WO2013157565A1 - Film de polyimide thermoadhésif, méthode de production d'un film de polyimide thermoadhésif, et stratifié polyimide/métal utilisant un film de polyimide thermoadhésif - Google Patents

Film de polyimide thermoadhésif, méthode de production d'un film de polyimide thermoadhésif, et stratifié polyimide/métal utilisant un film de polyimide thermoadhésif Download PDF

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WO2013157565A1
WO2013157565A1 PCT/JP2013/061356 JP2013061356W WO2013157565A1 WO 2013157565 A1 WO2013157565 A1 WO 2013157565A1 JP 2013061356 W JP2013061356 W JP 2013061356W WO 2013157565 A1 WO2013157565 A1 WO 2013157565A1
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heat
polyimide
fusible
film
layer
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PCT/JP2013/061356
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English (en)
Japanese (ja)
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暢 飯泉
英雄 有原
英治 升井
圭一 柳田
拓郎 河内山
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宇部興産株式会社
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Priority claimed from JP2012095606A external-priority patent/JP2015129200A/ja
Priority claimed from JP2012282249A external-priority patent/JP2015128821A/ja
Application filed by 宇部興産株式会社 filed Critical 宇部興産株式会社
Publication of WO2013157565A1 publication Critical patent/WO2013157565A1/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
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • 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
    • 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
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/10—Batteries
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of 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 C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention relates to a heat-fusible polyimide film, a method for producing a heat-fusible polyimide film, and a polyimide metal laminate using the heat-fusible polyimide film.
  • Polyimide films are widely used as substrate materials such as flexible printed boards (FPC) and tape automated bonding (TAB).
  • FPC flexible printed boards
  • TAB tape automated bonding
  • an adhesive such as an epoxy resin or an acrylic resin can be used.
  • Patent Document 1 discloses a polyimide film having a heat-fusible property in which a heat-fusible polyimide layer is laminated on a heat-resistant polyimide layer. Is disclosed.
  • the present inventors set the types and blending ratios of the tetracarboxylic dianhydride component and the diamine component as the components of the heat-fusible polyimide film, and the conditions for producing the polyimide film.
  • the present invention was completed by earnest examination.
  • a multilayer heat-fusible polyimide film comprising a heat-fusible polyimide layer and a heat-resistant polyimide layer laminated in contact with the heat-fusible polyimide layer,
  • the heat-fusible polyimide layer is obtained from a tetracarboxylic dianhydride component and a diamine component, and the tetracarboxylic dianhydride component of the heat-fusible polyimide layer is a total tetracarboxylic dianhydride component.
  • 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is contained in an amount of 50 mol% or more, and the diamine component of the heat-fusible polyimide layer is 2,2-bis [4 -(4-aminophenoxy) phenyl] propane in excess of 50 mol%,
  • the heat-resistant polyimide layer is obtained from a tetracarboxylic dianhydride component and a diamine component, and the tetracarboxylic dianhydride component of the heat-resistant polyimide layer is the total tetracarboxylic dianhydride component, Containing 50 mol% or more of 3 ′, 4,4′-biphenyltetracarboxylic dianhydride,
  • a 18 ⁇ m copper foil is superposed on the heat-fusible polyimide layer of the heat-fusible polyimide film, and is higher by 30 ° C.
  • the polyimide metal laminate obtained by thermocompression bonding with a press pressure of 3 MPa and a press time of 1 minute in the following temperature range has a peel strength measured by the method of JIS C6471 of 0.5 N / mm or more.
  • Heat-sealable polyimide film (2) The heat according to (1), wherein the diamine component of the heat-fusible polyimide layer contains 70 mol% or more of 2,2-bis [4- (4-aminophenoxy) phenyl] propane in all diamines. Fusible polyimide film.
  • the tetracarboxylic dianhydride component of the heat-fusible polyimide layer is 50% of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride in the total tetracarboxylic dianhydride component.
  • the tetracarboxylic dianhydride component of the heat-fusible polyimide layer is 50% of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride in the total tetracarboxylic dianhydride component.
  • a polyimide precursor solution (a) that gives a heat-resistant polyimide layer and a polyimide precursor solution (b) that gives a heat-fusible polyimide layer are cast from an extrusion die on a support and laminated. Forming a thin film-like body, drying the thin-film body at a temperature of 140 ° C.
  • the polyimide precursor solution (a) is obtained from a tetracarboxylic dianhydride component and a diamine component, and the tetracarboxylic dianhydride component of the polyimide precursor solution (a) is all tetracarboxylic dianhydride.
  • 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is contained in an amount of 50 mol% or more
  • the polyimide precursor solution (b) is obtained from a tetracarboxylic dianhydride component and a diamine component, and the tetracarboxylic dianhydride component of the polyimide precursor solution (b) is all tetracarboxylic dianhydride.
  • 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is contained in an amount of 50 mol% or more, and the diamine component of the polyimide precursor solution (b) is 2,2-
  • a method for producing a heat-fusible polyimide film comprising more than 50 mol% of bis [4- (4-aminophenoxy) phenyl] propane.
  • (9) A polyimide metal laminate obtained by laminating a metal layer in contact with the heat-fusible polyimide layer of the heat-fusible polyimide film described in any one of (1) to (6) above.
  • a heat-fusible polyimide film having excellent heat resistance and excellent adhesion to a metal layer can be obtained.
  • the laminated body (polyimide metal laminated body) with high peeling strength of a polyimide film and a metal layer can be obtained by thermocompression-bonding this heat-fusible polyimide film and metal layers, such as copper foil.
