TWI664241B - Salt-forming dyes and colored hardening resin compositions - Google Patents

Abstract

The salt-forming dye of the present invention is formed of a monovalent cationic dye, a divalent anionic compound, and a monovalent cationic compound having no color-developing group.

Description

Salt-forming dyes and colored hardening resin compositions

The present invention relates to a salt-forming dye and colored hardening resin composition

A dye is used as a coloring agent for a color filter included in a liquid crystal display device or the like or a solid-state imaging element. As the dye, for example, a compound represented by the formula (A-III-1) is described in WO2012 / 128318 (in the formula, Et represents an ethyl group).

The present invention includes the following inventions.

[1] A salt-forming dye formed of a monovalent cationic dye, a divalent anionic compound, and a monovalent cationic compound having no color-developing group.

[2] The salt-forming dye according to [1], which is formed of a monovalent anionic dye formed by a monovalent cationic dye and a divalent anionic compound, and a monovalent cationic compound having no color-developing group.

[3] The salt-forming dye according to [1] or [2], wherein the divalent anionic compound is an aromatic compound having two identical monovalent anions, or a heteroaromatic compound having two identical monovalent anions.

[4] The salt-forming dye according to [3], wherein the monovalent anion is a sulfonate anion.

[5] of [1] to [4], a salt of a dye, wherein the divalent anion is a compound of formula (1b) represented by ^{_{the, - O 3 SR 1b -SO 3}} - (1b )

(In the formula, R ^1b represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent.)

[6] The salt-forming dye according to any one of [1] to [5], wherein the monovalent cationic dye is a compound represented by formula (1-a),

[In the formula (1-A), R ^1A to R ^8A each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 20 carbon atoms is included -CH ₂ -may be substituted with -O-; R ^9A to R ^12A each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group having 6 to 20 carbon atoms which may have a substituent -Hydrocarbon groups, -CH ₂ -contained in alkyl groups having 1 to 20 carbon atoms may be substituted with -O-; A represents aromatic hydrocarbon groups having 6 to 20 carbon atoms which may have a substituent, or A heteroaromatic hydrocarbon group having 2 to 10 carbon atoms].

[7] The salt-forming dye according to any one of [1] to [6], wherein the monovalent cationic compound having no chromogenic group has at least one member selected from the group consisting of a polymerizable group, a silicon atom, and a phosphorus atom. Compounds in the group that do not have a chromophore.

[8] A coloring agent comprising the salt-forming dye according to any one of [1] to [7].

[9] A coloring curable resin composition comprising the coloring agent according to the above [8], a resin, a polymerizable compound, and a polymerization initiator.

[10] A coating film formed from the colored curable resin composition according to the above [9].

[11] A color filter formed from the coloring curable resin composition according to the above [9].

[12] A display device including the color filter as described in [11] above.

<Salt-forming dye (I)>

The dye of the present invention is a salt-forming dye (hereinafter sometimes referred to as a salt-forming dye (I)) formed of a monovalent cationic dye, a divalent anionic compound, and a compound having a monovalent cation and no color-developing group.

In the present invention, a monovalent anionic dye is usually formed from a monovalent cationic dye and a divalent anionic compound. Hereinafter, this anionic dye may be referred to as "anionic dye (I-1)". The salt-forming dye (I) can be formed from an anionic dye (I-1) and a monovalent cationic compound having no color-developing group.

In addition to the anionic dye (I-1), the salt-forming dye of the present invention is further formed of a monovalent cationic compound having no color-developing group, and thus has a higher chroma than the anionic dye (I-1).

Examples of the monovalent cationic dye include a cation having two or more phenyl groups. Specific examples of the cationic dye include a compound represented by formula (1-a) and a tautomer of the compound.

[In the formula (1-a), R ^1A to R ^8A each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 20 carbon atoms, and the alkyl group having 1 to 20 carbon atoms is included in -CH ₂ -may be replaced by -O-.

R ^9A to R ^12A each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and an alkyl group having 1 to 20 carbon atoms The contained -CH ₂ -may be replaced by -O-.

A represents an aromatic hydrocarbon group having 6 to 20 carbons which may have a substituent, or a heteroaromatic hydrocarbon group having 2 to 10 carbons which may have a substituent]

Examples of the halogen atom represented by R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A, and R ^8A include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred. Or chlorine atom.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A, and R ^8A include straight-chain, branched-chain, and cyclic alkyl groups. Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, third butyl, pentyl, hexyl, heptyl, 2-ethylhexyl, Octyl, nonyl, decyl, undecyl, dodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl, cyclo Octyl, cycloheptyl, cyclodecyl, decahydronaphthyl, adamantyl, 2-alkyladamantane-2-yl, 1- (adamantane-1-yl) alkane-1-yl, Methyl, methyl Base and different base.

The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms.

-CH ₂ -contained in the alkyl group having 1 to 20 carbon atoms represented by R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A, and R ^8A may be substituted with -O-. However, when -CH ₂ -contained in an alkyl group having 1 to 20 carbon atoms is substituted with -O-, -O- is not included as a carbon number.

-CH ₂ -contained in the alkyl group having 1 to 20 carbon atoms represented by R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A, and R ^8A is replaced with -O-, and Examples of the bases include the bases described below. In the formula, * represents a bond.

Examples of R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A, and R ^8A include alkyl groups having 1 to 20 carbon atoms represented by R ^9A , R ^10A , R ^11A, and R ^12A . The alkyl groups having 1 to 20 carbon atoms are the same.

-CH ₂ -contained in the alkyl group having 1 to 20 carbon atoms represented by R ^9A , R ^10A , R ^11A and R ^12A may be substituted with -O-. However, in the case where -CH ₂ -contained in the alkyl group having 1 to 20 carbon atoms is substituted with -O-, -O- is not included in the carbon number.

Examples of the group in which -CH ₂ -included in the alkyl group having 1 to 20 carbon atoms represented by R ^9A , R ^10A , R ^11A, and R ^12A is substituted with -O- include R ^1A and R ^2A -CH ₂ -contained in the alkyl group having 1 to 20 carbon atoms represented by R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A is substituted with -O- .

Examples of the substituent that the alkyl group having 1 to 20 carbon atoms represented by R ^9A , R ^10A , R ^11A, and R ^12A may have include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; an amine group and Dimethylamino and the like -NR ¹¹¹ R ¹¹² (R ¹¹¹ and R ¹¹² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).

Examples of the alkyl group having 1 to 20 carbon atoms which may have a substituent represented by R ^9A , R ^10A , R ^11A and R ^12A include the groups described below. * Indicates a bond with a nitrogen atom.

Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R ^9A , R ^10A , R ^11A and R ^12A include a phenyl group, a naphthyl group and an anthracenyl group.

Examples of the substituent which the aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R ^9A , R ^10A , R ^11A, and R ^12A may have include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and iodine; a chloromethyl group; Haloalkyl groups having 1 to 6 carbons such as trifluoromethyl; alkoxy groups having 1 to 6 carbons such as methoxy and ethoxy; hydroxy; sulfamoyl; methylsulfonyl ~ 6 alkylsulfonyl.

Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms represented by A include a phenyl group and a naphthyl group, and an aromatic hydrocarbon group having 6 to 10 carbon atoms is preferred.

The heteroaromatic hydrocarbon group having 2 to 10 carbon atoms represented by A may have at least one heteroatom as a constituent element of the ring.

Examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom.

Examples of the heteroaromatic hydrocarbon group having 2 to 10 carbon atoms represented by A include pyridyl, imidazolyl, pyrazolyl, Oxazolyl, iso An oxazolyl, thiazolyl, isothiazolyl, benzothiazolyl, benzoisothiazolyl, thienyl, benzothienyl, preferably a heteroaromatic hydrocarbon group having 2 to 8 carbon atoms, more preferably having at least one The heteroaromatic hydrocarbon group having 2 to 8 carbon atoms of the nitrogen atom is more preferably a heteroaromatic hydrocarbon group having 2 to 8 carbon atoms (for example, a thiazolyl group) having a nitrogen atom and a sulfur atom.

