JP2003071928A - Heat-shrinkable polystyrenic resin film, and label and container using the same - Google Patents

Heat-shrinkable polystyrenic resin film, and label and container using the same

Info

Publication number
JP2003071928A
JP2003071928A JP2001267620A JP2001267620A JP2003071928A JP 2003071928 A JP2003071928 A JP 2003071928A JP 2001267620 A JP2001267620 A JP 2001267620A JP 2001267620 A JP2001267620 A JP 2001267620A JP 2003071928 A JP2003071928 A JP 2003071928A
Authority
JP
Japan
Prior art keywords
heat
label
container
film
resin film
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
Application number
JP2001267620A
Other languages
Japanese (ja)
Other versions
JP2003071928A5 (en
Inventor
Yoshiaki Takegawa
善紀 武川
Katsuya Ito
勝也 伊藤
Satoshi Hayakawa
聡 早川
Tadashi Tahoda
多保田  規
Shigeru Yoneda
茂 米田
Katsuhiko Nose
克彦 野瀬
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyobo Co Ltd
Original Assignee
Toyobo Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Toyobo Co Ltd filed Critical Toyobo Co Ltd
Priority to JP2001267620A priority Critical patent/JP2003071928A/en
Publication of JP2003071928A publication Critical patent/JP2003071928A/en
Publication of JP2003071928A5 publication Critical patent/JP2003071928A5/ja
Pending legal-status Critical Current

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  • Details Of Rigid Or Semi-Rigid Containers (AREA)
  • Packages (AREA)
  • Laminated Bodies (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a heat-shrinkable polystyrenic resin film suitable as a packaging material used for the coating, bundling, wrapping or the like of a container or the like, having excellent adaptability especially with respect to the packaging of an article necessary for preventing deterioration due to light and having high stiffness suitable for a case undergoing a peculiar process such as a mounting process for covering a bottle or the like, and a label and a container using the same. SOLUTION: The heat-shrinkable polystyrenic resin film is characterized in that the maximum heat shrinkage factor of the change ratio of length after heat treatment for heating the film for one minute at each temperature from 100 to 150 deg.C at every 10 deg.C is not less than 40% in the main shrink direction of the film, the mean value T of the transmissivity of near ultraviolet rays is not more than 0.5 in such a case that the film is applied to the bottle as the label shape of the cylindrical tubular transparent container wherein a main shrink axis direction becomes a cylindrical cross-sectional direction and the container is irradiated with near ultraviolet rays from the outside of the container to the inside thereof from a direction vertical to the rotary symmetric axis of the container in a state after heat shrinkage and the compression strength in the up and down direction of a cylindrical body, which has a square bottom surface and is formed from a label comprising the film and having a folding diameter of 175 mm and a length of 120 mm in the direction crossing the main shrink axis direction at a right angle, is not less than 5,000 mN.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【発明の属する技術分野】本発明は、容器等の被覆、結
束、外装などに用いられる包装材として好適な熱収縮性
ポリスチレン系樹脂フィルム、特に光線による劣化を防
止する必要のある物品の包装への優れた適用性を有し、
ボトルに被せる装着工程などの特有の工程を経る場合に
適した腰の強さを有する熱収縮性ポリスチレン系樹脂フ
ィルム、これを用いたラベルおよび容器に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-shrinkable polystyrene resin film suitable as a packaging material used for covering, binding, and packaging containers, etc., and particularly to packaging of articles that need to be prevented from deterioration by light rays. Has excellent applicability to
The present invention relates to a heat-shrinkable polystyrene-based resin film having a waist strength suitable for a specific process such as a mounting process for covering a bottle, a label and a container using the same.

【0002】[0002]

【従来の技術】熱収縮性フィルムは、収縮性という機能
を有するため、接着剤や留め具等の固定手段を用いず、
フィルム自体の収縮力と賦形性によって対象物に積層一
体化させることができる。従って、積層や被覆による対
象物の機械的保護ばかりでなく、結束、封緘などの機能
も有する。さらに熱収縮フィルム自体に特殊な機能を有
する場合、積層により、対象物に後付にてその特殊機能
を付加することができる。この性質は、対象物の保存や
流通時における保護と、表示性および意匠性の付与が主
目的である包装分野に於いて有効に用いられている。例
えば、ガラス製およびプラスチック製のボトルを含む瓶
や、缶などの各種容器、及びパイプ、棒、木材、各種棒
状体などの長尺物、または枚様体等の、被覆用、結束
用、外装用又は封緘用として利用される。具体的には、
表示、保護、結束、および機能化による商品価値の向上
などを目的として、瓶のキャップ部、肩部、及び胴部の
一部又は全体を被覆する用途に用いられる。さらに、
箱、瓶、板、棒、ノートなどの被包装物を複数個ずつ集
積して包装する用途や、被包装物にフィルムを密着させ
て該フィルムにより包装する(スキンパッケージ)用途
などにも用いられる。このときフィルムにあらかじめ表
示、意匠目的の造形が付与されている場合、ラベルとい
う商品となる。
2. Description of the Related Art Since a heat-shrinkable film has a function of shrinkability, it does not use a fixing means such as an adhesive or a fastener,
It can be laminated and integrated with an object by the shrinkage force and shapeability of the film itself. Therefore, it not only has a function of mechanically protecting the object by stacking or coating, but also has a function of binding and sealing. Further, when the heat-shrinkable film itself has a special function, the special function can be added to the object later by laminating. This property is effectively used in the packaging field whose main purpose is to protect objects during storage and distribution, and to impart displayability and design. For example, bottles including glass and plastic bottles, various containers such as cans, and long objects such as pipes, rods, wood, various rod-shaped bodies, or sheet-like bodies for covering, binding, and exterior. It is used as a seal or a seal. In particular,
It is used for covering a part or the whole of the cap, shoulder, and body of a bottle for the purpose of labeling, protection, bundling, and enhancement of commercial value through functionalization. further,
It is also used for the purpose of packing a plurality of items to be packed such as boxes, bottles, plates, rods, notebooks, etc., and for the purpose of bringing a film into close contact with the item to be packed and packaging it with the film (skin package). . At this time, when the film is preliminarily displayed and shaped for the purpose of design, it becomes a product called a label.

【0003】熱収縮性フィルムの素材としては、ポリ塩
化ビニル、ポリスチレン、ポリエステル、ポリアミド、
脂肪族系ポリオレフィン、およびその誘導体、塩酸ゴム
などが用いられている。通常、これらの素材からなるフ
ィルムをチューブ状に成形し、例えば瓶にかぶせたり、
パイプなどを集積した後、熱収縮させることにより包装
や結束が行なわれる。しかし、従来の熱収縮性フィルム
は、いずれも耐熱性が乏しく、高温でのボイル処理やレ
トルト処理に耐えないため、食品、衛生用品、医薬品用
途に適用する場合、高温での殺菌処理ができないという
欠点がある。例えばレトルト処理を行うと、従来のフィ
ルムは処理中に破損しやすいという問題点があった。
Materials for the heat-shrinkable film include polyvinyl chloride, polystyrene, polyester, polyamide,
Aliphatic polyolefins and their derivatives, hydrochloric acid rubber, etc. are used. Usually, a film made of these materials is formed into a tube shape, for example, by covering it with a bottle,
After accumulating pipes, etc., they are heat-shrinked to be packaged and bound. However, conventional heat-shrinkable films have poor heat resistance and cannot withstand boil treatment or retort treatment at high temperatures, and therefore cannot be sterilized at high temperatures when applied to food, hygiene products, and pharmaceutical applications. There are drawbacks. For example, when the retort treatment is performed, the conventional film has a problem that it is easily damaged during the treatment.

【0004】従来の熱収縮性フィルムの場合、ポリ塩化
ビニル系樹脂からなるフィルムは、熱収縮特性は極めて
良好であるものの、ラベルとする場合などの印刷時のイ
ンクとの接着性が悪く、さらにフィルム化に際して配合
する添加剤のゲル状物を生成しやすいため、印刷面にピ
ンホールを発生し易い。さらに、環境性の点から、廃
棄、焼却が難しいという問題がある。ポリエステル系樹
脂からなるフィルムは、耐熱性、寸法安定性、耐溶剤性
等に優れるが、所望の熱収縮特性、接着性等を達成する
ためには精密な製造条件の制御技術が必要であり、コス
ト等の問題があった。
In the case of a conventional heat-shrinkable film, a film made of a polyvinyl chloride resin has a very good heat-shrinkage property, but has a poor adhesion to ink during printing such as a label. Since it is easy to form a gel material of the additive to be added when forming a film, pinholes are easily generated on the printed surface. Furthermore, there is a problem that disposal and incineration are difficult from the environmental point of view. A film made of a polyester resin is excellent in heat resistance, dimensional stability, solvent resistance, etc., but it requires precise control of manufacturing conditions in order to achieve desired heat shrinkage characteristics, adhesiveness, etc. There were problems such as cost.

