JP2002166472A - Heat-shrinkable polypropylene resin film - Google Patents
Heat-shrinkable polypropylene resin filmInfo
- Publication number
- JP2002166472A JP2002166472A JP2000368320A JP2000368320A JP2002166472A JP 2002166472 A JP2002166472 A JP 2002166472A JP 2000368320 A JP2000368320 A JP 2000368320A JP 2000368320 A JP2000368320 A JP 2000368320A JP 2002166472 A JP2002166472 A JP 2002166472A
- Authority
- JP
- Japan
- Prior art keywords
- heat
- film
- polypropylene resin
- resin film
- shrinkable
- 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.)
- Withdrawn
Links
- -1 polypropylene Polymers 0.000 title claims abstract description 55
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 36
- 229920005989 resin Polymers 0.000 title claims abstract description 35
- 239000011347 resin Substances 0.000 title claims abstract description 35
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 229920005604 random copolymer Polymers 0.000 claims description 11
- 229920005673 polypropylene based resin Polymers 0.000 claims description 9
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 8
- 230000005484 gravity Effects 0.000 claims description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 abstract description 18
- 239000005020 polyethylene terephthalate Substances 0.000 abstract description 18
- 238000000926 separation method Methods 0.000 abstract description 6
- 229920001577 copolymer Polymers 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 229920001038 ethylene copolymer Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920000092 linear low density polyethylene Polymers 0.000 description 3
- 239000004707 linear low-density polyethylene Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 229920006257 Heat-shrinkable film Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000009998 heat setting Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 239000002654 heat shrinkable material Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、透明性と低温収縮
性に優れ、かつ比重法によりポリエチレンテレフタレー
ト製ボトル、ポリエチレンテレフタレートフィルムなど
の成形体、特に、その破砕物との分別が可能な熱収縮性
ポリプロピレン系樹脂フィルム、好ましくは、シュリン
クラベル用熱収縮性ポリプロピレン系樹脂フィルムに関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-shrinkable material which is excellent in transparency and low-temperature shrinkage, and which can be separated from a molded product such as a polyethylene terephthalate bottle and a polyethylene terephthalate film by a specific gravity method, particularly, a crushed product thereof. The present invention relates to a heat-shrinkable polypropylene-based resin film, preferably a heat-shrinkable polypropylene-based resin film for shrink labels.
【０００２】[0002]
【従来の技術】近年、包装物品の外観向上のために外
装、内容物の直接衝撃を避けるための包装、タイト包
装、ガラスビン又はプラスチックボトルの保護と商品の
表示を兼ねたラベル包装などを目的として、シュリンク
ラベルが広く使用されている。2. Description of the Related Art In recent years, for the purpose of improving the external appearance of packaged articles, packaging for avoiding direct impact of the contents, tight packaging, label packaging for protecting glass bottles or plastic bottles and labeling goods, etc. , Shrink labels are widely used.
【０００３】プラスチック製の熱収縮性ラベルの印刷は
グラビア印刷されることが多く、通常３〜５色、中には
７色以上も印刷されることがある。熱収縮性フィルムが
最終製品（ラベル）となったときは、フィルム面上の印
刷面はラベル内面となり、フィルムを通して外面から印
刷面を見ることとなるためにヘイズが高い（不透明）と
容器の内容物の商品価値が大きく低下し、問題となる。The printing of heat-shrinkable labels made of plastic is often performed by gravure printing, and usually 3 to 5 colors, and sometimes 7 or more colors. When the heat-shrinkable film becomes the final product (label), the printed surface on the film surface becomes the label inner surface, and since the printed surface is viewed from the outer surface through the film, the haze is high (opaque) and the contents of the container The commercial value of goods is greatly reduced, which is a problem.
【０００４】また、低温収縮性に劣るとボトルにセット
されたラベルが、シュリンクトンネルを通して仕上げる
際にしっかりとフィットせず、仕上がりムラが見られ問
題となる。On the other hand, if the low-temperature shrinkage is inferior, the label set on the bottle does not fit firmly when finishing through a shrink tunnel, resulting in a problem of uneven finish.
【０００５】これらの目的に使用される収縮性フィルム
を製造するのに用いるプラスチック素材としてはポリ塩
化ビニル、ポリスチレン、ポリエチレンテレフタレー
ト、ポリプロピレンなどが知られている。[0005] As a plastic material used for producing a shrinkable film used for these purposes, polyvinyl chloride, polystyrene, polyethylene terephthalate, polypropylene and the like are known.
