JPH0363133A - Heat-shrinkable multilayer film - Google Patents
Heat-shrinkable multilayer filmInfo
- Publication number
- JPH0363133A JPH0363133A JP1200814A JP20081489A JPH0363133A JP H0363133 A JPH0363133 A JP H0363133A JP 1200814 A JP1200814 A JP 1200814A JP 20081489 A JP20081489 A JP 20081489A JP H0363133 A JPH0363133 A JP H0363133A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- multilayer film
- resin
- heat
- polyamide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920005989 resin Polymers 0.000 claims abstract description 46
- 239000011347 resin Substances 0.000 claims abstract description 46
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 239000004952 Polyamide Substances 0.000 claims abstract description 15
- 229920002647 polyamide Polymers 0.000 claims abstract description 15
- 229920006020 amorphous polyamide Polymers 0.000 claims abstract description 10
- 230000004888 barrier function Effects 0.000 claims abstract description 10
- 239000004953 Aliphatic polyamide Substances 0.000 claims abstract description 9
- 229920003231 aliphatic polyamide Polymers 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 abstract description 12
- 239000005022 packaging material Substances 0.000 abstract description 5
- 239000000178 monomer Substances 0.000 abstract description 3
- 229920001519 homopolymer Polymers 0.000 abstract description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 2
- 229920002554 vinyl polymer Polymers 0.000 abstract description 2
- 229920000098 polyolefin Polymers 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 36
- 239000007789 gas Substances 0.000 description 8
- 235000013372 meat Nutrition 0.000 description 8
- 239000004677 Nylon Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920001778 nylon Polymers 0.000 description 6
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 6
- 239000005038 ethylene vinyl acetate Substances 0.000 description 4
- 229920006122 polyamide resin Polymers 0.000 description 4
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical group O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 229920000554 ionomer Polymers 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920006257 Heat-shrinkable film Polymers 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical class C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000012793 heat-sealing layer Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920006350 polyacrylonitrile resin Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 235000020991 processed meat Nutrition 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006012 semi-aromatic polyamide Polymers 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は熱収縮率が改良されに熱収縮性多層フィルムに
関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a heat-shrinkable multilayer film with improved heat shrinkage rate.
〈従来の技術〉
従来よりポリアミド系樹脂層を含む熱収縮性多層フィル
ムは各包装分野において散見されるが、これらは、ポリ
アミド系樹脂として主にナイロン６、ナイロン６６等の
樹脂族系ポリアミド樹脂を用いていた。こうした脂肪族
系ポリアミド樹脂を用いた熱収縮性多層フィルムはガス
バリアー性、強靭性等に優れており、食肉用包装材料等
として多用されてきた。<Prior art> Heat-shrinkable multilayer films containing polyamide resin layers have been seen here and there in various packaging fields, but these films mainly use resin group polyamide resins such as nylon 6 and nylon 66 as polyamide resins. I was using it. Heat-shrinkable multilayer films using such aliphatic polyamide resins have excellent gas barrier properties, toughness, etc., and have been widely used as packaging materials for meat.
〈発明が解決しようとする問題点〉
しかし乍ら上記した熱収縮性多層フィルムは脂肪族系ポ
リアミド樹脂をその少なくとも一層に用いているため、
必要なガスバリアー性、強靭性等を得るためにはある程
度の厚さが必要となるが、そうするとどうしても延伸性
、熱収縮性がもう一つ十分でなくなり、用途の拡大を図
る上で問題となっていた。<Problems to be solved by the invention> However, since the above heat-shrinkable multilayer film uses an aliphatic polyamide resin in at least one layer thereof,
In order to obtain the necessary gas barrier properties, toughness, etc., a certain degree of thickness is required, but this inevitably results in insufficient stretchability and heat shrinkage, which poses a problem in expanding the range of uses. was.
く問題点を解決するための手段〉
本発明者らは延伸性に優れ、かつ熱収縮性に優れる多層
フィルムを提供すべく種々検討を繰り返した結果ついに
本発明に到達したもので、その特徴とするところは熱収
縮性多層フィルムにおける少なくも一層が脂肪族系ポリ
アミド樹脂６０〜９５重量％と非晶質系ポリアミド樹脂
４０〜５重量％とを含有するポリアミド系重合体により
構成されてなる点にある。Means for Solving the Problems> The present inventors have finally arrived at the present invention as a result of repeated studies in order to provide a multilayer film with excellent stretchability and heat shrinkability. The point is that at least one layer in the heat-shrinkable multilayer film is composed of a polyamide polymer containing 60 to 95% by weight of an aliphatic polyamide resin and 40 to 5% by weight of an amorphous polyamide resin. be.
