CN116367999A - Polyarylene sulfide resin composition, and biaxially stretched film and laminate using same - Google Patents

Abstract

Provided are a resin composition which has excellent continuous extrusion film forming properties and stretchability and which can provide a biaxially stretched film obtained with a low dielectric constant and excellent toughness, and a laminate using the same. The discovery is as follows: the present invention has been completed by setting the fluidity before and after residence in a specific range in a resin composition comprising a polyarylene sulfide resin (a) and a fluorine-containing resin (B) having a reactive functional group, thereby having a low dielectric constant and excellent toughness in a biaxially stretched film.

Description

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

Technical Field

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

Background

In recent years, in the field of flexible printed circuit boards (FPCs) and Flexible Flat Cables (FFCs), with the development of clouds, ioT (Internet of Things: internet of things), etc., the improvement of automatic driving technology of automobiles, and the development of electric automobiles and hybrid vehicles, cables and antennas capable of handling a large amount of data, transmitting at high speed and without damage have been demanded. However, conventionally, polyimide (PI) films have been used for FPC substrates, and polyester films (PET films, etc.) have been used for FCC substrates, and it cannot be said that the FPC substrates have dielectric characteristics that can be used for next-generation high-speed transmission.

On the other hand, films using polyarylene sulfide resins typified by polyphenylene sulfide resins (PPS resins) are used as insulating materials for capacitors and motors and heat-resistant tapes because they are excellent in heat resistance, flame retardancy, chemical resistance, and electrical insulation. Since polyarylene sulfide resins have excellent dielectric characteristics compared with PI and PET, they can be suitably used in the fields of FPC and FFC. However, in order to cope with the next generation high-speed transmission, further lowering of the dielectric constant is required.

As a method for improving this, for example, patent document 1 proposes a method in which inorganic particles are contained in PPS resin and voids are formed during biaxial stretching. However, the film described in patent document 1 can sufficiently achieve the effect of lowering the dielectric constant, but the mechanical properties of the film are reduced due to the presence of voids. Therefore, a layer containing no inorganic particles is laminated on the surface layer, but sufficient mechanical strength is not obtained. In addition, lamination is required, and in stretching of the laminate, uniformity of adhesion between layers and stretchability of each layer is important, and from the viewpoint of production, it tends to be very difficult.

In order to achieve both excellent properties of PPS resin and fluororesin, several attempts to blend two resins have been reported. For example, patent document 2 proposes a resin composition in which dispersion particle diameters before and after retention are stabilized by using a resin composition composed of PPS resin and a fluororesin having a functional group. However, the proposals described in these patents are made mainly for injection molding applications, and in film applications requiring continuous extrudability, stability of viscosity is important, but there is no description. In addition, the biaxially stretched film having a low dielectric constant is not described.

Prior art literature

Patent literature

Patent document 1: japanese patent application laid-open No. 2018-83415

Patent document 2: japanese patent laid-open No. 2015-110732

Disclosure of Invention

Problems to be solved by the invention

The present invention provides a resin composition which is excellent in continuous extrusion film forming property and stretchability and which can provide a biaxially stretched film obtained with a low dielectric constant and excellent toughness, and a laminate using the same.

Means for solving the problems

The present inventors have made intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by setting the fluidity before and after residence within a specific range in a resin composition comprising a polyarylene sulfide resin (a) and a fluorine-containing resin (B) having a reactive functional group, and have completed the present invention.

That is, the present invention relates to the following (1) to (8).

(1) A polyarylene sulfide resin composition which is a resin composition comprising at least 51 to 95 mass% of a polyarylene sulfide resin (A) and 5 to 49 mass% of a fluorine-containing resin (B) having a reactive functional group as raw materials and having a continuous phase and a disperse phase, wherein the biaxially stretched film using the resin composition has a dielectric constant of 3.2 or less,

The continuous phase contains a polyarylene sulfide resin (A),

the dispersed phase contains a fluorine-containing resin (B) having a reactive functional group.

(2) The ratio of the fluidity (melt flow rate 1) of the resin composition after residence at 330 ℃ for 5 minutes to the fluidity (melt flow rate 2) of the resin composition after residence at 330 ℃ for 30 minutes is preferably 0.2 to 4.5 inclusive.

(3) The fluorine-containing resin (B) having a reactive functional group is preferably a fluorine-containing resin having at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxyl group, an epoxy group, and an isocyanate group.

(4) Further, the modified elastomer (C) to which a reactive group is added is preferably contained in an amount of 1 to 20 mass%.

(5) The modified elastomer (C) is preferably composed 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 the group consisting of 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 (1) to (6).

(8) The laminate of the present invention is a laminate comprising the biaxially stretched film of (7) above and a metal layer disposed on at least one surface of the biaxially stretched film.

Effects of the invention

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 characteristics and excellent toughness.

