JPS645614B2 - - Google Patents
Info
- Publication number
- JPS645614B2 JPS645614B2 JP57177552A JP17755282A JPS645614B2 JP S645614 B2 JPS645614 B2 JP S645614B2 JP 57177552 A JP57177552 A JP 57177552A JP 17755282 A JP17755282 A JP 17755282A JP S645614 B2 JPS645614 B2 JP S645614B2
- Authority
- JP
- Japan
- Prior art keywords
- polyethylene
- density polyethylene
- weight
- ethylene
- resin composition
- 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
- 239000011342 resin composition Substances 0.000 claims description 17
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 14
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 14
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 11
- 229920013716 polyethylene resin Polymers 0.000 claims description 10
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 9
- 239000004700 high-density polyethylene Substances 0.000 claims description 9
- 229920000098 polyolefin Polymers 0.000 claims description 7
- 229920004889 linear high-density polyethylene Polymers 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 239000004711 α-olefin Substances 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 5
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000010030 laminating Methods 0.000 claims description 3
- -1 Polyethylene Polymers 0.000 description 23
- 239000004698 Polyethylene Substances 0.000 description 17
- 229920000573 polyethylene Polymers 0.000 description 17
- 239000010410 layer Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 8
- 239000004677 Nylon Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229920001778 nylon Polymers 0.000 description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000005336 cracking Methods 0.000 description 5
- 230000006353 environmental stress Effects 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 239000010959 steel Substances 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
- JNPCNDJVEUEFBO-UHFFFAOYSA-N 1-butylpyrrole-2,5-dione Chemical compound CCCCN1C(=O)C=CC1=O JNPCNDJVEUEFBO-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
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-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
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-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
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-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
- 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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001413 amino acids 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
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 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
- 239000011248 coating agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 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
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000007788 liquid 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
