CN111065691B - Dye compound having polymerizable group and polymer containing the same as monomer unit - Google Patents
Dye compound having polymerizable group and polymer containing the same as monomer unit Download PDFInfo
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- CN111065691B CN111065691B CN201880058803.9A CN201880058803A CN111065691B CN 111065691 B CN111065691 B CN 111065691B CN 201880058803 A CN201880058803 A CN 201880058803A CN 111065691 B CN111065691 B CN 111065691B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
- C09B69/105—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing a methine or polymethine dye
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F20/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/10—The polymethine chain containing an even number of >CH- groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
Abstract
The present invention provides a novel dye compound having a polymerizable group, which is excellent in color characteristics, heat resistance, light resistance and solvent resistance. Also disclosed is a polymer containing a novel dye compound having a polymerizable group as a monomer unit. The dye compound of the present invention has a polymerizable group and has a structure represented by the following general formula (1).
[ in the formula, R1、R2And R3Each independently represents a group selected from-R4‑NR′‑CO‑L1‑(OCO‑R5C＝CR6R7)n、‑L1‑NR′CO‑R5C＝CR6R7and-NR' CO-R5C＝CR6R7The polymerizable group in (1), and the like. X1Represents an oxygen atom or N-Y, and may be represented by R1And X1To form a ring. Y represents a substituent. X2represents-O-, -S-, -Se-, -NR-8-or-CR9R10‑]。
Description
Technical Field
The present invention relates to a dye compound having a polymerizable group and a polymer containing the same as a monomer unit.
Background
A large number of pyrazolone-based pigments and pyrazolopyrizole-based pigments have been synthesized so far, and their usefulness has been confirmed and widely used. In recent years, the use of the composition has been widely spreading in various applications such as photographic photosensitive materials, heat-sensitive transfer recording materials, color toners, optical recording media, and inkjet.
Further, the properties required for the above-mentioned applications include, for example, a spectral characteristic preferable for color reproduction, solubility in a desired organic solvent, a large molecular absorption coefficient, fastness to light and heat, fastness to various chemicals, ease of synthesis, stability, and the like.
On the other hand, in order to improve these, a large number of pyrazolone-based pigments and pyrazolazole-based pigments have been proposed, and for example, improvement of light and heat fastness has been proposed (patent documents 1 to 6), but solubility is insufficient, and therefore further improvement is desired.
Patent document 7 proposes an improvement in solvent solubility, and the coating is performed in the form of a solution or dispersion in the above-mentioned applications, but since the coating is made soluble in a desired organic solvent, the coating often becomes soluble in other organic solvents, and as a result, the solvent resistance after coating becomes weak.
On the other hand, there is a problem of solvent resistance even in other dyes, and as a countermeasure therefor, for example, in patent document 8, the heat resistance and solvent resistance are improved by polymerizing a triphenylmethane-based dye, but the light resistance inherent in the dye is not improved and is insufficient. In addition, the polymer dye has a problem in use for various applications because of its low solubility.
Patent document 9 proposes a solution for improving solvent resistance by having a polymerizable group, but this solution is not sufficient, and further improvement is desired, and research is required.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2006-15668
Patent document 2: japanese patent laid-open No. 2006-63171
Patent document 3: japanese laid-open patent publication No. 9-226259
Patent document 4: japanese laid-open patent publication No. 10-62978
Patent document 5: japanese laid-open patent publication No. 10-264541
Patent document 6: japanese patent laid-open publication No. 2006-307161
Patent document 7: japanese patent laid-open publication No. 2006-16564
Patent document 8: japanese patent laid-open publication No. 2000-162429
Patent document 9: japanese laid-open patent publication No. 2015-147825
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made in view of the above problems and circumstances, and an object of the present invention is to provide a novel dye compound having a polymerizable group, which has excellent solubility in an organic solvent and can realize a polymer having excellent heat resistance, light resistance and solvent resistance. The dye can be easily put into various forms of use by having excellent solubility in an organic solvent and can be converted into a dye having excellent solvent resistance by heat or light treatment by having a polymerizable group. Also disclosed is a polymer containing a novel dye compound having a polymerizable group as a monomer unit.
Means for solving the problems
The present inventors have made extensive studies and, as a result, have found that the above object can be achieved by the following constitution.
1. A dye compound having a polymerizable group, which has a structure represented by the following general formula (1).
[ solution 1]
[ in the formula,
R1、R2and R3Each independently represents a group selected from-R4-NR′-CO-L1-(OCO-R5C＝CR6R7)n、-L1-NR′CO-R5C＝CR6R7and-NR' CO-R5C＝CR6R7The polymerizable group, the alkyl group, and the aryl group or the heterocyclic group which may have a substituent(s) respectively in (1). R' represents an alkyl group. L is1Represents an alkylene or arylene group。R4Represents a single bond, alkylene or arylene. R5、R6And R7Represents a hydrogen atom, an alkyl group, a carboxyl group, an alkoxycarbonyl group or an aryl group.
X1Represents an oxygen atom or N-Y, and may be represented by R1And X1Forming a ring. Y represents a substituent.
X2represents-O-, -S-, -Se-, -NR-8-or-CR9R10-。R8、R9And R10Represents a group selected from-R4-NR′-CO-L1-(OCO-R5C＝CR6R7)n、-L1-NR′CO-R5C＝CR6R7and-NR' CO-R5C＝CR6R7The polymerizable group in (1), an alkyl group, an aryl group or a heterocyclic group.
Z is the group of atoms necessary to form a ring and represents-CR11＝CR12-or-CR13R14-CR15R16-。
R11～R16Represents a hydrogen atom or a substituent, R11And R12May be bonded to each other to form a ring.
R1、R2、R3、R8、R9、R10、R11、R12、R13、R14、R15、R16Or at least one of Y has a radical selected from the group consisting of-R4-NR′-CO-L1-(OCO-R5C＝CR6R7)n、-L1-NR′CO-R5C＝CR6R7and-NR' CO-R5C＝CR6R7The polymerizable group in (1).
n represents an integer of 1 to 3. ]
2. The dye compound having a polymerizable group according to claim 1, wherein R in the general formula (1) is1、R2、R3、R8、R9、R10、R11、R12、R13、R14、R15、R16Or at least two of Y haveThe polymerizable group, or the R1、R2、R3、R8、R9、R10、R11、R12、R13、R14、R15、R16Or Y has a plurality of the polymerizable groups.
3. The dye compound having a polymerizable group according to claim 1 or 2, wherein the dye compound represented by the general formula (1) has a structure represented by the following general formula (2).
