JP2005254458A - Heat-shrinkable olefinic laminated film - Google Patents
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本発明は、自然収縮性に優れ、フィルム表面での収縮時の指紋付着部白化現象が抑制された、特にラベル用として品質バランスの良い熱収縮性オレフィン系積層フィルムに関する。 The present invention relates to a heat-shrinkable olefin-based laminated film that has excellent natural shrinkage and suppresses the phenomenon of whitening of a fingerprint-adhered portion when shrinking on the film surface, and has a good quality balance especially for labels.
ジュース等の清涼飲料水は瓶あるいはペットボトルといった容器に充填されて販売される。その際、他商品との差別化や商品の視認性向上のために、容器外側に、内面に印刷が施された熱収縮性ラベルを装着する場合が多い。ラベルの材質としてはポリスチレン、ポリエステル、ポリ塩化ビニル、ポリオレフィン等がある。 Soft drinks such as juice are sold in containers such as bottles or PET bottles. At that time, in order to differentiate from other products and improve the visibility of the products, a heat-shrinkable label whose inner surface is printed is often attached to the outside of the container. Examples of the label material include polystyrene, polyester, polyvinyl chloride, and polyolefin.
また、容器がペットボトルの場合、リサイクルのために使用後回収したペットボトルからフレークやペレットに再生されることが多くなってきている。この工程の概略を以下に説明する。回収されたペットボトル（通常、ポリエチレン製等の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、ペットボトルは数ｍｍ〜１０ｍｍ角に粉砕され、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やキャップが除去される。更に、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。こうして得たペットボトル粉砕体から、再生ペットフレークまたは再生ペットペレットが得られる。 In addition, when the container is a plastic bottle, the plastic bottle collected after use for recycling is often recycled into flakes and pellets. An outline of this process will be described below. Collected PET bottles (usually with polyethylene caps and heat-shrinkable labels) can be used for other containers such as glass bottles, cans, and PVC bottles by hand, weight separator, X-ray inspection, etc. Sorted out from Next, the PET bottle is pulverized into several mm to 10 mm square, and the heat-shrinkable label pulverized body and cap having a specific gravity of less than 1 are removed by a specific gravity separator. Further, the heat-shrinkable label pulverized body having a specific gravity of 1 or more is removed by the wind separator. Recycled pet flakes or regenerated pet pellets are obtained from the PET bottle pulverized body thus obtained.
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やキャップ）と水に沈むもの（比重が１以上の熱収縮性ラベルやペットボトル粉砕体）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、比重分離機で除去できる比重が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 means that a pulverized body is put in water and floats in water (a heat-shrinkable label or cap having a specific gravity of less than 1) and a thing that sinks in water (a heat-shrinkable label or plastic bottle having a specific gravity of 1 or more) The wind power separator is a device that expands the pulverized body and blows the heat-shrinkable label pulverized body by blowing air from below. From each principle, the specific gravity separator has a large throughput per unit time, while that of the wind separator is small. For this reason, a heat-shrinkable label having a specific gravity of less than 1 that can be removed by a specific gravity separator is desired.
また、近年ペットボトルに被覆するラベル用途では、需要の増大が見込まれているため、ボトルへのラベル被覆工程において比較的短時間、なおかつ比較的低温で高度な収縮仕上がり外観が得られることが要求され、つまり、最近のペットボトルおよびビンにおけるシュリンクフィルムのラベリング工程は主に蒸気シュリンカーが主流となっており、さらに無菌充填や、内容物の温度による品質低下等を回避するために、シュリンカーの温度を下げる必要が出てきている。そのため、フィルムはなるべく低温で収縮を開始することを要求され、シュリンカーに入り、ラベルが低温の状態において収縮を開始するとともに、シュリンカー通過後、優れた収縮仕上がりが得られることを要求されている。
同時に、自然収縮性率の小さいフィルムの要求も要求されてきている。これは室温下において徐々に収縮がおこる現象で、フィルム寸法が変化したり、ロール巻きにした状態では変形などが起きたりして包装時や二次加工時にトラブルが生じる場合がある。
In recent years, demand for labeling on PET bottles is expected to increase, so it is necessary to obtain a highly shrink-finished appearance at a relatively short time and at a relatively low temperature in the label coating process on bottles. In other words, the shrink film labeling process in recent PET bottles and bottles is mainly steam shrinker. Furthermore, in order to avoid aseptic filling and quality deterioration due to temperature of contents, shrinker It is necessary to lower the temperature. Therefore, the film is required to start shrinking at as low a temperature as possible, enters the shrinker, starts to shrink in the low temperature state, and is required to obtain an excellent shrink finish after passing through the shrinker. Yes.
At the same time, there is a demand for a film having a low natural shrinkage rate. This is a phenomenon in which shrinkage occurs gradually at room temperature, and there are cases where troubles occur during packaging or secondary processing due to changes in film dimensions, deformation, etc. when rolled.
前記ラベルの材質のうちポリスチレン、ポリエステル、ポリ塩化ビニルラベルは比重が１より大きいため、リサイクル工程において比重分離機で分離できないという問題がある。一方、ポリオレフィンラベルは比重が１未満であるが、腰や光沢が不十分であり、有機溶剤によるセンターシール加工では製造することができないという問題がある。さらに、ポリオレフィンラベルは熱収縮温度を高くしないと収縮しないため、耐熱性のない、例えば非耐熱ペットボトルには使用できないという問題がある。 Among the label materials, polystyrene, polyester, and polyvinyl chloride labels have a specific gravity greater than 1, and thus cannot be separated by a specific gravity separator in the recycling process. On the other hand, the polyolefin label has a specific gravity of less than 1, but has a problem that its waist and gloss are insufficient and cannot be produced by center seal processing with an organic solvent. Furthermore, since the polyolefin label does not shrink unless the heat shrink temperature is raised, there is a problem that it has no heat resistance, for example, cannot be used for a non-heat resistant PET bottle.
そこで、これらの問題について検討したところ、環状オレフィン系樹脂等の非晶質樹脂からなる層とポリオレフィン系樹脂からなる層とが積層された比重１以下のシュリンクフィルムが見出された。この環状オレフィン系樹脂からなる熱収縮性フィルムは透明性、光沢に優れ、適度の腰を有するため種々の包装材料として数多く検討されている。例えば特許文献１では、密度０．９４ｇ／ｃｍ３未満のオレフィン系樹脂を主成分とする層を中間層とし、環状ポリオレフィン系樹脂を主成分とする層を表裏面に設けて積層体を形成し、その積層体を３〜６倍延伸することで得られる、比重が０．９６未満である熱収縮性フィルムが開示されている。しかし、環状オレフィン系樹脂で表裏面を形成する熱収縮性フィルムは、フィルム表面に指紋等の油脂が付着した状態で熱収縮をさせると、その油脂付着部分に白化を生じ美観を損ねるといった問題が生じ易い。また、特許文献２では、指紋付着部の白化防止を目的とし、環状オレフィン１００重量部に対し直鎖状低密度ポリエチレンを６０〜１５０重量部ブレンドした表裏層とプロピレン−α−オレフィンランダム共重合体を主とする中間層からなる積層熱収縮フィルムが開示されている。しかしながら、本発見者らの知見に依れば、自然収縮率が大きいという欠点を有していた。 Therefore, when these problems were examined, a shrink film having a specific gravity of 1 or less in which a layer made of an amorphous resin such as a cyclic olefin resin and a layer made of a polyolefin resin were laminated was found. The heat-shrinkable film made of this cyclic olefin resin is excellent in transparency and gloss, and has an appropriate waist, so that it has been studied as a variety of packaging materials. For example, in Patent Document 1, a layer composed mainly of an olefin resin having a density of less than 0.94 g / cm 3 is used as an intermediate layer, and layers having a cyclic polyolefin resin as a main component are provided on the front and back surfaces to form a laminate. A heat-shrinkable film having a specific gravity of less than 0.96, obtained by stretching the laminate 3-6 times, is disclosed. However, heat-shrinkable films that form the front and back surfaces with a cyclic olefin resin have the problem that, when heat-shrinkable with fingerprints and other oils attached to the film surface, the oil-attached parts are whitened and the appearance is impaired. It is likely to occur. Moreover, in patent document 2, the front and back layer which blended 60-150 weight part of linear low density polyethylene with 100 weight part of cyclic olefins, and the propylene-alpha-olefin random copolymer aiming at the whitening prevention of a fingerprint adhesion part. A laminated heat-shrinkable film comprising an intermediate layer mainly composed of is disclosed. However, according to the findings of the present inventors, there was a drawback that the natural shrinkage rate was large.
