CN115637046A - Polyarylene sulfide resin composition, and biaxially stretched film, laminate, and circuit board using same - Google Patents

Abstract

The present invention relates to a polyarylene sulfide resin composition, and a biaxially stretched film, a laminate, and a circuit board using the same. Providing: a resin composition which can be directly thermally bonded to a metal or a resin molded body at a temperature not higher than the melting point of a polyarylene sulfide resin, a biaxially stretched film using the same, and a laminate having good appearance. The present inventors have found that the following resin composition can be used to solve the problems, and have completed the present invention: the polyarylene sulfide resin (A) is used as a main component, and the thermoplastic resin (B) and the carbodiimide compound (C) are contained in addition to the polyarylene sulfide resin (A) having a glass transition temperature of 140 ℃ or higher or a melting point of 270 ℃ or lower.

Description

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

Technical Field

The present invention relates to: a polyarylene sulfide resin composition having excellent thermal adhesion to a metal and/or resin molded body and low dielectric characteristics, and a biaxially stretched film, a laminate, and a circuit board using the same.

Background

In recent years, with the development of cloud and IoT (Internet of Things), electric vehicles and hybrid vehicles, and the improvement of technologies for automatic operation of vehicles, a great deal of data processing, high speed, and simultaneous multiple connections have been carried out, and low transmission loss is required in the field of flexible printed circuit boards (FPCs). However, since polyimide films (PI) used as substrates of many FPCs have poor dielectric properties and are not suitable for the same application, research and production of FPCs using Liquid Crystal Polymers (LCP) as substitute films are actively conducted. However, LCP has a high difficulty in film formation, and thus has few manufacturers who can form films, and when used for high-speed transmission, it is required to be laminated with a copper foil having a low roughness.

On the other hand, films using polyarylene sulfide resins represented by polyphenylene sulfide resins (PPS) are excellent in heat resistance, flame retardancy, chemical resistance, and electrical insulation, and therefore are used as insulating materials for capacitors and motors, and heat resistant belts. Since polyarylene sulfide resins have excellent dielectric properties compared to PI and PET, they are used in the field of flexible printed circuit boards (FPC). However, polyarylene sulfide films generally have the following problems: the adhesive properties and adhesion properties with metals and other resins are low, and the reactivity with adhesives is poor. As a means for improving this, for example, patent document 1 describes a biaxially stretched film in which a polyarylene sulfide resin and a thermoplastic resin other than the polyarylene sulfide resin are laminated on at least one surface of a metal plate.

Documents of the prior art

Patent literature

Patent document 1: japanese patent laid-open publication No. 2007-276456

Disclosure of Invention

Problems to be solved by the invention

However, patent document 1 does not describe that a biaxially stretched film containing a polyarylene sulfide resin and a thermoplastic resin other than the polyarylene sulfide resin is directly bonded to a metal in a laminate in which a layer containing a low-melting-point polyphenylene sulfide resin or a non-oriented polyphenylene sulfide sheet and a metal plate are directly laminated. Further, a layer containing a low-melting-point polyphenylene sulfide resin needs to be formed into a multilayer by coextrusion of a polyarylene sulfide resin and a thermoplastic resin layer different from the polyarylene sulfide resin, or formed into a laminate with a non-oriented polyphenylene sulfide sheet, and there is a problem of poor productivity.

Accordingly, the present invention provides: a resin composition which can be directly thermally bonded to a metal or a resin molded body at a temperature not higher than the melting point of a polyarylene sulfide resin, a biaxially stretched film using the same, and a laminate and a circuit board having good appearance.

Means for solving the problems

The present inventors have conducted intensive studies and, as a result, have found that: the present inventors have completed the present invention by solving the above problems by using a resin composition which contains a polyarylene sulfide resin (a) as a main component, and a thermoplastic resin (B) other than the polyarylene sulfide resin (a) having a glass transition temperature of 140 ℃ or higher or a melting point of 270 ℃ or lower, and a carbodiimide compound (C).

That is, the present invention relates to the following (1) to (16). Relates to the following steps:

(1) A polyarylene sulfide resin composition which comprises a polyarylene sulfide resin (A) as a main component, and a thermoplastic resin (B) other than the polyarylene sulfide resin (A) having a glass transition temperature of 140 ℃ or higher or a melting point of 270 ℃ or lower and a carbodiimide compound (C) as raw materials, the polyarylene sulfide resin composition having a continuous phase and a dispersed phase,

the continuous phase comprises a polyarylene sulfide resin (A),

the dispersed phase contains a thermoplastic resin (B) other than the polyarylene sulfide resin (A).

(2) The resin composition according to claim 1, wherein the thermoplastic resin (B) other than the polyarylene sulfide resin as the dispersed phase has an average dispersion diameter of 5 μm or less.

(3) The resin composition according to 1 or 2, wherein a ratio of a blending amount of the thermoplastic resin (B) other than the polyarylene sulfide resin is in a range of 1 to 49% by mass with respect to 100% by mass of the total amount of the polyarylene sulfide resin (A), the thermoplastic resin (B) and the carbodiimide compound (C).

(4) The resin composition according to any one of claims 1 to 3, wherein the thermoplastic resin (B) other than the polyarylene sulfide resin is at least one resin selected from the group consisting of polyphenylene ether resins, polycarbonate resins, polyether sulfone resins, polyphenylene sulfone resins, polyether imide resins and polysulfone resins.

(5) The resin composition according to any one of claims 1 to 4, wherein the blending amount of the carbodiimide compound (C) is contained in a ratio of 0.1 to 5% by mass with respect to the total mass of the polyarylene sulfide resin (A), the thermoplastic resin (B) and the carbodiimide compound (C).

(6) The resin composition according to any one of claims 1 to 5, further comprising a modified elastomer (D) to which a reactive group is imparted.

(7) The resin composition according to claim 6, wherein the modified elastomer (D) comprises an olefin polymer having at least 1 functional group selected from the group consisting of an epoxy group and an acid anhydride group.

