JPS62201229A - Heat shrinkable film - Google Patents
Heat shrinkable filmInfo
- Publication number
- JPS62201229A JPS62201229A JP4417086A JP4417086A JPS62201229A JP S62201229 A JPS62201229 A JP S62201229A JP 4417086 A JP4417086 A JP 4417086A JP 4417086 A JP4417086 A JP 4417086A JP S62201229 A JPS62201229 A JP S62201229A
- Authority
- JP
- Japan
- Prior art keywords
- stretching
- film
- copolymer
- olefin
- heat absorbing
- 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.)
- Granted
Links
- 229920006257 Heat-shrinkable film Polymers 0.000 title abstract description 7
- 238000002844 melting Methods 0.000 claims abstract description 18
- 230000008018 melting Effects 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 229920001577 copolymer Polymers 0.000 claims abstract description 14
- 239000004711 α-olefin Substances 0.000 claims abstract description 11
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000005977 Ethylene Substances 0.000 claims abstract description 6
- 229920005684 linear copolymer Polymers 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229920000573 polyethylene Polymers 0.000 claims description 17
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 5
- 239000011347 resin Substances 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 abstract description 4
- 238000001125 extrusion Methods 0.000 abstract 1
- 230000002045 lasting effect Effects 0.000 abstract 1
- -1 polypropylene Polymers 0.000 description 11
- 239000004698 Polyethylene Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 238000004806 packaging method and process Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012803 melt mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 235000013550 pizza Nutrition 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229920006300 shrink film Polymers 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は収縮包装材料に関するもので、より詳細には特
定のエチレン−α−オレフィン共重合体を主とする組成
物を原料とし、低温収縮性に優れ、厚みムラが小さいプ
ラスチック包装フィルムに関するものであ石。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to shrink packaging materials, and more specifically, the present invention relates to shrink packaging materials, and more specifically, it is made from a composition mainly containing a specific ethylene-α-olefin copolymer, and This relates to plastic packaging films with excellent properties and small thickness irregularities.
(従来の技術)
従来熱収縮性フィルムとしてはポリ塩化ビニル、ポリプ
ロピレン2軸延伸フイルム、ポリエチレン系フィルムな
どが知られている。このうちポリエチレン系フィルムは
丸ダイより押出されたチューブをそのまま気体の圧力に
よってブローアツプする謂ゆるインフレーション法によ
り製造されるもので、l)、安価であること、ヒートシ
ール部の強度が大きいことなどの特徴から収縮包装用途
に広く使用されている。(Prior Art) Conventionally known heat-shrinkable films include polyvinyl chloride, biaxially stretched polypropylene films, and polyethylene films. Among these, polyethylene film is manufactured by the so-called inflation method, in which a tube extruded from a round die is blown up using gas pressure. Due to its characteristics, it is widely used for shrink wrapping applications.
(発明が解決しようとする問題点)
インフレ法により製造されるポリエチレン系熱収縮フィ
ルムはその製法から有効な分子配向が行なわれていない
為、フィルム強度が小さく伸びが大きく融点近い温度で
ないと高い収縮率を示さず、緒特性は必らずしも満足の
ゆくものではない。(Problems to be solved by the invention) Polyethylene heat-shrinkable films manufactured by the inflation method do not have effective molecular orientation due to the manufacturing method, so the film has low strength and elongation, resulting in high shrinkage unless the temperature is close to the melting point. The performance characteristics are not necessarily satisfactory.
かかる欠点を改良すべくポリエチレン系フィルムに電離
性放射線を照射して分子間架橋を生せしめた後加熱延伸
する方法によった謂ゆる照射ポリエチレンフィルムは、
延伸による配向効果が認められ強度は大きく伸度は小さ
くなるなどの改良はあるもののヒートシール性が悪いこ
と、屑の回収が出来ないこと、放射線処理によるコスト
アップが免れ難いなどの欠点を持つ。In order to improve these defects, so-called irradiated polyethylene film is produced by irradiating a polyethylene film with ionizing radiation to cause intermolecular crosslinking, and then heating and stretching the film.
Although there are improvements such as increased strength and decreased elongation due to the orientation effect of stretching, it still has drawbacks such as poor heat sealability, inability to collect waste, and inevitable cost increases due to radiation treatment.