[ solution 2]
[ in the formula,
R1、R2、R3and R17Each independently represents a group selected from-R4-NR′-CO-L1-(OCO-R5C＝CR6R7)n、-L1-NR′CO-R5C＝CR6R7and-NR' CO-R5C＝CR6R7The polymerizable group, the alkyl group, and the aryl group or the heterocyclic group which may have a substituent(s) respectively in (1). R' represents an alkyl group. L is1Represents an alkylene group or an arylene group. R4Represents a single bond, alkylene or arylene. R5、R6And R7Represents a hydrogen atom, an alkyl group, a carboxyl group, an alkoxycarbonyl group or an aryl group. R1、R2、R3Or R17At least two of them having a polymerizable group, or R1、R2、R3Or R17At least one of them has a plurality of the polymerizable groups.
n represents an integer of 1 to 3. n1 represents an integer of 0 to 4. ]
4. The dye compound having a polymerizable group according to claim 3, wherein the dye compound having a polymerizable group represented by the above general formula (2) has a structure represented by the following general formula (3).
[ solution 3]
[ in the formula,
R18represents an alkyl group or an aryl group. R19represents-CO-L1-(OCO-R5C＝CR6R7)n、-CO-R5C＝CR6R7or-CO-CR20R21R22。
R5、R6、R7Represents a hydrogen atom, an alkyl group, a carboxyl group, an alkoxycarbonyl group or an aryl group. R20、R21、R22Each independently represents an alkyl group, an aryl group, a hydrogen atom, -OCOR23。R23Represents an alkyl group or an aryl group.
R2And R17Each independently represents a group selected from-R4-NR′-CO-L1-(OCO-R5C＝CR6R7)n、-L1-NR′CO-R5C＝CR6R7and-NR' CO-R5C＝CR6R7The polymerizable group, the alkyl group, and the aryl group or the heterocyclic group which may have a substituent(s) respectively in (1).
R3Is represented by-L1-NR′CO-R5C＝CR6R7The polymerizable group, the alkyl group, the aryl group which may have a substituent, or the hydrogen atom.
R' represents an alkyl group. L is1Represents an alkylene group or an arylene group. R4Represents a single bond, alkylene or arylene.
R2、R3、R17Or R19At least two of them having a polymerizable group, or R2、R3、R17Or R19Has a plurality of polymerizable groups.
n represents an integer of 1 to 3. n2 represents an integer of 0 to 4. n3 represents an integer of 0 to 5. ]
5. A polymer containing the pigment compound having a polymerizable group according to any one of items 1 to 4 as a monomer unit.
ADVANTAGEOUS EFFECTS OF INVENTION
The above-described means of the present invention can provide a novel dye compound having a polymerizable group, which has excellent solubility and can realize a polymer having excellent heat resistance, light resistance and solvent resistance. Further, a polymer containing a novel dye compound having a polymerizable group as a monomer unit can be provided.
The mechanism of the present invention for developing the effect or the mechanism of action is not clear, but is presumed as follows. The dye compound having a polymerizable group of the present invention has an amido group at a bonding portion, and thus, it is confirmed that heat resistance is improved. Further, the solubility is considered to be improved by substituting the hydrogen atom on the nitrogen of the amido group with an alkyl group or the like.
Detailed Description
The present invention and its constituent elements, as well as the embodiments and modes for carrying out the present invention will be described in detail below. In the present application, "to" is used to include numerical values recited before and after the "to" as the lower limit value and the upper limit value.
The dye compound having a polymerizable group of the present invention is characterized by having a structure represented by the following general formula (1). In a preferred embodiment, the dye compound having a structure represented by the following general formula (1) preferably has a structure represented by the following general formula (2) or the following general formula (3). When the dye compound having a polymerizable group of the present invention has two or more polymerizable groups, a dye compound having more excellent solvent resistance can be formed.
[ solution 4]
R shown in general formulas (1), (2) and (3)1、R2、R3And R17Each independently represents a group selected from-R4-NR′-CO-L1-(OCO-R5C＝CR6R7)n、-L1-NR′CO-R5C＝CR6R7and-NR' CO-R5C＝CR6R7The polymerizable group in (1), the alkyl group, and the aryl group or the heterocyclic group each of which may have a substituent. R' represents an alkyl group. L is1Represents an alkylene group or an arylene group. R4Represents a single bond, alkylene or arylene. R5、R6And R7Represents a hydrogen atom, an alkyl group, a carboxyl group, an alkoxycarbonyl group or an aryl group. n represents an integer of 1 to 3.
L represented by the general formula (1), (2) or (3)1Represents a linking group, an alkylene group or an arylene group. They may or may not have a substituent.
As represented by L in the general formula (1), (2) or (3)1Examples of the substituent of the linking group include a halogen atom, a cyano group and an alkyl group. However, the present invention is not limited to these examples.
R' in the general formula (1), (2) or (3) represents an alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. They may or may not have a substituent. However, the present invention is not limited to these examples.
Examples of the substituent for these groups represented by R' in the general formula (1), (2) or (3) include a halogen atom, a cyano group and an alkyl group. However, the present invention is not limited to these examples.
R shown in general formula (1), (2) or (3)5、R6And R7Each represents a hydrogen atom, an alkyl group, a carboxyl group, an alkoxycarbonyl group or an aryl group. Examples of the alkyl group include a methyl group, an ethyl group, and a butyl group, examples of the alkyl group of the alkoxycarbonyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a hexyl group, a 2-ethylhexyl group, a 3, 5, 5-trimethylhexyl group, and an octyl group, examples of the aryl group include a phenyl group, a naphthyl group, and hydrogen atoms, a carboxyl group, and a methyl group are preferable. However, the present invention is not limited to these examples.
As in formula (1), (2) or (3) by R1、R2、R3And R17Alkyl, aryl or heterocyclyl radicals which may be mentioned for example in the case of alkylExamples thereof include methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, hexyl, octyl, dodecyl, tridecyl, tetradecyl, and pentadecyl. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the heterocyclic group include a pyridine ring, a pyrazole ring, an imidazole ring, a pyrazine ring, a pyrimidine ring, a triazine ring, a thiazole ring, an oxazole ring, a quinoline ring, a benzothiazole ring, and a benzoxazole ring. However, the present invention is not limited to these examples. These groups may have a substituent.
As R in the general formula (3)18Examples of the alkyl group and the aryl group include methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, hexyl, 2-ethylhexyl, 3, 5, 5-trimethylhexyl, octyl, dodecyl, tridecyl, tetradecyl, and pentadecyl. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the heterocyclic ring include a pyridine ring, a pyrazole ring, an imidazole ring, a pyrazine ring, a pyrimidine ring, a triazine ring, a thiazole ring, an oxazole ring, a quinoline ring, a benzothiazole ring, and a benzoxazole ring. However, the present invention is not limited to these examples.
