WO2017002567A1 - 樹脂組成物、樹脂積層体及び樹脂積層金属箔 - Google Patents
樹脂組成物、樹脂積層体及び樹脂積層金属箔 Download PDFInfo
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- WO2017002567A1 WO2017002567A1 PCT/JP2016/067118 JP2016067118W WO2017002567A1 WO 2017002567 A1 WO2017002567 A1 WO 2017002567A1 JP 2016067118 W JP2016067118 W JP 2016067118W WO 2017002567 A1 WO2017002567 A1 WO 2017002567A1
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- 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
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- 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
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- 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
- B32B15/082—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 vinyl resins; comprising acrylic resins
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- 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
- B32B15/18—Layered products comprising a layer of metal comprising iron or steel
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
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- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
- C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions 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 C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
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- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
- H05K3/385—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by conversion of the surface of the metal, e.g. by oxidation, whether or not followed by reaction or removal of the converted layer
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- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
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- 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
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/206—Insulating
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- 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
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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- 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
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/538—Roughness
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/546—Flexural strength; Flexion stiffness
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- 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
- B32B2307/70—Other properties
- B32B2307/718—Weight, e.g. weight per square meter
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- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/25—Incorporating silicon atoms into the molecule
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- 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
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- C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0154—Polyimide
Definitions
- the present invention provides a resin composition obtained by blending a specific modified block copolymer hydride with a crosslinking aid, a resin laminate obtained by laminating the resin composition and a polyimide resin film, and at least a polyimide resin film.
- the present invention relates to a resin laminated metal foil in which a metal foil is laminated on one side through a layer made of the resin composition.
- the flexible printed circuit board is an important member for internal wiring of devices and component mounting boards.
- Flexible printed circuit boards include two-layer CCL (Copper Clad Laminate) in which an insulating film such as a polyimide film and copper foil are directly bonded, and three-layer CCL in which the insulating film and copper foil are bonded via an adhesive. It has been known.
- the two-layer CCL is superior in reliability at high temperatures because it does not involve an adhesive, but requires a process such as applying a polyamic acid solution, which is a polyimide precursor, to a copper foil, drying, and heating imidization. However, manufacturing is not always easy.
- the three-layer CCL is made by adhering an insulating film such as a polyimide film and a copper foil with an adhesive, so that it is industrially easy to manufacture and inexpensive, and the insulating film and the copper foil are bonded. Excellent in properties. For this reason, three-layer CCL is mainly used in general purpose applications.
- the adhesive used for the production of the three-layer CCL is required to have properties such as adhesion, electrical insulation, chemical resistance, and solder heat resistance.
- adhesives that satisfy these requirements polyamide / epoxy, polyester / epoxy, phenol / butyral, nitrile rubber / epoxy, acrylic, urethane, and the like are known.
- Patent Documents 1 to 4 A number of methods for applying a silane coupling agent to the surface of a copper foil have been proposed as one means for improving the adhesive strength of a copper foil having a small surface roughness (for example, Patent Documents 1 to 4).
- Patent Documents 1 to 4 a method of treating the copper foil surface with a metal alcoholate (Patent Document 5), or bonding with a base material on the copper foil surface
- Patent Document 6 A method of covering the surface with a polysiloxane film (Patent Document 6) has also been proposed.
- Patent Document 6 A method of covering the surface with a polysiloxane film
- Patent Document 8 discloses that a modified block copolymer hydride in which an alkoxysilyl group is introduced into a block copolymer hydride has adhesion to glass and metal, and also has an electrical insulation property. Since it is excellent, it is disclosed that it can be used as a sealing material for solar cells.
- the present invention has been made in view of the above-described circumstances, and is a novel resin composition excellent in adhesiveness to a polyimide resin film and a metal foil having a small surface roughness and excellent in electrical insulation, and this resin composition And a resin laminated metal foil obtained by laminating a polyimide resin film and a metal foil having a small surface roughness by using the resin composition as an adhesive.
- a novel resin composition excellent in adhesiveness to a polyimide resin film and a metal foil having a small surface roughness and excellent in electrical insulation and this resin composition
- a resin laminated metal foil obtained by laminating a polyimide resin film and a metal foil having a small surface roughness by using the resin composition as an adhesive.
- the following resin compositions (1) to (3), a resin laminate and a resin product metal foil are provided.
- the weight fraction of the entire polymer block [A] in the entire block copolymer is wA
- the weight fraction of the entire polymer block [B] in the entire block copolymer is wB
- ADVANTAGE OF THE INVENTION According to this invention, it is excellent in the adhesiveness with respect to a polyimide-type resin film and metal foil with small surface roughness, and the novel resin composition excellent in electrical insulation, and using this resin composition as an adhesive agent
- a resin-laminated copper foil obtained by laminating a polyimide resin film and a metal foil having a small surface roughness is provided.
- the resin laminated metal foil of the present invention is suitably used for the production of a high-density flexible printed circuit board.
- resin composition [F] contains a specific modified block copolymer hydride [E] and a crosslinking aid. .
- the modified block copolymer hydride [E] used in the present invention has at least two polymer blocks [A] having a structural unit derived from an aromatic vinyl compound as a main component and a structural unit derived from a chain conjugated diene compound. Of the main chain and side chain carbon-carbon unsaturated bonds and aromatic ring carbon-carbon unsaturated bonds of the block copolymer [C] consisting of at least one polymer block [B]. This is obtained by introducing an alkoxysilyl group into the block copolymer hydride [D] in which 90% or more is hydrogenated.
- the block copolymer [C] is composed mainly of at least two polymer blocks [A] having a structural unit derived from an aromatic vinyl compound as a main component, and a structural unit derived from a chain conjugated diene compound. It is a block copolymer consisting of one polymer block [B].
- the polymer block [A] has a structural unit derived from an aromatic vinyl compound as a main component.
- the content of the structural unit derived from the aromatic vinyl compound in the polymer block [A] is usually 95% by weight or more, preferably 97% by weight or more, based on all the structural units in the polymer block [A]. Preferably it is 99 weight% or more.
- the heat resistance of the resin composition [F] may be lowered.
- the polymer block [A] may contain components other than the structural unit derived from the aromatic vinyl compound.
- the other components include structural units derived from chain conjugated dienes and / or structural units derived from other vinyl compounds.
- the content thereof is usually 5% by weight or less, preferably 3% by weight or less, more preferably 1% by weight or less, based on all structural units in the polymer block [A].
- aromatic vinyl compound examples include styrene; ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, Styrenes having an alkyl group as a substituent such as 5-t-butyl-2-methylstyrene; Styrenes having a halogen atom as a substituent such as 4-monochlorostyrene, dichlorostyrene, 4-monofluorostyrene; 4-phenyl Examples thereof include styrenes having an aryl group as a substituent such as styrene; styrenes having an alkoxy group as a substituent such as 4-methoxystyrene and 3,5-dimethoxystyrene; Among these, in terms of hygroscopicity, those
- chain conjugated diene and other vinyl compounds examples include those similar to the chain conjugated diene and other vinyl compounds that are structural units of the polymer block [B] described later.
- the polymer block [B] has a structural unit derived from a chain conjugated diene compound as a main component.
- the content of the structural unit derived from the chain conjugated diene compound in the polymer block [B] is usually 80% by weight or more, preferably 90% by weight or more, based on all the structural units in the polymer block [B]. More preferably, it is 95 weight% or more.
- the polymer block [B] may contain components other than the structural unit derived from the chain conjugated diene compound.
- examples of other components include structural units derived from aromatic vinyl compounds and / or structural units derived from other vinyl compounds.
- the content thereof is usually 20% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less, based on all structural units in the polymer block [B].
- the resin composition [F] is excellent in thermal shock resistance and adhesiveness at low temperatures.
- the chain conjugated diene compound is not particularly limited as long as it is a conjugated diene compound having a chain structure.
- chain conjugated diene compounds having no polar group such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene are preferable from the viewpoint of hygroscopicity.
- 1,3-butadiene and isoprene are particularly preferable.
- vinyl compounds include chain vinyl compounds, cyclic vinyl compounds, unsaturated cyclic acid anhydrides, unsaturated imide compounds, and the like. These compounds may have a substituent such as a nitrile group, an alkoxycarbonyl group, a hydroxycarbonyl group, or a halogen atom.
- the weight fraction of the entire block copolymer [C] in the entire polymer block [A] is wA
- the entire block copolymer [C] in the entire polymer block [B] is 30:70 to 60:40, preferably 35:65 to 55:45, more preferably 40:60 to 50 : 50.
- a resin composition [F] having adhesiveness and appropriate heat resistance can be obtained.
- the number of polymer blocks [A] in the block copolymer [C] is usually 3 or less, preferably 2 and the number of polymer blocks [B] is usually 2 or less, preferably 1 It is.
- the plurality of polymer blocks [A] may be the same as or different from each other.
- the polymer blocks [B] may be the same or different from each other.
- the block form of the block copolymer [C] may be a chain type block or a radial type block, but a chain type block is preferred because of its excellent mechanical strength.
- the most preferred form of the block copolymer [C] is the [A]-[B]-[A] type triblock copolymer in which the polymer block [A] is bonded to both ends of the polymer block [B]. It is.
