KR102450273B1 - Colored composition - Google Patents

Abstract

[식 (Ⅰ) 중, R^N1 및 R^N2는, 서로 독립적으로, 치환기를 가지고 있어도 되는 탄소수 1∼40의 지방족 탄화수소기를 나타낸다. R^N3은, 치환기를 가지고 있어도 되는 탄소수 1∼40의 탄화수소기 또는 치환기를 가지고 있어도 되는 복소환기를 나타낸다. R¹∼R⁸은, 서로 독립적으로, 수소 원자, -CO-R¹⁰², -COO-R¹⁰¹, -OCO-R¹⁰², -O-R¹⁰², -SO₂-R¹⁰¹, -SO₂N(R¹⁰²)₂, -CON(R¹⁰²)₂, -N(R¹⁰²)₂, -NHCO-R¹⁰², 할로겐 원자, 시아노기, 니트로기, -SO₃M, -CO₂M, 치환기를 가지고 있어도 되는 탄소수 1∼40의 탄화수소기 또는 치환기를 가지고 있어도 되는 복소환기를 나타낸다. R¹⁰¹은, 치환기를 가지고 있어도 되는 탄소수 1∼40의 탄화수소기 또는 치환기를 가지고 있어도 되는 복소환기를 나타낸다. R¹⁰²는, 수소 원자, 치환기를 가지고 있어도 되는 탄소수 1∼40의 탄화수소기 또는 치환기를 가지고 있어도 되는 복소환기를 나타낸다. M은 수소 원자 또는 알칼리 금속 원자를 나타낸다. R¹⁰¹, R¹⁰² 및 M이 복수 존재하는 경우, 그들은 동일해도 되고 상이해도 된다. A^{g -}는 g가의 아니온을 나타낸다. g는 1∼14의 정수를 나타낸다.]The coloring composition containing the compound and resin represented by Formula (I).

[In formula (I), R ^N1 and R ^N2 each independently represent an aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have a substituent. R ^N3 represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent. R ¹ to R ⁸ are each independently a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , -SO ₂ N(R ¹⁰² ) ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , halogen atom, cyano group, nitro group, -SO ₃ M, -CO ₂ M, number of carbon atoms which may have a substituent It represents the hydrocarbon group of 1-40 or the heterocyclic group which may have a substituent. R ¹⁰¹ represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent. R ¹⁰² represents a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent. M represents a hydrogen atom or an alkali metal atom. When two or more R ¹⁰¹ , R ¹⁰² and M exist, they may be the same or different. A ^{g -} represents a g-valent anion. g represents an integer from 1 to 14.]

Description

Coloring composition {COLORED COMPOSITION}

The present invention relates to compounds useful as colorants and to coloring compositions.

Dye is used for color display using reflected light or transmitted light in, for example, textile materials, liquid crystal display devices, and inkjet fields. As such a dye, coumarin 6 represented by the following formula is known (Japanese Patent Laid-Open No. 2006-154740).

The present invention includes the following inventions.

[1] The coloring composition containing the compound and resin represented by Formula (I).

[In formula (I), R ^N1 and R ^N2 each independently represent an aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have a substituent.

R ^N3 represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent.

R ¹ to R ⁸ are each independently a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -COCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , - SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² ,-NHCO-N(R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON(R ¹⁰² ) ) ₂ , a halogen atom, a cyano group, a nitro group, -SO ₃ M, -CO ₂ M, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.

R ¹⁰¹ represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent.

R ¹⁰² represents a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.

M represents a hydrogen atom or an alkali metal atom.

When two or more R ¹⁰¹ , R ¹⁰² and M exist, they may be the same or different.

A ^{g -} represents a g-valent anion. g represents an integer from 1 to 14.]

[2] The coloring composition according to [1], wherein A ^{g -} is an anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen as essential elements, or a fluorine-containing anion.

[3] The coloring composition according to [1] or [2], wherein A ^{g −} is an anion containing at least one element selected from the group consisting of tungsten and phosphorus and oxygen as essential elements, or a fluorine-containing anion.

[4] The coloring composition according to any one of [1] to [3], wherein A ^{g −} is an anion containing at least one element selected from the group consisting of tungsten and phosphorus and oxygen as essential elements.

[5] The coloring composition according to any one of [1] to [4], wherein R ^N1 and R ^N2 are each independently an alkyl group having 1 to 10 carbon atoms which may have a substituent.

[6] The coloring composition according to any one of [1] to [5], further comprising a solvent.

[7] The coloring composition according to any one of [1] to [6], further comprising a yellow colorant, an orange colorant, or a red colorant.

[8] A colored curable composition comprising the colored composition according to any one of [1] to [7], and a polymerizable compound.

[9] The colored curable composition according to [8], further comprising a polymerization initiator.

[10] A color filter formed of the colored composition according to any one of [1] to [7] or the colored curable composition according to [8] or [9].

[11] A liquid crystal display device comprising the color filter according to [10].

[12] A compound represented by formula (I-B).

[In formula (I-B), R ^N1 and R ^N2 each independently represent an aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have a substituent.

R ^N3 represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent.

R ¹ to R ⁸ are each independently a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -COCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , - SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² ,-NHCO-N(R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON(R ¹⁰² ) ) ₂ , a halogen atom, a cyano group, a nitro group, -SO ₃ M, -CO ₂ M, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.

R ¹⁰¹ represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent.

R ¹⁰² represents a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.

M represents a hydrogen atom or an alkali metal atom.

When two or more R ¹⁰¹ , R ¹⁰² and M exist, they may be the same or different.

B ^{h −} represents an anion having an h valence containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen as essential elements.

h represents an integer from 1 to 14.]

[13] The compound according to [12], wherein B ^{h −} is an anion containing oxygen as essential elements and at least one element selected from the group consisting of tungsten and phosphorus.

[14] The compound according to [12] or [13], wherein R ^N1 and R ^N2 are each independently an alkyl group having 1 to 10 carbon atoms which may have a substituent.

The coloring composition of this invention contains the compound (Hereinafter, it may be called compound (I).) and resin (it may be hereafter called resin (B)) which are represented by Formula (I).

Compound (I) includes its tautomers and salts thereof.

Compound (I) can be used as a colorant.

The coloring composition of this invention may contain the 1 type, or 2 or more types of compound (I).

The coloring composition of this invention may contain the solvent (Hereinafter, it may be called solvent (E).).

Moreover, it is preferable that the compound (I) is disperse|distributed to the solvent (E).

The coloring composition of the present invention may be a coloring agent other than the compound (I) (hereinafter, referred to as a coloring agent (A1). In the following, the compound (I) and the coloring agent (A1) are collectively referred to as a “colorant (A)” In some cases.) may be included.

The coloring agent (A1) may contain 1 type, or 2 or more types of coloring agents.

The colorant (A1) preferably contains a yellow colorant, an orange colorant or a red colorant.

Moreover, the colored curable composition of this invention contains a compound (I), at least one of resin (B), and a solvent (E), and a polymeric compound (C).

The colored curable composition of this invention may contain the polymerization initiator (D).

The colored curable composition of the present invention may contain the polymerization initiator auxiliary (D1).

The coloring composition of this invention may also contain a leveling agent (F) and antioxidant further.

<Compound (I)>

Compound (I) is a compound represented by formula (I).

[In formula (I), R ^N1 and R ^N2 each independently represent an aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have a substituent.

R ^N3 represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent.

R ¹ to R ⁸ are each independently a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -COCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , - SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² ,-NHCO-N(R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON(R ¹⁰² ) ) ₂ , a halogen atom, a cyano group, a nitro group, -SO ₃ M, -CO ₂ M, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.

R ¹⁰¹ represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent.

R ¹⁰² represents a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.

M represents a hydrogen atom or an alkali metal atom.

When two or more R ¹⁰¹ , R ¹⁰² and M exist, they may be the same or different.

A ^g- represents a g-valent anion.

g represents an integer from 1 to 14.]

The carbon number of the aliphatic hydrocarbon group represented by R ^N1 and R ^N2 is 1 to 40, preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 15, particularly preferably 1 -10.

The aliphatic hydrocarbon group represented by R ^N1 and R ^N2 may be saturated or unsaturated, and may be linear or alicyclic.

Examples of the saturated or unsaturated chain aliphatic hydrocarbon group represented by R ^N1 and R ^N2 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, straight-chain alkyl groups such as heptadecyl group, octadecyl group and icosyl group; isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, (2-ethyl)butyl group, isopentyl group, neopentyl group, tert-pentyl group, (1-methyl)pentyl group, (2- methyl) pentyl group, (1-ethyl) pentyl group, (3-ethyl) pentyl group, isohexyl group, (5-methyl) hexyl group, (2-ethyl) hexyl group and (3-ethyl) heptyl group branched chain alkyl groups and the like; Vinyl group, 1-propenyl group, 2-propenyl group (allyl group), (1-methyl)ethenyl group, 2-butenyl group, 3-butenyl group, 1,3-butadienyl group, (1-(2-pro alkenyl groups such as phenyl))ethenyl, (1,2-dimethyl)propenyl, and 2-pentenyl; and the like. The number of carbon atoms in the saturated or unsaturated chain hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 15, particularly preferably 1 to 10, still more preferably 1 -8. Especially more preferably, it is 1-5. Especially, it is especially preferable that it is a C1-C10, More preferably, it is a C1-C8 linear or branched alkyl group, and a methyl group or an ethyl group is especially preferable.

Examples of the saturated or unsaturated alicyclic hydrocarbon group represented by R ^N1 and R ^N2 include a cyclopropyl group, 1-methylcyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, 1-methylcyclohexyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 1,2-dimethylcyclohexyl group, 1,3-dimethylcyclohexyl group, 1,4-dimethylcyclohexyl group, 2, 3-dimethylcyclohexyl group, 2,4-dimethylcyclohexyl group, 2,5-dimethylcyclohexyl group, 2,6-dimethylcyclohexyl group, 3,4-dimethylcyclohexyl group, 3,5-dimethylcyclohexyl group Sil group, 2,2-dimethylcyclohexyl group, 3,3-dimethylcyclohexyl group, 4,4-dimethylcyclohexyl group, cyclooctyl group, 2,4,6-trimethylcyclohexyl group, 2,2,6, cycloalkyl groups such as 6-tetramethylcyclohexyl group, 3,3,5,5-tetramethylcyclohexyl group, 4-pentylcyclohexyl group, 4-octylcyclohexyl group and 4-cyclohexylcyclohexyl group; Cycloalkenyl groups, such as a cyclohexenyl group (For example, cyclohexa-2-ene, cyclohexa-3-ene), a cycloheptenyl group, and a cyclooctenyl group; A norbornane group, an adamantyl group, bicyclo [2,2,2] octane, etc. are mentioned. The saturated or unsaturated alicyclic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, still more preferably 4 to 20 carbon atoms, still more preferably 4 to 15 carbon atoms, and particularly more Preferably it is 5-15, Most preferably, it is 5-10. Among them, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group are particularly preferable.

The aliphatic hydrocarbon group represented by R ^N1 and R ^N2 is a combination of the above aliphatic hydrocarbon group and an aromatic hydrocarbon group having 1 to 40 carbon atoms (for example, at least one of a chain hydrocarbon group and an alicyclic hydrocarbon group and an aromatic hydrocarbon group) one contribution.

Examples of such an aromatic hydrocarbon group include a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 4-vinylphenyl group, o-isopropylphenyl group, m-isopropylphenyl group, p-isopropylphenyl group, o-tert-butylphenyl group, m-tert-butylphenyl group , p-tert-butylphenyl group, mesityl group, 4-ethylphenyl group, 4-butylphenyl group, 4-pentylphenyl group, 2,6-bis(2-propyl)phenyl group, 4-cyclohexylphenyl group, 2,4,6- Trimethylphenyl group, 4-octylphenyl group, 4-vinylphenyl group, 1-naphthyl group, 2-naphthyl group, 5,6,7,8-tetrahydro-1-naphthyl group, 5,6,7,8-tetrahydro- aromatic hydrocarbon groups such as 2-naphthyl group, fluorenyl group, phenanthryl group, anthryl group and pyrenyl group; and the like. The aromatic hydrocarbon group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 15 carbon atoms.

As a group combining the above aliphatic hydrocarbon group and an aromatic hydrocarbon group having 1 to 40 carbon atoms (for example, at least one of a chain hydrocarbon group and an alicyclic hydrocarbon group and an aromatic hydrocarbon group), benzyl group, phenethyl group, 1-methyl group Aralkyl groups, such as a -1-phenylethyl group; arylalkenyl groups such as a phenylethenyl group (phenylvinyl group); Aryl alkynyl groups, such as a phenylethynyl group; a phenyl group to which one or more phenyl groups such as a biphenylyl group and a terphenylyl group are bonded; A cyclohexylmethylphenyl group, a benzylphenyl group, (dimethyl(phenyl)methyl)phenyl group, etc. are mentioned. The group represented by R ^N1 and R ^N2 is a combination of the above hydrocarbon groups (for example, a chain hydrocarbon group and an alicyclic hydrocarbon group), for example, a cyclopropylmethyl group, a cyclopropylethyl group, a cyclobutylmethyl group, and a cyclobutyl group. It may be an alkyl group to which one or more alicyclic hydrocarbon groups such as an ethyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexylmethyl group, a 2-methylcyclohexylmethyl group, a cyclohexylethyl group and an adamantylmethyl group are bonded.

The hydrocarbon group preferably has 4 to 30 carbon atoms, more preferably 6 to 30 carbon atoms, still more preferably 6 to 20 carbon atoms, still more preferably 4 to 20 carbon atoms, still more preferably 4 to 15 carbon atoms. and particularly preferably 6 to 15.

The hydrocarbon group represented by R ^N3 , R ¹ to R ⁸ , R ¹⁰¹ and R ¹⁰² has 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, still more preferably 1 to 40 carbon atoms. 15, particularly preferably 1 to 10.

The hydrocarbon group having 1 to 40 carbon atoms represented by R ^N3 , R ¹ to R ⁸ , R ¹⁰¹ and R ¹⁰² may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and the aliphatic hydrocarbon group may be saturated or unsaturated, and may be chain or alicyclic.

Examples of the saturated or unsaturated chain hydrocarbon group represented by R ^N3 , R ¹ to R ⁸ , R ¹⁰¹ and R ¹⁰² include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a de straight-chain alkyl groups such as a sil group, an undecyl group, a dodecyl group, a heptadecyl group, an octadecyl group and an icosyl group; isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, (2-ethyl)butyl group, isopentyl group, neopentyl group, tert-pentyl group, (1-methyl)pentyl group, (2- methyl) pentyl group, (1-ethyl) pentyl group, (3-ethyl) pentyl group, isohexyl group, (5-methyl) hexyl group, (2-ethyl) hexyl group and (3-ethyl) heptyl group branched chain alkyl groups and the like; Vinyl group, 1-propenyl group, 2-propenyl group (allyl group), (1-methyl)ethenyl group, 2-butenyl group, 3-butenyl group, 1,3-butadienyl group, (1-(2-pro alkenyl groups such as phenyl))ethenyl, (1,2-dimethyl)propenyl, and 2-pentenyl; and the like. The number of carbon atoms in the saturated or unsaturated chain hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 15, particularly preferably 1 to 10, still more preferably 1 to 8. Especially, it is especially preferable that it is a C1-C10, More preferably, it is a C1-C8 linear or branched alkyl group, and a methyl group or an ethyl group is especially preferable.

Examples of the saturated or unsaturated alicyclic hydrocarbon group represented by R ^N3 , R ¹ to R ⁸ , R ¹⁰¹ and R ¹⁰² include a cyclopropyl group, 1-methylcyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cyclohep group. Tyl group, 1-methylcyclohexyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 1,2-dimethylcyclohexyl group, 1,3-dimethylcyclohexyl group, 1, 4-dimethylcyclohexyl group, 2,3-dimethylcyclohexyl group, 2,4-dimethylcyclohexyl group, 2,5-dimethylcyclohexyl group, 2,6-dimethylcyclohexyl group, 3,4-dimethylcyclohexyl group Sil group, 3,5-dimethylcyclohexyl group, 2,2-dimethylcyclohexyl group, 3,3-dimethylcyclohexyl group, 4,4-dimethylcyclohexyl group, cyclooctyl group, 2,4,6-trimethylcyclo Hexyl group, 2,2,6,6-tetramethylcyclohexyl group, 3,3,5,5-tetramethylcyclohexyl group, 4-pentylcyclohexyl group, 4-octylcyclohexyl group, 4-cyclohexyl group Cycloalkyl groups, such as a chlorohexyl group; Cycloalkenyl groups, such as a cyclohexenyl group (For example, cyclohexa-2-ene, cyclohexa-3-ene), a cycloheptenyl group, and a cyclooctenyl group; norbornane group, adamantyl group, bicyclo[2.2.2]octane, etc. are mentioned. The number of carbon atoms in the saturated or unsaturated alicyclic hydrocarbon group is preferably 3 to 30, more preferably 3 to 20, still more preferably 4 to 20, still more preferably 4 to 15, Especially more preferably, it is 5-15, Most preferably, it is 5-10. Among them, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group are particularly preferable.

Examples of the aromatic hydrocarbon group represented by R ^N3 , R ¹ to R ⁸ , R ¹⁰¹ and R ¹⁰² include a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-dimethylphenyl group, and 2,4-dimethyl Phenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 4-vinylphenyl group, o-isopropylphenyl group, m-isopropylphenyl group, p-iso Propylphenyl group, o-tert-butylphenyl group, m-tert-butylphenyl group, p-tert-butylphenyl group, mesityl group, 4-ethylphenyl group, 4-butylphenyl group, 4-pentylphenyl group, 2,6-bis(2- Propyl) phenyl group, 4-cyclohexylphenyl group, 2,4,6-trimethylphenyl group, 4-octylphenyl group, 4-vinylphenyl group, 1-naphthyl group, 2-naphthyl group, 5,6,7,8-tetrahydro- aromatic hydrocarbon groups such as 1-naphthyl group, 5,6,7,8-tetrahydro-2-naphthyl group, fluorenyl group, phenanthryl group, anthryl group and pyrenyl group; and the like. The aromatic hydrocarbon group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 15 carbon atoms.

