JP2005111857A - Heat fusion-bonding propylene polymer laminated film and its application - Google Patents
Heat fusion-bonding propylene polymer laminated film and its application Download PDFInfo
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- JP2005111857A JP2005111857A JP2003350193A JP2003350193A JP2005111857A JP 2005111857 A JP2005111857 A JP 2005111857A JP 2003350193 A JP2003350193 A JP 2003350193A JP 2003350193 A JP2003350193 A JP 2003350193A JP 2005111857 A JP2005111857 A JP 2005111857A
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- propylene
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- olefin
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- 229920001155 polypropylene Polymers 0.000 title claims abstract description 38
- 239000004711 α-olefin Substances 0.000 claims abstract description 59
- 239000000203 mixture Substances 0.000 claims abstract description 42
- 229920005604 random copolymer Polymers 0.000 claims abstract description 34
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 29
- 229920000098 polyolefin Polymers 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 4
- 230000004927 fusion Effects 0.000 claims abstract 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 78
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 77
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- 239000005977 Ethylene Substances 0.000 claims description 34
- 238000002844 melting Methods 0.000 claims description 19
- 230000008018 melting Effects 0.000 claims description 19
- 239000012793 heat-sealing layer Substances 0.000 claims description 11
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- 235000013311 vegetables Nutrition 0.000 claims description 4
- 239000005001 laminate film Substances 0.000 claims description 2
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- IYYGCUZHHGZXGJ-UHFFFAOYSA-N but-1-ene;ethene;prop-1-ene Chemical compound C=C.CC=C.CCC=C IYYGCUZHHGZXGJ-UHFFFAOYSA-N 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
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- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Laminated Bodies (AREA)
- Wrappers (AREA)
Abstract
Description
本発明は高速、低圧下における低温ヒートシール性、密封性、ラミネート強度に優れ、且つ耐ブロッキング性、包装材料に好適なスリップ性、透明性等を有する熱融着性プロピレン系重合体積層フィルム及びその用途に関する。 The present invention is a heat-fusible propylene-based polymer laminated film having excellent high-speed, low-temperature heat-sealability under low pressure, sealing properties, laminate strength, and having blocking resistance, slip properties suitable for packaging materials, transparency, and the like. Regarding its use.
プロピレン系ランダム共重合体から得られるフィルムは低密度ポリエチレン、線状低密度ポリエチレン等のエチレン系重合体から得られるフィルムに比べて、ヒートシール強度、透明性、腰の強さ、耐ブロッキング性、ホットタック性、耐傷付き性、耐熱性等に優れるので、菓子、パン、野菜、麺等の食品、或いはシャツ、ズボン等の衣料品を始めとする日用品等あらゆる分野の製品の包装材料として広く使用されている。そして、かかるプロピレン系ランダム共重合体からなるフィルムは低密度ポリエチレン、線状低密度ポリエチレン等のエチレン系重合体からなるフィルムに比べると低温ヒートシール性に劣ることから、その改良が常に要求されている。低温ヒートシール性を改良する方法としては、例えば結晶性プロピレンランダム共重合体と１−ブテン系ランダム共重合体との組成物（特許文献１）、メタロセン触媒を用いた重合方法により得られるプロピレン・α―オレフィンランダム共重合体（例えば、特許文献２）等、種々提案されている。しかしながら、いずれのフィルムも低温ヒートシール性と剛性、密封性、ラミネート強度、耐ブロッキング性等のバランスに優れるものは得られていない。 Films obtained from propylene random copolymers are heat-seal strength, transparency, waist strength, blocking resistance compared to films obtained from ethylene polymers such as low-density polyethylene and linear low-density polyethylene. Excellent hot tack, scratch resistance, heat resistance, etc., so it is widely used as a packaging material for foods such as confectionery, bread, vegetables, noodles, and daily goods such as clothing such as shirts and pants. Has been. And since a film made of such a propylene-based random copolymer is inferior in low-temperature heat-sealability as compared with a film made of an ethylene-based polymer such as low-density polyethylene and linear low-density polyethylene, its improvement is always required. Yes. Examples of the method for improving the low temperature heat sealability include a composition of a crystalline propylene random copolymer and a 1-butene random copolymer (Patent Document 1), and a propylene-polymer obtained by a polymerization method using a metallocene catalyst. Various α-olefin random copolymers (for example, Patent Document 2) have been proposed. However, none of the films has a good balance of low-temperature heat sealability and rigidity, sealing properties, laminate strength, blocking resistance, and the like.
そこで本発明は、高速、低圧下における低温ヒートシール性、密封性、ラミネート強度に優れ、且つ耐ブロッキング性、包装材料に好適なスリップ性、透明性等を有する熱融着性プロピレン系重合体積層フィルムを得ることを目的として種々検討した。 Accordingly, the present invention provides a heat-fusible propylene polymer laminate having excellent high-temperature, low-temperature heat-sealability under low pressure, hermeticity, and laminate strength, as well as anti-blocking properties, slip properties suitable for packaging materials, and transparency. Various studies were conducted for the purpose of obtaining a film.
すなわち本発明は、ＤＳＣに基づく結晶融解曲線から求められたピーク温度（Ｔｐ）が１１０〜１４０℃及び融解開始温度（Ｔｓ）と融解終了温度（Ｔｅ）との差（Ｔｅ−Ｔｓ）が４５℃未満のプロピレン・α―オレフィン共重合体（Ａ）及び密度が０．８６５〜０．９１０ｇ／ｃｍ３のエチレン・α−オレフィンランダム共重合体（Ｂ）とのプロピレン系重合体組成物（Ｃ）から得られる熱融着層の片面に、前記プロピレン・α―オレフィン共重合体（Ａ）から得られる中間層を介して、プロピレン系重合体（Ｄ）及び前記エチレン・α−オレフィンランダム共重合体（Ｂ）とのオレフィン系重合体組成物（Ｅ）から得られるラミネート層を有してなることを特徴とする熱融着性プロピレン系重合体積層フィルム及びその用途に関する。 That is, in the present invention, the peak temperature (Tp) determined from the DSC-based crystal melting curve is 110 to 140 ° C., and the difference (Te−Ts) between the melting start temperature (Ts) and the melting end temperature (Te) is 45 ° C. Propylene / α-olefin copolymer (A) and a propylene-based polymer composition (C) with an ethylene / α-olefin random copolymer (B) having a density of 0.865 to 0.910 g / cm 3 The propylene-based polymer (D) and the ethylene / α-olefin random copolymer are interposed on one side of the heat-sealing layer obtained from the intermediate layer obtained from the propylene / α-olefin copolymer (A). The present invention relates to a heat-fusible propylene-based polymer laminated film characterized by comprising a laminate layer obtained from the olefin polymer composition (E) with (B) and its use.
本発明の熱融着性プロピレン系重合体積層フィルムは高速、低圧下における低温ヒートシール性に優れている。本発明の熱融着性プロピレン系重合体積層フィルムは更に、密封性、耐衝撃性に優れ、且つ耐ブロッキング性、包装材料に好適な剛性、スリップ性、透明性等にも優れている。 The heat-fusible propylene-based polymer laminated film of the present invention is excellent in low-temperature heat sealability at high speed and low pressure. The heat-fusible propylene-based polymer laminated film of the present invention is further excellent in sealing properties and impact resistance, as well as blocking resistance, rigidity suitable for packaging materials, slip properties, transparency, and the like.