(8) The resin composition according to claim 6 or 7, wherein the amount of the modified elastomer (D) is 1 to 15% by mass based on 100% by mass of the total of the polyarylene sulfide resin (A), the thermoplastic resin (B) other than the polyarylene sulfide resin, the carbodiimide compound (C) and the modified elastomer (D).

(9) The resin composition according to any one of claims 6 to 8, wherein the modified elastomer (D) has an α -olefin content of 50 to 95% by mass based on the total mass of the modified elastomer.

(10) The resin composition according to any one of claims 1 to 9, further comprising 0.01 to 5 mass% of a silane coupling agent (E) containing at least 1 functional group selected from an epoxy group, an amino group and an isocyanate group.

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

(12) The resin composition according to claim 11, wherein the styrene- (meth) acrylic acid copolymer (F) is contained in an amount of 0.1 to 10% by mass.

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

(14) A biaxially stretched laminate film having at least 1 layer comprising the resin composition described in any one of 1 to 12.

(15) A laminate, comprising: 13 or 14 or a biaxially stretched laminated film; and 1 or more of a metal layer or a resin molded article disposed on at least one surface of the biaxially stretched film or the biaxially stretched laminated film.

(16) A circuit board comprising the biaxially stretched film, the biaxially stretched laminated film or the laminate of any one of claims 13 to 15.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a biaxially stretched film using a resin composition comprising a polyarylene sulfide resin (a), a thermoplastic resin (B) other than the polyarylene sulfide resin (a) having a glass transition temperature of 140 ℃ or higher or a melting point of 270 ℃ or lower, and a carbodiimide compound (C) can be used to maintain the excellent heat resistance, flame retardancy, chemical resistance, and moist heat resistance originally possessed by the polyarylene sulfide resin (a), and can be directly thermally bonded to a metal or resin molded body at a temperature lower than the melting point of the polyarylene sulfide resin.

Detailed Description

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

[ resin composition ]

The resin composition comprises a polyarylene sulfide resin (hereinafter, may be referred to as "PAS resin") as a main component, and a thermoplastic resin other than the polyarylene sulfide resin having a glass transition temperature of 140 ℃ or higher or a melting point of 270 ℃ or lower, and a carbodiimide compound as raw materials. In this case, the resin composition has a continuous phase containing a polyarylene sulfide resin and a dispersed phase containing a thermoplastic resin (B) other than the polyarylene sulfide resin having a glass transition temperature of 140 ℃ or higher or a melting point of 270 ℃ or lower.

The average dispersion diameter of the dispersed phase is 5 μm or less, preferably 0.5 to 5 μm, and more preferably 0.5 to 3 μm. If the dispersion diameter is less than 0.5. Mu.m, the adhesiveness to a metal or resin body is poor. When the average dispersion diameter of the dispersed phase is in the range of 0.5 to 5 μm, the film properties are maintained, and a uniform stretched film excellent in adhesion to metals can be obtained. In the present specification, the "average dispersion diameter of the dispersed phase" is a value measured by the method described in examples.

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

Here, R in the structure represented by the formula (1) ¹ Preferably both are hydrogen atoms. With the above-mentioned structure, the mechanical strength of the PAS resin (A) can be further improved. As R ¹ Examples 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 in a para position) and a structure represented by formula (3) (i.e., a structure in which a sulfur atom is bonded to an aromatic ring in a meta position).

Among these, the structure represented by formula (1) is preferably the structure represented by formula (2). If the PAS resin (a) has the structure shown in formula (2), the heat resistance and crystallinity can be further improved.

The PAS-based resin (a) may contain not only the structure represented by the above formula (1) but also structures represented by the following formulae (4) to (7) as repeating units.

The structures represented by the formulae (4) to (7) are preferably contained in an amount of 30 mol% or less, more preferably 10 mol% or less, based on the total repeating units constituting the PAS-based resin (a). With the above-mentioned structure, the heat resistance and mechanical strength of the PAS resin (A) 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 (a) 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.

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 repeating units constituting the PAS resin (a). With the above-mentioned structure, the content of chlorine atoms in the PAS based resin (A) can be reduced.

The characteristics of the PAS resin (a) 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 100 to 2000Pa · s, and more preferably 120 to 1600Pa · s from the viewpoint of good balance between flowability and mechanical strength.

Further, the PAS based resin (A) is particularly preferably: the Gel Permeation Chromatography (GPC) measurement has a peak in the molecular weight range of 25000 to 40000, a ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) in the range of 5 to 10, and a non-Newtonian index in the range of 0.9 to 1.3. By using the PAS based resin (A), the content of chlorine atoms in the PAS based resin (A) itself can be reduced to a range of 800 to 2000ppm without lowering the mechanical strength of the film, and the PAS based resin (A) can be easily used for halogen-free electronic/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 based on gel permeation chromatography ]

The device comprises the following steps: ultra-high temperature polymer molecular weight distribution measuring device (Senshu Scientific Co., ltd., SSC-7000 made by Ltd.)

Column: UT-805L (Showa Denko K.K.)

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 in a calibration with a UV detector (360 nm).

The method for producing the PAS-based resin (a) is not particularly limited, and examples thereof include the following: method 1) of polymerizing a dihalo-aromatic compound by adding a polyhaloaromatic compound or other copolymerizable components as required in the presence of sulfur and sodium carbonate; method 2) of polymerizing a dihalo-aromatic compound by adding a polyhaloaromatic compound and/or other copolymerizable components as needed in a polar solvent in the presence of a thioether reagent or the like; method 3), adding other copolymerization components as required to perform self-condensation on p-chlorothiophenol; and the like. Among these production methods, the method 2) is preferable because it is general.

In the reaction, a carboxylic acid, an alkali metal salt of a sulfonic acid, or an alkali hydroxide may be added to adjust the degree of polymerization.

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

2-1) in which a water-containing thioether is introduced into a mixture comprising a heated organic polar solvent and a dihalo-aromatic compound at such a rate that water can be removed from the reaction mixture, and the dihalo-aromatic compound is reacted with the thioether by adding the polyhaloaromatic compound to the organic polar solvent if necessary, wherein the amount of water in the reaction system is controlled to be in the range of 0.02 to 0.5 mol relative to 1 mol of the organic polar solvent, thereby producing a PAS resin (A) (see Japanese patent laid-open publication No. Hei 07-228699).

