WO2013136807A1 - ポリイミド前駆体ワニス、ポリイミド樹脂、及びその用途 - Google Patents

ポリイミド前駆体ワニス、ポリイミド樹脂、及びその用途 Download PDF

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WO2013136807A1
WO2013136807A1 PCT/JP2013/001743 JP2013001743W WO2013136807A1 WO 2013136807 A1 WO2013136807 A1 WO 2013136807A1 JP 2013001743 W JP2013001743 W JP 2013001743W WO 2013136807 A1 WO2013136807 A1 WO 2013136807A1
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polyimide precursor
polyimide
precursor varnish
diamine
component
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PCT/JP2013/001743
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English (en)
French (fr)
Japanese (ja)
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飯田　健二
繁夫 木場
清水 今川
裕介 富田
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三井化学株式会社
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • 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
    • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
    • 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
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • 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
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
    • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention relates to a polyimide precursor varnish comprising a composition including a polyimide precursor and a solvent. Moreover, it is related with the polyimide resin formed by imidizing the molding obtained from the polyimide precursor varnish. Furthermore, it is related with the use which uses the said polyimide precursor varnish or a polyimide resin.
  • Wire wiring and cables have a structure in which a metal conductor is coated with an insulating coating material and a conductor portion is protected.
  • Various products have been developed for insulation coatings depending on the application, but engineering plastics such as polyamide, polyamideimide, polyesterimide, and polyimide are used for insulation coating materials such as electric wires and motor windings. Yes.
  • polyimide exhibits extremely excellent characteristics from the viewpoints of heat resistance, electrical insulation, mechanical strength, and the like, and is therefore used for motor windings that are used in particularly severe environments.
  • polyimides include KAPTON, VESPEL (registered trademark, manufactured by Dupont) consisting of bis (4-aminophenyl) ether and pyromellitic dianhydride, bis (4-aminophenyl) ether and 3,3 Examples include Iupilex (registered trademark, manufactured by Ube Industries) and AURUM (registered trademark, manufactured by Mitsui Chemicals), which are polyimides composed of ', 4,4'-biphenyltetracarboxylic dianhydride.
  • Patent Document 1 a polyimide having a repeating structural unit represented by the following general formula (I) is heated and melted in an extruder at a temperature range of 300 ° C. or higher and 450 ° C. or lower to coat a conductor, cooled and solidified to be insulated.
  • a method of manufacturing an insulated wire for forming a body is described.
  • R is an aliphatic group having 2 or more carbon atoms, a cyclic aliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group directly or via a cross-linking member.
  • Patent Document 2 discloses an insulated wire using p-phenylenediamine and 4,4′-diaminodiphenyl ether as diamine and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride as acid dianhydride. Has been.
  • Patent Document 3 discloses a repeating unit represented by the following general formula (II) in order to obtain an insulating paint and an insulated wire that can form an insulating film having heat resistance, high adhesion to a conductor, and low dielectric constant.
  • An insulating paint made of a polyimide resin having a repeating unit represented by the following general formula (III) has been proposed.
  • X 1 is a tetravalent aromatic group having an aromatic ether structure represented by the following formula (IV)
  • Y 1 is a divalent aromatic group having an aromatic ether structure.
  • X 2 is a tetravalent alicyclic group
  • Y 2 is a divalent alicyclic group containing an alicyclic structure
  • m and n are repeat numbers, each being a positive integer.
  • JP-A-2-210713 Japanese Patent Laid-Open No. 7-37439 JP 2010-189510 A
  • the present invention has been made in view of the above background, and the object of the present invention is to provide a material having excellent insulating properties and mechanical strength and satisfying both heat resistance and low water absorption. It is to provide a polyimide precursor varnish, a polyimide resin, and uses thereof.
  • the polyimide precursor varnish according to the present invention is a polyimide precursor varnish composed of a composition including a polyimide precursor and a solvent, and the composition is coated and heated at 5 ° C./min and 300 ° C.
  • the glass transition temperature is 290 ° C. or higher
  • the water absorption is 2.0% or less
  • the tensile elongation at break is 55% or more.
  • the polyimide precursor varnish disclosed herein is obtained by polycondensation of diamine and acid dianhydride, and the diamine is at least the total amount of the diamine.
  • the diamine component A represented by the chemical formula (1) which is 19 mol% or more and 56 mol% or less with respect to the total amount, and the chemical formula (2) which is 44 mol% or more and 81 mol% or less with respect to the total amount of the diamine.
  • the acid dianhydride component represented by the chemical formula (3) is 60 mol% or more and 100 mol% or less with respect to the total amount of the acid dianhydride.
  • C and acid dianhydride component D represented by chemical formula (4) which is 0 mol% or more and 40 mol% or less with respect to the total amount of the acid dianhydride.
  • X represents a divalent group such as a single bond, oxygen atom, sulfur atom, sulfone group, carbonyl group, methylene group, isopropylidene group or hexafluoroisopropylidene group
  • Y represents a divalent group of a single bond, an oxygen atom, a sulfur atom, a sulfone group, a carbonyl group, a methylene group, an isopropylidene group or a hexafluoroisopropylidene group
  • the polyimide precursor varnish disclosed herein has a total of 47. diamine component A and diamine component B with respect to the total of diamine and acid dianhydride. 5 to 52.5 mol%, copolymerized so that the total of the acid dianhydride component C and the acid dianhydride component D satisfies 47.5 to 52.5 mol%.
  • the diamine component B is 4,4′-bis (3-aminophenoxy) biphenyl described by the chemical formula (5).
  • the diamine component A is 4,4′-diaminodiphenyl ether described by the chemical formula (6).
  • the acid dianhydride component D is 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride described by the chemical formula (7). There are things that are things.
