JPH0564657B2 - - Google Patents
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- Publication number
- JPH0564657B2 JPH0564657B2 JP2179786A JP2179786A JPH0564657B2 JP H0564657 B2 JPH0564657 B2 JP H0564657B2 JP 2179786 A JP2179786 A JP 2179786A JP 2179786 A JP2179786 A JP 2179786A JP H0564657 B2 JPH0564657 B2 JP H0564657B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- film
- bag
- copolymer
- ethylene
- 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
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- 239000000203 mixture Substances 0.000 claims description 17
- 229920001400 block copolymer Polymers 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 10
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 6
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 150000001993 dienes Chemical class 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical group CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical class C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000004278 EU approved seasoning Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
(イ) 産業上の利用分野
本発明は、耐熱性と耐ピンホール性に優れたバ
ツグインボツクス用フイルムに関する。
(ロ) 従来の技術
従来より、液体輸送用のワンウエイ容器とし
て、段ボール箱を外装とし、ポリオレフイン等熱
可塑性合成樹脂の容器、フイルム袋を内装とし
た、所謂バツグインボツクスは、段ボール箱の持
つ強度、剛性や軽量性、印刷適性等と、熱可塑性
合成樹脂の持つ耐水性、耐薬品性、ガスバリア性
等とが組み合わされた合理的な容器として、従前
の金属缶やガラス瓶等に代つて多く用いられてい
る。
このバツグインボツクスの内装がフイルム袋で
ある場合には、特に液体内容物において、フイル
ム袋は、輸送時の連続した不規則振動により、屈
曲変形させられ、さらに、その変形によつて外装
段ボールに擦られ、また、内袋が多量の場合には
相互に擦られるという、ピンホール、亀裂の発生
し易い条件下で使用されることから、特に耐ピン
ホール性に優れたフイルムを用いることが不可欠
である。
一方、近年、果汁飲料、液体調味料、食用酢等
のフイルム袋への充填において、70〜90℃程度の
高温充填が増加してきており、内袋フイルムとし
ては、前述の耐ピンホール性はもとより、それら
高温充填に耐え得る耐熱性も求められている。
しかしながら、内袋として従来より用いられて
いるエチレン−酢酸ビニル共重合体樹脂フイルム
は、前述の耐ピンホール性には優れるものの、高
温充填時の変形が大きく耐熱性を満足し得るもの
ではない。また、ポリエチレン、ポリプロピレン
等の他のポリオレフイン樹脂フイルムは、耐熱性
は満足するものの、耐ピンホール性に劣るという
致命的欠陥があり、さらに、それらに柔軟性を付
与し耐ピンホール性を改良すべくエチレン−プロ
ピレン共重合体ゴム等を混合することも考えられ
るが、それとて耐熱性と耐ピンホール性の両者を
同時に満足することは困難であり、また、ヒート
シール性が不良になるという新らたな問題も発生
する。
(ハ) 発明が解決しようとする問題点
本発明は、バツグインボツクス用フイルムにお
ける前述の問題に鑑みてなされたものであり、そ
の目的とするところは、耐熱性と耐ピンホール性
に優れたバツグインボツクス用フイルムを提供す
るにある。
(ニ) 問題点を解決するための手段
本発明のバツグインボツクス用フイルムは、直
鎖状低密度ポリエチレン70〜95重量％と、一般式
Ａ（−Ｂ−Ａ）ｎ（ここで、Ａはモノビニル置換芳
香族炭化水素の重合体ブロツク、Ｂは共役ジエン
のエラストマー性重合体ブロツク、ｎは１〜５の
整数である。）で表わされるブロツク共重合体の
水素添加誘導体30〜５重量％との組成物からな
る。
ここで、直鎖状低密度ポリエチレンとは、プロ
ピレン、ブテン−１、ヘキセン−１，４−メチル
ペンテン−１、オクテン−１等、C3〜C8の分子
骨格であるα−オレフインを１〜20重量％含有す
るエチレン−α−オレフイン共重合体で、遷移金
属化合物と有機金属化合物とを組合せた触媒を用
いてイオン反応によりエチレンとC3〜C8の分子
骨格であるα−オレフインを１つ以上含んで共重
合させて生成される樹脂であり、一般的に知られ
ている酸素ラジカルを開始剤とし高圧力下でラジ
カル反応によりエチレンを重合させて生成される
分岐状低密度ポリエチレンとは、分子構造、溶融
特性、結晶化特性、固体物性、延伸特性において
異なつた性能を有するものである。
本発明においては、この直鎖状低密度ポリエチ
レンは、密度が0.910〜0.940ｇ／cm2、好ましくは
0.916〜0.935ｇ／cm2で、MFRが0.1〜５ｇ／10分、
好ましくは0.1〜１ｇ／10分の範囲に含まれるも
のがよい。直鎖状低密度ポリエチレンの密度が
0.910ｇ／cm2未満になるとフイルムの耐熱性が悪