【０００６】しかしながら、ポリ塩化ビニルラベルは、
シュリンク特性には優れているが、焼却時に塩素ガスを
発生し環境汚染などの問題を抱えている。However, polyvinyl chloride labels are
Although it has excellent shrink characteristics, it generates chlorine gas during incineration and has problems such as environmental pollution.
【０００７】また、ポリスチレン、ポリエチレンテレフ
タレートラベルについては、熱収縮性は良好であるが、
ポリエチレンテレフタレートボトルとの比重が近値であ
るため、浮遊分離が困難となりポリエチレンテレフタレ
ートボトルのリサイクル性を妨げる。また、十分な熱収
縮性を得るために耐熱性の悪いポリマーを使用している
ため、レトルト殺菌を行うと溶融ポリマーによる印刷イ
ンキ流れを生じる。Further, polystyrene and polyethylene terephthalate labels have good heat shrinkability,
Since the specific gravity of the polyethylene terephthalate bottle is close to that of the polyethylene terephthalate bottle, floating separation becomes difficult, and the recyclability of the polyethylene terephthalate bottle is hindered. Further, since a polymer having poor heat resistance is used to obtain sufficient heat shrinkage, retort sterilization causes a printing ink flow due to a molten polymer.
【０００８】一方、ポリプロピレンフィルムは延伸が容
易にでき、そのフィルムは透明性が良好なフィルムであ
るが、低温収縮性、業務用ラップフィルムやシュリンク
包装用フィルムとして大きな欠点がある。On the other hand, a polypropylene film can be easily stretched and is a film having good transparency, but has significant drawbacks such as low-temperature shrinkage and commercial wrap film and shrink packaging film.
【０００９】これらの欠点を解決する方策としてエチレ
ンを３〜５ｗｔ％程度共重合したプロピレン−エチレン
ランダム共重合体や、エチレンを１〜３ｗｔ％、１−ブ
テンを３〜１０ｗｔ％程度共重合したプロピレン・エチ
レン−１−ブテン三元ランダム共重合体を２軸延伸処理
されたフィルムがあるが、透明、光沢が優れているもの
の、低温収縮性に劣るといった欠点を有している。ま
た、低温収縮性を向上させるために共重合量を増加させ
ると、透明性が劣る結果となる。As a measure for solving these drawbacks, a propylene-ethylene random copolymer obtained by copolymerizing ethylene in an amount of about 3 to 5% by weight or a propylene copolymer obtained by copolymerizing ethylene in an amount of about 1 to 3% by weight and 1-butene in an amount of about 3 to 10% by weight. -There is a film obtained by biaxially stretching an ethylene-1-butene tertiary random copolymer, but has a defect that it is excellent in transparency and gloss, but is inferior in low-temperature shrinkage. Further, when the amount of copolymerization is increased in order to improve the low-temperature shrinkability, the transparency becomes poor.
【００１０】他に、線状低密度ポリエチレン樹脂を芯層
として、プロピレン−エチレン共重合体を両表皮層とし
た多層の熱収縮フィルムが知られている。（特開昭５８
−１６６０４９号公報）In addition, a multilayer heat-shrinkable film is known in which a linear low-density polyethylene resin is used as a core layer and a propylene-ethylene copolymer is used as both skin layers. (Japanese Patent Laid-Open No. 58
16606049)
【００１１】しかし、本発明者らの知見によれば、確か
に、線状低密度ポリエチレン樹脂とプロピレン−エチレ
ン共重合体との双方の利点を合わせ持ち、透明、光沢が
優れ、耐引裂特性もある程度改良されているものの、低
温収縮性については、不十分であった。However, according to the findings of the present inventors, it is true that both the advantages of the linear low-density polyethylene resin and the propylene-ethylene copolymer are combined, the transparency and gloss are excellent, and the tear resistance is also high. Although improved to some extent, the low-temperature shrinkability was insufficient.
【００１２】[0012]
【発明が解決しようとする課題】上記従来の熱収縮性ポ
リプロピレン系樹脂フィルムは、透明、光沢が優れてい
るものの、低温収縮性に劣るといった欠点を有してお
り、また、低温収縮性を向上させるために共重合成分を
増加させると、透明性が劣るという問題があった。ま
た、後者のフィルムは、線状低密度ポリエチレン樹脂と
プロピレン−エチレン共重合体との双方の利点を合わせ
持ち、透明性、光沢が優れ、耐引裂特性もある程度改良
されているものの、低温収縮性については、不十分であ
った。The above-mentioned conventional heat-shrinkable polypropylene-based resin film has excellent transparency and gloss, but has the drawback of being inferior in low-temperature shrinkage, and has an improved low-temperature shrinkage. When the amount of the copolymer component is increased in order to reduce the transparency, there is a problem that the transparency is deteriorated. In addition, the latter film has the advantages of both a linear low-density polyethylene resin and a propylene-ethylene copolymer, and is excellent in transparency, gloss, and tear resistance. About was insufficient.
