KR20210012997A - Polyarylene sulfide resin composition, and biaxially stretched film and laminate using the same - Google Patents

Abstract

It is an object of the present invention to provide a resin composition in which the resulting biaxially stretched film is excellent in stretch uniformity and dielectric properties. Specifically, as a resin composition having at least a polyarylene sulfide resin, a polyphenylene ether resin, a styrene-(meth)acrylic acid copolymer, and an elastomer as a raw material, a continuous phase and a dispersed phase, wherein the continuous phase, A resin composition comprising a polyarylene sulfide resin, wherein the dispersed phase contains a polyphenylene ether resin and an elastomer, and the average dispersion diameter of the dispersed phase is 5 μm or less, and a biaxially stretched film thereof.

Description

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

The present invention relates to a polyarylene sulfide resin composition having excellent stretchability and low dielectric constant, and a biaxially stretched film and a laminate using the same.

In recent years, in the field of flexible printed circuit boards (FPC) and flexible flat cables (FFC), the development of cloud and Internet of Things (IoT), and the like, improvement of technology for automatic driving of automobiles, and the development of electric vehicles and hybrid vehicles are accompanied. Accordingly, there is a demand for a cable or antenna capable of processing a large amount of data and transmitting at high speed and without loss. However, conventionally, polyimide (PI) films are used for FPC substrates and polyester films (PET films, etc.) are used for FCC substrates, and it cannot be said that they have dielectric properties capable of coping with the next generation of high-speed transmission.

However, films using polyarylene sulfide resin typified by polyphenylene sulfide resin (PPS) are excellent in heat resistance, flame retardancy, chemical resistance, and electrical insulation, so they are used in insulating materials for capacitors and motors, and heat-resistant tapes. . Since the polyarylene sulfide resin has excellent dielectric properties compared to PI or PET, it can be applied to the field of a flexible printed wiring board (FPC) or a flexible flat cable (FFC).

For example, in Patent Document 1, (A) polyphenylene ether-based resin forms a dispersed phase, (B) polyphenylene sulfide forms a continuous phase, and the average dispersion diameter of the polyphenylene ether-based resin is 0.1 to 10. Μm, the ratio of the average dispersion diameter in the longitudinal direction to the average dispersion diameter in the width direction is 1 to 4, and the average aspect ratio of the dispersed phase in the cross section in the length direction of the film and the cross section in the thickness direction of the film in the width direction is 2 to 125. The invention according to the biaxially stretched thermoplastic resin film is described. Patent Document 1 describes that the biaxially stretched thermoplastic resin film has excellent surface appearance, mechanical properties, and heat dimensional stability.

In addition, Patent Document 1 discloses that conventionally, a polymer alloy in which polyphenylene sulfide, which has a low glass transition temperature, and polyphenylene ether having a high glass transition temperature, is mixed with polyphenylene sulfide, which is easy to heat shrink, has excellent heat resistance, molding processability, and impact resistance. What was known is described.

In addition, as a method of improving the toughness of a polyphenylene sulfide film, a method of ultrafine dispersion of another thermoplastic resin in the range of 30 to 300 nm in polyphenylene sulfide is disclosed.

In addition, it is described that the biaxially stretched thermoplastic resin film can be used as a printed circuit board material, a peripheral part of a printed circuit board, a semi-circuit board material, or the like.

Japanese Patent Publication No. 2009-179766

However, although the biaxially stretched thermoplastic resin film described in Patent Literature 1 exhibits a constant dielectric constant, it has been found that it is difficult to stretch uniformly, and that non-uniformity may occur in the dispersion phase of the obtained film.

Therefore, it is an object of the present invention to provide a resin composition in which the resulting biaxially stretched film is excellent in stretch uniformity and dielectric properties.

In order to solve the above problems, the inventors of the present invention conducted an examination of the properties. As a result, by using a styrene-(meth)acrylic acid copolymer and an elastomer together with a polyarylene sulfide-based resin and a polyphenylene ether-based resin, it was found that the above problems could be solved, and the present invention was completed. .

That is, the object of the present invention is achieved by the following means.

(1) A resin composition having at least a polyarylene sulfide resin, a polyphenylene ether resin, a styrene-(meth)acrylic acid copolymer, and an elastomer as a raw material, a continuous phase and a dispersed phase, wherein the continuous phase is poly A resin composition comprising an arylene sulfide resin, wherein the dispersed phase contains a polyphenylene ether resin and an elastomer, and the average dispersion diameter of the dispersed phase is 5 μm or less;

(2) The content of the polyphenylene ether-based resin is 1 to 40% by mass based on the total mass of the polyarylene sulfide resin, polyphenylene ether-based resin, styrene-(meth)acrylic acid copolymer, and elastomer. , The resin composition according to the above (1);

(3) The content of the styrene-(meth)acrylic acid copolymer is 0.5 to 10 mass with respect to the total mass of the polyarylene sulfide resin, polyphenylene ether resin, styrene-(meth)acrylic acid copolymer, and elastomer. % Of the resin composition according to (1) or (2) above;

(4) (1) to (3), wherein the (meth)acrylic acid content of the styrene-(meth)acrylic acid copolymer is 1 to 30 mass% with respect to the total mass of the styrene-(meth)acrylic acid copolymer. The resin composition according to any one of claims;

(5) The content of the elastomer is 3 to 20% by mass based on the total mass of the polyarylene sulfide resin, polyphenylene ether resin, styrene-(meth)acrylic acid copolymer, and elastomer. The resin composition according to any one of-(4);

(6) The elastomer is a copolymer of α-olefin and glycidyl ether of α,β-unsaturated carboxylic acid, and α-olefin and glycidyl ether of α,β-unsaturated carboxylic acid, (meta) The resin composition according to any one of (1) to (5), containing at least one selected from the group consisting of a copolymer with an acrylic acid ester;

(7) The resin composition according to the above (6), wherein the ?-olefin content of the elastomer is 50 to 95% by mass relative to the total mass of the elastomer;

(8) A biaxially stretched film obtained by biaxially stretching the resin composition according to any one of (1) to (7) above;

(9) A laminate comprising the biaxially stretched film according to (8) and a metal layer disposed on at least one surface of the biaxially stretched film.

