TWI714597B - Colored curable resin composition, color filter and display device - Google Patents

Abstract

The subject of the present invention is to provide a coloring curable resin composition, a color filter, and a display device with good solvent resistance. The colored curable resin composition contains a colorant (A), a binder resin (B), a polymerizable compound (C) and a polymerization initiator (D), and the colorant (A) is composed of a cation having a pigment skeleton A coloring agent with a compound containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and an anion of a compound of oxygen. The binder resin (B) is composed of the following resin (B1) and resin (B2) ), the weight average molecular weight of (B1) is 3,000 or more and less than 12,000, the acid value in terms of solid content is 20~200mg-KOH/g, and the weight average molecular weight of (B2) is 12,000 or more and 100,000 or less, solid The acid value in terms of ingredients is 20~200mg-KOH/g.

Description

Colored curable resin composition, color filter and display device Invention field

The present invention relates to a coloring curable resin composition, a color filter and a display device.

Background of the invention

For liquid crystal display devices, solid-state imaging devices, and the like, color filters formed of a coloring curable resin composition are used. For example, Patent Document 1 describes a coloring curable resin composition containing a compound represented by the following formula (1-8) and C.I. Pigment Blue 15:6.

Prior art literature Patent literature

Patent Document 1: Japanese Patent Application Publication No. 2013-50693

Summary of the invention

The object of the present invention is to provide a colored curable resin composition having good solvent resistance.

The present invention includes the following schemes.

(1) A colored curable resin composition comprising: a colorant (A), a binder resin (B), a polymerizable compound (C), and a polymerization initiator (D), characterized in that the colorant (A) is A coloring agent containing a compound composed of a cation having a pigment skeleton and an anion containing a compound of at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus, and oxygen, and the binder resin (B) contains the following resin The binder resin of (B1) and resin (B2), the weight average molecular weight of (B1) is 3,000 or more and less than 12,000, the acid value in terms of solid content is 20~200mg-KOH/g, and the weight average molecular weight of (B2) is From 12,000 to 100,000, the acid value in terms of solid content is 20 to 200 mg-KOH/g.

(2) The colored curable resin composition according to (1), wherein the resin (B1) contains a structural unit derived from at least one selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and a source It is a copolymer of structural units of monomers having a cyclic ether structure with 2 to 4 carbon atoms and ethylenically unsaturated bonds.

(3) The colored curable resin composition according to (1) or (2), wherein the compound (Aa) is a compound represented by formula (AI), (chemical formula 2)

[In formula (AI), R ⁴¹ to R ⁴⁴ each independently represent a hydrogen atom, a saturated hydrocarbon group with 1 to 20 carbons, an optionally substituted aromatic hydrocarbon group with 6 to 20 carbons, or a substituted carbon number An aralkyl group of 7 to 30. In the saturated hydrocarbon group with 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a substituted or unsubstituted amino group or halogen atom, and the carbon number of the saturated hydrocarbon group is 2 to 20 In this case, the methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom or -CO-. However, in this saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent methylene groups are not substituted by oxygen atoms at the same time, and the methylene groups at the terminal are not substituted by oxygen atoms or -CO-. R ⁴¹ and R ⁴² may bond and form a ring with the nitrogen atom to which they are bonded, and R ⁴³ and R ⁴⁴ may bond and form a ring with the nitrogen atom to which they are bonded.

R ⁴⁷ to R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, and an alkyl group having 1 to 8 carbon atoms, and the methylene group constituting the alkyl group may be substituted with an oxygen atom or -CO-. R ⁴⁸ and R ⁵² may be combined with each other to form -NH-, -O-, -S- or -SO ₂ -. However, in this alkyl group, adjacent methylene groups are not substituted by oxygen atoms at the same time, and the terminal methylene groups are not substituted by oxygen atoms or -CO-.

Ring T ¹ represents an optionally substituted aromatic heterocyclic ring having 3 to 10 carbon atoms.

[Y] ^m- represents any m-valent anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen as essential elements.

m represents any natural number. ]

(4) A color filter formed of the coloring curable resin composition described in any one of (1) to (3).

(5) A display device including the color filter described in (4).

The colored curable resin composition of the present invention has good solvent resistance.

In addition, in this specification, when a plurality of constituent elements are exemplified in parallel, as long as there is no particular limitation, each element can be used alone or in combination of multiple types.

p1: The shape of the pattern evaluated as ○

p2: The shape of the pattern evaluated as △

Fig. 1 is a schematic diagram showing the cross-sectional shape of a color filter.

Detailed ways

The colored curable resin composition of the present invention contains a colorant (A), a binder resin (B), a polymerizable compound (C), and a polymerization initiator (D).

Colorant (A)

The coloring agent (A) contains a compound (Aa) composed of a cation having a pigment skeleton and an anion of a compound containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen (hereinafter, sometimes referred to as Compound (Aa)). The colorant (A) may further include a dye (Ab).

Compound (Aa)

The pigment skeleton in the present invention refers to a partial structure of a compound that selectively absorbs visible light (wavelength: 400 to 750 nm) and has an inherent color, and this partial structure includes a structure for discovering characteristics of an inherent color.

The pigment skeleton of the cation constituting the compound (Aa) includes an azo dye skeleton, a xanthene dye skeleton, an azine dye skeleton, a phthalocyanine dye skeleton, an acridine dye skeleton, an anthraquinone dye skeleton, and a squaraine dye skeleton A pigment skeleton having an onium structure; a triarylmethane skeleton; a pigment skeleton in which one or more of the aromatic hydrocarbon rings of the triarylmethane skeleton is an aromatic heterocyclic ring, etc. Among them, more preferably one or more of the xanthene dye skeleton, triarylmethane skeleton, and triarylmethane skeleton of the aromatic hydrocarbon ring is an aromatic heterocyclic dye skeleton, and more preferably one or more of the aromatic hydrocarbon ring of the triarylmethane skeleton It is the pigment skeleton of the aromatic heterocyclic ring.

The anion derived from a compound containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen is preferably, for example, a heteropolyacid anion containing tungsten and an isopolyanion containing tungsten, more preferably a phosphotungstic acid anion , Silicotungstate anion and tungsten are similar to polyacid anion.

Heteropolyacid anions containing tungsten and homopolyacid anions containing tungsten can include Kaykin type phosphotungstic acid ion α-[PW ₁₂ O ₄₀ ] ^3- , Dawson type phosphotungstic acid ion α-[P ₂ W ₁₈ O ₆₂ ] ^6- , β-[P ₂ W ₁₈ O ₆₂ ] ^6- , Kaykin-type silicotungstic acid ion α-[SiW ₁₂ O ₄₀ ] ^4- , β-[SiW ₁₂ O ₄₀ ] ^4- , γ-[ SiW ₁₂ O ₄₀ ] ^4- , [P ₂ W ₁₇ O ₆₁ ] ^10- , [P ₂ W ₁₅ O ₅₆ ] ^12- , [H ₂ P ₂ W ₁₂ O ₄₈ ] ^12- , [NAP ₅ W ₃₀ O ₁₁₀ ] ^14- , α-[SiW ₉ O ₃₄ ] ^10- , γ-[SiW ₁₀ O ₃₆ ] ^8- , α-[SiW ₁₁ O ₃₉ ] ^8- , β-[SiW ₁₁ O ₃₉ ] ^8- , [W ₆ O ₁₉ ] ^2- , [W ₁₀ O ₃₂ ] ^4- , WO ₄ ^2- and their mixtures.

The compound (Aa) composed of a cation having a pigment skeleton and an anion of a compound containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen includes CI Pigment Red 81, 81:1, and 81: 2, 81: 3, 81:4, 81:5, 169; C.I. Pigment Violet 1, 1:1, 1:2, 2:2, etc.

In addition, the compound (Aa) composed of a cation having a triarylmethane pigment skeleton and an anion of a compound containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen includes CI Pigment Blue 1, 1 : 1, 1: 2, 1: 3, 2, 2: 1, 2: 2, 3, 8, 9, 10, 11, 12, 18, 19, 24, 24: 1, 53, 56, 56: 1 , 57, 58, 59, 60, 61, 62, etc.

The compound (Aa) is preferably a compound represented by formula (A-I) (hereinafter also referred to as (A-I)).

[In formula (AI), R ⁴¹ to R ⁴⁴ each independently represent a hydrogen atom, a saturated hydrocarbon group with 1 to 20 carbons, an optionally substituted aromatic hydrocarbon group with 6 to 20 carbons, or a substituted carbon number An aralkyl group of 7 to 30. In the saturated hydrocarbon group with 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a substituted or unsubstituted amino group or halogen atom, and the carbon number of the saturated hydrocarbon group is 2 to 20 In this case, the methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom or -CO-. However, in this saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent methylene groups are not substituted by oxygen atoms at the same time, and the methylene groups at the terminal are not substituted by oxygen atoms or -CO-. R ⁴¹ and R ⁴² may bond and form a ring with the nitrogen atom to which they are bonded, and R ⁴³ and R ⁴⁴ may bond and form a ring with the nitrogen atom to which they are bonded.

R ⁴⁷ to R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, and an alkyl group having 1 to 8 carbon atoms, and the methylene group constituting the alkyl group may be substituted with an oxygen atom or -CO-. R ⁴⁸ and R ⁵² may be combined with each other to form -NH-, -O-, -S- or -SO ₂ -.

Ring T ¹ represents an optionally substituted aromatic heterocyclic ring having 3 to 10 carbon atoms.

[Y] ^m- represents any m-valent anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen.

m represents any natural number.

In addition, when multiple cations represented by the following formula are contained in one molecule, they may have the same structure or different structures.