本発明者らは、ポリエチレン系収縮フィルムについて原
料面技術面より種々検討を加え、ヒートシール性や耐衝
撃性等のポリエチレン系フィルムの優れた特性を生かし
たまま、延伸配向により熱収縮性を改良したポリエチレ
ン系熱収縮フィルム及びその製法を見い出した。(特公
昭57−36.142)この発明によって得られるフィ
ルムは謂ゆるインフレーションフィルムと異なυ融点以
下でも収縮包装するに必要な収縮率と収縮応力を発現−
し、被包装物に密着する良好な収縮包装性をもつもので
あるが、延伸チューブの安定性延伸の均一性が必らずし
も満足ゆくものでなく、厚みムラが大きい欠点を持つと
共に、延伸配向効果が十分に成シ難くこの為低温での収
縮特性に難を残していた。The present inventors conducted various studies on polyethylene-based shrink films from the raw material and technical aspects, and improved the heat-shrinkability by stretching and orientation while taking advantage of the excellent properties of polyethylene films such as heat-sealability and impact resistance. We have discovered a heat-shrinkable polyethylene film and its manufacturing method. (Japanese Patent Publication No. 57-36.142) The film obtained by this invention exhibits the shrinkage rate and shrinkage stress necessary for shrink wrapping even below the υ melting point, which is different from the so-called blown film.
However, although it has good shrink-wrapping properties that tightly adhere to the packaged object, the stability of the stretched tube and the uniformity of stretching are not necessarily satisfactory, and it has the disadvantage of large thickness unevenness. It was difficult to achieve a sufficient stretching orientation effect, and therefore the shrinkage properties at low temperatures remained problematic.
(問題点を解決するだめの手段)
本発明者らは、延伸配向効果を大きくすると共に、延伸
の安定性均一性を向上させるべく鋭意検討した結果、エ
チレン系重合体を特定することによって本発明に到達し
た。(Means for Solving the Problems) As a result of intensive studies aimed at increasing the stretching orientation effect and improving the stability and uniformity of stretching, the present inventors have identified an ethylene-based polymer, thereby inventing the present invention. reached.
即ち本発明は、エチレンとα−オレフィンとの線状共重
合体の1種又は2種以上を含み、この共重合体又は共重
合体混合物のDSCの測定による融解曲線について融点
(吸熱メインピーク温度)より10℃低r温度以下の吸
熱面積が全吸熱面積の55チ以上であるエチレン系重合
体組成物を溶融押出しし、冷却固化して得られるフィル
ムを縦横それぞれ2倍以上延伸して得られる90℃にお
ける面積収縮率が20%以上であシ厚みムラが20%以
下である熱収縮性フィルムである。That is, the present invention includes one or more linear copolymers of ethylene and α-olefin, and the melting point (endothermic main peak temperature) of the copolymer or copolymer mixture measured by DSC is ) is obtained by melt-extruding an ethylene polymer composition whose endothermic area at a temperature below 10°C is 55 inches or more of the total endothermic area, and stretching the film obtained by cooling and solidifying the film by at least twice the length and width. It is a heat-shrinkable film having an area shrinkage rate of 20% or more and thickness unevenness of 20% or less at 90°C.
本発明に用いられるエチレン系重合体組成物の主な樹脂
はエチレン−α−オレフィン線状共重合体であり、1種
単独であるか211以上の混合物であることができる。The main resin of the ethylene polymer composition used in the present invention is an ethylene-α-olefin linear copolymer, which may be used alone or in a mixture of 211 or more.
エチレンと共重合されるα−オレフィンとしてはブテン
−1、ペンテン−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、デセン−1、ウン
デセン−1、ドデセン−1などがある。これらの共重合
は、いわゆるチーグラーナツタ型触媒を使った低中圧法
によって行なうことが出来、これらの製造法については
、特公昭50−32270.49−35345、特開昭
55−78004、特開昭55−86804、特開昭5
4−154488などに開示される技術によることが出
来る。α−オレフィンの含量は0.5〜10モルチの範
囲が好ましい。α-olefins copolymerized with ethylene include butene-1, pentene-1, hexene-1, heptene-1, octene-1,4 methylpentene-1, decene-1, undecene-1, dodecene-1, etc. be. These copolymerizations can be carried out by a low-medium pressure method using a so-called Ziegler-Natsuta type catalyst, and their production methods are described in Japanese Patent Publication No. 50-32270.49-35345, Japanese Patent Application Laid-open No. 55-78004, 55-86804, Japanese Unexamined Patent Publication No. 5
4-154488, etc. can be used. The content of α-olefin is preferably in the range of 0.5 to 10 mol.