プロピレン・α−オレフィンランダム共重合体（Ａ）
本発明に係わるプロピレン・α−オレフィン共重合体（Ａ）は、ＤＳＣに基づく結晶融解曲線から求められたピーク温度（Ｔｐ）が１１０〜１４０℃、好ましくは１１５〜１３０℃、融解開始温度（Ｔｓ）と融解終了温度（Ｔｅ）との差（Ｔｅ−Ｔｓ）が４５℃未満、好ましくは３０〜４０℃の範囲にあり、好ましくは融解開始温度（Ｔｓ）とピーク温度（Ｔｐ）との差（Ｔｐ−Ｔｓ）が３５℃未満、より好ましくは２５〜３４℃の範囲にある。プロピレン・α−オレフィン共重合体（Ａ）のα―オレフィンの含有量は上記熱融解特性を有する限りとくに制限はされないが、通常はα―オレフィンの含有量は１．０〜２０重量％、より好ましくは１．５〜１５重量％の範囲にある。α―オレフィンとしては、エチレン、１−ブテン、１−ヘキセン、４−メチル・１−ペンテン、１−オクテン等が例示できる。これらの中では、エチレン及び／又は１−ブテンとのランダム共重合体が好ましい。又、ＭＦＲ（メルトフローレート；ＡＳＴＭ Ｄ−１２３８ 荷重２１６０ｇ、温度２３０℃）はフィルムとすることができる限り特に限定はされないが、通常０．５〜２０ｇ／１０分、好ましくは２〜１０ｇ／１０分の範囲にある。本発明に係わるプロピレン・α−オレフィン共重合体（Ａ）は通常、分子量分布（重量平均分子量Ｍｗと数平均分子量Ｍｎとの比で表される）が２〜３の範囲にある。
本発明に係わるプロピレン・α―オレフィン共重合体（Ａ）は、後述のエチレン・α−オレフィンランダム共重合体（Ｂ）とともに熱融着性プロピレン系重合体積層フィルムの熱融着層及び必要に応じ中間層の原料となる。
本発明に係わるプロピレン・α−オレフィン共重合体（Ａ）の上記ピーク温度（Ｔｐ）、融解開始温度（Ｔｓ）及び融解終了温度（Ｔｅ）は以下の方法で測定した。プロピレン・α−オレフィン共重合体（Ａ）約５ｍｇを秤量し、セイコ−電子工業株式会社製の示差走査熱量計（タイプＤＳＣ２２０モジュ−ル）を用いて、昇温速度；１０℃／分で２００℃まで昇温し、２００℃で５分間保持した後、降温速度；１００℃／分で０℃まで冷却し、再度、昇温速度；１０℃／分で０℃〜２００℃まで昇温したときの融解曲線を測定し、かかる融解曲線から、ＡＳＴＭ Ｄ３４１９の方法に習い、融解曲線からピ−ク温度（Ｔｐ）、融解開始温度（Ｔｓ）、融解終了温度（Ｔｅ）を求めた。尚、本発明では、ＡＳＴＭ Ｄ３４１９に記載の（Ｔｐｍ１）を（Ｔｐ）、（Ｔｅｉｍ）を（Ｔｓ）及び（Ｔｅｆｍ）を（Ｔｅ）とした。
Propylene / α-olefin random copolymer (A)
The propylene / α-olefin copolymer (A) according to the present invention has a peak temperature (Tp) determined from a crystal melting curve based on DSC of 110 to 140 ° C., preferably 115 to 130 ° C., and a melting start temperature (Ts). ) And the melting end temperature (Te) (Te−Ts) is less than 45 ° C., preferably in the range of 30-40 ° C., preferably the difference between the melting start temperature (Ts) and the peak temperature (Tp) ( Tp−Ts) is less than 35 ° C., more preferably in the range of 25 to 34 ° C. The α-olefin content of the propylene / α-olefin copolymer (A) is not particularly limited as long as it has the above-mentioned heat melting characteristics, but usually the α-olefin content is 1.0 to 20% by weight, more Preferably it exists in the range of 1.5 to 15 weight%. Examples of the α-olefin include ethylene, 1-butene, 1-hexene, 4-methyl / 1-pentene, 1-octene and the like. In these, the random copolymer with ethylene and / or 1-butene is preferable. The MFR (melt flow rate; ASTM D-1238 load 2160 g, temperature 230 ° C.) is not particularly limited as long as it can be made into a film, but is usually 0.5 to 20 g / 10 minutes, preferably 2 to 10 g / 10. In the range of minutes. The propylene / α-olefin copolymer (A) according to the present invention usually has a molecular weight distribution (expressed by a ratio of the weight average molecular weight Mw and the number average molecular weight Mn) in the range of 2 to 3.
The propylene / α-olefin copolymer (A) according to the present invention includes a heat-fusible layer of a heat-fusible propylene-based polymer laminated film together with an ethylene / α-olefin random copolymer (B) to be described later and the necessity. In response, it becomes a raw material for the intermediate layer.
The peak temperature (Tp), melting start temperature (Ts) and melting end temperature (Te) of the propylene / α-olefin copolymer (A) according to the present invention were measured by the following methods. About 5 mg of propylene / α-olefin copolymer (A) is weighed, and using a differential scanning calorimeter (type DSC220 module) manufactured by Seiko Denshi Kogyo Co., Ltd., the heating rate is 200 ° C./min. When the temperature was raised to 0 ° C. and held at 200 ° C. for 5 minutes, the temperature was lowered to 0 ° C. at 100 ° C./min, and the temperature was raised again from 0 ° C. to 200 ° C. at 10 ° C./min. From this melting curve, the peak temperature (Tp), the melting start temperature (Ts), and the melting end temperature (Te) were determined from the melting curve according to the method of ASTM D3419. In the present invention, (Tpm1) described in ASTM D3419 is (Tp), (Tim) is (Ts), and (Tefm) is (Te).
エチレン・α−オレフィンランダム共重合体（Ｂ）
本発明に係るエチレン・α−オレフィンランダム共重合体（Ｂ）は、炭素数３以上、好ましくは４〜１０のα−オレフィンとのランダム共重合体で、好ましくは密度が０．８６５〜０．９１０ｇ／ｃｍ３、更に好ましくは０．８７５〜０．９００ｇ／ｃｍ３、好ましくはエチレン含有量が７０〜９５モル％、更に好ましくは８０〜９３モル％、好ましくはＸ線による結晶化度が５〜４０％、更に好ましくは７〜３０％、好ましくはＧＰＣで測定した分子量分布（Ｍｗ／Ｍｎ）が３以下、更に好ましくは２．５以下であり、好ましくはＤＳＣによる昇温速度１０℃／分での吸熱曲線から求めた融点が４０〜１００℃、更に好ましくは６０〜９０℃であり、メルトフローレート（１９０℃）が好ましくは０．０１〜２０ｇ／１０分、更には０．１〜５ｇ／１０分の範囲にある。
本発明に係るエチレン・α−オレフィンランダム共重合体（Ｂ）は、前記熱プロピレン・α−オレフィン共重合体（Ａ）とともに融着性プロピレン系重合体積層フィルムの熱融着層の原料となり、又、後述のプロピレン系重合体（Ｄ）とともにラミネ−ト層の原料となる。
Ethylene / α-olefin random copolymer (B)
The ethylene / α-olefin random copolymer (B) according to the present invention is a random copolymer with an α-olefin having 3 or more carbon atoms, preferably 4 to 10 carbon atoms, and preferably has a density of 0.865 to 0.8. 910 g / cm 3, more preferably 0.875~0.900g / cm 3, preferably ethylene content of 70 to 95 mol%, more preferably 80 to 93 mol%, preferably crystallinity by X-ray 5 -40%, more preferably 7-30%, preferably the molecular weight distribution (Mw / Mn) measured by GPC is 3 or less, more preferably 2.5 or less, preferably the heating rate by DSC is 10 ° C / min. The melting point determined from the endothermic curve at 40 to 100 ° C., more preferably 60 to 90 ° C., and the melt flow rate (190 ° C.) is preferably 0.01 to 20 g / 10 minutes, and more preferably 0. It is in the range of ~5g / 10 minutes.
