JP3286594B2 - Heat shrinkable label film and PET bottle on which label made of the film is attached - Google Patents
Heat shrinkable label film and PET bottle on which label made of the film is attachedInfo
- Publication number
- JP3286594B2 JP3286594B2 JP08944598A JP8944598A JP3286594B2 JP 3286594 B2 JP3286594 B2 JP 3286594B2 JP 08944598 A JP08944598 A JP 08944598A JP 8944598 A JP8944598 A JP 8944598A JP 3286594 B2 JP3286594 B2 JP 3286594B2
- Authority
- JP
- Japan
- Prior art keywords
- heat
- resin
- shrinkable label
- film
- weight
- 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 - Fee Related
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- Details Of Rigid Or Semi-Rigid Containers (AREA)
- Laminated Bodies (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、使用済みＰＥＴボ
トルから再生ＰＥＴフレークまたは再生ＰＥＴペレット
を得る再生工程において、ＰＥＴボトルから分離しやす
い熱収縮性ラベル用フィルムとそれが装着されたＰＥＴ
ボトルに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-shrinkable label film which can be easily separated from a PET bottle in a recycling step of obtaining a recycled PET flake or a recycled PET pellet from a used PET bottle, and a PET to which the label is attached.
About bottles.
【０００２】[0002]
【従来の技術】容器包装リサイクル法が施行されたこと
もあり、ＰＥＴボトルのリサイクルが活発化してきてい
る。リサイクル方法としては、回収したＰＥＴボトルを
洗浄、殺菌等をして再度使用する方法も考えられるが、
一般には、回収したＰＥＴボトルから再生ＰＥＴフレー
クまたは再生ＰＥＴペレットを得る方法が採用されてい
る。この工程の概略を以下に説明する。2. Description of the Related Art Recycling of PET bottles has become active due to the enforcement of the Containers and Packaging Recycling Law. As a recycling method, a method of cleaning and sterilizing the collected PET bottle and reusing it is also conceivable.
Generally, a method of obtaining a recycled PET flake or a recycled PET pellet from the collected PET bottle is adopted. The outline of this step will be described below.
【０００３】回収されたＰＥＴボトル（通常、アルミキ
ャップや熱収縮性ラベルが付いている状態にある）は、
人手、重量分離機、Ｘ線検査等によって、ガラス瓶、
缶、塩ビボトル等他の容器から選別される。次いで、Ｐ
ＥＴボトルは数ｍｍ〜１０ｍｍ角に粉砕される。次い
で、比重分離機によって、比重が１未満の熱収縮性ラベ
ル粉砕体が除去される。次いで、風力分離機によって、
比重が１以上の熱収縮性ラベル粉砕体が除去される。次
いで、アルミ分離機によって、アルミキャップ粉砕体が
除去される。こうして得たＰＥＴボトル粉砕体から、所
期の再生ＰＥＴフレークまたは再生ＰＥＴペレットが得
られる。[0003] The recovered PET bottles (usually with aluminum caps or heat-shrinkable labels) are
Glass bottles by hand, weight separator, X-ray inspection, etc.
Sorted from other containers such as cans and PVC bottles. Then P
The ET bottle is ground to several mm to 10 mm square. Next, the heat-shrinkable crushed label having a specific gravity of less than 1 is removed by a specific gravity separator. Then, by a wind separator,
The heat-shrinkable crushed label having a specific gravity of 1 or more is removed. Next, the aluminum cap pulverized body is removed by the aluminum separator. From the pulverized PET bottle thus obtained, desired regenerated PET flakes or regenerated PET pellets are obtained.
【０００４】前記した比重分離機とは、粉砕体を水中に
入れ、水に浮くもの（比重が１未満の熱収縮性ラベル）
と水に沈むものとを分離する装置であり、また、風力分
離機とは、粉砕体を拡げて、下から風を当て熱収縮性ラ
ベル粉砕体を吹き飛ばす装置である。各々の原理から、
比重分離機は単位時間当たりの処理能力が大きいのに対
し、風力分離機のそれは小さい。このため、比重分離機
で除去される、即ち、比重が１未満の熱収縮性ラベルが
要望されている。The above-mentioned specific gravity separator is a device in which a pulverized body is put in water and floats on water (a heat-shrinkable label having a specific gravity of less than 1).
A wind separator is a device that spreads a crushed body and blows the wind from below to blow off the heat-shrinkable crushed label body. From each principle,
While the specific gravity separator has a large processing capacity per unit time, that of the wind separator is small. Therefore, a heat-shrinkable label that is removed by a specific gravity separator, that is, has a specific gravity of less than 1 is desired.
【０００５】比重が１未満の熱収縮性ラベルとして、熱
収縮性のポリエチレン系樹脂フィルムやポリプロピレン
系樹脂フィルムからなるラベルがある。また、特公平５
−４３５９０号公報では、プロピレン系重合体と直鎖状
エチレン・ユニットおよび少なくとも１種以上の炭素数
４〜１０個のα−オレフィン・ユニットからなるポリオ
レフィンブロック共重合体との混合物からなるフィルム
が開示されている。As heat-shrinkable labels having a specific gravity of less than 1, there are labels made of heat-shrinkable polyethylene resin films and polypropylene resin films. In addition, special fair 5
JP-A-43590 discloses a film comprising a mixture of a propylene-based polymer and a polyolefin block copolymer comprising a linear ethylene unit and at least one α-olefin unit having 4 to 10 carbon atoms. Have been.