- the molecular weight of the block copolymer [C] is a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, and is usually 40,000 to 200. , Preferably 45,000 to 150,000, more preferably 50,000 to 100,000. Further, the molecular weight distribution (Mw / Mn) of the block copolymer [C] is preferably 3 or less, more preferably 2 or less, and particularly preferably 1.5 or less. When Mw and Mw / Mn are within the above ranges, a resin composition [F] having good heat resistance and mechanical strength can be obtained.
- the manufacturing method of block copolymer [C] is not specifically limited, A well-known method is employable.
- the content of the aromatic vinyl compound in the monomer mixture (a) is usually 95% by weight or more, preferably 97% by weight or more, more preferably 99% by weight or more.
- the content of the chain conjugated diene compound in the monomer mixture (b) is usually 80% by weight or more, preferably 90% by weight or more, more preferably 95% by weight or more.
- the block copolymer hydride [D] is obtained by hydrogenating the carbon-carbon unsaturated bond of the main chain and the side chain and the carbon-carbon unsaturated bond of the aromatic ring of the block copolymer [C]. Is a molecule.
- the hydrogenation rate is usually 90% or more, preferably 97% or more, more preferably 99% or more. The higher the hydrogenation rate, the better the heat resistant and durable resin composition [F].
- the hydrogenation rate of the block copolymer hydride [D] can be determined by measuring 1 H-NMR of the block copolymer hydride [D].
- the molecular weight of the block copolymer hydride [D] is a polystyrene-reduced weight average molecular weight (Mw) measured by GPC using THF as a solvent, and is usually 40,000 to 200,000, preferably 45,000 to 150. , 50,000, more preferably 50,000 to 100,000.
- the molecular weight distribution (Mw / Mn) of the block copolymer hydride [D] is preferably 3 or less, more preferably 2 or less, and particularly preferably 1.5 or less. When Mw and Mw / Mn are within the above ranges, a resin composition [F] having good heat resistance and mechanical strength can be obtained.
- the hydrogenation method and reaction mode of the unsaturated bond are not particularly limited, and may be carried out according to a known method, but a hydrogenation method that can increase the hydrogenation rate and has little polymer chain cleavage reaction is preferable. Examples of such a hydrogenation method include methods described in WO 2011/096389 pamphlet, WO 2012/043708 pamphlet and the like.
- the block copolymer hydride [D] can be isolated from the resulting solution.
- the form of the isolated block copolymer hydride [D] is not limited, it can usually be formed into a pellet shape and used for the subsequent additive blending or alkoxysilyl group introduction reaction.
- Modified block copolymer hydride [E] The modified block copolymer hydride [E] is obtained by introducing an alkoxysilyl group into the block copolymer hydride [D]. By introducing an alkoxysilyl group into the block copolymer hydride [D], strong adhesion to the copper foil and the polyimide resin film can be imparted.
- alkoxysilyl group examples include a tri (C1-6 alkoxy) silyl group such as a trimethoxysilyl group and a triethoxysilyl group; a methyldimethoxysilyl group, a methyldiethoxysilyl group, an ethyldimethoxysilyl group, and an ethyldiethoxysilyl group.
- the alkoxysilyl group is bonded to the block copolymer hydride [D] via a divalent organic group such as an alkylene group having 1 to 20 carbon atoms or an alkyleneoxycarbonylalkylene group having 2 to 20 carbon atoms. You may do it.
- the amount of the alkoxysilyl group introduced into the block copolymer hydride [D] is usually 0.1 to 10 parts by weight, preferably 0.2 to 100 parts by weight per 100 parts by weight of the block copolymer hydride [D]. 5 parts by weight, more preferably 0.5 to 3 parts by weight.
- the introduction amount of the alkoxysilyl group is too large, the resulting modified block copolymer hydride [E] undergoes cross-linking between the alkoxysilyl groups decomposed with a small amount of moisture during storage, gelling, or melt molding There is a possibility that the fluidity at the time is lowered and the adhesiveness to the copper foil or the polyimide resin film is lowered.
- there are too few introduction amounts of an alkoxy silyl group there exists a possibility that the adhesiveness with respect to copper foil or a polyimide-type resin film may fall.
- the modified block copolymer hydride [E] can be produced according to a known method. For example, the method described in WO2012 / 043708 pamphlet, WO2013 / 176258 pamphlet etc. is mentioned.
- the ethylenically unsaturated silane compound to be used is not particularly limited as long as it is graft-polymerized with the block copolymer hydride [D] and introduces an alkoxysilyl group into the block copolymer hydride [D].
- vinyltrialkoxysilane compounds such as vinyltrimethoxysilane and vinyltriethoxysilane; allyltrialkoxysilane compounds such as allyltrimethoxysilane and allyltriethoxysilane; dialkoxyalkylvinylsilanes such as dimethoxymethylvinylsilane and diethoxymethylvinylsilane Compound; p-styryltrialkoxysilane compounds such as p-styryltrimethoxysilane and p-styryltriethoxysilane; 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxy (Meth) acryloxyalkyltrialkoxysilane compounds such as silane and 3-methacryloxypropyltriethoxysilane; 3-methacryloxypropylmethyldimethyl Kishishiran, 3-methacryloxy
- the amount of the ethylenically unsaturated silane compound used is usually 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, more preferably 0, per 100 parts by weight of the block copolymer hydride [D]. .5-3 parts by weight.
- peroxide those having a one-minute half-life temperature of 170 to 190 ° C. are preferably used.
- t-butyl cumyl peroxide, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, di-t-butyl peroxide, Di (2-t-butylperoxyisopropyl) benzene or the like is preferably used.
- the amount of peroxide used is usually 0.05 to 2 parts by weight, preferably 0.1 to 1 part by weight, more preferably 0.2 to 100 parts by weight per 100 parts by weight of the block copolymer hydride [D]. 0.5 weight.
- the method of reacting the block copolymer hydride [D] with the ethylenically unsaturated silane compound in the presence of a peroxide is not particularly limited.
- an alkoxysilyl group can be introduced into the block copolymer hydride [D] by kneading at a desired temperature for a desired time in a biaxial kneader.
- the kneading temperature by the biaxial kneader is usually 180 to 220 ° C, preferably 185 to 210 ° C, more preferably 190 to 200 ° C.
- the heat kneading time is usually about 0.1 to 10 minutes, preferably about 0.2 to 5 minutes, and more preferably about 0.3 to 2 minutes. What is necessary is just to knead
- the form of the obtained modified block copolymer hydride [E] is not limited, it can usually be formed into a pellet shape and then used for blending additives such as a crosslinking aid.
- the molecular weight of the modified block copolymer hydride [E] is not substantially different from the molecular weight of the block copolymer hydride [D] used as a raw material because the amount of alkoxysilyl groups introduced is small.
- the cross-linking reaction and cleavage reaction of the polymer occur simultaneously, and the molecular weight distribution of the modified block copolymer hydride [E] is large. Become.
- the molecular weight of the modified block copolymer hydride [E] is a polystyrene-equivalent weight average molecular weight (Mw) measured by GPC using THF as a solvent, and is usually 40,000 to 200,000, preferably 50,000 to 150,000, more preferably 60,000 to 100,000.
- Mw / Mn The molecular weight distribution (Mw / Mn) is preferably 3.5 or less, more preferably 2.5 or less, and particularly preferably 2.0 or less. When Mw and Mw / Mn are within the above ranges, the heat resistance and mechanical strength of the modified block copolymer hydride [E] are maintained.
- the resin composition [F] of the present invention contains the above-mentioned modified block copolymer hydride [E] and a crosslinking aid.
- a crosslinking aid By blending a crosslinking aid with the modified block copolymer hydride [E], it can be cross-linked and infusible by treatment such as heating or irradiation with high energy rays, and heat resistance can be improved.
- Crosslinking aid As the crosslinking aid used, triallyl isocyanurate, triallyl cyanurate, diallyl phthalate, diallyl fumarate, diallyl maleate, trimeryl trimellitate, triallyl melitrate, diallyl melitrate, divinylbenzene, vinyl butyrate or Polyfunctional vinyl compounds such as vinyl stearate; Ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate having 9 to 14 ethylene glycol repeats, trimethylolpropane trimethacrylate, allyl methacrylate, 2-methyl-1 , 8-octanediol dimethacrylate, polyfunctional methacrylate compounds such as 1,9-nonanediol dimethacrylate; And polyfunctional acrylate compounds such as polyethylene glycol diacrylate, 1,6-hexan
- the amount of the crosslinking aid used is usually 0.1 to 15 parts by weight, preferably 0.2 to 10 parts by weight, more preferably 0.5 parts per 100 parts by weight of the modified block copolymer hydride [E]. ⁇ 5 parts by weight.
- the amount of the crosslinking aid used is too small, the effect of improving the heat resistance of the resin composition [F] is small, and when the amount used is too large, the electrical insulating properties may be deteriorated.
- the method of blending the crosslinking block hydride [E] with the crosslinking aid there is no particular limitation on the method of blending the crosslinking block hydride [E] with the crosslinking aid.
- a method in which a modified block copolymer hydride [E] and a crosslinking aid are added and then melt-kneaded using a twin-screw kneader, an extruder, or the like, and mixed uniformly; organic materials such as toluene and xylene Examples include a method in which the modified block copolymer hydride [E] is dissolved in a solvent, and a crosslinking assistant is added to the solution and mixed uniformly.
- an organic peroxide, an antioxidant, a flame retardant, and the like can be blended in order to improve mechanical properties and chemical properties.
