JP4498913B2 - Biaxially stretched ethylene polymer multilayer film - Google Patents
Biaxially stretched ethylene polymer multilayer film Download PDFInfo
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本発明は、縦横何れの方向にも容易に引裂け、且つ透明性、収縮性に優れ、しかもヒートシール性及び耐屈曲性にも優れる二軸延伸エチレン重合体多層フィルムに関する。 The present invention relates to a biaxially stretched ethylene polymer multilayer film that can be easily torn in both longitudinal and lateral directions, is excellent in transparency and shrinkage, and is also excellent in heat sealability and bending resistance.
エチレン・α−オレフィンランダム共重合体、所謂線状低密度ポリエチレン（ＬＬＤＰＥ）は、高圧法低密度ポリエチレンに比べ、透明性、耐ストレスクラッキング性、低温ヒートシール性、ヒートシール強度、耐衝撃性等に優れておりその特徴を活かして食品包装用のシーラントとして広く用いられている。中でも、シングルサイト触媒で重合されたエチレン・α−オレフィンランダム共重合体は、更に透明性、低温ヒートシール性、夾雑物シール性、ホットタック性にも優れている。 Ethylene / α-olefin random copolymer, so-called linear low density polyethylene (LLDPE) is more transparent, stress cracking resistance, low temperature heat sealability, heat seal strength, impact resistance, etc. than high pressure method low density polyethylene It is widely used as a sealant for food packaging taking advantage of its characteristics. Among them, the ethylene / α-olefin random copolymer polymerized with a single site catalyst is further excellent in transparency, low-temperature heat sealability, contaminant sealability, and hot tack property.
エチレン・α−オレフィンランダム共重合体フィルムの透明性、機械的強度等を改良する方法としてエチレン・α−オレフィンランダム共重合体を特定の条件下で二軸延伸する方法（特許文献１）、エチレン・α−オレフィンランダム共重合体及びエチレン・α−オレフィンランダム共重合体に高密度ポリエチレンあるいは高圧法低密度ポリエチレンを加えてなる組成物を二軸延伸してなる収縮フィルム（特許文献２）が提案されている。 A method of biaxially stretching an ethylene / α-olefin random copolymer under specific conditions as a method for improving the transparency, mechanical strength, etc. of the ethylene / α-olefin random copolymer film (Patent Document 1), ethylene・ Proposed shrink film (Patent Document 2) formed by biaxial stretching of α-olefin random copolymer and ethylene / α-olefin random copolymer with high-density polyethylene or high-pressure low-density polyethylene added Has been.
また、二軸延伸ＬＬＤＰＥフィルムにヒートシール性を付与するために、７０〜９９重量％のチーグラー−ナッタ触媒で製造された線状低密度ポリエチレンと１〜３０重量％のメタロセン触媒で製造された線状低密度ポリエチレンを含む心層に０．８６〜０．９７ｇ／ｃｍ3の範囲の密度を有するエチレンポリマー及び／またはコポリマーを含む少なくと
も１つの表皮層を有する包装用の二軸延伸多層フィルム（特許文献３）、密度が０．９０より小さいエチレン・α―オレフィンプラストマーコポリマー２０〜３５重量％と密度が少なくとも０．９１２でありかつ０．９１４よりも小さいＶＬＤＰＥ６５〜８０重量％とのブレンド物からなる第一外層及び第二外層を有する二軸延伸された熱収縮性多層延伸フィルム（特許文献４）が提案されている。
Also, in order to give heat-sealability to the biaxially stretched LLDPE film, a linear low density polyethylene produced with 70 to 99 wt% Ziegler-Natta catalyst and a wire produced with 1 to 30 wt% metallocene catalyst. Biaxially stretched multilayer film for packaging having at least one skin layer comprising an ethylene polymer and / or copolymer having a density in the range of 0.86 to 0.97 g / cm 3 in a core layer comprising a low density polyethylene Reference 3) from a blend of 20-35 wt% ethylene / α-olefin plastomer copolymer with a density less than 0.90 and 65-80 wt% VLDPE with a density of at least 0.912 and less than 0.914. A biaxially stretched heat-shrinkable multilayer stretched film (Patent Document 4) having a first outer layer and a second outer layer is proposed. ing.
しかしながら、かかる方法で得られる二軸延伸ＬＬＤＰＥフィルムあるいは二軸延伸多層ＬＬＤＰＥフィルムは透明性、引張強度等が強くなると共に、引裂き強度も強くなることから、易引裂き性フィルムとしては使用できない虞がある。
本発明は、縦横何れの方向にも容易に引裂け、且つ透明性、収縮性に優れると共にヒートシール性及び耐屈曲性にも優れる二軸延伸エチレン重合体フィルムを提供することを課題とする。 It is an object of the present invention to provide a biaxially stretched ethylene polymer film that can be easily torn in both the longitudinal and lateral directions and that is excellent in transparency and shrinkage, as well as heat sealability and flex resistance.
本発明によれば、下記の二軸延伸エチレン重合体多層フィルムが提供されて、上記課題が解決される。
（１）密度が９１５〜９３８Ｋｇ／ｍ3、示差走査熱量計（ＤＳＣ）により得られる融
解熱量（ΔＨT）が１００〜１４０Ｊ／ｇ、融解開始温度〜１１０℃の範囲の融解熱量（
ΔＨL）が５０〜８０Ｊ／ｇ、１１０℃〜融解終了温度の範囲の融解熱量（ΔＨH）が３５〜８０Ｊ／ｇの範囲にあり、（ΔＨH）／（ΔＨL）が０．５〜１．５の範囲にあるエチレン系重合体（Ａ）から得られる二軸延伸エチレン重合体フィルム基材層の少なくとも片面に、密度が８９０〜９１０Ｋｇ／ｍ3の範囲のエチレン・α―オレフィンランダム共重合
体（Ｂ）から得られる熱融着層が積層されてなることを特徴とする二軸延伸エチレン重合体多層フィルム。
According to the present invention, the following biaxially stretched ethylene polymer multilayer film is provided to solve the above problems.
(1) Heat of fusion with a density of 915 to 938 Kg / m 3 , a heat of fusion (ΔH T ) obtained by a differential scanning calorimeter (DSC) of 100 to 140 J / g, and a melting start temperature of 110 ° C. (
ΔH L ) is 50 to 80 J / g, heat of fusion (ΔH H ) in the range of 110 ° C. to melting end temperature is in the range of 35 to 80 J / g, and (ΔH H ) / (ΔH L ) is 0.5 to An ethylene / α-olefin random copolymer having a density in the range of 890 to 910 kg / m 3 is formed on at least one surface of the biaxially stretched ethylene polymer film base layer obtained from the ethylene polymer (A) in the range of 1.5. A biaxially stretched ethylene polymer multilayer film, wherein a heat-fusible layer obtained from the polymer (B) is laminated.
（２）二軸延伸エチレン重合体フィルム基材層が、ＭＤ方向の延伸倍率が３〜１４倍、ＴＤ方向の延伸倍率が３〜１４倍の範囲にある上記（１）記載の二軸延伸エチレン重合体多層フィルム。 (2) The biaxially stretched ethylene polymer film substrate layer has a stretch ratio in the MD direction of 3 to 14 times and a stretch ratio in the TD direction of 3 to 14 times. Polymer multilayer film.
（３）エチレン系重合体（Ａ）が、密度が８９５〜９２５Ｋｇ／ｍ3のエチレン・α−
オレフィンランダム共重合体（ａ１）成分と、密度が９２６〜９７０Ｋｇ／ｍ3のエチレ
ン系重合体（ａ２）成分とからなるエチレン共重合体組成物（Ａ−１）である上記（１）に記載の二軸延伸エチレン重合体多層フィルム。
(3) Ethylene-based polymer (A) having an ethylene / α- density of 895 to 925 Kg / m 3
In the above (1), which is an ethylene copolymer composition (A-1) comprising an olefin random copolymer (a1) component and an ethylene polymer (a2) component having a density of 926 to 970 Kg / m 3. Biaxially stretched ethylene polymer multilayer film.
（４）エチレン共重合体組成物（Ａ−１）が、エチレン・α−オレフィンランダム共重合体（ａ１）成分が５〜９５重量部及びエチレン系重合体（ａ２）成分が９５〜５重量部〔（ａ１）＋（ａ２）＝１００重量部〕からなる上記（３）に記載の二軸延伸エチレン重合体多層フィルム。 (4) The ethylene copolymer composition (A-1) is an ethylene / α-olefin random copolymer (a1) component of 5 to 95 parts by weight and an ethylene-based polymer (a2) component of 95 to 5 parts by weight. The biaxially stretched ethylene polymer multilayer film according to the above (3), comprising [(a1) + (a2) = 100 parts by weight].
（５）エチレン系重合体（Ａ）が、密度が８９５〜９２５Ｋｇ／ｍ3のエチレン・α−
オレフィンランダム共重合体（ａ１）成分、密度が９２６〜９７０Ｋｇ／ｍ3のエチレン
系重合体（ａ２）成分及び密度が９１０〜９３５Ｋｇ／ｍ3の高圧法低密度ポリエチレン
（ａ３）とからなるエチレン共重合体組成物（Ａ−２）である上記（１）に記載の二軸延伸エチレン重合体多層フィルム。
(5) An ethylene polymer (A) having a density of 895 to 925 Kg / m 3 and ethylene / α-
Olefin random copolymer (a1) component, an ethylene polymer having a density of 926~970Kg / m 3 (a2) component and density ethylene copolymer consisting of a high-pressure low-density polyethylene 910~935Kg / m 3 (a3) The biaxially stretched ethylene polymer multilayer film according to (1), which is the polymer composition (A-2).
（６）エチレン共重合体組成物（Ａ−２）が、エチレン・α−オレフィンランダム共重合体（ａ１）成分を５〜９５重量部及びエチレン系重合体（ａ２）成分を９５〜５重量部〔（ａ１）＋（ａ２）＝１００重量部〕の割合で含有する上記（５）に記載の二軸延伸エチレン重合体多層フィルム。 (6) The ethylene copolymer composition (A-2) is 5 to 95 parts by weight of the ethylene / α-olefin random copolymer (a1) component and 95 to 5 parts by weight of the ethylene-based polymer (a2) component. The biaxially stretched ethylene polymer multilayer film according to the above (5), which is contained at a ratio of [(a1) + (a2) = 100 parts by weight].
（７）エチレン重合体組成物（Ａ−２）が、エチレン・α−オレフィンランダム共重合体（ａ１）成分とエチレン系重合体（ａ２）成分との合計量が５０〜９５重量部及び高圧法低密度ポリエチレン（ａ３）が５０〜５重量部〔［（ａ１）＋（ａ２）］＋（ａ３）＝１００重量部〕からなる上記（５）または（６）に記載の二軸延伸エチレン重合体多層フィルム。 (7) The ethylene polymer composition (A-2) contains 50 to 95 parts by weight of the total amount of the ethylene / α-olefin random copolymer (a1) component and the ethylene-based polymer (a2) component, and the high pressure method. The biaxially stretched ethylene polymer according to the above (5) or (6), wherein the low density polyethylene (a3) is 50 to 5 parts by weight [[(a1) + (a2)] + (a3) = 100 parts by weight]. Multilayer film.
（８）エチレン系重合体（ａ２）成分が、密度が９２６〜９４５Ｋｇ／ｍ3のエチレン
系重合体（ａ２−１）成分と密度が９４６〜９７０Ｋｇ／ｍ3のエチレン系重合体（ａ２
−２）成分とからなる上記（３）ないし（７）のいずれかに記載の二軸延伸エチレン重合体多層フィルム。
(8) ethylene polymer component (a2) is an ethylene polymer having a density of 926~945Kg / m 3 (a2-1) ethylene polymer component and a density 946~970Kg / m 3 (a2
-2) The biaxially stretched ethylene polymer multilayer film according to any one of (3) to (7), comprising the component.
（９）エチレン系重合体（ａ２）成分が、エチレン系重合体（ａ２−１）成分を１〜９９重量部及びエチレン系重合体（ａ２−２）成分を９９〜１重量部〔（ａ２−１）＋（ａ２−２）＝１００重量部〕の割合で含有する上記（８）に記載の二軸延伸エチレン重合体多層フィルム。 (9) The ethylene polymer (a2) component is 1 to 99 parts by weight of the ethylene polymer (a2-1) component and 99 to 1 part by weight of the ethylene polymer (a2-2) component [(a2- 1) + (a2-2) = 100 parts by weight] The biaxially stretched ethylene polymer multilayer film as described in (8) above.
（１０）二軸延伸エチレン重合体多層フィルムのＭＤ方向の引裂き強度およびＴＤ方向の引裂き強度のうち一方を（ＴS）、他方を（ＴW）（但し、ＴS＞ＴWである。）としたときに、引裂き強度（ＴS）が８０〜１０Ｎ／ｃｍ、（ＴW）／（ＴS）が０．１０〜１の範
囲にある上記（１）ないし（９）のいずれかに記載の二軸延伸エチレン重合体多層フィルム。
(10) One of the tear strength in the MD direction and the tear strength in the TD direction of the biaxially stretched ethylene polymer multilayer film is (T S ) and the other is (T W ) (where T S > T W. ) The tear strength (T S ) is 80 to 10 N / cm, and (T W ) / (T S ) is in the range of 0.10 to 1, according to any one of (1) to (9) above. Biaxially stretched ethylene polymer multilayer film.
（１１）二軸延伸エチレン重合体多層フィルムの基材層の他の片面に熱可塑性樹脂フィルムが積層されてなる上記（１）ないし（９）のいずれかに記載の二軸延伸エチレン重合体多層フィルム。 (11) The biaxially stretched ethylene polymer multilayer according to any one of (1) to (9), wherein a thermoplastic resin film is laminated on the other surface of the base layer of the biaxially stretched ethylene polymer multilayer film. the film.
（１２）熱可塑性樹脂フィルムが、二軸延伸されてなる上記（１１）に記載の二軸延伸エチレン重合体多層フィルム。
（１３）熱可塑性樹脂がポリエステル、ポリアミド若しくはポリプロピレンのいずれかである上記（１１）または（１２）に記載の二軸延伸エチレン重合体多層フィルム。
(12) The biaxially stretched ethylene polymer multilayer film according to the above (11), wherein the thermoplastic resin film is biaxially stretched.
(13) The biaxially stretched ethylene polymer multilayer film according to the above (11) or (12), wherein the thermoplastic resin is any one of polyester, polyamide or polypropylene.