【０００６】[0006]
【発明が解決しようとする課題】ポリスチレン等の熱収
縮性フィルムから熱収縮性ラベルを得る一般的な工程は
以下の如くである。即ち、熱収縮性フィルムを製造し、
片面にグラビア印刷を施し、次いで、スリッター機で所
定の幅に数丁取りする。次いで、印刷面が内側にくるよ
うに、フィルムの縦方向を軸として幅方向が円周方向に
なるようにして、一方のフィルム端に溶剤を塗布しなが
ら封筒貼り形状で筒状にする（この工程をセンターシー
ルという。加工速度は１２０〜１４０ｍ／分である。図
２、図３参照）。次いで、この筒状フィルムを所定の長
さに切り取って、所期のラベルを得る。A general process for obtaining a heat-shrinkable label from a heat-shrinkable film such as polystyrene is as follows. That is, to produce a heat shrinkable film,
Gravure printing is performed on one side, and then several pieces are cut to a predetermined width by a slitter. Then, the width direction is set to be the circumferential direction around the longitudinal direction of the film so that the printing surface is on the inside, and the solvent is applied to one end of the film to form a tubular shape in an envelope pasting shape (this The process is called center sealing, and the processing speed is 120 to 140 m / min (see FIGS. 2 and 3). Next, the tubular film is cut into a predetermined length to obtain an intended label.
【０００７】一方、ポリエチレン系フィルム、ポリプロ
ピレン系フィルム、あるいはプロピレン系重合体とポリ
オレフィンブロック重合体との混合物からなるフィルム
等、ポリオレフィンフィルムは耐溶剤性がよいので、溶
剤でセンターシールすることができない。このため、印
刷面と反対面にコロナ処理をし、且つ、溶剤の代わりに
溶剤に溶解したウレタン系等の接着剤を用いてセンター
シールするか、または、超音波でセンターシールする方
法を採らざるを得ない。On the other hand, polyolefin films such as a polyethylene film, a polypropylene film, and a film made of a mixture of a propylene polymer and a polyolefin block polymer have good solvent resistance and cannot be center-sealed with a solvent. For this reason, a method of performing corona treatment on the surface opposite to the printing surface and sealing the center using an urethane-based adhesive or the like dissolved in the solvent instead of the solvent, or employing a method of center-sealing with ultrasonic waves is not adopted. Not get.
【０００８】しかしながら、接着剤を用いる方法では、
コロナ処理が必要であるばかりか、接着剤を安定して塗
布することが難しいので加工速度を５０〜７０ｍ／分に
落として、しかも、正常に塗布ができているかどうか人
がつきっきりで監視している必要がある。また、得られ
たセンターシール部の接着力が正常かどうかの確認は、
溶剤がポリオレフィンフィルムに拡散し、接着剤の硬化
がほぼ完全になってから行う必要があるので、センター
シール後１２時間以上、通常２４時間程度経過した後で
ないとできないという問題がある。さらに、接着剤には
熱収縮性がないので、得られたラベルを容器に熱収縮さ
せて装着した後のシール強度が低下する。このため、そ
の後で受ける加熱工程、即ち、中味商品のホット充填、
ボイル処理等の熱処理工程でシール部が剥離し易いとい
う問題がある。また、超音波でセンターシールする方法
では、加工速度が３０〜５０ｍ／分と遅く、しかもシー
ル部が波打ち状になり見栄えが悪いという欠点がある。However, in the method using an adhesive,
In addition to the need for corona treatment, it is difficult to apply the adhesive stably. Therefore, reduce the processing speed to 50 to 70 m / min. Need to be. Also, to confirm whether the obtained center seal has a normal adhesion,
Since the solvent must be diffused into the polyolefin film and the adhesive must be hardened almost completely, there is a problem that it cannot be performed until 12 hours or more, usually about 24 hours after the center sealing. Furthermore, since the adhesive does not have heat shrinkage, the seal strength after the resulting label is heat shrunk and attached to a container is reduced. For this reason, the subsequent heating process, that is, hot filling of the contents,
There is a problem that the seal portion is easily peeled off in a heat treatment process such as a boiling process. In addition, the method of center sealing by ultrasonic waves has a disadvantage that the processing speed is as slow as 30 to 50 m / min, and the seal portion is wavy, resulting in poor appearance.
【０００９】本発明が解決しようとする第１の課題は、
熱収縮性ラベルの比重が１未満であり、且つ、溶剤でセ
ンターシールができる、ＰＥＴボトルのリサイクルに有
利な熱収縮性ラベル用フィルムを提供することにある。The first problem to be solved by the present invention is as follows.
An object of the present invention is to provide a heat-shrinkable label film which has a specific gravity of less than 1 and can be center-sealed with a solvent and which is advantageous for recycling PET bottles.
【００１０】第２の課題は、リサイクルに有利なＰＥＴ
ボトルを提供することにある。The second problem is that PET is advantageous for recycling.
To provide a bottle.
【００１１】[0011]
【課題を解決するための手段】課題を解決するために本
発明は、ポリオレフィン樹脂層（但し発泡樹脂層は除
く）を芯材とし、その両面に押出成形用接着樹脂の層を
介して下記のポリスチレン系樹脂を主成分とする樹脂層
が積層された、比重が０．９９以下である熱収縮性ラベ
ル用フィルムであることを特徴とする。ポリスチレン系
樹脂：ブタジエン含有量１０〜４０重量％比重１．０２
〜１．０８のスチレン−ブタジエンブロック共重合体１
００重量部にポリスチレンを２〜５０重量部混合した樹
脂、又は、イソプレン含有量１０〜４０重量％比重１．
０２〜１．０８のスチレン−イソプレンブロック共重合
体１００重量部にポリスチレンを２〜５０重量部混合し
た樹脂。In order to solve the problems, the present invention comprises a polyolefin resin layer (excluding a foamed resin layer) as a core material, and an extruded adhesive resin layer formed on both surfaces thereof by the following method. A heat-shrinkable label film having a specific gravity of 0.99 or less, on which a resin layer mainly composed of a polystyrene resin is laminated. Polystyrene resin: butadiene content 10 to 40% by weight Specific gravity 1.02
Styrene-butadiene block copolymer 1
A resin obtained by mixing 2 to 50 parts by weight of polystyrene with 00 parts by weight, or an isoprene content of 10 to 40% by weight.
A resin obtained by mixing 2 to 50 parts by weight of polystyrene with 100 parts by weight of a styrene-isoprene block copolymer of 02 to 1.08.
