WO2018221321A1

WO2018221321A1 - Resin composition and method of production thereof, and resin film

Info

Publication number: WO2018221321A1
Application number: PCT/JP2018/019660
Authority: WO
Inventors: 勇樹市村; 岡田　光弘
Original assignee: 住友化学株式会社
Priority date: 2017-05-31
Filing date: 2018-05-22
Publication date: 2018-12-06
Also published as: JP2020122030A

Abstract

Disclosed is a resin composition comprising: a component (A), which is at least one kind selected from the group consisting of an ethylene-α,β-unsaturated carboxylic acid alkyl ester copolymer, an ethylene-α,β-unsaturated carboxylic acid copolymer, and an ethylene-saturated aliphatic carboxylic acid α,β-unsaturated alcohol ester copolymer; and a component (B), which is a polyphenylene ether including a repeating unit represented by formula (1). The content of the component (B) is 1 to 35 parts by mass when the total amount of component (A) and component (B) is taken to be 100 parts by mass.

Description

Resin composition and method for producing the same, and resin film

The present invention relates to an ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymer, an ethylene-α, β-unsaturated carboxylic acid copolymer, and an ethylene-saturated aliphatic carboxylic acid α, β-unsaturated alcohol ester. The present invention relates to a resin composition containing an ethylene copolymer selected from copolymers, a method for producing the same, and a resin film.

The manufacturing process of a flexible printed circuit board may include a hot press process in which a coverlay film for forming a surface protective layer is bonded to the flexible printed circuit board. During this hot pressing, a release film is generally inserted between the coverlay film and the press plate. As a material for this release film, a resin composition containing an ethylene-α, β-unsaturated carboxylic acid copolymer or an ethylene-α, β-unsaturated carboxylic acid derivative copolymer may be used (for example, a patent) References 1, 2).

On the other hand, an ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymer may be used in order to improve the stress crack resistance of the polyphenylene ether resin (for example, Patent Documents 3 and 4).

JP-A-3-293126 JP 2003-211602 A Japanese Patent Laid-Open No. 10-025412 JP 09-316321 A

In the production of release films, ethylene copolymers such as ethylene-α, β-unsaturated carboxylic acid copolymers are molded together with other high-melting-point thermoplastic resins to impart release properties to the release film. Sometimes. It has been clarified that the heat received during the molding process may cause thermal decomposition of the ethylene copolymer. From the viewpoint of working environment and the like, it is desired that thermal decomposition during molding is suppressed as much as possible.

On the other hand, in order to ensure the flexibility of a resin film such as a release film, it is also necessary that the resin composition containing an ethylene copolymer has an appropriate flexibility.

Accordingly, one aspect of the present invention is an ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymer, an ethylene-α, β-unsaturated carboxylic acid copolymer, and an ethylene-saturated aliphatic carboxylic acid α, β-. With respect to a resin composition containing an ethylene copolymer selected from unsaturated alcohol ester copolymers, an object is to suppress thermal decomposition at high temperatures while maintaining appropriate flexibility.

One aspect of the present invention is:
Component (A): ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymer, ethylene-α, β-unsaturated carboxylic acid copolymer, and ethylene-saturated aliphatic carboxylic acid α, β-unsaturated alcohol At least one ethylene copolymer selected from the group consisting of ester copolymers;
Component (B): A resin composition containing polyphenylene ether containing a repeating unit represented by the following formula (1) (hereinafter sometimes referred to as “modified resin composition”) is provided. In particular, the content of component (B) is 1 to 35 parts by mass, where the total of component (A) and component (B) is 100 parts by mass.

In the formula, R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom or a hydrocarbyl group having 1 to 10 carbon atoms which may have one or more substituents. Indicates. A plurality of R ¹ , R ² , R ³ and R ⁴ in the same molecule may be the same or different.

The above-mentioned modified resin composition is suppressed from thermal decomposition at high temperatures while maintaining appropriate flexibility.

The modified resin composition may contain a continuous phase containing the component (A) and dispersed particles containing the component (B) dispersed in the continuous phase. In that case, the average dispersed particle diameter of the dispersed particles may be 5 μm or less. Thereby, the effect of the thermal decomposition suppression by polyphenylene ether (component (B)) is especially remarkable.

The modified resin composition can be produced, for example, by a method including a step of melt kneading a raw material mixture containing the component (A) and the component (B). The raw material mixture may be melt-kneaded while heating to 50 to 350 ° C.