次に本発明における問題点を解決するための手段な績々
述べることにする。Next, the means for solving the problems in the present invention will be described.
本発明に係る樹脂族系ポリアミド樹脂とはナイロン６、
ナイロン６６、ナイロン６１０．ナイロン１２などの他
にナイロン６−６６共重合体、ナイロン６−６１０共重
合体などのコポリアミドを例示することができ、主鎖も
しくは側鎖に芳香族環を有しない構造の６のならば、特
に制限はない。The resin family polyamide resin according to the present invention is nylon 6,
Nylon 66, nylon 610. In addition to nylon 12, examples include copolyamides such as nylon 6-66 copolymer and nylon 6-610 copolymer. , there are no particular restrictions.
また非晶質系ポリアミド樹脂とは、結晶性がないものか
、結晶性の乏しいもの等を総称しており、一般には主鎖
および／または側鎖等に芳香族環を有する半芳香族性の
ポリアミドを例示できる。具体的にはテレフタル酸、イ
ソフタル酸等のジカルボン酸とへキサメチレンジアミン
等のジアミンとの重合体、三元共重合体等を例示できる
が特に制限はない、こうした非晶質系ポリアミド樹脂は
高温時のガスバリアー性に優れ、例えばある種の非晶質
系ポリアミドはその２５μｍフィルムのＯ％ＲＨの酸素
透過度が３９ ｃ ｃ ／ ｍ ”２４ｈｒ （２３℃
）、１００％ＲＨでは１７ｃｃ／ｍ” ・２４ｈｒ （
２３℃）程度の値を確保することもできる。In addition, amorphous polyamide resin is a general term for those that have no crystallinity or have poor crystallinity, and are generally semi-aromatic polyamide resins that have aromatic rings in the main chain and/or side chains. An example is polyamide. Specific examples include polymers and terpolymers of dicarboxylic acids such as terephthalic acid and isophthalic acid and diamines such as hexamethylene diamine, but there are no particular limitations. Such amorphous polyamide resins can be used at high temperatures. For example, some amorphous polyamides have an oxygen permeability of 39 cc/m at O%RH for 24 hr (23°C).
), 17cc/m” at 100%RH ・24hr (
It is also possible to secure a value of about 23°C.
本発明に係る多層フィルムとしては、その少なくとも一
層が、脂肪族系ポリアミド樹脂と非晶質系ポリアミド系
樹脂を特定量含むポリアミド系重合体であればよい、ま
たかかる多層フィルムの厚さについては、特に制限はな
いが、通常は３０〜１００μｍ５好ましくは４０〜７０
μｍ程度を例示できる。尚前記したポリアミド系重合体
中にはその他適宜の第三成分が添加されていてもいこう
に差しつかえない。The multilayer film according to the present invention may have at least one layer made of a polyamide polymer containing a specific amount of an aliphatic polyamide resin and an amorphous polyamide resin, and the thickness of the multilayer film may be as follows: There is no particular limit, but usually 30 to 100 μm5 preferably 40 to 70 μm
An example is about μm. It should be noted that any other appropriate third component may be added to the polyamide polymer described above.
