TW201728680A - Polyamide resin composition and film - Google Patents

Polyamide resin composition and film Download PDF

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TW201728680A
TW201728680A TW105134214A TW105134214A TW201728680A TW 201728680 A TW201728680 A TW 201728680A TW 105134214 A TW105134214 A TW 105134214A TW 105134214 A TW105134214 A TW 105134214A TW 201728680 A TW201728680 A TW 201728680A
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polyamine
mass
poly
resin composition
film
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TW105134214A
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藪直靖
佐野英男
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宇部興產股份有限公司
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    • 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 other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C08L23/0876—Neutralised polymers, 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

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

聚醯胺樹脂組成物及薄膜Polyamide resin composition and film

本發明關於一種聚醯胺樹脂組成物、及包含該聚醯胺樹脂組成物之薄膜。The present invention relates to a polyamide resin composition and a film comprising the polyamide resin composition.

由聚醯胺樹脂組成物構成之薄膜(以下，「由聚醯胺樹脂組成物構成之薄膜」有時稱為「聚醯胺薄膜」、「樹脂薄膜」。)，其氣體阻隔性、強韌性、耐針孔性、耐熱性、透明性等各種特性優異。因此，聚醯胺薄膜多使用在各種領域。具體而言，聚醯胺薄膜例如也可用作食品包裝構件等(參照專利文獻1。)。 ［先前技術文獻］ ［專利文獻］A film composed of a polyamide resin composition (hereinafter, "a film composed of a polyamide resin composition" may be referred to as a "polyamide film" or a "resin film"), and its gas barrier properties and toughness. It is excellent in various properties such as pinhole resistance, heat resistance, and transparency. Therefore, polyimide films are used in various fields. Specifically, the polyamide film can also be used as a food packaging member or the like (see Patent Document 1). [Prior Technical Literature] [Patent Literature]

［專利文獻1］日本特開2001-341253號公報[Patent Document 1] Japanese Patent Laid-Open Publication No. 2001-341253

［發明所欲解決之課題］ 順便提及，例如聚醯胺薄膜用作食品包裝構件的情況下，進行加熱殺菌時會將聚醯胺薄膜加熱。故，在此種情況下，要求聚醯胺薄膜具有優異的熱耐久性。[Problems to be Solved by the Invention] Incidentally, for example, in the case where a polyamide film is used as a food packaging member, the polyimide film is heated during heat sterilization. Therefore, in this case, the polyamide film is required to have excellent heat durability.

本發明之主要目的在於提供一種能提供具優異熱耐久性之聚醯胺薄膜的聚醯胺樹脂組成物、及薄膜。 ［解決課題之手段］SUMMARY OF THE INVENTION A primary object of the present invention is to provide a polyamide resin composition and a film which can provide a polyamide film having excellent heat durability. [Means for solving the problem]

基於上述課題，本案發明人們進行研究的結果，藉由下列手段＜1＞，較佳為藉由＜2＞～＜11＞，可解決上述課題。 ＜1＞一種聚醯胺樹脂組成物，包含：聚醯胺樹脂、0.1質量%～5質量%之烯烴系彈性體、0.01質量%～1質量%之抗氧化劑、及0.01質量%～3質量%之離子聚合物樹脂。 ＜2＞如＜1＞之聚醯胺樹脂組成物，其中，該聚醯胺樹脂包含脂肪族聚醯胺樹脂。 ＜3＞如＜1＞之聚醯胺樹脂組成物，其中，該聚醯胺樹脂包含聚醯胺6。 ＜4＞如＜1＞至＜3＞中任一項之聚醯胺樹脂組成物，其中，該烯烴系彈性體包含乙烯-丙烯酸乙酯共聚物。 ＜5＞如＜1＞至＜3＞中任一項之聚醯胺樹脂組成物，其中，該烯烴系彈性體包含乙烯-丙烯酸乙酯共聚物，且該乙烯-丙烯酸乙酯共聚物中之丙烯酸含量為5質量%～30質量%。 ＜6＞如＜1＞至＜5＞中任一項之聚醯胺樹脂組成物，其中，該抗氧化劑包含苯酚系抗氧化劑。 ＜7＞如＜1＞至＜6＞中任一項之聚醯胺樹脂組成物，其中，該離子聚合物樹脂包含乙烯-甲基丙烯酸共聚物及乙烯-丙烯酸共聚物中之至少一者。 ＜8＞如＜1＞至＜7＞中任一項之聚醯胺樹脂組成物，其中，該烯烴系彈性體及離子聚合物樹脂各自獨立地包含乙烯-甲基丙烯酸共聚物及乙烯-丙烯酸共聚物中之至少一者。 ＜9＞如＜1＞至＜8＞中任一項之聚醯胺樹脂組成物，其中，該聚醯胺樹脂組成物所包含之聚醯胺樹脂之99質量%以上為脂肪族聚醯胺樹脂。 ＜10＞一種薄膜，包含如＜1＞至＜9＞中任一項之聚醯胺樹脂組成物。 ＜11＞如＜10＞之薄膜，其係延伸薄膜。 ［發明之效果］Based on the above problems, the inventors of the present invention have solved the above problems by the following means <1>, preferably by <2> to <11>. <1> A polyamide resin composition comprising: a 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, and 0.01% by mass to 3% by mass Ionic polymer resin. <2> The polyamide resin composition according to <1>, wherein the polyamide resin comprises an aliphatic polyamide resin. <3> The polyamide resin composition according to <1>, wherein the polyamide resin comprises polyamine 6. The polyamine resin composition according to any one of <1> to <3> wherein the olefin-based elastomer comprises an ethylene-ethyl acrylate copolymer. The polyamine resin composition according to any one of <1> to <3> wherein the olefin-based elastomer comprises an ethylene-ethyl acrylate copolymer, and the ethylene-ethyl acrylate copolymer The acrylic acid content is 5 mass% to 30 mass%. <6> The polyamide resin composition according to any one of <1> to <5> wherein the antioxidant comprises a phenol antioxidant. The polyamine resin composition according to any one of <1> to <6> wherein the ionic polymer resin comprises at least one of an ethylene-methacrylic acid copolymer and an ethylene-acrylic acid copolymer. The polyamine resin composition according to any one of <1> to <7> wherein the olefin-based elastomer and the ionic polymer resin each independently comprise an ethylene-methacrylic acid copolymer and an ethylene-acrylic acid. At least one of the copolymers. The polyimide composition of 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 polyamine Resin. <10> A film comprising the polyamine resin composition according to any one of <1> to <9>. <11> A film of <10> which is an extended film. [Effects of the Invention]

根據本發明，可提供一種能提供具優異熱耐久性之聚醯胺薄膜的聚醯胺樹脂組成物、及薄膜。According to the present invention, it is possible to provide a polyamide resin composition and a film which can provide a polyamide film having excellent heat durability.

以下所記載之本發明之構成要素的說明係基於本發明之代表性實施態樣而進行，但本發明並不限定於該等實施態樣。 本說明書中，用「～」表示之數值範圍意指包含「～」之前後記載之數值作為下限值及上限值的範圍。又，「(甲基)丙烯酸基」表示「丙烯酸基」及「甲基丙烯酸基」之兩者、或任一者。The description of the constituent elements of the present invention described below is based on a representative embodiment of the present invention, but the present invention is not limited to the embodiments. In the present specification, the numerical range expressed by "~" means a range including the numerical values described before and after "~" as the lower limit and the upper limit. Moreover, "(meth)acrylic group" means either or both of "acrylic group" and "methacrylic group".

本發明之聚醯胺樹脂組成物包含：聚醯胺樹脂、0.1質量%～5質量%之烯烴系彈性體、0.01質量%～1質量%之抗氧化劑、及0.01質量%～3質量%之離子聚合物樹脂。藉由為如此之構成，可獲得熱水處理後之各種物性優異的聚醯胺薄膜。The polyamidamide resin composition of the present invention comprises: a 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, and 0.01% by mass to 3% by mass of an ion. Polymer resin. With such a configuration, a polyimide film having excellent physical properties after hot water treatment can be obtained.

［聚醯胺樹脂］ 就聚醯胺樹脂而言，例如可列舉脂肪族聚醯胺之均聚物或使用數種形成該等之原料單體而得之共聚物等(亦即，係脂肪族聚醯胺樹脂，為均聚物或共聚物)。脂肪族聚醯胺之均聚物或使用數種形成該等之原料單體而得之共聚物的具體例，例如可列舉聚己內醯胺(聚醯胺6)、聚十一烷醯胺(聚醯胺11)、聚十二烷醯胺(聚醯胺12)、聚乙烯己二醯胺(聚醯胺26)、聚四亞甲基丁二醯胺(聚醯胺44)、聚四亞甲基戊二醯胺(聚醯胺45)、聚四亞甲基己二醯胺(聚醯胺46)、聚四亞甲基辛二醯胺(聚醯胺48)、聚四亞甲基壬二醯胺(聚醯胺49)、聚四亞甲基癸二醯胺(聚醯胺410)、聚四亞甲基十二醯胺(聚醯胺412)、聚五亞甲基丁二醯胺(聚醯胺54)、聚五亞甲基戊二醯胺(聚醯胺55)、聚五亞甲基己二醯胺(聚醯胺56)、聚五亞甲基辛二醯胺(聚醯胺58)、聚五亞甲基壬二醯胺(聚醯胺59)、聚五亞甲基癸二醯胺(聚醯胺510)、聚五亞甲基十二醯胺(聚醯胺512)、聚六亞甲基丁二醯胺(聚醯胺64)、聚六亞甲基戊二醯胺(聚醯胺65)、聚六亞甲基己二醯胺(聚醯胺66)、聚六亞甲基辛二醯胺(聚醯胺68)、聚六亞甲基壬二醯胺(聚醯胺69)、聚六亞甲基癸二醯胺(聚醯胺610)、聚六亞甲基十二醯胺(聚醯胺6與聚醯胺12之共聚物)、聚六亞甲基十四醯胺(聚醯胺614)、聚六亞甲基十六醯胺(聚醯胺616)、聚六亞甲基十八醯胺(聚醯胺618)、聚九亞甲基己二醯胺(聚醯胺96)、聚九亞甲基辛二醯胺(聚醯胺98)、聚九亞甲基壬二醯胺(聚醯胺99)、聚九亞甲基癸二醯胺(聚醯胺910)、聚九亞甲基十二醯胺(聚醯胺912)、聚十亞甲基己二醯胺(聚醯胺106)、聚十亞甲基辛二醯胺(聚醯胺108)、聚十亞甲基壬二醯胺(聚醯胺109)、聚十亞甲基癸二醯胺(聚醯胺1010)、聚十亞甲基十二醯胺(聚醯胺1012)、聚十二亞甲基己二醯胺(聚醯胺126)、聚十二亞甲基辛二醯胺(聚醯胺128)、聚十二亞甲基壬二醯胺(聚醯胺129)、聚十二亞甲基癸二醯胺(聚醯胺1210)、聚十二亞甲基十二醯胺(聚醯胺1212)等。[Polyuramine Resin] The polyamine resin may, for example, be a homopolymer of an aliphatic polyamine or a copolymer obtained by using a plurality of raw material monomers to be formed (that is, an aliphatic group). Polyamine resin, which is a homopolymer or a copolymer). Specific examples of the homopolymer of the aliphatic polyamine or the copolymer obtained by using the raw material monomers to form the raw materials include, for example, polycaprolactam (polyamine 6) and polyundecinamide. (polyamide 11), polydodecyl decylamine (polyamide 12), polyethylene hexamethyleneamine (polyamine 26), polytetramethylene decylamine (polyamine 44), poly Tetramethylene glutamine (polyamide 45), polytetramethylene hexamethylenediamine (polyamine 46), polytetramethylene octyl decylamine (polyamine 48), polytetrazol Methyl decylamine (polyamide 49), polytetramethylene decylamine (polyamine 410), polytetramethylene decylamine (polyamide 412), polypentamethylene Butanediamine (polyamide 54), polypentamethylene pentamethyleneamine (polyamide 55), polypentamethylene hexamethylenediamine (polyamine 56), polypentamethylene octane Indoleamine (polyamide 58), polypentamethylene decylamine (polyamide 59), polypentamethylene decylamine (polyamine 510), polypentamethylene dodecylamine (polyamide 512), polyhexamethylene butyric acid (polyamine 64), polyhexamethylene pentane amine (polyamine 65), polyhexamethylene hexamethylenediamine (poly Indoleamine 66), Polyhexa Kesin diamine (polyamide 68), polyhexamethylene decylamine (polyamine 69), polyhexamethylene decylamine (polyamide 610), polyhexamethylene ten Diamine (copolymer of polyamine 6 and polyamido 12), polyhexamethylenetetradecylamine (polyamide 614), polyhexamethylene hexadecanamide (polyamide 616), Polyhexamethylene octadecylamine (polyamide 618), poly-n-methylene hexamethylenediamine (polyamine 96), poly-n-methylene octyl decylamine (polyamine 98), poly-nine Methylene quinone diamine (polyamide 99), poly-n-methylene quinone diamine (polyamide 910), poly-n-methylene dodecylamine (polyamide 912), poly-tenthene Dihexylamine (polyamide 106), poly-methylene octyl decylamine (polyamine 108), polydecamethylene decylamine (polyamine 109), polydecamethylene oxime Diamine (polyamide 1010), polydecamethylene dodecylamine (polyamine 1012), polydodesethylene hexamethylenediamine (polyamine 126), polytetramethylene octyl Diamine (polyamide 128), polydodecyl decylamine (polyamide 129), polydodesethylene decylamine (polyamine 1210), polydodel methylene Dodecylamine (polyamine 1212) and the like.

