KR102062295B1 - Red colored curable resin composition - Google Patents

Abstract

[식 (１ａ)에서, R¹ 내지 R⁴는 서로 독립적으로 수소 원자, 탄소수 1 내지 20개의 1가의 포화 탄화수소기 또는 치환기를 가지고 있어도 되는 탄소수 6 내지 10개의 1가의 방향족 탄화수소기를 나타낸다. R⁵는 -OH, -SO₃ ^-, -SO₃H 등을 나타낸다. R⁶ 및 R⁷은 각각 독립적으로 수소 원자 또는 탄소수 1 내지 6개의 알킬기를 나타낸다. m은 0 내지 5의 정수를 나타낸다. a는 0 또는 1의 정수를 나타낸다. X는 할로겐 원자를 나타낸다. R⁸은 탄소수 1 내지 20개의 1가의 포화 탄화수소기를 나타낸다. R⁹ 및 R¹⁰은 서로 독립적으로 수소 원자 또는 치환기를 가지고 있어도 되는 탄소수 1 내지 20개의 1가의 포화 탄화수소기를 나타냄]Red color curable which is a coloring agent containing a coloring agent, resin, a polymeric compound, and a polymerization initiator, and a coloring agent containing the compound represented by Formula (1a), and a pigment chosen from the group which consists of a yellow pigment, an orange pigment, and a red pigment. Resin composition.

[In formula (1a), R <^1> -R <^4> represents a C6-C10 monovalent aromatic hydrocarbon group which may independently have a hydrogen atom, a C1-C20 monovalent saturated hydrocarbon group, or a substituent. R ⁵ represents —OH, —SO ₃ ^— , —SO ₃ H, or the like. 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. a represents the integer of 0 or 1. X represents a halogen atom. R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. R ⁹ and R ¹⁰ each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a hydrogen atom or a substituent;

Description

Red coloring curable resin composition {RED COLORED CURABLE RESIN COMPOSITION}

The present invention relates to a red 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. It is known to use a pigment or dye as a coloring agent in such a colored curable resin composition [Yasuzu Suzuki, "Until a clear liquid crystal display is made", the first edition, Nikkan Kogyo Shimbun, 2005 March, page 112].

The red colored curable resin composition is required to be able to manufacture a high brightness red color filter.

The present invention includes the following inventions.

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

Red coloring curable resin composition whose coloring agent is a coloring agent containing the compound represented by Formula (1a), and a pigment chosen from the group which consists of a yellow pigment, an orange pigment, and a red pigment.

[In formula (1a), R <^1> -R <^4> represents a C6-C10 monovalent aromatic hydrocarbon group which may have a hydrogen atom, a C1-C20 monovalent saturated hydrocarbon group, or a substituent independently of each other, The said saturated hydrocarbon The hydrogen atom contained in the group may be substituted with a C6-C10 aromatic hydrocarbon group or a halogen atom, and the hydrogen atom contained in the said aromatic hydrocarbon group may be substituted with the C1-C3 alkoxy group, and is contained in the said saturated hydrocarbon group CH ₂ -may be substituted with -O-, -CO-, or -NR ^11- . R ¹ and R ² may be combined with a nitrogen atom to form a ring containing a nitrogen atom, and R ³ and R ⁴ may be combined with a nitrogen atom to form a ring containing a 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 two or more, some R <^5> may be the same or different.

a represents the integer of 0 or 1.

X represents a halogen atom.

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

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 ⁹ and R ¹⁰ each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a hydrogen atom or a substituent, and -CH ₂ -contained in the saturated aliphatic hydrocarbon group is -O-, -CO-,- NH- or -NR ⁸ -may be substituted, and R ⁹ and R ¹⁰ may be bonded to each other to form a nitrogen-containing heterocycle of 3 to 10 atoms by combining with one of the nitrogen atoms.

R ¹¹ independently of each other 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]

[2] The pigment is C.I. Pigment Yellow 138, 139, 150, C.I. Pigment Red The red colored curable resin composition as described in [1] which is at least 1 sort (s) chosen from the group which consists of 177, 242, and 254.

[3] A red color filter formed from the red colored curable resin composition according to [1] or [2].

[4] A display device comprising the red color filter according to [3].

According to the red colored curable resin composition of this invention, a high brightness red color filter can be manufactured.

The red colored curable resin composition of this invention contains a coloring agent (A), resin (i), a polymeric compound (C), and a polymerization initiator (D).

A coloring agent (A) contains the compound represented by Formula (1a) (henceforth "a compound (1a)"), and a pigment (A2). Furthermore, a coloring agent (A) may contain dye (it differs from compound (1a)) (henceforth "dye (A3)").

It is preferable that the red coloring curable resin composition of this invention contains a solvent (E) further.

In addition, the red colored curable resin composition of this invention may contain 1 or more types chosen from the group which consists of a polymerization initiator (D1) and surfactant (F) as needed.

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

<Coloring agent (A)>

Compound (1a) is represented by formula (1a).

[In formula (1a), R <^1> -R <^4> represents a C6-C10 monovalent aromatic hydrocarbon group which may have a hydrogen atom, a C1-C20 monovalent saturated hydrocarbon group, or a substituent independently of each other, The said saturated hydrocarbon The hydrogen atom contained in the group may be substituted with a C6-C10 aromatic hydrocarbon group or a halogen atom, and the hydrogen atom contained in the said aromatic hydrocarbon group may be substituted with the C1-C3 alkoxy group, and is contained in the said saturated hydrocarbon group CH ₂ -may be substituted with -O-, -CO-, or -NR ^11- . R ¹ and R ² may be combined with a nitrogen atom to form a ring containing a nitrogen atom, and R ³ and R ⁴ may be combined with a nitrogen atom to form a ring containing a 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 two or more, some R <^5> may be the same or different.

a represents the integer of 0 or 1.

X represents a halogen atom.

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

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 ⁹ and R ¹⁰ each independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a hydrogen atom or a substituent, and -CH ₂ -contained in the saturated aliphatic hydrocarbon group is -O-, -CO-,- NH- or -NR ⁸ -may be substituted, and R ⁹ and R ¹⁰ may be bonded to each other to form a nitrogen-containing heterocycle of 3 to 10 atoms by combining with one of the nitrogen atoms.

