritol hexaacrylate (KAYARAD® DPHA; manufactured by Nihon Kayaku Co., Ltd.),

Polymerization initiator (D): 11 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (trademark) OXE01; made by BASF Corporation),

Polymerization initiator (D); (D-2); 5.4 parts of 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one (irgacure (registered trademark) 907; manufactured by BASF Corporation),

Polymerization initiation aid (D1); 9 parts of 2,4-diethyl thioxanthone (KAYACURE (registered trademark) DETX-S; product of Nippon Kayaku Co., Ltd.),

Surfactant: 0.15 part of polyether modified silicone oil (Toray Silicone SH8400; Toray Dow Corning Co., Ltd. product),

Solvent (E): 15 parts of propylene glycol monomethyl ether acetates, and

Solvent (E); 571 parts of ethyl lactate

It mixed and obtained the coloring photosensitive resin composition.

Example 10

A colored photosensitive resin composition was obtained in the same manner as in Example 9 except that the compound represented by the formula (1-30) was changed to the compound represented by the formula (1-34).

Example 11

A colored photosensitive resin composition was obtained in the same manner as in Example 9 except that the compound represented by the formula (1-30) was changed to the compound represented by the formula (1-35).

Example 12

A colored photosensitive resin composition was obtained in the same manner as in Example 9 except that the compound represented by the formula (1-30) was changed to the compound represented by the formula (1-38).

<Production of pattern>

After apply | coating the coloring photosensitive resin composition on the glass substrate (Eagle 2000; Corning Corporation make) of 5 cm x 5 cm by the spin coating method, it prebaked at 100 degreeC for 3 minutes. After cooling, the distance between the substrate coated with the colored photosensitive resin composition and the quartz glass photomask was set to 80 µm, and the exposure dose (365 nm standard) was 60 mJ / cm 2 under an atmospheric atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation). Irradiated with light. As a photomask, the thing in which the 50 micrometer line and space pattern was formed was used. After light irradiation, the coating film was immersed in a developer (aqueous solution containing 0.05% potassium hydroxide and 0.2% sodium butylnaphthalenesulfonate in mass fraction, respectively) at 25 ° C. for 60 seconds, and post-baked at 230 ° C. for 30 minutes in an oven after washing with water. Was performed to obtain a pattern.

<Measurement of film thickness>

About the obtained pattern, the film thickness was measured using the film thickness measuring apparatus (DEKTAK3; the Nippon Shinku Gijutsu Co., Ltd. product). The results are shown in Tables 2 and 3.

<Color evaluation>

Spectroscopy was measured on the obtained pattern using a colorimeter (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the xy chromaticity coordinates (x, y) in the XYZ color system of the CIE using the characteristic function of the C light source. Tristimulus value Y was measured. The larger the value of Y, the higher the brightness. The results are shown in Tables 2 and 3.

<Pattern Shape Evaluation>

The shape was observed about the obtained pattern using the scanning electron microscope (S-4000; the Hitachi High Technologies Co., Ltd.). If it was a shape shown by following (p1) (so-called forward taper shape), it was set as (circle), and if it was a shape shown by (p2), it was set as (triangle | delta) and if it was a shape shown by (p3), it was set as x. If it is a shape shown by (p1), when an inorganic film is laminated | stacked on a pattern, there exists a tendency which a crack and peeling do not occur easily. The results are shown in Tables 2 and 3.

<Sensitivity evaluation>

About the obtained pattern, the line | wire width was measured using the scanning electron microscope (S-4000; the Hitachi High-Technologies Corporation). The thicker the line width, the higher the sensitivity.

It was confirmed from the said result that the coloring photosensitive resin composition of this invention can be pattern-formed with high sensitivity. From this point, according to the coloring photosensitive resin composition of this invention, it turns out that it is possible to manufacture a color filter with high productivity.

Since the coloring photosensitive resin composition of this invention has high sensitivity, a pattern can be formed with a small exposure amount.

Claims (6)

Containing a colorant, a binder resin, a polymerizable compound and a polymerization initiator,
The colorant is a colorant including a dye,
The said polymerization initiator is a polymerization initiator containing an oxime compound and an alkylphenone compound, The coloring photosensitive resin composition characterized by the above-mentioned. The method of claim 1,
It further contains a thioxanthone compound, The coloring photosensitive resin composition characterized by the above-mentioned. The method of claim 1,
Content of the said oxime compound is 20 mass% or more and 98 mass% or less with respect to content of the said polymerization initiator, The coloring photosensitive resin composition characterized by the above-mentioned. The method of claim 1,
The coloring agent is a coloring photosensitive resin composition, characterized in that the coloring agent containing a pigment and a dye. The color filter formed by the coloring photosensitive resin composition of any one of Claims 1-4. A display device comprising the color filter according to claim 5.