WO2015133578A1 - シアニン系着色組成物 - Google Patents
シアニン系着色組成物 Download PDFInfo
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- WO2015133578A1 WO2015133578A1 PCT/JP2015/056528 JP2015056528W WO2015133578A1 WO 2015133578 A1 WO2015133578 A1 WO 2015133578A1 JP 2015056528 W JP2015056528 W JP 2015056528W WO 2015133578 A1 WO2015133578 A1 WO 2015133578A1
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- 0 CC(CC(CCCCC(C1)[C@]1C1CC1)CC=*C)C(C*)=C1CCCCC1 Chemical compound CC(CC(CCCCC(C1)[C@]1C1CC1)CC=*C)C(C*)=C1CCCCC1 0.000 description 3
- IKCGNIZAYAJVCB-BQYQJAHWSA-N CC(C(OCCOC(/C=C/c1ccccc1N)=O)=O)=C Chemical compound CC(C(OCCOC(/C=C/c1ccccc1N)=O)=O)=C IKCGNIZAYAJVCB-BQYQJAHWSA-N 0.000 description 1
- RFXMQENNADYFOF-BQYQJAHWSA-N CC(C(OCCOC(/C=C/c1ccccc1[N+]([O-])=O)=O)=O)=C Chemical compound CC(C(OCCOC(/C=C/c1ccccc1[N+]([O-])=O)=O)=O)=C RFXMQENNADYFOF-BQYQJAHWSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/62—Monocarboxylic acids having ten or more carbon atoms; Derivatives thereof
- C08F120/68—Esters
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- 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
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
- C07D209/14—Radicals substituted by nitrogen atoms, not forming part of a nitro radical
- C07D209/16—Tryptamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
- C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/10—The polymethine chain containing an even number of >CH- groups
- C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
- C09B69/105—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing a methine or polymethine dye
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/13—Environmental stress cracking resistance
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/08—Homopolymers or copolymers of acrylic acid esters
Definitions
- the present invention relates to a cyanine-based coloring compound, a polymer having a monomer unit derived from the compound, and a coloring composition comprising the polymer.
- Color pixel formation methods in the production of color filters such as liquid crystal display devices and solid-state image sensors include dyeing methods using dyes as dyes, dye dispersion methods, pigment dispersion methods using pigments, electrodeposition methods, and printing methods. Etc. are known. In recent years, improvements in luminance and contrast are particularly required as the characteristics of color filters. According to the pigment dispersion method using a pigment, since heat resistance and light resistance are higher than those of dyes, a color pixel with little deterioration in a heating process at the time of panel manufacture and high long-term reliability can be obtained. Therefore, the pigment dispersion method has become mainstream at present.
- a dye having an absorption band at a specific wavelength blocks light of harmful wavelengths or reduces the transmittance. Therefore, if it is added to various products, it can give a role as a filter.
- a dye that cuts blue light visible light of 380 to 500 nm
- peripheral materials such as eyeglass lenses and frames and covers thereof.
- Patent Document 4 a method of dyeing dyes by penetrating and diffusing the surface of the lens. However, since it is surface processing, it may not become uniform dyeing
- Patent Document 5 there is a method of preparing a plastic lens that blocks ultraviolet rays up to 400 nm by mixing a specific monomer with an ultraviolet absorber and polymerizing.
- the ultraviolet absorber is not directly bonded to the monomer, there is a problem that unevenness is likely to occur during polymerization.
- An object of the present invention is to provide a cyanine-based coloring composition having higher heat resistance than conventional coloring compositions.
- the present inventors considered using a cyanine compound instead of an azo compound as a raw material for the coloring composition.
- cyanine compounds having an anion having a specific structure as a counter anion and having an ethylenically unsaturated bond or It has been found that by using a polymer having a monomer unit derived from the compound as a dye, a colored composition having excellent heat resistance can be obtained, and the present invention has been completed. Since the coloring composition of the present invention has extremely high heat resistance as compared with general dyes, it can be used without any problem for coloring resins having an injection molding temperature exceeding 200 ° C.
- the colored composition of the present invention since there is an ethylenically unsaturated group in the molecule of the compound of the present invention, by using the colored composition of the present invention as a polymer, bleeding out during use over time is suppressed, and elution into a solvent such as ethanol Is also suppressed, and more uniform dyeing than conventional dyes is possible.
- the present invention is a compound represented by the following general formula (1), a polymer having a monomer unit derived from the compound represented by the following general formula (1), a colored composition comprising the above compound or the above polymer, and
- the present invention relates to a coloring composition for a color filter comprising the compound or the polymer.
- R 1 to R 4 each independently represents a hydrogen atom, a nitro group, a halogeno group, a cyano group, an amide group, a carboxyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms
- Group an alkyloxycarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, or an arylcarbonyl group having 7 to 10 carbon atoms
- R 5 and R 6 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an arylalkyl group having 7 to 13 carbon atoms, or an alkyl group having 1 to 6 carbon atoms as a substituent of a phenyl group.
- R 7 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an arylalkyl group having 7 to 13 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, a carboxyl group, a halogeno group, or a cyano group as a substituent.
- a phenylalkyl group having 7 to 9 carbon atoms, n R 8 s independently represent a nitro group, a halogeno group, a cyano group, an amide group, a carboxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 2 to 4 carbon atoms.
- An ⁇ represents an anion including an aryl
- the compound or polymer of the present invention When the compound or polymer of the present invention is used as a colored composition, even when heated at 230 ° C. for 30 minutes, there is little fading due to heating and a high heat resistance effect is exhibited. That is, the compound or polymer of the present invention has a heat resistance effect superior to that of conventional coloring compositions, and also has excellent solvent resistance and weather resistance. Therefore, the colored composition of the present invention can be applied to various uses, and is used for forming colored pixels such as color filters used in liquid crystal display devices (LCD) and solid-state imaging devices (CCD, CMOS, etc.), printing inks. It can be used for applications such as inkjet inks and paints, and is particularly suitable for color filters of liquid crystal display devices.
- LCD liquid crystal display devices
- CCD solid-state imaging devices
- CMOS CMOS, etc.
- the colored composition of the present invention can be molded into a sheet, film, bottle, cup or the like by a conventionally known molding method and used as a colored resin molded product. Therefore, it can be used for applications such as eyeglasses, contact lenses, and color contact lenses, and can also be used for similar applications by forming a multilayer structure with a known resin. In addition, it can also be used for applications such as optical films, hair coloring agents, labeling substances for compounds and biological substances, and materials for organic solar cells.
- An anion containing an aryl group having an electron-withdrawing substituent, a sulfonyl group having an electron-withdrawing substituent, or a halogenated alkyl group An anion containing an aryl group having an electron-withdrawing substituent represented by An ⁇ in the general formula (1), a sulfonyl group having an electron-withdrawing substituent or a halogenated alkyl group (hereinafter referred to as the anion according to the present invention).
- a sulfonyl group having an electron-withdrawing substituent for example, a sulfonate anion, a nitrogen anion (N ⁇ )
- a quaternary boron anion, a nitrate ion, a phosphate ion, and the like for example, a sulfonate anion, a nitrogen anion, and a quaternary boron anion are preferable, and a quaternary boron anion is more preferable.
- Examples of the electron-withdrawing substituent in the aryl group having an electron-withdrawing substituent or the sulfonyl group having an electron-withdrawing substituent of the anion according to the present invention include, for example, a halogenated alkyl group having 1 to 3 carbon atoms, Examples thereof include a halogeno group and a nitro group. Among them, a halogenated alkyl group having 1 to 3 carbon atoms and a halogeno group are preferable, and a halogeno group is particularly preferable.
- halogenated alkyl group having 1 to 3 carbon atoms as the electron-withdrawing substituent examples include, for example, a chloromethyl group, a trichloromethyl group, a 2-chloroethyl group, a 2,2,2-trichloroethyl group, and a 2-chloropropyl group.
- chloroalkyl groups such as 3-chloropropyl group, 2-chloro-2-propyl group; bromomethyl group, tribromomethyl group, 2-bromoethyl group, 2,2,2-tribromoethyl group, 2-bromopropyl Groups, bromoalkyl groups such as 3-bromopropyl group, 2-bromo-2-propyl group; iodomethyl group, triiodomethyl group, 2-iodoethyl group, 2,2,2-triiodoethyl group, 2-iodopropyl Group, iodoalkyl group such as 3-iodopropyl group, 2-iodo-2-propyl group, etc .; fluoromethyl group, trifluoromethyl group, 2 Fluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, pentafluoroethyl group
- the electron-withdrawing substituent in the aryl group having an electron-withdrawing substituent of the anion according to the present invention is preferably one having a strong electron-withdrawing force, such as a trifluoromethyl group, a fluoro group, or a nitro group.
- a fluoro group and a nitro group are more preferred.
- the electron-withdrawing substituent in the sulfonyl group having an electron-withdrawing substituent of the anion according to the present invention includes a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and a fluoro group. preferable.
- Examples of the aryl group in the aryl group having an electron-withdrawing substituent of an anion according to the present invention include a phenyl group and a naphthyl group, and a phenyl group is preferable.
- aryl group having an electron-withdrawing substituent in the anion according to the present invention include those represented by the following general formulas (11) and (12).
- m represents an integer of 1 to 5
- m R 41 s each independently represent a halogenated alkyl group having 1 to 3 carbon atoms, a halogen atom or a nitro group, and * represents a bond. Represents.
- k represents an integer of 1 to 7.
- R 41 and * are the same as described above.
- K R 41 may be the same or different.
- m is preferably 2 to 5 when R 41 is a halogen atom, more preferably 3 to 5, and still more preferably 5.
- R 41 is a nitro group, it is preferably 1 to 3, and more preferably 1.
- R 41 is a halogenated alkyl group, 1 to 5 is preferable.
- k is preferably 2 to 7 when R 41 is a halogen atom.
- R 41 is a nitro group, it is preferably 1 to 3, and more preferably 1.
- R 41 is a halogenated alkyl group, 1 to 7 is preferred.
- the halogenated alkyl group having 1 to 3 carbon atoms of R 41 in the general formula (11) and the general formula (12) is an alkyl halide having 1 to 3 carbon atoms in the electron-withdrawing substituent in the anion according to the present invention.
- the same thing as a group is mentioned, A preferable thing is also the same.
- Examples of the halogen atom in the general formula (11) and the general formula (12) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among them, a fluorine atom is preferable.
- R 41 in the general formula (11) and the general formula (12) are the same as the preferred examples of the electron-withdrawing substituent in the anion according to the present invention.
- Specific examples of the group represented by the general formula (11) include a trifluoromethylphenyl group, a di (trifluoromethyl) phenyl group, a tri (trifluoromethyl) phenyl group, a monofluorophenyl group, a difluorophenyl group, Trifluorophenyl, perfluorophenyl, monochlorophenyl, dichlorophenyl, trichlorophenyl, perchlorophenyl, monobromophenyl, dibromophenyl, tribromophenyl, perbromophenyl, monoiodophenyl, di Examples include iodophenyl group, triiodophenyl group, periodiophenyl group, nitrophenyl group, dinitrophenyl group, trinitrophenyl group, and the like. Difluorophenyl group, trifluorophenyl group, perfluorophenyl group, etc.
- Specific examples of the group represented by the general formula (12) include a trifluoromethylnaphthyl group, a di (trifluoromethyl) naphthyl group, a tri (trifluoromethyl) naphthyl group, a monofluoronaphthyl group, a difluoronaphthyl group, Trifluoronaphthyl group, perfluoronaphthyl group, monochloronaphthyl group, dichloronaphthyl group, trichloronaphthyl group, perchloronaphthyl group, monobromonaphthyl group, dibromonaphthyl group, tribromonaphthyl group, perbromonaphthyl group, monoiodonaphthyl group , Diiodonaphthyl group, triiodonaphthyl group, periodonaphthyl group,
- the aryl group having an electron-withdrawing substituent in the anion according to the present invention is preferably a group represented by the general formula (11), specifically, a trifluoromethylphenyl group, a nitrophenyl group, Dinitrophenyl group, trinitrophenyl group, monofluorophenyl group, difluorophenyl group, trifluorophenyl group, and perfluorophenyl group are preferable, and difluorophenyl group, trifluorophenyl group, nitrophenyl group, and perfluorophenyl group are more preferable.
- a nitrophenyl group and a perfluorophenyl group are more preferred, and a perfluorophenyl group is particularly preferred.
- Examples of the sulfonyl group having an electron-withdrawing substituent in the anion according to the present invention include —SO 2 —CF 3 , —SO 2 —C 2 F 5 , —SO 2 —C 3 F 7 , —SO 2 —F , —SO 2 —Cl, —SO 2 —Br, —SO 2 —I, and the like.
- halogenated alkyl group in the anion according to the present invention examples include a halogenated alkyl group having 1 to 3 carbon atoms, such as a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a trichloromethyl group, and a pentachloro group.
- Examples include ethyl group, heptachloropropyl group, tribromomethyl group, pentabromoethyl group, heptabromopropyl group, triiodomethyl group, pentaiodoethyl group, heptaiodopropyl group, trifluoromethyl group, pentafluoroethyl Group, heptafluoropropyl group and the like are preferable.
- anion containing an aryl group having an electron-withdrawing substituent, a sulfonyl group having an electron-withdrawing substituent, or a halogenated alkyl group according to the present invention include the following general formulas (13) to (18). ). (In the formula, R 41 and m are the same as above. M R 41 may be the same or different.)
- R 41 and k are the same as above.
- the k R 41 s may be the same or different.
- R 41 and k are the same as above.
- the k R 41 s may be the same or different.
- R 42 to R 45 each independently represents a halogenated alkyl group having 1 to 3 carbon atoms, a halogen atom or a nitro group, and m 1 to m 4 each independently represents 1 to 5 M 1 R 42 may be the same or different, and m 2 R 43 , m 3 R 44, and m 4 R 45 may be the same or different. Good.
- each R 46 independently represents a halogenated alkyl group having 1 to 3 carbon atoms or a halogen atom, and at least one of the four R 46 is an alkyl halide having 1 to 3 carbon atoms. Represents a group.
- R 47 and R 48 each independently represent a halogenated alkyl group having 1 to 3 carbon atoms or a halogen atom, and R 47 and R 48 are halogenated alkylene groups having 2 to 3 carbon atoms) May be formed.
- R 41 and m in the general formula (13) examples include those listed in the following table.
- the m R 41's are independent of each other, but the same case is preferable.
- anion represented by the general formula (13) include the following.
- R 41 and m in the general formulas (14) and (15) include those described in the following table.
- the m R 41's are independent of each other, but the same case is preferable.
- Examples of the halogenated alkyl group having 1 to 3 carbon atoms in R 42 to R 45 in the general formula (16) include the same as the halogenated alkyl group in the anion according to the present invention, and preferred ones are also the same.
- Examples of the halogen atom in R 42 to R 45 in the general formula (16) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among them, a fluorine atom is preferable.
- anion represented by the general formula (16) include, for example, the following formula.
- Examples of the halogenated alkyl group for R 46 in the general formula (17) include the same ones as the halogenated alkyl group in the anion according to the present invention, and preferred ones are also the same.
- Examples of the halogen atom in R 46 of the general formula (17) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among them, a fluorine atom is preferable.
- anion represented by the general formula (17) include, for example, CF 3 BF 3 ⁇ , C 2 F 5 BF 3 ⁇ , C 3 F 7 BF 3 ⁇ , (CF 3 ) 4 B ⁇ , (C 2 F 5 ) 4 B ⁇ , (C 3 F 7 ) 4 B ⁇ and the like.
- Examples of the halogenated alkyl group in R 47 and R 48 of the general formula (18) include the same ones as the halogenated alkyl group in the anion according to the present invention, and preferable ones are also the same.
- Examples of the halogen atom in R 47 and R 48 in the general formula (18) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among them, a fluorine atom is preferable.
- Examples of the halogenated alkylene group having 2 to 3 carbon atoms formed by R 47 and R 48 in the general formula (18) include a tetrafluoroethylene group and a hexafluoropropylene group.
- the anion according to the present invention is preferably the one represented by the general formula (16), the general formula (17) or the general formula (18), more preferably the one represented by the general formula (16).
- the following formula is particularly preferable.
- the compound of the present invention is a compound represented by the general formula (1).
- the alkyl group having 1 to 6 carbon atoms in R 1 to R 4 and R 8 in the general formula (1) may be linear, branched or cyclic, and is preferably linear.
- the carbon number is preferably 1 to 3.
- methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methylpropyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, 1-ethyl A propyl group, a 1-methylbutyl group, a cyclopentyl group, a hexyl group, a 1-methylpentyl group, a 1-ethylbutyl group, a cyclohexyl group and the like can be mentioned.
- a methyl group, an ethyl group and an n-propyl group are preferable.
- the alkoxy group having 1 to 6 carbon atoms in R 1 to R 4 and R 8 in the general formula (1) may be linear, branched or cyclic, and is preferably linear.
- the carbon number is preferably 1 to 3. Specific examples include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a t-butoxy group, a hexyloxy group, and the like, and a methoxy group, an ethoxy group, a propoxy group, and the like are preferable.
- the alkyloxycarbonyl group having 2 to 4 carbon atoms in R 1 to R 4 and R 8 in the general formula (1) may be linear, branched or cyclic, and is preferably linear. Specific examples include a methyloxycarbonyl group, an ethyloxycarbonyl group, a propyloxycarbonyl group, and the like.
- the alkylcarbonyloxy group having 2 to 4 carbon atoms in R 1 to R 4 and R 8 in the general formula (1) may be linear, branched or cyclic, and is preferably linear. Specific examples include a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, and the like.
- N in the general formula (1) is preferably 0 to 2, and more preferably 0.
- Examples of the arylcarbonyl group having 7 to 10 carbon atoms in R 1 to R 4 and R 8 in the general formula (1) include a phenylcarbonyl group and a naphthylcarbonyl group, and a phenylcarbonyl group is preferable.
