JP4449690B2 - Polyamide film - Google Patents
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- JP4449690B2 JP4449690B2 JP2004301601A JP2004301601A JP4449690B2 JP 4449690 B2 JP4449690 B2 JP 4449690B2 JP 2004301601 A JP2004301601 A JP 2004301601A JP 2004301601 A JP2004301601 A JP 2004301601A JP 4449690 B2 JP4449690 B2 JP 4449690B2
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- 229920002647 polyamide Polymers 0.000 title claims description 155
- 239000004952 Polyamide Substances 0.000 title claims description 152
- 239000010410 layer Substances 0.000 claims description 166
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 claims description 40
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 36
- 238000000465 moulding Methods 0.000 claims description 26
- 229920005992 thermoplastic resin Polymers 0.000 claims description 24
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 22
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 16
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 claims description 12
- 229960002684 aminocaproic acid Drugs 0.000 claims description 12
- 238000004806 packaging method and process Methods 0.000 claims description 12
- 235000011037 adipic acid Nutrition 0.000 claims description 11
- 239000001361 adipic acid Substances 0.000 claims description 11
- 150000004985 diamines Chemical class 0.000 claims description 9
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 9
- 239000002356 single layer Substances 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 238000000034 method Methods 0.000 description 21
- 239000004840 adhesive resin Substances 0.000 description 17
- 229920006223 adhesive resin Polymers 0.000 description 17
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 235000013305 food Nutrition 0.000 description 12
- 239000000853 adhesive Substances 0.000 description 11
- 230000001070 adhesive effect Effects 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 8
- 230000004888 barrier function Effects 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000005022 packaging material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 229920001684 low density polyethylene Polymers 0.000 description 4
- 239000004702 low-density polyethylene Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920006280 packaging film Polymers 0.000 description 3
- 239000012785 packaging film Substances 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 230000002940 repellent Effects 0.000 description 3
- 239000005871 repellent Substances 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920003231 aliphatic polyamide Polymers 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012792 core layer Substances 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 229920001384 propylene homopolymer Polymers 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- 229920000007 Nylon MXD6 Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 235000014443 Pyrus communis Nutrition 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229920003233 aromatic nylon Polymers 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- ALBYIUDWACNRRB-UHFFFAOYSA-N hexanamide Chemical compound CCCCCC(N)=O ALBYIUDWACNRRB-UHFFFAOYSA-N 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229920006281 multilayer packaging film Polymers 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000020991 processed meat Nutrition 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 235000013580 sausages Nutrition 0.000 description 1
- 229920006300 shrink film Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000021055 solid food Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
Landscapes
- Wrappers (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Polyamides (AREA)
Description
本発明は、食品などの包装用又はシュリンク包装用、ソーセージなどの流動体または半流動体状の食品、加工肉やハムなどの固形状の食品等を充填し、包装するためのケーシング用に用いることができる、酸素バリア性に優れ、熱水収縮性に優れる少なくとも１層のポリアミド層を有する単層又は多層のポリアミドフィルム又は、延伸されたポリアミドフィルムに関するものである。 INDUSTRIAL APPLICABILITY The present invention is used for casings for filling and packaging food or other packaging or shrink packaging, fluid or semi-fluid food such as sausage, solid food such as processed meat or ham, etc. The present invention relates to a single-layer or multilayer polyamide film having at least one polyamide layer having excellent oxygen barrier properties and excellent hot water shrinkability, or a stretched polyamide film.
従来、食品包装用フィルムとして、ポリアミド層を有するフィルムが用いられている。
特許文献１には、カプロアミドを主たる構成単位とし、他の２種の脂肪族ポリアミドを１３〜５０重量％の範囲で共重合し、融点が１５０〜２００℃の範囲である３元共重合ポリアミドを１つの層として含む耐レトルト性包装材料が開示されている。
特許文献２には、（ａ）ポリアミドからなる内層と、（ｂ）エステル、無水物及びカルボン酸の群から選択される少なくとも１つの官能部分を有する少なくとも１種のエチレン重合体を少なくとも６０重量％含むコア層と、
（ｃ）ポリアミドからなる外層と、を含む管状二軸延伸熱収縮性多層フィルム食品ケーシングであって、該コア層（ｂ）が該内層（ａ）と該外層（ｃ）との間に配置され、そして該多層フィルムが少なくとも１つの方向において９０℃で少なくとも１０％の収縮値を有することからなる管状二軸延伸熱収縮性多層フィルム食品ケーシングが開示されている。
特許文献３には、少なくとも一層のポリアミド系樹脂組成物層を有する単層または多層の包装用フィルムまたはシートにおいて、該ポリアミド系樹脂組成物層が、脂肪族ナイロン（共）重合体成分（１）と芳香族ナイロン（共）重合体成分（２）とを含む共重合ナイロン（ｃ）を少なくとも５重量％の割合で含有するポリアミド系樹脂組成物からなる層（Ａ）であることを特徴とする包装用フィルムまたはシートが開示されている。
Conventionally, films having a polyamide layer have been used as food packaging films.
Patent Document 1 discloses a terpolymer polyamide having caproamide as a main structural unit, copolymerizing two other aliphatic polyamides in a range of 13 to 50% by weight, and having a melting point in a range of 150 to 200 ° C. A retort resistant packaging material comprising one layer is disclosed.
Patent Document 2 includes at least 60% by weight of at least one ethylene polymer having (a) an inner layer composed of polyamide and (b) at least one functional moiety selected from the group of esters, anhydrides, and carboxylic acids. Including a core layer,
(C) a tubular biaxially stretched heat-shrinkable multilayer film food casing comprising an outer layer made of polyamide, wherein the core layer (b) is disposed between the inner layer (a) and the outer layer (c). And a tubular biaxially oriented heat shrinkable multilayer film food casing comprising the multilayer film having a shrinkage value of at least 10% at 90 ° C. in at least one direction.
In Patent Document 3, in a single-layer or multilayer packaging film or sheet having at least one polyamide-based resin composition layer, the polyamide-based resin composition layer includes an aliphatic nylon (co) polymer component (1). And a layer (A) made of a polyamide-based resin composition containing a copolymer nylon (c) containing at least 5% by weight of a copolymer nylon component (2) and an aromatic nylon (co) polymer component (2). A packaging film or sheet is disclosed.
また三元共重合ポリアミドとしては、（Ａ）ε−カプロラクタム及び／又はε−アミノカプロン酸の成分、（Ｂ）１２−アミノドデカン酸及び／又はω−ラウロラクタムの成分、（Ｃ）ヘキサメチレンジアミンとアジピン酸の当モル塩とを共重合して得られるポリアミドフィルムとしては、特許文献１、特許文献４、特許文献５及び特許文献６に開示されている。 Further, as the terpolymer polyamide, (A) ε-caprolactam and / or ε-aminocaproic acid component, (B) 12-aminododecanoic acid and / or ω-laurolactam component, (C) hexamethylenediamine and Polyamide films obtained by copolymerization with an equimolar salt of adipic acid are disclosed in Patent Document 1, Patent Document 4, Patent Document 5 and Patent Document 6.
本発明の目的は、食品等の包装材料、シュリンク包装材料、食品ケーシング用材料として、酸素ガスバリア性に優れ、突き刺し性に優れ、熱水収縮率の大きいポリアミド層を有するポリアミドフィルムを提供することにある。 An object of the present invention is to provide a polyamide film having a polyamide layer having excellent oxygen gas barrier properties, excellent piercing properties, and a high hot water shrinkage rate as packaging materials for foods, shrink packaging materials, and food casing materials. is there.
