KR20230129424A - Polyarylene sulfide resin composition, and biaxially stretched film and laminate using the same - Google Patents

Abstract

It is possible to provide a resin composition that has excellent continuous extrusion film forming properties and stretchability, and that can have excellent adhesion to metals with a low dielectric constant in the resulting biaxially stretched film, and a laminate using a film containing the resin composition. A resin composition consisting of a polyarylene sulfide resin (A), a fluorinated resin (B), and a thermoplastic resin (C) other than the fluorinated resin (B) with a glass transition temperature of 140°C or higher or a melting point of 270°C or lower, and It was discovered that the above problem could be solved by using a film containing the resin composition, and the present invention was completed.

Description

Polyarylene sulfide resin composition, and biaxially stretched film and laminate using the same

The present invention relates to a polyarylene sulfide resin composition with excellent film forming and stretching properties, low dielectric constant, and excellent adhesion to metal, and biaxially stretched films and laminates using the same.

Recently, in the field of flexible printed wiring boards (FPC) and flexible flat cables (FFC), with the development of cloud and IoT (Internet of Things), improvements in automobile automatic driving technology, and the development of electric vehicles and hybrid vehicles. , cables and antennas that can process large amounts of data and transmit it at high speed and without loss are required. However, conventionally, polyimide (PI) films have been used as FPC substrates, and polyester films (PET films, etc.) have been used as FCC substrates, and these cannot be said to have dielectric properties that can support the next-generation high-speed transmission.

However, films using polyarylene sulfide resins, such as polyphenylene sulfide resin (PPS), are excellent in heat resistance, flame retardancy, chemical resistance, and electrical insulation, and are therefore used as insulating materials for condensers and motors, as well as heat-resistant tapes. there is. Polyarylene sulfide resin has superior dielectric properties compared to PI or PET, so it can be suitably applied to the fields of FPC and FFC. However, to cope with next-generation high-speed transmission, additional low dielectric constant and low dielectric loss tangent are required. In addition, in order to use it as an FCCL or FPC base film, adhesiveness to metals such as copper by heating is required.

As an improvement in this, for example, Patent Document 1 proposes a method of making PPS resin contain inorganic particles and forming pores during biaxial stretching. However, in the film described in Patent Document 1, although the effect of lowering the dielectric constant is sufficiently obtained, the mechanical properties of the film deteriorate due to the presence of vacancies. Therefore, although a layer containing no inorganic particles is laminated on the surface layer, sufficient mechanical strength is not obtained. In addition, it is necessary to laminate, and when stretching a laminate, matching the adhesion and stretchability between layers is important, and tends to be very difficult from a production standpoint. Moreover, when using it as an FCCL or FPC base film, sufficient adhesion to metals such as copper cannot be obtained by heating.

In addition, in order to achieve both the excellent properties of PPS resin and fluorine resin, several attempts to blend both resins have been reported. For example, Patent Document 2 proposes a resin composition consisting of a PPS resin and a fluororesin containing a functional group, which aims to stabilize the dispersed particle size before and after retention. However, the proposals described in these patents were proposed for the main purpose of injection molding use, and there is no description of a biaxially stretched film with a low dielectric constant, and it does not affect the physical properties of the film, and the dispersion of the dispersed phase in the film is not disclosed. There is no description of the hardness or adhesion to metal.

Japanese Patent Publication No. 2018-83415 Japanese Patent Publication No. 2015-110732

The present invention provides a resin composition that is excellent in continuous extrusion film forming properties and stretchability, and has a low dielectric constant in the obtained biaxially stretched film and can have excellent adhesion to metal, and a laminate using such a film. .

The present inventors conducted intensive studies to solve the above problems, and as a result, a polyarylene sulfide resin (A), a fluorine-containing resin (B), a fluorine-containing resin ( It was discovered that the above problem could be solved by using a resin composition made of a thermoplastic resin (C) other than B), and the present invention was completed.

That is, the present invention relates to the following (1) to (11).

(1) A thermoplastic resin (C) containing polyarylene sulfide resin (A) as the main component, a fluorinated resin (B), and a glass transition temperature of 140°C or higher or a melting point of 270°C or lower other than the fluorinated resin (B). It is a resin composition using as a raw material and having a continuous phase and a dispersed phase,

The continuous phase contains a polyarylene sulfide-based resin (A),

The dispersed phase relates to a polyarylene sulfide-based resin composition containing a fluorinated resin (B) and a thermoplastic resin (C) other than the fluorinated resin (B).

(2) The polyarylene sulfide resin composition according to (1), wherein the polyarylene sulfide resin (A) is 51 to 95% by mass.

(3) The average dispersion diameter of the above-mentioned dispersed phase, the fluorinated resin (B) and the thermoplastic resin (C) other than the fluorinated resin (B) with a glass transition temperature of 140°C or higher or melting point of 270°C or lower, is 0.5 μm to 7 μm, ( The resin composition according to 1) or (2).

(4) Any one of (1) to (3), wherein the fluorinated resin (B) is a fluorinated resin having at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, and an isocyanate group. The resin composition described in .

(5) The ratio of the amount of the fluorinated resin (B) mixed is 100% by mass of the total amount of the polyarylene sulfide resin (A), the fluorinated resin (B), and the thermoplastic resin (C) other than the fluorinated resin, The resin composition according to any one of (1) to (3), which is 5 to 49% by mass.

(6) The thermoplastic resin (C) other than the fluorinated resin (B) having a glass transition temperature of 140°C or higher or a melting point of 270°C or lower is polyphenylene ether resin, polycarbonate resin, polyethersulfone resin, or polyphenylsulfone. The resin composition according to any one of (1) to (5), which is at least one polymer selected from the group consisting of resin and polyetherimide resin.

(7) The ratio of the thermoplastic resin (C) other than the fluorinated resin (B) having a glass transition temperature of 140°C or higher or a melting point of 270°C or lower is polyarylene sulfide resin (A), fluorinated resin (B), The resin composition according to any one of (1) to (6), which is 1 to 40% by mass based on a total amount of 100% by mass of the thermoplastic resin (C) other than the fluorine-containing resin.

(8) The resin composition according to any one of (1) to (7), further comprising a modified elastomer (D) to which a reactive group is imparted.

(9) The resin composition according to (8), wherein the modified elastomer (D) is an olefin polymer having at least one functional group selected from the group consisting of an epoxy group and an acid anhydride group.

(10) The mixing ratio of the modified elastomer (D) is 100 in total for the polyarylene sulfide resin (A), the fluorinated resin (B), the thermoplastic resin other than the fluorinated resin (C), and the modified elastomer (D). The resin composition according to (8) or (9), which is in the range of 1 to 15% by mass, based on mass%.

(11) The resin composition according to any one of (1) to (10), further comprising a styrene-(meth)acrylic acid copolymer (E).

(12) The resin composition according to (11), wherein the blending amount of the styrene-(meth)acrylic acid copolymer (E) is in the range of 0.5 to 10 mass%.

(13) A biaxially stretched film obtained by biaxially stretching the resin composition according to any one of (1) to (12).

(14) A biaxially stretched laminated film having at least one layer made of the resin composition according to any one of (1) to (12).

(15) A laminate comprising the biaxially stretched film or biaxially stretched laminated film according to (13) or (14), and a metal layer disposed on at least one side of the biaxially stretched film or biaxially stretched laminated film.

It's about.

According to the present invention, a resin composition is provided that has excellent continuous extrusion film forming properties and stretchability, and the obtained biaxially stretched film can have low dielectric properties and excellent adhesion to metal.

Hereinafter, modes for carrying out the present invention will be described in detail.