又，作為聚醯胺樹脂，例如也可理想地使用聚間亞二甲苯己二醯胺(聚醯胺MXD6)、聚間亞二甲苯辛二醯胺(聚醯胺MXD8)、聚間亞二甲苯壬二醯胺(聚醯胺MXD9)、聚間亞二甲苯癸二醯胺(聚醯胺MXD10)、聚間亞二甲苯十二醯胺(聚醯胺MXD12)、聚間亞二甲苯對苯二甲醯胺(聚醯胺MXDT)、聚間亞二甲苯間苯二甲醯胺(聚醯胺MXDI)、聚間亞二甲苯六氫對苯二甲醯胺(聚醯胺MXDT(H))、聚間亞二甲苯萘二甲醯胺(聚醯胺MXDN)、聚對亞二甲苯己二醯胺(聚醯胺PXD6)、聚對亞二甲苯辛二醯胺(聚醯胺PXD8)、聚對亞二甲苯壬二醯胺(聚醯胺PXD9)、聚對亞二甲苯癸二醯胺(聚醯胺PXD10)、聚對亞二甲苯十二醯胺(聚醯胺PXD12)、聚對亞二甲苯對苯二甲醯胺(聚醯胺PXDT)、聚對亞二甲苯間苯二甲醯胺(聚醯胺PXDI)、聚對亞二甲苯六氫對苯二甲醯胺(聚醯胺PXDT(H))、聚對亞二甲苯萘二甲醯胺(聚醯胺PXDN)、聚對伸苯基對苯二甲醯胺(PPTA)、聚對伸苯基間苯二甲醯胺(PPIA)、聚間伸苯基對苯二甲醯胺(PMTA)、聚間伸苯基間苯二甲醯胺(PMIA)、聚(2,6-萘二亞甲基己二醯胺)(聚醯胺2,6-BAN6)、聚(2,6-萘二亞甲基辛二醯胺)(聚醯胺2,6-BAN8)、聚(2,6-萘二亞甲基壬二醯胺)(聚醯胺2,6-BAN9)、聚(2,6-萘二亞甲基癸二醯胺)(聚醯胺2,6-BAN10)、聚(2,6-萘二亞甲基十二醯胺)(聚醯胺2,6-BAN12)、聚(2,6-萘二亞甲基對苯二甲醯胺)(聚醯胺2,6-BANT)、聚(2,6-萘二亞甲基間苯二甲醯胺)(聚醯胺2,6-BANI)、聚(2,6-萘二亞甲基六氫對苯二甲醯胺)(聚醯胺2,6-BANT(H))、聚(2,6-萘二亞甲基萘二甲醯胺)(聚醯胺2,6-BANN)、聚(1,3-環己烷二亞甲基己二醯胺)(聚醯胺1,3-BAC6)、聚(1,3-環己烷二亞甲基辛二醯胺(聚醯胺1,3-BAC8)、聚(1,3-環己烷二亞甲基壬二醯胺)(聚醯胺1,3-BAC9)、聚(1,3-環己烷二亞甲基癸二醯胺)(聚醯胺1,3-BAC10)、聚(1,3-環己烷二亞甲基十二醯胺)(聚醯胺1,3-BAC12)、聚(1,3-環己烷二亞甲基對苯二甲醯胺)(聚醯胺1,3-BACT)、聚(1,3-環己烷二亞甲基間苯二甲醯胺)(聚醯胺1,3-BACI)、聚(1,3-環己烷二亞甲基六氫對苯二甲醯胺)(聚醯胺1,3-BACT(H))、聚(1,3-環己烷二亞甲基萘二甲醯胺)(聚醯胺1,3-BACN)、聚(1,4-環己烷二亞甲基己二醯胺)(聚醯胺1,4-BAC6)、聚(1,4-環己烷二亞甲基辛二醯胺)(聚醯胺1,4-BAC8)、聚(1,4-環己烷二亞甲基壬二醯胺)(聚醯胺1,4-BAC9)、聚(1,4-環己烷二亞甲基癸二醯胺)(聚醯胺1,4-BAC10)、聚(1,4-環己烷二亞甲基十二醯胺)(聚醯胺1,4-BAC12)、聚(1,4-環己烷二亞甲基對苯二甲醯胺)(聚醯胺1,4-BACT)、聚(1,4-環己烷二亞甲基間苯二甲醯胺)(聚醯胺1,4-BACI)、聚(1,4-環己烷二亞甲基六氫對苯二甲醯胺)(聚醯胺1,4-BACT(H))、聚(1,4-環己烷二亞甲基萘二甲醯胺)(聚醯胺1,4-BACN)、聚(4,4’-亞甲基雙環伸己基己二醯胺)(聚醯胺PACM6)、聚(4,4’-亞甲基雙環伸己基辛二醯胺)(聚醯胺PACM8)、聚(4,4’-亞甲基雙環伸己基壬二醯胺)(聚醯胺PACM9)、聚(4,4’-亞甲基雙環伸己基癸二醯胺)(聚醯胺PACM10)、聚(4,4’-亞甲基雙環伸己基十二醯胺)(聚醯胺PACM12)、聚(4,4’-亞甲基雙環伸己基十四醯胺)(聚醯胺PACM14)、聚(4,4’-亞甲基雙環伸己基十六醯胺)(聚醯胺PACM16)、聚(4,4’-亞甲基雙環伸己基十八醯胺)(聚醯胺PACM18)、聚(4,4’-亞甲基雙環伸己基對苯二甲醯胺)(聚醯胺PACMT)、聚(4,4’-亞甲基雙環伸己基間苯二甲醯胺)(聚醯胺PACMI)、聚(4,4’-亞甲基雙環伸己基六氫對苯二甲醯胺)(聚醯胺PACMT(H))、聚(4,4’-亞甲基雙環伸己基萘二甲醯胺)(聚醯胺PACMN)、聚(4,4’-亞甲基雙(2-甲基-環伸己基)己二醯胺)(聚醯胺MACM6)、聚(4,4’-亞甲基雙(2-甲基-環伸己基)辛二醯胺)(聚醯胺MACM8)、聚(4,4’-亞甲基雙(2-甲基-環伸己基)壬二醯胺)(聚醯胺MACM9)、聚(4,4’-亞甲基雙(2-甲基-環伸己基)癸二醯胺)(聚醯胺MACM10)、聚(4,4’-亞甲基雙(2-甲基-環伸己基)十二醯胺)(聚醯胺MACM12)、聚(4,4’-亞甲基雙(2-甲基-環伸己基)十四醯胺)(聚醯胺MACM14)、聚(4,4’-亞甲基雙(2-甲基-環伸己基)十六醯胺)(聚醯胺MACM16)、聚(4,4’-亞甲基雙(2-甲基-環伸己基)十八醯胺)(聚醯胺MACM18)、聚(4,4’-亞甲基雙(2-甲基-環伸己基)對苯二甲醯胺)(聚醯胺MACMT)、聚(4,4’-亞甲基雙(2-甲基-環伸己基)間苯二甲醯胺)(聚醯胺MACMI)、聚(4,4’-亞甲基雙(2-甲基-環伸己基)六氫對苯二甲醯胺)(聚醯胺MACMT(H))、聚(4,4’-亞甲基雙(2-甲基-環伸己基)萘二甲醯胺)(聚醯胺MACMN)、聚(4,4’-伸丙基雙環伸己基己二醯胺)(聚醯胺PACP6)、聚(4,4’-伸丙基雙環伸己基辛二醯胺)(聚醯胺PACP8)、聚(4,4’-伸丙基雙環伸己基壬二醯胺)(聚醯胺PACP9)、聚(4,4’-伸丙基雙環伸己基癸二醯胺)(聚醯胺PACP10)、聚(4,4’-伸丙基雙環伸己基十二醯胺)(聚醯胺PACP12)、聚(4,4’-伸丙基雙環伸己基十四醯胺)(聚醯胺PACP14)、聚(4,4’-伸丙基雙環伸己基十六醯胺)(聚醯胺PACP16)、聚(4,4’-伸丙基雙環伸己基十八醯胺)(聚醯胺PACP18)、聚(4,4’-伸丙基雙環伸己基對苯二甲醯胺)(聚醯胺PACPT)、聚(4,4’-伸丙基雙環伸己基間苯二甲醯胺)(聚醯胺PACPI)、聚(4,4’-伸丙基雙環伸己基六氫對苯二甲醯胺)(聚醯胺PACPT(H))、聚(4,4’-伸丙基雙環伸己基萘二甲醯胺)(聚醯胺PACPN)、聚異佛酮己二醯胺(聚醯胺IPD6)、聚異佛酮辛二醯胺(聚醯胺IPD8)、聚異佛酮壬二醯胺(聚醯胺IPD9)、聚異佛酮癸二醯胺(聚醯胺IPD10)、聚異佛酮十二醯胺(聚醯胺IPD12)、聚異佛酮對苯二甲醯胺(聚醯胺IPDT)、聚異佛酮間苯二甲醯胺(聚醯胺IPDI)、聚異佛酮六氫對苯二甲醯胺(聚醯胺IPDT(H))、聚異佛酮萘二甲醯胺(聚醯胺IPDN)、聚四亞甲基對苯二甲醯胺(聚醯胺4T)、聚四亞甲基間苯二甲醯胺(聚醯胺4I)、聚四亞甲基六氫對苯二甲醯胺(聚醯胺4T(H))、聚四亞甲基萘二甲醯胺(聚醯胺4N)、聚五亞甲基對苯二甲醯胺(聚醯胺5T)、聚五亞甲基間苯二甲醯胺(聚醯胺5I)、聚五亞甲基六氫對苯二甲醯胺(聚醯胺5T(H))、聚五亞甲基萘二甲醯胺(聚醯胺5N)、聚六亞甲基對苯二甲醯胺(聚醯胺6T)、聚六亞甲基間苯二甲醯胺(聚醯胺6I)、聚六亞甲基六氫對苯二甲醯胺(聚醯胺6T(H))、聚六亞甲基萘二甲醯胺(聚醯胺6N)、聚(2-甲基五亞甲基對苯二甲醯胺)(聚醯胺M5T)、聚(2-甲基五亞甲基間苯二甲醯胺)(聚醯胺M5I)、聚(2-甲基五亞甲基六氫對苯二甲醯胺)(聚醯胺M5T(H))、聚(2-甲基五亞甲基萘二甲醯胺(聚醯胺M5N)、聚九亞甲基對苯二甲醯胺(聚醯胺9T)、聚九亞甲基間苯二甲醯胺(聚醯胺9I)、聚九亞甲基六氫對苯二甲醯胺(聚醯胺9T(H))、聚九亞甲基萘二甲醯胺(聚醯胺9N)、聚(2-甲基八亞甲基對苯二甲醯胺)(聚醯胺M8T)、聚(2-甲基八亞甲基間苯二甲醯胺)(聚醯胺M8I)、聚(2-甲基八亞甲基六氫對苯二甲醯胺)(聚醯胺M8T(H))、聚(2-甲基八亞甲基萘二甲醯胺)(聚醯胺M8N)、聚三甲基六亞甲基對苯二甲醯胺(聚醯胺TMHT)、聚三甲基六亞甲基間苯二甲醯胺(聚醯胺TMHI)、聚三甲基六亞甲基六氫對苯二甲醯胺(聚醯胺TMHT(H))、聚三甲基六亞甲基萘二甲醯胺(聚醯胺TMHN)、聚十亞甲基對苯二甲醯胺(聚醯胺10T)、聚十亞甲基間苯二甲醯胺(聚醯胺10I)、聚十亞甲基六氫對苯二甲醯胺(聚醯胺10T(H))、聚十亞甲基萘二甲醯胺(聚醯胺10N)、聚十一亞甲基對苯二甲醯胺(聚醯胺11T)、聚十一亞甲基間苯二甲醯胺(聚醯胺11I)、聚十一亞甲基六氫對苯二甲醯胺(聚醯胺11T(H))、聚十一亞甲基萘二甲醯胺(聚醯胺11N)、聚十二亞甲基對苯二甲醯胺(聚醯胺12T)、聚十二亞甲基間苯二甲醯胺(聚醯胺12I)、聚十二亞甲基六氫對苯二甲醯胺(聚醯胺12T(H))、聚十二亞甲基萘二甲醯胺(聚醯胺12N)、或使用數種該等聚醯胺樹脂之原料單體而得之共聚物等。Further, as the polyamine resin, for example, polymethylene xylene hexamethylenediamine (polyamine MXD6), polymethylene xylene octane amide (polyamine MXD8), polymethylene ii can also be preferably used. Toluene decylamine (polyamine MXD9), polymethylene xylene decylamine (polyamide MXD10), polymethylene xylene decylamine (polyamine MXD12), polymethylene xylene Benzoguanamine (polyamine MXDT), polymethylene xylene metaxylamine (polyamine MXDI), polymethylene xylene hexahydroterephthalamide (polyamine MXDT (H )), polymethylene xylene naphthylamine (polyamine MXDN), poly-p-xylene hexamethylenediamine (polyamine PXD6), poly-p-xylene octane amide (polyamine PXD8) ), poly-p-xylylene diamine (polyamine PXD9), poly-p-xylylene diamine (polyamine PXD10), poly-p-xylene dodecylamine (polyamine PXD12), Poly-p-xylene terephthalamide (polyamine PXDT), poly-p-xylene meta-xylamine (polyamine PXDI), poly-p-xylene hexahydro-p-xylamine ( Polyamide PXDT(H)), poly-p-xylylene naphthylamine (polyamine PXDN), poly-p-phenylene Terephthalamide (PPTA), polyparaphenylene phthalic acid (PPIA), poly(phenylene terephthalamide) (PMTA), poly(phenylene isophthalate) Amine (PMIA), poly(2,6-naphthalenediethylene hexamethylenediamine) (polyamine 2,6-BAN6), poly(2,6-naphthalenedimethyleneoctylamine) (poly Indole 2,6-BAN8), poly(2,6-naphthalene dimethylene decylamine) (polyamine 2,6-BAN9), poly(2,6-naphthalene dimethylene fluorene dioxime) Amine) (polyamine 2,6-BAN10), poly(2,6-naphthalenediethylenedodecylamine) (polyamine 2,6-BAN12), poly(2,6-naphthalene dimethylene) (p-xylyleneamine) (polyamine 2,6-BANT), poly(2,6-naphthalenedimethylene m-xylyleneamine) (polyamine 2,6-BANI), poly( 2,6-naphthalene dimethylene hexahydrophthalamide) (polyamine 2,6-BANT (H)), poly(2,6-naphthalenedi-dimethylnaphthalene) Polyamide 2,6-BANN), poly(1,3-cyclohexanedimethylene hexanediamine) (polyamine 1,3-BAC6), poly(1,3-cyclohexanedi Methyl octyl decylamine (polyamine 1,3-BAC8), poly(1,3-cyclohexane dimethylene hydrazine diamine) (polyamine 1,3-BAC9), poly (1, 3-cyclohexane dimethylene quinone diamine (polyamine 1,3-BAC10), poly(1,3-cyclohexane dimethylene twelve Amine) (polyamine 1,3-BAC12), poly(1,3-cyclohexanedimethylene terephthalamide) (polyamine 1,3-BACT), poly(1,3- Cyclohexane dimethylene isophthalamide) (polyamine 1,3-BACI), poly(1,3-cyclohexane dimethylene hexahydrobenzamide) (poly fluorene) Amine 1,3-BACT(H)), poly(1,3-cyclohexanedimethylenenaphthalene) (polyamine 1,3-BACN), poly(1,4-cyclohexane Dimethylene hexamethylenediamine) (polyamine 1,4-BAC6), poly(1,4-cyclohexanedimethylene octylamine) (polyamine 1,4-BAC8), poly (1,4-cyclohexanedimethylidene quinone diamine) (polyamido 1,4-BAC9), poly(1,4-cyclohexanedimethylene quinone diamine) (polyamine) 1,4-BAC10), poly(1,4-cyclohexanedimethylenedodecylamine) (polyamido 1,4-BAC12), poly(1,4-cyclohexanedimethylene pair) Benzoxamine) (polyamine 1,4-BACT), poly(1,4-cyclohexanedimethylene m-xylyleneamine) (polyamine 1,4-BACI), poly( 1,4-cyclohexanedimethylene hexahydrophthalamide) (polyamine 1,4-BACT (H)), poly(1,4-cyclohexane dimethylene naphthalene) Indoleamine (polyamine 1,4-BACN), poly(4,4'-methylenebiscyclohexylhexamethyleneamine) (polyamine PACM6), poly(4,4'- Methylene bicyclohexyl octyl octylamine) (polyamine PACM8), poly(4,4'-methylenebiscyclohexyl decylamine) (polyamine PACM9), poly(4,4'- Methylene bicyclohexyl decylamine (polyamido PACM10), poly(4,4'-methylenebiscyclohexyldecylamine) (polyamine PACM12), poly(4,4'- Methylene bicyclohexyl hexyl decylamine) (polyamido PACM14), poly(4,4'-methylenebiscyclohexylhexadecaneamine) (polyamine PACM16), poly(4,4'- Methylene bicyclohexyl octadecylamine (polyamide PACM18), poly(4,4'-methylenebiscyclohexyl p-xylyleneamine) (polyamine PACMT), poly (4,4 '-methylenebicyclohexylhexyl phthaliminamine (polyamide PACMI), poly(4,4'-methylenebiscyclohexylhexahydrop-xylyleneamine) (polyamine PACMT ( H)), poly(4,4'-methylenebiscyclohexylnaphthalenylamine) (polyamine PACMN), poly(4,4'-methylenebis(2-methyl-cyclohexyl) Dihexylamine) (polyamine MACM6), poly(4,4'-methylenebis(2-methyl-cyclohexyl)octylamine) (polyamine MACM8), poly(4, 4'-methylenebis(2-methyl-cyclohexyl)decylamine (polyamine MACM9), poly(4 , 4'-methylenebis(2-methyl-cyclohexyl)decylamine (polyamine amine MACM10), poly(4,4'-methylenebis(2-methyl-cyclohexyl) ) dodecylamine (polyamine MACM12), poly(4,4'-methylenebis(2-methyl-cyclohexyl)tetradecylamine) (polyamine MACM14), poly(4, 4'-methylenebis(2-methyl-cyclohexyl)hexadecane) (polyamine MACM16), poly(4,4'-methylenebis(2-methyl-cyclohexyl) Octadecane) (polyamine MACM18), poly(4,4'-methylenebis(2-methyl-cyclohexyl)terephthalamide) (polyamine MACMT), poly(4 , 4'-methylenebis(2-methyl-cyclohexyl)m-xylyleneamine) (polyamine MACMI), poly(4,4'-methylenebis(2-methyl-ring) Hexyl) hexahydro-p-xylguanamine) (polyamine MACMT (H)), poly(4,4'-methylenebis(2-methyl-cyclohexyl)naphthyldimethylamine) Polyamine MACMN), poly(4,4'-propylbiscyclohexylhexamethylenediamine) (polyamine PACP6), poly(4,4'-propylbiscyclohexyloctylamine) Polyamine PACP8), poly(4,4'-propylbiscyclohexyldecylamine) (polyamine PACP9), poly(4,4'-propylbiscyclohexyldecylamine) Polyamine PACP10) Poly(4,4'-propyl propylcyclohexyldecylamine) (polyamine PACP12), poly(4,4'-propyl bis-cyclohexyltetradecylamine) (polyamine PACP14), Poly(4,4'-propyl propylcyclohexylhexadecane) (polyamine PACP16), poly(4,4'-propylbiscyclohexyl octadecylamine) (polyamine PACP18), Poly(4,4'-propyl bis-cyclohexyl-p-xylyleneamine) (polyamine PACPT), poly(4,4'-propyl bis-cyclohexyl-xylylene phthalamide) Amine PACPI), poly(4,4'-propylbiscyclohexylhexahydrop-xylyleneamine) (polyamine PACPT(H)), poly(4,4'-propyl propylcyclohexylnaphthalene) Dimethylguanamine) (polyamido PACPN), polyisophorone hexamethylenediamine (polyamide IPD6), polyisophorone octaneamine (polyamine IPD8), polyisoxanthone oxime (Polyuramine IPD9), polyisophorone decylamine (polyamide IPD10), polyisophorone dodecylamine (polyamine IPD12), polyisophorone terephthalamide (polyfluorene) Amine IPDT), polyisophorone m-xylamine (polyamine IPDI), polyisophorone hexahydroterephthalamide (polyamine IPDT (H)), polyisophorone naphthalene Indoleamine (polyamine IPDN), polytetramethylene pair Dimethylamine (polyamine 4T), polytetramethylene meta-xylamine (polyamine 4I), polytetramethylene hexahydrophthalamide (polyamine 4T (H) ), polytetramethylene naphthylamine (polyamine 4N), polypentamethylene terephthalamide (polyamine 5T), polypentamethylene metabenzamide (poly) Indole 5I), polypentamethylene hexahydrophthalamide (polyamine 5T(H)), polypentamethylene naphthylamine (polyamine 5N), polyhexamethylene Para-xylamine (polyamine 6T), polyhexamethylene meta-xylamine (polyamine 6I), polyhexamethylene hexahydro-p-xylamine (polyamine 6T ( H)), polyhexamethylene naphthylamine (polyamine 6N), poly(2-methylpentamethyleneparaben) (polyamine M5T), poly (2-A) 5-pentamethylene m-xylamine (polyamine M5I), poly(2-methylpentamethylenehexahydrop-xylyleneamine) (polyamine M5T(H)), poly( 2-methylpentamethylenenaphthalene (polyamine M5N), poly-n-methylene-p-xylamine (polyamine 9T), poly-n-methylene metabenzamide ( Polyamido 9I), poly-n-methylene hexahydro-p-xylamine (polyamine 9T(H)), poly-nine Naphthyldimethylamine (polyamine 9N), poly(2-methyl octamethyl-p-xylyleneamine) (polyamine M8T), poly(2-methyl octamethyl-m-phenylene) Myramine) (polyamine M8I), poly(2-methyl octamethylene hexahydroterephthalamide) (polyamine M8T (H)), poly (2-methyl octamethylene) Naphthylamine (polyamine M8N), polytrimethylhexamethylene terephthalamide (polyamine TMHT), polytrimethylhexamethylene metabenzamide (poly Indole TMHI, polytrimethylhexamethylene hexahydrophthalamide (polyamine TMHT(H)), polytrimethylhexamethylenenaphthalene (polyamine TMHN) , poly-methylene-p-xylyleneamine (polyamine 10T), poly-methylene meta-xylyleneamine (polyamine 10I), poly-methylene hexahydro-p-xylamine (Polymeramine 10T (H)), poly-methylene naphthalene dimethyl decylamine (polyamine 10N), polyundecethylene terephthalamide (polyamine 11T), poly eleven Methyl m-xylylene amide (polyamine 11I), polyundecethylene hexahydrophthalamide (polyamine 11T (H)), polyundecethylene naphthylamine (polyamido 11N), polydodecyl-p-xylamine (polyamine 12T) , poly-t-methylene meta-xylylene amide (polyamine 12I), poly-dodecyl hexahydro-p-xylamine (polyamine 12T (H)), polytetramethylene Naphthyldimethylamine (polyamine 12N) or a copolymer obtained by using a plurality of raw material monomers of the polyamidamide resins.