2-2), a dihalo-aromatic compound is reacted with an alkali metal hydrosulfide and an organic acid alkali metal salt by adding a polyhaloaromatic compound and/or other copolymerization components as needed in the presence of a solid alkali metal sulfide and an aprotic polar organic solvent, and 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 a sulfur source and the amount of water in the reaction system is controlled to be in the range of 0.02 mol or less relative to 1 mol of the aprotic polar organic solvent, thereby producing a PAS-based resin (a) (see pamphlet of WO 2010/058713).

Specific examples of the dihalogenated 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, p' -dihalodiphenyl ether, 4 '-dihalobenzophenone, 4' -dihalodiphenylsulfone, 4 '-dihalodiphenylsulfoxide, 4' -dihalodiphenylsulfide, and a compound 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.

The post-treatment method of the reaction mixture containing the PAS-based resin (a) obtained in the polymerization step may be any known and commonly used method. The post-treatment method is not particularly limited, and examples thereof include the following methods (1) to (5).

(1) In the method of (1), after the polymerization reaction is completed, the solvent is distilled off from the reaction mixture under reduced pressure or normal pressure as it is, or after adding an acid or an alkali, the solvent is distilled off under reduced pressure or normal pressure, and then the solid obtained after the solvent distillation removal 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 the low-molecular polymer), acetone, methyl ethyl ketone, or an alcohol, and further neutralized, washed with water, filtered, and dried.

(2) In the method (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 (a)) such as acetone, methyl ethyl ketone, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons, aliphatic hydrocarbons or the like is added as a settling agent to the reaction mixture, and a solid product such as the PAS resin (a) and an inorganic salt is settled, filtered, washed and dried.

(3) In the method of (1), after the polymerization reaction is completed, a reaction solvent (or an organic solvent having a solubility equivalent to that of the low-molecular polymer) is added to the reaction mixture and stirred, then the low-molecular polymer is filtered and removed, and then washed with a solvent such as water, acetone, methyl ethyl ketone, or alcohols 1 or 2 times or more, followed by neutralization, water washing, filtration, and drying.

(4) In the method (2), after the polymerization reaction is completed, water is added to the reaction mixture, washing with water and filtration are carried out, and when washing with water is carried out as necessary, acid treatment is carried out by adding acid, and drying is carried out.

(5) In the method (2), after the polymerization reaction is completed, the reaction mixture is filtered, washed with the reaction solvent 1 or 2 times or more as necessary, and further washed with water, filtered and dried.

Examples of the acid usable in the method (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, 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.

Examples of the hydrogen salt include sodium hydrogen sulfide, disodium hydrogen phosphate, and sodium hydrogen carbonate. Among these, organic acids which cause little corrosion to metal materials in actual use are preferable.

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

In particular, when the PAS-based resin (a) obtained by the post-treatment in the above-mentioned method (4) is mixed with the modified elastomer (D) by increasing the amount of the acid group bonded to the molecular terminal thereof, the effect of improving the dispersibility thereof can be obtained. As the acid group, a carboxyl group is particularly preferable.

The content of the PAS resin (a) in the resin composition may be 50 to 93% by mass, preferably 60 to 90% by mass. When the content of the PAS based resin (A) is within the above range, the heat resistance and chemical resistance of the film can be further improved.

The melting point of the PAS resin (A) obtained in the above is preferably 270 ℃ or higher. When the temperature is 270 ℃ or higher, deformation of the film and outflow of the resin at the time of thermal bonding to a metal or resin molded article can be suppressed, and a laminate having a good appearance can be obtained.

[ thermoplastic resin (B) other than polyarylene sulfide resin ]

The thermoplastic resin (B) other than the polyarylene sulfide resin (A) (hereinafter, may be referred to as "thermoplastic resin (B)") of the present invention may be a thermoplastic resin other than PAS resin having a glass transition temperature of 140 ℃ or higher or a melting point of 270 ℃ or lower. In the case of the thermoplastic resin (B) having a glass transition temperature of 140 ℃ or higher or a melting point of 270 ℃ or lower, when the stretched film obtained from the resin composition of the present invention is bonded to a metal or a resin molded product, the stretched film can be directly thermally bonded to the metal at a temperature of not higher than the melting point of the PPS resin. Since the PPS resin is thermally bonded at a temperature not higher than the melting point of the PPS resin, the stretched film can be bonded without deformation, the properties of the biaxially stretched film can be maintained, and the quality after thermal bonding is not deteriorated. In addition, if the thermoplastic resin having the above thermal characteristics is used, the heat resistance of the PPS resin can be maintained.

The thermoplastic resin (B) other than the PAS resin (a) may be a thermoplastic resin having a glass transition temperature of 140 ℃ or higher or a melting point of 270 ℃ or lower, and examples thereof include various polymers such as polycarbonate, polyphenylene ether, polyether sulfone, polyphenylene sulfone, polyether imide, and polysulfone, and a blend containing at least 1 of these polymers. These resins may be used alone or in combination. Among them, polyphenylene ether is preferable from the viewpoint of low dielectric characteristics and miscibility with PAS.

The polyphenylene ether resin (hereinafter, may be referred to as "PPE resin") is a component having a function of making the biaxially stretched film low in dielectric constant and dielectric loss tangent.

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

In the above formula, R ² Each independently represents a hydrogen atom, a halogen atom, a primary alkyl group having 1 to 7 carbon atoms, a secondary alkyl group having 1 to 7 carbon atoms, a phenyl group, a haloalkyl group, an aminoalkyl group, a hydrocarbyloxy group, or 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 resins 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), and copolymers of 2, 6-dimethylphenol and other phenols (e.g., 2,3, 6-trimethylphenol and 2-methyl-6-butylphenol).

Among these, 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-based resin is preferably 1000 or more, more preferably 1500 to 50000, still more preferably 1500 to 30000.