[In the formula, the rings T ¹ , R ⁴¹ to R ⁴⁴ and R ⁴⁷ to R ⁵⁴ have the same definitions as above. ]

The aromatic heterocyclic ring of ring T ¹ may be a single ring or a condensed ring.

The substituents that the aromatic heterocyclic ring of ring T ¹ may contain include halogen atoms, cyano groups, optionally substituted alkyl groups having 1 to 20 carbon atoms, and optionally substituted aromatic hydrocarbon groups having 6 to 20 carbon atoms. , Amino groups which may have substituents, etc. The ring T ¹ preferably contains an amino group which may have a substituent such as an alkyl group having 1 to 10 carbon atoms.

Among them, the aromatic heterocyclic ring of ring T ¹ is preferably an aromatic heterocyclic ring containing a nitrogen atom, and more preferably a five-membered aromatic heterocyclic ring containing a nitrogen atom.

Furthermore, the ring T ^{1 is} particularly preferably a ring represented by formula (Ab2-y1).

[R ⁵⁶ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group that may have a substituent.

X2 represents an oxygen atom, -NR ⁵⁷ -or a sulfur atom.

R ⁵⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

R ⁴⁵ and R ⁴⁶ are each independently an optionally substituted saturated hydrocarbon group having 1 to 20 carbons, an alkyl group having 2 to 20 carbons, and the methylene group contained in the alkyl group represents a group that may be substituted by an oxygen atom , An optionally substituted aromatic hydrocarbon group, an optionally substituted aralkyl group or a hydrogen atom. R ⁴⁵ and R ⁴⁶ may be combined and form a ring together with the nitrogen atom to which they are bonded.

However, the adjacent methylene groups are not substituted by oxygen atoms at the same time, and the methylene group at the end of the alkyl group is not substituted by oxygen atoms.

^* Indicates the atomic bond to the carbocation. ]

The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ⁴¹ to R ⁴⁶ and R ⁵⁶ may be any of linear, branched and cyclic. The linear or branched saturated hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, two Linear alkyl groups such as decaalkyl; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl. The saturated hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 6 carbon atoms.

The cyclic saturated hydrocarbon group represented by R ⁴¹ to R ⁴⁶ and R ⁵⁶ may be monocyclic or polycyclic. Examples of the cyclic saturated hydrocarbon group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl. The cyclic saturated hydrocarbon group preferably has 3 to 10 carbon atoms, and more preferably 6 to 10 carbon atoms.

The saturated hydrocarbon groups of R ⁴¹ to R ⁴⁶ and R ⁵⁶ may be substituted by substituted or unsubstituted amino groups or halogen atoms. Examples of substituted amino groups include alkylamino groups such as dimethylamino and diethylamino. In addition, examples of the halogen atom include fluorine, chlorine, bromine, and iodine. In addition, when the halogen atom is a fluorine atom, it is preferably a perfluoroalkyl unit such as a trifluoromethyl unit, a pentafluoroethyl unit, and a heptafluoropropyl unit.

The alkyl group having 1 to 8 carbons represented by R ⁴⁷ to R ⁵⁴ includes groups having 1 to 8 carbons in the linear or branched saturated hydrocarbon group exemplified by the saturated hydrocarbon group represented by R ⁴¹ .

In addition, the alkyl group having 1 to 10 carbon atoms represented by R ⁵⁷ includes groups having 1 to 10 carbon atoms in the linear or branched saturated hydrocarbon group exemplified by the saturated hydrocarbon group represented by R ⁴¹ .

When the saturated hydrocarbon group (preferably alkyl group) represented by R ⁴¹ to R ⁴⁶ has 2 or more carbon atoms, the methylene group contained in the saturated hydrocarbon group (preferably alkyl group) may be substituted with an oxygen atom or -CO-, and preferably may be substituted with oxygen Atom substitution. In addition, oxygen atoms may be inserted between the methylene groups constituting the saturated hydrocarbon group (preferably an alkyl group). The saturated hydrocarbon group (preferably an alkyl group) preferably has 2-10 carbon atoms, more preferably 2-8 carbon atoms. In addition, when the methylene group is substituted by an oxygen atom or -CO-, the number of carbons between the terminal and the oxygen atom or -CO-, or between the oxygen atom or -CO- and the oxygen atom or -CO- is, for example, 1 to 5. , Preferably 2~3, more preferably 2. However, adjacent methylene groups are not substituted by oxygen atoms at the same time, and the methylene group at the end of the alkyl group is not substituted by oxygen atoms.

In addition, the optionally substituted aromatic hydrocarbon group represented by R ⁴¹ to R ⁴⁶ and R ⁵⁶ preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and still more preferably 6 to 12 carbon atoms. The aromatic hydrocarbon group includes phenyl, tolyl, xylyl, naphthyl, anthracenyl, phenanthryl, biphenyl, terphenyl, etc., preferably phenyl, naphthyl, tolyl, xylyl, especially Phenyl is preferred. In addition, the aromatic hydrocarbon group may have 1 or 2 or more substituents. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, iodine atom, and bromine atom; and chloromethyl, trifluoromethyl, etc. have a carbon number of 1~ 6 haloalkyl; methoxy, ethoxy and other alkoxy groups with carbon numbers of 1 to 6; hydroxy; aminosulfonyl; methylsulfonyl and other alkylsulfonyl groups with 1 to 6 carbons; C1-C6 alkoxycarbonyl groups such as methoxycarbonyl and ethoxycarbonyl.

The aralkyl groups that may have substituents represented by R ⁴¹ to R ⁴⁶ include the groups described as the above aromatic hydrocarbon groups and alkylene groups having 1 to 5 carbon atoms such as methylene, ethylene, and propylene. Group.

The ring formed by combining R ⁴¹ and R ⁴² with the nitrogen atom to which they are combined, the ring formed by combining R ⁴³ and R ⁴⁴ with the nitrogen atom to which they are combined, and the nitrogen atom to which R ⁴⁵ and R ^{46 are} combined and combined with them The rings formed together include pyrrolidine ring, morpholine ring, piperidine ring, piperazine ring and other nitrogen-containing non-aromatic 4-7 membered rings, preferably pyrrolidine ring, piperazine ring, etc. have only one nitrogen atom as a heteroatom The 4~7 member ring.

Among them, R ⁴¹ to R ⁴⁴ and R ^{56 are} preferably a saturated hydrocarbon group having 1 to 20 carbons or an aromatic hydrocarbon group that may have a substituent, and more preferably each independently a saturated hydrocarbon group having 1 to 8 carbons or a group represented by the following formula . In the following formula, ^* represents an atomic bond to a nitrogen atom.

(Chemical formula 6)

Preferably, R ⁴⁵ to R ⁴⁶ are each independently a saturated hydrocarbon group with 1 to 20 carbons, a group in which an oxygen atom is inserted between the carbon atoms of an alkyl group with 2 to 20 carbons, or an aromatic hydrocarbon group that may have a substituent Or it is preferable that R ⁴⁵ and R ^{46 are} combined and form a ring together with the nitrogen atom to which they are combined. More preferably, R ⁴⁵ to R ⁴⁶ are each independently a saturated hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group, or a group represented by the following formula, or R ⁴⁵ and R ^{46 are} combined to form a heteroatom having only one The mode of the 4- to 7-membered ring of the nitrogen atom. In the following formula, ^* represents an atomic bond to a nitrogen atom.

In addition, the alkyl group with 1 to 8 carbon atoms represented by R ⁴⁷ to R ⁵⁴ and the group in which the methylene group of the alkyl group with 2 to 8 carbon atoms is substituted with an oxygen atom or -CO- can be exemplified by the aforementioned corresponding to R ⁴¹ to R ⁴⁶ Select a group with 8 or less carbon atoms in the group.

From the viewpoint of ease of synthesis, R ⁴⁷ to R ^{54 are} preferably each independently a hydrogen atom, a halogen atom, or a C 1-8 alkyl group, and more preferably each independently are a hydrogen atom, a methyl group, a fluorine atom, or a chlorine atom.

The cation part of formula (A-I) includes cation 1 to cation 14 represented by formula (A-I-1) shown in Table 1 below.

In Table 1, Ph1 to Ph9 refer to groups represented by the following formula. In the formula, ^* represents an atomic bond.

Among them, the cationic portion of formula (A-I) is preferably cation 1 to cation 6, cation 11 to cation 14, particularly preferably cation 1, cation 2, or cation 12 to cation 14, and most preferably cation 12.

As the compound (Aa), compounds represented by the following formulae can be mentioned.

(Table 2)

(table 3)

The content of the compound (Aa) in the colored curable resin composition relative to the total solid content is usually 1% by mass or more and 70% by mass or less, preferably 5% by mass or more and 60% by mass or less, more preferably 10% by mass More than and 60% by mass or less, particularly preferably 15% by mass or more and 50% by mass or less. In addition, the content of the compound (Aa) relative to the colorant (A) is preferably 20% by mass or more, more preferably 40% by mass or more, still more preferably 60% by mass or more, particularly preferably 80% by mass or more, and preferably 100% by mass or less. When the content of the aforementioned compound (Aa) is within the above range, it is easier to obtain the desired spectral and color density. In addition, in this specification, "the total amount of solid content" refers to the component from the colored curable resin composition of the present invention excluding the solvent The total measurement. The total amount of solid content and the content of each component corresponding to it can be measured by known analysis methods such as liquid chromatography and gas chromatography, for example.

Compound (A-I) can be produced according to the method described in JP 2015-28121 A.