【００１２】また、ポリオレフィン樹脂層がエチレンが
０．２〜１０モル％のエチレン−プロピレンランダム共
重合体を主成分とする層であることを特徴とし、さらに
は、このエチレン−プロピレンランダム共重合体１００
重量部に石油樹脂２〜５０重量部を混合した樹脂系を主
成分とする層であることを特徴とする。Further, the polyolefin resin layer is characterized in that it is a layer containing an ethylene-propylene random copolymer containing 0.2 to 10 mol% of ethylene as a main component. 100
It is a layer mainly composed of a resin system in which 2 to 50 parts by weight of a petroleum resin is mixed in parts by weight.
【００１３】また、接着樹脂の層がＭＦＲ０．２〜６０
ｇ／１０ｍｉｎの接着樹脂の層であることを特徴とし、
さらには、接着樹脂の層が酸変性ポリエチレン樹脂を主
成分とする層であることを特徴とし、さらには、酸変性
ポリエチレン樹脂が比重０．８８〜０．９０の酸変性超
低密度ポリエチレン樹脂であることを特徴とする。The adhesive resin layer has an MFR of 0.2 to 60.
g / 10 min of an adhesive resin layer,
Further, the adhesive resin layer is a layer containing an acid-modified polyethylene resin as a main component, and the acid-modified polyethylene resin is an acid-modified ultra-low density polyethylene resin having a specific gravity of 0.88 to 0.90. There is a feature.
【００１４】また、共押出し技術、延伸技術によって製
造された熱収縮性ラベル用フィルムであることを特徴と
する。Further, the present invention is characterized in that it is a heat-shrinkable label film produced by a co-extrusion technique or a stretching technique.
【００１５】さらには、前記した熱収縮性ラベル用フィ
ルムからなるラベルが装着された、リサイクルに有利な
ＰＥＴボトルであることを特徴とする。Further, the present invention is characterized in that the PET bottle is provided with a label comprising the above-mentioned heat-shrinkable label film and is advantageous for recycling.
【００１６】[0016]
【発明の実施の形態】本発明の実施の形態を以下に詳述
する。Embodiments of the present invention will be described in detail below.
【００１７】本発明のポリオレフィン樹脂とは、比重が
０．９６以下、好ましくは０．９４以下、さらに好まし
くは０．９２以下の、エチレン、プロピレン、Ｃ数が４
〜１２のα−オレフィンの単独重合体、これらオレフィ
ン２種以上からなる共重合体、またはこれらの重合体の
混合物をいう。比重が０．９６を超えると、本発明の、
比重が０．９９以下である熱収縮性ラベル用フィルムを
得るに際し、接着樹脂、ポリスチレン系樹脂を主成分と
する樹脂の選定や各層の厚み構成比に対する制限が大き
くなり、好ましくない。なお、オレフィン以外の単量
体、例えば、酢酸ビニル、アクリル酸及びその誘導体、
メタクリル酸及びその誘導体等、各種ビニル化合物と前
記のオレフィンとの共重合体や、変性ポリオレフィン、
あるいはアイオノマー等の架橋構造体も、比重が前記を
満たすものであれば本発明に含まれる。The polyolefin resin of the present invention has a specific gravity of 0.96 or less, preferably 0.94 or less, more preferably 0.92 or less, ethylene, propylene, and a C number of 4 or less.
To -12, a homopolymer of two or more of these olefins, or a mixture of these polymers. When the specific gravity exceeds 0.96, of the present invention,
In obtaining a heat-shrinkable label film having a specific gravity of 0.99 or less, the selection of a resin mainly composed of an adhesive resin and a polystyrene-based resin and a restriction on the thickness composition ratio of each layer are unfavorably increased. Incidentally, monomers other than olefins, for example, vinyl acetate, acrylic acid and its derivatives,
Methacrylic acid and its derivatives, such as copolymers of various vinyl compounds and the olefins, modified polyolefins,
Alternatively, a crosslinked structure such as an ionomer is also included in the present invention as long as the specific gravity satisfies the above.
【００１８】熱収縮特性、透明性、フィルムの腰等の点
から、好ましいポリオレフィン樹脂として、エチレン−
プロピレンランダム共重合体が挙げられる。なかでも、
エチレンが０．２〜１０モル％の、比重が０．８８〜
０．９２のエチレン−プロピレンランダム共重合体が好
ましい。さらには、エチレンが０．２〜１０モル％のエ
チレン−プロピレンランダム共重合体１００重量部に石
油樹脂２〜５０重量部を混合した樹脂系がより好まし
い。石油樹脂とは、脂肪族炭化水素、脂環族炭化水素、
水素添加炭化水素等からなる、比重が０．９１〜１．０
０の樹脂をいう。From the viewpoints of heat shrinkage characteristics, transparency, film stiffness and the like, a preferred polyolefin resin is ethylene-
Propylene random copolymer is mentioned. Above all,
0.2 to 10 mol% ethylene, specific gravity 0.88 to
A 0.92 ethylene-propylene random copolymer is preferred. Further, a resin system in which 2 to 50 parts by weight of a petroleum resin is mixed with 100 parts by weight of an ethylene-propylene random copolymer containing 0.2 to 10 mol% of ethylene is more preferable. Petroleum resins are aliphatic hydrocarbons, alicyclic hydrocarbons,
Made of hydrogenated hydrocarbon or the like, specific gravity of 0.91 to 1.0
0 resin.