The content of the thermoplastic resin (B) in the resin composition may be 1 to 49 mass%, preferably 3 to 40 mass%. When the content of the thermoplastic resin (B) is within the above range, the biaxially stretched film can be directly thermally bonded to a metal or a resin molded product at a temperature not higher than the melting point of the polyphenylene sulfide resin while maintaining the physical properties thereof.

[ carbodiimide Compound (C) ]

The carbodiimide compound (C) of the present invention means: a compound having a carbodiimide group (-N = C = N-) in a molecule. The carbodiimide compound is capable of reacting with an active hydrogen group. The active hydrogen group is, for example, a carboxyl group, an amino group, and a hydroxyl group. By the presence of the carbodiimide compound (C) in the resin composition, the polyarylene sulfide resin (a) or the thermoplastic resin (B) reacts with the carbodiimide compound (C), whereby the cohesive force of the resin composition can be increased, and further, the interaction between the resin composition and the metal can be increased, whereby the adhesiveness can be improved.

The carbodiimide compound includes polycarbodiimide and monocarbodiimide. Polycarbodiimide has a plurality of carbodiimide groups in a molecule. The monocarbodiimides have only 1 carbodiimide group in the molecule.

The polycarbodiimide includes aliphatic polycarbodiimides whose main chain is composed of aliphatic hydrocarbons, aromatic polycarbodiimides whose main chain is composed of aromatic hydrocarbons, and cyclic polycarbodiimides.

The monocarbodiimide includes aliphatic monocarbodiimide, aromatic monocarbodiimide, and cyclic monocarbodiimide.

The content of the carbodiimide compound of the present invention is preferably 0.1% by mass or more and 5% by mass or less, more preferably 0.3% by mass or more and 3% by mass or less, and further preferably 0.5% by mass or more and 2% by mass or less. When the content is 0.1% by mass or more, the effect of improving the adhesion between the metal and the resin molded article is exhibited. If the content is 5% by mass or less, gelation is suppressed. Further, by adding the carbodiimide compound, the flowability of the resin composition can be improved, the extrusion processability can be improved, and a biaxially stretched film having good appearance can be obtained.

[ modified elastomer (D) ]

The modified elastomer (D) is in principle contained in the dispersed phase of the resin composition. The modified elastomer (D) has a function of improving the mechanical strength (tensile properties, folding strength, etc.) of the film by having a reactive group capable of reacting with at least one of the PAS resin (a) and the thermoplastic resin (B).

The reactive group of the modified elastomer (D) is preferably at least 1 selected from the group consisting of an epoxy group and an acid anhydride group, and more preferably an epoxy group. These reactive groups can rapidly react with the functional groups at the molecular terminals of the PAS resin (A) and the thermoplastic resin (B).

Examples of the modified elastomer (D) include: a copolymer comprising a repeating unit based on an α -olefin and a repeating unit based on a vinyl polymerizable compound having the above functional group; and copolymers comprising repeating units based on an α -olefin, repeating units based on a vinyl polymerizable compound having the above functional group, and repeating units based on an acrylate, and the like.

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

Examples of the vinyl polymerizable compound having a functional group include α, β -unsaturated carboxylic acids and esters thereof such as acrylic acid, methacrylic acid, acrylic acid esters, and methacrylic acid esters, α, β -unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, and unsaturated dicarboxylic acids having 4 to 10 carbon atoms, mono-or diesters thereof, and anhydrides thereof, esters thereof, and 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).

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

Examples of the alkenyl group having 1 to 6 carbon atoms include 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.

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

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

Examples of the alkyl group having 1 to 6 carbon atoms include 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, a3, 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 repeating unit based on the α -olefin in the modified elastomer (D) is preferably 50 to 95% by mass, more preferably 50 to 80% by mass. When the ratio of the repeating unit based on the α -olefin is within the above range, the film can be improved in the stretching uniformity, the folding strength, and the like.

The proportion 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, more preferably 2 to 20% by mass. 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.

The content of the modified elastomer (D) in the resin composition is preferably 1 to 15% by mass, more preferably 2 to 10% by mass. When the content of the modified elastomer (D) is within the above range, the effect of improving the folding strength of the film can be remarkably exhibited.

[ styrene-methacrylic acid copolymer (F) ]

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 fluidity of the resin composition and the stretchability of the film.

In addition, the styrene- (meth) acrylic acid copolymer (F) also has the following functions: as described later, the reaction with the modified elastomer (D) which is considered by the present inventors to function also as a compatibilizer improves the interfacial adhesion between the PAS resin (a) and the thermoplastic resin (B), and improves the mechanical strength (folding strength, etc.) of the film.

The styrene-methacrylic acid copolymer (F) is a copolymer of a styrene monomer and a methacrylic acid monomer.

The styrene monomer is not particularly limited, and styrene and derivatives thereof 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-based monomers may be used alone in 1 kind, or in combination of 2 or more kinds.

Examples of the methacrylic monomer include, in addition to methacrylic acid, alkyl methacrylates having a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. In this case, the substituent is not particularly limited, and examples thereof include 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. When the compound has 2 or more substituents, the substituents may be the same or different.

Specific examples of the alkyl methacrylate having a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and the like. Among these, methacrylic acid is preferred as the alkyl methacrylate from the viewpoint of compatibility with the modified elastomer (D) and reactivity. These methacrylic monomers may be used alone in 1 kind, or in combination in 2 or more kinds.

The content of the methacrylic acid-based repeating unit contained in the styrene- (meth) acrylic acid copolymer (F) is preferably 1 to 30% by mass, more preferably 1 to 20% by mass, and still more preferably 1 to 18% by mass of the total repeating units. In this case, the styrene- (meth) acrylic acid copolymer (F) can have good compatibility with the thermoplastic resin (B) and the modified elastomer (D), and the tensile uniformity, the folding strength, and the like of the film can be further improved.

In the polymerization reaction of the styrene- (meth) acrylic acid copolymer (F), 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 preferred. Among them, the polymerization system is particularly preferably continuous bulk polymerization for productivity. For example, a styrene- (meth) acrylic acid copolymer (F) having excellent properties can be obtained by performing continuous bulk polymerization using an apparatus in which 1 or more stirring reactors and a tubular reactor having a plurality of mixing units each having a movable part fixed therein are installed.