According to the present invention, a resin composition in which the obtained biaxially stretched film is excellent in stretch uniformity and dielectric properties is provided.

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

[Resin composition]

The resin composition includes at least a polyarylene sulfide resin (hereinafter sometimes referred to as ``PAS resin''), a polyphenylene ether resin (hereinafter referred to as ``PPE resin''), and styrene-( It uses meth)acrylic acid and an elastomer as raw materials. At this time, the resin composition has a continuous phase and a dispersed phase, wherein the continuous phase contains a polyarylene sulfide resin, and the dispersed phase contains a polyphenylene ether resin and an elastomer. Further, most of the styrene-(meth)acrylic acid is contained in the dispersed phase.

Since the continuous phase is a PAS resin, the resulting biaxially stretched film can have suitable dielectric properties.

The average dispersion diameter of the dispersed phase is 5 µm or less, preferably 3 µm or less, and more preferably 0.5 to 3 µm. When the average dispersion diameter of the dispersed phase is 5 µm or less, a uniform stretched film can be obtained. In addition, in this specification, the "average dispersion diameter of the dispersed phase" shall adopt a value measured by the method described in Examples.

[Polyarylene sulfide resin]

The polyarylene sulfide (PAS) resin used in the present invention is usually a main component of the resin composition, and, as a rule, is included in the continuous phase of the resin composition.

The PAS resin has a resin structure in which an aromatic ring and a sulfur atom are bonded to each other as a repeating unit.

As a specific example of a polyarylene sulfide resin, resin which has the structural part represented by following structural formula (1) as a repeating unit is mentioned.

In the above formulas, 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 is each independently of 1 to 4 It is an integer.

Here, the structural moiety represented by the structural formula (1), in particular R ¹ in the formula is the art, it is preferred that a hydrogen atom in view of the mechanical strength of the PAS resin. Examples of all of R ¹ being hydrogen atoms include those bonded at the para-position represented by the following structural formula (2), and those bonded at the meta-position represented by the following structural formula (3).

Among these, in particular, it is preferable from the viewpoint of heat resistance and crystallinity of the PAS resin that the bonding of the sulfur atom to the aromatic ring in the repeating unit is a structure bonded at the para position represented by the structural formula (2).

Further, the PAS resin may contain not only the structural moieties represented by the structural formula (1), but also the structural moieties represented by the structural formulas (4) to (7) below.

In the case of including structural moieties represented by structural formulas (4) to (7), the structural moiety represented by structural formulas (4) to (7) is 30 moles from the total of structural moieties represented by structural formula (1). It is preferably contained in% or less, and more preferably 10 mol% or less in terms of heat resistance and mechanical strength of the PAS resin.

When the structural moieties represented by the above structural formulas (4) to (7) are included in the PAS resin, any of a random copolymer and a block copolymer may be used as their bonding mode.

In addition, the PAS resin may have a trifunctional structural moiety represented by the following structural formula (8) or a naphthyl sulfide bond in its molecular structure.

The trifunctional structural moiety represented by the structural formula (8), naphthyl sulfide bond, etc., is preferably 1 mol% or less with respect to the total number of moles with other structural moieties, and substantially from the viewpoint of reducing the content of chlorine atoms in the PAS resin. Is more preferably not included.

Such PAS resin can be produced, for example, by the following (1) to (4).

(1) a method of reacting sodium sulfide and p-dichlorobenzene in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfone solvent such as sulfolane,

(2) a method of polymerizing p-dichlorobenzene in the presence of sulfur and sodium carbonate,

(3) A method of polymerization in the presence of sodium sulfide or sodium hydrosulfide and sodium hydroxide or hydrogen sulfide and sodium hydroxide in a polar solvent,

(4) Method by self-condensation of p-chlorothiophenol.

Among these, the method of reacting sodium sulfide and p-dichlorobenzene in an amide solvent such as N-methylpyrrolidone and dimethylacetamide in (1) or a sulfone solvent such as sulfolane is easy to control the reaction. It is preferable in terms of excellent productivity.

In addition, from the viewpoint of industrially efficient production of linear and high molecular weight PAS resin, in particular, solid alkali metal sulfide, dichlorobenzene, alkali metal hydrosulfide and organic acid alkali metal salt are essential among the above method (1). Particularly preferred is a method of preparing a reaction slurry serving as a component and heating it to perform polymerization in a heterogeneous system. Specifically, such a polymerization method,

Process 1:

Hydrous alkali metal sulfide, or,

Hydrous alkali metal hydrosulfide and alkali metal hydroxide,

With N-methylpyrrolidone,

A non-hydrolyzable organic solvent,

The process of producing a slurry (I) by reacting while dehydrating,

Process 2:

Next, in the slurry (I),

Dichlorobenzene,

The alkali metal hydrosulfide, and

Alkali metal salt of the hydrolyzate of N-methylpyrrolidone

The process of performing polymerization by reacting

A method including a is preferable from the viewpoint of productivity.