本発明が解決しようとする課題はかかる熱収縮性フィルムに要求される、自然収縮性と耐指紋付着性が良好で、かつ収縮性に優れた熱収縮性オレフィン系積層フィルムを提供することにある。 The problem to be solved by the present invention is to provide a heat-shrinkable olefin-based laminated film which is required for such a heat-shrinkable film, has good natural shrinkage and anti-fingerprint adhesion, and is excellent in shrinkage. .
本発明では
１ 表裏層がガラス転移温度が５５℃〜１０５℃の環状オレフィン系共重合樹脂７０〜９０重量％に対し低密度ポリエチレン１０〜３０重量％をブレンドした樹脂組成物で構成され、中間層がオレフィン系樹脂を主成分とする樹脂組成物から構成されている少なくとも３層からなる熱収縮性オレフィン系積層フィルムを構成すること
２ 前記中間層の主成分であるオレフィン系樹脂の結晶融解ピーク温度（Ｔｍ）が１３５〜１７０℃であり、かつ動的粘弾性測定により周波数１０Ｈｚ、温度９０℃で測定した貯蔵弾性率（Ｅ‘）が３．０×１０６〜５．０×１０8Ｐａである熱収縮性オレフィン系積層フィルムを構成すること
３ 積層フィルムの厚みが表裏層/中間層/表裏層＝１/６/１〜１/２/１の範囲で構成すること
により前記問題を解決するに至った。
In the present invention, the front and back layers are composed of a resin composition obtained by blending 10 to 30% by weight of low density polyethylene with 70 to 90% by weight of cyclic olefin copolymer resin having a glass transition temperature of 55 to 105 ° C. Constituting a heat-shrinkable olefin-based laminated film composed of at least three layers composed of a resin composition containing olefin-based resin as a main component 2 Crystal melting peak temperature of olefin-based resin as a main component of the intermediate layer (Tm) is 135 to 170 ° C., and the storage elastic modulus (E ′) measured by dynamic viscoelasticity measurement at a frequency of 10 Hz and a temperature of 90 ° C. is 3.0 × 10 6 to 5.0 × 10 8 Pa. Constructing a certain heat-shrinkable olefin-based laminated film 3 Solving the above problems by constructing the laminated film in the range of front / back layer / intermediate layer / front / back layer = 1/6/1 to 1/2/1 It was decided.
本発明によれば、自然収縮性と耐指紋付着性が良好で、かつ収縮性に優れた熱収縮性オレフィン系積層フィルムが提供できる。 According to the present invention, it is possible to provide a heat-shrinkable olefin-based laminated film having good natural shrinkage and fingerprint resistance and excellent shrinkage.
以下、発明を詳細に説明する。
本発明で使用する環状オレフィン系樹脂とは一般的な総称であり、具体的には、（ａ）環状オレフィンの開環（共）重合体を必要に応じ水素添加した重合体、（ｂ）環状オレフィンの付加（共）重合体、（ｃ）環状オレフィンとエチレン、プロピレン等α−オレフィンとのランダム共重合体、（ｄ）前記（ａ）〜（ｃ）を不飽和カルボン酸やその誘導体等で変性したグラフト変性体等が例示できる。環状オレフィンとしては特に限定するものではなく、例えばノルボルネンやテトラシクロドデセンが例示できる。この環状オレフィン系共重合樹脂は、具体的には日本ゼオン製の商品名「ＺＥＯＮＯＲ」や三井化学（（株））製の商品名「アペル」やＴｉｃｏｎａ社製の商品名「Ｔｏｐａｓ」を例示することができる。また環状オレフィン系樹脂の比重は一般的には１．００〜１．０５である。
Hereinafter, the invention will be described in detail.
The cyclic olefin resin used in the present invention is a general generic name. Specifically, (a) a polymer obtained by hydrogenating a ring-opened (co) polymer of a cyclic olefin as necessary, (b) cyclic Addition (co) polymers of olefins, (c) random copolymers of cyclic olefins and α-olefins such as ethylene and propylene, (d) (a) to (c) above with unsaturated carboxylic acids or their derivatives Examples include modified graft modified products. The cyclic olefin is not particularly limited, and examples thereof include norbornene and tetracyclododecene. Specific examples of the cyclic olefin copolymer resin include a product name “ZEONOR” manufactured by Nippon Zeon Co., Ltd., a product name “Apel” manufactured by Mitsui Chemicals, Inc., and a product name “Topas” manufactured by Ticona. be able to. The specific gravity of the cyclic olefin resin is generally 1.00 to 1.05.
上記環状オレフィン系樹脂のガラス転移温度は、好ましくは５５〜１０５℃、より好ましくは５５〜９０℃であることが望ましい。５５℃未満では、自然収縮性が高くなる傾向にあり、１０５℃を超えると、約７０〜９０℃の蒸気シュリンカー温度における主延伸方向の熱収縮率が小さくなりすぎる傾向にある。 The glass transition temperature of the cyclic olefin resin is preferably 55 to 105 ° C, more preferably 55 to 90 ° C. If it is less than 55 ° C., the natural shrinkage tends to be high, and if it exceeds 105 ° C., the thermal shrinkage in the main stretching direction at a steam shrinker temperature of about 70 to 90 ° C. tends to be too small.
本発明の上記表裏層にブレンドされる低密度ポリエチレンは、エチレンと炭素数４〜８までのα−オレフィンの共重合体であり、チーグラー触媒及びメタロセン触媒系のＬＤＰＥおよびＬＬＤＰＥを挙げることが出来る。 The low density polyethylene blended in the front and back layers of the present invention is a copolymer of ethylene and an α-olefin having 4 to 8 carbon atoms, and examples thereof include Ziegler catalyst and metallocene catalyst type LDPE and LLDPE.
上記低密度ポリエチレンの密度は０．９００〜０．９３０ｇ／ｃｍ３が好ましく、より好ましくは０．９０５〜０．９２５ｇ／ｃｍ３である。密度が０．９００ｇ／ｃｍ３未満の場合、ポリエチレンの融点が低く、該フィルム表面の耐熱性が低下する為、例えば装着ライン上やボトルウォーマ内でフィルムがブロッキングする現象が生じやすい。一方密度が０．９３０ｇ／ｃｍ３を超える場合には延伸時にフィルムのヘーズが悪くなりやすい。 The density of the low density polyethylene is preferably 0.900 to 0.930 g / cm 3 , more preferably 0.905 to 0.925 g / cm 3 . When the density is less than 0.900 g / cm 3 , the melting point of polyethylene is low, and the heat resistance of the film surface is lowered. For example, the phenomenon that the film is blocked on the mounting line or in the bottle warmer is likely to occur. On the other hand, when the density exceeds 0.930 g / cm 3 , the haze of the film tends to deteriorate during stretching.
また低密度ポリエチレンのＭＦＲ（１９０℃、２１．１８Ｎ）は好ましくは１．０〜１５ｇ／１０ｍｉｎ、より好ましくは１．５〜１０ｇ／１０ｍｉｎである。ＭＦＲが１．０ｇ／１０ｍｉｎ未満の場合には環状オレフィン系樹脂との混練分散が悪くなり、透明性の悪いフィルムとなる傾向にある。一方、ＭＦＲが１５ｇ／１０ｍｉｎを超える場合、ブレンド樹脂の溶融粘度の低下により安定した吐出が困難となり、均一な厚みのフィルムが得られにくい。 Moreover, MFR (190 degreeC, 21.18N) of a low density polyethylene becomes like this. Preferably it is 1.0-15 g / 10min, More preferably, it is 1.5-10 g / 10min. When the MFR is less than 1.0 g / 10 min, the kneading dispersion with the cyclic olefin-based resin is deteriorated, and the film tends to have poor transparency. On the other hand, when the MFR exceeds 15 g / 10 min, stable discharge becomes difficult due to a decrease in the melt viscosity of the blend resin, and it is difficult to obtain a film having a uniform thickness.