The hydrocarbon group represented by R ^N3 , R ¹ to R ⁸ , R ¹⁰¹ and R ¹⁰² is a combination of the above-mentioned hydrocarbon groups (for example, at least one of an aromatic hydrocarbon group, a chain hydrocarbon group and an alicyclic hydrocarbon group). aralkyl groups such as a benzyl group, a phenethyl group, and a 1-methyl-1-phenylethyl group; arylalkenyl groups such as a phenylethenyl group (phenylvinyl group); Aryl alkynyl groups, such as a phenylethynyl group; a phenyl group to which one or more phenyl groups such as a biphenylyl group and a terphenylyl group are bonded; A cyclohexylmethylphenyl group, a benzylphenyl group, (dimethyl(phenyl)methyl)phenyl group, etc. are mentioned.

The group represented by R ^N3 , R ¹ to R ⁸ , R ¹⁰¹ and R ¹⁰² is a combination of the above hydrocarbon groups (eg, a chain hydrocarbon group and an alicyclic hydrocarbon group), for example, a cyclopropylmethyl group, a cyclo Even if it is an alkyl group to which one or more alicyclic hydrocarbon groups such as propylethyl group, cyclobutylmethyl group, cyclobutylethyl group, cyclopentylmethyl group, cyclopentylethyl group, cyclohexylmethyl group, 2-methylcyclohexylmethyl group, cyclohexylethyl group, adamantylmethyl group are bonded do.

Preferably carbon number of the said hydrocarbon group is 4-30, More preferably, it is 6-30, More preferably, it is 6-20, More preferably, it is 4-20, More preferably, it is 4-15. and particularly preferably 6 to 15.

The aliphatic hydrocarbon group represented by R ^N1 and R ^N2 and the hydrocarbon group represented by R ^N3 , R ¹ to R ⁸ , R ¹⁰¹ and R ¹⁰² may have a substituent. The substituent may be monovalent or divalent. As for the divalent substituent, it is preferable that two bonding hands couple|bond with the same carbon atom to form a double bond.

As the monovalent substituent,

Methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, (2-ethyl)hexyloxy group, hep Tyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group, (2-ethyl)hexyloxy group, icosyloxy group, 1-phenylethoxy group, 1-methyl-1-phenyl ethoxy group, phenyloxy group, o-tolyloxy group, 2,3-dimethylphenyloxy group, 2,4-dimethylphenyloxy group, 2,5-dimethylphenyloxy group, 2,6-dimethylphenyloxy group, 3,4-dimethylphenyloxy group, 3,5-dimethylphenyloxy group, 2,2-dicyanophenyloxy group, 2,3-dicyanophenyloxy group, 2,4-dicyanophenyloxy group, 2, 5-dicyanophenyloxy group, 2,6-dicyanophenyloxy group, 3,4-dicyanophenyloxy group, 3,5-dicyanophenyloxy group, 4-methoxyphenyloxy group, 2-methoxy C1-C10, such as a phenyloxy group, 3-methoxyphenyloxy group, 4-ethoxyphenyloxy group, 2-ethoxyphenyloxy group, 3-ethoxyphenyloxy group, and groups represented by the following formula A hydrocarbon group having 20 (preferably 1 to 10 carbon atoms) or a derivatized group thereof (e.g., a carboxy group, a sulfo group, a nitro group, a hydroxyl group, a halogen (preferably a chlorine atom), an alkylsulfamoyl group having 1 to 10 carbon atoms ( preferably an oxy group in which a group derivatized with an octylsulfamoyl group) or the like) is bonded to one side;

Methylthio group, ethylthio group, propylthio group, butylthio group, tert-butylthio group, pentylthio group, hexylthio group, (2-ethyl)hexylthio group, heptylthio group, octylthio group, nonylthio group , a sulfanyl group to which a hydrocarbon group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) is bonded, such as decylthio group, undecylthio group, dodecylthio group, icosylthio group, phenylthio group and o-tolylthio group;

an epoxy group, an oxetanyl group, a tetrahydrofuryl group, a tetrahydropyranyl group;

formyl group; Acetyl group, propanoyl group, butanoyl group, 2,2-dimethylpropanoyl group, pentanoyl group, hexanoyl group, (2-ethyl)hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, decanoyl group, undecanoyl group , dodecanoyl group, henicosanoyl group, benzoyl group, and the like, and a hydrocarbon group having 1 to 20 carbon atoms (preferably 1 to 11 carbon atoms), such as a group represented by the following formula, or a derivatized group thereof (for example, A carboxyl group, a sulfo group, a nitro group, a hydroxyl group, a halogen (preferably a chlorine atom), a group derivatized with an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably an octylsulfamoyl group), etc.) bonded to a carbonyl group (the carbonyl group When it is set as an alkanoyl group, carbon number becomes like this. Preferably it is 2-12);

Methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, tert-butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, (2-ethyl)hexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, nonyloxycarbonyl group , a decyloxycarbonyl group, an undecyloxycarbonyl group, a dodecyloxycarbonyl group, an icosyloxycarbonyl group, a phenyloxycarbonyl group, an o-tolyloxycarbonyl group, and a group having 1 to 20 carbon atoms (preferably carbon atoms) 1 to 10) a hydrocarbon group or a derivatized group thereof (for example, a carboxy group, a sulfo group, a nitro group, a hydroxyl group, a halogen (preferably a chlorine atom), an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably octylsulfamo) oxycarbonyl group) to which a group derivatized with diary) and the like;

amino group; N-methylamino group, N,N-dimethylamino group, N-ethylamino group, N,N-diethylamino group, N-propylamino group, N,N-dipropylamino group, N-isopropylamino group, N,N-diiso group Propylamino group, N-butylamino group, N,N-dibutylamino group, N-isobutylamino group, N,N-diisobutylamino group, N-sec-butylamino group, N,N-disec-butylamino group, N- tert-butylamino group, N,N-ditert-butylamino group, N-pentylamino group, N,N-dipentylamino group, N-(1-ethylpropyl)amino group, N,N-di(1-ethylpropyl)amino group , N-hexylamino group, N,N-dihexylamino group, N-(2-ethyl)hexylamino group, N,N-di(2-ethyl)hexylamino group, N-heptylamino group, N,N-diheptylamino group, N-octylamino group, N,N-dioctylamino group, N-nonylamino group, N,N-dinonylamino group, N-phenylamino group, N,N-diphenylamino group, N,N-ethylmethylamino group, N,N -Propylmethylamino group, N,N-isopropylmethylamino group, N,N-butylmethylamino group, N-decylamino group, N,N-decylmethylamino group, N-undecylamino group, N,N-undecylmethylamino group, N-dodecylamino group, N,N-dodecylmethylamino group, N-icosylamino group, N,N-icosylmethylamino group, N,N-tert-butylmethylamino group, N,N-phenylmethylamino group, etc.; and One or two hydrocarbon groups having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), such as a group represented by the following formula, or a derivatized group thereof (for example, a carboxy group, a sulfo group, a nitro group, a preferably a chlorine atom), an amino group substituted with an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably a group derivatized with an octylsulfamoyl group) or the like;

sulfamoyl group; N-methylsulfamoyl group, N,N-dimethylsulfamoyl group, N-ethylsulfamoyl group, N,N-diethylsulfamoyl group, N-propylsulfamoyl group, N,N-dipropylsulfamoyl group, N-isopropylsulfamoyl group, N,N-diisopropylsulfamoyl group, N-butylsulfamoyl group, N,N-dibutylsulfamoyl group, N-isobutylsulfamoyl group, N,N-diiso Butylsulfamoyl group, N-sec-butylsulfamoyl group, N,N-disec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N,N-ditert-butylsulfamoyl group, N-pen Tylsulfamoyl group, N,N-dipentylsulfamoyl group, N-(1-ethylpropyl)sulfamoyl group, N,N-di(1-ethylpropyl)sulfamoyl group, N-hexylsulfamoyl group, N,N -dihexylsulfamoyl group, N-(2-ethyl)hexylsulfamoyl group, N,N-di(2-ethyl)hexylsulfamoyl group, N-heptylsulfamoyl group, N,N-diheptylsulfamoyl group, N -octylsulfamoyl group, N,N-dioctylsulfamoyl group, N,N-octylmethylsulfamoyl group, N-nonylsulfamoyl group, N,N-dinonylsulfamoyl group, N-phenylsulfamoyl group, N, N-diphenylsulfamoyl group, N,N-ethylmethylsulfamoyl group, N,N-propylmethylsulfamoyl group, N,N-isopropylmethylsulfamoyl group, N,N-butylmethylsulfamoyl group, N -decylsulfamoyl group, N,N-decylmethylsulfamoyl group, N-undecylsulfamoyl group, N,N-undecylmethylsulfamoyl group, N-dodecylsulfamoyl group, N,N-dodecylmethylsulfamo diary, N-icosylsulfamoyl group, N,N-icosylmethylsulfamoyl group, N,N-tert-butylmethylsulfamoyl group, N,N-phenylmethylsulfamoyl group, etc., and One or two C1-C20 (preferably C1-C10) hydrocarbon groups such as a group or a derivatized group thereof (for example, a carboxy group, a sulfo group, a nitro group, a hydroxyl group, a halogen (preferably a chlorine atom)) , a sulfamoyl group substituted with an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably a group derivatized with an octylsulfamoyl group) or the like;

formylamino group; Acetylamino group, propanoylamino group, butanoylamino group, 2,2-dimethylpropanoylamino group, pentanoylamino group, hexanoylamino group, (2-ethyl)hexanoylamino group, heptanoylamino group, octanoylamino group, nonanoyl amino group, decanoylamino group, undecanoylamino group, dodecanoylamino group, henicosanoylamino group, benzoylamino group, and groups having 1 to 20 carbon atoms (preferably 1 to 12 carbon atoms) Derivatized with a hydrocarbon group or a derivatized group thereof (for example, a carboxy group, a sulfo group, a nitro group, a hydroxyl group, a halogen (preferably a chlorine atom), an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably an octylsulfamoyl group), etc. an amino group substituted by the carbonyl group to which the group is bonded (when the carbonylamino group is an alkanoylamino group, the carbon number is preferably 1 to 12);

hydroxyl group; Halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom;

a carboxyl group, —CO ₂ M ² (M ² is an alkali metal, preferably lithium, sodium, potassium); a sulfo group, —SO ₃ M ² (M ² is an alkali metal, preferably lithium, sodium, potassium); nitro group; cyano group; formyloxy group; Acetoxy group, propanoyloxy group, butanoyloxy group, 2,2-dimethylpropanoyloxy group, pentanoyloxy group, hexanoyloxy group, (2-ethyl) hexanoyloxy group, heptanoyloxy group, octanoyloxy group, no Nanoyloxy group, decanoyloxy group, undecanoyloxy group, dodecanoyloxy group, henicosanoyloxy group, benzoyloxy group, etc., and a group represented by the following formulas having 1 to 20 carbon atoms (preferably having 1 carbon atom) to 10) a hydrocarbon group or a derivatized group thereof (for example, a carboxy group, a sulfo group, a nitro group, a hydroxyl group, a halogen (preferably a chlorine atom), an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably an octylsulfamoyl group) ) to which a carbonyloxy group (in the case of using the carbonyloxy group as an alkanoyloxy group, the carbon number is preferably 1 to 10) bonded thereto;

Methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, pentylsulfonyl group, hexylsulfonyl group, (2-ethyl)hexylsulfonyl group, heptylsulfonyl group, octylsulfonyl group, nonylsulfonyl group, decylsulfonyl group, unde Hydrocarbons having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), such as a silsulfonyl group, a dodecylsulfonyl group, an icosylsulfonyl group, a phenylsulfonyl group, a p-tolylsulfonyl group, and a group represented by the following formula derivatized with a group or its derivatized group (for example, a carboxy group, a sulfo group, a nitro group, a hydroxyl group, a halogen (preferably a chlorine atom), an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably an octylsulfamoyl group), etc. a sulfonyl group to which the group) is bonded;

carbamoyl group; N-methylcarbamoyl group, N,N-dimethylcarbamoyl group, N-ethylcarbamoyl group, N,N-diethylcarbamoyl group, N-propylcarbamoyl group, N,N-dipropylcarbamoyl group, N-isopropylcarbamoyl group, N,N-diisopropylcarbamoyl group, N-butylcarbamoyl group, N,N-dibutylcarbamoyl group, N-isobutylcarbamoyl group, N,N-diiso Butylcarbamoyl group, N-sec-butylcarbamoyl group, N,N-disec-butylcarbamoyl group, N-tert-butylcarbamoyl group, N,N-ditert-butylcarbamoyl group, N-pentyl group Carbamoyl group, N,N-dipentylcarbamoyl group, N-(1-ethylpropyl)carbamoyl group, N,N-di(1-ethylpropyl)carbamoyl group, N-hexylcarbamoyl group, N, N-dihexylcarbamoyl group, N-(2-ethyl)hexylcarbamoyl group, N,N-di(2-ethyl)hexylcarbamoyl group, N-heptylcarbamoyl group, N,N-diheptylcarbamo Diyl, N-octylcarbamoyl group, N,N-dioctylcarbamoyl group, N-nonylcarbamoyl group, N,N-octylmethylcarbamoyl group, N,N-octylbutylcarbamoyl group, N,N- dinonylcarbamoyl group, N-phenylcarbamoyl group, N,N-diphenylcarbamoyl group, N,N-ethylmethylcarbamoyl group, N,N-propylmethylcarbamoyl group, N,N-isopropylmethyl Carbamoyl group, N,N-butylmethylcarbamoyl group, N-decylcarbamoyl group, N,N-decylmethylcarbamoyl group, N-undecylcarbamoyl group, N,N-undecylmethylcarbamoyl group, N-dodecylcarbamoyl group, N,N-dodecylmethylcarbamoyl group, N-icosylcarbamoyl group, N,N-icosylmethylcarbamoyl group, N,N-tert-butylmethylcarbamoyl group, One or two hydrocarbon groups having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), such as N,N-phenylmethylcarbamoyl group, and a group represented by the following formula, or a derivatized group thereof (for example, a carbamoyl group substituted with a carboxy group, a sulfo group, a nitro group, a hydroxyl group, a halogen (preferably a chlorine atom), a group derivatized with an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably an octylsulfamoyl group), etc.);

Trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluoro All of the hydrogen atoms such as octyl group, perfluorononyl group, perfluorodecyl group, perfluorodecyl group, perfluorododecyl group, perfluoroicosyl group, perfluorocyclohexyl group, perfluorophenyl group a hydrocarbon group having 1 to 20 carbon atoms substituted with a fluorine atom;

Perfluoroethylmethyl group, perfluoropropylmethyl group, perfluoroisopropylmethyl group, perfluorobutylmethyl group, perfluoropentylmethyl group, perfluorohexylmethyl group, perfluoroheptylmethyl group, perfluorooctylmethyl group, purple A linear or branched chain having 1 to 20 carbon atoms in which all hydrogen atoms, such as a luoronylmethyl group, perfluorodecylmethyl group, perfluoroundecylmethyl group, perfluorododecylmethyl group, and perfluoroicosylmethyl group, are substituted with fluorine atoms A hydrocarbon group having 1 to 20 carbon atoms substituted with an alkyl group of;

Some hydrogen atoms such as 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group and 2,4,6-trifluorophenyl group are substituted with fluorine having 1 to 20 carbon atoms (preferably from 1 to 20 carbon atoms) The hydrocarbon group of 10);

-CO-SH, -CO-S-CH ₃ , -CO-S-CH ₂ CH ₃ , -CO-S-CH ₂ -CH ₂ -CH ₃ , -CO-S-CH ₂ -CH ₂ -CH ₂ a thiocarbonyl group bonded to an alkyl group having 1 to 20 carbon atoms (preferably 2 to 10 carbon atoms) such as -CH ₃ , a thiocarbonyl group bonded to an aryl group having 6 to 20 carbon atoms such as -CO-SC ₆ H ₅ ;

*-COCO-R represented by the following formula (wherein R is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms (for example, one of the hydrocarbon groups listed above, which satisfies 1 to 20 carbon atoms), or its a derivatized group (for example, a carboxyl group, a sulfo group, a nitro group, a hydroxyl group, a halogen (preferably a chlorine atom), an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably an octylsulfamoyl group), etc.) ) of the group;

*-NRCONR ₂ represented by the following formula (wherein R is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms (for example, a hydrocarbon group having 1 to 20 carbon atoms among the hydrocarbon groups listed above), or a derivative thereof a chemical group (for example, a carboxy group, a sulfo group, a nitro group, a hydroxyl group, a halogen (preferably a chlorine atom), an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably an octylsulfamoyl group), etc.); The R may be the same as or different from each other, and may be bonded to each other to form a ring);

*-OCONR ₂ represented by the following formula (wherein R is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms (for example, one satisfying the hydrocarbon group having 1 to 20 carbon atoms among the hydrocarbon groups listed above), or a derivative thereof a chemical group (for example, a carboxy group, a sulfo group, a nitro group, a hydroxyl group, a halogen (preferably a chlorine atom), an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably an octylsulfamoyl group), etc.); The R may be the same as or different from each other, and may be bonded to each other to form a ring);

*-NRCOOR represented by the following formula (wherein R is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms (for example, a hydrocarbon group having 1 to 20 carbon atoms among the hydrocarbon groups listed above), or a derivatized group thereof (For example, a carboxy group, a sulfo group, a nitro group, a hydroxyl group, a halogen (preferably a chlorine atom), a group derivatized with an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably an octylsulfamoyl group), etc.), and the R is the same as or different from each other, and may be bonded to each other to form a ring);

*-OP(O)(OR) ₂ such as *-OP(O)(OCH ₃ ) ₂ (wherein R is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms (for example, among the hydrocarbon groups listed above) one having 1 to 20 carbon atoms), or a derivatized group thereof (for example, a carboxy group, a sulfo group, a nitro group, a hydroxy group, a halogen (preferably a chlorine atom), an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably a chlorine atom) octylsulfamoyl group)), and the R may be the same or different from each other, and may be bonded to each other to form a ring);

*-SiR ₃ (such as *-Si(CH ₃ ) ₃ , *-Si(CH ₂ CH ₃ ) ₃ , *-Si(C ₆ H ₅ ) ₃ and *-Si(CH(CH ₃ ) ₂ ) ₃ In the formula, R is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms (for example, a hydrocarbon group having 1 to 20 carbon atoms among the hydrocarbon groups listed above), or a derivatized group thereof (for example, a carboxy group, sulfo group, nitro group) group, a hydroxyl group, a halogen (preferably a chlorine atom), a group derivatized with an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably an octylsulfamoyl group), etc.), wherein R may be the same as or different from each other, group may be bonded to each other to form a ring); and the like.

