JP2012177034A - Resin composition for molding extrusion laminate - Google Patents
Resin composition for molding extrusion laminate Download PDFInfo
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- JP2012177034A JP2012177034A JP2011040668A JP2011040668A JP2012177034A JP 2012177034 A JP2012177034 A JP 2012177034A JP 2011040668 A JP2011040668 A JP 2011040668A JP 2011040668 A JP2011040668 A JP 2011040668A JP 2012177034 A JP2012177034 A JP 2012177034A
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- 238000000465 moulding Methods 0.000 title claims abstract description 29
- 238000001125 extrusion Methods 0.000 title claims abstract description 25
- 239000011342 resin composition Substances 0.000 title claims abstract description 25
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 32
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000005977 Ethylene Substances 0.000 claims abstract description 28
- 229920001577 copolymer Polymers 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
- 229920001684 low density polyethylene Polymers 0.000 claims abstract description 21
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 21
- 239000012968 metallocene catalyst Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 238000003475 lamination Methods 0.000 claims description 10
- 239000000155 melt Substances 0.000 claims description 8
- 238000005259 measurement Methods 0.000 claims description 6
- 238000007789 sealing Methods 0.000 abstract description 17
- 239000005022 packaging material Substances 0.000 abstract description 7
- 239000012793 heat-sealing layer Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 12
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 7
- 238000004898 kneading Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 5
- 241000251468 Actinopterygii Species 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 241000283216 Phocidae Species 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- -1 polyethylene terephthalate Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 2
- 241001671982 Pusa caspica Species 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000004278 EU approved seasoning Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N n-hexene Natural products CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明は特定のエチレン・１−ブテン共重合体を主体とする押出ラミネート成形用樹脂組成物に関する。この押出ラミネート成形用樹脂組成物は、低温ヒートシール性とヒートシール強度が良好で易引裂性にも優れるため、各種包装材料等のヒートシール層を形成する材料として好適に用いることができる。 The present invention relates to a resin composition for extrusion laminate molding mainly comprising a specific ethylene / 1-butene copolymer. Since this extrusion laminate molding resin composition has good low-temperature heat sealability and heat seal strength and excellent tearability, it can be suitably used as a material for forming a heat seal layer such as various packaging materials.
従来、各種包装材料等のヒートシール層として、高圧ラジカル法低密度ポリエチレン、チーグラー系触媒を用いた直鎖状低密度ポリエチレン、あるいはこれらの混合物が用いられてきたが、近年は低温ヒートシール性や機械的強度の改善のため、メタロセン系触媒による直鎖状低密度ポリエチレンが用いられるようになっている。 Conventionally, high-pressure radical method low-density polyethylene, linear low-density polyethylene using a Ziegler-based catalyst, or a mixture thereof has been used as a heat-sealing layer for various packaging materials. In order to improve mechanical strength, linear low-density polyethylene using a metallocene catalyst has been used.
例えば、メタロセン系触媒により製造されたエチレン・α−オレフィン共重合体と、高圧ラジカル法で製造された低密度ポリエチレンとを含む押出ラミネート成形用樹脂組成物が特許文献１に、易引裂性フィルム用樹脂組成物が特許文献２に記載されている。
また、メタロセン系触媒により製造されたエチレン・１−ブテン共重合体と、高圧ラジカル法で製造された低密度ポリエチレンとを含む易引裂性フィルムが特許文献３に記載されている。
For example, Patent Document 1 discloses a resin composition for extrusion laminate molding comprising an ethylene / α-olefin copolymer produced by a metallocene catalyst and a low density polyethylene produced by a high pressure radical method. A resin composition is described in Patent Document 2.
Patent Document 3 discloses an easy tear film comprising an ethylene / 1-butene copolymer produced by a metallocene catalyst and a low density polyethylene produced by a high pressure radical method.
これらの材料は積層体のヒートシール層として広く用いられ、洗剤、調味料等の各種液体包装や、菓子、医薬品等のその他一般的な包装に利用されている。 These materials are widely used as a heat seal layer of a laminate, and are used for various liquid packaging such as detergents and seasonings, and other general packaging such as confectionery and pharmaceuticals.