R in the general formula (3)19represents-CO-CR20R21R22，R20、R21、R22Each independently represents an alkyl group, an aryl group, a carboxyl group, an alkoxycarbonyl group, a hydrogen atom or-OCOR23，R23Represents an alkyl group or an aryl group.
X in the general formula (1)1Represents an oxygen atom or N-Y, and when N-Y is represented, R may be substituted1And X1Forming a ring. Examples of the ring to be formed include structures represented by the following general formulae (4), (5), (6) and (7). However, the present invention is not limited to these examples.
[ solution 5]
In general formula (4) to general formula (7), R2' represents an alkyl group, an aryl group, a heterocyclic group and a polymerizable group, R24、R25、R26And R27Represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or a polymerizable group, and may further have a substituent. The symbol "indicates the linking site".]
As represented by R in the general formulae (4), (5), (6) and (7)2Examples of the alkyl group, aryl group, heterocyclic group and polymerizable group represented by' may include the groups represented by the above general formulae (1), (2) and (3)1、R2And R3The same groups.
As represented by R in the general formulae (4), (5), (6) and (7)2The substituents for these groups represented by' may include halogen atoms, cyano groups and alkyl groups. However, the present invention is not limited to these examples.
X in the general formula (1)2represents-O-, -S-, -Se-, -NR-8-or-CR9R10-S-is preferable, and-O-is most preferable.
R in the general formula (1)8Represents a hydrogen atom, an alkyl group or a polymerizable group, and the above-mentioned R is mentioned1、R2And R3The same groups, synthetically preferred, are as R3The same substituent may further have a substituent.
As in the general formula (1) by R8The substituents of these groups include halogen atoms, cyano groups and alkyl groups. However, the present invention is not limited to these examples.
R in the general formula (1)9And R10Represents a hydrogen atom, an alkyl group or a polymerizable group, and the polymerizable group includes the group represented by R1、R2And R3Examples of the alkyl group in the same group include a methyl group, an ethyl group, a butyl group and the like, and preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and may further have a substituent.
As in the general formula (1) by R9And R10The substituents of these groups include halogen atoms, cyano groups and alkyl groups. However, the present invention is not limited to these examples.
Z in the formula (1) is an atomic group necessary for forming a five-membered ring, and represents-CR11＝CR12-、-CR13R14-CR15R16-，R11And R12May be bonded to each other to form a ring, R11～R16Represents a hydrogen atom or a substituent.
In the general formula (1), the substituent for Z is not particularly limited, and examples thereof include an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aryl group, a cyano group, and a halogen atom. Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Examples of the alkyl group include an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a dodecyl group, a tridecyl group, a tetradecyl group, and a pentadecyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a tert-butoxy group, an isobutoxy group, and a pentyloxy group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. Examples of the aryl group include a phenyl group and a naphthyl group, and an alkyl group and an alkoxy group are preferable, and a hydrogen atom and an alkyl group are more preferable. In addition, R11And CR12The ring may be bonded to each other to form a ring, and examples thereof include a cyclopentane ring, a cyclohexane ring, a benzene ring, a pyridine ring, and a naphthalene ring, and the benzene ring is preferable and may further have a substituent. However, the present invention is not limited to these examples.
The dye compound having a polymerizable group represented by the above general formula (1), (2) or (3) may be a copolymer with other monomers, and the monomer is not particularly limited, and examples thereof include acrylic, styrene, and vinyl. However, the present invention is not limited to these examples.
The structure of the polymer containing, as a monomer unit, the dye compound having a polymerizable group represented by the general formula (1), (2) or (3) of the present invention is not particularly limited, and is represented by, for example, general formula (8). However, the present invention is not limited to these examples. Further, since the polymers having the structure represented by the general formula (8) are linked by covalent bonds, the heat resistance is improved, and the compatibility with other polymers is improved, so that the polymers can be mixed.
[ solution 6]
[ in the general formula (8), Dye1A dye structural unit M representing the dye compound according to the present invention1Represents another monomer structural unit, n1 represents the composition of the dye compound according to the present invention, and n2 represents another monomer composition. The symbol "indicates the linking site".]
Examples of the polymerization initiator used for polymerizing the polymerizable monomer include, but are not particularly limited to, tert-butyl peroxyisobutyrate, 2, 5-dimethyl-2, 5-bis (benzoyldioxy) hexane, 1, 4-bis [ alpha- (tert-butyldioxy) -isopropoxy ] benzene, di-tert-butyl peroxide, 2, 5-dimethyl-2, 5-bis (tert-butyldioxy) hexylene peroxide, alpha- (isopropylphenyl) -isopropyl peroxide, 2, 5-bis (hydroperoxy) -2, 5-dimethylhexane, tert-butyl hydroperoxide, 1-bis (tert-butyldioxy) -3, 3, 5-trimethylcyclohexane, butyl-4, 4-bis (tert-butyldioxy) valerate, cyclohexanone peroxide, and the like, Organic peroxides such as 2, 2 ', 5, 5' -tetrakis (t-butylperoxycarbonyl) benzophenone, 3 ', 4, 4' -tetrakis (t-amylperoxycarbonyl) benzophenone, 3 ', 4, 4' -tetrakis (t-hexylperoxycarbonyl) benzophenone, 3 '-bis (t-butylperoxycarbonyl) -4, 4' -dicarboxybenzophenone, t-butyl peroxybenzoate and di-t-butyl diperoxyiisophthalate, quinones such as 9, 10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, octamethylanthraquinone and 1, 2-benzoanthraquinone, benzoin methyl ether, benzoin ethyl ether, alpha-methylbenzoin and alpha-phenylbenzoin, benzoin derivatives such as benzoin methyl ether, benzoin ethyl ether, alpha-methylbenzoin and alpha-phenylbenzoin, Triarylphosphonium salt compounds such as triphenylphosphonium chloride, triphenylphosphonium bromide, tris (4-methoxyphenyl) phosphonium tetrafluoroborate, tris (p-methoxyphenyl) phosphonium hexafluorophosphate, tris (4-ethoxyphenyl) phosphonium tetrafluoroborate and the like, diphenyliodonium chloride, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium methanesulfonate, diphenyliodonium toluenesulfonate, diphenyliodonium bromide, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, bis (p-tert-butylphenyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium methanesulfonate, bis (p-tert-butylphenyl) iodonium toluenesulfonate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, bis (p-tert-butylphenyl) iodonium tetrafluoroborate, tris (p-methoxyphenyl) phosphonium tetrafluoroborate, Diaryliodonium salt compounds such as bis (p-tert-butylphenyl) iodonium chloride, bis (p-chlorophenyl) iodonium chloride and bis (p-chlorophenyl) iodonium tetrafluoroborate, and iron arene complexes. However, the present invention is not limited to these examples.
