JP4163112B2 - POLYOLEFIN RESIN MATERIAL, LAMINATE USING SAME, METHOD FOR PRODUCING THE SAME, AND MOLDED ARTICLES - Google Patents

Description

【００８４】
【表２】

【００８５】
［実施例１〜３］
エチレン共重合体（Ａ１１ａ）、（Ａ１２ａ）および（Ａ２ａ）を７０質量部と（Ｂ１）ＬＤＰＥを３０質量部とを配合し、酸化防止剤等の添加剤を配合せずにタンブラーミキサーでドライブレンドした後、１７０℃でペレタイズして樹脂組成物を得た。そして、φ９０ｍｍ径の押出機を有する押出ラミネート成形機（モダンマシナリー社製）を使用し、成形温度３１５℃で、樹脂組成物を溶融押出して、ラミネート速度１００ｍ／分、ラミネート厚み３０μｍ、コート幅８６０ｍｍで、基材であるアルミニウム箔（＃３０）、ポリエチレンテレフタレート（ＰＥＴ：３０μｍ）上に押出ラミネートして積層体を得た。これらの積層体から試験片を採取し、接着強度を調べた。その結果を表３に示した。
【００８６】
［比較例１〜５］
エチレン共重合体（Ａ１１ａ）を７０質量部と（Ｂ１）ＬＤＰＥを３０質量部とを配合し、酸化防止剤、ステアリン酸カルシウム、ハイドロタルサイト等の添加剤を配合しタンブラーミキサーでドライブレンドした後、１７０℃でペレタイズして樹脂組成物を得た。そして、実施例１と同様にして押出ラミネートして積層体を得た。この積層体から試験片を採取し、接着強度を調べた。その結果を表３に示した。
【００８７】
［比較例６］
（Ｂ１）ＬＤＰＥを１００質量部に酸化防止剤を配合し実施例１と同様にして押出ラミネートして積層体を得た。この積層体から試験片を採取し、接着強度を調べた。その結果を表３に示した。
【００８８】
【表３】

【００８９】
［実施例４］
エチレン共重合体（Ａ１１ａ）を７０質量部と（Ｂ１）ＬＤＰＥを３０質量部とを配合し、タンブラーミキサーでドライブレンドした後、１７０℃でペレタイズして樹脂組成物を得た。そして、φ９０ｍｍ径の押出機を有する押出ラミネート成形機（モダンマシナリー社製）を使用し、成形温度３２０℃で、樹脂組成物を溶融押出して、ラミネート速度１００ｍ／分、ラミネート厚み２５μｍ、コート幅８６０ｍｍで、基材であるアルミニウム箔＃３０上に押出ラミネートして積層体を得た。そして、この積層体から試験片を採取し、接着強度およびヒートシール強度を調べた。その結果を表４に示した。
なお、この押出ラミネートの際、ＩＲ測定用サンプルを得るために、幅２１０ｍｍ×長さ２９７ｍｍの上質紙に、厚み１００μｍ×幅５０ｍｍ×長さ１００ｍｍの四フッ化ビニリデン製粘着テープ（日東電工製ニトフロン粘着テープＮｏ．９２３Ｓ）を貼合したサンプル採取用紙を用意し、これを基材層をなす基材の一部に、四フッ化ビニリデン製粘着テープがポリオレフィン系樹脂材料層の接着面と接するように貼合した。それとともに、ＥＳＣＡ測定用サンプルを得るために、幅２１０ｍｍ×長さ２９７ｍｍをコロナ処理していないＰＥＴフィルムを、ポリオレフィン系樹脂材料層接着面と接するように基材に貼合した。
【００９０】
［表面酸化度］
積層体の四フッ化ビニリデン製粘着テープを貼合した部分を幅１０ｍｍ、長さ５０ｍｍの大きさで２枚切り出し、四フッ化ビニリデン製粘着テープ表面からポリオレフィン系樹脂材料層を剥離してＩＲ測定用サンプルを得た。ＩＲ測定用サンプルであるポリオレフィン系樹脂材料層の酸化処理された面を日本分光（株）製ＦＴ−ＩＲ（ＩＲ−３００型）を用い、窒素パージしながらＡＴＲ法で表面赤外スペクトルを測定した。
なお、測定において、分解能４ｃｍ^−１、積算回数２００回とした。また、ＡＴＲ測定用結晶板は材質がＫＲＳ−５（臭化タリウム結晶）で幅２０ｍｍ×長さ５０ｍｍ×厚み２ｍｍ、角度４５°の台形状断面のものを用い、その両面にサンプルを密着させた。
得られた表面赤外スペクトルにおいて、１７２０ｃｍ^−１付近のカルボニル基の吸収ピークを、酸化度合いを示す吸収ピークとして選び、このピークの両側の谷部を結んでベースラインとすることにより、このピークの吸光度（Ｉ（１７２０））を求めた。次に、１３７０ｃｍ^−１付近のメチル基の吸収ピークを、基準ピークとして選び、１３３０ｃｍ^−１付近および１４００ｃｍ^−１付近の２点間を結んでベースラインとして１３７０ｃｍ^−１の吸光度（Ｉ（１３７０））を求めた。そして、表面酸化度Ｏｒを上述した（式８）に基づいて算出した。その結果を表４に示す。
【００９１】
［酸素原子濃度］
酸素原子濃度（Ｏｃ）とは、ポリオレフィン系樹脂材料層（ＩＩ）の、基材層（Ｉ）と接している面において、ＥＳＣＡ法により測定された酸素Ｏｌｓ補正ピーク強度：Ｏと、炭素Ｃｌｓ補正ピーク強度：Ｃとを（式７）に代入して求めた値である。酸素原子濃度により接着表面の酸素原子導入量が定量化できる。
（式７） Ｏｃ＝Ｏ／（Ｃ＋Ｏ）×１００（％）
【００９２】
［接着強度］
上記工程によって得られた積層体を、４０℃で２日間、その後２３℃で１日間の状態調整した。これを幅１５ｍｍ、長さ１５０ｍｍの長方形に切り出し、基材層とポリオレフィン系樹脂材料層との界面で剥離し、ＪＩＳ Ｋ６８５４に準拠して、剥離速度３００ｍｍ／分の条件でＴ型剥離を行って剥離強度を測定し、この剥離強度を接着強度とした。その結果を表４に示す。
【００９３】
［実施例５］
エチレン共重合体（Ａ１１ａ）の代わりにエチレン共重合体（Ａ１２ａ）を配合した以外は実施例４と同様にして積層体を得た。この積層体について接着強度、酸素原子濃度および表面酸化度を調べた。その結果を表４に示す。
【００９４】
［実施例６］
エチレン共重合体（Ａ１１ａ）の代わりにエチレン共重合体（Ａ２ａ）を配合した以外は実施例４と同様にして積層体を得た。この積層体について接着強度、酸素原子濃度および表面酸化度を調べた。その結果を表４に示す。
【００９５】
［実施例７］
基材としてアルミニウム箔＃３０の代わりにポリエチレンテレフタレートフィルム（ＰＥＴ）＃１２を用い、成形温度を３１０℃にした以外は実施例４と同様にして積層体を得た。この積層体について接着強度、酸素原子濃度および表面酸化度を調べた。その結果を表４に示す。
【００９６】
［実施例８］
エチレン共重合体（Ａ１１ａ）の代わりにエチレン共重合体（Ａ２ａ）を用い、基材としてアルミニウム箔＃３０の代わりにポリエチレンテレフタレートフィルム（ＰＥＴ）＃１２を用いた以外は実施例４と同様にして積層体を得た。この積層体について接着強度、酸素原子濃度および表面酸化度を調べた。その結果を表４に示す。
【００９７】
［実施例９］
基材としてアルミニウム箔＃３０の代わりに二軸延伸ナイロンフィルム（ＯＮｙ）＃１５を用いた以外は実施例４と同様にして積層体を得た。この積層体について接着強度、酸素原子濃度および表面酸化度を調べた。その結果を表４に示す。
【００９８】
［実施例１０］
基材としてアルミニウム箔＃３０の代わりにポリエチレンテレフタレートフィルム（ＰＥＴ）＃１２を用い、成形温度を３００℃にし、オゾン処理した以外は実施例４と同様にして積層体を得た。この積層体について接着強度、酸素原子濃度および表面酸化度を調べた。その結果を表４に示す。
【００９９】
［比較例７］
エチレン共重合体（Ａ１１ａ）の代わりに、ＯＤＣＢ可溶分の質量平均分子量が外れる一般メタロセン触媒によるエチレン共重合体（Ａ３ａ）を配合した以外は実施例４と同様にして積層体を得た。この積層体について接着強度、酸素原子濃度および表面酸化度を調べた。その結果を表４に示す。
【０１００】
［比較例８］
エチレン共重合体（Ａ１１ａ）を配合せず、（Ｂ１）ＬＤＰＥを１００質量部とした以外は実施例４と同様にして積層体を得た。この積層体について接着強度、酸素原子濃度および表面酸化度を調べた。その結果を表５に示す。
【０１０１】
［比較例９］
エチレン共重合体（Ａ１１ａ）の代わりにチーグラー触媒によるＬＬＤＰＥ（Ａ４ａ）を配合した以外は実施例４と同様にして積層体を得た。この積層体について接着強度を調べた。その結果を表５に示す。
【０１０２】
［比較例１０］
基材としてアルミニウム箔＃３０の代わりにＰＥＴ＃１２を用いた以外は比較例７と同様にして積層体を得た。この積層体について接着強度、酸素原子濃度および表面酸化度を調べた。その結果を表５に示す。
【０１０３】
［比較例１１］
基材としてアルミニウム箔＃３０の代わりにＰＥＴ＃１２を用いた以外は比較例８と同様にして積層体を得た。この積層体について接着強度、酸素原子濃度および表面酸化度を調べた。その結果を表５に示す。
【０１０４】
［比較例１２］
基材としてアルミニウム箔＃３０の代わりにＯＮｙ＃１５を用いた以外は比較例７と同様にして積層体を得た。この積層体について接着強度、酸素原子濃度および表面酸化度を調べた。その結果を表５に示す。
【０１０５】
［比較例１３］
基材としてアルミニウム箔＃３０の代わりにＯＮｙ＃１５を用いた以外は比較例８と同様にして積層体を得た。この積層体について接着強度、酸素原子濃度および表面酸化度を調べた。その結果を表５に示す。
【０１０６】
［比較例１４］
成形温度を３００℃にし、オゾン処理した以外は比較例９と同様にして積層体を得た。この積層体について接着強度、酸素原子濃度および表面酸化度を調べた。その結果を表５に示す。
【０１０７】
［比較例１５］
成形温度を３００℃にし、オゾン処理した以外は比較例１０と同様にして積層体を得た。この積層体について接着強度、酸素原子濃度および表面酸化度を調べた。その結果を表５に示す。
【０１０８】
【表４】

【０１０９】
【表５】

【０１１０】
実施例４〜１０は本願請求項１の範囲を満たしているので、接着強度が高かった。
一方、比較例７のエチレン共重合体（Ａ３ａ）は、ＯＤＣＢ可溶分のＭｗが高く、接着強度は向上していない。
比較例８，１０，１２，１４は、ポリオレフィン系樹脂材料層が高圧ラジカル重合法低密度ポリエチレンのみなので、接着強度が低かった。また、比較例９，１１，１３，１５は、市販のチーグラー系触媒によるエチレン・α−オレフィン共重合体（Ａ４ａ）と高圧ラジカル重合法低密度ポリエチレンとが配合されたものであったため、接着強度は低かった。
【０１１１】
［実施例１１〜１８］
表６に示す割合で、エチレン共重合体（Ａ１１ｂ）、（Ａ１２ｂ）、（Ａ２ｂ）およびＬＤＰＥ（Ｂ１）を配合し、酸化防止剤およびハロゲン吸収剤（ステアリン酸カルシウム）を添加せずにタンブラーミキサーでドライブレンドした後、プラコー製（スクリュー径５５ｍｍφ）の押出機を用い、成形温度１４０℃、フィルム幅３００ｍｍ、ブロー比２．７の成形条件でインフレーション法により厚さ３０μｍの単層フィルムを成形した。この単層フィルムについてダートインパクト強度、引裂強度、ヒートシール温度、ハロゲン濃度を測定し、臭気とフィッシュアイの評価を行った。結果を表６に示す。臭気、フィッシュアイともに問題は見られなかった。
【０１１２】
［比較例１６］
（Ｂ１）ＬＤＰＥのみで実施例１１と同様にインフレーションフィルムを成形し、評価した結果を表６に示した。ＬＤＰＥのみであるのでダートインパクト強度が低いものである。
【０１１３】
［比較例１７］
実施例１２の（Ａ１１ｂ）のエチレン共重合体の代わりにのメタロセン触媒によるエチレン共重合体（Ａ３ｂ）に代えた以外は実施例１１と同様にして評価した結果を表６に示した。成形温度が高く、臭気、フィッシュアイが多いものであった。
【０１１４】
［比較例１８〜１９］
表６に示す組成で、市販のチーグラー系触媒による線状低密度ポリエチレン（ＬＬＤＰＥ）単独または該ＬＬＤＰＥ（Ａ４ｂ）およびＬＤＰＥ（Ｂ１）を配合し、実施例１１と同様に単層フィルムを成形した。結果を表６に示す。ＬＬＤＰＥ（Ａ４ｂ）の割合が多い場合、成形温度が低いため、単層フィルムを成形できなかった。
【０１１５】
［比較例２０〜２１］
表６に示す割合で、チーグラーナッタ触媒を用いた線状低密度ポリエチレンＬＬＤＰＥ（Ａ４ｂ）および該ＬＬＤＰＥとＬＤＰＥ（Ｂ１）を配合し、これに、酸化防止剤としてイルガノックス１０７６を１０００ｐｐｍ、イルガフォス１６８を１５００ｐｐｍ、ハロゲン吸収剤としてステアリン酸カルシウム１５００ｐｐｍを添加し、タンブラーミキサーでドライブレンドした後、プラコー製（スクリュー径５５ｍｍφ）の押出機を用い、成形温度１８０℃、フィルム幅３００ｍｍ、ブロー比２．７の成形条件でインフレーション法により厚さ３０μｍの単層フィルムを成形した。結果を表６に示す。添加剤が配合されているため臭気、ハロゲン濃度が高いものであった。
【０１１６】
［比較例２２］
酸化防止剤、ハロゲン吸収剤を添加しない以外は、比較例２１と同様にして単層フィルムを成形した。結果を表６に示す。添加剤がない状態で樹脂温度が高いため樹脂劣化が進行してしたものと思われ、臭気、フィッシュアイが多いものであった。
【０１１７】
【表６】

