CN114514117A - Biaxially stretched laminate film, laminate, and method for producing same - Google Patents

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

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Publication number
CN114514117A
CN114514117A CN202080071395.8A CN202080071395A CN114514117A CN 114514117 A CN114514117 A CN 114514117A CN 202080071395 A CN202080071395 A CN 202080071395A CN 114514117 A CN114514117 A CN 114514117A
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resin
biaxially stretched
meth
film
mass
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CN114514117B (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 Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention provides a film which can well and directly thermally bond a metal layer and a polyarylene sulfide resin at a temperature below the melting point of the polyarylene sulfide resin and can realize low dielectric constant and low dielectric loss tangent, a laminated body using the film, and a manufacturing method thereof. A biaxially stretched laminate film in which a resin layer comprising a film obtained by biaxially stretching a resin composition (A) produced by using a polyphenylene ether resin and a styrene- (meth) acrylic acid copolymer as raw materials in a polyarylene sulfide resin and having a specific morphology is disposed as a layer directly bonded to a metal or a resin molded body, a laminate obtained by bonding the biaxially stretched laminate film to a metal layer and/or a resin molded body, and methods for producing the same.

Description

Biaxially stretched laminate film, laminate, and method for producing same
Technical Field
The present invention relates to a biaxially stretched laminate film, a laminate, and methods for producing the same, and more particularly, to a polyarylene sulfide biaxially stretched laminate film which is excellent in thermal adhesion to a metal and/or resin molded body and has low dielectric characteristics, a laminate using the same, and methods for producing the same.
Background
In recent years, in the field of flexible printed circuit boards (FPCs) and Flexible Flat Cables (FFCs), with the development of cloud terminals, Internet of Things (IoT), etc., the advancement of automotive autonomous driving technology, and the development of electric vehicles and hybrid vehicles, cables and antennas capable of processing a large amount of data and transmitting data at high speed without loss are required. However, in the past, Polyimide (PI) films have been used as FPC substrates, and polyester films (PET films and the like) have been used as FCC substrates, and thus it has not been said that they have dielectric characteristics capable of coping with next-generation high-speed transmission. 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 engine oil impregnation. However, polyester films have a problem of poor heat resistance.
On the other hand, films using polyarylene sulfide resins represented by polyphenylene sulfide resin (PPS) are excellent in heat resistance, flame retardancy, chemical resistance, and electrical insulation, and thus are used as insulating materials for condensers and motors, and heat-resistant tapes. Polyarylene sulfide resins have excellent dielectric properties compared to PI and PET, and therefore, are used in the fields of flexible printed circuit boards (FPC), Flexible Flat Cables (FFC), and the like. However, polyarylene sulfide films generally have problems of low adhesiveness and adhesion to metals and other resins, and poor reactivity with adhesives. As a method for improving this problem, for example, patent document 1 describes a laminate in which a resin layer made OF a resin composition containing polyphenylene sulfide as a main component is laminated on at least one surface OF a metal plate without using an adhesive, and the degree OF orientation OF the resin layer is in the range OF 0.65 to 0.9.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent 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 a 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 on the metal plate. Further, since thermocompression bonding is performed substantially at the melting point or more of the polyphenylene sulfide resin, it is difficult to obtain a laminate having a good appearance.
Accordingly, an object of the present invention is 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 realize a low dielectric constant and a low dielectric loss tangent, a laminate using the film, and methods 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-mentioned 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 acid copolymer as raw materials in a polyarylene sulfide resin and has a specific morphology (morpholinoy) is disposed as a layer directly bonded to a metal or a resin molded body, and have completed the present invention.
That is, the present invention relates to the following (1) to (16).
(1) The present invention relates to a biaxially stretched laminate film characterized by having a structure in which at least 2 resin layers are directly laminated,
in the above-mentioned biaxially stretched laminated film,
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 acid 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 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 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 item (1), wherein the content of the polyphenylene ether resin is in the range of 3 to 40 parts by mass relative to 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 item (1), wherein the ratio of the amount of the styrene- (meth) acrylic acid copolymer is in the range of 0.5 to 10 parts by mass relative to 100 parts by mass of the total of the polyarylene sulfide resin, the polyphenylene ether resin and the styrene- (meth) acrylic acid copolymer.
(6) The present invention relates to the biaxially stretched laminated film according to the above (1), wherein the styrene- (meth) acrylic acid copolymer has a (meth) acrylic acid content in a range of 1 to 30 mass% with respect to the total mass of the styrene- (meth) acrylic acid copolymer.
(7) The present invention relates to the biaxially stretched laminate film according to the above (1), wherein the resin composition (a) further contains an elastomer.
(8) The present invention relates to the biaxially stretched laminated film according to the above (1), wherein the ratio of the amount of the elastomer blended is in the range of 3 to 15 parts by mass relative to 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 laminate film according to the above (1), wherein the elastomer contains at least 1 selected from the group consisting of a copolymer of an α -olefin and a glycidyl ester of an α, β -unsaturated carboxylic acid, and a copolymer of an α -olefin, a glycidyl ester of an α, β -unsaturated carboxylic acid, and a (meth) acrylate.
(10) The present invention relates to the biaxially stretched laminated film according to the item (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 laminate 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, wherein 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 a resin layer (a) of the biaxially stretched laminate film according to any one of (1) to (11) is joined to at least 1 selected from the group consisting of a metal layer and a resin molded body.
(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 including the laminate according to (12) above.
(15) The present invention relates to an insulator for an engine, which comprises the laminate according to (12) above.
(16) The present invention relates to a method for producing a biaxially stretched laminated film, characterized in that it is a method for producing a biaxially stretched laminated film having a structure in which at least 2 resin layers are directly laminated,
which comprises a step of biaxially stretching an unstretched laminate sheet having a structure in which at least 2 resin layers are directly laminated,
in the above-mentioned biaxially stretched laminated film,
at least 1 layer of a resin layer (A) comprising a biaxially stretched film obtained by biaxially stretching a resin composition (A) which comprises a continuous phase and a dispersed phase and is produced from at least a polyarylene sulfide resin, a polyphenylene ether resin and a styrene- (meth) acrylic acid copolymer,
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.
(17) The present invention relates to a method for producing a laminate by bonding a resin layer (a) of the biaxially stretched laminate film described in any one of (1) to (11) above 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, 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 further reduce the dielectric constant and the dielectric loss tangent, a laminate using the film, and methods for producing the film and the laminate can be provided.
Detailed Description
Hereinafter, the biaxially stretched laminate film and the laminate of the present invention will be described in detail 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) composed of a biaxially stretched film of a resin composition (A) having a continuous phase and a dispersed phase, and the resin composition (A) contains 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 raw materials,
the continuous phase comprises a polyarylene sulfide resin,
the dispersed phase comprises 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 a main component and is mainly contained in the continuous phase.
The PAS resin used in the present invention is a polymer containing, as a repeating unit, a structure in which an aromatic ring is bonded to a sulfur atom (specifically, a structure represented by the following formula (1)).
[ solution 1]
Figure BDA0003590236640000051
In the above formula, R1Each 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 the formula (1)1Preferably both are hydrogen atoms. With such a configuration, the mechanical strength of the PAS resin can be further improved. As R1Examples of the structure represented by formula (1) in which all hydrogen atoms are present include a structure represented by 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 formula (3) (i.e., a structure in which a sulfur atom is bonded to an aromatic ring at the meta-position). The PAS resin may be a copolymer of the formula (2) and the formula (3), and 80 mol% or more of the copolymerized PAS resin is composed of the formula (2), and is preferably in the range of 85 mol% or more and 95 mol% or less, and preferably 92 mol% or less. The above range is preferable because the melting point can be lowered while maintaining the film. The copolymerization mode of the copolymerization component is not particularly limited, and a random copolymer is preferred.