【００１９】本発明の接着樹脂とは、ポリオレフィン樹
脂層とポリスチレン系樹脂を主成分とする樹脂層とを接
着させる樹脂をいい、必要とする接着強度が得られるも
のであれば特に限定するものではない。例えば、変性ポ
リオレフィン、アイオノマー、エチレン−エチルアクリ
レート等が挙げられる。接着樹脂のＭＦＲは０．２〜６
０ｇ／１０ｍｉｎ、好ましくは１〜３０ｇ／１０ｍｉ
ｎ、さらに好ましくは２〜１０ｇ／１０ｍｉｎの範囲に
あるものが望ましい。ＭＦＲが０．２ｇ／１０ｍｉｎ未
満であると、押出し成形することが難しくなる傾向にあ
る。ＭＦＲが６０ｇ／１０ｍｉｎを超えると加熱時に軟
化するので、熱収縮時、あるいは中味商品のホット充
填、ボイル処理等の加熱処理時にフィルムに皺が入り、
好ましくない。The adhesive resin of the present invention refers to a resin for bonding a polyolefin resin layer and a resin layer containing a polystyrene resin as a main component, and is not particularly limited as long as required adhesive strength can be obtained. Absent. For example, modified polyolefin, ionomer, ethylene-ethyl acrylate and the like can be mentioned. MFR of adhesive resin is 0.2-6
0 g / 10 min, preferably 1 to 30 g / 10 mi
n, more preferably in the range of 2 to 10 g / 10 min. If the MFR is less than 0.2 g / 10 min, extrusion molding tends to be difficult. If the MFR exceeds 60 g / 10 min, the film softens when heated, so that the film wrinkles during heat shrinkage, or during heat treatment such as hot filling of content items and boiling treatment,
Not preferred.
【００２０】ポリスチレン系樹脂を主成分とする樹脂層
との安定した接着力という点から、好ましい接着樹脂と
して、マレイン酸、フマル酸、その他の不飽和カルボン
酸またはそれらの無水物で変性した酸変性ポリエチレン
樹脂が挙げられる。なかでも、比重が０．８８〜０．９
０の酸変性超低密度ポリエチレン樹脂が、安定した接着
力のみならず比重が小さいという点から、より好まし
い。From the viewpoint of stable adhesion to a resin layer containing a polystyrene resin as a main component, a preferred adhesive resin is an acid-modified resin modified with maleic acid, fumaric acid, another unsaturated carboxylic acid or anhydride thereof. A polyethylene resin may be used. Above all, specific gravity is 0.88-0.9
The acid-modified ultra-low density polyethylene resin of 0 is more preferable from the viewpoint of not only stable adhesive strength but also low specific gravity.
【００２１】センターシール用溶剤としては、樹脂（フ
ィルム）を溶解する溶剤と溶解しない溶剤との混合系
が、シール部の見栄えという点から好ましい。何故な
ら、樹脂（フィルム）を溶解する溶剤のみでは樹脂（フ
ィルム）へのアタックが強すぎて、シール部が波打ち、
見栄えが悪くなるからである。このような混合系として
は、例えば、ポリスチレン系樹脂の場合ＴＨＦ（テトラ
ヒドロフラン）／ｎ−ヘキサン系が例示できる。As the solvent for the center seal, a mixed system of a solvent that dissolves the resin (film) and a solvent that does not dissolve is preferable from the viewpoint of the appearance of the seal portion. Because the solvent to dissolve the resin (film) alone is too strong to attack the resin (film), the seal part is wavy,
This is because it looks bad. As such a mixed system, for example, in the case of a polystyrene resin, THF (tetrahydrofuran) / n-hexane is exemplified.
【００２２】溶剤シール適性、熱収縮特性、フィルムの
腰、比重等の点から、ポリスチレン系樹脂として、ブタ
ジエンまたはイソプレンが１０〜４０重量％の、比重が
１．０２〜１．０８のスチレン−ブタジエンブロック共
重合体またはスチレン−イソプレンブロック共重合体１
００重量部にポリスチレンを２〜５０重量部混合した樹
脂系が好ましい。From the viewpoints of solvent sealing suitability, heat shrinkage properties, film rigidity, specific gravity, etc., styrene-butadiene containing 10 to 40% by weight of butadiene or isoprene and having a specific gravity of 1.02 to 1.08 as a polystyrene resin. Block copolymer or styrene-isoprene block copolymer 1
A resin system obtained by mixing 2 to 50 parts by weight of polystyrene to 00 parts by weight is preferable.
【００２３】本発明の熱収縮性ラベル用フィルムの比重
は０．９９以下であり、好ましくは０．９７以下、さら
に好ましくは０．９５以下である。０．９９を超える
と、フィルムに印刷されるインキの固形分の比重が１よ
り大きいので、得られた熱収縮性ラベルの比重が１以上
となり、比重分離機で分離することができない。比重が
１より小さければ小さいほど、分離速度が早くなり、単
位時間当たりの処理能力が上がるので、ＰＥＴボトルの
リサイクルに益々有利となる。The specific gravity of the heat shrinkable label film of the present invention is 0.99 or less, preferably 0.97 or less, more preferably 0.95 or less. If it exceeds 0.99, the specific gravity of the solid content of the ink printed on the film is greater than 1, so that the specific gravity of the obtained heat-shrinkable label becomes 1 or more and cannot be separated by a specific gravity separator. The smaller the specific gravity is, the faster the separation speed is and the higher the processing capacity per unit time is, so that it is more advantageous for recycling PET bottles.
【００２４】前記比重値を達成するためには、熱収縮特
性やフィルムの腰等を勘案しながら、ポリオレフィン樹
脂層と接着樹脂層とポリスチレン系樹脂を主成分とする
樹脂層の厚み構成比を適宜決めればよい。熱収縮性ラベ
ル用フィルムの厚さは特に限定はないが、通常２０〜１
００μｍのものが一般的である。In order to achieve the above specific gravity, the thickness composition ratio of the polyolefin resin layer, the adhesive resin layer, and the resin layer containing polystyrene resin as a main component is appropriately adjusted in consideration of the heat shrinkage characteristic, the stiffness of the film, and the like. You just have to decide. The thickness of the heat shrinkable label film is not particularly limited, but is usually 20 to 1
Those having a size of 00 μm are generally used.
