WO2022091473A1

WO2022091473A1 - Polyarylene sulfide resin composition, and, biaxially stretched film and layered body using same

Info

Publication number: WO2022091473A1
Application number: PCT/JP2021/022024
Authority: WO
Inventors: 一範小橋; 啓介山田
Original assignee: Dic株式会社
Priority date: 2020-10-29
Filing date: 2021-06-10
Publication date: 2022-05-05
Also published as: JPWO2022091473A1; TW202229457A; JP7392847B2; KR20230095071A; CN116367999A

Abstract

Provided is a resin composition of excellent continuous extrusion film-forming ability and stretchability, which can achieve excellent toughness with a low permittivity in a biaxially stretched film obtained therefrom. Also provided is a layered body using such a film.　The present inventors discovered that excellent toughness with a low permittivity is achieved in a biaxially stretched film by setting the fluidity before and after dwelling to be within a specific range for a resin composition comprising (A) a polyarylene sulfide-based resin and (B) a fluorine-based resin having a reactive functional group, and thus arrived at the present invention.

Description

Polyarylene sulfide resin composition, biaxially stretched film and laminate using this

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

In recent years, in the fields of flexible printed wiring boards (FPC) and flexible flat cables (FFC), the development of clouds and IoT (Internet of Things), the improvement of automatic driving technology for automobiles, and the development of electric vehicles and hybrid vehicles. Therefore, there is a demand for cables and antennas that can process a large amount of data and transmit at high speed and without loss. However, conventionally, a polyimide (PI) film is used as the FPC base material, and a polyester film (PET film, etc.) is used as the FCC base material, and it is said that the FPC base material has dielectric properties capable of supporting next-generation high-speed transmission. I can't say. It was

On the other hand, a film using a polyarylene sulfide resin represented by a polyphenylene sulfide resin (PPS resin) has excellent heat resistance, flame retardancy, chemical resistance, and electrical insulation, so that it is an insulating material for capacitors and motors, and heat resistance. Used for tape. Since the polyarylene sulfide resin has excellent dielectric properties as compared with PI and PET, it can be suitably applied to the fields of FPC and FFC. However, in order to support next-generation high-speed transmission, it is necessary to further reduce the dielectric constant.

As a method for improving this, for example, Patent Document 1 proposes a method in which inorganic particles are contained in a PPS resin to form pores during biaxial stretching. However, in the film described in Patent Document 1, although the effect of lowering the dielectric constant can be sufficiently obtained, the mechanical properties of the film are deteriorated due to the presence of pores. Therefore, although a layer containing no inorganic particles is laminated on the surface layer, sufficient mechanical strength cannot be obtained. In addition, it is necessary to stack them, and in stretching the laminated body, it is important to match the adhesiveness between the layers and the stretchability of each layer, which tends to be very difficult from the viewpoint of production.

In addition, some attempts to combine both resins have been reported in order to achieve both the excellent properties of the PPS resin and the fluororesin. For example, Patent Document 2 proposes a resin composition composed of a PPS resin and a fluororesin containing a functional group, in which the dispersed particle size is stabilized before and after retention. However, the proposals described in these patents have been proposed mainly for injection molding applications, and although stability of viscosity is important for film applications that require continuous extrusion, there is no description. Further, there is no description as a biaxially stretched film having a low dielectric constant.

Japanese Unexamined Patent Publication No. 2018-83415 JP-A-2015-110732

The present invention provides a resin composition having excellent continuous extrusion film forming property and stretchability, having a low dielectric constant and having excellent toughness in the obtained biaxially stretched film, and a laminate using such a film. There is something in it.

As a result of sincere studies to solve the above problems, the present inventors have retained in the resin composition composed of the polyarylene sulfide resin (A) and the fluorine-containing resin (B) having a reactive functional group. We have found that the above problems can be solved by setting the front-back fluidity within a specific range, and have completed the present invention.
That is, the present invention relates to the following (1) to (8).

(1) A resin having a continuous phase and a dispersed phase, which is made from at least 51 to 95% by mass of a polyarylene sulfide resin (A) and 5 to 49% by mass of a fluororesin (B) having a reactive functional group. A composition having a dielectric constant of 3.2 or less in a biaxially stretched film using the resin composition.
The continuous phase contains a polyarylene sulfide resin (A) and contains.
The dispersed phase is a polyarylene sulfide resin composition containing a fluorine-containing resin (B) having a reactive functional group.

(2) The fluidity of the resin composition after being retained at 330 ° C. for 5 minutes (melt flow rate 1) and the fluidity of the resin composition after being retained at 330 ° C. for 30 minutes (melt flow rate 2). The ratio of melt flow rate 1 to melt flow rate 2 is preferably 0.2 or more and 4.5 or less.

(3) The fluorine-containing resin (B) having a reactive functional group is a fluorine-containing resin having at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group and an isocyanate group. It is preferable to have.
(4) Further, it is preferable to contain 1 to 20% by mass of the modified elastomer (C) to which the reactive group is added.
(5) The modified elastomer (C) is preferably made of an olefin polymer having at least one functional group selected from the group consisting of an epoxy group and an acid anhydride group.

(6) It is preferable to contain 0.05 to 5% by mass of the silane coupling compound (D) containing at least one functional group selected from an epoxy group, an amino group and an isocyanate group.
(7) The film of the present invention is a biaxially stretched film obtained by biaxially stretching the resin composition according to any one of the above items (1) to (6).
(8) The laminate of the present invention is a laminate containing the biaxially stretched film according to (7) above and a metal layer arranged on at least one surface of the biaxially stretched film.

