JPH0564103B2 - - Google Patents
Info
- Publication number
- JPH0564103B2 JPH0564103B2 JP5934686A JP5934686A JPH0564103B2 JP H0564103 B2 JPH0564103 B2 JP H0564103B2 JP 5934686 A JP5934686 A JP 5934686A JP 5934686 A JP5934686 A JP 5934686A JP H0564103 B2 JPH0564103 B2 JP H0564103B2
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- eva
- vinyl acetate
- copolymer
- fatty acid
- 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 - Lifetime
Links
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 18
- 239000000853 adhesive Substances 0.000 claims description 17
- 230000001070 adhesive effect Effects 0.000 claims description 17
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 17
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 17
- 229930195729 fatty acid Natural products 0.000 claims description 17
- 239000000194 fatty acid Substances 0.000 claims description 17
- 150000004665 fatty acids Chemical class 0.000 claims description 17
- 229920001038 ethylene copolymer Polymers 0.000 claims description 14
- 239000010410 layer Substances 0.000 claims description 13
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 10
- 239000011229 interlayer Substances 0.000 claims description 10
- 229920005992 thermoplastic resin Polymers 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 7
- 238000007127 saponification reaction Methods 0.000 claims description 7
- 229920005990 polystyrene resin Polymers 0.000 claims description 6
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229920005669 high impact polystyrene Polymers 0.000 description 8
- 239000004797 high-impact polystyrene Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920006267 polyester film Polymers 0.000 description 3
- 229920005672 polyolefin resin Polymers 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical class CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 2
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical class CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005639 Lauric acid Chemical class 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-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
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 150000002148 esters Chemical class 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
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Chemical class CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process 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
- 239000003208 petroleum Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003097 polyterpenes Chemical class 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Description