The ethylene / α-olefin random copolymer (B) according to the present invention is a raw material for the heat-fusible layer of the fusible propylene-based polymer laminated film together with the thermal propylene / α-olefin copolymer (A), Further, it becomes a raw material for the laminate layer together with the propylene polymer (D) described later.
プロピレン系重合体（Ｄ）
本発明に係わるプロピレン系重合体（Ｄ）は、プロピレンの単独重合体、またはプロピレンと１０重量％以下、好ましくは５重量％以下のα−オレフィンとの共重合体である。α−オレフィンは、プロピレン以外の通常炭素数２〜１０のα−オレフィンであって、例えば、エチレン、１−ブテン、３−メチル−１−ブテン、１―ペンテン、３―メチル―１―ペンテン、４−メチル−１−ペンテン、１―へキセン、１―オクテン等を挙げることができる。かかるプロピレン系重合体（Ｄ）は、フィルムとして成形できる限り、特に限定はされないが、ＭＦＲ（メルトフローレート；ＡＳＴＭ Ｄ−１２３８ 荷重２１６０ｇ、温度２３０℃）が、通常０．１〜１００ｇ／１０分、好ましくは１〜５０ｇ／１０分の範囲にある。
本発明に係わるプロピレン重合体（Ｄ）は、熱融着性プロピレン系重合体積層フィルムラミネート層の原料となる。
Propylene polymer (D)
The propylene polymer (D) according to the present invention is a homopolymer of propylene or a copolymer of propylene and an α-olefin of 10% by weight or less, preferably 5% by weight or less. The α-olefin is usually an α-olefin having 2 to 10 carbon atoms other than propylene, such as ethylene, 1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene and the like can be mentioned. The propylene-based polymer (D) is not particularly limited as long as it can be molded as a film, but MFR (melt flow rate; ASTM D-1238 load 2160 g, temperature 230 ° C.) is usually 0.1 to 100 g / 10 min. , Preferably in the range of 1-50 g / 10 min.
The propylene polymer (D) according to the present invention is a raw material for the heat-fusible propylene polymer laminated film laminate layer.
プロピレン系重合体組成物（Ｃ）
本発明に係わるプロピレン系重合体組成物（Ｃ）は、前記プロピレン・α−オレフィン共重合体（Ａ）と前記エチレン・α−オレフィンランダム共重合体（Ｂ）とから得られる組成物であり、好ましくはプロピレン・α−オレフィン共重合体（Ａ）が７０〜９５重量％、更に好ましくは７５〜９０重量％、エチレン・α−オレフィンランダム共重合体（Ｂ）が３０〜５重量％、更に好ましくは２５〜１０重量％の範囲にある。
プロピレン・α−オレフィン共重合体（Ａ）が７０重量％未満では、熱融着性プロピレン系重合体積層フィルムを得る際に、製膜時にベタツキが発生し、その結果、得られる積層フィルムの滑性が劣り、巻き取り時のシワが発生する虞がある。又、得られる熱融着性プロピレン系重合体積層フィルムの剛性、滑性、耐ブロッキング性が劣る虞もある。一方、９５重量％を越えると得られる熱融着性プロピレン系重合体積層フィルムの低温ヒートシール性が改良されず、ヒートシール強度も劣る虞がある。
本発明に係わるプロピレン系重合体組成物（Ｃ）は組成物を構成する成分として上記特性を有するプロピレン・α−オレフィン共重合体（Ａ）を用いることにより、低温ヒートシール性の改良材であるエチレン・α−オレフィンランダム共重合体（Ｂ）の量を減らすことが可能であり、その結果、フィルム成形時の製膜性が改良され、また得られる熱融着性プロピレン系重合体フィルムの耐ブロッキング性、密封性が改良される。
プロピレン共重合体組成物（Ｃ）のＭＦＲ（メルトフローレート；ＡＳＴＭ Ｄ−１２３８ 荷重２１６０ｇ、温度２３０℃）はフィルム成形が可能な限り特に限定はされないが、通常０．１〜５０ｇ／１０分、好ましくは０．３〜３０ｇ／１０分の範囲にある。
Propylene polymer composition (C)
The propylene-based polymer composition (C) according to the present invention is a composition obtained from the propylene / α-olefin copolymer (A) and the ethylene / α-olefin random copolymer (B), Preferably, the propylene / α-olefin copolymer (A) is 70 to 95% by weight, more preferably 75 to 90% by weight, and the ethylene / α-olefin random copolymer (B) is 30 to 5% by weight, more preferably. Is in the range of 25 to 10% by weight.
When the propylene / α-olefin copolymer (A) is less than 70% by weight, stickiness occurs during film formation when a heat-fusible propylene-based polymer laminated film is obtained, and as a result, the resulting laminated film slips. Inferior, there is a risk of wrinkling during winding. In addition, the heat-fusible propylene-based polymer laminated film obtained may be inferior in rigidity, slipperiness and blocking resistance. On the other hand, if it exceeds 95% by weight, the low temperature heat sealability of the heat-fusible propylene polymer laminated film obtained is not improved, and the heat seal strength may be inferior.
The propylene-based polymer composition (C) according to the present invention is an improved material for low-temperature heat sealability by using the propylene / α-olefin copolymer (A) having the above characteristics as a component constituting the composition. It is possible to reduce the amount of the ethylene / α-olefin random copolymer (B). As a result, the film-forming property at the time of film forming is improved, and the heat-resistant propylene-based polymer film has a resistance to resistance. Blocking and sealing properties are improved.
The MFR (melt flow rate; ASTM D-1238 load 2160 g, temperature 230 ° C.) of the propylene copolymer composition (C) is not particularly limited as long as film forming is possible, but usually 0.1 to 50 g / 10 min. Preferably it exists in the range of 0.3-30 g / 10min.
オレフィン系重合体組成物（Ｅ）
本発明に係わるオレフィン系重合体組成物（Ｅ）は、前記プロピレン系重合体（Ｄ）と前記エチレン・α−オレフィンランダム共重合体（Ｂ）とから得られる組成物であり、好ましくはプロピレン系重合体（Ｄ）が７０〜９５重量％、更に好ましくは７５〜９０重量％、エチレン・α−オレフィンランダム共重合体（Ｂ）が３０〜５重量％、更に好ましくは２５〜１０重量％の範囲にある。プロピレン系重合体（Ｄ）が７０重量％未満では、熱融着性プロピレン系重合体積層フィルムを得る際に、製膜時にベタツキが発生し、その結果、得られる積層フィルムの滑性が劣り、巻き取り時のシワが発生する虞がある。また、得られる熱融着性プロピレン系重合体積層フィルムの剛性、滑性、耐ブロッキング性が劣る虞もある。一方、９５重量％を越えると得られる熱融着性プロピレン系重合体積層フィルムの低温ヒートシール性が改良されず、ヒートシール強度も劣る虞がある。
本発明に係わるオレフィン系重合体組成物（Ｅ）は組成物を構成する成分としてプロピレン系重合体（Ｄ）としてプロピレンの単独重合体を用いることにより、特に耐熱性と剛性が向上し、その結果、フィルム成形時の製膜性が改良され、また得られる熱融着性プロピレン系重合体フィルムの耐ブロッキング性が改良される。
オレフィン系重合体組成物（Ｅ）のＭＦＲ（メルトフローレート；ＡＳＴＭ Ｄ−１２３８ 荷重２１６０ｇ、温度２３０℃）はフィルム成形が可能な限り特に限定はされないが、通常０．１〜５０ｇ／１０分、好ましくは０．３〜３０ｇ／１０分の範囲にある。
Olefin polymer composition (E)
The olefin polymer composition (E) according to the present invention is a composition obtained from the propylene polymer (D) and the ethylene / α-olefin random copolymer (B), preferably a propylene polymer. The polymer (D) is 70 to 95% by weight, more preferably 75 to 90% by weight, and the ethylene / α-olefin random copolymer (B) is 30 to 5% by weight, more preferably 25 to 10% by weight. It is in. When the propylene-based polymer (D) is less than 70% by weight, when obtaining a heat-fusible propylene-based polymer laminated film, stickiness occurs during film formation, and as a result, the resulting laminated film has poor lubricity, There is a risk of wrinkling during winding. In addition, the resulting heat-fusible propylene polymer laminated film may be inferior in rigidity, slipperiness and blocking resistance. On the other hand, if it exceeds 95% by weight, the low temperature heat sealability of the heat-fusible propylene polymer laminated film obtained is not improved, and the heat seal strength may be inferior.
