WO2018043451A1 - ポリメチン化合物 - Google Patents
ポリメチン化合物 Download PDFInfo
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- WO2018043451A1 WO2018043451A1 PCT/JP2017/030844 JP2017030844W WO2018043451A1 WO 2018043451 A1 WO2018043451 A1 WO 2018043451A1 JP 2017030844 W JP2017030844 W JP 2017030844W WO 2018043451 A1 WO2018043451 A1 WO 2018043451A1
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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
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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
- C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
- C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
Definitions
- the present invention relates to a polymethine compound having a specific structure.
- Polymethine compounds are optical absorbers, sensitizers, dyes, etc., optical films and optical filters used for displays and optical lenses, photosensitive photographic materials, dyed articles, paints, inks, electrophotographic photosensitive members, toners, thermal recording papers, Widely used in transfer ribbons, optical recording dyes, solar cells, photoelectric conversion elements, semiconductor materials, clinical laboratory reagents, laser treatment dyes, dyeing, and the like.
- Patent Document 1 discloses a silver halide photographic light-sensitive material containing a methine dye compound
- Patent Document 2 discloses a polymethine compound and an optical filter and an optical recording material using the compound
- Patent Document 3 discloses a photoelectric conversion element containing a polymethine compound
- Patent Document 4 discloses an acid merocyanine dye.
- Patent Documents 1 to 4 have insufficient light resistance and heat resistance.
- An object of the present invention is to provide a polymethine compound having excellent light resistance and heat resistance.
- R 1 , R 2 , R 3 , R 4 , R 6 and R 7 are each independently a hydrogen atom, a hydroxyl group, a nitro group, a cyano group, a halogen atom, a carboxyl group, a sulfonic acid group, or a sulfonamide.
- the alkyl part of the group represented by R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 is a branched side chain or cyclic May be alkyl, may have a substituent, R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 10 and R 11, and R 12 and R 1 may be combined to form a ring.
- the ring may have a substituent, m is an integer from 1 to 6, When m ⁇ 2, a plurality of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and X may be the same or different.
- R 13 represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms
- the methylene group in the hydrocarbon group having 1 to 30 carbon atoms represented by R 13 is —COO—, —O—, —OCO—, —NHCO—, —NH—, —CONH—, or a combination thereof.
- E m + represents an m-valent cation
- L m ⁇ represents an m-valent anion
- A is hydrogen of a group represented by R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 or R 9.
- A may be a linking group represented by the following formula ( ⁇ ).
- X 1 is> NR 14 , a hydrocarbon group having 1 to 30 carbon atoms, a group having 2 to 20 carbon atoms containing a heterocyclic ring, or the following ( ⁇ -1), ( ⁇ -2) or Represents a group represented by ( ⁇ -3), Z 1 and Z 2 each independently represent a direct bond, —O—, —S—, —SO 2 —, —SO—,> NR 14 , or> PR 15 ; R 14 and R 15 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms,
- the methylene group in the groups represented by R 14 and R 15 is an oxygen atom by a group —COO—, —O—, —OCO—, —NHCO—, —NH—, —CONH—, or a combination thereof. May be replaced under the condition that is not adjacent.
- the group represented by the above formula ( ⁇ ) is in the range of 1 to 35 carbon atoms, and * in the formula means bonding
- R 21 represents a phenyl group substituted by a hydrocarbon group having 1 to 30 carbon atoms or an alkoxy group having 1 to 10 carbon atoms
- R 22 represents an alkoxy group having 1 to 10 carbon atoms
- the hydrogen atom of the hydrocarbon group having 1 to 30 carbon atoms and the alkoxy group having 1 to 10 carbon atoms may be replaced with a halogen atom
- d is an integer from 0 to 4
- * In the formula means bonding with an adjacent group at the * portion.
- R 23 and R 24 each independently represents a hydrocarbon group having 1 to 30 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms, or a heterocyclic ring. Represents a group having 2 to 20 carbon atoms or a halogen atom,
- the hydrogen atom in the group represented by R 23 and R 24 may be replaced with a halogen atom,
- the methylene group in the groups represented by R 23 and R 24 may be replaced by an unsaturated bond, —O—, —S—, or a combination thereof in a condition where oxygen atoms are not adjacent to each other.
- X 2 represents a hydrocarbon group having 1 to 30 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocyclic ring;
- the methylene group in the group represented by X 2 is —COO—, —O—, —OCO—, —NHCO—, —NH—, —CONH—, —O—CONH—, —NHCO—O—, or Depending on the combination of these, oxygen atoms may not be adjacent to each other.
- Z 1 , Z 2 and Z 3 are each independently the same as the group represented by Z 1 and Z 2 in the above formula ( ⁇ ).
- X 3 represents a carbon atom, a hydrocarbon group having 1 to 30 carbon atoms, or a group having 2 to 20 carbon atoms containing a heterocyclic ring;
- the methylene group in the group represented by X 3 is —COO—, —O—, —OCO—, —NHCO—, —NH—, —CONH—, —O—CONH—, —NHCO—O—, or
- oxygen atoms may not be adjacent to each other.
- Z 1 , Z 2 , Z 3 and Z 4 are each independently the same as the group represented by Z 1 and Z 2 in the above formula ( ⁇ ).
- X 4 represents a hydrocarbon group having 1 to 30 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocyclic ring;
- the methylene group in the group represented by X 4 is —COO—, —O—, —OCO—, —NHCO—, —NH—, —CONH—, —O—CONH—, —NHCO—O—, or
- oxygen atoms may be replaced under non-adjacent conditions
- Z 1 , Z 2 , Z 3 , Z 4 and Z 5 are each independently the same as the group represented by Z 1 and Z 2 in the above formula ( ⁇ ).
- X 5 represents a hydrocarbon group having 1 to 30 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocyclic ring;
- the methylene group in the group represented by X 5 is —COO—, —O—, —OCO—, —NHCO—, —NH—, —CONH—, —O—CONH—, —NHCO—O—, or
- oxygen atoms may not be adjacent to each other.
- Z 1 , Z 2 , Z 3 , Z 4 , Z 5 and Z 6 are each independently the same as the groups represented by Z 1 and Z 2 in the above formula ( ⁇ ).
- the group represented by the general formula ( ⁇ ) is in the range of 2 to 35 carbon atoms, and * in the formula means that it is bonded to an adjacent group at the * portion.
- the present invention also provides the polymethine compound represented by the following general formula (II).
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and X are the same as those in the general formula (I).
- the present invention also provides the polymethine compound represented by the following general formula (III).
- R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , R 9 and X are the same as those in the general formula (I), and X 1 , Z 1 and Z 2 Is the same as the above general formula ( ⁇ ).
- the present invention also provides the polymethine compound, wherein R 9 in the general formulas (I), (II) and (III) is a group represented by the following formula ( ⁇ ).
- R 31 , R 32 , R 33 , R 34 and R 35 are each independently a hydrogen atom, hydroxyl group, nitro group, cyano group, halogen atom, carboxyl group, sulfonic acid group, —SO 2 NR 36.
- R 37 represents a hydrocarbon group having 1 to 30 carbon atoms, a group having 2 to 20 carbon atoms containing a heterocyclic ring, or a metallocenyl group;
- One or more of R 31 , R 32 , R 33 , R 34 and R 35 are —SO 2 NR 36 R 37 , R 36 and R 37 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a group having 2 to 20 carbon atoms containing a heterocyclic ring, or a metallocenyl group,
- the methylene groups in the groups represented by R 31 , R 32 , R 33 , R 34 , R 35 , R 36 and R 37 are —O—, —S—, —CO—, —COO—, —OCO—.
- R 31 , R 32 , R 33 , R 34 , R 35 , R 36 and R 37 may be a branched side chain or cyclic alkyl, and may have a substituent, R 31 and R 32 , R 32 and R 33 , R 33 and R 34 , R 34 and R 35, and R 36 and R 37 may combine to form a ring, and the formed ring has a substituent. May have. )
- the present invention also provides a composition containing the above polymethine compound, and an optical film and an optical filter using the composition.
- the polymethine compound of the present invention has a structure represented by the above general formula (I).
- Examples of the halogen atom represented by R 1 , R 2 , R 3 , R 4 , R 6 and R 7 include fluorine, chlorine, bromine and iodine.
- the hydrocarbon group having 1 to 30 carbon atoms represented by R 1 , R 2 , R 3 , R 4 , R 6 , R 7 is not particularly limited, but preferably has 1 to 20 carbon atoms.
- Alkyl groups, alkenyl groups having 2 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, cycloalkylalkyl groups having 4 to 20 carbon atoms, aryl groups having 6 to 30 carbon atoms, and the number of carbon atoms Represents an arylalkyl group having 7 to 30 carbon atoms, an arylalkenyl group having 8 to 30 carbon atoms, etc., and has a high absorbance; therefore, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a carbon atom A cycloalkyl group having 3 to 10 carbon atoms, a cycloalkylalkyl group having 4 to 10 carbon atoms, an
- alkyl group having 1 to 20 carbon atoms examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl. 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl and the like.
- alkyl group having 1 to 10 carbon atoms examples include methyl, Ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl and isodecyl, etc. But It is below.
- alkenyl group having 2 to 20 carbon atoms examples include vinyl, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 5-hexenyl, 2 -Heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl, 3-cyclohexenyl, 2,5-cyclohexadienyl-1-methyl, and 4 , 8,12-tetradecatrienylallyl and the like.
- alkenyl group having 2 to 10 carbon atoms examples include vinyl, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3- Pentenyl, 2-hexenyl, 3-hexenyl, 5-hexenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl , 3-octenyl, 3-nonenyl and 4-decenyl and the like.
- the above cycloalkyl group having 3 to 20 carbon atoms means a saturated monocyclic or saturated polycyclic alkyl group having 3 to 20 carbon atoms in total.
- the cycloalkyl group having 3 to 10 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronap
- cycloalkylalkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in total, in which hydrogen atoms of the alkyl group are replaced with cycloalkyl groups.
- Examples of the cycloalkylalkyl group having 4 to 10 carbon atoms include cyclopropylmethyl , Cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, cyclononylmethyl, 2-cyclobutylethyl, 2-cyclopentylethyl, 2-cyclohexylethyl, 2-cycloheptylethyl, 2-cyclooctylethyl 3-cyclobutylpropyl, 3-cyclopentylpropyl, 3-cyclohexylpropyl, 3-cycloheptylpropyl, 4-cyclobutylbutyl, 4-cyclopentylbutyl, 4-cyclohexylbutyl, bicyclo 1.1.0] butyl, bicyclo [1.1.1] pentyl, bicyclo [2.1.0] pentyl, bicyclo [3.1.0] hexyl
- Examples of the aryl group having 6 to 30 carbon atoms include one or more of phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl, the alkyl group, the alkenyl group, the carboxyl group, and the halogen atom.
