KR102092349B1 - Colored photosensitive resin composition, color filter and display device - Google Patents

Abstract

The present invention relates to a colored curable resin composition, comprising a colorant (A), a binder resin (B), a polymerizable compound (C) and a polymerization initiator (D) comprising a compound (Aa) of a specific structure, and the polymerization The sex compound (C) relates to a colored curable resin composition comprising a first polymerizable compound (C1) and a second polymerizable compound (C2).

Description

Colored curable resin composition, color filter and display device {COLORED PHOTOSENSITIVE RESIN COMPOSITION, COLOR FILTER AND DISPLAY DEVICE}

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

A color filter formed of a colored curable resin composition is used in a liquid crystal display device and a solid-state imaging element. For example, Patent Document 1 discloses a colored curable resin composition comprising C.I. Pigment Blue 15: 6 and a xanthene dye.

Special Publication 2013-50693

An object of the present invention is to provide a colored curable resin composition capable of producing a color filter having a high development speed, high brightness, and good linearity when forming a colored pattern.

The present invention includes the following inventions.

[1] It contains a coloring agent (A), a binder resin (B), a polymerizable compound (C) and a polymerization initiator (D), and the coloring agent (A) is a cation having a pigment skeleton and tungsten, molybdenum, silicon and phosphorus A colorant comprising a compound (Aa) consisting of an anion of a compound containing at least one element and oxygen selected from the group consisting of, wherein the polymerizable compound (C) is a first polymerization having two or more ethylenically unsaturated bonds A colored curable resin composition comprising a sex compound (C1) and a second polymerizable compound (C2) having more ethylenically unsaturated bonds than the first polymerizable compound (C1).

[2] In the above [1], the number of ethylenically unsaturated bonds of the first polymerizable compound (C1) is 2 or more and 4 or less, and the ethylenically unsaturated bonds of the second polymerizable compound (C2) are Colored curable resin composition whose number is 5 or more and 8 or less.

[3] In the above [1] or [2], the ratio of the first polymerizable compound (C1) to the sum of the first polymerizable compound (C1) and the second polymerizable compound (C2) Colored curable resin composition of 5% by weight or more and 50% by weight or less.

[4] The colored curable resin composition according to the above [1], wherein the compound (Aa) is a compound represented by formula (A-I).

[Formula 1]

[In the formula (AI), R ⁴¹ to R ⁴⁴ are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or 7 to 7 carbon atoms which may have a substituent. 30 represents an aralkyl group, and in the saturated hydrocarbon group having 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a substituted or unsubstituted amino group or halogen atom, and the saturated hydrocarbon group has 2 to 20 carbon atoms. In the case of, the methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom or -CO-. R ⁴¹ and R ⁴² may combine to form a ring with the nitrogen atom to which they are attached, and R ⁴³ and R ⁴⁴ may combine to form a ring with the nitrogen atom to which they are attached.

R ⁴⁷ to R ⁵⁴ each independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or an alkyl group having 1 to 8 carbon atoms, and when the carbon number of the alkyl group is 2 to 8, the methylene group constituting the alkyl group is an oxygen atom or -CO-. R ⁴⁸ and R ⁵² may combine with each other to form -NH-, -O-, -S- or -SO _2- .

Ring T ¹ represents an aromatic heterocycle having 3 to 10 carbon atoms which may have a substituent.

[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 an arbitrary natural number.]

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

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

The colored curable resin composition of the present invention can produce a color filter having a pattern having a high development speed, high brightness, and good linearity when forming a colored pattern.

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).

In addition, when multiple components are exemplified in parallel in this specification, it means that each element can be used alone or in combination of multiple kinds, unless otherwise specified.

Coloring agent (A)

The colorant (A) is a compound (Aa) consisting of a cation having a pigment skeleton and an anion of a compound containing oxygen and at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus (hereinafter compound (Aa)) D). 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 having an intrinsic color by selectively absorbing visible light (wavelength; 400 to 750 nm), and the partial structure has a structure for expressing a characteristic that it has an intrinsic color. It is included.

The pigment skeletons of the cations constituting the compound (Aa) include onium in the azo pigment skeleton, xanthene pigment skeleton, azine pigment skeleton, cyanine pigment skeleton, acridine pigment skeleton, anthraquinone pigment skeleton, and squarium pigment skeleton. A pigment skeleton having a structure; Triarylmethane pigment skeleton; And a dye skeleton obtained by aromatic heterocyclization of one or more of the aromatic hydrocarbon rings of the triarylmethane skeleton. Especially, it is a pigment | skeleton which carried out aromatic heterocyclization of one or more of the aromatic hydrocarbon ring of a triarylmethane pigment | skeleton.

Anions derived from at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and oxygen-containing compounds include tungsten-containing heteropolyacid anions and tungsten-containing isopolyacid anions. Preferably, a phosphorus tungstate anion, a silicon tungstate anion, and a tungsten-based isopoly acid anion are mentioned.

Examples of tungsten-containing heteropolyacid anions and tungsten-containing isopolyacid anions are Keggin-type tungsten acid ion α- [PW ₁₂ O ₄₀ ] ^3- , Dawson-type phosphorus tungstate acid ion α- [P ₂ W ₁₈ O ₆₂ ] ^6- , β- [P ₂ W ₁₈ O ₆₂ ] ^6- , kegin-type silicon tungstate ions 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 mixtures thereof.

It is preferable that the compound (Aa) is a compound represented by formula (A-I) (hereinafter referred to as (A-I)).

[Formula 2]

[In the formula (AI), R ⁴¹ to R ⁴⁴ are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or 7 to 7 carbon atoms which may have a substituent. 30 represents an aralkyl group, and in the saturated hydrocarbon group having 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a substituted or unsubstituted amino group or halogen atom, and the saturated hydrocarbon group has 2 to 20 carbon atoms. In the case of, the methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom or -CO-. R ⁴¹ and R ⁴² may combine to form a ring together with the nitrogen atom to which they are attached, and R ⁴³ and R ⁴⁴ may combine to form a ring together with the nitrogen atom to which they are attached.

R ⁴⁷ to R ⁵⁴ each independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms, and when the alkyl group has 2 to 8 carbon atoms, the methylene group constituting the alkyl group is an oxygen atom or -CO-. R ⁴⁸ and R ⁵² may combine with each other to form -NH-, -O-, -S- or -SO _2- .

Ring T ¹ represents an aromatic heterocycle having 3 to 10 carbon atoms which may have a substituent.

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

m represents an arbitrary natural number.

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

[Formula 3]

[Wherein, ring T ¹ , R ⁴¹ ~ R ⁴⁴ and R ⁴⁷ ~ R ⁵⁴ are the same as above, respectively.]]

The aromatic hetero ring of ring T ¹ may be monocyclic or condensed. The aromatic heterocycle represented by ring T ¹ has 3 to 10 carbon atoms, and preferably 3 to 8 carbon atoms.

As the substituent which the aromatic hetero ring of ring T ¹ may have, a halogen atom, a cyano group, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (preferably an alkyl group having 1 to 20 carbon atoms), or a substituent And an aromatic hydrocarbon group having 6 to 20 carbon atoms or an amino group which may have a substituent, preferably a saturated hydrocarbon group having 1 to 20 carbon atoms (preferably an alkyl group having 1 to 20 carbon atoms), an amino group that may have a substituent. Or a C6-C20 aromatic hydrocarbon group which may have a substituent is mentioned.

Among them, the aromatic hetero ring of the ring T ¹ is preferably an aromatic hetero ring containing a nitrogen atom, and more preferably a 5-membered pentacyclic aromatic hetero ring containing a nitrogen atom. Ring T ¹ preferably has an amino group which may have a substituent such as an alkyl group having 1 to 10 carbon atoms.

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

[Formula 4]

[In formula (Ab2-y1), R ⁵⁶ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which 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 independently a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent group, or 7 to 30 carbon atoms which may have a substituent group. If it represents an aralkyl group and the saturated hydrocarbon group has 2 to 20 carbon atoms, the methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom or -CO-. R ⁴⁵ and R ⁴⁶ may combine to form a ring with the nitrogen atom to which they are attached.

* Indicates a valent bond with the carbohydrate cation.]

The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ⁴¹ to R ⁴⁶ and R ⁵⁶ may be any of straight chain, branched chain and cyclic. Saturated hydrocarbon groups of straight or branched chains include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl and icosyl groups. Alkyl groups; And branched chain alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, and 2-ethylhexyl group. 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 a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group. The cyclic saturated hydrocarbon group preferably has 3 to 10 carbon atoms, and more preferably 6 to 10 carbon atoms.

Saturated hydrocarbon groups represented by R ⁴¹ to R ⁴⁶ and R ⁵⁶ include groups represented by the following formula. In the following formula, * represents a valent bond.