本発明は、少なくとも１層のポリアミド層を有する単層又は多層のポリアミドフィルムであり、
ポリアミド層が、５０〜９０重量％の（Ａ）ε−カプロラクタム及びε−アミノカプロン酸から選ばれる成分と、（Ｂ）１２−アミノドデカン酸及びω−ラウロラクタムから選ばれる成分及び（Ｃ）ヘキサメチレンジアミンとアジピン酸の当モル塩との合計量（Ｂ成分とＣ成分の合計量）１０〜５０重量％とを共重合（Ａ成分、Ｂ成分及びＣ成分の３成分を含み、３成分の合計量が１００重量％である）して得られるポリアミドであり、
水冷インフレーション成形により製造されることを特徴とするポリアミドフィルムである。
The present invention is a monolayer or multilayer polyamide film having at least one polyamide layer,
The polyamide layer comprises 50 to 90% by weight of a component selected from (A) ε-caprolactam and ε-aminocaproic acid, (B) a component selected from 12-aminododecanoic acid and ω-laurolactam, and (C) hexamethylene. Copolymerized total amount of diamine and equimolar salt of adipic acid (total amount of B component and C component) 10 to 50% by weight (including 3 components of A component, B component and C component) The amount of which is 100% by weight)
A polyamide film manufactured by water-cooled inflation molding.
本発明のポリアミドフィルムの好ましい態様を以下に示す。本発明ではこれらの態様は組合せることができる。
（１）ポリアミドフィルムは、水冷インフレーション成形により製造されたフィルムをさら延伸して得られるポリアミドフィルムであること。
（２）ポリアミドフィルムは、水冷インフレーション成形により製造されたフィルムをさら同時二軸延伸又は逐次二軸延伸して得られるポリアミドフィルムであること。
（３）ポリアミド層の（Ａ）ε−カプロラクタム及びε−アミノカプロン酸から選ばれる成分が、７６〜８４重量％であること。
（４）ポリアミド層の（Ｂ）１２−アミノドデカン酸及びω−ラウロラクタムから選ばれる成分が、６〜１４重量％であること。
（５）ポリアミドフィルムは、ポリアミド層のほかに、さらに熱可塑性樹脂層を有する少なくとも２層以上であること。
（６）ポリアミドフィルムが、シュリンク包装用のポリアミドフィルムであること。
（７）ポリアミドフィルムが、ケーシング包装用のポリアミドフィルムであること。
Preferred embodiments of the polyamide film of the present invention are shown below. In the present invention, these embodiments can be combined.
(1) The polyamide film is a polyamide film obtained by further stretching a film produced by water-cooled inflation molding.
(2) The polyamide film is a polyamide film obtained by further simultaneous biaxial stretching or sequential biaxial stretching of a film produced by water-cooled inflation molding.
(3) The component selected from (A) ε-caprolactam and ε-aminocaproic acid in the polyamide layer is 76 to 84% by weight.
(4) The component selected from (B) 12-aminododecanoic acid and ω-laurolactam in the polyamide layer is 6 to 14% by weight.
(5) The polyamide film should be at least two layers having a thermoplastic resin layer in addition to the polyamide layer.
(6) The polyamide film is a polyamide film for shrink wrapping.
(7) The polyamide film is a polyamide film for casing packaging.
本発明のポリアミドフィルムは、水冷インフレーション成形により製造されたフィルム又は、水冷インフレーション成形により製造されたフィルムをさらに同時二軸延伸など延伸された延伸フィルムであり、シュリンク包装用やケーシング包装用に用いることができる食品等の包装材料として、酸素ガスバリア性に優れ、突き刺し性に優れ、熱水収縮性の大きいフィルムである。 The polyamide film of the present invention is a film produced by water-cooled inflation molding or a stretched film obtained by further stretching the film produced by water-cooled inflation molding, such as simultaneous biaxial stretching, and used for shrink packaging and casing packaging. As a packaging material for foods and the like, it is a film having excellent oxygen gas barrier properties, excellent piercing properties, and high hot water shrinkage.
本発明のポリアミドフィルムは、
少なくとも１層のポリアミド層を有する単層又は多層のポリアミドフィルムであり、
ポリアミド層が、５０〜９０重量％の（Ａ）ε−カプロラクタム及びε−アミノカプロン酸から選ばれる成分と、（Ｂ）１２−アミノドデカン酸及びω−ラウロラクタムから選ばれる成分及び（Ｃ）ヘキサメチレンジアミンとアジピン酸の当モル塩との合計量（Ｂ成分とＣ成分の合計量）１０〜５０重量％とを共重合（Ａ成分、Ｂ成分及びＣ成分の３成分を含み、３成分の合計量が１００重量％である）して得られるポリアミドであり、
水冷インフレーション成形により製造されることを特徴とするポリアミドフィルムである。
The polyamide film of the present invention is
A single-layer or multi-layer polyamide film having at least one polyamide layer;
The polyamide layer comprises 50 to 90% by weight of a component selected from (A) ε-caprolactam and ε-aminocaproic acid, (B) a component selected from 12-aminododecanoic acid and ω-laurolactam, and (C) hexamethylene. Copolymerized total amount of diamine and equimolar salt of adipic acid (total amount of B component and C component) 10 to 50% by weight (including 3 components of A component, B component and C component) The amount of which is 100% by weight)
A polyamide film manufactured by water-cooled inflation molding.
好ましくは本発明のポリアミドフィルムは、
少なくとも１層のポリアミド層を有する単層又は多層のポリアミドフィルムであり、
ポリアミド層が、５０〜９０重量％の（Ａ）ε−カプロラクタム及びε−アミノカプロン酸から選ばれる成分と、（Ｂ）１２−アミノドデカン酸及びω−ラウロラクタムから選ばれる成分及び（Ｃ）ヘキサメチレンジアミンとアジピン酸の当モル塩との合計量（Ｂ成分とＣ成分の合計量）１０〜５０重量％とを共重合（Ａ成分、Ｂ成分及びＣ成分の３成分を含み、３成分の合計量が１００重量％である）して得られるポリアミドであり、
水冷インフレーション成形により製造されたフィルムをさらに延伸して得られることを特徴とするポリアミドフィルムである。
Preferably, the polyamide film of the present invention is
A single-layer or multi-layer polyamide film having at least one polyamide layer;
The polyamide layer comprises 50 to 90% by weight of a component selected from (A) ε-caprolactam and ε-aminocaproic acid, (B) a component selected from 12-aminododecanoic acid and ω-laurolactam, and (C) hexamethylene. Copolymerized total amount of diamine and equimolar salt of adipic acid (total amount of B component and C component) 10 to 50% by weight (including 3 components of A component, B component and C component) The amount of which is 100% by weight)
A polyamide film obtained by further stretching a film produced by water-cooled inflation molding.
好ましくは本発明のポリアミドフィルムは、
少なくとも１層のポリアミド層と、少なくとも１層の熱可塑性樹脂層との２層以上の多層のポリアミドフィルムであり、
ポリアミド層が、５０〜９０重量％の（Ａ）ε−カプロラクタム及びε−アミノカプロン酸から選ばれる成分と、（Ｂ）１２−アミノドデカン酸及びω−ラウロラクタムから選ばれる成分及び（Ｃ）ヘキサメチレンジアミンとアジピン酸の当モル塩との合計量（Ｂ成分とＣ成分の合計量）１０〜５０重量％とを共重合（Ａ成分、Ｂ成分及びＣ成分の３成分を含み、３成分の合計量が１００重量％である）して得られるポリアミドであり、
水冷インフレーション成形により製造されることを特徴とするポリアミドフィルムである。
Preferably, the polyamide film of the present invention is
A multilayer polyamide film of two or more layers of at least one polyamide layer and at least one thermoplastic resin layer;
The polyamide layer comprises 50 to 90% by weight of a component selected from (A) ε-caprolactam and ε-aminocaproic acid, (B) a component selected from 12-aminododecanoic acid and ω-laurolactam, and (C) hexamethylene. Copolymerized total amount of diamine and equimolar salt of adipic acid (total amount of B component and C component) 10 to 50% by weight (including 3 components of A component, B component and C component) The amount of which is 100% by weight)
A polyamide film manufactured by water-cooled inflation molding.