Examples of the hydrated alkali metal sulfide used herein include a liquid or solid hydrated product of a compound such as lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide and cesium sulfide. The solid content concentration of the hydrous alkali metal sulfide is preferably 10 to 80% by mass, more preferably 35 to 65% by mass.

In addition, examples of the hydrous alkali metal hydrosulfide include liquid or solid hydrous compounds of compounds such as lithium hydrosulfide, sodium hydrosulfide, potassium hydrosulfide, rubidium hydrosulfide and cesium hydrosulfide. Among these, a hydrated product of lithium hydrosulfide and a hydrated product of sodium hydrosulfide are preferred, and a hydrated product of sodium hydrosulfide is particularly preferred. Moreover, it is preferable that the solid content concentration of the said hydrous alkali metal hydrosulfide is 10 to 80 mass %.

Further, examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, and aqueous solutions thereof. Among these, lithium hydroxide, sodium hydroxide, and potassium hydroxide are preferable, and sodium hydroxide is particularly preferable. Moreover, in the case of using an aqueous solution of an alkali metal hydroxide, an aqueous solution having a concentration of 20% by mass or more is preferable from the viewpoint of easy dehydration treatment in Step 1.

Among the PAS resins thus obtained, in particular, in the measurement using gel permeation chromatography (GPC), the peak has a molecular weight in the range of 25,000 to 30,000, and the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) When (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, the chlorine atom content of the PAS resin itself is 1,500 to 2,000 ppm without lowering the mechanical strength of the molded article. It is preferable in that it can be reduced to the range of and the halogen-free application to electronic/electric parts applications becomes easy.

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

[Measurement conditions by gel permeation chromatography]

Device; Ultra-high temperature polymer molecular weight distribution measuring device (SSC-7000 manufactured by Senshu Chemical)

column; UT-805L (made by Showa Denko Corporation)

Column temperature; 210℃

menstruum; 1-chloronaphthalene

Measurement method: Using a UV detector (360 nm), six types of monodisperse polystyrene are used for calibration, and the molecular weight distribution and peak molecular weight are measured.

Since the PAS resin described above can also reduce the amount of residual metal ions to improve moisture resistance properties and reduce the residual amount of low-molecular-weight impurities generated during polymerization, after preparing the PAS resin , It is preferable that it is treated with an acid and then washed with water.

The acid that can be used here is preferable in that acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid, and propyl acid do not decompose in the PAS resin and the amount of remaining metal ions can be efficiently reduced, and acetic acid and hydrochloric acid are more preferable. .

The method of acid treatment includes a method of immersing the PAS resin in an acid or aqueous acid solution. At this time, you may further stir or heat as needed.

Here, the specific method of the acid treatment is, for example, in the case of using acetic acid, a method of first heating an aqueous acetic acid solution of pH 4 to 80 to 90°C, immersing the PAS resin therein, and stirring for 20 to 40 minutes. Can be lifted.

The PAS resin subjected to acid treatment in this way is then washed several times with water or hot water in order to physically remove the remaining acid or salt. The water used at this time is preferably distilled water or deionized water.

Further, the PAS resin provided for the acid treatment is preferably a powder or granular material, and specifically, may be a granular material such as a pellet, or may be a slurry state after polymerization.

From the viewpoint of heat resistance and chemical resistance, the content rate of the PAS resin is preferably 50 to 96% by mass based on the total mass of the PAS resin, polyphenylene ether resin, styrene-(meth)acrylic acid copolymer, and elastomer. It is more preferable that it is 60-90 mass %.

[Polyphenylene ether resin]

The polyphenylene ether resin is contained in the dispersion phase of the resin composition as a rule. The PPE-based resin in the dispersed phase has a function of reducing the dielectric constant of the obtained biaxially oriented film.

The polyphenylene ether resin is a homopolymer and/or a copolymer having a structural moiety represented by the following structural formula (9).

In the above formula, R ² is 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, At least two carbon atoms are halohydrocarbonoxy groups separating a halogen atom and an oxygen atom, and m is each independently an integer of 1 to 4.

Specific examples of the polyphenylene ether resin 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), poly(2,6-dichloro-1,4-phenylene ether), and 2,6-dimethylphenol and other phenols (for example, , A polyphenylene ether copolymer such as a copolymer with 2,3,6-trimethylphenol or 2-methyl-6-butylphenol). Among them, poly(2,6-dimethyl-1,4-phenylene ether) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferable, and poly(2,6-dimethyl- 1,4-phenylene ether) is more preferred.

The number average molecular weight of the polyphenylene ether resin is preferably 1000 or more, more preferably 1500 to 500,000, and still more preferably 1500 to 30000.

The content rate of the polyphenylene ether resin is preferably 1 to 40 mass% with respect to the total mass of the PAS resin, polyphenylene ether resin, styrene-(meth)acrylic acid copolymer, and elastomer, and stretch uniformity, It is more preferable that it is 2 to 25 mass% from a viewpoint of tear strength etc., and it is still more preferable that it is 3 to 18 mass% from a viewpoint of tear strength and dielectric constant.

[Styrene-(meth)acrylic acid copolymer]

Most of the styrene-(meth)acrylic acid copolymer is contained in the dispersion phase of the resin composition. The styrene-(meth)acrylic acid copolymer in the dispersed phase reacts with an elastomer that also functions as a compatibilizer, thereby improving the interfacial adhesion between the PAS resin and the polyphenylene ether resin, and improving the mechanical strength (tear strength, etc.). It can have a function.

The styrene-(meth)acrylic acid copolymer is not particularly limited, and is a copolymer obtained by copolymerizing a styrene-based monomer and a (meth)acrylic acid monomer. In addition, in this specification, "(meth)acryl" means "methacryl" and/or "acrylic".