本発明の二軸延伸エチレン重合体多層フィルムは、縦横何れの方向にも容易に引裂け、且つ透明性、収縮性に優れ、しかもヒートシール性及び耐屈曲性にも優れる。 The biaxially stretched ethylene polymer multilayer film of the present invention is easily torn in both the longitudinal and lateral directions, is excellent in transparency and shrinkage, and is also excellent in heat sealability and bending resistance.
以下、本発明に係る二軸延伸エチレン重合体多層フィルムについて詳細に説明する。
［エチレン系重合体（Ａ）］
本発明の二軸延伸エチレン重合体多層フィルムの二軸延伸エチレン重合体フィルム基材層を形成するエチレン系重合体（Ａ）は、密度が９１５〜９３８Ｋｇ／ｍ3、好ましくは
９２０〜９３５Ｋｇ／ｍ3、示差走査熱量計（ＤＳＣ）により得られる融解熱量（ΔＨT）が１００〜１４０Ｊ／ｇ、好ましくは１１５〜１３５Ｊ／ｇ、融解開始温度〜１１０℃の範囲の融解熱量（ΔＨL）が５０〜８０Ｊ／ｇ、好ましくは５５〜８０Ｊ／ｇ、１１０℃
〜融解終了温度の範囲の融解熱量（ΔＨH）が３５〜８０Ｊ／ｇ、好ましくは４５〜８０
Ｊ／ｇの範囲にあり、（ΔＨH）／（ΔＨL）が０．５〜１．５、好ましくは０．６５〜１．４の範囲にあるエチレン系重合体である。
Hereinafter, the biaxially stretched ethylene polymer multilayer film according to the present invention will be described in detail.
[Ethylene polymer (A)]
The density of the ethylene polymer (A) forming the biaxially stretched ethylene polymer film substrate layer of the biaxially stretched ethylene polymer multilayer film of the present invention is 915 to 938 Kg / m 3 , preferably 920 to 935 Kg / m. 3. The heat of fusion (ΔH T ) obtained by a differential scanning calorimeter (DSC) is 100 to 140 J / g, preferably 115 to 135 J / g, and the heat of fusion (ΔH L ) in the range of the melting start temperature to 110 ° C. is 50. -80 J / g, preferably 55-80 J / g, 110 ° C
The heat of fusion (ΔH H ) in the range of the melting end temperature is 35-80 J / g, preferably 45-80.
It is an ethylene polymer in the range of J / g and (ΔH H ) / (ΔH L ) in the range of 0.5 to 1.5, preferably in the range of 0.65 to 1.4.
密度が上記範囲外、あるいは（ΔＨT）が上記範囲外のエチレン系重合体は、二軸延伸
多層フィルムの成形が困難な場合がある、また、（ΔＨH）が３５Ｊ／ｇ未満、あるいは
（ΔＨH）／（ΔＨL）が０．５未満のエチレン系重合体は、二軸延伸多層フィルムを成形しても、一方向の引裂き強度が大きくなり、縦横何れの方向にも容易に引裂ける二軸延伸多層フィルムが得られない虞がある。
An ethylene polymer having a density outside the above range or (ΔH T ) outside the above range may make it difficult to form a biaxially stretched multilayer film, and (ΔH H ) is less than 35 J / g, or ( An ethylene polymer having ΔH H ) / (ΔH L ) of less than 0.5 has a high tear strength in one direction even when a biaxially stretched multilayer film is formed, and can be easily torn in any direction. There is a possibility that a biaxially stretched multilayer film cannot be obtained.
本発明に係るエチレン系重合体（Ａ）は、フィルム形成能がある限り、メルトフローレート（ＭＦＲ：ＡＳＴＭ Ｄ１２３８ 荷重２１６０ｇ、温度１９０℃）は特に限定はされないが、通常、０．５〜１０ｇ／１０分、好ましくは０．８〜５ｇ／１０分の範囲にある。 As long as the ethylene-based polymer (A) according to the present invention has film-forming ability, the melt flow rate (MFR: ASTM D1238 load 2160 g, temperature 190 ° C.) is not particularly limited, but usually 0.5 to 10 g / It is in the range of 10 minutes, preferably 0.8-5 g / 10 minutes.
本発明に係るエチレン系重合体（Ａ）の密度は、後述するように密度勾配管により測定される。
本発明に係るエチレン系重合体（Ａ）の各熱融解量は、示差走査熱量計（ＤＳＣ）を用いて、以下の方法で測定した値である。
The density of the ethylene polymer (A) according to the present invention is measured by a density gradient tube as described later.
Each heat melting amount of the ethylene polymer (A) according to the present invention is a value measured by the following method using a differential scanning calorimeter (DSC).
示差走査熱量計（ＤＳＣ）としてティ・エイ・インスツルメント社製 Ｑ１００を用い、試料約５ｍｇを精秤し、ＪＩＳ Ｋ ７１２２に準拠し、１０℃から加熱速度：１０℃／分で１８０℃迄昇温して試料を一旦融解させた後、１８０℃に１０分間維持し、冷却速度
：１０℃／分で１０℃迄降温して結晶化させた後、１０℃に５分間維持した後、再度加熱速度：１０℃／分で１８０℃迄昇温して熱融解曲線を得、得られた熱融解曲線から、試料の熱融解量（ΔＨT）、得られた熱融解曲線を１１０℃で二分し、融解開始温度〜１１０
℃の範囲の融解熱量（ΔＨL）及び１１０℃〜融解終了温度の範囲の融解熱量（ΔＨH）を求めた。
Using Q100 made by TI Instruments as a differential scanning calorimeter (DSC), accurately weigh about 5 mg of sample, and according to JIS K 7122, heating rate from 10 ° C. to 180 ° C. at 10 ° C./min. The sample was melted once by heating, then maintained at 180 ° C. for 10 minutes, cooled to 10 ° C. at a cooling rate of 10 ° C./minute, crystallized, then maintained at 10 ° C. for 5 minutes, and again Heating rate: The temperature was raised to 180 ° C. at 10 ° C./min to obtain a thermal melting curve. From the obtained thermal melting curve, the thermal melting amount of the sample (ΔH T ), and the obtained thermal melting curve was divided into 110 minutes at 110 ° C. Melting start temperature to 110
The heat of fusion (ΔH L ) in the range of ° C. and the heat of fusion (ΔH H ) in the range of 110 ° C. to the end of melting temperature were determined.
本発明で用いられるエチレン系重合体（Ａ）の（ΔＨL）は、主としてエチレン系重合
体（Ａ）に含まれる低密度成分に由来し、（ΔＨH）は、主としてエチレン系重合体（Ａ
）に含まれる高密度成分に由来するものであり、（ΔＨH）／（ΔＨL）が上記範囲にあるということは、換言すれば、本発明に係るエチレン系重合体（Ａ）は、特定の範囲の組成分布を有するエチレン系重合体とも言えるものである。
(ΔH L ) of the ethylene polymer (A) used in the present invention is mainly derived from a low density component contained in the ethylene polymer (A), and (ΔH H ) is mainly produced from the ethylene polymer (A
) Is derived from a high-density component contained in ()), and (ΔH H ) / (ΔH L ) is in the above range, in other words, the ethylene polymer (A) according to the present invention is specified. It can also be said that it is an ethylene polymer having a composition distribution in the range.
したがって、本発明に係るエチレン系重合体（Ａ）は、チーグラー触媒、シングルサイト触媒等を適宜選択し、得られるエチレン系重合体の組成分布（密度分布）を調整することにより得られるが、密度の異なるエチレン系重合体を適宜混合することによっても得られる。その場合は、密度の異なるエチレン系重合体、例えば、密度が８９５〜９１５ｋｇ／ｍ3の範囲にある重合体の量及び密度が９１５〜９６５ｋｇ／ｍ3の範囲にある重合体の量を夫々増減することによっても得られる。 Therefore, the ethylene polymer (A) according to the present invention can be obtained by appropriately selecting a Ziegler catalyst, a single site catalyst, etc., and adjusting the composition distribution (density distribution) of the resulting ethylene polymer. It can also be obtained by appropriately mixing different ethylene polymers. In that case, different ethylene polymer density, for example, the amount of the respective increase or decrease of the polymer amount and density of the polymer having a density in the range of 895~915kg / m 3 is in the range of 915~965kg / m 3 Can also be obtained.
本発明で用いられるエチレン系重合体（Ａ）は、特には、密度の異なるエチレン系重合体を混合することにより得られる下記エチレン共重合体組成物（Ａ−１）またはエチレン共重合体組成物（Ａ−２）が好ましい。
［エチレン共重合体組成物（Ａ−１）］
本発明で用いられるエチレン共重合体組成物（Ａ−１）は、密度が８９５〜９２５Ｋｇ／ｍ3、好ましくは９００〜９２０Ｋｇ／ｍ3の範囲にあるエチレン・α−オレフィン共重合体（ａ１）成分と密度が９２６〜９７０Ｋｇ／ｍ3、好ましくは９３０〜９６５Ｋｇ／
ｍ3の範囲にあるエチレン系重合体（ａ２）成分とからなるエチレン共重合体組成物であ
り、好ましくは、エチレン・α−オレフィンランダム共重合体（ａ１）成分が５〜９５重量部、より好ましくは２０〜８０重量部及びエチレン系重合体（ａ２）成分が９５〜５重量部、より好ましくは８０〜２０重量部〔（ａ１）＋（ａ２）＝１００重量部〕の範囲にある。
The ethylene polymer (A) used in the present invention is, in particular, the following ethylene copolymer composition (A-1) or ethylene copolymer composition obtained by mixing ethylene polymers having different densities. (A-2) is preferred.
[Ethylene copolymer composition (A-1)]
The ethylene copolymer composition (A-1) used in the present invention has an ethylene / α-olefin copolymer (a1) having a density in the range of 895 to 925 Kg / m 3 , preferably 900 to 920 Kg / m 3. Components and density are 926-970 kg / m 3 , preferably 930-965 kg /
It is an ethylene copolymer composition comprising an ethylene polymer (a2) component in the range of m 3 , preferably 5 to 95 parts by weight of the ethylene / α-olefin random copolymer (a1) component, Preferably, 20 to 80 parts by weight and the ethylene polymer (a2) component are in the range of 95 to 5 parts by weight, more preferably 80 to 20 parts by weight [(a1) + (a2) = 100 parts by weight].
本発明で用いられるエチレン共重合体組成物（Ａ−１）は、フィルム形成能がある限り、メルトフローレート（ＭＦＲ：ＡＳＴＭ Ｄ１２３８ 荷重２１６０ｇ、温度１９０℃）は特に限定はされないが、通常、０．５〜１０ｇ／１０分、好ましくは０．８〜５ｇ／１０分の範囲にある。
［エチレン共重合体組成物（Ａ−２）］
本発明で用いられるエチレン共重合体組成物（Ａ−２）は、密度が８９５〜９２５Ｋｇ／ｍ3、好ましくは９００〜９２０Ｋｇ／ｍ3の範囲にあるエチレン・α−オレフィンランダム共重合体（ａ１）成分、密度が９２６〜９７０Ｋｇ／ｍ3、好ましくは９３０〜９６
５Ｋｇ／ｍ3の範囲にあるエチレン系重合体（ａ２）成分及び密度が９１０〜９３５Ｋｇ
／ｍ3、好ましくは９１５〜９３０Ｋｇ／ｍ3の範囲にある高圧法低密度ポリエチレン（ａ３）とからなるエチレン共重合体組成物である。エチレン共重合体組成物（Ａ−２）は、（ａ１）、（ａ２）および（ａ３）のうち、エチレン・α−オレフィンランダム共重合体（ａ１）成分が、好ましくは５〜９５重量部、より好ましくは２０〜８０重量部及びエチレン系重合体（ａ２）成分が９５〜５重量部、より好ましくは４０〜７０重量部〔（ａ１）＋（ａ２）＝１００重量部〕の範囲にあることが望ましい。また、エチレン共重合体組成物（Ａ−２）は、エチレン・α−オレフィンランダム共重合体（ａ１）成分＋エチレン系重合体（ａ２）成分が、好ましくは５０〜９５重量部、好ましくは６０〜９０重量部及び高圧法低密度ポリエチレン（ａ３）が５０〜５重量部、好ましくは３０〜１０重量部〔
［（ａ１）＋（ａ２）］＋（ａ３）＝１００重量部〕の範囲にあることが望ましい。
As long as the ethylene copolymer composition (A-1) used in the present invention has film-forming ability, the melt flow rate (MFR: ASTM D1238 load 2160 g, temperature 190 ° C.) is not particularly limited, but is usually 0. .5 to 10 g / 10 min, preferably 0.8 to 5 g / 10 min.
[Ethylene copolymer composition (A-2)]
The ethylene copolymer composition (A-2) used in the present invention has an ethylene / α-olefin random copolymer (a1) having a density in the range of 895 to 925 Kg / m 3 , preferably 900 to 920 Kg / m 3. ) Component, density is 926 to 970 Kg / m 3 , preferably 930 to 96
Ethylene polymer (a2) component in the range of 5 kg / m 3 and density is 910-935 kg
/ M 3 , preferably an ethylene copolymer composition comprising high-pressure low-density polyethylene (a3) in the range of 915 to 930 Kg / m 3 . In the ethylene copolymer composition (A-2), among the components (a1), (a2) and (a3), the ethylene / α-olefin random copolymer (a1) component is preferably 5 to 95 parts by weight, More preferably, 20 to 80 parts by weight and the ethylene-based polymer (a2) component are in the range of 95 to 5 parts by weight, more preferably 40 to 70 parts by weight [(a1) + (a2) = 100 parts by weight]. Is desirable. In the ethylene copolymer composition (A-2), the ethylene / α-olefin random copolymer (a1) component + ethylene-based polymer (a2) component is preferably 50 to 95 parts by weight, preferably 60 parts. To 90 parts by weight and 50 to 5 parts by weight, preferably 30 to 10 parts by weight of high-pressure low-density polyethylene (a3) [
It is desirable to be in the range of [(a1) + (a2)] + (a3) = 100 parts by weight].
