CN114514117B - Biaxially stretched laminated film, laminate, and method for producing same - Google Patents

Biaxially stretched laminated film, laminate, and method for producing same Download PDF

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Publication number
CN114514117B
CN114514117B CN202080071395.8A CN202080071395A CN114514117B CN 114514117 B CN114514117 B CN 114514117B CN 202080071395 A CN202080071395 A CN 202080071395A CN 114514117 B CN114514117 B CN 114514117B
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resin
biaxially stretched
meth
laminate
styrene
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CN114514117A (en
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小桥一范
山田启介
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DIC Corp
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DIC Corp
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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
    • B32B27/285—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 polyethers
    • 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
    • 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
    • B32B7/03—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 with respect to the orientation of features
    • B32B7/035—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 with respect to the orientation of features using arrangements of stretched films, e.g. of mono-axially stretched films arranged alternately
    • 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
    • B32B15/082—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
    • 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
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • 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
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/02—Polythioethers; Polythioether-ethers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B17/00—Insulators or insulating bodies characterised by their form
    • H01B17/56—Insulating bodies
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/04—Flexible cables, conductors, or cords, e.g. trailing cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/08—Flat or ribbon cables
    • 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
    • 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
    • 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
    • H05K1/0393—Flexible materials
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
    • B32B2038/0028—Stretching, elongating
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/02—Synthetic macromolecular particles
    • B32B2264/0214—Particles made of materials belonging to B32B27/00
    • B32B2264/0221—Thermoplastic elastomer particles
    • 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
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • 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
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention provides a film which can be used for directly and thermally bonding a metal layer and a polyarylene sulfide resin at a temperature lower than the melting point of the polyarylene sulfide resin and can realize low dielectric constant and low dielectric loss tangent, a laminate using the film, and a method for producing the same. A biaxially stretched laminated film, a laminate obtained by bonding a biaxially stretched laminated film to a metal layer and/or a resin molded body, and a method for producing the same, wherein a resin layer comprising a biaxially stretched film of a resin composition (A) produced by using a polyphenylene ether resin and a styrene- (meth) acrylic copolymer as raw materials in a polyarylene sulfide resin and having a specific form is arranged as a layer directly bonded to a metal or a resin molded body.

Description

Biaxially stretched laminated film, laminate, and method for producing same
Technical Field
The present invention relates to a biaxially stretched laminate film, a laminate, and a method for producing the same, and more particularly, to a polyarylene sulfide biaxially stretched laminate film excellent in heat adhesion to a metal and/or resin molded body and having low dielectric characteristics, a laminate using the same, and a method for producing the same.
Background
In recent years, in the fields of flexible printed circuit boards (FPCs) and Flexible Flat Cables (FFCs), with the development of cloud, internet of things (Internet of Things, ioT) and the like, the development of automatic driving technology of automobiles, electric automobiles and hybrid automobiles, cables and antennas capable of handling a large amount of data and transmitting at high speed without loss have been demanded. However, conventionally, polyimide (PI) films have been used as FPC substrates, and polyester films (PET films, etc.) have not been said to have dielectric characteristics that can be used for next-generation high-speed transmission. Further, as an insulating material used around an engine used in a next-generation automobile such as an electric automobile or a hybrid automobile, a laminate of a polyester film and aramid paper is used from the viewpoint of the impregnation of engine oil. However, polyester films have a problem of poor heat resistance.
On the other hand, a film using a polyarylene sulfide resin typified by polyphenylene sulfide resin (PPS) is excellent in heat resistance, flame retardancy, chemical resistance, and electrical insulation properties, and therefore is used as an insulating material for a condenser and an engine, and a heat-resistant adhesive tape. Polyarylene sulfide resins have excellent dielectric characteristics compared with PI and PET, and thus can be used in the fields of flexible printed wiring boards (FPCs), flexible Flat Cables (FFCs), and the like. However, polyarylene sulfide films generally have problems such as low adhesion to metals and other resins, low adhesion, and lack of reactivity with adhesives. As a method for improving this problem, for example, patent document 1 describes a laminate characterized in that a resin layer formed OF a resin composition containing polyphenylene sulfide as a main component is laminated on at least one surface OF a metal plate without an adhesive, and the degree OF orientation OF the resin layer is in the range OF 0.65 to 0.9.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication No. 2005-88273
Disclosure of Invention
Problems to be solved by the invention
However, the laminate described in patent document 1 has excellent adhesion to metal, but has a high dielectric constant and a high dielectric loss tangent, and cannot sufficiently cope with high-speed transmission, although the polyphenylene sulfide resin layer is directly laminated to the metal plate. Further, since the thermal compression bonding is performed substantially at or above the melting point of the polyphenylene sulfide resin, it is difficult to obtain a laminate having a good appearance.
Accordingly, the present invention provides a film which enables direct thermal adhesion between a metal layer and a polyarylene sulfide resin at a temperature equal to or lower than the melting point of the polyarylene sulfide resin, has excellent adhesion, and can achieve a low dielectric constant and a low dielectric loss tangent, a laminate using the film, and a method for producing the film and the laminate.
Means for solving the problems
The present inventors have conducted intensive studies and as a result, have found that the above problems can be solved by using a biaxially stretched laminated film in which a resin layer composed of a film obtained by biaxially stretching a resin composition (a) which is produced by using a polyphenylene ether resin and a styrene- (meth) acrylic copolymer as raw materials in a polyarylene sulfide resin and has a specific morphology (morphology) is arranged as a layer directly bonded to a metal or a resin molded body.
That is, the present invention relates to the following (1) to (16).
(1) The present invention relates to a biaxially stretched laminated film having a structure in which at least 2 resin layers are directly laminated,
in the biaxially stretched laminate film described above,
at least 1 layer is a resin layer (A) comprising a biaxially stretched film of a resin composition (A) which comprises a continuous phase and a disperse phase, and which comprises at least a polyarylene sulfide resin, a polyphenylene ether resin and a styrene- (meth) acrylic acid copolymer as raw materials,
the continuous phase comprises a polyarylene sulfide resin,
the dispersed phase contains a polyphenylene ether resin,
the average dispersion diameter of the dispersed phase is in the range of 5 μm or less.
(2) The present invention relates to the biaxially stretched laminated film according to the above (1), wherein the styrene- (meth) acrylic acid copolymer is a copolymer obtained by copolymerizing a styrene-based monomer and a (meth) acrylic acid monomer, and the (meth) acrylic acid monomer is (meth) acrylic acid.
(3) The present invention relates to the biaxially stretched laminate film according to the above (1), wherein the polyarylene sulfide resin has an acid group.
(4) The present invention relates to the biaxially stretched laminated film according to the above (1), wherein the content of the polyphenylene ether resin is in the range of 3 to 40 parts by mass based on 100 parts by mass of the total of the polyarylene sulfide resin, the polyphenylene ether resin, and the styrene- (meth) acrylic acid copolymer.
(5) The present invention relates to the biaxially stretched laminated film according to the above (1), wherein the ratio of the blending amount of the styrene- (meth) acrylic copolymer is in the range of 0.5 to 10 parts by mass based on 100 parts by mass of the total of the polyarylene sulfide resin, the polyphenylene ether resin and the styrene- (meth) acrylic copolymer.
(6) The present invention relates to the biaxially stretched laminated film according to the above (1), wherein the (meth) acrylic acid content of the styrene- (meth) acrylic acid copolymer is in the range of 1 to 30 mass% relative to the total mass of the styrene- (meth) acrylic acid copolymer.
(7) The present invention relates to the biaxially stretched laminated film according to the above (1), wherein the resin composition (A) further comprises an elastomer.
(8) The present invention relates to the biaxially stretched laminated film according to the above (1), wherein the ratio of the blending amount of the elastomer is in the range of 3 to 15 parts by mass based on 100 parts by mass of the total of the polyarylene sulfide resin, the polyphenylene ether resin, the styrene- (meth) acrylic copolymer and the elastomer.
(9) The present invention relates to the biaxially stretched laminated film according to the above (1), wherein the elastomer comprises at least 1 selected from the group consisting of copolymers of α -olefins and glycidyl esters of α, β -unsaturated carboxylic acids, and copolymers of α -olefins, glycidyl esters of α, β -unsaturated carboxylic acids and (meth) acrylic acid esters.
(10) The present invention relates to the biaxially stretched laminated film according to the above (9), wherein the content of the α -olefin in the elastomer is in the range of 50 to 95% by mass based on the total mass of the elastomer.
(11) The present invention relates to the biaxially stretched laminated film according to the above (1), which has a structure in which at least the resin layer (a) and the resin layer (B) are directly laminated, and the resin layer (B) is a biaxially stretched film of a resin composition containing a polyarylene sulfide resin.
(12) The present invention relates to a laminate having a structure in which the resin layer (a) of the biaxially stretched laminate film according to any one of (1) to (11) and at least 1 selected from the group consisting of a metal layer and a resin molded body are bonded.
(13) The present invention relates to a flexible printed wiring board comprising the laminate according to (12) above.
(14) The present invention relates to a flexible flat cable comprising the laminate according to (12) above.
(15) The present invention relates to an engine insulator comprising the laminate according to (12) above.
(16) The present invention relates to a method for producing a biaxially stretched laminated film having a structure in which at least 2 resin layers are directly laminated,
Comprising a step of biaxially stretching an unstretched laminate sheet having a structure in which at least 2 resin layers are directly laminated,
in the biaxially stretched laminate film described above,
at least 1 layer is a resin layer (A) comprising a biaxially stretched film obtained by biaxially stretching a resin composition (A) which comprises at least a polyarylene sulfide resin, a polyphenylene ether resin and a styrene- (meth) acrylic acid copolymer as raw materials and has a continuous phase and a disperse phase,
the continuous phase comprises a polyarylene sulfide resin,
the dispersed phase contains a polyphenylene ether resin,
the average dispersion diameter of the dispersed phase in the resin layer (A) is 5 μm or less.
