KR20220101100A - Biaxially stretched laminated film, laminate, and manufacturing method thereof - Google Patents

Abstract

To provide a film capable of and good direct thermal bonding at a temperature below the melting point of a metal layer and a polyarylene sulfide resin and capable of low dielectric constant and low dielectric loss tangent, a laminate using the same, and a manufacturing method thereof.
A resin layer consisting of a film obtained by biaxially stretching a resin composition (A) having a specific morphology formed by preparing a polyarylene sulfide resin with a polyphenylene ether-based resin and a styrene-(meth)acrylic acid copolymer as raw materials; A biaxially stretched laminated film arranged as a layer to be directly adhered to a metal or a resin molded body, a laminate formed by contacting the biaxially stretched laminated film with a metal layer and/or a resin molded body, and a method for producing them.

Description

Biaxially stretched laminated film, laminate, and manufacturing method thereof

The present invention relates to a biaxially stretched laminated film, a laminate, and a method for producing them, and more specifically, a polyarylene sulfide-based biaxially stretched laminate having excellent thermal adhesion with a metal and/or resin molded body and low dielectric properties. It relates to a film, a laminate using the same, and a manufacturing method thereof.

In recent years, in the field of flexible printed wiring board (FPC) and flexible flat cable (FFC), power generation such as ground and IoT (Internet of Things), improvement of technology for autonomous driving of automobiles, and development of electric vehicles and hybrid vehicles Therefore, there is a demand for a cable or antenna capable of processing a large amount of data or transmitting it at high speed and without loss. However, conventionally, polyimide (PI) films have been used for FPC substrates and polyester films (PET films, etc.) have been used for FCC substrates. In addition, a laminate of a polyester film and an aramid paper is used from the viewpoint of the immersion property of motor oil for an insulating material used around a motor employed in next-generation automobiles such as electric vehicles and hybrid vehicles. However, there is a problem that the polyester film is inferior in heat resistance.

On the other hand, a film using a polyarylene sulfide resin typified by polyphenylene sulfide resin (PPS) is excellent in heat resistance, flame resistance, chemical resistance, and electrical insulation, so it is used as an insulating material for capacitors and motors, and heat-resistant tape. have. Since polyarylene sulfide resin has excellent dielectric properties compared to PI or PET, it can be applied to fields such as flexible printed wiring boards (FPC) and flexible flat cables (FFC). However, a polyarylene sulfide film has the subject that the adhesiveness and adhesiveness of a metal and other resin are low in general, and the reactivity with an adhesive agent is insufficient. As an improvement on this, for example, in Patent Document 1, a resin layer composed of a resin composition containing polyphenylene sulfide as a main component on at least one surface of a metal plate is a laminate as a laminate without an adhesive interposed therebetween. A laminate is described, characterized in that the degree of orientation OF is in the range of 0.65 to 0.9.

Japanese Patent Laid-Open No. 2005-88273

However, in the laminate described in Patent Document 1, a polyphenylene sulfide resin layer and a metal plate are directly laminated, and although it has excellent adhesion to a metal, the dielectric constant and dielectric loss tangent are high, so that it cannot sufficiently cope with high-speed transmission. Moreover, since thermocompression is carried out substantially above the melting|fusing point of polyphenylene sulfide resin, it is difficult to obtain a thing with favorable external appearance.

Therefore, in the present invention, the metal layer and the polyarylene sulfide resin can be directly thermally bonded at a temperature below the melting point of the polyarylene sulfide resin, and the adhesiveness is good, and the dielectric constant and the low dielectric loss tangent are further reduced. It is to provide a possible film, a laminate using the same, and a manufacturing method thereof.

As a result of earnest examination, the present inventors prepared a resin composition (A) in which a specific morphology was formed by using, as a raw material, a polyphenylene ether-based resin and a styrene-(meth)acrylic acid copolymer to a polyarylene sulfide resin. By using a biaxially stretched laminated film in which a resin layer made of a biaxially stretched film is disposed as a layer to be directly adhered to a metal or a resin molded body, it has been found that the above problems can be solved, and the present invention has been completed.

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

(1) The present invention is a biaxially stretched laminated film having a structure in which at least two resin layers are directly laminated,

The biaxially stretched laminated film,

At least one layer is formed by blending at least a polyarylene sulfide resin, a polyphenylene ether-based resin, and a styrene-(meth)acrylic acid copolymer as raw materials, and the resin composition (A) having a continuous phase and a dispersed phase It is a resin layer (A) consisting of a biaxially oriented film,

The continuous phase comprises a polyarylene sulfide resin,

The dispersed phase contains a polyphenylene ether-based resin,

The average dispersion diameter of the said dispersed phase is the range of 5 micrometers or less, It relates to the biaxially stretched laminated|multilayer film characterized by the above-mentioned.

(2) In the present invention, 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 (meth)acrylic acid. ) It relates to the biaxially stretched laminated|multilayer film as described in.

(3) The present invention relates to the biaxially stretched laminated film according to (1), wherein the polyarylene sulfide resin has an acid group.

(4) In the present invention, the content of the polyphenylene ether-based resin is 3 to 40 with respect to a total of 100 parts by mass of the polyarylene sulfide resin, the polyphenylene ether-based resin, and the styrene-(meth)acrylic acid copolymer. It relates to the biaxially stretched laminated|multilayer film as described in said (1) which is the range of mass parts.

(5) In the present invention, the ratio of the blending amount of the styrene-(meth)acrylic acid copolymer is 100 parts by mass in total of the polyarylene sulfide resin, polyphenylene ether-based resin and styrene-(meth)acrylic acid copolymer. , It relates to the biaxially stretched laminated|multilayer film as described in said (1) which is the range of 0.5-10 mass parts.

(6) In the present invention, the (meth)acrylic acid content of the styrene-(meth)acrylic acid copolymer is in the range of 1 to 30% by mass relative to the total mass of the styrene-(meth)acrylic acid copolymer, ( It relates to the biaxially stretched laminated|multilayer film as described in 1).

(7) The present invention relates to the biaxially stretched laminated film according to the above (1), wherein the resin composition (A) further contains an elastomer.

(8) In this invention, the ratio of the compounding quantity of the said elastomer is 3-15 with respect to a total of 100 mass parts of polyarylene sulfide resin, polyphenylene ether-type resin, styrene- (meth)acrylic acid copolymer, and an elastomer. It relates to the biaxially stretched laminated|multilayer film as described in said (1) which is the range of mass parts.

(9) The present invention provides that the elastomer comprises a copolymer of an α-olefin and a glycidyl ester of an α,β-unsaturated carboxylic acid, and an α-olefin and a glycidyl ester of an α,β-unsaturated carboxylic acid; , It relates to the biaxially stretched laminated|multilayer film as described in said (1) containing at least 1 selected from the group which consists of copolymers of (meth)acrylic acid ester.

(10) The present invention relates to the biaxially stretched laminated film according to the above (9), wherein the α-olefin content of the elastomer is in the range of 50 to 95 mass % with respect to the total mass of the elastomer.

(11) The present invention is a biaxially stretched film of a resin composition having a structure in which at least the resin layer (A) and the resin layer (B) are directly laminated, and the resin layer (B) contains a polyarylene sulfide resin Phosphorus, it relates to the biaxially stretched laminated|multilayer film as described in said (1).

(12) The present invention has a structure in which the resin layer (A) of the biaxially stretched laminated film according to any one of (1) to (11), and at least one selected from the group consisting of a metal layer and a resin molded body are in contact with each other. It relates to a laminated body having

(13) This invention relates to the flexible printed wiring board provided with the laminated body as described in said (12).

(14) This invention relates to the flexible flat cable provided with the laminated body as described in said (12).

(15) This invention relates to the insulator for motors provided with the laminated body as described in said (12).

(16) The present invention provides a method for producing a biaxially stretched laminated film having a structure in which at least two resin layers are directly laminated,

having a step of biaxially stretching an unstretched laminated sheet having a structure in which at least two resin layers are directly laminated;

The biaxially stretched laminated film,

At least one layer is at least polyarylene sulfide resin, polyphenylene ether-based resin, and a styrene- (meth) acrylic acid copolymer as raw materials, the resin composition (A) having a continuous phase and a dispersed phase by biaxial stretching A resin layer (A) comprising a biaxially stretched film comprising

The continuous phase comprises a polyarylene sulfide resin,

The dispersed phase contains a polyphenylene ether-based resin,

The average dispersion diameter of the dispersed phase in the said resin layer (A) is 5 micrometers or less, It relates to the manufacturing method of the biaxially stretched laminated|multilayer film characterized by the above-mentioned.

(17) The present invention provides for bonding the resin layer (A) of the biaxially stretched laminated film according to any one of (1) to (11) above, and at least one selected from the group consisting of a metal layer and a resin molded body. , to a method for manufacturing a laminate.

According to the present invention, direct thermal bonding between the metal layer and the polyarylene sulfide resin at a temperature below the melting point of the polyarylene sulfide resin is possible, and the adhesiveness is good, and further low dielectric constant and low dielectric loss tangent are possible. A film, a laminate using the same, and a manufacturing method thereof can be provided.

Hereinafter, the biaxially stretched laminated|multilayer film and laminated body of this invention are demonstrated in detail based on suitable embodiment.

The biaxially stretched laminated|multilayer film of this invention,

Having a structure in which at least two resin layers are directly laminated,

At least one layer includes at least a polyarylene sulfide resin (hereinafter, also referred to as “PAS resin”), a polyphenylene ether-based resin (hereinafter also referred to as “PPE-based resin”), and styrene- (meta ) A resin layer (A) comprising a biaxially stretched film of a resin composition (A) having a continuous phase and a dispersed phase, which is formed by blending an acrylic acid copolymer as a raw material,

The continuous phase comprises a polyarylene sulfide resin,

The dispersed phase contains a polyphenylene ether-based resin,

It is characterized in that the average dispersion diameter of the dispersed phase is in the range of 5 µm or less.