本発明の係るエチレン共重合体組成物（Ａ−２）は、フィルム形成能がある限り、メルトフローレート（ＭＦＲ：ＡＳＴＭ Ｄ１２３８ 荷重２１６０ｇ、温度１９０℃）は特に限定はされないが、通常、０．５〜１０ｇ／１０分、好ましくは０．８〜５ｇ／１０分の範囲にある。
［エチレン・α−オレフィン共重合体（ａ１）］
本発明の二軸延伸エチレン重合体多層フィルムの二軸延伸エチレン重合体フィルム基材層を形成するエチレン共重合体組成物（Ａ−１）またはエチレン共重合体組成物（Ａ−２）を構成する成分であるエチレン・α−オレフィン共重合体（ａ１）は、密度が８９５〜９２５Ｋｇ／ｍ3、好ましくは９００〜９２０Ｋｇ／ｍ3の範囲にあるエチレンと炭素数４以上のα−オレフィン、例えば、１−ブテン、１−ヘプテン、１−ヘキセン、１−オクテン、４−メチル−１−ペンテン等のα−オレフィン、好ましくは炭素数が６以上のα−オレフィンとのランダム共重合体である。本発明に係るエチレン・α−オレフィン共重合体（ａ１）は前記範囲の密度であれば、１種あるいは２種以上の混合物であってもよい。
As long as the ethylene copolymer composition (A-2) according to the present invention has a film-forming ability, the melt flow rate (MFR: ASTM D1238 load 2160 g, temperature 190 ° C.) is not particularly limited. It is in the range of 5 to 10 g / 10 minutes, preferably 0.8 to 5 g / 10 minutes.
[Ethylene / α-olefin copolymer (a1)]
The ethylene copolymer composition (A-1) or the ethylene copolymer composition (A-2) forming the biaxially stretched ethylene polymer film substrate layer of the biaxially stretched ethylene polymer multilayer film of the present invention is constituted. The ethylene / α-olefin copolymer (a1), which is a component to be used, has an density of 895 to 925 Kg / m 3 , preferably 900 to 920 Kg / m 3 , and an α-olefin having 4 or more carbon atoms, for example, , 1-butene, 1-heptene, 1-hexene, 1-octene, 4-methyl-1-pentene and the like, and preferably a random copolymer with an α-olefin having 6 or more carbon atoms. The ethylene / α-olefin copolymer (a1) according to the present invention may be one type or a mixture of two or more types as long as the density is in the above range.
本発明に係るエチレン・α−オレフィン共重合体（ａ１）のメルトフローレート（ＭＦＲ：ＡＳＴＭ Ｄ１２３８ 荷重２１６０ｇ、温度１９０℃）は、後述のエチレン系重合体（ａ２）との組成物（Ａ−１）またはエチレン系重合体（ａ２）と高圧法低密度ポリエチレン（ａ３）との組成物（Ａ−２）とした際に、フィルム形成能がある限りとくに限定はされないが、通常０．０１〜１０ｇ／１０分、好ましくは０．２〜５ｇ／１０分の範囲にある。 The melt flow rate (MFR: ASTM D1238 load 2160 g, temperature 190 ° C.) of the ethylene / α-olefin copolymer (a1) according to the present invention is a composition (A-1) with an ethylene polymer (a2) described later. ) Or the composition (A-2) of the ethylene-based polymer (a2) and the high-pressure method low-density polyethylene (a3) is not particularly limited as long as it has a film-forming ability, but is usually 0.01 to 10 g. / 10 minutes, preferably in the range of 0.2 to 5 g / 10 minutes.
また、かかるエチレン・α−オレフィン共重合体（ａ１）は、分子量分布（重量平均分子量：Ｍｗ、と数平均分子量：Ｍｎ、との比：Ｍｗ／Ｍｎで表示）が通常１．５〜４．０、好ましくは１．８〜３．５の範囲にある。このＭｗ／Ｍｎはゲル透過クロマトグラフィー（ＧＰＣ）によって測定できる。 Further, the ethylene / α-olefin copolymer (a1) has a molecular weight distribution (weight average molecular weight: Mw, number average molecular weight: Mn, ratio: Mw / Mn) is usually 1.5 to 4. 0, preferably in the range of 1.8 to 3.5. This Mw / Mn can be measured by gel permeation chromatography (GPC).
また、エチレン・α−オレフィン共重合体（ａ１）は、示差走査熱量計（ＤＳＣ）の昇温速度１０℃／分で測定した吸熱曲線から求めた鋭いピークが１個ないし複数個あり、該ピークの最高温度、すなわち融点が通常７０〜１３０℃、好ましくは８０〜１２０℃の範囲にある。 The ethylene / α-olefin copolymer (a1) has one to a plurality of sharp peaks determined from an endothermic curve measured at a heating rate of 10 ° C./min with a differential scanning calorimeter (DSC). The maximum temperature, i.e., the melting point, is usually in the range of 70 to 130 ° C, preferably 80 to 120 ° C.
上記のようなエチレン・α−オレフィン共重合体（ａ１）は、チーグラー触媒、シングルサイト触媒等を用いた従来公知の製造法により調整することができるが、シングルサイト触媒（メタロセン触媒）により得られた共重合体がとくに好ましい。このメタロセン化合物を含む触媒は、（ａ）遷移金属のメタロセン化合物と、（ｂ）有機アルミニウムオキシ化合物と、（ｃ）担体とから形成されることが好ましく、さらに必要に応じて、これらの成分と（ｄ）有機アルミニウム化合物および／または有機ホウ素化合物とから形成さていてもよい。 The ethylene / α-olefin copolymer (a1) as described above can be prepared by a conventionally known production method using a Ziegler catalyst, a single site catalyst or the like, but is obtained by a single site catalyst (metallocene catalyst). Particularly preferred are copolymers. The catalyst containing the metallocene compound is preferably formed from (a) a transition metal metallocene compound, (b) an organoaluminum oxy compound, and (c) a carrier, and if necessary, these components and (D) It may be formed from an organoaluminum compound and / or an organoboron compound.
なお、このようなメタロセン化合物を含むオレフィン重合用触媒、および触媒を用いたエチレン・α−オレフィン共重合体（ａ１）の調整方法は、たとえば特開平８−２６９２７０号公報に記載されている。
［エチレン系重合体（ａ２）］
本発明の二軸延伸エチレン重合体多層フィルムの二軸延伸エチレン重合体フィルム基材層を形成するエチレン共重合体組成物（Ａ−１）またはエチレン共重合体組成物（Ａ−２）を構成する他の成分であるエチレン系重合体（ａ２）は、密度が９２６〜９７０Ｋｇ／ｍ3、好ましくは９３０〜９６５Ｋｇ／ｍ3の範囲にあるエチレンの単独重合体またはエチレンと炭素数３以上のα−オレフィン、例えば、プロピレン、１−ブテン、１−ヘプテン
、１−ヘキセン、１−オクテン、４−メチル−１−ペンテン等のα−オレフィンとのランダム共重合体である。本発明に係るエチレン系重合体（ａ２）は前記範囲の密度であれば、１種あるいは２種以上の混合物であってもよい。
An olefin polymerization catalyst containing such a metallocene compound and a method for adjusting the ethylene / α-olefin copolymer (a1) using the catalyst are described in, for example, JP-A-8-269270.
[Ethylene polymer (a2)]
The ethylene copolymer composition (A-1) or the ethylene copolymer composition (A-2) forming the biaxially stretched ethylene polymer film substrate layer of the biaxially stretched ethylene polymer multilayer film of the present invention is constituted. The ethylene polymer (a2) which is the other component is an ethylene homopolymer having a density in the range of 926 to 970 Kg / m 3 , preferably 930 to 965 Kg / m 3 , or ethylene and α having 3 or more carbon atoms. -Random copolymers with [alpha] -olefins such as propylene, 1-butene, 1-heptene, 1-hexene, 1-octene, 4-methyl-1-pentene. The ethylene polymer (a2) according to the present invention may be one type or a mixture of two or more types as long as the density is in the above range.
エチレン系重合体（ａ２）のメルトフローレート（ＭＦＲ：ＡＳＴＭ Ｄ１２３８ 荷重２１６０ｇ、温度１９０℃）は、前述のエチレン系重合体（ａ１）との組成物（Ａ−１）及びエチレン系重合体（ａ１）及び後述の高圧法低密度ポリエチレン（ａ３）との組成物（Ａ−２）とした際に、フィルム形成能がある限りとくに限定はされないが、通常０．０１〜１００ｇ／１０分、好ましくは０．１〜８０ｇ／１０分の範囲にある。 The melt flow rate (MFR: ASTM D1238 load 2160 g, temperature 190 ° C.) of the ethylene polymer (a2) is the composition (A-1) with the ethylene polymer (a1) and the ethylene polymer (a1). ) And a composition (A-2) with a high-pressure method low-density polyethylene (a3) described later, although there is no particular limitation as long as it has a film-forming ability, usually 0.01 to 100 g / 10 minutes, preferably It exists in the range of 0.1-80g / 10min.
エチレン系重合体（ａ２）は、さらには、密度が９２６〜９４５Ｋｇ／ｍ3、好ましく
は９３５〜９４５Ｋｇ／ｍ3の範囲のエチレン系重合体（ａ２−１）成分と密度が９４６
〜９７０Ｋｇ／ｍ3、好ましくは９５０〜９６５Ｋｇ／ｍ3の範囲のエチレン系重合体（ａ２−２）成分と低密度成分と高密度成分を併用すると、より縦／横方向の何れにも容易に引裂け易い二軸延伸エチレン重合体多層フィルムが得られる。
The ethylene polymer (a2) has a density of 946 to 946 kg / m 3 , preferably 935 to 945 Kg / m 3 and preferably 946 to 945 kg / m 3.
˜970 Kg / m 3 , preferably 950 to 965 Kg / m 3 in the range of ethylene polymer (a2-2) component, low density component and high density component are used in combination in both longitudinal and lateral directions. A biaxially stretched ethylene polymer multilayer film that is easy to tear is obtained.
エチレン系重合体（ａ２）としてエチレン系重合体（ａ２−１）成分とエチレン系重合体（ａ２−２）成分を用いる場合は、エチレン系重合体（ａ２−１）成分を１〜９９重量部、好ましくは３０〜７０重量部及びエチレン系重合体（ａ２−２）成分を９９〜１重量部、好ましくは７０〜３０重量部〔（ａ２−１）＋（ａ２−２）＝１００重量部〕の割合とすることが望ましい。 When the ethylene polymer (a2-1) component and the ethylene polymer (a2-2) component are used as the ethylene polymer (a2), 1 to 99 parts by weight of the ethylene polymer (a2-1) component is used. , Preferably 30 to 70 parts by weight and 99 to 1 part by weight of ethylene polymer (a2-2) component, preferably 70 to 30 parts by weight [(a2-1) + (a2-2) = 100 parts by weight] It is desirable to make the ratio.
また、かかるエチレン系重合体（ａ２）は、分子量分布（重量平均分子量：Ｍｗ、と数平均分子量：Ｍｎ、との比：Ｍｗ／Ｍｎで表示）が通常１．５〜４．０、好ましくは１．８〜３．５の範囲にある。このＭｗ／Ｍｎはゲル透過クロマトグラフィー（ＧＰＣ）によって測定できる。 Further, the ethylene polymer (a2) has a molecular weight distribution (weight average molecular weight: Mw, ratio of number average molecular weight: Mn: expressed as Mw / Mn) is usually 1.5 to 4.0, preferably It is in the range of 1.8 to 3.5. This Mw / Mn can be measured by gel permeation chromatography (GPC).
また、エチレン系重合体（ａ２）は、示差走査熱量計（ＤＳＣ）の昇温速度１０℃／分で測定した吸熱曲線から求めた鋭いピークが１個ないし複数個あり、該ピークの最高温度、すなわち融点が通常１２２〜１３５℃、の範囲にある。 The ethylene polymer (a2) has one or more sharp peaks determined from an endothermic curve measured at a heating rate of 10 ° C./min of a differential scanning calorimeter (DSC), the maximum temperature of the peak, That is, the melting point is usually in the range of 122 to 135 ° C.
上記のようなエチレン系重合体（ａ２）は、チーグラー触媒、シングルサイト触媒等を用いた従来公知の製造法により調整することができる。特に、エチレン系重合体（ａ２）としてエチレン系重合体（ａ２−１）を用いる場合は、シングルサイト触媒（メタロセン触媒）により得られた共重合体がとくに好ましい。このメタロセン化合物を含む触媒は、（ａ）遷移金属のメタロセン化合物と、（ｂ）有機アルミニウムオキシ化合物と、（ｃ）担体とから形成されることが好ましく、さらに必要に応じて、これらの成分と（ｄ）有機アルミニウム化合物および／または有機ホウ素化合物とから形成さていてもよい。 The ethylene polymer (a2) as described above can be prepared by a conventionally known production method using a Ziegler catalyst, a single site catalyst or the like. In particular, when the ethylene polymer (a2-1) is used as the ethylene polymer (a2), a copolymer obtained with a single site catalyst (metallocene catalyst) is particularly preferable. The catalyst containing the metallocene compound is preferably formed from (a) a transition metal metallocene compound, (b) an organoaluminum oxy compound, and (c) a carrier, and if necessary, these components and (D) It may be formed from an organoaluminum compound and / or an organoboron compound.
なお、このようなメタロセン化合物を含むオレフィン重合用触媒、および触媒を用いたエチレン・α−オレフィン共重合体（ａ２）の調整方法は、たとえば特開平８−２６９２７０号公報に記載されている。 An olefin polymerization catalyst containing such a metallocene compound and a method for adjusting the ethylene / α-olefin copolymer (a2) using the catalyst are described in, for example, JP-A-8-269270.
一方、エチレン系重合体（ａ２）としてエチレン系重合体（ａ２−２）を用いる場合は、シングルサイト触媒（メタロセン触媒）により得られる重合体であってもよいが、従来公知のチーグラー触媒等で製造されている、所謂高密度ポリエチレンであってもよい。
［高圧法低密度ポリエチレン（ａ３）］
本発明の二軸延伸エチレン重合体多層フィルムの二軸延伸エチレン重合体フィルム基材層を形成するエチレン共重合体組成物（Ａ−２）を構成する他の一つ成分である高圧法低密度ポリエチレン（ａ３）は、密度が９１０〜９３５Ｋｇ／ｍ3、好ましくは９１５〜９
３０Ｋｇ／ｍ3の範囲にある。かかる高圧法低密度ポリエチレンは、高圧下で重合される
エチレンの単独重合体、若しくは５重量％以下の、他のα−オレフィンあるいは酢酸ビニル等のビニル化合物との共重合体で、低密度ポリエチレンの範疇に入るエチレン系重合体である。
On the other hand, when the ethylene polymer (a2-2) is used as the ethylene polymer (a2), a polymer obtained by a single site catalyst (metallocene catalyst) may be used, but a conventionally known Ziegler catalyst or the like may be used. The so-called high density polyethylene produced may be used.