R ¹¹ independently of each other 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 monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ to R ⁴ include a phenyl group, tolyl group, xylyl group, mesityl group, propylphenyl group and butylphenyl group.

As the halogen atom which may have a substituent group of the aromatic ^{hydrocarbon, -R 8 -, -OH, -OR} 8 -, -SO 3 -, -SO 3 H, -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 them, as the substituent _{^{-SO 3 -, -SO 3 H,}} -SO 3 - Z + and -SO ₂ NR ⁹ R ¹⁰ are preferred, and -SO ₃ ^- Z ⁺ and -SO ₂ NR ⁹ R ¹⁰ are more preferably Do. Examples of Z ⁺ -SO ₃ ^{- -} -SO ₃ in this case is N ⁺ (R ¹¹⁾ ₄ are preferred. If R <^1> -R <^4> is such a group, in the red colored curable resin composition of this invention containing a compound (1a), the generation of a foreign material is few and can form the color filter excellent in heat resistance.

As a ring which R <^1> and R <^2> combine with each other and form as one with a nitrogen atom, and a ring which R <^3> and R <^4> combine with each other and form as one with a 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 icosyl 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.

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

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

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

-SO ₂ R ⁸ there may be mentioned such as methyl sulfonyl group, ethyl sulfonyl, butyl sulfonyl group, sulfonyl group, hexyl, octyl sulfonyl group, sulfonyl group Aiko chamber.

-SO ₃ R ⁸ Examples of the like can be mentioned a methoxy group fabric treatment, fabric treatment ethoxy group, a propoxy group Four treatments, tert- butoxy procedure Four group, hexyloxy group Four treatments, Aiko -1,3 procedure Four groups.

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

N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N-sec-butylsulf Pamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) sulfamoyl group, N- (1, 2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (2-methylbutyl) sulfamoyl group, N- ( 3-methylbutyl) sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexyl sulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamo Diary, N-heptyl sulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octyl sulfamoyl group, N- (2-ethylhexyl) N-1 substituted sulfamoyl groups, such as 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 R <^9> and R <^10> , a C1-C20 monovalent saturated hydrocarbon group may have a substituent. Examples of the substituent include a hydroxy group and a halogen atom.

R ⁹ and R ¹⁰ may be bonded to each other and form one with a nitrogen atom to form a nitrogen-containing heterocycle (heterocycle including one or more nitrogen atoms in the ring) of 3 to 10 atoms. As said heterocycle, the following are mentioned, for example.

R ⁵ is ^{_{-CO 2 H, -CO 2 - Z}} +, -CO 2 R 8, -SO 3 -, -SO 3 - Z +, -SO 3 H and -SO ₂ NHR ⁹ are preferred, -SO ₃ ^-, -SO ₃ ^- Z ^+, a -SO ₃ H and -SO ₂ NHR ⁹ is more preferred.

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

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

Examples of the aralkyl group having 7 to 10 carbon atoms in R ⁸ and R ¹¹ include a benzyl group, a phenylethyl group and a phenylbutyl group.

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 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 (1a), if R ¹¹ is such a group, a color filter with less foreign matter can be formed from the red colored curable resin composition of the present invention containing the compound (1a). .

As compound (1a), the compound represented by Formula (2a) (henceforth "compound (2a)") is more preferable. Compound (2a) may be a tautomer thereof.

In the formula (2a), R ²¹ to R ²⁴ each independently represents hydrogen, -R ²⁶ or a substituent of C 6 -C 10 monovalent aromatic hydrocarbon group which optionally has. R ²¹ and R ²² may be combined with a nitrogen atom to form a ring containing a nitrogen atom, and R ²³ and R ²⁴ may be combined with a nitrogen atom to form a ring containing a 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 two or more, some R <^25> may be same or different.

a1 represents the integer of 0 or 1.

X1 represents a halogen atom.

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

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;

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms for R ²¹ to R ²⁴ include the same groups as those mentioned as the aromatic hydrocarbon group for R ¹ to R ⁴ . Hydrogen atoms contained to said aromatic hydrocarbon is -SO ₃ ^- or may be substituted with Z1 ^+, -SO ₃ R ²⁶ or _{^{-SO 2 NHR 26 -, -SO 3}} H, -SO 3.

And R ²¹ to R ²⁴ as a combination of R ²¹ and R ²³ is a hydrogen atom, R ²² and R ²⁴ is a group having 6 to 10 carbon atoms of the monovalent aromatic hydrocarbon group, hydrogen atom is contained 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. Even more preferred combinations are those in which 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 -SO _2. NHR ²⁶ is substituted.

If R <^21> -R <^24> is such a group, the color filter excellent in heat resistance can be formed from the red colored curable resin composition of this invention containing a compound (2a).

A ring containing a nitrogen atom in which R ²¹ and R ²² are bonded to each other to form one with a nitrogen atom; and a ring containing a nitrogen atom in which R ²³ and R ²⁴ are bonded to each other and formed as one with a nitrogen atom as R; ^The same thing as the ring which ¹ and R <^2> combine with each other and forms as one with a nitrogen atom is mentioned. Among these, aliphatic heterocycles are preferable. As said aliphatic heterocycle, the following are mentioned, for example.

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

When R ²¹ to R ²⁴ are -R ²⁶ , each of -R ²⁶ is preferably a methyl group or an ethyl group. Also, -SO ₃ R ^26, and -SO ₂ NHR ²⁶ R ²⁶ as the carbon number of 3 to 20 branched alkyl group is preferable, and even more preferably having 6 to 12 branched chain alkyl group in, and is a 2-ethylhexyl group Even more preferred. If R <^26> is such a group, the color filter with few generation | occurrence | production of a foreign material can be formed from the red coloring curable resin composition of this invention containing compound (2a).

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

The N ⁺ (R ²⁷⁾ R _4, as the four ²⁷ from two or more is 5 to 20 carbon atoms of the monovalent saturated hydrocarbon group is preferred. Moreover, 20-80 pieces are preferable and, as for the sum total carbon number of four R <^27> , 20-60 pieces are more preferable. When ⁺ N (R ²⁷ ) ₄ is present in the compound (2a), the red colored curable resin composition in which R ²⁷ contains the compound (2a) in such a group can form a color filter with less generation of foreign matters.