Another aspect of the present invention relates to a resin film containing the modified resin composition. The resin film may be a single layer film containing the modified resin composition and another thermoplastic resin different from the component (A) and the component (B), or the modified resin composition The multilayer film which has the intermediate | middle layer to contain and the surface layer which is laminated | stacked on the at least one surface of an intermediate | middle layer, and contains the other thermoplastic resin different from a component (A) and a component (B) may be sufficient. Surface layers containing other thermoplastic resins may be laminated on both sides of the intermediate layer.

Since these resin films have moderate flexibility and heat resistance, they are useful as, for example, release films used in the production of flexible printed boards.

The other thermoplastic resin different from the component (A) and the component (B) may be at least one of poly (4-methyl-1-pentene) and polybutylene terephthalate. Although these have a high melting point exceeding 200 ° C., the thermal decomposition of the modified resin composition is sufficiently suppressed even under high temperature conditions required when molding the modified resin composition together with these. The

With respect to a resin composition containing an ethylene copolymer such as an ethylene-α, β-unsaturated carboxylic acid copolymer, thermal decomposition at high temperatures can be suppressed while maintaining appropriate flexibility.

It is a transmission electron micrograph of the resin composition produced in the Example.

Hereinafter, some embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

<Resin composition>
The resin composition (modified resin composition) according to one embodiment comprises component (A): ethylene-α, β-unsaturated carboxylic acid copolymer, ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymer And at least one ethylene copolymer selected from the group consisting of a copolymer and an ethylene-saturated aliphatic carboxylic acid α, β-unsaturated alcohol ester copolymer, and component (B): represented by the following formula (1) And polyphenylene ether containing repeating units. This modified resin composition is usually a thermoplastic resin composition.

In the formula (1), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, or a hydrocarbon having 1 to 10 carbon atoms which may have one or more substituents. Indicates a carbyl group. A plurality of R ¹ , R ² , R ³ and R ⁴ in the same molecule may be the same or different.

The content of the component (B) in the modified resin composition is 1 to 35 parts by mass with the total of the component (A) and the component (B) being 100 parts by mass. The content of the component (B) may be 25 parts by mass or less, or 20 parts by mass or less from the viewpoint of maintaining appropriate flexibility. The content of the component (B) may be 2 parts by mass or more, 4 parts by mass or more, or 5 parts by mass or more from the viewpoint of suppressing thermal decomposition of the modified resin composition.

The ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymer that can be used as the ethylene copolymer of component (A) is a monomer unit derived from ethylene (hereinafter also referred to as “ethylene unit”). And a monomer unit derived from an α, β-unsaturated carboxylic acid alkyl ester (hereinafter also referred to as “α, β-unsaturated carboxylic acid alkyl ester unit”) as a main monomer unit. is there.

The ethylene unit content in the ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymer is 50% by mass or more and 60% by mass based on the mass of the ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymer. % Or more, or 70% by mass or more, or 98% by mass or less, or 95% by mass or less. The content of the α, β-unsaturated carboxylic acid alkyl ester unit in the ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymer is the mass of the ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymer. As a reference, it may be 2% by mass or more, or 5% by mass or more, or 50% by mass or less, 40% by mass or less, or 30% by mass or less. When the content of the ethylene unit and the α, β-unsaturated carboxylic acid alkyl ester unit is within these ranges, the layer or film containing the ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymer and the others described below There exists a tendency for adhesiveness with the thermoplastic resin of this to become high.

The ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymer may contain other monomer units other than ethylene units and α, β-unsaturated carboxylic acid alkyl ester units, but ethylene-α, β- The total proportion of ethylene units and α, β-unsaturated carboxylic acid alkyl ester units in the unsaturated carboxylic acid alkyl ester copolymer is based on the mass of the ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymer. Usually, it is 90 to 100% by mass, and may be 95 to 100% by mass. The ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymer may be substantially free of monomer units having an epoxy group. The content of the monomer unit having an epoxy group may be 0 to 1% by mass based on the mass of the ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymer, or 0% by mass (ie, It does not include a monomer unit having an epoxy group.

The α, β-unsaturated carboxylic acid alkyl ester constituting the ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymer is, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, N-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, hexyl methacrylate, octyl methacrylate, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, And at least one selected from the group consisting of isobutyl acrylate.