[High pressure low density polyethylene (a3)]
High pressure method low density which is another one component constituting the ethylene copolymer composition (A-2) for forming the biaxially stretched ethylene polymer film substrate layer of the biaxially stretched ethylene polymer multilayer film of the present invention The polyethylene (a3) has a density of 910 to 935 Kg / m 3 , preferably 915 to 9
It is in the range of 30 kg / m 3 . The high-pressure method low-density polyethylene is a homopolymer of ethylene polymerized under high pressure, or a copolymer of 5% by weight or less with other α-olefin or vinyl compound such as vinyl acetate. It is an ethylene polymer that falls into the category.
密度が９１０Ｋｇ／ｍ3未満の高圧法低密度ポリエチレンは、前記エチレン共重合体組
成物（Ａ−２）として二軸延伸多層フィルムを成形した場合に得られるフィルムがブロッキングし易く、引裂き強度が強く、本発明の目的が達成出来ない虞がある。
The high-pressure low-density polyethylene having a density of less than 910 kg / m 3 is easy to block when the biaxially stretched multilayer film is molded as the ethylene copolymer composition (A-2), and has high tear strength. The object of the present invention may not be achieved.
高圧法低密度ポリエチレン（ａ３）のメルトフローレート（ＭＦＲ：ＡＳＴＭ Ｄ１２
３８ 荷重２１６０ｇ、温度１９０℃）は、前述のエチレン系重合体（ａ１）及びエチレン系重合体（ａ１）との組成物（Ａ−２）とした際に、フィルム形成能がある限りとくに限定はされないが、通常、０．１〜３０ｇ／１０分、好ましくは０．１〜１０ｇ／１０分の範囲にある。
High pressure method low density polyethylene (a3) melt flow rate (MFR: ASTM D12)
38 load 2160 g, temperature 190 ° C.) is not particularly limited as long as it has a film-forming ability when the composition (A-2) with the above-mentioned ethylene polymer (a1) and ethylene polymer (a1) is used. However, it is usually in the range of 0.1 to 30 g / 10 min, preferably 0.1 to 10 g / 10 min.
本発明に係るエチレン共重合体組成物（Ａ−１）及びエチレン共重合体組成物（Ａ−２）は、各々別個にエチレン・α−オレフィンランダム共重合体（ａ１）、エチレン系重合体（ａ２）及び高圧法低密度ポリエチレン（ａ３）を得た後、ヘンシェルミキサー、タンブラーブレンダー、Ｖ−ブレンダー等によりドライブレンドする方法またはドライブレンドした後、単軸押出機、多軸押出機、バンバリーミキサー等により溶融混練することにより得られる。 The ethylene copolymer composition (A-1) and the ethylene copolymer composition (A-2) according to the present invention are each independently an ethylene / α-olefin random copolymer (a1), an ethylene polymer ( After obtaining a2) and high-pressure method low density polyethylene (a3), dry blending with a Henschel mixer, tumbler blender, V-blender or the like, or after dry blending, single screw extruder, multi-screw extruder, Banbury mixer, etc. Obtained by melt kneading.
本発明に係るエチレン共重合体組成物（Ａ−１）はまた、連続・多段重合プロセスにより、複数の重合器を用いて、エチレン・α−オレフィンランダム共重合体（ａ１）とエチレン系重合体（ａ２）を夫々重合した後、混合してエチレン共重合体組成物（Ａ−１）とする方法、１個の重合器を用いて、先にエチレン・α−オレフィンランダム共重合体（ａ１）若しくはエチレン系重合体（ａ２）を重合した後、続いてエチレン系重合体（ａ２）若しくはエチレン・α−オレフィンランダム共重合体（ａ１）を重合する方法等、種々公知の重合方法を採り得る。 The ethylene copolymer composition (A-1) according to the present invention can also be obtained by using a plurality of polymerizers by a continuous / multistage polymerization process to produce an ethylene / α-olefin random copolymer (a1) and an ethylene polymer. A method in which (a2) is polymerized and then mixed to obtain an ethylene copolymer composition (A-1). Using one polymerizer, an ethylene / α-olefin random copolymer (a1) Alternatively, various known polymerization methods such as a method of polymerizing the ethylene polymer (a2) and then polymerizing the ethylene polymer (a2) or the ethylene / α-olefin random copolymer (a1) can be employed.
本発明に係るエチレン系重合体（Ａ）、エチレン共重合体組成物（Ａ−１）、エチレン共重合体組成物（Ａ−２）若しくはそれら組成物を構成するエチレン・α−オレフィン共重合体（ａ１）、エチレン系重合体（ａ２）または高圧法低密度ポリエチレン（ａ３）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。
［エチレン・α―オレフィンランダム共重合体（Ｂ）］
本発明の二軸延伸エチレン重合体多層フィルムの熱融着層を形成するエチレン・α―オレフィンランダム共重合体（Ｂ）は、密度が８９０〜９１０Ｋｇ／ｍ3、好ましくは９０
０〜９０７Ｋｇ／ｍ3の範囲にある。
Ethylene polymer (A), ethylene copolymer composition (A-1), ethylene copolymer composition (A-2), or ethylene / α-olefin copolymer constituting these compositions according to the present invention (A1), ethylene-based polymer (a2) or high-pressure method low-density polyethylene (a3), as long as the object of the present invention is not impaired, commonly used antioxidants, weathering stabilizers, antistatic agents, antifogging agents An additive such as an anti-blocking agent, a lubricant, a nucleating agent, a pigment, or other polymers can be blended as necessary.
[Ethylene / α-olefin random copolymer (B)]
The ethylene / α-olefin random copolymer (B) forming the heat-sealing layer of the biaxially stretched ethylene polymer multilayer film of the present invention has a density of 890 to 910 kg / m 3 , preferably 90.
It is in the range of 0 to 907 Kg / m 3 .
密度が８９０Ｋｇ／ｍ3未満のエチレン・α―オレフィンランダム共重合体は二軸延伸
エチレン重合体多層フィルムを製造する際、特に後述のフラット方式（テンター方式）により二軸延伸する場合に延伸ロールあるいはテンタークリップに融着する虞があり、また、得られる二軸延伸エチレン重合体多層フィルムもブロッキングし易い。一方、密度が９１０Ｋｇ／ｍ3を超えるエチレン・α―オレフィンランダム共重合体は得られる二軸延伸
エチレン重合体多層フィルムのヒートシール性が劣る。
An ethylene / α-olefin random copolymer having a density of less than 890 kg / m 3 is used to produce a biaxially stretched ethylene polymer multilayer film, particularly when it is biaxially stretched by the flat method (tenter method) described later, There is a possibility of fusion to the tenter clip, and the resulting biaxially stretched ethylene polymer multilayer film is also likely to be blocked. On the other hand, an ethylene / α-olefin random copolymer having a density exceeding 910 kg / m 3 is inferior in heat sealability of the resulting biaxially stretched ethylene polymer multilayer film.
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、フィルム形成能がある限り、メルトフローレート（ＭＦＲ：ＡＳＴＭ Ｄ１２３８ 荷重２１６０ｇ、温度１
９０℃）は特に限定はされないが、通常、０．５〜１０ｇ／１０分、好ましくは０．８〜５ｇ／１０分の範囲にある。
The ethylene / α-olefin random copolymer (B) according to the present invention has a melt flow rate (MFR: ASTM D1238 load 2160 g, temperature 1) as long as it has a film-forming ability.
90 ° C) is not particularly limited, but is usually in the range of 0.5 to 10 g / 10 minutes, preferably 0.8 to 5 g / 10 minutes.
また、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）は上記エチレン系重合体（ａ２）と同様にチーグラー触媒、シングルサイト触媒等を用いた従来公知の製造法により調整することができる。 Further, the ethylene / α-olefin random copolymer (B) according to the present invention can be prepared by a conventionally known production method using a Ziegler catalyst, a single site catalyst or the like in the same manner as the ethylene polymer (a2). it can.
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）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。
［二軸延伸エチレン重合体多層フィルム］
本発明の二軸延伸エチレン重合体多層フィルムは、前記エチレン系重合体（Ａ）、好ましくはエチレン共重合体組成物（Ａ−１）若しくはエチレン共重合体組成物（Ａ−２）から形成され得る二軸延伸エチレン重合体フィルム基材層の少なくとも片面に、前記エチレン・α―オレフィンランダム共重合体（Ｂ）から得られる熱融着層が積層されてなる多層フィルムである。
In the ethylene / α-olefin random copolymer (B) according to the present invention, an antioxidant, a weathering stabilizer, an antistatic agent, an antifogging agent, and an antiblocking agent which are usually used within a range not impairing the object of the present invention. Additives such as agents, lubricants, nucleating agents, pigments, or other polymers can be blended as necessary.
[Biaxially stretched ethylene polymer multilayer film]
The biaxially stretched ethylene polymer multilayer film of the present invention is formed from the ethylene polymer (A), preferably the ethylene copolymer composition (A-1) or the ethylene copolymer composition (A-2). The biaxially stretched ethylene polymer film substrate layer is a multilayer film in which a heat-sealing layer obtained from the ethylene / α-olefin random copolymer (B) is laminated on at least one surface.
本発明の二軸延伸エチレン重合体多層フィルムは、好ましくは多層フィルムのＭＤ方向の引裂き強度およびＴＤ方向の引裂き強度のうち一方を（ＴS）、他方を（ＴW）（但し、ＴS≧ＴWである。）としたときに、引裂き強度（ＴS）が８０〜１０Ｎ／ｃｍ、好ましく
は７５〜１５Ｎ／ｃｍ、特に好ましくは６０〜２０Ｎ／ｃｍ、（ＴW）／（ＴS）が０．１０〜１、好ましくは０．２０〜１の範囲にある二軸延伸エチレン重合体多層フィルムであり、好ましくはＭＤ方向およびＴＤ方向のうちの一方向の延伸倍率が３〜１４倍、好ましくは５〜１０倍及び他方向の延伸倍率が３〜１４倍、好ましくは５〜１０倍の範囲にある。
In the biaxially stretched ethylene polymer multilayer film of the present invention, preferably, one of the tear strength in the MD direction and the tear strength in the TD direction of the multilayer film is (T S ) and the other is (T W ) (where T S ≧ T W. ), the tear strength (T S ) is 80 to 10 N / cm, preferably 75 to 15 N / cm, particularly preferably 60 to 20 N / cm, (T W ) / (T S ). Is a biaxially stretched ethylene polymer multilayer film in the range of 0.10 to 1, preferably 0.20 to 1, preferably a unidirectional stretch ratio of 3 to 14 times in the MD direction and the TD direction, Preferably, the draw ratio in the other direction is 5 to 10 times, preferably 3 to 14 times, preferably 5 to 10 times.
なお、引裂き強度は、後述するようにＪＩＳ Ｐ８１１６及びＡＳＴＭ １９２２を参考にして、東洋精機製作所製軽荷重引裂試験機を用いて測定される。
引裂き強度（ＴS）が８０Ｎ／ｃｍを越える二軸延伸多層フィルムは、引裂き強度が強
く、易引裂き性に劣ったフィルムとなり、１０Ｎ／ｃｍ未満の二軸延伸多層フィルムは引裂き強度が弱過ぎて、包装材料として耐え得ない虞がある。（ＴW）／（ＴS）が０．１０未満の二軸延伸多層フィルムは引裂き性に方向性が生じ、縦／横何れかの方向に裂け得ないフィルムとなる。
The tear strength is measured using a light load tear tester manufactured by Toyo Seiki Seisakusho with reference to JIS P8116 and ASTM 1922 as described later.
A biaxially stretched multilayer film having a tear strength (T S ) of more than 80 N / cm has a high tear strength and is inferior to easy tear, and a biaxially stretched multilayer film having a tear strength of less than 10 N / cm has a too low tear strength. There is a fear that it cannot be endured as a packaging material. A biaxially stretched multilayer film having (T W ) / (T S ) of less than 0.10 has a directionality in tearability, and becomes a film that cannot be torn in either the longitudinal or transverse direction.
一方向の延伸倍率が５倍未満又は他方向の延伸倍率が３倍未満の二軸延伸多層フィルムは引裂き強度が強く、本発明の目的を達成し得ない虞がある。
本発明の二軸延伸エチレン重合体多層フィルムは、好ましくは透明性（ヘイズ）が０．５〜１５％、引張弾性率が２００ＭＰａ以上、インパクト強度が１５ＫＪ／ｍ以上、１２０℃での熱収縮率が２０％以上の範囲にある。本発明の二軸延伸エチレン重合体多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、二軸延伸エチレン重合体フィルム基材層の厚さが約１０〜２００μｍ、好ましくは約１５〜１３０μｍ、熱融着層の厚さが約０．２〜６０μｍ、好ましくは約０．４〜４０μｍの範囲、二軸延伸エチレン重合体多層フィルム全体の厚さが、約１０〜３２０μｍ、好ましくは約１５〜２３０μｍの範囲にある。
A biaxially stretched multilayer film having a stretch ratio in one direction of less than 5 times or a stretch ratio in other directions of less than 3 times has a high tear strength and may not achieve the object of the present invention.
The biaxially stretched ethylene polymer multilayer film of the present invention preferably has a transparency (haze) of 0.5 to 15%, a tensile elastic modulus of 200 MPa or more, an impact strength of 15 KJ / m or more, and a heat shrinkage rate at 120 ° C. Is in the range of 20% or more. Although the thickness of the biaxially stretched ethylene polymer multilayer film of the present invention can be variously determined depending on the application, the thickness of the biaxially stretched ethylene polymer film substrate layer is usually about 10 to 200 μm, preferably about 15 to 130 μm. The thickness of the heat-sealing layer is about 0.2 to 60 μm, preferably about 0.4 to 40 μm, and the total thickness of the biaxially stretched ethylene polymer multilayer film is about 10 to 320 μm, preferably about 15 It is in the range of ~ 230 μm.
本発明の二軸延伸エチレン重合体多層フィルムの熱融着層は二軸延伸エチレン重合体フィルム基材層の片面に形成されていても、両面に形成されていてもよい。熱融着層が両面に形成された二軸延伸エチレン重合体多層フィルムはオーバーラップ包装用フィルム、水物充填用包装体用シーラントフィルム、あるいは、貼り合わせ用基材フィルムとして使用
し得る。
The heat fusion layer of the biaxially stretched ethylene polymer multilayer film of the present invention may be formed on one side or both sides of the biaxially stretched ethylene polymer film substrate layer. The biaxially stretched ethylene polymer multilayer film in which the heat-sealing layer is formed on both sides can be used as an overlap packaging film, a water-filling packaging sealant film, or a bonding base film.
