JPH0214186B2 - - Google Patents
Info
- Publication number
- JPH0214186B2 JPH0214186B2 JP2298981A JP2298981A JPH0214186B2 JP H0214186 B2 JPH0214186 B2 JP H0214186B2 JP 2298981 A JP2298981 A JP 2298981A JP 2298981 A JP2298981 A JP 2298981A JP H0214186 B2 JPH0214186 B2 JP H0214186B2
- Authority
- JP
- Japan
- Prior art keywords
- stretching
- block copolymer
- aromatic hydrocarbon
- vinyl aromatic
- block
- 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
- 229920001400 block copolymer Polymers 0.000 claims description 26
- 229920000642 polymer Polymers 0.000 claims description 22
- -1 vinyl aromatic hydrocarbon Chemical class 0.000 claims description 20
- 229920002554 vinyl polymer Polymers 0.000 claims description 20
- 150000001993 dienes Chemical class 0.000 claims description 16
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
- 239000007822 coupling agent Substances 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 150000002900 organolithium compounds Chemical class 0.000 claims description 3
- 239000005049 silicon tetrachloride Substances 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- 230000000903 blocking effect Effects 0.000 claims 1
- 238000000034 method Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000002372 labelling Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920006257 Heat-shrinkable film Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
Description
本発明は、透明で低温延伸性及び低温収縮性に
優れ、しかも良好な機械的強度を有するブロツク
共重合体の１軸延伸フイルム、シート又はチユー
ブに関する。
収縮包装はこれまでの包装技術では避けられな
かつたダブツキやシワがきれいに解決でき、又商
品に密着した包装や異形物の包装が迅速にできる
ことから最近特に食品包装用にその利用が増加し
ている。従来、収縮包装用フイルム、シート等の
素材としては、低温収縮性、透明性、機械的強度
等の要求特性を満足することから塩化ビニル樹脂
が主に使用されている。しかし塩化ビニル樹脂は
塩化ビニルモノマーや可塑剤類の衛生上の問題、
焼却時の塩化水素の発生問題等からその代替品が
強く要望されている。
一方、ビニル芳香族炭化水素と共役ジエンから
成るブロツク共重合体樹脂は上記の様な諸問題を
有せず、しかも良好な透明性と耐衝撃性を有する
ことから食品包装容器の素材として広く利用され
つつある。しかしながら、従来知られているブロ
ツク共重合体は延伸温度が高く、又収縮を起す温
度も高いため熱収縮包装用素材としては不適当で
あつた。
例えば特開昭49−102494号公報及び特開昭49−
108177号公報にはそれぞれスチレン系炭化水素含
有量50〜95重量％のブロツク共重合体及び該ブロ
ツク共重合体にスチレン系樹脂を配合した組成物
を２軸延伸した包装用フイルムが記載されている
が、かかるフイルムは熱収縮温度が100℃以上で
なければ十分な収縮率は得られない。
かかるブロツク共重合体の低温収縮性を改良す
る方法も特開昭50−6673号公報で試みられてい
る。この方法はチユーブラ法を適用することによ
つて有効な高度の配向が起こるような温度域で膨
張延伸して同時２軸配向を行い、良好な低温熱収
縮性を持つフイルムを製造する方法である。しか
しながら、この方法においては原料樹脂のブタジ
エン含有量の多寡に応じて極めて厳選された温度
範囲で膨張延伸を開始し、しかも膨張開始点から
膨張終了点に至る延伸帯域のフイルムに厳密にコ
ントロールされた温度勾配をつけなければ所望の
低温熱収縮性を持つフイルムが得られず、従つて
容易に実施し難いという欠点を有する。しかもか
かる方法を利用して通常のブロツク共重合体から
１軸延伸フイルムを得ようとしても延伸時にフイ
ルムが破断してフイルム成形ができないという問
題を有している。
周知の如く、２軸延伸フイルムやシートは収縮
時縦横両方向に収縮するため通常の収縮包装にお
いては好適な包装用材料になりうるが、ラベル用
として用いる場合にはそれがかえつて欠点とな
り、ラベル用には利用できない。一般に熱収縮性
フイルムをラベル用に使用する場合、概略予め被
包装品の長さに合せてカツトされたフイルムを熱
収縮させて被包装品に密着させるため横方向には
熱収縮するが縦方向にはほとんど熱収縮しないも
のでなければならない。
従つてラベル用フイルムとしては１軸延伸フイ
ルムが使用されるが、ブロツク共重合体の低温収
縮性フイルムは未だ知られていず、しかも従来の
ブロツク共重合体に公知の２軸延伸条件をそのま
ま１軸延伸に利用しても良好な低温収縮性を示す
フイルムは得られない。
かかる現状に鑑み、本発明者らは低温収縮性に
優れ、ラベル用に好適なブロツク共重合体１軸延
伸フイルム、シート等を得る方法について鋭意検
討を進めた結果、ブロツク共重合体を構成するビ
ニル芳香族炭化水素重合体ブロツクがある特定の
範囲の分子量を有するブロツク共重合体を用い、
しかも比較的低温において特定の延伸倍率で延伸
することによりその目的が達成されることを見い
出し、本発明を完成するに至つた。
即ち、本発明は、一般構造式
（Ａ−Ｂ）o ……(イ)
Ａ−Ｂ−Ａ ……(ロ)
Ｂ（−Ａ−Ｂ）o ……(ハ)
〔（Ｂ−Ａ）o〕−n+2Ｘ ……(ニ)
〔（Ａ−Ｂ）o〕−n+2Ｘ ……(ホ)
〔（Ｂ−Ａ−）oＢ〕−n+2Ｘ ……(ヘ)
〔（Ａ−Ｂ−）oＡ〕−n+2Ｘ ……(ト)
（上式において、Ａはビニル芳香族炭化水素重合