更に本発明の目的に支障をきたさない範囲であれば高圧
法ポリエチレン、エチレン−酢酸ビニル共重合体アイオ
ノマー、エチレン−プロピレン共重合体等々を混合使用
することが出来る。Further, high-pressure polyethylene, ethylene-vinyl acetate copolymer ionomer, ethylene-propylene copolymer, etc. can be mixed and used within a range that does not impede the purpose of the present invention.
又、滑剤、ブロッキング防止剤、帯電防止剤。Also, lubricant, anti-blocking agent, antistatic agent.
防曇剤等の添加剤が、それぞれの有効な作用を具備させ
る目的で適宜使用されるのは当然である。It goes without saying that additives such as antifogging agents are used as appropriate to provide their respective effective effects.
本発明に使用する樹脂は、前記のポリエチレン系重合体
組成物であって示差走査熱量計の測定による融解曲線に
ついて融点(吸熱メインピーク)より10℃低い温度以
下の吸熱面積が全吸熱面積の55チ以上である必要がめ
る。この条件を満たさないものは、延伸の均一性が容易
に得られず、均一性を得る為延伸温度を高くすると延伸
の持続安定性が損われるばかシでなく、延伸配向効果の
発現が少なく、低温での収縮性能が十分でなくなる。こ
の条件を満たすものは融点以下10℃よりも低温で、特
別の狭い温度勾配の範囲に限定しなくても均一かつ安定
した延伸が可能であるばかシでなく、延伸配向効果が大
きく90℃における面積収縮率が20%以上であシ厚み
ムラが20%以下である実用性に優れた熱収縮性フィル
ムが得られる。The resin used in the present invention is the above-mentioned polyethylene polymer composition, and the endothermic area of the melting curve measured by a differential scanning calorimeter is 55% of the total endothermic area at a temperature 10°C lower than the melting point (endothermic main peak). Must be at least 100%. If this condition is not met, it is not easy to obtain uniformity of stretching, and if the stretching temperature is increased to obtain uniformity, the sustained stability of stretching is impaired, and the stretching orientation effect is less likely to occur. Shrinkage performance at low temperatures becomes insufficient. Products that meet this condition are not foolproof as they can be stretched uniformly and stably at a temperature below the melting point of 10°C without being limited to a narrow temperature gradient range, and have a large stretching orienting effect at 90°C. A highly practical heat-shrinkable film having an area shrinkage rate of 20% or more and a thickness unevenness of 20% or less can be obtained.
ここで述べた示差走査熱量計による測定には、試料6〜
8mgをアルミノヤンに封入し、窒素気流下にて190
℃まで昇温しこの温度で1時間保持し、次いで約10℃
/ minで室温まで冷却したのち昇温速度10℃/
mi n 、感度25■/secで得た融解曲線を用い
るものである。For measurements using the differential scanning calorimeter described here, samples 6 to
8 mg was sealed in Aluminum Yang and heated to 190 ml under a nitrogen stream.
℃ and held at this temperature for 1 hour, then about 10℃
After cooling to room temperature at / min, heating rate is 10℃/
A melting curve obtained at min and a sensitivity of 25 μ/sec is used.
本発明に用いられる延伸用原反フィルムの製造及び延伸
は公知の方法で行なうことができるが、以下管状製膜・
延伸の場合を例に挙げ、詳しく説明する。The raw film for stretching used in the present invention can be manufactured and stretched by known methods, but the following describes the process of forming a tubular film.
This will be explained in detail by taking the case of stretching as an example.
まず、前記の特定範囲の樹脂を加熱溶融し、混練し、チ
ューブ状に押出し、冷却固化して原反とする。First, the above-mentioned specific range of resin is heated and melted, kneaded, extruded into a tube shape, and cooled and solidified to obtain a raw fabric.
得られたチューブ状原反を例えば第1図で示すようなチ
ューブラ−延伸装置に供給し、有効な高度の配向が起る
温度域、例えば樹脂の融点以下10℃、更に好ましくは
20℃よりも低い温度で、膨張延伸して同時2軸配向を
行なわしめる。延伸倍率は縦横同一でなくとも良いが良
好な強度等の物性を得る為には縦横いずれの方向にも2
倍以上、好ましくは2.5倍以上である。The obtained tubular original fabric is fed to a tubular stretching apparatus such as that shown in FIG. Simultaneous biaxial orientation is achieved by expansion and stretching at a low temperature. The stretching ratio does not have to be the same in the vertical and horizontal directions, but in order to obtain good physical properties such as strength, the stretching ratio should be 2 in both the vertical and horizontal directions.