Although it does not specifically limit as a styrene-type monomer, Styrene and its derivatives are mentioned. Examples of the styrene derivative 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; And methoxystyrene. These styrene-based monomers may be used alone or in combination of two or more.

Examples of the (meth)acrylic acid monomer include acrylic acid and methacrylic acid, as well as (meth)acrylate alkyl esters having a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. At this time, the substituent is not particularly limited, but a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, a hydroxyl group, and the like can be mentioned. Moreover, you may have one substituent and may have two or more. In the case of having two or more substituents, each of the substituents may be the same or different. Specific examples of the (meth)acrylate alkyl ester having a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, T-butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, hydroxyethyl (meth)acrylate, and hydroxypropyl (meth)acrylate. Among these, it is preferable that it is (meth)acrylic acid from a viewpoint of compatibility and reactivity with an elastomer. Moreover, these (meth)acrylic acid monomers may be used alone or in combination of two or more.

The (meth)acrylic acid content of the styrene-(meth)acrylic acid copolymer is preferably 1 to 30% by mass, more preferably 3 to 20% by mass with respect to the total mass of the styrene-(meth)acrylic acid copolymer. It is preferable, and it is more preferable that it is 5-18 mass% from a viewpoint of a stretch uniformity, tear strength, etc. When the content of (meth)acrylic acid is 1% by mass or more, it is preferable because good compatibility with the elastomer can be obtained. On the other hand, if the content of (meth)acrylic acid is 30% by mass or less, it is preferable because good compatibility with the polyphenylene ether resin can be obtained.

In the polymerization reaction of the styrene-(meth)acrylic acid copolymer, various general-purpose polymerization methods of 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, continuous bulk polymerization is particularly preferred from the viewpoint of production efficiency. For example, continuous bulk polymerization is carried out by introducing a tubular reactor in which at least one agitated reactor and a plurality of mixing elements without moving parts are fixed therein. Thus, an excellent resin can be obtained. Although thermal polymerization can be carried out without using a polymerization initiator, it is preferable to use various radical polymerization initiators. In addition, polymerization aids such as suspending agents and emulsifying agents required for polymerization may be those used in the production of ordinary polystyrene.

In order to reduce the viscosity of the reactant in 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, or Sol, cyanobenzene, dimethylformamide, N,N-dimethylacetamide, methyl ethyl ketone, etc. are mentioned. Moreover, these organic solvents may be used individually or may be used in combination of 2 or more types.

The radical polymerization initiator is not particularly limited, and for example, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)butane, 2,2-bis( Peroxyketals such as 4,4-di-butylperoxycyclohexyl)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 disinamoyl peroxide; peroxy esters such as t-butylperoxybenzoate, di-t-butylperoxyisophthalate, and t-butylperoxyisopropyl 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], and the like. These radical polymerization initiators can be used alone or in combination of two or more.

Moreover, you may add a chain transfer agent so that the molecular weight of the resin composition obtained may not become excessively too large. As the chain transfer agent, a monofunctional chain transfer agent having one chain transfer group may be used, or a multifunctional chain transfer agent having a plurality of chain transfer groups may be used.

Examples of the monofunctional chain transfer agent include alkyl mercaptans and thioglycolic acid esters.

Examples of the polyfunctional chain transfer agent include hydroxy groups in polyhydric alcohols such as ethylene glycol, neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, and sorbitol with thioglycolic acid or 3-mercaptopropionic acid. And things that were made up.

The above-described chain transfer agent may be used alone or in combination of two or more.

Further, in order to suppress the gel formation of the obtained resin composition, it is possible to use a long-chain alcohol, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyoleyl ether, polyoxyethylene alkenyl ether, or the like.

The content rate of the styrene-(meth)acrylic acid copolymer is preferably 0.5 to 10% by mass with respect to the total mass of the PAS resin, polyphenylene ether resin, styrene-(meth)acrylic acid copolymer, and elastomer, and 0.5 to It is more preferable that it is 5 mass %, from a viewpoint of stretch uniformity, tear strength, etc., it is more preferable that it is 0.5-3 mass %, and it is especially preferable that it is 1-3 mass %.

[Styrene resin]

The resin composition may contain a styrene resin. The styrenic resin is, as a rule, contained in the dispersed phase of the resin composition. In addition, since the styrene resin is particularly highly compatible with the polyphenylene ether resin, it may be included in a form compatible with or close to the polyphenylene ether resin. The styrenic resin has a function of improving fluidity during melting. In addition, in this specification, "styrene resin" means a resin other than the above-described styrene-methacrylic acid copolymer, and containing a styrene-based monomer as a main monomer unit.

Although it does not specifically limit as said styrene-type resin, A polymer of a styrene-type monomer is mentioned. At this time, as the styrene-based monomer, the above-described one may be used.

The styrenic resin may be a homopolymer of a styrenic monomer, or a copolymer obtained by copolymerizing two or more types. Further, rubber-modified styrene (high-impact styrene) using a rubber component such as polybutadiene, styrene-butadiene copolymer, polyisoprene, and butadiene-isoprene copolymer may be used.

Among these, the styrene resin is preferably polystyrene, which is a homopolymer of styrene.

In addition, the above-described styrene resins may be used alone or in combination of two or more.

[Elastomer]

The elastomer is, as a rule, contained in the dispersed phase of the resin composition. The elastomer in the dispersed phase also functions as a compatibilizer between the PSA resin and the polyphenylene ether resin, and has a function of improving mechanical strength (tear strength, etc.) by finely dispersing the dispersed phase. In addition, by using in combination with a styrene-(meth)acrylic acid copolymer, the adhesion of the interface between the PSA resin and the polyphenylene ether resin is further improved, and the mechanical strength (tear strength, etc.) is further improved through the elastomer. do.