好ましくは本発明のポリアミドフィルムは、
少なくとも１層のポリアミド層と、少なくとも１層の熱可塑性樹脂層との２層以上の多層のポリアミドフィルムであり、
ポリアミド層が、５０〜９０重量％の（Ａ）ε−カプロラクタム及びε−アミノカプロン酸から選ばれる成分と、（Ｂ）１２−アミノドデカン酸及びω−ラウロラクタムから選ばれる成分及び（Ｃ）ヘキサメチレンジアミンとアジピン酸の当モル塩との合計量（Ｂ成分とＣ成分の合計量）１０〜５０重量％とを共重合（Ａ成分、Ｂ成分及びＣ成分の３成分を含み、３成分の合計量が１００重量％である）して得られるポリアミドであり、
水冷インフレーション成形により製造されたフィルムをさらに延伸して得られることを特徴とするポリアミドフィルムである。
Preferably, the polyamide film of the present invention is
A multilayer polyamide film of two or more layers of at least one polyamide layer and at least one thermoplastic resin layer;
The polyamide layer comprises 50 to 90% by weight of a component selected from (A) ε-caprolactam and ε-aminocaproic acid, (B) a component selected from 12-aminododecanoic acid and ω-laurolactam, and (C) hexamethylene. Copolymerized total amount of diamine and equimolar salt of adipic acid (total amount of B component and C component) 10 to 50% by weight (including 3 components of A component, B component and C component) The amount of which is 100% by weight)
A polyamide film obtained by further stretching a film produced by water-cooled inflation molding.
ポリアミド層は、
５０〜９０重量％の（Ａ）ε−カプロラクタム及びε−アミノカプロン酸から選ばれる成分（Ａ成分）と、（Ｂ）１２−アミノドデカン酸及びω−ラウロラクタムから選ばれる成分（Ｂ成分）及び（Ｃ）ヘキサメチレンジアミンとアジピン酸の当モル塩（Ｃ成分）との合計量（Ｂ成分とＣ成分の合計量）１０〜５０重量％とのＡ成分、Ｂ成分及びＣ成分を含む成分を共重合（Ａ成分、Ｂ成分及びＣ成分の合計量が１００重量％である）して得られるポリアミドからなる層である。
ポリアミド層のＡ成分は、好ましくは７６〜８４重量％である。
ポリアミド層のＢ成分は、好ましくは６〜１４重量％である。
The polyamide layer
50 to 90% by weight of (A) a component selected from ε-caprolactam and ε-aminocaproic acid (component A), and (B) a component selected from 12-aminododecanoic acid and ω-laurolactam (component B) and ( C) The total amount of hexamethylenediamine and the equimolar salt of adipic acid (C component) (the total amount of B component and C component) is 10 to 50% by weight, and the components including A component, B component and C component are combined. This is a layer made of polyamide obtained by polymerization (the total amount of the component A, component B and component C is 100% by weight).
The component A of the polyamide layer is preferably 76 to 84% by weight.
The B component of the polyamide layer is preferably 6 to 14% by weight.
ポリアミド層のＡ成分、Ｂ成分及びＣ成分の構成の具体例を以下に示す（但し、Ａ成分、Ｂ成分及びＣ成分の合計量は、１００重量％である）。
（Ｉ）ポリアミド層は、Ａ成分が５０〜９０重量％と、Ｂ成分とＣ成分との合計量が１０〜５０重量％とを共重合（Ａ成分、Ｂ成分及びＣ成分の３成分を含む）して得られるポリアミドからなるポリアミド層である。
（II）ポリアミド層は、Ａ成分が５０〜９０重量％、Ｂ成分が６〜１４重量％、残りがＣ成分であり、Ｂ成分とＣ成分との合計量が１０〜５０重量％であり、Ａ成分、Ｂ成分及びＣ成分の３成分を共重合して得られるポリアミドからなるポリアミド層が好ましい。
（III）ポリアミド層は、Ａ成分が７６〜８４重量％と、Ｂ成分とＣ成分との合計量が１６〜２４重量％とを共重合（Ａ成分、Ｂ成分及びＣ成分の３成分を含む）して得られるポリアミドからなるポリアミド層が好ましい。
（IV）ポリアミド層は、Ａ成分が７６〜８４重量％、Ｂ成分が６〜１４重量％、残りがＣ成分であり、Ｂ成分とＣ成分との合計量が１６〜２４重量％であり、Ａ成分、Ｂ成分及びＣ成分の３成分を共重合して得られるポリアミドからなるポリアミド層が好ましい。
Specific examples of the constitution of the A component, the B component and the C component of the polyamide layer are shown below (however, the total amount of the A component, the B component and the C component is 100% by weight).
(I) The polyamide layer is a copolymer of 50 to 90% by weight of component A and 10 to 50% by weight of the total amount of component B and component C (including three components of component A, component B and component C). Is a polyamide layer made of polyamide.
(II) In the polyamide layer, the A component is 50 to 90% by weight, the B component is 6 to 14% by weight, the rest is the C component, and the total amount of the B component and the C component is 10 to 50% by weight, A polyamide layer made of polyamide obtained by copolymerizing three components of A component, B component and C component is preferred.
(III) The polyamide layer is a copolymer of 76 to 84% by weight of component A and 16 to 24% by weight of the total amount of component B and component C (including three components of component A, component B and component C). The polyamide layer made of polyamide obtained by
(IV) The polyamide layer is 76 to 84% by weight of the A component, 6 to 14% by weight of the B component, the rest is the C component, and the total amount of the B and C components is 16 to 24% by weight, A polyamide layer made of polyamide obtained by copolymerizing three components of A component, B component and C component is preferred.
ポリアミド層を構成するポリアミドの製造は、溶融重合、溶液重合や固相重合等公知のポリアミドの重合方法で行うことができる。製造装置としては、バッチ式反応釜、一槽式ないし多槽式の連続反応装置、管状連続反応装置、一軸型混練押出機、二軸型混練押出機等の混練反応押出機等、公知のポリアミド製造装置を用いることができる。重合方法としては溶融重合、溶液重合や固相重合等の公知の方法を用い、常圧、減圧、加圧操作を繰り返して重合することができる。これらの重合方法は単独で、あるいは適宜、組合せて用いることができる。 The polyamide constituting the polyamide layer can be produced by a known polyamide polymerization method such as melt polymerization, solution polymerization or solid phase polymerization. Production equipment includes known polyamides such as batch reaction kettles, single tank or multi-tank continuous reaction apparatuses, tubular continuous reaction apparatuses, kneading reaction extruders such as uniaxial kneading extruders and biaxial kneading extruders, etc. Manufacturing equipment can be used. As a polymerization method, a known method such as melt polymerization, solution polymerization, or solid phase polymerization can be used, and polymerization can be performed by repeating normal pressure, reduced pressure, and pressure operations. These polymerization methods can be used alone or in appropriate combination.
本発明のポリアミドフィルムは、ポリアミド層のほかに、熱可塑性樹脂層を内層及び／又は外層に有することができる。
熱可塑性樹脂層としては、低密度ポリエチレン、直鎖状低密度ポリエチレン、アイオノマー、エチレン−アクリル酸共重合体、エチレン−酢酸ビニル共重合体、エチレン−アクリル酸エステル共重合体、エチレン−メタクリル酸共重合体などのエチレン系樹脂、エチレン−αオレフィン共重合体、プロピレン単独重合体、プロピレンと炭素数２〜８のα−オレフィンとの共重合体などのプロピレン系樹脂などのオレフィン系樹脂、ポリエステル、ポリビニルアルコールなど、及びこれらを延伸したものなどを用いることができる。
これらの中で水蒸気バリア性を確保するときには非極性ポリオレフィンである低密度ポリエチレン、直鎖状低密度ポリエチレン、エチレン−αオレフィン共重合体、プロピレン単独重合体、プロピレンと炭素数２〜８のα−オレフィンとの共重合体などのプロピレン系樹脂などを使用することが好まれる。また、ガスバリア性の強化のために、エチレン−酢酸ビニル共重合体あるいは、ナイロンＭＸＤ６等からなる層を挿入することもできる。
The polyamide film of the present invention can have a thermoplastic resin layer in the inner layer and / or outer layer in addition to the polyamide layer.
The thermoplastic resin layer includes low density polyethylene, linear low density polyethylene, ionomer, ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid copolymer. Olefin resins such as ethylene resins such as polymers, ethylene-α olefin copolymers, propylene homopolymers, propylene resins such as copolymers of propylene and α-olefins having 2 to 8 carbon atoms, polyesters, Polyvinyl alcohol etc. and those obtained by stretching these can be used.
