JP5660852B2 - Polyolefin heat shrinkable film with excellent shrink finish - Google Patents
Polyolefin heat shrinkable film with excellent shrink finish Download PDFInfo
- Publication number
- JP5660852B2 JP5660852B2 JP2010242433A JP2010242433A JP5660852B2 JP 5660852 B2 JP5660852 B2 JP 5660852B2 JP 2010242433 A JP2010242433 A JP 2010242433A JP 2010242433 A JP2010242433 A JP 2010242433A JP 5660852 B2 JP5660852 B2 JP 5660852B2
- Authority
- JP
- Japan
- Prior art keywords
- propylene
- temperature
- heat
- ethylene
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920000098 polyolefin Polymers 0.000 title claims description 14
- 229920006257 Heat-shrinkable film Polymers 0.000 title claims description 13
- 238000002844 melting Methods 0.000 claims description 44
- 230000008018 melting Effects 0.000 claims description 44
- 229920001577 copolymer Polymers 0.000 claims description 32
- 229920005989 resin Polymers 0.000 claims description 32
- 239000011347 resin Substances 0.000 claims description 32
- 239000002344 surface layer Substances 0.000 claims description 26
- 239000012968 metallocene catalyst Substances 0.000 claims description 23
- 239000012792 core layer Substances 0.000 claims description 21
- 239000010410 layer Substances 0.000 claims description 20
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 15
- 239000005977 Ethylene Substances 0.000 claims description 15
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 14
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 14
- 238000005259 measurement Methods 0.000 claims description 6
- 239000004711 α-olefin Substances 0.000 claims description 6
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 4
- 238000004806 packaging method and process Methods 0.000 description 27
- -1 polypropylene Polymers 0.000 description 17
- 230000037303 wrinkles Effects 0.000 description 13
- 238000010521 absorption reaction Methods 0.000 description 10
- 229920005604 random copolymer Polymers 0.000 description 8
- 229920006300 shrink film Polymers 0.000 description 8
- 239000011342 resin composition Substances 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 230000001771 impaired effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005629 polypropylene homopolymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- WXCZUWHSJWOTRV-UHFFFAOYSA-N but-1-ene;ethene Chemical compound C=C.CCC=C WXCZUWHSJWOTRV-UHFFFAOYSA-N 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000002654 heat shrinkable material Substances 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920005638 polyethylene monopolymer Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Description
本発明は収縮包装材料に関し、より詳しくは、収縮仕上がり性に優れたポリオレフィン系熱収縮性フィルムに関する。 The present invention relates to a shrink wrap material, and more particularly, to a polyolefin-based heat shrinkable film excellent in shrink finish.
従来、熱収縮性包装材料としては、ポリ塩化ビニル系シュリンクフィルム、ポリプロピレン系シュリンクフィルム、ポリエチレン系シュリンクフィルム等が知られていが、低価格、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。しかしながら、ポリプロピレン系シュリンクフィルムは耐熱性等に優れるものの、低温収縮性、耐引裂性に乏しい等の欠点を有している。一方、ポリエチレン系シュリンクフィルムは、低温収縮性、耐引裂性等に優れるものの、耐熱性に乏しい等の欠点を有している。 Conventionally, polyvinyl chloride shrink film, polypropylene shrink film, polyethylene shrink film, and the like are known as heat shrinkable packaging materials, but polypropylene, in terms of low cost, easy disposal after use, etc. Polyolefin shrink films such as polyethylene are preferably used. However, although the polypropylene-based shrink film is excellent in heat resistance and the like, it has drawbacks such as low temperature shrinkage and poor tear resistance. On the other hand, the polyethylene-based shrink film has defects such as poor heat resistance, although it is excellent in low-temperature shrinkage and tear resistance.
これらの欠点を改善すべく、エチレン系樹脂に架橋処理を施したポリエチレン系架橋シュリンクフィルムが開示されている（特許文献１）。これらのポリエチレン系架橋シュリンクフィルムは、低温収縮性、耐熱性、耐引裂性等に優れるものの、架橋処理を施されているため、製造工程や規格外製品で発生するスクラップを再利用し難く、製品のコストアップを招く、省資源性が低下するといった問題を有していた。 In order to improve these drawbacks, a polyethylene-based crosslinked shrink film obtained by crosslinking an ethylene-based resin has been disclosed (Patent Document 1). These polyethylene-based cross-linked shrink films are excellent in low-temperature shrinkage, heat resistance, tear resistance, etc., but because they are cross-linked, it is difficult to reuse scrap generated in manufacturing processes and non-standard products. There are problems such as cost increase and resource saving.
また、プロピレン系樹脂、エチレン系樹脂を表層や内部層に、単独又はブレンド系で積層したポリオレフィン系熱収縮性フィルム（特許文献２〜７）が開示されている。これらのフィルムは、低温収縮性や耐熱性等が依然不十分であり、化粧品や薬品等の高価な商品を包装する際に必要とされる高度な収縮仕上がり性が得られないという課題を有していた。 Moreover, the polyolefin-type heat-shrinkable film (patent documents 2-7) which laminated | stacked propylene-type resin and ethylene-type resin on the surface layer and the inner layer individually or by the blend type | system | group is disclosed. These films still have insufficient low-temperature shrinkage, heat resistance, etc., and have a problem that the high shrinkage finish required for packaging expensive products such as cosmetics and drugs cannot be obtained. It was.
本発明は、架橋を行うことなく優れた低温収縮性、耐熱性が得られ、高価な商品を包装する際に必要とされる高度な収縮仕上がり性を発現可能な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ものである。 The present invention provides a polyolefin-based heat-shrinkable film that has excellent low-temperature shrinkage and heat resistance without crosslinking, and can exhibit the high degree of shrinkage finish required when packaging expensive products. It is an object to do.
