JP2019064743A - Sealant film for packaging medium using plant-derived polyethylene, laminated film for packaging medium, and packaging bag - Google Patents

Sealant film for packaging medium using plant-derived polyethylene, laminated film for packaging medium, and packaging bag Download PDF

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JP2019064743A
JP2019064743A JP2018218098A JP2018218098A JP2019064743A JP 2019064743 A JP2019064743 A JP 2019064743A JP 2018218098 A JP2018218098 A JP 2018218098A JP 2018218098 A JP2018218098 A JP 2018218098A JP 2019064743 A JP2019064743 A JP 2019064743A
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polyethylene
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JP6662437B2 (en
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松下　田恵子
Taeko Matsushita
田恵子 松下
文 宮坂
Fumi Miyasaka
文 宮坂
政人 油野
Masato Yuno
政人 油野
伊藤　克伸
Katsunobu Ito
克伸 伊藤
良彦 鈴木
Yoshihiko Suzuki
良彦 鈴木
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Dai Nippon Printing Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

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Abstract

To provide a film which enables saving of oil resources using as raw material plant-derived polyethylene-based resin, which is a renewable resource, and is eco-friendly due to emission reduction of carbon dioxide, and to provide a packaging bag using the film.SOLUTION: Films F1 to F4 are constituted by a resin composition 1 containing straight-chain low-density plant-derived polyethylene-based resin obtained by a vapor phase polymerization method. Further, a laminated film 3 is made by laminating the films F1 to F4 as sealant films with a substrate film 5 and a packaging bag 6 includes the laminated film 3.SELECTED DRAWING: Figure 2

Description

ポリエチレン系樹脂からなるフィルムに関し、より詳細には、このポリエチレン系樹脂が、植物由来ポリエチレン系樹脂を含む包装材用シーラントフィルムおよび包装材用積層フィルム、これらのフィルムを用いた包装袋に関する。   The present invention relates to a film made of a polyethylene resin, and more particularly to a sealant film for a packaging material, a laminated film for a packaging material, and a packaging bag using these films, wherein the polyethylene resin comprises a plant-derived polyethylene resin.

従来、例えば、シャンプーやリンスなどの詰め替えや、食品などの包材として用いられるパウチなどに代表される包装袋は、シーラントフィルムおよび基材フィルムからなる包装材料で構成されており、環境問題や石油など枯渇資源の節約に対応し、これら石油資源の包装材料への使用量低減のため、カーボンニュートラルな材料としてのポリ乳酸系樹脂に、エチレン−α−オレフィン共重合体およびエポキシ基を有する重合体をそれぞれ所定量含有させた生分解性の樹脂組成物を含む包装袋（例えば特許文献１）がある。   Conventionally, packaging bags typified by, for example, refills such as shampoos and rinses and pouches used as packaging materials for foods and the like are made of a packaging material composed of a sealant film and a base film, and environmental problems and petroleum Etc. In order to reduce the consumption of these petroleum resources to packaging materials in response to the saving of depleted resources, polylactic acid based resin as a carbon neutral material, ethylene-α-olefin copolymer and polymer having epoxy group There is a packaging bag (for example, patent document 1) containing the biodegradable resin composition which each contained a predetermined amount.

特開２００９−１５５５１６号公報JP, 2009-155516, A

しかし、このような包装袋では、上述したように、包装袋を構成する樹脂組成物に石油由来原料以外の生分解性樹脂を含有させて石油由来原料の比率を下げているものの、石油系樹脂と比較して引裂強度やヒートシール強度などの加工適性が著しく劣り、生産性を向上させることができないという問題があった。
従って、この発明の目的は、再生可能資源である植物由来のポリエチレン系樹脂を原料に用いて、石油資源の節約を可能とするとともに、二酸化炭素の排出量削減による環境にやさしい包装材用シーラントフィルムおよび包装材用積層フィルム、ならびにこれらのフィルムを用いた加工適性に優れる包装袋を提供することにある。 However, in such a packaging bag, as described above, although the resin composition constituting the packaging bag contains a biodegradable resin other than the petroleum-derived material to reduce the ratio of the petroleum-derived material, the petroleum-based resin Compared with the above, the processing aptitude such as the tear strength and the heat seal strength is remarkably inferior, and there is a problem that the productivity can not be improved.
Accordingly, an object of the present invention is to use a plant-based polyethylene resin as a renewable resource as a raw material to save petroleum resources, and to use an environmentally friendly sealant film for packaging materials by reducing carbon dioxide emissions. It is an object of the present invention to provide a laminated film for packaging material and a packaging bag which is excellent in processability using these films.

このため、請求項１に記載の発明に係る包装材用シーラントフィルムは、ポリエチレン系樹脂からなるフィルムであって、植物由来エチレンと石油由来α−オレフィンとの気相重合法にて得られた直鎖状低密度の植物由来ポリエチレン系樹脂を５〜９０重量％と、石油由来ポリエチレン系樹脂を１０〜９５重量％とを含む樹脂組成物による単層構成のフィルムをヒートシール性フィルムとすることを特徴とする。   For this reason, the sealant film for packaging materials according to the invention according to claim 1 is a film made of a polyethylene-based resin, which is obtained by direct gas phase polymerization of plant-derived ethylene and petroleum-derived α-olefin. Using a heat-sealable film as a film having a single-layer structure comprising a resin composition containing 5 to 90% by weight of a chain-like low density plant-derived polyethylene resin and 10 to 95% by weight a petroleum-derived polyethylene resin It features.

請求項２に記載の発明に係る包装材用シーラントフィルムは、請求項１に記載のフィルムにおいて、前記ポリエチレン系樹脂は、放射性炭素年代測定１４Ｃの測定値から算定するバイオマス度を有するエチレン−α−オレフィン共重合体であることを特徴とする。 The sealant film for a packaging material according to the invention described in claim 2 is the film according to claim 1, wherein the polyethylene resin has a biomass degree calculated from the measured value of radiocarbon dating 14 C ethylene-α -It is characterized by being an olefin copolymer.

請求項３に記載の発明は、請求項１または２に記載の包装材用シーラントフィルムにおいて、前記α−オレフィンが、ブテン−１またはヘキセン−１またはこれらの混合物、密度が０．９１０〜０．９２５ｇ／ｃｍ３、メルトフローレートが０．５〜４．０ｇ／１０分の物性を有することを特徴とする。 The invention according to claim 3 is the sealant film for packaging material according to claim 1 or 2, wherein the α-olefin is butene-1 or hexene-1 or a mixture thereof, and the density is 0.910 to 0. It is characterized in that it has physical properties of 925 g / cm 3 and a melt flow rate of 0.5 to 4.0 g / 10 min.

請求項４に記載の発明に係る包装材用積層フィルムは、請求項１ないし３のいずれか１項に記載の包装材用シーラントフィルムを、基材フィルムと積層させたことを特徴とする。   The laminated film for a packaging material according to the invention of claim 4 is characterized in that the sealant film for a packaging material according to any one of claims 1 to 3 is laminated with a base film.

請求項５に記載の発明に係る包装袋は、請求項４に記載の包装材用積層フィルムを用いてなることを特徴とする。   The packaging bag which concerns on invention of Claim 5 is characterized by using the laminated film for packaging materials of Claim 4. It is characterized by the above-mentioned.

請求項１に記載の発明によれば、ポリエチレン系樹脂からなるフィルムであって、植物由来エチレンと石油由来α−オレフィンとの気相重合法にて得られた直鎖状低密度の植物由来ポリエチレン系樹脂を５〜９０重量％と、石油由来ポリエチレン系樹脂を１０〜９５重量％とを含む樹脂組成物による単層構成のフィルムをヒートシール性フィルムとするので、ポリエチレン系樹脂からなる包装材用シーラントフィルムの構成を、全て石油由来の樹脂組成物に依存する状態から、この石油由来のポリエチレン系樹脂に、石油由来のポリエチレン系樹脂と性能的に違いがなく、カーボンニュートラルなサトウキビなど植物由来のポリエチレン系樹脂を混成（置換）することで、石油資源の使用量を削減するとともに、包装材用シーラントフィルム製造および廃棄時の二酸化炭素排出量を抑制することができる。従って、環境負荷を低減させたポリエチレン系樹脂からなる包装材用シーラントフィルムを提供することができる。さらに、包装材用シーラントフィルムを構成するポリエチレン系樹脂の石油由来の使用比率を低下させることができる。従って、石油資源の節約および環境負荷を低減させたポリエチレン系樹脂からなる包装材用シーラントフィルムを提供することができる。   According to the invention described in claim 1, a linear low density plant-derived polyethylene obtained by a vapor phase polymerization method of a plant-derived ethylene and a petroleum-derived α-olefin, which is a film comprising a polyethylene-based resin A heat sealable film is a film having a single-layer structure comprising a resin composition containing 5 to 90% by weight of a base resin and 10 to 95% by weight of a petroleum-derived polyethylene resin. Since the composition of the sealant film depends entirely on the resin composition derived from petroleum, this petroleum-derived polyethylene resin has no difference in performance from the polyethylene-derived resin derived from petroleum, and is derived from plants such as carbon neutral sugar cane By mixing (substituting) a polyethylene-based resin, the amount of petroleum resources used can be reduced, and a sealant film for packaging materials It is possible to suppress granulation and carbon dioxide emissions at the time of disposal. Therefore, the sealant film for packaging materials which consists of polyethylene-type resin which reduced the environmental impact can be provided. Furthermore, the petroleum-derived use ratio of the polyethylene-based resin that constitutes the sealant film for packaging material can be reduced. Therefore, it is possible to provide a sealant film for packaging material made of a polyethylene-based resin with reduced petroleum resources and reduced environmental impact.

