WO2009101885A1 - Polyimide - Google Patents

Polyimide Download PDF

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Publication number
WO2009101885A1
WO2009101885A1 PCT/JP2009/051880 JP2009051880W WO2009101885A1 WO 2009101885 A1 WO2009101885 A1 WO 2009101885A1 JP 2009051880 W JP2009051880 W JP 2009051880W WO 2009101885 A1 WO2009101885 A1 WO 2009101885A1
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group
formula
substituted
unsubstituted
same
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PCT/JP2009/051880
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French (fr)
Japanese (ja)
Inventor
Masatoshi Hasegawa
Yukihiro Isogai
Suguru Ohara
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Kyowa Hakko Chemical Co., Ltd.
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Publication of WO2009101885A1 publication Critical patent/WO2009101885A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/1053—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the tetracarboxylic moiety
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
    • C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/16—Polyester-imides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/303—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups H01B3/38 or H01B3/302
    • H01B3/306—Polyimides or polyesterimides
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10—Substrates, e.g. flexible substrates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to an electrical insulating film in various electronic devices, a substrate for liquid crystal display (LCD), a substrate for organic electroluminescence display (ELD), a substrate for electronic paper, a substrate for solar cell, an interlayer insulating film and a protective film for semiconductor elements,
  • the present invention relates to polyimide useful for liquid crystal alignment films, optical waveguide materials, and the like.
  • polyimide for example, general formula (VIII)
  • a polyimide obtained by reacting a tetracarboxylic dianhydride represented by (wherein Y represents a divalent aromatic group or the like) and a diamine (Patent Document 1) is known, but is high. It does not satisfy the required performance such as heat resistance.
  • the present invention provides polyimide having high heat resistance and the like.
  • P 1 , P 2 and P 3 are the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, a formyl group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group
  • X and A are the same Or differently, a substituted or unsubstituted alkylene group, a divalent group formed by removing two hydrogen atoms on a carbon atom from a substituted or unsubstituted polycyclic unsaturated hydrocarbon, a substituted or unsubsti
  • m represents an integer of 0 to 3
  • R 1 and R 2 are the same or different and each represents a halogen atom, a cyano group, a formyl group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group.
  • Alkenyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkanoyloxy group or substituted or unsubstituted alkoxyl group, q and r are the same or different and represent an integer of 0 to 4, q Each of R 1 may be the same or different when R is an integer of 2 to 4, and each of R 2 may be the same or different when r is an integer of 2 to 4, and Z 1 is a single bond, an oxygen atom, A sulfur atom, SO 2 , a C 1-4 alkylene group which may be substituted by a fluorine atom, or the formula (III)
  • R 5 and R 6 are the same or different and each represents a halogen atom, a cyano group, a formyl group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted group, Represents an alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkanoyloxy group or a substituted or unsubstituted alkoxyl group, and e and f are the same or different and represent 0 to Each of R 5 may be the same or different when e is an integer of 2 to 4, and each of R 6 may be the same or different when f is an integer of 2 to 4.
  • Each of R 1 , q and Z 1 may be the same or different when m is 2 or 3]
  • n represents an integer of 0 to 3
  • R 3 and R 4 are the same or different and are each a halogen atom, a cyano group, a formyl group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group, A cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkanoyloxy group or a substituted or unsubstituted alkoxyl group, sa and ua are the same or different and represent an integer of 0 to 4; When sa is an integer from 2 to 4, each R 3 may be the same or different, and when ua is an integer from 2 to 4 , each R 4 may be the same or different, and sb and ub are the same or different.
  • Te 0 represents an integer 2
  • Z 2 is a single bond, an oxygen atom, a sulfur atom, alkyl of SO 2 or a fluorine atom and 1 carbon atoms and optionally substituted 4
  • sa, polyimide having a repeating unit each of sb and Z 2 is represented by representing the same or may be different).
  • R a and R b represents a hydroxyl group and the other is —NH—A— (wherein A is as defined above]
  • R c and R d represents a hydroxyl group and the other represents a divalent group represented by —NH—.
  • Formula (I) characterized by imidizing a polyimide precursor
  • polyimide having high heat resistance and the like can be provided.
  • compound (VI) the compound represented by formula (VI) is referred to as compound (VI).
  • the polyimide which has a repeating unit represented by Formula (I) is called polyimide (I)
  • the polyimide precursor which has a repeating unit represented by Formula (V) is called polyimide precursor (V).
  • examples of the alkyl group, the alkyl part of the alkanoyloxy group and the alkyl part of the alkoxyl group include linear or branched alkyl groups having 1 to 10 carbon atoms, specifically Are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, A decyl group etc. are mentioned.
  • Examples of the cycloalkyl group include cycloalkyl groups having 5 to 7 carbon atoms, and specific examples include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
  • Examples of the alkenyl group include linear or branched alkenyl groups having 2 to 10 carbon atoms, such as ethenyl group, 1-propenyl group, allyl group, butenyl group, pentenyl group, hexenyl group, A heptenyl group, an octenyl group, a nonenyl group, a decenyl group, etc. are mentioned.
  • Examples of the aryl group include aryl groups having 6 to 10 carbon atoms, and specific examples include a phenyl group and a naphthyl group.
  • Examples of the aralkyl group include aralkyl groups having 7 to 10 carbon atoms, and specific examples include a benzyl group, a phenylethyl group, and a phenylpropyl group.
  • Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Examples of the alkylene group include groups generated by removing one hydrogen atom from the alkyl groups exemplified above.
  • alkylene group having 1 to 4 carbon atoms examples include a methylene group, an ethylene group, a trimethylene group, a propylene group, a dimethylmethylene group, a tetramethylene group, and an ethylethylene group.
  • polycyclic unsaturated hydrocarbon examples include, for example, a condensed polycyclic hydrocarbon in which a 3- to 8-membered ring is condensed, or a non-adjacent double bond having the largest number of non-adjacent double bonds (indene, naphthalene, anthracene, azulene). , Fluorene, etc.), partially hydrogenated compounds thereof (indane, tetrahydronaphthalene, tetrahydroanthracene, etc.) and the like.
  • polycyclic saturated hydrocarbon examples include bicyclic or tricyclic saturated hydrocarbons in which a 3- to 8-membered ring is condensed. Specific examples thereof include perhydroindene, perhydronaphthalene, perhydro Anthracene, bicyclo [3.2.1] octane, bicyclo [2.2.1] heptane, tricyclo [3.3.1.13,7] decane and the like can be mentioned.
  • Examples of the substituent of the alkyl group, alkenyl group, alkanoyloxy group, alkoxyl group and alkylene group include, for example, the same or different 1 to 3 substituents, specifically, a halogen atom, cyano group, formyl group, hydroxyl group Groups and the like.
  • the halogen atom has the same meaning as described above.
  • Examples of the substituent of the cycloalkyl group, aryl group, aralkyl group, polycyclic unsaturated hydrocarbon and polycyclic saturated hydrocarbon include, for example, the same or different 1 to 5 substituents, specifically, halogen Atom, cyano group, formyl group, hydroxyl group, alkyl group, alkanoyloxy group, alkoxyl group and the like can be mentioned.
  • a halogen atom, an alkyl group, an alkanoyloxy group and an alkoxyl group have the same meanings as described above.
  • the number of substitution of fluorine atoms in the alkylene group having 1 to 4 carbon atoms which may be substituted with fluorine atoms is from 0 to a substitutable number.
  • P 1 , P 2 and P 3 are preferably hydrogen atoms.
  • X and A are the same or different and are preferably the formula (II) or the formula (IV), more preferably the formula (II).
  • R 1 and R 2 are the same or different and are a methyl group or a trifluoromethyl group
  • q and r are the same or different and are 0 or 1
  • Z 1 Is an oxygen atom, a sulfur atom, SO 2 , a C 1-4 alkylene group which may be substituted by a fluorine atom or formula (III), and when Z 1 is formula (III), e and f are 0 Preferably there is.
  • a preferred group when A is the formula (II) has the same meaning as a preferred group when the X is the formula (II).
  • R 3 and R 4 are the same or different and are a methyl group or a trifluoromethyl group, sa and ua are the same or different and are 0 or 1, sb and It is preferable that ub is 1.
  • a preferred group when A is the formula (IV) has the same meaning as a preferred group when X is the formula (IV).
  • P 1 , P 2 and P 3 are preferably hydrogen atoms.
  • X is preferably of formula (II) or formula (IV).
  • the preferred group when X is the formula (II) in the formula (VI) has the same meaning as the preferred group when X is the formula (II) in the formula (I) and the formula (V).
  • the preferred group when X is the formula (IV) in the formula (VI) has the same meaning as the preferred group when X is the formula (IV) in the formula (I) and the formula (V).
  • each of P 1 , P 2 , P 3 , X and A may be the same or different.
  • each of P 1 , P 2 , P 3 , X, R a , R b , R c and R d is the same. Or it may be different.
  • Compound (VII) which is a raw material of compound (VI) can be produced, for example, according to reaction formula (1).
  • Compound (a) can be obtained by a known method, for example, “Experimental Chemistry Course (Vol. 19) Organic Synthesis I Hydrocarbon / Halogen Compound”, 4th edition, Maruzen Co., 1992, p. It can be obtained by manufacturing according to the method described in 173-194.
  • the compound (b) is obtained by mixing the compound (a) with a mixed gas of carbon monoxide and hydrogen in a solvent such as acetonitrile in the presence of a catalyst at 40 to 160 ° C. and 1 to 20 MPa for 0.2 to 50 hours. It can be manufactured by processing.
  • the catalyst examples include known noble metal catalysts (for example, cobalt-based catalysts, rhodium-based catalysts, platinum-based catalysts, etc.) used for hydroformylation. Specifically, for example, Co 2 (CO) 8 , Co 4 (CO ) 12 , Co 6 (CO) 16 , HCo (CO) 4 , [Co (CO) 3 (C 5 H 6 )] 2 , Rh 4 (CO) 12 , Rh 6 (CO) 16 , RhCl (PPh 3 ) 3 , [RhCl (CO) 2 ] 2 , HRh (CO) (PPh 3 ) 3 , Rh (CO) 2 (acac), Rh (CO) (PPh 3 ) (acac), and the like.
  • noble metal catalysts for example, cobalt-based catalysts, rhodium-based catalysts, platinum-based catalysts, etc.
  • C 5 H 6 represents cyclopentadiene
  • Ph represents a phenyl group
  • acac represents an acetylacetonate group.
  • the amount of the catalyst used is preferably 5 to 5000 ppm (as a metal), more preferably 10 to 2000 ppm (as a metal) with respect to the compound (a).
  • the catalyst is preferably used in combination with a phosphorus compound such as triphenylphosphine.
  • the amount of the phosphorus compound used when the catalyst and the phosphorus compound are used in combination is preferably 1 to 500 times mol of the catalyst.
  • the molar ratio of carbon monoxide to hydrogen in the mixed gas of carbon monoxide and hydrogen is preferably 0.2 to 5 (carbon monoxide / hydrogen).
  • Compound (b) is a known oxidizing agent such as oxone (registered trademark; manufactured by DuPont, containing 43% by weight of potassium hydrogen persulfate), hydrogen peroxide solution, etc. in a solvent at 0 to 100 ° C. and 0.2%.
  • Compound (c) can be produced by treating for ⁇ 50 hours.
  • the solvent include acetonitrile, methanol, a mixed solvent thereof and the like.
  • Compound (c) is treated with an acid anhydride such as acetic anhydride, propionic anhydride, maleic anhydride, phthalic anhydride in a solvent such as 1,4-dioxane at 0 to 200 ° C. for 0.2 to 50 hours.
  • an acid anhydride such as acetic anhydride, propionic anhydride, maleic anhydride, phthalic anhydride in a solvent such as 1,4-dioxane at 0 to 200 ° C. for 0.2 to 50 hours.
  • Compound (VII) can also be obtained by, for example, producing according to the method described in US Pat. No. 3,413,317. ⁇ Method for Producing Compound (VI)> Compound (VI) can be produced, for example, according to reaction formulas (2) and (3).
  • compound (VI) is obtained by reacting compound (VII) with a halogenating agent to obtain an acid halide represented by formula (d) [hereinafter referred to as compound (d)],
  • compound (d) can be produced by reacting a diol represented by HO—X—OH (wherein X is as defined above).
  • Reaction formula (2) Compound (d) can be produced, for example, by reacting a halogenating agent with compound (VI) at 0 to 120 ° C. for 1 to 24 hours.
  • the amount of the halogenating agent to be used is preferably 1 to 100 moles compared to Compound (VII).
  • a solvent such as hexane, toluene, ethyl acetate, ⁇ -butyrolactone, N-methyl-2-pyrrolidone or tetrahydrofuran may be used.
  • a catalyst such as N, N-dimethylformamide or pyridine may be used.
  • halogenating agent examples include known halogenating agents such as SOW 2 (wherein W is as defined above), phosphorus trichloride, oxalyl chloride, benzoic acid chloride, among which SOW 2 is preferable, Thionyl chloride is more preferred.
  • SOW 2 is used as the halogenating agent
  • unreacted SOW 2 is preferably distilled off from the resulting reaction mixture after the reaction.
  • the method of distilling off include a method of adding an azeotropic agent such as benzene and toluene and distilling off SOW 2 and the azeotropic agent from the reaction mixture.
  • the compound (d) may be purified by methods usually used in organic synthetic chemistry (various chromatographic methods, recrystallization methods, distillation methods, etc.).
  • Compound (VI) is, for example, a compound (d) and a diol represented by HO—X—OH (wherein X is as defined above), preferably -10 in a solvent in the presence of a base. It can be produced by reacting at -50 ° C for 1-100 hours.
  • a diol represented by HO—X—OH may be simply referred to as a diol.
  • Specific examples of the diol include, for example, hydroquinone, 2-methylhydroquinone, resorcinol, catechol, 2-phenylhydroquinone, 4,4′-biphenol, 3,4′-biphenol, 2,2′-biphenol, 4,4 ′.
  • the amount of the compound (d) used is preferably 2.1 to 10 moles relative to the diol.
  • the base include amines such as pyridine, triethylamine and N, N-dimethylaniline, and inorganic bases such as potassium carbonate and sodium hydroxide.
  • the amount of the base used is preferably 1 to 10 moles compared to the compound (d).
  • An epoxy compound such as propylene oxide may be used in place of the base.
  • the solvent examples include ether solvents such as tetrahydrofuran and 1,4-dioxane, ketone solvents such as acetone and methyl ethyl ketone, aromatic hydrocarbon solvents such as toluene and xylene, dichloromethane, chloroform, 1,2-dichloroethane, and the like. And amide solvents such as N-methyl-2-pyrrolidone, dimethylacetamide and N, N-dimethylformamide, ester solvents such as ⁇ -butyrolactone, ethyl acetate and butyl acetate, and dimethyl sulfoxide. These solvents may be used alone or in combination of two or more.
  • ether solvents such as tetrahydrofuran and 1,4-dioxane
  • ketone solvents such as acetone and methyl ethyl ketone
  • aromatic hydrocarbon solvents such as toluene and xylene
  • the compound (VI) may be purified by methods usually used in organic synthetic chemistry (various chromatographic methods, recrystallization methods, distillation methods, etc.).
  • the isolated compound (VI) is preferably heated at 100 to 250 ° C. under reduced pressure for 1 to 50 hours.
  • the hydrolyzate of compound (VI) is contained as an impurity in compound (VI)
  • the hydrolyzate can be converted to compound (VI) by the heating.
  • the polyimide precursor (V) is represented by, for example, one or more kinds of tetracarboxylic dianhydrides including the compound (VI) and H 2 NA—NH 2 (wherein A is as defined above). It can be produced by reacting with diamine in a solvent at 0 to 100 ° C. for 1 to 300 hours.
  • the diamine represented by H 2 N—A—NH 2 may be simply referred to as diamine.
  • diamines include, for example, 4,4′-methylenedicyclohexylamine, 3,3′-dimethyl-4,4′-methylenedicyclohexylamine, 3,3′-diethyl-4,4′-methylenedicyclohexylamine, 3,3 ′, 5,5′-tetramethyl-4,4′-methylenedicyclohexylamine, 3,3 ′, 5,5′-tetraethyl-4,4′-methylenedicyclohexylamine, isophoronediamine, trans-1, 4-cyclohexanediamine, cis-1,4-cyclohexanediamine, 1,4-cyclohexanebis (methylamine), 2,5-bis (aminomethyl) bicyclo [2.2.1] heptane, 2,6-bis ( Aminomethyl) bicyclo [2.2.1] heptane, 3,8-bis (aminomethyl) tricyclo [5.2 .1.0] decane, tricyclo [
  • tetracarboxylic dianhydrides containing compound (VI) When two or more kinds of tetracarboxylic dianhydrides containing compound (VI) are used, two or more kinds of compounds (VI) may be used, and one or more kinds of compounds (VI) and one or more kinds of compounds ( A tetracarboxylic dianhydride other than VI) may be used in combination.
  • tetracarboxylic dianhydrides other than compound (VI) include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4.
  • the amount of one or more types of compound (VI) used is the amount of tetracarboxylic acid dihydrate used. It is preferably 20 mol% or more, more preferably 50 mol% or more, based on the total amount of anhydride.
  • the amount of diamine used is preferably 0.8 to 1.2 moles, more preferably 0.95 to 1.05 moles, based on the total amount of tetracarboxylic dianhydride used. Further, it is preferably 0.99 to 1.01 times mole.
  • the solvent examples include amide solvents such as N, N-dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -caprolactone, ⁇ - Cyclic ester solvents such as methyl- ⁇ -butyrolactone, carbonate solvents such as ethylene carbonate and propylene carbonate, glycol solvents such as triethylene glycol, m-cresol, p-cresol, 3-chlorophenol, 4-chlorophenol, etc. Phenolic solvents, acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide and the like.
  • amide solvents such as N, N-dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇
  • the sum of the weight of the diamine used and the weight of the tetracarboxylic acid anhydride used is preferably 5 to 40% based on the weight of the reaction solution.
  • the sum of the weight of the diamine used and the weight of the tetracarboxylic anhydride used is preferably 5 to 30% with respect to the weight of the reaction solution.
  • the intrinsic viscosity at 30 ° C. of a 0.5 wt% dimethylacetamide solution of the polyimide precursor (V) is preferably 0.1 dL / g or more.
  • the polyimide precursor (V) having an intrinsic viscosity of 0.1 dL / g has excellent film forming properties.
  • the intrinsic viscosity is 0.1 dL.
  • the film obtained by using the polyimide precursor (V) which is / g has effects such as being hard to crack.
  • the number average molecular weight of the polyimide precursor (V) is preferably 2,000 to 1,000,000.
  • the obtained solution of the polyimide precursor (V) may be used as it is for the production of the later-described polyimide (for example, Journal of Applied Polymer Science, 1986, Vol. 32, p. 3133, Polymer, 1993). 34, p. 849, etc.).
  • the polyimide precursor (V) may be purified by a method usually used in polymer chemistry (such as reprecipitation) as necessary.
  • the polyimide (I) can be produced, for example, by imidizing the polyimide precursor (V).
  • imidizing the polyimide precursor (V) the amic acid unit contained in the polyimide precursor (V) is converted into an imide unit.
  • the method for imidizing the polyimide precursor (V) include thermal imidization and chemical imidization.
  • a method for producing polyimide (I) by thermal imidization for example, a method for producing polyimide (I) by heating polyimide precursor (V) in a solvent at 150 to 400 ° C. for 0.5 to 200 hours. Etc.
  • the solvent examples include amide solvents such as N, N-dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -caprolactone, ⁇ - Cyclic ester solvents such as methyl- ⁇ -butyrolactone, carbonate solvents such as ethylene carbonate and propylene carbonate, glycol solvents such as triethylene glycol, m-cresol, p-cresol, 3-chlorophenol, 4-chlorophenol, etc. Phenolic solvents, acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide and the like.
  • amide solvents such as N, N-dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇
  • polyimide (I) may be purified by a method usually used in polymer chemistry (such as reprecipitation).
  • the obtained polyimide (I) is dissolved in, for example, dimethylacetamide to form a solution, which is applied onto a substrate such as glass, copper, aluminum, stainless steel, or silicon, and then the substrate is heated at 40 to 180 ° C. for 1 to
  • a polyimide (I) film can be produced by drying for 5 hours, and preferably heating at 150 to 400 ° C. for 0.5 to 5 hours.
  • a solution of the polyimide precursor (V) is applied on a substrate such as glass, copper, aluminum, stainless steel, or silicon, and then the substrate is heated at 40 to 180 ° C. for 5 minutes.
  • a method of producing a polyimide (I) film by drying for 5 hours to obtain a polyimide precursor (V) film, and then heating the film at 150 to 400 ° C. for 5 minutes to 5 hours. It is done.
