KR102595637B1 - Polyarylene sulfide resin composition, and biaxially stretched films and laminates using the same - Google Patents

Abstract

The purpose of the present invention is to provide a resin composition in which the obtained biaxially stretched film has excellent stretching uniformity and dielectric properties. Specifically, it is a resin composition having a continuous phase and a dispersed phase, using at least polyarylene sulfide resin, polyphenylene ether resin, styrene-(meth)acrylic acid copolymer, and elastomer as raw materials, wherein the continuous phase is: A resin composition containing a polyarylene sulfide resin, the dispersed phase containing a polyphenylene ether-based resin and an elastomer, and an average dispersion diameter of the dispersed phase being 5 μm or less, and a biaxially stretched film thereof are provided.

Description

Polyarylene sulfide resin composition, and biaxially stretched films and laminates using the same

The present invention relates to a polyarylene sulfide resin composition with excellent stretchability and low dielectric constant, and biaxially stretched films and laminates using the same.

Recently, the field of flexible printed wiring boards (FPC) and flexible flat cables (FFC) has been accompanied by developments in cloud and IoT (Internet of Things), improvements in technology for automatic driving of automobiles, and developments in electric vehicles and hybrid vehicles. Therefore, there is a need for cables and antennas that can process large amounts of data and transmit it at high speed and without loss. However, conventionally, polyimide (PI) films have been used as FPC substrates, and polyester films (PET films, etc.) have been used as FCC substrates, and they cannot be said to have dielectric properties that can support the next generation of high-speed transmission.

However, films using polyarylene sulfide resins, such as polyphenylene sulfide resin (PPS), are excellent in heat resistance, flame retardancy, chemical resistance, and electrical insulation, and are therefore used as insulating materials for condensers and motors, as well as heat-resistant tapes. . Polyarylene sulfide resin has superior dielectric properties compared to PI or PET, so it can be applied to the fields of flexible printed wiring boards (FPC) and flexible flat cables (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. ㎛, 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 longitudinal cross section of the film and the thickness direction cross section of the film in the width direction is 2 to 125. An invention according to a biaxially stretched thermoplastic resin film is described. Patent Document 1 describes that the biaxially stretched thermoplastic resin film is excellent in surface appearance, mechanical properties, and heat dimensional stability.

In addition, Patent Document 1 states that a polymer alloy obtained by mixing polyphenylene ether, which has a high glass transition temperature, with polyphenylene sulfide, which has a conventionally low glass transition temperature and is prone to heat shrinkage, has excellent heat resistance, moldability, impact resistance, etc. What was known is described.

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

And, it is described that the biaxially stretched thermoplastic resin film can be used for printed board materials, printed board peripheral components, half-circuit board materials, etc.

Japanese Patent Application Publication No. 2009-179766

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

Therefore, the purpose of the present invention is to provide a resin composition in which the resulting biaxially stretched film has excellent stretching uniformity and dielectric properties.

The present inventors conducted thorough studies to solve the above problems. As a result, it was found that the above problems could be solved by using styrene-(meth)acrylic acid copolymer and elastomer along with polyarylene sulfide resin and polyphenylene ether resin, and the present invention was completed. .

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

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

(2) The content of the polyphenylene ether resin is 1 to 40% 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 described in (1) above;

(3) The content of the styrene-(meth)acrylic acid copolymer is 0.5 to 10 mass with respect to the total mass of 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) above, wherein the (meth)acrylic acid content of the styrene-(meth)acrylic acid copolymer is 1 to 30% by mass relative to the total mass of the styrene-(meth)acrylic acid copolymer. The resin composition according to any one of the above;

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

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

(7) The resin composition according to (6) above, wherein the α-olefin content of the elastomer is 50 to 95% by mass based on 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) above and a metal layer disposed on at least one surface of the biaxially stretched film.

