JP2017074982A - Polyolefin heat-shrinkable film - Google Patents
Polyolefin heat-shrinkable film Download PDFInfo
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Abstract
Description
本発明はオーバーラップ用のポリオレフィン系熱収縮性包装材料に関し、より詳しくは、インキ等との接着性が改善されたポリオレフィン系熱収縮性フィルムで、従来使用されているポリオレフィン系熱収縮性フィルムと同様の熱収縮性と高速自動包装適性を有する熱収縮性ポリオレフィンフィルムに関する。 The present invention relates to a polyolefin-based heat-shrinkable packaging material for overlap, and more specifically, a polyolefin-based heat-shrinkable film having improved adhesion to ink and the like, and a polyolefin-based heat-shrinkable film conventionally used The present invention relates to a heat-shrinkable polyolefin film having the same heat-shrinkability and high-speed automatic packaging suitability.
従来、熱収縮性包装材料として、コスト、使用後の廃棄処理の容易さなどの点でポリプロピレン、ポリエチレン等のポリオレフィン系シュリンクフィルムが好んで用いられているが、ポリオレフィン系熱収縮性フィルムの表面が不活性なため、汎用インキとの接着性に乏しく、特殊かつ比較的高価な塩素化ＰＰ系インキやポリアミド硝化棉ワニス系のインキが使用されている。 Conventionally, polyolefin shrink films such as polypropylene and polyethylene are preferably used as heat-shrinkable packaging materials in terms of cost and ease of disposal after use. Since it is inactive, it has poor adhesion to general-purpose inks, and special and relatively expensive chlorinated PP ink and polyamide nitrile varnish ink are used.
一方、プラスチックフィルムの接着性を改善する手段として一般的にはコロナ放電処理、プラズマ処理、フレーム処理、コーティングなどで表面を活性化させる方法が知られている。しかしこれらの表面活性方法だと熱収縮包装に一般的に用いられる溶断シール時においてシール部の強度が著しく低下する問題があった。
またこの解決方法として酸変性した改質オレフィンやその他のイオン性を有する改質オレフィンをベースとなるオレフィンに適量混合することによってインキ接着性と熱収縮包装を両立させることが提案されている。しかしながらインキ接着性は改善されるものの溶断シール強度向上には限定された効果しか得られず、インキ接着性と包装適性の両立ができず実用性は低かった。
On the other hand, as a means for improving the adhesiveness of a plastic film, a method is generally known in which the surface is activated by corona discharge treatment, plasma treatment, flame treatment, coating or the like. However, these surface activation methods have a problem in that the strength of the seal portion is significantly reduced at the time of fusing sealing generally used for heat shrink packaging.
As a solution to this problem, it has been proposed to combine ink adhesion and heat shrink packaging by mixing an appropriate amount of acid-modified olefin or other ionic modified olefin with the base olefin. However, although the ink adhesion is improved, only a limited effect can be obtained to improve the fusing seal strength, and the ink adhesion and the packaging suitability cannot be achieved, and the practicality is low.
また、水添テルペン樹脂は、フィルムに柔軟性を与えること（特許文献１）、シュリンクラベル用フィルムにおいて、低温収縮性を向上させるために、テルペン樹脂を表面層に添加すること（特許文献２）、ストレッチ性とシュリンク性、耐擦過性付与のために、表面層に水添テルペン樹脂を添加することが記載されている。さらに、水添テルペン樹脂は、粘着性を付与させる目的で使用することもある（特許文献４）。 Further, hydrogenated terpene resin gives flexibility to a film (Patent Document 1), and in a film for shrink label, terpene resin is added to a surface layer in order to improve low-temperature shrinkage (Patent Document 2). In addition, it is described that a hydrogenated terpene resin is added to a surface layer in order to impart stretchability, shrinkage, and scratch resistance. Furthermore, hydrogenated terpene resin may be used for the purpose of imparting tackiness (Patent Document 4).
以上、オーバーラップ用のポリオレフィン系熱収縮性包装材料に関して、意匠性付与のための印刷適性と熱収縮性、高速自動包装適性を両立した包装材料が求められていた。 As described above, regarding the polyolefin-based heat-shrinkable packaging material for overlap, a packaging material having both printability for designability, heat-shrinkability, and high-speed automatic packaging property has been demanded.