【０１１８】
【発明の効果】
以上説明したように、本発明のポリオレフィン系樹脂材料は、上述の（ａ）〜（ｅ）の特定の要件を満足するエチレン（共）重合体（Ａ）１００〜１０質量％と、（Ｂ）他のポリオレフィン系樹脂０〜９０質量％とを含み、ＯＤＣＢ可溶分の質量平均分子量が８０００〜３００００の範囲である特定のエチレン（共）重合体（Ａ）を用い、かつ実質的に添加剤が配合されていないポリオレフィン系樹脂材料であって、低温ヒートシール性、接着強度、引裂強度、耐衝撃性、透明性、成形加工性等に優れる。また、樹脂中に実質的にハロゲン含有しないので食品、医療、電子材料等のポリオレフイン容器等が要求される分野、特に乳等省令に適合する食品用容器等に好適である。
また、エチレン（共）重合体（Ａ）を含有するポリオレフィン系樹脂材料は、低温成形が可能で、ハロゲンフリーであることから、従来の酸化防止剤、酸吸収剤等の添加剤が存在しなくても、成形可能である。
また、本発明によれば、ポリオレフィン系樹脂材料層（ＩＩ）と基材層（Ｉ）とが高い接着強度で接着されている。したがって、この特定のエチレン（共）重合体を特定範囲に酸化させると、アンカーコート剤を使用する必要がないので、溶剤などの溶出がなく、ポリオレフィン系樹脂積層体が提供できる。さらに、アンカーコート剤を用いないことにより、コストが低下し、作業が簡略化する。また、溶剤を使用しなくなるので環境上の問題、臭気の問題がなくなる。
また、本願発明の成形体の一態様である積層体は、接着強度、引裂強度、耐衝撃性、低温ヒートシール性、透明性、成形加工性等に優れ、食品、医療、電子材料等のポリオレフイン容器等が要求される分野、特に乳等省令に適合する食品用容器等に好適である。
また、本発明のバッグインボックス用内袋は、少なくとも最内層に前記フィルムまたはシート、あるいは前記積層体を用いているので、引裂強度、耐衝撃性、低温ヒートシール性、透明性、成形加工性等に優れ、ポリオレフイン内袋が要求される分野に好適である。
また、本発明の医療用容器または包装体は、少なくとも最内層に前記フィルムまたはシート、あるいは前記積層体を用いているので、引裂強度、耐衝撃性、低温ヒートシール性、透明性、成形加工性等に優れ、ポリオレフイン容器や包装体が要求される医療分野に好適である。
【図面の簡単な説明】
【図１】 図１は、本発明におけるエチレン（共）重合体（Ａ）のＴ_７５−Ｔ_２５の〔式１〕の説明図である。
【図２】 図２は、本発明におけるエチレン（共）重合体（Ａ１）の溶出温度−溶出量曲線を示すグラフである。
【図３】 図３は、典型的なメタロセン系触媒によるエチレン共重合体の溶出温度−溶出量曲線を示すグラフである。
【図４】 図４は、本発明におけるエチレン（共）重合体（Ａ２）の溶出温度−溶出量曲線を示すグラフである。
【図５】 図５Ａおよび図５Ｂは、ＩＲ測定用サンプルを作製する方法を示す図であって、図５Ａはラミネート工程を示す斜視図であり、図５Ｂはサンプル採取用紙を示す斜視図である。
【図６】 図６Ａは、積層体におけるサンプル採取用紙の貼合部分を示す断面図であり、図６Ｂは、積層体におけるサンプル採取用紙の貼合部分において、ポリオレフィン系樹脂材料層を分離した際の断面図である。[0001]
BACKGROUND OF THE INVENTION
  The present invention relates to a polyolefin-based resin material, a laminate using the same, a method for producing the same, and a molded article thereof. In particular, in a specific range where the mass average molecular weight of an ODCB soluble component is 8000 to 30000, an antioxidant, a steer Since there is no blending of additives such as calcium phosphate, the amount of impurities and low-volume components eluted is small, and substantially no halogen is contained, this is a polyolefin resin material with high low-temperature heat sealability and high adhesive strength. In addition, a laminate using the polyolefin resin material has high adhesive strength without using an anchor coating agent, and is excellent in tear strength, impact resistance, transparency, and particularly useful as a sealant layer. It is used in fields where polyolefin packaging materials such as electronic materials and containers are required.
[0002]
[Prior art]
  Conventionally, a high-pressure radical method low-density polyethylene or the like is generally used as a resin for a packaging material or a sealant material. However, the high-pressure radical method low-density polyethylene has the problems that the low-temperature heat sealability, tear strength, impact resistance, waist strength, and the like are inferior. In recent years, in order to improve productivity, more stringent low-temperature heat sealability, high adhesive strength, heat resistance, and the like are required, and an alternative to the high-pressure radical method low-density polyethylene is required.
  As an alternative to the high-pressure radical method low-density polyethylene, linear low-density polyethylene, high-density polyethylene, and the like are conceivable.
However, linear low density polyethylene has excellent tear strength, impact resistance, etc., but low temperature heat sealability, molding processability, etc. are inferior, and high density polyethylene has excellent heat resistance, mechanical strength, etc. The heat-sealing adhesive strength, transparency, tear strength, impact resistance, etc. were inferior.
  In addition, linear low density polyethylene and high density polyethylene obtained by ionic polymerization have a higher molding temperature than the high pressure radical method low density polyethylene. Is added. In addition, linear low density polyethylene and the like produced by ionic polymerization generally contain a halogen element such as chlorine as a catalyst residue. Therefore, halogen absorbents (acid neutralizers) such as calcium stearate and hydrotalcite. Etc. had to be added. In addition, these linear low-density polyethylene and high-density polyethylene not only have a significantly low adhesive strength, but also have a relatively large amount of low-molecular weight components, so that they are transferred to contacted objects such as contents, and milk and dairy products There is a problem that it is difficult to comply with the Japanese Food Sanitation Law (Ministry of Health and Welfare Notification No. 52: Ordinance of the Ministry of Milk, etc.) prescribed for food packaging. In addition, the low temperature heat sealability is not satisfactory, and the high speed moldability is inferior.
  As a material excellent in the low-temperature heat-sealing property, a linear low-density polyethylene using a metallocene-based catalyst has recently been mentioned, and has attracted attention as a packaging material and a sealant material.
  However, even in the case of linear low-density polyethylene using such a general metallocene catalyst, additives such as the above-mentioned antioxidants, halogen absorbers, and lubricants are used at the time of molding, thereby improving adhesion and cleanliness. Have a problem. In general, even when halogen absorbers are used, halogen elements still remain in the resin, and there is a problem in the cleanliness of the product. Packaging materials such as milk and dairy products, paper containers, etc. ) Did not fit.
  In order to solve the above problems, the present inventors have previously proposed a polyolefin molded body, a laminate and the like in which additives are not blended in JP-A Nos. 2001-341249 and 2001-342306.
  JP-A-2001-341249 and JP-A-2001-342306 are incorporated herein.
[0003]
[Problems to be solved by the invention]
  The present invention has been found that the adhesiveness to the substrate is dramatically improved by selecting the mass average molecular weight of the ODCB soluble part at 23 ° C. of the polyolefin resin material within a specific range. It is.
  An object of the present invention is to use a polyolefin-based resin material that has high low-temperature heat sealability, high adhesive strength, tear strength, impact resistance, transparency, high-speed moldability, and the like, without using an anchor coating agent, and its polyolefin It provides laminates using resin materials, methods for producing the same, and molded products made of them, and has high interlaminar adhesion strength, and is particularly applicable to food sanitation standards (such as milk and dairy products). It provides sealant materials, packaging materials, food containers, paper containers, etc. that are used in the fields of food, medical care, electronic materials, etc. that conform to the Ministerial Ordinance of Milk) and require cleanliness.
[0004]
[Means for Solving the Problems]
  As a result of intensive studies to solve the above-mentioned problems, the present inventors have taken into consideration that the adhesive strength is reduced by blending additives such as antioxidants, acid neutralizers such as calcium stearate and hydrotalcite. Ethylene that satisfies the specific parameters of preventing the decrease in the adhesive strength, substantially using no additive, and having a mass-average molecular weight of an orthodichlorobenzene (ODCB) soluble content in the range of 8000-30000 By making it a polymer, it synergistically increases the adhesion strength to the substrate, etc., and there is little elution of low molecular weight components to the product, and low temperature heat sealability, tear strength, impact resistance, transparency, high speed molding Polyolefin resin material having excellent properties or the like, or the ethylene (co) polymer and other polyolefin resin such as high-pressure radical method low density polyethylene Polyolefin-based resin materials can be provided, particularly useful as adhesive materials such as sealant layers with low-temperature heat sealability and high adhesive strength, or useful as polyolefin packaging materials for films, laminates, paper containers, etc. The inventor has completed the present invention.
[0005]
  That is, (1) the polyolefin resin material of the present invention comprises (A) 100 to 10% by mass of an ethylene (co) polymer that satisfies the following (a) to (e):
(A) Density is 0.86-0.97 g / cm³,
(B) a melt flow rate of 0.01 to 200 g / 10 minutes,
(C) molecular weight distribution (Mw / Mn) is 1.5 to 4.5,
(D) The mass average molecular weight of the o-dichlorobenzene (ODCB) soluble component at 23 ° C. is in the range of 8000 to 30000,
(E) Temperature T at which 25% of the total elution temperature obtained from the integral dissolution curve of elution temperature-elution volume curve by continuous temperature rising elution fractionation method (TREF) is eluted₂₅And the temperature T at which 75% of the total elution occurs₇₅Difference with T₇₅-T₂₅And the density d is
(Formula 1) T₇₅-T₂₅≦ −670 × d + 644
(B) It contains 0-90 mass% of other polyolefin resin, and the additive is not mix | blended substantially in the said polyolefin resin material, It is characterized by the above-mentioned.
(2) In addition, the ethylene (co) polymer (A) was further eluted by 25% of the total solution obtained from the integral dissolution curve of the elution temperature-elution amount curve by (f) continuous temperature rising elution fractionation method (TREF). Temperature T₂₅And the temperature T at which 75% of the total elution occurs₇₅Difference with T₇₅-T₂₅And the density d is
(Formula 2) d <0.950 g / cm³When,
T₇₅-T₂₅≧ −300 × d + 285,
d ≧ 0.950 g / cm³When,
T₇₅-T₂₅≧ 0
It is an ethylene (co) polymer (A) satisfying the relationship of
(3) Further, the ethylene (co) polymer (A) further has (g) an orthodichlorobenzene (ODCB) soluble amount X (mass%) at 25 ° C., a density d and a melt flow rate (MFR).
(Formula 3) When d−0.008log MFR ≧ 0.93
X <2.0
(Formula 4) d-0.008log MFR <0.93
X <9.8 × 10³× (0.9300-d + 0.008logMFR)²Satisfying the relationship of +2.0,
And (h) an ethylene (co) polymer (A1) having a plurality of peaks in an elution temperature-elution amount curve by continuous temperature rising elution fractionation (TREF).
(4) Further, the ethylene (co) polymer (A) further has (i) one peak of an elution temperature-elution amount curve by continuous temperature rising elution fractionation (TREF),
And (j) one to two or more melting points, and the highest melting point T_mlAnd the density d is (Equation 5) T_ml≧ 150 × d-19
It is an ethylene (co) polymer (A2) that satisfies the above relationship.
(5) In addition, the ethylene (co) polymer (A2) further has (k) melt tension (MT) and melt flow rate (MFR).
(Formula 6) logMT ≦ −0.572 × logMFR + 0.3
It satisfies the requirements of
(6) Further, the halogen content in the ethylene (co) polymer (A) is 10 ppm or less.
(7) The ethylene (co) polymer (A) is produced in the presence of a catalyst containing at least an organic cyclic compound having a conjugated double bond and a transition metal compound of Group IV of the periodic table. It is characterized by being.
[0006]
(8) Further, the molded article of the present invention is characterized in that the polyolefin resin material is produced by at least one molding method of extrusion molding, injection molding, blow molding, and rotational molding.
(9) Moreover, the laminate of the present invention comprises at least the base material (I) and (A) 100 to 10% by mass of an ethylene (co) polymer satisfying the following (a) to (e):
(A) Density is 0.86-0.97 g / cm³,
(B) a melt flow rate of 0.01 to 200 g / 10 minutes,
(C) molecular weight distribution (Mw / Mn) is 1.5 to 4.5,
(D) The mass average molecular weight of the o-dichlorobenzene (ODCB) soluble component at 23 ° C. is in the range of 8000 to 30000,
(E) Temperature T at which 25% of the total elution temperature obtained from the integral dissolution curve of elution temperature-elution volume curve by continuous temperature rising elution fractionation method (TREF) is eluted₂₅And the temperature T at which 75% of the total elution occurs₇₅Difference with T_{7 5}-T₂₅And the density d is
(Formula 1) T₇₅-T₂₅≦ −670 × d + 644
(B) a polyolefin-based resin material layer (II) containing 0 to 90% by mass of other polyolefin-based resin and containing substantially no additive, and formed without an anchor coat agent layer. It is characterized by becoming.
(10) Further, the surface of the laminate-based polyolefin resin material layer (II) in contact with the base material layer (I) is (i) an oxygen atom concentration of 1.8% by mass or more and (b) ) The surface oxidation degree is 0.10 or more.
(11) Further, the base material (I) of the laminate is composed of at least one of a thermoplastic film, a metal foil, a metal oxide or inorganic vapor deposition film, paper, a nonwoven fabric, and a woven fabric. To do.
(12) In addition, another polyolefin resin in the polyolefin resin material layer (II) of the laminate is a high-pressure low-density polyethylene.
[0007]
(13) Moreover, the manufacturing method of the laminated body of this invention is the ethylene (co) which satisfies the following (a)-(e), without using an anchor coating agent for at least base material (I). 100 to 10% by mass of the polymer,
(A) Density is 0.86-0.97 g / cm³,
(B) A melt flow rate of 0.01 to 200 g / 10 minutes,
(C) molecular weight distribution (Mw / Mn) is 1.5 to 4.5,
(D) The mass average molecular weight of the o-dichlorobenzene (ODCB) soluble component at 23 ° C. is in the range of 8000 to 30000,
(E) Temperature T at which 25% of the total elution temperature obtained from the integral dissolution curve of elution temperature-elution volume curve by continuous temperature rising elution fractionation method (TREF) is eluted₂₅And the temperature T at which 75% of the total elution occurs₇₅Difference with T₇₅-T₂₅And the density d is
(Formula 1) T₇₅-T₂₅≦ −670 × d + 644
(B) Forming a polyolefin resin material (II) containing 0 to 90% by mass of other polyolefin resin and substantially not containing additives at a molding temperature of 200 to 350 ° C. It is characterized by.
(14) Moreover, the manufacturing method of the laminated body of this invention WHEREIN: The surface which contact | connects the base material (I) of the said melt-extruded molten resin film is (i) oxygen atom concentration is 1.8 mass% or more, The molten resin film is laminated on the substrate (I) while being oxidized so that the degree of oxidation is 0.10 or more.
(15) Moreover, the manufacturing method of the laminated body of this invention is characterized by the said oxidation treatment being air oxidation treatment and / or ozone treatment in the range of 200-350 degreeC resin temperature of a molten resin film. .
(16) Moreover, the container or bag of this invention consists of said polyolefin resin material or a laminated body.
(17) Further, the paper container of the present invention is characterized in that it comprises at least a paper layer (I-1) and / or a barrier layer (I-2) and a polyolefin resin material layer (II) as a heat seal layer. To do.
(18) Further, the paper container of the present invention comprises a plastic layer (I-3) / paper layer (I-1) / polyolefin resin material layer (II-1) / barrier layer (I-2) / heat seal layer. It is characterized by being laminated in the order of (polyolefin resin material layer (II-2)).
[0008]
DETAILED DESCRIPTION OF THE INVENTION
  Hereinafter, the present invention will be described in detail.
  The ethylene (co) polymer (A) in the present invention is obtained by copolymerizing ethylene homopolymer or ethylene and an α-olefin having 3 to 20 carbon atoms, preferably 3 to 12 carbon atoms. It is an ethylene / α-olefin copolymer.
  Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene and 1-dodecene. Further, the total content of these α-olefins is usually 30 mol% or less, preferably 3 to 20 mol% or less.
[0009]
  The (a) density of the ethylene (co) polymer (A) in the present invention is 0.86 to 0.97 g / cm.³, Preferably 0.89-0.95 g / cm³More preferably, 0.90 to 0.94 g / cm³Range. Density is 0.86 g / cm³If it is less than 1, the rigidity (waist strength) and heat resistance will be poor. The density is 0.97 g / cm³If it exceeds, tear strength, impact resistance and the like may be insufficient.
[0010]
  The (b) melt flow rate (hereinafter referred to as MFR) of the ethylene (co) polymer (A) in the present invention is 0.01 to 200 g / 10 minutes, preferably 0.05 to 100 g / 10 minutes, more preferably. Is in the range of 0.1-80 g / min. If the MFR is less than 0.01 g / 10 min, the moldability is inferior, and if it exceeds 200 g / 10 min, the tear strength, impact resistance, etc. may be inferior.
[0011]
  The (c) molecular weight distribution (Mw / Mn) of the ethylene (co) polymer (A) in the present invention is in the range of 1.5 to 4.5, preferably 2.0 to 4.0, more preferably 2. It is in the range of 5-3.0. If Mw / Mn is less than 1.5, moldability is inferior, and if Mw / Mn exceeds 4.5, tear strength, impact resistance and the like may be inferior.
  Here, the molecular weight distribution (Mw / Mn) of the ethylene (co) polymer is determined by gel permeation chromatography (GPC) to obtain a mass average molecular weight (Mw) and a number average molecular weight (Mn), and a ratio (Mw) / Mn).
[0012]
  The mass average molecular weight (Mw) of the (d) ODCB soluble component of the ethylene (co) polymer (A) of the present invention is in the range of 8000 to 30000, preferably 10000 to 28000, more preferably 13,000 to 27000. It is desirable.
  When the mass average molecular weight is less than 8000, stickiness or blocking of the molded product is caused. In addition, the molecular chains are not easily entangled, the cohesive failure does not occur, and there is a possibility that it does not contribute to the improvement of the adhesive strength. Further, when the mass average molecular weight (Mw) exceeds 30000, the resin at the time of melting does not sufficiently permeate into a substrate such as paper, and the anchor effect is not exhibited, so that there is a concern that the adhesive force is reduced. Thus, unless the mass average molecular weight (Mw) is in a specific range as in the present invention, both the penetration force and the anchor effect are not satisfied.
  Here, in the method for measuring the mass average molecular weight (Mw) of the ODCB soluble component, first, the sample concentration is set to 0.05 mass% in ODCB to which an antioxidant (for example, butylhydroxytoluene) is added. In addition, it is heated and dissolved at 140 ° C. Next, the container containing the sample and ODCB is allowed to stand overnight at room temperature (23 ° C.), filtered through a polyvinylidene fluoride filter, and the filtrate is collected. Then, the filtrate is subjected to GPC (gel permeation chromatography) to measure the mass average molecular weight.
[0013]
  The ethylene (co) polymer (A) in the present invention is, for example, as shown in FIG. 1, (e) the whole obtained from an integral elution curve of an elution temperature-elution amount curve by a continuous temperature rising elution fractionation method (TREF). 25% of elution temperature T₂₅And the temperature T at which 75% of the total elution occurs₇₅Difference with T₇₅-T₂₅And the density d is the following (formula 1) T₇₅-T₂₅It is necessary to satisfy the relationship of ≦ −670 × d + 644. T₇₅-T₂₅If the density d does not satisfy the relationship of the above (formula 1), the low temperature heat sealability may be deteriorated.
  The measuring method of TREF is as follows. First, a sample is added to ODCB to which an antioxidant (for example, butylhydroxytoluene) is added so that the sample concentration becomes 0.05 mass%, and heated and dissolved at 140 ° C. 5 ml of this sample solution is injected into a column filled with glass beads, cooled to 25 ° C. at a cooling rate of 0.1 ° C./min, and the sample is deposited on the surface of the glass beads. Next, the sample is sequentially eluted while increasing the column temperature at a constant rate of 50 ° C./hr while flowing ODCB through the column at a constant flow rate. At this time, the concentration of the sample eluted in the solvent was set to the wave number 2925 cm of the asymmetric stretching vibration of methylene.^-1Is continuously detected by measuring the absorption with respect to an infrared detector. From this value, the concentration of the ethylene copolymer in the solution is quantitatively analyzed to determine the relationship between the elution temperature and the elution rate. According to the TREF analysis, since a change in elution rate with respect to a temperature change can be continuously analyzed with a very small amount of sample, a relatively fine peak that cannot be detected by a fractionation method can be detected.
[0014]
  The ethylene (co) polymer (A) in the present invention further has one peak of the elution temperature-elution amount curve by (f) continuous temperature rising elution fractionation method (TREF).₇₅-T₂₅And the density d satisfies the following relationship (Formula 2).
(Formula 2) d <0.950 g / cm³When
T₇₅-T₂₅≧ −300 × d + 285
d ≧ 0.950 g / cm³When
T₇₅-T₂₅≧ 0
  T₇₅-T₂₅And the density d satisfy the relationship of the above (formula 2), the heat seal strength and the heat resistance are further improved.
[0015]
  The ethylene (co) polymer (A) in the present invention is an ethylene (co) polymer (A1) that further satisfies the requirements of (g) and (h) described below, or (i) and (j) described below. The ethylene (co) polymer of the ethylene (co) polymer (A2) that satisfies the requirements of
[0016]
  In the present invention, the amount (% by mass) of the ODCB soluble content at 25 ° C. of the ethylene (co) polymer (A1), the density d, and the MFR have the following relationships (Formula 3) and (Formula 4). Satisfied,
(Formula 3) When d−0.008log MFR ≧ 0.93,
X <2.0
(Formula 4) When d−0.008 log MFR <0.93,
X <9.8 × 10³× (0.9300-d + 0.008logMFR)²+2.0 is satisfied, preferably,
When d-0.008log MFR ≧ 0.93,
X <1.0
If d−0.008log MFR <0.93,
X <7.4 × 10³× (0.9300-d + 0.008logMFR)²+2.0 is satisfied, and more preferably,
When d-0.008log MFR ≧ 0.93,
X <0.5
If d−0.008log MFR <0.93,
X <5.6 × 10³× (0.9300-d + 0.008logMFR)²The relationship of +2.0 is satisfied.
  Here, the amount X of soluble ODCB at 25 ° C. is measured by the following method. A sample of 0.5 g is heated with 20 ml of ODCB at 135 ° C. for 2 hours to completely dissolve the sample, and then cooled to 25 ° C. The solution is allowed to stand at 25 ° C. overnight and then filtered through a Teflon filter to collect the filtrate. This filtrate, which is a sample solution, was subjected to a wave number of 2925 cm of asymmetric stretching vibration of methylene using an infrared spectrometer.^-1The absorption peak intensity in the vicinity is measured, and the sample concentration is calculated using a calibration curve prepared in advance. From this value, the amount of soluble ODCB at 25 ° C. is obtained.
  The ODCB soluble component at 25 ° C. is a highly branched component and a low molecular weight component contained in the ethylene (co) polymer, which causes a decrease in heat resistance and stickiness of the surface of the molded product. This content is desirable to be low because it causes surface blocking. The amount of ODCB solubles is affected by the α-olefin content and molecular weight of the entire copolymer, ie, density and MFR. Accordingly, the fact that the density and the amount of soluble components of MFR and ODCB satisfying the above relationship indicate that the α-olefin contained in the entire copolymer is less unevenly distributed.
[0017]
  The ethylene (co) polymer (A1) in the present invention has a plurality of peaks in the elution temperature-elution amount curve determined by (h) continuous temperature rising elution fractionation method (TREF). The peak temperature on the high temperature side of the plurality of peaks is particularly preferably between 85 ° C and 100 ° C. The presence of this peak increases the melting point, increases the crystallinity, and improves the heat resistance and rigidity of the molded body.
[0018]
  The ethylene (co) polymer (A2) in the present invention has (i) 1 to 2 or more melting points, and (j) the highest melting point T._mlAnd the density d satisfy the following relationship (Formula 5).
(Formula 5) T_ml≧ 150 × d-19
Melting point T_mlWhen the density d satisfies the relationship of the above (formula 5), the heat resistance is improved.
  Among the ethylene (co) polymers (A2), an ethylene (co) polymer that further satisfies the following requirement (k) is preferable.
(K) The melt tension (MT) and the melt flow rate (MFR) satisfy the relationship of the following (formula 6).
(Formula 6) logMT ≦ −0.572 × logMFR + 0.3
  When MT and MFR satisfy the relationship of the above (formula 6), moldability such as film molding becomes good.
[0019]
  Here, as shown in FIG. 2, the ethylene (co) polymer (A1) has a special peak having a plurality of peaks in the elution temperature-elution amount curve obtained by the continuous temperature rising elution fractionation method (TREF). This is an ethylene / α-olefin copolymer. On the other hand, the ethylene (co) polymer of FIG. 3 is an ethylene (co) polymer having substantially one peak in the elution temperature-elution amount curve obtained by the continuous temperature rising elution fractionation method (TREF). This is an ethylene copolymer produced by a typical metallocene catalyst.
  In addition, as shown in FIG. 4, the ethylene (co) polymer (A2) has one TREF peak, but the conventional ethylene copolymer based on a metallocene catalyst has the above (formula 2). This is not satisfactory and is clearly distinguished from the conventional ethylene copolymer produced by a typical metallocene catalyst.
[0020]
  The ethylene (co) polymer (A) in the present invention is not particularly limited to a catalyst, a production method and the like as long as the above parameters are satisfied, but preferably an organic cyclic compound having at least a conjugated double bond and a cycle. A linear ethylene (co) polymer obtained by polymerizing ethylene or copolymerizing ethylene and an α-olefin in the presence of a catalyst containing a Group IV transition metal compound is desirable. Such a linear ethylene (co) polymer has a narrow molecular weight distribution and composition distribution, so it has excellent mechanical properties, heat sealability, heat blocking resistance, etc., and also has good heat resistance. .
[0021]
  In the production of the ethylene (co) polymer (A) in the present invention, it is particularly desirable to polymerize with a catalyst obtained by mixing the following compounds a1 to a4.
  a1: General formula Me¹R¹ _pR² _q(OR³)_rX¹ _4-pqrA compound represented by the formula:¹Represents zirconium, titanium, hafnium, R¹And R³Are each a hydrocarbon group having 1 to 24 carbon atoms, R²Is a 2,4-pentanedionate ligand or a derivative thereof, a benzoylmethanato ligand, a benzoylacetonate ligand or a derivative thereof, X¹Represents a halogen atom, and p, q and r are integers satisfying the ranges of 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, 0 ≦ r ≦ 4 and 0 ≦ p + q + r ≦ 4, respectively)
