JP2018040001A - Coloring composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring composition and a coloring curable resin composition having reduced sublimability.SOLUTION: The present invention provides a coloring composition containing a compound represented by formula (I) and a resin. [where Rand Rindependently represent a C1-40 aliphatic hydrocarbon group; Ris a C1-40 hydrocarbon group or a heterocyclic group; R-Rindependently represent H, -CO-Ror the like; Ris H, a C1-40 hydrocarbon group or the like; Ais a g-valent anion; g is an integer of 1-14].SELECTED DRAWING: None

Description

  The present invention relates to a compound and a coloring composition useful as a coloring agent.

  Dyes are used for color display using reflected light or transmitted light in the fields of fiber materials, liquid crystal display devices, ink jets, and the like. As such a dye, coumarin 6 represented by the following formula is known (Patent Document 1).

JP 2006-154740 A

In the step of producing a color filter from a colored composition containing coumarin 6 or a colored curable composition, the problem is that the colorant contained in each composition sublimates.
This invention makes it a subject to provide the coloring composition and coloring curable composition with which sublimation property was reduced. Another object of the present invention is to provide a coumarin compound having high heat resistance and reduced sublimation.

The present invention includes the following inventions.
[1] A colored composition comprising a compound represented by formula (I) and a resin.

[In the formula (I),
R ^N1 and R ^N2 each independently represent a C 1-40 aliphatic hydrocarbon group which may have a substituent.
R ^N3 represents a hydrocarbon group or optionally substituted heterocyclic group having carbon atoms of 1 to 40 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 , —O—R 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, an optionally substituted hydrocarbon group having 1 to 40 carbon atoms or a substituent. Represents a good heterocyclic group.
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.
^R102 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 a plurality of R ¹⁰¹ , R ¹⁰² and M are present, they may be the same or different.
A ^g− represents a g-valent anion.
g represents an integer of 1 to 14. ]
[2] A ^g- is, tungsten, molybdenum, silicon, and at least one element selected from the group consisting of phosphorus, anion containing and oxygen as essential elements, or a fluorine-containing anion [1] coloration according Composition.
[3] A ^g- is at least one element selected from the group consisting of tungsten and phosphorus, anion containing and oxygen as essential elements, or a fluorine-containing anion [1] according to any one of - [2] Coloring composition.
[4] A ^g- is at least one element selected from the group consisting of tungsten and phosphorus is an anion containing and oxygen as essential elements [1] - coloring composition according to any one of [3].
[5] The colored composition according to any one of [1] to [4], wherein R ^N1 and R ^N2 are independently an alkyl group having 1 to 10 carbon atoms which may have a substituent.
[6] The colored composition according to any one of [1] to [5], further including a solvent.
[7] The colored 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 from 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 (IB).

[In the formula (IB),
R ^N1 and R ^N2 each independently represent a C 1-40 aliphatic hydrocarbon group which may have a substituent.
R ^N3 represents a hydrocarbon group or optionally substituted heterocyclic group having carbon atoms of 1 to 40 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 , —O—R 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, an optionally substituted hydrocarbon group having 1 to 40 carbon atoms or a substituent. Represents a good heterocyclic group.
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.
^R102 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 a plurality of R ¹⁰¹ , R ¹⁰² and M are present, they may be the same or different.
B ^h- represents an h-valent anion 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 of 1 to 14. ]
[13] The compound according to [12], wherein B ^h- is an anion containing at least one element selected from the group consisting of tungsten and phosphorus and oxygen as essential elements.
[14] The compound according to [12] or [13], wherein R ^N1 and R ^N2 are independently an alkyl group having 1 to 10 carbon atoms which may have a substituent.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the technique which can reduce the sublimation property in the colored composition and colored curable composition containing a coumarin type compound. Moreover, according to the present invention, a coumarin compound having high heat resistance and reduced sublimation property can be provided.

The colored composition of the present invention includes a compound represented by formula (I) (hereinafter sometimes referred to as compound (I)) and a resin (hereinafter sometimes referred to as resin (B)).
Compound (I) includes tautomers and salts thereof.
Compound (I) can be used as a colorant.
1 type, or 2 or more types of compounds (I) may be contained in the coloring composition of this invention.
The colored composition of the present invention may contain a solvent (hereinafter sometimes referred to as a solvent (E)).
Further, the compound (I) is preferably dispersed in the solvent (E).
The coloring composition of the present invention may be referred to as a coloring agent other than compound (I) (hereinafter referred to as coloring agent (A1). In the following, compound (I) and coloring agent (A1) are referred to as “coloring agent (A)”. May be collectively referred to as “.”.
The colorant (A1) may contain one or more colorants.
The colorant (A1) preferably contains a yellow colorant, an orange colorant, or a red colorant.
Moreover, the colored curable composition of this invention contains compound (I), resin (B), and polymeric compound (C). In other words, the colored curable composition of the present invention includes the colored composition of the present invention and a polymerizable compound (C).
The colored curable composition of the present invention may contain a polymerization initiator (D).
The colored curable composition of the present invention may contain a polymerization initiation assistant (D1).
The coloring composition of the present invention may further contain a leveling agent (F) and an antioxidant.

<Compound (I)>
Compound (I) is a compound represented by the formula (I).

[In the formula (I),
R ^N1 and R ^N2 each independently represent a C 1-40 aliphatic hydrocarbon group which may have a substituent.
R ^N3 represents a hydrocarbon group or optionally substituted heterocyclic group having carbon atoms of 1 to 40 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 , —O—R 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, an optionally substituted hydrocarbon group having 1 to 40 carbon atoms or a substituent. Represents a good heterocyclic group.
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.
^R102 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 a plurality of R ¹⁰¹ , R ¹⁰² and M are present, they may be the same or different.
A ^g− represents a g-valent anion.
g represents an integer of 1 to 14. ]

The number of carbon atoms of the aliphatic hydrocarbon groups represented by R ^N1 and R ^N2 are 1 to 40, preferably 1 to 30, more preferably from 1 to 20, more preferably it is 1 to 15 Especially preferably, it is 1-10.

The aliphatic hydrocarbon group represented by R ^N1 and R ^N2 may be saturated or unsaturated, and may be a chain or an alicyclic ring.

Examples of the saturated or unsaturated chain aliphatic hydrocarbon group represented by R ^N1 and R ^N2 include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, Linear alkyl groups such as decyl group, undecyl group, dodecyl group, 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- Branched alkyl groups such as methyl) hexyl group, (2-ethyl) hexyl group and (3-ethyl) heptyl group; vinyl group, 1-propenyl 2-propenyl group (allyl group), (1-methyl) ethenyl group, 2-butenyl group, 3-butenyl group, 1,3-butadienyl group, (1- (2-propenyl)) ethenyl group, (1, Alkenyl groups such as 2-dimethyl) propenyl group and 2-pentenyl group; and the like. The carbon number of 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, More preferably, it is 1-8. 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 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, 2,2-dimethylcyclohexyl group, 3,3-dimethylcyclohexyl group, 4 4-dimethylcyclohexyl group, cyclooctyl group, 2,4,6-trimethylcyclohexyl group, 2,2,6,6-tetramethylcyclohexyl group, 3,3,5,5-tetramethylcyclohexyl group, 4-pentylcyclohexyl Group, a cycloalkyl group such as 4-octylcyclohexyl group, 4-cyclohexylcyclohexyl group; a cycloalkenyl group such as cyclohexenyl group (for example, cyclohex-2-ene, cyclohex-3-ene), cycloheptenyl group, cyclooctenyl group; norbornane group , An adamantyl group, bicyclo [2.2.2] octane, and the like. The carbon number of the saturated or unsaturated alicyclic hydrocarbon group is preferably 3 to 30, more preferably 3 to 20, still more preferably 4 to 20, and still more preferably 4 to 15. More preferably 5 to 15 and most preferably 5 to 10. Of these, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group are particularly preferable.

The aliphatic hydrocarbon groups represented by R ^N1 and R ^N2 are the above-described aliphatic hydrocarbon groups and aromatic hydrocarbon groups having 1 to 40 carbon atoms (for example, chain hydrocarbon groups and alicyclic hydrocarbons). It may be a group in which at least one of the groups and an aromatic hydrocarbon group) are combined.
Such aromatic hydrocarbon groups include phenyl, o-tolyl, m-tolyl, p-tolyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2,3-dimethyl. Phenyl 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, 1-naphthyl group, 2-naphthyl group, 5,6,7,8-tetrahydro-1-naphthyl group, 5,6,7,8 -Aromatic hydrocarbon groups such as tetrahydro-2-naphthyl group, fluorenyl group, phenanthryl group, anthryl group, 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.
A group obtained by 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) As aralkyl groups such as benzyl group, phenethyl group, 1-methyl-1-phenylethyl group; arylalkenyl groups such as phenylethenyl group (phenylvinyl group); arylalkynyl groups such as phenylethynyl group; It is done.
The groups represented by R ^N1 and R ^N2 are, for example, a cyclopropylmethyl group, a cyclopropylethyl group as a group in which the above-mentioned hydrocarbon groups (for example, a chain hydrocarbon group and an alicyclic hydrocarbon group) are combined. One or more alicyclic hydrocarbon groups such as a group, cyclobutylmethyl group, cyclobutylethyl group, cyclopentylmethyl group, cyclopentylethyl group, cyclohexylmethyl group, 2-methylcyclohexylmethyl group, cyclohexylethyl group, adamantylmethyl group, etc. May be an alkyl group to which is bonded.
The number of carbon atoms of the combined group is preferably 4 to 30, more preferably 4 to 20, still more preferably 4 to 15, 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, Preferably it is 1-15, Most preferably, it is 1-10.

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. The hydrogen 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, and a heptyl group. , Octyl group, nonyl group, decyl group, undecyl group, dodecyl group, heptadecyl group, octadecyl group, icosyl group, and other linear alkyl groups; 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 Branched alkyl groups such as isohexyl group, (5-methyl) hexyl group, (2-ethyl) hexyl group and (3-ethyl) heptyl group; vinyl group, -Propenyl group, 2-propenyl group (allyl group), (1-methyl) ethenyl group, 2-butenyl group, 3-butenyl group, 1,3-butadienyl group, (1- (2-propenyl)) ethenyl group, Alkenyl groups such as (1,2-dimethyl) propenyl group and 2-pentenyl group; and the like. The saturated or unsaturated chain hydrocarbon group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, still more preferably 1 to 15 carbon atoms, and particularly preferably 1 to 10 carbon atoms. More preferably, it is 1-8. 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 ^N3 , R ^{1 to} R ⁸ , R ¹⁰¹ and R ¹⁰² include a cyclopropyl group, a 1-methylcyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a 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-dimethyl Cyclohexyl 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 2,2-dimethylcyclohexyl group, 3,3-dimethyl Cyclohexyl group, 4,4-dimethylcyclohexyl group, cyclooctyl group, 2,4,6-trimethylcyclohexyl group, 2,2,6,6-tetramethylcyclohexyl group, 3,3,5,5-tetramethylcyclohexyl group Cycloalkyl groups such as 4-pentylcyclohexyl group, 4-octylcyclohexyl group and 4-cyclohexylcyclohexyl group; cyclohexenyl groups (eg cyclohex-2-ene, cyclohex-3-ene), cycloheptenyl groups, cyclooctenyl groups and the like Alkenyl group; norbornane group, adamantyl group, bicyclo [2.2.2] octane and the like. The number of carbon atoms of the saturated or unsaturated alicyclic hydrocarbon group is preferably 3 to 30, more preferably 3 to 20, still more preferably 4 to 20, and still more preferably 4 to It is 15, More preferably, it is 5-15, Most preferably, it is 5-10. Of these, 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-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl 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) An phenyl group, a 4-cyclohexylphenyl group, a 2,4,6-trimethylphenyl group, a 4-octylphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 5,6,7,8-tetrahydro-1-naphthyl group, And aromatic hydrocarbon groups such as 5,6,7,8-tetrahydro-2-naphthyl group, fluorenyl group, phenanthryl group, anthryl group and pyrenyl group. 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 groups represented by R ^N3 , R ^{1 to} R ⁸ , R ¹⁰¹ and R ¹⁰² are the hydrocarbon groups listed above (for example, aromatic hydrocarbon groups, chain hydrocarbon groups and alicyclic hydrocarbons). A combination of at least one group), an aralkyl group such as a benzyl group, a phenethyl group, or a 1-methyl-1-phenylethyl group; an arylalkenyl group such as a phenylethenyl group (phenylvinyl group) An arylalkynyl group 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, and a (dimethyl (phenyl) methyl) phenyl group It is done.
The groups represented by R ^N3 , R ^{1 to} R ⁸ , R ¹⁰¹ and R ¹⁰² are, for example, groups obtained by combining the above-described hydrocarbon groups (for example, chain hydrocarbon groups and alicyclic hydrocarbon groups). 1 such as cyclopropylmethyl group, cyclopropylethyl group, cyclobutylmethyl group, cyclobutylethyl group, cyclopentylmethyl group, cyclopentylethyl group, cyclohexylmethyl group, 2-methylcyclohexylmethyl group, cyclohexylethyl group, adamantylmethyl group, etc. It may be an alkyl group having two or more alicyclic hydrocarbon groups bonded thereto.
The number of carbon atoms of the combined group is preferably 4 to 30, more preferably 4 to 20, still more preferably 4 to 15, and particularly preferably 6 to 15.