According to the present invention, there is provided a resin composition which is excellent in continuous extrusion film forming property and stretchability, and the obtained biaxially stretched film can have low dielectric property and excellent toughness.

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

[Resin composition]
The resin composition is made from at least a polyarylene sulfide-based resin (hereinafter, may be referred to as "PAS-based resin") and a fluorine-containing resin having a reactive functional group as raw materials. At this time, the resin composition has a continuous phase and a dispersed phase, and at this time, the continuous phase contains a polyarylene sulfide-based resin, and the dispersed phase contains a fluorine-containing resin having a reactive functional group. include.

Fluidity of the resin composition after staying at 330 ° C. for 5 minutes (melt flow rate 1, the melt flow rate referred to here is a measure indicating the fluidity of the resin in a molten state; hereinafter, “MFR1”). A resin composition having a MFR1 / MFR2 ratio of 0.2 or more and 4.5 or less in terms of fluidity (melt flow rate 2, hereinafter, “MFR2”) after staying at 330 ° C. for 30 minutes. When the MFR1 / MFR2 ratio is larger than 4.5, the reactivity between the PAS-based resin (A) and the fluorine-containing resin (B) having a reactive functional group proceeds, and the thickening of the resin composition is large. This means that gelation or the like occurs during continuous film formation, causing problems such as a rapid increase in the resin pressure of the extruder and breakage during stretching. When the MFR1 / MFR2 ratio is smaller than 0.2, the PAS-based resin (A) and the fluorine-containing resin (B) having a reactive functional group are decomposed during continuous film formation, and the viscosity is reduced. This means that stable film formation becomes difficult. Therefore, if the fluidity ratio after 5 minutes and 30 minutes at 330 ° C. is within the above range, stable film-forming property and stretchability are obtained, and the resin composition is optimal for continuous extrusion film-forming property and stretchability. ..

The average dispersion diameter of the dispersed phase in the resin composition is 5 μm or less, preferably 3 μm or less, and more preferably 0.5 to 3 μm. When the average dispersion diameter of the dispersed phase is 3 μm or less, a uniform stretched film can be obtained.

[Polyarylene sulfide resin (A)]
The polyarylene sulfide-based resin (A) (PAS-based resin (A)) is the main component of the resin composition and is a component having a function of imparting excellent heat resistance and toughness to the film.
The PAS-based resin (A) is a polymer containing a structure in which an aromatic ring and a sulfur atom are bonded (specifically, a structure represented by the following formula (1)) as a repeating unit.

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

Here, it is preferable that R ¹ in the structure represented by the formula (1) is a hydrogen atom. With such a configuration, the mechanical strength of the PAS-based resin (A) can be further increased. The structure represented by the formula (1) in which all R ^1s are hydrogen atoms is the structure represented by the following formula (2) (that is, the structure in which the sulfur atom is bonded to the aromatic ring at the para position). , And a structure represented by the following formula (3) (that is, a structure in which a sulfur atom is bonded to an aromatic ring at the meta position).

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

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

The structures represented by the formulas (4) to (7) are preferably contained in an amount of 30 mol% or less, more preferably 10 mol% or less, in all the repeating units constituting the PAS-based resin (A). .. With such a configuration, the heat resistance and mechanical strength of the PAS-based resin (A) can be further enhanced.
Further, the bonding mode of the structures represented by the formulas (4) to (7) may be either a random shape or a block shape.

Further, the PAS-based resin (A) may contain a trifunctional structure represented by the following formula (8), a naphthyl sulfide structure, or the like as a repeating unit in its molecular structure.

The structure represented by the formula (8), the naphthyl sulfide structure and the like are preferably contained in an amount of 1 mol% or less, and substantially not contained in all the repeating units constituting the PAS-based resin (A). More preferred. With such a configuration, the content of chlorine atoms in the PAS-based resin (A) can be reduced.
The characteristics of the PAS-based resin (A) are not particularly limited as long as the effects of the present invention are not impaired, but the melt viscosity (V6) at 300 ° C. is preferably 50 to 2000 Pa · s, and further flows. It is more preferably 80 to 1500 Pa · s because the balance between the properties and the mechanical strength is good.

Further, the PAS-based resin (A) has a peak in the molecular weight range of 25,000 to 40,000 as measured by gel permeation chromatography (GPC), and has a weight average molecular weight (Mw) and a number average molecular weight (Mw). It is particularly preferable that the ratio (Mw / Mn) to Mn) is in the range of 5 to 10 and the non-Newton index is in the range of 0.9 to 1.3. By using the PAS-based resin (A), the chlorine atom content in the PAS-based resin (A) itself can be reduced to the range of 800 to 2,000 ppm without lowering the mechanical strength of the film, and the halogen can be used. It will be easy to apply to free electronic and electrical component applications.

In this specification, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw / Mn) adopt the values measured by gel permeation chromatography (GPC), respectively. The measurement conditions of GPC are as follows.
[Measurement conditions by gel permeation chromatography]
Equipment: Ultra-high temperature polymer molecular weight distribution measuring device (SSC-7000 manufactured by Senshu Kagaku Co., Ltd.)
Column: UT-805L (manufactured by Showa Denko KK)
Column temperature: 210 ° C
Solvent: 1-Chloronaphthalene Measurement method: Measure the molecular weight distribution and peak molecular weight using 6 types of monodisperse polystyrene for calibration with a UV detector (360 nm).