- Aromatic monocyclic or condensed ring structure such as substituted phenyl, biphenylyl, naphthyl, anthryl, for example, 4-chlorophenyl, 4-carboxylphenyl, 4-vinylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl
- aryl group having 6 to 10 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl and naphthyl, the alkyl group, the alkenyl group, the carboxyl group, and the like. Substituted with one or more groups, halogen atoms, etc.
- Aryl or biphenylyl, naphthyl, etc. for example, 4-chlorophenyl, 4-carboxylphenyl, 4-vinylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl, etc. monocyclic or condensed aromatic hydrocarbons
- a ring or a connecting structure thereof is exemplified.
- the arylalkyl group having 7 to 30 carbon atoms means a group having a total of 7 to 30 carbon atoms in which the hydrogen atom of the alkyl group is replaced with an aryl group.
- benzyl, ⁇ -methyl examples include benzyl, ⁇ , ⁇ -dimethylbenzyl, 2-phenylethyl, 2-phenylpropyl, 3-phenylpropyl, diphenylmethyl, triphenylmethyl, triphenylpropyl, naphthylpropyl, and the like.
- An arylalkyl group means a group having a total of 7 to 20 carbon atoms in which the hydrogen atom of the alkyl group is replaced with an aryl group.
- benzyl, ⁇ -methylbenzyl, ⁇ , ⁇ -dimethylbenzyl Dimethylbenzyl, 2-phenylethyl, 2-phenylpropyl, 3-phenylpropyl, diphenylmethyl Triphenylmethyl and naphthyl propyl, and the like.
- the arylalkenyl group having 8 to 30 carbon atoms means a group having a total of 8 to 30 carbon atoms in which the hydrogen atom of the alkenyl group is replaced with an aryl group, and examples thereof include styryl, cinnamyl, -Phenyl-2-propenyl, 3-phenyl-2-propenyl, 2-phenyl-4-pentenyl, 2-phenyl-4-hexenyl, 2,2-diphenylethylenyl, 3,3-phenyl-2-propenyl, 2 -Naphthyl-2-propenyl, 3-naphthyl-2-propenyl, 3-naphthyl-2-phenyl-2-propenyl, 5-anthracenyl-2-phenyl-4-hexenyl and 5-anthracenyl-2-naphthyl-4-hexenyl
- a group having 2 to 20 carbon atoms containing a heterocyclic ring represented by R 1 , R 2 , R 3 , R 4 , R 6 and R 7 is a group having 2 to 20 carbon atoms containing at least one heterocyclic ring.
- 20 groups are meant, and the number of carbon atoms means the number of carbon atoms in the whole group. In the following description, when the number of carbon atoms of a group containing a heterocyclic ring is specified, all means the number of carbon atoms of the entire group.
- Examples of the group having 2 to 20 carbon atoms containing the heterocyclic ring include pyridyl, pyrimidyl, pyridazyl, piperazyl, piperidyl, pyranyl, pyrazolyl, triazyl, pyrrolidyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl.
- the hydrocarbon group having 1 to 30 carbon atoms or the group having 2 to 20 carbon atoms containing the heterocyclic ring may have the following substituents.
- 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
- the substituent include substituents other than alkyl groups and arylalkyl groups among the substituents exemplified below.
- the substituent is preferably a monocyclic or condensed aromatic hydrocarbon ring (part of the ring structure).
- aromatic hydrocarbon ring or the substituent of the linking structure thereof includes substituents other than the aryl group among the substituents exemplified below.
- Preferred substituents 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.
- alkyl group examples include an aromatic hydrocarbon ring having a monocyclic or condensed ring structure or an alkyl group to which a linking structure thereof is bonded.
- an alkyl group, an arylalkyl group, and an arylalkenyl group are an aromatic hydrocarbon of an arylalkyl group having 7 to 30 carbon atoms or an arylalkenyl group having 8 to 30 carbon atoms. Replace with a ring.
- substituent having 2 to 20 carbon atoms containing a heterocyclic ring examples include substituents other than the group containing a heterocyclic ring among the substituents exemplified below.
- the hydrocarbon group having 1 to 30 carbon atoms or the group having 2 to 20 carbon atoms containing the heterocyclic ring has a substituent containing a carbon atom among the following substituents
- the total number of carbon atoms including substituents shall satisfy the specified range. That is, when the hydrocarbon group having 1 to 30 carbon atoms has a substituent containing a carbon atom, the range of the number of carbon atoms including the substituent is 1 to 30 as a whole, and includes a heterocyclic ring.
- the group having 2 to 20 carbon atoms has a substituent containing a carbon atom, the range of the number of carbon atoms including the substituent is 2 to 30 as a whole.
- the 20 alkyl groups have a substituent containing a carbon atom
- the range of the number of carbon atoms is 1 to 20 as a whole including the substituent.
- substituents examples include methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, tert-amyl, cyclopentyl, hexyl, 2-hexyl, and 2-ethyl.
- Substituted amino groups sulfonamido groups, sulfonyl-containing groups, carboxylic acid groups, cyano groups, sulfonic acid groups, hydroxyl groups, nitro groups, mercapto groups, imide groups, carbamoyl groups, phosphoric acid groups, and the like. May be substituted.
- acidic groups such as the carboxylic acid group, sulfonic acid group, and phosphoric acid group may form salts with various cations
- substituted amino group eg, diethylamino group, dimethylamino group
- various anions and salts may be formed.
- the cation include alkali metal ions, alkaline earth metal ions, transition metal cations, ammonium having 4 or more carbon atoms, amidinium, guanidinium cations, and the anions include, for example, monovalent ones.
- halide ions such as chloride ion, bromide ion, iodide ion, fluoride ion; perchlorate ion, chlorate ion, thiocyanate ion, hexafluorophosphate ion, hexafluoroantimonate ion, tetrafluoroboro Inorganic anions such as acid ions; methanesulfonate ion, dodecylsulfonate ion, benzenesulfonate ion, toluenesulfonate ion, trifluoromethanesulfonate ion, pentafluorobenzenesulfonate ion, diphenylamine-4-sulfonate ion 2-amino-4-methyl-5-chlorobenzenesulfonic acid ion, 2-amino-5-nitrobenzenesulfonic acid ion, phthalocyanine
- Examples of the metallocenyl group represented by R 1 , R 2 , R 3 , R 4 , R 6 and R 7 include ferrocenyl, nickelocenyl, cobaltyl, ferrocene alkyl, ferrocene alkoxy and the like.
- R 1 , R 2 , R 3 , R 4 , R 6 and R 7 are particularly preferably a hydrogen atom or a group represented by the following formula.
- the hydrocarbon group having 1 to 30 carbon atoms represented by R 5 and R 9 and the group having 2 to 20 carbon atoms containing a heterocyclic ring are respectively R 1 , R 2 , R 3 , R 4 , R This is the same as the hydrocarbon group having 1 to 30 carbon atoms represented by 6 and R 7 and the group having 2 to 20 carbon atoms containing a heterocyclic ring.
- R 5 is particularly preferably a group represented by the following formula.
- R 9 is particularly preferably a group represented by the following formula.
- the halogenated alkyl group having 1 to 20 carbon atoms represented by R 8 means a group in which one or more hydrogen atoms in the alkyl group having 1 to 20 carbon atoms are replaced with a halogen atom. Examples thereof include fluoromethyl, difluoromethyl, trifluoromethyl, pentafluoroethyl, 4-trifluoromethylphenyl and 4-trifluoromethylbenzoyl.
- the aryl group having 6 to 20 carbon atoms represented by R 8 is the same as the aryl group having 6 to 20 carbon atoms described as an example of the hydrocarbon group having 1 to 30 carbon atoms.
- the halogen atom capable of substituting the aryl group having 6 to 20 carbon atoms represented by R 8 is the same as the halogen atom represented by R 1 , R 2 , R 3 , R 4 , R 6 and R 7. .
- Examples of the fluorinated alkyl group capable of substituting the aryl group having 6 to 20 carbon atoms represented by R 8 include fluoromethyl, difluoromethyl, trifluoromethyl, pentafluoroethyl and the like.
- R 8 is particularly preferably a group represented by the following formula.
- the hydrocarbon group having 1 to 30 carbon atoms, the group having 2 to 20 carbon atoms containing a heterocyclic ring and the metallocenyl group represented by R 10 and R 11 are respectively R 1 , R 2 , R 3 , R 4 , R 6 and R 7 are the same as the hydrocarbon group having 1 to 30 carbon atoms, the group having 2 to 20 carbon atoms containing a heterocyclic ring, and the metallocenyl group.
- CR 10 R 11 is particularly preferably a group represented by the following formula.
- the hydrocarbon group having 1 to 30 carbon atoms represented by R 12 and the group having 2 to 20 carbon atoms containing a heterocyclic ring are respectively R 1 , R 2 , R 3 , R 4 , R 6 and R 7 is the same as the hydrocarbon group having 1 to 30 carbon atoms and the group having 2 to 20 carbon atoms containing a heterocyclic ring.
- R 1 , R 2 , R 3 , R 4 , R 6 and R 7 is the same as the hydrocarbon group having 1 to 30 carbon atoms and the group having 2 to 20 carbon atoms containing a heterocyclic ring.
- N-Me is particularly preferable.
- the ring structure formed by combining R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 10 and R 11 , R 12 and R 1 includes a cyclopentane ring, C5-C16 aliphatic ring such as cyclohexane ring and cycloheptane ring, C6-C16 aromatic ring such as benzene ring, naphthalene ring and anthracene ring, piperidine ring, piperazine ring, pyrrolidine ring, morpholine Phosphorus ring, thiomorpholine ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, quinoline ring, isoquinoline ring, imidazole ring, oxazole ring, imidazolidine ring, pyrazolidine ring, isoxazolidine
- the hydrocarbon group having 1 to 30 carbon atoms represented by R 13 is a hydrocarbon group having 1 to 30 carbon atoms represented by R 1 , R 2 , R 3 , R 4 , R 6 and R 7. It is the same.
- “A is linked in the form of replacing the hydrogen atom of the group represented by R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 or R 9 ”.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 9 are hydrogen atoms, it means that they are connected in a form that replaces the hydrogen atoms.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 9 are each a hydrocarbon group having 1 to 30 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocyclic ring In some cases, it means that the hydrogen atoms contained in these groups are connected in a way that replaces them.
- R 8 is substituted with a halogenated alkyl group, an aryl group having 6 to 20 carbon atoms, or a hydroxyl group, nitro group, cyano group, halogen atom, carboxyl group, sulfonic acid group, sulfonamide group or fluorinated alkyl group
- aryl group having 6 to 20 atoms it means that they are linked in the form of replacing a hydrogen atom contained in those groups.
- A represents a plurality of hydrogen atoms of the same substituent of the polymethine compound represented by the general formula (I) In some cases, they are linked in a form that replaces hydrogen atoms, and in some cases they are linked in a form that replaces hydrogen atoms of different substituents, but it is preferable to link in a form that replaces hydrogen atoms of the same substituent.