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

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

[Resin composition]

The resin composition contains at least polyarylene sulfide resin (hereinafter sometimes referred to as “PAS resin”), polyphenylene ether-based resin (hereinafter sometimes referred to as “PPE-based resin”), and styrene-( It is made from meta)acrylic acid and elastomer. At this time, the resin composition has a continuous phase and a dispersed phase. At this time, the continuous phase contains a polyarylene sulfide resin, and the dispersed phase contains a polyphenylene ether-based resin and an elastomer. In addition, most of the styrene-(meth)acrylic acid is contained in the dispersed phase.

When the continuous phase is 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. If 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 the value measured by the method described in the Examples.

[Polyarylene sulfide resin]

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

The PAS resin has a resin structure in which a repeating unit is a structure in which an aromatic ring and a sulfur atom are bonded.

Specific examples of polyarylene sulfide resins include resins whose repeating units are structural moieties represented by the following structural formula (1).

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

Here, it is preferable that all of the structural moieties represented by the structural formula (1), especially R ¹ in the formula, are hydrogen atoms from the viewpoint of the mechanical strength of the PAS resin. Examples of those in which R ¹ is all a hydrogen atom include those bonded at the para position represented by structural formula (2) below, and those bonded at the meta position represented by structural formula (3) below.

Among these, it is preferable that the bond of the sulfur atom to the aromatic ring in the repeating unit is bonded at the para position as shown in the structural formula (2) from the viewpoint of heat resistance and crystallinity of the PAS resin.

In addition, the PAS resin may contain not only the structural moiety represented by the structural formula (1), but also structural moieties represented by the following structural formulas (4) to (7).

When including structural moieties represented by structural formulas (4) to (7), the structural moieties represented by the structural formulas (4) to (7) are 30 mol in total with the structural moieties represented by the structural formula (1). It is preferable that it contains % or less, and from the viewpoint of heat resistance and mechanical strength of the PAS resin, it is more preferable that it is 10 mol% or less.

When the PAS resin contains structural moieties represented by the structural formulas (4) to (7), their bonding mode may be either a random copolymer or a block copolymer.

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

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

Such PAS resin can be manufactured, 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 polymerizing 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 (1) of reacting sodium sulfide with p-dichlorobenzene in an amide-based solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfone-based solvent such as sulfolane is easy to control the reaction, and is used in industrial applications. It is desirable because it has excellent productivity.

In addition, since linear and high molecular weight PAS resins can be manufactured efficiently industrially, among the above method (1), solid alkali metal sulfide, dichlorobenzene, alkali metal hydrosulfide, and organic acid alkali metal salt are essential. A method of preparing a reaction slurry containing the ingredients and heating it to perform polymerization in a heterogeneous system is particularly preferable. This polymerization method is specifically,

Process 1:

Hydrous alkali metal sulfide, or

Hydrous alkali metal hydrosulfide and alkali metal hydroxide,

N-methylpyrrolidone,

non-hydrolyzable organic solvent,

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

Process 2:

Next, in the slurry (I),

dichlorobenzene,

The alkali metal hydrosulfide,

Alkali metal salt of the hydrolyzate of N-methylpyrrolidone

A process of polymerizing by reacting

A method comprising a is preferable in terms of productivity.

Examples of the hydrous alkali metal sulfide used here include liquid or solid hydrous compounds of compounds 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, and more preferably 35 to 65% by mass.

In addition, examples of the hydrous alkali metal hydrosulfide include liquid or solid hydrous products of compounds such as lithium hydrosulfide, sodium hydrosulfide, potassium hydrosulfide, rubidium hydrosulfide, and cesium hydrosulfide. Among these, hydrated products of lithium hydrosulfide and hydrated sodium hydrosulfide are preferable, and hydrated products of sodium hydrosulfide are particularly preferable. Additionally, the solid content concentration of the hydrous alkali metal hydrosulfide is preferably 10 to 80 mass%.