［産業上の利用分野］
本発明は接着性が良好な樹脂積層物に関する。
更に詳しくは、高級脂肪酸金属塩を含んだエチ
レン系共重合体をエチレン−酢酸ビニル共重合体
ケン化物層と他の熱可塑性樹脂基材層の層間接剤
着とした積層物に関する。
［従来の技術］
エチレン−酢酸ビニル共重合体ケン化物、特に
高ケン化物のフイルムは各種フイルム、積層物の
基材として用いられるが、このものはガスバリア
性、耐油性に優れている反面、水分の透過性が大
きいために、食品包装用容器、フイルム等に用い
られる単一の材料として使用されることは少な
く、通常ポリスチレン系樹脂又はポリオレフイン
系樹脂と積層して用いられることが多い。
このようなエチレン−酢酸ビニル共重合体ケン
化物の内、エチレン含量が20〜55モル％、ケン化
率が90％以上の高ケン化物（以下Ｈ−EVA−
OH）は異種基材との接着性が弱いため、通常Ｈ
−EV−OHとポリオレフイン系樹脂を積層する
際の層間接着剤として、不飽和カルボン酸で変性
したポリオレフイン系樹脂が用いられる。
一方、Ｈ−EVA−OHと、これとの積層相手と
して一般に用いられるポリスチレン系樹脂の層間
接着剤としては、種々の樹脂及び樹脂組成物が提
案されているが、Ｈ−EVA−OHとポリスチレン
系樹脂両者に対し充分満足な接着性を有する接着
剤組成物は未だ見出されていない。
本発明者らはＨ−EVA−OHと種々の樹脂、特
にポリスチレン系樹脂との接着剤として、エチレ
ン系共重合体につき種々検討した。特に接着剤と
して汎用されている、エチレン−酢酸ビニル共重
合体ケン化物、即ち、酢酸ビニル含量が10〜50重
量％のエチレン−酢酸ビニル共重合体のケン化物
（以下Ｌ−EVA−OH）につき種々検討したが、
Ｌ−EVA−OHはポリスチレン系樹脂に対する接
着力には優れているものの、Ｈ−EVA−OHに対
する接着性が小さく、このままでは実用には供し
得ないことが判つた。
［発明が解決しようとする問題点］
本発明の目的は、エチレン系共重合体を層間接
着剤とした接着性の良好な、Ｈ−EVA−OH層と
他の熱可塑性樹脂基材層との積層物を提供するこ
とにある。
［問題を解決するための手段］
本発明は、Ｅ−EVA−OH層と他の熱可塑性樹
脂基材層との層間接着剤として高級脂肪酸金属塩
を含んだエチレン系共重合体を用いたことが特徴
である。
本発明で用いるエチレン系共重合体はエチレン
含量が２〜99モル％の通常のものである。エチレ
ン系共重合体の例としては、(1)エチレン−不飽和
エステル共重合体がある。エチレンとの共重合体
モノマーである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、安息香酸
ビニル、アクリル酸メチル、アクリル酸エチル、
アクリル酸プロピル、メタクリル酸メチル、メタ
クリル酸エチル等がある。又、(2)エチレン−ビニ
ルエステル共重合体のケン化物がある。このエチ
レンとの共重合モノマーであるビニルエステルと
しては酢酸ビニル、酪酸ビニル、プロピオン酸ビ
ニル、安息香酸ビニル等がある。
これらのエチレン系共重合体の内、高級脂肪酸
金属塩を含有させた場合、特に酢酸ビニル含量が
10〜50重量％のエチレン−酢酸ビニル共重合体の
ケン化物（Ｌ−EVA−OH）がＥ−EVA−OHに
対する接着性の点で好ましい。酢酸ビニル含量が
10重量％未満及び50重量％を越えるとＥ−EVA
−OHに対する接着強度が小さくなり好ましくな
い。Ｌ−EVA−OHのケン化率については10〜75
％の物が好ましい。このケン化率が10％未満のＬ
−EVA−OHは、Ｈ−EVA−OHに対する接着強
度が小さく、高級脂肪酸金属塩をこれに添加して
も実用的な強度を得るまでに達しない。又、ケン
化率が75％を越えると高級脂肪酸金属塩の添加効
果が小さくなる。
本発明で用いる高級脂肪酸金属塩としては、炭
素数７〜23の飽和又は不飽和の脂肪酸の金属塩が
用いられる。
例えばステアリン酸、ラウリン酸、パルミチン
酸のナトリウム、カルシウム、リチウム、マグネ
シウム、亜鉛、アルミニウム、バリウム塩等を挙
げることができる。上記脂肪酸金属塩は各単独で
用いても二種以上混合しても良い。更にこれらの
脂肪酸金属塩には遊離脂肪酸が本発明の効果を害
さない範囲で微量程度含まれていても良い。上記
脂肪酸金属塩の添加量はＬ−EVA−OHに対して
0.001〜0.2重量％が適当である。この量が0.001重
量％未満ではＨ−EVA−OHに対する接着性改善
効果がみられず、又、0.2重量％を超えて用いて
もＨ−EVA−OHに対する接着性のそれ以上の改
良効果は期待できない。本発明の層間接着剤とし
て用いる高級脂肪酸金属塩を含むエチレン系共重
合体には、本発明の効果を損わない限り、通常熱
可塑性樹脂に配合される各種酸化防止材、耐候
剤、帯電防止剤、滑剤、可塑剤、充填剤等の各種
添加剤を配合することができ、更に、これに、接
着性を損わない範囲で他の熱可塑性樹脂、ゴム
類、ワツクス類、又ロジン系樹脂、ポリテルペン
系樹脂、石油樹脂等の粘着付与剤を添加できる。
本発明の積層物の基材として用いるＨ−EVA
−OHは前述の汎用の包装材として用いられるも
ので、エチレン含量20〜55モル％、ケン化率90％
以上のものである。エチレン含量、ケン化率が上
記範囲外のものはガスバリア性、耐油性に欠け、
ガスバリア性多層容器、フイルムの構成層として
は通常用いられない。
本発明で用いる高級脂肪酸の金属塩を含むエチ
レン系共重合体はＥ−EVA−OH層とポリスチレ
ン系樹脂層との層間接着剤として有効に用いられ
るが、Ｈ−EVA−OHと積層するその他の熱可塑
性樹脂基材として、通常のポリオレフイン系、ポ
リ塩化ビニル系の樹脂の有効に用いられる。
本発明で用いるエチレン系共重合体と高級脂肪
酸金属塩は、必要に応じて添加する前記した添加
剤と共に、押出機、ロール、バンバリーミキサー
等にて溶融混練した後ペレツト化して用いる。
本発明のＨ−EVA−OHと他の熱可塑性樹脂基
材とを高級脂肪酸金属塩を添加したエチレン系共
重合体を層間接着剤として積層する方法として