  • the heat-fusible polyimide film of the present invention is a multilayer heat-fusible polyimide film including a heat-fusible polyimide layer and a heat-resistant polyimide layer laminated in contact with the heat-fusible polyimide layer.
  • the heat-fusible polyimide film of the present invention is a single-layer heat-fusible polyimide film composed of only a heat-fusible polyimide layer or a multilayer heat-fusing film including a heat-fusible polyimide layer as a surface layer. It is a conductive polyimide film.
  • thermal fusion means that the softening point of the polyimide film surface is less than 350 ° C.
  • the softening point is a temperature at which the object is softened suddenly when heated.
  • the glass transition temperature (Tg) is used for amorphous polyimide, and the melting point is used for crystalline polyimide.
  • Tg glass transition temperature
  • thermoplastic thermoplastic
  • the “heat-sealable polyimide layer” includes “a single-layer heat-sealable polyimide film”.
  • the heat-fusible polyimide layer is obtained by polymerizing a tetracarboxylic dianhydride component and a diamine component.
  • the heat-fusible polyimide layer comprises 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride as a tetracarboxylic dianhydride component, and 50 mol% or more of the total tetracarboxylic dianhydride component. Including.
  • the content of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride in the total tetracarboxylic dianhydride component is preferably 70 mol% or higher, more preferably 80 mol% or higher, more preferably 90 mol%. More than mol%. Further, the total tetracarboxylic dianhydride component may contain 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride exceeding 0 and less than 50 mol%, preferably 10 to 30 mol%. Thereby, a polyimide metal laminate having high peel strength can be obtained.
  • the heat-fusible polyimide layer contains 2,2-bis [4- (4-aminophenoxy) phenyl] propane as a diamine component in an amount exceeding 50 mol% in the total diamine.
  • the content of 2,2-bis [4- (4-aminophenoxy) phenyl] propane in all diamines is preferably 60 mol% or more from the viewpoint of obtaining a polyimide film having excellent heat resistance and low water absorption, which will be described later. More preferably, it is 65 mol% or more, and most preferably 70 mol% or more and 100% or less.
  • tetracarboxylic dianhydride component of the heat-fusible polyimide layer the above two acid components and other tetracarboxylic dianhydride components can be used in combination.
  • Other tetracarboxylic dianhydride components include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride Bis (3,4-dicarboxyphenyl) sulfide dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2 -Bis (3,4-dicarboxyphenyl) propane dianhydride, 1,4-hydroquinone dibenzoate-3,3 ', 4,4'-tetracarboxylic dianhydride and the like.
  • the above 2,2-bis [4- (4-aminophenoxy) phenyl] propane and another diamine component can be used in combination.
  • the diamine component used in combination include 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3 , 3′-diaminobenzophenone, 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sul
  • 1,3-bis (4-aminophenoxy) benzene and 1,4-bis (4-aminophenoxy) benzene can be preferably used. Furthermore, 1,3-bis (4-aminophenoxy) benzene is particularly preferred.
  • the diamine component to be used in combination can be used alone or in combination of two or more.
  • aromatic diamines such as paraphenylene diamine and metaphenylene diamine, modified products thereof, and aliphatic diamines such as hexamethylene diamine and tetramethylene diamine can be used in combination as long as the characteristics of the present invention are not impaired.
  • paraphenylenediamine it is preferable to use paraphenylenediamine together.
  • the heat-fusible polyimide layer preferably contains 25% by mole or more of paraphenylenediamine in all diamines. Thereby, the heat resistance of a polyimide metal laminated body further improves, and the peeling strength with a metal layer also becomes high.
  • the heat-resistant polyimide layer is obtained by polymerizing a tetracarboxylic dianhydride component and a diamine component.
  • the heat-resistant polyimide contains 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride as a tetracarboxylic dianhydride component in an amount of 50 mol% or more in the total tetracarboxylic dianhydride component.
  • the diamine component of the heat-resistant polyimide is not particularly limited.
  • paraphenylenediamine 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, m-tolidine, and 4,4′-diaminobenzanilide.
  • the total amount of these diamine components is preferably 70 mol% or more, more preferably 80 mol% or more, and more preferably 90 mol% or more in the total diamine components.
  • the diamine component of the heat-resistant polyimide contains 70 mol% or more of paraphenylenediamine in the total diamine.
  • Examples of the combination of an acid component and a diamine component that can provide a heat-resistant polyimide layer include the following.
  • a combination comprising 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (s-BPDA), paraphenylenediamine (PPD), and, if necessary, 4,4-diaminodiphenyl ether (DADE).
  • s-BPDA 4,4′-biphenyltetracarboxylic dianhydride
  • PPD paraphenylenediamine
  • DADE 4,4-diaminodiphenyl ether
  • s-BPDA 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride
  • PMDA pyromellitic dianhydride
  • PPD paraphenylenediamine
  • DADE 4,4 if necessary
  • s-BPDA / PMDA is preferably 50/50 to 90/10.
  • PPD and DADE are used in combination, PPD / DADE is preferably 90/10 to 10/90, for example.
  • DADE / PPD is preferably 90/10 to 10/90.
  • s-BPDA 4,4′-biphenyltetracarboxylic dianhydride
  • PPD diamine
  • the combination of (1) is preferable because of excellent heat resistance. Furthermore, tetracarboxylic acid containing 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride as a main component (for example, 70 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more).
  • a heat-resistant polyimide layer obtained from a dianhydride component and a diamine component containing paraphenylenediamine as a main component for example, 70 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more
  • a heat-fusible polyimide film excellent in low linear expansion coefficient, high elastic modulus, and dimensional stability can be obtained.