Specific examples of the component (A) ethylene-α, β unsaturated carboxylic acid alkyl ester copolymer include ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-n-propyl acrylate. Copolymer, ethylene-isopropyl acrylate copolymer, ethylene-n-butyl acrylate copolymer, ethylene-t-butyl acrylate copolymer, ethylene-isobutyl acrylate copolymer, ethylene-methyl methacrylate copolymer Polymer, ethylene-ethyl methacrylate copolymer, ethylene-n-propyl methacrylate copolymer, ethylene-isopropyl methacrylate copolymer, ethylene-n-butyl methacrylate copolymer, ethylene-t-butyl methacrylate And copolymers and ethylene-isobutyl methacrylate copolymers . Component (A) may contain one or more selected from these. Component (A) is an ethylene-methyl acrylate copolymer, an ethylene-ethyl acrylate copolymer, an ethylene-methyl methacrylate copolymer and an ethylene-ethyl methacrylate copolymer, or an ethylene-methyl acrylate copolymer. It may be at least one selected from a copolymer and an ethylene-methyl methacrylate copolymer.

The ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymer is produced by a usual production method, for example, a high-pressure radical polymerization method.

The ethylene-α, β-unsaturated carboxylic acid copolymer that can be used as the ethylene copolymer of component (A) is a monomer unit derived from ethylene (hereinafter also referred to as “ethylene unit”) and α. , Β-unsaturated carboxylic acid-derived monomer unit (hereinafter also referred to as “α, β-unsaturated carboxylic acid unit”) as a main monomer unit.

The ethylene unit content in the ethylene-α, β-unsaturated carboxylic acid copolymer is 50% by mass or more, 60% by mass or more based on the mass of the ethylene-α, β-unsaturated carboxylic acid copolymer, or 70 mass% or more may be sufficient, and 98 mass% or less or 95 mass% or less may be sufficient. The content of the α, β-unsaturated carboxylic acid unit in the ethylene-α, β-unsaturated carboxylic acid copolymer is 2% by mass or more based on the mass of the ethylene-α, β-unsaturated carboxylic acid copolymer. Or 5 mass% or more, 50 mass% or less, 40 mass% or less, or 30 mass% or less. When the content of the ethylene unit and the α, β-unsaturated carboxylic acid unit is within these ranges, the layer or film containing the ethylene-α, β-unsaturated carboxylic acid copolymer and other thermoplastic resins described later There exists a tendency for adhesiveness with etc. to become high.

The ethylene-α, β-unsaturated carboxylic acid copolymer may contain other monomer units other than ethylene units and α, β-unsaturated carboxylic acid units. The total proportion of ethylene units and α, β-unsaturated carboxylic acid units in the copolymer is usually 90 to 100% by mass based on the mass of the ethylene-α, β-unsaturated carboxylic acid copolymer. 95 to 100% by mass. The ethylene-α, β-unsaturated carboxylic acid copolymer may be substantially free of monomer units having an epoxy group. The content of the monomer unit having an epoxy group may be 0 to 1% by mass based on the mass of the ethylene-α, β-unsaturated carboxylic acid copolymer, or 0% by mass (ie, epoxy group). May not be included).

The α, β-unsaturated carboxylic acid constituting the ethylene-α, β-unsaturated carboxylic acid copolymer is, for example, acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, 3-butenoic acid, angelic acid, tiglic acid Or at least one selected from the group consisting of 4-pentenoic acid, 2-ethyl-2-butenoic acid, 10-undecenoic acid, oleic acid, propiolic acid, 2-butynoic acid, and 9-octadesinic acid .

Specific examples of the ethylene-α, β unsaturated carboxylic acid copolymer of component (A) include ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-crotonic acid copolymer, ethylene-isocroton. Acid copolymer, ethylene- (3-butenoic acid) copolymer, ethylene-angelic acid copolymer, ethylene-tiglic acid copolymer, ethylene- (4-pentenoic acid) copolymer, ethylene- (2- Ethyl-2-butenoic acid) copolymer, ethylene- (10-undecenoic acid) copolymer, ethylene-oleic acid copolymer, ethylene-propiolic acid copolymer, ethylene- (2-butynoic acid) copolymer And ethylene- (9-octadesinic acid) copolymers. Component (A) may contain one or more selected from these. Component (A) may be at least one selected from an ethylene-acrylic acid copolymer and an ethylene-methacrylic acid copolymer.

The ethylene-α, β-unsaturated carboxylic acid copolymer is produced by a usual production method, for example, a high-pressure radical polymerization method.