[Formula 5]

The saturated hydrocarbon group of R ⁴¹ to R ⁴⁶ and R ⁵⁶ may be substituted with a substituted or unsubstituted amino group or halogen atom. As a substituted amino group, alkylamino groups, such as a dimethylamino group and diethylamino group, are mentioned, for example. In addition, examples of the halogen atom include fluorine, chlorine, bromine, and iodine. Moreover, when a halogen atom is a fluorine atom, it is preferable that it is a perfluoroalkyl group, such as a trifluoromethyl unit, a pentafluoroethyl unit, and a heptafluoropropyl unit.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ⁴⁷ to R ⁵⁴ include a group having 1 to 8 carbon atoms among the straight or branched chain saturated hydrocarbon groups illustrated as a saturated hydrocarbon group represented by R ⁴¹ .

Further, examples of the alkyl group having 1 to 10 carbon atoms represented by R ⁵⁷ include a group having 1 to 10 carbon atoms among the straight or branched chain saturated hydrocarbon groups illustrated as a saturated hydrocarbon group represented by R ⁴¹ .

When the number of carbon atoms of the saturated hydrocarbon group (preferably an alkyl group) represented by R ⁴¹ to R ⁵⁴ is 2 to 20, the methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom or -CO-, preferably oxygen. It may be substituted with an atom. Moreover, an oxygen atom may be inserted between the methylene groups constituting the saturated hydrocarbon group. In this case, the saturated hydrocarbon group is preferably a straight-chain or branched-chain saturated hydrocarbon group (ie, a straight-chain or branched-chain alkyl group), and more preferably a straight-chain saturated hydrocarbon group (ie, a straight-chain alkyl group). The preferable number of carbon atoms of the saturated hydrocarbon group in which the methylene group may be substituted with an oxygen atom or -CO- is 2 to 10, and more preferably 2 to 8. The saturated hydrocarbon group (preferably an alkyl group) preferably has 2 to 10 carbon atoms, and more preferably 2 to 8 carbon atoms. Further, when the methylene group is substituted with an oxygen atom or -CO-, the number of carbon atoms 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 It is 2 to 3, more preferably 2.

In addition, the R ⁴¹ ~ R ⁴⁶ and R ⁵⁶ aromatic hydrocarbon group which may have a substituent represented by the carbon number of 6 to 20 is preferable, more preferably having 6 to 15, more preferably having 6 to 12. Examples of the aromatic hydrocarbon group include phenyl group, tril group, xylyl group, naphthyl group, anthryl group, phenanthryl group, biphenyl group, terphenyl group, and the like, preferably phenyl group, naphthyl group, tril group, xylyl group. , And particularly preferably a phenyl group. In addition, the aromatic hydrocarbon group may have 1 or 2 or more substituents, and the substituents include halogen atoms such as fluorine atom, chlorine atom, iodine atom and bromine atom; A haloalkyl group having 1 to 6 carbon atoms such as a chloromethyl group and a trifluoromethyl group; Alkoxy groups having 1 to 6 carbon atoms such as methoxy groups and ethoxy groups; Hydroxy group; Sulfamoyl group; Alkylsulfonyl groups having 1 to 6 carbon atoms such as methylsulfonyl group; Alkoxycarbonyl groups having 1 to 6 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group; And the like.

Examples of the aralkyl group which may have a substituent group represented by R ⁴¹ to R ⁴⁶ include groups in which alkane diyl groups having 1 to 5 carbon atoms, such as methylene group, ethylene group, and propylene group, are bonded to groups described as the aromatic hydrocarbon group. .

R ⁴¹ and R ⁴² combine to form a ring with the nitrogen atom to which they are attached, R ⁴³ and R ⁴⁴ combine to form a ring with the nitrogen atom to which they are attached, and R ⁴⁵ and R ⁴⁶ combine to form a group of these Examples of the ring formed together with the nitrogen atom to be bonded include a nitrogen-containing non-aromatic 4- to 7-membered ring such as a pyrrolidine ring, a morpholine ring, a piperidine ring, and a piperadine ring, preferably pyrroli As a hetero atom, such as a din ring and a piperidine ring, the 4-7 member ring which has only one nitrogen atom is mentioned.

Among them, R ⁴¹ to R ⁴⁴ and R ⁵⁶ are preferably a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group which may have a substituent, and each independently a saturated hydrocarbon group having 1 to 8 carbon atoms or a group represented by the following formula It is more preferable. In the following formula, * represents a valent bond with a nitrogen atom.

[Formula 6]

R ⁴⁵ to R ⁴⁶ are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group which may have a group or a substituent in which an oxygen atom is inserted between carbon atoms of an alkyl group having 2 to 20 carbon atoms, or R ⁴⁵ and R ⁴⁶ are It is preferred to combine to form a ring with the nitrogen atom to which they are attached. 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 bonded to form one nitrogen atom as a hetero atom It formed a 4 to 7-membered ring having only bays. In the following formula, * represents a valent bond with a nitrogen atom.

[Formula 7]

R ⁴⁷ to R ⁵⁴ are preferably each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms, and more preferably each independently a hydrogen atom, a methyl group, a fluorine atom, or a chlorine atom.

Examples of the cation portion of the formula (A-I) include cations 1 to cation 16 represented by the formula (A-I-1) as shown in Table 1 below.

[Formula 8]

In Table 1, Ph1 to Ph9 mean groups represented by the following formula. In the formula, * represents a bond.

[Formula 9]

In Table 1, Me represents a methyl group, Et is ethyl, iPr is an isopropyl group, Bu is an n-butyl group, and EOE is an ethoxyethyl group, respectively.

Among these, cation 1 to cation 6, cation 11 to cation 16 are preferred as the cation portion of formula (AI), cation 1, cation 2 or cation 12 to cation 16 are particularly preferred, and most preferably cation 12 and 15 , 16.

The compound (Aa) includes a compound represented by the following formula.

The content of the coloring agent (Aa) in the coloring curable resin composition is usually 1% by weight or more and 70% by weight or less, preferably 5% by weight or more and 60% by weight or less, more preferably 10% by weight or more and 60% by weight with respect to the total amount of solid content. % Or less, particularly preferably 15% to 50% by weight. In addition, the content of the compound (Aa) is preferably 20% by weight or more, more preferably 40% by weight or more, more preferably 60% by weight or more, particularly preferably 80% by weight with respect to the total amount of the colorant (A) It is more than 100% by weight. When the content ratio of the compound (Aa) is within the above range, it is easier to obtain desired spectroscopy and color density. In addition, in this specification, the "total amount of solid content" refers to the total amount of components excluding the solvent from the colored curable resin composition of the present invention. The total amount of the solid content and the content (content) of each component thereof can be measured by known analytical methods such as liquid chromatography and gas chromatography.

Compound (A-I) can be produced according to the method described in Japanese Patent Application Laid-open No. 2015-28121.

Dye (Ab)

Dyestuffs include, for example, compounds known to have color in addition to pigments in the color index (published by The Society of Dyers and Colourists) or known dyes described in dyeing notes (dyeing yarns). Also, the dye is different from the compound (Aa). Xanthene dyes are particularly preferred.

The xanthene dye is a dye containing a compound having a xanthene skeleton in a molecule, and the xanthene dye is more preferably a compound represented by the following formula (a1-1) (hereinafter referred to as compound (a1-1)). desirable. The compound (a1-1) may be a tautomer thereof.

[Formula 10]

[In the formula (a1-1), R ¹ to R ⁴ are independently a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a monovalent aromatic group having 6 to 10 carbon atoms which may have a substituent. It represents a hydrocarbon group, and the methylene group (-CH _2- ) contained in the saturated hydrocarbon group may be substituted with -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 together may form a ring containing a nitrogen atom.

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

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

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

a represents the integer of 0 or 1.

X represents a halogen atom.

Z ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and 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 each 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 -is -O-, -CO-, -NH-, Or it may be substituted with -NR ^8- , R ⁹ and R ¹⁰ may be bonded to 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 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.]

The xanthene dye is more preferably a compound represented by the following formula (a1-2) (hereinafter referred to as compound (a1-2)). The compound (a1-2) may be a tautomer.

[Formula 11]

[In formula (a1-2), R ²¹ and R ²² independently of each other represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon groups of R ²¹ and R ²² are 6 to 10 carbon atoms. It may be substituted with an aromatic hydrocarbon group or a halogen atom, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 3 carbon atoms, and -CH ₂ -contained in the saturated hydrocarbon group of R ²¹ and R ²² is -O It may be substituted with-, -CO-, or -NR ^11- .

R ²³ and R ²⁴ each independently represent an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms.