(17) The present invention relates to a method for producing a laminate, which comprises bonding the resin layer (a) of the biaxially stretched laminate film described in any one of (1) to (11) to at least 1 selected from the group consisting of a metal layer and a resin molded body.
Effects of the invention
According to the present invention, it is possible to provide a film which can directly thermally bond a metal layer and a polyarylene sulfide resin at a temperature equal to or lower than the melting point of the polyarylene sulfide resin, has good adhesion, and can achieve low dielectric constant and low dielectric loss tangent, a laminate using the film, and a method for producing the film and the laminate.
Detailed Description
The biaxially stretched laminated film and the laminated body of the present invention will be described in detail below based on preferred embodiments.
The biaxially stretched laminated film of the present invention is characterized in that,
has a structure in which at least 2 resin layers are directly laminated,
at least 1 layer is a resin layer (A) comprising a biaxially stretched film of a resin composition (A) containing at least a polyarylene sulfide resin (hereinafter also referred to as "PAS resin"), a polyphenylene ether resin (hereinafter also referred to as "PPE resin"), and a styrene- (meth) acrylic copolymer as a raw material, having a continuous phase and a dispersed phase,
the continuous phase comprises a polyarylene sulfide resin,
the dispersed phase contains a polyphenylene ether resin,
the average dispersion diameter of the dispersed phase is in the range of 5 μm or less.
The resin composition (A) used in the present invention is obtained by blending a polyarylene sulfide resin as an essential raw material. In the resin composition (A) used in the present invention, the PAS resin is mainly contained in the continuous phase.
The PAS resin used in the present invention is a polymer comprising a structure in which an aromatic ring and a sulfur atom are bonded (specifically, a structure represented by the following formula (1)) as a repeating unit.
[ chemical 1]
In the above formula, R 1 Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a nitro group, an amino group, a phenyl group, a methoxy group, or an ethoxy group, and n is an integer of 1 to 4.
Wherein R in the structure represented by formula (1) 1 Preferably hydrogen atoms. With such a constitution, the mechanical strength of the PAS resin can be further improved. As R 1 The structure represented by the formula (1) each having a hydrogen atom includes a structure represented by the following formula (2) (i.e., a structure in which a sulfur atom is bonded to an aromatic ring at the para-position) and a structure represented by the following formula (3) (i.e., a structure in which a sulfur atom is bonded to an aromatic ring at the meta-position). Further, the PAS resin may be a copolymer of the formula (2) and the formula (3), and 80 mol% or more of the PAS resin is preferably in the range of 85 mol% or more to 95 mol% or less, more preferably 92 mol% or less, of the PAS resin. If the content is within the above range, the film can be maintained and the melting point can be reduced, which is preferable. The copolymerization system of the copolymerization component is not particularly limited, and a random copolymer is preferable.
[ chemical 2]
Among them, the structure represented by formula (1) is preferably the structure represented by formula (2). The PAS resin having the structure represented by the formula (2) can further improve heat resistance and crystallinity.
The PAS resin may contain, as a repeating unit, not only the structure represented by the above formula (1) but also the structures represented by the following formulas (4) to (7).
[ chemical 3]
The structures represented by the formulae (4) to (7) are preferably contained in an amount of 30 mol% or less, more preferably 10 mol% or less, of all the recurring units constituting the PAS resin. With such a constitution, the heat resistance and mechanical strength of the PAS resin can be further improved.
The bonding patterns of the structures represented by the formulae (4) to (7) may be random or block.
The PAS resin may contain a 3-functional structure represented by the following formula (8), a naphthalene sulfide structure, or the like as a repeating unit in its molecular structure.
[ chemical 4]
The structure represented by the formula (8), the naphthalene sulfide structure, and the like are preferably contained in an amount of 1 mol% or less, more preferably substantially none, of the total repeating units constituting the PAS resin. With such a constitution, the content of chlorine atoms in the PAS resin can be reduced.
The characteristics of the PAS resin are not particularly limited as long as the effect of the present invention is not impaired, and the melt viscosity (V6) at 300℃is preferably in the range of 100 Pa.s or more, more preferably 120 Pa.s or more to preferably 2000 Pa.s or less, and still more preferably 1600 Pa.s or less. In this range, the balance between fluidity and mechanical strength is good, and thus preferable.
Further, the PAS resin preferably has a peak in the molecular weight 25,000 ～ 40,000 range in the measurement using Gel Permeation Chromatography (GPC). Further, the molecular weight is preferably in the range described above and the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is in the range of 5 to 10. Further, it is particularly preferable that the molecular weight range, the ratio (Mw/Mn) range, and the non-Newtonian index range be 0.9 to 1.3. The use of such a PAS resin is preferable because the content of chlorine atoms in the PAS resin itself can be reduced to a range of 1,500 to 2,000ppm without lowering the mechanical strength at the time of film formation, and the PAS resin can be easily used for halogen-free electronic and electric parts.
In the present specification, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw/Mn) are each values measured by Gel Permeation Chromatography (GPC). Further, the measurement conditions of GPC are as follows.
[ measurement conditions for gel permeation chromatography ]
The device comprises: ultra-high temperature polymer molecular weight distribution measuring apparatus (SSC-7000 manufactured by Senshu scientific Co., ltd.)
Column: UT-805L (Zhaohe electric company)
Column temperature: 210 DEG C
Solvent: 1-chloronaphthalene
The measuring method comprises the following steps: using a UV detector (360 nm), 6 monodisperse polystyrenes were used for calibration and the molecular weight distribution and peak molecular weight were determined.
The method for producing the PAS resin is not particularly limited, and examples thereof include:
(Process 1) a process comprising polymerizing a dihaloaromatic compound, if necessary, a polyhaloaromatic compound or other copolymerization component, in the presence of sulfur and sodium carbonate;
(Process 2) a process wherein a dihaloaromatic compound is added in a polar solvent in the presence of a thioetherification agent or the like, and if necessary, a polyhaloaromatic compound or other copolymerization component is added to conduct polymerization; (Process 3) a method of adding parachlorothiophenol and, if necessary, other copolymerization components to conduct self-condensation. Among these production methods, the method (Process 2) is generally preferred.
In the reaction, an alkali metal salt or an alkali metal hydroxide of a carboxylic acid or a sulfonic acid may be added to adjust the polymerization degree.
Among the above methods (method 2), the following method (method 2-1) or the method (method 2-2) is particularly preferable.
In the method of (production method 2-1), an aqueous thioetherification agent is introduced into a heated mixture containing an organic polar solvent and a dihaloaromatic compound at a rate that enables removal of water from the reaction mixture, and the dihaloaromatic compound and a thioetherification agent are added to the organic polar solvent, and if necessary, the polyhaloaromatic compound is added, and at the time of the reaction, the amount of water in the reaction system is controlled to be in the range of 0.02 to 0.5 mol relative to 1 mol of the organic polar solvent, whereby the PAS resin (A) is produced (see JP-A07-228699).
In the method of (production method 2-2), a dihaloaromatic compound and optionally a polyhaloaromatic compound or other copolymerizable component are added in the presence of a solid alkali metal sulfide and an aprotic polar organic solvent, and when an alkali metal hydrosulfide is reacted with an alkali metal salt of an organic acid, the amount of the alkali metal salt of the organic acid is controlled to be in the range of 0.01 to 0.9 mol relative to 1 mol of the sulfur source and the amount of water in the reaction system is controlled to be in the range of 0.02 mol or less relative to 1 mol of the aprotic polar organic solvent, whereby a PAS resin is produced (see WO 2010/058713).
Specific examples of the dihaloaromatic compound include p-dihalobenzene, m-dihalobenzene, o-dihalobenzene, 2, 5-dihalobenzene, 1, 4-dihalobenzene, 1-methoxy-2, 5-dihalobenzene, 4 '-dihalobenzene, 3, 5-dihalobenzoic acid, 2, 4-dihalobenzoic acid, 2, 5-dihalobenzene, 2, 4-dihalobenzene and p, p' -dihalodiphenyl ether, 4 '-dihalodiphenyl ketone, 4' -dihalodiphenyl sulfone, 4 '-dihalodiphenyl sulfoxide, 4' -dihalodiphenyl sulfide, and compounds each having an alkyl group having 1 to 18 carbon atoms in the aromatic ring of the above compound.
Examples of the polyhaloaromatic compound include 1,2, 3-trihalobenzene, 1,2, 4-trihalobenzene, 1,3, 5-trihalobenzene, 1,2,3, 5-tetrahalobenzene, 1,2,4, 5-tetrahalobenzene, and 1,4, 6-trihalonaphthalene.
The halogen atom contained in the above-mentioned compound is preferably a chlorine atom or a bromine atom.
As a method for post-treating the reaction mixture containing PAS resin obtained in the polymerization step, a known and conventional method can be used. Such post-treatment methods are not particularly limited, and examples thereof include the following methods (post-treatment 1) to (post-treatment 5).
In the method of (post-treatment 1), after completion of the polymerization reaction, the solvent is distilled off under reduced pressure or normal pressure, and then the solid matters after the solvent is distilled off are washed 1 or 2 times or more with water, a reaction solvent (or an organic solvent having the same solubility as the low molecular polymer), acetone, methyl ethyl ketone, alcohols and the like, followed by neutralization, washing with water, filtration and drying.
In the method of (post-treatment 2), after completion of the polymerization reaction, a solvent such as water, acetone, methyl ethyl ketone, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons, aliphatic hydrocarbons or the like (a solvent which is soluble in the polymerization solvent to be used and is a poor solvent at least for PAS resin) is added to the reaction mixture as a settling agent, and solid products such as PAS resin and inorganic salts are settled, filtered off, washed and dried.
In the method of (post-treatment 3), after the polymerization reaction is completed, the reaction solvent (or an organic solvent having the same solubility as the low molecular weight polymer) is added to the reaction mixture, and after stirring, the low molecular weight polymer is removed by filtration, and then washed 1 or 2 times or more with a solvent such as water, acetone, methyl ethyl ketone, or alcohol, followed by neutralization, washing with water, filtration, and drying.