請求項２に記載の発明によれば、ポリエチレン系樹脂は、放射性炭素年代測定１４Ｃの測定値から算定するバイオマス度を有するエチレン−α−オレフィン共重合体であるので、包装材用シーラントフィルムを構成するポリエチレン系樹脂の原料由来を、このバイオマス度を指標にして識別でき、包装材用シーラントフィルムの製造時から廃棄時まで由来原料を確認することができる。従って、原料由来の識別を可能としたポリエチレン系樹脂からなる包装材用シーラントフィルムを提供することができる。 According to the second aspect of the invention, since the polyethylene resin is an ethylene-α-olefin copolymer having a biomass degree calculated from the measured value of radiocarbon dating 14 C, the sealant film for packaging material is used. The origin of the raw material of the constituent polyethylene-based resin can be identified by using the degree of biomass as an index, and the derived raw material can be confirmed from the time of manufacture of the sealant film for packaging material to the time of disposal. Therefore, the sealant film for packaging materials which consists of a polyethylene-type resin which enabled identification derived from a raw material can be provided.

請求項３に記載の発明によれば、α−オレフィンが、ブテン−１またはヘキセン−１またはこれらの混合物、密度が０．９１０〜０．９２５ｇ／ｃｍ３、メルトフローレートが０．５〜４．０ｇ／１０分の物性を有するので、石油由来のポリエチレン系樹脂と物性的に違いがないため、既存のフィルム製造工程を用いることができ、包材の加工適性を損ねることなく原料を切替えることができる。従って、環境負荷の低減および生産効率に優れたポリエチレン系樹脂からなる包装材用シーラントフィルムを提供することができる。 According to the third aspect of the present invention, the α-olefin is butene-1 or hexene-1 or a mixture thereof, and the density is 0.910 to 0.925 g / cm 3 , and the melt flow rate is 0.5 to 4 As it has physical properties of 0 g / 10 min, there is no difference in physical properties from petroleum-derived polyethylene resins, so that existing film manufacturing processes can be used, and the raw materials can be switched without impairing the processing suitability of the packaging material Can. Therefore, the sealant film for packaging materials which consists of polyethylene-type resin which was excellent in reduction of environmental impact and production efficiency can be provided.

請求項４に記載の発明によれば、植物由来ポリエチレン系樹脂を含むポリエチレン系樹脂からなる包装材用シーラントフィルム（請求項１ないし３のいずれかに記載）を、基材フィルムと積層させた包装材用積層フィルムとするので、ヒートシールに用いるシーラントフィルムにおいても、このシーラントフィルムであるフィルムを構成するポリエチレン系樹脂の石油由来の使用比率を低下させることができ、石油資源の使用量を削減するとともに、包装材用積層フィルムの製造および廃棄時の二酸化炭素排出量を抑制することができる。従って、石油資源の節約および環境負荷を低減させたポリエチレン系樹脂からなる包装材用積層フィルムを提供することができる。   According to the invention as set forth in claim 4, a package in which a sealant film for packaging material (described in any one of claims 1 to 3) consisting of a polyethylene-based resin containing a plant-derived polyethylene-based resin is laminated with a substrate film Since it is used as a laminated film for materials, even in the sealant film used for heat sealing, it is possible to reduce the petroleum-derived use ratio of the polyethylene resin constituting the film which is this sealant film, and reduce the amount of petroleum resources used. At the same time, it is possible to suppress carbon dioxide emissions at the time of production and disposal of the laminated film for packaging material. Therefore, the laminated film for packaging materials which consists of polyethylene-type resin which saved the petroleum resource and reduced the environmental impact can be provided.

請求項５に記載の発明によれば、植物由来ポリエチレン系樹脂を含むポリエチレン系樹脂からなるフィルム（請求項１ないし３のいずれかに記載）を、基材フィルムと積層させた包装材用積層フィルム（請求項４に記載）を用いてなる包装袋であるので、包装袋を構成する包装材用積層フィルムにおけるポリエチレン系樹脂の石油由来の使用比率を低下させることができ、石油資源の使用量を削減するとともに、包装袋の製造および廃棄時の二酸化炭素排出量を抑制することができる。従って、石油資源の節約および環境負荷を低減させたポリエチレン系樹脂からなる包装袋を提供することができる。   According to the invention as set forth in claim 5, a laminated film for packaging material in which a film made of a polyethylene-based resin containing a plant-derived polyethylene-based resin (as described in any one of claims 1 to 3) is laminated with a substrate film. Since it is a packaging bag using (according to claim 4), it is possible to reduce the petroleum-derived use ratio of the polyethylene resin in the laminated film for packaging material constituting the packaging bag, and to use the amount of petroleum resources It is possible to reduce carbon dioxide emissions during the production and disposal of packaging bags as well as reducing them. Therefore, it is possible to provide a packaging bag made of a polyethylene-based resin with reduced petroleum resources and reduced environmental impact.

さらに、使い捨てとして世の中に数多く出回る包装袋を構成するポリエチレン系樹脂の石油由来の使用比率を低下させることができ、石油資源の使用量を削減するとともに、包装袋の製造および廃棄時の二酸化炭素排出量を抑制することができる。   Furthermore, it is possible to reduce the petroleum-derived use ratio of polyethylene-based resins that make up many packaging bags widely used in the world as disposables, reduce the amount of petroleum resources used, and emit carbon dioxide when manufacturing and disposing of packaging bags. The amount can be reduced.

サトウキビ由来のポリエチレン製造の一例を示すフロー図である。It is a flow figure showing an example of polyethylene production derived from sugarcane. 本願発明のサトウキビ由来の直鎖状低密度ポリエチレン系樹脂からなるフィルムを模式的に示す断面側面図である。It is a cross-sectional side view which shows typically the film which consists of a linear low density polyethylene-type resin derived from the sugarcane of this invention. 本願発明の樹脂組成物と、石油由来のポリエチレン系樹脂とを混合した単層構成のフィルムを模式的に示す断面側面図である。It is a cross-sectional side view which shows typically the film of the single layer structure which mixed the resin composition of this invention, and petroleum-derived polyethylene-type resin. 本願発明の中間層を樹脂組成物とした多層構造からなるフィルムを模式的に示す断面側面図である。It is a cross-sectional side view which shows typically the film which consists of a multilayer structure which made the intermediate | middle layer of this invention the resin composition. 本願発明の中間層を樹脂組成物および石油由来ポリエチレン系樹脂を混合した層とした多層構造からなるフィルムを模式的に示す断面側面図である。It is a cross-sectional side view which shows typically the film which consists of a multilayer structure which made the intermediate | middle layer of this invention the layer which mixed resin composition and petroleum origin polyethylene-type resin. 本願発明の積層フィルムの一例を模式的に示す断面側面図である。BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional side view which shows typically an example of the laminated | multilayer film of this invention. 本願発明の積層フィルムを用いて形成した包装袋の一例としてのスタンディングパウチを示す斜視図である。It is a perspective view which shows the standing pouch as an example of the packaging bag formed using the laminated | multilayer film of this invention.

以下、図面を参照しつつ本発明を実施するための最良の形態について説明する。食品や化粧品などに用いられるラミネートチューブなどに例示される容器や、シャンプーやリンスの詰め替えの包材として広く採用されているスタンディングパウチなどに例示される包装袋には、これら容器や包装袋が積層フィルムで構成されている。   Hereinafter, the best mode for carrying out the present invention will be described with reference to the drawings. These containers and packaging bags are laminated in a container exemplified by a laminated tube used for food and cosmetics, and a packaging pouch exemplified by a standing pouch widely adopted as a packaging material for refilling shampoo and rinse. It is made of film.