Although thermal polymerization may be performed 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 reaction mixture during the polymerization reaction, an organic solvent may be added to the reaction system. Examples of the organic solvent include toluene, ethylbenzene, xylene, acetonitrile, benzene, chlorobenzene, dichlorobenzene, anisole, cyanobenzene, dimethylformamide, N-dimethylacetamide, methyl ethyl ketone, and the like. These organic solvents may be used alone in 1 kind, or may be used in combination with 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 dicinnamoyl peroxide; peroxy esters such as t-butylperoxybenzoate, di-t-butylperoxyisophthalate, and t-butylperoxyisopropyl 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 of 2 or more kinds.

Further, a chain transfer agent may be added to the reaction system so that the molecular weight of the obtained styrene- (meth) acrylic acid copolymer (F) does not excessively increase.

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, thioglycolates, and the like. Examples of the polyfunctional chain transfer agent include: and compounds obtained by esterifying hydroxyl groups in polyhydric alcohols such as ethylene glycol, neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, and sorbitol with thioglycolic acid or 3-mercaptopropionic acid. These chain transfer agents may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

In addition, in order to suppress gelation of the obtained styrene- (meth) acrylic acid copolymer (F), 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 content of the styrene- (meth) acrylic acid copolymer (F) in the resin composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, and particularly preferably 1 to 5% by mass. When the content of the styrene- (meth) acrylic acid copolymer (F) is within the above range, the film can be further improved in the stretching uniformity, folding strength, and the like.

[ silane coupling agent (E) ]

In the present invention, the silane coupling agent is preferably used as a component having a function of improving the compatibility and interaction between the PAS resin (a) and other components (the thermoplastic resin (B) and the modified elastomer (D) other than the PAS resin), and the dispersibility of the other components in the PAS resin (a) is dramatically improved, and a good morphology can be formed.

The silane coupling agent (E) is preferably a compound having a functional group capable of reacting with a carboxyl group. The silane coupling agent is 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 the dispersibility of other components in the PAS resin (a) can be particularly improved.

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

Specific examples of the silane coupling agent include epoxy group-containing alkoxysilane compounds such as γ -glycidoxypropyltrimethoxysilane, γ -glycidoxypropyltriethoxysilane, β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, etc., isocyanate group-containing alkoxysilane compounds such as γ -isocyanatopropyltrimethoxysilane, γ -isocyanatopropyltriethoxysilane, γ -isocyanatopropylmethyldimethoxysilane, γ -isocyanatopropylmethyldiethoxysilane, γ -isocyanatopropylethyldimethoxysilane, γ -isocyanatopropylethyldiethoxysilane, γ -isocyanatopropyltrichlorosilane, etc., amino group-containing alkoxysilane compounds such as γ - (2-aminoethyl) aminopropylmethyldimethoxysilane, γ - (2-aminoethyl) aminopropyltrimethoxysilane, γ -aminopropyltrimethoxysilane, etc., hydroxyl group-containing alkoxysilane compounds such as γ -hydroxypropyltrimethoxysilane, γ -hydroxypropyltriethoxysilane, etc.

The content of the silane coupling agent in the resin composition is preferably 0.01 to 5% by mass, 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 resin (a) can be remarkably exhibited.

[ styrene resin ]

The resin composition may comprise a styrenic resin. Styrenic resins are in principle contained in the dispersed phase of the resin composition. In particular, the styrene-based resin may be compatible with or included in the polyphenylene ether-based resin in view of high compatibility with the polyphenylene ether-based resin. The styrene resin has a function of improving fluidity at the time of melting. In the present specification, the term "styrene resin" means: a resin having a styrene monomer as a main monomer unit, other than the above styrene-methacrylic acid copolymer.

The styrene resin is not particularly limited, and may be a polymer of a styrene monomer. In this case, the styrene-based monomer can be used as described above.

The styrene resin may be a homopolymer of a styrene monomer or a copolymer obtained by copolymerizing 2 or more kinds of styrene monomers. Examples thereof include: a copolymer of an unsaturated monomer having a glycidyl group and/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 a hydrogenated block copolymer obtained by further subjecting the block copolymer to a hydrogenation reaction. Further, rubber-modified styrene (high impact styrene) using a rubber component such as polybutadiene, a styrene-butadiene copolymer, polyisoprene, or a butadiene-isoprene copolymer may be used.

The styrene resin may be used alone, or 2 or more kinds thereof may be used in combination.

[ additives ]

The resin composition may contain a plasticizer, a weather-resistant agent, an antioxidant, a heat stabilizer, an ultraviolet stabilizer, a lubricant, an antistatic agent, a colorant, a conductive agent, and the like, as long as the effects of the present invention are not impaired.

The method for producing the resin composition is not particularly limited, and the following methods may be mentioned: the PAS resin (a) is uniformly mixed with other components (the thermoplastic resin (B) and the carbodiimide (C) other than the PAS resin) and, if necessary, other components (the modified elastomer (D) and the silane coupling agent (F)) in a tumbler mixer, a henschel mixer, or the like, and then fed into a twin-screw extruder to be melt-kneaded, which may be either or both of kneading in a shear flow field and kneading in a tensile flow field.

The melt kneading is preferably performed under the condition that the ratio of the discharge amount (kg/hour) of the kneaded material to the screw rotation speed (rpm) (discharge amount/screw rotation speed) is 0.02 to 0.2 (kg/hour/rpm).

If further detailed, the following method is preferred: the respective components were charged into a twin-screw extruder, and melt-kneaded under the conditions of a set temperature of 300 ℃ and a resin temperature of a strand die of about 330 ℃. 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. Particularly, from the viewpoint of improving the dispersibility of each component, the discharge amount of the kneaded product is preferably 20 to 35 kg/hr at a rotation speed of 250 rpm. Accordingly, the ratio of the discharge amount (kg/hour) of the kneaded material to the screw rotation speed (rpm) (discharge amount/screw rotation speed) is more preferably 0.08 to 0.14 (kg/hour/rpm).