  • an acid component capable of obtaining a heat-resistant polyimide layer in addition to the above-mentioned acid component, other tetracarboxylic dianhydride components and / or other diamine components are used in combination as long as the desired properties are not impaired. be able to.
  • tetracarboxylic dianhydride components include 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4) -Dicarboxyphenyl) sulfide dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4- Dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis [( 3,4-dicarboxyphenoxy) phenyl] propane dianhydride and the like.
  • diamine components include metaphenylene diamine, 2,4-toluenediamine, 3,3′-diaminodiphenyl sulfide, 3,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfide, 3,3′- Diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3 ' -Diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2-di (3-aminophenyl) propane, 2,2-di (4-aminophenyl)
  • the thickness of the heat-sealable polyimide film is not particularly limited, but in the case of a heat-sealable polyimide film having a three-layer structure having a heat-sealable polyimide layer on both sides of the heat-resistant polyimide layer, the thickness of the heat-stable polyimide layer Is preferably 3 to 70 ⁇ m, more preferably 8 to 50 ⁇ m.
  • the thickness of the single layer of the heat-fusible polyimide layer is preferably 0.5 to 15 ⁇ m, and more preferably 1 to 12.5 ⁇ m.
  • the total thickness of the heat-fusible polyimide layers on both sides is preferably 1 to 30 ⁇ m, and more preferably 2 to 25 ⁇ m.
  • the heat-fusible polyimide film obtained in the present invention is excellent in heat resistance, particularly solder heat resistance.
  • the water absorption rate of the heat-fusible layer of the heat-fusible polyimide film is, for example, 0.6% or less, preferably 0.5% or less.
  • the linear expansion coefficient of the heat-fusible polyimide film is, for example, 16 to 22 ppm / ° C.
  • the elastic modulus of the heat-fusible polyimide film is, for example, 5.5 to 8 GPa. The method for measuring the water absorption rate, the linear expansion coefficient, and the elastic modulus will be described in the Examples section.
  • the single-layer heat-fusible polyimide film composed only of the heat-fusible polyimide layer described above will be described.
  • the single-layer heat-fusible polyimide layer is obtained by polymerizing a tetracarboxylic dianhydride component and a diamine component.
  • the heat-fusible polyimide contains 50 mol% or more of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride in at least all tetracarboxylic dianhydride components, and 2,3,3 ′, 4 It may contain more than 0 and less than 50 mol% of '-biphenyltetracarboxylic dianhydride.
  • 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is preferably 70 mol% or more, more preferably 80 mol% or more, more preferably 90 mol%.
  • a polyimide metal laminate having a high peel strength which will be described later, contains 10 to 30 mol% of 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride in the total tetracarboxylic dianhydride component. From the viewpoint of obtaining.
  • the diamine component contains an amount exceeding 50 mol% of 2,2-bis [4- (4-aminophenoxy) phenyl] propane in the total diamine.
  • the content of 2,2-bis [4- (4-aminophenoxy) phenyl] propane in the total diamine is 70 mol% or more and 100% or less from the viewpoint of obtaining a polyimide film having excellent heat resistance and low water absorption, which will be described later. preferable.
  • the thickness of the single-layer heat-fusible polyimide film is not particularly limited, but is 75 ⁇ m or less, preferably 8 to 50 ⁇ m, and more preferably 10 to 50 ⁇ m.
  • the description content of the said "multilayer heat-fusible polyimide film" is applicable as it is.
  • the multilayer heat-fusible polyimide film is a polyimide that gives a heat-fusible polyimide layer on one or both sides of a self-supporting film obtained from a polyimide precursor solution (polyamic acid solution) (a) that gives a heat-resistant polyimide layer. It can be obtained by applying a precursor solution (polyamic acid solution) (b) and imidizing by heating and drying the resulting multilayer self-supporting film.
  • the self-supporting film obtained from the polyimide precursor solution (a) that gives the heat-resistant polyimide layer is substantially the same in terms of the tetracarboxylic acid component and the diamine component, or a slight excess of either component.
  • a polyamic acid solution [polyimide precursor solution (a)] obtained by reacting in a solvent can be cast on a support and dried by heating.
  • the polyimide precursor solution (b) that gives the heat-fusible polyimide layer also has a tetracarboxylic acid component and a diamine component that are substantially equimolar, or a slight excess of either component in an organic solvent. It is obtained by reacting.
  • the polyimide precursor solution (b) that gives the heat-fusible polyimide layer was prepared by using 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride as a tetracarboxylic dianhydride component,
  • the carboxylic dianhydride component contains 50 mol% or more
  • the diamine component contains 2,2-bis [4- (4-aminophenoxy) phenyl] propane in excess of 50 mol% in the total diamine.
  • the polyimide precursor solution (polyamic acid solution) (a) that gives the heat-resistant polyimide layer is obtained by adding 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride in the total tetracarboxylic dianhydride component. Contains 50 mol% or more.
  • the polyimide precursor solution (b) for providing the heat-fusible polyimide layer may contain 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride.
  • 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride may be contained in the total tetracarboxylic dianhydride component in an amount of less than 50 mol%, preferably 10 to 30 mol%. Thereby, the polyimide metal laminated body with high peeling strength can be obtained.
  • Examples of the organic solvent for producing the polyimide precursor solution include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N, N-diethylformamide, Examples thereof include amides such as hexamethylsulfuramide, sulfoxides such as dimethyl sulfoxide and diethyl sulfoxide, and sulfones such as dimethyl sulfone and diethyl sulfone. These solvents may be used alone or in combination.
