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WO2017073559A1 - Polyamide resin composition and film - Google Patents

Polyamide resin composition and film Download PDF

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Publication number
WO2017073559A1
WO2017073559A1 PCT/JP2016/081578 JP2016081578W WO2017073559A1 WO 2017073559 A1 WO2017073559 A1 WO 2017073559A1 JP 2016081578 W JP2016081578 W JP 2016081578W WO 2017073559 A1 WO2017073559 A1 WO 2017073559A1
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WO
WIPO (PCT)
Prior art keywords
polyamide
mass
polyamide resin
resin composition
film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2016/081578
Other languages
French (fr)
Japanese (ja)
Inventor
直靖 薮
英男 佐野
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ube Corp
Original Assignee
Ube Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ube Industries Ltd filed Critical Ube Industries Ltd
Priority to JP2017547801A priority Critical patent/JP6838555B2/en
Priority to KR1020187014647A priority patent/KR20180079366A/en
Priority to CN201680063088.9A priority patent/CN108350270B/en
Publication of WO2017073559A1 publication Critical patent/WO2017073559A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
    • C08L23/0876—Salts thereof, i.e. ionomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a polyamide resin composition and a film containing the same.
  • a film made of a polyamide resin composition (hereinafter, a "film made of a polyamide resin composition” may be referred to as a "polyamide film” or a “resin film”) has gas barrier properties, toughness, pinhole resistance, heat resistance It is excellent in various characteristics such as elasticity and transparency. For this reason, polyamide films are widely used in various fields. Specifically, the polyamide film is also used as, for example, a food packaging member (see Patent Document 1).
  • the polyamide film when a polyamide film is used as a food packaging member, the polyamide film may be heated upon heat sterilization. Therefore, in such a case, excellent thermal durability is required for the polyamide film.
  • the main object of the present invention is to provide a polyamide resin composition that can provide a polyamide film having excellent thermal durability, and a film.
  • the problems are solved by the following means ⁇ 1>, preferably by ⁇ 2> to ⁇ 11>.
  • ⁇ 1> Polyamide resin, 0.1% by mass to 5% by mass of olefin elastomer, 0.01% by mass to 1% by mass of antioxidant, and 0.01% by mass to 3% by mass of ionomer resin
  • the polyamide resin composition containing.
  • ⁇ 2> The polyamide resin composition according to ⁇ 1>, wherein the polyamide resin comprises an aliphatic polyamide resin.
  • ⁇ 4> The polyamide resin composition according to any one of ⁇ 1> to ⁇ 3>, wherein the olefin-based elastomer contains an ethylene-ethyl acrylate copolymer.
  • ⁇ 5> The ⁇ 1> to ⁇ 3>, wherein the olefin-based elastomer contains an ethylene-ethyl acrylate copolymer, and the acrylic acid content of the ethylene-ethyl acrylate copolymer is 5% by mass to 30% by mass.
  • ⁇ 6> The polyamide resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein the antioxidant comprises a phenolic antioxidant.
  • ⁇ 7> The polyamide resin composition according to any one of ⁇ 1> to ⁇ 6>, wherein the ionomer resin comprises at least one of an ethylene-methacrylic acid copolymer and an ethylene-acrylic acid copolymer.
  • the olefin elastomer and the ionomer resin each independently contain at least one of an ethylene-methacrylic acid copolymer and an ethylene-acrylic acid copolymer The polyamide resin composition as described.
  • the polyamide resin composition which can provide the polyamide film which has the outstanding thermal durability, and a film can be provided.
  • the polyamide resin composition according to the present invention comprises a polyamide resin, 0.1% by mass to 5% by mass of an olefin elastomer, 0.01% by mass to 1% by mass of an antioxidant, and 0.01% by mass to And 3% by mass of ionomer resin.
  • polyamide resin for example, homopolymers of aliphatic polyamides and copolymers using several kinds of raw material monomers forming these (i.e., aliphatic polyamide resins, homopolymers or copolymers Of the Specific examples of homopolymers of aliphatic polyamides and copolymers using several kinds of raw material monomers forming these include, for example, polycaproamide (polyamide 6), poêtcane amide (polyamide 11), polydodecane Amide (polyamide 12), polyethylene adipamide (polyamide 26), polytetramethylene succinamide (polyamide 44), polytetramethylene glutamide (polyamide 45), polytetramethylene adipamide (polyamide 46), polytetramethylene Suberamide (polyamide 48), polytetramethylene azelamide (polyamide 49), polytetramethylene sebacamide (polyamide 410), polytetramethylene dodecamide
  • polyamide resin for example, polymethaxylylene adipamide (polyamide MXD6), polymethaxylylene beramide (polyamide MXD8), polymethaxylylene aceramide (polyamide MXD9), polymethaxylylene sebacamide (polyamide MXD10) Polymethaxylylene dodecamide (polyamide MXD12), polymethaxylylene terephthalamide (polyamide MXDT), polymethaxylylene isophtalamide (polyamide MXDI), polymethaxylylene hexahydroterephthalamide (polyamide MXDT (H)), polymers Taxylylene naphthalamide (polyamide MXDN), polyparaxylylene adipamide (polyamide PXD6), polyparaxylylenes beramide (polyamide PXD8), polyparaxylylene Ramid (polyamide PXD9), polyparaxylylene
  • polycaproamide polyamide 6
  • polymetaxylylene adipamide polyamide MXD 6
  • polyundecane amide polyamide 11
  • polydodecane amide polyamide 12
  • polyhexamethylene adipate Pamide polyamide 66
  • polyhexamethylene decamide polyamide 610
  • polyhexamethylene dodecamide copolymer of polyamide 6 and polyamide 12
  • polydecamethylene decamide polyamide 1010
  • polydecamethylene dodecamide Polyamide 1012
  • at least one homopolymer selected from the group consisting of polydodecamethylene dodecamide polyamide 1212
  • at least one homopolymer selected from the group consisting of proamide polyamide 6
  • poêtcane amide polyamide 11
  • polydodecane amide polydodecane amide
  • 90% by mass or more of the polyamide resin contained in the polyamide resin composition according to the present invention is preferably an aliphatic polyamide resin (for example, polyamide 6), and 95% by mass or more is an aliphatic polyamide resin (for example, polyamide) 6) is more preferably, 99% by mass or more is an aliphatic polyamide resin (for example, polyamide 6), and substantially 100% by mass is an aliphatic polyamide resin (for example, polyamide 6) Is more preferred.
  • substantially 100% by mass means that all polyamide resins are aliphatic polyamide resins (e.g., polyamide 6) except for those which are unintentionally mixed with impurities and the like.
  • the total amount of polyamide resin in the polyamide resin composition according to the present invention is preferably 80% by mass or more, more preferably 85% by mass or more, still more preferably 90% by mass or more, and further preferably 92% by mass or more of the composition. . 99.88 mass% or less is preferable, and the total amount of the said polyamide resin may be 99 mass% or less.
  • a polyamide resin only 1 type of the said polyamide resin may be used independently, and multiple types of polyamide resin may be mixed and used. When mix
  • the olefin elastomer is copolymerized with at least one selected from ethylene and propylene and at least one selected from an ⁇ , ⁇ -unsaturated carboxylic acid monomer and an ⁇ , ⁇ -unsaturated carboxylic acid ester monomer Polymer.
  • Examples of the ⁇ , ⁇ -unsaturated carboxylic acid monomer include acrylic acid and methacrylic acid.
  • ⁇ -unsaturated carboxylic acid ester monomers methyl ester, ethyl ester, propyl ester, butyl ester, pentyl ester, hexyl ester, heptyl ester, octyl ester, nonyl ester, decyl ester of these unsaturated carboxylic acids Or a mixture of these.
  • olefin-based elastomer only one of the above-mentioned olefin-based elastomers may be used alone, or plural types of olefin-based elastomers may be mixed and used.
  • ethylene- (meth) acrylic acid ester copolymer obtained by copolymerizing ethylene and (meth) acrylic acid ester monomer is preferable, and specifically, ethylene-ethyl acrylate copolymer, ethylene-methyl Acrylate copolymer, ethylene-ethyl methacrylate copolymer and the like are more preferable.
  • an ethylene-ethyl acrylate copolymer is preferably used as an olefin elastomer from the viewpoint of the thermal stability at the time of molding and the effect of adding a small amount.
  • the content of (meth) acrylic acid ester in the ethylene- (meth) acrylic acid ester copolymer is preferably 5 to 30% by mass.
  • the content of the olefin-based elastomer is 0.1% by mass to 5% by mass of the polyamide resin composition.
  • the content of the olefin elastomer is preferably 0.5% by mass or more, more preferably 0.8% by mass or more, and still more preferably 1% by mass or more.
  • transparency of the resin film using a polyamide resin composition can be maintained by content of an olefin type elastomer being 5 mass% or less.
  • the content of the olefin elastomer is preferably 4% by mass or less, more preferably 3.5% by mass or less, and still more preferably 3% by mass or less.
  • olefin-based elastomer only one type may be used alone, or a plurality of olefin-based elastomers may be mixed and used. When using multiple types, it is preferable that a total amount becomes the said range.
  • the content of the ethylene-ethyl acrylate copolymer is preferably 0.1% by mass to 5% by mass.
  • the content of the ethylene-ethyl acrylate copolymer is more preferably 0.5% by mass or more, still more preferably 0.8% by mass or more, and 1% by mass or more. Is more preferred.
  • the content of the ethylene-ethyl acrylate copolymer is more preferably 4% by mass or less, still more preferably 3.5% by mass or less, and still more preferably 3% by mass or less preferable.
  • olefin elastomer only one of the above-mentioned ethylene-ethyl acrylate copolymers may be used alone, or a plurality of olefin elastomers may be mixed and used. When using multiple types, it is preferable that a total amount becomes the said range.
  • a phenol type antioxidant represented by Irganox 1098, a hindered amine type antioxidant, a phosphorus type antioxidant represented by IRGAFOS 168 etc., a sulfur type antioxidant, a hydrazine type antioxidant, an amide
  • a system antioxidant etc. are mentioned, a phenol type antioxidant is used preferably in this invention.
  • N ′, N′-bis-3- examples include '-5'di-t-butyl-4'-hydroxyphenyl) propionyl hexamethylene diamine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and the like.
  • N ′, N′-bis-3- (3′-5′-di-t-butyl-4′-hydroxyphenyl) propionylhexamethylene diamine is preferably used as a phenolic antioxidant.
  • the content of the antioxidant is 0.01% by mass to 1% by mass.
  • the content of the antioxidant is preferably 0.05% by mass or more, more preferably 0.08% by mass or more, and still more preferably 0.1% by mass or more .
  • the content of the antioxidant exceeds 1% by mass, long-term heat resistance can be expected, but from the viewpoint of practical material cost, the content of the antioxidant is 1% by mass or less, 0 .8 mass% or less is preferable, 0.5 mass% or less is more preferable, 0.3 mass% or less is more preferable.
  • antioxidant only 1 type of the said antioxidant may be used independently, and multiple types of antioxidant may be mixed and used. When using multiple types, it is preferable that a total amount becomes the said range.
  • the ionomer resin is an olefin / unsaturated carboxylic acid in which the side chain carboxyl group of the main chain consisting of an olefin unit and an ⁇ , ⁇ -unsaturated carboxylic acid unit is partially neutralized with metal ions (crosslinking via metal ions) It is a copolymer.
  • the olefin examples include ethylene and propylene. Among them, ethylene is preferably used. As the ⁇ , ⁇ -unsaturated carboxylic acid, acrylic acid and methacrylic acid are preferably used, but other ⁇ , ⁇ -unsaturated carboxylic acid esters may be copolymerized. In the present invention, in particular, the ionomer resin preferably contains at least one of an ethylene-methacrylic acid copolymer and an ethylene-acrylic acid copolymer.
  • the metal ion component of the neutralized carboxyl group includes, in addition to alkali metal ions such as lithium ion, sodium ion, potassium ion, magnesium ion, calcium ion, strontium ion and barium ion, alkaline earth metal ion, aluminum ion, tin ion, Examples thereof include titanium ions, manganese ions, iron ions, nickel ions, copper ions, zinc ions and cadmium ions. Only one of these metal ion components may be used, or two or more thereof may be used.
  • the degree of neutralization of the carboxyl groups of the ionomer resin (the ratio of the number of neutralized carboxyl groups to the total number of carboxyl groups (the ratio of the number of neutralized carboxyl groups / the total number of carboxyl groups) x 100 (unit:%)) is 20% to 80% Is preferable, and 30% to 70% is more preferable.
  • the degree of neutralization of the carboxyl group of the ionomer resin is 20% or more, the transparency of the obtained film becomes good, which is preferable. It is preferable for the degree of neutralization of the carboxyl group of the ionomer resin to be 80% or less, since the decrease in melt flowability of the ionomer resin is avoided and the transparency of the obtained film is improved.
  • the content of the ionomer resin in the polyamide resin composition is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more in the polyamide resin composition from the viewpoint of compatibility with the polyamide resin and the olefin elastomer. More preferably, it is 0.1 mass% or more. Similarly, from the viewpoint of film transparency, 3% by mass or less is preferable, more preferably 1% by mass or less, and still more preferably 0.6% by mass or less.
  • the ionomer resin may be contained alone or in combination of two or more kinds in the polyamide resin composition. When 2 or more types are contained, it is preferable that a total amount becomes said range.
  • the ionomer resin may react with the ionomer resin or with other components in the polyamide resin composition or film, but this case is also included in the range of the polyamide resin composition or film according to the present invention. Needless to say.
  • the mass ratio (ionomer resin / olefin elastomer) of the ionomer resin to the olefin elastomer in the polyamide resin composition is preferably 0.04 to 0.4.
  • the lower limit value of the mass ratio is more preferably 0.05 or more, and the upper limit value of the mass ratio is more preferably 0.3 or less.
  • the olefin elastomer and the ionomer resin independently contain at least one of an ethylene-methacrylic acid copolymer and an ethylene-acrylic acid copolymer. In such a case, the compatibility between the two is improved, and the above effect is more effectively exhibited.
  • the polyamide resin composition according to the present invention may contain, for example, an antiblocking agent, a lubricant, a nucleating agent, a foaming agent, a stabilizer, a coupling agent and the like in addition to the above components, but is not limited thereto.
  • Each of these additives may be contained alone or in combination of two or more. However, the content of these additives is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, based on the total mass of the polyamide resin composition. Is 1% by mass or less.
  • the polyamide resin composition which concerns on this invention may contain thermoplastic resins other than a polyamide resin, it is preferable not to contain.
  • the thermoplastic resin other than the polyamide resin contained in the polyamide resin composition according to the present invention is preferably 1% by mass or less of the polyamide resin.
  • the method for producing the polyamide resin composition is not particularly limited, and various additives may be blended if necessary, and various methods conventionally known can be adopted.
  • the polyamide resin composition is, for example, a method of dry blending uniformly to a specific ratio using a tumbler or a mixer, or a method of melt-kneading a mixture obtained by dry blending with a melt kneader, It can manufacture by the method etc. which carry out the dry blending with the remainder, after knead
  • Melt-kneading can be performed using kneaders, such as a single-screw extruder, a twin-screw extruder, a kneader, and a Banbury mixer.
  • the film according to the present invention comprises the polyamide resin composition according to the present invention.
  • the film according to the present invention is preferably formed of a polyamide resin composition.
  • the thickness of the film according to the present invention is preferably 1 to 300 ⁇ m.
  • the film according to the present invention may be, for example, a stretched film.
  • the polyamide resin composition is melt-kneaded using an extruder, extruded into a film form using a die such as a T-die or a coat hanger die, cast on a casting roll surface, and then cooled. Contained films can be produced.
  • the produced film may be subjected to a stretching treatment to form a stretched film. In that case, the produced film may be uniaxially stretched to be a uniaxially stretched film, or may be biaxially stretched to be a biaxially stretched film.
  • the film laminate according to the present invention is a laminate of a plurality of films including the film according to the present invention.
  • the film laminate according to the present invention can be produced, for example, by thermocompression bonding a plurality of films including the film according to the present invention.
  • the produced film laminate may be subjected to a stretching treatment to form a stretched film laminate.
  • the produced film laminate may be uniaxially stretched to be a uniaxially stretched film laminate, or may be biaxially stretched to be a biaxially stretched film laminate.
  • the film laminated body which concerns on this invention may be comprised, for example by the core layer and the skin layer which covers each of both surfaces of a core layer.
  • the skin layer be constituted of the polyamide resin composition according to the present invention.
  • the core layer is made of a barrier resin such as polymetaxylylene adipamide (polyamide MXD6) or ethylene-vinyl alcohol copolymer
  • the skin layer is made of the polyamide resin composition according to the present invention.
  • the film according to the present invention contains the polyamide resin 6, it is a packaging material for food, and is preferably used particularly for applications to be heat-treated.
  • a preferred embodiment of the present invention is a film according to the present invention, which is a film laminate of a film containing polyamide resin 6 and a barrier layer (for example, ethylene-vinyl alcohol copolymer (EVOH)). .
  • the details of the film laminate can be referred to the description of JP-A-2001-341253, the contents of which are incorporated herein.
  • a laminate in which the composition constituting the layer B is replaced with the polyamide resin composition according to the present invention in JP-A-2001-341253 is preferable.
  • Polyamide resin Polyamide 6 (hereinafter also referred to as "PA 6", trade name: UBE nylon 1022 B (manufactured by Ube Industries, Ltd.))
  • Olefin-based elastomer ethylene-ethyl acrylate copolymer (hereinafter, also referred to as "ethylene-ethyl acrylate resin”, trade name: UBE polyethylene ZE 708 (manufactured by Ube Maruzen Polyethylene Co., Ltd.)
  • Acrylic in ethylene-ethyl acrylate copolymer The content of acid ester is 16% by mass.
  • Olefin-based elastomer ethylene-ethyl acrylate copolymer, trade name: UBE polyethylene ZE 742 (manufactured by Ube Maruzen Polyethylene Corporation) The content of acrylic ester in the ethylene-ethyl acrylate copolymer is 25% by mass.
  • Antioxidant Phenolic antioxidant, Irganox 1098 (manufactured by BASF)
  • Ionomer resin Zn 2+ ionomer of ethylene-methacrylic acid copolymer, degree of neutralization of carboxyl group of ionomer resin 60%, trade name: HIMIRAN 1706 (manufactured by Mitsui & DuPont Co., Ltd.)
  • Example 1 Dry blend of 98.7% by mass of polyamide 6, 1% by mass of ethylene-ethyl acrylate copolymer (ZE 708), 0.1% by mass of antioxidant, and 0.2% by mass of ionomer resin The mixture was mixed to obtain a polyamide resin composition.
  • the film which consists of a polyamide resin composition was obtained using the Pravo T-die shaping
  • the set temperature of the extruder was 200 to 260 ° C.
  • the temperature of the die was 260 ° C.
  • the temperature of the cooling roll was 30 ° C. Films with thicknesses of 100 ⁇ m and 50 ⁇ m were produced by changing the winding speed of the roll.
  • Example 2 The content of polyamide 6 in the polyamide resin composition is 96.1% by mass, the content of ethylene-ethyl acrylate copolymer (ZE 708) is 3% by mass, and the content of antioxidant is 0.3% by mass.
  • a film of a polyamide resin composition was produced in the same manner as in Example 1 except that the content of the ionomer resin was 0.6% by mass.
  • Example 3 The content of polyamide 6 in the polyamide resin composition is 99.3% by mass, the content of ethylene-ethyl acrylate copolymer (ZE 708) is 0.5% by mass, and the content of antioxidant is 0.1% %, And a polyamide film was produced in the same manner as in Example 1 except that the content of the ionomer resin was 0.1% by mass.
  • Example 4 The content of polyamide 6 in the polyamide resin composition is 98.7% by mass, the content of ethylene-ethyl acrylate copolymer (ZE 742) is 1% by mass, and the content of antioxidant is 0.1% by mass.
  • a polyamide film was produced in the same manner as in Example 1 except that the content of the ionomer resin was 0.2% by mass.
  • Example 5 The content of polyamide 6 in the polyamide resin composition is 96.1% by mass, the content of ethylene-ethyl acrylate copolymer (ZE 742) is 3% by mass, and the content of antioxidant is 0.3% by mass.
  • a polyamide film was produced in the same manner as in Example 1 except that the ionomer resin content was 0.6% by mass.
  • Example 1 A polyamide film was produced in the same manner as in Example 1 using only polyamide 6 to prepare a polyamide film.
  • Example 2 A polyamide film was produced in the same manner as in Example 1 except that the content of polyamide 6 in the polyamide resin composition was 99.9% by mass, and the ethylene-ethyl acrylate copolymer (ZE 708) and the ionomer resin were not used. .
  • the content of the polyamide 6 in the polyamide resin composition is 99.0 mass%, the content of the ethylene-ethyl acrylate copolymer (ZE 708) is 1 mass%, and the antioxidant and the ionomer resin are not used.
  • a polyamide film was produced in the same manner as in Example 1.
  • the content of polyamide 6 in the polyamide resin composition is 97.0% by mass, the content of ethylene-ethyl acrylate copolymer (ZE 708) is 3% by mass, and no antioxidant and ionomer resin are used.
  • a polyamide film was produced in the same manner as in Example 1.
  • the content of polyamide 6 in the polyamide resin composition is 99.0 mass%, ethylene-ethyl acrylate copolymer and antioxidant are not used, and the content of ionomer resin is 1 mass%.
  • a polyamide film was produced in the same manner as in Example 1.
  • the content of polyamide 6 in the polyamide resin composition is 98.8% by mass, the content of ethylene-ethyl acrylate copolymer (ZE 708) is 1% by mass, and the content of ionomer resin is 0.2% by mass.
  • a polyamide film was produced in the same manner as in Example 1 except that no inhibitor was used.
  • the haze value of the biaxially stretched film was measured by Haze Meter manufactured by Nippon Denshoku Kogyo Co., Ltd. according to ASTM D-1003. Specifically, a 100 ⁇ m thick film is preheated for 60 seconds at 100 ° C. using a biaxial drawing machine BIX-703 manufactured by Iwamoto Seisakusho, and then the extrusion direction (MD direction) at T die forming and the right angle thereof After stretching in 3.0 directions at a deformation rate of 150 mm / sec in two directions (TD direction), heat treatment is performed with heated air at 200 ° C. for 30 seconds, and then cooled and taken out from the stretching tank. A biaxially stretched film of about 15 ⁇ m was obtained. The above-mentioned haze value was measured using the obtained biaxially stretched film.
  • Elongation retention (%) tensile elongation at break after hot water treatment (%) / tensile elongation at break before hot water treatment (%) x 100
  • the film using the polyamide resin composition according to the present invention was high in tensile elongation at break and elongation retention, and also excellent in pinhole resistance even after hot water treatment. Furthermore, as is clear from the comparison of Example 1 with Comparative Example 3 and Example 2 with Comparative Example 4, it was possible to significantly lower the haze by blending the antioxidant and the ionomer resin. In addition, when no antioxidant was contained (Comparative Examples 5 to 7), various physical properties after the hot water treatment were remarkably inferior. In particular, the performance was inferior to the case where a film consisting only of a polyamide resin was used (Comparative Example 1). When the ionomer antioxidant was not contained (comparative example 8), the haze became high.
  • polyamide resin composition As a polyamide resin composition, polyamide 6 as a polyamide resin, UBE polyethylene ZE 708 as an olefin elastomer, and HIMIRAN 1706 as an ionomer resin were blended so as to have the mass ratio shown in Table 3.
  • the obtained polyamide resin composition was used to form an unstretched single-layer film having a thickness of 100 ⁇ m according to Example 1. Furthermore, it carried out similarly to the method as described in the item of haze, and obtained a 15-micrometer-thick stretched single layer film. The tensile elastic modulus of the obtained stretched single-layer film is measured at 23 ° C.