[ film ]

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

In one embodiment of the above film, the PAS-based resin (a) is used as a matrix (continuous phase), and particles (dispersed phase) containing the thermoplastic resin (B) other than the PAS-based resin are dispersed in the matrix.

The carbodiimide compound (C) and the modified elastomer (D) are present as the surface of the particles of the thermoplastic resin (B) (i.e., the interface between the matrix and the particles), the interior of the particles of the thermoplastic resin (B), or as particles (dispersed phase) different from the particles of the thermoplastic resin (B).

The present inventors also considered that the modified elastomer (D) functions as a compatibilizer for the PAS resin (a) and the thermoplastic resin (B), and particles are finely dispersed in the matrix, whereby the film can be prevented from breaking during stretching, and the mechanical strength (folding strength, etc.) of the film can be improved. Further, the present inventors considered that the adhesion at the interface between the matrix and the particles via the modified elastomer (D) was further improved by using the silane coupling agent in combination, and the mechanical strength (folding strength and the like) of the film was further improved.

The average particle diameter (average dispersion diameter) of the particles (dispersed phase) dispersed in the matrix in a film state is preferably 5 μm or less, more preferably 0.5 to 5 μm, and still more preferably 0.5 to 3 μm. When the average particle diameter of the particles is within the above range, the biaxially stretched film maintains its performance and has good adhesion to a metal or resin molded article.

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

The biaxially stretched film of the present invention may have at least one layer comprising the resin composition of the present invention in the outermost layer, and may be a layer comprising another resin composition directly laminated or a layer comprising another resin composition laminated via an adhesive layer or the like.

The method for producing the biaxially stretched laminated film used in the present invention is not particularly limited, and for example, when a laminated structure is formed, the following coextrusion method can be mentioned: the resin or resin mixture used for each resin layer is heated and melted in a separate extruder, laminated in a molten state in a desired lamination configuration by a coextrusion lamination die method, a feedblock method, or the like, and then formed into a sheet shape by inflation, 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 biaxial stretching, the unstretched sheet obtained in the above-described manner is biaxially stretched.

As the stretching method, a sequential biaxial stretching method, a simultaneous biaxial stretching method, or a method combining them can be used.

In the case of biaxial stretching by the sequential biaxial stretching method, for example, the obtained unstretched sheet is heated on a heating roll set, stretched in multiple stages of 1 stage or 2 or more (preferably 2 to 3.8 times) in the longitudinal direction (MD direction) by 1.5 to 4 times, and then cooled on a cooling roll set at 30 to 60 ℃.

The stretching temperature is preferably from the glass transition temperature (Tg) to Tg +40 ℃ of the PAS based resin (A), more preferably from Tg +5 to Tg +30 ℃ and still more preferably from Tg +5 to Tg +20 ℃.

Next, stretching is performed in the width direction (TD direction) by a method using a tenter. Both ends of the film obtained by stretching in the MD direction were fixed with clips, introduced into a tenter, and subjected to TD stretching.

The stretch ratio is preferably 1.5 to 4 times, and more preferably 2 to 3.8 times.

The stretching temperature is preferably from Tg to Tg +40 ℃, more preferably from Tg +5 to Tg +30 ℃, and still more preferably from Tg +5 to Tg +20 ℃.

The stretched film edges are then heat set under tension or relaxed widthwise.

The heat-setting temperature is not particularly limited, but is preferably 200 to 280 ℃, more preferably 220 to 280 ℃, and still more preferably 240 to 275 ℃. The heat setting may be performed in 2 stages with the heat setting temperature changed. In this case, the heat-setting temperature in the 2 nd stage is preferably +10 to 40 ℃ higher than the heat-setting temperature in the 1 st stage. The heat resistance and mechanical strength of the stretched film obtained by heat-setting at a heat-setting temperature in this range are further improved.

The heat setting time is preferably 1 to 60 seconds.

The stretched film is cooled while being relaxed in the width direction in a temperature range of 50 to 275 ℃. The relaxation rate is preferably 0.5 to 10%, more preferably 2 to 8%, and still more preferably 3 to 7%.

The thickness of the biaxially stretched film or biaxially stretched laminate film is not particularly limited, but is preferably 10 to 300. Mu.m, more preferably 10 to 200. Mu.m, and still more preferably 10 to 150. Mu.m. The biaxially stretched film or biaxially stretched laminated film having the above-mentioned thickness has sufficient mechanical strength and insulation properties.

The biaxially stretched film of the present invention may be subjected to a surface treatment for the purpose of improving the adhesion between the biaxially 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), oxidation treatment by chemicals, ultraviolet rays, electron radiation rays, and the like. Among them, plasma treatment is preferable.

[ laminate ]

According to an aspect of the present invention, a laminate is provided. The laminate comprises the biaxially stretched film and a metal layer or a resin molded body directly disposed on at least one outermost resin layer of the biaxially stretched film. The present invention also includes a circuit board obtained by etching a metal layer from a laminate in which the metal layer is laminated on a biaxially stretched film.

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 can have a structure of metal layer-biaxially stretched film, metal layer-biaxially stretched film-metal layer-biaxially stretched film, metal layer-biaxially stretched film-metal layer, or the like.

Examples of a method for forming the metal layer include a vacuum vapor deposition method, sputtering, plating, and the like for a metal. The metal layer may be formed by a method of overlapping the biaxially stretched film and the metal foil and heat-sealing the same.

The flexible copper-clad laminate obtained by the present invention includes a biaxially stretched film having low dielectric characteristics, and therefore, the flexible printed circuit board formed by a circuit is a circuit board having low transmission loss in a high frequency band by etching of a conductor.

Examples of the resin molded article include, but are not limited to, extrusion molded articles, injection molded articles, and fiber sheets of polyolefin resins, polyester resins, nylon resins, polyarylene sulfide resins, aromatic polyamides, liquid crystal resins, and the like.