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 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
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 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
- 230000035699 permeability Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 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
- 238000003756 stirring Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Wrappers (AREA)
Description
本発明はポリエチレン樹脂組成物とエチレン―
酢酸ビニル共重合体けん化物などの樹脂とを積層
してなる積層物に関する。
従来からポリエチレンは透明性、柔軟性、衛生
性、加工性等の諸性質にすぐれ、かつ比較的安価
に得られることから、各種食品や化学品などの包
装や容器として広い範囲で用いられている。しか
し、ポリエチレンは気体透過性が大きいなどの欠
点があるため、包装や容器の資材としては単独で
は用いられず、他の材料、例えばポリアミド、エ
チレン―酢酸ビニル共重合体ケン化物などの高分
子材料との積層物が検討されている。
しかしながらポリエチレンは無極性材料である
ためほとんど接着力を有しておらず、積層物とし
て利用するには様々な問題がある。
近年、これらの欠点を改善するために、(1)ポリ
エチレンを不飽和カルボン酸またはその無水物で
変性する方法、(2)変性ポリエチレンに他の重合
体、例えばエチレン―酢酸ビニル共重合体ケン化
物、熱可塑性ポリエステル、ポリビニルアルコー
ルなどをブレンドする方法などが提案されている
（特開昭53−39381号公報、特開昭52−124080号公
報、特開昭52−103480号公報）。
しかし、これらの方法で得られた積層物は、そ
の初期接着力は充分であるが、耐久性に劣り、経
時的に接着性が低下するという欠点がある。また
耐環境応力亀裂性を充分でなく、化学品の容器や
鋼管の防食被覆などに適用するには困難があり、
利用上大きな制限があつた。
本発明の目的は、上記の欠点を解消した接着
性、耐環境応力亀裂性にすぐれたポリエチレン樹
脂組成物を用いた積層物を提供することである。
すなわち、本発明は［Ａ］(a)エチレンと0.2〜
20モル％の炭素数４〜８のα―オレフインからな
る直鎖状低密度ポリエチレン99.9〜65重量％と(b)
不飽和カルボン酸もしくはその誘導体によつて変
性された前記直鎖状低密度ポリエチレンまたは高
密度ポリエチレン0.1〜35重量％からなるポリエ
チレン樹脂組成物と［Ｂ］エチレン―酢酸ビニル
共重合体けん化物、ポリアミド、ポリエステルお
よびポリオレフインよりなる群から選ばれた樹脂
とを積層してなる積層物を提供するものである。
本発明のポリエチレン樹脂組成物積層物におけ
る［Ａ］(a)成分である直鎖状低密度ポリエチレン
は、エチレンと0.2〜20モル％、好ましくは１〜
10モル％の他のα―オレフインとからなるもので
ある。ここでα―オレフインの量が共重合体の
0.2モル％未満の場合には耐久接着性および耐環
境応力亀裂性が不充分であり、20モル％を越える
と強度その他の物性が著しく低下するので好まし
くない。また、エチレンと共重合させる他のα―
オレフインとしては、炭素数４〜８のもの、具体
的にはブテン―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、これらを１種あるいは２種以上を併用す
ればよい。
この直鎖状低密度ポリエチレンは、中圧ないし
低圧でイオン重合（気相重合、溶液重合）などに
よつて製造されるもので、密度が0.910〜
0.960g／cm3、好ましくは0.915〜１／930g／cm3、
メルトインデツクス（MI）が0.1〜30g／10分、
好ましくは0.5〜12g／10分のものである。すなわ
ち、本質的にエチレンと共重合するところのα―
オレフインの残基のみからなる短鎖分枝を有する
エチレン共重合体であり、直鎖状低密度ポリエチ
レンとして近時知られるようになつたエチレン共
重合体である。
したがつて、従来高圧法ラジカル重合により得
られていた長鎖分枝を有する低密度ポリエチレン
共重合体とは本質的に異なるものである。
一方、本発明の［Ａ］(b)成分としては、上記の
直鎖状低密度ポリエチレンまたは高密度ポリエチ
レンを不飽和カルボン酸もしくはその誘導体によ
つて変性したものを用いる。ここで高密度ポリエ
チレンとは、従来中、低圧法により得られている
密度0.940〜0.970g／cm3のポリエチレンをいい、
他のα―オレフインとの共重合体を含む。
ここで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る。ま
た、その誘導体としては、酸無水物、エステル、
アミド、イミド、金属塩などがあり、例えば無水
マレイン酸、無水イタコン酸、無水シトラコン
酸、アクリル酸メチル、メタアクリル酸メチル、
アクリル酸エチル、アクリル酸ブチル、マレイン
酸モノエチルエステル、アクリルアミド、ヤレイ
ン酸モノアミド、マレイミド、Ｎ―ブチルマレイ
ミド、アクリル酸ナトリウム、メタアクリル酸ナ
トリウムなどをあげることができる。
これらの不飽和カルボン酸またはその誘導体に
よつて上記直鎖状低密度ポリエチレンまたは高密
度ポリエチレンを変性するには、その方法は特に
制限されず公知の種々の方法を用いて行なうこと
ができる。例えば直鎖状低密度ポリエチレン等と
無水マレイン酸等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
り進行する。反応に際しては、スチレンなどの他
のビニルモノマーあるいは液状ゴム、熱可塑性ゴ
ムなどのゴム類を共存させることもできる。
このようにして変性された直鎖状低密度ポリエ
チレンまたは高密度ポリエチレン中の不飽和カル
ボン酸またはその誘導体の含有量は通常は0.001
〜15重量％、好ましくは0.005〜10重量％、更に
好ましくは0.05〜５重量％の範囲である。この変
性体は、必ずしもすべてが変性されたものでなく