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Abstract

Provided are: a polyamide resin composition that can yield a polyamide film having excellent thermal durability; and a polyamide film. The polyamide resin composition comprises a polyamide resin, 0.1-5 mass% of an olefinic elastomer, 0.01-1 mass% of an antioxidant, and 0.01-3 mass% of an ionomer resin.

Description

ポリアミド樹脂組成物、フィルムPolyamide resin composition, film

　本発明は、ポリアミド樹脂組成物、それを含むフィルムに関する。 The present invention relates to a polyamide resin composition and a film containing the same.

　ポリアミド樹脂組成物からなるフィルム（以下、「ポリアミド樹脂組成物からなるフィルム」を「ポリアミドフィルム」、「樹脂フィルム」と称することがある。）は、ガスバリア性、強靱性、耐ピンホール性、耐熱性、透明性等の各種特性に優れている。このため、ポリアミドフィルムは、種々の分野で多用されている。具体的には、ポリアミドフィルムは、例えば、食品包装部材等としても用いられている（特許文献１を参照。）。 A film made of a polyamide resin composition (hereinafter, a "film made of a polyamide resin composition" may be referred to as a "polyamide film" or a "resin film") has gas barrier properties, toughness, pinhole resistance, heat resistance It is excellent in various characteristics such as elasticity and transparency. For this reason, polyamide films are widely used in various fields. Specifically, the polyamide film is also used as, for example, a food packaging member (see Patent Document 1).

特開２００１－３４１２５３号公報JP 2001-341253 A

　ところで、例えば、食品包装部材としてポリアミドフィルムが用いられるような場合には、加熱殺菌に際してポリアミドフィルムが加熱される場合がある。従って、このような場合には、ポリアミドフィルムに優れた熱的耐久性が要求される。 By the way, for example, when a polyamide film is used as a food packaging member, the polyamide film may be heated upon heat sterilization. Therefore, in such a case, excellent thermal durability is required for the polyamide film.

　本発明に係る主な目的は、優れた熱的耐久性を有するポリアミドフィルムを提供し得るポリアミド樹脂組成物、及び、フィルムを提供することにある。 The main object of the present invention is to provide a polyamide resin composition that can provide a polyamide film having excellent thermal durability, and a film.

　上記課題のもと、本発明者が検討を行った結果、下記手段＜１＞により、好ましくは＜２＞～＜１１＞により、上記課題は解決された。
＜１＞ポリアミド樹脂と、０．１質量％～５質量％のオレフィン系エラストマーと、０．０１質量％～１質量％の酸化防止剤と、０．０１質量％～３質量％のアイオノマー樹脂と、を含む、ポリアミド樹脂組成物。
＜２＞前記ポリアミド樹脂が脂肪族ポリアミド樹脂を含む、＜１＞に記載のポリアミド樹脂組成物。
＜３＞前記ポリアミド樹脂がポリアミド６を含む、＜１＞に記載のポリアミド樹脂組成物。
＜４＞前記オレフィン系エラストマーが、エチレン－エチルアクリレート共重合体を含む、＜１＞～＜３＞のいずれか一つに記載のポリアミド樹脂組成物。
＜５＞前記オレフィン系エラストマーが、エチレン－エチルアクリレート共重合体を含み、前記エチレン－エチルアクリレート共重合体におけるアクリル酸含有量が５質量％～３０質量％である、＜１＞～＜３＞のいずれか一つに記載のポリアミド樹脂組成物。
＜６＞前記酸化防止剤がフェノール系酸化防止剤を含む、＜１＞～＜５＞のいずれか一つに記載のポリアミド樹脂組成物。
＜７＞前記アイオノマー樹脂が、エチレン－メタクリル酸共重合体及びエチレン－アクリル酸共重合体の少なくとも一方を含む、＜１＞～＜６＞のいずれか一つに記載のポリアミド樹脂組成物。
＜８＞前記オレフィン系エラストマー及びアイオノマー樹脂が、それぞれ独立に、エチレン－メタクリル酸共重合体及びエチレン－アクリル酸共重合体の少なくとも一方を含む、＜１＞～＜７＞のいずれか一つに記載のポリアミド樹脂組成物。
＜９＞前記ポリアミド樹脂組成物に含まれるポリアミド樹脂の９９質量％以上が脂肪族ポリアミド樹脂である、＜１＞～＜８＞のいずれか一つに記載のポリアミド樹脂組成物。
＜１０＞＜１＞～＜９＞のいずれか一つに記載のポリアミド樹脂組成物を含むフィルム。
＜１１＞延伸フィルムである、＜１０＞に記載のフィルム。 Based on the above problems, as a result of investigations by the present inventor, the problems are solved by the following means <1>, preferably by <2> to <11>.
<1> Polyamide resin, 0.1% by mass to 5% by mass of olefin elastomer, 0.01% by mass to 1% by mass of antioxidant, and 0.01% by mass to 3% by mass of ionomer resin And, the polyamide resin composition containing.
<2> The polyamide resin composition according to <1>, wherein the polyamide resin comprises an aliphatic polyamide resin.
The polyamide resin composition as described in <1> in which the <3> above-mentioned polyamide resin contains the polyamide 6.
<4> The polyamide resin composition according to any one of <1> to <3>, wherein the olefin-based elastomer contains an ethylene-ethyl acrylate copolymer.
<5> The <1> to <3>, wherein the olefin-based elastomer contains an ethylene-ethyl acrylate copolymer, and the acrylic acid content of the ethylene-ethyl acrylate copolymer is 5% by mass to 30% by mass. The polyamide resin composition as described in any one of the above.
<6> The polyamide resin composition according to any one of <1> to <5>, wherein the antioxidant comprises a phenolic antioxidant.
<7> The polyamide resin composition according to any one of <1> to <6>, wherein the ionomer resin comprises at least one of an ethylene-methacrylic acid copolymer and an ethylene-acrylic acid copolymer.
<8> In any one of <1> to <7>, the olefin elastomer and the ionomer resin each independently contain at least one of an ethylene-methacrylic acid copolymer and an ethylene-acrylic acid copolymer The polyamide resin composition as described.
<9> The polyamide resin composition according to any one of <1> to <8>, wherein 99% by mass or more of the polyamide resin contained in the polyamide resin composition is an aliphatic polyamide resin.
The film containing the polyamide resin composition as described in any one of <10><1>-<9>.
The film as described in <10> which is a <11> stretched film.