本発明者らは、かかる課題を解決すべく鋭意検討した結果、本発明に到達したものである。すなわち、本発明は、メタロセン触媒により製造されるプロピレン−ブテン−１共重合体１０〜６０重量部とプロピレン系樹脂４０〜９０重量部からなる表層、及びエチレン系樹脂からなる芯層の少なくとも３層からなり、縦横２軸延伸したポリオレフィン系熱収縮性フィルムを提供し、好ましくは、下記イ）〜二）からなることを特徴とするポリオレフィン系熱収縮性フィルムを提供するものである。イ）表層のメタロセン触媒により製造されるプロピレン−ブテン−１共重合体の示差走査熱量計（以下ＤＳＣと記す）によって測定される融解ピーク温度が６０〜９０℃、ロ）表層プロピレン系樹脂の、ＤＳＣによって測定される融解ピーク温度が１２０〜１６５℃、メルトフローレート（以下ＭＦＲと記す。測定温度２３０℃、荷重２．１６ｋｇｆ）が０．３〜１０．０ｇ／１０分、ハ）芯層エチレン系樹脂が、密度０．８６５〜０．９２５ｇ／ｃｍ3、さらに好ましくは０．８７０〜０．９１０ｇ／ｃｍ3、メルトインデックス（以下ＭＩと記す。測定温度１９０℃、荷重２．１６ｋｇｆ）０．５〜４．０ｇ／１０分のエチレン−αオレフィン共重合体１種または２種以上からなる、ニ）表層のメタロセン触媒により製造されるプロピレン−ブテン−１共重合体が、ＤＳＣを用いた測定において、溶融開始温度から溶融ピーク温度よりも２０℃低い温度までの間に吸収された熱量の総量が上記溶融開始温度から上記溶融終了温度までの間に吸収された全熱量の４０％以下である。 The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve such problems. That is, the present invention provides at least three layers of a surface layer composed of 10 to 60 parts by weight of a propylene-butene-1 copolymer produced by a metallocene catalyst and 40 to 90 parts by weight of a propylene-based resin, and a core layer composed of an ethylene-based resin. And a polyolefin-based heat-shrinkable film stretched biaxially and transversely, preferably a polyolefin-based heat-shrinkable film comprising the following a) to 2). A) The melting peak temperature measured by a differential scanning calorimeter (hereinafter referred to as DSC) of a propylene-butene-1 copolymer produced by a surface metallocene catalyst is 60 to 90 ° C. Melting peak temperature measured by DSC is 120 to 165 ° C., melt flow rate (hereinafter referred to as MFR, measuring temperature 230 ° C., load 2.16 kgf) is 0.3 to 10.0 g / 10 min, c) core layer ethylene The resin has a density of 0.865 to 0.925 g / cm 3 , more preferably 0.870 to 0.910 g / cm 3 , a melt index (hereinafter referred to as MI, measurement temperature 190 ° C., load 2.16 kgf). Propylene produced by a metallocene catalyst on the surface layer, consisting of one or more ethylene-α-olefin copolymers of 5 to 4.0 g / 10 min. The total amount of heat absorbed between the melting start temperature and the temperature 20 ° C. lower than the melting peak temperature in the measurement using DSC for the butene-1 copolymer is from the melting start temperature to the melting end temperature. It is 40% or less of the total heat absorbed during the period.
本発明のポリオレフィン系熱収縮性フィルムは、低温収縮性等に優れたメタロセン触媒で製造されたプロピレン−ブテン−１共重合体と、耐熱性等に優れたプロピレン系樹脂からなる表層、低温収縮性と耐引裂性等に優れたエチレン系樹脂からなる芯層の少なくとも３層からなり、縦横２軸延伸することで、優れた低温収縮性、耐熱性が得られ、高価な商品を包装する際に必要とされる高度な収縮仕上がり性を発現することができる、という効果を奏する。 The polyolefin heat-shrinkable film of the present invention is a surface layer composed of a propylene-butene-1 copolymer produced with a metallocene catalyst excellent in low-temperature shrinkage and the like, and a propylene resin excellent in heat resistance and the like, and low-temperature shrinkage It consists of at least three layers of a core layer made of an ethylene-based resin with excellent tear resistance, etc., and by stretching in the vertical and horizontal directions, excellent low temperature shrinkage and heat resistance can be obtained, and when packaging expensive products There is an effect that the required high degree of shrink finish can be achieved.
以下、本発明を詳細に説明する。
本発明において、表層に用いるプロピレン−ブテン−１共重合体は、メタロセン触媒で製造されるものであり、表層の樹脂１００重量部中に１０〜６０重量部含まれ、主に低温収縮性を付与する作用を成す。メタロセン触媒で製造されるプロピレン−ブテン−１共重合体の表層中の組成が１０重量部未満では低温収縮性が不足し、６０重量部を超えると滑り性が低下し、双方の場合において、高価な商品を包装する際に必要とされる高度な収縮仕上がり性を発現することができないので好ましくない。
Hereinafter, the present invention will be described in detail.
In the present invention, the propylene-butene-1 copolymer used for the surface layer is produced with a metallocene catalyst, and is contained in 10 to 60 parts by weight in 100 parts by weight of the resin on the surface layer, and mainly imparts low temperature shrinkage. To act. If the composition in the surface layer of the propylene-butene-1 copolymer produced with the metallocene catalyst is less than 10 parts by weight, the low temperature shrinkage is insufficient, and if it exceeds 60 parts by weight, the slipping property is lowered. It is not preferable because the high degree of shrinkage finish required for packaging a new product cannot be expressed.
また、表層に用いるメタロセン触媒により製造されるプロピレン−ブテン−１共重合体は、ＤＳＣによって測定される融解ピーク温度が６０〜９０℃であることが好ましい。融解ピーク温度が６０℃未満では滑り性が低下し易く、９０℃超えると低温収縮性が低下し易い。 The propylene-butene-1 copolymer produced by the metallocene catalyst used for the surface layer preferably has a melting peak temperature measured by DSC of 60 to 90 ° C. If the melting peak temperature is less than 60 ° C, the slipperiness tends to decrease, and if it exceeds 90 ° C, the low temperature shrinkage tends to decrease.
さらに、表層のメタロセン触媒により製造されるプロピレン−ブテン−１共重合体は、ＤＳＣを用いた測定において、溶融開始温度から溶融ピーク温度よりも２０℃低い温度までの間に吸収された熱量の総量が上記溶融開始温度から上記溶融終了温度までの間に吸収された全熱量の３９％以下、好ましくは３０％以下、さらには好ましくは２０％以下であることが望ましい。３９％を超えると、滑り性が低下し易くなる。 Further, the propylene-butene-1 copolymer produced by the metallocene catalyst of the surface layer is the total amount of heat absorbed from the melting start temperature to a temperature 20 ° C. lower than the melting peak temperature in the measurement using DSC. Is not more than 39%, preferably not more than 30%, more preferably not more than 20% of the total amount of heat absorbed between the melting start temperature and the melting end temperature. If it exceeds 39%, the slipperiness tends to decrease.