The aliphatic hydrocarbon groups represented by R ^N1 and R ^N2 and the hydrocarbon groups 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. In the divalent substituent, two bonds are preferably bonded to 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, heptyloxy group, Octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group, (2-ethyl) hexyloxy group, icosyloxy group, 1-phenylethoxy group, 1-methyl-1-phenylethoxy 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-dicia Phenyloxy 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-methoxyphenyloxy group, 3-methoxyphenyloxy group, 4-ethoxyphenyloxy group, 2-ethoxyphenyloxy group, 3-ethoxyphenyloxy group, etc. And a hydrocarbon group 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, carboxy group, sulfo group, nitro group, hydroxy group, halogen) (Preferably a chlorine atom), an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably octylsulfamoyl) Oxy group derivatized group) is bonded to one side the like);

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

Epoxy group, oxetanyl group, tetrahydrofuryl group, 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, A hydrocarbon group having 1 to 20 carbon atoms (preferably having a carbon number of 1 to 11) such as a dodecanoyl group, a heicosanoyl group, a benzoyl group, and the like, or a derivatized group thereof (for example, a carboxy group) , A carbonyl group bonded with a sulfo group, a nitro group, a hydroxy group, a halogen (preferably a chlorine atom), a C1-C10 alkylsulfamoyl group (preferably an octylsulfamoyl group), etc. Group (when the carbonyl group is an alkanoyl group, the carbon number is preferably 2 to 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, decyloxycarbonyl group, undecyloxycarbonyl group, dodecyloxycarbonyl group, icosyloxycarbonyl group, phenyloxycarbonyl group, o-tolyloxycarbonyl group and the like, and the following formulas A hydrocarbon group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) such as a group or a derivatized group thereof (for example, carboxy group, sulfo group, nitro group, hydroxy group, halogen (preferably chlorine atom), carbon number 10 oxycarbonyl group alkylsulfamoyl group (preferably octyl sulfamoyl group) were derivatized with such groups) is bonded to;

An 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-diisopropylamino group, N-butylamino group, N, N-dibutylamino group, N-isobutylamino group, N, N-diisobutylamino group, N-sec-butylamino group, N, N-disec-butyl Amino 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) Xylamino 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-ico One of a silmethylamino group, an N, N-tert-butylmethylamino group, an N, N-phenylmethylamino group, and a group represented by the following formula: Two hydrocarbon groups having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) or derivatized groups thereof (for example, carboxy group, sulfo group, nitro group, hydroxy group, halogen (preferably chlorine atom), 1 carbon atom An amino group substituted with 10 to 10 alkylsulfamoyl groups (preferably a group derivatized with an octylsulfamoyl group or the like);

A sulfamoyl group;
N-methylsulfamoyl group, N, N-dimethylsulfamoyl group, N-ethylsulfamoyl group, N, N-diethylsulfamoyl group, N-propylsulfamoyl group, N, N-dipropyls Rufamoyl group, N-isopropylsulfamoyl group, N, N-diisopropylsulfamoyl group, N-butylsulfamoyl group, N, N-dibutylsulfamoyl group, N-isobutylsulfamoyl group, N, N-diisobutylsulfamoyl group, N-sec-butylsulfamoyl group, N, N-disec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N, N-ditert-butylsulfur Famoyl group, N-pentylsulfamoyl group, N, N-dipentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, , 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-ethylmethyl Sulfamoyl 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-dodecylmethylsulfamoyl group, N-icosylsulfamoyl group, N, N-icosylmethylsulfamoyl group, N, N-tert-butylmethylsulfamoyl group, N, N-phenylmethylsulfa 1 or 2 hydrocarbon group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) such as a moyl group and the group represented by the following formula or a derivatized group thereof (for example, carboxy group, sulfo group) , A nitro group, a hydroxy group, a halogen (preferably a chlorine atom), an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably an octylsulfamoyl group), etc. A sulfamoyl group substituted with

  Formylamino group; acetylamino group, propanoylamino group, butanoylamino group, 2,2-dimethylpropanoylamino group, pentanoylamino group, hexanoylamino group, (2-ethyl) hexanoylamino group, heptanoyl Amino group, octanoylamino group, nonanoylamino group, decanoylamino group, undecanoylamino group, dodecanoylamino group, heicosanoylamino group, benzoylamino group, etc., and groups represented by the following formulae Or a hydrocarbon group having 1 to 20 carbon atoms (preferably 1 to 12 carbon atoms) or a derivatized group thereof (for example, carboxy group, sulfo group, nitro group, hydroxy group, halogen (preferably chlorine atom), carbon number 1 10 to 10 alkylsulfamoyl groups (preferably octylsulfamoyl groups) and the like) Carbonyl amino group (if the alkanoylamino group the carbonyl group, the carbon number is preferably 1 to 12);

A hydroxy group;
Halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom;
Carboxy group, —CO ₂ M ² (M ² is alkali metal, preferably lithium, sodium, potassium); sulfo group, —SO ₃ M ² (M ² is alkali metal, preferably lithium, sodium, potassium); Nitro group A cyano group;
Formyloxy group; acetoxy group, propanoyloxy group, butanoyloxy group, 2,2-dimethylpropanoyloxy group, pentanoyloxy group, hexanoyloxy group, (2-ethyl) hexanoyloxy group, heptanoyloxy Carbon such as a group, octanoyloxy group, nonanoyloxy group, decanoyloxy group, undecanoyloxy group, dodecanoyloxy group, heicosanoyloxy group, benzoyloxy group, and the group represented by the following formula A hydrocarbon group having 1 to 20 (preferably 1 to 10 carbons) 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), A group to which an alkyl sulfamoyl group (preferably a group derivatized with an octyl sulfamoyl group) is bound. Boniruokishi group (if the alkanoyloxy group and the carbonyl group, the carbon number is preferably 1 to 10);

  Methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, pentylsulfonyl group, hexylsulfonyl group, (2-ethyl) hexylsulfonyl group, heptylsulfonyl group, octylsulfonyl group, nonylsulfonyl group, decylsulfonyl group, un Decylsulfonyl group, dodecylsulfonyl group, icosylsulfonyl group, phenylsulfonyl group, p-tolylsulfonyl group and the like, and groups having 1 to 20 carbon atoms (preferably having 1 to 10 carbon atoms) such as groups represented by the following formulae: Hydrocarbon group or derivatized group thereof (for example, carboxy group, sulfo group, nitro group, hydroxy group, halogen (preferably chlorine atom), alkylsulfamoyl group having 1 to 10 carbon atoms (preferably octylsulfamoyl group) A group derivatized with a sulfonyl group) ;

A 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-diisobutylcarbamoyl group, N-sec-butylcarbamoyl group, N, N-disec- Butylcarbamoyl group, N-tert-butylcarbamoyl group, N, N-ditert-butylcarbamoyl group, N-pentylcarbamoyl group, N, N-dipentylcarbamoyl group, N- (1-ethylpropyl) carbamoyl group, N, N-di (1-ethylpropyl) carba Yl 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-diheptylcarbamoyl group, N-octylcarbamoyl group, N, N-dioctylcarbamoyl group, N-nonylcarbamoyl group, N, N-octylmethylcarbamoyl group, N, N-octylbutylcarbamoyl group, N, N-di Nonylcarbamoyl group, N-phenylcarbamoyl group, N, N-diphenylcarbamoyl group, N, N-ethylmethylcarbamoyl group, N, N-propylmethylcarbamoyl group, N, N-isopropylmethylcarbamoyl group, N, N-butyl Methylcarbamoyl 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-icosyl 1 or 2 carbon atoms (preferably carbon atoms) such as a methylcarbamoyl group, an N, N-tert-butylmethylcarbamoyl group, an N, N-phenylmethylcarbamoyl group, and a group represented by the following formula A hydrocarbon group having 1 to 10) 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 carbamoyl group substituted with a group derivatized with an octylsulfamoyl group) or the like;

Trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, Carbonization of 1 to 20 carbon atoms in which fluorine atoms are substituted for all hydrogen atoms such as perfluorodecyl group, perfluoroundecyl group, perfluorododecyl group, perfluoroicosyl group, perfluorocyclohexyl group, perfluorophenyl group, etc. A hydrogen group;
Perfluoroethylmethyl group, perfluoropropylmethyl group, perfluoroisopropylmethyl group, perfluorobutylmethyl group, perfluoropentylmethyl group, perfluorohexylmethyl group, perfluoroheptylmethyl group, perfluorooctylmethyl group, perfluoro A straight chain having 1 to 20 carbon atoms in which all hydrogen atoms such as nonylmethyl group, perfluorodecylmethyl group, perfluoroundecylmethyl group, perfluorododecylmethyl group and perfluoroicosylmethyl group are substituted with fluorine atoms Or a hydrocarbon group having 1 to 20 carbon atoms substituted by a branched alkyl group;

  1 to 20 carbon atoms (preferably carbon atoms) in which part of hydrogen atoms such as 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group and 2,4,6-trifluorophenyl group are substituted with fluorine. 1-10) hydrocarbon radicals;

-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 1 to 10 carbon atoms) such as —CH _3; and an aryl group having 6 to 20 carbon atoms such as —CO—S—C ₆ H _5. A thiocarbonyl group;

  * -COCO-R as represented by the following formula (wherein R is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms (for example, satisfying 1 to 20 carbon atoms among the hydrocarbon groups mentioned above) Or a derivatized group thereof (for example, carboxy group, sulfo group, nitro group, hydroxy group, halogen (preferably chlorine atom), alkyl sulfamoyl group having 1 to 10 carbon atoms (preferably octyl sulfamoyl group) A group derived from, etc.)

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

  * -NRCOOR as represented by the following formula (wherein R is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms (for example, those satisfying 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 hydroxy group, a halogen (preferably a chlorine atom), an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably an octylsulfamoyl group), etc. A derivatized group), wherein the Rs may be the same or different from each other and may be bonded to each other to form a ring;

_{* -OP (O) (OCH 3} ) in such _{2 * -OP (O) (OR} ) 2 ( wherein, R represents a hydrogen atom, a hydrocarbon group (e.g., hydrocarbon groups mentioned above having 1 to 20 carbon atoms Or a derivatized group thereof (for example, carboxy group, sulfo group, nitro group, hydroxy group, halogen (preferably chlorine atom), alkyl sulfamoyl group having 1 to 10 carbon atoms) A group derived from (preferably an octylsulfamoyl group) or the like, and the Rs may be the same or different from each other, and may be bonded to each other to form a ring;
* -SiR ₃ (* -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, those satisfying 1 to 20 carbon atoms among the hydrocarbon groups listed above), or a derivatizing group thereof (for example, a carboxy group, sulfo group). A group, a nitro group, a hydroxy group, a halogen (preferably a chlorine atom), a C1-C10 alkylsulfamoyl group (preferably an octylsulfamoyl group) and the like, and the R is Groups that may be the same or different from each other and may be bonded to each other to form a ring);
Etc.

As the divalent substituent, an oxo group, a thioxo group, an imino group, an imino group substituted with an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), or an aryl group having 6 to 20 carbon atoms is substituted. And imino groups. Examples of the imino group substituted with an 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. Can be mentioned. Examples of the imino group substituted with an aryl group include C ₆ H ₅ —N═.

Aliphatic hydrocarbon group having 1 to 40 carbon atoms represented by R ^N1 and R ^N2, and R ^N3, R ¹ ~R ^8, the hydrocarbon group having 1 to 40 carbon atoms represented by R ¹⁰¹ and R ¹⁰² Substituents preferably include those of group s1. The derivatizing groups shown below are 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 an octylsulfamoyl group), and the like. A derivatized group is preferred.
[Group s1]
An oxy group having a hydrocarbon group having 1 to 20 carbon atoms or a derivatizing group thereof bonded to one side;
A carbonyl group to which a hydrocarbon group having 1 to 20 carbon atoms or a derivatizing group thereof is bonded;
An oxycarbonyl group to which a hydrocarbon group having 1 to 20 carbon atoms or a derivatizing group thereof is bonded;
An amino group;
An amino group substituted by one or two hydrocarbon groups having 1 to 20 carbon atoms or a derivatizing group thereof;
A sulfamoyl group;
A sulfamoyl group substituted with one or two hydrocarbon groups having 1 to 20 carbon atoms or a derivatizing group thereof;
A carbonylamino group to which a hydrocarbon group having 1 to 20 carbon atoms or a derivatizing group thereof is bonded;
A hydroxy group;
A 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.);
A nitro group;
A cyano group;
A carbonyloxy group to which a hydrocarbon group of 1 to 20 carbon atoms or a derivatizing group thereof is bonded;
A sulfonyl group to which a hydrocarbon group having 1 to 20 carbon atoms or a derivatizing group thereof is bonded;
A carbamoyl group;
A carbamoyl group substituted with one or two hydrocarbon groups having 1 to 20 carbon atoms or a derivatizing group thereof;
A hydrocarbon group having 1 to 20 carbon atoms in which all of the hydrogen atoms are substituted by fluorine atoms;
A hydrocarbon group having 1 to 20 carbon atoms substituted with a linear or branched alkyl group having 1 to 20 carbon atoms in which all of the hydrogen atoms are substituted with fluorine atoms;
A hydrocarbon group having 1 to 20 carbon atoms in which a part of hydrogen atoms is substituted by fluorine;
Oxo group

The substituent of the hydrocarbon group having 1 to 40 carbon atoms is more preferably a substituent of group s2.
[Group s2]
An oxy group having a hydrocarbon group having 1 to 10 carbon atoms or a derivatizing group thereof bonded to one side;
A carbonyl group to which a hydrocarbon group having 1 to 10 carbon atoms or a derivatizing group thereof is bonded;
An oxycarbonyl group to which a hydrocarbon group having 1 to 10 carbon atoms or a derivatizing group thereof is bonded;
An amino group;
An amino group substituted with one or two hydrocarbon groups having 1 to 10 carbon atoms or a derivatizing group thereof;
A sulfamoyl group;
A sulfamoyl group substituted with one or two hydrocarbon groups having 1 to 10 carbon atoms or a derivatizing group thereof;
A carbonylamino group to which a hydrocarbon group having 1 to 10 carbon atoms or a derivatizing group thereof is bonded;
A hydroxy group;
Fluorine atom, chlorine atom, 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.);
A nitro group;
A cyano group;
A carbonyloxy group to which a hydrocarbon group having 1 to 10 carbon atoms or derivatization thereof is bonded;
A sulfonyl group to which a hydrocarbon group having 1 to 10 carbon atoms or a derivatizing group thereof is bonded;
A carbamoyl group;
A carbamoyl group substituted with one or two hydrocarbon groups having 1 to 10 carbon atoms or a derivatizing group thereof;
A hydrocarbon group having 1 to 10 carbon atoms in which all of the hydrogen atoms are substituted by fluorine atoms;
A hydrocarbon group having 1 to 10 carbon atoms substituted by a linear or branched alkyl group having 1 to 10 carbon atoms in which all of the hydrogen atoms are substituted with fluorine atoms;
A hydrocarbon group having 1 to 10 carbon atoms in which a part of hydrogen atoms is substituted by fluorine;
Oxo group