は、(1)あらかじめそれぞれのフイルムシートを製
造しておき、三者を熱圧着する方法、(2)それぞれ
を別個の押出機で溶融し、同一のダイスより共押
出しする等の方法がある。
［発明の効果］
以上のように、高級脂肪酸金属塩を添加したエ
チレン系共重合体を層間接着剤として用いること
により、Ｈ−EVA−OH層と他の熱可塑性樹脂基
材層とからなる接着性の良好な積層物を得ること
ができる。
次に実施例で本発明を更に詳細に説明する。
実施例１〜８、比較例１
エチレン−酢酸ビニル共重合体（酢酸ビニル含
量28重量％）の40％ケン化物(A)（Ｌ−EVA−
OH）及び表−１に示した高級脂肪酸金属塩を表
−１に示した配合に従い８インチのロールにて溶
融混合しペレツト化した。この組成物ペレツトを
25mm径の押出機によつてＴダイより溶融押出しし
て、延伸ポリエステルフイルム（12μ）／ポリエ
チレン（30μ）複合基材のポリエチレン面に対
し、加工速度20ｍ／min、コート厚さ20μの条件
で押出しコーテイング加工を行なつた。
得られたラミネート物をエチレン含量32モル
％、ケン化率99.6％のエチレン−酢酸ビニル共重
合体ケン化物(B)（Ｈ−EVA−OH）の厚さ約
300μのシートおよび、ハイインパクトポリスチ
レン（HIPS）の厚さ約300μのシートに対してそ
れぞれヒートシールして、そのヒートシール強度
を測定した。その結果を表−１に示すが、表−１
から供給脂肪酸金属塩を添加したエチレン−酢酸
ビニル共重合体ケン化物(A)は無添加のものと比較
しスチレン系樹脂に対する高い接着強度を保持し
つつエチレン−酢酸ビニル共重合体ケン化物(B)に
対する接着強度が大巾に高くなつていることが判
る。
実施例 ９
エチレン−酢酸ビニル共重合体（酢酸ビニル含
量28重量％）の30％ケン化物（Ｌ−EVA−OH）
99.9重量％及びステアリン酸リチウム0.1重量％
を、８インチのロールにて溶融混合しペレツト化
した。この組成物ペレツトを実施例１と同様に延
伸ポリエステルフイルム／ポリエチレン複合基材
にラミネートした。得られたラミネート物を実施
例１のエチレン−酢酸ビニル共重合体ケン化物
（Ｈ−EVA−OH）(B)およびHIPSに対しヒート
シールし実施例１と同様にヒートシール強度を測
定した。
その結果、本実施例の組成物のＨ−EVA−OH
に対するヒートシール強度が650ｇ／15mm、
HIPSに対する強度が790ｇ／15mmであるのに対
して、ステアリン酸リチウム無添加のものはＨ−
EVA−OHに対するヒートシール強度が220ｇ／
15mm、HIPSに対する強度が770ｇ／15mmであつ
た。
実施例 10
エチレン−酢酸ビニル共重合体（酢酸ビニル含
量28重量％）の80％ケン化物（Ｌ−EVA−OH）
50重量％、エチレン−酢酸ビニル共重合体（酢酸
ビニル含量28重量％）（Ｌ−EVA−OH）の49.9
重量％及びステアリン酸リチウム0.1重量％を、
８インチのロールにて溶融混合しペレツト化し
た。この組成物ペレツトを実施例１と同様に延伸
ポリエステルフイルム／ポリエチレン複合基材に
ラミネートした。得られたラミネート物を、実施
例１のＨ−EVA−OH(B)およびHIPSに対しヒー
トシールし実施例１と同様にヒートシール強度を
測定した。
その結果、本実施例の組成物がＨ−EVA−OH
に対するヒートシール強度が700ｇ／15mm、
HIPSに対する強度が720ｇ／15mmであるのに対
して、ステアリン酸リチウム無添加（エチレン−
酢酸ビニル共重合体ケン化物50重量％、エチレン
−酢酸ビニル共重合体50重量％）のものはＨ−
EVA−OHに対するヒートシール強度が270ｇ／
15mm、HIPSに対する強度が700ｇ／15mmであつ
た。
[Industrial Application Field] The present invention relates to a resin laminate with good adhesiveness. More specifically, the present invention relates to a laminate in which an ethylene copolymer containing a higher fatty acid metal salt is used as an interlayer adhesive between a saponified ethylene-vinyl acetate copolymer layer and another thermoplastic resin base layer. [Prior art] A saponified ethylene-vinyl acetate copolymer, especially a highly saponified film, is used as a base material for various films and laminates, but although this material has excellent gas barrier properties and oil resistance, it is moisture resistant. Because of its high permeability, it is rarely used as a single material for food packaging containers, films, etc., and is usually used in a laminated form with polystyrene resin or polyolefin resin. Among these saponified ethylene-vinyl acetate copolymers, highly saponified products (hereinafter referred to as H-EVA-
OH) has weak adhesion to different substrates, so H