- A replaces the polymethine compound represented by one general formula (I) with the hydrogen atom of the group represented by R 5 , and the other general formula (I).
- the polymethine compound represented by the general formula (I) can be linked in such a form that the polymethine compound represented by) is replaced with the hydrogen atom of the group represented by R 5 .
- A replaces the polymethine compound represented by one general formula (I) with the hydrogen atom of the group represented by R 5
- the other polymethine compound represented by the general formula (I) is represented by R 9 .
- Two polymethine compounds represented by the general formula (I) can be linked by replacing the hydrogen atom of the group.
- a hydrocarbon group having 1 to 30 carbon atoms represented by X 1 and a group having 2 to 20 carbon atoms containing a heterocyclic ring are each represented by R 1 , R 2 , R 3 , R 4 derived by removing one arbitrary hydrogen atom from a hydrocarbon group having 1 to 30 carbon atoms and a group having 2 to 20 carbon atoms containing a heterocyclic ring represented by R 6 and R 7 Is a valent group.
- the hydrocarbon group having 1 to 30 carbon atoms represented by R 14 and R 15 is a carbon atom represented by R 1 , R 2 , R 3 , R 4 , R 6 and R 7. This is the same as the hydrocarbon group of 1 to 30.
- the hydrocarbon group having 1 to 30 carbon atoms represented by R 21 and R 22 is represented by R 1 , R 2 , R 3 , R 4 , R 6 and R 7. This is the same as the hydrocarbon group having 1 to 30 carbon atoms.
- the alkoxy group having 1 to 10 carbon atoms in the group represented by R 21 and the alkoxy group having 1 to 10 carbon atoms in the group represented by R 22 include methyloxy , Ethyloxy, propyloxy, isopropyloxy, butyloxy, sec-butyloxy, tert-butyloxy, isobutyloxy, amyloxy, isoamyloxy, tert-amyloxy, hexyloxy, cyclohexyloxy, heptyloxy, isoheptyloxy, tert-heptyloxy, n -Octyloxy, isooctyloxy, tertiary octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy and the like.
- the halogen atom in the formula ( ⁇ -1) is the same as the halogen atom represented by R 1 , R 2 , R 3
- the hydrocarbon group having 1 to 30 carbon atoms represented by R 23 and R 24 and the group having 2 to 20 carbon atoms containing a heterocyclic ring are each represented by R 1 , This is the same as the hydrocarbon group having 1 to 30 carbon atoms represented by R 2 , R 3 , R 4 , R 6 and R 7 and the group having 2 to 20 carbon atoms containing a heterocyclic ring.
- the halogen atoms in the general formula ( ⁇ -3) are all the same as the halogen atoms represented by R 1 , R 2 , R 3 , R 4 , R 6 and R 7 .
- Examples of the aryloxy group having 6 to 20 carbon atoms represented by R 23 and R 24 include phenyloxy, naphthyloxy, 2-methylphenyloxy, 3-methylphenyloxy, 4-methylphenyloxy, 4-vinylphenyl 2-oxy, 3-iso-propylphenyloxy, 4-iso-propylphenyloxy, 4-butylphenyloxy, 4-tert-butylphenyloxy, 4-hexylphenyloxy, 4-cyclohexylphenyloxy, 4-octylphenyl Oxy, 4- (2-ethylhexyl) phenyloxy, 2,3-dimethylphenyloxy, 2,4-dimethylphenyloxy, 2,5-dimethylphenyloxy, 2.6-dimethylphenyloxy, 3.4-dimethylphenyl Oxy, 3.5-dimethylphenyloxy 2,4-di-tert-butylphenyloxy, 2,5-di-
- the ring structure formed by combining R 23 in the above formula ( ⁇ -3) is R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 10 and R 11 , the same as the ring structure formed by combining R 12 and R 1 .
- the hydrocarbon group having 1 to 30 carbon atoms represented by X 2 , X 3 , X 4 or X 5 is R 1 Derived by removing 2, 3, 4 or 5 arbitrary hydrogen atoms from a hydrocarbon group having 1 to 30 carbon atoms represented by R 2 , R 3 , R 4 , R 6 and R 7 Trivalent, tetravalent, pentavalent or hexavalent hydrocarbon group.
- a group having 2 to 20 carbon atoms containing a heterocyclic ring represented by X 2 , X 3 , X 4 or X 5 is R 1 , R 2 , R 3 , R 4 , R 6 and Trivalent, tetravalent, pentavalent derived by removing 2, 3, 4 or 5 arbitrary hydrogen atoms from a group having 2 to 20 carbon atoms containing a heterocyclic ring represented by R 7 Or it is a hexavalent group.
- the halogen atoms represented by R 31 , R 32 , R 33 , R 34 and R 35 are halogens represented by R 1 , R 2 , R 3 , R 4 , R 6 and R 7. Same as atom.
- R 31 , R 32 , R 33 , R 34 , R 35 , R 36 and R 37 a hydrocarbon group having 1 to 30 carbon atoms, a group having 2 to 20 carbon atoms containing a heterocyclic ring, and a metallocenyl
- the groups are each a hydrocarbon group having 1 to 30 carbon atoms represented by R 1 , R 2 , R 3 , R 4 , R 6 and R 7 , or a group having 2 to 20 carbon atoms containing a heterocyclic ring. And the same as the metallocenyl group.
- the ring structures formed by combining R 31 and R 32 , R 32 and R 33 , R 33 and R 34 , R 34 and R 35 and R 36 and R 37 are R 1 and R 2 , R 2 and R 3. , R 3 and R 4 , R 4 and R 5 , R 10 and R 11 , and R 12 and R 1 are the same as the ring structure formed by bonding.
- the hydrocarbon group having 1 to 30 carbon atoms represented by 32 , R 33 , R 34 , R 35 , R 36 , R 37 is an unsubstituted one; a halogen atom such as fluorine, chlorine or bromine; Group, sulfonamido group, sulfonyl group, carboxyl group, cyano group, sulfonic acid group, hydroxyl group, nitro group, mercapto group, imide group, carbamoyl group, phosphoric acid group, etc .; methylene group in alkyl group , —SO 2 NH—, —NHSO 2 —, —O—, —OCO—, —NHCO— or —CONH—; terminal of an alkyl
- the terminal methyl group of the hydrocarbon group having 1 to 30 carbon atoms represented by 32 , R 33 , R 34 , R 35 , R 36 , R 37 is an acidic group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. May have substituents that form salts with various cations, or may have substituents that form salts with various anions after quaternizing the substituted amino group.
- the cations that form 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, vanadium, ammonium having 4 or more carbon atoms, and the like, and as anions that form salts with quaternized substituted amino groups, Monovalent ions such as chloride ions, bromide ions, iodide ions, fluoride ions, etc .; perchlorate ions, hexafluorophosphate ions, hexafluoroantimonate ions, tetrafluoroborate ions, etc.
- 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,
- Inorganic anion methanesulfonate ion, dodecylsulfone Organic sulfonate anions such as ions; heteropolyacid ions such as phosphomolybdate ions, bistrifluoromethylsulfonylimide ions, bisperfluorobutanesulfonylimide ions, tetrakis (pentafluorophenyl) borate ions, tris (fluoroalkylsulfonyl) ) Carbanion, tetrakispentafluorophenylborate anion and the like.
- heteropolyacid ions such as phosphomolybdate ions, bistrifluoromethylsulfonylimide ions, bisperfluorobutanesulfonylimide ions, tetrakis (pentafluorophenyl) borate ions, tris (fluoroalkylsulfonyl) ) Carban
- the substituent that has formed the above-described salt can be obtained by using a precipitant that lakes an acidic dye or a precipitant that lakes a basic dye.
- the precipitating agent that lakes the acidic dye include barium chloride, aluminum chloride, alkaline earth metal salts, manganese salts, and sodium salts.
- the precipitating agent that lakes the basic dye include , Phosphotungstic molybdic acid, phosphotungstic acid, phosphomolybdic acid, silicon tungsten molybdic acid, silicon molybdic acid, tannic acid, tartaric acid, kaolin, green clay, higher fatty acids, etc., in aqueous solution or aqueous dispersion as required It can be obtained by heating and filtration.
- the m-valent cation represented by E m + includes, as the divalent cation, alkaline earth metal ions such as magnesium, calcium, strontium and barium; transition metal cations such as zinc, copper and nickel; Examples of the trivalent cation include typical metal ions such as aluminum; transition metal cations such as cobalt and iron. Examples of the tetravalent or higher cation include transition metal cations such as manganese.
- the m-valent anion represented by L m- includes divalent anions such as tungstate ion, molybdate ion (MoO 4 2 ⁇ ) chromate ion and the like. Phosphomolybdate ion, phosphotungstic acid ion, phosphotungstomolybdate ion, vanadate ion, etc. are mentioned. Examples of the tetravalent anion include silicotungstate ion and the like. Examples thereof include phosphovanad molybdate ions and molybdate ions (Mo 7 O 24 6 ⁇ ).
- the polymethine compound of the present invention represented by the above general formula (I) can have a structure as shown in the following general formula, but may be either structural formula or any structural formula.
- the structural isomers represented by can be used in isolation or as a mixture thereof.
- the NR 5 group and the R 6 group are in the cis configuration (Z configuration) with respect to the double bond, but these groups are in the trans configuration (E configuration).
- the above general formula (I) is defined as including all geometric isomers resulting from these carbon-carbon double bonds.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and X are the same as those in the general formula (I).
- polymethine compound of the present invention represented by the above general formula (I) include the following compound Nos. 1-No. 75.
- the polymethine compound represented by the general formula (II) is preferable because of its excellent solubility or dispersibility in a solvent.
- the polymethine compound represented by the general formula (III) is preferable because of its low sublimation property.
- polymethine compound represented by the following general formula (IV) is preferable because of its low sublimation property.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and X are the same as those in the general formula (I), and X 1 , Z 1 and Z 2 Is the same as the above general formula ( ⁇ ).
- a polymethine compound in which R 9 in the general formulas (I) to (III) is a group represented by the above formula ( ⁇ ) is preferable as a red auxiliary colorant because it exhibits an appropriate absorption wavelength range.
- the absorption wavelength region is preferably 450 to 550 nm, more preferably 500 to 550 nm.
- R 8 in the above general formulas (I) to (IV) is a trifluoromethyl group or a 4-nitrophenyl group are preferred because they are particularly excellent in light resistance and heat resistance.
- a compound in which X in the above general formulas (I) to (IV) is> CR 10 R 11 or a sulfur atom is preferable because it is excellent in light resistance and heat resistance, and particularly> CR 10 R 11 is more preferable. Furthermore, those in which R 10 and R 11 in CR 10 R 11 are methyl groups are more preferable because they are particularly excellent in heat resistance.
- a compound in which m is 1 is preferable because it is excellent in solubility or dispersibility in a solvent.
- a compound in which m is 2 is preferable because of its low sublimability.