  • the polyimide resin according to the present invention is formed by imidizing a molded product obtained from the polyimide precursor varnish of the above embodiment. Moreover, in the preferable one aspect
  • An electronic component according to the present invention is an electronic component comprising a conductor and an insulating coating material covering the conductor, wherein at least a part of the insulating coating material is obtained from the polyimide precursor varnish of the above aspect.
  • a suitable example of the electronic component is an insulated wire.
  • the heat-resistant tape according to the present invention includes a support base material and a bonding layer formed on the support base material, and the support base material is formed by immobilizing a molded product obtained from the polyimide precursor varnish of the above aspect. It contains a polyimide resin formed as a component.
  • the heat resistant paint according to the present invention includes the polyimide precursor varnish of the above aspect.
  • the aerospace adhesive according to the present invention includes the polyimide precursor varnish of the above aspect or a gel film formed from the polyimide precursor varnish.
  • a polyimide precursor varnish, a polyimide resin, and uses thereof that have excellent insulating properties and mechanical strength, and that can provide a material that has both heat resistance and low water absorption.
  • a material that has both heat resistance and low water absorption There is an excellent effect of being able to.
  • the raw material excellent in the low water absorption can be provided.
  • the typical sectional view showing an example of the insulated wire concerning this embodiment The typical sectional view showing an example of the insulated wire concerning a modification.
  • any number A to any number B means a range larger than the numbers A and A but smaller than the numbers B and B.
  • the polyimide precursor varnish according to the present invention is composed of a composition including a polyimide precursor and a solvent. More specifically, the coating film thickness after drying obtained by coating a polyimide precursor varnish as a composition and heat-treating at 5 ° C./min and 300 ° C. for 1 hour in a nitrogen atmosphere.
  • a polyimide film having a range of 20 ⁇ m or more and 60 ⁇ m or less hereinafter simply referred to as “polyimide film”
  • a glass transition temperature is 290 ° C.
  • the polyimide resin of the present invention is formed by imidizing a molded product obtained from the polyimide precursor varnish of the present invention.
  • the molded product is a coating film, a film, a sheet, a molded product, a gel film, or the like.
  • the polyimide precursor varnish may be coated to 300 to 400 ⁇ m.
  • the production method of the said polyimide film is not specifically limited, The following method is mentioned as an example. That is, the polyimide precursor varnish is applied on a glass plate with a 300-400 ⁇ m gap applicator using a desktop coating machine. Then, immediately using an explosion-proof dryer, the temperature is raised from room temperature to 5 ° C./min in a nitrogen atmosphere as described above, and held at 300 ° C. for 1 hour. Then, after sufficiently cooling by natural cooling, the polyimide film is peeled from the glass plate by being immersed in warm water for 24 hours. Then, by sufficiently drying, the coating film thickness after drying is made to be 20 to 60 ⁇ m.
  • the polyimide precursor varnish according to the present invention only needs to satisfy the above characteristics (i) to (iii) when a polyimide film having the above film thickness is produced.
  • Use of the polyimide precursor varnish of the present invention The film thickness of the embodiment is not specified. That is, the polyimide precursor varnish of the present invention can be used to obtain films, sheets, and molded articles having various film thicknesses.
  • the glass transition temperature of (i) is more preferably 295 ° C. or higher, and further preferably 300 ° C. or higher.
  • the water absorption rate of (ii) is more preferably 1.9% or less, and further preferably 1.8% or less.
  • the tensile elongation at break of (iii) is more preferably 70% or more, and particularly preferably 100% or more.
  • the dielectric constant of the polyimide resin at a measurement frequency of 1 Hz is preferably 3.6 or less, more preferably 3.5 or less. More preferably, it is 4 or less.
  • the water absorption rate of this specification says the value measured with the following method. That is, the polyimide film is cut into a size of 50 mm ⁇ 50 mm, dried at 150 ° C. for 5 minutes, and then immediately measured for mass. Then, it is immersed in ion exchange water at 23 ° C. for 24 hours. After immersion, the moisture attached to the surface of the sample taken out from the water tank is sufficiently blown off using an air gun or the like, the mass is measured, and the value calculated from the following formula (1) is taken as the water absorption rate.
  • Water absorption rate ⁇ (Sample weight after immersion)-(Sample weight before immersion) ⁇ ⁇ (Sample weight before immersion) ..Formula (1)
  • the tensile elongation at break means a value measured by the following method. That is, the polyimide film was cut into a size of 140 mm in length ⁇ 10 mm in width, the actual measurement length was 100 mm (of which 20 mm at both ends was the pulling region), and the room temperature (23 The strip-shaped film sample was pulled at a speed of 50 mm / min. The value calculated from (length of polyimide film at break) / (original length of polyimide film) at this time is taken as the tensile break elongation.
  • the polyimide precursor which is a component of the polyimide precursor varnish of the present invention can be obtained by polycondensation of diamine and acid dianhydride.
  • suitable polyimide precursors for satisfying the above characteristics will be described.
  • the polyimide precursor of the present invention is not limited as long as it satisfies the above characteristics (i) to (iii), but preferred monomers include the following aspects. That is, the diamine is at least 19 mol% and not more than 56 mol% with respect to the total amount of the diamine, and the diamine component A represented by the chemical formula (1) and at least 44 mol% and 81 mol with respect to the total amount of the diamine. There exists an aspect which uses the diamine component B shown by Chemical formula (2) which is% or less as a structural component.
  • X represents a single bond, an oxygen atom, a sulfur atom, a sulfone group, a carbonyl group, a methylene group, an isopropylidene group, or a hexafluoroisopropylidene group.
  • the acid dianhydride is an acid dianhydride component C that is pyromellitic dianhydride represented by the chemical formula (3) that is at least 60 mol% and not more than 100 mol% with respect to the total amount of the acid dianhydride, And there exists an aspect which uses the acid dianhydride component D shown by Chemical formula (4) which is 0 mol% or more and 40 mol% or less with respect to the total amount of the said acid dianhydride as a structural component.