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

As compound (1a), the compound represented by Formula (3a) (henceforth "a compound (3a)") is more preferable. Compound (3a) may be a tautomer thereof.

[In formula (3a), R <^31> and R <^32> represents a C1-C10 monovalent saturated hydrocarbon group independently of each other, and the hydrogen atom contained in the said saturated hydrocarbon group is substituted by a C6-C10 aromatic hydrocarbon group or a halogen atom, The hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 3 carbon atoms, and -CH ₂ -included in the saturated hydrocarbon group is substituted with -O-, -CO- or -NR ^11- . You may be.

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 with a nitrogen atom to form a ring containing a nitrogen atom, and R ³² and R ³⁴ may be combined with a nitrogen atom 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, 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.

R ¹¹ has the same meaning as described above]

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms for R ³¹ and R ³² include a group having 1 to 10 carbon atoms for R ⁸ .

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms that may have as the substituent include the same groups as those for R ¹ .

As a C1-C3 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, etc. are mentioned.

R ³¹ and R ³² are each independently a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms.

Examples of the alkyl group having 1 to 4 carbon atoms in R ³³ and R ³⁴ include methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, sec-butyl group and tert-butyl group.

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

R ³³ and R ³⁴ are preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

The integer of 0-2 is preferable, and, as for p and q, 0 and 1 are more preferable.

As compound (1a), the compound represented, for example by Formula (1-1)-Formula (1-42) is mentioned. Further, R ⁴⁰ in formula represents a group having 1 to 20 carbon atoms of the monovalent saturated hydrocarbon group, preferably having 6 to 12 carbon atoms and still more preferably of branched-chain alkyl group, is a 2-ethylhexyl group.

As the compound (1a), a commercially available xanthene dye (for example, "Chugai Aminol Fast Pink RH / C" manufactured by Chugaikasei Co., Ltd. and "Rhodamin 6G" manufactured by Taoka Chemical Co., Ltd.) can be used. Can be. Moreover, you may synthesize | combine with reference to JP2010-32999-A, using commercially available xanthene dye as a starting material.

Examples of the pigment A2 include yellow pigments, orange pigments, and red pigments 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 Yellow pigments such as, 147, 148, 150, 153, 154, 166, 173, 194, and 214;

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

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

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

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

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

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

C.I. Black pigments, such as pigment black 1 and 7, may be included.

Pigments are C.I. Pigment Yellow 138, 139, 150, C.I. Pigment Red 177, 242 and 254 is one or more selected from the group consisting of C.I. Pigment Red 177, 242 and 254 are more preferably one or more selected from the group consisting of. By including said pigment, optimization of the transmission spectrum as a red color filter becomes easy, and the light resistance and chemical-resistance of a color filter become favorable.

Pigments may be rosin-treated, surface-treated using a pigment derivative having an acidic or basic group introduced therein, graft treatment on the surface of the pigment with a high molecular compound, atomization by sulfuric acid atomization, or the like, or removing impurities. To this end, washing with an organic solvent, water, or the like, removal with ionic impurities by ion exchange, or the like may be performed.

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

Examples of the pigment dispersant include pigment dispersants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic. These pigment dispersants may be used alone or in combination of two or more thereof. As a pigment dispersant, brand names KP [made by Shin-Etsu Chemical Co., Ltd.], Floren [made by Kyoeisha Chemical Co., Ltd.], Solsperth [made by Geneca Co., Ltd.], EFKA (made by CIBA company), Ajisper [Ajinomoto Fine Co., Ltd.] Techno Co., Ltd.], Disperbyk (made by BIC Chem), etc. are mentioned.

When using a pigment dispersant, its usage-amount is preferably 1 mass% or more and 100 mass% or less with respect to the total amount of 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 said range, there exists a tendency for the pigment dispersion liquid of a uniform dispersion state to be obtained.

Dye (A3) is not specifically limited, A well-known dye can be used, For example, a solvent dye, an acid dye, direct dye, a mordant dye, etc. are mentioned, The dye which is soluble in an organic solvent is preferable.

Examples of the dye (A3) include compounds classified as dyes in the color index (Published by The Society of Dyers and Colourists), and known dyes described in dyeing notes (Shishensha). Moreover, according to chemical structure, azo dye, cyanine dye, triphenylmethane dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinone imine dye, methine dye, azomethine dye, squarylium dye, acridine dye , Styryl dyes, coumarin dyes, quinoline dyes and nitro dyes. Among these, organic solvent soluble dye is preferable.

Specifically, C.I. Solvent yellow 4, 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, 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 and the like. 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, 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, 33, 34, 35, 37, 40, 42, 44, 57, 66, 73, 76, 80, 88, 97, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426;

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, 17, 19, 34 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, 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 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

C.I. C.I. such as direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104 and the like. Direct dyes,

C.I. Dispulse yellow 51, 54, 76;

C.I. Disperse dyes such as disperse violet 26 and 27,

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

C.I. Reactive Orange 16 et al. C.I. 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, 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 and the like.

Such dye may be appropriately selected in accordance with the spectral spectrum of the desired color filter.

When a coloring agent (A) contains dye (A3), 1-90 mass% is preferable with respect to the total amount of dye (A3), and, as for content of dye (A3), 1-50 mass% is more preferable.

The content ratio of the compound (1a) and the pigment (A2) is preferably 1:99 to 99: 1 on a mass basis, more preferably 2:98 to 50:50, and even more preferably 5:95 to 30:70. . By setting it as such a ratio, optimization of a transmission spectrum becomes easy and the color filter obtained tends to be excellent in contrast, lightness, heat resistance, and chemical-resistance.

The content of the colorant (A) is preferably 5 to 60% by mass, more preferably 8 to 50% by mass, still more preferably 10 to 40% by mass with respect to the total amount of solids. When content of a coloring agent (A) exists in the said range, since the color density at the time of setting it as a color filter can be sufficient, and a resin and a polymeric compound (C) can be contained in a composition in a required amount, sufficient mechanical strength is sufficient. Color filters can be formed.