Among these, when ensuring the water vapor barrier property, low density polyethylene, linear low density polyethylene, ethylene-α olefin copolymer, propylene homopolymer, propylene and α-carbon having 2 to 8 carbon atoms, which are nonpolar polyolefins. It is preferable to use a propylene resin such as a copolymer with olefin. In order to enhance the gas barrier property, a layer made of ethylene-vinyl acetate copolymer or nylon MXD6 can be inserted.
本発明のポリアミドフィルムは、水冷インフレーション成形により製造することができ、好ましくは水冷インフレーション成形により製造されたフィルムを、さらに一軸延伸、同時二軸延伸又は逐次二軸延伸などの延伸を行うことにより製造することができる。 The polyamide film of the present invention can be produced by water-cooled inflation molding, preferably produced by further stretching a film produced by water-cooled inflation molding such as uniaxial stretching, simultaneous biaxial stretching, or sequential biaxial stretching. can do.
本発明のポリアミドフィルムを製造する方法としては、ポリアミド層などの各層の樹脂成分を押出機などを用いて溶融混練し、リング状などのダイにより筒状などの形状に押し出したものを、水で冷却する水冷式チューブラー法が適用される。 As a method for producing the polyamide film of the present invention, a resin component of each layer such as a polyamide layer is melt-kneaded using an extruder or the like, and extruded into a cylindrical shape or the like by a die such as a ring shape. A cooling water-cooled tubular method is applied.
本発明のポリアミドフィルムは、水冷インフレーション成形により未延伸フィルムを製造し、引続き連続して延伸を実施しても良いし、未延伸フィルムを製造し一旦ロール状などに巻き取り、さらに別工程として延伸を実施しても良く、公知の熱延伸方法により、延伸フィルムとして用いることができる。
本発明のポリアミドフィルムは、水冷インフレーション成形により製造されたフィルムを、さらに５０℃から１３０℃の範囲で一軸又は二軸に延伸して、延伸したポリアミドフィルムを得ることができる。延伸方法は、通常に行われているポリアミドフィルムの延伸方法、例えば加熱ロールによる一軸延伸、二軸延伸方法については、チューブラー法による同時二軸延伸法や加熱ロール／テンターによる逐次二軸延伸法で成形できる。延伸倍率は、特に決まっているわけではないが、通常は２倍以上、好ましくは２〜６倍、より好ましくは２．５〜５倍である。
このような本発明の延伸されたポリアミドフィルムは、シュリンク包装用フィルム又はケーシング包装用フィルムとして好適に使用でき、５０℃の熱水収縮試験による熱収縮率が１０％以上、好ましくは１５％以上であり、７０℃での熱水収縮試験による熱収縮率が１５％以上、好ましくは１７％以上、さらに好ましくは２０％以上であり、９０℃での熱水収縮試験による熱収縮率が２０％以上、好ましくは２５％以上、さらに好ましくは２７％以上である。
The polyamide film of the present invention may be produced by water-cooled inflation molding to produce an unstretched film, and may be continuously stretched, or the unstretched film is produced and wound into a roll, etc., and further stretched as a separate process. And can be used as a stretched film by a known heat stretching method.
The polyamide film of the present invention can be obtained by stretching a film produced by water-cooled inflation molding uniaxially or biaxially in the range of 50 ° C. to 130 ° C. to obtain a stretched polyamide film. As for the stretching method, a conventional method for stretching a polyamide film, for example, uniaxial stretching by a heating roll, biaxial stretching method, a simultaneous biaxial stretching method by a tubular method or a sequential biaxial stretching method by a heating roll / tenter is used. Can be molded. The draw ratio is not particularly determined, but is usually 2 times or more, preferably 2 to 6 times, more preferably 2.5 to 5 times.
Such a stretched polyamide film of the present invention can be suitably used as a film for shrink wrapping or a film for casing wrapping, and has a heat shrinkage rate of 10% or more, preferably 15% or more by a hot water shrinkage test at 50 ° C. Yes, the heat shrinkage rate by the hot water shrinkage test at 70 ° C. is 15% or more, preferably 17% or more, more preferably 20% or more, and the heat shrinkage rate by the hot water shrinkage test at 90 ° C. is 20% or more. , Preferably 25% or more, more preferably 27% or more.
本発明のポリアミドフィルムの層構成としては、ポリアミド層単独の層、ポリアミド層と熱可塑性樹脂層との２層、ポリアミド層／（接着剤又は接着性樹脂層）／熱可塑性樹脂層との３層、ポリアミド層及び熱可塑性樹脂層と、これらの層以外の層との少なくとも３層以上、ポリアミド層、熱可塑性樹脂層及び（接着剤又は接着性樹脂層）と、これらの層以外の層との少なくとも４層以上などを挙げることができる。
具体的には、ポリアミド層／（接着剤又は接着性樹脂層）／熱可塑性樹脂層、ポリアミド層／（接着剤又は接着性樹脂層）／熱可塑性樹脂層／（接着剤又は接着性樹脂層）／熱可塑性樹脂層、熱可塑性樹脂層／（接着剤又は接着性樹脂層）／ポリアミド層／（接着剤又は接着性樹脂層）／熱可塑性樹脂層、などを挙げることができ、接着剤又は接着性樹脂層は必要に応じて設けることができる。
The polyamide film of the present invention is composed of a single polyamide layer, two layers of a polyamide layer and a thermoplastic resin layer, and three layers of polyamide layer / (adhesive or adhesive resin layer) / thermoplastic resin layer. A polyamide layer and a thermoplastic resin layer and at least three layers other than these layers, a polyamide layer, a thermoplastic resin layer and (adhesive or adhesive resin layer), and a layer other than these layers There may be mentioned at least 4 layers.
Specifically, polyamide layer / (adhesive or adhesive resin layer) / thermoplastic resin layer, polyamide layer / (adhesive or adhesive resin layer) / thermoplastic resin layer / (adhesive or adhesive resin layer) / Thermoplastic resin layer, thermoplastic resin layer / (adhesive or adhesive resin layer) / polyamide layer / (adhesive or adhesive resin layer) / thermoplastic resin layer, etc. The functional resin layer can be provided as necessary.
本発明のポリアミドフィルムが多層の場合、本発明のポリアミドフィルムは、ポリアミド層と熱可塑性樹脂層、又はポリアミド層、接着性樹脂層及び熱可塑性樹脂層とは、各層の樹脂成分を溶融状態で同時に又は逐次に、押出すことにより製造することができる。
また、本発明のポリアミドフィルムは、ポリアミド層を有するフィルムと、熱可塑性樹脂層、又は接着性樹脂層及び熱可塑性樹脂層とを有するフィルムをそれぞれ製造し、フィルムを直接又は、接着剤又は接着性樹脂を介して、はり合わせて製造することができる。
When the polyamide film of the present invention is a multilayer, the polyamide film of the present invention is composed of a polyamide layer and a thermoplastic resin layer, or a polyamide layer, an adhesive resin layer and a thermoplastic resin layer. Or it can manufacture by extruding sequentially.
Moreover, the polyamide film of the present invention produces a film having a polyamide layer and a thermoplastic resin layer, or a film having an adhesive resin layer and a thermoplastic resin layer, respectively, and the film is directly or adhesive or adhesive. It can be manufactured by bonding through a resin.
接着性樹脂層としては、不飽和カルボン酸またはその誘導体から選ばれた少なくとも一種のモノマーをグラフトした酸変性ポリエチレンなどの酸変性ポリオレフィン樹脂などを用いることができる。 As the adhesive resin layer, an acid-modified polyolefin resin such as acid-modified polyethylene grafted with at least one monomer selected from an unsaturated carboxylic acid or a derivative thereof can be used.
