KR20130054156A - Colored curable resin composition - Google Patents

Abstract

PURPOSE: A colored curable resin composition is provided to form a composition layer with narrow bead width. CONSTITUTION: A colored curable resin composition comprises a coloring agent, resin, polymerizable compound, photopolymerization initiator, fluoro surfactant, and solvent. The coloring agent comprises dye. The solvent comprises the ethyl lactate. The amount of the fluoro surfactant is 0.01-0.1 wt% based on total weight of the colored curable resin composition. The amount of the solvent is 70-95 wt% based on total weight of the colored curable resin composition. The coloring agent additionally includes pigment.

Description

Colored curable resin composition {COLORED CURABLE RESIN COMPOSITION}

The present invention relates to a colored curable resin composition.

Colored curable 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 such colored curable resin composition, the colored curable resin composition containing 4-hydroxy-4-methyl- 2-pentanone and propylene glycol monomethyl ether acetate as a fluorine-type surfactant and a solvent is known (JP2010-244027-A) . Moreover, the colored curable resin composition containing propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and ethyl lactate as a solvent is known (JP2010-211198-A).

When the colored curable resin composition is applied by a method of rotating and applying the substrate, such as the spin coating method and the slit and spin method, a composition layer having a desired film thickness is formed at the center of the substrate, but the outer peripheral edge of the substrate has a film thickness. Thick portions, so-called beads, may be formed. The beads are peeled off in the form of small scales during the heat treatment or conveyance of the substrate in the next step, which causes dust in the apparatus or adheres to the surface of the color filter formed on the substrate. For this reason, the EBR (edge bead rinse) process which melt | dissolves and removes the beads in the organic solvent is performed. When the width | variety of the beads in the formed composition layer was large, there existed a problem that the large area of the composition layer formed in the board | substrate had to be removed by EBR process, and the effective area of a board | substrate became narrow.

The said colored curable resin composition conventionally known may not always be able to fully narrow the bead width of the composition layer formed from this colored curable resin composition.

The present invention includes the following inventions.

[1] a colorant, a resin, a polymerizable compound, a polymerization initiator, a fluorine-based surfactant and a solvent,

Colorants include dyes,

The solvent contains ethyl lactate,

Colored curable resin composition whose content of a fluorine-type surfactant is 0.01 mass% or more and 0.1 mass% or less with respect to the total amount of colored curable resin composition.

[2] The colored curable resin composition according to [1], wherein the content of the solvent is 70% by mass or more and 95% by mass or less with respect to the total amount of the colored curable resin composition.

[3] The colored curable resin composition according to [1] or [2], wherein the colorant further contains a pigment.

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

[5] A display device comprising the color filter according to [4].

According to the colored curable resin composition of this invention, a composition layer with a narrow bead width can be formed.

The colored curable resin composition of this invention contains a coloring agent (A), resin (B), a polymeric compound (C), a polymerization initiator (D), a fluorine-type surfactant (F), and a solvent (E).

Colorant (A) comprises dye (A1).

The solvent (E) contains ethyl lactate.

The colored curable resin composition of this invention may also contain a polymerization start adjuvant (D1) as needed.

In this specification, the compound illustrated by each component can be used individually or in combination of multiple types unless there is particular rejection.

<Coloring agent (A)>

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

The dye (A1) is not particularly limited, and known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of the dyes include compounds classified as dyes in the Color Index (Published by The Society of Dyers and Colourists), and known dyes described in dyeing notes (Shiksensha). In addition, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes , Styryl dyes, coumarin dyes, quinoline dyes and nitro dyes. Of these, organic solvent-soluble dyes are preferred.

Specifically, C.I. Solvent Yellow 4 (hereinafter, the description of CI Solvent Yellow is omitted and described only by number), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 117, 162, 163 , 167, 189;

C.I. Solvent Red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247;

C.I. Solvent Orange 2, 7, 11, 15, 26, 56, 77, 86;

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, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;

C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, Solvent dyes,

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, 112, 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, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 266, 268, 270, 274, 277, 280, 281, 272, 277, 278, 279, 252, 257, 258, 260, 261, 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. C.I. such as acid green 1, 3, 5, 9, 16, 25, 27, 28, 41, 50, 58, 63, 65, 80, 104, 105, 106, 109 and the like. Acid dyes,

C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 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, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

C.I. Direct Orange 26, 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 Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, Direct dyes,

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

C.I. Disperse Violet 26, 27;

C.I. Disperse Blue 1, 14, 56, 60, etc. C.I. Disperse dyes,

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. C.I. of Basic Green 1 et al. Basic dyes,

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

C.I. Reactive Orange 16;

C.I. C.I. of Reactive Red 36 et al. Reactive dyes,

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, 27, 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. 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 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53, etc. Modern dyes,

C.I. C.I. Bat dye etc. are mentioned.

What is necessary is just to select these dyes suitably according to the spectral spectrum of a desired color filter.

As the dye (A1), xanthene dye (Aa) is preferable.

Xanthene dye (Aa) is a dye containing the compound which has a xanthene frame | skeleton in a molecule | numerator. Xanthene dyes (Aa) are for example C.I. Acid Red 51 (hereafter, the description of C.I. Acid Red is omitted and described by numbers only. Others are the same), 52, 87, 91, 92, 94, 95, 98, 289, 388, and 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. The reactive red 36 (rose bengal B), sulforhodamine G, the xanthene dye of JP2010-32999-A, the xanthene dye of JP4492760-B publication, etc. are mentioned. It is preferable to melt | dissolve in the organic solvent.

Among these, as xanthene dye (Aa), the dye containing the compound represented by General formula (1a) (Hereinafter, it may be called "compound (1a)") is preferable. When using compound (1a), 50 mass% or more of content of compound (1a) in xanthene dye (Aa) is preferable, More preferably, it is 70 mass% or more, More preferably, it is 90 mass% or more. In particular, it is preferable to use only compound (1a) as xanthene dye (Aa).

[In formula (1a), R ¹ ~R ⁴ are each independently a hydrogen atom, -R ⁸ or a substituent monovalent aromatic hydrocarbon group of 6 to 10 carbon atoms good. R ¹ and R ² may form a ring containing a nitrogen atom together with a nitrogen atom, and R ³ and R ⁴ may form a ring containing a nitrogen atom together with the nitrogen atom.

R ⁵ is _{^{-OH, -SO 3 -, -SO 3}} H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ NR ⁹ R ¹⁰ is shown.

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

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

a represents the integer of 0 or 1.

X represents a halogen atom.

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

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

R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and R ⁹ and R ¹⁰ are bonded to each other to form a 3 to 10 membered nitrogen containing compound together with a nitrogen atom. A summon may be formed.

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

Examples of the C6-C10 monovalent aromatic hydrocarbon group representing R ¹ to R ⁴ include a phenyl group, toluyl group, xylyl group, mesityl group, propylphenyl group and butylphenyl group.