Dye (Ab)

Examples of the dye include compounds having a hue other than pigments classified in the Color Rendering Index (published by The Society of Dyers and Colourists), and known dyes described in Dyeing Notes (Dyeing and Textile Co., Ltd.). Xanthene dyes and azo dyes (for example, monoazo dyes, diazo dyes, trisazo dyes, metal complex salt azo dyes, etc.) are particularly preferred.

The xanthene dye is more preferably a compound represented by the following formula (a1-1) (hereinafter also referred to as a compound (a1-1)). Compound (a1-1) may be its tautomer.

[In formula (a1-1), R ¹ to R ⁴ independently represent a hydrogen atom, a monovalent saturated hydrocarbon group with 1 to 20 carbons that may have a substituent, or a 1 to 10 carbons that may have a substituent A valence aromatic hydrocarbon group, the methylene group (-CH ₂ -) contained in the saturated hydrocarbon group may be substituted by -O-, -CO- or -NR ¹¹ -. R ¹ and R ² may together form a ring containing a nitrogen atom, and R ³ and R ⁴ may together form a ring containing a nitrogen atom.

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

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

m represents an integer from 0 to 5. When m is 2 or more, a plurality of R ⁵ may be the same or different.

A represents an integer of 0 or 1.

X represents a halogen atom.

Z ⁺ represents ⁺ N(R ¹¹ ) ₄ , NA ⁺ or K ⁺ , and the four R ¹¹ may be the same or different.

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

R ⁹ and R ¹⁰ independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ -contained in the saturated hydrocarbon group may be -O-, -CO-,- NH- or -NR ⁸ -substituted, R ⁹ and R ¹⁰ may be combined with each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom.

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

In addition, the xanthene dye is particularly preferably a compound represented by formula (a1-2).

[In formula (a1-2), R ²¹ and R ²² each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbons, and the hydrogen atoms contained in the saturated hydrocarbon groups of R ²¹ and R ²² may be replaced by 6 to 6 carbons. 10 is substituted with an 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 carbons, and the -CH ₂ -contained in the saturated hydrocarbon group of R ²¹ and R ²² may be Replaced by -O-, -CO- or -NR ¹¹ -.

R ²³ and R ²⁴ independently represent an alkyl group having 1 to 4 carbons, an alkylsulfanyl group having 1 to 4 carbons, or an alkylsulfanyl group having 1 to 4 carbons.

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

P and q represent an integer of 0-5 independently of each other. When P is 2 or more, multiple R ²³ may be the same or different, and when q is 2 or more, multiple R ²⁴ may be the same or different.

R ¹¹ represents the same meaning as above. ]

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbons in R ²¹ and R ²² include groups having 1 to 10 carbons in R ⁸ .

Examples of the optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms include the same groups as those in R ¹ .

Examples of the alkoxy group having 1 to 3 carbon atoms include a methoxy group, an ethoxy group, and a propoxy group.

R ²¹ and R ^{22 are} preferably monovalent saturated hydrocarbon groups having 1 to 3 carbon atoms (for example, methyl, ethyl, propyl, isopropyl) independently of each other.

Examples of the alkyl group having 1 to 4 carbon atoms in R ²³ and R ²⁴ include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, and tert-butyl.

Examples of the alkyl mercapto groups having 1 to 4 carbon atoms in R ²³ and R ²⁴ include methyl mercapto, ethyl mercapto, propyl mercapto, butyl mercapto, and isopropyl mercapto.

The alkylsulfonyl groups having 1 to 4 carbon atoms in R ²³ and R ²⁴ include methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl and isopropylsulfonyl. Wait.

R ²³ and R ^{24 are} preferably alkyl groups having 1 to 4 carbon atoms, more preferably methyl and ethyl groups, and still more preferably methyl groups.

P and q are preferably integers of 0-2, preferably 1 or 2.

Among them, the sulfonamide compound of C.I. Acid Red 289, the quaternary ammonium salt of C.I. Acid Red 289, the sulfonamide compound of C.I. Acid Violet 102, and the quaternary ammonium salt of C.I. Acid Violet 102 are preferable.

Examples of xanthene dyes include CI Acid Red 51 (hereinafter the description of CI Acid Red is omitted, and only the number is described. The same below.), 52, 87, 92, 94, 388, CI Acid Violet 9, 30 , CI Basic Red 1 (Rhodamine 6G), 2, 3, 4, 8, CI Basic Red 10 (Rhodamine B), 11, CI Basic Violet 10, 11, 25, CI Solvent Red 218, CI Mordant Agent Red 27, CI Remazol Red 36 (Rose Red B), Sulorhodamine G, the xanthene dye described in JP 2010-32999 A, the xanthene dye described in Patent No. 4492760, and the like.

As other dyes, azo dyes, thiazole dyes, oxazine dyes, phthalocyanine dyes, quinophthalone dyes, etc. can also be used, and various known dyes can also be used.

Examples of azo dyes include: CI direct yellow (hereinafter the description of CI direct yellow is omitted, and only the number is described) 2, 33, 34, 35, 39, 50, 69, 70, 71, 86, 93, 94, 95, 98, 102, 109, 129, 136, 141; CI direct orange 41, 46, 56, 61, 64, 70, 96, 97, 106, 107; CI Direct Red 79, 82, 83, 84, 97, 98, 99, 106, 107, 172, 173, 176, 177, 179, 181, 182, 204, 207, 211, 213, 218, 221, 222, 232 , 233, 243, 246, 250; CI direct purple 47, 52, 54, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; CI direct Blue 51, 57, 71, 81, 84, 85, 90, 93, 94, 95, 98, 100, 101, 113, 149, 150, 153, 160, 162, 163, 164, 166, 167, 170, 172 , 188, 192, 193, 194, 196, 198, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250 , 251, 252, 256, 257, 259, 260, 268, 274, 275; CI Direct Green 27, 34, 37, 65, 67, 68, 69, 72, 77, 79, 82, etc.; CI Acid Red 1, 3, 4, 6, 8, 11, 12, 14, 18, 26, 27, 33, 37, 53, 57, 88, 106, 108, 111, 114, 131, 137, 138, 151, 154, 158, 159, 173, 184, 186, 215, 257, 266, 296, 337; CI Acid Orange 7, 10, 12, 19, 20, 22, 28, 30, 52, 56, 74, 127; CI Acid Violet 11, 56, 58; CI Acid Yellow 1, 17, 18, 23, 25, 36, 38, 42, 44, 54, 59, 72, 78, 151; CI Acid Brown 2, 4, 13, 248; CI Acid Blue 92 , 102, 113, 117, etc.; For example, CI Basic Red 17, 22, 23, 25, 29, 30, 38, 39, 46, 46: 1, 82; CI Basic Orange 2, 24, 25; CI Basic Violet 18; CI Basic Yellow 15, 24, 25, 32, 36, 41, 73, 80; CI Basic Brown 1; CI Basic Blue 41, 54, 64, 66, 67, 129, etc.

The aforementioned azo dye is preferably a metal complex salt azo dye. A metal complex salt azo dye is a compound in which a ligand containing an azo skeleton forms a complex with a central metal. The central metal is preferably chromium, cobalt, or nickel.

The metal complex salt azo dye is more preferably, for example, a compound represented by the following formula (a2-1) (hereinafter also referred to as a compound (a2-1)). Compound (a2-1) may be a tautomer.

[In formula (a2-1), R ⁷¹ to R ⁸⁸ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group with 1 to 8 carbon atoms, a nitro group, -SO ₂ NHR ⁹¹ , -SO ₃ H or -SO ₂ CH ₃ .

R ⁸⁹ and R ⁹⁰ each independently represent a hydrogen atom, a methyl group, or an ethyl group.

R ⁹¹ each independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbons, and an alkoxyalkyl group having 2 to 15 carbons.

A ¹ to A ⁴ each independently represent ^* -O-, ^* -O-CO-, and ^* -CO-O-. ^* Represents the atomic bond bonded to M.

M represents Cr or Co.

n represents an integer from 1 to 5.

D ⁺ represents a hydrogen cation (hydron) or a monovalent metal cation. ]

The metal complex salt azo dyes include C.I. Solvent Red 125, 130; C.I. Solvent Yellow 21, and the compounds described in JP 2010-170116 A or JP 2011-215572 A.

The colorant (A) may further include a pigment (Ac).

Examples of the pigment include pigments classified as pigments in the color rendering index (published by The Society of Dyers And Colourists) (except for the compound (Aa)), and these can be used alone or in combination of two or more.

Specifically, include: CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128 , 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214 and other yellow pigments; CI pigment orange 13, 31, 36, 38, 40, 42, 43, 51 , 55, 59, 61, 64, 65, 71, 73 and other orange pigments; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215 , 216, 224, 242, 254, 255, 264, 265 and other red pigments; CI pigment blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments; CI pigment violet 1, 19, 23, Purple pigments such as 29, 32, 36, 38; and C.I. Pigment Green 7, 36, 58 and other green pigments.

The pigment (Ac) can be dispersed by containing a pigment dispersant to obtain a pigment dispersion in which the pigment dispersant is uniformly dispersed in a solution. The pigments are dispersed separately, or multiple types can be mixed for dispersion treatment.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, acrylic, and other pigment dispersants. These pigment dispersants can be used alone or in combination of two or more kinds. As the trade name of the pigment dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), FLOREN (manufactured by Kyoeisha Chemical Co., Ltd.), SOLSPERSE (manufactured by Zelikon Corporation), EFKA (registered trademark) (manufactured by BASF Corporation), AJISPER FINETECHNO company), DISPERBYK (registered trademark) (manufactured by BYK company), etc.

