JP6454171B2 - Biaxially stretched ethylene polymer multilayer film - Google Patents
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- JP6454171B2 JP6454171B2 JP2015025296A JP2015025296A JP6454171B2 JP 6454171 B2 JP6454171 B2 JP 6454171B2 JP 2015025296 A JP2015025296 A JP 2015025296A JP 2015025296 A JP2015025296 A JP 2015025296A JP 6454171 B2 JP6454171 B2 JP 6454171B2
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Description
本発明は、落袋強度に優れ、且つ、耐屈曲性に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 having excellent bag drop strength and excellent 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、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 and mechanical strength of the ethylene / α-olefin random copolymer film, ethylene / α-olefin random A shrinkable film formed by biaxially stretching a composition obtained by adding high-density polyethylene or high-pressure low-density polyethylene to a copolymer and an ethylene / α-olefin random copolymer has been proposed.
また、耐屈曲性が優れる二軸延伸エチレン系多層フィルムとして、密度が９１５〜９３８Ｋｇ／ｍ3の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８９０Ｋｇ／ｍ3〜９１０Ｋｇ／ｍ3のエチレン・α‐オレフィンランダム共重合体から得られる熱融着層が積層されてなる二軸延伸エチレン重合体多層フィルムが提案されている（特許文献1）。 Moreover, as a biaxially stretched ethylene-based multilayer film having excellent bending resistance, the density is 890 kg / m 3 to 910 kg / m on at least one side of the biaxially stretched ethylene polymer film substrate layer having a density of 915 to 938 kg / m 3. A biaxially stretched ethylene polymer multilayer film in which heat-sealing layers obtained from 3 ethylene / α-olefin random copolymers are laminated has been proposed (Patent Document 1).
特許文献1に記載された二軸延伸エチレン系重合体多層フィルムは、耐屈曲性（耐ピンホール性）は優れるものの、用途によっては、落袋強度が十分ではない。
また、耐屈曲性が優れる二軸延伸エチレン系多層フィルムの別の方策として、密度が８９５〜９４５Kg／ｍ３のエチレン・α−オレフィンランダム共重合体 もしくは、上記共重合体と、密度が９１０〜９３５Ｋｇ／ｍ３の高圧法低密度ポリエチレンからなる密度が８９５〜９４５の組成物を二軸延伸し、ΔＮｘｚとΔＮｙｚの値がいずれも５×１０−３〜４．５×１０−２であることを特徴とするフィルムが提案されている（特許文献２）
さらに、落袋強度が改良された二軸延伸エチレン系多層フィルムとして、密度が８９５〜９２０Ｋｇ／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（ｂ）を４０質量％以上含むエチレン系重合体組成物から得られる基材層の少なくとも片面に、密度が９１０〜９３８Ｋｇ／ｍ3の範囲にあり、且つ、基材層を構成するエチレン・α‐オレフィンランダム共重合体（ｂ）の密度より高い密度を有するエチレン系重合体（Ａ）から得られる表層が積層されてなり、且つ、基材層及び表層が共に二軸延伸されてなる二軸延伸エチレン重合体多層フィルムが提案されている。(特許文献３)
特許文献３に記載された二軸延伸エチレン系重合体多層フィルムは耐屈曲性、落袋強度が優れる。一方で用途の拡大により、耐屈曲性と落体性能のさらなる向上が望まれている。
Although the biaxially stretched ethylene polymer multilayer film described in Patent Document 1 is excellent in bending resistance (pinhole resistance), the falling bag strength is not sufficient depending on the application.
Further, as another measure of the biaxially stretched ethylene multilayer film having excellent bending resistance, an ethylene / α-olefin random copolymer having a density of 895 to 945 kg / m 3 or the above copolymer and a density of 910 to 935 kg A composition having a density of 895 to 945 made of a high pressure method low density polyethylene of / m3 is biaxially stretched, and the values of ΔNxz and ΔNyz are both 5 × 10 −3 to 4.5 × 10 −2 Has been proposed (Patent Document 2).
Furthermore, as a biaxially stretched ethylene-based multilayer film with improved bag drop strength, an ethylene-based film containing 40% by mass or more of an ethylene / α-olefin random copolymer (b) having a density in the range of 895 to 920 kg / m 3 Density of the ethylene / α-olefin random copolymer (b) having a density in the range of 910 to 938 Kg / m 3 on at least one surface of the base material layer obtained from the polymer composition and constituting the base material layer A biaxially stretched ethylene polymer multilayer film in which a surface layer obtained from an ethylene-based polymer (A) having a higher density is laminated and the base material layer and the surface layer are both biaxially stretched has been proposed. . (Patent Document 3)
The biaxially stretched ethylene polymer multilayer film described in Patent Document 3 is excellent in bending resistance and bag drop strength. On the other hand, due to the expansion of applications, further improvement in bending resistance and falling body performance is desired.
本発明は、耐屈曲性に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。さらには用途によっては落袋強度の向上も要求されることから、落体性能と耐屈曲性の向上を両立させる二軸延伸エチレン重合体フィルムを提供することを付随する課題とする。 An object of the present invention is to provide a biaxially stretched ethylene polymer film having excellent bending resistance. Furthermore, since the improvement of the bag drop strength is also required depending on the application, it is an accompanying problem to provide a biaxially stretched ethylene polymer film that achieves both a drop drop performance and an improved bending resistance.
本発明は、密度が８９５〜９２０Ｋｇ／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（ｂ）を４０質量％以上含むエチレン系重合体組成物（Ｂ）から得られる基材層の少なくとも片面に、密度が９１０〜９３８Ｋｇ／ｍ3の範囲にあり、且つ、基材層を構成するエチレン・α‐オレフィンランダム共重合体（ｂ）の密度より高い密度を有するエチレン系重合体（Ａ）から得られる表層が積層されてなり、且つ、基材層及び表層が共に二軸延伸し、表層または基材層のうち厚い方の層の面配向度(ΔＮp)を０．００７から０．０２０の間に制御した二軸延伸エチレン重合体多層フィルムである。 The present invention provides a base material layer obtained from an ethylene-based polymer composition (B) containing 40% by mass or more of an ethylene / α-olefin random copolymer (b) having a density in the range of 895 to 920 Kg / m 3 . An ethylene-based polymer (A) having a density in the range of 910 to 938 Kg / m 3 on at least one surface and higher than the density of the ethylene / α-olefin random copolymer (b) constituting the base material layer (A) And the base layer and the surface layer are both biaxially stretched, and the surface orientation degree (ΔNp) of the thicker layer of the surface layer or the base layer is 0.007 to 0.00. A biaxially stretched ethylene polymer multilayer film controlled during 020.