  • the concentration of all monomers in the organic solvent when carrying out the polymerization reaction of the polyimide precursor can be appropriately selected according to the purpose of use.
  • the concentration of all monomers in the organic solvent is preferably 5 to 40% by mass, more preferably 6 to 35% by mass, and 10 to 30%. It is particularly preferable that the content is% by mass.
  • a tetracarboxylic acid component and a diamine component are substantially equimolar, or either component (acid component or diamine).
  • Component) is slightly mixed and mixed, and the reaction is carried out at a reaction temperature of 100 ° C. or lower, preferably 80 ° C. or lower, more preferably 0 to 60 ° C. for about 0.2 to 60 hours to obtain a polyamic acid (polyimide precursor) solution.
  • the solution viscosity of the polyimide precursor solution (a) and the polyimide precursor solution (b) can be appropriately selected depending on the purpose (coating, casting, etc.) to be used.
  • the rotational viscosity measured at 30 ° C. is about 100 from the viewpoint of workability in handling the polyimide precursor solution. It is preferably ⁇ 5000 poise, more preferably 500 to 4,000 poise, and particularly preferably about 1000 to 3,000 poise.
  • polyimide precursor is 1 to 100 centipoise from the viewpoint of workability in handling the polyimide precursor solution. It is preferably 3 to 50 centipoise, more preferably 5 to 20 centipoise. Therefore, it is desirable to carry out the polymerization reaction to such an extent that the produced polyamic acid (polyimide precursor) exhibits the above viscosity. Moreover, said organic solvent can be added to the manufactured polyamic acid solution, and solution viscosity can also be adjusted.
  • the polyimide precursor solution (a) self-supporting film used as the heat-resistant polyimide layer may be, for example, a polyimide precursor solution (a) or a suitable support (for example, a metal, ceramic, plastic roll, or metal belt). ) To form a film having a uniform thickness, and then heated to 50 to 210 ° C., particularly 60 to 200 ° C. using a heat source such as hot air or infrared rays, It can be obtained by gradually removing and drying until it becomes self-supporting (for example, to the extent that it can be peeled off from the support).
  • a heat source such as hot air or infrared rays
  • a polyimide precursor solution (b) that gives a heat-fusible polyimide layer is applied to one side or both sides of the self-supporting film of the polyimide precursor solution (a) thus obtained.
  • the polyimide precursor solution (b) may be applied to the self-supporting film peeled from the support, or may be applied to the self-supporting film on the support before peeling from the support.
  • the polyimide precursor solution (b) can be applied to the self-supporting film of the polyimide precursor solution (a), for example, gravure coating method, spin coating method, silk screen method, dip coating method, spray coating method. , Known coating methods such as bar coating, knife coating, roll coating, blade coating and die coating.
  • the self-supporting film of the polyimide precursor solution (a) preferably has a surface on which the polyimide precursor solution (b) can be applied uniformly.
  • the self-supporting film of the polyimide precursor solution (a) preferably has a loss on heating in the range of 20 to 40% by mass, and preferably has an imidization ratio in the range of 8 to 40%. If the heating weight loss and imidization rate are within the above ranges, the mechanical properties of the self-supporting film will be sufficient, and it will be easier to cleanly apply the polyimide precursor solution (b) on the upper surface of the self-supporting film, and imidization will occur.
  • production of a foam, a crack, a craze, a crack, crack, etc. is not observed in the polyimide film obtained later, and the adhesive strength of a heat resistant polyimide layer and a heat-fusible polyimide layer becomes enough.
  • the imidization ratio of the self-supporting film can be calculated by measuring the IR spectrum of the self-supporting film and its fully cured product (polyimide film) by the ATR method and using the ratio of the peak area of the vibration band.
  • the vibration band peak an asymmetric stretching vibration band of an imide carbonyl group, a benzene ring skeleton stretching vibration band, or the like is used.
  • imidation rate measurement there is also a method using a Karl Fischer moisture meter described in JP-A-9-316199.
  • a fine inorganic or organic filler can be mix
  • inorganic additives include particulate or flat inorganic fillers, such as particulate titanium dioxide powder, silicon dioxide (silica) powder, magnesium oxide powder, aluminum oxide (alumina) powder, and zinc oxide powder.
  • inorganic oxide powder such as, inorganic nitride powder such as particulate silicon nitride powder and titanium nitride powder, inorganic carbide powder such as silicon carbide powder, inorganic such as particulate calcium carbonate powder, calcium sulfate powder and barium sulfate powder Mention may be made of salt powder.
  • organic additive examples include polyimide particles and thermosetting resin particles. These additives may be used in combination of two or more. About the usage-amount and shape (size, aspect ratio) of an additive, it is preferable to select according to a use purpose. Moreover, in order to disperse these additives uniformly, a means known per se can be applied.
  • the maximum heating temperature of the heat treatment for imidation is preferably 350 ° C. to 600 ° C., more preferably 380 to 520 ° C., more preferably 390 to 500 ° C., and more preferably 400 to 480 ° C.
  • the heat treatment for imidization is preferably performed in stages, and is first subjected to primary heat treatment at a temperature of 200 ° C. or higher and lower than 300 ° C. for 1 minute to 60 minutes, and then at a temperature of 300 ° C. or higher and lower than 350 ° C. for 1 minute. Secondary heat treatment for ⁇ 60 minutes, and then the maximum heating temperature of 350 ° C. to 600 ° C., preferably 450 to 590 ° C., more preferably 490 to 580 ° C., more preferably 500 to 580 ° C. for 1 minute to 30 minutes.