Examples of the elastomer include a copolymer of an α-olefin and an α,β-unsaturated glycidyl ester, and a copolymer of an α-olefin and an α,β-unsaturated glycidyl ester and an acrylic acid ester. That is, in one embodiment, the elastomer is a copolymer of an α-olefin and an α,β-unsaturated glycidyl ester, and an α-olefin, an α,β-unsaturated glycidyl ester, and an acrylic acid ester. It includes at least one selected from the group consisting of copolymers of.

Ethylene, propylene, 1-butene, etc. are mentioned as said α-olefin. Among these, it is preferable to use ethylene.

Although it does not specifically limit as said α,β-unsaturated glycidyl ester, a compound represented by the following formula (10) can be mentioned.

In the above formula, R ³ is an alkenyl group having 1 to 6 carbon atoms. The alkenyl group having 1 to 6 carbon atoms is not particularly limited, but vinyl group, 1-propenyl group, 2-propenyl group, 1-methylethenyl group, 1-butenyl group, 2-butenyl group, 1-methyl-1 -Prophenyl group, 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. are mentioned.

In addition, each of R ⁴ independently represents a hydrogen atom, a halogen atom, and 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.

The alkyl group having 1 to 6 carbon atoms is not particularly limited, but a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, 2-methylbutyl group , 3-methylbutyl group, 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, 2,4-dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, etc. are mentioned.

As a specific example of the said α,β-unsaturated glycidyl ester, glycidyl acrylate, glycidyl methacrylate, etc. are mentioned. Among these, it is preferable that it is glycidyl methacrylate.

When the elastomer is a copolymer of an α-olefin and an α,β-unsaturated glycidyl ester, or a copolymer of an α-olefin and an α,β-unsaturated glycidyl ester and an acrylic acid ester, α in the elastomer The content rate of the ?-unsaturated glycidyl ester is preferably 1 to 30% by mass, more preferably 2 to 20% by mass. When the content rate of the α,β-unsaturated glycidyl ester is 1% by mass or more, it is preferable because the target improvement effect is obtained. On the other hand, if it is 30 mass% or less, since good extrusion stability can be obtained, it is preferable.

In addition, if the elastomer is a copolymer of an α-olefin and an α,β-unsaturated glycidyl ester, or a copolymer of an α-olefin and an α,β-unsaturated glycidyl ester and an acrylic acid ester, the elastomer It is preferable that it is 50-95 mass %, and, as for the content rate of the α-olefin in it, it is more preferable that it is 50-80 mass% from a viewpoint of drawing uniformity, tear strength, etc.

The content rate of the elastomer is preferably 1 to 30% by mass, more preferably 3 to 20% by mass based on the total mass of the PAS resin, polyphenylene ether resin, styrene-(meth)acrylic acid copolymer, and elastomer. It is preferable, and it is more preferable that it is 7-20 mass% from a viewpoint of dielectric constant, tear strength, etc.

[Alkoxysilane having an amino group]

The resin composition may further contain an alkoxysilane having an amino group. By using an alkoxysilane having an amino group, the dispersibility of the polyphenylene ether-based resin can be dramatically improved, and a good morphology can be formed.

Specific examples of the alkoxysilane having an amino group include γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, and γ-aminopropyltrimethoxysilane. I can.

The blending amount of the alkoxysilane having an amino group is preferably 0.01 to 5% by mass, and 0.1 to 3, based on the total mass of the PAS resin, polyphenylene ether resin, styrene-(meth)acrylic acid copolymer, and elastomer. It is more preferable that it is mass %.

[additive]

A plasticizer, a weathering agent, an antioxidant, a heat stabilizer, an ultraviolet stabilizer, a lubricant, an antistatic agent, a colorant, a conductive agent, and the like may be added to the resin composition as long as the effect of the present invention is not impaired.

<Production method of resin composition>

The method for preparing the above resin composition is not particularly limited, but the PAS resin, polyphenylene ether resin, styrene-(meth)acrylic acid copolymer, elastomer, and other compounding components as necessary may be added to a tumbler or a Henschel mixer, etc. Then, a method of mixing uniformly with a twin screw extruder and melt-kneading is mentioned. At this time, the melt-kneading is preferably carried out under conditions in which the ratio (discharge amount/screw rotation speed) between the discharge amount (kg/hr) of the resin component and the screw rotation speed (rpm) is 0.02 to 0.2 (kg/hr·rpm). Do. By the above production method, a resin composition having an average dispersion diameter of 5 μm or less of the dispersed phase can be produced.

In more detail with respect to the above manufacturing method, a method in which each of the above-described components is introduced into a twin-screw extruder and melt-kneaded under a temperature condition of about 300°C and 330°C is exemplified. At this time, the discharge amount of the resin component is in the range of 5 to 50 kg/hr at a rotation speed of 250 rpm. Especially, it is preferable that it is 20-35 kg/hr especially from a dispersibility point. Therefore, it is more preferable that the ratio (discharge amount/screw rotation speed) of the discharge amount (kg/hr) of the resin component and the screw rotation speed (rpm) is particularly preferably 0.08 to 0.14 (kg/hr·rpm). Further, the torque of the twin-screw extruder is preferably in a range in which the maximum torque is 20 to 100 (Å), particularly 25 to 80 (Å), in view of good dispersibility of the polyphenylene ether resin and elastomer.

<Biaxially oriented film>

According to one aspect of the present invention, a biaxially stretched film is provided. The biaxially stretched film is formed by biaxially stretching the resin composition described above.