しかしながら、特許文献３に記載の易引裂性フィルムは、易引裂性に優れているが、低温ヒートシール性とヒートシール強度には、改善の余地があった。そこで、本発明は、低温ヒートシール性とヒートシール強度が良好で易引裂性に優れた各種包装材料等のヒートシール層を形成することができる押出ラミネート成形用樹脂組成物を提供することを目的とする。 However, although the easy tear film described in Patent Document 3 is excellent in easy tear, there is room for improvement in the low temperature heat sealability and the heat seal strength. Then, this invention aims at providing the resin composition for extrusion lamination molding which can form heat seal layers, such as various packaging materials excellent in low-temperature heat-sealability and heat-seal strength, and excellent in easy tearability. And
以上の目的を達成するため、本発明者らは、鋭意検討した結果、特定のエチレン・１−ブテン共重合体と低密度ポリエチレンとを用いることで、低温ヒートシール性とヒートシール強度が良好で易引裂性に優れたヒートシール層を形成できる押出ラミネート成形用樹脂組成物を得ることができることを見出し、本発明に至った。すなわち、本発明は、メタロセン触媒の存在下に、エチレン８０〜９９．９モル％及び１−ブテン０．１〜２０モル％を共重合させて得られる下記特性（ａ−１）〜（ａ−３）を有するエチレン・１−ブテン共重合体（Ａ）６５〜９５重量％と、管状反応容器を用いた高圧ラジカル法で製造された下記特性（ｂ−１）〜（ｂ−２）を有する低密度ポリエチレン（Ｂ）５〜３５重量％とを含む押出ラミネート成形用樹脂組成物である。
（ａ−１）密度（ｄ）が０．８９０〜０．９１０ｇ／ｃｍ３である。
（ａ−２）１９０℃における２．１６ｋｇ荷重でのメルトフローレート（ＭＦＲ）が６〜３０ｇ／１０分である。
（ａ−３）示差走査熱量計（ＤＳＣ）測定による融点ピークを１以上有し、そのうち最も高い融点（Ｔｍ１）と密度（ｄ）との関係が、下記の式（１）を満たす。
In order to achieve the above object, the present inventors have intensively studied, and as a result, by using a specific ethylene / 1-butene copolymer and low density polyethylene, the low temperature heat sealability and heat seal strength are good. The inventors have found that a resin composition for extrusion laminate molding capable of forming a heat seal layer excellent in easy tearability can be obtained, and the present invention has been achieved. That is, the present invention provides the following characteristics (a-1) to (a-) obtained by copolymerizing 80 to 99.9 mol% of ethylene and 0.1 to 20 mol% of 1-butene in the presence of a metallocene catalyst. 3) having an ethylene / 1-butene copolymer (A) of 65 to 95% by weight and the following characteristics (b-1) to (b-2) produced by a high-pressure radical method using a tubular reaction vessel It is a resin composition for extrusion lamination molding containing 5 to 35% by weight of low density polyethylene (B).
(A-1) The density (d) is 0.890 to 0.910 g / cm 3 .
(A-2) The melt flow rate (MFR) at 2.16 kg load at 190 ° C. is 6 to 30 g / 10 minutes.
(A-3) It has one or more melting point peaks by differential scanning calorimeter (DSC) measurement, and the relationship between the highest melting point (T m1 ) and density (d) satisfies the following formula (1).
（ｂ−２）密度が０．９１６〜０．９１９ｇ／ｃｍ３である。
(B-2) The density is 0.916 to 0.919 g / cm 3 .
また、本発明は、少なくとも前記の押出ラミネート成形用樹脂組成物からなる層と基材層とを含む積層体である。 Moreover, this invention is a laminated body containing the layer which consists of the said resin composition for extrusion lamination molding at least, and a base material layer.
本発明の押出ラミネート成形用樹脂組成物は、低温ヒートシール性とヒートシール強度が良好で易引裂性にも優れるため、食品、医薬品、一般雑貨、衣料品、工業材料等の各種包装材として好適に用いることができる。 The resin composition for extrusion laminate molding of the present invention is suitable as various packaging materials for foods, pharmaceuticals, general goods, clothing, industrial materials and the like because it has good low-temperature heat sealability and heat seal strength and excellent tearability. Can be used.
本発明で用いるエチレン・１−ブテン共重合体（Ａ）は、メタロセン触媒を用いてエチレン８０〜９９．９モル％と、１−ブテン０．１〜２０モル％とを共重合させて得られる。好ましくはエチレン８７〜９９．５モル％と、１−ブテン０．５〜１３モル％、より好ましくはエチレン９０〜９９モル％と、１−ブテン１〜１０モル％とを共重合させて得られる共重合体である。 The ethylene / 1-butene copolymer (A) used in the present invention is obtained by copolymerizing 80 to 99.9 mol% of ethylene and 0.1 to 20 mol% of 1-butene using a metallocene catalyst. . Preferably it is obtained by copolymerizing ethylene 87-99.5 mol%, 1-butene 0.5-13 mol%, more preferably ethylene 90-99 mol%, 1-butene 1-10 mol%. It is a copolymer.
重合に用いるメタロセン触媒としては、周期律表第４族の遷移金属からなるメタロセン化合物を有機アルミニウム化合物及び／又はイオン性化合物により活性化させたもの等、公知の触媒を用いることができる。エチレン・１−ブテン共重合体は、例えば気相重合反応、液相重合反応などの方法により製造することが出来る。好ましくはメタロセン触媒含有固体成分を気相流動床反応器に供給し、気相状態でエチレンと１−ブテンとを共重合させる連続式気相流動床重合法で製造するのが好ましい。 As the metallocene catalyst used for the polymerization, known catalysts such as those obtained by activating a metallocene compound composed of a transition metal of Group 4 of the periodic table with an organoaluminum compound and / or an ionic compound can be used. The ethylene / 1-butene copolymer can be produced by a method such as a gas phase polymerization reaction or a liquid phase polymerization reaction. The metallocene catalyst-containing solid component is preferably supplied to a gas phase fluidized bed reactor, and is preferably produced by a continuous gas phase fluidized bed polymerization method in which ethylene and 1-butene are copolymerized in the gas phase.