The resin composition (A) used for this invention uses polyarylene sulfide resin as an essential raw material, and mix|blends it. In the resin composition (A) used for this invention, PAS resin is a main component, and is mainly contained in a continuous phase.

The PAS resin used in the present invention is a polymer including, as a repeating unit, a structure in which an aromatic ring and a sulfur atom are bonded (specifically, a structure represented by the following formula (1)).

In the 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, an ethoxy group, and n is each independently, each of 1 to 4 is an integer

Here, it is preferable that all of R< ¹ > in the structure represented by Formula (1) are a hydrogen atom. With such a structure, the mechanical strength of PAS resin can be raised more. As the structure represented by the formula (1) in which all R ¹ are hydrogen atoms, the structure represented by the following formula (2) (that is, a structure in which a sulfur atom is bonded at a para position to the aromatic ring), and the following formula (3) The structure shown (that is, the structure in which a sulfur atom couple|bonds at meta position with respect to an aromatic ring) is mentioned. Moreover, the PAS resin of the copolymer of Formula (2) and Formula (3) may be sufficient, and, as for the copolymerized PAS resin, 80 mol% or more is comprised by Formula (2), Preferably it is 95 mol% or more from 85 mol% or more. mol% or less, preferably 92 mol% or less. If it is the said range, since a film is hold|maintained and melting|fusing point can be reduced, it is preferable. Although the aspect of copolymerization of a copolymerization component is not specifically limited, It is preferable that it is a random copolymer.

Among these, it is preferable that the structure represented by Formula (1) is a structure represented by Formula (2). If it is PAS resin which has a structure represented by Formula (2), heat resistance and crystallinity can be improved more.

Moreover, PAS resin may contain not only the structure represented by the said Formula (1), but the structure represented by following formula (4)-(7) as a repeating unit.

It is preferable that 30 mol% or less is contained in all the repeating units which comprise PAS resin, and, as for the structure represented by Formula (4)-(7), it is more preferable that 10 mol% or less is contained. By such a structure, the heat resistance and mechanical strength of PAS resin can be raised more.

Moreover, any one of a random shape and a block shape may be sufficient as a coupling|bonding mode of the structure represented by Formula (4) - (7).

Moreover, the PAS resin may contain the trifunctional structure represented by following formula (8), a naphthyl sulfide structure, etc. as a repeating unit in the molecular structure.

The structure represented by the formula (8), the naphthyl sulfide structure, etc. are preferably contained in an amount of 1 mol% or less in all the repeating units constituting the PAS resin, and more preferably not substantially contained. According to such a structure, content of the chlorine atom in PAS resin can be reduced.

Moreover, the characteristic of PAS resin is although it does not specifically limit unless the effect of this invention is impaired, The melt viscosity (V6) in 300 degreeC becomes like this. Preferably it is 100 Pa.s or more, More preferably, it is 120 Pa.s. From the above, Preferably it is 2000 Pa*s or less, More preferably, it is the range of 1600 Pa*s or less. In this range, the balance between fluidity and mechanical strength becomes good, which is preferable.

Moreover, it is preferable that PAS resin has a peak in the range of molecular weight 25,000-40,000 in the measurement using gel permeation chromatography (GPC). Moreover, it is the range of the said molecular weight, and it is preferable that the ratio (Mw/Mn) of a weight average molecular weight (Mw) and a number average molecular weight (Mn) exists in the range of 5-10. Moreover, it is especially preferable that the range of the said molecular weight, the range of the said ratio (Mw/Mn), and also the range of a non-Newtonian index exist in the range of 0.9-1.3. By using such a PAS resin, the content of chlorine atoms in the PAS resin itself can be reduced to a range of 1,500 to 2,000 ppm without reducing the mechanical strength when a film is made, and halogen-free electron and electricity It is preferable because it becomes easy to apply to a component use.

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

[Measurement conditions by gel permeation chromatography]

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

A column: UT-805L (made by Showa Denko)

Column temperature: 210 degrees Celsius

Solvent: 1-chloronaphthalene

Measurement method: The molecular weight distribution and peak molecular weight are measured using 6 types of monodisperse polystyrene for calibration with a UV detector (360 nm).

Although it does not specifically limit as a manufacturing method of PAS resin, For example,

(Production method 1) A method of polymerizing a dihalogenoaromatic compound in the presence of sulfur and sodium carbonate, if necessary, adding a polyhalogenoaromatic compound or other copolymerization components;

(Manufacturing method 2) A method of polymerizing a dihalogenoaromatic compound in a polar solvent in the presence of a sulfiding agent or the like, if necessary by adding a polyhalogenoaromatic compound or other copolymerization components;

(Manufacturing method 3) The method of adding another copolymerization component, if necessary, and making p-chlorothiophenol self-condensate, etc. are mentioned. Among these manufacturing methods, the method of the said (Manufacturing method 2) is general and preferable.

In addition, in the case of reaction, in order to adjust the polymerization degree, you may add alkali metal salt of carboxylic acid or sulfonic acid, or alkali hydroxide.

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

In the method of (Method 2-1), a hydrous sulfiding agent is introduced into a mixture containing a heated organic polar solvent and a dihalogenoaromatic compound at a rate at which water can be removed from the reaction mixture, in the organic polar solvent When the dihalogenoaromatic compound and the sulfidation agent are reacted by adding a polyhalogenoaromatic compound as needed, the amount of water in the reaction system is controlled in the range of 0.02 to 0.5 mol per 1 mol of the organic polar solvent. A system resin (A) is produced (refer to Japanese Patent Application Laid-Open No. Hei 07-228699).

In the method of (Method 2-2), a dihalogenoaromatic compound and, if necessary, a polyhalogenoaromatic compound or other copolymerization components are added in the presence of a solid alkali metal sulfide and an aprotic polar organic solvent, When the alkali metal hydrosulfide and the organic acid alkali metal salt are reacted, the amount of the organic acid alkali metal salt is controlled in the range of 0.01 to 0.9 mol per 1 mol of sulfur atom, and the water content in the reaction system is adjusted to 1 mol of the aprotic polar organic solvent. By controlling in the range of 0.02 mol or less, PAS resin is manufactured (refer WO2010/058713 pamphlet).

Specific examples of the dihalogeno aromatic compound include p-dihalobenzene, m-dihalobenzene, o-dihalobenzene, 2,5-dihalotoluene, 1,4-dihalonaphthalene, 1-methoxy-2, 5-dihalobenzene, 4,4'-dihalobiphenyl, 3,5-dihalobenzoic acid, 2,4-dihalobenzoic acid, 2,5-dihalonitrobenzene, 2,4-dihalonitrobenzene, 2 ,4-dihaloanisole, p,p'-dihalodiphenyl ether, 4,4'-dihalobenzophenone, 4,4'-dihalodiphenylsulfone, 4,4'-dihalodiphenylsulfoxide, 4 ,4'-dihalodiphenyl sulfide, and compounds having an alkyl group in the range of 1 to 18 carbon atoms in the aromatic ring of each compound are mentioned.

Moreover, as a polyhalogeno aromatic compound, 1,2,3-trihalobenzene, 1,2,4-trihalobenzene, 1,3,5-trihalobenzene, 1,2,3,5 -tetrahalobenzene, 1,2,4,5-tetrahalobenzene, 1,4,6-trihalonaphthalene, etc. are mentioned.

Moreover, it is preferable that the halogen atom contained in the said compound is a chlorine atom and a bromine atom.

A well-known and usual method is used for the post-treatment method of the reaction mixture containing the PAS resin obtained by the polymerization process. Although it does not specifically limit as such a post-processing method, For example, the method of the following (post-processing 1) - (post-processing 5) is mentioned.

In the method of (Post-treatment 1), after the polymerization reaction is completed, first, the reaction mixture as it is or after adding an acid or a base, the solvent is distilled off under reduced pressure or normal pressure, and then the solid material after solvent distillation is distilled off with water, It is washed once or twice or more with a solvent such as a reaction solvent (or an organic solvent having an equivalent solubility to a low molecular weight polymer), acetone, methyl ethyl ketone, or alcohol, and further neutralized, washed with water, filtered and dried.

In the method of (post-treatment 2), after completion of the polymerization reaction, a solvent such as water, acetone, methyl ethyl ketone, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons and aliphatic hydrocarbons (soluble in the polymerization solvent used, Further, at least for the PAS resin, a solvent that is a poor solvent) is added as a precipitant to precipitate solid products such as the PAS resin and inorganic salt, and these are separated by filtration, washed and dried.

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

In the method of (Post-Treatment 4), after completion of the polymerization reaction, water is added to the reaction mixture for washing with water, filtration, and optionally washing with water, acid treatment is performed by adding an acid, followed by drying.

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

Examples of the acid usable in the method (post-treatment 4) include saturated fatty acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, and monochloroacetic acid, and unsaturated fatty acids such as acrylic acid, crotonic acid, and oleic acid. , aromatic carboxylic acids such as benzoic acid, phthalic acid and salicylic acid, dicarboxylic acids such as maleic acid and fumaric acid, organic acids such as sulfonic acids such as methanesulfonic acid and paratoluenesulfonic acid, hydrochloric acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, phosphoric acid, etc. and inorganic acids.

Moreover, as a hydrogen salt, sodium hydrogen sulfide, disodium hydrogen phosphate, sodium hydrogen carbonate etc. are mentioned, for example. However, in use in an actual machine, the organic acid with little corrosion with respect to a metal member is preferable.

In addition, in the method of the said (post-processing 1) - (post-processing 5), drying of PAS resin may be performed in vacuum, and may be performed in air or inert gas atmosphere like nitrogen.