In the general formula (8), n 1: the molar ratio of n2 is preferably 100: 0-5: 95, or higher. More preferably 90: 10-10: 90, or more.
Representative examples of the dye compound having a polymerizable group of the present invention represented by the above general formula (1), (2) or (3) are listed below, but the present invention is not limited to these. In the following compounds, the symbol "represents a linking site".
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The dye compound having a polymerizable group of the present invention is preferably dissolved in a solvent described below, and is not particularly limited as long as the dye compound having a polymerizable group can be dissolved without causing an obstacle to performance maintenance and processing. The solvent preferably used for the pigment compound having a polymerizable group of the present invention includes aromatic solvents such as toluene and xylene, acetate solvents such as ethyl acetate and propylene glycol monomethyl ether acetate, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, nitrogen-containing solvents such as N, N-dimethylformamide and N-methyl-2-pyrrolidone, halogenated hydrocarbon solvents such as dichloromethane and 1, 1, 2-trichloroethane, alcohol solvents such as methanol, ethanol, trifluoroethanol and butanol, and ether solvents such as tetrahydrofuran, 1, 4-dioxane and propylene glycol monomethyl ether.
The pigment compound having a polymerizable group of the present invention may contain various additives depending on the purpose and use. Examples of the surfactant include an aqueous resin, a nonaqueous resin, an anionic surfactant, a cationic surfactant, a nonionic surfactant, a zwitterionic surfactant, a surface tension modifier, a viscosity modifier, a non-resistance modifier, an antifoaming agent, and a mildewproofing agent.
The pigment compound having a polymerizable group of the present invention can be processed in a state of being dissolved or dispersed in a solvent containing the additive. The amount of the additive or the pigment compound having a polymerizable group in the solvent is appropriately determined according to the purpose. The processing method is not particularly limited, and the processing can be carried out by a conventionally known method such as kneading, bar coating, blade coating, micro gravure coating, knife coating, dip coating, and the like.
Examples of the support to be coated with the coating liquid containing the pigment compound having a polymerizable group of the present invention include, but are not particularly limited to, a glass plate, a sheet, a film, and a plate of plastic or the like.
Examples
Representative examples of The synthesis of The present dye are shown below, and they can be synthesized by referring to conventionally known methods described in Japanese patent application laid-open Nos. 2006-63171, 2006-16564, 2015-147825, etc. "The cyano Dyes and Related Compounds", F.Hamer, Interscience pub issuers, 1964.
Example 1 Synthesis of an intermediate of Compound 112 (Compound 3A)
[ solution 51]
6.74g of Compound 1A and 1.52g of triethylamine were added to 100ml of dichloromethane at room temperature, and after cooling to an internal temperature of-10 ℃ or lower, a solution of Compound 2A in dichloromethane (3.08 g) was added dropwise at 0 ℃ or lower. After completion of the dropwise addition, the reaction was carried out at 0 ℃ or lower for 4 hours. Adding 1N-HCl 15ml at below 15 deg.C, transferring to separating funnel, removing water layer, washing organic layer with water, neutralizing, concentrating under reduced pressure, refining the obtained residue by column chromatography, precipitating with hexane (precipitation), filtering, and drying to obtain orange red solid. The structure is formed by MASS,1H-NMR and IR SpectroscopyTo be identified.
Example 2 Synthesis of intermediate of Compound 112 (Compound 4A)
[ solution 52]
To 100ml of acetonitrile were added 7.57g of Compound 3A, 100ml of 1N-HCl and 3.32g of potassium iodide, and the mixture was heated to an internal temperature of 100 ℃ to effect a reaction for 1 hour. The reaction solution was cooled to 0 ℃ or lower, neutralized, washed with water, the organic layer was concentrated under reduced pressure, and the obtained residue was purified by column chromatography to obtain an orange-red solid. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 3 Synthesis of Compound 112
[ Hua 53]
6.72g of Compound 4A and 3.24g of triethylamine were added to 100ml of dichloromethane, and after cooling to an internal temperature of 0 ℃ or lower, a dichloromethane solution of 2.72g of acryloyl chloride was added dropwise at 0 ℃ or lower. After completion of the dropwise addition, the reaction was carried out at an internal temperature of 0 ℃ or lower for 4 hours. Adding 35ml of 1N-HCl at 15 deg.C or below, transferring to a separating funnel, removing the aqueous layer, washing the organic layer with water, neutralizing, concentrating under reduced pressure, purifying the obtained residue by column chromatography, precipitating with hexane, filtering, and drying to obtain orange red solid. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 4 Synthesis of exemplary Compound 113
[ solution 54]
Example was synthesized in the same manner as in example 3, except that compound 5A was used instead of compound 4A used in example 3A compound 113 is shown. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 5 Synthesis of exemplary Compound 226
An exemplary compound 226 was synthesized in the same manner as in example 3, except that compound 6A was used instead of compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 6 Synthesis of Compound 109
[ solution 56]
An exemplary compound 109 was synthesized in the same manner as in example 3, except that compound 7A was used instead of compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 7 Synthesis of exemplary Compound 151
[ solution 57]
An exemplary compound 151 was synthesized in the same manner as in example 3, except that compound 8A was used instead of compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 8 Synthesis of Compound 153
[ solution 58]
Except for substituting for the compound used in example 3An exemplary compound 153 was synthesized in the same manner as in example 3, except that the compound 9A was used as the compound 4A. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 9 Synthesis of Compound 117
[ chemical 59]
An exemplary compound 117 was synthesized in the same manner as in example 3, except that compound 10A was used instead of compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 10 Synthesis of Compound 118
[ solution 60]
An exemplary compound 118 was synthesized in the same manner as in example 3, except that compound 11A was used instead of compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 11 Synthesis of Compound 187
[ solution 61]
An exemplary compound 187 was synthesized in the same manner as in example 3, except that compound 12A was used instead of compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 12 Synthesis of Compound 188
[ solution 62]
An exemplary compound 188 was synthesized in the same manner as in example 3, except that compound 13A was used instead of compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 13 Synthesis of Compound 233
[ solution 63]
An exemplary compound 233 was synthesized in the same manner as in example 3, except that compound 14A was used instead of compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 14 Synthesis of Compound 326
[ solution 64]
An exemplary compound 326 was synthesized in the same manner as in example 3, except that compound 15A was used instead of compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 15 Synthesis of exemplary Compound 327
[ solution 65]
An exemplary compound 327 was synthesized in the same manner as in example 3, except that compound 16A was used instead of compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 16 Synthesis of exemplary Compound 336
[ solution 66]
An exemplary compound 336 was synthesized in the same manner as in example 3, except that compound 17A was used instead of compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 17 Synthesis of Compound 303
[ solution 67]
An exemplary compound 303 was synthesized in the same manner as in example 3, except that compound 18A was used instead of compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 18 Synthesis of Compound 330
[ solution 68]