Coloring mixture

Regarding the production of the colored curable resin composition of the present invention, it is preferable that the compound (Aa) is dissolved or dispersed in a solvent and mixed to prepare a colored mixed liquid. The colored mixture is prepared by mixing a binder resin (B), a polymerizable compound (C), a polymerization initiator (D), etc. to prepare a colored curable resin composition, which can further improve the color filter formed from the colored curable resin composition. The heat resistance of the light sheet.

As the solvent, a solvent that can be used as the solvent (E) of the colored curable resin composition can be used. The solvent is, for example, an ether ester solvent. More preferably, one hydroxyl group of the alkyl glycol or polyalkyl glycol is etherified, and the remaining hydroxyl group is esterified, for example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether ethyl Ester, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol Monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, etc. They can be singly or contain multiple types.

In the colored mixed liquid, the content of the solvent is, for example, 1 to 50 parts by mass, preferably 2 to 30 parts by mass, and more preferably 3 to 10 parts by mass relative to 1 part by mass of the compound (Aa).

It is preferable to use a dispersant for preparing a colored mixed liquid by dispersing the compound (Aa) in a solvent. As the dispersant, for example, known pigment dispersants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, acrylic, etc. can be used. These pigment dispersants can be used alone or in combination of two or more kinds. As the pigment dispersant, the trade names KP (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), FLOREN (manufactured by Kyoeisha Chemical Co., Ltd.), SOLSPERSE (manufactured by Zelikon Co., Ltd.), EFKA (manufactured by BASF Co., Ltd.), AJISPER (manufactured by Ajinomoto FineTechno Co., Ltd.) , DISPERBYK (manufactured by BYK), etc.

The content of the dispersant in the colored mixed liquid is, for example, 1 to 1000 parts by mass relative to 100 parts by mass of the compound (Aa), preferably 3 to 100 parts by mass, more preferably 5 to 50 parts by mass, and particularly preferably 10 to 30 parts by mass.

When the colorant (A) contains the dye (Ab), the color mixture may contain a part or all of the dye (Ab) in advance, and preferably contains all of the dye (Ab) in advance. When the coloring mixture contains the dye (Ab), the amount of the dye (Ab) is, for example, 0.1 to 20 parts by mass relative to 100 parts by mass of the compound (Aa), preferably 0.5 to 10 parts by mass, and more preferably 1 to 5 parts by mass.

When the compound (Aa) is dispersed in a solvent to prepare a colored mixed liquid, the colored mixed liquid may contain a part or all of the binder resin (B) contained in the colored curable resin composition, and preferably contains a part in advance. By including the binder resin (B) in advance, the manufacturing process can be further improved Dispersion stability when color curable resin composition. The content of the binder resin (B) in the color mixture is, for example, 1 to 300 parts by mass, preferably 10 to 100 parts by mass, and more preferably 20 to 70 parts by mass relative to 100 parts by mass of the compound (Aa).

In the colored curable resin composition, the content of the colorant (A) relative to the total solid content is usually 1% by mass or more and 80% by mass or less, preferably 5% by mass or more and 70% by mass or less, more preferably 10% by mass % Or more and 70% by mass or less, particularly preferably 15% by mass or more and 65% by mass or less. When the content of the colorant (A) is within the above range, it is easier to obtain the desired spectral and color density. In addition, in this specification, "the total amount of solid content" refers to the total amount of the components from the colored curable resin composition of the present invention except for the solvent. The total amount of solid content and the content of each component corresponding to it can be measured by known analysis methods such as liquid chromatography and gas chromatography, for example.

When the colorant (A) contains the dye (Ab), the mass ratio (Aa/Ab) of the compound (Aa) to the dye (Ab) is preferably 1 or more, more preferably 2 or more, still more preferably 5 or more, particularly preferably 7 Above, it is preferably 600 or less, more preferably 300 or less, still more preferably 100 or less, still more preferably 50 or less, and particularly preferably 20 or less.

Furthermore, when the pigment (Ac) is included, the ratio (Aa/Ac) of the compound (Aa) to the dye (Ac) is preferably 0.1 or more, more preferably 0.5 or more, still more preferably 0.7 or more, preferably 20 or less, and more preferably 10 Below, 8 or less is more preferable.

When the colorant (A) contains the dye (Ab), the aforementioned coloring mixture containing the dye (Ab) or the mixture containing the dye (Ab) and the solvent can be prepared in advance liquid.

Adhesive resin (B)

The binder resin (B) is not particularly limited, but is preferably an alkali-soluble binder resin, and more preferably has at least one monomer (a) derived from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride (hereinafter sometimes It is a polymer of structural units called "(a)").

The binder resin (B) is preferably a structural unit derived from a monomer (b) (hereinafter sometimes referred to as "(b)") having a cyclic ether structure with a carbon number of 2 to 4 and an ethylenically unsaturated bond and the specific Copolymers of other structural units.

Other structural units may include structural units derived from monomer (c) that is polymerizable with monomer (a) (but monomer (a) and monomer (c) are different, sometimes referred to as "(c)" hereinafter)) , Structural units with ethylenically unsaturated bonds, etc.

(a) Examples include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and P-vinylbenzoic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid , Itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid Unsaturated dicarboxylic acids such as dicarboxylic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid; methyl-5-norbornene-2,3-dicarboxylic acid, 5- Bicyclic unsaturated compounds containing carboxyl groups such as carboxynorbornene, 5,6-dicarboxynorbornene, 5-carboxymethylnorbornene, 5-carboxyethylnorbornene, etc.; maleic anhydride, citraconic anhydride , Itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetra Hydrogen phthalic anhydride, dimethyltetrahydrophthalic anhydride and Carboxylic anhydrides such as unsaturated dicarboxylic anhydrides such as 5,6-dicarboxynorbornene anhydride.

Succinic acid mono[2-(meth)acryloyloxyethyl], phthalic acid mono[2-(meth)acryloyloxyethyl] [(Meth)acryloxyalkyl] esters; such as α-(hydroxymeth)acrylic acid and unsaturated acrylates containing hydroxyl and carboxyl groups in the same molecule.

Among them, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferred from the viewpoint of copolymerization reactivity or the viewpoint of the solubility of the aqueous alkali solution to the obtained binder resin.

(b) It refers to the cyclic ether structure (for example, at least one selected from the group consisting of ethylene oxide, oxetane, and tetrahydrofuran) having a carbon number of 2 to 4 and the polymerizability of ethylenically unsaturated bonds Compound. (b) It is preferably a monomer having a cyclic ether structure with 2 to 4 carbon atoms and a (meth)acryloxy group.

(b) Monomers (b1) having oxiranyl groups and ethylenically unsaturated bonds (hereinafter also referred to as "(b1)"), monomers having oxetanyl groups and ethylenically unsaturated bonds can be cited The monomer (b2) (hereinafter also referred to as "(b2)") and the monomer (b3) (hereinafter also referred to as "(b3)") having a tetrahydrofuran group and an ethylenically unsaturated bond.

(b1) Examples include monomers (b1-1) having a structure in which linear or branched aliphatic unsaturated hydrocarbons are epoxidized (hereinafter also referred to as "(b1-1)") and those having alicyclic Monomer (b1-2) having a structure in which unsaturated hydrocarbons are epoxidized (hereinafter also referred to as "(b1-2)").

(b1-1) Preferably, a monomer having a glycidyl group and an ethylenically unsaturated bond. (b1-1) Specific examples include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, and β-ethylglycidyl (meth)propylene Ester, glycidyl vinyl ether, o-vinylbenzyl 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(glycidyl etheroxymethyl)benzene Ethylene, 2,4-bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl) Styrene, 2,3,4-tris(glycidoxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyl) Glycidoxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene and 2,4,6-tris(glycidyloxymethyl)styrene.

(b1-2) Examples include vinylcyclohexenemonoxide (vinylcyclohexenemonoxide), 1,2-epoxy-4-vinylcyclohexane (for example, CEL2000 (registered trademark); manufactured by Daicel), 3,4-cyclohexene Oxycyclohexyl methyl (meth) acrylate (for example, CYM A400 (registered trademark) A400; manufactured by Daicel), 3,4-epoxycyclohexyl methyl (meth) acrylate (for example, CYM M100; manufactured by Daicel) ), the compound represented by formula (1) and the compound represented by formula (2).

[In the formula, R ^a and R ^b each independently 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 by a hydroxyl group. X ^a and X ^b each independently represent a single bond, ^* -R ^c -, ^* -R ^c -O-, ^* -R ^c -S-, or ^* -R ^c -NH-. R ^c represents an alkanediyl group having 1 to 6 carbon atoms. ^* Represents the atomic bond bonded to O. ]

The compound represented by formula (1) and the compound represented by formula (2) may be used alone, respectively, or the compound represented by formula (1) and the compound represented by formula (2) may be used in combination. When they are used in combination, the ratio of the compound represented by formula (1) and the compound represented by formula (2) (compound represented by formula (1): compound represented by formula (2)) is preferably 5:95 to 95 on a molar basis: 5. More preferably 10:90~90:10, still more preferably 20:80~80:20.

(b2) A monomer having an oxetanyl group and a (meth)acryloxy group is more preferable. (b3) A monomer having a tetrahydrofuran group and a (meth)acryloxy group is more preferable.

From the viewpoint of further improving the reliability of the resulting color filter such as heat resistance and chemical resistance, (b) is preferably (b1), from the viewpoint of excellent storage stability of the colored curable resin composition , (B1) is preferably (b1-2).