In particular, in the PAS resin post-treated by the method of (Post-Treatment 4), the amount of acid groups bonded to the molecular terminals thereof increases, thereby obtaining an effect of increasing the dispersibility of the dispersed phase. As an acidic radical, it is especially preferable that it is a carboxyl group.

The ratio of the compounding quantity of the PAS resin in the resin composition (A) is preferably 50 parts by mass or more, more preferably 50 parts by mass or more, with respect to a total of 100 parts by mass of the PAS resin, the PPE-based resin, and the styrene-(meth)acrylic acid copolymer. is in the range of 60 parts by mass or more, preferably 93 parts by mass or less, and more preferably 90 parts by mass or less. If it is the said range, since the heat resistance and chemical-resistance of a film can be improved more, it is preferable.

Moreover, the resin composition (A) used for this invention uses polyphenylene ether type resin as an essential raw material, and mix|blends it.

The PPE-based resin is, as a rule, contained in the dispersed phase of the resin composition (A). The PPE-based resin in the dispersed phase is a component having a function of lowering the dielectric constant and lowering the dielectric loss tangent of the obtained biaxially stretched laminated film.

The PPE-based resin means a polymer having an ether bond directly bonded to an aromatic ring in the main chain, and is a polymer containing, for example, a structure represented by the following formula (9) in a repeating unit.

In the above formula, R ² is each independently a hydrogen atom, a halogen atom, a primary alkyl group having 1 to 7 carbon atoms, a secondary alkyl group having 1 to 7 carbon atoms, a phenyl group, a haloalkyl group, an aminoalkyl group, a hydrocarbon oxy group, At least two carbon atoms are halohydrocarbon oxy groups separating a halogen atom and an oxygen atom, and m is each independently an integer of 1-4.

Specific examples of the PPE-based 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), a homopolymer such as poly(2,6-dichloro-1,4-phenylene ether), or 2,6-dimethylphenol and other phenols (for example, 2, a copolymer of 3,6-trimethylphenol or 2-methyl-6-butylphenol), 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2- Bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride, 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl-2 A polycondensation reaction product of aromatic bis (ether anhydride) such as ,2-propane dianhydride and m-phenylenediamine or p-phenylenediamine, dihydroxydiphenylsulfone, 2,2-bis(4-hydroxy and polycondensation reaction products of phenyl)propane or 4,4'-dihydroxybiphenyl or their alkali metal salts and dichlorodiphenylsulfone.

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

It is preferable that it is 1,000 or more, as for the number average molecular weight of PPE-type resin, it is more preferable that it is 1,500-50,000, It is more preferable that it is 1,500-30,000.

The ratio of the compounding amount of the PPE-based resin in the resin composition (A) is preferably 3 parts by mass or more, more preferably 3 parts by mass or more, with respect to a total of 100 parts by mass of the PAS resin, the PPE-based resin, and the styrene-(meth)acrylic acid copolymer. Preferably from 5 mass parts or more, Preferably it is 40 mass parts or less, More preferably, it is the range of 35 mass parts or less. Within the above range, the dielectric properties (low dielectric constant, low dielectric loss tangent) of the biaxially stretched laminated film and the effect of improving direct thermal bonding with a metal or resin molded article at a temperature below the melting point of the polyphenylene sulfide resin are more excellent.

The resin composition (A) used for this invention uses a styrene- (meth)acrylic acid copolymer as an essential raw material, and mix|blends it. In addition, "(meth)acrylic acid" shall mean "acrylic acid" and/or "methacrylic acid."

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 is a component having a function of improving the stretchability of the biaxially laminated stretched film.

The styrene-methacrylic acid copolymer is a copolymer of a styrene-based monomer and a (meth)acrylic acid-based monomer.

Although it does not specifically limit as a styrene-type monomer, Styrene and its derivative(s) are mentioned. Examples of the styrene derivative include alkyl styrenes 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; fluorostyrene, chlorostyrene, Halogenated styrenes, such as a bromostyrene, dibromostyrene, and iodine styrene; Nitrostyrene; Acetyl styrene; Methoxy styrene, etc. are mentioned. These styrenic monomers may be used individually by 1 type, or may be used in combination of 2 or more type.

Examples of the (meth)acrylic acid-based monomer include (meth)acrylic acid alkyl esters having a substituted or unsubstituted C1-C6 alkyl group other than acrylic acid and methacrylic acid. In this case, although it does not specifically limit as a substituent, Halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, a hydroxyl group, etc. are mentioned. In addition, the substituent may have only one, and may have it two or more. When it has two or more substituents, each substituent may be same or different. As a specific example of the (meth)acrylic acid alkylester which has a substituted or unsubstituted C1-C6 alkyl group, (meth)acrylate methyl, (meth)acrylate, (meth)acrylate n-propyl, (meth)acrylate n-butyl, (meth)acrylic acid t-butyl, (meth)acrylic acid n-hexyl, (meth)acrylic acid cyclohexyl, (meth)acrylic acid hydroxyethyl, (meth)acrylic acid hydroxypropyl, etc. are mentioned. Especially, it is preferable that it is (meth)acrylic acid from a compatibility and a reactive viewpoint. In addition, these (meth)acrylic acid type monomers may be used individually by 1 type, or may be used in combination of 2 or more type.

The content rate of the repeating unit based on (meth)acrylic acid contained in the styrene-(meth)acrylic acid copolymer can obtain good compatibility and further improve the stretching uniformity, bending strength, etc. of the biaxially oriented laminated film. , Preferably from 1 mass % or more, preferably 30 mass % or less, more preferably 20 mass % or less, even more preferably 18 mass % or less with respect to the total mass of a styrene- (meth)acrylic acid copolymer. is the range

For the polymerization reaction of a styrene-(meth)acrylic acid copolymer, the general-purpose polymerization method of a styrene-type monomer can be applied.

The polymerization method is not particularly limited, but bulk polymerization, suspension polymerization, or solution polymerization is preferred. Among them, from the viewpoint of production efficiency, the polymerization system is particularly preferably continuous block polymerization. For example, by performing continuous bulk polymerization using an apparatus equipped with one or more stirred reactors and a tubular reactor having a plurality of mixing elements fixed therein having no moving parts, styrene-( A meth)acrylic acid copolymer can be obtained.

In addition, although thermal polymerization can also be carried out without using a polymerization initiator, it is preferable to use various radical polymerization initiators. Moreover, the compound used in manufacture of a normal polystyrene can be used as polymerization adjuvant, such as a suspending agent and an emulsifier required for a polymerization reaction.

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 such an organic solvent include toluene, ethylbenzene, xylene, acetonitrile, benzene, chlorobenzene, dichlorobenzene, anisole, cyanobenzene, dimethylformamide, N,N-dimethylacetamide, methylethylketone. and the like. These organic solvents may be used individually by 1 type, or may be used in combination of 2 or more type.

Examples of the radical polymerization initiator include 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)butane, 2,2-bis(4,4-dibutyl). Peroxyketals such as peroxycyclohexyl)propane; Hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide; di-t-butyl peroxide, dicumyl peroxide, and di-t-hexyl peroxide dialkyl peroxides such as; diacyl peroxides such as benzoyl peroxide and dicinamoyl peroxide; t-butylperoxybenzoate, di-t-butylperoxyisophthalate, t-butylperoxyisopropyl monocarbonate Peroxyesters such as; N,N'-azobisisobutylnitrile, N,N'-azobis(cyclohexane-1-carbonitrile), N,N'-azobis(2-methylbutyronitrile) , N,N'-azobis(2,4-dimethylvaleronitrile), N,N'-azobis[2-(hydroxymethyl)propionitrile], etc. are mentioned. These radical polymerization initiators may be used individually by 1 type, or may be used in combination of 2 or more type.

Moreover, you may add a chain transfer agent to the reaction system so that the molecular weight of the styrene-(meth)acrylic acid copolymer obtained may not become large too much too much. As the chain transfer agent, either a monofunctional chain transfer agent having one chain transfer group or a polyfunctional chain transfer agent having a plurality of chain transfer groups can be used. Examples of the monofunctional chain transfer agent include alkyl mercaptans and thioglycolic acid esters. As a polyfunctional chain transfer agent, the hydroxyl group in polyhydric alcohols, such as ethylene glycol, neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, is esterified with thioglycolic acid or 3-mercaptopropionic acid. compounds, and the like. These chain transfer agents may be used individually by 1 type, or may be used in combination of 2 or more type.

In addition, in order to suppress the gelation of the resulting styrene-(meth)acrylic acid copolymer, it is also recommended to use long-chain alcohols, polyoxyethylene alkyl ethers, polyoxyethylene lauryl ethers, polyoxyoleyl ethers, polyoxyethylene alkenyl ethers, etc. It is possible.

Preferably the ratio of the compounding quantity of the styrene-(meth)acrylic acid copolymer in a resin composition (A) is 0.5 mass with respect to a total of 100 mass parts of PAS resin, PPE type resin, and a styrene-(meth)acrylic acid copolymer. Part or more, More preferably, it is 1 mass part or more, Preferably it is 10 mass parts or less, More preferably, it is the range of 5 mass parts or less. If it is the said range, favorable compatibility is acquired, and the extending|stretching uniformity of a biaxially stretched laminated|multilayer film, bending-resistant strength, etc. can be improved more.

The resin composition (A) used for this invention is mix|blended using an elastomer as arbitrary raw materials as needed. When using an elastomer, the said elastomer is contained in the dispersed phase of the resin composition (A) in principle. The elastomer in the dispersed phase also functions as a compatibilizer for the PAS resin and the PPE-based resin, and has a function of improving mechanical strength (such as tear strength) when the dispersed phase is finely dispersed. In addition, by combined use with the styrene-(meth)acrylic acid copolymer, the adhesiveness of the interface between the PAS resin and the PPE-based resin through the elastomer is further improved, and the mechanical strength (break-resistant strength, tear strength, etc.) is further improved do.