また、本発明の二軸延伸エチレン重合体多層フィルムの二軸延伸エチレン重合体フィルム基材層は一層であっても二層以上、即ち、中間層とラミネート層の多層であってもよい。 The biaxially stretched ethylene polymer film base material layer of the biaxially stretched ethylene polymer multilayer film of the present invention may be a single layer or two or more layers, that is, a multilayer of an intermediate layer and a laminate layer.
本発明の二軸延伸エチレン重合体多層フィルムは、印刷性あるいは後述の他の熱可塑性樹脂フィルムを含め他の基材との接着性を改良するために、二軸延伸エチレン重合体多層フィルムの他の片面、基材層が二層以上であればラミネート層の表面を、両面が熱融着層であればその一方の表面を、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等の表面活性化処理を行っておいてもよい。 The biaxially stretched ethylene polymer multilayer film of the present invention is used in addition to the biaxially stretched ethylene polymer multilayer film in order to improve the printability or adhesion to other substrates including other thermoplastic resin films described later. If one side of the substrate layer is two or more layers, the surface of the laminate layer, and if both sides are heat fusion layers, one surface thereof, for example, corona treatment, flame treatment, plasma treatment, undercoat treatment, etc. A surface activation treatment may be performed.
本発明の二軸延伸エチレン重合体多層フィルムの他の片面（ラミネート面）に、両面が熱融着層であればその一方の表面に熱可塑性樹脂フィルムが積層されていてもよい。
かかる熱可塑性樹脂フィルムとしては、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から得られるフィルムを例示することができる。
If the both surfaces of the biaxially stretched ethylene polymer multilayer film of the present invention (laminate surface) are heat-sealing layers, a thermoplastic resin film may be laminated on one surface thereof.
Examples of the thermoplastic resin film include 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 a mixture thereof. The film to be used can be exemplified.
また、かかる熱可塑性樹脂フィルムは、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種または２種以上の共押し出し成形、押出しラミネート、ドライラミネート、サーマルラミネート等で得られる積層体であっても良い。中でも、二軸延伸熱可塑性フィルム、とくにポリプロピレン、ポリエチレンテレフタレート、ポリアミドからなる二軸延伸熱可塑性フィルムが好ましい。 The thermoplastic resin film may be an unstretched film or a stretched film, or a laminate obtained by one or more types of coextrusion molding, extrusion lamination, dry lamination, thermal lamination, and the like. It may be the body. Among them, a biaxially stretched thermoplastic film, particularly a biaxially stretched thermoplastic film made of polypropylene, polyethylene terephthalate, or polyamide is preferable.
本発明の二軸延伸エチレン重合体多層フィルムには、紙、アルミニウム箔等からなる基材と積層してもよい。
［二軸延伸エチレン重合体多層フィルムの製造方法］
本発明の二軸延伸エチレン重合体多層フィルムは、種々公知の方法、例えば、二軸延伸エチレン重合体フィルム基材層を形成する前記エチレン系重合体（Ａ）と熱融着層を形成する前記エチレン・α―オレフィンランダム共重合体（Ｂ）とを共押出し成形し、チューブラー方式又はフラット方式（テンター方式）により、上記範囲で縦（ＭＤ）方向及び横（ＴＤ）方向に二軸延伸することにより得られる。二軸延伸は同時二軸延伸でも、逐次二軸延伸でもよい。これら方式の中でも、フラット方式により得られる二軸延伸エチレン重合体多層フィルムが、より透明性に優れるので好ましい。
The biaxially stretched ethylene polymer multilayer film of the present invention may be laminated with a substrate made of paper, aluminum foil or the like.
[Method for producing biaxially stretched ethylene polymer multilayer film]
The biaxially stretched ethylene polymer multilayer film of the present invention is formed by various known methods, for example, the above-mentioned ethylene-based polymer (A) that forms a biaxially stretched ethylene polymer film substrate layer and the above-mentioned heat-bonding layer. Coextrusion molding of ethylene / α-olefin random copolymer (B) and biaxial stretching in the longitudinal (MD) and transverse (TD) directions within the above range by the tubular method or flat method (tenter method) Can be obtained. Biaxial stretching may be simultaneous biaxial stretching or sequential biaxial stretching. Among these methods, a biaxially stretched ethylene polymer multilayer film obtained by a flat method is preferable because it is more excellent in transparency.
フラット方式による場合は、通常、押出し成形して得た多層シートを９０〜１２５℃の温度範囲で縦方向に延伸した後、９０〜１３０℃の温度範囲で横方向に延伸することにより得られる。二軸延伸した後は、用途により、８０〜１４０℃の温度範囲でヒートセットを行ってもよい。ヒートセットの温度は目的とする熱収縮率に応じて変える事が出来る。 In the case of the flat method, it is usually obtained by stretching a multilayer sheet obtained by extrusion molding in the longitudinal direction in a temperature range of 90 to 125 ° C and then stretching in the lateral direction in a temperature range of 90 to 130 ° C. After biaxial stretching, heat setting may be performed in a temperature range of 80 to 140 ° C. depending on the application. The temperature of the heat set can be changed according to the desired heat shrinkage rate.
本発明の二軸延伸エチレン重合体多層フィルムの非熱融着層面に、両面が熱融着層であればその一方の表面に他の熱可塑性樹脂フィルムを積層する場合は種々公知の方法、例えば、必要二応じてコロナ処理した二軸延伸エチレン重合体多層フィルムのラミネート面あるいは両面が熱融着層であればその一方の表面にウレタン型接着剤、イソシアネート系接着剤を塗布した後、熱可塑性樹脂フィルムとドライラミネートする方法あるいは、ラミネート面あるいは両面が熱融着層と熱可塑性樹脂フィルムとを高圧法低密度ポリエチレンを
用いて押出しラミネートする方法を採り得る。
When both surfaces of the biaxially stretched ethylene polymer multilayer film of the present invention are heat fusion layers, if the other thermoplastic resin film is laminated on one surface, various known methods, for example, If the laminate surface or both surfaces of the biaxially stretched ethylene polymer multilayer film subjected to corona treatment if necessary are heat-sealable layers, after applying urethane type adhesive or isocyanate adhesive on one surface, thermoplasticity A method of dry laminating with a resin film, or a method of extruding and laminating a heat-sealing layer and a thermoplastic resin film on a laminating surface or both sides using a high-pressure low-density polyethylene can be employed.
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。
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）メルトフローレート（ｇ／１０分）
ＡＳＴＭ Ｄ１２３８に準拠し、荷重２１６０ｇ、温度１９０℃の条件で測定した。
（２）密度（Ｋｇ／ｍ3）
ＭＦＲを測定して得た重合体ストランドを１２０℃で２時間処理し、１時間かけて室温（２３℃）まで徐冷した後、ＪＩＳ Ｋ ７１１２に準拠し、Ｄ法（密度勾配管）により測定した。
（３）ヘイズ（曇価）（％）
Ｈａｚｅ Ｍｅｔｅｒ（日本電色工業社製 ＮＤＨ−２０００）を使用してフィルム１枚の曇り度をＪＩＳ Ｋ ７１３６に準拠して測定した。
（４）引張試験
多層フィルムから長さ方向がフィルムの流れ方向（ＭＤ）、幅方向（ＴＤ）となるように１５ｍｍ幅、２００ｍｍ長さの短冊状の試験片を切出し、オリエンテック社製テンシロンＲＴ１２２５型を使用してＪＩＳ Ｋ ７１２７に準拠してヤング率と破断強伸度を測定した。
（５）引裂き強度（Ｎ／ｃｍ）
軽荷重引裂試験機（東洋精機製作所製：振り子の左端に容量ウェイトＢ：７９ｇを取り付け）を使用し、多層フィルムから引裂き方向に長さ６３．５ｍｍ（長辺）及び引裂き方向と直角方向に幅５０ｍｍ（短辺）の長方形の試験片を切出し、短辺の中央に端から１２．７ｍｍの切り込みを入れて複数枚の試験片を用意する。しかる後、試験機の指針（置き針）が２０〜８０の範囲に収まるように、試験片を複数枚重ねて予備テストを行い、測定に用いる試験片の枚数を調整した後、引裂き試験を行い、以下の式により引裂き強度（Ｎ／ｃｍ）を求めた。なお、試験機の測定レンジ（Ｒ）は２００とした。
EXAMPLES Next, although this invention is demonstrated through an Example, this invention is not limited by these Examples.
Various test methods and evaluation methods in the present invention are as follows.
(1) Melt flow rate (g / 10 min)
Based on ASTM D1238, the load was 2160 g and the temperature was 190 ° C.
(2) Density (Kg / m 3 )
The polymer strand obtained by measuring MFR was treated at 120 ° C. for 2 hours, slowly cooled to room temperature (23 ° C.) over 1 hour, and then measured by the D method (density gradient tube) according to JIS K 7112. did.
(3) Haze (cloudiness value) (%)
The haze of one film was measured according to JIS K 7136 using Haze Meter (NDH-2000 manufactured by Nippon Denshoku Industries Co., Ltd.).
(4) Tensile test A strip-shaped test piece having a width of 15 mm and a length of 200 mm was cut out from the multilayer film so that the length direction is the film flow direction (MD) and the width direction (TD), and Tensilon RT1225 manufactured by Orientec Co., Ltd. Using a mold, Young's modulus and tensile strength at break were measured in accordance with JIS K 7127.
(5) Tear strength (N / cm)
Use a light-load tear tester (Toyo Seiki Seisakusho: capacity weight B: 79g attached to the left end of the pendulum), length 63.5mm (long side) in the tear direction from the multilayer film, and width in the direction perpendicular to the tear direction A rectangular test piece of 50 mm (short side) is cut out, and a 12.7 mm cut is made in the center of the short side from the end to prepare a plurality of test pieces. After that, a preliminary test is performed by stacking a plurality of test pieces so that the indicator (placement needle) of the testing machine is within the range of 20 to 80, and the tear test is performed after adjusting the number of test pieces used for measurement. The tear strength (N / cm) was determined by the following formula. The measurement range (R) of the testing machine was 200.
Ｔ＝（Ａ×０．００１×９．８１×Ｒ／１００）／（ｔ）
Ｔ：引裂強度（Ｎ／ｃｍ）
Ａ：指針の指した値（ｇ）
ｔ：重ねた試験片の合計厚み（ｃｍ）
（６）衝撃強度（ＫＪ／ｍ）
東洋精機製作所製のフィルムインパクトテスターを使用し、先端形状は０．５インチ径半球を使用し、多層フィルムから１００ｍｍ四方の正方形の試験片を切り出し、２３℃の雰囲気温度化にてインパクト強度を測定した。
（７）熱収縮率（％）
多層フィルムの長さ方向がフィルムの流れ方向（ＭＤ）、幅方向（ＴＤ）となるように１５ｍｍ幅、２００ｍｍ長さの短冊状の試験片を切り出し、１５０ｍｍ間隔に穴を開け、これを所定温度のオーブン内に１５分間放置後、取り出して室温まで放冷した後に穴の距離を測定し収縮率を測定した。
（８）耐屈曲性
テスター産業製のゲルボフレックステスターを使用し、多層フィルムから２１０ｍｍ幅、２９７ｍｍ長さの試験片を切り出し、屈曲角度４４０度、屈曲速度４０回／分で、２３℃、−１０℃、−３０℃の各雰囲気下で、１０００回および３０００回の屈曲試験を行った後、屈曲試験後の試験片で袋をつくり、三菱ガス化学製のエージレスシールチェックでピンホール数を測定した。
（９）ヒートシール強度
東洋精機製ヒートシールテスターを使用し、多層フィルムから１００ｍｍ幅、１５０ｍ
ｍ長さの試験片を切り出し、半分に折ってヒーターが８０℃〜１４０℃で圧力が０．２ＭＰａで、シール時間が１秒で、ヒートシールを行った後、シールした試験片を幅１５ｍｍの試験片に切り出し、オリエンテック製テンシロンＲＴ１２２５型を使用し、剥離強度を測定した。
（１０）突刺し強度
オリエンテック製テンシロンＲＴ１２２５型を使用し、多層フィルムから６０ｍｍ幅、２００〜３００ｍｍ程度の試験片を切り出し、ＪＩＳ Ｚ１７０７に準拠して、突き刺し強度を測定した。
T = (A × 0.001 × 9.81 × R / 100) / (t)
T: Tear strength (N / cm)
A: Value indicated by the pointer (g)
t: Total thickness of stacked specimens (cm)
(6) Impact strength (KJ / m)
Using a film impact tester manufactured by Toyo Seiki Seisakusho Co., Ltd., using a 0.5 inch diameter hemisphere at the tip, cutting out a 100 mm square test piece from the multilayer film, and measuring the impact strength at an ambient temperature of 23 ° C did.
(7) Thermal shrinkage (%)
A strip-shaped test piece of 15 mm width and 200 mm length is cut out so that the length direction of the multilayer film is the film flow direction (MD) and the width direction (TD), and holes are formed at intervals of 150 mm. The sample was left in the oven for 15 minutes, taken out and allowed to cool to room temperature, and then the distance between the holes was measured to measure the shrinkage.
(8) Bending resistance Using a tester industry gelvo flex tester, a test piece having a width of 210 mm and a length of 297 mm was cut out from the multilayer film, and the bending angle was 440 degrees and the bending speed was 40 times / min. After each 1000 and 3000 bend tests in each atmosphere of 10 ° C and -30 ° C, make a bag with the test piece after the bend test and measure the number of pinholes with an ageless seal check made by Mitsubishi Gas Chemical did.
(9) Heat seal strength Use heat seal tester made by Toyo Seiki, 100mm wide, 150m from multilayer film
An m-length test piece was cut out, folded in half, the heater was 80 ° C. to 140 ° C., the pressure was 0.2 MPa, the sealing time was 1 second, and after heat sealing, the sealed test piece was 15 mm wide. It cut out to the test piece and peel strength was measured using the tensilon RT1225 type made from Orientec.
(10) Puncture strength Using a Tensilon RT1225 type manufactured by Orientec, a test piece having a width of about 60 mm and about 200 to 300 mm was cut out from the multilayer film, and the puncture strength was measured according to JIS Z1707.