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

p and q represent the integer of 0-5 independently of each other. When p is 2 or more, a plurality of R ³³ may be the same or different, and when q is 2 or more, the plurality of 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 carbon atoms of R ²¹ and R ²² include groups having 1 to 10 carbon atoms among those of R ⁸ .

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms which may be taken as a substituent include the same groups as those of 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 each independently a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms (eg, methyl group, ethyl group, propyl group, isopropyl group).

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

Examples of the alkyl sulfanyl group having 1 to 4 carbon atoms in R ²³ and R ²⁴ include methylsulfanyl group, ethylsulfanyl group, propylsulfanyl group, butylsulfanyl group and isopropylsulfanyl group.

Examples of the alkylsulfonyl group having 1 to 4 carbon atoms in R ²³ and R ²⁴ include methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group and isopropylsulfonyl group.

R ²³ and R ²⁴ are preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and more preferably a methyl group.

p and q are preferably integers from 0 to 2, and 1 or 2 is preferred.

Among them, the xanthene dyes are preferably sulfonamides of C.I. acid red 289, quaternary ammonium salts of C.I. acid red 289, sulfonamides of C.I. acid violet 102 or quaternary ammonium salts of C.I. acid violet 102.

As the xanthene dye, for example, CI acid red 51 (hereinafter, the description of CI acid red is omitted and only described by number. Others are the same.), 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 Modern Red 27 , CI Reactive Red 36 (Rose Bengal B), sulforhodamine G, xanthene dyes described in Japanese Patent Application Publication No. 2010-32999, and xanthene dyes described in Patent No. 4242760.

The coloring agent (A) may further contain a pigment (Ac).

The pigment (Ac) is not particularly limited and a known pigment can be used. For example, pigments classified as pigments in the color index (published by The Society of Dyers and Colourists) can be used alone or in combination of two or more.

Coloring mixture

In preparing 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 solution. The heat resistance of the color filter formed from the color curable resin composition can be further increased by mixing the color mixture solution, the binder resin (B), the polymerizable compound (C), and the polymerization initiator (D) to prepare a color curable resin composition.

Any solvent that can be used as the solvent (E) of the colored curable resin composition can be used as the solvent. Examples of the solvent include an ether ester solvent, preferably a solvent in which one hydroxy group of alkylene glycol or polyalkylene glycol is etherified, and the remaining hydroxy group is esterified, for example, propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate And the like. These may contain single or multiple types.

The content of the solvent in the colored mixed solution is, for example, 1 to 50 parts by weight, preferably 2 to 30 parts by weight, and more preferably 3 to 10 parts by weight based on 1 part by weight of the compound (Aa).

It is preferable to use a dispersing agent in preparing a colored mixed solution by dispersing the compound (Aa) in a solvent. As the dispersant, known pigment dispersants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic can be used. These pigment dispersants may be used alone or in combination of two or more. As the pigment dispersant, KP (made by Shin-Etsu Chemical Industry Co., Ltd.), Proren (manufactured by Gongyoung Chemical Co., Ltd.), Solsperth (manufactured by Geneca Co., Ltd.), EFKA (manufactured by BASF), Azisper (Ajinomoto Fine) Techno Co., Ltd.) and Disperbyk (manufactured by BICKEMISA).

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

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

When a colored mixture is prepared by dispersing the compound (Aa) in a solvent, the colored mixed solution may contain a part or all of the binder resin (B) contained in the colored curable resin composition, preferably a part in advance. By including the binder resin (B) in advance, dispersion stability when produced with a colored curable resin composition can be further improved. The content of the binder resin (B) in the colored mixed solution is, for example, 1 to 300 parts by weight, preferably 10 to 100 parts by weight, and more preferably 20 to 70 parts by weight with respect to 100 parts by weight of the compound (Aa).

The content of the coloring agent (A) in the coloring curable resin composition is usually 1% by weight or more and 80% by weight or less, preferably 5% by weight or more and 70% by weight or less, more preferably 10% by weight or more and 70% by weight with respect to the total amount of solid content. It is less than or equal to 15% by weight, particularly preferably greater than or equal to 15% by weight and less than or equal to 65% by weight. When the content rate of the colorant (A) is within the above range, desired spectroscopy and color density are more easily obtained. In addition, in this specification, the "total amount of solid content" refers to the total amount of components excluding the solvent from the colored curable resin composition of the present invention. The total amount of the solid content and the content of each component thereof can be measured by known analytical methods such as liquid chromatography and gas chromatography.

When the colorant (A) contains a dye (Ab), the ratio (Aa / Ab) of the compound (Aa) to the dye (Ab) is preferably 2 or more by weight, more preferably 5 or more, and more preferably Is 10 or more, particularly preferably 12 or more, preferably 400 or less, more preferably 100 or less, further preferably 30 or less, particularly preferably 20 or less, and even more preferably 18 or less.

When the coloring agent (A) contains the dye (Ab), the coloring mixture solution containing the dye (Ab) or the mixing solution containing the dye (Ab) and the solvent may be prepared in advance.

Binder resin (B)

The binder resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and at least one monomer (b1) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter also referred to as "(b1)"). It is more preferable that it is a polymer having a structural unit derived from.

The binder resin (B) is preferably a copolymer having a structural unit derived from a monomer (b2) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (referred to as "(b2)") and other structural units. .

Other structural units include monomers (b1) and copolymerizable monomers (b3) (however, they are different from monomers (b1) and monomers (b2), hereinafter also referred to as "(b3)"), ethylenically unsaturated bonds And structural units having the same.

(b1) includes unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinyl benzoic acid;

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

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hepto-2-ene, 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene , A bicyclo unsaturated compound containing a carboxyl group such as 5-carboxymethylbicyclo [2.2.1] hepto-2-ene, 5-carboxyethylbicyclo [2.2.1] hepto-2-ene;

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

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

and unsaturated acrylates containing hydroxy groups and carboxyl groups in the same molecule, such as α- (hydroxymethyl) acrylic acid.

Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferred from the viewpoint of copolymerization reactivity and solubility of the resulting resin in an aqueous alkali solution.

(b2) refers to a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. . (b2) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

As (b2), a monomer having an oxyranyl group and an ethylenically unsaturated bond (b2-1) (hereinafter referred to as "(b2-1)"), a monomer having an oxetanyl group and an ethylenically unsaturated bond (b2-2) (hereinafter "(B2-2)" and a monomer (b2-3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter referred to as "(b2-3)").

As the (b2-1), a monomer (b2-1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as "(b2-1-1)") and an alicyclic unsaturated hydrocarbon And a monomer (b2-1-2) having an epoxidized structure (hereinafter referred to as "(b2-1-2)").

As (b2-1-1), a monomer having a glycidyl group and an ethylenically unsaturated bond is preferable. As (b2-1-1), glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinyl Benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycidyl ether, α-methyl-p-vinylbenzylglycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyl Oxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene , 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene and 2,4,6-tris (glycidyloxymethyl) styrene You can.

As (b2-1-2), vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide (registered trademark) 2000; manufactured by Daicel Corporation), 3,4- Epoxycyclohexylmethyl (meth) acrylate (for example, cyclomer (registered trademark) A400; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, cyclomer M100; Daicel Co., Ltd.), the compound represented by Formula (1), and the compound represented by Formula (2).

[Formula 12]

[Wherein, 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 with a hydroxy 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 a bonding hand with O.]

The compound represented by Formula (1) and the compound represented by Formula (2) may be used alone, or a compound represented by Formula (1) and a compound represented by Formula (2) may be used in combination. When using these together, the ratio of the compound represented by Formula (1) and the compound represented by Formula (2) (the compound represented by Formula (1): the compound represented by Formula (2)) is preferably on a molar basis. It is 5: 95-95: 5, More preferably, it is 10: 90-90: 10, More preferably, it is 20: 80-80: 20.

As (b2-2), a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. As (b2-3), a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable.

It is preferable that (b2) is (b2-1) in that the reliability of heat filter, chemical resistance, etc. of the obtained color filter can be further increased, and (b2-1) from the viewpoint of excellent storage stability of the colored curable resin composition. ) Is more preferably (b2-1-2).

Examples of the (b3) include a hydroxy group-containing (meth) acrylic acid ester monomer (b3-1) and a dicarbonylamide derivative monomer (b3-2).

As a hydroxy group-containing (meth) acrylic acid ester monomer (b3-1), 2-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4- Hydroxybutyl (meth) acrylate, 1,3-butanediol (meth) acrylate, 1,4-butanediol (meth) acrylate, 1,6-hexanediol (meth) acrylate, 3-methylpentanediol (meth And hydroxy group-containing alkyl (meth) acrylic acid esters such as acrylates.

The hydroxy group-containing (meth) acrylic acid ester monomer is preferably a hydroxyalkyl (meth) acrylic acid ester having an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, further It is preferably a hydroxy group-containing (meth) acrylic acid ester having an alkyl group having 1 to 4 carbon atoms.