The hydrocarbon group having 1 to 40 carbon atoms having a substituent represented by R ^N3 , R ^{1 to} R ⁸ , R ^{101 or} R ¹⁰² has 1 to 40 carbon atoms having a monovalent or divalent substituent. A hydrocarbon group, preferably a saturated or unsaturated chain hydrocarbon group having 1 to 30 carbon atoms having a monovalent or divalent substituent, and 3 to 3 carbon atoms having a monovalent or divalent substituent. 30 saturated or unsaturated alicyclic hydrocarbon group, monovalent or divalent substituent hydrocarbon group having 6 to 30 carbon atoms or a combination of hydrocarbon groups, monovalent or 2 A group having 1 to 30 carbon atoms having a valent substituent, and
More preferably, a saturated or unsaturated chain hydrocarbon group having 1 to 20 carbon atoms having a substituent of group s1, or a saturated or unsaturated alicyclic hydrocarbon group having 3 to 20 carbon atoms having a substituent of group s1. A group having 6 to 20 carbon atoms having a substituent of group s1 or a combination of hydrocarbon groups, and a group having 1 to 20 carbon atoms having a substituent of group s1,
Particularly preferably, it is a saturated or unsaturated chain hydrocarbon group having 1 to 15 carbon atoms having a substituent of group s2, or a saturated or unsaturated alicyclic hydrocarbon group having 3 to 15 carbon atoms having a substituent of group s2. , A group having a substituent of group s2 and a combination of an aromatic hydrocarbon group having 6 to 15 carbon atoms or a hydrocarbon group, and 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 preferably has a hetero atom as a ring component. Heterocycle containing. Examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom.
The number of carbon atoms in the heterocyclic group is preferably 3-30, more preferably 3-22, even more preferably 3-20, still more preferably 3-18, and even more preferably 3. ~ 15, particularly preferably 3-14.

As a heterocyclic ring containing a nitrogen atom,
Monocyclic saturated heterocycles such as aziridine, azetidine, pyrrolidine, piperidine, piperazine;
Pyrrols such as 2,5-dimethylpyrrole, pyrazoles such as 2-methylpyrazole and 3-methylpyrazole, 5-membered unsaturated heterocyclic rings such as imidazole, 1,2,3-triazole and 1,2,4-triazole ;
6-membered unsaturated heterocyclic rings such as pyrimidine such as pyridine, pyridazine and 6-methylpyrimidine, pyrazine and 1,3,5-triazine;
Indazole, indoline, isoindoline, indole, indolizine, benzimidazole, quinoline, isoquinoline, quinoxaline such as 5,6,7,8-tetrahydro (3-methyl) quinoxaline, 3-methylquinoxaline, quinazoline, cinnoline, phthalazine, naphthyridine , Condensed bicyclic heterocycles such as purine, pteridine, benzopyrazole, benzopiperidine;
And condensed tricyclic heterocycles such as carbazole, acridine and phenazine.

As a heterocyclic ring containing an oxygen atom,
Monocyclic saturated heterocycles such as oxirane, oxetane, tetrahydrofuran, tetrahydropyran, 1,3-dioxane, 1,4-dioxane, 1-cyclopentyldioxolane;
Bicyclic saturated heterocycles such as 1,4-dioxaspiro [4.5] decane, 1,4-dioxaspiro [4.5] nonane;
Lactone heterocycles such as α-acetolactone, β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone;
5-membered unsaturated heterocyclic rings such as furan such as 2,3-dimethylfuran and 2,5-dimethylfuran;
6-membered unsaturated heterocyclic rings such as 2H-pyran and 4H-pyran;
Fused bicyclic heterocycles such as benzopyran such as 1-benzofuran and 4-methylbenzopyran, benzodioxole, chroman and isochroman;
And condensed tricyclic heterocycles such as xanthene and dibenzofuran;

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

As a heterocyclic ring containing a nitrogen atom and an oxygen atom,
Monocyclic saturated heterocycles such as morpholine, 2-pyrrolidone, 2-methyl-2-pyrrolidone, 2-piperidone, 2-methyl-2-piperidone;
Monocyclic unsaturated heterocycles such as oxazole such as 4-methyloxazole, isoxazole such as 2-methylisoxazole and 3-methylisoxazole;
Condensed bicyclic heterocycles such as benzoxazole, benzisoxazole, benzoxazine, benzodioxane, benzimidazoline;
And condensed tricyclic heterocycles such as phenoxazine.

As a heterocyclic ring containing a nitrogen atom and a sulfur atom,
Monocyclic heterocycles such as thiazole such as 3-methylthiazole and 2,4-dimethylthiazole;
Fused bicyclic heterocycles such as benzothiazole;
Condensed tricyclic heterocycles such as phenothiazine; and the like.

  The heterocyclic ring may be a group obtained by combining the hydrocarbon groups listed above, and examples thereof include a tetrahydrofurylmethyl group.

  Furthermore, the heterocyclic ring may be represented by the following formula.

The heterocyclic group may be a heterocyclic group formed by combining two or more of R ^{1 to} R ⁸ . Such a heterocyclic group has two or more ring structures together with the benzene ring to which R ^{1 to} R ⁸ are bonded. Examples of the two or more ring structures include structures of the following formulas.

  In addition, the bonding position of the above heterocyclic ring is a portion from which an arbitrary hydrogen atom contained in each ring is eliminated.

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 an aliphatic hydrocarbon group represented by R ^N1 and R ^N2 , and a hydrocarbon group represented by R ^N3 , R ^{1 to} R ⁸ , R ¹⁰¹ and R ^102. The same thing as a group is mentioned. When the heterocyclic ring contains a nitrogen atom as a constituent element, the above-described hydrocarbon group may be bonded to the nitrogen atom as a substituent.
Preferred examples of the substituent include an aliphatic hydrocarbon group represented by R ^N1 and R ^N2 , and a hydrocarbon group represented by R ^N3 , R ^{1 to} R ⁸ , R ¹⁰¹ and R ^102. Examples of the preferred substituents are the same.
^{Examples of} the heterocyclic group having a substituent represented by R ^N3 , R ^{1 to} R ⁸ , R ^{101, or} R ¹⁰² include a heterocyclic group having a monovalent or divalent substituent, and preferably a group of s1 Examples include a heterocyclic group having a substituent, and more preferable examples include a heterocyclic group having a substituent of group s2.
The hydrocarbon group or heterocyclic group may have one or more substituents (first substituent), and the two or more substituents are independent of each other. They may be the same or different. Further, the first substituent may have another substituent (second substituent) bonded to a hydrocarbon group contained in a part thereof. The second substituent can 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 , —O—R 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, halogen Atoms, —SO ₃ M, and —CO ₂ M will be described.

As —CO—R ¹⁰² , 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 A hydrocarbon group having 1 to 40 carbon atoms (preferably 1 to 20 carbon atoms) or a derivative thereof, such as a group, a decanoyl group, an undecanoyl group, a dodecanoyl group, a heicosanoyl group, a benzoyl group, and the like A derivatized group (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 an octylsulfamoyl group), etc. Group is a carbonyl group (when the carbonyl group is an acyl group, the carbon number is 2 to 41). ) And include groups corresponding to the -CO-R ¹⁰² in the compounds shown in Tables 1 groups and Japanese Patent Application No. 2017-016290 corresponding to -CO-R ¹⁰² in the compounds shown in 10 Table 1-966 It is done. A carbonyl group to which a hydrocarbon group having 1 to 11 carbon atoms (more preferably 1 to 10 carbon atoms) or a derivatizing group thereof is bonded (when the carbonyl group is an alkanoyl group, the carbon number is more preferably 2). And a group corresponding to —CO—R ¹⁰² in the compounds shown in Tables 1 to 10.

-COO-R ¹⁰¹ includes 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, Heptyloxycarbonyl group, octyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, undecyloxycarbonyl group, dodecyloxycarbonyl group, phenyloxycarbonyl group, icosyloxycarbonyl group, etc. A hydrocarbon group having 1 to 40 carbon atoms (preferably 1 to 20 carbon atoms) or a derivatized group thereof (for example, carboxy group, sulfo group, nitro group, hydroxy group, halogen (preferably chlorine atom), carbon, etc. Number 1-1 A group corresponding to —COO—R ¹⁰¹ in the compounds shown in Tables 1 to 10 and an oxycarbonyl group to which 0 alkylsulfamoyl group (preferably a group derivatized with octylsulfamoyl group) or the like is bonded. And groups corresponding to —COO—R ¹⁰¹ in the compounds shown in Tables 1 to 966 of Japanese Patent Application No. 2017-016290.
Preferable examples include an oxycarbonyl group to which a hydrocarbon group having 1 to 10 carbon atoms or a derivatizing group thereof is bonded, and a group corresponding to —COO—R ¹⁰¹ in the compounds shown in Tables 1 to 10.

The --OCO-R ^102, formyloxy group; acetoxy group, propanoyloxy group, butanoyloxy group, 2,2-dimethylpropanoyloxy group, pentanoyloxy group, hexanoyloxy group, (2-ethyl) Hexanoyloxy group, heptanoyloxy group, octanoyloxy group, nonanoyloxy group, decanoyloxy group, undecanoyloxy group, dodecanoyloxy group, heicosanoyloxy group, benzoyloxy group, and the above formula 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 hydroxy group, a halogen (preferably a chlorine atom) ), Derived from an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably an octylsulfamoyl group), etc. In the compounds shown in Tables 1 to 10 and -OCO-R ¹⁰² in the case where the carbonyloxy group is bonded to the carbonyloxy group (when the carbonyloxy group is an acyloxy group, the carbon number is 2 to 41). And groups corresponding to —OCO—R ¹⁰² in the compounds shown in Tables 1 to 966 of Japanese Patent Application No. 2017-016290, preferably 1 to 11 carbon atoms (more preferably 1 to 10 carbon atoms). In the compounds shown in Tables 1 to 10 and the carbonyloxy group to which the hydrocarbon group or the derivatizing group thereof is bonded (when the carbonyloxy group is an acyloxy group, the carbon number is more preferably 2 to 12). And groups corresponding to —OCO—R ¹⁰² .

The -COCO-R ^102, methyl oxalyl group, an ethyl oxalyl group, a propyl oxalyl group, butyl oxalyl group, pentyl oxalyl group, a hexyl oxalyl group, (2-ethyl) hexyl oxalyl group, heptyl oxalyl group, an octyl oxalyl group, nonyl Oxalyl group, decyloxalyl group, undecyloxalyl group, dodecyloxalyl group, icosyloxalyl group, cyclopentyloxalyl group, cyclohexyloxalyl group, phenyloxalyl group, p-tolyloxalyl group, etc., and groups represented by the above formula A hydrocarbon group having 1 to 40 carbon atoms (preferably 1 to 20 carbon atoms) or a derivatized group thereof (for example, carboxy group, sulfo group, nitro group, hydroxy group, halogen (preferably chlorine atom), 10 alkylsulfamoys And a group corresponding to -COCO-R ¹⁰² in the compounds shown in Tables 1 to 10 and Japanese Patent Application No. 2017-016290. In the compounds shown in Tables 1 to 966, groups corresponding to —COCO—R ¹⁰² are exemplified.

—O—R ¹⁰² includes a hydroxy group; a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, and heptyloxy. Group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group, (2-ethyl) hexyloxy group, icosyloxy group, 1-phenylethoxy group, 1-methyl-1-phenylethoxy group, phenyl Oxy 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-methoxyphenyloxy group, 3-methoxyphenyloxy group, 4-ethoxyphenyloxy group, 2-ethoxyphenyloxy group, 3-ethoxyphenyloxy group, etc. A hydrocarbon group having 1 to 40 carbon atoms (preferably 1 to 20 carbon atoms) such as a group represented by the formula: or a derivatized group thereof (for example, carboxy group, sulfo group, nitro group, hydroxy group, halogen (preferably Chlorine atom), an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably an octylsulfamoyl group), etc. The -O-R ¹⁰² in the compound group) are shown in -O-R ¹⁰² corresponding to group and Japanese Patent Application No. 2017-016290 Patent table 1-966 in the compound represented by group as well as Tables 1 to 10 bound Applicable groups and the like can be mentioned.
Preferred examples include an oxy group to which a hydrocarbon group having 1 to 10 carbon atoms or a derivatizing group thereof is bonded, and a group corresponding to —O—R ¹⁰² in the compounds shown in Tables 1 to 10.

As —SO ₂ —R ¹⁰¹ , methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, pentylsulfonyl group, hexylsulfonyl group, (2-ethyl) hexylsulfonyl group, heptylsulfonyl group, octylsulfonyl group, 1 to 40 carbon atoms such as a nonylsulfonyl group, a decylsulfonyl group, an undecylsulfonyl group, a dodecylsulfonyl group, an icosylsulfonyl group, a phenylsulfonyl group, a p-tolylsulfonyl group, and a group represented by the above formula Preferably a hydrocarbon group having 1 to 20 carbon atoms or a derivatized group thereof (for example, carboxy group, sulfo group, nitro group, hydroxy group, halogen (preferably chlorine atom), alkyl sulfamoyl group having 1 to 10 carbon atoms. (Preferably octylsulfamoyl group) In the compounds shown in Tables 1 to 10 and the groups corresponding to —SO ₂ —R ¹⁰¹ in the compounds shown in Tables 1 to 10 and the compounds shown in Tables 1 to 966 of Japanese Patent Application No. 2017-016290, —SO ₂ —R ^{And the} like, and the like. Preferably, the hydrocarbon group having 1 to 10 carbon atoms or the sulfonyl group to which the derivatizing group is bonded and the compounds shown in Tables 1 to 10 correspond to —SO ₂ —R ¹⁰¹ . And the like.