上述聚醯胺樹脂之具體例中，宜使用選自於由聚己內醯胺(聚醯胺6)、聚間亞二甲苯己二醯胺(聚醯胺MXD6)、聚十一烷醯胺(聚醯胺11)、聚十二烷醯胺(聚醯胺12)、聚六亞甲基己二醯胺(聚醯胺66)、聚六亞甲基癸二醯胺(聚醯胺610)、聚六亞甲基十二醯胺(聚醯胺6與聚醯胺12之共聚物)、聚十亞甲基癸二醯胺(聚醯胺1010)、聚十亞甲基十二醯胺(聚醯胺1012)、及聚十二亞甲基十二醯胺(聚醯胺1212)構成之群組中之至少1種均聚物、及/或使用數種形成該等之原料單體而得之共聚物更佳，使用選自於由聚己內醯胺(聚醯胺6)、聚十一烷醯胺(聚醯胺11)、聚十二烷醯胺(聚醯胺12)、聚六亞甲基己二醯胺(聚醯胺66)構成之群組中之至少1種均聚物、及/或使用數種形成該等之原料單體而得之共聚物尤佳，聚己內醯胺(聚醯胺6)特佳。 本發明之聚醯胺樹脂組成物所包含之聚醯胺樹脂，其90質量%以上宜為脂肪族聚醯胺樹脂(例如，聚醯胺6)較佳，95質量%以上為脂肪族聚醯胺樹脂(例如，聚醯胺6)更佳，99質量%以上為脂肪族聚醯胺樹脂(例如，聚醯胺6)尤佳，實質上100質量%為脂肪族聚醯胺樹脂(例如，聚醯胺6)又更佳。實質上100質量%不包括無意間摻入雜質等，係指全部聚醯胺樹脂為脂肪族聚醯胺樹脂(例如，聚醯胺6)。In the specific example of the above polyamido resin, it is preferred to use a polycaprolactam (polyamine 6), polymethylene xylene hexamethylenediamine (polyamine MXD6), polyundecinamide (polyamide 11), polydodecyl decylamine (polyamide 12), polyhexamethylene hexamethylenediamine (polyamine 66), polyhexamethylene decylamine (polyamine 610) ), polyhexamethylene dodecylamine (copolymer of polyamido 6 and polydecylamine 12), polydecamethylene decylamine (polyamine 1010), polydecylmethyl fluorene At least one homopolymer of the group consisting of an amine (polyamide 1012) and polydodedomene dodecylamine (polyamide 1212), and/or using a plurality of raw material sheets forming the same The resulting copolymer is more preferably selected from the group consisting of polycaprolactam (polyamine 6), polyundecylamine (polyamine 11), and polydodecylamine (polyamine 12). And at least one homopolymer of the group consisting of polyhexamethylene hexamethylenediamine (polyamide 66), and/or copolymers obtained by using a plurality of raw material monomers forming the materials Polyhexylamine (polyamine 6) is particularly preferred. Preferably, 90% by mass or more of the polyamine resin contained in the polyamide resin composition of the present invention is an aliphatic polyamine resin (for example, polyamine 6), and 95% by mass or more is an aliphatic polyfluorene. An amine resin (for example, polyamine 6) is more preferable, and 99% by mass or more is preferably an aliphatic polyamine resin (for example, polyamine 6), and substantially 100% by mass is an aliphatic polyamide resin (for example, Polyamide 6) is even better. In essence, 100% by mass does not include inadvertent incorporation of impurities or the like, and means that all of the polyamide resin is an aliphatic polyamide resin (for example, polyamine 6).