上記エチレン・１−ブテン共重合体（Ａ）の密度は０．８９０〜０．９１０ｇ／ｃｍ３が好ましく、０．８９５〜０．９１０ｇ／ｃｍ３がより好ましく、０．９００〜０．９１０ｇ／ｃｍ３が特に好ましい。密度がこの範囲より高いとシール開始温度が高くなり好ましくなく、低いと耐熱性、耐ブロッキング性、押出ラミネート成形時のロールリリース性が悪化する。 The density of the ethylene-1-butene copolymer (A) is preferably from 0.890~0.910g / cm 3, more preferably 0.895~0.910g / cm 3, 0.900~0.910g / cm 3 is particularly preferred. When the density is higher than this range, the sealing start temperature becomes high, which is not preferable. When the density is low, heat resistance, blocking resistance, and roll release property at the time of extrusion lamination molding deteriorate.
１９０℃における２．１６ｋｇ荷重でのメルトフローレート（ＭＦＲ）は５〜５０ｇ／１０分が好ましく、６〜４０ｇ／１０分がより好ましく、１０〜３０ｇ／１０分が特に好ましい。ＭＦＲがこの範囲より高いとネックインが大きくなり、ヒートシール強度が低下する。また、低いと成形時の押出機負荷が大きくなる、引裂強度が高くなって易引裂性に劣るなどの問題が生じる。 The melt flow rate (MFR) at a load of 2.16 kg at 190 ° C. is preferably 5 to 50 g / 10 minutes, more preferably 6 to 40 g / 10 minutes, and particularly preferably 10 to 30 g / 10 minutes. If the MFR is higher than this range, the neck-in increases and the heat seal strength decreases. On the other hand, when it is low, problems such as an increase in the load on the extruder at the time of molding and an increase in tear strength and inferior easy tearability occur.
分子量分布（Ｍｗ／Ｍｎ）は、３〜７の範囲であることが好ましく、３．２〜６．５の範囲であることがさらに好ましく、３．５〜６の範囲であることが特に好ましい。分子量分布（Ｍｗ／Ｍｎ）が上記範囲より小さい場合、成形加工時に押出機などの成形機の負荷が大きくなるために好ましくなく、大きい場合は、製膜したフィルムの耐ブロッキング性、ヒートシール性が悪化する。 The molecular weight distribution (Mw / Mn) is preferably in the range of 3 to 7, more preferably in the range of 3.2 to 6.5, and particularly preferably in the range of 3.5 to 6. When the molecular weight distribution (Mw / Mn) is smaller than the above range, it is not preferable because the load on a molding machine such as an extruder becomes large at the time of molding, and when it is large, the film formed has blocking resistance and heat sealability. Getting worse.
上記エチレン・１−ブテン共重合体（Ａ）は、示差走査熱量計（ＤＳＣ）測定による融点ピークを１つ以上有していることが好ましく、密度が０．８９０〜０．９１０ｇ／ｃｍ３の範囲において融点ピークを２つ以上有していることが特に好ましい。さらに、これらのうち最も高い融点Ｔｍ１（℃）と密度ｄ（ｇ／ｃｍ３）は、上記密度範囲において下記の式（１）を満たしていることが好ましい。 The ethylene / 1-butene copolymer (A) preferably has one or more melting point peaks as determined by differential scanning calorimetry (DSC), and has a density of 0.890 to 0.910 g / cm 3 . It is particularly preferable to have two or more melting point peaks in the range. Furthermore, among these, it is preferable that the highest melting point T m1 (° C.) and density d (g / cm 3 ) satisfy the following formula (1) in the above density range.
具体的には、密度が０．９００ｇ／ｃｍ３未満の重合体では融点が１１３℃以下、０．９００〜０．９１０ｇ／ｃｍ３の重合体では１１４．５℃以下であるのが好ましい。 Specifically, the density is a melting point of 113 ° C. or less in the polymer of less than 0.900 g / cm 3, preferably not more than 114.5 ° C. at polymer 0.900~0.910g / cm 3.
本発明で用いる低密度ポリエチレン（Ｂ）は、管状反応容器を用いた高圧ラジカル法で製造され、密度は０．９１６〜０．９１９ｇ／ｃｍ３であるのが好ましい。また、１９０℃における２．１６ｋｇ荷重でのメルトフローレート（ＭＦＲ）は１．５〜２．５ｇ／１０分であるのが好ましい。ＭＦＲの値がこの範囲より大きいとネックインが大きくなり、小さいと上記エチレン・１−ブテン共重合体と均一に混合するのが難しくなる。また、槽型反応容器を用いた高圧ラジカル法で製造された低密度ポリエチレンを用いると、押出ラミネート成形時の溶融延展性が劣るため、溶融延展膜の端部が不安定になり所望の成形幅にて成形できないなどの問題が起きる。 The low density polyethylene (B) used in the present invention is produced by a high-pressure radical method using a tubular reaction vessel, and the density is preferably 0.916 to 0.919 g / cm 3 . The melt flow rate (MFR) at a load of 2.16 kg at 190 ° C. is preferably 1.5 to 2.5 g / 10 minutes. When the MFR value is larger than this range, the neck-in becomes large, and when the MFR value is small, it becomes difficult to uniformly mix with the ethylene / 1-butene copolymer. Also, if low density polyethylene produced by a high-pressure radical method using a tank-type reaction vessel is used, the melt spreadability at the time of extrusion lamination molding is inferior, so the end of the melt spread film becomes unstable and the desired molding width Problems such as inability to mold.