An exemplary compound 330 was synthesized in the same manner as in example 3, except that compound 19A was used instead of compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 19 Synthesis of Compound 271
[ solution 69]
An exemplary compound 271 was synthesized in the same manner as in example 3, except that compound 20A was used instead of compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 20 Synthesis of Compound 4
[ solution 70]
An exemplary compound 4 was synthesized in the same manner as in example 3, except that the compound 21A was used instead of the compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 21 Synthesis of Compound 12
[ solution 71]
An exemplary compound 12 was synthesized in the same manner as in example 3, except that compound 22A was used instead of compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 22 Synthesis of Compound 13
[ chemical formula 72]
An exemplary compound 13 was synthesized in the same manner as in example 3, except that compound 23A was used instead of compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 23 Synthesis of Compound 32
[ solution 73]
Except that instead of the compound used in example 34A and compound 24A, an exemplary compound 32 was synthesized in the same manner as in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 24 Synthesis of Compound 40
[ chemical formula 74]
An exemplary compound 40 was synthesized in the same manner as in example 3, except that compound 25A was used instead of compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 25 Synthesis of Compound 47
[ solution 75]
An exemplary compound 47 was synthesized in the same manner as in example 3, except that compound 26A was used instead of compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 26 Synthesis of Compound 57
[ 76]
An exemplary compound 57 was synthesized in the same manner as in example 3, except that compound 27A was used instead of compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 27 Synthesis of Compound 69
[ solution 77]
An exemplary compound 69 was synthesized in the same manner as in example 3, except that compound 28A was used instead of compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 28 Synthesis of Compound 73
[ solution 78]
An exemplary compound 73 was synthesized in the same manner as in example 3, except that a compound 29A was used instead of the compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 29 Synthesis of Compound 75
[ solution 79]
An exemplary compound 75 was synthesized in the same manner as in example 3, except that compound 30A was used instead of compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 30 Synthesis of Compound 81
[ solution 80]
An exemplary compound 81 was synthesized in the same manner as in example 3, except that the compound 31A was used instead of the compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 31 Synthesis of Compound 89
[ solution 81]
An exemplary compound 89 was synthesized in the same manner as in example 3, except that compound 32A was used instead of compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 32 Synthesis of Compound 121
[ solution 82]
An exemplary compound 121 was synthesized in the same manner as in example 3, except that compound 33A was used instead of compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 33 Synthesis of Compound 135
[ solution 83]
An exemplary compound 135 was synthesized in the same manner as in example 3, except that compound 34A was used instead of compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 34 Synthesis of Compound 140
[ solution 84]
An exemplary compound 140 was synthesized in the same manner as in example 3, except that compound 35A was used instead of compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy for identification。
Example 35 Synthesis of exemplary Compound 164
[ solution 85]
An exemplary compound 164 was synthesized in the same manner as in example 3, except that compound 36A was used instead of compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 36 Synthesis of Compound 182
[ solution 86]
An exemplary compound 182 was synthesized in the same manner as in example 3, except that compound 37A was used instead of compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 37 Synthesis of Compound 208
[ solution 87]
An exemplary compound 208 was synthesized in the same manner as in example 3, except that compound 38A was used instead of compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 38 Synthesis of Compound 221
[ solution 88]
Except that instead of compound 4A used in example 3, it was usedAn exemplary compound 221 was synthesized in a manner similar to that of example 3, except that the compound 39A was used. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 39 Synthesis of Compound 249
[ solution 89]
An exemplary compound 249 was synthesized in the same manner as in example 3, except that compound 40A was used instead of compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 40 Synthesis of Compound 255
[ solution 90]
An exemplary compound 255 was synthesized in the same manner as in example 3, except that the compound 41A was used instead of the compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 41 Synthesis of Compound 278
[ solution 91]
An exemplary compound 278 was synthesized by the same method as in example 3, except that the compound 42A was used instead of the compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 42 Synthesis of Compound 289
[ solution 92]
An exemplary compound 289 was synthesized in the same manner as in example 3, except that the compound 43A was used instead of the compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 43 Synthesis of Compound 307
[ solution 93]
An exemplary compound 307 was synthesized in the same manner as in example 3, except that compound 44A was used instead of compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 44 Synthesis of Compound 311
[ solution 94]
An exemplary compound 311 was synthesized in the same manner as in example 3, except that compound 45A was used instead of compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 45 Synthesis of Compound 316
[ solution 95]
An exemplary compound 316 was synthesized in the same manner as in example 3, except that compound 46A was used instead of compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 46 Synthesis of Compound 342
[ solution 96]
An exemplary compound 342 was synthesized in the same manner as in example 3, except that compound 47A was used instead of compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 47 Synthesis of Compound 349
[ solution 97]
An exemplary compound 349 was synthesized in the same manner as in example 3, except that compound 48A was used instead of compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 48 Synthesis of Compound 353
[ solution 98]
An exemplary compound 353 was synthesized in the same manner as in example 3, except that the compound 49A was used instead of the compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 49 Synthesis of Compound 365
[ solution 99]
An exemplary compound 365 was synthesized in the same manner as in example 3, except that compound 50A was used instead of compound 4A used in example 3. The structure is formed by MASS,1H-NMR and IR SpectroscopyTo be identified.
Example 50 Synthesis of Compound 78
[ solution 100]
After 10g of compound 29A was dissolved in 150mL of acetonitrile, 2.8g of compound 51A, 0.68g of N, N-dimethylaminopyridine and 0.01g of p-methoxyphenol were added. The reaction vessel was heated to 50 ℃ in a water bath and allowed to react for 5 hours. After cooling to room temperature, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain exemplary compound 78. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 51 Synthesis of Compound 102
[ solution 101]
An exemplary compound 102 was synthesized in the same manner as in example 50, except that compound 52A was used instead of compound 29A used in example 50. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 52 Synthesis of Compound 115
[ solution 102]
An exemplary compound 115 was synthesized in the same manner as in example 50, except that compound 53A was used instead of compound 29A used in example 50. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 53 Synthesis of Compound 129
[ solution 103]
An exemplary compound 129 was synthesized in the same manner as in example 50, except that compound 54A was used instead of compound 29A used in example 50. The structure is formed by MASS,1H-NMR and IR spectroscopy.