  • the lower limit value of pyromellitic dianhydride represented by the chemical formula (3) is more preferably 70 mol% or more, and further preferably 80 mol% or more.
  • the upper limit value of the acid dianhydride component D represented by the chemical formula (4) is more preferably 30 mol% or less, and further preferably 20 mol% or less.
  • Y represents a divalent group such as a single bond, oxygen atom, sulfur atom, sulfone group, carbonyl group, methylene group, isopropylidene group or hexafluoroisopropylidene group.
  • Preferred examples of the diamine component B of the chemical formula (2) include bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy). ) Phenyl] ketone, 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (3-aminophenoxy) phenyl] propane 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane and the like.
  • diamine component B 4,4′-bis (3-aminophenoxy) biphenyl described by the chemical formula (5) can be given.
  • diamine component A of the chemical formula (1) examples include 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether and the like. From the viewpoint of improving crystallinity, 4,4′-diaminodiphenyl ether represented by the chemical formula (6) is particularly preferable.
  • the diamine is preferably such that the diamine component A is 19 to 56 mol% with respect to the total amount of diamine and the diamine component B is 44 to 81 mol% with respect to the total amount of diamine. By setting it as this range, it is possible to achieve both low water absorption and high Tg more effectively.
  • the lower limit of the diamine component A with respect to the total amount of diamine is more preferably 20 mol% or more, further preferably 24 mol% or more, particularly preferably 30 mol% or more, and most preferably 39 mol% or more.
  • the upper limit value of the diamine component A relative to the total amount of diamine is more preferably 51 mol% or less, and further preferably 50 mol% or less.
  • the lower limit value of the diamine component B relative to the total amount of diamine is more preferably 49 mol% or more, and the upper limit value is more preferably 80 mol% or less, still more preferably 76 mol% or less, particularly preferably 70 mol% or less, and 61 mol%. The following are most preferred.
  • a diamine other than the above chemical formulas (1) and (2) may be used as long as the above-mentioned polyimide film satisfies the characteristics (i) to (iii).
  • the other diamine is preferably an aromatic diamine.
  • aromatic diamines include, for example, p-phenylenediamine, m-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, 4,4′-diaminobiphenyl, 3,3′-diaminobiphenyl, 4,4 '-Diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,1-bis (4-aminophenyl) ethane, 1,1-bis (3-aminophenyl) ethane, 2,2-bis (4-aminophenyl) Propane, 2,2-bis (3-aminophenyl) propane, 2,2-bis (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis- ( 3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 3,3′-diaminodiphenyl s
  • Preferred examples of the acid dianhydride component D represented by the chemical formula (4) include 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetra Carboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2,2-bis (3 4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3 -Dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride, 2,2-
  • 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4 ′ -More preferred are diphenyl ether tetracarboxylic dianhydride and p-phenylenedioxydi (4-phthalic acid) dianhydride. Particularly preferred is 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride described by the chemical formula (7).
  • the acid dianhydride component C may be used alone, or in addition to the acid dianhydride component C, the acid dianhydride component D may be added.
  • the acid dianhydride component D one type of compound may be used, or two or more types may be mixed and used.
  • an acid dianhydride other than the chemical formulas (3) and (4) can be used as long as the characteristics (i) to (iii) are satisfied.
  • the other acid dianhydride is preferably an aromatic acid dianhydride.
  • aromatic dianhydrides 1,2,3,4-benzenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,4 5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6, 7-anthracene tetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, and the like.
  • the number average molecular weight of the polyimide precursor according to this embodiment is not particularly limited, but can be, for example, in the range of 5,000 to 1,000,000. A preferred range is 5,000 to 50,000.
  • the number average molecular weight of the polyimide precursor can be measured by gel permeation chromatography (GPC).
  • the ratio of the polyimide precursor acid dianhydride and diamine during synthesis is not particularly limited, but the total of diamine component A and diamine component B is 47.5 to 52.5 mol with respect to the total of diamine and acid dianhydride. %, And the acid dianhydride component C and the acid dianhydride component D are preferably copolymerized in a range satisfying 47.5 to 52.5 mol%.
  • Polymerization can be performed in a solid phase system, but is preferably performed in a liquid phase system.
  • the polymerization concentration is, for example, about 20 to 30% by mass.
  • the reaction solvent is not particularly limited, but preferably has a boiling point of 100 ° C. or higher.
  • a solvent used for polymerization of a polyimide precursor can be suitably used.
  • it dissolves at least one reactant, preferably both acid dianhydrides and diamines.
  • Specific examples include N, N-dimethylformamide, N, N-dimethylacetamide, cresol, dimethyl sulfoxide, N-methyl-2-pyrrolidone, tetramethylurea and the like.
  • These solvents can be used alone or in combination with other solvents such as benzonitrile, dioxane, xylene or toluene.
  • the production of the polyimide precursor can be performed without using a catalyst, but a catalyst may be used as appropriate.
  • the catalyst is not particularly limited as long as it does not depart from the spirit of the present invention.
  • the amount of the catalyst used may be appropriately adjusted in consideration of the properties of the catalyst itself such as the volatility of the catalyst and the acid strength, and the reaction conditions.
  • the order and method of charging the raw materials, the solvent, and other catalysts added as necessary are not particularly limited.
  • the reaction temperature is not particularly limited as long as the necessary number average molecular weight (Mn) is obtained, but is usually 20 ° C. or higher and 100 ° C. or lower when polyamic acid is polymerized as a polyimide precursor.
  • the reaction time is not limited to a range that is sufficient to obtain the required degree of polymerization.
  • the reaction is preferably performed in an inert gas atmosphere such as nitrogen.