本発明において、二軸延伸エチレン重合体多層フィルムが、縦方向（ＭＤ）の延伸倍率が２〜１４倍、横方向（ＴＤ）の延伸倍率が２〜１４倍の範囲にあることが好ましい。
また本発明において、エチレン系重合体組成物（Ｂ）の密度が、９００〜９２５Ｋｇ／ｍ3の範囲にあることが好ましい。
また発明のエチレン系重合体（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）であることが好ましい。
さらに本発明は、上記二軸延伸エチレン重合体多層フィルムの少なくとも片面に熱可塑性樹脂フィルムが積層されてなる二軸延伸エチレン重合体多層フィルムである。
また本発明は、この積層された二軸延伸エチレン重合体多層フィルムを熱融着層として用いてなる包装材料である。
In the present invention, the biaxially stretched ethylene polymer multilayer film preferably has a stretching ratio in the machine direction (MD) of 2 to 14 times and a stretching ratio in the transverse direction (TD) of 2 to 14 times.
In the present invention, the density of the ethylene polymer composition (B) is preferably in the range of 900 to 925 Kg / m 3 .
The ethylene polymer of the invention (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 ) And an ethylene copolymer composition (A-2) composed of high-pressure low-density polyethylene (a3) having a density of 910 to 935 Kg / m 3 .
Furthermore, the present invention is a biaxially stretched ethylene polymer multilayer film in which a thermoplastic resin film is laminated on at least one surface of the above biaxially stretched ethylene polymer multilayer film.
Moreover, this invention is a packaging material which uses this laminated biaxially stretched ethylene polymer multilayer film as a heat sealing | fusion layer.
また本発明者らは鋭意研究した結果、耐屈曲性、落袋性能の双方を両立させるためには、面配向度ΔＰを制御することが有効であることを見出した。耐屈曲性、落袋性能の双方を両立させるため、本発明において表層または基材層のうち厚い方の層の面配向度(ΔＮp)を０．００７から０．０１６の間に制御した二軸延伸エチレン重合体多層フィルムであることが好ましい。 In addition, as a result of intensive studies, the present inventors have found that it is effective to control the degree of plane orientation ΔP in order to achieve both flexibility and bag drop performance. In order to achieve both flexibility and bag drop performance, the biaxiality in which the surface orientation degree (ΔNp) of the thicker layer of the surface layer or the base material layer is controlled between 0.007 and 0.016 in the present invention. A stretched ethylene polymer multilayer film is preferred.
本発明の二軸延伸エチレン重合体多層フィルムは、耐屈曲性に優れる。 The biaxially stretched ethylene polymer multilayer film of the present invention is excellent in bending resistance.
［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基材層を構成する成分であるエチレン・α‐オレフィンランダム共重合体（ｂ）は、密度が８９５〜９２０Ｋｇ／ｍ3、好ましくは８９５〜９１５Ｋｇ／ｍ3、より好ましくは９００〜９１０Ｋｇ／ｍ3の範囲にある。
本発明に係るエチレン・α‐オレフィンランダム共重合体（ｂ）は、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（ｂ）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。
密度が上記範囲のエチレン・α‐オレフィンランダム共重合体を用いた場合は、得られる二軸延伸エチレン重合体多層フィルムの落袋強度が向上する。
本発明に係るエチレン・α‐オレフィンランダム共重合体（ｂ）は、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、０．１〜１０ｇ／１０分、好ましくは０．５〜５ｇ／１０分の範囲にある。
[Ethylene / α-olefin random copolymer (b)]
The ethylene / α-olefin random copolymer (b) which is a component constituting the base layer of the biaxially stretched ethylene polymer multilayer film of the present invention has a density of 895 to 920 Kg / m 3 , preferably 895 to 915 Kg / m 3 , more preferably in the range of 900 to 910 Kg / m 3 .
The ethylene / α-olefin random copolymer (b) according to the present invention comprises ethylene and an α-olefin having 4 or more carbon atoms, such as 1-butene, 1-heptene, 1-hexene, 1-octene, 4-methyl. It is a random copolymer with an α-olefin such as -1-pentene, preferably an α-olefin having 6 or more carbon atoms. The ethylene / α-olefin copolymer (b) 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.
When an ethylene / α-olefin random copolymer having a density in the above range is used, the bag drop strength of the resulting biaxially stretched ethylene polymer multilayer film is improved.
As long as the ethylene / α-olefin random copolymer (b) 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 is usually 0. .1 to 10 g / 10 min, preferably 0.5 to 5 g / 10 min.
［エチレン系重合体組成物（Ｂ）］
本発明の二軸延伸エチレン重合体多層フィルムの基材層を形成するエチレン系重合体組成物（Ｂ）は、前記エチレン・α‐オレフィンランダム共重合体（ｂ）を４０質量％以上含む、すなわち、エチレン・α‐オレフィンランダム共重合体（ｂ）単身であってもよく、好ましくはエチレン・α‐オレフィンランダム共重合体（ｂ）を４０〜８５質量％、より好ましくは５０〜８０質量％、最も好ましくは６５〜７５質量％の範囲で含むエチレン系重合体組成物である。
[Ethylene polymer composition (B)]
The ethylene polymer composition (B) forming the base layer of the biaxially stretched ethylene polymer multilayer film of the present invention contains 40% by mass or more of the ethylene / α-olefin random copolymer (b), The ethylene / α-olefin random copolymer (b) may be single, preferably 40 to 85% by mass, more preferably 50 to 80% by mass of the ethylene / α-olefin random copolymer (b), Most preferably, it is an ethylene polymer composition contained in the range of 65 to 75% by mass.
本発明に係るエチレン系重合体組成物に含まれる他のエチレン系重合体は、例えば、密度が９１５〜９７０Ｋｇ／ｍ3、好ましくは９２６〜９６５Ｋｇ／ｍ3の範囲にあるエチレン・α−オレフィン共重合体あるいはエチレン単独重合体、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であり、密度が異なる二種以上のエチレン・α−オレフィン共重合体あるいはエチレン単独重合体、もしくは、密度が異なる二種以上のエチレン・α−オレフィン共重合体あるいはエチレン単独重合体と高圧法低密度ポリエチレンを含んでいてもよい。 The other ethylene polymer contained in the ethylene polymer composition according to the present invention is, for example, an ethylene / α-olefin copolymer having a density in the range of 915 to 970 Kg / m 3 , preferably 926 to 965 Kg / m 3. Polymer or ethylene homopolymer, high-pressure low-density polyethylene having a density in the range of 910 to 935 Kg / m 3 , preferably 915 to 930 Kg / m 3 , and two or more kinds of ethylene / α-olefin having different densities A polymer or an ethylene homopolymer, or two or more kinds of ethylene / α-olefin copolymers or ethylene homopolymers having different densities and high-pressure low-density polyethylene may be included.
上記エチレン・α−オレフィン共重合体は、エチレンと炭素数３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−オレフィンとのランダム共重合体である。 The ethylene / α-olefin copolymer is an α-olefin having 3 or more carbon atoms such as ethylene and α-olefin such as 1-butene, 1-heptene, 1-hexene, 1-octene and 4-methyl-1-pentene. -Random copolymers with olefins.