Group is a monovalent aromatic hydrocarbon having a carbon number of 6 to 10 that represents the R ¹ ~R ^4, hydrogen atoms are halogen atoms included since this is an aromatic ^{hydrocarbon, -R 8, -OH, -OR 8} , -SO 3 -, -SO 3 H, Or may be substituted with -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ R ⁸ , -SR ⁸ , -SO ₂ R ⁸ , -SO ₃ R ^8, or -SO ₂ NR ⁹ R ¹⁰ . Among these substituent _{^{groups, -SO 3 -, -SO 3 H}} , -SO 3 - Z + and -SO ₂ NR ⁹ R at least one member selected from the group consisting of ¹⁰ is preferred, and -SO ₃ ^- Z ⁺ and -SO One or more types selected from the group consisting of ₂ NR ⁹ R ¹⁰ are more preferable. In the case of -SO ₃ ^- Z ⁺ roneun -SO ₃ ^- is N ⁺ (R ¹¹⁾ ₄ are preferred. If R <^1> -R <^4> is these groups, the colored curable resin composition containing a compound (1a) can form the color filter with little generation | occurrence | production of a foreign material and excellent in heat resistance.

R ¹ and R ² may form a ring containing a nitrogen atom together with a nitrogen atom, and R ³ and R ⁴ may form a ring containing a nitrogen atom together with the nitrogen atom. As a ring containing this nitrogen atom, the following are mentioned, for example.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms for R ⁸ to R ¹¹ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group and hexa Linear alkyl groups such as decyl group and isocyl group; Branched chain alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group and 2-ethylhexyl group; C3-C20 alicyclic saturated hydrocarbon groups, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecyl group, are mentioned.

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

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

Examples of —SR ⁸ include methylsulfanyl group, ethylsulfanyl group, butylsulfanyl group, hexylsulfanyl group, decylsulfanyl group and isocylsulfanyl group.

Examples of —SO ₂ R ⁸ include methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, hexylsulfonyl group, decylsulfonyl group and isocylsulfonyl group.

Examples of —SO ₃ R ⁸ include a methoxysulfonyl group, ethoxysulfonyl group, propoxysulfonyl group, tert-butoxysulfonyl group, hexyloxysulfonyl group, and isocyloxysulfonyl group.

-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.

Also, -CH ₂ R ^9, and which includes carbon atoms, a monovalent saturated hydrocarbon group of 1 to 20 represent the R ^10, hydrogen atoms may be substituted by -OH or halogen atoms included in the groups, saturated hydrocarbon, the saturated hydrocarbon groups - 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 nitrogen-containing heterocycle together with a nitrogen atom. As this heterocycle, the following are mentioned, for example.

As a C1-C6 alkyl group which shows R <^6> and R <^7> , a C1-C6 thing is mentioned among the linear alkyl group and branched alkyl group mentioned above.

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

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

As said ⁺ N (R <^11> ) ₄ , it is preferable that two or more of four R <^11> is a C5-C20 monovalent saturated hydrocarbon group. Moreover, 20-80 are preferable and, as for the total carbon number of four R <^11> , 20-60 are more preferable. When ⁺ N (R ¹¹ ) ₄ is present in the compound (1a), if R ¹¹ is these groups, the colored curable resin composition containing the compound (1a) can form a color filter with few foreign substances.

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

As xanthene dye (Aa), the dye containing the compound represented by General formula (2a) (Hereinafter, it may be called "compound (2a)") is more preferable. When using compound (2a), 50 mass% or more of content of compound (2a) in xanthene dye (Aa) is preferable, More preferably, it is 70 mass% or more, More preferably, it is 90 mass% or more.

[In the formula (2a), R ²¹ ~R ²⁴ are each independently a hydrogen atom, or a substituent -R ²⁶ represents a monovalent aromatic hydrocarbon group of 6 to 10 carbon atoms good.

R ²¹ and R ²² may form a ring containing a nitrogen atom together with the nitrogen atom, and R ²³ and R ²⁴ may form a ring containing a nitrogen atom together with the nitrogen atom.

R ²⁵ represents —SO ₃ ^— , —SO ₃ H, —SO ₃ ^— Z 1 ^+, or —SO ₂ NHR ²⁶ .

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

a1 represents the integer of 0 or 1.

X1 represents a halogen atom.

R <^26> represents a C1-C20 monovalent saturated hydrocarbon group.

Z1 ⁺ represents ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ .

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 which shows R <^21> -R <^24> , the group similar to what was mentioned as an aromatic hydrocarbon group in said R <^1> -R <^4> is mentioned. Hydrogen atoms contained groups are aromatic hydrocarbon is -SO ₃ ^- may be substituted with Z1 ^+, -SO ₃ R ²⁶ or _{^{-SO 2 NHR 26 -, -SO 3}} H, -SO 3.

R ²¹ ~R ²⁴ of the combination is preferably R ²¹ and R ²³ is a hydrogen atom, R ²² and R ²⁴ is a hydrogen atom is contained as a first phase-valent aromatic hydrocarbon group of a carbon number of 6 to 10, the aromatic hydrocarbon groups -SO _{^{3 -, -SO 3 H, -SO}} 3 - as Z1 ^+, -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ is preferably substituted. A more preferable combination is that R ²¹ and R ²³ are hydrogen atoms, R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon group are -SO ₃ ^- Z 1 ⁺ or- It is substituted with SO ₂ NHR ²⁶ .

In addition, it is preferable that R ²¹ and R ²² form an aliphatic heterocycle including a nitrogen atom together with the nitrogen atom, and R ²³ and R ²⁴ together with the nitrogen atom form an aliphatic heterocycle including a nitrogen atom.

If R <^21> -R <^24> is these groups, the colored curable resin composition containing a compound (2a) can form the color filter excellent in heat resistance.

As said aliphatic heterocycle, the following are mentioned, for example.

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

It is preferable that -R <^26> when R <^21> -R <^24> is -R <^26> is respectively independently a methyl group or an ethyl group. Further, as R ²⁶ in -SO ₃ R ^26, and -SO ₂ NHR ²⁶ is preferably a branched alkyl group of 3 to 20 carbon atoms preferably, and a branched alkyl group having a carbon number of 6 to 12 and more preferably, a 2-ethylhexyl group More preferred. If R <^26> is these groups, the colored curable resin composition containing a compound (2a) can form the color filter with few generation | occurrence | production of a foreign material.

Z1 ⁺ is ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ²⁷ ) ₄ .

To the ⁺ N (R ²⁷⁾ ₄ roneun four R ²⁷ 2 or more is a monovalent saturated hydrocarbon group having a carbon number of 5 to 20 is preferred. Moreover, 20-80 are preferable and, as for the sum total carbon number of four R <^27> , 20-60 are more preferable. When ⁺ N (R ²⁷ ) ₄ is present in the compound (2a), the colored curable resin composition in which R ²⁷ contains the compound (2a) in these groups can form a color filter with less generation of foreign matter.

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

As compound (2a), the compound represented, for example by General formula (1-1)-General formula (1-25) is mentioned. In the formula, R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched alkyl group having 6 to 12 carbon atoms, more preferably 2-ethylhexyl group. Among these, sulfonamides of CI acid red 289, quaternary ammonium salts of CI acid red 289, sulfonamides of CI acid violet 102 or quaternary ammonium salts of CI acid violet 102 are preferable. As such a compound, the compound etc. which are represented by General formula (1-1)-General formula (1-8), General formula (1-11), or General formula (1-12), etc. are mentioned, for example.

