Classifications

• • 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
  • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
  • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
• • 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
  • 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
  • B32B15/088—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 comprising polyamides
• • 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
  • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
• • 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
• • 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
  • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
  • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
• • 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
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
• • 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
  • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
  • B32B2309/02—Temperature
• • 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

Definitions

• the present invention relates to a method for producing a copper clad laminate using a heat-fusible polyimide film.
• Polyimide films are widely used as substrate materials such as flexible printed wiring boards (hereinafter also referred to as “FPC”) and tape automated bonding (hereinafter also referred to as “TAB”).
• FPC flexible printed wiring boards
• TAB tape automated bonding
• examples of a method for bonding a polyimide film and a copper foil include a method using an adhesive such as an epoxy resin or an acrylic resin.
• Patent Documents 1 and 2 disclose a heat-fusible polyimide film in which a heat-fusible polyimide layer is laminated on a heat-resistant polyimide layer, and a method for producing a copper-clad laminate using the same. ing.
• an object of the present invention is to provide a method for producing a copper clad laminate using a heat-fusible polyimide film having excellent heat resistance and excellent adhesion to a metal layer.
• the present invention relates to the following items.
• a method for producing a copper clad laminate having a step of thermocompression bonding by superimposing a copper foil on a heat-fusible polyimide film The heat-fusible polyimide film includes a heat-fusible polyimide layer and a heat-resistant polyimide layer laminated in contact with the heat-fusible polyimide layer,
• the polyimide constituting the heat-fusible polyimide layer is obtained from a tetracarboxylic acid component and a diamine component,
• the tetracarboxylic acid component contains 10 to 30 mol% of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and 70 to 90 mol% of pyromellitic dianhydride,
• the diamine component contains more than 50 mol% of 2,2-bis [4- (4-aminophenoxy) phenyl] propane;
• the heat-sealable polyimide film used in the present invention includes a heat-sealable polyimide layer (hereinafter also simply referred to as “heat-sealable layer”) and a heat-resistant polyimide laminated in contact with the heat-sealable polyimide layer. It is a multilayer polyimide film including a layer (hereinafter also referred to as “core layer”).
• the heat-fusible polyimide film has at least a two-layer structure having at least one heat-fusible layer and at least one core layer.
• the heat-sealable polyimide film may have a three-layer structure in which the same or different heat-seal layers are disposed on each surface of the core layer.
• 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, and the glass transition temperature (Tg) is a softening point for amorphous polyimide, and the melting point is a softening point for crystalline polyimide.
• the heat-fusible polyimide layer (heat-fusible layer) is made of a heat-fusible polyimide obtained from a tetracarboxylic acid component and a diamine component.
• the tetracarboxylic acid component contains at least 80 mol% of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride in total.
• the tetracarboxylic acid component is more preferably composed of these compounds.
• the content of these components is preferably 10 to 30 mol%, particularly 15 to 25 mol% of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride in the total tetracarboxylic acid components.
• Pyromellitic dianhydride is preferably 70 to 90 mol%, particularly preferably 75 to 85 mol%.
• the diamine component preferably contains 2,2-bis [4- (4-aminophenoxy) phenyl] propane in an amount exceeding 50 mol% in the total diamine component.
• the content of 2,2-bis [4- (4-aminophenoxy) phenyl] propane in the total diamine component is preferably 70 mol% or more, more preferably 80 mol% or more, most preferably 90 mol% or more and 100%. It is as follows.
• the two tetracarboxylic acid components and other tetracarboxylic acid components can be used in combination.
• examples of other tetracarboxylic acid components used in combination include 3,3 ′, 4,4′-benzophenonetetracarboxylic 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- And dicarboxyphenyl) propane dianhydride and 1,4-hydroquinone dibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride.
• the tetracarboxylic acid component to be used in combination can be used alone or in combination of two
• 2,2-bis [4- (4-aminophenoxy) phenyl] propane and other diamine components can be used in combination.
• diamine components 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- (3-aminophenoxy) ) Pheny
• the heat-fusible polyimide constituting the heat-fusible layer is non-crystalline, which improves the peel strength between the heat-fusible layer and the heat-resistant polyimide layer, and peels the heat-fusible layer from the copper foil. It is preferable from the viewpoint of improving the strength.
• a thermally fusible polyimide being amorphous means that it has a glass transition temperature but no melting point is observed.
• a method of using a compound having an ether bond as a tetracarboxylic acid component or a diamine component may be employed.