Examples of the divalent substituent include an oxo group, a thioxo group, an imino group, an imino group substituted by an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), and an imino group substituted by an aryl group having 6 to 20 carbon atoms. have. Examples of the imino group substituted by the alkyl group include CH ₃ -N=, CH ₃ -CH ₂ -N=, CH ₃ -(CH ₂ ) ₂ -N=, CH ₃ -(CH ₂ ) ₃ -N=, and the like. . Examples of the imino group substituted by the aryl group include C ₆ H ₅ -N=.

As a substituent of a C1-C40 hydrocarbon group, Preferably, the substituent of group s1 is mentioned. The derivatizing group shown below is preferably a group derivatized with a carboxy group, a sulfo group, a nitro group, a hydroxyl group, a halogen (preferably a chlorine atom), or an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably an octylsulfamoyl group). do.

[group s1]

an oxy group in which a hydrocarbon group having 1 to 20 carbon atoms or a derivative thereof is bonded to one side;

a carbonyl group to which a hydrocarbon group having 1 to 20 carbon atoms or a derivative thereof is bonded;

an oxycarbonyl group to which a hydrocarbon group having 1 to 20 carbon atoms or a derivative thereof is bonded;

amino group; an amino group substituted with one or two C1-C20 hydrocarbon groups or derivatives thereof; sulfamoyl group; a sulfamoyl group substituted with one or two hydrocarbon groups having 1 to 20 carbon atoms or a derivative thereof;

a carbonylamino group to which a hydrocarbon group having 1 to 20 carbon atoms or a derivative thereof is bonded;

hydroxyl group; halogen atom; -CO ₂ M (preferably a carboxy group) (M represents a hydrogen atom or an alkali metal atom, preferably a hydrogen atom); -SO ₃ M (preferably a sulfo group) (M represents a hydrogen atom or an alkali metal atom, preferably a hydrogen atom.);

nitro group; cyano group; a carbonyloxy group to which a hydrocarbon group having 1 to 20 carbon atoms or a derivatized group thereof is bonded; a sulfonyl group to which a hydrocarbon group having 1 to 20 carbon atoms or a derivative thereof is bonded; carbamoyl group; a carbamoyl group substituted with one or two hydrocarbon groups having 1 to 20 carbon atoms or a derivative thereof; a hydrocarbon group having 1 to 20 carbon atoms in which all hydrogen atoms are substituted with fluorine atoms;

a C1-C20 hydrocarbon group substituted by a C1-C20 linear or branched alkyl group in which all the hydrogen atoms are substituted with the fluorine atom; a hydrocarbon group having 1 to 20 carbon atoms in which a part of hydrogen atoms are substituted with fluorine; oxo.

As a substituent of a C1-C40 hydrocarbon group, More preferably, the substituent of group s2 is mentioned.

[group s2]

an oxy group in which a hydrocarbon group having 1 to 10 carbon atoms or a derivative thereof is bonded to one side;

a carbonyl group to which a hydrocarbon group having 1 to 10 carbon atoms or a derivative thereof is bonded;

an oxycarbonyl group to which a hydrocarbon group having 1 to 10 carbon atoms or a derivative thereof is bonded;

amino group; an amino group substituted with one or two hydrocarbon groups having 1 to 10 carbon atoms;

sulfamoyl group; a sulfamoyl group substituted with one or two hydrocarbon groups having 1 to 10 carbon atoms or a derivative thereof; a carbonylamino group to which a hydrocarbon group having 1 to 10 carbon atoms or a derivative thereof is bonded; hydroxyl group; a fluorine atom, a chlorine atom, and a bromine atom;

-CO ₂ M (preferably a carboxy group) (M represents a hydrogen atom or an alkali metal atom, preferably a hydrogen atom); -SO ₃ M (preferably a sulfo group) (M represents a hydrogen atom or an alkali metal atom, preferably a hydrogen atom.); nitro group; cyano group; a carbonyloxy group to which a hydrocarbon group having 1 to 10 carbon atoms or a derivative thereof is bonded; a sulfonyl group to which a hydrocarbon group having 1 to 10 carbon atoms or a derivative thereof is bonded; carbamoyl group; a carbamoyl group substituted with one or two hydrocarbon groups having 1 to 10 carbon atoms or a derivative thereof; a hydrocarbon group having 1 to 10 carbon atoms in which all hydrogen atoms are substituted with fluorine atoms; a hydrocarbon group having 1 to 10 carbon atoms in which all of the hydrogen atoms are substituted with a fluorine atom; a hydrocarbon group having 1 to 10 carbon atoms in which a part of hydrogen atoms are substituted with fluorine; oxo.

Examples of the hydrocarbon group having 1 to 40 carbon atoms having a substituent represented by R ^N3 , R ¹ to R ⁸ , R ¹⁰¹ and R ¹⁰² include a hydrocarbon group having 1 to 40 carbon atoms having a monovalent or divalent substituent, preferably is a saturated or unsaturated chain hydrocarbon group having 1 to 30 carbon atoms having a monovalent or divalent substituent, a saturated or unsaturated alicyclic hydrocarbon group having 3 to 30 carbon atoms having a monovalent or divalent substituent, having a monovalent or divalent substituent Examples of the group combining an aromatic hydrocarbon group having 6 to 30 carbon atoms or a hydrocarbon group include a group having 1 to 30 carbon atoms having a monovalent or divalent substituent;

More preferably, a saturated or unsaturated chain hydrocarbon group having 1 to 20 carbon atoms having a substituent of group s1, a saturated or unsaturated alicyclic hydrocarbon group having 3 to 20 carbon atoms having a substituent of group s1, and 6 carbon atoms having a substituent of group s1 Examples of the -20 aromatic hydrocarbon group or the group combining hydrocarbon groups include a C1-C20 group having a substituent of group s1,

Particularly preferably, a saturated or unsaturated chain hydrocarbon group having 1 to 15 carbon atoms having a substituent of group s2, a saturated or unsaturated alicyclic hydrocarbon group having 3 to 15 carbon atoms having a substituent of group s2, and 6 carbon atoms having a substituent of group s2 Examples of the aromatic hydrocarbon group of ∼15 or the group combining hydrocarbon groups include a group having 1 to 15 carbon atoms having a substituent of group s2.

The heterocyclic group represented by R ^N3 , R ¹ to R ⁸ , R ¹⁰¹ and R ¹⁰² may be monocyclic or polycyclic, and is preferably a heterocyclic group containing a hetero atom as a component of the ring. A nitrogen atom, an oxygen atom, a sulfur atom, etc. are mentioned as a hetero atom.

The heterocyclic group preferably has 3 to 30 carbon atoms, more preferably 3 to 22 carbon atoms, still more preferably 3 to 20 carbon atoms, still more preferably 3 to 18 carbon atoms, still more preferably 3 to 15 carbon atoms. , particularly preferably 3 to 14.

As a heterocyclic ring containing a nitrogen atom,

monocyclic saturated heterocycles such as aziridine, azetidine, pyrrolidine, piperidine and piperazine;

pyrroles such as 2,5-dimethylpyrrole, pyrazoles such as 2-methylpyrazole and 3-methylpyrazole, and 5-membered rings such as imidazole, 1,2,3-triazole and 1,2,4-triazole systemic unsaturated heterocycle;

6-membered ring unsaturated heterocycles such as pyrimidines such as pyridine, pyridazine and 6-methylpyrimidine, pyrazine, and 1,3,5-triazine;

Quinoxes such as indazole, indoline, isoindoline, indole, indolidine, benzimidazole, quinoline, isoquinoline, 5,6,7,8-tetrahydro(3-methyl)quinoxaline, and 3-methylquinoxaline condensed bicyclic heterocycles such as saline, quinazoline, cinnoline, phthalazine, naphthyridine, purine, pteridine, benzopyrazole, and benzopiperidine;

Condensed tricyclic heterocycles, such as carbazole, acridine, and phenazine; and the like.

Examples of the heterocycle containing an oxygen atom include monocyclic saturated heterocycles such as oxylane, oxetane, tetrahydrofuran, tetrahydropyran, 1,3-dioxane, 1,4-dioxane, and 1-cyclopentyldioxolane; bicyclic saturated heterocycles such as 1,4-dioxaspiro[4.5]decane and 1,4-dioxaspiro[4.5]nonane;

lactone-based heterocycles such as α-acetolactone, β-propiolactone, γ-butyrolactone, γ-valerolactone and δ-valerolactone;

5-membered ring system unsaturated heterocycles, such as furans, such as 2, 3- dimethylfuran and 2, 5- dimethylfuran;

6-membered ring unsaturated heterocycles such as 2H-pyran and 4H-pyran;

Condensed bicyclic heterocyclic rings, such as benzopyran, such as 1-benzofuran and 4-methylbenzopyran, benzodioxole, chroman, and isochroman;

Condensed tricyclic heterocycles, such as xanthene and dibenzofuran; and the like.

As a heterocyclic ring containing a sulfur atom, 5-membered ring system saturated heterocycles, such as dithiolane; 6-membered ring saturated heterocycles such as thiane, 1,3-dithiane, and 2-methyl 1,3-dithiane; 5-membered ring unsaturated heterocyclic rings such as thiophene such as 3-methylthiophene and 2-carboxythiophene, and benzothiopyran such as 4H-thiopyran and benzotetrahydrothiopyran; condensed bicyclic heterocycles such as benzothiophene; condensed tricyclic heterocycles such as thianthrene and dibenzothiophene; and the like.

Examples of the heterocycle containing a nitrogen atom and an oxygen atom include monocyclic saturated heterocyclic rings such as morpholine, 2-pyrrolidone, 2-methyl-2-pyrrolidone, 2-piperidone and 2-methyl-2-piperidone. Summons;

Monocyclic unsaturated heterocyclic rings, such as isoxazole, such as oxazole, such as 4-methyloxazole, 2-methylisoxazole, and 3-methylisoxazole;

Condensed bicyclic heterocyclic rings, such as benzoxazole, benzoisooxazole, benzoxazine, benzodioxane, and benzoimidazoline; condensed tricyclic heterocycles such as phenoxazine; and the like.

As a heterocyclic ring containing a nitrogen atom and a sulfur atom, Monocyclic heterocyclic rings, such as thiazole, such as 3-methylthiazole and 2, 4- dimethylthiazole; Condensed bicyclic heterocycles, such as benzothiazole;

condensed tricyclic heterocycles such as phenothiazine; and the like.

The heterocyclic ring may be a contribution combining the above-mentioned hydrocarbon groups, and examples thereof include a tetrahydrofurylmethyl group.

In addition, the said heterocyclic ring may be represented by the following formula|equation.

The heterocyclic group may be a heterocyclic group formed by bonding two or more of R ¹ to R ³ and R ⁵ to R ⁸ . Such a heterocyclic group has a ring structure of two or more rings together with the benzene ring to which R ¹ to R ³ and R ⁵ to R ⁸ are bonded. As a ring structure of this two or more rings, the structure of the following formula is mentioned, for example.

In addition, the bonding position of the said heterocyclic ring is the part from which arbitrary hydrogen atoms contained in each ring were removed.

The heterocyclic group represented by R ^N3 , R ¹ to R ⁸ , R ¹⁰¹ and R ¹⁰² may have a substituent. Examples of the substituent include the same substituents as the substituents which the aliphatic hydrocarbon group represented by R ^N1 and R ^N2 and the hydrocarbon group represented by R ^N3 , R ¹ to R ⁸ , R ¹⁰¹ and R ¹⁰² may have. In addition, when the said heterocyclic ring contains the nitrogen atom as its structural element, the hydrocarbon group mentioned above may couple|bond with this nitrogen atom as a substituent.

Preferred examples of the substituent include the same as preferred substituents which the aliphatic hydrocarbon group represented by R ^N1 and R ^N2 and the hydrocarbon group represented by R ^N3 , R ¹ to R ⁸ , R ¹⁰¹ and R ¹⁰² may have. .

Examples of the heterocyclic group having a substituent represented by R ^N3 , R ¹ to R ⁸ , R ¹⁰¹ and R ¹⁰² include a heterocyclic group having a monovalent or divalent substituent, preferably a heterocyclic group having a substituent of group s1. and, more preferably, a heterocyclic group having a substituent of group s2.

The number of substituents (1st substituent) which the said hydrocarbon group or heterocyclic group may have may be 1, 2 or more, and 2 or more substituents may mutually independently be the same or different. In addition, as for the said 1st substituent, the other substituent (2nd substituent) may couple|bond with the hydrocarbon group contained in the part. The second substituent may be selected from the same groups as the first substituent.

Hereinafter, R ¹ to R ⁸ of -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -COCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , -SO ₂ N(R ¹⁰² ) ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , -NHCO-N(R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON(R ¹⁰² ) ₂ , a halogen atom, -SO ₃ M and -CO ₂ M will be described.

-CO-R ¹⁰² is a formyl group; Acetyl group, propanoyl group, butanoyl group, 2,2-dimethylpropanoyl group, pentanoyl group, hexanoyl group, (2-ethyl)hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, decanoyl group, undecanoyl group , dodecanoyl group, henicosanoyl group, benzoyl group, etc., and a group represented by the above formulas, such as a hydrocarbon group having 1 to 40 carbon atoms (preferably 1 to 20 carbon atoms) or a derivatized group thereof (for example, a carboxy group, and a carbonyl group to which a sulfo group, a nitro group, a hydroxyl group, a halogen (preferably a chlorine atom), or a group derivatized with an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably an octylsulfamoyl group) is bonded, preferably Examples thereof include a carbonyl group to which a hydrocarbon group having 1 to 10 carbon atoms is bonded (when the carbonyl group is an acyl group, it has 2 to 41 carbon atoms). Preferably, a carbonyl group having 1 to 11 carbon atoms (more preferably 1 to 10 carbon atoms) or a derivatized group bonded thereto (when the carbonyl group is an alkanoyl group, more preferably 2 to 12 carbon atoms) and the like.

-COO-R ¹⁰¹ is a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a butoxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonyl group, a (2-ethyl)hexyloxycarbonyl group, a heptyloxycarbonyl group, and an octyl group. oxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, undecyloxycarbonyl group, dodecyloxycarbonyl group, phenyloxycarbonyl group, icosyloxycarbonyl group, and groups represented by the above formulas having 1 to 40 carbon atoms (preferably carbon atoms) and an oxycarbonyl group to which a hydrocarbon group of 1 to 20) is bonded, preferably a hydrocarbon group having 1 to 10 carbon atoms or a derivatized group thereof (for example, a carboxy group, a sulfo group, a nitro group, a hydroxyl group, a halogen (preferably a chlorine atom) ), an oxycarbonyl group to which a group derivatized with an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably an octylsulfamoyl group) or the like is bonded.

Preferably, a hydrocarbon group having 1 to 10 carbon atoms or an oxycarbonyl group to which a derivative thereof is bonded is mentioned.

-OCO-R ¹⁰² is a formyloxy group; Acetoxy group, propanoyloxy group, butanoyloxy group, 2,2-dimethylpropanoyloxy group, pentanoyloxy group, hexanoyloxy group, (2-ethyl) hexanoyloxy group, heptanoyloxy group, octanoyloxy group, no Nanoyloxy group, decanoyloxy group, undecanoyloxy group, dodecanoyloxy group, henicosanoyloxy group, benzoyloxy group, and the like, and groups represented by the above formulas having 1 to 40 carbon atoms (preferably having 1 carbon atoms). to 20) include an oxy group to which a carbonyl group to which a hydrocarbon group is bonded, more preferably a hydrocarbon group having 1 to 10 carbon atoms or a derivatized group thereof (for example, a carboxy group, a sulfo group, a nitro group, a hydroxyl group, a halogen (preferably A carbonyloxy group (a group derivatized with a carbonyloxy group, an alkylsulfamoyl group (preferably an octylsulfamoyl group), etc.) to which a chlorine atom)) is bonded (when the carbonyloxy group is an acyloxy group, the number of carbon atoms is 2 to 41) and the like, preferably a carbonyloxy group having 1 to 11 carbon atoms (more preferably 1 to 10 carbon atoms) or a derivatized group bonded thereto (the carbonyloxy group is an acyloxy group). In this case, carbon number is more preferably 2-12) etc. are mentioned.

As -COCO-R ¹⁰² , methyloxalyl group, ethyloxalyl group, propyloxalyl group, butyloxalyl group, pentyloxalyl group, hexyloxalyl group, (2-ethyl)hexyloxalyl group, heptyloxalyl group group, octyloxalyl group, nonyloxalyl group, decyloxalyl group, undecyloxalyl group, dodecyloxalyl group, icosyloxalyl group, cyclopentyloxalyl group, cyclohexyloxalyl group, phenyloxalyl group, p - a hydrocarbon group having 1 to 40 carbon atoms (preferably 1 to 20 carbon atoms) or a derivatized group thereof (for example, a carboxy group, a sulfo group, a nitro group, a hydroxyl group, , a halogen (preferably a chlorine atom), an oxalyl group bonded with an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably a group derivatized with an octylsulfamoyl group) or the like.