　本発明によれば、優れた熱的耐久性を有するポリアミドフィルムを提供し得るポリアミド樹脂組成物、及び、フィルムを提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the polyamide resin composition which can provide the polyamide film which has the outstanding thermal durability, and a film can be provided.

　以下に記載する本発明における構成要素の説明は、本発明に係る代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に限定されるものではない。
　本明細書において、「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。また、「（メタ）アクリル」は、「アクリル」及び「メタクリル」の双方、又は、いずれかを表す。 The description of the components in the present invention described below may be made based on the representative embodiments according to the present invention, but the present invention is not limited to such embodiments.
In the present specification, a numerical range represented using “to” means a range including numerical values described before and after “to” as the lower limit value and the upper limit value. Moreover, "(meth) acryl" represents both or any of "acryl" and "methacryl".

　本発明に係るポリアミド樹脂組成物は、ポリアミド樹脂と、０．１質量％～５質量％のオレフィン系エラストマーと、０．０１質量％～１質量％の酸化防止剤と、０．０１質量％～３質量％のアイオノマー樹脂とを含む。このような構成とすることにより、熱水処理後の各種物性に優れたポリアミドフィルムが得られる。 The polyamide resin composition according to the present invention comprises a polyamide resin, 0.1% by mass to 5% by mass of an olefin elastomer, 0.01% by mass to 1% by mass of an antioxidant, and 0.01% by mass to And 3% by mass of ionomer resin. By adopting such a configuration, a polyamide film excellent in various physical properties after the hot water treatment can be obtained.

　〔ポリアミド樹脂〕
　ポリアミド樹脂としては、例えば、脂肪族ポリアミドの単独重合体やこれらを形成する原料単量体を数種用いた共重合体等（すなわち、脂肪族ポリアミド樹脂であって、単独重合体又は共重合体のもの）が挙げられる。脂肪族ポリアミドの単独重合体やこれらを形成する原料単量体を数種用いた共重合体の具体例としては、例えば、ポリカプロアミド（ポリアミド６）、ポリウンデカンアミド（ポリアミド１１）、ポリドデカンアミド（ポリアミド１２）、ポリエチレンアジパミド（ポリアミド２６）、ポリテトラメチレンスクシナミド（ポリアミド４４）、ポリテトラメチレングルタミド（ポリアミド４５）、ポリテトラメチレンアジパミド（ポリアミド４６）、ポリテトラメチレンスベラミド（ポリアミド４８）、ポリテトラメチレンアゼラミド（ポリアミド４９）、ポリテトラメチレンセバカミド（ポリアミド４１０）、ポリテトラメチレンドデカミド（ポリアミド４１２）、ポリペンタメチレンスクシナミド（ポリアミド５４）、ポリペンタメチレングルタミド（ポリアミド５５）、ポリペンタメチレンアジパミド（ポリアミド５６）、ポリペンタメチレンスベラミド（ポリアミド５８）、ポリペンタメチレンアゼラミド（ポリアミド５９）、ポリペンタメチレンセバカミド（ポリアミド５１０）、ポリペンタメチレンドデカミド（ポリアミド５１２）、ポリヘキサメチレンスクシナミド（ポリアミド６４）、ポリヘキサメチレングルタミド（ポリアミド６５）、ポリヘキサメチレンアジパミド（ポリアミド６６）、ポリヘキサメチレンスベラミド（ポリアミド６８）、ポリヘキサメチレンアゼラミド（ポリアミド６９）、ポリヘキサメチレンセバカミド（ポリアミド６１０）、ポリヘキサメチレンドデカミド（ポリアミド６とポリアミド１２との共重合体）、ポリヘキサメチレンテトラデカミド（ポリアミド６１４）、ポリヘキサメチレンヘキサデカミド（ポリアミド６１６）、ポリヘキサメチレンオクタデカミド（ポリアミド６１８）、ポリノナメチレンアジパミド（ポリアミド９６）、ポリノナメチレンスベラミド（ポリアミド９８）、ポリノナメチレンアゼラミド（ポリアミド９９）、ポリノナメチレンセバカミド（ポリアミド９１０）、ポリノナメチレンドデカミド（ポリアミド９１２）、ポリデカメチレンアジパミド（ポリアミド１０６）、ポリデカメチレンスベラミド（ポリアミド１０８）、ポリデカメチレンアゼラミド（ポリアミド１０９）、ポリデカメチレンセバカミド（ポリアミド１０１０）、ポリデカメチレンドデカミド（ポリアミド１０１２）、ポリドデカメチレンアジパミド（ポリアミド１２６）、ポリドデカメチレンスベラミド（ポリアミド１２８）、ポリドデカメチレンアゼラミド（ポリアミド１２９）、ポリドデカメチレンセバカミド（ポリアミド１２１０）、ポリドデカメチレンドデカミド（ポリアミド１２１２）等が挙げられる。 [Polyamide resin]
As the polyamide resin, for example, homopolymers of aliphatic polyamides and copolymers using several kinds of raw material monomers forming these (i.e., aliphatic polyamide resins, homopolymers or copolymers Of the Specific examples of homopolymers of aliphatic polyamides and copolymers using several kinds of raw material monomers forming these include, for example, polycaproamide (polyamide 6), porundecane amide (polyamide 11), polydodecane Amide (polyamide 12), polyethylene adipamide (polyamide 26), polytetramethylene succinamide (polyamide 44), polytetramethylene glutamide (polyamide 45), polytetramethylene adipamide (polyamide 46), polytetramethylene Suberamide (polyamide 48), polytetramethylene azelamide (polyamide 49), polytetramethylene sebacamide (polyamide 410), polytetramethylene dodecamide (polyamide 412), polypentamethylene succinamide (polyamide 54), poly Pentamethylene Rutamide (polyamide 55), polypentamethylene adipamide (polyamide 56), polypentamethylene suberamide (polyamide 58), polypentamethylene aceramide (polyamide 59), polypentamethylene sebacamide (polyamide 510), polypenta Methylene dodecamide (polyamide 512), polyhexamethylene succinamide (polyamide 64), polyhexamethylene glutamide (polyamide 65), polyhexamethylene adipamide (polyamide 66), polyhexamethylene suberamide (polyamide 68), Polyhexamethylene azelamide (polyamide 69), polyhexamethylene sebacamide (polyamide 610), polyhexamethylene dodecamide (copolymer of polyamide 6 and polyamide 12), polyhexamethylene tetrade (Polyamide 614), polyhexamethylene hexadecamide (polyamide 616), polyhexamethylene octadecamide (polyamide 618), polynonamethylene adipamide (polyamide 96), polynona methylene suberamide (polyamide 98), poly Nonamethylene aceramide (polyamide 99), polynonamethylene sebacamide (polyamide 910), polynonamethylene dodecamide (polyamide 912), polydecamethylene adipamide (polyamide 106), polydecamethylene suberamide (polyamide 108) , Polydecamethylene aceramide (polyamide 109), polydecamethylene sebacamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012), polydodecamethylene adipamide (polyamide 126), poly Examples thereof include dodecamethylenesuberamide (polyamide 128), polydodecamethylene aceramide (polyamide 129), polydodecamethylene sebacamide (polyamide 1210), and polydodecamethylene dodecamide (polyamide 1212).