• the glass transition temperature of the heat-fusible polyimide constituting the heat-fusible layer is preferably 250 ° C. to 320 ° C. More preferably, it is 300 degreeC. A method for measuring the glass transition temperature will be described in detail in Examples described later.
• the heat resistant polyimide layer (core layer) is made of a heat resistant polyimide obtained from a tetracarboxylic acid component and a diamine component.
• the heat-resistant polyimide preferably contains more than 50 mol% of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride as a tetracarboxylic acid component in the total tetracarboxylic acid component.
• the heat-resistant polyimide may contain other tetracarboxylic acid components as tetracarboxylic acid components in addition to 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride.
• the total amount of the other tetracarboxylic acid components is preferably 70 mol% or more, more preferably 80 mol% or more, and more preferably 90 mol% or more in the total tetracarboxylic acid components.
• the heat-resistant polyimide preferably contains p-phenylenediamine as a diamine component in an amount exceeding 50 mol% in the total diamine component.
• the heat-resistant polyimide may contain other diamine components in addition to p-phenylenediamine as a diamine component.
• p-phenylenediamine contains more than 50 mol% in the total diamine component, and is further selected from 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, m-tolidine and 4,4′-diaminobenzanilide. It is preferable to contain at least one diamine component.
• the total amount of the other 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.
• Examples of the combination of a tetracarboxylic acid component and a diamine component that can obtain a heat-resistant polyimide include the following. (1) 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (hereinafter also referred to as “s-BPDA”), p-phenylenediamine (hereinafter also referred to as “PPD”), and if necessary.
• s-BPDA 4,4′-biphenyltetracarboxylic dianhydride
• PPD p-phenylenediamine
• a combination containing 4,4-diaminodiphenyl ether hereinafter also referred to as “DADE”).
• the PPD / DADE (molar ratio) is preferably 100/0 to 85/15.
• s-BPDA 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (s-BPDA) and pyromellitic dianhydride (hereinafter also referred to as “PMDA”) and p-phenylenediamine (PPD) And a combination containing 4,4-diaminodiphenyl ether (DADE) if necessary.
• s-BPDA / PMDA is preferably 55/45 to 90/10.
• PPD and DADE are used in combination
• PPD / DADE is preferably 55/45 to 90/10, for example.
• a combination comprising 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (s-BPDA) and p-phenylenediamine (PPD).
• a fine inorganic or organic filler (hereinafter also referred to as “additive”) can be blended as necessary.
• the inorganic additive include inorganic fillers such as particles or flat shapes. Specifically, for example, particulate titanium dioxide powder, silicon dioxide (silica) powder, magnesium oxide powder, aluminum oxide (alumina) powder, inorganic oxide powder such as zinc oxide powder, particulate silicon nitride powder, titanium nitride Examples thereof include inorganic nitride powder such as powder, inorganic carbide powder such as silicon carbide powder, and inorganic salt powder such as fine-particle calcium carbonate powder, calcium sulfate powder, and barium sulfate 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 thickness of the heat-sealable polyimide film used in the present invention is not particularly limited, but in the case of a heat-sealable polyimide film having a three-layer structure each having a heat-sealable polyimide layer on both sides of the heat-resistant polyimide layer,
• the thickness of the conductive polyimide layer is preferably 3 to 70 ⁇ m, and more preferably 8 to 50 ⁇ m.
• the thickness 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 film is preferably 1 to 30 ⁇ m, and more preferably 2 to 25 ⁇ m.
• the heat-fusible polyimide film used in the present invention is preferably excellent in heat resistance, for example, solder heat resistance is preferably 280 ° C. or higher, particularly 300 ° C. or higher.
• the tear strength of the heat-fusible polyimide film is preferably 1.7 N / mm or more, particularly 1.9 N / mm or more. The solder heat resistance and tear strength measurement methods will be described in the Examples section.
• the heat-fusible polyimide film used in the present invention is a polyimide that gives heat-fusible polyimide on one or both sides of a self-supporting film obtained from a polyimide precursor solution (polyamic acid solution) (a) that gives heat-resistant polyimide. 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 heat-resistant polyimide has a tetracarboxylic acid component and a diamine component in substantially equimolar amounts, or one component is slightly more than the other component.
• the polyimide precursor solution (a) obtained by reacting in an organic solvent in excess can be cast on a support, and the cast can be dried by heating.
• the polyimide precursor solution (b) that gives the heat-fusible polyimide also has a tetracarboxylic acid component and a diamine component in substantially equimolar amounts, or one component is slightly excessive with respect to the other component. It can be obtained by reacting in an organic solvent.