The method for producing the PAS-based resin (A) is not particularly limited, but for example, 1) a dihalogeno aromatic compound, if necessary, a polyhalogeno aromatic compound or other copolymerization component in the presence of sulfur and sodium carbonate. In addition, a method of polymerizing, 2) a method of polymerizing a dihalogeno aromatic compound in the presence of a sulfide agent or the like in a polar solvent, if necessary, by adding a polyhalogeno aromatic compound or other copolymerization component. ) A method of self-condensing p-chlorthiophenol by adding other copolymerization components if necessary can be mentioned. Among these manufacturing methods, the method 2) above is general-purpose and preferable.
At the time of the reaction, an alkali metal salt of a carboxylic acid or a sulfonic acid or an alkali hydroxide may be added in order to adjust the degree of polymerization.

Among the above methods 2), the following method 2-1) or 2-2) is particularly preferable.
In the method of 2-1), a hydrous sulfide agent is introduced into a mixture containing a heated organic polar solvent and a dihalogeno aromatic compound at a rate at which water can be removed from the reaction mixture, and the dihalogeno fragrance is introduced in the organic polar solvent. When the group compound and the sulfidizing agent are added to the polyhalogeno aromatic compound as required and reacted, the water content in the reaction system is adjusted to 0.02 to 0.5 mol with respect to 1 mol of the organic polar solvent. The PAS-based resin (A) is produced by controlling the range (see Japanese Patent Application Laid-Open No. 07-228699).
In the method of 2-2), a dihalogeno aromatic compound and, if necessary, a polyhalogeno aromatic compound or other copolymerization component are added in the presence of a solid alkali metal sulfide and an aprotonic polar organic solvent, and the alkali metal is added. When reacting with hydrosulfide and the organic acid alkali metal salt, the amount of the organic acid alkali metal salt should be controlled in the range of 0.01 to 0.9 mol with respect to 1 mol of the sulfur source, and in the reaction system. The PAS-based resin (A) is produced by controlling the water content of the above in the range of 0.02 mol or less with respect to 1 mol of the aprotonic polar organic solvent (see 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, and 4,4'. -Dihalobiphenyl, 3,5-dihalobenzoic acid, 2,4-dihalobenzoic acid, 2,5-dihalonitrobenzene, 2,4-dihalonitrobenzene, 2,4-dihaloanisole, p, p'- Dihalodiphenyl ether, 4,4'-dihalobenzophenone, 4,4'-dihalodiphenyl sulfone, 4,4'-dihalodiphenyl sulfoxide, 4,4'-dihalodiphenyl sulfide, and aromatic rings of each of the above compounds. Examples thereof include compounds having an alkyl group having an number of carbon atoms in the range of 1 to 18.
Examples of the polyhalogeno aromatic compound include 1,2,3-trihalobenzene, 1,2,4-trihalobenzene, 1,3,5-trihalobenzene, 1,2,3,5-tetrahalobenzene, 1, Examples thereof include 2,4,5-tetrahalobenzene and 1,4,6-trihalonaphthalene.
The halogen atom contained in the above compound is preferably a chlorine atom or a bromine atom.

As a method for post-treating the reaction mixture containing the PAS-based resin (A) obtained in the polymerization step, a known and commonly used method is used. The post-treatment method is not particularly limited, and examples thereof include the following methods (1) to (5).
In the method (1), after the polymerization reaction is completed, the reaction mixture is first used as it is, or an acid or a base is added, and then the solvent is distilled off under reduced pressure or normal pressure, and then the solid substance after the solvent is distilled off is water. It is washed once or twice or more with a reaction solvent (or an organic solvent having equivalent solubility in a low molecular weight polymer), acetone, methyl ethyl ketone, alcohols, etc., and further neutralized, washed with water, filtered and dried.
In the method (2), after the completion of the polymerization reaction, a solvent such as water, acetone, methyl ethyl ketone, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons, and aliphatic hydrocarbons is added to the reaction mixture (as the polymerization solvent used). A solvent that is soluble and at least a poor solvent for the PAS-based resin (A)) is added as a precipitating agent to precipitate solid products such as the PAS-based resin (A) and inorganic salts. These are filtered, washed and dried.

In the method (3), after the polymerization reaction was completed, a reaction solvent (or an organic solvent having the same solubility as that of a low molecular weight polymer) was added to the reaction mixture, and the mixture was stirred and then filtered to remove the low molecular weight polymer. After that, it is washed once or twice or more with a solvent such as water, acetone, methyl ethyl ketone, alcohols, etc., and then neutralized, washed with water, filtered and dried.
In the method (4), after the completion of the polymerization reaction, water is added to the reaction mixture, and the reaction mixture is washed with water, filtered, and if necessary, acid is added at the time of washing with water, and the mixture is treated with acid and dried.
In the method (5), after the 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 that can be used in the method (4) above include saturated fatty acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid and monochloroacetic acid, and unsaturated acids such as acrylic acid, crotonic acid and oleic acid. Aromatic carboxylic acids such as fatty acids, benzoic acid, phthalic acid and salicylic acid, dicarboxylic acids such as maleic acid and fumaric acid, organic acids such as sulfonic acid such as methanesulfonic acid and paratoluenesulfonic acid, hydrochloric acid, sulfuric acid, sulfite and nitrate. , Inorganic acids such as nitrite and phosphoric acid.
Examples of the hydrogen salt include sodium hydrogen sulfide, disodium hydrogen phosphate, sodium hydrogen carbonate and the like. However, when used in an actual machine, an organic acid that does not corrode metal members is preferable.
In the methods (1) to (5) above, the PAS-based resin (A) may be dried in a vacuum, in the air, or in an atmosphere of an inert gas such as nitrogen. ..