- R 1 to R 4 in the general formula (1) are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Among them, a hydrogen atom is preferable, and all hydrogen atoms are preferable.
- n R 8 in the general formula (1) include independently an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and the like. Of these, an alkoxy group is preferred.
- the alkyl group having 1 to 6 carbon atoms in R 5 and R 6 in the general formula (1) may be linear, branched or cyclic, and is preferably linear.
- the carbon number is preferably 1 to 3.
- Examples of the arylalkyl group having 7 to 13 carbon atoms in R 5 and R 6 of the general formula (1) include a benzyl group, a phenylethyl group, a phenylpropyl group, a naphthylmethyl group, a naphthylethyl group, a naphthylpropyl group, and the like. And the benzyl group is preferred.
- the alkyl group having 1 to 6 carbon atoms as the substituent of the phenyl group in R 5 and R 6 in the general formula (1) is the same as the alkyl group having 1 to 6 carbon atoms in the R 5 in the general formula (1). And preferred ones are the same.
- halogeno group as the substituent of the phenyl group in R 5 and R 6 of the general formula (1) include a fluoro group, a chloro group, a bromo group, and an iodo group.
- Examples of the phenylalkyl group of the phenylalkyl group having 7 to 9 carbon atoms having a substituent in R 5 and R 6 of the general formula (1) include a benzyl group, a phenylethyl group, and a phenylpropyl group. preferable.
- the carbon number of 7 to 9 does not include the carbon number of the substituent.
- the carbon number of the group having a substituent represents a number not including the carbon number of the substituent.
- phenylalkyl group having 7 to 9 carbon atoms having a substituent at R 5 and R 6 in the general formula (1) include, for example, methylbenzyl group, ethylbenzyl group, propylbenzyl group, nitrobenzyl group, dinitro group.
- examples include benzyl group, fluorobenzyl group, chlorobenzyl group, bromobenzyl group, iodobenzyl group, cyanobenzyl group, amidobenzyl group and the like.
- R 5 and R 6 in the general formula (1) are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and among them, a methyl group, an ethyl group, and a propyl group are preferable.
- a methyl group is particularly preferred.
- Examples of the alkyl group having 1 to 6 carbon atoms in R 7 of the general formula (1) include the same as the alkyl group having 1 to 6 carbon atoms in R 5 of the above general formula (1), and preferable ones are also the same. is there.
- Examples of the arylalkyl group having 7 to 13 carbon atoms in R 7 of the general formula (1) include the same as the arylalkyl group having 7 to 13 carbon atoms in R 5 and R 6 of the general formula (1), The preferred ones are the same.
- the alkoxy group having 1 to 6 carbon atoms as the substituent of the alkyl group having 1 to 6 carbon atoms in R 7 in the general formula (1) includes the carbon number in R 1 to R 4 and R 8 in the general formula (1). Examples thereof are the same as the alkoxy groups 1 to 6 and preferable ones are also the same.
- Examples of the halogeno group as a substituent of the alkyl group having 1 to 6 carbon atoms in R 7 of the general formula (1) include a fluoro group, a chloro group, a bromo group, and an iodo group.
- the alkyloxycarbonyl group having 2 to 4 carbon atoms as the substituent of the alkyl group having 1 to 6 carbon atoms in R 7 in the general formula (1) may be linear, branched or cyclic, Is preferred. Specific examples include a methyloxycarbonyl group, an ethyloxycarbonyl group, a propyloxycarbonyl group, and the like.
- Examples of the alkyl group having 1 to 6 carbon atoms having a substituent at R 7 in formula (1) include the same alkyl groups as those having 1 to 6 carbon atoms in R 5 of formula (1). The preferred ones are the same.
- alkyl group having 1 to 6 carbon atoms having a substituent at R 7 in the general formula (1) include, for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a methoxyethyl group, an ethoxyethyl group, and a propoxy group.
- Aryloxycarbonyl ethyl group, ethyloxycarbonylmethyl groups include ethyloxycarbonyl ethyl.
- the alkoxy group having 1 to 6 carbon atoms as the substituent of the phenylalkyl group having 7 to 9 carbon atoms in R 7 in the general formula (1) includes carbons in R 1 to R 4 and R 8 in the general formula (1). Examples thereof are the same as those of the alkoxy group of 1 to 6, and preferable ones are also the same.
- Examples of the halogeno group as a substituent of the phenylalkyl group having 7 to 9 carbon atoms in R 7 of the general formula (1) include a fluoro group, a chloro group, a bromo group, and an iodo group.
- Examples of the phenylalkyl group of the phenylalkyl group having 7 to 9 carbon atoms in R 7 of the general formula (1) include a benzyl group, a phenylethyl group, and a phenylpropyl group, and a benzyl group is preferable.
- Examples of the phenylalkyl group having 7 to 9 carbon atoms having a substituent in R 7 of the general formula (1) include a methoxybenzyl group, an ethoxybenzyl group, a propyloxybenzyl group, a fluorobenzyl group, a chlorobenzyl group, a bromobenzyl group, Examples include iodobenzyl group and amidobenzyl group.
- R 7 in the general formula (1) is preferably an alkyl group having 1 to 6 carbon atoms, and among them, a methyl group, an ethyl group, and an n-propyl group are preferable.
- Examples of the arylene group that the alkylene chain having 1 to 21 carbon atoms in A 1 of the general formula (1) has in the chain include a phenylene group and a naphthylene group, and a phenylene group is preferable.
- an alkylene group having 1 to 21 carbon atoms having at least one group selected from —O—, —OCO—, —COO—, a vinylene group, and an arylene group in its chain “—O—, —OCO—, —COO—, an alkylene group having at least one group selected from a vinylene group and an arylene group in a chain and having a hydroxyl group as a substituent.
- “An alkylene group having 1 to 21 carbon atoms having a hydroxyl group as a substituent” and “an alkylene group having 1 to 21 carbon atoms” are linear or branched as the alkylene group having 1 to 21 carbon atoms.
- alkylene group having 1 to 21 carbon atoms having at least one group selected from —O—, —OCO—, —COO—, a vinylene group and an arylene group” in A 1 of the general formula (1) examples thereof include groups represented by the following general formulas (6-1) to (6-6).
- R 51 s each independently represent an alkylene group having 1 to 10 carbon atoms, and X 1 represents —O—, —OCO—, COO—, a vinylene group or an arylene group.
- the alkylene group having 1 to 10 carbon atoms in R 51 of the general formula (6-1) preferably has 1 to 6 carbon atoms, and more preferably has 1 to 3 carbon atoms.
- Methylene group, ethylene group and propylene group are more preferable, and ethylene group is particularly preferable.
- Specific examples of the group represented by the general formula (6-1) include the following general formula (wherein X 11 represents —O—, —OCO—, COO—, vinylene group or arylene group). To express). —CH 2 —X 11 —CH 2 — —CH 2 —X 11 —C 2 H 4 — —CH 2 —X 11 —C 3 H 6 — —CH 2 —X 11 —C 4 H 8 — —CH 2 —X 11 —C 5 H 10 — —CH 2 —X 11 —C 6 H 12 — —C 2 H 4 —X 11 —CH 2 — -C 2 H 4 -X 11 -C 2 H 4 - -C 2 H 4 -X 11 -C 3 H 6- -C 2 H 4 -X 11 -C 4 H 8 - -C 2 H 4 -X 11 -C 5 H 10- -C 2 H 4 -X 11 -C 6 H 12 - —C 3 H
- X 11 in the group represented by the general formula (6-1) is preferably —OCO—, COO— or the like, more preferably —OCO—.
- More specific and preferred specific examples of the group represented by the general formula (6-1) include those represented by the following formulae. —CH 2 —OCO—CH 2 — —CH 2 —OCO—C 2 H 4 — —CH 2 —OCO—C 3 H 6 — —CH 2 —OCO—C 4 H 8 — —CH 2 —OCO—C 5 H 10 — —CH 2 —OCO—C 6 H 12 — —C 2 H 4 —OCO—CH 2 — —C 2 H 4 —OCO—C 2 H 4 — —C 2 H 4 —OCO—C 3 H 6 — —C 2 H 4 —OCO—C 4 H 8 — —C 2 H 4 —OCO—C 5 H 10 — —C 2 H 4 —OCO—C 6 H 12 — —C 3 H 6 —OCO—C 6 —OCO—C 6 H 12 — —C 3 H 6 —OCO—CH 2 —OC
- Preferable specific examples of the group represented by the general formula (6-2) include, for example, the following general formula (wherein X 11 are each independently —O—, —OCO—, COO—, vinylene group). Or a phenylene group). —CH 2 —X 11 —C 2 H 4 —X 11 —CH 2 — —CH 2 —X 11 —C 2 H 4 —X 11 —C 2 H 4 — —C 2 H 4 —X 11 —C 2 H 4 —X 11 —CH 2 — —C 2 H 4 —X 11 —C 2 H 4 —X 11 —C 2 H 4 —X 11 —C 2 H 4 —X 11 —C 2 H 4 —X 11 —C 3 H 6 — -C 2 H 4 -X 11 -C 2 H 4 -X 11 -C 4 H 8 - -C 2 H 4 -X 11 -C 2 H 4 -X 11 -C 5 H 10- -C
- X 11 in the group represented by the general formula (6-2) is preferably —OCO—, COO— or the like.
- Preferable specific examples of the group represented by the general formula (6-3) include, for example, the following general formula (wherein p7 is the same as above). —CH 2 — (C 2 H 4 O) p7 —CH 2 — —CH 2 — (C 2 H 4 O) p7 —C 2 H 4 — —CH 2 — (C 2 H 4 O) p7 —C 3 H 6 — —C 2 H 4 — (C 2 H 4 O) p7 —CH 2 — -C 2 H 4 - (C 2 H 4 O) p7 -C 2 H 4 - -C 2 H 4 - (C 2 H 4 O) p7 -C 3 H 6 - -C 2 H 4 - (C 2 H 4 O) p7 -C 4 H 8 - -C 2 H 4 - (C 2 H 4 O) p7 -C 5 H 10 - -C 2 H 4 - (C 2 H 4 O) p7
- Preferable specific examples of the group represented by the general formula (6-4) include, for example, the following general formula (wherein p9 is the same as above). —CH 2 — (CH 2 CH (CH 3 ) O) p9 —CH 2 — —CH 2 — (CH 2 CH (CH 3 ) O) p9 —C 2 H 4 — —CH 2 — (CH 2 CH (CH 3 ) O) p9 —C 3 H 6 — —C 2 H 4 — (CH 2 CH (CH 3 ) O) p9 —CH 2 — —C 2 H 4 — (CH 2 CH (CH 3 ) O) p9 —C 2 H 4 — —C 2 H 4 — (CH 2 CH (CH 3 ) O) p9 —C 3 H 6 — —C 2 H 4 — (CH 2 CH (CH 3 ) O) p9 —C 3 H 6 — —C 2 H 4 — (CH 2 CH (CH 3 )
- alkylene group having 1 to 10 carbon atoms in R 53 of the general formula (6-5) include the same as those of R 51 in the general formula (6-1).
- X 2 in the general formula (6-5) is preferably a —COO— group.
- Preferable specific examples of the group represented by the general formula (6-5) include, for example, the following formulae. -COO-CH 2 -, - COO -C 2 H 4 -, - COO-C 3 H 6 -, -COO-C 4 H 8 -, - COO-C 5 H 10 -, - COO-C 6 H 12 -, —O—CH 2 —, —O—C 2 H 4 —, —O—C 3 H 6 —, —O—C 4 H 8 —, —O—C 5 H 10 —, —O—C 6 H 12 -, —OCO—CH 2 —, —OCO—C 2 H 4 —, —OCO—C 3 H 6 —, —OCO—C 4 H 8 —, —OCO—C 5 H 10 —, —OCO—C 6 H 12 - Among these, the following formula is preferable.
- alkylene group having 1 to 10 carbon atoms in R 54 of the general formula (6-6) include the same as R 51 of the general formula (6-1).
- the group represented by the general formula (6-6) include, for example, the following formulae. —CH ⁇ CH—COO—CH 2 —, —CH ⁇ CH—COO—C 2 H 4 —, —CH ⁇ CH—COO—C 3 H 6 —, —CH ⁇ CH—COO—C 4 H 8 —, —CH ⁇ CH—COO—C 5 H 10 —, —CH ⁇ CH—COO—C 6 H 12 — Among these, the following formula is preferable. —CH ⁇ CH—COO—CH 2 —, —CH ⁇ CH—COO—C 2 H 4 —, —CH ⁇ CH—COO—C 3 H 6 —
- alkylene group having 1 to 21 carbon atoms having at least one group selected from —O—, —OCO—, —COO—, a vinylene group and an arylene group” in A 1 of the general formula (1) Among these specific examples, the groups represented by the general formulas (6-1), (6-2), (6-5), and (6-6) are preferable, and the group represented by the general formula (6-5) Is more preferable.
- the chain has at least one group selected from “—O—, —OCO—, —COO—, a vinylene group and an arylene group, and a hydroxyl group as a substituent.
- Examples of the “alkylene group having 1 to 21 carbon atoms” include a group represented by the following general formula (7-1) or (7-2).
- R 52 s each independently represent a hydroxyl group as a substituent or an unsubstituted alkylene group having 1 to 10 carbon atoms, and X 1 is the same as above, provided that At least one of R 52 represents a C 1-6 alkylene group having a hydroxyl group as a substituent.
- the alkylene group having 1 to 10 carbon atoms having a hydroxyl group as a substituent in R 52 of the above general formulas (7-1) and (7-2) preferably has 1 to 6 carbon atoms, and has 1 to 3 carbon atoms. More preferred are those having 1 or 2 hydroxyl groups.
- hydroxymethylene group hydroxyethylene group, hydroxypropylene group, hydroxybutylene group, hydroxypentylene group, hydroxyhexylene group, hydroxymethylpentylene group, hydroxy-n-heptylene group, hydroxy-n- Examples include octylene group, hydroxy-n-nonylene group, hydroxy-n-decylene group, hydroxycyclopentylene group, hydroxycyclohexylene group, dihydroxyethylene group, and dihydroxypropylene group.
- Examples of the alkylene group having 1 to 10 carbon atoms in R 51 of the above general formulas (6-1) and (6-2) include the same, and preferable examples thereof are also the same.
- Examples of the arylene group in X 1 of the general formulas (7-1) and (7-2) include a phenylene group and a naphthylene group, and a phenylene group is preferable.
- Preferable specific examples of the group represented by the general formula (7-1) include the following general formula (wherein X 11 represents —O—, —OCO—, COO—, vinylene group or phenylene group).
- X 11 represents —O—, —OCO—, COO—, vinylene group or phenylene group.
- Preferable specific examples of the group represented by the general formula (7-2) include, for example, the following general formula (wherein X 11 is independently —O—, —OCO—, COO—, vinylene group) Or represents a phenylene group.) —CH 2 —X 11 —C 3 H 5 (OH) —X 11 —CH 2 — —C 2 H 4 —X 11 —C 3 H 5 (OH) —X 11 —C 2 H 4 — —C 2 H 4 —X 11 —C 3 H 5 (OH) —X 11 —C 3 H 6 — —C 2 H 4 —X 11 —C 3 H 5 (OH) —X 11 —C 4 H 8 — —C 2 H 4 —X 11 —C 3 H 5 (OH) —X 11 —C 5 H 10 — -C 2 H 4 -X 11 -C 3 H 5 (OH) -X 11 -C 6 H 12 - —C 3 H 6 —
- Examples of the “alkylene group having 1 to 21 carbon atoms having a hydroxyl group as a substituent” in A 1 of the general formula (1) include groups represented by the following general formula (8). - (CH 2) p10 -R 56 - (CH 2) p10 - (8) (Wherein R 56 represents an alkylene group having 1 to 9 carbon atoms having a hydroxyl group as a substituent, and p10 represents an integer of 0 to 6).
- the alkylene group having 1 to 9 carbon atoms having the hydroxyl group as a substituent in R 56 of the general formula (8) preferably has 1 to 6 carbon atoms, and more preferably has 1 to 3 carbon atoms.
- a 1 in the general formula (1) is an alkylene group having 1 to 21 carbon atoms having at least one group selected from —O—, —OCO—, —COO—, a vinylene group and an arylene group in the chain, or An alkylene group having 1 to 21 carbon atoms is preferred.
- a group represented by general formula (6-1), a group represented by general formula (6-2), a group represented by general formula (6-5), A group represented by the formula (6-6) and an alkylene group having 1 to 12 carbon atoms are more preferred, a group represented by the general formula (6-5) and an alkylene group having 1 to 6 carbon atoms are more preferred, The group represented by 6-5) is particularly preferred.
- a 1 is preferably ortho-position or para-position, more preferably para-position, relative to the —HN— group.
- a 2 is preferably —O—.
- R 1 to R 7 , R 8 , R 12 , n, A 1 and A 2 in the general formula (1) include those described in the following table.
- the ortho position described in column A 1 means being in the ortho position relative to the —HN— group, and all other A 1 means being in the para position relative to the —HN— group.
- An ⁇ in the general formula (1) is described in the above anion containing an aryl group having an electron-withdrawing substituent, a sulfonyl group having an electron-withdrawing substituent, or a halogenated alkyl group. It is as follows.
- the compound of the present invention includes, for example, (I) a compound represented by the following general formula (20), a compound represented by the following general formula (21), a compound represented by the general formula (22), or a general formula (23). After reacting with the compound shown, by performing a salt exchange reaction, or (II) reacting the compound represented by the following general formula (24) with the compound represented by the following general formula (25), It is produced by conducting an exchange reaction.
- a 11 represents a hydroxyl group as a substituent or an unsubstituted alkylene group having 1 to 6 carbon atoms.