本発明は、上記状況を鑑み、従来使用されているポリオレフィン系熱収縮性フィルムと同様の熱収縮性と高速自動包装適性を有する熱収縮性ポリオレフィンフィルムであって、且つインキとの接着性を向上させたポリオレフィン系熱収縮性フィルムを提供することを課題とする。 In view of the above situation, the present invention is a heat-shrinkable polyolefin film having the same heat-shrinkability and high-speed automatic packaging suitability as a polyolefin-based heat-shrinkable film that has been used in the past, and has improved adhesion to ink. It is an object of the present invention to provide a polyolefin heat-shrinkable film.
本発明者らは、鋭意検討した結果、ある特定の改質剤量をオレフィン樹脂に配合することによって解決した。
すなわち本発明は、
（１）ポリオレフィンかならなる熱収縮性フィルムであって、１２０℃のＭＤ及びＴＤの熱収縮率が１０〜７０％であり、少なくとも片方の表面層の組成がＡ及びＢの混合樹脂で構成され、ＡとＢの比が重量当たり９７/３〜４０/６０であることを特徴とする接着性に優れた二軸延伸ポリオレフィン系熱収縮性フィルム
Ａ：ＪＩＳＫ７２０６に準じ１０Ｎ及び昇温速度 ５０℃／時間で測定した軟化点が１００〜１３５℃であり、ＭＦＲが０．５〜６ポリプロピレン樹脂
Ｂ：ポリエーテルとポリオレフィンのブロック共重合体であり、表面固有抵抗値が１０７〜１０１０Ωの変性ポリオレフィン樹脂又はＪＩＳＫ２２０７で測定した軟化点が８５〜１３５℃である水添テルペン樹脂
（２）Ａ及びＢの混合で構成される表面層の厚みが０．１μｍ以上であることを特徴とする（１）記載の二軸延伸ポリオレフィン熱収縮性フィルム
（３）フィルムのヘーズが７％未満である（１）又は（２）記載の二軸延伸ポリオレフィン熱収縮性フィルム
に係るものである。
As a result of intensive studies, the present inventors have solved the problem by blending a specific amount of modifier into the olefin resin.
That is, the present invention
(1) A heat-shrinkable film made of polyolefin, which has a heat shrinkage ratio of MD and TD of 120 ° C. of 10 to 70%, and the composition of at least one surface layer is composed of a mixed resin of A and B. A biaxially stretched polyolefin heat-shrinkable film excellent in adhesiveness, characterized in that the ratio of A to B is 97/3 to 40/60 per weight. A: 10N according to JISK7206 and heating rate of 50 ° C. / A softening point measured in time is 100 to 135 ° C., an MFR is 0.5 to 6 polypropylene resin B: a block copolymer of polyether and polyolefin, and a surface specific resistance value is 10 7 to 10 10 Ω The thickness of the surface layer composed of a mixture of polyolefin resin or hydrogenated terpene resins (2) A and B having a softening point of 85 to 135 ° C. measured by JIS K2207 is 0.1 μm. The biaxially stretched polyolefin heat-shrinkable film according to (1), wherein the film has a haze of less than 7%, characterized in that the biaxially stretched polyolefin heat-shrinkable according to (1) or (2) It concerns the film.
本発明は、従来使用されているポリオレフィン系熱収縮性フィルムと同様の熱収縮性と高速自動包装適性を有する熱収縮性ポリオレフィンフィルムであり、且つインキとの接着性が向上したため、包装時や包装後のインキ剥がれなどのトラブルが改善するだけでなく、フィルムへのインキ接着性が良いため、汎用のインキを使用することができ、インキのコストを削減することが可能である。 The present invention is a heat-shrinkable polyolefin film having the same heat-shrinkability and high-speed automatic packaging suitability as a polyolefin-based heat-shrinkable film that has been used in the past, and has improved adhesion to ink. Not only troubles such as subsequent ink peeling are improved, but since ink adhesion to the film is good, general-purpose ink can be used, and the cost of ink can be reduced.
以下、本発明を詳細に説明する。
本発明における表面層に用いられるポリプロピレン樹脂は、ＪＩＳＫ７２０６に準じ１０N 及び昇温速度 ５０℃／時間で測定した軟化点が９０〜１３５℃である。軟化点が１００℃未満だと室温付近で収縮が起こる場合があり好ましくない。また軟化点が１３５℃以上だと熱収縮包装時のトンネル温度が過剰に高くなるばかりでなく、良好な熱収縮率を得ることができない。
ポリプロピレン樹脂のＭＦＲは、０．５〜６である。より好ましくは１〜４である。ＭＦＲが０．５より小さいと押出時の負荷が高くなるばかりでなく、混合する他樹脂との混練が難しくなるので好ましくない。またＭＦＲが６より大きいと後に述べる高速包装時のシール性の低下が大きく好ましくない。本発明に用いられるポリプロピレン樹脂は軟化点とＭＦＲが既定の範囲にあれば１種ないしは2種以上の混合物でも構わない。例えば高い軟化のポリプロピレン樹脂に低軟化点のポリプロピレンを混合して使用することにより、目的に軟化点に調整することができる。ポリプロピレン樹脂とはプロピレンを主原料としα−オレフィンの共重合体、例えばプロピレン−エチレン、プロピレン−ブテン共重合体、及びプロピレン−エチレン−ブテン３元共重合体等により軟化点を適宜調整できる。
Hereinafter, the present invention will be described in detail.