　また、ポリアミド樹脂として、例えば、ポリメタキシリレンアジパミド（ポリアミドＭＸＤ６）、ポリメタキシリレンスベラミド（ポリアミドＭＸＤ８）、ポリメタキシリレンアゼラミド（ポリアミドＭＸＤ９）、ポリメタキシリレンセバカミド（ポリアミドＭＸＤ１０）、ポリメタキシリレンドデカミド（ポリアミドＭＸＤ１２）、ポリメタキシリレンテレフタラミド（ポリアミドＭＸＤＴ）、ポリメタキシリレンイソフタラミド（ポリアミドＭＸＤＩ）、ポリメタキシリレンヘキサヒドロテレフタラミド（ポリアミドＭＸＤＴ（Ｈ））、ポリメタキシリレンナフタラミド（ポリアミドＭＸＤＮ）、ポリパラキシリレンアジパミド（ポリアミドＰＸＤ６）、ポリパラキシリレンスベラミド（ポリアミドＰＸＤ８）、ポリパラキシリレンアゼラミド（ポリアミドＰＸＤ９）、ポリパラキシリレンセバカミド（ポリアミドＰＸＤ１０）、ポリパラキシリレンドデカミド（ポリアミドＰＸＤ１２）、ポリパラキシリレンテレフタラミド（ポリアミドＰＸＤＴ）、ポリパラキシリレンイソフタラミド（ポリアミドＰＸＤＩ）、ポリパラキシリレンヘキサヒドロテレフタラミド（ポリアミドＰＸＤＴ（Ｈ））、ポリパラキシリレンナフタラミド（ポリアミドＰＸＤＮ）、ポリパラフェニレンテレフタラミド（ＰＰＴＡ）、ポリパラフェニレンイソフタラミド（ＰＰＩＡ）、ポリメタフェニレンテレフタラミド（ＰＭＴＡ）、ポリメタフェニレンイソフタラミド（ＰＭＩＡ）、ポリ（２，６－ナフタレンジメチレンアジパミド）（ポリアミド２，６－ＢＡＮ６）、ポリ（２，６－ナフタレンジメチレンスベラミド）（ポリアミド２，６－ＢＡＮ８）、ポリ（２，６－ナフタレンジメチレンアゼラミド）（ポリアミド２，６－ＢＡＮ９）、ポリ（２，６－ナフタレンジメチレンセバカミド）（ポリアミド２，６－ＢＡＮ１０）、ポリ（２，６－ナフタレンジメチレンドデカミド）（ポリアミド２，６－ＢＡＮ１２）、ポリ（２，６－ナフタレンジメチレンテレフタラミド）（ポリアミド２，６－ＢＡＮＴ）、ポリ（２，６－ナフタレンジメチレンイソフタラミド）（ポリアミド２，６－ＢＡＮＩ）、ポリ（２，６－ナフタレンジメチレンヘキサヒドロテレフタラミド）（ポリアミド２，６－ＢＡＮＴ（Ｈ））、ポリ（２，６－ナフタレンジメチレンナフタラミド）（ポリアミド２，６－ＢＡＮＮ）、ポリ（１，３－シクロヘキサンジメチレンアジパミド）（ポリアミド１，３－ＢＡＣ６）、ポリ（１，３－シクロヘキサンジメチレンスベラミド（ポリアミド１，３－ＢＡＣ８）、ポリ（１，３－シクロヘキサンジメチレンアゼラミド）（ポリアミド１，３－ＢＡＣ９）、ポリ（１，３－シクロヘキサンジメチレンセバカミド）（ポリアミド１，３－ＢＡＣ１０）、ポリ（１，３－シクロヘキサンジメチレンドデカミド）（ポリアミド１，３－ＢＡＣ１２）、ポリ（１，３－シクロヘキサンジメチレンテレフタラミド）（ポリアミド１，３－ＢＡＣＴ）、ポリ（１，３－シクロヘキサンジメチレンイソフタラミド）（ポリアミド１，３－ＢＡＣＩ）、ポリ（１，３－シクロヘキサンジメチレンヘキサヒドロテレフタラミド）（ポリアミド１，３－ＢＡＣＴ（Ｈ））、ポリ（１，３－シクロヘキサンジメチレンナフタラミド）（ポリアミド１，３－ＢＡＣＮ）、ポリ（１，４－シクロヘキサンジメチレンアジパミド）（ポリアミド１，４－ＢＡＣ６）、ポリ（１，４－シクロヘキサンジメチレンスベラミド）（ポリアミド１，４－ＢＡＣ８）、ポリ（１，４－シクロヘキサンジメチレンアゼラミド）（ポリアミド１，４－ＢＡＣ９）、ポリ（１，４－シクロヘキサンジメチレンセバカミド）（ポリアミド１，４－ＢＡＣ１０）、ポリ（１，４－シクロヘキサンジメチレンドデカミド）（ポリアミド１，４－ＢＡＣ１２）、ポリ（１，４－シクロヘキサンジメチレンテレフタラミド）（ポリアミド１，４－ＢＡＣＴ）、ポリ（１，４－シクロヘキサンジメチレンイソフタラミド）（ポリアミド１，４－ＢＡＣＩ）、ポリ（１，４－シクロヘキサンジメチレンヘキサヒドロテレフタラミド）（ポリアミド１，４－ＢＡＣＴ（Ｈ））、ポリ（１，４－シクロヘキサンジメチレンナフタラミド）（ポリアミド１，４－ＢＡＣＮ）、ポリ（４，４’－メチレンビスシクロヘキシレンアジパミド）（ポリアミドＰＡＣＭ６）、ポリ（４，４’－メチレンビスシクロヘキシレンスベラミド）（ポリアミドＰＡＣＭ８）、ポリ（４，４’－メチレンビスシクロヘキシレンアゼラミド）（ポリアミドＰＡＣＭ９）、ポリ（４，４’－メチレンビスシクロヘキシレンセバカミド）（ポリアミドＰＡＣＭ１０）、ポリ（４，４’－メチレンビスシクロヘキシレンドデカミド）（ポリアミドＰＡＣＭ１２）、ポリ（４，４’－メチレンビスシクロヘキシレンテトラデカミド）（ポリアミドＰＡＣＭ１４）、ポリ（４，４’－メチレンビスシクロヘキシレンヘキサデカミド）（ポリアミドＰＡＣＭ１６）、ポリ（４，４’－メチレンビスシクロヘキシレンオクタデカミド）（ポリアミドＰＡＣＭ１８）、ポリ（４，４’－メチレンビスシクロヘキシレンテレフタラミド）（ポリアミドＰＡＣＭＴ）、ポリ（４，４’－メチレンビスシクロヘキシレンイソフタラミド）（ポリアミドＰＡＣＭＩ）、ポリ（４，４’－メチレンビスシクロヘキシレンヘキサヒドロテレフタラミド）（ポリアミドＰＡＣＭＴ（Ｈ））、ポリ（４，４’－メチレンビスシクロヘキシレンナフタラミド）（ポリアミドＰＡＣＭＮ）、ポリ（４，４’－メチレンビス（２－メチル－シクロヘキシレン）アジパミド）（ポリアミドＭＡＣＭ６）、ポリ（４，４’－メチレンビス（２－メチル－シクロヘキシレン）スベラミド）（ポリアミドＭＡＣＭ８）、ポリ（４，４’－メチレンビス（２－メチル－シクロヘキシレン）アゼラミド）（ポリアミドＭＡＣＭ９）、ポリ（４，４’－メチレンビス（２－メチル－シクロヘキシレン）セバカミド）（ポリアミドＭＡＣＭ１０）、ポリ（４，４’－メチレンビス（２－メチル－シクロヘキシレン）ドデカミド）（ポリアミドＭＡＣＭ１２）、ポリ（４，４’－メチレンビス（２－メチル－シクロヘキシレン）テトラデカミド）（ポリアミドＭＡＣＭ１４）、ポリ（４，４’－メチレンビス（２－メチル－シクロヘキシレン）ヘキサデカミド）（ポリアミドＭＡＣＭ１６）、ポリ（４，４’－メチレンビス（２－メチル－シクロヘキシレン）オクタデカミド）（ポリアミドＭＡＣＭ１８）、ポリ（４，４’－メチレンビス（２－メチル－シクロヘキシレン）テレフタラミド）（ポリアミドＭＡＣＭＴ）、ポリ（４，４’－メチレンビス（２－メチル－シクロヘキシレン）イソフタラミド）（ポリアミドＭＡＣＭＩ）、ポリ（４，４’－メチレンビス（２－メチル－シクロヘキシレン）ヘキサヒドロテレフタラミド）（ポリアミドＭＡＣＭＴ（Ｈ））、ポリ（４，４’－メチレンビス（２－メチル－シクロヘキシレン）ナフタラミド）（ポリアミドＭＡＣＭＮ）、ポリ（４，４’－プロピレンビスシクロヘキシレンアジパミド）（ポリアミドＰＡＣＰ６）、ポリ（４，４’－プロピレンビスシクロヘキシレンスベラミド）（ポリアミドＰＡＣＰ８）、ポリ（４，４’－プロピレンビスシクロヘキシレンアゼラミド）（ポリアミドＰＡＣＰ９）、ポリ（４，４’－プロピレンビスシクロヘキシレンセバカミド）（ポリアミドＰＡＣＰ１０）、ポリ（４，４’－プロピレンビスシクロヘキシレンドデカミド）（ポリアミドＰＡＣＰ１２）、ポリ（４，４’－プロピレンビスシクロヘキシレンテトラデカミド）（ポリアミドＰＡＣＰ１４）、ポリ（４，４’－プロピレンビスシクロヘキシレンヘキサデカミド）（ポリアミドＰＡＣＰ１６）、ポリ（４，４’－プロピレンビスシクロヘキシレンオクタデカミド）（ポリアミドＰＡＣＰ１８）、ポリ（４，４’－プロピレンビスシクロヘキシレンテレフタラミド）（ポリアミドＰＡＣＰＴ）、ポリ（４，４’－プロピレンビスシクロヘキシレンイソフタラミド）（ポリアミドＰＡＣＰＩ）、ポリ（４，４’－プロピレンビスシクロヘキシレンヘキサヒドロテレフタラミド）（ポリアミドＰＡＣＰＴ（Ｈ））、ポリ（４，４’－プロピレンビスシクロヘキシレンナフタラミド）（ポリアミドＰＡＣＰＮ）、ポリイソホロンアジパミド（ポリアミドＩＰＤ６）、ポリイソホロンスベラミド（ポリアミドＩＰＤ８）、ポリイソホロンアゼラミド（ポリアミドＩＰＤ９）、ポリイソホロンセバカミド（ポリアミドＩＰＤ１０）、ポリイソホロンドデカミド（ポリアミドＩＰＤ１２）、ポリイソホロンテレフタラミド（ポリアミドＩＰＤＴ）、ポリイソホロンイソフタラミド（ポリアミドＩＰＤＩ）、ポリイソホロンヘキサヒドロテレフタラミド（ポリアミドＩＰＤＴ（Ｈ））、ポリイソホロンナフタラミド（ポリアミドＩＰＤＮ）、ポリテトラメチレンテレフタラミド（ポリアミド４Ｔ）、ポリテトラメチレンイソフタラミド（ポリアミド４Ｉ）、ポリテトラメチレンヘキサヒドロテレフタラミド（ポリアミド４Ｔ（Ｈ））、ポリテトラメチレンナフタラミド（ポリアミド４Ｎ）、ポリペンタメチレンテレフタラミド（ポリアミド５Ｔ）、ポリペンタメチレンイソフタラミド（ポリアミド５Ｉ）、ポリペンタメチレンヘキサヒドロテレフタラミド（ポリアミド５Ｔ（Ｈ））、ポリペンタメチレンナフタラミド（ポリアミド５Ｎ）、ポリヘキサメチレンテレフタラミド（ポリアミド６Ｔ）、ポリヘキサメチレンイソフタラミド（ポリアミド６Ｉ）、ポリヘキサメチレンヘキサヒドロテレフタラミド（ポリアミド６Ｔ（Ｈ））、ポリヘキサメチレンナフタラミド（ポリアミド６Ｎ）、ポリ（２－メチルペンタメチレンテレフタラミド）（ポリアミドＭ５Ｔ）、ポリ（２－メチルペンタメチレンイソフタラミド）（ポリアミドＭ５Ｉ）、ポリ（２－メチルペンタメチレンヘキサヒドロテレフタラミド）（ポリアミドＭ５Ｔ（Ｈ））、ポリ（２－メチルペンタメチレンナフタラミド（ポリアミドＭ５Ｎ）、ポリノナメチレンテレフタラミド（ポリアミド９Ｔ）、ポリノナメチレンイソフタラミド（ポリアミド９Ｉ）、ポリノナメチレンヘキサヒドロテレフタラミド（ポリアミド９Ｔ（Ｈ））、ポリノナメチレンナフタラミド（ポリアミド９Ｎ）、ポリ（２－メチルオクタメチレンテレフタラミド）（ポリアミドＭ８Ｔ）、ポリ（２－メチルオクタメチレンイソフタラミド）（ポリアミドＭ８Ｉ）、ポリ（２－メチルオクタメチレンヘキサヒドロテレフタラミド）（ポリアミドＭ８Ｔ（Ｈ））、ポリ（２－メチルオクタメチレンナフタラミド）（ポリアミドＭ８Ｎ）、ポリトリメチルヘキサメチレンテレフタラミド（ポリアミドＴＭＨＴ）、ポリトリメチルヘキサメチレンイソフタラミド（ポリアミドＴＭＨＩ）、ポリトリメチルヘキサメチレンヘキサヒドロテレフタラミド（ポリアミドＴＭＨＴ（Ｈ））、ポリトリメチルヘキサメチレンナフタラミド（ポリアミドＴＭＨＮ）、ポリデカメチレンテレフタラミド（ポリアミド１０Ｔ）、ポリデカメチレンイソフタラミド（ポリアミド１０Ｉ）、ポリデカメチレンヘキサヒドロテレフタラミド（ポリアミド１０Ｔ（Ｈ））、ポリデカメチレンナフタラミド（ポリアミド１０Ｎ）、ポリウンデカメチレンテレフタラミド（ポリアミド１１Ｔ）、ポリウンデカメチレンイソフタラミド（ポリアミド１１Ｉ）、ポリウンデカメチレンヘキサヒドロテレフタラミド（ポリアミド１１Ｔ（Ｈ））、ポリウンデカメチレンナフタラミド（ポリアミド１１Ｎ）、ポリドデカメチレンテレフタラミド（ポリアミド１２Ｔ）、ポリドデカメチレンイソフタラミド（ポリアミド１２Ｉ）、ポリドデカメチレンヘキサヒドロテレフタラミド（ポリアミド１２Ｔ（Ｈ））、ポリドデカメチレンナフタラミド（ポリアミド１２Ｎ）やこれらポリアミド樹脂の原料単量体を数種用いた共重合体等も好ましく用いられる。 In addition, as a polyamide resin, for example, polymethaxylylene adipamide (polyamide MXD6), polymethaxylylene beramide (polyamide MXD8), polymethaxylylene aceramide (polyamide MXD9), polymethaxylylene sebacamide (polyamide MXD10) Polymethaxylylene dodecamide (polyamide MXD12), polymethaxylylene terephthalamide (polyamide MXDT), polymethaxylylene isophtalamide (polyamide MXDI), polymethaxylylene hexahydroterephthalamide (polyamide MXDT (H)), polymers Taxylylene naphthalamide (polyamide MXDN), polyparaxylylene adipamide (polyamide PXD6), polyparaxylylenes beramide (polyamide PXD8), polyparaxylylene Ramid (polyamide PXD9), polyparaxylylene sebacamide (polyamide PXD10), polyparaxylylene decamide (polyamide PXD12), polyparaxylylene terephthalamide (polyamide PXDT), polyparaxylylene isophtalamide (polyamide PXDI), polyparaxylylene hexahydroterephthalamide (polyamide PXDT (H)), polyparaxylylene naphthalamide (polyamide PXDN), polyparaphenylene terephthalamide (PPTA), polyparaphenylene isophthalamide (PPIA) , Polymetaphenylene terephthalamide (PMTA), polymetaphenylene isophthalamide (PMIA), poly (2, 6-naphthalene dimethylene adipamide) (polyamide 2, 6-BAN 6), poly (2, 6-naphthalene Methylene suberamide) (polyamide 2, 6-BAN 8), poly (2, 6- naphthalene dimethylene aceramide) (polyamide 2, 6- BAN 9), poly (2, 6- naphthalene dimethylene sebacamide) (polyamide 2 , 6-BAN 10), poly (2, 6-naphthalene dimethylene dodecamide) (polyamide 2, 6-BAN 12), poly (2, 6- naphthalene dimethylene terephthalamide) (polyamide 2, 6- BANT), poly (2,6-Naphthalene dimethylene isophthalamide) (polyamide 2,6-BANI), poly (2,6-naphthalene dimethylene hexahydroterephthalamide) (polyamide 2,6-BANT (H)), poly ( 2,6-Naphthalene dimethylene naphthalamide) (polyamide 2,6-BANN), poly (1,3-cyclohexanedimer Tyrene adipamide) (polyamide 1,3-BAC6), poly (1,3-cyclohexanedimethylene suberamide (polyamide 1,3-BAC8), poly (1,3-cyclohexanedimethylene aceramide) (polyamide 1,3-BAC9) ), Poly (1,3-cyclohexanedimethylene sebacamide) (polyamide 1,3-BAC10), poly (1,3-cyclohexanedimethylene dodecamide) (polyamide 1,3-BAC12), poly (1,3) -Cyclohexanedimethylene terephthalamide) (polyamide 1,3-BACT), poly (1,3-cyclohexanedimethyleneisophthalamide) (polyamide 1,3-BACI), poly (1,3-cyclohexanedimethylene hexahydro) Terephthalamide) (polyamide 1,3-BACT (H)), poly (1, 1 -Cyclohexanedimethylene naphthalamide) (polyamide 1,3-BACN), poly (1,4-cyclohexanedimethylene adipamide) (polyamide 1,4-BAC6), poly (1,4-cyclohexanedimethylene suberamide) (Polyamide 1,4-BAC8), poly (1,4-cyclohexanedimethylene aceramide) (polyamide 1,4-BAC9), poly (1,4-cyclohexanedimethylene sebacamide) (polyamide 1,4-BAC10) ), Poly (1,4-cyclohexanedimethylene dodecamide) (polyamide 1,4-BAC12), poly (1,4-cyclohexanedimethylene terephthalamide) (polyamide 1,4-BACT), poly (1,4 -Cyclohexane dimethylene isophthalamide) (polyamide 1,4-BACI), poly ( , 4-Cyclohexanedimethylenehexahydroterephthalamide) (polyamide 1,4-BACT (H)), poly (1,4-cyclohexanedimethylene naphthalamide) (polyamide 1,4-BACN), poly (4,4 '-Methylenebiscyclohexylene adipamide) (polyamide PACM 6), poly (4,4'-methylene biscyclohexylene suberamide) (polyamide PACM 8), poly (4,4'-methylene biscyclohexylene aceramide) (polyamide) PACM 9), poly (4,4'-methylenebiscyclohexylene cebacamide) (polyamide PACM 10), poly (4,4'-methylene biscyclohexylene decamide) (polyamide PACM 12), poly (4,4'-methylene) Biscyclohexylene tetradecamide (polyamide) PACM 14), poly (4,4'-methylenebiscyclohexylene hexadecamide) (polyamide PACM 16), poly (4,4'-methylene biscyclohexylene octadecamide) (polyamide PACM 18), poly (4,4'-) Methylenebiscyclohexylene terephthalamide) (polyamide PACMT), poly (4,4'-methylenebiscyclohexylene isophtalamide) (polyamide PACMI), poly (4,4'-methylenebiscyclohexylene hexahydroterephthalamide) (Polyamide PACMT (H)), poly (4,4'-methylene biscyclohexylene naphthalamide) (polyamide PACMN), poly (4,4'-methylene bis (2-methyl-cyclohexylene) adipamide) (polyamide MACM 6), Poly (4,4'- Tylenebis (2-methyl-cyclohexylene) suberamide) (polyamide MACM 8), poly (4,4'-methylenebis (2-methyl-cyclohexylene) aceramide) (polyamide MACM 9), poly (4,4'-methylenebis (2-) Methyl-cyclohexylene) sebacamide) (polyamide MACM 10), poly (4,4'-methylenebis (2-methyl-cyclohexylene) dodecamide) (polyamide MACM 12), poly (4,4'-methylenebis (2-methyl-cyclohexylene) ) Tetradecamide) (polyamide MACM 14), poly (4,4'-methylenebis (2-methyl-cyclohexylene) hexadecamide) (polyamide MACM 16), poly (4,4'-methylenebis (2-methyl-cyclohexylene) octadecamide) (polyamide MACM 16) Liamido MACM 18), poly (4,4'-methylenebis (2-methyl-cyclohexylene) terephthalamide) (polyamide MACMT), poly (4,4'-methylenebis (2-methyl-cyclohexylene) isophthalamide) (polyamide MACMI), Poly (4,4'-methylenebis (2-methyl-cyclohexylene) hexahydroterephthalamide) (polyamide MACMT (H)), poly (4,4'-methylenebis (2-methyl-cyclohexylene) naphthalamide) (polyamide) MACMN), poly (4,4'-propylenebiscyclohexylene adipamide) (polyamide PACP6), poly (4,4'-propylene biscyclohexylene suberamide) (polyamide PACP8), poly (4,4'-propylene) Biscyclohexylene Polyamide PACP9), poly (4,4'-propylenebiscyclohexylene cebacamide) (polyamide PACP10), poly (4,4'-propylenebiscyclohexylene decamide) (polyamide PACP12), poly (4, 4'-Propylene biscyclohexylene tetradecamide) (polyamide PACP14), poly (4,4'-propylene biscyclohexylene hexadecamide) (polyamide PACP16), poly (4,4'-propylene biscyclohexylene octadecamide) ) (Polyamide PACP 18), poly (4,4′-propylenebiscyclohexylene terephthalamide) (polyamide PACPT), poly (4,4′-propylenebiscyclohexylene isophtalamide) (polyamide PACPI), poly (4,4, 4 ' Propylene biscyclohexylene hexahydroterephthalamide) (polyamide PACPT (H)), poly (4,4'-propylenebiscyclohexylene naphthalamide) (polyamide PACPN), polyisophorone adipamide (polyamide IPD6), polyisophorone bee Ramide (polyamide IPD 8), polyisophorone azelamide (polyamide IPD 9), polyisophorone sebacamide (polyamide IPD 10), polyisophoron de decamide (polyamide IPD 12), polyisophorone terephthalamide (polyamide IPDT), polyisophorone isophtalamide (polyamide IPD 8) Polyamide IPDI), polyisophorone hexahydroterephthalamide (polyamide IPDT (H)), polyisophorone naphthalamide (polyamide IPDN), polytetramethylene tere Phthalamide (polyamide 4T), polytetramethylene isophthalamide (polyamide 4I), polytetramethylene hexahydroterephthalamide (polyamide 4T (H)), polytetramethylene naphthalamide (polyamide 4N), polypentamethylene terepheramide (polyamide 4N) Polyamide 5T), polypentamethylene isophthalamide (polyamide 5I), polypentamethylene hexahydroterephthalamide (polyamide 5T (H)), polypentamethylene naphthalamide (polyamide 5N), polyhexamethylene terephthalamide (polyamide 6T) ), Polyhexamethylene isophthalamide (polyamide 6I), polyhexamethylene hexahydroterephthalamide (polyamide 6T (H)), polyhexamethylene naphthalamide (polyamide 6N), poly (2-methyl) Pentamethylene terephthalamide) (polyamide M5T), poly (2-methylpentamethylene isophthalamide) (polyamide M5I), poly (2-methylpentamethylene hexahydroterephthalamide) (polyamide M5T (H)), poly ( 2-Methylpentamethylene naphthalamide (polyamide M5N), polynonamethylene terephthalamide (polyamide 9T), polynonamethylene isophthalamide (polyamide 9I), polynonamethylene hexahydroterephthalamide (polyamide 9T (H)), Polynonamethylene naphthalamide (polyamide 9N), poly (2-methyloctamethylene terephthalamide) (polyamide M8T), poly (2-methyloctamethylene isophtalamide) (polyamide M8I), poly (2-methyloctamethylene hexaamide) Hydrote Phthalamide) (polyamide M 8 T (H)), poly (2-methyl octamethylene naphthalamide) (polyamide M 8 N), polytrimethylhexamethylene terephthalamide (polyamide TMHT), polytrimethylhexamethylene isophthalamide (polyamide TMHI), poly Trimethylhexamethylenehexahydroterephthalamide (polyamide TMHT (H)), polytrimethylhexamethylene naphthalamide (polyamide TMHN), polydecamethylene terephthalamide (polyamide 10T), polydecamethylene isophthalamide (polyamide 10I), poly Decamethylene hexahydroterephthalamide (polyamide 10T (H)), polydecamethylene naphthalamide (polyamide 10N), polyundecamethylene terephthalamide (polyamide 11T) Polyundecamethylene isophthalamide (polyamide 11I), polyundecamethylene hexahydroterephthalamide (polyamide 11T (H)), polyundecamethylene naphthalamide (polyamide 11N), polydodecamethylene terephthalamide (polyamide 12T) For polydodecamethylene isophthalamide (polyamide 12I), polydodecamethylene hexahydroterephthalamide (polyamide 12T (H)), polydodecamethylene naphthalamide (polyamide 12N), and the raw material monomers of these polyamide resins Copolymers and the like are preferably used.