In the method of (post-treatment 4), after the completion of the polymerization reaction, water is added to the reaction mixture to perform water washing, filtration, acid treatment with an acid at the time of water washing as needed, and drying are performed.
In the method of (post-treatment 5), after the completion of the polymerization reaction, the reaction mixture is filtered, washed 1 or more times with a reaction solvent as needed, and further washed with water, filtered and dried.
Examples of the acid that can be used in the method of the above (post-treatment 4) include saturated fatty acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, monochloroacetic acid, unsaturated fatty acids such as acrylic acid, crotonic acid, oleic acid, aromatic carboxylic acids such as benzoic acid, phthalic acid, salicylic acid, dicarboxylic acids such as maleic acid and fumaric acid, and organic acids such as sulfonic acids such as methanesulfonic acid and p-toluenesulfonic acid; inorganic acids such as hydrochloric acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, and phosphoric acid.
Examples of the hydrogen salt include sodium hydrosulfide, disodium hydrogen phosphate, and sodium hydrogencarbonate. However, in practical use, an organic acid having little corrosion to the metal member is preferable.
In the methods (post-treatments 1) to (post-treatment 5), the drying of the PAS resin may be performed in vacuum or in an inert gas atmosphere such as air or nitrogen.
In particular, the PAS resin after the post-treatment by the method of (post-treatment 4) has an effect of improving the dispersibility of the dispersed phase because the amount of the acid groups bonded to the molecular terminals thereof increases. The acid group is particularly preferably a carboxyl group.
The proportion of the PAS resin in the resin composition (A) is preferably 50 parts by mass or more, more preferably 60 parts by mass or more to preferably 93 parts by mass or less, more preferably 90 parts by mass or less, based on 100 parts by mass of the total of the PAS resin, the PPE resin and the styrene- (meth) acrylic copolymer. If the content is within the above range, the heat resistance and chemical resistance of the film can be further improved, which is preferable.
The resin composition (a) used in the present invention is prepared by blending a polyphenylene ether resin as an essential raw material.
The PPE-based resin is in principle contained in the dispersed phase of the resin composition (A). The PPE-based resin in the dispersed phase is a component having a function of making the resulting biaxially stretched laminated film low in dielectric constant and low in dielectric loss tangent.
The PPE resin means a polymer having an ether bond directly bonded to an aromatic ring in the main chain, and for example, a polymer having a structure represented by the following formula (9) in the repeating unit.
[ chemical 5]
In the above formula, R 2 Each independently represents a hydrogen atom, a halogen atom, a primary alkyl group having 1 to 7 carbon atoms, a secondary alkyl group having 1 to 7 carbon atoms, a phenyl group, a haloalkyl group, an aminoalkyl group, a hydrocarbyloxy group, a halohydrocarbonyloxy group having at least 2 carbon atoms with a halogen atom and an oxygen atom interposed therebetween, and m is an integer of 1 to 4.
Specific examples of the PPE-based resin include homopolymers such as poly (2, 6-dimethyl-1, 4-phenylene ether), poly (2-methyl-6-ethyl-1, 4-phenylene ether), poly (2-methyl-6-phenyl-1, 4-phenylene ether), and homopolymers such as poly (2, 6-dichloro-1, 4-phenylene ether), copolymers of 2, 6-dimethylphenol with other phenols (for example, 2,3, 6-trimethylphenol, 2-methyl-6-butylphenol), polycondensates of 2, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride, 2-bis [4- (2, 3-dicarboxyphenoxy) phenyl ] propane dianhydride, polycondensates of 4- (2, 3-dicarboxyphenoxy) -4'- (3, 4-dicarboxyphenoxy) diphenyl-2, 2-propane dianhydride with m-phenylenediamine or p-phenylenediamine, and alkali metal salts of dihydroxydiphenyl sulfone, 2-bis (4-hydroxyphenyl) propane or 4' -dihydroxybiphenyl sulfone.
Among them, the PPE-based resin is preferably poly (2, 6-dimethyl-1, 4-phenylene ether) or a copolymer of 2, 6-dimethylphenol and 2,3, 6-trimethylphenol, more preferably poly (2, 6-dimethyl-1, 4-phenylene ether).
The number average molecular weight of the PPE-based resin is preferably 1,000 or more, more preferably 1,500 to 50,000, and still more preferably 1,500 to 30,000.
The ratio of the amount of the PPE resin to be blended in the resin composition (A) is preferably 3 parts by mass or more, more preferably 5 parts by mass or more and preferably 40 parts by mass or less, still more preferably 35 parts by mass or less, based on 100 parts by mass of the total of the PAS resin, the PPE resin and the styrene- (meth) acrylic copolymer. When the content is within the above range, the biaxially stretched laminated film is further excellent in dielectric characteristics (low dielectric constant and low dielectric loss tangent) and in improving effect of direct thermal adhesion to a metal or resin molded body at a temperature equal to or lower than the melting point of the polyphenylene sulfide resin.
The resin composition (A) used in the present invention is obtained by blending a styrene- (meth) acrylic acid copolymer as an essential raw material. By "(meth) acrylic" is meant "acrylic" and/or "methacrylic".
The styrene- (meth) acrylic copolymer is mostly contained in the dispersed phase of the resin composition. The styrene- (meth) acrylic acid copolymer in the disperse phase is a component having a function of improving the stretchability of the biaxially laminated stretched film.
The styrene-methacrylic acid copolymer is a copolymer of a styrene-based monomer and a (meth) acrylic acid-based monomer.
The styrene monomer is not particularly limited, and styrene and its derivatives may be mentioned. Examples of the styrene derivative include alkylstyrenes such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene, and octylstyrene; halogenated styrenes such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, and iodostyrene; nitrostyrene; acetyl styrene; methoxystyrene, and the like. These styrene monomers may be used alone or in combination of 1 or more than 2.
Examples of the (meth) acrylic monomer include, in addition to acrylic acid and methacrylic acid, alkyl (meth) acrylates having a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. In this case, the substituent is not particularly limited, and examples thereof include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, hydroxyl group, and the like. The number of substituents may be 1 or 2 or more. In the case of having 2 or more substituents, each substituent may be the same or different. Specific examples of the alkyl (meth) acrylate having a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, hydroxyethyl (meth) acrylate, and hydroxypropyl (meth) acrylate. Among them, (meth) acrylic acid is preferable from the viewpoints of compatibility and reactivity. The (meth) acrylic monomer may be used alone or in combination of 1 or more than 2 kinds.
The content of the repeating unit based on (meth) acrylic acid contained in the styrene- (meth) acrylic acid copolymer is preferably in the range of 1% by mass or more and preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 18% by mass or less relative to the total mass of the styrene- (meth) acrylic acid copolymer, from the viewpoint of obtaining good compatibility, further improving the stretching uniformity and folding strength of the biaxially stretched laminated film, and the like.
As the polymerization reaction of the styrene- (meth) acrylic acid copolymer, a general-purpose polymerization method of a styrene-based monomer can be applied.
The polymerization method is not particularly limited, and bulk polymerization, suspension polymerization, or solution polymerization is preferable. Among them, the polymerization method is particularly preferably continuous bulk polymerization in view of productivity. For example, a styrene- (meth) acrylic acid copolymer excellent in characteristics can be obtained by performing continuous bulk polymerization using an apparatus in which 1 or more stirred reactors and a tubular reactor having a plurality of mixing elements without movable portions fixed therein are assembled.
Although thermal polymerization can be performed without using a polymerization initiator, various radical polymerization initiators are preferably used. The polymerization auxiliary agent such as a suspending agent and an emulsifier required for the polymerization reaction may be a compound used for the production of a usual polystyrene.
In order to reduce the viscosity of the reactants in the polymerization reaction, an organic solvent may be added to the reaction system. Examples of such an organic solvent include toluene, ethylbenzene, xylene, acetonitrile, benzene, chlorobenzene, dichlorobenzene, anisole, cyanobenzene, dimethylformamide, N-dimethylacetamide, and methylethylketone. These organic solvents may be used alone or in combination of 1 or more than 2.
Examples of the radical polymerization initiator include peroxone such as 1, 1-bis (t-butylperoxy) cyclohexane, 2-bis (t-butylperoxy) butane, and 2, 2-bis (4, 4-dibutylperoxy cyclohexyl) propane; hydroperoxides such as cumene hydroperoxide and tert-butyl hydroperoxide; dialkyl peroxides such as di-t-butyl peroxide, dicumyl peroxide, and di-t-hexyl peroxide; diacyl peroxides such as benzoyl peroxide and dicannamyl peroxide; peroxyesters such as t-butyl peroxybenzoate, di-t-butyl peroxyisophthalate, t-butyl peroxyisopropyl monocarbonate, and the like; n, N ' -azobisisobutyronitrile, N ' -azobis (cyclohexane-1-carbonitrile), N ' -azobis (2-methylbutyronitrile), N ' -azobis (2, 4-dimethylvaleronitrile), N ' -azobis [2- (hydroxymethyl) propionitrile ], and the like. These radical polymerization initiators may be used alone or in combination of 1 or more than 2.
Further, a chain transfer agent may be added to the reaction system so as not to excessively increase the molecular weight of the resulting styrene- (meth) acrylic acid copolymer. As the chain transfer agent, a monofunctional chain transfer agent having 1 chain transfer group may be used, or a multifunctional chain transfer agent having a plurality of chain transfer groups may be used. Examples of the monofunctional chain transfer agent include alkylthio alcohols and thioglycolate esters. Examples of the polyfunctional chain transfer agent include compounds obtained by esterifying hydroxyl groups of polyhydric alcohols such as ethylene glycol, neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, and sorbitol with thioglycolic acid or 3-mercaptopropionic acid. These chain transfer agents may be used alone or in combination of 1 or more than 2.