環状オレフィンと低密度ポリエチレンの割合は、環状オレフィン系樹脂７０〜９０重量％に対して１０〜３０重量％、が好ましい。１０重量％未満の場合には前記の指紋白化現象に対する効果が薄いほか、オレフィン系樹脂からなる中間層との層間接着力が乏しく、該フィルム製袋時や印刷時に層間剥離が生じやすい。一方、３０重量％を超える場合には透明性に劣る、腰が低い、自然収縮率が大きい等の問題が生じるほか、該フィルムに印刷を施す際のインキ密着性が極端に悪くなる。表裏層の樹脂組成、即ち環状オレフィン系樹脂や低密度ポリエチレンの種類は、同じものであっても異なるものであってもよい。 The ratio of the cyclic olefin to the low density polyethylene is preferably 10 to 30% by weight with respect to 70 to 90% by weight of the cyclic olefin resin. If it is less than 10% by weight, the effect on the above-mentioned fingerprint whitening phenomenon is low, and the interlayer adhesion with the intermediate layer made of olefin resin is poor, and delamination is likely to occur during film-making or printing. On the other hand, when it exceeds 30% by weight, problems such as inferior transparency, low waist, and large natural shrinkage occur, and ink adhesion when printing on the film is extremely deteriorated. The resin composition of the front and back layers, that is, the types of cyclic olefin resin and low density polyethylene may be the same or different.
さらに、上記表裏層には、炭化水素樹脂類を添加しても良い。炭化水素樹脂類を添加することにより、フィルム表面の光沢度が向上するという効果が得られる。炭化水素樹脂類の添加量は、環状オレフィン系樹脂と直鎖状低密度ポリエチレンとの樹脂組成物８０〜９５重量％に対して好ましくは５〜２５重量％である。添加量が５重量％未満の場合、添加による効果が小さく、２０重量％を超える場合には、脆いフィルムとなり易いほか、フィルム同士でブロッキングし易くなる。 Further, hydrocarbon resins may be added to the front and back layers. By adding hydrocarbon resins, the effect of improving the glossiness of the film surface can be obtained. The addition amount of the hydrocarbon resins is preferably 5 to 25% by weight with respect to 80 to 95% by weight of the resin composition of the cyclic olefin resin and the linear low density polyethylene. When the addition amount is less than 5% by weight, the effect of the addition is small, and when it exceeds 20% by weight, the film tends to be brittle and the films are easily blocked.
本発明の中間層に用いられるオレフィン系樹脂とは、収縮特性、延伸特性および経済性の点からプロピレン−エチレン共重合体、プロピレン−エチレン−ブテン−１共重合体、エチレン−α−オレフィン共重合体およびリアクタータイプのポリプロピレン系エラストマーが好ましい。また、これら２種以上のブレンド組成物から構成されても良い。 The olefin resin used for the intermediate layer of the present invention is a propylene-ethylene copolymer, a propylene-ethylene-butene-1 copolymer, an ethylene-α-olefin copolymer from the viewpoints of shrinkage characteristics, stretching characteristics and economy. Combined and reactor type polypropylene elastomers are preferred. Moreover, you may be comprised from these 2 or more types of blend compositions.
上記オレフィン系樹脂の示差走査熱量計(ＤＳＣ)により測定される融解温度は好ましくは１１０〜１７０℃、より好ましくは１３０〜１６０℃である。融解温度が１００℃以下の場合、耐熱性が不十分であり、例えばボトル装着時やボトルウォーマ内でブロッキングが発生した際、破断しやすい。一方１７０℃を超える場合は低温での延伸特性が低下するほか、良好な低温収縮が得られない。 The melting temperature of the olefin resin measured by a differential scanning calorimeter (DSC) is preferably 110 to 170 ° C, more preferably 130 to 160 ° C. When the melting temperature is 100 ° C. or lower, the heat resistance is insufficient. On the other hand, when the temperature exceeds 170 ° C., the drawing property at low temperature is deteriorated and good low temperature shrinkage cannot be obtained.
上記オレフィン系樹脂の動的粘弾性測定(周波数１０Ｈｚ、ひずみ０．１％)により得られる９０℃における貯蔵弾性率(E’)は、好ましくは３．０×１０６〜５．０×１０7Ｐａ、より好ましくは５．０×１０６〜３．０×１０7Ｐａである。９０℃における貯蔵弾性率が３．０×１０６Ｐａより低い場合、延伸過程における材料の弾性率が低下し、厚みの良好な製膜が困難である。一方９０℃における貯蔵弾性率が５．０×１０7Ｐａより高い場合、延伸の際に応力が高くなるため、分子配向がつよく行われる。その結果、常温付近に於いても残留応力による収縮応力が強くはたらく為、自然収縮が大きくなり易い。また、良好な収縮特性を得ることが難しいといった問題も生じる。 The storage elastic modulus (E ′) at 90 ° C. obtained by dynamic viscoelasticity measurement (frequency 10 Hz, strain 0.1%) of the olefin resin is preferably 3.0 × 10 6 to 5.0 × 10 7. Pa, more preferably 5.0 × 10 6 to 3.0 × 10 7 Pa. When the storage elastic modulus at 90 ° C. is lower than 3.0 × 10 6 Pa, the elastic modulus of the material in the stretching process is lowered, and it is difficult to form a film having a good thickness. On the other hand, when the storage elastic modulus at 90 ° C. is higher than 5.0 × 10 7 Pa, the stress is increased during stretching, so that the molecular orientation is vigorously performed. As a result, since the shrinkage stress due to the residual stress works strongly even at around room temperature, the natural shrinkage tends to increase. There is also a problem that it is difficult to obtain good shrinkage characteristics.
上記オレフィン系樹脂を主とする中間層組成物には、収縮特性を良くする目的で、炭化水素樹脂類を添加してもよい。添加する割合は本発明のオレフィン系樹脂６０〜９０重量％に対し炭化水素樹脂類を１０〜４０重量％が好ましい。炭化水素樹脂添加が１０重量％より少ない場合、収縮特性に対する効果が薄い。一方４０重量％より多い場合、炭化水素樹脂が積層界面に凝集するため、層間接着が極度に低下するほか、耐衝撃性の悪いフィルムになり易い。ここでいう炭化水素樹脂類とは脂肪族系炭化水素樹脂、芳香族系炭化水素樹脂、脂環族系炭化水素樹脂、又はそれらの水素添加物等一般に石油樹脂と呼称されるもの、あるいはロジン、ロジンエステル、テルペン樹脂等を指す。 Hydrocarbon resins may be added to the intermediate layer composition mainly composed of the olefin resin for the purpose of improving the shrinkage characteristics. The ratio of addition is preferably 10 to 40% by weight of hydrocarbon resins with respect to 60 to 90% by weight of the olefinic resin of the present invention. When the addition of hydrocarbon resin is less than 10% by weight, the effect on shrinkage characteristics is weak. On the other hand, when the content is more than 40% by weight, the hydrocarbon resin aggregates at the lamination interface, so that the interlayer adhesion is extremely lowered and a film having poor impact resistance tends to be formed. As used herein, the hydrocarbon resins are aliphatic hydrocarbon resins, aromatic hydrocarbon resins, alicyclic hydrocarbon resins, or hydrogenated products such as those generally called petroleum resins, or rosin, It refers to rosin ester, terpene resin and the like.
また上記オレフィン系樹脂には、成型加工性や熱収縮フィルムの物性を改良する目的で、本発明の効果を阻害しない範囲で、酸化防止剤、紫外線吸収剤、滑剤、光安定剤などの添加剤、改質剤を添加することも可能である。 In addition, the olefin-based resin has additives such as antioxidants, ultraviolet absorbers, lubricants, light stabilizers and the like within the range that does not impair the effects of the present invention for the purpose of improving the molding processability and physical properties of the heat shrinkable film. It is also possible to add a modifier.
本発明において、フィルムの層構成は表裏層と中間層からなる少なくとも３層構成のものであれば限定されない。３層構成では表裏層と中間層の厚みは前記各作用を損なわないように設定すればよいが、より効果的に発現するためには上記環状オレフィン系樹脂を主とする表裏層と上記オレフィン系樹脂を１／６／１〜１／２／１が望ましい。１／６／１よりも中間層の比率が大きい場合、自然収縮が大きくなり易く、また腰の低いフィルムになり易い。一方１／２／１よりも中間層の比率が小さい場合、比重が０．９５０ｇ／ｃｍ３よりも高くなり易い。 In the present invention, the layer structure of the film is not limited as long as it has at least three layers composed of front and back layers and an intermediate layer. In the three-layer configuration, the thicknesses of the front and back layers and the intermediate layer may be set so as not to impair each of the above actions. The resin is preferably 1/6/1 to 1/2/1. When the ratio of the intermediate layer is larger than 1/6/1, the natural shrinkage tends to increase, and the film tends to have a low waist. On the other hand, when the ratio of the intermediate layer is smaller than 1/2/1, the specific gravity tends to be higher than 0.950 g / cm 3 .