本發明之聚醯胺樹脂組成物中之聚醯胺樹脂之合計量宜為組成物之80質量%以上較佳，85質量%以上更佳，90質量%以上尤佳，92質量%以上又更佳。前述聚醯胺樹脂之合計量宜為99.88質量%以下較佳，也可為99質量%以下。 就聚醯胺樹脂而言，上述聚醯胺樹脂可1種單獨使用，亦可將多種聚醯胺樹脂混合使用。摻合多種時，合計量宜為上述範圍較佳。The total amount of the polyamide resin in the polyamide resin composition of the present invention is preferably 80% by mass or more, more preferably 85% by mass or more, more preferably 90% by mass or more, and even more preferably 92% by mass or more. good. The total amount of the polyamide resin is preferably 99.88 mass% or less, and may be 99 mass% or less. In the case of the polyamide resin, the above polyamine resin may be used singly or in combination of a plurality of polyamide resins. When a plurality of kinds are blended, the total amount is preferably in the above range.

［烯烴系彈性體］ 烯烴系彈性體係將選自於乙烯及丙烯中之至少1種和選自於α,β-不飽和羧酸單體及α,β-不飽和羧酸酯單體中之至少1種予以共聚而得的聚合物。[Olefin-based elastomer] The olefin-based elastomer system is selected from at least one selected from the group consisting of ethylene and propylene, and selected from the group consisting of α,β-unsaturated carboxylic acid monomers and α,β-unsaturated carboxylic acid ester monomers. At least one polymer obtained by copolymerization.

作為α,β-不飽和羧酸單體，可列舉丙烯酸及甲基丙烯酸等。Examples of the α,β-unsaturated carboxylic acid monomer include acrylic acid and methacrylic acid.

作為α,β-不飽和羧酸酯單體，可列舉該等不飽和羧酸之甲酯、乙酯、丙酯、丁酯、戊酯、己酯、庚酯、辛酯、壬酯、癸酯或該等之混合物等。Examples of the α,β-unsaturated carboxylic acid ester monomer include methyl ester, ethyl ester, propyl ester, butyl ester, pentyl ester, hexyl ester, heptyl ester, octyl ester, decyl ester, and oxime of the unsaturated carboxylic acid. Ester or a mixture of these, and the like.

作為烯烴系彈性體，可列舉乙烯・α,β-不飽和羧酸系共聚物、丙烯・α,β-不飽和羧酸系共聚物、乙烯・丙烯・α,β-不飽和羧酸系共聚物、乙烯・α,β-不飽和羧酸酯系共聚物、丙烯・α,β-不飽和羧酸酯系共聚物、乙烯・丙烯・α,β-不飽和羧酸酯系共聚物、乙烯・α,β-不飽和羧酸/不飽和羧酸酯系共聚物、丙烯・α,β-不飽和羧酸/不飽和羧酸酯系共聚物、乙烯・丙烯・α,β-不飽和羧酸/不飽和羧酸酯系共聚物。就烯烴系彈性體而言，上述烯烴系彈性體可1種單獨使用，亦可將多種烯烴系彈性體混合使用。Examples of the olefin-based elastomer include an ethylene/α,β-unsaturated carboxylic acid copolymer, a propylene/α,β-unsaturated carboxylic acid copolymer, and an ethylene/propylene/α,β-unsaturated carboxylic acid copolymer. , 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, 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,β-unsaturated carboxylic acid An acid/unsaturated carboxylic acid ester copolymer. In the olefin-based elastomer, the olefin-based elastomer may be used singly or in combination of a plurality of olefin-based elastomers.

該等中，乙烯與(甲基)丙烯酸酯單體共聚而得之乙烯-(甲基)丙烯酸酯共聚物為較佳，具體而言，乙烯-丙烯酸乙酯共聚物、乙烯-丙烯酸甲酯共聚物、乙烯-甲基丙烯酸乙酯共聚物等更佳。其中，以成形時的熱穩定性和少量添加時的效果的觀點觀之，乙烯-丙烯酸乙酯共聚物可理想地用作烯烴系彈性體。Among these, an ethylene-(meth) acrylate copolymer obtained by copolymerizing ethylene with a (meth) acrylate monomer is preferable, specifically, an ethylene-ethyl acrylate copolymer and an ethylene-methyl acrylate copolymer. A material, an ethylene-ethyl methacrylate copolymer or the like is more preferable. Among them, the ethylene-ethyl acrylate copolymer is desirably used as an olefin-based elastomer from the viewpoint of thermal stability at the time of molding and an effect at the time of small addition.