It is at least twice as large, preferably at least 2.5 times.
延伸装置から取シ出したフィルムは必要に応じてアニー
リングすることが出来る。The film taken out from the stretching device can be annealed if necessary.
以下本発明を実施例に基いて具体的に説明する。The present invention will be specifically described below based on Examples.
なお実施例中に示した測定項目は次の方法によった。The measurement items shown in the examples were determined by the following method.
1、面積収縮率
縦横共10crnの正方形に切シ取ったフィルムを所定
温度のグリセリン浴中に10秒間浸漬し、次式により算
出した。1. Area shrinkage rate A film cut into a square with a length and width of 10 crn was immersed in a glycerin bath at a predetermined temperature for 10 seconds, and the shrinkage rate was calculated using the following formula.
面積収縮率=100−AXB
但し、A、Bは浸漬後の縦横それぞれの長さく単位はm
)を示す。Area shrinkage rate = 100-AXB However, A and B are the vertical and horizontal lengths after immersion, and the unit is m.
) is shown.
2、厚みムラ
接触型電子マイクロメーター(安立電気(株)製に30
6C型)を使用しフルスケール8μmで測定したチュー
ブ円周方向のチャートについて最大値(Tmax) ’
最小値(Tmin )及び平均値(T)を求め、次式よ
り算出した。2. Thickness uneven contact type electronic micrometer (manufactured by Anritsu Electric Co., Ltd.)
Maximum value (Tmax) for the chart in the tube circumferential direction measured at a full scale of 8 μm using a 6C model)
The minimum value (Tmin) and average value (T) were determined and calculated using the following formula.
1゛
但し、Tは、測定フィルムの10m間隔に相当するチャ
ート位置から読み取った値の算術平均値。1. However, T is the arithmetic mean value of the values read from chart positions corresponding to 10 m intervals on the measurement film.
実施例1゜
25℃における密度0.9221/cJ 、メルトイン
デクスO,[’/10分のエチレン−ブテン−1共重合
体であってDSCによる融解曲線について主ピーク温度
が126℃であ、j5116℃以下の吸熱面積が全吸熱
面積の63.8%であったエチレン系重合体tl−17
0〜230℃で溶融混練し230℃に保った環状ダイス
より押出し、冷却水を循環している円筒状マンドレルの
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
却して引取シ、直径約66%厚み250μのチューブ状
未延伸フィルムを得た。この未延伸フィルムを原反とし
、これを第1図に示した2軸延伸装置に導き、95〜1
05℃で縦横それぞれ4倍に延伸した。延伸されたフィ
ルムはチーーブ状アニーリング装置にて75℃の熱風で
10秒間アニーリングした後、室温に冷却し折シ畳んで
巻き取った。Example 1 An ethylene-butene-1 copolymer with a density at 25°C of 0.9221/cJ, a melt index of O, ['/10 min, and a main peak temperature of 126°C in the melting curve by DSC, j5116 Ethylene polymer tl-17 whose endothermic area below ℃ was 63.8% of the total endothermic area
The mixture is melted and kneaded at 0 to 230°C, extruded through an annular die kept at 230°C, and cooled by sliding on the outer surface of a cylindrical mandrel in which cooling water is circulated. A tubular unstretched film having a thickness of about 66% and 250 μm was obtained. This unstretched film was used as a raw material, and it was introduced into a biaxial stretching apparatus shown in FIG.
The film was stretched 4 times in length and width at 05°C. The stretched film was annealed with hot air at 75° C. for 10 seconds in a tube-shaped annealing device, then cooled to room temperature, folded, and rolled up.
延伸チューブの安定性は良好で延伸点の上下動やチュー
ブの揺動もなく、又、ネッキングなどの不均一延伸状態
も観察されなかった。The stability of the stretched tube was good, with no vertical movement of the stretching point or swinging of the tube, and no uneven stretching conditions such as necking were observed.
得られた延伸フィルムは厚み16μで900の面積収縮
率は31.5%、厚みムラは15%であった。このフィ
ルムを用い直径15crn厚さ約1crnのピザパイを
予備包装し110℃の熱風が吹きつけている収縮トンネ
ル中を約3秒間通過させた。びりたシと密着した良好な
包装状態となり、被包装物にも変化は認められなかった
。The obtained stretched film had a thickness of 16 μm, an area shrinkage rate of 900 of 31.5%, and a thickness unevenness of 15%. A pizza pie having a diameter of 15 crn and a thickness of about 1 crn was prepackaged using this film and passed through a shrink tunnel in which hot air at 110° C. was blown for about 3 seconds. The packaging was in a good condition with the cracks tightly attached, and no change was observed in the packaged items.