この際、多層フィルムの構成としては２Ｈ以上、好まし
くは３〜６層程度のものを例示できる。多層化する際、
他の層として使用する樹脂は特に制限はなく、各種の樹
脂層を適宜に朝み合せて用いればよい０通常用いられる
樹脂としてはポリオレフィン系樹脂層を先ず例示できる
。こうしたポリオレフィン系樹脂としては、例えばオレ
フィン類の単独重合体、相互共重合体、他の共重合可能
なモノマー例えば他のビニル系七ノマー等との共重合体
及びこれらの変性共重合体等を例示できる。具体的には
例えば低密度から高密度に亙る各種密度のポリエチレン
（線状低密度ポリエチレンを含む）、ポリプロピレン、
ポリブテン、これらの相互共重合体、アイオノマー樹脂
、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、変性ポリオレフィン系樹脂等を例示できる
。ここで変性ポリオレフィン系樹脂としては、上記オレ
フィン類の単独又は共重合体等に例えばマレイン酸、フ
マル酸、アクリル酸等の不飽和カルボン酸又はその酸無
水物、エステル若しくは金属塩等の誘導体を共重合例え
ばグラフト共重合した変性重合体を代表的なものとして
例示でき、上記変性重合体の単独又は他の成分、例えば
他のポリオレフィン系樹脂との混合物等も前記変性ポリ
オレフィン系樹脂の中に含まれる。この際特に好ましい
ポリオレフィン系樹脂は低密度ポリエチレン、線状低密
度ポリエチレン、アイオノマー樹脂、変性ポリオレフィ
ン系樹脂、エチレン−酢酸ビニル共重合体等である。上
記ポリオレフィン系樹脂は単独で或は２種以上混合して
用いられ得る。こうしたポリオレフィン系樹脂からなる
層は必要ならばヒートシール層として使用することも可
能であり便利である。In this case, the structure of the multilayer film may be 2H or more, preferably about 3 to 6 layers. When creating multiple layers,
There are no particular restrictions on the resins used for the other layers, and various resin layers may be used in appropriate combinations.As a commonly used resin, a polyolefin resin layer can be exemplified first. Examples of such polyolefin resins include homopolymers and mutual copolymers of olefins, copolymers with other copolymerizable monomers, such as other vinyl heptanomers, and modified copolymers thereof. can. Specifically, for example, polyethylene of various densities ranging from low density to high density (including linear low density polyethylene), polypropylene,
Examples include polybutene, mutual copolymers thereof, ionomer resins, ethylene-acrylic acid copolymers, ethylene-vinyl acetate copolymers, and modified polyolefin resins. Here, the modified polyolefin resin may be a single or copolymer of the above-mentioned olefins combined with an unsaturated carboxylic acid such as maleic acid, fumaric acid, or acrylic acid, or its acid anhydride, ester, or derivative such as a metal salt. Typical examples include modified polymers obtained by polymerization, such as graft copolymerization, and the modified polyolefin resins include the above-mentioned modified polymers alone or with other components, such as mixtures with other polyolefin resins. . Particularly preferred polyolefin resins include low density polyethylene, linear low density polyethylene, ionomer resins, modified polyolefin resins, and ethylene-vinyl acetate copolymers. The above polyolefin resins may be used alone or in combination of two or more. A layer made of such a polyolefin resin can be conveniently used as a heat-sealing layer if necessary.
またガスバリアー性樹脂も他の層に用いられる樹脂の一
つとして例示でき、こうしたガスバリヤ−性を有する樹
脂には、ナイロン６、ナイロン６６、これらの共重合体
等の脂肪族系ポリアミド樹脂（ナイロン）、芳香族系ポ
リアミド樹脂、ポリアクリロニトリル系樹脂、ポリ塩化
ビニリデン系樹脂、エチレン−ビニルアルコール共重合
体（例えばエチレン含有機２０〜６０モル％、けん化度
９０％以上のエチレン−Ｍ酸ビニル共重合体けん化物）
等を例示することができ、更にはポリエステル系樹脂等
も例示できる。Gas barrier resins can also be exemplified as one of the resins used in other layers, and examples of such gas barrier resins include aliphatic polyamide resins (nylon ), aromatic polyamide resins, polyacrylonitrile resins, polyvinylidene chloride resins, ethylene-vinyl alcohol copolymers (e.g., ethylene-vinyl alcohol copolymers containing 20 to 60 mol% of ethylene and having a saponification degree of 90% or more) combined saponified product)
Further examples include polyester resins and the like.
こうした多層フィルムの中でより好ましい態様としては
チューブ状フィルムであって、かつ外側から順に本発明
に係るポリアミド系重合体層、ガスバリアー性樹脂層、
変性ポリオレフィン系樹脂層の少なくとも三層を基本構
成とするものを例示でき、こうした多層フィルムは基本
構成さえ端えていれば他はいかなる層構成であっても差
しつかえない。A more preferable embodiment of such a multilayer film is a tubular film, and in order from the outside, the polyamide polymer layer according to the present invention, the gas barrier resin layer,
An example is a film having a basic structure of at least three modified polyolefin resin layers, and such a multilayer film may have any other layer structure as long as the basic structure is complete.