-OR ¹⁰² is a hydroxyl group; Methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group Group, decyloxy group, undecyloxy group, dodecyloxy group, (2-ethyl)hexyloxy group, icosyloxy group, 1-phenylethoxy group, 1-methyl-1-phenylethoxy group, phenyloxy group, 2 , 3-dimethylphenyloxy group, 2,4-dimethylphenyloxy group, 2,5-dimethylphenyloxy group, 2,6-dimethylphenyloxy group, 3,4-dimethylphenyloxy group, 3,5-dimethylphenyl Oxy group, 2,2-dicyanophenyloxy group, 2,3-dicyanophenyloxy group, 2,4-dicyanophenyloxy group, 2,5-dicyanophenyloxy group, 2,6-dicyanophenyl Oxy group, 3,4-dicyanophenyloxy group, 3,5-dicyanophenyloxy group, 4-methoxyphenyloxy group, 2-methoxyphenyloxy group, 3-methoxyphenyloxy group, 4-e A hydrocarbon group having 1 to 40 carbon atoms (preferably 1 to 20 carbon atoms), such as oxyphenyloxy group, 2-ethoxyphenyloxy group, 3-ethoxyphenyloxy group, and groups represented by the above formulas, or A derivatized group (for example, a carboxyl group, a sulfo group, a nitro group, a hydroxyl group, a halogen (preferably a chlorine atom), an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably an octylsulfamoyl group), etc.) The oxy group which couple|bonded is mentioned, Preferably the oxy group etc. which the C1-C10 hydrocarbon group couple|bonded are mentioned.

Preferably, a hydrocarbon group having 1 to 10 carbon atoms or an oxy group to which a derivative thereof is bonded is mentioned.

-SO ₂ -R ¹⁰¹ is a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, a pentylsulfonyl group, a hexylsulfonyl group, a (2-ethyl)hexylsulfonyl group, a heptylsulfonyl group, an octylsulfonyl group, and a nonylsulfonyl group. nyl group, decylsulfonyl group, undecylsulfonyl group, dodecylsulfonyl group, icosylsulfonyl group, phenylsulfonyl group, p-tolylsulfonyl group, etc., and a group represented by the above formula having 1 to 40 carbon atoms (preferably A hydrocarbon group having 1 to 20 carbon atoms or a derivatized group thereof (for example, a carboxy group, a sulfo group, a nitro group, a hydroxyl group, a halogen (preferably a chlorine atom), an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably octyl sulfide) a sulfonyl group) to which a group derivatized with a pamoyl group)) is bonded, and preferably a hydrocarbon group having 1 to 10 carbon atoms or a sulfonyl group to which a derivatized group thereof is bonded.

-SO ₂ N(R ¹⁰² ) ₂ as a sulfamoyl group;

N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N-sec-butylsulfur Pamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N-(1-ethylpropyl)sulfamoyl group, N-hexylsulfamoyl group, N-(2-ethyl)hexylsulfamoyl group, N-heptylsulfamoyl group, N-octylsulfamoyl group, N-nonylsulfamoyl group, N-decylsulfamoyl group, N-undecylsulfamoyl group, N-dodecylsulfamoyl group, N-icosylsulfamoyl group, N - One C1-C40 (preferably C1-C20) hydrocarbon group, such as a phenylsulfamoyl group, and the group represented by the above formula, or its derivatization group (For example, a carboxy group, a sulfo group, a nitro group) , a sulfamoyl group substituted with a hydroxyl group, a halogen (preferably a chlorine atom), or a group derivatized with an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably an octylsulfamoyl group) or the like;

N,N-dimethylsulfamoyl group, N,N-ethylmethylsulfamoyl group, N,N-diethylsulfamoyl group, N,N-propylmethylsulfamoyl group, N,N-dipropylsulfamoyl group, N ,N-isopropylmethylsulfamoyl group, N,N-diisopropylsulfamoyl group, N,N-tert-butylmethylsulfamoyl group, N,N-diisobutylsulfamoyl group, N,N-disec -Butylsulfamoyl group, N,N-ditert-butylsulfamoyl group, N,N-butylmethylsulfamoyl group, N,N-dibutylsulfamoyl group, N,N-dipentylsulfamoyl group, N,N -di(1-ethylpropyl)sulfamoyl group, N,N-dihexylsulfamoyl group, N,N-di(2-ethyl)hexylsulfamoyl group, N,N-diheptylsulfamoyl group, N,N-octyl group Methylsulfamoyl group, N,N-dioctylsulfamoyl group, N,N-dinonylsulfamoyl group, N,N-decylmethylsulfamoyl group, N,N-undecylmethylsulfamoyl group, N,N-dodecyl group 2 carbon atoms, such as a methylsulfamoyl group, N,N-icosylmethylsulfamoyl group, N,N-phenylmethylsulfamoyl group, N,N-diphenylsulfamoyl group, and a group represented by the above formula A hydrocarbon group having 1 to 40 (preferably 1 to 20 carbon atoms) or a derivatized group thereof (eg, a carboxy group, a sulfo group, a nitro group, a hydroxy group, a halogen (preferably a chlorine atom), an alkylsulfamo having 1 to 10 carbon atoms) and a sulfamoyl group substituted with a diyl (preferably a group derivatized with an octylsulfamoyl group), etc.;

A sulfamoyl group preferably substituted with one or two hydrocarbon groups having 1 to 10 carbon atoms or a derivative thereof is mentioned.

-CON(R ¹⁰² ) ₂ is a carbamoyl group;

N-methylcarbamoyl group, N-ethylcarbamoyl group, N-propylcarbamoyl group, N-isopropylcarbamoyl group, N-butylcarbamoyl group, N-isobutylcarbamoyl group, N-sec-butylcarbamoyl group Bamoyl group, N-tert-butylcarbamoyl group, N-pentylcarbamoyl group, N-(1-ethylpropyl)carbamoyl group, N-hexylcarbamoyl group, N-(2-ethyl)hexylcarbamoyl group, N-heptylcarbamoyl group, N-octylcarbamoyl group, N-nonylcarbamoyl group, N-decylcarbamoyl group, N-undecylcarbamoyl group, N-dodecylcarbamoyl group, N-icosylcarbamo group A hydrocarbon group having 1 to 40 carbon atoms (preferably 1 to 20 carbon atoms) or a derivatized group thereof (eg, a carboxy group, a sulfo group, , a carbamoyl group substituted with a nitro group, a hydroxyl group, a halogen (preferably a chlorine atom), or a group derivatized with an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably an octylsulfamoyl group) or the like;

N,N-dimethylcarbamoyl group, N,N-ethylmethylcarbamoyl group, N,N-diethylcarbamoyl group, N,N-propylmethylcarbamoyl group, N,N-dipropylcarbamoyl group, N ,N-isopropylmethylcarbamoyl group, N,N-diisopropylcarbamoyl group, N,N-tert-butylmethylcarbamoyl group, N,N-diisobutylcarbamoyl group, N,N-disec -Butylcarbamoyl group, N,N-ditert-butylcarbamoyl group, N,N-butylmethylcarbamoyl group, N,N-dibutylcarbamoyl group, N,N-butyloctylcarbamoyl group, N, N-dipentylcarbamoyl group, N,N-di(1-ethylpropyl)carbamoyl group, N,N-dihexylcarbamoyl group, N,N-di(2-ethyl)hexylcarbamoyl group, N, N-diheptylcarbamoyl group, N,N-octylmethylcarbamoyl group, N,N-dioctylcarbamoyl group, N,N-dinonylcarbamoyl group, N,N-decylmethylcarbamoyl group, N, N-undecylmethylcarbamoyl group, N,N-dodecylmethylcarbamoyl group, N,N-icosylmethylcarbamoyl group, N,N-phenylmethylcarbamoyl group, N,N-diphenylcarbamoyl group and two hydrocarbon groups having 1 to 40 carbon atoms (preferably 1 to 20 carbon atoms) or a derivatized group thereof (for example, a carboxy group, a sulfo group, a nitro group, a hydroxyl group, a halogen ( preferably a chlorine atom), a carbamoyl group substituted with a C1-C10 alkylsulfamoyl group (preferably a group derivatized with an octylsulfamoyl group), etc.;

Preferably, the carbamoyl group etc. which were substituted by 1 or 2 C1-C10 hydrocarbon groups or its derivatization group are mentioned.

-N(R ¹⁰² ) ₂ is an amino group; N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, N-isobutylamino group, N-sec-butylamino group, N-tert-butylamino group, N-pentylamino group , N-hexylamino group, N-(2-ethyl)hexylamino group, N-heptylamino group, N-octylamino group, N-nonylamino group, N-decylamino group, N-undecylamino group, N-dodecylamino group, N- A hydrocarbon group having 1 to 40 carbon atoms (preferably 1 to 20 carbon atoms), such as an icosylamino group, N-phenylamino group, and a group represented by the above formula, or a derivatized group thereof (for example, a carboxy group, a sulfo group , an amino group substituted with a nitro group, a hydroxyl group, a halogen (preferably a chlorine atom), an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably an octylsulfamoyl group) or the like);

N,N-dimethylamino group, N,N-ethylmethylamino group, N,N-diethylamino group, N,N-propylmethylamino group, N,N-dipropylamino group, N,N-isopropylmethylamino group, N, N-diisopropylamino group, N,N-tert-butylmethylamino group, N,N-diisobutylamino group, N,N-disec-butylamino group, N,N-ditert-butylamino group, N,N- Butylmethylamino group, N,N-dibutylamino group, N,N-dipentylamino group, N,N-di(1-ethylpropyl)amino group, N,N-dihexylamino group, N,N-di(2-ethyl) ) Hexylamino group, N,N-diheptylamino group, N,N-dioctylamino group, N,N-dinonylamino group, N,N-decylmethylamino group, N,N-undecylmethylamino group, N,N-dode A sylmethylamino group, N,N-icosylmethylamino group, N,N-phenylmethylamino group, N,N-diphenylamino group, etc., and a group represented by the above formulas having 2 to 40 carbon atoms (preferably A hydrocarbon group having 1 to 20 carbon atoms or a derivatized group thereof (for example, a carboxy group, a sulfo group, a nitro group, a hydroxyl group, a halogen (preferably a chlorine atom), an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably octyl sulfide) an amino group substituted with a group derivatized with a pamoyl group), etc.);

Preferably, one or two C1-C10 hydrocarbon groups, or an amino group substituted with its derivatization group, etc. are mentioned.

-NHCO-R ¹⁰² is a formylamino group; Acetylamino group, propanoylamino group, butanoylamino group, 2,2-dimethylpropanoylamino group, pentanoylamino group, hexanoylamino group, (2-ethyl)hexanoylamino group, heptanoylamino group, octanoylamino group, nonanoyl amino group, decanoylamino group, undecanoylamino group, dodecanoylamino group, henicosanoylamino group, benzoylamino group, and groups having 1 to 40 carbon atoms (preferably 1 to 20 carbon atoms) Derivatized with a hydrocarbon group or a derivatized group thereof (for example, a carboxy group, a sulfo group, a nitro group, a hydroxyl group, a halogen (preferably a chlorine atom), an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably an octylsulfamoyl group), etc. a carbonylamino group to which the group formed) is bonded (when the carbonylamino group is an acylamino group, the carbon number is 1 to 40);

Preferably, a hydrocarbon group having 1 to 10 carbon atoms or a carbonylamino group to which a derivatized group thereof is bonded (when the carbonylamino group is an alkanoylamino group, the carbon number is more preferably 1 to 10) and the like.

As -NHCON(R ¹⁰² ) ₂ , the groups mentioned above are mentioned.

As -NHCOOR ¹⁰² , the group mentioned above is mentioned.

Examples of -OCON(R ¹⁰² ) ₂ include the groups listed above.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are preferable.

As M of -SO ₃ M and -CO ₂ M, a hydrogen atom; Alkali metal atoms, such as a lithium atom, a sodium atom, and a potassium atom, are mentioned, Preferably a hydrogen atom, a sodium atom, and a potassium atom are mentioned.

The -CO-R ¹⁰² , -COO-R ¹⁰² , -OCO-R ¹⁰² , -COCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰² , -SO ₂ N(R ¹⁰² ) ₂ , -CON(R ¹⁰² ) ₂ , -N(R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , -NHCON(R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON(R ¹⁰² ) ₂ Substituent (first substituent) included in 2 is one or Two or more may be sufficient, and two or more substituents may mutually independently be the same or different.

In addition, as for the said 1st substituent, the other substituent (2nd substituent) may couple|bond with the hydrocarbon group contained in the part. The second substituent may be selected from the same groups as the first substituent.

The compound represented by Formula (I) may have the partial structure shown below in addition to said group.

R ^N1 and R ^N2 are preferably an aliphatic hydrocarbon group, an aralkyl group, a (cycloalkyl)alkyl group, an aliphatic hydrocarbon group substituted with a hydroxyl group, or an aliphatic hydrocarbon group substituted with an oxy group bonded to one side of a hydrocarbon group having 1 to 20 carbon atoms, straight-chain Or a branched alkyl group, a linear or branched alkenyl group, a cycloalkyl group, an aralkyl group, a (cycloalkyl)alkyl group, a linear or branched alkyl group substituted with a hydroxy group, or a straight or branched chain alkyl group substituted with an alkoxy group is more preferable. do.

R ^N1 and R ^N2 may be the same or different.

It is preferable that R ^N3 is an aliphatic hydrocarbon group, It is more preferable that it is a linear or branched alkyl group, It is more preferable that it is a linear alkyl group.

It is preferable that ^R4 is a hydrogen atom, and it is more preferable that R1 ^{- R8} is a hydrogen atom.

A ^{g -} in the compound represented by formula (I) represents a g-valent anion. g represents an integer of 1 to 14, preferably an integer of 1 to 10, more preferably an integer of 1 to 8, further preferably an integer of 1 to 6, particularly preferably 1 An integer of -4 is represented.

A well-known anion is mentioned as A ^g- . Specifically, as A ^g- ,

halide ions, such as a fluoride ion, a chloride ion, a bromide ion, and an iodide ion;

OH ^- ; CN ^- ; NO ₃ ^- ; NO ₂ ^- ; ClO ^- ; ClO ₂ ^- ; ClO ₃ ^- ; ClO ₄ ^- ; MnO ₄ ^- ; CH ₃ CO ₂ ^- , C ₆ H ₅ CO ₂ ^- ; tosylate anion; HCO ₃ ^- ; H ₂ PO ₄ ^- ; HSO ₄ ^- ; HS ^- ; SCN ^- ; H(COO) ₂ ^- ; [Al(OH) ₄ ] ^- , [Al(OH) ₄ (H ₂ O) ₂ ] ^- ; [Ag(CN) ₂ ] ^- ; [Cr(OH) ₄ ] ^- ; [AuCl ₄ ] ^- ; O ^{2 -} ; S ^2- ; O ₂ ^2- ; SO ₄ ^2- , HSO ₄ ^- ; SO ₃ ^2- ; S ₂ O ₃ ^2- ; CO ₃ ^2- ; CrO ₄ ^2- ; Cr ₂ O ₇ ^2- ; (COO) ₂ ^2- ; HPO ₄ ^2- ; [Zn(OH) ₄ ] ^2- ; [Zn(CN) ₄ ] ^2- ; [CuCl ₄ ] ^2- ; PO ₄ ^3- ; [Fe(CN) ₆ ] ^3- ; [Ag(S ₂ O ₃ ) ₂ ] ^3- ; [Fe(CN) ₆ ] ^4- ; C1 _- C20 alkoxy ions ^, such as _CH3O- , _CH3CH2O- ^, _{( CH3} ) _3CO- , C6 ^- C20 aryloxy ion, such as _C6H5O- ^;

fluorine-containing anion; and an anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen as essential elements.

A ^{g −} is a fluorine-containing anion or an anion containing oxygen as an essential element and at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus from the viewpoint of improving heat resistance and reducing sublimation properties. Preferably, it is an anion containing at least one element selected from the group consisting of tungsten and phosphorus and oxygen as an essential element, or a fluorine-containing anion, and at least one selected from the group consisting of tungsten and phosphorus. It is more preferable that it is an anion containing an element and oxygen as essential elements.

Examples of the fluorine-containing anion include CF ₃ CO ₂ ⁻ and groups represented by the following formulas (III), (IV), (V) and (VI).

[In formula (III), W ³ and W ⁴ each independently represent a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms, or W ³ and W ⁴ are taken together to form a fluorinated egg having 1 to 4 carbon atoms. Represents a Candiyl journal.]

[In formula (IV), W ⁵ to W ⁷ each independently represent a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms.]

[In formula (V), Y ¹ represents a fluorinated alkanediyl group having 1 to 4 carbon atoms.]

[In formula (VI), Y ² represents a fluorinated alkyl group having 1 to 4 carbon atoms.]

In the formulas (III), (IV) and (VI), the perfluoroalkyl group is preferable as the fluorinated alkyl group having 1 to 4 carbon atoms. Examples of the perfluoroalkyl group include -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , -CF(CF ₃ ) ₂ , -CF ₂ CF ₂ CF ₂ CF ₃ , -CF ₂ CF(CF ₃ ) ₂ , -C(CF ₃ ) ₃ , and the like.

In formulas (III) and (V), the fluorinated alkanediyl group having 1 to 4 carbon atoms is preferably a perfluoroalkanediyl group, -CF ₂ -, -CF ₂ CF ₂ -, -CF ₂ CF ₂ CF ₂ - , -C(CF ₃ ) ₂ -, -CF ₂ CF ₂ CF ₂ CF ₂ -, and the like.

As the anion represented by the formula (III) (hereinafter sometimes referred to as "anion (III)"), the anion represented by the formulas (III-1) to (III-6) (hereinafter "anion (III)" on (III-1)" to "anion (III-6)" in some cases).

Examples of the anion represented by the formula (IV) (hereinafter sometimes referred to as “anion (IV)”) include the anion (IV-1) represented by the formula (IV-1).

As the anion represented by the formula (V) (hereinafter sometimes referred to as “anion (V)”), the anion represented by the formulas (V-1) to (V-4) (hereinafter “anion”), respectively (V-1)" to "anion (V-4)") are mentioned.

As the anion represented by the formula (VI) (hereinafter sometimes referred to as "anion (VI)"), the anion represented by the formulas (VI-1) to (VI-4) (hereinafter "anion"), respectively (VI-1)" to "anion (VI-4)") are mentioned.