実施例2゜
25℃における密度0.917117cm’、メルトイ
ンデクス2.3F710分のエチレン−オクテン−1共
重合体であってDSCによる融解曲線につ込て主ピーク
温度が121℃であり、111℃以下の吸熱面積が全吸
熱面積の57%であるエチレン系重合体を使用し、延伸
温度を90〜100℃とした他は実施例1と同様にして
延伸した。Example 2 An ethylene-octene-1 copolymer with a density of 0.917117 cm' at 25°C and a melt index of 2.3F710 minutes, whose main peak temperature was 121°C in the melting curve by DSC and 111°C. Stretching was carried out in the same manner as in Example 1, except that an ethylene polymer having the following endothermic area of 57% of the total endothermic area was used, and the stretching temperature was 90 to 100°C.
延伸点の上下動やチューブの揺動もなく、延伸チューブ
の安定性は良好で、又、不均一な延伸状態も観察されな
かった。There was no vertical movement of the stretching point or swinging of the tube, and the stability of the stretched tube was good, and no uneven stretching was observed.
得られた延伸フィルムは平均厚み16μで厚みムラは8
チであり90℃の面積収縮率は27%であった。このフ
ィルムを用いて高さ75瓢最大径40mの、j? IJ
スチレン製容器に充填された乳酸菌飲料を5個ずつ集積
し予備包装し100℃の熱風収縮トンネル中を3秒間通
過させた。The obtained stretched film had an average thickness of 16 μm and a thickness unevenness of 8 μm.
The area shrinkage rate at 90° C. was 27%. Using this film, a j? I.J.
Five lactic acid bacteria drinks filled in styrene containers were collected and prepackaged, and passed through a hot air shrink tunnel at 100° C. for 3 seconds.
短い収縮時間にも拘らず良好な収縮包装状態となった。Good shrink packaging was obtained despite the short shrinkage time.
実施例3゜
25℃における密度0.925117cm3、メルトイ
ンデクス1.ON/1(lのエチレン−4−メチルペン
テン−1共重合体70重量%と25℃における密度が0
.92317cm’メルトインデクス0.8.9/10
分のエチレン−ブテン−1共重合体30重量%との溶融
混合物であってDSCによる融解曲線について主ピーク
温度が124℃で、1)、114℃以下の吸熱面積が全
吸熱面積の58.8%であったエチレン系重合体組成物
を170〜230℃で溶融混練し、230℃に保った環
状ダイスより押出し、冷却水を循環している円筒状マン
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
により冷却して引取シ、直径約66瓢厚み320μのチ
ーーブ状未延伸フィルムを得た。この未延伸フィルムを
2軸延伸装置に導き95〜105℃で縦4.3倍横3.
8倍に延伸した後75℃で10秒間アニーリングし折り
畳んで巻き取った。Example 3: Density at 25°C: 0.925117cm3, melt index: 1. ON/1 (70% by weight of ethylene-4-methylpentene-1 copolymer and a density of 0 at 25°C)
.. 92317cm' Melt index 0.8.9/10
Regarding the melting curve by DSC of a melt mixture with 30% by weight of ethylene-butene-1 copolymer, the main peak temperature is 124°C, 1), the endothermic area below 114°C is 58.8 of the total endothermic area % of the ethylene polymer composition was melt-kneaded at 170 to 230°C, extruded through an annular die maintained at 230°C, and the outer surface of the ethylene polymer composition was melt-kneaded at 170 to 230°C and extruded through an annular die maintained at 230°C. The film was cooled by passing through a water tank and taken out to obtain an unstretched film having a diameter of about 66 mm and a thickness of 320 μm. This unstretched film is introduced into a biaxial stretching device at 95 to 105°C, 4.3 times vertically and 3 times horizontally.
After stretching 8 times, it was annealed at 75° C. for 10 seconds, folded, and rolled up.
延伸点の上下動やチーーブの揺動もなく延伸チューブの
安定性は良好で、又、ネッキング、縦割れなどの不均一
延伸も観察されなかった。The stability of the stretched tube was good, with no vertical movement of the stretching point or swinging of the tube, and no uneven stretching such as necking or longitudinal cracking was observed.