[ solution 2]
Figure BDA0003590236640000052
Among them, the structure represented by formula (1) is preferably the structure represented by formula (2). The PAS resin having the structure represented by formula (2) can further improve heat resistance and crystallinity.
In addition, the PAS resin may include, as repeating units, not only the structures represented by the above formula (1), but also the structures represented by the following formulae (4) to (7).
[ solution 3]
Figure BDA0003590236640000061
The structure represented by the formulae (4) to (7) is preferably contained in an amount of 30 mol% or less, more preferably 10 mol% or less, based on the total repeating units constituting the PAS resin. With such a configuration, the heat resistance and mechanical strength of the PAS resin can be further improved.
The bonding pattern of the structures represented by the formulae (4) to (7) may be random or block.
The PAS resin may contain, as a repeating unit, a 3-functional structure represented by the following formula (8), a naphthalene sulfide structure, or the like in its molecular structure.
[ solution 4]
Figure BDA0003590236640000062
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, and more preferably substantially not contained in all the repeating units constituting the PAS resin. With such a configuration, the content of chlorine atoms in the PAS resin can be reduced.
Further, the characteristics of the PAS resin are not particularly limited as long as the effects of the present invention are not impaired, and the melt viscosity (V6) at 300 ℃ is preferably 100Pa · s or more, more preferably 120Pa · s or more and preferably 2000Pa · s or less, more preferably 1600Pa · s or less. In this range, the balance between the fluidity and the mechanical strength is favorable, and therefore, the range is preferable.
Further, the PAS resin preferably has a peak in a molecular weight range of 25,000 to 40,000 in a measurement using Gel Permeation Chromatography (GPC). Further, the above molecular weight range is preferable 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 and the ratio (Mw/Mn) range are within a range of 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 in the production of a film, and the PAS resin is easily applied to 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 values measured by Gel Permeation Chromatography (GPC). The measurement conditions of GPC are as follows.
[ measurement conditions for gel permeation chromatography ]
The device comprises the following steps: ultra-high temperature Polymer molecular weight distribution measuring device (SSC-7000 made by Senshu science Co., Ltd.)
Column: UT-805L (made by SHOWA AND ELECTRIC WORKING CORPORATION)
Column temperature: 210 deg.C
Solvent: 1-chloronaphthalene
The determination method comprises the following steps: the molecular weight distribution and peak molecular weight were determined using 6 monodisperse polystyrenes for calibration using a UV detector (360 nm).
The production method of the PAS resin is not particularly limited, and examples thereof include:
(preparation method 1) a method of polymerizing by adding a dihalo-aromatic compound and, if necessary, a polyhaloaromatic compound or other copolymerization components in the presence of sulfur and sodium carbonate;
(preparation method 2) a method of adding a dihalo-aromatic compound, if necessary, a polyhaloaromatic compound or other copolymerization components to a polar solvent in the presence of a thioether reagent or the like to conduct polymerization; (preparation method 3) a method of adding p-chlorothiophenol and, if necessary, other copolymerizable components to perform self-condensation. Among these production methods, the method of the above (production method 2) is generally used and 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 degree of polymerization.
Among the above-mentioned methods (production method 2), the following methods (production method 2-1) and (production method 2-2) are particularly preferable.
In the method (production method 2-1), a water-containing thioether agent is introduced into a heated mixture containing an organic polar solvent and a dihalo-aromatic compound at a rate at which water can be removed from the reaction mixture, the dihalo-aromatic compound and the thioether agent are added to the organic polar solvent, and a polyhaloaromatic compound is added as needed, and the water content 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 during the reaction, thereby producing a PAS resin (A) (see Japanese patent laid-open publication (Kokai) No. H07-228699).
In the method of (production method 2-2), a dihalo-aromatic compound and, if necessary, 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 reacting an alkali metal hydrosulfide with an organic acid alkali metal salt, the amount of the organic acid alkali metal salt is controlled to be in the range of 0.01 to 0.9 mol relative to 1 mol of the sulfur source, and the water content 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, thereby producing a PAS resin (see WO2010/058713 pamphlet).
Specific examples of the dihalo-aromatic compound include p-dihalobenzene, m-dihalobenzene, o-dihalobenzene, 2, 5-dihalotoluene, 1, 4-dihalonaphthalene, 1-methoxy-2, 5-dihalobenzene, 4 '-dihalobiphenyl, 3, 5-dihalobenzoic acid, 2, 4-dihalobenzoic acid, 2, 5-dihalonitrobenzene, 2, 4-dihaloanisole, p' -dihalodiphenyl ether, 4 '-dihalobenzophenone, 4' -dihalodiphenyl sulfone, 4 '-dihalodiphenyl sulfoxide, 4' -dihalodiphenyl sulfide, and compounds having an alkyl group having 1 to 18 carbon atoms in the aromatic ring of each of the above compounds.
Further, examples of the polyhalogenated aromatic compound include 1,2, 3-trihalobenzene, 1,2, 4-trihalobenzene, 1,3, 5-trihalobenzene, 1,2,3, 5-tetrahalobenzene, 1,2,4, 5-tetrahalobenzene, 1,4, 6-trihalonaphthalene and the like.
The halogen atom contained in the above compound is preferably a chlorine atom or a bromine atom.
As a method for post-treating a reaction mixture containing a PAS resin obtained in the polymerization step, a known and conventional method can be used. The post-treatment method is not particularly limited, and examples thereof include the following methods (post-treatment 1) to (post-treatment 5).
In the method of the post-treatment 1, after the polymerization reaction is completed, the reaction mixture is distilled off under reduced pressure or atmospheric pressure as it is or after adding an acid or an alkali, and then the solid matter from which the solvent has been distilled off is washed 1 or 2 times or more with a solvent such as water, a reaction solvent (or an organic solvent having a solubility equivalent to that of a low-molecular polymer), acetone, methyl ethyl ketone, or an alcohol, and further neutralized, washed with water, filtered, and dried.
In the method (post-treatment 2), after the polymerization reaction is completed, a solvent (a solvent which is soluble in the polymerization solvent used and is a poor solvent for at least the PAS resin) such as acetone, methyl ethyl ketone, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons, aliphatic hydrocarbons or the like is added as a precipitant to the reaction mixture, and the solid product such as the PAS resin, inorganic salt or the like is precipitated, filtered, washed and dried.
In the method of the post-treatment 3, after the polymerization reaction is completed, a reaction solvent (or an organic solvent having the same solubility as the low-molecular polymer) is added to the reaction mixture, stirred, filtered to remove the low-molecular polymer, washed with a solvent such as water, acetone, methyl ethyl ketone, or alcohols 1 or 2 times or more, and then neutralized, washed with water, filtered, and dried.
In the method of the post-treatment 4, after the completion of the polymerization reaction, water is added to the reaction mixture to wash and filter the reaction mixture, and if necessary, an acid is added to wash the reaction mixture with water to perform an acid treatment, and the reaction mixture is dried.
In the method of the post-treatment 5, after the polymerization reaction is completed, the reaction mixture is filtered, washed with the reaction solvent as needed 1 or 2 times or more, and further washed with water, filtered and dried.
Examples of the acid usable in the method of the above-mentioned (post-treatment 4) include saturated fatty acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid and monochloroacetic acid, unsaturated fatty acids such as acrylic acid, crotonic acid and oleic acid, aromatic carboxylic acids such as benzoic acid, phthalic acid and 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; hydrochloric acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, phosphoric acid, and other inorganic acids.
Examples of the hydrogen salt include sodium hydrosulfide, disodium hydrogenphosphate, and sodium hydrogencarbonate. However, in actual use, an organic acid which causes little corrosion to metal members is preferable.