【００１３】本発明は、上記従来の熱収縮性ポリプロピ
レン系樹脂フィルムの有する問題点を解決し、低温収縮
性が良好で、透明性も満足することができ、また、ポリ
エチレンテレフタレート製ボトル、ポリエチレンテレフ
タレートフィルムなどの成形体、特にその破砕物との浮
遊分離を簡単に行なうことが出来、リサイクル性を向上
させることができる、熱収縮性ポリプロピレン系樹脂フ
ィルムを提供することにある。The present invention solves the above-mentioned problems of the conventional heat-shrinkable polypropylene-based resin film, has good low-temperature shrinkability, can satisfy transparency, and has a polyethylene terephthalate bottle, polyethylene terephthalate, etc. An object of the present invention is to provide a heat-shrinkable polypropylene-based resin film that can easily perform floating separation from a molded product such as a film, particularly a crushed product thereof, and can improve recyclability.
【００１４】[0014]
【課題を解決するための手段】上記目的を達成するた
め、本発明の熱収縮性ポリプロピレン系樹脂フィルム
は、ポリプロピレン系樹脂からなるフィルムであって、
該ポリプロピレン系樹脂からなるフィルムの温湯中にお
ける収縮率が、主収縮方向において７０℃の温水中で１
０秒処理した後の収縮率が５％以上であり、９０℃の温
水中で１０秒処理した後の収縮率が３０％以上であるこ
とを特徴とする。In order to achieve the above object, the heat-shrinkable polypropylene resin film of the present invention is a film made of a polypropylene resin,
The shrinkage ratio of the film made of the polypropylene resin in hot water is 1 in hot water of 70 ° C in the main shrinkage direction.
The shrinkage rate after the treatment for 0 seconds is 5% or more, and the shrinkage rate after the treatment for 10 seconds in warm water at 90 ° C. is 30% or more.
【００１５】上記の構成からなる本発明の熱収縮性ポリ
プロピレン系樹脂フィルムは、低温収縮性が良好で、透
明性も満足することができ、また、ポリエチレンテレフ
タレート製ボトル、ポリエチレンテレフタレートフィル
ムなどの成形体、特にその破砕物との浮遊分離を簡単に
行なうことが出来、リサイクル性を向上させることがで
きる。The heat-shrinkable polypropylene-based resin film of the present invention having the above-mentioned structure has good low-temperature shrinkage and satisfactory transparency, and is a molded product such as a polyethylene terephthalate bottle and a polyethylene terephthalate film. In particular, floating separation from the crushed material can be easily performed, and recyclability can be improved.
【００１６】この場合、熱収縮性ポリプロピレン系樹脂
フィルムは、比重を１．０以下とすることができる。In this case, the heat-shrinkable polypropylene resin film can have a specific gravity of 1.0 or less.
【００１７】また、熱収縮性ポリプロピレン系樹脂フィ
ルムは、９０℃の温水中で１０秒処理した後のヘイズを
８％以下とすることができる。The haze of the heat-shrinkable polypropylene resin film after being treated in hot water at 90 ° C. for 10 seconds can be reduced to 8% or less.
【００１８】また、熱収縮性ポリプロピレン系樹脂フィ
ルムは、ポリプロピレン系樹脂を、１−ブテン単位の含
有量が５〜５０モル％の範囲のポリプロピレン系樹脂と
することができる。In the heat-shrinkable polypropylene resin film, the polypropylene resin may be a polypropylene resin having a 1-butene unit content in the range of 5 to 50 mol%.
【００１９】さらに、熱収縮性ポリプロピレン系樹脂フ
ィルムは、ポリプロピレン系樹脂を、プロピレン−１−
ブテンランダム共重合体とすることができる。Further, the heat-shrinkable polypropylene resin film is obtained by converting a polypropylene resin into propylene-1-
It can be a butene random copolymer.
【００２０】[0020]
【発明の実施の形態】以下、本発明の熱収縮性ポリプロ
ピレン系樹脂フィルムの実施の形態を説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the heat-shrinkable polypropylene resin film of the present invention will be described.