  • the solvent in the solution of the polyimide precursor (V) include those mentioned above as the solvent used for thermal imidization.
  • a method for producing polyimide (I) by chemical imidization for example, a polyimide precursor (V) in a solvent in the presence of an amine such as pyridine or triethylamine is heated at 0 to 50 ° C. with a chemical imidizing agent such as acetic anhydride. And a method of treating for 1 to 48 hours.
  • the amount of the chemical imidizing agent used is preferably 1 to 100 times mol for the amic acid unit contained in the polyimide precursor (V).
  • the amount of amine used is preferably 0.1 to 50 times the mole of the chemical imidizing agent.
  • the solvent include those listed above as solvents used for thermal imidization.
  • polyimide (I) may be purified by a method commonly used in polymer chemistry (reprecipitation or the like).
  • the obtained polyimide (I) is dissolved in, for example, dimethylacetamide to form a solution, which is applied onto a substrate such as glass, copper, aluminum, stainless steel, or silicon.
  • a polyimide (I) film can be produced by drying for 1 to 5 hours.
  • the polyimide (I) film is preferably further heated at 150 to 400 ° C. for 0.5 to 5 hours.
  • the polyimide precursor (V) film is immersed in a solution containing an amine such as pyridine or triethylamine and a chemical imidizing agent such as acetic anhydride. And a method for producing a polyimide (I) film.
  • the polyimide (I) film is preferably further heated at 150 to 400 ° C. for 0.5 to 5 hours.
  • the polyimide (I) is obtained by treating the polyimide precursor (V) with N, N-dicyclohexylcarbodiimide, trifluoroacetic anhydride or the like to obtain a polymer having an isoimide unit, and then heating the polymer having the isoimide unit.
  • N, N-dicyclohexylcarbodiimide, trifluoroacetic anhydride or the like for example, the method described in Polymer Journal, 1994, Vol. 26, p. 315, etc.
  • the amic acid unit contained in the polyimide precursor (V) is converted into an isoimide unit, and then the isoimide unit is converted into an imide unit.
  • the polyimide (I) of the present invention Since the polyimide (I) of the present invention has high heat resistance, it is useful for liquid crystal display (LCD) substrates, organic electroluminescence display (ELD) substrates, and the like.
  • the polyimide (I) of the present invention has transparency, low dielectric constant, light transmittance, birefringence, deflection temperature under load, various hardness, water absorption, strength against tension and bending, elastic modulus, Young's modulus, flexibility Excellent in electrical properties, electrical insulation, arc resistance, chemical resistance, hot water resistance, solubility in various solvents, etc.
  • ⁇ FT-IR spectrum> A Fourier transform infrared spectrophotometer (FT-IR5300 or FT-IR350) manufactured by JASCO Corporation was used. ⁇ 1 H-NMR spectrum> An NMR spectrophotometer (ECP400) manufactured by JEOL Ltd. was used. ⁇ Melting point> Using a differential scanning calorimeter (DSC3100) manufactured by Bruker Ax, measurement was performed in a nitrogen atmosphere at a heating rate of 2 ° C./min (DSC analysis). ⁇ Intrinsic viscosity> Using an Ostwald viscometer, the intrinsic viscosity of a 0.5 wt% polyimide precursor solution (solvent: dimethylacetamide) was measured at 30 ° C.
  • TMA4000 Bruker AXS thermomechanical analyzer
  • Example 1 Synthesis of Compound (VI-1) 1.8 g of 5-chlorocarbonyl-2,3-bicyclo [2.2.1] heptanedicarboxylic anhydride obtained by the same procedure as in Synthesis Example 4 (8.0 mmol) and 8.2 mL of anhydrous tetrahydrofuran were charged to the reactor, the reactor was sealed with a septum cap, and cooled to 0 ° C. in an ice bath. A solution obtained by mixing 0.4 g (4.0 mmol) of hydroquinone, 1.3 mL (16.0 mmol) of pyridine and 2.0 mL of anhydrous tetrahydrofuran was slowly added dropwise to the reactor using a syringe in an ice bath.
  • the crude product was recrystallized from a mixed solvent of acetic anhydride and toluene (volume ratio 1: 1) to obtain 0.1 g of Compound (VI-2).
  • the obtained compound (VI-2) was subjected to DSC analysis. A sharp endothermic peak (melting point) was observed at 260.8 ° C. in the DSC curve, which showed that the obtained compound (VI-2) was of high purity.
  • Example 3 Synthesis of Compound (VI-3) 2.6 g (13.1 mmol) of 4,4′-bicyclohexanol (trans-trans type), 6.4 mL (78.9 mmol) of pyridine and 55.7 mL of anhydrous tetrahydrofuran was charged to the reactor, the reactor was sealed with a septum cap, and cooled to 0 ° C. in an ice bath. 6.0 g (26.3 mmol) of 5-chlorocarbonyl-2,3-bicyclo [2.2.1] heptanedicarboxylic acid anhydride obtained by operating in the same manner as in Synthesis Example 4 and 20.3 mL of anhydrous tetrahydrofuran were mixed.
  • the crude product was recrystallized from acetic anhydride to obtain 0.5 g of Compound (VI-5).
  • DSC analysis of the obtained compound (VI-5) was performed. In the DSC curve, a sharp endothermic peak (melting point) was observed at 316.8 ° C., indicating that the obtained compound (VI-5) was of high purity.
  • Example 6 Synthesis of Compound (VI-6) 3.3 g of 5-chlorocarbonyl-2,3-bicyclo [2.2.1] heptanedicarboxylic anhydride obtained by the same procedure as in Synthesis Example 4 14.4 mmol) and 5.6 mL of anhydrous tetrahydrofuran were charged to the reactor, and the reactor was sealed with a septum cap and cooled to 0 ° C. in an ice bath.
  • the crude product was recrystallized from a mixed solvent of acetic anhydride and acetic acid (volume ratio 1: 2) to obtain 0.2 g of Compound (VI-6).
  • DSC analysis of the obtained compound (VI-6) was performed. In the DSC curve, a sharp endothermic peak (melting point) was observed at 235.3 ° C., indicating that the obtained compound (VI-6) was of high purity.
  • Examples 7 to 30 Production of polyimide precursors (V-1) to (V-24) Using the combination of diamine and tetracarboxylic dianhydride shown in Table 1 as raw materials, the following operations are performed. As a result, solutions of polyimide precursors (V-1) to (V-24) were obtained. A well-dried sealed reactor equipped with a stirrer was charged with 5 mmol of diamine and dimethylacetamide, then 5 mmol of tetracarboxylic dianhydride was gradually added at room temperature, and then stirred for the time shown in Table 1 to obtain a clear and viscous solution. A solution of a polyimide precursor was obtained.
  • Examples 31 to 54 Production of polyimides (I-1) to (I-24) Using the polyimide precursors shown in Table 2 as raw materials, the following operations were performed to obtain polyimides (I-1) to (I -24) was obtained.
  • Each of the polyimide precursor solutions obtained in Examples 7 to 30 was charged into a reactor, and then a chemical imidization reagent (acetic anhydride / pyridine mixed solution, volume ratio 7/3) was dropped into the reactor at room temperature. Subsequently, it stirred at room temperature for 24 hours.
  • the amount of acetic anhydride in the chemical imidizing reagent used at this time is a 5-fold molar amount with respect to the amic acid unit contained in the polyimide precursor (V).
  • polyimides (I-1) to (I-24) 1 g of each of the polyimides (I-1) to (I-24) was dissolved in 3 g of dimethylacetamide, the resulting solution was applied to a glass substrate by bar coating, and the glass substrate was dried at 60 ° C. for 2 hours.
  • the glass substrate is heated under the heat treatment conditions shown in Table 2, and the polyimide film formed on the glass substrate is peeled off from the substrate, whereby transparent polyimides (I-1) to (I- 24) was obtained.
  • a polyimide precursor (X-1) is obtained by performing the same operation as in Example 7 except that the tetracarboxylic dianhydride represented by the formula (VIII-1) is used in place of the compound (VI-1). It was.
  • polyimide (XI-1) was obtained by performing the same operation as in Example 31 except that the polyimide precursor (X-1) was used instead of the polyimide precursor (V-1).
  • a film of polyimide (XI-1) was obtained by performing the same operation as in Example 31 except that polyimide (XI-1) was used instead of polyimide (I-1).
  • Table 3 shows the physical properties of the polyimide (XI-1) film.
  • a polyimide precursor (X-2) is obtained by performing the same operation as in Example 9 except that the tetracarboxylic dianhydride represented by the formula (VIII-1) is used in place of the compound (VI-1). It was.
  • a polyimide (XI-2) was obtained by performing the same operation as in Example 31 except that the polyimide precursor (X-2) was used instead of the polyimide precursor (V-1).
  • a polyimide (XI-2) film was obtained by performing the same operation as in Example 31 except that polyimide (XI-2) was used instead of polyimide (I-1).
  • Table 3 shows the physical properties of the polyimide (XI-2) film.
  • Polyimide (I-1) had lower CTE and higher Tg compared to polyimide (XI-1).
  • polyimide having high heat resistance and the like can be provided.

Abstract

Disclosed is a polyimide having a repeating unit represented by formula (I), or the like. [In the formula (I), P1, P2 and P3 each represents a hydrogen atom or the like; and X and A may be the same or different and each represents a group represented by formula (II) or the like.] [In the formula (II), m represents an integer of 0-3; R1 and R2 may be the same or different and each represents an alkyl group or the like; q and r may be the same or different and each represents an integer of 0-4; and Z1 represents a single bond, an oxygen atom, SO2 or the like.]

Description

ポリイミドPolyimide
　本発明は、各種電子デバイスにおける電気絶縁膜、液晶ディスプレー（ＬＣＤ）用基板、有機エレクトロルミネッセンスディスプレー（ＥＬＤ）用基板、電子ペーパー用基板、太陽電池用基板、半導体素子の層間絶縁膜および保護膜、液晶配向膜、光導波路材料等に有用なポリイミド等に関する。 The present invention relates to an electrical insulating film in various electronic devices, a substrate for liquid crystal display (LCD), a substrate for organic electroluminescence display (ELD), a substrate for electronic paper, a substrate for solar cell, an interlayer insulating film and a protective film for semiconductor elements, The present invention relates to polyimide useful for liquid crystal alignment films, optical waveguide materials, and the like.
　現在、ＬＣＤまたはＥＬＤにはガラス基板が用いられているが、近年の大画面化の動向に伴い、基板の軽量化および生産性向上が求められている。その解決方法としてガラス基板の替わりに、より軽量で成型加工が容易なポリイミド等のプラスチック基板の採用が期待されている。 Currently, glass substrates are used for LCDs or ELDs, but with the trend of larger screens in recent years, there is a demand for lighter substrates and improved productivity. As a solution to this problem, it is expected to use a plastic substrate such as polyimide that is lighter and easier to mold instead of the glass substrate.
　ポリイミドとしては、例えば、一般式（ＶＩＩＩ） As polyimide, for example, general formula (VIII)
Figure JPOXMLDOC01-appb-C000017
 （式中、Ｙは２価の芳香族基等を表す）で表されるテトラカルボン酸二無水物とジアミンとを反応させて得られるポリイミド（特許文献１）等が知られているが、高い耐熱性等の要求性能を満足するものではない。
Figure JPOXMLDOC01-appb-C000017
 A polyimide obtained by reacting a tetracarboxylic dianhydride represented by (wherein Y represents a divalent aromatic group or the like) and a diamine (Patent Document 1) is known, but is high. It does not satisfy the required performance such as heat resistance.
国際公開第２００６／１２９７７１号パンフレットInternational Publication No. 2006/129771 Pamphlet
　本発明は、高い耐熱性等を有するポリイミド等を提供する。 The present invention provides polyimide having high heat resistance and the like.
　より具体的には、以下の発明が提供される。 More specifically, the following inventions are provided.
（１）　式（Ｉ） (1) Formula (I)
Figure JPOXMLDOC01-appb-C000018
 ［式中、Ｐ１、Ｐ２およびＰ３は、同一または異なって、水素原子、ハロゲン原子、シアノ基、ホルミル基、ヒドロキシル基、置換もしくは非置換のアルキル基、置換もしくは非置換のシクロアルキル基、置換もしくは非置換のアルケニル基、置換もしくは非置換のアリール基、置換もしくは非置換のアラルキル基、置換もしくは非置換のアルカノイルオキシ基または置換もしくは非置換のアルコキシル基を表し、ＸおよびＡは、同一または異なって、置換もしくは非置換のアルキレン基、置換もしくは非置換の多環式不飽和炭化水素から炭素原子上の水素原子を２つ除くことにより生じる２価の基、置換もしくは非置換の多環式飽和炭化水素から炭素原子上の水素原子を２つ除くことにより生じる２価の基、式（ＩＩ）
Figure JPOXMLDOC01-appb-C000018
 [Wherein P 1 , P 2 and P 3 are the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, a formyl group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group Represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkanoyloxy group or a substituted or unsubstituted alkoxyl group, and X and A are the same Or differently, a substituted or unsubstituted alkylene group, a divalent group formed by removing two hydrogen atoms on a carbon atom from a substituted or unsubstituted polycyclic unsaturated hydrocarbon, a substituted or unsubstituted polycycle A divalent group formed by removing two hydrogen atoms on a carbon atom from a saturated hydrocarbon of formula (II)
Figure JPOXMLDOC01-appb-C000019
 ［式中、ｍは０～３の整数を表し、Ｒ１およびＲ２は、同一または異なって、ハロゲン原子、シアノ基、ホルミル基、ヒドロキシル基、置換もしくは非置換のアルキル基、置換もしくは非置換のアルケニル基、置換もしくは非置換のアリール基、置換もしくは非置換のアルカノイルオキシ基または置換もしくは非置換のアルコキシル基を表し、ｑおよびｒは、同一または異なって、０～４の整数を表し、ｑが２～４の整数であるときＲ１のそれぞれは同一または異なってよく、ｒが２～４の整数であるときＲ２のそれぞれは同一または異なってよく、Ｚ１は単結合、酸素原子、硫黄原子、ＳＯ２、フッ素原子が置換していてもよい炭素数１～４のアルキレン基、または式（ＩＩＩ）
Figure JPOXMLDOC01-appb-C000019
 [Wherein, m represents an integer of 0 to 3, and R 1 and R 2 are the same or different and each represents a halogen atom, a cyano group, a formyl group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group. Alkenyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkanoyloxy group or substituted or unsubstituted alkoxyl group, q and r are the same or different and represent an integer of 0 to 4, q Each of R 1 may be the same or different when R is an integer of 2 to 4, and each of R 2 may be the same or different when r is an integer of 2 to 4, and Z 1 is a single bond, an oxygen atom, A sulfur atom, SO 2 , a C 1-4 alkylene group which may be substituted by a fluorine atom, or the formula (III)
Figure JPOXMLDOC01-appb-C000020
 （式中、Ｒ５およびＲ６は、同一または異なって、ハロゲン原子、シアノ基、ホルミル基、ヒドロキシル基、置換もしくは非置換のアルキル基、置換もしくは非置換のシクロアルキル基、置換もしくは非置換のアルケニル基、置換もしくは非置換のアリール基、置換もしくは非置換のアラルキル基、置換もしくは非置換のアルカノイルオキシ基または置換もしくは非置換のアルコキシル基を表し、ｅおよびｆは、同一または異なって、０～４の整数を表し、ｅが２～４の整数であるときＲ５のそれぞれは同一または異なってよく、ｆが２～４の整数であるときＲ６のそれぞれは同一または異なってよい）を表し、ｍが２または３であるときＲ１、ｑおよびＺ１のそれぞれは同一または異なってよい］または式（ＩＶ）
Figure JPOXMLDOC01-appb-C000020
 (Wherein R 5 and R 6 are the same or different and each represents a halogen atom, a cyano group, a formyl group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted group, Represents an alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkanoyloxy group or a substituted or unsubstituted alkoxyl group, and e and f are the same or different and represent 0 to Each of R 5 may be the same or different when e is an integer of 2 to 4, and each of R 6 may be the same or different when f is an integer of 2 to 4. Each of R 1 , q and Z 1 may be the same or different when m is 2 or 3] or formula (IV)
Figure JPOXMLDOC01-appb-C000021
 （式中、ｎは０～３の整数を表し、Ｒ３およびＲ４は、同一または異なって、ハロゲン原子、シアノ基、ホルミル基、ヒドロキシル基、置換もしくは非置換のアルキル基、置換もしくは非置換のシクロアルキル基、置換もしくは非置換のアルケニル基、置換もしくは非置換のアルカノイルオキシ基または置換もしくは非置換のアルコキシル基を表し、ｓａおよびｕａは、同一または異なって、０～４の整数を表し、ｓａが２～４の整数であるときＲ３のそれぞれは同一または異なってよく、ｕａが２～４の整数であるときＲ４のそれぞれは同一または異なってよく、ｓｂおよびｕｂは、同一または異なって、０～２の整数を表し、Ｚ２は単結合、酸素原子、硫黄原子、ＳＯ２またはフッ素原子が置換していてもよい炭素数１～４のアルキレン基を表し、ｎが２または３であるときＲ３、ｓａ、ｓｂおよびＺ２のそれぞれは同一または異なっていてもよい）を表す］で表される繰り返し単位を有するポリイミド。
Figure JPOXMLDOC01-appb-C000021
 (Wherein n represents an integer of 0 to 3, and R 3 and R 4 are the same or different and are each a halogen atom, a cyano group, a formyl group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group, A cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkanoyloxy group or a substituted or unsubstituted alkoxyl group, sa and ua are the same or different and represent an integer of 0 to 4; When sa is an integer from 2 to 4, each R 3 may be the same or different, and when ua is an integer from 2 to 4 , each R 4 may be the same or different, and sb and ub are the same or different. Te, 0 represents an integer 2, Z 2 is a single bond, an oxygen atom, a sulfur atom, alkyl of SO 2 or a fluorine atom and 1 carbon atoms and optionally substituted 4 Represents an emission radical, n when it is 2 or 3 R 3, sa, polyimide having a repeating unit each of sb and Z 2 is represented by representing the same or may be different).
（２）　式（Ｖ） (2) Formula (V)
Figure JPOXMLDOC01-appb-C000022
 ［式中、Ｐ１、Ｐ２、Ｐ３およびＸはそれぞれ前記と同義であり、ＲａおよびＲｂの一方はヒドロキシル基を表し他方は－ＮＨ－Ａ－（式中、Ａは前記と同義である）で表される２価の基を表し、ＲｃおよびＲｄの一方はヒドロキシル基を表し他方は－ＮＨ－で表される２価の基を表す］で表される繰り返し単位を有するポリイミド前駆体をイミド化することを特徴とする式（Ｉ）
Figure JPOXMLDOC01-appb-C000022
 [Wherein P 1 , P 2 , P 3 and X are as defined above, one of R a and R b represents a hydroxyl group and the other is —NH—A— (wherein A is as defined above] In which one of R c and R d represents a hydroxyl group and the other represents a divalent group represented by —NH—. Formula (I) characterized by imidizing a polyimide precursor
Figure JPOXMLDOC01-appb-C000023
 （式中、Ｐ１、Ｐ２、Ｐ３、ＸおよびＡはそれぞれ前記と同義である）で表される繰り返し単位を有するポリイミドの製造方法。
Figure JPOXMLDOC01-appb-C000023
 (Wherein P 1 , P 2 , P 3 , X and A are as defined above), a method for producing a polyimide having a repeating unit.
（３）　式（Ｖ） (3) Formula (V)
Figure JPOXMLDOC01-appb-C000024
 （式中、Ｐ１、Ｐ２、Ｐ３、Ｘ、Ｒａ、Ｒｂ、ＲｃおよびＲｄはそれぞれ前記と同義である）で表される繰り返し単位を有するポリイミド前駆体。
Figure JPOXMLDOC01-appb-C000024
 (Wherein P 1 , P 2 , P 3 , X, R a , R b , R c and R d are as defined above), and a polyimide precursor having a repeating unit.
（４）　式（ＶＩ） (4) Formula (VI)
Figure JPOXMLDOC01-appb-C000025
 （式中、Ｐ１、Ｐ２、Ｐ３およびＸはそれぞれ前記と同義である）で表されるテトラカルボン酸二無水物を含む１種類以上のテトラカルボン酸二無水物とＨ２Ｎ－Ａ－ＮＨ２（式中、Ａは前記と同義である）で表されるジアミンとを反応させることを特徴とする式（Ｖ）
Figure JPOXMLDOC01-appb-C000025
 (Wherein P 1 , P 2 , P 3 and X are as defined above) and one or more types of tetracarboxylic dianhydrides including H 2 NA Formula (V), characterized by reacting with a diamine represented by —NH 2 (wherein A is as defined above)
Figure JPOXMLDOC01-appb-C000026
 （式中、Ｐ１、Ｐ２、Ｐ３、Ｘ、Ｒａ、Ｒｂ、ＲｃおよびＲｄはそれぞれ前記と同義である）で表される繰り返し単位を有するポリイミド前駆体の製造方法。
Figure JPOXMLDOC01-appb-C000026
 (Wherein P 1 , P 2 , P 3 , X, R a , R b , R c and R d are as defined above), a method for producing a polyimide precursor having a repeating unit.