In the above-mentioned methods (post-treatment 1) to (post-treatment 5), the drying of the PAS resin may be performed in a vacuum, or may be performed in an inert gas atmosphere such as air or nitrogen.
In particular, the PAS resin after-treated by the above-mentioned method (post-treatment 4) has an effect of improving the dispersibility of the dispersed phase because the amount of acid groups bonded to the molecular terminals thereof is increased. 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, relative to 100 parts by mass of the total of the PAS resin, the PPE-based resin, and the styrene- (meth) acrylic acid copolymer. The above range is preferable because the heat resistance and chemical resistance of the film can be further improved.
The resin composition (a) used in the present invention is obtained by blending a polyphenylene ether resin as an essential raw material.
The PPE based resin is contained in the dispersed phase of the resin composition (A) in principle. The PPE resin in the dispersed phase is a component having a function of reducing the dielectric constant and the dielectric loss tangent of the obtained biaxially stretched laminated film.
The PPE-based resin means a polymer having an ether bond directly bonded to an aromatic ring in the main chain, and is, for example, a polymer having a structure represented by the following formula (9) in a repeating unit.
[ solution 5]
Figure BDA0003590236640000101
In the above formula, R2Each 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 halohydrocarbyloxy group having at least 2 carbon atoms with a halogen atom and an oxygen atom interposed therebetween, and each m independently represents 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 poly (2, 6-dichloro-1, 4-phenylene ether), copolymers of 2, 6-dimethylphenol with other phenols (e.g., 2,3, 6-trimethylphenol and 2-methyl-6-butylphenol), 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride, 2-bis [4- (2, 3-dicarboxyphenoxy) phenyl ] propane dianhydride, poly (phenylene ether) and poly (phenylene ether), Polycondensates of aromatic bis (ether anhydride) such as 4- (2, 3-dicarboxyphenoxy) -4 '- (3, 4-dicarboxyphenoxy) diphenyl-2, 2-propane dianhydride with m-phenylenediamine or p-phenylenediamine, and polycondensates of dihydroxydiphenyl sulfone, 2-bis (4-hydroxyphenyl) propane, 4' -dihydroxybiphenyl, or alkali metal salts thereof with dichlorodiphenyl 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, and more preferably poly (2, 6-dimethyl-1, 4-phenylene ether).
The number average molecular weight of the PPE resin is preferably 1,000 or more, more preferably 1,500 to 50,000, and still more preferably 1,500 to 30,000.
The compounding amount of the PPE-based resin in the resin composition (a) is preferably 3 parts by mass or more, more preferably 5 parts by mass or more to preferably 40 parts by mass or less, and still more preferably 35 parts by mass or less, per 100 parts by mass of the total of the PAS resin, the PPE-based resin, and the styrene- (meth) acrylic acid copolymer. When the amount is within the above range, the biaxially stretched laminate film has more excellent dielectric characteristics (a lower dielectric constant and a lower dielectric loss tangent) and an effect of improving direct thermal adhesion to a metal or a resin molded product at a temperature not higher 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. In addition, "(meth) acrylic acid" means "acrylic acid" and/or "methacrylic acid".
The styrene- (meth) acrylic acid copolymer is mostly contained in the dispersed phase of the resin composition. The styrene- (meth) acrylic acid copolymer in the dispersed 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 styrenic monomer and a (meth) acrylic acid monomer.
The styrene monomer is not particularly limited, and styrene and its derivatives are exemplified. 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, iodostyrene, etc.; nitrostyrene; acetyl styrene; methoxystyrene, and the like. These styrene monomers may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The (meth) acrylic monomer may be an alkyl (meth) acrylate having a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, in addition to acrylic acid and methacrylic acid. In this case, the substituent is not particularly limited, and examples thereof include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, a hydroxyl group and the like. The number of substituents may be only 1, or may be 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, hydroxypropyl (meth) acrylate, and the like. Among them, (meth) acrylic acid is preferable from the viewpoint of compatibility and reactivity. These (meth) acrylic monomers may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The content of the (meth) acrylic acid-based repeating unit contained in the styrene- (meth) acrylic acid copolymer is preferably in the range of 1 mass% or more and preferably 30 mass% or less, more preferably 20 mass% or less, and still more preferably 18 mass% or less with respect to the total mass of the styrene- (meth) acrylic acid copolymer, from the viewpoint of obtaining good compatibility, further improving the stretching uniformity, folding strength, and the like of the biaxially stretched laminated film.
As the polymerization reaction of the styrene- (meth) acrylic acid copolymer, a general 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 system is particularly preferably continuous bulk polymerization in view of production efficiency. For example, a styrene- (meth) acrylic acid copolymer having excellent characteristics can be obtained by performing continuous bulk polymerization using an apparatus in which 1 or more stirring reactors and a tubular reactor in which a plurality of mixing elements having no movable parts are fixed are assembled.
Although thermal polymerization can be carried out without using a polymerization initiator, various radical polymerization initiators are preferably used. Further, as polymerization aids such as a suspending agent and an emulsifier necessary for the polymerization reaction, compounds used in the production of general polystyrene can be used.
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 in 1 kind, or may be used in combination in 2 or more kinds.
Examples of the radical polymerization initiator include peroxy ketals such as 1, 1-bis (t-butylperoxy) cyclohexane, 2-bis (t-butylperoxy) butane and 2, 2-bis (4, 4-dibutylperoxycyclohexyl) 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 dicumyl peroxide; peroxy esters such as t-butyl peroxybenzoate, di-t-butyl peroxyisophthalate and t-butyl peroxyisopropyl monocarbonate; 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 in 1 kind, or may be used in combination in 2 or more kinds.
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, and a polyfunctional chain transfer agent having a plurality of chain transfer groups may also be used. Examples of the monofunctional chain transfer agent include alkyl mercaptans and thioglycolates. Examples of the polyfunctional chain transfer agent include compounds obtained by esterifying hydroxyl groups in polyhydric alcohols such as ethylene glycol, neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, and sorbitol with thioglycolic acid and 3-mercaptopropionic acid. These chain transfer agents may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
In addition, in order to suppress gelation of the obtained 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 proportion of the styrene- (meth) acrylic acid copolymer in the resin composition (a) is preferably in the 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, and still more preferably 5 parts by mass or less, per 100 parts by mass of the total of the PAS resin, the PPE resin, and the styrene- (meth) acrylic acid copolymer. When the amount is within the above range, good compatibility can be obtained, and the stretching uniformity, the folding strength, and the like of the biaxially stretched laminate film can be further improved.
The resin composition (a) used in the present invention is obtained by blending an elastomer as an optional raw material, if necessary. 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 for the PAS resin and the PPE resin, and has a function of improving mechanical strength (tear strength, etc.) by finely dispersing the dispersed phase. Further, by using a styrene- (meth) acrylic acid copolymer in combination, the adhesion at the interface between the PAS resin and the PPE resin is further improved by the elastomer, and the mechanical strength (folding strength, tear strength, etc.) is further improved.
The elastomer more preferably has a functional group capable of reacting with at least one of the PAS resin and the PPE-based resin (hereinafter, also referred to as "functional group-containing elastomer"), 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 elastomer having a functional group may have is preferably at least 1 selected from the group consisting of an epoxy group and an acid anhydride group, and is more preferably an epoxy group. These functional groups are reactive with the functional groups at the molecular terminals of the PAS resin and the PPE resin.
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 elastomers include copolymers containing repeating units based on α -olefins and repeating units based on vinyl polymerizable compounds having the above functional groups; and copolymers containing repeating units derived from an α -olefin, repeating units derived from a vinyl polymerizable compound having the above functional group, and repeating units derived from an acrylate ester.