本発明のフィルムは公知の方法によって製造することができる。フィルムの形態としては平面状、チューブ状の何れであってもよいが、生産性（原反フィルムの幅方向に製品として数丁取りが可能）や内面に印刷が可能という点から平面状がより好ましい。平面状の場合の製造方法としては、例えば、複数の押出機を用いて樹脂を溶融し、Ｔダイから共押出し、チルドロールで冷却固化し、縦方向にロール延伸をし、横方向にテンター延伸をし、アニールし、冷却し、（印刷が施される場合にはその面にコロナ放電処理をして、）巻取機にて巻き取ることによりフィルムを得る方法が例示できる。また、チューブラー法により製造したフィルムを切り開いて平面状とする方法も適用できる。 The film of the present invention can be produced by a known method. The shape of the film may be either flat or tube-like, but it is more flat from the viewpoint of productivity (a few products can be taken in the width direction of the original film) and printing on the inner surface. preferable. As a production method in the case of a flat shape, for example, a resin is melted using a plurality of extruders, co-extruded from a T die, cooled and solidified with a chilled roll, roll-stretched in the vertical direction, and tenter-stretched in the horizontal direction. An example is a method of obtaining a film by winding, annealing, cooling, and winding with a winder (corona discharge treatment is applied to the surface when printing is performed). Moreover, the method of cutting open the film manufactured by the tubular method and making it flat is also applicable.
延伸倍率はオーバーラップ用等、二方向に収縮させる用途では、縦方向が２〜１０倍、横方向が２〜１０倍、好ましくは縦方向が３〜６倍、横方向が３〜６倍程度が望ましい。一方、収縮ラベル用等、主として一方向に収縮させる用途では、主収縮方向に相当する方向が２〜１０倍、好ましくは４〜８倍、それと直交する方向が１〜２倍（１倍とは延伸していないという意味）、好ましくは１．１〜１．５倍の、実質的には一軸延伸の範疇にある倍率比を選定するのが望ましい。通常の二軸延伸の倍率で得られるフィルムは主収縮方向と直交する方向の熱収縮率も大きくなるので、例えば、収縮ラベルとして用いる場合、容器に装着するとき容器の高さ方向にもフィルムが熱収縮する、いわゆる縦引け現象が起こり、好ましくない。 In applications where the stretching ratio is contracted in two directions, such as for overlap, the longitudinal direction is 2 to 10 times, the transverse direction is 2 to 10 times, preferably the longitudinal direction is 3 to 6 times, and the transverse direction is about 3 to 6 times. Is desirable. On the other hand, in applications that shrink mainly in one direction, such as for shrink labels, the direction corresponding to the main shrinking direction is 2 to 10 times, preferably 4 to 8 times, and the direction perpendicular to it is 1 to 2 times (1 times is It is desirable to select a magnification ratio of 1.1 to 1.5 times, preferably in the category of uniaxial stretching. Since the film obtained at a normal biaxial stretching ratio also has a large thermal shrinkage rate in the direction perpendicular to the main shrinkage direction, for example, when used as a shrinkage label, the film also extends in the height direction of the container when it is attached to the container. A so-called vertical shrinkage phenomenon that heat shrinks occurs, which is not preferable.
以下に、この発明について実施例を用いて説明する。尚、実施例に示す測定値及び評価は次のように行った。ここで、積層フィルムの引き取り（流れ）方向を「縦」方向、その直角方向を「横」方向と記載する。 The present invention will be described below with reference to examples. In addition, the measured value and evaluation which are shown to an Example were performed as follows. Here, the take-up (flow) direction of the laminated film is referred to as a “longitudinal” direction, and a direction perpendicular thereto is referred to as a “lateral” direction.
［熱収縮率］
積層フィルムを、縦１００ｍｍ、横１００ｍｍの大きさに切り取り、９０℃の温水バスに１０秒間浸漬し収縮量を測定した。熱収縮率は、横方向について収縮前の原寸に対する収縮量の比（％）で表した。
[Heat shrinkage]
The laminated film was cut to a size of 100 mm in length and 100 mm in width, and immersed in a hot water bath at 90 ° C. for 10 seconds, and the amount of shrinkage was measured. The thermal shrinkage rate was expressed as a ratio (%) of the shrinkage amount to the original size before shrinkage in the lateral direction.
［貯蔵弾性率］
測定試料を４ｍｍ、横６０ｍｍに切り出し、粘弾性スペクトロメーターＤＶＡ−２００（アイティ計測株式会社製）を用い、振動周波数１０Ｈｚ、ひずみ０．１％、昇温速度１℃/分、チャック間２５ｍｍで横方向について測定を行った。
[Storage modulus]
A measurement sample was cut out to 4 mm and 60 mm in width, using a viscoelastic spectrometer DVA-200 (made by IT Measurement Co., Ltd.), with a vibration frequency of 10 Hz, a strain of 0.1%, a heating rate of 1 ° C./min, and a width of 25 mm between chucks. The direction was measured.
［自然収縮率］
フィルムを縦１００ｍｍ、横１０００ｍｍの大きさに切りだし、３０℃の雰囲気の恒温槽に３０日間保管後、横方向の長さＡ（ｍｍ）を測定し、下記式より自然収縮率を算出した
自然収縮率（％）＝（１０００−Ａ）×１００÷１０００
[Natural shrinkage]
The film was cut into a size of 100 mm in length and 1000 mm in width, stored in a thermostatic chamber at 30 ° C. for 30 days, the length A (mm) in the horizontal direction was measured, and the natural shrinkage was calculated from the following formula.
Natural shrinkage (%) = (1000−A) × 100 ÷ 1000
［収縮仕上がり評価］
フィルムを縦１２０ｍｍ、横２３７ｍｍの大きさに切り出し、横の両端をトテラヒドロフラン(ＴＨＦ)にて溶剤シールし円筒状とした。この円筒状フィルムを容量２８０ミリリットルの円筒形ペットボトルに装着し、蒸気加熱方式で長さ３ｍの収縮トンネルで回転させずに約１０秒で通過させた。蒸気温度は９７℃、トンネル雰囲気温度は８７〜９５℃であった。フィルム装着後の発生したシワ、アバタ、ゆがみなどを目視で観察し、実用上問題ないものを○、実用上問題のあるものを×として評価した。
[Shrinkage finish evaluation]
The film was cut into a size of 120 mm in length and 237 mm in width, and both ends on the sides were solvent-sealed with terahydrofuran (THF) to form a cylinder. This cylindrical film was attached to a cylindrical plastic bottle having a capacity of 280 ml, and was passed through the steam heating system in about 10 seconds without being rotated in a contraction tunnel having a length of 3 m. The vapor temperature was 97 ° C. and the tunnel atmosphere temperature was 87 to 95 ° C. Wrinkles, avatars, distortions and the like generated after film mounting were visually observed, and those having no problem in practice were evaluated as ◯ and those having problems in practical use were evaluated as x.
［指紋白化現象の評価］
熱収縮性フィルムを、縦１００ｍｍ、横２１０ｍｍの大きさに切り取り、縦１３０ｍｍ、横１５０ｍｍ、チャック代１０ｍｍである固定枠にフィルムがたるんだ状態でセットし、指紋をフィルム表面に付着し、固定枠ごと９０℃の温水バスに１０秒間浸漬し、浸積後直ちに冷水の中に付けることで約２０％熱収縮させた状態のフィルムを採取する。２０％熱収縮させた後のフィルムの表面の菜種油をふき取り、菜種油を塗布した部位の白化を目視にて確認した。白化が見られないものについては○、白化は見られないが塗布部に跡がのこるものについては△、白化が見られたものについては×とした。
[Evaluation of fingerprint whitening phenomenon]
The heat-shrinkable film is cut into a size of 100 mm in length and 210 mm in width, set in a fixed frame with a length of 130 mm, width of 150 mm, and chuck allowance of 10 mm with the film sagging, and a fingerprint is attached to the film surface. Each film is immersed in a hot water bath at 90 ° C. for 10 seconds, and immediately after immersion, the film is heat-shrinked by about 20% by being immersed in cold water. The rapeseed oil on the surface of the film after 20% heat shrinkage was wiped off, and the whitening of the part where the rapeseed oil was applied was visually confirmed. The case where whitening was not observed was marked as ◯, the case where whitening was not observed but a mark remained on the coated part was marked as Δ, and the case where whitening was observed was marked as x.