多層チューブを構成する各層の樹脂として種々の組合わ
せを採用できることは以上の説明で明らかであるが、更
に好ましい組合わせ例を例示すると以下の通りである。Although it is clear from the above description that various combinations can be employed as resins for each layer constituting the multilayer tube, more preferable combinations are exemplified as follows.
尚下記において各アルファベット記号は下記の樹脂を表
示するものとし、チューブ状フィルムの場合は最初の記
号を外層とする。また、アンダーラインは請求の範囲第
２項に係る基本構成を示す。In the following, each alphabetic symbol represents the following resin, and in the case of a tubular film, the first symbol represents the outer layer. Moreover, the underlined line indicates the basic configuration according to claim 2.
Ａ：本発明のポリアミド系重合体 Ｂ：変性ポリオレフィン系樹脂 Ｃ：ポリオレフずン系樹脂 Ｄ：１Ｍに用いる重合体以外のガスバリヤ−性団脂 Ａ／Ｂ／Ｃ，Ａ／Ｄ／Ｃ。A: Polyamide polymer of the present invention B: Modified polyolefin resin C: Polyolefin resin D: Gas barrier resin other than the polymer used for 1M A/B/C, A/D/C.
Ｂ ／ Ａ ／ Ｂ％Ｂ／Ｄ／Ｂ、Ａ乙且Ｚ１、Ｂ／Ａ
／Ｂ／Ｃ，Ｂ／Ｄ／Ｂ／Ｃ３
ＮＺ旦Ｚ１／Ｃ，Ａ／Ｂ／Ｄ／Ｂ。B/A/B%B/D/B, A and Z1, B/A
/B/C, B/D/B/C3 NZdan Z1/C, A/B/D/B.
Ｂ／Ｄ／Ａ／Ｂ、Ｂ／ｌ旦Ｚ里、 Ｃ／Ｂ／Ｄ／Ｂ／Ｃ，Ａ／Ｂ／Ｄ／Ｂ／Ｃ。B/D/A/B, B/l Dan Zuri, C/B/D/B/C, A/B/D/B/C.
Ｂ／Ａ乙旦１３／Ｃ％Ｆ３／Ｄ／Ａ／Ｂ／Ｃ。B/A Otodan 13/C%F3/D/A/B/C.
Ｂ／１１．／１１．／Ｂ／Ｃ，Ｄ／Ａ／１３／Ｃ１Ａ／
Ｂ／Ｃ，、／Ｃ−！
向上記においてＣ−＋及びＣ−３は夫々異なるポリオレ
フィン系樹脂を、ＩＩ、及びＤ−ｔは夫々異なるガスバ
リヤ−性樹脂を示す。B/11. /11. /B/C, D/A/13/C1A/
B/C,,/C-! In the above description, C-+ and C-3 represent different polyolefin resins, and II and D-t represent different gas barrier resins.
上記組合せにおいてＢをアイオノマー樹脂に代えたもの
、また最外層を塩化ビニリデン系樹脂層（１））におき
かえたもの又は塩化ビニリデン系樹脂を更にコートした
ものも包含される。またＤとしてエチレン−ビニルアル
コール共重合体、脂肪族系ポリアミド樹脂（この場合、
できるだけ薄くしないと熱収縮性を阻害する恐れがあり
、３〜ＩＯμｍ程度の厚さを例示できる。）、塩化ビニ
リデン系樹脂を使用することもできる。The above combinations include those in which B is replaced with an ionomer resin, those in which the outermost layer is replaced with a vinylidene chloride resin layer (1)), or those further coated with a vinylidene chloride resin. In addition, as D, ethylene-vinyl alcohol copolymer, aliphatic polyamide resin (in this case,
If it is not made as thin as possible, heat shrinkability may be inhibited, and a thickness of about 3 to 10 μm can be exemplified. ), vinylidene chloride resins can also be used.
本発明は共押出等適宜の装置を用いインフレート法によ
りチューブ状フィルム、もしくは共押出Ｔダイ法により
フラット状フィルム等として成膜すればよいが、特に制
限はない、しかしながら熱収縮性を有する必要があり、
更に必要ならばガスバリヤ−性を有するものが好ましく
、熱収縮性については特に制限はないが、例えば８０℃
での温水に３０秒浸漬した際に走行方向に２０％以上。In the present invention, the film may be formed as a tube-shaped film by the inflation method using an appropriate device such as co-extrusion, or a flat-shaped film by the co-extrusion T-die method, but there is no particular restriction, however, it is necessary to have heat shrinkability. There is,
Furthermore, if necessary, it is preferable to have gas barrier properties, and there are no particular restrictions on heat shrinkability, but for example, at 80°C.