- a 12 represents the number of carbon atoms having at least one group selected from —O—, —OCO—, —COO—, a vinylene group and an arylene group in the chain) 1 to 15 carbon atoms having at least one group selected from an alkylene group, -O-, -OCO-, -COO-, a vinylene group and an arylene group in the chain, and a hydroxyl group as a substituent.
- the alkylene group having 1 to 6 carbon atoms having the hydroxyl group of A 11 as a substituent preferably has 1 to 3 carbon atoms, and preferably has 1 or 2 hydroxyl groups.
- unsubstituted alkylene group having 1 to 6 carbon atoms of A 11 in the general formula (20) methylene group, ethylene group, propylene group, methylethylene group, butylene group, 1-methylpropylene group, 2-methylpropylene Group, pentylene group, methylbutylene group, 1,2-dimethylpropylene group, 1-ethylpropylene group, hexylene group and the like, methylene group, ethylene group and propylene group are more preferable, and ethylene group is particularly preferable.
- R 1 to R 8 , An ⁇ , and A 11 in the general formula (20) are the combinations of R 1 to R 8 described in the table of the compound of the present invention, and the general formula (16). in indicated by an -, and a methylene group, an ethylene group, and those of a combination of a 11 appropriately selected from propylene.
- the compound represented by the general formula (20) may be a commercially available product or a compound synthesized by a method known per se.
- a 12 has at least one group selected from —O—, —OCO—, —COO—, a vinylene group and an arylene group in the chain,
- alkylene group having 1 to 15 carbon atoms having a hydroxyl group as a substituent include groups represented by the following general formulas (6-1 ′) to (6-4 ′).
- R 51 s each independently represents an alkylene group having 1 to 10 carbon atoms, and X 1 is the same as above, provided that the total number of carbon atoms in the formula is 15 or less).
- R 51 s each independently represent the same as above, and p7 represents an integer of 1 to 9, provided that the total number of carbon atoms in the formula is 15 or less).
- R 51 s each independently represent the same as described above, and p9 represents an integer of 1 to 9, provided that the total number of carbon atoms in the formula is 15 or less).
- Preferred specific examples of the groups represented by the general formulas (6-1 ′) to (6-4 ′) include preferred specific examples of the groups represented by the general formulas (6-1) to (6-4). The thing which applied is mentioned.
- Examples of the alkylene group of 1 to 15 include groups represented by the following general formula (7-1 ′) or (7-2 ′).
- the alkylene group having 1 to 15 carbon atoms of A 12 in the general formulas (21), (22), and (23) is linear or branched, preferably 1 to 6 carbon atoms, 1 to 3 is more preferable.
- the alkylene group having 1 to 15 carbon atoms having a hydroxyl group as a substituent is, for example, a group represented by the following general formula (8 ′) Is mentioned.
- R 56 represents an alkylene group having 1 to 9 carbon atoms having a hydroxyl group as a substituent
- p10 represents an integer of 0 to 6. However, the total number of carbon atoms in the formula is 15 or less. is there.),
- Preferred examples of the group represented by the general formula (8 ') include those according to the preferred specific examples of the group represented by the general formula (8).
- Preferable specific examples of the general formula (21) include the following general formula (21 ′). [Wherein R 12 is the same as above. A ′ 12 represents the above general formula (6-1 ′), (6-2 ′) or an alkylene group having 1 to 6 carbon atoms. ]
- Examples of the alkylene group having 1 to 6 carbon atoms in A ′ 12 include a methylene group, an ethylene group, a propylene group, a methylethylene group, a butylene group, a 1-methylpropylene group, a 2-methylpropylene group, a pentylene group, a methylbutylene group, A 1,2-dimethylpropylene group, a 1-ethylpropylene group, a hexylene group and the like can be mentioned.
- a methylene group, an ethylene group and a propylene group are more preferable, and an ethylene group is particularly preferable.
- the amount of the compound represented by the general formula (21) to be used is 1 to 5 mol times, preferably 1 to 2 mol times that of the compound represented by the general formula (20).
- the solvent examples include ethers such as diethyl ether, diisopropyl ether, ethyl methyl ether, tetrahydrofuran, 1,4-dioxane, dimethoxyethane; for example, chloromethane, methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, chlorobenzene and the like.
- Halogenated hydrocarbons such as n-hexane, benzene, toluene, xylene and the like; nitriles such as acetonitrile; and amides such as N, N-dimethylformamide, and the like. Hydrogens are preferred.
- the dehydrating condensing agent is not particularly limited as long as it is generally used as a dehydrating condensing agent.
- inorganic dehydrating agents such as diphosphorus pentoxide and anhydrous zinc chloride; for example, dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethyl-3
- Carbodiimides such as-(3-dimethylaminopropylcarbodiimide) hydrochloride; for example, polyphosphoric acid, acetic anhydride, sulfuric acid, carbonyldiimidazole, p-toluenesulfonic acid and the like, and carbodiimides are preferred.
- the amount of the dehydrating condensing agent to be used is 1 to 10 mol times, preferably 1 to 5 mol times based on the compound represented by the general formula (22).
- a catalyst such as dimethylaminopyridine may be used in order to improve the efficiency of the dehydrating condensing agent.
- the amount of the catalyst used is 0.1 to 10 mole times the compound represented by the general formula (22).
- the reaction may be performed at a temperature of usually 1 to 10 hours, preferably 3 to 5 hours.
- the by-product hydrochloric acid gas can be adsorbed and the reaction can be promoted.
- the amount of the molecular sieve used is usually 1 to 5 times the weight of the compound represented by the general formula (20), preferably 1 to 3 times the weight. *
- the amount of the compound represented by the general formula (22) is usually 1 to 5 times, preferably 1 to 3 times the amount of the compound represented by the general formula (20).
- Examples of the solvent include the same solvents as those used in the reaction of the compound represented by the general formula (20) and the compound represented by the general formula (21).
- the salt exchange reaction in the method for producing a compound of the present invention includes a compound represented by the general formula (20), a compound represented by the general formula (21), a compound represented by the general formula (22) or the general formula (23). What is necessary is just to make it by making the salt of the anion based on this invention contact the compound obtained by making this react in a solvent.
- the salt exchange reaction is usually carried out at 10 to 50 ° C., preferably 20 to 30 ° C. for 0.1 to 10 hours, preferably 0.1 to 6 hours.
- the solvent used in this case include the same solvents as those used in the reaction of the compound represented by the general formula (20) and the compound represented by the general formula (21).
- anion salt according to the present invention examples include the anion, sodium salt, potassium salt, lithium salt and the like, and potassium or lithium salt is preferable.
- the amount of the anion salt according to the present invention is usually 1 to 2 mol, preferably 1 to 1.5 mol, per 1 mol of the compound represented by the general formula (20).
- the compound represented by the general formula (20) and the compound represented by the general formula (21) are reacted, specifically, for example, first, the compound represented by the general formula (20) and the general formula (20) are represented. 1 to 2 moles of the compound represented by the general formula (21) and 0.1 to 1 moles of the dimethylaminopyridine of the compound represented by the general formula (20) and the general formula (20) In the presence of 1 to 5 moles of carbodiimides of the compounds shown, in halogenated hydrocarbon solvents such as chloromethane, methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, chlorobenzene at 10 to 30 ° C. for 5 to 5 Let react for 30 hours.
- halogenated hydrocarbon solvents such as chloromethane, methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, chlorobenzene at 10 to 30 ° C
- a lithium salt of boron represented by the above general formula (16) is added to the obtained reaction product in an amount of 1 to 2 moles of the compound represented by the general formula (20), and chloromethane, methylene chloride, chloroform
- the compound of the present invention can be obtained by reacting in a halogenated hydrocarbon solvent such as carbon tetrachloride, dichloroethane, trichloroethane and chlorobenzene at 10 to 50 ° C. for 0.1 to 6 hours.
- the compound of the present invention is produced by subjecting the compound represented by the general formula (20) to a salt exchange reaction, followed by the salt exchanged compound represented by the general formula (20) and the general formula (21). Or a compound represented by the general formula (22) or a compound represented by the general formula (23).
- the salt exchange reaction in this case may be performed by bringing the compound represented by the general formula (20) into contact with the salt of the anion according to the present invention in a solvent.
- a solvent, reaction conditions, etc. the same thing as the said salt exchange reaction is mentioned.
- reaction of the compound represented by the general formula (20) after the salt exchange reaction with the compound represented by the general formula (21), the compound represented by the general formula (20) after the salt exchange reaction and the general formula (22) The reaction conditions and other conditions for the reaction of the compound shown and the reaction of the compound shown by the general formula (20) with the compound shown by the general formula (23) after the salt exchange reaction are as follows. Is the same.
- the compound represented by the general formula (20) is reacted with the compound represented by the general formula (22), specifically, for example, first, the compound represented by the general formula (20) is converted into, for example, the above general formula (16). 1 to 2 moles of the lithium salt of the compound represented by the general formula (20) is added, and halogenated hydrocarbons such as chloromethane, methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, and chlorobenzene are added. The reaction is carried out in a solvent at 10 to 50 ° C. for 0.1 to 6 hours.
- the compound of the present invention can be obtained by reacting in a halogenated hydrocarbon solvent such as methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, chlorobenzene and the like at 70 to 90 ° C. for 3 to 5 hours.
- a halogenated hydrocarbon solvent such as methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, chlorobenzene and the like at 70 to 90 ° C. for 3 to 5 hours.
- Preferable combinations of R 1 to R 7 in the general formula (24) include those according to the combinations of R 1 to R 7 described in the table of the compound of the present invention.
- R ′ 8 represents an alkoxyl group having 1 to 6 carbon atoms.
- Examples of the alkoxy group having 1 to 6 carbon atoms in R ′ 8 include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentyloxy group, an n-hexyloxy group, and the like.
- Group, ethoxy group and n-propoxy group are preferable, and methoxy group is more preferable.
- the reaction may be performed for a time, preferably 1 to 10 hours.
- the amount of the compound represented by the general formula (24) used is 1 to 5 times by mole, preferably 1 to 2 times by mole, that of the compound represented by the general formula (25).
- carboxylic acids such as acetic acid, propionic acid and butyric acid may be used alone, nitriles such as acetonitrile, ethers such as tetrahydrofuran and 1,4-dioxane, toluene, chloromethane, and methylene chloride.
- Organic solvents such as acetic acid, propionic acid, butyric acid, benzenesulfonic acid, p-toluenesulfonic acid, acetic acid, sulfuric acid, organic solvents such as halogenated hydrocarbons such as chloroform, carbon tetrachloride, dichloroethane, trichloroethane, and chlorobenzene
- An inorganic acid such as nitric acid may be mixed.
- the amount of the acid used is 1 to 100 times, preferably 2 to 50 times the amount of the compound represented by the general formula (24). Specific examples include acetic acid and a mixed solvent of acetonitrile and acetic acid, and acetic acid is preferable.
- the compound represented by the general formula (24) and the compound represented by the general formula (25) are reacted, specifically, for example, first, the compound represented by the general formula (24) and the general formula (24) are represented.
- the compound represented by the general formula (25) of 1 to 2 moles of the compound is reacted at 40 to 60 ° C. for 1 to 10 hours in a solvent such as acetic acid. Thereafter, for example, saturated saline is added to the obtained reaction product, and then a lithium salt of boron represented by the general formula (16) is added in an amount of 1 to 2 times the molar amount of the compound represented by the general formula (24).
- the polymer of the present invention is a polymer having monomer units derived from the compound of the present invention.
- the weight average molecular weight (Mw) of the polymer of the present invention is usually 2,000 to 100,000, preferably 2,000 to 50,000, more preferably 2,000 to 30,000.
- the degree of dispersion (Mw / Mn) is usually 1.00 to 5.00, preferably 1.00 to 3.00.
- the polymer of the present invention may be a homopolymer or a copolymer as long as it has a monomer unit derived from the compound represented by the general formula (1), but a copolymer is preferred.
- Examples of the copolymer include a monomer unit derived from the compound represented by the general formula (1) and a compound represented by the following general formula (2), general formula (3), general formula (4), or general formula (5). Examples thereof include those derived from 1 to 2 types of derived monomer units.
- R 21 represents a hydrogen atom or a methyl group
- R 22 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a hydroxylalkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms.
- R 23 represents an alkylene group having 1 to 3 carbon atoms
- R 24 represents a phenyl group having a hydroxyl group as a substituent or an unsubstituted phenyl group, or an alkyl group having 1 to 3 carbon atoms
- q represents an integer of 1 to 3
- R 25 to R 27 represent an alkyl group having 1 to 3 carbon atoms
- R 28 represents an alkylene group having 1 to 3 carbon atoms
- R 31 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
- R 32 represents a hydrogen atom or a dialkylaminoalkyl group having 3 to 9 carbon atoms
- R 31 and R 32 may form a morpholino group with a nitrogen atom adjacent to R 31 and R 32 ).
- R 33 represents a phenyl group or a pyrrolidino group, and R 21 is the same as above.
- R 35 represents a nitrogen atom or an oxygen atom
- j represents 0 when R 35 is an oxygen atom
- R 34 represents a hydrogen atom.
- An alkyl group having 1 to 20 carbon atoms, a hydroxylalkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an alkylcycloalkyl group having 1 to 10 carbon atoms, and a halogenated group having 6 to 7 carbon atoms It represents a cycloalkyl group, an aryl group having 6 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms having an alkyl group having 1 to 6 carbon atoms as a substituent, or a halogenated aryl group having 6 to 10 carbon atoms.
- R 21 in the general formula (2) is preferably a methyl group.
- the alkyl group having 1 to 18 carbon atoms in R 22 of the general formula (2) may be linear, branched or cyclic, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and n-butyl.
- Examples of the hydroxylalkyl group having 1 to 10 carbon atoms in R 22 of the general formula (2) include a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group, and a hydroxyhexyl group.
- Examples of the aryl group having 6 to 10 carbon atoms in R 22 of the general formula (2) include a phenyl group and a naphthyl group.
- Examples thereof include an arylalkyl group having 7 to 13 carbon atoms in R 22 of the general formula (2), a benzyl group, a phenylethyl group, a phenylpropyl group, a naphthylmethyl group, a naphthylethyl group, a naphthylpropyl group, and the like, and a benzyl group is preferable. .
- Examples of the alkoxyalkyl group having 2 to 9 carbon atoms in R 22 of the general formula (2) include a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, a methoxybutyl group, a methoxypentyl group, a methoxyhexyl group, a methoxyheptyl group, and a methoxy group.
- Octyl group ethoxymethyl group, ethoxyethyl group, ethoxypropyl group, ethoxybutyl group, ethoxypentyl group, ethoxyhexyl group, ethoxyheptyl group, propoxymethyl group, propoxyethyl group, propoxypropyl group, propoxybutyl group, propoxypentyl group And propoxyhexyl group.
- Examples of the alkoxyalkoxyalkyl group having 3 to 9 carbon atoms in R 22 of the general formula (2) include a methoxymethoxymethyl group, a methoxymethoxyethyl group, a methoxymethoxypropyl group, an ethoxymethoxymethyl group, an ethoxymethoxyethyl group, and an ethoxymethoxypropyl group.
- Examples of the aryloxyalkyl group having 7 to 13 carbon atoms in R 22 of the general formula (2) include a phenoxymethyl group, a phenoxyethyl group, a phenoxypropyl group, a naphthyloxymethyl group, a naphthyloxyethyl group, and a naphthyloxypropyl group. Can be mentioned.
- Examples of the morpholinoalkyl group having 5 to 7 carbon atoms in R 22 of the general formula (2) include a morpholinomethyl group, a morpholinoethyl group, a morpholinopropyl group, and the like.
- Examples of the trialkylsilyl group having 3 to 9 carbon atoms in R 22 of the general formula (2) include a trimethylsilyl group, a tolylethylsilyl group, a tripropylsilyl group, a dimethylethylsilyl group, and a diethylmethylsilyl group.
- Examples of the alicyclic hydrocarbon group having 6 to 10 carbon atoms having oxygen in R 22 of the general formula (2) include a dicyclopentenyloxyethyl group.
- Examples of the alicyclic hydrocarbon group having 6 to 10 carbon atoms that does not contain oxygen in R 22 of the general formula (2) include a cyclohexyl group, an isobornyl group, and a dicyclopentanyl group.
- Examples of the dialkylaminoalkyl group having 3 to 9 carbon atoms in R 22 of the general formula (2) include a dimethylaminomethyl group, a dimethylaminoethyl group, a dimethylaminopropyl group, a diethylaminomethyl group, a diethylaminoethyl group, a diethylaminopropyl group, A propylaminomethyl group, a dipropylaminoethyl group, a dipropylaminopropyl group, etc. are mentioned.
- Examples of the fluorinated alkyl group having 1 to 18 carbon atoms in R 22 of the general formula (2) include 2,2,2-trifluoroethyl group, 2,2,3,3-tetrafluoropropyl group, 2,2, 3,3-tetrafluoropropyl group, 2,2,3,3,4,4-hexafluoropropyl group, 2,2,3,3,4,4,5,5-octafluoropentyl group, 3,3 , 4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl; 2- (heptadecafluorooctyl) ethyl group, etc. .
- N-alkylenephthalimide group having 1 to 6 carbon atoms in R 22 of the general formula (2) examples include 2-phthalimidoethyl group and 2-tetrahydrophthalimidoethyl group.
- Examples of the alkylene group having 1 to 3 carbon atoms in R 23 in the general formula (2-1) include a methylene group, an ethylene group, and a propylene group, and an ethylene group is preferable.
- examples of the phenyl group having or not substituted with the hydroxyl group of R 24 include a hydroxyphenyl group and a phenyl group.
- Examples of the alkyl group having 1 to 3 carbon atoms of R 24 in the general formula (2-1) include a methyl group, an ethyl group, and a propyl group.