The polypropylene resin used for the surface layer in the present invention has a softening point of 90 to 135 ° C. measured at 10 N and a heating rate of 50 ° C./hour according to JISK7206. When the softening point is less than 100 ° C., shrinkage may occur near room temperature, which is not preferable. On the other hand, when the softening point is 135 ° C. or higher, not only the tunnel temperature during heat shrink wrapping becomes excessively high, but also a good heat shrinkage rate cannot be obtained.
The MFR of the polypropylene resin is 0.5-6. More preferably, it is 1-4. If the MFR is less than 0.5, not only is the load during extrusion high, but also kneading with other resins to be mixed becomes difficult, such being undesirable. On the other hand, if MFR is larger than 6, the deterioration of the sealing performance at the time of high-speed packaging, which will be described later, is not preferable. The polypropylene resin used in the present invention may be one kind or a mixture of two or more kinds as long as the softening point and MFR are in a predetermined range. For example, the softening point can be adjusted to the purpose by mixing and using a polypropylene having a low softening point in a polypropylene resin having a high softening point. With the polypropylene resin, the softening point can be appropriately adjusted by using α-olefin copolymer such as propylene-ethylene, propylene-butene copolymer, and propylene-ethylene-butene terpolymer with propylene as the main raw material.
本発明において、ポリプロピレン樹脂と混合して使用される改質樹脂は以下の2種の内、いずれかが使用される。
一つはポリエーテルとポリオレフィンのブロック共重合体であり、表面固有抵抗が１０７〜１０１０Ωの変性ポリオレフィン樹脂である。ポリエーテルはイオン性を有しないがそのエーテル結合により極性を有しインキ等との接着性を発現する。またこのブロック共重合体はポリプロピレン樹脂との相溶性に優れ透明性を阻害しないばかりか包装時の溶断シール性の低下が極めて少ない。表面固有抵抗値が１０７Ω未満だとポリエーテル成分が多くなりポリプロピレン樹脂との相溶性が悪くなり好ましくない。また１０１０Ωより大きいとインキ接着性の向上効果が不十分となり好ましくない。ポリエーテルとポリオレフィンのブロック共重合体のＭＦＲは１９０℃、２１．１８Ｎで０．２〜２０が好ましい。これを外れると混合するポリプロピレン樹脂との混練が難しくなる。
In the present invention, one of the following two types of modified resins used in combination with a polypropylene resin is used.
One is a block copolymer of polyether and polyolefin, which is a modified polyolefin resin having a surface resistivity of 10 7 to 10 10 Ω. Polyether does not have ionicity, but has polarity due to its ether bond and exhibits adhesiveness with ink or the like. Further, this block copolymer is excellent in compatibility with polypropylene resin and does not hinder the transparency, and the degradation of the fusing sealability during packaging is extremely small. When the surface specific resistance is less than 10 7 Ω, the polyether component is increased and the compatibility with the polypropylene resin is deteriorated. On the other hand, if it is larger than 10 10 Ω, the effect of improving ink adhesion is insufficient, which is not preferable. The MFR of the block copolymer of polyether and polyolefin is 190 ° C., 21.18 N, and preferably 0.2-20. If it deviates, kneading with the polypropylene resin to be mixed becomes difficult.
ポリプロピレン樹脂と混合される他の一つは水添テルペン樹脂でありＪＩＳＫ２２０７で測定した軟化点が８５〜１３５℃である。軟化点が８５℃より低い場合、ポリプロピレン樹脂との相溶性が悪くなり、ヘーズの悪化を招くため好ましくない。また常温でのべたつくことによりフィルム同士のブロッキング等の可能性もあり好ましくない。軟化点が１３５℃より大きい場合、ポリプロピレン樹脂との相溶性が悪くなり、ヘーズの悪化を招くため好ましくない。またフィルムの熱収縮が小さくなる場合があり、好ましくない。 Another one mixed with the polypropylene resin is a hydrogenated terpene resin having a softening point of 85 to 135 ° C. measured by JISK2207. When the softening point is lower than 85 ° C., the compatibility with the polypropylene resin is deteriorated and haze is deteriorated. Further, stickiness at normal temperature may cause blocking between films, which is not preferable. When the softening point is higher than 135 ° C., the compatibility with the polypropylene resin is deteriorated and haze is deteriorated. Moreover, the thermal shrinkage of the film may be small, which is not preferable.