  a2: General formula Me²R⁴ _m(OR⁵)_nX² _z-mnA compound represented by the formula:²Is a group I-III element of the periodic table, R⁴And R⁵Are each a hydrocarbon group having 1 to 24 carbon atoms, X2 is a halogen atom or a hydrogen atom (however, X²Me is a hydrogen atom²Is limited to a group III element in the periodic table), z is Me²And m and n are integers satisfying the ranges of 0 ≦ m ≦ z and 0 ≦ n ≦ z, respectively, and 0 ≦ m + n ≦ z)
  a3: an organic cyclic compound having a conjugated double bond
  a4: Modified organoaluminum oxy compound and / or boron compound containing Al—O—Al bond
[0022]
  Further details will be described below.
  General formula Me of the catalyst component a1¹R¹ _pR² _q(OR³)_rX¹ _4-pqrIn the formula of the compound represented by¹Represents zirconium, titanium, and hafnium, and the types of these transition metals are not limited, and a plurality of them can be used, but it is particularly preferable that zirconium having excellent weather resistance of the copolymer is included. R¹And R³Are each a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms. Specifically, alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group and butyl group; alkenyl groups such as vinyl group and allyl group; phenyl group, tolyl group, xylyl group, mesityl group, indenyl group and naphthyl group And aryl groups such as benzyl group, trityl group, phenethyl group, styryl group, benzhydryl group, phenylbutyl group, and neofoyl group.
  These may be branched. R²Represents a 2,4-pentanedionato ligand or a derivative thereof, a benzoylmethanato ligand, a benzoylacetonate ligand or a derivative thereof. X¹Represents a halogen atom such as fluorine, iodine, chlorine and bromine. p and q are integers satisfying the ranges of 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, 0 ≦ r ≦ 4, and 0 ≦ p + q + r ≦ 4, respectively.
[0023]
  Examples of the compound represented by the general formula of the catalyst component a1 include tetramethylzirconium, tetraethylzirconium, tetrabenzylzirconium, tetrapropoxyzirconium, tripropoxymonochlorozirconium, tetraethoxyzirconium, tetrabutoxyzirconium, tetrabutoxytitanium, tetrabutoxy Hafnium and the like, especially Zr (OR) such as tetrapropoxyzirconium and tetrabutoxyzirconium₄Compounds are preferred, and two or more of these may be used in combination. Specific examples of the 2,4-pentanedionato ligand or derivative thereof, benzoylmethanato ligand, benzoylacetonate ligand or derivative thereof include tetra (2,4-pentandionato) zirconium. , Tri (2,4-pentanedionato) chloride zirconium, di (2,4-pentandedionato) dichloride zirconium, (2,4-pentandedionato) trichloride zirconium, di (2,4-pentandedionato) Diethoxide zirconium, di (2,4-pentanedionato) di-n-propoxide zirconium, di (2,4-pentanedionato) di-n-butoxide zirconium, di (2,4-pentane) Diato) dibenzylzirconium, di (2,4-pentanedionate) dineoyl zirconium, tetra ( Benzoylmethanato) zirconium, di (dibenzoylmethanato) diethoxide zirconium, di (dibenzoylmethanato) di-n-propoxide zirconium, di (dibenzoylmethanato) di-n-butoxidezirconium, di (benzoyl) Acetonato) diethoxide zirconium, di (benzoylacetonato) di-n-propoxide zirconium, di (benzoylacetonato) di-n-butoxide zirconium and the like.
[0024]
  General formula Me of the catalyst component a2²R⁴ ₀(OR⁵)_nX² _z-mnIn the formula of the compound represented by²Represents a group I-III element of the periodic table, such as lithium, sodium, potassium, magnesium, calcium, zinc, boron, aluminum and the like. R4 and R5 are each a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group. Alkyl groups such as vinyl groups and allyl groups; aryl groups such as phenyl groups, tolyl groups, xylyl groups, mesityl groups, indenyl groups and naphthyl groups; benzyl groups, trityl groups, phenethyl groups, styryl groups, benzhydryls Aralkyl groups such as a group, phenylbutyl group, and neofoyl group. These may be branched. X²Represents a halogen atom such as fluorine, iodine, chlorine and bromine or a hydrogen atom. However, X²Me is a hydrogen atom²Is limited to Group III elements of the periodic table exemplified by boron, aluminum and the like. Z is Me²M and n are integers satisfying the ranges of 0 ≦ m ≦ z and 0 ≦ n ≦ z, respectively, and 0 ≦ m + n ≦ z.
[0025]
  Examples of the compound represented by the general formula of the catalyst component a2 include organic lithium compounds such as methyl lithium and ethyl lithium; organic magnesium compounds such as dimethyl magnesium, diethyl magnesium, methyl magnesium chloride, and ethyl magnesium chloride; dimethyl zinc and diethyl Organic zinc compounds such as zinc; organic boron compounds such as trimethylboron and triethylboron; trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, tridecylaluminum, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum Sesquichloride, diethylaluminum ethoxide, diethylaluminum hydride Any derivative of an organic aluminum compound, and the like.
[0026]
  The organic cyclic compound having a conjugated double bond of the catalyst component a3 is cyclic, having one or more rings having 2 or more, preferably 2 to 4, more preferably 2 to 3 conjugated double bonds. A cyclic hydrocarbon compound having 4 to 24 carbon atoms, preferably 4 to 12 carbon atoms; the cyclic hydrocarbon compound is partially a hydrocarbon residue having 1 to 6 carbon atoms (typically having 1 to A cyclic hydrocarbon compound substituted with 12 alkyl groups or an aralkyl group; having 1 or 2 rings having 2 or more, preferably 2 to 4, more preferably 2 to 3 conjugated double bonds An organosilicon compound having a cyclic hydrocarbon group having a total carbon number of 4 to 24, preferably 4 to 12; the cyclic hydrocarbon group is partially a hydrocarbon residue or alkali metal salt (sodium 1-6) Or lithium salt) Organosilicon compounds are included. Particularly preferred is one having a cyclopentadiene structure in any of the molecules.
[0027]
  Suitable examples of the compound include cyclopentadiene, indene, azulene, or alkyl, aryl, aralkyl, alkoxy or aryloxy derivatives thereof. Moreover, the compound which these compounds couple | bonded (bridge | crosslinked) via the alkylene group (The carbon number is 2-8 normally, Preferably 2-3) is also used suitably.
[0028]
  The organosilicon compound having a cyclic hydrocarbon group can be represented by the following general formula.
A_LSiR_4-L
  Here, A represents the cyclic hydrogen group exemplified by cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group, and substituted indenyl group, and R represents methyl group, ethyl group, propyl group, isopropyl group, butyl group An alkyl group such as a group; an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group; an aryl group such as a phenyl group; an aryloxy group such as a phenoxy group; an aralkyl group such as a benzyl group; To 24, preferably 1 to 12 hydrocarbon residues or hydrogen, L is 1 ≦ L ≦ 4, preferably 1 ≦ L ≦ 3.
[0029]
  Specific examples of the organic cyclic hydrocarbon compound of component a3 include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, propylcyclopentadiene, butylcyclopentadiene, 1,3-dimethylcyclopentadiene, 1-methyl-3-ethylcyclopentadiene. 1-methyl-3-propylcyclopentadiene, 1-methyl-3-butylcyclopentadiene, 1,2,4-trimethylcyclopentadiene, pentamethylcyclopentadiene, indene, 4-methyl-1-indene, 4,7- Cyclopolyene having 5 to 24 carbon atoms such as dimethylindene, cycloheptatriene, methylcycloheptatriene, cyclooctatetraene, azulene, fluorene, methylfluorene, or substituted cyclopolyene, monocyclope Tajienirushiran, biscyclopentadienyl silane, tris cyclopentadienyl silane, mono indenyl silane, bis indenyl silane, and tris indenyl silane.
[0030]
  The modified organoaluminum oxy compound containing an Al—O—Al bond of the catalyst component a4 is obtained by reacting an alkylaluminum compound with water to obtain a modified organoaluminum oxy compound usually referred to as an aluminoxane. Usually, it contains 1 to 100, preferably 1 to 50 Al—O—Al bonds. The modified organoaluminum oxy compound may be linear or cyclic.
[0031]
  The reaction between organoaluminum and water is usually carried out in an inert hydrocarbon. As the inert hydrocarbon, aliphatic, alicyclic and aromatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, benzene, toluene and xylene are preferable.
  The reaction ratio (water / Al molar ratio) between water and the organoaluminum compound is usually 0.25 / 1 to 1.2 / 1, preferably 0.5 / 1 to 1/1.
[0032]
  Examples of boron compounds include triethylaluminum tetra (pentafluorophenyl) borate, tri (ethylpentafluorophenyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, and butyl. Ammonium tetra (pentafluorophenyl) borate, N, N-dimethylanilinium tetra (pentafluorophenyl) borate, N, N-dimethylanilinium tetra (3,5-difluorophenyl) borate, trityltetrakispentafluoroborate, ferroce Examples thereof include nitrotetrakispentafluoroborate and trispentafluoroborane. Among these, N, N-dimethylanilinium tetra (pentafluorophenyl) borate, trityltetrakispentafluoroborate, ferrocenium tetrakispentafluoroborate, and trispentafluoroborane are preferable.
  The catalyst may be used by mixing and contacting a1 to a4, but it is preferable to use the catalyst supported on an inorganic carrier and / or a particulate polymer carrier (a5).
[0033]
  Examples of the inorganic carrier and / or particulate polymer carrier (a5) include carbonaceous materials, metals, metal oxides, metal chlorides, metal carbonates or mixtures thereof, thermoplastic resins, thermosetting resins, and the like. Suitable metals that can be used for the inorganic carrier include iron, aluminum, nickel and the like.
  Specifically, SiO₂, Al₂O₃, MgO, ZrO₂TiO₂, B₂O₃, CaO, ZnO, BaO, ThO₂Etc. or a mixture thereof, SiO 2₂-Al₂O₃, SiO₂-V₂O₅, SiO₂-TiO₂, SiO₂-V₂O₅, SiO₂-MgO, SiO₂-Cr₂O₃Etc. Among these, SiO₂And Al₂O₃The main component is at least one component selected from the group consisting of:
  As the organic compound, any of a thermoplastic resin and a thermosetting resin can be used. Specifically, particulate polyolefin, polyester, polyamide, polyvinyl chloride, poly (meth) acrylate, polystyrene, Examples include norbornene, various natural polymers, and mixtures thereof.
[0034]
  The inorganic carrier and / or the particulate polymer carrier can be used as they are, but preferably, as a pretreatment, these carriers are contacted with an organoaluminum compound or a modified organoaluminum compound containing an Al—O—Al bond. After that, it can also be used as component a5.
[0035]
  The method for producing the ethylene (co) polymer (A) in the present invention is produced by a gas phase polymerization method, a slurry polymerization method, a solution polymerization method, etc. substantially free of a solvent in the presence of the catalyst, Illustrated for aliphatic hydrocarbons such as butane, pentane, hexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, etc. with oxygen and water turned off Produced in the presence or absence of an inert hydrocarbon solvent. The polymerization conditions are not particularly limited, but the polymerization temperature is usually 15 to 350 ° C., preferably 20 to 200 ° C., more preferably 50 to 110 ° C., and the polymerization pressure is usually normal pressure to 70 kg / cm in the case of the low-medium pressure method.²G, preferably normal pressure to 20 kg / cm²G, usually 1500 kg / cm for high pressure method²G or less is desirable. The polymerization time is usually from 3 minutes to 10 hours, preferably from about 5 minutes to 5 hours in the case of the low and medium pressure method. In the case of the high pressure method, it is usually 1 minute to 30 minutes, preferably about 2 minutes to 20 minutes. In addition, the polymerization is not particularly limited to a one-stage polymerization method, but also a two-stage or more multi-stage polymerization method in which polymerization conditions such as hydrogen concentration, monomer concentration, polymerization pressure, polymerization temperature, and catalyst are different from each other. A particularly preferable production method includes the method described in JP-A-5-132518.
[0036]
  The ethylene (co) polymer (A) in the present invention is a halogen concentration of at most 10 ppm, preferably 5 ppm or less, more preferably, by using a catalyst having no halogen such as chlorine in the above catalyst components. Can be substantially free (ND: 2 ppm or less). By using such a halogen-free ethylene (co) polymer (A) such as chlorine, it becomes unnecessary to use a conventional acid neutralizer (halogen absorber), and chemical stability and hygiene And can provide a molded body such as a polyolefin-based resin single-layer film and a laminate using the film, and is particularly suitably used as a packaging material in the food, medical, electronic fields and the like.
[0037]
  (B) Other polyolefin resins in the present invention include ethylene-based (co) polymers by a high-pressure radical polymerization method, high / medium / low-pressure methods using Ziegler-type catalysts, and other ethylene homopolymers by known methods. , A copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms, a polypropylene resin, and the like.
  Examples of the high-pressure radical polymerization ethylene-based (co) polymer include low-density polyethylene (LDPE), ethylene-vinyl ester copolymer obtained by high-pressure radical polymerization, ethylene and α, β-unsaturated carboxylic acid or its Examples thereof include a copolymer with a derivative.
[0038]
  The MFR of the LDPE is in the range of 0.01 to 200 g / 10 minutes, preferably 0.05 to 100 g / 10 minutes, more preferably 0.1 to 80 g / 10 minutes. If it is this range, melt tension will become an appropriate range and a moldability will improve. The density of LDPE is 0.91 to 0.94 g / cm.³More preferably, 0.91 to 0.935 g / cm³Range. If it is this range, melt tension will become an appropriate range and a moldability will improve. The melt tension of LDPE is 1.5 to 25 g, preferably 3 to 20 g, more preferably 3 to 15 g. Moreover, the molecular weight distribution Mw / Mn of LDPE is 3.0-12, Preferably it is 4.0-8.0.
[0039]
  The ethylene-vinyl ester copolymer is vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate, trifluoroacetic acid, which are mainly produced by high-pressure radical polymerization. It is a copolymer with vinyl ester monomers such as vinyl. Among these, vinyl acetate is particularly preferable. Further, a copolymer composed of 50 to 99.5% by mass of ethylene, 0.5 to 50% by mass of vinyl ester, and 0 to 49.5% by mass of other copolymerizable unsaturated monomers is preferable. In particular, the vinyl ester content is 3 to 30% by mass, preferably 5 to 25% by mass. The MFR of the ethylene / vinyl ester copolymer is in the range of 0.01 to 200 g / 10 minutes, preferably 0.05 to 100 g / 10 minutes, and more preferably 0.1 to 50 g / 10 minutes.
[0040]
  Examples of the copolymer of ethylene and an α, β-unsaturated carboxylic acid or a derivative thereof include ethylene / (meth) acrylic acid or an alkyl ester copolymer thereof, and these comonomers include acrylic acid, methacrylic acid, and the like. Acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, cyclohexyl acrylate, Examples include cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, glycidyl acrylate, and glycidyl methacrylate. Among these, alkyl esters such as methyl and ethyl of (meth) acrylic acid are particularly preferable. In particular, the content of (meth) acrylic acid ester is in the range of 3 to 30% by mass, preferably 5 to 25% by mass. The MFR of the copolymer of ethylene and α, β-unsaturated carboxylic acid or derivative thereof is 0.01 to 200 g / 10 minutes, preferably 0.05 to 100 g / 10 minutes, more preferably 0.1 to 80 g / 10 minutes.
[0041]
  As an ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms by a high, medium or low pressure method using the Ziegler type catalyst or the like and other known methods, a density of 0.94 to 0 is used. .97 g / cm³High density polyethylene, density 0.91-0.94 g / cm³Linear low density polyethylene (LLDPE), density 0.86-0.91 g / cm³Very low density polyethylene (VLDPE), density 0.86-0.91 g / cm³And ethylene / α-olefin copolymer rubber such as ethylene / propylene copolymer rubber and ethylene / propylene / diene copolymer rubber.
[0042]
  The LLDPE by the Ziegler type catalyst has a density of 0.91 to 0.94 g / cm.³, Preferably 0.91 to 0.93 g / cm³The α-olefin is a copolymer having 3 to 20 carbon atoms, preferably 4 to 12 carbon atoms. Specifically, propylene, 1-butene, 4 -Methyl-1-pentene, 1-hexene, 1-octene and the like.
[0043]
  Further, the very low density polyethylene (VLDPE) by the Ziegler type catalyst has a density of 0.86 to 0.91 g / cm.³, Preferably 0.88-0.905 g / cm³It is an ethylene / α-olefin copolymer in the range of 5 and is a polyethylene having intermediate properties between LLDPE and ethylene / α-olefin copolymer rubber (EPR, EPDM).
The ethylene / α-olefin copolymer rubber has a density of 0.86 to 0.91 g / cm.³Ethylene / propylene copolymer rubber, ethylene / propylene / diene copolymer rubber, and the like. Examples of the ethylene / propylene rubber include a random copolymer (EPM) mainly composed of ethylene and propylene, and Examples of the third component include a random copolymer (EPDM) containing as a main component a diene monomer (dicyclopentadiene, ethylidene norbornene, or the like).
[0044]
  Polypropylene resins include propylene homopolymers, copolymers of propylene and other α-olefins, for example, random copolymers with α-olefins such as ethylene, 1-butene, 1-pentene, 1-hexene. A polymer, a block copolymer, etc. are mentioned.
[0045]
  The polyolefin resin material of the present invention comprises a resin material containing 100 to 10% by mass of an ethylene (co) polymer (A) and (B) 0 to 90% by mass of another polyolefin resin. When the ethylene (co) polymer (A) is less than 10% by mass, or (B) other polyolefin resin is more than 90% by mass, low temperature heat sealability, adhesive strength, flexibility, tear strength, heat fusion And properties such as chemical resistance may be impaired.
  Also, depending on the purpose, application, etc., the blending ratio of the polyolefin resin material of the present invention and other polyolefin resin is different, but when the purpose is to maintain low-temperature heat sealability, adhesive strength and high-speed moldability It is desirable to blend the high-pressure radical method low-density polyethylene in a proportion of 5 to 40% by mass.
[0046]
  The first feature of the polyolefin resin material of the present invention is that the mass average molecular weight (Mw) of the ODCB soluble component at 23 ° C. of the ethylene (co) polymer (A) is in the range of 8000 to 30000. This ODCB-soluble component is a highly branched component (rubber component) and a low molecular weight component generally contained in an ethylene (co) polymer, causing heat resistance and stickiness of the product, sanitary deterioration and blocking. However, by making the mass average molecular weight (Mw) of the ODCB soluble content in the range of 8000 to 30000 as in the present invention, the stickiness of the product is prevented, and the presence of an appropriate high molecular weight rubber component, At the time of melting, the molten resin penetrates into a base material such as paper or polyethylene terephthalate, exhibits an anchor effect on the base material after solidification, and improves the adhesive strength. Therefore, if the mass average molecular weight of the permeated resin is low, the peel strength after solidification is low, and the adhesive strength cannot be improved.
[0047]
  The second feature of the polyolefin resin material of the present invention is that it does not substantially contain additives. That is, conventionally, since the deterioration of the resin occurs, the additive is blended, but the adhesive strength is sacrificed. However, by using a specific polyolefin resin material as in the present invention, an antioxidant, an antiblocking agent, a lubricant, an acid absorbent (= acid neutralizer), an antistatic agent, an antifogging agent, and an ultraviolet absorber. It has been found that the adhesive strength can be remarkably maintained due to the synergistic effect with the first feature, which can be molded without adding additives such as.
  In the present invention, the additive is not substantially added is an additive that does not impair the adhesive strength, an additive that does not migrate to the contacted object, a property of the clean molded body of the present invention that does not change the contacted object This means that it does not prevent the use of additives that do not essentially impede, and when ordinary additives are used, the adhesive strength or cleanliness is greater than the adhesive strength of the ingredients without additives. It means that it does not decrease. In particular, additives that reduce the adhesive strength such as antioxidants, acid neutralizers, additives that elute to the outside, for example, if the contents are liquid, they are eluted in the liquid It means an additive, an additive in which odor is transferred, or an additive that is unevenly distributed on the film surface with time.
  In the present invention, since these additives are not contained in the polyolefin resin material, it is possible to provide a molded article such as a polyolefin film, a laminate, and a container that is hygienic and has no odor transfer to the product. it can.
  In particular, in the present invention, since the ethylene (co) polymer (A) is produced using a halogen-free catalyst, it is not necessary to add an acid neutralizing agent such as calcium stearate or hydrotalcite. Further, since there is no decrease in adhesive strength due to these additives, it is particularly suitably used as a sealant material.
[0048]
  The third feature of the polyolefin-based resin material in the present invention is that the reason is not clear at the time of film molding, but by including the ethylene (co) polymer (A), low temperature molding, specifically 110 to Film formation at a low temperature of 200 ° C. is possible, 120 to 180 ° C. is more preferable, and formation in the range of 120 to 160 ° C. is possible.
  In the case of laminate molding, when high speed is required, molding can be performed at 200 to 330 ° C, preferably 260 to 320 ° C. In particular, when used in combination with surface treatment techniques such as ozone treatment and corona treatment, low temperature molding at around 300 ° C. is possible.
  If low temperature molding as described above is performed, the resin is hardly deteriorated by heat, and there is an advantage that it is not necessary to add an antioxidant. Moreover, since the resin blocking is reduced by molding at a low temperature, it is not necessary to add an antiblocking agent or the like.
[0049]
  The molded body of the present invention is a molded body characterized in that the polyolefin-based resin material is produced by at least one molding method selected from extrusion molding, injection molding, blow molding, and rotational molding. Specific examples thereof include films, sheets, tapes, bags, pouches, liquid containers, paper containers, cups, retort containers, medical containers, electronic material containers, and the like. In particular, containers, bags, or packages for food, medical use, electronic materials and the like are suitable.
[0050]
  A preferred embodiment of the molded body of the present invention is a laminate such as a sealant material.
  That is, the laminate of the present invention comprises (A) 100 to 10% by mass of an ethylene (co) polymer that satisfies the following (a) to (e):
(A) Density is 0.86-0.97 g / cm³,
(B) A melt flow rate of 0.01 to 200 g / 10 minutes,
(C) molecular weight distribution (Mw / Mn) is 1.5 to 4.5,
(D) The mass average molecular weight of the o-dichlorobenzene (ODCB) soluble component at 23 ° C. is in the range of 8000 to 30000.
(E) Temperature T at which 25% of the total elution temperature obtained from the integral dissolution curve of elution temperature-elution volume curve by continuous temperature rising elution fractionation method (TREF) is eluted₂₅And the temperature T at which 75% of the total elution occurs₇₅Difference with T₇₅-T₂₅And the density d is
(Formula 1) T₇₅-T₂₅≦ −670 × d + 644
(B) Polyolefin resin material layer comprising 0 to 90% by mass of other polyolefin resin (II) Without using an anchor coating agent, a base material layer comprising at least one base material (I) The laminate formed above.
[0051]
  The laminate preferably has the polyolefin resin material layer (II) Of the base material layer (I) Is characterized in that (a) the oxygen atom concentration is 1.8% by mass or more and (b) the surface oxidation degree is 0.10 or more. Preferably, the degree of oxidation is (b) the oxygen atom concentration (Oc) of 1.8 to 40% by mass, and (b) the degree of surface oxidation (Or) is 0.10 to 2.0, more preferably (b) ) Oxygen atom concentration (Oc) of 2.0 to 40% by mass, and (b) Surface oxidation degree (Or) of 0.12 to 1.8, more preferably (a) Oxygen atom concentration (Oc) of 2. 2 to 40% by mass, and (b) the degree of surface oxidation (Or) is 0.15 to 1.5, particularly preferably (b) the oxygen atom concentration is 2.5 to 40% by mass and (b) the degree of surface oxidation ( Or) is in the range of 0.20 to 1.2.
  Within such a range, the amount of oxygen-containing functional groups such as carbonyl groups that contribute to adhesion increases, and the average mass molecular weight of the ODCB-soluble component is in an appropriate range, and anchors are formed in the substrate. Since the effect is exhibited, the adhesive strength is remarkably improved.
[0052]
  Here, the oxygen atom concentration (Oc) is a polyolefin resin material layer (II), Base material layer (I) Is a value obtained by substituting oxygen O1s corrected peak intensity: O and carbon C1s corrected peak intensity: C, measured by the ESCA method, into (Equation 7). The oxygen atom introduction amount on the bonding surface can be quantified by the oxygen atom concentration.
(Formula 7) Oc = O / (C + O) × 100 (%)
[0053]
  The surface oxidation degree (Or) is a polyolefin resin material layer (II), Base material layer (I) Is a value indicating the degree to which a compound having an oxygen-containing group such as a carbonyl group or an aldehyde group, which is considered to contribute to adhesion, is produced by the oxidation treatment. The surface oxidation degree (Or) is 1720 cm due to absorption of the carbonyl group in the absorbance spectrum by the surface FT-IR (ATR) method.^-1The height of the nearby peak is I (1720), 1370 (1369) cm due to pitch absorption of the methylene group.^-1When the height of a nearby peak is I (1370), it can be obtained by (Equation 8).