Moreover, as xanthene dye (Aa), the dye containing the compound represented by General formula (3a) (Hereinafter, it may be called "compound (3a)") is more preferable. When using compound (3a), 50 mass% or more of content of compound (3a) in xanthene dye (Aa) is preferable, More preferably, it is 70 mass% or more, More preferably, it is 90 mass% or more.

In Formula (3a), R ³¹ and R ³² independently represent an alkyl group having 1 to 4 carbon atoms.

R ³³ and R ³⁴ each independently 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 form a ring containing a nitrogen atom together with the nitrogen atom, and R ³² and R ³⁴ may form a ring containing a nitrogen atom together with the nitrogen atom.

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

Examples of the alkyl group having 1 to 4 carbon atoms for R ³¹ , R ³² , R ³³ and R ³⁴ include methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group and the like. Can be mentioned.

Examples of the alkylsulfanyl group having 1 to 4 carbon atoms for R ³³ and R ³⁴ include methylsulfanyl group, ethylsulfanyl group, propylsulfanyl group, butylsulfanyl group, isopropylsulfanyl group and the like.

Examples of the alkyl sulfonyl group having 1 to 4 carbon atoms for R ³³ and R ³⁴ include methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, isopropylsulfonyl group and the like.

It is preferable that R <^31> and R <^32> are a C1-C3 alkyl group mutually independently. R ³³ and R ³⁴ are preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

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

Examples of the compound (3a) include compounds represented by the formulas (1-26) to (1-35), respectively. Especially, the compound represented by General formula (1-26)-General formula (1-32) is preferable at the point which is excellent in solubility to an organic solvent.

The xanthene dye (Aa) is a commercially available xanthene dye (for example, "Chugai Aminol Fast Pink RH / C" manufactured by Chugaikasei Co., Ltd., "Rhodamin 6G" manufactured by Taokakagaku Kogyo Co., Ltd.). It is available. Moreover, you may synthesize | combine with reference to Unexamined-Japanese-Patent No. 2010-32999 using commercially available xanthene dye as a starting material.

The pigment (A2) is not particularly limited, and known pigments can be used, and examples thereof include compounds classified as pigments in the Color Index (Published by The Society of Dyers and Colourists).

As the pigment, for example, C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139 Yellow pigments such as, 147, 148, 150, 153, 154, 166, 173, 180, 185, 194, 214, 219;

C.I. Orange pigments such as Pigment Orange 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, 265, etc. Red pigment;

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

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, and 58;

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

C.I. Pigment black 1, pigment black 7, and the like.

Pigments include C.I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60, etc. Blue pigment and C.I. Pigment violet 1, 19, 23, 29, 32, 36, 38, etc. Violet pigments are preferable, C.I. Pigment Blue 15: 3, 15: 6 and C.I. Pigment Violet 23 is more preferred, and C.I Pigment Blue 15: 6 is more preferred. By including said pigment, optimization of a transmission spectrum is easy and the light resistance and chemical-resistance of a color filter become favorable.

Pigment (A2) is optionally treated with rosin treatment, surface treatment using a pigment derivative having an acidic group or basic group, etc., graft treatment on the surface of the pigment with a high molecular compound, atomization treatment by sulfuric acid atomization or the like, or removing impurities. The cleaning treatment by an organic solvent, water, or the like to be removed, the removal treatment by an ion exchange method of ionic impurities, or the like may be performed.

It is preferable that pigment (A2) has a uniform particle diameter. By containing a pigment dispersant and performing a dispersion process, the pigment dispersion liquid of the state in which the pigment was disperse | distributed uniformly in the solution can be obtained.

Examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic. These pigment dispersants may be used independently and may be used in combination of 2 or more type. As the pigment dispersant, KP [manufactured by Shin-Etsukagaku Kogyo Co., Ltd.], Floren [manufactured by Kyoeisha Kagaku Co., Ltd.], Solsperth [manufactured by Geneka Co., Ltd.], EFKA (manufactured by CIBA), Ajisper [Manufactured by Ajinomoto Fine Techno Co., Ltd.], Disperbyk (manufactured by Vikchem Co., Ltd.) and the like.

When using a pigment dispersant, the usage-amount is preferably 1 mass% or more and 100 mass% or less with respect to pigment (A2), More preferably, they are 5 mass% or more and 50 mass% or less. When the usage-amount of a pigment dispersant exists in the said range, there exists a tendency which can obtain the pigment dispersion liquid of a uniform dispersion state.

When the pigment (A2) is included, the content ratio of the dye (A1) and the pigment (A2) is preferably 1:99 to 99: 1 on a mass basis, more preferably 1:99 to 70:30, and 2: 98-50: 50 are 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.

Especially as a coloring agent (A), the coloring agent containing xanthene dye (Aa) and a blue pigment is preferable, and xanthene dye (Aa) and C.I. More preferred is a colorant comprising Pigment Blue 15: 6. 1: 99-70: 30 are preferable on a mass basis, and, as for content ratio of a xanthene dye (Aa) and a blue pigment, 2: 98-50: 50 are more preferable.

Content of a coloring agent (A) becomes like this. Preferably it is 5-60 mass% with respect to the total amount of solid content, More preferably, it is 8-50 mass%, More preferably, it is 10-40 mass%. When content of a coloring agent (A) exists in the said range, since the color concentration at the time of setting it as a color filter is sufficient, and a resin (B) and a polymeric compound (C) can be contained in a composition in a required amount, mechanical strength is Sufficient color filters can be formed.

Here, "total amount of solid content" in this specification means the quantity which subtracted content of a solvent from the total amount of the colored curable resin composition of this invention. The total amount of solids and the content of each component thereof can be measured by known analytical means such as, for example, liquid chromatography or gas chromatography.

<Resin (B)>

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

At least one selected from the group consisting of a resin [K1] unsaturated carboxylic acid and an unsaturated carboxylic anhydride (hereinafter may be referred to as "(a)"), a cyclic ether structure having 2 to 4 carbon atoms, and Copolymer with monomer (b) (hereinafter sometimes referred to as "(b)") having an ethylenically unsaturated bond;

Monomer (c) copolymerizable with resin [K2] (a) and (b) and (a) (however different from (a) and (b)) (hereinafter may be referred to as "(c)") Copolymers with;

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

Resin [K4] Resin which (b) was made to react with the copolymer of (a) and (c);

Resin [K5] Resin which (a) was made to react with the copolymer of (b) and (c);

Resin [K6] Resin which (a) was made to react with the copolymer of (b) and (c), and the carboxylic acid anhydride was made to react further.

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

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

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2- N, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methyl ratio Bicyclo unsaturated compounds containing carboxyl groups such as cyclo [2.2.1] hept-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hept-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 acid anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride;

Unsaturated mono [(meth) acryloyloxyalkyl of a divalent or higher polyhydric carboxylic acid such as succinate mono [2- (meth) acryloyloxyethyl] and phthalate mono [2- (meth) acryloyloxyethyl] ] Esters;

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

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

In addition, in this specification, "(meth) acryloyl" shows 1 or more types chosen from the group which consists of acryloyl and methacryloyl. Notation, such as "(meth) acrylic acid" and "(meth) acrylate", has the same meaning.