The ethylene-saturated aliphatic carboxylic acid α, β-unsaturated alcohol ester copolymer that can be used as the ethylene copolymer of component (A) is a monomer unit derived from ethylene (hereinafter also referred to as “ethylene unit”). And monomer units derived from saturated aliphatic carboxylic acid α, β-unsaturated alcohol esters (hereinafter also referred to as “saturated aliphatic carboxylic acid α, β-unsaturated alcohol ester units”). It is a copolymer contained as a monomer unit.

The ethylene unit content in the ethylene-saturated aliphatic carboxylic acid α, β-unsaturated alcohol ester copolymer is 50 based on the mass of the ethylene-saturated aliphatic carboxylic acid α, β-unsaturated alcohol ester copolymer. It may be not less than mass%, not less than 60 mass%, or not less than 70 mass%, and may be not more than 98 mass% or not more than 95 mass%. The content of the saturated aliphatic carboxylic acid α, β-unsaturated alcohol ester unit in the ethylene-saturated aliphatic carboxylic acid α, β-unsaturated alcohol ester copolymer is determined by the ethylene-saturated aliphatic carboxylic acid α, β-unsaturated content. It may be 2% by mass or more, or 5% by mass or more based on the mass of the saturated alcohol ester copolymer, and may be 50% by mass or less, 40% by mass or less, or 30% by mass or less. A layer containing an ethylene-saturated aliphatic carboxylic acid α, β-unsaturated alcohol ester copolymer when the content of the ethylene unit and the saturated aliphatic carboxylic acid α, β-unsaturated alcohol ester unit is within these ranges. Or there exists a tendency for the adhesiveness of a film, the below-mentioned other thermoplastic resin, etc. to become high.

The ethylene-saturated aliphatic carboxylic acid α, β-unsaturated alcohol ester copolymer may contain other monomer units other than ethylene units and saturated aliphatic carboxylic acid α, β-unsaturated alcohol ester units, The total proportion of ethylene units and saturated aliphatic carboxylic acid α, β-unsaturated alcohol ester units in the ethylene-saturated aliphatic carboxylic acid α, β-unsaturated alcohol ester copolymer is expressed as ethylene-saturated aliphatic carboxylic acid α. Based on the mass of the, β-unsaturated alcohol ester copolymer, it is usually 90 to 100% by mass, and may be 95 to 100% by mass. The ethylene-saturated aliphatic carboxylic acid α, β-unsaturated alcohol ester copolymer may contain substantially no monomer unit having an epoxy group. The content of the monomer unit having an epoxy group may be 0 to 1% by mass based on the mass of the ethylene-saturated aliphatic carboxylic acid α, β-unsaturated alcohol ester copolymer. % (That is, not including a monomer unit having an epoxy group).

The saturated aliphatic carboxylic acid α, β-unsaturated alcohol ester constituting the ethylene-saturated aliphatic carboxylic acid α, β-unsaturated alcohol alkyl ester copolymer is composed of a saturated aliphatic carboxylic acid and an α, β-unsaturated alcohol. And an ester compound formed by The saturated aliphatic carboxylic acid α, β-unsaturated alcohol ester may be a saturated aliphatic carboxylic acid vinyl alcohol ester. Examples thereof include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, and pivalic acid. Vinyl, vinyl hexanoate, vinyl heptanoate, vinyl octanoate, vinyl nonanoate, vinyl decanoate, vinyl undecanoate, vinyl dodecanoate, vinyl tridecanoate, and vinyl tetradecanoate. The saturated aliphatic carboxylic acid α, β-unsaturated alcohol ester constituting the ethylene-saturated aliphatic carboxylic acid α, β-unsaturated alcohol alkyl ester copolymer is one or more selected from these. Also good.

Specific examples of the ethylene-saturated aliphatic carboxylic acid α, β-unsaturated alcohol ester copolymer of component (A) include ethylene-vinyl acetate copolymer, ethylene-vinyl propionate copolymer, ethylene-vinyl butyrate. Copolymer, ethylene-vinyl valerate copolymer, ethylene-vinyl pivalate copolymer, ethylene-vinyl hexanoate copolymer, ethylene-vinyl heptanoate copolymer, ethylene-vinyl octanoate copolymer, ethylene -Vinyl nonanoate copolymer, ethylene-vinyl decanoate copolymer, ethylene-vinyl undecanoate copolymer, ethylene-vinyl dodecanoate copolymer, ethylene-vinyl tridecanoate copolymer, and ethylene-vinyl tetradecanoate A copolymer is mentioned. Component (A) may contain one or more selected from these. Component (A) may be at least one selected from an ethylene-vinyl acetate copolymer and an ethylene-vinyl propionate copolymer.