  • the solid content concentration in the reaction system (in the reactor) is not particularly limited, but is usually 5% by mass to 50% by mass.
  • reaction apparatus is not particularly limited, Super Blend (Sumitomo Heavy Industries, Ltd.), Aiko Chemical Mixer (Aikosha Seisakusho), Planetary Mixer (Inoue Seisakusho), Trimix (Inoue Seisakusho), etc. These kneaders can be mentioned.
  • the concentration of the resin solid content in the polyimide precursor varnish is preferably 5 to 50% by mass, more preferably 10 to 30% by mass, from the viewpoint of improving the coatability.
  • the solvent is not particularly limited, but is preferably a polar solvent.
  • polar solvents include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, dimethyl sulfoxide, hexamethyl phosphor
  • a mixed solvent with 3,5-trimethylbenzene, 1,2,4-trimethylbenzene or the like is included.
  • any additive may be added to the polyimide precursor varnish according to the present invention without departing from the spirit of the present invention.
  • an adhesion assistant, an adhesive, an antioxidant, an ultraviolet absorber, a colorant, or the like may be added.
  • a surface modifier such as a silane coupling agent may be added.
  • preferable additives include epoxy, bismaleimide, and nadiimide. From the viewpoint of heat resistance and reactivity, it is preferable to add bismaleimide having a molecular weight of 600 or less.
  • the polyimide precursor according to the present invention may be a single type or a mixture of a plurality of types.
  • the polyimide precursor varnish of the present invention may be mixed with a polymer different from the polyimide precursor according to the present invention without departing from the spirit of the present invention. That is, in the polyimide resin obtained from the polyimide precursor varnish, other polymers may be included without departing from the spirit of the present invention. Moreover, in the polyimide precursor varnish, what was partially imidized may be contained.
  • Conventional polyimide resins generally have a water absorption rate exceeding 2.0% due to imide groups. For this reason, for example, when a polyimide resin is applied as an insulating coating material for a conductor of an insulated wire, there is a problem in that transmission loss increases due to the insulating coating material. In addition, the conventional polyimide resin has a problem in that poor insulation is likely to occur due to water absorption under high humidity heat.
  • the polyimide structure as in Patent Document 1 By adopting the polyimide structure as in Patent Document 1, it is possible to relatively reduce the imide group density and improve the water absorption rate. However, since the glass transition temperature is lowered due to this, there is a problem in terms of heat resistance. Thus, the polyimide resin has a trade-off relationship between low water absorption and heat resistance, and it has been difficult to satisfy both low water absorption and heat resistance. In addition, when molding by melt extrusion molding method as in Patent Document 1, molding at a high temperature of 400 ° C. or higher is generally necessary, and since it is close to the thermal decomposition temperature of the resin, it is necessary to precisely control the molding conditions. was there.
  • the above-mentioned polyimide film has a glass transition temperature of 290 ° C. or higher, a water absorption rate of 2.0% or less, and a tensile breaking elongation of 55% or more. It is possible to provide a polyimide resin excellent in balance and having a high glass transition temperature and a high mechanical strength. More specifically, by setting the glass transition temperature to 290 ° C. or higher, excellent reliability and durability can be realized even in a high temperature environment. For example, it can be used for a long time even in an environment of about 250 ° C.
  • the water absorption rate to 2.0% or less, a low transmission loss can be realized when used as an insulating coating material for covering a conductor.
  • the tensile elongation at break is 55% or more, excellent mechanical strength can be realized, and excellent reliability and durability can be realized.
  • the flexibility is excellent.
  • the method of applying the polyimide precursor varnish of the present invention it has an excellent merit that it can be dried by heating at 400 ° C. or lower and it is easy to form a thin film.
  • the above-mentioned excellent balance between low water absorption, high glass transition temperature, and high mechanical strength By using the diamine having the above-mentioned specific structure as the polyimide precursor, and using the acid dianhydride having the above-mentioned specific structure, the above-mentioned excellent balance between low water absorption, high glass transition temperature, and high mechanical strength. It is possible to easily provide a polyimide resin having the effect described above. By introducing pyromellitic dianhydride of chemical formula (3) or pyromellitic dianhydride and chemical formula (4) as acid dianhydride and using diamines of chemical formulas (1) and (2) When the polyimide resin is used, the imide group density can be lowered and the crystallinity can be improved while realizing the rigidity. As a result, we consider that we succeeded in balancing low water absorption, high glass transition temperature and high mechanical strength. In addition, the polyimide resin obtained has an excellent merit that low dielectric constant can be realized.
  • mBP 4,4′-bis (3-aminophenoxy) biphenyl
  • s-BPDA 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride
  • polyimide resin has excellent chemical resistance. Therefore, there is an excellent merit that it can be used even in severe conditions such as high temperature and high humidity and in applications where chemical resistance is required.
  • the polyimide precursor varnish of the present invention it is possible to provide a material having excellent insulating properties and mechanical strength, and having both heat resistance and low water absorption, so various electronic parts such as insulated wires, heat resistant tape, heat resistance It can be suitably used for a wide range of applications including paints and aerospace adhesives.
  • an example of the embodiment formed using the polyimide precursor varnish of the present invention will be described.
  • FIG. 1A is a schematic cross-sectional view showing an example of an insulated wire according to the present invention.
  • the insulated wire 1 has a conductor 10 and an insulating coating layer 20 formed of an insulating coating material.
  • the conductor 10 is not particularly limited as long as it can function as an electric wire.
  • the conductor 10 is made of a conductive material such as oxygen-free copper, copper, aluminum, an aluminum alloy, or a combination thereof.
  • the insulating coating layer 20 covers the conductor 10 and is made of a polyimide resin formed using a polyimide precursor varnish. Between the conductor 10 and the insulating coating layer 20, an adhesion layer that improves the bonding may be provided. In the example of FIG.