[Resin composition]

The resin composition contains polyarylene sulfide resin (hereinafter sometimes referred to as “PAS resin”) as the main component, and contains other materials other than fluorine-containing resin and fluorine-containing resin with a glass transition temperature of 140°C or higher or a melting point of 270°C or lower. It is made of thermoplastic resin as a raw material. At this time, the resin composition has a continuous phase and a dispersed phase. At this time, the continuous phase contains a polyarylene sulfide resin, and the dispersed phase includes a fluorine-containing resin and a glass transition temperature of 140°C or higher or a melting point of 270. It includes thermoplastic resins (C) other than fluorinated resins with a temperature of ℃ or lower.

The average dispersion diameter of the dispersed phase is 0.5 to 7 μm, preferably 0.5 to 5 μm or less, and more preferably 0.5 to 3 μm. If the average dispersion diameter of the dispersed phase is within the range of 0.5 to 7 μm, a uniform stretched film that maintains film properties and has excellent adhesion to metal can be obtained. In addition, in the present invention specification, the “average dispersion diameter of the dispersed phase” shall adopt the value measured by the method described in the Examples.

[Polyarylene sulfide resin (A)]

Polyarylene sulfide-based resin (A) (PAS-based resin (A)) is the main component of the resin composition and is a component that has the function of providing excellent heat resistance, chemical resistance, and dielectric properties to the film.

PAS-based resin (A) is a polymer containing a structure in which an aromatic ring and a sulfur atom are bonded (specifically, a structure represented by the following formula (1)) as a repeating unit.

(In the above formula, R ¹ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a nitro group, an amino group, a phenyl group, a methoxy group, and an ethoxy group, and n each independently represents 1 to 4 carbon atoms. is the integer of .)

Here, it is preferable that all R ¹ in the structure represented by formula (1) are hydrogen atoms. With this structure, the mechanical strength of the PAS-based resin (A) can be further increased. Examples of the structure represented by formula (1) in which all R ¹ are hydrogen atoms include the structure represented by formula (2) below (i.e., a structure in which a sulfur atom is bonded to the aromatic ring at the para position), and the structure represented by formula (3) below. The structure shown (i.e., a structure in which a sulfur atom is bonded to an aromatic ring at a meta position) is included.

Among these, the structure represented by formula (1) is preferably the structure represented by formula (2). If it is a PAS-based resin (A) having a structure represented by formula (2), heat resistance and crystallinity can be further improved.

In addition, the PAS-based resin (A) may contain not only the structure represented by the above formula (1) but also the structure represented by the following formulas (4) to (7) as repeating units.

The structures represented by formulas (4) to (7) are preferably contained in an amount of 30 mol% or less, and more preferably 10 mol% or less, in all repeating units constituting the PAS-based resin (A). With this structure, the heat resistance and mechanical strength of the PAS-based resin (A) can be further improved.

Additionally, the coupling style of the structures represented by formulas (4) to (7) may be either a random shape or a block shape.

In addition, the PAS-based resin (A) may contain a trifunctional structure represented by the following formula (8), a naphthyl sulfide structure, etc. as repeating units in its molecular structure.

The structure represented by formula (8), the naphthyl sulfide structure, etc. are preferably contained in 1 mol% or less in all repeating units constituting the PAS resin (A), and it is more preferable that they are not contained substantially. . With this structure, the content of chlorine atoms in the PAS-based resin (A) can be reduced.

In addition, the characteristics of the PAS-based resin (A) are not particularly limited as long as they do not impair the effect of the present invention, but the melt viscosity (V6) at 300°C is preferably 100 to 2000 Pa·s, and From the point that the balance between fluidity and mechanical strength becomes good, it is more preferable that it is 120 to 1600 Pa·s.

In addition, the PAS-based resin (A) has a peak in the molecular weight range of 25,000 to 40,000 in measurement using gel permeation chromatography (GPC), and the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) It is particularly preferable that (Mw/Mn) is in the range of 5 to 10 and the non-Newtonian index is in the range of 0.9 to 1.3. By using such a PAS-based resin (A), the content of chlorine atoms in the PAS-based resin (A) itself can be reduced to the range of 500 to 2,000 ppm without lowering the mechanical strength of the film, making it halogen-free. Application to electronic and electrical components becomes easier.

In addition, in this specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw/Mn) each adopt values measured by gel permeation chromatography (GPC). In addition, the measurement conditions of GPC are as follows.

[Measurement conditions by gel permeation chromatography]

Apparatus: Ultra-high temperature polymer molecular weight distribution measuring device (SSC-7000 manufactured by Senshu Science Co., Ltd.)

Column: UT-805L (manufactured by Showa Denko)

Column temperature: 210℃

Solvent: 1-chloronaphthalene

Measurement method: Measure the molecular weight distribution and peak molecular weight using a UV detector (360 nm) using six types of monodisperse polystyrene for calibration.

The method for producing the PAS-based resin (A) is not particularly limited, but includes, for example: 1) in the presence of sulfur and sodium carbonate, a dihalogeno aromatic compound, if necessary, a polyhalogeno aromatic compound or other copolymerization components; 2) A method of polymerizing a dihalogeno aromatic compound in a polar solvent in the presence of a sulfidating agent, etc., by adding a polyhalogeno aromatic compound or other copolymerization components if necessary, 3) Examples include a method of self-condensing p-chlorothiophenol by adding other copolymerization components if necessary. Among these manufacturing methods, method 2) above is universal and preferable.

Additionally, during the reaction, in order to control the degree of polymerization, an alkali metal salt of carboxylic acid or sulfonic acid, or alkali hydroxide may be added.

Among the methods of 2) above, the following method of 2-1) or method of 2-2) is particularly preferable.

In the method of 2-1), a hydrous sulfidating agent is introduced into a mixture containing a heated organic polar solvent and a dihalogeno aromatic compound at a rate that allows water to be removed from the reaction mixture, and the organic polar solvent is added to the mixture containing the dihalogeno aromatic compound. When reacting the dihalogeno aromatic compound and the sulfidizing agent by adding a polyhalogeno aromatic compound as necessary, the amount of moisture in the reaction system is controlled to be in the range of 0.02 to 0.5 mole per mole of organic polar solvent, PAS-based resin (A) is produced (see Japanese Patent Publication No. Hei 07-228699).

In the method of 2-2), in the presence of solid alkali metal sulfide and an aprotic polar organic solvent, a dihalogeno aromatic compound and, if necessary, a polyhalogeno aromatic compound or other copolymerization components are added, and the alkali metal is added. When reacting hydrosulfide and 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 mole per mole of sulfur source, and the moisture content in the reaction system is controlled to be 0.02 mole per mole of aprotic polar organic solvent. PAS-based resin (A) is manufactured by controlling within the following range (refer to pamphlet WO2010/058713).

Specific examples of dihalogeno aromatic compounds include p-dihalobenzene, m-dihalobenzene, o-dihalobenzene, 2,5-dihalotoluene, 1,4-dihalonaphthalene, 1-methoxy-2, 5-dihalobenzene, 4,4'-dihalobiphenyl, 3,5-dihalobenzoic acid, 2,4-dihalobenzoic acid, 2,5-dihalonitrobenzene, 2,4-dihalonitrobenzene, 2 ,4-dihaloanisole, p,p'-dihalodiphenyl ether, 4,4'-dihalobenzophenone, 4,4'-dihalodiphenyl sulfone, 4,4'-dihalodiphenyl sulfoxide, 4 , 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.

Additionally, polyhalogeno aromatic compounds include 1,2,3-trihalobenzene, 1,2,4-trihalobenzene, 1,3,5-trihalobenzene, and 1,2,3,5. -Tetrahalobenzene, 1,2,4,5-tetrahalobenzene, 1,4,6-trihalonaphthalene, etc. are mentioned.

Additionally, the halogen atom contained in the above compound is preferably a chlorine atom or a bromine atom.