(b) is a polymeric compound which has an ethylenically unsaturated bond with a C2-C4 cyclic ether structure (for example, 1 or more types chosen from the group which consists of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring). As for (b), the monomer which has a C2-C4 cyclic ether structure and a (meth) acryloyloxy group is preferable.

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

As (b), for example, a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)") and a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter "( b2) ", and the monomer (b3) which may have a tetrahydrofuryl group and ethylenically unsaturated bond (Hereinafter, it may be called" (b3) ").

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

Examples of (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether and o-vinyl benzyl. Glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α -Methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxy Methyl) 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, and 2,4,6-tris (glycidyloxymethyl) styrene Can be.

(b1-2) include, for example, vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane [eg, ceoxide 2000; Daicel Kagaku Kogyo Co., Ltd. product, 3, 4- epoxycyclohexyl methyl (meth) acrylate [for example, cyclomer A400; Daicel Kagaku Kogyo Co., Ltd.], 3, 4- epoxycyclohexyl methyl (meth) acrylate [for example, cyclomer M100; Daicel Kagaku Kogyo Co., Ltd.], the compound represented by general formula (I), the compound represented by general formula (II), etc. are mentioned.

[Formula (I) and Formula (II), R ^b1 and R ^b2 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxy group.

X ^b1 and X ^b2 represent a single bond, -R ^b3- , * -R ^b3 -O-, * -R ^b3 -S- or * -R ^b3 -NH-.

R ^b3 represents 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 and tert-butyl group.

Examples of the alkyl group in which the hydrogen atom is substituted with hydroxy include a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy A hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, etc. are mentioned.

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

Examples of alkanediyl groups include methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl and hexane-1 And a 6-diyl group.

X ^b1 and X ^b2 are preferably a single bond, a methylene group, an ethylene group, * -CH ₂ -O- and * -CH ₂ CH ₂ -O-, and more preferably a single bond and * -CH ₂ CH ₂ -O- (* represents the number of bonds with O).

Examples of the compound represented by the formula (I) include a compound represented by any one of the formulas (I-1) to (I-15). Among them, general formula (I-1), general formula (I-3), general formula (I-5), general formula (I-7), general formula (I-9) or general formula (I-11) to general formula (I-15) The compound represented by) is preferable, and the compound represented by general formula (I-1), general formula (I-7), general formula (I-9), or general formula (I-15) is more preferable.

Examples of the compound represented by the formula (II) include a compound represented by any one of the formulas (II-1) to (II-15). Among them, the formulas (II-1), (II-3), (II-5), (II-7), (II-9) or (II-11) to (II-15) The compound represented by) is preferable, and the compound represented by general formula (II-1), general formula (II-7), general formula (II-9), or general formula (II-15) is more preferable.

The compound represented by general formula (I) and the compound represented by general formula (II) may be used independently, respectively, and may mix and use in arbitrary ratios. When used in combination, the content ratio of the compound represented by the formula (I) and the compound represented by the formula (II) is preferably 5:95 to 95: 5, more preferably 10:90 to 90 on a molar basis. : 10, More preferably, it is 20: 80-80: 20.

As (b2), 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, 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 (b3), the monomer which has a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, biscoat V # 150, manufactured by Osaka Yuki Chemical Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

It is preferable that (b) is (b1) from the point which can improve reliability, such as heat resistance and chemical-resistance, of the color filter obtained. Moreover, (b1-2) is more preferable at the point which is excellent in the storage stability of colored curable resin composition.

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-methylcyclo Hexyl (meth) acrylate, tricyclo [5.2.1.0 ^2.6 ] decane-8-yl (meth) acrylate (in the art, it is commonly known as "dicyclopentanyl (meth) acrylate." May be referred to as cyclodecyl (meth) acrylate), tricyclo [5.2.1.0 ^2.6 ] decen-8-yl (meth) acrylate (as the common name in the art, “dicyclopentenyl (meth) acrylate) And dicyclopentanyl) Cethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naph (Meth) acrylic acid esters such as methyl (meth) acrylate and benzyl (meth) acrylate;

Hydroxy 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;

2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept- Ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept- 2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept- Cyclohexyl [2.2.1] hept-2-ene, 5,6-bis Ratios such as s (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene and 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene Cyclo unsaturated compounds;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butylate, N-succinimidyl Dicarbonylimide derivatives such as -6-maleimide caproate, N-succinimidyl-3-maleimide propionate and N- (9-acridinyl) maleimide;

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

Among these, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, etc. are preferable at the point of copolymerization reactivity and heat resistance.

In resin [K1], the ratio of the structural unit derived from each is in all the structural units which comprise resin [K1],

structural unit derived from (a); 2 to 60 mol%

structural unit derived from (b); It is preferable that it is 40-98 mol%,

structural unit derived from (a); 10-50 mol%

structural unit derived from (b); It is more preferable that it is 50-90 mol%.

When the ratio of the structural unit of resin [K1] exists in the said range, there exists a tendency which is excellent in the storage stability of colored curable resin composition, the developability at the time of forming a colored pattern, and the solvent resistance of the obtained colored pattern.

Resin [K1] is, for example, the method described in the document "Experimental method of polymer synthesis" (by Takayuki Otsu, first publication, March 1, 1972 issued by Hakko Sho Chemical Co., Ltd.) and the citations described in this 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 put in a reaction vessel, and, for example, oxygen is replaced by nitrogen to make a deoxygen atmosphere, and a method of heating and keeping warm while stirring is given. Can be. In addition, the polymerization initiator, solvent, etc. which are used here are not specifically limited, What is normally used in the said field | area 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.) are mentioned. As a solvent, what is necessary is just to melt | dissolve each monomer, and the solvent mentioned later used for colored curable resin composition, etc. are mentioned.

In addition, the obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and may use what was taken out as solid (powder) by methods, such as reprecipitation. In particular, by using the solvent used for the colored curable resin composition of this invention as a solvent at the time of this superposition | polymerization, the solution after reaction can be used as it is, and a manufacturing process can be simplified.

In resin [K2], the ratio of the structural unit derived from each is in the whole structural unit which comprises resin [K2],

structural unit derived from (a); 2 to 45 mol%

structural unit derived from (b); 2 to 95 mol%

structural unit derived from (c); It is preferable that it is 1-65 mol%,

structural unit derived from (a); 5-40 mol%

structural unit derived from (b); 5 to 80 mol%

structural unit derived from (c); It is more preferable that it is 5-60 mol%.

When the ratio of the structural unit of resin [K2] exists in the above-mentioned range, there exists a tendency which is excellent in the storage stability of the colored curable resin composition, the developability at the time of forming a colored pattern, and the solvent resistance, heat resistance, and mechanical strength of the obtained colored pattern. .

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

In resin [K3], the ratio of the structural unit derived from each is in the whole structural unit which comprises resin [K3],

structural unit derived from (a); 2 to 60 mol%

structural unit derived from (c); It is preferable that it is 40-98 mol%,

structural unit derived from (a); 10-50 mol%

Structural unit derived from (c): It is more preferable that 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] is obtained by obtaining the copolymer of (a) and (c), and adding the C2-C4 cyclic ether which (b) has to the carboxylic acid and / or carboxylic anhydride which (a) has can do.