本発明に係るエチレン系重合体組成物（Ｂ）は、密度が、９００〜９２５Ｋｇ／ｍ3の範囲にあることが好ましく、更には、９０４〜９２２Ｋｇ／ｍ3の範囲にあることが好ましい、
密度が上記範囲内にあると、得られる二軸延伸エチレン重合体多層フィルムの落袋強度、耐屈曲性が向上する。
Ethylene polymer composition according to the present invention (B) has a density of, preferably in the range of 900~925Kg / m 3, more preferably in the range of 904~922Kg / m 3,
When the density is within the above range, the falling bag strength and the bending resistance of the obtained biaxially stretched ethylene polymer multilayer film are improved.
本発明に係るエチレン系重合体組成物（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 composition (B) 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 It is in the range of 10 g / 10 min, preferably 0.8-5 g / 10 min.
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）あるいはエチレン系重合体組成物（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。 In the ethylene / α-olefin random copolymer (b) or the ethylene polymer composition (B) according to the present invention, an antioxidant, a weather stabilizer, and the like that are usually used within a range not impairing the object of the present invention, Additives such as antistatic agents, antifogging agents, antiblocking agents, lubricants, nucleating agents, pigments or other polymers can be blended as necessary.
［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少なくとも片面の表層、好ましくは両表面を形成するエチレン系重合体（Ａ）は、密度が９１０〜９３８Ｋｇ／ｍ3、好ましくは９２０〜９３５Ｋｇ／ｍ3の範囲にあり、且つ、基材層を構成するエチレン・α‐オレフィンランダム共重合体（ｂ）の密度より高い密度を有する。密度が上記範囲のエチレン系重合体を用いた場合は、得られる二軸延伸エチレン重合体多層フィルムの落袋強度が向上する。
[Ethylene polymer (A)]
The ethylene polymer (A) which forms at least one surface of the biaxially stretched ethylene polymer multilayer film of the present invention, preferably both surfaces, has a density of 910 to 938 Kg / m 3 , preferably 920 to 935 Kg / m 3. And a density higher than that of the ethylene / α-olefin random copolymer (b) constituting the base material layer. When an ethylene polymer having a density in the above range is used, the bag drop strength of the resulting biaxially stretched ethylene polymer multilayer film is improved.
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）は、特に、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。 In particular, the ethylene polymer (A) according to the present invention includes the following ethylene copolymer composition (A-1) or ethylene copolymer composition (A) obtained by mixing ethylene polymers having different densities. -2) is preferred.
［エチレン共重合体組成物（Ａ−１）］
本発明に係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質量％、より好ましくは２０〜８０質量％及びエチレン系重合体（ａ２）成分が９５〜５質量％、より好ましくは８０〜２０質量％〔（ａ１）＋（ａ２）＝１００質量％〕の範囲にある。
本発明に係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。
[Ethylene copolymer composition (A-1)]
The ethylene copolymer composition (A-1) according to the present invention has an ethylene / α-olefin copolymer (a1) component having a density of 895 to 925 Kg / m 3 , preferably 900 to 920 Kg / m 3. and density 926~970Kg / m 3, preferably ethylene copolymer composition comprising ethylene polymer (a2) component in the range 930~965Kg / m 3, preferably ethylene · alpha-olefin The random copolymer (a1) component is 5 to 95% by mass, more preferably 20 to 80% by mass, and the ethylene polymer (a2) component is 95 to 5% by mass, more preferably 80 to 20% by mass [(a1 ) + (A2) = 100 mass%].
As long as the ethylene copolymer composition (A-1) 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. It is in the range of 5 to 10 g / 10 minutes, preferably 0.8 to 5 g / 10 minutes.
［エチレン共重合体組成物（Ａ−２）］
本発明に係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９３０〜９６５Ｋｇ／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質量％、より好ましくは２０〜８０質量％及びエチレン系重合体（ａ２）成分が９５〜５質量％、より好ましくは４０〜７０質量％〔（ａ１）＋（ａ２）＝１００質量％〕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質量％、好ましくは６０〜９０質量％及び高圧法低密度ポリエチレン（ａ３）が５０〜５質量％、好ましくは３０〜１０質量％〔［（ａ１）＋（ａ２）］＋（ａ３）＝１００質量％〕の範囲にあることが望ましい。
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。
[Ethylene copolymer composition (A-2)]
The ethylene copolymer composition (A-2) according to 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 926~970Kg / m 3, preferably ethylene polymer (a2) component and the density in the range of 930~965Kg / m 3 is 910~935Kg / m 3, preferably of 915~930Kg / m 3 It is an ethylene copolymer composition comprising high-pressure low-density polyethylene (a3) in the range. The ethylene copolymer composition (A-2) is preferably an ethylene / α-olefin random copolymer (a1) component of (a1), (a2) and (a3), preferably 5 to 95% by mass, More preferably, 20 to 80% by mass and the ethylene polymer (a2) component is in the range of 95 to 5% by mass, more preferably 40 to 70% by mass [(a1) + (a2) = 100% by mass]. Is desirable. The ethylene copolymer composition (A-2) is preferably an ethylene / α-olefin random copolymer (a1) component + ethylene polymer (a2) component, preferably 50 to 95% by mass, preferably 60 ~ 90% by mass and high-pressure method low density polyethylene (a3) is in the range of 50 to 5% by mass, preferably 30 to 10% by mass [[(a1) + (a2)] + (a3) = 100% by mass]. It is desirable.
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.
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).
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れていてもよい。 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。 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.
［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少なくとも片面の表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。
[Ethylene polymer (a2)]
It is the other component which comprises the ethylene copolymer composition (A-1) or the ethylene copolymer composition (A-2) which forms the surface layer of at least one side of the biaxially stretched ethylene polymer multilayer film of the present invention. The ethylene polymer (a2) is a homopolymer of ethylene having a density in the range of 926 to 970 Kg / m 3 , preferably 930 to 965 Kg / m 3 , or ethylene and an α-olefin having 3 or more carbon atoms, such as propylene , 1-butene, 1-heptene, 1-hexene, 1-octene, 4-methyl-1-pentene, and other random copolymers. 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。
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質量％、好ましくは３０〜７０質量％及びエチレン系重合体（ａ２−２）成分を９９〜１質量％、好ましくは７０〜３０質量％〔（ａ２−１）＋（ａ２−２）＝１００質量％〕の割合とすることが望ましい。
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。
The ethylene polymer (a2) has a density of 926 to 945 Kg / m 3 , preferably 935 to 945 Kg / m 3 , and a density of 946 to 970 Kg / m. 3 , preferably 950 to 965 Kg / m 3 in the range of the ethylene polymer (a2-2) component, the low density component, and the high density component are used in combination. An axially stretched ethylene polymer multilayer film is obtained.