The elastomer is more preferably one having a functional group capable of reacting with at least one of the PAS resin and the PPE-based resin (hereinafter also referred to as "functional group-containing elastomer"), whereby the mechanical strength of the biaxially stretched laminated film ( bending strength, tear strength, etc.) can be further improved.

As a functional group which the functional group containing elastomer may have, it is preferable that it is at least 1 sort(s) chosen from the group which consists of an epoxy group and an acid anhydride group, and it is more preferable that it is an epoxy group. These functional groups can react with the functional group of the molecular terminal which PAS resin and PPE-type resin have.

It is preferable that it is an olefin resin which has at least 1 sort(s) of functional group chosen from the group which consists of an epoxy group and an acid anhydride group as an elastomer.

As such an elastomer, a copolymer comprising a repeating unit based on an α-olefin and a repeating unit based on a vinyl polymerizable compound having the above functional group, a repeating unit based on an α-olefin and a vinyl polymerizable compound having the above functional group, a copolymer including a repeating unit based on the acrylic acid ester and a repeating unit based on an acrylic acid ester.

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

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

Although it does not specifically limit as (alpha), (beta)- unsaturated glycidyl ester, The compound etc. which are represented by following formula (10) are mentioned.

In said formula, R< ³ > is a C1-C6 alkenyl group.

Examples of the alkenyl group having 1 to 6 carbon atoms include a vinyl group, 1-propenyl group, 2-propenyl group, 1-methylethenyl group, 1-butenyl group, 2-butenyl group, 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. are mentioned.

R ⁴ is each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a 2-methylbutyl group, and a 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 group, 2,4-dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, and the like.

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

The ?-olefin content of the elastomer is preferably in the range from 50 mass % or more, preferably 95 mass % or less, more preferably 80 mass % or less, to the total mass of the elastomer. If the ratio of the repeating unit based on alpha-olefin is the said range, the extending|stretching uniformity of a biaxially stretched laminated|multilayer film, bending-resistant strength, etc. can be improved.

Further, the proportion of the repeating unit based on the vinyl polymerizable compound having a functional group in the elastomer is preferably 1% by mass or more, more preferably 2% by mass or more, preferably 30% by mass or less, more preferably It is the range of 20 mass % or less. If the ratio for which the repeating unit based on the vinyl polymeric compound which has a functional group occupies is the said range, not only the improvement effect made into the objective but favorable extrusion stability is acquired.

When blending an elastomer, the proportion of the blending amount of the elastomer in the resin composition (A) is preferably 3 parts by mass in total of the PAS resin, PPE-based resin, styrene-(meth)acrylic acid copolymer, and elastomer. It is a mass part or more, More preferably, it is the range from 5 mass parts or more, Preferably it is 15 mass parts or less, More preferably, it is the range of 10 mass parts or less. If it is the said range, the dielectric characteristic (low-dielectric constant-ization and low-dielectric loss tangent formation) of a biaxially stretched laminated|multilayer film, bending strength, etc. can be improved more.

The resin composition (A) used for this invention mix|blends a silane coupling agent as arbitrary raw materials as needed. The silane coupling agent can improve the compatibility (interaction) between the PAS resin and other components (PPE-based resin, styrene-methacrylic acid copolymer, and an elastomer which may be optionally contained). In addition, the silane coupling agent By using , the dispersibility of the other components in the PAS resin is remarkably improved, and a good morphology can be formed.

It is preferable that a silane coupling agent is a compound which has a functional group which can react with a carboxyl group. When such a silane coupling agent reacts with another component, it couple|bonds strongly with these. As a result, the effect of a silane coupling agent is exhibited more notably, and the dispersibility of the other component in PAS resin can be improved especially.

As such a silane coupling agent, the compound which has an epoxy group, an isocyanato group, an amino group, or a hydroxyl group is mentioned, for example.

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

When mix|blending a silane coupling agent, the ratio of the compounding quantity of the silane coupling agent in a resin composition (A) is 100 mass parts in total of PAS resin, PPE-type resin, a styrene- (meth)acrylic acid copolymer, and a silane coupling agent. , preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, preferably 5 parts by mass or less, more preferably 2.5 parts by mass or less. If it is the said range, the dispersibility of the other component in PAS resin can further be improved.

The resin composition (A) used in the present invention may contain, if necessary, a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, an ultraviolet stabilizer, a lubricant, an antistatic agent, a colorant, a conductive agent, etc. You may mix|blend a well-known additive.

Although it does not specifically limit as a method of manufacturing the resin composition (A) used for this invention, Each essential raw material and each arbitrary raw material and additive as needed are dry uniformly with a tumbler, a Henschel mixer, etc. as needed. A method of mixing, then introducing into a twin-screw extruder, heating to a temperature equal to or higher than the temperature at which the resin species melts, and melting and kneading is exemplified.

It is preferable to perform this melt-kneading on the conditions from which the ratio (discharge amount/screw rotation speed) of the discharge amount (kg/hr) of a kneaded material and screw rotation speed (rpm) becomes 0.02-0.2 (kg/hr·rpm).

In more detail, the method of injecting each raw material component into a twin screw extruder and melt-kneading under the temperature conditions of about 300 degreeC of set temperature and about 330 degreeC of resin temperature in a strand die is preferable. At this time, the discharge amount of a kneaded material becomes the range of 5-50 kg/hr at 250 rpm of rotations. In particular, from the viewpoint of improving the dispersibility of each component, it is preferable that the discharge amount of the kneaded material is 20 to 35 kg/hr at a rotational speed of 250 rpm. Therefore, it is more preferable that the ratio (discharge amount/screw rotation speed) of the discharge amount (kg/hr) of a kneaded material and the screw rotation speed (rpm) is 0.08-0.14 (kg/hr·rpm).

The biaxially stretched laminated|multilayer film of this invention has a structure in which at least two resin layers were laminated|stacked directly. And at least one layer of this biaxially stretched laminated|multilayer film is a resin layer (A) which consists of a biaxially stretched film of the said resin composition (A). And the manufacturing method of the biaxially stretched laminated|multilayer film of this invention has the process of biaxially stretching the unstretched laminated sheet which has the structure in which at least two resin layers were laminated|stacked directly.

In one embodiment of such a biaxially stretched laminated film, the resin layer (A) uses a PAS resin as a matrix (continuous phase), and particles (dispersed phase) containing a PPE-based resin are dispersed in this matrix. In the resin layer (A), the matrix (continuous phase) and the particles (dispersed phase) are derived from the continuous phase and the dispersed phase in the resin composition (A) constituting them, respectively. As for the matrix and the particles, since the matrix (continuous phase) is composed of a PAS resin, it is possible to obtain a biaxially oriented laminated film that retains the original properties of the PAS resin, such as heat resistance, flame retardancy, chemical resistance, and heat-and-moisture resistance.

In addition, the styrene-methacrylic acid copolymer exists in the particle|grains of a PPE-type resin, or as particle|grains (dispersed phase) different from the particle|grains (dispersed phase) of a PPE-type resin. In addition, when the resin composition (A) contains an elastomer, the elastomer is the surface of the PPE-based resin (that is, the interface between the matrix and the particles), in the particles of the PPE-based resin, or as particles (dispersed phase) different from the particles of the PPE-based resin. exist.

Further, the present inventors found that the elastomer also functions as a compatibilizer for the PAS resin and the PPE-based resin, whereby the particles are finely dispersed in the matrix, so that the mechanical strength (such as the bending resistance) of the biaxially stretched laminated film is further improved. I'm thinking. In addition, the present inventors have found that, by combined use with a silane coupling agent, the adhesiveness of the interface between the matrix and the particles via the elastomer is further improved, and the mechanical strength (such as bending resistance) of the biaxially stretched laminated film is further improved. also thinking

In the resin layer (A), the average particle diameter (average dispersion diameter) of the particles (dispersed phase) dispersed in the matrix (continuous phase) is preferably 5 µm or less, more preferably 3 µm or less, and the lower limit is not particularly limited. However, it is more preferably 0.5 µm or more. A uniform and homogeneous biaxially laminated stretched film can be obtained as the average particle diameter of particle|grains is the said range. In addition, in this specification, "the average particle diameter of particle|grains" is measured as follows.

First, the biaxially oriented film of the resin layer (A) was prepared by ultra-thin sectioning, (I) in a direction parallel to the longitudinal direction and perpendicular to the film plane, (II) parallel to the width direction and perpendicular to the film plane. cut in the direction Next, a scanning electron microscope (SEM) photograph of the cut surfaces (I) and (II) of the cut film was taken at a magnification of 2000, respectively, and arbitrary 50 particles of the obtained SEM photograph were selected, the cut surface (I) and The maximum diameter of each particle in (II) is measured, and the average particle diameter is computed by adding up the two directions of cut surfaces (I) and (II).

In addition, if the cut film is stained with ruthenic acid and subjected to STEM-EDS analysis, the components constituting the matrix and particles of the film can be analyzed.

The structure of the biaxially stretched laminated film of the present invention is not particularly limited as long as it has a structure in which at least two resin layers are directly laminated. For example, a laminated film in which the resin layers (A) are directly laminated may be used. , It is good also as a laminated|multilayer film in which the said resin layer (A) and the resin layer different from the said resin layer (A) were laminated|stacked directly. By setting it as the said structure, adhesion|attachment with a metal or a resin molded object is possible at the temperature below the melting|fusing point of PAS resin, and low-dielectric property corresponding to high-speed transmission can be implement|achieved.