（５）　式（ＶＩ） (5) Formula (VI)
Figure JPOXMLDOC01-appb-C000027
 （式中、Ｐ１、Ｐ２、Ｐ３およびＸはそれぞれ前記と同義である）で表されるテトラカルボン酸二無水物。
Figure JPOXMLDOC01-appb-C000027
 (Wherein P 1 , P 2 , P 3 and X are as defined above), tetracarboxylic dianhydride.
（６）　式（ＶＩＩ） (6) Formula (VII)
Figure JPOXMLDOC01-appb-C000028
 （式中、Ｐ１、Ｐ２およびＰ３はそれぞれ前記と同義である）で表される酸無水物とハロゲン化剤とを反応させることにより酸ハライドを得、次いで、該酸ハライドとＨＯ－Ｘ－ＯＨ（式中、Ｘは前記と同義である）で表されるジオールとを反応させることを特徴とする式（ＶＩ）
Figure JPOXMLDOC01-appb-C000028
 (Wherein P 1 , P 2 and P 3 are as defined above), an acid halide and a halogenating agent are reacted to obtain an acid halide, and then the acid halide and HO— Reacting with a diol represented by X—OH (wherein X is as defined above),
Figure JPOXMLDOC01-appb-C000029
 （式中、Ｐ１、Ｐ２、Ｐ３およびＸおよびＡはそれぞれ前記と同義である）で表されるテトラカルボン酸二無水物の製造方法。
Figure JPOXMLDOC01-appb-C000029
 (Wherein P 1 , P 2 , P 3 and X and A are as defined above), a method for producing a tetracarboxylic dianhydride.
（７）　式（ＶＩＩ） (7) Formula (VII)
Figure JPOXMLDOC01-appb-C000030
 （式中、Ｐ１、Ｐ２およびＰ３はそれぞれ前記と同義である）で表される酸無水物とハロゲン化剤とを反応させることにより酸ハライドを得、次いで、該酸ハライドとＨＯ－Ｘ－ＯＨ（式中、Ｘは前記と同義である）で表されるジオールとを反応させることにより式（ＶＩ）
Figure JPOXMLDOC01-appb-C000030
 (Wherein P 1 , P 2 and P 3 are as defined above), an acid halide and a halogenating agent are reacted to obtain an acid halide, and then the acid halide and HO— By reacting with a diol represented by X—OH (wherein X is as defined above), the compound of formula (VI)
Figure JPOXMLDOC01-appb-C000031
 （式中、Ｐ１、Ｐ２、Ｐ３およびＸはそれぞれ前記と同義である）で表されるテトラカルボン酸二無水物を得、次いで、該テトラカルボン酸二無水物を含む１種類以上のテトラカルボン酸二無水物とＨ２Ｎ－Ａ－ＮＨ２（式中、Ａは前記と同義である）で表されるジアミンとを反応させることにより式（Ｖ）
Figure JPOXMLDOC01-appb-C000031
 (Wherein P 1 , P 2 , P 3 and X are as defined above), and then one or more kinds of tetracarboxylic dianhydrides containing the tetracarboxylic dianhydride By reacting tetracarboxylic dianhydride with a diamine represented by H 2 N—A—NH 2 (wherein A is as defined above), the compound represented by the formula (V)
Figure JPOXMLDOC01-appb-C000032
 （式中、Ｐ１、Ｐ２、Ｐ３、Ｘ、Ｒａ、Ｒｂ、ＲｃおよびＲｄはそれぞれ前記と同義である）で表される繰り返し単位を有するポリイミド前駆体を得、次いで、該ポリイミド前駆体をイミド化することを特徴とする式（Ｉ）
Figure JPOXMLDOC01-appb-C000032
 (Wherein P 1 , P 2 , P 3 , X, R a , R b , R c and R d are as defined above), a polyimide precursor having a repeating unit represented by Formula (I) characterized by imidizing the polyimide precursor
Figure JPOXMLDOC01-appb-C000033
 （式中、Ｐ１、Ｐ２、Ｐ３、ＸおよびＡはそれぞれ前記と同義である）で表される繰り返し単位を有するポリイミドの製造方法。
Figure JPOXMLDOC01-appb-C000033
 (Wherein P 1 , P 2 , P 3 , X and A are as defined above), a method for producing a polyimide having a repeating unit.
（８）　ＸおよびＡが、同一または異なって、式（ＩＩ）または式（ＩＶ）である上記（１）記載のポリイミド。 (8) The polyimide according to the above (1), wherein X and A are the same or different and are represented by formula (II) or formula (IV).
（９）　ＸおよびＡが、同一または異なって、式（ＩＩ）である上記（１）記載のポリイミド。
（１０）　Ｐ１、Ｐ２およびＰ３が水素原子である上記（１）、（８）または（９）記載のポリイミド。 (9) The polyimide according to the above (1), wherein X and A are the same or different and are represented by the formula (II).
(10) The polyimide according to the above (1), (8) or (9), wherein P 1 , P 2 and P 3 are hydrogen atoms.
（１１）　ＸおよびＡが、同一または異なって、式（ＩＩ）または式（ＩＶ）である上記（３）記載のポリイミド前駆体。 (11) The polyimide precursor according to the above (3), wherein X and A are the same or different and are represented by formula (II) or formula (IV).
（１２）　ＸおよびＡが、同一または異なって、式（ＩＩ）である上記（３）記載のポリイミド前駆体。 (12) The polyimide precursor according to the above (3), wherein X and A are the same or different and are represented by the formula (II).
（１３）　Ｐ１、Ｐ２およびＰ３が水素原子である上記（３）、（１１）または（１２）記載のポリイミド前駆体。 (13) The polyimide precursor according to the above (3), (11) or (12), wherein P 1 , P 2 and P 3 are hydrogen atoms.
（１４）　Ｘが式（ＩＩ）または式（ＩＶ）である上記（５）記載のテトラカルボン酸二無水物。 (14) The tetracarboxylic dianhydride according to the above (5), wherein X is formula (II) or formula (IV).
（１５）　Ｘが式（ＩＩ）である上記（５）記載のテトラカルボン酸二無水物。 (15) The tetracarboxylic dianhydride according to the above (5), wherein X is the formula (II).
（１６）　Ｐ１、Ｐ２およびＰ３が水素原子である上記（５）、（１４）または（１５）記載のテトラカルボン酸二無水物。 (16) The tetracarboxylic dianhydride according to the above (5), (14) or (15), wherein P 1 , P 2 and P 3 are hydrogen atoms.
　本発明により、高い耐熱性等を有するポリイミド等を提供できる。 According to the present invention, polyimide having high heat resistance and the like can be provided.
　以下、式（ＶＩ）で表される化合物を化合物（ＶＩ）という。他の式番号で表される低分子化合物についても同様である。
　また、式（Ｉ）で表される繰り返し単位を有するポリイミドをポリイミド（Ｉ）といい、式（Ｖ）で表される繰り返し単位を有するポリイミド前駆体をポリイミド前駆体（Ｖ）という。 Hereinafter, the compound represented by formula (VI) is referred to as compound (VI). The same applies to the low molecular weight compounds represented by other formula numbers.
Moreover, the polyimide which has a repeating unit represented by Formula (I) is called polyimide (I), and the polyimide precursor which has a repeating unit represented by Formula (V) is called polyimide precursor (V).
　式中の各基の定義において、アルキル基、アルカノイルオキシ基のアルキル部分およびアルコキシル基のアルキル部分としては、例えば、直鎖または分岐状の炭素数１～１０のアルキル基が挙げられ、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、２－エチルヘキシル基、ノニル基、デシル基等が挙げられる。 In the definition of each group in the formula, examples of the alkyl group, the alkyl part of the alkanoyloxy group and the alkyl part of the alkoxyl group include linear or branched alkyl groups having 1 to 10 carbon atoms, specifically Are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, A decyl group etc. are mentioned.
　シクロアルキル基としては、例えば、炭素数５～７のシクロアルキル基が挙げられ、具体的には、シクロペンチル基、シクロヘキシル基、シクロヘプチル基等が挙げられる。
　アルケニル基としては、例えば、直鎖または分岐状の炭素数２～１０のアルケニル基が挙げられ、具体的には、エテニル基、１－プロペニル基、アリル基、ブテニル基、ペンテニル基、ヘキセニル基、ヘプテニル基、オクテニル基、ノネニル基、デセニル基等が挙げられる。
　アリール基としては、例えば、炭素数６～１０のアリール基が挙げられ、具体的には、フェニル基、ナフチル基等が挙げられる。
　アラルキル基としては、例えば、炭素数７～１０のアラルキル基が挙げられ、具体的には、ベンジル基、フェニルエチル基、フェニルプロピル基等が挙げられる。
　ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。
　アルキレン基としては、例えば、前記に例示したアルキル基から水素原子を１つ除くことにより生じる基が挙げられる。
　炭素数１～４のアルキレン基の具体例としては、例えば、メチレン基、エチレン基、トリメチレン基、プロピレン基、ジメチルメチレン基、テトラメチレン基、エチルエチレン基等が挙げられる。 Examples of the cycloalkyl group include cycloalkyl groups having 5 to 7 carbon atoms, and specific examples include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
Examples of the alkenyl group include linear or branched alkenyl groups having 2 to 10 carbon atoms, such as ethenyl group, 1-propenyl group, allyl group, butenyl group, pentenyl group, hexenyl group, A heptenyl group, an octenyl group, a nonenyl group, a decenyl group, etc. are mentioned.
Examples of the aryl group include aryl groups having 6 to 10 carbon atoms, and specific examples include a phenyl group and a naphthyl group.
Examples of the aralkyl group include aralkyl groups having 7 to 10 carbon atoms, and specific examples include a benzyl group, a phenylethyl group, and a phenylpropyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkylene group include groups generated by removing one hydrogen atom from the alkyl groups exemplified above.
Specific examples of the alkylene group having 1 to 4 carbon atoms include a methylene group, an ethylene group, a trimethylene group, a propylene group, a dimethylmethylene group, a tetramethylene group, and an ethylethylene group.
　多環式不飽和炭化水素としては、例えば、３～８員の環が縮合した二環または三環性で非隣接２重結合が最多の縮合多環式炭化水素（インデン、ナフタレン、アントラセン、アズレン、フルオレン等）、これらの部分水素化化合物（インダン、テトラヒドロナフタレン、テトラヒドロアントラセン等）等が挙げられる。 Examples of the polycyclic unsaturated hydrocarbon include, for example, a condensed polycyclic hydrocarbon in which a 3- to 8-membered ring is condensed, or a non-adjacent double bond having the largest number of non-adjacent double bonds (indene, naphthalene, anthracene, azulene). , Fluorene, etc.), partially hydrogenated compounds thereof (indane, tetrahydronaphthalene, tetrahydroanthracene, etc.) and the like.
　多環式飽和炭化水素としては、例えば、３～８員の環が縮合した二環または三環性の飽和炭化水素等が挙げられ、具体的には、ペルヒドロインデン、ペルヒドロナフタレン、ペルヒドロアントラセン、ビシクロ［３．２．１］オクタン、ビシクロ［２．２．１］ヘプタン、トリシクロ［３．３．１．１３，７］デカン等が挙げられる。 Examples of the polycyclic saturated hydrocarbon include bicyclic or tricyclic saturated hydrocarbons in which a 3- to 8-membered ring is condensed. Specific examples thereof include perhydroindene, perhydronaphthalene, perhydro Anthracene, bicyclo [3.2.1] octane, bicyclo [2.2.1] heptane, tricyclo [3.3.1.13,7] decane and the like can be mentioned.
　アルキル基、アルケニル基、アルカノイルオキシ基、アルコキシル基およびアルキレン基の置換基としては、例えば、同一または異なって１～３個の置換基、具体的には、ハロゲン原子、シアノ基、ホルミル基、ヒドロキシル基等が挙げられる。ここで、ハロゲン原子は前記と同義である。
　シクロアルキル基、アリール基、アラルキル基、多環式不飽和炭化水素および多環式飽和炭化水素の置換基としては、例えば、同一または異なって１～５個の置換基、具体的には、ハロゲン原子、シアノ基、ホルミル基、ヒドロキシル基、アルキル基、アルカノイルオキシ基、アルコキシル基等が挙げられる。ここで、ハロゲン原子、アルキル基、アルカノイルオキシ基およびアルコキシル基はそれぞれ前記と同義である。
　フッ素原子が置換していてもよい炭素数１～４のアルキレン基におけるフッ素原子の置換数は、０～置換可能な数である。 Examples of the substituent of the alkyl group, alkenyl group, alkanoyloxy group, alkoxyl group and alkylene group include, for example, the same or different 1 to 3 substituents, specifically, a halogen atom, cyano group, formyl group, hydroxyl group Groups and the like. Here, the halogen atom has the same meaning as described above.
Examples of the substituent of the cycloalkyl group, aryl group, aralkyl group, polycyclic unsaturated hydrocarbon and polycyclic saturated hydrocarbon include, for example, the same or different 1 to 5 substituents, specifically, halogen Atom, cyano group, formyl group, hydroxyl group, alkyl group, alkanoyloxy group, alkoxyl group and the like can be mentioned. Here, a halogen atom, an alkyl group, an alkanoyloxy group and an alkoxyl group have the same meanings as described above.
The number of substitution of fluorine atoms in the alkylene group having 1 to 4 carbon atoms which may be substituted with fluorine atoms is from 0 to a substitutable number.
　式（Ｉ）および式（Ｖ）の各基において、
　　Ｐ１、Ｐ２およびＰ３が水素原子であるのが好ましい。
　　ＸおよびＡが、同一または異なって、式（ＩＩ）または式（ＩＶ）であるのが好ましく、式（ＩＩ）であるのがより好ましい。
　Ｘが式（ＩＩ）であるとき、Ｒ１およびＲ２が、同一または異なって、メチル基またはトリフルオロメチル基であり、ｑおよびｒが、同一または異なって、０または１であり、Ｚ１が酸素原子、硫黄原子、ＳＯ２、フッ素原子が置換してもよい炭素数１～４のアルキレン基または式（ＩＩＩ）であり、Ｚ１が式（ＩＩＩ）であるときｅおよびｆが０であるのが好ましい。
　Ａが式（ＩＩ）であるときの好ましい基は、前記Ｘが式（ＩＩ）であるときの好ましい基と同義である。
　Ｘが式（ＩＶ）であるとき、Ｒ３およびＲ４が、同一または異なって、メチル基またはトリフルオロメチル基であり、ｓａおよびｕａが、同一または異なって、０または１であり、ｓｂおよびｕｂが１であるのが好ましい。
　Ａが式（ＩＶ）であるときの好ましい基は、前記Ｘが式（ＩＶ）であるときの好ましい基と同義である。 In each group of formula (I) and formula (V):
P 1 , P 2 and P 3 are preferably hydrogen atoms.
X and A are the same or different and are preferably the formula (II) or the formula (IV), more preferably the formula (II).
When X is the formula (II), R 1 and R 2 are the same or different and are a methyl group or a trifluoromethyl group, q and r are the same or different and are 0 or 1, and Z 1 Is an oxygen atom, a sulfur atom, SO 2 , a C 1-4 alkylene group which may be substituted by a fluorine atom or formula (III), and when Z 1 is formula (III), e and f are 0 Preferably there is.
A preferred group when A is the formula (II) has the same meaning as a preferred group when the X is the formula (II).
When X is formula (IV), R 3 and R 4 are the same or different and are a methyl group or a trifluoromethyl group, sa and ua are the same or different and are 0 or 1, sb and It is preferable that ub is 1.
A preferred group when A is the formula (IV) has the same meaning as a preferred group when X is the formula (IV).
　式（ＶＩ）の各基において、
　　Ｐ１、Ｐ２およびＰ３が水素原子であるのが好ましい。
　　Ｘが、式（ＩＩ）または式（ＩＶ）であるのが好ましい。
　式（ＶＩ）においてＸが式（ＩＩ）であるときの好ましい基は、前記式（Ｉ）および式（Ｖ）においてＸが式（ＩＩ）であるときの好ましい基と同義である。
　式（ＶＩ）においてＸが式（ＩＶ）であるときの好ましい基は、前記式（Ｉ）および式（Ｖ）においてＸが式（ＩＶ）であるときの好ましい基と同義である。
ポリイミド（Ｉ）に含まれる式（Ｉ）で表される繰り返し単位のそれぞれにおいて、Ｐ１、Ｐ２、Ｐ３、ＸおよびＡのそれぞれは、同一または異なってよい。
　ポリイミド前駆体（Ｖ）に含まれる式（Ｖ）で表される繰り返し単位のそれぞれにおいて、Ｐ１、Ｐ２、Ｐ３、Ｘ、Ｒａ、Ｒｂ、ＲｃおよびＲｄのそれぞれは、同一または異なってよい。 In each group of formula (VI):
P 1 , P 2 and P 3 are preferably hydrogen atoms.
X is preferably of formula (II) or formula (IV).
The preferred group when X is the formula (II) in the formula (VI) has the same meaning as the preferred group when X is the formula (II) in the formula (I) and the formula (V).
The preferred group when X is the formula (IV) in the formula (VI) has the same meaning as the preferred group when X is the formula (IV) in the formula (I) and the formula (V).
In each of the repeating units represented by the formula (I) contained in the polyimide (I), each of P 1 , P 2 , P 3 , X and A may be the same or different.
In each of the repeating units represented by the formula (V) contained in the polyimide precursor (V), each of P 1 , P 2 , P 3 , X, R a , R b , R c and R d is the same. Or it may be different.
次に、本発明の化合物（ＶＩ）、ポリイミド前駆体（Ｖ）およびポリイミド（Ｉ）の製造方法について説明する。 Next, the manufacturing method of the compound (VI) of this invention, a polyimide precursor (V), and a polyimide (I) is demonstrated.
　化合物（ＶＩ）の原料である化合物（ＶＩＩ）は、例えば、反応式（１）に従って製造することができる。 Compound (VII) which is a raw material of compound (VI) can be produced, for example, according to reaction formula (1).
Figure JPOXMLDOC01-appb-C000034
 （式中、Ｐ１、Ｐ２およびＰ３は、それぞれ前記と同義である）
Figure JPOXMLDOC01-appb-C000034
 (Wherein P 1 , P 2 and P 3 are as defined above)
反応式（１）
　化合物（ａ）は公知の方法、例えば、「実験化学講座（第１９巻）有機合成Ｉ　炭化水素・ハロゲン化合物」，第４版，丸善株式会社，１９９２年，ｐ．１７３－１９４に記載の方法等に準じて製造することにより得ることができる。 Reaction formula (1)
Compound (a) can be obtained by a known method, for example, “Experimental Chemistry Course (Vol. 19) Organic Synthesis I Hydrocarbon / Halogen Compound”, 4th edition, Maruzen Co., 1992, p. It can be obtained by manufacturing according to the method described in 173-194.
　化合物（ｂ）は、例えば、触媒の存在下、アセトニトリル等の溶媒中、一酸化炭素と水素の混合気体で化合物（ａ）を４０～１６０℃で、１～２０ＭＰａで、０．２～５０時間処理することにより製造することができる。 For example, the compound (b) is obtained by mixing the compound (a) with a mixed gas of carbon monoxide and hydrogen in a solvent such as acetonitrile in the presence of a catalyst at 40 to 160 ° C. and 1 to 20 MPa for 0.2 to 50 hours. It can be manufactured by processing.