• the polyimide precursor solution (b) that gives the heat-fusible polyimide contains 10 to 30 of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride as a tetracarboxylic acid component in all tetracarboxylic acid components. Containing 70 to 90 mol% of pyromellitic dianhydride, and containing more than 50 mol% of 2,2-bis [4- (4-aminophenoxy) phenyl] propane as the diamine component in the total diamine. Is preferred.
• the polyimide precursor solution (a) that gives the heat-resistant polyimide contains 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride as a tetracarboxylic acid component in an amount exceeding 50 mol% in the total tetracarboxylic acid components.
• the diamine component contains p-phenylenediamine in an amount of more than 50 mol% in the total diamine.
• the polyimide precursor solution (b) and / or the polyimide precursor solution (a) has a phosphorus stabilizer such as triphenyl phosphite or phosphoric acid for the purpose of limiting the gelation of polyamic acid (polyimide precursor).
• Triphenyl and the like can be added in the range of 0.01 to 1% by mass with respect to the solid content (polymer) concentration during polyamic acid polymerization. From the viewpoint of the surface state of the film and productivity, it is preferable to add a phosphate ester or a salt of a tertiary amine and a phosphate ester to the polyamic acid solution.
• phosphate ester examples include distearyl phosphate ester and monostearyl phosphate ester.
• salts 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 preferably 0.05 to 10% by mass with respect to the polyamic acid (polyimide precursor). More preferably, it can be used in a proportion of 0.05 to 5% by mass, particularly preferably 0.1 to 2% by mass.
• imidization of the polyimide precursor is promoted at a relatively low temperature to form a polyimide film, so that these basic organic compounds avoid insufficient imidization. Can be used for purposes.
• 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.
• 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 tetracarboxylic acid component and the diamine component 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 one component (an acid component or a diamine component) ) In a slight excess with respect to the other component, and is preferably reacted at a reaction temperature of 100 ° C. or lower, more preferably 80 ° C. or lower, more preferably 0 to 60 ° C. for about 0.2 to 60 hours.
• a polyimide precursor (polyamic acid) solution can be obtained.
• 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 30 ° C. from the viewpoint of workability in handling the polyimide precursor solution. It is preferably 100 to 5000 poise, more preferably 500 to 4000 poise, and particularly preferably about 1000 to 3000 poise.
• polyimide precursor is 1 to 100 centipoise from the viewpoint of workability to handle 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 self-supporting film obtained from the polyimide precursor solution (a) that gives the heat-resistant polyimide can be obtained, for example, by using the polyimide precursor solution (a) as a suitable support (for example, a metal, ceramic, plastic roll, or metal belt). Etc.) to form a film having a uniform thickness, and then heated to 50 to 210 ° C., more preferably 60 to 200 ° C. using a heat source such as hot air or infrared rays. Then, the solvent can be gradually removed and dried until it becomes self-supporting (for example, to the extent that it can be peeled off from the support).
• a suitable support for example, a metal, ceramic, plastic roll, or metal belt.
• Etc. to form a film having a uniform thickness, and then heated to 50 to 210 ° C., more preferably 60 to 200 ° C. using a heat source such as hot air or infrared rays.
• the solvent can be gradually removed and dried until it becomes self-support
• the self-supporting film giving heat-resistant polyimide preferably has a loss on heating in the range of 20 to 40% by mass and an imidation 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. Foaming, cracks, crazes, cracks, cracks, etc. are unlikely to occur in the polyimide film obtained later, and the adhesive strength between the heat-resistant polyimide layer and the heat-fusible polyimide layer is sufficient.
• the loss on heating of the self-supporting film is a value obtained by drying the film to be measured at 400 ° C. for 30 minutes, and calculating from the weight before drying (W 1 ) and the weight after drying (W 2 ) by the following formula. .
• Loss on heating (% by mass) ⁇ (W 1 ⁇ W 2 ) / W 1 ⁇ ⁇ 100
• the imidation ratio of the self-supporting film can be calculated by measuring the IR spectra of the self-supporting film and its full-cure product (polyimide film) by the ATR method and using the ratio of the vibration band peak area.
• an asymmetric stretching vibration band of an imide carbonyl group, a benzene ring skeleton stretching vibration band, or the like can be used.
• imidation rate measurement there is also a method using a Karl Fischer moisture meter described in JP-A-9-316199.
• a polyimide precursor solution (b) that gives heat-fusible polyimide is applied to one side or both sides of the self-supporting film.