- the organic peroxide used has a decomposition start temperature equal to or higher than the temperature at which the resin composition [F] is adhered to the polyimide resin film or copper foil, usually 100 ° C. or higher, preferably 120 ° C. or higher, more preferably 140 ° C. or higher.
- the temperature at which the half-life (time required for 50% decomposition) is 1 hour is usually 100 ° C. or higher, preferably 120 ° C. or higher, more preferably 140 ° C. or higher.
- organic peroxides include 1,1-di (t-butylperoxy) -2-methylcyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 2,5-dimethyl.
- the compounding amount of the organic peroxide is usually 5 parts by weight or less, preferably 4 parts by weight or less, more preferably 3 parts by weight or less with respect to 100 parts by weight of the modified block copolymer hydride [E].
- amount of the organic peroxide used is too large, the storage stability of the resin composition [F] decreases, and the mechanical strength of the resin composition [F] after heat crosslinking may decrease.
- the resin composition [F] is blended with an organic peroxide by dissolving the modified block copolymer hydride [E] and a crosslinking aid in an organic solvent, adding the organic peroxide to this solution, A method in which the peroxide is dissolved at a temperature at which it is difficult to decompose and mixed uniformly is preferred.
- antioxidant, a flame retardant, etc. can be mix
- the compounding amount of these additives is usually 10 parts by weight or less, preferably 5 parts by weight or less, more preferably 3 parts by weight or less with respect to 100 parts by weight of the modified block copolymer hydride [E].
- antioxidants examples include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like.
- phenolic antioxidants include 3,5-di-t-butyl-4-hydroxytoluene, dibutylhydroxytoluene, 2,2'-methylenebis (6-t-butyl-4-methylphenol), 4,4 ' -Butylidenebis (3-t-butyl-3-methylphenol), 4,4'-thiobis (6-t-butyl-3-methylphenol), ⁇ -tocophenol, 2,2,4-trimethyl-6-hydroxy -7-t-butylchroman, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, [pentaerythritol tetrakis [3- (3,5-di -T-butyl-4-hydroxyphenyl) propionate]] and the like.
- Examples of phosphorus antioxidants include distearyl pentaerythritol diphosphite, bis (2,4-ditertiarybutylphenyl) pentaerythritol diphosphite, tris (2,4-ditertiarybutylphenyl) phosphite, tetrakis (2 , 4-ditertiary butylphenyl) 4,4′-biphenyl diphosphite, trinonylphenyl phosphite and the like.
- Examples of sulfur-based antioxidants include distearyl thiodipropionate and dilauryl thiodipropionate.
- Examples of the flame retardant include inorganic flame retardants such as halogen compounds and antimony compounds usually used for flame retardants such as resins.
- Examples of the halogen compound include tetrabromobisphenol A, brominated epoxy, and halogenated polycarbonate.
- Examples of the inorganic flame retardant include antimony trioxide, antimony tetroxide, antimony pentoxide, sodium pyroantimonate, aluminum hydroxide and the like.
- the method of blending an antioxidant, a flame retardant and the like with the resin composition [F] is not particularly limited.
- the method of melt-kneading the resin composition and the method of blending in the form of a solution can be mentioned in the same manner as blending the crosslinking aid.
- the resin composition [F] produced as described above is used for bonding a polyimide resin film or a copper foil in a solid state such as a pellet or film, or in a solution state dissolved or dispersed in an organic solvent. Can be used.
- the resin composition [F] is used as an adhesive for a polyimide resin film or copper foil
- the resin composition [F] is bonded by thermocompression bonding to the base material before cross-linking and infusibilization by heating or irradiation with high energy rays. Further, it is cross-linked by heating or irradiation with high energy rays to impart heat resistance.
- the temperature at which the resin composition [F] is adhered to the polyimide resin film or copper foil is usually 100 to 250 ° C., preferably 120 to 230 ° C., more preferably 140 to 200 ° C.
- the bonding temperature is below 100 ° C., strong adhesiveness cannot be obtained, and when it exceeds 250 ° C., the mechanical strength of the resin composition [F] may be reduced.
- Examples of the method for improving the heat resistance of the resin composition [F] after the resin composition [F] is bonded to the polyimide resin film or copper foil include a method by heating and a method by irradiation with high energy rays. .
- the heat treatment is usually performed at 130 to 200 ° C., preferably 140 to 180 ° C., more preferably 140 to 160 ° C.
- the irradiation dose is usually 25 to 500 kGy, preferably 50 to 400 kGy, more preferably 100 to 300 kGy. When the irradiation dose is less than this range, the effect of improving the heat resistance of the resin composition [F] becomes small, and when it exceeds this range, the economy may be inferior.
- resin laminate [G] has a layer composed of the resin composition [F] laminated on at least one surface of a polyimide resin film. Is.
- the polyimide resin film used in the present invention is a film made of a polymer having an imide structure in a repeating structural unit. Specific examples include a polyimide film, a polyamideimide film, a polyetherimide film, and a bismaleimide resin film.
- the thickness of the polyimide resin film is not particularly limited, but is usually 10 to 200 ⁇ m, preferably 20 to 150 ⁇ m, more preferably 30 to 100 ⁇ m. When the thickness is within this range, the electrical insulation, mechanical strength, flexibility and the like are good, and it is preferable as an insulating film for a flexible printed board.
- the thickness of the resin composition [F] layer laminated on the polyimide resin film is usually 2 to 500 ⁇ m, preferably 5 to 200 ⁇ m, more preferably 10 to 100 ⁇ m. A thickness within this range is preferable because it has sufficient adhesion to the roughened surface of the metal foil, and has good flexibility and mechanical strength.
- An advantageous resin laminated metal foil is provided.
- the resin laminate [G] is firmly bonded to another metal foil such as a glass plate, an aluminum foil or a stainless steel foil, or another polyimide resin film via a layer made of the resin composition [F].
- a composite multilayer laminate can be provided.
- the resin laminated metal foil of the present invention (hereinafter sometimes referred to as “resin laminated metal foil [H]”) has a layer made of the resin composition [F] on at least one side of a polyimide resin film.
- the metal foil is laminated.
- the metal foil include copper foil, aluminum foil, nickel foil, chrome foil, gold foil, silver foil, and the like, and copper foil is particularly preferable.
- As the copper foil a rolled copper foil, a copper foil whose surface is roughened, or the like can be used.
- the thickness of the metal foil to be used is not particularly limited. The thickness of the metal foil is usually 1.5 to 70 ⁇ m.
- the surface roughened state of the metal foil is not particularly limited and may be appropriately selected depending on the purpose of use.
- the surface roughness of the metal foil used is usually 3.0 ⁇ m or less, preferably 1.5 ⁇ m or less in terms of the maximum height roughness Rz. More preferably, it is 1.0 ⁇ m or less. If the maximum height roughness Rz is within this range, a flexible printed circuit board with a small transmission loss in the high frequency region can be obtained, and further, the obtained metal foil of the three-layer CCL can be removed by etching. The transparency is good and the flexible printed circuit board can be easily positioned during assembly.
- the method of adhering the polyimide resin film and the metal foil using the resin composition [F] of the present invention is not particularly limited.
- a layer made of the resin composition [F] is formed on the surface of the metal foil by applying to the surface of the metal foil and evaporating the solvent, and the polyimide resin film is formed through the layer made of the resin composition [F].
- the method etc. which are made to face and thermocompression-bond can be mentioned.
- the temperature is usually 100 to 250 ° C., preferably 120 to 220 ° C., more preferably 140 to 200 ° C.
- the pressure is usually 0.05 to 2.0 MPa, preferably 0.1 to 1.0 MPa, more preferably.
- the obtained resin-laminated metal foil [H] is further crosslinked in the resin composition [F] layer by a treatment such as heating in an oven or irradiating high energy rays such as ⁇ rays and electron beams. It can also be advanced to improve heat resistance.
- the layer structure of the resin laminated metal foil [H] of the present invention is not particularly limited.
- a layer composed of a polyimide resin film / resin composition [F] / a three-layer structure such as a metal foil a layer composed of a metal foil / resin composition [F] / a polyimide resin film / resin composition [F]
- a five-layer structure such as a layer / metal foil made of
- the resin-laminated metal foil [H] of the present invention can be used as a material for manufacturing a flexible printed circuit board. Also, when using a metal foil having a low surface roughness, a polyimide resin film and a metal foil are used. Since it can adhere
- Evaluation in this example is performed by the following method.
- Mw Weight average molecular weight
- Mw / Mn molecular weight distribution
- the molecular weights of the block copolymer [C] and the block copolymer hydride [D] were measured at 38 ° C. by GPC using THF as an eluent and obtained as standard polystyrene equivalent values.
- As a measuring apparatus HLC8020GPC manufactured by Tosoh Corporation was used.
- Hydrogenation rate The hydrogenation rate of the main chain, side chain, and aromatic ring of the block copolymer hydride [D] was calculated by measuring a 1 H-NMR spectrum.
- a 180 ° peel test was performed according to JIS K 6854-2 at a peel rate of 100 mm / min, and the peel strength was measured. Evaluation of adhesiveness evaluated that adhesiveness was favorable ((circle)) when peeling strength was 10 N / cm or more, and it was inadequate (x) when less than 10 N / cm.
- Block copolymer hydride [D 1 ] Block copolymer hydride [D 1 ]
- a pressure-resistant reactor equipped with a stirrer, and a diatomaceous earth supported nickel catalyst (product name “E22U”, nickel supported amount 60%, manufactured by JGC Catalysts & Chemicals, Inc.) as a hydrogenation catalyst.