（実施例１）
上記表裏層となるエチレンと環状オレフィンとのランダム共重合体（三井化学株式会社製 「ＡＰＥＬ８００８Ｔ」、Ｔｇ：７５℃）７０重量％と低密度ポリエチレン（日本ポリケム株式会社製 「ＬＦ４４０ＨＢ」、Ｔｍ：１１３℃）２０重量％と水添テルペン樹脂（ヤスハラケミカル株式会社製 「クリアロンＰ１５０」）１０重量％とのブレンドポリマー組成物、中間層となるエチレン−プロピレンゴム（出光石油化学株式会社製「ＰＥＲ Ｔ３１０Ｅ」、Ｔｍ：１５５℃）５５重量％と低密度ポリエチレン（日本ポリケム株式会社製 「 ＬＦ４４０ＨＢ」、Ｔｍ：１１３℃）３０重量％と脂肪族飽和炭化水素樹脂（荒川化学工業株式会社製 「アルコンＰ１４０」）１５重量％のブレンドポリマー組成物を、それぞれ同方向２軸押出機を用いて溶融混練し組成物のペレットを得た。この組成物をそれぞれ別個の押出機に投入後、各層の厚みが表裏層/中間層/表裏層＝１/４/１となるよう３層ダイスより共押出しし、５０℃キャストロールで引き取り固化させて幅２００ｍｍ、厚さ２００μｍの未延伸積層シートを得た。テンター延伸設備内にて、温度９０℃で一軸方向に４倍延伸し、膜厚５０μｍの熱収縮性フィルムを作成した。この熱収縮フィルムの結果を表１に示す。８０℃１０秒で収縮させたが、指紋付着部に白化は見られず、フィルム外観は美麗なものであった。また、自然収縮性も良好であった。
(Example 1)
70% by weight of a random copolymer of ethylene and cyclic olefin (Mitsui Chemical Co., Ltd. “APEL8008T”, Tg: 75 ° C.) and low density polyethylene (“LF440HB” manufactured by Nippon Polychem Co., Ltd.), Tm: 113 ° C) 20 wt% and hydrogenated terpene resin (Yasuhara Chemical Co., Ltd. “Clearon P150”) 10 wt% blend polymer composition, intermediate layer ethylene-propylene rubber (Idemitsu Petrochemical Co., Ltd. “PER T310E”, 55% by weight (Tm: 155 ° C.) and low density polyethylene (“LF440HB” manufactured by Nippon Polychem Co., Ltd.), 30% by weight and aliphatic saturated hydrocarbon resin (“Alcon P140” manufactured by Arakawa Chemical Industries, Ltd.) 15 Each of the blend polymer compositions of the weight percent was used in the same direction twin screw extruder The mixture was melt-kneaded to obtain composition pellets. This composition was put into separate extruders, then co-extruded from a three-layer die so that the thickness of each layer would be front / back layer / intermediate layer / front / back layer = 1/4/1, and taken and solidified by a 50 ° C. cast roll. Thus, an unstretched laminated sheet having a width of 200 mm and a thickness of 200 μm was obtained. In a tenter stretching facility, the film was stretched 4 times in a uniaxial direction at a temperature of 90 ° C. to prepare a heat-shrinkable film having a thickness of 50 μm. The results of this heat shrink film are shown in Table 1. Although the film was shrunk at 80 ° C. for 10 seconds, no whitening was observed at the fingerprint adhesion part, and the film appearance was beautiful. Moreover, the natural shrinkage was also good.
（実施例２）
上記表裏層となるエチレンと環状オレフィンとのランダム共重合体（三井化学株式会社製 「ＡＰＥＬ８００８Ｔ」、Ｔｇ：７５℃）７０重量％と、低密度ポリエチレン（日本ポリケム株式会社製 「ＬＦ４４０ＨＢ」）２０重量％と、水添テルペン樹脂（ヤスハラケミカル株式会社製 「クリアロンＰ１５０」）１０重量％とのブレンドポリマー組成物、エチレン−プロピレンーブレン三元共重合体（サンアロマー株式会社製 「Ａｄｓｙｌ５Ｃ３０Ｆ」、Ｔｍ：１４６℃）５０重量％と低密度ポリエチレン（日本ポリケム株式会社製 「ＬＦ４４０ＨＢ」）５０重量％とのブレンドポリマー組成物を、それぞれ同方向２軸押出機を用いて溶融混練し組成物のペレットを得た。この組成物をそれぞれ別個の押出機に投入後、各層の厚みが表裏層/中間層/表裏層＝１/４/１となるよう３層ダイスより共押出しし、５０℃キャストロールで引き取り固化させて幅２００ｍｍ、厚さ２００μｍの未延伸積層シートを得た。これをテンター延伸設備内にて、温度９０℃で一軸方向に４倍延伸し、膜厚５０μｍの熱収縮性フィルムを作成した。この熱収縮フィルムの結果を表１に示す。８０℃１０秒で収縮させたが、指紋付着部に白化は見られず、フィルム外観は美麗なものであった。また、自然収縮性も良好であった。
(Example 2)
Random copolymer of ethylene and cyclic olefin (Mitsui Chemical Co., Ltd. “APEL8008T”, Tg: 75 ° C.) 70 wt% and low density polyethylene (Nippon Polychem Co., Ltd. “LF440HB”) 20 wt. % And hydrogenated terpene resin ("Clearon P150" manufactured by Yashara Chemical Co., Ltd.) 10% by weight, ethylene-propylene-brene terpolymer ("Adsyl5C30F" manufactured by Sun Allomer Co., Ltd.), Tm: 146 ° C ) A blend polymer composition of 50% by weight and 50% by weight of low density polyethylene (“LF440HB” manufactured by Nippon Polychem Co., Ltd.) was melt-kneaded using a same-direction twin screw extruder to obtain pellets of the composition. This composition was put into separate extruders, then co-extruded from a three-layer die so that the thickness of each layer would be front / back layer / intermediate layer / front / back layer = 1/4/1, and taken and solidified by a 50 ° C. cast roll. Thus, an unstretched laminated sheet having a width of 200 mm and a thickness of 200 μm was obtained. This was stretched 4 times in a uniaxial direction at a temperature of 90 ° C. in a tenter stretching facility to prepare a heat-shrinkable film having a thickness of 50 μm. The results of this heat shrink film are shown in Table 1. Although the film was shrunk at 80 ° C. for 10 seconds, no whitening was observed at the fingerprint adhesion part, and the film appearance was beautiful. Moreover, the natural shrinkage was also good.