  • a tertiary heat treatment is desirable. This heat treatment can be performed using a known apparatus such as a hot air furnace or an infrared heating furnace.
  • this heat treatment is preferably performed by fixing the self-supporting film of the polyimide precursor solution (a) coated with the polyimide precursor solution (b) with a pin tenter, a clip or the like.
  • the polyimide precursor solution (b) and / or the polyimide precursor solution (a) is used for the purpose of limiting the gelation of the polyamic acid (polyimide precursor).
  • Phenyl and the like can be added in the range of 0.01 to 1% with respect to the solid content (polymer) concentration during polyamic acid polymerization.
  • a phosphate ester or a salt of a tertiary amine and a phosphate ester to the polyamic acid solution.
  • these addition amounts are preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the polyimide or polymer.
  • Specific examples of the phosphate ester include distearyl phosphate ester and monostearyl phosphate ester.
  • Examples of the salt of tertiary amine and phosphate ester include monostearyl phosphate ester triethanolamine salt.
  • thermal imidization thermal imidization
  • chemical imidization chemical imidization
  • a basic organic compound can be added to the polyimide precursor solution (b) and / or the polyimide precursor solution (a) for the purpose of promoting imidization.
  • imidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-phenylimidazole, benzimidazole, isoquinoline, substituted pyridine and the like are 0.05 to 10% by mass with respect to the polyamic acid (polyimide precursor), preferably It can be used in a proportion of 0.05 to 5% by mass, particularly preferably 0.1 to 2% by mass. These can be used to avoid insufficient imidization to form polyimide films at relatively low temperatures.
  • the multilayer polyimide film of the present invention is obtained by a coextrusion-casting film forming method (also simply referred to as a coextrusion method), a heat-resistant polyimide layer dope solution (also referred to as a polyamic acid solution or a polyimide precursor solution), It can also be produced by a method of obtaining a multilayer polyimide film by laminating, drying and imidizing with a dope solution of a heat-fusible polyimide layer.
  • a coextrusion-casting film forming method also simply referred to as a coextrusion method
  • a heat-resistant polyimide layer dope solution also referred to as a polyamic acid solution or a polyimide precursor solution
  • a method of obtaining a multilayer polyimide film by laminating, drying and imidizing with a dope solution of a heat-fusible polyimide layer for example, a method described in JP-A-3-180343 (Japanese Patent Public
  • this co-extrusion method first uses an extrusion molding machine having two or more layers of extrusion dies, and the dope solution of the heat-resistant polyimide layer and the heat-sealable polyimide from the discharge port of the dies.
  • a layered dope solution is cast on a support to form a laminated thin film.
  • the thin film on the support is dried to form a multilayer self-supporting film, then the multilayer self-supporting film is peeled off from the support, and finally the multilayer self-supporting film is heat-treated. It is to do.
  • the dope solution in contact with the support may be either a dope solution that provides a heat-resistant polyimide layer or a dope solution that provides a heat-fusible polyimide layer.
  • the drying is preferably performed by drying the thin film at a temperature exceeding 135 ° C., specifically 140 ° C. or higher, preferably 145 ° C. or higher to form a self-supporting film. Thereby, the peeling strength of the polyimide metal laminated body mentioned later improves.
  • a dope solution supply port is provided, and a dope solution passage is formed from each supply port toward each manifold, and a flow path at the bottom of the manifold is formed.
  • the gap between the lip portions can be adjusted by a lip adjustment bolt.
  • the distance between the gaps of the flow path is adjusted by each choke bar.
  • Each of the manifolds preferably has a hanger coat type shape.
  • the double-layer extrusion die has respective dope supply ports on the left and right sides of the upper portion of the die, and the dope solution passages are immediately joined at the junction where the partition plate is provided.
  • a dope solution flow path communicates from the junction to the manifold, and a dope solution passage (lip portion) at the bottom of the manifold communicates with the slit-like discharge port.
  • a structure feed block type double-layer die or single manifold type double-layer die in which the dope solution is discharged on the support in the form of a groove film from the discharge port may be used.
  • a multilayer extrusion polyimide film can be produced by a molding method similar to the two-layer extrusion molding by using three or more dies for extrusion molding. That is, when a heat-resistant polyimide layer dope and a heat-fusible polyimide layer dope are used, a two-layer heat-fusible polyimide film can be obtained. In addition, in the case of a layer configuration of a heat-fusible polyimide layer dope liquid-a heat-resistant polyimide layer dope liquid-a heat-fusible polyimide layer dope liquid, a three-layer heat-fusible polyimide film is obtained. You can also.
  • the multilayer polyimide film of the present invention is obtained by applying a polyamic acid solution of a heat-fusible polyimide to a heat-resistant polyimide film, heating and drying to imidize the heat-fusible layer. You can also.
  • a heat resistant polyimide film a film obtained by forming the heat resistant polyimide film composition by a known method or a commercially available polyimide film can be used.
  • heat-resistant polyimide films examples include Upilex (registered trademark) manufactured by Ube Industries, Kapton EN (registered trademark) manufactured by Toray DuPont, Apical NPI (registered trademark) manufactured by Kaneka Corporation, and the like. .
  • the amic acid solution of the heat-fusible polyimide film to be applied and the drying conditions can be performed in the same manner as in the application to the self-supporting film.
  • it is desirable to surface-treat a heat resistant polyimide film before coating examples of the surface treatment method include corona treatment, plasma treatment, alkali treatment, etching treatment, coupling agent treatment, or a combination thereof.