In addition, examples of the alkali metal hydroxides 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 preferred, and sodium hydroxide is particularly preferred. Moreover, when using an aqueous solution of an alkali metal hydroxide, an aqueous solution with a concentration of 20% by mass or more is preferable because the dehydration treatment in step 1 is easy.

Among the PAS resins obtained in this way, they have a peak in the molecular weight range of 25,000 to 30,000, especially when measured using gel permeation chromatography (GPC), and the ratio between 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 maintained at 1,500 to 2,000 ppm without reducing the mechanical strength of the molded product. This is desirable because it can be reduced to the range of , making it easy to apply to halogen-free electronic and electrical components.

In addition, in this specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw/Mn) are measured using the values measured by gel permeation chromatography (GPC). Additionally, 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 Company)

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

column temperature; 210℃

menstruum; 1-Chloronaphthalene

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

The above-described PAS resin further improves moisture resistance characteristics by reducing the amount of residual metal ions and can reduce the residual amount of low molecular weight impurities generated by-product during polymerization, so after manufacturing the PAS resin. , it is preferable that it is treated with acid and then washed with water.

As acids that can be used here, acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid, and propylic acid are preferred because they do not decompose in the PAS resin and can efficiently reduce the amount of remaining metal ions, and acetic acid and hydrochloric acid are more preferred. .

A method of acid treatment includes immersing the PAS resin in an acid or an acid aqueous solution. At this time, further stirring or heating may be performed as needed.

Here, the specific method of the acid treatment is, taking the case of using acetic acid as an example, first heating an aqueous solution of acetic acid at pH 4 to 80 to 90°C, immersing the PAS resin in it, and stirring for 20 to 40 minutes. I can hear it.

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

In addition, the PAS resin used for the acid treatment is preferably in the form of powder or granular material. Specifically, it may be a granular body such as a pellet, or may be in a slurry state after polymerization.

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

[Polyphenylene ether-based resin]

In principle, polyphenylene ether-based resin is contained in the dispersed phase of the resin composition. The PPE-based resin in the dispersed phase has the function of lowering the dielectric constant of the resulting biaxially stretched film.

Polyphenylene ether-based resin is a homopolymer and/or copolymer having a structural portion represented by the following structural formula (9).

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 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 polyphenylene ether resin include poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), and poly(2-phenylene ether). methyl-6-phenyl-1,4-phenylene ether), poly(2,6-dichloro-1,4-phenylene ether), and 2,6-dimethylphenol and other phenols (e.g. , 2,3,6-trimethylphenol or 2-methyl-6-butylphenol), and polyphenylene ether copolymers such as copolymers can also be mentioned. Among them, poly(2,6-dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, is preferred, and poly(2,6-dimethyl- 1,4-phenylene ether) is more preferred.

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

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

[Styrene-(meth)acrylic acid copolymer]

Most of the styrene-(meth)acrylic acid copolymer is contained in the dispersed 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 mechanical strength (tear strength, etc.). It can have functions.

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.”

The styrene-based monomer is not particularly limited and includes styrene and its derivatives. 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; Methoxystyrene, etc. can be mentioned. These styrene-based monomers may be used individually, or may be used in combination of two or more types.

Examples of (meth)acrylic acid monomers include acrylic acid and methacrylic acid, as well as (meth)acrylic acid alkyl esters having a substituted or unsubstituted alkyl group of 1 to 6 carbon atoms. At this time, the substituent is not particularly limited, and includes halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom, and hydroxyl group. Additionally, it may have one substituent or two or more substituents. When having two or more substituents, each substituent may be the same or different from each other. Specific examples of (meth)acrylic acid alkyl esters 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, Examples include t-butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, hydroxyethyl (meth)acrylate, and hydroxypropyl (meth)acrylate. Among these, (meth)acrylic acid is preferable from the viewpoint of compatibility and reactivity with the elastomer. Moreover, these (meth)acrylic acid monomers may be used individually, or may be used in combination of two or more types.