As a post-treatment method for the reaction mixture containing the PAS-based resin (A) obtained through the polymerization process, a known and commonly used method is used. This post-processing method is not particularly limited, but examples include the following methods (1) to (5).

In the method (1), after completion of the polymerization reaction, the reaction mixture is first removed as is or an acid or base is added, the solvent is distilled off under reduced pressure or normal pressure, and the solid after the solvent distillation is then mixed with water or a reaction solvent ( or an organic solvent having equivalent solubility to low-molecular-weight polymers), acetone, methyl ethyl ketone, alcohol, etc., and washed once or twice or more, and further neutralized, washed with water, filtered, and dried.

In the method (2), after completion of the polymerization reaction, a solvent (soluble in the polymerization solvent used and at least For PAS-based resin (A), a poor solvent) is added as a precipitant to precipitate solid products such as PAS-based resin (A) and inorganic salts, and these are separated by filtration, washed, and dried.

In the method (3), after completion of the polymerization reaction, a reaction solvent (or an organic solvent with equivalent solubility to the low molecular weight polymer) is added to the reaction mixture, stirred, and then filtered to remove the low molecular weight polymer, followed by water, acetone, Washed once or twice or more with a solvent such as methyl ethyl ketone or alcohol, then neutralized, washed with water, filtered and dried.

In method (4), after completion of the polymerization reaction, water is added to the reaction mixture, washed with water, filtered, and if necessary, acid is added during water washing, treated with acid, and dried.

In the method (5), after completion of the polymerization reaction, the reaction mixture is filtered, if necessary, washed with a reaction solvent once or twice or more, and further washed with water, filtered, and dried.

Examples of acids that can be used in the method (4) above 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, and benzoic acid. , aromatic carboxylic acids such as phthalic acid and salicylic acid, dicarboxylic acids such as maleic acid and fumaric acid, organic acids such as sulfonic acids such as methanesulfonic acid and p-toluenesulfonic acid, and inorganic acids such as hydrochloric acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, and phosphoric acid. You can.

Moreover, examples of hydrogen salts include sodium hydrogen sulfide, disodium hydrogen phosphate, and sodium hydrogen carbonate. However, for practical use, organic acids that are less corrosive to metal members are preferable.

In addition, in the methods (1) to (5) above, drying of the PAS-based resin (A) may be performed in a vacuum, in air, or in an inert gas atmosphere such as nitrogen.

In particular, the PAS-based resin (A) post-treated by the method (4) above increases the amount of acid groups bonded to the terminal of the molecule, resulting in the fluorinated resin (B) having a glass transition temperature of 140°C or higher, or a melting point of 270°C. When mixed with a thermoplastic resin (C) other than a fluorinated resin at a temperature of ℃ or lower, a modified elastomer (D), or a styrene-(meth)acrylic acid copolymer (E), the effect of increasing their dispersibility is obtained. As an acid group, it is especially preferable that it is a carboxyl group.

The content of PAS-based resin (A) as the main component in the resin composition may be 51 to 95 mass%, but is preferably 60 to 90 mass%. If the content of the PAS-based resin (A) is within the above range, the heat resistance and chemical resistance inherent to the PAS resin can be imparted to the film, and stretchability can also be maintained. In addition, in the present invention, as a main component, it means containing the specific resin in an amount of 50% by mass or more, preferably 60% by mass or more, relative to the total mass of the resin components used to form the resin composition. It means that it contains.

[Fluorine-containing resin (B)]

The structure of the fluorine-containing resin (B) is not particularly limited, but is comprised of at least one type of fluoroolefin unit. For example, tetrafluoroethylene polymer, copolymers with perfluoro(alkylvinyl ether), hexafluoropropylene, vinylidene fluoride, vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene, and ethylene. , copolymers with non-fluorinated ethylene-based monomers that do not contain fluorine, such as propylene, butene, and alkyl vinyl ethers. Specifically, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-perfluoro(alkylvinyl ether) copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-tetra Examples include fluoroethylene-hexafluoropropylene copolymer, polyvinylidene fluoride, and polychlorotrifluoroethylene. Among them, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-perfluoro(alkylvinyl ether) copolymer, and tetrafluoroethylene-hexafluoropropylene copolymer are preferred because they are easily melt extrudable. .

Among the fluorine-containing resins (B), fluorine-containing resins (B) having a functional group are preferable. The fluorinated resin (B) having a functional group has at least one type of reactive functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, and an isocyanate group. Two or more types of these reactive functional groups may be contained. Among them, a carbonyl group-containing group is preferable because it has excellent reactivity with the PAS-based resin (A). Examples of the carbonyl group-containing group include groups having a carbonyl group between the carbon atoms of the hydrocarbon group, carbonate group, carboxyl group, haloformyl group, alkoxycarbonyl group, acid anhydride group, and polyfluoroalkoxycarbonyl group.

As a method of introducing a reactive functional group into the fluorinated resin (B) having a functional group, (1) when producing the main chain of the fluorinated resin having a functional group by a polymerization reaction, a monomer having a reactive functional group is used. (2) A chain transfer agent that generates a radical having a reactive functional group is used, and a fluorinated resin (B) having a functional group is produced through a polymerization reaction. (3) A polymerization initiator that generates a radical having a reactive functional group is used to produce a fluorinated resin (B) having a functional group through a polymerization reaction. (4) A method of modifying the fluororesin by methods such as oxidation and thermal decomposition. (5) A method of mixing a compound or resin that is compatible with a fluororesin and contains the above-mentioned functional group is included.

Examples of the reactive functional group-containing monomer include a carboxyl group-containing monomer, an epoxy group-containing monomer, a hydroxy group-containing monomer, and an isocyanate group-containing monomer.

As monomers having a carboxyl group-containing group, unsaturated dicarboxylic acids (maleic acid, itaconic acid, citraconic acid, crotonic acid, hymic acid, 5-norbornene-2,3-dicarboxylic acid), their unsaturated dicarboxylic acid anhydrides, and unsaturated monocarboxylic acids. (acrylic acid, methacrylic acid), vinyl esters (vinyl acetate, vinyl chloroacetate, vinyl butanoate, vinyl pivalate, vinyl benzoate, vinyl crotonate), etc.

Examples of the hydroxyl group-containing monomer include hydroxyl group-containing vinyl ester, hydroxyl group-containing vinyl ether, hydroxyl group-containing allyl ether, hydroxyl group-containing (meth)acrylate, hydroxyethyl crotonate, and allyl alcohol.

As epoxy group-containing monomers, unsaturated glycidyl ethers (allyl glycidyl ether, 2-methylallyl glycidyl ether, vinyl glycidyl ether, etc.), unsaturated glycidyl esters (glycidyl acrylate, glycidyl methacrylate, etc.) dill, etc.).

As an isocyanate group-containing monomer, 2-(meth)acryloyloxyethyl isocyanate, 2-(2-(meth)acryloyloxyethoxy)ethyl isocyanate, 1,1-bis((meth)acryloyloxymethyl ) Ethyl isocyanate, etc. can be mentioned.

The amount of reactive functional group contained in the fluorinated resin (B) having a functional group is preferably 0.01 to 3 mol%, and more preferably 0.03 to 2 mol%, based on the total units constituting the fluorinated resin (B) having a functional group. And 0.05 to 1 mol% is more preferable. If the amount of reactive functional group is within the above range, reactivity with PAS resin is excellent and deterioration of fluidity can be suppressed.

The melting point of the fluorinated resin (B) used in the present invention is not particularly limited, but is 170°C to 320°C, preferably 180°C to 310°C, and more preferably 190°C to 300°C. If the melting point of the fluorinated resin (B) is within the above range, heat resistance can be maintained and good melt extrusion stability can be obtained.