この積層フィルムには、基材フィルムに、ヒートシール材として積層フィルムの内面に使用するシーラントフィルムを積層させるものがあり、基材フィルムの材質として、例えばポリエチレン系樹脂などが用いられるとともに、シーラントフィルムの材質には、積層体として例えば中間層を挟んで直鎖状低密度ポリエチレン系樹脂が用いられている。   This laminate film includes a substrate film on which a sealant film used as a heat seal material is laminated on the inner surface of the laminate film, and as a material of the substrate film, for example, a polyethylene resin is used For the material of (1), for example, a linear low density polyethylene-based resin is used as a laminate with an intermediate layer interposed therebetween.

このように、積層フィルムの材質には、プラスチック樹脂であるポリエチレン系樹脂が多く用いられているが、従来、このポリエチレン系樹脂は、出発原料を石油とする石油化学由来により製造されており、例えば、上述した直鎖状低密度ポリエチレン系樹脂は、原油の精製などにより得られたエチレンと、コモノマー種としてのα−オレフィンとを、メタロセン触媒の存在下、気相において、１２０℃以上などの高温で共重合させたものである。なお、α−オレフィンは、一般式Ｒ−ＣＨ＝ＣＨ２（式中、Ｒは炭素数１以上のアルキル基）で表される、プロピレン、１−ブテン、１−ペンテン、１−ヘキセン、１−ヘプテン、１−オクテン、１−ノネン、１−デセン、４−メチル−１−ペンテン、４−メチル−１−ヘキセン、４，４−ジメチル−１−ペンテン、オクタデセンなど例示することができる。また、メタロセン触媒は特に限定しないが、例えば、シクロペンタジエニル基、置換基を有するシクロペンタジエニル基（置換シクロペンタジエニル基）、インデニル基、置換インデニル基から選ばれる１種類の基と、フルオレニル基、置換フルオレニル基から選ばれる１種類の基が、架橋基により架橋された配位子を有する周期表第４族の遷移金属化合物を挙げることができ、その代表例としてジフェニルメチレン（１−シクロペンタジエニル）（９−フルオレニル）ジルコニウムジクロリド、ジフェニルメチレン（３−メチル−１−シクロペンタジエニル）（９−フルオレニル）ジルコニウムジクロリド、ジフェニルメチレン（１−シクロペンタジエニル）（２，７−ジメチル−９−フルオレニル）ジルコニウムジクロリド、ジフェニルメチレン（１−シクロペンタジエニル）（２，７−ジ−ｔ−ブチル−９−フルオレニル）ジルコニウムジクロリド、ジフェニルメチレン（１−インデニル）（９−フルオレニル）ジルコニウムジクロリド、ジフェニルメチレン（４−フェニル−１−インデニル）（９−フルオレニル）ジルコニウムジクロリド、ジフェニルメチレン（４−フェニル−１−インデニル）（２，７−ジ−ｔ−ブチル−９−フルオレニル）ジルコニウムジクロリド等のジクロル体および上記メタロセン化合物のジメチル体、ジエチル体、ジヒドロ体、ジフェニル体、ジベンジル体等を例示するメタロセン化合物を主成分として含むメタロセン触媒が用いられる。また、メタロセン触媒は、例えば、シクロペンタジエニル基、置換基を有するシクロペンタジエニル基（置換シクロペンタジエニル基）、インデニル基、置換インデニル基から選ばれる１種類の基と、フルオレニル基、置換フルオレニル基から選ばれる１種類の基が、架橋基により架橋された配位子を有する周期表第４族の遷移金属化合物を挙げることができ、その代表例としてジフェニルメチレン（１−シクロペンタジエニル）（９−フルオレニル）ジルコニウムジクロリド、ジフェニルメチレン（３−メチル−１−シクロペンタジエニル）（９−フルオレニル）ジルコニウムジクロリド、ジフェニルメチレン（１−シクロペンタジエニル）（２，７−ジメチル−９−フルオレニル）ジルコニウムジクロリド、ジフェニルメチレン（１−シクロペンタジエニル）（２，７−ジ−ｔ−ブチル−９−フルオレニル）ジルコニウムジクロリド、ジフェニルメチレン（１−インデニル）（９−フルオレニル）ジルコニウムジクロリド、ジフェニルメチレン（４−フェニル−１−インデニル）（９−フルオレニル）ジルコニウムジクロリド、ジフェニルメチレン（４−フェニル−１−インデニル）（２，７−ジ−ｔ−ブチル−９−フルオレニル）ジルコニウムジクロリド等のジクロル体および上記メタロセン化合物のジメチル体、ジエチル体、ジヒドロ体、ジフェニル体、ジベンジル体などを例示するメタロセン化合物を主成分とするものである。 As described above, a polyethylene-based resin which is a plastic resin is often used as the material of the laminated film, but conventionally, this polyethylene-based resin is manufactured from petrochemicals using petroleum as a starting material, for example The linear low density polyethylene-based resin described above is a high temperature such as 120.degree. C. or higher in the gas phase in the presence of a metallocene catalyst and ethylene obtained by crude oil purification and the like and .alpha.-olefin as a comonomer species. Copolymerized with The α-olefin is represented by the general formula R-CH = CH 2 (wherein R is an alkyl group having 1 or more carbon atoms), propylene, 1-butene, 1-pentene, 1-hexene, 1- Heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, octadecene and the like can be exemplified. The metallocene catalyst is not particularly limited, and, for example, one kind of group selected from a cyclopentadienyl group, a substituted cyclopentadienyl group (substituted cyclopentadienyl group), an indenyl group and a substituted indenyl group And a transition metal compound of Group 4 of the periodic table having a ligand in which one type of group selected from a fluorenyl group and a substituted fluorenyl group is crosslinked by a crosslinking group, and diphenylmethylene (1 -Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-methyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (1-cyclopentadienyl) (2,7 -Dimethyl-9-fluorenyl) zirconium dichloride, diphenyl Thiylene (1-cyclopentadienyl) (2,7-di-tert-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (4-phenyl-1) -Dichloro bodies such as -indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (4-phenyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride and dimethyl bodies of the above metallocene compounds The metallocene catalyst which has as a main component the metallocene compound which illustrates a diethyl body, a dihydro body, a diphenyl body, a dibenzyl body etc. is used. Moreover, the metallocene catalyst includes, for example, one kind of group selected from a cyclopentadienyl group, a substituted cyclopentadienyl group (substituted cyclopentadienyl group), an indenyl group and a substituted indenyl group, a fluorenyl group, A transition metal compound of Group 4 of the periodic table having a ligand in which one type of group selected from substituted fluorenyl groups is cross-linked by a cross-linking group can be mentioned, and a representative example thereof is diphenylmethylene (1-cyclopentadiphenyl). Enyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-methyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (1-cyclopentadienyl) (2,7-dimethyl-9) -Fluorenyl) zirconium dichloride, diphenylmethylene (1- Ropentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (4-phenyl-1-indenyl) (9-fluorenyl ) Dichloro bodies such as zirconium dichloride, diphenylmethylene (4-phenyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride and dimethyl, diethyl or dihydro bodies of the above metallocene compounds A metallocene compound having a diphenyl compound, a dibenzyl compound and the like as an example is a main component.

しかしながら、石油など枯渇資源の節約志向とともに、二酸化炭素排出量の増加による地球温暖化など環境問題の意識が高まる中で、上述したような石油由来によるポリエチレン系樹脂では、石化製品の製造から廃棄に至るまでの間に、石油原料の持つ固定化した二酸化炭素が大量に排出されてしまうため、上記志向に沿うことができない。   However, with an increasing awareness of environmental problems such as global warming due to an increase in carbon dioxide emissions, as well as saving resources such as oil and other depleted resources, polyethylene-based resins derived from petroleum as described above have been changed from manufacturing petrochemical products to disposal. In the meantime, the fixed carbon dioxide possessed by petroleum raw materials is discharged in large quantities, so the above intention can not be met.

このような問題を踏まえ、近年、プラスチック類を、カーボンニュートラルで再生可能資源である植物から製造する技術の開発が進んでおり、その中でも、プラスチック類中で最も多く生産されているポリエチレンを、バイオマス系のサトウキビを出発原料として生産する技術が確立した。（加工技術研究会編、コンバーテック２００９．９、Ｐ６３〜６７）なお、カーボンニュートラルとは、植物の生育時の二酸化炭素吸収量と、燃焼時の二酸化炭素排出量とが略同一であることをいう。   Based on these problems, in recent years, development of technology to produce plastics from plants that are carbon neutral and renewable resources is in progress, and among them, polyethylene, which is the most produced in plastics, is a biomass Technology was established to produce sugarcane as a starting material. Note that carbon neutral means that carbon dioxide absorption during plant growth and carbon dioxide emissions during combustion are approximately the same. Say.