• 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. Coating is preferably performed uniformly on one or both sides of the self-supporting film with the polyimide precursor solution (b). Therefore, 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 method for applying the polyimide precursor solution (b) to the self-supporting film obtained from the polyimide precursor solution (a) is not particularly limited.
• gravure coating, spin coating, silk screen, dip Known coating methods such as a coating method, a spray coating method, a bar coating method, a knife coating method, a roll coating method, a blade coating method, and a die coating method can be exemplified.
• the self-supporting film of the polyimide precursor solution (a) coated with the polyimide precursor solution (b) is heated and imidized to obtain a heat-fusible polyimide film.
• 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 preferably at a maximum heating temperature of 350 ° C. to 600 ° C., more preferably 450 to 590 ° C., more preferably 490 to 580 ° C., and even more preferably 500 to 580 ° C. It is desirable to perform a third heat treatment for 30 minutes.
• This heat treatment can be performed using a known apparatus such as a hot air furnace or an infrared heating furnace. Further, 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 heat-fusible polyimide film used in the present invention is a dope solution (polyamic acid solution, polyimide precursor) that gives a heat-resistant polyimide layer by a coextrusion-casting film forming method (hereinafter also simply referred to as “coextrusion method”). It can also be produced by a method of laminating, drying, and imidizing a solution that is also referred to as a solution) and a dope solution that gives a heat-fusible polyimide layer.
• this coextrusion method for example, a method described in JP-A-3-180343 (Japanese Patent Publication No. 7-102661) can be used.
• an extrusion molding machine having two or more layers of extrusion dies is used.
• a dope solution for providing a heat-resistant polyimide layer and a dope solution for providing a heat-fusible polyimide layer are cast on a support from the discharge port of the die, thereby forming a laminated thin film.
• the thin film-like body on the said support body is dried, and a multilayer self-supporting film is formed.
• the multilayer self-supporting film is peeled off from the support, and finally the multilayer self-supporting film is heat-treated.
• 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.
• 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. Note that the description in the above-mentioned “manufacturing method by coating method” can be applied as it is to the drying conditions, heating conditions and the like after the continuous extrusion onto the support in the coextrusion-casting film forming method.
• 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, if a dope liquid that provides a heat-resistant polyimide layer and a dope liquid that provides a heat-fusible polyimide layer are used, a two-layer heat-fusible polyimide film can be obtained.
• the first dope solution for providing a heat-fusible polyimide layer-the dope solution for providing a heat-resistant polyimide layer-the second dope solution for providing a heat-fusible polyimide layer three layers of heat are used.
• a fusible polyimide film can also be obtained.
• the first dope solution and the second dope solution may be the same or different.
• the copper clad laminate is formed by laminating a copper foil on the heat-fusible polyimide layer of the heat-fusible polyimide film. Copper foil may be laminated on both sides of the heat-fusible polyimide film, or copper foil may be laminated only on one side of the heat-fusible polyimide film.
• the heat-fusible polyimide film having a heat-fusible polyimide layer on one side or both sides is used.
• stacking copper foil on both surfaces the said heat-fusible polyimide film which has a heat-fusible polyimide layer on both surfaces is used.
• the copper foil include rolled copper foil and electrolytic copper foil.
• the thickness of the copper foil is not particularly limited, but is preferably 2 to 35 ⁇ m, and particularly preferably 5 to 18 ⁇ m.
• a copper foil with a carrier for example, a copper foil with an aluminum foil carrier can be used.
• the heat-fusible polyimide film on which both sides of the heat-fusible polyimide layer are formed is overlapped with copper foil on both sides, and the heat-fusible polyimide film and the copper foil are subjected to thermocompression bonding.
• a copper-clad laminate in which copper foil is laminated on both sides of the adhesive polyimide film can be obtained.
• a copper foil is laminated on the heat-fusible polyimide layer on one side of the heat-fusible polyimide film having the heat-fusible polyimide layer formed on at least one side to heat the heat-fusible polyimide film and the copper foil.
• the heat-fusible polyimide film and the copper foil are continuously thermocompression bonded under heating with at least a pair of pressure members.
• the temperature of the pressure part is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, and even more preferably 70 ° C. or higher than the glass transition temperature of the heat-fusible polyimide.
• the heating temperature is preferably 420 ° C. or less from the viewpoint of preventing thermal deterioration of the heat-fusible polyimide film and the copper foil.