化し、0.940ｇ／cm3を越えると耐ピンホール性が
損われる。また、MFRが0.1ｇ／10分未満になる
とフイルムをダイ間隙より溶融押出しする際、異
常流動が発生し均一なフイルムが得られなくな
り、５ｇ／10分を越えるとフイルムの成膜安定性
が悪化すると共に、機械的強度の劣るものとな
る。
また、本発明におけるブロツク共重合体の水素
添加誘導体とは、重合体ブロツクＡを構成する単
量体のモノビニル置換芳香族炭化水素がスチレン
であるのが好ましく、α−メチルスチレン、ビニ
ルトルエンその他の低級アルキル置換スチレン、
ビニルナフタレン等も用いられ、また、重合体ブ
ロツクＢにおける共役ジエン単量体はブタジエン
あるいはイソプレンが好ましく、また、両者の混
合物でもよく、重合体ブロツクＢを形成するため
にブタジエンが単一の共役ジエン単量体として用
いられる場合には、ブロツク共重合体が水素添加
されて二重結合が飽和された後にエラストマー性
を保持しているために、ポリブジエンブロツクに
おけるミクロ構造中１，２−ミクロ構造が20〜50
％となる重合条件が採用されていることが好まし
く、より好ましくは１，２−ミクロ構造が35〜45
％のものである。また、ブロツク共重合体中の重
合体ブロツクＡの重量平均分子量は5000〜
125000、重合体ブロツクＢのそれは15000〜
250000の範囲にあることが好ましい。
これらのブロツク共重合体の製造方法として
は、数多くの方法が提案されている。代表的な方
法としては、例えば特公昭40−23798号公報に記
載された方法があつて、リチウム触媒またはチー
グラー型触媒を用いて不活性溶媒中でブロツク共
重合を行なわせる。
これらのブロツク共重合体の水素添加処理は、
例えば特公昭42−8704号、同43−6636号あるいは
同46−20814号等の各公報に記載された方法によ
り、不活性溶媒中で水素添加触媒の存在下に行な
われる。この水素添加では、重合体ブロツクＢ中
のオレフイン型二重結合の少なくとも50％、好ま
しくは80％以上が水素添加され、重合体ブロツク
Ａ中の不飽和結合の25％以下が水素添加される。
このような水素添加されたブロツク共重合体の一
つとして、シエルケミカル社より「KRATON−
Ｇ」という商品名で市販されているものがある。
本発明における組成物は、前記直鎖状低密度ポ
リエチレンが70〜95重量％、好ましくは80〜90重
量％と、前記ブロツク共重合体の水素添加誘導体
が30〜５重量％、好ましくは20〜10重量％とから
なる。前記ブロツク共重合体の水素添加誘導体が
５重量％未満では、組成物フイルムの耐ピンホー
ル性が劣り、30重量％を越えると、組成物フイル
ムの熱収縮が大きくなつて変形が著しくなるのみ
ならず、膜厚均一性に欠け、耐ブロツキンング性
が劣るフイルムしか得られなくなる。
以上の組成物からなる本発明のバツグインボツ
クス用フイルムは、組成物を公知のＴダイ成形、
インフレーシヨン成形等でフイルム成形すること
により得られる。また、その際、本発明フイルム
とポリプロピレン、ポリアミド等の他材料フイル
ムとを公知の方法で積層して複合化することも可
能である。
本発明のフイルムの厚みは、単層とする場合に
は、通常50〜90μであり、他材料フイルムと積層
する場合にはそれ以下とすることも可能である。
(ホ) 実施例
実施例 １
エチレン−ブテン−１共重合体（ブテン−１含
有量７重量％、密度0.921ｇ／cm3、MFR0.35ｇ／
10分）85重量％と水添ブロツク共重合体（シエル
ケミカル社製、「KRATON−G1652」）15重量％
との組成物を、口径65mm、Ｌ／D26の押出機を用
いて、ダイス温度230℃でインフレーシヨン成形
することにより、厚み80μのフイルムを製造し
た。
得られたフイルムから打ち抜いた210mm×290mm
のサンプルを、ゲルボフレツクステスターを用い
て室温にて4000回の屈曲を繰り返した後、フイル
ムに発生したピンホール数を数えることにより、
耐ピンホール性を評価した。
さらに、縦575mm×横570mmの大きさのフイルム
袋を作製してそれを二重袋とし、85℃の温水を充
填、ヒートシールした後、286mm×286mm×270mm
の段ボール箱に入れ、1G／振幅１インチの上下
水平振動を１時間繰り返すことにより振動試験を
実施し、液漏れの有無、二重袋間の密着の有無、
および寸法の変化を観察した。
結果を表に示す。
実施例 ２
エチレン−ブテン−１共重合体と水添ブロツク
共重合体の組成比を、各々、75重量％、25重量％
とした外は、実施例１と同様にしてフイルムを製
造し、評価した。
実施例 ３
エチレン−ブテン−１共重合体と水添ブロツク
共重合体の組成比を、各々、95重量％、５重量％
とした外は、実施例１と同様にしてフイルムを製
造し、評価した。
実施例 ４
エチレン−４−メチルペンテン−１共重合体
（４−メチルペンテン−１含有量３重量％、密度
0.920ｇ／cm3、MFR0.5ｇ／10分）90重量％と、実
施例１で用いたと同じ水添ブロツク共重合体10重
量％との組成物を用いた外は、実施例１と同様に
してフイルムを製造し、評価した。
比較例 １
実施例１で用いたと同じエチレン−ブテン−１
共重合体のみを用いた外は、実施例１と同様にし
てフイルムを製造し、評価した。
比較例 ２
エチレン−ブテン−１共重合体と水添ブロツク
共重合体の組成比を、各々、60重量％、40重量％
とした外は、実施例１と同様にしてフイルムを製
造し、評価した。
比較例 ３
高密度ポリエチレン（密度0.952ｇ／cm3、
MFR0.35ｇ／10分）65重量％と、実施例１で用
いたと同じ水添ブロツク共重合体35重量％との組
成物を用いた外は、実施例１と同様にしてフイル
ムを製造し、評価した。
比較例 ４
実施例１で用いたと同じエチレン−ブテン−１
共重合体70重量％とエチレン−プロピレン共重合
体ゴム（プロピレン含有量26重量％）30重量％と
の組成物を用いた外は、実施例１と同様にしてフ
イルムを製造し、評価した。
比較例 ５
実施例１で用いたと同じエチレン−ブテン−１
共重合体90重量％とエチレン−プロピレン共重合
体ゴム（プロピレン含有量26重量％）10重量％と
の組成物を用いた外は、実施例１と同様にしてフ
イルムを製造し、評価した。