　上述したポリアミド樹脂の具体例のなかでも、ポリカプロアミド（ポリアミド６）、ポリメタキシリレンアジパミド（ポリアミドＭＸＤ６）、ポリウンデカンアミド（ポリアミド１１）、ポリドデカンアミド（ポリアミド１２）、ポリヘキサメチレンアジパミド（ポリアミド６６）、ポリヘキサメチレンデカミド（ポリアミド６１０）、ポリヘキサメチレンドデカミド（ポリアミド６とポリアミド１２との共重合体）、ポリデカメチレンデカミド（ポリアミド１０１０）、ポリデカメチレンドデカミド（ポリアミド１０１２）、及びポリドデカメチレンドデカミド（ポリアミド１２１２）からなる群より選ばれる少なくとも１種の単独重合体、及び／又はこれらを形成する原料単量体を数種用いた共重合体を用いることがより好ましく、ポリカプロアミド（ポリアミド６）、ポリウンデカンアミド（ポリアミド１１）、ポリドデカンアミド（ポリアミド１２）、ポリヘキサメチレンアジパミド（ポリアミド６６）からなる群より選ばれる少なくとも１種の単独重合体、及び／又はこれらを形成する原料単量体を数種用いた共重合体を用いることがさらに好ましく、ポリカプロアミド（ポリアミド６）が特に好ましい。
　本発明に係るポリアミド樹脂組成物に含まれるポリアミド樹脂は、その９０質量％以上が脂肪族ポリアミド樹脂（例えば、ポリアミド６）であることが好ましく、９５質量％以上が脂肪族ポリアミド樹脂（例えば、ポリアミド６）であることがより好ましく、９９質量％以上が脂肪族ポリアミド樹脂（例えば、ポリアミド６）であることがさらに好ましく、実質的に１００質量％が脂肪族ポリアミド樹脂（例えば、ポリアミド６）であることが一層好ましい。実質的に１００質量％とは、不純物等意図せず配合するものを除き、すべてのポリアミド樹脂が脂肪族ポリアミド樹脂（例えば、ポリアミド６）であることをいう。 Among the specific examples of the polyamide resin described above, polycaproamide (polyamide 6), polymetaxylylene adipamide (polyamide MXD 6), polyundecane amide (polyamide 11), polydodecane amide (polyamide 12), polyhexamethylene adipate Pamide (polyamide 66), polyhexamethylene decamide (polyamide 610), polyhexamethylene dodecamide (copolymer of polyamide 6 and polyamide 12), polydecamethylene decamide (polyamide 1010), polydecamethylene dodecamide (Polyamide 1012) and at least one homopolymer selected from the group consisting of polydodecamethylene dodecamide (polyamide 1212), and / or a copolymer using several kinds of raw material monomers forming these Is more preferably poly At least one homopolymer selected from the group consisting of proamide (polyamide 6), porundecane amide (polyamide 11), polydodecane amide (polyamide 12), polyhexamethylene adipamide (polyamide 66), and / or these It is more preferable to use a copolymer in which several kinds of raw material monomers for forming are used, and polycaproamide (polyamide 6) is particularly preferable.
90% by mass or more of the polyamide resin contained in the polyamide resin composition according to the present invention is preferably an aliphatic polyamide resin (for example, polyamide 6), and 95% by mass or more is an aliphatic polyamide resin (for example, polyamide) 6) is more preferably, 99% by mass or more is an aliphatic polyamide resin (for example, polyamide 6), and substantially 100% by mass is an aliphatic polyamide resin (for example, polyamide 6) Is more preferred. The term "substantially 100% by mass" means that all polyamide resins are aliphatic polyamide resins (e.g., polyamide 6) except for those which are unintentionally mixed with impurities and the like.

　本発明に係るポリアミド樹脂組成物における、ポリアミド樹脂の合計量は、組成物の８０質量％以上が好ましく、８５質量％以上がより好ましく、９０質量％以上がさらに好ましく、９２質量％以上が一層好ましい。前記ポリアミド樹脂の合計量は、９９．８８質量％以下が好ましく、９９質量％以下であってもよい。
　ポリアミド樹脂として、上記ポリアミド樹脂の１種のみを単独で用いてもよいし、複数種類のポリアミド樹脂を混合して用いてもよい。複数種類を配合する場合、合計量が上記範囲となることが好ましい。 The total amount of polyamide resin in the polyamide resin composition according to the present invention is preferably 80% by mass or more, more preferably 85% by mass or more, still more preferably 90% by mass or more, and further preferably 92% by mass or more of the composition. . 99.88 mass% or less is preferable, and the total amount of the said polyamide resin may be 99 mass% or less.
As a polyamide resin, only 1 type of the said polyamide resin may be used independently, and multiple types of polyamide resin may be mixed and used. When mix | blending multiple types, it is preferable that a total amount becomes said range.

　〔オレフィン系エラストマー〕
　オレフィン系エラストマーは、エチレン及びプロピレンから選ばれる少なくとも１種と、α，β－不飽和カルボン酸単量体及びα，β－不飽和カルボン酸エステル単量体から選ばれる少なくとも１種とを共重合した重合体である。 [Olefin-based elastomer]
The olefin elastomer is copolymerized with at least one selected from ethylene and propylene and at least one selected from an α, β-unsaturated carboxylic acid monomer and an α, β-unsaturated carboxylic acid ester monomer Polymer.

　α，β－不飽和カルボン酸単量体としては、アクリル酸及びメタクリル酸などが挙げられる。 Examples of the α, β-unsaturated carboxylic acid monomer include acrylic acid and methacrylic acid.

　α，β－不飽和カルボン酸エステル単量体としては、これら不飽和カルボン酸のメチルエステル、エチルエステル、プロピルエステル、ブチルエステル、ペンチルエステル、ヘキシルエステル、ヘプチルエステル、オクチルエステル、ノニルエステル、デシルエステル又はこれらの混合物などが挙げられる。 As α, β-unsaturated carboxylic acid ester monomers, methyl ester, ethyl ester, propyl ester, butyl ester, pentyl ester, hexyl ester, heptyl ester, octyl ester, nonyl ester, decyl ester of these unsaturated carboxylic acids Or a mixture of these.

　オレフィン系エラストマーとしては、エチレン・α，β－不飽和カルボン酸系共重合体、プロピレン・α，β－不飽和カルボン酸系共重合体、エチレン・プロピレン・α，β－不飽和カルボン酸系共重合体、エチレン・α，β－不飽和カルボン酸エステル系共重合体、プロピレン・α，β－不飽和カルボン酸エステル系共重合体、エチレン・プロピレン・α，β－不飽和カルボン酸エステル系共重合体、エチレン・α，β－不飽和カルボン酸／不飽和カルボン酸エステル系共重合体、プロピレン・α，β－不飽和カルボン酸／不飽和カルボン酸エステル系共重合体、エチレン・プロピレン・α，β－不飽和カルボン酸／不飽和カルボン酸エステル系共重合体を挙げることができる。オレフィン系エラストマーとして、上記オレフィン系エラストマーの１種のみを単独で用いてもよいし、複数種類のオレフィン系エラストマーを混合して用いてもよい。 As olefin elastomers, ethylene / α, β-unsaturated carboxylic acid copolymer, propylene / α, β-unsaturated carboxylic acid copolymer, ethylene / propylene / α, β-unsaturated carboxylic acid co-polymer Polymer, ethylene · α, β-unsaturated carboxylic acid ester copolymer, propylene · α, β-unsaturated carboxylic acid ester copolymer, ethylene · propylene · α, β-unsaturated carboxylic acid ester copolymer Polymer, ethylene / α, β-unsaturated carboxylic acid / unsaturated carboxylic acid ester copolymer, propylene / α, β-unsaturated carboxylic acid / unsaturated carboxylic acid ester copolymer, ethylene / propylene / α Examples thereof include β-unsaturated carboxylic acid / unsaturated carboxylic acid ester type copolymers. As the olefin-based elastomer, only one of the above-mentioned olefin-based elastomers may be used alone, or plural types of olefin-based elastomers may be mixed and used.

　これらの中でも、エチレンと（メタ）アクリル酸エステル単量体とを共重合したエチレン－（メタ）アクリル酸エステル共重合体が好ましく、具体的には、エチレン－エチルアクリレート共重合体、エチレン－メチルアクリレート共重合体、エチレン－エチルメタクリレート共重合体等がより好ましい。なかでも、成形時の熱的安定性と少量添加での効果の観点からエチレン－エチルアクリレート共重合体がオレフィン系エラストマーとして好ましく用いられる。 Among these, ethylene- (meth) acrylic acid ester copolymer obtained by copolymerizing ethylene and (meth) acrylic acid ester monomer is preferable, and specifically, ethylene-ethyl acrylate copolymer, ethylene-methyl Acrylate copolymer, ethylene-ethyl methacrylate copolymer and the like are more preferable. Among them, an ethylene-ethyl acrylate copolymer is preferably used as an olefin elastomer from the viewpoint of the thermal stability at the time of molding and the effect of adding a small amount.

　本発明では特に、エチレン－（メタ）アクリル酸エステル共重合体における（メタ）アクリル酸エステルの含有量が５～３０質量％であることが好ましい。このような範囲とすることにより、フィルムの耐ピンホール性をより向上させることができる。 In the present invention, in particular, the content of (meth) acrylic acid ester in the ethylene- (meth) acrylic acid ester copolymer is preferably 5 to 30% by mass. By setting it as such a range, the pinhole resistance of a film can be improved more.

　本発明に係るポリアミド樹脂組成物において、オレフィン系エラストマーの含有量は、ポリアミド樹脂組成物の０．１質量％～５質量％である。オレフィン系エラストマーの含有量を０．１質量％以上とすることにより、ポリアミド樹脂組成物を用いた樹脂フィルムの耐ピンホール性を改善することができる。同様の観点から、オレフィン系エラストマーの含有量は、０．５質量％以上であることが好ましく、０．８質量％以上であることがより好ましく、１質量％以上であることがさらに好ましい。また、オレフィン系エラストマーの含有量を５質量％以下とすることにより、ポリアミド樹脂組成物を用いた樹脂フィルムの透明性を維持することができる。同様の観点から、オレフィン系エラストマーの含有量は、４質量％以下であることが好ましく、３．５質量％以下であることがより好ましく、３質量％以下であることがさらに好ましい。 In the polyamide resin composition according to the present invention, the content of the olefin-based elastomer is 0.1% by mass to 5% by mass of the polyamide resin composition. By setting the content of the olefin elastomer to 0.1% by mass or more, the pinhole resistance of the resin film using the polyamide resin composition can be improved. From the same viewpoint, the content of the olefin elastomer is preferably 0.5% by mass or more, more preferably 0.8% by mass or more, and still more preferably 1% by mass or more. Moreover, transparency of the resin film using a polyamide resin composition can be maintained by content of an olefin type elastomer being 5 mass% or less. From the same viewpoint, the content of the olefin elastomer is preferably 4% by mass or less, more preferably 3.5% by mass or less, and still more preferably 3% by mass or less.

　オレフィン系エラストマーは、１種のみを単独で用いてもよいし、複数種類のオレフィン系エラストマーを混合して用いてもよい。複数種類用いる場合、合計量が上記範囲となることが好ましい。 As the olefin-based elastomer, only one type may be used alone, or a plurality of olefin-based elastomers may be mixed and used. When using multiple types, it is preferable that a total amount becomes the said range.