　触媒としてはヒドロホルミル化に用いられる公知の貴金属触媒（例えば、コバルト系触媒、ロジウム系触媒、白金系触媒等）が挙げられ、具体的には、例えば、Ｃｏ２（ＣＯ）８、Ｃｏ４（ＣＯ）１２、Ｃｏ６（ＣＯ）１６、ＨＣｏ（ＣＯ）４、［Ｃｏ（ＣＯ）３（Ｃ５Ｈ６）］２、Ｒｈ４（ＣＯ）１２、Ｒｈ６（ＣＯ）１６、ＲｈＣｌ（ＰＰｈ３）３、［ＲｈＣｌ（ＣＯ）２］２、ＨＲｈ（ＣＯ）（ＰＰｈ３）３、Ｒｈ（ＣＯ）２（ａｃａｃ）、Ｒｈ（ＣＯ）（ＰＰｈ３）（ａｃａｃ）等が挙げられる。ここで、Ｃ５Ｈ６はシクロペンタジエンを表し、Ｐｈはフェニル基を表し、ａｃａｃはアセチルアセトナート基を表す。触媒の使用量は、化合物（ａ）に対して５～５０００ｐｐｍ（金属として）であるのが好ましく、１０～２０００ｐｐｍ（金属として）であるのがより好ましい。触媒はトリフェニルフォスフィン等のリン化合物と併用することが好ましい。触媒とリン化合物とを併用するときのリン化合物の使用量は、触媒に対して１～５００倍モルであるのが好ましい。
　一酸化炭素と水素の混合気体における一酸化炭素と水素のモル比は０．２～５（一酸化炭素／水素）であるのが好ましい。 Examples of the catalyst include known noble metal catalysts (for example, cobalt-based catalysts, rhodium-based catalysts, platinum-based catalysts, etc.) used for hydroformylation. Specifically, for example, Co 2 (CO) 8 , Co 4 (CO ) 12 , Co 6 (CO) 16 , HCo (CO) 4 , [Co (CO) 3 (C 5 H 6 )] 2 , Rh 4 (CO) 12 , Rh 6 (CO) 16 , RhCl (PPh 3 ) 3 , [RhCl (CO) 2 ] 2 , HRh (CO) (PPh 3 ) 3 , Rh (CO) 2 (acac), Rh (CO) (PPh 3 ) (acac), and the like. Here, C 5 H 6 represents cyclopentadiene, Ph represents a phenyl group, and acac represents an acetylacetonate group. The amount of the catalyst used is preferably 5 to 5000 ppm (as a metal), more preferably 10 to 2000 ppm (as a metal) with respect to the compound (a). The catalyst is preferably used in combination with a phosphorus compound such as triphenylphosphine. The amount of the phosphorus compound used when the catalyst and the phosphorus compound are used in combination is preferably 1 to 500 times mol of the catalyst.
The molar ratio of carbon monoxide to hydrogen in the mixed gas of carbon monoxide and hydrogen is preferably 0.2 to 5 (carbon monoxide / hydrogen).
　化合物（ｂ）を、例えば、溶媒中、オキソン（登録商標；デュポン社製、過硫酸水素カリウム４３重量％含有）、過酸化水素水等の公知の酸化剤で、０～１００℃で０．２～５０時間処理することにより化合物（ｃ）を製造することができる。溶媒としては、例えば、アセトニトリル、メタノール、これらの混合溶媒等が挙げられる。 Compound (b) is a known oxidizing agent such as oxone (registered trademark; manufactured by DuPont, containing 43% by weight of potassium hydrogen persulfate), hydrogen peroxide solution, etc. in a solvent at 0 to 100 ° C. and 0.2%. Compound (c) can be produced by treating for ˜50 hours. Examples of the solvent include acetonitrile, methanol, a mixed solvent thereof and the like.
　化合物（ｃ）を、例えば、１，４－ジオキサン等の溶媒中、無水酢酸、無水プロピオン酸、無水マレイン酸、無水フタル酸等の酸無水物で０～２００℃で０．２～５０時間処理することにより化合物（ＶＩＩ）を製造することができる。 Compound (c) is treated with an acid anhydride such as acetic anhydride, propionic anhydride, maleic anhydride, phthalic anhydride in a solvent such as 1,4-dioxane at 0 to 200 ° C. for 0.2 to 50 hours. Thus, compound (VII) can be produced.
　化合物（ＶＩＩ）は、例えば、米国特許第３，４１３，３１７号明細書に記載の方法等に準じて製造することにより得ることもできる。
＜化合物（ＶＩ）の製造方法＞
　化合物（ＶＩ）は、例えば、反応式（２）および（３）に従って製造することができる。 Compound (VII) can also be obtained by, for example, producing according to the method described in US Pat. No. 3,413,317.
<Method for Producing Compound (VI)>
Compound (VI) can be produced, for example, according to reaction formulas (2) and (3).
Figure JPOXMLDOC01-appb-C000035
 （式中、Ｐ１、Ｐ２、Ｐ３およびＸは、それぞれ前記と同義であり、Ｗはハロゲン原子を表す）
Figure JPOXMLDOC01-appb-C000035
 (Wherein P 1 , P 2 , P 3 and X are as defined above, and W represents a halogen atom)
　ここで、ハロゲン原子は前記と同義であり、以下も同様である。
　具体的には、例えば、化合物（ＶＩ）は、化合物（ＶＩＩ）とハロゲン化剤とを反応させることにより式（ｄ）で表される酸ハライド［以下、化合物（ｄ）という］を得、次いで、化合物（ｄ）とＨＯ－Ｘ－ＯＨ（式中、Ｘは前記と同義である）で表されるジオールとを反応させることにより製造することができる。 Here, the halogen atom has the same meaning as described above, and the same applies to the following.
Specifically, for example, compound (VI) is obtained by reacting compound (VII) with a halogenating agent to obtain an acid halide represented by formula (d) [hereinafter referred to as compound (d)], The compound (d) can be produced by reacting a diol represented by HO—X—OH (wherein X is as defined above).
反応式（２）
　化合物（ｄ）は、例えば、ハロゲン化剤と化合物（ＶＩ）とを０～１２０℃で１～２４時間反応させることにより製造することができる。ハロゲン化剤の使用量は、化合物（ＶＩＩ）に対して１～１００倍モルであるのが好ましい。反応の際に、例えば、ヘキサン、トルエン、酢酸エチル、γ－ブチロラクトン、Ｎ－メチル－２－ピロリドン、テトラヒドロフラン等の溶媒を用いてもよい。また、反応の際にＮ，Ｎ－ジメチルホルムアミドやピリジン等の触媒を用いてもよい。 Reaction formula (2)
Compound (d) can be produced, for example, by reacting a halogenating agent with compound (VI) at 0 to 120 ° C. for 1 to 24 hours. The amount of the halogenating agent to be used is preferably 1 to 100 moles compared to Compound (VII). In the reaction, for example, a solvent such as hexane, toluene, ethyl acetate, γ-butyrolactone, N-methyl-2-pyrrolidone or tetrahydrofuran may be used. In the reaction, a catalyst such as N, N-dimethylformamide or pyridine may be used.
　ハロゲン化剤としては、ＳＯＷ２（式中、Ｗは前記と同義である）、三塩化リン、オキザリルクロリド、安息香酸クロリド等の公知のハロゲン化剤が挙げられ、中でも、ＳＯＷ２が好ましく、塩化チオニルがより好ましい。
　ハロゲン化剤としてＳＯＷ２を用いたとき、反応後、得られた反応混合物から未反応のＳＯＷ２を留去するのが好ましい。留去する方法としては、例えば、ベンゼン、トルエン等の共沸剤を添加し、ＳＯＷ２と共沸剤とを反応混合物から留去する方法等が挙げられる。 Examples of the halogenating agent include known halogenating agents such as SOW 2 (wherein W is as defined above), phosphorus trichloride, oxalyl chloride, benzoic acid chloride, among which SOW 2 is preferable, Thionyl chloride is more preferred.
When SOW 2 is used as the halogenating agent, unreacted SOW 2 is preferably distilled off from the resulting reaction mixture after the reaction. Examples of the method of distilling off include a method of adding an azeotropic agent such as benzene and toluene and distilling off SOW 2 and the azeotropic agent from the reaction mixture.
反応後、必要に応じて、化合物（ｄ）を有機合成化学で通常用いられる方法（各種クロマトグラフィー法、再結晶法、蒸留法等）で精製してもよい。 After the reaction, if necessary, the compound (d) may be purified by methods usually used in organic synthetic chemistry (various chromatographic methods, recrystallization methods, distillation methods, etc.).
反応式（３）
　化合物（ＶＩ）は、例えば、化合物（ｄ）とＨＯ－Ｘ－ＯＨ（式中、Ｘは前記と同義である）で表されるジオールとを、好ましくは塩基の存在下、溶媒中、－１０～５０℃で１～１００時間反応させることにより製造することができる。以下、ＨＯ－Ｘ－ＯＨ（式中、Ｘは前記と同義である）で表されるジオールを、単にジオールということもある。
ジオールの具体例としては、例えば、ヒドロキノン、２－メチルヒドロキノン、レゾルシノール、カテコール、２－フェニルヒドロキノン、４，４’－ビフェノール、３，４’－ビフェノール、２，２’－ビフェノール、４，４’－ジヒドロキシジフェニルエーテル、４，４’－ジヒドロキシジフェニルスルホン、９，９－ビス（４－ヒドロキシフェニル）フルオレン、２，６－ナフタレンジオール、１，４－ナフタレンジオール、１，５－ナフタレンジオール、１，８－ナフタレンジオール等の芳香族ジオール、１，４－ジヒドロキシシクロヘキサン、１，３－ジヒドロキシシクロヘキサン、１，２－ジヒドロキシシクロヘキサン、４，４’－ビシクロヘキサノール、トリシクロ［３．３．１．１３，７］デカン－１，３－ジオール等の脂環式ジオール等が挙げられる。 Reaction formula (3)
Compound (VI) is, for example, a compound (d) and a diol represented by HO—X—OH (wherein X is as defined above), preferably -10 in a solvent in the presence of a base. It can be produced by reacting at -50 ° C for 1-100 hours. Hereinafter, a diol represented by HO—X—OH (wherein X is as defined above) may be simply referred to as a diol.
Specific examples of the diol include, for example, hydroquinone, 2-methylhydroquinone, resorcinol, catechol, 2-phenylhydroquinone, 4,4′-biphenol, 3,4′-biphenol, 2,2′-biphenol, 4,4 ′. -Dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylsulfone, 9,9-bis (4-hydroxyphenyl) fluorene, 2,6-naphthalenediol, 1,4-naphthalenediol, 1,5-naphthalenediol, 1,8 -Aromatic diols such as naphthalenediol, 1,4-dihydroxycyclohexane, 1,3-dihydroxycyclohexane, 1,2-dihydroxycyclohexane, 4,4′-bicyclohexanol, tricyclo [3.3.1.13,7] Alicyclic geo such as decane-1,3-diol Le, and the like.
　化合物（ｄ）の使用量は、ジオールに対して２．１～１０倍モルであるのが好ましい。
　塩基としては、例えば、ピリジン、トリエチルアミン、Ｎ，Ｎ－ジメチルアニリン等のアミン、炭酸カリウム、水酸化ナトリウム等の無機塩基等が挙げられる。塩基の使用量は、化合物（ｄ）に対して１～１０倍モルであるのが好ましい。塩基の代わりにプロピレンオキシド等のエポキシ化合物を用いてもよい。
　溶媒としては、例えば、テトラヒドロフラン、１，４－ジオキサン等のエーテル系溶媒、アセトン、メチルエチルケトン等のケトン系溶媒、トルエン、キシレン等の芳香族炭化水素系溶媒、ジクロロメタン、クロロホルム、１，２－ジクロロエタン等の含ハロゲン溶媒、Ｎ－メチル－２－ピロリドン、ジメチルアセトアミド、Ｎ，Ｎ－ジメチルホルムアミド等のアミド系溶媒、γ-ブチロラクトン、酢酸エチル、酢酸ブチル等のエステル系溶媒、ジメチルスルホキシド等が挙げられる。これらの溶媒は単独で、または２種類以上混合して用いてもよい。 The amount of the compound (d) used is preferably 2.1 to 10 moles relative to the diol.
Examples of the base include amines such as pyridine, triethylamine and N, N-dimethylaniline, and inorganic bases such as potassium carbonate and sodium hydroxide. The amount of the base used is preferably 1 to 10 moles compared to the compound (d). An epoxy compound such as propylene oxide may be used in place of the base.
Examples of the solvent include ether solvents such as tetrahydrofuran and 1,4-dioxane, ketone solvents such as acetone and methyl ethyl ketone, aromatic hydrocarbon solvents such as toluene and xylene, dichloromethane, chloroform, 1,2-dichloroethane, and the like. And amide solvents such as N-methyl-2-pyrrolidone, dimethylacetamide and N, N-dimethylformamide, ester solvents such as γ-butyrolactone, ethyl acetate and butyl acetate, and dimethyl sulfoxide. These solvents may be used alone or in combination of two or more.
　反応後、必要に応じて、化合物（ＶＩ）を有機合成化学で通常用いられる方法（各種クロマトグラフィー法、再結晶法、蒸留法等）で精製してもよい。
　単離した化合物（ＶＩ）を、減圧下、１００～２５０℃で１～５０時間加熱することが好ましい。化合物（ＶＩ）中に不純物として化合物（ＶＩ）の加水分解物が含まれる場合、前記加熱により該加水分解物を化合物（ＶＩ）に変換することができる。 After the reaction, if necessary, the compound (VI) may be purified by methods usually used in organic synthetic chemistry (various chromatographic methods, recrystallization methods, distillation methods, etc.).
The isolated compound (VI) is preferably heated at 100 to 250 ° C. under reduced pressure for 1 to 50 hours. When the hydrolyzate of compound (VI) is contained as an impurity in compound (VI), the hydrolyzate can be converted to compound (VI) by the heating.
　本発明によって得られる化合物（ＶＩ）の具体例を以下の式に示す。 Specific examples of the compound (VI) obtained by the present invention are shown in the following formula.
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
＜ポリイミド前駆体（Ｖ）の製造方法＞
　ポリイミド前駆体（Ｖ）は、例えば、化合物（ＶＩ）を含む１種類以上のテトラカルボン酸二無水物とＨ２Ｎ－Ａ－ＮＨ２（式中、Ａは前記と同義である）で表されるジアミンとを溶媒中、０～１００℃で１～３００時間反応させることにより製造することができる。以下、Ｈ２Ｎ－Ａ－ＮＨ２（式中、Ａは前記と同義である）で表されるジアミンを、単にジアミンということもある。 <Method for producing polyimide precursor (V)>
The polyimide precursor (V) is represented by, for example, one or more kinds of tetracarboxylic dianhydrides including the compound (VI) and H 2 NA—NH 2 (wherein A is as defined above). It can be produced by reacting with diamine in a solvent at 0 to 100 ° C. for 1 to 300 hours. Hereinafter, the diamine represented by H 2 N—A—NH 2 (wherein A is as defined above) may be simply referred to as diamine.
　ジアミンの具体例としては、例えば、４，４’－メチレンジシクロヘキシルアミン、３，３’－ジメチル－４，４’－メチレンジシクロヘキシルアミン、３，３’－ジエチル－４，４’－メチレンジシクロヘキシルアミン、３，３’ ，５，５’－テトラメチル－４，４’－メチレンジシクロヘキシルアミン、３，３’ ，５，５’－テトラエチル－４，４’－メチレンジシクロヘキシルアミン、イソホロンジアミン、トランス－１，４－シクロヘキサンジアミン、シス－１，４－シクロヘキサンジアミン、１，４－シクロヘキサンビス（メチルアミン）、２，５－ビス（アミノメチル）ビシクロ［２．２．１］ヘプタン、２，６－ビス（アミノメチル）ビシクロ［２．２．１］ヘプタン、３，８－ビス（アミノメチル）トリシクロ［５．２．１．０］デカン、トリシクロ［３．３．１．１３，７］デカン－１，３－ジアミン、２，２－ビス（４－アミノシクロヘキシル）プロパン、２，２－ビス（４－アミノシクロヘキシル）ヘキサフルオロプロパン、１，３－プロパンジアミン、１，４－テトラメチレンジアミン、１，５－ペンタメチレンジアミン、１，６－ヘキサメチレンジアミン、１，７－ヘプタメチレンジアミン、１，８－オクタメチレンジアミン、１，９－ノナメチレンジアミン等の脂肪族ジアミン、ｐ－フェニレンジアミン、ｍ－フェニレンジアミン、２，４－ジアミノトルエン、２，５－ジアミノトルエン、２，４－ジアミノキシレン、２，４－ジアミノジュレン、４，４’－メチレンジアニリン、３，３’－ジメチル－４，４’－メチレンジアニリン、３，３’－ジエチル－４，４’－メチレンジアニリン、２，２’－ジメチル－４，４’－メチレンジアニリン、２，２’－ジエチル－４，４’－メチレンジアニリン、３，３’ ， ５，５’－テトラメチル－４，４’－メチレンジアニリン、３，３’ ， ５，５’－テトラエチル－４，４’－メチレンジアニリン、２，２’ ， ６，６’－テトラメチル－４，４’－メチレンジアニリン、２，２’ ， ６，６’－テトラエチル－４，４’－メチレンジアニリン、４，４’－ジアミノジフェニルエーテル、３，４’－ジアミノジフェニルエーテル、３，３’－ジアミノジフェニルエーテル、２，４’－ジアミノジフェニルエーテル、２，２’－ジアミノジフェニルエーテル、４，４’－ジアミノジフェニルスルホン、３，３’－ジアミノジフェニルスルホン、４，４’－ジアミノベンゾフェノン、３，３’－ジアミノベンゾフェノン、４，４’－ジアミノベンズアニリド、ベンジジン、３，３’－ジヒドロキシベンジジン、３，３’－ジメトキシベンジジン、ｏ－トリジン、ｍ－トリジン、２，２’－ビス（トリフルオロメチル）ベンジジン、１，４－ビス（４－アミノフェノキシ）ベンゼン、１，４－ビス（３－アミノフェノキシ）ベンゼン、１，３－ビス（４－アミノフェノキシ）ベンゼン、１，３－ビス（３－アミノフェノキシ）ベンゼン、４，４’－ビス（４－アミノフェノキシ）ビフェニル、ビス［３－（３－アミノフェノキシ）フェニル］スルホン、ビス［４－（３－アミノフェノキシ）フェニル］スルホン、ビス［４－（４－アミノフェノキシ）フェニル］スルホン、２，２－ビス［４－（４－アミノフェノキシ）フェニル］プロパン、２，２－ビス［４－（４－アミノフェノキシ）フェニル］ヘキサフルオロプロパン、２，２－ビス（４－アミノフェニル）ヘキサフルオロプロパン、ｐ－ターフェニレンジアミン等の芳香族ジアミン等が挙げられる。これらのジアミンは単独で、または２種類以上混合して用いてもよい。 Specific examples of diamines include, for example, 4,4′-methylenedicyclohexylamine, 3,3′-dimethyl-4,4′-methylenedicyclohexylamine, 3,3′-diethyl-4,4′-methylenedicyclohexylamine, 3,3 ′, 5,5′-tetramethyl-4,4′-methylenedicyclohexylamine, 3,3 ′, 5,5′-tetraethyl-4,4′-methylenedicyclohexylamine, isophoronediamine, trans-1, 4-cyclohexanediamine, cis-1,4-cyclohexanediamine, 1,4-cyclohexanebis (methylamine), 2,5-bis (aminomethyl) bicyclo [2.2.1] heptane, 2,6-bis ( Aminomethyl) bicyclo [2.2.1] heptane, 3,8-bis (aminomethyl) tricyclo [5.2 .1.0] decane, tricyclo [3.3.1.13,7] decane-1,3-diamine, 2,2-bis (4-aminocyclohexyl) propane, 2,2-bis (4-aminocyclohexyl) ) Hexafluoropropane, 1,3-propanediamine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylene Diamine, aliphatic diamine such as 1,9-nonamethylenediamine, p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,4-diaminoxylene, 2,4- Diaminodurene, 4,4'-methylenedianiline, 3,3'-dimethyl-4,4'-methylenedianiline, 3,3 ' Diethyl-4,4′-methylenedianiline, 2,2′-dimethyl-4,4′-methylenedianiline, 2,2′-diethyl-4,4′-methylenedianiline, 3,3 ′, 5 5′-tetramethyl-4,4′-methylenedianiline, 3,3 ′, 5,5′-tetraethyl-4,4′-methylenedianiline, 2,2 ′, 6,6′-tetramethyl-4 , 4′-methylenedianiline, 2,2 ′, 6,6′-tetraethyl-4,4′-methylenedianiline, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′- Diaminodiphenyl ether, 2,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyls Hong, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzanilide, benzidine, 3,3'-dihydroxybenzidine, 3,3'-dimethoxybenzidine, o-tolidine, m -Tolidine, 2,2'-bis (trifluoromethyl) benzidine, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (4- Aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, bis [3- (3-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2 Bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, p -Aromatic diamines such as terphenylenediamine. These diamines may be used alone or in combination of two or more.