The glass transition temperature of the fluorinated resin (B) used in the present invention is not particularly limited, but is 110°C or lower, and is more preferably 100°C or lower. If the fluorine-containing resin (B) has the above glass transition temperature, during stretching after mixing with the PAS-based resin (A), the dispersed phase of the fluorinated resin (B) is also stretched at the stretching temperature of the PAS-based resin (A). , peeling at the interface between the PAS-based resin (A), which is a continuous phase, and the fluorinated resin (B), which is a dispersed phase, can be suppressed. As a result, a film that can suppress fracture during stretching and has excellent mechanical properties is obtained.

The content of the fluorinated resin (B) in the resin composition may be 5 to 49% by mass, but is preferably 10 to 40% by mass. When the content of the fluorine-containing resin (B) is within the above range, the effect of improving the dielectric properties (lower dielectric constant) of the film is more significantly exhibited.

In the present invention, it is also possible to use a fluorinated resin containing a reactive functional group together with the fluorinated resin (B).

[Thermoplastic resin (C) other than fluorine-containing resin (B)]

The thermoplastic resin (C) (hereinafter sometimes referred to as “thermoplastic resin (C)”) other than the fluorinated resin (B) of the present invention is a fluorinated resin with a glass transition temperature of 140°C or higher or a melting point of 270°C or lower. Any thermoplastic resin other than resin may be used. If the thermoplastic resin (C) has a glass transition temperature of 140°C or higher or a melting point of 270°C or lower, when bonding the stretched film obtained from the resin composition of the present invention to a metal, the stretched film and the metal can be thermally bonded at the melting point or lower of the PPS resin. You can. Because of thermal bonding below the melting point of the PPS resin, bonding becomes possible without deforming the stretched film. Additionally, if it is a thermoplastic resin with the above-mentioned thermal properties, the heat resistance of the PPS resin can be maintained.

The thermoplastic resin (C) other than the fluorinated resin (B) may be any thermoplastic resin other than the fluorinated resin with a glass transition temperature of 140°C or higher or a melting point of 270°C or lower. For example, polycarbonate, polyphenylene ether, Various polymers such as polyethersulfone, polyphenylenesulfone, polyetherimide, and blends containing at least one of these polymers can be used. Among them, polyphenylene ether is preferable from the viewpoint of low dielectric properties and miscibility with PAS.

As the thermoplastic resin (C) contained in the resin composition of the present invention, polyphenylene ether-based resin (hereinafter sometimes referred to as “PPE-based resin”) is preferably used.

PPE-based resin is a polymer containing the structure represented by the following formula (9) as a repeating unit.

In the above formula, R ² is each independently 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 hydrocarbonoxy group, It is a halohydrocarbonoxy group in which at least two carbon atoms separate a halogen atom from an oxygen atom, and m is each independently an integer of 1 to 4.

Specific examples of PPE-based resins include poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), and poly(2-methyl-6). -Phenyl-1,4-phenylene ether), monopolymers such as poly(2,6-dichloro-1,4-phenylene ether), 2,6-dimethylphenol and other phenols (e.g., 2,3-phenylene ether) , 6-trimethylphenol or 2-methyl-6-butylphenol) copolymers, etc. can be mentioned.

Among these, the PPE-based resin is preferably poly(2,6-dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, and poly(2 ,6-dimethyl-1,4-phenylene ether) is more preferable.

The number average molecular weight of the PPE-based resin is preferably 1,000 or more, more preferably 1,500 to 50,000, and still more preferably 1,500 to 30,000.

The content of the thermoplastic resin (C) in the resin composition of the present invention may be 1 to 40% by mass, but is preferably 5 to 35% by mass. If the content of the thermoplastic resin (C) is within the above range, the physical properties of the stretched film are maintained, and the effect of improving adhesion to the metal becomes more noticeable.

[Modified elastomer (D)]

The modified elastomer (D) has a reactive group capable of reacting with at least one of the PAS-based resin (A), the fluorinated resin (B), and the thermoplastic resin (C), thereby improving the mechanical strength (fold resistance, etc.) of the film. It is an ingredient that has a function.

The reactive group that the modified elastomer (D) has is preferably at least one selected from the group consisting of an epoxy group and an acid anhydride group, and more preferably an epoxy group. These reactive groups can react quickly with the functional groups at the molecular ends of the PAS-based resin (A), fluorinated resin (B), and thermoplastic resin (C).

Such modified elastomer (D) includes a copolymer containing a repeating unit based on an α-olefin, a repeating unit based on a vinyl polymerizable compound having the above functional group, a repeating unit based on an α-olefin, and the above functional group. and a copolymer containing a repeating unit based on a vinyl polymerizable compound and a repeating unit based on an acrylic acid ester.

Examples of the α-olefin include α-olefins having 2 to 8 carbon atoms, such as ethylene, propylene, and butene-1.

In addition, vinyl polymerizable compounds having functional groups include α,β-unsaturated carboxylic acids and their esters such as acrylic acid, methacrylic acid, acrylic acid ester, and methacrylic acid ester, maleic acid, fumaric acid, itaconic acid, and other carbon atoms of 4 to 10. α,β-unsaturated dicarboxylic acids such as unsaturated dicarboxylic acids, mono- or diesters thereof, and acid anhydrides thereof, esters thereof, acid anhydrides thereof, and α,β-unsaturated glycidyl esters.

The α,β-unsaturated glycidyl ester is not particularly limited, but includes compounds represented by the following formula (10).

In the above formula, R ³ is an alkenyl group having 1 to 6 carbon atoms.

Examples of alkenyl groups having 1 to 6 carbon atoms include vinyl group, 1-propenyl group, 2-propenyl group, 1-methylethenyl group, 1-butenyl group, 2-butenyl group, 1-methyl-1-propenyl group, and 1- Methyl-2-propenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-methyl-1 -pentenyl group, 1-methyl-3-pentenyl group, 1,1-dimethyl-1-butenyl group, 1-hexenyl group, 3-hexenyl group, etc.

R ⁴ each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 2-methylbutyl, and 3-methylbutyl. , 2,2-dimethylpropyl group, hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group group, 2,4-dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, etc.

Specific examples of α,β-unsaturated glycidyl ester include glycidyl acrylate and glycidyl methacrylate, and glycidyl methacrylate is preferable.

The proportion of repeating units based on α-olefin in the modified elastomer (D) is preferably 50 to 95% by mass, and more preferably 50 to 80% by mass. If the ratio occupied by the repeating unit based on α-olefin is within the above range, the stretching uniformity, fold resistance, etc. of the film can be improved.

Moreover, the ratio of the repeating unit based on the vinyl polymerizable compound having a functional group in the modified elastomer (D) is preferably 1 to 30% by mass, and more preferably 2 to 20% by mass. If the ratio occupied by the repeating unit based on the vinyl polymerizable compound having a functional group is within the above range, not only the desired improvement effect but also good extrusion stability can be obtained.

The content of the modified elastomer (D) in the resin composition is preferably 1 to 15 mass%, and more preferably 3 to 10 mass%. When the content of the modified elastomer (D) is within the above range, the effect of improving the dielectric properties, tear resistance, etc. of the film is significantly exhibited.

[Styrene-methacrylic acid copolymer (E)]

The resin composition preferably further contains styrene-methacrylic acid copolymer (E). Styrene-methacrylic acid copolymer (E) is a component that has the function of improving fluidity and dispersibility of the dispersed phase.

In addition, if the styrene-methacrylic acid copolymer (E) also functions as a compatibilizer as described later, it reacts with the modified elastomer (D) considered by the present inventors, and the PAS-based resin (A) and the thermoplastic resin (C) Among them, polyphenylene ether-based resin also has the function of increasing interfacial adhesion and improving the mechanical strength (fold resistance, etc.) of the biaxially stretched film.