ポリプロピレン樹脂と前記改質樹脂の混合樹脂は少なくとも片方の表面層に配置される。この面がインキとの接着性が良好な面となり印刷に適する。両面印刷される場合は両方の表面層に配置すればよい。ポリプロピレン樹脂と改質樹脂の比は重量当たり９７／３〜４０/６０混合する必要がある。改質樹脂が３未満では、十分なインキ接着性が得られず好ましくない。 The mixed resin of the polypropylene resin and the modified resin is disposed on at least one surface layer. This surface has good adhesion to ink and is suitable for printing. What is necessary is just to arrange | position to both surface layers when printing on both sides. The ratio of polypropylene resin to modified resin should be 97/3 to 40/60 per weight. If the modified resin is less than 3, it is not preferable because sufficient ink adhesion cannot be obtained.
本発明の層構成は、多層構成として芯層に異なるポリオレフィン系樹脂用いることができる。ポリエチレン系樹脂を芯層に用いた場合、低温での熱収縮率が高くなり包装時の仕上がりが良くなる。また、本発明の目的に支障をきたさない範囲で、プロピレン系樹脂、プロピレン単重合体、エチレン系樹脂の混合物のスクラップを再利用して用いることもできる。 In the layer structure of the present invention, different polyolefin resins can be used for the core layer as a multilayer structure. When a polyethylene resin is used for the core layer, the heat shrinkage rate at a low temperature is high, and the finish at the time of packaging is improved. In addition, a scrap of a mixture of a propylene resin, a propylene homopolymer, and an ethylene resin can be reused as long as the object of the present invention is not hindered.
本発明における、ポリオレフィン系熱収縮性フィルムの厚みは用途に応じて適宜、選択すればよいが、収縮仕上がり性や高速包装適性を有効に発現させるという点では、６〜３５μｍ程度が好ましい。 The thickness of the polyolefin heat-shrinkable film in the present invention may be appropriately selected according to the use, but is preferably about 6 to 35 μm from the viewpoint of effectively expressing the shrink finish and high-speed packaging suitability.
本発明における表層の改質樹脂を含むポリプロピレン樹脂層の厚みとしては、０．１μｍ以上が必要である。また好ましくは１μｍ以上、より好ましくは２μｍ以上である。０．１μｍ未満になると十分なインキ接着性を得られない。また芯層の樹脂と相性によっては包装時のシール性が低下するので、適宜表層の厚みを選択する必要がある。 The thickness of the polypropylene resin layer containing the surface modification resin in the present invention is required to be 0.1 μm or more. Further, it is preferably 1 μm or more, more preferably 2 μm or more. If it is less than 0.1 μm, sufficient ink adhesion cannot be obtained. Moreover, since the sealing performance at the time of packaging deteriorates depending on the compatibility with the resin of the core layer, it is necessary to appropriately select the thickness of the surface layer.
本発明において、滑剤、ブロッキング防止剤、帯電防止剤、防曇剤、酸化防止剤、核剤等の添加剤がそれぞれの有効な作用を具備させる目的で適宜使用することができる。
本発明のフィルムのヘーズは７％未満が好ましい。ポリプロピレン樹脂と改質樹脂の混合層はその良好な相溶性によって透明性を阻害させない。添加剤も適宜選択することによって、フィルムのヘーズは５％未満の良好な透明性を得ることができる。
In the present invention, additives such as a lubricant, an anti-blocking agent, an antistatic agent, an antifogging agent, an antioxidant, and a nucleating agent can be appropriately used for the purpose of providing each effective action.
The haze of the film of the present invention is preferably less than 7%. The mixed layer of the polypropylene resin and the modified resin does not hinder the transparency due to its good compatibility. By selecting an additive as appropriate, the film can have a good transparency with a haze of less than 5%.