　化合物（ＶＩ）を含む２種類以上のテトラカルボン酸二無水物を使用するとき、２種類以上の化合物（ＶＩ）を用いてもよく、１種類以上の化合物（ＶＩ）と１種類以上の化合物（ＶＩ）以外のテトラカルボン酸二無水物とを併用してもよい。
　化合物（ＶＩ）以外のテトラカルボン酸二無水物としては、例えば、ピロメリット酸二無水物、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物、３，３’，４，４’－ベンゾフェノンテトラカルボン酸二無水物、３，３’，４，４’－ビフェニルエーテルテトラカルボン酸二無水物、３，３’，４，４’－ビフェニルスルホンテトラカルボン酸二無水物、２，２’－ビス（３，４－ジカルボキシフェニル）ヘキサフルオロプロパン酸二無水物、２，２’－ビス（３，４－ジカルボキシフェニル）プロパン酸二無水物、ハイドロキノンビス（トリメリテートアンハイドライド）、１，４，５，８－ナフタレンテトラカルボン酸二無水物、２，３，６，７－ナフタレンテトラカルボン酸二無水物等の芳香族テトラカルボン酸二無水物、ビシクロ［２．２．２］オクト－７－エン－２，３，５，６－テトラカルボン酸二無水物、ビシクロ［２．２．１］ヘプタンテトラカルボン酸二無水物、テトラヒドロフラン－２，３，４，５－テトラカルボン酸二無水物、ジシクロヘキシル－３，３’ ，４，４’－テトラカルボン酸二無水物、シス、シス、シス－１，２，４，５－シクロヘキサンテトラカルボン酸二無水物、１，２，３，４－シクロブタンテトラカルボン酸二無水物、１，２，３，４－シクロペンタンテトラカルボン酸二無水物等の脂環式テトラカルボン酸二無水物等が挙げられる。
　１種類以上の化合物（ＶＩ）と１種類以上の化合物（ＶＩ）以外のテトラカルボン酸二無水物とを併用するときの１種類以上の化合物（ＶＩ）の使用量は、使用するテトラカルボン酸二無水物の全量に対して２０モル％以上であるのが好ましく、５０モル％以上であるのがより好ましい。 When two or more kinds of tetracarboxylic dianhydrides containing compound (VI) are used, two or more kinds of compounds (VI) may be used, and one or more kinds of compounds (VI) and one or more kinds of compounds ( A tetracarboxylic dianhydride other than VI) may be used in combination.
Examples of tetracarboxylic dianhydrides other than compound (VI) include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4. '-Benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylsulfone tetracarboxylic dianhydride, 2, 2'-bis (3,4-dicarboxyphenyl) hexafluoropropanoic dianhydride, 2,2'-bis (3,4-dicarboxyphenyl) propanoic dianhydride, hydroquinone bis (trimellitic anhydride) ), 1,4,5,8-naphthalenetetracarboxylic dianhydride, aromatic tetracarboxylic dianhydrides such as 2,3,6,7-naphthalenetetracarboxylic dianhydride, bicyclo [2 2.2.2] Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.1] heptanetetracarboxylic dianhydride, tetrahydrofuran-2,3,4, 5-tetracarboxylic dianhydride, dicyclohexyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, cis, cis, cis-1,2,4,5-cyclohexanetetracarboxylic dianhydride, And alicyclic tetracarboxylic dianhydrides such as 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,2,3,4-cyclopentanetetracarboxylic dianhydride.
When one or more types of compound (VI) and one or more types of tetracarboxylic dianhydride other than compound (VI) are used in combination, the amount of one or more types of compound (VI) used is the amount of tetracarboxylic acid dihydrate used. It is preferably 20 mol% or more, more preferably 50 mol% or more, based on the total amount of anhydride.
　ジアミンの使用量は、使用するテトラカルボン酸二無水物の全量に対して０．８～１．２倍モルであるのが好ましく、０．９５～１．０５倍モルであるのがより好ましく、さらには０．９９～１．０１倍モルであるのが好ましい。
　溶媒としては、例えば、Ｎ，Ｎ－ジメチルホルムアミド、ジメチルアセトアミド、Ｎ－メチルピロリドン等のアミド系溶媒、γ－ブチロラクトン、γ－バレロラクトン、δ－バレロラクトン、γ－カプロラクトン、ε－カプロラクトン、α－メチル－γ－ブチロラクトン等の環状エステル系溶媒、エチレンカーボネート、プロピレンカーボネート等のカーボネート系溶媒、トリエチレングリコール等のグリコール系溶媒、ｍ－クレゾール、ｐ－クレゾール、３－クロロフェノール、４－クロロフェノール等のフェノール系溶媒、アセトフェノン、１，３－ジメチル－２－イミダゾリジノン、スルホラン、ジメチルスルホキシド等が挙げられる。 The amount of diamine used is preferably 0.8 to 1.2 moles, more preferably 0.95 to 1.05 moles, based on the total amount of tetracarboxylic dianhydride used. Further, it is preferably 0.99 to 1.01 times mole.
Examples of the solvent include amide solvents such as N, N-dimethylformamide, dimethylacetamide, N-methylpyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α- Cyclic ester solvents such as methyl-γ-butyrolactone, carbonate solvents such as ethylene carbonate and propylene carbonate, glycol solvents such as triethylene glycol, m-cresol, p-cresol, 3-chlorophenol, 4-chlorophenol, etc. Phenolic solvents, acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide and the like.
　ジアミンとして芳香族ジアミンを使用するとき、使用するジアミンの重量と使用するテトラカルボン酸無水物の重量との和は、反応液の重量に対して５～４０％であるのが好ましい。また、ジアミンとして脂肪族ジアミンのみを使用するとき、使用するジアミンの重量と使用するテトラカルボン酸無水物の重量との和は、反応液の重量に対して５～３０％であるのが好ましい。 When an aromatic diamine is used as the diamine, the sum of the weight of the diamine used and the weight of the tetracarboxylic acid anhydride used is preferably 5 to 40% based on the weight of the reaction solution. When only an aliphatic diamine is used as the diamine, the sum of the weight of the diamine used and the weight of the tetracarboxylic anhydride used is preferably 5 to 30% with respect to the weight of the reaction solution.
　ポリイミド前駆体（Ｖ）の０．５重量％ジメチルアセトアミド溶液の３０℃における固有粘度は０．１ｄＬ／ｇ以上であるのが好ましい。該固有粘度が０．１ｄＬ／ｇであるポリイミド前駆体（Ｖ）は優れた製膜性を有する。例えば、ポリイミド前駆体（Ｖ）の溶液をガラス等の基板上に塗布し、次いで、該基板を乾燥する等の方法によりポリイミド前駆体（Ｖ）の膜を得るとき、該固有粘度が０．１ｄＬ／ｇであるポリイミド前駆体（Ｖ）を使用して得た膜はひび割れにくい等の効果を有する。ポリイミド前駆体（Ｖ）の数平均分子量は、２０００～１００００００であるのが好ましい。 The intrinsic viscosity at 30 ° C. of a 0.5 wt% dimethylacetamide solution of the polyimide precursor (V) is preferably 0.1 dL / g or more. The polyimide precursor (V) having an intrinsic viscosity of 0.1 dL / g has excellent film forming properties. For example, when a polyimide precursor (V) film is obtained by applying a solution of the polyimide precursor (V) onto a substrate such as glass and then drying the substrate, the intrinsic viscosity is 0.1 dL. The film obtained by using the polyimide precursor (V) which is / g has effects such as being hard to crack. The number average molecular weight of the polyimide precursor (V) is preferably 2,000 to 1,000,000.
　反応後、得られたポリイミド前駆体（Ｖ）の溶液をそのまま後述のポリイミドの製造に用いてもよい（例えば、Ｊｏｕｒｎａｌ　ｏｆ　Ａｐｐｌｉｅｄ　Ｐｏｌｙｍｅｒ　Ｓｃｉｅｎｃｅ，１９８６年，第３２巻，ｐ．３１３３、Ｐｏｌｙｍｅｒ，１９９３年，第３４巻，ｐ．８４９記載の方法等）。また、反応後、必要に応じて、ポリイミド前駆体（Ｖ）を高分子化学で通常用いられる方法（再沈殿等）で精製してもよい。 After the reaction, the obtained solution of the polyimide precursor (V) may be used as it is for the production of the later-described polyimide (for example, Journal of Applied Polymer Science, 1986, Vol. 32, p. 3133, Polymer, 1993). 34, p. 849, etc.). In addition, after the reaction, the polyimide precursor (V) may be purified by a method usually used in polymer chemistry (such as reprecipitation) as necessary.
＜ポリイミド（Ｉ）の製造方法＞
　ポリイミド（Ｉ）は、例えば、ポリイミド前駆体（Ｖ）をイミド化することにより製造することができる。ポリイミド前駆体（Ｖ）をイミド化する際には、ポリイミド前駆体（Ｖ）に含まれるアミド酸単位がイミド単位に変換される。ポリイミド前駆体（Ｖ）をイミド化する方法としては、例えば、熱イミド化、化学イミド化等が挙げられる。
　熱イミド化によりポリイミド（Ｉ）を製造する方法としては、例えば、ポリイミド前駆体（Ｖ）を溶媒中、１５０～４００℃で０．５～２００時間加熱することによりポリイミド（Ｉ）を製造する方法等が挙げられる。 <Production method of polyimide (I)>
The polyimide (I) can be produced, for example, by imidizing the polyimide precursor (V). When imidizing the polyimide precursor (V), the amic acid unit contained in the polyimide precursor (V) is converted into an imide unit. Examples of the method for imidizing the polyimide precursor (V) include thermal imidization and chemical imidization.
As a method for producing polyimide (I) by thermal imidization, for example, a method for producing polyimide (I) by heating polyimide precursor (V) in a solvent at 150 to 400 ° C. for 0.5 to 200 hours. Etc.
　溶媒としては、例えば、Ｎ，Ｎ－ジメチルホルムアミド、ジメチルアセトアミド、Ｎ－メチルピロリドン等のアミド系溶媒、γ－ブチロラクトン、γ－バレロラクトン、δ－バレロラクトン、γ－カプロラクトン、ε－カプロラクトン、α－メチル－γ－ブチロラクトン等の環状エステル系溶媒、エチレンカーボネート、プロピレンカーボネート等のカーボネート系溶媒、トリエチレングリコール等のグリコール系溶媒、ｍ－クレゾール、ｐ－クレゾール、３－クロロフェノール、４－クロロフェノール等のフェノール系溶媒、アセトフェノン、１，３－ジメチル－２－イミダゾリジノン、スルホラン、ジメチルスルホキシド等が挙げられる。 Examples of the solvent include amide solvents such as N, N-dimethylformamide, dimethylacetamide, N-methylpyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α- Cyclic ester solvents such as methyl-γ-butyrolactone, carbonate solvents such as ethylene carbonate and propylene carbonate, glycol solvents such as triethylene glycol, m-cresol, p-cresol, 3-chlorophenol, 4-chlorophenol, etc. Phenolic solvents, acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide and the like.
　熱イミド化後、必要に応じて、ポリイミド（Ｉ）を高分子化学で通常用いられる方法（再沈殿等）で精製してもよい。得られたポリイミド（Ｉ）を、例えば、ジメチルアセトアミド等に溶解して溶液とし、ガラス、銅、アルミニウム、ステンレス、シリコン等の基板上に塗布し、次いで、該基板を４０～１８０℃で１～５時間乾燥し、好ましくは、次いで１５０～４００℃で０．５～５時間加熱することによりポリイミド（Ｉ）の膜を製造することができる。
　熱イミド化によりポリイミド（Ｉ）を製造するその他の方法としては、例えば、ポリイミド前駆体（Ｖ）の膜を１５０～４００℃で５分間～５時間加熱することによりポリイミド（Ｉ）を製造する方法等が挙げられ、具体的には、例えば、ポリイミド前駆体（Ｖ）の溶液をガラス、銅、アルミニウム、ステンレス、シリコン等の基板上に塗布し、次いで、該基板を４０～１８０℃で５分間～５時間乾燥することによりポリイミド前駆体（Ｖ）の膜を得、次いで、該膜を１５０～４００℃で５分間～５時間加熱することによりポリイミド（Ｉ）の膜を製造する方法等が挙げられる。ポリイミド前駆体（Ｖ）の溶液における溶媒としては、熱イミド化に用いる溶媒として前記に挙げたものが例示される。 After thermal imidization, if necessary, polyimide (I) may be purified by a method usually used in polymer chemistry (such as reprecipitation). The obtained polyimide (I) is dissolved in, for example, dimethylacetamide to form a solution, which is applied onto a substrate such as glass, copper, aluminum, stainless steel, or silicon, and then the substrate is heated at 40 to 180 ° C. for 1 to A polyimide (I) film can be produced by drying for 5 hours, and preferably heating at 150 to 400 ° C. for 0.5 to 5 hours.
As another method of producing polyimide (I) by thermal imidization, for example, a method of producing polyimide (I) by heating a film of polyimide precursor (V) at 150 to 400 ° C. for 5 minutes to 5 hours Specifically, for example, a solution of the polyimide precursor (V) is applied on a substrate such as glass, copper, aluminum, stainless steel, or silicon, and then the substrate is heated at 40 to 180 ° C. for 5 minutes. And a method of producing a polyimide (I) film by drying for 5 hours to obtain a polyimide precursor (V) film, and then heating the film at 150 to 400 ° C. for 5 minutes to 5 hours. It is done. Examples of the solvent in the solution of the polyimide precursor (V) include those mentioned above as the solvent used for thermal imidization.
　化学イミド化によりポリイミド（Ｉ）を製造する方法としては、例えば、ポリイミド前駆体（Ｖ）を溶媒中、ピリジン、トリエチルアミン等のアミンの存在下、無水酢酸等の化学イミド化剤で０～５０℃で１～４８時間処理する方法等が挙げられる。化学イミド化剤の使用量は、ポリイミド前駆体（Ｖ）に含まれるアミド酸単位に対して１～１００倍モルであるのが好ましい。アミンの使用量は、化学イミド化剤に対して０．１～５０倍モルであるのが好ましい。溶媒としては、熱イミド化に用いる溶媒として前記に挙げたものが例示される。
　化学イミド化後、必要に応じて、ポリイミド（Ｉ）を高分子化学で通常用いられる方法（再沈殿等）で精製してもよい。得られたポリイミド（Ｉ）を、例えば、ジメチルアセトアミド等に溶解して溶液とし、ガラス、銅、アルミニウム、ステンレス、シリコン等の基板上に塗布し、次いで、該基板を４０～１８０℃で０．１～５時間乾燥することによりポリイミド（Ｉ）の膜を製造することができる。該ポリイミド（Ｉ）の膜を、さらに１５０～４００℃で０．５～５時間加熱するのが好ましい。
　化学イミド化によりポリイミド（Ｉ）を製造するその他の方法としては、例えば、前記ポリイミド前駆体（Ｖ）の膜をピリジン、トリエチルアミン等のアミンと無水酢酸等の化学イミド化剤とを含む溶液に浸漬することによりポリイミド（Ｉ）の膜を製造する方法等が挙げられる。該ポリイミド（Ｉ）の膜を、さらに１５０～４００℃で０．５～５時間加熱するのが好ましい。 As a method for producing polyimide (I) by chemical imidization, for example, a polyimide precursor (V) in a solvent in the presence of an amine such as pyridine or triethylamine is heated at 0 to 50 ° C. with a chemical imidizing agent such as acetic anhydride. And a method of treating for 1 to 48 hours. The amount of the chemical imidizing agent used is preferably 1 to 100 times mol for the amic acid unit contained in the polyimide precursor (V). The amount of amine used is preferably 0.1 to 50 times the mole of the chemical imidizing agent. Examples of the solvent include those listed above as solvents used for thermal imidization.
After chemical imidization, if necessary, polyimide (I) may be purified by a method commonly used in polymer chemistry (reprecipitation or the like). The obtained polyimide (I) is dissolved in, for example, dimethylacetamide to form a solution, which is applied onto a substrate such as glass, copper, aluminum, stainless steel, or silicon. A polyimide (I) film can be produced by drying for 1 to 5 hours. The polyimide (I) film is preferably further heated at 150 to 400 ° C. for 0.5 to 5 hours.
As another method for producing polyimide (I) by chemical imidization, for example, the polyimide precursor (V) film is immersed in a solution containing an amine such as pyridine or triethylamine and a chemical imidizing agent such as acetic anhydride. And a method for producing a polyimide (I) film. The polyimide (I) film is preferably further heated at 150 to 400 ° C. for 0.5 to 5 hours.
　ポリイミド（Ｉ）は、例えば、ポリイミド前駆体（Ｖ）をＮ，Ｎ－ジシクロヘキシルカルボジイミド、トリフルオロ無水酢酸等で処理することによりイソイミド単位を有するポリマーを得、次いで、該イソイミド単位を有するポリマーを加熱することにより製造することもできる（例えば、Ｐｏｌｙｍｅｒ　Ｊｏｕｒｎａｌ，１９９４年，第２６巻，ｐ．３１５記載の方法等）。このポリイミド（Ｉ）の製造方法では、ポリイミド前駆体（Ｖ）に含まれるアミド酸単位がイソイミド単位に変換され、次いで、該イソイミド単位がイミド単位に変換される。 For example, the polyimide (I) is obtained by treating the polyimide precursor (V) with N, N-dicyclohexylcarbodiimide, trifluoroacetic anhydride or the like to obtain a polymer having an isoimide unit, and then heating the polymer having the isoimide unit. (For example, the method described in Polymer Journal, 1994, Vol. 26, p. 315, etc.). In this method for producing polyimide (I), the amic acid unit contained in the polyimide precursor (V) is converted into an isoimide unit, and then the isoimide unit is converted into an imide unit.
　本発明のポリイミド（Ｉ）は高い耐熱性を有するため、液晶ディスプレー（ＬＣＤ）用基板、有機エレクトロルミネッセンスディスプレー（ＥＬＤ）用基板等に有用である。また、本発明のポリイミド（Ｉ）は、透明性、低誘電率、光線透過率、複屈折率、荷重たわみ温度、各種硬度、吸水率、引っ張りおよび曲げに対する強度、弾性率、ヤング率、可撓性、電気絶縁性、耐アーク性、耐薬品性、耐熱水性、各種溶媒への溶解性等に優れる。 Since the polyimide (I) of the present invention has high heat resistance, it is useful for liquid crystal display (LCD) substrates, organic electroluminescence display (ELD) substrates, and the like. In addition, the polyimide (I) of the present invention has transparency, low dielectric constant, light transmittance, birefringence, deflection temperature under load, various hardness, water absorption, strength against tension and bending, elastic modulus, Young's modulus, flexibility Excellent in electrical properties, electrical insulation, arc resistance, chemical resistance, hot water resistance, solubility in various solvents, etc.
　以下、本発明を合成例および実施例により具体的に説明する。 Hereinafter, the present invention will be specifically described with reference to synthesis examples and examples.
＜ＦＴ－ＩＲスペクトル＞
　日本分光社製フーリエ変換赤外分光光度計（ＦＴ－ＩＲ５３００またはＦＴ－ＩＲ３５０）を用いた。
＜１Ｈ－ＮＭＲスペクトル＞
　日本電子社製ＮＭＲ分光光度計（ＥＣＰ４００）を用いた。
＜融点＞
　ブルカーエイエックス社製示差走査熱量分析装置（ＤＳＣ３１００）を用いて、窒素雰囲気中、昇温速度２℃／分で測定した（ＤＳＣ分析）。
＜固有粘度＞
　オストワルド粘度計を用いて、０．５重量％ポリイミド前駆体溶液（溶媒：ジメチルアセトアミド）の固有粘度を３０℃で測定した。
＜ガラス転移温度（Ｔｇ）＞
　動的粘弾性測定によりポリイミド膜のガラス転移温度を求めた。ポリイミド膜は、長さ２０ｍｍ、幅５ｍｍ、膜厚約２０μｍのものを用いた。ブルカーエイエックスエス社製熱機械分析装置（ＴＭＡ４０００）を用いて、周波数０．１Ｈｚ、昇温速度５℃／分にてポリイミド膜のガラス転移温度を測定した。
＜線熱膨張係数（ＣＴＥ）＞
　ブルカーエイエックスエス社製熱機械分析装置（ＴＭＡ４０００）を用いて、１００℃から２００℃まで５℃／分でポリイミド膜を昇温させたときのポリイミド膜の伸び率ΔＬ／Ｌ０（ΔＬ；ポリイミド膜の伸び、Ｌ０；ポリイミド膜の測定前の長さ）を測定した（ポリイミド膜：長さ２０ｍｍ×幅５ｍｍ、チャック間長１５ｍｍ、膜厚１μｍ当たり荷重０．５ｇ）。該伸び率を測定時の温度幅［１００（Ｋ）］で割り算することによりポリイミド膜の線膨張係数を求めた。
＜カットオフ波長＞
　日本分光社製紫外可視分光光度計（Ｖ－５３０）を用いて、２００ｎｍから９００ｎｍの光の透過率を測定した。２００ｎｍから９００ｎｍの範囲で透過率が０．５％以下となる最短波長をカットオフ波長とした。カットオフ波長が短い程、ポリイミド膜の透明性が良好であることを意味する。
＜誘電率（εｃａｌ）＞
　アタゴ社製アッベ屈折計（４Ｔまたは１Ｔ）を用いて、ポリイミド膜の面と平行な方向における屈折率（ｎｉｎ）とポリイミド膜の面と垂直な方向における屈折率（ｎｏｕｔ）を測定し、下記式により１ＭＨｚにおけるポリイミド膜の誘電率（εｃａｌ）を求めた。
ポリイミド膜の平均屈折率；ｎａｖ＝（２ｎｉｎ＋ｎｏｕｔ）／３
ポリイミド膜の誘電率；εｃａｌ＝１．１×ｎａｖ ２ <FT-IR spectrum>
A Fourier transform infrared spectrophotometer (FT-IR5300 or FT-IR350) manufactured by JASCO Corporation was used.