本発明の押出ラミネート成形用樹脂組成物は、上記エチレン・１−ブテン共重合体（Ａ）６５〜９５重量％と、上記低密度ポリエチレン（Ｂ）５〜３５重量％とを含む組成物である。低密度ポリエチレン（Ｂ）の量がこの範囲より多くなるとヒートシール強度が低下し、また、臭気が問題となる場合がある。 The resin composition for extrusion laminate molding of the present invention is a composition comprising 65 to 95% by weight of the ethylene / 1-butene copolymer (A) and 5 to 35% by weight of the low density polyethylene (B). . When the amount of the low density polyethylene (B) is more than this range, the heat seal strength is lowered and the odor may be a problem.
樹脂組成物の各成分の混合方法、混合装置、混合設備については特に制限はなく、公知の単軸押出機（混練機）、二軸押出機（混練機）、二軸押出機と単軸押出機（混練機）を直列に接続したタンデム型混練装置、カレンダー、バンバリーミキサー、混練ロール、ブラベンダー、プラストグラフ、ニーダー等の装置などを用いることができる。この際、必要に応じて各種添加剤を使用することもできる。 There are no particular restrictions on the mixing method, mixing apparatus, and mixing equipment for each component of the resin composition. Known single-screw extruder (kneading machine), twin-screw extruder (kneading machine), twin-screw extruder and single-screw extrusion A tandem kneading apparatus, a calendar, a Banbury mixer, a kneading roll, a brabender, a plastograph, a kneader, or the like, in which machines (kneading machines) are connected in series, can be used. At this time, various additives may be used as necessary.
このようにして得られる本発明の樹脂組成物を用いて押出ラミネート成形する場合に基材層として用いられる基材としては、上質紙、クラフト紙等の紙、アルミニウム箔等の金属箔、二軸延伸ナイロン等のナイロン系基材、二軸延伸ＰＥＴ（ポリエチレンテレフタレート）フィルム等のポリエステル系基材、二軸延伸ポリプロピレン（ＯＰＰ）等のポリオレフィン系基材等が挙げられる。 In the case of extrusion lamination molding using the resin composition of the present invention thus obtained, the base material used as a base material layer is paper such as fine paper, kraft paper, metal foil such as aluminum foil, biaxial Examples thereof include nylon base materials such as stretched nylon, polyester base materials such as biaxially stretched PET (polyethylene terephthalate) film, and polyolefin base materials such as biaxially stretched polypropylene (OPP).
これらの基材上に、本発明の樹脂組成物を公知の方法で押出ラミネート成形することにより、低温ヒートシール性とヒートシール強度が良好で易引裂性に優れた積層体が得られる。 By extrusion-molding the resin composition of the present invention on these substrates by a known method, a laminate having good low temperature heat sealability and heat seal strength and excellent tearability can be obtained.
本発明の樹脂組成物を厚さ３０μｍのフィルムにした場合の引取方向（ＭＤ）に対して垂直方向（横方向）（ＴＤ）の引裂強度は、１０〜１００ｇ／１５ｍｍの範囲であるのが好ましく、２０〜９０ｇ／１５ｍｍの範囲であるのがさらに好ましく、３０〜８０ｇ／１５ｍｍの範囲であるのが特に好ましい。引裂強度が高すぎると包装に用いたときの開封性が悪くなり、低すぎると破袋しやすくなる。 When the resin composition of the present invention is formed into a film having a thickness of 30 μm, the tear strength in the direction perpendicular to the take-off direction (MD) (transverse direction) (TD) is preferably in the range of 10 to 100 g / 15 mm. The range of 20 to 90 g / 15 mm is more preferable, and the range of 30 to 80 g / 15 mm is particularly preferable. If the tear strength is too high, the unsealing property when used for packaging is deteriorated, and if it is too low, the bag is easily broken.
樹脂組成物自体の引裂強度が高い場合であっても、積層体の層間接着強度が、５００ｇ／１５ｍｍ以上の場合には、積層体全体の引裂性は基材そのものの引裂性を反映し、引裂性の良い基材を利用すれば引裂性は良好となる。しかし、層間接着強度が３００ｇ／１５ｍｍ以下の場合、引裂時に樹脂組成物層の剥離が起こり、樹脂組成物そのものの引裂強度が積層体全体の引裂性に大きな影響を与えることとなり、引裂性の良い基材を利用しても、易引裂性を向上させることができない。なお、積層体を包装材料として用いる場合、全ての包装材料に当てはまるものではないが、３００ｇ／１５ｍｍ以下の層間接着強度であっても、包装という内容物を保護する機能は損なわれない場合がある。 Even when the tear strength of the resin composition itself is high, if the interlayer adhesion strength of the laminate is 500 g / 15 mm or more, the tearability of the entire laminate reflects the tearability of the substrate itself, If a base material with good properties is used, the tearability will be good. However, when the interlayer adhesive strength is 300 g / 15 mm or less, the resin composition layer is peeled off at the time of tearing, and the tear strength of the resin composition itself has a great influence on the tearability of the entire laminate. Even if a substrate is used, the easy tearability cannot be improved. In addition, when using a laminated body as a packaging material, it does not apply to all packaging materials, but even if it is an interlayer adhesive strength of 300 g / 15 mm or less, the function which protects the content of packaging may not be impaired. .