In order to suppress gelation of the resulting styrene- (meth) acrylic acid copolymer, a long-chain alcohol, a polyoxyethylene alkyl ether, a polyoxyethylene lauryl ether, a polyoxyethylene oleyl ether, a polyoxyethylene alkenyl ether, or the like may be used.
The ratio of the amount of the styrene- (meth) acrylic acid copolymer to be blended in the resin composition (a) is preferably in a range of 0.5 parts by mass or more, more preferably 1 part by mass or more and preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, relative to 100 parts by mass of the total of the PAS resin, the PPE-based resin and the styrene- (meth) acrylic acid copolymer. When the content is within the above range, good compatibility can be obtained, and the stretching uniformity, the folding strength, and the like of the biaxially stretched laminated film can be further improved.
The resin composition (a) used in the present invention is prepared by blending an elastomer as an optional raw material as required. In the case of using an elastomer, the elastomer is in principle contained in the dispersed phase of the resin composition (a). The elastomer in the dispersed phase also functions as a compatibilizer between the PAS resin and the PPE resin, and has a function of improving mechanical strength (such as tear strength) by micro-dispersing the dispersed phase. In addition, the use of a styrene- (meth) acrylic acid copolymer further improves the adhesion of the interface between the PAS resin and the PPE resin by means of an elastomer, and further improves the mechanical strength (such as folding strength and tear strength).
The elastomer more preferably has a functional group (hereinafter also referred to as "functional group-containing elastomer") capable of reacting with at least one of the PAS resin and the PPE resin, and thus the mechanical strength (folding strength, tear strength, etc.) of the biaxially stretched laminate film can be further improved.
The functional group that the functional group-containing elastomer may have is preferably at least 1 selected from the group consisting of an epoxy group and an acid anhydride group, and more preferably an epoxy group. These functional groups can react with functional groups at molecular terminals of PAS resins and PPE resins.
As the elastomer, an olefin resin having at least 1 functional group selected from the group consisting of an epoxy group and an acid anhydride group is preferable.
Examples of such an elastomer include a copolymer containing a repeating unit based on an α -olefin and a repeating unit based on a vinyl polymerizable compound having the above functional group; copolymers comprising repeating units based on alpha-olefins, repeating units based on vinyl polymerizable compounds having the above functional groups, and repeating units based on acrylic esters, and the like.
Examples of the α -olefin include an α -olefin having 2 to 8 carbon atoms such as ethylene, propylene, butene-1, and the like.
Examples of the vinyl polymerizable compound having a functional group include α, β -unsaturated carboxylic acids such as acrylic acid, methacrylic acid, acrylic acid ester, and methacrylic acid ester, and esters thereof, maleic acid, fumaric acid, itaconic acid, and other unsaturated dicarboxylic acids having 4 to 10 carbon atoms, monoesters and diesters thereof, and anhydrides thereof, α, β -unsaturated dicarboxylic acids such as esters and anhydrides thereof, and α, β -unsaturated glycidyl esters.
The α, β -unsaturated glycidyl ester is not particularly limited, and examples thereof include compounds represented by the following formula (10).
[ chemical 6]
In the above formula, R 3 Is an alkenyl group having 1 to 6 carbon atoms.
Examples of the alkenyl group having 1 to 6 carbon atoms include vinyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-pentenyl, 1-methyl-3-pentenyl, 1-dimethyl-1-butenyl, 1-hexenyl, 3-hexenyl and the like.
R 4 Each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-dimethylbutyl, 2, 3-dimethylbutyl, 2, 4-dimethylbutyl, 3-dimethylbutyl, 2-ethylbutyl and the like.
Specific examples of the α, β -unsaturated glycidyl ester include glycidyl acrylate and glycidyl methacrylate, and glycidyl methacrylate is preferable.
The α -olefin content of the elastomer is preferably in a range of 50 mass% or more and preferably 95 mass% or less, more preferably 80 mass% or less, relative to the total mass of the elastomer. If the proportion of the repeating units based on the α -olefin is in the above range, the stretching uniformity, the folding strength, and the like of the biaxially stretched laminated film can be improved.
The proportion of the repeating unit based on the vinyl polymerizable compound having a functional group in the elastomer is preferably in the range of 1% by mass or more, more preferably 2% by mass or more to preferably 30% by mass or less, more preferably 20% by mass or less. If the proportion of the repeating unit based on the vinyl-polymerizable compound having a functional group is in the above range, not only the effect of improving is aimed, but also good extrusion stability can be obtained.
In the case of blending an elastomer, the ratio of the blending amount of the elastomer in the resin composition (a) is preferably in the range of 3 parts by mass or more, more preferably 5 parts by mass or more to preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less, relative to 100 parts by mass of the total of the PAS resin, the PPE resin, the styrene- (meth) acrylic copolymer, and the elastomer. When the content is within the above range, the dielectric characteristics (low dielectric constant and low dielectric loss tangent) and the folding strength of the biaxially stretched laminated film can be further improved.
The resin composition (a) used in the present invention is prepared by blending a silane coupling agent as an optional raw material as required. The silane coupling agent can improve the compatibility (interaction) between the PAS resin and other components (PPE resin, styrene-methacrylic acid copolymer and optionally an elastomer). In addition, by using the silane coupling agent, dispersibility of other components in the PAS resin is dramatically improved, and a good form can be formed.
The silane coupling agent is preferably a compound having a functional group capable of reacting with a carboxyl group. Such silane coupling agents are firmly bonded to other components by reacting with them. As a result, the effect of the silane coupling agent can be more remarkably exhibited, and particularly, the dispersibility of other components in the PAS resin can be improved.
Examples of the silane coupling agent include compounds having an epoxy group, an isocyanate group, an amino group, or a hydroxyl group.
Specific examples of the silane coupling agent include alkoxysilane compounds having an epoxy group such as γ -glycidoxypropyl trimethoxysilane, γ -glycidoxypropyl triethoxysilane, β - (3, 4-epoxycyclohexyl) ethyl trimethoxysilane, alkoxysilane compounds having an amino group such as γ -isocyanatopropyl trimethoxysilane, γ -isocyanatopropyl triethoxysilane, γ -isocyanatopropyl methyldimethoxysilane, γ -isocyanatopropyl methyldiethoxysilane, γ -isocyanatopropyl ethyldimethoxysilane, γ -isocyanatopropyl ethyldiethoxysilane, γ -isocyanatopropyl trichlorosilane, alkoxysilane compounds having an isocyanate group such as γ - (2-aminoethyl) aminopropyl methyldimethoxysilane, γ - (2-aminoethyl) aminopropyl trimethoxysilane, γ -aminopropyl trimethoxysilane, alkoxysilane compounds having an amino group such as γ -hydroxypropyl trimethoxysilane, γ -hydroxypropyl triethoxysilane, and the like.
When the silane coupling agent is blended, the ratio of the blending amount of the silane coupling agent in the resin composition (a) is preferably in a range of 0.01 parts by mass or more, more preferably 0.05 parts by mass or more and preferably 5 parts by mass or less, still more preferably 2.5 parts by mass or less, relative to 100 parts by mass of the total of the PAS resin, the PPE resin, the styrene- (meth) acrylic copolymer, and the silane coupling agent. When the content is within the above range, dispersibility of other components in the PAS resin can be further improved.
The resin composition (a) used in the present invention may contain known additives such as plasticizers, weather-proofing agents, antioxidants, heat stabilizers, ultraviolet stabilizers, lubricants, antistatic agents, colorants, and conductive agents, if necessary, within a range that does not inhibit the effects of the present invention.
The method for producing the resin composition (a) used in the present invention is not particularly limited, and the following methods may be mentioned: the respective materials and optional materials and additives as needed are uniformly dry-mixed by a tumbler mixer, a henschel mixer or the like as needed, and then fed into a twin-screw extruder, heated to a temperature equal to or higher than the melting temperature of the resin seed, and melt-kneaded.
The melt kneading is preferably performed under conditions such that the ratio (discharge amount/screw revolution) of the kneaded product (kg/hr) to the screw revolution (rpm) is 0.02 to 0.2 (kg/hr·rpm).
More specifically, it is preferable to charge each raw material component into a twin-screw extruder and melt-knead the raw material component at a temperature of about 330 ℃ at a set temperature of 300 ℃ and a resin temperature at a drawing die. In this case, the discharge amount of the kneaded material is in the range of 5 to 50kg/hr at 250 rpm. In particular, from the viewpoint of improving the dispersibility of each component, the discharge amount of the kneaded material is preferably 20 to 35kg/hr at 250 rpm. Therefore, the ratio (discharge amount/screw revolution) of the discharge amount (kg/hr) of the kneaded material to the screw revolution (rpm) is more preferably 0.08 to 0.14 (kg/hr·rpm).
The biaxially stretched laminated film of the present invention has a structure in which at least 2 resin layers are directly laminated. At least 1 layer of the biaxially stretched laminated film is a resin layer (a) composed of a biaxially stretched film of the resin composition (a). The method for producing a biaxially stretched laminated film of the present invention further comprises a step of biaxially stretching an unstretched laminated sheet having a structure in which at least 2 resin layers are directly laminated.
In one embodiment of such a biaxially stretched laminate film, the resin layer (a) has a PAS resin as a matrix (continuous phase), and particles (dispersed phase) containing a PPE-based resin are dispersed in the matrix. In the resin layer (a), the matrix (continuous phase) and the particles (dispersed phase) are derived from the continuous phase and the dispersed phase, respectively, in the resin composition (a) constituting the same. Since the matrix (continuous phase) is composed of the PAS resin, the biaxially stretched laminate film can be obtained which maintains the properties of the PAS resin such as heat resistance, flame retardancy, chemical resistance, and wet heat resistance.
The styrene-methacrylic acid copolymer is present in the particles of the PPE-based resin or as particles (dispersed phase) different from the particles (dispersed phase) of the PPE-based resin.