Styrene-methacrylic acid copolymer (E) is a copolymer of a styrene-based monomer and a methacrylic acid-based monomer.

The styrene-based monomer is not particularly limited, but includes styrene and its derivatives. Examples of styrene derivatives include alkyl styrene such as methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, and octyl styrene; Halogenated styrenes such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, and iodostyrene; nitrostyrene; acetylstyrene; Methoxystyrene, etc. can be mentioned. These styrene-based monomers may be used individually or in combination of two or more types.

Examples of methacrylic acid-based monomers include, in addition to methacrylic acid, methacrylic acid alkyl esters having a substituted or unsubstituted alkyl group of 1 to 6 carbon atoms. In this case, the substituent is not particularly limited, but includes halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom, and hydroxyl group. In addition, the substituent may have only one or two or more substituents. When having two or more substituents, each substituent may be the same or different.

Specific examples of methacrylic acid alkyl esters having a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, and t-methacrylate. Butyl, n-hexyl methacrylate, cyclohexyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, etc. are mentioned. Among them, from the viewpoint of compatibility and reactivity with the modified elastomer (D), it is preferable that the methacrylic acid alkyl ester is methacrylic acid. In addition, these methacrylic acid-based monomers may be used individually by 1 type, or may be used in combination of 2 or more types.

The content of repeating units based on methacrylic acid contained in the styrene-methacrylic acid copolymer (E) is preferably 1 to 30% by mass, more preferably 1 to 20% by mass, of the total repeating units, It is more preferable that it is 1-18 mass %. In this case, good compatibility of the styrene-methacrylic acid copolymer (E) with the PPE-based resin (C) and the modified elastomer (D) is obtained, and the stretching uniformity, tear resistance, etc. of the biaxially stretched film can be further improved. there is.

For the polymerization reaction of the styrene-methacrylic acid copolymer (E), a widely used method for polymerizing styrene-based monomers can be applied.

The polymerization method is not particularly limited, but bulk polymerization, suspension polymerization, or solution polymerization is preferable. Among them, from the viewpoint of production efficiency, continuous bulk polymerization is particularly preferable as the polymerization method. For example, by performing continuous bulk polymerization using an apparatus equipped with one or more stirred reactors and a tubular reactor in which a plurality of mixing elements without moving parts are fixed, styrene-metapolymerization with excellent properties can be produced. Crylic acid copolymer (E) can be obtained.

In addition, thermal polymerization can be carried out without using a polymerization initiator, but it is preferable to use various radical polymerization initiators. Additionally, polymerization aids such as suspensions and emulsifiers required for the polymerization reaction can be compounds used in the production of ordinary polystyrene.

In order to reduce the viscosity of the reactants in the polymerization reaction, an organic solvent may be added to the reaction system. Examples of such organic solvents include toluene, ethylbenzene, xylene, acetonitrile, benzene, chlorobenzene, dichlorobenzene, anisole, cyanobenzene, dimethylformamide, N,N-dimethylacetamide, methyl ethyl ketone, etc. can be mentioned. These organic solvents may be used individually by one type, or may be used in combination of two or more types.

As a radical polymerization initiator, for example, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)butane, 2,2-bis(4,4-dibutyl) Peroxyketals such as peroxycyclohexyl)propane; Hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide; dialkyl peroxides such as di-t-butyl peroxide, dicumyl peroxide, and di-t-hexyl peroxide; diacyl peroxides such as benzoyl peroxide and dicinamoyl peroxide; Peroxy esters such as t-butyl peroxybenzoate, di-t-butyl peroxyisophthalate, and t-butyl peroxyisopropyl monocarbonate; N,N'-azobisisobutylnitrile, N,N'-azobis(cyclohexane-1-carbonitrile), N,N'-azobis(2-methylbutyronitrile), N,N'-azo Bis(2,4-dimethylvaleronitrile), N,N'-azobis[2-(hydroxymethyl)propionitrile], etc. can be mentioned. These radical polymerization initiators may be used individually by one type, or may be used in combination of two or more types.

Additionally, a chain transfer agent may be added to the reaction system so that the molecular weight of the resulting styrene-methacrylic acid copolymer (E) does not become excessively large.

As the chain transfer agent, either a monofunctional chain transfer agent having one chain transfer group or a polyfunctional chain transfer agent having a plurality of chain transfer groups can be used.

Examples of monofunctional chain transfer agents include alkyl mercaptans and thioglycolic acid esters. As a multifunctional chain transfer agent, the hydroxyl group in polyhydric alcohols such as ethylene glycol, neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, and sorbitol is esterified with thioglycolic acid or 3-mercaptopropionic acid. Compounds, etc. can be mentioned. These chain transfer agents may be used individually, or may be used in combination of two or more types.

In addition, in order to suppress gelation of the obtained styrene-methacrylic acid copolymer (E), long-chain alcohols, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyoleyl ether, polyoxyethylene alkenyl ether, etc. are also used. It is possible.

The content of the styrene-methacrylic acid copolymer (E) in the resin composition is preferably 0.5 to 10 mass%, more preferably 0.5 to 5 mass%, and particularly preferably 1 to 5 mass%. . If the content of the styrene-methacrylic acid copolymer (E) is within the above range, the stretching uniformity, tear resistance, etc. of the biaxially stretched film can be further improved.

In the present invention, the function of increasing the compatibility (interaction) of the PAS-based resin (A) with other components (fluorinated resin (B), thermoplastic resin other than fluorinated resin (C), modified elastomer (D)) is provided. It is preferable to use a silane coupling agent as a component, and the dispersibility of other components in the PAS-based resin (A) is greatly improved, and a good morphology can be formed.

The silane coupling agent is preferably a compound having a functional group that can react with a carboxyl group. This silane coupling agent is any one of PAS-based resin (A), fluorinated resin (B), thermoplastic resin other than fluorinated resin (C), modified elastomer (D), and styrene-methacrylic acid copolymer (E). By reacting with them, it bonds strongly with them. As a result, the effect of the silane coupling agent is more significantly exhibited, and the dispersibility of the fluorinated resin (B), thermoplastic resins other than the fluorinated resin (C), and modified elastomer (D) in the PAS resin (A) can be particularly increased.

Examples of such silane coupling agents include compounds having an epoxy group, an isocyanate group, an amino group, or a hydroxyl group.

Specific examples of silane coupling agents include alkoxy groups containing epoxy groups such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. Silane compound, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldiethoxysilane Alkoxysilane compounds containing isocyanato groups such as cyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane, γ-(2-aminoethyl)aminopropylmethyl Amino group-containing alkoxysilane compounds such as dimethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-hydroxypropyltrimethoxysilane, γ-hydroxypropyl and hydroxyl group-containing alkoxysilane compounds such as triethoxysilane.

The content of the silane coupling agent in the resin composition is preferably 0.01 to 5% by mass, and more preferably 0.05 to 2.5% by mass. When the content of the silane coupling agent is within the above range, the effect of improving the dispersibility of other components in the PAS-based resin (A) is significantly exhibited.

[Styrene-based resin]

The resin composition may contain a styrene-based resin. Styrene-based resin is, in principle, contained in the dispersed phase of the resin composition. In addition, since styrene-based resins are particularly highly compatible with polyphenylene ether-based resins, they may be included in a form compatible with or close to polyphenylene ether resins. The styrene-based resin has a function of improving fluidity when melted. In addition, in this specification, “styrene-based resin” means a resin other than the above-mentioned styrene-methacrylic acid copolymer, with styrene-based monomer as the main monomer unit.

The styrene-based resin is not particularly limited, but includes polymers of styrene-based monomers. At this time, as the styrene-based monomer, the ones described above can be used.