一般的に、押出ラミネート成形による積層体の製造において、ポリエチレン組成物と異素材である基材との接着強度を大きくさせるために、基材への特殊な前処理（表面処理、接着付与剤コーティングなど）や溶融した組成物へのオゾン処理、組成物へ配合する添加剤の削減、接着が良好な基材選定、生産速度の低減、など、多大な手間と設備費用がかかる手法を用いている。しかし、本発明の樹脂組成物は、３００ｇ／１５ｍｍ以下の層間接着強度の場合であっても、積層体の易引裂性は良好であるため、上記のような接着強度を大きくする手法を用いる必要がない。 In general, in the production of laminates by extrusion laminate molding, special pretreatment (surface treatment, adhesion-imparting agent coating) is applied to the base material in order to increase the adhesive strength between the polyethylene composition and the base material that is a different material. Etc.) and ozone treatment of the molten composition, reduction of additives to be added to the composition, selection of a substrate with good adhesion, reduction of production speed, etc. . However, even if the resin composition of the present invention has an interlayer adhesive strength of 300 g / 15 mm or less, the laminate is easy to tear, and thus it is necessary to use a technique for increasing the adhesive strength as described above. There is no.
以下、実施例に基づいて本発明を具体的に説明する。実施例における各測定方法は以下の通りである。 Hereinafter, the present invention will be specifically described based on examples. Each measuring method in an Example is as follows.
［メルトフローレート（ＭＦＲ）］
ＪＩＳ Ｋ７２１０（１９０℃、２．１６ｋｇ荷重）に準じて測定した。
［密度］
ＪＩＳ Ｋ７１１２に準じて測定した。
［融点］
ＪＩＳ Ｋ７１２１に準じ、アニール速度５℃／分（０℃まで）、融点測定時１０℃／分の昇温速度で測定した。
［コモノマー濃度］
公知の方法により、１Ｈ−ＮＭＲスペクトルより算出した。
［分子量分布］
Ｗａｔｅｒｓ社製 ＧＰＣ／Ｖ２０００を用いて以下の条件で測定し、標準ポリスチレン換算の値を算出した。
カラム：ＳＨＯＤＥＸ ＡＴ−８０６Ｍ×２本
移動相：劣化防止剤入りＯＤＣＢ
温度：１４５℃
［押出機負荷］
押出ラミネート成形時のスクリューモーターの電流値を目視で読み取った。
［ネックイン］
押出ラミネート成形時のＴダイスから押し出された樹脂組成物が積層された幅を用い、（Ｔダイス幅）−（積層樹脂幅）をネックインとした。
［フィッシュアイ（ＦＥ）］
組成物を６５ｍｍφフルフライトスクリュー、圧縮比２．７、Ｌ／Ｄ２８の単軸押出機（池貝鉄鋼製）にて２００℃、４０ｋｇ／時間の条件で溶融混練してペレット状物を調製した。これを３０ｍｍφ押出機、コートハンガータイプＴダイス（幅３００ｍｍ）、ダイ直下樹脂温度２００℃、成形速度１２ｍ／分で、厚み３０μｍの単層フィルムとし、フィルム１ｍ２あたりに含まれる５００μｍ以上の長さを有するゲル状の突起物（フィッシュアイ）をＣＣＤカメラによる欠点検出器にて測定した。
［エルメン引裂］
ＦＥ測定で作成した３０μｍのフィルムを用い、ＪＩＳ Ｋ７１２８に準じて、ＴＤ方向のエルメンドルフ引裂強度を測定した。
［接着強度］
積層体をＭＤ方向に１５ｍｍ幅の短冊状に切り出し、長手方向の一方より基材と樹脂組成物を剥離させ、各々の層をつまみ、速度３００ｍｍ／ｍｉｍにて、Ｔ字状の形状を保ちながら、剥離していない部分を剥離させる際の抵抗力を接着強度とする。
[Melt flow rate (MFR)]
The measurement was performed according to JIS K7210 (190 ° C., 2.16 kg load).
[density]
The measurement was performed according to JIS K7112.
[Melting point]
According to JIS K7121, the annealing rate was 5 ° C./min (up to 0 ° C.), and the melting point was measured at a heating rate of 10 ° C./min.
[Comonomer concentration]
It computed from the < 1 > H-NMR spectrum by the well-known method.
[Molecular weight distribution]
Measurement was performed under the following conditions using GPC / V2000 manufactured by Waters, and a value in terms of standard polystyrene was calculated.
Column: SHODEX AT-806M x 2 Mobile phase: ODCB with anti-degradation agent
Temperature: 145 ° C
[Extruder load]
The current value of the screw motor at the time of extrusion lamination molding was read visually.