【００２１】本発明の熱収縮性ポリプロピレン系フィル
ムを形成するポリプロピレン系樹脂は、プロピレンホモ
ポリマーからなるもの、プロピレンにエチレンやブテン
などを共重合したものが挙げられるが、好ましくは１−
ブテン単位を含むものである。さらに、１−ブテン単位
の含有量は５〜５０モル％、特に、１０〜４０モル％の
範囲であることが好ましく、さらに、単独のプロピレン
−１−ブテンランダム共重合体から構成されるものある
いは、２種類以上の異なる組成のプロピレン−１−ブテ
ンランダム共重合体の混合物が好ましい。プロピレン−
１−ブテンランダム共重合体は、ブテン含有量が５モル
％未満では低温収縮性が必ずしも充分ではなく、また、
５０モル％を越えると、フィルムがブロッキングを生じ
たり、あるいは、保管時に自然収縮を生じたりする傾向
にあり、実用にそぐわない。The polypropylene resin forming the heat-shrinkable polypropylene film of the present invention may be a propylene homopolymer, or a copolymer of propylene with ethylene or butene.
It contains butene units. Further, the content of the 1-butene unit is preferably in the range of 5 to 50 mol%, particularly preferably 10 to 40 mol%, and furthermore, one composed of a single propylene-1-butene random copolymer or A mixture of two or more types of propylene-1-butene random copolymers having different compositions is preferred. Propylene-
When the 1-butene random copolymer has a butene content of less than 5 mol%, the low-temperature shrinkage is not always sufficient,
If it exceeds 50 mol%, the film tends to cause blocking or to naturally contract during storage, which is not practical.
【００２２】共重合体中の１−ブテン単位は、赤外分光
光度計を用いて７７０ｃｍ-1の特性吸収から測定するこ
とができる。なお、赤外分光光度計による測定は、プロ
ピレン−１−ブテンランダム共重合体について、Ｃ−Ｎ
ＭＲによる定量値により検量線を作製し定量した。The 1-butene unit in the copolymer can be measured from the characteristic absorption at 770 cm -1 using an infrared spectrophotometer. In addition, the measurement by an infrared spectrophotometer was carried out on a propylene-1-butene random copolymer by using C-N
A calibration curve was prepared based on the quantitative value by MR and quantified.
【００２３】また、プロピレン−１−ブテンランダム共
重合体の冷キシレン可溶部（ＣＸＳ）は１〜６０重量
％、より好ましくは２〜５０重量％である。The content of the cold xylene-soluble portion (CXS) of the propylene-1-butene random copolymer is 1 to 60% by weight, more preferably 2 to 50% by weight.
【００２４】上記共重合体のメルトフローレート（ＭＦ
Ｒ）は、通常５〜１５ｇ／１０分、好ましくは４〜１０
ｇ／１０分である。The melt flow rate (MF) of the above copolymer
R) is generally 5 to 15 g / 10 min, preferably 4 to 10 g / 10 min.
g / 10 minutes.
【００２５】また、上記共重合体の融点は、通常１００
〜１５０℃、好ましくは１１０〜１４０℃である。The melting point of the above copolymer is usually 100
To 150 ° C, preferably 110 to 140 ° C.
【００２６】本発明の熱収縮性ポリプロピレン系フィル
ムを形成するポリプロピレン系樹脂は、上記のほか、本
発明の目的、効果を損なわない範囲で、ポリプロピレン
単独重合体、プロピレン・エチレン共重合体、プロピレ
ン・ブテン・エチレン共重合体、エチレン・プロピレン
共重合体、プロピレン・４−メチルペンテン−１共重合
体、ブテン・エチレン共重合体、ブテン・エチレン・プ
ロピレン共重合体、ポリエステル、ポリアミドなどの１
又は２種以上の重合体を混合することができる。また、
帯電防止剤、耐ブロッキング剤、滑剤、防曇剤、安定剤
及び造核剤などの添加剤を適宜混合してもよい。The polypropylene resin forming the heat-shrinkable polypropylene film of the present invention may be any of the above-mentioned polypropylene homopolymers, propylene / ethylene copolymers, propylene / ethylene copolymers as long as the objects and effects of the present invention are not impaired. 1 of butene / ethylene copolymer, ethylene / propylene copolymer, propylene / 4-methylpentene-1 copolymer, butene / ethylene copolymer, butene / ethylene / propylene copolymer, polyester, polyamide, etc.
Alternatively, two or more polymers can be mixed. Also,
Additives such as antistatic agents, antiblocking agents, lubricants, antifogging agents, stabilizers and nucleating agents may be appropriately mixed.