- Specific examples of the group represented by the general formula (2-1) include 2-hydroxy-3-phenoxymethyl group, 2-hydroxy-3-phenoxyethyl group, 2-hydroxy-3-phenoxypropyl group, methyltrimethylene Examples thereof include a glycol group, a methyltriethylene glycol group, and a methyltripropylene glycol group. Among them, a 2-hydroxy-3-phenoxypropyl group, a methyltripropylene glycol group, a methyltriethylene glycol group, and the like are preferable.
- Examples of the alkyl group having 1 to 3 carbon atoms in R 25 to R 27 in the general formula (2-2) include a methyl group, an ethyl group, and a propyl group, and a methyl group is preferable.
- Examples of the alkylene group having 1 to 3 carbon atoms in R 28 in the general formula (2-2) include a methylene group, an ethylene group, and a propylene group.
- Specific examples of the group represented by the general formula (2-2) include trimethyl ammonium methyl group, trimethyl ammonium ethyl group, triethyl ammonium methyl group, triethyl ammonium ethyl group and the like.
- Preferred examples of the group represented by the general formula (2-3) include those represented by the following formula.
- Preferred specific examples of the general formula (2) include methacrylic acid, benzyl methacrylate, hydroxyethyl methacrylate, methyl methacrylate and the like, and among them, methacrylic acid, benzyl methacrylate and the like are preferable.
- Examples of the alkyl group having 1 to 3 carbon atoms in R 31 of the general formula (3) include a methyl group, an ethyl group, and a propyl group.
- Examples of the dialkylaminoalkyl group having 3 to 9 carbon atoms in R 32 of the general formula (3) include a dimethylaminomethyl group, a dimethylaminoethyl group, a dimethylaminopropyl group, a diethylaminomethyl group, a diethylaminoethyl group, a diethylaminopropyl group, A propylaminomethyl group, a dipropylaminoethyl group, a dipropylaminopropyl group, etc. are mentioned.
- Examples of the alkyl group of 1 to 3 include the same groups as those described above for R 31 .
- Examples of the hydroxyalkyl group having 1 to 6 carbon atoms in R 32 of the general formula (3) include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group, and a hydroxyhexyl group.
- An ethyl group is preferred.
- Preferred examples of general formula (3) include (meth) acrylamide, N, N-dimethylacrylamide, hydroxyethyl (meth) acrylamide, 4-acryloylmorpholine, and the like.
- Preferred specific examples of the general formula (4) include styrene, ⁇ -methylstyrene, N-vinylpyrrolidone and the like.
- the alkyl group having 1 to 20 carbon atoms in R 34 in the general formula (5) may be linear, branched or cyclic.
- Examples of the hydroxylalkyl group having 1 to 10 carbon atoms in R 34 of the general formula (5) include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group, a hydroxyhexyl group, a hydroxyheptyl group, Examples thereof include a hydroxyoctyl group, a hydroxynonyl group, and a hydroxydecyl group.
- Examples of the halogenated alkyl group having 1 to 10 carbon atoms in R 34 of the general formula (5) include a chloromethyl group, a chloroethyl group, a chloro n-propyl group, a chloroisopropyl group, a chloro n-butyl group, and a chloro tert-butyl group.
- chloro-n-pentyl group chloro-n-hexyl group, chloro-n-heptyl group, chloro-n-octyl group, chloro-n-nonyl group, chloro-n-decyl group, methyl fluoride group, fluorine Ethyl fluoride group, fluoride-n-propyl group, isopropyl fluoride group, fluoride-n-butyl group, fluoride-tert-butyl group, fluoride-n-pentyl group, fluoride-n-hexyl group, fluorine Fluorinated n-heptyl group, fluorinated n-octyl group, fluorinated n-nonyl group, fluorinated n-decyl group and the like.
- Examples of the alkylcycloalkyl group having 1 to 10 carbon atoms in R 34 of the general formula (5) include a methylcyclohexyl group, an ethylcyclohexyl group, a propylcyclohexyl group, and a butylcyclohexyl group.
- Examples of the halogenated cycloalkyl group having 6 to 7 carbon atoms in R 34 of the general formula (5) include a chlorocyclohexyl group, a fluorinated cyclohexyl group, a bromocyclohexyl group, a chlorocycloheptyl group, a fluorinated cycloheptyl group, and a bromocycloheptyl group. Groups and the like.
- Examples of the aryl group having 6 to 10 carbon atoms in R 34 of the general formula (5) include a phenyl group and a naphthyl group.
- Examples of the aryl group having 6 to 10 carbon atoms having a substituent of an alkyl group having 1 to 6 carbon atoms in R 34 of the general formula (5) include a methylphenyl group, an ethylphenyl group, an n-propylphenyl group, and n-butyl. Examples thereof include a phenyl group, an n-pentylphenyl group, and an n-hexylphenyl group.
- Examples of the halogenated aryl group having 6 to 10 carbon atoms in R 34 of the general formula (5) include a chlorophenyl group, a phenyl fluoride group, a chloronaphthyl group, and a fluorinated naphthyl group.
- Preferred specific examples of the general formula (5) include maleic anhydride, maleimide, N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N- (2-ethylhexyl) Maleimide, N- (2-hydroxyethyl) maleimide, N- (2-chlorohexyl) maleimide, N-cyclohexylmaleimide, N- (2-methylcyclohexyl) maleimide, N- (2-ethylcyclohexyl) maleimide, N- ( 2-Chlorocyclohexyl) maleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (2-ethylphenyl) maleimide, N- (2-chlorophenyl) maleimide and the like.
- copolymer of the present invention include the following combinations of monomer units, among which the combination 1 is preferable.
- a copolymer comprising a compound represented by the general formula (1) and two kinds of compounds represented by the general formula (2) is preferable.
- two types of compounds represented by the general formula (2) include those in which R 21 in the general formula (2) is a hydrogen atom or a methyl group and R 22 is a hydrogen atom, and in the general formula (2) R 21 is a hydrogen atom or a methyl group, and R 22 is an arylalkyl group having 7 to 13 carbon atoms.
- the weight ratio of the monomer unit derived from the compound represented by the general formula (1) and the monomer unit derived from the compound represented by the general formula (2), the general formula (3), the general formula (4) or the general formula (5) is The monomer unit derived from the compound represented by the general formula (1) is usually 1 to 90% by weight, preferably 5%, based on the total weight of the obtained polymer. ⁇ 85% by weight.
- copolymer of the present invention include a polymer comprising a monomer unit derived from the compound represented by the general formula (1) and one or two monomer units derived from the compound represented by the following general formula (2 ′). Can be mentioned.
- R 21 is the same as above.
- R ′ 22 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a hydroxylalkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or 7 carbon atoms. Represents an arylalkyl group having ⁇ 13 or an alkoxyalkyl group having 2 to 9 carbon atoms.
- R ′ 22 has an alkyl group having 1 to 18 carbon atoms, a hydroxyl alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 13 carbon atoms, and an alkyl group having 2 to 9 carbon atoms.
- Specific examples of the alkoxyalkyl group include the same as those for R 22 above.
- R ′ 22 is preferably a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an arylalkyl group having 7 to 13 carbon atoms, or the like, preferably a hydrogen atom or an arylalkyl group having 7 to 13 carbon atoms.
- R 21 and R ′ 22 in the compound represented by the general formula (2 ′) are as follows.
- the polymer of the present invention is produced, for example, as follows. That is, the polymer of the present invention can be obtained by subjecting the compound of the present invention to a known polymerization reaction as a monomer.
- the compound of the present invention and the compound represented by the general formula (2), the general formula (3), the general formula (4) or the general formula (5) are used during the polymerization reaction. One or two of these may be mixed so that the ratio of monomer units derived from each monomer in the finally obtained polymer is as described above, and then polymerized.
- the polymerization reaction is performed as follows, for example.
- the compound of the present invention represented by the general formula (1) is further converted into one of the compounds represented by the general formula (2), the general formula (3), the general formula (4) or the general formula (5).
- Two types are dissolved in a suitable solvent having a volume of 1 to 10 times the total volume, such as toluene, 1,4-dioxane, tetrahydrofuran, isopropanol, methyl ethyl ketone, propylene glycol monomethyl ether acetate, etc.
- the polymerization initiator 0.01 to 30% by weight of the polymerization initiator relative to the total amount, for example, azoisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylpro Pionate), 2,2′-azobis (2-methylbutyronitrile), benzoyl peroxide, lauroyl peroxide, and the like, and reacted at 50 to 150 ° C. for 1 to 20 hours. . After the reaction, it may be treated according to a conventional method for obtaining a polymer.
- the coloring composition of the present invention contains at least one compound or polymer of the present invention.
- the coloring composition can be suitably used for a color filter.
- the colored composition can form an excellent colored cured film having heat resistance. Therefore, the colored composition of the present invention is used for forming colored pixels such as color filters used in liquid crystal display devices (LCDs) and solid-state imaging devices (CCD, CMOS, etc.), printing inks, inkjet inks, and paints. It can be used, and is particularly suitable for a color filter of a liquid crystal display device.
- the colored composition of the present invention can be molded into a sheet, film, bottle, cup or the like by a conventionally known molding method and used as a colored resin molded product.
- the colored composition of the present invention may contain additives ordinarily used in this field in addition to the compound or polymer of the present invention according to each application.
- the colored composition of the present invention when used as a colored resin, preferably contains at least one compound or polymer of the present invention and is mixed with other resins. More preferably, the polymer of the present invention contains at least one polymer and is mixed with other resins.
- other resin For example, polyolefin resin, polystyrene resin, polyester resin, polyamide resin, polyurethane resin, polycarbonate resin, epoxy resin, acrylic resin, acrylonitrile resin, ABS resin etc. are mentioned. More specifically, a homopolymer or a copolymer derived from the compound represented by the above general formula (2), general formula (3), general formula (4) or / and general formula (5) is preferable.
- a homopolymer derived from the compound represented by formula (3), formula (4) or formula (5) is more preferred.
- a homopolymer derived from the compound represented by the general formula (2) is preferable, and a homopolymer derived from the compound represented by the general formula (2 ′) is more preferable.
- the mixing ratio should just be suitably set according to the color of the coloring resin calculated
- the coloring composition of the present invention contains a lubricant, an antistatic agent, an ultraviolet ray, in addition to the compound or polymer of the present invention and, if necessary, other resins, as long as the objects and effects of the present invention are not hindered.
- a lubricant an antistatic agent, an ultraviolet ray
- Commonly used in this field such as inhibitor, antioxidant, light stabilizer, dispersant, processing stabilizer, processing aid, impact modifier, filler, reinforcing agent, telephoto agent, plasticizer, foaming agent, etc.
- An additive may be included.
- the colored composition of the present invention has excellent weather resistance with little dye elution even when contacted with a solvent.
- the colored composition of the present invention is a pigment, a polymerization initiator, a solvent, a binder resin, a radical polymerizable monomer, an oligomer, or a crosslinking agent, as necessary.
- the coloring composition contains the compound or polymer of the present invention in an amount of 1 to 50%, preferably 5 to 30%, based on the weight of the coloring composition.
- the weight of the coloring composition here means the weight of the solid component excluding the solvent, and represents the same meaning in the present invention hereinafter.
- the pigment may be any pigment used for producing a blue or green coloring pattern, and examples thereof include phthalocyanine pigments.
- phthalocyanine pigments include those containing magnesium, titanium, iron, cobalt, nickel, copper, zinc, and aluminum as a central metal.
- Pigment blue 79 C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 37, C.I. I. Pigment green 58, chloroaluminum phthalocyanine, hydroxyaluminum phthalocyanine, aluminum phthalocyanine oxide, zinc phthalocyanine, C.I. I. Pigment blue 15, C.I. I. Pigment Blue 15: 6, Pigment Blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment Green 58 is preferable. I. Pigment blue 15: 6, C.I. I. Pigment Green 58 is preferable.
- the content of the pigment is 10 to 50% by weight, preferably 10 to 30% by weight, based on the weight of the coloring composition.
- the coloring composition of the present invention contains the above pigment, it preferably contains a pigment dispersant.
- the pigment dispersant include polyamidoamine and salts thereof, polycarboxylic acid and salts thereof, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, and (meth) acrylic copolymer. , Naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, alkanol amine and the like.
- the pigment dispersants may be used alone or in combination of two or more. The content thereof is usually 1 to 80% by weight, preferably 10 to 60% by weight, based on the weight of the pigment.
- the polymerization initiator known thermal polymerization initiators and photopolymerization initiators can be used, and photopolymerization initiators are preferred. Specifically, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1- ON, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one Acetophenones such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone; benzoins such as benzoin, benzoin isopropyl ether and benzoin isobutyl ether; 2,4,6-trimethylbenzoyldiphenylphosphine oxide Acylphos
- Benzophenone methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, Benzophenone series such as acrylated benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3′-dimethyl-4-methoxybenzophenone; 2-isopropylthioxanthone, 2,4- Thioxanthone series such as dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone; Aminobenzophenone series such as Michler ketone, 4,4′-diethylaminobenzophenone; 1- [4- (phenylthio ) Phenyl] -1,2-octanedione 2- (o
- the above polymerization initiators may be used alone or in combination of two or more.
- the content thereof is 1 to 50% by weight, preferably 5 to 30% by weight, based on the weight of the coloring composition.
- the solvent may be appropriately selected according to the components contained in the coloring composition. Specifically, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, oxy Methyl acetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, 3-methoxypropionic acid Methyl, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, eth
- the binder resin may be any resin that is soluble in an alkaline developer used in the production of a color filter.
- carboxyl group-containing ethylenically unsaturated monomer examples include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, ⁇ -chloroacrylic acid, ethacrylic acid and cinnamic acid; maleic acid and maleic anhydride Unsaturated dicarboxylic acids (anhydrides) such as fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid; trivalent or higher unsaturated polycarboxylic acids (anhydrides), 2- (Meth) acryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl 2-hydroxypropyl phthalate, 2-acryloyloxyethyl 2-hydroxyethylphthalic acid and the like.
- unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, ⁇ -ch
- the content of the binder resin is 10% to 50% by weight, preferably 20% to 50% by weight, based on the weight of the coloring composition.
- radical polymerizable monomer or oligomer examples include polyethylene glycol diacrylate (having 2 to 14 ethylene groups), polyethylene glycol dimethacrylate (having 2 to 14 ethylene groups), and trimethylolpropane.
- crosslinking agent examples include (a) an epoxy resin, (b) a melamine compound, a guanamine compound, and a glycoluril substituted with at least one substituent selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group.
- a compound or a urea compound (c) a phenol compound, a naphthol compound or a hydroxyanthracene compound substituted with at least one substituent selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group.
- Functional epoxy resins are preferred.
- the content of the crosslinking agent is 10% to 50% by weight, preferably 20% to 50% by weight, based on the weight of the coloring composition.
- the coloring composition of the present invention may contain a polymerization inhibitor, a surfactant, an additive and the like in addition to those described above, and are not particularly limited as long as they are known per se. There is no limitation as long as it is an amount usually used in this field.
- the coloring composition of the present invention is prepared by mixing the aforementioned components.
- Example 1 Synthesis of Polymerizable Dye (Dye Monomer 2) of the Present Invention (1) Construction of Dye Skeleton In a round bottom flask equipped with a stirrer, 2- (1,3,3, -trimethylindoline-2-ylidene) Acetaldehyde (Compound 1) 10.0 g (5.0 mmol, Wako Pure Chemical Industries, Ltd.), 2- (4-aminophenyl) ethanol (Compound 2) 6.8 g (5.0 mmol, Tokyo Chemical Industry Co., Ltd.) And 50 mL of acetic acid were added and reacted at 40 ° C. for 3.5 hours.
- 2- (1,3,3, -trimethylindoline-2-ylidene) Acetaldehyde Compound 10.0 g (5.0 mmol, Wako Pure Chemical Industries, Ltd.)
- 2- (4-aminophenyl) ethanol Compound 2 6.8 g (5.0 mmol, Tokyo Chemical Industry Co., Ltd.)
- Example 2 Synthesis of polymerizable pigment (dye monomer 3) (1)
- To 0 g (16.8 mmol) 100 mL of methylene chloride was added and dissolved.
- 11.5 g (16.8 mmol, manufactured by Tosoh Finechem Co., Ltd.) of lithium salt of tetrakis (pentafluorophenyl) boron (IV) and 100 mL of ion-exchanged water were added and dissolved, followed by reaction at room temperature for 30 minutes.
- Example 3 Synthesis of polymerizable pigment (dye monomer 4)
- polymerizable group 13.7 g of 4-aminobenzoic acid (Compound 10) (Wako Pure Chemical Industries, Ltd.) was introduced into a round bottom flask equipped with a stirrer.
- 2-hydroxyethyl methacrylate compound 11
- 4-dimethylaminopyridine 3.7 g
- methylene chloride 180 mL
- Example 4 Synthesis of polymerizable pigment (dye monomer 5) (1) Introduction of polymerizable group In a round bottom flask equipped with a stirrer, 7.2 g of 4-nitrophenylacetic acid (compound 14) (Wako Pure Chemical Industries, Ltd.) ), 2-hydroxyethyl methacrylate (compound 11) 5.2 g (manufactured by Wako Pure Chemical Industries, Ltd.), 4-dimethylaminopyridine 1.5 g (manufactured by Wako Pure Chemical Industries, Ltd.) and chloride 80 mL of methylene (Wako Pure Chemical Industries, Ltd.) was added.
- 4-nitrophenylacetic acid compound 14
- 2-hydroxyethyl methacrylate compound 11
- 4-dimethylaminopyridine 1.5 g
- chloride 80 mL of methylene (Wako Pure Chemical Industries, Ltd.) was added.
- Example 6 Synthesis of polymerizable pigment (dye monomer 7)
- Introduction of polymerizable group 2.7 g of 4,5-dimethoxy-2-nitrobenzoic acid (compound 22) was introduced into a round bottom flask equipped with a stirrer.