得られたフィルムは平均厚み20μで厚みムラは10%
であシ90℃の面積収縮率は25.8%であった。この
フィルムを用いて実施例1と同条件で収縮包装を行なっ
た。密着状態良好な包装となシ、被包装物にも変化は認
められなかった。The average thickness of the obtained film was 20μ, and the thickness unevenness was 10%.
The area shrinkage rate at 90°C was 25.8%. Shrink wrapping was performed using this film under the same conditions as in Example 1. The packaging had good adhesion, and no change was observed in the packaged items.
比較例1゜
25℃における密度0.918 、!i’ /cm3メ
ルトインデクス1.0.9/10分のエチレン−ブテン
−1共重合体であってDSCによる融解曲線について主
ピーク温度が120℃で、110℃以下の吸熱面積が全
吸熱面積の49%であったエチレン系重合体を実施例1
と同様な方法、条件で製膜・延伸・アニーリングした。Comparative Example 1 Density at 25°C: 0.918,! i'/cm3 Melt index: 1.0.9/10 minutes The melting curve of an ethylene-butene-1 copolymer by DSC has a main peak temperature of 120°C, and the endothermic area below 110°C is the total endothermic area. Example 1
The film was formed, stretched, and annealed using the same method and conditions as .
このような低い延伸温度では延伸チューブは揺動し、延
伸部にはネッキング現象も見られた。延伸チー−ブの安
定性を増すべく延伸温度を下げるとネッキングは激しく
なシネ均一さが増した。ネッキングを緩和すべく延伸温
度を103y108℃に上げると延伸チー−ブの上下動
・揺動けひどくなシ安定性が悪くなった。At such a low stretching temperature, the stretched tube swayed, and a necking phenomenon was also observed in the stretched portion. When the stretching temperature was lowered to increase the stability of the drawn tube, necking was severe and cine uniformity increased. When the stretching temperature was raised to 103°C and 108°C to alleviate necking, the stability deteriorated due to severe up-and-down movement and shaking of the stretching tube.
延伸温度103〜108℃で得られた延伸フィルムは平
均厚み16μで厚みムラは27チであ夛、90℃での面
積収縮率は15.4%であった。The stretched film obtained at a stretching temperature of 103 to 108°C had an average thickness of 16 μm, a thickness unevenness of 27 cm, and an area shrinkage rate of 15.4% at 90°C.
このフィルムは平面性が悪く、自動包装機での1連続包
装に適さなかった。又、実施例1と同条件での収縮工程
においても皺、凹凸が多く良好な包装状態とならなかっ
た。熱風温度を上げた夛、収縮トンネルの通過時間を長
くすることにより良好な包装状態が得られたが、この条
件では被包装物の一部が溶融変形し商品価値が著るしく
低下したものとなった。This film had poor flatness and was not suitable for continuous packaging using an automatic packaging machine. Further, even in the shrinking process under the same conditions as in Example 1, there were many wrinkles and irregularities, and the packaging was not in a good condition. Good packaging conditions were obtained by increasing the temperature of the hot air and increasing the time it took to pass through the shrink tunnel, but under these conditions some of the items to be packaged melted and deformed, resulting in a significant decrease in product value. became.
比較例2゜
25℃における密度0.921、メルトインデクス0.
751!/10分のエチレン−ヘキセン−1共重合体6
0重量%と25℃における密度0.920メルトインデ
クス1.0g/10分のエチレン−オクテン−1共重合
体40重量%との溶融混合物であってDSCによる融解
曲線について主ピーク温度が127℃でlfi 117
℃以下の吸熱面積が全吸熱面積の50.4%であったエ
チレン系重合体組成物を実施例3と同様な方法条件で製
膜延伸アニーリングした。Comparative Example 2: Density at 25°C: 0.921, melt index: 0.
751! /10 min ethylene-hexene-1 copolymer 6
0% by weight and 40% by weight of an ethylene-octene-1 copolymer with a density of 0.920 melt index 1.0 g/10 min at 25°C, with a main peak temperature of 127°C for the melting curve by DSC. lfi 117
An ethylene polymer composition having an endothermic area of 50.4% of the total endothermic area below .degree. C. was film-formed and stretched and annealed under the same method conditions as in Example 3.