Examples

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(example 1)

1. Resin composition and production of biaxially stretched film

83.5 mass% of polyphenylene sulfide resin (A) (product of DIC Corporation, linear melting point 285 ℃, melt viscosity at 300 ℃ (V6) 160 pas), 15 mass% of polyphenylene ether resin (B) (product of Mitsubishi Engineering-Plastics Corporation, glass transition temperature 210 ℃, hereinafter sometimes referred to as "PPE"), 1 mass% of carbodiimide compound (C) (product of Nisshinbo Chemical Inc., "Carbodilite HMV-15CA", aliphatic carbodiimide, softening temperature 70 ℃, thermal decomposition temperature (5% weight reduction temperature) 330 ℃), and 0.5 mass% of 3-glycidoxypropyltriethoxysilane were uniformly mixed in a mixer drum to obtain a mixture.

The polyphenylene sulfide resin has a carboxyl group at a molecular end thereof.

Hereinafter, the polyphenylene sulfide resin is referred to as "PPS" and the 3-glycidoxypropyltriethoxysilane is referred to as "silane coupling agent".

Next, the mixture obtained above was fed into a twin-screw extruder (manufactured by Nippon Steel works, ltd. "TEX-30. Alpha.") having an exhaust port. Then, in the discharge amount of 20 kg/hour, screw speed 300rpm, barrel set temperature 300 degrees, in the strand die resin temperature is about 300 degrees C conditions for melt extrusion, strand form discharge, in the temperature of 30 degrees C water cooling, cutting and manufacturing resin composition.

Then, the resin composition was dried at 140 ℃ for 3 hours, and then charged into a single screw extruder of a full-flight screw, and melted at 280 to 310 ℃. The molten resin composition was extruded from a T-die, and then closely cooled on a cooling roll set at 40 ℃.

Then, the obtained unstretched sheet was biaxially stretched at 100 ℃ by 3.0X 3.0 times using a batch biaxial stretcher (manufactured by Kokusho Seisakusho Co., ltd.) to obtain a film having a thickness of 50 μm. The obtained film was fixed to a mold frame and heat-set in an oven at 275 ℃ to produce a biaxially stretched film.

The obtained biaxially stretched film was directly superposed on a rolled copper foil (18 μm in thickness and rz0.9 μm) and pressed under a pressure of 270 ℃/5MPa for 15 seconds in a hot press to produce a laminate of the copper foil and the stretched film.

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

First, resin composition pellets were cut in a direction perpendicular to the flow direction by a microtome method. Subsequently, a Scanning Electron Microscope (SEM) photograph was taken 2000 × of each cut surface of the cut pellet, and the obtained image was enlarged to a size of A3. Next, arbitrary 50 particles of the enlarged SEM photograph were selected, and the maximum diameter of each particle in the cut surface was measured to calculate the average particle diameter.

As a result, the average particle diameter of the particles in the resin composition pellets was 0.9. Mu.m.

In addition, SEM-EDS analysis of the cut resin pellets was performed, and the components of the matrix and particles constituting the resin composition pellets were analyzed. The result is judged: the component constituting the matrix is PPS, and the component constituting the particles is PPE resin.

(example 2)

A resin composition, a biaxially stretched film and a laminate were produced in the same manner as in example 1 except for using a polycarbonate resin (manufactured by Mitsubishi Engineering Plastics Chemical co., ltd., glass transition temperature 145 ℃, hereinafter sometimes referred to as "PC") as the thermoplastic resin (B) other than the PAS-based resin.

The average particle diameter of the particles in the resin composition was measured in the same manner as in example 1, and found to be 1.2 μm.

(example 3)

A resin composition, a biaxially stretched film and a laminate were produced in the same manner as in example 1, except that a polyether sulfone resin (manufactured by BASF corporation, glass transition temperature 225 ℃, hereinafter, sometimes referred to as "PES") was used as the thermoplastic resin (B) other than the PAS-based resin.

The average particle diameter of the particles in the resin composition was measured in the same manner as in example 1, and the result was 1.6 μm.

(example 4)

A resin composition, a biaxially stretched film and a laminate were produced in the same manner as in example 1 except that a polyphenylene sulfone resin (manufactured by BASF corporation, glass transition temperature 220 ℃ C., hereinafter sometimes referred to as "PPSU") was used as the thermoplastic resin (B) other than the PAS resin.

The average particle diameter of the particles in the resin composition was measured in the same manner as in example 1, and the result was 1.4 μm.

(example 5)

A resin composition, a biaxially stretched film and a laminate were produced in the same manner as in example 1 except that a polyetherimide resin (manufactured by SABIC, having a glass transition temperature of 216 ℃ C., hereinafter sometimes referred to as "PEI") was used as the thermoplastic resin (B) other than the PAS resin.

The average particle diameter of the particles in the resin composition was measured in the same manner as in example 1, and the result was 1.8 μm.

(example 6)

A resin composition, a biaxially stretched film and a laminate were produced in the same manner as in example 1, except that a polysulfone resin (manufactured by SOLVAY corporation, glass transition temperature 190 ℃, hereinafter sometimes referred to as "PSU") was used as the thermoplastic resin (B) other than the PAS-based resin.

The average particle diameter of the particles in the resin composition was measured in the same manner as in example 1, and found to be 1.0 μm.

(example 7)

80.5 mass% of the PPS resin (a), 15 mass% of the PPE resin (B), 1 mass% of the carbodiimide compound (C) (carbodiimide HMV-15 CA), and 1 mass% of the modified elastomer having a reactive group (D) were Bondfast 7L (manufactured by sumitomo chemical co., ltd., ethylene/glycidyl methacrylate/methyl acrylate =70/3/27 (mass%), and hereinafter may be referred to as "BF7L". ) A resin composition, a biaxially stretched film and a laminate were produced in the same manner as in example 1 except for the formulation of 3% by mass and 0.5% by mass of 3-glycidoxypropyltriethoxysilane.

The average particle diameter of the particles in the resin composition was measured in the same manner as in example 1, and found to be 1.0 μm.