When the structure of the biaxially stretched laminated film of the present invention is a laminated film in which the resin layers (A) are directly laminated, the same resin layers (A) may be laminated directly to each other, but for example, The same resin layer (A) may be directly laminated|stacked except that film thickness differs. In addition, the resin layer (A) composed of a biaxially stretched film of the same resin composition (A) may be directly laminated with each other, except that the mixing ratio of the above essential to optional raw material components to the average dispersion diameter of the dispersed phase are different. .

Moreover, from a viewpoint of being able to provide various functions, the structure of the biaxially stretched laminated|multilayer film of this invention is the resin layer (A) which consists of a biaxially stretched film of the said resin composition (A), and the said resin composition (A) It is good also as a laminated|multilayer film in which the resin layer (it is also simply described as "resin layer (B)") which consists of a biaxially stretched film of the resin composition (B) containing a different thermoplastic resin laminated|stacked directly. Here, the resin layer (B) may be made of a biaxially stretched film of a resin composition containing a thermoplastic resin, but as a resin composition containing the thermoplastic resin, PAS resin, polyamide, polyetherimide, polyethersulfone, Various polymers such as polysulfone, polyester (especially aromatic polyesters such as polyethylene terephthalate and polybutylene terephthalate are preferable), polyarylate, polyamideimide, polycarbonate, polyether ether ketone, and liquid crystal polymer; It is preferable that it is a resin composition containing the mixture containing at least 1 sort(s) of these polymers, and it is more preferable that it is a resin composition containing a PAS resin.

As PAS resin contained in the resin composition (B) used for this invention, the thing similar to what was demonstrated with the said PAS resin can be used. Although the ratio in particular of the PAS resin contained in this resin composition (B) is not limited, It is preferable that it is 60 mass parts or more, and 65 mass parts or more is especially preferable. The resin composition (B) can be formulated using resin species or additives other than the PAS resin as a raw material, for example, the polyphenylene ether-based resin, the styrene-(meth)acrylic acid copolymer, and the elastomer. , the silane coupling agent, further polyamide, polyetherimide, polyethersulfone, polysulfone, polyester (especially aromatic polyesters such as polyethylene terephthalate and polybutylene terephthalate are preferable), polyarylate, Various polymers, such as polyamideimide, polycarbonate, polyether ether ketone, and a liquid crystal polymer, and the mixture containing at least 1 sort(s) of these polymers can be used. The method of manufacturing the resin composition (B) used for this invention is also the same as that of the said resin composition (A).

Moreover, the layer which has a void|hole may be sufficient as the resin layer which comprises at least one layer of the biaxially stretched laminated|multilayer film of this invention. By having the vacancy, it is possible to further improve the dielectric properties, in particular, lower the dielectric constant. As a method of manufacturing the biaxially stretched laminated|multilayer film containing the layer which has voids, the method of forming voids in a well-known sheet thru|or a film is employable. For example, in the method for producing a biaxially stretched laminated film of the present invention, further comprising a step of blending a pore former in a resin composition, and biaxially stretching an unstretched sheet of a resin composition containing the pore former A craze is formed at the interface between the resin and the pore former, and a biaxially stretched laminated film including a layer having pores can be manufactured (it may be referred to as a craze method). Moreover, as another method, in the manufacturing method of the biaxially stretched laminated|multilayer film of this invention, further, the process of mix|blending a pore former in a resin composition, and the unstretched sheet manufactured using the resin composition containing a pore former or a step of contacting the biaxially oriented film with a solvent that dissolves the pore former (sometimes referred to as a removal solvent) to remove the pore former, whereby the unstretched sheet or the biaxially stretched film and a method of forming pores (sometimes referred to as a solvent removal method). In the case of forming pores in the unstretched sheet, thereafter, it is laminated with another unstretched sheet and biaxially stretched to obtain a biaxially stretched laminated film including a layer having pores.

As the pore-forming agent, fine particles of calcium carbonate are preferable, but inorganic fine particles such as fine particles of magnesium sulfate, fine particles of calcium oxide, fine particles of calcium hydroxide and fine particles of silica can be exemplified. A solid solvent (referred to as a solid solvent) or a liquid solvent (referred to as a liquid solvent) at room temperature can also be used. Examples of the liquid solvent include aliphatic or cyclic hydrocarbons such as nonane, decane, decalin, paraxylene, undecane, dodecane and liquid paraffin, and mineral oil fractions having boiling points corresponding to these, and dibutylphthalate and dioctyl. At room temperature, such as a phthalate, a liquid phthalic acid ester is mentioned, It is preferable to use a nonvolatile liquid solvent like liquid paraffin. Moreover, as a solid solvent, although it becomes miscible with polyolefin in the state of hot melt-kneading, a solid solvent is mentioned at room temperature, Stearyl alcohol, ceryl alcohol, paraffin wax, etc. can be used. Moreover, since there exists a possibility that extending|stretching nonuniformity etc. may generate|occur|produce when only a solid solvent is used, it is preferable to use a liquid solvent together. On the other hand, specific examples of the removal solvent include, for example, acidic aqueous solutions such as hydrochloric acid, chlorinated hydrocarbons such as methylene chloride and carbon tetrachloride, hydrocarbons such as pentane, hexane and heptane, fluorohydrocarbons such as trifluoroethane, diethyl ether, dioxane Easily volatile solvents, such as ether, such as methyl ethyl ketone, are mentioned. Moreover, as a removal solvent, the solvent used as the surface tension in 25 degreeC of 24 mN/m or less disclosed in Unexamined-Japanese-Patent No. 2002-256099 other than the above can be used. By using a solvent having such a surface tension, shrinkage and densification of the network caused by the surface tension of the gas-liquid interface generated inside the pores during drying after removing the pore former can be suppressed, and as a result, the pores The porosity and permeability of the branch layer are further improved. In the layer having voids, the porosity is not particularly limited, but from the viewpoint of excellent mechanical strength and dielectric properties, preferably 20% or more, more preferably 30% or more, preferably 70% or less, more Preferably, it is in the range of up to 60% or less. However, as for the porosity, the porosity layer in the biaxially stretched laminated film is subjected to ultra-thin sectioning, (I) in a direction parallel to the longitudinal direction and perpendicular to the film plane, (II) parallel to the width direction and the film Cut in the direction perpendicular to the plane. Next, a scanning electron microscope (SEM) photograph of the cut surfaces (I) and (II) of the cut film is taken at a magnification of 2000, respectively, and when the area of the obtained SEM photograph is 100, It refers to the ratio of the area. In addition, at that time, if no voids are observed, the porosity becomes 0%. Each ratio in the cut surfaces (I) and (II) is measured, and what is averaged by adding up the two directions of the cut surfaces (I) and (II) is called "porosity". In the present invention, when the pore-forming agent is used to form pores, the ratio of the compounding amount of the pore-forming agent may be appropriately adjusted so that the porosity falls within the above range, and each specific gravity of the resin composition and the pore-forming agent and the pore-forming agent Since it differs depending on whether the agent is left (craze method) or removed (solvent removal method), it cannot be defined uniformly, but for example, with respect to a total of 100 parts by mass of the resin composition and the pore former, preferably 70 parts by mass or less, more preferably 50 parts by mass or less, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 20 parts by mass or more, particularly preferably 30 parts by mass or more. to be.

When the biaxially stretched laminated|multilayer film of this invention has a laminated structure of a resin layer (A) and a resin layer (B), as a laminated structure, (A)/(B), (A)/(B)/(A) , (A)/(B)/(A)/(B), (A)/(B)/(A)/(B)/(A), etc. can be mentioned, but are not limited thereto. . Especially, the target structure of (A)/(B)/(A), (A)/(B)/(A)/(B)/(A) is preferable at the point which suppresses the curl of a biaxially stretched laminated|multilayer film. do. In addition, the notation of "/" means that it is in direct contact, for example, "(A)/(B)" means that each resin layer (A) and the resin layer (B) have a structure in which the resin layer (B) is directly laminated. do it by doing

The biaxially stretched laminated|multilayer film of this invention WHEREIN: It is preferable that the thickness of a resin layer (A) is the range of 2 micrometers or more, More preferably, it is the range of 10 micrometers or more. By making the thickness of a resin layer (A) into the range of 2 micrometers or more, it becomes easy to obtain high adhesiveness. In addition, although an upper limit is not limited, It is preferable that it is the range to 150 micrometers or less, More preferably, it is the range to 100 micrometers or less. Other than the resin layer (A) layer, for example, the thickness of the resin layer (B) is arbitrary.

The method for producing the biaxially oriented laminated film used in the present invention is not particularly limited, but an unstretched laminated sheet having a structure in which at least two resin layers are directly laminated is prepared, and then the obtained unstretched laminated sheet is subjected to 2 The method of axial stretching is mentioned. For example, in the case of a laminated structure, the resin or resin mixture used for each resin layer is heated and melted with a separate extruder, and the target in a molten state by a method such as a co-extrusion lamination die method or a feed block method. A co-extrusion method in which a resin layer is directly laminated in a laminated configuration, and then molded into a sheet shape by inflation or a T-die/chill roll method or the like is exemplified. This co-extrusion method is preferable since it is possible to adjust the ratio of the thickness of each layer comparatively freely, and the unstretched laminated sheet excellent also in cost performance is obtained.

Next, in the case of biaxial stretching, the unstretched laminated sheet obtained above is biaxially stretched.

The draw ratio in the longitudinal direction (MD direction) of the biaxially oriented film is preferably 2 times or more, more preferably 2.5 times, preferably 4 times or less, more preferably 3.8 times or less.

Moreover, the draw ratio in the width direction (TD direction) of a biaxially stretched film becomes like this. Preferably it is 2 times or more, More preferably, it is 2.5 times, Preferably it is 4 times or less, More preferably, it is 3.8 times or less. .