- (Manufactured by Wako Pure Chemical Industries, Ltd.) 1.6 g of 2-hydroxyethyl methacrylate (Compound 11) (manufactured by Wako Pure Chemical Industries, Ltd.), 0.4 g of 4-dimethylaminopyridine (Wako Pure Chemical Industries, Ltd.) Co., Ltd.) and 20 mL of methylene chloride (Wako Pure Chemical Industries, Ltd.) were added.
- Example 7 Synthesis of polymerizable pigment (dye monomer 8) (1) Introduction of polymerizable group 3.9 g of 2-nitrocinnamic acid (compound 26) (Wako Pure Chemical Industries, Ltd.) in a round bottom flask equipped with a stirrer Manufactured by Co., Ltd.), 2.6 g of 2-hydroxyethyl methacrylate (compound 11) (manufactured by Wako Pure Chemical Industries, Ltd.), 0.7 g of 4-dimethylaminopyridine (manufactured by Wako Pure Chemical Industries, Ltd.), and 40 mL of methylene chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added.
- 2-nitrocinnamic acid compound 26
- 2-hydroxyethyl methacrylate compound 11
- 4-dimethylaminopyridine manufactured by Wako Pure Chemical Industries, Ltd.
- 40 mL of methylene chloride manufactured by Wako Pure Chemical Industries, Ltd.
- Example 8 Synthesis of polymerizable pigment (dye monomer 9) (1) Introduction of polymerizable group In a round bottom flask equipped with a stirrer, 1.9 g of 4-nitrocinnamic acid (compound 30) (Tokyo Chemical Industry ( Co., Ltd.), 20 ml of toluene (manufactured by Wako Pure Chemical Industries, Ltd.) and 1 ml of N, N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.) were added and heated to 60 ° C. Thionyl chloride 1.3g (made by Wako Pure Chemical Industries Ltd.) was inject
- Thionyl chloride 1.3g (made by Wako Pure Chemical Industries Ltd.) was inject
- Example 9 27.9 g of propylene glycol monomethyl ether acetate (manufactured by Wako Pure Chemical Industries, Ltd.) was placed in a 200 ml round bottom flask equipped with a synthesis stirrer for dye polymer 2 , a cooling tube, a thermometer, and a nitrogen introduction tube. Then, heating was performed under a nitrogen stream until the internal temperature reached 90 ° C.
- Example 11 Evaluation of heat resistance of dye monomer 2 (230 ° C., 0.5 hour)
- the heat resistance of the dye monomer 2 obtained in Example 1 was evaluated as follows. (1) Synthesis of polymer containing no dye 98.5 g of propylene glycol monomethyl ether acetate was placed in a 500 mL round bottom flask equipped with a stirrer, a cooling tube, a thermometer and a nitrogen introducing tube, and the internal temperature was reduced under a nitrogen stream. Heated to 90 ° C.
- Examples 12 to 16 Evaluation of heat resistance of dye monomers 3 to 6 and 9 (230 ° C., 0.5 hour) Except that the dye monomers 3 to 6 and 9 were used in place of the dye monomer 2 in Example 11, the operation was performed according to the method of Example 11, and the heat resistance of each of the dye monomers 3 to 6 and 9 was evaluated.
- the results and the maximum absorption wavelength (nm) in the methanol solution (MeOH) solution are shown in Table 1 together with the results of Example 11.
- Examples 17 to 18 Maximum absorption wavelengths of dye monomers 7 and 8 Maximum absorption wavelengths (nm) of the monomers 7 and 8 in a methanol solution (MeOH) are shown in Table 1.
- Example 19 Evaluation of heat resistance of dye polymers 2 and 3 (230 ° C., 0.5 hour)
- the heat resistance of the dye polymer 2 solution obtained in Example 9 was evaluated as follows. That is, each of the obtained dye polymer 2 solutions was spin-coated on a 3-inch glass wafer (Eagle XG manufactured by Corning) and then dried for 90 seconds on a hot plate heated to 90 ° C. to form a thin film having a thickness of 1 micron. Obtained. Each thin film obtained was measured for absorbance ( ⁇ a) at the maximum absorption wavelength using a spectrophotometer (Spectrophotometer UV-2550, manufactured by Shimadzu Corporation), and then on a hot plate heated to 230 ° C. for 30 minutes.
- ⁇ a absorbance
- Example 20 Evaluation of heat resistance of dye polymer 3 (230 ° C., 0.5 hour) The heat resistance of the dye polymer 3 was evaluated by operating according to the method of Example 19 except that the dye polymer 3 solution was used instead of the dye polymer 2 solution in Example 19. The results are shown in Table 1 together with the results of Examples 11 to 19.
- Basic Yellow 13 which is a known yellow dye, did not leave any dye after heating, whereas the dye monomer and polymer of the present invention showed a high dye residual ratio and high heat resistance. It turns out to have. That is, it was found that the compound of the present invention having a polymerizable group and having tetrakis (pentafluorophenyl) boron as an anion and a polymer derived from the compound have excellent heat resistance. It has also been found that the dye polymer exhibits higher heat resistance than the dye monomer.
- dye monomers 2 to 9 have a maximum absorption wavelength of 410 to 430 nm. Therefore, transparent materials using these dyes alone or in combination can reduce the transmission of light of a specific wavelength.
- Example 21 Synthesis of Dye Polymer 4 105 g of propylene glycol monomethyl ether acetate (manufactured by Daicel Corporation) was placed in a 2000 ml round bottom flask equipped with a stirrer, a cooling tube, a thermometer, and a nitrogen introduction tube, under a nitrogen stream. The mixture was heated until the internal temperature reached 95 ° C.
- Example 22 Molding of colored plate containing dye polymer 4 0.5 part by weight of the dye polymer 4 obtained above and 99.5 parts by weight of a commercially available methyl methacrylate resin (Acrypet MD001 (manufactured by Mitsubishi Rayon)) in the same direction It melt-mixed using the rotating biaxial extruder, and the colored resin pellet was obtained. Next, the obtained resin pellets were processed by an electric injection molding machine to prepare a colored plate of 150 mm ⁇ 150 mm ⁇ t2 mm.
- Example 23 Dissolution resistance test of colored plate containing dye polymer 4
- the colored plate prepared in Example 22 was cut into a size of 40 mm ⁇ 30 mm ⁇ t2 mm, and then an aqueous ethanol solution in which 50 parts of ethanol and 50 parts of ion-exchanged water were mixed. It was immersed in 80 ml and stored in a constant temperature bath at 40 ° C. for 200 hours. The ethanol solution was taken out, and the spectrum of the ethanol aqueous solution was measured using a spectrophotometer (Spectrophotometer UV-2500 manufactured by Shimadzu Corporation).
- Comparative Example 4 Elution Resistance Test of Colored Plate Containing Basic Yellow 13
- Example 23 the same procedure was used except that the colored plate prepared in Comparative Example 3 was used, and the elution rate of Basic Yellow 13 was calculated. The results are shown in Table 2 together with the results of Example 23.
- the colored plate using the dye polymer of the present invention can be a colored material having excellent elution resistance.
- Example 24 Weather Resistance Test
- the colored plate prepared in Example 22 was cut into 65 mm ⁇ 65 mm ⁇ t2 mm, and a device specified in JIS B7754: 1991 [Ci4000 (manufactured by Atlas)] was used, and a xenon arc lamp under the following conditions. An accelerated weathering test according to the formula was performed.
- the colored plate containing the dye polymer has excellent weather resistance as compared with the molded plate containing Basic Yellow 13.
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Abstract
Description
一方、カラーフィルターの黄色染料としては、シアニン系着色化合物、バルビツール酸アゾ系着色化合物(特許文献1)、アゾ系着色化合物(特許文献2)、ピリドンアゾ系化合物(特許文献3)等が通常用いられている。しかし、上記アゾ系化合物のアゾ基は、ラジカル反応を阻害することが知られている。このため、アゾ系化合物を原料としてカラーフィルターを製造する場合、重合反応が進まず充分な強度の硬化膜が得られない可能性があった。
(式中、R1~R4は、それぞれ独立して、水素原子、ニトロ基、ハロゲノ基、シアノ基、アミド基、カルボキシル基、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基、炭素数2~4のアルキルオキシカルボニル基、炭素数2~4のアルキルカルボニルオキシ基、又は炭素数7~10のアリールカルボニル基を表し、
R5及びR6は、それぞれ独立して、水素原子、炭素数1~6のアルキル基、炭素数7~13のアリールアルキル基、或いは、フェニル基の置換基として、炭素数1~6のアルキル基、ニトロ基、ハロゲノ基又はシアノ基を有する、炭素数7~9のフェニルアルキル基を表し、
R7は、水素原子、炭素数1~6のアルキル基、炭素数7~13のアリールアルキル基、置換基として、炭素数1~6のアルコキシ基、ヒドロキシル基、カルボキシル基、ハロゲノ基、シアノ基、アミド基又は炭素数2~4のアルキルオキシカルボニル基を有する、炭素数1~6のアルキル基、或いは、フェニル基の置換基として、炭素数1~6のアルコキシ基、ハロゲノ基又はアミド基を有する、炭素数7~9のフェニルアルキル基を表し、
n個のR8は、それぞれ独立して、ニトロ基、ハロゲノ基、シアノ基、アミド基、カルボキシル基、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基、炭素数2~4のアルキルオキシカルボニル基、炭素数2~4のアルキルカルボニルオキシ基、又は炭素数7~10のアリールカルボニル基を表し、
R12は、水素原子又はメチル基を表し、
A1は、-O-、-OCO-、-COO-、ビニレン基及びアリーレン基から選ばれる少なくとも1つの基を鎖中に有する炭素数1~21のアルキレン基、-O-、-OCO-、-COO-、ビニレン基及びアリーレン基から選ばれる少なくとも1つの基を鎖中に有し、且つ、ヒドロキシル基を置換基として有する炭素数1~21のアルキレン基、炭素数1~21のアルキレン基、或いは、ヒドロキシル基を置換基として有する炭素数1~21のアルキレン基を表し、A2は-NH-または-O-を表す。
An-は、電子吸引性の置換基を有するアリール基、電子吸引性の置換基を有するスルホニル基、又はハロゲン化アルキル基を含むアニオンを表す。)
一般式(1)のAn-で示される電子吸引性の置換基を有するアリール基、電子吸引性の置換基を有するスルホニル基又はハロゲン化アルキル基を含むアニオン(以下、これらを本発明に係るアニオンと略記する場合がある)としては、電子吸引性の置換基を有するアリール基、電子吸引性の置換基を有するスルホニル基、又はハロゲン化アルキル基を含む、例えばスルホン酸アニオン、窒素アニオン(N-)、4級ホウ素アニオン、硝酸イオン、燐酸イオン等が挙げられ、スルホン酸アニオン、窒素アニオン、4級ホウ素アニオンが好ましく、4級ホウ素アニオンがより好ましい。