Example 54 Synthesis of copolymer (1)
[ solution 104]
To 30ml of dioxane, 2.6g of the exemplified compound 112 and 0.29g of methyl acrylate were added, and the mixture was stirred and mixed in a nitrogen stream. After stirring and mixing, 0.03g of tert-butyl peroxyisobutyrate was added to a nitrogen stream, heated to 80 ℃ and allowed to polymerize for 4 hours. Then, the reaction mixture was cooled and purified by reprecipitation using 300ml of hexane, whereby 2.5g of copolymer (1) was obtained. In the following structural formula, the symbol represents a linking site.
Example 55 Synthesis of copolymer (2)
[ solution 105]
2.4g of a copolymer (2) was obtained in the same manner as in example 54, except that 2.5g of the example compound 113 was used instead of the example compound 112 used in example 54.
Comparative example 1 Synthesis of comparative Compound A
The following comparative compound a described in japanese patent application laid-open No. 2015-147825 was synthesized.
[ solution 106]
Comparative example 2 Synthesis of comparative Compound B
The following comparative compound B described in japanese patent application laid-open No. 2015-147825 was synthesized.
[ solution 107]
Comparative example 3 Synthesis of comparative Compound C
The following comparative compound C described in Japanese patent application laid-open No. 2006-16564 was synthesized.
[ solution 108]
Comparative example 4 Synthesis of copolymer (3)
2.4g of a copolymer (3) was obtained in the same manner as in example 54, except that 2.5g of the comparative compound A was used in place of the example compound 112 used in example 54.
[ solution 109]
Comparative example 5 Synthesis of copolymer (4)
2.4g of a copolymer (4) was obtained in the same manner as in example 54, except that 2.5g of the comparative compound B was used in place of the example compound 112 used in example 54.
[ solution 110]
Evaluation of solubility
The dye compound having a polymerizable group of the present invention, the polymer containing the same as a monomer unit (the copolymer of the present invention), and the comparative material (the comparative compound and the comparative copolymer) were dissolved in methanol, ethyl acetate, toluene, ethylene glycol, and N-methyl-2-pyrrolidone (NMP), respectively, so as to form a concentration of 3 mass%, and the solubility thereof was evaluated by visual evaluation on a 4-grade basis based on the following evaluation criteria. The results are shown in tables I and II.
Very good: completely dissolve immediately
O: completely dissolved by shaking overnight at room temperature.
And (delta): completely dissolved by heating.
X: even when heated, there is a dissolution residue.
Preferably, the value is O or more.
[ Table 1]
TABLE I
[ Table 2]
TABLE II
Preparation of coated sample
(example 56)
The pigment compound having a polymerizable group of the present invention and azobisisobutyronitrile as a photopolymerization initiator are dissolved in 1: 1 to 150 μm thick synthetic paper (ユポ FPG-150: manufactured by Wangzi oil Co., Ltd.), the obtained coloring solution was applied and dried to a wet film thickness of 60 μm, and then exposed to light using a high-pressure mercury lamp (3kW, 200 mJ/cm)2) To prepare a coated sample. By adjusting the dye concentration of each solution, a coating sample (hereinafter referred to as a coating film a) having a reflection concentration of 1 at the maximum absorption wavelength was prepared, and performance evaluation was performed.
Example 57
The dye compound having a polymerizable group of the present invention is dissolved in 1: 1 to prepare coating samples, the obtained coloring solutions were applied and dried to a wet film thickness of 60 μm on synthetic paper (ユポ FPG-150: manufactured by prince oil chemical Co., Ltd.) having a thickness of 150 μm, respectively. By adjusting the dye concentration of each solution, a coating sample (hereinafter referred to as a coating film B) having a reflection concentration of 1 at the maximum absorption wavelength was prepared, and performance evaluation was performed.
In comparative dyes a to C (comparative compounds), coating samples (coating films a and B) were also prepared in the same manner as in examples 56 and 57. Further, with respect to the copolymers (1) to (4), a coating sample (coating film B) was also prepared in the same manner as in example 57.
Evaluation of light resistance
The coated film a and the samples coated with the comparative dyes (comparative compounds a to C) produced in the same manner as in example 56 and the copolymers (1) to (4) produced in the same manner as in example 57 were exposed to light for 120 hours using a xenon arc lamp lightfastness tester, and then the residual ratio of the reflection spectrum density at the maximum absorption wavelength from the visible region of the unexposed sample was evaluated. The results are shown in tables III and IV.
The light resistance (%) was obtained as (maximum absorption wavelength concentration of exposed sample/maximum absorption wavelength concentration of unexposed sample) × 100, and 4-grade evaluation was performed based on the following evaluation criteria.
Very good: light resistance of 95% or more
O: the light resistance is more than 90% and less than 95%
And (delta): the light resistance is more than 80% and less than 90%
X: light resistance less than 80%
If the value is equal to or greater than O, there is no practical problem.