てもよく、未変性ポリエチレンをブレンドしたも
のであつてもよい。
本発明のポリエチレン樹脂組成物積層物におい
ては、［Ａ］(a)成分として直鎖状低密度ポリエチ
レンを用い、［Ａ］(b)成分として変性された直鎖
状低密度ポリエチレンまたは高密度ポリエチレン
のいずれかを用いる。
ここで［Ａ］(a)成分と［Ａ］(b)成分の配合割合
は、［Ａ］(a)成分が99.9〜65重量％、好ましくは
98〜80重量％であり、［Ａ］(b)成分が0.1〜35重量
％、好ましくは２〜20重量％である。
以上の如き構成の本発明の［Ａ］層として用い
るポリエチレン樹脂組成物は、他の樹脂に対する
接着性が著しくすぐていると共に、その接着力は
熱、水、塩水などを加えても劣化することがな
く、しかも耐環境応力亀裂性もすぐれたものであ
る。従つてこの樹脂組成物は他の樹脂と積層物を
形成したり、他の樹脂とのブレンドを作る場合に
すぐれた性質を発揮する。なお、上記樹脂組成物
には、上述した成分のほかに、必要に応じて相溶
性のあるゴム、エチレン―酢酸ビニル共重合体な
どを加えることもできる。ゴムとしてはエチレン
―プロピレンコポリマー、エチレン―プロピレン
―ジエンターポリマーなどのエチレン―プロピレ
ンゴムが好ましく、上記樹脂組成物100重量部に
対して25重量部以下、好ましくは３〜15重量部の
範囲で配合することが有効である。また、酸化防
止剤、紫外線吸収剤等の各種添加剤等を適宜加え
ることができることは勿論である。
本発明のポリエチレン樹脂組成物積層物は上記
のポリエチレン樹脂組成物（〔Ａ〕層）と特定の
材料（〔Ｂ〕層）とを積層してなる積層物である。
ここで〔Ｂ〕層を構成する材料として、エチレン
―酢酸ビニル共重合体けん化物、ポリアミド、ポ
リエステルまたはポリオレフインを用いる。エチ
レン―酢酸ビニル共重合体けん化物としては、そ
の組成は特に限定されないが、好ましくはエチレ
ン含量が25〜50モル％のエチレン―酢酸ビニル共
重合体を、そのけん化度が93％以上、望ましくは
96％以上となるようにけん化することにより得ら
れるものがよい。この範囲外のものであると、ガ
スバリヤー性、耐油性などに劣るものとなるので
好ましくない。
また、ポリアミドはジアミンとジカルボン酸の
縮合、アミノ酸の自己縮合およびラクタムの開環
重合により得られる酸アミド結合を有する線状合
成高分子であり、具体的には６―ナイロン（ポリ
カプロアミド）；６，６―ナイロン（ポリヘキサ
メチレンアデイフアミド）；６，10―ナイロン
（ポリヘキサメチレンセバカミド）；11―ナイロン
（ポリウンデカミド）；12―ナイロン等が使用でき
る。
次に、ポリエステルとしては、ポリエチレンテ
レフタレート、ポリブチレンテレフタレートなど
がある。また、ポリオレフインとしては、各種の
ものがあるが、例えば高密度ポリエチレン、低密
度ポリエチレン、直鎖状低、中密度ポリエチレ
ン、ポリプロピレンあるいはこれらの共重合体等
をあげることができる。
本発明の積層物は、ポリエチレン樹脂組成物層
（〔Ａ〕層）とエチレン―酢酸ビニル共重合体けん
化物などの層（〔Ｂ〕層）からなる二層積層物で
あるが、必要に応じてＡ−Ｂ−Ａ、Ｂ−Ａ−Ｂ、
ポリオレフイン―Ａ−Ｂ、ポリオレフイン―Ａ−
Ｂ−Ａ−ポリオレフインなどの多層積層物とする
こともできる。
本発明の積層物は、熱圧着法、ダイ内ラミネー
ト法、ダイ外ラミネート法等の公知の手段を適用
することにより所望のシート、フイルムを得、さ
らにはブロー成形によりブロー成形品を得ること
ができる。
このようにして得られた本発明の積層物は、層
間接着（剥離）強度が著しく向上しており、しか
もガスバリヤー性、耐油性、耐水性などの性質も
改良されており、また熱成形性が良好であると共
に耐環境応力亀裂性においてもすぐれているとい
う特色を有している。そのためこの積層物は、各
種食品、飲料あるいは化学品等の包装もしくは容
器の資材として利用されるほか、各種用途の鋼管
の被覆資材などとして有効に利用しうるものであ
る。
次に、本発明の実施例を示す。
製造例
(1) 変性ポリエチレンＡの製造
低密度エチレン共重合体（MI26g／10分、密度
0.92g／cm2、ブテン―１含有量2.1重量％）100重
量部、無水マレイン酸10重量部およびジクミルパ
ーオキサイド0.5重量部をキシレン600重量部に加
えて加熱溶解し、125℃で２時間撹拌しながら反
応させた。次いで、反応物を大量のアセトン中に
入れ、反応生成物を沈澱分別し、乾燥して無水マ
レイン酸変性ポリエチレンＡを得た。得られた変
性ポリエチレンの無水マレイン酸含有量は3.0重
量％であり、またMIは0.9g／10分であつた。
(2) 変性ポリエチレンＢの製造
原料ポリエチレンとして、MI13g／10分、密度
0.95g／cm3の高密度ポリエチレンを用いたこと以
外は上記(1)と同様の操作を行ない、変性ポリエチ
レンＢを得た。得られた変性ポリエチレンの無水
マレイン酸含有量は3.5重量％あり、またMIは
0.1g／10分あつた。
(3) 変性ポリエチレンＣの製造
低密度ポリエチレン（MI23g／10分、密度
0.90g／cm3）を用いて上記(1)と同様の操作を行な
い、変性ポリエチレンＣを得た。得られた変性ポ
リエチレンの無水マレイン酸含有量は3.1重量％
あり、またMIは0.8g／10分あつた。
実施例１〜９および比較例１〜３
第１表［Ａ］層配合組成からなる配合物を200
℃で混練押し出ししてペレツトを得た。このペレ
ツトと［Ｂ］層として、それぞれエチレン―酢酸
ビニル共重合体けん化物、６―ナイロン、ポリエ
チレンテレフタレート、ポリオレフインを共押し
出し成形して各層200μの二層シートを製造した。
成形温度は樹脂組成物／エチレン―酢酸ビニル共
重合体ケン化物の場合は220℃、樹脂組成物／６
―ナイロンの場合は240℃、樹脂組成物／ポリエ
チレンテレフタレートの場合は260℃、樹脂組成
物／ポリオレフインの場合は200℃であり、引取
速度は5m／分であつた。180゜剥離強度の結果を
第１表および第２表に示す。
The present invention relates to a polyethylene resin composition and an ethylene-