Detailed Description

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

[ resin composition ]

The resin composition is prepared from at least a polyarylene sulfide resin (hereinafter, sometimes referred to as "PAS resin") and a fluorine-containing resin having a reactive functional group. In this case, the resin composition has a continuous phase and a dispersed phase, and in this case, the continuous phase contains a polyarylene sulfide resin, and the dispersed phase contains a fluorine-containing resin having a reactive functional group.

The resin composition has a ratio MFR1/MFR2 of 0.2 to 4.5 inclusive, which is a ratio of fluidity (melt flow rate 1, herein referred to as "MFR 1") after residence at 330 ℃ for 5 minutes, to fluidity (melt flow rate 2, herein referred to as "MFR 2") after residence at 330 ℃ for 30 minutes, which is a measure of fluidity of a resin in a molten state. When the MFR1/MFR2 ratio is more than 4.5, the reactivity of the PAS resin (a) with the fluorine-containing resin (B) having a reactive functional group proceeds, which means that the tackifying of the resin composition is large, gelation occurs during continuous film formation, and the like, and defects such as rapid rise in the resin pressure of the extruder and breakage during stretching occur. When the MFR1/MFR2 ratio is less than 0.2, decomposition of the PAS resin (A) and the fluorine-containing resin (B) having a reactive functional group proceeds during continuous film formation, which means that the viscosity is reduced and stable film formation is difficult. Therefore, if the fluidity ratio after 5 minutes and 30 minutes at 330℃is within the above range, stable film forming property and stretchability are obtained, and the resin composition having the best continuous extrusion film forming property and stretchability is obtained.

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. If 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 resin (a) (PAS resin (a)) is a 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 resin (A) is a polymer containing a structure in which an aromatic ring is bonded to a sulfur atom (specifically, a structure represented by the following formula (1)) as a repeating unit.

[ chemical 1]

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

Here, R in the structure represented by formula (1) ¹ Preferably hydrogen atoms. With such a constitution, the mechanical strength of the PAS resin (A) can be further improved. As R ¹ The structure represented by the formula (1) in which the sulfur atoms are bonded to the aromatic ring in the para-position, and the structure represented by the formula (3) in which the sulfur atoms are bonded to the aromatic ring in the meta-position are exemplified as the structures represented by the formula (2).

[ chemical 2]

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

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

[ chemical 3]

The structures represented by the formulae (4) to (7) are preferably contained in an amount of 30 mol% or less, more preferably 10 mol% or less, of all the recurring units constituting the PAS resin (A). With such a constitution, the heat resistance and mechanical strength of the PAS resin (A) can be further improved.

The bonding method of the structures represented by the formulas (4) to (7) may be any of random and block.

The PAS resin (A) may contain a 3-functional structure represented by the following formula (8), a naphthalene sulfide structure, or the like as a repeating unit in its molecular structure.

[ chemical 4]

The structure represented by the formula (8), the naphthalene sulfide structure, and the like are preferably contained in an amount of 1 mol% or less, more preferably substantially none, of the total repeating units constituting the PAS resin (A). With such a constitution, the content of chlorine atoms in the PAS resin (A) can be reduced.

The characteristics of the PAS resin (A) are not particularly limited as long as the effect of the present invention is not impaired, and the melt viscosity (V6) at 300℃is preferably 50 to 2000 Pa.s, and more preferably 80 to 1500 Pa.s in view of the balance between fluidity and mechanical strength.

Further, the PAS resin (A) is particularly preferably: in the measurement using Gel Permeation Chromatography (GPC), a peak is present in the range of molecular weight 25,000 ～ 40,000, the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is in the range of 5 to 10, and the non-newtonian index is in the range of 0.9 to 1.3. By using such a PAS resin (A), the chlorine atom content of the PAS resin (A) itself can be reduced to a range of 800 to 2,000ppm without reducing the mechanical strength of the film, and the PAS resin (A) can be easily applied to halogen-free electronic and electric parts.

In the present specification, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw/Mn) are each values measured by Gel Permeation Chromatography (GPC). The measurement conditions of GPC are as follows.

[ measurement conditions based on gel permeation chromatography ]

The device comprises: ultra-high temperature polymer molecular weight distribution measuring apparatus (SSC-7000 manufactured by Senshu scientific Co., ltd.)

Chromatographic column: UT-805L (Zhaohe electric company)

Chromatographic column temperature: 210 DEG C

Solvent: 1-chloronaphthalene

The measuring method comprises the following steps: the molecular weight distribution and peak molecular weight were determined using 6 monodisperse polystyrenes in calibration with a UV detector (360 nm).

The method for producing the PAS resin (A) is not particularly limited, and examples thereof include the following methods: 1) A method of polymerizing a dihaloaromatic compound by adding a polyhaloaromatic compound or other copolymerization component as required in the presence of sulfur and sodium carbonate; 2) A method of polymerizing a dihalo-aromatic compound by adding a polyhalo-aromatic compound or other copolymerization component as required in a polar solvent in the presence of a thioetherification agent or the like; 3) And optionally adding other copolymerization components to self-condense p-chlorophenol. Among these production methods, the method of 2) above is general and preferable.