　特に、本発明に係るポリアミド樹脂組成物において、エチレン－エチルアクリレート共重合体の含有量は、０．１質量％～５質量％であることが好ましい。エチレン－エチルアクリレート共重合体の含有量を０．１質量％以上とすることにより、ポリアミド樹脂組成物を用いた樹脂フィルムの耐ピンホール性をより効果的に改善することができる。同様の観点から、エチレン－エチルアクリレート共重合体の含有量は、０．５質量％以上であることがより好ましく、０．８質量％以上であることがさらに好ましく、１質量％以上であることが一層好ましい。また、エチレン－エチルアクリレート共重合体の含有量を５質量％以下とすることにより、ポリアミド樹脂組成物を用いた樹脂フィルムの透明性をより高く維持することができる。同様の観点から、エチレン－エチルアクリレート共重合体の含有量は、４質量％以下であることがより好ましく、３．５質量％以下であることがさらに好ましく、３質量％以下であることが一層好ましい。 In particular, in the polyamide resin composition according to the present invention, the content of the ethylene-ethyl acrylate copolymer is preferably 0.1% by mass to 5% by mass. By setting the content of the ethylene-ethyl acrylate copolymer to 0.1% by mass or more, the pinhole resistance of the resin film using the polyamide resin composition can be more effectively improved. From the same viewpoint, the content of the ethylene-ethyl acrylate copolymer is more preferably 0.5% by mass or more, still more preferably 0.8% by mass or more, and 1% by mass or more. Is more preferred. Further, by setting the content of the ethylene-ethyl acrylate copolymer to 5% by mass or less, the transparency of the resin film using the polyamide resin composition can be maintained higher. From the same viewpoint, the content of the ethylene-ethyl acrylate copolymer is more preferably 4% by mass or less, still more preferably 3.5% by mass or less, and still more preferably 3% by mass or less preferable.

　オレフィン系エラストマーとして、上記エチレン－エチルアクリレート共重合体の１種のみを単独で用いてもよいし、複数種類のオレフィン系エラストマーを混合して用いてもよい。複数種類用いる場合、合計量が上記範囲となることが好ましい。 As the olefin elastomer, only one of the above-mentioned ethylene-ethyl acrylate copolymers may be used alone, or a plurality of olefin elastomers may be mixed and used. When using multiple types, it is preferable that a total amount becomes the said range.

　〔酸化防止剤〕
　酸化防止剤としては、イルガノックス１０９８に代表されるフェノール系酸化防止剤、ヒンダードアミン系酸化防止剤、ＩＲＧＡＦＯＳ１６８等に代表されるリン系酸化防止剤、イオウ系酸化防止剤、ヒドラジン系酸化防止剤、アミド系酸化防止剤等が挙げられるが、本発明においてはフェノール系酸化防止剤が好ましく用いられる。具体例として、例えば、ビス［３－（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオン酸］［エチレンビス（オキシエチレン）］、Ｎ’，Ｎ’－ビス－３－（３’－５’ジ－ｔ－ブチル－４’－ヒドロキシフェニル）プロピオニルヘキサメチレンジアミン、ペンタエリトリトールテトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオナート］等が挙げられる。なかでも、Ｎ’，Ｎ’－ビス－３－（３’－５’ジ－ｔ－ブチル－４’－ヒドロキシフェニル）プロピオニルヘキサメチレンジアミンがフェノール系酸化防止剤として好ましく用いられる。 〔Antioxidant〕
As an antioxidant, a phenol type antioxidant represented by Irganox 1098, a hindered amine type antioxidant, a phosphorus type antioxidant represented by IRGAFOS 168 etc., a sulfur type antioxidant, a hydrazine type antioxidant, an amide Although a system antioxidant etc. are mentioned, a phenol type antioxidant is used preferably in this invention. As a specific example, for example, bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid] [ethylene bis (oxyethylene)], N ′, N′-bis-3- (3 Examples include '-5'di-t-butyl-4'-hydroxyphenyl) propionyl hexamethylene diamine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and the like. Among them, N ′, N′-bis-3- (3′-5′-di-t-butyl-4′-hydroxyphenyl) propionylhexamethylene diamine is preferably used as a phenolic antioxidant.

　本発明に係るポリアミド樹脂組成物において、酸化防止剤の含有量は、０．０１質量％～１質量％である。酸化防止剤の含有量を０．０１質量％以上とすることにより、ポリアミド樹脂組成物を用いた樹脂フィルムの熱水処理後の物性低下や耐屈曲性の低下を抑えることができる。同様の観点から、酸化防止剤の含有量は、０．０５質量％以上であることが好ましく、０．０８質量％以上であることがより好ましく、０．１質量％以上であることがさらに好ましい。酸化防止剤の含有量を１質量％を超えるとより長期間の耐熱性が期待できるが、実用性のある材料コストの観点から、酸化防止剤の含有量は、１質量％以下であり、０．８質量％以下が好ましく、０．５質量％以下がさらに好ましく、０．３質量％以下が一層好ましい。 In the polyamide resin composition according to the present invention, the content of the antioxidant is 0.01% by mass to 1% by mass. By setting the content of the antioxidant to 0.01% by mass or more, it is possible to suppress the decrease in physical properties and the decrease in flexibility after the hot water treatment of the resin film using the polyamide resin composition. From the same viewpoint, the content of the antioxidant is preferably 0.05% by mass or more, more preferably 0.08% by mass or more, and still more preferably 0.1% by mass or more . If the content of the antioxidant exceeds 1% by mass, long-term heat resistance can be expected, but from the viewpoint of practical material cost, the content of the antioxidant is 1% by mass or less, 0 .8 mass% or less is preferable, 0.5 mass% or less is more preferable, 0.3 mass% or less is more preferable.

　酸化防止剤として、上記酸化防止剤の１種のみを単独で用いてもよいし、複数種類の酸化防止剤を混合して用いてもよい。複数種類用いる場合、合計量が上記範囲となることが好ましい。 As an antioxidant, only 1 type of the said antioxidant may be used independently, and multiple types of antioxidant may be mixed and used. When using multiple types, it is preferable that a total amount becomes the said range.

　〔アイオノマー樹脂〕
　アイオノマー樹脂は、オレフィン単位とα，β－不飽和カルボン酸単位とからなる主鎖の側鎖カルボキシル基を金属イオンで部分的に中和（金属イオンを介して架橋）したオレフィン／不飽和カルボン酸共重合体である。 Ionomer resin
The ionomer resin is an olefin / unsaturated carboxylic acid in which the side chain carboxyl group of the main chain consisting of an olefin unit and an α, β-unsaturated carboxylic acid unit is partially neutralized with metal ions (crosslinking via metal ions) It is a copolymer.

　オレフィンとしては、エチレン、プロピレン等が例示されるが、中でもエチレンが好ましく用いられる。α，β－不飽和カルボン酸としては、アクリル酸、メタクリル酸が好ましく用いられるが、他のα，β－不飽和カルボン酸エステルが共重合されていても構わない。
　本発明では、特に、アイオノマー樹脂が、エチレン－メタクリル酸共重合体及びエチレン－アクリル酸共重合体の少なくとも一方を含むことが好ましい。 Examples of the olefin include ethylene and propylene. Among them, ethylene is preferably used. As the α, β-unsaturated carboxylic acid, acrylic acid and methacrylic acid are preferably used, but other α, β-unsaturated carboxylic acid esters may be copolymerized.
In the present invention, in particular, the ionomer resin preferably contains at least one of an ethylene-methacrylic acid copolymer and an ethylene-acrylic acid copolymer.

　中和カルボキシル基の金属イオン成分としては、リチウムイオン、ナトリウムイオン、カリウムイオン、マグネシウムイオン、カルシウムイオン、ストロンチウムイオン、バリウムイオン等のアルカリ金属イオン、アルカリ土類金属イオンの他、アルミニウムイオン、スズイオン、チタンイオン、マンガンイオン、鉄イオン、ニッケルイオン、銅イオン、亜鉛イオン、カドミウムイオン等が挙げられる。これらの金属イオン成分の１種のみを用いてもよいし、２種以上を用いてもよい。これらの中でも亜鉛イオン、ナトリウムイオンを金属イオン成分として用いることがポリアミド樹脂との親和性向上の観点から好ましく、亜鉛イオンがさらに好ましい。アイオノマー樹脂のカルボキシル基の中和度（全カルボキシル基数に対する中和カルボキシル基数の割合（中和カルボキシル基数の割合／全カルボキシル基数）×１００（単位：％））は、２０％～８０％であることが好ましく、３０％～７０％であることがより好ましい。アイオノマー樹脂のカルボキシル基の中和度が２０％以上であると、得られるフィルムの透明性が良好となり好ましい。アイオノマー樹脂のカルボキシル基の中和度が８０％以下であると、アイオノマー樹脂の溶融流動性の低下が避けられ、得られるフィルムの透明性が良好となるので好ましい。 The metal ion component of the neutralized carboxyl group includes, in addition to alkali metal ions such as lithium ion, sodium ion, potassium ion, magnesium ion, calcium ion, strontium ion and barium ion, alkaline earth metal ion, aluminum ion, tin ion, Examples thereof include titanium ions, manganese ions, iron ions, nickel ions, copper ions, zinc ions and cadmium ions. Only one of these metal ion components may be used, or two or more thereof may be used. Among these, it is preferable to use zinc ion or sodium ion as the metal ion component from the viewpoint of improving the affinity to the polyamide resin, and zinc ion is more preferable. The degree of neutralization of the carboxyl groups of the ionomer resin (the ratio of the number of neutralized carboxyl groups to the total number of carboxyl groups (the ratio of the number of neutralized carboxyl groups / the total number of carboxyl groups) x 100 (unit:%)) is 20% to 80% Is preferable, and 30% to 70% is more preferable. When the degree of neutralization of the carboxyl group of the ionomer resin is 20% or more, the transparency of the obtained film becomes good, which is preferable. It is preferable for the degree of neutralization of the carboxyl group of the ionomer resin to be 80% or less, since the decrease in melt flowability of the ionomer resin is avoided and the transparency of the obtained film is improved.

　ポリアミド樹脂組成物におけるアイオノマー樹脂の含有量は、ポリアミド樹脂およびオレフィン系エラストマーとの相溶性の観点から、ポリアミド樹脂組成物中に０．０１質量％以上が好ましく、より好ましくは０．０５質量％以上であり、さらに好ましくは０．１質量％以上である。同様に、フィルムの透明性の観点から３質量％以下が好ましく、より好ましくは１質量％以下であり、一層好ましくは０．６質量％以下である。アイオノマー樹脂は、ポリアミド樹脂組成物中に、１種のみ含まれていてもよいし、２種以上含まれていてもよい。２種以上含まれている場合、合計量が上記範囲となることが好ましい。
　また、アイオノマー樹脂が、ポリアミド樹脂組成物又はフィルム中において、アイオノマー樹脂同士又は他の成分と反応している場合もあるが、この場合も本発明に係るポリアミド樹脂組成物又はフィルムの範囲に含まれることは言うまでもない。 The content of the ionomer resin in the polyamide resin composition is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more in the polyamide resin composition from the viewpoint of compatibility with the polyamide resin and the olefin elastomer. More preferably, it is 0.1 mass% or more. Similarly, from the viewpoint of film transparency, 3% by mass or less is preferable, more preferably 1% by mass or less, and still more preferably 0.6% by mass or less. The ionomer resin may be contained alone or in combination of two or more kinds in the polyamide resin composition. When 2 or more types are contained, it is preferable that a total amount becomes said range.
Also, in some cases, the ionomer resin may react with the ionomer resin or with other components in the polyamide resin composition or film, but this case is also included in the range of the polyamide resin composition or film according to the present invention. Needless to say.

　本発明では、また、ポリアミド樹脂組成物における、アイオノマー樹脂とオレフィン系エラストマーとの質量比（アイオノマー樹脂／オレフィン系エラストマー）が０．０４～０．４であることが好ましい。前記質量比率の下限値は０．０５以上がより好ましく、前記質量比の上限値は０．３以下であることがより好ましい。このような範囲とすることにより、得られるフィルムの引張弾性率がより向上する傾向にある。
　特に、オレフィン系エラストマー及びアイオノマー樹脂が、それぞれ独立に、エチレン－メタクリル酸共重合体及びエチレン－アクリル酸共重合体の少なくとも一方を含むことが好ましい。このような場合、両者の相溶性が向上し、上記効果がより効果的に発揮される。 In the present invention, the mass ratio (ionomer resin / olefin elastomer) of the ionomer resin to the olefin elastomer in the polyamide resin composition is preferably 0.04 to 0.4. The lower limit value of the mass ratio is more preferably 0.05 or more, and the upper limit value of the mass ratio is more preferably 0.3 or less. By setting it as such a range, the tensile modulus of elasticity of the obtained film tends to be further improved.
In particular, it is preferable that the olefin elastomer and the ionomer resin independently contain at least one of an ethylene-methacrylic acid copolymer and an ethylene-acrylic acid copolymer. In such a case, the compatibility between the two is improved, and the above effect is more effectively exhibited.

　〔その他の成分〕
　本発明に係るポリアミド樹脂組成物は、上記成分に加え、例えば、アンチブロッキング剤、滑剤、核剤、発泡剤、安定剤及びカップリング剤などを含んでいてもよいが、これらに限定されない。これらの添加剤は、それぞれ、１種のみ含まれていてもよいし、２種以上含まれていてもよい。但し、これらの添加剤の配合量は、ポリアミド樹脂組成物の合計質量に対して１０質量％以下が好ましく、より好ましくは５質量％以下であり、さらに好ましくは３質量％以下であり、一層好ましくは１質量％以下である。上記添加剤を配合する場合、配合量の下限値としては、ポリアミド樹脂組成物の合計質量に対して０．０１質量％以上であることが好ましい。
　また、本発明に係るポリアミド樹脂組成物は、ポリアミド樹脂以外の熱可塑性樹脂を含んでいてもよいが、含んでいない方が好ましい。具体的には、本発明に係るポリアミド樹脂組成物に含まれるポリアミド樹脂以外の熱可塑性樹脂は、ポリアミド樹脂の１質量％以下であることが好ましい。 [Other ingredients]
The polyamide resin composition according to the present invention may contain, for example, an antiblocking agent, a lubricant, a nucleating agent, a foaming agent, a stabilizer, a coupling agent and the like in addition to the above components, but is not limited thereto. Each of these additives may be contained alone or in combination of two or more. However, the content of these additives is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, based on the total mass of the polyamide resin composition. Is 1% by mass or less. When mix | blending the said additive, it is preferable that it is 0.01 mass% or more with respect to the total mass of a polyamide resin composition as a lower limit of a compounding quantity.
Moreover, although the polyamide resin composition which concerns on this invention may contain thermoplastic resins other than a polyamide resin, it is preferable not to contain. Specifically, the thermoplastic resin other than the polyamide resin contained in the polyamide resin composition according to the present invention is preferably 1% by mass or less of the polyamide resin.

　ポリアミド樹脂組成物の製造方法は特に制限がなく、必要に応じて各種添加剤を配合し、従来から知られている各種の方法を採用することができる。ポリアミド樹脂組成物は、例えば、タンブラーやミキサーを用いて、特定の割合になるように均一にドライブレンドする方法、やドライブレンドで得られた混合物を溶融混練機にて、溶融混練する方法、一部を溶融混練機にて混練した上で、残りとドライブレンドする方法等により製造することができる。溶融混練は、単軸押出機、二軸押出機、ニーダー、バンバリーミキサー等の混練機を使用して行うことができる。 The method for producing the polyamide resin composition is not particularly limited, and various additives may be blended if necessary, and various methods conventionally known can be adopted. The polyamide resin composition is, for example, a method of dry blending uniformly to a specific ratio using a tumbler or a mixer, or a method of melt-kneading a mixture obtained by dry blending with a melt kneader, It can manufacture by the method etc. which carry out the dry blending with the remainder, after knead | mixing a part with a melt-kneader. Melt-kneading can be performed using kneaders, such as a single-screw extruder, a twin-screw extruder, a kneader, and a Banbury mixer.