(Formula 8) Or = I (1720) / I (1370)
  Since this value is calculated based on the longitudinal absorption of methylene groups, it is difficult to compare between polymers with different molecular weights. However, more detailed information on surface oxidation can be obtained by measuring (a) above. can get.
[0054]
  The measurement of the oxygen atom concentration (Oc) and the measurement of the surface oxidation degree (Or) are performed after the laminating step, but when the base material layer (I) and the polyolefin resin material layer (II) are adhered to each other. It becomes difficult to obtain a sample for measuring the oxidation-treated surface of the polyolefin resin material layer (II). Therefore, an ESCA measurement sample and an IR measurement sample are prepared in the laminating step. In order to obtain a sample for IR measurement, first, before laminating, as shown in FIG. 5A, paper 13 as shown in FIG. 5B is formed on a part of the surface of the base material 12 on which the molten resin film 11 is laminated. The sample collection paper 15 on which the vinylidene tetrafluoride adhesive tape 14 (non-adhesive surface) is bonded is used by using a double-sided adhesive tape or the like so that the vinylidene tetrafluoride adhesive tape 14 contacts the molten resin film 11. Paste. Next, after laminating the molten resin film 11 on the base material 12 to obtain the laminated body 10, the bonded portion of the sample collection paper 15 of the laminated body 10 is cut out. As shown in FIG. 6A, the laminated body of the pasting portion of the sample collection paper 15 is formed by solidifying the base material layer (I) 16 composed of the base material 12, paper 13, vinylidene tetrafluoride adhesive tape 14, and the molten resin film 11. The polyolefin-based resin material layers (II) 17 formed in this order are laminated in this order. Since the adhesive tape 14 made of vinylidene tetrafluoride and the polyolefin resin material layer (II) 17 are not bonded, as shown in FIG. 6B, the polyolefin resin material layer (II) 17 is separated to obtain an oxidized surface. A polyolefin-based resin material layer (II) 17 in which 18 is completely exposed is obtained. Using the polyolefin-based resin material layer (II) 17 thus obtained alone as an IR measurement sample, the IR of the oxidation-treated surface 18 is measured.
  In addition, the ESCA measurement sample uses a polyethylene terephthalate (PET) film in which one side is untreated and the other side is corona-treated in place of the sample collection paper 15 in the above-described method for obtaining the IR measurement sample. . The corona surface of this PET film is bonded onto the base material layer 12, the untreated surface of the PET film is set to the polyolefin-based resin material layer (II) side, and an ESCA measurement sample is prepared in the same manner as the IR measurement sample described above. obtain. Then, the ESCA of the surface in contact with the PET film (untreated surface) is measured.
[0055]
  The base material used for the base material layer (I) in the present invention includes a film or sheet, a plate-like body and the like. Examples of the base layer (I) include polypropylene resins, polyamide resins, polyester resins, saponified ethylene-vinyl acetate copolymers, polyvinylidene chloride, polycarbonate, and other thermoplastic plastic films or sheets (extensions thereof) , Printed matter), metal foil or metal plate such as aluminum, iron, copper, or alloys based on these, vapor-deposited films of inorganic oxides such as silica-deposited plastic films, alumina-deposited plastic films, gold, silver, aluminum, etc. A vapor-deposited film such as a metal other than these metals or a compound other than these metal oxides, paper, paperboard, cellophane, woven fabric, non-woven fabric, and the like are used.
[0056]
  Specific examples of the laminate include SLL / paper, SLL / paper / SLL, SLL / OPP, SLL / OPP / SLL, SLL / PA, SLL / PA / SLL, SLL / ONY, SLL / ONY / SLL, SLL / PEs, SLL / PEs / SLL, SLL / OPEs, SLL / OPEs / SLL, SLL / EVOH, SLL / EVOH / SLL, SLL / nonwoven fabric, SLL / Al foil, SLL + HDPE / paper / SLL, paper / SLL / CPP, PET / SLL / CPP, paper / SLL / Al foil / SLL, paper / SLL / deposited PET / SLL, paper / SLL / EVOH / SLL, and the like.
  Here, SLL is the ethylene (co) polymer (A) in the present invention, OPP is biaxially stretched polypropylene, PA is polyamide, ONY is biaxially stretched polyamide, PEs is polyester, and OPEs is biaxial. Stretched polyester, EVOH is saponified ethylene-vinyl acetate copolymer, Al foil is aluminum foil, HDPE is high-density polyethylene, CPP is cast polypropylene film, evaporated PET is metal such as aluminum, alumina, silica, etc. It is a polyethylene terephthalate which vapor-deposited this inorganic oxide.
[0057]
  In the above-described laminate, the polyolefin resin material layer (II) comprising the ethylene (co) polymer (A) of the present invention or a resin composition containing the same is formed on the base material layer (I). The surface of the polyolefin resin material layer (II) in contact with the base material layer (I) is (i) an oxygen atom concentration (Oc) of 1.8% by mass or more, and (b) a surface oxidation degree ( Or) is 0.10 or more.
  The ethylene (co) polymer (A) of the present invention is easily oxidized and has a high molecular weight component sufficient to cause cohesive failure, having a penetrating ability to the base material. Therefore, the surface of the polyolefin-based resin material layer (II) in contact with the base material has a sufficient amount of oxygen-containing functional groups contributing to adhesion, and the polyolefin-based resin material layer ( II) and the base material layer (I) are bonded with high adhesive strength. Therefore, this laminate does not require the use of an anchor coat agent (adhesive) and contains additives.BeenIt is clean with little solvent elution. Furthermore, by not using an anchor coat agent, the cost is reduced and the operation is simplified. In addition, since no solvent is used, environmental problems and odor problems are eliminated.
[0058]
  Next, the manufacturing method of the laminated body of this invention is demonstrated. In the method for producing a laminate of the present invention, first, a polyolefin resin material comprising a resin composition containing the above-described ethylene (co) polymer (A) or ethylene (co) polymer (A) is obtained using a T-die or the like. The molten resin film is melt-extruded at a molding temperature of 200 to 350 ° C., and at least one surface of the molten resin film is (i) an oxygen atom concentration of 1.8% by mass or more and (b) a surface oxidation degree of 0.10. While performing the oxidation treatment as described above, the molten resin film is laminated on the base material so that the oxidized surface of the molten resin film is in contact with the base material to obtain a laminate.
[0059]
  The oxidation treatment is to bring oxygen, air, or ozone into contact with the molten resin film. At that time, the oxidation treatment may be performed with air, or the oxidation treatment may be forcibly performed using an oxidation treatment apparatus.
  Specific examples of the oxidation treatment method include ozone treatment, ultraviolet treatment, plasma treatment, corona treatment, and the like, but ozone treatment is particularly desirable because of its efficiency.
  The temperature of the oxidation treatment is not particularly limited, but preferably applied to a molten resin film because it is easy and efficient to oxidize, and is preferably at or above the melting point of the resin, preferably 200 to 320 ° C.
  When the polyolefin-based resin material layer (II) and the base material layer (I) are laminated by such oxidation treatment, the layers can be firmly laminated at a lower temperature.
[0060]
  The amount of ozone treatment in the oxidation treatment with ozone is 5 g / Nm, although it varies depending on the type and conditions of the substrate.³× 1Nm³/ Hr ~ 100g / Nm³× 20Nm³/ Hr (ie, 5 to 2000 g / hr), preferably 10 g / Nm³× 1.5Nm³/ Hr ~ 70g / Nm³× 10Nm³/ Hr (ie 15-700 g / hr), more preferably 15 g / Nm³× 2Nm³/ Hr-50g / Nm³× 8Nm³/ Hr (ie, 30 to 400 g / hr).
  When the ozone treatment amount is less than 5 g / hr, the oxidation treatment becomes insufficient, and the polyolefin resin material layer (II) And base material layer (I) And the adhesive strength exceeds 2000 g / hr, the resin material may be deteriorated.
  Further, it is desirable that the base material is subjected to corona discharge treatment or the like. At that time, the corona discharge treatment amount is 1 to 300 w min / m.², Preferably 5 to 200 w min / m²More preferably, 10 to 100 w min / m²It is. The laminated body can drastically improve the adhesive strength by combining the oxidation treatment with ozone and the corona discharge treatment.
[0061]
  In the present invention, the production method of the laminate is not limited, but the extrusion lamination method is particularly preferred from the standpoint of continuous production.
  In the case of the extrusion laminating method, the resin temperature of the molten resin film is preferably in the range of 200 to 350 ° C, and preferably in the range of 250 to 330 ° C.
  When the resin temperature is lower than 200 ° C., the adhesive strength between the polyolefin-based resin material layer (II) and the base material layer (I) may be lowered in the obtained laminate. On the other hand, when the resin temperature of the molten resin film exceeds 350 ° C., the resin deteriorates, and the intended characteristics may not be obtained.
[0062]
  The film of the present invention can be formed by various methods. For example, an air-cooled inflation method, a water-cooled inflation method, a T-die method, or the like is suitable, and the air-cooled inflation method is particularly suitable in terms of economy and moldability.
  The air-cooled blown film can be produced by an air-cooled blown film production apparatus. For example, a resin material is extruded through a circular die from an extruder at a temperature of 110 to 200 ° C., and contacted with air blown out from an air-cooled air ring. It is made to cool by making it cool, and after making it solidify and taking up with a pinch roll, it winds up to a frame. In addition to the air-cooled method inflation film, a water-cooled method inflation film and a T-die method film can also be produced, and a single layer film having good transparency, low-temperature impact properties, and the like can be obtained. The thickness of the film produced by such a method is preferably about 5 to 200 μm, more preferably about 10 to 100 μm from the viewpoint of ease of use.
[0063]
  The heat seal temperature of the film is 120 ° C. or lower, preferably 115 ° C. or lower, more preferably 110 ° C. or lower.
  The heat seal temperature according to the present invention is determined as follows. A single-layer film having a thickness of 80 μm is prepared, and a test piece having a heat seal width of 15 mm and a length of 80 mm is cut out therefrom. Test specimens were heat sealed for 1.0 second and heat sealed pressure 1.5 kgf / cm.²Then, a heat test is performed at a tensile speed of 300 mm / min to obtain a heat seal strength (gf / 15 mm width). Heat sealing is performed by changing the sealing temperature at several points, and the heat sealing strength is obtained as described above in a tensile test. A graph of the seal temperature and the heat seal strength is created, a sheet temperature at which the heat seal strength is 500 gf / 15 mm width is obtained from the graph, and this temperature is set as the heat seal temperature.
[0064]
  Moreover, it is desirable that the film has a dart impact strength of 600 g or more measured in accordance with ASTM D-1709 B method. If the dirt impact strength is less than 600 g, bag breakage, pinholes and the like are likely to occur.
  The film preferably has a tear strength measured in accordance with JIS P8116 of 90 kg / cm or more in the MD direction and 150 kg / cm or more in the TD direction. If the tear strength is less than 90 kg / cm in the MD direction and less than 150 kg / cm in the TD direction, there is a possibility that bag breakage, pinholes, etc. may occur.
  The film preferably has a static friction coefficient measured in accordance with ASTM D1894 in the range of 0.10 to 0.40. If the coefficient of static friction is less than 0.10, the surface of the single layer film becomes slippery and the loadability when it is made into a bag is deteriorated, and if it exceeds 0.40, the storage property of the contents is deteriorated.
[0065]
  Moreover, a container or a bag is mentioned as another suitable embodiment of the molded object of this invention. In particular, it is optimal as a paper container because it is free of adhesive strength and additives, and is used as a container for milk, juice, liquor and the like.
[0066]
  The first aspect of the paper container of the present invention is composed of a laminate comprising at least a paper layer (I-1) and / or a barrier layer (I-2) and a polyolefin resin material layer (II) as a heat seal layer. The
  In addition, the second aspect is the plastic layer (I-3) / paper layer (I-1) / polyolefin resin material layer (II-1) / barrier layer (I-2) / heat seal layer (polyolefin resin). The material layers (II-2)) are laminated in this order.
  More specifically, paper / SLL, paper / SLL / Al foil / SLL, paper / SLL / Al₂O₃Deposition PET / SLL, Paper / SLL / SiO₂Deposition PET / SLL, Paper / SLL, Paper / SLL / EVOH / SLL, Paper / SLL, Paper / SLL / Al foil / SLL / PET / SLL, Paper / SLL / Al foil / SLL / EVOH / SLL, PE / Paper / SLL / Al foil / SLL, PE / paper / SLL / Al₂O₃Deposition PET / SLL, PE / paper / SLL / SiO₂Deposition PET / SLL, PE / paper / SLL, PE / paper / SLL / EVOH / SLL, PE / paper / SLL, PE / paper / SLL / Al foil / SLL / PET / SLL, PE / paper / SLL / Al foil / SLL / EVOH / SLL and the like.
  (However, SLL: ethylene polymer of the present invention, Al foil: aluminum foil, Al₂O₃: Alumina, PET: Polyester resin, SiO₂: Silica, EVOH: Saponified product of ethylene-vinyl acetate copolymer. )
[0067]
  Another embodiment of the molded body of the present invention includes an inner bag for bag-in-box.
  The inner bag for a bag-in-box according to the present invention uses a film, a sheet, or the laminate made of a polyolefin resin material containing the specific ethylene (co) polymer (A) in at least the innermost layer of the inner bag. It is characterized by this.
[0068]
  Further, as another embodiment of the molded article of the present invention, a film, sheet or laminate made of a polyolefin resin material containing the specific ethylene (co) polymer (A) in at least the innermost layer of the container or package It uses the body and is applied to inner bags for bag-in-boxes, medical containers and the like.
  The inner bag for a bag-in-box, a medical container, a package or the like is generally formed of a single layer film or a laminate with a substrate. When the inner bag for a bag-in-box is made of a laminate, it is composed of a laminate of two or more layers of linear polyolefin having the same type and different density, or a linear polyolefin / adhesive / barrier property. It is often composed of a barrier resin such as resin / adhesive / linear polyolefin. Films and laminates made of the polyolefin resin material of the present invention can be suitably used as their heat seal layers.
[0069]
  As a more preferred specific example, it is composed of at least one intermediate layer (II) and a plurality of three or more layers having the outer layer (I) and the outer layer (III) formed on both sides, and the density of the intermediate layer (d2 ) And the density (d1) of the outer layer (I) and the density (d3) of the outer layer (III) are d2 ≦ d1, d3, and at least a heat seal layer film forming the innermost layer It is comprised with the film of invention.
  Further, the film other than the innermost layer may be composed of ordinary linear polyethylene, or may be composed entirely of the film of the present invention. These linear polyethylenes have a density of 0.86 to 0.95 g / cm.³, Preferably density 0.90 to 0.94 g / cm³It is desirable to be selected within the range.
  For example, the outer layer I (d = 0.92 to 0.94 g / cm³) / Inner layer II (d = 0.89-0.92 g / cm)³) / Outer layer III (d = 0.92 to 0.94 g / cm)³) Can be selected.
[0070]
  These molded articles used for inner bags for bag-in-boxes, medical containers or packaging bodies can be molded by extrusion molding such as inflation film and cast film, hollow molding, or the like.
[0071]
【Example】
  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated in more detail, this invention is not limited by these Examples.
  The test method in this example is as follows.
[density]
  Conforms to JIS K6760.
[MFR]
  Conforms to JIS K6760.
[Mw / Mn]
  GPC (Waters 150C type) was used, and ODCB at 135 ° C. was used as a solvent. The column used was Shodex HT806M.
[TREF]
  With the column kept at 140 ° C., a sample was injected into the column, the temperature was lowered to 25 ° C. at 0.1 ° C./min, the polymer was deposited on glass beads, and the column was heated under the following conditions. The polymer concentration eluted at each temperature was detected with an infrared detector.
(Solvent: ODCB, flow rate: 1 ml / min, heating rate: 50 ° C./hr, detector: infrared spectrometer (wavelength 2925 cm^-1), Column: 0.8 cmφ × 12 cmL (filled with glass beads), sample concentration: 0.05 mass%)
[Dirt impact strength]
  It conformed to ASTM D-1709 B method.
[Tear strength]
  Conforms to JIS P8116.
[Static friction coefficient]
  Conforms to ASTM D1894.
[Heat seal temperature]
  A single-layer film having a thickness of 80 μm was prepared, a test piece having a heat seal width of 15 mm and a length of 80 mm was prepared, a heat seal time of 1.0 second, and a heat seal pressure of 1.5 kgf / cm.²Then, a heat test was conducted at a tensile rate of 300 mm / min to obtain a heat seal strength (gf / 15 mm width). Heat sealing was performed by changing the sealing temperature at several points, and the heat sealing strength was obtained as described above in a tensile test. A graph of the sealing temperature and the heat sealing strength was prepared, a sheet temperature at which the heat sealing strength was 500 gf / 15 mm width was determined from the graph, and this temperature was defined as the heat sealing temperature.
[Halogen concentration]
  When measured by a fluorescent X-ray method and 10 ppm or more of chlorine was detected, this was used as an analytical value. When it was less than 10 ppm, it was measured with a TOX-100 type chlorine / sulfur analyzer manufactured by Dia Instruments Co., Ltd., and 2 ppm or less was regarded as ND, which was not substantially included.
[0072]
[Odor evaluation method]
(Evaluation sample)
  The formed film was cut into a 10 cm square, and 100 sheets thereof were stacked, and this was put into a glass bottle with a lid having an internal volume of 1 liter. The glass bottle was left in a heating oven maintained at 60 ° C. for 1 hour, and the glass bottle was taken out and immediately subjected to sensory evaluation by a panel.
(Standard sample)
  MFR = 2.0 g / 10 min, density = 0.922 g / cm³A single-layer film having a thickness of 30 μm was formed by an inflation method at a forming temperature of 160 ° C. using a high-pressure radical method LDPE containing no additive. This film was placed in a glass bottle fitted with a gas introduction / exhaust port having an internal volume of 1 liter in the same manner as described above, covered, and heated at 60 ° C. for 5 hours at a flow rate of 5 liters / minute for 24 hours. The standard sample thus obtained was heated under the same conditions as the evaluation sample, and the odor superiority or inferiority between the evaluation sample / standard sample was compared and evaluated.
  The odor of the evaluation sample compared to the odor of the standard sample,
  Approximate equivalent --0 points
  Somewhat inferior --- 1 point
  Inferior ---- 2 points
The odor was determined based on the total score of the sensory test by 10 panelists. That is, the smaller the score, the better the odor.
[0073]
[Fish Eye Measurement Method]
  0.3m from the molded film²The sample was cut out and placed on a polarizing plate irradiated with a fluorescent lamp from below, and the fish eyes were counted visually. The number of fish eyes measured for fish eyes with a diameter of 0.1 mm or more is measured area 0.1 m²The number of fish eyes was converted to the number per hit. 15 / 0.1m²The following are good products.
[0074]
  The various components used in the examples are as follows.
  The ethylene copolymer (A11) was polymerized by the following method.
[Preparation of solid catalyst]
[Solid catalyst (I)]
  To a catalyst preparation apparatus equipped with an electromagnetic induction stirrer, 1000 ml of toluene purified under nitrogen, tetrapropoxyzirconium (Zr (OPr)₄) 26 g, 22 g of indene and 88 g of methylbutylcyclopentadiene were added, 100 g of tripropylaluminum was added dropwise over 100 minutes while maintaining at 90 ° C., and then reacted at the same temperature for 2 hours. After cooling to 40 ° C., 2424 ml of a toluene solution of methylalumoxane (concentration 3.3 mmol / ml) was added and stirred for 2 hours. Next, silica (surface area of 300 m) previously calcined at 450 ° C. for 5 hours.²/ G) After adding 2000 g and stirring at room temperature for 1 hour, nitrogen blowing and vacuum drying were performed at 40 ° C. to obtain a solid catalyst (A) having good fluidity.
[0075]
[Gas phase polymerization]
  Using a continuous fluidized bed gas phase polymerization apparatus, polymerization temperature 65 ° C., total pressure 20 kgf / cm²With G, ethylene and 1-hexene were copolymerized. The solid catalyst (a) was continuously supplied, and ethylene, 1-hexene, hydrogen, and the like were supplied so as to maintain a predetermined molar ratio, and polymerization was performed to obtain an ethylene copolymer (A11a). Moreover, the polymerization conditions were changed to obtain an ethylene copolymer (A11b). The measurement results of the physical properties of the copolymer are shown in Tables 1 and 2.
[0076]
  The ethylene copolymer (A12) was polymerized by the following method.
[Preparation of solid catalyst]
[Solid catalyst (b)]
  To a catalyst preparation apparatus equipped with an electromagnetic induction stirrer, 1000 ml of toluene purified under nitrogen, tetrabutoxyzirconium (Zr (OBu))₄) 31 g and 74 g of indene were added, and 127 g of triisobutylaluminum was added dropwise over 100 minutes while maintaining the temperature at 90 ° C., and then reacted at the same temperature for 2 hours. After cooling to 40 ° C., 2424 ml of a toluene solution of methylalumoxane (concentration: 3.3 mmol / ml) was added and stirred for 2 hours. Next, silica (surface area of 300 m) previously calcined at 450 ° C. for 5 hours.²/ G) After adding 2000 g and stirring at room temperature for 1 hour, nitrogen blowing and drying under reduced pressure were performed at 40 ° C. to obtain a solid catalyst (B) having good fluidity.
[0077]
[Gas phase polymerization]
  Using a continuous fluidized bed gas phase polymerization apparatus, polymerization temperature 70 ° C., total pressure 20 kgf / cm²With G, ethylene and 1-hexene were copolymerized. The solid catalyst (B) was continuously supplied, and polymerization was carried out by supplying ethylene, 1-hexene and hydrogen so as to maintain a predetermined molar ratio, thereby obtaining an ethylene copolymer (A12a). Moreover, the polymerization conditions were changed to obtain an ethylene copolymer (A12b). The measurement results of the physical properties of the copolymer are shown in Tables 1 and 2.
[0078]
  The ethylene copolymer (A2) was polymerized by the following method.
[Preparation of solid catalyst]
[Solid catalyst (C)]
  To a catalyst preparation apparatus equipped with an electromagnetic induction stirrer, 1000 ml of toluene purified under nitrogen, tetrapropoxyzirconium (Zr (OPr)₄) 26 g, indene 74 g and methylpropylcyclopentadiene 78 g were added, and 100 g of tripropylaluminum was added dropwise over 100 minutes while maintaining the temperature at 90 ° C., followed by reaction at the same temperature for 2 hours. After cooling to 40 ° C., 2133 ml of a toluene solution of methylalumoxane (concentration: 3.3 mmol / ml) was added and stirred for 2 hours. Next, silica (surface area of 300 m) previously calcined at 450 ° C. for 5 hours.²/ G) After adding 2000 g and stirring at room temperature for 1 hour, nitrogen blowing and drying under reduced pressure were performed at 40 ° C. to obtain a solid catalyst (C) having good fluidity.
[0079]
[Gas phase polymerization]
  Using a continuous fluidized bed gas phase polymerization apparatus, polymerization temperature 80 ° C., total pressure 20 kgf / cm²With G, ethylene and 1-hexene were copolymerized. The solid catalyst (C) was continuously supplied, and ethylene, 1-hexene and hydrogen were supplied so as to maintain a predetermined molar ratio, and polymerization was performed to obtain an ethylene copolymer (A2a). Moreover, the polymerization conditions were changed to obtain an ethylene copolymer (A2b). The measurement results of the physical properties of the copolymer are shown in Tables 1 and 2.
[0080]
[Production of ethylene / hexene-1 copolymer (A3) using metallocene catalyst]
  Purified toluene is put into a pressure reactor equipped with a stirrer substituted with nitrogen, 1-hexene is added, and a mixed solution of bis (n-butylcyclopentadienyl) zirconium dichloride and methylalumoxane (MAO) is added. After adding (Al / Zr molar ratio = 200), the temperature was raised to 80 ° C. to prepare a metallocene catalyst. Next, ethylene is put in, and the total pressure is 8 kg / cm while continuously polymerizing ethylene.³The ethylene copolymer (A3a) was produced by carrying out the polymerization while maintaining the same. In addition, ethylene copolymer (A3b) was produced by changing the polymerization conditions. The measurement results of the physical properties of the copolymer are shown in Tables 1 and 2.
[0081]
(A4a) Linear low density polyethylene using commercially available Ziegler catalyst
(LLDPE) Density: 0.910 g / cm³, MFR: 10 g / 10 min,
  Comonomer: 4-methyl-pentene-1
(A4b) Linear low density polyethylene using commercially available Ziegler catalyst
(LLDPE) Density: 0.919 g / cm³, MFR: 2.0 g / 10 min
  Comonomer: 4-methyl-pentene-1
  The physical properties of the ethylene copolymer are shown in Tables 1 and 2.
[0082]
  In addition, the following low density polyethylene was used as compounding resin.
(B1) Branched low-density polyethylene by a commercial high-pressure radical polymerization method
(LDPE) Density: 0.922 g / cm³, MFR: 1.0 g / 10 min
[0083]
[Table 1]