In addition, as will be described later, the average dispersion diameter of the biaxially oriented film is carried out under Tg or less of the resin (particularly polyphenylene ether) constituting the dispersed phase in the resin composition under the production conditions (temperature conditions, etc.) Therefore, the dispersed phase is not deformed, and the average dispersion diameter in the resin composition is maintained.

The draw ratio of the biaxially stretched film in the longitudinal direction (MD direction) is preferably 2 to 4 times, and more preferably 2.5 to 3.8 times.

In addition, the draw ratio in the width direction (TD direction) of the biaxially stretched film is preferably 2 to 4 times, and more preferably 2.5 to 3.8 times.

In addition, the ratio of the draw ratio in the width direction (TD direction) of the biaxially stretched film to the draw ratio in the width direction (MD direction) of the biaxially stretched film (length direction (TD direction))/(width direction (MD direction)) is , 0.8 to 1.2 is preferable, and 0.9 to 1.1 is more preferable.

<Biaxially oriented film manufacturing method>

The method for producing the biaxially stretched film is not particularly limited, and a known method may be employed. For example, after drying the resin composition at 140° C. for 3 hours or more and under reduced pressure of 10 mmhg or less, it is introduced into an extruder heated to 280 to 320° C. Thereafter, the molten resin passed through the extruder is discharged from a T-die in a sheet form, and cooled and solidified by intimate contact with a cooling roll having a surface temperature of 20 to 50°C to obtain an unoriented sheet.

Next, the unstretched sheet is biaxially stretched. As the stretching method, a sequential biaxial stretching method, a simultaneous biaxial stretching method, or a method in which these are combined 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 2 to 4 times in the longitudinal direction (MD direction), preferably 2.5 to 3.8 times Or, it is stretched in two or more stages. The stretching temperature is in the range of the glass transition temperature (Tg) of the PAS resin to Tg+40°C, preferably, Tg+5°C to Tg+30°C, more preferably Tg+5°C to Tg+20°C. . After that, it is cooled with a 30 to 60 degreeC cooling roll group.

Next, it stretches in the width direction (TD direction) by a method using a tenter. Both ends of the film stretched in the MD direction are gripped with a clip, guided by a tenter, and stretched in the TD direction. The draw ratio is in the range of 2 to 4 times, preferably 2.5 to 3.8 times. The stretching temperature is in the range of Tg to Tg+40°C, preferably Tg+5°C to Tg+30°C, more preferably Tg+5°C to Tg+20°C.

Next, the stretched film is heat-set under tension or while relaxing in the width direction. The heat setting temperature is not particularly limited, but is in the range of 200 to 275°C, preferably 220 to 275°C, and more preferably 240 to 270°C. It may be carried out in two stages by changing the heat setting temperature. In that case, it is preferable to make the heat setting temperature of the 2nd stage higher than the 1st stage +10-40 degreeC. It is preferable to perform heat setting time in the range of 1 to 60 seconds. In addition, in heat setting, since the biaxially stretched film is heated, even if the resin constituting the dispersed phase (especially polyphenylene ether) melts during the heat setting process, the molten resin cannot move, and with the completion of heat setting, It solidifies by cooling. As a result, the average dispersion diameter of the dispersed phase is maintained before and after heat setting.

This film is further 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 still more preferably 3 to 7%.

[Laminate]

According to one aspect of the present invention, a laminate is provided. The laminate includes the above-described biaxially stretched film and a metal layer disposed on at least one surface of the biaxially stretched film.

Although it does not specifically limit as said metal layer, Copper, aluminum, zinc, titanium, nickel, an alloy containing these, etc. are mentioned.

Moreover, a single layer may be sufficient as a metal layer, and two layers may be sufficient as it. When the metal layer is two layers, each metal phase may be the same or different.

In one embodiment, the laminate is a metal layer-biaxially stretched film, a metal layer-biaxially stretched film-metal layer, a metal layer-biaxially stretched film-metal layer-biaxially stretched film, a metal layer-metal layer-biaxially stretched film, metal layer-metal layer-biaxially stretched film -It can have a configuration such as a metal layer.

Moreover, as a method of forming a metal layer, methods, such as a vacuum vapor deposition method, sputtering, and plating of a metal, are mentioned. Moreover, you may form a metal layer by the method of superposing|stacking the above-mentioned biaxially stretched film and a metal foil and thermally welding.

The laminate provided with the metal layer can be suitably used for next-generation high-speed transmission because the biaxially oriented film has excellent dielectric properties. Further, in the laminate, since the biaxially stretched film is excellent in stretch uniformity, it is excellent in thickness uniformity and can suppress non-uniformity in dielectric constant.

(Example)

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

[Example 1]

89 parts by mass of MA520 (linear PPS, manufactured by DIC Corporation), a polyphenylene sulfide resin (PPS resin), PX-100 (manufactured by Asahi Chemical Co., Ltd.), a polyphenylene ether resin (PPE resin) ) 5 parts by mass, Leurex A-14P, a styrene-methacrylic acid copolymer (SMAA) (methacrylic acid content: 14% by mass, manufactured by DIC Corporation), 1 part by mass, Bondfast 7L, an elastomer (ethylene/gly Cidyl methacrylate/methyl acrylate = 70/3/27 (mass%), 5 parts by mass of Sumitomo Chemical Co., Ltd.) were uniformly mixed with a tumbler to obtain a mixture.

Then, the mixture obtained above was put into the twin screw extruder "TEX-30α" with vent manufactured by Nihon Seiko Co., Ltd. It melt-extruded under conditions of a discharge amount of 20 kg/hr, screw rotation speed of 300 rpm, and a set temperature of 300°C, discharged into strands, cooled with water at a temperature of 30°C, and cut to prepare a resin composition.