  • the insulating coating layer 20 may be a laminated structure of layers, or may be a laminated structure of three or more layers.
  • a plurality of layers are laminated, a plurality of polyimide resins formed using the polyimide precursor varnish according to the present invention may be laminated, or a laminate of another insulating layer and the polyimide resin of the present invention may be used.
  • the other insulating layer is not particularly limited, but can be appropriately designed according to needs, such as a material that improves the adhesion to the conductor 10 or a highly flexible material.
  • the thickness of the insulating coating layer 20 can be arbitrarily set according to the application and is not particularly limited, but can be set to about 1 to 100 ⁇ m, for example.
  • a more preferable lower limit value of the insulating coating layer 20 is 10 ⁇ m or more, and a more preferable range is 20 ⁇ m or more.
  • the insulating coating layer 20 is obtained by applying a polyimide precursor varnish to the conductor 10, drying it, and baking it.
  • the coating method is not particularly limited, a method of directly or indirectly coating the outer periphery of the conductor 10 can be exemplified.
  • the polyimide precursor is converted into polyimide by baking. In the case where a plurality of insulating coating layers are laminated, it can be formed by repeating the coating and baking process.
  • a known forming method can be used as appropriate.
  • the baking step is not particularly limited, but is preferably performed in an inert gas, and can be performed, for example, in a nitrogen atmosphere.
  • the heating condition is not particularly limited as long as it can be converted from the polyimide precursor to the polyimide, and examples include heating at about 200 to 400 ° C. for 1 minute to 10 hours.
  • the conductor 10 and the insulating coating layer 20 described above have examples in which the cross section has a round cross section, the cross section is not particularly limited, and may be independently a rectangular shape, an elliptical shape, or the like. .
  • the insulated wire of the present invention since the polyimide resin obtained from the polyimide precursor varnish according to the present invention is used for at least one layer of the insulating coating layer 20, the mechanical strength is excellent. Therefore, the internal conductor 10 can be appropriately protected even when a strong external force is applied.
  • the polyimide resin according to the present invention is excellent in low water absorption, when used as the insulated wire 1, low transmission loss can be realized.
  • the polyimide resin according to the present invention is excellent in chemical resistance and heat resistance, it can be suitably used even under severe conditions such as high temperature and high humidity.
  • FIG. 2 is a schematic cross-sectional view showing an example of the heat-resistant tape of the present invention.
  • the heat-resistant tape 2 includes a support base 30 and a bonding layer 31. Between the support base material 30 and the joining layer 31, you may provide the intermediate
  • a support base 30 and a bonding layer 31 that have heat resistance are used in order to ensure heat resistance that can be used even in a high temperature region around 200 ° C.
  • the support substrate 30 includes a polyimide resin layer formed from at least the polyimide precursor varnish of the present invention.
  • the support substrate 30 may be composed of a single layer or a plurality of polyimide resin layers, or may be a laminate of a layer made of another material and a polyimide resin layer.
  • Other materials are not limited as long as they do not depart from the spirit of the present invention, and examples thereof include metal foils such as aluminum foil, metal layers, plastic films, and the like. What is excellent in bondability with the polyimide resin layer formed from the polyimide precursor varnish of this invention, and excellent in heat resistance is preferable.
  • the bonding layer 31 is not particularly limited as long as it can be bonded to the adherend and does not depart from the gist of the present invention, but an adhesive layer is usually used.
  • the bonding layer 31 include a silicone pressure sensitive adhesive, a rubber pressure sensitive adhesive, and an acrylic pressure sensitive adhesive. From the viewpoint of increasing the heat resistance of the bonding layer 31, it is preferably thermosetting.
  • the thickness and size of the heat-resistant tape 2 can be appropriately designed according to various uses.
  • the thickness of the support base 30 is preferably about 2 to 100 ⁇ m.
  • the lower limit value of the support substrate 30 is more preferably 5 ⁇ m or more, and further preferably 10 ⁇ m or more.
  • the upper limit value of the support substrate 30 is more preferably 50 ⁇ m or less, and further preferably 30 ⁇ m or less.
  • the thickness of the bonding layer 31 can be about 3 to 100 ⁇ m, for example.
  • the adhesive force can be adjusted by adjusting the thicknesses of the support base 30 and the bonding layer 31.
  • a heat-resistant tape excellent in followability and a high-rigidity heat-resistant tape can be provided by appropriately selecting the thickness, the material of the bonding layer, and the laminated form according to the required use.
  • the heat-resistant tape 2 can be manufactured by various methods, and the following methods can be exemplified. That is, a gel film is obtained by continuously extruding or coating a polyimide precursor varnish in a film form on a rotating support. Next, the gel film is peeled from the support, and imidized by stretching, drying, and heat treatment to obtain the support substrate 30. Thereafter, the bonding layer 31 is formed thereon by a conventionally known coating method.
  • the coating method is not particularly limited, and examples thereof include a roll coater method, a reverse roll coater method, a gravure roll method, a bar coat method, a comma coater method, and a die coater method.
  • the drying conditions of the applied pressure-sensitive adhesive may be appropriately adjusted depending on the pressure-sensitive adhesive to be used, but in general, it is dried for 10 seconds to 10 minutes in a temperature range of 80 to 200 ° C.
  • the gel film referred to in the present invention is a film containing a polyimide precursor and / or a polyimide precursor mixed with a partially imidized polyimide resin, and a solvent.
  • the gel film has a film thickness of about 1 to 100 ⁇ m and a solvent content of about 1 to 70% by mass.
  • the heat-resistant tape 2 is not limited to the example of FIG. 2 and can take various forms. For example, it is good also as a double-sided tape which provided the joining layer on both surfaces of the support base material 30. FIG. Moreover, it is good also as a structure which laminates
  • the size of the heat-resistant tape 2 of the present invention is not particularly limited, and includes a sheet-like one in addition to a so-called tape-like form having a strip shape. Further, the gel film itself obtained from the polyimide precursor varnish can be used as the heat-resistant tape 2 without providing the bonding layer 31.