[Neck-in]
The width of the laminated resin composition extruded from the T-dies during extrusion lamination molding was used, and (T-die width) − (laminated resin width) was defined as a neck-in.
[Fisheye (FE)]
The composition was melt-kneaded with a 65 mmφ full flight screw, compression ratio 2.7, L / D28 single screw extruder (Ikegai Steel) at 200 ° C. and 40 kg / hour to prepare pellets. This is a 30 mmφ extruder, a coat hanger type T die (width 300 mm), a resin temperature immediately below the die of 200 ° C., a molding speed of 12 m / min, and a single layer film having a thickness of 30 μm, and a length of 500 μm or more contained per 1 m 2 of film. A gel-like protrusion (fish eye) having a surface area was measured with a defect detector using a CCD camera.
[Elmen tear]
Elmendorf tear strength in the TD direction was measured according to JIS K7128 using a 30 μm film prepared by FE measurement.
[Adhesive strength]
The laminate is cut into a strip of 15 mm width in the MD direction, the base material and the resin composition are peeled off from one side in the longitudinal direction, and each layer is pinched while maintaining a T-shape at a speed of 300 mm / mim The resistance when peeling off the part that has not been peeled is defined as the adhesive strength.
実施例で用いた重合体は以下の通りである。
［エチレン・１−ブテン共重合体（Ａ）］
メタロセン触媒を用いて気相法プロセスで重合して得られたパウダー状の重合体に、過熱劣化防止剤としてチバスペシャリティケミカルズ製イルガノックス１０７６およびイルガフォス１６８を各１０００ｐｐｍ、中和剤としてステアリン酸カルシウムを５００ｐｐｍ配合し、４５ｍｍ三条二軸押出機（池貝鉄鋼製）を用いて２００℃設定で溶融混練して得たペレットである。
［低密度ポリエチレン（Ｂ）］
管状反応容器を用いた高圧ラジカル法で製造された低密度ポリエチレンで、形状はペレット状である。
The polymers used in the examples are as follows.
[Ethylene / 1-butene copolymer (A)]
A powdery polymer obtained by polymerizing by a gas phase process using a metallocene catalyst was mixed with 1000 ppm of Irganox 1076 and Irgaphos 168 manufactured by Ciba Specialty Chemicals as anti-overheating degradation agents, and 500 ppm of calcium stearate as a neutralizing agent. It is a pellet obtained by blending and melting and kneading at a setting of 200 ° C. using a 45 mm three-spindle twin screw extruder (manufactured by Ikekai Steel).
[Low density polyethylene (B)]
It is a low-density polyethylene manufactured by a high-pressure radical method using a tubular reaction vessel and has a pellet shape.
（実施例１）
表１に示した特性を有するエチレン・１−ブテン共重合体（Ａ）と低密度ポリエチレン（Ｂ）とを含む組成物と、表面処理していないアルミ基材（７μｍ）とを用いて、インナーデュッケルタイプＴダイス（幅５００ｍｍ）を備えた押出ラミネーターにて、ダイ直下樹脂温度３１０℃、エアーギャップ１２０ｍｍ、成形速度１００ｍ／ｍｉｎの条件で押出ラミネート成形して積層体を得た。得られた積層体におけるアルミ基材と組成物の接着強度は、１００ｇ／１５ｍｍであった。
この積層体の組成物面同士を重ね合わせ、幅５ｍｍ（長さ３００ｍｍ）のヒートシールバーを用いて、圧力２ｋｇ／ｃｍ２、時間１秒の条件で、ＭＤ方向と直角にシールしたサンプルを、温度（バー片側のみ設定）を６０℃から１３０℃まで５℃毎のシール温度で作成した。このサンプルのシール部を１５ｍｍ幅の短冊に切り取って、５００ｍｍ／分の速度でシール面同士を剥離させ、強度が５０ｇを超えた温度をシール開始温度とした。また、温度１３０℃でシールしたサンプルの１５ｍｍ幅の短冊を、５００ｍｍ／分の速度でシール面を剥離させたときの最大応力を測定し、１３０℃シール強度を測定した。
カット性は、この積層体を用いて水１００ｃｃをなるべく空気が入らないように充填した袋サイズ１００×１５０ｍｍの４方シール袋（ＭＤ方向が長い袋）の長手方向の上部一箇所にノッチをつくったものを用い、このノッチを起点として、ＴＤ方向に水をこぼさないように袋を引き裂いた際の開封のしやすさで評価した。成人男女５名にて各５袋評価し、○：最後まで開封しやすい、△：最後まで開封できるが抵抗力が強い、×：抵抗が強く最後まで開封できない、の各指標で表した。
臭気は、積層体１ｍ２を２ｃｍ四方にカットし、５００ｃｃのガラス製広口ビンにいれて５０℃１時間加熱した後に感じる強さを成人男女５名にて評価し、５段階（５が最も強い臭気）で表した。
これらの結果を表１にまとめた。
Example 1
Using a composition containing an ethylene / 1-butene copolymer (A) and low density polyethylene (B) having the characteristics shown in Table 1, and an aluminum substrate (7 μm) that has not been surface-treated, Using an extrusion laminator equipped with a Duckel type T die (width 500 mm), a laminate was obtained by extrusion lamination molding under conditions of a resin temperature immediately below the die of 310 ° C., an air gap of 120 mm, and a molding speed of 100 m / min. The adhesive strength between the aluminum substrate and the composition in the obtained laminate was 100 g / 15 mm.