体ブロツクであり、Ｂは共役ジエンを主とする重
合体ブロツクである。ＡブロツクとＢブロツクと
の境界は必ずしも明瞭に区別される必要はない。
Ｘは例えば四塩化ケイ素、四塩化スズなどのカツ
プリング剤の残基又は多官能有機リチウム化合物
等の開始剤の残基を示す。ｍ及びｎはそれぞれ１
以上の整数である。）
のいずれかで表わされ、しかもビニル芳香族炭化
水素重合体ブロツクの数平均分子量が20000ない
し50000で、ビニル芳香族炭化水素と共役ジエン
との重量比が60：40ないし95：５であるブロツク
共重合体を延伸温度60ないし120℃、延伸倍率1.5
ないし８倍で押出方向と直交する方向に実質的に
１軸延伸してなる延伸方向における80℃の熱収縮
率が40〜80％、延伸方向に対して直交方向におけ
る80℃の熱収縮率が15％未満、延伸方向における
引張弾性率が7000Kg／cm2以上であるブロツク共重
合体１軸延伸フイルム、シート又はチユーブに関
する。
本発明のブロツク共重合体１軸延伸フイルム、
シート又はチユーブは低温において優れた収縮性
を有するため、高温に加熱すると変質や変形を生
じる様な物品のラベリング、例えばプラスチツク
成形品のラベリングに適する。
以下、本発明を詳細に説明する。
本発明においては、少なくとも１個、好ましく
は２個以上のビニル芳香族炭化水素重合体ブロツ
クと少なくとも１個、好ましくは２個以上の共役
ジエンを主体とする重合体ブロツクとを有するブ
ロツク共重合体を使用する。ここで共役ジエンを
主体とする重合体ブロツクとは、共役ジエンの含
有量が50重量％以上、好ましくは70重量％以上、
更に好ましくは90重量％以上の重合体ブロツクで
ある。共役ジエンを主体とする重合体ブロツク中
に共重合されているビニル芳香族炭化水素は重合
体ブロツク中に均一に分布していても、またテー
パー（漸減）状に分布していてもよい。
尚、ビニル芳香族炭化水素重合体ブロツクと共
役ジエンを主体とする重合体ブロツクとの間にビ
ニル芳香族炭化水素の含有量が50重量％を超える
部分がある場合には、該部分は共役ジエンを主体
とする重合体ブロツクに含めるものとする。ブロ
ツク共重合体中のビニル芳香族炭化水素と共役ジ
エンとの重量比は60：40ないし95：５、好ましく
は75：25ないし90：10、更に好ましくは78：22な
いし88：12である。ビニル芳香族炭化水素の含有
量が60重量％未満の場合は引張強度や剛性が劣り
フイルム、シート等として不適当であり、又95重
量％を超える場合は耐衝撃性が劣るため好ましく
ない。
本発明で使用するブロツク共重合体において、
ビニル芳香族炭化水素重合体ブロツクの数平均分
子量は20000ないし50000である。ビニル芳香族炭
化水素重合体ブロツクの数平均分子量が20000未
満の場合には引張強度や剛性が劣り、又50000を
超える場合は低温での１軸延伸ができず、しかも
低温収縮性が劣るため好ましくない。尚、ビニル
芳香族炭化水素重合体ブロツクの数平均分子量
は、例えばゲルパーミエーシヨンクロマトグラフ
イー（GPC）で測定することにより求めること
ができる。
本発明において特に好ましいブロツク共重合体
は、共役ジエンを主体とする重合体ブロツクが実
質上共役ジエン単独重合体で構成されているブロ
ツク共重合体である。ここで共役ジエンを主体と
する重合体ブロツクが実質上共役ジエン単独重合
体で構成されているブロツク重合体とは、共役ジ
エンを主体とする重合体ブロツク中に共重合して
いるビニル芳香族炭化水素の量が少ないブロツク
共重合体、換言すればビニル芳香族炭化水素重合
体ブロツクに組込まれていないビニル芳香族炭化
水素の量が少ないブロツク共重合体を意味し、具
体的には下式で表示される非ブロツク率が15重量
％以下、好ましくは10重量％以下、更に好ましく
は５重量％以下のブロツク共重合体である。
The present invention relates to a uniaxially stretched film, sheet, or tube made of a block copolymer that is transparent, has excellent low-temperature stretchability and low-temperature shrinkability, and has good mechanical strength. Shrink packaging has been increasingly used in recent years, especially for food packaging, as it can effectively eliminate the bagging and wrinkles that were unavoidable with conventional packaging technology, and it can also quickly wrap products tightly or irregularly shaped items. . Conventionally, vinyl chloride resin has been mainly used as a material for shrink wrapping films, sheets, etc. because it satisfies required properties such as low-temperature shrinkability, transparency, and mechanical strength. However, vinyl chloride resin has hygienic problems due to vinyl chloride monomer and plasticizers.
There is a strong demand for alternatives due to the problem of hydrogen chloride generation during incineration. On the other hand, block copolymer resins made of vinyl aromatic hydrocarbons and conjugated dienes do not have the above problems and have good transparency and impact resistance, so they are widely used as materials for food packaging containers. It is being done. However, conventionally known block copolymers are unsuitable as materials for heat-shrinkable packaging because of their high stretching temperatures and high shrinkage temperatures. For example, JP-A-49-102494 and JP-A-49-
