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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English (en)
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/fr

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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.

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  • Chemical & Material Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

L'invention porte sur un polyimide ayant une unité répétitive représentée par la formule (I) ou similaire. [Dans la formule (I), P1, P2 et P3 représentent chacun un atome d'hydrogène ou similaire; et X et A peuvent être identiques ou différents et chacun représente un groupe représenté par la formule (II) ou similaire.] [Dans la formule (II), m représente un entier compris entre 0 et 3; R1 et R2 peuvent être identiques ou différents et représentent chacun un groupe alkyle ou similaire; q et r peuvent être identiques ou différents et représentent chacun un entier compris entre 0 et 4; et Z1 représente une simple liaison, un atome d'oxygène, SO2 ou similaire.]
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Cited By (8)

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WO2010131566A1 (fr) * 2009-05-11 2010-11-18 富士フイルム株式会社 Dianhydride d'acide tétracarboxylique et polymère
WO2011121850A1 (fr) * 2010-03-29 2011-10-06 日立化成工業株式会社 Polyamide-imide ayant un squelette de nadimide et son procédé d'obtention
WO2011121847A1 (fr) * 2010-03-29 2011-10-06 日立化成工業株式会社 Procédé de fabrication d'un polyamide-imide ayant un squelette de nadimide
WO2011121848A1 (fr) * 2010-03-29 2011-10-06 日立化成工業株式会社 Polyamide-imide ayant un squelette de norbornane et son procédé de fabrication
JPWO2012029734A1 (ja) * 2010-09-02 2013-10-28 東レ株式会社 感光性組成物、それから形成された硬化膜および硬化膜を有する素子
WO2019163703A1 (fr) * 2018-02-21 2019-08-29 Ｊｘｔｇエネルギー株式会社 Composition de résine précurseur de polyimide
JP2021031452A (ja) * 2019-08-27 2021-03-01 Jnc株式会社 ノルボルナン骨格とシクロヘキサジオン骨格とを有するジアルデヒド化合物およびその製造法
TWI735667B (zh) * 2016-09-28 2021-08-11 日商日產化學工業股份有限公司 酸二酐及其利用

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JP2007002023A (ja) * 2005-06-21 2007-01-11 Fujifilm Holdings Corp フィルムおよび画像表示装置
WO2007058156A1 (fr) * 2005-11-15 2007-05-24 Mitsubishi Chemical Corporation Compose d'acide tetracarboxylique, polyimide de celui-ci, et son procede de production

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JP2007002023A (ja) * 2005-06-21 2007-01-11 Fujifilm Holdings Corp フィルムおよび画像表示装置
WO2007058156A1 (fr) * 2005-11-15 2007-05-24 Mitsubishi Chemical Corporation Compose d'acide tetracarboxylique, polyimide de celui-ci, et son procede de production

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WO2010131566A1 (fr) * 2009-05-11 2010-11-18 富士フイルム株式会社 Dianhydride d'acide tétracarboxylique et polymère
WO2011121850A1 (fr) * 2010-03-29 2011-10-06 日立化成工業株式会社 Polyamide-imide ayant un squelette de nadimide et son procédé d'obtention
WO2011121847A1 (fr) * 2010-03-29 2011-10-06 日立化成工業株式会社 Procédé de fabrication d'un polyamide-imide ayant un squelette de nadimide
WO2011121848A1 (fr) * 2010-03-29 2011-10-06 日立化成工業株式会社 Polyamide-imide ayant un squelette de norbornane et son procédé de fabrication
CN102791770A (zh) * 2010-03-29 2012-11-21 日立化成工业株式会社 具有降冰片烷骨架的聚酰胺酰亚胺及其制造方法
CN102791770B (zh) * 2010-03-29 2014-05-07 日立化成株式会社 具有降冰片烷骨架的聚酰胺酰亚胺及其制造方法
JPWO2012029734A1 (ja) * 2010-09-02 2013-10-28 東レ株式会社 感光性組成物、それから形成された硬化膜および硬化膜を有する素子
JP5765235B2 (ja) * 2010-09-02 2015-08-19 東レ株式会社 感光性組成物、それから形成された硬化膜および硬化膜を有する素子
TWI735667B (zh) * 2016-09-28 2021-08-11 日商日產化學工業股份有限公司 酸二酐及其利用
WO2019163703A1 (fr) * 2018-02-21 2019-08-29 Ｊｘｔｇエネルギー株式会社 Composition de résine précurseur de polyimide
KR20200123172A (ko) * 2018-02-21 2020-10-28 에네오스 가부시키가이샤 폴리이미드 전구체 수지 조성물
JPWO2019163703A1 (ja) * 2018-02-21 2021-02-04 Ｅｎｅｏｓ株式会社 ポリイミド前駆体樹脂組成物
CN111742012A (zh) * 2018-02-21 2020-10-02 引能仕株式会社 聚酰亚胺前体树脂组合物
KR102429867B1 (ko) 2018-02-21 2022-08-05 에네오스 가부시키가이샤 폴리이미드 전구체 수지 조성물
JP7203082B2 (ja) 2018-02-21 2023-01-12 Ｅｎｅｏｓ株式会社 ポリイミド前駆体樹脂組成物
JP2021031452A (ja) * 2019-08-27 2021-03-01 Jnc株式会社 ノルボルナン骨格とシクロヘキサジオン骨格とを有するジアルデヒド化合物およびその製造法
JP7247817B2 (ja) 2019-08-27 2023-03-29 Jnc株式会社 ノルボルナン骨格とシクロヘキサジオン骨格とを有するジアルデヒド化合物およびその製造法

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