延伸部のネッキング現象は顕著であり、ネッキングを緩
和すべく延伸温度を上げると延伸チューブの揺動がひど
く安定した延伸状態は得られなかった。The necking phenomenon in the stretched portion was remarkable, and when the stretching temperature was raised to alleviate necking, the stretched tube was so shaken that a stable stretched state could not be obtained.
延伸温度105〜112℃で得られた延伸フィルムは平
均厚み16μで厚みムラは23チであシ90℃での面積
収縮率は16.4チであった。The stretched film obtained at a stretching temperature of 105 to 112°C had an average thickness of 16 μm, thickness unevenness of 23 cm, and area shrinkage rate at 90° C. of 16.4 cm.
(作用及び効果)
原料樹脂としてエチレンとα−オレフィンとの線状共重
合体、又はそれらの混合物の内、示差走査熱量計による
原料の融解時の融解曲線において、融点(吸熱メインビ
ーク)より10℃低い温度以下の部分の吸熱面積が全吸
熱面積の55%以上であるものを用いることにより、融
点以下比較的低い温度で安定して延伸可能でアシ、その
結果厚みムラは小さくなシ、且配向効率が向上し、低温
における熱収縮率がすぐれた収縮性フィルムを安定して
製造することができだ。(Function and Effect) Among linear copolymers of ethylene and α-olefin, or mixtures thereof, as the raw material resin, in the melting curve of the raw material measured by differential scanning calorimeter, the melting point (endothermic main peak) is 10 By using a material in which the endothermic area of the part below the low temperature is 55% or more of the total endothermic area, it can be stably stretched at a relatively low temperature below the melting point, and as a result, the thickness unevenness is small. It is possible to stably produce a shrinkable film with improved orientation efficiency and excellent heat shrinkage rate at low temperatures.
第1図は本発明の実施例に用いた設備の説明用断面図で
ある。FIG. 1 is an explanatory sectional view of equipment used in an embodiment of the present invention.
Claims (1)
又は2種以上を含み、この共重合体又は共重合体混合物
の示差走査熱量計(以下DSCと略す)の測定による融
解曲線について、融点(吸熱メインピーク)より10℃
低い温度以下の吸熱面積が全吸熱面積の55%以上であ
るエチレン系重合体組成物を溶融押出しし冷却固化して
得られるフィルムを縦横それぞれ2倍以上延伸して得ら
れる90℃における面積収縮率が20%以上であり、厚
みムラが20%以下である熱収縮性フィルム。 2、α−オレフィンがブテン−1、ペンテン−1、ヘキ
セン−1、オクテン−1、4−メチルペンテン−1の群
より選ばれた1種以上である特許請求の範囲第1項記載
の熱収縮性フィルム。[Claims] 1. A differential scanning calorimeter (hereinafter abbreviated as DSC) of a linear copolymer of ethylene and α-olefin, including one or more linear copolymers of this copolymer or a copolymer mixture. Regarding the melting curve measured by
Area shrinkage rate at 90°C obtained by stretching a film obtained by melt-extruding an ethylene polymer composition whose endothermic area below a low temperature is 55% or more of the total endothermic area, cooling and solidifying it, and stretching it twice or more in both length and width. is 20% or more, and the thickness unevenness is 20% or less. 2. The heat shrinkage according to claim 1, wherein the α-olefin is one or more selected from the group of 1-butene, 1-pentene, 1-hexene, 1-octene, and 1-4-methylpentene. sex film.