（実施例３）
上記表裏層となるエチレンと環状オレフィンとのランダム共重合体（三井化学株式会社製 「ＡＰＥＬ８００８Ｔ」、Ｔｇ：７５℃）７０重量％と低密度ポリエチレン（日本ポリケム株式会社製 「ＬＦ４４０ＨＢ」）２０重量％と水添テルペン樹脂（ヤスハラケミカル株式会社製 「クリアロンＰ１５０」）１０重量％とのブレンドポリマー組成物、中間層となるメタロセン系ＰＰ（日本ポリケム株式会社製 「ＸＫ１１６５」）２５重量％と低密度ポリエチレン（日本ポリケム株式会社製「 ＬＦ４４０ＨＢ」）６０重量％と脂肪族飽和炭化水素樹脂（荒川化学工業株式会社製 「アルコンＰ１４０」）１５重量％のブレンドポリマー組成物を、それぞれ同方向２軸押出機を用いて溶融混練し組成物のペレットを得た。この組成物をそれぞれ別個の押出機に投入後、各層の厚みが表裏層/中間層/表裏層＝１/４/１となるよう３層ダイスより共押出しし、５０℃キャストロールで引き取り固化させて幅２００ｍｍ、厚さ２００μｍの未延伸積層シートを得た。テンター延伸設備内にて、温度９０℃で一軸方向に４倍延伸し、膜厚５０μｍの熱収縮性フィルムを作成した。この熱収縮フィルムの結果を表１に示す。８０℃１０秒で収縮させたが、指紋付着部に白化は見られず、フィルム外観は美麗なものであった。また、自然収縮性も良好であった。
(Example 3)
Random copolymer of ethylene and cyclic olefin (Mitsui Chemicals Co., Ltd. “APEL8008T”, Tg: 75 ° C.) 70% by weight and low density polyethylene (Nippon Polychem Co., Ltd. “LF440HB”) 20% by weight And hydrogenated terpene resin (Yasuhara Chemical Co., Ltd. “Clearon P150”) 10 wt% blend polymer composition, intermediate layer metallocene PP (Nihon Polychem Co., Ltd. “XK1165”) 25 wt% and low density polyethylene ( Nippon Polychem Co., Ltd. “LF440HB”) 60% by weight and aliphatic saturated hydrocarbon resin (Arakawa Chemical Industries Co., Ltd. “Arcon P140”) 15% by weight blend polymer compositions, respectively, using the same direction twin screw extruder The mixture was melt-kneaded to obtain composition pellets. This composition was put into separate extruders, then co-extruded from a three-layer die so that the thickness of each layer would be front / back layer / intermediate layer / front / back layer = 1/4/1, and taken and solidified by a 50 ° C. cast roll. Thus, an unstretched laminated sheet having a width of 200 mm and a thickness of 200 μm was obtained. In a tenter stretching facility, the film was stretched 4 times in a uniaxial direction at a temperature of 90 ° C. to prepare a heat-shrinkable film having a thickness of 50 μm. The results of this heat shrink film are shown in Table 1. Although the film was shrunk at 80 ° C. for 10 seconds, no whitening was observed at the fingerprint adhesion part, and the film appearance was beautiful. Moreover, the natural shrinkage was also good.
（実施例４）
上記表裏層となる環状オレフィン（三井化学株式会社製 「ＺＥＯＮＯＲ７５０Ｒ」、Ｔｇ：７０℃）６５重量％と低密度ポリエチレン（日本ポリケム株式会社製 「ＬＦ４４０ＨＢ」、Ｔｍ：１１３℃）２５重量％と水添テルペン樹脂（ヤスハラケミカル株式会社製 「クリアロンＰ１５０」）１０重量％とのブレンドポリマー組成物、中間層となるエチレン−プロピレンゴム（出光石油化学株式会社製 「ＰＥＲ Ｔ３１０Ｅ」、Ｔｍ：１５５℃）５５重量％と低密度ポリエチレン（日本ポリケム株式会社製 「ＬＦ４４０ＨＢ」、Ｔｍ：１１３℃）３０重量％と脂肪族飽和炭化水素樹脂（荒川化学工業株式会社製 「アルコンＰ１４０」）１５重量％のブレンドポリマー組成物を、それぞれ同方向２軸押出機を用いて溶融混練し組成物のペレットを得た。この組成物をそれぞれ別個の押出機に投入後、各層の厚みが表裏層/中間層/表裏層＝１/４/１となるよう３層ダイスより共押出しし、５０℃キャストロールで引き取り固化させて幅２００ｍｍ、厚さ２００μｍの未延伸積層シートを得た。テンター延伸設備内にて、温度９０℃で一軸方向に４倍延伸し、膜厚５０μｍの熱収縮性フィルムを作成した。この熱収縮フィルムの結果を表１に示す。８０℃１０秒で収縮させたが、指紋付着部に白化は見られず、フィルム外観は美麗なものであった。また、自然収縮性も良好であった。
Example 4
Cyclic olefin ("ZEONOR 750R" manufactured by Mitsui Chemicals, Tg: 70 ° C) 65% by weight and low density polyethylene ("LF440HB" manufactured by Nippon Polychem, Tm: 113 ° C) 25% by weight and hydrogenated Blend polymer composition with 10% by weight of terpene resin (Yasuhara Chemical Co., Ltd. “Clearon P150”), ethylene-propylene rubber as an intermediate layer (“PER T310E” manufactured by Idemitsu Petrochemical Co., Ltd., Tm: 155 ° C.) 55% by weight A blend polymer composition of 30% by weight of low density polyethylene (Nippon Polychem “LF440HB”, Tm: 113 ° C.) and 15% by weight of an aliphatic saturated hydrocarbon resin (“Arcon P140” manufactured by Arakawa Chemical Industries, Ltd.) , Each of which is melt-kneaded using the same direction twin screw extruder and pellets of the composition Got. This composition was put into separate extruders, then co-extruded from a three-layer die so that the thickness of each layer would be front / back layer / intermediate layer / front / back layer = 1/4/1, and taken and solidified by a 50 ° C. cast roll. Thus, an unstretched laminated sheet having a width of 200 mm and a thickness of 200 μm was obtained. In a tenter stretching facility, the film was stretched 4 times in a uniaxial direction at a temperature of 90 ° C. to prepare a heat-shrinkable film having a thickness of 50 μm. The results of this heat shrink film are shown in Table 1. Although the film was shrunk at 80 ° C. for 10 seconds, no whitening was observed at the fingerprint adhesion part, and the film appearance was beautiful. Moreover, the natural shrinkage was also good.
（比較例１）
上記表裏層となるエチレンと環状オレフィンとのランダム共重合体（三井化学株式会社製 「ＡＰＥＬ８００８Ｔ」、Ｔｇ：７５℃）９０重量％と水添テルペン樹脂（ヤスハラケミカル株式会社製 「クリアロンＰ１５０」）１０重量％とのブレンドポリマー組成物、エチレン−プロピレン−ブテン−１−三元共重合体（サンアロマー株式会社製 「Ａｄｓｙｌ５Ｃ３０Ｆ」）９０重量％と低密度ポリエチレン（日本ポリケム株式会社製 「ＬＦ４４０ＨＢ」）１０重量％とのブレンドポリマー組成物を、それぞれ同方向２軸押出機を用いて溶融混練し組成物のペレットを得た。この組成物をそれぞれ別個の押出機に投入後、各層の厚みが表裏層/中間層/表裏層＝１/４/１となるよう３層ダイスより共押出しし、５０℃キャストロールで引き取り固化させて幅２００ｍｍ、厚さ２００μｍの未延伸積層シートを得た。これをテンター延伸設備内にて、温度８０℃で一軸方向に４倍延伸し、膜厚５０μｍの熱収縮性フィルムを作成した。ただし、予熱時間は３０秒、延伸速度は３０００％／分であった。この熱収縮フィルムの結果を表１に示す。８０℃１０秒で収縮させたが、指紋付着部に白化現象が生じたうえ、自然収縮率が大きいという結果が得られた。
(Comparative Example 1)
90% by weight of a random copolymer of ethylene and cyclic olefin (Mitsui Chemical Co., Ltd. “APEL8008T”, Tg: 75 ° C.) and 10% by weight of hydrogenated terpene resin (Yasuhara Chemical Co., Ltd. “Clearon P150”). Polymer blend, 90% by weight of ethylene-propylene-butene-1-ternary copolymer (“Adsyl5C30F” manufactured by Sun Allomer Co., Ltd.) and 10% by weight of low density polyethylene (“LF440HB” manufactured by Nippon Polychem Co., Ltd.) The polymer blends were melt-kneaded using the same-direction twin-screw extruder to obtain pellets of the composition. This composition was put into separate extruders, then co-extruded from a three-layer die so that the thickness of each layer would be front / back layer / intermediate layer / front / back layer = 1/4/1, and taken and solidified by a 50 ° C. cast roll. Thus, an unstretched laminated sheet having a width of 200 mm and a thickness of 200 μm was obtained. This was stretched 4 times in a uniaxial direction at a temperature of 80 ° C. in a tenter stretching facility to prepare a heat-shrinkable film having a thickness of 50 μm. However, the preheating time was 30 seconds and the stretching speed was 3000% / min. The results of this heat shrink film are shown in Table 1. Although the film was shrunk at 80 ° C. for 10 seconds, a whitening phenomenon occurred at the fingerprint adhering portion and the natural shrinkage rate was large.