In addition, the ratio of the draw ratio in the transverse direction (TD direction) of the biaxially oriented film to the draw ratio in the longitudinal direction (MD direction) of the biaxially oriented film (width direction (TD direction)/(length direction (MD direction))) From the viewpoint of easily balancing the physical properties in the longitudinal direction and the physical properties in the width direction, preferably 0.8 or more, more preferably 0.9 or more, preferably 1.3 or less, more preferably 1.2 or less.

As an extending|stretching method, the sequential biaxial stretching method, the simultaneous biaxial stretching method, or the method of combining these can be used.

When biaxially stretching by the sequential biaxial stretching method, for example, the obtained unstretched sheet is heated with a heating roll group, and in the longitudinal direction (MD direction), preferably 2 times or more, more preferably 2.5 From fold, preferably 4 times or less, more preferably 3.8 times or less, after extending|stretching in 1 stage or 2 or more stages in multiple stages, it cools with a 30-60 degreeC cooling roll group.

Further, the stretching temperature is preferably higher than the glass transition temperature (Tg) of the PAS resin, more preferably (Tg+5°C) or higher, preferably (Tg+40°C) or lower, more preferably (Tg). +30°C) or less, more preferably (Tg+20°C) or less.

Next, it extends|stretches in the width direction (TD direction) by the method of using a tenter. The both ends of the film extended|stretched in MD direction are hold|grown with a clip, and it guides to a tenter, and extends|stretches in TD direction.

Moreover, a draw ratio becomes like this. Preferably it is 2 times or more, More preferably, it is the range from 2.5 times, Preferably it is 4 times or less, More preferably, it is the range of 3.8 times or less.

Further, the stretching temperature is preferably Tg or higher, more preferably (Tg+5°C) or higher, (Tg+40°C) or lower, more preferably (Tg+30°C) or lower, still more preferably ( Tg+20°C) or less.

Next, it is preferable to heat-set this stretched film under tension or while relaxing in the width direction.

Although the heat setting temperature is not specifically limited, Preferably it is 200 degreeC or more, More preferably, it is 220 degreeC or more, More preferably, it is 240 degreeC or more, Preferably it is 280 degreeC or less, More preferably, it is up to 275 degreeC. is the range In addition, you may perform heat setting in two stages by changing the heat setting temperature. In this case, it is preferable to set the heat setting temperature of the second stage to +10 to 40°C higher than the heat setting temperature of the first stage. The heat resistance and mechanical strength of the stretched film heat-fixed at the heat setting temperature of this range improve more.

Moreover, it is preferable that heat setting time is between 1 to 60 second.

Moreover, this film is cooled in the temperature zone of 50-275 degreeC, relaxing in the width direction. Although the relaxation rate is not specifically limited, Preferably it is 0.5 % or more, More preferably, it is 2 % or more, More preferably, it is 3 % or more, Preferably it is 10 % or less, More preferably, it is 8 % or less, More preferably. It is usually in the range of 7% or less.

Although the thickness of the biaxially stretched laminated|multilayer film is not specifically limited, Preferably it is the sum total of each layer, and the thickness of each layer becomes like this. Preferably it is 2 micrometers or more, More preferably, it is 10 micrometers or more, Preferably it is 300 micrometers or less. , 200 µm or less, more preferably up to 100 µm or less. More specifically, from the viewpoint of exhibiting sufficient mechanical strength and dielectric properties, the thickness of the biaxially oriented laminated film is preferably 10 µm or more, preferably 300 µm or less, more preferably 200 µm or less, still more preferably range up to 150 μm or less.

You may surface-treat the biaxially laminated stretched film of this invention for the purpose of improving the adhesiveness of the biaxially laminated|stretched film of this invention, and a metal or resin molded object. Examples of the surface treatment include corona discharge treatment (including corona treatment under various gas atmospheres), plasma treatment (including plasma treatment under various gas atmospheres), oxidation treatment with chemicals, ultraviolet rays, electron irradiation, etc. . Among them, plasma treatment is preferable.

According to one aspect of the present invention, a laminate is provided. The laminate has a structure in which at least one selected from the group consisting of a resin layer (A) of a biaxially stretched laminated film, a metal layer, and a resin molded body is in contact. The said laminated body contains the above-mentioned biaxially stretched laminated|multilayer film, and the metal layer or resin molded object arrange|positioned directly on the outermost resin layer surface of at least one of the said biaxially stretched laminated|multilayer film.

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

In addition, 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, the respective metal phases may be the same or different.

In one embodiment, a laminated body is, for example, a metal layer-two-axially-stretched laminated|multilayer film, a metal layer-two-axially stretched laminated|multilayer film - a metal layer, a metal layer, a biaxially stretched laminated|multilayer film - a metal layer, a biaxially stretched laminated|multilayer film, a metal layer - a metal layer - It may have a structure, such as a biaxially stretched laminated|multilayer film, a metal layer - a metal layer - a biaxially stretched laminated|multilayer film - a metal layer. In addition, the notation of "-" means that it is in direct contact, for example, "metal layer biaxially oriented laminated film" shall mean that each metal layer and the biaxially oriented laminated film are directly bonded to each other.

Moreover, as a method of adhering a metal layer and a biaxially stretched laminated|multilayer film, methods, such as a vacuum vapor deposition method, sputtering, and plating, are mentioned for a metal. Moreover, you may form a metal layer by the method of superposing|stacking the above-mentioned biaxially stretched laminated|multilayer film and metal foil, and making it heat-weld.

The laminated body with the metal layer has excellent dielectric properties (low dielectric constant, low dielectric tangent) of the biaxially stretched laminated film, so flexible printed wiring boards and flexible flat cables, especially 100 Gbps and 1 Tbps, are compatible with wireless transmission rates. It can be used suitably for next-generation high-speed transmission such as possible electronic and electrical equipment. Moreover, since the biaxially stretched laminated|multilayer film has the outstanding heat resistance and insulation, it can use suitably for the insulator for motors.

In one embodiment, the laminate may have, for example, a resin molded body biaxially stretched laminated film, a resin molded body biaxially stretched laminated film-resin molded body, a resin molded body biaxially stretched laminated film-metal layer, etc. have.

Moreover, as a method of adhering a resin molding and a biaxially-stretched laminated|multilayer film, the method of thermally bonding, such as thermal welding, superposing|stacking the above-mentioned biaxially-stretching laminated|multilayer film and a resin molded object is mentioned.

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

In addition, a flat molded product is sometimes called a film or a sheet depending on the thickness. For example, according to the Polymer Dictionary (Edited by the Society of Polymers, Asakura Bookstore, 1971), less than 200 μm is used as a film, and 200 μm or more. is described as a sheet, and according to the McGraw-Hill Dictionary of Scientific and Technological Terms (Daily Industrial News, 1996), it is described that a thin flat object with a maximum thickness of 250 μm and a minimum thickness of about 25 μm is referred to as a film. , in some cases, there is a technical field in which less than 100 µm is used as a film and 100 µm or more is distinguished as a sheet. As such, in general, it is difficult to distinguish between a film and a sheet. Therefore, in the present invention, the terms "sheet" and "film" are not distinguished from each other based only on the difference in names. For example, "sheet" is a concept that includes a thin planar object, a member that can be called a thin film or a film, and therefore "film" is a concept that includes a thin planar object, a member called a thin film or a sheet. cannot be distinguished solely by the difference between

Example

Next, although an Example demonstrates this invention in more detail, this invention is not limited to these.

1. Each ingredient used

[Polyarylene sulfide resin (a-1)]

PPS resin a-1: Linear polyphenylene sulfide resin (manufactured by DIC Corporation, melt viscosity (V6) at 280 ° C. and 300 ° C. of 160 Pa·s, produced using only para-dichlorobenzene as dichlorobenzene)

PPS resin a-2: the linear polyphenylene sulfide resin prepared in Reference Example 1 below

[Reference Example 1]

[Adjustment of polyphenylene sulfide resin (a-2)]

In a 150-liter autoclave, 19.222 kg of flaky sodium sulfide (60.9 mass %) and 45.0 kg of N-methyl- 2-pyrrolidone were put. The temperature was raised to 204° C. while stirring under a nitrogen stream, and 4.438 kg of water was distilled out (the amount of water remaining was 1.14 mol per 1 mol of sodium sulfide). Thereafter, the autoclave was sealed and cooled to 180° C., and 21.721 kg of para-dichlorobenzene, 3.833 kg of meta-dichlorobenzene (molar ratio of both [(p)/(m)] = 85/15) and N-methyl-2-p 18.0 kg of rollidone was added. At a liquid temperature of 150° C., it was pressurized to 1 kg/cm ² using nitrogen gas to initiate temperature increase. While stirring at the liquid temperature of 220 degreeC for 3 hours, 80 degreeC refrigerant|coolant was made to flow through the coil wound on the outer side of the upper part of an autoclave, and it cooled. After that, the temperature was raised and the mixture was stirred at a liquid temperature of 260°C for 3 hours. The upper part of the autoclave was kept constant so that the liquid temperature did not fall while cooling. The highest pressure during the reaction was 8.91 kg/cm ² . The obtained slurry was washed twice with warm water and filtered to obtain a filter cake containing about 50% by mass of water. Next, 60 kg of water and 100 g of acetic acid were added to this filter cake to re-slurry, and after stirring at 50 degreeC for 30 minutes, it filtered again. At this time, the pH of the slurry was 4.6. After adding 60 kg of water to the filter cake obtained here and stirring for 30 minutes, operation to filter again was repeated 5 times. The obtained filter cake was dried at 120 degreeC in a hot-air circulation dryer for 4.5 hours, and white powdery polyphenylene sulfide resin (a-2) was obtained. (Hereinafter, it abbreviate|omits as PPS resin a-2.) It was 230 degreeC of melting|fusing point, and melt viscosity (V6) in 300 degreeC was 45 Pa*s.