- E22U diatomaceous earth supported nickel catalyst
- 8.0 parts and 100 parts dehydrated cyclohexane were added and mixed.
- the inside of the reactor was replaced with hydrogen gas, and hydrogen was supplied while stirring the solution.
- a hydrogenation reaction was performed at a temperature of 190 ° C. and a pressure of 4.5 MPa for 6 hours.
- the weight average molecular weight (Mw) of the block copolymer hydride [D 1 ] contained in the reaction solution obtained by the hydrogenation reaction was 49,900, and the molecular weight distribution (Mw / Mn) was 1.06.
- the reaction solution is filtered to remove the hydrogenation catalyst, and then the phenol-based antioxidant pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) ) Propionate] (product name “Songnox 1010”, manufactured by Matsubara Sangyo Co., Ltd.) 2.0 parts of xylene solution in which 0.1 part was dissolved was added and dissolved.
- the above solution was filtered through a metal fiber filter (pore size 0.4 ⁇ m, manufactured by Nichidai Co., Ltd.) to remove minute solids, and then a cylindrical concentration dryer (product name “Contro”, manufactured by Hitachi, Ltd.) ), The solvent cyclohexane, xylene and other volatile components were removed from the solution at a temperature of 260 ° C. and a pressure of 0.001 MPa or less.
- the molten polymer was extruded into a strand form from a die, and after cooling, 95 parts of pellets of a block copolymer hydride [D 1 ] were produced by a pelletizer.
- the resulting block-like block copolymer hydride [D 1 ] had a weight average molecular weight (Mw) of 49,500, a molecular weight distribution (Mw / Mn) of 1.10, and a hydrogenation rate of almost 100%. .
- Modified block copolymer hydride [E 1 ] With respect to 100 parts of the pellet of the obtained block copolymer hydride [D 1 ], 2.0 parts of vinyltrimethoxysilane and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane ( 0.2 parts of a product name “Perhexa (registered trademark) 25B” (manufactured by NOF Corporation) was added. This mixture was kneaded using a twin screw extruder at a resin temperature of 200 ° C. and a residence time of 60 to 70 seconds, extruded into a strand, air cooled, cut with a pelletizer, and modified block copolymer having an alkoxysilyl group. 96 parts of a pellet of combined hydride [E 1 ] was obtained.
- a peak based on a proton of a methoxy group was observed at 3.6 ppm, and it was confirmed from a peak area ratio that 1.8 parts of vinyltrimethoxysilane was bonded to 100 parts of the block copolymer hydride [D 1 ]. It was.
- Example 1 Production of resin composition [F 1 ] 3 parts of triallyl isocyanurate were mixed with 100 parts of the pellet of the modified block copolymer hydride [E 1 ] obtained in Production Example 1, and a 37 mm ⁇ screw was used.
- T-die type film melt extrusion molding machine (T-die width 300 mm) having a biaxial kneading machine, a cast roll (with an embossed pattern), and an extrusion sheet molding machine equipped with a rubber nip roll and a sheet take-up device
- F 1 ] (thickness 50, 100, 400 ⁇ m, width 230 mm) was obtained.
- the film of the obtained resin composition [F 1 ] was wound up and collected on a roll.
- the film of the resin composition [F 1 ] was stacked and compression molded at 150 ° C. to produce a sheet having a thickness of 3 mm. After the sheet was irradiated with gamma rays in the same manner as described above, a test piece was cut out from the sheet, and the dielectric constant and dielectric loss tangent at a frequency of 1 GHz were measured. The dielectric constant was 2.19 and the dielectric loss tangent was 0.0019, which was a sufficiently small value.
- the obtained resin laminate [G 1- (F)] has a state in which the resin composition [F 1 ] and the polyimide film [a 1 ] are weakly bonded to a peel strength of 2 N / cm or less. Is.
- This resin laminate [G 1- (F 1 / a 1 )] can be firmly bonded by further thermocompression bonding. Further, the copper foil via the resin composition [F 1], aluminum foil, stainless steel foil, glass, ITO-deposited glass, even for ceramics by heating compression bonding was strongly bonded.
- the resin laminate [G 1- (F 1 / a 1 )] obtained above was pressurized for 15 minutes at a temperature of 170 ° C. and a pressure of 0.1 MPa using the vacuum laminator.
- the peel strength was 29 N / cm.
- the evaluation of adhesiveness was ( ⁇ ).
- the resin composition [F 1 ] is bonded to each resin film.
- the peel strength was 2 N / cm or less, and the evaluation was (x) for any resin film.
- Example 5 Production of resin-laminated copper foil [H 1- (a 1 / F 1 / Cu)]
- This laminate is cut into a length of 200 mm and a width of 200 mm, vacuum deaerated using a vacuum laminator for 5 minutes at a temperature of 170 ° C., and then pressed for 15 minutes at a pressure of 0.1 MPa to form a resin laminate.
- Copper foil [H 1- (a 1 / F 1 / Cu)] was produced.
- a film (thickness 50 ⁇ m) / copper foil made of copolymer hydride [E 1 ] was laminated in this order. This laminate is cut into a length of 200 mm and a width of 200 mm, vacuum deaerated using a vacuum laminator for 5 minutes at a temperature of 170 ° C., and then pressed for 15 minutes at a pressure of 0.1 MPa to form a resin laminate.
- a copper foil [H 2- (a 1 / E 1 / Cu)] was produced.
- the resin laminated copper foil [H 2- (a 1 / E 1 / Cu)] was irradiated with gamma rays (dose 100 kGy) in the same manner as in Example 1.
- a test piece having a width of 100 mm and a length of 200 mm was cut out from a resin-laminated copper foil [H 2- (a 1 / E 1 / Cu)] irradiated with gamma rays and held in an oven at 260 ° C. for 60 seconds.
- the copolymer hydride [E 1 ] layer With the deformation of the copolymer hydride [E 1 ] layer, a part of the polyimide film was peeled off from the copper foil, and the heat resistance was insufficient.
- the resulting block-like block copolymer hydride [D 2 ] had a weight average molecular weight (Mw) of 53,700, a molecular weight distribution (Mw / Mn) of 1.11 and a hydrogenation rate of almost 100%. .
- Modified block copolymer hydride [E 2 ] Using the obtained block copolymer hydride [D 2 ] pellets, 94 parts of a modified block copolymer hydride [E 2 ] pellet having an alkoxysilyl group was obtained in the same manner as in Production Example 1. The obtained modified block copolymer hydride [E 2 ] was analyzed in the same manner as in Production Example 1, and vinyltrimethoxysilane 1.8% was added to 100 parts of the block copolymer hydride [D 2 ]. It was confirmed that the parts were combined.
- a test piece was prepared in the same manner as in Example 1 except that the film of the resin composition [F 2 ] was used instead of the resin composition [F 1 ], and the dielectric constant and dielectric loss tangent at a frequency of 1 GHz were measured.
- the dielectric constant was 2.2 and the dielectric loss tangent was 0.0018, which was a sufficiently small value.
- Example 7 resin laminate [G 4 - (F 2 / a 1)] of manufacturing the resin composition in place of the film of [F 1], using a film of the resin composition [F 2] (thickness 400 [mu] m) except that, the same procedure as in example 2, by crimping at 110 ° C., the resin composition [F 2] / polyimide film [a 1] 2-layer structure of the resin laminate of [G 4 - (F 2 / a 1 )] was produced.
- the resulting resin laminate [G 4 - (F 2 / a 1)] , the resin composition [F 2] and a polyimide film [a 1] and is in a state where the peeling strength is adhered weakly below 2N / cm Is.
- the resin laminate [G 4 - (F 2 / a 1)] can be strongly bonded by further heat and pressure. Further, through the resin composition [F 2], a copper foil was firmly bonded by also heat-pressing the aluminum foil, stainless steel foil, glass, ITO-deposited glass, ceramics or the like. Resin laminate obtained above - the [G 4 (F 2 / a 1)], using a vacuum laminator at a temperature 170 ° C., and pressurized for 15 minutes at bonding pressure 0.1 MPa. The resulting resin laminate [G 4 - (F 2 / a 1)] using, was evaluated adhesion to polyimide film of the resin composition [F 2] [a 1] , peel strength 32N / cm And the evaluation was ( ⁇ ).
- Example 8 Production of resin laminated copper foil [H 3- (Cu / F 2 / a 1 / F 2 / Cu)] The same polyimide film [a 1 ] and copper foil (thickness used in Example 5) 18 ⁇ m, maximum height roughness Rz: 1.5 ⁇ m), a film (thickness 50 ⁇ m) of the resin composition [F 2 ] produced in Example 6 was used, and a copper foil / resin composition [F 2 ] / polyimide film. Lamination was performed in the order of [a 1 ] / resin composition [F 2 ] / copper foil. This laminate is cut into a length of 200 mm and a width of 200 mm, vacuum degassed at 170 ° C.
- a resin laminated copper foil [H 3- (Cu / F 2 / a 1 / F 2 / Cu)] in which a copper foil was laminated on both sides of was prepared.
- the resin composition [F] obtained by blending the modified block copolymer hydride [E] of the present invention with a crosslinking aid is crosslinked when irradiated with gamma rays, which are high energy rays, and has heat resistance at a temperature of 260 ° C.