First, the copolymer of (a) and (c) is manufactured similarly to the method described as a manufacturing method of resin [K1]. In this case, it is preferable that the ratio of the structural unit derived from each is the ratio similar to what was illustrated by resin [K3].

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

Subsequent to the preparation of the copolymer of (a) and (c), the atmosphere in the flask was replaced with nitrogen to air, and (b) a reaction catalyst of carboxylic acid or carboxylic anhydride with a cyclic ether [such as tris (dimethyl Aminomethyl) phenol and the like] and a polymerization inhibitor (for example, hydroquinone and the like) and the like can be put into the flask and reacted at, for example, 60 ° C to 130 ° C for 1 to 10 hours, thereby producing a resin [K4].

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 of the colored curable resin composition, the developability at the time of forming a pattern, and the solvent resistance, heat resistance, mechanical strength, and the sensitivity of the pattern obtained to become favorable. Since the reactivity of a cyclic ether is high and it is hard to remain unreacted (b), as (b) used for resin [K4], (b1) is preferable and (b1-1) is more preferable.

As for the usage-amount of the said reaction catalyst, 0.001-5 mass parts is preferable with respect to 100 mass parts of total amounts of (a), (b) and (c). As for the usage-amount of the said polymerization inhibitor, 0.001-5 mass parts is preferable with respect to 100 mass parts of total amounts of (a), (b) and (c).

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 facility, polymerization, and the like.

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

structural unit derived from (b); 5 to 95 mol%

structural unit derived from (c); It is preferable that it is 5-95 mol%,

structural unit derived from (b); 10 to 90 mol%

structural unit derived from (c); It is more preferable that it is 10-90 mol%.

Moreover, the carboxylic acid or carboxylic anhydride which (a) has in the cyclic ether derived from (b) which the copolymer of (b) and (c) has on the same conditions as the manufacturing method of resin [K4] Resin [K5] can be obtained by making it react.

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

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.

Carboxylic anhydrides include 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- dicarboxy bicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride), etc. are mentioned. As for the usage-amount of carboxylic anhydride, 0.5-1 mol is preferable with respect to 1 mol of usage-amount of (a).

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 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 ] decylacrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decylacrylate / (meth) acrylic acid / vinyltoluene copolymer, 3 Resin [K2] such as -methyl-3- (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer; Resins such as benzyl (meth) acrylate / (meth) acrylic acid copolymer and styrene / (meth) acrylic acid copolymer; Resin 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, and resin which added glycidyl (meth) acrylate to the tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer; Of resin, tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate which made (meth) acrylic acid react with the copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate Resins [K5], such as resin which made (meth) acrylic acid react with the copolymer; Resin [K6], such as resin which further made tetrahydrophthalic anhydride react with resin which (meth) acrylic acid reacted with the copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate, is mentioned. .

Especially, as resin (B), resin [K1], resin [K2], and resin [K3] are preferable.

Preferably the weight average molecular weight of polystyrene conversion of resin (B) is 3,000-100,000, More preferably, it is 5,000-50,000, More preferably, it is 5,000-30,000. When the molecular weight is in the above-described range, the coating film hardness is improved, the residual film ratio is also high, the solubility in the developing solution of the unexposed part is good, and the resolution tends to be improved.

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

The acid value of resin (B) becomes like this. Preferably it is 50-170 mg-KOH / g, More preferably, it is 60-150 mg-KOH / g, More preferably, it is 70-135 mg-KOH / g. The acid value is a value measured as the amount of potassium hydroxide required to neutralize 1 g of the resin (mg), and can be obtained by titration using, for example, an aqueous potassium hydroxide solution.

Content of resin (B) becomes like this. Preferably it is 7-65 mass% with respect to the total amount of solid content, More preferably, it is 13-60 mass%, More preferably, it is 17-55 mass%. When content of resin (B) exists in the said range, there exists a tendency for the resolution of a coloring pattern and the residual film rate of a coloring pattern to improve.

<Polymeric Compound (C)>

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

Especially, as a polymeric compound (C), it is preferable that it 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 tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( Meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritolhepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- ( (Meth) acryloyloxyethyl) isocyanurate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate, Propylene glycol modified dipentaerythritol hexa (meth) acrylate, Pro-lactone and the like can be modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate.

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

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

It is preferable that content of a polymeric compound (C) is 7-65 mass% with respect to the total amount of solid content, More preferably, it is 13-60 mass%, More preferably, it is 17-55 mass%. When content of a polymeric compound (C) exists in the said range, there exists a tendency for the residual film rate and chemical-resistance of a coloring pattern to improve.

<Polymerization Initiator (D)>

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

Examples of the polymerization initiator (D) include alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyl oxime compounds, biimidazole compounds and the like.

The O-acyl oxime compound is a compound having a partial structure represented by the formula (d1).

Hereinafter, * represents a bond number.

As the O-acyl oxime compound, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1 -One-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6 -(2-methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl -2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentyl propane-1-one-2-imine, etc. are mentioned. You may use commercially available products, such as Irgacure (trademark) OXE01, OXE02 (above BASF Corporation), and N-1919 (ADEKA Corporation).

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

Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4- Morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane-1 -On etc. can be mentioned. You may use commercially available products, such as Irgacure (trademark) 369, 907, and 379 (above, BASF Corporation make).

Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1- [4- (2-hydroxy Oligomers and α, of hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one (alpha)-diethoxy acetophenone, benzyl dimethyl ketal, etc. are mentioned.

In view of sensitivity, a compound having a partial structure represented by the formula (d2) is preferable as the alkylphenone compound.

Triazine compounds include 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 (trichloro To methyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) Tenyl] -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 and 2,4-bis (trichloromethyl) -6 -[2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

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).

Biimidazole compounds include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl)- 4,4 ', 5,5'-tetraphenylbiimidazole (see eg JPH06-75372-A, JPH06-75373-A, etc.), 2,2'-bis (2-chlorophenyl) -4,4' , 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'- Temid (trialkoxyphenyl) biimidazole (see, eg, JPS48-38403-B, JPS62-174204-A, etc.) and imidazole in which the phenyl group at the 4,4'5,5'-position is substituted by a carboalkoxy group A compound (for example, JPH07-10913-A etc.) is mentioned.

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-ethyl anthraquinone, and campquinone; Butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. It is preferable to use these in combination with the polymerization start adjuvant (D1) (especially amines) mentioned later.

Acid generators include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-ace Methoxyphenyl methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodiumhexafluoro Onium salts such as roantimonate, nitrobenzyltosylates, benzointosylates, and the like.

As the polymerization initiator (D), a polymerization initiator containing at least one member selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyl oxime compounds and biimidazole compounds is preferable, and O- The polymerization initiator containing an acyl oxime compound is more preferable, and the polymerization initiator containing an O-acyl oxime compound and an alkylphenone compound is more preferable.

Content of a polymerization initiator (D) becomes like this. Preferably it is 0.1-40 mass parts, More preferably, it is 5-35 mass parts with respect to 100 mass parts of total amounts of resin (B) and a polymeric compound (C). Is 10-30 mass parts. When content of a polymerization initiator (D) exists in the said range, since there exists a tendency for high sensitivity and shortening an exposure time, productivity improves.