Here, the "total amount of solid content" in this specification means the quantity remove | excluding content of a solvent from the total amount of a red coloring curable resin composition. The total amount of solids and the content of each component thereof can be measured, for example, by known analysis means such as liquid chromatography or gas chromatography.

<Resin>

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

Resin [1] At least one selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride (hereinafter referred to as "a"), a cyclic ether structure having 2 to 4 carbon atoms and ethylenically unsaturated Copolymers of monomers having a bond (hereinafter referred to as "(iii)");

The resin (a) and (b) and the air of the monomer (c) copolymerizable with (a), but different from (a) and (v) (hereinafter referred to as "(c)"). coalescence;

Copolymers of the resins (a) and (c);

Resin [4] Resin which (v) was made to react with the copolymer of (a) and (c);

Resin [A5] (a) was made to react the copolymer of (b) and (c);

Resin [6] Resin which (a) was made to react with the copolymer of (b) and (c), and the carboxylic anhydride was made to react.

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, metaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetra Unsaturated dicarboxylic acids such as hydrophthalic acid and 1,4-cyclohexene dicarboxylic 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 a carboxyl group such as [2.2.1] hepto-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hepto-2-ene;

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

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

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

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

Moreover, 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.

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

As (iii), for example, a monomer (X1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter referred to as "(X1)") and a monomer (X2) having an oxetanyl group and an ethylenically unsaturated bond [hereinafter, "(B2)", the monomer (3) (henceforth "(3)") etc. which have a tetrahydrofuryl group and ethylenically unsaturated bond are mentioned.

(X1) refers to, for example, a monomer having a structure in which a linear or branched unsaturated aliphatic hydrocarbon is epoxidized (X1-1) (hereinafter referred to as "(X1-1)") and an unsaturated alicyclic hydrocarbon is epoxy. Monomer (X12) (hereinafter, referred to as "(X1-2)") having a structured structure is mentioned.

As (191-1) glycidyl (meth) acrylate, (beta) -methylglycidyl (meth) acrylate, (beta) -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, and o-vinyl benzylglycol 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.

Examples of (B1-2) include vinylcyclohexene monooxide and 1,2-epoxy-4-vinylcyclohexane [for example, ceroxide 2000; Daicel Corporation], 3, 4- epoxycyclohexylmethyl (meth) acrylate [for example, cyclomer A400; Daicel Corporation], 3, 4- epoxycyclohexylmethyl (meth) acrylate [for example, cyclomer M100; Daicel Corporation], the compound represented by Formula (I), the compound represented by Formula (II), etc. are mentioned.

[Formula (I) and Formula (II), R <^b1> and R <^b2> represent a hydrogen atom or a C1-C4 alkyl group, and the hydrogen atom contained in the said alkyl group may be substituted by the hydroxy group.

X ^b1 and X ^b2 represents a single bond (單結合), -R ^b3 - represents the, -R * ^b3 -O-, -S- or ^b3 * -R * -R ^b3 -NH-.

R ^b3 represents an alkanediyl group having 1 to 6 carbon atoms.

* Represents a coupling arm with O]

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

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

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

Examples of the alkanediyl group 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 ^b1 and X ^{b2 are} preferably a single bond, a methylene group, an ethylene group, * -CH ₂ -O- or * -CH ₂ CH ₂ -O-, and more preferably a single bond or * -CH ₂ CH _2- O- (* denotes a bond arm with O).

As a compound represented by Formula (I), the compound etc. which are represented by either of Formula (I-1)-Formula (I-15) are mentioned. Among these, formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-V), or formulas (I- 11) to formula (I-15) ) Is preferable, and the compound represented by formula (I-1), formula (I-7), formula (I-X) or formula (I-15) is more preferable.

Examples of the compound represented by formula (II) include compounds represented by any one of formulas (II-1) to (II-15). Among these, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-V) or formulas (II-1 11) to formula (II-15) ) Is preferable, and the compound represented by formula (II-1), formula (II-7), formula (II-1) or formula (II-15) is more preferable.

The compound represented by Formula (I) and the compound represented by Formula (II) may be used independently, respectively, and may mix and use in arbitrary ratios. When using in mixture, the content rate of the compound represented by Formula (I) and the compound represented by Formula (II) is preferably from 5:95 to 95: 5, more preferably from 10:90 to 90: on a molar basis. 10, even more preferably 20:80 to 80:20.

As (b2), the monomer which has an oxetanyl group and a (meth) acryloyloxy group is more preferable. As (b2), 3-methyl-3-methacryloyloxy methyl oxetane, 3-methyl-3- acryloyloxy methyl oxetane, 3-ethyl-3-methacryloyloxy methyl oxetane, 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 (iii) include tetrahydrofurfuryl acrylate (for example, biscot V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

It is preferable that (b) is (b1) from the point which can further improve reliability, such as heat resistance and chemical-resistance of the color filter obtained. Furthermore, (b 1-2) is more preferable at the point which is excellent in the storage stability of a red 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 -Methylcyclohexyl (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" Also referred to as "tricyclodecyl (meth) acrylate", tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (in the art, the common name is "dicyclopentenyl ( Methacrylate)), dicycle Lofentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, aryl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, (Meth) acrylic acid esters such as naphthyl (meth) acrylate and benzyl (meth) acrylate;

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

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

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

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

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

Among these, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexyl maleimide and N-benzyl maleimide are preferable from the viewpoint 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 units derived from (iii); 40 to 98 mol%

Is preferably,

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

structural units derived from (iii); 50 to 90 mol%

More preferably.

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

Resin [1] is, for example, the method described in the document "Experimental method of polymer synthesis" [Okasu Takayuki, published by Chemical Co., Ltd., First Edition, First Edition, issued March 1, 1972] and the documents described above. It may be prepared with reference to the cited literature.

Specifically, a method of heating and keeping warm while stirring in a deoxygen atmosphere by placing predetermined amounts of (a) and (iii), a polymerization initiator, a solvent, and the like into a reaction vessel and replacing oxygen with nitrogen, for example, is mentioned. . Moreover, 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.], an organic peroxide (benzoyl peroxide, etc.) Examples of the solvent may be those obtained by dissolving respective monomers, and examples thereof include a solvent described later as the solvent (E) of the red colored curable resin composition of the present invention.