The resin composition was put into a single screw extruder of a full flight screw and melted under the conditions of 280°C to 300°C. After the melted resin composition was extruded from the T-die, it was adhered and cooled with a chilled roll set at 40°C to prepare an unstretched PPS resin sheet.

The unstretched PPS resin sheet was biaxially stretched at a rate of 3.0×3.0 times at 100° C. using a batch-type biaxial stretching machine (manufactured by Imoto Seiko Co., Ltd.) to obtain a film having a thickness of 35 μm. And the obtained film was fixed to a mold, and a biaxially stretched film was produced by heat setting treatment with a 260 degreeC oven.

About the produced biaxially stretched film, the average dispersion diameter of a dispersed phase was measured by the following method.

Specifically, the produced biaxially stretched film was cut by an ultra-thin sectioning method in (a) a direction parallel to the length direction and perpendicular to the film surface, and (b) a direction parallel to the width direction and perpendicular to the film surface. The cut surfaces (A) and (B) of the cut film were photographed with a scanning electron microscope (SEM) of 2000 times each, and the obtained image was enlarged to A3 size. Select 50 randomly dispersed phases in the enlarged SEM photo, measure the maximum diameter of each of the disperse phases at the fracture surfaces (A) and (B), and calculate the average diameter by combining the two directions of the cut surfaces (A) and (B). did.

As a result, the average dispersion diameter of the dispersed phase of the produced biaxially stretched film was 1.3 µm.

[Example 2]

A resin composition and a biaxially stretched sheet were produced in the same manner as in Example 1, except that 79 parts by mass of PPS resin, 15 parts by mass of PPE-based resin, 1 part by mass of SMAA, and 5 parts by mass of elastomer were used.

Moreover, when the average dispersion diameter of the dispersed phase of the biaxially stretched sheet was measured in the same manner as in Example 1, it was 1.4 µm.

[Example 3]

A resin composition and a biaxially stretched sheet were prepared in the same manner as in Example 1 except that 74 parts by mass of PPS resin, 20 parts by mass of PPE-based resin, 1 part by mass of SMAA, and 5 parts by mass of elastomer were used.

Moreover, when the average dispersion diameter of the dispersed phase of the biaxially stretched sheet was measured in the same manner as in Example 1, it was 1.7 µm.

[Example 4]

A resin composition and a biaxially stretched sheet were produced in the same manner as in Example 1 except that 64 parts by mass of PPS resin, 30 parts by mass of PPE-based resin, 1 part by mass of SMAA, and 5 parts by mass of elastomer were used.

Moreover, when the average dispersion diameter of the dispersed phase of the biaxially stretched sheet was measured in the same manner as in Example 1, it was 1.7 µm.

[Example 5]

A resin composition and a biaxially stretched sheet were manufactured in the same manner as in Example 1 except that 75 parts by mass of PPS resin, 15 parts by mass of PPE-based resin, 5 parts by mass of SMAA, and 5 parts by mass of elastomer were used.

Moreover, when the average dispersion diameter of the dispersed phase of the biaxially stretched sheet was measured in the same manner as in Example 1, it was 1.9 µm.

[Example 6]

A resin composition and a biaxially stretched sheet were produced in the same manner as in Example 1, except that the draw ratio was set to 3.5×3.5 times.

Moreover, when the average dispersion diameter of the dispersed phase of the biaxially stretched sheet was measured in the same manner as in Example 1, it was 1.2 µm.

[Example 7]

A resin composition and a biaxially stretched sheet were prepared in the same manner as in Example 6, except that 84 parts by mass of PPS resin, 10 parts by mass of PPE-based resin, 1 part by mass of SMAA, and 5 parts by mass of elastomer were used.

Moreover, when the average dispersion diameter of the dispersed phase of the biaxially stretched sheet was measured in the same manner as in Example 1, it was 1.5 µm.

[Example 8]

A resin composition and a biaxially stretched sheet were produced in the same manner as in Example 6, except that 79 parts by mass of PPS resin, 15 parts by mass of PPE-based resin, 1 part by mass of SMAA, and 5 parts by mass of elastomer were used.

Moreover, when the average dispersion diameter of the dispersed phase of the biaxially stretched sheet was measured in the same manner as in Example 1, it was 1.6 µm.

[Example 9]

A resin composition and a biaxially stretched sheet were prepared in the same manner as in Example 8, except that SMAA having a methacrylic acid content of 3% by mass was used as the styrene-methacrylic acid copolymer (SMAA).

Moreover, when the average dispersion diameter of the dispersed phase of the biaxially stretched sheet was measured in the same manner as in Example 1, it was 1.5 µm.

[Example 10]

A resin composition and a biaxially stretched sheet were prepared in the same manner as in Example 8, except that SMAA having a methacrylic acid content of 20% by mass was used as the styrene-methacrylic acid copolymer (SMAA).

Moreover, when the average dispersion diameter of the dispersed phase of the biaxially stretched sheet was measured in the same manner as in Example 1, it was 1.8 µm.

[Example 11]

A resin composition and a biaxially stretched sheet were produced in the same manner as in Example 6, except that 74 parts by mass of PPS resin, 15 parts by mass of PPE-based resin, 1 part by mass of SMAA, and 10 parts by mass of elastomer were used.

Moreover, when the average dispersion diameter of the dispersed phase of the biaxially stretched sheet was measured in the same manner as in Example 1, it was 1.5 µm.

[Example 12]

A resin composition and a biaxially stretched sheet were produced in the same manner as in Example 6 except that 69 parts by mass of PPS resin, 15 parts by mass of PPE-based resin, 1 part by mass of SMAA, and 15 parts by mass of elastomer were used.