< 1 H-NMR spectrum>
An NMR spectrophotometer (ECP400) manufactured by JEOL Ltd. was used.
<Melting point>
Using a differential scanning calorimeter (DSC3100) manufactured by Bruker Ax, measurement was performed in a nitrogen atmosphere at a heating rate of 2 ° C./min (DSC analysis).
<Intrinsic viscosity>
Using an Ostwald viscometer, the intrinsic viscosity of a 0.5 wt% polyimide precursor solution (solvent: dimethylacetamide) was measured at 30 ° C.
<Glass transition temperature (Tg)>
The glass transition temperature of the polyimide film was determined by dynamic viscoelasticity measurement. A polyimide film having a length of 20 mm, a width of 5 mm, and a film thickness of about 20 μm was used. The glass transition temperature of the polyimide film was measured at a frequency of 0.1 Hz and a heating rate of 5 ° C./min using a Bruker AXS thermomechanical analyzer (TMA4000).
<Linear thermal expansion coefficient (CTE)>
Elongation rate ΔL / L0 (ΔL: polyimide film) of polyimide film when the temperature of the polyimide film is increased from 100 ° C. to 200 ° C. at 5 ° C./min using a Bruker AXS thermomechanical analyzer (TMA4000) (L0; length before measurement of polyimide film) was measured (polyimide film: length 20 mm × width 5 mm, length between chucks 15 mm, load 0.5 g per film thickness of 1 μm). The linear expansion coefficient of the polyimide film was determined by dividing the elongation by the temperature range [100 (K)] at the time of measurement.
<Cutoff wavelength>
Using a UV-visible spectrophotometer (V-530) manufactured by JASCO Corporation, the transmittance of light from 200 nm to 900 nm was measured. The shortest wavelength at which the transmittance was 0.5% or less in the range of 200 nm to 900 nm was defined as the cutoff wavelength. The shorter the cutoff wavelength, the better the transparency of the polyimide film.
<Dielectric constant (ε cal )>
Using an Abbe refractometer (4T or 1T) manufactured by Atago Co., Ltd., the refractive index (n in ) in the direction parallel to the surface of the polyimide film and the refractive index (n out ) in the direction perpendicular to the surface of the polyimide film are measured, The dielectric constant (ε cal ) of the polyimide film at 1 MHz was determined by the following formula.
Average refractive index of polyimide film; n av = (2n in + n out ) / 3
Dielectric constant of polyimide film; ε cal = 1.1 × n av 2
［合成例１］５－ホルミル－２，３－ビシクロ［２．２．１］ヘプタンジカルボン酸無水物の合成
　２，３－（ビシクロ［２．２．１］ヘプト－５－エン）ジカルボン酸無水物は、シクロペンタジエンと無水マレイン酸とを「実験化学講座（第１９巻）有機合成Ｉ　炭化水素・ハロゲン化合物」，第４版，丸善株式会社，１９９２年，ｐ．１７３に記載の方法に準じて反応させることにより製造して得た。
　内容１リットルのステンレス製の電磁攪拌機付きオートクレーブに、２，３－（ビシクロ［２．２．１］ヘプト－５－エン）ジカルボン酸無水物１１８ｇ（０．７２ｍｏｌ）、アセトニトリル２００ｍＬ、Ｒｈ（ＣＯ）（ＰＰｈ３）（ａｃａｃ）７ｍｇおよびトリフェニルフォスフィン３７６ｍｇを仕込み、オートクレーブの内圧を５ＭＰａに保ちながら約３０分でオートクレーブの内温を１２０℃まで昇温し、次いで、１２０℃、５ＭＰａで４時間攪拌した。昇温および反応の際に、圧力調節弁を通して一酸化炭素と水素との１／１混合ガス（モル比）をオートクレーブに供給することにより、オートクレーブの内圧を常に５ＭＰａに保持した。 [Synthesis Example 1] Synthesis of 5-formyl-2,3-bicyclo [2.2.1] heptanedicarboxylic anhydride 2,3- (bicyclo [2.2.1] hept-5-ene) dicarboxylic anhydride The product is cyclopentadiene and maleic anhydride, “Experimental Chemistry Course (Vol. 19) Organic Synthesis I Hydrocarbon / Halogen Compounds”, 4th edition, Maruzen Co., Ltd., 1992, p. It was obtained by reacting according to the method described in 173.
Contents In a 1 liter stainless steel autoclave with a magnetic stirrer, 118 g (0.72 mol) of 2,3- (bicyclo [2.2.1] hept-5-ene) dicarboxylic acid anhydride, 200 mL of acetonitrile, Rh (CO) (PPh 3 ) (acac) 7 mg and triphenylphosphine 376 mg were charged, and the internal temperature of the autoclave was raised to 120 ° C. in about 30 minutes while maintaining the internal pressure of the autoclave at 5 MPa. Stir. During the temperature increase and the reaction, a 1/1 mixed gas (molar ratio) of carbon monoxide and hydrogen was supplied to the autoclave through the pressure control valve, so that the internal pressure of the autoclave was always maintained at 5 MPa.
　反応後、反応液を１２０℃から１０℃まで１時間で冷却し、次いで、１０℃で３時間反応液を攪拌した。析出した沈殿を濾取し、該沈殿を乾燥して５－ホルミル－２，３－ビシクロ［２．２．１］ヘプタンジカルボン酸無水物１３４ｇを得た（収率９６％）。
１Ｈ－ＮＭＲ（アセトン－ｄ６，δｐｐｍ）；１．４０－１．５３（ｍ，１Ｈ），１．６５－１．７３（ｍ，１Ｈ），２．０９－２．１８（ｍ，１Ｈ），２．４８－２．５７（ｍ，１Ｈ），２．８１－２．８８（ｂｒ，１Ｈ），３．１２－３．２１（ｄ，２Ｈ），３．６０－３．６８（ｍ，１Ｈ），３．７０－３．７８（ｍ，１Ｈ），９．６６（ｓ，１Ｈ） After the reaction, the reaction solution was cooled from 120 ° C. to 10 ° C. over 1 hour, and then the reaction solution was stirred at 10 ° C. for 3 hours. The deposited precipitate was collected by filtration and dried to obtain 134 g of 5-formyl-2,3-bicyclo [2.2.1] heptanedicarboxylic acid anhydride (yield 96%).
1 H-NMR (acetone-d 6 , δ ppm); 1.40-1.53 (m, 1H), 1.65-1.73 (m, 1H), 2.09-2.18 (m, 1H) ), 2.48-2.57 (m, 1H), 2.81-2.88 (br, 1H), 3.12-3.21 (d, 2H), 3.60-3.68 (m) , 1H), 3.70-3.78 (m, 1H), 9.66 (s, 1H)
［合成例２］２，３，５－ビシクロ［２．２．１］ヘプタントリカルボン酸の合成
　５－ホルミル－２，３－ビシクロ［２．２．１］ヘプタンジカルボン酸無水物１３４ｇ、アセトニトリル１３８０ｍＬおよびメタノール１３８０ｍＬを四つ口フラスコに仕込み、次いで、２７６ｇのオキソン（登録商標；デュポン社製、過硫酸水素カリウム４３重量％含有）を加え、６時間攪拌した。反応液を濾過し、濾液に１モル／Ｌの塩酸水溶液６９０ｍＬを加えた。得られた溶液をメチルイソブチルケトン９９０ｍＬで３回抽出し、さらに、メチルイソブチルケトン５９０ｍＬで２回抽出し、得られた有機層をあわせて飽和食塩水で洗浄し、有機層を無水硫酸マグネシウムで乾燥し、溶媒を留去して２，３，５－ビシクロ［２．２．１］ヘプタントリカルボン酸１２４ｇを得た（収率７９％）。
１Ｈ－ＮＭＲ（Ｄ２Ｏ，δｐｐｍ）；１．４２－１．６３（ｍ，２Ｈ），１．６９－１．８２（ｍ，１Ｈ），１．８５－１．９８（ｍ，１Ｈ），２．６５－２．７１（ｂｒ，１Ｈ），２．７９－２．８６（ｂｒ，１Ｈ），３．００－３．１９（ｍ，２Ｈ），３．２０－３．３０（ｍ，１Ｈ），９．５０－１５．２５（ｍ，３Ｈ） Synthesis Example 2 Synthesis of 2,3,5-bicyclo [2.2.1] heptanetricarboxylic acid 134 g of 5-formyl-2,3-bicyclo [2.2.1] heptanedicarboxylic acid anhydride, 1380 mL of acetonitrile and 1380 mL of methanol was charged into a four-necked flask, and then 276 g of oxone (registered trademark; manufactured by DuPont, containing 43% by weight of potassium hydrogen persulfate) was added and stirred for 6 hours. The reaction solution was filtered, and 690 mL of a 1 mol / L hydrochloric acid aqueous solution was added to the filtrate. The resulting solution was extracted three times with 990 mL of methyl isobutyl ketone, and further extracted twice with 590 mL of methyl isobutyl ketone. The resulting organic layers were combined and washed with saturated brine, and the organic layer was dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain 124 g of 2,3,5-bicyclo [2.2.1] heptanetricarboxylic acid (yield 79%).
1 H-NMR (D 2 O, δ ppm); 1.42-1.63 (m, 2H), 1.69-1.82 (m, 1H), 1.85-1.98 (m, 1H) , 2.65-2.71 (br, 1H), 2.79-2.86 (br, 1H), 3.00-3.19 (m, 2H), 3.20-3.30 (m, 1H), 9.50-15.25 (m, 3H)
［合成例３］２，３，５－ビシクロ［２．２．１］ヘプタントリカルボン酸２，３－無水物の合成
　２，３，５－ビシクロ［２．２．１］ヘプタントリカルボン酸２．０５ｇ（９ｍｍｏｌ）、無水１，４－ジオキサン１８ｍＬおよび無水酢酸０．９３ｍＬ（９．９ｍｍｏｌ）の混合物を窒素雰囲気下、１２０℃で４時間還流した。得られた反応液の溶媒を留去した後、残渣にトルエンを加えた。析出した結晶を濾取し、該結晶を６０℃で１２時間真空乾燥して２，３，５－ビシクロ［２．２．１］ヘプタントリカルボン酸２，３－無水物１．７８ｇを得た。
ＦＴ－ＩＲ；１８５１ｃｍ－１，１７８２ｃｍ－１
融点；１６６℃ Synthesis Example 3 Synthesis of 2,3,5-bicyclo [2.2.1] heptanetricarboxylic acid 2,3-anhydride 2,3,5-bicyclo [2.2.1] heptanetricarboxylic acid 2.05 g (9 mmol), 18 mL of anhydrous 1,4-dioxane and 0.93 mL (9.9 mmol) of acetic anhydride were refluxed at 120 ° C. for 4 hours under a nitrogen atmosphere. After the solvent of the obtained reaction liquid was distilled off, toluene was added to the residue. The precipitated crystals were collected by filtration, and the crystals were vacuum-dried at 60 ° C. for 12 hours to obtain 1.78 g of 2,3,5-bicyclo [2.2.1] heptanetricarboxylic acid 2,3-anhydride.
FT-IR; 1851 cm −1 , 1782 cm −1
Melting point: 166 ° C
［合成例４］５－クロロカルボニル－２，３－ビシクロ［２．２．１］ヘプタンジカルボン酸無水物の合成
　合成例３と同様に操作して得た２，３，５－ビシクロ［２．２．１］ヘプタントリカルボン酸２，３－無水物２．１ｇ（１０ｍｍｏｌ）に塩化チオニル５０ｍＬを加え、８０℃で２時間還流した。反応液にトルエンを加えて塩化チオニルを共沸留去した。析出した結晶を濾取し、該結晶を室温で１２時間真空乾燥して５－クロロカルボニル－２，３－ビシクロ［２．２．１］ヘプタンジカルボン酸無水物２．２９ｇを得た。
融点；１６６℃ [Synthesis Example 4] Synthesis of 5-chlorocarbonyl-2,3-bicyclo [2.2.1] heptanedicarboxylic anhydride 2,3,5-bicyclo [2. 2.1] 50 mL of thionyl chloride was added to 2.1 g (10 mmol) of heptanetricarboxylic acid 2,3-anhydride, and the mixture was refluxed at 80 ° C. for 2 hours. Toluene was added to the reaction solution, and thionyl chloride was distilled off azeotropically. The precipitated crystals were collected by filtration, and the crystals were vacuum-dried at room temperature for 12 hours to obtain 2.29 g of 5-chlorocarbonyl-2,3-bicyclo [2.2.1] heptanedicarboxylic anhydride.
Melting point: 166 ° C
［実施例１］化合物（ＶＩ－１）の合成
　合成例４と同様に操作して得た５－クロロカルボニル－２，３－ビシクロ［２．２．１］ヘプタンジカルボン酸無水物１．８ｇ（８．０ｍｍｏｌ）および無水テトラヒドロフラン８．２ｍＬを反応器に仕込み、反応器をセプタムキャップでシールし、氷浴中で０℃に冷却した。ヒドロキノン０．４ｇ（４．０ｍｍｏｌ）、ピリジン１．３ｍＬ（１６．０ｍｍｏｌ）および無水テトラヒドロフラン２．０ｍＬを混合して得た溶液をシリンジを用いて前記の反応器に氷浴下、ゆっくりと滴下し、次いで、０℃で数時間攪拌し、次いで、室温で２４時間撹拌した。析出した白色の沈殿を濾取し、該沈殿を水で洗浄し、１６０℃で１２時間真空乾燥して、化合物（ＶＩ－１）の粗生成物１．２ｇを得た（収率６４．３％）。該粗生成物を無水酢酸とγ－ブチロラクトンの混合溶媒（体積比１：１）より再結晶して化合物（ＶＩ－１）０．４ｇを得た。
　得られた化合物（ＶＩ－１）のＤＳＣ分析を行った。ＤＳＣ曲線において３２４．５℃にシャープな吸熱ピーク（融点）が観測されたことから、得られた化合物（ＶＩ－１）は高純度であることがわかった。
１Ｈ－ＮＭＲ（ＤＭＳＯ－ｄ６，δｐｐｍ）；１．５４－１．６３（ｍ，２Ｈ），１．６３－１．７４（ｍ，４Ｈ），２．０３－２．１５（ｍ，２Ｈ），２．６２－２．７１（ｍ，２Ｈ），２．７５－２．８４（ｍ，２Ｈ），３．０７－３．１６（ｍ，２Ｈ），３．５２－３．６０（ｍ，２Ｈ），３．６１－３．７０（ｍ，２Ｈ），７．２０（ｓ，４Ｈ） Example 1 Synthesis of Compound (VI-1) 1.8 g of 5-chlorocarbonyl-2,3-bicyclo [2.2.1] heptanedicarboxylic anhydride obtained by the same procedure as in Synthesis Example 4 (8.0 mmol) and 8.2 mL of anhydrous tetrahydrofuran were charged to the reactor, the reactor was sealed with a septum cap, and cooled to 0 ° C. in an ice bath. A solution obtained by mixing 0.4 g (4.0 mmol) of hydroquinone, 1.3 mL (16.0 mmol) of pyridine and 2.0 mL of anhydrous tetrahydrofuran was slowly added dropwise to the reactor using a syringe in an ice bath. Then, it was stirred at 0 ° C. for several hours and then at room temperature for 24 hours. The precipitated white precipitate was collected by filtration, washed with water, and vacuum-dried at 160 ° C. for 12 hours to obtain 1.2 g of a crude product of compound (VI-1) (yield 64.3). %). The crude product was recrystallized from a mixed solvent of acetic anhydride and γ-butyrolactone (volume ratio 1: 1) to obtain 0.4 g of Compound (VI-1).
The obtained compound (VI-1) was subjected to DSC analysis. A sharp endothermic peak (melting point) was observed at 324.5 ° C. in the DSC curve, which showed that the obtained compound (VI-1) was of high purity.
1 H-NMR (DMSO-d 6 , δ ppm); 1.54-1.63 (m, 2H), 1.63-1.74 (m, 4H), 2.03-2.15 (m, 2H) ), 2.62-2.71 (m, 2H), 2.75-2.84 (m, 2H), 3.07-3.16 (m, 2H), 3.52-3.60 (m) , 2H), 3.61-3.70 (m, 2H), 7.20 (s, 4H)
［実施例２］化合物（ＶＩ－２）の合成
　合成例４と同様に操作して得た５－クロロカルボニル－２，３－ビシクロ［２．２．１］ヘプタンジカルボン酸無水物４．３ｇ（１８．７ｍｍｏｌ）および無水テトラヒドロフラン１９．２ｍＬを反応器に仕込み、反応器をセプタムキャップでシールし、氷浴中で０℃に冷却した。４，４’－ビフェノール１．７ｇ（９．３ｍｍｏｌ）、ピリジン３．０ｍＬ（３７．３ｍｍｏｌ）および無水テトラヒドロフラン７．８ｍＬを混合して得た溶液をシリンジを用いて前記の反応器に氷浴下、ゆっくりと滴下し、次いで、０℃で数時間攪拌し、次いで、室温で２４時間撹拌した。析出した橙白色の沈殿を濾取し、該沈殿を水で洗浄し、１６０℃で１２時間真空乾燥して、化合物（ＶＩ－２）の粗生成物３．２ｇを得た（収率６１．０％）。該粗生成物を無水酢酸とトルエンの混合溶媒（体積比１：１）より再結晶して化合物（ＶＩ－２）０．１ｇを得た。
　得られた化合物（ＶＩ－２）のＤＳＣ分析を行った。ＤＳＣ曲線において２６０．８℃にシャープな吸熱ピーク（融点）が観測されたことから、得られた化合物（ＶＩ－２）は高純度であることがわかった。
１Ｈ－ＮＭＲ（ＤＭＳＯ－ｄ６，δｐｐｍ）；１．５５－１．６６（ｍ，２Ｈ），１．６５－１．７７（ｍ，４Ｈ），２．０５－２．１８（ｍ，２Ｈ），２．６３－２．７３（ｍ，２Ｈ），２．７５－２．８４（ｍ，２Ｈ），３．０８－３．１８（ｍ，２Ｈ），３．５２－３．６１（ｍ，２Ｈ），３．６２－３．７２（ｍ，２Ｈ），７．２８（ｄ，４Ｈ），７．７０（ｄ，４Ｈ） [Example 2] Synthesis of compound (VI-2) 4.3 g of 5-chlorocarbonyl-2,3-bicyclo [2.2.1] heptanedicarboxylic anhydride obtained by the same procedure as in Synthesis Example 4 18.7 mmol) and 19.2 mL of anhydrous tetrahydrofuran were charged to the reactor, which was sealed with a septum cap and cooled to 0 ° C. in an ice bath. A solution obtained by mixing 1.7 g (9.3 mmol) of 4,4′-biphenol, 3.0 mL (37.3 mmol) of pyridine and 7.8 mL of anhydrous tetrahydrofuran was added to the above reactor in an ice bath using a syringe. , Slowly added dropwise, then stirred at 0 ° C. for several hours and then at room temperature for 24 hours. The precipitated orange-white precipitate was collected by filtration, washed with water, and vacuum dried at 160 ° C. for 12 hours to obtain 3.2 g of a crude product of compound (VI-2) (yield 61. 0%). The crude product was recrystallized from a mixed solvent of acetic anhydride and toluene (volume ratio 1: 1) to obtain 0.1 g of Compound (VI-2).
The obtained compound (VI-2) was subjected to DSC analysis. A sharp endothermic peak (melting point) was observed at 260.8 ° C. in the DSC curve, which showed that the obtained compound (VI-2) was of high purity.