You may further include the polymerization start adjuvant (D1) with a polymerization initiator (D). A polymerization start adjuvant (D1) is a compound or sensitizer used in order to accelerate superposition | polymerization of the photopolymerizable compound in which superposition | polymerization started with a polymerization initiator.

An amine compound, an alkoxy anthracene compound, a thioxanthone compound, a carboxylic acid compound, etc. are mentioned as a polymerization start adjuvant (D1).

As the amine compound, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminoisobenzoic acid isoamyl, 2-dimethylaminoethyl benzoate, 4-dimethylamino 2-ethylhexyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (collectively Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4,4 '-Bis (ethylmethylamino) benzophenone and the like can be cited, and among these, 4,4'-bis (diethylamino) benzophenone is preferable. You may use a commercial item, such as EAB-F (made by Hodogaya Kagaku Kogyo Co., Ltd.).

Alkoxy anthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibu Methoxy anthracene, 2-ethyl-9,10-dibutoxy anthracene, and the like.

Thioxanthone compounds include 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone and 1-chloro-4-propoxy Orcanthone etc. are mentioned.

Carboxylic acid compounds include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chloro Phenyl sulfanyl acetic acid, dichlorophenyl sulfanyl acetic acid, N-phenylglycine, phenoxy acetic acid, naphthyl thioacetic acid, N-naphthyl glycine, naphthoxy acetic acid, etc. are mentioned.

As a polymerization start adjuvant (D1), a thioxanthone compound is preferable.

When using these 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 resin (B) and a polymeric compound (C), More preferably, it is 1-20 mass It is wealth. When the amount of the polymerization initiation assistant (D1) is in this range, the coloring pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.

&Lt; Solvent (E) >

The solvent (E) contains ethyl lactate.

As for content of ethyl lactate, 100 mass% or less is preferable more than 50 mass% with respect to the total amount of a solvent (E), More preferably, they are 55 mass% or more and 90 mass% or less. When content of ethyl lactate is in the said range, the bead width of the composition layer formed from the colored curable resin composition of this invention can be narrowed.

The solvent (E) may contain a solvent other than ethyl lactate. It does not specifically limit as this solvent, The solvent normally used in the said field | area can be used. For example, an ester solvent (solvent containing -COO- in a molecule and no -O-), an ether solvent (solvent containing -O- in a molecule and not containing -COO-), an ether ester solvent ( Solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule and not containing -COO-), alcoholic solvents, aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide It can select from etc., and can use.

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

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

As an ether ester solvent, methyl methoxy acetate, ethyl methoxy acetate, butyl acetate, methyl ethoxy acetate, ethyl ethoxy acetate, methyl 3-methoxy propionate, ethyl 3-methoxy propionate, and methyl 3-ethoxy propionate , Ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2- Methyl methyl propionate, 2-ethoxy-2-methyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono Propyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate Bit, di, and the like ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate.

As ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclo Pentanone, cyclohexanone, isophorone, etc. are mentioned.

Alcohol solvents 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.

The organic solvent whose boiling point in 1 atm is 120 degreeC or more and 180 degrees C or less is preferable among the said solvents from an applicability | paintability and a dry point. Such solvents include ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and 4-hydroxy 4-methyl-2-pentanone is preferable, and ethylene glycol monobutyl ether and propylene glycol monomethyl ether are more preferable.

Content of a solvent (E) becomes like this. Preferably it is 70 mass% or more and 95 mass% or less with respect to the total amount of colored curable resin composition, More preferably, it is 75 mass% or more and 90 mass% or less, More preferably, it is 76 mass% or more It is 82 mass% or less. In other words, solid content of colored curable resin composition becomes like this. Preferably it is 5 mass% or more and 30 mass% or less, More preferably, it is 10 mass% or more and 25 mass% or less, More preferably, it is 18 mass% or more and 24 mass% or less. When content of a solvent (E) exists in the said range, the bead width of the composition layer formed from the colored curable resin composition of this invention can be narrowed. Moreover, since flatness at the time of application | coating becomes favorable and a color filter does not run short when a color filter is formed, there exists a tendency for display characteristics to become favorable.

<Fluorinated Surfactant (F)>

As a fluorine-type surfactant (F), surfactant etc. which have a fluorocarbon chain | strand are mentioned in a molecule | numerator. These may have a polymeric group in a side chain.

Surfactants having a fluorocarbon chain in the molecule include, for example, fluoride (registered trademark) FC430, fluoride FC431 (manufactured by Sumitomo 3M Co., Ltd.), mega pack (registered trademark) F142D, mega pack F171, mega pack F172, mega Pack F173, Mega Pack F177, Mega Pack F183, Mega Pack F554, Mega Pack R30, Mega Pack RS-718-K (manufactured by DIC Corporation), F-Top® EF301, F-top EF303, F-top EF351, F-top EF352 [manufactured by Mitsubishi Material Denshi Kasei Co., Ltd.], Supron (registered trademark) S381, Supron S382, Supron SC101, Supron SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (Co., Ltd.) Daikin Fine Chemical Co., Ltd. make), etc. are mentioned.

In addition, surfactants having a siloxane bond and a fluorocarbon chain in molecules such as Megapack® R08, Megapack BL20, Megapack F475, Megapack F477, and Megapack F443 (manufactured by DIC Corporation) are also mentioned. have.

The content of the fluorine-based surfactant (F) is preferably 0.01% by mass or more and 0.1% by mass or less with respect to the total amount of the colored curable resin composition, preferably 0.02% by mass or more and 0.8% by mass or less, and more preferably 0.02% by mass. 0.7 mass% or more. In addition, content of the said pigment dispersant is not contained in this content. When content of a fluorine-type surfactant (F) exists in the said range, the bead width of the composition layer formed from the colored curable resin composition of this invention can be narrowed.

&Lt; Other components >

The colored curable resin composition of the present invention may contain additives known in the art, such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents and the like, as necessary.

<The manufacturing method of colored curable resin composition>

The colored curable resin composition of this invention is a coloring agent (A), resin (B), a polymeric compound (C), a polymerization initiator (D), and a fluorine-type surfactant (F), and the polymerization start adjuvant used as needed ( It can prepare by mixing D1) and other components with a solvent (E).

When the pigment (A2) is included, it is preferable to mix the pigment (A2) with the solvent (E) beforehand 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. At this time, you may mix | blend a part or all of the said pigment dispersant and resin (B) as needed. In the obtained pigment dispersion liquid, the remainder of the resin (B) and the polymerizable compound (C) and the polymerization initiator (D) used as needed, the remainder of the solvent (E), the fluorine-based surfactant (F) and other components, etc. The desired colored curable resin composition can be prepared by mixing so that it may become concentration.

It is preferable to dissolve dye (A1) beforehand in a solvent and to prepare a solution. It is preferable to filter this solution with the filter of about 0.01-1 micrometer of pore diameters.

It is preferable to filter the colored curable resin composition mixed and prepared as mentioned above with the filter of about 0.01-10 micrometers of pore diameters.