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

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

2-1) introducing an aqueous thioetherification agent into a heated mixture comprising an organic polar solvent and a dihaloaromatic compound at a rate that enables removal of water from the reaction mixture, adding the dihaloaromatic compound and a thioetherification agent to the organic polar solvent, and if necessary adding the polyhaloaromatic compound, and controlling the water content in the reaction system to a range of 0.02 to 0.5 mol relative to 1 mol of the organic polar solvent at the time of the reaction, thereby producing a PAS-based resin (A) (see JP-A-07-228699).

2-2) by adding a dihaloaromatic compound and optionally a polyhaloaromatic compound or other copolymerizable component in the presence of a solid alkali metal sulfide and an aprotic polar organic solvent, and controlling the amount of the alkali metal salt of an organic acid to a range of 0.01 to 0.9 mol relative to 1 mol of the sulfur source and controlling the amount of water in the reaction system to a range of 0.02 mol or less relative to 1 mol of the aprotic polar organic solvent when reacting the alkali metal hydrosulfide with the alkali metal salt of an organic acid (see WO 2010/058713).

Specific examples of the dihaloaromatic compound include p-dihalobenzene, m-dihalobenzene, o-dihalobenzene, 2, 5-dihalobenzene, 1, 4-dihalobenzene, 1-methoxy-2, 5-dihalobenzene, 4 '-dihalobenzene, 3, 5-dihalobenzoic acid, 2, 4-dihalobenzoic acid, 2, 5-dihalobenzene, 2, 4-dihalobenzene, p, p' -dihalodiphenyl ether, 4 '-dihalobenzophenone, 4' -dihalodiphenyl sulfone, 4 '-dihalodiphenyl sulfoxide, 4' -dihalodiphenyl sulfide, and a compound having an alkyl group having 1 to 18 carbon atoms in the aromatic ring of each of the above compounds.

Examples of the polyhaloaromatic compound include 1,2, 3-trihalobenzene, 1,2, 4-trihalobenzene, 1,3, 5-trihalobenzene, 1,2,3, 5-tetrahalobenzene, 1,2,4, 5-tetrahalobenzene, and 1,4, 6-trihalonaphthalene.

The halogen atom contained in the above-mentioned compound is preferably a chlorine atom or a bromine atom.

The post-treatment method of the reaction mixture containing the PAS resin (A) obtained by the polymerization step may be any known and customary method. Such post-treatment methods are not particularly limited, and examples thereof include the following methods (1) to (5).

(1) In the method (2) of (a), after completion of the polymerization reaction, the solvent is distilled off under reduced pressure or normal pressure after the reaction mixture is directly or after the addition of an acid or a base, and then the solid after the removal of the solvent by distillation is washed 1 or more times with water, a reaction solvent (or an organic solvent having the same solubility as the low molecular polymer), a solvent such as acetone, methyl ethyl ketone, alcohol, etc., followed by further neutralization, washing with water, filtration and drying.

(2) In the method (a), after the completion of the polymerization reaction, a solvent such as water, acetone, methyl ethyl ketone, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons, aliphatic hydrocarbons or the like (a solvent which is soluble in the polymerization solvent used and is a poor solvent at least for the PAS resin (a)) is added to the reaction mixture as a settling agent, and the solid products such as the PAS resin (a) and the inorganic salt are settled, and these are filtered, washed and dried.

(3) In the method (2) of (a) after completion of the polymerization reaction, a reaction solvent (or an organic solvent having an equivalent solubility to the low molecular weight polymer) is added to the reaction mixture and stirred, and after filtration and removal of the low molecular weight polymer, the reaction mixture is washed 1 or more times with a solvent such as water, acetone, methyl ethyl ketone, alcohols, etc., and then neutralized, washed with water, filtered and dried.

(4) In the method (2), after the polymerization reaction is completed, water is added to the reaction mixture, water washing is performed, filtration is performed, and if necessary, acid treatment is performed by adding acid thereto during water washing, and drying is performed.

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

Examples of the acid that can be used in the method (4) include: saturated fatty acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, and monochloroacetic acid; unsaturated fatty acids such as acrylic acid, crotonic acid, and oleic acid; aromatic carboxylic acids such as benzoic acid, phthalic acid, and salicylic acid; dicarboxylic acids such as maleic acid and fumaric acid; organic acids such as sulfonic acids including methanesulfonic acid and p-toluenesulfonic acid; inorganic acids such as hydrochloric acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, and phosphoric acid.

Examples of the hydrogen salt include sodium hydrogen sulfide, disodium hydrogen phosphate, and sodium hydrogencarbonate. However, in practical use, an organic acid having little corrosion to the metal member is preferable.

In the methods (1) to (5), the drying of the PAS resin (A) may be performed in vacuum or in an inert gas atmosphere such as air or nitrogen.