【００２７】具体的には、融点は、熱プレスにより作製
した厚さ０．５ｍｍのシートから切り出した約１０ｍｇ
の試片をＤＳＣ測定用サンプルに入れ、２３０℃で予備
加熱し、常温まで降温し、５分間保持した後、５℃／分
の速度で昇温し、そのサーモグラフから定量し、測定さ
れる。Specifically, the melting point was about 10 mg cut from a 0.5 mm thick sheet produced by hot pressing.
Is placed in a sample for DSC measurement, preheated at 230 ° C., cooled to room temperature, held for 5 minutes, then heated at a rate of 5 ° C./min, quantified from the thermograph and measured. .
【００２８】上記共重合体は、例えば触媒系として公知
のα−オレフィンの立体規則性重合用の触媒である、い
わゆるチーグラー・ナッタ触媒、すなわち周期律表第４
〜８族遷移金属化合物と周期律表第１〜３族典型金属の
有機化合物と、好ましくは電子供与体化合物の第３成分
とからなるものを使用して重合することにより得ること
ができる。The above-mentioned copolymer is, for example, a so-called Ziegler-Natta catalyst, which is a catalyst for stereoregular polymerization of an α-olefin known as a catalyst system, that is, No. 4 of the periodic table.
It can be obtained by polymerization using a compound consisting of a transition metal compound of Groups VIII to VIII, an organic compound of a typical metal of Groups 1 to 3 of the periodic table, and preferably a third component of an electron donor compound.
【００２９】重合法としては、溶剤中で重合する溶剤重
合法あるいは気相中で重合する気相重合法などが挙げら
れる。Examples of the polymerization method include a solvent polymerization method in which polymerization is performed in a solvent and a gas phase polymerization method in which polymerization is performed in a gas phase.
【００３０】上記樹脂組成物を得る方法は、特に限定さ
れるものではなく、公知の任意の方法、例えば押出溶融
ブレンド法、バンバリーブレンド法などが挙げられる。The method for obtaining the resin composition is not particularly limited, and may be any known method such as an extrusion melt blending method and a Banbury blending method.
【００３１】本発明の熱収縮性ポリプロピレン系樹脂フ
ィルムは、少なくとも一軸方向に延伸して得ることがで
きるが、特に低温収縮性が良好なフィルムを得るために
は、フィルムを延伸により十分配向させる必要がある。
例えばダイスを用いたＴダイキャスト法により成形され
たシートをテンター法又はロール延伸などの公知の延伸
方法により少なくとも、一軸方向、例えばＴＤ方向又は
ＭＤ方向に延伸して得られる。The heat-shrinkable polypropylene resin film of the present invention can be obtained by stretching at least uniaxially. In order to obtain a film having particularly good low-temperature shrinkability, it is necessary to orient the film sufficiently by stretching. There is.
For example, it is obtained by stretching a sheet formed by a T-die casting method using a die in at least a uniaxial direction, for example, a TD direction or an MD direction, by a known stretching method such as a tenter method or roll stretching.
【００３２】また、延伸は逐次二軸延伸、同時二軸延
伸、あるいはここに一軸延伸を組み合わせた延伸を行っ
ても良い。特に二軸延伸では直角方向の延伸は、どちら
か一方を先に行う逐次二軸延伸によるのが有効であり、
その順序はどちらが先でも良い。The stretching may be sequential biaxial stretching, simultaneous biaxial stretching, or a combination of uniaxial stretching and biaxial stretching. In particular, in the biaxial stretching, the stretching in the perpendicular direction is effective by successive biaxial stretching in which either one is performed first,
The order may be either.
【００３３】延伸条件は、主収縮方向に２．５〜９．０
倍、好ましくは３．０〜６．０倍に延伸し、上記方向と
直角方向に１．０〜２．０倍、好ましくは１．１〜１．
８倍延伸する。また、フィルムの延伸温度が非常に重要
な要素である。延伸温度４０℃から樹脂の融点より１０
℃低い温度、好ましくは４０℃以上の温度範囲で延伸す
ると、フィルムが十分配向し、良好な低温収縮性のある
延伸フィルムが得られる。このように、延伸温度、延伸
倍率を最適化することによって低温収縮性と透明性とを
両立することが可能となる。The stretching conditions are 2.5 to 9.0 in the main shrinkage direction.
Times, preferably 3.0-6.0 times, and 1.0-2.0 times, preferably 1.1-1.