  • the polyimide resin obtained from the polyimide precursor varnish of the present invention since the polyimide resin obtained from the polyimide precursor varnish of the present invention is used, it has excellent insulating properties and mechanical strength, and further has both heat resistance and low water absorption. In addition, it has excellent chemical resistance and weather resistance. Moreover, since it is excellent also in flexibility, it can be applied to adherends of various shapes. Therefore, for example, it is suitable as a masking tape used for heat equipment such as heat rolls and heaters, electrical insulation of members used under heating and pressurizing conditions, and a protective tape for printed circuit boards in the field of semiconductor manufacturing processes.
  • the heat-resistant paint of the present invention can contain a pigment as necessary.
  • the type of pigment is not particularly limited as long as it does not depart from the gist of the present invention, but as an example, carbon black, zinc phosphate, aluminum phosphate, calcium phosphate, magnesium phosphate, zinc molybdate, calcium molybdate, silica sand, calcium carbonate , Talc, clay, kaolin, precipitated barium sulfate and the like.
  • Anticorrosive pigments having heat resistance and corrosion resistance are preferred.
  • additives can be arbitrarily added to the heat-resistant paint of the present invention without departing from the spirit of the present invention.
  • examples include reinforcing materials, curing agents, asphalt emulsions, film-forming aids, antifoaming agents, dispersants, thickeners, plasticizers, antiseptics, antibacterial agents, rust inhibitors, and colorants.
  • Resin other than the polyimide precursor may be added to the heat resistant paint within a range not departing from the gist of the present invention.
  • the resin other than the polyimide precursor may be either a thermoplastic resin or a thermosetting resin, but is preferably a thermosetting resin from the viewpoint of heat resistance.
  • the solid content concentration of the heat-resistant paint of the present invention is not particularly limited as long as a coating film can be formed, but is preferably about 10 to 70% by mass. If it is less than 10% by mass, the thick film coatability is lowered, and if it exceeds 70% by mass, problems are likely to occur in the workability at the time of blending, storage stability and the like.
  • Examples of the heat-resistant paint coating method of the present invention include, for example, a method in which the above-described polyimide precursor varnish is applied to a surface to be coated, and heat treatment is performed under conditions that allow conversion from the polyimide precursor to polyimide.
  • the surface to be coated can be applied to various materials such as metal materials, ceramic materials, and plastic materials.
  • the surface to be coated may be subjected in advance to a surface treatment such as plasma treatment or blast treatment, or an undercoat layer may be formed.
  • the heat-resistant paint film is obtained by a method of imidization by heat treatment
  • a known method can be used without limitation as a coating method.
  • the method of forming a coating film by the coating method, the dipping method, the spray method, the brush coating method etc. can be illustrated.
  • the heat treatment condition is not particularly limited as long as it can be converted from a polyimide precursor to a polyimide.
  • it can be obtained by heating at about 200 to 400 ° C. for 1 minute to 10 hours. You may carry out in air
  • the polyimide resin obtained from the polyimide precursor varnish of the present invention since the polyimide resin obtained from the polyimide precursor varnish of the present invention is contained as a main component, it has excellent insulating properties and mechanical strength, and has both heat resistance and low water absorption. Can provide. In addition, it has excellent chemical resistance and weather resistance. Moreover, since it is excellent also in flexibility, it can be applied as a heat-resistant film on a surface to be coated having a wide variety of shapes. Specifically, it is suitable for electrical / electronic equipment, machines, automobiles, aerospace equipment, general industrial equipment, and the like. It is also suitable for applications exposed to high temperature environments.
  • the aerospace adhesive of the present invention may be composed only of the polyimide precursor varnish of the present invention, or may be mixed when other adhesive components such as a two-component type are used. Moreover, it may consist of a polyimide resin film obtained by imidizing a coating film of a polyimide precursor varnish.
  • the aerospace adhesive includes a polyimide precursor varnish.
  • a resin other than the polyimide precursor may be added without departing from the gist of the present invention.
  • the resin other than the polyimide precursor may be either a thermoplastic resin or a thermosetting resin, but is preferably at least partially compatible with the polyimide precursor, and is preferably a thermosetting resin from the viewpoint of heat resistance.
  • Suitable resins include epoxy resins, bismaleimide resins, acrylic resins, benzoxazole resins and the like.
  • the amount of the thermosetting resin is preferably 1 to 200 parts by mass, more preferably 5 to 100 parts by mass with respect to 100 parts by mass of the polyimide resin. It is desirable in that the film is suitable and the film formability is improved.
  • thermosetting resins those with various structures are commercially available, the industrial application range is wide, appropriate curing can be realized, and the crosslinking density can be controlled by the blending ratio, Epoxy resins are preferred.
  • the epoxy resin is not particularly limited as long as it contains at least two epoxy groups in the molecule.
  • phenol glycidyl ether type epoxy resins include bisphenol A, bisphenol AD, bisphenol S, bisphenol F or a condensate of halogenated bisphenol A and epichlorohydrin, glycidyl ether of phenol novolac resin, glycidyl ether of cresol novolac resin, bisphenol A novolak Examples thereof include glycidyl ether of resin, glycidyl ether of dicyclopentadiene-modified phenol novolac resin, and biphenyl type epoxy resin.
  • the inorganic substance filler may contain a curing agent as required, and examples thereof include a phenolic curing agent, an amine curing agent, an acid anhydride curing agent, and imidazoles.
  • blend the inorganic substance filler is blended for the purpose of imparting low thermal expansion, low hygroscopicity, high elasticity, high thermal conductivity, etc. to the adhesive, and also contributes to improving the strength of the film adhesive.
