JPH03146331A - Film - Google Patents
FilmInfo
- Publication number
- JPH03146331A JPH03146331A JP28401689A JP28401689A JPH03146331A JP H03146331 A JPH03146331 A JP H03146331A JP 28401689 A JP28401689 A JP 28401689A JP 28401689 A JP28401689 A JP 28401689A JP H03146331 A JPH03146331 A JP H03146331A
- Authority
- JP
- Japan
- Prior art keywords
- film
- styrene
- rubber
- particles
- gloss
- 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.)
- Pending
Links
- 239000010408 film Substances 0.000 claims abstract description 22
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004793 Polystyrene Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 229920002223 polystyrene Polymers 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 10
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 5
- 239000010409 thin film Substances 0.000 claims abstract description 5
- 239000002174 Styrene-butadiene Substances 0.000 claims abstract description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229920000642 polymer Polymers 0.000 claims abstract description 4
- 239000011115 styrene butadiene Substances 0.000 claims abstract description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 4
- 229920001519 homopolymer Polymers 0.000 claims abstract description 3
- 238000001802 infusion Methods 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 abstract description 4
- 239000005060 rubber Substances 0.000 abstract description 4
- 238000005336 cracking Methods 0.000 abstract description 3
- 238000002372 labelling Methods 0.000 abstract description 3
- 241000905957 Channa melasoma Species 0.000 abstract 1
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004794 expanded polystyrene Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000014214 soft drink Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Sealing Of Jars (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は、清涼飲料用等のビン、缶 又はボトルに装
着するための、シュリンクラベルやキャップシール等に
適した剛性、透明性、ストレスクランキング性に優れた
縦一軸延伸フィルムに関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a material with rigidity, transparency, and stress resistance suitable for shrink labels, cap seals, etc. to be attached to soft drink bottles, cans, or bottles. This invention relates to a longitudinally uniaxially stretched film with excellent ranking properties.
従来より、この分野には塩化ビニル系樹脂（ＰＶＣ）や
スチレン系樹脂特にスチレン−ブタジエンブロックポリ
マー（ＳＢＳ）を用いた横一軸延伸フィルムや発泡ポリ
スチレン（ＰＳ）を縦−軸に延伸したフィルム等が知ら
れている。しかし、ＰｖＣには廃棄物処理の問題、発泡
ＰＳには裏印刷が出来ないためのデイスプレー効果に劣
る問題へ（あった、また、延伸と収縮の方向性から見れ
ば＜ｉｆ−軸延伸の方が縦方向の収縮のためラウンドラ
ップ方式をとれるので、ラベリングマシンでの装着速度
が横一軸延伸に較べて２倍以上とれ、製袋工程も不要で
あることがわかっていた。横延伸では、横方向に収縮す
るので製袋工程が必要となって、装着時に開口して被せ
るという煩雑な方法をとらざるを得なかった。Traditionally, in this field, there have been horizontally uniaxially stretched films made of vinyl chloride resins (PVC) and styrene resins, especially styrene-butadiene block polymers (SBS), and films made of expanded polystyrene (PS) stretched longitudinally. Are known. However, PvC has problems with waste disposal, and foamed PS has problems with inferior display effects due to the inability to print on the back side. It was found that because the round-wrap method can be used to shrink in the longitudinal direction, the loading speed on the labeling machine can be more than twice that of horizontal uniaxial stretching, and there is no need for a bag-making process.With horizontal stretching, Since the bag contracts in the lateral direction, a bag-making process is required, which necessitates the complicated method of opening and covering the bag when it is worn.
しかし、従来の押出縦延伸法では、ＰＳ系フィルムは縦
一軸延伸後、容器に装着して収縮させれば延伸方向に沿
ってストレスクラックが発生するという課題があった。However, in the conventional extrusion longitudinal stretching method, there is a problem that stress cracks occur along the stretching direction when the PS film is placed in a container and shrunk after longitudinal uniaxial stretching.