The fluorine-containing anion may be at least one anion selected from the group consisting of CF ₃ CO ₂ ⁻ , anion (III), anion (IV), anion (V) and anion (VI). Among them, CF ₃ CO ₂ ^- , anion (III-1), anion (III-2), anion (III-6), anion (IV-1), anion (V-1), anion (VI-1), anion (VI-2), anion (VI-3) are preferable, CF ₃ CO ₂ ^- , anion (III-2), anion (IV-1), anion ( VI-1) is more preferable.

Examples of the anion include an anion containing oxygen as an essential element and at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus. The anion of heteropolyacid or isopolyacid containing tungsten as an essential element is preferable, and the anion of phosphotungstic acid, silicotungstic acid, and a tungsten-type isopolyacid is more preferable. Such anion is used for, for example, a colored compound represented by formula (I) having a fluorine-containing anion (preferably anion (VI-1)), and when anion exchanged, it contributes to heat resistance improvement. .

Examples of the anion of the heteropolyacid or isopolyacid containing tungsten as an essential element include Keggin type tungstate ion α-[PW ₁₂ O ₄₀ ] ^3- , Dawson type tungsten phosphate ion α-[P ₂ W ₁₈ O ₆₂ ] ^6- , β-[P ₂ W ₁₈ O ₆₂ ] ^6- , Kegin-type silicate tungstate ion α-[SiW ₁₂ O ₄₀ ] ^4- , β-[SiW ₁₂ O ₄₀ ] ^4- , γ-[SiW ₁₂ O ₄₀ ] ^4- , and as other examples [P ₂ W ₁₇ O ₆₁ ] ^10- , [P ₂ W ₁₅ O ₅₆ ] ^12- , [H ₂ P ₂ W ₁₂ O ₄₈ ] ^12- , [NaP ₅ W ₃₀ O ₁₁₀ ] ^14- , α-[SiW ₉ O ₃₄ ] ^10- , γ-[SiW ₁₀ O ₃₆ ] ^8- , α-[SiW ₁₁ O ₃₉ ] ^8- , β-[SiW ₁₁ O ₃₉ ] ^8- , [W ₆ O ₁₉ ] ^2- , [W ₁₀ O ₃₂ ] ^4- , WO ₄ ^2- , and the like. Among them, Keggin-type tungstic acid ion α-[PW ₁₂ O ₄₀ ] ^3- is more preferable.

The compound (I) is preferably a compound represented by the formula (I-B) (hereinafter sometimes referred to as compound (I-B)). When compound (I) is compound (I-B), it is excellent in heat resistance.

[In formula (I-B), R ^N1 , R ^N2 , R ^N3 , R ¹ to R ⁸ , R ¹⁰¹ , R ¹⁰² and M have the same meanings as above.

B ^{h −} represents an anion having an h valence containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen as essential elements.

h represents an integer from 1 to 14.]

In formula (I-B), as B ^{h -} , the same thing as the g-valent anion which has tungsten, molybdenum, etc. contained as A ^{g -} in formula (I) is mentioned.

In the formula (I-B), preferred B ^{h −} contains oxygen and at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus as A ^{g −} in the formula (I) as essential elements. Among the g-valent anions, the same as preferred ones are mentioned.

As compound (I), the compound shown in Tables 1-10, or its alkali metal salt is mentioned.

In addition, in Tables 1-10, "Me" represents a methyl group, "Et" represents an ethyl group, "Bu" represents a butyl group, "TBu" represents a tert-butyl group, "Hex" represents a hexyl group, "Oct" represents an octyl group, "2EH" represents a 2-ethylhexyl group, "CHM" represents a cyclohexylmethyl group, "CH" represents a cyclohexyl group, "PH" represents a phenyl group, "BZ"" represents a benzyl group, "NPR" represents a propyl group, "IPR" represents an isopropyl group, "IBu" represents an isobutyl group, "EOE" represents -CH ₂ CH ₂ OCH ₂ CH ₃ , "ALL " represents an allyl group, "HYE" represents a 2-hydroxyethyl group,

"COM" represents -CO-CH ₃ , "COE" represents -COO-CH ₂ CH ₃ , "OCM" represents -OCO-CH ₃ , "OME" represents -O-CH ₃ ,

"SOT" represents a tosyl group, "SNH" represents -SO ₂ NH-CH ₂ CH(CH ₂ CH ₃ )((CH ₂ ) ₃ CH ₃ ), "SN2" is -SO ₂ N(CH ₃ ) ) ((CH ₂ ) ₇ CH ₃ ), "CNM" represents -CONHCH ₃ , "CN2" represents -CON(CH ₃ )C ₆ H ₅ , and "NPH" represents -NHC ₆ H ₅ represents, "NOT" represents -N((CH ₂ ) ₇ CH ₃ ) ₂ , "NCO" represents -NHCO((CH ₂ ) ₄ CH ₃ ), "F" represents a fluorine atom, "Cl " represents a chlorine atom, "Br" represents a bromine atom, "CN" represents a cyano group,

"NO2" represents a nitro group, "SUA" represents -SO ₃ H, "CBA" represents -CO ₂ H, "CHO" represents -CHO,

"OCH" represents -OCOH, "OH" represents -OH, "SFM" represents -SO ₂ NH ₂ , "CBM" represents -CONH ₂ ,

"NH2" represents -NH2, "NCH" represents -NHCOH, "III- ₁ " to "III-6" represent anion (III-1) to anion (III-6),

"IV-1" represents anion (IV-1), "V-1" to "V-4" represent anion (V-1) to anion (V-4), and "VI-1" ' to "VI-4" represent anion (VI-1) to anion (VI-4).

Compound (I-1) is a compound represented by Formula (I-1), for example.

From the viewpoint of easy synthesis, it is preferably compound (I-1) to compound (I-312), more preferably compound (I-1) to compound (I-156), and compound (I-1) -Compound (I-24) is more preferred, and compound (I-13) -Compound (I-24) is particularly preferred.

Among them, compound (I) of the present invention is particularly preferably compound (I-14).

The compound (I) of the present invention includes a compound represented by formula (II) (hereinafter sometimes referred to as compound (II)) and a compound represented by formula (II-1) (hereinafter, compound (II-) 1) may be obtained by reacting. It may be obtained by making it react.

[In formulas (II) and (II-1), R ¹ to R ⁸ , R ^N1 , R ^N2 , R ^N3 and g have the same meanings as above, and A′ represents g electrons in A ^{g −} It indicates what has been given.]

An alkylating agent is mentioned as a compound represented by Formula (II-1). The alkylating agent is preferably an alkyl halide (such as methyl chloride, methyl bromide or methyl iodide) having 1 to 10 carbon atoms, more preferably an alkyl halide having 1 to 3 carbon atoms; dialkyl carbonate (such as dimethyl carbonate or diethyl carbonate) preferably having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms; dialkyl sulfuric acid (such as dimethyl sulfuric acid or diethyl sulfuric acid) having preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms; Alkyl alkanesulfonate preferably having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms (methyl methanesulfonate, ethyl ethanesulfonate, ethyl methanesulfonate, methyl ethanesulfonate, trifluoromethane methyl sulfonate, ethyl trifluoromethanesulfonate, etc.);

The alkylating agent is preferably a methylating agent, an ethylating agent, a propylating agent, or a butylating agent, and more preferably a methylating agent.

The amount of the alkylating agent to be used is preferably 1 mol or more and 20 mol or less, and more preferably 1 mol or more and 10 mol or less with respect to 1 mol of compound (II).

0 to 150 degreeC is preferable and, as for reaction temperature, 10-100 degreeC is more preferable. In order to make the solubility of the coloring compound precursor represented by Formula (I) sufficient, you may mix beforehand with a predetermined organic solvent at about 70-100 degreeC. 10 minutes - 24 hours are preferable, and, as for reaction time, 1 hour - 12 hours are more preferable.

The reaction is preferably performed in an organic solvent from the viewpoint of yield. Examples of the organic solvent include aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as hexane; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, methylene chloride and chloroform; alcohol solvents such as methanol, ethanol, isopropanol and butanol; nitro hydrocarbon solvents such as nitrobenzene; ketone solvents such as acetone and methyl isobutyl ketone; ester solvents such as ethyl acetate; ether solvents such as diethyl ether and tetrahydrofuran; nitrile solvents such as acetonitrile; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and 1-methyl-2-pyrrolidone; etc. are mentioned, An aromatic hydrocarbon solvent is preferable, and toluene and xylene are more preferable. To [ the usage-amount of an organic solvent / 1 mass part of compound (II) ], Preferably they are 1 mass part or more and 300 mass parts or less, More preferably, they are 1 mass part or more and 100 mass parts or less.

The method for obtaining the compound from the reaction mixture is not particularly limited, and various known methods can be employed. For example, the method of filtering the reaction mixture, for example, washing|cleaning with solvents, such as aromatic hydrocarbon solvents, such as toluene, and drying the obtained residue is mentioned. If necessary, it may further refine|purify by the method of recrystallizing using a solvent, or silica gel column chromatography. The obtained compound becomes a compound represented by Formula (I), for example.

Next, a method of exchanging anions in the compound represented by the formula (I) may be employed, and as the method, at least one element selected from the group consisting of tungsten, silicon and phosphorus and oxygen are included as essential elements. The method of adding a compound etc. are mentioned.

A compound containing at least one element selected from the group consisting of tungsten, silicon and phosphorus and oxygen as essential elements (herein, also referred to as an anion exchanger) can be produced by a known and customary method, but a commercially available product may be used as is. Examples of such a compound include corresponding heteropolyacids, isopolyacids, silicates, and phosphates, and tungstic phosphotungstic acid, silicotungstic acid, molybdic phosphomolybdic acid and molybdic silicic acid may be used.

The amount of the anion exchanger to be used is preferably 0.01 mol or more and 5 mol or less, and more preferably 0.01 mol or more and 1 mol or less with respect to 1 mol of the compound represented by formula (I).

As reaction temperature, 0-150 degreeC is preferable and 10-100 degreeC is more preferable. As reaction time, 10 minutes - 36 hours are preferable, and 10 minutes - 24 hours are more preferable.

From the viewpoint of yield, this reaction is preferably performed in water, an organic solvent, or a mixture thereof. Examples of the organic solvent include aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as hexane; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, methylene chloride and chloroform; alcohol solvents such as methanol, ethanol, isopropanol and butanol; nitro hydrocarbon solvents such as nitrobenzene; ketone solvents such as acetone and methyl isobutyl ketone; ester solvents such as ethyl acetate; ether solvents such as diethyl ether and tetrahydrofuran; nitrile solvents such as acetonitrile; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and 1-methyl-2-pyrrolidone; and the like. Examples of the solvent in which the above reaction is carried out include water, an alcohol solvent, a ketone solvent, an ether solvent, a nitrile solvent, an amide solvent, or a mixture thereof, More preferably, water, an alcohol solvent, a ketone solvent, a nitrile solvent, an amide solvent or a mixture thereof, more preferably water, an alcohol solvent, or a mixture thereof, particularly preferably water, methanol, or a mixture thereof.

To [ the usage-amount of an organic solvent / 1 mass part of compound represented by Formula (I) ], Preferably they are 1 mass part or more and 1000 mass parts or less, More preferably, they are 10 mass parts or more and 500 mass parts or less.

When such a method is employed, when anions of the compound represented by the formula (I) are exchanged, a compound suitable for improving heat resistance and reducing sublimability can be obtained.

Compound (II) is a compound represented by formula (VII) (hereinafter sometimes referred to as compound (VII)) and a compound represented by formula (VIII) (hereinafter sometimes referred to as compound (VIII)). ) can be prepared by reacting in the presence of a base.

[In formulas (VII) and (VIII), R ¹ to R ³ , R ⁵ to R ⁸ , R ^N1 and R ^N2 have the same meanings as above, and R ⁹ represents an alkyl group having 1 to 20 carbon atoms.]

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ⁹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group, and preferably a C1 group. -6 alkyl groups are mentioned.

Organic bases, such as triethylamine and piperidine, are mentioned as a base, The usage-amount is 0.05-20 mol normally with respect to 1 mol of compound (VII).

The amount of compound (VIII) to be used is usually 1 to 10 moles, preferably 1 to 4 moles, per 1 mole of compound (II).

The reaction of compound (VII) and compound (VIII) is usually carried out in the presence of a solvent, and the solvent is a nitrile solvent such as acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1- Alcohol solvents such as octanol, ether solvents such as tetrahydrofuran, ketone solvents such as acetone, ester solvents such as ethyl acetate, aliphatic hydrocarbon solvents such as hexane, aromatic hydrocarbon solvents such as toluene, halogenated hydrocarbons such as methylene chloride and chloroform solvents and amide solvents such as N,N-dimethylformaldehyde and N-methylpyrrolidone, preferably nitrile solvents, alcohol solvents and aromatic hydrocarbon solvents, more preferably acetonitrile, methanol and toluene. The usage-amount is 1-100 mass parts normally with respect to 1 mass part of compound (VII).

Reaction temperature is 0-200 degreeC normally, Preferably it is 0-150 degreeC. The reaction time is usually 0.5 to 36 hours.

After completion of the reaction, for example, the compound (II) can be extracted by mixing the obtained reaction mixture with a solvent in which the compound (II) is difficult to dissolve and filtering. If necessary, it may further refine|purify by the method of recrystallizing using a solvent, or silica gel column chromatography.

Compound (VII) may be referred to as a compound represented by formula (IX) (hereinafter, sometimes referred to as compound (IX)) and a compound represented by formula (X) (hereinafter referred to as compound (X)). ) can be prepared by reacting in a solvent.

[In formulas (IX) and (X), R ⁵ to R ⁹ have the same meanings as above, and R ¹⁰ represents an alkyl group having 1 to 4 carbon atoms.]

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ¹⁰ include a methyl group, an ethyl group, a propyl group and a butyl group.

The amount of compound (X) used is usually 1 to 5 moles, preferably 1 to 3 moles, per 1 mole of compound (IX).

Alcohol solvents, such as methanol, are mentioned as a solvent, The usage-amount is 1-200 mass parts normally with respect to 1 mass part of compound (IX).

The reaction temperature is usually -20 to 100°C, and the reaction time is usually 1 to 72 hours.

After completion of the reaction, for example, the compound (VII) can be extracted by mixing the reaction mixture with water or methanol as needed and then filtering. In addition, after completion of the reaction, for example, after mixing the reaction mixture and water if necessary, extraction with an organic solvent insoluble in water such as ethyl acetate, and concentrating the obtained organic layer, compound (VII) can also be extracted. have. If necessary, it may further refine|purify by the method of recrystallizing using a solvent, or silica gel column chromatography.

Compound (X) is, for example, J. Med. Chem. 2012, 55, it can manufacture according to well-known methods, such as the method of 3398-3413.

The coloring composition of this invention may contain 2 or more types of compound (I). Compound (I) can be used as a coloring agent (A) together with dyes or pigments (coloring agent (A1)) other than compound (I) as needed.

The coloring composition of this invention contains the said compound (I), at least one of resin (B), and a solvent (E), The said compound (I), and both resin (B), and a solvent (E) are contained It is preferable to do

<Resin (B)>

The resin (B) is preferably an alkali-soluble resin, and is derived from at least one monomer (a) (hereinafter sometimes referred to as “(a)”) selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride. It is more preferable that it is a polymer which has a structural unit to say.

Resin (B) is a structural unit derived from a monomer (b) (hereinafter sometimes referred to as “(b)”) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond, and others; It is preferable that it is a copolymer having a structural unit of

As another structural unit, the structural unit derived from the monomer (c) copolymerizable with the monomer (a) (however, the monomer (a) and the monomer (b) are different. Hereinafter, it may be referred to as "(c)").) , a structural unit having an ethylenically unsaturated bond, and the like.

As (a), For example, unsaturated monocarboxylic acids, such as acrylic acid, methacrylic acid, a crotonic acid, and 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, dimethyl unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid;

methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-carboxybicyclo[2.2.1]hept-2-ene, bicyclo unsaturated compounds containing a carboxy group, such as 5-carboxymethylbicyclo[2.2.1]hept-2-ene and 5-carboxyethylbicyclo[2.2.1]hept-2-ene;

carboxylic acid anhydrides such as anhydrides of the above unsaturated dicarboxylic acids other than fumaric acid and mesaconic acid;

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

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 from the point of copolymerization reactivity and the solubility point with respect to the aqueous alkali solution of resin obtained.

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

As (b), for example, a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b2)”) and a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”); and the like.

As (b1), for example, a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-1)") and an alicyclic unsaturated hydrocarbon and a monomer (b1-2) having a structure in which hydrocarbon is epoxidized (hereinafter sometimes referred to as “(b1-2)”).

As (b1-1), the monomer which has a glycidyl group and an ethylenically unsaturated bond is preferable. Specifically as (b1-1), glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl ether, vinyl Benzyl glycidyl ether, α-methylvinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis( Glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxy) methyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene and 2,4,6-tris(glycidyloxymethyl) Styrene etc. are mentioned.

As (b1-2), vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide (trademark) 2000; manufactured by Daicel Corporation), 3,4-epoxy Cyclohexylmethyl (meth) acrylate (for example, Cyclomer (registered trademark) A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, cyclomer ( registered trademark) M100 (manufactured by Daicel Corporation), a compound represented by formula (BI), a compound represented by formula (BII), and the like.

[In formulas (BI) and (BII), R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group .

X ^a and X ^b each independently represent a single bond, *-R ^c -, *-R ^c -O-, *-R ^c -S- or *-R ^c -NH-.

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

* indicates a bond with O.]

Examples of the compound represented by formula (BI) include compounds represented by any of formulas (BI-1) to (BI-15), preferably formulas (BI-1) and (BI-3) and compounds represented by formulas (BI-5), formula (BI-7), formula (BI-9) and formula (BI-11) to formula (BI-15), more preferably (BI-15). -1), the compound represented by a formula (BI-7), a formula (BI-9), and a formula (BI-15) is mentioned.