（比較例２）
上記表裏層となるエチレンと環状オレフィンとのランダム共重合体（三井化学株式会社製 「ＡＰＥＬ８００８Ｔ」、Ｔｇ：７５℃）９０重量％と水添テルペン樹脂（ヤスハラケミカル株式会社製 「クリアロンＰ１５０」）１０重量％とのブレンドポリマー組成物、低密度ポリエチレン（日本ポリケム株式会社製 「ＬＦ４４０ＨＢ」）２０重量％と、水添テルペン樹脂（ヤスハラケミカル株式会社製 「クリアロンＰ１５０」）１０重量％とのブレンドポリマー組成物、中間層となるエチレン−プロピレン−ブテン１-三元共重合体（サンアロマー株式会社製 「Ａｄｓｙｌ５Ｃ３０Ｆ」）９０重量％と低密度ポリエチレン（日本ポリケム株式会社製 「ＬＦ４４０ＨＢ」）１０重量％とのブレンドポリマー組成物を、それぞれ同方向２軸押出機を用いて溶融混練し組成物のペレットを得た。この組成物をそれぞれ別個の押出機に投入後、各層の厚みが表裏層/中間層/表裏層＝１/４/１となるよう３層ダイスより共押出しし、５０℃キャストロールで引き取り固化させて幅２００ｍｍ、厚さ２００μｍの未延伸積層シートを得た。これをテンター延伸設備内にて、温度１００℃で一軸方向に４倍延伸し、膜厚５０μｍの熱収縮性フィルムを作成した。ただし、予熱時間は３０秒、延伸速度は３０００％／分であった。この熱収縮フィルムの結果を表１に示す。８０℃１０秒で収縮させたが、指紋付着部に白化現象が生じたうえ、収縮率が低く被覆部の収縮不足が目立った。
(Comparative Example 2)
90% by weight of a random copolymer of ethylene and cyclic olefin (Mitsui Chemical Co., Ltd. “APEL8008T”, Tg: 75 ° C.) and 10% by weight of hydrogenated terpene resin (Yasuhara Chemical Co., Ltd. “Clearon P150”). A blend polymer composition of 20% by weight of a low density polyethylene (“LF440HB” manufactured by Nippon Polychem Co., Ltd.) and 10% by weight of a hydrogenated terpene resin (“Clearon P150” manufactured by Yashara Chemical Co., Ltd.), Blend polymer composition of 90% by weight of ethylene-propylene-butene 1-ternary copolymer (“Adsyl5C30F” manufactured by Sun Allomer Co., Ltd.) and 10% by weight of low density polyethylene (“LF440HB” manufactured by Nippon Polychem Co., Ltd.) serving as an intermediate layer The same direction twin screw extruder The mixture was melt-kneaded to obtain a pellet of the composition. This composition was put into separate extruders, then co-extruded from a three-layer die so that the thickness of each layer would be front / back layer / intermediate layer / front / back layer = 1/4/1, and taken and solidified by a 50 ° C. cast roll. Thus, an unstretched laminated sheet having a width of 200 mm and a thickness of 200 μm was obtained. This was stretched 4 times in a uniaxial direction at a temperature of 100 ° C. in a tenter stretching facility to prepare a heat-shrinkable film having a thickness of 50 μm. However, the preheating time was 30 seconds and the stretching speed was 3000% / min. The results of this heat shrink film are shown in Table 1. Shrinkage was performed at 80 ° C. for 10 seconds, but a whitening phenomenon occurred in the fingerprint-attached portion, and the shrinkage rate was low and the shrinkage of the coating portion was conspicuous.
（比較例３）
上記表裏層となるエチレンと環状オレフィンとのランダム共重合体（三井化学株式会社製品 「ＡＰＥＬ８００８Ｔ」、Ｔｇ：７５℃）４０重量％と低密度ポリエチレン（日本ポリケム株式会社製 「ＬＦ４４０ＨＢ」、Ｔｍ：１１３℃）５０重量％と水添テルペン樹脂（ヤスハラケミカル株式会社製 「クリアロンＰ１５０」）１０重量％とのブレンドポリマー組成物、中間層となるエチレン−プロピレンゴム（出光石油化学株式会社製 「ＰＥＲ Ｔ３１０Ｅ」、Ｔｍ：１５５℃）５５重量％と低密度ポリエチレン（日本ポリケム株式会社製 「ＬＦ４４０ＨＢ」、Ｔｍ：１１３℃）３０重量％と脂肪族飽和炭化水素樹脂（荒川化学工業株式会社製 「アルコンＰ１４０」）１５重量％のブレンドポリマー組成物を、それぞれ同方向２軸押出機を用いて溶融混練し組成物のペレットを得た。この組成物をそれぞれ別個の押出機に投入後、各層の厚みが表裏層/中間層/表裏層＝１/４/１となるよう３層ダイスより共押出しし、５０℃キャストロールで引き取り固化させて幅２００ｍｍ、厚さ２００μｍの未延伸積層シートを得た。テンター延伸設備内にて、温度９０℃で一軸方向に４倍延伸し、膜厚５０μｍの熱収縮性フィルムを作成した。この熱収縮フィルムの結果を表１に示す。８０℃１０秒で収縮させたが、指紋付着部に白化は生じなかったが、自然収縮性が大きい結果が得られた。
(Comparative Example 3)
Random copolymer of ethylene and cyclic olefin (Mitsui Chemicals Co., Ltd. product “APEL8008T”, Tg: 75 ° C.) 40% by weight and low density polyethylene (“LF440HB” manufactured by Nippon Polychem Co., Ltd.), Tm: 113 ° C) 50 wt% and hydrogenated terpene resin (Yasuhara Chemical Co., Ltd. “Clearon P150”) 10 wt% blend polymer composition, ethylene-propylene rubber (Idemitsu Petrochemical Co., Ltd. “PER T310E” as an intermediate layer, 55% by weight (Tm: 155 ° C.) and low density polyethylene (“LF440HB” manufactured by Nippon Polychem Co., Ltd.), 30% by weight and aliphatic saturated hydrocarbon resin (“Alcon P140” manufactured by Arakawa Chemical Industries, Ltd.) 15 Each blend polymer composition is used in the same direction twin screw extruder. And kneaded to obtain pellets of the composition. This composition was put into separate extruders, then co-extruded from a three-layer die so that the thickness of each layer would be front / back layer / intermediate layer / front / back layer = 1/4/1, and taken and solidified by a 50 ° C. cast roll. Thus, an unstretched laminated sheet having a width of 200 mm and a thickness of 200 μm was obtained. In a tenter stretching facility, the film was stretched 4 times in a uniaxial direction at a temperature of 90 ° C. to prepare a heat-shrinkable film having a thickness of 50 μm. The results of this heat shrink film are shown in Table 1. Although the film was shrunk at 80 ° C. for 10 seconds, whitening did not occur in the fingerprint-attached part, but a result with a large natural shrinkage was obtained.
（比較例４）
上記表裏層となるエチレンと環状オレフィンとのランダム共重合体（三井化学株式会社製 「ＡＰＥＬ８００８Ｔ」、Ｔｇ：７５℃）９０重量％と水添テルペン樹脂（ヤスハラケミカル株式会社製 「クリアロンＰ１５０」）１０重量％とのブレンドポリマー組成物、中間層となるエチレン−プロピレンゴム（出光石油化学株式会社製 「ＰＥＲ Ｔ３１０Ｅ」）５５重量％と低密度ポリエチレン（日本ポリケム株式会社製 「ＬＦ４４０ＨＢ」）３０重量％と脂肪族飽和炭化水素樹脂（荒川化学工業株式会社製 「アルコンＰ１４０」）１５重量％のブレンドポリマー組成物を、それぞれ同方向２軸押出機を用いて溶融混練し組成物のペレットを得た。この組成物をそれぞれ別個の押出機に投入後、各層の厚みが表裏層/中間層/表裏層＝１/４/１となるよう３層ダイスより共押出しし、５０℃キャストロールで引き取り固化させて幅２００ｍｍ、厚さ２００μｍの未延伸積層シートを得た。これをテンター延伸設備内にて、温度９０℃で一軸方向に４倍延伸し、膜厚５０μｍの熱収縮性フィルムを作成した。この熱収縮フィルムの結果を表１に示す。８０℃１０秒で収縮させると、指紋付着部の白化現象が生じた。
(Comparative Example 4)
90% by weight of a random copolymer of ethylene and cyclic olefin (Mitsui Chemical Co., Ltd. “APEL8008T”, Tg: 75 ° C.) and 10% by weight of hydrogenated terpene resin (Yasuhara Chemical Co., Ltd. “Clearon P150”). % Blended polymer composition, intermediate layer of ethylene-propylene rubber (Idemi Petrochemical Co., Ltd. “PER T310E”) 55 wt% and low density polyethylene (Nihon Polychem Co., Ltd. “LF440HB”) 30 wt% and fat A blend polymer composition of 15% by weight of a group saturated hydrocarbon resin (“Arcon P140” manufactured by Arakawa Chemical Industries, Ltd.) was melt-kneaded using a same-direction twin screw extruder to obtain pellets of the composition. This composition was put into separate extruders, then co-extruded from a three-layer die so that the thickness of each layer would be front / back layer / intermediate layer / front / back layer = 1/4/1, and taken and solidified by a 50 ° C. cast roll. Thus, an unstretched laminated sheet having a width of 200 mm and a thickness of 200 μm was obtained. This was stretched 4 times in a uniaxial direction at a temperature of 90 ° C. in a tenter stretching facility to prepare a heat-shrinkable film having a thickness of 50 μm. The results of this heat shrink film are shown in Table 1. When contracted at 80 ° C. for 10 seconds, a whitening phenomenon occurred in the fingerprint adhesion part.