(c) Examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, Base)-2-ethylhexyl acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, (meth)acrylate Yl)cyclohexyl acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate (commonly used in this technical field) The name is "dicyclopentyl (meth)acrylate." In addition, it is also called "tricyclodecyl (meth)acrylate"), tricyclo (meth)acrylate [5.2.1.0 ^2,6 ]decene- 8-yl ester (the common name in this technical field is "dicyclopentenyl (meth)acrylate"), dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, Adamantyl (meth)acrylate, propylene (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate, etc. (Meth) acrylate; (meth) acrylates containing hydroxyl groups such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; diethyl maleate, fumar Dicarboxylic acid diesters such as diethyl acid and diethyl itaconate; dicyclic unsaturated compounds such as norbornene, 5-methylnorbornene, 5-ethylnorbornene, etc.; N-phenyl Dicarboxyimide compounds such as maleimide, N-cyclohexylmaleimide, and N-benzylmaleimide; styrene, α-methylstyrene, m-methylstyrene , P-methylstyrene, vinyl toluene, P-methoxystyrene and other vinyl-containing aromatic compounds; vinyl-containing nitriles such as acrylonitrile and methacrylonitrile; vinyl chloride, vinylidene chloride Halogenated hydrocarbons such as ethylene; vinyl-containing amides such as acrylamide and methacrylamide; esters such as vinyl acetate; 1,3-butadiene, isoprene, and 2,3-dimethyl Diene based on 1,3-butadiene, etc.

Among them, from the viewpoints of copolymerization reactivity and heat resistance, vinyl group-containing aromatic compounds, dicarboxylic imine compounds, and bicyclic unsaturated compounds are preferred. Specifically, styrene, vinyl toluene, benzyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and norbornene.

The polymer having the structural unit derived from (a) can be obtained by It is manufactured by polymerizing the monomer introduced into the polymer structural unit in a solvent in the presence of a polymerization initiator. The solvent should just be a solvent which dissolves each monomer, and the solvent (E) of the coloring curable resin composition of this invention can mention the solvent etc. mentioned later.

Examples of the carboxylic anhydride include the acid anhydrides mentioned in (a).

The resin may be used alone or in combination of two or more kinds.

The weight average molecular weight in terms of polystyrene of the binder resin (B) is preferably 3,000 or more and 100,000 or less. When the molecular weight is within the aforementioned range, the hardness of the coating film increases, the residual film rate is high, the solubility of the unexposed portion to the developer is good, and the resolution of the colored pattern tends to increase. The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the binder resin (B) is preferably 1.1 to 6, more preferably 1.2 to 4, and still more preferably 1.3 to 3.

The acid value (in terms of solid content) of the binder resin (B) is preferably 20 to 200 mg-KOH/g. The acid value is a value measured by the amount (mg) of potassium hydroxide required to neutralize 1 g of the binder resin (B), and it can be determined, for example, by titration using an aqueous potassium hydroxide solution.

The binder resin (B) contains the following resin (B1) and resin (B2).

The weight average molecular weight of (B1) is 3,000 or more and less than 12,000, and the acid value in terms of solid content is 20 to 200 mg-KOH/g.

The weight average molecular weight of (B2) is 12,000 or more and 100,000 or less, and the acid value in terms of solid content is 20 to 200 mg-KOH/g.

By including resin (B1) and resin (B2), solvent resistance can be improved, and the resulting pattern shape is also good.

The weight average molecular weight of the resin (B1) is preferably 5,000 or more, more preferably It is selected to be 7,000 or more, more preferably 8,000 or more, and preferably 11,000 or less.

The acid value of the resin (B1) is preferably 50 mg-KOH/g or more in terms of solid content, more preferably 80 mg-KOH/g or more, preferably 180 mg-KOH/g or less, and more preferably 150 mg-KOH/g or less.

Furthermore, the resin (B1) preferably contains a structural unit derived from at least one monomer (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, and a cyclic ether derived from a carbon number of 2 to 4 The structure and the polymer of the structural unit of the ethylenically unsaturated bond monomer (b). As the resin (B1), one kind or two or more kinds of copolymers can be used.

In the binder resin (B), the resin (B1) is preferably 60% by mass or more, more preferably 70% by mass or more, preferably 95% by mass or less, and more preferably 90% by mass or less.

The weight average molecular weight of the resin (B2) is preferably 70,000 or less, more preferably 50,000 or less, still more preferably 30,000 or less, and preferably 13,000 or more.

The acid value of the resin (B2) is preferably 50 mg-KOH/g or more in terms of solid content, more preferably 80 mg-KOH/g or more, preferably 180 mg-KOH/g or less, and more preferably 150 mg-KOH/g or less.

The resin (B2) is preferably a polymer having at least a structural unit derived from at least one monomer (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, and more preferably has a structural unit derived from a monomer having a carbon number of 2 The cyclic ether structure of ~4 and the structural unit of the monomer (b) of the ethylenically unsaturated bond and/or the copolymer derived from the structural unit of the monomer (c) polymerizable with the monomer (a). Resin (B2) One kind or two or more kinds of copolymers can be used.

The content ratio (B1/B2) of the resin (B1) to the resin (B2) on a mass basis is preferably 1 or more, more preferably 3 or more, still more preferably 5 or more, preferably 15 or less, more preferably 10 or less, and further Preferably it is 8 or less.

In addition, the weight average molecular weight of the polymer (weight average molecular weight of 12,000 or more and 100,000 or less) derived from the aforementioned resin (B2) and the polymer derived from the aforementioned resin (B1) (weight average molecular weight of 3,000 or more and less than 12,000) The weight average molecular weight ratio (B2/B1) is preferably 1.2 or more, more preferably 2 or more, preferably 4 or less, and more preferably 3 or less.

When preparing the above-mentioned coloring mixture, the resin (B1) and the resin (B2) may be contained in the coloring mixture, and the resin (B1) is preferably contained. Moreover, when preparing the said coloring mixture, it is preferable that resin (B1) and resin (B2) are contained in the binder resin (B) remaining except the binder resin (B) derived from a coloring mixture.

The total of the resin (B1) and the resin (B2) in the binder resin (B) is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and particularly preferably 99% by mass or more.

The total content of the binder resin (B) relative to the total solid content is preferably 7 to 65% by mass, more preferably 10 to 60% by mass, still more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass. When the content of the binder resin (B) is within the aforementioned range, the colored pattern is easily formed, and the resolution and residual film rate of the colored pattern tend to increase.

Polymeric compound (C)

The polymerizable compound (C) is freely activated by a polymerization initiator Examples of the compound in which the radical and/or acid are polymerized include polymerizable compounds having ethylenically unsaturated bonds. The polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds, and more preferably a polymerizable compound having five or six ethylenically unsaturated bonds. The polymerizable compound (C) is preferably a compound having a (meth)acrylate structure.

The polymerizable compound with one ethylenically unsaturated bond includes nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, acrylic acid -2-hydroxyethyl, N-vinylpyrrolidone, (a), (b) and (c) above. Examples of polymerizable compounds having two ethylenically unsaturated bonds include ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and bis(acryloxyethyl) of bisphenol A Ether and 3-methyl-pentanediol di(meth)acrylate. The polymerizable compound having three or more ethylenically unsaturated bonds includes trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, Meth) acrylate, dipentaerythritol hexa(meth)acrylate, ethylene glycol modified pentaerythritol tetra(meth)acrylate, glycol modified dipentaerythritol hexa(meth)acrylate, propylene glycol modified Pentaerythritol tetra(meth)acrylate, propylene glycol-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate and caprolactone-modified dipentaerythritol hexa(meth)acrylate )Acrylate.

Among them, 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 or more and 1,500 or less.

The content of the polymerizable compound (C) in the colored curable resin composition of the present invention is usually 1-60% by mass, preferably 5-50% by mass, more preferably 10-40% by mass relative to the total solid content, and further It is preferably 12 to 37% by mass. The content ratio of the binder resin (B) to the polymerizable compound (C) (binder resin (B): polymerizable compound (C)) is usually 20:80~80:20, preferably 35:65~ on a mass basis. 80:20. When the content of the polymerizable compound (C) is within the aforementioned range, the residual film rate during the formation of the colored pattern and the chemical resistance of the color filter tend to increase.

Polymerization initiator (D)

The polymerization initiator (D) is not particularly limited as long as it is a compound that generates active radicals or acid to initiate polymerization under the action of light and heat, and known polymerization initiators can be used.

The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of an alkyl phenyl ketone compound, a triazine compound, an phosphine oxide compound, an O-oxime compound, and a biimidazole compound , More preferably a polymerization initiator containing an O-oxime compound.

O- oxime compounds include N-benzyloxy-1-(4-phenylthiophenyl)butan-1-one-2-imine, N-benzyloxy-1-(4 -Phenylthiophenyl)octan-1-one-2-imine, N-benzyloxy-1-(4-phenylthiophenyl)-3-cyclopentyl-1-one-2 -Imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]ethane-1-imine, N -Acetyloxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolylmethoxy)benzyl Group}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzyl)-9H- Carbazol-3-yl]-3-cyclopentylpropane-1-imine And N-benzyloxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one -2-imine. Commercial products such as IRGACURE OXE01, OXE02 (registered trademark) (above, manufactured by BASF Corporation), N-1919, NCI-930 (manufactured by ADEKA Corporation), etc. can be used. Among them, preferred are N-benzyloxy-1-(4-phenylthiophenyl)butan-1-one-2-imine, N-benzyloxy-1-(4-phenylthio Phenyl) oct-1-one-2-imine and N-benzyloxy-1-(4-phenylthiophenyl)-3-cyclopentyl-1-one-2-imine At least one selected from the group of, more preferably N-benzyloxy-1-(4-phenylthiophenyl)oct-1-one-2-imine.