In the case where the resin composition (a) contains an elastomer, the elastomer is present on the surface of the PPE-based resin (i.e., at the interface between the matrix and the particles), in the particles of the PPE-based resin, or as particles (dispersed phase) different from the particles of the PPE-based resin.
Further, the inventors have considered that since the elastomer also functions as a compatibilizer for a PAS resin and a PPE resin, the mechanical strength (folding strength, etc.) of the biaxially stretched laminate film is further improved by micro-dispersing the particles in the matrix. Further, the inventors have also considered that the combination with the silane coupling agent further improves the adhesion at the interface between the elastomer matrix and the particles, and further improves the mechanical strength (folding strength, etc.) of the biaxially stretched laminated film.
In the resin layer (a), the average particle diameter (average dispersion diameter) of particles (dispersed phase) dispersed in the matrix (continuous phase) is preferably 5 μm or less, more preferably 3 μm or less, and on the other hand, the lower limit value is not particularly limited, but more preferably 0.5 μm or more. If the average particle diameter of the particles is within the above range, a uniform and homogeneous biaxially laminated stretched film can be obtained. In the present specification, the "average particle diameter of particles" is measured as follows.
First, the biaxially stretched film of the resin layer (a) is cut by an ultrathin section method in the direction (I) parallel to the longitudinal direction and perpendicular to the film surface and (II) parallel to the width direction and perpendicular to the film surface. Next, 2000 times Scanning Electron Microscope (SEM) pictures were taken of the cut surfaces (I) and (II) of the cut film, 50 particles were selected from the obtained SEM pictures, the maximum diameter of each particle in the cut surfaces (I) and (II) was measured, and 2 directions of the cut surfaces (I) and (II) were combined to calculate an average particle diameter.
Further, if the membrane after the cleavage is stained with ruthenic acid and STEM-EDS analysis is performed, the components of the matrix and particles constituting the membrane can be analyzed.
The biaxially stretched laminated film of the present invention is not particularly limited as long as it has a structure in which at least 2 resin layers are directly laminated, and for example, it may be a laminated film in which the resin layers (a) are directly laminated, or a laminated film in which the resin layers (a) and a resin layer other than the resin layers (a) are directly laminated. With this configuration, adhesion to the metal or resin molded body can be performed at a temperature equal to or lower than the melting point of the PAS resin, and low dielectric characteristics corresponding to high-speed transmission can be achieved.
In the case where the biaxially stretched laminated film of the present invention is a laminated film in which the resin layers (a) are directly laminated on each other, the same resin layers (a) may be directly laminated on each other, for example, the same resin layers (a) except for the film thickness may be directly laminated. Further, the resin layers (a) formed of biaxially stretched films of the same resin composition (a) may be directly laminated, except that the blending ratio of the essential or arbitrary raw material components or the average dispersion diameter of the dispersed phase are different from each other.
In addition, from the viewpoint of being able to impart various functions, the biaxially stretched laminated film of the present invention may be configured as a laminated film in which a resin layer (a) formed of a biaxially stretched film of the above-described resin composition (a) and a resin layer (also simply referred to as "resin layer (B)") formed of a biaxially stretched film of a resin composition (B) containing a thermoplastic resin different from the above-described resin composition (a) are directly laminated. Here, the resin layer (B) may be formed of a biaxially stretched film of a resin composition containing a thermoplastic resin, and the resin composition containing a thermoplastic resin is preferably a resin composition containing a PAS resin, a polyamide, a polyetherimide, a polyethersulfone, a polysulfone, a polyester (particularly preferably an aromatic polyester such as polyethylene terephthalate or polybutylene terephthalate), a polyarylate, a polyamideimide, a polycarbonate, a polyetheretherketone, a liquid crystal polymer, or a polymer containing a blend of at least 1 of these polymers, and more preferably a resin composition containing a PAS resin.
The PAS resin contained in the resin composition (B) used in the present invention may be the same resins as those described for the PAS resin. The proportion of the PAS resin contained in the resin composition (B) is not particularly limited, but is preferably 60 parts by mass or more, particularly preferably 65 parts by mass or more. The resin composition (B) may contain, as a raw material, a resin species other than the PAS resin and an additive, and for example, the polyphenylene ether resin, the styrene- (meth) acrylic copolymer, the elastomer, the silane coupling agent, further polyamide, polyetherimide, polyethersulfone, polysulfone, polyester (particularly preferably aromatic polyester such as polyethylene terephthalate and polybutylene terephthalate), polyarylate, polyamideimide, polycarbonate, polyether ether ketone, a liquid crystal polymer, and various polymers including at least one of these polymers may be used. The method for producing the resin composition (B) used in the present invention is also similar to the above-mentioned resin composition (A).
In addition, the resin layer constituting at least one layer of the biaxially stretched laminated film of the present invention may be a layer having voids. By having the voids, the dielectric characteristics, particularly the dielectric constant, can be further improved. As a method for producing a biaxially stretched laminated film including a layer having voids, a known method of forming voids in a sheet or film can be used. For example, the biaxially stretched laminated film production method of the present invention may further include a step of blending a pore former into the resin composition, and may be produced by biaxially stretching an unstretched sheet of the resin composition containing the pore former to form fine cracks at the interface between the resin and the pore former, thereby producing a biaxially stretched laminated film containing a layer having voids (sometimes referred to as a fine crack method). Further, as another method, there are a step of adding a pore former to the resin composition and a step of bringing an unstretched sheet or biaxially stretched film produced from the resin composition containing the pore former into contact with a solvent (sometimes referred to as a solvent removal method) for dissolving the pore former to remove the pore former, thereby forming voids in the unstretched sheet or biaxially stretched film, and the like (sometimes referred to as a solvent removal method). In the case where voids are formed in an unstretched sheet, if the biaxially stretched sheet is laminated with another unstretched sheet and then biaxially stretched, a biaxially stretched laminated film including a layer having voids can be obtained.
The pore former is preferably calcium carbonate particles, and examples thereof include magnesium sulfate particles, calcium oxide particles, calcium hydroxide particles, and silica particles, and in the solvent removal method, a solvent that is solid at room temperature (23 ℃) or a solvent that is liquid at room temperature (referred to as a liquid solvent) may be used. Examples of the liquid solvent include aliphatic or cyclic hydrocarbons such as nonane, decane, decalin, paraxylene, undecane, dodecane, and liquid paraffin, mineral oil fractions having boiling points corresponding to these hydrocarbons, and phthalates such as dibutyl phthalate and dioctyl phthalate which are liquid at room temperature, and nonvolatile liquid solvents such as liquid paraffin are preferably used. The solid solvent is mixed with the polyolefin in a state of being heated and melted and kneaded, and examples thereof include solvents that are solid at room temperature, and stearyl alcohol, waxy alcohol, paraffin wax, and the like can be used. In addition, if only a solid solvent is used, there is a possibility that stretching unevenness may occur, and therefore, a liquid solvent is preferably used in combination. On the other hand, specific examples of the solvent to be removed include acidic aqueous solutions such as hydrochloric acid, chlorinated hydrocarbons such as methylene chloride and carbon tetrachloride, hydrocarbons such as pentane, hexane and heptane, fluorinated hydrocarbons such as ethane trifluoride, diethyl ether and diethyl ether Ethers such as alkanes, methyl ethyl ketone, and the like. In addition, as the removal solvent, a solvent having a surface tension of 24mN/m or less at 25℃as disclosed in Japanese patent application laid-open No. 2002-256099 may be used in addition to the above. By using a solvent having such a surface tension, shrinkage and densification of the network structure due to the surface tension of the gas-liquid interface generated inside the pores can be suppressed at the time of drying after the pore forming agent is removed, and as a result, the porosity and permeability of the layer having the pores are further improved. The porosity of the layer having pores is not particularly limited, but is preferably in the range of 20% or more, more preferably 30% or more to preferably 70% or less, more preferably 60% or less, from the viewpoint of excellent mechanical strength and dielectric characteristics. The porosity means a ratio of the areas of voids contained in an image obtained by ultrathin slicing a layer having voids in a biaxially stretched laminated film in a direction parallel to the longitudinal direction and perpendicular to the film surface and in a direction parallel to the width direction and perpendicular to the film surface, and then taking 2000-fold Scanning Electron Microscope (SEM) photographs of the cut surfaces (I) and (II) of the cut film, respectively, when the area of the obtained SEM photograph is taken as 100. At this time, if no void is observed, the void ratio becomes 0%. The ratio of each of the cut surfaces (I) and (II) was measured, and the average value obtained by combining the 2 directions of the cut surfaces (I) and (II) was defined as the "porosity". In the present invention, when pores are formed using a pore former, the ratio of the amount of the pore former to be mixed may be appropriately adjusted so that the porosity is within the above range, and the ratio may be different depending on the specific gravity of the resin composition and the pore former, and whether the pore former is left (microcrack method) or removed (solvent removal method), and thus it cannot be roughly specified, for example, the ratio is preferably 70 parts by mass or less, more preferably 50 parts by mass or less to preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 20 parts by mass or more, and particularly preferably 30 parts by mass or more, with respect to 100 parts by mass of the total of the resin composition and the pore former.
In the case where the biaxially stretched laminated film of the present invention has a laminated structure of the resin layer (a) and the resin layer (B), the laminated structure may be a multilayer structure such as (a)/(B)/(a)/(B)/(a), but is not limited thereto. Among them, from the viewpoint of suppressing curl of the biaxially stretched laminated film, a symmetrical structure of (a)/(B)/(a), (a)/(B)/(a)/(B) is preferable. The term "/" means direct bonding, and for example, "(a)/(B)" means a structure in which each of the resin layers (a) and (B) is directly laminated.
In the biaxially stretched laminated film of the present invention, the thickness of the resin layer (a) is preferably in the range of 2 μm or more, more preferably in the range of 10 μm or more. When the thickness of the resin layer (a) is in the range of 2 μm or more, high adhesion can be easily obtained. On the other hand, the upper limit is not limited, but is preferably in the range of 150 μm or less, and more preferably in the range of 100 μm or less. The thickness of the resin layer (B) is arbitrary, for example, other than the resin layer (a).