20% or more in the running direction when immersed in hot water for 30 seconds.
走行方向と直角方向に２０％以上、好ましくは前者、後
者共に２５〜４０％程度の熱収縮率のものを好適なもの
として例示できる。Suitable examples include those having a heat shrinkage rate of 20% or more in the direction perpendicular to the running direction, preferably about 25 to 40% in both the former and the latter.
熱収縮性を付与せしめるためには延伸を行う必要があり
、延伸については成膜−冷却後再加熱して行う方法を例
示でき、成膜と延伸を連続で行うも、別工程で行うもど
ちらでもよい、更に溶融延伸法、即ち押出し製膜と延伸
とを同時に行う方法により熱収縮性を付与して６よい。In order to impart heat shrinkability, it is necessary to perform stretching, and an example of stretching is a method in which film formation is performed by cooling and then reheating. Furthermore, heat shrinkability may be imparted by a melt-stretching method, that is, a method in which extrusion film formation and stretching are performed simultaneously.
延伸倍率ち特に制限はないが、例えば縦、横各々に２．
０〜５．０倍、好ましくは２．５〜４．０倍程度を例示
でき、延伸温度も特に制限はないが、通常は６０〜１０
０℃、好ましくは７０〜９０℃程度を例示できる。There is no particular restriction on the stretching ratio, but for example, the stretching ratio may be 2.
0 to 5.0 times, preferably about 2.5 to 4.0 times, and the stretching temperature is also not particularly limited, but usually 60 to 10 times.
An example is 0°C, preferably about 70 to 90°C.
本発明に係る熱収縮性多層フィルムの用途としては食肉
、加工肉、レトルト食品、水物食品等、食品用包装材料
、その他各種包装材料をあげることができ、またａ絞り
容器等に加工することも可能である。このように用途は
各方面に渡っており特に制限はない、包装形態としては
ヒートシールにより袋状としても、またクリップ等の金
環により１−１緘してもよく特に制限はないが、チュー
ブ状フィルムの場合は所定の寸法にカットするだけで包
装材料として便用することもでき、便利である。Applications of the heat-shrinkable multilayer film according to the present invention include meat, processed meat, retort foods, aquatic foods, food packaging materials, and various other packaging materials. is also possible. As described above, the applications are wide-ranging and there are no particular restrictions.The packaging form may be heat-sealed in the form of a bag, or wrapped in a metal ring such as a clip. In the case of film, it can be conveniently used as a packaging material by simply cutting it into a predetermined size.
以上は本発明の好ましい実施態様を例示したまでで、本
発明はかかる記載に制限を受けることなく、あらゆる実
施態様を取ることが可能である。The above is just an example of preferred embodiments of the present invention, and the present invention is capable of taking any embodiments without being limited to such descriptions.
〈実施例１〉
外層から順に、ナイロン６−６６共重合体７０重看％と
非晶質系ポリアミド樹脂３０重量％を含有するポリアミ
ド系重合体層、エチレン含有型４４モル％、けん化度９
９％以上のエチレン−酢酸ビニル共重合体けん化物層お
よび変性エチレン−酢酸ビニル共重合体を含有する樹脂
層となるように共押出し、インフレート成膜してなるチ
ューブ状フィルムを温度８０℃で縦、横付々３．Ｏ×２
．８倍にインフレーション延伸を行い、第１図実線に示
す如き、熱収縮率を有する多層熱収縮性フィルムを得た
。この際熱収縮率は温水浴、３０秒浸漬時の横方向の値
である。<Example 1> In order from the outer layer, a polyamide polymer layer containing 70% by weight of nylon 6-66 copolymer and 30% by weight of amorphous polyamide resin, 44% by weight of ethylene content, and a saponification degree of 9
A tubular film formed by coextrusion and blow-forming to form a saponified ethylene-vinyl acetate copolymer layer and a resin layer containing a modified ethylene-vinyl acetate copolymer of 9% or more was heated at a temperature of 80°C. Vertical and horizontal 3. O×2
．． Inflation stretching was performed 8 times to obtain a multilayer heat-shrinkable film having a heat-shrinkage rate as shown by the solid line in Figure 1. At this time, the heat shrinkage rate is the value in the lateral direction when immersed in a hot water bath for 30 seconds.