本発明のポリアミドフィルムの２層以上の構成の具体例としては、外層側より、ポリアミド層／接着性樹脂層／熱融着性を有するエチレン系樹脂層、ポリアミド層／接着性樹脂層／エチレン系樹脂層、ポリアミド層／接着性樹脂層／エチレン系樹脂層／接着性樹脂層／熱融着性を有するエチレン系樹脂層、などを挙げることができる。 Specific examples of the constitution of two or more layers of the polyamide film of the present invention include, from the outer layer side, polyamide layer / adhesive resin layer / ethylene resin layer having heat-fusibility, polyamide layer / adhesive resin layer / ethylene system. Examples thereof include resin layers, polyamide layers / adhesive resin layers / ethylene resin layers / adhesive resin layers / ethylene resin layers having heat-fusibility.
本発明のポリアミドフィルムは、最外層に印刷処理を施す場合があり、最外層を格子模様、紋（梨地）模様、台形模様、絹目模様、凹凸状などの公知のエンボス加工や、マット加工などを行うことができる。マット加工としては、例えば無機物又は有機物を添加することにより行うことが出来、その具体例としては、外層に、無機物として、シリカやタルク、マイカなどの酸化ケイ素系化合物やシラスバルーンなどの径が２０μｍ以下の微粒子を添加することにより行うことができる。 The polyamide film of the present invention may be subjected to a printing process on the outermost layer. The outermost layer may be a known embossing process such as a lattice pattern, a crest (pear texture) pattern, a trapezoidal pattern, a silk pattern, an uneven shape, or a mat process. It can be performed. Matting can be performed, for example, by adding an inorganic substance or an organic substance, and specific examples thereof include, as an outer layer, a diameter of a silicon oxide compound such as silica, talc, or mica, or a shirasu balloon as an inorganic substance having a diameter of 20 μm. It can be performed by adding the following fine particles.
本発明のポリアミドフィルム、このフィルムを構成するポリアミド層及びこの層を構成するポリアミド、熱可塑性樹脂層及びこの層を構成する熱可塑性樹脂などは、得られるフィルムや樹脂などの特性を損なわない範囲内で、熱安定剤,酸化防止剤，紫外線吸収剤,耐候剤，滑剤，フィラー,核剤，可塑剤，発泡剤，ブロッキング防止剤、防雲剤、難燃剤、染料、顔料，安定剤，カップリング剤等を含有することができる。 The polyamide film of the present invention, the polyamide layer constituting this film and the polyamide constituting this layer, the thermoplastic resin layer and the thermoplastic resin constituting this layer are within the range not impairing the properties of the resulting film or resin. Thermal stabilizers, antioxidants, UV absorbers, weathering agents, lubricants, fillers, nucleating agents, plasticizers, foaming agents, anti-blocking agents, anti-clouding agents, flame retardants, dyes, pigments, stabilizers, couplings An agent etc. can be contained.
本発明のポリアミドフィルムの層の厚みは、
（１）ポリアミド層単独の場合、ポリアミド層は１０〜１００μｍの範囲が好ましい、
（２）ポリアミド層と熱可塑性樹脂層との２層、又はポリアミド層／（接着剤又は接着性樹脂層）／熱可塑性樹脂層との３層以上の場合、ポリアミド層は２〜８０μｍの範囲、熱可塑性樹脂層は８〜１２０μｍの範囲が好ましい。
接着剤又は接着性樹脂の厚みは、目的に応じて適宜選択することができる。
The thickness of the polyamide film layer of the present invention is
(1) In the case of the polyamide layer alone, the polyamide layer is preferably in the range of 10 to 100 μm.
(2) In the case of two layers of a polyamide layer and a thermoplastic resin layer, or three layers or more of a polyamide layer / (adhesive or adhesive resin layer) / thermoplastic resin layer, the polyamide layer is in the range of 2 to 80 μm, The thermoplastic resin layer is preferably in the range of 8 to 120 μm.
The thickness of the adhesive or adhesive resin can be appropriately selected depending on the purpose.
本発明のポリアミドフィルムは、熱水収縮性が大きく、酸素バリア性に優れるために、食品包装用フィルム、食品包装用シュリンクフィルム、食品包装用ケーシングフィルムとして用いることができる。 Since the polyamide film of the present invention has high hot water shrinkage and excellent oxygen barrier properties, it can be used as a food packaging film, a food packaging shrink film, and a food packaging casing film.
以下に実施例を示して説明するが、本発明はこれらの例によって限定されるものではない。 Examples will be described below, but the present invention is not limited to these examples.
実施例及び比較例に示した測定値は以下の方法で測定する。
１）ポリアミドのηｒ（相対粘度）の測定： ＪＩＳ・Ｋ６８１０に準じて、９６重量％の濃硫酸を溶媒として、１重量／容量％のポリアミド濃度で、ウベローデ粘度計を用い、２５℃の温度で測定する。
２）融点： セイコーインスツルメンツ（株）製ＤＳＣ２１０型を用い、窒素ガス雰囲気下に試料のポリアミドを昇温速度１０℃／ｍｉｎで２５０℃まで加熱し、その温度で１０分間保持した後、１０℃／ｍｉｎの速度で３０℃まで冷却した直後、再度１０℃／ｍｉｎで２５０℃まで加熱し、再度加熱した過程に得られた吸熱ピークに達した時の加熱温度を融点とする。
３）ヘイズ： ＡＳＴＭ・Ｄ−１００３に準じて、スガ試験機社製直読式ヘイズメーターを使用して、ヘイズを測定する。
４）グロス（光沢度）： ＡＳＴＭ・Ｄ−５２３に準じて、スガ試験機社製デジタル変角光沢度計を使用して、グロスを測定する。
５）突刺強度： ＪＡＳ・Ｐ１０１９に準じて、ＴＯＹＯ ＢＡＬＤＷＩＮ社製テンシロンＵＴＭ−III−２００を使用して、突刺速度５０ｍｍ／ｍｉｎ、２３℃、５０％ＲＨの条件下で測定する。
６）酸素透過度： ＡＳＴＭ・Ｄ−３９８５−８１に準じて、モダンコントロール社製ＭＯＣＯＮ−ＯＸ−ＴＲＡＮ２／２０を使用して、２３℃、０％ＲＨの条件下で測定する。
The measured values shown in the examples and comparative examples are measured by the following method.
1) Measurement of ηr (relative viscosity) of polyamide: According to JIS K6810, 96 wt% concentrated sulfuric acid was used as a solvent at a polyamide concentration of 1 wt / vol%, using an Ubbelohde viscometer at a temperature of 25 ° C. taking measurement.
2) Melting point: Using a DSC210 model manufactured by Seiko Instruments Inc., the sample polyamide was heated to 250 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen gas atmosphere, held at that temperature for 10 minutes, then 10 ° C. / Immediately after cooling to 30 ° C. at a rate of min, the mixture is heated again to 250 ° C. at 10 ° C./min.
3) Haze: Haze is measured using a direct reading haze meter manufactured by Suga Test Instruments Co., Ltd. according to ASTM D-1003.
4) Gloss (Glossiness): Gloss is measured using a digital variable angle glossiness meter manufactured by Suga Test Instruments Co., Ltd. according to ASTM D-523.
5) Puncture strength: Measured under the conditions of a puncture speed of 50 mm / min, 23 ° C., and 50% RH using Tensilon UTM-III-200 manufactured by TOYO BALDWIN in accordance with JAS · P1019.
6) Oxygen permeability: Measured under conditions of 23 ° C. and 0% RH using MOCON-OX-TRAN 2/20 manufactured by Modern Control, in accordance with ASTM D-3985-81.
ヘイズ、グロス、突刺強度及び酸素透過度の評価は、水冷インフレーション成形して得られる３層の未延伸フィルムを、さらに以下の同時二軸延伸フィルムの製造方法により、同時二軸延伸して得られる、同時二軸延伸フィルムを用いて行う。
同時二軸延伸フィルムの製造方法： 所定雰囲気温度（８０℃）に温度調節された二軸延伸機ＢＩＸ−７０３型（岩本製作所製）の延伸槽に、縦９２ｍｍ、横９２ｍｍの未延伸の試料フィルムを取付け、雰囲気温度（「延伸時温度」と記載することもある。）で２０秒間予熱した後、フィルムの押出方向及び押出の直角方向の２方向に、１４０ｍｍ／秒の変形速度で２．８倍延伸した後、８０℃の加熱空気で１分間熱処理を行う。
Evaluation of haze, gloss, puncture strength and oxygen permeability is obtained by simultaneously biaxially stretching a three-layer unstretched film obtained by water-cooled inflation molding by the following simultaneous biaxially stretched film production method. Simultaneously biaxially stretched film is used.