本発明の表層に用いるプロピレン系樹脂とは、プロピレン含量が５０ｍｏｌ％以上からなる重合体のことであり、メタロセン触媒やチーグラー・ナッタ触媒等により製造された、ポリプロピレン単独重合体、プロピレンと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−ブテン共重合体等、及びプロピレン−エチレン−ブテン３元共重合体の中から選ばれる少なくとも一種以上からなり、表層の樹脂１００重量部中に４０〜９０重量部含まれ、主に耐熱性を付与する作用を成す。
プロピレン系樹脂の表層中の組成が４０重量部未満では耐熱性が低下し、９０重量部を超えると低温収縮性が低下し、双方の場合において、高価な商品を包装する際に必要とされる高度な収縮仕上がり性を発現することができないので好ましくない。
The propylene-based resin used for the surface layer of the present invention is a polymer having a propylene content of 50 mol% or more, and is a polypropylene homopolymer, propylene and α-olefin produced by a metallocene catalyst, a Ziegler-Natta catalyst, or the like. A copolymer of, for example, propylene-ethylene, propylene-butene copolymer, and the like, and propylene-ethylene-butene terpolymer. 90 parts by weight is contained, and mainly serves to impart heat resistance.
When the composition in the surface layer of the propylene-based resin is less than 40 parts by weight, the heat resistance is lowered, and when it exceeds 90 parts by weight, the low-temperature shrinkage is lowered. In both cases, it is required for packaging expensive products. This is not preferable because a high degree of shrinkage finish cannot be expressed.
また、表層に用いるプロピレン系樹脂はＤＳＣによって測定される融解ピーク温度が１２０〜１６５℃、ＭＦＲが０．３〜１０．０ｇ／１０分であることが好ましい。融解ピーク温度が１２０℃未満では耐熱性が低下し易く、１６５℃を超えると低温収縮性が低下し易く、ＭＦＲが０．３ｇ／１０分未満や、１０．０ｇ／１０分を超える場合には、透明性が低下し易い。 The propylene-based resin used for the surface layer preferably has a melting peak temperature measured by DSC of 120 to 165 ° C. and an MFR of 0.3 to 10.0 g / 10 minutes. If the melting peak temperature is less than 120 ° C, the heat resistance tends to be low, and if it exceeds 165 ° C, the low temperature shrinkage tends to be low, and if the MFR is less than 0.3 g / 10 min or 10.0 g / 10 min , Transparency tends to decrease.
本発明の芯層に用いるエチレン系樹脂とは、エチレン含量が５０ｍｏｌ％以上からなる重合体のことであり、プロピレン、ブテン−１、ペンテンー１、ヘキセン−１、ヘプテン−１、オクテン−１、４−メチルペンテン−１から成る群から選ばれた１種又は２種以上のα−オレフィンとエチレンとの共重合体、エチレン−酢酸ビニル共重合体、エチレン−脂肪族不飽和カルボン酸共重合体、エチレン−脂肪族不飽和カルボン酸エステル共重合体、アイオノマー樹脂、ポリエチレン単独重合体から選ばれる少なくとも１種以上からなり、主に低温収縮性、耐引裂性を付与する作用を成す。
芯層にエチレン系樹脂が使用されない場合には、低温収縮性、耐引裂性が不足し、高価な商品を包装する際に必要とされる高度な収縮仕上がり性を発現することができない他、包装品が破れやすい等の問題が生じるので好ましくない。
The ethylene-based resin used for the core layer of the present invention is a polymer having an ethylene content of 50 mol% or more. Propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, 4 A copolymer of one or more α-olefins selected from the group consisting of methylpentene-1 and ethylene, an ethylene-vinyl acetate copolymer, an ethylene-aliphatic unsaturated carboxylic acid copolymer, It consists of at least one selected from an ethylene-aliphatic unsaturated carboxylic acid ester copolymer, an ionomer resin, and a polyethylene homopolymer, and mainly serves to impart low-temperature shrinkage and tear resistance.
When ethylene-based resin is not used for the core layer, low-temperature shrinkage and tear resistance are insufficient, and the high shrinkage finish required for packaging expensive products cannot be expressed. This is not preferable because problems such as easy breakage of the product occur.
また、芯層に用いられるエチレン系樹脂は、密度０．８６５〜０．９２５ｇ／ｃｍ3、ＭＩ０．５〜４．０ｇ／１０分のエチレン−αオレフィン共重合体１種または２種以上からなることが好ましい。密度については、０．８７０〜０．９１０ｇ／ｃｍ3であることがさらに好ましい。密度が０．８６５ｇ／ｃｍ3未満の場合にはフィルムの引張弾性率が低下し、包装機での走行性が低下する傾向があり、０．９２５ｇ／ｃｍ3 を超えると低温収縮性が低下し易くなる。ＭＩが０．５ｇ／１０分未満のものは、押出時のモーター負荷が増大し易くなり、４．０ｇ／１０分を超えると延伸加工性、耐熱性の低下や、溶断シール時にピンホールやシール開きが発生し易くなる。 The ethylene resin used for the core layer is composed of one or more ethylene-α olefin copolymers having a density of 0.865 to 0.925 g / cm 3 and an MI of 0.5 to 4.0 g / 10 min. It is preferable. The density is more preferably 0.870 to 0.910 g / cm 3 . When the density is less than 0.865 g / cm 3, the tensile elastic modulus of the film tends to be lowered and the running property in the packaging machine tends to be lowered. When the density exceeds 0.925 g / cm 3 , the low temperature shrinkage is lowered. It becomes easy. When MI is less than 0.5 g / 10 min, the motor load at the time of extrusion tends to increase, and when it exceeds 4.0 g / 10 min, stretching workability and heat resistance decrease, and pinholes and seals at the time of fusing sealing Opening tends to occur.
表層及び／又は芯層は、本発明の目的に支障をきたさない範囲であれば、他の樹脂を混合することもできる。たとえば、表層にはエチレン系樹脂を混合して、芯層にはメタロセン触媒で製造されるプロピレン−ブテン−１共重合体や、プロピレン系樹脂を混合して用いる事が出来、これにより、要求される特性に応じて諸物性の調整を行う事が出来、またトリムや格外品等の再利用樹脂を混合使用する事も出来る。 The surface layer and / or the core layer can be mixed with other resins as long as the object of the present invention is not affected. For example, an ethylene-based resin can be mixed in the surface layer, and a propylene-butene-1 copolymer produced with a metallocene catalyst or a propylene-based resin can be mixed and used in the core layer. Various physical properties can be adjusted according to the characteristics to be used, and it is also possible to mix and use recycled resins such as trims and non-standard products.