- the dielectric constant and dielectric loss tangent are small and good (Examples 1 and 6).
- the resin composition [F] obtained by blending the modified block copolymer hydride [E] of the present invention with a crosslinking aid exhibits strong adhesiveness to the polyimide resin film (Examples 2, 3, and 4 and 7).
- the resin composition [F] of the present invention has low adhesion to polyethylene terephthalate film, polyphenylene sulfide film, polycarbonate film and polyether sulfone film (Comparative Examples 1, 2, 3, 4).
- the resin laminated copper foil in which the polyimide film and the copper foil are bonded via the resin composition [F] obtained by blending the modified block copolymer hydride [E] of the present invention with a crosslinking aid is the resin and the copper foil. (Examples 5 and 8).
- the heat resistance in the temperature of 260 degreeC is provided by irradiating a resin laminated copper foil with a gamma ray (Examples 5 and 8).
- the resin laminated copper foil in which the polyimide film and the copper foil are bonded only through the modified block copolymer hydride [E] without blending the crosslinking aid is excellent in the adhesion between the resin and the copper foil, Irradiation with gamma rays does not give heat resistance at 260 ° C. (Comparative Example 5).
- the resin composition of the present invention is excellent in adhesion and electrical insulation to polyimide resin films and copper foils with small surface roughness, and can be cross-linked to impart soldering heat resistance, thus producing a high-density flexible printed circuit board and the like. Useful for.
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Abstract
Description
しかしながら、表面粗度の小さい銅箔は樹脂基材との接着力が弱く、細密回路では接着力が不足し、高密度化への障害となっている。
しかしながら、これらの方法では、耐湿性や耐熱性等の様な耐環境性に対する接着特性は改善されるものの、初期の接着強度そのものは、電解銅箔の粗化処理によるアンカ-効果の低減分を十分に補うことができるものではなかった。
(1)芳香族ビニル化合物由来の構造単位を主成分とする、少なくとも2つの重合体ブロック[A]と、鎖状共役ジエン化合物由来の構造単位を主成分とする、少なくとも1つの重合体ブロック[B]とからなり、
全重合体ブロック[A]のブロック共重合体全体に占める重量分率をwAとし、全重合体ブロック[B]のブロック共重合体全体に占める重量分率をwBとしたときに、wAとwBとの比(wA:wB)が30:70~60:40であるブロック共重合体[C]の、主鎖及び側鎖の炭素-炭素不飽和結合及び芳香環の炭素-炭素不飽和結合の90%以上を水素化したブロック共重合体水素化物[D]に、
アルコキシシリル基が導入されてなる変性ブロック共重合体水素化物[E]と、
架橋助剤を含有することを特徴とする樹脂組成物。
(2)前記架橋助剤の含有量が、前記変性ブロック共重合体水素化物[E]100重量部に対して、0.1~15重量部である、(1)に記載の樹脂組成物。
(3)ポリイミド系樹脂フィルムの少なくとも片面に、(1)又は(2)に記載の樹脂組成物からなる層が積層されたものであることを特徴とする樹脂積層体。
(4)ポリイミド系樹脂フィルムの少なくとも片面に、(1)又は(2)に記載の樹脂組成物からなる層を介して金属箔が積層されたものであることを特徴とする樹脂積層金属箔。
(5)前記金属箔の表面粗度が、最大高さ粗さRzで3.0μm以下である、(4)に記載の樹脂積層金属箔。
本発明の樹脂積層金属箔は、高密度フレキシブルプリント基板の製造に好適に用いられる。
本発明の樹脂組成物(以下、「樹脂組成物[F]」ということがある。)は、特定の変性ブロック共重合体水素化物[E]と架橋助剤を含有するものである。
本発明に用いる変性ブロック共重合体水素化物[E]は、芳香族ビニル化合物由来の構造単位を主成分とする、少なくとも2つの重合体ブロック[A]と、鎖状共役ジエン化合物由来の構造単位を主成分とする、少なくとも1つの重合体ブロック[B]とからなるブロック共重合体[C]の、主鎖及び側鎖の炭素-炭素不飽和結合及び芳香環の炭素-炭素不飽和結合の90%以上が水素化されたブロック共重合体水素化物[D]に、アルコキシシリル基が導入されることにより得られたものである。
ブロック共重合体[C]は、芳香族ビニル化合物由来の構造単位を主成分とする、少なくとも2つの重合体ブロック[A]と、鎖状共役ジエン化合物由来の構造単位を主成分とする、少なくとも1つの重合体ブロック[B]とからなるブロック共重合体である。
重合体ブロック[A]中の芳香族ビニル化合物由来の構造単位の含有量は、重合体ブロック[A]中の全構造単位に対して、通常95重量%以上、好ましくは97重量%以上、より好ましくは99重量%以上である。
重合体ブロック[A]中の芳香族ビニル化合物由来の構造単位が少なすぎると、樹脂組成物[F]の耐熱性が低下するおそれがある。
鎖状共役ジエン化合物由来の構造単位が上記範囲にあると、樹脂組成物[F]の耐熱衝撃性、低温での接着性に優れる。
複数の重合体ブロック[A]は、互いに同一であっても、相異なっていても良い。また、重合体ブロック[B]が複数有る場合には、重合体ブロック[B]は、互いに同一であっても、相異なっていても良い。
ブロック共重合体[C]のブロックの形態は、鎖状型ブロックでもラジアル型ブロックでも良いが、鎖状型ブロックであるものが、機械的強度に優れ好ましい。ブロック共重合体[C]の最も好ましい形態は、重合体ブロック[B]の両端に重合体ブロック[A]が結合した、[A]-[B]-[A]型のトリブロック共重合体である。
前記モノマー混合物(a)中の芳香族ビニル化合物の含有量は、通常95重量%以上、好ましくは97重量%以上、より好ましくは99重量%以上である。また、前記モノマー混合物(b)中の鎖状共役ジエン化合物の含有量は、通常80重量%以上、好ましくは90重量%以上、より好ましくは95重量%以上である。
ブロック共重合体水素化物[D]は、上記のブロック共重合体[C]の主鎖及び側鎖の炭素-炭素不飽和結合及び芳香環の炭素-炭素不飽和結合を水素化して得られる高分子である。
その水素化率は通常90%以上、好ましくは97%以上、より好ましくは99%以上である。水素化率が高いほど、耐熱性や耐久性の良好な樹脂組成物[F]が得られる。
ブロック共重合体水素化物[D]の水素化率は、ブロック共重合体水素化物[D]の1H-NMRを測定することにより求めることができる。
変成ブロック共重合体水素化物[E]は、上記ブロック共重合体水素化物[D]に、アルコキシシリル基が導入されたものである。
ブロック共重合体水素化物[D]にアルコキシシリル基を導入することにより、銅箔及びポリイミド系樹脂フィルムに対する強固な接着性を付与することができる。
例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン等のビニルトリアルコキシシラン化合物;アリルトリメトキシシラン、アリルトリエトキシシラン等のアリルトリアルコキシシラン化合物;ジメトキシメチルビニルシラン、ジエトキシメチルビニルシラン等のジアルコキシアルキルビニルシラン化合物;p-スチリルトリメトキシシラン、p-スチリルトリエトキシシラン等のp-スチリルトリアルコキシシラン化合物;3-アクリロキシプロピルトリメトキシシラン、3-アクリロキシプロピルトリエトキシシラン、3-メタクリロキシプロピルトリメトキシシラン、3-メタクリロキシプロピルトリエトキシシラン等の(メタ)アクリロキシアルキルトリアルコキシシラン化合物;3-メタクリロキシプロピルメチルジメトキシシラン、3-メタクリロキシプロピルメチルジエトキシシラン等の(メタ)アクリロキシアルキルアルキルジアルコキシシラン化合物;等が好適に用いられる。これらのエチレン性不飽和シラン化合物は、それぞれ単独で用いてもよいし、2種以上を組み合せて使用してもよい。