The alpha-olefin includes alpha-olefins 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 dicarboxylic acids such as acrylic acid, methacrylic acid, acrylic acid esters, and methacrylic acid esters thereof, maleic acid, fumaric acid, itaconic acid, other unsaturated dicarboxylic acids having 4 to 10 carbon atoms, monoesters or diesters thereof, anhydrides thereof, and the like, esters thereof, anhydrides thereof, and α, β -unsaturated glycidyl esters.
The α, β -unsaturated glycidyl ester is not particularly limited, and examples thereof include a compound represented by the following formula (10).
[ solution 6]
Figure BDA0003590236640000141
In the above formula, R3An alkenyl group having 1 to 6 carbon atoms.
Examples of the alkenyl group having 1 to 6 carbon atoms include an ethenyl group, a 1-propenyl group, a 2-propenyl group, a 1-methylethenyl group, a 1-butenyl group, a 2-butenyl group, a 1-methyl-1-propenyl group, a 1-methyl-2-propenyl group, a 2-methyl-1-propenyl group, a 2-methyl-2-propenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, a 4 pentenyl group, a 1-methyl-1-pentenyl group, a 1-methyl-3-pentenyl group, a 1, 1-dimethyl-1-butenyl group, a 1-hexenyl group, and a 3-hexenyl group.
R4Each 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 a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 2, 2-dimethylpropyl group, a hexyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 4-methylpentyl group, a 2, 2-dimethylbutyl group, a 2, 3-dimethylbutyl group, a 2, 4-dimethylbutyl group, a 3, 3-dimethylbutyl group, and a 2-ethylbutyl group.
Specific examples of the α, β -unsaturated glycidyl ester include glycidyl acrylate, glycidyl methacrylate and the like, and glycidyl methacrylate is preferable.
The content of the α -olefin in the elastomer is preferably 50% by mass or more and preferably 95% by mass or less, more preferably 80% by mass or less, based on the total mass of the elastomer. If the ratio of the repeating unit based on the α -olefin is within the above range, the biaxially stretched laminate film can be improved in stretching uniformity, folding strength, and the like.
The proportion of the repeating unit based on the vinyl polymerizable compound having a functional group in the elastomer is preferably 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. When the ratio of the repeating unit based on the vinyl polymerizable compound having a functional group is within the above range, not only the intended improvement effect but also good extrusion stability can be obtained.
When the elastomer is blended, the blending amount of the elastomer in the resin composition (a) is preferably 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, per 100 parts by mass of the total of the PAS resin, the PPE resin, the styrene- (meth) acrylic copolymer, and the elastomer. When the amount is within the above range, the dielectric properties (reduction in dielectric constant and reduction in dielectric loss tangent), the folding strength, and the like of the biaxially stretched laminate film can be further improved.
The resin composition (a) used in the present invention is prepared by adding a silane coupling agent as an optional raw material as necessary. The silane coupling agent can improve the compatibility (interaction) between the PAS resin and other components (PPE resin, styrene-methacrylic acid copolymer, and elastomer which may be contained if necessary). Further, by using the silane coupling agent, the 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 strongly 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 such a 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 epoxy group-containing alkoxysilane compounds such as γ -glycidoxypropyltrimethoxysilane, γ -glycidoxypropyltriethoxysilane and β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, isocyanate group-containing alkoxysilane compounds such as γ -isocyanatopropyltrimethoxysilane, γ -isocyanatopropyltriethoxysilane, γ -isocyanatopropylmethyldimethoxysilane, γ -isocyanatopropylmethyldiethoxysilane, γ -isocyanatopropylethyldimethoxysilane, γ -isocyanatopropylethyldiethoxysilane and γ -isocyanatopropyltrichlorosilane, γ - (2-aminoethyl) aminopropylmethyldimethoxysilane, gamma-isocyanatopropyltriethoxysilane, gamma-isocyanatopropyltrimethoxysilane and the like, Amino group-containing alkoxysilane compounds such as γ - (2-aminoethyl) aminopropyltrimethoxysilane and γ -aminopropyltrimethoxysilane, and hydroxyl group-containing alkoxysilane compounds such as γ -hydroxypropyltrimethoxysilane and γ -hydroxypropyltriethoxysilane.
When a silane coupling agent is blended, the amount of the silane coupling agent blended in the resin composition (a) is preferably in the range of 0.01 parts by mass or more, more preferably 0.05 parts by mass or more to 5 parts by mass or less, and still more preferably 2.5 parts by mass or less, per 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, the 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 a plasticizer, a weather resistant agent, an antioxidant, a heat stabilizer, an ultraviolet stabilizer, a lubricant, an antistatic agent, a colorant, and a conductive agent, as necessary, in a range not to impair 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 essential raw materials and, if necessary, optional raw materials and additives are uniformly dry-mixed by a tumbler mixer, a henschel mixer, or the like, and then fed into a twin-screw extruder, heated to a temperature at which the resin species is melted or higher, and melt-kneaded.
The melt kneading is preferably carried out under the condition that the ratio of the discharge amount (kg/hr) of the kneaded material to the number of screw revolutions (rpm) (discharge amount/screw revolutions) is 0.02 to 0.2(kg/hr · rpm).
More specifically, it is preferable to use a method in which each raw material component is charged into a twin-screw extruder and melt-kneaded under a temperature condition of about 300 ℃ as a set temperature and about 330 ℃ as 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 a rotation speed of 250 rpm. Particularly, from the viewpoint of improving the dispersibility of each component, the discharge amount of the kneaded material is preferably 20 to 35kg/hr at a rotation speed of 250 rpm. Therefore, the ratio of the discharge amount (kg/hr) of the kneaded material to the number of screw revolutions (rpm) (discharge amount/number of screw revolutions) is more preferably 0.08 to 0.14(kg/hr rpm).
The biaxially stretched laminate 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) comprising a biaxially stretched film of the resin composition (a). The method for producing a biaxially stretched laminate film of the present invention includes a step of biaxially stretching an unstretched laminate sheet having a structure in which at least 2 resin layers are directly laminated.
In one embodiment of such a biaxially stretched laminated film, the resin layer (a) has a PAS resin as a matrix (continuous phase), and particles (dispersed phase) containing a PPE 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 resin layer (a). Since the substrate (continuous phase) is made of the PAS resin, the biaxially stretched laminate film can be obtained which maintains the heat resistance, flame retardancy, chemical resistance, moist heat resistance and other properties inherent in the PAS resin.
The styrene-methacrylic acid copolymer is present in the PPE resin particles or present as particles (dispersed phase) different from the PPE resin particles (dispersed phase).
When 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 present inventors have also considered that the mechanical strength (such as folding strength) of the biaxially stretched laminated film is further improved by the fine dispersion of the particles in the matrix because the elastomer also functions as a compatibilizer for the PAS resin and the PPE resin. Further, the present inventors also considered that the use of a silane coupling agent in combination further improves the adhesion at the interface between the elastomer matrix and the particles, and further improves the mechanical strength (such as folding strength) of the biaxially stretched laminated film.
In the resin layer (a), the average particle diameter (average dispersion diameter) of the particles (dispersed phase) dispersed in the matrix (continuous phase) is preferably 5 μm or less, more preferably 3 μm or less, and the lower limit is not particularly limited, but is more preferably 0.5 μm or more. If the average particle diameter of the particles is in the above range, a uniform and homogeneous biaxially laminated stretched film can be obtained. In the present specification, the "average particle size of particles" is measured as follows.