  • the single layer heat-fusible polyimide film contains 50 mol% or more of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride in at least all tetracarboxylic dianhydride components, A tetracarboxylic dianhydride component containing more than 0 and less than 50 mol% of 3 ′, 4′-biphenyltetracarboxylic dianhydride, and 2,2-bis [4- (4-aminophenoxy) phenyl in all diamines
  • a polyamic acid solution containing a diamine component containing more than 50 mol% of propane is cast or applied onto a carrier film, dried, and then heat-treated to obtain a heat-fusible polyimide film with a carrier film.
  • the polyamic acid solution is cast or coated on a carrier film and dried.
  • the drying temperature is, for example, 80 to 200 ° C., preferably 100 to 200 ° C.
  • a polyimide film can be suitably used as the carrier film.
  • a commercially available polyimide film can be used.
  • Upyorex registered trademark
  • Kapton EN registered trademark
  • Kaneka Corporation NPI registered trademark
  • the thickness of the polyimide film as the carrier film is preferably 50 ⁇ m or more, more preferably 75 to 125 ⁇ m.
  • a polyimide film as a carrier film is obtained by polymerizing a tetracarboxylic dianhydride component and a diamine component to obtain a polyamic acid solution, casting or coating the polyamic acid solution on a support, and drying it. After obtaining the support film, the self-support film is heated to imidize.
  • the surface that was in contact with the support when the polyamic acid solution was cast or applied onto the support was referred to as the B surface, and was not in contact with the support (air Side) surface.
  • the method for casting or coating is not particularly limited. For example, gravure coating, spin coating, silk screen, dip coating, spray coating, bar coating, knife coating, roll coating, blade coating And a method such as a die coating method.
  • the surface of the carrier film on which the polyamic acid solution is cast or applied may be either the A surface or the B surface, but it is preferable to cast or apply the polyamic acid solution on the B surface of the carrier film.
  • the adhesiveness with the metal of a heat-fusible polyimide film improves, and the peeling strength of the polyimide metal laminated body obtained by bonding together with a metal becomes high.
  • the thickness of the carrier film is 75 ⁇ m or more, preferably 75 to 125 ⁇ m, it is preferable to cast or apply the polyamic acid solution to the B surface of the carrier film.
  • the dried product (with a carrier film) is then heat-treated. Thereby, while remaining solvent is fully removed, imidation is advanced.
  • the temperature of the heat treatment is higher than the above drying temperature, preferably 100 to 400 ° C., more preferably 300 to 400 ° C.
  • the heat treatment time is, for example, 1 to 100 minutes.
  • the heat treatment is performed continuously or intermittently.
  • the heat treatment can be performed using an apparatus such as a hot air furnace or an infrared heating furnace.
  • a fixing device for the dried product (solidified film) for example, a belt-like or chain-like one provided with a large number of pins or gripping tools at equal intervals, the length of the solidified film supplied continuously or intermittently is used.
  • a device that can be installed in a pair along both side edges in the direction and can fix the film while moving the film continuously or intermittently with the movement of the film is suitable.
  • the solidified film fixing device can expand and contract the film being heat-treated in the width direction or the longitudinal direction at an appropriate elongation or contraction rate (particularly preferably an expansion ratio of about 0.5 to 5%). It may be a device.
  • the heat-welding polyimide film again, preferably 400 gf / mm 2 or less, particularly preferably under 300 gf / mm 2 or lower tension or under no tension, the temperature of 100 ⁇ 400 ° C., preferably 0.
  • a heat-fusible polyimide film having particularly excellent dimensional stability can be obtained.
  • the produced heat-fusible polyimide film with a long carrier film can be wound into a roll.
  • the carrier film can be peeled from the heat-fusible polyimide film with a carrier film to obtain a single-layer heat-fusible polyimide film.
  • the polyimide metal laminate of the present invention is formed by laminating a metal layer on the heat-fusible polyimide layer of the heat-fusible polyimide film of the present invention.
  • a metal layer may be laminated on both surfaces of the heat-fusible polyimide film, or a metal layer may be laminated only on one surface of the heat-fusible polyimide film.
  • the polyimide metal laminate of the present invention is laminated on one or both sides of the heat-fusible polyimide film having the heat-fusible polyimide layer on one or both sides of the outermost layer and the heat-fusible polyimide layer. You may do it.
  • the polyimide metal laminate of the present invention is obtained by laminating a metal layer on the heat-fusible polyimide layer of the heat-fusible polyimide film having the heat-fusible polyimide layer on at least one or both surfaces of the outermost layer. Formed.
  • the metal layer is formed on one side of the heat-fusible polyimide film
  • the heat-fusible polyimide film having the heat-fusible polyimide layer on one side or both sides of the outermost layer of the heat-fusible polyimide film is used.
  • the said heat-fusible polyimide film which has the said heat-fusible polyimide layer on both surfaces of the said heat-fusible polyimide film is used.
  • the surface of the heat-sealable polyimide film on which the metal layer is laminated is a carrier during the production of the single-layer heat-sealable polyimide film described above. It is preferable that the surface has no film.
  • the metal layer is laminated on one side or both sides of the heat-fusible polyimide film.
  • the metal layer is preferably a metal foil.
  • various metal foils such as copper, aluminum, gold, or an alloy of these alloys can be used.
  • copper foil is preferably used. Specific examples of the copper foil include rolled copper foil and electrolytic copper foil.
  • the thickness of the metal foil is not particularly limited, but is preferably 2 to 35 ⁇ m, and particularly preferably 5 to 18 ⁇ m.
  • a metal foil with a carrier for example, a copper foil with an aluminum foil carrier can be used.