  • the inorganic filler include inorganic insulators such as silica, alumina, silicon nitride, aluminum nitride, boron nitride, titania, glass, iron oxide, and ceramic. These can be used individually or in mixture of 2 or more types.
  • a coupling agent such as a silane coupling agent or a titanium-based coupling agent may be appropriately added to the adhesive as necessary, as long as the object of the present invention is not impaired.
  • a coupling agent contributes to the improvement of the adhesive strength in the adhesion interface with a to-be-adhered body or a filler.
  • the amount of solvent in the aerospace adhesive of the present invention is not particularly limited, but is usually adjusted so that the viscosity of the varnish has fluidity.
  • the amount of the polyimide precursor component usually contained in the varnish is in the range of 1 to 40% by mass, preferably 5 to 35% by mass, more preferably 10 to 30% by mass, the fluidity, workability, film formability, coating It is desirable in terms of workability.
  • the viscosity of the varnish is not particularly limited, but is appropriately selected within a range that is easy to handle, and may further contain a viscosity adjusting agent or the like as necessary.
  • the coated surface of the aerospace adhesive of the present invention is not particularly limited, and examples thereof include metal materials, ceramic materials, plastic materials, and the like.
  • the surface to be coated may be subjected in advance to a surface treatment such as plasma treatment or blast treatment, or an undercoat layer may be formed.
  • the aerospace adhesive may be applied as it is or may be formed on a base film.
  • a coating film forming method, a heat treatment method, and the like are not particularly limited. For example, the example demonstrated by the coating method of a heat-resistant paint can be given.
  • another embodiment of the aerospace adhesive of the present invention is a film.
  • a film-like adhesive is used, the above-described method using a gel film is preferable. That is, a gel film is obtained by continuously extruding or coating a polyimide precursor varnish in a film form on a rotating support, and the gel film is peeled from the support, and is manufactured by stretching, drying, and heat treatment. The method is preferred. Also, a method of obtaining a coating film on a glass substrate or a highly releasable polyimide film and peeling off after heat treatment, or peeling off a gel film applied on a release-treated PET film, Examples of the method include manufacturing by stretching, drying, and heat treatment.
  • the thickness of the film-like adhesive layer may be, for example, about 1 to 200 ⁇ m, although it depends on the application.
  • a film adhesive When a film adhesive is used, it can be sandwiched between objects to be bonded and thermocompression bonded.
  • the temperature at the time of pressure bonding is preferably higher than the glass transition temperature of the resin composition, and is usually 300 to 450 ° C., preferably 350 to 400 ° C. Within such a range, the polyimide composition can be sufficiently bonded without thermal decomposition.
  • the polyimide resin obtained from the polyimide precursor varnish of the present invention is contained as a main component, so that it has excellent insulating properties and mechanical strength, and has both heat resistance and low water absorption. To do. In addition, it has excellent chemical resistance and weather resistance. Moreover, since it is excellent also in flexibility, it is suitable as an aerospace adhesive used under severe high temperature environment and high humidity environment.
  • Example 1 Preparation of polyimide precursor varnish
  • 4,4′-diaminodiphenyl ether Wakayama Seika Co., Ltd.
  • 4,4′-ODA 4,4 in a dimethylacetamide solvent
  • m-BP diamines
  • PMDA pyromellitic dianhydride
  • the polyimide precursor varnish was applied on a glass plate with a 360 ⁇ m gap applicator using a desktop coater. Immediately after the coating, it was dried in a nitrogen atmosphere using an explosion-proof dryer. In drying, the temperature was raised from room temperature at 5 ° C./min and held at 300 ° C. for 1 hour. Then, it cooled naturally. After sufficiently cooling, the polyimide film was peeled off from the glass plate by being immersed in warm water for 24 hours to obtain a desired polyimide film sample. The film thickness after drying of the obtained polyimide film was 30 ⁇ m.
  • the water absorption of the produced film sample was evaluated by the water absorption rate.
  • the target sample was cut into a size of 50 mm ⁇ 50 mm, dried at 150 ° C. for 5 minutes, and immediately measured for mass. Then, it was immersed in ion exchange water at 23 ° C. for 24 hours. After immersion, the moisture attached to the surface of the sample taken out from the water tank was sufficiently blown off with an air gun, the mass was measured, and the water absorption was calculated from the above formula (1).
  • a sample having a water absorption rate of 2.0% or less was rated as ⁇ , and a sample having a water absorption rate exceeding 2.0% was rated as x.
  • Glass transition temperature evaluation heat resistance evaluation
  • RSA-III manufactured by TA instruments was used as Those having a glass transition temperature of 290 ° C. or higher were evaluated as “B” and those having a glass transition temperature of less than 290 ° C. as “C”.
  • the tensile mechanical strength of the produced polyimide film was measured. A sample was cut into a size of 140 mm length ⁇ 10 mm width, and 20 mm portions at both ends were used as a tensile region (actual measurement length was 100 mm). The tensile break elongation was measured by pulling a strip-shaped film sample at a speed of 50 mm / min. As a measuring device, AUTOGRAPH AGS-100D manufactured by Shimadzu Corporation was used.
  • a sample having a tensile elongation at break (also referred to simply as “elongation at break”) of 55% or more was evaluated as ⁇ , and a sample having a tensile elongation at break of less than 55% was evaluated as x.
  • a polyimide precursor varnish was prepared and evaluated in the same manner as in Example 1 except that it was blended at a molar ratio of 5.
  • 4-APB 1,3-bis (4-aminophenoxy) benzene
  • a polyimide precursor varnish was prepared and evaluated in the same manner as described above.
  • Table 1 shows the preparation ratio of the polyimide acid varnish
  • Table 2 shows the physical property values.
  • the polyimide film according to this example was excellent in low dielectric constant.