（比較例５）
上記表裏層となるエチレンと環状オレフィンとのランダム共重合体（三井化学株式会社製 「ＡＰＥＬ８００８Ｔ」、Ｔｇ：７５℃）９０重量％と水添テルペン樹脂（ヤスハラケミカル株式会社製 「クリアロンＰ１５０」）１０重量％とのブレンドポリマー組成物、中間層となるエチレン−プロピレンゴム（出光石油化学株式会社製 「ＰＥＲ Ｔ３１０Ｅ」）５５重量％と低密度ポリエチレン（日本ポリケム株式会社製 「ＬＦ４４０ＨＢ」）３０重量％と脂肪族飽和炭化水素樹脂（荒川化学工業株式会社製 「アルコンＰ１４０」）１５重量％のブレンドポリマー組成物を、それぞれ同方向２軸押出機を用いて溶融混練し組成物のペレットを得た。この組成物をそれぞれ別個の押出機に投入後、各層の厚みが表裏層/中間層/表裏層＝１/１０/１となるよう３層ダイスより共押出しし、５０℃キャストロールで引き取り固化させて幅２００ｍｍ、厚さ２００μｍの未延伸積層シートを得た。これをテンター延伸設備内にて、温度９０℃で一軸方向に４倍延伸し、膜厚５０μｍの熱収縮性フィルムを作成した。この熱収縮フィルムの結果を表１に示す。８０℃１０秒で収縮させたが、指紋付着部に白化現象が生じたうえ、自然収縮率が大きいという結果が得られた。
(Comparative Example 5)
90% by weight of a random copolymer of ethylene and cyclic olefin (Mitsui Chemical Co., Ltd. “APEL8008T”, Tg: 75 ° C.) and 10% by weight of hydrogenated terpene resin (Yasuhara Chemical Co., Ltd. “Clearon P150”). % Blended polymer composition, intermediate layer of ethylene-propylene rubber (Idemi Petrochemical Co., Ltd. “PER T310E”) 55 wt% and low density polyethylene (Nihon Polychem Co., Ltd. “LF440HB”) 30 wt% and fat A blend polymer composition of 15% by weight of a group saturated hydrocarbon resin (“Arcon P140” manufactured by Arakawa Chemical Industries, Ltd.) was melt-kneaded using a biaxial extruder in the same direction to obtain pellets of the composition. Each composition was put into separate extruders, then co-extruded from a three-layer die so that the thickness of each layer would be front / back layer / intermediate layer / front / back layer = 1/10/1, and taken and solidified by a 50 ° C. cast roll. Thus, an unstretched laminated sheet having a width of 200 mm and a thickness of 200 μm was obtained. This was stretched 4 times in a uniaxial direction at a temperature of 90 ° C. in a tenter stretching facility to prepare a heat-shrinkable film having a thickness of 50 μm. The results of this heat shrink film are shown in Table 1. Although the film was shrunk at 80 ° C. for 10 seconds, a whitening phenomenon occurred at the fingerprint adhering portion and the natural shrinkage rate was large.
Claims (5)
The heat-shrinkable olefin-based laminated film according to any one of claims 1 to 4, wherein the shrinkage in the main shrinkage direction after storage for 30 days in a 30 ° C environment is 2.5% or less.
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| JP2004064956A JP2005254458A (en) | 2004-03-09 | 2004-03-09 | Heat-shrinkable olefinic laminated film |
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| JP2004064956A JP2005254458A (en) | 2004-03-09 | 2004-03-09 | Heat-shrinkable olefinic laminated film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008049506A (en) * | 2006-08-22 | 2008-03-06 | Mitsubishi Plastics Ind Ltd | Stretch-shrink laminated film and its manufacturing method |
| JP2008307896A (en) * | 2007-05-15 | 2008-12-25 | Mitsubishi Plastics Inc | Laminated film, formed article using the same, heat shrinkable label, and container equipped with the label |
| JP2011104816A (en) * | 2009-11-13 | 2011-06-02 | C I Kasei Co Ltd | Heat-shrinkable polyolefinic film |
| WO2012035956A1 (en) * | 2010-09-15 | 2012-03-22 | 東レ株式会社 | Molding film and molding transfer foil |
| JP2012111068A (en) * | 2010-11-22 | 2012-06-14 | Dic Corp | Multilayer film and packaging material using the same |
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| US10232594B2 (en) | 2013-07-12 | 2019-03-19 | Upm Raflatac Oy | Multilayer film for label and a method for providing such |
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| US10858504B2 (en) | 2017-07-06 | 2020-12-08 | Exxonmobil Chemical Patents Inc. | Polyethylene compositions comprising cyclic-olefin copolymers |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09154479A (en) * | 1995-12-13 | 1997-06-17 | Mitsubishi Plastics Ind Ltd | Stretched film for wrapping food |
| JP2000202951A (en) * | 1999-01-18 | 2000-07-25 | Mitsubishi Plastics Ind Ltd | Heat shrinkable polyolefin laminated film |
| JP2002337231A (en) * | 2001-05-17 | 2002-11-27 | Japan Polychem Corp | Laminated film for shrink label of heat-shrinkable polyolefin and container to which the film is applied |
| JP2003053912A (en) * | 2001-08-16 | 2003-02-26 | Mitsubishi Plastics Ind Ltd | Heat-shrinkable laminated film |
| JP2003118041A (en) * | 2001-10-17 | 2003-04-23 | Japan Polychem Corp | Laminated film for heat-shrinkable polyolefinic shrink label and container provided therewith |
| JP2004066533A (en) * | 2002-08-02 | 2004-03-04 | Mitsubishi Plastics Ind Ltd | Heat-shrinkable laminated polyolefin film |
-
2004
- 2004-03-09 JP JP2004064956A patent/JP2005254458A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09154479A (en) * | 1995-12-13 | 1997-06-17 | Mitsubishi Plastics Ind Ltd | Stretched film for wrapping food |
| JP2000202951A (en) * | 1999-01-18 | 2000-07-25 | Mitsubishi Plastics Ind Ltd | Heat shrinkable polyolefin laminated film |
| JP2002337231A (en) * | 2001-05-17 | 2002-11-27 | Japan Polychem Corp | Laminated film for shrink label of heat-shrinkable polyolefin and container to which the film is applied |
| JP2003053912A (en) * | 2001-08-16 | 2003-02-26 | Mitsubishi Plastics Ind Ltd | Heat-shrinkable laminated film |
| JP2003118041A (en) * | 2001-10-17 | 2003-04-23 | Japan Polychem Corp | Laminated film for heat-shrinkable polyolefinic shrink label and container provided therewith |
| JP2004066533A (en) * | 2002-08-02 | 2004-03-04 | Mitsubishi Plastics Ind Ltd | Heat-shrinkable laminated polyolefin film |
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| JP2011104816A (en) * | 2009-11-13 | 2011-06-02 | C I Kasei Co Ltd | Heat-shrinkable polyolefinic film |
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