Stretch 8 times. Also, the stretching temperature of the film is a very important factor. Stretching temperature from 40 ° C to 10 from melting point of resin
When the film is stretched at a temperature lower by ° C, preferably at a temperature of 40 ° C or higher, the film is sufficiently oriented, and a stretched film having good low-temperature shrinkability can be obtained. Thus, by optimizing the stretching temperature and the stretching ratio, it is possible to achieve both low-temperature shrinkage and transparency.
【００３４】さらに、フィルムを延伸した後のヒートセ
ットは目的に応じて実施するが、夏期高温下での保管時
の寸法変化を防止するためには３０〜１５０℃の加熱ゾ
ーンを、約１秒〜３０秒間通すことが推奨される。ま
た、かかるヒートセットの前後どちらか一方又は両方で
最高７０％までの伸長をかけても良い。Further, the heat setting after stretching the film is carried out according to the purpose. In order to prevent a dimensional change during storage at a high temperature in summer, a heating zone at 30 to 150 ° C. is applied for about 1 second. It is recommended to pass for ~ 30 seconds. Further, elongation up to 70% may be applied before or after the heat setting, or both.
【００３５】本発明の熱収縮性ポリプロピレン系樹脂フ
ィルムの温湯中における収縮率は、主収縮方向におい
て、処理温度７０℃・処理時間１０秒で５％以上であ
り、９０℃・１０秒で３０％以上であるが、好ましくは
処理温度７０℃・処理時間１０秒で７％以上であり、９
０℃・１０秒で４０％以上である。The shrinkage ratio of the heat-shrinkable polypropylene resin film of the present invention in hot water is 5% or more in the main shrinkage direction at a treatment temperature of 70 ° C. and a treatment time of 10 seconds, and 30% at 90 ° C. for 10 seconds. However, it is preferably 7% or more at a processing temperature of 70 ° C. and a processing time of 10 seconds.
It is 40% or more at 0 ° C. for 10 seconds.
【００３６】本発明の熱収縮性ポリプロピレン系樹脂フ
ィルムは、単層又は積層から構成される。The heat-shrinkable polypropylene resin film of the present invention comprises a single layer or a laminate.
【００３７】本発明の熱収縮性ポリプロピレン系樹脂フ
ィルムは、その比重が１．０以下であるのが好ましい。
ポリエチレンテレフタレート製ボトル、ポリエチレンテ
レフタレートフィルムなどの成形体、特に、その破砕物
との分別には、水を用いて比重法により分別するのが分
別物を洗浄する工程と兼ねて有用であるが、ポリエチレ
ンテレフタレート製ボトル、ポリエチレンテレフタレー
トフィルムなどの成形体、特に、その破砕物が水の下部
に沈降し、ポリプロピレン系樹脂フィルムが浮遊する状
態が実用的である。The heat-shrinkable polypropylene resin film of the present invention preferably has a specific gravity of 1.0 or less.
Polyethylene terephthalate bottles, molded products such as polyethylene terephthalate film, especially for separation from crushed material, it is useful to separate by a specific gravity method using water is also useful as a step of washing the separated material, polyethylene It is practical to use a molded product such as a terephthalate bottle or a polyethylene terephthalate film, especially a crushed product settled under water and a polypropylene resin film floating.
【００３８】本発明においては、熱処理後のヘイズが８
％以下、好ましくは５％以下である。８％を越えると印
刷が見えにくい。In the present invention, the haze after the heat treatment is 8
% Or less, preferably 5% or less. If it exceeds 8%, the print is difficult to see.
【００３９】[0039]
【実施例】以下、本発明を実施例に基づき説明するが、
本発明はこれら実施例に限定されるものではない。実施
例及び比較例におけるデータ及び評価は、次の方法に従
って行った。Hereinafter, the present invention will be described based on examples.
The present invention is not limited to these examples. Data and evaluation in Examples and Comparative Examples were performed according to the following methods.
【００４０】（１）収縮率 長さ１００ｍｍ×１００ｍｍのサンプルを７０℃又は９
０℃の温湯にそれぞれ１０秒間浸漬したときのＭＤ方向
（延伸と直角方向）又はＴＤ方向（延伸方向）の加熱前
後の寸法を測定し、下記式に基づき収縮率を算出した。 収縮率(％)＝((加熱前寸法−加熱後寸法)／加熱前寸法)
×１００ ＪＩＳ−Ｚ−１７０９に準拠して測定を実施した。(1) Shrinkage rate A sample having a length of 100 mm × 100 mm was heated at 70 ° C. or 9 ° C.