図１は、サトウキビ由来のポリエチレン製造の一例を示すフロー図、図２は本願発明のサトウキビ由来の直鎖状低密度ポリエチレン系樹脂からなるフィルムを模式的に示す断面側面図である。   FIG. 1 is a flow chart showing an example of production of polyethylene derived from sugar cane, and FIG. 2 is a cross-sectional side view schematically showing a film made of a linear low density polyethylene resin derived from sugar cane according to the present invention.

この図１に示すように、畑より刈り取ったサトウキビをから取り出した糖液を加熱濃縮して結晶化させた粗糖と廃糖密とを遠心分離機で分離する。次いで、廃糖密を適切な濃度まで水で希釈し、酵母菌により発酵させてエタノールを生成する。そして、このバイオエタノールを加熱して触媒存在下で分子内脱水反応により得られたエチレンを、重合触媒により重合させてポリエチレンが得られる。なお、植物由来のエチレンおよびポリエチレンは、石油由来のエチレンおよびポリエチレンと品質同等性が確認されている。   As shown in FIG. 1, the sugar solution from which the sugarcane harvested from the field has been removed is removed by heating and concentration to crystallize crude sugar and crystallized waste sugar by means of a centrifugal separator. The waste molasses is then diluted with water to an appropriate concentration and fermented by yeast to produce ethanol. Then, this bioethanol is heated, and ethylene obtained by the intramolecular dehydration reaction in the presence of a catalyst is polymerized by a polymerization catalyst to obtain polyethylene. Plant-derived ethylene and polyethylene have been confirmed to have the same quality as petroleum-derived ethylene and polyethylene.

そこで、本願発明のフィルムに用いる直鎖状低密度ポリエチレン系樹脂は、上記のような出発原料を植物由来としたエチレンから生成するものであるが、この生成方法としては、石油由来のエチレンから直鎖状低密度ポリエチレン系樹脂を生成する場合と同じように、植物由来エチレンと、α−オレフィンとを、メタロセン触媒の存在下において気相重合法により共重合させることで得ることができる。   Then, although the linear low density polyethylene resin used for the film of this invention is produced from ethylene which made the above-mentioned starting materials a plant origin, as this production method, it is direct from ethylene derived from petroleum. As in the case of producing a linear low density polyethylene-based resin, it can be obtained by copolymerizing plant-derived ethylene and an α-olefin by gas phase polymerization in the presence of a metallocene catalyst.

本願発明では、上記のようにして得られた植物由来の直鎖状低密度ポリエチレン系樹脂を用いて容器や包装袋を構成した積層フィルムを形成するフィルムを製造することにより、積層フィルムに用いられる樹脂組成物（直鎖状低密度ポリエチレン系樹脂など）において、石油由来樹脂組成物の使用比率を低下させて、石油資源の節約を可能とするとともに、二酸化炭素の排出量削減による環境向上に貢献するものである。   In this invention, it is used for a laminated film by manufacturing the film which forms the laminated film which comprised the container and the packaging bag using the linear low density polyethylene type resin of plant origin obtained as mentioned above In resin compositions (such as linear low density polyethylene resins), the use ratio of petroleum-derived resin composition can be reduced to save oil resources and contribute to environmental improvement by reducing carbon dioxide emissions. It is

本願では、上記気相重合法にて得られたサトウキビ（サトウキビに限定されず、その他直鎖状低密度ポリエチレン系樹脂の製造原料となる植物であればよい）由来の直鎖状低密度ポリエチレン系樹脂からなる樹脂組成物１を用いて、図２に示すようなフィルムＦ１とすることができる。   In the present application, a linear low density polyethylene-based material derived from sugar cane (not limited to sugarcane and may be any plant as a raw material for producing a linear low density polyethylene-based resin) obtained by the above gas phase polymerization method It can be set as the film F1 as shown in FIG. 2 using the resin composition 1 which consists of resin.

また、上記サトウキビ由来の直鎖状低密度ポリエチレン系樹脂は、石油由来の直鎖状低密度ポリエチレン系樹脂と同様に、コモノマー種がブテン−１（Ｃ４）、密度が０．９１０〜０．９２５ｇ／ｃｍ３、メルトフローレート（ＭＦＲ）が０．５〜４．０ｇ／１０分の範囲、より好ましくは０．７〜３．５ｇ／１０分とした各物性を有することができ、そのエチレン−α−オレフィン共重合体が用いられる。このようなサトウキビ由来の直鎖状低密度ポリエチレン系樹脂からなる樹脂組成物を石油由来の直鎖状低密度ポリエチレン系樹脂に対して９０重量％を上限に適宜割合で含有させるものである。 In addition, the linear low density polyethylene-based resin derived from sugar cane has, as a petroleum-derived linear low density polyethylene-based resin, the comonomer type is butene-1 (C4) and the density is 0.910 to 0.925 g. / cm 3, a range melt flow rate (MFR) of 0.5 to 4.0 g / 10 min, more preferably may have respective physical properties was 0.7~3.5g / 10 min, the ethylene - An alpha-olefin copolymer is used. Such a resin composition comprising a linear low density polyethylene-based resin derived from sugar cane is contained in an appropriate ratio at an upper limit of 90% by weight with respect to a petroleum-derived linear low density polyethylene-based resin.

なお、上記物性評価では、密度（ｄ、単位：ｇ／ｃｍ３）として、１５０℃でプレス成形して得られた厚さ１ｍｍのシートを用い、ＪＩＳ Ｋ ６７６０（１９８１）に従って測定を行ったものである。また、メルトフローレート（ＭＦＲ、単位：ｇ／１０分）は、ＪＩＳ Ｋ ７２１０（１９９５）に準じ、試験温度１９０℃の条件にて、試験荷重２１．１８Ｎで測定したものである。 In addition, in the said physical-property evaluation, it measured according to JISK6760 (1981) using the sheet | seat of thickness 1mm obtained by press-molding at 150 degreeC as a density (d, unit: g / cm < 3 >) It is. Moreover, melt flow rate (MFR, unit: g / 10 minutes) is measured according to JIS K 7210 (1995) at a test temperature of 190 ° C. under a test load of 21.18 N.

さらには、上記サトウキビ由来の直鎖状低密度ポリエチレン系樹脂には、放射性炭素年代測定１４Ｃによるバイオマス度が、８０〜１００％を有する上記エチレン−α−オレフィン共重合体が用いられる。 Furthermore, the said ethylene-alpha-olefin copolymer which has 80 to 100% of biomass degree by radiocarbon dating 14 C is used for the linear low density polyethylene-type resin derived from the said sugarcane.

ここで、植物（バイオマス）由来と石油由来の樹脂組成物は、分子量や機械的性質・熱的性質のような物性に差を生じない。そこで、これらを区別するためには、一般的にバイオマス度が用いられている。このバイオマス度では、石油由来の樹脂組成物の炭素には、１４Ｃ（放射性炭素１４、半減期５７３０年）が含まれていないことから、この１４Ｃの濃度を加速器質量分析により測定し、樹脂組成物において、植物由来樹脂組成物の含有割合の指標にするものである。従って、植物由来の樹脂組成物を用いたフィルムであれば、そのフィルムのバイオマス度を測定すると、植物由来樹脂組成物の含有量に応じたバイオマス度が生じる。 Here, resin compositions derived from plants (biomass) and petroleum do not cause differences in physical properties such as molecular weight, mechanical properties and thermal properties. Therefore, in order to distinguish them, the degree of biomass is generally used. In this degree of biomass, carbon of petroleum-derived resin composition does not contain 14 C (radioactive carbon 14, half-life 5730), so the concentration of this 14 C is measured by accelerator mass spectrometry, and resin The composition is used as an indicator of the content ratio of the plant-derived resin composition. Therefore, if it is a film using the resin composition derived from plants, when the biomass degree of the film is measured, the biomass degree according to content of a plant origin resin composition will arise.

このバイオマス度の測定は、測定対象試料を燃焼して二酸化炭素を発生させ、真空ラインで精製した二酸化炭素を、鉄を触媒として水素で還元し、グラファイトを生成させる。そして、このグラファイトをタンデム加速器をベースとした１４Ｃ−ＡＭＳ専用装置（ＮＥＣ社製）に装着して、１４Ｃの計数、１３Ｃの濃度（１３Ｃ／１２Ｃ）、１４Ｃの濃度（１４Ｃ／１２Ｃ）の測定を行い、この測定値から標準現代炭素に対する試料炭素の１４Ｃ濃度の割合を算出する。この測定では、米国国立標準局（ＮＩＳＴ）から提供されたシュウ酸（ＨＯｘＩＩ）を標準試料とした。 In the measurement of the degree of biomass, a sample to be measured is burned to generate carbon dioxide, and carbon dioxide purified in a vacuum line is reduced with hydrogen using iron as a catalyst to generate graphite. Then, the graphite was attached to the tandem accelerator 14 C-AMS-only apparatus which is based on (manufactured by NEC Corp.), 14 C counts, the 13 C concentration (13 C / 12 C), the 14 C concentration (14 Measure C / 12 C) and calculate the ratio of 14 C concentration of sample carbon to standard modern carbon from this measurement value. In this measurement, oxalic acid (HOxII) provided by the National Institute of Standards (NIST) was used as a standard sample.