[0084]
[Table 2]

[0085]
[Examples 1 to 3]
  70 parts by mass of ethylene copolymers (A11a), (A12a) and (A2a) and 30 parts by mass of (B1) LDPE, dry blended with a tumbler mixer without additives such as antioxidants And pelletizing at 170 ° C. to obtain a resin composition. Then, using an extrusion laminating machine (manufactured by Modern Machinery) having a φ90 mm diameter extruder, the resin composition was melt extruded at a molding temperature of 315 ° C., a laminating speed of 100 m / min, a laminating thickness of 30 μm, and a coat width of 860 mm. Then, the laminate was obtained by extrusion laminating on aluminum foil (# 30) and polyethylene terephthalate (PET: 30 μm) as the base material. Test pieces were collected from these laminates and examined for adhesive strength. The results are shown in Table 3.
[0086]
[Comparative Examples 1-5]
  After blending 70 parts by weight of ethylene copolymer (A11a) and 30 parts by weight of (B1) LDPE, blending additives such as antioxidant, calcium stearate, hydrotalcite, etc., and dry blending with a tumbler mixer, The resin composition was obtained by pelletizing at 170 ° C. Then, extrusion lamination was performed in the same manner as in Example 1 to obtain a laminate. Test pieces were collected from this laminate and examined for adhesive strength. The results are shown in Table 3.
[0087]
[Comparative Example 6]
  (B1) LDPE was blended with 100 parts by mass of an antioxidant and extrusion laminated in the same manner as in Example 1 to obtain a laminate. Test pieces were collected from this laminate and examined for adhesive strength. The results are shown in Table 3.
[0088]
[Table 3]