In the olefin polymer composition (E) according to the present invention, by using a propylene homopolymer as the propylene polymer (D) as a component constituting the composition, heat resistance and rigidity are particularly improved. The film-forming property at the time of film forming is improved, and the blocking resistance of the heat-fusible propylene-based polymer film obtained is improved.
The MFR (melt flow rate; ASTM D-1238 load 2160 g, temperature 230 ° C.) of the olefin polymer composition (E) is not particularly limited as long as film molding is possible, but usually 0.1 to 50 g / 10 min. Preferably it exists in the range of 0.3-30 g / 10min.
本発明に係わるプロピレン・α−オレフィン共重合体（Ａ）、エチレン・α−オレフィンランダム共重合体（Ｂ）、プロピレン系重合体（Ｄ）、プロピレン系重合体組成物（Ｃ）あるいはオレフィン系重合体組成物（Ｅ）には本発明の目的を損なわない範囲で、通常用いられる酸化防止剤、耐候安定剤、帯電防止剤、防曇剤、ブロッキング防止剤、滑剤、核剤、顔料等の添加剤或いは他の重合体を必要に応じて配合することができる。
中でも、熱融着層を構成するプロピレン系重合体組成物（Ｃ）にはシリカ、タルク、雲母、ゼオライトや更には金属アルコキシドを焼成して得た金属酸化物等の無機化合物粒子、ポリメタクリル酸メチル、メラミンホルマリン樹脂、メラミン尿素樹脂、ポリエステル樹脂等の有機化合物粒子等、種々公知のブロッキング防止剤を０．０１〜１重量％添加しておくと、更に耐ブロッキング性が改良されたフィルムが得られるので好ましい。これらの中でも、シリカ、ポリメタクリル酸メチルが耐ブロッキング性、透明性の面から特に好ましい。
又、熱融着層を構成するプロピレン系重合体組成物（Ｃ）には、炭化水素系、脂肪酸系、高級アルコ−ル系、脂肪族アミド系、金属石鹸系、エステル系等、種々公知の滑剤を０．０１〜１重量％添加しておくと、更にスリップ性が改良されたフィルムが得られるので好ましい。これらの中でも即効性のあるエルカ酸アミドと遅効性のビスオレイン酸アミドあるいはベヘニン酸アミド等の併用系にするとフィルム成形直後とその後の裁断加工時、更には印刷、ラミネ−ト、製袋加工時等の作業性をバランス良く改善することができる。
更に、熱融着層を構成するプロピレン系重合体組成物（Ｃ）には、高密度ポリエチレン、ジベンジリデンソルビト−ル、クロル置換ジベンジリデンソルビト−ル、メチル置換ジベンジリデンソルビト−ル、ヒドロキシ−ジ−アルミニウム
、ビスソルビシ−ル、リン酸ビスナトリウムメチレンビスアシッドホスフェ−ト
ナトリウム塩等、種々公知の核剤（結晶化核剤）を０．０１〜１．０重量％添加しておくと、フィルム成形時のロ−ル跡の発生を抑えたり、直後でのスリップ性・ブロッキング性が改良されたフィルムが得られるので好ましい。これらの中でも比較的添加しやすく臭い等も問題ないポリエチレン結晶化核剤を利用するとフィルム成形直後の品質と加工適性をバランス良く改善することができる。また、中間層を構成するプロピレン・α―オレフィン共重合体（Ａ）にも、同様の種々公知の核剤（結晶化核剤）を添加しておくと同様の改善をすることができる。
ラミネート層を構成するオレフィン系重合体組成物（Ｅ）にも種々公知のブロッキング防止剤を０．０１〜１重量％添加しておくと、更に耐ブロッキング性が改良されたフィルムが得られるので好ましい。又、種々公知の滑剤を０．０１〜１重量％添加しておくと、更にスリップ性が改良されたフィルムが得られるので好ましい。
Propylene / α-olefin copolymer (A), ethylene / α-olefin random copolymer (B), propylene polymer (D), propylene polymer composition (C) or olefin heavy Addition of commonly used antioxidants, weathering stabilizers, antistatic agents, antifogging agents, antiblocking agents, lubricants, nucleating agents, pigments, etc. to the combined composition (E) within a range not impairing the object of the present invention An agent or other polymer can be blended as necessary.
Among them, the propylene polymer composition (C) constituting the heat-sealing layer includes silica, talc, mica, zeolite, and further inorganic compound particles such as metal oxide obtained by firing metal alkoxide, polymethacrylic acid Adding 0.01 to 1% by weight of various known anti-blocking agents such as organic compound particles such as methyl, melamine formalin resin, melamine urea resin, and polyester resin, a film with further improved blocking resistance is obtained. This is preferable. Among these, silica and polymethyl methacrylate are particularly preferable in terms of blocking resistance and transparency.
In addition, the propylene polymer composition (C) constituting the heat-sealing layer includes various known hydrocarbons, fatty acids, higher alcohols, aliphatic amides, metal soaps, esters, and the like. It is preferable to add a lubricant in an amount of 0.01 to 1% by weight because a film with improved slip properties can be obtained. Of these, the combination system of erucic acid amide with immediate effect and slow-acting bisoleic acid amide or behenic acid amide can be used immediately after film forming and at the time of subsequent cutting, as well as printing, laminating and bag making. Etc. can be improved in a balanced manner.
Furthermore, the propylene polymer composition (C) constituting the heat-sealing layer includes high-density polyethylene, dibenzylidene sorbitol, chloro-substituted dibenzylidene sorbitol, methyl-substituted dibenzylidene sorbitol, Various known nucleating agents (crystallization nucleating agents) such as hydroxy-di-aluminum, bissorbicyl, bissodium methylenebisacid phosphate sodium salt and the like are added in an amount of 0.01 to 1.0% by weight. In addition, it is preferable because it is possible to obtain a film in which the occurrence of a roll mark during film formation is suppressed and the slip property and blocking property immediately after the film are improved. Among these, the use of a polyethylene crystallization nucleating agent that is relatively easy to add and has no problem with odor can improve the quality and processability immediately after film formation in a well-balanced manner. The same improvement can be achieved by adding various known nucleating agents (crystallization nucleating agents) to the propylene / α-olefin copolymer (A) constituting the intermediate layer.
It is preferable to add 0.01 to 1% by weight of various known anti-blocking agents to the olefin polymer composition (E) constituting the laminate layer because a film with improved blocking resistance can be obtained. . Also, it is preferable to add 0.01 to 1% by weight of various known lubricants because a film with improved slip properties can be obtained.