Alkyl phenyl ketone compounds include 2-methyl-2-morpholinyl-1-(4-methylmercaptophenyl)propan-1-one, 2-dimethylamino-1-(4-morpholine) Phenyl)-2-benzylbutan-1-one and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl) ) Phenyl]butan-1-one. Commercial products such as IRGACURE 369, 907, 379 (above, manufactured by BASF Corporation) can be used.

The alkyl phenyl ketone compound can be 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)benzene Yl)-1-propanone, 1-hydroxycyclohexyl phenyl ketone, oligomer of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)-1-propanone, α,α -Diethoxyacetophenone and benzyl dimethyl ketal.

Examples of triazine compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine and 2,4-bis(trichloromethyl)- 6-piperonyl-1,3,5-triazine.

Examples of the phosphine oxide compound include 2,4,6-trimethylbenzyldiphenylphosphine oxide. Commercial products such as IRGACURE 819 (registered trademark) (manufactured by BASF Corporation) can be used.

Specific examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, JP 6-75372 and JP 6-75373 The compounds described in the gazette, Japanese Patent Application Publication No. 48-38403, Japanese Patent Application Publication No. 62-174204, Japanese Patent Application Publication No. 07-010913, and compounds represented by the following formula.

Other polymerization initiators include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, o-benzoin Methyl benzoate, 4-phenylbenzophenone, 4-benzyl-4'-methyl diphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl) ) Benzophenone compounds such as benzophenone and 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone and camphorquinone; 10-butyl -2-Chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds, etc. It is preferable to use these in combination with a polymerization initiation aid (especially an amine-based polymerization initiation aid) described later.

In addition, the polymerization initiator (D) preferably combines an O-acetoxime compound and at least one selected from the group consisting of an alkyl phenyl ketone compound, a triazine compound, an phosphine oxide compound, and a biimidazole compound (more preferably Alkyl phenyl ketone compound).

In the polymerization initiator (D), the O- oxime compound is preferably 20% by mass or more Above, 30% by mass or more is more preferable, and 100% by mass or less is preferable.

The content of the polymerization initiator (D) is usually 0.1 to 40 parts by mass, preferably 0.1 to 30 parts by mass, more preferably 1 to 30 parts by mass relative to 100 parts by mass of the total amount of the binder resin (B) and polymerizable compound (C) Parts, particularly preferably 1 to 20 parts by mass.

Polymerization initiator

The polymerization initiation assistant is a compound or a sensitizer for accelerating the polymerization of the polymerizable compound (C) which is polymerized by the polymerization initiator (D). When the coloring curable resin composition of the present invention contains a polymerization initiator, it is usually used in combination with a polymerization initiator (D).

Examples of the polymerization initiation aid include amine polymerization initiation aids, alkoxyanthracene polymerization initiation aids, thioxanthone polymerization initiation aids, and carboxylic acid polymerization initiation aids.

Amine polymerization initiators include alkanolamines such as triethanolamine, methyldiethanolamine, and triisopropanolamine; N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)diphenyl methanone (commonly known as: Michler's ketone), 4,4'-bis (diethylamino) benzophenone and 4,4 '- bis (ethylmethylamino) benzophenone, wherein 4,4 Alkylalkyl benzophenones such as'-bis(diethylamino)benzophenone. Among them, alkylaminobenzophenone and 4,4'-bis(diethylamino)benzophenone are preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can be used.

Alkoxyanthracene-based polymerization initiators include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl -9,10-diethoxyanthracene, 9,10-dibutoxyanthracene and 2-ethyl-9,10-dibutoxyanthracene.

The thioxanthone-based polymerization initiators include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1 -Chloro-4-propoxythioxanthone.

Examples of the carboxylic acid polymerization initiation aid include thiophenylacetic acid, methylthiophenylacetic acid, and N-phenylglycine.

When a polymerization initiation assistant is used, the content thereof is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass relative to 100 parts by mass of the total amount of the binder resin (B) and the polymerizable compound (C). When the content of the polymerization initiation assistant is within this range, a colored pattern can be formed with higher sensitivity, so that the productivity of the color filter tends to increase.

Solvent (E)

The aforementioned colored curable resin composition may contain a solvent (E). The solvent (E) is not limited, and a solvent commonly used in this field can be used alone or in combination of two or more. Specifically, ester solvents (solvents containing -COO- but not -O- in the molecule), ether solvents (solvents containing -O- but not -COO- in the molecule), ether ester solvents (containing -COO- and -O- solvents), ketone solvents (solvents containing -CO- but not -COO- in the molecule), alcohol solvents (containing OH but not -O-, -CO- and -COO in the molecule) -Solvents), aromatic hydrocarbon solvents, amide solvents and dimethyl sulfide.

Ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate Ester, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, cyclohexyl acetate, and γ-butyl Lactone.

The ether solvent can include ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, 3-methoxy-1 -Butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, two Ethylene glycol dibutyl ether, anisole.

The ether ester solvent includes methyl methoxyacetate, methyl ethoxyacetate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2 -Methyl methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxy Butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethyl Glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, and propylene glycol diacetate.

The ketone solvent includes 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, Cyclopentanone, cyclohexanone and isodimethylacetone.

Examples of the alcohol solvent include butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerol.

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

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

These solvents can combine two or more types.

Among the above solvents, from the viewpoint of coating properties and drying properties, An organic solvent having a boiling point of 120°C or more and 210°C or less at 1 atm is preferable. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxy ethyl propionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and diethylene glycol monomethyl ether are preferred. Ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, cyclohexanone, N , N-dimethylformamide and N-methylpyrrolidone, more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, cyclohexanone, ethyl 3-ethoxypropionate, N,N-dimethylformamide and N-methyl Pyrrolidone.

The content of the solvent (E) is usually 70 to 95% by mass relative to the total amount of the colored curable resin composition, preferably 75 to 92% by mass, and more preferably 75 to 90% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating is good, and the color density at the time of forming the color filter is not insufficient, so the display characteristics tend to become good.

Leveling agent

The aforementioned colored curable resin composition may contain a leveling agent. The leveling agent includes organosilicon surfactants, fluorine surfactants, and organosilicon surfactants having fluorine atoms. They may have a polymerizable group on the side chain.

Examples of the organosilicon surfactant include surfactants having siloxane bonds in the molecule. Specific examples include TORAY SILICONE DC3PA, the same SH7PA, the same DC11PA, the same SH21PA, the same SH28PA, the same SH29PA, the same SH30PA, the same SH8400 (manufactured by Toray Dow Corning), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (trust Yue Chemical Industry Company), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (manufactured by Momentive Advanced Materials Co., Ltd.).

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specific examples include FLUORAD FC430, the same FC431 (registered trademark) (manufactured by Sumitomo 3M), MEGAFACE F142D, the same F171, the same F172, the same F173, the same F177, the same F183, the same F554, the same R30, the same RS-718-K ( Registered trademark) (made by DIC), FTOP EF301, same as EF303, same as EF351, same as EF352 (registered trademark) (manufactured by Mitsubishi Materials Electronics Co., Ltd.), SURFLON S381, same as S382, same as SC101, same as SC105 (registered trademark) (Asahi Glass Company made) and E5844 (made by Daikin Fine Chemical Research Institute).

Examples of the organosilicon surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples include MEGAFACE R08, the same BL 20, the same F475, the same F477 and the same F443 (registered trademark) (manufactured by DIC).

The content of the leveling agent relative to the total amount of the colored curable resin composition is usually 0.0005 mass% or more and 0.6 mass% or less, preferably 0.001 mass% or more and 0.5 mass% or less, more preferably 0.001 mass% or more and 0.2 mass% or less , More preferably 0.002 mass% or more and 0.1 mass% or less, particularly preferably 0.005 mass% or more and 0.07 mass% or less. When the content of the leveling agent is within the above range, the color can improve the flatness of the filter.

The content of leveling agent is relative to the solid content of the colored curable resin composition The total amount is usually 0.001 mass% or more and 2.0 mass% or less, preferably 0.002 mass% or more and 1.5 mass% or less, more preferably 0.004 mass% or more and 1.0 mass% or less, still more preferably 0.008 mass% or more and 0.5 mass% or less, especially It is preferably 0.01% by mass or more and 0.3% by mass or less.

Other ingredients

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

Method for producing colored curable resin composition

The colored curable resin composition of the present invention can be, for example, mixed with a colorant (A), a binder resin (B), a polymerizable compound (C), a polymerization initiator (D), a solvent (E), and leveling if necessary. Agent, polymerization initiator and other ingredients. The coloring agent (Aa) is added, and further coloring agents such as pigments can be mixed. The pigment is preferably mixed in advance with a part or all of the solvent (E) until the average particle diameter of the pigment is 0.2 μm or less, and used in the state of a dispersed pigment dispersion using a ball mill. At this time, part or all of the aforementioned pigment dispersant and binder resin (B) can be blended as necessary.

It is preferable to filter the mixed colored curable resin composition with a filter having a pore diameter of about 0.01 to 10 μm.

Manufacturing method of color filter

As a method of producing a colored pattern from the colored curable resin composition of the present invention, a photolithography method, an inkjet method, a printing method, etc. may be mentioned. Among them, photolithography is preferred. The photolithography method is to apply a colored curable resin composition on a substrate, dry and form a colored composition layer, and expose the colored composition layer through a photomask. Methods of development. In the photolithography method, by not using a photomask and/or not developing during exposure, it is possible to form a colored coating film as a cured product of the colored composition layer. The colored pattern and colored coating film formed in this way can be used as the color filter of the present invention.