本発明の層構成は、少なくとも３層以上の層構成であり、例えばＡ／Ｂ／Ａの３層構成、Ａ／Ａ＋Ｂ／Ｂ／Ａ＋Ｂ／Ａ、Ａ／Ｂ／Ａ＋Ｂ／Ｂ／Ａ等の５層構成が挙げられる。中でも、Ａ＋Ｂ層を設けた層構成は、諸物性の調整や再利用樹脂の混合使用がやりやすくなり、好適である。
Ａ＋Ｂ層における、メタロセン触媒で製造されるプロピレン−ブテン−１共重合体、プロピレン系樹脂とエチレン系樹脂の混合比率は、本発明の目的に支障をきたさない範囲であれば、特に制限はない。
The layer structure of the present invention is a layer structure of at least three layers. For example, A / B / A three-layer structure, A / A + B / B / A + B / A, A / B / A + B / B / A, etc. A layer structure is mentioned. Among them, the layer structure provided with the A + B layer is preferable because it is easy to adjust various physical properties and to mix and use recycled resins.
The mixing ratio of the propylene-butene-1 copolymer produced with the metallocene catalyst and the propylene-based resin and the ethylene-based resin in the A + B layer is not particularly limited as long as the object of the present invention is not hindered.
本発明の各層の厚み構成比については特に限定されないが、芯層の厚み比率が全体厚みに対し４０〜８０％の範囲内であることが好ましい。芯層の厚み比率が４０％未満では耐引裂性が低下し易くなり、８０％を超えると耐熱性が低下し易くなる。フィルムの全体厚みも特に限定されないが、熱収縮性包装材料用途としては７〜３５μｍであることが好ましい。 Although it does not specifically limit about the thickness structural ratio of each layer of this invention, It is preferable that the thickness ratio of a core layer exists in the range of 40 to 80% with respect to the whole thickness. If the thickness ratio of the core layer is less than 40%, the tear resistance tends to be lowered, and if it exceeds 80%, the heat resistance tends to be lowered. Although the total thickness of the film is not particularly limited, it is preferably 7 to 35 μm as a heat shrinkable packaging material.
本発明の目的に支障をきたさない範囲であれば、滑剤、ブロッキング防止剤、帯電防止剤、防曇剤、酸化防止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。 As long as it does not interfere with the object of the present invention, additives such as lubricants, antiblocking agents, antistatic agents, antifogging agents, and antioxidants should be used appropriately for the purpose of providing each effective action. Can do.
次に、本発明のフィルムの製造方法を示す。前記の樹脂を用いて本発明のフィルムを製造する方法は、公知の縦横２軸延伸方法で行うことができる。
以下、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、メタロセン触媒により製造されるプロピレン−ブテン−１共重合体とプロピレン系樹脂の混合物を表層、及びエチレン系樹脂を芯層となるように、３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フィルムを作製する。得られたチューブ状未延伸フィルムを、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、例えば芯層樹脂の融点以下１０℃よりも低い温度で、好ましくは融点以下１５℃よりも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、縦横とも延伸倍率３〜６倍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、希望によりアニーリングすることができ、このアニーリングにより保存中の自然収縮を抑制することができる。
Next, the manufacturing method of the film of this invention is shown. The method for producing the film of the present invention using the above resin can be carried out by a known longitudinal and transverse biaxial stretching method.
Hereinafter, the case of three-layer laminated annular film-forming stretching will be described as an example.
First, a mixture of a propylene-butene-1 copolymer produced with a metallocene catalyst and a propylene-based resin is melt-kneaded with three extruders so that a surface layer and an ethylene-based resin become a core layer, and a three-layer ring It is co-extruded in a ring shape from a die, and once cooled and solidified without stretching, a tubular unstretched film is produced. The obtained tubular unstretched film is supplied to a tubular stretching apparatus, and is in a highly orientable temperature range, for example, at a temperature lower than 10 ° C below the melting point of the core layer resin, preferably lower than 15 ° C below the melting point. By applying a gas pressure to the inside of the tube at a temperature and expanding and stretching, simultaneous biaxial orientation is caused at a stretching ratio of 3 to 6 in both length and width. The film taken out from the stretching apparatus can be annealed as desired, and the natural shrinkage during storage can be suppressed by this annealing.
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、実施例及び比較例おける測定及び評価の方法は、以下に示す通りに行った。
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.
In addition, the method of the measurement and evaluation in an Example and a comparative example was performed as shown below.
１．フィルム厚み：ＪＩＳ−Ｚ１７０９に準じて測定した。 1. Film thickness: measured according to JIS-Z1709.
２．厚み比：フィルムの断面を顕微鏡で観察することにより測定した。 2. Thickness ratio: Measured by observing the cross section of the film with a microscope.
３．ヘイズ：ＪＩＳ−Ｋ７１０５に準じて測定した。 3. Haze: Measured according to JIS-K7105.
４．ＭＩ：ＪＩＳ−Ｋ７２１０に準じて、１９０℃、２．１６ｋｇ荷重条件で測定した。 4). MI: Measured according to JIS-K7210 at 190 ° C. and 2.16 kg load condition.
５．ＭＦＲ：ＪＩＳ−Ｋ７２１０に準じて、２３０℃、２．１６ｋｇ荷重条件で測定した。 5. MFR: Measured under conditions of 230 ° C. and 2.16 kg load according to JIS-K7210.
６．低温吸収割合：ＤＳＣを用いた測定において、（溶融開始温度から溶融ピーク温度よりも２０℃低い温度までの間に吸収された熱量の総量）／（上記溶融開始温度から上記溶融終了温度までの間に吸収された全熱量）×１００、で導かれる低温側の吸収熱量の全熱量に対する割合を測定した。 6). Low-temperature absorption ratio: In measurement using DSC, (total amount of heat absorbed from the melting start temperature to a temperature 20 ° C. lower than the melting peak temperature) / (between the melting start temperature and the melting end temperature) The total amount of heat absorbed by the low-temperature-side absorbed heat led to the total amount of heat was measured.