The dimensions before and after heating in the MD direction (direction perpendicular to the stretching) or TD direction (stretching direction) when immersed in hot water at 0 ° C. for 10 seconds were measured, and the shrinkage was calculated based on the following equation. Shrinkage (%) = ((dimension before heating-dimension after heating) / dimension before heating)
× 100 The measurement was performed according to JIS-Z-1709.
【００４１】（２）ヘイズ ９０℃の温水中で１０秒処理した後、ＪＩＳ−Ｋ−７１
０５に準拠して日本電色工業社製ヘイズメーターＮＤＨ
１００１ＤＰを使用し測定を実施した。(2) Haze After treatment in hot water at 90 ° C. for 10 seconds, JIS-K-71
Haze meter NDH manufactured by Nippon Denshoku Industries Co., Ltd.
The measurement was performed using 1001DP.
【００４２】（３）主収縮方向 フィルムを延伸方向とその直角方向に１０ｃｍ×１０ｃ
ｍの正方形に裁断し、８０℃±０．５℃の温水中に無荷
重状態で１０秒間処理して熱収縮させた後、フィルムの
縦及び横方向の寸法を測定し、収縮率の大きい方向を主
収縮方向とした。(3) Main shrinkage direction The film is stretched 10 cm × 10 c in the direction perpendicular to the stretching direction.
m, and heat shrink it by treating it in hot water at 80 ° C ± 0.5 ° C under no load for 10 seconds, measure the length and width of the film, and measure the direction of the large shrinkage. Was defined as the main contraction direction.
【００４３】（４）ポリマーの融点 理学電気社製サーモフレックスシリーズのＰＴＣ−１０
Ａを温調機とした外熱式ＤＳＣを使用し測定を実施し
た。(4) Melting point of polymer PTC-10 of Thermoflex series manufactured by Rigaku Corporation
The measurement was carried out using an externally heated DSC using A as a temperature controller.
【００４４】（５）ＭＦＲ ＪＩＳ−Ｋ−７２１０に基づき測定を実施した。(5) MFR Measurement was performed based on JIS-K-7210.
【００４５】（６）ブテンの量 １−ブテン単位は、赤外分光光度計（FTIR-8100M／島津
製作所社製）を用い、Ｃ−ＮＭＲによる定量値により検
量線を作成し７７０ｃｍ-1の特性吸収により測定した。(6) Amount of butene The 1-butene unit was determined by using an infrared spectrophotometer (FTIR-8100M / manufactured by Shimadzu Corporation) to prepare a calibration curve based on quantitative values by C-NMR and to obtain a characteristic of 770 cm -1 . It was measured by absorption.
【００４６】（実施例１）プロピレン・１−ブテンラン
ダム共重合体（住友化学工業社製、住友ノーブレン、１
−ブテン単位の含有量２７モル％、融点１３０℃、メル
トフローレート５ｇ／分）１００重量％を含有する樹脂
組成物を２２０℃でＴダイから押し出し、１５℃の冷却
ドラムに巻き付け、急冷し、未延伸シートを作製した。
このシートを５０℃で加熱した後、６０℃でＴＤ方向へ
６倍延伸し、さらに延伸速度は２０００％／分で実施
し、厚さ６０μｍの横一軸延伸シュリンクラベルフィル
ムを得た。得られたフィルムを９０℃で１０秒熱処理す
ることにより、収縮率が縦方向５％、横方向４２％で、
ヘイズが４．８％で低温収縮性並びに透明性の良好なラ
ベルが得られた。Example 1 Propylene / 1-butene random copolymer (Sumitomo Noblen, manufactured by Sumitomo Chemical Co., Ltd.)
A resin composition containing a butene unit content of 27 mol%, a melting point of 130 ° C. and a melt flow rate of 5 g / min) of 100% by weight is extruded from a T-die at 220 ° C., wound around a cooling drum at 15 ° C. and quenched An unstretched sheet was produced.
After heating the sheet at 50 ° C., the sheet was stretched 6 times in the TD direction at 60 ° C., and the stretching was performed at a stretching speed of 2000% / minute to obtain a 60 μm thick uniaxially stretched shrink label film. By subjecting the obtained film to heat treatment at 90 ° C. for 10 seconds, the shrinkage ratio is 5% in the vertical direction and 42% in the horizontal direction.
A label having a haze of 4.8% and excellent low-temperature shrinkage and transparency was obtained.