The styrene-based resin may be a homopolymer of styrene-based monomers, or may be a copolymer formed by copolymerizing two or more types. For example, a copolymer of an unsaturated monomer having a glycidyl group or an oxazoline group and a monomer containing styrene as a main component, a block copolymer obtained by copolymerizing a styrene monomer and a conjugated diene compound, and this block copolymer can be further hydrogenated. and hydrogenated block copolymers obtained by addition reaction. Additionally, rubber-modified styrene (high impact styrene) may be used using rubber components such as polybutadiene, styrene-butadiene copolymer, polyisoprene, and butadiene-isoprene copolymer.

In addition, the styrene-based resin mentioned above may be used individually, or may be used in combination of two or more types.

[additive]

The resin composition may contain a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, an ultraviolet ray stabilizer, a lubricant, an antistatic agent, a colorant, a conductive agent, etc., as long as the effect of the present invention is not impaired.

＜Resin composition and manufacturing method＞

The method for producing the resin composition is not particularly limited, but includes PAS-based resin (A), fluorinated resin (B), thermoplastic resin other than fluorinated resin (C), modified elastomer (D), and styrene-(meth)acrylic acid. A method includes uniformly mixing the copolymer (E) and, if necessary, other components using a tumbler or Henschel mixer, and then melting and kneading the mixture by putting it into a twin screw extruder, and this melt kneading is kneading in a shear flow field. , kneading in an elongated flow field, or both may be used. This melt kneading is preferably performed under conditions where the ratio (discharge amount/screw rotation speed) of the discharge amount (kg/hr) of the kneaded material and the screw rotation speed (rpm) is 0.02 to 0.2 (kg/hr·rpm).

The set temperature at the time of mixing is selected to be in the range of +5 to 70℃, and +10 to 50℃ higher than the melting point of the resin with the higher melting point among PAS resin (A) and fluorinated resin (B). desirable. When the set temperature is lower than the melting point of the PAS-based resin (A) and the fluorinated resin (B), the viscosity of the composition may decrease due to the presence of the PAS-based resin (A) or the fluorinated resin (B) that does not partially melt. It is undesirable in terms of productivity because it increases significantly and increases the load on the twin-screw extruder.

In more detail, a method of putting each component into a twin-screw extruder and melt-kneading the ingredients at the above set temperature under temperature conditions of about 310°C, which is the resin temperature in the strand die, is preferable. At this time, the discharge amount of the kneaded material is in the range of 5 to 50 kg/hr at a rotation speed of 250 rpm. In particular, from the viewpoint of improving the dispersibility of each component, it is preferable that the discharge amount of the kneaded material is 20 to 35 kg/hr at a rotation speed of 250 rpm. Therefore, it is more preferable that the ratio (discharge amount/screw rotation speed) of the discharge amount of the kneaded material (kg/hr) and screw rotation speed (rpm) is 0.08 to 0.14 (kg/hr·rpm).

＜Film＞

The film of the present invention is formed from the above resin composition.

In one embodiment of such a film, the PAS-based resin (A) is used as a matrix (continuous phase), and particles (dispersed phase) containing the fluorinated resin (B) and the thermoplastic resin (C) are dispersed in this matrix.

In addition, the modified elastomer (D) is on the surface of the particles of the fluorinated resin (B) or thermoplastic resin (C) (i.e., the interface between the matrix and the particles), inside the particles of the fluorinated resin (B) or thermoplastic resin (C), Alternatively, it exists as particles (disperse phase) separate from the particles of the fluorinated resin (B) and thermoplastic resin (C).

In addition, the present inventors have found that the modified elastomer (D) also functions as a compatibilizer for the PAS-based resin (A), the fluorinated resin (B), and the thermoplastic resin (C), so that the particles are finely dispersed in the matrix, thereby improving the mechanical properties of the film. I think the strength is improving. In addition, the present inventors believe that the combined use with a silane coupling agent further improves the adhesion at the interface between the matrix and the particles via the modified elastomer (D), thereby further improving the mechanical strength of the film.

The film is preferably a biaxially stretched film obtained by biaxially stretching a sheet obtained from a resin composition.

When a biaxially stretched film is used, the PAS-based resin (A) constituting the matrix crystallizes while its molecular chain is stretched, so a film with high dimensional accuracy can be obtained.

The stretch ratio in the longitudinal direction (MD direction) of the biaxially stretched film is preferably 1.5 to 4 times, and more preferably 2.0 to 3.8 times.

Moreover, the stretch ratio in the width direction (TD direction) of the biaxially stretched film is preferably 1.5 to 4 times, and more preferably 2.0 to 3.8 times.

In addition, the ratio of the stretch ratio in the width direction (TD direction) of the biaxially stretched film to the stretch ratio in the longitudinal direction (MD direction) of the biaxially stretched film (width direction (TD direction)/(longitudinal direction (MD direction)) is: It is preferable that it is 0.8 to 1.3, and since it is easy to balance the physical properties in the longitudinal direction and the physical properties in the width direction, it is more preferable that it is 0.9 to 1.2.

＜Manufacturing method of biaxially stretched film＞

A biaxially stretched film is manufactured as follows, for example.

First, the resin composition is dried at 140°C for more than 3 hours and then placed into an extruder heated to 280-320°C.

Thereafter, the molten resin composition (i.e., kneaded product) that has passed through the extruder is discharged in the form of a sheet (film) from a T die.

Next, the sheet-shaped kneaded material is cooled and solidified by bringing it into close contact with a cooling roll with a surface temperature of 20 to 50°C. As a result, an unstretched sheet in a non-oriented state is obtained.

Next, the unstretched sheet is biaxially stretched. As a stretching method, a sequential biaxial stretching method, a simultaneous biaxial stretching method, or a method combining these can be used.

In the case of biaxial stretching by the sequential biaxial stretching method, for example, the obtained unstretched sheet is heated with a group of heating rolls and stretched 1.5 to 4 times (preferably 2.0 to 3.8 times) in the longitudinal direction (MD direction), After stretching in one or two or more stages, it is cooled with a group of cooling rolls at 30 to 60°C.

In addition, the stretching temperature is preferably between the glass transition temperature (Tg) of the PAS resin (A) and Tg+40°C, more preferably between Tg+5°C and Tg+30°C, and more preferably between Tg+5°C and Tg. +20°C is more preferred.

Next, it is stretched in the width direction (TD direction) by using a tenter. Both ends of the film stretched in the MD direction are held by clips, guided to a tenter, and stretched in the TD direction.

Moreover, the draw ratio is preferably 1.5 to 4 times, and more preferably 2.0 to 3.8 times.

Moreover, the stretching temperature is preferably from Tg to Tg+40°C, more preferably from Tg+5°C to Tg+30°C, and even more preferably from Tg+5°C to Tg+20°C.

Next, this stretched film is heat set while being tensioned or relaxed in the width direction.

The heat setting temperature is not particularly limited, but is preferably 200 to 280°C, more preferably 220 to 280°C, and even more preferably 240 to 275°C. Additionally, heat setting may be performed in two stages by changing the heat setting temperature. In this case, it is desirable to set the heat setting temperature of the second stage +10 to 40°C higher than the heat setting temperature of the first stage. The heat resistance and mechanical strength of a stretched film heat-set at a heat-setting temperature in this range are further improved.

Moreover, the heat setting time is preferably 1 to 60 seconds.

Additionally, this film is cooled while relaxing in the width direction in a temperature zone of 50 to 270°C. The relaxation rate is preferably 0.5 to 10%, more preferably 2 to 8%, and even more preferably 3 to 7%.

[Laminate]

The laminate of the present invention has the above-mentioned film (preferably a biaxially stretched film or a biaxially stretched laminated film) and a metal layer formed on at least one surface side of the film.