[ Table 3]
TABLE III
| Pigment compound | Light resistance | Remarks for note |
| Exemplary Compound 4 | ◎ | The invention |
| Exemplary Compound 12 | ◎ | The invention |
| Exemplary Compound 13 | ◎ | The invention |
| Exemplary Compound 32 | ◎ | The invention |
| Exemplary Compound 40 | ◎ | The invention |
| Exemplary Compound 47 | ◎ | The invention |
| Exemplary Compound 57 | ◎ | The invention |
| Exemplary Compound 69 | ◎ | The invention |
| Exemplary Compound 73 | ◎ | The invention |
| Exemplary Compound 75 | ◎ | The invention |
| Exemplary Compound 78 | ◎ | The invention |
| Exemplary Compound 81 | ◎ | The invention |
| Exemplary Compound 89 | ◎ | The invention |
| Exemplary Compound 102 | ◎ | The invention |
| Exemplary Compound 109 | ◎ | The invention |
| Exemplary Compound 112 | ◎ | The invention |
| Exemplary Compound 113 | ◎ | The invention |
| Exemplary Compound 115 | ◎ | The invention |
| Exemplary Compound 117 | ◎ | The invention |
| Exemplary Compound 118 | ◎ | The invention |
| Exemplary Compound 121 | ◎ | The invention |
| Exemplary Compound 129 | ◎ | The invention |
| Exemplary Compound 135 | ◎ | The invention |
| Exemplary Compound 140 | ◎ | The invention |
| Exemplary Compound 151 | ◎ | The invention |
| Exemplary Compound 153 | ◎ | Hair brushMing dynasty |
| Exemplary Compound 164 | ◎ | The invention |
| Exemplary Compound 182 | ◎ | The invention |
| Exemplary Compound 187 | ◎ | The invention |
| Exemplary Compound 188 | ◎ | The invention |
| Exemplary Compound 208 | ◎ | The invention |
| Exemplary Compound 221 | ◎ | The invention |
| Exemplary Compound 227 | ◎ | The invention |
| Exemplary Compound 233 | ◎ | The invention |
| Exemplary Compounds 249 | ◎ | The invention |
| Exemplary Compound 255 | ◎ | The invention |
| Exemplary Compound 271 | ◎ | The invention |
| Exemplary Compound 278 | ◎ | The invention |
| Exemplary Compounds 289 | ◎ | The invention |
| Exemplary Compound 303 | ◎ | The invention |
| Exemplary Compound 307 | ◎ | The invention |
| Exemplary Compound 311 | ◎ | The invention |
| Exemplary Compound 316 | ◎ | The invention |
| Exemplary Compound 326 | ◎ | The invention |
| Exemplary Compound 327 | ◎ | The invention |
| Exemplary Compound 330 | ◎ | The invention |
| Exemplary Compound 336 | ◎ | The invention |
| Exemplary Compound 342 | ◎ | The invention |
| Exemplary Compound 349 | ◎ | The invention |
| Exemplary Compound 353 | ◎ | The invention |
| Exemplary Compound 365 | ◎ | The invention |
| Comparative Compound A | Δ | Comparative example |
| Comparative Compound B | ○ | Comparative example |
| Comparative Compound C | ○ | Comparative example |
[ Table 4]
TABLE IV
| Copolymer | Light resistance | Remarks for note |
| Copolymer (1) | ◎ | The invention |
| Copolymer (2) | ◎ | The invention |
| Copolymer (3) | ○ | Comparative example |
| Copolymer (4) | ○ | Comparative example |
Evaluation of Heat resistance
The coated film a and the samples coated with the comparative dyes (comparative compounds a to C) produced by the same method as in example 56 and the copolymers (1) to (4) produced by the same method as in example 57 were stored at 77 ℃ and 10% RH or less for 7 days, and the residual ratio obtained from the concentration ratio before and after the start of storage was evaluated. The results are shown in tables V and VI.
The heat resistance (%) was obtained as (concentration after storage/concentration before storage) × 100, and 4-grade evaluation was performed based on the following evaluation criteria.
Very good: the heat resistance is more than 95%
O: the heat resistance is more than 80 percent and less than 95 percent
And (delta): the heat resistance is more than 60 percent and less than 80 percent
X: the heat resistance is less than 60 percent
If the value is equal to or greater than O, there is no practical problem.
[ Table 5]
TABLE V
| Pigment compound | Heat resistance | Remarks for note |
| Exemplary Compound 4 | ◎ | The invention |
| Exemplary Compound 12 | ◎ | The invention |
| Exemplary Compound 13 | ◎ | The invention |
| Exemplary Compound 32 | ○ | The invention |
| Exemplary Compound 40 | ◎ | The invention |
| Exemplary Compound 47 | ○ | The invention |
| Exemplary Compound 57 | ○ | The invention |
| Exemplary Compound 69 | ○ | The invention |
| Exemplary Compound 73 | ◎ | The invention |
| Exemplary Compound 75 | ○ | The invention |
| Exemplary Compound 78 | ◎ | The invention |
| Exemplary Compound 81 | ○ | The invention |
| Exemplary Compound 89 | O | The invention |
| Exemplary Compound 102 | ◎ | The invention |
| Exemplary Compound 109 | ◎ | The invention |
| Exemplary Compound 112 | ○ | The invention |
| Exemplary Compound 113 | ○ | The invention |
| Exemplary Compound 115 | ◎ | The invention |
| Exemplary Compound 117 | ○ | The invention |
| Exemplary Compound 118 | ○ | The invention |
| Exemplary Compound 121 | ◎ | The invention |
| Exemplary Compound 129 | ◎ | The invention |
| Exemplary Compound 135 | ◎ | The invention |
| Exemplary Compound 140 | ○ | The invention |
| Exemplary Compound 151 | ◎ | The invention |
| Exemplary Compound 153 | ◎ | The invention |
| Exemplary Compound 164 | ○ | The invention |
| Exemplary Compound 182 | ○ | The invention |
| Exemplary Compound 187 | ○ | The invention |
| Exemplary Compound 188 | ○ | The invention |
| Exemplary Compound 208 | ○ | The invention |
| Exemplary Compound 221 | ○ | The invention |
| Exemplary Compound 227 | ○ | The invention |
| Exemplary Compound 233 | ○ | The invention |
| Exemplary Compounds 249 | ◎ | The invention |
| Exemplary Compound 255 | ○ | The invention |
| Exemplary Compound 271 | ○ | The invention |
| Exemplary Compound 278 | ○ | The invention |
| Exemplary Compounds 289 | ○ | The invention |
| Exemplary Compound 303 | ◎ | The invention |
| Exemplary Compound 307 | ○ | The invention |
| Exemplary Compound 311 | ◎ | The invention |
| Exemplary Compound 316 | ◎ | The invention |
| Exemplary Compound 326 | ◎ | The invention |
| Exemplary Compound 327 | ◎ | The invention |
| Exemplary Compound 330 | ◎ | The invention |
| Exemplary Compound 336 | ○ | The invention |
| Exemplary Compound 342 | ◎ | The invention |
| Exemplary Compound 349 | ◎ | The invention |
| Exemplary Compound 353 | ◎ | The invention |
| Exemplary Compound 365 | ◎ | The invention |
| Comparative Compound A | Δ | Comparative example |
| Comparative Compound B | Δ | Comparative example |
| Comparative Compound C | ○ | Comparative example |
[ Table 6]
TABLE VI
| Copolymer | Heat resistance | Remarks for note |
| Copolymer (1) | ◎ | The invention |
| Copolymer (2) | ◎ | The invention |
| Copolymer (3) | ○ | Comparative example |
| Copolymer (4) | ○ | Comparative example |
Evaluation of solvent resistance
The obtained coating film a, coating film B, and each comparative material (comparative compound and comparative copolymer) were immersed in methanol, ethyl acetate, toluene, ethylene glycol, and NMP, respectively, at 25 ℃ for 30 minutes. The samples before and after the treatment were evaluated for the residual ratio obtained from the reflection spectrum density at the maximum absorption wavelength in the visible region before the immersion, and are shown in tables VII and VIII.