<Manufacturing Method of Color Filter>

The photolithographic method, the inkjet method, the printing method, etc. are mentioned as a method of manufacturing the coloring pattern of a color filter with the colored curable resin composition of this invention. Especially, the photolithographic method is preferable. The photolithographic method is a method of applying the colored curable resin composition to a substrate, drying to form a composition layer, and exposing and developing the composition layer through a photomask. In the photolithography method, the colored coating film which is the hardened | cured material of the said composition layer can be formed by not using a photomask at the time of exposure, and / or not developing.

The film thickness of the produced color filter is not specifically limited, It can adjust suitably according to the objective, a use, etc., for example, 0.1-30 micrometers, Preferably it is 0.1-20 micrometers, More preferably, it is 0.5-6 micrometers.

As a board | substrate, glass plates, such as quartz glass, borosilicate glass, alumina silicate glass, and soda-lime glass which silica-coated the surface, resin plates, such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate, silicon, and aluminum on the said board | substrate , Silver, and a silver / copper / palladium alloy thin film or the like are used. Separate color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates.

Formation of each color pixel by the photolithographic method can be carried out under known or conventional conditions or conditions. For example, it can produce as follows.

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

As a coating method, a spin coat method, the slit coat method, the slit and spin coat method, etc. are mentioned. In particular, the colored curable resin composition of the present invention is useful because it can form a composition layer having a narrow bead width when used in a coating method such as a spin coating method or a slit and spin coating method at high speed.

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

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

The film thickness of a composition layer is not specifically limited, What is necessary is just to select suitably according to the film thickness of the target color filter.

Subsequently, the composition layer is exposed through a photomask for forming a desired colored pattern. The pattern on the said photomask is not specifically limited, The pattern 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, the light of 350 nm or less is cut using the filter which cuts this wavelength range, or the light of 436 nm, 408 nm, and 365 nm vicinity is used using the bandpass filter which extracts these wavelength ranges. It may take out selectively. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp etc. are mentioned.

Since it is possible to irradiate parallel light rays uniformly to the entire exposure surface or to accurately position the photomask and the substrate, it is preferable to use an exposure apparatus such as a mask aligner and a stepper.

The coloring pattern is formed on a board | substrate by developing the composition layer after exposure contacting with a developing solution. By development, the unexposed part of a composition layer melt | dissolves in a developing solution and is removed. As a developing solution, aqueous solution of alkaline compounds, such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, tetramethylammonium hydroxide, 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 puddle method, a dipping method and a spray method. In addition, you may tilt the board | substrate at arbitrary angles at the time of image development.

It is preferable to wash with water after image development.

Moreover, it is preferable to post-bake to the obtained coloring pattern. 150 degreeC-250 degreeC is preferable, and, as for post-baking temperature, 160 degreeC-235 degreeC is more preferable. 1-120 minutes are preferable and, as for post-baking time, 10 to 60 minutes are more preferable.

The colored pattern and colored coating film obtained in this way are useful as a color filter, and this color filter is useful as a color filter used for a display apparatus (for example, a liquid crystal display device, an organic EL device, etc.), an electronic paper, a solid-state image sensor, etc.

Example

Next, an Example is given and this invention is demonstrated further more concretely. In the examples,% and parts indicating content to amount of use are based on mass unless otherwise specified.

Synthesis Example 1

In a flask equipped with a cooling tube and a stirring device, a mixture of a compound represented by the formula (A1-1a) and a compound represented by the formula (A1-1b) (trade name Chugai Aminol Fast Pink R; manufactured by Chugaikasei Co., Ltd.) was prepared. 150 parts of chloroform and 8.9 parts of N, N-dimethylformamide were added thereto, and 10.9 parts of thionyl chloride was added dropwise while keeping the temperature at 20 ° C. or lower under stirring. After completion of the dropwise addition, the temperature was raised to 50 ° C, held at the same temperature for 5 hours for reaction, and then cooled to 20 ° C. 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 lower under stirring. Thereafter, the reaction was stirred at the same temperature for 5 hours. Subsequently, the obtained reaction mixture was distilled off the solvent by 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, dried under reduced pressure at 60 ° C, and a mixture of the compounds represented by dyes A1-1 [Chemical Formulas (A1-1-1) to (A1-1-8)] ) Obtained 11.3 parts.

[Synthesis Example 2]

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 and heated to 70 ° C while stirring. Subsequently, the molar ratio of 84 parts of methacrylic acid and the compound represented by 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate [compound represented by General formula (I-1) and general formula (II-1)] Mixed at 50:50] 336 parts were dissolved in 140 parts 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 parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 95 parts of ethyl lactates was dripped in the flask over 4 hours using the other dropping funnel. After completion of the dropwise addition of the polymerization initiator solution, the mixture was kept at 70 ° C. for 4 hours, and then cooled to room temperature, followed by weight average molecular weight (Mw) 8.0 × 10 ³ , molecular weight distribution of 2.5, solid content of 48%, and solid content conversion. The acid value obtained the resin B1 solution which is 104 mg-KOH / g. Resin B1 has the following structural unit.

[Synthesis Example 3]

210 parts of propylene glycol monomethyl ether acetates were introduce | transduced into the flask provided with the stirrer, the thermometer, the reflux cooling tube, the dropping funnel, and the nitrogen inlet tube, and the atmosphere in the flask was made into nitrogen from air. Then, it heated up at 100 degreeC, 70.5 parts (0.40 mol) of benzyl methacrylate, 43.0 parts (0.5 mol) of methacrylic acid, dicyclopentanyl methacrylate [pancryl FA-513M; Hitachikasei Co., Ltd.] The solution which added 3.6 parts of 2,2'- azobisisobutyronitrile to the mixture which consists of 22.0 parts (0.10 mol) and 215 parts of propylene glycol monomethyl ether acetates is dripped, and it is continued at 100 degreeC. Further stirred.

Subsequently, the atmosphere in the flask was changed from nitrogen to air, and 35.5 parts of glycidyl methacrylate [0.25 mol, (50 mol% based on the carboxyl group of methacrylic acid used in this reaction)], tris (dimethylaminomethyl) phenol 0.9 Part and 0.145 part of hydroquinone were charged into a flask, and the reaction was continued at 110 ° C to obtain a resin B2 solution having a weight average molecular weight (Mw) of 3.0 x 10 ⁴ , a solid content of 29%, and an acid value of solid content of 79 mgKOH / g. . Resin B2 has the following structural unit.

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

Device; K2479 [manufactured by Shimadzu Seisakusho Corporation]

column; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ℃

menstruum; THF (tetrahydrofuran)

Flow rate; 1.0 ml / min

Detector; RI

Calibration standards; 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.

