JPH0160421B2 - - Google Patents
Info
- Publication number
- JPH0160421B2 JPH0160421B2 JP58090619A JP9061983A JPH0160421B2 JP H0160421 B2 JPH0160421 B2 JP H0160421B2 JP 58090619 A JP58090619 A JP 58090619A JP 9061983 A JP9061983 A JP 9061983A JP H0160421 B2 JPH0160421 B2 JP H0160421B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- layer
- vinyl acetate
- multilayer structure
- acetate copolymer
- 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 60
- 239000011347 resin Substances 0.000 claims description 60
- 239000000463 material Substances 0.000 claims description 24
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 21
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 229920005672 polyolefin resin Polymers 0.000 claims description 14
- 239000004840 adhesive resin Substances 0.000 claims description 8
- 229920006223 adhesive resin Polymers 0.000 claims description 8
- 229920005990 polystyrene resin Polymers 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 6
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 50
- 238000000034 method Methods 0.000 description 12
- -1 polypropylene Polymers 0.000 description 11
- 239000004743 Polypropylene Substances 0.000 description 10
- 229920001155 polypropylene Polymers 0.000 description 9
- 239000005977 Ethylene Substances 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000005003 food packaging material Substances 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000003856 thermoforming Methods 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
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- XLYMOEINVGRTEX-ARJAWSKDSA-N Ethyl hydrogen fumarate Chemical compound CCOC(=O)\C=C/C(O)=O XLYMOEINVGRTEX-ARJAWSKDSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-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
- 239000004698 Polyethylene Substances 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
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- UIERETOOQGIECD-ARJAWSKDSA-N angelic acid Chemical compound C\C=C(\C)C(O)=O UIERETOOQGIECD-ARJAWSKDSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 235000013365 dairy product Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene 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
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 229910052751 metal Chemical class 0.000 description 1
- 239000002184 metal Chemical class 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
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000573 polyethylene 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
- 238000012545 processing Methods 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 235000021067 refined food Nutrition 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Wrappers (AREA)
- Laminated Bodies (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Description
【発明の詳細な説明】
本発明は、多層構造材料の製造方法に関するも
のであり、詳しくは食品包装材料などに用いられ
る多層構造材料を安価に、かつ生産性よく製造す
ることを可能にした多層構造材料の製造方法に関
するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a multilayer structure material, and more specifically, a method for manufacturing a multilayer structure material, which makes it possible to manufacture a multilayer structure material used for food packaging materials at low cost and with high productivity. The present invention relates to a method for manufacturing structural materials.
従来、エチレン−酢酸ビニル共重合体けん化物
はガスバリヤー性にすぐれているため、食品包装
用材料として非常に適しており、広く用いられて
いる。しかしながら、エチレン−酢酸ビニル共重
合体けん化物の単層フイルムとして用いられるこ
とは少なく、耐熱性、防湿性、耐油性、成形性、
二次加工性などの改良を目的としてポリプロピレ
ンなどのポリオレフイン系樹脂あるいはポリスチ
レン、スチレン−ブタジエン共重合体などのスチ
レン系樹脂を両外層とした多層構造材料とし、そ
れぞれの樹脂の有する特徴を併せ持つている材料
として使用されている。 Conventionally, saponified ethylene-vinyl acetate copolymers have excellent gas barrier properties and are therefore very suitable and widely used as food packaging materials. However, saponified ethylene-vinyl acetate copolymer is rarely used as a single-layer film, and it has poor heat resistance, moisture resistance, oil resistance, moldability,
For the purpose of improving secondary processability, it is a multilayer material with both outer layers made of polyolefin resins such as polypropylene, or styrene resins such as polystyrene and styrene-butadiene copolymer, and combines the characteristics of each resin. used as a material.
これら多層構造材料は通常、共押出成形法によ
りシートまたはフイルム状に成形されているが、
多層構造のため、押出成形開始後均一な製品を得
るまでの不良品や耳部トリミングにより発生する
多量のスクラツプのため、その製品コストは非常
に高くなつている。 These multilayered materials are usually formed into sheets or films by coextrusion.