—SO ₂ N (R ¹⁰² ) ₂ includes a sulfamoyl group;
N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N- sec-butylsulfamoyl 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-phenylsulfamoyl group, etc., and groups represented by the above formula A hydrocarbon group having 1 to 40 carbon atoms (preferably 1 to 20 carbon atoms) or a derivatized group thereof (for example, carboxy group, sulfo group, nitro group, hydroxy group, halogen (preferably chlorine atom), carbon number In a sulfamoyl group substituted with 1 to 10 alkylsulfamoyl groups (preferably a group derivatized with an octylsulfamoyl group, etc.) and compounds shown in Tables 1 to 10, —SO ₂ NH (R ^102Z ) (Provided that R ^102Z is the same as R ¹⁰² except that it does not become a hydrogen atom) and the compounds shown in Tables 1 to 966 of Japanese Patent Application No. 2017-016290, —SO ₂ NH (R ^102Z ) (Provided that R ^102Z is the same as R ¹⁰² except that it does not become a hydrogen atom);

N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-dipropylsulfamoyl group 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-dipentylsulfa Moyl group, N, N-di (1-ethylpropyl) sulfamoyl group, N, N-dihexylsulfamoyl group, N, N-di (2-ethyl) hexyls Famoyl group, N, N-diheptylsulfamoyl group, N, N-octylmethylsulfamoyl group, N, N-dioctylsulfamoyl group, N, N-dinonylsulfamoyl group, N, N-decyl Methylsulfamoyl group, N, N-undecylmethylsulfamoyl group, N, N-dodecylmethylsulfamoyl group, N, N-icosylmethylsulfamoyl group, N, N-phenylmethylsulfamoyl Two hydrocarbon groups having 1 to 40 carbon atoms (preferably 1 to 20 carbon atoms) such as a group, N, N-diphenylsulfamoyl group, and the group represented by the above formula, or a derivatized group thereof ( For example, carboxy group, sulfo group, nitro group, hydroxy group, halogen (preferably chlorine atom), alkyl sulfamoyl group having 1 to 10 carbon atoms (preferably octyl sulfamoyl) ^{_{) -SO 2 N (R 102Z)}} 2 ( provided that at sulfamoyl groups and compounds shown in Tables 1 to 10 are replaced by derivatized groups) in such, except that R ^102Z is not a hydrogen atom, R in the compounds shown in Table 1 to 966 of the corresponding group and Japanese Patent Application No. 2017-016290 the same as a) and _{^{102 -SO 2 N (R 102Z)}} 2 ( where except that R ^102Z is not a hydrogen atom, The same as R ¹⁰² ), and the like.
Preferably, it corresponds to —SO ₂ N (R ¹⁰² ) ₂ in one or two sulfamoyl groups substituted with one or two hydrocarbon groups having 1 to 10 carbon atoms or derivatized groups thereof, and compounds shown in Tables 1 to 10. Groups and the like.

—CON (R ¹⁰² ) ₂ includes 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, 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- One of nonylcarbamoyl group, N-decylcarbamoyl group, N-undecylcarbamoyl group, N-dodecylcarbamoyl group, N-icosylcarbamoyl group, N-phenylcarbamoyl group, etc., and a group represented by the above formula 1 to 40 carbon atoms (preferably carbon 1-20) hydrocarbon group or derivatized group thereof (for example, carboxy group, sulfo group, nitro group, hydroxy group, halogen (preferably chlorine atom), alkyl sulfamoyl group having 1 to 10 carbon atoms (preferably octyl) A carbamoyl group substituted with a group derivatized with a sulfamoyl group) or the like) and -CONH (R ^102Z ) in the compounds shown in Tables 1 to 10 (except that R ^102Z does not become a hydrogen atom, -CONH in R ¹⁰² with a compound represented corresponding to the group, and Japanese Patent Application No. 2017-016290 Patent table 1-966 same at a) (R ^102Z) (where except that R ^102Z is not a hydrogen atom, R ¹⁰² And 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) hexyl Rucarbamoyl 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, etc. Two hydrocarbon groups having 1 to 40 carbon atoms (preferably 1 to 20 carbon atoms) such as a group to be synthesized or a derivatized group thereof (for example, carboxy group, sulfo group, nitro group, hydroxy group, halogen (preferably chlorine atom) ), A C 1-10 alkylsulfamoyl group (preferably an octylsulfamoyl group), etc. Groups) -CON (R ^102Z) ₂ (provided that the compounds shown in carbamoyl groups and Tables 1 to 10 substituted by, except that R ^102Z is not a hydrogen atom, corresponding to the same in a) and R ¹⁰² And -CON (R ^102Z ) ₂ (provided that R ^102Z is the same as R ¹⁰² except that it does not become a hydrogen atom) in the compounds shown in Tables 1 to 966 of Japanese Patent Application No. 2017-016290. Groups, etc.
Preferably, one or two hydrocarbon groups having 1 to 10 carbon atoms or a carbamoyl group substituted with a derivatizing group thereof, and a group corresponding to —CON (R ¹⁰² ) ₂ in the compounds shown in Tables 1 to 10 Is mentioned.

—N (R ¹⁰² ) ₂ includes 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-un A decylamino group, an N-dodecylamino group, an N-icosylamino group, an N-phenylamino group, and the like, and one of 1 to 40 carbon atoms (preferably 1 to 20 carbon atoms) such as a group represented by the above formula A hydrocarbon group 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 alkyl group having 1 to 10 carbon atoms; -NH (R ^102Z) (except that in Amoiru group (preferably octyl sulfamoylamino group) amino group as well as compounds shown in Tables 1 to 10 are replaced by derivatized groups) in such, R ^102Z is a hydrogen atom -NH (R ^102Z ) (provided that R ^102Z does not become a hydrogen atom) in the group corresponding to R ¹⁰² and the compounds shown in Tables 1 to 966 of Japanese Patent Application No. 2017-016290. Except for the above, it is the same as R ¹⁰² ), etc.

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- Ndecylmethylamino group, N, N-dodecylmethylamino group, N, N-icosylmethylamino group, N, N-phenylmethylamino group, N, N-diphenylamino group, etc., and the above formula Two hydrocarbon groups having 1 to 40 carbon atoms (preferably 1 to 20 carbon atoms) such as a group or a derivatized group thereof (for example, carboxy group, sulfo group, nitro group, hydroxy group, halogen (preferably chlorine atom) In the compounds shown in Tables 1 to 10 and 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, -N (R ^102Z) ₂ (provided that, R ^102Z, except that not a hydrogen atom, the compounds shown in Table 1 to 966 groups and Japanese Patent Application No. 2017-016290 corresponding to same in a) and R ¹⁰² N (R ^102Z) ₂ (provided that, R ^102Z, except that not a hydrogen atom, same as is as R ¹⁰²⁾ and a group corresponding to, and the like,
Preferably, one or two hydrocarbon groups having 1 to 10 carbon atoms or an amino group substituted with a derivatizing group thereof, and a group corresponding to —N (R ¹⁰² ) ₂ in the compounds shown in Tables 1 to 10 Is mentioned.

—NHCO—R ¹⁰² includes formylamino group; acetylamino group, propanoylamino group, butanoylamino group, 2,2-dimethylpropanoylamino group, pentanoylamino group, hexanoylamino group, (2-ethyl ) Hexanoylamino group, heptanoylamino group, octanoylamino group, nonanoylamino group, decanoylamino group, undecanoylamino group, dodecanoylamino group, heicosanoylamino group, benzoylamino group, etc. A hydrocarbon group having 1 to 40 carbon atoms (preferably 1 to 20 carbon atoms) such as a group represented by the above formula or a derivatized group thereof (for example, carboxy group, sulfo group, nitro group, hydroxy group, halogen (preferably Is a chlorine atom), an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably an octylsulfamoyl group), etc. In the compounds shown in Tables 1 to 10 and —NHCO—R ^102, a carbonylamino group to which a carbonylamino group is bonded (when the carbonylamino group is an acylamino group, the number of carbon atoms is 1 to 40). And groups corresponding to —NHCO—R ¹⁰² in the compounds shown in Tables 1 to 966 of Japanese Patent Application No. 2017-016290, and the like.
Preferably a carbonylamino group to which a hydrocarbon group having 1 to 10 carbon atoms or a derivatizing group thereof is bonded (when the carbonylamino group is an alkanoylamino group, the carbon number is more preferably 1 to 10) and Table 1 In the compounds shown in Table 10, groups corresponding to —NHCO—R ¹⁰² and the like can be mentioned.

-NHCON (R ¹⁰² ) ₂ includes the groups listed above and the groups corresponding to -NHCON (R ¹⁰² ) ₂ in the compounds shown in Tables 1 to 10, Tables 1 to 966 of Japanese Patent Application No. 2017-016290. In the compounds represented by the above, groups corresponding to —NHCON (R ¹⁰² ) ₂ and the like can be mentioned.

The -NHCOOR ^102, -NHCOOR ¹⁰² group, in the compounds shown in Table 1 to 966 of Japanese Patent Application No. 2017-016290 corresponding to -NHCOOR ¹⁰² in the compound represented by group as well as Tables 1 to 10 given above And the like group.

Examples of —OCON (R ¹⁰² ) ₂ include groups listed above and groups corresponding to —OCON (R ¹⁰² ) ₂ in the compounds shown in Tables 1 to 10, Tables 1 to 966 of Japanese Patent Application No. 2017-016290. And a group corresponding to —OCON (R ¹⁰² ) ₂ in the compound represented by

As the halogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom are preferable.
Examples of M in —SO ₃ M and —CO ₂ M include a hydrogen atom; an alkali metal atom such as a lithium atom, a sodium atom and a potassium atom, preferably a hydrogen atom, a sodium atom and a potassium atom.

The ^{-CO-R 102, -COO-R} 102, -OCO-R 102, -COCO-R 102, -O-R 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, substituent (first substituent) contained in -OCON (R ¹⁰²⁾ ₂ May be one or more, and the two or more substituents may be the same or different independently of each other.
Further, the first substituent may have another substituent (second substituent) bonded to a hydrocarbon group contained in a part thereof. The second substituent can be selected from the same groups as the first substituent.

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

R ^N1 and R ^N2 are an aliphatic hydrocarbon group, an aralkyl group, a (cycloalkyl) alkyl group, an aliphatic hydrocarbon group substituted by a hydroxy group, or an oxy group in which a hydrocarbon group having 1 to 20 carbon atoms is bonded to one side Is preferably a substituted aliphatic hydrocarbon group, a linear or branched alkyl group, a linear or branched alkenyl group, a cycloalkyl group, an aralkyl group, a (cycloalkyl) alkyl group, It is more preferably a linear or branched alkyl group substituted with a hydroxy group, or a linear or branched alkyl group substituted with an alkoxy group.
R ^N1 and R ^N2 may be the same or different.
R ^N3 is preferably an aliphatic hydrocarbon group, more preferably a linear or branched alkyl group, and even more preferably a linear alkyl group.
R ⁴ is preferably a hydrogen atom, and R ^{1 to} R ⁸ are more preferably a hydrogen atom.

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

^Examples of A ^g- include known anions. As ^Ag- , specifically,
Halide ions such as fluoride ions, chloride ions, bromide ions, iodide ions;
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- ;
_{^{CH 3 O -, CH 3 CH}} 2 O -, (CH 3) 3 CO - C 1 -C 20 alkoxyiminocarboxylic ions such _as, C _{6 H} 5 O ^- having 6 to 20 carbon atoms such as aryloxy ion;
Fluorine-containing anion;
Examples thereof include an anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen as essential elements.

^Ag- is a fluorine-containing anion or an anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen as essential elements from the viewpoint of improving heat resistance and reducing sublimation. It is more preferable that it 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, and at least one selected from the group consisting of tungsten and phosphorus. More preferably, the anion contains two elements and oxygen as essential elements.

Examples of the fluorine-containing anion include CF ₃ CO ₂ ^- and the following formulas (III), (IV),
Examples include groups represented by (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 combined to form a carbon number. 1 to 4 fluorinated alkanediyl groups are represented. ]

Wherein (IV), W ⁵ ~W ^7, independently of each other, 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 fluorinated alkyl group having 1 to 4 carbon atoms is preferably a perfluoroalkyl group. 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 the formulas (III) and (V), the fluorinated alkanediyl group having 1 to 4 carbon atoms is preferably a perfluoroalkanediyl group, and —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 formula (III-1) to the formula (III-6) (hereinafter referred to as “anion (III)”). III-1) "to" anion (III-6) ").

  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 formula (V-1) to the formula (V-4) (hereinafter referred to as “anion (V)”). -1) "to" anion (V-4) ").

  As the anion represented by the formula (VI) (hereinafter sometimes referred to as “anion (VI)”), the anion represented by the formula (VI-1) to the formula (VI-4) (hereinafter referred to as “anion (VI)”). -1) "to" anion (VI-4) ").

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), An anion (VI-2) and an anion (VI-3) are preferable, and CF ₃ CO ₂ ⁻ , an anion (III-2), an anion (IV-1), and an anion (VI-1) are more preferable.

  Examples of the anion include an anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and oxygen as essential elements. An anion of heteropolyacid or isopolyacid containing tungsten as an essential element is preferred, and anions of phosphotungstic acid, silicotungstic acid and tungsten-based isopolyacid are more preferred. Such an anion is used for the coloring compound represented by the formula (I) having, for example, a fluorine-containing anion (preferably an anion (VI-1)).

Examples of such anions of heteropolyacid or isopolyacid containing tungsten as an essential element include Keggin type phosphotungstate ion α- [PW ₁₂ O ₄₀ ] ³⁻ , Dawson type phosphotungstate ion α- [P ₂ W ₁₈ O ₆₂ ] ⁶⁻ , β- [P ₂ W ₁₈ O ₆₂ ] ⁶⁻ , Keggin silicotungstate ion α- [SiW ₁₂ O ₄₀ ] ⁴⁻ , β- [SiW ₁₂ O ₄₀ ] ⁴⁻ , γ -[SiW ₁₂ O ₄₀ ] ⁴⁻ , and other examples include [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 these, Keggin type phosphotungstate ion α- [PW ₁₂ O ₄₀ ] ³⁻ is more preferable.