Production method of simultaneous biaxially stretched film: Unstretched sample film of 92 mm in length and 92 mm in width in a stretching tank of a biaxial stretching machine BIX-703 type (manufactured by Iwamoto Seisakusho) whose temperature is adjusted to a predetermined atmospheric temperature (80 ° C) After preheating for 20 seconds at ambient temperature (sometimes referred to as “stretching temperature”), 2.8 at a deformation rate of 140 mm / second in two directions, ie, the film extrusion direction and the orthogonal direction of extrusion. After being stretched, heat treatment is performed with heated air at 80 ° C. for 1 minute.
７）延伸性： 延伸時の応力、延伸時の延伸機チャックの把持性、延伸されたフィルムの延伸ムラの有無を総合して判断する。延伸機は岩本製作所製ＢＩＸ７０３ラボ延伸機を使用して測定する。
評価：◎：延伸機チャック把持が十分で均一な延伸ができた場合、○：均一な延伸が出来た場合、△：延伸できるがムラを生じた場合。
８）熱水収縮率： 同時二軸延伸直後のフィルムのＭＤ方向の長さＡ（ｍｍ）を測定し、所定温度（５０℃、７０℃又は９０℃）に設定したウォーターバスに同フィルムを１分間浸漬した後、２３℃、５０％ＲＨの環境下に２４時間放置し、浸漬放置後の同箇所の長さＢ（ｍｍ）を測定し、下記数式（１）に従い熱水収縮率（％）を算出した。
7) Stretchability: Judgment is made by comprehensively considering the stress during stretching, the gripping property of the stretching machine chuck during stretching, and the presence or absence of stretching unevenness in the stretched film. The stretching machine is measured using a BIX703 laboratory stretching machine manufactured by Iwamoto Seisakusho.
Evaluation: ：: When the stretching machine chuck is sufficiently gripped and uniform stretching is possible, ○: Uniform stretching is possible, Δ: Stretching is possible but unevenness occurs.
8) Hot water shrinkage ratio: The length A (mm) in the MD direction of the film immediately after simultaneous biaxial stretching was measured, and the film was placed in a water bath set at a predetermined temperature (50 ° C, 70 ° C or 90 ° C). After soaking for 30 minutes, leave it in an environment of 23 ° C. and 50% RH for 24 hours, measure the length B (mm) of the same part after standing soaked, and shrink the hot water according to the following formula (1) (%) Was calculated.
（重合例１）
７０Ｌのオ−トクレ−ブにε−カプロラクタム１６．０ｋｇ、ＡＨ塩水溶液（５０ｗｔ％水溶液）４．０ｋｇ、１２−アミノドデカン酸２．０ｋｇおよび蒸留水２．０ｋｇを仕込み、重合槽内を窒素置換したのち、密閉して１８０℃まで昇温し、次いで攪拌しながら重合槽内を１７．５ｋｇｆ／ｃｍ２Ｇに調圧しながら、重合槽内温度を２４０℃まで昇温した。重合温度が２４０℃に達して２ｈｒ後に重合槽内の圧力を約２ｈｒかけて常圧に放圧した。放圧後、窒素気流下で１ｈｒ重合した後、２ｈｒ減圧重合を行った。窒素を導入して常圧に復圧後、攪拌機を止めて、ストランドとして抜き出しペレット化した。このポリアミドペレットを沸騰水中に入れ、攪拌下に約１２時間、洗浄して未反応モノマーを抽出除去した後、１００℃で２４時間減圧乾燥した。このようにして得たポリアミドの相対粘度は３．８８であり、融点は１８８℃であった。このポリアミドをＰＡ−１と称す。
(Polymerization example 1)
A 70 L autoclave was charged with 16.0 kg of ε-caprolactam, 4.0 kg of AH salt aqueous solution (50 wt% aqueous solution), 2.0 kg of 12-aminododecanoic acid and 2.0 kg of distilled water, and the inside of the polymerization tank was replaced with nitrogen. Then, it was sealed and heated up to 180 ° C., and then the temperature in the polymerization vessel was raised to 240 ° C. while adjusting the pressure in the polymerization vessel to 17.5 kgf / cm 2 G while stirring. 2 hours after the polymerization temperature reached 240 ° C., the pressure in the polymerization tank was released to normal pressure over about 2 hours. After releasing the pressure, the mixture was polymerized for 1 hr under a nitrogen stream and then subjected to vacuum polymerization for 2 hr. Nitrogen was introduced and the pressure was restored to normal pressure. Then, the stirrer was stopped, and the strand was extracted and pelletized. The polyamide pellets were placed in boiling water, washed with stirring for about 12 hours to extract and remove unreacted monomers, and then dried under reduced pressure at 100 ° C. for 24 hours. The polyamide thus obtained had a relative viscosity of 3.88 and a melting point of 188 ° C. This polyamide is referred to as PA-1.
（重合例２）
７０Ｌのオ−トクレ−ブにε−カプロラクタム１６．０ｋｇ、ＡＨ塩水溶液（５０ｗｔ％水溶液）２．４ｋｇ、１２−アミノドデカン酸２．８ｋｇおよび蒸留水２．８ｋｇを仕込み、重合例１と同様の方法で実施し相対粘度３．８９、融点１８８℃のポリアミドを得た。このポリアミドをＰＡ−２と称す。
(Polymerization example 2)
A 70 L autoclave was charged with 16.0 kg of ε-caprolactam, 2.4 kg of an AH salt aqueous solution (50 wt% aqueous solution), 2.8 kg of 12-aminododecanoic acid and 2.8 kg of distilled water. And a polyamide having a relative viscosity of 3.89 and a melting point of 188 ° C. was obtained. This polyamide is referred to as PA-2.
（重合例３）
７０Ｌのオ−トクレ−ブにε−カプロラクタム１６．０ｋｇ、ＡＨ塩水溶液（５０ｗｔ％水溶液）８．０ｋｇを仕込み、重合例１と同様の方法で実施し相対粘度３．９２、融点１８９℃のポリアミドを得た。このポリアミドをＰＡ−３と称す。
(Polymerization Example 3)
A 70 L autoclave was charged with 16.0 kg of ε-caprolactam and 8.0 kg of an AH salt aqueous solution (50 wt% aqueous solution), and the same procedure as in Polymerization Example 1 was carried out. Polyamide having a relative viscosity of 3.92 and a melting point of 189 ° C. Got. This polyamide is referred to as PA-3.
（重合例４）
７０Ｌのオ−トクレ−ブにε−カプロラクタム１６．０ｋｇ、１２−アミノドデカン酸４．０ｋｇおよび蒸留水４．０ｋｇを仕込み、重合例１と同様の方法で実施し相対粘度３．８３、融点１９８℃のポリアミドを得た。このポリアミドをＰＡ−４と称す。
(Polymerization example 4)
A 70 L autoclave was charged with 16.0 kg of ε-caprolactam, 4.0 kg of 12-aminododecanoic acid and 4.0 kg of distilled water, and the same procedure as in Polymerization Example 1 was carried out. A polyamide at 0 ° C. was obtained. This polyamide is referred to as PA-4.
（重合例５）
７０Ｌのオ−トクレ−ブにε−カプロラクタム１７．０ｋｇ、ＡＨ塩水溶液（５０ｗｔ％水溶液）６．０ｋｇを仕込みおよび蒸留水１．０ｋｇを仕込み、重合例１と同様の方法で実施し相対粘度３．９２、融点１９８℃のポリアミドを得た。このポリアミドをＰＡ−５と称す。
(Polymerization Example 5)
A 70 L autoclave was charged with 17.0 kg of ε-caprolactam, 6.0 kg of an AH salt aqueous solution (50 wt% aqueous solution) and 1.0 kg of distilled water, and the same procedure as in Polymerization Example 1 was carried out. A polyamide with a melting point of 192 ° C. was obtained. This polyamide is referred to as PA-5.