The film thickness of the produced color filter can be appropriately adjusted according to the purpose, application, etc., and is usually 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

The substrate can be a glass plate, an adhesive resin plate, silicon, aluminum, silver, silver/copper/palladium alloy thin film, etc. formed on the aforementioned substrate. Other color filter layers, adhesive resin layers, transistors, circuits, etc. can be formed on these substrates.

The formation of pixels of each color by photolithography can be performed by known or customary equipment and conditions. For example, it can be produced as follows.

First, a colored curable resin composition is coated on a substrate, and volatile components such as a solvent are removed by heating and drying (baking) and/or under reduced pressure, and then dried to obtain a smooth colored composition layer. The coating method includes spin coating, slit coating, and slit spin coating.

Next, the coloring composition layer is exposed through a photomask for forming a target coloring pattern. In order to be able to irradiate the entire exposure surface with uniform parallel light or to properly align the photomask with the substrate on which the coloring composition layer is formed, exposure devices such as a mask aligner and a stepper are preferably used. By contacting the exposed coloring composition layer with a developing solution for development, a coloring pattern is formed on the substrate. By development, the unexposed part of the colored composition layer is dissolved and removed in the developer. The developer is preferably an aqueous solution of alkaline compounds such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, and tetramethylammonium hydroxide. The development method may be any of a slurry method, a dipping method, and a spray method. Furthermore, when developing The substrate is inclined at any angle. It is preferable to wash with water after development.

Preferably, the resulting colored pattern is further post-baked. In order to impart various characteristics, the color filter having a colored pattern and a colored coating film obtained by the above treatment may be further subjected to surface coating treatment.

The color filter formed from the colored curable resin composition of the present invention can be advantageously used as a color filter for display devices (for example, liquid crystal display devices, organic EL devices, e-books, etc.) and solid-state imaging devices.

(Example)

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples, and it is undoubtedly possible to implement appropriate changes within the scope of the above and below, and they are all included in the technical scope of the present invention. In addition, in the following, unless otherwise specified, "parts" means "parts by mass", and "%" means "% by mass".

Synthesis example 1

The following reactions were carried out in a nitrogen atmosphere. After putting 15.3 parts of N-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60 parts of N,N-dimethylformamide in a flask equipped with a cooling tube and a stirring device, the mixed solution was cooled with ice. After 5.7 parts of 60% sodium hydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was gradually added over 30 minutes under ice cooling, the mixture was stirred for 1 hour while raising the temperature to room temperature. A mixture of 4,4 '- difluoro benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.4 parts was gradually added in small reaction was stirred for 24 hours. After gradually adding a small amount of ice water 200 to the reaction solution, it was left at room temperature for 15 hours, and water was removed by decantation to obtain a viscous solid as a residue. After adding 60 parts of methanol to this viscous solid, it was stirred at room temperature for 15 hours. After filtering the precipitated solid, it was purified by column chromatography. The purified pale yellow solid was dried at 60°C under reduced pressure to obtain 9.8 parts of the compound represented by the formula (CI-18).

The following reactions were carried out in a nitrogen atmosphere. Put 8.2 parts of the compound represented by the formula (BI-7), 10 parts of the compound represented by the formula (CI-18), and 20 parts of toluene in a flask with a cooling tube and a stirring device, then add 12.2 parts of phosphonium chloride and Stir at 95~100°C for 3 hours. Next, after cooling the reaction mixture to room temperature, it diluted with 170 parts of 2-propanol. Next, after pouring the diluted reaction solution into 300 parts of saturated brine, 100 parts of toluene was added and stirred for 30 minutes. Then, the stirring was stopped, and after standing for 30 minutes, it was separated into an organic layer and an aqueous layer. After removing the water layer by a liquid separation operation, the organic layer was washed with 300 parts of saline. An appropriate amount of Glauber's salt was added to the organic layer and stirred for 30 minutes, then filtered and dried to obtain an organic layer. The solvent was removed from the obtained organic layer with an evaporator to obtain a blue-violet solid. Furthermore, the purple solid was dried at 60°C under reduced pressure to obtain 18.4 parts of a compound represented by formula (A-II-18).

The following reactions were carried out in a nitrogen atmosphere. After putting 8 parts of the compound represented by Formula (A-II-18) and 396 parts of methanol in a flask equipped with a cooling tube and a stirring device, it stirred at room temperature for 30 minutes, and prepared the blue solution. Next, after adding 396 parts of water to the blue solution, it was further stirred at room temperature for 30 minutes to obtain a reaction solution.

53 parts of water was put in the beaker, and 11.8 parts of Kelkin-type phosphotungstic acid (manufactured by Aldrich) and 53 parts of methanol were put in the water, and mixed at room temperature in an air atmosphere to prepare a phosphotungstic acid solution.

The obtained phosphotungstic acid solution was dropped into the previously prepared reaction solution over 1 hour. After further stirring for 30 minutes at room temperature, a blue solid was obtained by filtration. After dispersing the obtained blue solid in 200 parts of methanol for 1 hour, the filtration operation was repeated twice. The blue solid obtained by this operation was dried under reduced pressure at 60°C to obtain 17.1 parts of a compound represented by formula (A-I-18).

Synthesis Example 2

20 parts of the compound represented by formula (1x) and 200 parts of N-propyl-2,6-dimethylaniline (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed under shading conditions, and the resulting solution was stirred at 110°C for 6 hours . Cool the resulting reaction solution to room temperature Then, it was added to a mixed solution of 800 parts of water and 50 parts of 35% by weight hydrochloric acid and stirred at room temperature for 1 hour, and crystals were precipitated. The precipitated crystals are obtained as the residue of suction filtration, and then dried to obtain the compound represented by formula (1-32).

Synthesis Example 3

After adding 65 parts of water to 7.5 parts of 2-amino-4-methylsulfonyl-6-nitrophenol, 1.3 parts of sodium hydroxide was added and dissolved. Under ice cooling, 6.1 parts of a 35% sodium nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) aqueous solution was added, followed by gradually adding 19.4 parts of 35% hydrochloric acid to dissolve and stir for 2 hours to obtain a suspension containing diazonium salt. Next, an aqueous solution of 5.6 parts of amide sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) dissolved in 26 parts of water was slowly added to deactivate excess sodium nitrite.

Next, 5.6 parts of 3-methyl-1-phenyl-5-pyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.) was suspended in 70 parts of water, and the pH was adjusted to 8.0 using sodium hydroxide. Here, while appropriately adding 10% sodium hydroxide solution to maintain the pH in the range of 7 to 7.5, the aforementioned suspension containing the diazonium salt is dropped over 15 minutes. After completion of the dropping, stirring was continued for 30 minutes to obtain a yellow suspension. Stir for 1 hour. The yellow solid obtained by filtration was dried at 60° C. under reduced pressure to obtain 11.7 parts of the compound represented by formula (p-2) (yield 87%).

(Chemical formula 19)

Put 10 parts of the compound of formula (p-2) into 100 parts of dimethylformamide (manufactured by Tokyo Chemical Industry Co., Ltd.) and dissolve, add chromium(III) ammonium dodecahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) ) 3.1 parts of sodium acetate (manufactured by Wako Pure Chemical Industries, Ltd.) 1.1 parts, and then heated to reflux for 4.5 hours. After cooling to room temperature, the reaction solution was poured into 1500 parts of 20% salt water, and the red-orange solid obtained after filtration was dried at 60° C. to obtain 13.6 parts of the compound represented by formula (z-2) (yield 63%).

Synthesis Example 4

An appropriate amount of nitrogen gas was introduced into a flask with a reflux cooler, a dropping funnel and a stirrer to replace the nitrogen atmosphere, 371 parts by weight of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 85°C while stirring. Then, 54 parts by weight of acrylic acid, acrylic acid-3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]dec-8-yl ester and/or acrylic acid-3,4-epoxy tricyclo[ 5.2.1.0 ^2,6 ] 225 parts by weight of a mixture of dec-9-yl esters, 81 parts by weight of vinyl toluene (isomer mixture), and 80 parts by weight of 1-methoxy-2-propyl acetate Mixed solution. On the other hand, 30 parts by weight of the polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) was dropped over 5 hours and dissolved in 160 parts by weight of 1-methoxy-2-propyl acetate. In the solution. After dripping the initiator solution, keep it for 4 hours and then cool to room temperature to obtain a copolymer B1 with a type B viscosity (23°C) of 246mPa‧s, a solid content of 37.5%, and an acid value of 43mg-KOH/g. . The weight average molecular weight Mw of the resulting copolymer was 10,600, and the degree of dispersion was 2.01.

Synthesis Example 5

An appropriate amount of nitrogen was poured into a 1-L flask equipped with a reflux cooling tube, a dropping funnel, and a stirrer, and the nitrogen atmosphere was replaced. Add 141 parts by weight of ethyl lactate and 178 parts by weight of propylene glycol monomethyl ether acetate, and heat to 85°C while stirring. Next, 38 parts by weight of acrylic acid, acrylic acid-3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]dec-8-yl ester and/or acrylic acid-3,4-epoxy tricyclo[ 5.2.1.0 25 parts by weight of mixture of ^2,6 ]dec-9-yl ester, 137 parts by weight of cyclohexyl maleimide, 50 parts by weight of 2-hydroxyethyl methacrylate, propylene glycol monomethyl ether acetate 338 parts by weight of mixed solution. On the other hand, a mixed solution in which 5 parts by weight of 2,2-azobisisobutyronitrile was dissolved in 88 parts by weight of propylene glycol monomethyl ether acetate was dropped over 6 hours. After the dripping is finished, keep it at the same temperature for 4 hours and then cool to room temperature to obtain a copolymer B2 with a type B viscosity (23°C) of 23mPa‧s, a solid content of 25.6%, and a solution acid value of 28mg-KOH/g . The weight average molecular weight Mw of the resulting copolymer was 8,600, and the degree of dispersion was 2.1.