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

In resin [K2], the ratio of the structural unit derived from each is in the all the structural units which comprise resin [K2],

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

structural units derived from (iii); 2 to 95 mol%

structural unit derived from (c); 1 to 65 mol%

Is preferably,

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

structural units derived from (iii); 5 to 80 mol%

structural unit derived from (c); 5 to 60 mol%

More preferably.

When the ratio of the structural unit of resin [2] is in the said range, it is the tendency which was excellent in the storage stability of the red 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. There is this.

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 all the structural units which comprise resin [K3],

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

structural unit derived from (c); 40 to 98 mol%

Is preferably,

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

structural unit derived from (c); 50 to 90 mol%

More preferably.

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

Resin [4] can be manufactured 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 be.

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 same ratio as what was heard with 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 production of the copolymers of (a) and (c), the atmosphere in the flask was replaced with nitrogen from air, and (i) a reaction catalyst of carboxylic acid or carboxylic anhydride with a cyclic ether [for example, Tris (dimethylaminomethyl) phenol and the like] and a polymerization inhibitor (for example, hydroquinone and the like) and the like are placed in a flask and reacted at 60 to 130 ° C. for 1 to 10 hours to produce a resin [4]. Can be.

The use amount of (iii) is preferably 5 to 80 moles, more preferably 10 to 75 moles, relative to 100 moles of (a). By setting it as this range, there exists a tendency for the balance of the storage stability of the red 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 (iv), as (v) used for resin [4], (b1) is preferable and (b1-1) is still 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), (iii) 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), (iv) and (c).

Reaction conditions, such as a mixing | blending method, reaction temperature, and time, can be suitably adjusted in consideration of a heat generation amount by a manufacturing facility, superposition | polymerization, etc. In addition, the mixing method and the reaction temperature can be appropriately adjusted in consideration of the amount of heat generated by the production equipment, polymerization, and the like in the same manner as the polymerization conditions.

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

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

structural units derived from (iii); 5 to 95 mol%

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

Is preferably,

structural units derived from (iii); 10 to 90 mol%

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

More preferably.

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

As for the usage-amount of (a) made to react with said copolymer, 5-80 mol is preferable with respect to 100 mol of (iv). Since the reactivity of a cyclic ether is high and it is hard to remain unreacted, (b) is preferable as (b) used for resin [k5], and (b1-1) is still more preferable.

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

As the carboxylic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetra Hydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene anhydride (hymic acid anhydride), and the like. As for the usage-amount of carboxylic anhydride, 0.5-1 mol is preferable with respect to 1 mol of use of (a).

Specific examples of the resin include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer and 3,4-epoxycyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid air. Resins such as coalescing [X1]; Glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxy cicyclo [5.2 .1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid / vinyltoluene / dicyclophene Resins such as tenyl (meth) acrylate copolymer and 3-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; Glycidyl (meth) to a resin in which glycidyl (meth) acrylate is added to a benzyl (meth) acrylate / (meth) acrylic acid copolymer, and tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer Resin, 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 which made (meth) acrylic acid react with the copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate, and tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate Resins such as resins in which (meth) acrylic acid is reacted with a copolymer; Resins, such as resin which made tetrahydrophthalic anhydride react with resin which (meth) acrylic acid reacted with the copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate, etc. are mentioned. .

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

The weight average molecular weight of polystyrene conversion of 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 the molecular weight is in the above range, the coating film hardness is improved, the residual film ratio is also high, and the solubility in the developer of the unexposed part is good, so that the resolution tends to be improved.

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

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

The content of the resin is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, still more preferably 17 to 55% by mass relative to the solid content of the red colored curable resin composition. When content of resin exists in the said range, there exists a tendency for the solubility to the developing solution of an unexposed part to be high.

<Polymeric Compound (C)>

A polymerizable compound (C) is a compound which can superpose | polymerize with the active radical and / or acid which generate | occur | produce from a polymerization initiator (D) by the action of light or heat, For example, the compound etc. which have a polymerizable ethylenically unsaturated bond, etc. are mentioned. These are mentioned, Preferably a (meth) acrylic acid ester compound is mentioned.

As said polymeric compound (C), the polymeric compound which has three or more ethylenically unsaturated bonds is preferable. As such a polymeric compound, a trimethylol propane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acryl Elate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (Meth) acryloyloxyethyl) isocyanate, 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, caprolactone modified pentaerythritol Tri (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. are mentioned. Among these, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

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) is not particularly limited so long as it is a compound capable of generating an active radical, an acid, or the like by the action of light or heat and can initiate 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 formula (d1). Hereinafter, * represents a coupling arm.

As the O-acyl oxime compound, for example, 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-carbazole- 3-yl] -3-cyclopentylpropan-1-one-2-imine, etc. are mentioned. You may use commercially available products, such as Ilgacure (trademark) OXE01, OXE02 (above, BASF Corporation), and N-1919 (ADEKA Corporation).

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

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

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

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

As the triazine compound, for example, 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 and the like.

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

As a biimidazole compound, it is 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole, 2,2'-bis (2,3-dichloro, for example). Phenyl) -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'-tetra (trialkoxyphenyl) biimidazole (see, eg, JPS48-38403-B, JPS62-174204-A, etc.), phenyl group at 4,4 ', 5,5'-position And imidazole compounds substituted with carboalkoxy groups (see, for example, JPH07-10913-A).

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

As the acid generator, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate , 4-acetoxyphenyl methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyl iodonium p-toluenesulfonate, Onium salts, such as diphenyl iodonium hexafluoro antimonate, nitrobenzyl tosylates, benzoin tosylate, etc. are mentioned.

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- More preferred are polymerization initiators containing acyloxime compounds, and even more preferred are polymerization initiators containing O-acyl oxime compounds and alkylphenone compounds.

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

<Polymerization start preparation (D1)>

The polymerization initiator (D1) is a compound or sensitizer used to promote the polymerization of the photopolymerizable compound in which polymerization is initiated by the polymerization initiator. When it contains a polymerization initiator (D1), it is normally used in combination with a polymerization initiator (D).