  The compound (I) is preferably a compound represented by the formula (IB) (hereinafter may be referred to as the compound (IB)). When compound (I) is compound (IB), the heat resistance is excellent.

[In formula (IB), R ^N1 , R ^N2 , R ^N3 , R ^{1 to} R ⁸ , R ¹⁰¹ , R ¹⁰² and M represent the same meaning as described above.
B ^h- represents an h-valent anion 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 of 1 to 14. ]

In formula ( ^IB ), B ^h- represents oxygen and at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus listed as ^Ag- in formula (I). Examples thereof include the same g-valent anions contained as essential elements.

In the formula ( ^IB ), preferable B ^h- is preferably at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus mentioned as A ^g- in the formula (I), oxygen, and The same thing as the preferable thing in the g valence anion which contains as an essential element is mentioned.

Examples of the compound (I) include compounds shown in the following Tables 1 to 10 or alkali metal salts thereof.
In Tables 1 to 10 below,
“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” represents —SO ₂ N (CH ₃ ) ((CH ₂ ) ₇ CH ₃ ),
“CNM” represents —CONHCH ₃ ;
“CN2” represents —CON (CH ₃ ) C ₆ H ₅ ,
“NPH” represents —NHC ₆ H ₅ ,
"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 ;
“NH ₂ ” represents —NH ₂ ,
“NCH” represents —NHCOH;
“III-1” to “III-6” represent anions (III-1) to (III-6),
“IV-1” represents an anion (IV-1),
“V-1” to “V-4” represent anions (V-1) to (V-4),
“VI-1” to “VI-4” are anions (VI-1) to anions (VI-4).
Represents.

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

From the viewpoint of easy synthesis, compound (I-1) to compound (I-312) are preferable, compound (I-1) to compound (I-156) are more preferable, and compound (I -1) to Compound (I-24) are more preferable, and Compound (I-13) to Compound (I-24) are particularly preferable.
Especially, it is especially preferable that the compound (I) of the present invention is the compound (I-14).

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 referred to as compound (II). -1) may be obtained by reacting, and at least one element selected from the group consisting of tungsten, silicon, and phosphorus, and oxygen may be obtained from the obtained compound. You may obtain by further making the compound contained as an essential element react.
Further, as a method of exchanging A ^g- of Compound (I) to another A ^g-, the compound obtained above with respect to (I), RG-A '' (RG is a hydrogen atom, an alkali metal atom ( preferably, lithium atom, sodium atom, potassium atom), .A '' is representative of a hydrocarbon group having 1 to 20 carbon atoms, different from the a ^g- compound obtained in the above (I) have a ^g- The compound (I) having an ^{Ag g} different from the ^{Ag g} of the compound (I) obtained above may be obtained by reacting the compound ( ^g ).

[In the formulas (II) and (II-1), R ^{1 to} R ⁸ , R ^N1 , R ^N2 , R ^N3 and g represent the same meaning as described above, and A ′ represents an electron in the above ^{Ag −} . Represents g given. ]

Examples of the compound represented by the formula (II-1) include alkylating agents. The alkylating agent is preferably an alkyl halide such as an alkyl halide having 1 to 10 carbon atoms, more preferably 1 to 3 carbon atoms (such as methyl chloride, methyl bromide or methyl iodide); preferably 2 carbon atoms. -10, more preferably 2-6 carbon atoms, still more preferably dialkyl carbonates having 2-4 carbon atoms (such as dimethyl carbonate or diethyl carbonate); preferably 1-10 carbon atoms, more preferably 1-6 carbon atoms. More preferably a dialkyl sulfuric acid having 1 to 4 carbon atoms (such as dimethyl sulfuric acid or diethyl sulfuric acid); preferably an alkane sulfone having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms. Acid alkyl (methyl methanesulfonate, ethyl ethanesulfonate, ethyl methanesulfonate, methyl ethanesulfonate, trifluoromethanesulfate Methyl phosphate, ethyl trifluoromethanesulfonate, etc.); and the like.
The alkylating agent is preferably a methylating agent, an ethylating agent, a propylating agent, a butylating agent, or the like, 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, more preferably 1 mol or more and 10 mol or less, per 1 mol of compound (II).
0-150 degreeC is preferable and, as for reaction temperature, 10-100 degreeC is more preferable. In order to make the colored compound precursor represented by the formula (I) sufficiently soluble, it may be preliminarily mixed with a predetermined organic solvent at about 70 to 100 ° C. The reaction time is preferably 10 minutes to 24 hours, more preferably 1 hour to 12 hours.

The reaction is preferably performed in an organic solvent from the viewpoint of yield. Examples of organic solvents 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; methanol, ethanol, isopropanol, butanol, etc. Alcohol solvents; 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; N, N-dimethylformamide Amide solvents such as N, N-dimethylacetamide and 1-methyl-2-pyrrolidone; aromatic hydrocarbon solvents are preferred, and toluene and xylene are more preferred.
The amount of the organic solvent to be used is preferably 1 part by mass or more and 300 parts by mass or less, more preferably 1 part by mass or more and 100 parts by mass or less with respect to 1 part by mass of the compound (II).

  The method for obtaining the compound from the reaction mixture is not particularly limited, and various known methods can be employed. For example, the reaction mixture can be filtered, washed with a solvent such as an aromatic hydrocarbon solvent such as toluene, and the resulting residue can be dried. If necessary, it may be further purified by a method of recrystallization using a solvent or silica column chromatography. The obtained compound is, for example, a compound represented by the formula (I).

Next, a method of exchanging anions of 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, oxygen, And (RG) _g A ″ (RG is a hydrogen atom, an alkali metal atom (preferably a lithium atom, sodium, etc.). Atom, potassium atom), and a hydrocarbon group having 1 to 20 carbon atoms.A ″ gave g electrons to ^{Ag −} different from ^{Ag −} that the compound (I) obtained above has. And the like.) And the like.

  A compound containing at least one element selected from the group consisting of tungsten, silicon, and phosphorus and oxygen as essential elements (hereinafter, also referred to as an anion exchange agent) should be produced by a known and conventional method. However, a commercially available product may be used as it is. Such compounds include, for example, the corresponding heteropolyacid salts, isopolyacid salts, or silicates, phosphates, etc., and may be phosphotungstic acid, silicotungstic acid, phosphomolybdic acid and silicomolybdic acid Good.

The amount of the anion exchange agent used is preferably 0.01 mol or more and 5 mol or less, more preferably 0.01 mol or more and 1 mol or less, with respect to 1 mol of the compound represented by the formula (I).
As reaction temperature, 0-150 degreeC is preferable and 10-100 degreeC is more preferable. The reaction time is preferably 10 minutes to 36 hours, more preferably 10 minutes to 24 hours.

(RG) _g A ″ includes those obtained by giving g electrons to A ^g− mentioned above, and g RG (RG is a hydrogen atom, an alkali metal atom (preferably a lithium atom, a sodium atom) , A potassium atom) and a hydrocarbon group having 1 to 20 carbon atoms.

The amount of (RG) _g A ″ used is preferably 0.01 mol or more and 5 mol or less, more preferably 0.01 mol or more and 1 mol, per 1 mol of the compound represented by the formula (I). It is as follows.
The reaction temperature is preferably 0 to 150 ° C, more preferably 10 to 100 ° C. The reaction time is preferably 10 minutes to 36 hours, and more preferably 10 minutes to 24 hours.

This reaction is preferably performed in water, an organic solvent or a mixture thereof from the viewpoint of yield. Examples of organic solvents 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; methanol, ethanol, isopropanol, butanol, etc. Alcohol solvents; 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; N, N-dimethylformamide Amide solvents such as N, N-dimethylacetamide and 1-methyl-2-pyrrolidone; Examples of the solvent in which the above reaction is performed include water, alcohol solvent, ketone solvent, ether solvent, nitrile solvent, amide solvent or a mixture thereof, and more preferably water, alcohol solvent, ketone solvent, nitrile solvent, amide solvent. Or a mixture thereof, more preferably water, an alcohol solvent or a mixture thereof, and particularly preferably water, methanol or a mixture thereof.
The amount of the organic solvent to be used is preferably 1 part by mass or more and 1000 parts by mass or less, more preferably 10 parts by mass or more and 500 parts by mass or less with respect to 1 part by mass of the compound represented by the formula (I).

  The method for obtaining the compound from the reaction mixture is not particularly limited, and various known methods can be employed. For example, the reaction mixture is filtered, washed with a solvent such as water or an alcohol solvent such as methanol, and the resulting residue is dried. If necessary, it may be further purified by a method of recrystallization using a solvent or silica column chromatography.

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

  Compound (II) may be referred to as a compound represented by formula (VII) (hereinafter sometimes referred to as compound (VII)) and a compound represented by formula (VIII) (hereinafter referred to as compound (VIII)). ) 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 represent the same meaning as described above, and R ⁹ represents an alkyl having 1 to 20 carbon atoms. Represents a group. ]

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ⁹ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, and the like. Is an alkyl group having 1 to 6 carbon atoms.

Examples of the base include organic bases such as triethylamine and piperidine, and the amount used is usually 0.05 to 20 mol with respect to 1 mol of compound (VII).
The amount of compound (VIII) to be used is generally 1 to 10 mol, preferably 1 to 4 mol, per 1 mol of compound (II).

The reaction between compound (VII) and compound (VIII) is usually carried out in the presence of a solvent, such as a nitrile solvent such as acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol. Alcohol solvents such as 1-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, methylene chloride, chloroform And amide solvents such as N, N-dimethylformaldehyde and N-methylpyrrolidone, preferably nitrile solvents, alcohol solvents and aromatic hydrocarbon solvents, more preferably acetonitrile and methanol. And toluene. The amount of its use is 1-100 mass parts normally with respect to 1 mass part of compounds (VII).
The reaction temperature is usually 0 to 200 ° C, preferably 0 to 150 ° C. The reaction time is usually 0.5 to 36 hours.

  After completion of the reaction, for example, the compound (II) can be taken out by mixing a solvent in which the compound (II) is hardly dissolved and the obtained reaction mixture and filtering. If necessary, it may be further purified by a method of recrystallization using a solvent or silica column chromatography.

  Compound (VII) is sometimes 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)). ) In a solvent.

[In Formula (IX) and Formula (X), R ^{5 to} R ⁹ represent the same meaning as described 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) to be used is generally 1 to 5 mol, preferably 1 to 3 mol, per 1 mol of compound (IX).
As a solvent, alcohol solvents, such as methanol, are mentioned, The usage-amount is 1-200 mass parts normally with respect to 1 mass part of compounds (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, if necessary, the reaction mixture and water or methanol are mixed and then filtered to take out the compound (VII). Moreover, after completion | finish of reaction, for example, after mixing a reaction mixture and water as needed, extraction with water insoluble in organic solvents, such as ethyl acetate, and concentrating the obtained organic layer, a compound ( VII) can also be removed. If necessary, it may be further purified by a method of recrystallization using a solvent or silica column chromatography.

  Compound (X) is, for example, J.I. Med. Chem. It can be produced according to a known method such as the method described in 2012, 55, 3398-3413.

  The coloring composition of this invention may contain 2 or more types of compounds (I). Compound (I) can be used as a colorant (A) together with a dye or pigment (colorant A1) other than compound (I) as necessary.

<Resin (B)>
The resin (B) is preferably an alkali-soluble resin, and is at least one monomer (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride (hereinafter referred to as “(a)”). In some cases, the polymer is preferably a polymer having a structural unit derived from.
The resin (B) is a structural unit derived from the monomer (b) having a C2-C4 cyclic ether structure and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”), and others. A copolymer having the following structural unit is preferable.
As other structural units, the monomer (c) copolymerizable with the monomer (a) (however, different from the monomer (a) and the monomer (b). Hereinafter, “(c)”) And a structural unit having an ethylenically unsaturated bond, and the like.

Examples of (a) include acrylic acid, methacrylic acid, crotonic acid, and unsaturated monocarboxylic acids such as o-, m-, and p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, Bicyclounsaturated 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 anhydrides such as the above unsaturated dicarboxylic acid anhydrides excluding fumaric acid and mesaconic acid;
Unsaturated mono [(meth) acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Kind;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Of these, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferable from the viewpoint of copolymerization reactivity and the solubility of the resulting resin in an alkaline aqueous solution.

(B) refers to a polymerizable compound having a C2-C4 cyclic ether structure (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. (B) is preferably a monomer having a C2-C4 cyclic ether and a (meth) acryloyloxy group.
Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), and a single monomer having an oxetanyl group and an ethylenically unsaturated bond. Monomer (b2) (hereinafter sometimes referred to as “(b2)”) and monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”) Can be mentioned.

  Examples of (b1) include a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as “(b1-1)”). And a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as “(b1-2)”).

(B1-1) is preferably a monomer having a glycidyl group and an ethylenically unsaturated bond. Specifically as (b1-1), glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, vinylbenzyl 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 (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (Glycidyloxymethyl) styrene and 2, , 6- tris (glycidyloxy) styrene, and the like.
Examples of (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide (registered trademark) 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (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), formula ( A compound represented by BI) and a compound represented by formula (BII).

[In formula (BI) and formula (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 is a hydroxy group May be substituted.
X ^a and X ^b are each independently a single ^{bond, * - R c -, *} - R c -O -, * - represents the R ^c -S- or * -R ^c -NH-.
R ^c represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]

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

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

  The compound represented by formula (BI) and the compound represented by formula (BII) may be used alone or in combination with a compound represented by formula (BI) and a compound represented by formula (BII). May be. When these are used in combination, the content ratio of the compound represented by Formula (BI) and the compound represented by Formula (BII) is preferably 5:95 to 95: 5, more preferably 10: It is 90-90: 10, More preferably, it is 20: 80-80: 20.