Publication No. 108177 describes a packaging film obtained by biaxially stretching a block copolymer having a styrene hydrocarbon content of 50 to 95% by weight, and a composition in which the block copolymer is blended with a styrene resin. However, such a film cannot achieve sufficient shrinkage unless the heat shrinkage temperature is 100°C or higher. A method for improving the low-temperature shrinkability of such block copolymers has also been attempted in JP-A-50-6673. This method is a method of manufacturing a film with good low-temperature heat shrinkability by simultaneously performing biaxial orientation by expanding and stretching in a temperature range where effective high degree of orientation occurs by applying the tubular method. . However, in this method, expansion and stretching is started in a very carefully selected temperature range depending on the butadiene content of the raw material resin, and the film is strictly controlled in the stretching zone from the expansion start point to the expansion end point. Unless a temperature gradient is provided, a film having the desired low-temperature heat shrinkability cannot be obtained, and therefore it has the drawback that it is difficult to implement easily. Moreover, even if such a method is used to obtain a uniaxially stretched film from an ordinary block copolymer, there is a problem in that the film breaks during stretching, making it impossible to form the film. As is well known, biaxially stretched films and sheets shrink in both the vertical and horizontal directions during shrinkage, so they can be suitable packaging materials for ordinary shrink wrapping, but when used for labels, this becomes a disadvantage, and the label Not available for use. Generally, when heat-shrinkable film is used for labels, the film is cut in advance to fit the length of the packaged product and then heat-shrinked to adhere tightly to the packaged product, so it shrinks in the horizontal direction but not in the vertical direction. It must have little heat shrinkage. Therefore, a uniaxially stretched film is used as a label film, but a low-temperature shrinkable film made of a block copolymer is not yet known. Even when used for axial stretching, a film exhibiting good low-temperature shrinkability cannot be obtained. In view of the current situation, the present inventors have conducted extensive studies on methods for obtaining block copolymer uniaxially stretched films, sheets, etc., which have excellent low-temperature shrinkability and are suitable for labels. Using a block copolymer in which the vinyl aromatic hydrocarbon polymer block has a molecular weight within a certain range,
Furthermore, the inventors have discovered that the object can be achieved by stretching at a specific stretching ratio at a relatively low temperature, and have completed the present invention. That is, the present invention is based on the general structural formula (A-B) o ... (a) A-B-A ... (b) B (-A-B) o ... (c) [(B-A) o ]− n +2 X … (d) [(A−B) o ] − n+2 (A-B-) o A]- n+2 The boundary between A block and B block does not necessarily need to be clearly distinguished.