The ethylene-saturated aliphatic carboxylic acid α, β-unsaturated alcohol ester copolymer is produced by a usual production method, for example, a high-pressure radical polymerization method.

The melt flow rate (MFR) of ethylene copolymers such as ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymers is 0.2 g / 10 min or more, 0.5 g / 10 min or more, 1.0 g. / 10 min or more, 1.5 g / min or more, 5 g / 10 min or more, 10 g / 10 min or more, or 15 g / 10 min or more, 300 g / 10 min or less, 200 g / 10 min or less, 150 g / It may be 10 minutes or less, 50 g / 10 minutes or less, or 30 g / 10 minutes or less. If the MFR is too small, the load on the extruder may increase in the process of extruding the resin composition. If the MFR is too large, neck-in may increase when the resin composition is processed. Here, the MFR of the ethylene copolymer is measured under conditions of a temperature of 190 ° C. and a load of 21.18 N according to JIS K7210.

The durometer A hardness of an ethylene copolymer such as an ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymer may be 50 to 98 from the viewpoint of mechanical strength and flexibility. From the same viewpoint, the durometer A hardness of the ethylene copolymer may be 60 to 96, or 70 to 94. The durometer A hardness is measured according to JIS K 6253. The durometer A hardness of the ethylene copolymer is mainly composed of α, β-unsaturated carboxylic acid alkyl ester unit, α, β-unsaturated carboxylic acid unit, or saturated aliphatic carboxylic acid α, β-unsaturated alcohol ester. It can adjust with content of.

The modified resin composition according to an embodiment contains polyphenylene ether (hereinafter sometimes referred to as “PPE”) containing a repeating unit represented by the above formula (1). The PPE can be known. In formula (1), the hydrocarbyl group as R ¹ , R ² , R ³ or R ⁴ may be, for example, an alkyl group, an aralkyl group, an aryl group, or an alkenyl group. The hydrocarbyl group may have, for example, one or more substituents selected from a halogen atom, a hydrocarbyloxy group, a nitro group, a sulfonyl group, and a silyl group.

Examples of the alkyl group include linear alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, and n-octyl group; Branched alkyl groups such as isopropyl, isobutyl, t-butyl, isopentyl, neopentyl, and 2-ethylhexyl; and cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and A cyclic alkyl group such as a cyclooctyl group can be exemplified. The alkyl group may be a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or may be a linear or branched alkyl group having 1 to 10 carbon atoms. . Examples of the aralkyl group include a benzyl group and a phenethyl group. The aralkyl group may be an aralkyl group having 7 to 10 carbon atoms. Examples of the aryl group include a phenyl group, a tolyl group, and a xylyl group. The aryl group may be an aryl group having 6 to 10 carbon atoms. Examples of the alkenyl group include linear alkenyl groups such as vinyl group, allyl group, 3-butenyl group, and 5-hexenyl group; branched alkenyl groups such as isobutenyl group and 5-methyl-3-pentenyl group; And cyclic alkenyl groups such as 2-cyclohexenyl group and 3-cyclohexenyl group. The alkenyl group may be an alkenyl group having 2 to 10 carbon atoms. R ¹ , R ² , R ³ and R ⁴ in the formula (1) may be a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

PPE is, for example, poly (2,6-dimethylphenylene-1,4-ether), poly (2,6-diethylphenylene-1,4-ether), poly (2,6-dibromophenylene-1,4). -Ether), poly (2-methyl-6-ethylphenylene-1,4-ether), poly (2-chloro-6-methylphenylene-1,4-ether), poly (2-methyl-6-isopropylphenylene) -1,4-ether), poly (2,6-di-n-propylphenylene-1,4-ether), poly (2-chloro-6-bromophenylene-1,4-ether), poly (2- Chloro-6-ethylphenylene-1,4-ether), poly (2-methylphenylene-1,4-ether), poly (2-chlorophenylene-1,4-ether), poly (2-phenylphenol) Nylene-1,4-ether), poly (2-methyl-6-phenylphenylene-1,4-ether), poly (2-bromo-6-phenylphenylene-1,4-ether) and poly (2,4 It can be selected from homopolymers such as' -methylphenylphenylene-1,4-ether) and two or more copolymers selected from monomers of these polymers.