The method for producing the biaxially stretched laminate film used in the present invention is not particularly limited, and there may be mentioned a method of producing an unstretched laminate sheet having a structure in which at least 2 resin layers are directly laminated, and then biaxially stretching the obtained unstretched laminate sheet. For example, when the laminate structure is formed, the following coextrusion method is used: the resin or resin mixture used for each resin layer is heated and melted in different extruders, and the resin layers are directly laminated in a molten state according to a desired lamination composition by a method such as a coextrusion lamination die method or a feed block method, and then molded into a sheet by a blowing method, a T-die chill roll method, or the like. The coextrusion method is preferable because the ratio of the thicknesses of the respective layers can be relatively freely adjusted, and an unstretched laminate sheet excellent in cost performance can be obtained.
Next, in the case of biaxial stretching, the unstretched laminate sheet obtained as described above is biaxially stretched.
The stretching ratio in the longitudinal direction (MD direction) of the biaxially stretched film is preferably in the range of 2 times or more, more preferably 2.5 times to preferably 4 times or less, and still more preferably 3.8 times or less.
The stretching ratio in the width direction (TD direction) of the biaxially stretched film is preferably in the range of 2 times or more, more preferably 2.5 times to preferably 4 times or less, and still more preferably 3.8 times or less.
In view of the ease of balancing the physical properties in the longitudinal direction and the physical properties in the width direction, the ratio of the stretching magnification in the width direction (TD direction) of the biaxially stretched film to the stretching magnification in the longitudinal direction (MD direction) of the biaxially stretched film (width direction (TD direction)/(longitudinal direction (MD direction)) is preferably in the range of 0.8 or more, more preferably 0.9 or more to preferably 1.3 or less, and still more preferably 1.2 or less.
As the stretching method, a sequential biaxial stretching method, a simultaneous biaxial stretching method, or a method combining them can be used.
In the case of biaxially stretching by the sequential biaxial stretching method, for example, the obtained unstretched sheet is heated by a heated roll set, stretched in a range of preferably 2 times or more, more preferably 2.5 times or less to preferably 4 times or less, more preferably 3.8 times or less in the longitudinal direction (MD direction), and then cooled by a cooled roll set at 30 to 60 ℃ in 1 or 2 or more stages.
The stretching temperature is preferably in the range of not less than the glass transition temperature (Tg) of the PAS resin, more preferably not less than (tg+5 ℃) and not more than (tg+40 ℃) and more preferably not more than (tg+30 ℃) and still more preferably not more than (tg+20 ℃).
Next, stretching was performed in the width direction (TD direction) by a method using a tenter. Both ends of the film stretched in the MD direction were gripped by clips, and introduced into a tenter to be stretched in the TD direction.
The stretch ratio is preferably in the range of 2 times or more, more preferably 2.5 times or less to preferably 4 times or less, and still more preferably 3.8 times or less.
The stretching temperature is preferably in the range of Tg or higher, more preferably (tg+5℃ C.) or higher and (tg+40℃ C.) or lower, more preferably (tg+30℃ C.) or lower, and still more preferably (tg+20℃ C.) or lower.
Then, the stretched film is preferably thermally fixed under tension or thermally fixed while being relaxed in the width direction.
The heat fixing temperature is not particularly limited, and is preferably in the range of 200℃or more, more preferably 220℃or more, still more preferably 240℃or more to 280℃or less, and still more preferably 275℃or less. It should be noted that the thermal fixing may be performed in 2 stages by changing the thermal fixing temperature. In this case, the hot setting temperature in the 2 nd stage is preferably set to +10 to 40 ℃ higher than the hot setting temperature in the 1 st stage. The heat resistance and mechanical strength of the stretched film having a heat-set temperature in this range are further improved.
Further, the heat setting time is preferably 1 to 60 seconds.
Further, the film is cooled while being relaxed in the width direction in a temperature range of 50 to 275 ℃. The relaxation rate is not particularly limited, and is preferably in the range of 0.5% or more, more preferably 2% or more, further preferably 3% or more to preferably 10% or less, more preferably 8% or less, further preferably 7% or less.
The thickness of the biaxially stretched laminated film is not particularly limited, and is preferably the sum of the layers, and the thickness of each layer is preferably in the range of 2 μm or more, more preferably 10 μm or more to preferably 300 μm or less, 200 μm or less, and further preferably 100 μm or less. More specifically, the thickness of the biaxially stretched laminated film is preferably in the range of 10 μm or more and 300 μm or less, more preferably 200 μm or less, and still more preferably 150 μm or less, from the viewpoint of being able to exert sufficient mechanical strength and dielectric properties.
The biaxially laminated stretched film of the present invention may be subjected to a surface treatment for the purpose of improving the adhesion between the biaxially laminated stretched film and the metal or resin molded article. Examples of the surface treatment include corona discharge treatment (including corona treatment in various gas atmospheres), plasma treatment (including plasma treatment in various gas atmospheres), and oxidation treatment by a chemical agent, ultraviolet rays, electron irradiation, and the like. Among them, plasma treatment is preferable.
According to one aspect of the present invention, a laminate is provided. The laminate has a structure in which a resin layer (A) of a biaxially stretched laminate film is bonded to at least 1 selected from the group consisting of a metal layer and a resin molded body. The laminate includes the biaxially stretched laminate film, and a metal layer or a resin molded body directly disposed on at least one outermost resin layer surface of the biaxially stretched laminate film.
The metal layer is not particularly limited, and examples thereof include copper, aluminum, zinc, titanium, nickel, an alloy containing the same, and the like.
The metal layer may be a single layer or 2 layers. In the case where the metal layer is 2 layers, the respective metal phases may be the same or different.
In one embodiment, the laminate may be composed of, for example, a metal layer-biaxially stretched laminate film-metal layer-biaxially stretched laminate film, a metal layer-biaxially stretched laminate film-metal layer, or the like. The "-" means direct bonding, and for example, the "metal layer-biaxially stretched laminated film" means a structure in which each metal layer and the biaxially stretched laminated film are directly bonded.
Examples of the method for bonding the metal layer to the biaxially stretched laminate film include vacuum deposition, sputtering, and plating of a metal. The metal layer may be formed by a method of overlapping the biaxially stretched laminated film and the metal foil and thermally welding the overlapped film and the metal foil.
The laminate provided with the metal layer has excellent dielectric characteristics (low dielectric constant and low dielectric loss tangent) and can therefore be suitably used for high-speed transmission of new generation such as flexible printed wiring boards, flexible flat cables, and particularly electronic/electric devices capable of coping with wireless transmission speeds of 100Gbps and even 1 Tbps. Further, the biaxially stretched laminated film has excellent heat resistance and insulation properties, and thus can be suitably used for an insulator for an engine.
In one embodiment, the laminate may be composed of, for example, a resin molded body-biaxially stretched laminate film-resin molded body, a resin molded body-biaxially stretched laminate film-metal layer, or the like.
The method of bonding the biaxially stretched laminate film to the resin molded body includes a method of bonding the biaxially stretched laminate film to the resin molded body by heat bonding such as heat welding.
Examples of the resin molded article include, but are not limited to, an extrusion molded article such as a polyolefin resin, a polyester resin, a nylon resin, a polyarylene sulfide resin, an aromatic polyamide, and a liquid crystal resin, an injection molded article, and a fiber sheet.
The planar shaped article is sometimes referred to as a film or sheet depending on the thickness, and for example, a distinction between a film of less than 200 μm and a sheet of 200 μm or more is described in a polymer dictionary (the society for high molecular weight, toward a bookstore, 1971), and a thin planar shaped article of a maximum thickness of 250 μm to a minimum thickness of 25 μm is described in a McGraw-Hill science and technology dictionary (the journal of the industry, 1996), depending on the case, a distinction is also described in a technical field in which a film of less than 100 μm and a sheet of 100 μm or more are described. As such, it is generally difficult to distinguish the film from the sheet. Thus, in the present invention, the terms "sheet" and "film" are merely based on differences in terms of designation and do not distinguish one from another. For example, a "sheet" is a concept including a member such as a thin planar object, a film, or a membrane, and thus, a "membrane" is a concept including a member such as a thin planar object, a film, or a sheet, and cannot be distinguished only by the difference in terms.
Examples
The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
1. The components used are
[ polyarylene sulfide resin (a-1) ]
PPS resin a-1: linear polyphenylene sulfide resin (resin produced by DIC Co., ltd., melting point 280 ℃ C., melt viscosity at 300 ℃ C. (V6) 160 Pa.s) and using p-dichlorobenzene alone as dichlorobenzene)
PPS resin a-2: linear polyphenylene sulfide resin produced in reference example 1 below
Reference example 1 preparation of polyphenylene sulfide resin (a-2)
19.222kg of flaky sodium sulfide (60.9 mass%) and 45.0kg of N-methyl-2-pyrrolidone were placed in a 150 liter autoclave. While stirring under a nitrogen stream, the temperature was raised to 204℃and 4.438kg of water was distilled off (the amount of water remaining was 1.14 moles per 1 mole of sodium sulfide). Then, the autoclave was sealed and cooled to 180℃and p-dichlorobenzene 21.721kg and m-dichlorobenzene 3.833kg (molar ratio [ (p)/(m) ]=85/15) were charged with 18.0kg of N-methyl-2-pyrrolidone. The temperature was raised by pressurizing with nitrogen gas to 1kg/cm2 at a liquid temperature of 150 ℃. Stirring was carried out at a liquid temperature of 220℃for 3 hours while cooling by flowing a refrigerant of 80℃through a coil wound around the outside of the upper part of the autoclave. Then, the temperature was raised, and after stirring at 260℃for 3 hours, the temperature was lowered and the cooling of the upper part of the autoclave was stopped. The upper part of the autoclave was cooled so that the liquid temperature was kept constant without decreasing. The highest pressure in the reaction was 8.91kg/cm2. The resulting slurry was washed with warm water 2 times and filtered to obtain a cake containing about 50% by mass of water. Then, 60kg of water and 100g of acetic acid were added to the cake to reslurry, and the mixture was stirred at 50℃for 30 minutes and then filtered again. At this time, the pH of the slurry was 4.6. The filter cake obtained here was repeatedly subjected to filtration again after 5 times of addition of 60kg of water and stirring for 30 minutes. The obtained cake was dried in a heated air circulation dryer at 120℃for 4.5 hours to obtain a white powdery polyphenylene sulfide resin (a-2) (hereinafter abbreviated as PPS resin a-2.). The melting point was 230℃and the melt viscosity (V6) at 300℃was 45 Pa.s.