- the polymethine compound of the present invention represented by the above general formula (I) is not particularly limited by its production method, and can be obtained by a method using a known general reaction.
- m 1
- the compound can be synthesized by a method in which a reaction product of an indolenine quaternary salt and an amidine compound is reacted with a compound having active methylene as shown in the following reaction formula 1.
- R 41 , R 42 and R 43 are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a carbon atom
- An q- represents a q-valent anion, q is 1 or 2
- p represents a coefficient for maintaining a neutral charge
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and X are the same as those in the general formula (I).
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and X are the same as those in the general formula (I), and X 1 , Z 1 And Z 2 are the same as those in the above formula ( ⁇ ), R 41 , R 42 , R 43 , An q ⁇ , q and p are the same as those in the above reaction formula 1, and X * is a halogen atom. .
- the polymethine compound of the present invention is an optical film, an optical filter, a photosensitive photographic material, a dye, a paint, an ink, an electrophotographic photoreceptor, a toner, a thermal recording paper, a transfer ribbon, an optical as a light absorber, a sensitizer, a dye, and the like. It can be used for applications such as recording dyes, solar cells, photoelectric conversion elements, semiconductor materials, clinical examination reagents, laser treatment dyes, and dyeing.
- the polymethine compound of the present invention is particularly suitable as a light absorber used for an optical film or an optical filter.
- the composition of this invention contains the polymethine compound of this invention, and is used for said various use.
- the composition of the present invention usually contains a resin corresponding to the use in addition to the polymethine compound of the present invention.
- the composition of the present invention further includes necessary components according to the use, for example, optional components such as an organic solvent described later, a light absorber other than the polymethine compound of the present invention, various stabilizers, and the like. It can be contained in an amount.
- the use amounts of the polymethine compound of the present invention and the binder resin are not particularly limited, and are appropriately determined according to the application.
- the optical film and optical filter of the present invention are, for example, an optical film such as an antireflection film, a retardation film, a polarizing film, an orientation film, a protective film, a viewing angle improving film, a brightness improving film, a light shielding film, and an electromagnetic shielding film.
- an optical filter such as a low-pass filter or a color filter, it can be used for a display or an optical lens of an image display device, and is produced using the composition of the present invention containing the polymethine compound of the present invention. Except for this, it can be the same as the conventional optical film and optical filter.
- the optical filter which is one of the uses of the polymethine compound of the present invention will be described in detail below.
- the optical filter of the present invention is produced using the composition of the present invention, and has a layer composed of the composition.
- the layer composed of the composition may be any of the layers described later.
- a binder resin is usually added to the composition of the present invention.
- the binder resin depends on the type of the layer constituted by the composition of the present invention. Typical examples include natural polymer materials such as gelatin, casein, starch, cellulose derivatives, alginic acid, or polymethyl methacrylate, polyvinyl.
- Synthetic polymer materials such as butyral, polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl chloride, styrene-butadiene copolymer, polystyrene, polyester, polyether, polycarbonate, polyamide, polyimide, polyurethane, melamine resin, cyclic olefin resin, adhesives described below, etc. Is mentioned.
- the amount of the polymethine compound of the present invention used is usually 1 to 1000 mg / m 2 , preferably 5 to 100 mg / m 2 per unit area of the optical filter. is there. If the amount used is less than 1 mg / m 2 , the light absorption effect cannot be sufficiently exerted, and if the amount used exceeds 1000 mg / m 2 , the color of the filter becomes too strong and the display quality and the like are deteriorated. There is also a fear that the brightness may be lowered.
- the polymethine compound of the present invention is a mixture of a plurality of types, the amount of the polymethine compound of the present invention used is the total amount.
- the amount of the polymethine compound of the present invention and the binder resin used in the composition of the present invention is not limited, but is usually as follows.
- the present invention when producing the optical filter of the present invention having an adhesive layer composed of the composition of the present invention, the present invention with respect to 100 parts by mass of the solid content of the adhesive which is the binder resin.
- the polymethine compound is 0.0001 to 50 parts by mass, preferably 0.001 to 5.0 parts by mass
- the solvent such as methyl ethyl ketone is 0.1 to 1000 parts by mass, preferably 1.0 to 500 parts by mass.
- a pressure-sensitive adhesive solution (coating solution) was prepared, and this pressure-sensitive adhesive solution was applied to a transparent support such as a PET film that had been subjected to easy adhesion treatment, and then dried to a thickness of 2 to 400 ⁇ m, preferably 5 to 40 ⁇ m.
- the optical filter of the present invention having the adhesive layer is obtained.
- an optional component such as a light absorber other than the polymethine compound of the present invention and various stabilizers is contained in the composition of the present invention, or when a layer other than the adhesive layer is constituted by the composition of the present invention.
- the blending ratio of each component may conform to the above-described blending ratio.
- the optical filter of the present invention When used for a display of an image display device, it is usually disposed on the front surface of the display.
- the optical filter of the present invention may be directly attached to the surface of the display.
- the optical filter When a front plate is provided in front of the display, the optical filter is attached to the front side (outside) or the back side (display side) of the front plate. May be.
- the optical filter of the present invention there may be mentioned one provided with any layer such as an optical filter layer, an undercoat layer, an antireflection layer, a hard coat layer, a lubricating layer, an adhesive layer, etc. on a transparent support.
- the polymethine compound of the present invention may be configured to be contained in any one of a transparent support or a layer such as an undercoat layer, an antireflection layer, a hard coat layer, a lubricating layer, and an adhesive layer.
- the one containing the polymethine compound of the present invention in the adhesive layer is preferable because the production process can be reduced and the laminated optical filter can be produced at low cost.
- the adhesive layer is formed of the adhesive.
- the adhesive include silicone-based, urethane-based, and acrylic-based adhesives, polyvinyl butyral-based adhesives, polyvinyl ether-based adhesives, ethylene-vinyl acetate-based adhesives, polyolefin-based adhesives, and SBR-based adhesives.
- known transparent adhesives for laminated glass such as rubber adhesives, can be used, among which acrylic adhesives, particularly acidic acrylic adhesives are preferably used.
- the acrylic pressure-sensitive adhesive is not particularly limited, and a homopolymer or a plurality of monomers having a reactive functional group such as a carboxyl group, a hydroxyl group, an amide group, an amino group, and an epoxy group and an ethylenically unsaturated double bond Copolymers combining species, or monomers having the above reactive functional groups and ethylenically unsaturated double bonds, and ethylenically unsaturated compounds such as (meth) acrylic monomers and vinyl monomers
- a copolymer with a monomer having a double bond can be used, and a metal chelate compound, an isocyanate compound, a melamine compound, Those containing a crosslinking agent such as an epoxy compound, an amine compound, an aziridine compound, and an oxazoline compound can be used.
- acrylic pressure-sensitive adhesive commercially available ones can be used.
- Davy Bond 5541 (Diabond), SK Dyne AS-1925, KP-2230, SK-1811L (Soken Chemical), DX2- PDP-19 (manufactured by Nippon Shokubai Co., Ltd.), AT-3001 (manufactured by Syden Chemical Co., Ltd.), Olivevine BPS5896 (manufactured by Toyo Ink Co., Ltd.), CS-9611 (manufactured by Nitto Denko Corporation), and the like.
- the polymethine compound of the present invention In the production of the optical filter of the present invention having the above-mentioned adhesive layer, the polymethine compound of the present invention, other light absorbers other than the polymethine compound of the present invention, various stabilizers, etc., the transparent support and any of the various layers
- the composition is used as the adhesive. It is only necessary to bond two adjacent members of the transparent support and any of the layers.
- a well-known separator film such as an easily adhered polyethylene terephthalate film can be provided on the surface of the adhesive layer.
- the material for the transparent support examples include inorganic materials such as glass; cellulose esters such as diacetylcellulose, triacetylcellulose (TAC), propionylcellulose, butyrylcellulose, acetylpropionylcellulose, and nitrocellulose; polyamide; polycarbonate Polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate; polystyrene Polyolefins such as polyethylene, polypropylene and polymethylpentene; acrylic resins such as polymethyl methacrylate; polycarbonate; poly Polymer materials such as sulfone; polyethersulfone; polyetherketone; polyetherimide; polyoxyethylene, norbornene resin.
- the transmittance of the transparent support is preferably 80% or more
- the transparent support in addition to the polymethine compound of the present invention, other light absorbers, infrared absorbers, ultraviolet absorbers, fluorescence quenchers, phenol-based, phosphorus-based, sulfur-based antioxidants, flame retardants, Lubricants, antistatic agents, inorganic fine particles, light fastness-imparting agents, aromatic nitroso compounds, aminium compounds, iminium compounds, transition metal chelate compounds, viscosity minerals, etc. can be added.
- the surface treatment can also be performed.
- the light absorber for adjusting the color tone, the light absorption for preventing reflection of external light and reflection.
- the image display device is a plasma display
- a light absorber for preventing infrared remote control malfunction is used.
- trimethine indolium compound, trimethine benzoxazolium compound, trimethine benzothiazolium compound are used for removing orange light having a wavelength of 450 to 620 nm.
- Trimethine cyanine derivatives such as pentamethine oxazolium compounds, pentamethine cyanine derivatives such as pentamethine thiazolium compounds, squarylium dye derivatives, azomethine dye derivatives, xanthene dye derivatives, azo dye derivatives, oxonol dye derivatives, benzylidene dye derivatives
- Examples of the light absorber for preventing reflection or reflection of external light include trimethine indolium compound, trimethine oxazolium compound, trimethine thiazolium compound, indolidene trimethine thiazonium. Trimethine cyanine derivatives such as compounds; phthalocyanine derivatives; naphthalocyanine derivatives; porphyrin derivatives; dipyrromethene metal chelate compounds.
- Examples of the above-mentioned light absorber for preventing infrared remote control malfunction include diimonium compounds; pentamethine benzoindolium compounds, pentamethine benzoxazolium compounds, pentamethine benzothiazolium compounds, etc. Pentamethine cyanine derivatives; heptamethine indolium compounds, heptamethine benzoindolium compounds, heptamethine oxazolium compounds, heptamethine benzoxazolium compounds, heptamethine thiazolium compounds, heptamethine benzothiazolium compounds, etc.
- Methine cyanine derivatives squarylium derivatives; nickel complexes such as bis (stilbenedithiolato) compounds, bis (benzenedithiolato) nickel compounds, bis (camphagethiolato) nickel compounds; Derivatives; azo dye derivatives; phthalocyanine derivatives; porphyrin derivatives; dipyrromethene metal chelate compounds, and the like.
- Examples of the inorganic fine particles that can be added to the transparent support include silicon dioxide, titanium dioxide, barium sulfate, calcium carbonate, talc, and kaolin.
- Examples of the various surface treatments that can be applied to the transparent support include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser. Treatment, mixed acid treatment, ozone oxidation treatment and the like.
- the undercoat layer that can be provided in the optical filter of the present invention is a layer that is used between the transparent support and the optical filter layer when an optical filter layer containing a light absorber is provided separately from each arbitrary layer. .