プロピレン系重合体の製造方法
本発明に係わるプロピレン・α−オレフィン共重合体（Ａ）及びプロピレン重合体（Ｄ）は種々公知の方法、例えば、典型的には固体状チタン触媒成分と有機金属化合物触媒成分から形成される触媒、あるいはこれら両成分および電子供与体から形成される触媒を用いて製造することができる。
固体状チタン触媒成分としては、各種方法で製造された三塩化チタンまたは三塩化チタン組成物、あるいはマグネシウム、ハロゲン、電子供与体、好ましくは芳香族カルボン酸エステルまたはアルキル基含有エーテルおよびチタンを必須成分とする、比表面積が好適には１００ｍ２／ｇ以上の担体付チタン触媒成分が挙げられる。特に後者の担体付触媒成分を用いて製造された重合体が好適である。
Propylene Polymer Production Method The propylene / α-olefin copolymer (A) and the propylene polymer (D) according to the present invention may be produced by various known methods, for example, typically a solid titanium catalyst component and an organometallic compound. It can be produced using a catalyst formed from a catalyst component, or a catalyst formed from both of these components and an electron donor.
As a solid titanium catalyst component, titanium trichloride or a titanium trichloride composition produced by various methods, or magnesium, halogen, an electron donor, preferably an aromatic carboxylic acid ester or an alkyl group-containing ether and titanium are essential components. And a supported titanium catalyst component having a specific surface area of preferably 100 m 2 / g or more. In particular, a polymer produced using the latter supported catalyst component is preferred.
有機金属化合物触媒成分としては、有機アルミニウム化合物が好適であり、具体的には、トリアルキルアルミニウム、ジアルキルアルミニウムハライド、アルキルアルミニウムセスキハライド、アルキルアルミニウムジハライドなどが挙げられる。これらの化合物のうち、好適な有機金属化合物触媒成分は、使用する上記チタン触媒成分の種類によって異なる。
電子供与体は、窒素、リン、イオウ、酸素、ケイ素、ホウ素などを含む有機化合物であり、好適な具体例としては、これらの元素を有する有機エステル、有機エーテルなどを挙げることができる。
担体付触媒成分を用いた重合体の製造方法に関しては、たとえば特開昭５０−１０８３８５号、特開昭５０−１２６５９０号、特開昭５１−２０２９７号、特開昭５１−２８１８９号、特開昭５２−１５１６９１号などの各公報に開示されている。
The organometallic compound catalyst component is preferably an organoaluminum compound, and specific examples include trialkylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, alkylaluminum dihalide, and the like. Among these compounds, a suitable organometallic compound catalyst component varies depending on the type of the titanium catalyst component used.
The electron donor is an organic compound containing nitrogen, phosphorus, sulfur, oxygen, silicon, boron, and the like. Suitable specific examples include organic esters and organic ethers having these elements.
With respect to the method for producing a polymer using a catalyst component with a carrier, for example, JP-A-50-108385, JP-A-50-126590, JP-A-51-20297, JP-A-51-28189, JP It is disclosed in each publication such as Sho 52-151691.
本発明に係わるプロピレン・α−オレフィン共重合体（Ａ）は、特にはシングルサイト触媒を用いて製造することができる。シングルサイト触媒は、活性点が均一（シングルサイト）である触媒であり、例えばメタロセン触媒（いわゆるカミンスキー触媒）やブルックハート触媒などがあげられる。例えばメタロセン触媒は、メタロセン系遷移金属化合物と、有機アルミニウム化合物および上記メタロセン系遷移金属化合物と反応してイオン対を形成する化合物からなる群から選ばれる少なくとも一種の化合物とからなる触媒であり、無機物に担持されていてもよい。
前記メタロセン系遷移金属化合物としては、例えば特開平５−２０９０１４号、特開平６−１００５７９号、特開平１−３０１７０４号、特開平３−１９３７９６号、特開平５−１４８２８４号、特開２０００−２０４３１号等に記載された化合物などがあげられる。
The propylene / α-olefin copolymer (A) according to the present invention can be produced particularly using a single site catalyst. The single site catalyst is a catalyst having a uniform active site (single site), and examples thereof include a metallocene catalyst (so-called Kaminsky catalyst) and a Brookhart catalyst. For example, a metallocene catalyst is a catalyst comprising a metallocene transition metal compound, at least one compound selected from the group consisting of an organoaluminum compound and a compound that forms an ion pair by reacting with the metallocene transition metal compound, and an inorganic substance. It may be carried on.
Examples of the metallocene transition metal compound include JP-A-5-209014, JP-A-6-1005209, JP-A-1-301704, JP-A-3-193966, JP-A-5-148284, and JP-A-2000-20431. And the like, and the like.
有機アルミニウム化合物としては、アルキルアルミニウム、または鎖状あるいは環状アルミノキサン等があげられる。上記鎖状あるいは環状アルミノキサンは、アルキルアルミニウムと水とを接触させることにより生成される。例えば重合時にアルキルアルミニウムを加えておいて、後で水を添加するか、あるいは錯塩の結晶水または有機、無機化合物の吸着水とアルキルアルミニウムとを反応させることにより得られる。
前記メタロセン系遷移金属化合物と反応してイオン対を形成する化合物は、例えば特表平１−５０１９５０号、特開平３−２０７７０４号、特開２００２−２０４３１号等に記載された化合物などがあげられる。シングルサイト触媒を担持させる前記無機物としては、シリカゲル、ゼオライト、珪藻土等があげられる。
重合方法としては、塊状重合、溶液重合、懸濁重合、気相重合等があげられる。これらの重合はバッチ法であっても連続法であっても良い。重合条件は通常、重合温度；−１００〜＋２５０℃、重合時間；５分〜１０時間、反応圧力；常圧〜３００Ｋｇ／ｃｍ２（ゲージ圧）である。
Examples of the organoaluminum compound include alkylaluminum, chain or cyclic aluminoxane, and the like. The chain or cyclic aluminoxane is produced by bringing alkylaluminum into contact with water. For example, it can be obtained by adding alkylaluminum at the time of polymerization and adding water later, or by reacting crystallization water of a complex salt or adsorbed water of an organic or inorganic compound with alkylaluminum.
Examples of the compound that reacts with the metallocene transition metal compound to form an ion pair include compounds described in JP-A-1-501950, JP-A-3-207704, JP-A-2002-20431, and the like. . Examples of the inorganic substance that supports the single-site catalyst include silica gel, zeolite, diatomaceous earth, and the like.
Examples of the polymerization method include bulk polymerization, solution polymerization, suspension polymerization, gas phase polymerization and the like. These polymerizations may be batch processes or continuous processes. The polymerization conditions are usually a polymerization temperature: −100 to + 250 ° C., a polymerization time: 5 minutes to 10 hours, a reaction pressure; a normal pressure to 300 Kg / cm 2 (gauge pressure).