Examples of the substituent in the aromatic hydrocarbon group having 6 to 20 carbon atoms represented by A include a halogen atom, an amino group which may have a substituent, and an alkyl group having 1 to 6 carbon atoms.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, third butyl, pentyl, neopentyl, and Jiji.

Examples of the substituent in the amine group include an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, and an aromatic hydrocarbon group which may have a substituent.

In A, examples of the alkyl group having 1 to 20 carbon atoms include straight-chain, branched-chain, and cyclic alkyl groups. Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, N-butyl, second butyl, third butyl, pentyl, hexyl, heptyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl, cyclopropyl , Cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl, cyclooctyl, cycloheptyl, cyclodecyl, decahydronaphthyl, adamantyl, 2- Alkyladamantane-2-yl, 1- (adamantane-1-yl) alkane-1-yl, Methyl, methyl Base and different base.

Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms represented by A as a substituent include a phenyl group and a naphthyl group.

Examples of the substituent in the aromatic hydrocarbon group include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; an alkoxy group having 1 to 4 carbon atoms such as a methoxy group and an ethoxy group; a methyl group and an ethyl group Alkyl groups having 1 to 4 carbon atoms such as propyl, isopropyl, butyl, second butyl, and third butyl.

Examples of the amine group having a substituent include an alkylamine group such as a methylamino group and an ethylamino group; a phenylamino group, a 2-fluorophenylamino group, a 2-chlorophenylamino group, (p-methyl Phenylamino groups such as oxyphenyl) amino groups and (o-methylphenyl) amino groups; Dialkylamino groups such as dimethylamino and diethylamino groups; N-phenyl-N-methylamino groups Alkylphenyls such as N- (o-methylphenyl) -N-methylamino, N- (o-methylphenyl) -N-ethyl, N-phenyl-N-isopropylamino Amine.

Examples of the substituent which the heteroaromatic hydrocarbon group having 2 to 10 carbon atoms represented by A may have: a halogen atom, an alkyl group having 1 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. And an amine group which may have a substituent.

As a halogen atom, an alkyl group having 1 to 20 carbon atoms, and a substituent having 6 to 20 carbon atoms Specific examples of the aromatic hydrocarbon group and the amine group which may have a substituent include the examples given as the substituent which the aromatic hydrocarbon group may have, respectively.

Examples of the base represented by A include the base represented by formula (A1-1) to the base represented by formula (A1-13), and the base represented by formula (A1-2) and the formula (A1-7) are preferred. ), The base represented by formula (A1-8) and the base represented by formula (A1-9), and further preferably the base represented by formula (A1-8) and the base represented by formula (A1-9) The base of representation.

The monovalent cationic dye represented by the formula (1-a) is preferably a compound represented by the formula (1-a-1) and a tautomer thereof.

[In the formula (1-a-1), X represents an oxygen atom or a sulfur atom.

R ⁴⁵ and R ⁴⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbons which may have a substituent or an aromatic hydrocarbon group having 6 to 20 carbons which may have a substituent, and the carbon number 1 which may have a substituent is 1 -CH ₂ -contained in the ~ 20 alkyl group may be substituted with -O-.

R ⁵⁵ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

R ^1A ~ R ^12A respectively have the same meaning as above]

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ⁴⁵ and R ⁴⁶ include straight chain, branched chain, and cyclic alkyl groups. Specific examples thereof include methyl, ethyl, n-propyl, Isopropyl, n-butyl, second butyl, third butyl, pentyl, hexyl, heptyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl , Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl, cyclooctyl, cycloheptyl, cyclodecyl, decahydronaphthyl, adamantane Base, 2-alkyladamantane-2-yl, 1- (adamantane-1-yl) alkane-1-yl, Methyl, methyl Base and different base.

Examples of the substituent which the alkyl group having 1 to 20 carbon atoms represented by R ⁴⁵ and R ⁴⁶ may have include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; an amine group and a dimethylamino group- NR ¹¹¹ R ¹¹² (R ¹¹¹ and R ¹¹² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).

Examples of the alkyl group having 1 to 20 carbon atoms which may have a substituent represented by R ⁴⁵ and R ⁴⁶ include the alkyl group having 1 to 20 carbon atoms represented by R ^9A , R ^10A , R ^11A, and R ^12A . The same substituents.

Examples of the aromatic hydrocarbon group represented by R ⁴⁵ and R ⁴⁶ include a phenyl group, a tolyl group, and a naphthyl group.

Examples of the substituent which the aromatic hydrocarbon group represented by R ⁴⁵ and R ⁴⁶ may have include a C1-C4 alkyl group such as a methyl group and an ethyl group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; ; Alkoxy groups with 1 to 6 carbons, such as methoxy and ethoxy; Haloalkyls with 1 to 6 carbons, such as chloromethyl and trifluoromethyl; Hydroxyl; Aminosulfonyl; Methylsulfonyl Alkylsulfonyl groups with 1 to 6 carbon atoms.

Examples of the aromatic hydrocarbon group which may have a substituent represented by R ⁴⁵ and R ⁴⁶ include the groups described below. * Indicates a bond with a nitrogen atom.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ⁵⁵ include those having 1 to 20 carbon atoms represented by R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A, and R ^8A . The same alkyl group.

Examples of the aromatic hydrocarbon group which may have a substituent represented by R ⁵⁵ are the same as the aromatic hydrocarbon group which may have a substituent represented by R ⁴⁵ and R ⁴⁶ .

R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A, and R ^{8A are} preferably each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms, and more preferably, they are each independently A hydrogen atom, a methyl group, a fluorine atom, or a chlorine atom.

R ^9A , R ^10A , R ^11A, and R ^12A are each preferably independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and more preferably each independently is It may have a halogen atom, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an alkyl group having 1 to 8 carbon atoms.

R ⁴⁵ and R ⁴⁶ are each preferably an alkyl group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and more preferably a halogen atom having 1 to 6 carbon atoms and independently A haloalkyl group having 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms in a hydroxy group, or an alkyl group having 1 to 8 carbon atoms.

R ^{55 is} preferably an alkyl group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and more preferably a halogen alkyl group having 1 to 6 carbon atoms and a carbon number of 1 which may have a halogen atom. An alkoxy group of 6 to 6 or an aromatic hydrocarbon group of 6 to 20 carbons or an alkyl group of 1 to 8 carbons.

Examples of the monovalent cationic dye include a compound represented by the formula (1-a-2) to a compound represented by the formula (1-a-14), and a compound represented by the formula (1-a-2), The compound represented by formula (1-a-3), the compound represented by formula (1-a-5), and the compound represented by formula (1-a-6).

The divalent anionic compound means a compound having a total of two valences of anions in the compound, preferably a compound having two monovalent anions, and more preferably a compound having two identical monovalent anions.

Examples of the monovalent anion include a sulfonate anion [-SO ₃ ^-] or carboxylate anions [-COO ^-], preferably a sulfonate anion.

The divalent anionic compound is preferably an aromatic compound having two monovalent anions or a heteroaromatic compound having two monovalent anions, more preferably an aromatic compound having two monovalent anions, and still more preferably at least The aromatic compound having one sulfonate anion is particularly preferably a compound represented by the formula (1-b).

_{^{- O 3 SR 1b -SO 3 -}} (1b)

(In the formula, R ^1b represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent.)

Examples of the aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R ^1b include a phenyl group, a naphthyl group, and an anthryl group, and a phenyl group or a naphthyl group is preferred.

Examples of the substituent which the aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R ^1b may have include a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom; a nitro group; a hydroxyl group; an amine group; a methyl group, an ethyl group, 1 to 4 alkyl groups such as propyl, isopropyl, butyl, second butyl, and third butyl; or methoxy, ethoxy, propoxy, isopropoxy, butoxy Alkoxy groups having 1 to 4 carbon atoms such as, second butoxy group and third butoxy group; preferably a hydroxyl group or an amine group.

When the aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R ^1b is a phenyl group, it is preferable that the other monovalent anion is located at the meta or ortho position with respect to one monovalent anion.

When the aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R ^1b is a naphthyl group, a monovalent anion is preferably bonded to a carbon atom that is not adjacent to a carbon atom to which another anion is bonded.

Examples of the divalent anionic compound include a compound represented by the formula (1-b-1) to a compound represented by the formula (1-b-13).

The divalent anionic compound is preferably a compound represented by formula (1-b-1), a compound represented by formula (1-b-2), a compound represented by formula (1-b-3), and formula (1- b-9) and a compound represented by formula (1-b-10).

Examples of the anionic dye (I-1) include the anionic dye represented by the formula (I-1a) ~ the anionic dye represented by the formula (I-9a), and preferably the anionic dye represented by the formula (I-4a) ~ An anionic dye represented by the formula (I-6a).

As a monovalent cationic compound which does not have a color-developing group (hereinafter this compound is sometimes referred to as a "monovalent cationic compound"), it is preferable to have at least one member selected from the group consisting of a polymerizable group, a silicon atom, and a phosphorus atom A monovalent cationic compound having a substituent in which it does not have a chromogenic group.

Examples of the polymerizable group include a group having an ethylenically unsaturated bond, and specific examples thereof include an alkenyl group, an acrylfluorenyl group, and a methacrylfluorenyl group.

The monovalent cation preferably has an ammonium ion [-NH ₄ ⁺ ].

Examples of the monovalent cationic compound having a polymerizable group include compounds represented by formula (Z-1).

[In the formula (Z-1), R ¹ represents an alkanediyl group having 1 to 10 carbon atoms, and -CH ₂ -contained in the alkanediyl group may be substituted with -O-, -CO-, -NR ^11- , -OCO-, -COO-, -OCONH-, -CONH-, or -NHCO-.

R ¹¹ represents an alkanediyl group having 1 to 10 carbon atoms]

Examples of the alkanediyl group having 1 to 10 carbon atoms represented by R ¹ and R ¹¹ include linear, branched, and cyclic alkanediyl groups. Specific examples thereof include methylene, ethylidene, Propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane Alkane-1,8-diyl, ethane-1,1-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-2,2-diyl, pentane-2 , 4-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, 2-methylbutane-1 , 4-diyl, cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, Alkane-1,4-diyl, Alkan-2,5-diyl, adamantane-1,5-diyl, and adamantane-2,6-diyl are preferably alkanediyl having 1 to 8 carbon atoms.

Examples of the group in which -CH ₂ -contained in the alkanediyl group having 1 to 10 carbon atoms represented by R ¹ is substituted with -O- include the following groups (* indicates a bonding bond).

Examples of the group in which -CH ₂ -contained in the alkanediyl group having 1 to 10 carbon atoms represented by R ¹ is substituted with -CO- include the following groups (* indicates a bonding bond).

Examples of the group in which -CH ₂ -contained in the alkanediyl group having 1 to 10 carbon atoms represented by R ¹ is substituted with -NR ¹¹ -include the following groups (* indicates a bonding bond) .

Examples of the group in which -CH ₂ -contained in the alkanediyl group having 1 to 10 carbon atoms represented by R ¹ is substituted with -OCO- include the following groups (* indicates a bonding bond).

Examples of the group in which -CH ₂ -contained in the alkanediyl group having 1 to 10 carbon atoms represented by R ¹ is substituted with -COO- include the following groups (* indicates a bonding bond).

Examples of the group in which -CH ₂ -contained in the alkanediyl group having 1 to 10 carbon atoms represented by R ¹ is substituted with -OCONH- include the following groups (* indicates a bonding bond).

Examples of the group in which -CH ₂ -contained in the alkanediyl group having 1 to 10 carbon atoms represented by R ¹ is substituted with -CONH- include the following groups (* indicates a bonding bond).

Examples of the group in which -CH ₂ -contained in the alkanediyl group having 1 to 10 carbon atoms represented by R ¹ is substituted with -NHCO- include the following groups (* indicates a bonding bond).

Examples of the cationic compound having a polymerizable group include a compound represented by formula (Z-1-1) to a compound represented by formula (Z1-1-3), and a compound represented by formula (Z-1-1) is preferred Combination Thing.

Examples of the cationic compound having a silicon atom include compounds represented by formula (Z-2).

[In the formula (Z-2), R ² represents an alkanediyl group having 1 to 10 carbon atoms, and -CH ₂ -contained in the alkanediyl group may be substituted with -O-, -CO-, -NR ^21- , -OCO-, -COO-, -OCONH-, -CONH-, or -NHCO-.

R ⁴⁰ , R ⁴¹ and R ⁴² each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.

q represents an integer from 1 to 10]

Examples of the alkanediyl group having 1 to 10 carbon atoms represented by R ² and R ²¹ are the same as the alkanediyl group having 1 to 10 carbon atoms represented by R ¹ and R ¹¹ .

-CH ₂ -contained in the alkanediyl group having 1 to 10 carbon atoms represented by R ² is substituted with -O-, -CO-, -NR ^21- , -OCO-, -COO-, -OCONH- Examples of the group consisting of -CONH- or -NHCO- include -CH ₂ -which is contained in an alkanediyl group having 1 to 10 carbon atoms represented by R ¹ and substituted with -O-, -CO-,- NR ^11- , -OCO-, -COO-, -OCONH-, -CONH-, or -NHCO- have the same base.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ⁴⁰ , R ⁴¹ and R ⁴² include methyl, ethyl, propyl, isopropyl, butyl, second butyl and third butyl, Methyl or ethyl is preferred.

Examples of the alkoxy group having 1 to 4 carbon atoms represented by R ⁴⁰ , R ⁴¹ and R ⁴² include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and a second butoxy group. And a third butoxy group, preferably a methoxy group or an ethoxy group.

R ⁴⁰ , R ⁴¹ and R ^{42 are} preferably the same base.

R ⁴⁰ , R ⁴¹ and R ⁴² are each preferably a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms, and more preferably a methoxy group or an ethoxy group.

q is preferably an integer of 1 to 8, more preferably an integer of 1 to 3.

Examples of the cationic compound having a silicon atom include a compound represented by formula (Z-2-1) to a compound represented by formula (Z-2-12), and a compound represented by formula (Z-2-1) is preferred. Compound ~ Compound represented by formula (Z-2-6).

Examples of the cationic compound having a phosphorus atom include compounds represented by formula (Z-3).

[In formula (Z-3), R ⁵⁰ , R ⁵¹ , R ^52, and R ⁵³ each independently represent an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a substituted phenyl group]

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ⁵⁰ , R ⁵¹ , R ⁵² and R ⁵³ include methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, Tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 1-methylbutyl, 1,1,3,3-tetramethylbutyl, 1,5-dimethylhexyl and 2-ethylhexyl and the like are preferably methyl, ethyl or 2-ethylhexyl.

Examples of the alkenyl group having 2 to 10 carbon atoms represented by R ⁵⁰ , R ⁵¹ , R ^52, and R ⁵³ include vinyl, isopropenyl, pentenyl, and hexenyl, and vinyl is preferred.

Examples of the substituent of the phenyl group represented by R ⁵⁰ , R ⁵¹ , R ⁵² and R ⁵³ include methyl, ethyl, propyl, isopropyl, butyl, second butyl, and third butyl. C1-C4 alkyl groups; methoxy, ethoxy, propoxy, C1-C4 alkoxy groups.

Examples of the cationic compound having a phosphorus atom include a compound represented by the formula (Z-3-1) to a compound represented by the formula (Z-3-6). The cation having a phosphorus atom is preferably a compound represented by the formula (Z-3-1) or a compound represented by the formula (Z-3-2).

Examples of the salt-forming dye (I) include dyes represented by formula (I-1) to dyes represented by formula (I-47). The salt-forming dye (I) is preferably a dye represented by formula (I-16) ~ a dye represented by formula (I-27) and a dye represented by formula (I-33) ~ represented by formula (I-47) The dyes are more preferably dyes represented by formula (I-16), dyes represented by formula (I-19), dyes represented by formula (I-27), dyes represented by formula (I-33) ~ A dye represented by the formula (I-35).

Next, a method for producing the salt-forming dye (I) will be described.

The salt-forming dye (I) can be obtained by mixing an anionic dye (I-1) with a monovalent cationic compound in water. Obtained by reaction. The sequence of this reaction is described below.

The anionic dye (I-1) can be obtained by reacting a monovalent cationic dye with a divalent anionic compound in water.

The reaction temperature of the monovalent cationic dye and the divalent anionic compound is preferably 0 ° C to 120 ° C, and more preferably 10 ° C to 100 ° C. The reaction time is preferably 1 to 24 hours, and more preferably 3 to 8 hours.

As a method for obtaining the anionic dye (I-1) from the reaction mixture, various known methods can be adopted. For example, the method may be a method in which a precipitate generated after filtration is taken out and washed with water. If necessary, it can be further purified by a known method such as recrystallization.

When the monovalent cationic dye is represented by the formula (I-a), it can be produced, for example, by reacting a compound represented by the formula (C-II) with a compound represented by the formula (C-III). The reaction can be carried out in the presence of an organic solvent or without a solvent.

[Wherein R ^1A to R ^12A and A are the same as the above definitions]

The amount of the compound represented by the formula (C-III) in the reaction is 1 mole, preferably 1 to 8 moles, and more preferably 1 to 3 moles relative to the compound represented by the formula (C-II).

The reaction temperature is preferably 30 ° C to 180 ° C, and more preferably 80 ° C to 130 ° C. The reaction time is preferably 1 hour to 12 hours, and more preferably 3 hours to 8 hours.

In terms of yield, the reaction of the compound represented by the formula (C-III) with the compound represented by the formula (C-II) is preferably carried out in the presence of an organic solvent. Examples of the organic solvent include: hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and chloroform; alcohol solvents such as methanol, ethanol, isopropanol, and butanol; and nitro hydrocarbon solvents such as nitrobenzene ; Ketone solvents such as methyl isobutyl ketone; amine solvents such as 1-methyl-2-pyrrolidone and the like.

The usage-amount of an organic solvent is 1-300 mass parts with respect to 1 mass part of compounds represented by Formula (C-II), Preferably it is 2-200 mass parts.

In terms of yield, the reaction of the compound represented by the formula (C-III) with the compound represented by the formula (C-II) is preferably carried out in the presence of a condensing agent. Examples of the condensing agent include phosphoric acid, polyphosphoric acid, phosphonium chloride, sulfuric acid, and thionyl chloride.

The usage-amount of a condensing agent is 1-20 mass parts with respect to 1 mass part of compounds represented by Formula (C-II), More preferably, it is 1-5 mass parts.

As a method for obtaining a monovalent anionic dye from the reaction mixture, various known methods can be adopted. For example, the method of mixing the reaction mixture with alcohol (methanol, etc.) and filtering out the crystal | crystallization which precipitated is mentioned.

The method of obtaining a monovalent anionic dye is preferably a method of adding a reaction mixture to an alcohol. The temperature when the reaction mixture is added is preferably -100 to 50 ° C, and more preferably -80 to 0 ° C. In addition, it is preferably stirred at the same temperature for 0.5 to 2 hours. The crystals taken out by filtration are preferably washed with water or the like and then dried. Further, if necessary, it can be further purified by a known method such as recrystallization.

The salt-forming dye (I) can be obtained by reacting the anionic dye (I-1) with a monovalent cationic compound as described above.

The reaction temperature of the anionic dye (I-1) and the monovalent cationic compound is preferably 0 to 120 ° C, and more preferably 10 to 100 ° C. The reaction time is preferably 1 to 24 hours, and more preferably 3 to 8 hours.

As a method for obtaining the salt-forming dye (I) from the reaction mixture, various known methods can be adopted. For example, the method may be a method in which a precipitate generated after filtration is taken out and washed with water. If necessary, it can be further purified by a known method such as recrystallization.

The colored curable resin composition of the present invention contains a colored agent (A) containing a salt-forming dye (I), a resin (B), a polymerizable compound (C), and a polymerization initiator (D). Furthermore, a solvent (E) may be contained.

<Colorant (A)>

The colorant (A) contains two or more kinds of salt-forming dyes (I).

In addition to the salt-forming dye (I), the colorant (A) may contain other dyes (A2), pigments (P), or a mixture thereof for color adjustment, that is, to adjust the spectral characteristics.

Examples of the dye (A2) include dyes such as oil-soluble dyes, acid dyes, amine salts of acid dyes, and sulfonamide derivatives of acid dyes. Examples include dyes classified in the Dye Index (published by The Society of Dyers and Colourists). Compounds, or well-known dyes described in Dyeing Notes (Seishinsha). According to the chemical structure, coumarin dyes; gold-containing azo dyes; pyridone azo dyes; barbituric acid azo dyes; quinophthalone dyes; methine dyes; cyanine dyes; anthraquinones Dyes; triphenylmethane dyes; Dyes; Tetraazaporphyrin dyes; Phthalocyanine dyes; and mixtures of these.

The content of the salt-forming dye (I) is preferably 3 to 99.9% by mass, more preferably 4 to 80% by mass, and still more preferably 5 to 30% by mass relative to the total amount of the colorant (A). If the content of the salt-forming dye (I) is within the above range, the brightness when the color filter is made is high, and therefore it is preferable.

As the pigment (P), a known pigment can be used, and examples thereof include pigments classified as pigments in the Dye Index (published by The Society of Dyers and Colourists).

Examples: CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 and other yellow pigments; C.I. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; C.I. pigment green 7, 36, 58 and other green pigments.

The pigment (P) is preferably CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 and other yellow pigments; CI Pigment Green 7, 36, 58 and other green pigments, more preferably CI Pigment Yellow 150 , 185 and CI Pigment Green 58. By containing the pigment, it is easy to optimize the transmission spectrum, and the light resistance and chemical resistance of the color filter become good.

The content of the colorant (A) is preferably 5 to 60% by mass, more preferably 8 to 55% by mass, and still more preferably 10 to 50% by mass with respect to the total amount of the solid components. When the content of the colorant (A) is within the above range, the color density when the color filter is made is sufficient, and the resin (B) or the polymerizable compound (C) can be contained in the composition in a necessary amount. A pattern with sufficient mechanical strength can be formed.

The total amount of the solid components refers to an amount obtained by removing the content of the solvent from the total amount of the colored curable resin composition. The total amount of the solid component and the content of each component relative thereto can be measured by a known analysis method such as liquid chromatography or gas chromatography.

<Resin (B)>

The resin (B) is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6].

Resin [K1]: at least one kind (Ba) (hereinafter sometimes referred to as "(Ba)") selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride and a cyclic ring having 2 to 4 carbon atoms Copolymer of an ether structure and an ethylenically unsaturated monomer (Bb) (hereinafter sometimes referred to as "(Bb)"); resin [K2]: (Ba), (Bb), and (Ba) Copolymer of monomer (Bc) (which is different from (Ba) and (Bb)) (hereinafter sometimes referred to as "(Bc)"); resin [K3]: copolymerization of (Ba) and (Bc) Thing Resin [K4]: Resin made by reacting the copolymers of (Bb) and (Ba) and (Bc); Resin [K5]: Resin made by reacting the copolymers of (Ba) and (Bb) and (Bc) Resin; Resin [K6]: A resin made by reacting the copolymers of (Ba) and (Bb) with (Bc), and then reacting with carboxylic anhydride.

Examples of (Ba) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, butenoic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid; maleic acid, fumaric acid Oxalic acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1 Unsaturated dicarboxylic acids such as 2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid; methyl-5-decane Ene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methyl Dicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2 -Ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene, and other bicyclic unsaturated compounds containing a carboxyl group; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl o Phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyl Unsaturated dicarboxylic anhydrides such as tetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] heptan-2-ene anhydride; succinate mono [2- (meth) acrylic acid ethoxyethyl Unsaturated mono [(meth) acryloxyalkyl] esters of polybasic carboxylic acids of two or more members such as methyl] ester, mono [2- (meth) acryloxyethyl] phthalate; Unsaturated acrylates such as α- (hydroxymethyl) acrylic acid containing a hydroxyl group and a carboxyl group in the same molecule.

Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferable in terms of copolymerization reactivity or the solubility of the obtained resin in an alkaline aqueous solution.

(Bb) refers to a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an ethylene oxide ring, an oxetane ring, and a tetrahydrofuran ring) and ethylenic unsaturation Bondable polymerizable compound. (Bb) A monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acrylic fluorenyloxy group is preferred.

In addition, in this specification, "(meth) acrylic acid" means at least 1 sort (s) chosen from the group which consists of acrylic acid and methacrylic acid. The expressions "(meth) acrylfluorenyl" and "(meth) acrylate" have the same meaning.

Examples of (Bb) include a monomer having an ethylene oxide group and an ethylenically unsaturated bond; a monomer having an oxetanyl group and an ethylenically unsaturated bond; and a tetrahydrofuran group and an ethylenically unsaturated bond. Of monomers, etc.

As (Bb), a monomer having an ethylene oxide group and an ethylenically unsaturated bond is preferred in terms of further improving the reliability such as heat resistance and chemical resistance of the obtained color filter. .

Examples of (Bc) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, second butyl (meth) acrylate, and third (meth) acrylate Butyl, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate Ester, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl ester (in this technology As a common name in the field, it is called "dicyclopentyl (meth) acrylate". It is also sometimes called "tricyclodecyl (meth) acrylate"), and tricyclo (meth) acrylate [5.2.1.0 ^2,6 ] decene-8-yl ester (known in the technical field as "dicyclopentenyl (meth) acrylate"), dicyclopentyloxyethyl (meth) acrylate, (Meth) acrylic acid Ester, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, (meth) (Meth) acrylates such as benzyl acrylate; 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate (meth) acrylates containing hydroxyl groups; diethyl maleate Dicarboxylic acid diesters such as esters, diethyl fumarate, diethyl iconate; bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2- Ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] Hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-bis (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6- Bis (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene 5-hydroxymethyl-5-methyl Bicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene , 5-phenoxycarbonyl bicyclo [2.2.1] hept-2-ene, 5,6-bis (third butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis ( Cyclohexyloxycarbonyl) Bicyclic [2.2.1] Hept-2-ene and other bicyclic unsaturated compounds; N-phenylcis-butenedifluorenimide, N-cyclohexylcisbutenedifluorenimine, N-benzyl Cis-butenediamidoimide, N-butanediamidoimino-3-cisbutanediamidoimide benzoate, N-butadieneimido-4-cisbutenediamidoimide Butyrate, N-Butanediimino-6-cis-butenediamidohexanoate, N-Butadienimino-3-cisbutanediiminopropionate, N- (9-acridinyl) dicarbonylfluorenimine derivatives such as maleimidine diimide; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p- Methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2 , 3-dimethyl-1,3-butadiene and the like.

Among these, in terms of copolymerization reactivity and heat resistance, styrene, vinyltoluene, N-phenylcis-butenedifluorenimide, and N-cyclohexylcisbutenedifluorene are preferred. Amine, N-benzylcis-butenediamidine, bicyclo [2.2.1] hept-2-ene, etc.

Examples of the resin (B) include 3,4-epoxycyclohexyl methyl (meth) acrylate / (meth) acrylic acid copolymer and 3,4-epoxy tricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (Meth) acrylic copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic copolymer, glycidyl (meth) acrylate / styrene / (Meth) acrylic acid copolymer, acrylic acid 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl ester / (meth) acrylic acid / N-cyclohexyl maleimide diimide copolymer, 3-methyl Resins such as 3- (meth) acryloxymethyloxetane / (meth) acrylic acid / styrene copolymer [K2]; benzyl (meth) acrylate / (meth) acrylic acid copolymerization Resin, resin such as styrene / (meth) acrylic copolymer [K3]; resin obtained by adding glycidyl (meth) acrylate to benzyl (meth) acrylate / (meth) acrylic copolymer, Tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer added with glycidyl (meth) acrylate, tricyclodecyl (meth) acrylate / (meth) Addition of benzyl acrylate / (meth) acrylic copolymer (meth) Resins made of glycidyl acrylate [K4]; resins obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate and (meth) acrylic acid, Tricyclodecyl methacrylate / styrene / glycidyl (meth) acrylate copolymer reacted with (meth) acrylic acid and other resins [K5]; Tricyclodecyl (meth) acrylate A copolymer of (glycidyl / (meth) acrylate) reacts with (meth) acrylic acid and causes the obtained resin to further react with tetrahydrophthalic anhydride [K6] and the like.

The resin (B) is preferably a resin [K1] and a resin [K2].

Resin (B) can refer to the method described in the document "Experimental Methods of Polymer Synthesis" (Otsu Takayuki Publishing Co., Ltd., 1st Edition, First Press, March 1, 1972) and the document Manufactured by cited documents.

The obtained copolymer may be directly used as a solution after the reaction, a concentrated or diluted solution may be used, or a solid (powder) may be extracted by a method such as reprecipitation. In particular, since the solvent contained in the colored curable resin composition of the present invention is used as a solvent during the polymerization, the solution after the reaction can be directly used for the preparation of the colored curable resin composition of the present invention, thus simplifying the present invention. The manufacturing process of the colored hardening resin composition of this invention.

The polystyrene equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 30,000. When the molecular weight is within the above range, the hardness of the color filter increases, the residual film rate is high, the solubility of the unexposed portion in the developing solution is good, and the resolution of the colored pattern tends to increase.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, more preferably 1.2 to 4.

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

The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass with respect to the total amount of the solid components. When the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution and the residual film rate of the colored pattern tend to increase.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound that can be polymerized by using an active radical and / or an acid generated from the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond. (Meth) acrylate compounds.

The polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, four Pentaerythritol nona (meth) acrylate, isocyanuric acid tri (2- (meth) acryloxyethyl) ester, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol Hexa (meth) acrylate, propylene glycol-modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone Modified dipentaerythritol hexa (meth) acrylate and the like.

As the polymerizable compound having three or more ethylenically unsaturated bonds, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferred.

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

The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass with respect to the total amount of the solid components. When the content of the polymerizable compound (C) is within the above range, the residual film rate at the time of forming a colored pattern and the chemical resistance of the color filter tend to be improved.

<Polymerization initiator (D)>

The polymerization initiator (D) may be a known polymerization initiator as long as it is a compound that can start polymerization by generating active radicals, acids, and the like by the action of light or heat. Examples of the polymerization initiator that generates living radicals include O-fluorenyl oxime compounds, benzoalkyl ketone compounds, Compounds, fluorenyl phosphine oxide compounds, and biimidazole compounds.

Examples of the O-fluorenyl oxime compound include N-benzyloxy-1- (4-phenylmercaptophenyl) butane-1-one-2-imine and N-benzyloxy- 1- (4-phenylmercaptophenyl) octane-1-one-2-imine, N-benzyloxy-1- (4-phenylmercaptophenyl) -3-cyclopentylpropane- 1-keto-2-imine, N-ethoxyl-1- [9-ethyl-6- (2-methylbenzyl) -9H-carbazol-3-yl] ethane-1 -Imine, N-ethoxyl-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxane Pentylmethoxy) benzyl} -9H-carbazol-3-yl] ethane-1-imine, N-ethoxyl-1- [9-ethyl-6- (2-methyl Benzamyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzyloxy-1- [9-ethyl-6- (2- Methylbenzyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-one-2-imine and the like. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF), and N-1919 (made by ADEKA) can also be used. Among these, the O-fluorenyl oxime compound is preferably selected from the group consisting of N-benzyloxy-1- (4-phenylmercaptophenyl) butane-1-one-2-imine, and N-benzyloxy 1- (4-phenylmercaptophenyl) octane-1-one-2-imine and N-benzyloxy-1- (4-phenylmercaptophenyl) -3-cyclopentyl At least one of the group consisting of propane-1-one-2-imine, more preferably N-benzyloxy-1- (4-phenylmercaptophenyl) octane-1-one-2 -Imine. In the case of these O-fluorenyl oxime compounds, a high-color color filter tends to be obtained.

Examples of the benzoalkyl ketone compound include 2-methyl-2- Phenyl-1- (4-methylmercaptophenyl) propane-1-one, 2-dimethylamino-1- (4- Phenylphenyl) -2-benzylbutane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4- Phenyl) phenyl] butane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxy Ethoxy) phenyl] propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propane-1-one oligomer Compounds, α, α-diethoxyacetophenone, benzophenone dimethyl ketal, etc. Commercial products such as Irgacure (registered trademark) 369, 907, and 379 (above manufactured by BASF) can also be used.

As three Compounds include: 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-tris , 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-tri , 2,4-bis (trichloromethyl) -6-sunfloweryl-1,3,5-tri , 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) vinyl] -1,3,5-tris Wait.

Examples of the fluorenylphosphine oxide compound include 2,4,6-trimethylbenzylfluorenyldiphenylphosphine oxide and the like. Commercial products such as Irgacure (registered trademark) 819 (manufactured by BASF) can also be used.

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-di (Chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (see Japanese Patent Laid-Open No. 6-75372, Japanese Patent Laid-Open No. 6-75373, etc.), 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra ( (Alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (dialkoxyphenyl) biimidazole, 2,2'- Bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (trialkoxyphenyl) biimidazole (refer to Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 62-174204 Etc.), imidazole compounds in which the 4,4-', 5,5'-phenyl group is substituted with an alkoxycarbonyl group (see Japanese Patent Laid-Open No. 7-10913, etc.) and the like.

Further, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone and methyl benzophenethylbenzoate , 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetrakis (third butylperoxycarbonyl) diphenyl Benzophenone compounds such as ketone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone and other quinone compounds; 10-butyl-2- Chloracridone, benzodiazone, methyl phenylglyoxylate, titanocene compounds, etc.

Examples of the acid-generating polymerization initiator include 4-hydroxyphenyldimethylfluorene p-toluenesulfonate, 4-hydroxyphenyldimethylfluorene hexafluoroantimonate, and 4-ethoxyfluorenyl p-toluenesulfonic acid. Phenyldimethylphosphonium, 4-Ethyloxyphenylmethylbenzyl hexafluoroantimonate, triphenylphosphonium p-toluenesulfonate, triphenylphosphonium hexafluoroantimonate, diphenyl p-toluenesulfonic acid Onium salts such as osmium, diphenylphosphonium hexafluoroantimonate, nitrobenzyl tosylate, benzoin tosylate, and the like.

As the polymerization initiator (D), it is preferable to include a polymer selected from the group consisting of an O-fluorenyl oxime compound, an benzoyl ketone compound, A polymerization initiator of at least one of the group consisting of a compound, a fluorenylphosphine oxide compound, and a biimidazole compound, more preferably a polymerization initiator containing an O-fluorenyl oxime compound.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is within the above-mentioned range, there is a tendency that the sensitivity is increased and the exposure time is shortened, so the productivity of the color filter is improved.

<Solvent (E)>

The solvent (E) can be used as a solvent generally used in this field. Examples include: ester solvents (solvents containing -COO- but not containing -O- in the molecule), ether solvents (solvents containing -O- and not containing -COO- in the molecule), ether ester solvents (containing- COO- and -O- solvents), ketone solvents (solvents containing -CO- and not including -COO- in the molecule), alcohol solvents (containing OH in the molecule and -O-, -CO- and -COO- Solvents), aromatic hydrocarbon solvents, amidine solvents, dimethyl sulfene.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and isoamyl acetate. , Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, cyclamate Hexanol acetate and γ-butyrolactone.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and Ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, Tetrahydrofuran, tetrahydropyran, 1,4-di Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyl ether and Methylanisole.

Examples of the ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxypropionic acid. Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionic acid Ethyl ester, 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2- Ethoxy-2-methylpropanoate, 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, and diethylene glycol monobutyl ether acetate.

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, and 4-methyl-2- Pentanone, cyclopentanone, cyclohexanone and isophorone.

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

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

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

In terms of coating properties and drying properties, the solvent (E) is preferably an organic solvent having a boiling point of 120 ° C. to 210 ° C. at 1 atm.

As the solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diethyl ether are preferred. Diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone and N, N-dimethylformamide, more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, N, N- Dimethylformamide, N-methylpyrrolidone, and ethyl 3-ethoxypropionate.

The content of the solvent (E) is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass based on the total amount of the colored curable resin composition of the present invention.

The total amount of solid components of the colored curable resin composition is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating becomes good, and the color density is not insufficient when forming a color filter. On the other hand, the display characteristics tend to be good.

<Other ingredients>

The colored hardening resin composition of the present invention may optionally contain a polymerization initiation aid, a leveling agent, a filler, other polymer compounds, an adhesion promoter, an antioxidant, a light stabilizer, and a chain transfer agent. Known additives.

<Manufacturing method of colored curable resin composition>

The coloring curable resin composition of the present invention can be prepared by, for example, coloring agent (A), resin (B), polymerizable compound (C), polymerization initiator (D), and solvent (E) as needed, A leveling agent, a polymerization initiation aid, and other ingredients are prepared by mixing.

When the pigment (P) is contained as the colorant (A), the pigment (P) is preferably partially or fully mixed with the solvent (E) in advance, and dispersed with a bead mill or the like until the average particle diameter of the pigment becomes approximately 0.2 μm or less. At this time, part or all of the pigment dispersant and resin (B) may be blended as necessary. The target coloring curable resin composition can be prepared by mixing the remaining components in the pigment dispersion liquid thus obtained so as to have a specific concentration.

Dyes such as salt-forming dyes can be separately dissolved in a part or all of the solvent (E) to prepare a solution.

The solution is preferably filtered with a filter having a pore size of about 0.01 to 1 μm.

It is preferable to filter the colored hardening resin composition after mixing with a filter having a pore size of 0.1 to 10 μm.

<Manufacturing method of color filter>

The color filter of the present invention is formed of the coloring curable resin composition.

Examples of the method for producing a color filter from the colored hardening resin composition of the present invention include a photolithography method, an inkjet method, and a printing method, and the photolithography method is preferred.

The photolithography method is a method in which a colored curable resin composition is coated on a substrate and dried to form a colored composition layer, the colored composition layer is exposed through a photomask, and a colored pattern is developed. .

In the photolithography method, a colored coating film can be formed as a cured product of the coloring composition layer described above because a photomask is not used and / or development is not performed during exposure. The color filter of the present invention may be a coating film including a colored pattern or a colored coating film.