Moreover, when the average dispersion diameter of the dispersed phase of the biaxially stretched sheet was measured in the same manner as in Example 1, it was 1.3 µm.

[Example 13]

Resin composition in the same manner as in Example 8, except that Bond Fast E (ethylene/glycidyl methacrylate = 88/12 (mass%), manufactured by Sumitomo Chemical Co., Ltd.) was used as the elastomer. And a biaxially stretched sheet.

Moreover, when the average dispersion diameter of the dispersed phase of the biaxially stretched sheet was measured in the same manner as in Example 1, it was 2.8 µm.

[Comparative Example 1]

A resin composition and a biaxially stretched sheet were prepared in the same manner as in Example 1, except that 100 parts by mass of PPS resin was used, and no PPE-based resin, SMAA, or elastomer was used.

[Comparative Example 2]

A resin composition and a biaxially stretched sheet were prepared in the same manner as in Example 1, except that 95 parts by mass of PPS resin and 5 parts by mass of elastomer were used, and PPE-based resin and SMAA were not used.

Moreover, when the average dispersion diameter of the dispersed phase of the biaxially stretched sheet was measured in the same manner as in Example 1, it was 0.5 µm.

[Comparative Example 3]

A resin composition and a biaxially stretched sheet were produced in the same manner as in Example 1, except that 90 parts by mass of PPS resin, 5 parts by mass of PPE-based resin, and 5 parts by mass of elastomer were used, and SMAA was not used.

Moreover, when the average dispersion diameter of the dispersed phase of the biaxially stretched sheet was measured in the same manner as in Example 1, it was 2 µm.

Compositions of the resin compositions and biaxially stretched sheets prepared in Examples 1 to 13 and Comparative Examples 1 to 3 are shown in Table 1 below.

[Table 1]

Physical properties of the biaxially stretched sheets produced in Examples 1 to 13 and Comparative Examples 1 to 3 were evaluated.

[permittivity]

A strip having a width of 2 mm and a length of 150 mm was produced from the biaxially stretched sheet. Next, the prepared strip was allowed to stand for 24 hours in an environment of 23°C and 50% Rh, and then the dielectric constant at a frequency of 1 GHz was measured by a cavity resonance method using the ADMS010c series (manufactured by AET Co., Ltd.). The obtained results are shown in Table 2 below.

[Elongation uniformity]

A grid-like stamp (grid size 10 x 10 (mm)) was stamped on the unstretched sheet in an unoriented state, and stretched at a predetermined magnification. The situation of the grid of the obtained biaxially stretched film was observed visually, and it evaluated according to the following criteria. The obtained results are shown in Table 2 below.

◎; More than 90% of the grid on the entire surface of the film is square

○; More than 80% and less than 90% of the grid on the front of the film are square

△; More than 50% and less than 80% of the grid on the front of the film are square

×; Less than 50% of the grid on the front of the film is square

[Tear strength]

A sample was punched out from the biaxially stretched film in a shape conforming to JIS K6732:2006. After the punched sample was allowed to stand in a constant temperature chamber of 23°C and 50% Rh, a tear test was performed at a rate of 200 mm/min using a tensile tester (manufactured by A&D Co., Ltd.) to measure the tear strength. The obtained results are shown in Table 2 below.

[Table 2]

As is also apparent from the description of Table 2, it can be seen that the resulting biaxially stretched film has excellent stretch uniformity and dielectric properties.

Claims (9)

As a resin composition having a continuous phase and a dispersed phase, comprising at least a polyarylene sulfide resin, a polyphenylene ether resin, a styrene-(meth)acrylic acid copolymer, and an elastomer as raw materials,
The continuous phase includes a polyarylene sulfide resin,
The dispersed phase contains a polyphenylene ether resin and an elastomer,
The resin composition, wherein the average dispersion diameter of the dispersed phase is 5 μm or less. The method of claim 1,
The resin composition, wherein the content rate of the polyphenylene ether resin is 1 to 40 mass% with respect to the total mass of the polyarylene sulfide resin, polyphenylene ether resin, styrene-(meth)acrylic acid copolymer, and elastomer. . The method according to claim 1 or 2,
The content of the styrene-(meth)acrylic acid copolymer is 0.5 to 10% by mass with respect to the total mass of the polyarylene sulfide resin, polyphenylene ether resin, styrene-(meth)acrylic acid copolymer, and elastomer, Resin composition. The method according to any one of claims 1 to 3,
The resin composition, wherein the (meth)acrylic acid content of the styrene-(meth)acrylic acid copolymer is 1 to 30 mass% with respect to the total mass of the styrene-(meth)acrylic acid copolymer. The method according to any one of claims 1 to 4,
The resin composition, wherein the content rate of the elastomer is 3 to 20% by mass based on the total mass of the polyarylene sulfide resin, polyphenylene ether resin, styrene-(meth)acrylic acid copolymer, and elastomer. The method according to any one of claims 1 to 5,
The elastomer is a copolymer of α-olefin and glycidyl ether of α,β-unsaturated carboxylic acid, and α-olefin, glycidyl ether of α,β-unsaturated carboxylic acid, and (meth)acrylic acid ester A resin composition comprising at least one selected from the group consisting of a copolymer of. The method of claim 6,
The resin composition, wherein the ?-olefin content of the elastomer is 50 to 95 mass% with respect to the total mass of the elastomer. A biaxially stretched film obtained by biaxially stretching the resin composition according to any one of claims 1 to 7. A laminate comprising the biaxially stretched film according to claim 8 and a metal layer disposed on at least one surface of the biaxially stretched film.