When an ethylene polymer (a2-1) component and an ethylene polymer (a2-2) component are used as the ethylene polymer (a2), the ethylene polymer (a2-1) component is 1 to 99% by mass. , Preferably 30 to 70% by mass and 99 to 1% by mass, preferably 70 to 30% by mass of the ethylene-based polymer (a2-2) component [(a2-1) + (a2-2) = 100% by mass] It is desirable to make the ratio.
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).
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れていてもよい。
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。
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。
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.
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.
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.
［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少なくとも片面の表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９１５〜９３０Ｋｇ／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。
[High pressure low density polyethylene (a3)]
High-pressure low-density polyethylene (a3), which is another component constituting the ethylene copolymer composition (A-2) that forms the surface layer of at least one surface of the biaxially stretched ethylene polymer multilayer film of the present invention, The density is in the range of 910 to 935 Kg / m 3 , preferably 915 to 930 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。
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 Ｄ１２３８ 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。
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.
The melt flow rate (MFR: ASTM D1238 load 2160 g, temperature 190 ° C.) of the high-pressure low-density polyethylene (a3) is a composition (A−) with the above-described ethylene polymer (a1) and ethylene polymer (a1). In the case of 2), there is no particular limitation as long as it has a film-forming ability, but it is usually in the range of 0.1 to 30 g / 10 minutes, preferably 0.1 to 10 g / 10 minutes.
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。
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) 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.
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。 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.
［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、前記密度が８９５〜９１５Ｋｇ／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（ｂ）を４０質量％以上含むエチレン系重合体組成物（Ｂ）から得られる基材層の少なくとも片面に、密度が９１０〜９３８Ｋｇ／ｍ3の範囲にあり、且つ、基材層を構成するエチレン・α‐オレフィンランダム共重合体（ｂ）の密度より高い密度を有するエチレン系重合体（Ａ）から得られる表層が積層されてなり、且つ、基材層及び表層が共に二軸延伸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である。
[Biaxially stretched ethylene polymer multilayer film]
The biaxially stretched ethylene polymer multilayer film of the present invention is an ethylene polymer composition containing 40% by mass or more of an ethylene / α-olefin random copolymer (b) having a density in the range of 895 to 915 Kg / m 3 . From the density of the ethylene / α-olefin random copolymer (b) having a density in the range of 910 to 938 Kg / m 3 on at least one surface of the base material layer obtained from (B) and constituting the base material layer. A biaxially stretched ethylene polymer multilayer film characterized in that a surface layer obtained from an ethylene polymer (A) having a high density is laminated, and the base material layer and the surface layer are both biaxially stretched. is there.
本発明の二軸延伸エチレン系多層フィルムは、前記基材層の両面に、前記密度が９１０〜９３８Ｋｇ／ｍ3の範囲にあるエチレン系重合体（Ａ）から得られる表層が積層されていてもよい。両面に密度が９１０〜９３８Ｋｇ／ｍ3の範囲にあるエチレン系重合体（Ａ）からなる表層を積層する場合は、密度が上記範囲にある限り、両面の表面層の各密度は同じ密度であっても、異なる密度であってもよい。 In the biaxially stretched ethylene multilayer film of the present invention, the surface layer obtained from the ethylene polymer (A) having the density in the range of 910 to 938 Kg / m 3 is laminated on both surfaces of the base material layer. Good. When a surface layer made of an ethylene polymer (A) having a density in the range of 910 to 938 Kg / m 3 is laminated on both sides, each density of the surface layers on both sides is the same as long as the density is in the above range. Or different densities.
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、表層の厚さが約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。 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 surface layer is about 0.2-60 μm, preferably about 0.4-40 μm, and the total thickness of the biaxially stretched ethylene polymer multilayer film is about 10-320 μm, preferably about 15-230 μm. Is in range.
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。
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。
本発明の二軸延伸エチレン重合体多層フィルムは、種々用途により、少なくとも片面に熱可塑性樹脂フィルムが積層されていてもよい。
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.
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.
The biaxially stretched ethylene polymer multilayer film of the present invention may have a thermoplastic resin film laminated on at least one side depending on various applications.
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。 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。
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。
Further, the thermoplastic resin film may be an unstretched film or a stretched film, or a laminate obtained by one or two or more types of coextrusion molding, extrusion lamination, dry lamination, thermal lamination, or 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.
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.
［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、基材層を形成する前記密度が８９５〜９１５Ｋｇ／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（ｂ）を４０質量％以上含むエチレン系重合体組成物（Ｂ）と表層を形成する前記密度が９１０〜９３８Ｋｇ／ｍ3の範囲にあり、且つ、基材層を構成するエチレン・α‐オレフィンランダム共重合体（ｂ）の密度より高い密度を有するエチレン系重合体（Ａ）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。
また、フラット方式で、表層または基材層のうち厚い方の層のΔＮｐを０．００７０〜０．０１６０に制御するために低倍率延伸（面倍率３０倍以下）を行う場合、厚薄が最良な方式は、同時二軸延伸方式である。
[Method for producing biaxially stretched ethylene polymer multilayer film]
The biaxially stretched ethylene polymer multilayer film of the present invention can be obtained by various known methods, for example, an ethylene / α-olefin random copolymer (b) in which the density for forming the base material layer is in the range of 895 to 915 Kg / m 3. ) And the ethylene-based polymer composition (B) containing 40% by mass or more, the density forming the surface layer is in the range of 910 to 938 kg / m 3 , and the ethylene / α-olefin random copolymer constituting the base material layer Coextruded with an ethylene polymer (A) having a density higher than that of the polymer (b), and in the above range in the longitudinal (MD) direction and lateral (TD) by the tubular system or flat system (tenter system). ) Obtained by biaxial stretching in the direction. 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.
Moreover, when performing low magnification stretching (a surface magnification of 30 times or less) in order to control ΔNp of the thicker layer of the surface layer or the base material layer to 0.0070 to 0.0160 by the flat method, the thickness is the best. The method is a simultaneous biaxial stretching method.
フラット方式の逐次二軸延伸による場合は、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、通常、２．０〜７．０倍、好ましくは２．３〜５．５倍延伸した後、９０〜１３０℃の温度範囲で横方向に、通常、５．０〜１２．０倍、好ましくは６．０〜１０．５倍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、目的とする面配向度(ΔＮｐ)に応じて変える事が出来る。
また、フラット方式の同時二軸延伸による場合は、通常押出し成形して得た多層シートを８０〜１４０℃の温度範囲で縦方向、横方向ともに、通常、２．０〜１４．０倍、好ましくは２．５〜６．５倍に延伸することにより得られる。二軸延伸した後は、８０〜１４０℃の温度範囲でヒートセットを行っても良い。ヒートセットの温度は、目的とする面配向度(ΔＮｐ)に応じて変える事ができる。また、ヒートセット時に緩和を行っても良い。
In the case of flat-type sequential biaxial stretching, the multilayer sheet obtained by extrusion molding is usually 2.0 to 7.0 times, preferably 2.3 times in the longitudinal direction in a temperature range of 90 to 125 ° C. After stretching by ˜5.5 times, the film is obtained by stretching by 5.0 to 12.0 times, preferably 6.0 to 10.5 times in the transverse 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 setting can be changed according to the desired degree of plane orientation (ΔNp).