比較例 ６
実施例１で用いたと同じエチレン−ブテン−１
共重合体85重量％と、エチレン−酢酸ビニル共重
合体（酢酸ビニル含有量15重量％、密度0.940
ｇ／cm3、MFR0.5ｇ／10分）15重量％との組成物
を用いた外は、実施例１と同様にしてフイルムを
製造し、評価した。
比較例 ７
比較例６で用いたと同じエチレン−酢酸ビニル
共重合体のみを用いた外は、実施例１と同様にし
てフイルムを製造し、評価した。
(a) Industrial Application Field The present invention relates to a film for bag-in boxes that has excellent heat resistance and pinhole resistance. (b) Conventional technology Conventionally, so-called bag-in boxes have been used as one-way containers for transporting liquids, with a cardboard box as the exterior and a container made of thermoplastic synthetic resin such as polyolefin, or a film bag as the interior. It is widely used in place of conventional metal cans and glass bottles as a rational container that combines rigidity, lightness, printability, etc. with the water resistance, chemical resistance, gas barrier properties, etc. of thermoplastic synthetic resin. It is being When the interior of this bag-in box is a film bag, the film bag is bent and deformed due to continuous irregular vibrations during transportation, especially for liquid contents, and the deformation causes the outer cardboard to bend. It is essential to use a film that has particularly excellent pinhole resistance because it is used under conditions where pinholes and cracks are likely to occur, as the inner bags are likely to be rubbed and, if there are a large number of inner bags, rubbed against each other. It is. On the other hand, in recent years, when filling film bags with fruit juice drinks, liquid seasonings, edible vinegar, etc., high-temperature filling at temperatures of around 70 to 90°C has been increasing. , heat resistance that can withstand such high-temperature filling is also required. However, although the ethylene-vinyl acetate copolymer resin film conventionally used as the inner bag has excellent pinhole resistance, it is deformed during high-temperature filling and cannot satisfy the heat resistance. Although other polyolefin resin films such as polyethylene and polypropylene have satisfactory heat resistance, they have the fatal flaw of poor pinhole resistance. It may be possible to mix ethylene-propylene copolymer rubber, etc., but it is difficult to satisfy both heat resistance and pinhole resistance at the same time, and there are also new problems such as poor heat sealing properties. Other problems may also occur. (c) Problems to be Solved by the Invention The present invention has been made in view of the above-mentioned problems with film for bag-in boxes, and its purpose is to provide a film with excellent heat resistance and pinhole resistance. To provide film for bag-in boxes. (d) Means for solving the problems The film for bag-in boxes of the present invention