本發明中，尤其乙烯-(甲基)丙烯酸酯共聚物中之(甲基)丙烯酸酯之含量宜為5～30質量%較佳。藉由成為如此之範圍，可進一步改善薄膜的耐針孔性。In the present invention, the content of the (meth) acrylate in the ethylene-(meth) acrylate copolymer is preferably from 5 to 30% by mass. By being such a range, the pinhole resistance of the film can be further improved.

本發明之聚醯胺樹脂組成物中，烯烴系彈性體之含量為聚醯胺樹脂組成物之0.1質量%～5質量%。藉由烯烴系彈性體之含量為0.1質量%以上，可改善使用聚醯胺樹脂組成物之樹脂薄膜的耐針孔性。以同樣的觀點觀之，烯烴系彈性體之含量宜為0.5質量%以上較佳，0.8質量%以上更佳，1質量%以上尤佳。又，藉由烯烴系彈性體之含量為5質量%以下，可維持使用聚醯胺樹脂組成物之樹脂薄膜的透明性。以同樣的觀點觀之，烯烴系彈性體之含量宜為4質量%以下較佳，3.5質量%以下更佳，3質量%以下尤佳。In the polyamine resin composition of the present invention, the content of the olefin-based elastomer is from 0.1% by mass to 5% by mass based on the polyamine resin composition. When the content of the olefin-based elastomer is 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-based elastomer is preferably 0.5% by mass or more, more preferably 0.8% by mass or more, and particularly preferably 1% by mass or more. In addition, the content of the olefin-based elastomer is 5% by mass or less, and the transparency of the resin film using the polyamide resin composition can be maintained. From the same viewpoint, the content of the olefin-based elastomer is preferably 4% by mass or less, more preferably 3.5% by mass or less, and particularly preferably 3% by mass or less.

烯烴系彈性體可1種單獨使用，亦可將多種烯烴系彈性體混合使用。使用多種時，合計量宜為上述範圍較佳。The olefin-based elastomer may be used singly or in combination of a plurality of olefin-based elastomers. When a plurality of types are used, the total amount is preferably in the above range.

尤其本發明之聚醯胺樹脂組成物中，乙烯-丙烯酸乙酯共聚物之含量宜為0.1質量%～5質量%較佳。藉由乙烯-丙烯酸乙酯共聚物之含量為0.1質量%以上，可更有效地改善使用聚醯胺樹脂組成物之樹脂薄膜的耐針孔性。以同樣的觀點觀之，乙烯-丙烯酸乙酯共聚物之含量宜為0.5質量%以上更佳，0.8質量%以上尤佳，1質量%以上又更佳。又，藉由乙烯-丙烯酸乙酯共聚物之含量為5質量%以下，可將使用聚醯胺樹脂組成物之樹脂薄膜的透明性維持在更高水平。以同樣的觀點觀之，乙烯-丙烯酸乙酯共聚物之含量宜為4質量%以下更佳，3.5質量%以下尤佳，3質量%以下又更佳。In particular, the content of the ethylene-ethyl acrylate copolymer in the polyamide resin composition of the present invention is preferably from 0.1% by mass to 5% by mass. When the content of the ethylene-ethyl acrylate copolymer is 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 preferably 0.5% by mass or more, more preferably 0.8% by mass or more, and still more preferably 1% by mass or more. In addition, the content of the ethylene-ethyl acrylate copolymer is 5% by mass or less, and the transparency of the resin film using the polyamide resin composition can be maintained at a higher level. From the same viewpoint, the content of the ethylene-ethyl acrylate copolymer is preferably 4% by mass or less, more preferably 3.5% by mass or less, and still more preferably 3% by mass or less.

就烯烴系彈性體而言，上述乙烯-丙烯酸乙酯共聚物可1種單獨使用，亦可將多種烯烴系彈性體混合使用。使用多種時，合計量宜為上述範圍較佳。In the olefin-based elastomer, the ethylene-ethyl acrylate copolymer may be used singly or in combination of a plurality of olefin-based elastomers. When a plurality of types are used, the total amount is preferably in the above range.

［抗氧化劑］ 就抗氧化劑而言，可列舉IRGANOX1098為代表的苯酚系抗氧化劑、受阻胺系抗氧化劑、IRGAFOS168等為代表的磷系抗氧化劑、硫系抗氧化劑、聯胺系抗氧化劑、醯胺系抗氧化劑等，本發明中宜使用苯酚系抗氧化劑較佳。作為具體例，例如可列舉雙[3-(3-第三丁基-4-羥基-5-甲基苯基)丙酸][伸乙基雙(氧乙烯)]、N’,N’-雙-3-(3’-5’二-第三丁基-4’-羥基苯基)丙醯基己二胺、新戊四醇肆[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯]等。其中，N’,N’-雙-3-(3’-5’二-第三丁基-4’-羥基苯基)丙醯基己二胺可理想地用作苯酚系抗氧化劑。[Antioxidant] Examples of the antioxidant include a phenol-based antioxidant represented by IRGANOX 1098, a hindered amine-based antioxidant, a phosphorus-based antioxidant typified by IRGAFOS 168, a sulfur-based antioxidant, a hydrazine-based antioxidant, and a guanamine. It is an antioxidant, etc., and it is preferable to use a phenol type antioxidant in this invention. Specific examples include bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid] [extended ethyl bis(oxyethylene)], N', N'- Bis-3-(3'-5'di-tert-butyl-4'-hydroxyphenyl)propanylhexamethylenediamine, neopentyl quinone [3-(3,5-di-t-butyl) -4-hydroxyphenyl)propionate] and the like. Among them, N',N'-bis-3-(3'-5'di-t-butyl-4'-hydroxyphenyl)propanylhexamethylenediamine is preferably used as a phenol-based antioxidant.

本發明之聚醯胺樹脂組成物中，抗氧化劑之含量為0.01質量%～1質量%。藉由抗氧化劑之含量為0.01質量%以上，可抑制使用聚醯胺樹脂組成物之樹脂薄膜之熱水處理後的物性降低、耐折曲性降低。以同樣的觀點觀之，抗氧化劑之含量宜為0.05質量%以上較佳，0.08質量%以上更佳，0.1質量%以上尤佳。抗氧化劑之含量超過1質量%的話，可期待更長期間的耐熱性，以具實用性材料成本的觀點觀之，抗氧化劑之含量為1質量%以下，0.8質量%以下較佳，0.5質量%以下尤佳，0.3質量%以下又更佳。In the polyamine resin composition of the present invention, the content of the antioxidant is from 0.01% by mass to 1% by mass. When the content of the antioxidant is 0.01% by mass or more, the physical properties of the resin film using the polyamide resin composition after the hot water treatment are lowered and the bending resistance is lowered. 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 particularly preferably 0.1% by mass or more. When the content of the antioxidant is more than 1% by mass, heat resistance for a longer period of time can be expected, and from the viewpoint of practical material cost, the content of the antioxidant is 1% by mass or less, preferably 0.8% by mass or less, and 0.5% by mass. The following is particularly preferable, and 0.3% by mass or less is more preferable.

就抗氧化劑而言，上述抗氧化劑可1種單獨使用，亦可將多種抗氧化劑混合使用。使用多種時，合計量宜為上述範圍較佳。In the case of the antioxidant, the above antioxidants may be used singly or in combination of a plurality of antioxidants. When a plurality of types are used, the total amount is preferably in the above range.

［離子聚合物樹脂］ 關於離子聚合物樹脂，係將烯烴單元與α,β-不飽和羧酸單元構成之主鏈的側鏈羧基以金屬離子進行部分中和(介由金屬離子交聯)而得的烯烴/不飽和羧酸共聚物。[Ion Polymer Resin] In the ionic polymer resin, the side chain carboxyl group of the main chain composed of the olefin unit and the α,β-unsaturated carboxylic acid unit is partially neutralized by metal ions (crosslinked by metal ions). The resulting olefin/unsaturated carboxylic acid copolymer.

烯烴可例示乙烯、丙烯等，其中，宜使用乙烯較佳。α,β-不飽和羧酸宜使用丙烯酸、甲基丙烯酸較佳，亦可將其他α,β-不飽和羧酸酯予以共聚。 本發明中，尤其離子聚合物樹脂宜包含乙烯-甲基丙烯酸共聚物及乙烯-丙烯酸共聚物中之至少一者較佳。The olefin may, for example, be ethylene, propylene or the like. Among them, ethylene is preferably used. As the α,β-unsaturated carboxylic acid, acrylic acid or methacrylic acid is preferably used, and other α,β-unsaturated carboxylic acid esters may be copolymerized. In the present invention, it is preferred that the ionic polymer resin particularly contains at least one of an ethylene-methacrylic acid copolymer and an ethylene-acrylic acid copolymer.

作為中和羧基的金屬離子成分，可列舉鋰離子、鈉離子、鉀離子、鎂離子、鈣離子、鍶離子、鋇離子等鹼金屬離子；鹼土類金屬離子；鋁離子、錫離子、鈦離子、錳離子、鐵離子、鎳離子、銅離子、鋅離子、鎘離子等。該等金屬離子成分可1種單獨使用，亦使用2種以上。該等中，將鋅離子、鈉離子作為金屬離子成分使用的話，考量改善和聚醯胺樹脂的親和性的觀點為較佳，鋅離子尤佳。離子聚合物樹脂之羧基的中和度(中和羧基數相對於全部羧基數的比例(中和羧基數/全部羧基數)×100(單位：%))宜為20%～80%較佳，30%～70%更佳。離子聚合物樹脂之羧基的中和度為20%以上的話，獲得之薄膜的透明性變得良好而較佳。離子聚合物樹脂之羧基的中和度為80%以下的話，可避免離子聚合物樹脂的熔融流動性降低，獲得之薄膜的透明性變得良好，故較佳。Examples of the metal ion component that neutralizes the carboxyl group include alkali metal ions such as lithium ions, sodium ions, potassium ions, magnesium ions, calcium ions, barium ions, and cesium ions; alkaline earth metal ions; aluminum ions, tin ions, titanium ions, Manganese ion, iron ion, nickel ion, copper ion, zinc ion, cadmium ion, and the like. These metal ion components may be used alone or in combination of two or more. In the above, when zinc ions and sodium ions are used as the metal ion component, it is preferable from the viewpoint of improving the affinity with the polyamide resin, and zinc ions are particularly preferable. The degree of neutralization of the carboxyl group of the ionic polymer resin (the ratio of the number of neutralized carboxyl groups to the total number of carboxyl groups (the number of neutralized carboxyl groups / the total number of carboxyl groups) × 100 (unit: %)) is preferably from 20% to 80%. 30% to 70% is better. When the degree of neutralization of the carboxyl group of the ionic polymer resin is 20% or more, the transparency of the obtained film becomes good and is preferable. When the degree of neutralization of the carboxyl group of the ionic polymer resin is 80% or less, the melt fluidity of the ionic polymer resin can be prevented from being lowered, and the transparency of the obtained film becomes good, which is preferable.