First, the biaxially stretched film of the resin layer (a) was cut by a microtome method in (I) a direction parallel to the longitudinal direction and perpendicular to the film surface, and (II) a direction parallel to the width direction and perpendicular to the film surface. Next, Scanning Electron Microscope (SEM) photographs were taken at 2000 × magnification for each of the cut surfaces (I) and (II) of the cut film after cutting, arbitrary 50 particles in the obtained SEM photographs were selected, 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 the average particle diameter.
Further, if the cut film is stained with ruthenic acid and subjected to STEM-EDS analysis, the composition of the matrix and particles constituting the film can be analyzed.
The structure of the biaxially stretched laminate 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, a laminate film in which the resin layers (a) are directly laminated, or a laminate film in which the resin layer (a) and a resin layer other than the resin layer (a) are directly laminated may be used. With this configuration, the PAS resin can be bonded to the metal or resin molded body 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 laminate film of the present invention is configured as a laminate film in which the resin layers (a) are directly laminated, the same resin layers (a) may be directly laminated, or the same resin layers (a) other than the different film thicknesses may be directly laminated, for example. Further, the resin layer (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 optional raw material components or the average dispersion diameter of the dispersed phase is 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 a laminated film in which a resin layer (a) formed from a biaxially stretched film of the resin composition (a) and a resin layer (also simply referred to as "resin layer (B)") formed from a biaxially stretched film of a resin composition (B) containing a thermoplastic resin, which is different from the resin composition (a), are directly laminated. Here, the resin layer (B) may be 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 various polymers such as 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, and a liquid crystal polymer, and a blend containing 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 resin as described for the above 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, and particularly preferably 65 parts by mass or more. The resin composition (B) may contain resin species or additives other than the PAS resin as a raw material, and for example, various polymers such as the polyphenylene ether resin, the styrene- (meth) acrylic acid copolymer, the elastomer, the silane coupling agent, and further polyamide, polyetherimide, polyethersulfone, polysulfone, polyester (particularly preferably aromatic polyester such as polyethylene terephthalate or polybutylene terephthalate), polyarylate, polyamideimide, polycarbonate, polyether ether ketone, and liquid crystal polymer, and a blend containing at least 1 of these polymers may be used. The method for producing the resin composition (B) used in the present invention is also the same as the above resin composition (a).
Further, the resin layer constituting at least one layer of the biaxially stretched laminated film of the present invention may be a layer having a void. 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 for forming voids in a sheet or a film can be used. For example, the method for producing a biaxially stretched laminate film according to the present invention may further include a step of blending a pore-forming agent into the resin composition, and the biaxially stretching an unstretched sheet of the resin composition containing the pore-forming agent may form fine cracks at the interface between the resin and the pore-forming agent, thereby producing a biaxially stretched laminate film containing a layer having voids (which may be referred to as a fine crack method). In addition, as another method, there may be mentioned a method (sometimes referred to as a solvent removal method) in which the method for producing a biaxially stretched laminated film of the present invention further comprises a step of adding a pore-forming agent to the resin composition, and a step of removing the pore-forming agent by bringing an unstretched sheet or biaxially stretched film produced from the resin composition containing the pore-forming agent into contact with a solvent (sometimes referred to as a removal solvent) in which the pore-forming agent is dissolved, thereby forming a void in the unstretched sheet or biaxially stretched film. In the case where the void is formed in the unstretched sheet, if biaxial stretching is performed after lamination with another unstretched sheet, a biaxially stretched laminate film including a layer having the void can be obtained.
The pore former is preferably calcium carbonate fine particles, and examples thereof include inorganic fine particles such as magnesium sulfate fine particles, calcium oxide fine particles, calcium hydroxide fine particles, and silica fine particles, and in the solvent removal method, a solvent which is solid at room temperature (23 ℃) (referred to as a solid solvent) or a solvent which 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, p-xylene, undecane, dodecane, and liquid paraffin, mineral oil fractions having boiling points corresponding to those of the aliphatic or cyclic hydrocarbons, and phthalic acid esters which are liquid at room temperature such as dibutyl phthalate and dioctyl phthalate, and a nonvolatile liquid solvent such as liquid paraffin is preferably used. The solid solvent is a solvent which is solid at room temperature, and stearyl alcohol, wax alcohol, paraffin wax, or the like can be used as the solid solvent and is mixed with the polyolefin in a heated, melted, and kneaded state. Since uneven stretching may occur if only a solid solvent is used, it is preferable to use a liquid solvent 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, and fluorination such as ethane trifluorideHydrocarbons, diethyl ethers, di
Figure BDA0003590236640000201
Ethers such as alkanes, and volatile solvents such as methyl ethyl ketone. In addition, as the removal solvent, in addition to the above, a solvent having a surface tension of 24mN/m or less at 25 ℃ as disclosed in Japanese patent laid-open No. 2002-256099 can be used. By using a solvent having such a surface tension, it is possible to suppress shrinkage and densification of the network structure due to the surface tension of the gas-liquid interface generated inside the pores at the time of drying after removing the pore former, and as a result, the porosity and permeability of the layer having pores are further improved. The porosity of the layer having pores is not particularly limited, but is preferably 20% or more, more preferably 30% or more to 70% or less, and still more preferably 60% or less, from the viewpoint of excellent mechanical strength and dielectric characteristics. The porosity is a ratio of an area of a hole contained in an image obtained by cutting a layer having a hole in a biaxially stretched laminate film by a microtome method, (I) in a direction parallel to a longitudinal direction and perpendicular to a film surface, (II) in a direction parallel to a width direction and perpendicular to the film surface, and then taking Scanning Electron Microscope (SEM) photographs of the cut surfaces (I) and (II) of the cut film at a magnification of 2000 times, respectively, and assuming that the area of the obtained SEM photograph is 100. In this case, if no voids were observed, the porosity was 0%. The ratio of each of the cut surfaces (I) and (II) was measured, and the value obtained by combining 2 directions of the cut surfaces (I) and (II) and averaging the two directions was defined as "porosity". In the present invention, when the pore forming agent is used to form pores, the proportion of the pore forming agent to be blended may be appropriately adjusted so that the porosity falls within the above range, and the pore forming agent may be left (fine crack method) or removed (solvent removal method) depending on the specific gravities of the resin composition and the pore forming agent, and therefore cannot be generally specified, and for example, the proportion 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, further preferably 20 parts by mass or more, and particularly preferably 30 parts by mass or more, based on 100 parts by mass of the total of the resin composition and the pore forming agentThe above range.
When the biaxially stretched laminate film of the present invention has a laminate structure of the resin layer (a) and the resin layer (B), examples of the laminate structure include, but are not limited to, multilayer structures such as (a)/(B), (a)/(B)/(a), and the like. Among them, from the viewpoint of suppressing the curl of the biaxially stretched laminate film, a symmetrical configuration of (a)/(B)/(a) and (a)/(B)/(a) is preferable. The "/" sign means direct bonding, and for example "(a)/(B)" means a structure in which the resin layers (a) and (B) are directly laminated.
In the biaxially stretched laminate film of the present invention, the thickness of the resin layer (a) is preferably in the range of 2 μm or more, and more preferably in the range of 10 μm or more. By setting the thickness of the resin layer (a) to a range of 2 μm or more, high adhesiveness 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) other than the resin layer (a) is arbitrary, for example.
The method for producing the biaxially stretched laminate film used in the present invention is not particularly limited, and examples thereof include a method for 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 used, the following coextrusion method can be 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 configuration by a coextrusion lamination die method, a feedblock method, or the like, and then molded into a sheet shape by an inflation method, a T-die chill roll method, or the like. This 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 performing biaxial stretching, the unstretched laminate sheet obtained as described above is subjected to biaxial stretching.
The stretch ratio in the longitudinal direction (MD direction) of the biaxially stretched film is 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.