熱融着性プロピレン系重合体積層フィルム
本発明の熱融着性プロピレン系重合体積層フィルムは、前記プロピレン系重合体組成物（Ｃ）から得られる熱融着層の片面に、前記プロピレン・α―オレフィン共重合体（Ａ）から得られる中間層を介して、前記オレフィン系重合体組成物（Ｅ）から得られるラミネート層を有してなる
熱融着性プロピレン系重合体積層フィルムの厚さは用途により種々決定され得るが、通常熱融着層の厚さが１〜８０μｍ、好ましくは２〜５０μｍ、中間層の厚さが８〜４９８μｍ、好ましくは１６〜９６μｍ、ラミネート層の厚さが１〜８０μｍ、好ましくは２〜５０μｍの範囲にあり、多層フィルム全体の厚さが、１０〜５００μｍ、好ましくは２０〜１００μｍの範囲にある。
本発明の熱融着性プロピレン系重合体積層フィルムは、プロピレン系重合体組成物（Ｃ）から得られる熱融着層、前記プロピレン系重合体（Ｄ）または前記プロピレン・α―オレフィン共重合体（Ａ）から得られる中間層及び前記オレフィン系重合体組成物（Ｅ）から得られるラミネート層を有することにより、低温ヒートシ−ル性、耐ブロッキング性、密封性、耐衝撃性、スリップ性、剛性、透明性等に優れる。
また、中間層として前記プロピレン・α―オレフィン共重合体（Ａ）を用いることにより、易引裂性に優れる。
本発明の熱融着性プロピレン系重合体積層フィルムは、印刷性あるいは他のフィルムとの接着性を改良するために、ラミネート層の表面を、たとえば、コロナ処理、火炎処理、プラズマ処理、アンダーコート処理等で表面活性化処理を行っておいてもよい。
Heat-fusible propylene-based polymer laminated film The heat-fusible propylene-based polymer laminated film of the present invention has the propylene / α on one side of a heat-fusible layer obtained from the propylene-based polymer composition (C). -Thickness of heat-fusible propylene-based polymer laminate film having a laminate layer obtained from the olefin-based polymer composition (E) through an intermediate layer obtained from the olefin-based copolymer (A) The thickness of the heat-sealing layer is usually 1 to 80 μm, preferably 2 to 50 μm, the thickness of the intermediate layer is 8 to 498 μm, preferably 16 to 96 μm, and the thickness of the laminate layer is The thickness is in the range of 1 to 80 μm, preferably 2 to 50 μm, and the total thickness of the multilayer film is in the range of 10 to 500 μm, preferably 20 to 100 μm.
The heat-fusible propylene-based polymer laminated film of the present invention includes a heat-fusible layer obtained from the propylene-based polymer composition (C), the propylene-based polymer (D), or the propylene / α-olefin copolymer. By having an intermediate layer obtained from (A) and a laminate layer obtained from the olefin polymer composition (E), low-temperature heat seal properties, blocking resistance, sealing properties, impact resistance, slip properties, rigidity Excellent in transparency.
Further, by using the propylene / α-olefin copolymer (A) as an intermediate layer, it is excellent in easy tearability.
The heat-fusible propylene-based polymer laminated film of the present invention can be applied to the surface of a laminate layer, for example, corona treatment, flame treatment, plasma treatment, undercoat, in order to improve printability or adhesion to other films. Surface activation treatment may be performed by treatment or the like.
本発明の熱融着性プロピレン系重合体積層フィルムは、低温ヒートシ−ル性、耐ブロッキング性、包装材料に好適な耐衝撃性、スリップ性、剛性、透明性、易引裂性等を有する熱融着性プロピレン系重合体積層フィルムとしてそのままでも包装用フィルム、中でもうどんなどの麺類やもやしなど野菜類の包装用フィルムとして好適に使用し得る。
又、用途によっては熱融着性プロピレン系重合体積層フィルムのラミネート層に後述の基材層を貼り合せて種々用途に用いることもできる。
The heat-fusible propylene-based polymer laminated film of the present invention has a low temperature heat seal property, blocking resistance, impact resistance suitable for packaging materials, slip property, rigidity, transparency, easy tear property, etc. It can be suitably used as an adhesive propylene-based polymer laminated film as it is as a packaging film, and as a packaging film for vegetables such as any noodles and bean sprouts.
Further, depending on the use, a base material layer described later can be bonded to the laminate layer of the heat-fusible propylene polymer laminated film and used for various purposes.
本発明の熱融着性プロピレン系重合体積層フィルムは公知の種々公知のフィルム成形方法を採用し得る。その際、フィルム成形する前に、熱融着層を構成する上記組成のプロピレン系重合体組成物（Ｃ）を予め用意しておいてもよいし、プロピレン・α−オレフィン共重合体（Ａ）及びエチレン・α−オレフィンランダム共重合体（Ｂ）を所定量計量して直接フィルム成形機に投入してもよい。又、同じくラミネート層も前記組成のオレフィン系重合体組成物（Ｅ）を予め用意しておいてもよいし、エチレン・α−オレフィンランダム共重合体（Ｂ）及びプロピレン系重合体（Ｄ）を所定量計量して直接フィルム成形機に投入してもよい。かかる積層フィルムは夫々別個にフィルムを成形後貼り合せてもよいが、三層構造の多層ダイを用いて共押出し成形による方法が最も好ましい。 The heat-fusible propylene-based polymer laminated film of the present invention can employ various known film forming methods. At that time, before forming the film, the propylene polymer composition (C) having the above composition constituting the heat-sealing layer may be prepared in advance, or the propylene / α-olefin copolymer (A). Further, a predetermined amount of the ethylene / α-olefin random copolymer (B) may be weighed and directly fed into the film forming machine. Similarly, the laminate layer may be prepared in advance with the olefin polymer composition (E) having the above composition, or the ethylene / α-olefin random copolymer (B) and the propylene polymer (D). A predetermined amount may be measured and put directly into the film forming machine. Such laminated films may be individually laminated after being molded, but a method by coextrusion molding using a multilayer die having a three-layer structure is most preferable.
基材層
本発明に係わる基材層は、熱可塑性樹脂からなるシート状またはフィルム状のもの、紙、アルミニウム箔等からなる。熱可塑性樹脂としては、種々公知の熱可塑性樹脂、例えば、ポリオレフィン（ポリエチレン、ポリプロピレン、ポリ４−メチル・１−ペンテン、ポリブテン等）、ポリエステル（ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等）、ポリアミド（ナイロン−６、ナイロン−６６、ポリメタキシレンアジパミド等）、ポリ塩化ビニル、ポリイミド、エチレン・酢酸ビニル共重合体もしくはその鹸化物、ポリビニルアルコール、ポリアクリロニトリル、ポリカーボネート、ポリスチレン、アイオノマー、あるいはこれらの混合物等を例示することができる。これらのうちでは、ポリプロピレン、ポリエチレンテレフタレート、ポリアミド等、延伸性、透明性が良好な熱可塑性樹脂が好ましい。又、かかる熱可塑性樹脂フィルムからなる基材は、無延伸フィルムであっても、延伸フィルムであっても良いし、１種或いは２種以上の共押し出し品、押出しラミ品、ドライラミ品等の積層体であっても良い。
又、基材層の片面あるいは両面を、本発明の熱融着性プロピレン系重合体積層フィルムのラミネート層との接着性を改良するために、例えば、コロナ処理、火炎処理、プラズマ処理、アンダーコート処理、プライマーコート処理、フレーム処理等の表面活性化処理を行っておいてもよい。基材層の厚さは、通常５〜１０００μｍ、好ましくは９〜１００μｍの範囲にある。
Base Material Layer The base material layer according to the present invention is made of a sheet or film made of thermoplastic resin, paper, aluminum foil or the like. As the thermoplastic resin, various known thermoplastic resins such as polyolefin (polyethylene, polypropylene, poly-4-methyl / 1-pentene, polybutene, etc.), polyester (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), polyamide (Nylon-6, nylon-66, polymetaxylene adipamide, etc.), polyvinyl chloride, polyimide, ethylene / vinyl acetate copolymer or saponified product thereof, polyvinyl alcohol, polyacrylonitrile, polycarbonate, polystyrene, ionomer, or these And the like. Of these, thermoplastic resins having good stretchability and transparency, such as polypropylene, polyethylene terephthalate, and polyamide, are preferable. Further, the substrate made of such a thermoplastic resin film may be an unstretched film or a stretched film, and a laminate of one or more coextruded products, extruded laminate products, dry laminate products, etc. It may be the body.