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 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] decene-9-yl (meth) acrylate, dicyclopentanyl oxyethyl (main ) Acrylates, isobornyl (meth) acrylates, adamantyl (meth) acrylates, allyl (meth) acrylates, propargyl (meth) acrylates, phenyl (meth) acrylates, naphthyl (meth) acrylates, and benzyl (meth) acrylates Acid esters;
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 itaconate;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-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-methylbicyclo [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-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5 , 6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, etc. A bicyclo unsaturated compound;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate and N- (9-acridinyl) maleimide;
Vinyl group-containing aromatic compounds such as styrene, α-methylstyrene, vinyltoluene and p-methoxystyrene; vinyl group-containing nitriles such as (meth) acrylonitrile; halogenated hydrocarbons such as vinyl chloride and vinylidene chloride; (meth) acrylamide Vinyl group-containing amides such as; esters such as vinyl acetate; dienes such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene;
Of these, styrene, vinyltoluene, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, tricyclo [5.2.1] from the viewpoints of copolymerization reactivity and heat resistance. .0 ^2,6] decan-9-yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decene-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 and benzyl (meth) acrylate are preferred.

The structural unit having an ethylenically unsaturated bond is preferably a structural unit having a (meth) acryloyl group. Resins having such a structural unit include a polymer having a structural unit derived from (a) or (b), an ethylenically unsaturated bond and a group capable of reacting with the group (a) or (b). It can obtain by adding the monomer which has.
Such structural units include a structural unit obtained by adding glycidyl (meth) acrylate to a (meth) acrylic acid unit, a structural unit obtained by adding 2-hydroxyethyl (meth) acrylate to a maleic anhydride unit, and glycidyl (meta And a structural unit obtained by adding (meth) acrylic acid to an acrylate unit. Moreover, when these structural units have a hydroxy group, the structural unit which further added the 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 polymerizing 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 polymerization initiators, azo compounds (2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.) As the solvent, any solvent that dissolves each monomer may be used.

In addition, the obtained polymer may use the solution after the reaction as it is, may use a concentrated or diluted solution, or is taken out as a solid (powder) by a method such as reprecipitation. May be used.
If necessary, a reaction catalyst (for example, tris (dimethylaminomethyl) phenol) of a carboxylic acid or carboxylic acid anhydride and a cyclic ether, a polymerization inhibitor (for example, hydroquinone) or the like may be used.
Carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride, and the like.

As the resin (B), specifically, 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- cyclohexyl maleimide / 2-hydroxyethyl (meth) Acrylate copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6] decyl (meth) acrylate / (meth) acrylic acid / vinyl toluene 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- (meta ) Acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer, benzyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid co Examples thereof include polymers and resins described in JP-A-9-106071, JP-A-2004-29518, and JP-A-2004-361455.
Especially, as resin (B), the copolymer containing the structural unit derived from (a) and the structural unit derived from (b) is preferable.
Two or more kinds of the resin (B) may be combined. In this case, the resin (B) is at least 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate. / (Meth) acrylic acid 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- It is preferable that 1 or more chosen from an epoxy tricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (meth) acrylic acid / 2-ethylhexyl (meth) acrylate copolymer is included.

  The polystyrene equivalent weight average molecular weight (Mw) of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000. 000. The dispersity [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

  The acid value (solid value converted value) 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. It is. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin (B), and can be determined by titration with an aqueous potassium hydroxide solution, for example. .

  In the coloring composition, the content of the resin (B) is preferably 3 to 99% by mass, more preferably 5 to 99% by mass, and further preferably 7 to 95% by mass with respect to the total amount of the solid content. %.

  The colored composition of the present invention preferably contains a solvent (hereinafter sometimes referred to as a solvent (E)). A coloring composition may further improve dispersion stability by including a solvent (E).

<Solvent (E)>
Solvent (E) is, for example, an ester solvent (a solvent containing —COO— in the molecule and not containing —O—), an ether solvent (a solvent containing —O— in the molecule and not containing —COO—), 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 (containing OH in the molecule) , -O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents and dimethyl sulfoxide.

  As ester solvents, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

  Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 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, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, include phenetol and methyl anisole and the like.

  Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, propylene glycol monopropyl 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 and the like.

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

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.
Two or more of these solvents may be used in combination.

  The content of the solvent (E) is preferably 40 to 99% by mass, more preferably 50 to 95% by mass, based on the total amount of the colored composition.

  In the colored composition of the present invention, the compound (I) is preferably dispersed in the solvent (E).

  Compound (I) is optionally treated with rosin, surface treatment with a derivative having an acidic group or basic group introduced, graft treatment on the surface of compound (I) with a polymer compound, etc., and atomization of sulfuric acid Atomization treatment by a method or the like, cleaning treatment with an organic solvent or water for removing impurities, removal treatment by an ion exchange method of ionic impurities, or the like may be performed. The particle size of compound (I) is preferably substantially uniform. Compound (I) can be in a state in which Compound (I) is uniformly dispersed in the dispersion by dispersing the compound (I).

  Examples of the dispersant include surfactants, and any of cationic, anionic, nonionic and amphoteric surfactants may be used. Specific examples include polyester-based, polyamine-based, and acrylic surfactants. These dispersants may be used alone or in combination of two or more. As the dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Geneca Corporation), EFKA (registered trademark) (Manufactured by BASF Corp.), Ajisper (registered trademark) (manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by BYK Chemie Corp.), BYK (registered trademark) (manufactured by BYK Chemie Corp.) Can be mentioned.

  When the dispersant is used, the amount of the dispersant (solid content) used is preferably 300 parts by mass or less, more preferably 5 parts by mass or more and 100 parts by mass or less, relative to 100 parts by mass of the compound (I). . When the usage-amount of a dispersing agent exists in the said range, there exists a tendency for the coloring composition of a more uniform dispersion 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. % By mass.

  In the coloring composition, the content of the compound (I) 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 solid content of the coloring composition. More preferably, it is 2 mass% or more and 75 mass% or less.

  The colored composition of the present invention may contain a colorant other than the compound (I) (hereinafter sometimes referred to as colorant (A1)). The colorant (A1) may contain one or more colorants. The colorant (A1) preferably contains a yellow colorant, an orange colorant, or a red colorant.

<Colorant (A1)>
The colorant (A1) may be a dye or a pigment. As the dye, known dyes can be used, and examples thereof include dyes described in Color Index (published by The Society of Dyers and Colorists) and dyeing notes (Color Dyeing). Further, according to the chemical structure, azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, and the like can be given. These dyes may be used alone or in combination of two or more.

Specific examples include dyes having the following color index (CI) numbers. 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 1 etc.

As the pigment, known pigments can be used, and examples thereof include pigments classified as pigments according to a color index (published by The Society of Dyers and Colorists). These can be used alone or in combination of two or more.
Specifically, C.I. 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, Yellow pigments such as 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214;
C. I. Orange pigments such as CI 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, Red pigments such as 268, 269, 273;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60;
C. I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. And green pigments such as CI Pigment Green 7, 36, 58, and 59.

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

The yellow colorant is the above-mentioned C.I. I. Solvent Yellow 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162; C.I. 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, 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, Yellow pigments such as 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214;
May be selected.
As the yellow colorant, yellow dyes and yellow pigments are preferable, yellow pigments are more preferable, quinophthalone yellow pigments, metal-containing yellow pigments, and isoindoline yellow pigments are more preferable. I. Pigment Yellow 129, 138, 139, 150, 185 are particularly preferred.

The orange colorant is the above-mentioned C.I. 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 CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
May be selected.
As the orange colorant, an orange dye and an orange pigment are preferable, an orange pigment is more preferable, and C.I. I. Pigment Orange 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. 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, Red pigments such as 268, 269, 273;
May be selected.
As the red colorant, red dyes and red pigments are preferable, and azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, perylene dyes, azo pigments, diketopyrrolopyrrole pigments, anthraquinone pigments, xanthene pigments, and perylene pigments are more preferable. Preferably, C.I. I. Acid Red 52, C.I. I. Pigment Red 144, 177, 179, 242, 254, and 269 are more preferable.

  Moreover, you may use the xanthene compound etc. of Unexamined-Japanese-Patent No. 2013-235257 as a yellow colorant, an orange colorant, or a red colorant.

  When the coloring composition of the present invention contains the colorant (A1) and the solvent (E), after preparing a colorant (A1) -containing liquid containing the colorant (A1) and the solvent (E) in advance, the coloration You may prepare a coloring composition using an agent (A1) containing liquid. When the colorant (A1) does not dissolve in the solvent (E), the colorant (A1) -containing liquid can be prepared by dispersing the colorant (A1) in the solvent (E) and mixing. The coloring agent (A1) -containing liquid may contain a part or all of the solvent (E) contained in the coloring composition.

  The coloring composition of the present invention comprises a compound represented by formula (I), a resin, a solvent (E), and a colorant (A1) -containing liquid containing a colorant (A1) and a solvent (E). It is preferable to manufacture by mixing. As the manufacturing method, a compound represented by the formula (I), a resin, and a solvent (E) are mixed by a bead mill or the like to prepare a colored composition, and the resulting colored composition and a colorant ( A method of mixing the colorant (A1) -containing liquid containing A1) and the solvent (E) is preferable.

  If necessary, the colorant (A1) is rosin treatment, surface treatment using a colorant derivative having an acidic group or basic group introduced, or the like. Graft treatment on the surface of the colorant (A1) with a polymer compound or the like. Further, atomization treatment by a sulfuric acid atomization method or the like, cleaning treatment with an organic solvent or water for removing impurities, removal treatment by an ion exchange method of ionic impurities, or the like may be performed. The particle diameter of the colorant (A1) is preferably substantially uniform. The colorant (A1) can be in a state where the colorant (A1) is uniformly dispersed in the colorant (A1) -containing liquid by carrying out a dispersion treatment by containing a dispersant. Each of the colorants (A1) may be subjected to dispersion treatment alone, or a plurality of types may be mixed and dispersed.

  Examples of the dispersant include surfactants, and any of cationic, anionic, nonionic and amphoteric surfactants may be used. Specific examples include polyester-based, polyamine-based, and acrylic surfactants. These dispersants may be used alone or in combination of two or more. As the dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Geneca Corporation), EFKA (registered trademark) (Manufactured by BASF Corp.), Ajisper (registered trademark) (manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by BYK Chemie Corp.), BYK (registered trademark) (manufactured by BYK Chemie Corp.) Can be mentioned.

  When a dispersant is used to prepare the colorant (A1) -containing liquid, the amount of the dispersant (solid content) used is preferably 300 parts by mass or less with respect to 100 parts by mass of the colorant (A1). Yes, more preferably 5 parts by mass or more and 100 parts by mass or less. When the usage-amount of this dispersing agent exists in the said range, there exists a tendency for the colorant (A1) containing liquid of a more uniform dispersion state to be obtained.

  The content of the colorant (A1) in the colorant (A1) -containing liquid is usually 0.1 to 60% by mass, preferably 0.5 to 50% by mass, in the total amount of the colorant (A1) -containing liquid. More preferably, it is 1-40 mass%.

  In the colorant (A1) -containing liquid, the content of the colorant (A1) 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 solids. More preferably, it is 2 mass% or more and 75 mass% or less.

When the colorant (A1) -containing liquid containing the colorant (A1) and the solvent (E) is prepared in advance, the colorant (A1) -containing liquid is used to prepare the coloring composition of the present invention. The agent (A1) -containing liquid may contain a part or all of the resin (B) contained in the colored composition, preferably a part thereof in advance. By including the resin (B) in advance, the dispersion stability of the liquid containing the colorant (A1) can be further improved.
Content of resin (B) in a 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 10-100 mass parts.

In the coloring composition, the content of the colorant (A) combined with the compound (I) and the colorant (A1) is usually 1% by mass or more and 90% by mass or less with respect to the total amount of solids, preferably It is 1 mass% or more and 80 mass% or less, More preferably, it is 2 mass% or more and 75 mass% or less.
The content of the compound (I) is usually 0.001% by mass or more, preferably 0.003% by mass or more, more preferably 0.005% by mass or more, based on the total amount of the colorant (A). Is 100% by mass or less, preferably 99.999% by mass or less, more preferably 99.997% by mass or less.
When the colorant (A1) is contained, the content of the colorant (A1) is preferably 0.1 parts by mass or more, and 0.5 parts by mass or more with respect to 100 parts by mass of the compound (I). More preferably, it is 1 mass part or more, More preferably, it is 10000 mass part or less, More preferably, it is 5000 mass part or less.

  The colored curable composition of the present invention contains compound (I), resin (B) and polymerizable compound (C). In other words, the colored curable composition of the present invention includes a colored composition containing the compound (I) and the resin (B) and the polymerizable compound (C).

<Polymerizable compound (C)>
The polymerizable compound (C) is a compound that can be polymerized by active radicals and / or acids generated from the polymerization initiator (D), such as 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 nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone. And the above-mentioned monomer (a), monomer (b) and monomer (c).

  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, and triethylene glycol di (Meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.

  Especially, it is preferable that a polymeric compound (C) is a polymeric compound which has 3 or more of ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol 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, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. Preferably, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are used.

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

  The content of the polymerizable compound (C) is preferably 1 to 65% by mass, more preferably 3 to 60% by mass, with respect to the total amount of solids in the colored curable composition, and 5 More preferably, it is -55 mass%.

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

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid or the like by the action of light or heat and initiating polymerization, and a known polymerization initiator can be used.
Examples of the polymerization initiator (D) include O-acyloxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, and acylphosphine oxide compounds.

  Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane- 1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- (4-phenylsulfanylphenyl)- 3-cyclopentylpropane-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-y N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazole-3- Yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine and N-benzoyloxy Examples include -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropan-1-one-2-imine. Moreover, as O-acyl oxime compounds, commercially available products such as Irgacure OXE01, OXE02 (above, manufactured by BASF Corporation) and N-1919 (produced by ADEKA Corporation) may be used. Among these, as O-acyloxime compounds, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane- Preferred is at least one selected from the group consisting of 1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, and N-benzoyl Oxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine is more preferred.