1 H-NMR (DMSO-d 6 , δ ppm); 1.55-1.66 (m, 2H), 1.65-1.77 (m, 4H), 2.05-2.18 (m, 2H) ), 2.63-2.73 (m, 2H), 2.75-2.84 (m, 2H), 3.08-3.18 (m, 2H), 3.52-3.61 (m) , 2H), 3.62-3.72 (m, 2H), 7.28 (d, 4H), 7.70 (d, 4H)
［実施例３］化合物（ＶＩ－３）の合成
　４，４’－ビシクロヘキサノール（トランス－トランス型）２．６ｇ（１３．１ｍｍｏｌ）、ピリジン６．４ｍＬ（７８．９ｍｍｏｌ）および無水テトラヒドロフラン５５．７ｍＬを反応器に仕込み、反応器をセプタムキャップでシールし、氷浴中で０℃に冷却した。合成例４と同様に操作して得た５－クロロカルボニル－２，３－ビシクロ［２．２．１］ヘプタンジカルボン酸無水物６．０ｇ（２６．３ｍｍｏｌ）および無水テトラヒドロフラン２０．３ｍＬを混合して得た溶液をシリンジを用いて前記の反応器に氷浴下、ゆっくりと滴下し、次いで、０℃で数時間攪拌し、次いで、室温で２４時間撹拌した。析出した橙白色の沈殿を濾取し、該沈殿を水で洗浄し、１６０℃で１２時間真空乾燥して、化合物（ＶＩ－３）の粗生成物４．１ｇを得た（収率５３．０％）。該粗生成物をジオキサンより再結晶して化合物（ＶＩ－３）３．０ｇを得た。
１Ｈ－ＮＭＲ（ＤＭＳＯ－ｄ６，δｐｐｍ）；１．０５－１．１５（ｍ，４Ｈ），１．１５－１．３４（ｍ，４Ｈ），１．３６－１．４９（ｍ，２Ｈ），１．５０－１．６３（ｍ，４Ｈ），１．６４－１．７８（ｍ，４Ｈ），１．８２－１．９９（ｍ，６Ｈ），２．２１－２．３５（ｍ，２Ｈ），２．６５－２．７８（ｍ，２Ｈ），２．７９－２．８９（ｍ，２Ｈ），３．２８－３．４３（ｍ，２Ｈ），３．４５－３．５４（ｍ，２Ｈ），３．５４－３．６４（ｍ，２Ｈ），４．４５－４．５９（ｍ，２Ｈ） Example 3 Synthesis of Compound (VI-3) 2.6 g (13.1 mmol) of 4,4′-bicyclohexanol (trans-trans type), 6.4 mL (78.9 mmol) of pyridine and 55.7 mL of anhydrous tetrahydrofuran Was charged to the reactor, the reactor was sealed with a septum cap, and cooled to 0 ° C. in an ice bath. 6.0 g (26.3 mmol) of 5-chlorocarbonyl-2,3-bicyclo [2.2.1] heptanedicarboxylic acid anhydride obtained by operating in the same manner as in Synthesis Example 4 and 20.3 mL of anhydrous tetrahydrofuran were mixed. The solution obtained in this manner was slowly dropped into the reactor using a syringe in an ice bath, then stirred at 0 ° C. for several hours, and then stirred at room temperature for 24 hours. The precipitated orange-white precipitate was collected by filtration, washed with water, and vacuum-dried at 160 ° C. for 12 hours to obtain 4.1 g of a crude product of compound (VI-3) (yield 53. 0%). The crude product was recrystallized from dioxane to obtain 3.0 g of compound (VI-3).
1 H-NMR (DMSO-d 6 , δ ppm); 1.05-1.15 (m, 4H), 1.15-1.34 (m, 4H), 1.36-1.49 (m, 2H) ), 1.50-1.63 (m, 4H), 1.64-1.78 (m, 4H), 1.82-1.99 (m, 6H), 2.21-2.35 (m , 2H), 2.65-2.78 (m, 2H), 2.79-2.89 (m, 2H), 3.28-3.43 (m, 2H), 3.45-3.54 (M, 2H), 3.54-3.64 (m, 2H), 4.45-4.59 (m, 2H)
[実施例４] 化合物（ＶＩ－４）の合成
　合成例４と同様に操作して得た５－クロロカルボニル－２，３－ビシクロ［２．２．１］ヘプタンジカルボン酸無水物７．５ｇ（３２．７ｍｍｏｌ）および無水テトラヒドロフラン２５．２ｍＬを反応器に仕込み、反応器をセプタムキャップでシールし、氷浴中で０℃に冷却した。９，９－ビス（４－ヒドロキシフェニル）フルオレン５．２ｇ（１４．９ｍｍｏｌ）、ピリジン５．３ｍＬ（６５．４ｍｍｏｌ）および無水テトラヒドロフラン１７．６ｍＬを混合して得た溶液をシリンジを用いて前記の反応器に氷浴下、ゆっくりと滴下し、次いで、０℃で数時間攪拌し、次いで、室温で２４時間撹拌した。反応液を濾過し、濾液をエバポレーターで濃縮し、残渣を水に注いだ。析出した沈殿を濾取し、該沈殿を１５０℃で１２時間真空乾燥して、化合物（ＶＩ－４）の粗生成物９．４ｇを得た（収率８６．５％）。該粗生成物を無水酢酸と酢酸の混合溶媒（体積比２：１）より再結晶して化合物（ＶＩ－４）２．９ｇを得た。
　得られた化合物（ＶＩ－４）のＤＳＣ分析を行った。ＤＳＣ曲線において２８４．２℃にシャープな吸熱ピーク（融点）が観測されたことから、得られた化合物（ＶＩ－４）は高純度であることがわかった。
１Ｈ－ＮＭＲ（ＤＭＳＯ－ｄ６，δｐｐｍ）；１．５０－１．７４（ｍ，６Ｈ），１．９８－２．１１（ｍ，２Ｈ），２．５６－２．７０（ｍ，２Ｈ），２．７２－２．８２（ｍ，２Ｈ），３．０１－３．１２（ｍ，２Ｈ），３．４８－３．５８（ｍ，２Ｈ），３．５９－３．６８（ｍ，２Ｈ），６．９０－７．２５（ｍ，８Ｈ），７．２９－７．５７（ｍ，６Ｈ），７．９５（ｄ，２Ｈ） [Example 4] Synthesis of compound (VI-4) 7.5 g of 5-chlorocarbonyl-2,3-bicyclo [2.2.1] heptanedicarboxylic anhydride obtained by operating in the same manner as in Synthesis Example 4 ( 32.7 mmol) and 25.2 mL of anhydrous tetrahydrofuran were charged to the reactor, which was sealed with a septum cap and cooled to 0 ° C. in an ice bath. A solution obtained by mixing 5.2 g (14.9 mmol) of 9,9-bis (4-hydroxyphenyl) fluorene, 5.3 mL (65.4 mmol) of pyridine and 17.6 mL of anhydrous tetrahydrofuran was mixed with the above solution using a syringe. The reaction vessel was slowly added dropwise in an ice bath and then stirred at 0 ° C. for several hours and then at room temperature for 24 hours. The reaction solution was filtered, the filtrate was concentrated with an evaporator, and the residue was poured into water. The deposited precipitate was collected by filtration and dried in vacuo at 150 ° C. for 12 hours to obtain 9.4 g of a crude product of compound (VI-4) (yield: 86.5%). The crude product was recrystallized from a mixed solvent of acetic anhydride and acetic acid (volume ratio 2: 1) to obtain 2.9 g of compound (VI-4).
The obtained compound (VI-4) was subjected to DSC analysis. A sharp endothermic peak (melting point) was observed at 284.2 ° C. in the DSC curve, which showed that the obtained compound (VI-4) was of high purity.
1 H-NMR (DMSO-d 6 , δ ppm); 1.50-1.74 (m, 6H), 1.98-2.11 (m, 2H), 2.56-2.70 (m, 2H) ), 2.72-2.82 (m, 2H), 3.01-3.12 (m, 2H), 3.48-3.58 (m, 2H), 3.59-3.68 (m) , 2H), 6.90-7.25 (m, 8H), 7.29-7.57 (m, 6H), 7.95 (d, 2H)
［実施例５］化合物（ＶＩ－５）の合成
　合成例４と同様に操作して得た５－クロロカルボニル－２，３－ビシクロ［２．２．１］ヘプタンジカルボン酸無水物９．１ｇ（３９．８ｍｍｏｌ）および無水テトラヒドロフラン３０．７ｍＬを反応器に仕込み、反応器をセプタムキャップでシールし、氷浴中で０℃に冷却した。２－メチルヒドロキノン２．５ｇ（１９．９ｍｍｏｌ）、ピリジン６．４ｍＬ（７９．６ｍｍｏｌ）および無水テトラヒドロフラン８．３ｍＬを混合して得た溶液をシリンジを用いて前記の反応器に氷浴下、ゆっくりと滴下し、次いで、０℃で数時間攪拌し、次いで、室温で２４時間撹拌した。析出した橙白色の沈殿を濾取し、該沈殿を水で洗浄し、１６０℃で１２時間真空乾燥して、化合物（ＶＩ－５）の粗生成物６．９ｇを得た（収率６８．６％）。該粗生成物を無水酢酸より再結晶して化合物（ＶＩ－５）０．５ｇを得た。
　得られた化合物（ＶＩ－５）のＤＳＣ分析を行った。ＤＳＣ曲線において３１６．８℃にシャープな吸熱ピーク（融点）が観測されたことから、得られた化合物（ＶＩ－５）は高純度であることがわかった。
１Ｈ－ＮＭＲ（ＤＭＳＯ－ｄ６，δｐｐｍ）；１．５３－１．７６（ｍ，６Ｈ），２．００－２．１６（ｍ、５Ｈ），２．６０－２．６８（ｍ，１Ｈ），２．６８－２．７５（ｍ，１Ｈ），２．７５－２．８５（ｍ，２Ｈ），３．０６－３．１７（ｍ，２Ｈ），３．５１－３．６１（ｍ，２Ｈ），３．６１－３．７２（ｍ，２Ｈ），６．９９－７．０６（ｍ，１Ｈ），７．０７－７．２２（ｍ，２Ｈ） [Example 5] Synthesis of compound (VI-5) 9.1 g of 5-chlorocarbonyl-2,3-bicyclo [2.2.1] heptanedicarboxylic anhydride obtained by operating in the same manner as in Synthesis Example 4. 39.8 mmol) and 30.7 mL of anhydrous tetrahydrofuran were charged to the reactor, the reactor was sealed with a septum cap and cooled to 0 ° C. in an ice bath. A solution obtained by mixing 2.5 g (19.9 mmol) of 2-methylhydroquinone, 6.4 mL (79.6 mmol) of pyridine and 8.3 mL of anhydrous tetrahydrofuran was slowly added to the above reactor in an ice bath using a syringe. And then stirred at 0 ° C. for several hours and then at room temperature for 24 hours. The precipitated orange-white precipitate was collected by filtration, washed with water, and vacuum-dried at 160 ° C. for 12 hours to obtain 6.9 g of a crude product of compound (VI-5) (yield: 68. 6%). The crude product was recrystallized from acetic anhydride to obtain 0.5 g of Compound (VI-5).
DSC analysis of the obtained compound (VI-5) was performed. In the DSC curve, a sharp endothermic peak (melting point) was observed at 316.8 ° C., indicating that the obtained compound (VI-5) was of high purity.
1 H-NMR (DMSO-d 6 , δ ppm); 1.53-1.76 (m, 6H), 2.00-2.16 (m, 5H), 2.60-2.68 (m, 1H) ), 2.68-2.75 (m, 1H), 2.75-2.85 (m, 2H), 3.06-3.17 (m, 2H), 3.51-3.61 (m) , 2H), 3.61-3.72 (m, 2H), 6.99-7.06 (m, 1H), 7.07-7.22 (m, 2H)
［実施例６］化合物（ＶＩ－６）の合成
　合成例４と同様に操作して得た５－クロロカルボニル－２，３－ビシクロ［２．２．１］ヘプタンジカルボン酸無水物３．３ｇ（１４．４ｍｍｏｌ）および無水テトラヒドロフラン５．６ｍＬを反応器に仕込み、反応器をセプタムキャップでシールし、氷浴中で０℃に冷却した。４，４’－ジヒドロキシジフェニルエーテル１．５ｇ（７．２ｍｍｏｌ）、ピリジン１．８ｍＬ（２１．６ｍｍｏｌ）および無水テトラヒドロフラン２．５ｍＬを混合して得た溶液をシリンジを用いて前記の反応器に氷浴下、ゆっくりと滴下し、次いで、０℃で数時間攪拌し、次いで、室温で２４時間撹拌した。析出した白色の沈殿を濾取し、該沈殿を水で洗浄し、１２０℃で１２時間真空乾燥して、化合物（ＶＩ－６）の粗生成物２．０ｇを得た（収率４７．６％）。該粗生成物を無水酢酸と酢酸の混合溶媒（体積比１：２）より再結晶して化合物（ＶＩ－６）０．２ｇを得た。
　得られた化合物（ＶＩ－６）のＤＳＣ分析を行った。ＤＳＣ曲線において２３５．３℃にシャープな吸熱ピーク（融点）が観測されたことから、得られた化合物（ＶＩ－６）は高純度であることがわかった。
１Ｈ－ＮＭＲ（ＤＭＳＯ－ｄ６，δｐｐｍ）；１．５３－１．６３（ｍ，２Ｈ），１．６３－１．７３（ｍ，４Ｈ），２．０２－２．１４（ｍ，２Ｈ），２．５８－２．６９（ｍ，２Ｈ），２．７３－２．８３（ｍ，２Ｈ），３．０５－３．１５（ｍ，２Ｈ），３．５０－３．６０（ｍ，２Ｈ），３．６１－３．７０（ｍ，２Ｈ），７．０４（ｄ，４Ｈ），７．１８（ｄ，４Ｈ） Example 6 Synthesis of Compound (VI-6) 3.3 g of 5-chlorocarbonyl-2,3-bicyclo [2.2.1] heptanedicarboxylic anhydride obtained by the same procedure as in Synthesis Example 4 14.4 mmol) and 5.6 mL of anhydrous tetrahydrofuran were charged to the reactor, and the reactor was sealed with a septum cap and cooled to 0 ° C. in an ice bath. A solution obtained by mixing 1.5 g (7.2 mmol) of 4,4′-dihydroxydiphenyl ether, 1.8 mL (21.6 mmol) of pyridine and 2.5 mL of anhydrous tetrahydrofuran was added to the reactor with an ice bath using a syringe. The solution was slowly added dropwise, followed by stirring at 0 ° C. for several hours and then at room temperature for 24 hours. The precipitated white precipitate was collected by filtration, washed with water, and vacuum-dried at 120 ° C. for 12 hours to obtain 2.0 g of a crude product of compound (VI-6) (yield 47.6). %). The crude product was recrystallized from a mixed solvent of acetic anhydride and acetic acid (volume ratio 1: 2) to obtain 0.2 g of Compound (VI-6).
DSC analysis of the obtained compound (VI-6) was performed. In the DSC curve, a sharp endothermic peak (melting point) was observed at 235.3 ° C., indicating that the obtained compound (VI-6) was of high purity.
1 H-NMR (DMSO-d 6 , δ ppm); 1.53-1.63 (m, 2H), 1.63-1.73 (m, 4H), 2.02-2.14 (m, 2H) ), 2.58-2.69 (m, 2H), 2.73-2.83 (m, 2H), 3.05-3.15 (m, 2H), 3.50-3.60 (m , 2H), 3.61-3.70 (m, 2H), 7.04 (d, 4H), 7.18 (d, 4H)
＜ポリイミド前駆体の製造、ポリイミドの製造およびポリイミド膜の評価＞
　実施例７～３０のポリイミド前駆体の製造に用いたジアミンを下記に示す。 <Manufacture of polyimide precursor, manufacture of polyimide and evaluation of polyimide film>
The diamines used in the production of the polyimide precursors of Examples 7 to 30 are shown below.
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
［実施例７～３０］ポリイミド前駆体（Ｖ－１）～（Ｖ－２４）の製造
　表１に記載のジアミンとテトラカルボン酸二無水物との組み合わせを原料として用い、以下の操作を行うことによりポリイミド前駆体（Ｖ－１）～（Ｖ－２４）の溶液を得た。
　よく乾燥した攪拌機付密閉反応器中にジアミン５ｍｍｏｌおよびジメチルアセトアミドを仕込み、次いで、テトラカルボン酸二無水物５ｍｍｏｌを室温で徐々に加え、次いで、表１に記載の時間攪拌して、透明で粘稠なポリイミド前駆体の溶液を得た。表１中、濃度は以下の式：
　　　濃度（重量％）＝（ｗ１＋ｗ２）／（ｗ１＋ｗ２＋ｗ３）ｘ１００
（式中、ｗ１は使用したジアミンの重量を表し、ｗ２は使用したテトラカルボン酸二無水物の重量を表し、ｗ３は使用したジメチルアセトアミドの重量を表す）で計算した値を表す。 [Examples 7 to 30] Production of polyimide precursors (V-1) to (V-24) Using the combination of diamine and tetracarboxylic dianhydride shown in Table 1 as raw materials, the following operations are performed. As a result, solutions of polyimide precursors (V-1) to (V-24) were obtained.
A well-dried sealed reactor equipped with a stirrer was charged with 5 mmol of diamine and dimethylacetamide, then 5 mmol of tetracarboxylic dianhydride was gradually added at room temperature, and then stirred for the time shown in Table 1 to obtain a clear and viscous solution. A solution of a polyimide precursor was obtained. In Table 1, the concentration is the following formula:
Concentration (% by weight) = (w1 + w2) / (w1 + w2 + w3) × 100
(Wherein w1 represents the weight of the diamine used, w2 represents the weight of the tetracarboxylic dianhydride used, and w3 represents the weight of the dimethylacetamide used).
　ポリイミド前駆体（Ｖ－１）の溶液を室温で１ヶ月間、または－２０℃で１ヶ月間放置したとき沈澱の生成およびゲル化は全く起こらず、ポリイミド前駆体（Ｖ－１）の溶液は極めて高い溶液貯蔵安定性を示した。表１にポリイミド前駆体（Ｖ－１）～（Ｖ－２４）の固有粘度を示す。 When the polyimide precursor (V-1) solution was allowed to stand at room temperature for 1 month or at -20 ° C. for 1 month, no precipitation and gelation occurred, and the polyimide precursor (V-1) solution was It showed very high solution storage stability. Table 1 shows the intrinsic viscosities of polyimide precursors (V-1) to (V-24).
［実施例３１～５４］ポリイミド（Ｉ－１）～（Ｉ－２４）の製造
　表２に記載のポリイミド前駆体を原料として用い、以下の操作を行うことによりポリイミド（Ｉ－１）～（Ｉ－２４）を得た。
　実施例７～３０で得たポリイミド前駆体の溶液のそれぞれを反応器に仕込み、次いで、化学イミド化試薬（無水酢酸／ピリジン混合溶液、体積比７／３）を室温で反応器に滴下し、次いで、室温で２４時間攪拌した。このとき用いた化学イミド化試薬中の無水酢酸量は、ポリイミド前駆体（Ｖ）に含まれるアミド酸単位に対して５倍モル量である。反応器の内容物を大量のメタノール中に注ぎ、析出した固体を濾取し、乾燥して、ポリイミド（Ｉ－１）～（Ｉ－２４）を得た。
　ポリイミド（Ｉ－１）～（Ｉ－２４）のそれぞれ１ｇをジメチルアセトアミド３ｇに溶解し、得られた溶液をバーコーティングによりガラス基板に塗付し、該ガラス基板を６０℃で２時間乾燥し、該ガラス基板を表２に記載の熱処理条件で加熱し、該ガラス基板上に生成したポリイミド膜を該基板から剥離することにより、膜厚約２０μmの透明なポリイミド（Ｉ－１）～（Ｉ－２４）の膜を得た。該ポリイミド（Ｉ－１）～（Ｉ－２４）の膜を指で１８０°折り曲げたときこれらの膜は破断しなかったことから、ポリイミド（Ｉ－１）～（Ｉ－２４）は優れた可撓性を有することがわかった。
　表３にポリイミド膜の物性を示す。 [Examples 31 to 54] Production of polyimides (I-1) to (I-24) Using the polyimide precursors shown in Table 2 as raw materials, the following operations were performed to obtain polyimides (I-1) to (I -24) was obtained.
Each of the polyimide precursor solutions obtained in Examples 7 to 30 was charged into a reactor, and then a chemical imidization reagent (acetic anhydride / pyridine mixed solution, volume ratio 7/3) was dropped into the reactor at room temperature. Subsequently, it stirred at room temperature for 24 hours. The amount of acetic anhydride in the chemical imidizing reagent used at this time is a 5-fold molar amount with respect to the amic acid unit contained in the polyimide precursor (V). The contents of the reactor were poured into a large amount of methanol, and the precipitated solid was collected by filtration and dried to obtain polyimides (I-1) to (I-24).
1 g of each of the polyimides (I-1) to (I-24) was dissolved in 3 g of dimethylacetamide, the resulting solution was applied to a glass substrate by bar coating, and the glass substrate was dried at 60 ° C. for 2 hours. The glass substrate is heated under the heat treatment conditions shown in Table 2, and the polyimide film formed on the glass substrate is peeled off from the substrate, whereby transparent polyimides (I-1) to (I- 24) was obtained. Since the films of the polyimides (I-1) to (I-24) were not broken when they were bent 180 ° with a finger, the polyimides (I-1) to (I-24) were excellent. It was found to have flexibility.
Table 3 shows the physical properties of the polyimide film.