The constituent material (metal material) of the metal layer is not particularly limited, but includes copper, aluminum, zinc, titanium, nickel, and alloys containing these.

In addition, the metal layer may have a single-layer structure or a laminated structure of two or more layers. When the metal layers have a laminated structure, each layer may be made of the same metal material or may be made of different metal materials.

In one embodiment, the laminate may have a structure such as metal layer-film, metal layer-film-metal layer, metal layer-film-metal layer-film, metal layer-metal layer-film, metal layer-metal layer-film-metal layer, etc.

Additionally, methods for forming the metal layer include vacuum deposition of metal, sputtering, plating, etc. Additionally, the metal layer may be formed by overlapping the film and metal foil and heat welding them.

Since the film has excellent dielectric properties, such a laminate can be processed and used into a flexible printed wiring board (FPC) or flexible flat cable (FFC) suitable for next-generation high-speed transmission.

Additionally, if a biaxially stretched film with excellent stretching uniformity is used, the laminate has excellent thickness uniformity, and variation in dielectric constant can be suppressed.

Additionally, for example, an intermediate layer having a function of improving adhesion between the film and the metal layer may be provided.

Although the film and laminate of the present invention have been described above, the present invention is not limited to the configuration of the above-described embodiment.

For example, the film and the laminate of the present invention may each be added with any other configuration to the above-described embodiment, or may be replaced with any configuration that exerts the same function.

Example

Next, the present invention will be described in more detail through examples, but the present invention is not limited to these.

[Example 1]

1. Preparation of resin composition and biaxially stretched film

69.5% by mass of polyphenylene sulfide resin (A) (manufactured by DIC Corporation, linear type, melting point of 280°C, melt viscosity (V6) 110Pa·s at 300°C), and 20% by mass of fluorine-containing resin (B). (manufactured by AGC Corporation, has a functional group, "AH-2000", melting point 240°C), and 10% by mass of polyphenylene ether-based resin (C) (manufactured by Mitsubishi Engineering Plastics, poly(2,6-dimethyl-1, 4-phenylene ether), glass transition temperature 210 degrees), and 0.5% by mass of 3-glycidoxypropyltriethoxysilane were uniformly mixed with a tumbler to obtain a mixture.

Additionally, polyphenylene sulfide resin has a carboxyl group at the terminal of the molecule.

Hereinafter, polyphenylene sulfide resin is referred to as “PPS,” polyphenylene ether-based resin is referred to as “PPE,” and 3-glycidoxypropyltriethoxysilane is referred to as “silane coupling agent.”

Next, the mixture obtained above was put into a twin-screw extruder equipped with a vent (“TEX-30α” manufactured by Nippon Steel Works Co., Ltd.). Afterwards, the strand is melted and extruded under the following conditions: discharge rate of 20kg/hr, screw rotation speed of 300rpm, cylinder setting temperature of raw material supply port side of 200℃, other cylinder setting temperature of 280~320℃, and resin temperature of 300℃ in strand die. It was discharged into a shape, cooled with water at a temperature of 30°C, and then cut to prepare a resin composition.

Next, this resin composition was dried at 140°C for 3 hours, then put into a full-flight screw single-screw extruder and melted under conditions of 280 to 310°C. After extruding the molten resin composition from a T die, it was closely cooled with a chill roll set at 40°C to produce an unstretched sheet.

Next, the produced unstretched sheet was biaxially stretched 3.0 × 3.0 times at 100°C using a batch biaxial stretching machine (manufactured by Imoto Manufacturing Co., Ltd.) to obtain a film with a thickness of 50 μm. Additionally, the obtained film was fixed to a mold and heat-set in an oven at 275°C to produce a biaxially stretched film.

The average particle diameter of the particles in the produced resin composition was measured as follows.

Specifically, the prepared biaxially stretched film was cut by an ultra-thin sectioning method in (a) a direction parallel to the longitudinal direction and perpendicular to the film plane, and (b) a direction parallel to the width direction and perpendicular to the film plane. Scanning electron microscope (SEM) photographs were taken at 2000 times the cut surfaces (a) and (b) of the cut film, respectively, and the obtained images were enlarged to A3 size. Randomly selecting 50 dispersed phases in the enlarged SEM photo, measuring the maximum diameter of each dispersed phase on the cut surfaces (a) and (b), the average diameter was calculated by adding the two directions of the cut surfaces (a) and (b). .

As a result, the average particle diameter of the particles in the biaxially stretched film was 1.5 μm.

In addition, SEM-EDS analysis was performed on the cut biaxially stretched film, and the components constituting the matrix and particles of the resin composition were analyzed. As a result, it was found that the component constituting the matrix was PPS, and the component constituting the particles was a fluorine-containing resin and PPE resin.

[Example 2]

A resin composition and a biaxially stretched film were produced in the same manner as in Example 1, except that “EA-2000” (melting point 300°C) manufactured by AGC Corporation was used as the fluorine-containing resin (B).

In addition, the average particle diameter of the particles in the biaxially stretched film was measured in the same manner as in Example 1, and was found to be 1.6 μm.

Additionally, as a result of analyzing the components of the resin composition in the same manner as in Example 1, it was found that particles of fluorinated resin and PPE resin were dispersed in the PPS matrix.

[Example 3]

The same procedure as in Example 2 was carried out except that polycarbonate resin (manufactured by Mitsubishi Engineering Plastics Chemicals, glass transition temperature 145°C, hereinafter referred to as “PC”) was used as the thermoplastic resin (C), and a resin composition and two-screw A stretched film was prepared.

Additionally, the average particle diameter of the particles in the biaxially stretched film was measured in the same manner as in Example 1, and was found to be 1.3 μm.

Additionally, as a result of analyzing the components of the resin composition in the same manner as in Example 1, it was found that particles of fluorinated resin and PC resin were dispersed in the PPS matrix.

[Example 4]

Resin composition and biaxial stretching were carried out in the same manner as in Example 2, except that polyethersulfone resin (manufactured by BASF Corporation, glass transition temperature 225°C, hereinafter referred to as “PES”) was used as the thermoplastic resin (C). The film was manufactured.

In addition, the average particle diameter of the particles in the biaxially stretched film was measured in the same manner as in Example 1, and was found to be 1.8 μm.

Additionally, as a result of analyzing the components of the resin composition in the same manner as in Example 1, it was found that particles of fluorinated resin and PES resin were dispersed in the PPS matrix.

[Example 5]

The same procedure as in Example 2 was carried out, except that polyphenylene sulfone resin (manufactured by BASF Corporation, glass transition temperature 220°C, hereinafter referred to as “PPSU”) was used as the thermoplastic resin (C) other than the fluorinated resin. , a resin composition and a biaxially stretched film were prepared.

Additionally, the average particle diameter of the particles in the biaxially stretched film was measured in the same manner as in Example 1, and was found to be 1.5 μm.

In addition, as a result of analyzing the components of the resin composition in the same manner as in Example 1, it was found that particles of fluorinated resin and PPSU resin were dispersed in the PPS matrix.

[Example 6]

74.5% by mass of PPS resin, 20% by mass of EA-2000, and 5% by mass of polyetherimide resin (manufactured by SABIC Corporation, glass transition temperature 216°C, hereinafter sometimes referred to as “PEI”) to the thermoplastic resin (C). A resin composition and a biaxially stretched film were produced in the same manner as in Example 1 except that .

Additionally, the average particle diameter of the particles in the biaxially stretched film was measured in the same manner as in Example 1, and was found to be 1.9 μm.

Additionally, as a result of analyzing the components of the resin composition in the same manner as in Example 1, it was found that particles of fluorinated resin and PEI resin were dispersed in the PPS matrix.