(b3-1) is preferably hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate And more preferably 2-hydroxyethyl (meth) acrylate.

As the monomer (b3-2) of the dicarbonylimide derivative, dicarbonylimide having aromatic hydrocarbon groups such as N-phenylmaleimide and N-trimaleimide, N-cyclohexylmaleimide, and N-cycloheptylmaleimide And dicarbonylimides having aralkyl groups such as dicarbonylimide having an alicyclic hydrocarbon group, N-benzylmaleimide, and N-phenethylmaleimide.

The monomer (b3-2) of the dicarbonylimide derivative is preferably an N-substituted maleimide having a hydrocarbon group having 4 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, It is more preferable that it is an N-substituted maleimide having an aralkyl group or a succinimidyl group having 7 to 20 carbon atoms. The substituent of the N-substituted maleimide is more preferably an alicyclic hydrocarbon group having 4 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 16 carbon atoms, or an aralkyl group having 7 to 16 carbon atoms.

The hydrogen atom contained in the hydrocarbon group may be substituted with an amino group, an alkoxy group having 1 to 5 carbon atoms, a phenylamino group, a halogen atom, or a hydroxy group.

In particular, the monomer of the dicarbonylimide derivative is preferably an N-substituted maleimide having an alicyclic hydrocarbon group having 4 to 20 carbon atoms, N-cyclohexylmaleimide, N-cycloheptylmaleimide, and N-cyclooctylmaleimide , N-cyclododecyl maleimide is more preferable, and N-cyclohexyl maleimide is more preferable.

As (b3), monomers (b3-3) other than (b3-1) and (b3-2), methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec -Butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate , Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.O ^2,6 ] decane-8-yl (meth) acrylate (In the related technical field, it is known as "dicyclopentanyl (meth) acrylate" by its common name. It is also called "tricyclodecyl (meth) acrylate."), Tricyclo [5.2.1.O ^2,6 ] Decene-8-yl (meth) acrylate (known in the art as "dicyclopentenyl (meth) acrylate" as a common name. C.), dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, aryl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) (Meth) acrylic acid esters such as acrylate, naphthyl (meth) acrylate, and benzyl (meth) acrylate; Dicarboxylic acid diesters such as diethyl maleate, diethyl phthalate, and diethyl itaconic acid;

Bicyclo unsaturated compounds such as bicyclo [2.2.1] hepto-2-ene, 5-methylbicyclo [2.2.1] hepto-2-ene, and 5-ethylbicyclo [2.2.1] hepto-2-ene ;

Vinyl group-containing aromatic compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene; Vinyl group-containing nitriles such as acrylonitrile and methacrylonitrile; Halogenated hydrocarbons such as vinyl chloride and vinylidene chloride; Vinyl group-containing amides such as acrylamide and methacrylamide; Esters such as vinyl acetate; Dienes of 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene; And the like.

Among these, (b3-3), from the viewpoint of copolymerization reactivity and heat resistance, vinyl group-containing aromatic compounds and bicyclo unsaturated compounds are preferable. Specifically, styrene, vinyl toluene, benzyl (meth) acrylate, tricyclo [5.2.1.O ^2,6 ] decane-8-yl (meth) acrylate, and bicyclo [2.2.1] hepto-2- Yen is preferred.

The monomer constituting the structural unit derived from (b1) can be produced by polymerizing the monomer constituting the structural unit of the polymer in a solvent in the presence of a polymerization initiator. As a solvent, what is necessary is just to dissolve each monomer, and the solvent etc. which are mentioned later as a solvent (E) of the colored curable resin composition of this invention are mentioned.

If necessary, a reaction catalyst (for example, tris (dimethylaminomethyl) phenol) and a polymerization inhibitor (for example, hydroquinone, etc.) of a carboxylic acid or a carboxylic acid anhydride with a cyclic ether may be used.

Examples of the carboxylic anhydride include acid anhydrides exemplified in (b1).

The resins can be used alone or in combination of two or more.

The polystyrene equivalent weight average molecular weight of the binder resin (B) is usually 3,000 to 100,000, preferably 4,000 to 50,000, more preferably 5,000 to 35,000, further preferably 5,000 to 30,000, and most preferably 5,500 to It is 30,000. When the molecular weight is within the above range, the coating film hardness is improved, the residual film ratio is high, the solubility in the unexposed portion of the developer is good, and the resolution of the colored pattern tends to be improved. 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, more preferably 1.3 to 3 It is more preferable.

The acid value (in terms of solid content) of the binder resin (B) is preferably 1 to 170 mg-KOH / g, more preferably 15 to 150 mg-KOH / g, more preferably 80 mg-KOH / g to 135 mg-KOH / g. The acid value is a value measured by the amount of potassium hydroxide (mg) required to neutralize 1 g of the binder resin (B), and can be obtained by titration using, for example, an aqueous potassium hydroxide solution.

Especially, it is preferable that a binder resin (B) contains a structural unit derived from (b1) and a structural unit derived from (b2) at least.

In addition, it is preferable that the binder resin (B) of the present invention includes a structural unit derived from (b3), and a structural unit derived from a hydroxy group-containing (meth) acrylic acid ester monomer (b3-1) and a dicarbonylimide derivative. It is more preferable to include at least one (preferably both) of the structural unit derived from the monomer (b3-2).

In this case, the binder resin (B) preferably contains copolymers of (b1), (b2), (b3-1), and (b3-2). The content ratio of this copolymer is preferably 50% by weight or more, more preferably 60% by weight or more, and even more preferably 100% by weight or less in the binder resin (B).

The sum of (b3-1) and (b3-2) is preferably 25% by weight or more and 90% by weight or less, more preferably 35% by weight or more, more preferably among all the monomers constituting the binder resin (B). Is 40% by weight or more, particularly preferably 45% by weight or more, more preferably 90% by weight or less, and still more preferably 80% by weight or less.

The total content of the binder resin (B) is preferably 7 to 65% by weight, more preferably 10 to 60% by weight, more preferably 13 to 60% by weight, and particularly preferably 17 to 55% by weight based on the total amount of solid content. Weight percent. When the content of the binder resin (B) is within the above range, it is easy to form a colored pattern, and there is a tendency that the resolution and residual film ratio of the colored pattern are improved.

Polymerizable compound (C)

As the polymerizable compound (C), a polymerizable compound having two or more ethylenically unsaturated bonds is used, and among them, two or more compounds having different numbers of ethylenically unsaturated bonds are used as the polymerizable compound (C). . That is, the polymerizable compound (C) is a first polymerizable compound (C1) having two or more ethylenically unsaturated bonds and a second polymerizable compound having more ethylenically unsaturated bonds than the first polymerizable compound (C1). (C2).

The difference between the number of ethylenically unsaturated bonds of the first polymerizable compound (C1) and the number of ethylenically unsaturated bonds of the second polymerizable compound (C2) is preferably 2 or more, and preferably 4 or less. In addition, the number of ethylenically unsaturated bonds of the first polymerizable compound (C1) is preferably 2 or more and 4 or less. The number of ethylenically unsaturated bonds of the second polymerizable compound (C2) is preferably 5 or more, and preferably 8 or less.

In addition, when the first polymerizable compound (C1) or the second polymerizable compound (C2) includes two or more polymerizable compounds, the number of ethylenically unsaturated bonds is the first polymerizable compound (C1) or It is taken as the value calculated | required by weighted average with respect to the 2nd polymerizable compound (C2). Specifically, the value obtained by multiplying the weight ratio and the number of ethylenically unsaturated bonds for each type of the polymerizable compound included is the sum.

The first polymerizable compound (C1) and the second polymerizable compound (C2) are preferably compounds having a (meth) acrylic acid ester structure, and more preferably compounds having an acrylic acid ester structure. Further, the polymerizable compounds (C1) and (C2) are more preferably (meth) acrylic acid esters (preferably acrylic acid esters) of the polyol compound.

Examples of the polyol compound include diols such as alkanediol and benzenediol; Triols such as trimethylolpropane, tris (hydroxyethyl) isocyanurate, and tris (hydroxymethyl) ethyl succinic acid; Tetraols such as pentaerythritol; Hexaols such as dipentaerythritol; Octaol, such as tripentaerythritol; Decaol such as tetrapentaerythritol; And the like.