X represents, for example, a residue of a coupling agent such as silicon tetrachloride or tin tetrachloride, or a residue of an initiator such as a polyfunctional organolithium compound. m and n are each 1
is an integer greater than or equal to ), and the number average molecular weight of the vinyl aromatic hydrocarbon polymer block is 20,000 to 50,000, and the weight ratio of the vinyl aromatic hydrocarbon to the conjugated diene is 60:40 to 95:5. Stretching the block copolymer at a temperature of 60 to 120℃ and a stretching ratio of 1.5.
The heat shrinkage rate at 80°C in the stretching direction obtained by substantially uniaxially stretching in the direction orthogonal to the extrusion direction at 40 to 80%, and the heat shrinkage rate at 80°C in the direction orthogonal to the stretching direction is 40 to 80%. The present invention relates to a uniaxially stretched block copolymer film, sheet or tube having a tensile modulus of less than 15% and a tensile modulus in the stretching direction of 7000 Kg/cm 2 or more. The block copolymer uniaxially stretched film of the present invention,
Since the sheet or tube has excellent shrinkability at low temperatures, it is suitable for labeling articles that would undergo deterioration or deformation when heated to high temperatures, such as labeling plastic molded articles. The present invention will be explained in detail below. In the present invention, a block copolymer having at least one, preferably two or more vinyl aromatic hydrocarbon polymer blocks and at least one, preferably two or more conjugated diene-based polymer blocks is used. use. Here, the polymer block mainly composed of conjugated diene means that the content of conjugated diene is 50% by weight or more, preferably 70% by weight or more,
More preferably, it is a polymer block of 90% by weight or more. The vinyl aromatic hydrocarbon copolymerized into the polymer block mainly composed of conjugated diene may be uniformly distributed in the polymer block or may be distributed in a tapered (gradually decreasing) manner. In addition, if there is a portion containing more than 50% by weight of vinyl aromatic hydrocarbon between the vinyl aromatic hydrocarbon polymer block and the polymer block mainly composed of conjugated diene, the portion contains conjugated diene. It shall be included in the polymer block mainly composed of. The weight ratio of vinyl aromatic hydrocarbon to conjugated diene in the block copolymer is from 60:40 to 95:5, preferably from 75:25 to 90:10, more preferably from 78:22 to 88:12. If the vinyl aromatic hydrocarbon content is less than 60% by weight, the tensile strength and rigidity will be poor, making it unsuitable for films, sheets, etc. If it exceeds 95% by weight, the impact resistance will be poor, which is undesirable. In the block copolymer used in the present invention,
The vinyl aromatic hydrocarbon polymer block has a number average molecular weight of 20,000 to 50,000. If the number average molecular weight of the vinyl aromatic hydrocarbon polymer block is less than 20,000, the tensile strength and rigidity will be poor, and if it exceeds 50,000, it will not be possible to uniaxially stretch at low temperatures, and the low-temperature shrinkability will be poor, so it is preferable. do not have. The number average molecular weight of the vinyl aromatic hydrocarbon polymer block can be determined, for example, by measurement using gel permeation chromatography (GPC). A particularly preferred block copolymer in the present invention is a block copolymer in which the polymer block mainly composed of a conjugated diene is substantially composed of a conjugated diene homopolymer. Here, a block polymer in which a polymer block mainly composed of a conjugated diene is substantially composed of a conjugated diene homopolymer is a vinyl aromatic carbide copolymer copolymerized in a polymer block mainly composed of a conjugated diene. It means a block copolymer with a small amount of hydrogen, in other words, a block copolymer with a small amount of vinyl aromatic hydrocarbon that is not incorporated into the vinyl aromatic hydrocarbon polymer block, and specifically, it is expressed by the following formula. The block copolymer has a displayed unblocked ratio of 15% by weight or less, preferably 10% by weight or less, and more preferably 5% by weight or less.