Further, in the case of simultaneous biaxial stretching in the flat method, the multilayer sheet obtained by normal extrusion molding is usually 2.0 to 14.0 times in the longitudinal and lateral directions at a temperature range of 80 to 140 ° C., preferably Is obtained by stretching 2.5 to 6.5 times. After biaxial stretching, heat setting may be performed in a temperature range of 80 to 140 ° C. The temperature of the heat setting can be changed according to the target degree of plane orientation (ΔNp). Further, relaxation may be performed during heat setting.
本発明の二軸延伸エチレン重合体多層フィルムの片面に、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、必要に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基材層あるいは表層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。
参考形態の例を以下に付記する。
１．
密度が８９５〜９２０Ｋｇ／ｍ 3 の範囲にあるエチレン・α‐オレフィンランダム共重合体（ｂ）を４０質量％以上含むエチレン系重合体組成物（Ｂ）から得られる基材層の少なくとも片面に、密度が９１０〜９３８Ｋｇ／ｍ 3 の範囲にあり、且つ、基材層を構成するエチレン・α‐オレフィンランダム共重合体（ｂ）の密度より高い密度を有するエチレン系重合体（Ａ）から得られる表層が積層されてなり、且つ、基材層及び表層が共に二軸延伸され、基材層または表層のうち厚い方の層の面配向度（ΔＮｐ）が０．００７０〜０．０２０に制御されてい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。
２．
二軸延伸エチレン重合体多層フィルムが、縦方向（ＭＤ）の延伸倍率が２〜１４倍、横方向（ＴＤ）の延伸倍率が２〜１４倍の範囲にある１．に記載の二軸延伸エチレン重合体多層フィルム。
３．
エチレン系重合体組成物（Ｂ）の密度が、９００〜９２５Ｋｇ／ｍ 3 の範囲にある１．または２．に記載の二軸延伸エチレン重合体多層フィルム。
４．
エチレン系重合体（Ａ）が、密度が８９５〜９２５Ｋｇ／ｍ 3 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／ｍ 3 のエチレン系重合体（ａ２）成分及び密度が９１０〜９３５Ｋｇ／ｍ 3 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１．乃至３．のいずれか１つに記載の二軸延伸エチレン重合体多層フィルム。
５．
前記二軸延伸エチレン重合体多層フィルムの少なくとも片面に熱可塑性樹脂フィルムが積層されてなる１．乃至４．のいずれか１つに記載の二軸延伸エチレン重合体多層フィルム。
６．
前記熱可塑性樹脂フィルムが、二軸延伸されてなる５．に記載の二軸延伸エチレン重合体多層フィルム。
７．
前記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。
８．
５．乃至７．のいずれか１つに記載の二軸延伸エチレン重合体多層フィルムを熱融着層として用いてなる包装材料。
When a thermoplastic resin film is laminated on one side of the biaxially stretched ethylene polymer multilayer film of the present invention, various known methods, for example, a base layer of a biaxially stretched ethylene polymer multilayer film subjected to corona treatment if necessary Alternatively, after applying urethane type adhesive or isocyanate type adhesive on the surface of the surface layer, dry lamination with the thermoplastic resin film, or the laminated surface or both sides of the heat fusion layer and the thermoplastic resin film are high pressure low density A method of extrusion lamination using polyethylene may be employed.
Examples of reference forms are appended below.
1.
On at least one surface of the base material layer obtained from the ethylene-based polymer composition (B) containing 40% by mass or more of the ethylene / α-olefin random copolymer (b) having a density in the range of 895 to 920 Kg / m 3 , Obtained from an ethylene-based polymer (A) having a density in the range of 910 to 938 Kg / m 3 and having a density higher than that of the ethylene / α-olefin random copolymer (b) constituting the base material layer. The surface layer is laminated, and both the base material layer and the surface layer are biaxially stretched, and the plane orientation degree (ΔNp) of the thicker layer of the base material layer or the surface layer is controlled to 0.0070 to 0.020. A biaxially stretched ethylene polymer multilayer film characterized by comprising:
2.
1. The biaxially stretched ethylene polymer multilayer film has a stretch ratio in the machine direction (MD) of 2 to 14 times and a stretch ratio in the transverse direction (TD) of 2 to 14 times. 2. A biaxially stretched ethylene polymer multilayer film described in 1.
3.
1. The density of the ethylene polymer composition (B) is in the range of 900 to 925 Kg / m 3 . Or 2. 2. A biaxially stretched ethylene polymer multilayer film described in 1.
4).
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 1. An ethylene copolymer composition (A-2) comprising a high-pressure low-density polyethylene (a3) having a density of 910 to 935 Kg / m 3 . To 3. A biaxially stretched ethylene polymer multilayer film according to any one of the above.
5).
1. A thermoplastic resin film is laminated on at least one side of the biaxially stretched ethylene polymer multilayer film. To 4. A biaxially stretched ethylene polymer multilayer film according to any one of the above.
6).
4. The thermoplastic resin film is biaxially stretched. 2. A biaxially stretched ethylene polymer multilayer film described in 1.
7).
4. The thermoplastic resin is any one of polyester, polyamide or polypropylene. Or 6. 2. A biaxially stretched ethylene polymer multilayer film described in 1.
8).
5). To 7. A packaging material using the biaxially stretched ethylene polymer multilayer film according to any one of the above as a heat-sealing layer.
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を測定して得たエチレン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）を使用して二軸延伸エチレン重合体多層フィルム１枚の曇り度をＪＩＳ Ｋ ７１３６に準拠して測定した。
（４）引張試験
二軸延伸エチレン重合体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（ＭＰａ）を測定した。
（５）熱収縮率（％）
二軸延伸エチレン重合体多層フィルムから１００ｍｍ幅の正方形な試験片を切り出し、１００℃のオーブン内に１５分静置した。その後、オーブン内から試験片を取り出し、２３℃の雰囲気温度下で３０分以上静置後、正方形の試験片の各辺の長さを測定し、変化量とした。熱収縮率は、以下の式から算出した。
熱収縮値＝（１００−Ａ）／１００×１００
Ａ；オーブン内静置後の正方形の辺の長さ
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 ethylene 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 subjected to D method (density gradient tube) according to JIS K 7112. It was measured.
(3) Haze (cloudiness value) (%)
The haze of one biaxially stretched ethylene polymer multilayer 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 biaxially stretched ethylene polymer multilayer film so that the length direction is the film flow direction (MD) and the width direction (TD). The Young's modulus (MPa) was measured based on JIS K 7127 using Tensilon RT1225 manufactured by Orientec.