Due to the multilayer structure, the product cost is very high due to a large amount of scrap generated from defective products and edge trimming from the start of extrusion until a uniform product is obtained.
そこで、省資源、製品コストの低下を図るため
にスクラツプ回収品を原料樹脂に混入することも
考えられるが、通常の方法ではエチレン−酢酸ビ
ニル共重合体けん化物の耐熱性が低いために、ゲ
ルを生成しやすいという欠点がある。特に、酸化
チタンなどを添加した着色製品にあつてはゲル発
生が促進され、長時間の連続運転ができないとい
う大きな欠点がある。 Therefore, in order to conserve resources and reduce product costs, it may be possible to mix recovered scrap products into the raw resin, but with the usual method, the heat resistance of the saponified ethylene-vinyl acetate copolymer is low, so the gel The disadvantage is that it is easy to generate In particular, colored products containing titanium oxide or the like have a major disadvantage in that gel formation is promoted and continuous operation for long periods of time is not possible.
また、混入した回収樹脂中のエチレン−酢酸ビ
ニル共重合体けん化物が製品表面に現われるた
め、ダイでの焼けの発生が激しく、製品の表面状
態が悪化するとともに、製品の耐水性などが十分
でなくなる。さらに、二次的な熱成形時において
製品に穴があくなどの大きな問題点がある。従つ
て、回収樹脂の利用にはおのずと限界があり、製
品コストを低下させるまでには至つておらず、本
質的な解決策が望まれていた。 In addition, the saponified ethylene-vinyl acetate copolymer contained in the recovered resin appears on the product surface, resulting in severe die burns, deteriorating the surface condition of the product, and making it difficult to maintain sufficient water resistance. It disappears. Furthermore, there are major problems such as holes being formed in the product during secondary thermoforming. Therefore, there are limits to the use of recovered resin, and product costs have not yet been reduced, and a substantial solution has been desired.
本発明者らは、これら従来技術の種々の問題点
を解決すべき鋭意研究を重ねた結果、特定された
成形方法を採用することによつて回収樹脂の利用
度を向上することができるとともに、製品の表面
状態や性能上問題のない多層構造材料を長期連続
運転により製造できることを見いだした。本発明
はこれらの知見にもとづいて完成されたものであ
る。 As a result of intensive research to solve various problems of these conventional techniques, the present inventors have been able to improve the utilization of recovered resin by adopting the specified molding method, and We discovered that it is possible to manufacture multilayered materials without problems in product surface condition or performance through long-term continuous operation. The present invention was completed based on these findings.
すなわち、本発明はエチレン−酢酸ビニル共重
合体けん化物を中間層とし、接着性樹脂を介して
ポリオレフイン系樹脂およびポリスチレン系樹脂
から選ばれた樹脂からなる外層で形成された多層
構造材料の製造方法において、少なくとも一方の
外層を二層とするとともに、その内側層を形成す
る樹脂に回収樹脂を混入して押出成形することを
特徴とする多層構造材料の製造方法を提供するも
のである。 That is, the present invention provides a method for producing a multilayer structural material formed of an intermediate layer made of a saponified ethylene-vinyl acetate copolymer and an outer layer made of a resin selected from polyolefin resins and polystyrene resins via an adhesive resin. Provided is a method for producing a multilayer structure material, characterized in that at least one outer layer is made into two layers, and the resin forming the inner layer is mixed with recovered resin and extrusion molded.
以下、本発明の多層構造材料を構成する樹脂お
よび製造方法について詳述する。 Hereinafter, the resin constituting the multilayer structure material of the present invention and the manufacturing method will be described in detail.