- the undercoat layer is formed as a layer containing a polymer having a glass transition temperature of ⁇ 60 to 60 ° C., a layer having a rough surface on the optical filter layer side, or a layer containing a polymer having an affinity for the polymer of the optical filter layer. To do.
- the undercoat layer is provided on the surface of the transparent support on which the optical filter layer is not provided, thereby improving the adhesion between the transparent support and the layer provided thereon (for example, an antireflection layer or a hard coat layer).
- the thickness of the undercoat layer is preferably 2 nm to 20 ⁇ m, more preferably 5 nm to 5 ⁇ m, still more preferably 20 nm to 2 ⁇ m, still more preferably 50 nm to 1 ⁇ m, and most preferably 80 nm to 300 nm.
- the undercoat layer containing a polymer having a glass transition temperature of ⁇ 60 to 60 ° C. adheres the transparent support and the optical filter layer due to the tackiness of the polymer. Polymers having a glass transition temperature of ⁇ 60 to 60 ° C.
- the glass transition temperature is preferably 50 ° C. or less, more preferably 40 ° C. or less, further preferably 30 ° C. or less, still more preferably 25 ° C. or less, and further preferably 20 ° C. or less. Most preferred.
- the undercoat layer having a rough surface of the optical filter layer forms an optical filter layer on the rough surface, thereby bonding the transparent support and the optical filter layer.
- the undercoat layer having a rough surface of the optical filter layer can be easily formed by applying a polymer latex.
- the average particle size of the latex is preferably 0.02 to 3 ⁇ m, and more preferably 0.05 to 1 ⁇ m.
- Examples of the polymer having an affinity for the binder polymer of the optical filter layer include acrylic resins, cellulose derivatives, alginic acid, gelatin, casein, starch, polyvinyl alcohol, polyvinyl butyral, polyvinyl pyrrolidone, soluble nylon, and polymer latex.
- the optical filter of the present invention may be provided with two or more undercoat layers. In the undercoat layer, a solvent for swelling the transparent support, a matting agent, a surfactant, an antistatic agent, a coating aid, a hardening agent, and the like may be added.
- a low refractive index layer is essential.
- the refractive index of the low refractive index layer is lower than the refractive index of the transparent support.
- the refractive index of the low refractive index layer is preferably 1.20 to 1.55, and more preferably 1.30 to 1.50.
- the thickness of the low refractive index layer is preferably 50 to 400 nm, and more preferably 50 to 200 nm.
- the low refractive index layer is a layer made of a fluorine-containing polymer having a low refractive index (Japanese Patent Laid-Open Nos.
- a layer obtained by a sol-gel method Japanese Patent Laid-Open Nos. 5-208811, JP-A-6-299091, and JP-A-7-168003
- a layer containing fine particles Japanese Patent Publication No. 60.
- voids can be formed in the low refractive index layer as microvoids between the fine particles or within the fine particles.
- the layer containing fine particles preferably has a porosity of 3 to 50% by volume, and more preferably has a porosity of 5 to 35% by volume.
- a layer having a high refractive index (medium / high refractive index layer) is preferably laminated.
- the refractive index of the high refractive index layer is preferably 1.65 to 2.40, more preferably 1.70 to 2.20.
- the refractive index of the middle refractive index layer is adjusted to be an intermediate value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer.
- the refractive index of the medium refractive index layer is preferably 1.50 to 1.90, and more preferably 1.55 to 1.70.
- the thickness of the middle / high refractive index layer is preferably 5 nm to 100 ⁇ m, more preferably 10 nm to 10 ⁇ m, and most preferably 30 nm to 1 ⁇ m.
- the haze of the middle / high refractive index layer is preferably 5% or less, more preferably 3% or less, and most preferably 1% or less.
- the middle / high refractive index layer can be formed using a polymer binder having a relatively high refractive index.
- polymers having a high refractive index examples include polystyrene, styrene copolymer, styrene-butadiene copolymer, polyvinyl chloride, polycarbonate, polyamide, melamine resin, phenol resin, epoxy resin, cyclic (alicyclic or aromatic) isocyanate and polyol. And the like obtained by the reaction.
- Polymers having other cyclic (aromatic, heterocyclic, alicyclic) groups and polymers having a halogen atom other than fluorine as a substituent also have a high refractive index. You may use the polymer formed by the polymerization reaction of the monomer which introduce
- inorganic fine particles may be dispersed in the polymer binder.
- the refractive index of the inorganic fine particles is preferably 1.80 to 2.80.
- the inorganic fine particles are preferably formed from a metal oxide or sulfide.
- the metal oxide or sulfide include titanium oxide (for example, rutile, rutile / anatase mixed crystal, anatase, amorphous structure), tin oxide, indium oxide, zinc oxide, zirconium oxide, and zinc sulfide.
- titanium oxide, tin oxide, and indium oxide are particularly preferable.
- the inorganic fine particles are mainly composed of oxides or sulfides of these metals, and can further contain other elements.
- the main component means a component having the largest content (mass%) among the components constituting the particles.
- examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S.
- a medium / high refractive index layer can also be formed using a polymer.
- the surface of the antireflection layer can be provided with an antiglare function (function of scattering incident light on the surface and preventing the scenery around the film from moving to the film surface).
- an antiglare function function of scattering incident light on the surface and preventing the scenery around the film from moving to the film surface.
- it has an anti-glare function by forming fine irregularities on the surface of the transparent film and forming an antireflection layer on the surface, or by forming irregularities on the surface with an embossing roll after forming the antireflection layer.
- An antireflection layer can be obtained.
- An antireflection layer having an antiglare function generally has a haze of 3 to 30%.
- the hard coat layer that can be provided in the optical filter of the present invention has a hardness higher than the hardness of the transparent support.
- the hard coat layer preferably contains a crosslinked polymer.
- the hard coat layer can be formed using an acrylic, urethane, or epoxy polymer, oligomer, or monomer (for example, an ultraviolet curable resin).
- a hard coat layer can also be formed from a silica-based material.
- a lubricating layer can be formed on the surface of the antireflection layer (low refractive index layer).
- the lubricating layer has a function of imparting slipperiness to the surface of the low refractive index layer and improving scratch resistance.
- the lubricating layer can be formed using polyorganosiloxane (for example, silicon oil), natural wax, petroleum wax, higher fatty acid metal salt, fluorine-based lubricant or derivative thereof.
- the thickness of the lubricating layer is preferably 2 to 20 nm.
- an organic solvent can be used at the same time, and the organic solvent is not particularly limited, and various known solvents can be appropriately used.
- Alcohols such as isopropanol; ether alcohols such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, butyl diglycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, ethyl acetate, butyl acetate, methoxyacetate Esters such as ethyl; acrylic acid esters such as ethyl acrylate and butyl acrylate; fluorinated alcohols such as 2,2,3,3-tetrafluoropropanol; hydrocarbons such as hexane, benzene, toluene and xylene Methylene dichloride, dichloroethane,
- the undercoat layer, antireflection layer, hard coat layer, lubricating layer, optical filter layer, etc. can be formed by a general coating method.
- a coating method a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, an extrusion coating method using a hopper (described in US Pat. No. 2,681,294), etc. Is mentioned.
- Two or more layers may be formed by simultaneous application. Regarding the simultaneous application method, US Pat. No. 2,761,789, US Pat. No. 2,941,898, US Pat. No. 3,508,947, US Pat. No. 3,526,528 and Yuji Harasaki “Coating Engineering”, page 253 (published by Asakura Shoten in 1973) There is a description.
- an organic solvent is contained in the composition of the present invention to form the coating liquid of the present invention.
- concentration (solid content) of the coating liquid containing the polymethine compound of the present invention, the binder resin, the organic solvent and optional components such as a light absorber other than the polymethine compound of the present invention and various stabilizers is 1 to 50% by mass, In particular, the content is preferably 10 to 30% by mass.
- Example 1 Compound No. 1 Production of Compound No. 1 The production of 1 and its intermediate is shown below.
- Step 2 Production of intermediate 1B>
- 1,1,2,3-tetramethyl-1H-benz [e] indolium iodide (245.86 g, 0.7 mol), N, N′-diphenylformamidine (164.85 g, 0.84 mol) ), BuOH (636.1 g) was added, and the reaction was performed at an internal temperature of 85 ° C. for 3 hours.
- water (12.6 g, 0.7 mol) was added dropwise and stirred for 30 minutes. Ethyl acetate was added dropwise thereto, and the precipitated solid was filtered off and dried at 80 ° C. under reduced pressure. 262.1 g of intermediate 1B was obtained (yield 82.4%).
- ⁇ Maximum absorption wavelength ( ⁇ max) and molar extinction coefficient ( ⁇ )> Compound No. 1-No. 7 or No. 43-No. 10 mg of 46 was weighed and placed in a 100 ml volumetric flask. Chloroform was added to the marked line and shaken with ultrasound for 10 minutes to obtain a uniform solution. 2 ml was taken out from the obtained solution with a whole pipette, put into an empty 100 ml volumetric flask, and then chloroform was added to the marked line to prepare a measurement sample. The above measurement sample was subjected to the following measurements using JASCO U-3900.
- the above measurement sample is put in a quartz cell having an optical path length of 1 cm, the absorbance is measured at 300 nm / min in the visible light region of 800 to 300 nm at intervals of 0.5 nm, and the maximum is measured at 600 to 400 nm.
- the wavelength at which absorbance is obtained is ⁇ max.
- the molar extinction coefficient ⁇ was calculated from the absorbance at ⁇ max and its molecular weight using the Lambert Beer law. The results are shown in [Table 1].
- ⁇ Decomposition temperature> A differential thermal simultaneous thermogravimetry apparatus TG-DTA6200 manufactured by Seiko Instruments Inc. was used. Compound No. was applied to the sample aluminum pan. 1-No. 7 or No. 43-No. 2 mg of 46 was weighed and measured at a nitrogen flow of 200 ml / min, a heating rate of 10 ° C./min, and a measurement temperature range of 35 ° C. to 550 ° C. The decomposition temperature was calculated from the intersection point of the TG curve with a weight loss of 0% and the tangent line with a weight loss of 10%. The results are shown in [Table 1].
- Tetrabutylammonium perchlorate (Nacalai Tesque Polarography Reagent) is dissolved in dehydrated dichloromethane at a concentration of 0.1 M, and a dye (Compound No. 3, No. 4 or Comparative Compound No. 3) is added to this solution. Dissolved at 1.0 ⁇ 10 ⁇ 3 M. 5 ml of this dye solution is put into an electrochemical cell, an Ag / AgCl reference electrode, a platinum wire type counter electrode, and a platinum working electrode are attached, swept from ⁇ 0.4 V to 1.5 V with a BAS electrochemical analyzer 600 C, and oxidized potential The peak value of was determined.
- the polymethine compounds (Compound No. 3 and No. 4) of the present invention are comparative compounds (Comparative Compound No. 3) in which the group corresponding to R 8 in the general formula (I) is a methyl group. It is clear that the oxidation potential is higher than that.
- the coating solution obtained above was applied to a 188 ⁇ m thick polyethylene terephthalate film that had been subjected to easy adhesion treatment using bar coater # 30, and then dried at 70 ° C. for 15 minutes to produce an optical filter (film thickness 7-8 ⁇ m). did.
- ADVANTAGE OF THE INVENTION According to this invention, it is excellent in light resistance and heat resistance, and can provide the polymethine compound suitable for an optical film and an optical filter.
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Abstract
Description
本発明は、上記知見に基づき成されたものであり、下記一般式(I)で表されるポリメチン化合物を提供するものである。
R5及びR9は、それぞれ独立に、水素原子、炭素原子数1~30の炭化水素基、又は複素環を含有する炭素原子数2~20の基を表し、
R8は、炭素原子数1~20のハロゲン化アルキル基、炭素原子数6~20のアリール基、又は、水酸基、ニトロ基、シアノ基、ハロゲン原子、カルボキシル基、スルホン酸基、スルホンアミド基若しくはフッ化アルキル基で置換された炭素原子数6~20のアリール基を表し、
Xは、>CR10R11、酸素原子、硫黄原子又は>NR12を表し、
R10及びR11は、それぞれ独立に、水素原子、炭素原子数1~30の炭化水素基、複素環を含有する炭素原子数2~20の基又はメタロセニル基を表し、
R12は、水素原子、炭素原子数1~30の炭化水素基、複素環を含有する炭素原子数2~20の基を表し、
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11及びR12で表される基中のメチレン基は、-O-、-S-、-CO-、-COO-、-OCO-、-COS-、-OCS-、-SO2-、-SO3-、-NH-、-CONH-、-NHCO-、-SO2NH-、-NH-SO2-、-N=CH-、-CH=CH―、又はこれらを組み合わせた基によって、酸素原子が隣り合わない条件で、置き換わっている場合もあり、
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11及びR12で表される基のアルキル部分は、分岐側鎖又は環状アルキルである場合があり、置換基を有する場合もあり、
R1とR2、R2とR3、R3とR4、R4とR5、R10とR11及びR12とR1は、それぞれ結合して環を形成する場合があり、形成した環は置換基を有する場合もあり、
mは1~6の整数であり、
m≧2の場合、複数存在するR1、R2、R3、R4、R5、R6、R7、R8、R9及びXは、それぞれ同一である場合があり、異なる場合もあり、
m=1の場合、Aは、存在せず、m≧2のとき、Aは、直接結合、窒素原子、>NR13、酸素原子、硫黄原子、-SO2-、-SO-、リン原子、>PR13、Em+、Lm-又は下記(i)、(ii)、(iii)、(iv)若しくは(v)に示すいずれかの連結基を表し、
R13は、水素原子、又は炭素原子数1~30の炭化水素基を表し、
R13で表される炭素原子数1~30の炭化水素基中のメチレン基は、-COO-、-O-、-OCO-、-NHCO-、-NH-、-CONH-、又はこれらを組み合わせた基によって、酸素原子が隣り合わない条件で、置き換わっている場合もあり、
Em+はm価の陽イオンを表し、Lm-はm価の陰イオンを表し、
m≧2でAがEm+又はLm-でない場合、AはR1、R2、R3、R4、R5、R6、R7、R8又はR9で表される基の水素原子に置き換わる形で連結する。)
(i)m=2のとき、Aは、下記式(α)で表される連結基である場合がある。
Z1及びZ2は、それぞれ独立に、直接結合、-O-、-S-、-SO2-、-SO-、>NR14、又は>PR15を表し、
R14及びR15は、それぞれ独立に、水素原子、又は炭素原子数1~30の炭化水素基を表し、
R14及びR15で表される基中のメチレン基は、-COO-、-O-、-OCO-、-NHCO-、-NH-、-CONH-、又はこれらを組み合わせた基によって、酸素原子が隣り合わない条件で、置き換わっていてもよい。
但し、上記式(α)で表される基は炭素原子数1~35の範囲内であり、式中の*は、*部分で、隣接する基と結合することを意味する。)
上記の炭素原子数1~30の炭化水素基及び炭素原子数1~10のアルコキシ基の水素原子はハロゲン原子で置き換わっている場合があり、
dは0~4の整数であり、
式中の*は、*部分で、隣接する基と結合することを意味する。)
R23及びR24で表される基中の水素原子は、ハロゲン原子で置き換わっている場合があり、
R23及びR24で表される基中のメチレン基は、不飽和結合、-O-、-S-、又はこれらを組み合わせた基によって、酸素原子が隣り合わない条件で、置き換わっている場合があり、
R23は、隣接するR23同士が結合して環を形成する場合があり、
eは0~4の数を表し、fは0~8の数を表し、gは0~4の数を表し、hは0~4の数を表し、gとhの数の合計は2~4であり、
式中の*は、*部分で、隣接する基と結合することを意味する。)
(ii)m=3のとき、Aは、下記式(β)で表される連結基である場合がある。
X2で表される基中のメチレン基は、-COO-、-O-、-OCO-、-NHCO-、-NH-、-CONH-、-O-CONH-、-NHCO-O-、又はこれらを組み合わせた基によって、酸素原子が隣り合わない条件で、置き換わっている場合もあり、
Z1、Z2及びZ3は、それぞれ独立に、上記式(α)におけるZ1及びZ2で表される基と同じである。
但し、上記一般式(β)で表わされる基は炭素原子数1~35の範囲内であり、式中の*は、*部分で、隣接する基と結合することを意味する。)
(iii)m=4のとき、Aは、下記式(γ)で表される連結基である。
X3で表される基中のメチレン基は、-COO-、-O-、-OCO-、-NHCO-、-NH-、-CONH-、-O-CONH-、-NHCO-O-、又はこれらを組み合わせた基によって、酸素原子が隣り合わない条件で、置き換わっている場合もあり、
Z1、Z2、Z3及びZ4は、それぞれ独立に、上記式(α)におけるZ1及びZ2で表される基と同じである。
但し、上記一般式(γ)で表される基は炭素原子数1~35の範囲内であり、式中の*は、*部分で、隣接する基と結合することを意味する。)
(iv)m=5のとき、Aは、下記式(δ)で表される連結基である。
X4で表される基中のメチレン基は、-COO-、-O-、-OCO-、-NHCO-、-NH-、-CONH-、-O-CONH-、-NHCO-O-、又はこれらを組み合わせた基によって、酸素原子が隣り合わない条件で置き換わっている場合もあり、
Z1、Z2、Z3、Z4及びZ5は、それぞれ独立に、上記式(α)におけるZ1及びZ2で表される基と同じである。
但し、上記一般式(δ)で表される基は炭素原子数2~35の範囲内であり、式中の*は、*部分で、隣接する基と結合することを意味する。)
(v)m=6のとき、Aは、下記式(ε)で表される連結基である。
X5で表される基中のメチレン基は、-COO-、-O-、-OCO-、-NHCO-、-NH-、-CONH-、-O-CONH-、-NHCO-O-、又はこれらを組み合わせた基によって、酸素原子が隣り合わない条件で、置き換わっている場合もあり、
Z1、Z2、Z3、Z4、Z5及びZ6は、それぞれ独立に、上記式(α)におけるZ1及びZ2で表される基と同じである。
但し、上記一般式(ε)で表される基は炭素原子数2~35の範囲内であり、式中の*は、*部分で、隣接する基と結合することを意味する。)
R31、R32、R33、R34及びR35のうち、一つ以上は、-SO2NR36R37であり、
R36及びR37は、それぞれ独立に、水素原子、炭素原子数1~30の炭化水素基、複素環を含有する炭素原子数2~20の基又はメタロセニル基を表し、
R31、R32、R33、R34、R35、R36及びR37で表される基中のメチレン基は、-O-、-S-、-CO-、-COO-、-OCO-、-COS-、-OCS-、-SO2-、-SO3-、-NH-、-CONH-、-NHCO-、-SO2NH-、-NH-SO2-、-N=CH-、-CH=CH―、又はこれらを組み合わせた基によって、酸素原子が隣り合わない条件で、置き換わっている場合もあり、
R31、R32、R33、R34、R35、R36及びR37で表される基のアルキル部分は、分岐側鎖又は環状アルキルである場合があり、置換基を有する場合もあり、
R31とR32、R32とR33、R33とR34、R34とR35及びR36とR37は、それぞれ結合して環を形成する場合があり、形成した環は置換基を有する場合もある。)
上記炭素原子数1~30の炭化水素基が炭素原子数1~20のアルキル基、炭素原子数3~20のシクロアルキル基又は炭素原子数4~20のシクロアルキルアルキル基である場合、置換基としては、以下に例示の置換基のうち、アルキル基、アリールアルキル基以外の置換基が挙げられる。
上記炭素原子数1~30の炭化水素基が炭素原子数6~30のアリール基である場合、置換基としては、好ましくは単環若しくは縮環構造の芳香族系炭化水素環(環構造の部分のみをいう。以下、「芳香族系炭化水素環」において同じ。)又はその連結構造の置換基としては、以下に例示の置換基のうち、アリール基以外の置換基が挙げられる。
上記炭素原子数1~30の炭化水素基が炭素原子数2~20のアルケニル基、炭素原子数7~30のアリールアルキル基又は炭素原子数8~30のアリールアルケニル基である場合、好ましい置換基としては、下記に例示の中でも、単環若しくは縮環構造の芳香族系炭化水素環又はその連結構造が結合したアルキル基が挙げられる。
但し、以下に例示の置換基のうち、アルキル基、アリールアルキル基、アリールアルケニル基は、炭素原子数7~30のアリールアルキル基又は炭素原子数8~30のアリールアルケニル基の芳香族系炭化水素環に置換する。