[0089]
[Example 4]
  70 parts by mass of ethylene copolymer (A11a) and 30 parts by mass of (B1) LDPE were blended and dry blended with a tumbler mixer, and then pelletized at 170 ° C. to obtain a resin composition. Then, using an extrusion laminating machine (manufactured by Modern Machinery Co., Ltd.) having a φ90 mm diameter extruder, the resin composition was melt extruded at a molding temperature of 320 ° C., a laminating speed of 100 m / min, a laminating thickness of 25 μm, and a coat width of 860 mm. Then, the laminate was obtained by extrusion laminating on the aluminum foil # 30 as the base material. And the test piece was extract | collected from this laminated body, and adhesive strength and heat seal strength were investigated. The results are shown in Table 4.
  In this extrusion lamination, in order to obtain a sample for IR measurement, an adhesive tape made of vinylidene tetrafluoride having a thickness of 100 μm, a width of 50 mm and a length of 100 mm was used on a high-quality paper having a width of 210 mm × a length of 297 mm (Nitoflon manufactured by Nitto Denko Corporation). A sample-collecting paper with adhesive tape No. 923S) is prepared, and the adhesive tape made of vinylidene tetrafluoride is in contact with the adhesive surface of the polyolefin resin material layer on a part of the base material forming the base material layer. Bonded to. At the same time, in order to obtain a sample for ESCA measurement, a PET film having a width of 210 mm and a length of 297 mm, which was not corona-treated, was bonded to the base material so as to be in contact with the polyolefin resin material layer adhesion surface.
[0090]
[Surface oxidation degree]
  Cut out two pieces of laminate with vinylidene tetrafluoride adhesive tape 10mm wide and 50mm long, peel off the polyolefin resin material layer from the surface of the vinylidene tetrafluoride adhesive tape, and IR measurement A sample was obtained. The surface of the polyolefin resin material layer, which is an IR measurement sample, subjected to oxidation treatment was measured by an ATR method while purging with nitrogen using an FT-IR (IR-300 type) manufactured by JASCO Corporation. .
  In measurement, resolution is 4 cm.^-1The number of integrations was 200. The crystal plate for ATR measurement was made of KRS-5 (thallium bromide crystal) with a trapezoidal cross section with a width of 20 mm, a length of 50 mm, a thickness of 2 mm, and an angle of 45 °. .
  In the obtained surface infrared spectrum, 1720 cm^-1The absorption peak (I (1720)) of this peak was determined by selecting the absorption peak of the nearby carbonyl group as an absorption peak indicating the degree of oxidation, and connecting the valleys on both sides of this peak to form a baseline. Next, 1370 cm^-1Select the absorption peak of the nearby methyl group as the reference peak, 1330 cm^-1Near and 1400cm^-11370cm as a base line connecting two nearby points^-1The absorbance (I (1370)) of was determined. And surface oxidation degree Or was computed based on (Formula 8) mentioned above. The results are shown in Table 4.
[0091]
[Oxygen atom concentration]
  Oxygen atom concentration (Oc) is a polyolefin resin material layer (II), Base material layer (I) Is a value obtained by substituting oxygen Ols-corrected peak intensity: O and carbon Cls-corrected peak intensity: C, measured by the ESCA method, into (Equation 7). The oxygen atom introduction amount on the bonding surface can be quantified by the oxygen atom concentration.
(Formula 7) Oc = O / (C + O) × 100 (%)
[0092]
[Adhesive strength]
  The laminate obtained by the above process was conditioned at 40 ° C. for 2 days and then at 23 ° C. for 1 day. This was cut into a rectangle with a width of 15 mm and a length of 150 mm, peeled off at the interface between the base material layer and the polyolefin resin material layer, and subjected to T-type peeling at a peeling speed of 300 mm / min in accordance with JIS K6854. The peel strength was measured, and this peel strength was defined as the adhesive strength. The results are shown in Table 4.
[0093]
[Example 5]
  A laminate was obtained in the same manner as in Example 4 except that the ethylene copolymer (A12a) was blended in place of the ethylene copolymer (A11a). The laminate was examined for adhesive strength, oxygen atom concentration, and surface oxidation degree. The results are shown in Table 4.
[0094]
[Example 6]
  A laminate was obtained in the same manner as in Example 4 except that the ethylene copolymer (A2a) was blended in place of the ethylene copolymer (A11a). The laminate was examined for adhesive strength, oxygen atom concentration, and surface oxidation degree. The results are shown in Table 4.
[0095]
[Example 7]
  A laminate was obtained in the same manner as in Example 4 except that polyethylene terephthalate film (PET) # 12 was used instead of aluminum foil # 30 as a base material and the molding temperature was 310 ° C. The laminate was examined for adhesive strength, oxygen atom concentration, and surface oxidation degree. The results are shown in Table 4.
[0096]
[Example 8]
  The same procedure as in Example 4 was conducted except that the ethylene copolymer (A2a) was used instead of the ethylene copolymer (A11a), and the polyethylene terephthalate film (PET) # 12 was used instead of the aluminum foil # 30 as the base material. A laminate was obtained. The laminate was examined for adhesive strength, oxygen atom concentration, and surface oxidation degree. The results are shown in Table 4.
[0097]
[Example 9]
  A laminate was obtained in the same manner as in Example 4 except that biaxially stretched nylon film (ONy) # 15 was used instead of aluminum foil # 30 as the base material. The laminate was examined for adhesive strength, oxygen atom concentration, and surface oxidation degree. The results are shown in Table 4.
[0098]
[Example 10]
  A laminate was obtained in the same manner as in Example 4 except that polyethylene terephthalate film (PET) # 12 was used instead of aluminum foil # 30 as a substrate, the molding temperature was set to 300 ° C., and ozone treatment was performed. The laminate was examined for adhesive strength, oxygen atom concentration, and surface oxidation degree. The results are shown in Table 4.
[0099]
[Comparative Example 7]
  A laminate was obtained in the same manner as in Example 4 except that, instead of the ethylene copolymer (A11a), an ethylene copolymer (A3a) based on a general metallocene catalyst whose mass average molecular weight deviates from the ODCB soluble content was blended. The laminate was examined for adhesive strength, oxygen atom concentration, and surface oxidation degree. The results are shown in Table 4.
[0100]
[Comparative Example 8]
  A laminate was obtained in the same manner as in Example 4 except that the ethylene copolymer (A11a) was not blended and (B1) LDPE was changed to 100 parts by mass. The laminate was examined for adhesive strength, oxygen atom concentration, and surface oxidation degree. The results are shown in Table 5.
[0101]
[Comparative Example 9]
  A laminate was obtained in the same manner as in Example 4 except that LLDPE (A4a) using a Ziegler catalyst was blended instead of the ethylene copolymer (A11a). The adhesive strength of this laminate was examined. The results are shown in Table 5.
[0102]
[Comparative Example 10]
  A laminate was obtained in the same manner as in Comparative Example 7 except that PET # 12 was used instead of aluminum foil # 30 as the base material. The laminate was examined for adhesive strength, oxygen atom concentration, and surface oxidation degree. The results are shown in Table 5.
[0103]
[Comparative Example 11]
  A laminate was obtained in the same manner as in Comparative Example 8 except that PET # 12 was used instead of aluminum foil # 30 as the substrate. The laminate was examined for adhesive strength, oxygen atom concentration, and surface oxidation degree. The results are shown in Table 5.
[0104]
[Comparative Example 12]
  A laminate was obtained in the same manner as in Comparative Example 7 except that ONy # 15 was used instead of aluminum foil # 30 as the base material. The laminate was examined for adhesive strength, oxygen atom concentration, and surface oxidation degree. The results are shown in Table 5.
[0105]
[Comparative Example 13]
  A laminate was obtained in the same manner as in Comparative Example 8 except that ONy # 15 was used as the substrate instead of aluminum foil # 30. The laminate was examined for adhesive strength, oxygen atom concentration, and surface oxidation degree. The results are shown in Table 5.
[0106]
[Comparative Example 14]
  A laminate was obtained in the same manner as in Comparative Example 9 except that the molding temperature was 300 ° C. and the ozone treatment was performed. The laminate was examined for adhesive strength, oxygen atom concentration, and surface oxidation degree. The results are shown in Table 5.
[0107]
[Comparative Example 15]
  A laminate was obtained in the same manner as in Comparative Example 10 except that the molding temperature was 300 ° C. and the ozone treatment was performed. The laminate was examined for adhesive strength, oxygen atom concentration, and surface oxidation degree. The results are shown in Table 5.
[0108]
[Table 4]