中間層を形成するエチレン−酢酸ビニル共重合
体けん化物としては、エチレン含量が25〜80モル
％、好ましくは30〜70モル％のエチレン−酢酸ビ
ニル共重合体を、そのけん化度が90％以上、好ま
しくは95％以上となるようにけん化することによ
つて得られるものを用いることができる。ここで
エチレン成分が少なすぎるものは溶融押出成形性
が十分でなく、他方エチレン成分が多すぎるとガ
スバリヤー性が低いので好ましくない。 The saponified ethylene-vinyl acetate copolymer forming the intermediate layer is an ethylene-vinyl acetate copolymer with an ethylene content of 25 to 80 mol%, preferably 30 to 70 mol%, and a saponified degree of 90% or more. , preferably 95% or more, can be used. If the ethylene component is too small, the melt extrusion moldability will not be sufficient, while if the ethylene component is too large, the gas barrier properties will be low, which is not preferable.
次に、外層を形成する樹脂としてはポリオレフ
イン系樹脂あるいはポリスチレン系樹脂があり、
これら外層樹脂としては同一もしくは同系の樹脂
を用いることが一般的であるが、別々の樹脂を用
いることもできる。 Next, the resin that forms the outer layer is polyolefin resin or polystyrene resin.
Although it is common to use the same or similar resins as these outer layer resins, different resins can also be used.
ここでポリオレフイン系樹脂としては、ポリプ
ロピレン、プロピレンと他のα−オレフインとの
ランダム共重合体、ブロツク共重合体、さらには
高密度ポリエチレン、中密度ポリエチレン、低密
度ポリエチレン、エチレンと他のα−オレフイン
との共重合体などを例示することができる。 Examples of polyolefin resins include polypropylene, random copolymers of propylene and other α-olefins, block copolymers, high-density polyethylene, medium-density polyethylene, low-density polyethylene, ethylene and other α-olefins, etc. Examples include copolymers with
また、ポリスチレン系樹脂としては、一般用ポ
リスチレン、耐衝撃性ポリスチレン、スチレン−
無水マレイン酸共重合体、スチレン−アクリロニ
トリル共重合体、スチレン−ブタジエン共重合
体、スチレン−イソプレン共重合体などを例示す
ることができる。 In addition, polystyrene resins include general purpose polystyrene, high-impact polystyrene, and styrene-based resins.
Examples include maleic anhydride copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, and styrene-isoprene copolymer.
これらポリオレフイン系樹脂やポリスチレン系
樹脂はそれぞれ単独の樹脂を用いてもよいが、同
系の樹脂を二種以上混合して用いることも可能で
ある。また必要により、エチレン−プロピレンゴ
ム、エチレン−プロピレン−ジエンゴム、スチレ
ン−ブタジエンゴムなどのゴム類や各種安定剤、
帯電防止剤、着色剤などを加えることもできる。 Each of these polyolefin resins and polystyrene resins may be used alone, but it is also possible to use a mixture of two or more resins of the same type. In addition, if necessary, rubbers such as ethylene-propylene rubber, ethylene-propylene-diene rubber, styrene-butadiene rubber, and various stabilizers,
Antistatic agents, coloring agents, etc. can also be added.
次に、中間層としてのエチレン−酢酸ビニル共
重合体けん化物と外層用樹脂とを接着するための
接着性樹脂としては、これら両樹脂を接着できる
ものであればよく、特に制限されるものではな
い。たとえば外層樹脂がポリオレフイン系樹脂で
ある場合には不飽和カルボン酸またはその誘導体
によつて変性されたポリオレフイン系樹脂が用い
られる。ここでポリオレフイン系樹脂としては、
ポリエチレン、ポリプロピレン、ポリブテン−
１、ポリ−４−メチルペンテン−１などのオレフ
イン単独重合体、エチレン、プロピレン、ブテン
−１などのα−オレフインと共重合可能な炭素数
２〜20のα−オレフインあるいは不飽和エステル
との共重合体などがある。この場合に用いるα−
オレフインとしてはプロピレン、ブテン−１、ペ
ンテン−１、ヘキセン−１、４−メチル−ペンテ
ン−１、オクテン−１などがあり、不飽和エステ
ルとしては酢酸ビニル、酪酸ビニル、プロピオン
酸ビニル、アクリル酸メチル、アクリル酸プロピ
ル、メタアクリル酸メチル、メタアクリル酸エチ
ルなどがある。 Next, the adhesive resin for bonding the saponified ethylene-vinyl acetate copolymer as the intermediate layer and the resin for the outer layer is not particularly limited as long as it can bond both resins. do not have. For example, when the outer layer resin is a polyolefin resin, a polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof is used. Here, as polyolefin resin,
Polyethylene, polypropylene, polybutene
1. Olefin homopolymers such as poly-4-methylpentene-1, copolymerizable α-olefins with 2 to 20 carbon atoms or unsaturated esters that can be copolymerized with α-olefins such as ethylene, propylene, butene-1, etc. There are polymers, etc. α− used in this case
Olefins include propylene, butene-1, pentene-1, hexene-1, 4-methyl-pentene-1, octene-1, etc., and unsaturated esters include vinyl acetate, vinyl butyrate, vinyl propionate, and methyl acrylate. , propyl acrylate, methyl methacrylate, and ethyl methacrylate.