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61044170A JPH0613192B2 (en) | 1986-03-03 | 1986-03-03 | Heat shrinkable film |
CA000530633A CA1297651C (en) | 1986-03-03 | 1987-02-26 | Heat shrinkable film |
DK102087A DK102087A (en) | 1986-03-03 | 1987-02-27 | shrink |
AU69568/87A AU589498B2 (en) | 1986-03-03 | 1987-02-27 | Heat shrinkable film |
EP87102895A EP0240705B1 (en) | 1986-03-03 | 1987-02-28 | Heat shrinkable film |
DE3788970T DE3788970T2 (en) | 1986-03-03 | 1987-02-28 | Heat shrinkable film. |
US07/020,980 US4801652A (en) | 1986-03-03 | 1987-03-02 | Heat shrinkable film |
FI870891A FI87930C (en) | 1986-03-03 | 1987-03-02 | Heat shrinkable film |
MX005449A MX168639B (en) | 1986-03-03 | 1987-03-03 | SHRINKABLE FILM WITH HEAT |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61044170A JPH0613192B2 (en) | 1986-03-03 | 1986-03-03 | Heat shrinkable film |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS62201229A true JPS62201229A (en) | 1987-09-04 |
JPH0613192B2 JPH0613192B2 (en) | 1994-02-23 |
Family
ID=12684114
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP61044170A Expired - Fee Related JPH0613192B2 (en) | 1986-03-03 | 1986-03-03 | Heat shrinkable film |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0613192B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2623744A1 (en) * | 1987-11-30 | 1989-06-02 | Kaysersberg Sa | PROCESS FOR PRODUCING THERMOPLASTIC THERMOREABLE TRICABLE FILM BY SUCCESSIVE STRETCHING |
WO2005049702A1 (en) * | 2003-11-21 | 2005-06-02 | Asahi Kasei Life & Living Corporation | Low-temperature shrinkable film |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5571529A (en) * | 1978-11-27 | 1980-05-29 | Mitsubishi Plastics Ind Ltd | Thermal contractive soft film |
JPS572488A (en) * | 1980-05-16 | 1982-01-07 | Zahnradfabrik Friedrichshafen | High pressure pump with flow controlling valve |
JPS57181828A (en) * | 1981-04-23 | 1982-11-09 | Du Pont | Shrinkable film of ethylene/alpha- olefin copolymer |
-
1986
- 1986-03-03 JP JP61044170A patent/JPH0613192B2/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5571529A (en) * | 1978-11-27 | 1980-05-29 | Mitsubishi Plastics Ind Ltd | Thermal contractive soft film |
JPS572488A (en) * | 1980-05-16 | 1982-01-07 | Zahnradfabrik Friedrichshafen | High pressure pump with flow controlling valve |
JPS57181828A (en) * | 1981-04-23 | 1982-11-09 | Du Pont | Shrinkable film of ethylene/alpha- olefin copolymer |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2623744A1 (en) * | 1987-11-30 | 1989-06-02 | Kaysersberg Sa | PROCESS FOR PRODUCING THERMOPLASTIC THERMOREABLE TRICABLE FILM BY SUCCESSIVE STRETCHING |
EP0319401A2 (en) * | 1987-11-30 | 1989-06-07 | Bollore Technologies | Method of producing a shrinkable film |
WO2005049702A1 (en) * | 2003-11-21 | 2005-06-02 | Asahi Kasei Life & Living Corporation | Low-temperature shrinkable film |
KR100720191B1 (en) * | 2003-11-21 | 2007-05-23 | 아사히 가세이 라이프 앤드 리빙 가부시키가이샤 | Low-temperature shrinkable film |
Also Published As
Publication number | Publication date |
---|---|
JPH0613192B2 (en) | 1994-02-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4801652A (en) | Heat shrinkable film | |
AU624253B2 (en) | Bioriented film | |
JP2904903B2 (en) | Polyethylene film | |
US5306549A (en) | Biaxially stretched polyethylene film | |
JP4915749B2 (en) | Polyolefin multilayer shrink film | |
JP3258830B2 (en) | Polyolefin-based heat-shrinkable laminated film | |
JP3751965B2 (en) | Polyolefin multilayer shrink film | |
US5635286A (en) | Heat shrinkable polyethylene laminate film | |
US20120164421A1 (en) | Polymeric Films And Methods To Manufacture Same | |
JPS62201229A (en) | Heat shrinkable film | |
JP3004314B2 (en) | Polyethylene heat-shrinkable laminated film | |
JPS6310639A (en) | Heat-shrinkable film and production thereof | |
JPH1199600A (en) | Polyolefinic laminated stretch shrink film | |
JP2011126247A (en) | Polyolefin-based thin film multilayered shrink film | |
JP2003145695A (en) | Method for manufacturing polyethylenic heat-shrinkable film | |
JP3748639B2 (en) | Polyolefin resin composition | |
WO1989001402A1 (en) | Process for producing heat-shrinkable polyethylene film | |
KR100203444B1 (en) | Ldpe film and there manufacturing method | |
JP3068920B2 (en) | Polyethylene heat-shrinkable laminated film | |
CA2118002C (en) | Heat shrinkable polyethylene laminate film | |
JPH09239926A (en) | Heat shrinkable laminated polyolefin film | |
JPH054276A (en) | Manufacture of polyethylene biaxially oriented film | |
JPH08151454A (en) | Thermally shrinkable polypropylene film | |
JPH0367015B2 (en) | ||
WO1990001409A1 (en) | Process for producing heat-shrinkable polyethylene film |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
LAPS | Cancellation because of no payment of annual fees |