本発明の実施例及び比較例で用いた重合体及び組成物は次の通りである。
（ｉ）エチレン・α−オレフィンランダム共重合体（ａ１）
（１）エチレン・１−ヘキセンランダム共重合体（ａ１−１）：メタロセン触媒を用いた重合体、密度；９０５Ｋｇ／ｍ3、ＭＦＲ；０．５ｇ／１０分。
The polymers and compositions used in the examples and comparative examples of the present invention are as follows.
(I) Ethylene / α-olefin random copolymer (a1)
(1) Ethylene / 1-hexene random copolymer (a1-1): polymer using metallocene catalyst, density: 905 Kg / m 3 , MFR: 0.5 g / 10 min.
（２）エチレン・１−ヘキセンランダム共重合体（ａ１−２）：メタロセン触媒を用いた重合体、密度；９１５Ｋｇ／ｍ3、ＭＦＲ；０．５ｇ／１０分。
（ii）エチレン・α−オレフィンランダム共重合体（ｂ）
（１）エチレン・１−ヘキセンランダム共重合体（ｂ−１）：メタロセン触媒を用いた重合体、密度；９１８Ｋｇ／ｍ3、ＭＦＲ；４．０ｇ／１０分、融解熱量（ΔＨT）；１０３．２Ｊ／ｇ、融解開始温度〜１１０℃の範囲の融解熱量（ΔＨL）；６９．８Ｊ／ｇ、
１１０℃〜融解終了温度の範囲の融解熱量（ΔＨH）；３３．４Ｊ／ｇ及び（ΔＨH）／（ΔＨL）；０．４８。
（iii）エチレン系重合体（ａ２）
（ａ２−１）
（１）エチレン・１−ヘキセンランダム共重合体（ａ２−１−１）：メタロセン触媒を用いた重合体、密度；９３０Ｋｇ／ｍ3、ＭＦＲ；６０ｇ／１０分。
(2) Ethylene / 1-hexene random copolymer (a1-2): polymer using metallocene catalyst, density: 915 Kg / m 3 , MFR: 0.5 g / 10 min.
(Ii) ethylene / α-olefin random copolymer (b)
(1) Ethylene / 1-hexene random copolymer (b-1): polymer using metallocene catalyst, density: 918 Kg / m 3 , MFR: 4.0 g / 10 min, heat of fusion (ΔH T ); 103 .2 J / g, heat of fusion (ΔH L ) in the range of melting onset temperature to 110 ° C .; 69.8 J / g,
Heat of fusion (ΔH H ) in the range of 110 ° C. to end of melting temperature; 33.4 J / g and (ΔH H ) / (ΔH L ); 0.48.
(Iii) Ethylene polymer (a2)
(A2-1)
(1) Ethylene / 1-hexene random copolymer (a2-1-1): polymer using metallocene catalyst, density: 930 Kg / m 3 , MFR: 60 g / 10 min.
（２）エチレン・１−ヘキセンランダム共重合体（ａ２−１−２）：メタロセン触媒を用いた重合体、密度；９４５Ｋｇ／ｍ3、ＭＦＲ；６０ｇ／１０分。
（ａ２−２）
（１）エチレン・プロピレン・１−ブテンランダム共重合体（ａ２−２−１）：チーグラー触媒を用いた重合体、密度；９５８Ｋｇ／ｍ3、ＭＦＲ；０．９ｇ／１０分。
（iv）高圧法低密度ポリエチレン（ａ３）
（１）高圧法低密度ポリエチレン（ａ３−１）：密度；９２３Ｋｇ／ｍ3、ＭＦＲ；０
．６ｇ／１０分。
(2) Ethylene / 1-hexene random copolymer (a2-1-2): polymer using metallocene catalyst, density: 945 Kg / m 3 , MFR: 60 g / 10 min.
(A2-2)
(1) Ethylene / propylene / 1-butene random copolymer (a2-2-1): polymer using Ziegler catalyst, density: 958 Kg / m 3 , MFR: 0.9 g / 10 min.
(Iv) High pressure method low density polyethylene (a3)
(1) High pressure method low density polyethylene (a3-1): density; 923 kg / m 3 , MFR; 0
. 6 g / 10 minutes.
（２）高圧法低密度ポリエチレン（ａ３−２）：密度；９１７Ｋｇ／ｍ3、ＭＦＲ；７
ｇ／１０分。
（ｖ）エチレン重合体組成物（Ａ−１）
（１）エチレン重合体組成物（Ａ−１−１）
前記エチレン・１−ヘキセンランダム共重合体（ａ１−２）及びエチレン・１−ヘキセンランダム共重合体（ａ２−１−２）を６０：４０（重量部）の割合でドライブレンドした後、池貝鉄工社製二軸押出機（４６ｍｍφ）を用いて、温度１９０℃、押出量５０Ｋｇ／時の条件で溶融混練し、エチレン重合体組成物（Ａ−１−１）を得た。
(2) High pressure method low density polyethylene (a3-2): Density; 917 Kg / m 3 , MFR; 7
g / 10 minutes.
(V) Ethylene polymer composition (A-1)
(1) Ethylene polymer composition (A-1-1)
After dry blending the ethylene / 1-hexene random copolymer (a1-2) and the ethylene / 1-hexene random copolymer (a2-1-2) at a ratio of 60:40 (parts by weight), Ikekai Iron Works Using a twin screw extruder (46 mmφ), melt kneading was performed at a temperature of 190 ° C. and an extrusion rate of 50 kg / hour to obtain an ethylene polymer composition (A-1-1).
得られたエチレン重合体組成物（Ａ−１−１）は密度；９２５Ｋｇ／ｍ3、ＭＦＲ；２
．５ｇ／１０分、融解熱量（ΔＨT）；１１７．５Ｊ／ｇ、融解開始温度〜１１０℃の範
囲の融解熱量（ΔＨL）；６５．３Ｊ／ｇ、１１０℃〜融解終了温度の範囲の融解熱量（
ΔＨH）；５２．２Ｊ／ｇ及び（ΔＨH）／（ΔＨL）；０．８０であった。
（vi）エチレン重合体組成物（Ａ−２）
（１）エチレン重合体組成物（Ａ−２−１）
前記エチレン・１−ヘキセンランダム共重合体（ａ１−２）、エチレン・１−ヘキセンランダム共重合体（ａ２−１−２）及び高圧法低密度ポリエチレン（ａ３−１）を５１：３４：１５（重量部）の割合でドライブレンドした後、池貝鉄工社製二軸押出機（４６ｍｍφ）を用いて、温度１９０℃、押出量５０Ｋｇ／時の条件で溶融混練し、エチレン重合体組成物（Ａ−２−１）を得た。
The obtained ethylene polymer composition (A-1-1) has a density of 925 Kg / m 3 and an MFR of 2
. 5 g / 10 min, heat of fusion (ΔH T ); 117.5 J / g, heat of fusion in the range of melting onset temperature to 110 ° C. (ΔH L ); 65.3 J / g, melting in the range of 110 ° C. to end of melting temperature Calorie (
ΔH H ); 52.2 J / g and (ΔH H ) / (ΔH L ); 0.80.
(Vi) Ethylene polymer composition (A-2)
(1) Ethylene polymer composition (A-2-1)
The ethylene / 1-hexene random copolymer (a1-2), the ethylene / 1-hexene random copolymer (a2-1-2) and the high-pressure low-density polyethylene (a3-1) were mixed with 51:34:15 ( After being dry blended at a ratio of parts by weight), the mixture was melt-kneaded using a twin screw extruder (46 mmφ) manufactured by Ikekai Tekko Co., Ltd. under conditions of a temperature of 190 ° C. and an extrusion rate of 50 kg / hour, to obtain an ethylene polymer composition (A- 2-1) was obtained.
得られたエチレン重合体組成物（Ａ−２−１）は密度；９２５Ｋｇ／ｍ3、ＭＦＲ；が
１．９ｇ／１０分、融解熱量（ΔＨT）；１２６．０Ｊ／ｇ、融解開始温度〜１１０℃の
範囲の融解熱量（ΔＨL）；７６．１Ｊ／ｇ、１１０℃〜融解終了温度の範囲の融解熱量
（ΔＨH）；４９．９Ｊ／ｇ及び（ΔＨH）／（ΔＨL）；０．６６であった。
The obtained ethylene polymer composition (A-2-1) had a density; 925 Kg / m 3 , MFR; 1.9 g / 10 min, heat of fusion (ΔH T ); 126.0 J / g, melting start temperature to Heat of fusion in the range of 110 ° C. (ΔH L ); 76.1 J / g, heat of fusion in the range of 110 ° C. to end of melting temperature (ΔH H ); 49.9 J / g and (ΔH H ) / (ΔH L ); It was 0.66.
（２）エチレン重合体組成物（Ａ−２−２）
前記エチレン・１−ヘキセンランダム共重合体（ａ１−１）、エチレン・１−ヘキセンランダム共重合体（ａ２−１−１）、エチレン・プロピレン・１−ブテンランダム共重合体（ａ２−２−１）及び高圧法低密度ポリエチレン（ａ３−２）を３６：２４：２５：１５（重量部）の割合でドライブレンドした後、池貝鉄工社製二軸押出機（４６ｍｍφ）を用いて、温度１９０℃、押出量５０Ｋｇ／時の条件で溶融混練し、エチレン重合体組成物（Ａ−２−２）を得た。
(2) Ethylene polymer composition (A-2-2)
The ethylene / 1-hexene random copolymer (a1-1), ethylene / 1-hexene random copolymer (a2-1-1), ethylene / propylene / 1-butene random copolymer (a2-2-1) ) And high-pressure low-density polyethylene (a3-2) at a ratio of 36: 24: 25: 15 (parts by weight), and then using a twin screw extruder (46 mmφ) manufactured by Ikekai Tekko Co., Ltd. at a temperature of 190 ° C. The mixture was melt-kneaded under conditions of an extrusion rate of 50 kg / hour to obtain an ethylene polymer composition (A-2-2).
得られたエチレン重合体組成物（Ａ−２−２）は密度；９２７Ｋｇ／ｍ3、ＭＦＲ；２
．０ｇ／１０分、融解熱量（ΔＨT）；１２７．１Ｊ／ｇ、融解開始温度〜１１０℃の範
囲の融解熱量（ΔＨL）；６３．５５Ｊ／ｇ、１１０℃〜融解終了温度の範囲の融解熱量
（ΔＨH）；６３．５５Ｊ／ｇ及び（ΔＨH）／（ΔＨL）；１．００であった。
（vii）エチレン・α―オレフィンランダム共重合体（Ｂ）
（１）エチレン・１−オクテンランダム共重合体（Ｂ−１）；メタロセン触媒にて重合されたもの；密度 ９０３ｋｇ／ｍ3、ＭＦＲ ３．８ｇ／１０ｍｉｎ．。
（２）エチレン・１−オクテンランダム共重合体（Ｂ−２）；メタロセン触媒にて重合されたもの；密度 ９０９ｋｇ／ｍ3、ＭＦＲ ２．０ｇ／１０ｍｉｎ。
（３）エチレン・１−ブテンランダム共重合体（Ｂ−３）；メタロセン触媒にて重合されたもの；密度８８５ｋｇ／ｍ3、ＭＦＲ２．０ｇ／１０ｍｉｎ
（４）エチレン・α―オレフィンランダム共重合体組成物（Ｂ−４）；Ｂ−１とＢ−３を６０／４０重量％でブレンドしたもの；密度８９２ｋｇ／ｍ3、ＭＦＲ２．６ｇ／１０ｍ
ｉｎ。
（viii）エチレン重合体組成物（Ｃ）
（１）エチレン重合体組成物（Ｃ−１）
エチレン・１−オクテンランダム共重合体組成物（ダウ・ケミカル社製、商品名 エリート ５２２０Ｇ）、密度；９１７Ｋｇ／ｍ3、ＭＦＲ；３．５ｇ／１０分、融解熱量（
ΔＨT）；１０１．５Ｊ／ｇ、融解開始温度〜１１０℃の範囲の融解熱量（ΔＨL）；７１．７４Ｊ／ｇ、１１０℃〜融解終了温度の範囲の融解熱量（ΔＨH）；２９．７６Ｊ／ｇ
及び（ΔＨH）／（ΔＨL）；０．４１。
実施例１
二軸延伸エチレン重合体フィルム基材層用のエチレン系重合体（Ａ）として、前記エチレン重合体組成物（Ａ−２−１）を、及び熱融着層用のエチレン・α―オレフィンランダム共重合体（Ｂ）としてエチレン・１−オクテンランダム共重合体（Ｂ−１）を用い、３台の押出を備えた二軸延伸フィルム成形機を用いて溶融押出しし、Ｔ−ダイで賦形した後、冷却ロール上にて急冷し厚さ約２ｍｍの三層シート（Ｂ−１／Ａ−２−１／Ｂ−１＝５／９０／５の層比）を得た。このシートを１１２℃に加熱しフィルムの流れ方向（縦方向）に５倍延伸した。この５倍延伸したシートを１２０℃に加熱し流れ方向に対して直交する方向（横方向）に８．５倍延伸して厚さ４７μｍの二軸延伸エチレン重合体多層フィル
ムを得た。かかる二軸延伸エチレン重合体多層フィルムの物性等を前記記載の方法で測定した。
The resulting ethylene polymer composition (A-2-2) has a density of 927 Kg / m 3 and an MFR of 2
. 0 g / 10 minutes, heat of fusion (ΔH T ); 127.1 J / g, heat of fusion in the range of melting onset temperature to 110 ° C. (ΔH L ); 63.55 J / g, melting in the range of 110 ° C. to end of melting temperature The amount of heat (ΔH H ); 63.55 J / g and (ΔH H ) / (ΔH L ); 1.00.
(Vii) Ethylene / α-olefin random copolymer (B)
(1) Ethylene / 1-octene random copolymer (B-1); polymerized with a metallocene catalyst; density 903 kg / m 3 , MFR 3.8 g / 10 min. .
(2) Ethylene / 1-octene random copolymer (B-2); polymerized with a metallocene catalyst; density 909 kg / m 3 , MFR 2.0 g / 10 min.
(3) Ethylene / 1-butene random copolymer (B-3); polymerized by metallocene catalyst; density 885 kg / m 3 , MFR 2.0 g / 10 min
(4) Ethylene / α-olefin random copolymer composition (B-4); B-1 and B-3 blended at 60/40 wt%; density 892 kg / m 3 , MFR 2.6 g / 10 m
in.