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

For the polymerization reaction of the styrene-(meth)acrylic acid copolymer, various commonly used polymerization methods of styrene-based monomers can be applied. There is no particular limitation on the polymerization method, but block polymerization, suspension polymerization, or solution polymerization are preferable. Among them, continuous bulk polymerization is particularly preferable from the viewpoint of production efficiency. For example, continuous bulk polymerization is performed by introducing a tubular reactor in which one or more stirring reactors and a plurality of mixing elements without moving parts are fixed inside. 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. Additionally, polymerization aids such as suspending agents and emulsifiers required for polymerization can 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, and 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 two or more types.

The radical polymerization initiator is not particularly limited and includes, 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 dicinamoyl peroxide; Peroxy esters such as t-butyl peroxybenzoate, di-t-butyl peroxyisophthalate, and t-butyl peroxyisopropyl monocarbonate; N,N'-azobisisobutylnitrile, N,N'-azobis(cyclohexane-1-carbonitrile), N,N'-azobis(2-methylbutyronitrile), N,N'-azo Bis(2,4-dimethylvaleronitrile), N,N'-azobis[2-(hydroxymethyl)propionitrile], etc. can be mentioned. These radical polymerization initiators can be used alone or in combination of two or more types.

Additionally, a chain transfer agent may be added to prevent the molecular weight of the resulting resin composition from becoming excessively large. As the chain transfer agent, either a monofunctional chain transfer agent having one chain transfer group or a polyfunctional chain transfer agent having multiple chain transfer groups can be used.

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

As a multifunctional chain transfer agent, the hydroxyl group in polyhydric alcohols such as ethylene glycol, neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, and sorbitol is esterified with thioglycolic acid or 3-mercaptopropionic acid. Things like being angry can be mentioned.

The above-mentioned chain transfer agent may be used individually, or may be used in combination of two or more types.

Additionally, in order to suppress gel generation in the resulting resin composition, it is also possible to use long-chain alcohols, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyoleyl ether, polyoxyethylene alkenyl ether, etc.

The content of the styrene-(meth)acrylic acid copolymer is preferably 0.5 to 10% by mass, based on the total mass of the PAS resin, polyphenylene ether resin, styrene-(meth)acrylic acid copolymer, and elastomer, and is preferably 0.5 to 10% by mass. It is more preferable that it is 5 mass %, from the viewpoint of stretching 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-based resin]

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

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

The styrene-based resin may be a homopolymer of styrene-based monomers, or may be a copolymer formed by copolymerizing two or more types. Additionally, it may be rubber-modified styrene (high impact styrene) using rubber components such as polybutadiene, styrene-butadiene copolymer, polyisoprene, and butadiene-isoprene copolymer.

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

Moreover, the above-mentioned styrene resin may be used individually, or may be used in combination of 2 or more types.

[Elastomer]

The elastomer is, in principle, 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-based resin, and has the function of improving mechanical strength (tearing strength, etc.) by microdispersing the dispersed phase. In addition, by using it in combination with a styrene-(meth)acrylic acid copolymer, the adhesion at the interface between the PSA resin and the polyphenylene ether resin is further improved through the elastomer, and the mechanical strength (tear strength, etc.) is further improved. do.

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

Examples of the α-olefin include ethylene, propylene, and 1-butene. Among these, it is preferable to use ethylene.

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

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 includes vinyl group, 1-propenyl group, 2-propenyl group, 1-methylethenyl group, 1-butenyl group, 2-butenyl group, and 1-methyl-1. -propenyl 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.

In addition, 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.

The alkyl group having 1 to 6 carbon atoms is not particularly limited, but includes methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, and 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, Examples include 2,3-dimethylbutyl group, 2,4-dimethylbutyl group, 3,3-dimethylbutyl group, and 2-ethylbutyl group.