[ polyphenylene ether-based resin (b) ]
PPE: poly (2, 6-dimethyl-1, 4-phenylene ether)
PPS has a carboxyl group at its molecular end, and PPE has a hydroxyl group at its molecular end.
[ styrene-methacrylic acid copolymer (c) ]
Styrene resin c-1: styrene and methacrylic acid were reacted at 97.5:2.5 mass ratio of copolymer polymerized
Styrene resin c-2: styrene and methacrylic acid were reacted at 80.0:20.0 mass ratio of copolymer polymerized
Elastomer (d)
Elastomer d-1: ethylene, glycidyl methacrylate and methyl acrylate were reacted at 70:3:27 mass ratio of polymerized glycidyl group modified elastomer (manufactured by Sumitomo chemical Co., ltd., "BONDFAST 7L")
Elastomer d-2: ethylene, glycidyl methacrylate were reacted at 88:12 mass ratio of polymerized glycidyl group modified elastomer (manufactured by Sumitomo chemical Co., ltd., "BONDFAST E")
Elastomer d-3: maleic anhydride-modified elastomer (Sanjing Chemicals, "Toughmer MH 7020")
[ silane coupling agent ]
Silane coupling agent: gamma-aminopropyl trimethoxysilane
EXAMPLE 1 production of resin composition (A) and resin layer (A)
86.5 parts by mass of PPS resin a-1, 5 parts by mass of PPE, 3 parts by mass of styrene resin c-1, 5 parts by mass of elastomer d-1 and 0.5 part by mass of a silane coupling agent were uniformly mixed by a drum mixer to obtain a mixture.
Next, the mixture was fed into a twin screw extruder (manufactured by Nippon Steel Co., ltd., "TEX-30. Alpha.") with a belt conveyor. Then, the resin composition (A-1) was produced by melt-extruding at a discharge rate of 20kg/hr, a screw revolution rate of 300rpm, and a set temperature of 300℃and discharging the melt in the form of strands, cooling the strands with water at a temperature of 30℃and cutting the strands.
Next, the resin composition (a-1) was fed into a single-screw extruder with a full-flight screw, melted at 280 ℃ to 300 ℃, extruded from a T die, and cooled by a cooling roll set at 40 ℃ in a close contact manner to produce an unstretched polyarylene sulfide resin sheet. Further, the unstretched polyarylene sulfide resin sheet was stretched to 3.5X3.5 times at 100℃by using a batch biaxial stretcher manufactured by well-established manufacturing, thereby obtaining a biaxially stretched film having a thickness of 35. Mu.m. Further, the obtained biaxially stretched film was fixed to a mold frame, and heat-setting treatment was performed by using an oven at 275 ℃. The biaxially stretched film was used to evaluate dielectric properties.
The biaxially stretched film obtained above was cut by an ultrathin section method in a direction perpendicular to the film surface. Then, the cut film was dyed with ruthenic acid, and STEM-EDS analysis was performed to analyze the components of the matrix and particles constituting the biaxially stretched film. As a result, it was found that the component constituting the matrix was PPS and the component constituting the particles was PPE. The elastomer is present as individually dispersed particles or at the interface of the matrix and the particles of PPE.
EXAMPLES 2 TO 9 preparation of resin composition (A) and resin layer (A)
Resin compositions (A-2 to A-9) for resin layers (A-2 to A-9) were produced in the same manner as in example 1 except that the blending amounts of PPS resin a-1, PPE, styrene resin, modified elastomer and silane coupling agent were changed as shown in Table 1, and biaxially stretched films using the obtained resin compositions (A-2 to A-9) were produced in the same manner as in example 1 except that the stretching ratio was changed to 3X 3.
Further, as a result of analyzing the constituent components of the biaxially stretched film by the same method as in example 1, it was found that particles of PPE were dispersed in a matrix of PPS. The elastomer is present as individually dispersed particles or at the interface of the matrix and the particles of PPE.
EXAMPLE 10 production of resin composition (A) and resin layer (A)
A resin composition (A-10) for a resin layer (A-10) was produced in the same manner as in example 2, except that 30.6 parts by mass of PPS resin a-2, 45.9 parts by mass of PPS resin a-1, 15 parts by mass of PPE, 3 parts by mass of styrene resin c-1, 5 parts by mass of elastomer d-1 and 0.5 part by mass of a silane coupling agent were uniformly mixed by a drum mixer to obtain a mixture, and a biaxially stretched film using the obtained resin composition (A-10) was produced, and the dielectric characteristics were evaluated.
Further, the components of the biaxially stretched film were analyzed by the same method as in example 1, and it was found that particles of PPE were dispersed in a matrix of PPS. The elastomer is present as individually dispersed particles or at the interface of the matrix and the particles of PPE.
Comparative example 1 production of resin composition (A) and resin layer (A)
A biaxially stretched film was obtained in the same manner as in example 1, except that a resin composition (cA-1) containing 94.5 parts by mass of PPS resin a-1, 5 parts by mass of elastomer d-1 and 0.5 part by mass of a silane coupling agent was used instead of the resin composition containing 86.5 parts by mass of PPS resin a-1, 5 parts by mass of PPE, 3 parts by mass of styrene resin c-1, 5 parts by mass of elastomer d-1 and 0.5 part by mass of a silane coupling agent. The dielectric constant and dielectric loss tangent of the obtained biaxially stretched film were measured.
Comparative example 2 production of resin composition (A) and resin layer (A)
A biaxially stretched film was obtained in the same manner as in example 1, except that a resin composition (cA-2) comprising 89.5 parts by mass of PPS resin a-1, 5 parts by mass of PPE, 5 parts by mass of elastomer d-1 and 0.5 part by mass of a silane coupling agent was used instead of the resin composition comprising 86.5 parts by mass of PPS resin a-1, 5 parts by mass of PPE, 3 parts by mass of styrene resin c-1, 5 parts by mass of elastomer d-1 and 0.5 part by mass of a silane coupling agent. The dielectric constant and dielectric loss tangent of the obtained biaxially stretched film were measured.
Comparative example 3 production of resin composition (A) and resin layer (A)
PPS resin a-1 was fed into a twin screw extruder "TEX-30. Alpha." made of Steel, japan, co., ltd., melt extruded at a screw rotation speed of 300rpm at a set temperature of 300℃and discharged in the form of strands at a discharge rate of 20kg/hr, cooled with water at a temperature of 30℃and cut to prepare a melt. Next, the kneaded material was fed into a single-screw extruder with a full-flight screw, melted at 280 to 300 ℃, extruded from a T die, and cooled by a cooling roll set at 40 ℃ in a close contact manner to prepare an unstretched polyarylene sulfide resin sheet. Further, the unstretched polyarylene sulfide resin sheet was stretched to 3.5X3.5 times at 100℃by using a batch biaxial stretcher manufactured by well-established manufacturing, thereby obtaining a biaxially stretched film having a thickness of 35. Mu.m. Further, the obtained biaxially stretched film was fixed to a mold frame, and heat-setting treatment was performed by using an oven at 270 ℃. The dielectric constant and dielectric loss tangent of the obtained biaxially stretched film were measured.
Reference example 2
[ preparation of resin composition (B) ]
PPS resin a-1 was fed into a twin screw extruder (manufactured by Nippon Steel Co., ltd., "TEX-30. Alpha.") for a belt conveyor. Then, the resin composition (B-1) was produced by melt-extruding at a discharge rate of 20kg/hr, a screw revolution rate of 300rpm, and a set temperature of 300℃and discharging the melt in the form of strands, cooling the strands with water at a temperature of 30℃and cutting the strands.
Reference example 3
60 parts by mass of PPS resin a-1 and 40 parts by mass of calcium carbonate (CaCO 3, manufactured by Wakuku-tiku Co., ltd., average particle size: 3 μm) were fed into a twin-screw extruder (manufactured by Nippon Steel Co., ltd., "TEX-30. Alpha.") with a belt conveyor. Then, the resin composition (B-2) was produced by melt-extruding at a discharge rate of 20kg/hr, a screw revolution rate of 300rpm, and a set temperature of 300℃and discharging the melt in the form of strands, cooling the strands with water at a temperature of 30℃and cutting the strands.
Example 11 production of biaxially stretched laminate film and laminate
The resin compositions (A-1) and (B-1) were fed to an extruder (40 mm in diameter) for the resin layer (A) and an extruder (40 mm in diameter) for the resin layer (B), melted at 280 to 300℃and fed to a coextrusion sheet producing apparatus (feed block and T die temperature: 300 ℃) of the T die/chill roll method having a feed block, and after melt extrusion, the resultant sheet was cooled by a chill roll set at 40℃in close contact with each other to produce a coextrusion laminated unstretched sheet composed of 3 layers of the resin layer (A)/the resin layer (B)/the resin layer (A).
Next, the obtained laminate was biaxially stretched to 3.5X3.5 times at 100℃by using a batch biaxial stretching machine (manufactured by Kyowa Kagaku Co., ltd.), to thereby obtain a film having a thickness of 50. Mu.m. Further, the obtained film was fixed to a mold frame, and heat-fixing treatment was performed by using an oven at 275 ℃.