mは、R41がハロゲン原子の場合は2~5が好ましく、3~5がより好ましく、5が更に好ましい。R41がニトロ基の場合は1~3が好ましく、1がより好ましい。R41がハロゲン化アルキル基の場合は、1~5が好ましい。
(式中、R41、mは上記と同じ。m個のR41は同一でも異なっていてもよい。)
(式中、R42~R45は、それぞれ独立して、炭素数1~3のハロゲン化アルキル基、ハロゲン原子又はニトロ基を表し、m1~m4は、それぞれ独立して、1~5の整数を表す。m1個のR42は、同一でも異なっていてもよく、m2個のR43、m3個のR44及びm4個のR45も、それぞれ同一でも異なっていてもよい。)
一般式(16)のR42~R45におけるハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられ、中でもフッ素原子が好ましい。
一般式(17)のR46におけるハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられ、中でもフッ素原子が好ましい。
本発明の化合物は、一般式(1)で示される化合物である。
(式中、2つのR51は、それぞれ独立して、炭素数1~10のアルキレン基を表し、X1は-O-、-OCO-、COO-、ビニレン基又はアリーレン基を表す。)
(式中、3つのR51は、それぞれ独立して上記と同じものを表し、X1は上記と同じ。)
(式中、2つのR51は、それぞれ独立して上記と同じものを表し、p7は、1~9の整数を表す。)
(式中、2つのR51は、それぞれ独立して上記と同じものを表し、p9は、1~9の整数を表す。)
(式中、X2は-O-、-OCO-、又は-COO-基を表し、R53は、炭素数1~10のアルキレン基を表す。)
-CH=CH-COO-R54- (6-6)
(式中、R54は、炭素数1~10のアルキレン基を表す。)
-CH2-X11-CH2-
-CH2-X11-C2H4-
-CH2-X11-C3H6-
-CH2-X11-C4H8-
-CH2-X11-C5H10-
-CH2-X11-C6H12-
-C2H4-X11-CH2-
-C2H4-X11-C2H4-
-C2H4-X11-C3H6-
-C2H4-X11-C4H8-
-C2H4-X11-C5H10-
-C2H4-X11-C6H12-
-C3H6-X11-CH2-
-C3H6-X11-C2H4-
-C3H6-X11-C3H6-
-C3H6-X11-C4H8-
-C3H6-X11-C5H10-
-C3H6-X11-C6H12-
-CH2-X11-C6H10-
-C2H4-X11-C6H10-
-C3H6-X11-C6H10-
-CH2-OCO-CH2-
-CH2-OCO-C2H4-
-CH2-OCO-C3H6-
-CH2-OCO-C4H8-
-CH2-OCO-C5H10-
-CH2-OCO-C6H12-
-C2H4-OCO-CH2-
-C2H4-OCO-C2H4-
-C2H4-OCO-C3H6-
-C2H4-OCO-C4H8-
-C2H4-OCO-C5H10-
-C2H4-OCO-C6H12-
-C3H6-OCO-CH2-
-C3H6-OCO-C2H4-
-C3H6-OCO-C3H6-
-C3H6-OCO-C4H8-
-C3H6-OCO-C5H10-
-C3H6-OCO-C6H12-
-CH2-OCO-C6H10-
-C2H4-OCO-C6H10-
-C3H6-OCO-C6H10-
-CH2-X11-C2H4-X11-CH2-
-CH2-X11-C2H4-X11-C2H4-
-C2H4-X11-C2H4-X11-CH2-
-C2H4-X11-C2H4-X11-C2H4-
-C2H4-X11-C2H4-X11-C3H6-
-C2H4-X11-C2H4-X11-C4H8-
-C2H4-X11-C2H4-X11-C5H10-
-C2H4-X11-C2H4-X11-C6H12-
-C3H6-X11-C2H4-X11-CH2-
-C3H6-X11-C2H4-X11-C2H4-
-C3H6-X11-C2H4-X11-C3H6-
-C3H6-X11-C2H4-X11-C4H8-
-C3H6-X11-C2H4-X11-C5H10-
-C3H6-X11-C2H4-X11-C6H12-
-C4H8-X11-C2H4-X11-CH2-
-C4H8-X11-C2H4-X11-C2H4-
-C4H8-X11-C2H4-X11-C3H6-
-C4H8-X11-C2H4-X11-C4H8-
-C4H8-X11-C2H4-X11-C5H10-
-C4H8-X11-C2H4-X11-C6H12-
-C5H10-X11-C2H4-X11-CH2-
-C5H10-X11-C2H4-X11-C2H4-
-C5H10-X11-C2H4-X11-C3H6-
-C5H10-X11-C2H4-X11-C4H8-
-C5H10-X11-C2H4-X11-C5H10-
-C5H10-X11-C2H4-X11-C6H12-
-C6H12-X11-C2H4-X11-CH2-
-C6H12-X11-C2H4-X11-C2H4-
-C6H12-X11-C2H4-X11-C3H6-
-C6H12-X11-C2H4-X11-C4H8-
-C6H12-X11-C2H4-X11-C5H10-
-C6H12-X11-C2H4-X11-C6H12-
-CH2-X11-C3H6-X11-CH2-
-C2H4-X11-C3H6-X11-C2H4-
-C2H4-X11-C3H6-X11-C3H6-
-C2H4-X11-C3H6-X11-C4H8-
-C2H4-X11-C3H6-X11-C5H10-
-C2H4-X11-C3H6-X11-C6H12-
-C3H6-X11-C3H6-X11-C2H4-
-C3H6-X11-C3H6-X11-C3H6-
-C3H6-X11-C3H6-X11-C4H8-
-C3H6-X11-C3H6-X11-C5H10-
-C3H6-X11-C3H6-X11-C6H12-
-C4H8-X11-C3H6-X11-C4H8-
-C5H10-X11-C3H6-X11-C5H10-
-C6H12-X11-C3H6-X11-C6H12-
-C2H4-X11-CH2-X11-C2H4-
-C2H4-X11-C4H8-X11-C2H4-
-C2H4-X11-C5H10-X11-C2H4-
-C2H4-X11-C6H12-X11-C2H4-
-C2H4-X11-C6H10-X11-C2H4-
-CH2-OCO-C2H4-COO-C2H4-
-CH2-OCO-C3H6-COO-C3H6-
-C4H8-OCO-C2H4-COO-CH2-
-C4H8-OCO-C2H4-COO-C2H4-
-C4H8-OCO-C2H4-COO-C3H6-
-C4H8-OCO-C2H4-COO-C4H8-
-C4H8-OCO-C2H4-COO-C5H10-
-C4H8-OCO-C2H4-COO-C6H12-
-C5H10-OCO-C2H4-COO-CH2-
-C5H10-OCO-C2H4-COO-C2H4-
-C5H10-OCO-C2H4-COO-C3H6-
-C5H10-OCO-C2H4-COO-C4H8-
-C5H10-OCO-C2H4-COO-C5H10-
-C5H10-OCO-C2H4-COO-C6H12-
-C6H12-OCO-C2H4-COO-CH2-
-C6H12-OCO-C2H4-COO-C2H4-
-C6H12-OCO-C2H4-COO-C3H6-
-C6H12-OCO-C2H4-COO-C4H8-
-C6H12-OCO-C2H4-COO-C5H10-
-C6H12-OCO-C2H4-COO-C6H12-
-CH2-OCO-C3H6-COO-CH2-
-C2H4-OCO-C3H6-COO-C2H4-
-C2H4-OCO-C3H6-COO-C3H6-
-C2H4-OCO-C3H6-COO-C4H8-
-C2H4-OCO-C3H6-COO-C5H10-
-C2H4-OCO-C3H6-COO-C6H12-
-C3H6-OCO-C3H6-COO-C2H4-
-C3H6-OCO-C3H6-COO-C3H6-
-C3H6-OCO-C3H6-COO-C4H8-
-C3H6-OCO-C3H6-COO-C5H10-
-C3H6-OCO-C3H6-COO-C6H12-
-C4H8-OCO-C3H6-COO-C4H8-
-C5H10-OCO-C3H6-COO-C5H10-
-C6H12-OCO-C3H6-COO-C6H12-
-C2H4-OCO-CH2-COO-C2H4-
-C2H4-OCO-C4H8-COO-C2H4-
-C2H4-OCO-C5H10-COO-C2H4-
-C2H4-OCO-C6H12-COO-C2H4-
-C2H4-OCO-C6H10-COO-C2H4-
-CH2-(C2H4O)p7-CH2-
-CH2-(C2H4O)p7-C2H4-
-CH2-(C2H4O)p7-C3H6-
-C2H4-(C2H4O)p7-CH2-
-C2H4-(C2H4O)p7-C2H4-
-C2H4-(C2H4O)p7-C3H6-
-C2H4-(C2H4O)p7-C4H8-
-C2H4-(C2H4O)p7-C5H10-
-C2H4-(C2H4O)p7-C6H12-
-C2H4-(C2H4O)p7-CH2-
-C2H4-(C2H4O)p7-C2H4-
-C2H4-(C2H4O)p7-C3H6-
-C3H6-(C2H4O)p7-CH2-
-C3H6-(C2H4O)p7-C2H4-
-C3H6-(C2H4O)p7-C3H6-
-CH2-(CH2CH(CH3)O)p9-CH2-
-CH2-(CH2CH(CH3)O)p9-C2H4-
-CH2-(CH2CH(CH3)O)p9-C3H6-
-C2H4-(CH2CH(CH3)O)p9-CH2-
-C2H4-(CH2CH(CH3)O)p9-C2H4-
-C2H4-(CH2CH(CH3)O)p9-C3H6-
-C2H4-(CH2CH(CH3)O)p9-C4H8-
-C2H4-(CH2CH(CH3)O)p9-C5H10-
-C2H4-(CH2CH(CH3)O)p9-C6H12-
-C2H4-(CH2CH(CH3)O)p9-CH2-
-C2H4-(CH2CH(CH3)O)p9-C2H4-
-C2H4-(CH2CH(CH3)O)p9-C3H6-
-C3H6-(CH2CH(CH3)O)p9-CH2-
-C3H6-(CH2CH(CH3)O)p9-C2H4-
-C3H6-(CH2CH(CH3)O)p9-C3H6-
-COO-CH2-、-COO-C2H4-、-COO-C3H6-、
-COO-C4H8-、-COO-C5H10-、-COO-C6H12-、
-O-CH2-、-O-C2H4-、-O-C3H6-、-O-C4H8-、-O-C5H10-、-O-C6H12-、
-OCO-CH2-、-OCO-C2H4-、-OCO-C3H6-、-OCO-C4H8-、-OCO-C5H10-、-OCO-C6H12-
中でも、下記式が好ましい。
-COO-CH2-、-COO-C2H4-、-COO-C3H6-、-COO-C4H8-、-COO-C5H10-、-COO-C6H12-
更に、下記式がより好ましい。
-COO-CH2-、-COO-C2H4-、-COO-C3H6-
-CH=CH-COO-CH2-、-CH=CH-COO-C2H4-、
-CH=CH-COO-C3H6-、-CH=CH-COO-C4H8-、
-CH=CH-COO-C5H10-、-CH=CH-COO-C6H12-
中でも、下記式が好ましい。
-CH=CH-COO-CH2-、-CH=CH-COO-C2H4-、
-CH=CH-COO-C3H6-
(式中、2つのR52は、それぞれ独立して、ヒドロキシル基を置換基として有する若しくは無置換の炭素数1~10のアルキレン基を表し、X1は上記と同じである。但し、2つのR52のうちの少なくとも1つは、ヒドロキシル基を置換基として有する炭素数1~6のアルキレン基を表す。)、
(式中、3つのR52は、それぞれ独立して、上記と同じであり、2つのX1も、それぞれ独立して、上記と同じである。但し、3つのR52のうちの少なくとも1つは、ヒドロキシル基を置換基として有する炭素数1~10のアルキレン基を表し、上記式中の炭素数の総数は21以下である。)、
上記一般式(6-1)及び(6-2)のR51における炭素数1~10のアルキレン基と同じものが挙げられ、好ましいものも同じである。
-CH2-X11-C3H5(OH)-
-CH2-X11-C4H7(OH)-
-CH2-X11-C5H9(OH)-
-CH2-X11-C6H11(OH)-
-C2H4-X11-C3H5(OH)-
-C2H4-X11-C4H7(OH)-
-C2H4-X11-C5H9(OH)-
-C2H4-X11-C6H11(OH)-
-C3H6-X11-C3H5(OH)-
-C3H6-X11-C4H7(OH)-
-C3H6-X11-C5H9(OH)-
-C3H6-X11-C6H11(OH)-
-C3H5(OH)-X11-CH2-
-C3H5(OH)-X11-C2H4-
-C3H5(OH)-X11-C3H6-
-C3H5(OH)-X11-C4H8-
-C3H5(OH)-X11-C5H10-
-C3H5(OH)-X11-C6H12-
-C3H5(OH)-X11-C3H5(OH)-
-C3H5(OH)-X11-C4H7(OH)-
-C3H5(OH)-X11-C5H9(OH)-
-C3H5(OH)-X11-C6H11(OH)-
-CH2-X11-C3H5(OH)-X11-CH2-
-C2H4-X11-C3H5(OH)-X11-C2H4-
-C2H4-X11-C3H5(OH)-X11-C3H6-
-C2H4-X11-C3H5(OH)-X11-C4H8-
-C2H4-X11-C3H5(OH)-X11-C5H10-
-C2H4-X11-C3H5(OH)-X11-C6H12-
-C3H6-X11-C3H5(OH)-X11-C2H4-
-C3H6-X11-C3H5(OH)-X11-C3H6-
-C3H6-X11-C3H5(OH)-X11-C4H8-
-C3H6-X11-C3H5(OH)-X11-C5H10-
-C3H6-X11-C3H5(OH)-X11-C6H12-
-C4H8-X11-C3H5(OH)-X11-C4H8-
-C5H10-X11-C3H5(OH)-X11-C5H10-
-C6H12-X11-C3H5(OH)-X11-C6H12-
-C2H4-X11-C3H5(OH)-X11-C3H5(OH)-
-C2H4-X11-C3H5(OH)-X11-C4H7(OH)-
-C2H4-X11-C3H5(OH)-X11-C5H9(OH)-
-C2H4-X11-C3H5(OH)-X11-C6H11(OH)-
-C3H6-X11-C3H5(OH)-X11-C2H3(OH)-
-C3H6-X11-C3H5(OH)-X11-C3H5(OH)-
-C4H8-X11-C3H5(OH)-X11-C4H7(OH)-
-C5H10-X11-C3H5(OH)-X11-C5H9(OH)-
-C6H12-X11-C3H5(OH)-X11-C6H11(OH)-
-(CH2)p10-R56-(CH2)p10- (8)
(式中、R56は、ヒドロキシル基を置換基として有する炭素数1~9のアルキレン基を表し、p10は、0~6の整数を表す。)、
-CH2-C6H9(OH)-CH2-、
-C2H4-C6H9(OH)-C2H4-、
-C3H6-C6H9(OH)-C3H6-、
-CH2-CH(OH)-C2H4-
-CH2-CH(OH)-C3H6-
-CH2-CH(OH)-C4H8-
-C2H4-CH(OH)-CH2-
-C2H4-CH(OH)-C2H4-
-C2H4-CH(OH)-C3H6-
-CH2-C2H4(OH)-C2H4-
-CH2-C2H4(OH)-C3H6-
-CH2-C2H4(OH)-C4H8-
-C2H4-C2H4(OH)-CH2-
-C2H4-C2H4(OH)-C2H4-
-C2H4-C2H4(OH)-C3H6-
等が挙げられる。
本発明の化合物は、例えば(I)下記一般式(20)で示される化合物を、下記一般式(21)で示される化合物、一般式(22)で示される化合物、又は一般式(23)で示される化合物と反応させた後、塩交換反応を行うことにより、或いは(II)下記一般式(24)で示される化合物を、下記一般式(25)で示される化合物と反応させた後、塩交換反応を行うことにより製造される。
(式中、2つのR51は、それぞれ独立して、炭素数1~10のアルキレン基を表し、X1は上記と同じ。但し、式中の炭素数の総数は15以下である。)、
(式中、3つのR51は、それぞれ独立して上記と同じものを表し、X1は上記と同じ。但し、式中の炭素数の総数は15以下である。)、
(式中、2つのR51は、それぞれ独立して上記と同じものを表し、p7は、1~9の整数を表す。但し、式中の炭素数の総数は15以下である。)、
(式中、2つのR51は、それぞれ独立して上記と同じものを表し、p9は、1~9の整数を表す。但し、式中の炭素数の総数は15以下である。)、
(式中、R52及びX1は、上記と同じ。但し、式中の炭素数の総数は15以下である。)、
(式中、R52及びX1は、上記と同じ。但し、式中の炭素数の総数は15以下である。)、
上記一般式(7-1’)又は(7-2’)で示される基の好ましい具体例としては、上記一般式(7-1)又は(7-2)で示される基の好ましい具体例に準じたものが挙げられる。
(式中、R56は、ヒドロキシル基を置換基として有する炭素数1~9のアルキレン基を表し、p10は、0~6の整数を表す。但し、式中の炭素数の総数は15以下である。)、
上記一般式(21)で示される化合物の使用量は、一般式(20)で示される化合物の1~5モル倍であり、好ましくは1~2モル倍である。
この場合の塩交換反応は、一般式(20)で示される化合物に、本発明に係るアニオンの塩を溶媒中で接触させることによりなされればよい。ここで用いられる本発明に係るアニオンの塩や、溶媒、反応条件等については、上記塩交換反応と同じものが挙げられる。
また、塩交換反応後の一般式(20)で示される化合物と一般式(21) で示される化合物の反応、塩交換反応後の一般式(20)で示される化合物と一般式(22) で示される化合物の反応並びに、塩交換反応後の一般式(20)で示される化合物と一般式(23) で示される化合物の反応の反応条件やその他の条件は、上記本発明の化合物の製造方法と同じである。
[式中、R12、n、A1は、上記と同じ。R’8は、炭素数1~6のアルコキシル基を表す。]
上記R’8における炭素数1~6のアルコキシル基としては、メトキシ基、エトキシ基、n-プロポキシ基、n-ブトキシ基、、n-ペンチルオキシ基、n-ヘキシルオキシ基等が挙げられ、メトキシ基、エトキシ基、n-プロポキシ基が好ましく、メトキシ基がより好ましい。
上記一般式(24)で示される化合物の使用量は、一般式(25)で示される化合物の1~5モル倍であり、好ましくは1~2モル倍である。
本発明のポリマーは、上記本発明の化合物由来のモノマー単位を有するポリマーである。
基、炭素数7~13のアリールアルキル基、炭素数2~9のアルコキシアルキル基、炭素数3~9のアルコキシアルコキシアルキル基、炭素数7~13のアリールオキシアルキル基、炭素数5~7のモルホリノアルキル基、炭素数3~9のトリアルキルシリル基、酸素原子を有する又は酸素原子を有さない炭素数6~10の脂環式炭化水素基、炭素数3~9のジアルキルアミノアルキル基、炭素数1~18のフッ化アルキル基、又は炭素数1~6のN-アルキレンフタルイミド基、下記一般式(2-1)で示される基
下記一般式(2-2)で示される基
1~3のアルキル基としては、上記R31と同じものが挙げられる。
本発明のポリマーは、例えば以下の如く製造される。即ち、本発明の化合物をモノマーとして自体公知の重合反応に付すことにより、本発明のポリマーを得ることができる。本発明のポリマーがコポリマーの場合には、重合反応の際に、上記本発明の化合物と一般式(2)、一般式(3)、一般式(4)又は一般式(5)で示される化合物の1~2種とを、最終的に得られるポリマー中の各モノマーに由来するモノマー単位の比率が上記の如くなるように混合した後、重合させればよい。