【００２５】次に熱収縮性ラベル用フィルムの製造方法
について説明する。フィルムは公知の共押出し技術、延
伸技術によって製造される。例えば、ポリオレフィン樹
脂層を芯材とし、その両面に接着樹脂層を介してポリス
チレン系樹脂を主成分とする樹脂層がくるようにして、
Ｔダイからフラット状シートを共押出し、冷却して引き
取り、縦方向に１〜２倍ロール延伸し、横方向に３〜１
０倍テンター延伸し、幅方向に０〜１０％弛緩させつつ
アニールし、次いで巻き取ることにより熱収縮性フィル
ムが得られる。延伸は公知の同時２軸延伸法によっても
よい。また、丸ダイからチューブ状シートを共押出し、
チューブ状で延伸してもよいし、シートを切り開いてフ
ラット状とし、前記したように延伸してもよい。なお、
得られた熱収縮性ラベル用フィルムから熱収縮性ラベル
を得る工程は前記した通りである。Next, a method for producing a heat shrinkable label film will be described. The film is manufactured by a known co-extrusion technique or stretching technique. For example, a polyolefin resin layer as a core material, and a resin layer mainly composed of a polystyrene-based resin is provided on both surfaces thereof with an adhesive resin layer interposed therebetween,
A flat sheet is co-extruded from a T-die, cooled and taken off, roll-stretched 1-2 times in the longitudinal direction, and 3 to 1 in the transverse direction.
A heat-shrinkable film is obtained by stretching the film ten times with a tenter, annealing the film while relaxing it in the width direction by 0 to 10%, and winding the film. Stretching may be performed by a known simultaneous biaxial stretching method. Also, co-extrude a tubular sheet from a round die,
The sheet may be stretched in a tubular shape, or the sheet may be cut open to form a flat shape and stretched as described above. In addition,
The step of obtaining a heat-shrinkable label from the obtained heat-shrinkable label film is as described above.
【００２６】かくして得られた熱収縮性ラベル用フィル
ムの熱収縮率は、横方向２０％以上、縦方向５％以下、
通常、横方向３０％以上、縦方向３％以下である。ま
た、接着樹脂層とポリスチレン系樹脂を主成分とする樹
脂層との層間剥離強度は、２００ｇ／ｃｍ以上、通常３
００ｇ／ｃｍ以上である（ポリオレフィン樹脂層と接着
樹脂層とはよく接着しており、剥離不可能である）。The heat shrinkage ratio of the heat shrinkable label film thus obtained is 20% or more in the horizontal direction and 5% or less in the vertical direction.
Usually, it is 30% or more in the horizontal direction and 3% or less in the vertical direction. The delamination strength between the adhesive resin layer and the resin layer containing polystyrene resin as a main component is 200 g / cm or more, usually 3 g / cm 2.
It is not less than 00 g / cm (the polyolefin resin layer and the adhesive resin layer are well bonded and cannot be peeled off).
【００２７】熱収縮性ラベル用フィルムから熱収縮性ラ
ベルを得る方法は前記した通りであり、得られた熱収縮
性ラベルのシール強度は、４５０ｇ／ｃｍ以上、通常、
５５０ｇ／ｃｍ以上である。The method for obtaining a heat-shrinkable label from the film for a heat-shrinkable label is as described above, and the obtained heat-shrinkable label has a sealing strength of 450 g / cm or more.
It is 550 g / cm or more.
【００２８】[0028]
【実施例】次に本発明の代表的な実施例を挙げて説明す
る。EXAMPLES Next, typical examples of the present invention will be described.
【００２９】本発明において使用した物性値の測定方法
は次の通りである。The method for measuring physical properties used in the present invention is as follows.
【００３０】熱収縮性ラベル用フィルムの熱収縮率は、
以下の方法による。即ち、縦×横１００ｍｍ×１００ｍ
ｍ角に試料を切り取る。次いで、この試料を８０℃の温
水浴に５秒間浸漬させ、すぐに冷水で冷却した後、縦方
向及び横方向の長さＬ（ｍｍ）を測定する。そして１０
０−Ｌを縦方向、横方向の熱収縮率とする。The heat shrinkage of the heat shrinkable label film is as follows:
The following method is used. That is, vertical x horizontal 100mm x 100m
Cut the sample into m-squares. Next, this sample is immersed in a warm water bath at 80 ° C. for 5 seconds, immediately cooled with cold water, and then the length L (mm) in the vertical and horizontal directions is measured. And 10
Let 0-L be the heat shrinkage in the vertical and horizontal directions.
【００３１】接着樹脂層とポリスチレン系樹脂を主成分
とする樹脂層との層間剥離強度は、新東科学（株）製Ｈ
ＥＩＤＯＮ−１７型剥離試験機を用い、試料幅１ｃｍ、
Ｔ型剥離、剥離速度２０ｃｍ／分で測定した。The delamination strength between the adhesive resin layer and the resin layer containing polystyrene resin as a main component was measured by Shinto Kagaku Co., Ltd.
Using an EIDON-17 peel tester, sample width 1 cm,
T-type peeling was measured at a peeling speed of 20 cm / min.
【００３２】熱収縮性ラベルのシール強度は、以下の方
法による。即ち、筒状ラベルを円周方向に１ｃｍ幅に切
り取る。次いで、シール部のシールしろの部分と、他片
の端部とを、それぞれ新東科学（株）製ＨＥＩＤＯＮ−
１７型剥離試験機にセットし、剥離速度２０ｃｍ／分で
測定した。The sealing strength of the heat shrinkable label is determined by the following method. That is, the cylindrical label is cut to a width of 1 cm in the circumferential direction. Next, the seal margin part of the seal part and the end of the other piece are each connected to HEIDON- manufactured by Shinto Kagaku Co., Ltd.
The sample was set in a 17-type peel tester and measured at a peel speed of 20 cm / min.
【００３３】（実施例１） エチレンが３．９モル％のエチレン−プロピレンランダ
ム共重合体１００重量部に石油樹脂３０重量部混合した
樹脂系（比重が０．９２のＡ層）と、無水マレイン酸変
性超低密度ポリエチレン（比重が０．８９のＢ層）と、
ブタジエンが１５重量％のスチレン−ブタジエンブロッ
ク共重合体１００重量部にポリスチレン１８重量部を混
合した樹脂系（比重が１．０４のＣ層）とを、それぞれ
別の押出機に投入し、Ｃ／Ｂ／Ａ／Ｂ／Ｃの積層体とな
るように２４０℃でＴダイより押出し、３０℃の冷却ロ
ールで冷却固化させた後、９０℃で横方向に６倍テンタ
ー延伸し、引き続き同テンター内で幅方向に８％弛緩さ
せつつ、８０℃×５秒間アニールし、厚さが５０μｍの
熱収縮性ラベル用フィルムを得た（各層の厚さは４μｍ
／２μｍ／３８μｍ／２μｍ／４μｍ）。得られた熱収
縮性ラベル用フィルムの物性値を表１に示す。Example 1 A resin system (layer A having a specific gravity of 0.92) obtained by mixing 30 parts by weight of a petroleum resin with 100 parts by weight of an ethylene-propylene random copolymer containing 3.9 mol% of ethylene, and maleic anhydride Acid-modified ultra low density polyethylene (layer B having a specific gravity of 0.89);
A resin system in which 100 parts by weight of a styrene-butadiene block copolymer having 15% by weight of butadiene and 18 parts by weight of polystyrene were mixed (a C layer having a specific gravity of 1.04) was charged into separate extruders. After being extruded from a T-die at 240 ° C. so as to form a laminate of B / A / B / C, and cooled and solidified by a cooling roll at 30 ° C., the tenter is stretched 6 times in the transverse direction at 90 ° C. The film was annealed at 80 ° C. for 5 seconds while relaxing 8% in the width direction in the above to obtain a heat-shrinkable label film having a thickness of 50 μm (the thickness of each layer was 4 μm).
/ 2 μm / 38 μm / 2 μm / 4 μm). Table 1 shows the physical property values of the obtained heat shrinkable label film.
【００３４】 [0034]
【００３５】（実施例２） 実施例１で得たフィルムをスリッター機で幅９６０ｍｍ
にスリットした。次いで、フィルムの片面にグラビア印
刷機で５色印刷を施した。印刷図柄は、フィルムの幅方
向に３丁取りで、フィルムの流れ方向に非印刷部が６ｍ
ｍの幅で間欠的にある図柄を使用した。次いで、スリッ
ター機で３丁にスリットした。次いで、シール溶剤とし
てＴＨＦ／ｎ−ヘキサン系を用いて、速度１３０ｍ／分
でセンターシールした。次いで、非印刷部の中央でカッ
トして、折り径５７ｍｍ、長さ８３ｍｍの熱収縮性ラベ
ルを得た。シール強度は５９０ｇ／ｃｍであった。次い
で、図１で示すように、ＰＥＴボトルに熱収縮性ラベル
を被せ、湿熱方式の収縮トンネル（長さ３ｍ、蒸気圧
０．３ｋｇ／ｃｍ２）を用いて８０℃×５秒間で熱収縮
させた。ラベルはタイトにボトルに装着しており、皺、
あばた、縦引け、フィルムの白化、図柄のゆがみ等異常
は無かった。Example 2 The film obtained in Example 1 was 960 mm wide by a slitter.
Slit. Next, five-color printing was performed on one side of the film using a gravure printing machine. The print pattern is three in the width direction of the film, and the non-printed part is 6 m in the film flow direction.
An intermittent pattern with a width of m was used. Next, three slits were made with a slitter. Next, center sealing was performed at a speed of 130 m / min using a THF / n-hexane system as a sealing solvent. Next, cutting was performed at the center of the non-printing portion to obtain a heat-shrinkable label having a folded diameter of 57 mm and a length of 83 mm. The seal strength was 590 g / cm. Next, as shown in FIG. 1, a PET bottle is covered with a heat-shrinkable label, and heat-shrinked at 80 ° C. for 5 seconds using a wet-heat shrink tunnel (length 3 m, vapor pressure 0.3 kg / cm 2 ). Was. The label is attached to the bottle tightly, wrinkles,
There were no abnormalities such as pocking, vertical shrinkage, whitening of the film, and distortion of the design.
【００３６】（実施例３） このようにして得た１００本のＰＥＴボトルに９８℃の
温水をホット充填し、アルミキャップをした。ホット充
填後のラベルの状態は、充填前と全く同じく異常がなか
った。また、ラベル同士が融着することも無かった。Example 3 100 PET bottles thus obtained were hot-filled with hot water at 98 ° C. and capped with aluminum. The state of the label after hot filling was completely the same as before filling. Also, there was no fusion between the labels.
【００３７】次いで、１００本のＰＥＴボトルの水を捨
て、再度アルミキャップを被せた。次いでこれらを粉砕
機で７〜１０ｍｍ角に粉砕し、比重分離機にかけたとこ
ろ、熱収縮性ラベル粉砕体はすばやく水に浮かび、アル
ミキャップとＰＥＴボトルの粉砕体は水に沈んだ。Next, the water in the 100 PET bottles was discarded, and the PET bottle was covered again with an aluminum cap. Then, these were pulverized to 7 to 10 mm square by a pulverizer and then subjected to a specific gravity separator. As a result, the heat-shrinkable label pulverized body quickly floated on water, and the pulverized body of the aluminum cap and the PET bottle was submerged in water.
【００３８】[0038]
【発明の効果】本発明は、以上詳述したような形態で実
施され、以下に記載されるような効果を奏す。The present invention is embodied in the form described in detail above and has the following effects.
【００３９】本発明の熱収縮性ラベル用フィルムは溶剤
でセンターシールができるので、シール加工が簡単にで
き、シール加工速度も早く、また、シール強度も強く且
つ安定している。また、熱収縮性のない接着剤によるシ
ールではないので、得られたラベルをＰＥＴボトルに熱
収縮装着させても、シール強度の低下がない。このた
め、中味商品のホット充填、ボイル処理等以後の加熱工
程時にもシール部が剥離することがない。また、フィル
ムは共押出し、共延伸により製造されるので、１つの製
造工程でフィルムが得られるのみならず、接着樹脂層も
熱収縮性があるので、熱収縮、ホット充填、ボイル処理
等の加熱工程で皺が入ることもない。また、ラベルは比
重が１より小さいので比重分離機で分離することがで
き、ＰＥＴボトルのリサイクルに有利である。また、本
発明の熱収縮性ラベル用フィルムから得られたラベルが
装着されたＰＥＴボトルは、リサイクルに有利なボトル
である。Since the heat-shrinkable label film of the present invention can be subjected to center sealing with a solvent, the sealing can be easily performed, the sealing speed is high, and the sealing strength is strong and stable. In addition, since the seal is not a seal made of an adhesive having no heat shrinkage, the seal strength does not decrease even if the obtained label is heat shrunk to a PET bottle. For this reason, the sealing portion does not peel off even during a heating step after hot filling of content items, boil processing, and the like. In addition, since the film is manufactured by co-extrusion and co-stretching, not only can the film be obtained in one manufacturing step, but also the adhesive resin layer has heat shrinkage, so that heat such as heat shrinkage, hot filling, and boil processing can be used. No wrinkles are formed in the process. Further, since the label has a specific gravity of less than 1, it can be separated by a specific gravity separator, which is advantageous for recycling PET bottles. A PET bottle to which a label obtained from the heat shrinkable label film of the present invention is attached is a bottle that is advantageous for recycling.
【図１】本発明のフィルムから得られた熱収縮性ラベ
ル、及びそれが装着されたＰＥＴボトルを示す斜視図で
ある。FIG. 1 is a perspective view showing a heat-shrinkable label obtained from a film of the present invention and a PET bottle to which the label is attached.
【図２】センターシール加工を説明する断面図である。FIG. 2 is a cross-sectional view illustrating a center sealing process.
【図３】熱収縮性ラベルの断面図である。FIG. 3 is a cross-sectional view of a heat-shrinkable label.
１、１’ 熱収縮性ラベル ２ 熱収縮性ラベル用フィルム ３ 印刷部 ４ シール溶剤塗布用ノズル ５ ＰＥＴボトル 1, 1 'heat-shrinkable label 2 film for heat-shrinkable label 3 printing section 4 nozzle for applying sealing solvent 5 PET bottle
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平６−27885（ＪＰ，Ａ) 特開 平４−97841（ＪＰ，Ａ) 特開 平６−31874（ＪＰ，Ａ) 特開 平３−138145（ＪＰ，Ａ) 特開 平８−90738（ＪＰ，Ａ) 特開 平６−23890（ＪＰ，Ａ) 特開 平５−96620（ＪＰ，Ａ) 実開 昭55−69042（ＪＰ，Ｕ) (58)調査した分野(Int.Cl.7，ＤＢ名) G09F 3/04 B32B 1/00 - 35/00 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-6-27885 (JP, A) JP-A-4-97841 (JP, A) JP-A-6-31874 (JP, A) 138145 (JP, A) JP-A-8-90738 (JP, A) JP-A-6-23890 (JP, A) JP-A-5-9620 (JP, A) Japanese Utility Model Laid-Open No. 55-69042 (JP, U) (58) Field surveyed (Int. Cl. 7 , DB name) G09F 3/04 B32B 1/00-35/00
Claims (8)
除く）を芯材とし、その両面に押出成形用接着樹脂の層
を介して下記のポリスチレン系樹脂を主成分とする樹脂
層が積層された、比重が０．９９以下である熱収縮性ラ
ベル用フィルム。ポリスチレン系樹脂：ブタジエン含有
量１０〜４０重量％比重１．０２〜１．０８のスチレン
−ブタジエンブロック共重合体１００重量部にポリスチ
レンを２〜５０重量部混合した樹脂、又は、イソプレン
含有量１０〜４０重量％比重１．０２〜１．０８のスチ
レン−イソプレンブロック共重合体１００重量部にポリ
スチレンを２〜５０重量部混合した樹脂。 1. A polyolefin resin layer (provided that a foamed resin layer is
Excluding) as a core material, and a resin layer containing the following polystyrene resin as a main component laminated on both surfaces thereof via an adhesive resin layer for extrusion molding, for a heat-shrinkable label having a specific gravity of 0.99 or less. the film. Polystyrene resin: Contains butadiene
Styrene having an amount of 10 to 40% by weight and a specific gravity of 1.02 to 1.08
-Polystyrene is added to 100 parts by weight of butadiene block copolymer.
Resin mixed with 2 to 50 parts by weight of len, or isoprene
Steel with a content of 10 to 40% by weight and a specific gravity of 1.02 to 1.08
100 parts by weight of len-isoprene block copolymer
Resin containing 2 to 50 parts by weight of styrene.
２〜１０モル％のエチレン−プロピレンランダム共重合
体を主成分とする層である、請求項１に記載の熱収縮性
ラベル用フィルム。2. The polyolefin resin layer according to claim 1, wherein said polyolefin resin layer contains ethylene in an amount of 0.1 to 0.2.
The heat-shrinkable label film according to claim 1, which is a layer mainly composed of 2 to 10 mol% of an ethylene-propylene random copolymer.
２〜１０モル％のエチレン−プロピレンランダム共重合
体１００重量部に石油樹脂２〜５０重量部を混合した樹
脂系を主成分とする層である、請求項１に記載の熱収縮
性ラベル用フィルム。3. The polyolefin resin layer according to claim 1, wherein said polyolefin resin layer has a content of ethylene of 0.1%.
The heat-shrinkable label film according to claim 1, wherein the layer is a resin-based layer obtained by mixing 2 to 50 parts by weight of a petroleum resin with 100 parts by weight of an ethylene-propylene random copolymer of 2 to 10 mol%. .
６０ｇ／１０ｍｉｎの接着樹脂を主成分とする層であ
る、請求項１〜３のいずれか１項に記載の熱収縮性ラベ
ル用フィルム。4. The adhesive resin layer for extrusion molding has an MFR of 0.2 to 0.2.
The heat-shrinkable label film according to any one of claims 1 to 3, wherein the heat-shrinkable label film is a layer containing an adhesive resin of 60 g / 10 min as a main component.
チレン樹脂を主成分とする層である、請求項１〜４のい
ずれか１項に記載の熱収縮性ラベル用フィルム。5. The heat-shrinkable label film according to claim 1, wherein the layer of the adhesive resin for extrusion molding is a layer containing an acid-modified polyethylene resin as a main component.
０．９０の酸変性超低密度ポリエチレン樹脂である、請
求項５に記載の熱収縮性ラベル用フィルム。6. An acid-modified polyethylene resin having a specific gravity of 0.88 or less.
The heat-shrinkable label film according to claim 5, which is an acid-modified ultra-low-density polyethylene resin of 0.90.
た、請求項１〜６のいずれか１項に記載の熱収縮性ラベ
ル用フィルム。7. Manufactured by coextrusion technology, drawing technology.
The heat-shrinkable label film according to any one of claims 1 to 6 .
縮性ラベル用フィルムからなるラベルが装着されたＰＥ
Ｔボトル。8. A heat collector according to claim 1, wherein
PE attached with label made of shrinkable label film
T bottle .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08944598A JP3286594B2 (en) | 1998-03-17 | 1998-03-17 | Heat shrinkable label film and PET bottle on which label made of the film is attached |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08944598A JP3286594B2 (en) | 1998-03-17 | 1998-03-17 | Heat shrinkable label film and PET bottle on which label made of the film is attached |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11262981A JPH11262981A (en) | 1999-09-28 |
| JP3286594B2 true JP3286594B2 (en) | 2002-05-27 |
Family
ID=13970891
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP08944598A Expired - Fee Related JP3286594B2 (en) | 1998-03-17 | 1998-03-17 | Heat shrinkable label film and PET bottle on which label made of the film is attached |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3286594B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005118288A1 (en) * | 2004-06-03 | 2005-12-15 | Mitsubishi Plastics, Inc. | Heat shrink laminate film, molding utilizing the film, heat shrink label and container |
| EP1925446A1 (en) | 2006-11-27 | 2008-05-28 | C.I. Kasei Co., Ltd | Heat shrinkable multi-layer film and method for preparing the same |
| WO2014010406A1 (en) | 2012-07-10 | 2014-01-16 | 株式会社フジシールインターナショナル | Shrink film and shrink label |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4593759B2 (en) * | 1999-11-16 | 2010-12-08 | 株式会社フジシールインターナショナル | Labeled container |
| JP2002029514A (en) * | 2000-07-18 | 2002-01-29 | Dainippon Printing Co Ltd | Heat shrinking cylindrical label and its manufacturing method |
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| JP5025191B2 (en) * | 2005-08-31 | 2012-09-12 | 三菱樹脂株式会社 | Heat-shrinkable laminated film, molded product using the film, heat-shrinkable label, and container |
| BRPI0620471A2 (en) * | 2005-11-15 | 2011-11-08 | Dow Global Technologies Inc | multilayer oriented shrink film and shrink label |
| US20090061245A1 (en) | 2006-03-31 | 2009-03-05 | Fuji Seal International, Inc. | Shrink Film |
| JP5042730B2 (en) * | 2006-06-30 | 2012-10-03 | 三菱樹脂株式会社 | Heat-shrinkable laminated film, molded article using the film, heat-shrinkable label, and container |
| JP2008284757A (en) * | 2007-05-16 | 2008-11-27 | Fuji Seal International Inc | Shrink film and shrink label |
| JP4980802B2 (en) * | 2007-06-27 | 2012-07-18 | 株式会社フジシールインターナショナル | Shrink film and shrink label |
| JP5560042B2 (en) | 2007-12-27 | 2014-07-23 | 株式会社フジシールインターナショナル | Shrink film and cylindrical shrink label |
| US9555419B2 (en) | 2012-05-07 | 2017-01-31 | Eastman Chemical Company | Films containing foamable inks or coatings and process for separating similar density materials |
| JP2015520420A (en) * | 2012-06-05 | 2015-07-16 | エーブリー デニソン コーポレイションＡｖｅｒｙ Ｄｅｎｎｉｓｏｎ Ｃｏｒｐｏｒａｔｉｏｎ | Label with information dye |
| FR2997342B1 (en) * | 2012-10-26 | 2014-12-05 | Sleever Int | MULTILAYER THERMORETRACTABLE PLASTIC FILM |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5752019Y2 (en) * | 1978-11-06 | 1982-11-12 | ||
| EP0418836A3 (en) * | 1989-09-22 | 1991-11-21 | Hercules Incorporated | Multilayer oriented film containing polypropylene and co-polyester |
| JP2911565B2 (en) * | 1990-08-16 | 1999-06-23 | 三井・デュポンポリケミカル株式会社 | Laminate |
| JPH06102362B2 (en) * | 1991-10-07 | 1994-12-14 | 三井東圧化学株式会社 | Method for manufacturing label composed of laminated film |
| JP2615303B2 (en) * | 1992-03-13 | 1997-05-28 | 三井東圧化学株式会社 | Heat shrinkable label |
| JPH0759390B2 (en) * | 1992-03-23 | 1995-06-28 | 三井東圧化学株式会社 | label |
| JPH0631881A (en) * | 1992-07-14 | 1994-02-08 | Mitsubishi Kasei Corp | Laminate |
| JP2874462B2 (en) * | 1992-07-20 | 1999-03-24 | 凸版印刷株式会社 | Multi-layer plastic structure |
| JP3493474B2 (en) * | 1994-09-20 | 2004-02-03 | 大倉工業株式会社 | Polyolefin-based heat-shrinkable multilayer film |
-
1998
- 1998-03-17 JP JP08944598A patent/JP3286594B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005118288A1 (en) * | 2004-06-03 | 2005-12-15 | Mitsubishi Plastics, Inc. | Heat shrink laminate film, molding utilizing the film, heat shrink label and container |
| EP1925446A1 (en) | 2006-11-27 | 2008-05-28 | C.I. Kasei Co., Ltd | Heat shrinkable multi-layer film and method for preparing the same |
| WO2014010406A1 (en) | 2012-07-10 | 2014-01-16 | 株式会社フジシールインターナショナル | Shrink film and shrink label |
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| Publication number | Publication date |
|---|---|
| JPH11262981A (en) | 1999-09-28 |
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