【表】
香族炭化水素の重量） 水
素重合体ブロツクの重量）
非ブロツク率＝[Table] Weight of aromatic hydrocarbon) Weight of hydrogen polymer block)
Non-blocking rate =
Claims (1)
体ブロツクであり、Ｂは共役ジエンを主とする重
合ブロツクである。ＡブロツクとＢブロツクとの
境界は必ずしも明瞭に区別される必要はない。Ｘ
は例えば四塩化ケイ素、四塩化スズなどのカツプ
リング剤の残基又は多官能有機リチウム化合物等
の開始剤の残基を示す。ｍ及びｎはそれぞれ１以
上の整数である。） のいずれかで表わされ、しかもビニル芳香族炭化
水素重合体ブロツクの数平均分子量が20000ない
し50000で、ビニル芳香族炭化水素と共役ジエン
との重量比が60：40ないし95：５であるブロツク
共重合体を延伸温度70ないし100℃、延伸倍率２
ないし６倍で押出方向と直交する方向に実質的に
１軸延伸してなる延伸方向における80℃の熱収縮
率40〜80％、延伸方向に対して直交方向における
80℃の熱収縮率が15％未満、延伸方向における引
張弾性率が7000Kg／cm2以上であるブロツク共重合
体１軸延伸フイルム、シート又はチユーブ。 ２ ブロツク共重合体の非ブロツク率が15重量％
以下である特許請求の範囲第１項記載のフイル
ム、シート又はチユーブ。 ３ 一般構造式 （Ａ−Ｂ）o ……(イ) Ａ−Ｂ−Ａ ……(ロ) Ｂ（−Ａ−Ｂ）o ……(ハ) 〔（Ｂ−Ａ）o〕−n+2Ｘ ……(ニ) 〔（Ａ−Ｂ）o〕−n+2Ｘ ……(ホ) 〔（Ｂ−Ａ−）oＢ〕−n+2Ｘ ……(ヘ) 〔（Ａ−Ｂ−）oＡ〕−n+2Ｘ ……(ト) （上式において、Ａはビニル芳香族炭化水素重合
体ブロツクであり、Ｂは共役ジエンを主とする重
合体ブロツクである。ＡブロツクとＢブロツクと
の境界は必ずしも明瞭に区別される必要はない。
Ｘは例えば四塩化ケイ素、四塩化スズなどのカツ
プリング剤の残基又は多官能有機リチウム化合物
等の開始剤の残基を示す。ｍ及びｎはそれぞれ１
以上の整数である。） のいずれかで表わされ、しかもビニル芳香族炭化
水素重合体ブロツクの数平均分子量が20000ない
し50000で、ビニル芳香族炭化水素と共役ジエン
との重量比が60：40ないし95：５であるブロツク
共重合体を延伸温度70ないし100℃、延伸倍率２
ないし６倍で押出方向と直交する方向に実質的に
１軸延伸してなる延伸方向における80℃の熱収縮
率が40〜80％、延伸方向に対して直交方向におけ
る80℃の熱収縮率が15％未満、延伸方向における
引張弾性率が7000Kg／cm2以上であるブロツク共重
合体１軸延伸ラベル用フイルム、シート又はチユ
ーブ。[Claims] 1 General structural formula (A-B) o ... (B) A-B-A ... (B) B (-A-B) o ... (C) [(B-A) o 〕− n+2 X ...... (d) [(A-B) o ]- n+ 2 [(A-B-) o A]- n+2 .The boundary between A block and B block does not necessarily need to be clearly distinguished.X
represents, for example, the residue of a coupling agent such as silicon tetrachloride or tin tetrachloride, or the residue of an initiator such as a polyfunctional organolithium compound. m and n are each integers of 1 or more. ), and the number average molecular weight of the vinyl aromatic hydrocarbon polymer block is 20,000 to 50,000, and the weight ratio of the vinyl aromatic hydrocarbon to the conjugated diene is 60:40 to 95:5. Stretching the block copolymer at a temperature of 70 to 100℃ and a stretching ratio of 2.