The present invention relates to a laminate formed by laminating a resin such as a saponified vinyl acetate copolymer. Polyethylene has traditionally been widely used as packaging and containers for various foods and chemicals, as it has excellent properties such as transparency, flexibility, hygiene, and processability, and can be obtained at a relatively low cost. . However, polyethylene has disadvantages such as high gas permeability, so it cannot be used alone as a material for packaging or containers, and other materials, such as polymeric materials such as polyamide and saponified ethylene-vinyl acetate copolymer, can be used instead. A laminate is being considered. However, since polyethylene is a nonpolar material, it has almost no adhesive strength, and there are various problems when using it as a laminate. In recent years, in order to improve these drawbacks, (1) methods of modifying polyethylene with unsaturated carboxylic acids or its anhydrides, and (2) methods of modifying polyethylene with other polymers, such as saponified ethylene-vinyl acetate copolymers, have been developed. , thermoplastic polyester, polyvinyl alcohol, etc. have been proposed (Japanese Patent Application Laid-Open No. 53-39381, JP-A-52-124080, JP-A-52-103480). However, although the laminates obtained by these methods have sufficient initial adhesive strength, they have the disadvantage that they are inferior in durability and their adhesiveness decreases over time. In addition, it does not have sufficient environmental stress cracking resistance, making it difficult to apply it to chemical containers and anticorrosion coatings for steel pipes.
There were major restrictions on its use. An object of the present invention is to provide a laminate using a polyethylene resin composition that eliminates the above-mentioned drawbacks and has excellent adhesiveness and environmental stress cracking resistance. That is, the present invention provides [A] (a) ethylene and 0.2 to
(b) 99.9 to 65% by weight of linear low density polyethylene consisting of 20 mol% of α-olefin having 4 to 8 carbon atoms;
A polyethylene resin composition consisting of 0.1 to 35% by weight of the linear low-density polyethylene or high-density polyethylene modified with an unsaturated carboxylic acid or a derivative thereof, and [B] saponified ethylene-vinyl acetate copolymer, polyamide , polyester, and a resin selected from the group consisting of polyolefin. The linear low density polyethylene which is the component [A](a) in the polyethylene resin composition laminate of the present invention contains ethylene in an amount of 0.2 to 20 mol%, preferably 1 to 20 mol%.
It consists of 10 mol% of other α-olefins. Here, the amount of α-olefin is
If it is less than 0.2 mol%, durable adhesiveness and environmental stress cracking resistance will be insufficient, and if it exceeds 20 mol%, strength and other physical properties will be markedly lowered, which is not preferable. In addition, other α-
Olefins include those with 4 to 8 carbon atoms, specifically 1-butene, 1-pentene, and 1-hexene.