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

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

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

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

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

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

In addition, when using a polymerization initiator (D1), the usage-amount thereof is 0.1-30 mass parts with respect to 100 mass parts of total amounts of resin (K) and a polymeric compound (C), More preferably, it is 1- 20 parts by mass. Moreover, with respect to 100 mass parts of content of a polymerization initiator (D), Preferably it is 20-100 mass parts, More preferably, it is 30-80 mass parts. If the amount of the polymerization initiator (D1) is in this range, the pattern can be formed with high sensitivity, and there is a tendency for a high-brightness color filter to be obtained.

<Solvent (E)>

Although solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. For example, an ester solvent (solvent containing -COO- in a molecule and not containing -O-), an ether solvent (solvent containing -O- in a molecule and not containing -COO-), 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 said ester solvent, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, Butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetic acid, ethyl acetoacetic acid, cyclohexanol acetate, gamma -butyrolactone, and the like.

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

As said 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, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono Propyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol Noethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like.

As the 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.

Methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin etc. are mentioned as said alcohol solvent.

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

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

Among the above solvents, an organic solvent having a boiling point of 120 ° C. or higher and 180 ° C. or lower at 1 atm (101.325 kPa) is preferable from the viewpoint of applicability and drying properties. Among these, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxy propionate ethyl, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxy Butyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone and N, N-dimethylformamide are preferred, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, More preferred are dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol and ethyl 3-ethoxypropionate.

Content of a solvent (E) in a red colored curable resin composition becomes like this. Preferably it is 70-95 mass% with respect to a red colored curable resin composition, More preferably, it is 75-92 mass%. In other words, solid content of red colored curable 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, since the flatness at the time of application | coating becomes good and a color filter will not run short, there exists a tendency for display characteristics to become favorable.

<Surfactant (F)>

Examples of the surfactant (F) include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having fluorine atoms. These may have a polymeric group in a side chain.

As said silicone type surfactant, surfactant etc. which have a siloxane bond are mentioned. Specifically, Torre silicon DC3PA, Torre silicon SH7PA, Torre silicon DC11PA, Torre silicon SH21PA, Torre silicon SH28PA, Torre silicon SH29PA, Torre silicon SH30PA, Torre silicon SH8400 [manufactured by Torre Dow Corning Co., Ltd.], KP321, KP322, KP323 , KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 [Momental Performance Materials Japan Corporation ]] Etc. are mentioned.

As said fluorine-type surfactant, surfactant etc. which have a fluorocarbon chain | strand are mentioned. Specifically, Floroid (trade name) FC430, Floride FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megapack (registered trademark) F142D, Megapack F171, Megapack F172, Megapack F173, Megapack F177, Megapack F183 , Megapack F554, Megapack R30, Megapack RS-718-K (manufactured by DIC Corporation), F-Top® EF301, F-top EF303, F-top EF351, F-top EF352 [Mitsubishi Material Electronic Chemicals ( Ltd.], Saffron (registered trademark) S381, Saffron S382, Saffron SC101, Saffron SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Research Institute, Inc.), 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 (R) R08, Mega Pack BL20, Mega Pack F475, Mega Pack F477, Mega Pack F443 (manufactured by DIC Corporation), and the like.

The content of the surfactant (F) is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.1% by mass or less with respect to the red colored curable resin composition, still more preferably 0.01% by mass. 0.05 mass% or more. However, content of the said pigment dispersant is not contained in content of the said surfactant (F). When content of surfactant (F) exists in said range, flatness of a coating film may become favorable.

<Other Ingredients>

The red colored curable resin composition of this invention may contain additives known in the art, 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 manufacturing method of a red coloring curable resin composition>

The red colored curable resin composition of this invention is compound (1a), a pigment (A2), resin (i), a polymeric compound (C), and a polymerization initiator (D), and dye which can be used as needed, for example. It can prepare by mixing A3), a polymerization start adjuvant (D1), a solvent (E), surfactant (F), and another component.

It is preferable to disperse | distribute pigment (A2) previously with a part or all of solvent (E) using a bead mill etc. until the average particle diameter of a pigment becomes about 0.2 micrometer or less. Under the present circumstances, you may mix | blend a part or all of the said pigment dispersant and resin as needed. Dye (A3) and polymerization initiator (A3) and remainder of compound (1a), resin (b), polymerizable compound (C) and polymerization initiator (D) and solvent (E) which are used in the obtained pigment dispersion liquid, and if necessary ( The target red coloring curable resin composition can be prepared by mixing D), a polymerization initiator adjuvant (D1), surfactant (F), and other components to a predetermined concentration.

The dye (A3) and the compound (1a) in the case of containing the dye (A3) may be dissolved in some or all of the solvent (E) in advance, respectively, to prepare a solution. It is preferable to filter the said solution with the filter of about 0.01-1 micrometer of pore diameters.

It is preferable to filter the red colored curable resin composition mixed and prepared as mentioned above with the filter of about 0.1-10 micrometers of pore diameters.

<Manufacturing method of a red color filter>

As a method of manufacturing the coloring pattern of a red color filter from the red coloring curable resin composition of this invention, the photolithographic method, the inkjet method, the printing method, etc. are mentioned. Among these, the photolithographic method is preferable. The photolithographic method is a method of apply | coating the said red colored curable resin composition to a board | substrate, drying to form a composition layer, exposing the said composition layer by photomask insertion, and developing. 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 and / or developing at the time of exposure.

Although the film thickness of the red color filter to produce is not specifically limited, It can adjust suitably according to an 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. .

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. And silver, and the thing which formed the silver / copper / palladium alloy thin film etc. can be used. Another color filter layer, a resin layer, a transistor, a circuit, etc. may be formed on such a board | substrate.

Formation of each color pixel by the photolithographic method can be performed by a known or conventional apparatus or conditions. For example, it can produce as follows.

First, a red 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 (prebake) and / or drying under reduced pressure, and a smooth composition layer is obtained.

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

30-120 degreeC is preferable and, as for the temperature in the case of heat-drying, 50-110 degreeC is more preferable. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 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.

Although 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 red color filter made into the objective.