In particular, the PAS resin (A) post-treated by the method of (4) can have an effect of improving the dispersibility of the PAS resin (A) by increasing the amount of the acid groups bonded to the molecular terminals thereof, and mixing the PAS resin with the fluorine-containing resin (B) having a reactive functional group, the modified elastomer (C) and the silane coupling agent (D). The acid group is particularly preferably a carboxyl group.

The content of the PAS resin (A) in the resin composition is preferably from 51 to 95% by mass, more preferably from 60 to 80% by mass. When the content of the PAS resin (A) is within the above range, the heat resistance and toughness of the film can be further improved.

[ fluorine-containing resin (B) having reactive functional group ]

The fluorine-containing resin (B) having a reactive functional group (fluorine-containing resin (B)) has at least one reactive functional group selected from the group consisting of a carbonyl-containing group, a hydroxyl group, an epoxy group, and an isocyanate group. These reactive functional groups may contain 2 or more. Among them, a carbonyl group-containing group is preferable in view of excellent reactivity with the PAS resin (A). Examples of the carbonyl group-containing group include a group having a carbonyl group between carbon atoms of a hydrocarbon group, a carbonate group, a carboxyl group, a haloformyl group, an alkoxycarbonyl group, an acid anhydride group, and a polyfluoroalkoxycarbonyl group.

As a method for introducing the reactive functional group of the fluorine-containing resin (B), the following method can be mentioned: (1) In the production of the main chain of the fluorine-containing resin having a reactive functional group by polymerization, a monomer having a reactive functional group is used. (2) The fluorine-containing resin (B) having a functional group is produced by polymerization using a chain transfer agent that generates a radical having a reactive functional group. (3) The fluorine-containing resin (B) having a functional group is produced by polymerization using a polymerization initiator that generates a radical having a reactive functional group. (4) And a method of modifying the fluorine-based resin by oxidation, thermal decomposition or the like. Further, there is a method (5) of blending a compound or resin which is compatible with the fluorine-based resin and contains the above functional group.

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

Examples of the monomer having a carboxyl group include unsaturated dicarboxylic acids (maleic acid, itaconic acid, citraconic acid, crotonic acid, nadic acid, 5-norbornene-2, 3-dicarboxylic acid, maleic acid), unsaturated dicarboxylic anhydrides thereof, unsaturated monocarboxylic acids (acrylic acid, methacrylic acid), vinyl esters (vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl pivalate, vinyl benzoate, and vinyl crotonate), and the like.

Examples of the hydroxyl group-containing monomer include hydroxyl group-containing vinyl esters, hydroxyl group-containing vinyl ethers, hydroxyl group-containing allyl ethers, hydroxyl group-containing (meth) acrylates, hydroxy ethyl crotonates, and allyl alcohols.

Examples of the epoxy group-containing monomer include unsaturated glycidyl ethers (allyl glycidyl ether, 2-methallyl glycidyl ether, vinyl glycidyl ether, etc.), and unsaturated glycidyl esters (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.

The amount of the reactive functional group contained in the fluorine-containing resin (B) is preferably 0.01 to 3 mol%, more preferably 0.03 to 2 mol%, and still more preferably 0.05 to 1 mol% of the total units constituting the fluorine-containing resin (B). If the amount of the reactive functional group is within the above range, the reactivity with the PAS resin is excellent, and deterioration of fluidity can be suppressed.

The structure of the fluorine-containing resin (B) is not particularly limited, and it is composed of at least one fluoroolefin unit. For example, tetrafluoroethylene polymer, copolymer with perfluoro (alkyl vinyl ether), hexafluoropropylene, vinylidene fluoride, vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene, and further copolymer with a non-fluorovinyl monomer containing no fluorine such as ethylene, propylene, butene, and alkyl vinyl ether can be mentioned. Specifically, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene-hexafluoropropylene copolymer, polyvinylidene fluoride, polychlorotrifluoroethylene, and the like can be cited. Among them, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer, 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℃to 340℃and preferably 180℃to 340℃and more preferably 190℃to 330 ℃. If the melting point of the fluorine-containing resin (B) is within the above range, the heat resistance can be maintained and the melt extrusion stability can be improved.

The glass transition temperature of the fluorine-containing resin (B) used in the present invention is not particularly limited, but is 130℃or lower, more preferably 120℃or lower and 110℃or lower. In the case of the fluorine-containing resin (B) having the glass transition temperature, peeling at the interface between the PAS resin (a) as the continuous phase and the fluorine-containing resin (B) as the dispersed phase can be suppressed in the stretching after mixing with the PAS resin (a). This can suppress breakage during stretching, and further can provide a film having excellent mechanical properties.

The content of the fluorine-containing resin (B) in the resin composition is 5 to 49% by mass, preferably 5 to 40% by mass. When the content of the fluorine-containing resin (B) is within the above range, the effect of improving the dielectric characteristics (lowering the dielectric constant) of the film can be more remarkably exhibited.