(Viii) Ethylene polymer composition (C)
(1) Ethylene polymer composition (C-1)
Ethylene / 1-octene random copolymer composition (manufactured by Dow Chemical Company, trade name: Elite 5220G), density: 917 Kg / m 3 , MFR: 3.5 g / 10 minutes, heat of fusion (
ΔH T ); 101.5 J / g, heat of fusion in the range of melting onset temperature to 110 ° C. (ΔH L ); 71.74 J / g, heat of fusion in the range of 110 ° C. to end of melting temperature (ΔH H ); 76J / g
And (ΔH H ) / (ΔH L ); 0.41.
Example 1
As the ethylene polymer (A) for the biaxially stretched ethylene polymer film base material layer, the ethylene polymer composition (A-2-1) and the ethylene / α-olefin random copolymer for the heat fusion layer are used. The ethylene / 1-octene random copolymer (B-1) was used as the polymer (B), melt-extruded using a biaxially stretched film molding machine equipped with three extrusions, and shaped with a T-die. Thereafter, it was rapidly cooled on a cooling roll to obtain a three-layer sheet having a thickness of about 2 mm (layer ratio of B-1 / A-2-1 / B-1 = 5/90/5). This sheet was heated to 112 ° C. and stretched 5 times in the film flow direction (longitudinal direction). The sheet stretched 5 times was heated to 120 ° C. and stretched 8.5 times in the direction perpendicular to the flow direction (lateral direction) to obtain a biaxially stretched ethylene polymer multilayer film having a thickness of 47 μm. The physical properties of the biaxially stretched ethylene polymer multilayer film were measured by the method described above.
結果を表１に示す。
実施例２
二軸延伸エチレン重合体フィルム基材層用のエチレン系重合体（Ａ）として、前記エチレン重合体組成物（Ａ−２−２）を、及び熱融着層用のエチレン・α―オレフィンランダム共重合体（Ｂ）としてエチレン・１−オクテンランダム共重合体（Ｂ−１）を用い、３台の押出を備えた二軸延伸フィルム成形機を用いて溶融押出しし、Ｔ−ダイで賦形した後、冷却ロール上にて急冷し厚さ約１．６ｍｍの三層シート（Ｂ−１／Ａ−２−２／Ｂ−１＝５／９０／５の層比）を得た。このシートを１１０℃に加熱しフィルムの流れ方向（縦方向）に６倍延伸した。この６倍延伸したシートを１１６℃に加熱し流れ方向に対して直交する方向（横方向）に８．５倍延伸して厚さ３２μｍの二軸延伸エチレン重合体多層フィルムを得た。かかる二軸延伸エチレン重合体多層フィルムの物性等を前記記載の方法で測定した。
The results are shown in Table 1.
Example 2
As the ethylene polymer (A) for the biaxially stretched ethylene polymer film base material layer, the ethylene polymer composition (A-2-2) and the ethylene / α-olefin random copolymer for the heat fusion layer are used. The ethylene / 1-octene random copolymer (B-1) was used as the polymer (B), melt-extruded using a biaxially stretched film molding machine equipped with three extrusions, and shaped with a T-die. Thereafter, it was rapidly cooled on a cooling roll to obtain a three-layer sheet (B-1 / A-2-2 / B-1 = 5/90/5 layer ratio) having a thickness of about 1.6 mm. This sheet was heated to 110 ° C. and stretched 6 times in the film flow direction (longitudinal direction). This 6-fold stretched sheet was heated to 116 ° C. and stretched 8.5 times in the direction perpendicular to the flow direction (lateral direction) to obtain a biaxially stretched ethylene polymer multilayer film having a thickness of 32 μm. The physical properties of the biaxially stretched ethylene polymer multilayer film were measured by the method described above.
結果を表１に示す。
実施例３
二軸延伸エチレン重合体フィルム基材層用のエチレン系重合体（Ａ）として、前記エチレン重合体組成物（Ａ−２−２）を、及び熱融着層用のエチレン・α―オレフィンランダム共重合体（Ｂ）としてエチレン・１−オクテンランダム共重合体（Ｂ−２）を用い、３台の押出を備えた二軸延伸フィルム成形機を用いて溶融押出しし、Ｔ−ダイで賦形した後、冷却ロール上にて急冷し厚さ約１．６ｍｍの三層シート（Ｂ−２／Ａ−２−２／Ｂ−２＝５／９０／５の層比）を得た。このシートを１１０℃に加熱しフィルムの流れ方向（縦方向）に６倍延伸した。この６倍延伸したシートを１１６℃に加熱し流れ方向に対して直交する方向（横方向）に８．５倍延伸して厚さ３１μｍの二軸延伸エチレン重合体多層フィルムを得た。かかる二軸延伸エチレン重合体多層フィルムの物性等を前記記載の方法で測定した。
The results are shown in Table 1.
Example 3
As the ethylene polymer (A) for the biaxially stretched ethylene polymer film base material layer, the ethylene polymer composition (A-2-2) and the ethylene / α-olefin random copolymer for the heat fusion layer are used. An ethylene / 1-octene random copolymer (B-2) was used as the polymer (B), melt-extruded using a biaxially stretched film molding machine equipped with three extrusions, and shaped with a T-die. Thereafter, it was rapidly cooled on a cooling roll to obtain a three-layer sheet (B-2 / A-2-2 / B-2 = 5/90/5 layer ratio) having a thickness of about 1.6 mm. This sheet was heated to 110 ° C. and stretched 6 times in the film flow direction (longitudinal direction). This 6-fold stretched sheet was heated to 116 ° C. and stretched 8.5 times in the direction perpendicular to the flow direction (lateral direction) to obtain a biaxially stretched ethylene polymer multilayer film having a thickness of 31 μm. The physical properties of the biaxially stretched ethylene polymer multilayer film were measured by the method described above.
結果を表１に示す。
実施例４
二軸延伸エチレン重合体フィルム基材層用及び非熱融着層用のエチレン系重合体（Ａ）として、前記エチレン重合体組成物（Ａ−２−２）を、及び熱融着層用のエチレン・α―オレフィンランダム共重合体（Ｂ）としてエチレン・１−オクテンランダム共重合体（Ｂ−１）を用い、３台の押出を備えた二軸延伸フィルム成形機を用いて溶融押出しし、Ｔ−ダイで賦形した後、冷却ロール上にて急冷し厚さ約２．４ｍｍの三層シート（Ｂ−１／Ａ−２−２／Ａ−２−２＝１０／８０／１０の層比）を得た。このシートを１１３℃に加熱しフィルムの流れ方向（縦方向）に７倍延伸した。この７倍延伸したシートを１１０℃に加熱し流れ方向に対して直交する方向（横方向）に８倍延伸して厚さ４２μｍの二軸延伸エチレン重合体多層フィルムを得た。かかる二軸延伸エチレン重合体多層フィルムの物性等を前記記載の方法で測定した。
The results are shown in Table 1.
Example 4
As the ethylene-based polymer (A) for the biaxially stretched ethylene polymer film base material layer and the non-heat-bonding layer, the ethylene polymer composition (A-2-2) and the heat-bonding layer are used. Using the ethylene / 1-octene random copolymer (B-1) as the ethylene / α-olefin random copolymer (B), melt extrusion using a biaxially stretched film molding machine equipped with three extrusions, After shaping with a T-die, it is rapidly cooled on a cooling roll and a three-layer sheet having a thickness of about 2.4 mm (B-1 / A-2-2 / A-2-2 = 10/80/10 layer) Ratio). This sheet was heated to 113 ° C. and stretched 7 times in the film flow direction (longitudinal direction). This 7-fold stretched sheet was heated to 110 ° C. and stretched 8 times in the direction perpendicular to the flow direction (lateral direction) to obtain a biaxially stretched ethylene polymer multilayer film having a thickness of 42 μm. The physical properties of the biaxially stretched ethylene polymer multilayer film were measured by the method described above.
結果を表１に示す。
実施例５
二軸延伸エチレン重合体フィルム基材層用及び非熱融着層用のエチレン系重合体（Ａ）として、前記エチレン重合体組成物（Ａ−２−２）を、及び熱融着層用のエチレン・α―オレフィンランダム共重合体（Ｂ）としてエチレン・１−オクテンランダム共重合体（Ｂ−３）を用い、３台の押出を備えた二軸延伸フィルム成形機を用いて溶融押出しし、Ｔ−ダイで賦形した後、冷却ロール上にて急冷し厚さ約１．８ｍｍの三層シート（Ｂ−３／Ａ−２−２／Ａ−２−２＝１０／８０／１０の層比）を得た。このシートを１１３℃に加熱
しフィルムの流れ方向（縦方向）に７倍延伸した。この７倍延伸したシートを１１０℃に加熱し流れ方向に対して直交する方向（横方向）に８倍延伸して厚さ３２μｍの二軸延伸エチレン重合体多層フィルムを得た。かかる二軸延伸エチレン重合体多層フィルムの物性等を前記記載の方法で測定した。
The results are shown in Table 1.
Example 5
As the ethylene-based polymer (A) for the biaxially stretched ethylene polymer film base material layer and the non-heat-bonding layer, the ethylene polymer composition (A-2-2) and the heat-bonding layer are used. Using ethylene / 1-octene random copolymer (B-3) as the ethylene / α-olefin random copolymer (B), melt extrusion using a biaxially stretched film molding machine equipped with three extrusions, After shaping with a T-die, it is rapidly cooled on a cooling roll and a three-layer sheet (B-3 / A-2-2 / A-2-2 = 10/80/10 layer having a thickness of about 1.8 mm) Ratio). This sheet was heated to 113 ° C. and stretched 7 times in the film flow direction (longitudinal direction). This 7-fold stretched sheet was heated to 110 ° C. and stretched 8 times in the direction perpendicular to the flow direction (lateral direction) to obtain a biaxially stretched ethylene polymer multilayer film having a thickness of 32 μm. The physical properties of the biaxially stretched ethylene polymer multilayer film were measured by the method described above.
結果を表１に示す。
実施例６
二軸延伸エチレン重合体フィルム基材層用及び非熱融着層用のエチレン系重合体（Ａ）として、前記エチレン重合体組成物（Ａ−２−２）を、及び熱融着層用のエチレン・α―オレフィンランダム共重合体（Ｂ）としてエチレン・αオレフィンランダム共重合体組成物（Ｂ−４）を用い、３台の押出を備えた二軸延伸フィルム成形機を用いて溶融押出しし、Ｔ−ダイで賦形した後、冷却ロール上にて急冷し厚さ約２ｍｍの三層シート（Ｂ−４／Ａ−２−２／Ａ−２−２＝５／８５／１０の層比）を得た。このシートを１１２℃に加熱しフィルムの流れ方向（縦方向）に５倍延伸した。この５倍延伸したシートを１１３℃に加熱し流れ方向に対して直交する方向（横方向）に１０倍延伸して厚さ３９μｍの二軸延伸エチレン重合体多層フィルムを得た。かかる二軸延伸エチレン重合体多層フィルムの物性等を前記記載の方法で測定した。
The results are shown in Table 1.
Example 6
As the ethylene-based polymer (A) for the biaxially stretched ethylene polymer film base material layer and the non-heat-bonding layer, the ethylene polymer composition (A-2-2) and the heat-bonding layer are used. Using ethylene / α-olefin random copolymer composition (B-4) as ethylene / α-olefin random copolymer (B), melt extrusion using a biaxially stretched film molding machine equipped with three extrusions After forming with a T-die, it is rapidly cooled on a cooling roll and a three-layer sheet having a thickness of about 2 mm (layer ratio of B-4 / A-2-2 / A-2-2 = 5/85/10) ) This sheet was heated to 112 ° C. and stretched 5 times in the film flow direction (longitudinal direction). The sheet stretched 5 times was heated to 113 ° C. and stretched 10 times in the direction perpendicular to the flow direction (lateral direction) to obtain a biaxially stretched ethylene polymer multilayer film having a thickness of 39 μm. The physical properties of the biaxially stretched ethylene polymer multilayer film were measured by the method described above.
結果を表１に示す。
実施例７
二軸延伸エチレン重合体フィルム基材層用のエチレン系重合体（Ａ）として、前記エチレン重合体組成物（Ａ−１−１）を、非熱融着層用のエチレン系重合体（Ａ）として、前記エチレン重合体組成物（Ａ−２−２）を、及び熱融着層用のエチレン・α―オレフィンランダム共重合体（Ｂ）としてエチレン・αオレフィンランダム共重合体組成物（Ｂ−１）を用い、３台の押出を備えた二軸延伸フィルム成形機を用いて溶融押出しし、Ｔ−ダイで賦形した後、冷却ロール上にて急冷し厚さ約１．６ｍｍの三層シート（Ｂ−１／Ａ−１−１／Ａ−２−２＝１０／８０／１０の層比）を得た。このシートを１１５℃に加熱しフィルムの流れ方向（縦方向）に５倍延伸した。この５倍延伸したシートを１１６℃に加熱し流れ方向に対して直交する方向（横方向）に８。５倍延伸して厚さ３７μｍの二軸延伸エチレン重合体多層フィルムを得た。かかる二軸延伸エチレン重合体多層フィルムの物性等を前記記載の方法で測定した。
The results are shown in Table 1.
Example 7
As the ethylene polymer (A) for the biaxially stretched ethylene polymer film substrate layer, the ethylene polymer composition (A-1-1) is used as the ethylene polymer (A) for the non-heat-sealing layer. As the ethylene polymer composition (A-2-2) and the ethylene / α-olefin random copolymer (B) for heat-sealing layer, the ethylene / α-olefin random copolymer composition (B- 1), and melt extruded using a biaxially stretched film molding machine equipped with three extrusions, shaped with a T-die, and then rapidly cooled on a cooling roll to form a triple layer having a thickness of about 1.6 mm A sheet (B-1 / A-1-1 / A-2-2 = 10/80/10 layer ratio) was obtained. This sheet was heated to 115 ° C. and stretched 5 times in the film flow direction (longitudinal direction). The 5-fold stretched sheet was heated to 116 ° C. and stretched 8.5 times in a direction perpendicular to the flow direction (lateral direction) to obtain a biaxially stretched ethylene polymer multilayer film having a thickness of 37 μm. The physical properties of the biaxially stretched ethylene polymer multilayer film were measured by the method described above.