複素環を含有する炭素原子数2~20の置換基としては、以下に例示の置換基のうち、複素環を含有する基以外の置換基が挙げられる。
尚、上記炭素原子数1~30の炭化水素基又は上記複素環を含有する炭素原子数2~20の基が、以下の置換基の中でも、炭素原子を含有する置換基を有する場合は、該置換基を含めた全体の炭素原子数が、規定された範囲を満たすものとする。つまり、炭素原子数1~30の炭化水素基が、炭素原子を含有する置換基を有する場合の炭素原子数の範囲は、置換基も含めた全体として1~30であり、複素環を含有する炭素原子数2~20の基が、炭素原子を含有する置換基を有する場合の炭素原子数の範囲は、置換基も含めた全体として2~30であり、また、例えば、炭素原子数1~20のアルキル基が、炭素原子を含有する置換基を有する場合の炭素原子数の範囲は、置換基も含めた全体として1~20である。
また、上記カルボン酸基、スルホン酸基及びリン酸基等の酸性基は、種々の陽イオンと塩を形成している場合もあり、上記置換アミノ基(例えば、ジエチルアミノ基、ジメチルアミノ基)は、四級化した後、例えばメチル基、エチル基等の炭化水素数1~10のアルキル基で四級化した後、種々の陰イオンと塩を形成している場合もある。上記陽イオンとしては、アルカリ金属イオン、アルカリ土類金属イオン、遷移金属カチオン、炭素原子数4以上のアンモニウム、アミジニウム、グアニジニウムカチオン等が挙げられ、陰イオンとしては、例えば、一価のものとして、塩化物イオン、臭化物イオン、ヨウ化物イオン、フッ化物イオン等のハロゲン化物イオン;過塩素酸イオン、塩素酸イオン、チオシアン酸イオン、ヘキサフルオロリン酸イオン、ヘキサフルオロアンチモン酸イオン、テトラフルオロホウ酸イオン等の無機系陰イオン;メタンスルホン酸イオン、ドデシルスルホン酸イオン、ベンゼンスルホン酸イオン、トルエンスルホン酸イオン、トリフルオロメタンスルホン酸イオン、ペンタフルオロベンゼンスルホン酸イオン、ジフェニルアミン-4-スルホン酸イオン、2-アミノ-4-メチル-5-クロロベンゼンスルホン酸イオン、2-アミノ-5-ニトロベンゼンスルホン酸イオン、フタロシアニンスルホン酸イオン、パーフルオロ-4-エチルシクロヘキサンスルホン酸イオン、ナフタレンモノスルホン酸、ナフタレンジスルホン酸、ナフタレントリスルホン酸、ナフチルアミンモノスルホン酸、ナフチルアミンジスルホン酸、ナフチルアミントリスルホン酸、ナフトールモノスルホン酸、ナフトールジスルホン酸、ナフトールトリスルホン酸等の有機スルホン酸系陰イオン;チオシアン酸イオン、リンタングステンモリブデン酸イオン、リンタングステン酸イオン、リンモリブデン酸イオン、タンニン酸イオン、酒石酸イオン、パルミチン酸イオン、ステアリン酸イオン、オレイン酸イオン、リノール酸イオン、オクチルリン酸イオン、ドデシルリン酸イオン、オクタデシルリン酸イオン、フェニルリン酸イオン、ノニルフェニルリン酸イオン、2,2’-メチレンビス(4,6-ジ-t-ブチルフェニル)ホスホン酸イオン等の有機リン酸系陰イオン、ビストリフルオロメチルスルホニルイミドイオン、ビスパーフルオロブタンスルホニルイミドイオン、テトラキス(ペンタフルオロフェニル)ホウ酸イオン、トリス(フルオロアルキルスルホニル)カルボアニオン、テトラキスペンタフルオロフェニルボレートアニオン等が挙げられる。
R8で表される炭素原子数6~20のアリール基は、炭素原子数1~30の炭化水素基の例として述べた上記炭素原子数6~20のアリール基と同様である。
R8で表される炭素原子数6~20のアリール基を置換し得るハロゲン原子は、R1、R2、R3、R4、R6及びR7で表されるハロゲン原子と同様である。
R8で表される炭素原子数6~20のアリール基を置換し得るフッ化アルキル基としては、フルオロメチル、ジフルオロメチル、トリフルオロメチル、ペンタフルオロエチル等が挙げられる。
>CR10R11としては、下記式で表される基が特に好ましい。
>NR12としては、>N-Meが特に好ましい。
式(α)において、R14及びR15で表される炭素原子数1~30の炭化水素基は、R1、R2、R3、R4、R6及びR7で表される炭素原子数1~30の炭化水素基と同様である。
式(α-1)において、R21で表される基中の炭素原子数1~10のアルコキシ基及びR22で表される基中の炭素原子数1~10のアルコキシ基としては、メチルオキシ、エチルオキシ、プロピルオキシ、イソプロピルオキシ、ブチルオキシ、第二ブチルオキシ、第三ブチルオキシ、イソブチルオキシ、アミルオキシ、イソアミルオキシ、第三アミルオキシ、ヘキシルオキシ、シクロヘキシルオキシ、ヘプチルオキシ、イソヘプチルオキシ、第三ヘプチルオキシ、n-オクチルオキシ、イソオクチルオキシ、第三オクチルオキシ、2-エチルヘキシルオキシ、ノニルオキシ、デシルオキシ等が挙げられる。
式(α-1)におけるハロゲン原子は、R1、R2、R3、R4、R6及びR7で表されるハロゲン原子と同様である。
上記一般式(α-3)におけるハロゲン原子はいずれも、R1、R2、R3、R4、R6及びR7で表されるハロゲン原子と同様である。
R23及びR24で表される炭素原子数6~20のアリールオキシ基としては、フェニルオキシ、ナフチルオキシ、2-メチルフェニルオキシ、3-メチルフェニルオキシ、4-メチルフェニルオキシ、4-ビニルフェニル二オキシ、3-iso-プロピルフェニルオキシ、4-iso-プロピルフェニルオキシ、4-ブチルフェニルオキシ、4-tert-ブチルフェニルオキシ、4-へキシルフェニルオキシ、4-シクロヘキシルフェニルオキシ、4-オクチルフェニルオキシ、4-(2-エチルヘキシル)フェニルオキシ、2,3-ジメチルフェニルオキシ、2,4-ジメチルフェニルオキシ、2,5-ジメチルフェニルオキシ、2.6-ジメチルフェニルオキシ、3.4-ジメチルフェニルオキシ、3.5-ジメチルフェニルオキシ、2,4-ジーtert-ブチルフェニルオキシ、2,5-ジーtert-ブチルフェニルオキシ、2,6-ジーtert-ブチルフェニルオキシ、2.4-ジーtert-ペンチルフェニルオキシ、2,5-tert-アミルフェニルオキシ、4-シクロへキシルフェニルオキシ、2,4,5-トリメチルフェニルオキシ、フェロセニルオキシ等の基及びこれらの基がハロゲン原子で置換された基が奉げられ、
炭素原子数6~20のアリールチオ基としては、上記炭素原子数6~20のアリールオキシ基の酸素原子を硫黄原子に置き換えた基等が奉げられる。
R31、R32、R33、R34、R35、R36及びR37で表される炭素原子数1~30の炭化水素基、複素環を含有する炭素原子数2~20の基及びメタロセニル基は、それぞれ、R1、R2、R3、R4、R6及びR7で表される炭素原子数1~30の炭化水素基、複素環を含有する炭素原子数2~20の基及びメタロセニル基と同様である。
R31とR32、R32とR33、R33とR34、R34とR35及びR36とR37が結合して形成する環構造は、R1とR2、R2とR3、R3とR4、R4とR5、R10とR11、R12とR1が結合して形成する環構造と同様である。
R1、R2、R3、R4、R5、R6、R7、R8、R9及びXは、上記一般式(I)と同じである。)
m=3以上のポリメチン化合物も、AがR5以外と連結する場合も、下記反応式2に示されるルートに準じて合成することができる。
本発明の組成物には、その他に、用途に応じて必要な成分や、例えば、後述する有機溶媒、本発明のポリメチン化合物以外の光吸収剤、各種安定剤等の任意成分等を、さらに必要量含有させることができる。
本発明の組成物において、本発明のポリメチン化合物及び上記バインダー樹脂等の使用量は特に制限されず、用途に応じて適宜決定される。
本発明の光学フィルム及び光学フィルタは、例えば、反射防止フィルム、位相差フィルム、偏光フィルム、配向フィルム、保護フィルム、視野角向上フィルム、輝度向上フィルム、遮光フィルム、電磁波シールドフィルム等の光学フィルムとして、又はローパスフィルタ、カラーフィルタ等の光学フィルタとして、画像表示装置のディスプレイや光学レンズ等に用いることができるものであり、本発明のポリメチン化合物を含有する本発明の組成物を用いて作製される点以外は、従来の光学フィルム及び光学フィルタと同様とすることができる。
本発明の光学フィルタは、本発明の組成物を用いて作製されたものであり、該組成物により構成された層を有する。該組成物により構成される層は、後述する各層の何れの層でもよい。本発明の光学フィルタを作製する際、本発明の組成物には、通常バインダー樹脂が配合される。該バインダー樹脂は、本発明の組成物により構成する層の種類によるが、代表例としては、例えば、ゼラチン、カゼイン、でんぷん、セルロース誘導体、アルギン酸等の天然高分子材料、或いは、ポリメチルメタクリレート、ポリビニルブチラール、ポリビニルピロリドン、ポリビニルアルコール、ポリ塩化ビニル、スチレン-ブタジエンコポリマー、ポリスチレン、ポリエステル、ポリエーテル、ポリカーボネート、ポリアミド、ポリイミド、ポリウレタン、メラミン樹脂、環状オレフィン樹脂等の合成高分子材料、後述する粘着剤等が挙げられる。
化合物No.1及びその中間体の製造について下記に示す。
フラスコに(4-ニトロベンゾイル)酢酸エチル(156.6g、0.66mol)、4-ヒドラジノベンゼンスルホンアミド塩酸塩(147.63g、0.66mol)、ピリジン(475.60g)を入れ、100℃で2時間攪拌後、これにメタノールを滴下して析出した固体をろ別し、減圧下、120度で溶剤留去し、中間体1Aの180.60gを得た(収率75.9%)。
2Lフラスコに1,1,2,3-テトラメチル-1H-ベンズ[e]インドリウム=ヨージド(245.86g、0.7mol)、N,N’-ジフェニルホルムアミジン(164.85g、0.84mol)、BuOH(636.1g)を加え、内温85℃で3時間反応を行った。HPLCで反応完結を確認し、水(12.6g、0.7mol)を滴下し30分攪拌後、これに酢酸エチルを滴下して析出した固体をろ別し、減圧下、80℃で乾燥し、中間体1Bの262.1gを得た(収率82.4%)。
2Lフラスコに中間体1B(113.6g、0.25mol)とピリジン(736g)を仕込み攪拌後、これに無水酢酸(38g、0.375mol)を常温で滴下し、50℃で撹拌を1時間行った。これに中間体1A(90.1g、0.25mol)を加え3時間反応後、油水分離(クロロホルム/水)を行い、取り出した水層に塩酸を酸性になるまで滴下し、ろ過をし、目的物を80.7g得た(収率54.4%)。
対応する中間体を用いて実施例1と同様の製造方法によって化合物No.2~7及び43~46を得た。
化合物No.1~No.7又はNo.43~No.46を10mg秤量し、100mlメスフラスコに入れ、これにクロロホルムを標線まで加え、超音波で10分震盪させ、均一化した溶液を得た。得られた溶液からホールピペットで2mlを取り出し、空の100mlメスフラスコに入れた後、これにクロロホルムを標線まで加え、測定サンプルを調製した。
上記測定サンプルについて、日本分光製U-3900にて下記の測定を行った。即ち、クロロホルムのベースラインを測定後、上記測定サンプルを光路長1cmのクォーツセルに入れ、800~300nmの可視光領域を0.5nm間隔にて300nm/minで吸光度測定し、600~400nmで最大吸光度となる波長をλmaxとした。また、λmaxの吸光度とその分子量から、ランベルトベールの法則を用い、モル吸光係数εを計算した。結果を[表1]に示す。