The PPE may further contain other monomer units in addition to the repeating unit of the formula (1). Other monomer units include, for example, monomers selected from polyhydric hydroxyaromatic compounds such as bisphenol A, tetrabromobisphenol A, resorcin, hydroquinone and novolac resins, styrene, and unsaturated compounds having an epoxy group. It can be a derived monomer unit. The proportion of monomer units other than the repeating unit of the formula (1) in PPE is usually 0 to 50% by mass and may be 1 to 25% by mass based on the mass of PPE.

PPE is, for example, a homopolymer of 2,6-dimethylphenol or 2,6-diphenylphenol, or 2,6-xylenol and 3-methyl-6-t-butylphenol or 2,3,6-trimethylphenol. The copolymer may be used.

The reduced viscosity of PPE may be 0.05 to 1.0 dL / g from the viewpoint of heat resistance of the modified resin composition and from the viewpoint of mechanical properties of the modified resin composition. The reduced viscosity of PPE may be 0.06 to 0.80 dL / g, or 0.07 to 0.70 dL / g. The reduced viscosity here means a value obtained by measurement according to JIS K 7367-1.

The Young's modulus measured by the tensile test of the modified resin composition may be 300 MPa or less, or 200 MPa or less, or 10 MPa or more, or from the viewpoint of cushioning properties and flexibility of the resin film obtained from the resin composition. It may be 20 MPa or more.

The modified resin composition may have a form including a continuous phase containing the component (A) and dispersed particles containing the component (B) dispersed in the continuous phase. The average dispersed particle size of the dispersed particles containing the component (B) may be 5 μm or less. When the average dispersed particle size of the dispersed particles is small, the thermal decomposition of the modified resin composition tends to be more effectively suppressed. From the same viewpoint, the average dispersed particle diameter of the dispersed particles may be 3 μm or less, 2 μm or less, or 1 μm or less. The average dispersed particle size of the dispersed particles is determined by observing an ultrathin section of the modified resin composition using a transmission electron microscope, and randomly extracting 15 or more dispersed particles of PPE from the observation field. It is the average value of the measured particle diameter when measuring the dispersed particle diameter. Here, the dispersed particle diameter of the dispersed particles is defined as follows: d = (major diameter), where the inner diameter in the direction in which the width of the dispersed particles is maximum is the major axis, and the inner diameter in the direction perpendicular to the major axis is the minor axis. (Length + minor axis length) / 2).

The modified resin composition can be produced, for example, by a method including a step of kneading a raw material mixture containing the component (A) and the component (B). The kneading method may be, for example, melt kneading or solvent kneading. Kneading can be performed using, for example, a twin-screw kneader or a lab plast mill. From the viewpoint of further reducing the average dispersed particle size of the dispersed particles containing PPE, melt kneading or solvent kneading using a biaxial kneader, or melt kneading using a biaxial kneader can be selected. As a biaxial kneader, the same direction biaxial kneading extruder is mentioned, for example. The maximum temperature of the raw material mixture at the time of kneading may be 50 to 350 ° C. from the viewpoint that the dispersed particle size can be reduced. From the same viewpoint, the raw material mixture may be heated to 100 to 320 ° C, 150 to 300 ° C, 200 to 280 ° C, or 240 to 280 ° C. The kneading time may be 1 second to 1800 seconds, 2 seconds to 600 seconds, or 3 seconds to 300 seconds.

<Resin film>
The resin film which concerns on one Embodiment has a 1 or more layer containing the modified resin composition which concerns on the above-mentioned embodiment. The resin film may be a single layer film containing the modified resin composition and another thermoplastic resin different from the component (A) and the component (B). Alternatively, the resin film includes an intermediate layer containing the modified resin composition and a surface layer containing another thermoplastic resin that is laminated on at least one surface of the intermediate layer and is different from the component (A) and the component (B). And a multilayer film having The surface layer may be laminated on both surfaces of the intermediate layer. The intermediate layer of the multilayer film may further contain another thermoplastic resin different from the component (A) and the component (B). The thickness of the single layer film may be, for example, 10 to 300 μm. In the multilayer film, the intermediate layer may have a thickness of 10 to 200 μm, and the surface layer may have a thickness of 10 to 100 μm. If the intermediate layer is too thin, the uniformity of the press pressure may be reduced during hot pressing, and if the intermediate layer is too thick, the resin may leak from the intermediate layer during hot pressing. If the surface layer is too thin, the resin film itself may be easily damaged. If the surface layer is too thick, followability to the surface shape of the flexible printed circuit board may be reduced. From the same viewpoint, the thickness of the entire multilayer film may be 300 μm or less.