Examples of the compound represented by formula (BII) include compounds represented by any one of formulas (BII-1) to (BII-15), preferably formulas (BII-1) and (BII-3) and compounds represented by formulas (BII-5), formula (BII-7), formula (BII-9) and formulas (BII-11) to formula (BII-15), more preferably formula ( BII-1), a compound represented by a formula (BII-7), a formula (BII-9), and a formula (BII-15) is mentioned.

The compound represented by Formula (BI) and the compound represented by Formula (BII) may be used individually, respectively, and the compound represented by Formula (BI) and the compound represented by Formula (BII) may be used together. When these are used together, the content ratio of the compound represented by the formula (BI) and the compound represented by the formula (BII) is preferably 5:95 to 95:5 on a molar basis, more preferably 10:90 to 90 :10, and more preferably 20:80 to 80:20.

As (c), for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2 -Ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-9-yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) ) acrylate, tricyclo [5.2.1.0 ^2,6 ] decen-9-yl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) (meth)acrylic acid esters such as acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (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]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybi Cyclo[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-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(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-methyl Bicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1] Hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxy Cycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene and 5,6-bis(cyclohexylox) bicyclo unsaturated compounds such as cycarbonyl)bicyclo[2.2.1]hept-2-ene;

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

Vinyl group-containing aromatic compounds, such as styrene, (alpha)-methylstyrene, vinyltoluene, and p-methoxystyrene; vinyl group-containing nitriles such as (meth)acrylonitrile; halogenated hydrocarbons such as vinyl chloride and vinylidene chloride; vinyl group-containing amides such as (meth)acrylamide; esters such as vinyl acetate; dienes such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene; and the like.

Of these, from the viewpoint of copolymerization reactivity and heat resistance, styrene, vinyltoluene, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl (meth)acrylate, and tricyclo[5.2.1.0 ^2,6 ]decane-9 -yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decen-9-yl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene, benzyl (meth)acrylate and the like are preferable.

The structural unit having an ethylenically unsaturated bond is preferably a structural unit having a (meth)acryloyl group. A resin having such a structural unit is obtained by adding a monomer having an ethylenically unsaturated bond to a group capable of reacting with the group of (a) or (b) to a polymer having a structural unit derived from (a) or (b). can

As such a structural unit, the structural unit which added glycidyl (meth)acrylate to the (meth)acrylic acid unit, the structural unit which added 2-hydroxyethyl (meth)acrylate to the maleic anhydride unit, and glycidyl The structural unit etc. which added (meth)acrylic acid to the (meth)acrylate unit are mentioned. Moreover, when such a structural unit has a hydroxyl group, the structural unit which further added carboxylic acid anhydride is also mentioned as a structural unit which has an ethylenically unsaturated bond.

The polymer having the structural unit derived from (a) can be produced, for example, by polymerization of a monomer constituting the structural unit of the polymer in a solvent in the presence of a polymerization initiator. A polymerization initiator, a solvent, etc. are not specifically limited, What is normally used in the said field|area can be used. For example, as a polymerization initiator, an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or an organic peroxide (benzoyl peroxide etc.) What is necessary is just to melt|dissolve each monomer as a solvent.

In addition, the obtained polymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and may use what was taken out as solid (powder) by methods, such as reprecipitation.

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

Examples of the carboxylic anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride; and the like.

Specifically as the resin (B), 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate / (meth) acrylic acid copolymer, 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(meth)acrylate/(meth)acrylic acid/N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ] Decyl (meth)acrylate/(meth)acrylic acid/N-cyclohexylmaleimide/2-hydroxyethyl (meth)acrylate copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth) ) acrylate/(meth)acrylic acid/vinyltoluene copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl(meth)acrylate/(meth)acrylic acid/2-ethylhexyl(meth)acrylate Copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / tricyclo [5.2.1.0 ^2,6 ] decenyl (meth) acrylate / (meth) acrylic acid / N- Cyclohexylmaleimide copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane/(meth)acrylic acid/styrene copolymer, benzyl(meth)acrylate/(meth)acrylic acid copolymer, styrene/( A meth)acrylic acid copolymer and the resin of each publication of Unexamined-Japanese-Patent No. 9-106071, Unexamined-Japanese-Patent No. 2004-29518, and Unexamined-Japanese-Patent No. 2004-361455, etc. are mentioned.

Especially, as resin (B), the copolymer containing the structural unit derived from (a) and the structural unit derived from (b) is preferable.

Resin (B) may combine 2 or more types, In this case, resin (B) is at least 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate/(meth)acrylic acid copolymer Copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl(meth)acrylate/(meth)acrylic acid/N-cyclohexylmaleimide/2-hydroxyethyl(meth)acrylate copolymer, 3 ,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl(meth)acrylate/(meth)acrylic acid/vinyltoluene copolymer, and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl(meth) ) It is preferable to include at least one selected from acrylate/(meth)acrylic acid/2-ethylhexyl (meth)acrylate copolymer.

Preferably the weight average molecular weight (Mw) of polystyrene conversion of resin (B) is 3,000-100,000, More preferably, it is 5,000-50,000, More preferably, it is 5,000-30,000. The degree of dispersion [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 (in terms of solid content) of the resin (B) is preferably 10 to 300 mg-KOH/g, more preferably 20 to 250 mg-KOH/g, and still more preferably 30 to 200 mg-KOH/g. Here, an acid value is a value measured as the quantity (mg) of potassium hydroxide required in order to neutralize 1 g of resin (B), For example, it can obtain|require by titrating using potassium hydroxide aqueous solution.

To [ the content rate of resin (B) in a coloring composition / total amount of solid content ], Preferably it is 3-99 mass %, More preferably, it is 5-99 mass %, More preferably, it is 7-95 mass %.

<Solvent (E)>

The solvent (E) is, for example, an ester solvent (a solvent containing -COO- in a molecule and not containing -O-), an ether solvent (containing -O- in a molecule and not containing -COO-), for example. solvent), ether ester solvent (solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (OH in the molecule) and solvents that do not contain -O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

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

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, phenetol and methyl anisole, etc. can be heard

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2-methyl Methyl propionate, 2-ethoxy-2-methyl ethyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl and ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and dipropylene glycol methyl ether acetate.

As a ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentane on, cyclohexanone, isophorone, and the like.

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

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

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

These solvents may use 2 or more types together.

Preferably the content rate of a solvent (E) is 40-99 mass % with respect to the total amount of a coloring composition, More preferably, it is 50-95 mass %.

The coloring composition of this invention WHEREIN: It is preferable that compound (I) is disperse|distributed to the solvent (E).

Compound (I) may be treated with rosin, surface treatment using a derivative into which an acidic or basic group is introduced, graft treatment on the surface of compound (I) with a high molecular compound, etc., atomization treatment by sulfuric acid atomization method, etc., impurities if necessary Washing treatment with an organic solvent, water, etc. for removing ionic impurities, removal treatment by ion exchange method, etc. It is preferable that the particle diameter of compound (I) is substantially uniform. Compound (I) can be made into a state in which compound (I) is uniformly dispersed in a dispersion liquid by containing a dispersing agent and performing a dispersion treatment.

Surfactants etc. are mentioned as a dispersing agent, Any surfactant of cationic, anionic, nonionic, and amphoteric type may be sufficient. Specifically, surfactants, such as a polyester type, a polyamine type, and an acryl type, etc. are mentioned. You may use these dispersing agents individually or in combination of 2 or more types. As a dispersing agent, if it shows by a brand name, KP (Shin-Etsu Chemical Co., Ltd. product), Florene (Kyoeisha Chemical Co., Ltd. product), Solsperse (trademark) (Zeneca Co., Ltd. product), EFKA (registered trademark) (manufactured by BASF Co., Ltd.), Azispa (registered trademark) (manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by Big Chemi Co., Ltd.), BYK (registered trademark) (manufactured by Big Chemi Co., Ltd.) ) and the like.

When using a dispersing agent, Preferably the usage-amount of a dispersing agent (solid content) is 300 mass parts or less with respect to 100 mass parts of compound (I), More preferably, they are 5 mass parts or more and 100 mass parts or less. When the usage-amount of a dispersing agent exists in said range, there exists a tendency for the coloring composition of a more uniform dispersed state to be obtained.

The content rate of compound (I) in a coloring composition is 0.1-60 mass % normally in the total amount of a coloring composition, Preferably it is 0.5-50 mass %, More preferably, it is 1-40 mass %.

The content rate of compound (I) in the coloring composition is 1 mass % or more and 90 mass % or less normally with respect to the total amount of solid content of a coloring composition, Preferably they are 1 mass % or more and 80 mass % or less, More preferably, they are 2 mass %. or more and 75 mass % or less.

The coloring composition of this invention may contain the coloring agent (Hereinafter, it may be called coloring agent (A1).) other than compound (I).). The coloring agent (A1) may contain 1 type, or 2 or more types of coloring agents. It is preferable that the colorant (A1) contains a yellow colorant, an orange colorant, or a red colorant.

<Colorant (A1)>

A coloring agent (A1) may be dye or a pigment may be sufficient as it. A well-known dye can be used as a dye, and the dye described in the color index (published by The Society of Dyers and Colorists) and the dyeing notebook (Shikisensha) is mentioned. According to the chemical structure, an azo dye, an anthraquinone dye, a triphenylmethane dye, a xanthene dye, a phthalocyanine dye, etc. are mentioned. You may use these dyes individually or in combination of 2 or more types.

Specifically, the dye of the following color index (C.I.) numbers is mentioned. C.I. Solvent Yellow 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162;

C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

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

C.I. Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141;

C.I. Disperse Yellow 51, 54, 76;

C.I. Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 99;

C.I. acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173;

C.I. Reactive Orange 16;

C.I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

C.I. Solvent Red 24, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247;

C.I. Acid Red 52, 73, 80, 91, 92, 97, 138, 151, 211, 274, 289;

C.I. acid violet 34, 102;

C.I. Disperse Violet 26, 27;

C.I. solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;

C.I. Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59:1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;

C.I. acid blue 25, 27, 40, 45, 78, 80, 112;

C.I. Direct Blue 40;

C.I. Disperse Blue 1, 14, 56, 60;

C.I. Solvent Green 1, 3, 5, 28, 29, 32, 33;

C.I. acid green 3, 5, 9, 25, 27, 28, 41;

C.I. Basic Green 1;

C.I. Bat Green 1st.

As a pigment, a well-known pigment can be used, For example, the pigment classified as a pigment by the color index (The Society of Dyers and Colorists publication) is mentioned. These can be used individually or in combination of 2 or more types.

Specifically, C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138 , 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214 yellow pigments;

C.I. Orange pigments, such as pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 179, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266 , 268, 269, 273 and other red pigments;

C.I. Blue pigments, such as pigment blue 15, 15:3, 15:4, 15:6, 60;

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

C.I. Green pigments, such as pigment green 7, 36, 58, 59, are mentioned.

The colorant (A1) is preferably a colorant containing at least one selected from a yellow colorant, an orange colorant, and a red colorant.

The yellow colorant is the above-mentioned C.I. Solvent Yellow 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162; C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

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

C.I. Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141;

C.I. yellow dyes such as Disperse Yellow 51, 54, and 76;

C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138 , 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214 yellow pigments;

It may be selected from among.

As a yellow colorant, a yellow dye and a yellow pigment are preferable, a yellow pigment is more preferable, a quinophthalone yellow pigment, a metal containing yellow pigment, and an isoindoline yellow pigment are still more preferable, C.I. Pigment yellow 129, 138, 139, 150 and 185 are particularly preferred.

The orange colorant is the C.I. Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 99;

C.I. acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173;

C.I. Reactive Orange 16;

C.I. orange dyes such as direct orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

C.I. Orange pigments, such as pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

It may be selected from among.

As an orange colorant, an orange dye and an orange pigment are preferable, and an orange pigment is more preferable, and C.I. Pigment oranges 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 are more preferable.

The red colorant is the above-mentioned C.I. Solvent Red 24, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247;

C.I. red dyes such as acid red 52, 73, 80, 91, 92, 97, 138, 151, 211, 274, 289;

C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 179, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266 , 268, 269, 273 and other red pigments;

It may be selected from among.

As a red colorant, a red dye and a red pigment are preferable, and azo dye, anthraquinone dye, triphenylmethane dye, xanthene dye, perylene dye, azo pigment, diketopyrrolopyrrole pigment, anthraquinone pigment, xanthene pigment, pe More preferred are rylene pigments, and C.I. Acid Red 52, C.I. Pigment red 144, 177, 179, 242, 254, and 269 are more preferable.

Moreover, as a yellow coloring agent, an orange coloring agent, or a red coloring agent, you may use the xanthene compound etc. which were described in Unexamined-Japanese-Patent No. 2013-235257.

When the coloring composition of this invention contains a coloring agent (A1) and a solvent (E), after preparing the coloring agent (A1) containing liquid containing a coloring agent (A1) and a solvent (E) beforehand, the said coloring agent (A1) containing liquid You may prepare a coloring composition using it. When a coloring agent (A1) does not melt|dissolve in a solvent (E), a coloring agent (A1) containing liquid can be prepared by dispersing and mixing a coloring agent (A1) in a solvent (E). The coloring agent (A1) containing liquid may contain a part or all of the solvent (E) contained in a coloring composition.

The coloring composition of this invention is manufactured by mixing the compound represented by Formula (I), a resin, a solvent (E), and the coloring agent (A1) containing liquid containing the coloring agent (A1) and the solvent (E) it is preferable As the manufacturing method, the compound represented by the formula (I), the resin, and the solvent (E) are mixed with a bead mill or the like to prepare a coloring composition, the obtained coloring composition, the coloring agent (A1) and the solvent (E) A method of mixing the colorant (A1) containing liquid is preferred.

The colorant (A1) is, if necessary, rosin treatment, surface treatment using a colorant derivative into which an acidic group or basic group is introduced, graft treatment on the surface of the colorant (A1) with a polymer compound, etc., atomization treatment by sulfuric acid atomization method, etc.; Washing treatment with an organic solvent, water, etc. for removing impurities, removal treatment of ionic impurities by an ion exchange method, etc. may be performed. It is preferable that the particle diameter of a coloring agent (A1) is substantially uniform. The coloring agent (A1) can be made into the state which disperse|distributed the coloring agent (A1) uniformly in the coloring agent (A1) containing liquid by making it contain a dispersing agent and performing a dispersion process. A coloring agent (A1) may carry out a dispersion process independently, respectively, and may mix and disperse|distribute multiple types.

Surfactants etc. are mentioned as a dispersing agent, Any surfactant of cationic, anionic, nonionic, and amphoteric type may be sufficient. Specifically, surfactants, such as a polyester type, a polyamine type, and an acryl type, etc. are mentioned. You may use these dispersing agents individually or in combination of 2 or more types. As a dispersing agent, if it shows by a brand name, KP (Shin-Etsu Chemical Co., Ltd. product), Florene (Kyoeisha Chemical Co., Ltd. product), Solsperse (trademark) (Zeneca Co., Ltd. product), EFKA (registered trademark) (manufactured by BASF Co., Ltd.), Azispa (registered trademark) (manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by Big Chemi Co., Ltd.), BYK (registered trademark) (manufactured by Big Chemi Co., Ltd.) ) and the like.

When using a dispersing agent in order to prepare the said colorant (A1) containing liquid, the usage-amount of the said dispersing agent (solid content) becomes like this with respect to 100 mass parts of coloring agents (A1) Preferably it is 300 mass parts or less, More preferably, it is 5 mass parts or more and 100 parts by mass or less. When the usage-amount of the said dispersing agent exists in the said range, there exists a tendency for the coloring agent (A1) containing liquid in a more uniformly dispersed state to be obtained.

The content rate of the coloring agent (A1) in the coloring agent (A1) containing liquid is 0.1-60 mass % normally in the total amount of the coloring agent (A1) containing liquid, Preferably it is 0.5-50 mass %, More preferably, it is 1-40 mass %to be.

The content rate of the coloring agent (A1) in the coloring agent (A1) containing liquid is usually 1 mass % or more and 90 mass % or less with respect to the total amount of solid content, Preferably it is 1 mass % or more and 80 mass % or less, More preferably, 2 mass % or more and 75 mass% or less.

After preparing the colorant (A1) containing liquid containing the colorant (A1) and the solvent (E) in advance, when the coloring composition of the present invention is prepared using the colorant (A1) containing liquid, the colorant (A1) containing liquid is , a part or all of the resin (B) contained in the coloring composition, and preferably a part of the resin (B) may be included in advance. By incorporating the resin (B) in advance, the dispersion stability of the colorant (A1)-containing liquid can be further improved.

Content of resin (B) in coloring agent (A1) containing liquid is 1-500 mass parts with respect to 100 mass parts of coloring agents (A1), Preferably it is 5-200 mass parts, More preferably, it is 10-200 mass parts. 100 parts by mass.

The content rate of the colorant (A) in which the compound (I) and the colorant (A1) are combined in the coloring composition is usually 1% by mass or more and 90% by mass or less, preferably 1% by mass or more and 80% by mass or less, with respect to the total amount of solid content. , More preferably, they are 2 mass % or more and 75 mass % or less.

The content of the compound (I) is usually 0.001 mass% or more, preferably 0.003 mass% or more, more preferably 0.005 mass% or more, in the total amount of the colorant (A), and the upper limit is 100 mass% or less, preferably 99.999 mass % or less, More preferably, it is 99.997 mass % or less.

When the colorant (A1) is included, the content of the colorant (A1) is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and still more preferably 1 part by mass or more with respect to 100 parts by mass of the compound (I). And it is preferable that it is 10000 mass parts or less, and it is more preferable that it is 5000 mass parts or less.

The colored curable composition of this invention contains a compound (I), at least one of resin (B), and a solvent (E), and a polymeric compound (C).

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound that can be polymerized with an active radical and/or an acid generated from the polymerization initiator (D), for example, a compound having a polymerizable ethylenically unsaturated bond, preferably ( It is a meth)acrylic acid ester compound.

Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, and 2-hydroxy Ethyl acrylate, N-vinylpyrrolidone, etc., and the above-mentioned monomer (a), monomer (b), and monomer (c) are mentioned.