[0109]
[Table 5]

[0110]
  Since Examples 4-10 satisfy | filled the range of this-application Claim 1, adhesive strength was high.
  On the other hand, the ethylene copolymer (A3a) of Comparative Example 7 has a high Mw content of ODCB and does not improve the adhesive strength.
  In Comparative Examples 8, 10, 12, and 14, since the polyolefin resin material layer was only high-pressure radical polymerization low-density polyethylene, the adhesive strength was low. In addition, Comparative Examples 9, 11, 13, and 15 were obtained by blending an ethylene / α-olefin copolymer (A4a) with a commercially available Ziegler-based catalyst and a high-pressure radical polymerization method low-density polyethylene. Was low.
[0111]
[Examples 11 to 18]
  In the ratio shown in Table 6, ethylene copolymers (A11b), (A12b), (A2b) and LDPE (B1) were blended, and a tumbler mixer was added without adding an antioxidant and a halogen absorbent (calcium stearate). After dry blending, a single layer film having a thickness of 30 μm was formed by an inflation method using a plako (screw diameter 55 mmφ) extruder under forming conditions of a forming temperature of 140 ° C., a film width of 300 mm, and a blow ratio of 2.7. The single layer film was measured for dart impact strength, tear strength, heat seal temperature, and halogen concentration to evaluate odor and fish eye. The results are shown in Table 6. There was no problem with either odor or fish eye.
[0112]
[Comparative Example 16]
  (B1) Inflation films were molded in the same manner as in Example 11 using only LDPE, and the evaluation results are shown in Table 6. Since only LDPE is used, the dart impact strength is low.
[0113]
[Comparative Example 17]
  Table 6 shows the results of evaluation conducted in the same manner as in Example 11 except that the ethylene copolymer (A3b) using a metallocene catalyst instead of the ethylene copolymer of Example 12 (A11b) was used. The molding temperature was high, and there were many odors and fish eyes.
[0114]
[Comparative Examples 18-19]
  In the composition shown in Table 6, a linear low density polyethylene (LLDPE) alone or LLDPE (A4b) and LDPE (B1) with a commercially available Ziegler catalyst were blended, and a single layer film was formed in the same manner as in Example 11. The results are shown in Table 6. When the ratio of LLDPE (A4b) was large, the molding temperature was low, and thus a single layer film could not be molded.
[0115]
[Comparative Examples 20-21]
  In the proportions shown in Table 6, linear low density polyethylene LLDPE (A4b) using a Ziegler-Natta catalyst and the LLDPE and LDPE (B1) were blended, and to this were added Irganox 1076 1000 ppm and Irgaphos 168 as antioxidants. 1500 ppm, calcium stearate 1500 ppm as a halogen absorbent, dry blended with a tumbler mixer, and molded using Plako (screw diameter 55 mmφ) extruder, molding temperature 180 ° C., film width 300 mm, blow ratio 2.7 A single-layer film having a thickness of 30 μm was formed by an inflation method under conditions. The results are shown in Table 6. Since the additive was blended, the odor and halogen concentration were high.
[0116]
[Comparative Example 22]
  A single layer film was formed in the same manner as Comparative Example 21 except that the antioxidant and the halogen absorbent were not added. The results are shown in Table 6. The resin temperature was high in the absence of additives, so the resin deterioration seems to have progressed, and there were many odors and fish eyes.
[0117]
[Table 6]