  • the dielectric constant of the polyimide film of Comparative Example 1 was 3.61
  • the dielectric constant of the polyimide film according to Example 2 was 3.35
  • the dielectric constant of the polyimide film according to Example 5 was 3. 33.
  • the glass transition temperature is 290 ° C. or more
  • the water absorption is 2.0% or less
  • the tensile elongation at break is 55% or more, in addition to excellent mechanical strength
  • the polyimide resin obtained from the polyimide precursor varnish according to the present invention has excellent insulating properties and mechanical properties, and also has excellent low water absorption and heat resistance. can do.
  • suitable applications include various electronic parts such as insulated wires, heat-resistant tapes, heat-resistant paints, and aerospace adhesives.

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63199237A (ja) * 1987-02-13 1988-08-17 Toray Ind Inc ポリイミド組成物
JPH0578484A (ja) * 1992-03-09 1993-03-30 Toray Ind Inc ポリイミド共重合体
JPH0741556A (ja) * 1993-07-29 1995-02-10 Kanegafuchi Chem Ind Co Ltd ポリイミド樹脂及びポリイミドフィルム
JPH07125134A (ja) * 1993-10-29 1995-05-16 Mitsui Toatsu Chem Inc ポリイミドフィルム・金属箔積層体およびその製造方法
JPH11199668A (ja) * 1997-10-23 1999-07-27 Kanegafuchi Chem Ind Co Ltd ポリイミド組成物及びそれからなるｔａｂ用テープとフレキシブルプリント基板
JP2006218767A (ja) * 2005-02-10 2006-08-24 Kaneka Corp ポリイミド系多層フィルムの製造方法およびその利用
JP2011195771A (ja) * 2010-03-23 2011-10-06 Kaneka Corp 接着フィルムの製造方法ならびにフレキシブル金属張積層板
JP2012224697A (ja) * 2011-04-18 2012-11-15 Sumitomo Electric Wintec Inc ポリイミド樹脂ワニス及びそれを用いた絶縁電線、電機コイル、モータ

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63199237A (ja) * 1987-02-13 1988-08-17 Toray Ind Inc ポリイミド組成物
JPH0578484A (ja) * 1992-03-09 1993-03-30 Toray Ind Inc ポリイミド共重合体
JPH0741556A (ja) * 1993-07-29 1995-02-10 Kanegafuchi Chem Ind Co Ltd ポリイミド樹脂及びポリイミドフィルム
JPH07125134A (ja) * 1993-10-29 1995-05-16 Mitsui Toatsu Chem Inc ポリイミドフィルム・金属箔積層体およびその製造方法
JPH11199668A (ja) * 1997-10-23 1999-07-27 Kanegafuchi Chem Ind Co Ltd ポリイミド組成物及びそれからなるｔａｂ用テープとフレキシブルプリント基板
JP2006218767A (ja) * 2005-02-10 2006-08-24 Kaneka Corp ポリイミド系多層フィルムの製造方法およびその利用
JP2011195771A (ja) * 2010-03-23 2011-10-06 Kaneka Corp 接着フィルムの製造方法ならびにフレキシブル金属張積層板
JP2012224697A (ja) * 2011-04-18 2012-11-15 Sumitomo Electric Wintec Inc ポリイミド樹脂ワニス及びそれを用いた絶縁電線、電機コイル、モータ

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10199137B2 (en) 2012-09-03 2019-02-05 Hitachi Metals, Ltd. Insulated wire and coil using the same
JP2014049377A (ja) * 2012-09-03 2014-03-17 Hitachi Metals Ltd 絶縁電線及びそれを用いたコイル
US10546667B2 (en) 2012-10-16 2020-01-28 Hitachi Metals, Ltd. Insulated wire and coil using same
JP2015130281A (ja) * 2014-01-08 2015-07-16 三井化学株式会社 多層絶縁電線
CN105139927A (zh) * 2015-06-30 2015-12-09 蓬莱市特种绝缘材料厂 一种核电机组用电磁线及其制备方法
JP2017027659A (ja) * 2015-07-15 2017-02-02 株式会社デンソー 絶縁電線
JP7140432B2 (ja) 2018-08-22 2022-09-21 ピーアイ・アドバンスド・マテリアルズ・カンパニー・リミテッド 芳香族カルボン酸を含む導体被覆用ポリイミドワニスおよびその製造方法
JP2021535243A (ja) * 2018-08-22 2021-12-16 ピーアイ・アドバンスド・マテリアルズ・カンパニー・リミテッド 芳香族カルボン酸を含む導体被覆用ポリイミドワニスおよびその製造方法
JP2021111448A (ja) * 2020-01-06 2021-08-02 日立金属株式会社 エナメル線及び塗料
JP7363488B2 (ja) 2020-01-06 2023-10-18 株式会社プロテリアル エナメル線及び塗料
CN111978725A (zh) * 2020-07-28 2020-11-24 凯正包装科技(广东)有限公司 一种抗菌耐高温老化的聚酰亚胺薄膜及其制备方法
CN113968971B (zh) * 2021-11-30 2022-05-27 富优特(山东)新材料科技有限公司 可溶性、低温快速酰亚胺化聚酰亚胺薄膜的制备方法
CN113968971A (zh) * 2021-11-30 2022-01-25 富优特(山东)新材料科技有限公司 可溶性、低温快速酰亚胺化聚酰亚胺薄膜的制备方法
CN114806396A (zh) * 2022-05-17 2022-07-29 住井科技(深圳)有限公司 使聚酰亚胺清漆兼具耐电涌性和耐湿热性的方法、聚酰亚胺清漆和绝缘电线
WO2023221232A1 (zh) * 2022-05-17 2023-11-23 住井科技(深圳)有限公司 使聚酰亚胺清漆兼具耐电涌性和耐湿热性的方法、聚酰亚胺清漆和绝缘电线

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