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

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

In addition, when the elastomer is a copolymer of α-olefin, α,β-unsaturated glycidyl ester, or a copolymer of α-olefin, α,β-unsaturated glycidyl ester, and acrylic acid ester, the elastomer The content of α-olefin in the film is preferably 50 to 95% by mass, and is more preferably 50 to 80% by mass from the viewpoint of stretching uniformity, tear strength, etc.

The content of the elastomer is preferably 1 to 30% by mass, and more preferably 3 to 20% by mass, relative to 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 viewpoints of dielectric constant, tearing strength, etc.

[Alkoxysilane with 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 resin is dramatically improved, and a good morphology can be formed.

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

The compounding amount of the alkoxysilane having the amino group is preferably 0.01 to 5% by mass, 0.1 to 3% 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 mass %.

[additive]

The resin composition may contain plasticizers, weathering agents, antioxidants, heat stabilizers, UV stabilizers, lubricants, antistatic agents, colorants, conductive agents, etc., as long as they do not impair the effects of the present invention.

<Method for producing resin composition>

The method for producing the above-mentioned resin composition is not particularly limited, but the PAS resin, polyphenylene ether-based resin, styrene-(meth)acrylic acid copolymer, elastomer, and other mixing components as necessary are mixed in a tumbler or Henschel mixer, etc. A method of mixing uniformly and then putting it into a twin-screw extruder to melt and knead is included. At this time, the melt kneading is preferably performed under conditions where the ratio (discharge amount/screw rotation speed) between the discharge amount of the resin component (kg/hr) 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 the dispersed phase of 5 μm or less can be produced.

If the above manufacturing method is described in more detail, a method of putting each of the above-mentioned components into a twin-screw extruder and melting and kneading them under temperature conditions of a set temperature of 300°C and a resin temperature of about 330°C is included. 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. Among these, it is preferable that it is 20 to 35 kg/hr, especially from the viewpoint of dispersibility. Therefore, it is more preferable that the ratio (discharge amount/screw rotation speed) between the discharge amount of the resin component (kg/hr) and the screw rotation speed (rpm) is particularly 0.08 to 0.14 (kg/hr·rpm). In addition, the torque of the twin-screw extruder is preferably in the range of 20 to 100 (Å), especially 25 to 80 (Å), in order to ensure good dispersibility of the polyphenylene ether-based resin and elastomer.

<Biaxially stretched film>

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

In addition, as will be described later, the average dispersion diameter of the biaxially stretched film is determined at or below the Tg of the resin (particularly polyphenylene ether) constituting the dispersed phase in the resin composition under the manufacturing conditions (temperature conditions, etc.) of the biaxially stretched film of the present invention. Therefore, the dispersed phase is not deformed and the average dispersion diameter in the resin composition is maintained.

The stretch 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.

Additionally, the stretch 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 stretch ratio in the longitudinal direction (MD direction) of the biaxially stretched film and the stretch ratio in the width direction (TD direction) of the biaxially stretched film (longitudinal direction (MD direction))/(width direction (TD direction)) is: It is preferable that it is 0.8 to 1.2, and it is more preferable that it is 0.9 to 1.1.

<Method for manufacturing biaxially stretched film>

The manufacturing method of the biaxially stretched film is not particularly limited, and known methods can be adopted. For example, the resin composition is dried at 140°C for 3 hours or more under reduced pressure of 10 mmhg or less, and then placed into an extruder heated to 280-320°C. Thereafter, the molten resin that has passed through the extruder is discharged from a T-die in the form of a sheet, and is cooled and solidified by being brought into close contact with a cooling roll with a surface temperature of 20 to 50°C to obtain an unoriented, unstretched sheet.

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

In the case of biaxial stretching by the sequential biaxial stretching method, for example, the obtained unstretched sheet is heated with a group of heating rolls and stretched 2 to 4 times in the longitudinal direction (MD direction), preferably 2.5 to 3.8 times in one stage. Or, stretch it 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 from Tg+5°C to Tg+30°C, more preferably from Tg+5°C to Tg+20°C. . Afterwards, it is cooled with a cooling roll group at 30 to 60°C.