Examples include 1,4-methylpentene-1 and octene-1, and these may be used alone or in combination of two or more. This linear low-density polyethylene is produced by ionic polymerization (gas phase polymerization, solution polymerization) under medium to low pressure, and has a density of 0.910 to
0.960g/cm 3 , preferably 0.915 to 1/930g/cm 3 ,
Melt index (MI) is 0.1 to 30g/10 minutes,
Preferably it is 0.5 to 12 g/10 minutes. That is, α- which essentially copolymerizes with ethylene.
It is an ethylene copolymer having short chain branches consisting only of olefin residues, and has recently come to be known as linear low-density polyethylene. Therefore, it is essentially different from low-density polyethylene copolymers having long chain branches conventionally obtained by high-pressure radical polymerization. On the other hand, as component [A](b) of the present invention, the above linear low density polyethylene or high density polyethylene modified with an unsaturated carboxylic acid or a derivative thereof is used. Here, high-density polyethylene refers to polyethylene with a density of 0.940 to 0.970 g/cm 3 that is conventionally obtained by a low-pressure method.
Contains copolymers with other α-olefins. Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, sorbic acid, mesaconic acid, and angelic acid. In addition, its derivatives include acid anhydrides, esters,
There are amides, imides, metal salts, etc., such as maleic anhydride, itaconic anhydride, citraconic anhydride, methyl acrylate, methyl methacrylate,
Examples include ethyl acrylate, butyl acrylate, monoethyl maleate, acrylamide, yaleic acid monoamide, maleimide, N-butylmaleimide, sodium acrylate, and sodium methacrylate. The method for modifying the linear low-density polyethylene or high-density polyethylene with these unsaturated carboxylic acids or derivatives thereof is not particularly limited, and various known methods can be used. For example, the process proceeds by adding a radical initiator to linear low-density polyethylene or the like and maleic anhydride in the presence or absence of a solvent and heating the mixture. During the reaction, other vinyl monomers such as styrene or rubbers such as liquid rubber and thermoplastic rubber may also be present. The content of unsaturated carboxylic acid or its derivative in linear low density polyethylene or high density polyethylene modified in this way is usually 0.001
It ranges from 15% to 15% by weight, preferably from 0.005 to 10% by weight, more preferably from 0.05 to 5% by weight. This modified product does not necessarily have to be entirely modified, and may be a blend of unmodified polyethylene. In the polyethylene resin composition laminate of the present invention, linear low density polyethylene is used as the component [A] (a), and modified linear low density polyethylene or high density polyethylene is used as the component [A] (b). Use one of the following. Here, the blending ratio of [A](a) component and [A](b) component is 99.9 to 65% by weight, preferably 99.9 to 65% by weight of [A](a) component.
The content of component [A](b) is 0.1 to 35% by weight, preferably 2 to 20% by weight. The polyethylene resin composition used as the [A] layer of the present invention having the above-mentioned structure has extremely good adhesion to other resins, and its adhesive strength does not deteriorate even when heat, water, salt water, etc. are applied. Moreover, it has excellent environmental stress cracking resistance. Therefore, this resin composition exhibits excellent properties when forming a laminate with other resins or creating a blend with other resins. In addition to the above-mentioned components, compatible rubbers, ethylene-vinyl acetate copolymers, and the like may be added to the resin composition, if necessary. The rubber is preferably ethylene-propylene rubber such as ethylene-propylene copolymer or ethylene-propylene-dien terpolymer, and is blended in an amount of 25 parts by weight or less, preferably 3 to 15 parts by weight, based on 100 parts by weight of the resin composition. It is effective to do so. It goes without saying that various additives such as antioxidants and ultraviolet absorbers can be added as appropriate. The polyethylene resin composition laminate of the present invention is a laminate formed by laminating the above polyethylene resin composition ([A] layer) and a specific material ([B] layer).