Further, the stretch ratio in the width direction (TD direction) of the biaxially stretched film is 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 view of facilitating the balance between the physical properties in the longitudinal direction and the physical properties in the width direction, the ratio (width direction (TD direction)/(longitudinal direction (MD direction)) of the stretching ratio in the width direction (TD direction)) of the biaxially stretched film to the stretching ratio in the longitudinal direction (MD direction) of the biaxially stretched film is preferably 0.8 or more, more preferably 0.9 or more and 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 of combining them may be used.
In the case of biaxial stretching by the sequential biaxial stretching method, for example, the obtained unstretched sheet is heated by a heating roll set, stretched in 1 stage or 2 stages or more in the 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 cooling roll set at 30 to 60 ℃.
The stretching temperature is preferably in the range of not lower than the glass transition temperature (Tg), more preferably not lower than (Tg +5 ℃) and not higher than (Tg +40 ℃), more preferably not higher than (Tg +30 ℃) and further preferably not higher than (Tg +20 ℃).
Next, stretching is performed in the width direction (TD direction) by a method using a tenter. Both ends of the film stretched in the MD direction were held by clips, introduced into a tenter, and stretched in the TD direction.
The stretch ratio is preferably 2 times or more, more preferably 2.5 times or less to preferably 4 times or less, and more preferably 3.8 times or less.
The stretching temperature is preferably not lower than Tg, more preferably not lower than (Tg +5 ℃) and not higher than (Tg +40 ℃), more preferably not higher than (Tg +30 ℃) and still more preferably not higher than (Tg +20 ℃).
Next, the stretched film is preferably heat-set under tension or while being relaxed in the width direction.
The heat-setting temperature is not particularly limited, but is preferably 200 ℃ or higher, more preferably 220 ℃ or higher, further preferably 240 ℃ or higher to 280 ℃ or lower, and further preferably 275 ℃ or lower. Note that the heat fixation can be performed in 2 stages with varying heat fixation temperatures. In this case, the heat setting temperature of the 2 nd stage is preferably +10 to 40 ℃ higher than the heat setting temperature of the 1 st stage. The heat resistance and mechanical strength of the stretched film heat-set at a heat-setting temperature in this range are further improved.
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, but is preferably 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 laminate film is not particularly limited, but 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 laminate film is preferably in the range of 10 μm or more to 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 exhibit sufficient mechanical strength and dielectric characteristics.
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 a 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 using a chemical agent, ultraviolet light, an electron beam, or the like. Among them, plasma treatment is preferable.
According to an aspect of the present invention, a laminate is provided. The laminate has a structure in which the resin layer (A) of the biaxially stretched laminate film is joined 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 the outermost resin layer surface of at least one of the biaxially stretched laminate films.
The metal layer is not particularly limited, and examples thereof include copper, aluminum, zinc, titanium, nickel, and alloys containing these metals.
The metal layer may be a single layer or 2 layers. When the metal layer is 2 layers, the metal phases may be the same or different.
In one embodiment, the laminate may have a structure 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 "-" mark means direct bonding, and for example, "metal layer-biaxially stretched laminated film" means a structure in which each metal layer and the biaxially stretched laminated film are directly bonded to each other.
Further, examples of the method for bonding the metal layer and the biaxially stretched laminated film include a method in which a metal is subjected to vacuum deposition, sputtering, plating, and the like. The metal layer may be formed by a method of overlapping the biaxially stretched laminate film and the metal foil and thermally welding them.
The laminate provided with the metal layer has excellent dielectric characteristics (low dielectric constant and low dielectric loss tangent) and therefore can be suitably used for next-generation high-speed transmission such as flexible printed wiring boards, flexible flat cables, and electronic/electrical devices capable of coping with radio 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 as an insulator for an engine.
In one embodiment, the laminate may have a structure of, for example, a resin molded article-biaxially stretched laminated film-resin molded article, a resin molded article-biaxially stretched laminated film-metal layer, or the like.
As a method for bonding a resin molded article and a biaxially stretched laminated film, there is a method in which the biaxially stretched laminated film and the resin molded article are stacked and thermally bonded by heat fusion or the like.
Examples of the resin molded article include, but are not limited to, an extrusion molded article, an injection molded article, and a fiber sheet, such as a polyolefin resin, a polyester resin, a nylon resin, a polyarylene sulfide resin, an aromatic polyamide, and a liquid crystal resin.
The flat shaped article may be referred to as a film or a sheet depending on the thickness, and for example, a distinction of a film having a thickness of less than 200 μm and a sheet having a thickness of 200 μm or more is described in a polymer dictionary (compiled by the society of polymer, to warehouse, 1971), and a distinction of a thin flat shaped article having a maximum thickness of 250 μm to a minimum thickness of 25 μm is described as a film in a university dictionary of McGraw-Hill science and technology (japanese news agency, 1996), and there is a technical field of distinguishing a film having a thickness of less than 100 μm and a sheet having a thickness of 100 μm or more, depending on the case. As such, it is generally difficult to distinguish between films and sheets. Therefore, in the present invention, the terms "sheet" and "film" are based on only the difference in designation and are not distinguished from each other. For example, since the term "sheet" is a concept including a member which may be called a thin planar object, a film, or a film, the term "film" is a concept including a member which may be called a thin planar object, a film, or a sheet, and cannot be distinguished by a difference in name.
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
[ polyarylene sulfide resin (a-1) ]
PPS resin a-1: linear polyphenylene sulfide resin (produced by DIC corporation, melting Point 280 ℃, melt viscosity at 300 ℃ (V6)160 pas, using only p-dichlorobenzene 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. The temperature was raised to 204 ℃ under a nitrogen stream with stirring, 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 21.721kg of p-dichlorobenzene and 3.833kg of m-dichlorobenzene (molar ratio of these compounds [ (p)/(m) ] -85/15) and 18.0kg of N-methyl-2-pyrrolidone were placed therein. The temperature was raised by pressurizing to 1kg/cm2 with nitrogen gas at a liquid temperature of 150 ℃. The mixture was stirred at a liquid temperature of 220 ℃ for 3 hours, and a refrigerant of 80 ℃ was flowed through a coil wound around the upper part of the autoclave to cool the mixture. Then, the temperature was raised, and after stirring at a liquid temperature of 260 ℃ for 3 hours, the temperature was lowered and the cooling of the upper part of the autoclave was stopped. During the cooling of the upper part of the autoclave, the liquid temperature was kept constant so as not to decrease. The highest pressure in the reaction was 8.91kg/cm 2. The resulting slurry was washed with warm water 2 times and filtered to obtain a cake containing about 50 mass% of water. Then, 60kg of water and 100g of acetic acid were added to the cake to form a slurry, and the slurry was stirred at 50 ℃ for 30 minutes and then filtered again. At this time, the pH of the slurry was 4.6. The operation of adding 60kg of water and stirring for 30 minutes and then filtering again was repeated 5 times for the cake obtained here. The obtained cake was dried at 120 ℃ for 4.5 hours in a hot air circulation dryer to obtain polyphenylene sulfide resin (a-2) (hereinafter abbreviated as PPS resin a-2) as a white powder. The melt viscosity (V6) was 45 pas at 230 ℃ and 300 ℃.
[ polyphenylene ether resin (b) ]
PPE: poly (2, 6-dimethyl-1, 4-phenylene ether)
The PPS has a carboxyl group at the molecular terminal thereof, and the PPE has a hydroxyl group at the molecular terminal thereof.