尚、各層の厚さは外層からｌ ２／ｌ Ｏ７２８μｍで
ある。Note that the thickness of each layer is l 2 /l O 728 μm from the outer layer.
〈比較例１〉
実施例１における外層としてナイロン６−６６共重合体
のみからなるポリアミド層を用いる以外、実施例１と同
様にして、熱収縮性多層フィルムを得た。このフィルム
の同条（’ｌ＝での熱収縮率は笛１図破線に示す通りで
あった。<Comparative Example 1> A heat-shrinkable multilayer film was obtained in the same manner as in Example 1 except that a polyamide layer consisting only of nylon 6-66 copolymer was used as the outer layer in Example 1. The heat shrinkage rate of this film in the same strip ('l=) was as shown by the broken line in Figure 1.
この図から６明らかなように本発明に係る実施例のもの
は、熱収縮率において比較例に比べ５〜ｌＯ％程度と良
好な値を示した。こうしたチューブ状フィルムを所定の
寸法にシール、カットし袋状として、その中に食肉類を
入れ、入り口をヒートシールして熱収縮せしめたところ
、食肉類とチューブ状フィルムとがぴったり密着してお
り、経時による肉汁の発生がおさえられた。これに対し
比較例のものを用い同様に包装を行ったところ、この包
装物はぴったりと密着はしているけれど、実施例程良好
でなく、こうした点でも本発明の効果がうかがえる。As is clear from this figure, the examples according to the present invention exhibited good thermal shrinkage rates of about 5 to 10% compared to the comparative examples. When such a tubular film was sealed and cut into a predetermined size to form a bag, meat was placed inside the bag, and the entrance was heat-sealed and heat-shrinked, the meat and the tubular film were in close contact with each other. , the occurrence of meat juices over time was suppressed. On the other hand, when a comparative example was used and packaged in the same manner, the packaged product adhered snugly, but not as well as in the example, and the effects of the present invention can be seen in this respect as well.
〈実施例２〉
外層から順に変性低密度ポリエチレンを含む樹脂層、ナ
イロン６−６６共重合体７５重量％と非晶質系ポリアミ
ド樹脂２５重量％を含有するポリアミド系重合体層、エ
チレン含有量４４モル％、けん化度９９％以上のエチレ
ン−酢酸ビニル共重合体けん化物層、変性低密度ポリエ
チレンを含む樹脂層および酢酸ビニル含有ｌｌｌ０重量
％のエチレン−酢酸ビニル共重合体層からなる五層フィ
ルムをチューブ状に共押出成膜し、しかる後温度８０℃
で、ｌｉｉ横、３．ＯＸ３．０倍にインフレーション法
により同時２軸延伸を行なって８０℃、温水浴、３０秒
における熱収縮率が縦方向に３２％、横方向に３０％の
フィルムを得た。こうして得たフィルムの厚さは外層か
ら順に５７１５／Ｉ Ｏ１５／ｌ Ｏｕｍであった。<Example 2> In order from the outer layer, a resin layer containing modified low-density polyethylene, a polyamide polymer layer containing 75% by weight of nylon 6-66 copolymer and 25% by weight of amorphous polyamide resin, and an ethylene content of 44%. A five-layer film consisting of a saponified ethylene-vinyl acetate copolymer layer with a mole% saponification degree of 99% or more, a resin layer containing modified low-density polyethylene, and an ethylene-vinyl acetate copolymer layer with a vinyl acetate content of 0% by weight. Co-extruded into a tube and then heated to 80°C.
So, lii side, 3. Simultaneous biaxial stretching was carried out by the inflation method to OX3.0 times to obtain a film having a heat shrinkage rate of 32% in the machine direction and 30% in the transverse direction at 80° C. in a hot water bath for 30 seconds. The thickness of the film thus obtained was 5715/I O15/l Oum in order from the outer layer.