As another thermoplastic resin, a resin film suitably used for a release film or the like can be obtained by using a resin imparting releasability to the resin film. Specific examples of the other thermoplastic resins include poly (4-methyl-1-pentene) and polybutylene terephthalate.

The single-layer film can be produced by forming a molding material containing a modified resin composition and other thermoplastic resins. Film formation can be performed by a solution method or a melting method. The multilayer film can be produced, for example, by co-extrusion of the modified resin composition and another thermoplastic resin using a multilayer T-die or a multilayer annular die. Other lamination methods such as other extrusion lamination methods and dry lamination methods may be used. When the other thermoplastic resin is poly (4-methyl-1-pentene) or polybutylene terephthalate, the heating temperature in the production by the melting method of the single layer film or the coextrusion molding of the multilayer film is usually It is about 200 to 300 ° C. Even in such a high-temperature process, the thermal decomposition of the modified resin composition can be sufficiently suppressed.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

The following raw materials were prepared.
Component (A) (ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymer)
A-1: manufactured by Sumitomo Chemical Co., Ltd., ACLIFT (registered trademark) WK307 (ethylene-methyl methacrylate copolymer, ethylene unit: 75 mass%, methyl methacrylate unit: 25 mass%, MFR: 7 g / 10 min)
A-2: manufactured by Sumitomo Chemical Co., Ltd., ACLIFT (registered trademark) WD106 (ethylene-methyl methacrylate copolymer, ethylene unit: 94.2% by mass, methyl methacrylate unit: 5.8% by mass, MFR: 0.32 g) / 10 minutes)
A-3: manufactured by Sumitomo Chemical Co., Ltd., ACLIFT (registered trademark) WK402 (ethylene-methyl methacrylate copolymer, ethylene unit: 75% by mass, methyl methacrylate unit: 25% by mass, MFR: 20 g / 10 min)
A-4: manufactured by Sumitomo Chemical Co., Ltd., ACLIFT (registered trademark) CG4002 (ethylene-methyl acrylate copolymer, ethylene unit: 70% by mass, methyl acrylate unit: 30% by mass, MFR: 7 g / 10 min)
A-5: Sumitomo Chemical, Sumitate (registered trademark) KA30 (ethylene-vinyl acetate copolymer, ethylene unit: 72% by mass, vinyl acetate unit: 28% by mass, MFR: 7 g / 10 min)
A-6: Mitsui DuPont Nuclele (registered trademark) N410 (ethylene-methacrylic acid copolymer, ethylene unit: 91% by mass, methacrylic acid unit: 9% by mass, MFR: 25 g / 10 min)
A-7: Arkema, Lotyl (registered trademark) 17BA04 (ethylene-butyl acrylate copolymer, ethylene unit: 83% by mass, butyl acrylate unit: 17% by mass, MFR: 4 g / 10 min)
Component (B) (polyphenylene ether)
B-1: manufactured by Asahi Kasei Corporation, Zylon (registered trademark) S201A (poly (2,6-dimethyl-1,4-phenylene ether), reduced viscosity: 0.52 dL / g)
B-2: manufactured by SABIC, Noryl (registered trademark) SA120 (poly (2,6-dimethyl-1,4-phenylene ether), reduced viscosity: 0.12 dL / g)

Example 1
95 parts by mass of A-1 from the main feed port was added to the same-direction twin screw extruder (KZW20TW, manufactured by Technobel Co., Ltd.) having nine Babels C1 to C9 arranged in order along the extrusion direction from the feed port. 5 parts by mass of B-1 was charged from the feed port and melt kneaded. The conditions for melting and kneading were set as follows. The obtained melt-kneaded product was cut with a pelletizer to obtain a pellet-shaped resin composition.
Barrel temperature C1: 50 ° C, C2: 150 ° C, C3 to C5: 250 ° C, C6, C7: 260 ° C, C8: 230 ° C, C9: 190 ° C
・ Nozzle head temperature: 150 ℃
・ Screw rotation speed: 300rpm
・ Discharge rate: 4kg / hour

FIG. 1 is a transmission electron micrograph of the resin composition of Example 1. Dispersed particles containing polyphenylene ether were dispersed in a continuous phase mainly composed of an ethylene-methyl methacrylate copolymer. The average dispersed particle size of these dispersed particles was 5 μm or less.

(Comparative Example 1)
The product pellet of A-1 was evaluated as it was as the resin composition of Comparative Example 1.