(example 8)

A resin composition, a biaxially stretched film and a laminate were produced in the same manner as in example 1 except that the carbodiimide compound (C) was changed to Carbodilite LA-1 (aliphatic carbodiimide manufactured by Nisshinbo Chemical inc., softening temperature 55 ℃ C., and thermal decomposition temperature (5% weight loss temperature) 350 ℃).

The average particle diameter of the particles in the resin composition was measured in the same manner as in example 1, and was found to be 1.1 μm.

Comparative example 1

PPS was fed into a vented twin-screw extruder "TEX-30. Alpha." made by Nippon Steel works, ltd., and melt-extruded at a discharge rate of 20 kg/hr, a screw rotation speed of 300rpm, a set temperature of 300 ℃ to be discharged in the form of strands, cooled in 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 on 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 3.5X 3.5 times in a batch biaxial stretcher of Seiki Seisaku-Sho, ltd., to obtain a biaxially stretched film having a thickness of 50 μm. The obtained biaxially stretched film was fixed to a mold frame, and heat-set in an oven at 275 ℃ to obtain a biaxially stretched film.

The obtained biaxially stretched film was directly laminated with a rolled copper foil (thickness 18 μm, rz0.9 μm), and pressed at 275 ℃ under a pressure of 5MPa for 15 seconds in a hot press to prepare a laminate of the copper foil and the stretched film.

Comparative example 2

The biaxially stretched film obtained in comparative example 1 was directly laminated with a rolled copper foil (thickness: 18 μm), and pressed at 300 ℃ under a pressure of 5MPa for 15 seconds in a press to produce a laminate of a copper foil and a film.

Comparative example 3

84.5 mass% of the PPS resin, 15 mass% of a polyetherimide resin (manufactured by SABIC, inc.' PEI), which is a thermoplastic resin (B) other than PAS series resin, and 0.5 mass% of 3-glycidoxypropyltriethoxysilane were uniformly mixed in a tumbler mixer to obtain a mixture. Other than this, a biaxially stretched film and a laminate were produced in the same manner as in example 1.

[ evaluation ]

1. Appearance of laminate

In the laminate after hot pressing of the film and the copper foil, the flow-out of the film was evaluated according to the following criteria.

Good: without resin outflow

X: with outflow of resin

2. Adhesion Property

The adhesiveness was determined in accordance with JIS K6854: the peel strength was measured by the test method specified in 1999 using a laminate of a copper foil and a biaxially stretched laminate film, and evaluated according to the following criteria.

Very good: 6N/cm or more

O: 4N/cm or more and less than 6N/cm

X: less than 4N/cm

The results are shown in tables 1 to 3.

[ Table 1]

[ Table 2]

[ Table 3]

The biaxially stretched laminated films and laminates obtained in examples 1 to 8 showed good appearance of the laminate and excellent adhesiveness.

In contrast, the stretched films and laminates obtained in comparative examples 1,2 and 3 had poor appearance and poor adhesiveness.

Claims (16)

1. A polyarylene sulfide resin composition which comprises a polyarylene sulfide resin (A) as a main component, and comprises a thermoplastic resin (B) other than the polyarylene sulfide resin (A) having a glass transition temperature of 140 ℃ or higher or a melting point of 270 ℃ or lower and a carbodiimide compound (C) as raw materials, and which has a continuous phase and a dispersed phase,

the continuous phase comprises a polyarylene sulfide resin (A),

the dispersed phase contains a thermoplastic resin (B) other than the polyarylene sulfide resin (A).

2. The resin composition according to claim 1, wherein the thermoplastic resin (B) other than the polyarylene sulfide resin as the dispersed phase has an average dispersion diameter of 5 μm or less.

3. The resin composition according to claim 1 or 2, wherein the ratio of the amount of the thermoplastic resin (B) other than the polyarylene sulfide resin is in the range of 1 to 49% by mass relative to 100% by mass of the total amount of the polyarylene sulfide resin (a), the thermoplastic resin (B), and the carbodiimide compound (C).

4. The resin composition according to any one of claims 1 to 3, wherein the thermoplastic resin (B) other than the polyarylene sulfide resin is at least one resin selected from the group consisting of polyphenylene ether resins, polycarbonate resins, polyether sulfone resins, polyphenylene sulfone resins, polyether imide resins, and polysulfone resins.

5. The resin composition according to any one of claims 1 to 4, wherein the blending amount of the carbodiimide compound (C) is contained in a ratio of 0.1 to 5% by mass with respect to the total mass of the polyarylene sulfide resin (A), the thermoplastic resin (B) and the carbodiimide compound (C).

6. The resin composition according to any one of claims 1 to 5, further comprising a modified elastomer (D) to which a reactive group is imparted.

7. The resin composition according to claim 6, wherein the modified elastomer (D) comprises an olefin-based polymer having at least 1 functional group selected from the group consisting of an epoxy group and an acid anhydride group.

8. The resin composition according to claim 6 or 7, wherein the amount of the modified elastomer (D) is 1 to 15% by mass based on 100% by mass of the total of the polyarylene sulfide resin (A), the thermoplastic resin (B) other than the polyarylene sulfide resin, the carbodiimide compound (C), and the modified elastomer (D).

9. The resin composition according to any one of claims 6 to 8, wherein the modified elastomer (D) has an α -olefin content of 50 to 95% by mass based on the total mass of the modified elastomer.

10. The resin composition according to any one of claims 1 to 9, further comprising 0.01 to 5 mass% of a silane coupling agent (E) containing at least 1 functional group selected from an epoxy group, an amino group, and an isocyanate group.

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

12. The resin composition according to claim 11, wherein the styrene- (meth) acrylic acid copolymer (F) is contained in an amount of 0.1 to 10% by mass.

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

14. A biaxially stretched laminated film having at least 1 layer comprising the resin composition described in any one of claims 1 to 12.

15. A laminate, comprising: a biaxially stretched film or a biaxially stretched laminated film according to claim 13 or 14; and 1 or more of a metal layer or a resin molded article disposed on at least one surface of the biaxially stretched film or biaxially stretched laminate film.

16. A circuit board comprising the biaxially stretched film, biaxially stretched laminated film or laminate according to any one of claims 13 to 15.