In particular, the PAS-based resin (A) post-treated by the method (4) above has a fluorine-containing resin (B) having a reactive functional group due to an increase in the amount of acid groups bonded to the molecular ends thereof. When mixed with the modified elastomer (C) or the silane coupling agent (D), the effect of enhancing their dispersibility can be obtained. The acid group is particularly preferably a carboxyl group.
The content of the PAS-based resin (A) in the resin composition may be 51 to 95% by mass, but preferably 60 to 80% by mass. When the content of the PAS-based resin (A) is in the above range, the heat resistance and toughness of the film can be further improved.

[Fluorine-containing resin (B) having a reactive functional group]
The fluorine-containing resin (B) having a reactive functional group (fluorine-containing resin (B)) is at least one reactive functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group and an isocyanate group. Has a group. Two or more of these reactive functional groups may be contained. Of these, a carbonyl group-containing group is preferable because it is excellent in reactivity with the PAS-based resin (A). Examples of the carbonyl group-containing group include a group having a carbonyl group between carbon atoms of the hydrocarbon group, a carbonate group, a carboxy group, a haloformyl group, an alkoxycarbonyl group, an acid anhydride group, a polyfluoroalkoxycarbonyl group and the like.

As a method for introducing the reactive functional group of the fluorine-containing resin (B), (1) it has a reactive functional group when producing the main chain of the fluorine-containing resin having the reactive functional group in the polymerization reaction. Use monomers. (2) A fluorine-containing resin (B) having a functional group is produced by a polymerization reaction using a chain transfer agent that generates a radical having a reactive functional group. (3) A fluorine-containing resin (B) having a functional group is produced by a polymerization reaction using a polymerization initiator that generates a radical having a reactive functional group. (4) Examples thereof include a method of modifying a fluororesin by a method such as oxidation or thermal decomposition. Further, (5) a method of blending a compound or a resin that is compatible with a fluororesin and contains the functional group can be mentioned.

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

Examples of the monomer having a carboxyl group-containing group include unsaturated dicarboxylic acids (maleic acid, itaconic acid, citraconic acid, crotonic acid, hymic acid, 5-norbornene-2,3-dicarboxylic acid, maleic acid) and their non-saturation. Examples thereof include saturated dicarboxylic acid anhydrides, unsaturated monocarboxylic acids (acrylic acid, methacrylic acid), vinyl esters (vinyl acetate, chloroacetic acid vinyl, vinyl butanoate, vinyl pivalate, vinyl benzoate, vinyl crotonate) and the like.

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

Examples of the epoxy group-containing monomer include unsaturated glycidyl ether (allyl glycidyl ether, 2-methylallyl glycidyl ether, vinyl glycidyl ether, etc.) and unsaturated glycidyl ester (glycidyl acrylate, glycidyl methacrylate, etc.).

Examples of the isocyanate group-containing monomer include 2- (meth) acryloyloxyethyl isocyanate, 2- (2- (meth) acryloyloxyethoxy) ethyl isocyanate, and 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate. Can be mentioned.

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

The structure of the fluorine-containing resin (B) is not particularly limited, but is composed of at least one fluoroolefin unit. For example, a tetrafluoroethylene polymer, a copolymer with perfluoro (alkyl vinyl ether), hexafluoropropylene, vinylidene fluoride, vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene, and further, ethylene, propylene, butene. , Copolymers with non-fluoroethylene-based monomers that do not contain fluorine, such as alkyl vinyl ethers, can also be mentioned. Specifically, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene- Examples thereof include hexafluoropropylene copolymer, polyvinylidene fluoride, polychlorotrifluoroethylene and the like. Of these, an ethylene-tetrafluoroethylene copolymer, a tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer, and a tetrafluoroethylene-hexafluoropropylene copolymer are preferable from the viewpoint of easy melt extrusion.

The melting point of the fluorine-containing resin (B) used in the present invention is not particularly limited, but is 170 ° C to 340 ° C, preferably 180 ° C to 340 ° C, and more preferably 190 ° C to 330 ° C. When the melting point of the fluorine-containing resin (B) is within the above range, maintenance of heat resistance and good melt extrusion stability can be obtained.

The glass transition temperature of the fluorine-containing resin (B) used in the present invention is not particularly limited, but is 130 ° C. or lower, more preferably 120 ° C. or lower and 110 ° C. or lower. In the case of the fluorine-containing resin (B) having the glass transition temperature, the PAS-based resin (A) which is a continuous phase and the fluorine-containing resin which is a dispersed phase are stretched after being mixed with the PAS-based resin (A). It is possible to suppress peeling at the interface with the resin (B). As a result, breakage during stretching can be suppressed, and a film having excellent mechanical characteristics can be obtained.

The content of the fluorine-containing resin (B) in the resin composition may be 5 to 49% by mass, but preferably 5 to 40% by mass. When the content of the fluorine-containing resin (B) is in the above range, the effect of improving the dielectric property (reducing the dielectric constant) of the film is more remarkable.

In the present invention, it is also possible to use the fluorine-containing resin (B) in combination with the fluorine-containing resin that does not contain a reactive functional group.

[Modified Elastomer (C)]
The modified elastomer (C) has a reactive group capable of reacting with at least one of the PAS-based resin (A) and the fluorine-containing resin (B), thereby improving the mechanical strength (folding resistance, etc.) of the film. It is a component with a function.
The reactive group of the modified elastomer (C) is preferably at least one selected from the group consisting of an epoxy group and an acid anhydride group, and more preferably an epoxy group. These reactive groups can rapidly react with the functional groups of the PAS-based resin (A) and the fluorine-containing resin (B).