　〔フィルム〕
　本発明に係るフィルムは、上記本発明に係るポリアミド樹脂組成物を含む。本発明に係るフィルムは、ポリアミド樹脂組成物から形成されることが好ましい。本発明に係るフィルムの厚さは、１～３００μｍが好ましい。本発明に係るフィルムは、例えば、延伸フィルムであってもよい。 〔the film〕
The film according to the present invention comprises the polyamide resin composition according to the present invention. The film according to the present invention is preferably formed of a polyamide resin composition. The thickness of the film according to the present invention is preferably 1 to 300 μm. The film according to the present invention may be, for example, a stretched film.

　本発明に係るフィルムを製造する方法としては、例えば、公知の製造方法を適用することができる。例えば、ポリアミド樹脂組成物を押出機を用いて溶融混練し、Ｔ－ダイやコートハンガーダイ等のダイを用いてフィルム状に押し出し、キャスティングロール面上にキャスティングした後に冷却することによりポリアミド樹脂組成物含有フィルムを製造することができる。製造したフィルムを延伸処理して、延伸フィルムとしてもよい。その場合、製造したフィルムを一軸延伸して一軸延伸フィルムとしてもよいし、二軸延伸して二軸延伸フィルムとしてもよい。 As a method for producing the film according to the present invention, for example, a known production method can be applied. For example, the polyamide resin composition is melt-kneaded using an extruder, extruded into a film form using a die such as a T-die or a coat hanger die, cast on a casting roll surface, and then cooled. Contained films can be produced. The produced film may be subjected to a stretching treatment to form a stretched film. In that case, the produced film may be uniaxially stretched to be a uniaxially stretched film, or may be biaxially stretched to be a biaxially stretched film.

　〔フィルム積層体〕
　本発明に係るフィルム積層体は、上記本発明に係るフィルムを含む複数のフィルムの積層体である。本発明に係るフィルム積層体は、例えば、本発明に係るフィルムを含む複数のフィルムを熱圧着することにより製造することができる。製造したフィルム積層体を延伸処理して、延伸フィルム積層体としてもよい。その場合、製造したフィルム積層体を一軸延伸して一軸延伸フィルム積層体としてもよいし、二軸延伸して二軸延伸フィルム積層体としてもよい。 [Film laminate]
The film laminate according to the present invention is a laminate of a plurality of films including the film according to the present invention. The film laminate according to the present invention can be produced, for example, by thermocompression bonding a plurality of films including the film according to the present invention. The produced film laminate may be subjected to a stretching treatment to form a stretched film laminate. In that case, the produced film laminate may be uniaxially stretched to be a uniaxially stretched film laminate, or may be biaxially stretched to be a biaxially stretched film laminate.

　本発明に係るフィルム積層体は、例えば、コア層と、コア層の両面のそれぞれを覆うスキン層とにより構成されていてもよい。この場合、コア層とスキン層とのうち、スキン層が、本発明に係るポリアミド樹脂組成物により構成されていることが好ましい。例えば、コア層が、ポリメタキシリレンアジパミド（ポリアミドＭＸＤ６）やエチレン－ビニルアルコール共重合体などのバリア性樹脂からなり、スキン層が、本発明に係るポリアミド樹脂組成物により構成されていることが好ましい。
　特に、本発明に係るフィルムが、ポリアミド樹脂６を含む場合、食品用包装材料であって、特に加熱処理される用途に好ましく用いられる。
　本発明の好ましい一実施形態として、本発明に係るフィルムであって、ポリアミド樹脂６を含むフィルムと、バリア層（例えば、エチレン－ビニルアルコール共重合体（ＥＶＯＨ））とのフィルム積層体が挙げられる。 The film laminated body which concerns on this invention may be comprised, for example by the core layer and the skin layer which covers each of both surfaces of a core layer. In this case, among the core layer and the skin layer, it is preferable that the skin layer be constituted of the polyamide resin composition according to the present invention. For example, the core layer is made of a barrier resin such as polymetaxylylene adipamide (polyamide MXD6) or ethylene-vinyl alcohol copolymer, and the skin layer is made of the polyamide resin composition according to the present invention. Is preferred.
In particular, when the film according to the present invention contains the polyamide resin 6, it is a packaging material for food, and is preferably used particularly for applications to be heat-treated.
A preferred embodiment of the present invention is a film according to the present invention, which is a film laminate of a film containing polyamide resin 6 and a barrier layer (for example, ethylene-vinyl alcohol copolymer (EVOH)). .

　フィルム積層体の詳細は、特開２００１－３４１２５３号公報の記載を参酌でき、これらの内容は本明細書に組み込まれる。特に、特開２００１－３４１２５３号公報において、Ｂ層を構成する組成物を、本発明に係るポリアミド樹脂組成物に置き換えた積層体が好ましい。 The details of the film laminate can be referred to the description of JP-A-2001-341253, the contents of which are incorporated herein. In particular, a laminate in which the composition constituting the layer B is replaced with the polyamide resin composition according to the present invention in JP-A-2001-341253 is preferable.

　以下、本発明について、具体的な実施例に基づいて、さらに詳細に説明するが、本発明は以下の実施例に何ら限定されるものではなく、その要旨を変更しない範囲において適宜変更して実施することが可能である。 EXAMPLES Hereinafter, the present invention will be described in more detail based on specific examples, but the present invention is not limited to the following examples at all, and the present invention is appropriately modified without changing the gist of the present invention. It is possible.

　なお、以下の実施例及び比較例では、以下の材料を用いた。
　ポリアミド樹脂：ポリアミド６（以下「ＰＡ６」とも称す、商品名：ＵＢＥナイロン１０２２Ｂ（宇部興産株式会社製））
　オレフィン系エラストマー：エチレン－エチルアクリレート共重合体（以下、「エチレン－エチルアクリレート樹脂」、とも称す）、商品名：ＵＢＥポリエチレンＺＥ７０８（宇部丸善ポリエチレン株式会社製））　エチレン－エチルアクリレート共重合体におけるアクリル酸エステルの含有量は１６質量％である。
オレフィン系エラストマー：エチレン－エチルアクリレート共重合体、商品名：ＵＢＥポリエチレンＺＥ７４２（宇部丸善ポリエチレン株式会社製））　エチレン－エチルアクリレート共重合体におけるアクリル酸エステルの含有量は２５質量％である。
　酸化防止剤：フェノール系酸化防止剤、イルガノックス（Ｉｒｇａｎｏｘ）１０９８（ＢＡＳＦ社製）
　アイオノマー樹脂：エチレン－メタクリル酸共重合体のＺｎ2+アイオノマー、アイオノマー樹脂のカルボキシル基の中和度６０％、商品名：ハイミラン１７０６（三井・デュポン株式会社製） In the following examples and comparative examples, the following materials were used.
Polyamide resin: Polyamide 6 (hereinafter also referred to as "PA 6", trade name: UBE nylon 1022 B (manufactured by Ube Industries, Ltd.))
Olefin-based elastomer: ethylene-ethyl acrylate copolymer (hereinafter, also referred to as "ethylene-ethyl acrylate resin", trade name: UBE polyethylene ZE 708 (manufactured by Ube Maruzen Polyethylene Co., Ltd.) Acrylic in ethylene-ethyl acrylate copolymer The content of acid ester is 16% by mass.
Olefin-based elastomer: ethylene-ethyl acrylate copolymer, trade name: UBE polyethylene ZE 742 (manufactured by Ube Maruzen Polyethylene Corporation) The content of acrylic ester in the ethylene-ethyl acrylate copolymer is 25% by mass.
Antioxidant: Phenolic antioxidant, Irganox 1098 (manufactured by BASF)
Ionomer resin: Zn 2+ ionomer of ethylene-methacrylic acid copolymer, degree of neutralization of carboxyl group of ionomer resin 60%, trade name: HIMIRAN 1706 (manufactured by Mitsui & DuPont Co., Ltd.)

　（実施例１）
　ポリアミド６を９８．７質量％と、エチレン－エチルアクリレート共重合体（ＺＥ７０８）を１質量％と、酸化防止剤を０．１質量％と、アイオノマー樹脂を０．２質量％とをドライブレンドにて混合し、ポリアミド樹脂組成物を得た。プラボー社製Ｔダイ成形装置（ダイ幅：３００ｍｍ）を用いて、ポリアミド樹脂組成物からなるフィルムを得た。押出機の設定温度を２００～２６０℃、ダイの温度を２６０℃、冷却ロールの温度を３０℃で成形した。ロールの巻き取り速度を変えて、厚み１００μｍと５０μｍのフィルムを作製した。 Example 1
Dry blend of 98.7% by mass of polyamide 6, 1% by mass of ethylene-ethyl acrylate copolymer (ZE 708), 0.1% by mass of antioxidant, and 0.2% by mass of ionomer resin The mixture was mixed to obtain a polyamide resin composition. The film which consists of a polyamide resin composition was obtained using the Pravo T-die shaping | molding apparatus (die width: 300 mm). The set temperature of the extruder was 200 to 260 ° C., the temperature of the die was 260 ° C., and the temperature of the cooling roll was 30 ° C. Films with thicknesses of 100 μm and 50 μm were produced by changing the winding speed of the roll.

　（実施例２）
　ポリアミド樹脂組成物におけるポリアミド６の含有量を９６．１質量％とし、エチレン－エチルアクリレート共重合体（ＺＥ７０８）の含有量を３質量％とし、酸化防止剤の含有量を０．３質量％とし、アイオノマー樹脂の含有量を０．６質量％としたこと以外は、実施例１と同様にしてポリアミド樹脂組成物からなるフィルムを作製した。 (Example 2)
The content of polyamide 6 in the polyamide resin composition is 96.1% by mass, the content of ethylene-ethyl acrylate copolymer (ZE 708) is 3% by mass, and the content of antioxidant is 0.3% by mass. A film of a polyamide resin composition was produced in the same manner as in Example 1 except that the content of the ionomer resin was 0.6% by mass.

　（実施例３）
　ポリアミド樹脂組成物におけるポリアミド６の含有量を９９．３質量％とし、エチレン－エチルアクリレート共重合体（ＺＥ７０８）の含有量を０．５質量％とし、酸化防止剤の含有量を０．１質量％とし、アイオノマー樹脂の含有量を０．１質量％としたこと以外は、実施例１と同様にしてポリアミドフィルムを作製した。 (Example 3)
The content of polyamide 6 in the polyamide resin composition is 99.3% by mass, the content of ethylene-ethyl acrylate copolymer (ZE 708) is 0.5% by mass, and the content of antioxidant is 0.1% %, And a polyamide film was produced in the same manner as in Example 1 except that the content of the ionomer resin was 0.1% by mass.

　（実施例４）
　ポリアミド樹脂組成物におけるポリアミド６の含有量を９８．７質量％とし、エチレン－エチルアクリレート共重合体（ＺＥ７４２）の含有量を１質量％とし、酸化防止剤の含有量を０．１質量％とし、アイオノマー樹脂の含有量を０．２質量％としたこと以外は、実施例１と同様にしてポリアミドフィルムを作製した。 (Example 4)
The content of polyamide 6 in the polyamide resin composition is 98.7% by mass, the content of ethylene-ethyl acrylate copolymer (ZE 742) is 1% by mass, and the content of antioxidant is 0.1% by mass. A polyamide film was produced in the same manner as in Example 1 except that the content of the ionomer resin was 0.2% by mass.

　（実施例５）
　ポリアミド樹脂組成物におけるポリアミド６の含有量を９６．１質量％とし、エチレン－エチルアクリレート共重合体（ＺＥ７４２）の含有量を３質量％とし、酸化防止剤の含有量を０．３質量％とし、アイオノマー樹脂の含有量を０．６質量％としたこと以外は、実施例１と同様にしてポリアミドフィルムを作製した。 (Example 5)
The content of polyamide 6 in the polyamide resin composition is 96.1% by mass, the content of ethylene-ethyl acrylate copolymer (ZE 742) is 3% by mass, and the content of antioxidant is 0.3% by mass. A polyamide film was produced in the same manner as in Example 1 except that the ionomer resin content was 0.6% by mass.

　（比較例１）
　ポリアミド６のみを用いてポリアミドフィルムを実施例１と同様にしてポリアミドフィルムを作製した。 (Comparative example 1)
A polyamide film was produced in the same manner as in Example 1 using only polyamide 6 to prepare a polyamide film.

　（比較例２）
　ポリアミド樹脂組成物におけるポリアミド６の含有量を９９．９質量％とし、エチレン－エチルアクリレート共重合体（ＺＥ７０８）及びアイオノマー樹脂を用いなかったこと以外は実施例１と同様にしてポリアミドフィルムを作製した。 (Comparative example 2)
A polyamide film was produced in the same manner as in Example 1 except that the content of polyamide 6 in the polyamide resin composition was 99.9% by mass, and the ethylene-ethyl acrylate copolymer (ZE 708) and the ionomer resin were not used. .

　（比較例３）
　ポリアミド樹脂組成物におけるポリアミド６の含有量を９９．０質量％とし、エチレン－エチルアクリレート共重合体（ＺＥ７０８）の含有量を１質量％とし、酸化防止剤及びアイオノマー樹脂を用いなかったこと以外は実施例１と同様にしてポリアミドフィルムを作製した。 (Comparative example 3)
The content of the polyamide 6 in the polyamide resin composition is 99.0 mass%, the content of the ethylene-ethyl acrylate copolymer (ZE 708) is 1 mass%, and the antioxidant and the ionomer resin are not used. A polyamide film was produced in the same manner as in Example 1.

　（比較例４）
　ポリアミド樹脂組成物におけるポリアミド６の含有量を９７．０質量％とし、エチレン－エチルアクリレート共重合体（ＺＥ７０８）の含有量を３質量％とし、酸化防止剤及びアイオノマー樹脂を用いなかったこと以外は実施例１と同様にしてポリアミドフィルムを作製した。 (Comparative example 4)
The content of polyamide 6 in the polyamide resin composition is 97.0% by mass, the content of ethylene-ethyl acrylate copolymer (ZE 708) is 3% by mass, and no antioxidant and ionomer resin are used. A polyamide film was produced in the same manner as in Example 1.

　（比較例５）
　ポリアミド樹脂組成物におけるポリアミド６の含有量を９９．０質量％とし、エチレン－エチルアクリレート共重合体、酸化防止剤を使用しなかったこと、アイオノマー樹脂の含有量を１質量％としたこと以外は、実施例１と同様にしてポリアミドフィルムを作製した。 (Comparative example 5)
The content of polyamide 6 in the polyamide resin composition is 99.0 mass%, ethylene-ethyl acrylate copolymer and antioxidant are not used, and the content of ionomer resin is 1 mass%. A polyamide film was produced in the same manner as in Example 1.