Here, as the material constituting the [B] layer, saponified ethylene-vinyl acetate copolymer, polyamide, polyester, or polyolefin is used. The composition of the saponified ethylene-vinyl acetate copolymer is not particularly limited, but it is preferable to use an ethylene-vinyl acetate copolymer with an ethylene content of 25 to 50 mol%, and a degree of saponification of 93% or more, preferably
Those obtained by saponification to a concentration of 96% or more are preferable. If it is outside this range, the gas barrier properties, oil resistance, etc. will be poor, which is not preferable. In addition, polyamide is a linear synthetic polymer having acid amide bonds obtained by condensation of diamine and dicarboxylic acid, self-condensation of amino acids, and ring-opening polymerization of lactam, and specifically, 6-nylon (polycaproamide); 6,6-nylon (polyhexamethylene adiphamide); 6,10-nylon (polyhexamethylene sebacamide); 11-nylon (polyundecamide); 12-nylon, etc. can be used. Next, examples of polyester include polyethylene terephthalate and polybutylene terephthalate. Further, there are various kinds of polyolefins, such as high-density polyethylene, low-density polyethylene, linear low- and medium-density polyethylene, polypropylene, and copolymers thereof. The laminate of the present invention is a two-layer laminate consisting of a polyethylene resin composition layer ([A] layer) and a layer of saponified ethylene-vinyl acetate copolymer ([B] layer). A-B-A, B-A-B,
Polyolefin-A-B, Polyolefin-A-
It can also be a multilayer laminate such as B-A-polyolefin. The laminate of the present invention can be obtained by applying known means such as thermocompression bonding, in-die lamination, or out-of-die lamination to obtain a desired sheet or film, and further, by blow molding to obtain a blow-molded product. can. The thus obtained laminate of the present invention has significantly improved interlayer adhesion (peel) strength, and also has improved properties such as gas barrier properties, oil resistance, and water resistance, and also has improved thermoformability. It has the characteristics of not only good hardness but also excellent environmental stress cracking resistance. Therefore, this laminate can be used effectively as a material for packaging or containers for various foods, beverages, chemicals, etc., and as a coating material for steel pipes for various purposes. Next, examples of the present invention will be shown. Production example (1) Production of modified polyethylene A Low density ethylene copolymer (MI26g/10min, density
0.92g/cm 2 , butene-1 content 2.1% by weight) 100 parts by weight, 10 parts by weight of maleic anhydride, and 0.5 parts by weight of dicumyl peroxide were added to 600 parts by weight of xylene, dissolved by heating, and heated at 125°C for 2 hours. The reaction was carried out with stirring. Next, the reaction product was poured into a large amount of acetone, and the reaction product was separated by precipitation and dried to obtain maleic anhydride-modified polyethylene A. The maleic anhydride content of the obtained modified polyethylene was 3.0% by weight, and the MI was 0.9 g/10 min. (2) Production of modified polyethylene B As raw material polyethylene, MI13g/10 minutes, density
Modified polyethylene B was obtained by carrying out the same operation as in (1) above, except that 0.95 g/cm 3 high-density polyethylene was used. The maleic anhydride content of the obtained modified polyethylene was 3.5% by weight, and the MI was
0.1g/10 minutes hot. (3) Production of modified polyethylene C Low density polyethylene (MI23g/10 minutes, density
Modified polyethylene C was obtained by carrying out the same operation as in (1) above using 0.90 g/cm 3 ). The maleic anhydride content of the obtained modified polyethylene was 3.1% by weight.
Yes, and MI was 0.8g/10 minutes. Examples 1 to 9 and Comparative Examples 1 to 3 Table 1 [A] Compounds consisting of layer compositions were prepared at 200%
The mixture was kneaded and extruded at ℃ to obtain pellets. The pellets were coextruded with saponified ethylene-vinyl acetate copolymer, 6-nylon, polyethylene terephthalate, and polyolefin as the layer [B] to produce a two-layer sheet with each layer having a thickness of 200 μm.
Molding temperature is 220℃ for resin composition/saponified ethylene-vinyl acetate copolymer, resin composition/6
- 240°C for nylon, 260°C for resin composition/polyethylene terephthalate, and 200°C for resin composition/polyolefin, and the drawing speed was 5 m/min. The results of the 180° peel strength are shown in Tables 1 and 2.