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

Next, this stretched film is heat fixed while being tensioned or relaxed in the width direction. There is no particular limitation on the heat setting temperature, but it is in the range of 200 to 275°C, preferably 220 to 275°C, more preferably 240 to 270°C. You can change the heat setting temperature and perform it in two stages. In that case, it is desirable to set the heat setting temperature of the second stage by +10 to 40°C higher than that of the first stage. The heat setting time is preferably in the range of 1 to 60 seconds. In addition, in heat setting, the biaxially stretched film is heated, so even if the resin (especially polyphenylene ether) constituting the dispersed phase melts during the heat setting process, the molten resin cannot move, and upon completion of heat setting, the melted resin cannot move. 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 in the range of 0.5 to 10%, more preferably in the range of 2 to 8%, and even more preferably in the range of 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.

The metal layer is not particularly limited, but examples include copper, aluminum, zinc, titanium, nickel, and alloys containing these.

Additionally, the metal layer may be a single layer or a two layer layer. When the metal layer is two layers, each metal phase may be the same or different from each other.

In one embodiment, the laminate includes 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, and a metal layer-metal layer-biaxially stretched film. -It may have a composition such as a metal layer.

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

A laminate provided with a metal layer can be suitably used for next-generation high-speed transmission because the biaxially stretched film has excellent dielectric properties. In addition, since the biaxially stretched film has excellent stretching uniformity, the above-described laminate has excellent thickness uniformity and can suppress non-uniformity in dielectric constant.

(Example)

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

[Example 1]

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

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

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

The unstretched PPS resin sheet was biaxially stretched at 3.0 × 3.0 times at 100°C using a batch biaxial stretching machine (manufactured by Moto Seisakujo Co., Ltd.) to obtain a film with a thickness of 35 μm. Then, the obtained film was fixed to a mold and heat-set in an oven at 260°C to produce a biaxially stretched film.

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

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

Additionally, the average dispersion diameter of the dispersed phase of the biaxially stretched sheet was measured in the same manner as in Example 1, and was found to be 1.4 μm.

[Example 3]

A resin composition and a biaxially stretched sheet were produced 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.

Additionally, the average dispersion diameter of the dispersed phase of the biaxially stretched sheet was measured in the same manner as in Example 1, and was found to be 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.

Additionally, the average dispersion diameter of the dispersed phase of the biaxially stretched sheet was measured in the same manner as in Example 1, and was found to be 1.7 μm.

[Example 5]

A resin composition and a biaxially stretched sheet were produced 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.

Additionally, the average dispersion diameter of the dispersed phase of the biaxially stretched sheet was measured in the same manner as in Example 1, and was found to be 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 stretching ratio was 3.5 × 3.5 times.

Additionally, the average dispersion diameter of the dispersed phase of the biaxially stretched sheet was measured in the same manner as in Example 1, and was found to be 1.2 μm.

[Example 7]

A resin composition and a biaxially stretched sheet were produced 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.

Additionally, the average dispersion diameter of the dispersed phase of the biaxially stretched sheet was measured in the same manner as in Example 1, and was found to be 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.

Additionally, the average dispersion diameter of the dispersed phase of the biaxially stretched sheet was measured in the same manner as in Example 1, and was found to be 1.6 μm.

[Example 9]

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

Additionally, the average dispersion diameter of the dispersed phase of the biaxially stretched sheet was measured in the same manner as in Example 1, and was found to be 1.5 μm.

[Example 10]

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

Additionally, the average dispersion diameter of the dispersed phase of the biaxially stretched sheet was measured in the same manner as in Example 1, and was found to be 1.8 μm.

[Example 11]

A resin composition and a biaxially stretched sheet were manufactured 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.