A sample that is laminated at right angles to the MD direction under the conditions of a pressure of 2 kg / cm 2 and a time of 1 second using a heat seal bar having a width of 5 mm (length: 300 mm), with the composition surfaces of this laminate laminated. The temperature (set only on one side of the bar) was created from 60 ° C. to 130 ° C. at a seal temperature of every 5 ° C. The seal part of this sample was cut into a strip having a width of 15 mm, the seal surfaces were peeled off at a speed of 500 mm / min, and the temperature at which the strength exceeded 50 g was defined as the seal start temperature. Moreover, the maximum stress when the strip surface of the 15 mm width strip of the sample sealed at a temperature of 130 ° C. was peeled off at a speed of 500 mm / min was measured, and the 130 ° C. seal strength was measured.
Cutability is made by making a notch in the upper part of the longitudinal direction of a 100x150mm bag size (bag with long MD direction) filled with 100cc of water so that air does not enter as much as possible. This was used as a starting point, and the ease of opening when the bag was torn so as not to spill water in the TD direction was evaluated. Five adult males and females evaluated each of the five bags, and each was represented by the following indicators: ○: easy to open to the end, Δ: open to the end but strong resistance, ×: strong resistance to open to the end.
Odor is evaluated by 5 adults (5 adults), with 5 adults (5 being the strongest), evaluating the strength felt after cutting the laminate 1m 2 into 2cm squares and placing it in a 500cc glass wide-mouth bottle and heating at 50 ° C for 1 hour. Odor).
These results are summarized in Table 1.
（実施例２〜５）
表１に示した特性を有するエチレン・１−ブテン共重合体（Ａ）と、低密度ポリエチレン（Ｂ）とを含む組成物を用いた以外は実施例１と同様に行った。得られた積層体におけるアルミ基材と組成物の接着強度は、８５〜１５０ｇ／１５ｍｍであった。結果を表１にまとめた。
(Examples 2 to 5)
The same procedure as in Example 1 was performed except that a composition containing an ethylene / 1-butene copolymer (A) having the characteristics shown in Table 1 and a low density polyethylene (B) was used. The adhesive strength between the aluminum substrate and the composition in the obtained laminate was 85 to 150 g / 15 mm. The results are summarized in Table 1.
（比較例１、２）
表１に示した密度が高いエチレン・１−ブテン共重合体を用いた以外は、実施例１と同様に行った。結果を表２にまとめた。
得られた積層体はシール開始温度が高く、低温シール性が劣っていた。
(Comparative Examples 1 and 2)
The same operation as in Example 1 was performed except that the ethylene / 1-butene copolymer having a high density shown in Table 1 was used. The results are summarized in Table 2.
The obtained laminate had a high sealing start temperature and was inferior in low-temperature sealing properties.
（比較例３）
表１に示した密度が高く、ＭＦＲが低いエチレン・１−ブテン共重合体を用いた以外は、実施例１と同様に行った。結果を表２にまとめた。
成形時の押出負荷が大きく、また、得られた積層体のシール開始温度が高く、低温シール性も劣っていた。さらに、引裂強度が大きく、カット性に問題があった。
(Comparative Example 3)
The same procedure as in Example 1 was performed except that an ethylene / 1-butene copolymer having a high density and a low MFR shown in Table 1 was used. The results are summarized in Table 2.
The extrusion load at the time of molding was large, and the obtained laminate had a high sealing start temperature, and the low-temperature sealing property was inferior. In addition, the tear strength was high, and there was a problem with cutability.
（比較例４、５）
エチレン・１−ブテン共重合体（Ａ）の代わりに、エチレン・１−ヘキセン共重合体を用いた以外は、実施例１と同様に行った。結果を表２にまとめた。
シール開始温度、１３０℃シール強度とも良好であったが、引裂強度が大きいためカット性が悪く、手で開封することが困難であった。
(Comparative Examples 4 and 5)
The same procedure as in Example 1 was conducted except that an ethylene / 1-hexene copolymer was used instead of the ethylene / 1-butene copolymer (A). The results are summarized in Table 2.
Both the sealing start temperature and the 130 ° C. sealing strength were good, but the tear strength was high, so the cutability was poor and it was difficult to open by hand.
（比較例６）
低密度ポリエチレン（Ｂ）の含有量が多い以外は、実施例１と同様に行った。結果を表２にまとめた。
１３０℃シール強度が低く、臭気がやや強かった。
(Comparative Example 6)
It carried out similarly to Example 1 except having much content of low density polyethylene (B). The results are summarized in Table 2.
The 130 ° C. seal strength was low and the odor was slightly strong.
（比較例７）
低密度ポリエチレン（Ｂ）を用いない以外は、実施例１と同様に行った。結果を表２にまとめた。
ネックインが大きく、成形性に問題があった。
(Comparative Example 7)
It carried out similarly to Example 1 except not using a low density polyethylene (B). The results are summarized in Table 2.