Further, in order to improve the adhesion of one or both sides of the base material layer to the laminate layer of the heat-fusible propylene polymer laminated film of the present invention, for example, corona treatment, flame treatment, plasma treatment, undercoat Surface activation treatment such as treatment, primer coating treatment, and frame treatment may be performed. The thickness of the base material layer is usually 5 to 1000 μm, preferably 9 to 100 μm.
次に本発明を、実施例を通して説明するが、本発明はそれら実施例によって限定されるものではない。 EXAMPLES Next, although this invention is demonstrated through an Example, this invention is not limited by these Examples.
本発明における各種試験法および評価法は次の通りである。
（１）ヒートシール強度（Ｎ／１５ｍｍ）
ヒートシール強度を測定する前に、予めフィルムを３８℃オ−ブン中で１５時間エ−ジングした後放冷した。フィルムの熱融着層面を重ね合せ、所定の温度で、幅５ｍｍのシールバーにより、０．２ＭＰａの圧力で１秒間、フィルムの流れ方向に対して直角方向にヒートシールした後放冷した。これから１５ｍｍ幅の試験片を切り取りクロスヘッド速度５００ｍｍ／分でヒートシール部を剥離し、その強度をヒートシール強度とした。
（２）耐ブロッキング性
耐ブロッキング性を測定する前に、フィルムを３８℃のオ−ブン中で１５時間エ−ジングした後放冷した。フィルムから２０ｍｍ×１００ｍｍ幅の短冊状の試験片を切り取り、熱融着性面を重ね合せたものを５個ずつ作製し、試験片の中央付近で十字方向に直角に市販のプレパラ−トではさむ。試験片とプレパラ−トが重なった５．２ｃｍ２の面積部分に４ｋｇの荷重を掛け、所定の温度条件で２日間エ−ジングした後、放冷する。その後熱融着層面を重ね合せたものをクロスヘッド速度３００ｍｍ／分で剪断剥離を行い、最大強度をブロッキング力とした。ブロッキング力をｎ＝５で評価し、平均値をブロッキング力（Ｎ／５．２ｃｍ２）とした。
（３） 幅方向（ＴＤ）の易引裂性強度（Ｎ）
易引裂性強度を測定する前に、予め多層フィルムを３８℃オ−ブン中で１５時間エ−ジングした後放冷した。フィルムから幅方向（ＴＤ）６５ｍｍ×流れ方向（ＭＤ）５０ｍｍ幅の短冊状の試験片を５枚切り取る。株式会社東洋精機製作所製の軽荷重引裂試験機を用い、フルスケ−ル１．９６Ｎの条件で引裂強度をｎ＝５で評価し、平均値を引裂強度力（Ｎ）とした。１．９６Ｎの条件で切れない場合はフルスケ−ル４．９０Ｎとして測定し、それでも切れない場合は４．９０Ｎ以上とした。
Various test methods and evaluation methods in the present invention are as follows.
(1) Heat seal strength (N / 15mm)
Before measuring the heat seal strength, the film was aged in a 38 ° C. oven for 15 hours and then allowed to cool. The heat-sealable layer surfaces of the film were superposed, and heat-sealed at a predetermined temperature with a seal bar having a width of 5 mm at a pressure of 0.2 MPa for 1 second in a direction perpendicular to the film flow direction, and then allowed to cool. From this, a test piece having a width of 15 mm was cut, and the heat seal part was peeled off at a crosshead speed of 500 mm / min, and the strength was defined as the heat seal strength.
(2) Blocking resistance Before measuring the blocking resistance, the film was aged in a 38 ° C. oven for 15 hours and then allowed to cool. Cut out strips of 20mm x 100mm width from the film, and make 5 pieces of heat-sealable surfaces, and sandwich them with a commercially available slide near the center of the test piece perpendicular to the cross direction. . A load of 4 kg is applied to the 5.2 cm 2 area where the test piece and the preparation overlap, and after aging for 2 days under a predetermined temperature condition, it is allowed to cool. Thereafter, the heat-sealing layer surfaces were overlapped and subjected to shear peeling at a crosshead speed of 300 mm / min, and the maximum strength was defined as a blocking force. The blocking force was evaluated at n = 5, and the average value was defined as the blocking force (N / 5.2 cm 2 ).
(3) Easy tear strength (N) in the width direction (TD)
Before measuring the easy tear strength, the multilayer film was aged in a 38 ° C. oven for 15 hours and then allowed to cool. Five strip-shaped test pieces having a width direction (TD) 65 mm × flow direction (MD) 50 mm width are cut out from the film. Using a light load tear tester manufactured by Toyo Seiki Seisakusho Co., Ltd., the tear strength was evaluated at n = 5 under the condition of full scale 1.96N, and the average value was taken as the tear strength (N). When it could not be cut under the condition of 1.96N, it was measured as full scale 4.90N, and when it was still not cut, it was set to 4.90N or more.
実施例及び比較例で使用した重合体は次の通りである。
（１） プロピレン・エチレンランダム共重合体（１）（ＰＥＲ）
エチレン含有量：３．１重量％、Ｔｓ：９４．０℃、Ｔｐ：１２６．６℃、Ｔｅ：１３１．４℃、Ｔｅ−Ｔｓ：３７．４℃、Ｔｐ−Ｔｓ：３２．６℃、Ｍｗ／Ｍｎ：２．７及びＭＦＲ：７ｇ／１０分。
（２） プロピレン・エチレン・１−ブテンランダム共重合体（ＰＥＢＲ−１）
エチレン含有量：２．２重量％、１−ブテン含有量：２．０重量％、Ｔｓ：９５．４℃、Ｔｐ：１３９．３℃、Ｔｅ：１５０．３℃、Ｔｅ−Ｔｓ：５４．９℃、Ｔｐ−Ｔｓ：４３．９℃、Ｍｗ／Ｍｎ：３．９及びＭＦＲ：７ｇ／１０分。
（３） プロピレン・エチレン・１−ブテンランダム共重合体（ＰＥＢＲ−２）
エチレン含有量：１．７重量％、１−ブテン含有量：２．０重量％、Ｔｓ：１０４．６℃、Ｔｐ：１４５．７℃、Ｔｅ：１５３．１℃、Ｔｅ−Ｔｓ：４８．５℃、Ｔｐ−Ｔｓ：４１．１℃、Ｍｗ／Ｍｎ：３．９及びＭＦＲ：７ｇ／１０分。
（４） エチレン・α−オレフィンランダム共重合体（ＥＢＲ）
エチレン・１−ブテンランダム共重合体、エチレン含有量：８０．２重量％、密度：０．８８６ｇ／ｃｍ３、結晶化度：１０％、融点：６９℃、ＭＦＲ：４．０ｇ／１０分（１９０℃）。
（５） プロピレン単独重合体（ＰＰ）
Ｔｍ：１６０℃、ＭＦＲ：７．０ｇ／１０分（２３０℃）。
The polymers used in Examples and Comparative Examples are as follows.
(1) Propylene / ethylene random copolymer (1) (PER)
Ethylene content: 3.1 wt%, Ts: 94.0 ° C, Tp: 126.6 ° C, Te: 131.4 ° C, Te-Ts: 37.4 ° C, Tp-Ts: 32.6 ° C, Mw / Mn: 2.7 and MFR: 7 g / 10 min.
(2) Propylene / ethylene / 1-butene random copolymer (PEBR-1)
Ethylene content: 2.2 wt%, 1-butene content: 2.0 wt%, Ts: 95.4 ° C, Tp: 139.3 ° C, Te: 150.3 ° C, Te-Ts: 54.9 C, Tp-Ts: 43.9 ° C, Mw / Mn: 3.9 and MFR: 7 g / 10 min.
