CN113316572A - Polymethine compounds - Google Patents

Polymethine compounds Download PDF

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CN113316572A
CN113316572A CN202080009560.7A CN202080009560A CN113316572A CN 113316572 A CN113316572 A CN 113316572A CN 202080009560 A CN202080009560 A CN 202080009560A CN 113316572 A CN113316572 A CN 113316572A
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冈田光裕
斋藤智美
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Adeka Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • 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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Abstract

The present invention addresses the problem of providing a polymethine compound having excellent light resistance and heat resistance. The present invention is a compound represented by formula (I). Preferably R in formula (I)2Is cyano, R3Is an alkyl group having 1 to 5 carbon atoms. In addition, Q in the formula (I) is preferably-CR11R12-. R in the following formula (I) is preferred1、R2、R3、R4、R6、R7、R8、R9And R101 or more of the groups are carboxyl or nitro, or R1、R2、R3、R4、R6、R7、R8、R9And R101 or more hydrogen atoms in the group represented are substituted with a carboxyl group or a nitro group.

Description

Polymethine compounds
Technical Field
The present invention relates to a polymethine compound having a specific structure.
Background
Polymethine compounds are widely used as light absorbers, sensitizers, dyes, and the like in photosensitive materials, dyes, paints, inks, electrophotographic photoreceptors, toners, thermal recording papers, transfer tapes, optical recording pigments, solar cells, photoelectric conversion elements, semiconductor materials, clinical test reagents, pigments for laser therapy, dyes, and the like.
Patent document 1 discloses a silver halide photographic light-sensitive material containing a methine dye compound. Patent document 2 discloses a photoelectric conversion element containing a polymethine compound. Patent document 3 discloses an acid merocyanine dye.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2003-057777
Patent document 2: US2013/0087682A1
Patent document 3: US2526632
Disclosure of Invention
Problems to be solved by the invention
However, the compounds described in patent documents 1 to 3 are insufficient in light resistance and heat resistance.
The purpose of the present invention is to provide a polymethine compound having excellent light resistance and heat resistance.
Means for solving the problems
The present inventors have made extensive studies and, as a result, have found that a polymethine compound having a specific structure can achieve the above object, and have completed the present invention.
The present invention provides the following [1] to [6 ].
[1] A compound represented by the formula (I).
[ chemical formula 1]
Figure BDA0003165812380000021
(in the formula, R2、R3、R4、R5、R7、R8、R9And R10Each independently represents a hydrogen atom, a hydroxyl group, a nitro group, a cyano group, a halogen atom, a carboxyl group, a sulfo group, a sulfamoyl group, a heterocyclic group, a metallocenyl group, a hydrocarbon group having 1 to 30 carbon atoms, or a group in which 1 or 2 or more methylene groups in the hydrocarbon group are substituted by a divalent group selected from the group I, wherein when 2 or more methylene groups are substituted by a divalent group selected from the group I, oxygen atoms of the divalent groups are not adjacent,
R1and R6Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a heterocyclic group, or a group in which 1 or 2 or more methylene groups in the hydrocarbon group are substituted with a divalent group selected from the group I, wherein when 2 or more methylene groups are substituted with a divalent group selected from the group I, oxygen atoms of the divalent group are not adjacent,
q represents-CR11R12-, oxygen atom, sulfur atom or-NR13-，
R11、R12And R13Each independently represents a hydrogen atom, a hydroxyl group, a nitro group, a cyano group, a halogen atom, a carboxyl group, a sulfo group, a sulfamoyl group, a heterocyclic group, a metallocenyl group, a hydrocarbon group having 1 to 30 carbon atoms, or a group in which 1 or 2 or more methylene groups in the hydrocarbon group are substituted by a divalent group selected from the group I, wherein when 2 or more methylene groups are substituted by a divalent group selected from the group I, oxygen atoms of the divalent groups are not adjacent,
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12and R131 to 30 carbon atomsHydrogen atoms or R in hydrocarbon radicals1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12And R13The hydrogen atom in the heterocyclic group represented by (a) may be substituted with a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an oxirane group, a vinyl group, a vinyloxy group, a sulfanyl group, a sulfamoyl group, an isocyanate group or a heterocyclic group,
R7and R8、R8And R9、R9And R10、R10And R11And R11And R12Each of which may be bonded to form a ring, and the ring may have a substituent,
m is an integer of 1 to 3,
when m is greater than or equal to 2, there are a plurality of R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13And Q may be the same or different from each other,
when m is 1, A is not present,
when m is 2 or more, A represents a direct bond, -NR14-, oxygen atom, sulfur atom, -SO2、-SO-、-PR14-、Em+A linking group represented by the following formula (a), formula (b) or (i) or (ii),
[ chemical formula 2]
Figure BDA0003165812380000031
R14Represents a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms or a group in which 1 or 2 or more methylene groups in the hydrocarbon group are substituted with a divalent group selected from the group II, wherein when 2 or more methylene groups are substituted with a divalent group selected from the group II, oxygen atoms of the divalent group are not adjacent,
Em+cation representing the valence of m，
m is more than or equal to 2, A is not Em+In the case of (A) and (R)1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12And R13The position of any one of the groups shown after removal is bonded,
denotes a bonding end.
Group I: -O-, -S-, -CO-, -COO-, -OCO-, -COS-, -OCS-, -SO2-、-SO3-、-NH-、-CONH-、-NHCO-、-SO2NH-、-NH-SO2-N-CH-or a divalent heterocyclic group
Group II: -COO-, -O-, -OCO-, -NHCO-, -NH-or-CONH-)
(i) When m is 2, a may be a linking group represented by the following formula (α).
[ chemical formula 3]
*-Z1-X1-Z2-*(α)
(in the formula, X1represents-NR15A divalent heterocyclic group, a group represented by the formula (. alpha. -1) or the formula (. alpha. -3), a hydrocarbon group having 1 to 30 carbon atoms, or a group in which 1 or 2 or more methylene groups in the hydrocarbon group are substituted with a divalent heterocyclic group,
Z1and Z2Independently represent a direct bond, -O-, -S-, -SO2-、-SO-、-NR15-or-PR16-，
R15And R16Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a group in which 1 or 2 or more methylene groups in the hydrocarbon group are substituted with a divalent group selected from the group III, wherein when 2 or more methylene groups are substituted with a divalent group selected from the group III, oxygen atoms of the divalent group are not adjacent,
denotes a bonding end.
Group III: -COO-, -O-, -OCO-, -NHCO-, -NH-or-CONH-)
[ chemical formula 4]
Figure BDA0003165812380000041
(in the formula, R21Represents a hydrocarbon group having 1 to 30 carbon atoms or a phenyl group substituted with an alkoxy group having 1 to 10 carbon atoms,
R22represents an alkoxy group having 1 to 10 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms or a halogen atom,
the hydrogen atoms of the hydrocarbon group having 1 to 30 carbon atoms and the alkoxy group having 1 to 10 carbon atoms are sometimes substituted with a halogen atom,
d represents an integer of 0 to 4,
denotes a bonding end. )
[ chemical formula 5]
Figure BDA0003165812380000042
(in the formula, R23And R24Each independently represents an aryloxy group having 6 to 20 carbon atoms, an arylsulfanyl group having 6 to 20 carbon atoms, a heterocyclic group, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a group in which 1 or 2 or more methylene groups in the hydrocarbon group are substituted with a divalent group selected from the group IV,
R23and R24The hydrogen atom in the group represented is sometimes substituted with a halogen atom or a heterocyclic group,
with respect to R23Sometimes adjacent R23Are bonded to each other to form a ring,
e represents a number of 0 to 4,
f represents a number of 0 to 8,
g represents a number of 0 to 4,
h represents a number of 0 to 4,
the sum of the numbers of g and h is 2 to 4,
denotes a bonding end.
Group IV: -O-or-S-)
(ii) When m is 3, a may be a linking group represented by the following formula (β).
[ chemical formula 6]
Figure BDA0003165812380000051
(in the formula, X2Represents a trivalent heterocyclic group, a hydrocarbon group having 1 to 30 carbon atoms, or a group in which 1 or 2 or more methylene groups in the hydrocarbon group are substituted with a divalent group selected from the group V, wherein when 2 or more methylene groups are substituted with a divalent group selected from the group V, oxygen atoms of the divalent group are not adjacent,
Z1、Z2and Z3Each independently of the other, Z in the formula (alpha)1And Z2The groups shown are the same groups and are,
the number of carbon atoms of the group represented by the formula (beta) is in the range of 1 to 35,
denotes a bonding end.
Group V: -COO-, -O-, -OCO-, -NHCO-, -NH-, -CONH-, -O-CONH-, -NHCO-O-or a divalent heterocyclic group)
[2] The compound according to [1], wherein it is represented by formula (II).
[ chemical formula 7]
Figure BDA0003165812380000061
(in the formula, R1、R2、R3、R4、R5、R6、R7、R8、R9、R10And Q is the same as the above formula (I).
[3] The compound according to [1], wherein it is represented by formula (III α), (III β) or (III γ).
[ chemical formula 8]
Figure BDA0003165812380000062
(in the formula, R1、R2、R3、R4、R6、R7、R8、R9、R10、Q、X1、Z1And Z2The same as the above formula (I). )
[4]According to [1]～[3]The compound according to any one of the above formulae (I), (II), (III α), (III β) and (III γ)2Is cyano, R3Is an alkyl group having 1 to 5 carbon atoms.
[5]According to [1]～[3]The compound according to any one of the above formulae (I), (II), (III α), (III β) and (III γ)2Is alkyl or haloalkyl.
[6]According to [1]～[4]The polymethine compound of any one of the formulae (I), (II), (III α), (III β) and (III γ) wherein Q is-CR11R12-。
[7]According to [6]The compound of (1), wherein R11And R12Each independently is an alkyl group having 1 to 20 carbon atoms.
[8]According to [1]～[7]The compound according to any one of the above formulae (I), (II), (III α), (III β) and (III γ)1、R2、R3、R4、R5、R6、R7、R8、R9And R101 or more of the groups represented are carboxyl or nitro, or
R in the formulae (I), (II), (III α), (III β) and (III γ)1、R2、R3、R4、R6、R7、R8、R9And R10More than 1 hydrogen atom in the group shown is replaced by carboxyl or nitro.
[9]According to [1]～[8]The compound according to any one of the above formulae (I), (II), (III α), (III β) and (III γ)4、R5、R7、R8、R9And R10At least 1 of the groups represented is a nitro group.
[10]According to [1]～[7]The compound according to any one of the above formulae (I), (II), (III α), (III β) and (III γ)1The group is alkyl with 1-20 carbon atoms or 1 or 2 of the alkylA group obtained by substituting the above methylene group with-O-, -COO-or-OCO-.
[11]According to [10 ]]The compound of the formula (I), (II), (III α), (III β) and (III γ)1The groups shown are substituted with hydroxyl or carboxyl groups.
[12]According to [1]～[7]The compound according to any one of the above formulae (I), (II), (III α), (III β) and (III γ)6The group is an alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a group in which 1 or 2 or more methylene groups in the alkyl group or the alkyl group of the arylalkyl group are substituted with-O-, -COO-or-OCO-.
[13]According to [12 ]]The compound of the formula (I), (II), (III α), (III β) and (III γ)1The groups shown are substituted with acidic groups.
[14]According to [1]～[7]The compound according to any one of the above formulae (I), (II), (III α), (III β) and (III γ)7、R8And R10At least 1 of which is a hydrogen atom.
[15]According to [1]～[7]The compound according to any one of the above formulae (I), (II), (III α), (III β) and (III γ)3Is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms.
[16] A resin composition comprising the compound according to any one of [1] to [15] and a resin.
[17] Use of the compound according to any one of [1] to [15] as a light absorbing agent.
[18] Use of the compound according to any one of [1] to [15] as a sensitizer.
Effects of the invention
According to the present invention, a polymethine compound having excellent light resistance and heat resistance can be provided.
Detailed Description
The compounds of the present invention will be described below based on preferred embodiments. The compounds of the present invention are so-called polymethine compounds. Therefore, the compound of the present invention is hereinafter also referred to as a polymethine compound.
The polymethine compound of the present invention has the structure represented by the above formula (I).
As R2、R3、R4、R5、R7、R8、R9、R10、R11、R12、R13、R23And R24Halogen atom represented by the formula (I), and optionally R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R21、R22、R23And R24Examples of the halogen atom contained in the group include fluorine, chlorine, bromine and iodine.
As R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R21、R22、R23And R24The hydrocarbon group having 1 to 30 carbon atoms is not particularly limited, and examples thereof include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkylalkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, and an arylalkenyl group having 8 to 30 carbon atoms.
The alkyl group having 1 to 20 carbon atoms may be linear or branched. Examples of the straight-chain alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and eicosyl. Examples of the branched alkyl group include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, tert-pentyl group, isooctyl group, 2-ethylhexyl group, tert-octyl group, isononyl group, and isodecyl group. In the present invention, the polymethine compound preferably has an alkyl group having 1 to 10 carbon atoms because of its high absorbance.
The alkenyl group having 2 to 20 carbon atoms may be a chain or a ring. When the alkenyl group is a chain, it may be a terminal alkenyl group having an unsaturated bond at the terminal, or an internal alkenyl group having an unsaturated bond inside. Examples of the terminal alkenyl group having 2 to 20 carbon atoms include a vinyl group, a 2-propenyl group, a 3-butenyl group, a 4-pentenyl group, and a 5-hexenyl group. Examples of the internal alkenyl group include a 2-butenyl group, 3-pentenyl group, 2-hexenyl group, 3-hexenyl group, 2-heptenyl group, 3-heptenyl group, 4-heptenyl group, 3-octenyl group, 3-nonenyl group, 4-decenyl group, 3-undecenyl group and 4-dodecenyl group. Examples of the cyclic alkenyl group include a 3-cyclohexenyl group, a 2, 5-cyclohexadienyl-1-methyl group, and a 4, 8, 12-tetradecatrienylallyl group. In the present invention, the polymethine compound preferably has an alkenyl group having 2 to 10 carbon atoms because of its high absorbance.
The cycloalkyl group having 3 to 20 carbon atoms is a saturated monocyclic or saturated polycyclic alkyl group having 3 to 20 carbon atoms as a whole. Examples of the saturated monocyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl groups. Examples of the saturated polycyclic alkyl group include an adamantyl group, a decahydronaphthyl group, an octahydropentalenyl group, a bicyclo [1.1.1] pentanyl group, and a tetradecahydroanthracenyl group. In the present invention, the polymethine compound preferably has a cycloalkyl group having 3 to 10 carbon atoms because of its high absorbance.
The C4-20 cycloalkylalkyl group is a group in which a hydrogen atom of an alkyl group is substituted with a cycloalkyl group and has 4-20 carbon atoms as a whole. The cycloalkyl group in the cycloalkylalkyl group may be monocyclic or polycyclic. In addition, the methylene group of the alkyl group in the cycloalkylalkyl group may be substituted by-CH ═ CH-.
Examples of the cycloalkylalkyl group having 4 to 20 carbon atoms, the cycloalkyl group of which is a monocyclic ring, include a cycloalkylmethyl group such as a cyclopropylmethyl group, a cyclobutylmethyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, a cycloheptylmethyl group, a cyclooctylmethyl group, a cyclononylmethyl group, and a cyclodecylmethyl group; cycloalkylethyl groups such as 2-cyclobutylethyl, 2-cyclopentylethyl, 2-cyclohexylethyl, 2-cycloheptylethyl, 2-cyclooctylethyl, 2-cyclononylethyl and 2-cyclodecylethyl; cycloalkylpropyl groups such as 3-cyclobutylpropyl, 3-cyclopentylpropyl, 3-cyclohexylpropyl, 3-cycloheptylpropyl, 3-cyclooctylpropyl, 3-cyclononylpropyl and 3-cyclodecylpropyl; cycloalkyl butyl groups such as 4-cyclobutyl butyl, 4-cyclopentylbutyl, 4-cyclohexylbutyl, 4-cycloheptylbutyl, 4-cyclooctylbutyl, 4-cyclononylbutyl and 4-cyclodecylbutyl. Examples of the cycloalkylalkyl group having 4 to 20 carbon atoms, the cycloalkyl group of which is polycyclic, include bicyclo [1.1.0] butyl, bicyclo [1.1.1] pentyl, bicyclo [2.1.0] pentyl, bicyclo [3.1.0] hexyl, bicyclo [2.1.1] hexyl, bicyclo [2.2.0] hexyl, bicyclo [4.1.0] heptyl, bicyclo [3.2.0] heptyl, bicyclo [3.1.1] heptyl, bicyclo [2.2.1] heptyl, bicyclo [5.1.0] octyl, bicyclo [4.2.0] octyl, bicyclo [4.1.1] octyl, bicyclo [3.3.0] octyl, bicyclo [3.2.1] octyl, bicyclo [2.2.2] octyl, spiro [4, 4] nonyl, spiro [4, 5] decyl, decahydronaphthyl, tricyclodecyl, tetracyclo-and cedronyl, cyclododecyl 3-3-adamantylpropyl, and decanaphthyl groups.
In the present invention, the polymethine compound preferably has a cycloalkylalkyl group having 4 to 10 carbon atoms because of its high absorbance.
The aryl group having 6 to 30 carbon atoms may have a monocyclic structure or a condensed ring structure. Further, the aryl group may be a group in which an aryl group having a monocyclic structure and an aryl group having a condensed structure are connected to each other, or a group in which an aryl group having a condensed structure and an aryl group having a condensed structure are connected to each other. Examples of the aryl group having a monocyclic structure include a phenyl group and a biphenyl group. Examples of the aryl group having a condensed ring structure include naphthyl, anthryl, and phenanthryl. The aryl group having 6 to 30 carbon atoms may have 1 or 2 or more substituents. Examples of the substituent include the alkyl group, the alkenyl group, the carboxyl group, and a halogen atom. Examples of the substituted aryl group having 6 to 30 carbon atoms include substituted aryl groups having a single ring structure such as a tolyl group, a xylyl group, an ethylphenyl group, a 4-chlorophenyl group, a 4-carboxyphenyl group, a 4-vinylphenyl group, a 4-methylphenyl group, and a 2, 4, 6-trimethylphenyl group. In the present invention, the polymethine compound preferably has 6 to 10 carbon atoms because of its high absorbance.
The arylalkyl group having 7 to 30 carbon atoms is a group in which 1 or 2 or more hydrogen atoms of the alkyl group are substituted with the aryl group and the whole group has 7 to 30 carbon atoms. Examples of the arylalkyl group having 7 to 30 carbon atoms include phenylalkyl groups such as benzyl, α -methylbenzyl, α -dimethylbenzyl, 2-phenylethyl, 2-phenylpropyl, 3-phenylpropyl, diphenylmethyl, triphenylmethyl, and triphenylpropyl; and naphthylalkyl groups such as naphthylpropyl. In the present invention, a group having 7 to 20 carbon atoms is preferred since the absorbance of the polymethine compound is high.
The arylalkenyl group having 8 to 30 carbon atoms is a group in which a hydrogen atom of the alkenyl group is substituted with the aryl group and which has 8 to 30 carbon atoms as a whole. Examples of the arylalkenyl group having 8 to 30 carbon atoms include styryl, cinnamyl, 2-phenyl-2-propenyl, 3-phenyl-2-propenyl, 2-phenyl-4-pentenyl, 2-phenyl-4-hexenyl, 2-diphenylvinyl, 3-phenyl-2-propenyl, 2-naphthyl-2-propenyl, 3-naphthyl-2-phenyl-2-propenyl, 5-anthryl-2-phenyl-4-hexenyl and 5-anthryl-2-naphthyl-4-hexenyl. In the present invention, an arylalkenyl group having 8 to 20 carbon atoms is preferred since the absorbance of the polymethine compound is high.
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R23And R24The heterocyclic group may have a monocyclic or condensed ring structure. Further, the heterocyclic group may be a heterocyclic group in which a monocyclic heterocyclic group and a monocyclic heterocyclic group are connected to each other, a heterocyclic group in which a monocyclic heterocyclic group and a condensed heterocyclic group are connected to each other, or a heterocyclic group in which a condensed heterocyclic group and a condensed heterocyclic group are connected to each other. As a single ringExamples of the heterocyclic group include pyridyl, pyrimidyl, pyridazinyl, piperazinyl, piperidinyl, pyranyl, pyrazolyl, triazinyl, pyrrolidinyl, imidazolyl, triazolyl, furyl, thienyl, thiadiazolyl, thiazolyl, oxazolyl, isothiazolyl, isoxazolyl, julolidinyl, morpholinyl, thiomorpholinyl, 2-pyrrolidin-1-yl, 2-piperidone-1-yl, 2, 4-dioxoimidazolidin-3-yl and 2, 4-dioxooxazolidin-3-yl. Examples of the heterocyclic group having a condensed ring structure include heterocyclic groups having a condensed ring structure such as a quinolyl group, an isoquinolyl group, a benzimidazolyl group, a benzofuranyl group, a benzothiophenyl group, a benzothiazolyl group, a benzoxazolyl group, and an indolyl group.
The hydrocarbon group having 1 to 30 carbon atoms and the heterocyclic group may have the following substituents.
When the hydrocarbon group having 1 to 30 carbon atoms is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms or a cycloalkylalkyl group having 4 to 20 carbon atoms, examples of the substituent include substituents other than alkyl and arylalkyl groups among the substituents exemplified below.
When the hydrocarbon group having 1 to 30 carbon atoms is an aryl group having 6 to 30 carbon atoms, examples of the substituent include substituents other than the aryl group among the substituents exemplified below.
When the hydrocarbon group having 1 to 30 carbon atoms is an alkenyl group having 2 to 20 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an arylalkenyl group having 8 to 30 carbon atoms, preferable substituents include the following exemplified substituents, among which an aromatic hydrocarbon ring (only a portion of the ring structure, hereinafter, the same applies to "aromatic hydrocarbon ring") having a monocyclic or condensed ring structure or an alkyl group having a connecting structure thereof is preferable.
Among the substituents exemplified below, the alkyl group, arylalkyl group and arylalkenyl group are substituted on an aromatic hydrocarbon ring of an arylalkyl group having 7 to 30 carbon atoms or an arylalkenyl group having 8 to 30 carbon atoms.
Examples of the substituent having 2 to 20 carbon atoms and containing a heterocyclic ring include substituents other than the group containing a heterocyclic ring among the substituents exemplified below.
When the hydrocarbon group having 1 to 30 carbon atoms has a substituent containing a carbon atom among the following substituents, the number of carbon atoms in the whole group including the substituent satisfies a predetermined range. That is, the number of carbon atoms in the case where the hydrocarbon group having 1 to 30 carbon atoms has a substituent having a carbon atom is in the range of 1 to 30 in terms of the whole number including the substituent, and the number of carbon atoms in the case where the alkyl group having 1 to 20 carbon atoms has a substituent having a carbon atom is in the range of 1 to 20 in terms of the whole number including the substituent.
Examples of the substituent include: an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a pentyl group, an isopentyl group, a tert-pentyl group, a cyclopentyl group, a hexyl group, a 2-ethylhexyl group, a 3-hexyl group (or a hexane-3-yl group), a cyclohexyl group, a dicyclohexyl group, a 1-methylcyclohexyl group, a heptyl group, a 2-heptyl group, a 3-heptyl group, an isoheptyl group, a tert-heptyl group, an n-octyl group, an isooctyl group, a tert-octyl group, a nonyl group, an isononyl group, a decyl group, or a lauryl group; alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, tert-butoxy, isobutoxy, pentyloxy, isopentyloxy, tert-pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, isoheptyloxy, tert-heptyloxy, n-octyloxy, isooctyloxy, tert-octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy and the like; alkylthio groups such as methylthio, ethylthio, propylthio, isopropylthio, butylthio, sec-butylthio, tert-butylthio, isobutylthio, pentylthio, isopentylthio, tert-pentylthio, hexylthio, cyclohexylthio, heptylthio, isoheptylthio, tert-heptylthio, n-octylthio, isooctylthio, tert-octylthio, and 2-ethylhexylthio; alkenyl groups such as vinyl, 1-methylvinyl, 2-propenyl, 1-methyl-3-propenyl (or 1-methyl-2-propenyl), 3-butenyl, 1-methyl-3-butenyl, isobutenyl, 3-pentenyl, 4-hexenyl, cyclohexenyl, bicyclohexenyl, heptenyl, octenyl, decenyl, pentadecenyl, eicosenyl, and tricosenyl; arylalkyl groups such as benzyl, phenethyl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl and the like; aryl groups such as phenyl and naphthyl; aryloxy groups such as phenoxy and naphthoxy; arylthio groups such as phenylthio and naphthylthio; a heterocyclic ring-containing group such as a pyridyl group, a pyrimidinyl group, a pyridazinyl group, a piperidyl group, a pyranyl group, a pyrazolyl group, a triazinyl group, a pyrrolyl group, a quinolyl group, an isoquinolyl group, an imidazolyl group, a benzimidazolyl group, a triazolyl group, a furyl group, a benzofuryl group, a thienyl group, a thiophenyl group, a benzothiophenyl group, a thiadiazolyl group, a thiazolyl group, a benzothiazolyl group, an oxazolyl group, a benzoxazolyl group, an isothiazolyl group, an isoxazolyl group, an indolyl group, a 2-pyrrolidone-1-yl group, a 2-piperidone-1-yl group, a 2, 4-dioxoimidazolidin-3-yl group, or a 2, 4-dioxooxazolidin-3-yl group; halogen atoms such as fluorine, chlorine, bromine and iodine; acyl groups such as acetyl, 2-chloroacetyl, propionyl, octanoyl, phenylcarbonyl (benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl, salicyloyl, oxalyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl, and carbamoyl; acyloxy groups such as acetoxy and benzoyloxy; amino, ethylamino, dimethylamino, diethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, chlorophenylamino, toluidino, anisylamino, N-methyl-anilino, diphenylamino, naphthylamino, 2-pyridylamino, methoxycarbonylamino, phenoxycarbonylamino, acetylamino, benzoylamino, formylamino, pivaloylamino, lauroylamino, carbamoylamino, N-dimethylaminocarbonylamino, N-diethylaminocarbonylamino, morpholinocarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, N-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino, phenoxycarbonylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, chlorophenylamino, tolylamino, and the like, Substituted amino groups such as sulfamoylamino, N-dimethylaminosulfonylamino, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino and the like; an acidic group such as a carboxyl group, a sulfosulfamoyl group, a sulfonyl group-containing group, a cyano group, a sulfo group, a phosphoric group, or a sulfamino group; hydroxyl, nitro, sulfanyl, imino, carbamoyl, and the like, which may be further substituted.
The acidic group such as the carboxyl group, sulfo group, sulfamino group, phosphoric group, or the like may form a salt with various cations, and the substituted amino group (e.g., diethylamino group, dimethylamino group) may be quaternized, for example, with an alkyl group having 1 to 10 carbon atoms such as a methyl group or an ethyl group, and then formed into a salt with various anions. Examples of the cation include alkali metal ions, alkaline earth metal ions, transition metal cations, ammonium having 4 or more carbon atoms, amidinium, guanidinium cations, and examples of the anion include monovalent anions such as halide ions including chloride, bromide, iodide, and fluoride; inorganic anions such as perchlorate, chlorate, thiocyanate, hexafluorophosphate, hexafluoroantimonate and tetrafluoroborate; organic sulfonic acid system anions such as methanesulfonate ion, dodecylsulfonate ion, benzenesulfonate ion, toluenesulfonate ion, trifluoromethanesulfonate ion, pentafluorobenzenesulfonate ion, diphenylamine-4-sulfonate ion, 2-amino-4-methyl-5-chlorobenzenesulfonate ion, 2-amino-5-nitrobenzenesulfonate ion, phthalocyanine sulfonate ion, perfluoro-4-ethylcyclohexane sulfonate ion, naphthalene monosulfonic acid, naphthalene disulfonic acid, naphthalene trisulfonic acid, naphthylamine monosulfonic acid, naphthylamine disulfonic acid, naphthylamine trisulfonic acid, naphthol monosulfonic acid, naphthol disulfonic acid, naphthol trisulfonic acid, and the like; thiocyanate ion, phosphotungstic acid ion, phosphomolybdate ion, tannate ion, tartrate ion, palmitate ion, stearate ion, oleate ion, linoleate ion, octylphosphate ion, dodecylphosphate ion, octadecylphosphate ion, phenylphosphate ion, nonylphenylphosphate ion, 2' -methylenebis (4, 6-di-t-butylphenyl) phosphonate ion and other organic phosphate anions, bistrifluoromethanesulfonylimide ion, bisterfluorobutanesulfonylimide ion, tetrakis (pentafluorophenyl) borate ion, tris (fluoroalkylsulfonyl) carbanion, tetrakis (pentafluorophenyl) borate anion and the like.
As R2、R3、R4、R5、R7、R8、R9、R10、R11、R12And R13Examples of the metallocene group include ferrocenyl, nickelocene group, cobaltocene group, ferrocenyl alkoxy, and the like.
As R7And R8、R8And R9、R9And R10、R10And R11、R11And R12And adjacent R13Examples of the ring structure formed by bonding to each other include cycloalkyl rings such as cyclopentane, cyclohexane, and cycloheptane rings; aromatic rings such as benzene rings; and heterocyclic rings such as a piperidine ring, a piperazine ring, a pyrrolidine ring, a morpholine ring, a thiomorpholine ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a quinoline ring, an isoquinoline ring, an imidazole ring, an oxazole ring, an imidazolidine ring, a pyrazolidine ring, an isoxazolidine ring, an iminooxazolidine ring, an isothiazolidine ring, a rhodanine ring, a thioxooxazolone ring, an hydantoin ring, an indandione ring, a thienylone ring, a pyrazolone ring, a pyridone ring, a pyrazolone dione ring, a rhodanine ring, a barbituric acid ring, a thiobarbituric acid ring, an oxazolone ring, a hydantoin ring, an hydantoin ring, a succinimide ring, and a maleimide ring, which may be fused with other rings. These rings sometimes have a general formula of R4、R5、R7、R8、R9And R10The same substituent such as the hydrocarbon group having 1 to 30 carbon atoms.
As X in formula (α)1Examples of the hydrocarbon group having 1 to 30 carbon atoms include those derived from R1And (c) a divalent group derived from a hydrocarbon group having 1 to 30 carbon atoms by removing any 1 hydrogen atom. Further, a group represented by the following formula (. alpha. -2) may be mentioned.
[ chemical formula 8A ]
Figure BDA0003165812380000141
(. represents a bonding end.)
As X in formula (α)1The divalent heterocyclic groups shown, and the divalent heterocyclic groups in groups I and VBy the reaction of R1And (c) a divalent group derived from the heterocyclic group shown by (a) and (b) by removing any 1 hydrogen atom.
When the group represented by the formula (α) contains a carbon atom, the number of carbon atoms is preferably in the range of 1 to 35.
In the formula (. alpha. -1), as R21Alkoxy group having 1 to 10 carbon atoms in the group and R22Examples of the alkoxy group having 1 to 10 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, tert-butoxy, isobutoxy, pentoxy, isopentoxy, tert-pentoxy, hexoxy, cyclohexyloxy, heptoxy, isoheptoxy, tert-heptoxy, n-octoxy, isooctoxy, tert-octoxy, 2-ethylhexoxy, nonoxy, and decyloxy.
In the above general formula (. alpha. -3), R is23And R24Examples of the aryloxy group having 6 to 20 carbon atoms include a phenoxy group, a naphthoxy group, a 2-methylphenyloxy group, a 3-methylphenyloxy group, a 4-vinylphenyldioxy group, a 3-isopropylphenyloxy group, a 4-butylphenyloxy group, a 4-tert-butylphenyloxy group, a 4-hexylphenyloxy group, a 4-cyclohexylphenyloxy group, a 4-octylphenyloxy group, a 4- (2-ethylhexyl) phenyloxy group, a 2, 3-dimethylphenyloxy group, a 2, 4-dimethylphenyloxy group, a 2, 5-dimethylphenyloxy group, a 2, 6-dimethylphenyloxy group, a 3, 4-dimethylphenyloxy group, a 3, 5-dimethylphenyloxy group, and a 2, 4-di-tert-butylphenyloxy group, 2, 5-di-tert-butylphenyloxy group, 2, 6-di-tert-butylphenyloxy group, 2, 4-di-tert-pentylphenyloxy group, 2, 5-tert-pentylphenyloxy group, 4-cyclohexylphenyloxy group, 2, 4, 5-trimethylphenyloxy group, ferrocenyloxy group and the like, and groups obtained by substituting these groups with a halogen atom.
In the above general formula (. alpha. -3), R is23And R24Examples of the arylsulfanyl group having 6 to 20 carbon atoms include a group obtained by replacing an oxygen atom of the aryloxy group having 6 to 20 carbon atoms with a sulfur atom.
R in the above formula (. alpha. -3)23Formed by bonding to each otherA ring structure and R7And R8、R8And R9、R9And R10、R10And R11、R11And R12And adjacent R13The ring structures formed by bonding to each other are the same.
In the above formula (. beta.), X2Each of the hydrocarbon groups having 1 to 30 carbon atoms represented by the formula (I) is represented by the formula (II)1And a trivalent hydrocarbon group derived by removing any 2 hydrogen atoms from the hydrocarbon group having 1 to 30 carbon atoms. Likewise, X2The trivalent heterocyclic radicals shown are respectively from R1、R2、R3、R4、R6And R7A trivalent group derived by removing any 2 hydrogen atoms from the heterocyclic group shown.
The terminal methyl group of the hydrocarbon group having 1 to 30 carbon atoms in the formula (I) may have a substituent obtained by forming a salt with various cations by an acidic group such as a carboxyl group, a sulfo group, or a phosphate group, or may have a substituent obtained by forming a salt with various anions after quaternizing a substituted amino group.
Among the substituents forming such salts, examples of cations forming salts with acidic groups include alkali metal ions such as lithium, sodium, and potassium, alkaline earth metal ions such as magnesium, calcium, strontium, and barium, typical metal ions such as aluminum, transition metal cations such as zinc, nickel, cobalt, copper, and vanadium, and ammonium having 4 or more carbon atoms, examples of anions forming salts with quaternized substituted amino groups include halide ions such as chloride, bromide, iodide, and fluoride; inorganic anions such as perchlorate ion, hexafluorophosphate ion, hexafluoroantimonate ion, tetrafluoroborate ion and the like; organic sulfonic acid anions such as methanesulfonate ion and dodecylsulfonate ion; heteropoly acid ions such as phosphomolybdate ions, bistrifluoromethylsulfonyl imide ions, bisterfluorobutanesulfonimide ions, tetrakis (pentafluorophenyl) borate ions, tris (fluoroalkylsulfonyl) carbanions, tetrakis (pentafluorophenyl) borate anions, and the like.
The substituent having a salt formed thereon can be obtained by using a precipitant for laking an acid dye or a precipitant for laking a basic dye. Examples of the precipitant for laking the acidic dye include barium chloride, aluminum chloride, alkaline earth metal salts, manganese salts, and sodium salts, and examples of the precipitant for laking the basic dye include phosphotungstic acid, phosphomolybdic acid, silicotungstomolybdic acid, silicomolybdic acid, tannic acid, tartaric acid, kaolin, smectite, and higher fatty acids, and the precipitant can be obtained by heating and filtering in an aqueous solution or aqueous dispersion as necessary.
A of the polymethine compounds of the invention in the above formula (I) is Em+In the case where m is 2 or more, and the moiety other than A in the formula (I) is r monovalent anions, these anions are Em+The m-valent cation bond state. The compounds No.5, No.11 and No.66 to No.77 are the same as the exemplified compounds described later.
Em+The m-valent cation is monovalent or more, preferably divalent or more. Examples of the divalent cation include alkaline earth metal ions such as magnesium, calcium, strontium, and barium; transition metal cations such as zinc, copper, and nickel, and the trivalent cation includes typical metal ions such as aluminum; transition metal cations such as cobalt and iron, and examples of cations having a valence of 4 or more include transition metal cations such as manganese.
The polymethine compound of the present invention represented by the above formula (I) may have a structure represented by the following formula, but may have any structural formula, and structural isomers represented by any structural formula may be used by separating them, or may be used as a mixture thereof. Further, in the following formula, NR6Radical and R5The groups are in cis configuration (Z configuration) with respect to the double bond, but compounds in which these groups are in trans configuration (E configuration) are also included in the polymethine compounds of the present invention. The above formula (I) is defined as a general formula containing all geometric isomers resulting from these carbon-carbon double bonds.
[ chemical formula 9]
Figure BDA0003165812380000161
(in the formula, R1、R2、R3、R4、R5、R6、R7、R8、R9、R10And Q is the same as the above formula (I).
In the formulae (II), (III α), (III β), and (III γ), as in the formula (I), there are geometric isomers in which the double bond is in the cis configuration (Z configuration) or the trans configuration (E configuration), respectively, but the polymethine compound of the present invention is defined as a compound including all the geometric isomers due to these carbon-carbon double bonds, without distinguishing them.
Specific examples of the polymethine compound of the present invention represented by the above formula (I) include the following compounds No.1 to No. 89.
[ chemical formula 10]
Figure BDA0003165812380000181
[ chemical formula 11]
Figure BDA0003165812380000191
[ chemical formula 12]
Figure BDA0003165812380000201
[ chemical formula 13]
Figure BDA0003165812380000211
[ chemical formula 14]
Figure BDA0003165812380000221
[ chemical formula 15]
Figure BDA0003165812380000231
[ chemical formula 16]
Figure BDA0003165812380000241
[ chemical formula 17]
Figure BDA0003165812380000251
[ chemical formula 18]
Figure BDA0003165812380000261
[ chemical formula 19]
Figure BDA0003165812380000271
[ chemical formula 20]
Figure BDA0003165812380000281
[ chemical formula 21]
Figure BDA0003165812380000291
[ chemical formula 22]
Figure BDA0003165812380000301
[ chemical formula 23]
Figure BDA0003165812380000311
[ chemical formula 24]
Figure BDA0003165812380000321
[ chemical formula 25]
Figure BDA0003165812380000331
[ chemical formula 26]
Figure BDA0003165812380000341
The polymethine compounds represented by the above formulae (I), (II), (III α), (III β) and (III γ) are preferably R4、R5、R7、R8、R9And R10At least 1 of the groups shown is nitro.
In the polymethine compounds represented by the above formulae (I), (II), (III α), (III β) and (III γ), R is1And R6At least 1 of the groups shown is preferably a group having an acidic group. The acidic group is preferably a carboxyl group, a sulfo group or a sulfamino group.
In the polymethine compounds represented by the above formulae (I), (II), (III α), (III β) and (III γ), R is a compound having high solubility in a solvent1And R6At least 1 of the groups shown is preferably a group having a branch.
In the polymethine compounds represented by the above formulae (I), (II), (III α), (III β) and (III γ), R is selected from the group consisting of heat resistance and solubility in a solvent1The group is preferably an alkyl group having 1 to 20 carbon atoms or a group in which 1 or 2 or more methylene groups in the alkyl group are substituted with-O-, -COO-or-OCO-. The number of carbon atoms of the alkyl group is preferably 1 to 10. In addition, the alkyl group is preferably unsubstituted, or toOne less hydrogen atom is replaced by a hydroxyl group or a carboxyl group.
In the polymethine compounds represented by the above formulae (I), (II), (III α), (III β) and (III γ), R is R from the viewpoint of heat resistance and solubility in a solvent of the compounds6The group is preferably an alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a group in which 1 or 2 or more of methylene groups in the alkyl group or methylene groups in the alkyl group of the arylalkyl group are substituted with-O-, -COO-or-OCO-. The number of carbon atoms of the alkyl group is preferably 1 to 10. The alkyl group and the arylalkyl group are preferably unsubstituted or at least one hydrogen atom is substituted with an acidic group such as a carboxyl group, a sulfo group, or a sulfoamino group.
The polymethine compounds represented by the above formulae (I), (II), (III α), (III β) and (III γ) are preferably R6Is a group represented by the following formula.
[ chemical formula 27]
Figure BDA0003165812380000361
(wherein means bonding to an adjacent group at the moiety.)
The polymethine compounds represented by the above formulae (I), (II), (III α), (III β) and (III γ) are preferably R3Is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, and more preferably an alkyl group having 1 to 20 carbon atoms. The number of carbon atoms of the alkyl group is preferably 1 to 4. The alkyl group is preferably unsubstituted or substituted with a halogen atom, cyano group, nitro group or carboxyl group, more preferably unsubstituted or substituted with a halogen atom. The aryl group is preferably substituted with a C1-4 haloalkyl group, a halogen atom, a cyano group, a nitro group or a carboxyl group.
The polymethine compounds represented by the above formulae (I), (II), (III α), (III β) and (III γ) are preferably R3Is a group represented by the following formula.
[ chemical formula 28]
Figure BDA0003165812380000371
(wherein means bonding to an adjacent group at the moiety.)
Q in the formulae (I), (II), (III α), (III β) and (III γ) is preferably-CR11R12-. as-CR11R12The group represented by the following formula is preferable.
[ chemical formula 29]
Figure BDA0003165812380000372
(wherein means bonding to an adjacent group at the moiety.)
The linking group represented by the formula (α) is preferably a group represented by the following formula.
[ chemical formula 30]
Figure BDA0003165812380000373
(wherein means bonding to an adjacent group at the moiety.)
The linking group represented by the formula (β) is preferably a group represented by the following formula.
[ chemical formula 31]
Figure BDA0003165812380000381
(wherein means bonding to an adjacent group at the moiety.)
Among the polymethine compounds represented by the formula (I) of the present invention, the polymethine compounds represented by the formula (II) are preferable because they have a sharp absorption wavelength region.
Among the polymethine compounds represented by formula (I) of the present invention, the polymethine compounds represented by the above formulae (III α), (III β) and (III γ) are preferred because of their high heat resistance.
R in the formulae (I), (II), (III α), (III β) and (III γ)2Is cyano, and R3The polymethine compound having an alkyl group of 1 to 5 carbon atoms is particularly preferable because of its excellent light resistance and heat resistance.
Q in the formulae (I), (II), (III α), (III β) and (III γ) is-CR11R12The polymethine compound (E) is particularly preferable because it is particularly excellent in light resistance and heat resistance. R11And R12Each independently preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group is preferably unsubstituted.
R in the formulae (I), (II), (III α), (III β) and (III γ)1、R2、R3、R4、R6、R7、R8、R9And R10Among the groups shown, a polymethine compound in which 1 or more is a carboxyl group or a nitro group is preferable because of its particularly excellent light resistance and heat resistance.
R in the formulae (I), (II), (III α), (III β) and (III γ)1、R2、R3、R4、R6、R7、R8、R9And R10The polymethine compound in which 1 or more hydrogen atoms in the group are substituted with a carboxyl group or a nitro group is preferable because of its particularly excellent light resistance and heat resistance.
R in the above formulae (I), (II), (III α), (III β) and (III γ)2The polymethine compound having a cyano group is particularly preferable because it is particularly excellent in light resistance and heat resistance.
R in the above formulae (I), (II), (III α), (III β) and (III γ)2The polymethine compound which is an alkyl group or a halogenated alkyl group is preferable because it is excellent in light resistance and heat resistance. R2The trifluoromethyl group is preferred because it is particularly excellent in light resistance and heat resistance.
R in the above formulae (I), (II), (III α), (III β) and (III γ)7、R8And R10At least 1 of them is preferably a hydrogen atom, more preferably all hydrogen atoms.
The polymethine of the present invention represented by the above formula (I)The base compound is not particularly limited in its production method, and can be obtained by a method utilizing a known general reaction. For example, when m is 1, N-methylmorpholine (hereinafter also referred to as NMM) and acetic anhydride (hereinafter also referred to as Ac) can be used as shown in the following reaction formula 12O) with pyridone bodies in the presence of a catalyst.
[ chemical formula 32]
Reaction scheme 1
Figure BDA0003165812380000391
(in the formula, R1～R10And Q is the same as the above formula (I), and An-represents a monovalent anion. )
When m is 2 and a is bonded to R in the formula (I), R is not particularly limited1The position of (3) can be determined by adding NMM and Ac as shown in the following reaction formula 22Reacting a specific indolenine quaternary salt with R in the presence of O1A method of reacting 2-mers of pyridone bodies crosslinked with each other.
[ chemical formula 33]
Reaction formula 2
Figure BDA0003165812380000401
(in the formula, A, R1～R10And Q is the same as the above formula (I), and An-represents a monovalent anion. )
The polymethine compound of the present invention is useful as a light absorber, sensitizer or the like for photosensitive photographic materials, dyes, paints, inks, electrophotographic photoreceptors, toners, thermal recording papers, transfer tapes, optical recording pigments, solar cells, photoelectric conversion elements, semiconductor materials, clinical test reagents, pigments for laser therapy, dyes or the like.
The composition of the present invention contains the polymethine compound of the present invention, and is used for various applications as described above. The composition of the present invention usually contains a resin according to the use in addition to the polymethine compound of the present invention.
The composition of the present invention may further contain, in addition to the above, optional components such as necessary components, for example, an organic solvent described later, a light absorbing agent other than the polymethine compound of the present invention, and various stabilizers, in an amount necessary for the purpose.
The amount of the polymethine compound of the present invention and the above-mentioned resin in the composition of the present invention is not particularly limited, and may be suitably determined depending on the application.
Examples
The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.
Production example 1-1 Synthesis of pyridone body 1
Butylamine (6.0g, 82.0mmol) and ethyl cyanoacetate (11.1g, 98.4mmol) were mixed at room temperature, heated to 70 ℃ under nitrogen and stirred for 2 h. Ethyl acetoacetate (15.0g, 114.9mmol) and piperidine (7.7g, 90.2mmol) were added dropwise, the mixture was heated to 100 ℃ and stirred for 8 hours. The reaction solution was cooled to room temperature, and then poured into hydrochloric acid (12.8g, 123.1mmol), followed by stirring for 1 hour. The precipitated white crystals were filtered to obtain 9.9g (yield 58.7%) of pyridone 1 described below.
[ chemical formula 34]
Figure BDA0003165812380000411
Production example 1-2 Synthesis of pyridone body 2
The same operation was carried out with the butylamine of production example 1-1 being changed to 1, 6-diaminohexane, whereby the following pyridone body 2 was obtained in a yield of 63.6%.
[ chemical formula 35]
Figure BDA0003165812380000412
Production examples 1 to 3 Synthesis of pyridone body 3
The same operation was carried out with ethyl acetoacetate from production example 1-1 changed to ethyl 4, 4, 4-trifluoroacetoacetate, whereby the following pyridone body 3 was obtained in a yield of 42.2%.
[ chemical formula 36]
Figure BDA0003165812380000421
Production examples 1 to 4 Synthesis of pyridone body 4
The same operation was carried out with the butylamine of production example 1-1 being changed to DL-1-amino-2-propanol, whereby the following pyridone body 4 was obtained in a yield of 57.6%.
[ chemical formula 37]
Figure BDA0003165812380000422
Production examples 1 to 5 Synthesis of pyridone body 5
The same operation was carried out with the butylamine of production example 1-1 being changed to 3-amino-1-propanol, whereby the following pyridone body 5 was obtained in a yield of 40.0%.
[ chemical formula 38]
Figure BDA0003165812380000423
Production examples 1 to 6 Synthesis of pyridone body 6
The same operation was carried out with respect to butylamine in production example 1-1 being changed to glycine ethyl ester hydrochloride, whereby the following pyridone body 6 was obtained in a yield of 67.6%.
[ chemical formula 39]
Figure BDA0003165812380000431
Production examples 1 to 7 Synthesis of pyridone body 7
The same operation was carried out with respect to butylamine in production example 1-1 being changed to 2-ethylhexylamine, whereby the following pyridone compound 7 was obtained in a yield of 78.3%.
[ chemical formula 40]
Figure BDA0003165812380000432
Production examples 1 to 8 Synthesis of pyridone body 8
The same operation was carried out with respect to the butylamine of production example 1-1 being changed to 3- (2-ethylhexyloxy) propylamine, whereby the following pyridone body 8 was obtained in a yield of 67.6%.
[ chemical formula 41]
Figure BDA0003165812380000441
[ PRODUCTION EXAMPLE 2-1] Synthesis of indolenine Quaternary salt 1
The known quaternary salt of benzindole (22.7g, 30.0mmol) and N, N' -diphenylformamidine (11.8g, 60.0mmol) were dissolved in DMAc at room temperature and stirred at 110 ℃ for 4 hours. N, N' -diphenylformamidine (7.4g, 37.5mmol) was added again, and the reaction was stopped by adding water (2.2g) after reacting at 110 ℃ for 4 hours. The precipitated crystals were crystallized from ethyl acetate to obtain the following indolenine quaternary salt 1 in a yield of 49.0%.
[ chemical formula 42]
Figure BDA0003165812380000442
[ PREPARATION EXAMPLE 2-2] Synthesis of Quaternary indolenine salt 3
The known indolenine quaternary salt 2(30.8g, 147.0mmol) and diiodohexane (2.38g, 70.0mmol) were dissolved in DMAc (53.0g), and the mixture was stirred at 110 ℃ for 4 hours. After cooling to 50 ℃ and crystallization from acetone (105g), 37.9g (yield: 71.5%) of the following indolenine quaternary salt 3 was obtained.
[ chemical formula 43]
Figure BDA0003165812380000451
[ PREPARATION EXAMPLES 2-3] Synthesis of Quaternary indolenine salt 5
The same procedures as for the known indolenine quaternary salt 4 described below were carried out except for changing the indolenine quaternary salt 2 of production example 2-1 to give the indolenine quaternary salt 5 described below quantitatively.
[ chemical formula 44]
Figure BDA0003165812380000452
[ PREPARATION EXAMPLES 2-4] Synthesis of Quaternary indolenine salt 7
The same procedures as for the known indolenine quaternary salt 6 described below were carried out except for changing the indolenine quaternary salt 2 of production example 2-1 to give the indolenine quaternary salt 7 described below quantitatively.
[ chemical formula 45]
Figure BDA0003165812380000453
[ PREPARATION EXAMPLES 2-5] Synthesis of Quaternary indolenine salt 8
Nitroindole (70mmol) and β -bromophenylether (84mmol) were dissolved in DMAc (53g) at room temperature and heated at 110 ℃ for 4 hours. After the reaction, an aqueous solution of chloroform and sodium perchlorate (70mmol) was added thereto, and oil-water separation was performed. The organic layer was concentrated to give the following indolenine quaternary salt 8 in 85% yield.
[ chemical formula 46]
Figure BDA0003165812380000461
[ PREPARATION EXAMPLES 2-6] Synthesis of Quaternary indolenine salt 9
The same procedures as for the above-mentioned indolenine quaternary salt 8 were carried out except for changing the indolenine quaternary salt 2 of production example 2-1 to give the following indolenine quaternary salt 9 quantitatively.
[ chemical formula 47]
Figure BDA0003165812380000462
Production examples 2 to 7 Synthesis of indolenine ester 1
Nitroindole (70.0mmol) and ethyl 4-bromopropionate (84.0mmol) were dissolved in DMAc (53.0g) at room temperature and stirred at 110 ℃ for 4 h. After cooling to 50 ℃ and crystallization from acetone (105g), the following indolenine ester 1 was obtained in 91.6% yield.
[ chemical formula 48]
Figure BDA0003165812380000471
Production examples 2 to 8 Synthesis of indolenine ester 2
The same procedures as in preparation example 2-1 were carried out except for changing the quaternary indolenine salt 2 to the above indolenine ester 1, whereby the following indolenine ester 2 was quantitatively obtained.
[ chemical formula 49]
Figure BDA0003165812380000472
EXAMPLE 1 Synthesis of Compound No.1
The pyridone 1(1.8g, 8.8mmol) and indolenine quaternary salt 1(4.0g, 8.8mmol) were dissolved in DMAc (21.0g) at room temperature, and stirred at 70 ℃ for 1 hour. Subsequently, N-methylmorpholine (1.8g, 17.6mmol) and acetic anhydride (7.7g) were added thereto, and the mixture was stirred at 50 ℃ for 1 hour under a nitrogen atmosphere. After cooling to room temperature, the precipitated red crude crystals were filtered. The crude crystals were dispersed in MeOH and stirred for 1 hour. The crystals were filtered, dried under reduced pressure, and then 2.0g (yield 51.2%) of the compound No.1 was obtained.
[ chemical formula 50]
Figure BDA0003165812380000481
EXAMPLE 2 Synthesis of Compound No.2
The same operation was carried out with the indolenine quaternary salt 1 of example 1 changed to the above indolenine quaternary salt 3, whereby the following compound No.2 was obtained in a yield of 27.9%.
[ chemical formula 51]
Figure BDA0003165812380000482
EXAMPLE 3 Synthesis of Compound No.3
The same operation was carried out with the change from pyridone body 1 of example 1 to pyridone body 2, whereby the following compound No.3 was obtained in a yield of 38.4%.
[ chemical formula 52]
Figure BDA0003165812380000483
Example 4 Synthesis of Compound No.4
Compound No.1(2.6g, 6.4mmol) was dissolved in concentrated sulfuric acid (11.9g) at room temperature, and stirred at 95 ℃ for 2 hours. The reaction mixture was poured into ice water, and the precipitated red crystals were filtered to obtain 2.1g (yield 76.4%) of the following compound No. 4.
[ chemical formula 53]
Figure BDA0003165812380000491
EXAMPLE 5 Synthesis of Compound No.5
After the above-mentioned compound No.4(1.8g, 4.2mmol) was dispersed in ion-exchanged water (181.0g) and stirred for 10 minutes at room temperature, a 5.3M aqueous solution of sodium hydroxide (0.8g) was added and stirred for 30 minutes. The reaction solution was DFP-filtered, and then 0.8M aqueous barium chloride solution (2.4g) was added dropwise thereto and stirred for 1 hour. The precipitated red crystals were collected by filtration to obtain 1.2g (yield: 62.6%) of Compound No. 5.
[ chemical formula 54]
Figure BDA0003165812380000492
EXAMPLE 6 Synthesis of Compound No.6
The same operation was carried out with the change from pyridone body 1 of example 1 to pyridone body 3, whereby compound No.6 was obtained in 52.4% yield.
[ chemical formula 55]
Figure BDA0003165812380000493
EXAMPLE 7 Synthesis of Compound No.7
The same operation was carried out with the pyridone body 1 of example 1 changed to the pyridone body 3 and the indolenine quaternary salt 1 changed to the indolenine quaternary salt 5, whereby the following compound No.7 was obtained in a yield of 15.8%.
[ chemical formula 56]
Figure BDA0003165812380000501
EXAMPLE 8 Synthesis of Compound No.8
Toluene (2.16g) and a 5M methanol solution (2.6mL, 1.3mmol) of sodium methoxide were mixed, and the above-mentioned compound No.7(0.76g, 1.3mmol) was added in several portions under ice-cooling. After stirring at this temperature for 4 hours, 2N hydrochloric acid was added dropwise. After stirring for 1 hour, the precipitated crystals were filtered. Toluene was added to the crystals, and after washing at room temperature for 30 minutes, the crystals were filtered again to obtain 0.56g (yield 78.0%) of the following compound No. 8.
[ chemical formula 57]
Figure BDA0003165812380000502
EXAMPLE 9 Synthesis of Compound No.9
The same operation was carried out with the change from pyridone body 1 of example 1 to pyridone body 3 and from indolenine quaternary salt 1 to indolenine quaternary salt 7, whereby the following compound No.9 was obtained in a yield of 10%.
[ chemical formula 58]
Figure BDA0003165812380000511
EXAMPLE 10 Synthesis of Compound No.10
The same operation was carried out with the compound No.7 used in example 8 changed to the compound No.9, whereby the following compound No.10 was obtained in a yield of 84.8%.
[ chemical formula 59]
Figure BDA0003165812380000512
EXAMPLE 11 Synthesis of Compound No.11
The same operation was carried out by changing the compound No.4 used in example 5 to the compound No.10, whereby the following compound No.11 was obtained in a yield of 91.3%.
[ chemical formula 60]
Figure BDA0003165812380000513
EXAMPLE 12 Synthesis of Compound No.12
The same operation was carried out by changing the indolenine quaternary salt 1 of example 1 to the indolenine quaternary salt 7, whereby the following compound No.12 was obtained in a yield of 40%.
[ chemical formula 61]
Figure BDA0003165812380000521
EXAMPLE 13 Synthesis of Compound No.13
The same operation was carried out with the compound No.7 used in example 8 changed to the compound No.12, so as to obtain the following compound No.13 with a yield of 85.0%.
[ chemical formula 62]
Figure BDA0003165812380000522
EXAMPLE 14 Synthesis of Compound No.14
The same operation was carried out with the change of pyridone body 1 of example 1 to pyridone body 4 and the change of indolenine quaternary salt 1 to indolenine quaternary salt 7, whereby the following compound No.14 was obtained in a yield of 36.2%.
[ chemical formula 63]
Figure BDA0003165812380000523
EXAMPLE 15 Synthesis of Compound No.15
The same operation was carried out with the compound No.7 used in example 8 changed to the compound No.14, whereby the following compound No.15 was obtained in a yield of 15.2%.
[ chemical formula 64]
Figure BDA0003165812380000531
EXAMPLE 16 Synthesis of Compound No.16
The same operation was carried out with changing pyridone body 1 of example 1 to pyridone body 5, whereby the following compound No.16 was obtained in a yield of 17.1%.
[ chemical formula 65]
Figure BDA0003165812380000532
EXAMPLE 17 Synthesis of Compound No.17
The same operation was carried out with the compound No.7 used in example 8 changed to the compound No.16, so as to obtain the following compound No.17 in a yield of 15.2%.
[ chemical formula 66]
Figure BDA0003165812380000533
EXAMPLE 18 Synthesis of Compound No.18
Compound No.17(2.4g, 4.8mmol), succinic anhydride (1.2g, 5.8mmol) and DMAP (0.1g, 1.2mmol) were dissolved in pyridine (4.8g), and stirring was carried out at 60 ℃ for 1.5 hours. After confirming the disappearance of the starting material by HPLC, the mixture was cooled to room temperature, and chloroform and 2N hydrochloric acid were added to adjust the pH to 4. After extraction, the organic layer was washed 2 times with 2N hydrochloric acid and 2 times with water. The organic layer was dried over sodium sulfate, filtered and concentrated under reduced pressure to give the crude product. The crude product was dispersed in water (24g), filtered and dried under reduced pressure to obtain 2.2g (yield 76.2%) of Compound No. 18.
[ chemical formula 67]
Figure BDA0003165812380000541
EXAMPLE 19 Synthesis of Compound No.19
The same operation was carried out by changing the indolenine quaternary salt 1 of example 1 to the indolenine quaternary salt 9, whereby the following compound No.19 was obtained in a yield of 60.0%.
[ chemical formula 68]
Figure BDA0003165812380000542
EXAMPLE 20 Synthesis of Compound No.20
The same operation was carried out with the change of pyridone body 1 of example 1 to pyridone body 4 and the change of indolenine quaternary salt 1 to indolenine quaternary salt 9, whereby the following compound No.20 was obtained in a yield of 69.2%.
[ chemical formula 69]
Figure BDA0003165812380000551
EXAMPLE 21 Synthesis of Compound No.21
The same operation was carried out with the compound No.7 used in example 8 changed to the compound No.20, so as to obtain the following compound No.21 in a yield of 92.7%.
[ chemical formula 70]
Figure BDA0003165812380000552
EXAMPLE 22 Synthesis of Compound No.22
The same operation was carried out with the compound No.17 used in example 18 changed to the compound No.21, so as to obtain the following compound No.22 in a yield of 79.6%.
[ chemical formula 71]
Figure BDA0003165812380000553
EXAMPLE 23 Synthesis of Compound No.23
The same operation was carried out with the indolenine quaternary salt 1 of example 1 changed to the above indolenine ester 2, whereby the following compound No.23 was obtained in a yield of 60.0%.
[ chemical formula 72]
Figure BDA0003165812380000561
EXAMPLE 24 Synthesis of Compound No.24
The same operation was carried out with the compound No.7 used in example 8 changed to the compound No.23, so as to obtain the following compound No.24 in a yield of 85.0%.
[ chemical formula 73]
Figure BDA0003165812380000562
EXAMPLE 25 Synthesis of Compound No.25
The same operation was carried out with the pyridone body 1 of example 1 changed to pyridone body 4 and with the indolenine quaternary salt 1 changed to the known indolenine quaternary salt 10 described below, whereby the following compound No.25 was obtained in a yield of 69.2%.
[ chemical formula 74]
Figure BDA0003165812380000563
EXAMPLE 26 Synthesis of Compound No.26
The same operation was carried out with the compound No.7 used in example 8 changed to the compound No.25, so as to obtain the following compound No.26 in a yield of 92.8%.
[ chemical formula 75]
Figure BDA0003165812380000571
EXAMPLE 27 Synthesis of Compound No.27
The same operation was carried out with the compound No.17 used in example 18 changed to the compound No.26, so as to obtain the following compound No.27 in a yield of 62.5%.
[ chemical formula 76]
Figure BDA0003165812380000572
EXAMPLE 28 Synthesis of Compound No.28
The same operation was carried out with the change of pyridone body 1 of example 1 to pyridone body 6 and the change of indolenine quaternary salt 1 to indolenine quaternary salt 10, whereby the following compound No.28 was obtained in a yield of 24.0%.
[ chemical formula 77]
Figure BDA0003165812380000581
EXAMPLE 29 Synthesis of Compound No.29
The same operation was carried out with the compound No.7 used in example 8 changed to the compound No.28, so that the following compound No.29 was obtained in a yield of 62.9%.
[ chemical formula 78]
Figure BDA0003165812380000582
EXAMPLE 30 Synthesis of Compound No.30
The same operation was carried out with the change of pyridone body 1 of example 1 to pyridone body 7 and the change of indolenine quaternary salt 1 to indolenine ester 2, whereby the following compound No.30 was obtained in a yield of 45.2%.
[ chemical formula 79]
Figure BDA0003165812380000583
EXAMPLE 31 Synthesis of Compound No.31
The same operation was carried out with the compound No.7 used in example 8 changed to the compound No.30, so as to obtain the following compound No.31 in a yield of 35.1%.
[ chemical formula 80]
Figure BDA0003165812380000591
EXAMPLE 32 Synthesis of Compound No.32
The same operation was carried out with the change of pyridone body 1 of example 1 to pyridone body 8 and the change of indolenine quaternary salt 1 to indolenine ester 2, whereby the following compound No.32 was obtained in a yield of 45.2%.
[ chemical formula 81]
Figure BDA0003165812380000592
EXAMPLE 33 Synthesis of Compound No.33
The same operation was carried out with the compound No.7 used in example 8 changed to the compound No.32, so as to obtain the following compound No.33 in a yield of 35.1%.
[ chemical formula 82]
Figure BDA0003165812380000593
EXAMPLE 34 Synthesis of Compound No.34
The same operation was carried out with the change of pyridone body 1 of example 1 to pyridone body 6 and the change of indolenine quaternary salt 1 to indolenine quaternary salt 9, whereby the following compound No.34 was obtained in a yield of 39.4%.
[ chemical formula 83]
Figure BDA0003165812380000601
EXAMPLE 35 Synthesis of Compound No.35
The same operation was carried out except for changing the compound No.7 used in example 8 to the compound No.34, whereby the following compound No.35 was obtained in a yield of 81.6%.
[ chemical formula 84]
Figure BDA0003165812380000602
EXAMPLE 36 Synthesis of Compound No.78
Compound No.9(0.7g, 2.0mmol) was dissolved in 1, 2-dichloroethane (7.2g), and thionyl chloride (0.72g, 6mmol) was added dropwise in an ice bath. After stirring at room temperature for 3 hours, the mixture was concentrated under reduced pressure to remove thionyl chloride. To this was added sulfanilamide (0.37g, 2.2mmol) and acetonitrile (7.2g) at room temperature, followed by stirring and dropwise addition of triethylamine (0.24g, 2.4 mmol). The resulting solution was stirred at room temperature for 3 hours, poured into hydrochloric acid water, and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous sodium sulfate, and concentrated. The crude product was subjected to column purification to obtain 0.15g (yield 10.5%) of the following compound No. 78.
[ chemical formula 85]
Figure BDA0003165812380000611
<1H-NMR>
The compounds obtained in examples 1 to 36 were dissolved in each ofIn deuterated solvent (DMSO-d6), measuring1H-NMR. The results are shown in Table 1.
TABLE 1-1
Figure BDA0003165812380000621
Tables 1 to 2
Figure BDA0003165812380000631
Tables 1 to 3
Figure BDA0003165812380000641
Tables 1 to 4
Figure BDA0003165812380000651
The compounds described in Table 2 below and comparative compounds Nos. 1 to 3 below were evaluated for their maximum absorption wavelength (. lamda.max), molar absorption coefficient (. epsilon.) and decomposition temperature.
The results are shown in Table 2.
< maximum absorption wavelength (. lamda.max) and molar absorptivity (. epsilon.) >)
10mg of the compound shown in Table 2 was weighed into a 100ml volumetric flask, chloroform was added to the flask until the line marked, and the mixture was ultrasonically shaken for 10 minutes to obtain a homogenized solution. From the resulting solution, 2ml was taken out by a fat pipette, and placed in an empty 50ml volumetric flask, to which chloroform was added up to the marked line to prepare a measurement sample.
The following measurement was carried out on the above measurement sample in Japanese Spectroscopy U-3900. Specifically, after measuring the chloroform baseline, the measurement sample was placed in a quartz cell having an optical path length of 1cm, absorbance measurement was performed at intervals of 0.5nm at 300nm/min in a visible light region of 800 to 300nm, and the wavelength at which the absorbance reaches the maximum at 600 to 400nm was defined as λ max. Further, from the absorbance of λ max and its molecular weight, the molar absorption coefficient ∈ was calculated using lambert beer's law.
< decomposition temperature >
The apparatus TG-DTA6200 was simultaneously measured using differential thermal gravimetry manufactured by Seiko Instruments. 2mg of each of the compounds shown in Table 2 was weighed into an aluminum sample pan, and the measurement was carried out under a nitrogen flow of 200ml/min, a temperature rise rate of 10 ℃/min, and a measurement temperature range of 35 ℃ to 550 ℃. The decomposition temperature was calculated from the intersection of the tangent line at 0% weight loss and the tangent line at 10% weight loss of the obtained TG curve. The evaluation results are shown in table 2.
[ chemical formula 86]
Comparative Compound No.1
Figure BDA0003165812380000661
[ chemical formula 87]
Comparative Compound No.2
Figure BDA0003165812380000671
[ chemical formula 88]
Comparative Compound No.3
Figure BDA0003165812380000672
TABLE 2
Compound (I) λmax(nm) ε Decomposition temperature (. degree.C.)
Evaluation example 1 Compound No.1 545.0 124000 310
Evaluation example 2 Compound No.2 545.5 199000 298
Evaluation example 3 Compound No.3 545.5 228000 308
Evaluation example 4 Compound No.5 540.0 121000 304
Evaluation example 5 Compound No.6 559.5 114000 274
Evaluation example 6 Compound No8 560.0 105000 235
Evaluation example 7 Compound No.10 561.0 107000 276
Evaluation example 8 Compound No.11 562.0 185000 228
Evaluation example 9 Compound No.13 546.0 124000 285
Evaluation example 10 Compound No.15 547.0 101000 240
Evaluation example 11 Compound No.18 559.5 124000 248
Evaluation example 12 Compound No.19 534.0 114000 299
Evaluation example 13 Compound No.24 536.0 115000 265
Evaluation example 14 Compound No.27 539.5 133000 233
Evaluation example 15 Compound No.29 539.0 131000 266
Evaluation example 16 Compound No31 536.0 103000 261
Evaluation example 17 Compound No.33 537.5 99200 245
Evaluation example 18 Compound No.35 534.0 134000 271
Evaluation example 19 Compound No.78 561.0 107000 250
Comparative evaluation example 1 Comparative Compound No.1 481 53200 -
Comparative evaluation example 2 Comparative Compound No.2 460 79000 -
Comparative evaluation example 3 Comparative Compound No.3 395.5 15700 -
As is clear from Table 2, the compound of the present invention exhibits strong absorption at 500 to 600nm, shows red to orange color, shows a decomposition temperature of 200 ℃ or higher, and has high heat resistance.
A coating solution was prepared by mixing 0.4g of a 0.5 mass% acetone solution of the compound shown in Table 3 and comparative compound No.4 below with 3.0g of a 25 mass% toluene solution of polymethyl methacrylate and subjecting the mixture to ultrasonic irradiation for 15 minutes.
[ chemical formula 89]
Comparative Compound No.4
Figure BDA0003165812380000681
TABLE 3
Name of Compound Coating liquid
Example 37 Compound No.1 Coating liquid No.1
Example 38 Compound No.2 Coating liquid No.2
Example 39 Compound No.3 Coating liquid No.3
Example 40 Compound No.5 Coating liquid No.4
EXAMPLE 41 Compound No.6 Coating liquid No.5
Example 42 Compound No.8 Coating liquid No.6
Example 43 Compound No.10 Coating liquid No.7
Example 44 Compound No.11 Coating liquid No.8
Example 45 Compound No.13 Coating liquid No.9
Example 46 Compound No.15 Coating liquid No.10
Example 47 Compound No.18 Coating liquid No.11
Example 48 Compound No.19 Coating liquid No.12
Example 49 Compound No.22 Coating liquid No.13
Example 50 Compound No.24 Coating liquid No.14
Example 51 Compound No.27 Coating liquid No.15
Example 52 Compound No.29 Coating liquid No.16
Example 53 Compound No.31 Coating liquid No.17
Example 54 Compound No.33 Coating liquid No.18
Example 55 Compound No.35 Coating liquid No.19
Comparative example 1 Comparative Compound No.4 Comparative coating liquid No.1
The obtained coating liquid was applied to a 188 μm-thick polyethylene terephthalate film subjected to adhesion treatment by a bar coater #30, and then dried at 70 ℃ for 15 minutes to prepare a coating film (film thickness 7 to 8 μm).
Evaluation examples 1 to 19 and comparative evaluation examples 1 and 2
The above-described coating film was subjected to a light resistance test.
Light resistance test
The coating film was irradiated with light for 48 hours by a xenon light resistance tester (Table Sun TS-2 manufactured by Suga tester Co., Ltd.) to evaluate the light resistance. In the evaluation, the absorbance at the absorption maximum wavelength of each coating film before and after light irradiation was measured, and the relative value (absorbance retention ratio) after light irradiation was calculated with the initial value (before light irradiation) as 100, and the light resistance was compared. The absorbance retention is preferably high. The results are shown in Table 4.
TABLE 4
Name of Compound Absorbance retention (%)
Evaluation example 20 Coating liquid No.1 46.5
Evaluation example 21 Coating liquid No.2 45.7
Evaluation example 22 Coating liquid No.3 95.7
Evaluation example 23 Coating liquid No.4 41.5
Evaluation example 24 Coating liquid No.5 77.7
Evaluation example 25 Coating liquid No.6 65.5
Evaluation example 26 Coating liquid No.7 65.5
Evaluation example 27 Coating liquid No.8 40.0
Evaluation example 28 Coating liquid No.9 51.4
Evaluation example 29 Coating liquid No.10 39.6
Evaluation example 30 Coating liquid No.11 70.6
Evaluation example 31 Coating liquid No.12 75.5
Evaluation example 32 Coating liquid No.13 92.3
Evaluation example 33 Coating liquid No.14 70.7
Evaluation example 34 Coating liquid No.15 66.8
Evaluation example 35 Coating liquid No.16 66.6
Evaluation example 36 Coating liquid No.17 93.7
Evaluation example 37 Coating liquid No.18 70.8
Evaluation example 38 Coating liquid No.19 70.0
Comparative evaluation example 3 Comparative coating liquid No.1 3.0
As is clear from table 4, the coating film using the polymethine compound of the present invention is excellent in light resistance.

Claims (18)

1. A compound of the formula (I),
Figure FDA0003165812370000011
in the formula, R2、R3、R4、R5、R7、R8、R9And R10Each independently represents a hydrogen atom, a hydroxyl group, a nitro group, a cyano group, a halogen atom, a carboxyl group, a sulfo group, a sulfamoyl group, a heterocyclic group, a metallocenyl group, a hydrocarbon group having 1 to 30 carbon atoms, or a group in which 1 or 2 or more methylene groups in the hydrocarbon group are substituted by a divalent group selected from the group I, wherein when 2 or more methylene groups are substituted by a divalent group selected from the group I, oxygen atoms of the divalent groups are not adjacent,
R1and R6Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a heterocyclic group, or a group in which 1 or 2 or more methylene groups in the hydrocarbon group are substituted with a divalent group selected from the group I, wherein when 2 or more methylene groups are substituted with a divalent group selected from the group I, oxygen atoms of the divalent group are not adjacent,
q represents-CR11R12-, oxygen atom, sulfur atom or-NR13-，
R11、R12And R13Each independently represents a hydrogen atom, a hydroxyl group, a nitro group, a cyano group, a halogen atom, a carboxyl group, a sulfo group, a sulfamoyl group, a heterocyclic group, a metallocenyl group, a hydrocarbon group having 1 to 30 carbon atoms, or a group in which 1 or 2 or more methylene groups in the hydrocarbon group are substituted by a divalent group selected from the group I, wherein when 2 or more methylene groups are substituted by a divalent group selected from the group I, oxygen atoms of the divalent groups are not adjacent,
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12and R13Hydrogen atom or R in the hydrocarbon group having 1 to 30 carbon atoms1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12And R13The hydrogen atom in the heterocyclic group represented by (A) may be substituted with a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an oxirane group, a vinyl group, a vinyloxy group, a sulfanyl group, a sulfamoyl group, an isocyanate group or a heterocyclic group,
R7and R8、R8And R9、R9And R10、R10And R11And R11And R12May be bonded to form a ring, and the ring may have a substituent,
m is an integer of 1 to 3,
when m is greater than or equal to 2, there are a plurality of R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13And Q may be the same or different from each other,
when m is 1, A is not present,
when m is 2 or more, A represents a direct bond, -NR14-, oxygen atom, sulfur atom, -SO2-、-SO-、-PR14-、Em+A linking group represented by the following formula (a), formula (b) or (i) or (ii),
Figure FDA0003165812370000021
R14represents a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms or a group in which 1 or 2 or more methylene groups in the hydrocarbon group are substituted with a divalent group selected from the group II, wherein when 2 or more methylene groups are substituted with a divalent group selected from the group II, oxygen atoms of the divalent group are not adjacent,
Em+represents a cation having a valence of m,
when m is more than or equal to 2 and A is not Em+In the case of (A) and (R)1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12And R13The position of any one of the groups shown after removal is bonded,
the x denotes a bonding end of the substrate,
group I: -O-, -S-, -CO-, -COO-, -OCO-, -COS-, -OCS-, -SO2-、-SO3-、-NH-、-CONH-、-NHCO-、-SO2NH-、-NH-SO2-, -N-CH-or a divalent heterocyclic radical
Group II: -COO-, -O-, -OCO-, -NHCO-, -NH-or-CONH-
(i) When m is 2, A may be a linking group represented by the following formula (. alpha.),
*-Z1-X1-Z2-* (α)
in the formula, X1represents-NR15A divalent heterocyclic group, a group represented by the formula (. alpha. -1) or the formula (. alpha. -3), a hydrocarbon group having 1 to 30 carbon atoms, or a group in which 1 or 2 or more methylene groups in the hydrocarbon group are substituted with a divalent heterocyclic group,
Z1and Z2Independently represent a direct bond, -O-, -S-, -SO2-、-SO-、-NR15-or-PR16-，
R15And R16Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a group in which 1 or 2 or more methylene groups in the hydrocarbon group are substituted with a divalent group selected from the group III, wherein when 2 or more methylene groups are substituted with a divalent group selected from the group III, oxygen atoms of the divalent group are not adjacent,
the x denotes a bonding end of the substrate,
group III: -COO-, -O-, -OCO-, -NHCO-, -NH-or-CONH-
Figure FDA0003165812370000031
In the formula, R21Represents a hydrocarbon group having 1 to 30 carbon atoms or a phenyl group substituted with an alkoxy group having 1 to 10 carbon atoms,
R22represents an alkoxy group having 1 to 10 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms or a halogen atom,
the hydrogen atoms of the C1-30 hydrocarbyl group and the C1-10 alkoxy group may be substituted by halogen atoms,
d represents an integer of 0 to 4,
the x denotes a bonding end of the substrate,
Figure FDA0003165812370000032
in the formula, R23And R24Each independently represents an aryloxy group having 6 to 20 carbon atoms, an arylsulfanyl group having 6 to 20 carbon atoms, a heterocyclic group, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a group in which 1 or 2 or more methylene groups in the hydrocarbon group are substituted with a divalent group selected from the group IV,
R23and R24The hydrogen atom in the group represented may be substituted with a halogen atom or a heterocyclic group,
with respect to R23Adjacent R23May be bonded to each other to form a ring,
e represents a number of 0 to 4,
f represents a number of 0 to 8,
g represents a number of 0 to 4,
h represents a number of 0 to 4,
the sum of the numbers of g and h is 2 to 4,
the x denotes a bonding end of the substrate,
group IV: -O-or-S-
(ii) When m is 3, A may be a linking group represented by the following formula (. beta.),
Figure FDA0003165812370000041
in the formula, X2Represents a trivalent heterocyclic group, a hydrocarbon group having 1 to 30 carbon atoms, or a divalent group in which 1 or 2 or more methylene groups in the hydrocarbon group are selected from the group VA group obtained by substitution wherein when 2 or more methylene groups are substituted with a divalent group selected from the group V below, oxygen atoms of the divalent group are not adjacent,
Z1、Z2and Z3Each independently of the other, Z in the formula (alpha)1And Z2The groups shown are the same groups and are,
the number of carbon atoms of the group represented by the formula (beta) is in the range of 1 to 35,
the x denotes a bonding end of the substrate,
group V: -COO-, -O-, -OCO-, -NHCO-, -NH-, -CONH-, -O-CONH-, -NHCO-O-or a divalent heterocyclic group.
2. The compound according to claim 1, wherein it is represented by formula (II),
Figure FDA0003165812370000051
in the formula, R1、R2、R3、R4、R5、R6、R7、R8、R9、R10And Q is the same as the formula (I).
3. The compound of claim 1, wherein it is represented by formula (III α), (III β) or (III γ),
Figure FDA0003165812370000052
in the formula, R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、Q、X1、Z1And Z2Is the same as the formula (I).
4. A compound according to any one of claims 1 to 3, wherein formula (I), (II), (III α), (III β)) And R in (III γ)2Is cyano, R3Is an alkyl group having 1 to 5 carbon atoms.
5. A compound according to any one of claims 1 to 3, wherein R in formulae (I), (II), (III α), (III β) and (III γ)2Is alkyl or haloalkyl.
6. A compound according to any one of claims 1 to 5, wherein Q in formulae (I), (II), (III α), (III β) and (III γ) is-CR11R12-。
7. The compound of claim 6, wherein R11And R12Each independently is an alkyl group having 1 to 20 carbon atoms.
8. A compound according to any one of claims 1 to 7, wherein R in formulae (I), (II), (III α), (III β) and (III γ)1、R2、R3、R4、R5、R6、R7、R8、R9And R101 or more of the groups represented are carboxyl or nitro, or
R in the formulae (I), (II), (III α), (III β) and (III γ)1、R2、R3、R4、R6、R7、R8、R9And R101 or more hydrogen atoms in the group represented are substituted with a carboxyl group or a nitro group.
9. A compound according to any one of claims 1 to 8, wherein R in formulae (I), (II), (III α), (III β) and (III γ)4、R5、R7、R8、R9And R10At least 1 of the groups represented is a nitro group.
10. A compound according to any one of claims 1 to 7, wherein R in formulae (I), (II), (III α), (III β) and (III γ)1The group is an alkyl group having 1 to 20 carbon atoms or a group in which 1 or 2 or more methylene groups in the alkyl group are substituted with-O-, -COO-or-OCO-.
11. The compound of claim 10, wherein R in formulas (I), (II), (III α), (III β), and (III γ)1The groups shown are substituted with hydroxyl or carboxyl groups.
12. A compound according to any one of claims 1 to 7, wherein R in formulae (I), (II), (III α), (III β) and (III γ)6The group is an alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a group in which 1 or 2 or more of methylene groups in the alkyl group or methylene groups in the alkyl group of the arylalkyl group are substituted with-O-, -COO-or-OCO-.
13. The compound of claim 12, wherein R in formulas (I), (II), (III α), (III β), and (III γ)1The groups shown are substituted with acidic groups.
14. A compound according to any one of claims 1 to 7, wherein R in said formulae (I), (II), (IIIa), (IIIβ) and (IIIγ)7、R8And R10At least 1 of which is a hydrogen atom.
15. A compound according to any one of claims 1 to 7, wherein R in said formulae (I), (II), (IIIa), (IIIβ) and (IIIγ)3Is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms.
16. A resin composition comprising the compound according to any one of claims 1 to 15 and a resin.
17. Use of a compound according to any one of claims 1 to 15 as a light absorber.
18. Use of a compound according to any one of claims 1 to 15 as a sensitizer.
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