〈発明の効果〉
本発明は多層フィルムにおける少なくとも一層に特定の
ポリアミド系重合体層を用いるため、熱収縮性が良好で
、各種包装材料として好適に用いられ、今後の用途拡大
に大きな期待が寄せられている。<Effects of the Invention> Since the present invention uses a specific polyamide polymer layer as at least one layer in the multilayer film, it has good heat shrinkability and can be suitably used as various packaging materials, and there are great expectations for future expansion of applications. It is being
例えば、被包装物を食肉類とする時は、熱収縮性が良好
で、食肉類とぴったりと密着して包装されるため、経時
による肉汁等の発生がおさえられ、こうした面でも本発
明のものは格別な効果が期待できる。For example, when the object to be packaged is meat, it has good heat shrinkability and is packaged in close contact with the meat, which prevents the generation of meat juices etc. over time. can be expected to have an exceptional effect.
第１図は温度と熱収量率の関係を示すグラフである。 FIG. 1 is a graph showing the relationship between temperature and heat yield rate.
Claims (1)
リアミド樹脂６０〜９５重量％と非晶質系ポリアミド樹
脂４０〜５重量％とを含有するポリアミド系重合体であ
ることを特徴とする熱収縮性多層フィルム。 ２）多層フィルムがチューブ状であり、外側から順に脂
肪族系ポリアミド樹脂６０〜９５重置％と非晶質系ポリ
アミド樹脂４０〜５重合％とを含有するポリアミド系重
合体層、ガスバリアー性樹脂層、変性ポリオレフィン系
樹脂層の少なくとも三層を基本構成とすることを特徴と
する熱収縮性多層フィルム。[Claims] 1) At least one layer in the multilayer film is a polyamide polymer containing 60 to 95% by weight of an aliphatic polyamide resin and 40 to 5% by weight of an amorphous polyamide resin. A heat-shrinkable multilayer film. 2) The multilayer film is tubular, and in order from the outside are a polyamide polymer layer containing 60 to 95 percent polymerization of aliphatic polyamide resin and 40 to 5 percent polymerization of amorphous polyamide resin, and a gas barrier resin. 1. A heat-shrinkable multilayer film characterized by having a basic structure of at least three layers: a polyolefin resin layer and a modified polyolefin resin layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1200814A JPH0363133A (en) | 1989-08-01 | 1989-08-01 | Heat-shrinkable multilayer film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1200814A JPH0363133A (en) | 1989-08-01 | 1989-08-01 | Heat-shrinkable multilayer film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0363133A true JPH0363133A (en) | 1991-03-19 |
Family
ID=16430642
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1200814A Pending JPH0363133A (en) | 1989-08-01 | 1989-08-01 | Heat-shrinkable multilayer film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0363133A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0585459A1 (en) * | 1992-03-18 | 1994-03-09 | Sumitomo Bakelite Company Limited | Multilayered stretched film |
| US5562996A (en) * | 1990-06-27 | 1996-10-08 | Gunze Limited | Multi-layer films |
| US6764729B2 (en) | 1992-06-05 | 2004-07-20 | Cryovac, Inc. | Backseamed casing and packaged product incorporating same |
| US7939147B2 (en) | 2002-01-25 | 2011-05-10 | Dupont Teijin Films U.S. Limited Partnership | Heat-sealable and shrinkable multi-layer polymeric film |
-
1989
- 1989-08-01 JP JP1200814A patent/JPH0363133A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5562996A (en) * | 1990-06-27 | 1996-10-08 | Gunze Limited | Multi-layer films |
| US5688456A (en) * | 1990-06-27 | 1997-11-18 | Gunze Limited | Process for preparation of multilayer films |
| EP0585459A1 (en) * | 1992-03-18 | 1994-03-09 | Sumitomo Bakelite Company Limited | Multilayered stretched film |
| EP0585459A4 (en) * | 1992-03-18 | 1994-08-24 | Sumitomo Bakelite Co | Multilayered stretched film |
| US6764729B2 (en) | 1992-06-05 | 2004-07-20 | Cryovac, Inc. | Backseamed casing and packaged product incorporating same |
| US7540834B2 (en) | 1992-09-25 | 2009-06-02 | Cryovac, Inc. | Backseamed casing and packaged product incorporating same |
| US7939147B2 (en) | 2002-01-25 | 2011-05-10 | Dupont Teijin Films U.S. Limited Partnership | Heat-sealable and shrinkable multi-layer polymeric film |
| US8394470B2 (en) | 2002-01-25 | 2013-03-12 | Dupont Teijin Films U.S. Limited Partnership | Heat-sealable and shrinkable multi-layer polymeric film |
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