本発明の樹脂組成物[F]は、上記の変性ブロック共重合体水素化物[E]、及び、架橋助剤を含有する。
変性ブロック共重合体水素化物[E]に架橋助剤を配合することにより、加熱や高エネルギー線照射等の処理により架橋させて不融化させ、耐熱性を向上させることができる。
用いる架橋助剤としては、トリアリルイソシアヌレート、トリアリルシアヌレート、ジアリルフタレート、ジアリルフマレート、ジアリルマレエート、トリメリルトリメリテート、トリアリルメリテート、ジアリルメリテート、ジビニルベンゼン、ビニルブチラート又はビニルステアレート等の多官能性ビニル化合物;
エチレングリコールジメタクリレート、ジエチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、テトラエチレングリコールジメタクリレート、エチレングリコールの繰り返し数が9~14のポリエチレングリコールジメタクリレート、トリメチロールプロパントリメタクリレート、アリルメタクリレート、2-メチル-1,8-オクタンジオールジメタクリレート、1,9-ノナンジオールジメタクリレートのような多官能性メタクリレート化合物;
ポリエチレングリコールジアクリレート、1,6-ヘキサンジオールジアクリレート、ネオペンチルグリコールジアクリレート、プロピレングリコールジアクリレートのような多官能性アクリレート化合物;等が挙げられる。
これらの架橋助剤は、それぞれ単独で使用してもよく、また2種以上を組合わせて使用してもよい。
樹脂組成物[F]には、機械的特性や化学的特性を向上させるために、有機過酸化物、酸化防止剤、難燃剤等を配合することができる。
樹脂組成物[F]に有機過酸化物を配合することにより、加熱時の架橋を促進することができる。
有機過酸化物の使用量が多過ぎる場合は、樹脂組成物[F]の保存安定性が低下し、また、加熱架橋後の樹脂組成物[F]の機械的強度が低下するおそれがある。
これらの添加剤の配合量は、変性ブロック共重合体水素化物[E]100重量部に対して、通常10重量部以下、好ましくは5重量部以下、より好ましくは3重量部以下である。
フェノール系酸化防止剤としては、3,5-ジ-t-ブチル-4-ヒドロキシトルエン、ジブチルヒドロキシトルエン、2,2’-メチレンビス(6-t-ブチル-4-メチルフェノール)、4,4’-ブチリデンビス(3-t-ブチル-3-メチルフェノール)、4,4’-チオビス(6-t-ブチル-3-メチルフェノール)、α-トコフェノール、2,2,4-トリメチル-6-ヒドロキシ-7-t-ブチルクロマン、テトラキス〔メチレン-3-(3’,5’-ジ-t-ブチル-4’-ヒドロキシフェニル)プロピオネート〕メタン、〔ペンタエリスリトールテトラキス[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート]〕等が挙げられる。
リン系酸化防止剤としては、ジステアリルペンタエリスリトールジホスファイト、ビス(2,4-ジターシャリーブチルフェニル)ペンタエリスリトールジホスファイト、トリス(2,4-ジターシャリーブチルフェニル)ホスファイト、テトラキス(2,4-ジターシャリーブチルフェニル)4,4’-ビフェニルジホスファイト、トリノニルフェニルホスファイト等が挙げられる。
イオウ系酸化防止剤としては、ジステアリルチオジプロピオネート、ジラウリルチオジプロピオネート等が挙げられる。
ハロゲン化合物としては、例えば、テトラブロモビスフェノールAや臭素化エポキシ系、ハロゲン化ポリカーボネート等が挙げられる。無機系難燃剤としては、三酸化アンチモン、四酸化アンチモン、五酸化アンチモン、ピロアンチモン酸ソーダ、水酸化アルミニウム等が挙げられる。
樹脂組成物[F]をポリイミド系樹脂フィルムや銅箔の接着剤として使用する場合は、加熱や高エネルギー線照射により架橋して不融化させる前に、基材に加熱圧着して接着させ、その後、更に加熱したり高エネルギー線を照射したりして架橋させ、耐熱性を付与する。
本発明の樹脂積層体(以下、「樹脂積層体[G]」ということがある。)は、ポリイミド系樹脂フィルムの少なくとも片面に、樹脂組成物[F]からなる層が積層されたものである。
ポリイミド系樹脂フィルムの厚みは特に限定されないが、通常10~200μm、好ましくは20~150μm、より好ましくは30~100μmである。厚みがこの範囲にあれば、電気絶縁性、機械的強度、屈曲性等が良好で、フレキシブルプリント基板用絶縁フィルムとして好ましい。
本発明の樹脂積層金属箔(以下、「樹脂積層金属箔[H]」ということがある。)は、ポリイミド系樹脂フィルムの少なくとも片面に、樹脂組成物[F]からなる層を介して、金属箔が積層されたものである。
金属箔としては、銅箔、アルミ箔、ニッケル箔、クロム箔、金箔、銀箔等が挙げられ、銅箔が特に好ましい。銅箔としては、圧延銅箔、それらを表面粗化した銅箔等が使用できる。使用する金属箔の厚みは特に制限されない。金属箔の厚みは、通常1.5~70μmである。
得られた樹脂積層金属箔[H]は、更にオーブン等で加熱したり、γ線や電子線等の高エネルギー線を照射したりする等の処理により樹脂組成物[F]層の架橋を更に進めて耐熱性を向上することもできる。
(1)重量平均分子量(Mw)及び分子量分布(Mw/Mn)
ブロック共重合体[C]及びブロック共重合体水素化物[D]の分子量は、THFを溶離液とするGPCにより、38℃において測定し、標準ポリスチレン換算値として求めた。測定装置としては、東ソー社製HLC8020GPCを用いた。
(2)水素化率
ブロック共重合体水素化物[D]の主鎖、側鎖及び芳香環の水素化率は、1H-NMRスペクトルを測定して算出した。
(3)樹脂組成物[F]からなる層と樹脂フィルムとの接着性の評価
樹脂組成物[F]からなる厚み300~400μmのフィルム/厚み50~200μmの樹脂フィルムの2層構成の剥離強度測定用の樹脂積層体サンプルを作製した。次いで、このサンプルを幅15mm×長さ150mmの大きさに切断して、剥離強度測定用の試験片とした。
この試験片の樹脂組成物[F]からなる層と樹脂フィルムの界面の一部を引き剥がして、樹脂フィルムのみを引張れるように引張り試験機(製品名「AGS-10KNX」、島津製作所社製)に固定し、剥離速度100mm/分で、JIS K 6854-2に準じて180°剥離試験を行い、剥離強度を測定した。
接着性の評価は、剥離強度が10N/cm以上の場合、接着性は良好(○)、10N/cmを下回る場合は不十分(×)と評価した。
ポリイミド系樹脂フィルム/樹脂組成物[F]からなる層/銅箔の3層構成の樹脂積層銅箔を作製し、このサンプルを幅15mm×長さ150mmの大きさに切断して、剥離強度測定用の試験片とした。
この試験片の樹脂組成物[F]からなる層と銅箔の界面の一部を引き剥がして、銅箔のみを引張れるように、上記と同様の引張り試験機に固定し、剥離速度100mm/分で、JIS K 6854-2に準じて180°剥離試験を行い、剥離強度を測定した。接着性の評価は、剥離強度が10N/cm以上の場合、接着性は良好(○)、10N/cmを下回る場合は不十分(×)と評価した。
(5)耐熱性の評価
ポリイミド系樹脂フィルム/樹脂組成物[F]からなる層/銅箔の3層構成の樹脂積層銅箔[H]を作製し、このサンプルを幅100mm×長さ200mmの大きさに切断して、耐熱性評価用の試験片とした。
この試験片を、汎用的なリフロー半田工程と同等の条件である温度260℃のオーブン中に60秒間保持した後、外観を目視検査して異常の有無を調べた。
耐熱性の評価は、外観検査で変形、剥離、発泡、膨れ等の異常が認められない場合を良好(○)、異常が認められる場合を不良(×)と評価した。
(6)誘電率・誘電正接の測定
樹脂組成物[F]からなる幅10mm×長さ30mm×厚み3mmの試験片を作製し、誘電率及び誘電正接を、ASTM D2520に準じて空洞共振器法により、周波数1GHz、温度:23℃、空気中で測定した。
(ブロック共重合体[C1])
内部が十分に窒素置換された、攪拌装置を備えた反応器に、脱水シクロヘキサン400部、脱水スチレン25.0部、及び、ジ-n-ブチルエーテル0.475部を入れた。全容を60℃で攪拌しながら、n-ブチルリチウムの15%シクロヘキサン溶液0.88部を加えて重合を開始させ、攪拌しながら60℃で60分反応させた。この時点で、反応液をガスクロマトグラフィー(GC)により分析した結果、重合転化率は99.5%であった。
その後、更に、反応液に脱水スチレンを25.0部加え、60℃で60分攪拌した。この時点で、反応液をGCにより分析した結果、重合転化率はほぼ100%であった。ここで、イソプロピルアルコール0.5部を加えて反応を停止させ、重合体溶液を得た。
重合体溶液に含まれるブロック共重合体[C1]の重量平均分子量(Mw)は47,200、分子量分布(Mw/Mn)は1.04、wA:wB=50:50であった。
次に、上記の重合体溶液を、攪拌装置を備えた耐圧反応器に移送し、水素化触媒として、珪藻土担持型ニッケル触媒(製品名「E22U」、ニッケル担持量60%、日揮触媒化成社製)8.0部、及び脱水シクロヘキサン100部を添加して混合した。反応器内部を水素ガスで置換し、さらに溶液を攪拌しながら水素を供給し、温度190℃、圧力4.5MPaにて6時間水素化反応を行った。
水素化反応により得られた反応溶液に含まれるブロック共重合体水素化物[D1]の重量平均分子量(Mw)は49,900、分子量分布(Mw/Mn)は1.06であった。
次いで、上記溶液を、金属ファイバー製フィルター(孔径0.4μm、ニチダイ社製)にて濾過して微小な固形分を除去した後、円筒型濃縮乾燥器(製品名「コントロ」、日立製作所社製)を用いて、温度260℃、圧力0.001MPa以下で、溶液から、溶媒であるシクロヘキサン、キシレン及びその他の揮発成分を除去した。溶融ポリマーをダイからストランド状に押出し、冷却後、ペレタイザーによりブロック共重合体水素化物[D1]のペレット95部を作製した。