また、変性に用いる不飽和カルボン酸として
は、アクリル酸、メタアクリル酸、マレイン酸、
フマル酸、イタコン酸、クロトン酸、シトラコン
酸、ソルビン酸、メサコン酸、アンゲリカ酸など
があり、その誘導体としては、酸無水物、エステ
ル、アミド、イミド、金属塩など、たとえば無水
マレイン酸、無水イタコン酸、アクリル酸メチ
ル、アクリル酸エチル、メタアクリル酸メチル、
マレイン酸モノエチルエステル、アクリルアミ
ド、マレイミド、アクリル酸ナトリウムなどをあ
げることができる。 In addition, unsaturated carboxylic acids used for modification include acrylic acid, methacrylic acid, maleic acid,
These include fumaric acid, itaconic acid, crotonic acid, citraconic acid, sorbic acid, mesaconic acid, and angelic acid, and their derivatives include acid anhydrides, esters, amides, imides, and metal salts, such as maleic anhydride and itaconic anhydride. acid, methyl acrylate, ethyl acrylate, methyl methacrylate,
Examples include maleic acid monoethyl ester, acrylamide, maleimide, and sodium acrylate.
不飽和カルボン酸またはその誘導体によつてポ
リオレフイン系樹脂を変性するには種々の方法が
あり、特に制限はなく、たとえば無水マレイン酸
などを溶媒の存在下あるいは不存在下でラジカル
開始剤を添加し加熱することにより反応を行なえ
ばよい。変性ポリオレフイン系樹脂中の不飽和カ
ルボン酸またはその誘導体の含有量は通常0.001
〜20重量％、好ましくは0.005〜10重量％であり、
未変性のポリオレフイン系樹脂との混合物の形で
用いることもできる。 There are various methods for modifying polyolefin resins with unsaturated carboxylic acids or derivatives thereof, and there are no particular limitations. For example, maleic anhydride can be modified with a radical initiator in the presence or absence of a solvent. The reaction may be carried out by heating. The content of unsaturated carboxylic acid or its derivatives in modified polyolefin resin is usually 0.001
~20% by weight, preferably 0.005-10% by weight,
It can also be used in the form of a mixture with an unmodified polyolefin resin.
一方、外層樹脂としてポリスチレン系樹脂を用
いる場合には、上記変性ポリオレフイン系樹脂に
エチレン−酢酸ビニル共重合体などを混入して中
間層−外層の両樹脂に対して接着性をもたせるよ
うにすることが好ましい。また、必要により接着
用樹脂をポリスチレン系樹脂層側にイソプレン−
スチレン共重合体、エチレン−酢酸ビニル共重合
体けん化物層側に変性ポリオレフイン含有樹脂が
対応するような二層とすることもできる。 On the other hand, when a polystyrene resin is used as the outer layer resin, an ethylene-vinyl acetate copolymer or the like is mixed into the modified polyolefin resin to provide adhesiveness to both the intermediate layer and outer layer resins. is preferred. Also, if necessary, add adhesive resin to the polystyrene resin layer side.
It is also possible to have two layers in which the modified polyolefin-containing resin corresponds to the styrene copolymer and saponified ethylene-vinyl acetate copolymer layer.