聚醯胺樹脂組成物中之離子聚合物樹脂之含量，以和聚醯胺樹脂及烯烴系彈性體的相容性的觀點觀之，於聚醯胺樹脂組成物中宜為0.01質量%以上較佳，更佳為0.05質量%以上，尤佳為0.1質量%以上。同樣，以薄膜的透明性的觀點觀之，宜為3質量%以下較佳，更佳為1質量%以下，又更佳為0.6質量%以下。就離子聚合物樹脂而言，於聚醯胺樹脂組成物中可僅含有1種，亦可含有2種以上。含有2種以上時，合計量宜為上述範圍較佳。 又，關於離子聚合物樹脂，在聚醯胺樹脂組成物或薄膜中，也會有離子聚合物樹脂彼此反應或與其他成分反應的情況，此種情況自不必說也包含於本發明之聚醯胺樹脂組成物或薄膜之範圍內。The content of the ionic polymer resin in the polyamide resin composition is preferably 0.01% by mass or more based on the compatibility with the polyamide resin and the olefin elastomer. More preferably, it is 0.05% by mass or more, and particularly preferably 0.1% by mass or more. Similarly, from the viewpoint of transparency of the film, it is preferably 3% by mass or less, more preferably 1% by mass or less, still more preferably 0.6% by mass or less. In the ionic polymer resin, the polyamine resin composition may contain only one type or two or more types. When two or more types are contained, the total amount is preferably in the above range. Further, in the ionic polymer resin, in the polyamide resin composition or the film, the ionic polymer resin may react with each other or with other components, and it is needless to say that it is also included in the present invention. Within the range of the amine resin composition or film.

本發明中，又，聚醯胺樹脂組成物中之離子聚合物樹脂與烯烴系彈性體的質量比(離子聚合物樹脂/烯烴系彈性體)宜為0.04～0.4較佳。前述質量比率的下限值宜為0.05以上更佳，前述質量比的上限值宜為0.3以下更佳。藉由成為如此之範圍，獲得之薄膜的拉伸彈性模量有進一步改善的傾向。 尤其烯烴系彈性體及離子聚合物樹脂宜各自獨立地包含乙烯-甲基丙烯酸共聚物及乙烯-丙烯酸共聚物中之至少一者較佳。此時，兩者的相容性提高，可更有效地發揮上述效果。In the present invention, the mass ratio of the ionic polymer resin to the olefin-based elastomer (ionic polymer resin/olefin-based elastomer) in the polyamide resin composition is preferably from 0.04 to 0.4. The lower limit of the mass ratio is preferably 0.05 or more, and the upper limit of the mass ratio is preferably 0.3 or less. By such a range, the tensile modulus of the obtained film tends to be further improved. In particular, it is preferred that at least one of the olefin-based elastomer and the ionic polymer resin independently comprise at least one of an ethylene-methacrylic acid copolymer and an ethylene-acrylic acid copolymer. At this time, the compatibility between the two is improved, and the above effects can be exerted more effectively.

［其他成分］ 本發明之聚醯胺樹脂組成物，除上述成分外，還可包含例如防黏連劑、潤滑劑、成核劑、發泡劑、穩定劑及偶聯劑等，但並不限定於該等。該等添加劑可分別僅含有1種，亦可含有2種以上。但，該等添加劑的摻合量相對於聚醯胺樹脂組成物之合計質量宜為10質量%以下較佳，更佳為5質量%以下，尤佳為3質量%以下，又更佳為1質量%以下。摻合上述添加劑時，摻合量的下限值相對於聚醯胺樹脂組成物之合計質量宜為0.01質量%以上較佳。 又，本發明之聚醯胺樹脂組成物也可包含聚醯胺樹脂以外之熱塑性樹脂，宜不包含較佳。具體而言，本發明之聚醯胺樹脂組成物所包含之聚醯胺樹脂以外之熱塑性樹脂宜為聚醯胺樹脂之1質量%以下較佳。[Other components] The polyamine resin composition of the present invention may contain, for example, an anti-blocking agent, a lubricant, a nucleating agent, a foaming agent, a stabilizer, a coupling agent, etc., in addition to the above components, but not Limited to these. These additives may be contained alone or in combination of two or more. However, the blending amount of the additives is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, still more preferably 1 based on the total mass of the polyamide resin composition. Below mass%. When the additive is blended, the lower limit of the blending amount is preferably 0.01% by mass or more based on the total mass of the polyamide resin composition. Further, the polyamide resin composition of the present invention may contain a thermoplastic resin other than the polyamide resin, and it is preferably not included. Specifically, the thermoplastic resin other than the polyamide resin contained in the polyamide resin composition of the present invention is preferably 1% by mass or less of the polyamine resin.

聚醯胺樹脂組成物之製造方法並無特別限制，必要時可摻合各種添加劑，並可採用習知的各種方法。聚醯胺樹脂組成物，例如，可藉由以下之方法製造：使用滾動機或混合機進行均勻地乾式摻配以成為特定比例的方法；或將以乾式摻配獲得之混合物利用熔融混練機進行熔融混練的方法；將一部分利用熔融混練機進行混練後，與剩餘部分進行乾式摻配的方法等。熔融混練可使用單軸擠壓機、雙軸擠壓機、捏合機、班伯里混合機(banbury mixer)等混練機進行。The method for producing the polyamide resin composition is not particularly limited, and various additives may be blended as necessary, and various conventional methods may be employed. The polyamide resin composition can be produced, for example, by a method of uniformly dry blending using a rolling machine or a mixer to obtain a specific ratio; or a mixture obtained by dry blending using a melt kneader A method of melt-kneading; a method in which a part of the mixture is kneaded by a melt kneading machine, and the remaining portion is dry-blended. The melt kneading can be carried out using a kneading machine such as a uniaxial extruder, a biaxial extruder, a kneader, or a banbury mixer.

［薄膜］ 本發明之薄膜包含上述本發明之聚醯胺樹脂組成物。本發明之薄膜宜由聚醯胺樹脂組成物形成較佳。本發明之薄膜之厚度宜為1～300μm較佳。本發明之薄膜，例如可為延伸薄膜。[Film] The film of the present invention comprises the above-described polyamine resin composition of the present invention. The film of the present invention is preferably formed of a polyamide resin composition. The thickness of the film of the present invention is preferably from 1 to 300 μm. The film of the present invention may be, for example, an extended film.

製造本發明之薄膜的方法，例如可適用公知的製造方法。例如，藉由將聚醯胺樹脂組成物利用擠壓機熔融混練，並利用T-模具、衣架型模具等模具擠製成薄膜狀，於澆鑄輥面上澆鑄後進行冷卻，可製造含有聚醯胺樹脂組成物之薄膜。亦可將製得之薄膜進行延伸處理而製成延伸薄膜。此時，可將製得之薄膜進行單軸延伸而製成單軸延伸薄膜，亦可進行雙軸延伸而製成雙軸延伸薄膜。As a method of producing the film of the present invention, for example, a known production method can be applied. For example, the polyamine resin composition is melt-kneaded by an extruder, and extruded into a film shape by a mold such as a T-die or a coat hanger mold, and cast on a casting roll surface to be cooled, thereby producing a polyfluorene-containing composition. A film of an amine resin composition. The obtained film may also be subjected to elongation treatment to form an extended film. In this case, the obtained film may be uniaxially stretched to form a uniaxially stretched film, or may be biaxially stretched to form a biaxially stretched film.

［薄膜疊層體］ 本發明之薄膜疊層體係包括上述本發明之薄膜的多層薄膜的疊層體。本發明之薄膜疊層體，例如可藉由將包括本發明之薄膜的多層薄膜進行熱壓接而製造。亦可將製得之薄膜疊層體進行延伸處理而製成延伸薄膜疊層體。此時，可將製得之薄膜疊層體進行單軸延伸而製成單軸延伸薄膜疊層體，亦可進行雙軸延伸而製成雙軸延伸薄膜疊層體。[Film Laminate] The film laminate system of the present invention comprises the laminate of the multilayer film of the film of the present invention described above. The film laminate of the present invention can be produced, for example, by thermocompression bonding a multilayer film including the film of the present invention. The obtained film laminate may be subjected to elongation treatment to form a stretched film laminate. In this case, the obtained film laminate may be uniaxially stretched to form a uniaxially stretched film laminate, or may be biaxially stretched to form a biaxially stretched film laminate.

本發明之薄膜疊層體，例如，可由核層(core layer)、和分別覆蓋核層之兩面的皮層(skin layer)構成。此時，核層與皮層之中，皮層宜由本發明之聚醯胺樹脂組成物構成較佳。例如，核層宜由聚間亞二甲苯己二醯胺(聚醯胺MXD6)、乙烯-乙烯醇共聚物等阻隔性樹脂構成，皮層宜由本發明之聚醯胺樹脂組成物構成較佳。 尤其本發明之薄膜包含聚醯胺樹脂6時，可理想地使用於食品用包裝材料，特別是可理想地使用於進行加熱處理之用途。 作為本發明之一較佳實施形態，可列舉係本發明之薄膜的包含聚醯胺樹脂6之薄膜和阻隔層(例如，乙烯-乙烯醇共聚物(EVOH))的薄膜疊層體。The film laminate of the present invention can be composed, for example, of a core layer and a skin layer covering both sides of the core layer. At this time, among the core layer and the skin layer, the skin layer is preferably composed of the polyamide resin composition of the present invention. For example, the core layer is preferably composed of a barrier resin such as polymethylene xylene hexamethylenediamine (polyamine MXD6) or an ethylene-vinyl alcohol copolymer, and the skin layer is preferably composed of the polyamine resin composition of the present invention. In particular, when the film of the present invention contains the polyamide resin 6, it can be preferably used for a food packaging material, and particularly preferably used for heat treatment. A preferred embodiment of the present invention includes a film laminate comprising a film of the polyamide resin 6 and a barrier layer (for example, an ethylene-vinyl alcohol copolymer (EVOH)).

薄膜疊層體的詳細內容可參酌日本特開2001-341253號公報之記載，該等內容援引於本說明書中。尤其將日本特開2001-341253號公報中構成B層之組成物替換為本發明之聚醯胺樹脂組成物而得的疊層體為較佳。 ［實施例］The details of the film laminate can be described in JP-A-2001-341253, the contents of which are incorporated herein by reference. In particular, a laminate obtained by substituting the composition of the layer B in the composition of the present invention with the polyamine resin composition of the present invention is preferably a laminate of JP-A-2001-341253. [Examples]

以下，基於具體的實施例針對本發明進行更詳細地說明，但本發明並不限定於以下之實施例，在不改變其要旨的範圍內可進行適當變更並實施。In the following, the present invention will be described in more detail with reference to the specific embodiments. However, the present invention is not limited thereto, and may be appropriately modified and implemented without departing from the spirit and scope of the invention.