(5) Thermal shrinkage (%)
A 100 mm wide square test piece was cut out from the biaxially stretched ethylene polymer multilayer film and allowed to stand in an oven at 100 ° C. for 15 minutes. Thereafter, the test piece was taken out from the oven and allowed to stand at an ambient temperature of 23 ° C. for 30 minutes or longer, and then the length of each side of the square test piece was measured and used as the amount of change. The thermal contraction rate was calculated from the following formula.
Heat shrink value = (100−A) / 100 × 100
A: Length of the side of the square after standing in the oven
(６)面配向度の測定
フィルムの屈折率をアッベ（ａｂｂｅ）屈折計ＤＲ−Ｍ２（（株）アタゴ製）を用いて、下記のＮｘ、Ｎｙ、ＮｚをＪＩＳ Ｋ ７１４２に準拠して測定した。接触液は、ヨウ化メチレンを用いた。すなわち、測定光としてＤ線（波長５８９ｎｍ）を使用して、フィルムの直交３方向の屈折率Ｎｘ、Ｎｙ、Ｎｚを測定し、その測定で得られた数値から以下の複屈折、面配向度を求めた。
Ｎｘ フィルム製造時の流れ方向（ＭＤ）の屈折率
Ｎｙ フィルム面の流れ方向に直交する方向（ＴＤ）の屈折率
Ｎｚ フィルムの厚み方向の屈折率
複屈折：ΔＮｘｚ＝Ｎｘ−Ｎｚ、ΔＮｙｚ＝Ｎｙ−Ｎｚ
面配向度：ΔＮｐ＝（１／２（ΔＮｘｚ＋ΔＮｙｚ））
表層または基材層のうち厚い方の層よりも屈折率の低い層が存在するときは、測定原理上の必要性から、低い層を切削などで取り除いて測定した。
（７）ヒートシール強度
１５μｍのＮｙ（銘柄：ユニチカ株式会社製ＯＮＢＣ−１５）と二軸延伸エチレン重合体多層フィルムをドライラミネートした。ドライラミネートしたフィルムを東洋精機製ヒートシールテスターを使用し、二軸延伸エチレン重合体多層フィルム面同士を合わせて、ヒーター温度が１００℃〜１６０℃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。
（８）耐屈曲性（個／ｍ2）
テスター産業製のゲルボフレックステスターを使用し、二軸延伸エチレン重合体多層フィルムから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、０℃、−３０℃の各雰囲気下で、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（個／ｍ2）を測定した。
(6) Measurement of plane orientation The refractive index of the film was measured according to JIS K 7142 using the Abbe refractometer DR-M2 (manufactured by Atago Co., Ltd.) according to JIS K 7142. . As the contact liquid, methylene iodide was used. That is, using the D-line (wavelength 589 nm) as measurement light, the refractive indexes Nx, Ny, and Nz in the three orthogonal directions of the film are measured, and the following birefringence and plane orientation degree are obtained from the numerical values obtained by the measurement. Asked.
Refractive index in the flow direction (MD) during production of the Nx film Ny Refractive index in the direction (TD) perpendicular to the flow direction of the film surface Nz Refractive index in the thickness direction of the film Birefringence: ΔNxz = Nx−Nz, ΔNyz = Ny− Nz
Plane orientation degree: ΔNp = (1/2 (ΔNxz + ΔNyz))
When a layer having a lower refractive index than the thicker layer of the surface layer or the base material layer exists, the measurement was performed by removing the lower layer by cutting or the like because of the necessity in the measurement principle.
(7) Ny (brand: ONBC-15 manufactured by Unitika Ltd.) having a heat seal strength of 15 μm and a biaxially stretched ethylene polymer multilayer film were dry laminated. Using a heat-seal tester manufactured by Toyo Seiki, the laminated films were dry-laminated, and the biaxially stretched ethylene polymer multilayer film surfaces were joined together. The heater temperature was 100 ° C to 160 ° C, the pressure was 0.2 MPa, and the sealing time was 1 second. Then, after performing heat sealing, the sealed test piece was cut into a test piece having a width of 15 mm, and peel strength was measured using Tensilon RT1225 type manufactured by Orientec.
(8) Bending resistance (pieces / m 2 )
Using a gelboflex tester manufactured by Tester Sangyo, a test piece having a width of 210 mm and a length of 297 mm was cut out from a biaxially stretched ethylene polymer multilayer film, bent at a bending angle of 440 degrees and a bending speed of 40 times / minute, 0 ° C., − In each atmosphere at 30 ° C., after 3000 bending tests, a bag was made with the test piece after the bending test, and the number of pinholes (pieces / m 2 ) was measured with an ageless seal check made by Mitsubishi Gas Chemical. .
（９）落袋試験
条件Ａ：落袋試験に用いる積層体として、二軸延伸ポリエチレンテレフタレートフィルム（厚さ：１２μｍ）、二軸延伸ポリアミドフィルム（厚さ：１５μｍ）および二軸延伸エチレン重合体多層フィルムを用意し、二軸延伸ポリエチレンテレフタレートフィルムと二軸延伸ポリアミドフィルムを、ラミネート機を使用してドライラミで貼り合わせた後、二軸延伸エチレン重合体多層フィルムを、二軸延伸ポリアミドフィルム側に、メイヤーバーでアンカー剤を膜状に広げ、ゴムローラーにて加圧しながら、貼り合わせ、積層体を得た。積層体は、二軸延伸ポリエチレンテレフタレートフィルム／二軸延伸ポリアミドフィルム／二軸延伸エチレン重合体多層フィルムである。なお、アンカー剤は、タケラックＡ３１０、タケネートＡ３（三井化学製）に、溶剤として酢酸エチル（廣島和光純薬製）を混合してしたものを使用した。得られた積層体は、４０℃で２４時間、加圧した状態で保管した。得られた積層体の二軸延伸エチレン重合体多層フィルム面の表層側が、包装袋の内面を向くように配置し、高さ方向１４０ｍｍ、横方向１００ｍｍの三方袋を作製した。なおシール幅は、１０ｍｍである。作製した袋に、水９０ｍｌを充填し、エア抜きを行った上で、口部を１０ｍｍ余らせ、その中側をシールした。このような袋を、５袋準備し、５℃の雰囲気下で１２時間静置した後、袋の面を水平にして、袋と同じ大きさの面を有す平板状の３００ｇの重りを落下方向と逆面に重ねるように載せ、高さ１００ｃｍから落下をさせた。破袋するまで落下を繰返し、破袋した回数を記録して、５袋分のデータを平均化した回数で評価した。回数が多いほど、性能が良い。１００回以上を良好として、○と判断し、１００回未満を不良として、×と判断した。
(9) Bag drop test condition A: As a laminate used for the bag drop test, a biaxially stretched polyethylene terephthalate film (thickness: 12 μm), a biaxially stretched polyamide film (thickness: 15 μm), and a biaxially stretched ethylene polymer multilayer Prepare a film, and after laminating a biaxially stretched polyethylene terephthalate film and a biaxially stretched polyamide film with dry lamination using a laminating machine, the biaxially stretched ethylene polymer multilayer film is placed on the biaxially stretched polyamide film side. The anchor agent was spread in the form of a film with a Mayer bar and bonded together while being pressed with a rubber roller to obtain a laminate. The laminate is a biaxially stretched polyethylene terephthalate film / biaxially stretched polyamide film / biaxially stretched ethylene polymer multilayer film. The anchor agent used was a mixture of Takelac A310, Takenate A3 (Mitsui Chemicals) and ethyl acetate (Made by Wakashima Pure Chemicals) as a solvent. The obtained laminate was stored under pressure at 40 ° C. for 24 hours. The resulting laminate was disposed so that the surface layer side of the biaxially stretched ethylene polymer multilayer film surface of the laminate was directed to the inner surface of the packaging bag, and a three-sided bag having a height direction of 140 mm and a lateral direction of 100 mm was produced. The seal width is 10 mm. The produced bag was filled with 90 ml of water, air was removed, the mouth was left 10 mm, and the inside was sealed. After preparing five such bags and allowing them to stand for 12 hours in an atmosphere of 5 ° C., the bag surface is leveled and a 300 g weight of a flat plate having the same size as the bag is dropped. It was placed so as to overlap with the direction opposite to the direction, and dropped from a height of 100 cm. The dropping was repeated until the bag was broken, the number of times the bag was broken was recorded, and the data was evaluated by averaging the data for five bags. The more times, the better the performance. 100 times or more was judged as good and judged as good, and less than 100 times was judged as bad and judged as x.