Next, the composition layer is exposed by sandwiching a photomask in order to form a desired colored pattern. Although the pattern on the said photomask is not specifically limited, The pattern according to the intended use can be used.

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

It is preferable to use exposure 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 position combination of a photomask and a board | substrate.

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 concentration in the aqueous solution of such an alkaline compound is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Furthermore, the developing solution may contain surfactant.

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

It is preferable to wash with water after image development.

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

The coloring pattern and colored coating film obtained in this way are useful as a red color filter. In particular, according to the red colored curable resin composition of the present invention, since a high-brightness red color filter can be produced, the red color filter is a display device (for example, a liquid crystal display device, an organic EL device, etc.), electronic paper, and solid-state imaging. It is useful as a red color filter used for an element.

Example

The present invention will be described more specifically with reference to the following examples. In the examples,% and parts indicating the content to the amount of use are based on mass unless otherwise specified.

In the following, the structure of the compound was confirmed by mass spectrometry (LC; Form Agilent 1200, MASS; Form Agilent LC / MSD).

Synthesis Example 1

12 parts of the compound represented by Formula (1), 60 parts of N-methyl-2-pyrrolidone, and 12.6 parts of piperidine (manufactured by Tokyo Kasei Co., Ltd.) were mixed, and the obtained mixture was stirred at 60 ° C for 5 hours. The reaction solution was cooled to room temperature, and then added into a mixed solution of 600 parts of water and 100 parts of 35% hydrochloric acid and stirred at room temperature for 1 hour. The precipitated crystals were obtained as a residue of suction filtration and dried to obtain 12.4 parts of the compound represented by the formula (1-447). Yield 83%.

Identification of the compound represented by formula (１-4７)

(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] + 503.4

Exact Mass: 502.2

Synthesis Example 2

15 parts of the compound represented by Formula (1), 75 parts of N-methyl-2-pyrrolidone, and 25.8 parts of decahydroquinoline (manufactured by Tokyo Kasei Co., Ltd.) were mixed, and the obtained mixture was stirred at 110 ° C for 24 hours. The reaction solution was cooled to room temperature, and then added into a mixed solution of 600 parts of water and 100 parts of 35% hydrochloric acid and stirred at room temperature for 1 hour. The precipitated crystals were obtained as a residue of suction filtration and dried to obtain 19.5 parts of the compound represented by the formula (1-4). The yield was 86%.

Identification of the compound represented by formula (1-4 ')

(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] + 611.4

Exact Mass: 610.3

Synthesis Example 3

20 parts of compounds represented by Formula (1) 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, after adding to 800 parts of water and 50 parts of 35% hydrochloric acid, and stirring at room temperature for 1 hour, crystal | crystallization precipitated. The precipitated crystals were obtained as a residue of suction filtration, and then dried to obtain 24 parts of the compound represented by the formula (1-5). Yield 80%.

Identification of the compound represented by formula (1-5)

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

Exact Mass: 602.2

Synthesis Example 4

The mixture obtained by mixing 12 parts of compounds represented by Formula (1), 60 parts of N-methyl-2-pyrrolidone, and 14.7 parts of 1-methyl piperidine (manufactured by Tokyo Kasei Co., Ltd.) was mixed at 60 ° C. for 5 hours. Stirred. The reaction solution was cooled to room temperature, and then added into a mixed solution of 600 parts of water and 100 parts of 35% hydrochloric acid and stirred at room temperature for 1 hour. The precipitated crystals were obtained as a residue of suction filtration and dried to obtain 13.8 parts of the compound represented by the formula (1-4). The yield was 88%.

Identification of the compound represented by formula (1-4 ')

(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] + 531.2

Exact Mass: 530.2

Synthesis Example 5

In a flask equipped with a cooling tube and a stirring device, 15 parts of 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 Chuga Kasei), chloroform 150 parts and 8.9 parts of N, N-dimethylformamide were added thereto, and 10.9 parts of thionyl chloride was added dropwise while maintaining 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. While maintaining the reaction solution after cooling to 20 degrees C or less under stirring, the liquid mixture of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was dripped, and it added. Thereafter, the reaction was stirred at the same temperature for 5 hours. Subsequently, the obtained reaction mixture was removed by evaporation of the solvent with a rotary evaporator, and then a small amount of methanol was added thereto, followed by vigorous stirring. This mixture was added to the liquid mixture of 375 parts of ion-exchange water, stirring, and the crystal | crystallization was deposited. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, dried under reduced pressure at 60 ° C, and dyes (a) [formula (A1-1-1) to formula (A1-1-1)). A mixture of compounds represented by] was obtained 11.3 parts.

Synthesis Example 6

In a flask equipped with a stirrer, a thermometer, a reflux cooler, and a dropping funnel, nitrogen was flowed at 0.02 L / min to a nitrogen atmosphere, and 305 parts of propylene glycol monomethyl ether acetate was added and heated to 70 ° C while stirring. Subsequently, 60 parts of acrylic acid and 3,4-epoxy cicyclocyclo [5.2.1.0 ^2.6 ] decyl acrylate [compound represented by the formula (I-1) and the compound represented by the formula (II-1) were mixed at a molar ratio of 50:50. 440 parts were dissolved in 140 parts of propylene glycol monomethyl ether acetate 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 225 parts of propylene glycol monomethyl ether acetates was dripped in the flask over 4 hours using the other dropping funnel. It was. After completion of the dropwise addition of the solution of the polymerization initiator, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature. The weight average molecular weight (Mw) was 9.1 × 10 ³ , the molecular weight distribution was 2.16, the solid content 34.8%, and the solid content conversion. A resin # 1 solution having an acid value of 81 mgKOH / g was obtained. Resin B1 has the structural unit shown below.

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.

Equipment: K2479 [manufactured by Shimadzu Corporation]

Column: SHIMADZU Shim-pack GPC-80M

Column temperature: 40 ℃

Solvent: THF (Tetrahydrofuran)

Flow rate: 1.0 mL / min

Detector: RI

Calibration standard: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500

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 10-12

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

1) The pigment was mixed with the pigment dispersant and the amount of propylene glycol monomethyl ether acetate described in the E-1 ² column and predispersed.