本発明において二軸延伸ポリオレフィン系熱収縮性フィルムとは、前記の樹脂を用いて、公知の縦横２軸延伸方法で行うことができる。特にチューブラー二軸延伸製膜法が高い熱収縮率のフィルムを得ることができる観点で最も好ましい。
以下、チューブラー３層積層環状製膜延伸の場合を例に挙げ、具体的に説明する。
まず、プロピレン系樹脂と改質樹脂を混合した両表面層、改質樹脂を含まないポリプロピレン樹脂を芯層とし、２台の押出機により溶融混練し、３層環状ダイより環状に共押出し、延伸することなく一旦急冷固化してチューブ状未延伸シートを作製する。
得られたチューブ状未延伸シートを、チューブラー延伸装置に供給し、高度の配向可能な温度範囲、ポリプロピレン樹脂の融点より１０〜７０℃低い温度で、チューブ内部にガス圧を適用して膨張延伸により、縦横の延伸倍率が、２〜５倍程度で同時二軸配向を起こさせる。延伸装置から取り出したフィルムは、希望により熱処理やアニーリングすることができ、これにより保存中の自然収縮を抑制することができる。このときの１２０℃熱収縮率は収縮仕上がり性を有効に発現させるという点でＭＤ及びＴＤの１２０℃熱収縮率は１０〜７０％、好ましくは３０〜６０％である。
In the present invention, the biaxially stretched polyolefin heat-shrinkable film can be formed by a known longitudinal and lateral biaxial stretching method using the above resin. In particular, the tubular biaxial stretching film forming method is most preferable from the viewpoint of obtaining a film having a high heat shrinkage rate.
Hereinafter, the case of tubular three-layer laminated annular film-forming stretching will be described as an example.
First, both surface layers mixed with a propylene-based resin and a modified resin, a polypropylene resin not containing a modified resin as a core layer, melt-kneaded with two extruders, co-extruded in a ring from a three-layer annular die, and stretched Without quenching, the tube is temporarily cooled and solidified to produce a tubular unstretched sheet.
The obtained tubular unstretched sheet is supplied to a tubular stretching apparatus, and is expanded and stretched by applying a gas pressure inside the tube at a temperature range capable of high orientation, a temperature lower than the melting point of polypropylene resin by 10 to 70 ° C. Thus, simultaneous biaxial orientation is caused when the longitudinal and lateral stretch ratios are about 2 to 5 times. The film taken out from the stretching apparatus can be heat-treated or annealed as desired, thereby suppressing natural shrinkage during storage. The 120 ° C. heat shrinkage at this time is 10 to 70%, preferably 30 to 60% in terms of the 120 ° C. heat shrinkage of MD and TD in terms of effectively expressing shrinkage finish.
以下、実施例により本発明を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
なお、本実施例の中で示した各物性測定は以下の方法によった。
１．インキ接着性評価方法
ザーンカップ＃３で１６．００〜１６．５０秒になるようにインキ（大日精化工業株式会社製、ラミックＳＲ739Ｒ藍Ｍ３改）を希釈剤（大日精化工業株式会社製、ラミック ＳＲＮｏ.３溶剤）で希釈し、乾燥後の塗布量が３ｇ／ｍ２になるようにポリプロピレン樹脂と改質樹脂の混合組成を配した面にコートした。乾燥は自然乾燥で２４Ｈ行い、セロハンテープ（ニチバン株式会社製、１５ｍｍ幅）を１０ｃｍ貼り付け、空気が抜けるまで擦った。
その後、勢いよくセロハンテープを剥し、インキの剥離量が５％未満であれば評価○、それ以上であれば×とした。
２．１２０℃熱収縮率
縦横それぞれ１００ｍｍの正方形に切り取ったフィルムを１２０℃のグリセリン浴中に１０秒間浸漬した後、水中で急冷し、縦横それぞれの長さを測定し、ＭＤ、ＴＤの熱収縮率を算出した。
３．ピロー収縮包装機適性評価方法（横シール性評価）
カップ麺のオーバーラップシュリンク包装で使用されるピロー型連続シュリンク包装機でフィルムの包装適性を評価した。フィルム幅を４４０ｍｍとし、嵩高７０ｍｍの市販のどんぶり型カップ麺をピロー包装した。包装機はトキワ工業製ＮＥＯ型、カット長２３０ｍｍ、包装速度３５ｍ／分、縦シールはローレット型、横シールは最も多く用いられている溶断型でシール刃温度を２００℃、受けの刃の温度を９０℃とした。シール後協和電機製L-2400FBトンネルを２．５秒、温度を仕上がりを見ながら１４０〜１７０℃に調整しフィルムを熱収縮させた。１００個包装後、２個以上横シール部分に直径２ｍｍ以上のピンホールが見られシール性不良と判断した場合を×、ピンホールの直径２ｍｍ以上が１個未満だった場合を○とした。
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.