Examples of the alkylphenone compound include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutane-1- ON and 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one. Commercial products such as Irgacure 369, 907, 379 (above, manufactured by BASF Corporation) may be used as the alkylphenone compound.
Examples of the alkylphenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, Mention may also be made of 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α, α-diethoxyacetophenone and benzyldimethyl ketal.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl) -4. , 4 ′, 5,5′-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 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 Publication No. 48-38403, Japanese Patent Laid-Open No. 62-17420) And imidazole compounds in which the phenyl group at the 4,4 ′, 5,5′-position is substituted with a carboalkoxy group (for example, see JP-A-7-10913). .

  As triazine compounds, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl)- 1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis ( Trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methyl) Phenyl) ethenyl -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

Furthermore, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone and 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, Examples include quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds.
These are preferably used in combination with a polymerization initiation assistant (D1) (particularly amines) described later.

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

  The content of the polymerization initiator (D) is preferably 0.001 to 40% by mass and more preferably 0.01 to 30% by mass in the total amount of solid content in the colored curable composition.

  The colored curable composition of the present invention may contain a polymerization initiation assistant (D1).

<Polymerization initiation aid (D1)>
The polymerization initiation assistant (D1) is a compound or a sensitizer used for accelerating the polymerization of the polymerizable compound that has been polymerized by the polymerization initiator. When the polymerization initiation assistant (D1) is contained, it is usually used in combination with the polymerization initiator (D).
Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

  Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4- 2-ethylhexyl dimethylaminobenzoate, 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 and the like, preferably 4,4′-bis (diethylamino) benzophenone. Moreover, you may use commercial items, such as EAB-F (made by Hodogaya Chemical 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 are exemplified.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

  Carboxylic acid compounds include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N -Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.

  When using these polymerization initiation assistants (D1), the content is preferably 0.001 to 30% by mass, more preferably 0.01 to 30% by mass in the total amount of solids in the colored curable composition. 20% by mass.

  The coloring composition of the present invention may further contain a leveling agent (F) and an antioxidant.

<Leveling agent (F)>
Examples of the leveling agent (F) include silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom. These may have a polymerizable group in the side chain.
Examples of the silicone surfactant include a surfactant having a siloxane bond in the molecule. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade names: manufactured by 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 (made by Momentive Performance Materials Japan GK) .

  Examples of the fluorosurfactant include a surfactant having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFac (registered trademark) F142D, F171, F172, F173, F177, F183, F183, F554, R30, RS-718-K (manufactured by DIC Corporation), Ftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals), Surflon (registered trademark) S381, S382, SC101, SC105 (Asahi Glass Co., Ltd.) and E5844 (Daikin Fine Chemical Laboratory Co., Ltd.).

  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, Megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Corporation), and the like can be given.

  When the leveling agent (F) is contained, the content is usually 0.0005% by mass or more and 1% by mass or less, preferably 0.001% by mass or more and 0.5% by mass with respect to the total amount of the colored composition. % Or less, more preferably 0.001% by mass or more and 0.2% by mass or less, further preferably 0.002% by mass or more and 0.1% by mass or less, and particularly preferably 0.005% by mass or more. It is 0.1 mass% or less. When the content of the leveling agent (F) is in the above range, the flatness of the color filter can be improved.

<Antioxidant>
From the viewpoint of improving the heat resistance and light resistance of the colorant, it is preferable to use an antioxidant alone or in combination of two or more. The antioxidant is not particularly limited as long as it is an antioxidant generally used industrially, and a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and the like can be used.

  Examples of the phenol-based antioxidant include Irganox 1010 (Irganox 1010: pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], manufactured by BASF Corporation). Irganox 1076 (Irganox 1076: octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, manufactured by BASF Corporation), 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 Corporation), 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 Corp.), 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, BASF Corp.), Irganox 1035 (Irganox 1035: Thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], BASF Corp.), Irganox 1135 ( Irganox 1135: benzenepropanoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy, C7-C9 side chain Rukirester, manufactured by BASF), Irganox 1520L (Irganox 1520L: 4,6-bis (octylthiomethyl) -o-cresol, manufactured by BASF), Irganox 3125 (Irganox 3125, BASF) Irganox 565: 2,4-bis (n-octylthio) -6- (4-hydroxy 3 ′, 5′-di-tert-butylanilino) -1,3,5-triazine, BASF ( Adeka Stub AO-80 (Adeka Stub 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, AD Co., Ltd. KA), Sumilizer BHT (Sumilizer BHT, manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer GA-80 (Sumizer GA-80, manufactured by Sumitomo Chemical Co., Ltd.), Sumizer GS (Sumizer GS, manufactured by Sumitomo Chemical Co., Ltd.), Examples include Cyanox 1790 (Cyanox 1790, manufactured by Cytec Co., Ltd.) and Vitamin E (produced by Eisai Co., Ltd.).

  Examples of the phosphorus antioxidant include Irgafos 168 (Irgafos 168: Tris (2,4-di-tert-butylphenyl) phosphite, manufactured by BASF Corporation), Irgafos 12 (Irgafos 12: Tris [2- [[2,4,8,10-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] ethyl] amine, manufactured by BASF Corp.) Irgafos 38 (Irgafos 38: bis (2,4-bis (1,1-dimethylethyl) -6-methylphenyl) ethyl ester phosphorous acid, manufactured by BASF Corp.), Adekastab 329K (produced by ADEKA Corp.), ADK STAB PEP36 (manufactured by ADEKA), ADK STAB PEP-8 (manufactured by ADEKA), Sandst b P-EPQ (manufactured by Clariant), Weston 618 (manufactured by Weston 618, GE), Weston 619G (manufactured by Weston 619G, GE), Ultranox 626 (manufactured by Ultranox 626, manufactured by GE) and Sumilizer GP (Sumilizer GP): 6- [3- (3-tert-Butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1.3.2] di Oxaphosphepine) (manufactured by Sumitomo Chemical Co., Ltd.).

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

<Other ingredients>
The coloring composition of the present invention may contain additives known in the art, such as a filler, other polymer compound, an adhesion promoter, a light stabilizer, and a chain transfer agent, if necessary.
Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycid. Xylpropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3- Methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-sulfanylpropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (amino Ethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and N-phenyl-3-aminopropyltriethoxy Silane etc. are mentioned.

<Color filter>
A color filter can be formed from the colored composition or colored curable composition of the present invention. Examples of the method for forming the colored pattern include a photolithographic method, an ink jet method, a printing method, and the like, and a photolithographic method is preferable. In the photolithographic method, the colored curable composition is applied to a substrate, dried to form a colored curable composition layer, and the colored curable composition layer is exposed through a photomask and developed. It is. In the photolithographic method, the colored curable composition preferably contains a polymerization initiator (D). In the photolithography method, a colored coating film that is a cured product of the colored curable composition layer can be formed by not using a photomask and / or not developing during exposure. The colored pattern and the 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 and application, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably. Is 0.5-6 μm.

  As the substrate, a glass plate, a resin plate, silicon, or an aluminum, silver, silver / copper / palladium alloy thin film formed on the substrate is used. On these substrates, another color filter layer, a resin layer, a transistor, a circuit, or the like may be formed.

Formation of each color pixel by the photolithographic method can be performed by a known or commonly used apparatus and conditions. For example, it can be produced as follows.
First, a colored curable composition is applied onto a substrate, dried by heating (prebaking) and / or drying under reduced pressure to remove volatile components such as a solvent, and a smooth colored curable composition layer is obtained.
Examples of the coating method include spin coating, slit coating, and slit and spin coating.

  Next, the colored curable composition layer is exposed through a photomask for forming a target colored pattern. An exposure apparatus such as a mask aligner and a stepper can be used to irradiate parallel light uniformly over the entire exposure surface and to perform accurate alignment between the photomask and the substrate on which the colored curable composition layer is formed. It is preferable to use it.

A colored pattern is formed on the substrate by developing the exposed colored curable composition layer in contact with a developer. By the development, the unexposed portion of the colored curable composition layer is dissolved and removed in the developer.
As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate and tetramethylammonium hydroxide is preferable.
The developing method may be any of paddle method, dipping method, spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development.
The substrate after development is preferably washed with water.
Furthermore, it is preferable to post-bake the obtained colored pattern.

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

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention.

  Unless otherwise specified, “%” and “part” in the examples represent mass% and mass part.

  In the following synthesis examples, the structure of the compound was confirmed by NMR (JMM-ECA-500; manufactured by JEOL Ltd.) or mass spectrometry (LC; Agilent 1200 model, MASS; Agilent LC / MSD6130 model).

The polystyrene-reduced weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by the GPC method under the following conditions.
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TSK-GELG2000HXL
Column temperature: 40 ° C
Solvent: Tetrahydrofuran Flow rate: 1.0 mL / min Analysis sample solid content concentration: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector: RI
Calibration standard materials: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The ratio (Mw / Mn) of the weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene obtained above was defined as the dispersity.

Example 1
Coumarin 6 (manufactured by Tokyo Chemical Industry Co., Ltd.) 14.4 parts 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 resulting residue was washed 6 times with 433 parts of toluene. This 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 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 the formula (I-2) and 1500 parts of methanol were mixed. To this mixture, a mixture of 10.4 parts of phosphotungstic acid hydrate (manufactured by Sigma Aldrich Japan Co., Ltd.) and 104 parts of methanol was added. This mixture was filtered, and the resulting residue was washed with 500 parts of methanol. This residue was dried under reduced pressure at 60 ° C. to obtain 12.4 parts of a compound represented by the formula (I-14).

<Identification of 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]
The differential scanning calorimetry of the compound obtained in Example 1 was performed using a differential thermothermal gravimetric simultaneous measurement apparatus (TG / DTA6200 manufactured by SII Nanotechnology). The amount of sample used for one measurement was 5 mg. The measurement temperature was first started at 45 ° C., heated at a rate of 5 ° C. per minute, and measured to 550 ° C. The temperature T ₅ (under nitrogen) at which the weight loss rate was 5% in a nitrogen atmosphere was determined. The results are 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
An appropriate amount of nitrogen was passed through a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, and 280 parts of propylene glycol monomethyl ether acetate was added and heated to 80 ° C. with stirring. Next, 38 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^{2, 6} ] A mixed solution of 289 parts of decan-9-yl acrylate and 125 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, a mixed solution prepared 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 the completion of dropping, the mixture was kept at the same temperature for 4 hours, and then cooled to room temperature to obtain a copolymer (resin B1) solution having a solid content of 35.0%. The obtained resin B1 had a weight average molecular weight (Mw) of 8,800, a dispersity of 2.1, and a solution acid value of 28 mg-KOH / g.

Synthesis example 2
An appropriate amount of nitrogen was passed through a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, and 257 parts of ethyl lactate was added and heated to 75 ° C. with stirring. Then 81 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^{2, 6} ] A mixed solution of 369 parts of decan-9-yl acrylate and 25 parts of ethyl lactate was added dropwise over 5 hours. Meanwhile, a mixed solution in which 11 parts of 2,2-azobis (2,4-dimethylvaleronitrile) was dissolved in 162 parts of ethyl lactate was added dropwise over 5 hours. After maintaining the same temperature for 5 hours after completion of dropping, 95 parts of ethyl lactate was added and cooled to room temperature to obtain a copolymer (resin B2) solution having a solid content of 47.7%. The obtained resin B2 had a weight average molecular weight (Mw) of 8,100, a dispersity of 1.9, and a solution acid value of 53 mg-KOH / g.

Synthesis example 3
A suitable amount of nitrogen was passed through a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, and 371 parts of propylene glycol monomethyl ether acetate was added and heated to 85 ° C. with stirring. Next, 54 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^{2, 6} ] A mixed solution of 225 parts of decan-9-yl acrylate, 81 parts of vinyltoluene (isomer mixture) and 80 parts of propylene glycol monomethyl ether acetate was added dropwise over 4 hours. On the other hand, a solution prepared 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, the solution was kept at the same temperature for 4 hours and then cooled to room temperature to obtain a copolymer (resin B3) solution having a solid content of 37.5%. The obtained resin B3 had a weight average molecular weight (Mw) of 10,600, a dispersity of 2.01, and a solution acid value of 43 mg-KOH / g.

Synthesis example 4
An appropriate amount of nitrogen was passed through a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, and 54 parts of ethyl lactate and 141 parts of propylene glycol monomethyl ether acetate were added and heated to 85 ° C. with stirring. Then 35 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^{2, 6} ] A mixed solution of 23 parts of decan-9-yl acrylate, 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. Meanwhile, a mixed solution prepared 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 of the dropwise addition, the mixture was kept at the same temperature for 4 hours and then cooled to room temperature to obtain a copolymer (resin B4) solution having a solid content of 24.4%. The obtained resin B4 had a weight average molecular weight (Mw) of 8,400, a dispersity of 2.1, and a solution acid value of 26 mg-KOH / g.

[Film thickness measurement]
The film thickness was measured using DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.

[Preparation of resin composition for sublimation test (SJS)]
Resin: methacrylic acid / benzyl methacrylate (molar ratio: 30/70) copolymer (manufactured by Taoka Chemical Co., Ltd., weight average molecular weight (Mw) 10700, acid value 70 mg KOH / g) 33.8% propylene glycol monomethyl ether acetate 40 parts of solution;
Polymerizable compound: dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 5.8 parts;
Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE01; manufactured by BASF Japan Ltd.) 0.58 parts;
Leveling agent: polyether-modified silicone (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.010 parts;
Solvent: 47 parts of propylene glycol monomethyl ether;
Solvent: 6.8 parts of propylene glycol monomethyl ether acetate were mixed to obtain a resin composition for sublimation test (SJS).