[ styrene-methacrylic acid copolymer (c) ]
Styrene resin c-1: styrene and methacrylic acid were mixed at a ratio of 97.5: 2.5 by mass ratio of the copolymer
Styrene resin c-2: styrene and methacrylic acid were mixed at a ratio of 80.0: 20.0 mass ratio of polymerized copolymer
[ elastomer (d) ]
Elastomer d-1: ethylene, glycidyl methacrylate and methyl acrylate were reacted at a molar ratio of 70: 3: 27 glycidyl group-modified elastomer obtained by polymerization (product of Sumitomo chemical Co., Ltd., "BONDFAST 7L")
Elastomer d-2: ethylene, glycidyl methacrylate, was reacted at 88: 12 (product of Sumitomo chemical Co., Ltd., "BONDFAST E")
Elastomer d-3: maleic anhydride-modified elastomer (manufactured by Mitsui chemical Co., Ltd., "Toughtmer MH 7020")
[ silane coupling agent ]
Silane coupling agent: gamma-aminopropyltrimethoxysilane
Example 1 production of resin composition (A) and resin layer (A)
86.5 parts by mass of the PPS resin a-1, 5 parts by mass of the PPE, 3 parts by mass of the styrene resin c-1, 5 parts by mass of the elastomer d-1 and 0.5 part by mass of the silane coupling agent were uniformly mixed by a tumbler mixer to obtain a mixture.
Then, the mixture was charged into a twin screw extruder (manufactured by Nippon Steel Co., Ltd., "TEX-30. alpha.") equipped with a conveyor belt. Then, the resin composition (A-1) was produced by melt-extruding the mixture under conditions of a discharge rate of 20kg/hr, a screw rotation rate of 300rpm, and a set temperature of 300 ℃ and discharging the extruded mixture in the form of strands, cooling the strands with water having a temperature of 30 ℃ and then cutting the cooled strands.
Then, the resin composition (A-1) was charged into a single-screw extruder of a full-flight screw, melted at 280 to 300 ℃, extruded from a T die, and then cooled in close contact with a cooling roll set at 40 ℃ to prepare an unstretched polyarylene sulfide resin sheet. Further, the unstretched polyarylene sulfide resin sheet was stretched at 100 ℃ by a 3.5X 3.5 times double shaft stretcher manufactured by Hill Seiki Seisakusho, to obtain a biaxially stretched film having a thickness of 35 μm. Further, the obtained biaxially stretched film was fixed to a mold frame, and heat-set treatment was performed using an oven at 275 ℃. The biaxially stretched film was used to evaluate dielectric characteristics.
The biaxially stretched film obtained above was cut in a direction perpendicular to the film surface by a microtome method. 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 a single dispersed particle or at the interface between the matrix and the PPE particle.
[ examples 2 to 9] production 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 compounding amounts of the 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 prepared in the same manner except that the stretching ratio was changed to 3X 3, and the dielectric properties were evaluated.
Further, as a result of analyzing the components of the biaxially stretched film by the same method as in example 1, it was found that PPE particles were dispersed in a PPS matrix. The elastomer is present as a single dispersed particle or at the interface between the matrix and the PPE particle.
EXAMPLE 10 production of resin composition (A) and resin layer (A)
A resin composition (A-10) for a resin layer (A-10) was prepared 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, and a biaxially stretched film using the obtained resin composition (A-10) was prepared to evaluate dielectric properties.
Further, as a result of analyzing the components of the biaxially stretched film by the same method as in example 1, it was found that PPE particles were dispersed in a PPS matrix. The elastomer is present as a single dispersed particle or at the interface between the matrix and the PPE particle.
Comparative example 1 production of comparative 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 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 was used in place of the resin composition containing 86.5 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. The dielectric constant and the dielectric loss tangent of the obtained biaxially stretched film were measured.
Comparative example 2 production of comparative 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) containing 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 in place 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 the dielectric loss tangent of the obtained biaxially stretched film were measured.
Comparative example 3 production of comparative resin composition (A) and resin layer (A)
PPS resin a-1 was fed into a twin screw extruder "TEX-30 α" with a conveyor belt, made by Nippon Steel works, K.K., and melt-extruded at a discharge rate of 20kg/hr, a screw rotation rate of 300rpm, a set temperature of 300 ℃ and a strand-like discharge, and the melt was cooled with water at a temperature of 30 ℃ and then cut to prepare a melt. Next, the kneaded mixture was fed into a single-screw extruder of a full-flight screw, melted at 280 to 300 ℃, and the melted resin was extruded from a T-die and then closely cooled by a cooling roll set at 40 ℃ to prepare an unstretched polyarylene sulfide resin sheet. Further, the unstretched polyarylene sulfide resin sheet was stretched at 100 ℃ by a 3.5X 3.5 times double shaft stretcher manufactured by Hill Seiki Seisakusho, to obtain a biaxially stretched film having a thickness of 35 μm. Further, the obtained biaxially stretched film was fixed to a mold frame, and heat-set treatment was performed in an oven at 270 ℃ to obtain a biaxially stretched film. The dielectric constant and the 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.") equipped with a conveyor belt. Then, the resin composition (B-1) was produced by melt-extruding the mixture under conditions of a discharge rate of 20kg/hr, a screw rotation rate of 300rpm, and a set temperature of 300 ℃ and discharging the mixture in the form of strands, cooling the strands with water having a temperature of 30 ℃ and then cutting the strands.
[ reference example 3]
60 parts by mass of PPS resin a-1 and 40 parts by mass of calcium carbonate (CaCO3, manufactured by shot-tail calcium Co., Ltd., average particle diameter 3 μm) were charged into a twin-screw extruder (manufactured by Nippon Steel Co., Ltd., "TEX-30. alpha.") with a conveyor belt. Then, the resin composition (B-2) was produced by melt-extruding the mixture under conditions of a discharge rate of 20kg/hr, a screw rotation rate of 300rpm, and a set temperature of 300 ℃ and discharging the mixture in the form of strands, cooling the strands with water having a temperature of 30 ℃ and then cutting the strands.
Example 11 production of biaxially stretched laminated film and laminate
The resin compositions (A-1) and (B-1) are supplied to an extruder (bore diameter: 40mm) for the resin layer (A) and an extruder (bore diameter: 40mm) for the resin layer (B), respectively, and melted at 280 to 300 ℃, and the melted resins are supplied to a co-extruded sheet manufacturing apparatus of a T-die cooling roll method having a feed block (feed block and T-die temperature: 300 ℃) to be melt-extruded, and then closely cooled by a cooling roll set to 40 ℃, whereby a co-extruded laminated unstretched sheet having a layer structure of 3 layers of the resin layer (A)/the resin layer (B)/the resin layer (A) is manufactured.
Then, the obtained laminated unstretched sheet was biaxially stretched at 100 ℃ by 3.5X 3.5 times using a batch biaxial stretcher (manufactured by Kokai Co., Ltd.), thereby obtaining a film having a thickness of 50 μm. Further, the obtained film was fixed to a mold frame, and subjected to a heat-fixing treatment using an oven at 275 ℃.
Next, the obtained biaxially stretched laminated film and an electrolytic copper foil (thickness 18 μm) were superposed so that the resin layer (a) of the biaxially stretched laminated film and the electrolytic copper foil were joined, and pressed at 270 ℃ and a pressure of 5MPa for 15 seconds by a press machine to prepare a laminate of a copper foil and a film.
Example 12 production of biaxially stretched laminated 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 as the resin layer (a) and the stretching ratio was changed to 3 × 3.
Examples 13 to 19 production of biaxially stretched laminated film and laminate
A biaxially stretched laminate film and a laminate were produced in the same manner as in example 12, except that the resin layer (a) was changed to the resin compositions (a-3 to a-9).
[ 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 obtained biaxially stretched laminated film and an electrolytic copper foil (thickness 18 μm) were superposed so that the resin layer (a) of the biaxially stretched laminated film and the electrolytic copper foil were joined, and pressed at 260 ℃ and a pressure of 5MPa for 15 seconds by a press machine to prepare a laminate of a copper foil and a film.