Examples of the polymerizable compound having two ethylenically unsaturated bonds include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tri Ethylene glycol di(meth)acrylate, the bis(acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, etc. are mentioned.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such a polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol penta(meth)acrylate. Pentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (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, caprolactone-modified pentaerythritol tetra (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate, preferably Dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are mentioned.

The weight average molecular weight of a polymeric compound (C) becomes like this. Preferably it is 150 or more and 2,900 or less, More preferably, they are 250 or more and 1,500 or less.

It is preferable that it is 1-65 mass % with respect to the total amount of solid content in a colored curable composition, as for content rate of a polymeric compound (C), It is more preferable that it is 3-60 mass %, It is more preferable that it is 5-55 mass %. .

The colored curable composition of this invention may contain the polymerization initiator (D).

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of initiating polymerization by generating an active radical, an acid, etc. under the action of light or heat, and a known polymerization initiator can be used.

Examples of the polymerization initiator (D) include an O-acyloxime compound, an alkylphenone compound, a biimidazole compound, a triazine compound, and an acylphosphine oxide compound.

As the O-acyloxime compound, for example, N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl) ) Octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-(4 -Phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-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-cyclopentylpropan-1-imine and N-benzoyloxy-1-[9-ethyl-6-( 2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine and the like. In addition, as an O-acyl oxime compound, you may use commercial items, such as Irgacure OXE01, OXE02 (above, BASF Corporation make), and N-1919 (made by ADEKA Corporation). Among them, as the O-acyloxime compound, 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-cyclopentylpropan-1-one-2-imine is preferable; N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine is more preferable.

Examples of the alkylphenone compound include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane. -1-one and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one; and the like. As an alkylphenone compound, you may use commercial items, such as Irgacure 369, 907, 379 (above, BASF Corporation make).

Examples of the alkylphenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane-1-one. one, 1-hydroxycyclohexylphenylketone, oligomer of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxyacetophenone and benzyldimethylketal can also be heard.

As the biimidazole compound, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3- dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, Japanese Patent Application Laid-Open No. 6-75372, Japanese Patent Application 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'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis (2-Chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (for example, Japanese Patent Application Laid-Open No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204 and the imidazole compound in which the phenyl group at the 4,4',5,5'-position is substituted with a carboalkoxy group (see, for example, Japanese Patent Application Laid-Open No. 7-10913, etc.) and the like.

Examples of the triazine compound include 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) To methyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl) tenyl]-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 and 2,4-bis(trichloromethyl)-6 -[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine etc. are mentioned.

2,4,6-trimethylbenzoyldiphenylphosphine oxide etc. are mentioned as an acylphosphine oxide compound.

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, o-benzoylbenzoate methyl, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone and 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.

It is preferable to use these in combination with the polymerization initiator adjuvant (D1) (especially amines) mentioned later.

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

Preferably the content rate of a polymerization initiator (D) is 0.001-40 mass % in the total amount of solid content in colored curable composition, More preferably, it is 0.01-30 mass %.

The colored curable composition of this invention may contain the polymerization initiator auxiliary (D1).

<Polymerization initiator (D1)>

The polymerization initiator adjuvant (D1) is a compound or sensitizer used in order to promote polymerization of a polymerizable compound whose polymerization is initiated by the polymerization initiator. When the polymerization initiator (D1) is included, it is usually used in combination with the polymerization initiator (D).

Examples of the polymerization initiator (D1) include an amine compound, an alkoxyanthracene compound, a thioxanthone compound, and a carboxylic acid compound.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and 4-dimethylaminobenzoic acid 2 -Ethylhexyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone and 4,4'- Bis(ethylmethylamino)benzophenone etc. are mentioned, Preferably 4,4'-bis(diethylamino)benzophenone is mentioned. Moreover, you may use commercial items, such as EAB-F (made by Hodogaya Chemical Industry Co., Ltd.), as an amine compound.

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and 9,10-dibutoxy. anthracene and 2-ethyl-9,10-dibutoxyanthracene; and the like.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythiok. Santon etc. are mentioned.

Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, and chlorophenylsulfanylacetic acid. Panylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc. are mentioned.

When using such a polymerization initiator adjuvant (D1), Preferably the content rate is 0.001-30 mass % in the total amount of solid content in a colored curable composition, More preferably, it is 0.01-20 mass %.

The coloring composition of this invention may also contain a leveling agent (F) and antioxidant further.

<Leveling agent (F)>

As a leveling agent (F), a silicone type surfactant, a fluorine type surfactant, and the silicone type surfactant which has a fluorine atom, etc. are mentioned. These may have a polymerizable group in a side chain.

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

As a fluorine-type surfactant, the surfactant etc. which have a fluorocarbon chain in a molecule|numerator are mentioned. Specifically, Florad (registered trademark) FC430, dong FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megapac (registered trademark) F142D, dong F171, dong F172, dong F173, dong F177, dong F183, dong F554, dong R30, RS-718-K (manufactured by DIC Corporation), EFTO (registered trademark) EF301, EF303, copper EF351, copper EF352 (manufactured by Mitsubishi Materials Electronics & Gassei Co., Ltd.), SURFRON (registered trademark) S381 , copper S382, copper SC101, copper SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Research Institute), and the like.

Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megapac (trademark) R08, Dong BL20, Dong F475, Dong F477, Dong F443 (DIC Co., Ltd. product), etc. are mentioned.

When containing a leveling agent (F), the content rate is 0.0005 mass % or more and 1 mass % or less normally with respect to the total amount of a coloring composition, Preferably they are 0.001 mass % or more and 0.5 mass % or less, More preferably, they are 0.001 mass %. It is 0.2 mass % or more, More preferably, they are 0.002 mass % or more and 0.1 mass % or less, Especially preferably, they are 0.005 mass % or more and 0.1 mass % or less. When the content rate of a leveling agent (F) exists in said range, the flatness of a color filter can be made favorable.

<Antioxidant>

It is preferable to use antioxidant individually or in combination of 2 or more types from a viewpoint of improving the heat resistance and light resistance of a coloring agent. The antioxidant is not particularly limited as long as it is an antioxidant generally used industrially, and phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like can be used.

Examples of the phenolic antioxidant include Irganox 1010 (Irganox 1010: pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], BASF ( Co.), Irganox 1076 (Irganox 1076: octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, BASF Co., Ltd.), Irganox 1330 (Irganox 1330: 3,3',3'',5,5',5''-hexa-tert-butyl-a,a',a''-(mesitylene-2,4,6-triyl) Tri-p-cresol, manufactured by BASF Co., Ltd.), Irganox 3114 (Irganox 3114: 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3, 5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Corporation), Irganox 3790 (Irganox 3790: 1,3,5-tris((4-tert-butyl) -3-hydroxy-2,6-xylyl)methyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Corporation), Irga Nox 1035 (Irganox 1035: thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], BASF Co., Ltd.), Irganox 1135 (Irganox 1135: Benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy, C7-C9 branched alkyl ester, manufactured by BASF Corporation), Irganox 1520L (Irganox 1520L: 4,6-bis (Octylthiomethyl)-o-cresol, manufactured by BASF Co., Ltd.), Irganox 3125 (Irganox 3125, BASF Co., Ltd.), Irganox 565 (Irganox 565: 2,4-bis (n-octylthio) )-6-(4-hydroxyl 3',5'-di-tert-butylanilino)-1,3,5-triazine, manufactured by BASF Co., Ltd.), adecastab AO-80 (adecastab AO-80: 3,9-bis(2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2,4,8, 10-tetraoxaspiro (5,5) undecane, manufactured by ADEKA Co., Ltd.), Sumilizer BHT (Sumi) lizer BHT, Sumitomo Chemical Co., Ltd.), Sumilizer GA-80 (Sumilizer GA-80, Sumitomo Chemical Co., Ltd.), Sumilizer GS (Sumilizer GS, Sumitomo Chemical Co., Ltd.), Cyanox 1790 (Cyanox) 1790, manufactured by Cytech Co., Ltd.) and vitamin E (manufactured by Eisai Co., Ltd.).

As said phosphorus antioxidant, Irgafos 168 (Irgafos 168: tris (2,4-di-tert- butylphenyl) phosphite, BASF Co., Ltd. product), Irgafos 12 (Irgafos 12: Tris), is, for example, [2-[[2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphin-6-yl]oxy]ethyl]amine, BASF (Note ) agent), Irgafos 38 (Irgafos 38: bis(2,4-bis(1,1-dimethylethyl)-6-methylphenyl)ethyl ester phosphorous acid, manufactured by BASF Co., Ltd.), adecastab 329K (Co., Ltd.) ) made by ADEKA), ADEKA STAB PEP36 (manufactured by ADEKA Corporation), ADEKA STAB PEP-8 (manufactured by ADEKA Corporation), Sandstab P-EPQ (manufactured by Clariant Corporation), Weston 618 (Weston 618, GE) ), Weston 619G (Weston 619G, manufactured by GE), Ultranox 626 (Ultranox 626, manufactured by GE) and Sumilizer GP (Sumilizer GP: 6-[3-(3-tert-butyl-4-hydro) Roxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenz[d,f][1.3.2]dioxaphospepine) (manufactured by Sumitomo Chemical Co., Ltd.), etc. can be heard

Examples of the sulfur-based antioxidant include dialkylthiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl and distearyl, and tetrakis[methylene(3-dodecylthio)propionate]methane β-alkyl mercaptopropionic acid ester compounds of polyols, such as these, etc. are mentioned.

<Other ingredients>

The coloring composition of this invention may also contain well-known additives in the said technical field, such as a filler, another high molecular compound, an adhesion promoter, an optical stabilizer, and a chain transfer agent, as needed.

As the adhesion promoter, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidoxypropyl Methyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane , 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-sulfanylpropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, N-2-(aminoethyl )-3-Aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-amino and propyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltriethoxysilane.

<Color filter>

A color filter can be formed from the coloring composition or coloring curable composition of this invention. A photolithography method, an inkjet method, a printing method etc. are mentioned as a method of forming a coloring pattern, Preferably the photolithographic method is mentioned. The photolithographic method is a method of apply|coating the said colored curable composition to a board|substrate, drying it, forming a colored curable composition layer, exposing the said colored curable composition layer through a photomask, and developing. In the photolithographic method, it is preferable that the colored curable composition contains the polymerization initiator (D). In the photolithography method, the colored coating film which is the hardened|cured material of the said colored curable composition layer can be formed by not using and/or not developing a photomask at the time of exposure. The colored pattern and colored coating film thus formed can be used as the color filter of the present invention.

The film thickness of the color filter to be produced is not particularly limited, and can be appropriately adjusted according to the purpose or use, and is, for example, 0.1 to 30 µm, preferably 0.1 to 20 µm, more preferably 0.5 to 6 µm. .

As the substrate, a glass plate, a resin plate, silicon, or a substrate in which an aluminum, silver, silver/copper/palladium alloy thin film or the like is formed on the substrate is used. Another color filter layer, a resin layer, a transistor, a circuit, etc. may be formed on such a board|substrate.

Formation of each color pixel by the photolithographic method can be performed with a well-known or customary apparatus and conditions. For example, it can be produced as follows.

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

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

Next, the colored curable composition layer is exposed through a photomask for forming the target colored pattern. It is preferable to use an exposure apparatus such as a mask aligner and a stepper, since it is possible to uniformly irradiate the entire exposure surface with parallel rays or to accurately align the photomask and the substrate on which the colored curable composition layer is formed. .

A coloring pattern is formed on a board|substrate by making a developing solution contact and developing the colored curable composition layer after exposure. By image development, the unexposed part of a colored curable composition layer melt|dissolves in a developing solution, and is removed.

As a developing solution, the aqueous solution of alkaline compounds, such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, and tetramethylammonium hydroxide, is preferable, for example.

The developing method may be any of a paddle method, a dipping method, and a spray method. In addition, you may incline a board|substrate at an arbitrary angle at the time of development.

It is preferable that the board|substrate after image development is washed with water.

Moreover, it is preferable to post-baking to the obtained coloring pattern.

The color filter is useful as a color filter used for a display device (eg, a liquid crystal display device, an organic EL device, an electronic paper, etc.) and a solid-state image sensor, and is particularly useful as a color filter used for a liquid crystal display device.

(Example)

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited by the following examples, needless to say, and is carried out with appropriate changes within the range that can be suitable for the gist of the preceding and latter period. It is of course also possible, and they are all included in the technical scope of the present invention.

In the examples, "%" and "parts" represent mass % and parts by mass unless otherwise specified.

In the following synthesis examples, the structure of the compound was determined by NMR (JMM-ECA-500; manufactured by Nippon Electronics Co., Ltd.) or mass spectrometry (LC; Agilent type 1200), MASS; Agilent product LC/MSD type 6130 ) was confirmed.

The measurement of the polystyrene conversion weight average molecular weight (Mw) and number average molecular weight (Mn) of resin was performed on condition of the following by GPC method.

Device: HLC-8120GPC (manufactured by Tosoh Corporation)

Column: TSK-GELG2000HXL

Column temperature: 40°C

Solvent: tetrahydrofuran

Flow rate: 1.0 mL/min

Solid content concentration of analysis sample: 0.001 to 0.01 mass %

Injection volume: 50 μL

Detector: RI

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

The ratio (Mw/Mn) of the polystyrene conversion weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained above was made into dispersibility.

Example 1

14.4 parts of coumarin 6 (manufactured by Tokyo Chemical Industry Co., Ltd.) and 737 parts of toluene were mixed and stirred at 87°C. To this mixture was added 10.1 parts of methyl trifluoromethanesulfonate. The mixture was stirred at 87° C. for 3 hours. The mixture was stirred at 10°C. The mixture was filtered, and the obtained residue was washed 6 times with 433 parts of toluene. The residue was dried under reduced pressure at 60°C to obtain 20.8 parts of a compound represented by the formula (I-2).

<Identification of the compound represented by formula (I-2)>

(mass spectrometry) ionization mode=ESI+:m/z=365[M-CF ₃ SO ₃ ] ⁺

Exact Mass:514

5.00 parts of the compound represented by Formula (I-2) and 1500 parts of methanol were mixed. To this mixture was added a mixture of 10.4 parts of phosphotungstic acid hydrate (manufactured by Sigma-Aldrich Japan Co., Ltd.) and 104 parts of methanol. The mixture was filtered, and the obtained residue was washed with 500 parts of methanol. The residue was dried under reduced pressure at 60°C to obtain 12.4 parts of the compound represented by the formula (I-14).

<Identification of the compound represented by formula (I-14)>

(mass spectrometry) ionization mode=ESI+:m/z=365[(M-PW ₁₂ O ₄₀ )/3] ⁺

Exact Mass:3974

[Heat resistance evaluation]

Differential scanning calorimetry of the compound obtained in Example 1 was performed using a differential thermal gravimetric simultaneous measurement apparatus (TG/DTA 6200 manufactured by SI Nanotechnology). The sample amount used for one measurement was 5 mg. The measurement temperature was initially started at 45° C., and the temperature was increased at a rate of 5° C. per minute to measure up to 550° C. The temperature T ₅ (under nitrogen) at which the weight reduction rate is 5% in a nitrogen atmosphere was determined. A result is shown in Table 11.

From the results in Table 11, it can be seen that the compound of the present invention has high heat resistance.

Synthesis Example 1

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, an appropriate amount of nitrogen was flowed, replaced with a nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was put, and the mixture was heated to 80°C while stirring. Then, 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-8-ylacrylate and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-9-ylacrylic A mixed solution of 289 parts of the mixture of the rate and 125 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, a mixed solution obtained by dissolving 33 parts of 2,2-azobis(2,4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion|finish of dripping, after hold|maintaining at the same temperature for 4 hours, it cooled to room temperature, and obtained the solution of the copolymer (resin (B1)) of 35.0% of solid content. The weight average molecular weight (Mw) of the obtained resin (B1) was 8800, the dispersion degree was 2.1, and the solution acid value was 28 mg-KOH/g.

Synthesis example 2

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, an appropriate amount of nitrogen was flowed into the flask, replaced with a nitrogen atmosphere, 257 parts of ethyl lactate was put, and the mixture was heated to 75°C while stirring. Then, 81 parts of methacrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-8-ylacrylate and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-9- A mixed solution of 369 parts of a mixture of monoacrylate and 25 parts of ethyl lactate was added dropwise over 5 hours. On the other hand, a mixed solution obtained by dissolving 11 parts of 2,2-azobis(2,4-dimethylvaleronitrile) in 162 parts of ethyl lactate was added dropwise over 5 hours. After completion|finish of dripping, after hold|maintaining at the same temperature for 5 hours, 95 parts of ethyl lactate was added, and it cooled to room temperature, and obtained the solution of the copolymer (resin (B2)) of 47.7% of solid content. The weight average molecular weight (Mw) of the obtained resin (B2) was 8100, the dispersion degree was 1.9, and the solution acid value was 53 mg-KOH/g.

Synthesis example 3

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, an appropriate amount of nitrogen was poured into the flask, replaced with a nitrogen atmosphere, 371 parts of propylene glycol monomethyl ether acetate was placed, and the mixture was heated to 85°C while stirring. Then, 54 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-8-ylacrylate and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-9-ylacrylic The mixed solution of 225 parts of the mixture of the rate, 81 parts of vinyltoluene (isomer mixture), and 80 parts of propylene glycol monomethyl ether acetate was dripped over 4 hours. On the other hand, a solution obtained by dissolving 30 parts of a polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) in 160 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of the dropwise addition of the initiator solution, it was maintained at the same temperature for 4 hours, then cooled to room temperature to obtain a solution of a copolymer (resin (B3)) having a solid content of 37.5%. The weight average molecular weight (Mw) of the obtained resin (B3) was 10600, the dispersion degree was 2.01, and the solution acid value was 43 mg-KOH/g.