Polymerizable compounds having two or more ethylenically unsaturated bonds include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di ( Polymerizable compounds having two ethylenically unsaturated bonds such as meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, and 3-methylpentanediol di (meth) acrylate; Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, 2,2,2-tris (meth) acryloyl Polymerizable compounds having three ethylenically unsaturated bonds such as oxymethylethylsuccinic acid; Ethylenically unsaturated bonds such as pentaerythritol tetra (meth) acrylate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate Polymerizable compound having four; Polymerizable compounds having five ethylenically unsaturated bonds such as dipentaerythritol penta (meth) acrylate; Dipentaerythritol hexa (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. Polymerizable compounds having six ethylenically unsaturated bonds; Polymerizable compounds having seven ethylenically unsaturated bonds such as tripentaerythritol hepta (meth) acrylate; Polymerizable compounds having eight ethylenically unsaturated bonds such as tripentaerythritol octa (meth) acrylate; Polymerizable compounds having nine ethylenically unsaturated bonds such as tetrapentaerythritol nona (meth) acrylate; Polymerizable compounds having 10 ethylenically unsaturated bonds such as tetrapentaerythritol deca (meth) acrylate; And the like.

The molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, more preferably 250 or more and 1,500 or less. In addition, the molecular weight of the first polymerizable compound (C1) is preferably 150 or more and less than 500, more preferably 200 or more and 450 or less. The molecular weight of the second polymerizable compound (C2) is preferably 500 or more and 2,900 or less, and more preferably 550 or more and 1,500 or less.

The proportion of the first polymerizable compound (C1) is preferably 5% by weight or more and 50% by weight or less, more preferably with respect to the sum of the first polymerizable compound (C1) and the second polymerizable compound (C2). It is 10% by weight or more and 35% by weight or less, and more preferably 15% by weight or more and 30% by weight or less.

The ratio of the sum of the first polymerizable compound (C1) and the second polymerizable compound (C2) contained in the polymerizable compound (C) is preferably 80% by weight in 100% by weight of the total amount of the polymerizable compound (C). It is at least weight%, more preferably at least 90% by weight, still more preferably at least 95% by weight, particularly preferably at least 98% by weight, and most preferably at most 100% by weight.

The polymerizable compound (C) may further include other polymerizable compounds (C3). Other polymerizable compounds (C3) include nonylphenylcarbitolacrylate, 2-hydroxy-3-phenoxypropylacrylate, 2-ethylhexylcarbitolacrylate, 2-hydroxyethylacrylate, and N-vinylpy A polymerizable compound having one ethylenically unsaturated bond such as lollydon, (a), (b) and (c) described above; And the like.

When the polymerizable compound (C) contains other polymerizable compounds (C3), the content thereof is preferably 2% by weight or more and 20% by weight or less, and 5% by weight or more and 10% by weight, among 100% by weight of the polymerizable compound (C). % Is more preferable.

The content rate of the polymerizable compound (C) in the colored curable resin composition of the present invention is preferably 1% by weight or more and 60% by weight or less, more preferably 5% by weight or more and 50% by weight or less, more preferably with respect to the total amount of solid content. It is 10% by weight or more and 40% by weight or less, particularly preferably 12% by weight or more and 37% by weight or less. The content ratio (binder resin (B): polymerizable compound (C)) of the binder resin (B) and the polymerizable compound (C) is preferably 20:80 to 80:20 on a weight basis, more preferably 35 : 65 to 80:20. When the content of the polymerizable compound (C) is within the above range, the residual film rate at the time of forming the colored pattern and the chemical resistance of the color filter tend to improve.

Polymerization initiator (D)

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating polymerization by generating active radicals, acids, and the like by light and thermal action, and a known polymerization initiator can be used. It is preferable that the polymerization initiator (D) is a photopolymerization initiator capable of initiating polymerization by the action of light.

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

O-acyloxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1 -On-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1- [9-ethyl-6 -(2-methylbenzoyl) -9H-carbazol-3-yl] ethan-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl) -2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethan-1-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropan-1-imine and N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropan-1-one-2-imine. You may use commercially available products, such as Ilgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF), N-1919, and NCI-930 (made by ADEKA). Among them, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2 At least one member selected from the group consisting of -imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine is preferred, and N-benzoyloxy-1 -(4-phenylsulfanylphenyl) octane-1-one-2-imine is more preferable.

The alkylphenone compound is 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutane -1-one and 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one. You may use commercial items, such as Ilgacure 369, 907, 379 (above, BASF Corporation).

The alkylphenone compound is 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propane-1- Oligomers of on, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α, α-diethoxyacetophenone and benzyldimethylke It can be ride.

Triazine compounds include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6-pipero Neil-1,3,5-triazine.

The acylphosphine oxide compound includes 2,4,6-trimethylbenzoyldiphenylphosphine oxide. You may use commercial items, such as Irgacure (registered trademark) 819 (manufactured by BASF).

As the biimidazole compound, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, Japanese Patent Publication No. Hei 6-75372, and Japanese Patent Publication No. 6-75373 , The compound described in Japanese Patent Application Publication No. 48-38403, Japanese Patent Application Publication No. 62-174204, Japanese Patent Application Publication No. Hei 07-010913, compounds represented by the following formulas, and the like.

[Formula 13]

Other polymerization initiators include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, methyl 2-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone , 2,4,6-trimethylbenzophenone and other benzophenone compounds; Quinone compounds such as 9,10-phenansrenquinone, 2-ethylanthraquinone, and camphorquinone; And 10-butyl-2-chloroacridone, benzyl, phenylglyoxylic acid methyl ester, and titanocene compounds. It is preferable to use these together with the polymerization start adjuvant mentioned later (especially amine polymerization start adjuvant).

Further, as the polymerization initiator (D), at least one selected from the group consisting of O-acyloxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds and biimidazole compounds (more preferably alkylphenone compounds) It is preferable to combine.

The content of the O-acyloxime compound in the polymerization initiator (D) is preferably 20% by weight or more, more preferably 30% by weight or more, and preferably 100% by weight or less.

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

Polymerization initiation aid

The polymerization initiation aid is a compound or sensitizer used to promote polymerization of the polymerizable compound (C) in which polymerization is initiated by the polymerization initiator (D). When the coloring curable resin composition of this invention contains a polymerization start adjuvant, it is generally used with a polymerization initiator (D).

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

Examples of the amine-based polymerization start aid include alkanolamines such as triethanolamine, methyldiethanolamine, and triisopropanolamine; N, N-dimethyl-p-toluidine, 4,4'-bis (dimethylamino) benzophenone (commonly called mihirazketone), 4,4'-bis (diethylamino) benzophenone and 4,4 And '-bis (ethylmethylamino) benzophenone, preferably alkylaminobenzophenone such as 4,4'-bis (diethylamino) benzophenone; And more preferably alkylaminobenzophenone, and more preferably 4,4'-bis (diethylamino) benzophenone. You may use commercial items, such as EAB-F (made by Hodogaya Chemical Industry Co., Ltd.).

Examples of the alkoxyanthracene-based polymerization initiation aids are 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and 9, And 10-dibutoxyanthracene and 2-ethyl-9,10-dibutoxyanthracene.

Examples of the thioxanthone polymerization initiators include 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichlorothioxanthone and 1-chloro-4-propone. And Fox City oxanthone.

Examples of carboxylic acid-based polymerization initiation aids include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, and N-phenylglycine.

In the case of using a polymerization initiation aid, the content is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the total amount of the binder resin (B) and the polymerizable compound (C). When the content of the polymerization initiation aid is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.

Solvent (E)

The solvent (E) is not limited, and solvents generally used in the field may be used alone or in combination of two or more. Specifically, an ester solvent (a solvent containing -COO- in a molecule and not containing -O-), an ether solvent (a solvent containing -O- in a molecule and not containing -COO-), an ether ester solvent (Solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule, not containing -COO-), alcohol solvent (containing OH in the molecule -O-, -CO- and -COO-free solvents), aromatic hydrocarbon solvents, amide solvents and dimethyl sulfoxide.

Ester solvents include methyl lactic acid, ethyl lactic acid, butyl lactic acid, methyl-2-hydroxyisobutanoic acid, ethyl acetate, butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionic acid, isopropyl butyric acid, ethyl butyric acid, butyl And butyric acid, methylpyruvic acid, ethylpyruvic acid, propylpyruvic acid, methyl acetoacetic acid, ethyl acetoacetic acid, cyclohexanol acetate and γ-butyrolactone.

Ether solvents 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 methylethyl ether, diethylene glycol dibutyl ether, anisole, Phenitol and methylanisole.

Ether ester solvents include butyl methoxyacetate, methyl ethoxyacetate, methyl-3-methoxypropionic acid, ethyl-3-ethoxypropionic acid, methyl-2-methoxypropionic acid, methyl-2-methoxy-2-methylpropionic acid , Ethyl-2-ethoxy-2-methylpropionic acid, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether Acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate and propylene glycol diacetate.

As a ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclo Pentanone, cyclohexanone and isophorone.

Alcoholic solvents include butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol and glycerin.