[ example 21]
A biaxially stretched film and a laminate were produced in the same manner as in example 12, except that the resin layer (B) was changed to the resin composition (B-2). The average porosity of the resin layer (B) was 55%.
Comparative example 4 production of biaxially stretched laminated film for comparison and laminate
A biaxially stretched laminated film and a laminate were produced in the same manner as in example 11, except that the resin composition (cA-1) was used for the resin layer (a).
Comparative example 5 production of biaxially stretched laminated film for comparison and laminate
A biaxially stretched laminated film and a laminate were produced in the same manner as in example 11, except that the resin composition (cA-2) was used for the resin layer (a).
Comparative example 6 production of biaxially stretched laminated film for comparison and laminate
A biaxially stretched laminated film and a laminate were produced in the same manner as in example 11, except that the 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 laminated film for comparison and laminate
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 (having a thickness of 18 μm), and the laminate was pressed at 270 ℃ and a pressure of 5MPa for 15 seconds by a press machine to prepare a laminate of a copper foil and a film.
[ evaluation ]
1. Dielectric constant and dielectric loss tangent
The dielectric constant and the dielectric loss tangent were measured in accordance with JIS C2565: 1992, by the cavity resonance method. Specifically, a short strip having a width of 2mm × a length of 150mm is made of an insulating film. Then, the prepared strands were left to stand at 23 ℃ for 24 hours in an atmosphere of 50% Rh, and then the dielectric constant and dielectric loss tangent at a frequency of 1GHz were measured by the cavity resonance method using ADMS010c series (product of AET Co., Ltd.). The following tables show "dielectric constant" and "dielectric loss tangent".
2. Adhesion Property
The adhesiveness is determined based on JIS K6854: the peel strength between the copper foil and the biaxially stretched laminate film was measured by a test method specified in 1999, and evaluated according to the following criteria. The following table shows "adhesiveness".
Very good: more than 8N/cm
O: 7N/cm or more and less than 8N/cm
And (delta): more than 6N/cm 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 having a grid pattern (grid size 10 × 10(mm)) was applied to an unstretched sheet in a non-oriented state, and the state of the grid pattern of the obtained biaxially stretched film was visually observed when the sheet was stretched at a predetermined magnification, and evaluated according to the following criteria. The obtained results are shown as "stretching uniformity" in the following table.
Very good: the square is formed by more than 9 parts of squares on the whole surface of the film
O: the number of the squares of 8 or more and less than 9 on the whole surface of the film becomes a square
And (delta): the number of the squares of 5 or more and less than 8 on the whole surface of the film becomes a square
X: less than 5 squares of the whole face of the film become squares
[ Table 1]
Figure BDA0003590236640000311
[ Table 2]
Figure BDA0003590236640000312
[ Table 3]
Figure BDA0003590236640000321
[ Table 4]
Figure BDA0003590236640000322
[ Table 5]
Figure BDA0003590236640000331
[ Table 6]
Figure BDA0003590236640000332
The biaxially stretched films used as the resin layers (A-1) to (A-10) obtained in examples 1 to 10 had low dielectric constants and low dielectric loss tangents, and exhibited excellent dielectric characteristics. In addition, the biaxially stretched laminated films and laminates obtained in examples 11 to 21 including the resin layer showed excellent adhesion to the metal layer.
In contrast, the biaxially stretched films, biaxially stretched laminated films and laminates obtained in comparative examples 1 and 4, comparative examples 2 and 5, and comparative examples 3,6 and 7, respectively, were inferior in dielectric characteristics and/or adhesiveness.
As is clear from the results, by using a biaxially stretched laminate film provided with a resin layer comprising a biaxially stretched film made of a resin composition obtained by blending a polyarylene ether resin, a styrene- (meth) acrylic acid copolymer and a polyarylene sulfide resin as raw materials and having a specific form, it is possible to exhibit a low dielectric constant and a low dielectric loss tangent while maintaining the excellent properties (heat resistance, flame retardancy, chemical resistance, and wet heat resistance) inherent in polyarylene sulfide resins. It has also been found that the polyarylene sulfide resin can be directly thermally bonded to a metal or a resin molded product at a temperature not higher than the melting point of the polyarylene sulfide resin.

Claims (17)

1. A biaxially stretched laminate film characterized by having a structure in which at least 2 resin layers are directly laminated,
in the biaxially stretched laminated film, in the case of the biaxially stretched laminated film,
at least 1 layer is a resin layer (A) composed of a biaxially stretched film of a resin composition (A) containing at least a polyarylene sulfide resin, a polyphenylene ether resin, and a styrene- (meth) acrylic acid copolymer as raw materials and having 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 [ mu ] m or less.
2. The biaxially stretched laminate film according to claim 1, wherein 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.
3. The biaxially stretched laminate film of claim 1, wherein the polyarylene sulfide resin has acid groups.
4. The biaxially stretched laminate film according to claim 1, wherein the ratio of the polyphenylene ether resin is in the range of 3 to 40 parts by mass relative to 100 parts by mass of the polyarylene sulfide resin, the polyphenylene ether resin and the styrene- (meth) acrylic acid copolymer in total.
5. The biaxially stretched laminate film according to claim 1, wherein the ratio of the amount of the styrene- (meth) acrylic acid copolymer is in the range of 0.5 to 10 parts by mass relative to 100 parts by mass of the polyarylene sulfide resin, the polyphenylene ether resin, the styrene- (meth) acrylic acid copolymer and the elastomer in total.
6. The biaxially stretched laminate film according to claim 1, wherein the styrene- (meth) acrylic acid copolymer has a (meth) acrylic acid content in a range of 1 to 30% by mass relative to the total mass of the styrene- (meth) acrylic acid copolymer.
7. The biaxially stretched laminate film according to claim 1, wherein said resin composition (a) further comprises an elastomer.
8. The biaxially stretched laminate film according to claim 1, wherein the ratio of the amount of the elastomer blended is within a range of 3 to 15 parts by mass relative to 100 parts by mass of the total of the polyarylene sulfide resin, the polyphenylene ether resin, the styrene- (meth) acrylic acid copolymer and the elastomer.
9. The biaxially stretched laminate film according to claim 1, wherein the elastomer comprises at least 1 selected from the group consisting of a copolymer of an α -olefin and a glycidyl ester of an α, β -unsaturated carboxylic acid, and a copolymer of an α -olefin, a glycidyl ester of an α, β -unsaturated carboxylic acid and a (meth) acrylate.
10. The biaxially stretched laminate film according to claim 9, wherein the elastomer has an α -olefin content in the range of 50 to 95 mass% with respect to the total mass of the elastomer.
11. The biaxially stretched laminate 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 comprising a polyarylene sulfide resin.
12. A laminate having a structure in which a resin layer (A) of the biaxially stretched laminate film according to any one of claims 1 to 11 is joined to at least 1 selected from the group consisting of a metal layer and a resin molded body.
13. A flexible printed wiring board comprising the laminate according to claim 12.
14. A flexible flat cable comprising the laminate according to claim 12.
15. An insulator for an engine, comprising the laminate according to claim 12.
16. A method for producing a biaxially stretched laminate film, characterized in that it is a method for producing a biaxially stretched laminate film having a structure in which at least 2 resin layers are directly laminated,
which comprises 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 laminated film, in the case of the biaxially stretched laminated film,
at least 1 layer is a resin layer (A) composed of a biaxially stretched film obtained by biaxially stretching a resin composition (A) which is prepared by blending 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 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 5 [ mu ] m or less.
17. 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 11 to at least 1 selected from the group consisting of a metal layer and a resin molded body.
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