JPH0310041Y2 - - Google Patents
Info
- Publication number
- JPH0310041Y2 JPH0310041Y2 JP1984178712U JP17871284U JPH0310041Y2 JP H0310041 Y2 JPH0310041 Y2 JP H0310041Y2 JP 1984178712 U JP1984178712 U JP 1984178712U JP 17871284 U JP17871284 U JP 17871284U JP H0310041 Y2 JPH0310041 Y2 JP H0310041Y2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- olefin resin
- density polyethylene
- laminate
- modified olefin
- 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.)
- Expired
Links
- 229920005989 resin Polymers 0.000 claims description 15
- 239000011347 resin Substances 0.000 claims description 15
- 229920005672 polyolefin resin Polymers 0.000 claims description 10
- -1 polypropylene Polymers 0.000 claims description 9
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 7
- 229920001155 polypropylene Polymers 0.000 claims description 7
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- 229920001903 high density polyethylene Polymers 0.000 claims description 3
- 239000004700 high-density polyethylene Substances 0.000 claims description 3
- 229920001179 medium density polyethylene Polymers 0.000 claims description 3
- 239000004701 medium-density polyethylene Substances 0.000 claims description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical class C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims 1
- 229920001684 low density polyethylene Polymers 0.000 claims 1
- 239000004702 low-density polyethylene Substances 0.000 claims 1
- 239000010410 layer Substances 0.000 description 12
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 239000012790 adhesive layer Substances 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 description 4
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 4
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
Landscapes
- Wrappers (AREA)
- Laminated Bodies (AREA)
Description
【考案の詳細な説明】
〔産業上の利用分野〕
本考案は高度の水分および酸素の遮断性に優
れ、かつ層間剥離を起さず、ボイル処理にも耐え
ることのできる、柔軟で層構成が簡易な積層体に
関するものである。
〔従来技術〕
従来、塩化ビニリデン系共重合体より成るフイ
ルムは、気体遮断性、強度、透明性、作業性他、
包装材料としての適性が優秀で、特に食品包装用
途に広く普及している。しかし反面において高価
であること、低温可撓性、ヒートシール性に乏し
いこと、また内容物が油性のものであるときはフ
イルム中の可塑剤が抽出されて内容物を汚染する
等の欠点を併有する。これらの欠点を補う為に例
えば特公昭53−24464号公報に見られるが如き、
エチレン系樹脂と塩化ビニリデン系樹脂との積層
フイルムが考案され広く使用されている。しかし
ここでいうエチレン系樹脂はエチレンと酢酸ビニ
ル等との共重合体であり、これらの樹脂は耐溶剤
性に乏しく、軟化点が低く、強度も弱いために、
その用途が限られていた。また従来塩化ビニリデ
ンとの接着層樹脂として使われていた、エチレン
アルキルアクリレート共重合樹脂、スチレン−ブ
タジエン共重合樹脂などもエチレン−酢酸ビニル
共重合体とほぼ同様の性質を持ち用途が限られて
いた。
また、エチレン−酢酸ビニル共重合体等を接着
層樹脂として用い、その外層にポリエチレン単体
等を積層した4層、5層のフイルムが考案され上
記欠点が改良されたが内容物が油性のものである
と接着力が減少したり、ボイル処理等を行うと接
着層の軟化点が低い為に変形を生じたり、高度の
多層ダイを用いる為の層流が乱れ均一な積層体が
得られないという欠点があつた。
〔考案の目的〕
本考案者らは、上記のような欠点を改良する為
に研究した結果、種々の接着性樹脂と塩化ビニリ
デン系樹脂との接着について調査した結果、酸変
性したポリオレフインが塩化ビニリデンと接着す
るという知見を得、更にこの知見に基づき種々研
究を進めて本考案を完成するに至つたものであ
る。その目的とするところは高度の水分および酸
素の遮断性に優れ、かつ層間剥離を越さず、ボイ
ル処理にも耐えることのできる、柔軟で、層構成
が簡易である積層体を提供するにある。
〔考案の構成〕
すなわち本考案は、塩化ビニリデン系樹脂層の
片面又は両面に酸変性オレフイン樹脂層を配した
積層体において、該酸変性オレフイン樹脂とし
て、中密度ポリエチレン、高密度ポリエチレン、
直鎖状低密度ポリエチレン、ポリプロピレンを不
飽和脂肪酸またはその無水物を化学的に結合させ
てなる酸変性オレフイン樹脂でビカツト軟化点が
90℃以上の樹脂を使用してなる積層体である。
本考案に用いる塩化ビニリデン系樹脂は、塩化
ビニリデンを主体として、これと塩化ビニル、ア
ルキルアクリレート、アクリル酸、アクリロニト
リルその他の共重合成分とを共重合した、二元又
は多元の共重合物である。
また本考案で用いる酸変性オレフイン樹脂と
は、中密度ポリエチレン、高密度ポリエチレン、
直鎖状低密度ポリエチレン、ポリプロピレンにア
クリル酸、メタクリル酸などの一塩基性不飽和脂
肪酸、あるいはマレイン酸、フマル酸、イタコン
酸などの二塩基性不飽和脂肪酸、さらには二塩基
性不飽和脂肪酸の無水物、すなわち、無水マレイ
ン酸等を化学的に結合させて得られるものでビカ
ツト軟化点が90℃以上のものである。ここではエ
チレン−酢酸ビニル共重合体を同様の方法で酸変
性した樹脂はビカツト軟化点が90゜未満になり、
高温での使用に耐えられず実用的ではない。本考
案における酸変性オレフイン樹脂の例としては、
三井石油化学製アドマー等がある。
〔考案の効果〕
本考案に従うと、従来のポリ塩化ビニリデンを
バリア層としてその両側にエチレン−酢酸ビニル
共重合体を配した構造の積層体では、高熱での処
理例えばボイル処理において、両外層の剥離、積
層体の変形が生じたが、本考案による積層体では
高温処理に耐えることができた。また従来より外
層にナイロン等の耐熱樹脂を配した積層体では高