Synthesis Example 6

An appropriate amount of nitrogen was poured into a 1-L flask equipped with a reflux cooling tube, a dropping funnel, and a stirrer, and the nitrogen atmosphere was replaced. Add 300 parts of diethylene glycol ethyl methyl acetate, and heat to 85°C while stirring. Next, 54 parts of acrylic acid, acrylic acid-3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]dec-8-yl ester and/or acrylic acid-3,4-epoxytricyclo[5.2. 1.0 ^2,6 ]dec-9-yl ester mixture (content ratio is 50:50 in molar ratio) 306 parts by weight and 24 parts of 2,2-azo (2,4-dimethylvaleronitrile) are dissolved in The solution in 316 parts of diethylene glycol ethyl methyl acetate was dropped into the flask. After completion of the dripping, it was kept at 85°C for 4 hours, and then cooled to room temperature to obtain a copolymer (resin B3). The solid content of resin B3 is 37.0%, and the viscosity measured under the B-type viscometer (23℃) is 88mPa‧s. The weight average molecular weight of the resin B3 was 7,500, the acid value in terms of solid content was 91 mg-KOH/g, and the molecular weight distribution was 1.93. Resin B3 has the following structural units.

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the aforementioned binder resin polymer was performed under the following conditions by the GPC method.

Device: K2479 (manufactured by Shimadzu Corporation)

Column: SHIMADZU Shim-Pack GPC-80M

Column temperature: 40℃

Solvent; THF (tetrahydrofuran)

Concentration of tested liquid: 25mg/mL (solvent: THF)

Flow rate: 1.0mL/min

Detector: RI

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

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

Examples 1 to 5 and Comparative Examples 1 and 2

Each component was mixed with the composition shown in Tables 4 to 5, and the colored curable resin composition was obtained.

table 5

In addition, in Tables 4 to 5, each component is shown as follows. In addition, the binder resin (B) is expressed in parts by mass in terms of solid content.

Coloring agent (A); 1-1: compound represented by formula (1-32)

Coloring agent (A); 1-2: compound represented by formula (z-2)

Coloring agent (A); A1-1: compound represented by formula (A-I-18)

Coloring agent (A); A1-2: C.I. Pigment Blue 15: 6

Coloring agent (A); A1-3: C.I. Pigment Red 254

Coloring agent (A); A1-4: C.I. Pigment Blue 1

Coloring agent (A); A1-5: C.I. Pigment Red 81

Dispersant: (BYK (registered trademark)-LNP6919 (manufactured by BYK))

Binder resin (B); (B-1): Binder resin (B-1)

Binder resin (B); (B-2): Binder resin (B-2)

Binder resin (B); (B-3): Binder resin (B-3)

Binder resin (B); (B-4): Copolymer of methacrylic acid and benzyl methacrylate (the ratio of methacrylic acid unit to benzyl methacrylate unit (molar ratio) is 35:65, acid value It is 135 mg-KOH/g, and the weight average molecular weight in terms of polyethylene is 25,000) (However, when mixing, a propylene glycol monomethyl ether acetate solution with a solid content of 34% was used).

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

Polymerization initiator (D); (D-1): N-benzyloxy-1-(4-phenylthiophenyl)oct-1-one-2-imine (IRGACUREOXE 01; manufactured by BASF; Oxime compound)

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); (F-1): polyether modified silicone oil (TORAY SILICONE SH8400; manufactured by Toray Dow Corning Corporation)

Coloring pattern production

After coating the colored curable resin composition on a 5 cm square glass substrate (EAGLE 2000; manufactured by Corning Corporation) by spin coating, it was placed on a hot plate and dried at 100°C for 3 minutes to form a colored The composition layer. After leaving to cool, the space between the substrate on which the coloring composition layer was formed and the quartz glass photomask was 80 μm, and the exposure machine (TME-150RSK; manufactured by Topcon) was exposed at 35 mJ/cm ² in an atmospheric atmosphere. The amount (365nm standard) is irradiated with light to the coloring composition layer. The photomask used a photomask that formed a 50 μm line width/space pattern. The light-irradiated coloring composition layer is immersed in a developer (an aqueous solution containing 0.05% potassium hydroxide and 0.2% sodium butyl naphthalene sulfonate in mass fractions) at 25° C. for development for 60 seconds. After washing with water , Bake in a heating oven at 230°C for 30 minutes to obtain a colored pattern.

Film thickness measurement

For the obtained colored pattern, the film thickness was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 6.

Chromaticity evaluation

For the obtained coloring pattern, use a color measuring machine (OSP-SP-200; manufactured by Olympus) to measure the spectroscopy, and use the characteristic function of the C light source to measure the xy chromaticity coordinates (x, y) in the XYZ coordinate system of CIE And lightness Y. The results are shown in Table 6.

Production of colored coating film

The colored curable resin composition was coated on a 5 cm square glass substrate (EAGLE 2000; manufactured by Corning Corporation) by a spin coating method, and then dried at a temperature of 100° C. for 3 minutes to form a colored composition layer. After leaving to cool, the space between the substrate on which the coloring composition layer was formed and the quartz glass photomask was 80 μm, and the exposure machine (TME-150RSK; manufactured by Topcon) was exposed at 35 mJ/cm ² in an atmospheric atmosphere. The amount (365nm standard) is irradiated with light to the coloring composition layer. The photomask used a photomask that formed a 50 μm line width/space pattern. It was baked in a heating oven at 230°C for 30 minutes to obtain a colored coating film.

Solvent resistance evaluation

The chromaticity of the obtained colored coating film was measured with a color measuring machine (OSP-SP-200; manufactured by Olympus). Next, the obtained colored coating film was immersed in a large excess amount of N-methyl-2-pyrrolidone stored at 23°C for 30 minutes, and the chromaticity of the colored coating film after immersion was measured in the same manner.

The color difference ΔEab* of the colored coating films of Examples 1 to 5 is 3 or less, and it is considered that there is almost no change in hue, and it is considered that it exhibits good characteristics as a color filter. The results are shown in Table 6.

Color pattern shape evaluation

With respect to the resulting colored pattern, the shape was observed using a scanning electron microscope (S-4000; manufactured by Hitachi High-Tech Co., Ltd.). If it is the shape shown in (p1) of FIG. 1 (that is, a forward taper), it is ○, and if it is the shape shown in (p2), it is Δ. In the shape shown in (p1), when an inorganic film is laminated on a colored pattern, cracks or peeling tend to be hard to occur. The results are shown in Table 6.

Industrial applicability

The colored curable resin composition of the present invention has good solvent resistance.

Claims (5)

A colored curable resin composition comprising: a colorant (A), a binder resin (B), a polymerizable compound (C) and a polymerization initiator (D), characterized in that the colorant (A) is composed of The coloring agent of the compound (Aa) composed of the cation of the pigment skeleton and the anion of the compound containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen, and the binder resin (B) contains the following resin The binder resin of (B1) and resin (B2), the weight average molecular weight of (B1) is 3,000 or more and less than 12,000, the acid value in terms of solid content is 20~200mg-KOH/g, and the weight average molecular weight of (B2) is 12,000 or more and 100,000 or less, the acid value in terms of solid content is 20 to 200 mg-KOH/g, and the ratio (B2/B1) of the weight average molecular weight of the resin (B2) and the resin (B1) is 125/53 or more and 3 or less. The colored curable resin composition of claim 1, wherein the resin (B1) is a structural unit derived from at least one selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and is derived from having a carbon number of 2 A copolymer of cyclic ether structure of ~4 and structural unit of monomer with ethylenic unsaturated bond. The colored curable resin composition of claim 1 or 2, wherein the compound (Aa) is a compound represented by formula (AI), (chemical formula 1)

In the formula (AI), R ⁴¹ to R ⁴⁴ each independently represent a hydrogen atom, a saturated hydrocarbon group with 1 to 20 carbons, an optionally substituted aromatic hydrocarbon group with 6 to 20 carbons, or a substituted carbon number 7 ~30 aralkyl group, in the saturated hydrocarbon group with 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a substituted or unsubstituted amino group or halogen atom, when the saturated hydrocarbon group has 2 to 20 carbon atoms , The methylene group contained in the saturated hydrocarbon group may be substituted by an oxygen atom or -CO-, but in the saturated hydrocarbon group with 2 to 20 carbon atoms, adjacent methylene groups are not substituted by oxygen atoms at the same time, and the terminal methylene groups are not Substituted by oxygen atom or -CO-, R ⁴¹ and R ⁴² can combine and form a ring with their combined nitrogen atom, R ⁴³ and R ⁴⁴ can combine and form a ring with their combined nitrogen atom, R ⁴⁷ ~R ⁵⁴ Each independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, the methylene group constituting the alkyl group may be substituted by an oxygen atom or -CO-, and R ⁴⁸ and R ⁵² may be combined with each other And form -NH-, -O-, -S- or -SO ₂ -, but in the alkyl group, adjacent methylene groups are not substituted by oxygen atoms at the same time, and the terminal methylene groups are not replaced by oxygen atoms or -CO- Substitution, ring T ¹ represents an aromatic heterocyclic ring with a carbon number of 3 to 10 that may have a substituent, [Y] ^m- represents an essential element containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and Any m-valent anion of oxygen, and m represents an arbitrary natural number of 1 or more. A color filter formed of the coloring curable resin composition according to any one of claims 1 to 3. A display device including the color filter as claimed in claim 4.

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