• the glass transition temperature of the heat-fusible polyimide is preferably 250 ° C. or higher, specifically, it is preferably thermocompression bonded in the temperature range of 300 ° C. or higher and 420 ° C. or lower, 350 ° C. As described above, it is more preferable to perform thermocompression bonding in a temperature range of 420 ° C. or less, and more preferable to perform thermocompression bonding in a temperature range of 360 ° C. or more and 420 ° C. or less.
• the pressure member examples include a pair of crimp metal rolls (the crimp part may be made of metal or ceramic sprayed metal), a double belt press, and a hot press.
• a pressure member that can be thermocompression-bonded and cooled under pressure is preferable, and among them, a hydraulic double belt press is particularly preferable.
• a copper-clad 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 copper foil and the reinforcing material are overlapped and continuously heated.
• a long copper-clad laminate can be produced by pressure bonding.
• the use of such a pressure member means that the heat-fusible polyimide film and the copper foil are used in a rolled state, and are continuously supplied to the pressure member, respectively, and the copper-clad laminate is rolled. It is particularly suitable when obtained by
• the copper clad laminate obtained by the production method of the present invention is obtained by firmly laminating a heat-fusible polyimide film and a copper foil.
• a copper clad laminate having a peel strength measured by the method of JIS C6471 of 0.5 N / mm or more, preferably 0.7 N / mm or more can be obtained.
• peeling state may be peeled off at the interface between the heat-resistant polyimide layer and the heat-fusible polyimide film, or peeled off at the interface between the heat-fusible polyimide layer and the copper foil. Therefore, the peel strength measured by the above-mentioned method is the peel strength at the interface having a weaker adhesive force. The method for measuring the peel strength will be described in the Examples section.
• the copper clad laminate obtained in the present invention has good moldability and can be directly subjected to drilling, bending, drawing, metal wiring formation, and the like. Therefore, the copper clad laminated board obtained by this invention can be used suitably as a raw material of electronic components and electronic devices, such as a printed wiring board, a flexible printed circuit board, and a TAB tape.
• the maximum temperature at which foaming was not confirmed was defined as the solder heat resistance temperature.
• Tear strength The tear strength of the heat-fusible polyimide film was measured by the method of IPC-TM-650 2.4.4.17.1. 4). Chemical resistance test A resist was printed on a part of one side of the obtained copper-clad laminate and immersed in an etching solution at 30 ° C. for 20 to 30 minutes to obtain a laminate in which the copper foil on one side was partially etched. . The obtained laminate was dried at 80 ° C. for 30 minutes. The laminate was immersed in a 10% by mass aqueous sodium hydroxide solution heated to 50 ° C. for 30 minutes, washed with water, and the appearance was confirmed.
• the obtained film was subjected to dynamic viscoelasticity measurement using a TA INSTRUMENTS RSA G2 type dynamic viscoelasticity measuring device under conditions of a heating rate of 10 ° C./min and a frequency of 1 Hz, and the tan ⁇ peak temperature was glass transition It was temperature.
• pyromellitic anhydride (PMDA) and benzophenonetetracarboxylic dianhydride (hereinafter also referred to as “BTDA”) as tetracarboxylic dianhydride components were added, and tetracarboxylic dianhydride component and diamine were added.
• the components were reacted to obtain a polyamic acid solution B having a monomer concentration of 18% by mass and a solution viscosity at 25 ° C. of 1800 poise.
• the molar ratio of BTDA and PMDA was 10:90, and the molar ratio of PPD, DADE and BAPP was 75:10:15.
• Example 1 From the three-layer extrusion die, the polyamic acid solution C (thermal fusion layer) -polyamic acid solution A (core layer) -polyamic acid solution C (thermal fusion layer) is formed on the upper surface of the smooth metal support.
• the polyamic acid solution A and the polyamic acid solution C were extruded and cast into a thin film.
• 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.
• Examples 2 to 5 Comparative Examples 1 to 4
• a heat-sealable polyimide film and a copper-clad laminate were obtained in the same manner as in Example 1 except that the type of polyamic acid was changed to that shown in the table.
• Each evaluation result is shown in Table 1.
• the copper clad laminate produced by the method of each example had higher peel strength than the copper clad laminate produced by the method of the comparative example, and had good solder heat resistance and resistance. It turns out that it is excellent in chemical properties.
• the present invention by heat-pressing a specific heat-fusible polyimide film and a copper foil under specific conditions, the heat resistance is excellent, and the polyimide film and the copper foil are A copper clad laminate having a high peel strength can be obtained.

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