Aromatic hydrocarbon solvents include benzene, toluene, xylene and mesitylene.

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

You may combine two or more of these solvents.

Among the above-mentioned solvents, an organic solvent having a boiling point at 1 atm of 120 ° C or more and 210 ° C or less is preferable in terms of coatability and dryness. In particular, propylene glycol monomethyl ether acetate, ethyl lactic acid, propylene glycol monomethyl ether, ethyl-3-ethoxypropionic acid, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, dipropylene glycol methyl ether acetate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, cyclohexanone. N, N-dimethylformamide and N-methylpyrrolidone are preferred, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether acetate, ethyl lactic acid, 3-me More preferred are methoxybutyl acetate, 3-methoxy-1-butanol, cyclohexanone, ethyl-3-ethoxypropionic acid, N, N-dimethylformamide and N-methylpyrrolidone.

The content of the solvent (E) is generally 70 to 95% by weight, preferably 75 to 92% by weight, more preferably 75 to 90% by weight, based on the total amount of the coloring curable resin composition. When the content ratio of the solvent (E) is in the above range, the flatness at the time of application becomes good, and when forming a color filter, the color density does not become insufficient, so the display characteristics tend to be improved.

Leveling agent

Leveling agents include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having fluorine atoms. These may have a polymerizable group in the side chain.

Examples of the silicone surfactant include surfactants having a siloxane bond in the molecule. Specifically, Toray silicone DC3PA, copper SH7PA, copper DC11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper SH8400 (manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, And KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials, Japan).

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Prorad (registered trademark) FC430, copper FC431 (Sumitomo 3M Co., Ltd.), Megaface (registered trademark) F142D, copper F171, copper F172, copper F173, copper F177, copper F183, copper F554, copper R30 , Copper RS-718-K (manufactured by DIC Corporation), F-top (registered trademark) EF301, copper EF303, copper EF351, copper EF352 (manufactured by Mitsubishi Material Electronic Chemical Co., Ltd.), sulfron (registered trademark) S381, Copper S382, Copper SC101, Copper SC105 (made by Asahi Glass Co., Ltd.) and E5844 (made by Daikin Fine Chemical Research Institute).

Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in a molecule. Specifically, Megaface (registered trademark) R08, copper BL20, copper F475, copper F477 and F443 (made by DIC Corporation) are mentioned.

The content rate of the leveling agent is generally 0.0005% by weight or more and 0.6% by weight or less, preferably 0.001% by weight or more and 0.5% by weight or less, more preferably 0.001% by weight or more and 0.2% by weight or less, based on the total amount of the coloring curable resin composition, More preferably, it is 0.002% by weight or more and 0.1% by weight or less, particularly preferably 0.005% by weight or more and 0.07% by weight or less. When the content rate of the leveling agent is within the above range, the flatness of the color filter can be improved.

Other ingredients

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

Manufacturing method of colored curable resin composition

The colored curable resin composition of the present invention is, for example, a compound (Aa), a binder resin (B), a polymerizable compound (C), a polymerization initiator (D) as a colorant (A), and a dye, a solvent, and leveling as necessary. Agents, polymerization initiation aids, and other components. As the coloring agent (A), a coloring agent such as a pigment may be added to the compound (Aa) and mixed. It is preferable that the pigment is premixed with a part or all of the solvent (E) and used in the state of a pigment dispersion liquid dispersed using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. At this time, part or all of the pigment dispersant and the binder resin (B) may be blended as necessary.

After mixing, it is preferable to filter the colored curable resin composition with a filter having a filter diameter of about 0.01 to 10 μm.

Manufacturing method of color filter

The photolithography method, the inkjet method, the printing method etc. are mentioned as a method of manufacturing the colored pattern which becomes a pixel from the colored curable resin composition of this invention. Among these, photolithography is preferred. The photolithography method is a method in which a colored curable resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed and developed through a photomask to obtain a colored pattern. In the photolithography method, a colored coating film which is a cured product of the colored composition layer can be formed by not using and / or not developing a photomask during exposure. The colored pattern or colored coated film thus formed can be used as the color filter of the present invention.

The thickness of the color filter to be produced can be appropriately adjusted according to the purpose or use, and is generally 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

As a substrate, a glass or resin plate, silicon, or an aluminum, silver, silver / copper / palladium alloy thin film formed on the substrate is used. Separate color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates.

The formation of each color pixel by the photolithography method can be carried out by known or conventional devices and conditions. For example, it can be prepared as follows.

First, the colored curable resin composition is applied onto a substrate, and volatile components such as a solvent are removed and dried by heating drying (pre-baking) and / or drying under reduced pressure to obtain a smooth colored composition layer. As a coating method, a spin coating method, a slit coating method, and a slit and spin coating method are mentioned.

Next, the coloring composition layer is exposed through a photomask for forming a desired coloring pattern. It is preferable to use an exposure apparatus such as a mask aligner and a stepper because it is possible to uniformly irradiate parallel light uniformly over the entire exposure surface or to accurately align the photomask and the substrate on which the coloring composition layer is formed. A colored pattern is formed on the substrate by developing the colored composition layer after exposure by contacting it with a developer. By development, the unexposed portion of the colored composition layer is dissolved in the developer and removed. As the developer, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, or tetramethylammonium hydroxide is preferred. The developing method may be any of a pudling process, a dipping method, and a spraying method. It is also possible to tilt the substrate at any angle during development. It is preferable to wash with water after development.

It is preferable to post-bak additionally to the obtained coloring pattern. The color filter having the colored pattern or colored coating thus obtained can be additionally subjected to a surface coating treatment to impart various characteristics.

The color filter formed from the colored curable resin composition of the present invention is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic papers, etc.) and solid-state imaging devices.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples, and it is of course possible to carry out appropriate changes in a range that can be suitable for the purpose of the latter period. All are included in the technical scope of the present invention. In the following, "parts" means "parts by weight" and "%" means "% by weight" unless otherwise specified.

Synthesis Example 1

The following reaction proceeded under a nitrogen atmosphere. 15.3 parts of N-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60 parts of N, N-dimethylformamide were added to a flask equipped with a cooling tube and a stirring device, and the mixed solution was ice-cooled. Under ice cooling, 5.7 parts of 60% sodium hydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was gradually added over 30 minutes, followed by stirring for 1 hour while raising the temperature to room temperature. 10.4 parts of 4,4'-difluorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) was gradually added to the reaction solution and stirred at room temperature for 24 hours. After the reaction solution was gradually added to 200 parts of ice water, the mixture was left standing at room temperature for 15 hours, and water was removed by decantation. As a result, a viscous solid was obtained as a residue. After adding 60 parts of methanol to this viscous solid, it was stirred at room temperature for 15 hours. The precipitated solid was separated by filtration and 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 formula (C-I-18).

[Formula 14]

The following reaction was performed under nitrogen atmosphere. Into a flask equipped with a cooling tube and a stirring device, 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 were added, and then 12.2 parts of phosphorus oxychloride were added. And stirred at 95 ° C to 100 ° C for 3 hours. After the reaction mixture was cooled to room temperature, it was diluted with 170 parts of isopropanol. The diluted reaction solution was poured into 300 parts of saturated saline, and then 100 parts of toluene was added and stirred for 30 minutes. Subsequently, the stirring was stopped and left standing for 30 minutes, and the organic layer and the water layer were separated. After the water layer was discarded by separating operation, the organic layer was washed with 300 parts of saturated brine. After adding an appropriate amount of the glauber salt to the organic layer and stirring for 30 minutes, it was filtered to obtain a dried organic layer. The obtained organic layer was evaporated to remove the solvent to obtain a blue-violet solid. Further, the blue-violet solid was dried under reduced pressure at 60 ° C. to obtain 18.4 parts of the compound represented by formula (A-II-18).

[Formula 15]

The following reaction was performed under nitrogen atmosphere. To a flask equipped with a cooling tube and a stirring device, 8 parts of a compound represented by formula (A-II-18) and 396 parts of methanol were added, followed by stirring at room temperature for 30 minutes to prepare a blue solution. Subsequently, 396 parts of water was added to the blue solution, followed by stirring at room temperature for 30 minutes to obtain a reaction solution.

53 parts of water was added to a beaker, and 11.8 parts of keggin-type tungsten acid (manufactured by Aldrich) and 53 parts of methanol were added to the water, and mixed under air atmosphere at room temperature to prepare a phosphorus tungsten acid solution.

The obtained phosphorus tungsten acid solution was dripped over the reaction solution prepared earlier over 1 hour. Then, the mixture was stirred at room temperature for 30 minutes and then filtered to obtain a blue solid. After the obtained blue solid was poured into 200 parts of methanol and dispersed for 1 hour, the operation of filtering was repeated twice. The blue solid obtained in the above operation was poured into 200 parts of water, dispersed for 1 hour, and then the operation of filtering was repeated twice. The blue solid obtained in the above operation was dried under reduced pressure at 60 ° C. to obtain 17.1 parts of the compound represented by formula (A-I-18).