これは、縦方向へのみ配向が進み、装着後の横方向の
応力に対して弱く、ストレスクラックが入るからである
。 尚、本発明に使用する樹脂は、例えば、特開昭４９
−８６４３４号公報等で他の樹脂との組成物として、別
の目的で別の用途に用いることは知られていたが、本発
明の如き使い方は報告されていない。また、５ＢＳ（つ
いても例えば、特開昭５７−２５３４９号公報他に多嶽
知られているが同様に本発明の如き使い方は報告されて
いない。This is because the orientation progresses only in the vertical direction and is weak against stress in the lateral direction after installation, resulting in stress cracks. Incidentally, the resin used in the present invention is, for example, disclosed in Japanese Patent Application Laid-open No. 49
Although it has been known that it can be used as a composition with other resins for other purposes in JP-A-86434, etc., the use as in the present invention has not been reported. Further, although 5BS is well known, for example, in Japanese Unexamined Patent Publication No. 57-25349 and others, the use as in the present invention has not been reported.
本発明者等は、この課題を解決するため鋭意研究の結果
、高光沢ゴム変成ポリスチレンとして知られている所謂
高光沢Ｈ１及び／又はＳＢＳを、インフレーション後、
縦一軸延伸したフィルムが目的に対して最も優れている
ことを見出し、本発明を完成した。As a result of intensive research to solve this problem, the present inventors have developed so-called high-gloss H1 and/or SBS, known as high-gloss rubber modified polystyrene, after inflation.
They discovered that a longitudinally uniaxially stretched film was the most excellent for the purpose, and completed the present invention.
即ち、本発明は、
ジエンゴム薄膜に包み込まれたスチレンホモポリマーの
粒子からなる不連続相が均一に分散しているポリスチレ
ン母体からなっており、該粒子の平均粒径が０゜１〜０
．７ ミクロンで薄膜の膜厚が平均粒径の１／４をこえ
ず、さらにジエンゴム含有量が１〜１０重量％であるゴ
ム変成ポリスチレン（高光沢Ｈ夏）及び／又はスチレン
ブロック（Ｓ）とブタジェンブロック（Ｂ）を有し（Ｓ
−Ｂ）ｎ−Ｂで示されるｎが２以上のスチレン−ブタジ
ェンブロックポリマ−（ＳＢＳ）を、インフーション法
によりブローアツプ比１．５〜４で横方向に配向角せ、
これを倍率１．５〜６倍に縦一軸延伸してなるフィルム
である。That is, the present invention consists of a polystyrene matrix in which a discontinuous phase consisting of styrene homopolymer particles wrapped in a diene rubber thin film is uniformly dispersed, and the average particle size of the particles is 0°1 to 0.
．． Rubber-modified polystyrene (high gloss H summer) and/or styrene block (S) with a thin film thickness of 7 microns not exceeding 1/4 of the average particle diameter and a diene rubber content of 1 to 10% by weight. Has Gen Block (B) (S
-B) A styrene-butadiene block polymer (SBS) in which n is 2 or more, represented by n-B, is oriented laterally at a blow-up ratio of 1.5 to 4 by an infusion method,
This is a film obtained by longitudinally uniaxially stretching this film at a magnification of 1.5 to 6 times.
本発明で使用するゴム変成ポリスチレンは、高光沢Ｈ１
として市販されており、上記条件に入るものとしてＢＡ
Ｓ Ｆ社の高光沢Ｈ１−５２５Ｋがあり、他の銘柄でも
条件に入りさえすれば使用できる。The rubber-modified polystyrene used in the present invention is high gloss H1
BA is commercially available as
High-gloss H1-525K from SF Company is available, and other brands can also be used as long as they meet the conditions.