contains 70 to 95% by weight of linear low-density polyethylene and the general formula A(-B-A)n (where A is 30 to 5% by weight of a hydrogenated derivative of a block copolymer represented by a monovinyl-substituted aromatic hydrocarbon polymer block, B is a conjugated diene elastomeric polymer block, and n is an integer from 1 to 5. consisting of a composition of Here, linear low-density polyethylene refers to propylene, butene-1, hexene-1,4-methylpentene-1, octene-1, etc., α-olefin having a molecular skeleton of C3 to C8 . An ethylene-α-olefin copolymer containing 20% by weight, in which ethylene and α-olefin, which has a molecular skeleton of C 3 to C 8 , are combined into 1 by ionic reaction using a catalyst that combines a transition metal compound and an organometallic compound. What is branched low-density polyethylene, which is a resin produced by copolymerizing ethylene containing two or more elements, and is produced by polymerizing ethylene through a radical reaction under high pressure using the commonly known oxygen radical as an initiator? , have different performance in molecular structure, melting properties, crystallization properties, solid physical properties, and stretching properties. In the present invention, this linear low density polyethylene has a density of 0.910 to 0.940 g/cm 2 , preferably
0.916~0.935g/ cm2 , MFR 0.1~5g/10min,
Preferably, the amount is in the range of 0.1 to 1 g/10 minutes. The density of linear low density polyethylene is
If it is less than 0.910 g/cm 2 , the heat resistance of the film will deteriorate, and if it exceeds 0.940 g/cm 3 , pinhole resistance will be impaired. Additionally, if the MFR is less than 0.1 g/10 minutes, abnormal flow will occur when melt extruding the film from the die gap, making it impossible to obtain a uniform film, and if it exceeds 5 g/10 minutes, the film formation stability will deteriorate. At the same time, the mechanical strength becomes inferior. Furthermore, in the hydrogenated derivative of the block copolymer in the present invention, it is preferable that the monovinyl-substituted aromatic hydrocarbon of the monomer constituting the polymer block A is styrene, and α-methylstyrene, vinyltoluene, etc. lower alkyl substituted styrene,
Vinylnaphthalene, etc. may also be used, and the conjugated diene monomer in polymer block B is preferably butadiene or isoprene, or a mixture of the two may be used. When used as a monomer, the 1,2-microstructure in the polybutene block retains its elastomeric properties after the block copolymer is hydrogenated to saturate the double bonds. 20-50 structures
It is preferable that polymerization conditions are adopted such that the 1,2-microstructure is 35 to 45%.