本願ではこのような樹脂組成物からなるフィルムの構成にすることで、全て石油由来の樹脂組成物に依存する状態から、この石油由来のポリエチレン系樹脂に、石油由来のポリエチレン系樹脂と性能的に違いがないサトウキビなど植物由来のポリエチレン系樹脂を混成（置換）することで、フィルム製造および廃棄時の二酸化炭素排出量を抑制することができる。   In the present application, by making a film composed of such a resin composition, it is possible to use this petroleum-derived polyethylene-based resin and the petroleum-derived polyethylene-based resin in terms of performance from the state entirely dependent on the petroleum-derived resin composition. By mixing (substituting) a plant-based polyethylene-based resin such as sugar cane which has no difference, carbon dioxide emissions at the time of film production and disposal can be suppressed.

また、本願発明の樹脂組成物１は、コモノマー種がブテン−１、密度が０．９１０〜０．９２０ｇ／ｃｍ３，メルトフローレートが０．７０〜１．３０ｇ／１０分のエチレン−α−オレフィン共重合体であるので、石油由来のポリエチレン系樹脂と物性的に違いがないため、既存のフィルム製造工程を用いることができ、包材の加工適性を損ねることなく原料を切替えることができる。 Further, the resin composition 1 of the present invention has a comonomer species of butene-1, a density of 0.910 to 0.920 g / cm 3 , and a melt flow rate of 0.70 to 1.30 g / 10 min. Since it is an olefin copolymer, there is no difference in physical properties from petroleum-derived polyethylene resins, so that existing film manufacturing processes can be used, and raw materials can be switched without impairing the processability of the packaging material.

さらに、本願発明の樹脂組成物１は、放射性炭素年代測定１４Ｃの測定値から算定するバイオマス度を有するエチレン−α−オレフィン共重合体であるので、フィルムを構成するポリエチレン系樹脂の原料由来を、このバイオマス度を指標にして識別でき、フィルムの製造時から廃棄時までの由来原料を確認することができる。 Furthermore, since the resin composition 1 of the present invention is an ethylene-α-olefin copolymer having a biomass degree calculated from the measurement value of radiocarbon dating 14 C, the raw material origin of the polyethylene resin constituting the film is This biomass degree can be identified as an index, and the raw material from the time of film production to the time of disposal can be confirmed.

次に、本願では、上述した樹脂組成物１と、後述する石油由来ポリエチレン系樹脂２とで、以下のようなフィルムに構成させることができる。図３は樹脂組成物と、石油由来のポリエチレン系樹脂とを混合した単層構成のフィルムを模式的に示す断面側面図、図４は中間層を樹脂組成物とした多層構造からなるフィルムを模式的に示す断面側面図、図５は中間層を樹脂組成物および石油由来ポリエチレン系樹脂を混合した層とした多層構造からなるフィルムを模式的に示す断面側面図である。   Next, in the present application, the following film can be formed by the resin composition 1 described above and the petroleum-derived polyethylene-based resin 2 described later. FIG. 3 is a cross-sectional side view schematically showing a single-layered film in which a resin composition and a petroleum-derived polyethylene-based resin are mixed, and FIG. 4 is a schematic view of a film having a multilayer structure in which the intermediate layer is a resin composition. FIG. 5 is a cross-sectional side view schematically showing a film having a multilayer structure in which the intermediate layer is a layer in which the resin composition and the petroleum-derived polyethylene-based resin are mixed.

この場合、上記樹脂組成物１を５〜９０重量％と、石油由来ポリエチレン系樹脂２を１０〜９５重量％とを、下記の（Ａ）または（Ｂ）あるいは（Ｃ）の要領にてフィルムを構成した。まず（Ａ）のフィルムＦ２として、図３に示すように、樹脂組成物１と、石油由来のポリエチレン系樹脂２とを混合した単層構成にすることができる。   In this case, 5 to 90% by weight of the resin composition 1 and 10 to 95% by weight of the petroleum-derived polyethylene resin 2 in the following manner (A) or (B) or (C) Configured. First, as the film F2 of (A), as shown in FIG. 3, it is possible to have a single layer configuration in which the resin composition 1 and the petroleum-derived polyethylene-based resin 2 are mixed.

また、（Ｂ）のフィルムＦ３として、図４に示すように、中間層を樹脂組成物１とし、外層および内層を石油由来ポリエチレン系樹脂２とした多層構成にすることもできる。   In addition, as the film F3 of (B), as shown in FIG. 4, the intermediate layer may be a resin composition 1, and the outer layer and the inner layer may be a petroleum-derived polyethylene resin 2 in a multilayer structure.

さらに、（Ｃ）のフィルムＦ４として、図５に示すように、中間層を樹脂組成物１と、石油由来ポリエチレン系樹脂２とを混合した層とし、外層および内層を石油由来ポリエチレン系樹脂２とした多層構成にすることもできる。   Further, as the film F4 of (C), as shown in FIG. 5, the intermediate layer is a layer obtained by mixing the resin composition 1 and the petroleum-derived polyethylene resin 2 and the outer layer and the inner layer are the petroleum-derived polyethylene resin 2 and It is also possible to have a multi-layered configuration.

このような構成にすることで、フィルムＦ２〜Ｆ４を構成するポリエチレン系樹脂２の石油由来の使用比率を低下させることができ、フィルム製造および廃棄時の二酸化炭素排出量を抑制することができる。加えて、（Ｂ）あるいは（Ｃ）のようなフィルムＦ３〜Ｆ４を構成する内外層に石油由来ポリエチレン系樹脂２を用いることで、既存の製造工程が有する特性でフィルムＦ３〜Ｆ４を製造することができる。   With such a configuration, the petroleum-derived use ratio of the polyethylene resin 2 constituting the films F2 to F4 can be reduced, and carbon dioxide emissions at the time of film production and disposal can be suppressed. In addition, by using the petroleum-derived polyethylene-based resin 2 in the inner and outer layers constituting the films F3 to F4 such as (B) or (C), the films F3 to F4 are manufactured with the characteristics of the existing manufacturing process. Can.

次に、本願では、上記フィルムＦ１〜Ｆ４を用いた積層フィルムにすることができる。図６は、積層フィルムの一例を模式的に示す断面側面図、図７は本願発明の積層フィルムを用いて形成した包装袋の一例としてのスタンディングパウチを示す斜視図である。   Next, in the present application, a laminated film using the films F1 to F4 can be obtained. FIG. 6 is a cross-sectional side view schematically showing an example of the laminated film, and FIG. 7 is a perspective view showing a standing pouch as an example of a packaging bag formed using the laminated film of the present invention.

まず、積層フィルム３は、この図６に示すように、上記フィルムＦ１〜Ｆ４のいずれかをシーラントフィルム４として、基材フィルム５と積層させる。   First, as shown in FIG. 6, the laminated film 3 laminates any one of the films F1 to F4 as the sealant film 4 with the base film 5.

なお、基材フィルム５としては、例えば、ポリエチレン系樹脂、ポリプロピレン系樹脂、環状ポリオレフィン系樹脂、ポリスチレン系樹脂、アクリロニトリル−スチレン共重合体（ＡＳ樹脂）、アクリロニトリル−ブタジエン−スチレン共重合体（ＡＢＳ樹脂）、ポリ塩化ビニル系樹脂、フッ素系樹脂、ポリ（メタ）アクリル系樹脂、ポリカーボネート系樹脂、ポリエチレンテレフタレート、ポリエチレンナフタレート等のポリエステル系樹脂、各種のナイロン等のポリアミド系樹脂、ポリイミド系樹脂、ポリアミドイミド樹脂、ポリアリールフタレート系樹脂、シリコーン系樹脂、ポリスルホン系樹脂、ポリフェニレンスルフィド系樹脂、ポリエーテルスルホン系樹脂、ポリウレタン系樹脂、アセタール系樹脂、セルロース系樹脂等の各種樹脂フィルムまたはシートを使用することができる。   In addition, as base film 5, for example, polyethylene resin, polypropylene resin, cyclic polyolefin resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin) ), Polyvinyl chloride resin, fluorine resin, poly (meth) acrylic resin, polycarbonate resin, polyester resin such as polyethylene terephthalate and polyethylene naphthalate, various polyamide resins such as nylon, polyimide resin, polyamide Imide resin, polyaryl phthalate resin, silicone resin, polysulfone resin, polyphenylene sulfide resin, polyether sulfone resin, polyurethane resin, acetal resin, cellulose resin, etc. It may be used fat film or sheet.

