KR102023656B1 - Salt formation dye and colored curable resin composition - Google Patents

Abstract

A salt forming dye formed from a monovalent cation dye, a divalent anion compound, and a monovalent cation compound having no chromophore.

Description

SALT FORMATION DYE AND COLORED CURABLE RESIN COMPOSITION

The present invention relates to a salt dye and a colored curable resin composition.

Dye is used as a coloring agent of the color filter contained in a liquid crystal display device, a solid-state image sensor, etc. As the dye, for example, a compound represented by the formula (A-III-1) is described in WO2012 / 128318 (wherein Et represents an ethyl group).

The present invention includes the following inventions.

[1] A salt forming dye formed from a monovalent cation dye, a divalent anion compound, and a monovalent cation compound having no coloring group.

[2] The salt-forming dye according to [1], which is formed from a monovalent cation dye and a monovalent anion dye formed from a divalent anion compound, and a monovalent cation compound having no coloring group.

[3] The salt salt dye according to [1] or [2], wherein the divalent anion 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] The salt forming dye according to any one of [1] to [4], wherein the divalent anion compound is a compound represented by formula (1-b).

(In formula, R <^1b> represents the C6-C18 aromatic hydrocarbon group which may have a substituent.)

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

[In formula (1-A), R <^1A> -R <^8A> respectively independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or a C1-C20 alkyl group, and -CH contained in a C1-C20 alkyl group ₂ -may be substituted with -O-.

R ^9A to R ^12A each independently represent 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 is contained in an alkyl group having 1 to 20 carbon atoms. CH ₂ -may be substituted with -O-.

A represents a C6-C20 aromatic hydrocarbon group which may have a substituent or a C2-C10 heteroaromatic hydrocarbon group which may have a substituent.]

[7] The monovalent cation compound having no chromophore is a compound having at least one substituent selected from the group consisting of a polymerizable group, a silicon atom and a phosphorus atom, and a compound having no chromophore. The salt salt dye in any one of them.

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

[9] A colored 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 colored curable resin composition according to the above [9].

[12] A display device comprising the color filter according to the above [11].

<Salting dye (Ⅰ)>

The dye of this invention may be called salt forming dye (henceforth salt dye (I)) formed from the monovalent cation dye, the bivalent anion compound, and the compound which has monovalent cation and does not have a coloring group. )to be.

In the present invention, a monovalent anionic dye is usually formed from a monovalent cation dye and a divalent anion compound. Hereinafter, the said anion dye may be called "anion dye (I-1)." The salt-forming dye (I) can be formed from an anion dye (I-1) and a monovalent cation compound having no coloring group.

In addition to anion dye (I-1), the salt-forming dye of this invention is formed from the monovalent cation compound which does not have a coloring group, and therefore has higher chromaticity than anion dye (I-1).

As monovalent cation dye, the cation which has two or more phenyl groups is mentioned. As a specific example of the said cation dye, the compound represented by Formula (1-a) and tautomers of this compound are mentioned.

[In formula (1-a), R <^1A> -R <^8A> respectively independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or a C1-C20 alkyl group, -CH contained in a C1-C20 alkyl group ₂ -may be substituted with -O-.

R ^9A to R ^12A each independently represent 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 is contained in an alkyl group having 1 to 20 carbon atoms. CH ₂ -may be substituted with -O-.

A represents a C6-C20 aromatic hydrocarbon group which may have a substituent, or a heteroaromatic hydrocarbon group which may have a C2-C10 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 preferably a fluorine atom Or a 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 a linear, branched and cyclic alkyl group. Specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, Nonyl group, decyl group, undecyl group, dodecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, methylcyclohexyl group, dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, Decahydronaphthyl group, adamantyl group, 2-alkyladamantan-2-yl group, 1- (adamantan-1-yl) alkane-1-yl group, norbornyl group, methylnorbornyl group and isobornyl group Can be mentioned.

As said alkyl group, Preferably it is a C1-C8 alkyl group, More preferably, it is a C1-C6 alkyl group, More preferably, it is a C1-C4 alkyl group.

-CH ₂ -contained in an 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 carbon number.

As the group in which -CH ₂ -contained in an 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 substituted with -O-, The group described in the above is mentioned. In the formula, * represents a bonding hand.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ^9A , R ^10A , R ^11A, and R ^12A include C 1 ¹ , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A, and R ^8A The same thing as the alkyl group of -20 is mentioned.

-CH ₂ -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, when -CH ₂ -contained in an alkyl group having 1 to 20 carbon atoms is substituted with -O-, -O- is not included in the carbon number.

As the group in which -CH ₂ -contained 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-, R ^1A , R ^2A , R ^3A , R ^4A , R ^5A, R ^6A, -CH ₂ contained in the alkyl group of 1 to 20 carbon atoms represented by R ^7A and R ^8A - may be the same groups substituted with a group -O-.

As a substituent which the C1-C20 alkyl group represented by R <^9A> , R <^10A> , R <^11A> and R <^12A> may have, Halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; -NR ¹¹¹ R ¹¹² (such as an amino group and a dimethylamino group) (R ¹¹¹ and R ¹¹² each independently represents 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 substituents represented by R ^9A , R ^10A , R ^11A and R ^12A include the groups described below. * Represents 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 anthracenyl group.

As a substituent which the C6-C20 aromatic hydrocarbon group represented by R <^9A> , R <^10A> , R <^11A> and R <^12A> may have, Halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; Haloalkyl groups having 1 to 6 carbon atoms such as a chloromethyl group and a trifluoromethyl group; C1-C6 alkoxy groups, such as a methoxy group and an ethoxy group; Hydroxyl group; Sulfamoyl group; C1-C6 alkylsulfonyl groups, such as a methylsulfonyl group, are mentioned.

As a C6-C20 aromatic hydrocarbon group represented by A, a phenyl group and a naphthyl group are mentioned, Preferably it is a C6-C10 aromatic hydrocarbon group.

The C2-C10 heteroaromatic hydrocarbon group represented by A should just have at least 1 hetero atom as a component of a 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 group, imidazolyl group, pyrazolyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, benzothiazolyl group and benzo Isothiazolyl group, thienyl group, and benzothienyl group, Preferably it is a C2-C8 heteroaromatic hydrocarbon group, More preferably, it is a C2-C8 heteroaromatic hydrocarbon group which has at least 1 nitrogen atom. More preferably, it is a C2-C8 heteroaromatic hydrocarbon group (for example, thiazolyl group) which has a nitrogen atom and a sulfur atom.

As a substituent in the C6-C20 aromatic hydrocarbon group represented by A, a halogen atom, the amino group which may have a substituent, and a C1-C6 alkyl group are mentioned.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.

Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group and hexyl group.

As a substituent in an amino group, the aromatic hydrocarbon group which may have a C1-C20 alkyl group, a C1-C6 haloalkyl group, and a substituent is mentioned.

In A, a C1-C20 alkyl group includes a linear, branched and cyclic alkyl group, and specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and sec-butyl group. , tert-butyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohex Real group, methylcyclohexyl group, dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, decahydronaphthyl group, adamantyl group, 2-alkyladamantan-2-yl group, 1- (adamantane -1-yl) alkane-1-yl group, norbornyl group, methyl norbornyl group, and isobornyl group is mentioned.

A phenyl group and a naphthyl group are mentioned as an aromatic hydrocarbon group which has as a substituent in the C6-C20 aromatic hydrocarbon group represented by A.

As a substituent in an aromatic hydrocarbon group, Halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; C1-C4 alkoxy groups, such as a methoxy group and an ethoxy group; And alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group and tert-butyl group.

As an amino group which has a substituent, Alkylamino groups, such as a methylamino group and an ethylamino group; Phenylamino groups such as phenylamino group, 2-fluorophenylamino group, 2-chlorophenylamino group (p-methoxyphenyl) amino group, and (o-methylphenyl) amino group; Dialkylamino groups such as dimethylamino group and diethylamino group; Alkylphenylamino groups such as N-phenyl-N-methylamino group, N- (o-methylphenyl) -N-methylamino group, N- (o-methylphenyl) -N-ethyl group and N-phenyl-N-isopropylamino group; Can be mentioned.

As a substituent which the C2-C10 heteroaromatic hydrocarbon group represented by A may have, a halogen atom, a C1-C20 alkyl group, the C6-C20 aromatic hydrocarbon group which may have a substituent, and the amino group which may have a substituent are mentioned. Can be.

As a specific example of the halogen atom, the C1-C20 alkyl group, the C6-C20 aromatic hydrocarbon group which may have a substituent, and the amino group which may have a substituent, the example shown as a substituent which the above-mentioned aromatic hydrocarbon group may have, respectively is mentioned. Can be.

As group represented by A, group represented by Formula (A1-1)-group represented by Formula (A1-13) can be mentioned, As group represented by Formula (A1-2), Formula (A1-7) The group represented, the group represented by formula (A1-8) and the group represented by formula (A1-9) are preferable, and the group represented by formula (A1-8) and the group represented by formula (A1-9) are further desirable.

It is preferable that the monovalent cation dye represented by Formula (1-a) is a compound represented by Formula (1-a-1), and its tautomer.

[In 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 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and having 1 to 20 carbon atoms which may have the above substituents. -CH ₂ -contained in the alkyl group of may be substituted with -O-.

R <^55> represents the C6-C20 aromatic hydrocarbon group which may have a hydrogen atom, a C1-C20 alkyl group, or a substituent.

R ^1A to R ^12A each represent the same meaning as described above.]

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ⁴⁵ and R ⁴⁶ include linear, branched and cyclic alkyl groups, and specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, cyclopropyl group, cyclobutyl group, cyclophene Tyl group, cyclohexyl group, methylcyclohexyl group, dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, decahydronaphthyl group, adamantyl group, 2-alkyladamantan-2-yl group, 1- (Adamantan-1-yl) alkane-1-yl group, norbornyl group, methyl norbornyl group, and isobornyl group is mentioned.

As a substituent which the C1-C20 alkyl group represented by R <^45> and R <^46> may have, Halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; -NR ¹¹¹ R ¹¹² (such as an amino group and a dimethylamino group) (R ¹¹¹ and R ¹¹² each independently represents 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 same alkyl groups having 1 to 20 carbon atoms represented by R ^9A , R ^10A , R ^11A and R ^12A .

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

As a substituent which the aromatic hydrocarbon group represented by R <^45> and R <^46> may have, C1-C4 alkyl groups, such as a methyl group and an ethyl group; Halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; C1-C6 alkoxy groups, such as a methoxy group and an ethoxy group; Haloalkyl groups having 1 to 6 carbon atoms such as a chloromethyl group and a trifluoromethyl group; Hydroxyl group; Sulfamoyl group; C1-C6 alkylsulfonyl groups, such as a methylsulfonyl group, are mentioned.

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

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ⁵⁵ include the same alkyl groups 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 . .

Examples of the aromatic hydrocarbon group which may have a substituent represented by R ⁵⁵ include the same ones 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 each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms, and each independently a hydrogen atom It is more preferable that they are a methyl group, a fluorine atom, or a chlorine atom.

R ^9A , R ^10A , R ^11A and R ^12A are each preferably 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,

It is more preferable that they are a C6-C20 aromatic hydrocarbon group which may have a halogen atom, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, or a hydroxyl group each independently, or a C1-C8 alkyl group.

It is preferable that R <^45> and R <^46> are a C6-C20 aromatic hydrocarbon group which may respectively independently have a C1-C20 alkyl group or a substituent,

It is more preferable that they are a C6-C20 aromatic hydrocarbon group which may have a halogen atom, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, or a hydroxyl group each independently, or a C1-C8 alkyl group.

It is preferable that R <^55> is a C6-C20 aromatic hydrocarbon group which may have a C1-C20 alkyl group or a substituent,

It is more preferable that it is a C6-C20 aromatic hydrocarbon group which may have a halogen atom, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, or a hydroxy group, or a C1-C8 alkyl group.

As monovalent cation dye, the compound represented by Formula (1-a-2)-the compound represented by Formula (1-a-14) are mentioned, Preferably it is represented by Formula (1-a-2) It is a compound represented by Formula (1-a-3), a compound represented by Formula (1-a-5), and a compound represented by Formula (1-a-6).

A bivalent anion compound means the compound which the valence of the anion in the said compound is a divalent total, It is preferable that it is a compound which has two monovalent anions, and the same monovalent anion is 2 It is more preferable that it is a compound which has a dog.

As the univalent anions, sulfonate anion [-SO ₃ ^-], or a carboxylate anion [-COO ^-] may be mentioned, preferably a sulfonate anion.

The divalent anion 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, It is more preferable that it is an aromatic compound which has at least 1 sulfonate anion, and it is especially preferable that it is a compound represented by Formula (1-b).

(In formula, R <^1b> represents the C6-C18 aromatic hydrocarbon group 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, naphthyl group and anthracenyl group, and preferably a phenyl group or a naphthyl group.

Group is an aromatic hydrocarbon of 6-18 carbon atoms represented by R ^1b substituent which may have a fluorine atom, halogen atom such as chlorine atom and bromine atom: nitro group: hydroxyl group: an amino group: methyl, ethyl, propyl, isopropyl, butyl An alkyl group having 1 to 4 carbon atoms such as a group, a sec-butyl group and a tert-butyl group: or a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group and a tert-butoxy group C1-C4 alkoxy group is mentioned, Preferably it is a hydroxyl group or an amino group.

When the C6-C18 aromatic hydrocarbon group represented by R < ^1b is a phenyl group, it is preferable that another monovalent anion is located in a meta position or an ortho position with respect to one monovalent anion.

When the C6-C18 aromatic hydrocarbon group represented by R < ^1b is a naphthyl group, it is preferable that one monovalent anion couple | bonds with the carbon atom which another anion couple | bonds with the carbon atom which is not adjacent to it. .

As a bivalent anion compound, the compound represented by the formula (1-b-1)-the compound represented by a formula (1-b-13) is mentioned.

The divalent anion 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), a formula It is a compound represented by (1-b-9) and a compound represented by a formula (1-b-10).

Examples of the anion dye (I-1) include anion dyes represented by formula (I-1a) to anion dyes represented by formula (I-9a), and anion dyes represented by formula (I-4a). Preferred dyes are anion dyes represented by formula (I-6a).

As a monovalent cation compound which does not have a coloring group (Hereinafter, this compound may be called "monovalent cation compound."), It has at least 1 substituent chosen from the group which consists of a polymeric group, a silicon atom, and a phosphorus atom. Furthermore, monovalent cation compounds which do not have a coloring group are preferable.

Examples of the polymerizable group include groups having an ethylenically unsaturated bond, and specific examples thereof include an alkenyl group, acryloyl group, and methacryloyl group.

Monovalent cations preferably have ammonium ions [-NH ₄ ⁺ ].

As a monovalent cation compound which has a polymeric group, the compound represented by Formula (Z-1) is mentioned.

Wherein (Z-1) of, R ¹ represents an alkanediyl group having a carbon number of 1~10, -CH ₂ contained in these alkanediyl group - is ^{-O-, -CO-, -NR 11 -,} -OCO It may be substituted by-, -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 a linear, branched and cyclic alkanediyl group, and specific examples thereof include a methylene group, an ethylene group, a propane-1,3-diyl group , Butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, ethane-1, 1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane-1,3- Diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group, cyclobutane-1,3-diyl group, cyclopentane-1 , 3-diyl group, cyclohexane-1,4-diyl group, norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, ah Tantan-2,6-diyl group is mentioned, Preferably it is a C1-C8 alkanediyl group.

Examples of the group in which -CH ₂ -in the alkenediyl group having 1 to 10 carbon atoms represented by R ¹ are substituted with -O- include the groups described below (* represents a bond).

Examples of the group in which -CH ₂ -included in the alkenediyl group having 1 to 10 carbon atoms represented by R ¹ are substituted with -CO- include the groups described below (* represents a bond).

A, -NR ¹¹ - - -CH ₂ contained in the alkanediyl group having 1 to 10 carbon atoms represented by R ¹ The group substituted by, it may be mentioned groups described in the following (* represents a binding hand).

Examples of the group in which -CH ₂ -in the alkenediyl group having 1 to 10 carbon atoms represented by R ¹ are substituted with -OCO- include the groups described below (* represents a bond).

Examples of the group in which -CH ₂ -in the alkenediyl group having 1 to 10 carbon atoms represented by R ¹ is substituted with -COO- include the groups described below (* represents a bond).

Examples of the group in which -CH ₂ -included in the alkenediyl group having 1 to 10 carbon atoms represented by R ¹ are substituted with -OCONH- include the groups described below (* represents a bond).

Examples of the group in which -CH ₂ -included in the alkenediyl group having 1 to 10 carbon atoms represented by R ¹ are substituted with -CONH- include the groups described below (* represents a bond).

Examples of the group in which -CH ₂ -included in the alkenediyl group having 1 to 10 carbon atoms represented by R ¹ are substituted with -NHCO- include the groups described below (* represents a bond).

As a cation compound which has a polymeric group, the compound represented by the formula (Z-1-1)-the compound represented by a formula (Z1-1-3) are mentioned, Preferably it is a formula (Z-1-1) It is a compound represented by.

As a cation compound which has a silicon atom, the compound represented by a formula (Z-2) is mentioned.

Wherein (Z-2) of, R ² represents an alkanediyl group having 1 to 10 carbon atoms Al, -CH ₂ contained in these alkanediyl group - is ^{-O-, -CO-, -NR 21 -,} -OCO It may be substituted by-, -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 of 1 to 10.]

As a C1-C10 alkanediyl group represented by R <^2> and R <^21> , the same thing as the C1-C10 alkanediyl group represented by R <^1> and R <^11> is mentioned.

-CH ₂ -contained in an alkanediyl group having 1 to 10 carbon atoms represented by R ² is -O-, -CO-, -NR ^21- , -OCO-, -COO-, -OCONH-, -CONH- Alternatively, the group substituted by -NHCO- is -O-, -CO-, -NR ^11- , -OCO-, or -CH ₂ -contained in an alkanediyl group having 1 to 10 carbon atoms represented by R ¹ . The same thing as the group substituted by COO-, -OCONH-, -CONH-, or -NHCO- is mentioned.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ⁴⁰ , R ⁴¹ and R ⁴² include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group and tert-butyl group, preferably methyl group or It is an ethyl group.

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

It is preferable that R ⁴⁰ , R ⁴¹ and R ^{42 be} the same group.

It is preferable that R <^40> , R <^41> and R <^42> are a hydroxyl group or a C1-C4 alkoxy group each independently, and it is more preferable that they are a methoxy group or an ethoxy group.

It is preferable that it is an integer of 1-8, and, as for q, it is more preferable that it is an integer of 1-3.

As a cation compound which has a silicon atom, the compound represented by Formula (Z-2-1)-the compound represented by Formula (Z-2-12) can be mentioned, and is represented by Formula (Z-2-1) The compound represented by a compound-a formula (Z-2-6) is preferable.

As a cation compound which has a phosphorus atom, the compound represented by a formula (Z-3) is mentioned.

[In formula (Z-3), R <^50> , R <^51> , R <^52> and R <^53> represent a C1-C10 alkyl group, a C2-C10 alkenyl group, or the phenyl group which may be substituted each independently.]

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ⁵⁰ , R ⁵¹ , R ⁵² and R ⁵³ are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n -Pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 1-methylbutyl group, 1,1,3,3-tetramethylbutyl group, 1,5-dimethylhexyl group and 2-ethylhex A practical group etc. are mentioned, Preferably it is a methyl group, an ethyl group, or 2-ethylhexyl group.

Examples of the alkenyl group having 2 to 10 carbon atoms represented by R ⁵⁰ , R ⁵¹ , R ⁵² and R ⁵³ include a vinyl group, isopropenyl group, pentenyl group, hexenyl group and the like, and are preferably vinyl groups.

Of R ^50, R ^51, R ^52, and as the phenyl group having a substituent represented by R ^53, 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec- butyl group and a tert- butyl group Alkyl groups; A methoxy group, an ethoxy group, a propoxy group, and a C1-C4 alkoxy group can be mentioned.

As a cation compound which has a phosphorus atom, the compound represented by a formula (Z-3-1)-the compound represented by a formula (Z-3-6) is mentioned. 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 dyes (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 the formula (I-16) to a dye represented by the formula (I-27) and a dye represented by the formula (I-33) to the formula (I-47). More preferably, a dye represented by formula (I-16), a dye represented by formula (I-19), a dye represented by formula (I-27), and a formula (I-33). It is a dye represented by-represented by Formula (I-35).

Next, the manufacturing method of salt forming dye (I) is demonstrated.

The salt-forming dye (I) can be obtained by reacting anion dye (I-1) with a monovalent cation compound in water. The sequence of this reaction is mentioned later.

Anion dye (I-1) can be obtained by making monovalent cation dye and a bivalent anion compound react in water.

0 degreeC-120 degreeC is preferable, and, as for reaction temperature of monovalent cation dye and a bivalent anion compound, 10 degreeC-100 degreeC is more preferable. 1 to 24 hours are preferable and, as for reaction time, 3 to 8 hours are more preferable.

The well-known various methods can be employ | adopted for the method of obtaining anion dye (I-1) from a reaction mixture. For example, the method by filtering the precipitate which generate | occur | produces after completion | finish of reaction, and wash | cleaning with water is mentioned. As needed, you may refine | purify further by well-known methods, such as recrystallization.

Monovalent cation dye can be manufactured by making the compound represented by Formula (C-II) react with the compound represented by Formula (C-III), for example when represented by Formula (I-a). Such reaction may be performed in presence of an organic solvent, and may be performed in absence of solvent.

[Wherein, R ^1A to R ^12A and A are the same as defined above, respectively.]

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

30 degreeC-180 degreeC is preferable, and, as for reaction temperature, 80 degreeC-130 degreeC is more preferable. 1 hour-12 hours are preferable, and, as for reaction time, 3 hours-8 hours are more preferable.

The reaction of the compound represented by the formula (C-III) and the compound represented by the formula (C-II) is preferably carried out in the presence of an organic solvent in terms of yield. As an organic solvent, Hydrocarbon solvent, such as toluene and xylene; Halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and chloroform; Alcohol solvents such as methanol, ethanol, isopropanol and butanol; Nitro hydrocarbon solvents such as nitrobenzene; Ketone solvents such as methyl isobutyl ketone; Amide solvents such as 1-methyl-2-pyrrolidone; Etc. can be mentioned.

The amount of the organic solvent used is preferably 1 to 300 parts by mass, more preferably 2 to 200 parts by mass with respect to 1 part by mass of the compound represented by the formula (C-II).

The reaction of the compound represented by the formula (C-III) and the compound represented by the formula (C-II) is preferably carried out in the presence of a condensing agent in terms of yield. Phosphoric acid, polyphosphoric acid, phosphorus oxychloride, sulfuric acid, thionyl chloride, etc. are mentioned as a condensing agent.

The amount of the condensing agent used is preferably 1 to 20 parts by mass, and more preferably 1 to 5 parts by mass with respect to 1 part by mass of the compound represented by formula (C-II).

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

As for the method of obtaining monovalent anion dye, the method of adding a reaction mixture to alcohol is preferable. The temperature at the time of adding a reaction mixture becomes like this. Preferably it is -100-50 degreeC, More preferably, it is -80-0 degreeC. Moreover, it is preferable to stir at about the same temperature for 0.5 to 2 hours after that. The crystals collected by filtration are preferably washed with water or the like and then dried. Moreover, you may refine | purify further by well-known methods, such as recrystallization as needed.

As mentioned above, salt-forming dye (I) can be obtained by reaction of anion dye (I-1) and a monovalent cation compound.

It is preferable that it is 0-120 degreeC, and, as for the reaction temperature of anion dye (I-1) and monovalent cation compound, it is more preferable that it is 10-100 degreeC. 1 to 24 hours are preferable and, as for reaction time, 3 to 8 hours are more preferable.

The well-known various methods can be employ | adopted for the method of acquiring salt-forming dye (I) from a reaction mixture. For example, the method by filtering the precipitate which generate | occur | produces after completion | finish of reaction, and wash | cleaning with water is mentioned. As needed, you may refine | purify further by well-known methods, such as recrystallization.

The colored curable resin composition of this invention contains the coloring agent (A) containing resin salt (I), resin (B), a polymeric compound (C), and a polymerization initiator (D). Moreover, you may contain a solvent (E).

<Colorant (A)>

A coloring agent (A) may contain 2 or more types of salt-forming dyes (I).

The coloring agent (A) may contain other dyes (A2), pigments (P), or a mixture thereof in addition to the salt dye (I) 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, sulfonamide derivatives of acid dyes, and the like as dyes in the color index (Published by The Society of Dyers and Colourists). The compound classified, and the well-known dye described in the dyeing note (Shiksen-sha) are mentioned. Moreover, according to the chemical structure, coumarin dyes: alloy azo dyes: pyridoneazo dyes: barbiturate azo dyes: quinophthalone dyes: methine dyes: cyanine dyes: anthraquinone dyes: trifetyl methane dyes: xanthene Dyes: tetraazaporphyrin dyes: phthalocyanine dyes; and mixtures thereof.

The content of the salt-forming dye (I) is preferably 3 to 99.9 mass%, more preferably 4 to 80 mass%, and still more preferably 5 to 30 mass%, based on the total amount of the colorant (A). When content of salt-forming dye (I) exists in said range, the brightness at the time of using a color filter is high, and it is preferable.

As pigment (P), a well-known pigment can be used and the pigment classified by the pigment in the color index (The Society of Dyers and Colourists) is mentioned.

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, Yellow pigments such as 139, 147, 148, 150, 153, 154, 166, 173, 194, 214;

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

Green pigments, such as C. I. pigment green 7, 36, 58, are mentioned.

As the pigment (P), CI pigment yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, Yellow pigments such as 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; Green pigments, such as C. I. pigment green 7, 36, 58, are preferable, and C. I. pigment yellow 150, 185, and C. I. pigment green 58 are more preferable. By including said pigment, optimization of a transmission spectrum is easy and the light resistance and chemical-resistance of a color filter become favorable.

Content of a coloring agent (A) becomes like this. Preferably it is 5-60 mass% with respect to the total amount of solid content, More preferably, it is 8-55 mass%, More preferably, it is 10-50 mass%. When content of a coloring agent (A) exists in said range, since the color density at the time of setting it as a color filter is enough, and a resin (B) and a polymeric compound (C) can be contained in a composition in a required amount, mechanical strength is sufficient Patterns can be formed.

The total amount of solid content means the quantity which subtracted content of a solvent from the total amount of colored curable resin composition. The total amount of solid content and content of each component with respect to this can be measured by well-known analytical means, such as liquid chromatography or gas chromatography, for example.

<Resin (B)>

It is preferable that resin (B) is alkali-soluble resin. As resin (B), the following resin [K1]-[K6], etc. are mentioned.

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

Resin [K2]; Copolymer with (Ba) and (Bb) and monomer (Bc) copolymerizable with (Ba) (but different from (Ba) and (Bb)) (Hereinafter, it may be called "(Bc).") ;

Resin [K3]; Copolymers of (Ba) and (Bc);

Resin [K4]; Resin which (Bb) was made to react with the copolymer of (Ba) and (Bc);

Resin [K5]; Resin which (Ba) was made to react with the copolymer of (Bb) and (Bc);

Resin [K6]; Resin which (Ba) was made to react the copolymer of (Bb) and (Bc), and carboxylic anhydride was made to react further.

As (Ba), unsaturated monocarboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, 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-cyclohexenedicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hepto-2-ene, 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-6-methylbicyclo [ 2.2.1] bicyclo unsaturated compounds containing carboxyl groups, such as hepto-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hepto-2-ene;

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

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

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

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

(Bb) 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. As for (Bb), the monomer which has a C2-C4 cyclic ether and a (meth) acryloyloxy group is preferable.

In addition, in this specification, "(meth) acrylic acid" represents at least 1 sort (s) chosen from the group which consists of acrylic acid and methacrylic acid. Notation, such as "(meth) acryloyl" and "(meth) acrylate", also has the same meaning.

As (Bb), the monomer which has an oxiranyl group and ethylenically unsaturated bond; Monomers having an oxetanyl group and an ethylenically unsaturated bond; The monomer etc. which have a tetrahydropril group and ethylenically unsaturated bond are mentioned.

As (Bb), since the reliability of heat resistance, chemical resistance, etc. of the color filter obtained can be made higher, it is preferable that it is a monomer which has an oxiranyl group and ethylenically unsaturated bond.

As (Bc), methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethyl hexyl ( Meta) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (Meth) acrylate and tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate (in the technical field, it is called "dicyclopentanyl (meth) acrylate" as a conventional name. It may be called "tricyclodecyl (meth) acrylate.", Tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (in this technical field, it is a common name as "dicyclophene" Tenyl (meth) acrylate.), Dicyclopentanyl jade Ethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (Meth) acrylic acid esters such as (meth) acrylate and benzyl (meth) acrylate;

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

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

Bicyclo [2.2.1] hepto-2-ene, 5-methylbicyclo [2.2.1] hepto-2-ene, 5-ethylbicyclo [2.2.1] hepto-2-ene, 5-hydroxybi Cyclo [2.2.1] hepto-2-ene, 5-hydroxymethylbicyclo [2.2.1] hepto-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hepto-2 -Ene, 5-methoxybicyclo [2.2.1] hepto-2-ene, 5-ethoxybicyclo [2.2.1] hepto-2-ene, 5,6-dihydroxybicyclo [2.2.1] hepto 2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hepto-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] hepto- 2-ene, 5,6-dimethoxybicyclo [2.2.1] hepto-2-ene, 5,6-diethoxybicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5-methyl Bicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] Hepto-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hepto-2-ene, 5-phenoxy Cycarbonylbicyclo [2.2.1] hepto-2-ene, 5,6-bi Ratios of s (tert-butoxycarbonyl) bicyclo [2.2.1] hepto-2-ene and 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hepto-2-ene Cyclo unsaturated compounds;

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

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

Among them, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hepto-2-ene and the like are preferable in terms of copolymerization reactivity and heat resistance. Do.

Examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid copolymer, and the like. Resin [K1];

Glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2 .1.0 ^2.6] decyl acrylate / (meth) resins such as acrylic acid / N- cyclohexyl maleimide copolymer, 3-methyl-3- (meth) acryloyloxyethyl-methyl oxetane / (meth) acrylic acid / styrene copolymer [K2];

Resins such as benzyl (meth) acrylate / (meth) acrylic acid copolymer and styrene / (meth) acrylic acid copolymer;

Resin which glycidyl (meth) acrylate was added to the benzyl (meth) acrylate / (meth) acrylic acid copolymer, and glycidyl (meth) to the tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer Resin [K4], such as resin which added the acrylate, and resin which added glycidyl (meth) acrylate to the tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer;

Of resin which made (meth) acrylic acid react with the copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate, and tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate Resins [K5], such as resin which made (meth) acrylic acid react with the copolymer;

Resin [K6] etc., such as resin in which tetrahydrophthalic anhydride was made to react with resin which (meth) acrylic acid reacted with the copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate, are mentioned. have.

As resin (B), resin [K1] and resin [K2] are preferable.

Resin (B) is based on the method described in the document "Experimental method of polymer synthesis" (Oka Takayuki, published by Kagakudojin Co., Ltd., First Edition March 1, 1972) and cited documents described in this document. It can manufacture by reference.

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

The weight average molecular weight of polystyrene conversion of resin (B) becomes like this. Preferably it is 3,000-100,000, More preferably, it is 5,000-50,000, More preferably, it is 5,000-30,000. When the molecular weight is in the above range, the hardness of the color filter is improved, the residual film ratio is high, the solubility in the developer of the unexposed part 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 resin (B) becomes like this. Preferably it is 1.1-6, More preferably, it is 1.2-4.

The acid value of resin (B) becomes like this. Preferably it is 50-170 mg-KOH / g, More preferably, it is 60-150 mg-KOH / g, More preferably, it is 70-135 mg-KOH / g to be. 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 titration using, for example, an aqueous potassium hydroxide solution.

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

<Polymerizable compound (C)>

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

It is preferable that a polymeric compound (C) is a polymeric compound which has three or more ethylenically unsaturated bonds. As such a polymeric compound, a trimethylol propane tri (meth) acrylate, a pentaerythritol tri (meth) acrylate, a pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipenta Erythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritolhepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) Acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol Modified pentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, car Prolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. are mentioned.

As a polymeric compound which has three or more ethylenically unsaturated bonds, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

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

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

<Polymerization Initiator (D)>

As the polymerization initiator (D), any compound capable of generating an active radical, an acid or the like by the action of light or heat and capable of initiating polymerization can use a known polymerization initiator. As a polymerization initiator which generates an active radical, an O-acyl oxime compound, an alkylphenone compound, a triazine compound, an acyl phosphine oxide compound, and a biimidazole compound are mentioned.

As the O-acyl oxime compound, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1- On-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl- 2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl)- 9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-one-2-imine and the like. You may use commercially available products, such as Irgacure (trademark) OXE01, OXE02 (above, BASF Corporation), and N-1919 (ADEKA Corporation). Among them, the O-acyl oxime compound is N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane At least one selected from the group consisting of -1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine is preferable, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine is more preferred. If it is these O-acyl oxime compounds, it exists in the tendency for a high brightness color filter to be obtained.

As the alkylphenone compound, 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propane-1-one and 2-dimethylamino-1- (4-morpholinophenyl) -2-benzyl Butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one, 2-hydroxy-2 -Methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenylketone And oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propane-1-one, α, α-diethoxyacetophenone, benzyldimethyl ketal and the like. You may use commercial items, such as Irgacure (trademark) 369, 907, 379 (above, BASF Corporation make).

As the triazine compound, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4- Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl ) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl ] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4 -Bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, etc. are mentioned.

2,4,6-trimethyl benzoyl diphenyl phosphine oxide etc. are mentioned as an acyl phosphine oxide compound. You may use commercial items, such as Irgacure 819 (made by BASF Corporation).

As a biimidazole compound, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4 , 4 ', 5,5'-tetraphenylbiimidazole (see JP-A-6-75372, JP-A-6-75373, etc.), 2,2'-bis (2- Chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimi Dazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4, 4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole (see JP-A-48-38403, JP-A-62-174204, etc.), 4,4', 5 And imidazole compounds (see JP-A-7-10913, etc.) in which the phenyl group at the 5'-position is substituted with a carboalkoxy group.

Furthermore, as a polymerization initiator (D), Benzoin compounds, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compound and the like.

Examples of the polymerization initiator for generating an acid include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodium p-toluenesulfonate, diphenyliodine Onium salts such as nium hexafluoro antimonate, nitrobenzyl tosylates, benzointosylates and the like.

As a polymerization initiator (D), the polymerization initiator containing at least 1 sort (s) chosen from the group which consists of an O-acyl oxime compound, an alkylphenone compound, a triazine compound, an acyl phosphine oxide compound, and a biimidazole compound is preferable, O is The polymerization initiator containing an acyl oxime compound is more preferable.

Content of a polymerization initiator (D) becomes like this. Preferably it is 0.1-30 mass parts with respect to 100 mass parts of total amounts of resin (B) and a polymeric compound (C), More preferably, it is 1-20 mass parts. When content of a polymerization initiator (D) exists in the said range, since there exists a tendency for high sensitivity and shortening an exposure time, productivity of a color filter improves.

<Solvent (E)>

The solvent (E) can use the solvent normally used in the said field | area. For example, 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-) and an ether ester Solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule and no -COO-), alcoholic solvents (containing OH in the molecule,- Solvents not containing O-, -CO- and -COO-); aromatic hydrocarbon solvents; amide solvents; dimethyl sulfoxide.

As the ester solvent, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutane, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate and butyric acid Butyl, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetic acid, ethyl acetoacetate, cyclohexanol acetate and γ-butyrolactone.

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

As an ether ester solvent, methyl methoxy acetate, ethyl methoxy acetate, methoxy acetate butyl, ethoxy acetate methyl, ethoxy acetate ethyl, 3-methoxy propionate methyl, 3-methoxy propionate ethyl, 3-ethoxy propionate methyl, Ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionic acid, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2-methyl Methyl propionate, 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl To ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl There may be mentioned the LE acetate and diethylene glycol monobutyl ether acetate.

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

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

Benzene, toluene, xylene, and mesitylene are mentioned as an aromatic hydrocarbon solvent.

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

As for the solvent (E), the organic solvent whose boiling point in 1 atm is 120 degreeC-210 degreeC from an applicability | paintability and a drying point is preferable.

As a solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxy propionate ethyl, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy- 4-methyl-2-pentanone and N, N-dimethylformamide are preferable,

Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, N, N-dimethylformamide, N-methylpyrrolidone, and ethyl 3-ethoxypropionate are more preferable.

Content of a solvent (E) becomes like this. Preferably it is 70-95 mass% with respect to the total amount of the colored curable resin composition of this invention, More preferably, it is 75-92 mass%.

The total amount of solid content of a colored curable resin composition becomes like this. Preferably it is 5-30 mass%, More preferably, it is 8-25 mass%. When content of a solvent (E) exists in the said range, flatness at the time of application | coating will become favorable, and when a color filter is formed, there exists a tendency for display characteristics to become favorable because color density does not run short.

<Other ingredients>

The colored curable resin composition of this invention is an additive known in the art, such as a polymerization start adjuvant, a leveling agent, a filler, other high molecular compounds, an adhesion promoter, antioxidant, an optical stabilizer, and a chain transfer agent as needed. It may include.

<Method for producing colored curable resin composition>

The colored curable resin composition of this invention is a coloring agent (A), resin (B), a polymeric compound (C), a polymerization initiator (D), and the solvent (E), a leveling agent, and polymerization used as needed, for example. It can prepare by mixing starting preparation and other components.

When a pigment (P) is included as a coloring agent (A), the pigment (P) is previously mixed with one part or all of the solvent (E), and until the average particle diameter of a pigment becomes about 0.2 micrometer or less, It is preferable to disperse | distribute using a bead mill etc. Under the present circumstances, you may mix | blend a part or all of the said pigment dispersant and resin (B) as needed. The target colored curable resin composition can be prepared by mixing the remaining components with the pigment dispersion liquid thus obtained so as to have a predetermined concentration.

Dye, such as salt salt, may be previously melt | dissolved in one part or all part of solvent (E), and a solution may be prepared.

It is preferable to filter this solution with the filter of about 0.01-1 micrometer of pore diameters.

It is preferable to filter the colored curable resin composition after mixing with the filter of 0.1-10 micrometers of pore diameters.

<Method of manufacturing color filter>

The color filter of this invention is formed from the above-mentioned colored curable resin composition.

As a method of manufacturing a color filter with the colored curable resin composition of this invention, the photolithographic method, the inkjet method, the printing method, etc. are mentioned, The photolithographic method is preferable.

The photolithographic method is a method of apply | coating a coloring curable resin composition to a board | substrate, drying to form a coloring composition layer, exposing the said coloring composition layer through a photomask, and developing a coloring pattern.

In the photolithographic method, the colored coating film which is the hardened | cured material of the said coloring composition layer can be formed by not using a photomask at the time of exposure, and / or not developing. The coating film containing a coloring pattern may be sufficient as the color filter of this invention, and a coloring coating film may be sufficient as it.

The film thickness of a color filter can be suitably adjusted according to an objective, a use, etc., and is 0.1-30 micrometers normally, Preferably it is 0.1-20 micrometers, More preferably, it is 0.5-6 micrometers.

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

Formation of the coloring pattern by the photolithographic method can be performed by a well-known or usual apparatus and conditions. For example, it can manufacture as follows.

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

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

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

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

What is necessary is just to select the film thickness of a coloring composition layer suitably according to the film thickness of the target color filter.

Next, a coloring composition layer is exposed through the photomask for forming the target coloring pattern. The pattern according to the intended use is used for the pattern on the said photomask.

As a light source used for exposure, the light source which produces the light of 250-450 nm wavelength is preferable. For example, light of less than 350 nm is cut using a filter that cuts this wavelength range, or light of around 436 nm, 408 nm, and 365 nm vicinity is used by using a band pass filter that extracts these wavelength ranges. It may take out selectively. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp etc. are mentioned.

It is preferable to use exposure apparatuses, such as a mask aligner and a stepper, since the parallel light beam can be irradiated uniformly to the whole exposure surface, or the exact alignment of a photomask and the board | substrate with a coloring composition layer can be performed.

A colored pattern is formed on a board | substrate by developing the coloring composition layer after exposure contacting with a developing solution. By development, the unexposed part of a coloring composition layer melt | dissolves in a developing solution and is removed. As a developing solution, aqueous solution of alkaline compounds, such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, and tetramethylammonium hydroxide, is preferable.

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

The developing method may be any of a paddle method, a dipping method, a spray method, and the like. In addition, during development, the substrate may be tilted at an arbitrary angle.

It is preferable to wash with water after image development.

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

EXAMPLE

Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples. In the examples,% and parts indicating the content or the amount of use are based on mass unless otherwise specified in advance.

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

Synthesis Example 1

The following reaction was performed in nitrogen atmosphere.

After adding 36.3 parts of potassium thiocyanate and 160 parts of acetone to the flask provided with a cooling tube and the stirring apparatus, it stirred at room temperature for 30 minutes. 50 parts of benzoic acid chloride (made by Tokyo Kasei Co., Ltd.) was dripped over the obtained mixture over 10 minutes, and it stirred at room temperature for 2 hours. After cooling the obtained reaction mixture, 45.7 parts of N-ethyl-o-toluidine (made by Tokyo Kasei Co., Ltd.) was dripped, and it stirred further at room temperature for 30 minutes. After cooling the obtained reaction mixture, 34.2 parts of 30% sodium hydroxide aqueous solution was dripped, and it stirred at room temperature for 30 minutes. 35.3 parts of chloroacetic acid were dripped at the obtained reaction mixture at room temperature, and it heated and refluxed for 7 hours. Subsequently, after cooling the reaction mixture 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 left 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 200 parts of 1 N hydrochloric acid, 200 parts of water, and 200 parts of saturated saline. Manganese was added to the organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The solvent was distilled off the obtained organic layer, and the pale yellow liquid was obtained. The pale yellow liquid obtained was purified by column chromatography. The purified pale yellow liquid was dried at 60 degreeC under reduced pressure, and 52.0 parts of compounds which are represented by a formula (B-I-1) were obtained.

The following reaction was performed in nitrogen atmosphere.

9.3 parts of the compound represented by Formula (B-I-1), 4,4'-bis (diethylamino) benzophenone (manufactured by Tokyo Kasei Co., Ltd.) in a flask equipped with a cooling tube and a stirring device 10 Part and 20 parts of toluene were added, 14.8 parts of phosphorus oxychloride was added, and it stirred at 95-100 degreeC for 3 hours. The obtained reaction mixture was cooled to room temperature and then diluted with 170 parts of isopropanol. The diluted reaction solution was poured into 300 parts of saturated saline solution, then 100 parts of toluene was added and stirred for 30 minutes. The obtained mixture was left to stand for 30 minutes and separated into an organic layer and an aqueous layer. The organic layer was obtained by performing liquid separation operation. The obtained organic layer was washed with 300 parts of saturated saline. Manganese was added to the organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The solvent was distilled off the obtained organic layer, and the blue-purple solid was obtained. The obtained blue-purple solid was dried at 60 degreeC under reduced pressure, and 19.8 parts of compounds represented by a formula (A-II-1) were obtained.

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

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

                          Exact Mass: 636.3

Synthesis Example 2

6.3 parts of compounds represented by formula (A-II-1) were dissolved in 500 parts of ion-exchanged water. 2.8 parts of 1, 5- dinaphthalene sulfonic acid (made by Tokyo Kasei Co., Ltd.) was added to the obtained mixture, and it stirred at 40 degreeC for 12 hours. After cooling the obtained reaction mixture at room temperature, the crystal | crystallization which produced was collected by filtration, and it washed with ion-exchange water, dried at 60 degreeC for 24 hours, and the solid 8.8 containing the compound represented by Formula (A-II-2). Got wealth.

Example 1

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

To the obtained aqueous solution, 2.2 parts of 3-aminopropylethoxysilane (made by Tokyo Kasei Co., Ltd.) was added, and it stirred at 30 degreeC for 12 hours. After cooling the obtained reaction mixture at room temperature, the crystal | crystallization which produced was collected by filtration, and it wash | cleaned with ion-exchange water, and dried at 60 degreeC for 24 hours, and obtained 11.1 parts of compounds represented by a formula (A2-Z2-4).