In the present invention, a fluorine-containing resin having no reactive functional group may be used in combination with the fluorine-containing resin (B).

[ modified elastomer (C) ]

The modified elastomer (C) is a component having a function of improving the mechanical strength (folding strength, etc.) of the film by having a reactive group capable of reacting with at least one of the PAS resin (a) and the fluorine-containing resin (B).

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 functional groups of the PAS resin (A) and the fluorine-containing resin (B).

Examples of such modified elastomer (C) include: copolymers comprising repeating units based on an alpha-olefin and repeating units based on a vinyl polymerizable compound having the above-mentioned functional group, copolymers comprising repeating units based on an alpha-olefin, repeating units based on a vinyl polymerizable compound having the above-mentioned functional group and repeating units based on an acrylic ester, and the like.

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

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

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

[ chemical 5]

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 vinyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-pentenyl, 1-methyl-3-pentenyl, 1-dimethyl-1-butenyl, 1-hexenyl and 3-hexenyl.

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

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

Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-dimethylbutyl, 2, 3-dimethylbutyl, 2, 4-dimethylbutyl, 3-dimethylbutyl, 2-ethylbutyl and the like.

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

The proportion of the repeating unit based on the α -olefin in the modified elastomer (C) is preferably 50 to 95% by mass, more preferably 50 to 80% by mass. If the proportion of the repeating units based on the α -olefin is in the above range, the stretching uniformity, the folding strength, and the like of the film can be improved.

The proportion 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. If the proportion of the repeating unit based on the vinyl-polymerizable compound having a functional group is within the above range, not only the intended improving 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 mass%, more preferably 1 to 5 mass%. When the content of the modified elastomer (C) is within the above range, the effect of improving the dielectric characteristics, the folding strength, and the like of the film can be significantly exhibited.

[ silane coupling agent (D) ]

The silane coupling agent (D) in the present invention is a component having a function of improving the compatibility (interaction) between the PAS resin (a) and the fluorine-containing resin (B) having a reactive functional group and the modified elastomer (C) as other components. By using the silane coupling agent (D), dispersibility of other components in the PAS resin (a) is dramatically improved, and a favorable form can be obtained.

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) is strongly bonded to the PAS resin (a) and the fluorine-containing resin (B) by reacting them. As a result, the effect of the silane coupling agent (D) can be more remarkably exhibited, and the dispersibility of the fluorine-containing resin (B) in the PAS resin (a) can be particularly improved.

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 epoxy group-containing alkoxysilane compounds such as γ -glycidoxypropyl trimethoxysilane, γ -glycidoxypropyl triethoxysilane, β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, and the like; isocyanate group-containing alkoxysilane compounds such as γ -isocyanatopropyl trimethoxysilane, γ -isocyanatopropyl triethoxysilane, γ -isocyanatopropyl methyldimethoxysilane, γ -isocyanatopropyl methyldiethoxysilane, γ -isocyanatopropyl ethyldimethoxysilane, γ -isocyanatopropyl ethyldiethoxysilane, and γ -isocyanatopropyl trichlorosilane; amino-containing alkoxysilane compounds such as γ - (2-aminoethyl) aminopropyl methyldimethoxy silane, γ - (2-aminoethyl) aminopropyl trimethoxy silane and γ -aminopropyl trimethoxy silane, and hydroxyl-containing alkoxysilane compounds such as γ -hydroxypropyl trimethoxy silane and γ -hydroxypropyl triethoxy silane.

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 within the above range, the effect of improving the dispersibility of other components in the PAS resin (a) can be significantly exhibited.

[ additive ]

The resin composition may contain plasticizers, weather-proofing agents, antioxidants, heat stabilizers, ultraviolet stabilizers, lubricants, antistatic agents, colorants, conductive agents, and the like as long as the effects of the present invention are not impaired.

Resin composition and method for producing the same

The method for producing the resin composition is not particularly limited, and the following methods are exemplified: the PAS resin (A), the fluorine-containing resin (B), the modified elastomer (C), the silane coupling agent (D) and other components as required are uniformly mixed in a tumbler mixer, a Henschel mixer or the like, and then fed into a twin-screw extruder to be melt-kneaded, wherein the melt-kneading may be either or both of kneading in a shear flow field and kneading in an extension flow field. The melt kneading is preferably performed under conditions such that the ratio (discharge amount/screw speed) of the kneaded product (kg/hr) to the screw speed (rpm) is 0.02 to 0.2 (kg/hr·rpm).

The temperature to be set during the mixing is selected to be in the range of +5 to 70℃and more preferably in the range of +10 to 50℃than the melting point of the resin having a higher melting point of the PAS resin (A) and the fluorine-containing resin (B). When the set temperature is lower than the melting points of the PAS resin (a) and the fluorine-containing resin (B), the presence of the PAS resin (a) or the fluorine-containing resin (B), which is not partially melted, greatly increases the viscosity of the composition, and increases the load on the biaxial extruder, which is not preferable in terms of productivity.