【0005】また、熱収縮性フィルムの有用性から、従
来、熱収縮性フィルムではないフィルム、ラベルが使用
されてきた分野にも熱収縮性フィルムが用いられるよう
になっている。特に飲料容器のラベルは、紙や熱収縮性
フィルムではないフィルムからなる貼り付けラベルから
熱収縮性ラベルに置き換わってきたものが多い。このよ
うな場合、容器及び内容物の保護のために特殊な機能が
必要とされ、特に光線による劣化を生じやすい被包装
物、例えば、緑茶、ジュース、ビール等の飲料、耐光性
の低い合成又は天然色素を含有する食品、化粧品、衛生
用品、医薬品などを収容する容器や包装物などは、被包
装物を光線、特に影響の大きい近紫外線から保護する機
能が求められている。従来の熱収縮性フィルムにおい
て、熱収縮性と被包装物の保護性を兼ね備えるものはな
かった。
Further, because of the usefulness of the heat-shrinkable film, the heat-shrinkable film has come to be used also in the field where films and labels which are not heat-shrinkable films have been used conventionally. In particular, many labels for beverage containers have been replaced with a heat-shrinkable label from a sticking label made of paper or a film that is not a heat-shrinkable film. In such a case, a special function is required for the protection of the container and the contents, and particularly, the object to be packaged which is likely to be deteriorated by light rays, for example, green tea, juice, beverages such as beer, low light resistance synthetic or BACKGROUND ART Containers and packages containing foods, cosmetics, hygiene products, pharmaceuticals, etc. containing natural pigments are required to have a function of protecting a packaged object from light rays, particularly near-ultraviolet rays which have a large influence. No conventional heat-shrinkable film has both heat-shrinkability and protection of the article to be packaged.

【0006】さらにPET製ボトルなどの収容物充填ラ
インやこれに連なる熱収縮性フィルムによる包装ライン
は高速化の傾向があり、用いられる熱収縮性フィルムに
対しても高速包装過程を経ても優れた収縮仕上がり外観
性が要求されるようになっている。なかでも、チューブ
状のラベル形状として、該ラベルを円筒形に開き、ボト
ルに被せる装着工程においては、いわゆる腰の弱いフィ
ルムの場合、ボトルに接触したときの衝撃によりラベル
が腰折れ状態で装着されたり、最悪の場合、ラベルが装
着用の器具とボトルとの間で圧縮されて挫屈状態とな
り、装着不能となる場合があった。特に、上記のような
食品、化粧品、衛生用品、医薬品などに使用される被覆
率が高く、長い円筒形などのラベルは装着時の安定性が
要求されるが、これを満たすものがなかった。
[0006] Further, the line for filling the contents such as PET bottles and the line for packaging the heat-shrinkable film connected thereto tend to be faster, and the heat-shrinkable film used is excellent even after the high-speed packaging process. Shrinkage finish appearance is required. Among them, in the case of a so-called weak film, the label is attached in a bent state due to the impact when it comes into contact with the bottle in the attaching process of opening the label into a cylindrical shape and covering it on the bottle as a tubular label shape. In the worst case, the label may be compressed between the mounting device and the bottle to be in a buckled state, which makes it impossible to mount the label. In particular, labels with long coverage such as foods, cosmetics, hygiene products, pharmaceuticals, etc. having a high coverage and long cylindrical shapes are required to have stability at the time of mounting, but none of them satisfy this requirement.

【0007】[0007]

【発明が解決しようとする課題】本発明は、ボトルに被
せる装着工程などの特有の工程を経る場合に適した腰の
強さを有し、熱収縮率が十分に大きく、熱収縮時にフィ
ルムに収縮むらが発生せず、美麗な外観をもち、複雑な
形状の容器に装着させても極めて高い被覆性が得られ、
光線による劣化の防止が必要な物品の包装に最適な熱収
縮性ポリスチレン系樹脂フィルム、これを用いたラベ
ル、及び容器を提供することを目的とする。
DISCLOSURE OF THE INVENTION The present invention has a waist strength suitable for a specific step such as a mounting step for covering a bottle, has a sufficiently large heat shrinkage ratio, and is formed into a film at the time of heat shrinkage. It has no shrinkage unevenness, has a beautiful appearance, and has extremely high coverage even when mounted on a container with a complicated shape.
An object of the present invention is to provide a heat-shrinkable polystyrene-based resin film, a label using the same, and a container that are most suitable for packaging of articles that need to be prevented from deterioration by light rays.

【0008】[0008]

【課題を解決するための手段】本発明は、主収縮方向に
おいて、100℃から10℃毎に150℃までの各温度
で、1分間加熱する処理後の、前記処理前の長さに対す
る長さ変化率の最大値である最大熱収縮率が40%以上
であり、主収縮軸方向が円筒形断面方向となる円筒形チ
ューブ状の透明容器のラベル形状としてボトルに装着さ
せ、熱収縮後の状態で、容器外部側から内側へ容器の回
転対称軸に垂直な方向から近紫外線を照射した場合の、
下記式1で表される近紫外線の透過率の平均値Tが0.
5以下であり、折り径175mm、主収縮軸方向と直行
する方向の長さ120mmのラベル形状とし、該ラベル
を底面が四角形の筒体とした場合の筒体の上下方向の圧
縮強度が5000mN以上であることを特徴とする熱収
縮性ポリスチレン系樹脂フィルム、これを用いたラベル
および容器である。 T=A/B 式1 A:熱収縮性ポリスチレン系樹脂フィルムを透明容器に
装着させた状態でのフィルム及び容器を透過する光エネ
ルギー密度の平均値(n=10) B:熱収縮性ポリスチレン系樹脂フィルムを装着させな
い状態での透明容器を透過する光エネルギー密度の平均
値(n=10)
According to the present invention, in the main shrinkage direction, the length relative to the length before the treatment after the treatment of heating for 1 minute at each temperature from 100 ° C. to every 10 ° C. to 150 ° C. The state after heat-shrinking, when the maximum heat-shrinkage rate, which is the maximum value of the rate of change, is 40% or more, and the main shrinkage axis direction is the cylindrical cross-section direction. In the case of irradiating near ultraviolet rays from the outside of the container to the inside in the direction perpendicular to the axis of rotational symmetry of the container,
The average value T of the transmittance of near-ultraviolet rays represented by the following formula 1 is 0.
5 or less, a folding shape of 175 mm, a length of 120 mm in a direction orthogonal to the main contraction axis direction, and when the label has a rectangular bottom surface, the vertical compression strength of the cylinder is 5000 mN or more. A heat-shrinkable polystyrene resin film, a label and a container using the same. T = A / B Formula 1 A: Average value of light energy density (n = 10) transmitted through the film and the container in the state where the heat-shrinkable polystyrene-based resin film is attached to the transparent container B: Heat-shrinkable polystyrene-based Average value of light energy density (n = 10) transmitted through the transparent container without the resin film attached

【0009】[0009]

【発明の実施の形態】本発明のフィルムを構成するポリ
スチレン系樹脂の構成は、後述の最大熱収縮率で表され
る熱収縮特性および近紫外線の平均透過率を現出可能で
あれば特に限定されないが、好ましくは、シンジオタク
ティック構造を有するポリスチレン系樹脂を含有するポ
リスチレン系樹脂であるのがよい。さらに好ましくは、
ポリスチレン系樹脂として、シンジオタクティック構造
を有するポリスチレン系樹脂を用いるのがよい。シンジ
オタクティック構造を有するポリスチレン系樹脂を用い
ることにより、機械的強度、加熱保存時などの耐熱性が
向上する。このようなポリスチレン系樹脂を用いること
により、ポリスチレンの密度が低く、リサイクル工程で
の分離に有利である点に加え、耐熱性、特に加熱保存時
などの耐熱性に優れ、フィルム形成後に経時的に収縮す
ることによる印刷ピッチの変化が低減し、ラベルとして
高精度の印刷を行うこともできる。更に印刷インクに含
まれる溶剤に対する耐久性も向上し、印刷性に優れる。
BEST MODE FOR CARRYING OUT THE INVENTION The constitution of the polystyrene resin constituting the film of the present invention is particularly limited as long as the heat shrinkage property represented by the maximum heat shrinkage ratio described later and the average transmittance of near-ultraviolet light can be expressed. However, it is preferably a polystyrene resin containing a polystyrene resin having a syndiotactic structure. More preferably,
As the polystyrene resin, it is preferable to use a polystyrene resin having a syndiotactic structure. By using a polystyrene resin having a syndiotactic structure, mechanical strength and heat resistance during heat storage are improved. By using such a polystyrene-based resin, the density of polystyrene is low, and in addition to being advantageous for separation in the recycling step, it is excellent in heat resistance, particularly heat resistance during heat storage, and after the film formation, Changes in the printing pitch due to contraction are reduced, and high-precision printing can be performed as a label. Further, the durability against the solvent contained in the printing ink is improved, and the printability is excellent.

【0010】上記シンジオタクティック構造を有するポ
リスチレン系樹脂は、側鎖であるフェニル基および/ま
たは置換フェニル基を核磁気共鳴法により定量するタク
テイシテイにおいて、ダイアッド(構成単位が二個)で
好ましくは75%以上、さらに好ましくは85%以上で
あるのがよく、また、ペンタッド(構成単位が5個)で
好ましくは30%以上、さらに好ましくは50%以上で
あるのがよい。
The polystyrene resin having the syndiotactic structure is preferably 75 diads (two constitutional units) in the tacticity of quantifying side chain phenyl groups and / or substituted phenyl groups by a nuclear magnetic resonance method. % Or more, more preferably 85% or more, and pentad (5 units) is preferably 30% or more, more preferably 50% or more.