【表】【table】
【表】【table】
Claims (1)
４〜８のα―オレフインからなる直鎖状低密度ポ
リエチレン99.9〜65重量％と(b)不飽和カルボン酸
もしくはその誘導体によつて変性された前記直鎖
状低密度ポリエチレンまたは高密度ポリエチレン
0.1〜35重量％からなるポリエチレン樹脂組成物
と［Ｂ］エチレン―酢酸ビニル共重合体けん化
物、ポリアミド、ポリエステルおよびポリオレフ
インよりなる群から選ばれた樹脂とを積層してな
る積層物。1 [A] (a) 99.9 to 65% by weight of linear low-density polyethylene consisting of ethylene and 0.2 to 20 mol% of α-olefin having 4 to 8 carbon atoms, and (b) unsaturated carboxylic acid or its derivative. The linear low-density polyethylene or high-density polyethylene modified by
A laminate obtained by laminating a polyethylene resin composition containing 0.1 to 35% by weight and a resin selected from the group consisting of [B] saponified ethylene-vinyl acetate copolymer, polyamide, polyester, and polyolefin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57177552A JPS5968351A (en) | 1982-10-12 | 1982-10-12 | Polyethylene resin composition and laminate thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57177552A JPS5968351A (en) | 1982-10-12 | 1982-10-12 | Polyethylene resin composition and laminate thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5968351A JPS5968351A (en) | 1984-04-18 |
| JPS645614B2 true JPS645614B2 (en) | 1989-01-31 |
Family
ID=16032942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57177552A Granted JPS5968351A (en) | 1982-10-12 | 1982-10-12 | Polyethylene resin composition and laminate thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5968351A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104017304A (en) * | 2014-06-01 | 2014-09-03 | 上海韬鸿化工科技有限公司 | Cold-resistant sheath material and cable |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH072875B2 (en) * | 1986-07-09 | 1995-01-18 | 宇部興産株式会社 | Modified linear low density polyethylene composition |
| JPH0444357Y2 (en) * | 1986-07-24 | 1992-10-20 | ||
| JPS6334137A (en) * | 1986-07-29 | 1988-02-13 | 新神戸電機株式会社 | Multilayer sheet |
| JPS6438233A (en) * | 1987-08-04 | 1989-02-08 | Showa Denko Kk | Multilayer construction |
| KR100895522B1 (en) | 2001-03-28 | 2009-04-30 | 니혼폴리올레핀 가부시키가이샤 | Adhesive resin composition and multilayer structure made with the same |
| JPWO2012133008A1 (en) * | 2011-03-25 | 2014-07-28 | 三井化学株式会社 | Adhesive resin composition and multilayer structure using the same |
| KR20200135464A (en) | 2018-04-25 | 2020-12-02 | 미쓰이 가가쿠 가부시키가이샤 | Adhesive resin composition and laminate |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5232654B2 (en) * | 1973-05-17 | 1977-08-23 | ||
| JPS5214684A (en) * | 1975-07-25 | 1977-02-03 | Mitsubishi Petrochem Co Ltd | Process for preparing a resinous laminate |
| JPS5225845A (en) * | 1975-08-25 | 1977-02-26 | Mitsui Petrochem Ind Ltd | Polyolefin composition having improved adhesivity with nylon resin |
| JPS5849573B2 (en) * | 1976-11-24 | 1983-11-05 | 三井化学株式会社 | Multilayer laminated structure |
| JPS5482A (en) * | 1977-06-03 | 1979-01-05 | Mitsubishi Chem Ind Ltd | Production of resin laminate |
| JPS6031669B2 (en) * | 1977-10-04 | 1985-07-23 | 三井化学株式会社 | Multilayer laminated structure |
| CA1157216A (en) * | 1978-09-15 | 1983-11-22 | William F. Briggs | Coextruded thermoplastic stretch-wrap |
| JPS55121058A (en) * | 1979-03-14 | 1980-09-17 | Mitsui Petrochemical Ind | Multilayer laminated structure |
| JPS57105349A (en) * | 1980-12-23 | 1982-06-30 | Mitsui Petrochemical Ind | Multilayer laminated structure |
| JPS6036217B2 (en) * | 1981-04-07 | 1985-08-19 | 東亜燃料工業株式会社 | Modified polyethylene composition |
-
1982
- 1982-10-12 JP JP57177552A patent/JPS5968351A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104017304A (en) * | 2014-06-01 | 2014-09-03 | 上海韬鸿化工科技有限公司 | Cold-resistant sheath material and cable |
| CN104017304B (en) * | 2014-06-01 | 2016-03-30 | 上海韬鸿化工科技有限公司 | Cold-resistant sheath material and cable |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5968351A (en) | 1984-04-18 |
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