本発明の多層構造材料の各層の厚みは特に制限
なく、その用途によつて任意に決定されるが、た
とえば中間層としてのエチレン−酢酸ビニル共重
合体けん化物層３〜50μ、接着性樹脂層３〜50μ、
外層樹脂層５〜800μなどである。 The thickness of each layer of the multilayer structure material of the present invention is not particularly limited and can be arbitrarily determined depending on its use, but for example, an ethylene-vinyl acetate copolymer saponified layer as an intermediate layer of 3 to 50 μm, an adhesive resin layer 3~50μ,
The outer resin layer has a thickness of 5 to 800 μm.
本発明の多層構造材料の製造方法としては、共
押出法、押出ラミネート法、共押出ラミネート法
などを採用することができるが、なかでも各層間
の接着強度の点で共押出法が望ましい。 Coextrusion methods, extrusion lamination methods, coextrusion lamination methods, etc. can be employed as methods for producing the multilayer structure material of the present invention, and among them, coextrusion methods are preferred from the viewpoint of adhesive strength between each layer.
本発明は、この多層構造材料の製造方法におい
て、外層樹脂層の少なくとも一方の側を二層にす
るとともに、その内層側を形成する樹脂に回収樹
脂を混入して押出成形することを特徴とするもの
である。ここで混入する回収樹脂の混入量は特に
制限されるものではないが、回収樹脂中のエチレ
ン−酢酸ビニル共重合体けん化物の含有量を考慮
することが好ましく、通常は回収樹脂混入層中の
エチレン−酢酸ビニル共重合体けん化物の含有量
が６重量％以下、好ましくは４重量％以下となる
ように加えることが望ましい。 The present invention is characterized in that, in the method for manufacturing this multilayer structure material, at least one side of the outer resin layer is made into two layers, and the recovered resin is mixed into the resin forming the inner layer side and extrusion molded. It is something. The amount of recovered resin mixed here is not particularly limited, but it is preferable to consider the content of saponified ethylene-vinyl acetate copolymer in the recovered resin, and usually the amount of the recovered resin mixed in the layer is It is desirable that the content of the saponified ethylene-vinyl acetate copolymer be 6% by weight or less, preferably 4% by weight or less.
本発明の製造方法にあつては、エチレン−酢酸
ビニル共重合体けん化物を含む樹脂の成形温度と
しては250℃以下で行なうことがゲルの発生抑制
として望ましく、また必要によりスクリーンメツ
シユとして150メツシユ以上のものを用いること
が好ましい。 In the production method of the present invention, it is desirable to mold the resin containing the saponified ethylene-vinyl acetate copolymer at a temperature of 250°C or lower to prevent gel formation, and if necessary, use a screen mesh of 150°C or less. It is preferable to use the above.
酸化チタンなどの着色剤を用いて着色製品を得
る場合の着色剤の添加は、回収樹脂を混入する層
ではなく、回収樹脂を含まない最外層樹脂に添加
することが望ましい。 When obtaining a colored product using a colorant such as titanium oxide, it is desirable to add the colorant to the outermost resin layer that does not contain the recovered resin, rather than to the layer in which the recovered resin is mixed.
本発明の製造方法にあつては、回収樹脂の量、
回収樹脂中のエチレン酢酸ビニル共重合体けん化
物量の含有量、着色の有無、外層樹脂の種類など
を考慮して外層樹脂中の二層の層比を適宜に決定
すればよい。 In the production method of the present invention, the amount of recovered resin,
The layer ratio of the two layers in the outer layer resin may be appropriately determined in consideration of the content of the saponified ethylene vinyl acetate copolymer in the recovered resin, the presence or absence of coloring, the type of the outer layer resin, and the like.