[Example 7]

66.5% by mass of PPS resin, 20% by mass of EA-2000, 10% by mass of PPE resin, Bond First 7L (manufactured by Sumitomo Chemical Co., Ltd., ethylene/glycidyl methacrylate/methyl acrylate = 70/) to a modified elastomer having a reactive group. A stretched film was obtained in the same manner as in Example 1, except that 3/27 (mass %), hereinafter referred to as “BF7L”) was 3 mass %, and the silane coupling agent was 0.5 mass %.

Additionally, as a result of analyzing the components of the resin composition in the same manner as in Example 1, it was found that particles of fluorinated resin and PPE resin were dispersed in the PPS matrix. The average particle diameter of the particles in the biaxially stretched film was measured in the same manner as in Example 1, and was found to be 1.5 μm. Additionally, the modified elastomer existed as individually dispersed particles or existed at the interface between the matrix and the particles of the fluorinated resin.

[Example 8]

63.5% by mass of PPS resin, 20% by mass of EA-2000, 10% by mass of PPE resin, 3% by mass of BF7L, 3% by mass of styrene-methacrylic acid (2.5% of methacrylic acid amount), and 0.5% by mass of silane coupling agent. A stretched film was obtained in the same manner as in Example 1, except that the weight percentage was changed.

Additionally, as a result of analyzing the components of the resin composition in the same manner as in Example 1, it was found that particles of fluorinated resin and PPE resin were dispersed in the PPS matrix. The average particle diameter of the particles in the biaxially stretched film was measured in the same manner as in Example 1, and was found to be 1.3 μm. Additionally, the modified elastomer existed as individually dispersed particles or existed at the interface between the matrix and the particles of the fluorinated resin.

[Comparative Example 1]

PPS resin-1 was put into a twin-screw extruder equipped with a vent (“TEX-30α” manufactured by Nippon Steel Works Co., Ltd.). Afterwards, it is melt-extruded and discharged in the form of a strand under the conditions of a discharge rate of 20 kg/hr, a screw rotation speed of 300 rpm, a set temperature of 320°C, and a resin temperature of about 300°C in the strand die, cooled with water at a temperature of 30°C, and then cut. A resin composition was prepared. Next, a stretched film was obtained in the same manner as in Example 1.

[Comparative Example 2]

A stretched film was obtained in the same manner as in Example 1, except that the PPS resin was 79.5% by mass, EA-2000 was 20% by mass, and the silane coupling agent was 0.5% by mass.

[Comparative Example 3]

A mixture of 79.5% by mass of PPS resin, 20% by mass of EA-2000, and 0.5% by mass of silane coupling agent was put into a twin-screw extruder with a vent (“TEX-30α” manufactured by Nippon Steel Works Co., Ltd.), and passed through the raw material supply port. A stretched film was obtained in the same manner as in Example 1, except that melt extrusion was performed under the conditions of a set temperature of 280°C for the side cylinder, a set temperature of 300°C for the two cylinders at the tip of the die, and a set temperature for the other cylinders of 240°C.

2. Evaluation

2-1. stretching

Success rate of obtaining a stretched film without breaking by performing biaxial stretching of 30 sheets.

[Evaluation standard]

◎: 90% or more

○: 70% or more

×: less than 70%

2-2. permittivity

The dielectric constant was determined based on the cavity resonance method specified in JIS C 2565:1992. Specifically, a strip of 2 mm in width x 150 mm in length was produced from a biaxially stretched sheet. Next, the produced strip was left to stand for 24 hours in an environment of 23°C and 50%Rh, and then the dielectric constant was measured at a frequency of 1 GHz by the cavity resonance method using the ADMS010c series (manufactured by AT Co., Ltd.).

[Evaluation standard]

○; Dielectric constant 3.2 or less

×; Dielectric constant greater than 3.2

2-3. adhesiveness

The rolled copper foil (thickness 18 μm, Rz 0.9 μm) and the stretched film were directly overlapped, and the copper foil and the stretched film were heat-pressed using a heat press at 270°C/5 MPa to produce a test piece.

Adhesion was evaluated according to the following standards by measuring the peel strength of the conductor and stretched film based on the test method specified in JIS K 6854:1999.

◎: 5N/cm or more

○: 4N/cm or more but less than 5N/cm

×: Less than 4N/cm

The above results are shown in Tables 1 to 3.

Claims (15)

Polyarylene sulfide resin (A) as the main component, fluorinated resin (B), and a thermoplastic resin (C) other than the fluorinated resin (B) with a glass transition temperature of 140°C or higher or a melting point of 270°C or lower as raw materials. It is a resin composition having a continuous phase and a dispersed phase,
The continuous phase includes polyarylene sulfide resin (A),
A polyarylene sulfide resin composition in which the dispersed phase contains a fluorinated resin (B) and a thermoplastic resin (C) other than the fluorinated resin (B). In claim 1,
A polyarylene sulfide resin composition in which the polyarylene sulfide resin (A) is 51 to 95% by mass. In claim 1 or claim 2,
A resin composition wherein the dispersed phase of the fluorinated resin (B) and the thermoplastic resin (C) other than the fluorinated resin (B) having a glass transition temperature of 140°C or higher or a melting point of 270°C or lower has an average dispersion diameter of 0.5 μm to 7 μm. The method according to any one of claims 1 to 3,
A resin composition wherein the fluorinated resin (B) is a fluorinated resin having at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, and an isocyanate group. The method according to any one of claims 1 to 3,
The ratio of the blending amount of the above-mentioned fluorinated resin (B) is 5 to 49% by mass with respect to 100% by mass of the total amount of the polyarylene sulfide resin (A), the fluorinated resin (B), and the thermoplastic resin (C) other than the fluorinated resin. % by mass of the resin composition. The method according to any one of claims 1 to 5,
The thermoplastic resin (C) other than the fluorinated resin (B) having a glass transition temperature of 140°C or higher or a melting point of 270°C or lower is polyphenylene ether resin, polycarbonate resin, polyethersulfone resin, polyphenylsulfone resin, poly A resin composition comprising at least one polymer selected from the group consisting of etherimide resin. The method according to any one of claims 1 to 6,
The ratio of the thermoplastic resin (C) other than the fluorinated resin (B) having a glass transition temperature of 140°C or higher or a melting point of 270°C or lower is polyarylene sulfide resin (A), fluorinated resin (B), and fluorinated resin. A resin composition that is 1 to 40% by mass with respect to 100% by mass of the total amount of other thermoplastic resins (C). The method according to any one of claims 1 to 7,
Additionally, a resin composition containing a modified elastomer (D) to which a reactive group is imparted. In claim 8,
A resin composition in which the modified elastomer (D) is made of an olefin-based polymer having at least one functional group selected from the group consisting of an epoxy group and an acid anhydride group. In claim 8 or claim 9,
The ratio of the amount of the modified elastomer (D) mixed is 100% by mass of the total of the polyarylene sulfide resin (A), the fluorinated resin (B), the thermoplastic resin other than the fluorinated resin (C), and the modified elastomer (D). A resin composition in the range of 1 to 15% by mass. The method according to any one of claims 1 to 10,
Additionally, a resin composition containing styrene-(meth)acrylic acid copolymer (E). In claim 11,
A resin composition in which the compounding amount of the styrene-(meth)acrylic acid copolymer (E) is in the range of 0.5 to 10 mass%. A biaxially stretched film obtained by biaxially stretching the resin composition according to any one of claims 1 to 12. A biaxially stretched laminated film having at least one layer made of the resin composition according to any one of claims 1 to 12. A laminate comprising the biaxially stretched film or biaxially stretched laminated film according to claim 13 or 14, and a metal layer disposed on at least one surface of the biaxially stretched film or biaxially stretched laminated film.