得られたペレット状のブロック共重合体水素化物[D1]の重量平均分子量(Mw)は49,500、分子量分布(Mw/Mn)は1.10、水素化率はほぼ100%であった。
得られたブロック共重合体水素化物[D1]のペレット100部に対して、ビニルトリメトキシシラン2.0部及び2,5-ジメチル-2,5-ジ(t-ブチルパーオキシ)ヘキサン(製品名「パーヘキサ(登録商標)25B」、日油社製)0.2部を添加した。この混合物を、二軸押出し機を用いて、樹脂温度200℃、滞留時間60~70秒で混練し、ストランド状に押出し、空冷した後、ペレタイザーによりカッティングし、アルコキシシリル基を有する変性ブロック共重合体水素化物[E1]のペレット96部を得た。
変性ブロック共重合体水素化物[E1]のFT-IRスペクトルを測定した。1090cm-1にSi-OCH3基、825cm-1と739cm-1にSi-CH2基に由来する新たな吸収帯が、ビニルトリメトキシシランのSi-OCH3基、Si-CH2基に由来する吸収帯(1075cm-1、808cm-1及び766cm-1)と異なる位置に観察された。
また、変性ブロック共重合体水素化物[E1]の1H-NMRスペクトル(重クロロホルム中)を測定した。3.6ppmにメトキシ基のプロトンに基づくピークが観察され、ピーク面積比からブロック共重合体水素化物[D1]の100部に対してビニルトリメトキシシラン1.8部が結合したことが確認された。
製造例1で得た変性ブロック共重合体水素化物[E1]のペレット100部にトリアリルイソシアヌレート3部を混合し、37mmφのスクリューを備えた二軸混練機を有するTダイ式フィルム溶融押出し成形機(Tダイ幅300mm)、キャストロール(エンボスパターン付き)、及び、ゴム製ニップロール及びシート引き取り装置を備えた押出しシート成形機を使用して、溶融樹脂温度200℃、Tダイ温度200℃、キャストロール温度80℃の成形条件にて押出し成形し、変性ブロック共重合体水素化物[E1]にトリアリルイソシアネートを配合した樹脂組成物[F1]からなるフィルム(厚み50、100、400μm、幅230mm)を得た。得られた樹脂組成物[F1]のフィルムはロールに巻き取り回収した。
樹脂組成物[F1]のフィルム(厚み400μm)を架橋させるために、ガンマ線照射(照射線量100kGy、コーガアイソトープ社)を行った。ガンマ線を照射した樹脂組成物[F1]のフィルムと未照射の樹脂組成物[F1]のフィルムから、幅100mm、長さ200mmの試験片をそれぞれ切り出し、オーブン中で260℃に60秒間保持したところ、ガンマ線を未照射のフィルムは溶融したが、ガンマ線を照射したフィルムは溶融せず形状を維持しており、架橋して耐熱性が高められたことが確認された。
熱プレス成形機を使用し、樹脂組成物[F1]のフィルムを重ねて、150℃で圧縮成型して厚み3mmのシートを作製した。このシートに上記と同様にガンマ線照射を行った後、シートから試験片を切り出し、周波数1GHzにおける誘電率及び誘電正接を測定した。誘電率は2.19、誘電正接は0.0019で、十分小さく良好な値であった。
樹脂組成物[F1]のフィルム(厚み400μm)とポリイミドフィルム[a1](製品名「カプトン(登録商標) 200H」、厚み50μm、東レ・デュポン社製)を重ね、この積層体を、縦200mm、横200mmに切断し、真空ラミネータ(PVL0202S、日清紡メカトロニクス社製)を使用して、120℃の温度で、5分間真空脱気した後、圧着圧力0.1MPaで1分間加圧することにより、樹脂組成物[F1]/ポリイミドフィルム[a1]の2層構成の樹脂積層体[G1-(F1/a1)]を作製した。
得られた樹脂積層体[G1-(F1/a1)]は、樹脂組成物[F1]とポリイミドフィルム[a1]とが剥離強度が2N/cm以下に弱く接着された状態のものである。この樹脂積層体[G1-(F1/a1)]は、さらに加熱圧着することにより強固に接着できる。また、樹脂組成物[F1]を介して銅箔、アルミニウム箔、ステンレス箔、ガラス、ITO蒸着ガラス、セラミックス等に対しても、加熱圧着することにより、強固に接着した。
ポリイミドフィルム[a1]に代えて、ポリイミドフィルム[a2](製品名「ユーピレックス(登録商標)-50S」、厚み50μm、宇部興産社製)又はポリイミドフィルム[a3](製品名「アピカル(登録商標) 50AH」、厚み50μm、カネカ社製)を使用する以外は実施例2と同様にして、樹脂積層体[G2―(F1/a2)]及び[G3―(F1/a3)]を作製した。
得られた樹脂積層体[G2-(F1/a2)]及び[G3―(F1/a3)]を使用し、樹脂組成物[F1]との接着性を評価したところ、剥離強度はそれぞれ28N/cm及び25N/cmであり、いずれも評価は(○)であった。
ポリイミドフィルム[a1]に代えて、(比較例1)ポリエチレンテレフタレートフィルム[b](製品名「ルミラー(登録商標) S10」、厚さ50μm、東レ社製)、(比較例2)ポリフェニレンスルフィドフィルム[c](製品名「トレリナ(登録商標) 3030」、厚み50μm、東レ社製)、(比較例3)ポリカーボネートフィルム[d](製品名「パンライト(登録商標) PC-2151」、厚さ200μm、帝人社製)又は(比較例4)ポリエーテルサルホンフィルム[e](製品名「スミライト(登録商標) FS-1300」、厚さ100μm、住友ベークライト社製)をそれぞれ使用する以外は、実施例2と同様にして、樹脂積層体[F1/b]、[F1/c]、[F1/d]及び[F1/e]を作製した。
得られた樹脂積層体[F1/b]、[F1/c]、[F1/d]及び[F1/e]を使用し、樹脂組成物[F1]の各樹脂フィルムに対する接着性を評価したところ、剥離強度はいずれも2N/cm以下であり、いずれの樹脂フィルムに対しても評価は(×)であった。
実施例2で使用したのと同じポリイミドフィルム[a1]/実施例1で製造した樹脂組成物[F1]のフィルム(厚み50μm)/銅箔(商品名「FV-WS」 厚み18μm、最大高さ粗さ(Rz):1.5μm、古河電工社製)をこの順に積層した。この積層体を、縦200mm、横200mmに切断し、真空ラミネータを使用して、170℃の温度で、5分間真空脱気した後、圧着圧力0.1MPaで15分間加圧することにより、樹脂積層銅箔[H1-(a1/F1/Cu)]を作製した。
樹脂積層銅箔[H1-(a1/F1/Cu)]を使用し、樹脂組成物[F1]の銅箔に対する接着性を評価したところ、樹脂組成物[F1]と銅箔の剥離強度は18N/cmであり、評価は(○)であった。
樹脂積層銅箔[H1-(a1/F1/Cu)]の樹脂組成物[F1]層の耐熱性を高めるために、樹脂積層銅箔[H1-(a1/F1/Cu)]に、実施例1と同様に、ガンマの照射(線量100kGy)を行った。
ガンマ線を照射した樹脂積層銅箔[H1-(a1/F1/Cu)]から、幅100mm、長さ200mmの試験片を切り出し、オーブン中で260℃に60秒間保持したところ、試験片の外観上の異常は認められず、耐熱性が高いことが確認された。一方、ガンマ線を未照射の樹脂積層銅箔[H1-(a1/F1/Cu)]を同条件で評価したところ、樹脂組成物[F1]層の変形にともなってポリイミドフィルムの一部が銅箔から剥離しており、耐熱性が不足していた。
製造例1で得た変性ブロック共重合体水素化物[E1]のペレットを使用する以外は実施例1と同様にして押出し成形して、変性ブロック共重合体水素化物[E1]からなるフィルム(厚み50μm、幅230mm)を得た。
次に、樹脂組成物[F1]に代えて、変性ブロック共重合体水素化物[E1]のフィルムを使用する以外は、実施例2と同様にして、ポリイミドフィルム[a1]/変性ブロック共重合体水素化物[E1]からなるフィルム(厚み50μm)/銅箔をこの順に積層した。この積層体を、縦200mm、横200mmに切断し、真空ラミネータを使用して、170℃の温度で、5分間真空脱気した後、圧着圧力0.1MPaで15分間加圧することにより、樹脂積層銅箔[H2-(a1/E1/Cu)]を作製した。
樹脂積層銅箔[H2-(a1/E1/Cu)]を使用し、変性ブロック共重合体水素化物[E1]の銅箔に対する接着性を評価したところ、変性ブロック共重合体水素化物[E1]と銅箔の剥離強度は20N/cmであり、評価は(○)であった。
樹脂積層銅箔[H2-(a1/E1/Cu)]に、実施例1と同様にガンマ線の照射(線量100kGy)を行った。ガンマ線を照射した樹脂積層銅箔[H2-(a1/E1/Cu)]から、幅100mm×長さ200mmの試験片を切り出し、オーブン中で260℃に60秒間保持したところ、変性ブロック共重合体水素化物[E1]層の変形にともなってポリイミドフィルムの一部が銅箔から剥離しており、耐熱性が不足していた。
(ブロック共重合体[C2])
製造例1において、スチレン30.0部、イソプレン60.0部、スチレン10.0部をそれぞれ3回に分けて、この順に加え、n-ブチルリチウム(15%シクロヘキサン溶液)を0.80部に変える以外は、製造例1と同様に重合反応及び反応停止操作を行った。
得られたブロック共重合体[C2]の重量平均分子量(Mw)は51,200、分子量分布(Mw/Mn)は1.04、wA:wB=40:60であった。
次に、上記の重合体溶液を、製造例1と同様にして水素化反応を行った。水素化反応後のブロック共重合体水素化物[D2]の重量平均分子量(Mw)は54,200、分子量分布(Mw/Mn)は1.06であった。
得られたブロック共重合体水素化物[D2]のペレットを使用し、製造例1と同様にしてアルコキシシリル基を有する変性ブロック共重合体水素化物[E2]のペレット94部を得た。
得られた変性ブロック共重合体水素化物[E2]は、製造例1と同様にして分析し、ブロック共重合体水素化物[D2]の100部に対して、ビニルトリメトキシシラン1.8部が結合したことが確認された。