結果を表１に示す。
比較例１
二軸延伸エチレン重合体フィルム基材層用及び非熱融着層用のエチレン系重合体（Ａ）として、前記エチレン・１−ヘキセンランダム共重合体（ｂ−１）を、及び熱融着層用のエチレン・α−オレフィンランダム共重合体（Ｂ）としてエチレン・１−オクテンランダム共重合体（Ｂ−１）を用い、３台の押出を備えた二軸延伸フィルム成形機を用いて溶融押出しし、Ｔ−ダイで賦形した後、冷却ロール上にて急冷し厚さ約１．６４ｍｍの三層シート（Ｂ−１／ｂ−１／ｂ−１＝５／９０／５の層比）を得た。このシートを１１１℃に加熱しフィルムの流れ方向（縦方向）に５倍延伸した。この５倍延伸したシートを１１５℃に加熱し流れ方向に対して直交する方向（横方向）に８倍延伸して厚さ４１μｍの二軸延伸エチレン重合体多層フィルムを得た。かかる二軸延伸エチレン重合体多層フィルムの物性等を前記記載の方法で測定した。
The results are shown in Table 1.
Comparative Example 1
As the ethylene-based polymer (A) for the biaxially stretched ethylene polymer film base material layer and the non-heat-fusion layer, the ethylene / 1-hexene random copolymer (b-1) and the heat-fusion layer The ethylene / 1-octene random copolymer (B-1) is used as the ethylene / α-olefin random copolymer (B) for melt extrusion using a biaxially stretched film molding machine equipped with three extrusions. Then, after forming with a T-die, it is rapidly cooled on a cooling roll and has a thickness of about 1.64 mm (layer ratio of B-1 / b-1 / b-1 = 5/90/5) Got. The sheet was heated to 111 ° C. and stretched 5 times in the film flow direction (longitudinal direction). This 5-fold stretched sheet was heated to 115 ° C. and stretched 8 times in the direction perpendicular to the flow direction (lateral direction) to obtain a biaxially stretched ethylene polymer multilayer film having a thickness of 41 μm. The physical properties of the biaxially stretched ethylene polymer multilayer film were measured by the method described above.
結果を表１に示す。 The results are shown in Table 1.
表１から明らかなように特定の融解熱量特性を有するエチレン重合体組成物から得られる二軸延伸エチレン重合体フィルム基材層とする二軸延伸エチレン重合体多層フィルム（
実施例１〜実施例７）は、ＭＤ方向及びＴＤ方向の何れの引裂強度の６０Ｎ／ｃｍ以下であり両方向の易引裂き性に優れ、且つヒートシール性も有していることが分かる。
実施例８
実施例４で得た二軸延伸エチレン重合体多層フィルム及び厚さ１５μｍの二軸延伸ポリアミドフィルム（商品名；エンブレム ユニチカ社製）を用い、二軸延伸エチレン重合体多層フィルムのラミネート層にアンカー剤を塗布した後、押出しラミネート機を用いて高圧法低密度ポリエチレン（商品名；ミラソン１１Ｐ 三井化学社製）を溶融押出しして、二軸延伸エチレン重合体多層フィルムのラミネート層と二軸延伸ポリアミドフィルムとを貼り合わせて二軸延伸エチレン重合体多層フィルムを得た。なおアンカー剤は、コロネートL、ニッポラン1100（ともに日本ポリウレタン工業）に、溶剤として酢酸エチル（広島
和光純薬製）を混合したものを使用した。かかる二軸延伸エチレン重合体多層フィルムの物性等を前記記載の方法で測定した。
As is clear from Table 1, a biaxially stretched ethylene polymer multilayer film (a biaxially stretched ethylene polymer film substrate layer obtained from an ethylene polymer composition having specific heat of fusion characteristics)
In Examples 1 to 7), it can be seen that the tear strength in either the MD direction or the TD direction is 60 N / cm or less, which is excellent in easy tearability in both directions, and also has heat sealability.
Example 8
The biaxially stretched ethylene polymer multilayer film obtained in Example 4 and a 15 μm thick biaxially stretched polyamide film (trade name; manufactured by Emblem Unitika Co., Ltd.) were used as an anchor agent for the laminate layer of the biaxially stretched ethylene polymer multilayer film. After coating, melt extrusion of high-pressure low-density polyethylene (trade name; Mirason 11P, manufactured by Mitsui Chemicals) using an extrusion laminating machine to laminate a biaxially stretched ethylene polymer multilayer film and a biaxially stretched polyamide film Were laminated to obtain a biaxially stretched ethylene polymer multilayer film. The anchor agent used was a mixture of Coronate L and Nipponran 1100 (both Nippon Polyurethane Industry) with ethyl acetate (manufactured by Hiroshima Wako Pure Chemical Industries) as a solvent. The physical properties of the biaxially stretched ethylene polymer multilayer film were measured by the method described above.
結果を表２に示す。
実施例９
実施例８で用いた二軸延伸ポリアミドフィルムに代えて厚さ１２μｍの二軸延伸ポリエチレンテレフタレートフィルム（商品名；ルミラー 東レ社製）を用いる以外は実施例８と同様に行い二軸延伸エチレン重合体多層フィルムを得た。かかる二軸延伸エチレン重合体多層フィルムの物性等を前記記載の方法で測定した。
The results are shown in Table 2.
Example 9
A biaxially stretched ethylene polymer was prepared in the same manner as in Example 8 except that a biaxially stretched polyethylene terephthalate film (trade name; manufactured by Lumirror Toray) with a thickness of 12 μm was used instead of the biaxially stretched polyamide film used in Example 8. A multilayer film was obtained. The physical properties of the biaxially stretched ethylene polymer multilayer film were measured by the method described above.
結果を表２に示す。
参考例１
実施例８で用いた二軸延伸エチレン重合体多層フィルムに代えて厚さ４０μｍの線状低密度ポリエチレンフィルム（商品名；Ｔ．Ｕ．Ｘ ＦＣＳ 東セロ社製）を用いる以外は実施例８と同様に行い積層フィルムを得た。かかる積層フィルムの物性等を前記記載の方法で測定した。
The results are shown in Table 2.
Reference example 1
The same as Example 8 except that a linear low density polyethylene film having a thickness of 40 μm (trade name: TUX FCS manufactured by Tosero Co., Ltd.) was used instead of the biaxially stretched ethylene polymer multilayer film used in Example 8. To obtain a laminated film. The physical properties of the laminated film were measured by the method described above.
結果を表２に示す。 The results are shown in Table 2.
表２から明らかなように特定の融解熱量特性を有するエチレン重合体組成物から得られる二軸延伸エチレン重合体フィルム基材層とする二軸延伸エチレン重合体多層フィルムと二軸延伸ポリアミドフィルム、あるいは二軸延伸ポリエチレンテレフタレートフィルムと積層してなる二軸延伸エチレン重合体多層フィルムは、かかる二軸延伸ポリアミドフィルム等と積層してもＭＤ方向及びＴＤ方向の何れの引裂強度の６０Ｎ／ｃｍ以下であり両方向の易引裂き性に優れ、且つ突刺し強度及び耐屈曲性にも優れている。 As is clear from Table 2, a biaxially stretched ethylene polymer multilayer film and a biaxially stretched polyamide film as a biaxially stretched ethylene polymer film base layer obtained from an ethylene polymer composition having specific heat of fusion characteristics, or A biaxially stretched ethylene polymer multilayer film laminated with a biaxially stretched polyethylene terephthalate film has a tear strength of 60 N / cm or less in either MD or TD direction even when laminated with such a biaxially stretched polyamide film. It excels in easy tearing in both directions, and has excellent piercing strength and bending resistance.
それに対して、二軸延伸ポリアミドフィルムと無延伸の線状低密度ポリエチレンフィルムとを貼り合わせた積層フィルムは引裂き強度が９６Ｎ／ｃｍと強く易引裂き性に劣り、しかも衝撃強度、耐屈曲性にも劣る。 In contrast, a laminated film made by laminating a biaxially stretched polyamide film and an unstretched linear low-density polyethylene film has a strong tear strength of 96 N / cm and is inferior in easy tearability, and also has impact strength and flex resistance. Inferior.
本発明の二軸延伸エチレン重合体多層フィルムは、縦横何れの方向にも容易に引裂け、且つ透明性、収縮性に優れ、しかもヒートシール性、耐屈曲性及び耐衝撃性にも優れるので、開封が容易なシュリンク包装やシュリンクラベルなどの用途に適している。また、内容物が液体や粉末などの包装用フィルムに使用することで、容易に引き裂け、開封時のショックで中身が飛び散らない易開封性包装袋としても使用できる。
Since the biaxially stretched ethylene polymer multilayer film of the present invention is easily torn in both the longitudinal and lateral directions, and is excellent in transparency and shrinkage, and also in heat sealability, flex resistance and impact resistance, It is suitable for applications such as shrink packaging and shrink labels that can be easily opened. Moreover, by using the contents for a packaging film such as liquid or powder, it can be used as an easy-open packaging bag that is easily torn and the contents are not scattered by a shock at the time of opening.
Claims (13)
（ΔＨT）が１００〜１４０Ｊ／ｇ、融解開始温度〜１１０℃の範囲の融解熱量（ΔＨL）が５０〜８０Ｊ／ｇ、１１０℃〜融解終了温度の範囲の融解熱量（ΔＨH）が３５〜８０
Ｊ／ｇの範囲にあり、（ΔＨH）／（ΔＨL）が０．５〜１．５の範囲にあるエチレン系重合体（Ａ）から得られる二軸延伸エチレン重合体フィルム基材層の少なくとも片面に、密度が８９０〜９１０Ｋｇ／ｍ3の範囲のエチレン・α―オレフィンランダム共重合体（Ｂ
）から得られる熱融着層が積層されてなることを特徴とする二軸延伸エチレン重合体多層フィルム。 The density is 915 to 938 Kg / m 3 , the heat of fusion (ΔH T ) obtained by a differential scanning calorimeter (DSC) is 100 to 140 J / g, and the heat of fusion (ΔH L ) in the range of the melting start temperature to 110 ° C. is 50 to The heat of fusion (ΔH H ) in the range of 80 J / g, 110 ° C. to melting end temperature is 35-80.
The biaxially stretched ethylene polymer film substrate layer obtained from the ethylene polymer (A) in the range of J / g and (ΔH H ) / (ΔH L ) in the range of 0.5 to 1.5 An ethylene / α-olefin random copolymer (B) having a density in the range of 890 to 910 kg / m 3 on at least one side.
2) a biaxially stretched ethylene polymer multilayer film, wherein the heat-fusible layer obtained from (1) is laminated.
ィンランダム共重合体（ａ１）成分と、密度が９２６〜９７０Ｋｇ／ｍ3のエチレン系重
合体（ａ２）成分とからなるエチレン共重合体組成物（Ａ−１）である請求項１記載の二軸延伸エチレン重合体多層フィルム。 Ethylene polymer (A) is an ethylene · alpha-olefin random copolymer having a density of 895~925Kg / m 3 (a1) component and an ethylene polymer having a density of 926~970Kg / m 3 (a2) component The biaxially stretched ethylene polymer multilayer film according to claim 1, which is an ethylene copolymer composition (A-1) comprising:
ィンランダム共重合体（ａ１）成分、密度が９２６〜９７０Ｋｇ／ｍ3のエチレン系重合
体（ａ２）成分及び密度が９１０〜９３５Ｋｇ／ｍ3の高圧法低密度ポリエチレン（ａ３
）とからなるエチレン共重合体組成物（Ａ−２）である請求項１記載の二軸延伸エチレン重合体多層フィルム。 Ethylene polymer (A) is an ethylene · alpha-olefin random copolymer having a density of 895~925Kg / m 3 (a1) component, an ethylene polymer having a density of 926~970Kg / m 3 (a2) component and High-pressure low-density polyethylene (a3 having a density of 910-935 kg / m 3
The biaxially stretched ethylene polymer multilayer film according to claim 1, which is an ethylene copolymer composition (A-2).
体（ａ２−１）成分と密度が９４６〜９７０Ｋｇ／ｍ3のエチレン系重合体（ａ２−２）
成分とからなる請求項３ないし７のいずれか１項に記載の二軸延伸エチレン重合体多層フィルム。 Ethylene polymer component (a2) is an ethylene polymer having a density of 926~945Kg / m 3 (a2-1) ethylene polymer component and a density 946~970Kg / m 3 (a2-2)
The biaxially stretched ethylene polymer multilayer film according to any one of claims 3 to 7, comprising a component.
請求項１ないし９のいずれか１項に記載の二軸延伸エチレン重合体多層フィルム。 When one of the tear strength in the MD direction and the tear strength in the TD direction of the biaxially stretched ethylene polymer multilayer film is (T S ) and the other is (T W ) (where T S > T W ). The biaxial stretching according to any one of claims 1 to 9, wherein the tear strength (T S ) is in the range of 80 to 10 N / cm, and (T W ) / (T S ) is in the range of 0.10 to 1. Ethylene polymer multilayer film.
The biaxially stretched ethylene polymer multilayer film according to claim 11 or 12, wherein the thermoplastic resin is any one of polyester, polyamide, and polypropylene.
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| JP4813438B2 (en) * | 2007-09-26 | 2011-11-09 | 株式会社プライムポリマー | Heat-sealable laminated film |
| JP2009096119A (en) * | 2007-10-18 | 2009-05-07 | Prime Polymer:Kk | Freshness keeping film and food packaging container |
| JP5766206B2 (en) * | 2010-11-22 | 2015-08-19 | 三井化学東セロ株式会社 | Biaxially stretched ethylene polymer multilayer film |
| JP6576451B2 (en) * | 2014-12-12 | 2019-09-18 | ダウ グローバル テクノロジーズ エルエルシー | Multilayer structure, laminate comprising multilayer structure, and article comprising laminate |
| MX2017016000A (en) * | 2015-06-30 | 2018-04-20 | Dow Global Technologies Llc | Multilayer structures and articles comprising the same. |
| JP6633908B2 (en) | 2015-12-17 | 2020-01-22 | 株式会社細川洋行 | High-strength polyethylene sealant film and package using the same |
| JP2018030313A (en) * | 2016-08-25 | 2018-03-01 | 凸版印刷株式会社 | Laminate film for package |
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| JP7375268B2 (en) * | 2018-07-25 | 2023-11-08 | Ｔｏｐｐａｎホールディングス株式会社 | Sealant films, packaging materials and packaging bodies |
| JP7308640B2 (en) | 2018-12-25 | 2023-07-14 | 株式会社プライムポリマー | LAMINATED BODY AND FLUID PACKAGING BAG USING THE SAME |
| EP4178799A1 (en) * | 2020-07-08 | 2023-05-17 | SABIC Global Technologies B.V. | Bi-directionally oriented multilayer film |
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