以上詳述したように、本発明の多層構造材料の
製造方法は、多量に発生する回収樹脂を原料樹脂
に混入することによつて樹脂の有効利用をはかる
ことを可能にしたものである。しかも、耐熱性の
低いエチレン−酢酸ビニル共重合体けん化物から
もたらされる製品表面の不良、ダイにおける焼け
の発生などを防止し、長時間連続運転を可能にし
たものである。特に着色製品において、着色剤に
よるゲルの発生の促進という従来技術の欠点を解
決することができたものである。 As described in detail above, the method for producing a multilayer structure material of the present invention makes it possible to effectively utilize the resin by mixing the recovered resin generated in large quantities into the raw resin. Moreover, it prevents defects on the surface of the product and burns on the die caused by the saponified ethylene-vinyl acetate copolymer, which has low heat resistance, and enables continuous operation for a long time. In particular, in colored products, the drawback of the prior art, which is the promotion of gel formation by colorants, can be overcome.
さらに、回収樹脂のインライン処理の採用によ
り、原料樹脂を100％利用して製品化することに
よる省資源、製品コストの大幅低下とともに、従
来のような廃棄樹脂の貯蔵、廃棄が不要となり、
設備費、作業性の点でもその改善効果は大きいも
のである。 Furthermore, by adopting in-line processing of recovered resin, 100% of the raw resin is used to produce products, which saves resources and significantly reduces product costs, and eliminates the need to store and dispose of waste resin as in the past.
The improvement effects are also significant in terms of equipment costs and workability.
従つて、多層構造材料としてのすぐれた特性と
安価な供給により、フイルム、シート、さらには
熱成形などによる二次成形品として飲料、乳製
品、加工食品など食品や医薬品などの包装材料と
しての利用を拡大するものである。 Therefore, due to its excellent properties as a multilayer structure material and its low cost of supply, it can be used as packaging materials for foods such as beverages, dairy products, processed foods, pharmaceuticals, etc. as films, sheets, and even secondary molded products by thermoforming. It is intended to expand the
以下実施例により本発明をさらに詳しく説明す
るが、本発明はこれら実施例に制限されるもので
はない。 The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited to these Examples.
実施例 １
第１図に示す多層構造材料の製造方法において
中間層Ｄとしてエチレン−酢酸ビニル共重合体け
ん化物（メルトインデツクスMI1.5ｇ／10分、エ
チレン含量40モル％、けん化度99％）10μ、接着
樹脂層Ｃ，Ｅとして無水マレイン酸変性ポリプロ
ピレン樹脂各5μ、外層樹脂層としてポリプロピ
レン樹脂（MI0.6ｇ／10分）40μからなるフイル
ムを共押出法により製造した。この際、外層樹脂
としてのポリプロピレン樹脂層は最外層Ａ，Ｇと
内側層Ｂ，Ｆ各20μの二層とするとともに、内側
層であるＢ，Ｆ層用原料ポリプロピレン樹脂に対
して回収樹脂粉砕物を40重量％混入して押出成形
し、外観良好な製品を１週間連続成形した。な
お、Ｂ，Ｆ層中のエチレン−酢酸ビニル共重合体
けん化物の含有量は４重量％であつた。Example 1 Saponified ethylene-vinyl acetate copolymer (melt index MI 1.5 g/10 minutes, ethylene content 40 mol%, saponification degree 99%) was used as the intermediate layer D in the method for producing a multilayer structure material shown in FIG. A film was produced by coextrusion, consisting of 10μ of maleic anhydride-modified polypropylene resin for the adhesive resin layers C and E, and 40μ of polypropylene resin (MI 0.6g/10 min) for the outer resin layer. At this time, the polypropylene resin layer as the outer layer resin is made of two layers, the outermost layer A, G and the inner layer B, F, each 20 μm in thickness, and the recovered resin pulverized material is used for the raw material polypropylene resin for the inner layer B, F layer. A product with a good appearance was continuously molded for one week. The content of saponified ethylene-vinyl acetate copolymer in layers B and F was 4% by weight.
実施例 ２
実施例１において、Ａ，Ｇ層樹脂に酸化チタン
２重量％を添加した以外は実施例１と同様に成形
を行ない外観良好な製品を１週間連続成形した。Example 2 Molding was carried out in the same manner as in Example 1 except that 2% by weight of titanium oxide was added to the A and G layer resins, and a product with a good appearance was continuously molded for one week.