(Pyrolysis behavior)
Each resin composition was analyzed by thermogravimetric analysis using a SDT2960 manufactured by TA Instruments under the conditions of a heating rate of 10 ° C./min, and the residual weight at 330 ° C. (the ratio of the residual mass to the initial mass) was measured. As shown in Table 1, the thermal decomposition of the α, β-unsaturated carboxylic acid alkyl ester copolymer was suppressed by adding polyphenylene ether.

(Examples 2 to 11, Comparative Examples 2 and 3)
The resin composition in the form of pellets was prepared by the raw material composition ratio shown in Table 2 by melt kneading using the same-direction twin-screw extruder under the same conditions as in Example 1, and the same heat as in Example 1 was obtained. Assessed by gravimetric analysis.

The resin composition was press-molded into a sheet at 260 ° C., and a test piece having a length of 120 mm, a width of 20 mm, and a thickness of 0.5 mm was produced from the obtained sheet. For each test piece, a stress-strain curve was obtained by a tensile test under conditions of a chuck interval of 60 mm and a tensile speed of 5 mm / min with a tensile tester, and the initial elastic modulus (Young's modulus) of each resin composition was measured therefrom.

Table 2 shows the measurement results. The resin compositions of Examples 2 to 11 exhibited moderately low Young's modulus capable of exhibiting cushioning properties while suppressing thermal decomposition. Although the thermal decomposition was suppressed, the resin compositions of Comparative Examples 2 and 3 were hard materials with a Young's modulus exceeding 300 MPa and insufficient cushioning properties.

(Examples 12 to 15, Comparative Examples 4 to 7)
The component (A) from the main feed port and the component (B) from the sub-feed port were introduced into the same unidirectional twin-screw extruder as in Example 1 in the raw material composition ratios shown in Table 1, and these were melt-kneaded. The conditions for melting and kneading were set as follows. The obtained melt-kneaded product was cut with a pelletizer to obtain a pellet-shaped resin composition.
Barrel temperature C1: 50 ° C, C2: 150 ° C, C3: 250 ° C, C4 to C6: 280 ° C, C7: 260 ° C, C8: 230 ° C, C9: 190 ° C
・ Nozzle head temperature: 150 ℃
・ Screw rotation speed: 300rpm
・ Discharge rate: 4kg / hour

(Pyrolysis behavior)
The residual weight at 330 ° C. of each resin composition was measured by the same thermogravimetric analysis as in Example 1. As shown in Table 3, it was confirmed that even in the resin compositions of Examples 12 to 15, thermal decomposition was suppressed as compared with Comparative Examples 4 to 7 not containing the component (B). In addition, the resin compositions of Examples 12 to 15 maintained moderate flexibility because the content of the component (B) was as low as 10 parts by mass.

Claims

Component (A): ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymer, ethylene-α, β-unsaturated carboxylic acid copolymer, and ethylene-saturated aliphatic carboxylic acid α, β-unsaturated alcohol At least one ethylene copolymer selected from the group consisting of ester copolymers;
Component (B): polyphenylene ether containing a repeating unit represented by the following formula (1);
Containing
The resin composition, wherein the content of the component (B) is 1 to 35 parts by mass with the total of the component (A) and the component (B) being 100 parts by mass.

[Wherein R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, a halogen atom, or a hydrocarbyl having 1 to 10 carbon atoms which may have one or more substituents. A plurality of R 1 , R 2 , R 3 and R 4 in the same molecule may be the same or different. ]
The resin composition includes a continuous phase containing the component (A), and dispersed particles dispersed in the continuous phase and containing the component (B), and the dispersed particles have an average dispersed particle size of 5 μm or less. The resin composition according to claim 1.
A method for producing a resin composition according to claim 1 or 2, comprising a step of melt kneading the raw material mixture containing the component (A) and the component (B).
The method according to claim 3, wherein the raw material mixture is melt-kneaded while being heated to 50 to 350 ° C.
A resin film containing the resin composition according to claim 1 or 2.
The resin film according to claim 5, which is a single layer film containing the resin composition and a thermoplastic resin different from the component (A) and the component (B).
A multilayer film having an intermediate layer containing the resin composition, and a surface layer containing another thermoplastic resin different from the component (A) and the component (B) laminated on at least one surface of the intermediate layer The resin film according to claim 5, wherein
The resin film according to claim 7, wherein the surface layer is laminated on both surfaces of the intermediate layer.
The resin film according to any one of claims 6 to 8, wherein the other thermoplastic resin is at least one of poly (4-methyl-1-pentene) and polybutylene terephthalate.