条件Ｂ：条件Ａのうち、三方袋のサイズを高さ方向２００ｍｍ、横方向１５０ｍｍに変更、水の充填量を４００ｍｌに変更、落下時の重りを５００ｇに変更、落下高さを５０ｃｍに変更した以外は、条件Ａと同様に行なった。３０回以上を良好として、○と判断し、３０回未満を不良として×と判断した。 Condition B: Among the conditions A, the size of the three-sided bag was changed to 200 mm in the height direction and 150 mm in the horizontal direction, the water filling amount was changed to 400 ml, the weight at the time of dropping was changed to 500 g, and the falling height was changed to 50 cm Except for this, the same procedure as in Condition A was performed. More than 30 times were judged as good and judged as good, and less than 30 times were judged as bad and judged as x.
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。
（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；９１８Ｋｇ／ｍ3、ＭＦＲ；３．８ｇ／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) Ethylene / 1-hexene random copolymer (a1-2): polymer using metallocene catalyst, density: 918 Kg / m 3 , MFR: 3.8 g / 10 min.
（ii）エチレン系重合体（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。
（iii）エチレン系重合体（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。
(Ii) Ethylene polymer (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.
(Iii) Ethylene polymer (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）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；９１７Ｋｇ／ｍ3、ＭＦＲ；７ｇ／１０分。
（ｖ）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（ａ１−１）、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（ａ３−１）を３６：２４：２５：１５（質量％）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。
得られたエチレン重合体組成物（Ａ−２−１）は密度；９２７Ｋｇ／ｍ3、ＭＦＲ；２．０ｇ／１０分であった。
(Iv) High pressure method low density polyethylene (a3)
(1) High-pressure method low-density polyethylene (a3-1): density: 917 Kg / m 3 , MFR: 7 g / 10 min.
(V) Ethylene polymer composition (A-2)
(1) Ethylene polymer composition (A-2-1)
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 method low density polyethylene (a3-1) at a ratio of 36: 24: 25: 15 (mass%), 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-2-1).
The obtained ethylene polymer composition (A-2-1) had a density of 927 Kg / m 3 and an MFR of 2.0 g / 10 minutes.
（vi）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）（前記（ａ１−１）に同じ）：メタロセン触媒を用いた重合体、密度；９０５Ｋｇ／ｍ3、ＭＦＲ；０．５ｇ／１０分。
（２）エチレン・１−ヘキセンランダム共重合体（ｂ−２）：メタロセン触媒を用いた重合体、密度；９０３Ｋｇ／ｍ3、ＭＦＲ；３．８ｇ／１０分。
（３）エチレン・１−ヘキセンランダム共重合体（ｂ−３）：メタロセン触媒を用いた重合体、密度；９１３Ｋｇ／ｍ3、ＭＦＲ；３．８ｇ／１０分。
（４）エチレン・１−ヘキセンランダム共重合体（ｂ−４）：メタロセン触媒を用いた重合体、密度；９１８Ｋｇ／ｍ3、ＭＦＲ；３．８ｇ／１０分。
(Vi) ethylene / α-olefin random copolymer (b)
(1) Ethylene / 1-hexene random copolymer (b-1) (same as (a1-1) above): polymer using metallocene catalyst, density: 905 Kg / m 3 , MFR: 0.5 g / 10 Minutes.
(2) Ethylene / 1-hexene random copolymer (b-2): Polymer using metallocene catalyst, density: 903 Kg / m 3 , MFR: 3.8 g / 10 min.
(3) Ethylene / 1-hexene random copolymer (b-3): polymer using metallocene catalyst, density: 913 Kg / m 3 , MFR: 3.8 g / 10 min.
(4) Ethylene / 1-hexene random copolymer (b-4): polymer using metallocene catalyst, density: 918 Kg / m 3 , MFR: 3.8 g / 10 min.
（vii）エチレン系重合体組成物（Ｂ）
（１）エチレン系重合体組成物（Ｂ−１）
前記エチレン重合体組成物（Ａ−２−１）：５０質量％および前記エチレン・１−ヘキセンランダム共重合体（ｂ−２）：５０質量％とをドライブレンドして、エチレン系重合体組成物（Ｂ−１）を得た。エチレン系重合体組成物（Ｂ−１）に含まれるエチレン・α‐オレフィンランダム共重合体（ｂ）の量は、６８質量％〔（ａ１−１）＋（ｂ−２）〕であり、密度；９１５Ｋｇ／ｍ3、ＭＦＲ；２．９ｇ／１０分である。
(Vii) Ethylene polymer composition (B)
(1) Ethylene polymer composition (B-1)
The ethylene polymer composition (A-2-1): 50% by mass and the ethylene / 1-hexene random copolymer (b-2): 50% by mass are dry blended to produce an ethylene polymer composition. (B-1) was obtained. The amount of the ethylene / α-olefin random copolymer (b) contained in the ethylene-based polymer composition (B-1) is 68% by mass [(a1-1) + (b-2)], and the density 915 Kg / m 3 , MFR; 2.9 g / 10 min.