【００４７】（比較例１）プロピレン・エチレン・１−
ブテンランダム共重合体（住友化学工業社製、住友ノー
ブレン、エチレン単位の含有量２．１重量％、１−ブテ
ン単位の含有量５．７重量％、融点１３８℃、メルトフ
ローレート５ｇ／分）１００重量％を含有する樹脂組成
物を２４０℃でＴダイから押し出し、１５℃の冷却ドラ
ムに巻き付け、急冷し、未延伸シートを作製した。この
シートを８０℃で加熱した後４０〜８０℃でＴＤ方向へ
延伸するも、どの温度でもフィルムが破断し、延伸する
ことができなかった。Comparative Example 1 Propylene-ethylene-1-
Butene random copolymer (Sumitomo Chemical Industries, Ltd., Sumitomo Noblene, ethylene unit content 2.1% by weight, 1-butene unit content 5.7% by weight, melting point 138 ° C, melt flow rate 5g / min) A resin composition containing 100% by weight was extruded from a T-die at 240 ° C., wound around a cooling drum at 15 ° C., and rapidly cooled to produce an unstretched sheet. After heating this sheet at 80 ° C. and stretching it in the TD direction at 40 to 80 ° C., the film was broken at any temperature and could not be stretched.
【００４８】[0048]
【発明の効果】本発明の熱収縮性ポリプロピレン系樹脂
フィルムによれば、低温収縮性が良好で、透明性も満足
することができ、また、ポリエチレンテレフタレート製
ボトル、ポリエチレンテレフタレートフィルムなどの成
形体、特にその破砕物との浮遊分離を簡単に行なうこと
が出来、リサイクル性を向上させることができる。ま
た、本発明の熱収縮性ポリプロピレン系樹脂フィルム
は、ポリ塩化ビニルのような環境問題もない。According to the heat-shrinkable polypropylene resin film of the present invention, the low-temperature shrinkability is good, the transparency can be satisfied, and molded products such as polyethylene terephthalate bottles and polyethylene terephthalate films can be obtained. In particular, floating separation from the crushed material can be easily performed, and recyclability can be improved. Further, the heat-shrinkable polypropylene resin film of the present invention does not have environmental problems such as polyvinyl chloride.
Claims (5)
であって、該ポリプロピレン系樹脂からなるフィルムの
温湯中における収縮率が、主収縮方向において７０℃の
温水中で１０秒処理した後の収縮率が５％以上であり、
９０℃の温水中で１０秒処理した後の収縮率が３０％以
上であることを特徴とする熱収縮性ポリプロピレン系樹
脂フィルム。1. A film made of a polypropylene resin, which has a shrinkage rate in hot water of 5% after being treated in hot water at 70 ° C. for 10 seconds in a hot shrinkage direction. % Or more,
A heat-shrinkable polypropylene resin film having a shrinkage ratio of 30% or more after treatment in hot water at 90 ° C. for 10 seconds.
る請求項１記載の熱収縮性ポリプロピレン系樹脂フィル
ム。2. The heat-shrinkable polypropylene resin film according to claim 1, wherein the specific gravity is 1.0 or less.
イズが８％以下であることを特徴とする請求項１又は２
記載の熱収縮性ポリプロピレン系樹脂フィルム。3. The haze after treatment in hot water at 90 ° C. for 10 seconds is 8% or less.
The heat-shrinkable polypropylene resin film according to the above.
位の含有量が５〜５０モル％の範囲のポリプロピレン系
樹脂であることを特徴とする請求項１、２又は３記載の
熱収縮性ポリプロピレン系樹脂フィルム。4. The heat-shrinkable polypropylene-based resin according to claim 1, wherein the polypropylene-based resin is a polypropylene-based resin having a 1-butene unit content in the range of 5 to 50 mol%. Resin film.
１−ブテンランダム共重合体であることを特徴とする請
求項４記載の熱収縮性ポリプロピレン系樹脂フィルム。5. The method according to claim 1, wherein the polypropylene resin is propylene-
The heat-shrinkable polypropylene resin film according to claim 4, which is a 1-butene random copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000368320A JP2002166472A (en) | 2000-12-04 | 2000-12-04 | Heat-shrinkable polypropylene resin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000368320A JP2002166472A (en) | 2000-12-04 | 2000-12-04 | Heat-shrinkable polypropylene resin film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002166472A true JP2002166472A (en) | 2002-06-11 |
Family
ID=18838594
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000368320A Withdrawn JP2002166472A (en) | 2000-12-04 | 2000-12-04 | Heat-shrinkable polypropylene resin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2002166472A (en) |
-
2000
- 2000-12-04 JP JP2000368320A patent/JP2002166472A/en not_active Withdrawn
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