More specifically, it is preferable to charge each component into a twin-screw extruder and melt-knead the components at the above-mentioned set temperature and at a temperature of about 310℃as the resin temperature at the drawing die. At this time, the discharge amount of the kneaded material is in the range of 5 to 50kg/hr at a rotation speed of 250 rpm. In particular, from the viewpoint of improving the dispersibility of each component, the discharge amount of the kneaded material is preferably 20 to 35kg/hr at a rotation speed of 250 rpm. Therefore, the ratio (discharge amount/screw rotation speed) of the discharge amount (kg/hr) of the kneaded material to the screw rotation speed (rpm) is more preferably 0.08 to 0.14 (kg/hr·rpm).

The average particle diameter (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 still more preferably 0.5 to 3 μm. If the average particle diameter of the particles is within the above range, a uniform and homogeneous film can be obtained. In the present specification, the "average particle diameter of particles" is a value measured by a method described in examples described below.

Film >

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

In one embodiment of such a film, the PAS 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) is present on the particle surface (i.e., interface between the matrix and the particles) of the fluorine-containing resin (B), in the particles of the fluorine-containing resin (B), or in the form of particles (dispersed phase) different from the particles of the fluorine-containing resin (B).

Further, the inventors of the present invention considered that the modified elastomer (C) also functions as a compatibilizer for the PAS resin (a) and the fluorine-containing resin (B), and the particles are finely dispersed in the matrix, thereby improving the mechanical strength of the film. Further, the inventors have also considered that the use of the silane coupling agent (D) in combination further improves the adhesion of the interface between the matrix of the modified elastomer (C) and the particles, and further improves the mechanical strength of the film.

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

When a biaxially stretched film is produced, the PAS resin (A) constituting the matrix is crystallized in a state in which the molecular chains thereof are stretched, and thus a film having 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 stretching ratio in the width direction (TD direction) of the biaxially stretched film 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 length direction (MD direction) of the biaxially stretched film (width direction (TD direction)/(length direction (MD direction)) is preferably 0.8 to 1.3, and more preferably 0.9 to 1.2 in terms of easily balancing the physical properties in the length direction with 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. The 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 composed of the resin composition of the present invention, and may be laminated with a layer composed of another resin composition directly or via an adhesive layer or the like.

The biaxially stretched film of the present invention may be subjected to a surface treatment for the purpose of improving the adhesion between the biaxially stretched film and a metal or resin molded article. Examples of the surface treatment include corona discharge treatment (corona treatment under various gas atmospheres), plasma treatment (plasma treatment under various gas atmospheres), and oxidation treatment with a chemical agent, ultraviolet rays, electron irradiation rays, and the like. Among them, plasma treatment is preferable.

Process for producing biaxially stretched film

The biaxially stretched film is produced, for example, as follows.

First, the resin composition is dried at 140℃for 3 hours or more and then fed into an extruder heated to 280 to 320 ℃.

Then, the resin composition in a molten state (i.e., kneaded product) passing through the extruder was discharged in the form of a sheet (film) by means of a T die.

Then, the sheet-like kneaded material is brought into close contact with a cooling roll having a surface temperature of 20 to 50 ℃ to be cooled and solidified. Thus, an unstretched sheet in a non-oriented state was obtained.

Subsequently, the unstretched sheet is biaxially stretched. The stretching method is not particularly limited, and a known method can be used. Sequential biaxial stretching methods, simultaneous biaxial stretching methods, or a method combining them may be used.

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

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

Next, stretching was performed in the width direction (TD direction) by a method using a tenter. Both ends of the film stretched in the MD direction were gripped by a jig, and introduced into a tenter to be stretched in the TD direction.

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

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

Subsequently, the stretched film is thermally fixed while being stretched or relaxed in the width direction.

The heat fixing temperature is not particularly limited, but is preferably 200 to 280 ℃, more preferably 220 to 280 ℃, and still more preferably 240 to 275 ℃. The thermal fixing may be performed in 2 stages by changing the thermal fixing temperature. In this case, the heat fixing temperature in the second stage is preferably set to +10 to 40 ℃ higher than the heat fixing temperature in the first stage. The heat resistance and mechanical strength of the stretched film thermally fixed at the heat-fixed temperature in this range are further improved.

The heat setting time is preferably 1 to 60 seconds.

Further, the film is cooled while being relaxed in the width direction in a temperature range of 50 to 270 ℃. The relaxation rate is preferably 0.5 to 10%, more preferably 2 to 8%, and still more preferably 3 to 7%.

[ laminate ]

The laminate of the present invention comprises the 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 an alloy containing the same.

The metal layer may have a single-layer structure or a stacked structure of 2 or more layers. In the case where the metal layers have a laminated structure, each layer may be made of the same metal material or may be made of different metal materials.

In one embodiment, the laminate may have a metal layer-film, a metal layer-film-metal layer-film, a metal layer-film-metal layer, or the like structure.