Next, the biaxially stretched laminated film and the electrolytic copper foil (thickness: 18 μm) thus obtained were laminated so that the resin layer (a) of the biaxially stretched laminated film and the electrolytic copper foil were joined, and the laminate of the copper foil and the film was produced by pressing at 270 ℃ under a pressure of 5MPa for 15 seconds by a press machine.
Example 12 production of biaxially stretched laminate film and laminate
A biaxially stretched laminate film and a laminate were produced in the same manner as in example 11, except that the resin composition (a-2) was used in the resin layer (a) and the stretching ratio was changed to 3×3.
Examples 13 to 19 biaxially stretched laminate film and laminate production
A biaxially stretched laminate film and a laminate were produced in the same manner as in example 12, except that the resin composition (a-3 to a-9) was changed to the resin layer (a).
Example 20
A biaxially stretched film was produced in the same manner as in example 12, except that the resin composition (a-10) was changed to the resin layer (a). Next, the biaxially stretched laminated film and the electrolytic copper foil (thickness: 18 μm) thus obtained were laminated so that the resin layer (a) of the biaxially stretched laminated film and the electrolytic copper foil were joined, and the laminate of the copper foil and the film was produced by pressing at 260 ℃ under a pressure of 5MPa for 15 seconds by a press machine.
Example 21
A biaxially stretched film and a laminate were produced in the same manner as in example 12, except that the resin composition (B-2) was changed to the resin layer (B). The average porosity of the resin layer (B) was 55%.
Comparative example 4 production of biaxially stretched laminate film and laminate for comparison
A biaxially stretched laminate film and a laminate were produced in the same manner as in example 11, except that the resin composition (cA-1) was used in the resin layer (a).
Comparative example 5 production of biaxially stretched laminate film for comparison and laminate
A biaxially stretched laminate film and a laminate were produced in the same manner as in example 11, except that the resin composition (cA-2) was used in the resin layer (a).
Comparative example 6 production of biaxially stretched laminate film and laminate
A biaxially stretched laminate film and a laminate were produced in the same manner as in example 11, except that PPS resin a-1 was used in the resin layer (a) instead of the resin composition (a-1).
Comparative example 7 production of biaxially stretched laminate film and laminate for comparison
The biaxially stretched laminated film obtained in comparative example 6 was subjected to plasma treatment so that the treated surface side of the film was superposed on an electrolytic copper foil (thickness: 18 μm), and was pressed at 270℃under a pressure of 5MPa for 15 seconds by a press machine, to prepare a laminate of copper foil and film.
[ evaluation ]
1. Dielectric constant and dielectric loss tangent
Measurement of dielectric constant and dielectric loss tangent based on JIS C2565: 1992. Specifically, a short bar having a width of 2mm×a length of 150mm was produced from the insulating film. Then, the prepared pellets were allowed to stand at 23℃for 24 hours in an atmosphere of 50% Rh, and then dielectric constant and dielectric loss tangent at a frequency of 1GHz were measured by a cavity resonance method using ADMS010c series (manufactured by AET, co., ltd.). The following table shows the "dielectric constant" and "dielectric loss tangent".
2. Adhesion to
Regarding the adhesiveness, based on JIS K6854: the peel strength of the copper foil and biaxially stretched laminate film was measured by the test method specified in 1999, and evaluated according to the following criteria. The following table shows "adhesiveness".
And (3) the following materials: 8N/cm or more
O: 7N/cm or more and less than 8N/cm
Delta: 6N/cm or more and less than 7N/cm
X: less than 6N/cm
The results are shown in tables 1 to 3.
3. Uniformity of stretching
A stamp in a square shape (square size 10×10 (mm)) was embossed on an unstretched sheet in a non-oriented state, and the square shape of a biaxially stretched film obtained when stretched at a predetermined magnification was visually observed and evaluated according to the following criteria. The results obtained are shown as "stretch uniformity" in the following table.
And (3) the following materials: square 9 or more of the square of the whole film
O: square with 8 or more and less than 9 of square of the whole surface of the film
Delta: square with square with 5 or more and less than 8
X: less than 5 squares of the film across the face
TABLE 1
TABLE 2
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TABLE 3
TABLE 4
TABLE 5
TABLE 6
The biaxially stretched films used as the resin layers (A-1) to (A-10) obtained in examples 1 to 10 were low in dielectric constant and low in dielectric loss tangent, and showed excellent results in dielectric characteristics. Further, the biaxially stretched laminated films and laminates obtained in examples 11 to 21 containing the resin layer showed excellent adhesion to the metal layer.
In contrast, the biaxially stretched films, biaxially stretched laminated films, and laminated bodies obtained in comparative examples 1 and 4, comparative examples 2 and 5, and comparative examples 3, 6, and 7, respectively, were poor in dielectric characteristics and/or adhesiveness.
As is clear from the results, by using a biaxially stretched laminated film in which a resin layer comprising a biaxially stretched film of a resin composition having a specific morphology and obtained by blending a polyphenylene ether resin, a styrene- (meth) acrylic copolymer and a polyarylene sulfide resin as raw materials is disposed, it is possible to maintain the excellent properties (heat resistance, flame retardancy, chemical resistance, moist heat resistance) inherent in the polyarylene sulfide resin, and to exhibit a low dielectric constant and a low dielectric loss tangent. It is also clear that the metal-resin composite material can be directly thermally bonded to a metal-resin molded body at a temperature not higher than the melting point of the polyarylene sulfide resin.

Claims (16)

1. A biaxially stretched laminated film having a structure in which at least 2 resin layers are directly laminated,
in the biaxially stretched laminate film described above,
at least 1 layer is a resin layer (A) composed of a biaxially stretched film of a resin composition (A) which contains at least a polyarylene sulfide resin, a polyphenylene ether resin, and a styrene- (meth) acrylic copolymer as raw materials and has a continuous phase and a dispersed phase,
the continuous phase comprises a polyarylene sulfide resin,
the dispersed phase comprises a polyphenylene ether resin,
the average dispersion diameter of the dispersed phase in the resin layer (A) is in the range of 5 μm or less,
the styrene- (meth) acrylic acid copolymer is a copolymer obtained by copolymerizing a styrene monomer and a (meth) acrylic acid monomer, and the (meth) acrylic acid monomer is (meth) acrylic acid.
2. The biaxially stretched laminated film according to claim 1, wherein the polyarylene sulfide resin has an acid group.
3. The biaxially stretched laminated film according to claim 1, wherein the ratio of the blending amount of the polyphenylene ether resin is in the range of 3 to 40 parts by mass based on 100 parts by mass of the total of the polyarylene sulfide resin, the polyphenylene ether resin and the styrene- (meth) acrylic acid copolymer.
4. The biaxially stretched laminated film according to claim 1, wherein the ratio of the blending amount of the styrene- (meth) acrylic copolymer is in the range of 0.5 to 10 parts by mass based on 100 parts by mass of the total of the polyarylene sulfide resin, the polyphenylene ether resin and the styrene- (meth) acrylic copolymer.
5. The biaxially stretched laminated film according to claim 1, wherein the (meth) acrylic acid content of the styrene- (meth) acrylic acid copolymer is in the range of 1 to 30 mass% relative to the total mass of the styrene- (meth) acrylic acid copolymer.
6. The biaxially stretched laminated film according to claim 1, wherein the resin composition (a) further comprises an elastomer.
7. The biaxially stretched laminated film according to claim 6, wherein the ratio of the amount of the elastomer to be blended is in the range of 3 to 15 parts by mass based on 100 parts by mass of the total of the polyarylene sulfide resin, the polyphenylene ether resin, the styrene- (meth) acrylic copolymer and the elastomer.
8. The biaxially stretched laminated film according to claim 6, wherein the elastomer comprises at least 1 selected from the group consisting of copolymers of an α -olefin and a glycidyl ester of an α, β -unsaturated carboxylic acid, and copolymers of an α -olefin, a glycidyl ester of an α, β -unsaturated carboxylic acid and a (meth) acrylate.
9. The biaxially stretched laminated film according to claim 8, wherein the α -olefin content of the elastomer is in the range of 50 to 95 mass% relative to the total mass of the elastomer.
10. The biaxially stretched laminated film according to claim 1, which has a structure in which at least the resin layer (a) and the resin layer (B) are directly laminated, the resin layer (B) being a biaxially stretched film of a resin composition containing a polyarylene sulfide resin.
11. A laminate comprising the biaxially stretched laminate film of any one of claims 1 to 10, wherein the resin layer (A) is bonded to at least 1 selected from the group consisting of a metal layer and a resin molded body.
12. A flexible printed wiring board comprising the laminate according to claim 11.
13. A flexible flat cable comprising the laminate of claim 11.
14. An engine insulator comprising the laminate according to claim 11.
15. A method for producing a biaxially stretched laminated film, characterized by comprising a step of directly laminating at least 2 resin layers,
comprising a step of biaxially stretching an unstretched laminate sheet having a structure in which at least 2 resin layers are directly laminated,
In the biaxially stretched laminate film described above,
at least 1 layer is a resin layer (A) comprising a biaxially stretched film obtained by biaxially stretching a resin composition (A) which comprises at least a polyarylene sulfide resin, a polyphenylene ether resin and a styrene- (meth) acrylic acid copolymer as raw materials and has a continuous phase and a disperse phase,
the continuous phase comprises a polyarylene sulfide resin,
the dispersed phase comprises a polyphenylene ether resin,
the average dispersion diameter of the dispersed phase in the resin layer (A) is 5 μm or less,
the styrene- (meth) acrylic acid copolymer is a copolymer obtained by copolymerizing a styrene monomer and a (meth) acrylic acid monomer, and the (meth) acrylic acid monomer is (meth) acrylic acid.
16. A method for producing a laminate, comprising bonding the resin layer (A) of the biaxially stretched laminate film according to any one of claims 1 to 10 to at least 1 selected from the group consisting of a metal layer and a resin molded body.
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