比較例
実施例１において、外層ポリプロピレン樹脂を
単層40μとし回収樹脂粉砕物を20重量％の割合で
原料に混入して成形を行なつたところ、エチレン
−酢酸ビニル共重合体けん化物が分離し、多層構
造材料の表面平滑性が著しく悪化し、数時間以上
運転することができなかつた。Comparative Example In Example 1, when the outer layer polypropylene resin was made into a single layer of 40 μm and the recovered resin pulverized product was mixed into the raw material at a ratio of 20% by weight and molded, the saponified ethylene-vinyl acetate copolymer was separated. However, the surface smoothness of the multilayer structure material deteriorated significantly, making it impossible to operate it for more than a few hours.
実施例 ３
第２図に示す多層構造材料の製造方法におい
て、接着樹脂層Ｈ，Ｉとして無水マレイン酸変性
ポリプロピレンとエチレン−酢酸ビニル共重合体
の１：２（重量比）の混合物を用い、一方の外層
ＪとしてHI−ポリスチレン20μを用いたこと以外
は実施例１に準じて成形を行なつた。この際、ポ
リプロピレン樹脂層Ｂ用原料樹脂に回収樹脂粉砕
物を20重量％混入し、共押出成形により外観良好
な製品を１週間連続成形した。Example 3 In the method for producing a multilayer structure material shown in FIG. 2, a 1:2 (weight ratio) mixture of maleic anhydride-modified polypropylene and ethylene-vinyl acetate copolymer was used as the adhesive resin layers H and I; Molding was carried out in accordance with Example 1, except that HI-polystyrene 20 μm was used as the outer layer J. At this time, 20% by weight of the recovered resin pulverized material was mixed into the raw material resin for the polypropylene resin layer B, and a product with a good appearance was continuously molded for one week by coextrusion molding.
第１図、第２図は多層構造材料および回収樹脂
の混入を示す説明図である。
FIG. 1 and FIG. 2 are explanatory diagrams showing the mixing of the multilayer structure material and the recovered resin.
Claims (1)
間層とし、接着性樹脂を介してポリオレフイン系
樹脂およびポリスチレン系樹脂から選ばれた樹脂
からなる外層で形成された多層構造材料の製造方
法において、少なくとも一方の外層を二層とする
とともに、その内側層を形成する樹脂に回収樹脂
を混入して押出成形することを特徴とする多層構
造材料の製造方法。 ２ 接着性樹脂が不飽和カルボン酸またはその誘
導体によつて変性されたポリオレフイン系樹脂で
ある特許請求の範囲第１項記載の製造方法。[Scope of Claims] 1 A multilayer structure material formed of a saponified ethylene-vinyl acetate copolymer as an intermediate layer and an outer layer made of a resin selected from a polyolefin resin and a polystyrene resin via an adhesive resin. A method for producing a multilayer structure material, characterized in that at least one of the outer layers is made into two layers, and a recovered resin is mixed into the resin forming the inner layer and extrusion molded. 2. The manufacturing method according to claim 1, wherein the adhesive resin is a polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58090619A JPS59215864A (en) | 1983-05-25 | 1983-05-25 | Manufacture of multilayer structure material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58090619A JPS59215864A (en) | 1983-05-25 | 1983-05-25 | Manufacture of multilayer structure material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59215864A JPS59215864A (en) | 1984-12-05 |
| JPH0160421B2 true JPH0160421B2 (en) | 1989-12-22 |
Family
ID=14003500
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58090619A Granted JPS59215864A (en) | 1983-05-25 | 1983-05-25 | Manufacture of multilayer structure material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59215864A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0635522B2 (en) * | 1985-08-05 | 1994-05-11 | 日本合成化学工業株式会社 | Molding resin composition |
| JPH036425Y2 (en) * | 1985-12-23 | 1991-02-19 | ||
| JPS63237924A (en) * | 1987-03-27 | 1988-10-04 | Toyo Seikan Kaisha Ltd | Manufacture of multi-layer vessel |