このような構成にすることで、ヒートシールに用いるシーラントフィルム４においても、このシーラントフィルム４である各フィルムＦ１〜Ｆ４を構成するポリエチレン系樹脂の石油由来の使用比率を低下させることができ、石油資源の節約とともに、積層フィルム３の製造および廃棄時の二酸化炭素排出量を抑制することができる。   With such a configuration, also in the sealant film 4 used for heat sealing, it is possible to reduce the petroleum-derived use ratio of the polyethylene-based resin that constitutes each of the films F1 to F4 that is the sealant film 4 Along with saving of resources, carbon dioxide emissions at the time of production and disposal of the laminated film 3 can be suppressed.

以上のような積層フィルム３を用い、積層フィルム３からなる２枚の側面シート７、８のシーラントフィルム４面同士を対向して配置し、積層フィルム３の下端部に少なくとも片面にシーラントフィルム４が積層された積層体からなる底面シート９を、シーラントフィルム４面を外面にして中央で山折りして挿入し、ガセット部を有する形式に形成されており、山折りされた底面シート９の両側下端近傍には、略半円形の底面シートの切り欠き部が設けられ、ガセット部が、周縁部を含む船底形の底部シール部でヒートシールされ底部が形成される。   The sealant film 4 of the two side sheets 7 and 8 made of the laminated film 3 is disposed opposite to each other using the laminated film 3 as described above, and the sealant film 4 is provided on at least one side of the lower end of the laminated film 3 Bottom sheet 9 made of laminated laminate is inserted into the center by mountain folding with the surface of sealant film 4 as the outer surface, and is formed in a form having a gusset portion, both lower ends of mountain folding bottom sheet 9 In the vicinity, a substantially semi-circular bottom sheet cutout portion is provided, and the gusset portion is heat-sealed by the bottom seal portion including the peripheral portion to form the bottom portion.

次いで、表裏の２枚の側面シート７、８の両側端縁部を側端縁シール部でヒートシールして胴部が形成され、上端部を残して内容物の充填口とする、図７に示すようなスタンディングパウチ形式に製袋されたパウチ（包装袋６）が形成される。そして、上端部の充填口に設けた上部シール部は、この部分から内容物を充填した後、例えば、脱気シールなどによりヒートシールして密封するものである。なお、図示しないが、胴部の上部などにレーザーにて開封用切れ目線を設けた注出口部を形成させてもよい。   Next, the side edges of the two side sheets 7, 8 on the front and back are heat sealed with the side edge seal portions to form a body, leaving the upper end as the filling port for the contents, as shown in FIG. A pouch (packaging bag 6) is formed which is made into a standing pouch type as shown. The upper seal portion provided at the filling port at the upper end portion is formed by heat sealing with a degassing seal or the like after the content is filled from this portion. In addition, although not shown in the drawings, it is also possible to form a spout portion provided with a slit for opening by laser on the upper portion of the body portion or the like.

このような構成にすることで、包装袋６を構成する積層フィルム３におけるポリエチレン系樹脂の石油由来の使用比率を低下させることができ、石油資源の節約とともに、包装袋６の製造および廃棄時の二酸化炭素排出量を抑制することができる。特にこの包装袋６が、詰め替え用スタンディングパウチであるので、使い捨てとして普及するこのような包装袋を構成するポリエチレン系樹脂の石油由来の使用比率を低下させるとともに、二酸化炭素排出量を大きく抑制することができる。   With such a configuration, it is possible to reduce the petroleum-derived use ratio of the polyethylene resin in the laminated film 3 constituting the packaging bag 6, and at the time of manufacturing and discarding the packaging bag 6 along with saving of petroleum resources. CO2 emissions can be reduced. In particular, since the packaging bag 6 is a standing pouch for refilling, it is possible to reduce the petroleum-derived use ratio of the polyethylene-based resin that constitutes such packaging bags that are disseminated as disposables, and to greatly suppress carbon dioxide emissions. Can.

なお、本願発明の樹脂組成物１からなるフィルムＦ１〜Ｆ４や、これらフィルムＦ１〜Ｆ４を用いた積層フィルム３を使用して、上述したスタンディングパウチに例示される包装袋６以外にも、ポリエチレン系樹脂を用いた樹脂組成物１から構成される、例えば、飲食品・化粧品・薬品・雑貨品などの内容物を収容するラミネートチューブ、液体紙容器などを含む容器や、容器の蓋材、あるいは容器のラベルなどを構成することができ、いっそう石油由来の使用比率を低下させるとともに、二酸化炭素排出量を大きく抑制することができる。   In addition, using the films F1 to F4 made of the resin composition 1 of the present invention, and the laminated films 3 using these films F1 to F4, polyethylene can be used other than the packaging pouch 6 exemplified in the above-mentioned standing pouch. A container comprising a resin composition 1 using a resin, for example, a laminate tube for containing contents such as food and drink, cosmetics, medicines, sundries, etc., a container including a liquid paper container, a lid of the container, or a container While being able to comprise the label etc. of, and reducing the use ratio derived from petroleum further, a carbon dioxide emission can be suppressed large.

次に、本願発明の植物由来ポリエチレン系樹脂（樹脂組成物１）を用いて構成したフィルムの実施例を説明する。   Next, the Example of the film comprised using the plant origin polyethylene-type resin (resin composition 1) of this invention is demonstrated.

スクリュー径３０ｍｍφ押出機を用いて、サトウキビ由来直鎖状低密度ポリエチレン系樹脂（樹脂組成物１）であるブラスケム社Ｃ４ＬＬ−ＬＬ１１８（ｄ＝０．９１６、ＭＦＲ＝１．０ｇ／１０分）を２００℃で溶融混練し、樹脂組成物を得た。次いで、上吹き空冷インフレーション共押出製膜機により、押出し温度２００℃、回転数６０ｒｐｍの加工条件において樹脂組成物を成形することで、厚み５０μｍの安定して外観の優れる図１に示すフィルムＦ１を製膜することができ、そのバイオマス度を測定すると、約８８％であった。なお、サトウキビ由来直鎖状低密度ポリエチレン系樹脂に含まれるコモノマー種のブテン−１（Ｃ４）は石油由来のものであり、その含有量は１〜１５モル％（以下同様）である。   Using a screw diameter of 30 mmφ extruder, the Braschem C4LL-LL118 (d = 0. 916, MFR = 1.0 g / 10 min), which is a sugarcane-derived linear low density polyethylene resin (resin composition 1) The mixture was melt-kneaded at ° C to obtain a resin composition. Next, the resin composition is molded with a top-blowing air-cooling inflation co-extrusion film-forming machine under the processing conditions of an extrusion temperature of 200 ° C. and a rotation number of 60 rpm to obtain a 50 μm thick film F1 shown in FIG. It was possible to form a film, and its biomass degree was about 88% when measured. The comonomer species butene-1 (C4) contained in the sugarcane-derived linear low density polyethylene resin is petroleum-derived, and the content thereof is 1 to 15 mol% (the same applies hereinafter).

これに対し、上記フィルムＦ１の比較例１として、石化由来Ｃ４ＬＬ直鎖状低密度ポリエチレン系樹脂を用いて、実施例１と同様にして、押出し温度２００℃、回転数６０ｒｐｍの加工条件で厚み５０μｍのフィルムに成形し、バイオマス度を測定すると、０％であった。   On the other hand, as Comparative Example 1 of the above-mentioned film F1, using a petrification-derived C4LL linear low density polyethylene resin, in the same manner as in Example 1, 50 μm thickness under processing conditions of an extrusion temperature of 200 ° C. and a rotation number of 60 rpm. It was molded into a film of 0% and the degree of biomass was measured to be 0%.