%belongs to. In addition, the weight average molecular weight of polymer block A in the block copolymer is 5000~
125,000, that of polymer block B is 15,000~
Preferably, it is in the range of 250,000. Many methods have been proposed for producing these block copolymers. A typical method is, for example, the method described in Japanese Patent Publication No. 40-23798, in which block copolymerization is carried out in an inert solvent using a lithium catalyst or a Ziegler type catalyst. The hydrogenation treatment of these block copolymers is
For example, the reaction is carried out in an inert solvent in the presence of a hydrogenation catalyst by the method described in Japanese Patent Publications No. 42-8704, No. 43-6636, or No. 46-20814. In this hydrogenation, at least 50%, preferably 80% or more of the olefinic double bonds in polymer block B are hydrogenated, and up to 25% of the unsaturated bonds in polymer block A are hydrogenated.
As one of such hydrogenated block copolymers, “KRATON-
There is one commercially available under the trade name "G". The composition of the present invention contains 70 to 95% by weight, preferably 80 to 90% by weight of the linear low density polyethylene, and 30 to 5% by weight, preferably 20 to 5% by weight of the hydrogenated derivative of the block copolymer. 10% by weight. If the hydrogenated derivative of the block copolymer is less than 5% by weight, the pinhole resistance of the composition film will be poor, and if it exceeds 30% by weight, the composition film will only undergo large thermal shrinkage and significant deformation. However, the resulting film lacks uniformity in film thickness and has poor blocking resistance. The film for bag-in boxes of the present invention comprising the above composition can be obtained by molding the composition into a conventional T-die molding process.
It can be obtained by film forming using inflation molding or the like. Further, in this case, it is also possible to form a composite by laminating the film of the present invention and a film made of other materials such as polypropylene or polyamide by a known method. The thickness of the film of the present invention is usually 50 to 90 μm when it is a single layer, and can be less than that when laminated with films of other materials. (E) Examples Example 1 Ethylene-butene-1 copolymer (butene-1 content 7% by weight, density 0.921 g/cm 3 , MFR 0.35 g/cm 3 )
10 minutes) 85% by weight and hydrogenated block copolymer (manufactured by Shell Chemical Co., "KRATON-G1652") 15% by weight
A film having a thickness of 80 μm was produced by inflation-molding the composition with an extruder having a diameter of 65 mm and an L/D of 26 at a die temperature of 230° C. 210mm x 290mm punched from the obtained film
After bending the sample 4000 times at room temperature using a gelbo flex tester, the number of pinholes generated in the film was counted.
Pinhole resistance was evaluated. Furthermore, we made a film bag measuring 575mm long x 570mm wide, made it into a double bag, filled it with 85°C warm water, heat sealed it, and made it into a 286mm x 286mm x 270mm bag.
A vibration test was conducted by placing the product in a cardboard box and repeating vertical and horizontal vibrations of 1G/1 inch amplitude for 1 hour to determine whether there was any leakage, whether there was close contact between the double bags, etc.
and changes in dimensions were observed. The results are shown in the table. Example 2 The composition ratios of ethylene-butene-1 copolymer and hydrogenated block copolymer were 75% by weight and 25% by weight, respectively.
A film was produced and evaluated in the same manner as in Example 1, except for the following. Example 3 The composition ratios of ethylene-butene-1 copolymer and hydrogenated block copolymer were 95% by weight and 5% by weight, respectively.
A film was produced and evaluated in the same manner as in Example 1, except for the following. Example 4 Ethylene-4-methylpentene-1 copolymer (4-methylpentene-1 content 3% by weight, density
The same procedure as in Example 1 was used except that a composition of 90% by weight (0.920g/cm 3 , MFR 0.5g/10min) and 10% by weight of the same hydrogenated block copolymer as used in Example 1 was used. A film was produced and evaluated. Comparative Example 1 Same ethylene-butene-1 as used in Example 1
A film was produced and evaluated in the same manner as in Example 1, except that only the copolymer was used. Comparative Example 2 The composition ratios of ethylene-butene-1 copolymer and hydrogenated block copolymer were 60% by weight and 40% by weight, respectively.