本発明で使用するＳＢＳは、両末端にスチレンブロック
、中間にブタジェンブロックを配置したスチレンリッチ
即ち樹脂型の従来から市販されているものを使用できる
０例えば、電気化学工業社のクリアレン７３０Ｌがある
。The SBS used in the present invention can be a conventionally commercially available styrene-rich resin type that has styrene blocks at both ends and a butadiene block in the middle.For example, there is Clearene 730L from Denki Kagaku Kogyo Co., Ltd. .
高光沢Ｈ１とＳＢＳの組成比は任意であるが、全部高光
沢Ｈ１か、大部分の高光沢Ｈ！に若干量のＳＢＳを混合
した組成物を用いる方が経済的である。勿論全部ＳＢＳ
でも本発明の条件内であれば問題ない。The composition ratio of high-gloss H1 and SBS is arbitrary, but either all high-gloss H1 or most of high-gloss H! It is more economical to use a composition in which a certain amount of SBS is mixed with the water. Of course all SBS
However, there is no problem as long as it is within the conditions of the present invention.
インフレーシシンの装置は一般的な装置でよく特別な措
定はないが、例えば日立造船社やプラコー社のものを使
用できる。The inflating device is a general device and there are no special provisions, but for example, those manufactured by Hitachi Zosen and Plako can be used.
インフレーション条件は、ブローアツプ比（インフレー
シロン時のグイ径とバブル径の比、以下ＢＵＲという）
１．５〜４好ましくは２〜３．５である。１．４未満で
は横方向の配向か弱くストレスクランクが発生し易い、
また、インフレーション段階でバブルが安定しにくく、
フィルム精度が良（ない、一方４を越えてもインフレー
シロン時の安定性とフィルム精度が悪くなる。The inflation conditions are blow-up ratio (ratio of bubble diameter to bubble diameter during inflation, hereinafter referred to as BUR).
It is 1.5-4, preferably 2-3.5. If it is less than 1.4, the lateral orientation is weak and stress cranking is likely to occur.
In addition, bubbles are difficult to stabilize during the inflation stage;
Film accuracy is good (no, on the other hand, if it exceeds 4, stability and film accuracy during inflation will deteriorate.
ドラフト率（押出方向へ、グイリップからの引落し比）
は５〜３０特に７〜１５が好ましい。５未満ではインフ
レーシロン時の安定性に欠ける傾向にあり、３０を越え
ると縦方向の配向が強くなり過ぎてストレスクラックが
発生し易くなる。Draft rate (in the extrusion direction, drawdown ratio from the grip)
is preferably 5 to 30, particularly preferably 7 to 15. If it is less than 5, stability during inflation tends to be lacking, and if it exceeds 30, the longitudinal orientation becomes too strong and stress cracks are likely to occur.
延伸温度は、９５〜１３５℃特に１００〜１２５°Ｃが
良＜、９５℃未満では破断が生じ易い、延伸時の機械的
負荷が大きくなる等の傾向がある。１３５”Ｃを越える
とシートのロールへの粘着が生じる恐れがある。この温
度範囲の低い方が収縮スピードアップ即ち、生産性向上
とエネルギーコスト低下の点で好ましいことは勿論であ
る。The stretching temperature is preferably 95 to 135°C, especially 100 to 125°C. If it is lower than 95°C, breakage tends to occur easily, and mechanical load during stretching tends to increase. If the temperature exceeds 135''C, there is a risk that the sheet will stick to the roll.Of course, lower temperatures in this range are preferable from the standpoint of speeding up shrinkage, improving productivity and reducing energy costs.
、ｙｌ−軸の延伸倍率は１．５〜６倍で２．０〜４倍が
好ましい、１．５倍未満ではシュリンク性に劣り、６倍
を越えると容器に装着収縮後ストレスクラックが発生し
易くなる。The stretching ratio of the yl-axis is 1.5 to 6 times, preferably 2.0 to 4 times.If it is less than 1.5 times, the shrinkability will be poor, and if it exceeds 6 times, stress cracks will occur after the container is attached and shrinks. It becomes easier.