セイコーインスツルメンツ製示差熱同時熱重量測定装置TG-DTA6200を用いた。試料アルミパンに化合物No.1~No.7又はNo.43~No.46を2mg秤量し、窒素フロー200ml/min、昇温スピード10℃/min、測定温度範囲35℃~550℃にて、測定を行った。得られたTG曲線の重量減少0%の接線と10%重量減少時の接線との交点から分解温度を算出した。結果を[表1]に示す。
化合物を重溶媒(DMSO-d6)にそれぞれ溶解し、1H-NMRを測定した。結果を[表2]に示す。
化合物No.3、No.4及び比較化合物No.3の酸化電位を下記の方法に従い評価した。結果を[表3]に示す。
過塩素酸テトラブチルアンモニウム(ナカライテスク製ポーラログラフィー用試薬)を脱水ジクロロメタンに0.1Mの濃度で溶解し、この溶液に色素(化合物No.3、No.4又は比較化合物No.3)を1.0×10-3Mで溶解させた。この色素溶液を電気化学セルに5ml入れ、Ag/AgCl参照電極と白金ワイヤー型対極、白金作用極を取り付け、BAS製電気化学アナライザー600Cにて-0.4V~1.5Vまで掃引し、酸化電位のピーク値を求めた。
化合物No.2~7若しくはNo.43~46又は上記比較化合物No.1~No.3の0.5質量%アセトン溶液0.4gと、ポリメチルメタクリレートの25質量%トルエン溶液3.0gを混合し、15分間超音波照射を行い、塗工液を調製した。詳細を[表4]に示す。
上記光学フィルタについて、以下の耐光性試験を行った。
光学フィルタに、キセノン耐光性試験機(ATLAS製SUNTESTCPS+)にて光を48時間照射した。光照射前後の光学フィルタの吸収極大波長における吸光度を測定し、初期値(光照射前)を100として光照射後の相対値(吸光度保持率)を算出した。吸光度保持率は高い方が好ましい。結果を[表5]に示す。
Claims (7)
- 下記一般式(I)で表されるポリメチン化合物。
R5及びR9は、それぞれ独立に、水素原子、炭素原子数1~30の炭化水素基、又は複素環を含有する炭素原子数2~20の基を表し、
R8は、炭素原子数1~20のハロゲン化アルキル基、炭素原子数6~20のアリール基、又は、水酸基、ニトロ基、シアノ基、ハロゲン原子、カルボキシル基、スルホン酸基、スルホンアミド基若しくはフッ化アルキル基で置換された炭素原子数6~20のアリール基を表し、
Xは、>CR10R11、酸素原子、硫黄原子又は>NR12を表し、
R10及びR11は、それぞれ独立に、水素原子、炭素原子数1~30の炭化水素基、複素環を含有する炭素原子数2~20の基又はメタロセニル基を表し、
R12は、水素原子、炭素原子数1~30の炭化水素基、複素環を含有する炭素原子数2~20の基を表し、
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11及びR12で表される基中のメチレン基は、-O-、-S-、-CO-、-COO-、-OCO-、-COS-、-OCS-、-SO2-、-SO3-、-NH-、-CONH-、-NHCO-、-SO2NH-、-NH-SO2-、-N=CH-、-CH=CH―、又はこれらを組み合わせた基によって、酸素原子が隣り合わない条件で、置き換わっている場合もあり、
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11及びR12で表される基のアルキル部分は、分岐側鎖又は環状アルキルである場合があり、置換基を有する場合もあり、
R1とR2、R2とR3、R3とR4、R4とR5、R10とR11及びR12とR1は、それぞれ結合して環を形成する場合があり、形成した環は置換基を有する場合もあり、
mは1~6の整数であり、
m≧2の場合、複数存在するR1、R2、R3、R4、R5、R6、R7、R8、R9及びXは、それぞれ同一である場合があり、異なる場合もあり、
m=1の場合、Aは、存在せず、m≧2のとき、Aは、直接結合、窒素原子、>NR13、酸素原子、硫黄原子、-SO2-、-SO-、リン原子、>PR13、Em+、Lm-又は下記(i)、(ii)、(iii)、(iv)若しくは(v)に示すいずれかの連結基を表し、
R13は、水素原子、又は炭素原子数1~30の炭化水素基を表し、
R13で表される炭素原子数1~30の炭化水素基中のメチレン基は、-COO-、-O-、-OCO-、-NHCO-、-NH-、-CONH-、又はこれらを組み合わせた基によって、酸素原子が隣り合わない条件で、置き換わっている場合もあり、
Em+はm価の陽イオンを表し、Lm-はm価の陰イオンを表し、
m≧2でAがEm+又はLm-でない場合、Aは、R1、R2、R3、R4、R5、R6、R7、R8又はR9で表される基の水素原子に置き換わる形で連結する。)
(i)m=2のとき、Aは、下記式(α)で表される連結基である場合がある。
Z1及びZ2は、それぞれ独立に、直接結合、-O-、-S-、-SO2-、-SO-、>NR14、又は>PR15を表し、
R14及びR15は、それぞれ独立に、水素原子、又は炭素原子数1~30の炭化水素基を表し、
R14及びR15で表される基中のメチレン基は、-COO-、-O-、-OCO-、-NHCO-、-NH-、-CONH-、又はこれらを組み合わせた基によって、酸素原子が隣り合わない条件で、置き換わっていてもよい。
但し、上記式(α)で表される基は炭素原子数1~35の範囲内であり、式中の*は、*部分で、隣接する基と結合することを意味する。)
上記の炭素原子数1~30の炭化水素基及び炭素原子数1~10のアルコキシ基の水素原子はハロゲン原子で置き換わっている場合があり、
dは0~4の整数であり、
式中の*は、*部分で、隣接する基と結合することを意味する。)
R23及びR24で表される基中の水素原子は、ハロゲン原子で置き換わっている場合があり、
R23及びR24で表される基中のメチレン基は、不飽和結合、-O-、-S-、又はこれらを組み合わせた基によって、酸素原子が隣り合わない条件で、置き換わっている場合があり、
R23は、隣接するR23同士が結合して環を形成する場合があり、
eは0~4の数を表し、fは0~8の数を表し、gは0~4の数を表し、hは0~4の数を表し、gとhの数の合計は2~4であり、
式中の*は、*部分で、隣接する基と結合することを意味する。)
(ii)m=3のとき、Aは、下記式(β)で表される連結基である場合がある。
X2で表される基中のメチレン基は、-COO-、-O-、-OCO-、-NHCO-、-NH-、-CONH-、-O-CONH-、-NHCO-O-、又はこれらを組み合わせた基によって、酸素原子が隣り合わない条件で、置き換わっている場合もあり、
Z1、Z2及びZ3は、それぞれ独立に、上記式(α)におけるZ1及びZ2で表される基と同じである。
但し、上記一般式(β)で表わされる基は炭素原子数1~35の範囲内であり、式中の*は、*部分で、隣接する基と結合することを意味する。)
(iii)m=4のとき、Aは、下記式(γ)で表される連結基である。
X3で表される基中のメチレン基は、-COO-、-O-、-OCO-、-NHCO-、-NH-、-CONH-、-O-CONH-、-NHCO-O-、又はこれらを組み合わせた基によって、酸素原子が隣り合わない条件で、置き換わっている場合もあり、
Z1、Z2、Z3及びZ4は、それぞれ独立に、上記式(α)におけるZ1及びZ2で表される基と同じである。
但し、上記一般式(γ)で表される基は炭素原子数1~35の範囲内であり、式中の*は、*部分で、隣接する基と結合することを意味する。)
(iv)m=5のとき、Aは、下記式(δ)で表される連結基である。
X4で表される基中のメチレン基は、-COO-、-O-、-OCO-、-NHCO-、-NH-、-CONH-、-O-CONH-、-NHCO-O-、又はこれらを組み合わせた基によって、酸素原子が隣り合わない条件で置き換わっている場合もあり、
Z1、Z2、Z3、Z4及びZ5は、それぞれ独立に、上記式(α)におけるZ1及びZ2で表される基と同じである。
但し、上記一般式(δ)で表される基は炭素原子数2~35の範囲内であり、式中の*は、*部分で、隣接する基と結合することを意味する。)
(v)m=6のとき、Aは、下記式(ε)で表される連結基である。
X5で表される基中のメチレン基は、-COO-、-O-、-OCO-、-NHCO-、-NH-、-CONH-、-O-CONH-、-NHCO-O-、又はこれらを組み合わせた基によって、酸素原子が隣り合わない条件で、置き換わっている場合もあり、
Z1、Z2、Z3、Z4、Z5及びZ6は、それぞれ独立に、上記式(α)におけるZ1及びZ2で表される基と同じである。
但し、上記一般式(ε)で表される基は炭素原子数2~35の範囲内であり、式中の*は、*部分で、隣接する基と結合することを意味する。) - 一般式(I)、(II)及び(III)中のR9が下記式(ζ)で表される基である請求項1~3の何れか一項に記載のポリメチン化合物。
R31、R32、R33、R34及びR35のうち、一つ以上は、-SO2NR36R37であり、
R36及びR37は、それぞれ独立に、水素原子、炭素原子数1~30の炭化水素基、複素環を含有する炭素原子数2~20の基又はメタロセニル基を表し、
R31、R32、R33、R34、R35、R36及びR37で表される基中のメチレン基は、-O-、-S-、-CO-、-COO-、-OCO-、-COS-、-OCS-、-SO2-、-SO3-、-NH-、-CONH-、-NHCO-、-SO2NH-、-NH-SO2-、-N=CH-、-CH=CH―、又はこれらを組み合わせた基によって、酸素原子が隣り合わない条件で、置き換わっている場合もあり、
R31、R32、R33、R34、R35、R36及びR37で表される基のアルキル部分は、分岐側鎖又は環状アルキルである場合があり、置換基を有する場合もあり、
R31とR32、R32とR33、R33とR34、R34とR35及びR36とR37は、それぞれ結合して環を形成する場合があり、形成した環は置換基を有する場合もある。) - 請求項1~4のいずれか一項に記載のポリメチン化合物を含有する組成物。
- 請求項5記載の組成物を用いた光学フィルム。
- 請求項5記載の組成物を用いた光学フィルタ。
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JPWO2018043451A1 (ja) | 2019-06-24 |
JP7000329B2 (ja) | 2022-01-19 |
TW201815783A (zh) | 2018-05-01 |
CN109511264B (zh) | 2021-06-08 |
TWI752078B (zh) | 2022-01-11 |
CN109511264A (zh) | 2019-03-22 |
KR102507765B1 (ko) | 2023-03-08 |
KR20190046755A (ko) | 2019-05-07 |
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