40 to 80% heat shrinkage at 80°C in the stretching direction, obtained by substantially uniaxially stretching in the direction perpendicular to the extrusion direction at a rate of 40 to 6 times, in the direction perpendicular to the stretching direction.
A uniaxially stretched block copolymer film, sheet or tube having a heat shrinkage rate of less than 15% at 80°C and a tensile modulus in the stretching direction of 7000 Kg/cm 2 or more. 2. The non-blocking rate of the block copolymer is 15% by weight.
A film, sheet or tube according to claim 1, which is as follows. 3 General structural formula (A-B) o ... (a) A-B-A ... (b) B (-A-B) o ... (c) [(B-A) o ] - n+2 X ...(d) [( A -B) o ]- n+2 X ......(e) [(B-A-) o B]- n+2 ) o A] - n+2 Boundaries with blocks do not necessarily need to be clearly distinguished.
X represents, for example, a residue of a coupling agent such as silicon tetrachloride or tin tetrachloride, or a residue of an initiator such as a polyfunctional organolithium compound. m and n are each 1
is an integer greater than or equal to ), and the number average molecular weight of the vinyl aromatic hydrocarbon polymer block is 20,000 to 50,000, and the weight ratio of the vinyl aromatic hydrocarbon to the conjugated diene is 60:40 to 95:5. Stretching the block copolymer at a temperature of 70 to 100℃ and a stretching ratio of 2.
The heat shrinkage rate at 80°C in the stretching direction obtained by substantially uniaxial stretching in the direction perpendicular to the extrusion direction at 40 to 6 times is 40 to 80%, and the heat shrinkage rate at 80°C in the direction perpendicular to the stretching direction is 40 to 80%. A block copolymer film, sheet or tube for uniaxially stretched labels having a tensile modulus of less than 15% and a tensile modulus in the stretching direction of 7000 Kg/cm 2 or more.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2298981A JPS57138921A (en) | 1981-02-20 | 1981-02-20 | Uniaxially stretched film, sheet or tube of block copolymer |
| DE8282101251T DE3260590D1 (en) | 1981-02-20 | 1982-02-18 | A film, sheet or tube of a block copolymer or a composition containing the same |
| EP82101251A EP0058952B1 (en) | 1981-02-20 | 1982-02-18 | A film, sheet or tube of a block copolymer or a composition containing the same |
| US06/349,863 US4386125A (en) | 1981-02-20 | 1982-02-18 | Film, sheet or tube of a block copolymer or a composition containing the same |
| AT82101251T ATE9096T1 (en) | 1981-02-20 | 1982-02-18 | BLOCK POLYMER FILM, SHEET OR TUBE AND COMPOSITION THEREOF. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2298981A JPS57138921A (en) | 1981-02-20 | 1981-02-20 | Uniaxially stretched film, sheet or tube of block copolymer |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12693683A Division JPS5964331A (en) | 1983-07-14 | 1983-07-14 | Uniaxial stretched film, sheet or tube of block copolymer and shrinkage thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57138921A JPS57138921A (en) | 1982-08-27 |
| JPH0214186B2 true JPH0214186B2 (en) | 1990-04-06 |
Family
ID=12097941
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2298981A Granted JPS57138921A (en) | 1981-02-20 | 1981-02-20 | Uniaxially stretched film, sheet or tube of block copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57138921A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7737216B2 (en) * | 2006-01-26 | 2010-06-15 | Chevron Phillips Chemical Company Lp | Monovinylarene conjugated diene block copolymer compositions for shrinkable films |
-
1981
- 1981-02-20 JP JP2298981A patent/JPS57138921A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57138921A (en) | 1982-08-27 |
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