（重合例６）
７０Ｌのオ−トクレ−ブにε−カプロラクタム１６．０ｋｇ、ＡＨ塩水溶液（５０ｗｔ％水溶液）６．０ｋｇ、１２−アミノドデカン酸１．０ｋｇおよび蒸留水１．０ｋｇを仕込み、重合例１と同様の方法で実施し相対粘度３．８８、融点１８９℃のポリアミドを得た。このポリアミドをＰＡ−６と称す。
(Polymerization Example 6)
A 70 L autoclave was charged with 16.0 kg of ε-caprolactam, 6.0 kg of AH salt aqueous solution (50 wt% aqueous solution), 1.0 kg of 12-aminododecanoic acid and 1.0 kg of distilled water. The process was carried out by the method to obtain a polyamide having a relative viscosity of 3.88 and a melting point of 189 ° C. This polyamide is referred to as PA-6.
（実施例１）
プラボー社製３種３層共押出水冷多層インフレーション成形機（ダイス口径１００ｍｍφ）を使用して、第一層（最外層）に撥水剤５００ｐｐｍを添加したＰＡ−１を、第二層にオレフィン系接着性樹脂（三井化学社製、商品名：アドマーＮＦ５１８）、第三層（最内層）に低密度ポリエチレン（宇部興産社製、商品名：ＵＢＥポリエチレンＦ２２２）をそれぞれ成形温度２６０℃で円筒上にサーキュラーダイよりブローアップ比１．５３で溶融押出しし、水温２２℃で冷却後、ピンチロールで折り畳みフィルム総厚み１００μｍの未延伸フィルムを作成した。
次に、このフィルムを用い、岩本製作所製ＢＩＸ７０３二軸延伸装置を使用し、延伸速度１４０ｍｍ／ｓｅｃ、延伸温度８０℃、延伸倍率２．８×２．８倍に同時二軸延伸した後、８０℃の加熱空気で１分間熱処理を行い、同時二軸延伸フィルムを作成し、延伸状態の確認と、各種物性を測定し、その結果を表１に示す。
Example 1
Using a three-layer co-extrusion water-cooled multi-layer inflation molding machine (die diameter: 100 mmφ) manufactured by Plavo, PA-1 with 500 ppm of water repellent added to the first layer (outermost layer), and olefin-based in the second layer Adhesive resin (made by Mitsui Chemicals, trade name: Admer NF518), low density polyethylene (made by Ube Industries, trade name: UBE polyethylene F222) as the third layer (innermost layer) on a cylinder at a molding temperature of 260 ° C. It was melt-extruded from a circular die at a blow-up ratio of 1.53, cooled at a water temperature of 22 ° C., and then folded with a pinch roll to produce an unstretched film having a total thickness of 100 μm.
Next, using this film, using a BIX703 biaxial stretching apparatus manufactured by Iwamoto Seisakusho, the film was simultaneously biaxially stretched at a stretching speed of 140 mm / sec, a stretching temperature of 80 ° C., and a stretching ratio of 2.8 × 2.8 times. A heat treatment was performed with heated air at 0 ° C. for 1 minute to prepare a simultaneous biaxially stretched film, confirmation of the stretched state and various physical properties were measured, and the results are shown in Table 1.
（実施例２）
第一層（最外層）に撥水剤５００ｐｐｍを添加したＰＡ−２を使用した以外は、実施例１と同様の方法で水冷インフレーション成形を行い、さらに同時二軸延伸を行い、同時二軸延伸フィルムを作成し、延伸状態の確認と、各種物性を測定し、その結果を表１に示す。
(Example 2)
Except for using PA-2 to which 500 ppm of water repellent is added to the first layer (outermost layer), water-cooled inflation molding is performed in the same manner as in Example 1, and simultaneous biaxial stretching is performed, and simultaneous biaxial stretching is performed. A film was prepared, the stretched state was confirmed, and various physical properties were measured. The results are shown in Table 1.
（比較例１〜３）
第一層（最外層）に撥水剤５００ｐｐｍを添加したＰＡ−３、ＰＡ−４又はＰＡ−５を使用した以外は、実施例１と同様の方法で水冷インフレーション成形を行い、さらに同時二軸延伸を行い、同時二軸延伸フィルムを作成し、延伸状態の確認と、各種物性を測定し、その結果を表１に示す。
(Comparative Examples 1-3)
Except for using PA-3, PA-4 or PA-5 in which 500 ppm of water repellent was added to the first layer (outermost layer), water-cooled inflation molding was carried out in the same manner as in Example 1, and simultaneous biaxial Stretching was performed to prepare a simultaneous biaxially stretched film, and the stretched state was confirmed and various physical properties were measured. Table 1 shows the results.
（比較例４）
プラボー社製３種３層共押出空冷多層インフレーション成形機（ダイス口径１００ｍｍφ）を使用して、第一層（最外層）に滑剤３００ｐｐｍを添加したＰＡ−６を、第二層にオレフィン系接着性樹脂（三井化学社製、商品名：アドマーＮＦ５１８）、第三層（最内層）に低密度ポリエチレン（宇部興産社製、商品名：ＵＢＥポリエチレンＦ２２２）を雰囲気温度２５℃、樹脂温度２５０℃、ブローアップ比１．５３の条件で、連続的に空冷インフレーション成形してフィルム総厚み６０μｍの未延伸フィルムを作成した。次に、このフィルムを用い、岩本製作所製ＢＩＸ７０３二軸延伸装置を使用し、延伸速度１４０ｍｍ／ｓｅｃ、延伸温度８０℃、延伸倍率２．８×２．８倍に同時二軸延伸した後、８０℃の加熱空気で１分間熱処理を行い、二軸延伸フィルムを作成し、延伸状態の確認と、各種物性を測定し、その結果を表１に示す。
(Comparative Example 4)
Using PABO 3 type 3 layer co-extrusion air-cooled multi-layer inflation molding machine (die diameter 100mmφ), PA-6 with 300ppm lubricant added to the first layer (outermost layer) and olefinic adhesion to the second layer Resin (made by Mitsui Chemicals, trade name: Admer NF518), low density polyethylene (made by Ube Industries, trade name: UBE polyethylene F222) for the third layer (innermost layer), ambient temperature 25 ° C., resin temperature 250 ° C., blow Under the condition of an up ratio of 1.53, air-cooled inflation molding was continuously performed to produce an unstretched film having a total film thickness of 60 μm. Next, using this film, using a BIX703 biaxial stretching apparatus manufactured by Iwamoto Seisakusho, the film was simultaneously biaxially stretched at a stretching speed of 140 mm / sec, a stretching temperature of 80 ° C., and a stretching ratio of 2.8 × 2.8 times. A biaxially stretched film was prepared by performing heat treatment with heated air at 0 ° C. for 1 minute, and the stretched state was confirmed and various physical properties were measured. Table 1 shows the results.
本発明のポリアミドフィルムは、水冷インフレーション成形により製造されたフィルム又は、水冷インフレーション成形により製造されたフィルムをさらに同時二軸延伸など延伸された延伸フィルムであり、食品等の包装材料として酸素ガスバリア性、突き刺し性及び熱水収縮性のバランスが優れる、シュリンク包装用又はケーシング包装用に好適に用いることができる。
本発明のポリアミドフィルムは、延伸成形性に優れ、光沢性及び透明性に優れる。
The polyamide film of the present invention is a film produced by water-cooled inflation molding or a stretched film obtained by further stretching the film produced by water-cooled inflation molding, such as simultaneous biaxial stretching, and has oxygen gas barrier properties as a packaging material for foods, It can be suitably used for shrink wrapping or casing wrapping, which has an excellent balance between piercing property and hot water shrinkability.
The polyamide film of the present invention is excellent in stretch moldability, and is excellent in gloss and transparency.