The method for forming the metal layer may be a method using vacuum deposition, sputtering, plating, or the like of a metal. The metal layer may be formed by a method of overlapping a film with a metal foil and thermally welding the film.

Such a laminate has excellent dielectric characteristics, and therefore can be processed into flexible printed circuit boards (FPCs) and Flexible Flat Cables (FFCs) suitable for next-generation high-speed transmission.

In addition, if a biaxially stretched film excellent in stretching uniformity is used, the thickness uniformity of the laminate is excellent, and variation in dielectric constant can be suppressed.

Further, an intermediate layer having a function of improving adhesion between the film and the metal layer may be provided between them.

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

The film and the laminate of the present invention have been described above, but the present invention is not limited to the configuration of the above embodiment.

For example, the film and the laminate of the present invention may be added to the above-described embodiments, or may be replaced with any structure that performs the same function.

Examples

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

1. Resin composition and production of biaxially stretched film

Example 1

84.5 parts by mass of polyphenylene sulfide resin-1 (line type, melting point 280 ℃ C., 300 ℃ C., 160 Pa.s) having a melt viscosity (V6) and 15 parts by mass of fluorine-containing resin (B) having a functional group (AH-2000, melting point 240 ℃ C., AGC) were uniformly mixed with 0.5 part by mass of 3-glycidoxypropyl triethoxysilane by a drum mixer to obtain a mixture.

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

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

Next, the mixture obtained above was fed into a twin-screw extruder with a vent (manufactured by Nippon Steel Co., ltd., "TEX-30. Alpha."). Then, the resin composition was produced by melt extrusion under conditions of a discharge amount of 20kg/hr, a screw rotation speed of 300rpm, a barrel set temperature of 320℃and a resin temperature at a drawing die of about 310℃and discharging the resin in the form of strands, cooling the resin composition with water having a temperature of 30℃and cutting the resin composition.

Then, the resin composition was dried at 140℃for 3 hours, and then fed into a single-screw extruder with a full-flight screw, and melted at 280 to 310 ℃. After extruding the molten resin composition from the T die, the resin composition was closely cooled by a cooling roll set at 40 ℃ to prepare an unstretched sheet.

Next, the obtained unstretched sheet was biaxially stretched to 3.0X3.0 times at 100℃by using a batch biaxial stretching machine (manufactured by Kyowa Kagaku Co., ltd.), to thereby obtain a film having a thickness of 50. Mu.m. Further, the obtained film was fixed to a die box, and heat-fixing treatment was performed in an oven at 275 ℃.

The average particle diameter 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 the microtome method. Next, 2000 times Scanning Electron Microscope (SEM) photographs of the cut surfaces of the particles after the cutting were taken, respectively, and the obtained images were enlarged to A3 size. Next, any 50 particles in the enlarged SEM photograph were selected, and the maximum diameter of each particle in the cut surface was measured to calculate the average particle diameter.

As a result, the average particle diameter of the particles of the resin composition particles was 1.3. Mu.m.

Further, SEM-EDS analysis of the cut resin particles was performed, and the components of the matrix and particles constituting the resin composition particles were analyzed. The results revealed 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) (product of AGC Co., ltd. "EA-2000" having a melting point of 300 ℃) was used as the fluorine-containing resin.

The average particle diameter of the particles in the biaxially stretched film was measured in the same manner as in example 1, and found to be 1.5. Mu.m.

Further, as a result of analyzing the constituent components of the resin composition particles by the same method as in example 1, it was found that particles of the fluorine-containing resin were dispersed in the matrix of PPS.

Example 3

A resin composition and a biaxially stretched film were produced in the same manner as in example 2 except that the PPS resin was changed to PPS resin-2 (linear type, manufactured by DIC corporation, melting point 280 ℃, melt viscosity (V6) 110pa·s at 300 ℃).

The average particle diameter of the particles in the biaxially stretched film was measured in the same manner as in example 1, and found to be 1.6. Mu.m.

Further, as a result of analyzing the constituent components of the resin particles in the same manner as in example 1, it was found that particles of the fluorine-containing resin were dispersed in the matrix of PPS.

Example 4

A stretched film was obtained in the same manner as in example 1 except that the PPS resin-2 was 79.5% by mass, the EA-2000 was 15% by mass, the modified elastomer bond 7L (ethylene/glycidyl methacrylate/methyl acrylate=70/3/27 (mass%), manufactured by sumitomo chemical company, ltd.) having a reactive group was 5% by mass, and the silane coupling agent was 0.5% by mass.

The composition of the resin particles was analyzed by the same method as in example 1, and it was found that particles of the fluorine-containing resin were dispersed in a matrix of PPS. The modified elastomer is present as particles dispersed alone or at the interface between the matrix and the particles of the fluorine-containing resin. The average particle diameter of fluorine-containing particles in the resin particles was measured and found to be 1.2. Mu.m.