【0011】本発明に使用するポリスチレン系樹脂を構
成するポリスチレン成分としては、ポリスチレン、ポリ
(p−、m−、またはo−メチルスチレン)、ポリ
(2,4−、2,5−、3,4−、または3,5−ジメ
チルスチレン)、ポリ(p−ターシャリーブチルスチレ
ン)等のポリ(アルキルスチレン)、ポリ(p−、m
−、またはo−クロロスチレン)、ポリ(p−、m−、
またはo−ブロモスチレン)、ポリ(p−、m−、また
はo−フルオロスチレン)、ポリ(o−メチル−p−フ
ルオロスチレン)等のポリ(ハロゲン化スチレン)、ポ
リ(p−、m−、またはo−クロロメチルスチレン)等
のポリ(ハロゲン化置換アルキルスチレン)、ポリ(p
−、m−、またはo−メトキシスチレン)、ポリ(p
−、m−、またはo−エトキシスチレン)等のポリ(ア
ルコキシスチレン)、ポリ(p−、m−、またはo−カ
ルボキシメチルスチレン)等のポリ(カルボキシアルキ
ルスチレン)ポリ(p−ビニルベンジルプロピルエーテ
ル)等のポリ(アルキルエーテルスチレン)、ポリ(p
−トリメチルシリルスチレン)等のポリ(アルキルシリ
ルスチレン)、さらにはポリ(ビニルベンジルジメトキ
シホスファイド)等が挙げられる。
As the polystyrene component constituting the polystyrene resin used in the present invention, polystyrene, poly (p-, m-, or o-methylstyrene), poly (2,4-, 2,5-, 3, 4- or 3,5-dimethylstyrene), poly (p-tertiarybutylstyrene), and other poly (alkylstyrene), poly (p-, m)
-Or o-chlorostyrene), poly (p-, m-,
Or poly (halogenated styrene) such as o-bromostyrene), poly (p-, m-, or o-fluorostyrene), poly (o-methyl-p-fluorostyrene), poly (p-, m-, Or poly (halogenated substituted alkylstyrene) such as o-chloromethylstyrene), poly (p
-, M-, or o-methoxystyrene), poly (p
-(M-, or o-ethoxystyrene) or other poly (alkoxystyrene), poly (p-, m-, or o-carboxymethylstyrene) or other poly (carboxyalkylstyrene) poly (p-vinylbenzylpropyl ether) ) Etc., poly (alkyl ether styrene), poly (p
-Trimethylsilylstyrene) and other poly (alkylsilylstyrenes), as well as poly (vinylbenzyldimethoxyphosphide) and the like.

【0012】本発明のフィルムを構成するポリスチレン
系樹脂は、熱収縮開始温度を低くすることや、耐衝撃性
の向上を目的として、フィルムの少なくとも1層を構成
するポリスチレン系樹脂に可塑化剤、相溶化剤等を、ポ
リスチレン重合時あるいは重合体へ配合するのが好まし
い。
The polystyrene resin constituting the film of the present invention is a plasticizer for the polystyrene resin constituting at least one layer of the film for the purpose of lowering the heat shrinkage initiation temperature and improving impact resistance. It is preferable to add a compatibilizer and the like during the polystyrene polymerization or to the polymer.

【0013】本発明においては、特に、フィルムの少な
くとも1層を構成するポリスチレン系樹脂に対し、熱可
塑性樹脂および/またはゴム成分を添加することが好ま
しい。上記熱可塑性樹脂としてはアタクチック構造を有
するポリスチレン、AS樹脂、ABS樹脂等のポリスチ
レン系樹脂をはじめ、ポリエチレンテレフタレート、ポ
リエチレンナフタレート、ポリブチレンテレフタレート
等のポリエステル系樹脂、ナイロン6、ナイロン66、
ナイロン12、ナイロン4、ポリヘキサメチレンアジパ
ミド等のポリアミド系樹脂、ポリエチレン、ポリプロピ
レン、ポリブテン等のポリオレフィン系樹脂等が挙げら
れる。上記ゴム成分としては、スチレン系化合物をその
構成成分として含有するゴム状共重合体が好ましく、ス
チレンとゴム成分から、それぞれ一種以上を選んで共重
合したランダム、ブロックまたはグラフト共重合体が挙
げられる。このようなゴム状共重合体としては、例えば
スチレン−ブタジエン共重合体ゴム、スチレン−イソプ
レンブロック共重合体、さらにこれらのブタジエン部分
の一部あるいは全部を水素化したゴム、アクリル酸メチ
ル−ブタジエン−スチレン共重合体ゴム、アクリロニト
リル−ブタジエン−スチレン共重合体ゴム、アクリロニ
トリル−アルキルアクリレート−ブタジエン−スチレン
共重合体ゴム、メタクリル酸メチル−アルキルアクリレ
ート−ブタジエン−スチレン共重合体ゴム等が挙げられ
る。上記の、スチレン系化合物をその構成成分として含
有するゴム状共重合体は、スチレン単位を有するため、
主としてシンジオタクチック構造を有するポリスチレン
系樹脂に対する分散性が良好であり、その結果、ポリス
チレン系樹脂に対する物性改良効果が大きい。特に、相
溶性調整剤としては、上記のスチレン系化合物をその構
成成分として含有するゴム状共重合体が好適である。
In the present invention, it is particularly preferable to add a thermoplastic resin and / or a rubber component to the polystyrene resin constituting at least one layer of the film. Examples of the thermoplastic resin include polystyrene-based resins having an atactic structure such as polystyrene, AS resin and ABS resin, polyester-based resins such as polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate, nylon 6, nylon 66,
Examples thereof include polyamide resins such as nylon 12, nylon 4 and polyhexamethylene adipamide, and polyolefin resins such as polyethylene, polypropylene and polybutene. The rubber component is preferably a rubbery copolymer containing a styrene compound as its constituent component, and examples thereof include random, block or graft copolymers obtained by copolymerizing at least one selected from styrene and the rubber component. . Examples of such a rubber-like copolymer include styrene-butadiene copolymer rubber, styrene-isoprene block copolymer, rubber obtained by hydrogenating a part or all of these butadiene moieties, methyl acrylate-butadiene- Examples thereof include styrene copolymer rubber, acrylonitrile-butadiene-styrene copolymer rubber, acrylonitrile-alkyl acrylate-butadiene-styrene copolymer rubber, and methyl methacrylate-alkyl acrylate-butadiene-styrene copolymer rubber. The above rubber-like copolymer containing a styrene compound as its constituent component has a styrene unit,
The dispersibility in polystyrene resin mainly having a syndiotactic structure is good, and as a result, the effect of improving physical properties in polystyrene resin is large. In particular, as the compatibility modifier, a rubbery copolymer containing the above-mentioned styrene compound as its constituent component is suitable.

【0014】ゴム成分としては、他に、天然ゴム、ポリ
ブタジエン、ポリイソプレン、ポリイソブチレン、ネオ
プレン、エチレン−プロピレン共重合体ゴム、ウレタン
ゴム、シリコーンゴム、アクリルゴム、ポリエーテル−
エステルゴム、ポリエステル−エステルゴム等が使用で
きる。
Other rubber components include natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, ethylene-propylene copolymer rubber, urethane rubber, silicone rubber, acrylic rubber, polyether-
Ester rubber, polyester-ester rubber and the like can be used.

【0015】本発明のフィルムを構成するポリスチレン
系樹脂の重量平均分子量は好ましくは10,000以
上、さらに好ましくは50,000以上である。重量平
均分子量が10,000未満のものは、フィルムの強伸
度特性や耐熱性が低下しやすい。重量平均分子量の上限
は特に限定されないが、1,500,000以上となる
と、延伸張力の増大に伴う破断の発生等が生じることが
あるため、1,500,000未満であることが好まし
い。
The weight average molecular weight of the polystyrene resin constituting the film of the present invention is preferably 10,000 or more, more preferably 50,000 or more. When the weight average molecular weight is less than 10,000, the strength / elongation property and heat resistance of the film are likely to decrease. The upper limit of the weight average molecular weight is not particularly limited, but if it is 1,500,000 or more, breakage may occur due to an increase in stretching tension, so that it is preferably less than 1,500,000.

【0016】本発明の熱収縮性ポリスチレン系樹脂フィ
ルムには、静電密着性、易滑性、延伸性、加工適性、耐
衝撃性等を向上させるためや、粗面化、不透明化、空洞
化、軽量化等を目的として、他の樹脂、可塑化剤、相溶
性調整剤、無機粒子、有機粒子、着色剤、酸化防止剤、
帯電防止剤等を適宜配合できる。
The heat-shrinkable polystyrene resin film of the present invention is used for improving electrostatic adhesion, slipperiness, stretchability, processability, impact resistance, etc., roughening, opacifying, and hollowing. , Other resins, plasticizers, compatibility modifiers, inorganic particles, organic particles, colorants, antioxidants, for the purpose of weight reduction,
An antistatic agent or the like can be appropriately added.

【0017】本発明のフィルムを構成する素材として、
上記のようなポリスチレン系樹脂を用いることにより、
各種の熱収縮特性に優れ、ラベル形成時などのインクと
の接着性などの印刷性に優れ、フィルムの印刷面にピン
ホールなどが発生することもない。さらに、廃棄性に優
れ、焼却された場合の環境への影響も少ない。
As the material constituting the film of the present invention,
By using a polystyrene resin as described above,
Excellent in various heat shrinkage properties, excellent printability such as adhesion to ink when forming a label, and no pinholes are formed on the printed surface of the film. Furthermore, it has excellent disposability and has little impact on the environment when incinerated.

【0018】上記のような本発明のフィルムを構成する
ポリスチレン系樹脂は、従来一般に使用される押し出し
法、カレンダー法等の方法によりフィルム状に形成され
る。フィルムの形状は、例えば平面状またはチューブ状
であり、特に限定されない。延伸方法も、従来一般に使
用されるロール延伸法、長間隙延伸法、テンター延伸
法、チューブラー延伸法等の方法を使用できる。上記方
法のいずれにおいても、延伸は逐次2軸延伸、同時2軸
延伸、1軸延伸、及びこれらの組合わせのいずれによっ
て行ってもよい。上記2軸延伸では、縦横方向の延伸は
同時に行われてもよいが、どちらか一方を先に行う逐次
2軸延伸が効果的であり、その縦横の順序はどちらが先
でもよい。本発明の熱収縮性ポリスチレン系樹脂フィル
ムを製造する場合の好ましい条件について以下に示す。
延伸倍率は1.0倍から6.0倍であるのが好ましく、
所定の一方向の倍率と該方向と直行する方向の倍率が同
じであっても異なっていてもよい。延伸工程において
は、フィルムを構成する樹脂のガラス転移温度(Tg)
以上(Tg+50)℃以下の温度で予熱を行うのが好ま
しい。延伸後の熱固定では、延伸を行った後に、30℃
〜150℃の加熱ゾーンを約1秒〜30秒通すことが好
ましい。また、フィルムの延伸後であって、熱固定を行
う前、もしくは行った後に、適度な度合で弛緩処理を行
ってもよい。さらに、上記延伸後、伸張あるいは緊張状
態に保ってフィルムにストレスをかけながら冷却する工
程、あるいは、該処理に引き続いて緊張状態を解除した
後にさらに冷却工程を付加してもよい。
The polystyrene resin constituting the film of the present invention as described above is formed into a film by a conventionally used method such as an extrusion method or a calender method. The shape of the film is, for example, a plane shape or a tube shape, and is not particularly limited. As the stretching method, conventionally used methods such as a roll stretching method, a long gap stretching method, a tenter stretching method and a tubular stretching method can be used. In any of the above methods, stretching may be performed by sequential biaxial stretching, simultaneous biaxial stretching, uniaxial stretching, or a combination thereof. In the above-mentioned biaxial stretching, stretching in the longitudinal and transverse directions may be performed simultaneously, but sequential biaxial stretching in which either one is performed first is effective, and the longitudinal and lateral directions may be performed first. Preferred conditions for producing the heat-shrinkable polystyrene resin film of the present invention are shown below.
The draw ratio is preferably 1.0 to 6.0 times,
The predetermined one direction magnification and the direction orthogonal to the predetermined direction may be the same or different. In the stretching step, the glass transition temperature (Tg) of the resin forming the film
Preheating is preferably performed at a temperature of (Tg + 50) ° C. or less. In heat setting after stretching, after stretching, 30 ° C
It is preferred to pass a heating zone of ~ 150 ° C for about 1 to 30 seconds. Further, after the film is stretched and before or after the heat setting, the relaxation treatment may be performed to an appropriate degree. Further, after the stretching, a step of cooling the film while applying a stress to the film while keeping it in a stretched or tensioned state, or a cooling step after releasing the tensioned state following the treatment may be added.

【0019】本発明の熱収縮性ポリスチレン系樹脂フィ
ルムは、2層以上の多層構成であるのが好ましい。多層
構成とすることにより、均等な収縮性、収縮後の高温条
件下での耐熱性、腰の強さが向上する。特に、本発明の
熱収縮性ポリスチレン系樹脂フィルムは、それぞれポリ
スチレン系樹脂からなる2層以上の多層構成であるのが
好ましく、少なくとも1層がシンジオタクティック構造
を有するポリスチレン系樹脂を含有するのが好ましい。
The heat-shrinkable polystyrene resin film of the present invention preferably has a multi-layer structure of two or more layers. By adopting a multi-layer structure, uniform shrinkability, heat resistance under high temperature conditions after shrinkage, and waist strength are improved. In particular, the heat-shrinkable polystyrene-based resin film of the present invention preferably has a multilayer structure of two or more layers each made of a polystyrene-based resin, and at least one layer contains a polystyrene-based resin having a syndiotactic structure. preferable.

【0020】2層以上の多層構成とする場合、積層方法
は特に限定されず、フィルム形成と同時に積層しても、
別個にフィルム形成した後積層しても良い。別個にフィ
ルム形成した後積層する場合、フィルムの延伸前あるい
は延伸後に、フィルムに溶解した樹脂を塗布するコーテ
ィング法、複数のフィルムやシートを接着するドライラ
ミネート法、サーマルラミネート法、フィルムに押出法
により積層する押出ラミネート法等が挙げられ、フィル
ム形成と同時に積層する場合、複数層を溶融共押出する
方法(CCF法)等が挙げられる。各層が互いに物性が
近い樹脂からなる場合、フィルムの延伸前にCCF法に
より積層する方法が好ましい。
In the case of a multi-layered structure having two or more layers, the laminating method is not particularly limited,
The films may be formed separately and then laminated. When laminating after film formation separately, before or after stretching the film, a coating method of applying a resin dissolved in the film, a dry laminating method of adhering a plurality of films or sheets, a thermal laminating method, an extrusion method to the film Examples thereof include an extrusion laminating method of laminating, and when laminating simultaneously with film formation, a method of melt coextruding a plurality of layers (CCF method) and the like can be mentioned. When each layer is made of a resin having physical properties close to each other, a method of laminating by a CCF method before stretching the film is preferable.

【0021】2層以上の多層構成とする場合、各層の層
構成や厚み比率は特に限定されないが、3層構成以上で
あって各表面層が同組成の樹脂からなる場合、中心層は
表面層より厚みが大きいのが好ましい。
In the case of a multilayer structure having two or more layers, the layer structure and thickness ratio of each layer are not particularly limited, but when the surface layer has three or more layers and each surface layer is made of a resin having the same composition, the central layer is the surface layer. It is preferably thicker.

【0022】本発明の熱収縮性ポリスチレン系樹脂フィ
ルムの全体厚さは特に限定されないが、6〜250μm
の範囲であるのが好ましい。
The total thickness of the heat-shrinkable polystyrene resin film of the present invention is not particularly limited, but is 6 to 250 μm.
The range is preferably.

【0023】本発明の熱収縮性ポリスチレン系樹脂フィ
ルムは、主収縮軸方向が円筒形断面方向となる円筒形チ
ューブ状の透明容器のラベル形状としてボトルに装着さ
せ、熱収縮後の、容器外部側から内側へ容器の回転対称
軸に垂直な方向から近紫外線を照射した場合の、下記式
1で表される近紫外線の透過率の平均値Tが0.5以下
である必要がある。好ましくは、近紫外線の透過率の平
均値Tが0.2以下、さらに好ましくは0.1以下、こ
とさらに好ましくは0.08以下であるのがよく、特に
好ましくは0.06以下である。近紫外線の透過率の平
均値Tが0.5を超えると、本発明の熱収縮性ポリスチ
レン系樹脂フィルムによる被包装物に対する遮光性が低
くなり、被包装物の光線による劣化を防止できない。 T=A/B 式1 A:熱収縮性ポリスチレン系樹脂フィルムを透明容器に
装着させた状態でのフィルム及び容器を透過する光エネ
ルギー密度の平均値(n=10) B:熱収縮性ポリスチレン系樹脂フィルムを装着させな
い状態での透明容器を透過する光エネルギー密度の平均
値(n=10)
The heat-shrinkable polystyrene resin film of the present invention is attached to a bottle as a label of a cylindrical tubular transparent container whose main shrinkage axis direction is a cylindrical cross-sectional direction, and after heat shrinking, the outside of the container. When the near-ultraviolet ray is irradiated from the inside to the inside in the direction perpendicular to the rotational symmetry axis of the container, the average value T of the transmittance of the near-ultraviolet ray represented by the following formula 1 must be 0.5 or less. The average value T of the transmittance of near-ultraviolet light is preferably 0.2 or less, more preferably 0.1 or less, still more preferably 0.08 or less, and particularly preferably 0.06 or less. When the average value T of the transmittance of near-ultraviolet rays exceeds 0.5, the heat-shrinkable polystyrene resin film of the present invention has a low light-shielding property with respect to an object to be packaged, and deterioration of the object to be packaged due to light rays cannot be prevented. T = A / B Formula 1 A: Average value of light energy density (n = 10) transmitted through the film and the container in the state where the heat-shrinkable polystyrene-based resin film is attached to the transparent container B: Heat-shrinkable polystyrene-based Average value of light energy density (n = 10) transmitted through the transparent container without the resin film attached

【0024】所望の近紫外線の平均透過率Tを得るため
の方法としては、熱収縮性フィルムを構成するポリスチ
レン系樹脂の種類や配合比の選択や、フィルムの結晶性
や相溶性の調節、厚みの調節、遮光剤、光吸収剤、UV
吸収剤、選択的光吸収剤等のフィルム中への配合および
/またはフィルム面への塗布、フィルム面への印刷等に
よる着色などの画像の形成、画像面積の増大、画像パタ
ーンの密度増大、画像濃度の増大などが挙げられる。さ
らに、ラベルとして被包装物に装着する際の被覆面積の
増大や、フィルムの熱収縮特性あるいは熱収縮条件の調
整による被包装物への密着強度の増大によっても、近紫
外線の平均透過率Tを低くすることができる。
As a method for obtaining the desired average transmittance T of near-ultraviolet rays, selection of the type and compounding ratio of the polystyrene resin constituting the heat-shrinkable film, adjustment of the crystallinity and compatibility of the film, and thickness Control, sunscreen, light absorber, UV
Blending of absorbers and selective light absorbers into the film and / or coating on the film surface, image formation such as coloring by printing on the film surface, increase in image area, increase in image pattern density, image Examples include increasing the concentration. Furthermore, the average transmittance T of the near-ultraviolet rays is also increased by increasing the coating area when the label is attached to the packaged item and increasing the adhesion strength to the packaged item by adjusting the heat shrinkage property of the film or the heat shrinkage condition. Can be lowered.

【0025】本発明の熱収縮性ポリスチレン系樹脂フィ
ルムは、主収縮方向において、100℃から10℃毎に
150℃までの各温度で、1分間加熱する処理後の、前
記処理前の長さに対する長さ変化率の最大値である最大
熱収縮率が40%以上である必要がある。最大熱収縮率
が40%未満であると、一般に使用されるボトルの胴部
分のラベル(胴ラベル)として使用する場合に収縮が不
足し、ボトルに密着させにくくなって、例えばPETボ
トル様の容器などは底部から肩部への全面に密着させる
ことができず、遮光性が不足する。特に、上記所望の近
紫外線の平均透過率Tを得るために、被覆面積を増大し
たり、被包装物への密着強度を増大させるには、上記最
大熱収縮率を40%以上とする必要がある。好ましくは
最大熱収縮率が60%以上であるのがよい。最大熱収縮
率が60%以上であると、PETボトル様の容器などの
底部から首部のほぼ全面に密着させることができる。さ
らに好ましくは70%以上であるのがよい。最大熱収縮
率が70%以上であると、PETボトル様の容器などの
底部から首部の上部まで全面に密着させることができ
る。特に好ましくは75%以上であるのがよい。最大熱
収縮率が75%以上であると、ビール瓶様の容器などの
底部から首部の上部まで全面に密着させることができ
る。
The heat-shrinkable polystyrene-based resin film of the present invention has a length in a main shrinkage direction after heating for 1 minute at each temperature from 100 ° C. to 10 ° C. up to 150 ° C. The maximum rate of thermal contraction, which is the maximum rate of change in length, must be 40% or more. When the maximum heat shrinkage ratio is less than 40%, shrinkage is insufficient when used as a label (body label) for a body portion of a commonly used bottle, and it becomes difficult to adhere to the bottle, for example, a PET bottle-like container. Cannot adhere to the entire surface from the bottom to the shoulder, resulting in insufficient light-shielding properties. In particular, in order to obtain the desired average transmittance T of the near-ultraviolet rays, in order to increase the coating area and the adhesion strength to the article to be packaged, it is necessary to set the maximum heat shrinkage rate to 40% or more. is there. It is preferable that the maximum heat shrinkage is 60% or more. When the maximum heat shrinkage ratio is 60% or more, it is possible to adhere to almost the entire surface from the bottom to the neck of a PET bottle-like container. More preferably, it is 70% or more. When the maximum heat shrinkage is 70% or more, it is possible to adhere the entire surface from the bottom of a PET bottle-like container to the top of the neck. It is particularly preferably at least 75%. When the maximum heat shrinkage is 75% or more, the entire surface from the bottom of a beer bottle-like container to the top of the neck can be adhered.

【0026】最大熱収縮率を上記範囲方法とする方法と
しては、例えば、熱収縮性フィルムを構成する樹脂の種
類や配合比、可塑剤などの添加剤の配合、フィルムの製
造条件の調整、特に高延伸倍率化、延伸温度を低めに設
定する、フィルムの結晶化度を調整するなどの方法が挙
げられる。
Examples of the method for setting the maximum heat shrinkage ratio within the above range include, for example, the types and blending ratios of resins constituting the heat shrinkable film, blending of additives such as plasticizers, adjustment of film production conditions, Examples of such methods include increasing the draw ratio, setting the draw temperature at a lower value, and adjusting the crystallinity of the film.

【0027】本発明の熱収縮性ポリスチレン系樹脂フィ
ルムは、折り径175mm、主収縮軸方向と直行する方
向の長さ120mmのラベル形状とし、該ラベルを底面
が四角形の筒体とした場合の筒体の上下方向の圧縮強度
が5000mN以上である必要がある。圧縮強度が50
00mN未満であると、チューブ状のラベル形状とし
て、該ラベルを円筒形に開き、ボトルに被せる装着工程
において、ラベルの腰折れや装着用の器具とボトルとの
間の挫屈状態により、装着不能となる。上記圧縮強度が
6000mN以上であると、軽度の腰折れなどの変形に
よるラベルの位置ずれも防止できて好ましい。
The heat-shrinkable polystyrene resin film of the present invention has a label shape having a folding diameter of 175 mm and a length of 120 mm in a direction perpendicular to the main shrinkage axis direction, and the label is a cylinder having a quadrangular bottom surface. The vertical compressive strength of the body must be 5000 mN or more. Compressive strength is 50
When it is less than 00 mN, it becomes unusable due to a tubular label shape, the label is opened into a cylindrical shape, and in the mounting step of covering the bottle, the label is bent or the buckling state between the mounting device and the bottle causes the label to become unmountable. Become. When the compressive strength is 6000 mN or more, it is possible to prevent displacement of the label due to deformation such as slight bending of the waist, which is preferable.

【0028】上記圧縮強度を上記範囲方法とする方法と
しては、例えば、フィルム厚みを大きくする方法も挙げ
られるが、コスト性の点からはフィルム厚みは65μm
以下であるのが好ましく、さらに好ましくは55μm以
下、透明性を考慮すると45μm以下であるのが特に好
ましい。従って、上記圧縮強度を上記範囲方法とするた
めには、原料樹脂を固くする方法、例えば、熱収縮性フ
ィルムを構成する樹脂の種類や配合比の調整や、各特性
を有する樹脂からなる2層以上の多層構造とする方法が
挙げられる。ポリスチレン系樹脂を使用する場合、立体
規則性の高い樹脂を使用する方法もあるが、低温収縮性
や高収縮性を維持するためには、樹脂の種類や配合比、
特にSBRなどのゴム成分の種類や配合比を調整する方
法および多層構成とする方法が好ましい。
As a method of setting the compressive strength in the above range method, for example, a method of increasing the film thickness can be mentioned, but from the viewpoint of cost, the film thickness is 65 μm.
It is preferably not more than 55 μm, more preferably not more than 55 μm, and particularly preferably not more than 45 μm in consideration of transparency. Therefore, in order to set the compressive strength to the above range method, a method of hardening the raw material resin, for example, adjustment of the type and compounding ratio of the resin constituting the heat-shrinkable film, and two layers made of a resin having each characteristic The method of making the above-mentioned multilayer structure is mentioned. When using a polystyrene resin, there is also a method of using a resin with high stereoregularity, but in order to maintain low-temperature shrinkage and high shrinkability, the type and blending ratio of the resin,
In particular, a method of adjusting the type and compounding ratio of rubber components such as SBR and a method of forming a multilayer structure are preferable.

【0029】本発明の熱収縮性ポリスチレン系樹脂フィ
ルムは、容器等の被覆、結束、外装などに用いられる包
装材として好適に用いられ、本発明のフィルムを用いる
ことにより美麗な外観を得ることができる。特に、本発
明のフィルムにより構成されるラベルは、被覆性に優
れ、容器の包装用として好適である。本発明の熱収縮性
ポリスチレン系樹脂フィルム及びラベルは、被覆面積が
大きい物品や、複雑な形状の物品、例えば細い首部を有
する容器などであっても、全体を均一に被覆できる。ま
た本発明の熱収縮性ポリスチレン系樹脂フィルムは、加
熱保存容器への優れた適用性を有し、本発明のフィルム
により構成されるラベルを装着した容器等は、収縮後に
高温条件下にさらされても、ラベルがその外観を安定し
て保持する。また、外部からの機械的な刺激や光線から
被包装物を保護でき、被包装物の劣化を防止できる。ま
た、ボトルに被せる装着工程などの特有の工程を経る場
合に適した腰の強さを有し、高速包装過程を経ても優れ
た収縮仕上がり外観性が得られる。従って、本発明の熱
収縮性ポリスチレン系樹脂フィルム及びラベルは耐熱プ
ラスチックボトル、ガラス瓶、金属容器、陶磁器等の種
々の容器の包装用として使用することができ、緑茶、ジ
ュース、ビール等の飲料、耐光性の低い合成又は天然色
素を含有する食品、化粧品、衛生用品、医薬品などを収
容する容器や包装物などの包装に好適である。
The heat-shrinkable polystyrene resin film of the present invention is preferably used as a packaging material used for covering, binding, and packaging of containers and the like, and a beautiful appearance can be obtained by using the film of the present invention. it can. In particular, the label composed of the film of the present invention has excellent coverage and is suitable for packaging containers. The heat-shrinkable polystyrene-based resin film and label of the present invention can be uniformly coated even on an article having a large coating area or an article having a complicated shape, such as a container having a thin neck. Further, the heat-shrinkable polystyrene resin film of the present invention has excellent applicability to a heat storage container, and a container equipped with a label composed of the film of the present invention is exposed to high temperature conditions after shrinkage. However, the label keeps its appearance stable. Further, the packaged item can be protected from external mechanical stimuli and light rays, and the packaged item can be prevented from deterioration. Further, it has a waist strength suitable for a specific process such as a mounting process for covering a bottle, and an excellent shrink finish appearance can be obtained even after a high-speed packaging process. Therefore, the heat-shrinkable polystyrene-based resin film and label of the present invention can be used for packaging various containers such as heat-resistant plastic bottles, glass bottles, metal containers, and ceramics, green tea, juice, beverages such as beer, light resistance. It is suitable for packaging of containers and packages containing foods, cosmetics, hygiene products, pharmaceuticals, etc. containing a synthetic or natural dye having low properties.

【0030】以下に、試験例、実施例を用いて本発明を
さらに具体的に説明するが、本発明はこれらに限定され
るものではない。
The present invention will be described in more detail below with reference to test examples and examples, but the present invention is not limited thereto.

【0031】試験例 1.試験方法 圧縮強度 実施例1〜7、比較例1、2,4の熱収縮性ポリスチレ
ン系樹脂フィルム、および比較例3のラベルを形成する
熱収縮性ポリスチレン系樹脂フィルムを、折り径175
mm、主収縮軸方向と直行する方向(非収縮方向)の長
さ120mmのラベル形状とし、該ラベルを折り返した
底面が四角形となる筒体を5点作成した。各筒体の上下
方向の圧縮強度(単位:mN)を、ストログラフ(東洋
精機(株)製、型式:V10−C)を用い、圧縮モー
ド、クロスヘッドスピード200mm/分で測定し、最
大値をフィルムの圧縮強度とした。
Test Example 1. Test Method Compressive Strength The heat-shrinkable polystyrene-based resin films of Examples 1 to 7 and Comparative Examples 1, 2 and 4 and the heat-shrinkable polystyrene-based resin film forming the label of Comparative Example 3 were folded with a folding diameter of 175.
mm, and a label shape having a length of 120 mm in a direction orthogonal to the main shrinkage axis direction (non-shrinkage direction), and five bottomed tubular bodies having a quadrangular bottom surface were prepared. The vertical compression strength (unit: mN) of each cylinder was measured using a strograph (manufactured by Toyo Seiki Co., Ltd., model: V10-C) at compression mode and crosshead speed of 200 mm / min, and the maximum value was obtained. Was defined as the compressive strength of the film.

【0032】(2)近紫外線の透過率 実施例1〜7、比較例1,2,4の熱収縮性ポリスチレ
ン系樹脂フィルムを、主収縮軸方向が下記容器の回転対
称軸に垂直な方向となるように、主収縮方向と直行する
方向の長さが23cmの円筒形チューブ状である透明容
器のフルラベル形状に形成し、透明な1.0リットルの
角形PETボトルに装着後、後述の試験(4)と同様に
して熱収縮させた。細い棒の先に半導体UVセンサー
(浜松ホトニクス製、G3614)をとりつけた計測器
を結線し、出力および光エネルギー密度(mW/c
)を較正して、上記ボトルの口部のキャップ中央に
設けられた直径5mmの穴から、上記計測器をボトル内
にボトルの回転対称軸に添って挿入した。光源(松下電
器社製ブラックライトブルーFL15BL−B、15
W、41cm)を、その中心軸が上記ボトルの回転対称
軸から15cm離れて、容器とほぼ平行に並ぶように配
置し、容器外部側から内側へ容器の回転対称軸に垂直な
方向からの近紫外線を照射した。ボトルの回転対称軸に
添って上記半導体UVセンサーを移動させ、ボトルの不
透明部分を除いた底部から口部までを10等分した各箇
所において、フィルム及びボトルを透過する光エネルギ
ー密度を測定し(A1〜A10)、この平均値Aを求め
た。次ぎに熱収縮性ポリスチレン系樹脂フィルムを除去
し、上記と同様にして、同一の測定個所で透明容器を透
過する光エネルギー密度を測定し(B1〜B10)、こ
の平均値Bを求めた。上記A,Bより、下記式1で表さ
れる近紫外線の透過率の平均値Tを算出した。なお、比
較例4のフィルムは、半調印刷を施した部分がボトルの
下半分を被覆するようにした。また、比較例3のラベル
を同様にボトルに装着して、近紫外線の透過率の平均値
Tを求めた。なお、「主収縮方向」は、フィルムの縦方
向及び横方向について、下記の最大熱収縮率を測定し、
該最大熱収縮率の大きい方向を主収縮方向とした。実施
例及び比較例のフィルムにおいては横方向が主収縮方向
であった。 T=A/B 式1 A:熱収縮性ポリスチレン系樹脂フィルムを透明容器に
装着させた状態でのフィルム及び容器を透過する光エネ
ルギー密度の平均値(n=10) B:熱収縮性ポリスチレン系樹脂フィルムを装着させな
い状態での透明容器を透過する光エネルギー密度の平均
値(n=10)
(2) Transmittance of near-ultraviolet rays The heat-shrinkable polystyrene resin films of Examples 1 to 7 and Comparative Examples 1, 2 and 4 were arranged such that the main shrinkage axis direction was perpendicular to the rotational symmetry axis of the container described below. As described above, a transparent container having a length of 23 cm in a direction orthogonal to the main shrinkage direction was formed into a full-label shape of a cylindrical tube, and mounted on a transparent 1.0-liter square PET bottle, and the test described later ( Thermal contraction was performed in the same manner as 4). A measuring instrument equipped with a semiconductor UV sensor (Hamamatsu Photonics, G3614) is connected to the tip of a thin rod, and output and light energy density (mW / c
m 2 ) was calibrated and the instrument was inserted into the bottle along the axis of rotational symmetry of the bottle through a 5 mm diameter hole provided in the center of the cap at the mouth of the bottle. Light source (Matsushita Electric Corporation Black Light Blue FL15BL-B, 15
W, 41 cm) is arranged such that the central axis thereof is 15 cm away from the rotational symmetry axis of the bottle and is aligned substantially parallel to the container, and is closer to the inside of the container from the direction perpendicular to the rotational symmetry axis of the container. Irradiated with ultraviolet rays. The semiconductor UV sensor was moved along the axis of rotational symmetry of the bottle, and the light energy density passing through the film and the bottle was measured at each of the 10 parts from the bottom to the mouth excluding the opaque portion of the bottle (( A1 to A10), and the average value A was determined. Next, the heat-shrinkable polystyrene resin film was removed, and the light energy density transmitted through the transparent container was measured at the same measurement points (B1 to B10) in the same manner as above, and the average value B was obtained. From A and B above, the average value T of the transmittance of near-ultraviolet rays represented by the following formula 1 was calculated. In the film of Comparative Example 4, the half-tone printed portion covered the lower half of the bottle. Also, the label of Comparative Example 3 was similarly attached to the bottle, and the average value T of the transmittance of near-ultraviolet rays was obtained. Incidentally, the "main shrinkage direction" is, in the longitudinal direction and the transverse direction of the film, the following maximum heat shrinkage rate is measured,
The direction in which the maximum heat shrinkage rate was large was defined as the main shrinkage direction. In the films of Examples and Comparative Examples, the lateral direction was the main shrinkage direction. T = A / B Formula 1 A: Average value of light energy density (n = 10) transmitted through the film and the container in the state where the heat-shrinkable polystyrene-based resin film is attached to the transparent container B: Heat-shrinkable polystyrene-based Average value of light energy density (n = 10) transmitted through the transparent container without the resin film attached

【0033】(3)最大熱収縮率 実施例1〜7、比較例1,2,4の熱収縮性ポリスチレ
ン系樹脂フィルム、および比較例3のラベルを形成する
熱収縮性ポリスチレン系樹脂フィルムを、主収縮方向を
長手方向として、幅15mmとなるように裁断し、長手
方向に200mm間隔で標線を記して試験片とした。1
00℃から10℃毎に150℃までの各温度に設定した
熱風循環式恒温器((株)鵬製作所製、FX−1:ダン
パー閉、クイックヒーターON)中に、試験片が恒温器
の中央に位置するように静置し、それぞれ1分間加熱し
た。恒温器中から、試験片を取り出して冷却した後、標
線間の距離(X:単位mm)を測定し、処理後の処理前
の長さに対する長さ変化率D(単位%)を下記の式2を
用いて算出した。この長さ変化率Dの内、最大値を最大
熱収縮率とした。 D(%)={(200−X)/200 }×100 式2
(3) Maximum heat shrinkage ratio The heat shrinkable polystyrene resin films of Examples 1 to 7 and Comparative Examples 1, 2 and 4 and the heat shrinkable polystyrene resin film forming the label of Comparative Example 3 were A test piece was obtained by cutting the main shrinkage direction in the longitudinal direction so as to have a width of 15 mm, and marking marked lines at intervals of 200 mm in the longitudinal direction. 1
In the hot air circulation type incubator (manufactured by Peng Seisakusho Co., Ltd., FX-1: damper closed, quick heater ON) set to each temperature from 00 ° C to 10 ° C every 150 ° C, the test piece is in the center of the incubator. Were allowed to stand and were heated for 1 minute. After the test piece was taken out of the incubator and cooled, the distance between the marked lines (X: unit mm) was measured, and the length change rate D (unit%) after the treatment to the length before the treatment was calculated as follows. It was calculated using Equation 2. Of the length change rates D, the maximum value was defined as the maximum heat shrinkage rate. D (%) = {(200−X) / 200} × 100 Formula 2

【0034】(4)収縮斑 実施例1〜7、比較例1、2,4の熱収縮性ポリスチレ
ン系樹脂フィルムにメタリック裏印刷を施し、後述のP
ETボトル用ラベルとなるサイズ(主収縮方向が円形の
断面となり、主収縮方向と直行する方向の長さが23c
m)の円筒形にチューブ化してラベルを形成した。上記
ラベル、およびメタリック裏印刷を施した比較例3のラ
ベルを1.0リットルの角形PETボトルに被せ、シュ
リンクトンネルを通過させた。シュリンクトンネルにお
ける条件は、第1ゾーンが100℃で滞留時間4.5
秒、第2ゾーンが140℃で滞留時間5秒とした。シュ
リンクトンネル通過後、熱収縮したラベルの収縮むらに
よる印刷の濃淡を目視により、下記の基準に従って評価
した。なお、比較例4のフィルムは、半調印刷を施した
部分がボトルの下半分を被覆するようにした。 ◎;むら、しわ、ゆるみ等の欠点が認められず、非常に
良好 ○;むら、しわ、ゆるみ等の欠点がほとんど認められ
ず、良好 △;むら、しわ、ゆるみ等の欠点が明確に認められ、良
好でない ×;むら、しわ、ゆるみ等の欠点が多く、不良
(4) Shrinkage unevenness The heat-shrinkable polystyrene resin films of Examples 1 to 7 and Comparative Examples 1, 2 and 4 were subjected to metallic back printing, and the P
ET bottle label size (main shrink direction is circular cross section, length in the direction orthogonal to main shrink direction is 23c
The label was formed by forming a tube into a cylinder of m). The above label and the label of Comparative Example 3 provided with metallic back printing were put on a 1.0-liter square PET bottle and passed through a shrink tunnel. The conditions in the shrink tunnel are 100 ° C in the first zone and a residence time of 4.5.
Second, the second zone was 140 ° C., and the residence time was 5 seconds. After passing through the shrink tunnel, the print density due to uneven shrinkage of the heat-shrinkable label was visually evaluated according to the following criteria. In the film of Comparative Example 4, the half-tone printed portion covered the lower half of the bottle. ⊚: Defects such as unevenness, wrinkles, and looseness are not recognized, and very good ○: Defects such as unevenness, wrinkles, and looseness are hardly recognized, and good Δ: Defects such as unevenness, wrinkles, and looseness are clearly recognized Poor, bad; many defects such as unevenness, wrinkles, looseness, etc.

【0035】2.試験結果 上記試験(1)〜(4)の結果を表2に示す。2. Test results Table 2 shows the results of the above tests (1) to (4).

【0036】[0036]

【実施例】[原料樹脂]表1に示す配合の各樹脂組成物
(組成物A〜G)をそれぞれ予め配合して溶融混練し、
押し出してペレタイズし、チップとした後、乾燥した。
EXAMPLES [Raw material resin] Each resin composition (compositions A to G) having the composition shown in Table 1 was previously compounded and melt-kneaded.
It was extruded, pelletized, made into chips and dried.

【0037】実施例1 表1における組成物Fと組成物Gとを、それぞれ30m
mφの単軸押出機に投入し、組成物Gが中心層(b
層)、組成物Fが両表面層(a層,c層)となる3層を
構成し、厚み比率がa層:b層:c層=1:2:1とな
るように、マルチマニフォールドダイより250℃で溶
融押出し、40℃の冷却ロールにエアーナイフ法により
密着させて冷却固化し、無定形シートを得た。該無定形
シートを、110℃に予熱し、延伸温度90℃で横方向
に倍率5.0倍に延伸した後、60℃で15秒熱固定処
理を行って、厚さ50μmの熱収縮性フィルムを得た。
該フィルムの片面の全面に半調印刷により画像を形成
し、実施例とした。
Example 1 Composition F and Composition G in Table 1 were each 30 m
The composition G was charged into a single-screw extruder of mφ, and the composition G was added to the central layer (b
Layer) and the composition F constitutes three layers which are both surface layers (a layer, c layer), and the thickness ratio is a layer: b layer: c layer = 1: 2: 1. Further, it was melt extruded at 250 ° C., and was brought into close contact with a cooling roll at 40 ° C. by an air knife method to be cooled and solidified to obtain an amorphous sheet. The amorphous sheet was preheated to 110 ° C., stretched at a stretching temperature of 90 ° C. in the transverse direction at a draw ratio of 5.0 times, and then heat-set at 60 ° C. for 15 seconds to obtain a heat-shrinkable film having a thickness of 50 μm. Got
An image was formed on the entire surface of one side of the film by halftone printing and used as an example.

【0038】実施例2 表1における組成物Fと組成物Gとを、それぞれ30m
mφの単軸押出機に投入し、組成物Fが中心層(b
層)、組成物Gが両表面層(a層,c層)となる3層を
構成するようにした以外は、実施例1と同様にして、厚
さ50μmの熱収縮性フィルムを得た。
Example 2 Composition F and composition G in Table 1 were each 30 m
The composition F was put into a single-screw extruder of mφ, and the composition F was mixed with the central layer (b
Layer) and the composition G was configured to form three layers to be both surface layers (a layer and c layer), and a heat-shrinkable film having a thickness of 50 μm was obtained in the same manner as in Example 1.

【0039】実施例3 表1における組成物Gと組成物Bとを、それぞれ30m
mφの単軸押出機に投入し、組成物Gが中心層(b
層)、組成物Bが両表面層(a層,c層)となる3層を
構成するようにした以外は、実施例1と同様にして、厚
さ50μmの熱収縮性フィルムを得た。
Example 3 Composition G and composition B in Table 1 were each 30 m
The composition G was charged into a single-screw extruder of mφ, and the composition G was added to the central layer (b
Layer) and the composition B was configured to form three layers which are both surface layers (layer a, layer c), and a heat-shrinkable film having a thickness of 50 μm was obtained in the same manner as in Example 1.

【0040】実施例4 表1における組成物Bと組成物Aとを、それぞれ30m
mφの単軸押出機に投入し、組成物Bが中心層(b
層)、組成物Aが両表面層(a層,c層)となる3層を
構成するようにした以外は、実施例1と同様にして、厚
さ50μmの熱収縮性フィルムを得た。
Example 4 Composition B and Composition A in Table 1 were each 30 m
The composition B was charged into a single-screw extruder of mφ, and the composition B was added to the central layer (b
Layer) and the composition A was configured to form three layers which are both surface layers (layer a, layer c), and a heat-shrinkable film having a thickness of 50 μm was obtained in the same manner as in Example 1.

【0041】実施例5 表1における組成物Cと組成物Aとを、それぞれ30m
mφの単軸押出機に投入し、組成物Cが中心層(b
層)、組成物Aが両表面層(a層,c層)となる3層を
構成するようにした以外は、実施例1と同様にして、厚
さ50μmの熱収縮性フィルムを得た。
Example 5 Composition C and Composition A in Table 1 were each 30 m
The composition C was charged into a single-screw extruder of mφ, and the composition C was added to the central layer (b
Layer) and the composition A was configured to form three layers which are both surface layers (layer a, layer c), and a heat-shrinkable film having a thickness of 50 μm was obtained in the same manner as in Example 1.

【0042】実施例6 表1における組成物Dと組成物Aとを、それぞれ30m
mφの単軸押出機に投入し、組成物Dが中心層(b
層)、組成物Aが両表面層(a層,c層)となる3層を
構成するようにした以外は、実施例1と同様にして、厚
さ50μmの熱収縮性フィルムを得た。
Example 6 Composition D and Composition A in Table 1 were each 30 m
The composition D was charged into a single-screw extruder of mφ, and the composition D was added to the central layer (b
Layer) and the composition A was configured to form three layers which are both surface layers (layer a, layer c), and a heat-shrinkable film having a thickness of 50 μm was obtained in the same manner as in Example 1.

【0043】実施例7 表1における組成物Eと組成物Aとを、それぞれ30m
mφの単軸押出機に投入し、組成物Eが中心層(b
層)、組成物Aが両表面層(a層,c層)となる3層を
構成するようにした以外は、実施例1と同様にして、厚
さ50μmの熱収縮性フィルムを得た。
Example 7 Composition E and Composition A in Table 1 were each 30 m
The composition E was charged into a single-screw extruder of mφ, and the composition E was added to the central layer (b
Layer) and the composition A was configured to form three layers which are both surface layers (layer a, layer c), and a heat-shrinkable film having a thickness of 50 μm was obtained in the same manner as in Example 1.

【0044】比較例1 表1における組成物Gのみを、それぞれ30mmφの単
軸押出機に投入し、中心層(b層)、両表面層(a層,
c層)の3層を構成するようにした以外は、実施例1と
同様にして、厚さ50μmの熱収縮性フィルムを得た。
Comparative Example 1 Only the composition G in Table 1 was charged into a single-screw extruder having a diameter of 30 mm, and the center layer (layer b) and both surface layers (layer a,
A heat-shrinkable film having a thickness of 50 μm was obtained in the same manner as in Example 1 except that the three layers (c layer) were formed.

【0045】比較例2 表1における組成物Fのみを、それぞれ30mmφの単
軸押出機に投入し、中心層(b層)、両表面層(a層,
c層)の3層を構成するようにした以外は、実施例1と
同様にして、厚さ50μmの熱収縮性フィルムを得た。
Comparative Example 2 Only the composition F in Table 1 was charged into a single screw extruder having a diameter of 30 mm, and the center layer (layer b) and both surface layers (layer a,
A heat-shrinkable film having a thickness of 50 μm was obtained in the same manner as in Example 1 except that the three layers (c layer) were formed.

【0046】比較例3 実施例1と同様にして厚さ50μmの熱収縮性ポリスチ
レン系樹脂フィルムを得、主収縮軸方向が円筒形断面方
向となり、主収縮方向と直行する方向の長さが10cm
の円筒形チューブ状である透明容器のラベル形状に成形
してラベルとした。
Comparative Example 3 A heat-shrinkable polystyrene resin film having a thickness of 50 μm was obtained in the same manner as in Example 1, the main shrinkage axis direction was the cylindrical cross-section direction, and the length in the direction orthogonal to the main shrinkage direction was 10 cm.
The label was formed by molding into a cylindrical tubular tubular transparent container label shape.

【0047】比較例4 フィルムの片面の半分のみに半調印刷により画像を形成
した以外は、実施例1と同様にして、厚さ50μmの熱
収縮性ポリスチレン系樹脂フィルムを得た。
Comparative Example 4 A heat-shrinkable polystyrene resin film having a thickness of 50 μm was obtained in the same manner as in Example 1 except that an image was formed by halftone printing on only one half of the film.

【0048】[0048]

【発明の効果】本発明の熱収縮性ポリスチレン系樹脂フ
ィルムは、ボトルに被せる装着工程などの特有の工程を
経る場合に適した腰の強さを有し、実用上充分に熱収縮
率が大きく、熱収縮時に、収縮工程での温度のゆらぎや
不均一にかかわりなく均等に収縮して、収縮むらが発生
せず、美麗な外観を呈する。さらに収縮後に高温条件下
にさらされても、たるみやしわが発生せず、その外観を
安定して保持する。また、表面積が大きく、口部が細い
などの複雑な形状の容器であっても全体を均一に被覆可
能であり、外部からの機械的な刺激や光線から被包装物
を保護でき、被包装物の劣化を防止できる。
EFFECT OF THE INVENTION The heat-shrinkable polystyrene-based resin film of the present invention has a waist strength suitable for peculiar steps such as a step of covering a bottle, and has a sufficiently large heat-shrinkage rate in practical use. During the heat shrinkage, it shrinks uniformly regardless of temperature fluctuations and nonuniformity in the shrinking process, so that uneven shrinkage does not occur and a beautiful appearance is exhibited. Further, even when exposed to high temperature conditions after shrinkage, slack and wrinkles do not occur and the appearance is stably maintained. In addition, even if the container has a large surface area and a complicated shape such as a narrow mouth, the whole can be uniformly coated, and the package can be protected from mechanical stimuli and light rays from the outside. Can be prevented from deteriorating.

【表1】 ゴム成分(G) G1:スチレン(30wt%)−ブタジエンブロック共
重合体
[Table 1] Rubber component (G) G1: Styrene (30 wt%)-butadiene block copolymer

【表2】 [Table 2]

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 FI テーマコート゛(参考) // B29K 25:00 B29K 25:00 B29L 7:00 B29L 7:00 9:00 9:00 (72)発明者 早川 聡 愛知県犬山市大字木津字前畑344番地 東 洋紡績株式会社犬山工場内 (72)発明者 多保田 規 愛知県犬山市大字木津字前畑344番地 東 洋紡績株式会社犬山工場内 (72)発明者 米田 茂 大阪府大阪市北区堂島浜二丁目2番8号 東洋紡績株式会社本社内 (72)発明者 野瀬 克彦 大阪府大阪市北区堂島浜二丁目2番8号 東洋紡績株式会社本社内 Fターム(参考) 3E062 AA09 AC02 DA07 JA04 JA08 JB05 JC02 JD05 JD08 3E067 AA11 AA22 AB26 AC01 BA18A BB14A BC03A CA01 CA12 EA29 EE04 FB01 4F100 AK12 AK12A AK12B AK12J AL05 BA01 BA02 BA03 BA04 BA05 BA16 DA01 EH20 EJ37 EJ38 GB16 GB90 JA02A JA02B JD09A JD09B JK05A JK05B JL04 YY00A YY00B 4F210 AA13 AE01 AG01 AG03 RA03 RC02 RG02 RG04 RG09 RG43─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) // B29K 25:00 B29K 25:00 B29L 7:00 B29L 7:00 9:00 9:00 (72) Inventor Satoshi Hayakawa 344 Maebata, Kizu, Ai, Inuyama, Aichi Prefecture, Inuyama Plant, Toyobo Co., Ltd. (72) Nori Tabota, 344 Maebata, Kizu, Inuyama, Aichi Prefecture, Toyobo Co., Ltd., Inuyama Plant (72) ) Inventor Shigeru Yoneda 2-8 Dojimahama, Kita-ku, Osaka-shi, Osaka Toyobo Co., Ltd. (72) Inventor Katsuhiko Nose 2-8 Dojimahama, Kita-ku, Osaka-shi, Osaka Toyobo Co., Ltd. F term (reference) 3E062 AA09 AC02 DA07 JA04 JA08 JB05 JC02 JD05 JD08 3E067 AA11 AA22 AB26 AC01 BA18A BB14A BC03A CA01 CA12 EA29 EE04 FB01 4F100 AK12 AK12A AK12B AK12J AL05 BA01 BA02 BA03 BA03 BA02 BA03 BA05 BA16 DA01 EH20 EJ37 EJ38 GB16 GB90 JA02A JA02B JD09A JD09B JK05A JK05B JL04 YY00A YY00B 4F210 AA13 AE01 AG01 AG03 RA03 RC02 RG02 RG04 RG09 RG43

Claims (6)

【特許請求の範囲】[Claims] 【請求項1】 主収縮方向において、100℃から10
℃毎に150℃までの各温度で、1分間加熱する処理後
の、前記処理前の長さに対する長さ変化率の最大値であ
る最大熱収縮率が40%以上であり、主収縮軸方向が円
筒形断面方向となる円筒形チューブ状の透明容器のラベ
ル形状としてボトルに装着させ、熱収縮後の状態で、容
器外部側から内側へ容器の回転対称軸に垂直な方向から
近紫外線を照射した場合の、下記式1で表される近紫外
線の透過率の平均値Tが0.5以下であり、折り径17
5mm、主収縮軸方向と直行する方向の長さ120mm
のラベル形状とし、該ラベルを底面が四角形の筒体とし
た場合の筒体の上下方向の圧縮強度が5000mN以上
であることを特徴とする熱収縮性ポリスチレン系樹脂フ
ィルム。 T=A/B 式1 A:熱収縮性ポリスチレン系樹脂フィルムを透明容器に
装着させた状態でのフィルム及び容器を透過する光エネ
ルギー密度の平均値(n=10) B:熱収縮性ポリスチレン系樹脂フィルムを装着させな
い状態での透明容器を透過する光エネルギー密度の平均
値(n=10)
1. From 100 ° C. to 10 in the main shrinking direction
The maximum heat shrinkage rate, which is the maximum value of the rate of change in length with respect to the length before the treatment, is 40% or more after the treatment of heating for 1 minute at each temperature up to 150 ° C. for each main shrinkage axis direction. It is attached to a bottle as a label of a cylindrical tube-shaped transparent container with a cylindrical cross-section, and after heat shrinking, it irradiates near-ultraviolet rays from the outside of the container to the inside in the direction perpendicular to the axis of rotational symmetry of the container. In this case, the average value T of the transmittance of near ultraviolet rays represented by the following formula 1 is 0.5 or less, and the folding diameter is 17
5 mm, length 120 mm in the direction orthogonal to the main contraction axis direction
The heat-shrinkable polystyrene-based resin film, wherein the label has the shape of a label, and when the label has a quadrangular bottom, the vertical compression strength of the barrel is 5000 mN or more. T = A / B Formula 1 A: Average value of light energy density (n = 10) transmitted through the film and the container in the state where the heat-shrinkable polystyrene-based resin film is attached to the transparent container B: Heat-shrinkable polystyrene-based Average value of light energy density (n = 10) transmitted through the transparent container without the resin film attached
【請求項2】 折り径175mm、主収縮軸方向と直行
する方向の長さ120mmのラベル形状とし、該ラベル
を底面が四角形の筒体とした場合の筒体の上下方向の圧
縮強度が6000mN以上であることを特徴とする請求
項1記載の熱収縮性ポリスチレン系樹脂フィルム。
2. A label having a folding diameter of 175 mm and a length of 120 mm in a direction orthogonal to the main contraction axis direction, and when the label has a rectangular bottom surface, the vertical compression strength of the cylinder is 6000 mN or more. The heat-shrinkable polystyrene-based resin film according to claim 1, wherein
【請求項3】 それぞれポリスチレン系樹脂からなる2
層以上の多層構成であることを特徴とする請求項1また
は2記載の熱収縮性ポリスチレン系樹脂フィルム。
3. Each of which is made of polystyrene resin
The heat-shrinkable polystyrene resin film according to claim 1 or 2, which has a multi-layered structure including at least one layer.
【請求項4】 それぞれポリスチレン系樹脂からなる2
層以上の多層構成であり、少なくとも1層がシンジオタ
クティック構造を有するポリスチレン系樹脂を含有する
ことを特徴とする請求項1乃至3のいずれか一項に記載
の熱収縮性ポリスチレン系樹脂フィルム。
4. A polystyrene resin 2
The heat-shrinkable polystyrene-based resin film according to any one of claims 1 to 3, wherein the heat-shrinkable polystyrene-based resin film has a multilayer structure including at least one layer and at least one layer contains a polystyrene-based resin having a syndiotactic structure.
【請求項5】 請求項1乃至4のいずれか一項に記載の
熱収縮性ポリスチレン系樹脂フィルムから構成されるこ
とを特徴とするラベル。
5. A label comprising the heat-shrinkable polystyrene resin film according to any one of claims 1 to 4.
【請求項6】 請求項5記載のラベルを装着してなる容
器。
6. A container provided with the label according to claim 5.
JP2001267620A 2001-09-04 2001-09-04 Heat-shrinkable polystyrenic resin film, and label and container using the same Pending JP2003071928A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2001267620A JP2003071928A (en) 2001-09-04 2001-09-04 Heat-shrinkable polystyrenic resin film, and label and container using the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2001267620A JP2003071928A (en) 2001-09-04 2001-09-04 Heat-shrinkable polystyrenic resin film, and label and container using the same

Publications (2)

Publication Number Publication Date
JP2003071928A true JP2003071928A (en) 2003-03-12
JP2003071928A5 JP2003071928A5 (en) 2006-12-14

Family

ID=19093725

Family Applications (1)

Application Number Title Priority Date Filing Date
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Country Status (1)

Country Link
JP (1) JP2003071928A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003073486A (en) * 2001-09-04 2003-03-12 Toyobo Co Ltd Heat-shrinkable polystyrene-based resin film, label and container using the same
JP2016079283A (en) * 2014-10-16 2016-05-16 シーアイ化成株式会社 Heat shrinkable polystyrene-based film, and heat shrinkable film label using the same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003073486A (en) * 2001-09-04 2003-03-12 Toyobo Co Ltd Heat-shrinkable polystyrene-based resin film, label and container using the same
JP2016079283A (en) * 2014-10-16 2016-05-16 シーアイ化成株式会社 Heat shrinkable polystyrene-based film, and heat shrinkable film label using the same

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