  • the heat-fusible polyimide film and the metal layer are thermocompression-bonded by superimposing a metal layer (metal foil or the like) on both sides of the heat-fusible polyimide film having the heat-fusible polyimide layer formed on both sides.
  • a metal layer metal foil or the like
  • a metal layer such as a metal foil
  • the heat-fusible polyimide film and the metal foil are heated at least by a pair of pressure members so that the temperature of the pressure part is 30 ° C. higher than the glass transition temperature of the heat-fusible polyimide and 420 ° C. or lower. It is preferable to perform thermocompression bonding continuously.
  • the pressure member examples include a pair of pressure-bonding metal rolls (the pressure-bonding portion may be made of metal or ceramic sprayed metal), a double belt press, and a hot press, and particularly capable of thermocompression bonding and cooling under pressure.
  • a hydraulic double belt press is particularly preferred.
  • a polyimide metal laminate can be easily obtained by roll lamination using a pair of crimped metal rolls.
  • the pressure member for example, a metal roll or preferably a double belt press is used, and the heat-fusible polyimide film, the metal foil, and the reinforcing material are superposed and continuously heated.
  • a long polyimide metal laminate can be produced by pressure bonding.
  • the heat-fusible polyimide film and the metal foil are used in a roll-wound state, and are continuously supplied to the pressure members, respectively, and are particularly suitable when the polyimide metal laminate is obtained in a roll-wound state. .
  • the heat-fusible polyimide film and the metal foil are firmly laminated.
  • the peel strength measured by the method of JIS C6471 is 0.5 N / mm or more, preferably 0.7 N / mm or more, more preferably 0.9 N / mm or more, and further preferably 1.3 N.
  • a polyimide metal laminate that is at least / mm can be obtained.
  • the peeling state includes a case where peeling occurs at the interface between the heat-resistant polyimide layer and the heat-fusible polyimide film, and a case where peeling occurs at the interface between the heat-fusible polyimide layer and the metal layer. Therefore, the measured peel strength is the peel strength of the surface with weaker adhesive force.
  • the peel strength measurement method is as follows.
  • a copper foil (3EC-VLP, manufactured by Mitsui Kinzoku Co., Ltd., 3 ⁇ -VLP, thickness 18 ⁇ m) is superimposed on the heat-fusible polyimide layer of the heat-fusible polyimide film, and 30 ° C. or more from the glass transition temperature of the heat-fusible polyimide.
  • a polyimide metal laminate in which a copper foil is laminated on a heat-fusible polyimide film is obtained by thermocompression bonding at a high temperature of 420 ° C. or less at a residual heat of 5 minutes, a press pressure of 3 MPa, and a press time of 1 minute.
  • the peel strength of this polyimide metal laminate is measured by the method of JIS C6471.
  • the glass transition temperature of the heat-fusible polyimide varies depending on the types of the tetracarboxylic dianhydride component and the diamine component that constitute the heat-fusible polyimide.
  • the said thermocompression bonding temperature is suitably set according to the glass transition temperature of the heat-fusible polyimide used.
  • the heat-fusible polyimide film of the present invention can be used as an adhesive sheet or an adhesive tape.
  • the polyimide metal laminate of the present invention has good moldability and can be directly subjected to drilling, bending, drawing, metal wiring formation, and the like. Moreover, the heat-fusible polyimide film of this invention can be used for the thermocompression bonding of the electronic circuit on wiring.
  • the heat-fusible polyimide film and the polyimide metal laminate of the present invention can be used as materials for electronic parts and electronic devices such as a printed wiring board, a flexible printed circuit board, and a TAB tape.
  • the heat-fusible polyimide film of the present invention includes a tab lead sealing material such as a lithium ion battery, a polymer battery, and an electric double layer capacitor using an aluminum laminate film as an outer bag, a cover lay of a flexible printed circuit board, and a ceramic package. It can be suitably used as an adhesive sheet that requires reliability at high temperatures, such as a bonding material between a cap and a cap.
  • the metal layer was mentioned as an adherend laminated
  • the adherend other than metal include ceramic, glass, and polyimide film.
  • solder heat resistance of polyimide metal laminate A resist is printed on one side of the obtained polyimide metal laminate and immersed in an etching solution at 30 ° C. for 20 to 30 minutes to obtain a laminate in which the metal layer on one side is etched. It was. The obtained laminate was dried at 80 ° C. for 30 minutes, and the sample conditioned for 24 hours or more in an environment of 23 ° C.-60% RH was floated in a solder bath at various temperatures for 10 seconds. It was confirmed. The maximum temperature at which foaming was not confirmed was defined as the solder heat resistance temperature.
  • Example 1 Multilayer heat-fusible polyimide film and polyimide metal laminate
  • a polyamic acid solution E thermal fusion layer
  • polyamic acid solution A core layer
  • polyamic acid solution E thermal fusion layer
  • the thin film casting was continuously dried with hot air at 145 ° C. to form a self-supporting film. After peeling the self-supporting film from the support, it is gradually heated from 200 ° C. to 460 ° C.
  • Table 2 shows the linear expansion coefficient and elastic modulus of the heat-fusible polyimide film.
  • a copper foil (3EC-VLP, manufactured by Mitsui Kinzoku Co., Ltd., 3 ⁇ m thickness) is superimposed on both sides of the obtained heat-fusible polyimide film, and the temperature is 300 ° C., the remaining heat is 5 minutes, the pressing pressure is 3 MPa, and the pressing time is 1.
  • stacked on both surfaces of the heat-fusible polyimide film was obtained by carrying out the thermocompression bonding in minutes. Each evaluation of the peeling strength of this polyimide metal laminated body and solder heat resistance was performed. The results are shown in Table 2.