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

As the substrate, glass plates such as quartz glass, borosilicate glass, alumina silicate glass, soda-lime glass coated with silicon dioxide, or polycarbonate, polymethyl methacrylate, or poly-p-phenylene can be used. Resin plates such as ethylene diformate, silicon, and aluminum, silver, silver / copper / palladium alloy films, and the like are formed on the substrate. Other color filter layers, resin layers, transistors, circuits, etc. can also be formed on these substrates.

The formation of the colored pattern by the photolithography method can be performed using a known or conventional device or conditions. For example, it can be produced as follows.

First, a colored curable resin composition is coated on a substrate, and volatile components such as solvents are removed and dried by heating (pre-baking) and / or drying under reduced pressure to obtain a smooth colored composition layer .

Examples of the coating method include a spin coating method, a slit coating method, and a slit-spin coating method.

In the case of heating and drying, the temperature is preferably 30 to 120 ° C, and more preferably 50 to 110 ° C. The heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.

In the case of drying under reduced pressure, it is preferably performed at a pressure of 50 to 150 Pa and 20 to 25 ° C.

The film thickness of the coloring composition layer may be appropriately selected according to the film thickness of the target color filter.

Next, the coloring composition layer is exposed through a mask for forming a target coloring pattern. The pattern on the reticle can be a pattern suitable for the intended use.

As a light source for exposure, light having a wavelength of 250 to 450 nm is preferable source. For example, it is also possible to use a filter that cuts off the wavelength region for light less than 350 nm, or to selectively extract the light near 436 nm, 408 nm, and 365 nm using a band-pass filter that extracts these wavelength regions. Specific examples include a mercury lamp, a light-emitting diode, a metal halide lamp, and a halogen lamp.

In order to uniformly radiate parallel light to the entire exposure surface, or to correctly position the mask and the substrate on which the coloring composition layer is formed, it is preferable to use an exposure device such as a mask alignment exposure machine and a stepping exposure machine.

A coloring pattern is formed on a substrate by developing the coloring composition layer after exposure with a developing solution. By development, the unexposed part of the coloring composition layer is dissolved in the developing solution and removed. As the developing solution, an aqueous solution of a basic compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide is preferred.

The concentration of the basic compound in the aqueous solution is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass. Furthermore, the developing solution may contain a surfactant.

The developing method may be any of a liquid coating method, a dipping method, and a spray method. Furthermore, the substrate can be inclined at an arbitrary angle during development.

After development, washing with water is preferred.

Preferably, the obtained colored pattern is post-baked. The post-baking temperature is preferably 150 to 250 ° C, and more preferably 160 to 235 ° C. The post-baking time is preferably 1 to 120 minutes, and more preferably 10 to 60 minutes.

[Example]

Hereinafter, the present invention will be described in more detail with examples, but the present invention is not limited to these examples. In the examples,% and parts indicating the content or the amount used are the basis of quality unless otherwise specified.

In the following synthesis examples, the structure of the compound was confirmed by mass analysis (LC; Model 1200 manufactured by Agilent, MASS; Model LC / MSD manufactured by Agilent).

Synthesis Example 1

The following reactions were performed under a nitrogen atmosphere.

After putting 36.3 parts of potassium thiocyanate and 160 parts of acetone into a flask equipped with a condenser and a stirring device, the mixture was stirred at room temperature for 30 minutes. To the obtained mixture, 50 parts of benzamidine chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes, and the mixture was stirred at room temperature for 2 hours. After the obtained reaction mixture was cooled in an ice bath, 45.7 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, and the mixture was stirred at room temperature for 30 minutes. After the obtained reaction mixture was cooled in an ice bath, 34.2 parts of a 30% sodium hydroxide aqueous solution was added dropwise, and the mixture was stirred at room temperature for 30 minutes. To the obtained reaction mixture, 35.3 parts of chloroacetic acid was added dropwise at room temperature, followed by heating and refluxing for 7 hours. Then, after the reaction mixture was left to cool to room temperature, the reaction solution was poured into 120 parts of water, and then 200 parts of toluene was added and stirred for 30 minutes. The obtained mixture was allowed to stand for 30 minutes, separated into an organic layer and an aqueous layer, and an organic layer was obtained by performing a liquid separation operation. The obtained organic layer was washed with one equivalent of 200 parts of hydrochloric acid, 200 parts of water, and 200 parts of saturated saline. Glauber's salt was added to the organic layer and stirred for 30 minutes, and then filtered to obtain a dried organic layer. The solvent of the obtained organic layer was distilled off to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried under reduced pressure at 60 ° C to obtain 52.0 parts of a compound represented by formula (B-I-1).

The following reactions were performed under a nitrogen atmosphere.

9.3 parts of the compound represented by formula (BI-1) and 4,4'-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) were put into a flask equipped with a condenser and a stirring device.10 Parts and 20 parts of toluene, 14.8 parts of phosphoric acid and chlorine were added and stirred at 95 to 100 ° C for 3 hours. The obtained reaction mixture was cooled to room temperature, and then diluted with 170 parts of isopropyl alcohol. Dilute it After the reaction solution was poured into 300 parts of saturated saline, 100 parts of toluene was added and stirred for 30 minutes. The obtained mixture was allowed to stand for 30 minutes, and as a result, was separated into an organic layer and an aqueous layer. An organic layer was obtained by performing a liquid separation operation. The obtained organic layer was washed with 300 parts of saturated saline. Glauber's salt was added to the organic layer and stirred for 30 minutes, and then filtered to obtain a dried organic layer. The solvent of the obtained organic layer was distilled off to obtain a blue-violet solid. The obtained blue-violet solid was dried under reduced pressure at 60 ° C to obtain 19.8 parts of a compound represented by the formula (A-II-1).

Identification of the compound represented by formula (A-II-1)

(Mass analysis) Ionization mode = ESI +: m / z = 601.3 [M-Cl] ⁺

Exact Mass: 636.3

Synthesis Example 2

6.3 parts of the compound represented by formula (A-II-1) was dissolved in 500 parts of ion-exchanged water. To the obtained mixture, 2.8 parts of 1,5-dinaphthalenesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 40 ° C for 12 hours. The obtained reaction mixture was cooled to room temperature, and the generated crystals were taken out by filtration, washed with ion-exchanged water, and then dried at 60 ° C for 24 hours to obtain a compound including the formula (A-II-2). 8.8 parts of solid.

Example 1

8.8 parts of solid containing the compound represented by formula (A-II-2) was dissolved in 500 parts of ion-exchanged water.

To the obtained aqueous solution was added 2.2 parts of 3-aminopropylethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), and the mixture was stirred at 30 ° C for 12 hours. After the obtained reaction mixture was cooled to room temperature, the generated crystals were taken out by filtration, washed with ion-exchanged water, and then dried at 60 ° C for 24 hours to obtain a compound represented by the formula (A2-Z2-4) 11.1 Serving.

Example 2

In Example 1, except that a salt of formula (d-1) was used instead of 3-aminopropylethoxysilane, synthesis was performed in the same manner to obtain the formula (A2-Z1-1) Of compounds.

Example 3

In Example 1, a salt of formula (d-2) was used in place of 3-aminopropylethoxysilane, except that the synthesis was performed in the same manner to obtain the formula (A2-Z3-1) Of compounds.

Synthesis Example 3

19 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane 171 parts of a mixture of alkane-9-yl esters (containing a molar ratio of 50:50) (trade name "E-DCPA", manufactured by Daicel Corporation) was dissolved in 40 parts of propylene glycol monomethyl ether acetate To obtain a solution (hereinafter sometimes referred to as solution (1)).

A solution (hereinafter sometimes referred to as a solution (2)) was obtained by dissolving 26 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) in 120 parts of propylene glycol monomethyl ether acetate.

The inside of a flask equipped with a reflux condenser, a dropping funnel, and a stirrer was set to a nitrogen atmosphere, and 100 parts of propylene glycol monomethyl ether acetate was placed, and heated to 85 ° C while stirring. Then, the obtained solution was added dropwise to the flask over about 5 hours. Then, the solution (2) was added dropwise to the flask over about 5 hours.