| JP2565508B2 (en) * | 1987-09-07 | 1996-12-18 | 株式会社クラレ | Laminate |
| JPH0717042B2 (en) * | 1989-02-17 | 1995-03-01 | 東洋製罐株式会社 | Multi-layer plastic container with excellent surface gloss |
| JPH02229036A (en) * | 1989-03-02 | 1990-09-11 | Yamato Esuron Kk | Synthetic resin laminated sheet |
| JP2003054591A (en) * | 2001-08-13 | 2003-02-26 | Nippon Synthetic Chem Ind Co Ltd:The | Squeezing multi-layered container |
| JP2003063542A (en) * | 2001-08-23 | 2003-03-05 | Nippon Synthetic Chem Ind Co Ltd:The | Squeezing-out multi-layer container |
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| JPS5321674A (en) * | 1976-08-10 | 1978-02-28 | Toyo Seikan Kaisha Ltd | Container* and producing method thereof |
| JPS5366983A (en) * | 1976-11-26 | 1978-06-14 | Mitsui Petrochem Ind Ltd | Laminated structure |
| JPS5420073A (en) * | 1977-07-18 | 1979-02-15 | Toyo Seikan Kaisha Ltd | Manufacture of multiilayer drawinggformed case |
| JPS5446281A (en) * | 1977-09-20 | 1979-04-12 | Mitsubishi Petrochem Co Ltd | Manufacture of resin laminate |
| JPS5453179A (en) * | 1977-10-04 | 1979-04-26 | Mitsui Petrochem Ind Ltd | Multi-layer laminate |
| JPS54113678A (en) * | 1978-02-27 | 1979-09-05 | Mitsubishi Chem Ind Ltd | Manufacturing of multi-layer blow-molded vessel |
| JPS57189A (en) * | 1980-06-04 | 1982-01-05 | Teijin Ltd | Molded body capable of converting light wave length |
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| JPS5711051A (en) * | 1980-06-24 | 1982-01-20 | Kureha Chemical Ind Co Ltd | Multilayer bottle |
| JPS57135110A (en) * | 1981-02-16 | 1982-08-20 | Toyo Seikan Kaisha Ltd | Manufacture of multilayer plastic vessel |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5450069U (en) * | 1977-09-16 | 1979-04-06 |
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1983
- 1983-05-25 JP JP58090619A patent/JPS59215864A/en active Granted
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5315546A (en) * | 1976-07-28 | 1978-02-13 | Hitachi Ltd | Protective relay system |
| JPS5321674A (en) * | 1976-08-10 | 1978-02-28 | Toyo Seikan Kaisha Ltd | Container* and producing method thereof |
| JPS5366983A (en) * | 1976-11-26 | 1978-06-14 | Mitsui Petrochem Ind Ltd | Laminated structure |
| JPS5420073A (en) * | 1977-07-18 | 1979-02-15 | Toyo Seikan Kaisha Ltd | Manufacture of multiilayer drawinggformed case |
| JPS5446281A (en) * | 1977-09-20 | 1979-04-12 | Mitsubishi Petrochem Co Ltd | Manufacture of resin laminate |
| JPS5453179A (en) * | 1977-10-04 | 1979-04-26 | Mitsui Petrochem Ind Ltd | Multi-layer laminate |
| JPS54113678A (en) * | 1978-02-27 | 1979-09-05 | Mitsubishi Chem Ind Ltd | Manufacturing of multi-layer blow-molded vessel |
| JPS57189A (en) * | 1980-06-04 | 1982-01-05 | Teijin Ltd | Molded body capable of converting light wave length |
| JPS5711052A (en) * | 1980-06-24 | 1982-01-20 | Kureha Chemical Ind Co Ltd | Multilayer bottle |
| JPS5711051A (en) * | 1980-06-24 | 1982-01-20 | Kureha Chemical Ind Co Ltd | Multilayer bottle |
| JPS57135110A (en) * | 1981-02-16 | 1982-08-20 | Toyo Seikan Kaisha Ltd | Manufacture of multilayer plastic vessel |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59215864A (en) | 1984-12-05 |
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