上記重合反応としては、例えば、以下の如くなされる。即ち、一般式(1)で示される本発明の化合物を、要すれば、更に一般式(2)、一般式(3)、一般式(4)又は一般式(5)で示される化合物の1~2種を、その総容量に対して1~10倍容量の適当な溶媒、例えばトルエン、1,4-ジオキサン、テトラヒドロフラン、イソプロパノール、メチルエチルケトン、プロピレングリコールモノメチルエーテルアセテート等に溶解し、溶解した化合物の全量に対して0.01~30重量%の重合開始剤、例えばアゾイソブチロニトリル、2,2’-アゾビス(2,4-ジメチルバレロニトリル)、2,2’-アゾビス(2-メチルプロピオネート)、2,2’-アゾビス(2-メチルブチロニトリル)、過酸化ベンゾイル、過酸化ラウロイル等の存在下、50~150℃で1~20時間反応させることにより行なわれる。反応後は高分子取得の常法に従って処理してもよい。
本発明の着色組成物は、上記本発明の化合物又はポリマーを少なくとも1種含むものである。該着色組成物は、カラーフィルター用として好適に用いることができる。該着色組成物は、耐熱性を有する優れた着色硬化膜を形成することができる。そのため、本発明の着色組成物は、液晶表示装置(LCD)や固体撮像素子(CCD、CMOS等)に用いられるカラーフィルター等の着色画素形成用途、印刷インキ、インクジェットインキ、および塗料等の用途に用いることができ、特に、液晶表示装置のカラーフィルター用として好適である。さらに、本発明の着色組成物は、従来公知の成形方法により、シート、フィルム、ボトル、カップ等に成形して着色樹脂成形物として使用するもできる。よって、メガネ、コンタクトレンズ、カラーコンタクトレンズ等の用途にも使用することができ、公知の樹脂との多層構造体とすることによっても同様の用途に使用することができる。その他にも、例えば光学フィルム、ヘアカラーリング剤、化合物や生体物質に対する標識物質、有機太陽電池の材料等の用途にも用いることが可能である。上記本発明の着色組成物は、各用途に合わせて、上記本発明の化合物又はポリマーの他に、この分野で通常用いられる添加剤等を含んでいてもよい。
(1)色素骨格の構築
攪拌装置を備えた丸底フラスコに、2-(1,3,3,-トリメチルインドリン-2-イリデン)アセトアルデヒド(化合物1)10.0g(5.0mmol、和光純薬工業(株)製)、2-(4-アミノフェニル)エタノール(化合物2)6.8g(5.0mmol、東京化成工業(株)製)、及び酢酸50mLを加え、40℃で3.5時間反応させた。更に、塩化メチレン(和光純薬工業(株)製)及び飽和食塩水を加えて有機層に目的物を抽出した後、有機層を飽和重曹水で2回洗浄し、飽和食塩水で洗浄した。その後、減圧濃縮によって溶媒を留去し、褐色固体のBasic Yellow13誘導体(化合物3)15.3g(収率86%)を得た。
攪拌装置を備えた丸底フラスコに、Basic Yellow13誘導体(化合物3)10.0g(28mmol)、NKエステルSA(2-メタクリロイルオキシエチルサクシネート、化合物4)7.8g(34mmol、新中村化学工業(株)製)、4‐ジメチルアミノピリジン1.0g(8.2mmol、和光純薬工業(株)製)、1-エチル-3-(3-ジメチルアミノプロピル)カルボジイミド塩酸塩(WSC)9.2g(48mmol、東洋紡(株)製)、及び塩化メチレン100mL(和光純薬工業(株)製)を加え、室温で24時間反応させた。次いで、イオン交換水を加えて有機層を洗浄し、減圧濃縮によって溶媒を留去した。さらにシリカゲルカラムで精製し、減圧濃縮にて溶媒を留去し、褐色固体の染料モノマー1(化合物5)を3.0g(収率30%)得た。
撹拌装置を備えた丸底フラスコ中で、染料モノマー1(化合物5)2.0g(3.5mmol)に塩化メチレン100mLを加えて溶解した。ここにテトラキス(ペンタフルオロフェニル)ホウ素(IV)のリチウム塩3.8g(5.5mmol、東ソー・ファインケム(株)製)及びイオン交換水100mLを加えて溶解後、室温で30分間反応させた。得られた有機溶媒を分液し、イオン交換水で洗浄した後、減圧濃縮によって溶媒を留去し、カウンターアニオンにテトラキス(ペンタフルオロフェニル)ホウ素(IV)アニオンを有する褐色固体の染料モノマー2(化合物6)2.6g(収率61%)を得た。
(1)塩交換反応
攪拌装置を備えた丸底フラスコ中、実施例1(1)と同様にして得たBasic Yellow13誘導体(化合物3)6.0g(16.8mmol)に塩化メチレン100mLを加えて溶解した。ここにテトラキス(ペンタフルオロフェニル)ホウ素(IV)のリチウム塩11.5g(16.8mmol、東ソー・ファインケム(株)製)及びイオン交換水100mLを加えて溶解後、室温で30分間反応させた。得られた有機溶媒を分液し、イオン交換水で洗浄した後、減圧濃縮によって溶媒を留去し、カウンターアニオンにテトラキス(ペンタフルオロフェニル)ホウ素(IV)アニオンを有するBasic Yellow13誘導体(化合物7)12.8g(収率76%)を得た。
攪拌装置を備えた丸底フラスコに、粉砕したモレキュラーシーブス3A 4.0g(和光純薬工業(株)製)、(1)で合成したテトラキス(ペンタフルオロフェニル)ホウ素(IV)アニオンを有するBasic Yellow13誘導体(化合物7)2.0g(2.0mmol)、メタクリル酸クロリド0.52g(5.0mmol、和光純薬工業(株)製)、及び1,2-ジクロロエタン40mLを加え、80℃で4時間還流反応させた。室温まで冷却後、飽和重曹水を加えて中和し、水層が中性になるまでイオン交換水で洗浄した。減圧濃縮にて溶媒を留去し、褐色固体の染料モノマー3(化合物9)2.0g(収率94%)を得た。
(1)重合性基の導入
攪拌装置を備えた丸底フラスコに、4-アミノ安息香酸(化合物10)13.7g(和光純薬工業(株)製)、メタクリル酸-2-ヒドロキシエチル(化合物11)13.7g(和光純薬工業(株)製)、4‐ジメチルアミノピリジン 3.7g(和光純薬工業(株)製)及び塩化メチレン 180mL(和光純薬工業(株)製)を加えた。ここに、1‐エチル‐3‐(3‐ジメチルアミノプロピル)カルボジイミド塩酸塩 23.0g(東洋紡(株)製)を加えて-5℃で7時間反応させた。室温まで昇温し、生じた固体をろ別後、酢酸エチル(和光純薬工業(株)製)と水を加えて抽出・洗浄し、減圧濃縮によって溶媒を留去した。得られた固体をメタノールから再結晶して白色固体のエステル体(化合物12)9.1g(収率37%)を得た。
攪拌装置を備えた丸底フラスコ中に、2-(1,3,3,-トリメチルインドリン-2-イリデン)アセトアルデヒド(化合物1)2.0g(和光純薬工業(株)製)、(1)で合成したエステル体(化合物12)2.5g及び酢酸10mL(和光純薬工業(株)製)を加え、55℃で5時間反応させた。室温まで冷却後、塩化メチレン(和光純薬工業(株)製)及び飽和食塩水を加えて室温で1時間撹拌した。次いで、有機層を水および重曹水で洗浄した。ここにテトラキス(ペンタフルオロフェニル)ホウ素(IV)のリチウム塩7.5g(東ソー・ファインケム(株)製)を加えて室温で0.5時間撹拌した。反応液を水洗後に減圧濃縮によって溶媒を留去し、濃橙色固体の染料モノマー4(化合物13)10.9g(収率98%)を得た。
(1)重合性基の導入
攪拌装置を備えた丸底フラスコ中に、4-ニトロフェニル酢酸(化合物14)7.2g(和光純薬工業(株)製)、メタクリル酸-2-ヒドロキシエチル(化合物11)5.2g(和光純薬工業(株)製)、4‐ジメチルアミノピリジン1.5g(和光純薬工業(株)製)及び塩化メチレン80mL(和光純薬工業(株)製)を加えた。ここに1‐エチル‐3‐(3‐ジメチルアミノプロピル)カルボジイミド塩酸塩11.5g(東洋紡(株)製)を加えて室温で2時間反応させた。反応液に水を加えて抽出・洗浄し、減圧濃縮によって溶媒を留去し、黒色オイルのエステル体(化合物15)11.7g(収率100%)を得た。
攪拌装置を備えた丸底フラスコ中に、(1)で得たエステル体(化合物15)11.7g及び酢酸90mL(和光純薬工業(株)製)を加えた後、亜鉛末14.4g(和光純薬工業(株)製)を分割投入した。室温で5時間反応させた後、不溶物をろ過し、塩化メチレン150mL(和光純薬工業(株)製)を加えて水洗した。さらに1mol/L塩酸で抽出、分液した水層に水酸化ナトリウム水溶液を加えてpHを10にした後、塩化メチレン150mLで抽出した。減圧濃縮によって溶媒を留去し、橙色液体(化合物16)5.7g(収率54%)を得た。
攪拌装置を備えた丸底フラスコ中で、2-(1,3,3,-トリメチルインドリン-2-イリデン)アセトアルデヒド(化合物1)2.0g(和光純薬工業(株)製)、(2)で合成したアニリン誘導体(化合物16)2.6g、酢酸10mL(和光純薬工業(株)製)を加え、55℃で6時間反応させた。室温まで冷却後、塩化メチレン(和光純薬工業(株)製)、飽和食塩水を加えて室温で1時間撹拌し、有機層を水、重曹水で洗浄した。ここにテトラキス(ペンタフルオロフェニル)ホウ素(IV)のリチウム塩7.5g(東ソー・ファインケム(株)製)を加えて、室温で0.5時間撹拌した。反応液を水洗後、減圧濃縮によって溶媒を留去し、濃橙色固体の染料モノマー5(化合物17)10.8g(収率96%)を得た。
(1)重合性基の導入
攪拌装置を備えた丸底フラスコ中に、3-メトキシ-4-ニトロフェニル酢酸(化合物18)2.0g(東京化成工業(株)製)、メタクリル酸-2-ヒドロキシエチル(化合物11)1.3g(和光純薬工業(株)製)、4‐ジメチルアミノピリジン0.4g(和光純薬工業(株)製)及び塩化メチレン80mL(和光純薬工業(株)製)を加えた。ここに1‐エチル‐3‐(3‐ジメチルアミノプロピル)カルボジイミド塩酸塩2.9g(東洋紡(株)製)を加え、室温で3時間反応させた。更に、水を加えて洗浄後、減圧濃縮によって溶媒を留去し、褐色オイルのエステル体(化合物19)3.1g(収率100%)を得た。
攪拌装置を備えた丸底フラスコ中に、(1)で得たエステル体(化合物19)3.1g及び酢酸20mL(和光純薬工業(株)製)を加えた後、亜鉛末3.3g(和光純薬工業(株)製)を分割投入した。室温で5時間反応させた後、不溶物をろ過し、塩化メチレン30mL(和光純薬工業(株)製)を加えて、水および重曹水で洗浄した。減圧濃縮によって溶媒を留去し、橙色液体(化合物20)1.9g(収率68%)を得た。
攪拌装置を備えた丸底フラスコ中に、2-(1,3,3,-トリメチルインドリン-2-イリデン)アセトアルデヒド(化合物1)1.8g(和光純薬工業(株)製)、(2)で合成したアニリン誘導体(化合物20)2.5g及び酢酸10mL(和光純薬工業(株)製)を加え、55℃で6時間反応させた。室温まで冷却後、塩化メチレン(和光純薬工業(株)製)及び飽和食塩水を加えて、室温で1時間撹拌し、有機層を水洗し、更に重曹水で洗浄した。ここにテトラキス(ペンタフルオロフェニル)ホウ素(IV)のリチウム塩6.7g(東ソー・ファインケム(株)製)を加えて、室温で0.5時間撹拌した。反応液を水洗後、減圧濃縮によって溶媒を留去し、濃橙色固体の染料モノマー6(化合物21)9.9g(収率97%)を得た。
(1)重合性基の導入
攪拌装置を備えた丸底フラスコ中に、4,5-ジメトキシ-2-ニトロ安息香酸(化合物22)2.7g(和光純薬工業(株)製)、メタクリル酸-2-ヒドロキシエチル(化合物11)1.6g(和光純薬工業(株)製)、4‐ジメチルアミノピリジン0.4g(和光純薬工業(株)製)及び塩化メチレン20mL(和光純薬工業(株)製)を加えた。ここに1‐エチル‐3‐(3‐ジメチルアミノプロピル)カルボジイミド塩酸塩3.5g(東洋紡(株)製)を加え、室温で3時間反応させた。更に、水を加えて洗浄後、減圧濃縮によって溶媒を留去し、褐色オイルのエステル体(化合物23)3.1g(収率77%)を得た。
攪拌装置を備えた丸底フラスコ中に、(1)で得たエステル体(化合物23)2.8g及び酢酸20mL(和光純薬工業(株)製)を加えた後、亜鉛末3.2g(和光純薬工業(株)製)を分割投入した。室温で4時間反応させた後、不溶物をろ過し、塩化メチレン70mL(和光純薬工業(株)製)を加えて、水および重曹水で洗浄した。次いで、減圧濃縮によって溶媒を留去してオイル成分を含む褐色固体を得た。これをメタノール30ml(和光純薬工業(株)製)で洗浄し、減圧乾燥して、淡褐色固体(化合物24)0.8g(収率33%)を得た。
攪拌装置を備えた丸底フラスコ中で、2-(1,3,3,-トリメチルインドリン-2-イリデン)アセトアルデヒド(化合物1)0.4g(和光純薬工業(株)製)、(2)で合成したアニリン誘導体(化合物24)0.8g及び酢酸15mL(和光純薬工業(株)製)を加え、55℃で4時間反応させた。室温まで冷却後、塩化メチレン(和光純薬工業(株)製)及び飽和食塩水を加えて、室温で1時間撹拌し、有機層を水洗し、更に重曹水で洗浄した。ここにテトラキス(ペンタフルオロフェニル)ホウ素(IV)のリチウム塩1.6g(東ソー・ファインケム(株)製)を加えて、室温で0.5時間撹拌した。反応液を水洗後、減圧濃縮によって溶媒を留去し、濃橙色固体の染料モノマー7(化合物25)2.8g(収率88%)を得た。
(1)重合性基の導入
攪拌装置を備えた丸底フラスコ中に、2-ニトロけい皮酸(化合物26)3.9g(和光純薬工業(株)製)、メタクリル酸-2-ヒドロキシエチル(化合物11)2.6g(和光純薬工業(株)製)、4‐ジメチルアミノピリジン0.7g(和光純薬工業(株)製)及び塩化メチレン40mL(和光純薬工業(株)製)を加えた。更に、ここに1‐エチル‐3‐(3‐ジメチルアミノプロピル)カルボジイミド塩酸塩5.8g(東洋紡(株)製)を加え、室温で2時間反応させた。次いで、水を加えて洗浄後、減圧濃縮によって溶媒を留去し、黄色オイルのエステル体(化合物27)6.1g(収率100%)を得た。
攪拌装置を備えた丸底フラスコ中に、(1)で得たエステル体(化合物27)3.1g及び酢酸21mL(和光純薬工業(株)製)を加えた後、亜鉛末3.3g(和光純薬工業(株)製)を分割投入した。室温で5時間反応後、不溶物をろ過し、塩化メチレン50mL(和光純薬工業(株)製)と水を加えて水洗した。さらに重曹水で中和後、減圧濃縮によって溶媒を留去し、褐色オイル(化合物28)2.5g(収率91%)を得た。
攪拌装置を備えた丸底フラスコ中に、2-(1,3,3,-トリメチルインドリン-2-イリデン)アセトアルデヒド(化合物1)0.7g(和光純薬工業(株)製)、(2)で合成したアニリン誘導体(化合物28)1.0g、及び酢酸10mL(和光純薬工業(株)製)を加え、55℃で5時間反応させた。更に、塩化メチレン(和光純薬工業(株)製)及び飽和食塩水を加えて、室温で1時間撹拌後、有機層を水洗し、更に重曹水で洗浄し、テトラキス(ペンタフルオロフェニル)ホウ素(IV)のリチウム塩7.5g(東ソー・ファインケム(株)製)を加えて、室温で0.5時間撹拌した。反応液を水洗後、減圧濃縮によって溶媒を留去し、濃橙色固体の染料モノマー8(化合物29)4.0g(収率97%)を得た。
(1)重合性基の導入
攪拌装置を備えた丸底フラスコ中に、4-ニトロけい皮酸(化合物30)1.9g(東京化成工業(株)製)、トルエン20ml(和光純薬工業(株)製)及びN,N-ジメチルホルムアミド1ml(和光純薬工業(株)製)を加え、60℃に加温した。ここに塩化チオニル1.3g(和光純薬工業(株)製)を注入し、70℃で2時間撹拌した。減圧濃縮によって過剰の塩化チオニルを除去して、4-ニトロけい皮酸クロライド(化合物31)のトルエン溶液を調製した。別の攪拌装置を備えた丸底フラスコに、メタクリル酸-2-ヒドロキシエチル(化合物11)1.3g(和光純薬工業(株)製)、トリエチルアミン1.0g(和光純薬工業(株)製)及びトルエン10mlを加えて水冷し、先に調製した4-ニトロけい皮酸クロライド(化合物32)のトルエン溶液を滴下後、室温で3時間反応させた。析出物のろ別した後、水洗し、減圧濃縮によって溶媒を留去し、橙色オイルの化合物322.3g(収率77%)を得た。
攪拌装置を備えた丸底フラスコ中に、(1)で得たエステル体(化合物32)2.3g及び酢酸20mL(和光純薬工業(株)製)を加えた後、亜鉛末2.9g(和光純薬工業(株)製)を分割投入した。室温で5時間反応させた後、不溶物をろ過し、塩化メチレン50mL(和光純薬工業(株)製)と水を加えて水洗した。さらに重曹水で中和後、減圧濃縮によって溶媒を留去し、褐色オイル(化合物33)1.8g(収率86%)を得た。
攪拌装置を備えた丸底フラスコ中に、2-(1,3,3,-トリメチルインドリン-2-イリデン)アセトアルデヒド(化合物1)1.3g(和光純薬工業(株)製)及び(2)で合成したアニリン誘導体(化合物33)1.8g、酢酸15mL(和光純薬工業(株)製)を加え、55℃で5時間反応させた。次いで、塩化メチレン(和光純薬工業(株)製)及び飽和食塩水を加えて、室温で1時間撹拌後、有機層を水洗、更に重曹水で洗浄し、テトラキス(ペンタフルオロフェニル)ホウ素(IV)のリチウム塩4.8g(東ソー・ファインケム(株)製)を加えて、室温で0.5時間撹拌した。反応液を水洗後、減圧濃縮によって溶媒を留去し、濃橙色固体の染料モノマー9(化合物34)7.1g(収率98%)を得た。
攪拌装置、冷却管、温度計、窒素導入管を備えた200mlの丸底フラスコに、プロピレングリコールモノメチルエーテルアセテート27.9g(和光純薬工業(株)製)を入れ、窒素気流下で内温が90℃になるまで加熱した。次いで、これを染料モノマー2(化合物6) 3.0g、ベンジルメタクリレート50.1g(和光純薬工業(株)製)、メタクリル酸6.9g(和光純薬工業(株)製)、ジメチル2,2´‐アゾビス(2-メチルプロピオネート)(和光純薬工業(株)製重合開始剤V‐601)9.6g、及びプロピレングリコールモノメチルエーテルアセテート27.9g(和光純薬工業(株)製)を混合した溶液を、2時間かけて滴下した。その後、得られた溶液を90℃で2時間反応させた。反応後、室温まで冷却し、プロピレングリコールモノメチルエーテルアセテート48.6gを加えて希釈し、染料ポリマーを得た(染料モノマー2/ベンジルメタクリレート/メタクリル酸=3.0/50.1/6.9)。これを染料ポリマー2溶液とする。
染料モノマー2 3.0gの代わりに、実施例2で得た染料モノマー3 3.0gを用いた以外は用いた他は、実施例9と同様にして、染料ポリマーを得た(染料モノマー3/ベンジルメタクリレート/メタクリル酸=3.0/50.1/6.9)。これを染料ポリマー3溶液とする。
攪拌装置を備えた丸底フラスコに、2-(1,3,3,-トリメチルインドリン-2-イリデン)アセトアルデヒド(化合物1)5.0g(24.8mmol、和光純薬工業(株)製)、p-アニシジン(化合物35)3.1g(25.1mmol、東京化成工業(株)製)、及び酢酸25mL(和光純薬工業(株)製)を加え、40℃で4時間反応させた。次いで、塩化メチレン(和光純薬工業(株)製)及び飽和食塩水を加えて有機層に目的物を抽出した後、有機層を飽和重曹水で2回洗浄し、飽和食塩水で洗浄した。その後、減圧濃縮によって溶媒を留去し、褐色固体のBasic Yellow13(化合物36)7.3g(収率86%)を得た。
実施例1で得た染料モノマー2の耐熱性を下記のように評価した。
(1)染料を含まないポリマーの合成
攪拌装置、冷却管、温度計及び窒素導入管を備えた500mLの丸底フラスコに、プロピレングリコールモノメチルエーテルアセテート98.5gを入れ、窒素気流下で内温が90℃になるまで加熱した。次いで、これに、ベンジルメタクリレート 186.2g、メタクリル酸25.6g、ジメチル2,2´‐アゾビス(2-メチルプロピオネート)(和光純薬工業(株)製重合開始剤V‐601)33.9g、及びプロピレングリコールモノメチルエーテルアセテート98.5gを混合した溶液を、2時間かけて滴下した。その後、得られた溶液を90℃で2時間反応させた。次に、100℃に昇温し、1時間反応させた。反応後、室温まで冷却し、プロピレングリコールモノメチルエーテルアセテート171.5gを加えて希釈し、淡黄色透明のポリマー溶液を得た。これをポリマーAとする。尚、ポリマーAの不揮発分濃度は35.9%であった。