７．引張弾性率：ＪＩＳ−Ｚ７１２７に準じて測定した。 7). Tensile modulus: measured according to JIS-Z7127.
８．１００℃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１００℃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、式（１）によりＭＤ、ＴＤの熱収縮率を算出した。
９．収縮包装仕上がり性：協和電機（株）製のL型シール式半折自動包装機（型式：AT-500）
にて、市販の化粧品ボトル容器を余裕率２０％の条件で予備包装し、フィルムの耐熱
限界５℃手前に設定した収縮トンネル内を５秒滞留させ、トンネル通過後の
包装サンプルの中から無作為に５つを選び、以下の基準で評価した。
＜評価基準＞
○：包装サンプルの四隅の角立ちが極めて小さく、小ジワも殆ど無く、見栄えが良い。
△：包装サンプルの四隅の角立ちや小ジワがやや目立つ。
×：包装サンプルの四隅の角立ちや小ジワが明らかに目立ち、外観を著しく損ねる。または、包装時にフィルムが走行不良を起こし、傷などが入って外観を損ねる。
9. Shrink packaging finish: Kyowa Denki Co., Ltd. L-shaped seal type half-fold automatic packaging machine (model: AT-500)
, Pre-wrapped a cosmetic bottle container on the market at a margin rate of 20%, stays in the shrink tunnel set at 5 ° C before the heat limit of the film for 5 seconds, and randomly selected from the packaging sample after passing through the tunnel Five were selected and evaluated according to the following criteria.
<Evaluation criteria>
○: The corners of the four corners of the packaging sample are extremely small, there are almost no wrinkles, and the appearance is good.
Δ: Corners and wrinkles at the four corners of the packaging sample are slightly noticeable.
X: The corners and wrinkles at the four corners of the packaging sample are clearly noticeable and the appearance is remarkably impaired. Or the film causes poor running at the time of packaging, and scratches and the like are damaged.
実施例１
表１に示すように、融解ピーク温度が７５℃、低温吸収割合が１０％の特性を有するメタロセン触媒により製造されるプロピレン−ブテン−１共重合体４５重量部、融解ピーク温度が１４５℃、ＭＦＲが２．３ｇ／１０分の特性を有するプロピレン−エチレンランダム共重合体５５重量部からなる樹脂組成物を両表面層とし、密度０．９０５ｇ／ｃｍ3、ＭＩ０．８ｇ／１０分であるエチレン−オクテン−１共重合体を芯層とし、３台の押出機で溶融混練した後、厚み比が１／５／１になるように各押出機の押出量を設定し、３層環状ダイスにより下向きに共押出した。形成された３層構成チューブを、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、未延伸フィルムを得た。得られた未延伸チューブをチューブラー二軸延伸装置に導き、９０〜１１０℃で縦横それぞれ５倍に延伸し、フィルム厚み１５μｍの積層二軸延伸フィルムを得た。
表１に示すように、得られたフィルムは、収縮包装仕上がり性に優れるもので、包装サンプルの四隅の角やコーナーシワが殆ど目立たない外観美麗な収縮包装体が得られた。その他、ヘイズ、引張弾性率、１００℃熱収縮率等の特性も良好であった。
Example 1
As shown in Table 1, 45 parts by weight of a propylene-butene-1 copolymer produced by a metallocene catalyst having a melting peak temperature of 75 ° C. and a low temperature absorption ratio of 10%, a melting peak temperature of 145 ° C., MFR Is a resin composition comprising 55 parts by weight of a propylene-ethylene random copolymer having a characteristic of 2.3 g / 10 min as both surface layers, and has an density of 0.905 g / cm 3 and MI 0.8 g / 10 min. After melt-kneading with three extruders using octene-1 copolymer as the core layer, the extrusion amount of each extruder is set so that the thickness ratio becomes 1/5/1, and downward with a three-layer annular die Were coextruded. The formed three-layered tube was cooled by passing through a water tank while the outer surface of a cylindrical cooling mandrel in which cooling water circulated was slid, and was taken out to obtain an unstretched film. The obtained unstretched tube was guided to a tubular biaxial stretching apparatus and stretched at 90 to 110 ° C. by 5 times in length and breadth to obtain a laminated biaxially stretched film having a film thickness of 15 μm.
As shown in Table 1, the obtained film was excellent in shrink-wrapping finish, and a shrink-wrapped body having a beautiful appearance in which corners and corner wrinkles of the four corners of the packaging sample were hardly noticeable was obtained. In addition, the properties such as haze, tensile elastic modulus, and 100 ° C. heat shrinkage were also good.
実施例２
実施例１において、融解ピーク温度が８３℃、低温吸収割合が１０％の特性を有するメタロセン触媒により製造されるプロピレン−ブテン−１共重合体６０重量部、融解ピーク温度が１２５℃、ＭＦＲが２．０ｇ／１０分の特性を有するプロピレン−エチレンランダム共重合体４０重量部からなる樹脂組成物を両表面層とし、密度０．９２０ｇ／ｃｍ3、ＭＩ１．０ｇ／１０分であるエチレン−オクテン−１共重合体を芯層とし、延伸倍率を縦横４倍とした以外は、実施例１と同様の方法で、フィルム厚み１５μｍの積層二軸延伸フィルムを得た。
表１に示すように、得られたフィルムは、収縮包装仕上がり性に優れるもので、包装サンプルの四隅の角やコーナーシワが殆ど目立たない外観美麗な収縮包装体が得られた。その他、ヘイズ、引張弾性率、１００℃熱収縮率等の特性も良好であった。
Example 2
In Example 1, 60 parts by weight of a propylene-butene-1 copolymer produced by a metallocene catalyst having a melting peak temperature of 83 ° C. and a low temperature absorption ratio of 10%, a melting peak temperature of 125 ° C., and an MFR of 2 A resin composition comprising 40 parts by weight of a propylene-ethylene random copolymer having a property of 0.0 g / 10 min is used as both surface layers, and ethylene-octene having a density of 0.920 g / cm 3 and MI of 1.0 g / 10 min A laminated biaxially stretched film having a film thickness of 15 μm was obtained in the same manner as in Example 1 except that 1 copolymer was used as the core layer and the stretching ratio was 4 times in the longitudinal and lateral directions.