The neck-in was large and there was a problem with moldability.
（比較例８、９）
エチレン・１−ブテン共重合体（Ａ）の代わりに、チーグラー・ナッタ触媒を用いて得られたエチレン・１−ブテン共重合体を用いた以外は、実施例１と同様に行った。結果を表２にまとめた。
シール開始温度が高く、１３０℃シール強度も低いため、シール性に問題があった。また、臭気もやや強かった。さらに、フィッシュアイが多く見られた。
(Comparative Examples 8 and 9)
It carried out similarly to Example 1 except having used the ethylene / 1-butene copolymer obtained using the Ziegler-Natta catalyst instead of the ethylene / 1-butene copolymer (A). The results are summarized in Table 2.
Since the sealing start temperature was high and the 130 ° C. sealing strength was low, there was a problem in sealing performance. Also, the odor was somewhat strong. In addition, many fish eyes were seen.
（比較例１０）
表１に示した低密度ポリエチレンのみを用いた以外は、実施例１と同様に行った。結果を表２にまとめた。
シール開始温度が高く、１３０℃シール強度も低いため、シール性に問題があった。また、臭気もやや強かった。
(Comparative Example 10)
The same operation as in Example 1 was carried out except that only the low density polyethylene shown in Table 1 was used. The results are summarized in Table 2.
Since the sealing start temperature was high and the 130 ° C. sealing strength was low, there was a problem in sealing performance. Also, the odor was somewhat strong.
（比較例１１、１２）
表１に示した高圧ラジカル法で製造された市販のエチレン・酢酸ビニル共重合体のみを用い、成形時のダイ直下温度を２５０℃とした以外は、実施例１と同様に行った。結果を表２にまとめた。
シール開始温度は良好であったが、１３０℃シール強度も低くシール性に問題があった。また、臭気が強く、フィッシュアイも多く見られた。
(Comparative Examples 11 and 12)
The same procedure as in Example 1 was carried out except that only a commercially available ethylene / vinyl acetate copolymer produced by the high-pressure radical method shown in Table 1 was used, and the temperature immediately below the die during molding was 250 ° C. The results are summarized in Table 2.
Although the sealing start temperature was good, the sealing strength at 130 ° C. was low and there was a problem in sealing performance. In addition, it had a strong odor and many fish eyes.
（比較例１３、１４）
低密度ポリエチレン（Ｂ）のＭＦＲが低いもの、高いものを用いた以外は、実施例１と同様に行った。結果を表２にまとめた。
ＭＦＲが低い低密度ポリエチレン（Ｂ）を用いた場合は、フィッシュアイが多くみられた。また、ＭＦＲが高い低密度ポリエチレン（Ｂ）を用いた場合は、ネックインが大きく、成形性に問題があった。
(Comparative Examples 13 and 14)
The same operation as in Example 1 was performed except that low density polyethylene (B) having a low MFR and a high MFR were used. The results are summarized in Table 2.
When low density polyethylene (B) having a low MFR was used, many fish eyes were observed. Moreover, when the low density polyethylene (B) having a high MFR was used, the neck-in was large and there was a problem in moldability.
Claims (2)
（ａ−１）密度（ｄ）が０．８９０〜０．９１０ｇ／ｃｍ３である。
（ａ−２）１９０℃における２．１６ｋｇ荷重でのメルトフローレート（ＭＦＲ）が６〜３０ｇ／１０分である。
（ａ−３）示差走査熱量計（ＤＳＣ）測定による融点ピークを１以上有し、そのうち最も高い融点（Ｔｍ１）と密度（ｄ）との関係が、下記の式（１）を満たす。
（ｂ−２）密度が０．９１６〜０．９１９ｇ／ｃｍ３である。 Ethylene having the following characteristics (a-1) to (a-3) obtained by copolymerizing 80 to 99.9 mol% of ethylene and 0.1 to 20 mol% of 1-butene in the presence of a metallocene catalyst 1-butene copolymer (A) 60 to 95% by weight and low density polyethylene (B) having the following characteristics (b-1) to (b-2) produced by a high-pressure radical method using a tubular reaction vessel A resin composition for extrusion lamination molding comprising 5 to 40% by weight.
(A-1) The density (d) is 0.890 to 0.910 g / cm 3 .
(A-2) The melt flow rate (MFR) at 2.16 kg load at 190 ° C. is 6 to 30 g / 10 minutes.
(A-3) It has one or more melting point peaks by differential scanning calorimeter (DSC) measurement, and the relationship between the highest melting point (T m1 ) and density (d) satisfies the following formula (1).
(B-2) The density is 0.916 to 0.919 g / cm 3 .
A laminate comprising at least a layer made of the resin composition for extrusion laminate molding according to claim 1 and a base material layer.
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| CN104558788A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Polyethylene composite with excellent puncture resistance and weather resistance |
| JP6420891B1 (en) * | 2017-12-08 | 2018-11-07 | 宇部丸善ポリエチレン株式会社 | Resin composition for extrusion lamination and laminate film |
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