以下、実施例をもって本発明をさらに説明するが、本発
明は、これらの実施例にとられれるものではない。The present invention will be further explained below with reference to Examples, but the present invention is not limited to these Examples.
実施例１
ＢＡＳ Ｆ社製高光沢Ｈ１−５２５Ｋを８０ｋｇ／時で
押出温度１９０″Ｃ，ドラフト率１５、ＢＵＲ２，Ｓで
インフレーションし、このフィルムを延伸倍率３、延伸
温度１２０℃で縦−軸に延伸した。その結果、成膜安定
性は良好で、フィルム厚さは４０μ、透明性はヘイズで
３％、剛性を表すヤング率は縦が１４０００で横が１３
０００各ｋｇ／ｃｊであった。また、耐ストレスクラッ
キングは良好であった。更に、熱収縮率も適度であった
０条件と結果を表にまとめた。Example 1 High-gloss H1-525K manufactured by BAS F was blown at 80 kg/hour at an extrusion temperature of 190''C, a draft rate of 15, and a BUR of 2,S, and this film was stretched along the longitudinal axis at a stretching ratio of 3 and a stretching temperature of 120°C. As a result, the film formation stability was good, the film thickness was 40μ, the transparency was 3% in terms of haze, and the Young's modulus, which represents rigidity, was 14,000 in the vertical direction and 13 in the horizontal direction.
000 each kg/cj. In addition, stress cracking resistance was good. Furthermore, the results and the 0 condition in which the heat shrinkage rate was appropriate are summarized in the table.
実施例２〜５
表の条件以外は実施例１と同様に行った。尚ＳＢＳは、
電気化学工業社製商品名クリアレン７３０Ｌを使用した
。Examples 2 to 5 The same procedures as in Example 1 were conducted except for the conditions listed in the table. Furthermore, SBS is
Clearen 730L (trade name, manufactured by Denki Kagaku Kogyo Co., Ltd.) was used.
比較例１〜４ 表の条件以外は実施例１と同様に行った。Comparative examples 1 to 4 The same procedure as in Example 1 was conducted except for the conditions listed in the table.
測定法
Ｏ成膜安定性
判定：２４時間以上連続してシワの発生等がなく、安定
に生産可能なものをＯとし、膜厚精度が土２５％を越え
、シワが入りやすい状態となり２４時間以上安定製造で
きないものを×とした。Measuring method O film formation stability judgment: O is a film that has no wrinkles for more than 24 hours and can be stably produced, and the film thickness accuracy exceeds 25% and wrinkles easily occur for 24 hours. Items that could not be stably manufactured were marked as ×.
Ｏ透明性（ヘイズ） ＪＩＳ Ｋ−７１０５に準拠した。O transparency (haze) Compliant with JIS K-7105.
Ｏヤング率 ＡＳＴＭ−Ｄ−８８２によった。O Young's modulus According to ASTM-D-882.
Ｏ耐ストレスクランキング
ＪＩＳ Ｋ−６７３２に準拠した（紫外線カーボンア
ーク２灯を用い、水噴霧１２分と無噴霧４８分を繰り返
した）、市販のワンウェイビンに装着、シュリンクさせ
たのち、上記条件でストレスクランクの発生時間を調査
した。O-stress cranking Compliant with JIS K-6732 (using two ultraviolet carbon arc lamps, 12 minutes of water spray and 48 minutes of no spray were repeated), attached to a commercially available one-way bin, allowed to shrink, and then subjected to the above conditions. The time required for stress crank to occur was investigated.
判定：１００時間以下でクラックを発生したものを×と
し、しなかったものを○とした。Judgment: Those that developed cracks in 100 hours or less were marked as x, and those that did not were marked as ○.
Ｏ熱収縮率 シリコンオイルのバスに３分間浸せき後測定。O heat shrinkage rate Measured after soaking in a silicone oil bath for 3 minutes.