染料モノマー2を0.5g、ポリマーA52.9g、及びプロピレングリコールモノメチルエーテルアセテート3.2gを混合し、染料モノマー混合溶液Bを調製した。
染料モノマー混合溶液Bを3インチのガラスウエハー(コーニング社製イーグルXG)にスピンコートした後、90℃に加熱したホットプレート上で90秒間乾燥して膜厚1ミクロンの薄膜を得た。得られた薄膜それぞれを、分光光度計(島津製作所製分光光度計UV-2550)を用いて極大吸収波長での吸光度(λa)を測定した。その後、230℃に加熱したホットプレート上で30分間加熱した後、再度、極大吸収波長での吸光度(λb)を測定した。測定したλaとλbの値から下記式より染料残存率(%)を求めた。その結果を表1に示す。尚、メタノール溶液(MeOH)溶液中の最大吸収波長(nm)も併せて表中に示す。
染料残存率(%)=(λb/λa)×100
実施例11における染料モノマー2の代わりに染料モノマー3~6及び9を用いた以外は、実施例11の方法にしたがって操作し、染料モノマー3~6及び9それぞれの耐熱性を評価した。その結果及びメタノール溶液(MeOH)溶液中の最大吸収波長(nm)を、実施例11の結果と合わせて表1に示す。
実施例17~18 染料モノマー7及び8の最大吸収波長
モノマー7及び8のメタノール溶液(MeOH)溶液中の最大吸収波長(nm)を表1に示す。
実施例9で得た染料ポリマー2溶液の耐熱性を下記のようにして評価した。
即ち、得られた染料ポリマー2溶液をそれぞれ3インチのガラスウエハー(コーニング社製イーグルXG)にスピンコートした後、90℃に加熱したホットプレート上で90秒間乾燥して膜厚1ミクロンの薄膜を得た。得られた薄膜それぞれを、分光光度計(島津製作所製分光光度計UV-2550)を用いて極大吸収波長での吸光度(λa)を測定し、その後、230℃に加熱したホットプレート上で30分間加熱した後、再度、極大吸収波長での吸光度(λb)を測定した。λaとλbの値から下記式より染料残存率(%)を求めた。その結果を、実施例11~18の結果と合わせて表1に示す。
染料残存率(%)=(λb/λa)×100
実施例19において染料ポリマー2溶液の代わりに染料ポリマー3溶液を用いた以外は、実施例19の方法にしたがって操作し、染料ポリマー3の耐熱性を評価した。その結果を、実施例11~19の結果と合わせて表1に示す。
染料モノマー2 0.5gの代わりにBasic Yellow13 0.5gを用いた他は、実施例5と同様にして、Basic Yellow13の耐熱性を評価した。その結果及びメタノール溶液(MeOH)溶液中の最大吸収波長(nm)を、実施例11~20の結果と合わせて表1に示す。
撹拌装置、冷却管、温度計、窒素導入管を備えた2000mlの丸底フラスコにプロピレングリコールモノメチルエーテルアセテート(ダイセル(株)製)105gを入れ、窒素気流下にて、内温が95℃になるまで加熱した。次いで、染料モノマー4 15g、メタクリル酸メチル(和光純薬工業(株)製)285g、2,2’-アゾビス(2-メチルプロピオン酸メチル) (商品名V-601 和光純薬工業(株)製)15gを混合し、該混合溶液を95℃にて2時間かけて丸底フラスコに滴下した。その後、得られた溶液を95℃にて2時間反応させた。反応後、室温まで冷却し、酢酸エチル1000gに溶解した。該混合溶液をn-ヘキサン4600ml中に注入して生じた沈殿物をろ取、減圧下にて乾燥し、約5重量部の染料モノマー4を含む染料ポリマー4 315gを得た。
上記で得た染料ポリマー4 0.5重量部と市販のメタクリル酸メチル樹脂(アクリペットMD001(三菱レイヨン製))99.5重量部を、同方向回転二軸押出機を用いて溶融混合し、着色した樹脂ペレットを得た。次いで、得られた樹脂ペレットを電動式射出成形機によって加工し、150mm×150mm×t2mmの着色板を作成した。
実施例22において、染料ポリマー4 0.5重量部の代わりにBasic Yellow 13を0.025重量部とメタクリル酸メチル樹脂100重量部を用いた以外は同様にして、着色板を作成した。
実施例22で作成した着色板を40mm×30mm×t2mmの大きさに裁断した後、エタノール50部とイオン交換水50部を混合したエタノール水溶液80ml中に浸漬し、40℃の恒温槽中で200時間保管した。エタノール溶液を取り出し、分光光度計(島津製作所製製分光光度計UV-2500)を用いて、エタノール水溶液の分光スペクトルを測定した。
測定サンプルの最大吸収波長における吸光度(λa)と予め測定したグラム吸光係数(ε)を用いて、エタノール水溶液中に溶出した染料モノマー4の重量を算出し、浸漬させた樹脂着色板中に含まれる染料モノマー4の重量を基準とした時の溶出率(%)を下記式により算出した。
溶出率(%)= [(λa×0.08/ε)/(着色板に含まれる染料の重量)]×100
※着色板中に含まれる染料の重量 = 板の重さ×0.00025
実施例23において、比較例3で作成した着色板を用いた以外は同様に操作し、Basic Yellow 13の溶出率を算出した。その結果を、実施例23の結果と合わせて表2に示す。
実施例22で作成した着色板を65mm×65mm×t2mmに裁断し、JIS B7754:1991に規定する装置[Ci4000(アトラス社製)]を使用し、下記条件でキセノンアーク灯式による促進耐候性試験を実施した。
(1)試験条件
放射照度:50w/m2(300-400nm)
フィルタガラス:内側 ボロシリケートSタイプ、外側 ソーダライム
ブラックパネル温度:63±2℃
槽内温度:38±2℃
相対湿度:50±10%RH
試験時間:50時間
(2)測色条件
測定:反射測定(8°:de)
標準光 :D65
測定孔径:φ5mm
色差(ΔE*ab)=[ (ΔL*)2+(Δa*)2+(Δb*)2 ] 1/2
Claims (15)
- 下記一般式(1)で示される化合物。
(式中、R1~R4は、それぞれ独立して、水素原子、ニトロ基、ハロゲノ基、シアノ基、アミド基、カルボキシル基、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基、炭素数2~4のアルキルオキシカルボニル基、炭素数2~4のアルキルカルボニルオキシ基、又は炭素数7~10のアリールカルボニル基を表し、
R5及びR6は、それぞれ独立して、水素原子、炭素数1~6のアルキル基、炭素数7~13のアリールアルキル基、或いは、フェニル基の置換基として、炭素数1~6のアルキル基、ニトロ基、ハロゲノ基又はシアノ基を有する、炭素数7~9のフェニルアルキル基を表し、nは0~4の整数を表し、
R7は、水素原子、炭素数1~6のアルキル基、炭素数7~13のアリールアルキル基、置換基として、炭素数1~6のアルコキシ基、ヒドロキシル基、カルボキシル基、ハロゲノ基、シアノ基、アミド基又は炭素数2~4のアルキルオキシカルボニル基を有する、炭素数1~6のアルキル基、或いは、フェニル基の置換基として、炭素数1~6のアルコキシ基、ハロゲノ基又はアミド基を有する、炭素数7~9のフェニルアルキル基を表し、
n個のR8は、それぞれ独立して、ニトロ基、ハロゲノ基、シアノ基、アミド基、カルボキシル基、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基、炭素数2~4のアルキルオキシカルボニル基、炭素数2~4のアルキルカルボニルオキシ基、又は炭素数7~10のアリールカルボニル基を表し、
R12は、水素原子又はメチル基を表し、
A1は、-O-、-OCO-、-COO-、ビニレン基及びアリーレン基から選ばれる少なくとも1つの基を鎖中に有する炭素数1~21のアルキレン基、-O-、-OCO-、-COO-及びアリーレン基から選ばれる少なくとも1つの基を鎖中に有し、且つ、ヒドロキシル基を置換基として有する炭素数1~21のアルキレン基、炭素数1~21のアルキレン基、或いは、ヒドロキシル基を置換基として有する炭素数1~21のアルキレン基を表し、A2は-NH-または-O-を表し、
An-は、電子吸引性の置換基を有するアリール基、電子吸引性の置換基を有するスルホニル基、又はハロゲン化アルキル基を含むアニオンを表す。) - An-における電子吸引性の置換基がハロゲン原子である、請求項1記載の化合物。
- An-における電子吸引性の置換基がフッ素原子である、請求項1記載の化合物。
- An-が、4級ホウ素アニオンである、請求項1記載の化合物。
- An-が、テトラキス(パーフルオロフェニル)ボレートアニオンである請求項1記載の化合物。
- 下記一般式(1)で示される化合物由来のモノマー単位を有するポリマー。
(式中、R1~R4は、それぞれ独立して、水素原子、ニトロ基、ハロゲノ基、シアノ基、アミド基、カルボキシル基、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基、炭素数2~4のアルキルオキシカルボニル基、炭素数2~4のアルキルカルボニルオキシ基、又は炭素数7~10のアリールカルボニル基を表し、
R5及びR6は、それぞれ独立して、水素原子、炭素数1~6のアルキル基、炭素数7~13のアリールアルキル基、或いは、フェニル基の置換基として、炭素数1~6のアルキル基、ニトロ基、ハロゲノ基又はシアノ基を有する、炭素数7~9のフェニルアルキル基を表し、nは0~4の整数を表し、
R7は、水素原子、炭素数1~6のアルキル基、炭素数7~13のアリールアルキル基、置換基として、炭素数1~6のアルコキシ基、ヒドロキシル基、カルボキシル基、ハロゲノ基、シアノ基、アミド基又は炭素数2~4のアルキルオキシカルボニル基を有する、炭素数1~6のアルキル基、或いは、フェニル基の置換基として、炭素数1~6のアルコキシ基、ハロゲノ基又はアミド基を有する、炭素数7~9のフェニルアルキル基を表し、
n個のR8は、それぞれ独立して、ニトロ基、ハロゲノ基、シアノ基、アミド基、カルボキシル基、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基、炭素数2~4のアルキルオキシカルボニル基、炭素数2~4のアルキルカルボニルオキシ基、又は炭素数7~10のアリールカルボニル基を表し、
R12は、水素原子又はメチル基を表し、
A1は、-O-、-OCO-、-COO-、ビニレン基及びアリーレン基から選ばれる少なくとも1つの基を鎖中に有する炭素数1~21のアルキレン基、-O-、-OCO-、-COO-及びアリーレン基から選ばれる少なくとも1つの基を鎖中に有し、且つ、ヒドロキシル基を置換基として有する炭素数1~21のアルキレン基、炭素数1~21のアルキレン基、或いは、ヒドロキシル基を置換基として有する炭素数1~21のアルキレン基を表し、A2は-NH-または-O-を表す。
An-は、電子吸引性の置換基を有するアリール基、電子吸引性の置換基を有するスルホニル基、又はハロゲン化アルキル基を含むアニオンを表す。) - An-における電子吸引性の置換基がハロゲン原子である、請求項6記載のポリマー。
- An-における電子吸引性の置換基がフッ素原子である、請求項6記載のポリマー。
- An-が、4級ホウ素アニオンである、請求項6記載のポリマー。
- An-が、テトラキス(パーフルオロフェニル)ボレートアニオンである請求項6記載のポリマー。
- ポリマーがコポリマーである、請求項6記載のポリマー。
- コポリマーが、下記一般式(2)、一般式(3)、一般式(4)又は一般式(5)で示されるモノマー由来のモノマー単位1~2種と上記一般式(1)で示される化合物由来のモノマー単位とを構成成分とするものである、請求項11記載のポリマー;
[式中、R21は、水素原子又はメチル基を表し、R22は、水素原子、炭素数1~18のアルキル基、炭素数1~10のヒドロキシルアルキル基、炭素数6~10のアリール基、炭素数7~13のアリールアルキル基、炭素数2~9のアルコキシアルキル基、炭素数3~9のアルコキシアルコキシアルキル基、炭素数7~13のアリールオキシアルキル基、炭素数5~7のモルホリノアルキル基、炭素数3~9のトリアルキルシリル基、酸素を有する又は酸素を有さない炭素数6~10の脂環式炭化水素基、炭素数3~9のジアルキルアミノアルキル基、炭素数1~18のフッ化アルキル基、又は炭素数1~6のN-アルキレンフタルイミド基、下記一般式(2-1)で示される基
(式中、R23は、炭素数1~3のアルキレン基を表し、R24は、ヒドロキシル基を置換基として有する又は無置換のフェニル基、或いは炭素数1~3のアルキル基を表し、qは1~3の整数を表す。)、
下記一般式(2-2)で示される基
(式中、R25~R27は炭素数1~3のアルキル基を表し、R28は炭素数1~3のアルキレン基を表す。)、又は下記一般式(2-3)で示される基
(式中、lは、1~6の整数を表し、R29はフェニレン基又はシクロへキシレン基を表す)を表す。]、
(式中、R30は上記と同じ。R31は、水素原子又は炭素数1~3のアルキル基を表し、R32は、水素原子、炭素数1~3のアルキル基、炭素数3~9のジアルキルアミノアルキル基、又は炭素数1~6のヒドロキシアルキル基を表す。R31とR32は、これらと隣接する窒素原子とでモルホリノ基を形成してもよい。)、
(式中、R33は、フェニル基、ピロリジノ基を表し、R21は上記と同じ。)
(式中、R35は、窒素原子又は酸素原子を表し、jは、R35が酸素原子の場合に0を表し、R35が窒素原子の場合には1を表す。R34は、水素原子、炭素数1~20のアルキル基、炭素数1~10のヒドロキシルアルキル基、炭素数1~10のハロゲン化アルキル基、炭素数1~10のアルキルシクロアルキル基、炭素数6~7のハロゲン化シクロアルキル基、炭素数6~10のアリール基、炭素数1~6のアルキル基を置換基として有する炭素数6~10のアリール基、又は、炭素数6~10のハロゲン化アリール基を表す。)。 - 請求項1記載の化合物又は請求項6記載のポリマーを含んでなる着色組成物。
- 請求項1記載の化合物又は請求項1記載のポリマーを含んでなるカラーフィルター用着色組成物。
- 請求項1記載の化合物又は請求項6記載のポリマーを含んでなる着色樹脂。
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Publication number | Priority date | Publication date | Assignee | Title |
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WO2017222006A1 (ja) | 2016-06-22 | 2017-12-28 | 和光純薬工業株式会社 | ケイ素含有複素環式化合物及び消光剤 |
CN108473784A (zh) * | 2016-03-29 | 2018-08-31 | 富士胶片和光纯药株式会社 | 多官能聚合型化合物及着色组合物 |
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Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2010037545A (ja) * | 2008-07-08 | 2010-02-18 | Fujifilm Corp | インクジェット用インク、カラーフィルタおよびその製造方法、ならびにそれを用いる液晶ディスプレイおよび画像表示デバイス |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4876166A (en) * | 1988-05-19 | 1989-10-24 | Eastman Kodak Company | Color filter array |
JPH0293422A (ja) | 1988-09-29 | 1990-04-04 | Hoya Corp | 遮光眼鏡レンズ |
JP2000103975A (ja) * | 1998-09-28 | 2000-04-11 | Idemitsu Kosan Co Ltd | ローダミン誘導体および色素、色変換膜ならびに有機エレクトロルミネッセンス素子 |
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JP5470058B2 (ja) | 2010-01-15 | 2014-04-16 | 凸版印刷株式会社 | カラーフィルタ用着色組成物、カラーフィルタ、その製造方法、及びそれを具備する液晶表示装置並びに有機el表示装置 |
JP2012083651A (ja) * | 2010-10-14 | 2012-04-26 | Nippon Kayaku Co Ltd | 着色樹脂組成物 |
JP2012208474A (ja) | 2011-03-14 | 2012-10-25 | Jsr Corp | カラーフィルタ用着色組成物、カラーフィルタ及び表示素子 |
JP5377595B2 (ja) * | 2011-03-25 | 2013-12-25 | 富士フイルム株式会社 | 着色感放射線性組成物、カラーフィルタ、着色パターンの製造方法、カラーフィルタの製造方法、固体撮像素子、及び液晶表示装置 |
JP2013054275A (ja) | 2011-09-06 | 2013-03-21 | Nikon-Essilor Co Ltd | 染色レンズおよびその製造方法 |
JP2013073104A (ja) * | 2011-09-28 | 2013-04-22 | Fujifilm Corp | 着色組成物、着色パターン、カラーフィルタ、その製造方法、パターン形成方法、固体撮像素子、及び画像表示装置 |
JP6065547B2 (ja) | 2011-11-28 | 2017-01-25 | 三菱化学株式会社 | 着色樹脂組成物、カラーフィルタ、液晶表示装置及び有機el表示装置 |
JP5482878B2 (ja) * | 2012-01-30 | 2014-05-07 | Jsr株式会社 | 着色剤、着色組成物、カラーフィルタ及び表示素子 |
JP5885542B2 (ja) | 2012-03-02 | 2016-03-15 | 富士フイルム株式会社 | 着色硬化性組成物およびカラーフィルタ |
JP2014037530A (ja) | 2012-07-19 | 2014-02-27 | Sumitomo Chemical Co Ltd | 染料用塩 |
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Publication number | Priority date | Publication date | Assignee | Title |
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108473784A (zh) * | 2016-03-29 | 2018-08-31 | 富士胶片和光纯药株式会社 | 多官能聚合型化合物及着色组合物 |
CN108473784B (zh) * | 2016-03-29 | 2021-01-12 | 富士胶片和光纯药株式会社 | 多官能聚合型化合物及着色组合物 |
WO2017222006A1 (ja) | 2016-06-22 | 2017-12-28 | 和光純薬工業株式会社 | ケイ素含有複素環式化合物及び消光剤 |
WO2019117134A1 (ja) | 2017-12-14 | 2019-06-20 | 三菱鉛筆株式会社 | 着色粒子水分散体 |
JPWO2019117134A1 (ja) * | 2017-12-14 | 2021-01-07 | 三菱鉛筆株式会社 | 着色粒子水分散体 |
JP7284895B2 (ja) | 2017-12-14 | 2023-06-01 | 三菱鉛筆株式会社 | 着色粒子水分散体 |
US11718758B2 (en) | 2017-12-14 | 2023-08-08 | Mitsubishi Pencil Company, Limited | Aqueous dispersion of colored particles |
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