此外，以下之實施例及比較例中係使用以下之材料。 聚醯胺樹脂：聚醯胺6(以下亦稱為「PA6」，商品名：UBE Nylon 1022B(宇部興產(股)公司製)) 烯烴系彈性體：乙烯-丙烯酸乙酯共聚物(以下，亦稱為「乙烯-丙烯酸乙酯樹脂」，商品名：UBE Polyethylene ZE708(宇部丸善聚乙烯(股)公司製))乙烯-丙烯酸乙酯共聚物中之丙烯酸酯之含量為16質量%。 烯烴系彈性體：乙烯-丙烯酸乙酯共聚物、商品名：UBE Polyethylene ZE742(宇部丸善聚乙烯(股)公司製))乙烯-丙烯酸乙酯共聚物中之丙烯酸酯之含量為25質量%。 抗氧化劑：苯酚系抗氧化劑、IRGANOX (Irganox)1098(BASF公司製) 離子聚合物樹脂：乙烯-甲基丙烯酸共聚物之Zn2 + 離子聚合物、離子聚合物樹脂之羧基的中和度60%、商品名：HIMILAN 1706(三井・杜邦(股)公司製)Further, in the following examples and comparative examples, the following materials were used. Polyamide: Polyamide 6 (hereinafter also referred to as "PA6", trade name: UBE Nylon 1022B (manufactured by Ube Industries, Ltd.)) Olefin-based elastomer: ethylene-ethyl acrylate copolymer (hereinafter, Also known as "ethylene-ethyl acrylate resin", the trade name: UBE Polyethylene ZE708 (manufactured by Ube Polyethylene Co., Ltd.)) The content of the acrylate in the ethylene-ethyl acrylate copolymer is 16% by mass. Olefin-based elastomer: ethylene-ethyl acrylate copolymer, trade name: UBE Polyethylene ZE742 (manufactured by Ube Polyethylene Co., Ltd.) The content of the acrylate in the ethylene-ethyl acrylate copolymer was 25% by mass. Antioxidant: phenol-based antioxidant, IRGANOX (Irganox) 1098 (manufactured by BASF Corporation) Ionic polymer resin: ethylene-methacrylic acid copolymer Zn 2 + ionomer, ionic polymer resin carboxyl group neutralization degree 60% , product name: HIMILAN 1706 (manufactured by Mitsui & DuPont Co., Ltd.)

(實施例1) 將98.7質量%之聚醯胺6、1質量%之乙烯-丙烯酸乙酯共聚物(ZE708)、0.1質量%之抗氧化劑、0.2質量%之離子聚合物樹脂利用乾式摻配進行混合，獲得聚醯胺樹脂組成物。使用PLABOR公司製T模成形裝置(模具寬度：300mm)，獲得由聚醯胺樹脂組成物構成之薄膜。於擠壓機之設定溫度200～260℃、模具之溫度260℃、冷卻輥之溫度30℃進行成形。改變輥的捲繞速度，以製作厚度100μm與50μm之薄膜。(Example 1) 98.7% by mass of polydecylamine 6, 1% by mass of ethylene-ethyl acrylate copolymer (ZE708), 0.1% by mass of an antioxidant, and 0.2% by mass of an ionic polymer resin were subjected to dry blending. Mixing to obtain a polyamide resin composition. A film composed of a polyamide resin composition was obtained using a T-die forming apparatus (mold width: 300 mm) manufactured by PLABOR Co., Ltd. The molding was carried out at a set temperature of 200 to 260 ° C of the extruder, a temperature of 260 ° C of the mold, and a temperature of 30 ° C of the cooling roll. The winding speed of the rolls was changed to produce a film having a thickness of 100 μm and 50 μm.

(實施例2) 將聚醯胺樹脂組成物中之聚醯胺6之含量設定為96.1質量%，乙烯-丙烯酸乙酯共聚物(ZE708)之含量設定為3質量%，抗氧化劑之含量設定為0.3質量%，離子聚合物樹脂之含量設定為0.6質量%，除此以外，和實施例1同樣製作由聚醯胺樹脂組成物構成之薄膜。(Example 2) The content of the polyamide 6 in the polyamide resin composition was set to 96.1% by mass, the content of the ethylene-ethyl acrylate copolymer (ZE708) was set to 3% by mass, and the content of the antioxidant was set to A film composed of a polyamide resin composition was produced in the same manner as in Example 1 except that the content of the ionic polymer resin was changed to 0.6% by mass.

(實施例3) 將聚醯胺樹脂組成物中之聚醯胺6之含量設定為99.3質量%，乙烯-丙烯酸乙酯共聚物(ZE708)之含量設定為0.5質量%，抗氧化劑之含量設定為0.1質量%，離子聚合物樹脂之含量設定為0.1質量%，除此以外，和實施例1同樣製作聚醯胺薄膜。(Example 3) The content of the polyamide 6 in the polyamide resin composition was set to 99.3% by mass, the content of the ethylene-ethyl acrylate copolymer (ZE708) was set to 0.5% by mass, and the content of the antioxidant was set to A polyimide film was produced in the same manner as in Example 1 except that the content of the ionic polymer resin was 0.1% by mass.

(實施例4) 將聚醯胺樹脂組成物中之聚醯胺6之含量設定為98.7質量%，乙烯-丙烯酸乙酯共聚物(ZE742)之含量設定為1質量%，抗氧化劑之含量設定為0.1質量%，離子聚合物樹脂之含量設定為0.2質量%，除此以外，和實施例1同樣製作聚醯胺薄膜。(Example 4) The content of the polyamine 6 in the polyimide resin composition was set to 98.7% by mass, the content of the ethylene-ethyl acrylate copolymer (ZE742) was set to 1% by mass, and the content of the antioxidant was set to A polyimide film was produced in the same manner as in Example 1 except that the content of the ionic polymer resin was changed to 0.2% by mass.

(實施例5) 將聚醯胺樹脂組成物中之聚醯胺6之含量設定為96.1質量%，乙烯-丙烯酸乙酯共聚物(ZE742)之含量設定為3質量%，抗氧化劑之含量設定為0.3質量%，離子聚合物樹脂之含量設定為0.6質量%，除此以外，和實施例1同樣製作聚醯胺薄膜。(Example 5) The content of the polyamide 6 in the polyamide resin composition was set to 96.1% by mass, the content of the ethylene-ethyl acrylate copolymer (ZE742) was set to 3% by mass, and the content of the antioxidant was set to A polyamide film was produced in the same manner as in Example 1 except that the content of the ionic polymer resin was 0.3% by mass.

(比較例1) 僅使用聚醯胺6並和實施例1同樣製作聚醯胺薄膜。(Comparative Example 1) A polyimide film was produced in the same manner as in Example 1 except that only polyamide 6 was used.

(比較例2) 將聚醯胺樹脂組成物中之聚醯胺6之含量設定為99.9質量%，未使用乙烯-丙烯酸乙酯共聚物(ZE708)及離子聚合物樹脂，除此以外，和實施例1同樣製作聚醯胺薄膜。(Comparative Example 2) The content of the polyamine 6 in the polyimide resin composition was set to 99.9% by mass, and the ethylene-ethyl acrylate copolymer (ZE708) and the ionic polymer resin were not used, and In Example 1, a polyimide film was produced in the same manner.

(比較例3) 將聚醯胺樹脂組成物中之聚醯胺6之含量設定為99.0質量%，乙烯-丙烯酸乙酯共聚物(ZE708)之含量設定為1質量%，未使用抗氧化劑及離子聚合物樹脂，除此以外，和實施例1同樣製作聚醯胺薄膜。(Comparative Example 3) The content of the polyamide 6 in the polyamide resin composition was set to 99.0% by mass, and the content of the ethylene-ethyl acrylate copolymer (ZE708) was set to 1% by mass, and no antioxidant or ions were used. A polyamide film was produced in the same manner as in Example 1 except for the polymer resin.

(比較例4) 將聚醯胺樹脂組成物中之聚醯胺6之含量設定為97.0質量%，乙烯-丙烯酸乙酯共聚物(ZE708)之含量設定為3質量%，未使用抗氧化劑及離子聚合物樹脂，除此以外，和實施例1同樣製作聚醯胺薄膜。(Comparative Example 4) The content of the polyamine 6 in the polyamide resin composition was set to 97.0% by mass, and the content of the ethylene-ethyl acrylate copolymer (ZE708) was set to 3% by mass, and no antioxidant or ions were used. A polyamide film was produced in the same manner as in Example 1 except for the polymer resin.

(比較例5) 將聚醯胺樹脂組成物中之聚醯胺6之含量設定為99.0質量%，未使用乙烯-丙烯酸乙酯共聚物、抗氧化劑，將離子聚合物樹脂之含量設定為1質量%，除此以外，和實施例1同樣製作聚醯胺薄膜。(Comparative Example 5) The content of the polyamidamide 6 in the polyimide resin composition was set to 99.0% by mass, and the content of the ionic polymer resin was set to 1 mass without using an ethylene-ethyl acrylate copolymer or an antioxidant. A polyimide film was produced in the same manner as in Example 1 except for the above.

(比較例6) 將聚醯胺樹脂組成物中之聚醯胺6之含量設定為97.0質量%，未使用乙烯-丙烯酸乙酯共聚物、抗氧化劑，離子聚合物樹脂之含量設定為3質量%，除此以外，和實施例1同樣製作聚醯胺薄膜。(Comparative Example 6) The content of the polyamine 6 in the polyimide resin composition was set to 97.0% by mass, and the ethylene-ethyl acrylate copolymer and the antioxidant were not used, and the content of the ionic polymer resin was set to 3% by mass. A polyimide film was produced in the same manner as in Example 1 except for the above.

(比較例7) 將聚醯胺樹脂組成物中之聚醯胺6之含量設定為98.8質量%，乙烯-丙烯酸乙酯共聚物(ZE708)之含量設定為1質量%，離子聚合物樹脂之含量設定為0.2質量%，未使用抗氧化劑，除此以外，和實施例1同樣製作聚醯胺薄膜。(Comparative Example 7) The content of the polyamide 6 in the polyamide resin composition was set to 98.8% by mass, and the content of the ethylene-ethyl acrylate copolymer (ZE708) was set to 1% by mass, and the content of the ionic polymer resin. A polyimide film was produced in the same manner as in Example 1 except that the antioxidant was used in an amount of 0.2% by mass.

(比較例8) 將聚醯胺樹脂組成物中之聚醯胺6之含量設定為98.9質量%，乙烯-丙烯酸乙酯共聚物(ZE708)之含量設定為1質量%，抗氧化劑之含量設定為0.1質量%，未使用離子聚合物樹脂，除此以外，和實施例1同樣製作聚醯胺薄膜。(Comparative Example 8) The content of the polyamide 6 in the polyamide resin composition was set to 98.9% by mass, the content of the ethylene-ethyl acrylate copolymer (ZE708) was set to 1% by mass, and the content of the antioxidant was set to A polyimide film was produced in the same manner as in Example 1 except that 0.1 mass% of the ionic polymer resin was not used.

(比較例9) 將聚醯胺樹脂組成物中之聚醯胺6之含量設定為99.6質量%，乙烯-丙烯酸乙酯共聚物(ZE708)之含量設定為0.25質量%，抗氧化劑之含量設定為0.1質量%，離子聚合物樹脂之含量設定為0.05質量%，除此以外，和實施例1同樣製作聚醯胺薄膜。(Comparative Example 9) The content of the polyamine 6 in the polyamide resin composition was set to 99.6% by mass, the content of the ethylene-ethyl acrylate copolymer (ZE708) was set to 0.25 mass%, and the content of the antioxidant was set to A polyimide film was produced in the same manner as in Example 1 except that the content of the ionic polymer resin was changed to 0.05% by mass.