A polyolefin resin modified with an unsaturated carboxylic acid is used as an interlayer adhesive when laminating -EV-OH and a polyolefin resin. On the other hand, various resins and resin compositions have been proposed as interlayer adhesives between H-EVA-OH and polystyrene resins, which are generally used as laminating partners. An adhesive composition that has sufficiently satisfactory adhesion to both resins has not yet been found. The present inventors have conducted various studies on ethylene copolymers as adhesives between H-EVA-OH and various resins, particularly polystyrene resins. In particular, saponified ethylene-vinyl acetate copolymer (hereinafter referred to as L-EVA-OH) with a vinyl acetate content of 10 to 50% by weight is commonly used as an adhesive. I have considered various things, but
Although L-EVA-OH has excellent adhesion to polystyrene resins, it has poor adhesion to H-EVA-OH, and it has been found that it cannot be put to practical use as it is. [Problems to be Solved by the Invention] The object of the present invention is to provide a bond between an H-EVA-OH layer and another thermoplastic resin base layer, which has good adhesion using an ethylene copolymer as an interlayer adhesive. Our goal is to provide laminates. [Means for solving the problem] The present invention uses an ethylene copolymer containing a higher fatty acid metal salt as an interlayer adhesive between the E-EVA-OH layer and another thermoplastic resin base layer. is a feature. The ethylene copolymer used in the present invention is a conventional copolymer having an ethylene content of 2 to 99 mol%. Examples of ethylene copolymers include (1) ethylene-unsaturated ester copolymers. Unsaturated esters that are copolymer monomers with ethylene include vinyl acetate, vinyl butyrate, vinyl propionate, vinyl benzoate, methyl acrylate, ethyl acrylate,
Examples include propyl acrylate, methyl methacrylate, and ethyl methacrylate. There is also (2) a saponified product of ethylene-vinyl ester copolymer. Vinyl esters that are copolymerizable monomers with ethylene include vinyl acetate, vinyl butyrate, vinyl propionate, vinyl benzoate, and the like. Among these ethylene copolymers, when higher fatty acid metal salts are added, the vinyl acetate content is particularly low.
A saponified product of 10 to 50% by weight of ethylene-vinyl acetate copolymer (L-EVA-OH) is preferred from the viewpoint of adhesiveness to E-EVA-OH. Vinyl acetate content
E-EVA if less than 10% by weight or more than 50% by weight
The adhesive strength against -OH becomes low, which is not preferable. The saponification rate of L-EVA-OH is 10 to 75.
% is preferred. L whose saponification rate is less than 10%
-EVA-OH has a low adhesive strength to H-EVA-OH, and even if a higher fatty acid metal salt is added thereto, it does not reach a level of practical strength. Moreover, when the saponification rate exceeds 75%, the effect of adding higher fatty acid metal salt becomes small. As the higher fatty acid metal salt used in the present invention, a metal salt of a saturated or unsaturated fatty acid having 7 to 23 carbon atoms is used. Examples include sodium, calcium, lithium, magnesium, zinc, aluminum, and barium salts of stearic acid, lauric acid, and palmitic acid. The above fatty acid metal salts may be used alone or in combination of two or more. Furthermore, these fatty acid metal salts may contain a trace amount of free fatty acids as long as they do not impair the effects of the present invention. The amount of the above fatty acid metal salt added is based on L-EVA-OH.
0.001-0.2% by weight is suitable. If this amount is less than 0.001% by weight, no effect of improving adhesion to H-EVA-OH will be observed, and even if it exceeds 0.2% by weight, no further improvement in adhesion to H-EVA-OH is expected. Can not. The ethylene copolymer containing a higher fatty acid metal salt used as the interlayer adhesive of the present invention may include various antioxidants, weathering agents, antistatic agents, etc. that are usually added to thermoplastic resins, as long as they do not impair the effects of the present invention. Various additives such as agents, lubricants, plasticizers, fillers, etc. can be blended, and in addition, other thermoplastic resins, rubbers, waxes, and rosin resins can be added as long as they do not impair adhesiveness. A tackifier such as polyterpene resin, petroleum resin, etc. can be added. H-EVA used as a base material for the laminate of the present invention
-OH is used as the general-purpose packaging material mentioned above, and has an ethylene content of 20 to 55 mol% and a saponification rate of 90%.
That's all. Those with ethylene content and saponification rate outside the above ranges lack gas barrier properties and oil resistance.
It is not normally used as a constituent layer of gas barrier multilayer containers or films. The ethylene copolymer containing metal salts of higher fatty acids used in the present invention is effectively used as an interlayer adhesive between the E-EVA-OH layer and the polystyrene resin layer, but other As the thermoplastic resin base material, ordinary polyolefin-based and polyvinyl chloride-based resins can be effectively used. The ethylene copolymer and higher fatty acid metal salt used in the present invention are melt-kneaded in an extruder, roll, Banbury mixer, etc. together with the above-mentioned additives added as necessary, and then pelletized. As a method for laminating the H-EVA-OH of the present invention and other thermoplastic resin base materials using an ethylene copolymer added with higher fatty acid metal salts as an interlayer adhesive, (1) each film sheet is laminated in advance. There are two methods: (2) melting each in separate extruders and coextruding them from the same die; and (2) melting each in separate extruders. [Effects of the Invention] As described above, by using an ethylene copolymer added with higher fatty acid metal salts as an interlayer adhesive, adhesiveness between an H-EVA-OH layer and another thermoplastic resin base layer can be achieved. A laminate with good properties can be obtained. Next, the present invention will be explained in more detail with reference to Examples. Examples 1 to 8, Comparative Example 1 40% saponified product (A) of ethylene-vinyl acetate copolymer (vinyl acetate content 28% by weight) (L-EVA-
OH) and the higher fatty acid metal salts shown in Table 1 were melt-mixed and pelletized using an 8-inch roll according to the formulation shown in Table 1. This composition pellet
Melt extrusion is performed through a T-die using a 25 mm diameter extruder, and extruded onto the polyethylene surface of a stretched polyester film (12 μ)/polyethylene (30 μ) composite base material at a processing speed of 20 m/min and a coating thickness of 20 μ. Coating processing was performed. The resulting laminate was made of saponified ethylene-vinyl acetate copolymer (B) (H-EVA-OH) with an ethylene content of 32 mol% and a saponification rate of 99.6% (H-EVA-OH).
A 300μ thick sheet and a 300μ thick sheet of high impact polystyrene (HIPS) were each heat sealed and their heat seal strength was measured. The results are shown in Table-1.
The saponified ethylene-vinyl acetate copolymer (A) with the addition of fatty acid metal salts supplied from Saponified ethylene-vinyl acetate copolymer (A) maintains higher adhesive strength to styrene resins than the one without additives. It can be seen that the adhesive strength against ) has significantly increased. Example 9 30% saponified product (L-EVA-OH) of ethylene-vinyl acetate copolymer (vinyl acetate content 28% by weight)
99.9% by weight and 0.1% by weight of lithium stearate
were melt-mixed using an 8-inch roll and pelletized. This composition pellet was laminated to a stretched polyester film/polyethylene composite substrate in the same manner as in Example 1. The obtained laminate was heat sealed against the saponified ethylene-vinyl acetate copolymer (H-EVA-OH) (B) of Example 1 and HIPS, and the heat seal strength was measured in the same manner as in Example 1. As a result, H-EVA-OH of the composition of this example
Heat seal strength is 650g/15mm,
The strength against HIPS is 790g/15mm, while the one without lithium stearate has H-
Heat seal strength against EVA-OH is 220g/
15mm, the strength against HIPS was 770g/15mm. Example 10 80% saponified product (L-EVA-OH) of ethylene-vinyl acetate copolymer (vinyl acetate content 28% by weight)
50% by weight, 49.9% of ethylene-vinyl acetate copolymer (vinyl acetate content 28% by weight) (L-EVA-OH)
wt% and lithium stearate 0.1 wt%,
The mixture was melt-mixed using an 8-inch roll and pelletized. This composition pellet was laminated to a stretched polyester film/polyethylene composite substrate in the same manner as in Example 1. The obtained laminate was heat-sealed to H-EVA-OH (B) and HIPS of Example 1, and the heat-seal strength was measured in the same manner as in Example 1. As a result, the composition of this example was H-EVA-OH
Heat seal strength is 700g/15mm,
The strength against HIPS is 720g/15mm, but no lithium stearate is added (ethylene-
50% by weight saponified vinyl acetate copolymer, 50% by weight ethylene-vinyl acetate copolymer) is H-
Heat seal strength against EVA-OH is 270g/
15mm, and the strength against HIPS was 700g/15mm.
【表】【table】
Claims (1)
体を、エチレン含量20〜55モル％、ケン化率90％
以上のエチレン−酢酸ビニル共重合体ケン化物層
と他の熱可塑性樹脂基材層との層間接着剤として
用いた積層物。 ２ エチレン系共重合体が、酢酸ビニル含量10〜
50重量％のエチレン−酢酸ビニル共重合体の10〜
75％ケン化物であり、基材がポリスチレン系樹脂
である特許請求の範囲第１項記載の積層物。[Claims] 1. An ethylene copolymer containing a higher fatty acid metal salt with an ethylene content of 20 to 55 mol% and a saponification rate of 90%.
A laminate used as an interlayer adhesive between the saponified ethylene-vinyl acetate copolymer layer and another thermoplastic resin base layer. 2 The ethylene copolymer has a vinyl acetate content of 10~
10 to 50% by weight of ethylene-vinyl acetate copolymer
The laminate according to claim 1, wherein the laminate is a 75% saponified product and the base material is a polystyrene resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5934686A JPS62216740A (en) | 1986-03-19 | 1986-03-19 | Laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5934686A JPS62216740A (en) | 1986-03-19 | 1986-03-19 | Laminate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62216740A JPS62216740A (en) | 1987-09-24 |
| JPH0564103B2 true JPH0564103B2 (en) | 1993-09-13 |
Family
ID=13110639
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5934686A Granted JPS62216740A (en) | 1986-03-19 | 1986-03-19 | Laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62216740A (en) |
-
1986
- 1986-03-19 JP JP5934686A patent/JPS62216740A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62216740A (en) | 1987-09-24 |
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