温処理には耐えられるものの、層構成が4層以上
になり、製造面、経済性の点でも問題があつた
が、本考案方法に従うと簡易な方法で耐熱性、耐
油性のある包装材が得られ、食肉等の包装材とし
て好適である。
実施例 1
2台の押出機を具えた共押出成膜装置により、
塩化ビニリデン樹脂A、ポリプロピレンをマレイ
ン酸により酸変性した酸変性ポリプロピレンBを
B−A−Bの順に積層したフイルムを作つた。各
層の厚みはB−A−Bの順で夫々40μ、10μ、40μ
で合計90μであつた。
実施例 2
実施例1において、酸変性ポリプロピレンの代
りにマレイン酸変性直鎖状ポリエチレンを用いて
実施例1と同様のフイルムを作つた。
比較例 1
実施例1において、酸変性ポリプロピレンの代
りにエチレン−酢酸ビニル共重合体を用いて実施
例1と同様のフイルムを作つた。
実施例1、2、比較例1を用いて、二枚重ね合
せにしてヒートシールを行い袋を作つた。この袋
に牛脂を充填して、ヒートシールにより密封し、
この袋30個のレトルト処理を処理条件60℃、30
分:70℃、30分:80℃、0分で各々行つた。結果
を表−1に示す。
【表】[Detailed description of the invention] [Industrial application field] The present invention has a flexible layer structure that has excellent moisture and oxygen barrier properties, does not cause delamination, and can withstand boiling treatment. This relates to a simple laminate. [Prior Art] Conventionally, films made of vinylidene chloride copolymers have poor gas barrier properties, strength, transparency, workability, etc.
It has excellent suitability as a packaging material, and is especially widely used in food packaging applications. However, on the other hand, it has disadvantages such as being expensive, having poor low-temperature flexibility and heat-sealing properties, and if the contents are oil-based, the plasticizer in the film may be extracted and contaminate the contents. have In order to compensate for these shortcomings, for example, as seen in Japanese Patent Publication No. 53-24464,
A laminated film of ethylene resin and vinylidene chloride resin has been devised and widely used. However, the ethylene resin referred to here is a copolymer of ethylene and vinyl acetate, etc., and these resins have poor solvent resistance, low softening point, and weak strength.
Its use was limited. Additionally, ethylene alkyl acrylate copolymer resins and styrene-butadiene copolymer resins, which were conventionally used as adhesive layer resins with vinylidene chloride, had properties similar to those of ethylene-vinyl acetate copolymers, and their applications were limited. . In addition, four- or five-layer films were devised in which ethylene-vinyl acetate copolymer or the like was used as the adhesive layer resin, and polyethylene alone was laminated on the outer layer, and the above drawbacks were improved, but the content was oil-based. If this happens, the adhesive force will decrease, and if the adhesive layer is subjected to boiling treatment, it will deform due to the low softening point of the adhesive layer, and the laminar flow required for using advanced multilayer dies will be disrupted, making it impossible to obtain a uniform laminate. There were flaws. [Purpose of the invention] As a result of research to improve the above-mentioned drawbacks, the present inventors investigated the adhesion between various adhesive resins and vinylidene chloride-based resins. Based on this knowledge, they conducted various research and completed the present invention. The objective is to provide a flexible laminate with a simple layer structure that has excellent moisture and oxygen barrier properties, does not suffer from delamination, and can withstand boiling treatment. . [Structure of the invention] That is, the invention provides a laminate in which an acid-modified olefin resin layer is arranged on one or both sides of a vinylidene chloride resin layer, and the acid-modified olefin resin is medium-density polyethylene, high-density polyethylene,
An acid-modified olefin resin made by chemically bonding linear low-density polyethylene or polypropylene with unsaturated fatty acids or their anhydrides, and has a high softening point.