As shown in Table 1, the obtained film was excellent in shrink-wrapping finish, and a shrink-wrapped body having a beautiful appearance in which corners and corner wrinkles of the four corners of the packaging sample were hardly noticeable was obtained. In addition, the properties such as haze, tensile elastic modulus, and 100 ° C. heat shrinkage were also good.
実施例３
実施例１において、融解ピーク温度が７５℃、低温吸収割合が１０％の特性を有するメタロセン触媒により製造されるプロピレン−ブテン−１共重合体１０重量部、融解ピーク温度が１３５℃、ＭＦＲが２．５ｇ／１０分の特性を有するプロピレン−エチレンランダム共重合体９０重量部からなる樹脂組成物を両表面層とし、密度０．８７０ｇ／ｃｍ3、ＭＩ１．０ｇ／１０分であるエチレン−オクテン−１共重合体を芯層とし、厚み比を１／４／１、延伸倍率を縦横４倍とした以外は、実施例１と同様の方法で、フィルム厚み１５μｍの積層二軸延伸フィルムを得た。
表１に示すように、得られたフィルムは、収縮包装仕上がり性に優れるもので、包装サンプルの四隅の角やコーナーシワが殆ど目立たない外観美麗な収縮包装体が得られた。その他、ヘイズ、引張弾性率、１００℃熱収縮率等の特性も良好であった。
Example 3
In Example 1, 10 parts by weight of a propylene-butene-1 copolymer produced by a metallocene catalyst having a melting peak temperature of 75 ° C. and a low temperature absorption ratio of 10%, a melting peak temperature of 135 ° C., and an MFR of 2 A resin composition comprising 90 parts by weight of a propylene-ethylene random copolymer having a characteristic of 5 g / 10 min is used as both surface layers, ethylene-octene having a density of 0.870 g / cm 3 and MI of 1.0 g / 10 min A laminated biaxially stretched film having a film thickness of 15 μm was obtained in the same manner as in Example 1 except that 1 copolymer was used as the core layer, the thickness ratio was 1/4/1, and the stretch ratio was 4 times in the longitudinal and lateral directions. .
As shown in Table 1, the obtained film was excellent in shrink-wrapping finish, and a shrink-wrapped body having a beautiful appearance in which corners and corner wrinkles of the four corners of the packaging sample were hardly noticeable was obtained. In addition, the properties such as haze, tensile elastic modulus, and 100 ° C. heat shrinkage were also good.
実施例４
実施例１において、融解ピーク温度が８３℃、低温吸収割合が１０％の特性を有するメタロセン触媒により製造されるプロピレン−ブテン−１共重合体２５重量部、融解ピーク温度が１３５℃、ＭＦＲが２．５ｇ／１０分の特性を有するプロピレン−エチレンランダム共重合体７５重量部からなる樹脂組成物を両表面層とし、密度０．８８５ｇ／ｃｍ3、ＭＩ３．６ｇ／１０分であるエチレン−ブテン−１共重合体を芯層とし、延伸倍率を縦横４倍とした以外は、実施例１と同様の方法で、フィルム厚み１５μｍの積層二軸延伸フィルムを得た。
表１に示すように、得られたフィルムは、収縮包装仕上がり性に優れるもので、包装サンプルの四隅の角やコーナーシワが殆ど目立たない外観美麗な収縮包装体が得られた。その他、ヘイズ、引張弾性率、１００℃熱収縮率等の特性も良好であった。
Example 4
In Example 1, 25 parts by weight of a propylene-butene-1 copolymer produced by a metallocene catalyst having a melting peak temperature of 83 ° C. and a low temperature absorption ratio of 10%, a melting peak temperature of 135 ° C., and an MFR of 2 Ethylene-butene having a density of 0.885 g / cm 3 and MI of 3.6 g / 10 min with a resin composition comprising 75 parts by weight of a propylene-ethylene random copolymer having the characteristics of 0.5 g / 10 min as both surface layers A laminated biaxially stretched film having a film thickness of 15 μm was obtained in the same manner as in Example 1 except that 1 copolymer was used as the core layer and the stretching ratio was 4 times in the longitudinal and lateral directions.
As shown in Table 1, the obtained film was excellent in shrink-wrapping finish, and a shrink-wrapped body having a beautiful appearance in which corners and corner wrinkles of the four corners of the packaging sample were hardly noticeable was obtained. In addition, the properties such as haze, tensile elastic modulus, and 100 ° C. heat shrinkage were also good.
実施例５
実施例１において、融解ピーク温度が７５℃、低温吸収割合が１０％の特性を有するメタロセン触媒により製造されるプロピレン−ブテン−１共重合体２０重量部、融解ピーク温度が１３５℃、ＭＦＲが２．５ｇ／１０分の特性を有するプロピレン−エチレンランダム共重合体８０重量部からなる樹脂組成物を両表面層とし、密度０．８９７ｇ／ｃｍ3、ＭＩ１．６ｇ／１０分であるエチレン−オクテン−１共重合体を芯層とし、延伸倍率を縦横４倍とした以外は、実施例１と同様の方法で、フィルム厚み１５μｍの積層二軸延伸フィルムを得た。
表１に示すように、得られたフィルムは、収縮包装仕上がり性に優れるもので、包装サンプルの四隅の角やコーナーシワが殆ど目立たない外観美麗な収縮包装体が得られた。その他、ヘイズ、引張弾性率、１００℃熱収縮率等の特性も良好であった。
Example 5
In Example 1, 20 parts by weight of a propylene-butene-1 copolymer produced by a metallocene catalyst having a melting peak temperature of 75 ° C. and a low temperature absorption ratio of 10%, a melting peak temperature of 135 ° C., and an MFR of 2 Ethylene-octene having a density of 0.897 g / cm 3 and MI of 1.6 g / 10 min with a resin composition comprising 80 parts by weight of a propylene-ethylene random copolymer having a characteristic of 0.5 g / 10 min as both surface layers A laminated biaxially stretched film having a film thickness of 15 μm was obtained in the same manner as in Example 1 except that 1 copolymer was used as the core layer and the stretching ratio was 4 times in the longitudinal and lateral directions.
As shown in Table 1, the obtained film was excellent in shrink-wrapping finish, and a shrink-wrapped body having a beautiful appearance in which corners and corner wrinkles of the four corners of the packaging sample were hardly noticeable was obtained. In addition, the properties such as haze, tensile elastic modulus, and 100 ° C. heat shrinkage were also good.