Synthesis Example 4

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, an appropriate amount of nitrogen was flowed into the flask, replaced with a nitrogen atmosphere, 54 parts of ethyl lactate and 141 parts of propylene glycol monomethyl ether acetate were put, and the mixture was heated to 85° C. while stirring. Then, 35 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-8-ylacrylate and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-9-ylacrylic A mixed solution of 23 parts of the mixture of the rate, 161 parts of cyclohexylmaleimide, 12 parts of 2-hydroxyethyl methacrylate, and 493 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, a mixed solution obtained by dissolving 3 parts of 2,2-azobis(2,4-dimethylvaleronitrile) in 78 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion|finish of dripping, after hold|maintaining at the same temperature for 4 hours, it cooled to room temperature, and obtained the solution of the copolymer (resin (B4)) of 24.4% of solid content. The weight average molecular weight (Mw) of the obtained resin (B4) was 8400, the dispersion degree was 2.1, and the solution acid value was 26 mg-KOH/g.

[Measurement of film thickness]

The film thickness is DEKTAK3; It was measured using the Nippon Vacuum Technology Co., Ltd. product.

[Preparation of resin composition for sublimation test (SJS)]

Resin: methacrylic acid/benzyl methacrylate (molar ratio: 30/70) copolymer (Taoka Chemical Industries, Ltd., weight average molecular weight (Mw) 10700, acid value 70 mg-KOH/g) 33.8% propylene glycol monomethyl 40 parts of ether acetate solution;

Polymeric compound: 5.8 parts of dipentaerythritol hexaacrylate (KAYARAD (trademark) DPHA; Nippon Kayaku Co., Ltd. product);

Polymerization initiator: 0.58 part of N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE01; manufactured by BASF Japan);

Leveling agent: 0.010 parts of polyether-modified silicone oil (Toray Silicone SH8400; Toray Dow Corning Co., Ltd.);

Solvent: 47 parts of propylene glycol monomethyl ether;

Solvent: 6.8 parts of propylene glycol monomethyl ether acetate

was mixed to obtain a resin composition for sublimation test (SJS).

[Formation of resin coating film (SJSM) for sublimation test]

On a 2-inch-wide glass substrate (Eagle XG; manufactured by Corning), the resin composition for sublimation test (SJS) obtained above was applied by spin coating, and the volatile components were volatilized at 100°C for 3 minutes. After cooling, using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.), it was irradiated with light at an exposure amount of 150 mJ/cm 2 (based on 365 nm) in an atmospheric atmosphere. It heated at 220 degreeC for 2 hours in oven, and formed the resin coating film for a sublimation test (SJSM) (film thickness 2.2 micrometers).

Example 2

Colorant (A): 14 parts of a compound represented by formula (I-2);

Resin (B): 480 parts of resin (B1) solution;

Solvent (E): 6.2 parts of propylene glycol monomethyl ether acetate;

solvent (E): 500 parts of N-methyl-2-pyrrolidone; and

Surfactant: 0.063 parts of polyether-modified silicone oil (Toray Silicone SH8400; Toray Dow Corning Co., Ltd.)

was mixed to obtain a coloring composition 1.

Example 3

Colorant (A): 36 parts of a compound represented by formula (I-14);

Resin (B): 410 parts of resin (B1) solution;

Solvent (E): 6.2 parts of propylene glycol monomethyl ether acetate;

solvent (E): 540 parts of N-methyl-2-pyrrolidone; and

Surfactant: 0.063 parts of polyether-modified silicone oil (Toray Silicone SH8400; Toray Dow Corning Co., Ltd.)

was mixed to obtain a coloring composition 2.

Example 4

Colorant (A): 10 parts of a compound represented by formula (I-14);

Resin (B): 97 parts of resin (B2) solution;

solvent (E): 180 parts of N-methyl-2-pyrrolidone;

solvent (E): 26 parts of 4-hydroxy-4-methyl-2-pentanone;

Solvent (E): 2.0 parts of propylene glycol monomethyl ether acetate; and

Surfactant: 0.020 part of polyether-modified silicone oil (Toray Silicone SH8400; Toray Dow Corning Co., Ltd.)

was mixed to obtain a coloring composition 3.

Example 5

Colorant (A): 10 parts of a compound represented by formula (I-14);

10 parts of dispersing agent (BYK-LPN 21324; Big Chemie Japan Co., Ltd. make);

Resin (B): 11 parts of resin (B1) solution, and

Solvent (E): 160 parts of propylene glycol monomethyl ether acetate

100 parts of a coloring composition in which a compound represented by formula (I-14) is dispersed using a bead mill;

Resin (B): 55 parts of resin (B1) solution;

Solvent (E): 3.6 parts of propylene glycol monomethyl ether acetate; and

Surfactant: Polyether-modified silicone oil (Toray Silicone SH8400; Toray Dow Corning Co., Ltd.) 0.010 parts

was mixed to obtain a coloring composition 4.

Comparative Example 1

Colorant (A): Coumarin 6 11 parts;

Resin (B): 350 parts of resin (B2) solution;

Solvent (E): 6.2 parts of propylene glycol monomethyl ether acetate;

solvent (E): 630 parts of N,N-dimethylformamide; and

Surfactant: 0.063 parts of polyether-modified silicone oil (Toray Silicone SH8400; Toray Dow Corning Co., Ltd.)

was mixed to obtain a coloring composition 5.

[Sublimation evaluation]

Example 6

On a 2 inch horizontal and vertical glass substrate (Eagle XG; manufactured by Corning), the coloring composition 1 was applied by spin coating, and then pre-baked at 100° C. for 3 minutes to form a coloring composition layer. Film thickness DEKTAK 3; It was measured using the Nippon Vacuum Technology Co., Ltd. product. This colored coating film and the resin coating film for a sublimation test (SJSM) obtained above were opposed to each other with a gap of 70 µm, and post-baking was performed at 220°C for 40 minutes. The color difference (ΔEab*) before and after heating of the resin coating film for sublimation test (SJSM) was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS). A color difference (ΔEab*) of 5.0 or more indicates that the colorant has sublimability. A result is shown in Table 12. In Table 12, ○ indicates that the colorant does not have sublimability, and × indicates that the colorant has sublimability.

Example 7

Sublimation evaluation was performed like Example 6 except having changed the coloring composition 1 into the coloring composition 2. A result is shown in Table 12.

Example 8

Except having changed the coloring composition 1 into the coloring composition 3, it carried out similarly to Example 6, and performed sublimation evaluation. A result is shown in Table 12.

Example 9

Except having changed the coloring composition 1 into the coloring composition 4, it carried out similarly to Example 6, and performed sublimation evaluation. A result is shown in Table 12.

Comparative Example 2

Except having changed the coloring composition 1 into the coloring composition 5, it carried out similarly to Example 6, and performed sublimation evaluation. A result is shown in Table 12.

It turned out that the coloring composition containing the compound of this invention reduced the sublimation of a coloring agent from said result.

Example 10

Colorant (A): 100 parts of a compound represented by formula (I-14);

130 parts of dispersing agent (BYK-LPN 21324; Big Chemie Japan Co., Ltd. product);

Resin (B): 170 parts of resin (B4) solution, and

Solvent (E): 610 parts of propylene glycol monomethyl ether acetate

380 parts of a coloring composition in which the compound represented by formula (I-14) is dispersed using a bead mill;

Colorant (A): C.I. Pigment Yellow 138 (pigment) 18 copies,

7.6 parts dispersant;

7.6 parts of resin, and

Solvent (E): 120 parts of propylene glycol monomethyl ether acetate

The total amount of the pigment dispersion in which the pigment was mixed and the pigment was dispersed using a bead mill;

Colorant (A): 4.2 parts of a compound represented by the following formula (prepared by the method described in Japanese Patent Application Laid-Open No. 2013-235257);

Resin (B): 21 parts of resin (B3) solution;

Polymeric compound (C): Polymeric compound (A9550; Shin-Nakamura Chemical Co., Ltd. product)

25 copies;

Polymerization initiator (D): 6.6 parts of a compound represented by the following formula (manufactured by Sangju Kangkang Electronic New Materials Co., Ltd.);

Solvent (E): 170 parts of 4-hydroxy-4-methyl-2-pentanone;

Solvent (E): 250 parts of propylene glycol monomethyl ether acetate; and

Surfactant: 0.075 parts of polyether-modified silicone oil (Toray Silicone SH8400; Toray Dow Corning Co., Ltd.)

was mixed to obtain a colored curable composition 1.

[Production of coloring patterns]

On a 2-inch-wide glass substrate (Eagle XG; manufactured by Corning), the colored curable composition 1 was applied by spin coating, and then prebaked at 100° C. for 3 minutes to form a colored curable composition layer. After cooling, the interval between the substrate on which the colored curable composition layer was formed and the quartz glass photomask was set to 200 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used in an atmospheric atmosphere at an exposure dose of 80 mJ/cm 2 (365 nm). standard) was exposed. In addition, as a photomask, the thing in which the line-and-space pattern of 100 micrometers was formed was used. The colored curable composition layer after exposure was developed by immersing it in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25°C for 70 seconds, followed by washing with water. The colored pattern was obtained by post-baking this colored coating film at 230 degreeC for 30 minute(s).

[Sublimation evaluation]

On a 2-inch-wide glass substrate (Eagle XG; manufactured by Corning), the colored curable composition 1 was applied by spin coating, and then prebaked at 100° C. for 3 minutes to form a colored curable composition layer. After cooling, the substrate on which the colored curable composition layer was formed was exposed using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) at an exposure dose of 80 mJ/cm 2 (based on 365 nm) in an atmospheric atmosphere. The colored curable composition layer after exposure was developed by immersing it in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25°C for 70 seconds, followed by washing with water.

film thickness, DEKTAK3; It was measured using the Nippon Vacuum Technology Co., Ltd. product.

This colored coating film and the resin coating film for a sublimation test (SJSM) obtained above were made to face each other with a space|interval of 70 micrometers, and it post-baked at 220 degreeC for 40 minute(s).

The color difference (ΔEab*) before and after heating of the resin coating film for sublimation test (SJSM) was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS). A color difference (ΔEab*) of 5.0 or more indicates that the colorant has sublimability. A result is shown in Table 13. In Table 13, ○ indicates that the colorant does not have sublimability, and × indicates that the colorant has sublimability.

Example 11

Colorant (A): 100 parts of a compound represented by formula (I-14);

130 parts of dispersing agent (BYK-LPN 21324; Big Chemie Japan Co., Ltd. product);

Resin (B): 170 parts of resin (B4) solution, and

Solvent (E): 610 parts of propylene glycol monomethyl ether acetate

340 parts of a coloring composition in which the compound represented by formula (I-14) was dispersed using a bead mill;

Colorant (A): C.I. Pigment Yellow 138 (pigment) 18 copies,

7.6 parts dispersant;

7.6 parts of resin, and

Solvent (E): 120 parts of propylene glycol monomethyl ether acetate

The total amount of the pigment dispersion in which the pigment was mixed and the pigment was dispersed using a bead mill;

Colorant (A): 7.8 parts of a compound represented by the following formula (prepared by the method described in Japanese Patent Application Laid-Open No. 2013-235257);

Resin (B): 27 parts of resin (B3) solution;

Polymeric compound (C): Polymeric compound (A9550; Shin-Nakamura Chemical Co., Ltd. product)

26 copies;

Polymerization initiator (D): 6.8 parts of a compound represented by the following formula (manufactured by Sangju Kangkang Electronic New Materials Co., Ltd.);

Solvent (E): 170 parts of 4-hydroxy-4-methyl-2-pentanone;

Solvent (E): 270 parts of propylene glycol monomethyl ether acetate; and

Surfactant: 0.075 parts of polyether-modified silicone oil (Toray Silicone SH8400; Toray Dow Corning Co., Ltd.)

was mixed to obtain a colored curable composition 2.

Except having changed the colored curable composition 1 into the colored curable composition 2, it carried out similarly to Example 10, and performed preparation of a colored pattern and sublimation evaluation. Table 13 shows the sublimation evaluation results.

Example 12

Colorant (A): 100 parts of a compound represented by formula (I-14);

130 parts of dispersing agent (BYK-LPN 21324; Big Chemie Japan Co., Ltd. product);

Resin (B): 170 parts of resin (B4) solution, and

Solvent (E): 610 parts of propylene glycol monomethyl ether acetate

290 parts of a coloring composition in which a compound represented by formula (I-14) is dispersed using a bead mill;

Colorant (A): C.I. Pigment Yellow 138 (pigment) 23 copies,

9.6 parts dispersant;

9.6 parts of resin, and

Solvent (E): 150 parts of propylene glycol monomethyl ether acetate

The total amount of the pigment dispersion in which the pigment was mixed and the pigment was dispersed using a bead mill;

Colorant (A): 5.1 parts of a compound represented by the following formula (prepared by the method described in Japanese Patent Application Laid-Open No. 2013-235257);

Resin (B): 31 parts of resin (B3) solution;

Polymeric compound (C): Polymeric compound (A9550; Shin-Nakamura Chemical Co., Ltd. product)

27 copies;

Polymerization initiator (D): 7.2 parts of a compound represented by the following formula (manufactured by Sangju Kanggang Electronics New Materials Co., Ltd.);

Solvent (E): 170 parts of 4-hydroxy-4-methyl-2-pentanone;

Solvent (E): 280 parts of propylene glycol monomethyl ether acetate; and

Surfactant: 0.075 parts of polyether-modified silicone oil (Toray Silicone SH8400; Toray Dow Corning Co., Ltd.)

was mixed to obtain a colored curable composition 3.

Except having changed the colored curable composition 1 into the colored curable composition 3, it implemented similarly to Example 10, and performed preparation of a colored pattern and sublimation evaluation. Table 13 shows the sublimation evaluation results.

Example 13

Colorant (A): 100 parts of a compound represented by formula (I-14);

130 parts of dispersing agent (BYK-LPN 21324; Big Chemie Japan Co., Ltd. product);

Resin (B): 170 parts of resin (B4) solution, and

Solvent (E): 610 parts of propylene glycol monomethyl ether acetate

270 parts of a coloring composition in which the compound represented by formula (I-14) was dispersed using a bead mill;

Colorant (A): C.I. Pigment Yellow 138 (pigment) 23 copies,

9.6 parts dispersant;

9.6 parts of resin, and

Solvent (E): 150 parts of propylene glycol monomethyl ether acetate

The total amount of the pigment dispersion in which the pigment was mixed and the pigment was dispersed using a bead mill;

Colorant (A): 7.4 parts of a compound represented by the following formula (prepared by the method described in Japanese Patent Application Laid-Open No. 2013-235257);

Resin (B): 35 parts of resin (B3) solution;

Polymeric compound (C): Polymeric compound (A9550; Shin-Nakamura Chemical Industry Co., Ltd. product)

27 copies;

Polymerization initiator (D): 7.3 parts of a compound represented by the following formula (manufactured by Sangju Kangkang Electronic New Materials Co., Ltd.);

Solvent (E): 170 parts of 4-hydroxy-4-methyl-2-pentanone;

Solvent (E): 290 parts of propylene glycol monomethyl ether acetate; and

Surfactant: 0.075 parts of polyether-modified silicone oil (Toray Silicone SH8400; Toray Dow Corning Co., Ltd.)

was mixed to obtain a colored curable composition 4.

Except having changed the colored curable composition 1 into the colored curable composition 4, it carried out similarly to Example 10, and performed preparation of a colored pattern and sublimation evaluation. Table 13 shows the sublimation evaluation results.

Example 14

Except having changed the compound represented by Formula (I-14) into the compound represented by Formula (I-2), it carried out similarly to Example 10, the colored curable composition 5 was obtained, preparation of a coloring pattern, and sublimation evaluation was done. Table 13 shows the sublimation evaluation results.

Example 15

Except having changed the compound represented by Formula (I-14) into the compound represented by Formula (I-2), it carried out similarly to Example 13, the colored curable composition 6 was obtained, preparation of a coloring pattern, and sublimation evaluation was done. Table 13 shows the sublimation evaluation results.

Comparative Example 3

Except having changed the compound represented by Formula (I-14) into coumarin 6, it carried out similarly to Example 10, the colored curable composition 7 was obtained, and preparation of a coloring pattern and sublimation evaluation were performed. Table 13 shows the sublimation evaluation results.

Comparative Example 4

Except having changed the compound represented by Formula (I-14) into coumarin 6, it carried out similarly to Example 13, the colored curable composition 8 was obtained, and preparation of a coloring pattern and sublimation evaluation were performed. Table 13 shows the sublimation evaluation results.

It turned out that the colored curable composition containing the compound of this invention reduced the sublimation of a coloring agent from said result.

The coloring composition and coloring curable composition of this invention can reduce the sublimability of a coloring agent, and are used suitably for display apparatuses, such as a color filter and a liquid crystal display device.

Claims (14)

The coloring composition containing the compound and resin represented by Formula (I).

[In formula (I), R ^N1 and R ^N2 each independently represent a C1-C8 linear or branched alkyl group.
R ^N3 represents a C1-C8 linear or branched alkyl group.
R ¹ to R ⁸ represent a hydrogen atom.
A ^g- is a g-valent anion, and represents the anion of phosphotungstic acid, silicotungstic acid, a tungsten-type isopolyacid, or the anion represented by Formula (VI). g represents an integer from 1 to 14.]

[In formula (VI), Y ² represents a fluorinated alkyl group having 1 to 4 carbon atoms.] delete delete delete delete The method of claim 1,
The coloring composition which further contains a solvent. The method of claim 1,
A coloring composition further comprising a yellow colorant, an orange colorant or a red colorant. A colored curable composition comprising the colored composition according to claim 1 and a polymerizable compound. 9. The method of claim 8,
A colored curable composition further comprising a polymerization initiator. The color filter formed from the coloring composition of any one of Claims 1, 6, and 7, or the colored curable composition of Claim 8 or 9. A liquid crystal display comprising the color filter according to claim 10 . A compound represented by formula (I-B).

[In formula (I-B), R ^N1 and R ^N2 each independently represent a C1-C8 linear or branched alkyl group.
R ^N3 represents a C1-C8 linear or branched alkyl group.
R ¹ to R ⁸ represent a hydrogen atom.
B ^h- is an anion of h valence, and represents the anion of phosphotungstic acid, silicotungstic acid, a tungsten-type isopolyacid, or the anion represented by Formula (VI).
h represents an integer from 1 to 14.]

[In formula (VI), Y ² represents a fluorinated alkyl group having 1 to 4 carbon atoms.] delete delete