In addition, each physical property measurement shown in a present Example was based on the following method.
1. Ink adhesion evaluation method Ink (made by Dainichi Seika Kogyo Co., Ltd., Ramic SR739R Indigo M3 Kai) is diluted with Dainichi Seika Co., Ltd. The surface was coated with a mixed composition of a polypropylene resin and a modified resin so that the coating amount after drying was 3 g / m 2. Drying was carried out by natural drying for 24H, and cellophane tape (manufactured by Nichiban Co., Ltd., 15 mm width) was applied for 10 cm and rubbed until air was removed.
Thereafter, the cellophane tape was peeled off vigorously, and the evaluation was good if the ink peel-off amount was less than 5%, and x if it was more.
2. 120 ° C heat shrinkage rate A film cut into a 100 mm square in both length and width was immersed in a glycerin bath at 120 ° C for 10 seconds, then rapidly cooled in water, measured in length and width, and MD and TD heat shrinkage. The rate was calculated.
3. Pillow shrink wrapping machine suitability evaluation method (lateral sealability evaluation)
The packaging suitability of the film was evaluated by a pillow type continuous shrink wrapping machine used in overlap shrink wrapping of cup noodles. A commercially available bowl-shaped cup noodle having a film width of 440 mm and a bulk of 70 mm was pillow-packaged. The packaging machine is NEO type manufactured by Tokiwa Kogyo Co., Ltd., cut length is 230mm, packaging speed is 35m / min, vertical seal is knurled type, horizontal seal is the most commonly used fusing type. The temperature was 90 ° C. After sealing, Kyowa Denki L-2400FB tunnel was adjusted to 140-170 ° C. while watching the finished temperature for 2.5 seconds, and the film was heat shrunk. After packaging 100 pieces, the case where 2 or more pinholes with a diameter of 2 mm or more were seen in the lateral seal portion and it was judged that the sealing performance was poor was marked as x, and the case where the pinhole diameter was 2 mm or more and less than 1 was marked as ◯.
本発明の実施例及び比較例に使用したポリプロピレン樹脂およびそれと混合して使用される改質樹脂は以下を用いた。
I．ＭＦＲ＝２．６（２３０℃、２１．１８Ｎ）、ＪＩＳＫ７２０６に準じ１０Ｎ、昇温速度５０℃／時間で測定した軟化点が１３１℃のプロピレン−エチレンランダム共重合体
II．ＭＦＲ＝５（２３０℃、２１．１８Ｎ）、ＪＩＳＫ７２０６に準じ１０Ｎ、昇温速度５０℃／時間で測定した軟化点が１１０℃のプロピレン−ブテン−エチレン共重合体
III．ＭＦＲ＝１５（２３０℃、２１．１８Ｎ）、ＪＩＳＫ７２０６に準じ１０Ｎ、昇温速度５０℃／時間で測定した軟化点が１２２℃のプロピレン−エチレンランダム共重合体
IV．ＭＦＲ＝２．０（２３０℃、２１．１８Ｎ）、ＪＩＳＫ７２０６に準じ１０Ｎ、昇温速度５０℃／時間で測定した軟化点が１５０℃のポリプロピレン樹脂
V．表面固有抵抗は５×１０７Ωがポリエーテルとポリオレフィンのブロック共重合体（商品名「ペレスタット２３０」（三洋化成製））
VI．表面固有抵抗が３×１０６Ωのポリエーテルとポリオレフィンのブロック共重合体（商品名「ぺレクトロンＰＶＨ」（三洋化成製））
VII．商品名「クリアロンＰ１２５」（ヤルハラケミカル（株）製）の水添テルペン樹脂でありＪＩＳＫ７２３４で測定した軟化点が１２５℃
VIII．商品名「クリアロンＰ１２５」（ヤルハラケミカル（株）製）の水添テルペン樹脂でありＪＩＳＫ７２３４で測定した軟化点が１０５℃
IX．商品名「Ｐ６４４Ｖ」（三菱化学製）の酸変性ポリオレフィン。
X．商品名「ダウレックス２０４５Ｇ」（ダウケミカル製）のＭＦＲ＝１．０（１９０℃、２１．１８Ｎ）、密度＝０．９１０の線状低密度ポリエチレン
The following was used for the polypropylene resin used for the Example and comparative example of this invention, and the modified resin used in mixture with it.