〔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組成物（Ｂ）として、前記エチレン重合体組成物（Ｂ−１）を、及び表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０．６〜０．７ｍｍの三層シート（Ａ−２−１／Ｂ−１／Ａ−２−１＝５／９０／５の層比）を得た。このシートを１０４℃に加熱し、フィルムの流れ方向（縦方向）に４．４倍、流れ方向に対して直交する方向（横方向）に４．４倍同時二軸延伸をして、厚さ約４０μｍ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。
結果を表１に示す。
[Example 1]
The ethylene polymer composition (B-1) as the ethylene polymer composition (B) for the biaxially stretched ethylene polymer film substrate layer, and the ethylene as the ethylene polymer (A) for the surface layer The polymer composition (A-2-1) was used, 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. A three-layer sheet having a thickness of about 0.6 to 0.7 mm (A-21 / B-1 / A-2-1 = 5/90/5 layer ratio) was obtained. This sheet is heated to 104 ° C., and simultaneously biaxially stretched 4.4 times in the film flow direction (longitudinal direction) and 4.4 times in the direction orthogonal to the flow direction (transverse direction). A biaxially stretched ethylene polymer multilayer film of about 40 μm was obtained. The physical properties of the biaxially stretched ethylene polymer multilayer film were measured by the method described above.
The results are shown in Table 1.
〔実施例２〕
実施例１と同様な方法を行い、二軸延伸エチレン重合体多層フィルムを得た。得られたフィルムを、縦方向／横方向同時に１０％緩和しながら、１１５℃の温度で熱処理を行って、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。結果を表１に示す。
[Example 2]
The same method as in Example 1 was performed to obtain a biaxially stretched ethylene polymer multilayer film. The obtained film was heat-treated at a temperature of 115 ° C. while relaxing 10% in the longitudinal direction / lateral direction simultaneously to obtain a biaxially stretched ethylene polymer multilayer film. The physical properties of the biaxially stretched ethylene polymer multilayer film were measured by the method described above. The results are shown in Table 1.
〔実施例３〕
実施例２の熱処理温度のみ１２０℃に変更し、その他同様な方法を行い、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。結果を表１に示す。
Example 3
Only the heat treatment temperature of Example 2 was changed to 120 ° C., and other similar methods were performed to obtain a biaxially stretched ethylene polymer multilayer film. The physical properties of the biaxially stretched ethylene polymer multilayer film were measured by the method described above. The results are shown in Table 1.
〔実施例４〕
実施例２の熱処理温度のみ１２２℃に変更し、その他同様な方法を行い、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。結果を表１に示す。
Example 4
Only the heat treatment temperature of Example 2 was changed to 122 ° C., and other similar methods were performed to obtain a biaxially stretched ethylene polymer multilayer film. The physical properties of the biaxially stretched ethylene polymer multilayer film were measured by the method described above. The results are shown in Table 1.
〔比較例１〕
実施例２の熱処理温度のみ１２４℃に変更し、その他同様な方法を行い、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。結果を表２に示す。
[Comparative Example 1]
Only the heat treatment temperature of Example 2 was changed to 124 ° C., and other similar methods were performed to obtain a biaxially stretched ethylene polymer multilayer film. The physical properties of the biaxially stretched ethylene polymer multilayer film were measured by the method described above. The results are shown in Table 2.
〔実施例５〕
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組成物（Ｂ）として、前記エチレン重合体組成物（Ｂ−１）を、及び表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１．５ｍｍの三層シート（Ａ−２−１／Ｂ−１／Ａ−２−１＝５／９０／５の層比）を得た。
このシートを用いて、縦方向（ＭＤ）はロールによる延伸を行い、その後、横方向（ＴＤ）はテンターにより延伸した。ロールによる延伸の温度は、９５℃であり、テンターによる延伸の温度は１１６℃である。テンター延伸後、１２７℃で熱処理を実施し、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。結果を表２に示す。
Example 5
The ethylene polymer composition (B-1) as the ethylene polymer composition (B) for the biaxially stretched ethylene polymer film substrate layer, and the ethylene as the ethylene polymer (A) for the surface layer The polymer composition (A-2-1) was used, 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. A three-layer sheet having a thickness of about 1.5 mm (layer ratio of A-2-1 / B-1 / A-2-1 = 5/90/5) was obtained.
Using this sheet, the longitudinal direction (MD) was stretched by a roll, and then the transverse direction (TD) was stretched by a tenter. The temperature for stretching by a roll is 95 ° C., and the temperature for stretching by a tenter is 116 ° C. After tenter stretching, heat treatment was performed at 127 ° C. to obtain a biaxially stretched ethylene polymer multilayer film. The physical properties of the biaxially stretched ethylene polymer multilayer film were measured by the method described above. The results are shown in Table 2.
〔参考例〕
実施例５のテンター延伸温度を１０４℃、熱処理温度を１１８℃に変更し、その他同条件で二軸延伸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。結果を表２に示す。
[Reference example]
The tenter stretching temperature of Example 5 was changed to 104 ° C. and the heat treatment temperature was changed to 118 ° C., and a biaxially stretched polymer multilayer film was obtained under the same conditions. The physical properties of the biaxially stretched ethylene polymer multilayer film were measured by the method described above. The results are shown in Table 2.
表１に示す結果から、ΔＮｐが０．００７〜０．０２０の範囲では、ピンホール数が５００以下で耐屈曲性優れていることがわかる。比較例1のΔＮｐが０．００６ではピンホール数が１０００以上になり、耐屈曲性が劣ることがわかる。以上より、耐屈曲性は、ΔＮｐが０．００７以上であれば、優れている。
また、表１に示す結果から、ΔＮｐが０．０１９になると、落体試験結果が、×と判断され、劣ることがわかる。よって、耐屈曲性と落体性能を両立させるためにはΔＮｐが０．００７〜０．０１６の範囲が好ましい。
From the results shown in Table 1, it can be seen that when ΔNp is in the range of 0.007 to 0.020, the number of pinholes is 500 or less and the bending resistance is excellent. It can be seen that when ΔNp of Comparative Example 1 is 0.006, the number of pinholes is 1000 or more, and the bending resistance is poor. From the above, the bending resistance is excellent when ΔNp is 0.007 or more.
From the results shown in Table 1, it can be seen that when ΔNp is 0.019, the falling body test result is judged as x, which is inferior. Therefore, ΔNp is preferably in the range of 0.007 to 0.016 in order to achieve both bending resistance and falling body performance.
本発明の二軸延伸エチレン重合体多層フィルムは、落袋強度に優れ、且つ、耐屈曲性、に優れ、しかもヒートシール性に優れるので、内容物が液体や粉末などの包装袋に適している。 The biaxially stretched ethylene polymer multilayer film of the present invention is suitable for packaging bags such as liquids and powders because it has excellent bag drop strength, excellent flex resistance, and excellent heat sealability. .
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