実施例１の樹脂組成物について次の各物性評価試験を行い、得られた結果を以下に記す。

Figure 2019064743
上記結果から、サトウキビ（植物）由来直鎖状低密度ポリエチレン系樹脂（実施例１）は、石化由来直鎖状低密度ポリエチレン系樹脂（比較例１）に比べて、引張破断強度や引裂強さが強く、腰やシール強度は同等の強度を有し、弾性率が低く柔軟であることが分かる。このように、植物由来直鎖状低密度ポリエチレン系樹脂は、石化由来直鎖状低密度ポリエチレン系樹脂と比較して同等以上の物性を有し、石化由来直鎖状低密度ポリエチレン系樹脂の製造加工適性と遜色ないことが実証された。 The following physical property evaluation tests were performed on the resin composition of Example 1, and the obtained results are described below.
Figure 2019064743
 From the above results, the sugarcane (plant) -derived linear low density polyethylene-based resin (Example 1) has a tensile breaking strength and tear strength compared to the petrification-derived linear low density polyethylene-based resin (Comparative Example 1) It can be seen that the waist and seal strength have similar strength, low elastic modulus and flexibility. Thus, the plant-derived linear low density polyethylene-based resin has physical properties equal to or higher than those of the petrification-derived linear low density polyethylene-based resin, and the production of the petrification-derived linear low density polyethylene-based resin It proved to be comparable with processing aptitude.

なお、引張破断強度（伸び）は、ＪＩＳ−Ｚ１７０２を参考にテンシロン万能試験機を用い、試験速度５００ｍｍ／ｍｉｎ． Ｎ＝３ ＪＩＳ−Ｋ７１２７試験片タイプ５（ダンベル片：最小平行巾６ｍｍ、チャック間距離８０ｍｍ）で行った。
弾性率（引張）は、ＪＩＳ−Ｋ７１７６参考にテンシロン万能試験機を用い、試験速度１ｍｍ／ｍｉｎ． １．５ｍｍ伸びた時の強度を測定したもので、Ｎ＝３ ＪＩＳ−Ｋ７１２７試験片タイプ２参考（短冊：巾１５ｍｍ、チャック間距離１５０ｍｍ）で行った。
腰は、ループスティフネステスターを用い、ループ長さ６０ｍｍ、サンプル巾１５ｍｍ、Ｎ＝３、押しつぶし距離１７ｍｍ（目盛り３）で行った。
シール強度は、ヒートシールテスターＴＰ−７０１Ｓを用い、片面加熱 １ｋｇｆ／ｃｍ２×１．０ｓ ＰＥＴ１２μｍを評価サンプルの上に載せてシールし、テンシロン万能試験機において試験速度３００ｍｍ／ｍｉｎ． 巾１５ｍｍ Ｎ＝３ １４０℃で行った。 The tensile breaking strength (elongation) was measured using a TENSILON universal testing machine with reference to JIS-Z1702 at a test speed of 500 mm / min. N = 3 JIS-K7127 test piece type 5 (dumbbell strip: minimum parallel width 6 mm, distance between chucks 80 mm).
The modulus of elasticity (tensile) was measured using a Tensilon universal tester in accordance with JIS-K7176, at a test speed of 1 mm / min. The strength was measured at an elongation of 1.5 mm, and N = 3 JIS-K7127 test piece type 2 reference (strip: width 15 mm, distance between chucks 150 mm).
The waist was measured using a loop stiffness tester with a loop length of 60 mm, a sample width of 15 mm, N = 3, and a crushing distance of 17 mm (scale 3).
The seal strength was measured using a heat seal tester TP-701S with one side heating 1 kgf / cm 2 × 1.0 s PET 12 μm placed on the evaluation sample and sealed, and the test speed 300 mm / min. It carried out by width 15 mm N = 3 140 degreeC.

スクリュー径３０ｍｍφ押出機を用いて、サトウキビ由来直鎖状低密度ポリエチレン系樹脂（樹脂組成物１）であるブラスケム社Ｃ４ＬＬ−ＬＬ１１８（ｄ＝０．９１６、ＭＦＲ＝１．０ｇ／１０分）を５０重量％と、石油由来直鎖状低密度ポリエチレン系樹脂２である宇部丸善ポリエチレンＬＤＰＥ−Ｆ１２０Ｎ（ｄ＝０．９２０、ＭＦＲ＝１．２ｇ／１０分）５０重量％を２００℃で溶融混練し、樹脂組成物を得た。次いで、上吹き空冷インフレーション共押出製膜機により、押出し温度２００℃、回転数６０ｒｐｍの加工条件において樹脂組成物を厚み１３０μｍの図３に示すフィルムＦ２に成形し、そのバイオマス度を測定すると、約４４％であった。   Using a screw diameter of 30 mmφ extruder, 50 of Braschem C4LL-LL118 (d = 0. 916, MFR = 1.0 g / 10 min), which is a sugarcane-derived linear low density polyethylene resin (resin composition 1) Melt-kneaded at 200 ° C., 50% by weight and 50% by weight of Ubemaruzan polyethylene LDPE-F 120 N (d = 0.920, MFR = 1.2 g / 10 min) which is petroleum-derived linear low density polyethylene resin 2 A resin composition was obtained. Next, the resin composition is formed into a film F2 shown in FIG. 3 having a thickness of 130 μm under processing conditions of an extrusion temperature of 200 ° C. and a rotation number of 60 rpm by a top blowing air-cooling inflation coextrusion film forming machine, and its biomass degree is measured. It was 44%.

第１層用および第３層用樹脂組成物として、スクリュー径３０ｍｍφ押出機を用いて、三井化学Ｃ６ＬＬ−エボリューＳＰ２０２０（ｄ＝０．９１６、ＭＦＲ＝２．３ｇ／１０分）を２００℃で溶融混練し、樹脂組成物を得た。同様に第２層用樹脂組成物として、スクリュー径３０ｍｍφ押出機を用いて、サトウキビ由来直鎖状低密度ポリエチレン系樹脂であるブラスケム社Ｃ４ＬＬ−ＬＬ１１８（ｄ＝０．９１６、ＭＦＲ＝１．０ｇ／１０分）を２００℃で溶融混練し、樹脂組成物を得た。なお、第１層：第２層：第３層の層比は１：１：１とした。次いで、二種三層の上吹き空冷インフレーション共押出製膜機により、押出し温度２００℃、回転数６０ｒｐｍの加工条件において樹脂組成物を厚み１３０μｍの図４に示すフィルムＦ３に成形し、そのバイオマス度を測定すると、約２９％であった。   Melt Mitsui Chemicals C6LL-Evolue SP 2020 (d = 0.916, MFR = 2.3 g / 10 min) at 200 ° C as a resin composition for the first layer and the third layer using an extruder with a screw diameter of 30 mmφ The mixture was kneaded to obtain a resin composition. Similarly, as a resin composition for the second layer, using a screw diameter of 30 mmφ extruder, Brass Chem C4LL-LL118 (d = 0. 916, MFR = 1.0 g / m) which is a linear low density polyethylene resin derived from sugar cane The mixture was melt-kneaded at 200 ° C. for 10 minutes to obtain a resin composition. The layer ratio of the first layer: the second layer: the third layer was 1: 1: 1. Next, the resin composition is formed into a film F3 shown in FIG. 4 having a thickness of 130 μm under processing conditions of an extrusion temperature of 200 ° C. and a rotation number of 60 rpm by two types and three layers of upper blowing air cooling inflation coextrusion film forming machine Was about 29%.

第１層用および第３層用樹脂組成物として、スクリュー径３０ｍｍφ押出機を用いて、三井化学Ｃ６ＬＬ−エボリューＳＰ２０２０（ｄ＝０．９１６、ＭＦＲ＝２．３ｇ／１０分）を２００℃で溶融混練し、樹脂組成物を得た。同様に第２層用樹脂組成物として、スクリュー径３０ｍｍφ押出機を用いて、サトウキビ由来直鎖状低密度ポリエチレン系樹脂であるブラスケム社Ｃ４ＬＬ−ＬＬ１１８（ｄ＝０．９１６、ＭＦＲ＝１．０ｇ／１０分）５０重量部と、宇部丸善ポリエチレンＬＤＰＥ−Ｆ１２０Ｎ（ｄ＝０．９２０、ＭＦＲ＝１．２ｇ／１０分）５０重量部とを２００℃で溶融混練し、樹脂組成物を得た。なお、第１層：第２層：第３層の層比は１：２：１とした。次いで、二種三層の上吹き空冷インフレーション共押出製膜機により、押出し温度２００℃、回転数６０ｒｐｍの加工条件において樹脂組成物を厚み１３０μｍの図５に示すフィルムＦ４に成形し、このバイオマス度を測定すると、約２２％であった。   Melt Mitsui Chemicals C6LL-Evolue SP 2020 (d = 0.916, MFR = 2.3 g / 10 min) at 200 ° C as a resin composition for the first layer and the third layer using an extruder with a screw diameter of 30 mmφ The mixture was kneaded to obtain a resin composition. Similarly, as a resin composition for the second layer, using a screw diameter of 30 mmφ extruder, Brass Chem C4LL-LL118 (d = 0. 916, MFR = 1.0 g / m) which is a linear low density polyethylene resin derived from sugar cane A resin composition was obtained by melt-kneading, at 200 ° C., 50 parts by weight of 10 minutes and 50 parts by weight of Ube Maruzen Polyethylene LDPE-F 120 N (d = 0.920, MFR = 1.2 g / 10 min). The layer ratio of the first layer: the second layer: the third layer was 1: 2: 1. Next, the resin composition is formed into a film F4 shown in FIG. 5 having a thickness of 130 μm under processing conditions of an extrusion temperature of 200 ° C. and a rotation number of 60 rpm by a two-kind three-layer upper blowing air cooling inflation coextrusion film forming machine. Was about 22%.