I. MFR = 2.6 (230 ° C., 21.18 N), 10N according to JISK7206, propylene-ethylene random copolymer having a softening point of 131 ° C. measured at a heating rate of 50 ° C./hour
II. MFR = 5 (230 ° C., 21.18 N), propylene-butene-ethylene copolymer having a softening point of 110 ° C. measured at 10 N in accordance with JISK7206 at a heating rate of 50 ° C./hour
III. MFR = 15 (230 ° C., 21.18 N), propylene-ethylene random copolymer having a softening point of 122 ° C. measured at 10 N according to JISK7206 at a heating rate of 50 ° C./hour
IV. MFR = 2.0 (230 ° C., 21.18 N), polypropylene resin having a softening point of 150 ° C. measured at 10 N according to JISK7206 at a heating rate of 50 ° C./hour
V. The surface resistivity is 5 × 10 7 Ω, a block copolymer of polyether and polyolefin (trade name “Pelestat 230” (manufactured by Sanyo Kasei)).
VI. Polyether and polyolefin block copolymer with a surface resistivity of 3 × 10 6 Ω (trade name “Perectron PVH” (manufactured by Sanyo Kasei))
VII. It is a hydrogenated terpene resin of trade name “Clearon P125” (manufactured by Yalhara Chemical Co., Ltd.), and its softening point measured by JISK7234 is 125 ° C.
VIII. It is a hydrogenated terpene resin of the trade name “Clearon P125” (manufactured by Yalhara Chemical Co., Ltd.) and has a softening point of 105 ° C. measured by JISK7234.
IX. An acid-modified polyolefin having a trade name “P644V” (manufactured by Mitsubishi Chemical).
X. Linear low density polyethylene with a trade name “Daulex 2045G” (Dow Chemical) MFR = 1.0 (190 ° C., 21.18 N), density = 0.910
実施例１
表１に示すように、Iのポリプロピレン樹脂とIVの改質樹脂を混合比９５：５でブレンドし、１台の押出機で溶融混練し多層環状ダイスの外層に、他の2台の押出機でIの樹脂を芯層と内層にそれぞれ表１の層比で共押出した。形成された溶融樹脂チューブを、内側は冷却水が循環している円筒状冷却マンドレルの外表面を摺動させながら、外側は水槽を通すことにより冷却して引き取り、２４０μｍの未延伸シートを得た。
このチューブ状未延伸シートをチューブラー二軸延伸装置に導き、縦横それぞれ４．０×４．０倍に延伸し、フィルム厚み１５μｍの二軸延伸熱収縮性フィルムを得た。
得られたフィルムのヘーズ、インキ接着性、１２０℃熱収縮性、ピロー包装適性を評価し表１に示した。
Example 1
As shown in Table 1, I polypropylene resin and IV modified resin were blended at a mixing ratio of 95: 5, melted and kneaded by one extruder, and the other two extruders were formed on the outer layer of the multilayer annular die. The resin I was coextruded into the core layer and the inner layer at the layer ratio shown in Table 1. The formed molten resin tube was cooled by passing through the water tank while the outer surface of the cylindrical cooling mandrel in which the cooling water circulated was slid, and the outer side was passed through to obtain a 240 μm unstretched sheet. .
This tubular unstretched sheet was guided to a tubular biaxial stretching apparatus and stretched 4.0 times and 4.0 times in the longitudinal and lateral directions to obtain a biaxially stretched heat-shrinkable film having a film thickness of 15 μm.
The haze, ink adhesion, 120 ° C. heat shrinkability, and pillow packaging suitability of the obtained film were evaluated and shown in Table 1.
実施例２〜４、６〜１０、１２、比較例１〜６
表１に示すようなポリプロピレン樹脂と改質樹脂とを混合し、表に示す層比により実施した以外は実施例1と同様の方法で二軸延伸熱収縮性フィルムを得た。
得られたフィルムのヘーズ、インキ接着性、１２０℃熱収縮性、ピロー包装適性を評価し表１に示した。
Examples 2-4, 6-10, 12, Comparative Examples 1-6
A biaxially stretched heat-shrinkable film was obtained in the same manner as in Example 1 except that the polypropylene resin and the modified resin as shown in Table 1 were mixed and the layer ratio shown in the table was used.
The haze, ink adhesion, 120 ° C. heat shrinkability, and pillow packaging suitability of the obtained film were evaluated and shown in Table 1.