Comparative example 1

PPS resin-1 was fed into a twin screw extruder with a vent (manufactured by Japanese Steel Co., ltd., "TEX-30. Alpha."). Then, the resin composition was produced by melt-extruding the resin at a discharge rate of 20kg/hr, a screw rotation speed of 300rpm, a set temperature of 320℃and a resin temperature at a drawing die of about 310℃and discharging the resin in the form of strands, cooling the resin with water at a temperature of 30℃and cutting the resin. Subsequently, a biaxially stretched film was obtained in the same manner as in example 1.

Comparative example 2

A biaxially stretched film was obtained in the same manner as in example 1, except that PPS resin-3 (crosslinked type, manufactured by DIC Co., ltd., melting point 280 ℃ C., melt viscosity at 300 ℃ C. (V6) 250 Pa.s) was used as the PPS resin.

Comparative example 3

A mixture was obtained by uniformly mixing 20% by mass of PPS resin-1, 64.5% by mass of PPS resin-3, 48% by mass of fluorine-containing resin AH-2000 15% by mass of silane coupling agent and 0.5% by mass of PPS resin by means of a drum mixer. Then, a biaxially stretched film was obtained in the same manner as in example 1 except that the above-mentioned compounding material was fed into a vented twin-screw extruder "TEX-30α" made by Nippon Steel Co., ltd, and melt-extruded at a discharge rate of 20kg/hr, a screw rotation speed of 300rpm, a set temperature of barrel 2 directly below the raw material feed port, a set temperature of barrel tip and die of 300℃and a set temperature of other barrel of 230℃to discharge in the form of strands.

2. Evaluation

2-1 ratio of MFR before and after heating retention (330 ℃ C.)

The mass of the molten steel was measured as MFR1 by a melt index apparatus, and the molten steel was retained at a cylinder temperature of 330℃under a load of 2.16kgf for 5 minutes and then discharged from a nozzle. The flow-out amount after 30 minutes of residence at a cylinder temperature of 330℃under a load of 2.16kgf was measured and used as MFR2.

[ evaluation criterion ]

And (2) the following steps: an MFR1/MFR2 of 0.2 or more and 4.5 or less

X: MFR1/MFR2 of less than 0.2 and greater than 4.5

2-2 film stability

Melt filtration was performed using a 150 μm mesh filter, continuous extrusion was performed for 5 hours, and the pressure increase was evaluated based on the resin pressure immediately after the start of the test and the resin pressure after 5 hours.

[ evaluation criterion ]

And (2) the following steps: the boosting pressure is below 2MPa

X: the boosting is more than 2MPa

2-3 dielectric constant

The dielectric constant is based on JIS C2565: 1992. Specifically, a long strip having a width of 2mm×a length of 150mm was produced from a biaxially stretched film. Then, the prepared long bar was allowed to stand at 23℃under 50% Rh for 24 hours, and then the dielectric constant at a frequency of 1GHz was measured by a cavity resonance method using ADMS010c series (manufactured by AET, inc.).

[ evaluation criterion ]

And (2) the following steps: dielectric constant of 3.2 or less

X: dielectric constant greater than 3.2

The results are shown in tables 1 and 2.

TABLE 1

TABLE 2

As is clear from tables 1 and 2, the film formation stability was excellent in examples 1 to 4, and the biaxially stretched films obtained were low in dielectric constant and excellent in tensile elongation.

Claims (8)

1. A polyarylene sulfide resin composition which comprises at least 51 to 95 mass% of a polyarylene sulfide resin (A) and 5 to 49 mass% of a fluorine-containing resin (B) having a reactive functional group as raw materials and has a continuous phase and a disperse phase, wherein in a biaxially stretched film using the resin composition, the dielectric constant is 3.2 or less,

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

the dispersed phase contains a fluorine-containing resin (B) having a reactive functional group.

2. The resin composition according to claim 1, wherein the ratio of the fluidity after residence at 330 ℃ for 5 minutes, namely, the melt flow rate 1 to the fluidity after residence for 30 minutes, namely, the melt flow rate 2, namely, the melt flow rate 1/melt flow rate 2, is 0.2 or more and 4.5 or less.

3. The resin composition according to claim 1 or 2, wherein 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-containing group, a hydroxyl group, an epoxy group and an isocyanate group.

4. The resin composition according to any one of claims 1 to 3, further comprising 1 to 20 mass% of a modified elastomer (C) to which a reactive group is added.

5. The resin composition according to any one of claims 1 to 4, wherein the modified elastomer (C) is composed 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. The resin composition according to any one of claims 1 to 5, further comprising 0.05 to 5 mass% of a silane coupling agent (D) containing at least one functional group selected from epoxy groups, amino groups, isocyanate groups.

7. A biaxially stretched film obtained by biaxially stretching the resin composition according to any one of claims 1 to 6.

8. A laminate comprising the biaxially stretched film according to claim 7, and at least one of a metal layer and a resin molded body disposed on at least one surface of the biaxially stretched film.