A film was produced and evaluated in the same manner as in Example 1, except for the following. Comparative Example 3 High-density polyethylene (density 0.952 g/cm 3 ,
A film was produced in the same manner as in Example 1, except that a composition of 65% by weight of MFR0.35g/10min) and 35% by weight of the same hydrogenated block copolymer as used in Example 1 was used. evaluated. Comparative Example 4 Same ethylene-butene-1 as used in Example 1
A film was produced and evaluated in the same manner as in Example 1, except that a composition of 70% by weight of the copolymer and 30% by weight of ethylene-propylene copolymer rubber (propylene content: 26% by weight) was used. Comparative Example 5 Same ethylene-butene-1 as used in Example 1
A film was produced and evaluated in the same manner as in Example 1, except that a composition of 90% by weight of the copolymer and 10% by weight of ethylene-propylene copolymer rubber (propylene content: 26% by weight) was used. Comparative Example 6 Same ethylene-butene-1 as used in Example 1
85% by weight copolymer and ethylene-vinyl acetate copolymer (vinyl acetate content 15% by weight, density 0.940
A film was produced and evaluated in the same manner as in Example 1, except that a composition with 15% by weight (g/cm 3 , MFR 0.5g/10min) was used. Comparative Example 7 A film was produced and evaluated in the same manner as in Example 1, except that only the same ethylene-vinyl acetate copolymer used in Comparative Example 6 was used.
【表】
(ヘ) 発明の効果
本発明のバツグインボツクス用フイルムは、耐
ピンホール性に優れるので、バツグインボツクス
の内袋として使用するにおいて液漏れの発生がな
く、さらに、耐熱性に優れるので、内容物の高温
充填が可能である等の効果を奏するものである。[Table] (F) Effects of the Invention The film for bag-in boxes of the present invention has excellent pinhole resistance, so there is no leakage when used as the inner bag of bag-in boxes, and furthermore, it has excellent heat resistance. Therefore, it is possible to fill the contents at high temperature.
Claims (1)
一般式Ａ（−Ｂ−Ａ）ｎ（ここで、Ａはモノビニル
置換芳香族炭化水素の重合体ブロツク、Ｂは共役
ジエンのエラストマー性重合体ブロツク、ｎは１
〜５の整数である。）で表わされるブロツク共重
合体の水素添加誘導体30〜５重量％との組成物か
らなるバツグインボツクス用フイルム。1 70-95% by weight of linear low-density polyethylene,
General formula A(-B-A)n (where A is a monovinyl-substituted aromatic hydrocarbon polymer block, B is a conjugated diene elastomeric polymer block, and n is 1
It is an integer of ~5. A bag-in-box film comprising a composition containing 30 to 5% by weight of a hydrogenated derivative of a block copolymer represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2179786A JPS62179543A (en) | 1986-02-03 | 1986-02-03 | Bag-in-box film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2179786A JPS62179543A (en) | 1986-02-03 | 1986-02-03 | Bag-in-box film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62179543A JPS62179543A (en) | 1987-08-06 |
| JPH0564657B2 true JPH0564657B2 (en) | 1993-09-16 |
Family
ID=12065039
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2179786A Granted JPS62179543A (en) | 1986-02-03 | 1986-02-03 | Bag-in-box film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62179543A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100307699B1 (en) * | 1993-02-03 | 2001-11-30 | 엑손 케미칼 패턴츠 인코포레이티드 | Thermoplastic Elastomer Copolymer Film |
| US6218470B1 (en) * | 1994-06-01 | 2001-04-17 | The Dow Chemical Company | Thermoplastic elastomeric blends |
-
1986
- 1986-02-03 JP JP2179786A patent/JPS62179543A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62179543A (en) | 1987-08-06 |
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| EXPY | Cancellation because of completion of term |