変性ブロック共重合体水素化物[E1]に代えて製造例2で得た変性ブロック共重合体水素化物[E2]のペレットを使用する以外は、実施例1と同様にして、変性ブロック共重合体水素化物[E2]100部にトリアリルイソシアネート10部を配合した樹脂組成物[F2]からなるフィルム(厚み50、100、400μm、幅230mm)を成形した。得られた樹脂組成物[F2]のフィルムはロールに巻き取り回収した。
樹脂組成物[F2]のフィルム(厚み400μm)を実施例1と同様に、ガンマ線照射(照射線量100kGy)を行った。ガンマ線を照射した樹脂組成物[F2]のフィルムを、オーブン中で260℃に60秒間保持したところ、フィルムは溶融せず形状を維持しており、耐熱性が高いことが確認された。
樹脂組成物[F1]に代えて、樹脂組成物[F2]のフィルムを使用する以外は実施例1と同様にして試験片を作製し、周波数1GHzにおける誘電率及び誘電正接を測定した。誘電率は2.2、誘電正接は0.0018で、十分小さく良好な値であった。
樹脂組成物[F1]のフィルムに代えて、樹脂組成物[F2]のフィルム(厚み400μm)を使用する以外は実施例2と同様にして、110℃で圧着することにより、樹脂組成物[F2]/ポリイミドフィルム[a1]の2層構成の樹脂積層体[G4-(F2/a1)]を作製した。
得られた樹脂積層体[G4-(F2/a1)]は、樹脂組成物[F2]とポリイミドフィルム[a1]とが剥離強度が2N/cm以下に弱く接着された状態のものである。この樹脂積層体[G4-(F2/a1)]は、さらに加熱圧着することにより強固に接着できる。また、樹脂組成物[F2]を介して、銅箔、アルミニウム箔、ステンレス箔、ガラス、ITO蒸着ガラス、セラミックス等に対しても加熱圧着することにより強固に接着した。
上記で得られた樹脂積層体[G4-(F2/a1)]を、真空ラミネータを使用して、温度170℃で、圧着圧力0.1MPaで15分間加圧した。得られた樹脂積層体[G4-(F2/a1)]を使用し、樹脂組成物[F2]のポリイミドフィルム[a1]に対する接着性を評価したところ、剥離強度は32N/cmであり、評価は(○)であった。
実施例5で使用したのと同じポリイミドフィルム[a1]、銅箔(厚み18μm、最大高さ粗さRz:1.5μm)、実施例6で製造した樹脂組成物[F2]のフィルム(厚み50μm)を使用し、銅箔/樹脂組成物[F2]/ポリイミドフィルム[a1]/樹脂組成物[F2]/銅箔の順に積層した。この積層体を、縦200mm、横200mmに切断し、真空ラミネータを使用して、170℃の温度で、5分間真空脱気した後、圧着圧力0.1MPaで20分間加圧することにより、ポリイミドフィルムの両面に銅箔が積層された樹脂積層銅箔[H3-(Cu/F2/a1/F2/Cu)]を作製した。
樹脂積層銅箔[H3-(Cu/F2/a1/F2/Cu)]を使用し、樹脂組成物[F2]の銅箔に対する接着性を評価したところ、樹脂組成物[F2]と銅箔の剥離強度は22N/cmであり、評価は(○)であった。
樹脂積層銅箔[H3-(Cu/F2/a1/F2/Cu)]に、実施例5と同様にガンマ線の照射(線量100kGy)を行った。ガンマ線を照射した樹脂積層銅箔[H3-(Cu/F2/a1/F2/Cu)]を使用して、実施例5と同様に耐熱性を評価したところ、試験片の外観上の異常は認められず、耐熱性が高いことが確認された。
一方、ガンマ線を未照射の樹脂積層銅箔[H3-(Cu/F2/a1/F2/Cu)]を同条件で評価したところ、樹脂組成物[F2]層の変形にともなってポリイミドフィルムの一部が銅箔から剥離しており、耐熱性が不足していた。
本発明の変性ブロック共重合体水素化物[E]に架橋助剤を配合してなる樹脂組成物[F]は、高エネルギー線であるガンマ線を照射すると架橋して、温度260℃での耐熱性が付与され、また、誘電率、誘電正接も小さく良好である(実施例1、6)。
本発明の変性ブロック共重合体水素化物[E]に架橋助剤を配合してなる樹脂組成物[F]は、ポリイミド系樹脂フィルムに対して強固な接着性を示す(実施例2、3、4及び7)。
一方、本発明の樹脂組成物[F]は、ポリエチレンテレフタレートフィルム、ポリフェニレンスルフィドフィルム、ポリカーボネートフィルム及びポリエーテルサルホンフィルムに対する接着性は低い(比較例1,2,3,4)。
本発明の変性ブロック共重合体水素化物[E]に架橋助剤を配合してなる樹脂組成物[F]を介して、ポリイミドフィルムと銅箔を接着した樹脂積層銅箔は、樹脂と銅箔の間の接着性に優れる(実施例5、8)。また、樹脂積層銅箔にガンマ線を照射することにより、温度260℃における耐熱性が付与される(実施例5、8)。
架橋助剤を配合せず、変性ブロック共重合体水素化物[E]のみを介してポリイミドフィルムと銅箔を接着した樹脂積層銅箔は、樹脂と銅箔の間の接着性には優れるが、ガンマ線を照射しても、260℃における耐熱性は付与されない(比較例5)。
Claims (5)
- 芳香族ビニル化合物由来の構造単位を主成分とする、少なくとも2つの重合体ブロック[A]と、鎖状共役ジエン化合物由来の構造単位を主成分とする、少なくとも1つの重合体ブロック[B]とからなり、
全重合体ブロック[A]のブロック共重合体全体に占める重量分率をwAとし、全重合体ブロック[B]のブロック共重合体全体に占める重量分率をwBとしたときに、wAとwBとの比(wA:wB)が30:70~60:40であるブロック共重合体[C]の、主鎖及び側鎖の炭素-炭素不飽和結合及び芳香環の炭素-炭素不飽和結合の90%以上を水素化したブロック共重合体水素化物[D]に、
アルコキシシリル基が導入されてなる変性ブロック共重合体水素化物[E]と、
架橋助剤を含有することを特徴とする樹脂組成物。 - 前記架橋助剤の含有量が、前記変性ブロック共重合体水素化物[E]100重量部に対して、0.1~15重量部である、請求項1に記載の樹脂組成物。
- ポリイミド系樹脂フィルムの少なくとも片面に、請求項1又は2に記載の樹脂組成物からなる層が積層されたものであることを特徴とする樹脂積層体。
- ポリイミド系樹脂フィルムの少なくとも片面に、請求項1又は2に記載の樹脂組成物からなる層を介して金属箔が積層されたものであることを特徴とする樹脂積層金属箔。
- 前記金属箔の表面粗度が、最大高さ粗さRzで3.0μm以下である、請求項4に記載の樹脂積層金属箔。
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KR20140034800A (ko) * | 2011-05-27 | 2014-03-20 | 히타치가세이가부시끼가이샤 | 기판 및 그 제조 방법, 방열 기판, 그리고 방열 모듈 |
EP3117990A4 (en) * | 2014-03-13 | 2017-11-15 | Zeon Corporation | Composite multi-layer sheet |
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2016
- 2016-06-08 JP JP2017526256A patent/JP6711356B2/ja active Active
- 2016-06-08 EP EP16817676.6A patent/EP3315552B1/en active Active
- 2016-06-08 KR KR1020187000163A patent/KR20180022771A/ko unknown
- 2016-06-08 US US15/579,671 patent/US20180170007A1/en not_active Abandoned
- 2016-06-08 WO PCT/JP2016/067118 patent/WO2017002567A1/ja active Application Filing
- 2016-06-08 CN CN201680034081.4A patent/CN107636070B/zh not_active Expired - Fee Related
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JP2006328410A (ja) * | 2001-03-26 | 2006-12-07 | Jsr Corp | 水添変性重合体及びその製造方法並びにそれを含む組成物 |
WO2003008466A1 (fr) * | 2001-07-18 | 2003-01-30 | Asahi Kasei Chemicals Corporation | Copolymere sequence modifie |
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US11950376B2 (en) * | 2018-03-30 | 2024-04-02 | Mitsui Mining & Smelting Co., Ltd. | Copper-clad laminate |
Also Published As
Publication number | Publication date |
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EP3315552A4 (en) | 2019-03-20 |
CN107636070B (zh) | 2021-03-26 |
KR20180022771A (ko) | 2018-03-06 |
JPWO2017002567A1 (ja) | 2018-04-19 |
EP3315552A1 (en) | 2018-05-02 |
US20180170007A1 (en) | 2018-06-21 |
JP6711356B2 (ja) | 2020-06-17 |
CN107636070A (zh) | 2018-01-26 |
EP3315552B1 (en) | 2023-03-01 |
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