[Polyphenylene ether-based resin (b)]

PPE: Poly(2,6-dimethyl-1,4-phenylene ether)

Moreover, PPS has a carboxyl group at the molecular terminal, and PPE has a hydroxyl group at the molecular terminal.

[Styrene-methacrylic acid copolymer (c)]

Styrene-based resin c-1: copolymer obtained by polymerizing styrene and methacrylic acid in a mass ratio of 97.5:2.5

Styrene-based resin c-2: copolymer formed by polymerizing styrene and methacrylic acid in a mass ratio of 80.0: 20.0

[elastomer (d)]

Elastomer d-1: A glycidyl-modified elastomer obtained by polymerizing ethylene, glycidyl methacrylate, and methyl acrylate in a mass ratio of 70:3:27 (manufactured by Sumitomo Chemical Co., Ltd., "Bond First 7L")

Elastomer d-2: glycidyl-modified elastomer obtained by polymerizing ethylene and glycidyl methacrylate in a mass ratio of 88:12 (manufactured by Sumitomo Chemical Co., Ltd., "Bond First E")

Elastomer d-3: Maleic anhydride-modified elastomer (manufactured by Mitsui Chemicals Co., Ltd., "Tapmer MH7020")

[Silane coupling agent]

Silane coupling agent: γ-aminopropyltrimethoxysilane

[Example 1] Preparation of resin composition (A) and resin layer (A)

86.5 parts by mass of PPS resin a-1, 5 parts by mass of PPE, 3 parts by mass of styrene resin c-1, 5 parts by mass of elastomer d-1, and 0.5 parts by mass of a silane coupling agent are uniformly mixed with a tumbler to a mixture got

Next, this mixture was put into a vented twin screw extruder (manufactured by Nippon Steel Works, "TEX-30α"). Then, melt-extruded 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., and discharged in a strand shape, cooled with water at a temperature of 30 ° C., and cut to prepare a resin composition (A-1) .

Next, the resin composition (A-1) is put into a single screw extruder of a full flight screw, melted at 280°C to 300°C, the molten resin is extruded from a T-die, and then closely cooled with a chill roll set at 40°C Thus, an unstretched polyarylene sulfide resin sheet was produced. Furthermore, this unstretched polyarylene sulfide resin sheet was extended|stretched 3.5x3.5 times at 100 degreeC with the batch type biaxial stretching machine manufactured by Imoto Seisakusho, and the biaxially stretched film with a thickness of 35 micrometers was obtained. Furthermore, the obtained biaxially stretched film was fixed to the formwork, the heat setting process was carried out in 275 degreeC oven, and the biaxially stretched film was obtained. The dielectric properties were evaluated using this biaxially oriented film.

Moreover, the biaxially oriented film obtained above was cut|disconnected in the direction perpendicular|vertical to the film plane by the ultra-thin sectioning method. Then, the cut film was dyed with ruthenic acid, subjected to STEM-EDS analysis, and the components constituting the matrix and particles of the biaxially oriented film were analyzed. As a result, it was found that the component constituting the matrix was PPS, and the component constituting the particles was PPE. In addition, the elastomer existed as a particle which disperse|distributed independently, or existed at the interface of a matrix and particle|grains of PPE.

[Examples 2 to 9] Preparation of resin composition (A) and resin layer (A)

For resin layers (A-2 to A-9) in the same manner as in Example 1, except that the blending amounts of PPS resin a-1, PPE, styrene resin, modified elastomer and silane coupling agent were changed as shown in Table 1. A biaxially stretched film using the resin composition (A-2 to A-9) obtained in the same manner was produced except for the production of the resin composition (A-2 to A-9) and changing the draw ratio to 3 × 3 times. Thus, the dielectric properties were evaluated.

Moreover, as a result of analyzing the structural component of a biaxially stretched film by the method similar to Example 1, it turned out that the particle|grains of PPE are disperse|distributing in the matrix of PPS. In addition, the elastomer existed as a particle which disperse|distributed independently, or existed at the interface of a matrix and particle|grains of PPE.

[Example 10] Preparation of resin composition (A) and resin layer (A)

30.6 parts by mass of PPS resin a-2, 45.9 parts by mass of PPS resin a-1, 15 parts by mass of PPE, 3 parts by mass of styrene resin c-1, 5 parts by mass of elastomer d-1, and 0.5 parts by mass of silane couple Except having uniformly mixed the ring agent with a tumbler to obtain a mixture, it carried out similarly to Example 2, manufacture of the resin composition (A-10) for resin layers (A-10), and the obtained resin composition (A-10) The used biaxially stretched film was produced, and the dielectric characteristic was evaluated.

Moreover, as a result of analyzing the structural component of a biaxially stretched film by the method similar to Example 1, it turned out that the particle|grains of PPE are disperse|distributing in the matrix of PPS. In addition, the elastomer existed as a particle which disperse|distributed independently, or existed at the interface of a matrix and particle|grains of PPE.

[Comparative Example 1] Preparation of comparative resin composition (A) and resin layer (A)

Instead of the resin composition which mix|blended 86.5 mass parts of PPS resin a-1, 5 mass parts PPE, 3 mass parts styrene resin c-1, 5 mass parts elastomer d-1, and 0.5 mass parts silane coupling agent, 94.5 mass parts A biaxially stretched film was prepared in the same manner as in Example 1 except that a resin composition (cA-1) in which parts by mass of PPS resin a-1, 5 parts by mass of elastomer d-1, and 0.5 parts by mass of a silane coupling agent were mixed was used. got it The dielectric constant and dielectric loss tangent of the obtained biaxially stretched film were measured.

[Comparative Example 2] Preparation of comparative resin composition (A) and resin layer (A)

86.5 parts by mass of PPS resin a-1, 5 parts by mass of PPE, 3 parts by mass of styrene resin c-1, 5 parts by mass of elastomer d-1, and 0.5 parts by mass of a silane coupling agent instead of the resin composition blended with 89.5 In the same manner as in Example 1, except that the resin composition (cA-2) in which parts by mass of PPS resin a-1, 5 parts by mass of PPE, 5 parts by mass of elastomer d-1, and 0.5 parts by mass of a silane coupling agent were blended was used. Thus, a biaxially stretched film was obtained. The dielectric constant and dielectric loss tangent of the obtained biaxially stretched film were measured.

[Comparative Example 3] Preparation of comparative resin composition (A) and resin layer (A)

PPS resin a-1 is put into a vented twin-screw extruder "TEX-30α" manufactured by Nippon Steel Works Co., Ltd., and melt-extruded at a discharge rate of 20 kg/hr, a screw rotation speed of 300 rpm, and a set temperature of 300 ° C. After cooling with water at 30°C, the melt was prepared by cutting. Next, the kneaded material is put into a single screw extruder of a full flight screw, melted at 280 ° C. to 300 ° C., and the molten resin is extruded from a T-die, then cooled in close contact with a chill roll set at 40 ° C., and undrawn poly An arylene sulfide resin sheet was produced. Furthermore, this unstretched polyarylene sulfide resin sheet was extended|stretched 3.5x3.5 times at 100 degreeC with the batch type biaxial stretching machine manufactured by Imoto Seisakusho, and the biaxially stretched film with a thickness of 35 micrometers was obtained. Furthermore, the obtained biaxially stretched film was fixed to the formwork, the heat setting process was carried out in 270 degreeC oven, and the biaxially stretched film was obtained. The dielectric constant and dielectric loss tangent of the obtained biaxially stretched film were measured.

[Reference Example 2]

[Preparation of resin composition (B)]

The PPS resin a-1 was put into a vented twin screw extruder (manufactured by Nippon Steel Works, "TEX-30α"). Then, melt-extruded 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., and discharged in a strand shape, cooled with water at a temperature of 30 ° C., and cut to prepare a resin composition (B-1) .

[Reference Example 3]

60 parts by mass of PPS resin a-1 and 40 parts by mass of calcium carbonate (CaCO ₃ , manufactured by Maruo Calcium Co., Ltd., average particle diameter 3 µm) were put into a vented twin-screw extruder (manufactured by Nippon Steel Works, "TEX-30α"). . Then, melt-extruded 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., and discharged in a strand shape, cooled with water at a temperature of 30 ° C., and cut to prepare a resin composition (B-2) .

[Example 11] Biaxially stretched laminated film, production of laminate

The resin compositions (A-1) and (B-1) are respectively supplied to an extruder (diameter 40 mm) for the resin layer (A) and an extruder (diameter 40 mm) for the resin layer (B) and melted at 280 to 300 ° C., The molten resin is supplied to a co-extrusion sheet manufacturing apparatus (feed block and T-die temperature: 300 ° C.) having a feed block and a T-die chill roll method, melt-extruded, and then cooled in close contact with a chill roll set at 40 ° C. The laminated constitution of the resin layer (A) / resin layer (B) / resin layer (A) produced a co-extrusion laminated unstretched sheet having a three-layer constitution.

Next, the produced laminated unstretched sheet was biaxially stretched at 3.5 x 3.5 times at 100°C using a batch-type biaxial stretching machine (manufactured by Imoto Seisakusho Co., Ltd.) to obtain a film having a thickness of 50 µm. Furthermore, the biaxially stretched laminated|multilayer film was manufactured by fixing the obtained film to a formwork, and heat-setting process in 275 degreeC oven.

Next, the obtained biaxially stretched laminated film and an electrolytic copper foil (thickness of 18 µm) were laminated so that the resin layer (A) of the biaxially stretched laminated film was in contact with the electrolytic copper foil, with a press machine at 270° C. under a pressure of 5 MPa for 15 seconds. It pressurized, and the laminated body of copper foil and a film was produced.