Figure JPOXMLDOC01-appb-T000038
Figure JPOXMLDOC01-appb-T000038
Figure JPOXMLDOC01-appb-T000039
Figure JPOXMLDOC01-appb-T000039
Figure JPOXMLDOC01-appb-T000040
Figure JPOXMLDOC01-appb-T000040
［比較例１］
　式（ＶＩＩＩ－１） [Comparative Example 1]
Formula (VIII-1)
Figure JPOXMLDOC01-appb-C000041
 で表されるテトラカルボン酸二無水物を国際公開第２００６／１２９７７１号パンフレットに記載の方法に準じて製造することにより得た。
Figure JPOXMLDOC01-appb-C000041
 It was obtained by producing a tetracarboxylic dianhydride represented by the method described in International Publication No. 2006/129771 pamphlet.
　化合物（ＶＩ－１）の代わりに式（ＶＩＩＩ－１）で表されるテトラカルボン酸二無水物を用いる以外は実施例７と同様な操作を行うことによりポリイミド前駆体（Ｘ－１）を得た。次いで、ポリイミド前駆体（Ｖ－１）の代わりにポリイミド前駆体（Ｘ－１）を用いる以外は実施例３１と同様な操作を行うことによりポリイミド（ＸＩ－１）を得た。次いで、ポリイミド（Ｉ－１）の代わりにポリイミド（ＸＩ－１）を用いる以外は実施例３１と同様な操作を行うことによりポリイミド（ＸＩ－１）の膜を得た。表３にポリイミド（ＸＩ－１）の膜の物性を示す。 A polyimide precursor (X-1) is obtained by performing the same operation as in Example 7 except that the tetracarboxylic dianhydride represented by the formula (VIII-1) is used in place of the compound (VI-1). It was. Next, polyimide (XI-1) was obtained by performing the same operation as in Example 31 except that the polyimide precursor (X-1) was used instead of the polyimide precursor (V-1). Next, a film of polyimide (XI-1) was obtained by performing the same operation as in Example 31 except that polyimide (XI-1) was used instead of polyimide (I-1). Table 3 shows the physical properties of the polyimide (XI-1) film.
［比較例２］
　化合物（ＶＩ－１）の代わりに式（ＶＩＩＩ－１）で表されるテトラカルボン酸二無水物を用いる以外は実施例９と同様な操作を行うことによりポリイミド前駆体（Ｘ－２）を得た。次いで、ポリイミド前駆体（Ｖ－１）の代わりにポリイミド前駆体（Ｘ－２）を用いる以外は実施例３１と同様な操作を行うことによりポリイミド（ＸＩ－２）を得た。次いで、ポリイミド（Ｉ－１）の代わりにポリイミド（ＸＩ－２）を用いる以外は実施例３１と同様な操作を行うことによりポリイミド（ＸＩ－２）の膜を得た。表３にポリイミド（ＸＩ－２）の膜の物性を示す。
　ポリイミド（Ｉ－１）はポリイミド（ＸＩ－１）に比べ低いＣＴＥおよび高いＴｇを有した。またポリイミド（Ｉ－３）はポリイミド（ＸＩ－２）に比べ低いＣＴＥおよび高いＴｇを有した。以上のことより、実施例で得られたポリイミドは高い耐熱性を有することがわかる。 [Comparative Example 2]
A polyimide precursor (X-2) is obtained by performing the same operation as in Example 9 except that the tetracarboxylic dianhydride represented by the formula (VIII-1) is used in place of the compound (VI-1). It was. Next, a polyimide (XI-2) was obtained by performing the same operation as in Example 31 except that the polyimide precursor (X-2) was used instead of the polyimide precursor (V-1). Next, a polyimide (XI-2) film was obtained by performing the same operation as in Example 31 except that polyimide (XI-2) was used instead of polyimide (I-1). Table 3 shows the physical properties of the polyimide (XI-2) film.
Polyimide (I-1) had lower CTE and higher Tg compared to polyimide (XI-1). Polyimide (I-3) had a lower CTE and a higher Tg than polyimide (XI-2). From the above, it can be seen that the polyimides obtained in the examples have high heat resistance.
　本発明により、高い耐熱性等を有するポリイミド等を提供できる。 According to the present invention, polyimide having high heat resistance and the like can be provided.

Claims (16)

  1. 　式（Ｉ）
    Figure JPOXMLDOC01-appb-C000001
     ［式中、Ｐ１、Ｐ２およびＰ３は、同一または異なって、水素原子、ハロゲン原子、シアノ基、ホルミル基、ヒドロキシル基、置換もしくは非置換のアルキル基、置換もしくは非置換のシクロアルキル基、置換もしくは非置換のアルケニル基、置換もしくは非置換のアリール基、置換もしくは非置換のアラルキル基、置換もしくは非置換のアルカノイルオキシ基または置換もしくは非置換のアルコキシル基を表し、ＸおよびＡは、同一または異なって、置換もしくは非置換のアルキレン基、置換もしくは非置換の多環式不飽和炭化水素から炭素原子上の水素原子を２つ除くことにより生じる２価の基、置換もしくは非置換の多環式飽和炭化水素から炭素原子上の水素原子を２つ除くことにより生じる２価の基、式（ＩＩ）
    Figure JPOXMLDOC01-appb-C000002
     ［式中、ｍは０～３の整数を表し、Ｒ１およびＲ２は、同一または異なって、ハロゲン原子、シアノ基、ホルミル基、ヒドロキシル基、置換もしくは非置換のアルキル基、置換もしくは非置換のアルケニル基、置換もしくは非置換のアリール基、置換もしくは非置換のアルカノイルオキシ基または置換もしくは非置換のアルコキシル基を表し、ｑおよびｒは、同一または異なって、０～４の整数を表し、ｑが２～４の整数であるときＲ１のそれぞれは同一または異なってよく、ｒが２～４の整数であるときＲ２のそれぞれは同一または異なってよく、Ｚ１は単結合、酸素原子、硫黄原子、ＳＯ２、フッ素原子が置換していてもよい炭素数１～４のアルキレン基、または式（ＩＩＩ）
    Figure JPOXMLDOC01-appb-C000003
     （式中、Ｒ５およびＲ６は、同一または異なって、ハロゲン原子、シアノ基、ホルミル基、ヒドロキシル基、置換もしくは非置換のアルキル基、置換もしくは非置換のシクロアルキル基、置換もしくは非置換のアルケニル基、置換もしくは非置換のアリール基、置換もしくは非置換のアラルキル基、置換もしくは非置換のアルカノイルオキシ基または置換もしくは非置換のアルコキシル基を表し、ｅおよびｆは、同一または異なって、０～４の整数を表し、ｅが２～４の整数であるときＲ５のそれぞれは同一または異なってよく、ｆが２～４の整数であるときＲ６のそれぞれは同一または異なってよい）を表し、ｍが２または３であるときＲ１、ｑおよびＺ１のそれぞれは同一または異なってよい］または式（ＩＶ）
    Figure JPOXMLDOC01-appb-C000004
     （式中、ｎは０～３の整数を表し、Ｒ３およびＲ４は、同一または異なって、ハロゲン原子、シアノ基、ホルミル基、ヒドロキシル基、置換もしくは非置換のアルキル基、置換もしくは非置換のシクロアルキル基、置換もしくは非置換のアルケニル基、置換もしくは非置換のアルカノイルオキシ基または置換もしくは非置換のアルコキシル基を表し、ｓａおよびｕａは、同一または異なって、０～４の整数を表し、ｓａが２～４の整数であるときＲ３のそれぞれは同一または異なってよく、ｕａが２～４の整数であるときＲ４のそれぞれは同一または異なってよく、ｓｂおよびｕｂは、同一または異なって、０～２の整数を表し、Ｚ２は単結合、酸素原子、硫黄原子、ＳＯ２またはフッ素原子が置換していてもよい炭素数１～４のアルキレン基を表し、ｎが２または３であるときＲ３、ｓａ、ｓｂおよびＺ２のそれぞれは同一または異なっていてもよい）を表す］で表される繰り返し単位を有するポリイミド。     Formula (I)
    Figure JPOXMLDOC01-appb-C000001
     [Wherein P 1 , P 2 and P 3 are the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, a formyl group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group Represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkanoyloxy group or a substituted or unsubstituted alkoxyl group, and X and A are the same Or differently, a substituted or unsubstituted alkylene group, a divalent group formed by removing two hydrogen atoms on a carbon atom from a substituted or unsubstituted polycyclic unsaturated hydrocarbon, a substituted or unsubstituted polycycle A divalent group formed by removing two hydrogen atoms on a carbon atom from a saturated hydrocarbon of formula (II)
    Figure JPOXMLDOC01-appb-C000002
     [Wherein, m represents an integer of 0 to 3, and R 1 and R 2 are the same or different and each represents a halogen atom, a cyano group, a formyl group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group. Alkenyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkanoyloxy group or substituted or unsubstituted alkoxyl group, q and r are the same or different and represent an integer of 0 to 4, q Each of R 1 may be the same or different when R is an integer of 2 to 4, and each of R 2 may be the same or different when r is an integer of 2 to 4, and Z 1 is a single bond, an oxygen atom, A sulfur atom, SO 2 , a C 1-4 alkylene group which may be substituted by a fluorine atom, or the formula (III)
    Figure JPOXMLDOC01-appb-C000003
     (Wherein R 5 and R 6 are the same or different and each represents a halogen atom, a cyano group, a formyl group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted group, Represents an alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkanoyloxy group or a substituted or unsubstituted alkoxyl group, and e and f are the same or different and represent 0 to Each of R 5 may be the same or different when e is an integer of 2 to 4, and each of R 6 may be the same or different when f is an integer of 2 to 4. Each of R 1 , q and Z 1 may be the same or different when m is 2 or 3] or formula (IV)
    Figure JPOXMLDOC01-appb-C000004
     (Wherein n represents an integer of 0 to 3, and R 3 and R 4 are the same or different and are each a halogen atom, a cyano group, a formyl group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group, A cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkanoyloxy group or a substituted or unsubstituted alkoxyl group, sa and ua are the same or different and represent an integer of 0 to 4; When sa is an integer from 2 to 4, each R 3 may be the same or different, and when ua is an integer from 2 to 4 , each R 4 may be the same or different, and sb and ub are the same or different. Te, 0 represents an integer 2, Z 2 is a single bond, an oxygen atom, a sulfur atom, alkyl of SO 2 or a fluorine atom and 1 carbon atoms and optionally substituted 4 Represents an emission radical, n when it is 2 or 3 R 3, sa, polyimide having a repeating unit each of sb and Z 2 is represented by representing the same or may be different).
  2. 　式（Ｖ）
    Figure JPOXMLDOC01-appb-C000005
     ［式中、Ｐ１、Ｐ２、Ｐ３およびＸはそれぞれ前記と同義であり、ＲａおよびＲｂの一方はヒドロキシル基を表し他方は－ＮＨ－Ａ－（式中、Ａは前記と同義である）で表される２価の基を表し、ＲｃおよびＲｄの一方はヒドロキシル基を表し他方は－ＮＨ－で表される２価の基を表す］で表される繰り返し単位を有するポリイミド前駆体をイミド化することを特徴とする式（Ｉ）
    Figure JPOXMLDOC01-appb-C000006
     （式中、Ｐ１、Ｐ２、Ｐ３、ＸおよびＡはそれぞれ前記と同義である）で表される繰り返し単位を有するポリイミドの製造方法。     Formula (V)
    Figure JPOXMLDOC01-appb-C000005
     [Wherein P 1 , P 2 , P 3 and X are as defined above, one of R a and R b represents a hydroxyl group and the other is —NH—A— (wherein A is as defined above] In which one of R c and R d represents a hydroxyl group and the other represents a divalent group represented by —NH—. Formula (I) characterized by imidizing a polyimide precursor
    Figure JPOXMLDOC01-appb-C000006
     (Wherein P 1 , P 2 , P 3 , X and A are as defined above), a method for producing a polyimide having a repeating unit.
  3. 　式（Ｖ）
    Figure JPOXMLDOC01-appb-C000007
     （式中、Ｐ１、Ｐ２、Ｐ３、Ｘ、Ｒａ、Ｒｂ、ＲｃおよびＲｄはそれぞれ前記と同義である）で表される繰り返し単位を有するポリイミド前駆体。     Formula (V)
    Figure JPOXMLDOC01-appb-C000007
     (Wherein P 1 , P 2 , P 3 , X, R a , R b , R c and R d are as defined above), and a polyimide precursor having a repeating unit.
  4. 　式（ＶＩ）
    Figure JPOXMLDOC01-appb-C000008
     （式中、Ｐ１、Ｐ２、Ｐ３およびＸはそれぞれ前記と同義である）で表されるテトラカルボン酸二無水物を含む１種類以上のテトラカルボン酸二無水物とＨ２Ｎ－Ａ－ＮＨ２（式中、Ａは前記と同義である）で表されるジアミンとを反応させることを特徴とする式（Ｖ）
    Figure JPOXMLDOC01-appb-C000009
     （式中、Ｐ１、Ｐ２、Ｐ３、Ｘ、Ｒａ、Ｒｂ、ＲｃおよびＲｄはそれぞれ前記と同義である）で表される繰り返し単位を有するポリイミド前駆体の製造方法。     Formula (VI)
    Figure JPOXMLDOC01-appb-C000008
     (Wherein P 1 , P 2 , P 3 and X are as defined above) and one or more types of tetracarboxylic dianhydrides including H 2 NA Formula (V), characterized by reacting with a diamine represented by —NH 2 (wherein A is as defined above)
    Figure JPOXMLDOC01-appb-C000009
     (Wherein P 1 , P 2 , P 3 , X, R a , R b , R c and R d are as defined above), a method for producing a polyimide precursor having a repeating unit.
  5. 　式（ＶＩ）
    Figure JPOXMLDOC01-appb-C000010
     （式中、Ｐ１、Ｐ２、Ｐ３およびＸはそれぞれ前記と同義である）で表されるテトラカルボン酸二無水物。     Formula (VI)
    Figure JPOXMLDOC01-appb-C000010
     (Wherein P 1 , P 2 , P 3 and X are as defined above), tetracarboxylic dianhydride.
  6. 　式（ＶＩＩ）
    Figure JPOXMLDOC01-appb-C000011
     （式中、Ｐ１、Ｐ２およびＰ３はそれぞれ前記と同義である）で表される酸無水物とハロゲン化剤とを反応させることにより酸ハライドを得、次いで、該酸ハライドとＨＯ－Ｘ－ＯＨ（式中、Ｘは前記と同義である）で表されるジオールとを反応させることを特徴とする式（ＶＩ）
    Figure JPOXMLDOC01-appb-C000012
     （式中、Ｐ１、Ｐ２、Ｐ３およびＸおよびＡはそれぞれ前記と同義である）で表されるテトラカルボン酸二無水物の製造方法。     Formula (VII)
    Figure JPOXMLDOC01-appb-C000011
     (Wherein P 1 , P 2 and P 3 are as defined above), an acid halide and a halogenating agent are reacted to obtain an acid halide, and then the acid halide and HO— Reacting with a diol represented by X—OH (wherein X is as defined above),
    Figure JPOXMLDOC01-appb-C000012
     (Wherein P 1 , P 2 , P 3 and X and A are as defined above), a method for producing a tetracarboxylic dianhydride.
  7. 　式（ＶＩＩ）
    Figure JPOXMLDOC01-appb-C000013
     （式中、Ｐ１、Ｐ２およびＰ３はそれぞれ前記と同義である）で表される酸無水物とハロゲン化剤とを反応させることにより酸ハライドを得、次いで、該酸ハライドとＨＯ－Ｘ－ＯＨ（式中、Ｘは前記と同義である）で表されるジオールとを反応させることにより式（ＶＩ）
    Figure JPOXMLDOC01-appb-C000014
     （式中、Ｐ１、Ｐ２、Ｐ３およびＸはそれぞれ前記と同義である）で表されるテトラカルボン酸二無水物を得、次いで、該テトラカルボン酸二無水物を含む１種類以上のテトラカルボン酸二無水物とＨ２Ｎ－Ａ－ＮＨ２（式中、Ａは前記と同義である）で表されるジアミンとを反応させることにより式（Ｖ）
    Figure JPOXMLDOC01-appb-C000015
     （式中、Ｐ１、Ｐ２、Ｐ３、Ｘ、Ｒａ、Ｒｂ、ＲｃおよびＲｄはそれぞれ前記と同義である）で表される繰り返し単位を有するポリイミド前駆体を得、次いで、該ポリイミド前駆体をイミド化することを特徴とする式（Ｉ）
    Figure JPOXMLDOC01-appb-C000016
     （式中、Ｐ１、Ｐ２、Ｐ３、ＸおよびＡはそれぞれ前記と同義である）で表される繰り返し単位を有するポリイミドの製造方法。     Formula (VII)
    Figure JPOXMLDOC01-appb-C000013
     (Wherein P 1 , P 2 and P 3 are as defined above), an acid halide and a halogenating agent are reacted to obtain an acid halide, and then the acid halide and HO— By reacting with a diol represented by X—OH (wherein X is as defined above), the compound of formula (VI)
    Figure JPOXMLDOC01-appb-C000014
     (Wherein P 1 , P 2 , P 3 and X are as defined above), and then one or more kinds of tetracarboxylic dianhydrides containing the tetracarboxylic dianhydride By reacting tetracarboxylic dianhydride with a diamine represented by H 2 N—A—NH 2 (wherein A is as defined above), the compound represented by the formula (V)
    Figure JPOXMLDOC01-appb-C000015
     (Wherein P 1 , P 2 , P 3 , X, R a , R b , R c and R d are as defined above), a polyimide precursor having a repeating unit represented by Formula (I) characterized by imidizing the polyimide precursor
    Figure JPOXMLDOC01-appb-C000016
     (Wherein P 1 , P 2 , P 3 , X and A are as defined above), a method for producing a polyimide having a repeating unit.
  8. 　ＸおよびＡが、同一または異なって、式（ＩＩ）または式（ＩＶ）である請求項１記載のポリイミド。 The polyimide according to claim 1, wherein X and A are the same or different and are represented by formula (II) or formula (IV).
  9. 　ＸおよびＡが、同一または異なって、式（ＩＩ）である請求項１記載のポリイミド。 The polyimide according to claim 1, wherein X and A are the same or different and are represented by formula (II).
  10. 　Ｐ１、Ｐ２およびＰ３が水素原子である請求項１、８または９記載のポリイミド。 The polyimide according to claim 1, 8 or 9, wherein P 1 , P 2 and P 3 are hydrogen atoms.
  11. 　ＸおよびＡが、同一または異なって、式（ＩＩ）または式（ＩＶ）である請求項３記載のポリイミド前駆体。 The polyimide precursor according to claim 3, wherein X and A are the same or different and are represented by formula (II) or formula (IV).
  12. 　ＸおよびＡが、同一または異なって、式（ＩＩ）である請求項３記載のポリイミド前駆体。 The polyimide precursor according to claim 3, wherein X and A are the same or different and have the formula (II).
  13. 　Ｐ１、Ｐ２およびＰ３が水素原子である請求項３、１１または１２記載のポリイミド前駆体。 The polyimide precursor according to claim 3, 11 or 12, wherein P 1 , P 2 and P 3 are hydrogen atoms.
  14. 　Ｘが式（ＩＩ）または式（ＩＶ）である請求項５記載のテトラカルボン酸二無水物。 The tetracarboxylic dianhydride according to claim 5, wherein X is formula (II) or formula (IV).
  15. 　Ｘが式（ＩＩ）である請求項５記載のテトラカルボン酸二無水物。 X is a formula (II), The tetracarboxylic dianhydride of Claim 5.
  16. 　Ｐ１、Ｐ２およびＰ３が水素原子である請求項５、１４または１５記載のテトラカルボン酸二無水物。 The tetracarboxylic dianhydride according to claim 5, 14 or 15, wherein P 1 , P 2 and P 3 are hydrogen atoms.
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JPWO2019163703A1 (en) * 2018-02-21 2021-02-04 Ｅｎｅｏｓ株式会社 Polyimide precursor resin composition
CN111742012A (en) * 2018-02-21 2020-10-02 引能仕株式会社 Polyimide precursor resin composition
KR102429867B1 (en) 2018-02-21 2022-08-05 에네오스 가부시키가이샤 Polyimide precursor resin composition
JP7203082B2 (en) 2018-02-21 2023-01-12 Ｅｎｅｏｓ株式会社 Polyimide precursor resin composition
JP2021031452A (en) * 2019-08-27 2021-03-01 Jnc株式会社 Dialdehyde compound having norbornane skeleton and cyclohexadione skeleton and method for producing the same
JP7247817B2 (en) 2019-08-27 2023-03-29 Jnc株式会社 Dialdehyde compound having norbornane skeleton and cyclohexadione skeleton and method for producing the same

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