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

Example 2
Colorant (A): 14 parts of a compound represented by formula (I-2);
Resin (B): Resin B1 solution 480 parts;
Solvent (E): propylene glycol monomethyl ether acetate 6.2 parts;
Solvent (E): 500 parts of N-methyl-2-pyrrolidone;
As well as surfactant: 0.063 parts of polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) was mixed to obtain 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): propylene glycol monomethyl ether acetate 6.2 parts;
Solvent (E): N-methyl-2-pyrrolidone 540 parts;
In addition, Surfactant: 0.063 parts of polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) was mixed to obtain Coloring Composition 2.

Example 4
Colorant (A): Compound represented by formula (I-14): 10 parts;
Resin (B): 97 parts of resin B2 solution;
Solvent (E): 180 parts of N-methyl-2-pyrrolidone;
Solvent (E): 26 parts 4-hydroxy-4-methyl-2-pentanone;
Solvent (E): 2.0 parts of propylene glycol monomethyl ether acetate; and Surfactant: Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) Got.

Example 5
Colorant (A): 10 parts of a compound represented by formula (I-14),
10 parts of a dispersant (BYK-LPN21324; manufactured by Big Chemie Japan Co., Ltd.)
Resin (B): 11 parts of resin B1 solution and solvent (E): 160 parts of propylene glycol monomethyl ether acetate, and a colored composition in which the compound represented by formula (I-14) is dispersed using a bead mill. Out of 100 copies;
Resin (B): 55 parts of resin B1 solution;
Solvent (E): Propylene glycol monomethyl ether acetate 3.6 parts; and Surfactant: Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) Got.

Comparative Example 1
Colorant (A): Coumarin 6 11 parts;
Resin (B): 350 parts of resin B2 solution;
Solvent (E): propylene glycol monomethyl ether acetate 6.2 parts;
Solvent (E): 630 parts of N, N-dimethylformamide;
Further, surfactant: polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.063 parts was mixed to obtain Coloring Composition 5.

[Sublimation evaluation]
Example 6
Coloring composition 1 was applied on a 2-inch square glass substrate (Eagle XG; manufactured by Corning) by spin coating, and then pre-baked at 100 ° C. for 3 minutes to form a coloring composition layer. The film thickness was measured using DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd. This colored coating film and the resin coating film for sublimation test (SJSM) obtained above were opposed to each other with a space of 70 μm between them, and post-baked 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. The results are shown in Table 12. In Table 12, ◯ indicates that the colorant does not have sublimability, and x indicates that the colorant has sublimability.

Example 7
Sublimation evaluation was performed in the same manner as in Example 6 except that the colored composition 1 was replaced with the colored composition 2. The results are shown in Table 12.

Example 8
Sublimation evaluation was performed in the same manner as in Example 6 except that the colored composition 1 was replaced with the colored composition 3. The results are shown in Table 12.

Example 9
Sublimation evaluation was performed in the same manner as in Example 6 except that the colored composition 1 was replaced with the colored composition 4. The results are shown in Table 12.

Comparative Example 2
Sublimation evaluation was performed in the same manner as in Example 6 except that the colored composition 1 was replaced with the colored composition 5. The results are shown in Table 12.

  From the above results, it was found that the coloring composition containing the compound of the present invention reduced the sublimation of the coloring agent.

Example 10
Colorant (A): 100 parts of a compound represented by formula (I-14),
130 parts of a dispersant (BYK-LPN21324; manufactured by Big Chemie Japan Co., Ltd.),
Resin (B): 170 parts of resin B4 solution and solvent (E): 610 parts of propylene glycol monomethyl ether acetate, and a colored composition in which the compound represented by formula (I-14) is dispersed using a bead mill. Of which 380 copies;
Colorant (A): C.I. I. Pigment yellow 138 (pigment) 18 parts,
7.6 parts of dispersant,
7.6 parts of resin and 120 parts of solvent (E): propylene glycol monomethyl ether acetate, and the total amount of the pigment dispersion in which the pigment was dispersed using a bead mill;
Colorant (A): Compound represented by the following formula (produced by the method described in JP2013-235257A) 4.2 parts;

Resin (B): Resin B3 solution 21 parts;
Polymerizable compound (C): polymerizable compound (A9550; manufactured by Shin-Nakamura Chemical Co., Ltd.)
25 parts;
Polymerization initiator (D): a compound represented by the following formula (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.)
6.6 parts;

Solvent (E): 170 parts of 4-hydroxy-4-methyl-2-pentanone;
Solvent (E): 250 parts of propylene glycol monomethyl ether acetate; and Surfactant: Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) Got.

[Preparation of colored pattern]
The colored curable composition 1 was applied by spin coating on a 2 inch square glass substrate (Eagle XG; manufactured by Corning), and then pre-baked at 100 ° C. for 3 minutes to form a colored curable composition layer. After cooling, the distance between the substrate on which the colored curable composition layer is formed and the quartz glass photomask is set to 200 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) is used in an air atmosphere at 80 mJ / It exposed with an exposure amount of cm ² (365 nm reference). A photomask having a 100 μm line and space pattern was used. The colored curable composition layer after exposure was developed by being immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 ° C. for 70 seconds, and washed with water. The colored coating film was post-baked at 230 ° C. for 30 minutes to obtain a colored pattern.

[Sublimation evaluation]
The colored curable composition 1 was applied by spin coating on a 2 inch square glass substrate (Eagle XG; manufactured by Corning), and then pre-baked 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 with an exposure amount (365 nm standard) of 80 mJ / cm ^{2 in} an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation). did. The colored curable composition layer after exposure was developed by being immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 ° C. for 70 seconds, and washed with water.
The film thickness was measured using DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.
This colored coating film and the resin coating film for sublimation test (SJSM) obtained above were opposed to each other with a space of 70 μm between them, and post-baked 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. The results are shown in Table 13. In Table 13, “◯” indicates that the colorant does not have sublimability, and “x” indicates that the colorant has sublimability.

Example 11
Colorant (A): 100 parts of a compound represented by formula (I-14),
130 parts of a dispersant (BYK-LPN21324; manufactured by Big Chemie Japan Co., Ltd.),
Resin (B): 170 parts of resin B4 solution and solvent (E): 610 parts of propylene glycol monomethyl ether acetate, and a colored composition in which the compound represented by formula (I-14) is dispersed using a bead mill. Of which 340 copies;
Colorant (A): C.I. I. Pigment yellow 138 (pigment) 18 parts,
7.6 parts of dispersant,
7.6 parts of resin and 120 parts of solvent (E): propylene glycol monomethyl ether acetate, and the total amount of the pigment dispersion in which the pigment was dispersed using a bead mill;
Colorant (A): Compound represented by the following formula (produced by the method described in JP2013-235257A) 7.8 parts;

Resin (B): 27 parts of resin B3 solution;
Polymerizable compound (C): polymerizable compound (A9550; manufactured by Shin-Nakamura Chemical Co., Ltd.)
26 parts;
Polymerization initiator (D): a compound represented by the following formula (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.)
6.8 parts;

Solvent (E): 170 parts of 4-hydroxy-4-methyl-2-pentanone;
Solvent (E): 270 parts of propylene glycol monomethyl ether acetate; and Surfactant: Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) Got.
Except having replaced the colored curable composition 1 with the colored curable composition 2, it implemented like Example 10 and produced the colored pattern and evaluated sublimation property. Table 13 shows the results of sublimation evaluation.

Example 12
Colorant (A): 100 parts of a compound represented by formula (I-14),
130 parts of a dispersant (BYK-LPN21324; manufactured by Big Chemie Japan Co., Ltd.),
Resin (B): 170 parts of resin B4 solution and solvent (E): 610 parts of propylene glycol monomethyl ether acetate, and a colored composition in which the compound represented by formula (I-14) is dispersed using a bead mill. Of which 290 parts;
Colorant (A): C.I. I. Pigment yellow 138 (pigment) 23 parts,
9.6 parts of dispersant,
9.6 parts of resin and 150 parts of solvent (E): propylene glycol monomethyl ether acetate, and the total amount of the pigment dispersion obtained by dispersing the pigment using a bead mill;
Colorant (A): Compound represented by the following formula (produced by the method described in JP2013-235257A) 5.1 parts;

Resin (B): 31 parts of resin B3 solution;
Polymerizable compound (C): polymerizable compound (A9550; manufactured by Shin-Nakamura Chemical Co., Ltd.)
27 parts;
Polymerization initiator (D): a compound represented by the following formula (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.)
7.2 parts;

Solvent (E): 170 parts of 4-hydroxy-4-methyl-2-pentanone;
Solvent (E): 280 parts of propylene glycol monomethyl ether acetate; and Surfactant: Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) Got.
Except having replaced the colored curable composition 1 with the colored curable composition 3, it implemented like Example 10 and produced the colored pattern and evaluated sublimation property. Table 13 shows the results of sublimation evaluation.

Example 13
Colorant (A): 100 parts of a compound represented by formula (I-14),
130 parts of a dispersant (BYK-LPN21324; manufactured by Big Chemie Japan Co., Ltd.),
Resin (B): 170 parts of resin B4 solution and solvent (E): 610 parts of propylene glycol monomethyl ether acetate, and a colored composition in which the compound represented by formula (I-14) is dispersed using a bead mill. Of which 270 parts;
Colorant (A): C.I. I. Pigment yellow 138 (pigment) 23 parts,
9.6 parts of dispersant,
9.6 parts of resin and 150 parts of solvent (E): propylene glycol monomethyl ether acetate, and the total amount of the pigment dispersion obtained by dispersing the pigment using a bead mill;
Colorant (A): Compound represented by the following formula (produced by the method described in JP2013-235257A) 7.4 parts;

Resin (B): 35 parts of resin B3 solution;
Polymerizable compound (C): polymerizable compound (A9550; manufactured by Shin-Nakamura Chemical Co., Ltd.)
27 parts;
Polymerization initiator (D): a compound represented by the following formula (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.)
7.3 parts;

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; manufactured by Toray Dow Corning Co., Ltd.) Got.
Except having replaced the colored curable composition 1 with the colored curable composition 4, it implemented like Example 10 and performed preparation of a colored pattern, and sublimation evaluation. Table 13 shows the results of sublimation evaluation.

Example 14
Except having replaced the compound represented by Formula (I-14) with the compound represented by Formula (I-2), it implemented similarly to Example 10 and obtained the colored curable composition 5, and colored Pattern preparation and sublimation evaluation were performed. Table 13 shows the results of sublimation evaluation.

Example 15
Except having replaced the compound represented by Formula (I-14) with the compound represented by Formula (I-2), it implemented similarly to Example 13 and obtained the colored curable composition 6, and colored Pattern preparation and sublimation evaluation were performed. Table 13 shows the results of sublimation evaluation.

Comparative Example 3
Except that the compound represented by the formula (I-14) was replaced with coumarin 6, it was carried out in the same manner as in Example 10 to obtain a colored curable composition 7, and a colored pattern was prepared and evaluated for sublimation. It was. Table 13 shows the results of sublimation evaluation.

Comparative Example 4
Except that the compound represented by the formula (I-14) is replaced with coumarin 6, it is carried out in the same manner as in Example 13 to obtain a colored curable composition 8, and a colored pattern is prepared and evaluated for sublimation. It was. Table 13 shows the results of sublimation evaluation.

  From the above results, it was found that the colored curable composition containing the compound of the present invention reduced the sublimation of the colorant.

  The colored composition and colored curable composition of the present invention can reduce the sublimability of the colorant, and are suitably used for display devices such as color filters and liquid crystal display devices.

Claims (14)

A coloring composition comprising a compound represented by formula (I) and a resin.

[In the formula (I),
R ^N1 and R ^N2 each independently represent a C 1-40 aliphatic hydrocarbon group which may have a substituent.
R ^N3 represents a hydrocarbon group or optionally substituted heterocyclic group having carbon atoms of 1 to 40 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 , —O—R 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, an optionally substituted hydrocarbon group having 1 to 40 carbon atoms or a substituent. Represents a good heterocyclic group.
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.
^R102 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 a plurality of R ¹⁰¹ , R ¹⁰² and M are present, they may be the same or different.
A ^g− represents a g-valent anion.
g represents an integer of 1 to 14. ] A ^g- is tungsten, molybdenum, silicon, and at least one element selected from the group consisting of phosphorus, anion containing and oxygen as essential elements, or coloring composition according to claim 1, wherein the fluorine-containing anion. A ^g- is at least one element selected from the group consisting of tungsten and phosphorus, anion containing and oxygen as essential elements, or coloring composition according to any one of claims 1 to 2 is a fluorine-containing anion. A ^g- is at least one element selected from the group consisting of tungsten and phosphorus, colored composition according to any one of claims 1 to 3 and oxygen is a anion containing as essential elements. The colored composition according to any one of claims 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.   Furthermore, the coloring composition in any one of Claims 1-5 containing a solvent.   Furthermore, the coloring composition in any one of Claims 1-6 containing a yellow coloring agent, an orange coloring agent, or a red coloring agent.   The coloring curable composition containing the coloring composition in any one of Claims 1-7, and a polymeric compound.   Furthermore, the colored curable composition of Claim 8 containing a polymerization initiator.   The color filter formed from the colored composition in any one of Claims 1-7, or the colored curable composition of Claim 8 or 9.   A liquid crystal display device comprising the color filter according to claim 10. A compound represented by formula (IB).

[In the formula (IB),
R ^N1 and R ^N2 each independently represent a C 1-40 aliphatic hydrocarbon group which may have a substituent.
R ^N3 represents a hydrocarbon group or optionally substituted heterocyclic group having carbon atoms of 1 to 40 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 , —O—R 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, an optionally substituted hydrocarbon group having 1 to 40 carbon atoms or a substituent. Represents a good heterocyclic group.
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.
^R102 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 a plurality of R ¹⁰¹ , R ¹⁰² and M are present, they may be the same or different.
B ^h- represents an h-valent anion 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 of 1 to 14. ] The compound according to claim 12, wherein B ^h- is an anion containing at least one element selected from the group consisting of tungsten and phosphorus and oxygen as essential elements. The compound according to claim 12 or 13, wherein R ^N1 and R ^N2 are independently an alkyl group having 1 to 10 carbon atoms which may have a substituent.