(3) Propylene / ethylene / 1-butene random copolymer (PEBR-2)
Ethylene content: 1.7 wt%, 1-butene content: 2.0 wt%, Ts: 104.6 ° C, Tp: 145.7 ° C, Te: 153.1 ° C, Te-Ts: 48.5 C, Tp-Ts: 41.1 ° C, Mw / Mn: 3.9 and MFR: 7 g / 10 min.
(4) Ethylene / α-olefin random copolymer (EBR)
Ethylene / 1-butene random copolymer, ethylene content: 80.2% by weight, density: 0.886 g / cm 3 , crystallinity: 10%, melting point: 69 ° C., MFR: 4.0 g / 10 min ( 190 ° C).
(5) Propylene homopolymer (PP)
Tm: 160 ° C., MFR: 7.0 g / 10 min (230 ° C.).
実施例１
熱融着層として、ＰＥＲ：８５重量％及びＥＢＲ：１５重量％とをドライブレンドしたプロピレン系重合体組成物を、中間層として、ＰＥＲ：１００重量％及びラミネート層としてＰＰ：８５重量％及びＥＢＲ：１５重量％とをドライブレンドしたオレフィン系重合体組成物をを夫々用意して別個の押出機に供給し、Ｔダイ法によって熱融着層／中間層／ラミネート層からなる三層共押出積層フィルムを得た。フィルムの総厚は３０μｍで、各層の厚みは熱融着層：中間層：表面層＝２．４μｍ：２３．７μｍ：３．９μｍであった。
得られた三層共押出積層フイルムの物性等を前記記載の方法で評価した。結果を表１に示す。
Example 1
A propylene polymer composition obtained by dry blending PER: 85% by weight and EBR: 15% by weight as a heat-sealing layer, PER: 100% by weight as an intermediate layer, PP: 85% by weight and EBR as a laminate layer : Three-layer coextrusion lamination consisting of heat-fusion layer / intermediate layer / laminate layer by T-die method by preparing olefin polymer compositions dry blended with 15% by weight and feeding them to separate extruders A film was obtained. The total thickness of the film was 30 μm, and the thickness of each layer was heat-fusion layer: intermediate layer: surface layer = 2.4 μm: 23.7 μm: 3.9 μm.
The physical properties of the obtained three-layer coextrusion laminated film were evaluated by the method described above. The results are shown in Table 1.
比較例１
実施例１の熱融着層に用いたプロピレン系重合体組成物に代えて、熱融着層として、ＰＥＢＲ−１：８５重量％及びＥＢＲ：１５重量％とをドライブレンドしたプロピレン系重合体組成物、中間層として、ＰＥＢＲ−２：１００重量％を用いる以外は実施例１と同様に行い、三層共押出積層フィルムを得た。
得られた三層共押出積層フィルムの物性等の評価結果を表１に示す。
Comparative Example 1
Instead of the propylene polymer composition used in the heat-sealing layer of Example 1, a propylene-based polymer composition obtained by dry blending PEBR-1: 85% by weight and EBR: 15% by weight as a heat-sealing layer. A three-layer coextruded laminated film was obtained in the same manner as in Example 1 except that PEBR-2: 100% by weight was used as the intermediate layer.
Table 1 shows evaluation results such as physical properties of the obtained three-layer coextrusion laminated film.
表１から明らかなように、本発明の特定のプロピレン・α―オレフィン共重合体を用いることにより、エチレン・α−オレフィンランダム共重合体との組成物から得られる熱融着層と前記プロピレン・α―オレフィン共重合体を用いて得られた熱融着性プロピレン系重合体積層フィルム（実施例１）は、従来のプロピレン・α―オレフィン共重合体を用いた組成物から得られる積層フィルム（比較例１）に比べて低温ヒ−トシ−ル性に優れているにもかかわらず耐ブロッキング性が優れていることが分る。また、密封性と易引裂性も優れている。 As is apparent from Table 1, by using the specific propylene / α-olefin copolymer of the present invention, the heat-sealed layer obtained from the composition with the ethylene / α-olefin random copolymer and the propylene / α-olefin copolymer are obtained. A heat-fusible propylene-based polymer laminated film (Example 1) obtained using an α-olefin copolymer is a laminated film obtained from a composition using a conventional propylene / α-olefin copolymer ( It can be seen that the blocking resistance is excellent in spite of the excellent low temperature heat sealability compared to Comparative Example 1). It also has excellent sealing properties and easy tearability.
本発明の熱融着性プロピレン系重合体積層フィルムは高速、低圧下における低温ヒートシール性に優れており、かかる特徴を活かして、特にうどんなどの麺類やもやしなどの野菜包装用の縦或いは横ピロ−包装用として好適である。
又、本発明の熱融着性プロピレン系重合体積層フィルムは更に、密封性、耐衝撃性に優れ、且つ耐ブロッキング性、包装材料に好適な剛性、スリップ性、透明性等を有し、ヒートシ−ルされた部分が奇麗な見栄えのする包装体が得られるので、かかる特徴を活かして、飴、せんべい、チョコレ−ト菓子、チョコレ−ト等のお菓子類、珍味等の嗜好品、ハム、ソーセージ、畜肉等の蓄肉加工品、靴下、化粧品等日用雑貨品等の包装材料（規格袋、自働包装用）にも好適である。本発明の熱融着性プロピレン系重合体フィルムは上記包装用材料に限らず、一般包装用フィルムとしては勿論のこと、あらゆる食品、日用品雑貨、医薬用、産業材関連の包装材料としても好適に用い得る。
本発明の熱融着性プロピレン系重合体積層フィルムは、一般的な熱融着性プロピレン系重合体フィルムに比べ、低温ヒ−トシ−ル性により上記性能を十分に発揮できるという特徴を有する。
The heat-fusible propylene-based polymer laminated film of the present invention is excellent in high-temperature and low-pressure heat-sealability under low pressure. Taking advantage of such characteristics, the vertical or horizontal for vegetable packaging such as udon noodles and bean sprouts are particularly useful. Suitable for pillow packaging.
In addition, the heat-fusible propylene-based polymer laminated film of the present invention further has excellent sealing properties, impact resistance, blocking resistance, rigidity suitable for packaging materials, slip properties, transparency, and the like. -Since the packaged portion having a beautiful appearance can be obtained, taking advantage of such characteristics, sweets such as rice cakes, rice crackers, chocolate confectionery, chocolates, etc., luxury items such as delicacies, ham, It is also suitable for packaging materials (standard bags, for automatic packaging) such as sausages, meat storage processed products such as livestock meat, socks, daily goods such as cosmetics. The heat-fusible propylene-based polymer film of the present invention is not limited to the packaging material described above, but is suitable not only as a general packaging film but also as a packaging material for all foods, daily necessities, pharmaceuticals, and industrial materials. Can be used.
The heat-fusible propylene-based polymer laminated film of the present invention has a feature that the above-mentioned performance can be sufficiently exhibited due to low-temperature heat sealability as compared with a general heat-fusible propylene-based polymer film.
Claims (7)
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| US20110261857A1 (en) * | 2008-05-05 | 2011-10-27 | Abbott Gmbh & Co. Kg | Method for evaluating the solubility of a crystalline substance in a polymer |
| JP2012006251A (en) * | 2010-06-24 | 2012-01-12 | Japan Polypropylene Corp | Propylene resin multilayer sheet, and package for heating treatment using the same |
| JP2012006252A (en) * | 2010-06-24 | 2012-01-12 | Japan Polypropylene Corp | Propylene resin multilayer sheet, and package for heating treatment using the same |
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