実施例５
表１に示すようなポリプロピレン樹脂と改質樹脂とを混合し、表に示す層比により４００μｍの未延伸シートを得た以外は実施例１と同様にして二軸延伸熱収縮性フィルムを得た。
得られたフィルムのヘーズ、インキ接着性、１２０℃熱収縮性、ピロー包装適性を評価し表１に示した。
Example 5
A biaxially stretched heat-shrinkable film was obtained in the same manner as in Example 1 except that a polypropylene resin and a modified resin as shown in Table 1 were mixed and an unstretched sheet of 400 μm was obtained according to the layer ratio shown in the table. .
The haze, ink adhesion, 120 ° C. heat shrinkability, and pillow packaging suitability of the obtained film were evaluated and shown in Table 1.
実施例１１
表１に示すようなポリプロピレン樹脂と改質樹脂とを混合し、表に示す層比により得たシートを延伸倍率３．０×３．０とした以外は実施例1と同様の方法で二軸延伸熱収縮性フィルムを得た。
得られたフィルムのヘーズ、インキ接着性、１２０℃熱収縮性、ピロー包装適性を評価し表１に示した。
Example 11
A polypropylene resin and a modified resin as shown in Table 1 were mixed, and the sheet obtained by the layer ratio shown in the table was biaxially treated in the same manner as in Example 1 except that the draw ratio was 3.0 × 3.0. A stretched heat-shrinkable film was obtained.
The haze, ink adhesion, 120 ° C. heat shrinkability, and pillow packaging suitability of the obtained film were evaluated and shown in Table 1.
表１より本発明の適切なポリプロピレン樹脂と改質樹脂の混合組成を表層に配する熱収縮フィルムは透明性良好と良好な収縮特性を有し、汎用性の高いインキとの接着性良好かつピロー連続高速包装時のシール性を両立できるものであった。一方、比較例１のように本発明の改質樹脂を配合しない場合は良好なインキ接着性が得られなかった。また比較例２のように一般的にオレフィン系の接着性改善改質樹脂と知られている酸変性ポリオレフィンは、インキ接着性が良好なものの、ピロー連続高速包装時の溶断シール性に劣り実用性は低いものである。 From Table 1, the heat shrinkable film having a suitable mixed composition of polypropylene resin and modified resin of the present invention arranged on the surface layer has good transparency and good shrinkage properties, good adhesion to highly versatile ink and pillows. The sealability at the time of continuous high-speed packaging was compatible. On the other hand, when the modified resin of the present invention was not blended as in Comparative Example 1, good ink adhesion was not obtained. In addition, as in Comparative Example 2, acid-modified polyolefin, which is generally known as an olefin-based adhesion-improving modified resin, has good ink adhesion, but is inferior in fusing and sealing properties during continuous continuous high-speed packaging. Is low.
本発明の熱収縮性包装材料は、インキとの接着性が改善されたポリオレフィン系熱収縮性フィルムで、従来使用されているポリオレフィン系熱収縮性フィルムと同様の高引張弾性率、高熱収縮率、高引裂強度、及び経時収縮が小さい等の特性バランスが優れ、高速自動包装に好適に用いられる。
The heat-shrinkable packaging material of the present invention is a polyolefin-based heat-shrinkable film with improved adhesion to ink, and has the same high tensile elastic modulus, high heat-shrinkage rate as conventional polyolefin-based heat-shrinkable films, It has excellent properties such as high tear strength and small shrinkage over time, and is suitable for high-speed automatic packaging.
Claims (3)
Ａ：ＪＩＳＫ７２０６に準じ１０N 及び昇温速度 ５０℃／時間で測定した軟化点が１００〜１３５℃であり、ＭＦＲが０．５〜６ポリプロピレン樹脂。
Ｂ：ポリエーテルとポリオレフィンのブロック共重合体であり、表面固有抵抗値が１０７〜１０１０Ωの変性ポリオレフィン樹脂又はＪＩＳＫ２２０７で測定した軟化点が８５〜１３５℃である水添テルペン樹脂。 A heat-shrinkable film made of polyolefin, having a heat shrinkage ratio of MD and TD of 120 ° C. of 10 to 70%, the composition of at least one surface layer is composed of a mixed resin of A and B, and A biaxially oriented polyolefin heat-shrinkable film having a B ratio of 97/3 to 40/60 per weight.
A: A polypropylene resin having a softening point of 100 to 135 ° C. and an MFR of 0.5 to 6 in accordance with JIS K7206, measured at 10 N and a heating rate of 50 ° C./hour.
B: A block copolymer of polyether and polyolefin, a modified polyolefin resin having a surface resistivity of 10 7 to 10 10 Ω, or a hydrogenated terpene resin having a softening point of 85 to 135 ° C. measured by JISK2207.
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