The solvent resistance (%) was determined as (maximum absorption wavelength concentration of the impregnated sample/maximum absorption wavelength concentration of the non-impregnated sample) × 100, and 4-grade evaluation was performed based on the following evaluation criteria.
Very good: solvent resistance of more than 90 percent
O: the solvent resistance is more than 80 percent and less than 90 percent
And (delta): the solvent resistance is more than 60 percent and less than 80 percent
X: solvent resistance is less than 60 percent
If the value is equal to or greater than ≈ o, there is no practical problem.
[ Table 7]
TABLE VII
[ Table 8]
TABLE VIII
As seen from tables I, II, III, IV, V, VI, VII and VIII, it was confirmed that: the pigment compound of the present invention has high solubility in an organic solvent, and is excellent in light resistance and heat resistance in a polymer containing the same as a monomer unit. Further, by introducing 1 or more polymerizable groups, the solvent resistance was successfully improved greatly.
As described above, the present invention can provide a dye having more excellent light resistance, heat resistance and solvent resistance than conventional pyrazolone-based dyes and pyrazolazole-based dyes.
Industrial applicability
The dye compound having a polymerizable group of the present invention has excellent solubility, and can realize a polymer having excellent heat resistance, light resistance and solvent resistance. By having excellent solubility in an organic solvent, it can be easily put into various forms for use.
Claims (3)
1. A dye compound having a polymerizable group, characterized by having a structure represented by the following general formula (3):
in the formula (I), the compound is shown in the specification,
R18represents methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, hexyl, 2-ethylhexyl, 3, 5, 5-trimethylhexyl, octyl, dodecyl, tridecyl, tetradecyl or pentadecyl,
R19represents-CO-L1-(OCO-R5C＝CR6R7)nor-CO-R5C＝CR6R7，
R5、R6、R7Represents a hydrogen atom, a methyl group, an ethyl group, a butyl group or an alkoxycarbonyl group,
R2each independently represents a group selected from-R4-NR′-CO-L1-(OCO-R5C＝CR6R7)n、-L1-NR′CO-R5C＝CR6R7and-NR' CO-R5C＝CR6R7The polymerizable group of (1), methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, 2-ethylhexyl group, 3, 5, 5-trimethylhexyl group or phenyl group,
R17each independently represents a group selected from-R4-NR′-CO-L1-(OCO-R5C＝CR6R7)n、-L1-NR′CO-R5C＝CR6R7and-NR' CO-R5C＝CR6R7The polymerizable group in (1) is a polymerizable group,
R3is represented by-L1-NR′CO-R5C＝CR6R7A polymerizable group represented by the formula, methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, hexyl, octyl, dodecyl, tridecyl, tetradecyl, pentadecyl or 3, 5, 5-trimethylhexyl,
r' represents methyl, ethyl, propyl or butyl, L1Represents an alkylene group, R4Represents a single bond or an alkylene group,
n represents an integer of 1 to 3, n2 represents an integer of 0 to 4, and n3 represents 1 or 2.
2. The dye compound having a polymerizable group according to claim 1, wherein R in the general formula (3)2Represents 2-ethylhexyl or 3, 5, 5-trimethylhexyl, R3Represents 3, 5, 5-trimethylhexyl.
3. A polymer comprising the pigment compound having a polymerizable group according to claim 1 or 2 as a monomer unit.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2017177293 | 2017-09-15 | ||
| JP2017-177293 | 2017-09-15 | ||
| PCT/JP2018/033941 WO2019054436A1 (en) | 2017-09-15 | 2018-09-13 | Dye compound having polymerizable group, and polymer containing same as monomer unit |
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| JP (1) | JP7115489B2 (en) |
| KR (1) | KR102328467B1 (en) |
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| JPH0643586A (en) * | 1992-07-24 | 1994-02-18 | Konica Corp | Silver halide photographic sensitive material |
| JPH09226259A (en) | 1995-12-20 | 1997-09-02 | Konica Corp | Heat sensitive transfer recording material and method for thermal transfer recording |
| JPH1062978A (en) | 1996-08-21 | 1998-03-06 | Konica Corp | Photoinitiator, photopolymerizable composition, method for generating radical, photosensitive material for producing planographic printing plate and production of planographic printing plate |
| JP3650865B2 (en) | 1997-03-28 | 2005-05-25 | コニカミノルタホールディングス株式会社 | Thermal transfer recording material |
| JP3736221B2 (en) | 1998-08-28 | 2006-01-18 | 凸版印刷株式会社 | Color filter and liquid crystal display device having the same |
| DE10111731A1 (en) * | 2001-03-09 | 2002-09-12 | Bayer Ag | Process for the production of asymmetrical methine dyes |
| JP4821095B2 (en) | 2004-07-05 | 2011-11-24 | コニカミノルタホールディングス株式会社 | Pyrazolone dye |
| JP4238184B2 (en) | 2004-07-05 | 2009-03-11 | 大日本印刷株式会社 | Thermal transfer recording material and thermal transfer recording method |
| DE102004036609A1 (en) * | 2004-07-28 | 2006-03-23 | Wella Ag | Cationic pyrazolone dyes, process for their preparation and colorants for keratin fibers containing these compounds |
| JP4617774B2 (en) | 2004-08-26 | 2011-01-26 | コニカミノルタホールディングス株式会社 | Color toner and color filter |
| JP5130630B2 (en) | 2005-03-28 | 2013-01-30 | コニカミノルタホールディングス株式会社 | Coloring composition, ink jet recording liquid, ink jet recording method, color toner, color filter, and metal chelate dye |
| JP5215538B2 (en) * | 2006-06-30 | 2013-06-19 | 富士フイルム株式会社 | Azo dye, coloring composition, thermal transfer recording ink sheet, thermal transfer recording method, color toner, ink jet ink and color filter |
| JP2008176176A (en) * | 2007-01-22 | 2008-07-31 | Konica Minolta Business Technologies Inc | Electrophotographic toner |
| JP2015147825A (en) * | 2014-02-05 | 2015-08-20 | コニカミノルタケミカル株式会社 | Novel pigment compound having polymerizable group |
| JP6326994B2 (en) * | 2014-06-12 | 2018-05-23 | Jsr株式会社 | Colored composition for color filter, colored cured film for color filter, display element, and colorant dispersion for color filter |
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| KR102328467B1 (en) | 2021-11-17 |
| CN111065691A (en) | 2020-04-24 |
| WO2019054436A1 (en) | 2019-03-21 |
| KR20200026948A (en) | 2020-03-11 |
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