It is a laminate made of resin with a temperature of 90°C or higher. The vinylidene chloride resin used in the present invention is a binary or multi-component copolymer consisting mainly of vinylidene chloride and copolymerized with vinyl chloride, alkyl acrylate, acrylic acid, acrylonitrile, and other copolymer components. In addition, the acid-modified olefin resin used in this invention includes medium density polyethylene, high density polyethylene,
Linear low-density polyethylene, polypropylene, monobasic unsaturated fatty acids such as acrylic acid, methacrylic acid, dibasic unsaturated fatty acids such as maleic acid, fumaric acid, itaconic acid, and even dibasic unsaturated fatty acids. It is an anhydride, that is, one obtained by chemically bonding maleic anhydride, etc., and has a Vikato softening point of 90°C or higher. Here, a resin obtained by acid-modifying an ethylene-vinyl acetate copolymer using a similar method has a Vikato softening point of less than 90°,
It cannot withstand use at high temperatures and is not practical. Examples of acid-modified olefin resins in the present invention include:
Examples include Mitsui Petrochemical's Admer. [Effects of the invention] According to the invention, in a conventional laminate having a structure in which polyvinylidene chloride is used as a barrier layer and ethylene-vinyl acetate copolymer is arranged on both sides, both outer layers are not easily formed during high heat treatment, such as boiling treatment. Although peeling and deformation of the laminate occurred, the laminate according to the present invention was able to withstand high-temperature treatment. In addition, conventional laminates with heat-resistant resin such as nylon on the outer layer can withstand high-temperature treatment, but the layer structure has four or more layers, which poses problems in terms of manufacturing and economic efficiency. According to the method, a heat-resistant and oil-resistant packaging material can be obtained by a simple method, and is suitable as a packaging material for meat, etc. Example 1 Using a coextrusion film forming apparatus equipped with two extruders,
A film was prepared by laminating vinylidene chloride resin A and acid-modified polypropylene B, which is obtained by acid-modifying polypropylene with maleic acid, in the order of B-A-B. The thickness of each layer is 40μ, 10μ, 40μ in the order of B-A-B.
The total amount was 90μ. Example 2 A film similar to that in Example 1 was produced using maleic acid-modified linear polyethylene instead of acid-modified polypropylene. Comparative Example 1 A film similar to that in Example 1 was made using ethylene-vinyl acetate copolymer instead of acid-modified polypropylene. Using Examples 1 and 2 and Comparative Example 1, bags were made by stacking two sheets and heat-sealing them. This bag is filled with beef tallow and sealed by heat sealing.
Processing conditions for 30 bags: 60℃, 30℃
Minutes: 70°C, 30 minutes: 80°C, 0 minutes. The results are shown in Table-1. 【table】
第1図は本考案の積層体の断面図である。 FIG. 1 is a sectional view of the laminate of the present invention.
Claims (1)
性オレフイン樹脂層また酸変性オレフイン樹脂を
含有するオレフイン樹脂層を配した積層体におい
て、該酸変性オレフイン樹脂として、中密度ポリ
エチレン、高密度ポリエチレン、直鎖状低密度ポ
リエチレン、ポリプロピレンを不飽和樹脂酸また
はその無水物を化学的に結合させてなる酸変性オ
レフイン樹脂でビカツト軟化点が90℃以上の樹脂
を使用してなる積層体。 In a laminate in which an acid-modified olefin resin layer or an olefin resin layer containing an acid-modified olefin resin is arranged on one or both sides of a vinylidene chloride-based resin layer, the acid-modified olefin resin is medium density polyethylene, high density polyethylene, linear chain A laminate made of acid-modified olefin resin, which is made by chemically bonding low-density polyethylene or polypropylene with an unsaturated resin acid or its anhydride, and has a Vikatsu softening point of 90°C or higher.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1984178712U JPH0310041Y2 (en) | 1984-11-27 | 1984-11-27 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1984178712U JPH0310041Y2 (en) | 1984-11-27 | 1984-11-27 |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6193232U JPS6193232U (en) | 1986-06-16 |
JPH0310041Y2 true JPH0310041Y2 (en) | 1991-03-13 |
Family
ID=30736276
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1984178712U Expired JPH0310041Y2 (en) | 1984-11-27 | 1984-11-27 |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0310041Y2 (en) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4872289A (en) * | 1971-10-28 | 1973-09-29 | ||
JPS5710812B2 (en) * | 1976-06-24 | 1982-03-01 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS642766Y2 (en) * | 1980-06-20 | 1989-01-24 |
-
1984
- 1984-11-27 JP JP1984178712U patent/JPH0310041Y2/ja not_active Expired
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4872289A (en) * | 1971-10-28 | 1973-09-29 | ||
JPS5710812B2 (en) * | 1976-06-24 | 1982-03-01 |
Also Published As
Publication number | Publication date |
---|---|
JPS6193232U (en) | 1986-06-16 |
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