After the dropwise addition of the solution (2) was completed, it was kept at the same temperature for about 3 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin (B-1)) having a solid content of 43.5%. The weight average molecular weight of the obtained resin (B-1) was 8000, the molecular weight distribution was 1.98, and the acid value in terms of solid content was 53 mg-KOH / g.

[Preparation of colored curable resin composition]

Example 4

The following colorant (A), resin (B), polymerizable compound (C), polymerization initiator (D), solvent (E), and leveling agent (F) are mixed to obtain color-hardenability Resin composition (1).

Colorant (A): 20 parts of the dye represented by formula (A2-Z2-4); Resin (B): 53 parts of resin (B-1) (in terms of solid content); Polymerizable compound (C): Dipentaerythritol 16 parts of hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.); polymerization initiator (D): N-benzyloxy-1- (4-phenylmercaptophenyl) octyl Alkan-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Corporation; O-fluorenyl oxime compound) 4 parts; solvent (E): 120 parts of propylene glycol monomethyl ether acetate; and 480 parts of 4-hydroxy-4-methyl-2-pentanone; and leveling agent (F): polyether-modified polysiloxane oil

(Toray Silicone SH8400; manufactured by Dow Corning Toray Co., Ltd.) 0.15 copies

Example 5

The following colorant (A), resin (B), polymerizable compound (C), polymerization initiator (D), solvent (E), and leveling agent (F) are mixed to obtain color-hardenability Resin composition (2).

Colorant (A): 21 parts of dye represented by formula (A2-Z1-1); Resin (B): 50 parts of resin (B-1) (in terms of solid content); polymerizable compound (C): dipentaerythritol 16 parts of hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.); polymerization initiator (D): N-benzyloxy-1- (4-phenylmercaptophenyl) octyl 4 parts of alkane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Corporation; O-fluorenyl oxime compound); solvent (E): 120 parts of propylene glycol monomethyl ether acetate; and 480 parts of 4-hydroxy-4-methyl-2-pentanone; and leveling agent (F): polyether-modified silicone oil

(Toray Silicone SH8400; manufactured by Dow Corning Toray Co., Ltd.) 0.15 copies

Example 6

The following colorant (A), resin (B), polymerizable compound (C), polymerization initiator (D), solvent (E), and leveling agent (F) are mixed to obtain color-hardenability Resin composition (3).

Colorant (A): 26 parts of the dye represented by the formula (A2-Z3-1); Resin (B): Resin (B-1) (solid content conversion) 50 parts; Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; Nippon Kayaku Co., Ltd.) 20 parts ; Polymerization initiator (D): N-benzyloxy-1- (4-phenylmercaptophenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; BASF Made by the company; 4 parts of O-fluorenyl oxime compound); solvent (E): 120 parts of propylene glycol monomethyl ether acetate; and 480 parts of 4-hydroxy-4-methyl-2-pentanone; and a leveling agent ( F): Polyether modified silicone oil

(Toray Silicone SH8400; manufactured by Dow Corning Toray Co., Ltd.) 0.15 copies

Comparative Example 1

The following colorant (A), resin (B), polymerizable compound (C), polymerization initiator (D), solvent (E), and leveling agent (F) are mixed to obtain color-hardenability Resin composition (1 ').

Colorant (A): 26 parts of the dye represented by the formula (A-III-1); Resin (B): 53 parts of the resin (B-1) (in terms of solid content); polymerizable compound (C): dipentaerythritol 16 parts of hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.); polymerization initiator (D): N-benzyloxy-1- (4-phenylmercaptophenyl) octyl 4 parts of alkane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Corporation; O-fluorenyl oxime compound); solvent (E): 120 parts of propylene glycol monomethyl ether acetate; and 480 parts of 4-hydroxy-4-methyl-2-pentanone; and leveling agent (F): polyether-modified silicone oil

(Toray Silicone SH8400; manufactured by Dow Corning Toray Co., Ltd.) 0.15 copies

Test example

[Production of color filters]

This colored curable resin composition was applied on a 2-inch square glass substrate (# 1737; manufactured by Corning) by a spin coating method, and then pre-baked at 100 ° C for 3 minutes to form a colored composition layer. . After cooling, exposure was performed using an exposure machine (TME-150RSK; manufactured by Topcon) in an atmospheric environment at an exposure amount (based on 365 nm) of 150 mJ / cm ² . Furthermore, no photomask is used. The coloring composition layer after exposure was post-baked at 180 ° C. for 20 minutes in an oven, thereby producing a color filter (film thickness: 2.8 μm).

[Evaluation of heat resistance]

The color filter was heated at 30 ° C for 20 minutes, and the color difference (ΔEab *) before and after heating of the color filter was measured using a color measuring machine (OSP-SP-200; manufactured by OLYMPUS).

The color difference (ΔEab *) of the coating film obtained from each of the colored photosensitive resin compositions of Examples 4, 5, 6, and Comparative Example 1 was determined. The results are shown in Table 1.

In addition, regarding the color difference (ΔEab *), a smaller value indicates a material having higher heat resistance.

[Industrial availability]

The colored curable resin composition containing the salt-forming dye of the present invention can provide a color filter exhibiting good heat resistance. This color filter is useful for a display device (a liquid crystal display device, an organic EL device, an electronic paper, etc.) and a solid-state imaging element.

Claims (11)

A salt-forming dye formed by a monovalent cationic dye, a divalent anionic compound, and a monovalent cationic compound without a color-developing group, wherein the monovalent cationic dye has the following formula (1-a-1): In the formula (1-a-1), X represents an oxygen atom or a sulfur atom; R ^1A to R ^8A each independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 20 carbon atoms, wherein the carbon -CH ₂ -contained in the alkyl group of 1 to 20 may be substituted by -O-; R ^9A to R ^12A each independently represents a hydrogen atom, an alkyl group of 1 to 20 carbons which may have a substituent, or An aromatic hydrocarbon group having 6 to 20 carbon atoms having a substituent, wherein -CH ₂ -contained in the alkyl group having 1 to 20 carbon atoms may be substituted with -O-; R ⁴⁵ and R ⁴⁶ each independently represent hydrogen An atom, an alkyl group having 1 to 20 carbons which may have a substituent or an aromatic hydrocarbon group having 6 to 20 carbons which may have a substituent, among which the alkyl group having 1 to 20 carbons which may have a substituent is included -CH ₂ -may be substituted with -O-; and R ⁵⁵ represents an alkyl group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. For example, the salt-forming dye of claim 1 is obtained from a monovalent anionic dye formed by the monovalent cationic dye and the divalent anionic compound, and a monovalent cationic compound having no color-developing group. The salt-forming dye according to claim 1 or 2, wherein the divalent anionic compound is an aromatic compound having two monovalent anions, or a heteroaromatic compound having two monovalent anions. The salt-forming dye according to claim 3, wherein the monovalent anion is a sulfonate anion. Item 1 or 2 dyes of the salified request, wherein the divalent anion is a compound of formula (1b) represented by _{^{the, O 3 SR 1b -SO 3 -}} (1b) ( wherein, R ^1b represents An aromatic hydrocarbon group having 6 to 18 carbon atoms with a substituent). For example, the salt-forming dye of claim 1 or 2, wherein the monovalent cationic compound having no chromophore has at least one substituent selected from the group consisting of a polymerizable group, a silicon atom, and a phosphorus atom, and does not have Chromogenic compounds. A coloring agent comprising a salt-forming dye according to any one of claims 1 to 6. A coloring curable resin composition comprising the coloring agent according to claim 7, a resin, a polymerizable compound, and a polymerization initiator. A coating film formed from the colored curable resin composition according to claim 8. A color filter formed of the coloring curable resin composition according to claim 8. A display device includes a color filter as claimed in claim 10.