Claims (5)
ポリアミド層が、７６〜８４重量％の（Ａ）ε−カプロラクタム及びε−アミノカプロン酸から選ばれる成分と、（Ｂ）１２−アミノドデカン酸及びω−ラウロラクタムから選ばれる成分及び（Ｃ）ヘキサメチレンジアミンとアジピン酸の当モル塩との合計量（Ｂ成分とＣ成分の合計量）１６〜２４重量％とを共重合（Ａ成分、Ｂ成分及びＣ成分の３成分を含み、３成分の合計量が１００重量％である）して得られるポリアミドであり、
前記ポリアミド層の（Ｂ）１２−アミノドデカン酸及びω−ラウロラクタムから選ばれる成分が、６〜１４重量％であり、
水冷インフレーション成形により製造されたシュリンク包装用ポリアミドフィルム。 A single-layer or multi-layer polyamide film having at least one polyamide layer;
The polyamide layer comprises 76 to 84 % by weight of a component selected from (A) ε-caprolactam and ε-aminocaproic acid, (B) a component selected from 12-aminododecanoic acid and ω-laurolactam, and (C) hexamethylene. Total amount of diamine and equimolar salt of adipic acid (total amount of B component and C component) 16-24 % by weight (including 3 components of A component, B component and C component, total of 3 components) The amount of which is 100% by weight)
The component selected from (B) 12-aminododecanoic acid and ω-laurolactam in the polyamide layer is 6 to 14% by weight,
Polyamide film for shrink packaging manufactured by water-cooled inflation molding.
ポリアミド層が、７６〜８４重量％の（Ａ）ε−カプロラクタム及びε−アミノカプロン酸から選ばれる成分と、（Ｂ）１２−アミノドデカン酸及びω−ラウロラクタムから選ばれる成分及び（Ｃ）ヘキサメチレンジアミンとアジピン酸の当モル塩との合計量（Ｂ成分とＣ 成分の合計量）１６〜２４重量％とを共重合（Ａ成分、Ｂ成分及びＣ成分の３成分を含み、３成分の合計量が１００重量％である）して得られるポリアミドであり、
前記ポリアミド層の（Ｂ）１２−アミノドデカン酸及びω−ラウロラクタムから選ばれる成分が、６〜１４重量％であり、
水冷インフレーション成形により製造されたフィルムをさらに延伸して得られたシュリンク包装用ポリアミドフィルム。 A single-layer or multi-layer polyamide film having at least one polyamide layer;
The polyamide layer comprises 76 to 84 % by weight of a component selected from (A) ε-caprolactam and ε-aminocaproic acid, (B) a component selected from 12-aminododecanoic acid and ω-laurolactam, and (C) hexamethylene. Copolymerized total amount of diamine and equimolar salt of adipic acid (total amount of B component and C component) 16 to 24 % by weight (including 3 components of A component, B component and C component) The amount of which is 100% by weight)
The component selected from (B) 12-aminododecanoic acid and ω-laurolactam in the polyamide layer is 6 to 14% by weight,
A polyamide film for shrink packaging obtained by further stretching a film produced by water-cooled inflation molding.
ポリアミド層が、７６〜８４重量％の（Ａ）ε−カプロラクタム及びε−アミノカプロン酸から選ばれる成分と、（Ｂ）１２−アミノドデカン酸及びω−ラウロラクタムから選ばれる成分及び（Ｃ）ヘキサメチレンジアミンとアジピン酸の当モル塩との合計量（Ｂ成分とＣ成分の合計量）１６〜２４重量％とを共重合（Ａ成分、Ｂ成分及びＣ成分の３成分を含み、３成分の合計量が１００重量％である）して得られるポリアミドであり、
前記ポリアミド層の（Ｂ）１２−アミノドデカン酸及びω−ラウロラクタムから選ばれる成分が、６〜１４重量％であり、
水冷インフレーション成形により製造されたケーシング包装用ポリアミドフィルム。 A single-layer or multi-layer polyamide film having at least one polyamide layer;
The polyamide layer comprises 76 to 84 % by weight of a component selected from (A) ε-caprolactam and ε-aminocaproic acid, (B) a component selected from 12-aminododecanoic acid and ω-laurolactam, and (C) hexamethylene. Total amount of diamine and equimolar salt of adipic acid (total amount of B component and C component) 16-24 % by weight (including 3 components of A component, B component and C component, total of 3 components) The amount of which is 100% by weight)
The component selected from (B) 12-aminododecanoic acid and ω-laurolactam in the polyamide layer is 6 to 14% by weight,
Polyamide film for casing packaging manufactured by water-cooled inflation molding.
ポリアミド層が、７６〜８４重量％の（Ａ）ε−カプロラクタム及びε−アミノカプロン酸から選ばれる成分と、（Ｂ）１２−アミノドデカン酸及びω−ラウロラクタムから選ばれる成分及び（Ｃ）ヘキサメチレンジアミンとアジピン酸の当モル塩との合計量（Ｂ成分とＣ 成分の合計量）１６〜２４重量％とを共重合（Ａ成分、Ｂ成分及びＣ成分の３成分を含み、３成分の合計量が１００重量％である）して得られるポリアミドであり、
前記ポリアミド層の（Ｂ）１２−アミノドデカン酸及びω−ラウロラクタムから選ばれる成分が、６〜１４重量％であり、
水冷インフレーション成形により製造されたフィルムをさらに延伸して得られたケーシング包装用ポリアミドフィルム。 A single-layer or multi-layer polyamide film having at least one polyamide layer;
The polyamide layer comprises 76 to 84 % by weight of a component selected from (A) ε-caprolactam and ε-aminocaproic acid, (B) a component selected from 12-aminododecanoic acid and ω-laurolactam, and (C) hexamethylene. Copolymerized total amount of diamine and equimolar salt of adipic acid (total amount of B component and C component) 16 to 24 % by weight (including 3 components of A component, B component and C component) The amount of which is 100% by weight)
The component selected from (B) 12-aminododecanoic acid and ω-laurolactam in the polyamide layer is 6 to 14% by weight,
A polyamide film for casing packaging obtained by further stretching a film produced by water-cooled inflation molding.
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| JP2004301601A JP4449690B2 (en) | 2004-10-15 | 2004-10-15 | Polyamide film |
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| US8802778B2 (en) | 2008-04-03 | 2014-08-12 | Bridgestone Sports Co., Ltd. | Golf ball material, golf ball and method for preparing golf ball material |
| JP5225177B2 (en) * | 2009-04-02 | 2013-07-03 | 興人ホールディングス株式会社 | Alcohol permeable polyamide film |
| PL2248858T3 (en) * | 2009-04-16 | 2017-12-29 | Flexopack S.A. | High abuse heat shrinkable film |
| CN106459404B (en) | 2014-06-02 | 2019-03-08 | 宇部兴产株式会社 | Polyamide and formed products comprising it |
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| JPS59212261A (en) * | 1983-05-17 | 1984-12-01 | 住友ベークライト株式会社 | Heat-shrinkable multilayer film |
| JPH07102660B2 (en) * | 1989-09-21 | 1995-11-08 | 東レ株式会社 | Retort resistant packaging material |
| JPH07138471A (en) * | 1993-11-19 | 1995-05-30 | Mitsubishi Chem Corp | Polyamide resin composition and packaging film prepared therefrom |
| JP3315518B2 (en) * | 1994-03-31 | 2002-08-19 | 旭化成株式会社 | Heat shrinkable multilayer film |
| JPH08108506A (en) * | 1994-10-12 | 1996-04-30 | Mitsubishi Chem Corp | Laminated film and packaging bag using the same |
| JP3505898B2 (en) * | 1996-03-01 | 2004-03-15 | 宇部興産株式会社 | Manufacturing method of sequential biaxially stretched polyamide film |
| JPH10195211A (en) * | 1996-12-27 | 1998-07-28 | Kureha Chem Ind Co Ltd | Film or sheet for packaging |
| JP3430881B2 (en) * | 1997-07-04 | 2003-07-28 | 宇部興産株式会社 | Ternary copolyamide |
| JPH11172022A (en) * | 1997-12-09 | 1999-06-29 | Ube Ind Ltd | Biaxially oriented polyamide film |
| JP2000238220A (en) * | 1999-02-25 | 2000-09-05 | Mitsubishi Plastics Ind Ltd | Composite film for packaging liquid beverage |
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