[0118]
【The invention's effect】
  As described above, the polyolefin-based resin material of the present invention includes 100 to 10% by mass of an ethylene (co) polymer (A) that satisfies the specific requirements (a) to (e) described above, and (B). A specific ethylene (co) polymer (A) containing 0 to 90% by mass of other polyolefin-based resin and having a mass average molecular weight of ODCB solubles in the range of 8000 to 30000, and substantially an additive Is a polyolefin-based resin material that is not blended, and is excellent in low-temperature heat sealability, adhesive strength, tear strength, impact resistance, transparency, moldability, and the like. Further, since the resin does not substantially contain a halogen, it is suitable for a field requiring a polyolefin container such as food, medical care, and electronic materials, particularly for a food container that complies with a ministerial ordinance.
  In addition, the polyolefin resin material containing the ethylene (co) polymer (A) can be molded at low temperature and is halogen-free, so there are no conventional additives such as antioxidants and acid absorbers. However, it can be molded.
  Further, according to the present invention, a polyolefin resin material layer (II) And base material layer (I) And are bonded with high adhesive strength. Therefore, when this specific ethylene (co) polymer is oxidized to a specific range, it is not necessary to use an anchor coating agent, so that there is no elution of a solvent or the like, and a polyolefin resin laminate can be provided. Furthermore, by not using an anchor coat agent, the cost is reduced and the operation is simplified. In addition, since no solvent is used, environmental problems and odor problems are eliminated.
  In addition, the laminate which is an embodiment of the molded body of the present invention is excellent in adhesive strength, tear strength, impact resistance, low temperature heat sealability, transparency, molding processability, etc., and polyolefins such as food, medical and electronic materials. It is suitable for fields that require containers and the like, especially for food containers that comply with ministerial ordinances such as milk.
  Moreover, since the inner bag for a bag-in-box of the present invention uses the film or sheet or the laminated body as at least the innermost layer, the tear strength, impact resistance, low-temperature heat sealability, transparency, moldability And is suitable for the field where polyolefin inner bags are required.
  In addition, since the medical container or package of the present invention uses the film or sheet or the laminate at least in the innermost layer, the tear strength, impact resistance, low temperature heat sealability, transparency, moldability And is suitable for the medical field where a polyolefin container and a package are required.
[Brief description of the drawings]
FIG. 1 shows T of ethylene (co) polymer (A) in the present invention.₇₅-T₂₅It is explanatory drawing of [Formula 1].
FIG. 2 is a graph showing an elution temperature-elution amount curve of an ethylene (co) polymer (A1) in the present invention.
FIG. 3 is a graph showing an elution temperature-elution amount curve of an ethylene copolymer with a typical metallocene catalyst.
FIG. 4 is a graph showing an elution temperature-elution amount curve of an ethylene (co) polymer (A2) in the present invention.
5A and 5B are diagrams showing a method for producing a sample for IR measurement, FIG. 5A is a perspective view showing a laminating step, and FIG. 5B is a perspective view showing a sample collection sheet. .
FIG. 6A is a cross-sectional view showing a pasting portion of the sample collection paper in the laminate, and FIG. 6B is a diagram showing the polyolefin resin material layer separated in the pasting portion of the sample collection paper in the laminate. FIG.

Claims (19)

(A) 100 to 10% by mass of an ethylene (co) polymer satisfying the following (a) to (e):
(A) Density is 0.86-0.97 g / cm ³ ,
(B) a melt flow rate of 0.01 to 200 g / 10 minutes,
(C) molecular weight distribution (Mw / Mn) is 1.5 to 4.5,
(D) The mass average molecular weight of the o-dichlorobenzene (ODCB) soluble component at 23 ° C. is in the range of 8000 to 30000,
(E) The difference between the temperature T _{25 at} which 25% of the total elution is obtained from the integral dissolution curve of the elution temperature-elution amount curve by the continuous temperature rising elution fractionation method (TREF) and the temperature T _{75 at} which 75% of the total is eluted. T ₇₅ -T ₂₅ and density d are
(Expression 1) T ₇₅ −T ₂₅ ≦ −670 × d + 644
(B) Other polyolefin resin 0-90 mass%
And a polyolefin-based resin material that is substantially free of additives. A temperature T _{25 at} which 25% of the ethylene (co) polymer (A) is further eluted from an integral dissolution curve of an elution temperature-elution amount curve by (f) continuous temperature rising elution fractionation method (TREF) Difference T ₇₅ −T _{25 from} temperature T _{75 at} which 75% of the total elutes and density d is (Expression 2) d <0.950 g / cm ³ T ₇₅ −T ₂₅ ≧ −300 × d + 285
When d ≧ 0.950 g / cm ³ , T ₇₅ −T ₂₅ ≧ 0
The polyolefin resin material according to claim 1, which is an ethylene (co) polymer (A) satisfying the relationship: The ethylene (co) polymer (A) further has (g) an orthodichlorobenzene (ODCB) soluble amount X (mass%) at 25 ° C., a density d and a melt flow rate (MFR).
(Formula 3) When d−0.008log MFR ≧ 0.93, X <2.0
(Formula 4) When d−0.008 log MFR <0.93, X <9.8 × 10 ³ × (0.9300−d + 0.008 log MFR) ² +2.0 is satisfied, and (h) continuous ascent Ethylene (co) polymer (A1) having a plurality of elution temperature-elution amount curve peaks by the temperature elution fractionation method (TREF)
The polyolefin resin material according to claim 1, wherein the polyolefin resin material is a polyolefin resin material. The ethylene (co) polymer (A) further has (i) one elution temperature-elution amount curve peak by continuous temperature rising elution fractionation (TREF), and (j) 1 to 2 melting point peaks. Having the highest melting point T _ml and density d,
(Formula 5) _Tml > = 150 * d-19
The polyolefin resin material according to claim 1 or 2, which is an ethylene (co) polymer (A2) satisfying the above relationship. The ethylene (co) polymer (A2) further has (k) melt tension (MT) and melt flow rate (MFR),
(Formula 6) logMT ≦ −0.572 × logMFR + 0.3
The polyolefin resin material according to claim 4, wherein: The polyolefin resin material according to any one of claims 1 to 5, wherein the (l) halogen content in the ethylene (co) polymer (A) is 10 ppm or less. The ethylene (co) polymer (A) is
(M) The catalyst is produced in the presence of a catalyst containing at least an organic cyclic compound having a conjugated double bond and a group IV transition metal compound in the periodic table. The polyolefin resin material according to one item.   A molded product produced by producing the polyolefin resin material according to any one of claims 1 to 7 by at least one of extrusion molding, injection molding, blow molding, and rotational molding. . The molded body according to claim 8 , at least the base material layer (I),
(A) 100 to 10% by mass of an ethylene (co) polymer satisfying the following (a) to (e):
(A) Density is 0.86-0.97 g / cm ³ ,
(B) a melt flow rate of 0.01 to 200 g / 10 minutes,
(C) molecular weight distribution (Mw / Mn) is 1.5 to 4.5,
(D) The mass average molecular weight of o-dichlorobenzene (ODCB) soluble component at 23 ° C. is in the range of 8000-30000. (E) Integration of elution temperature-elution amount curve by continuous temperature elution fractionation method (TREF) The difference T ₇₅ -T ₂₅ and the density d between the temperature T _{25 at} which 25% of the total elution is obtained from the melting curve and the temperature T _{75 at} which 75% of the total is eluted are
(Expression 1) T ₇₅ −T ₂₅ ≦ −670 × d + 644
(B) A polyolefin resin material layer (II) containing 0 to 90% by mass of other polyolefin resin and containing substantially no additive, and without an anchor coat agent layer. A laminate characterized by being made.   The surface of the polyolefin-based resin material layer (II) in contact with the base material layer (I) is (i) an oxygen atom concentration of 1.8% by mass or more, and (b) a surface oxidation degree of 0.10. It is the above, The laminated body of Claim 9 characterized by the above-mentioned.   The said base material layer (I) consists of at least any 1 type of a thermoplastic film, metal foil, a vapor deposition film of a metal oxide or an inorganic substance, paper, a nonwoven fabric, and a woven fabric. The laminated body of description.   The other polyolefin-based resin in the polyolefin-based resin material layer (II) is at least one selected from high-density polyethylene, linear low-density polyethylene, high-pressure radical method low-density polyethylene, polypropylene, or a mixture thereof. The laminate according to any one of claims 9 to 11, which is characterized in that Without using an anchor coat agent at least on the substrate (I),
(A) 100 to 10% by mass of an ethylene (co) polymer satisfying the following (a) to (e):
(A) Density is 0.86-0.97 g / cm ³ ,
(B) a melt flow rate of 0.01 to 200 g / 10 minutes,
(C) molecular weight distribution (Mw / Mn) is 1.5 to 4.5,
(D) The mass average molecular weight of the o-dichlorobenzene (ODCB) soluble component at 23 ° C. is in the range of 8000 to 30000,
(E) The difference between the temperature T _{25 at} which 25% of the total elution is obtained from the integral dissolution curve of the elution temperature-elution amount curve by the continuous temperature rising elution fractionation method (TREF) and the temperature T _{75 at} which 75% of the total is eluted. T ₇₅ -T ₂₅ and density d are
(Expression 1) T ₇₅ −T ₂₅ ≦ −670 × d + 644
(B) Other polyolefin resin 0-90 mass%
And a polyolefin resin material (II) substantially free of additives is melt-extruded at a molding temperature of 200 to 350 ° C. and laminated.   The surface of the melt-extruded molten resin film in contact with the substrate (I) is (b) an oxidation treatment so that the oxygen atom concentration is 1.8% by mass or more and (b) the surface oxidation degree is 0.10 or more. The method for producing a laminate according to claim 13, wherein the molten resin film is laminated on the substrate (I).   The method for producing a laminate according to claim 14, wherein the oxidation treatment is air oxidation treatment and / or ozone treatment at a resin temperature of the molten resin film in a range of 200 to 350 ° C. A container or bag comprising the polyolefin resin material or laminate according to any one of claims 1 to 12.   The paper container according to claim 16, wherein the container has at least a paper layer (I-1) and / or a barrier layer (I-2) and a polyolefin-based resin material layer (II) as a heat seal layer. .   The container is made of a plastic layer (I-3) / paper layer (I-1) / polyolefin resin material layer (II-1) / barrier layer (I-2) / heat seal layer (polyolefin resin material layer (II). The paper container according to claim 16, wherein the paper containers are laminated in the order of -2)). An inner bag for a back-in box, comprising the polyolefin resin material or the laminate according to any one of claims 1 to 12.

Images