(熱水處理) 上述實施例1～5、及比較例1～8之各例中，各製作2片厚度50μm之薄膜，對於各例中所製作之2片中的1片進行於135℃之水蒸氣環境下保持30分鐘的熱水處理。以下，未進行熱水處理的薄膜稱為「熱水處理前薄膜」，已進行熱水處理的薄膜稱為「熱水處理後薄膜」。(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 sheets produced in each of the examples was subjected to 135 ° C. Hot water treatment for 30 minutes in a water vapor environment. Hereinafter, the film which has not been subjected to hot water treatment is referred to as "film before hot water treatment", and the film which has been subjected to hot water treatment is referred to as "film after hot water treatment".

(霧度(透明性)) 利用日本電色工業(股)製Haze Meter，依照ASTM D-1003測定進行雙軸延伸而得之薄膜的霧度(haze)。具體而言，將厚度100μm之薄膜使用岩本製作所製的雙軸延伸機BIX-703型，於100℃預熱60秒後，在T模成形時之擠壓方向(MD方向)及其直角方向(TD方向)之2方向上以150mm/秒之變形速度延伸至3.0倍後，於200℃之加熱空氣中進行30秒熱處理，之後，進行冷卻並從延伸槽取出，獲得厚度15μm左右的雙軸延伸薄膜。使用獲得之雙軸延伸薄膜測定上述霧度。(Haze (transparency)) The haze of the film obtained by biaxial stretching was measured in accordance with ASTM D-1003 using a Haze Meter manufactured by Nippon Denshoku Industries Co., Ltd. Specifically, a film having a thickness of 100 μm is used in a biaxial stretching machine BIX-703 type manufactured by Iwahisa Seisakusho Co., Ltd., and after being preheated at 100 ° C for 60 seconds, the extrusion direction (MD direction) and the direction of the right angle of the T-die are formed ( In the two directions of the TD direction, the deformation speed was extended to 3.0 times at a deformation speed of 150 mm/sec, and then heat treatment was performed in a heated air of 200 ° C for 30 seconds, and then cooled and taken out from the stretching groove to obtain a biaxial extension having a thickness of about 15 μm. film. The above haze was measured using the obtained biaxially stretched film.

(拉伸斷裂伸長度及伸長度保持率) 利用A&D製TENSILON萬能材料試驗機RTA-10KN，依照ASTM D-882，以拉伸速度300mm/分、夾頭間距離50mm之條件測定厚度50μm之熱水處理前薄膜及熱水處理後薄膜各自的拉伸斷裂伸長度(%)。熱水處理後之拉伸斷裂伸長的伸長度保持率(%)由下式算出。(Tensile elongation at break and elongation retention) Using a TENSILON universal material testing machine RTA-10KN manufactured by A&D, the heat of 50 μm was measured in accordance with ASTM D-882 at a tensile speed of 300 mm/min and a distance between the chucks of 50 mm. Tensile elongation at break (%) of each film before water treatment and film after hot water treatment. The elongation retention ratio (%) of the tensile elongation at break after the hot water treatment was calculated by the following formula.

伸長度保持率(%)＝熱水處理後之拉伸斷裂伸長(%)/熱水處理前之拉伸斷裂伸長(%)×100Elongation retention rate (%) = tensile elongation at break (%) after hot water treatment / tensile elongation at break (%) before hot water treatment × 100

(蓋爾波•佛蘭克司試驗(Gelbo Flex test)(耐針孔性)) 利用理學工業(股)製、附恆溫槽之蓋爾波•佛蘭克司試驗機，依照MIL-B-131C，於23℃、50%相對濕度(RH)環境下，對於厚度50μm之熱水處理前薄膜及熱水處理後薄膜分別進行1000次的彎曲試驗後，將該薄膜設置在記錄紙上，之後塗抹墨汁，測定記錄紙上所記錄之黑點的數目。就其結果而言個數未達90個則判斷為「○」，個數為90個以上、未達120個判斷為「△」，個數為120個以上判斷為「×」。(Gelbo Flex test (pinhole resistance)) Using the Gilbert-Franks tester with a thermostat, according to MIL-B-131C, After performing a bending test for 1000 times on the film of hot water before the treatment of 50 μm and the film after hot water treatment at 23 ° C and 50% relative humidity (RH), the film was placed on a recording paper, and then ink was applied. The number of black dots recorded on the recording paper was measured. As a result, if the number is less than 90, it is judged as "○", the number is 90 or more, less than 120 is judged as "△", and the number is 120 or more and judged as "X".

【表1】 【表2】 【Table 1】 【Table 2】

由上述結果可知：使用本發明之聚醯胺樹脂組成物而得之薄膜，即使熱水處理後，拉伸斷裂伸長度及伸長度保持率亦高，針孔耐性亦優異。 進一步，由實施例1與比較例3、實施例2與比較例4之比較可知：藉由摻合抗氧化劑與離子聚合物樹脂，可使霧度格外降低。 又，不含抗氧化劑時(比較例5～7)，結果為熱水處理後之各種物性格外差。尤其使用僅由聚醯胺樹脂構成之薄膜時(比較例1)等，性能更差。 不含離子聚合物樹脂時(比較例8)，霧度變高。From the above results, it is understood that the film obtained by using the polyamide resin composition of the present invention has high tensile elongation at break and elongation retention even after hot water treatment, and is excellent in pinhole resistance. Further, from the comparison of Example 1 with Comparative Example 3, Example 2 and Comparative Example 4, it was found that the blending of the antioxidant and the ionic polymer resin can particularly reduce the haze. Further, when no antioxidant was contained (Comparative Examples 5 to 7), various physical properties after hot water treatment were exceptionally poor. In particular, when a film composed only of a polyamide resin (Comparative Example 1) or the like is used, the performance is further inferior. When the ionic polymer resin was not contained (Comparative Example 8), the haze was high.

(拉伸彈性模量) 就聚醯胺樹脂組成物而言，摻合聚醯胺6作為聚醯胺樹脂、UBE Polyethylene ZE708作為烯烴系彈性體、HIMILAN 1706作為離子聚合物樹脂以成為表3所示之質量比。 將獲得之聚醯胺樹脂組成物依照實施例1成形為厚度100μm之未延伸單層薄膜。進一步，和霧度之段落所記載的方法同樣獲得厚度15μm之延伸單層薄膜。利用拉伸試驗機(A&D製、TENSILON萬能材料試驗機RTA-10KN)，依照ASTM D-882)，於23℃、50%相對濕度(RH)之環境下測定獲得之延伸單層薄膜的拉伸彈性模量。結果顯示於下列表3中。 【表3】 由上述結果可知：烯烴系彈性體與離子聚合物樹脂之質量比率為實驗例A～實驗例D之範圍時，可確認到拉伸彈性模量顯著變高。亦即，可知本發明之薄膜，烯烴系彈性體與離子聚合物樹脂之質量比為0.04～0.4左右時，可達成高拉伸彈性模量。(Tensile Modulus) For the polyamide resin composition, polyamine 6 was blended as a polyamide resin, UBE Polyethylene ZE708 was used as an olefin elastomer, and HIMILAN 1706 was used as an ionic polymer resin. Show the quality ratio. The obtained polyamide resin composition was formed into an unstretched single-layer film having a thickness of 100 μm in accordance with Example 1. Further, an extended single-layer film having a thickness of 15 μm was obtained in the same manner as the method described in the paragraph of Haze. Using a tensile tester (A&D, TENSILON Universal Material Testing Machine RTA-10KN), according to ASTM D-882), the stretch of the obtained extended single layer film was measured at 23 ° C, 50% relative humidity (RH). Elastic Modulus. The results are shown in Table 3 below. 【table 3】 From the above results, it was found that when the mass ratio of the olefin-based elastomer to the ionic polymer resin was in the range of Experimental Example A to Experimental Example D, it was confirmed that the tensile elastic modulus was remarkably high. That is, it is understood that the film of the present invention has a high tensile modulus of elasticity when the mass ratio of the olefin-based elastomer to the ionic polymer resin is about 0.04 to 0.4.

無no

Claims (11)

一種聚醯胺樹脂組成物，包含： 聚醯胺樹脂； 0.1質量%～5質量%之烯烴系彈性體； 0.01質量%～1質量%之抗氧化劑；及 0.01質量%～3質量%之離子聚合物樹脂。A polyamide resin composition comprising: a 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; and 0.01% by mass to 3% by mass of an ionic polymerization Resin. 如申請專利範圍第1項之聚醯胺樹脂組成物，其中，該聚醯胺樹脂包含脂肪族聚醯胺樹脂。The polyamine resin composition of claim 1, wherein the polyamide resin comprises an aliphatic polyamide resin. 如申請專利範圍第1項之聚醯胺樹脂組成物，其中，該聚醯胺樹脂包含聚醯胺6。The polyamine resin composition of claim 1, wherein the polyamide resin comprises polyamine 6. 如申請專利範圍第1或2項之聚醯胺樹脂組成物，其中，該烯烴系彈性體包含乙烯-丙烯酸乙酯共聚物。The polyamine resin composition of claim 1 or 2, wherein the olefin-based elastomer comprises an ethylene-ethyl acrylate copolymer. 如申請專利範圍第1或2項之聚醯胺樹脂組成物，其中，該烯烴系彈性體包含乙烯-丙烯酸乙酯共聚物，且該乙烯-丙烯酸乙酯共聚物中之丙烯酸含量為5質量%～30質量%。The polyamine resin composition according to claim 1 or 2, wherein the olefin-based elastomer comprises an ethylene-ethyl acrylate copolymer, and the acrylic acid content in the ethylene-ethyl acrylate copolymer is 5% by mass. ～30% by mass. 如申請專利範圍第1或2項之聚醯胺樹脂組成物，其中，該抗氧化劑包含苯酚系抗氧化劑。The polyamine resin composition of claim 1 or 2, wherein the antioxidant comprises a phenolic antioxidant. 如申請專利範圍第1或2項之聚醯胺樹脂組成物，其中，該離子聚合物樹脂包含乙烯-甲基丙烯酸共聚物及乙烯-丙烯酸共聚物中之至少一者。The polyamine resin composition of claim 1 or 2, wherein the ionic polymer resin comprises at least one of an ethylene-methacrylic acid copolymer and an ethylene-acrylic acid copolymer. 如申請專利範圍第1或2項之聚醯胺樹脂組成物，其中，該烯烴系彈性體及離子聚合物樹脂各自獨立地包含乙烯-甲基丙烯酸共聚物及乙烯-丙烯酸共聚物中之至少一者。The polyamidamide resin composition according to claim 1 or 2, wherein the olefin-based elastomer and the ionic polymer resin each independently comprise at least one of an ethylene-methacrylic acid copolymer and an ethylene-acrylic acid copolymer. By. 如申請專利範圍第1或2項之聚醯胺樹脂組成物，其中，該聚醯胺樹脂組成物所包含之聚醯胺樹脂之99質量%以上為脂肪族聚醯胺樹脂。The polyamidamide resin composition of the first or second aspect of the invention, wherein 99% by mass or more of the polyamide resin contained in the polyamide resin composition is an aliphatic polyamide resin. 一種薄膜，包含如申請專利範圍第1至9項中任一項之聚醯胺樹脂組成物。A film comprising the polyamide resin composition as claimed in any one of claims 1 to 9. 如申請專利範圍第10項之薄膜，其係延伸薄膜。A film according to claim 10, which is an extended film.
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