Example 1

[Preparation of Colored Curable Resin Composition]

Pigment (A2): C.I. Pigment Blue 15: 6

27 parts of acrylic pigment dispersant

Solvent (E): 158 parts of propylene glycol monomethyl ether acetate

Solvent (E): 70 parts ethyl lactate

40 parts of ethylene glycol monobutyl ether

Were mixed to sufficiently disperse the pigment using a bead mill, and then

Dye A1 7.1 parts Dye A1

Resin (B): Resin B1 (solid content conversion) 48 parts

Polymerizable Compound (C): dipentaerythritol hexaacrylate

[Kayarad (registered trademark) DPHA: Nihon Kayaku Co., Ltd.] 44 copies

Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (irgacure® OXE 01; manufactured by BASF; O-acyl oxime compound 6.2

Polymerization initiator (D): 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one (irgacure (registered trademark) 907; manufactured by BASF; alkylphenone compound) 2.1 part

Polymerization start aid (D1): 2,4-diethyl thioxanthone [Kayacure® DETX-S; Nihon Kayaku Co., Ltd. product; Thioxanthone compound) 5.2 parts

Solvent (E): 473 parts of ethyl lactate

Solvent (E): 80 parts of propylene glycol monomethyl ether acetate

Fluorine-based surfactant (F): Mega Pack (registered trademark) F554 [manufactured by DIC Corporation] 0.036 parts

Was mixed and the colored curable resin composition 1 was obtained.

Example 2

[Preparation of Colored Curable Resin Composition]

Colored curable resin composition 2 was obtained like Example 1 except having changed the 0.027 part of usage-amount of a fluorine-type surfactant (F).

Example 3

[Preparation of Colored Curable Resin Composition]

Colored curable resin composition 3 was obtained like Example 1 except having changed the usage-amount of a fluorine-type surfactant (F) into 0.054 part.

Example 4

[Preparation of Colored Curable Resin Composition]

Colored curable resin composition 4 was obtained like Example 1 except having changed the usage-amount of a fluorine-type surfactant (F) into 0.072 parts.

Example 5

[Preparation of Colored Curable Resin Composition]

Colored curable resin composition 5 was obtained like Example 1 except having changed 473 parts of ethyl lactates to 409 parts, and also changing 80 parts of propylene glycol monomethyl ether acetate to 54 parts.

Example 6

[Preparation of Colored Curable Resin Composition]

Colored curable resin composition 6 was obtained like Example 1 except having changed 473 parts of ethyl lactates to 509 parts, and also changing 80 parts of propylene glycol monomethyl ether acetate to 97 parts.

Comparative Example 1

[Preparation of Colored Curable Resin Composition]

C.I. Pigment Blue 15: 6

5 parts of acrylic pigment dispersant

Propylene glycol monomethyl ether acetate 142 parts

Were mixed to sufficiently disperse the pigment using a bead mill, and then

Dye A1 3.5 parts

Resin B1 (solid content conversion) 31 parts

Dipentaerythritol hexaacrylate [Cayarad® DPHA; Nihon Kayaku Co., Ltd.] 31 parts

9.3 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [irgacure (registered trademark) OXE 01: manufactured by BASF Corporation]

170 parts of ethyl lactate

Propylene glycol monomethyl ether 255 parts

Was mixed to obtain colored curable resin composition H1.

Comparative Example 2

[Preparation of Colored Curable Resin Composition]

C.I. Pigment Blue Part 15: 6

10 parts of acrylic pigment dispersant

230 parts of propylene glycol monomethyl ether acetate

Were mixed to sufficiently disperse the pigment using a bead mill, and then

Dye A1 part 5

160 parts of resin B2 solution

Dipentaerythritol hexaacrylate [Cayarad® DPHA; Nihon Kayaku Co., Ltd.] 46 parts

N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Irgacure® OXE01; BASF Corporation] 14 parts

4-hydroxy-4-methyl-2-pentanone 510 parts

Mega pack F554 [manufactured by DIC Corporation] 0.03 parts

Was mixed to obtain colored curable resin composition H2.

[Measurement of Bead Width]

Colored curable resin composition is apply | coated by spin coating method so that the film thickness after post-baking on a square glass substrate (Eagle 2000; Corning Co., Ltd.) whose one side is 3 inches may be 2.8 micrometers, and then it is 100 degreeC in a clean oven. It was prebaked for 3 minutes to form a composition layer. After cooling, an exposure machine [TME-150RSK; Topcon Co., Ltd.] was irradiated with light at an exposure amount (365 nm) of 150 mJ / cm 2 under an air atmosphere. Subsequently, in the oven, it heated at 220 degreeC for 20 minutes, and produced the board | substrate for evaluation in which the coloring coating film was formed.

The film thickness from the end to the inner part of 1 cm toward the center at the end of the evaluation substrate was measured using a film thickness measuring apparatus [DEKTAK3; Nihon Shinkugi Jutsu Co., Ltd.] was measured continuously. (Circle) and the case where it exceeds 1.2 mm and (circle) and the case where it exceeds 1.2 mm were made into the case where the distance between the position where the film thickness becomes the largest, and the board | substrate for evaluation is 0.9 mm or less. When the bead width measured by the colored coating film after post-baking is narrow, it can be said that a bead width is also narrow also in the composition layer after prebaking. The results are shown in Table 1.

[Production of colored pattern]

The colored curable resin composition was apply | coated by the spin coat method on the square glass substrate (Eagle XG; Corning Co., Ltd.) whose one side is 2 inches, and it prebaked at 100 degreeC for 3 minutes, and the composition layer was formed. After cooling, the interval between the substrate on which the composition layer was formed and the quartz glass photomask having a pattern was set to 100 m, and an exposure machine [TME-150RSK; Topcon Co., Ltd.] was used to irradiate light at an exposure dose (365 nm standard) of 150 mJ / cm 2 under an air atmosphere. In addition, as a photomask, the mask in which the 100 micrometer line-and-space pattern was formed was used. After light irradiation, the composition layer after exposure was immersed in 23 degreeC for 60 second in aqueous developing solution containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide, and it post-baked for 40 minutes at 220 degreeC in the oven after washing with water. Was performed to obtain a coloring pattern.

[Film thickness measurement]

About the obtained coloring pattern, a film thickness was measured with a film thickness measuring apparatus [DEKTAK3; Nihon Shinkugi Jutsu Co., Ltd.] was used for the measurement. The results are shown in Table 1.

[Color evaluation]

About the obtained coloring pattern, a colorimeter [OSP-SP-200; Spectroscopy was measured using Olympus Co., Ltd., and the xy chromaticity coordinates (x, y) and tristimulus values Y in the XYZ colorimeter of CIE were measured using the characteristic function of the C light source. The larger the value of Y, the higher the brightness. The results are shown in Table 1.

According to the colored curable resin composition of the Example, it was confirmed that the composition layer with a narrow bead width can be formed. From this, according to the colored curable resin composition of this invention, a color filter can be manufactured with a high yield.

According to the colored curable resin composition of this invention, a composition layer with a narrow bead width can be formed.

Claims (5)

It contains a coloring agent, resin, a polymeric compound, a polymerization initiator, a fluorine-type surfactant, and a solvent,
Colorants include dyes,
The solvent contains ethyl lactate,
Colored curable resin composition whose content of a fluorine-type surfactant is 0.01 mass% or more and 0.1 mass% or less with respect to the total amount of colored curable resin composition. The colored curable resin composition of Claim 1 whose content of a solvent is 70 mass% or more and 95 mass% or less with respect to the total amount of a colored curable resin composition. The coloring curable resin composition of Claim 1 or 2 in which a coloring agent further contains a pigment. The color filter formed with the colored curable resin composition in any one of Claims 1-3. The display apparatus containing the color filter of Claim 4.