2) E-1 ²⁾ represents the sum total of propylene glycol monomethyl ether acetate content.

Moreover, in Table 1, each component shows the following. In addition, resin represents the mass part of conversion of solid content.

Compound (1a): A1-1: Compound represented by formula (1-447)

Compound (1a): A1-2: Compound represented by Formula (1-4 ')

Compound (1a): A1-3: Compound represented by Formula (1-5)

Compound (1a): A1-4: Compound represented by Formula (1-4 ')

Compound (1a): A1-5: Compound represented by Formula (1-41-1)

Compound (1a): A1-6: Compound represented by Formula (1-7)

Pigment (A2): A2-1: C.I. Pigment Red 254

Pigment (A2): A2-2: C.I. Pigment Red 242

Pigment (A2): A2-3: C.I. Pigment Red 177

Resin (B): Resin B1

Polymerizable compound (C): dipentaerythritol hexaacrylate [KAYARAD® DPHA; Nihon Kayaku Co., Ltd.]

Polymerization initiator (D): N-1919 (made by ADEKA Corporation; O-acyl oxime compound)

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

Polymerization initiator (D2): OXE01 (Ciba Specialty Chemicals)

Solvent (E): E-1: Propylene glycol monomethyl ether acetate

Solvent (E): E-2: Propylene glycol monomethyl ether

Solvent (E): E-3: Diacetone alcohol

Surfactant (F): fluorine-based surfactant [Megapack® F554; DIC Corporation]

[Production of colored pattern]

The red colored curable resin composition was apply | coated by the spin coat method on the glass substrate (Eagle XG; Corning Co., Ltd.) of 2-inch angle, and then prebaked at 100 degreeC for 3 minutes, and the composition layer was formed. After cooling, the interval between the composition layer on the substrate and the quartz glass photomask having the pattern was set to 100 µm, and the exposure machine [TME-150RSK; Topcon Co., Ltd.] was used to irradiate light at an exposure amount (365 nm standard) of 150 mJ / cm 2 under an air atmosphere. Moreover, as a photomask, the mask in which the 100-micrometer line and space pattern was formed was used. After light irradiation, the coating film was immersed in an aqueous developer containing 0.12% of nonionic surfactant and 2% of sodium carbonate at 23 ° C. for 80 seconds, developed, washed with water, and post-baked at 230 ° C. for 20 minutes in an oven. , Coloring pattern was obtained.

[Film thickness measurement]

About the obtained coloring pattern, film thickness measuring apparatus [DEKTAK3; The film thickness was measured using Japan Vacuum Technology Co., Ltd. product. The results are shown in Table 2.

[Color evaluation]

About the coloring pattern on the obtained glass substrate, 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 isochromatum coefficient of the C light source. The larger the value of Y, the higher the brightness. The results are shown in Table 2.

[Contrast Evaluation]

The same operation as the formation of the colored pattern was performed except that the photomask was not exposed and the image was not developed, thereby producing a colored coating film on a glass substrate. The contrast value was set to a blank value of 30000 by using a contrast colorimeter (CT-1; manufactured by Tsubosaka Electric Co., Ltd., detector; BM-5A, light source; F-10) to the colored coating film on the obtained glass substrate. Was measured. What put the colored coating film on a glass substrate in the polarizing film (POLAX-38S; made by Lukeo Corporation) was made into the measurement sample. The results are shown in Table 2.

Example 13

A red colored curable resin composition was prepared in the same manner as in Example 1 except that the compound represented by the formula (1-4) was changed to a dye (a). Operation similar to Example 1 is performed with respect to the said red colored curable resin composition, and a high brightness coloring pattern is obtained.

Example 14

The compound represented by formula (1-4) is C.I. A red colored curable resin composition was prepared in the same manner as in Example 1 except for changing to acid red 52. Operation similar to Example 1 is performed with respect to the said red colored curable resin composition, and a high brightness coloring pattern is obtained.

According to the red colored curable resin composition of this invention, a high brightness red color filter can be manufactured.

Claims (4)

Containing a colorant, a resin, a polymerizable compound and a polymerization initiator,
Red coloring curable resin composition whose said coloring agent is a coloring agent containing the compound represented by Formula (1a), and a pigment chosen from the group which consists of a yellow pigment, an orange pigment, and a red pigment.

[In the formula (1a), a combination of R ¹ and R ² is a combination of a saturated hydrocarbon group and a combination of a saturated hydrocarbon group, or a saturated hydrocarbon group and aromatic hydrocarbon group (1),
The combination of R ³ and R ⁴ is a combination of a saturated hydrocarbon group and a saturated hydrocarbon group or a combination of a saturated hydrocarbon group and an aromatic hydrocarbon group (1),
The said saturated hydrocarbon group is a C1-C20 monovalent saturated hydrocarbon group,
Said aromatic hydrocarbon group (1) is a C6-C10 monovalent aromatic hydrocarbon group which may have a substituent,
The hydrogen atom contained in the said saturated hydrocarbon group may be substituted by the C6-C10 aromatic hydrocarbon group (2) or a halogen atom, and the hydrogen atom contained in the said aromatic hydrocarbon group (2) may be substituted by the C1-C3 alkoxy group, Or -CH ₂ -contained in the saturated hydrocarbon group may be substituted with -O-, -CO-, or -NR ^11- . When the combination of R ¹ and R ^{2 and} the combination of R ³ and R ⁴ are each a combination of a saturated hydrocarbon group and a saturated hydrocarbon group, R ¹ and R ² , and R ³ and R ⁴ are each a nitrogen atom and It becomes one and forms the ring containing a nitrogen atom.
R ⁵ is -SO ₃ ^- shows a Z ^{+ -,} -SO ₃ H, or -SO _3.
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 two or more, some R <^5> may be the same or different.
a represents the integer of 0 or 1.
X represents a halogen atom.
Z ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ .
R ¹¹ independently of one another represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. The method of claim 1,
Red pigmentary curable resin composition wherein the pigment is at least one selected from the group consisting of CI Pigment Yellow 138, 139, 150, CI Pigment Red 177, 242 and 254. The red color filter formed with the red colored curable resin composition of Claim 1 or 2. A display device comprising the red color filter of claim 3.