[Formula 16]

Synthesis Example 2

The following reaction was performed under nitrogen atmosphere. Tris (dibenzylidene acetone) dipalladium (manufactured by Aldrich) 0.5 parts, XPhos (manufactured by Aldrich) 1.1 parts, sodium tert-butoxide (manufactured by Tokyo Chemical Industries, Ltd.) in a flask equipped with a cooling tube and a stirring device After adding 34 parts and 40 parts of 4,4'-dichlorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.), a solution of 43 parts of N-isopropyl aniline (manufactured by Wako Pure Chemical Industries, Ltd.) and 531 parts of toluene was added dropwise. . It heated up to 80 degreeC, stirred for 2 hours, and cooled to room temperature. After the reaction solution was filtered, separation and purification were performed using 200 parts of filtrate and 1 normal hydrochloric acid. The obtained organic layer was separated and purified by 200 parts of 5% sodium carbonate aqueous solution. The obtained organic layer was dried over 120 parts of magnesium sulfate, and the solid content was filtered off. The obtained organic layer was distilled and dried under reduced pressure at 60 ° C. to obtain 47 parts of the compound represented by formula (C-I-19).

[Formula 17]

The following reaction was performed under nitrogen atmosphere. To a flask equipped with a cooling tube and a stirring device, 1.9 parts of the compound represented by formula (BI-7), 3.1 parts of the compound represented by formula (CI-19) and 20 parts of toluene were added, and then 9.0 parts of phosphorus oxychloride were added. And stirred at 95 ~ 100 ℃ for 3 hours. After the reaction mixture was cooled to room temperature, it was diluted with 46.6 parts of isopropanol. The diluted reaction solution was poured into 149.1 parts of saturated brine, and then 124.2 parts of isopropanol was added and stirred for 30 minutes. After stirring was stopped and allowed to stand for 30 minutes, the organic layer and the water layer were separated. After the water layer was discarded by separating operation, the organic layer was washed twice with 91.6 parts of saturated saline. An appropriate amount of magnesium sulfate was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was removed with a solvent using an evaporator to obtain a blue-violet solid. Further, the blue-violet solid was dried under reduced pressure at 60 ° C. to obtain 4.0 parts of the compound represented by formula (A-II-19).

[Formula 18]

[Formula 19]

The following reaction was performed under nitrogen atmosphere. To a flask equipped with a cooling tube and a stirring device, 8 parts of the compound represented by formula (A-II-19) and 396 parts of methanol were added, followed by stirring at room temperature for 30 minutes to prepare a blue solution. Subsequently, 396 parts of water was added to the blue solution, followed by stirring at room temperature for 30 minutes to obtain a reaction solution.

53 parts of water was added to a beaker, and 11.8 parts of keggin-type tungsten acid (manufactured by Aldrich) and 53 parts of methanol were added to the water, and mixed under air atmosphere at room temperature to prepare a phosphorus tungsten acid solution.

The obtained phosphorus tungsten acid solution was dripped over the reaction solution prepared earlier over 1 hour. Then, the mixture was stirred at room temperature for 30 minutes and then filtered to obtain a blue solid. After the obtained blue solid was poured into 200 parts of methanol and dispersed for 1 hour, the operation of filtering was repeated twice. The blue solid obtained in the above operation was poured into 200 parts of water, dispersed for 1 hour, and then the operation of filtering was repeated twice. The blue solid obtained in the above operation was dried under reduced pressure at 60 ° C. to obtain 17.1 parts of the compound represented by formula (A-I-19).

[Formula 20]

Synthesis Example 3

The following reaction was performed under nitrogen atmosphere. Tris (dibenzylidene acetone) dipalladium (manufactured by Aldrich) 2.7 parts, XPhos (manufactured by Aldrich), 5.7 parts, sodium tert-butoxide (manufactured by Tokyo Chemical Industries, Ltd.) in a flask equipped with a cooling tube and a stirring device 25.3 parts, 30 parts of 4,4'-dichlorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and then 29 parts of 2,6-dimethylaniline (manufactured by Wako Pure Chemical Industries, Ltd.) and 154.6 parts of toluene were added dropwise. did. It heated up to 80 degreeC, stirred for 2 hours, and cooled to room temperature. The reaction solution was diluted with 900 parts of ethyl acetate, and then separated and purified with 900 parts of ion-exchanged water. The obtained organic layer was separated and purified by 900 parts of 1 normal hydrochloric acid, and then separated and purified by 900 parts of 5% sodium carbonate aqueous solution. The obtained organic layer was dried over 90 parts of magnesium sulfate, and the solid content was filtered off. After distilling the obtained organic layer with a rotary evaporator, the obtained solid was washed with 560 parts of toluene. The obtained solid was washed again with 186.9 parts of toluene, and then dried at 60 ° C. under reduced pressure to obtain 42.2 parts of the compound represented by formula (C-I-20-1).

[Formula 21]

The following reaction was performed under nitrogen atmosphere. Into a flask equipped with a cooling tube and a stirring device, 10.0 parts of a compound represented by formula (CI-20-1) and 75.2 parts of DMF were added and stirred for 30 minutes, followed by potassium tert-butoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) 8.0 parts were added. After stirring for 30 minutes, 11.1 parts of ethane iodide was added dropwise and stirred at 35 ° C for 3 hours. After the reaction solution was cooled to room temperature, it was added dropwise to 300 parts of ion-exchanged water and stirred for 30 minutes. The resulting suspension was filtered, and the residual solid was washed with 300 parts of ion-exchanged water. The obtained solid was washed with 74.8 parts of methanol, then washed with 41.0 parts of methanol, dried at 60 ° C under reduced pressure to obtain 1.6 parts of the compound represented by formula (C-I-20-2).

[Formula 22]

A compound represented by formula (A-I-20) was obtained in the same manner as in Example 1, except that the compound represented by formula (C-I-18) was changed to a compound represented by formula (C-I-20-2).

[Formula 23]

Synthesis Example 4

A compound represented by formula (C-I-21) was obtained in the same manner as in Synthesis Example 3, except that ethane iodide was changed to butane iodide.

[Formula 24]

A compound represented by formula (A-I-21) was obtained in the same manner as in Example 1, except that the compound represented by formula (C-I-18) was changed to a compound represented by formula (C-I-21).

[Formula 25]

Synthesis Example 5

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

[Formula 26]

Synthesis Example 6

To a flask equipped with a reflux cooler, a dropping funnel, and a stirrer, nitrogen was flowed at 0.02 L / min to replace it with a nitrogen atmosphere, and 200 parts of 3-methoxy-1-butanol and 105 parts of 3-methoxybutyl acetate were added to 70 ° C while stirring. Heated. Subsequently, the molar ratio of 60 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by formula (1-1) and a compound represented by formula (2-1) 50:50) A mixture of.) 240 parts of 3-methoxybutyl acetate was dissolved in 140 parts to prepare a solution, and the solution was added dropwise into a flask kept at 70 ° C for 4 hours using a dropping funnel. On the other hand, a solution in which 30 parts of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in 225 parts of 3-methoxybutyl acetate was added dropwise to the flask over 4 hours using another dropping funnel. After the dropping of the polymerization initiator solution was completed, the mixture was maintained at 70 ° C for 4 hours, and then cooled to room temperature to obtain a resin B-1b solution having a solid content of 32.6% and an acid value of 110 mg-KOH / g (in terms of solid content). The obtained resin B-1b had a weight average molecular weight Mw of 13,400 and a molecular weight distribution of 2.50.

[Formula 27]

Preparation of dispersion

10 parts of the compound represented by formula (AI-18), 2 parts of dispersant (BYK (registered trademark) -LPN6919 (manufactured by BIC Chemie Japan)), 4 parts of resin B-1b (in terms of solid content), propylene glycol monomethyl ether 84 parts of acetate and 300 parts of 0.2 mm zirconia beads were mixed and shaken vigorously for 6 hours using a paint conditioner (manufactured by Red Devil) to prepare a dispersion (1).

Synthesis Example 7

A 1 L flask equipped with a reflux cooler, a dropping funnel and a stirrer was replaced with a nitrogen atmosphere by flowing an appropriate amount of nitrogen, and 141 parts of ethyl lactic acid and 178 parts of propylene glycol monomethyl ether acetate were added and heated to 85 ° C while stirring. Subsequently, 38 parts of acrylic acid, 25 parts of 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] deca-8 or / and 9-ylacrylate, 137 parts of cyclohexylmaleimide, 2-hydroxyethyl methacryl A mixed solution of 50 parts of rate and 338 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, a mixed solution in which 5 parts of 2,2-azobisisobutylonitrile was dissolved in 88 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of dropping, the mixture was maintained at the same temperature for 4 hours, and then cooled to room temperature to obtain a copolymer having a B-type viscosity (23 ° C.) of 22 mPas and a 25.5% solid acid value of 28 mg-KOH / g. The resulting copolymer had a weight average molecular weight Mw of 7700 and a molecular weight distribution of 2.1.

Measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the binder resin was performed under the following conditions using the GPC method.

Device; K2479 (manufactured by Shimadzu Corporation)

column; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ℃

menstruum; THF (tetrahydrofuran)

Test sample concentration; 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 number average molecular weight in terms of polystyrene obtained above was defined as a molecular weight distribution (Mw / Mn).

Examples 1 to 7 and Comparative Example 1

Each component was mixed so as to have the composition indicated in Table 4 to obtain a colored curable resin composition.

A1-1 ¹⁾ Silver dispersant, B-1 ⁵⁾ and propylene glycol monomethyl ether acetate in the amounts described in the column E-1 ⁶⁾ were mixed and previously dispersed.

A1-2 ⁷⁾ was pre-dispersed by mixing propylene glycol monomethyl ether acetate in the amounts described in the dispersants, B-1 ⁵⁾ and E-1 ⁶⁾ .

A1-3 ⁸⁾ was pre-dispersed by mixing propylene glycol monomethyl ether acetate in the amounts described in the dispersants, B-1 ⁵⁾ and E-1 ⁶⁾ .

A1-4 ⁹⁾ was previously dispersed by mixing propylene glycol monomethyl ether acetate in the amounts described in the dispersants, B-1 ⁵⁾ and E-1 ⁶⁾ .

A1-5 ²⁾ was pre-dispersed by mixing an acrylic pigment dispersant, propylene glycol monomethyl ether acetate in the amounts described in columns B-1 ⁵⁾ and E-1 ⁶⁾ .

B-1 ³⁾ represents the total content of the resin B-1.

E-1 ⁴⁾ represents the sum of propylene glycol monomethyl ether acetate content.

In addition, each component in Table 4 shows the following. In addition, the binder resin (B) was expressed in parts by weight in terms of solid content.

Colorant (A); 1-1; Compound represented by formula (1-32)

Colorant (A); A1-1; Compound represented by formula (A-I-18)

Colorant (A); A1-2; Compound represented by formula (A-I-19)

Colorant (A); A1-3; Compound represented by formula (A-I-20)

Colorant (A); A1-4; Compound represented by formula (A-I-21)

Colorant (A); A1-5; C.I.Pigment Blue 15: 6

Dispersant; (BYK (registered trademark) -LPN6919 (manufactured by BIC Chemie Japan))

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

Polymerizable compound (C); (C1-1); Trimethylolpropane acrylate (KAYARAD TMPTA; manufactured by Nippon Chemical Co., Ltd.)

Polymerizable compound (C); (C1-2); Pentaerythritol triacrylate (A-TMM-3L; manufactured by Shin-Nakamura Chemical Co., Ltd.)

Polymerizable compound (C); (C1-3); 2,2,2-trisacryloyloxymethylethyl succinic acid (CBX-0; manufactured by Shin-Nakamura Chemical Co., Ltd.)

Polymerizable compound (C); (C1-4); Ethoxylated isocyanuric acid triacrylate (A-9300; manufactured by Shin-Nakamura Chemical Co., Ltd.)

Polymerizable compound (C); (C2-1); Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Chemical Co., Ltd.)

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

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

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

Leveling agent (F); (F-1); Polyether modified silicone oil (Toray Silicone SH8400; manufactured by Toray Industries)

Production of patterns

The colored curable resin composition was coated on a 5 cm square glass substrate (Eagle 2000; manufactured by Corning) by spin coating, and then prebaked at 100 ° C. for 3 minutes. After cooling, the distance between the substrate coated with the colored curable resin composition and the quartz glass photomask was set to 80 μm, and an exposure amount of 35 mJ / cm ² in an atmospheric atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) ( 365nm). As the photomask, a 50 μm line and space pattern was formed. After light irradiation, the coating film was immersed in a developing solution (an aqueous solution containing 0.05% of potassium hydroxide and 0.2% of sodium butylnaphthalenesulfonic acid in weight fractions) at 25 ° C for 60 seconds, and post-washed for 30 minutes at 230 ° C in an oven. A coloring pattern was obtained by baking.

Solubility evaluation

The 2-inch glass substrate (Eagle 2000; manufactured by Corning) was washed in the order of neutral detergent, water and ethanol and dried. After spin-coating the color curable resin composition on this glass substrate, it was pre-baked at 100 ° C for 3 minutes in a clean oven to form a color composition layer.

Subsequently, the substrate on which the coloring composition layer was formed was immersed in a developing solution having a liquid temperature of 25 ° C (aqueous solution containing 0.05% of potassium hydroxide and 0.2% of sodium butylnaphthalenesulfonic acid in weight fraction), followed by development of a 10 mm portion from the center of the substrate. The time at which dissolution ended was defined as the dissolution time. If the dissolution time is 25 seconds or less, solubility is good. The colored curable resin composition can be said to have high productivity because it is possible to produce a colored pattern in which development defects such as residues are suppressed even when the development time is short. Table 5 shows the results.

Film thickness measurement

The obtained colored pattern was measured for the film thickness using a film thickness measuring device (DEKTAK3; manufactured by Japan Vacuum Technology Co., Ltd.). Table 5 shows the results.

Chromaticity evaluation

The obtained coloring pattern is measured by spectroscopy using a colorimeter (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the xy chromaticity coordinates (x, y) and brightness in the XYZ colorimeter of the CIE using the characteristic function of the C light source. Y was measured. Table 5 shows the results.

Observation of linearity

After development, the washed substrate was observed for the linearity of the pattern formed using a scanning electron microscope (S-4000; manufactured by Hitachi High Technology). When the deviation width of the formed pattern was 1.0 μm or less, ○, and when the deviation width of the formed pattern exceeded 1.0 μm, and there was a problem with linearity, it is shown in Table 5.

The colored curable resin composition of the present invention can form a color filter having a high development speed, high brightness, and good linearity when forming a colored pattern.

Claims (6)

It contains a coloring agent (A), a binder resin (B), a polymerizable compound (C), and a polymerization initiator (D),
The colorant (A) is a cation having a pigment skeleton,
It includes a compound (Aa) consisting of an anion of a compound containing at least one element and oxygen selected from the group consisting of tungsten, molybdenum, silicon and phosphorus,
It is a colorant further comprising a xanthene dye,
The polymerizable compound (C) is a first polymerizable compound (C1) having two or more ethylenically unsaturated bonds and a second polymerizable compound having more ethylenically unsaturated bonds than the first polymerizable compound (C1). Colored curable resin composition comprising a compound (C2). The number of ethylenically unsaturated bonds of the first polymerizable compound (C1) is 2 or more and 4 or less, and the number of ethylenically unsaturated bonds of the second polymerizable compound (C2) is 5 or more and 8 The colored curable resin composition below. The coloring according to claim 1, wherein the proportion of the first polymerizable compound (C1) is 5 wt% or more and 50 wt% or less with respect to the sum of the first polymerizable compound (C1) and the second polymerizable compound (C2). Curable resin composition. The colored curable resin composition according to claim 1, wherein the compound (Aa) is a compound represented by formula (AI):
[Formula 1]

In formula (AI), R ⁴¹ to R ⁴⁴ are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or 7 to 30 carbon atoms which may have a substituent. Represents an aralkyl group, and in the saturated hydrocarbon group having 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a substituted or unsubstituted amino group or halogen atom, and the saturated hydrocarbon group has 2 to 20 carbon atoms. In this case, the methylene group included in the saturated hydrocarbon group may be substituted with an oxygen atom or -CO-, and R ⁴¹ and R ⁴² may combine to form a ring together with the nitrogen atom to which they are attached, and R ⁴³ and R ⁴⁴ are To form a ring with the nitrogen atom to which they are attached,
R ⁴⁷ to R ⁵⁴ each independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or an alkyl group having 1 to 8 carbon atoms, and when the carbon number of the alkyl group is 2 to 8, the methylene group constituting the alkyl group is an oxygen atom or -CO- may be substituted, R ⁴⁸ and R ⁵² may combine with each other to form -NH-, -O-, -S- or -SO _2- ,
Ring T ¹ represents an aromatic heterocycle having 3 to 10 carbon atoms which may have a substituent,
[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 an essential element,
m represents an arbitrary natural number. The color filter formed from the said coloring curable resin composition in any one of Claims 1-4. A display device comprising the color filter according to claim 5.