  • Example 2 A heat-fusible polyimide film was obtained in the same manner as in Example 1 except that the type of polyamic acid solution and the drying temperature of the cast were changed as shown in Table 2.
  • Table 2 shows the linear expansion coefficient and elastic modulus of the heat-fusible polyimide film.
  • a polyimide metal laminate was obtained in the same manner as in Example 1. Each evaluation of the peeling strength of this polyimide metal laminated body and solder heat resistance was performed. The results are shown in Table 2.
  • the drying temperature of the self-supporting film is 140 ° C. or higher, the peel strength of the polyimide metal laminate (interfacial strength between the heat-resistant polyimide layer and the heat-fusible polyimide layer) is improved.
  • the BAPP in the diamine component exceeds 50 mol%, preferably 65 mol% or more, particularly 70 mol% or more, the heat resistance of the polyimide metal laminate is excellent.
  • the core layer contains less s-BPDA as the tetracarboxylic dianhydride component, there is no problem in solder heat resistance, but the value of the linear expansion coefficient of the heat-fusible polyimide film increases, and the elastic modulus There was a tendency that the dimensional stability of the polyimide metal laminate decreased. More preferably, the core layer contains 50 mol% or more of s-BPDA as a tetracarboxylic dianhydride component.
  • the heat fusion layer when BAPP and PPD are used in combination as the diamine component, and the amount of PPD is 25 mol% or more in the total diamine component, the peel strength and solder heat resistance of the polyimide metal laminate are Even better.
  • a-BPDA in the tetracarboxylic dianhydride component is used for the heat-sealing layer, the peel strength of the polyimide metal laminate is improved.
  • a polyimide film having excellent heat resistance and excellent adhesion to the metal layer can be obtained. Moreover, it is excellent in heat resistance and can obtain the laminated body (polyimide metal laminated body) with high peeling strength of a polyimide film and a metal layer.

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  • Laminated Bodies (AREA)

Abstract

L'invention concerne un film de polyimide thermoadhésif qui offre une excellente résistance à la chaleur et une excellente adhésion à une couche de métal, une méthode de production du film de polyimide thermoadhésif, et un stratifié polyimide/métal utilisant le film de polyimide thermoadhésif. L'invention concerne un film de polyimide thermoadhésif multicouche comprenant une couche de polyimide thermoadhésive et une couche de polyimide résistant à la chaleur superposée en contact avec la couche de polyimide thermoadhésive, le film de polyimide thermoadhésif étant caractérisé en ce que : la couche de polyimide thermoadhésive comprend au moins 50 % molaires de dianhydride 3,3',4,4'-biphényle tétracarboxylique de la totalité des composants dianhydride tétracarboxylique et comprend au moins 50 % molaires de 2,2-bis[4-(4-aminophénoxy) phényl] propane de la totalité des diamines ; et la couche de polyimide résistant à la chaleur comprenant au moins 50 % molaires de dianhydride 3,3',4,4'-biphényle tétracarboxylique de la totalité des composants dianhydride tétracarboxylique, la force de détachement mesurée selon la méthode spécifiée dans JIS C6471 étant supérieure ou égale à 0,5 N/mm.
PCT/JP2013/061356 2012-04-19 2013-04-17 Film de polyimide thermoadhésif, méthode de production d'un film de polyimide thermoadhésif, et stratifié polyimide/métal utilisant un film de polyimide thermoadhésif WO2013157565A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2012095613 2012-04-19
JP2012-095613 2012-04-19
JP2012-095606 2012-04-19
JP2012095606A JP2015129200A (ja) 2012-04-19 2012-04-19 熱融着性ポリイミドフィルム、及びそれを用いたポリイミド金属積層体
JP2012282249A JP2015128821A (ja) 2012-04-19 2012-12-26 熱融着性ポリイミドフィルム、熱融着性ポリイミドフィルムの製造方法及び熱融着性ポリイミドフィルムを用いたポリイミド金属積層体
JP2012-282249 2012-12-26

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WO2016136897A1 (fr) * 2015-02-26 2016-09-01 宇部興産株式会社 Procédé de fabrication d'un stratifié revêtu de cuivre
WO2016159104A1 (fr) * 2015-03-31 2016-10-06 株式会社カネカ Film de polyimide multicouche, stratifié de feuille métallique souple, procédé de fabrication de stratifié de feuille métallique souple, et procédé de fabrication de carte de câblage imprimé rigide-souple
KR20190078559A (ko) 2016-10-31 2019-07-04 우베 고산 가부시키가이샤 금속 적층용 폴리이미드 필름 및 이것을 사용한 폴리이미드 금속 적층체
WO2023190555A1 (fr) * 2022-03-28 2023-10-05 Ｕｂｅ株式会社 Composition de précurseur de polyimide, film de polyimide et produit stratifié de film/substrat de polyimide

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KR20170122196A (ko) 2015-02-26 2017-11-03 우베 고산 가부시키가이샤 동장(銅張) 적층판의 제조방법
WO2016159104A1 (fr) * 2015-03-31 2016-10-06 株式会社カネカ Film de polyimide multicouche, stratifié de feuille métallique souple, procédé de fabrication de stratifié de feuille métallique souple, et procédé de fabrication de carte de câblage imprimé rigide-souple
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WO2023190555A1 (fr) * 2022-03-28 2023-10-05 Ｕｂｅ株式会社 Composition de précurseur de polyimide, film de polyimide et produit stratifié de film/substrat de polyimide

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