実施例６
実施例１において、融解ピーク温度が７５℃、低温吸収割合が１０％の特性を有するメタロセン触媒により製造されるプロピレン−ブテン−１共重合体４５重量部、融解ピーク温度が１４５℃、ＭＦＲが０．５ｇ／１０分の特性を有するプロピレン−エチレンランダム共重合体５５重量部からなる樹脂組成物を両表面層とした以外は、実施例１と同様の方法で、フィルム厚み１５μｍの積層二軸延伸フィルムを得た。
表２に示すように、得られたフィルムは、収縮包装仕上がり性に優れるもので、包装サンプルの四隅の角やコーナーシワが殆ど目立たない外観美麗な収縮包装体が得られた。その他、ヘイズ、引張弾性率、１００℃熱収縮率等の特性も良好であった。
Example 6
In Example 1, 45 parts by weight of a propylene-butene-1 copolymer produced by a metallocene catalyst having a melting peak temperature of 75 ° C. and a low temperature absorption ratio of 10%, a melting peak temperature of 145 ° C., and an MFR of 0 Laminated biaxial stretching with a film thickness of 15 μm in the same manner as in Example 1 except that the resin composition comprising 55 parts by weight of a propylene-ethylene random copolymer having a characteristic of 5 g / 10 min was used as both surface layers. A film was obtained.
As shown in Table 2, the obtained film was excellent in shrink-wrapping finish, and a shrink-wrapped body having a beautiful appearance in which corners and corner wrinkles of the four corners of the packaging sample were hardly noticeable was obtained. In addition, the properties such as haze, tensile elastic modulus, and 100 ° C. heat shrinkage were also good.
比較例１
実施例１において、融解ピーク温度が７５℃、低温吸収割合が１０％の特性を有するメタロセン触媒により製造されるプロピレン−ブテン−１共重合体５重量部、融解ピーク温度が１４５℃、ＭＦＲが２．３ｇ／１０分の特性を有するプロピレン−エチレンランダム共重合体９５重量部からなる層にした以外は、実施例１と同様の方法で、フィルム厚み１５μｍの積層二軸延伸フィルムを得た。
表２に示すように、得られたフィルムは、低温収縮性に劣るもので、１００℃熱収縮率が低いため、包装サンプルの四隅の角立ちや小ジワが明らかに目立ち、外観を著しく損ねる結果であった。
Comparative Example 1
In Example 1, 5 parts by weight of a propylene-butene-1 copolymer produced by a metallocene catalyst having a melting peak temperature of 75 ° C. and a low temperature absorption ratio of 10%, a melting peak temperature of 145 ° C., and an MFR of 2 A laminated biaxially stretched film having a film thickness of 15 μm was obtained in the same manner as in Example 1 except that the layer was composed of 95 parts by weight of a propylene-ethylene random copolymer having a characteristic of 3 g / 10 min.
As shown in Table 2, the obtained film is inferior in low-temperature shrinkage and has a low 100 ° C. heat shrinkage rate. As a result, the corners and wrinkles at the four corners of the packaging sample are clearly noticeable, and the appearance is remarkably impaired. Met.
比較例２
実施例１において、両表面層を融解ピーク温度が７５℃、低温吸収割合が１０％の特性を有するメタロセン触媒により製造されるプロピレン−ブテン−１共重合体１００重量部からなる層にした以外は、実施例１と同様の方法で、フィルム厚み１５μｍの積層二軸延伸フィルムを得た。
表２に示すように、得られたフィルムは、滑り性が劣るため、包装機でのフィルムの走行トラブルが散発し、収縮包装体に傷が入ることがあり、また、耐熱性が劣るため、包装サンプルの四隅の角立ちや小ジワがやや目立ち、外観を損ねる結果であった。
Comparative Example 2
In Example 1, except that both surface layers were layers composed of 100 parts by weight of a propylene-butene-1 copolymer produced by a metallocene catalyst having a melting peak temperature of 75 ° C. and a low temperature absorption ratio of 10%. In the same manner as in Example 1, a laminated biaxially stretched film having a film thickness of 15 μm was obtained.
As shown in Table 2, since the obtained film is inferior in slipperiness, the running trouble of the film in the packaging machine sporadically, the shrink wrapping body may be damaged, and the heat resistance is inferior, The corners and wrinkles at the four corners of the packaging sample were slightly noticeable and the appearance was impaired.
比較例３
実施例１において、芯層を融解ピーク温度が１６４℃、ＭＦＲが７．５ｇ／１０分の特性を有するポリプロピレン単独重合体からなる層にした以外は、実施例１と同様の方法で、フィルム厚み１５μｍの積層二軸延伸フィルムを得た。
表２に示すように、得られたフィルムは、低温収縮性に劣るもので、１００℃熱収縮率が低いため、包装サンプルの四隅の角立ちや小ジワが明らかに目立ち、外観を著しく損ねる結果であった。また、耐引裂性も劣るため、包装サンプルを運搬中に、包装フィルムが破れるトラブルも散発した。
Comparative Example 3
In Example 1, the film thickness was obtained in the same manner as in Example 1 except that the core layer was a layer made of a polypropylene homopolymer having a melting peak temperature of 164 ° C. and an MFR of 7.5 g / 10 min. A laminated biaxially stretched film of 15 μm was obtained.
As shown in Table 2, the obtained film is inferior in low-temperature shrinkage and has a low 100 ° C. heat shrinkage rate. As a result, the corners and wrinkles at the four corners of the packaging sample are clearly noticeable, and the appearance is remarkably impaired. Met. Moreover, since the tear resistance was poor, troubles in which the packaging film was broken during the transportation of the packaging sample were sporadic.
比較例４
実施例１において、両表面層を融解ピーク温度が１２０℃、低温吸収割合が５５％の特性を有するプロピレン−エチレン共重合体４５重量部、融解ピーク温度が１４５℃、ＭＦＲが２．３ｇ／１０分の特性を有するプロピレン−エチレンランダム共重合体５５重量部からなる層にした以外は、実施例１と同様の方法で、フィルム厚み１５μｍの積層二軸延伸フィルムを得た。
表２に示すように、得られたフィルムは、１００℃熱収縮率が低いため、包装サンプルの四隅の角立ちや小ジワがやや目立ち、また、滑り性が劣るため、包装機でのフィルムの走行トラブルが散発し、収縮包装体に傷が入って外観を損ねる結果であった。
Comparative Example 4
In Example 1, 45 parts by weight of a propylene-ethylene copolymer having a melting peak temperature of 120 ° C. and a low-temperature absorption ratio of 55% on both surface layers, a melting peak temperature of 145 ° C., and an MFR of 2.3 g / 10 A laminated biaxially stretched film having a film thickness of 15 μm was obtained in the same manner as in Example 1 except that the layer was made of 55 parts by weight of a propylene-ethylene random copolymer having the properties of minutes.