Examples of the modified elastomer (C) include a copolymer containing a repeating unit based on α-olefin and a repeating unit based on a vinyl polymerizable compound having the above functional group, a repeating unit based on α-olefin, and the above functional group. Examples thereof include a copolymer containing a repeating unit based on a vinyl polymerizable compound having the above, 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 such as acrylic acid, methacrylic acid, acrylic acid ester and methacrylic acid ester and their esters, maleic acid, fumaric acid, itaconic acid and others. Examples thereof include unsaturated dicarboxylic acids having 4 to 10 carbon atoms, mono or diesters thereof, α, β-unsaturated dicarboxylic acids such as acid anhydrides thereof, esters thereof and acid anhydrides thereof, α, β-unsaturated glycidyl esters and the like. Be done.

The α, β-unsaturated glycidyl ester is not particularly limited, and examples thereof include compounds represented by the following formula (10).

In the above formula, R ³ is an alkenyl group having 1 to 6 carbon atoms.
Examples of the alkenyl group having 1 to 6 carbon atoms include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-methylethenyl group, a 1-butenyl group, a 2-butenyl group, a 1-methyl-1-propenyl group and a 1-. Methyl-2-propenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4pentenyl group, 1-methyl-1- Examples thereof include a pentenyl group, a 1-methyl-3-pentenyl group, a 1,1-dimethyl-1-butenyl group, a 1-hexenyl group, a 3-hexenyl group and the like.

^R4 is an independently hydrogen atom, a halogen atom, and an alkyl group having 1 to 6 carbon atoms.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, 2-methylbutyl group and 3-methylbutyl group. 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-dimethyl Examples thereof include a butyl group, a 2,4-dimethylbutyl group, a 3,3-dimethylbutyl group and a 2-ethylbutyl group.

Specific examples of the α, β-unsaturated glycidyl ester include glycidyl acrylate and glycidyl methacrylate, and glycidyl methacrylate is preferable.
The ratio of the repeating unit based on α-olefin in the modified elastomer (C) is preferably 50 to 95% by mass, more preferably 50 to 80% by mass. When the ratio of the repeating unit based on α-olefin is within the above range, the stretch uniformity, folding resistance and the like of the film can be improved.
Further, the ratio of the repeating unit based on the vinyl polymerizable compound having a functional group in the modified elastomer (C) is preferably 1 to 30% by mass, more preferably 2 to 20% by mass. When the ratio of the repeating unit based on the vinyl polymerizable compound having a functional group is in the above range, not only the desired improvement effect but also good extrusion stability can be obtained.

The content of the modified elastomer (C) in the resin composition is preferably 1 to 20% by mass, more preferably 1 to 5% by mass. When the content of the modified elastomer (C) is within the above range, the effect of improving the dielectric properties, folding resistance and the like of the film is remarkably exhibited.

[Silane Coupling Agent (D)]
The silane coupling agent (D) in the present invention is compatible (mutually) with the PAS-based resin (A), the fluorine-containing resin (B) having a reactive functional group, which is another component, and the modified elastomer (C). It is a component having a function of enhancing action). By using the silane coupling agent (D), the dispersibility of other components in the PAS-based resin (A) is dramatically improved, and good morphology can be formed.

The silane coupling agent (D) is preferably a compound having a functional group capable of reacting with a carboxyl group. The silane coupling agent (D) reacts with the PAS-based resin (A) and the fluorine-containing resin (B) to firmly bond with them. As a result, the effect of the silane coupling agent (D) is exhibited more remarkably, and the dispersibility of the fluorine-containing resin (B) in the PAS-based resin (A) can be particularly enhanced.

Examples of the silane coupling agent (D) include compounds having an epoxy group, an isocyanate group, an amino group or a hydroxyl group.
Specific examples of the silane coupling agent (D) include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Group-containing alkoxysilane compound, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxy Isocyanato group-containing alkoxysilane compounds such as silane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) Examples thereof include amino group-containing alkoxysilane compounds such as aminopropyltrimethoxysilane and γ-aminopropyltrimethoxysilane, and hydroxyl group-containing alkoxysilane compounds such as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyltriethoxysilane.

The content of the silane coupling agent (D) in the resin composition is preferably 0.05 to 5% by mass, more preferably 0.1 to 3% by mass. When the content of the silane coupling agent (D) is in the above range, the effect of improving the dispersibility of other components in the PAS-based resin (A) is remarkably exhibited.

[Additive]
The resin composition contains a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, an ultraviolet stabilizer, a lubricant, an antistatic agent, a colorant, a conductive agent and the like as long as the effect of the present invention is not impaired. May be.

<Resin composition and manufacturing method>
The method for producing the resin composition is not particularly limited, but is limited to PAS-based resin (A), fluorine-containing resin (B), modified elastomer (C), silane coupling agent (D), and if necessary, others. There is a method of uniformly mixing the components of the above with a tumbler or a Henschel mixer, and then putting them into a twin-screw extruder for melt kneading. This melt kneading is carried out in a shear flow field or an extension flow field. Either one or both of the kneading may be used. In this melt kneading, the ratio (discharge amount / screw rotation speed) of the discharge amount (kg / hr) of the kneaded material to the screw rotation speed (rpm) is 0.02 to 0.2 (kg / hr · rpm). It is preferable to carry out under the conditions.

The set temperature at the time of mixing is selected in the range of +5 to 70 ° C. from the melting point of the resin having the higher melting point among the PAS-based resin (A) and the fluorine-containing resin (B), and the range of +10 to 50 ° C. is more. preferable. When the set temperature is lower than the melting points of the PAS-based resin (A) and the fluorine-containing resin (B), the composition is due to the presence of the PAS-based resin (A) or the fluorine-containing resin (B) that does not partially melt. This is not preferable in terms of productivity because the viscosity of the resin increases significantly and the load on the twin-screw extruder increases.
More specifically, a method in which each component is put into a twin-screw extruder and melt-kneaded at the set temperature under a temperature condition of a resin temperature of about 310 ° C. on a strand die is preferable. At this time, the discharge amount of the kneaded product is in the range of 5 to 50 kg / hr at a rotation speed of 250 rpm. In particular, from the viewpoint of enhancing the dispersibility of each component, the discharge amount of the kneaded product is preferably 20 to 35 kg / hr at a rotation speed of 250 rpm. Therefore, the ratio (discharge amount / screw rotation speed) between the discharge amount (kg / hr) of the kneaded product and the screw rotation speed (rpm) may be 0.08 to 0.14 (kg / hr · rpm). More preferred.

The average particle size (average dispersion diameter) of the particles (dispersed phase) dispersed in the matrix is preferably 5 μm or less, more preferably 3 μm or less, and further preferably 0.5 to 3 μm. When the average particle size of the particles is in the above range, a uniform and homogeneous film can be obtained. In this specification, the value measured by the method described in Examples described later is adopted as the “average particle size of particles”.

<Film>
The film of the present invention is formed from the above resin composition.
In one embodiment of such a film, the PAS-based resin (A) is used as a matrix (continuous phase), and particles (dispersed phase) containing the fluorine-containing resin (B) are dispersed in the matrix.
The modified elastomer (C) may be used on the surface of the particles of the fluorine-containing resin (B) (that is, at the interface between the matrix and the particles), in the particles of the fluorine-containing resin (B), or on the fluorine-containing resin (B). It exists as a particle (dispersed phase) different from the particle.

In addition, the present inventors also function as a compatibilizer between the PAS-based resin (A) and the fluorine-containing resin (B) in the modified elastomer (C), so that the particles are finely dispersed in the matrix. It is believed that this will improve the mechanical strength of the film. Furthermore, the present inventors further improve the adhesiveness of the interface between the matrix and the particles via the modified elastomer (C) and further improve the mechanical strength of the film when used in combination with the silane coupling agent (D). I also think that it will be done.

The film is preferably a biaxially stretched film formed by biaxially stretching a sheet obtained from a resin composition.
If the biaxially stretched film is used, the PAS-based resin (A) constituting the matrix crystallizes in a stretched state, so that a film with high dimensional accuracy can be obtained.

The stretching ratio in the longitudinal direction (MD direction) of the biaxially stretched film is preferably 1.5 to 4 times, more preferably 2 to 3.8 times.
The draw ratio of the biaxially stretched film in the width direction (TD direction) is preferably 1.5 to 4 times, more preferably 2 to 3.8 times.
The ratio of the stretching ratio in the width direction (TD direction) of the biaxially stretched film to the stretching ratio in the longitudinal direction (MD direction) of the biaxially stretched film (width direction (TD direction) / (longitudinal direction (MD direction)) is , 0.8 to 1.3, and more preferably 0.9 to 1.2 because it is easy to balance the physical properties in the longitudinal direction and the physical properties in the width direction.

The thickness of the biaxially stretched film of the present invention is not particularly limited, but is in the range of 300 μm or less, preferably 3 to 200 μm, and more preferably 5 to 150 μm. A biaxially stretched film having such a thickness can exhibit sufficient mechanical strength.

The biaxially stretched film of the present invention may have at least one layer made of the resin composition of the present invention, and layers made of other resin compositions are laminated directly or via an adhesive layer or the like. May be.

A surface treatment may be applied to the biaxially stretched film for the purpose of enhancing the adhesiveness between the biaxially stretched film of the present invention and the metal or resin molded body. The surface treatment includes 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 rays, etc. Can be mentioned. Above all, plasma treatment is preferable.

<Manufacturing method of biaxially stretched film>
The biaxially stretched film is manufactured, for example, as follows.
First, the resin composition is dried at 140 ° C. for 3 hours or more, and then put into an extruder heated to 280 to 320 ° C.
Then, the molten resin composition (that is, the kneaded product) that has passed through the extruder is discharged into a sheet (film) by a T-die.
Next, the sheet-shaped kneaded product is brought into close contact with a cooling roll having a surface temperature of 20 to 50 ° C. to be cooled and solidified. As a result, an unoriented sheet in an unoriented state is obtained.

Next, the unstretched sheet is biaxially stretched. The stretching method is not particularly limited, and a known method can be adopted. A sequential biaxial stretching method, a simultaneous biaxial stretching method, or a combination thereof can be used.
In the case of biaxial stretching by the sequential biaxial stretching method, for example, the obtained unstretched sheet is heated by a heating roll group and 1.5 to 4 times (preferably 2 to 3) in the longitudinal direction (MD direction). After stretching in one stage or multiple stages of two or more stages), it is cooled in a cooling roll group at 30 to 60 ° C.
The stretching temperature is preferably the glass transition temperature (Tg) to Tg + 40 ° C. of the PAS-based resin (A), more preferably Tg + 5 ° C. to Tg + 30 ° C., and further preferably Tg + 5 ° C. to Tg + 20 ° C. preferable.

Next, it is stretched in the width direction (TD direction) by a method using a tenter. Both ends of the film stretched in the MD direction are gripped with clips, guided to the tenter, and stretched in the TD direction.
The draw ratio is preferably 1.5 to 4 times, more preferably 2 to 3.8 times.
The stretching temperature is preferably Tg to Tg + 40 ° C, more preferably Tg + 5 ° C to Tg + 30 ° C, and even more preferably Tg + 5 ° C to Tg + 20 ° C.

Next, the stretched film is heat-fixed under tension or while relaxing in the width direction.
The heat fixing temperature is not particularly limited, but is preferably 200 to 280 ° C, more preferably 220 to 280 ° C, and even more preferably 240 to 275 ° C. The heat fixing may be performed in two stages by changing the heat fixing temperature. In this case, it is preferable that the heat fixing temperature of the second stage is higher than the heat fixing temperature of the first stage by +10 to 40 ° C. The stretched film heat-fixed at a heat-fixing temperature in this range has higher heat resistance and mechanical strength.
The heat fixing time is preferably 1 to 60 seconds.

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

[Laminate]
The laminated body of the present invention has the above-mentioned biaxially stretched film and a metal layer or a resin molded body provided on at least one surface side of the film.
The constituent material (metal material) of the metal layer is not particularly limited, and examples thereof include copper, aluminum, zinc, titanium, nickel, and alloys containing these.
The metal layer may have a single-layer structure or a laminated structure of two or more layers. When the metal layers have a laminated structure, each layer may be made of the same metal material or different metal materials.

In one embodiment, the laminate is a metal layer-film, metal layer-film-metal layer, metal layer-film-metal layer-film, metal layer-metal layer-film, metal layer-metal layer-film-metal layer. Etc. may have a structure such as.
Examples of the method for forming the metal layer include vacuum deposition of metal, sputtering, plating, and the like. Further, a metal layer may be formed by a method of superimposing a film and a metal foil and heat-welding them.

Since the film has excellent dielectric properties, such a laminate can be processed into a flexible printed wiring board (FPC) or a flexible flat cable (FFC) suitable for next-generation high-speed transmission.
Further, if a biaxially stretched film having excellent stretch uniformity is used, the laminated body has excellent thickness uniformity and can suppress variations in its dielectric constant.
Further, an intermediate layer having a function of improving the adhesion thereof may be provided between the film and the metal layer, for example.

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

Although the film and the laminate of the present invention have been described above, the present invention is not limited to the configuration of the above-described embodiment.
For example, the film and the laminate of the present invention may be added to any other configuration in the configuration described above, or may be replaced with any configuration that exhibits the same function.

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

1. 1. Production of Resin Composition and Biaxial Stretched Film [Example 1]
84.5 parts by mass of polyphenylene sulfide resin-1 (manufactured by DIC Corporation, linear type, melt viscosity (V6) 160 Pa · s at melting point 280 ° C., 300 ° C.) and a fluorine-containing resin having 15 parts by mass of functional groups. (B) (“AH-2000” manufactured by AGC Corporation, melting point 240 ° C.) and 0.5 parts by mass of 3-glycidoxypropyltriethoxysilane were uniformly mixed with a tumbler to obtain a mixture. ..

The polyphenylene sulfide resin has a carboxyl group at the molecular terminal thereof.
Hereinafter, the polyphenylene sulfide resin will be referred to as “PPS” and 3-glycidoxypropyltriethoxysilane will be referred to as “silane coupling agent”.

Next, the mixture obtained above was put into a twin-screw extruder with a vent (manufactured by Japan Steel Works, Ltd., "TEX-30α"). After that, it is melt-extruded under the conditions of a discharge rate of 20 kg / hr, a screw rotation speed of 300 rpm, a cylinder set temperature of 320 ° C., and a resin temperature of about 310 ° C. on a strand die, discharged into a strand shape, and cooled with water having a temperature of 30 ° C. , Cutting was performed to produce a resin composition.

Next, this resin composition was dried at 140 ° C. for 3 hours, and then charged into a single-screw extruder of a full flight screw and melted under the conditions of 280 to 310 ° C. The melted resin composition was extruded from the T-die and then closely cooled with a chill roll set at 40 ° C. to prepare an unstretched sheet.
Next, the produced unstretched sheet was biaxially stretched 3.0 × 3.0 times at 100 ° C. using a batch type biaxial stretching machine (manufactured by Imoto Seisakusho Co., Ltd.) to form a film having a thickness of 50 μm. Got Further, the obtained film was fixed to a mold and heat-fixed in an oven at 275 ° C. to produce a biaxially stretched film.

The average particle size of the particles in the produced resin composition was measured as follows.
First, the resin composition pellets were cut in a direction perpendicular to the flow direction by an ultrathin section method. Next, each of the cut surfaces of the cut pellets was photographed by a scanning electron microscope (SEM) at 2000 times, and the obtained image was enlarged to A3 size. Next, any 50 particles in the enlarged SEM photograph were selected, the maximum diameter of each particle on the cut surface was measured, and the average particle size was calculated.
As a result, the average particle size of the particles of the resin composition pellet was 1.3 μm.

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

[Example 2]
A resin composition and a biaxially stretched film were produced in the same manner as in Example 1 except that (B) (manufactured by AGC Inc., “EA-2000”, melting point 300 ° C.) was used as the fluorine-containing resin.
The average particle size of the particles in the biaxially stretched film was measured by the same method as in Example 1 and found to be 1.5 μm.
Further, as a result of analyzing the constituent components of the resin composition pellets by the same method as in Example 1, it was found that the particles of the fluorine-containing resin were dispersed in the PPS matrix.

[Example 3]
The resin composition is the same as in Example 2 except that the PPS resin is changed to PPS resin-2 (manufactured by DIC Corporation, linear type, melt viscosity (V6) 110 Pa · s at melting points 280 ° C. and 300 ° C.). And a biaxially stretched film was produced.
The average particle size of the particles in the biaxially stretched film was measured by the same method as in Example 1 and found to be 1.6 μm.
Further, as a result of analyzing the constituent components of the resin pellets by the same method as in Example 1, it was found that the particles of the fluorine-containing resin were dispersed in the PPS matrix.