Additionally, the average dispersion diameter of the dispersed phase of the biaxially stretched sheet was measured in the same manner as in Example 1, and was found to be 1.5 μm.

[Example 12]

A resin composition and a biaxially stretched sheet were manufactured 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.

Additionally, the average dispersion diameter of the dispersed phase of the biaxially stretched sheet was measured in the same manner as in Example 1, and was found to be 1.3 μm.

[Example 13]

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

Additionally, the average dispersion diameter of the dispersed phase of the biaxially stretched sheet was measured in the same manner as in Example 1, and was found to be 2.8 μm.

[Comparative Example 1]

A resin composition and a biaxially stretched sheet were produced in the same manner as in Example 1, except that 100 parts by mass of PPS resin was used and PPE-based resin, SMAA, and elastomer were not used.

[Comparative Example 2]

A resin composition and a biaxially stretched sheet were produced 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 no PPE-based resin or SMAA was used.

Additionally, the average dispersion diameter of the dispersed phase of the biaxially stretched sheet was measured in the same manner as in Example 1, and was found to be 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.

Additionally, the average dispersion diameter of the dispersed phase of the biaxially stretched sheet was measured in the same manner as in Example 1, and was found to be 2 μm.

The 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]

The physical properties of the biaxially stretched sheets manufactured in Examples 1 to 13 and Comparative Examples 1 to 3 were evaluated.

[permittivity]

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

[Stretch uniformity]

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

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

○; Between 80% and less than 90% of the grid on the front of the film is square.

△; More than 50% to less than 80% of the grid on the front of the film is square.

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

[Tearing Strength]

A sample was punched out from the biaxially stretched film into a shape based on JIS K6732:2006. After the punched sample was left standing in a constant temperature room at 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 Corporation) to measure the tear strength. The obtained results are shown in Table 2 below.

[Table 2]

As is also clear from the description in Table 2, it can be seen that the obtained biaxially stretched film has excellent stretching uniformity and dielectric properties.

Claims (9)

A resin composition having a continuous phase and a dispersed phase, using at least polyarylene sulfide resin, polyphenylene ether resin, styrene-(meth)acrylic acid copolymer, and elastomer as raw materials,
The continuous phase includes polyarylene sulfide resin,
The dispersed phase includes a polyphenylene ether-based resin and an elastomer,
The average dispersion diameter of the dispersed phase is 5 μm or less,
The styrene-(meth)acrylic acid copolymer is a copolymer obtained by copolymerizing a styrene-based monomer and a (meth)acrylic acid monomer, and the (meth)acrylic acid monomer is acrylic acid and/or methacrylic acid. According to paragraph 1,
A resin composition in which the content of the polyphenylene ether resin is 1 to 40% by mass based on the total mass of the polyarylene sulfide resin, polyphenylene ether resin, styrene-(meth)acrylic acid copolymer, and elastomer. . According to claim 1 or 2,
The content of the styrene-(meth)acrylic acid copolymer is 0.5 to 10% by mass based on the total mass of the polyarylene sulfide resin, polyphenylene ether resin, styrene-(meth)acrylic acid copolymer, and elastomer, Resin composition. According to claim 1 or 2,
A resin composition wherein the (meth)acrylic acid content of the styrene-(meth)acrylic acid copolymer is 1 to 30% by mass with respect to the total mass of the styrene-(meth)acrylic acid copolymer. According to claim 1 or 2,
A resin composition wherein the content of the elastomer is 3 to 20% by mass with respect to the total mass of the polyarylene sulfide resin, polyphenylene ether resin, styrene-(meth)acrylic acid copolymer, and elastomer. According to claim 1 or 2,
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 containing at least one selected from the group consisting of copolymers. According to clause 6,
A resin composition wherein the α-olefin content of the elastomer is 50 to 95% by mass based on the total mass of the elastomer. A biaxially stretched film obtained by biaxially stretching the resin composition according to claim 1 or 2. 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.