As shown in Table 2, since the heat shrinkage rate at 100 ° C. is low, the corners and small wrinkles at the four corners of the packaging sample are slightly noticeable, and the slipperiness is inferior. As a result, running troubles sporadically occurred, and the shrink-wrapped body was damaged and the appearance was damaged.
本発明の熱収縮性包装材料は、優れた低温収縮性、耐熱性が得られ、高価な商品を包装する際に必要とされる高度な収縮仕上がり性を発現することができるポリオレフィン系熱収縮性フィルムとして好適に用いることができる。
The heat-shrinkable packaging material of the present invention is a polyolefin-based heat-shrinkable material that has excellent low-temperature shrinkability and heat resistance, and can exhibit a high degree of shrinkage finish required when packaging expensive products. It can be suitably used as a film.
Claims (6)
The total amount of heat absorbed by the propylene-butene-1 copolymer produced by the metallocene catalyst of the surface layer from the melting start temperature to a temperature 20 ° C. lower than the melting peak temperature in the measurement using DSC is the above. 6. The total amount of heat absorbed between the melting start temperature and the melting end temperature is 39% or less, preferably 30% or less, more preferably 20% or less. The polyolefin-based heat-shrinkable film according to item.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010242433A JP5660852B2 (en) | 2009-11-05 | 2010-10-28 | Polyolefin heat shrinkable film with excellent shrink finish |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009254034 | 2009-11-05 | ||
| JP2009254034 | 2009-11-05 | ||
| JP2010242433A JP5660852B2 (en) | 2009-11-05 | 2010-10-28 | Polyolefin heat shrinkable film with excellent shrink finish |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2011116123A JP2011116123A (en) | 2011-06-16 |
| JP5660852B2 true JP5660852B2 (en) | 2015-01-28 |
Family
ID=44282009
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2010242433A Active JP5660852B2 (en) | 2009-11-05 | 2010-10-28 | Polyolefin heat shrinkable film with excellent shrink finish |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5660852B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7368663B2 (en) | 2019-03-13 | 2023-10-25 | 青島海爾洗滌電器有限公司 | Drum washing machine drainage sealing device and drum washing machine |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103009752B (en) * | 2012-12-25 | 2014-10-01 | 海南赛诺实业有限公司 | Polyolefin heat shrinkable film with low shrinkage temperature and manufacturing method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2916853B2 (en) * | 1993-05-31 | 1999-07-05 | 大倉工業株式会社 | Polyolefin-based heat-shrinkable laminated film |
| JPH10157032A (en) * | 1996-10-03 | 1998-06-16 | Sekisui Chem Co Ltd | Multilayer shrink film |
| JP2000000942A (en) * | 1998-06-18 | 2000-01-07 | Sekisui Chem Co Ltd | Heat-shrinkable film |
| JP4068978B2 (en) * | 2002-02-14 | 2008-03-26 | 三井化学株式会社 | Polyolefin resin composition and shrink film using the same |
| JP2005170011A (en) * | 2003-12-15 | 2005-06-30 | Sekisui Film Kk | Polyolefin resin-based heat-shrinkable film |
| JP2008149503A (en) * | 2006-12-15 | 2008-07-03 | Sekisui Film Kk | Heat-shrinkable multilayer polyolefin-based resin film |
| JP2009039950A (en) * | 2007-08-09 | 2009-02-26 | Sekisui Film Kk | Multi-layer polyolefin-based heat-shrinkable film |
-
2010
- 2010-10-28 JP JP2010242433A patent/JP5660852B2/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7368663B2 (en) | 2019-03-13 | 2023-10-25 | 青島海爾洗滌電器有限公司 | Drum washing machine drainage sealing device and drum washing machine |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2011116123A (en) | 2011-06-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5893091B2 (en) | Polyethylene-based crosslinked shrink film | |
| JP4915749B2 (en) | Polyolefin multilayer shrink film | |
| EP0732196B1 (en) | Heat-shrinkable polyolefin laminate film | |
| JP5587136B2 (en) | Polyolefin heat shrinkable film with excellent shrink finish | |
| JP3751965B2 (en) | Polyolefin multilayer shrink film | |
| JP5660852B2 (en) | Polyolefin heat shrinkable film with excellent shrink finish | |
| JP2010064369A (en) | Polypropylene-based multilayered shrink film | |
| JP5722081B2 (en) | Polyethylene-based crosslinked shrink film with excellent shrink finish | |
| JP4287875B2 (en) | Polyolefin laminated stretch shrink film | |
| JP5545627B2 (en) | Polyolefin thin film multilayer shrink film | |
| JP2016215480A (en) | Polyethylene crosslinked shrink film | |
| JP5399048B2 (en) | Polyethylene-based crosslinked shrink film | |
| JP2004017545A (en) | Low temperature shrinkable multilayered polyolefinic film and manufacturing method therefor | |
| JP3850545B2 (en) | Polyolefin heat shrinkable film | |
| JP6604835B2 (en) | Polyolefin heat shrinkable film | |
| JP3493474B2 (en) | Polyolefin-based heat-shrinkable multilayer film | |
| JP2011240619A (en) | Styrene heat-shrinkable film for over-wrap packing | |
| JP3068920B2 (en) | Polyethylene heat-shrinkable laminated film | |
| JP7461799B2 (en) | Gas barrier shrink film | |
| JPH0418347A (en) | Polyethylenic heat-shrinkable laminated film | |
| JP2010234656A (en) | Polypropylene and polyolefin multilayer shrink film with light shielding property | |
| JP5068130B2 (en) | Polyolefin-based multilayer shrink film and packaging method | |
| JP3859808B2 (en) | Polyolefin heat shrinkable film | |
| JP2007001102A (en) | Heat-shrinkable multilayer polyolefin film | |
| JP2015110719A (en) | Polyethylene-based heat-shrinkable film and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20130925 |
|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A711 Effective date: 20140117 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20140523 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20140527 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20141202 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20141202 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5660852 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |