JPH0212749B2 - - Google Patents
Info
- Publication number
- JPH0212749B2 JPH0212749B2 JP58093863A JP9386383A JPH0212749B2 JP H0212749 B2 JPH0212749 B2 JP H0212749B2 JP 58093863 A JP58093863 A JP 58093863A JP 9386383 A JP9386383 A JP 9386383A JP H0212749 B2 JPH0212749 B2 JP H0212749B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- resin
- modified resin
- ethylene
- polyolefin
- 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
- 239000010410 layer Substances 0.000 claims description 106
- 229920005989 resin Polymers 0.000 claims description 59
- 239000011347 resin Substances 0.000 claims description 59
- 239000004952 Polyamide Substances 0.000 claims description 20
- 229920002647 polyamide Polymers 0.000 claims description 20
- 229920000098 polyolefin Polymers 0.000 claims description 20
- 229920001577 copolymer Polymers 0.000 claims description 19
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical group O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- -1 polypropylene Polymers 0.000 claims description 13
- 239000004743 Polypropylene Substances 0.000 claims description 9
- 229920001155 polypropylene Polymers 0.000 claims description 9
- 239000012790 adhesive layer Substances 0.000 claims description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 6
- 239000002184 metal Chemical class 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000012792 core layer Substances 0.000 claims description 3
- 239000011229 interlayer Substances 0.000 description 13
- 230000001070 adhesive effect Effects 0.000 description 9
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 8
- 230000004888 barrier function Effects 0.000 description 8
- 239000010408 film Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 7
- 235000013305 food Nutrition 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 4
- 239000004840 adhesive resin Substances 0.000 description 4
- 229920006223 adhesive resin Polymers 0.000 description 4
- 230000032798 delamination Effects 0.000 description 4
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 4
- 239000005033 polyvinylidene chloride Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000005042 ethylene-ethyl acrylate Substances 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000010699 lard oil Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 238000007654 immersion Methods 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Packages (AREA)
- Wrappers (AREA)
- Laminated Bodies (AREA)
Description
本発明は高熱油処理あるいは特に加圧水レトル
ト処理が可能なバリヤー性に優れた耐熱性積層体
に関する。更に詳しくはポリアミド層もしくはポ
リオレフイン層と塩化ビニリデン樹脂層の間に耐
熱接着性樹脂を含む層を2層有することを特徴と
する耐熱性積層フイルム、シートに関するもので
ある。
近時、ボイルあるいはレトルト可能なバリヤー
性の積層体が食品包装分野において用いられ、耐
熱性、耐油性、強度の点からポリアミドを、バリ
ヤー性の点からポリ塩化ビニリデンを夫々1層以
上有する積層フイルムが提案されている。(例え
ば特公昭57−15546)。
しかし、ポリアミド層とポリ塩化ビニリデン層
との間の接着性は充分でなく、特に高温において
ボイル又はレトルトを行う用途に用いる場合には
高温における良好な接着強度を保持する接着剤層
が必要である。上述の特公昭57−15546において
は、ポリアミド層とポリ塩化ビニリデン層との間
にポリオレフイン変性樹脂層及びエチレン−酢酸
ビニル共重合体、エチレン−アクリル酸エステル
共重合体等の接着性樹脂層の2層を設置すること
により優れた接着効果のあることが示されてい
る。しかしながら、本願の目的とするような例え
ば120℃で30分以上もしくは130℃で10分以上加圧
水レトルト処理を行うごとき極めて苛酷な条件で
はその接着性は必らずしも充分でなく、より優れ
た接着性を有するバリヤー性耐熱積層体が要望さ
れていた。
本発明者はこの問題について鋭意研究の結果、
外層の耐熱樹脂層であるポリアミド層と芯層の塩
化ビニリデン樹脂層との間に特定の接着剤層を2
層設けることにより耐熱性、バリヤー性に優れ、
且つ苛酷な高熱油処理、加圧水レトルト処理にお
いても充分な実用的な層内接着力を有する耐熱性
積層体を得ることに成功した。
すなわち、本発明は、芯層が塩化ビニリデン樹
脂層D、一方の外層がポリアミド層A、他の外層
がポリアミドもしくはポリオレフインからなる層
Eであり、接着層がポリプロピレン変性樹脂又は
該樹脂90重量%以上とエチレン−アクリル酸エス
テル共重合体変性樹脂10重量%以下との混合物か
らなる層B及びポリプロピレン変性樹脂10〜30重
量%とエチレン−アクリル酸エステル共重合体変
性樹脂90〜70重量%との混合物からなる層Cから
なり、かつ
A/B/C/D/C/B/Eの順に構成された
極めて苛酷な条件下においても優れた層間接着性
を有する耐熱性積層体に関するものである。
以下、本発明を詳細に説明する。
本発明に使用するバリヤー層である塩化ビニリ
デン樹脂層Dは、65〜95重量%の塩化ビニリデン
及びこれと共重合可能な1種以上の不飽和単量体
5〜35重量%からなる塩化ビニリデン共重合体か
らなりたつ。塩化ビニリデンと共重合する単量体
としては塩化ビニル、アクリロニトリル、アクリ
ル酸エステル、アクリル酸等が好ましく用いられ
る。更に塩化ビニリデン共重合体に公知の添加剤
例えばジブチルセバケート、エポキシ化大豆油等
が含有されていてもよい。
一方の外層を形成するポリアミド層Aには、ナ
イロン6(ポリカプラミド)、ナイロン66(ポリヘ
キサメチレンアジパミド)、ナイロン6−66(6,
66の共重合体)、ナイロン610(ポリヘキサメチレ
ンセバケート)、ナイロン12(ラウロラクタムの開
環重合体)、ナイロン6−66−610(6,66,610の
共重合体)、ナイロン6−66−610−12(6,66,
610,12の共重合体)が使用される。又、他の外
層は上述のポリアミドもしくはポリオレフインか
らなる層Eからなり、ポリオレフインとしてはポ
リプロピレン又はプロピレンを90重量%以上含む
プロピレン−エチレン共重合体、ポリ4−メチル
ペンテン、ポリブテン、高密度ポリエチレン、中
密度ポリエチレン、線状低密度ポリエチレン
(LLDPE)等並びにこれらのポリマー同志のブレ
ンド物及びこれらのポリマーを少くとも50重量%
以上含む他のポリオレフイン(例えば低密度ポリ
エチレン、エチレン−酢酸ビニル共重合体、エチ
レン−エチルアクリレート共重合体)とのブレン
ド物が用いられ、結晶融点118℃以上のものが好
ましい。外層はフイルムに耐熱性、耐油性、機械
的強度を与えるために必要な層であり、少くとも
1層は特にこれらの性質に優れたポリアミドが使
用される。ポリアミドは両層に用いてもよいが、
特に耐熱ヒートシール性を重視する場合にはポリ
オレフインが食品に接する層に使用される。
本発明の最大の特色は、塩化ビニリデン樹脂層
とポリアミド層もしくはポリオレフイン層との層
間接着性を向上させるため特定の接着層を2層設
けたことにある。外層のポリアミド層もしくはポ
リオレフイン層と芯層の塩化ビニリデン樹脂層と
は接着性に乏しく、単に1層の接着層を設けた場
合は、今迄に知られた接着剤では苛酷な条件下で
充分な耐熱接着力を付与することができなかつ
た。本発明ではポリアミド層もしくはポリオレフ
イン層と塩化ビニリデン樹脂層との間にポリアミ
ド層もしくはポリオレフイン層に強固な接着力を
もつ層Bと塩化ビニリデン樹脂層に強固な接着力
をもつ層Cの2層を設け、しかもB層とC層が相
互に強力に接着するようにB層とC層に夫々特定
の耐熱性をもつ接着性樹脂を使用することにより
優れた耐熱性積層体を得ることができた。
B層にはポリアミドもしくはポリオレフインと
不可分に接着するポリオレフイン変性樹脂単独も
しくは該樹脂90重量%以上とエチレン−アクリル
酸エステル共重合体変性樹脂10重量%以下との混
合物が使用される。ポリオレフイン変性樹脂とし
ては、ポリオレフインをベースとしアクリル酸、
メタクリル酸、マレイン酸無水マレイン酸等の不
飽和カルボン酸もしくはその金属塩で変性(例え
ばグラフト重合)を行つた酸変性樹脂が用いられ
る。ポリオレフインとしてはポリプロピレンが望
ましく、不飽和カルボン酸の含量は酸変性樹脂の
10重量%以下が望ましい。かゝる酸変性樹脂とし
てはアドマー、モデイツク等の商品名のものが知
られている。
エチレン−アクリル酸エステル共重合体変性樹
脂に用いられるエチレン−アクリル酸エステル中
のアクリル酸エステルの含量は5〜25重量%が好
ましく、アクリル酸エステルとしてはアクリル酸
アルキルエステル(アルキル基の炭素数1〜8)
が好ましく使用される。該変性樹脂は、このエチ
レン−アクリル酸エステル共重合体をベースとし
てアクリル酸、メタクリル酸、マレイン酸、無水
マレイン酸等の不飽和カルボン酸で酸変性した樹
脂もしくはそれらの金属塩が用いられ、不飽和カ
ルボン酸の含量はエチレン−アクリル酸エステル
共重合体変性樹脂の10重量%以下が望ましい。こ
のエチレン−アクリル酸エステル共重合体変性樹
脂は特に塩化ビニリデン樹脂に優れた接着性を有
し耐熱性に富む接着性樹脂である。かゝる変性樹
脂としてはN−ポリマー等の商品名のものが知ら
れており、エチレン−アクリル酸エステル共重合
体に比し耐熱性に優れている。混合物をB層に使
用するときは、エチレン−アクリル酸エステル共
重合体変性樹脂は10重量%以下で用いられる。
C層としては、塩化ビニリデン樹脂層と比較的
接着性のよいポリオレフイン変性樹脂10〜30重量
%と極めて接着性のよいエチレン−アクリル酸エ
ステル共重合体変性樹脂90〜70重量%の混合物が
使用される。ポリオレフイン変性樹脂の割合が大
きすぎると塩化ビニリデン樹脂層との接着性が低
下し、その割合が小さすぎると耐熱性が低下し又
B層との接着性が低下する。
B,C層に使用することのできるエチレン−ア
クリル酸エステル共重合体変性樹脂は同一であつ
てもよく、又異つていてもよい。
本発明は、上述の組成の各層をA/B/C/
D/C/B/Eの順に積層する。このように積層
することにより少くとも一方の外層は耐熱性、機
械的強度に富むポリアミド層からなるため耐熱性
がよく、機械的性質に優れた積層体を得ることが
できる。又はB層はA層乃至E層と不可分に接着
し、バリヤー層であるD層はC層と強力に接着
し、且つB層とC層がよく接着するので強固な層
間接着力をもつ積層体が得られる。外層に隣接す
るとB層は耐熱性もつポリオレフイン変性樹脂も
しくは該樹脂を多量に含む混合物からなる為特に
耐熱性に富み、C層も該樹脂を含むため比較的耐
熱性がよいので本発明の積層体は高熱油処理、加
圧レトルト処理でも層間剥離を生じることがな
い。A層もしくはE層とD層の間にB層単独もし
くはC層単独の接着層を設けても接着力が充分で
なく、又単独層のみではポリオレフイン変性樹脂
とエチレン−アクリル酸エステル共重合体変性樹
脂の比を如何に変化させても本願の目的とする苛
酷な条件における接着性を保持することができな
い。
積層体全体の厚さは40〜1000μが好ましく、A
層とE層の合計は全層の63〜95%、B層の合計は
全層の0.5〜6%、C層の合計は全層の0.5〜6
%、D層は全層の4〜25%であることが好まし
い。A層とE層、若しくは2層あるB,C層は同
一の厚みであつても異つていてもよく又各B層及
び各C層は同一組成のものでも異つた組成のもの
でもよいが製造上の点からは同一であることが好
ましい。
本発明の積層体は一般公知の方法で製造するこ
とができる。即ち、複数の押出機を用い、各樹脂
を溶融し、筒状のものは環状ダイスを使用して筒
状に共押出され、平面状のものはT−ダイを使用
して平面状に共押出され積層される。又、別々に
作られたフイルムを積層し加熱ロールを通す等の
方法で接着して製造することができる。
このようにして得られた積層体は、薄膜をパウ
チにし例えば脂肪を含む食品等をパツクしてレト
ルト処理し、或いは厚膜を深絞り成型し容器とし
て食品を入れ缶づめ状でレトルト処理する等、食
品の高温レトルト包装に適している。更にブロー
モールドによりホツトフイル用、レトルト用の瓶
としても使用することができる。
本発明の積層体は上述のように耐熱性、耐油
性、機械的性質に優れているのみでなく、塩化ビ
ニリデン樹脂層に加えポリアミド層を少くとも1
層有するため、特にバリヤー性に優れ、又最内層
にポリオレフイン樹脂層を設けた場合には耐熱シ
ール性にも優れているという利点を有している。
以下、実施例について説明するが本発明は本発
明特許請求の範囲内である限り本実施例により限
定されるものではない。
実施例1〜5、比較例1〜5
各樹脂を4台もしくは5台の押出機で別々に押
出し、溶融された樹脂をT−ダイにて共押出し所
望の積層体とした。第1表に各層の組成とその層
間接着力を示す。A/B/C/D/C/B/E各
層の厚みは300μ/20μ/30μ/50μ/30μ/20μ/
300μであり、全厚みは750μであつた。
層間接着力の試験は次の通りである。
95℃×120分ラード油浸漬:積層体を10cm角に切
断し、95℃のラード油中に120分間浸漬し
層間接着力を測定した。
120℃×30分レトルト処理:積層体を10cm角に切
断し、120℃の加圧水中で30分レトルト処
理して冷却後、常温で層間接着力を測定し
た。
層間接着力の表示:層間接着力の測定はJISZ−
1521に基づく。
◎;300g/cm以上、〇;200〜300g/cm
△;30〜100g/cm
×;30g/cm未満
デラミ;層分離、熱処理によりデラミネーシ
ヨンを発生
The present invention relates to a heat-resistant laminate with excellent barrier properties that can be treated with high-temperature oil or, in particular, with pressurized water retort treatment. More specifically, the present invention relates to a heat-resistant laminated film or sheet having two layers containing a heat-resistant adhesive resin between a polyamide layer or a polyolefin layer and a vinylidene chloride resin layer. Recently, laminates with barrier properties that can be boiled or retorted have been used in the food packaging field, and are laminated films that have one or more layers each of polyamide for heat resistance, oil resistance, and strength, and polyvinylidene chloride for barrier properties. is proposed. (For example, Tokuko Sho 57-15546). However, the adhesion between the polyamide layer and the polyvinylidene chloride layer is not sufficient, and an adhesive layer that maintains good adhesive strength at high temperatures is required, especially when used in boiling or retorting applications at high temperatures. . In the above-mentioned Japanese Patent Publication No. 57-15546, two adhesive resin layers such as a polyolefin modified resin layer and an ethylene-vinyl acetate copolymer, an ethylene-acrylic ester copolymer, etc. are used between the polyamide layer and the polyvinylidene chloride layer. It has been shown that the layer provides excellent adhesion. However, under extremely harsh conditions, such as when pressurized water retort treatment is carried out at 120°C for 30 minutes or more or at 130°C for 10 minutes or more, as is the purpose of this application, the adhesion is not necessarily sufficient, and better There was a need for a barrier heat resistant laminate with adhesive properties. As a result of intensive research on this problem, the inventor found that
Two specific adhesive layers are placed between the polyamide layer, which is the outer heat-resistant resin layer, and the vinylidene chloride resin layer, which is the core layer.
By providing layers, it has excellent heat resistance and barrier properties,
Moreover, we succeeded in obtaining a heat-resistant laminate that has sufficient practical interlayer adhesion strength even in severe high-temperature oil treatment and pressurized water retort treatment. That is, in the present invention, the core layer is a vinylidene chloride resin layer D, one outer layer is a polyamide layer A, the other outer layer is a layer E made of polyamide or polyolefin, and the adhesive layer is a polypropylene modified resin or 90% by weight or more of the resin. Layer B consisting of a mixture of 10% by weight or less of an ethylene-acrylic ester copolymer modified resin and a mixture of 10 to 30% by weight of a polypropylene modified resin and 90 to 70% by weight of an ethylene-acrylic ester copolymer modified resin The present invention relates to a heat-resistant laminate which has excellent interlayer adhesion even under extremely severe conditions and is composed of layer C consisting of the following: A/B/C/D/C/B/E. The present invention will be explained in detail below. The vinylidene chloride resin layer D, which is a barrier layer used in the present invention, is a vinylidene chloride resin layer D consisting of 65 to 95% by weight of vinylidene chloride and 5 to 35% by weight of one or more unsaturated monomers copolymerizable therewith. Made of polymer. As the monomer copolymerized with vinylidene chloride, vinyl chloride, acrylonitrile, acrylic ester, acrylic acid, etc. are preferably used. Furthermore, the vinylidene chloride copolymer may contain known additives such as dibutyl sebacate and epoxidized soybean oil. Polyamide layer A forming one outer layer includes nylon 6 (polycapramide), nylon 66 (polyhexamethylene adipamide), nylon 6-66 (6,
66 copolymer), nylon 610 (polyhexamethylene sebacate), nylon 12 (laurolactam ring-opening polymer), nylon 6-66-610 (6,66,610 copolymer), nylon 6- 66-610-12 (6, 66,
610, 12 copolymer) is used. The other outer layer is layer E made of the above-mentioned polyamide or polyolefin, and the polyolefin is polypropylene or a propylene-ethylene copolymer containing 90% by weight or more of propylene, poly4-methylpentene, polybutene, high-density polyethylene, medium-sized polyolefin, etc. Density polyethylene, linear low density polyethylene (LLDPE) etc. and blends of these polymers and at least 50% by weight of these polymers
Blends with other polyolefins (for example, low-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer) containing the above are used, and those with a crystal melting point of 118° C. or higher are preferred. The outer layer is a layer necessary to impart heat resistance, oil resistance, and mechanical strength to the film, and at least one layer is made of polyamide, which is particularly excellent in these properties. Polyamide may be used for both layers, but
In particular, when heat-resistant heat-sealability is important, polyolefin is used for the layer that comes into contact with food. The most distinctive feature of the present invention is that two specific adhesive layers are provided to improve interlayer adhesion between the vinylidene chloride resin layer and the polyamide layer or polyolefin layer. The outer polyamide layer or polyolefin layer and the core vinylidene chloride resin layer have poor adhesion, and if only one adhesive layer is provided, the adhesives known up to now are not sufficient under harsh conditions. It was not possible to impart heat-resistant adhesive strength. In the present invention, two layers are provided between the polyamide layer or polyolefin layer and the vinylidene chloride resin layer: layer B having strong adhesive force to the polyamide layer or polyolefin layer, and layer C having strong adhesive force to the vinylidene chloride resin layer. Furthermore, an excellent heat-resistant laminate could be obtained by using an adhesive resin having a specific heat resistance for the B layer and the C layer, respectively, so that the B layer and the C layer are strongly bonded to each other. For layer B, a polyolefin-modified resin that inseparably adheres to polyamide or polyolefin may be used alone, or a mixture of 90% by weight or more of this resin and 10% by weight or less of an ethylene-acrylic acid ester copolymer-modified resin. Polyolefin-modified resins include polyolefin-based acrylic acid,
An acid-modified resin modified (eg, graft polymerized) with an unsaturated carboxylic acid such as methacrylic acid, maleic acid anhydride, or a metal salt thereof is used. Polypropylene is preferable as the polyolefin, and the content of unsaturated carboxylic acid is determined by the amount of acid-modified resin.
Desirably 10% by weight or less. As such acid-modified resins, products with trade names such as Admer and Modec are known. The content of acrylic ester in the ethylene-acrylic ester used in the ethylene-acrylic ester copolymer modified resin is preferably 5 to 25% by weight. ~8)
is preferably used. The modified resin is based on this ethylene-acrylic acid ester copolymer and is acid-modified with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, or maleic anhydride, or a metal salt thereof. The content of saturated carboxylic acid is preferably 10% by weight or less of the ethylene-acrylic acid ester copolymer modified resin. This ethylene-acrylic acid ester copolymer modified resin is an adhesive resin that has particularly excellent adhesion to vinylidene chloride resin and is rich in heat resistance. Such modified resins are known under trade names such as N-polymer, and have superior heat resistance compared to ethylene-acrylic acid ester copolymers. When the mixture is used in layer B, the ethylene-acrylic acid ester copolymer modified resin is used in an amount of 10% by weight or less. As the C layer, a mixture of 10 to 30% by weight of a polyolefin modified resin that has relatively good adhesion to the vinylidene chloride resin layer and 90 to 70% by weight of an ethylene-acrylic acid ester copolymer modified resin that has extremely good adhesion is used. Ru. If the proportion of the polyolefin modified resin is too large, the adhesion with the vinylidene chloride resin layer will be reduced, and if the proportion is too small, the heat resistance will be reduced and the adhesion with the B layer will be reduced. The ethylene-acrylic acid ester copolymer modified resins that can be used for the B and C layers may be the same or different. In the present invention, each layer having the above composition is A/B/C/
Stack them in the order of D/C/B/E. By laminating in this manner, at least one of the outer layers is made of a polyamide layer having high heat resistance and mechanical strength, so that a laminate with good heat resistance and excellent mechanical properties can be obtained. Alternatively, the B layer is inseparably adhered to the A to E layers, and the D layer, which is a barrier layer, is strongly adhered to the C layer, and the B layer and C layer are well bonded, so a laminate with strong interlayer adhesion. is obtained. Adjacent to the outer layer, the B layer is made of a heat-resistant polyolefin-modified resin or a mixture containing a large amount of the resin, so it has particularly high heat resistance, and the C layer also contains the resin and has relatively good heat resistance, so the laminate of the present invention does not cause delamination even when treated with high-temperature oil or pressurized retort treatment. Even if an adhesive layer such as B layer alone or C layer alone is provided between layer A or E and D layer, the adhesion strength is not sufficient, and if only a single layer is used, it is difficult to use polyolefin modified resin and ethylene-acrylic acid ester copolymer modified resin. No matter how the ratio of resins is changed, it is not possible to maintain adhesiveness under severe conditions, which is the objective of the present application. The thickness of the entire laminate is preferably 40 to 1000μ, and A
The total of the layer and E layer is 63-95% of the total layer, the total of the B layer is 0.5-6% of the total layer, and the total of the C layer is 0.5-6% of the total layer.
%, and the D layer preferably accounts for 4 to 25% of the total layer. The A layer and the E layer, or the two B and C layers, may have the same thickness or different thicknesses, and each B layer and each C layer may have the same composition or different compositions. From a manufacturing point of view, it is preferable that they be the same. The laminate of the present invention can be manufactured by a generally known method. That is, each resin is melted using multiple extruders, and the cylindrical one is coextruded into a cylindrical shape using an annular die, and the flat one is coextruded into a flat shape using a T-die. and laminated. Alternatively, it can be manufactured by laminating separately produced films and adhering them together by passing them through a heating roll or the like. The thus obtained laminate can be used to make a thin film into a pouch and, for example, pack food containing fat, and then retort it, or a thick film to be deep-drawn and used as a container into which food can be placed and retorted into a can. , suitable for high temperature retort packaging of food. Furthermore, by blow molding, it can be used as a hot film bottle or a retort bottle. The laminate of the present invention not only has excellent heat resistance, oil resistance, and mechanical properties as described above, but also has at least one polyamide layer in addition to the vinylidene chloride resin layer.
Since it has layers, it has an advantage of particularly excellent barrier properties, and when a polyolefin resin layer is provided as the innermost layer, it also has excellent heat-resistant sealing properties. Examples will be described below, but the present invention is not limited to these examples as long as it is within the scope of the claims. Examples 1 to 5, Comparative Examples 1 to 5 Each resin was extruded separately using four or five extruders, and the molten resins were coextruded using a T-die to form a desired laminate. Table 1 shows the composition of each layer and its interlayer adhesive strength. A/B/C/D/C/B/E thickness of each layer is 300μ/20μ/30μ/50μ/30μ/20μ/
The total thickness was 750μ. The interlayer adhesion test was as follows. Immersion in lard oil at 95°C for 120 minutes: The laminate was cut into 10 cm squares and immersed in lard oil at 95°C for 120 minutes to measure interlayer adhesion. Retort treatment at 120°C for 30 minutes: The laminate was cut into 10 cm squares, retorted in pressurized water at 120°C for 30 minutes, cooled, and then the interlayer adhesion was measured at room temperature. Indication of interlayer adhesion: Measurement of interlayer adhesion is based on JISZ-
Based on 1521. ◎; 300 g/cm or more, 〇; 200 to 300 g/cm △; 30 to 100 g/cm ×; Less than 30 g/cm Delamination: Delamination occurs due to layer separation and heat treatment
【表】【table】
【表】
第1表に示される通り、本発明の実施例はいず
れも各処理後の層間接着力が優れている。これに
対しポリプロピレン酸変性樹脂(P−300M)或
いはEEAのみを接着剤とした場合(比較例1,
5)はいずれも層間接着力が劣つていた。又、2
層の接着剤層を設けた場合でもポリプロピレン酸
変性樹脂とEEAの2層の場合は耐熱性不足でデ
ラミを生じ(比較例2)、ポリプロピレン酸変性
樹脂とEEA乃至EEA変性樹脂の割合が本発明の
範囲外の場合も矢張り層間接着力が劣り本発明の
目的を達成することができなかつた。
実施例 6
実施例1〜5と同様T−ダイ法によりA/B/
C/D/C/B/Eの積層体を得た。
ただし、A;CM−6041、20μ、
D;PVDC、8μ、B;P−300M、2μ、
E;5300B、20μ、
C;A−1600/P−300M=8/2、2μ
計56μ
上記構成のフイルムで脂肪16%を含むハムを10
個パツクし、シールして120℃×30分の加圧水レ
トルト処理したが、包装物は何等損傷なく耐熱油
に対して充分な実用性をもつていた。[Table] As shown in Table 1, all of the examples of the present invention have excellent interlayer adhesion after each treatment. On the other hand, when only polypropylene acid modified resin (P-300M) or EEA was used as adhesive (Comparative Example 1,
5) had poor interlayer adhesive strength. Also, 2
Even when an adhesive layer is provided, delamination occurs due to insufficient heat resistance in the case of two layers of polypropylene acid-modified resin and EEA (Comparative Example 2), and the ratio of polypropylene acid-modified resin and EEA or EEA-modified resin is lower than that of the present invention. Even outside the range, the interlayer adhesion strength was poor and the object of the present invention could not be achieved. Example 6 A/B/
A C/D/C/B/E laminate was obtained. However, A: CM-6041, 20μ, D: PVDC, 8μ, B: P-300M, 2μ, E: 5300B, 20μ, C: A-1600/P-300M=8/2, 2μ, total 56μ of the above configuration. 10 hams containing 16% fat in film
They were individually packaged, sealed, and subjected to pressurized water retort treatment at 120°C for 30 minutes, but the packages were not damaged in any way and had sufficient practicality for use with heat-resistant oil.
Claims (1)
がポリアミド層A、他の外層がポリアミドもしく
はポリオレフインからなる層E、接着層がポリオ
レフイン変性樹脂又は該樹脂90重量%以上とエチ
レン−アクリル酸エステル共重合体変性樹脂10重
量%以下との混合物からなる層B及びポリプロピ
レン変性樹脂10〜30重量%とエチレン−アクリル
酸エステル共重合体変性樹脂90〜70重量%との混
合物からなる層Cからなり、かつ A/B/C/D/C/B/Eの順に構成された
耐熱性積層体。 2 ポリオレフイン変性樹脂がポリプロピレンを
ベースとし不飽和カルボン酸で変性した酸変性樹
脂もしくはその金属塩である特許請求の範囲の範
囲第1項記載の耐熱性積層体。 3 エチレン−アクリル酸エステル共重合体変性
樹脂がエチレン−アクリル酸エステル共重合体を
ベースとし不飽和カルボン酸で変性した酸変性樹
脂もしくはその金属塩である特許請求の範囲第1
項又は第2項記載の耐熱性積層体。[Claims] 1 The core layer is a vinylidene chloride resin layer D, one outer layer is a polyamide layer A, the other outer layer is a layer E made of polyamide or polyolefin, and the adhesive layer is a polyolefin modified resin or 90% by weight or more of the resin. Layer B consisting of a mixture of 10% by weight or less of an ethylene-acrylic ester copolymer modified resin and a mixture of 10 to 30% by weight of a polypropylene modified resin and 90 to 70% by weight of an ethylene-acrylic ester copolymer modified resin A heat-resistant laminate consisting of layers C and configured in the order of A/B/C/D/C/B/E. 2. The heat-resistant laminate according to claim 1, wherein the polyolefin-modified resin is an acid-modified resin based on polypropylene and modified with an unsaturated carboxylic acid, or a metal salt thereof. 3. Claim 1, wherein the ethylene-acrylic ester copolymer-modified resin is an acid-modified resin based on an ethylene-acrylic ester copolymer and modified with an unsaturated carboxylic acid, or a metal salt thereof.
The heat-resistant laminate according to item 1 or 2.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9386383A JPS59218846A (en) | 1983-05-27 | 1983-05-27 | Heat-resisting laminate |
US06/578,680 US4578294A (en) | 1983-02-25 | 1984-02-09 | Heat-resistant laminates |
DE8484101817T DE3465272D1 (en) | 1983-02-25 | 1984-02-21 | Heat-resistant laminates |
EP19840101817 EP0117516B1 (en) | 1983-02-25 | 1984-02-21 | Heat-resistant laminates |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9386383A JPS59218846A (en) | 1983-05-27 | 1983-05-27 | Heat-resisting laminate |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS59218846A JPS59218846A (en) | 1984-12-10 |
JPH0212749B2 true JPH0212749B2 (en) | 1990-03-26 |
Family
ID=14094276
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP9386383A Granted JPS59218846A (en) | 1983-02-25 | 1983-05-27 | Heat-resisting laminate |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS59218846A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4788105A (en) * | 1986-09-09 | 1988-11-29 | W. R. Grace & Co. | Oxygen barrier laminates |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5430272A (en) * | 1977-08-12 | 1979-03-06 | Asahi Chem Ind Co Ltd | Laminated film |
JPS55126450A (en) * | 1979-03-26 | 1980-09-30 | Showa Denko Kk | Resin laminate |
JPS55130770A (en) * | 1979-03-30 | 1980-10-09 | Asahi Dow Ltd | Laminated film |
-
1983
- 1983-05-27 JP JP9386383A patent/JPS59218846A/en active Granted
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5430272A (en) * | 1977-08-12 | 1979-03-06 | Asahi Chem Ind Co Ltd | Laminated film |
JPS55126450A (en) * | 1979-03-26 | 1980-09-30 | Showa Denko Kk | Resin laminate |
JPS55130770A (en) * | 1979-03-30 | 1980-10-09 | Asahi Dow Ltd | Laminated film |
Also Published As
Publication number | Publication date |
---|---|
JPS59218846A (en) | 1984-12-10 |
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