１、本発明のフィルムは、耐ストレスクラツキング性良
好、即ち配向性が適度のため、ストレスが残らず、均一
に伸びる。1. The film of the present invention has good stress cracking resistance, that is, has moderate orientation, so it stretches uniformly without residual stress.
２、ラベリングマシンでの装着がスピーデイで、製袋工
程も不要のため、経済的である。2. It is economical because it can be quickly installed on a labeling machine and there is no need for a bag making process.
３、透明性やヤング率で表される剛性も従来品より優る
とも劣らない。3. The transparency and rigidity expressed by Young's modulus are also superior to conventional products.
４、高光沢Ｈ１とＳＢＳの割合を目的に応じて任意に変
えることができる。高光沢Ｈ１量を多くすれば経済的で
ある。4. The ratio of high gloss H1 and SBS can be changed arbitrarily depending on the purpose. It is economical to increase the amount of high gloss H1.
Claims (1)
粒子からなる不連続相が均一に分散しているポリスチレ
ン母体からなっており、該粒子の平均粒径が０．１〜０
．７ミクロンで薄膜の膜厚が平均粒径の１／４をこえず
、さらにジエンゴム含有量が１〜１０重量％であるゴム
変成ポリスチレン及び／又はスチレンブロック（Ｓ）と
ブタジエンブロック（Ｂ）を有し（Ｓ−Ｂ）＿ｎ−Ｂで
示されるｎが２以上のスチレン−ブタジエンブロックポ
リマーをインフーション法によりブローアップ比１．５
〜４で横方向に配向させ、これを倍率１．５〜６倍に縦
一軸延伸してなるフィルム。It consists of a polystyrene matrix in which a discontinuous phase consisting of styrene homopolymer particles wrapped in a thin diene rubber film is uniformly dispersed, and the average particle size of the particles is 0.1 to 0.
．． It has a rubber-modified polystyrene and/or styrene block (S) and a butadiene block (B) with a thin film thickness of 7 microns that does not exceed 1/4 of the average particle diameter and a diene rubber content of 1 to 10% by weight. A styrene-butadiene block polymer in which n is 2 or more, represented by (S-B)_n-B, was prepared at a blow-up ratio of 1.5 by an infusion method.
A film obtained by oriented in the transverse direction at a magnification of ~4 and uniaxially stretched longitudinally at a magnification of 1.5 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28401689A JPH03146331A (en) | 1989-11-01 | 1989-11-01 | Film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28401689A JPH03146331A (en) | 1989-11-01 | 1989-11-01 | Film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03146331A true JPH03146331A (en) | 1991-06-21 |
Family
ID=17673208
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28401689A Pending JPH03146331A (en) | 1989-11-01 | 1989-11-01 | Film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03146331A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996031556A2 (en) | 1995-03-27 | 1996-10-10 | Grupo Cydsa, S.A. De C.V. | Heat shrinkable films comprising styrene-butadiene copolymer and polyolefin blends |
| US5756577A (en) * | 1995-03-27 | 1998-05-26 | Grupo Cydsa, S.A. De C.V. | Styrene butadiene copolymer and polyolefin resins based shrink films |
| US7824773B2 (en) | 2006-07-27 | 2010-11-02 | Dow Global Technologies Inc. | Shrink labels of oriented polystyrene film containing small rubber particles and low rubber particle gel content and block copolymers |
-
1989
- 1989-11-01 JP JP28401689A patent/JPH03146331A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996031556A2 (en) | 1995-03-27 | 1996-10-10 | Grupo Cydsa, S.A. De C.V. | Heat shrinkable films comprising styrene-butadiene copolymer and polyolefin blends |
| US5756577A (en) * | 1995-03-27 | 1998-05-26 | Grupo Cydsa, S.A. De C.V. | Styrene butadiene copolymer and polyolefin resins based shrink films |
| US7824773B2 (en) | 2006-07-27 | 2010-11-02 | Dow Global Technologies Inc. | Shrink labels of oriented polystyrene film containing small rubber particles and low rubber particle gel content and block copolymers |
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