[Example 4]
79.5% by mass of PPS resin-2, 15% by mass of EA-2000, 7L of Bond First (ethylene / glycidylmethacrylate / methyl acrylate = 70/3/27 (% by mass)) to a modified elastomer having a reactive group, Sumitomo A stretched film was obtained in the same manner as in Example 1 except that the content was 5% by mass and the silane coupling agent was 0.5% by mass.
As a result of analyzing the constituent components of the resin pellets by the same method as in Example 1, it was found that the particles of the fluorine-containing resin were dispersed in the PPS matrix. The modified elastomer existed as particles dispersed alone or at the interface between the mattrix and the particles of the fluorine-containing resin. The average particle size of the fluorine-containing particles in the resin pellets was measured and found to be 1.2 μm.

[Comparative Example 1]
PPS resin-1 was put into a twin-screw extruder with a vent (manufactured by Japan Steel Works, Ltd., "TEX-30α"). After that, it is melt-extruded under the conditions of a discharge rate of 20 kg / hr, a screw rotation speed of 300 rpm, a set temperature of 320 ° C., and a resin temperature of about 310 ° C. on a strand die, discharged into a strand shape, cooled with water at a temperature of 30 ° C., and then cut. The resin composition was produced. Next, a biaxially stretched film was obtained in the same manner as in Example 1.

[Comparative Example 2]
A biaxially stretched film was prepared in the same manner as in Example 1 except that PPS resin-3 (crosslinked type, melt viscosity (V6) 250 Pa · s at melting point 280 ° C. and 300 ° C.) was used as the PPS resin. Obtained.

[Comparative Example 3]
PPS resin-1 20% by mass and PPS resin-3 64.5% by mass, and fluorine-containing resin AH-2000 15% by mass and silane coupling agent 0.5% by mass are uniformly mixed with a tumbler. A mixture was obtained. After that, the compound material was put into a twin-screw extruder "TEX-30α" with a vent manufactured by Japan Steel Works, Ltd., the discharge rate was 20 kg / hr, the screw rotation speed was 300 rpm, two cylinders directly under the raw material input port and the tip of the cylinder. A biaxially stretched film was obtained in the same manner as in Example 1 except that the die was melt-extruded at a set temperature of 300 ° C. and another cylinder set temperature of 230 ° C. and discharged in a strand shape.

2. 2. Evaluation 2-1. Ratio of MFR before and after heating retention (330 ° C) Using a melt indexer, the mass flowing out from the nozzle was measured after staying for 5 minutes under a cylinder temperature of 330 ° C and a load of 2.16 kgf, and used as MFR1. Further, the outflow amount after staying for 30 minutes under a cylinder temperature of 330 ° C. and a load of 2.16 kgf was measured and used as MFR2.
[Evaluation criteria]
〇: MFR1 / MFR2 0.2 or more and 4.5 or less ×: MFR1 / MFR2 smaller than 0.2, larger than 4.5

2-2. Film formation stability Melt filtration using a 150 μm mesh filter, continuous extrusion for 5 hours, and evaluation of pressurization from the resin pressure immediately after the start of the test and the resin pressure after 5 hours [evaluation criteria]
〇: Booster 2MPa or less ×: Booster 2MPa or less

2-3. Dielectric constant The dielectric constant was determined based on the cavity resonance method specified in JIS C 2565: 1992. Specifically, a strip having a width of 2 mm and a length of 150 mm was produced from the biaxially stretched film. Next, the produced strips were allowed to stand for 24 hours at 23 ° C. and 50% Rh, and then the dielectric constant at a frequency of 1 GHz was measured by a cavity resonance method using an ADMS010c series (manufactured by AET Co., Ltd.).
[Evaluation criteria]
〇; Dielectric constant 3.2 or less ×; Dielectric constant greater than 3.2

The above results are shown in Tables 1 and 2.

As is clear from Tables 1 and 2, it can be seen that in Examples 1 to 4, the film-forming stability was excellent, and the obtained biaxially stretched film had a low dielectric constant and excellent tensile elongation. It was

Claims

A resin composition having a continuous phase and a dispersed phase, using at least 51 to 95% by mass of the polyarylene sulfide resin (A) and 5 to 49% by mass of the fluororesin (B) having a reactive functional group as raw materials. The biaxially stretched film using the resin composition has a dielectric constant of 3.2 or less.
The continuous phase contains the polyarylene sulfide resin (A) and contains.
A polyarylene sulfide resin composition in which the dispersed phase contains a fluorine-containing resin (B) having a reactive functional group.
Ratio of fluidity (melt flow rate 1) after accumulating the resin composition at 330 ° C. for 5 minutes and fluidity (melt flow rate 2) after accumulating for 30 minutes Melt flow rate 1 / melt flow rate The resin composition according to claim 1, wherein 2 is 0.2 or more and 4.5 or less.
The fluorine-containing resin (B) having a reactive functional group is a fluorine-containing resin having at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, and an isocyanate group. , The resin composition according to claim 1 or 2.
The resin composition according to any one of claims 1 to 3, further comprising 1 to 20% by mass of the modified elastomer (C) to which a reactive group is added.
The resin composition according to any one of claims 1 to 4, wherein the modified elastomer (C) comprises an olefin polymer having at least one functional group selected from the group consisting of an epoxy group and an acid anhydride group. ..
Further, according to any one of claims 1 to 5, the silane coupling agent (D) containing 0.05 to 5% by mass of a silane coupling agent (D) containing at least one functional group selected from an epoxy group, an amino group and an isocyanate group. The resin composition described.
A biaxially stretched film obtained by biaxially stretching the resin composition according to any one of claims 1 to 6.
A laminated body comprising the biaxially stretched film according to claim 7 and any one or more of a metal layer or a resin molded body arranged on at least one surface of the biaxially stretched film.