Example 2

In Example 1, except having used the salt of formula (d-1) instead of 3-aminopropyl ethoxysilane, it synthesize | combined similarly and obtained the compound represented by Formula (A2-Z1-1).

Example 3

In Example 1, except having used the salt of Formula (d-2) instead of 3-aminopropylethoxysilane, it synthesize | combined similarly and obtained the compound represented by Formula (A2-Z3-1).

Synthesis Example 3

19 parts methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-ylacrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-9-ylacrylic 171 parts of rate mixtures (content: 50:50 in molar ratio) (brand name "E-DCPA", Daicel Corporation make) were melt | dissolved in 40 parts of propylene glycol monomethyl ether acetates, and the solution was obtained (hereinafter, solution (1) I may say).

26 parts of 2,2'- azobis (2, 4- dimethylvaleronitrile) were melt | dissolved in 120 parts of propylene glycol monomethyl ether acetate, and the solution was obtained (Hereinafter, it may be called solution (2).).

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

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

[Preparation of colored curable resin composition]

Example 4

Colored curable resin composition (1) was obtained by mixing the following coloring agent (A), resin (B), a polymeric compound (C), a polymerization initiator (D), a solvent (E), and a leveling agent (F).

Colorant (A): 20 parts of dye represented by formula (A2-Z2-4);

Resin (B): 53 parts of resin (B-1) (solid content conversion);

Polymerizable compound (C): 16 parts of dipentaerythritol hexaacrylate (KAYARAD® DPHA; manufactured by Nihon Kayaku Co., Ltd.);

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

(Toray Silicon SH8400; Toray Dow Corning Corporation) 0.15part

Example 5

Colored curable resin composition (2) was obtained by mixing the following coloring agent (A), resin (B), a polymeric compound (C), a polymerization initiator (D), a solvent (E), and a leveling agent (F).

Colorant (A): 21 parts of dye represented by formula (A2-Z1-1);

Resin (B): 50 parts of resin (B-1) (solid content conversion);

Polymerizable compound (C): 16 parts of dipentaerythritol hexaacrylate (KAYARAD® DPHA; manufactured by Nihon Kayaku Co., Ltd.);

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

(Toray Silicon SH8400; Toray Dow Corning Corporation) 0.15part

Example 6

Colored curable resin composition (3) was obtained by mixing the following coloring agent (A), resin (B), a polymeric compound (C), a polymerization initiator (D), a solvent (E), and a leveling agent (F).

Colorant (A): 26 parts of dye represented by formula (A2-Z3-1);

Resin (B): 50 parts of resin (B-1) (solid content conversion);

Polymeric compound (C): 20 parts of dipentaerythritol hexaacrylate (KAYARAD® DPHA; manufactured by Nihon Kayaku Co., Ltd.);

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

(Toray Silicon SH8400; Toray Dow Corning Corporation) 0.15part

Comparative Example 1

Colored curable resin composition (1 ') was obtained by mixing the following coloring agent (A), resin (B), a polymeric compound (C), a polymerization initiator (D), a solvent (E), and a leveling agent (F).

Colorant (A): 26 parts of dye represented by formula (A-III-1);

Resin (B): 53 parts of resin (B-1) (solid content conversion);

Polymerizable compound (C): 16 parts of dipentaerythritol hexaacrylate (KAYARAD® DPHA; manufactured by Nihon Kayaku Co., Ltd.);

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

(Toray Silicon SH8400; Toray Dow Corning Corporation) 0.15part

Test case

[Production of color filter]

After apply | coating this colored curable resin composition by the spin coat method on the glass substrate (# 1737 (made by Corning Corporation)) of a 2-inch square, it prebaked at 100 degreeC and formed the coloring composition layer. After cooling, an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used for exposure at an exposure amount (365 nm standard) of 150 mJ / cm 2 under an atmospheric atmosphere. In addition, a photomask was not used. The color filter (film thickness of 2.8 micrometers) was produced by performing the post-baking the coloring composition layer after exposure at 180 degreeC in oven for 20 minutes.

[Heat resistance evaluation]

The said color filter was heated at 30 degreeC for 20 minutes, and the color difference ((DELTA) Eab *) before and behind the heating of the said color filter was measured using the colorimeter (OSP-SP-200; the product made by OLYMPUS).

About the said coating film obtained from each coloring photosensitive resin composition of Example 4, Example 5, Example 6, and the comparative example 1, the color difference ((DELTA) Eab *) was calculated | required. The results are shown in Table 1.

In addition, color difference (DELTA) Eab * shows that it is a material which has high heat resistance, so that the value is small.

Table 1

The colored curable resin composition containing the salt-proof dye of this invention can provide the color filter which shows favorable heat resistance. The said color filter is useful for a display apparatus (liquid crystal display apparatus, organic electroluminescent apparatus, electronic paper, etc.) and a solid-state image sensor.

Claims (12)

In the salt-forming dye formed from monovalent cation dye, a bivalent anion compound, and the monovalent cation compound which does not have a coloring group,
The monovalent cation dye is a compound represented by formula (1-a-1),

[In formula (1-a-1), X represents an oxygen atom or a sulfur atom.
R ^1A to R ^8A each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or an alkyl group having 1 to 20 carbon atoms, and -CH ₂ -contained in an alkyl group having 1 to 20 carbon atoms is substituted with -O-. You may be.
R ^9A to R ^12A each independently represent 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 is contained in an alkyl group having 1 to 20 carbon atoms. CH ₂ -may be substituted with -O-.
R ⁴⁵ and R ⁴⁶ each independently represent 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 each having 1 to 20 carbon atoms which may have the substituent. -CH ₂ -contained in the alkyl group of 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.]
The divalent anion compound is a compound represented by formula (1-b),

[In formula (1-b), R <^1b> represents the C6-C18 aromatic hydrocarbon group which may have a substituent.]
The monovalent cation compound which does not have the said coloring group is a salt-forming dye which is a compound which has at least 1 substituent chosen from the group which consists of a polymeric group, a silicon atom, and a phosphorus atom, and does not have a coloring group. The method of claim 1,
A salt salt dye obtained from the monovalent anion dye formed from monovalent cation dye and a bivalent anion compound, and the monovalent cation compound which does not have a coloring group. delete delete delete delete delete The coloring agent containing the salt-forming dye of Claim 1 or 2. The colored curable resin composition containing the coloring agent of Claim 8, resin, a polymeric compound, and a polymerization initiator. The coating film formed from the colored curable resin composition of Claim 9. The color filter formed from the colored curable resin composition of Claim 9. A display device comprising the color filter according to claim 11.