[Example 12] Biaxially stretched laminated film, production of laminate

Using the resin composition (A-2) for the resin layer (A), except having changed the draw ratio to 3 x 3 times, it carried out similarly to Example 11, and produced the biaxially stretched laminated|multilayer film and laminated body.

[Examples 13-19] Biaxially stretched laminated film, production of laminate

For the resin layer (A), except having changed into the resin composition (A-3-A-9), it carried out similarly to Example 12, and produced the biaxially stretched laminated|multilayer film and laminated body.

[Example 20]

Except having changed into the resin composition (A-10) for resin layers (A), it carried out similarly to Example 12, and produced the biaxially stretched film. Next, the obtained biaxially stretched laminated film and an electrolytic copper foil (thickness 18 µm) were laminated so that the resin layer (A) of the biaxially stretched laminated film was in contact with the electrolytic copper foil, and the press machine was pressed at 260° C. under a pressure of 5 MPa for 15 seconds. It pressurized, and the laminated body of copper foil and a film was produced.

[Example 21]

Except having changed into the resin composition (B-2) for resin layers (B), it carried out similarly to Example 12, and produced the biaxially stretched film and laminated body. In addition, the average porosity of the resin layer (B) was 55%.

[Comparative Example 4] Preparation of comparative biaxially oriented laminated film and laminate

Except having used the resin composition (cA-1) for the resin layer (A), it carried out similarly to Example 11, and produced the biaxially stretched laminated|multilayer film and laminated body.

[Comparative Example 5] Preparation of comparative biaxially oriented laminated film and laminate

Except having used the resin composition (cA-2) for the resin layer (A), it carried out similarly to Example 11, and produced the biaxially stretched laminated|multilayer film and laminated body.

[Comparative Example 6] Preparation of comparative biaxially oriented laminated film and laminate

A biaxially stretched laminated film and a laminate were produced in the same manner as in Example 11 except that PPS resin a-1 was used instead of the resin composition (A-1) for the resin layer (A).

[Comparative Example 7] Preparation of comparative biaxially oriented laminated film and laminate

Plasma treatment was applied to the biaxially stretched laminated film obtained in Comparative Example 6, and the treated surface side of the film and an electrolytic copper foil (thickness 18 μm) were overlapped and pressed with a press machine at 270° C. under a pressure of 5 MPa for 15 seconds, and the copper foil and the film of the laminate was prepared.

[evaluation]

1. Permittivity and dielectric loss tangent

The dielectric constant and dielectric loss tangent were measured based on the cavity resonance method prescribed in JIS C 2565:1992. Specifically, a strip having a width of 2 mm and a length of 150 mm was produced from the insulating film. Next, the produced strip was left still for 24 hours in an environment of 23° C. and 50% Rh, and then the dielectric constant and dielectric loss tangent at a frequency of 1 GHz were measured by the cavity resonance method using the ADMS010c series (manufactured by AT Co., Ltd.). It is shown as "dielectric constant" and "dielectric loss tangent" in the following table|surface.

2. Adhesive

Adhesiveness measured the peeling strength of copper foil and a biaxially stretched laminated|multilayer film based on the test method prescribed|regulated to JISK6854:1999, and evaluated it according to the following criteria. It is shown as "adhesiveness" in the following table|surface.

◎: 8N/cm or more

○: 7N/cm or more and less than 8N/cm

△: 6N/cm or more and less than 7N/cm

×: Less than 6N/cm

The above results are shown in Tables 1-3.

3. Stretch uniformity

When a grid shape (grid size 10 × 10 (mm)) is stamped on a non-oriented unstretched sheet and stretched at a predetermined magnification, the condition of the grid of the obtained biaxially oriented film is visually observed, and the following standards evaluated accordingly. The obtained result is shown as "stretching uniformity" in the following table|surface.

◎; 90% or more of the grid of the entire film surface is a square

○; 80% or more and less than 90% of the grid of the entire film surface are square

△; 50% or more but less than 80% of the grid of the entire film surface is a square

×; less than 50% of the grid of the entire film surface is a square

The biaxially stretched films used as the resin layers (A-1) to (A-10) obtained in Examples 1 to 10 exhibited low dielectric constant, low dielectric loss tangent, and excellent dielectric properties. Moreover, the biaxially stretched laminated film and laminated body obtained in Examples 11-21 containing the said resin layer showed the result excellent in adhesiveness with a metal layer.

In contrast, the biaxially oriented films, biaxially oriented laminated films and laminates obtained in Comparative Examples 1 and 4, Comparative Examples 2 and 5, and Comparative Examples 3, 6 and 7, respectively, showed poor dielectric properties and/or adhesive properties. it was

From this result, it is made by blending a polyarylene sulfide resin with a polyphenylene ether-based resin and a styrene-(meth)acrylic acid copolymer as raw materials, and it is composed of a biaxially stretched film of a resin composition having a specific morphology. By using a biaxially stretched laminated film with a stratum, low dielectric constant and low dielectric loss tangent can be achieved while maintaining the excellent properties (heat resistance, incombustibility, chemical resistance, moist heat resistance) inherent in polyarylene sulfide resin. It became clear that there was Moreover, it became clear that direct thermal bonding with a metal or a resin molded object is possible below the melting|fusing point of polyarylene sulfide resin.

Claims (17)

A biaxially stretched laminated film having a structure in which at least two resin layers are directly laminated,
The biaxially stretched laminated film,
At least one layer is formed by blending at least a polyarylene sulfide resin, a polyphenylene ether-based resin, and a styrene-(meth)acrylic acid copolymer as raw materials, and the resin composition (A) having a continuous phase and a dispersed phase It is a resin layer (A) consisting of a biaxially oriented film,
The continuous phase comprises a polyarylene sulfide resin,
The dispersed phase contains a polyphenylene ether-based resin,
The average dispersion diameter of the dispersed phase in the said resin layer (A) is the range of 5 micrometers or less, The biaxially stretched laminated|multilayer film characterized by the above-mentioned. The method according to claim 1,
The styrene-(meth)acrylic acid copolymer is a copolymer obtained by copolymerizing a styrenic monomer and a (meth)acrylic acid monomer, and the (meth)acrylic acid monomer is (meth)acrylic acid. The method according to claim 1,
The said polyarylene sulfide resin has an acidic radical, the biaxially stretched laminated|multilayer film. The method according to claim 1,
The ratio of the blending amount of the polyphenylene ether-based resin is in the range of 3 to 40 parts by mass with respect to 100 parts by mass in total of the polyarylene sulfide resin, the polyphenylene ether-based resin and the styrene-(meth)acrylic acid copolymer, Biaxially stretched laminated film. The method according to claim 1,
The ratio of the compounding quantity of the said styrene-(meth)acrylic acid copolymer is 0.5-10 with respect to a total of 100 mass parts of polyarylene sulfide resin, polyphenylene ether type resin, styrene-(meth)acrylic acid copolymer, and an elastomer. The range of parts by mass, biaxially stretched laminated film. The method according to claim 1,
The (meth)acrylic acid content rate of the said styrene-(meth)acrylic acid copolymer is the range of 1-30 mass % with respect to the total mass of the said styrene-(meth)acrylic acid copolymer, The biaxially stretched laminated|multilayer film. The method according to claim 1,
The biaxially stretched laminated|multilayer film in which the said resin composition (A) contains an elastomer further. The method according to claim 1,
The ratio of the blending amount of the elastomer is in the range of 3 to 15 parts by mass relative to 100 parts by mass in total of the polyarylene sulfide resin, polyphenylene ether-based resin, styrene-(meth)acrylic acid copolymer, and elastomer, biaxial Stretched laminated film. The method according to claim 1,
The elastomer is a copolymer of an α-olefin and a glycidyl ester of an α,β-unsaturated carboxylic acid, and an α-olefin, a glycidyl ester of an α,β-unsaturated carboxylic acid and a (meth)acrylic acid ester The biaxially stretched laminated|multilayer film containing at least 1 selected from the group which consists of copolymers. 10. The method of claim 9,
The biaxially stretched laminated|multilayer film whose alpha-olefin content rate of the said elastomer is the range of 50-95 mass % with respect to the total mass of the said elastomer. The method according to claim 1,
A biaxially oriented laminated film having a structure in which at least the resin layer (A) and the resin layer (B) are directly laminated, and wherein the resin layer (B) is a biaxially oriented film of a resin composition containing a polyarylene sulfide resin. . A laminate having a structure in which at least one selected from the group consisting of the resin layer (A) of the biaxially stretched laminated film according to any one of claims 1 to 11 and a metal layer and a resin molded body is in contact with each other. The flexible printed wiring board provided with the laminated body of Claim 12. The flexible flat cable provided with the laminated body of Claim 12. The insulator for motors provided with the laminated body of Claim 12. A method for producing a biaxially stretched laminated film having a structure in which at least two resin layers are directly laminated, the method comprising:
having a step of biaxially stretching an unstretched laminated sheet having a structure in which at least two resin layers are directly laminated;
The biaxially stretched laminated film,
At least one layer is made by blending at least a polyarylene sulfide resin, a polyphenylene ether-based resin, and a styrene-(meth)acrylic acid copolymer as raw materials, and a resin composition (A) having a continuous phase and a dispersed phase A resin layer (A) comprising a biaxially stretched film formed by biaxial stretching,
The continuous phase comprises a polyarylene sulfide resin,
The dispersed phase contains a polyphenylene ether-based resin,
The average dispersion diameter of the dispersed phase in the said resin layer (A) is 5 micrometers or less, The manufacturing method of the biaxially stretched laminated|multilayer film characterized by the above-mentioned. The manufacturing method of a laminated body which adhere|attaches the resin layer (A) of the biaxially stretched laminated|multilayer film in any one of Claims 1-11, and at least 1 selected from the group which consists of a metal layer and a resin molded object.