　（比較例６）
　ポリアミド樹脂組成物におけるポリアミド６の含有量を９７．０質量％とし、エチレン－エチルアクリレート共重合体、酸化防止剤を使用しなかったこと、アイオノマー樹脂の含有量を３質量％としたこと以外は、実施例１と同様にしてポリアミドフィルムを作製した。 (Comparative example 6)
The content of polyamide 6 in the polyamide resin composition was 97.0% by mass, and the ethylene-ethyl acrylate copolymer and the antioxidant were not used, and the content of ionomer resin was 3% by mass. A polyamide film was produced in the same manner as in Example 1.

　（比較例７）
　ポリアミド樹脂組成物におけるポリアミド６の含有量を９８．８質量％とし、エチレン－エチルアクリレート共重合体（ＺＥ７０８）の含有量を１質量％、アイオノマー樹脂の含有量を０．２質量％とし、酸化防止剤を使用しなかったこと以外は、実施例１と同様にしてポリアミドフィルムを作製した。 (Comparative example 7)
The content of polyamide 6 in the polyamide resin composition is 98.8% by mass, the content of ethylene-ethyl acrylate copolymer (ZE 708) is 1% by mass, and the content of ionomer resin is 0.2% by mass. A polyamide film was produced in the same manner as in Example 1 except that no inhibitor was used.

　（比較例８）
　ポリアミド樹脂組成物におけるポリアミド６の含有量を９８．９質量％とし、エチレン－エチルアクリレート共重合体（ＺＥ７０８）の含有量を１質量％、酸化防止剤の含有量を０．１質量％とし、アイオノマー樹脂を使用しなかったこと以外は、実施例１と同様にしてポリアミドフィルムを作製した。 (Comparative example 8)
The content of polyamide 6 in the polyamide resin composition is 98.9% by mass, the content of ethylene-ethyl acrylate copolymer (ZE 708) is 1% by mass, and the content of antioxidant is 0.1% by mass, A polyamide film was produced in the same manner as in Example 1 except that no ionomer resin was used.

　（比較例９）
　ポリアミド樹脂組成物におけるポリアミド６の含有量を９９．６質量％とし、エチレン－エチルアクリレート共重合体（ＺＥ７０８）の含有量を０．２５質量％とし、酸化防止剤の含有量を０．１質量％とし、アイオノマー樹脂の含有量を０．０５質量％としたこと以外は、実施例１と同様にしてポリアミドフィルムを作製した。 (Comparative example 9)
The content of polyamide 6 in the polyamide resin composition is 99.6% by mass, the content of ethylene-ethyl acrylate copolymer (ZE 708) is 0.25% by mass, and the content of antioxidant is 0.1% %, And a polyamide film was produced in the same manner as in Example 1 except that the content of the ionomer resin was 0.05% by mass.

　（熱水処理）
　上記実施例１～５、ならびに、比較例１～８のそれぞれにおいて厚み５０μｍのフィルムを２枚ずつ作製し、各例において作製した２枚のうちの１枚に１３５℃の水蒸気雰囲気下に３０分保持する熱水処理を行った。以下、熱水処理を行わなかったフィルムを「熱水処理前フィルム」とし、熱水処理を行ったフィルムを「熱水処理後フィルム」とする。 (Hot water treatment)
In each of the above Examples 1 to 5 and Comparative Examples 1 to 8, two films each having a thickness of 50 μm were produced, and one of the two produced in each example was subjected to a steam atmosphere of 135 ° C. for 30 minutes. The hot water treatment to hold was performed. Hereinafter, a film which has not been subjected to the hot water treatment is referred to as a "pre-hot water treatment film", and a film which has been subjected to the hot water treatment is referred to as a "hot water treated film".

　（ヘイズ（透明性））
　日本電色工業（株）製、Ｈａｚｅ　Ｍｅｔｅｒにより、ＡＳＴＭ　Ｄ－１００３に準じて、二軸延伸したフィルムの曇価（ヘイズ率）を測定した。具体的には、厚み１００μｍのフィルムを岩本製作所製の二軸延伸機ＢＩＸ－７０３型を用いて、１００℃で、６０秒間予熱した後、Ｔダイ成形時の押出方向（ＭＤ方向）及びその直角方向（ＴＤ方向）の２方向に、１５０ｍｍ／秒の変形速度で３．０倍に延伸した後、２００℃の加熱空気で３０秒間熱処理を行い、その後、冷却して延伸槽から取り出して、厚み１５μｍ程度の二軸延伸フィルムを得た。得られた二軸延伸フィルムを用いて上記の曇価を測定した。 (Haze (transparency))
The haze value of the biaxially stretched film was measured by Haze Meter manufactured by Nippon Denshoku Kogyo Co., Ltd. according to ASTM D-1003. Specifically, a 100 μm thick film is preheated for 60 seconds at 100 ° C. using a biaxial drawing machine BIX-703 manufactured by Iwamoto Seisakusho, and then the extrusion direction (MD direction) at T die forming and the right angle thereof After stretching in 3.0 directions at a deformation rate of 150 mm / sec in two directions (TD direction), heat treatment is performed with heated air at 200 ° C. for 30 seconds, and then cooled and taken out from the stretching tank. A biaxially stretched film of about 15 μm was obtained. The above-mentioned haze value was measured using the obtained biaxially stretched film.

　（引張破断伸度及び伸度保持率）
　エー・アンド・デイ製、テンシロン万能材料試験機、ＲＴＡ－１０ＫＮにより、ＡＳＴＭ　Ｄ－８８２に準じて、引張速度３００ｍｍ/分、チャック間距離５０ｍｍの条件にて、厚み５０μｍの熱水処理前フィルム及び熱水処理後フィルムのそれぞれの引張破断伸度（％）を測定した。熱水処理後の引張破断伸びの伸度保持率（％）は下記の式から算出した。 (Tension elongation at break and elongation retention)
Hot water treated film with a thickness of 50 μm under conditions of a tensile speed of 300 mm / min and a distance between chucks of 50 mm according to ASTM D-882 according to ASTM D, made by A & D, Tensilon Universal Material Testing Machine, The tensile elongation at break (%) of each of the films after hot water treatment was measured. The elongation retention (%) of the tensile elongation at break after hot water treatment was calculated from the following equation.

　伸度保持率（％）＝熱水処理後の引張破断伸び（％）／熱水処理前の引張破断伸び（％）×１００ Elongation retention (%) = tensile elongation at break after hot water treatment (%) / tensile elongation at break before hot water treatment (%) x 100

　（ゲルボフレックス（耐ピンホール性））
　理学工業（株）製、恒温槽付ゲルボフレックステスターにより、ＭＩＬ－Ｂ－１３１Ｃに従い、２３℃、５０％相対湿度（ＲＨ）環境下で１０００回の屈曲テストを、厚み５０μｍの熱水処理前フィルム及び熱水処理後フィルムのそれぞれに対して行った後、そのフィルムを記録紙上に設置後、墨汁を塗り、記録紙上に記録された黒点の数を測定した。その結果、個数が９０個未満を「○」、個数が９０個以上、１２０個未満を「△」、個数が１２０個以上を「×」と判断した。 (Gerboflex (pinhole resistance))
Physician Industrial Co., Ltd. product, with a constant temperature bath Gelvoflex tester, according to MIL-B-131C, before flexing test of 1000 times under 50% relative humidity (RH) environment at a thickness of 50 μm according to MIL-B-131C After the film and the hot water treated film were respectively placed, the film was placed on a recording paper, then painted with black ink, and the number of black spots recorded on the recording paper was measured. As a result, it was judged that the number is less than 90 as “○”, the number is 90 or more and less than 120 as “Δ”, and the number is 120 or more as “x”.

Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002

　上記結果から明らかなとおり、本発明に係るポリアミド樹脂組成物を用いたフィルムは、熱水処理後も、引張破断伸度及び伸度保持率が高く、ピンホール耐性にも優れていた。
　さらに、実施例１と比較例３、実施例２と比較例４の比較から明らかな通り、酸化防止剤とアイオノマー樹脂を配合することにより、ヘイズを格段に低くすることが可能になった。
　また、酸化防止剤を含まないと（比較例５～７）、熱水処理後の各種物性が格段に劣る結果となった。特に、ポリアミド樹脂のみからなるフィルムを用いた場合（比較例１）などよりも性能が劣っていた。
　アイオノマー酸化防止剤を含まないと（比較例８）、ヘイズが高くなってしまった。 As is clear from the above results, the film using the polyamide resin composition according to the present invention was high in tensile elongation at break and elongation retention, and also excellent in pinhole resistance even after hot water treatment.
Furthermore, as is clear from the comparison of Example 1 with Comparative Example 3 and Example 2 with Comparative Example 4, it was possible to significantly lower the haze by blending the antioxidant and the ionomer resin.
In addition, when no antioxidant was contained (Comparative Examples 5 to 7), various physical properties after the hot water treatment were remarkably inferior. In particular, the performance was inferior to the case where a film consisting only of a polyamide resin was used (Comparative Example 1).
When the ionomer antioxidant was not contained (comparative example 8), the haze became high.

（引張弾性率）
　ポリアミド樹脂組成物として、ポリアミド樹脂としてポリアミド６、オレフィン系エラストマーとしてＵＢＥポリエチレンＺＥ７０８、アイオノマー樹脂としてハイミラン１７０６を表３に示す質量比となるように、配合した。
　得られたポリアミド樹脂組成物を実施例１に従い、厚みが１００μｍの未延伸単層フィルムを成形した。さらに、ヘイズの項目に記載の方法と同様にして、厚み１５μｍの延伸単層フィルムを得た。得られた延伸単層フィルムの引張弾性率を（引張試験機(エー・アンド・デイ製、テンシロン万能材料試験機ＲＴＡ－１０ＫＮ)により、ＡＳＴＭ　Ｄ－８８２）に従い、２３℃、５０％相対湿度（ＲＨ）の雰囲気下で測定した。結果を下記表３に示す。

Figure JPOXMLDOC01-appb-T000003
　上記結果から明らかな通り、オレフィン系エラストマーとアイオノマー樹脂の質量比率が実験例Ａ～実験例Ｄの範囲のときに、引張弾性率が顕著に高くなることが確認された。すなわち、本発明のフィルムは、オレフィン系エラストマーとアイオノマー樹脂の質量比が０．０４～０．４程度のときに、高い引張弾性率を達成することが分かった。 (Tensile modulus)
As a polyamide resin composition, polyamide 6 as a polyamide resin, UBE polyethylene ZE 708 as an olefin elastomer, and HIMIRAN 1706 as an ionomer resin were blended so as to have the mass ratio shown in Table 3.
The obtained polyamide resin composition was used to form an unstretched single-layer film having a thickness of 100 μm according to Example 1. Furthermore, it carried out similarly to the method as described in the item of haze, and obtained a 15-micrometer-thick stretched single layer film. The tensile elastic modulus of the obtained stretched single-layer film is measured at 23 ° C. and 50% relative humidity (according to ASTM D-882 using a tensile tester (A and D, made by Tensilon Universal Material Tester RTA-10KN) It measured in the atmosphere of RH). The results are shown in Table 3 below.
Figure JPOXMLDOC01-appb-T000003
 As apparent from the above results, when the mass ratio of the olefin elastomer to the ionomer resin is in the range of Experimental Example A to Experimental Example D, it is confirmed that the tensile elastic modulus is remarkably high. That is, it was found that the film of the present invention achieves high tensile modulus when the mass ratio of the olefin elastomer to the ionomer resin is about 0.04 to 0.4.

Claims (11)

　ポリアミド樹脂と、
　０．１質量％～５質量％のオレフィン系エラストマーと、
　０．０１質量％～１質量％の酸化防止剤と、
　０．０１質量％～３質量％のアイオノマー樹脂と、
　を含む、ポリアミド樹脂組成物。 Polyamide resin,
0.1% by mass to 5% by mass of an olefin-based elastomer,
0.01% by mass to 1% by mass of an antioxidant,
0.01% by mass to 3% by mass of ionomer resin,
A polyamide resin composition containing 　前記ポリアミド樹脂が脂肪族ポリアミド樹脂を含む、請求項１に記載のポリアミド樹脂組成物。 The polyamide resin composition according to claim 1, wherein the polyamide resin comprises an aliphatic polyamide resin. 　前記ポリアミド樹脂がポリアミド６を含む、請求項１に記載のポリアミド樹脂組成物。 The polyamide resin composition according to claim 1, wherein the polyamide resin comprises polyamide 6. 　前記オレフィン系エラストマーが、エチレン－エチルアクリレート共重合体を含む、請求項１～３のいずれか一項に記載のポリアミド樹脂組成物。 The polyamide resin composition according to any one of claims 1 to 3, wherein the olefin-based elastomer contains an ethylene-ethyl acrylate copolymer. 　前記オレフィン系エラストマーが、エチレン－エチルアクリレート共重合体を含み、前記エチレン－エチルアクリレート共重合体におけるアクリル酸含有量が５質量％～３０質量％である、請求項１～３のいずれか一項に記載のポリアミド樹脂組成物。 The said olefin-type elastomer contains ethylene-ethyl acrylate copolymer, Acrylic acid content in the said ethylene-ethyl acrylate copolymer is 5 mass%-30 mass%, The any one of Claims 1-3 The polyamide resin composition as described in-. 　前記酸化防止剤がフェノール系酸化防止剤を含む、請求項１～５のいずれか一項に記載のポリアミド樹脂組成物。 The polyamide resin composition according to any one of claims 1 to 5, wherein the antioxidant comprises a phenolic antioxidant. 　前記アイオノマー樹脂が、エチレン－メタクリル酸共重合体及びエチレン－アクリル酸共重合体の少なくとも一方を含む、請求項１～６のいずれか一項に記載のポリアミド樹脂組成物。 The polyamide resin composition according to any one of claims 1 to 6, wherein the ionomer resin contains at least one of an ethylene-methacrylic acid copolymer and an ethylene-acrylic acid copolymer. 　前記オレフィン系エラストマー及びアイオノマー樹脂が、それぞれ独立に、エチレン－メタクリル酸共重合体及びエチレン－アクリル酸共重合体の少なくとも一方を含む、請求項１～７のいずれか一項に記載のポリアミド樹脂組成物。 The polyamide resin composition according to any one of claims 1 to 7, wherein the olefin elastomer and the ionomer resin each independently contain at least one of an ethylene-methacrylic acid copolymer and an ethylene-acrylic acid copolymer. object. 　前記ポリアミド樹脂組成物に含まれるポリアミド樹脂の９９質量％以上が脂肪族ポリアミド樹脂である、請求項１～８のいずれか一項に記載のポリアミド樹脂組成物。 The polyamide resin composition according to any one of claims 1 to 8, wherein 99% by mass or more of the polyamide resin contained in the polyamide resin composition is an aliphatic polyamide resin. 　請求項１～９のいずれか一項に記載のポリアミド樹脂組成物を含むフィルム。 A film comprising the polyamide resin composition according to any one of claims 1 to 9. 　延伸フィルムである、請求項１０に記載のフィルム。 The film according to claim 10, which is a stretched film.
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