外層に厚み２５μｍの、基材フィルム５としての二軸延伸ナイロンフィルム（ＯＮｙ、東洋紡ハーデンＮ−１１０２）と、実施例４のフィルムＦ４とを用いて２液硬化型のウレタン系接着剤を使用し、ＯＮｙ面に該接着剤を約４ｇ／ｍ２塗布してポリエチレンのコロナ処理面をドライラミネーション法により貼合し、２層構成の図６に示す積層フィルム３を得、このバイオマス度を測定すると、約１８％であった。 Using a two-component curable urethane adhesive using a biaxially stretched nylon film (ONy, Toyobo Harden N-1102) as the base film 5 and a film F4 of Example 4 in the outer layer with a thickness of 25 μm Then, about 4 g / m 2 of the adhesive is applied to the ONy surface, and the corona-treated surface of polyethylene is bonded by the dry lamination method to obtain the laminated film 3 shown in FIG. , About 18%.

そして、この積層フィルム３を使用し、レーザーにて開封用切れ目線を設けた注出口部付詰め替え用スタンディングパウチ（包装袋６）を作成し、この詰め替え用スタンディングパウチに内容物を入れて口部を密封したものについて、内容物の漏れ、転倒、座屈、胴部の折れを観察したが、認められなかった。さらに１ｍの高さから落下テストを５回行ったが、破袋、漏れなどは全く認められなかった。   Then, using this laminated film 3, create a standing pouch (packing bag 6) for refilling with a spout portion provided with a slit for opening by laser using a laminated film, insert the contents into this refilling standing pouch, and open the mouth The leaked contents, overturning, buckling, and breakage of the trunk of the sealed product were observed but not observed. Furthermore, the drop test was conducted 5 times from a height of 1 m, but no bag breakage or leakage was observed at all.

外層に厚み２５μｍの、基材フィルム５としての二軸延伸ナイロンフィルム（ＯＮｙ、東洋紡ハーデンＮ−１１０２）と、中間層に、片面にアルミニウム蒸着された厚さ１２μｍのＶＭＰＥＴ（金属蒸着フィルムであり、ポリエチレンテレフタレートフィルムにアルミニウムを蒸着したもの）のアルミニウム蒸着面と積層し、さらにＶＭＰＥＴのポリエチレンテレフタレート面に２液硬化型のウレタン系接着剤を約４ｇ／ｍ２塗布して、実施例４のフィルムＦ４のコロナ処理面とをドライラミネーション法により貼合し、３層構成の積層フィルム３を得た。そして、この積層フィルム３を使用し、レーザーにて開封用切れ目線を設けた注出口部付詰め替え用スタンディングパウチ（包装袋６）を作成し、バイオマス度を測定すると、約１７％であった。 A biaxially stretched nylon film (ONy, Toyobo Harden N-1102) as the base film 5 having a thickness of 25 μm in the outer layer, and a 12 μm thick VMPET (metal-deposited film) aluminum-deposited on one side in the intermediate layer, A film F4 of Example 4 is laminated with an aluminum vapor-deposited surface of a polyethylene terephthalate film), and further coated with about 4 g / m 2 of a two-component curable urethane adhesive on a polyethylene terephthalate surface of VMPET. The laminate was bonded to the corona-treated surface by the dry lamination method to obtain a laminated film 3 having a three-layer structure. And using this laminated film 3, it was about 17% when a standing pouch (packing bag 6) for refilling with a spout with a slit for opening was provided with a laser and the degree of biomass was measured.

作成した詰め替え用スタンディングパウチに内容物を入れて口部を密封したものについて、内容物の漏れ、転倒、座屈、胴部の折れを観察したが、認められなかった。さらに１ｍの高さから落下テストを５回行ったが、破袋、漏れ等は全く認められなかった。   The contents were put in the prepared refilling standing pouch and the mouth was sealed. Leakage of the contents, overturning, buckling, and breakage of the trunk were observed, but were not observed. Furthermore, a drop test was conducted 5 times from a height of 1 m, but no bag breakage or leakage was observed at all.

上記実施例６の注出口部付詰め替え用スタンディングパウチにおける底材のみを、延伸ポリアミド（ＯＮＹ）／ＬＬＤＰＥ（直鎖状低密度ポリエチレン）からなる石油由来フィルムを用いて作成した詰め替え用スタンディングパウチに内容物を入れて口部を密封したものについて、内容物の漏れ、転倒、座屈、胴部の折れを観察したが、認められなかった。さらに１ｍの高さから落下テストを５回行ったが、破袋、漏れ等は全く認められなかった。従って、本願発明のスタンディングパウチの底材には、胴部と同じ植物由来を含む積層フィルム３でも、石油由来のフィルムでもどちらを用いてもよい。   Contents of only the bottom material in the stand-up pouch for refilling with a spout in the above Example 6 is a stand-up pouch for refilling made using a petroleum-derived film consisting of stretched polyamide (ONY) / LLDPE (linear low density polyethylene) In the case where the object was put in and the mouth was sealed, leakage of the contents, overturning, buckling, and breakage of the trunk were observed, but not observed. Furthermore, a drop test was conducted 5 times from a height of 1 m, but no bag breakage or leakage was observed at all. Therefore, as the bottom material of the standing pouch of the present invention, either a laminated film 3 containing the same plant origin as the trunk or a petroleum-derived film may be used.

実施例１同様に、スクリュー径３０ｍｍφ押出機を用いて、サトウキビ由来直鎖状低密度ポリエチレン系樹脂（樹脂組成物１）であるブラスケム社Ｃ４ＬＬ−ＬＬ３１８（ｄ＝０．９１８、ＭＦＲ＝２．７ｇ／１０分）を２００℃で溶融混練し、樹脂組成物を得た。次いで、Ｔダイキャスト製膜機により、押出し温度２２０℃、回転数４５ｒｐｍの加工条件において樹脂組成物を成形することで、厚み１２０μｍ（１種３層）の安定して外観の優れるフィルムを製膜することができ、そのバイオマス度を測定すると、約８８％であった。   Similarly to Example 1, using a screw diameter of 30 mmφ extruder, Brass Chem C4LL-LL 318 (d = 0. 918, MFR = 2.7 g), which is a linear low density polyethylene resin derived from sugar cane (resin composition 1) Melt-kneaded at 200 ° C. to obtain a resin composition. Next, the resin composition is molded by a T-die-cast film forming machine under processing conditions of an extrusion temperature of 220 ° C. and a rotation number of 45 rpm to form a film having a thickness of 120 μm (one kind three layers) with excellent appearance. The degree of biomass was about 88% when measured.

実施例１同様に、スクリュー径３０ｍｍφ押出機を用いて、サトウキビ由来直鎖状低密度ポリエチレン系樹脂（樹脂組成物１）であるブラスケム社Ｃ４ＬＬ−ＬＬ３１８（ｄ＝０．９１８、ＭＦＲ＝２．７ｇ／１０分）と、三井化学Ｃ６ＬＬ−エボリューＳＰ２０２０（ｄ＝０．９１８、ＭＦＲ＝３．８ｇ／１０分）とを７：３で２００℃において混練溶融し、Ｔダイキャスト製膜機により、押出し温度２２０℃、回転数４５ｒｐｍの加工条件において樹脂組成物を成形することで、厚み１２０μｍ（１種３層）の安定して外観の優れるフィルムを製膜することができ、そのバイオマス度を測定すると、約５９％であった。   Similarly to Example 1, using a screw diameter of 30 mmφ extruder, Brass Chem C4LL-LL 318 (d = 0. 918, MFR = 2.7 g), which is a linear low density polyethylene resin derived from sugar cane (resin composition 1) / 10 minutes) and Mitsui Chemicals C6LL-Evolue SP 2020 (d = 0. 918, MFR = 3.8 g / 10 min) by kneading at 200 ° C. at 7: 3 and extruding with a T die cast film forming machine By molding the resin composition under processing conditions of a temperature of 220 ° C. and a rotational speed of 45 rpm, it is possible to form a stable film with a thickness of 120 μm (one type and three layers) and an excellent appearance. , About 59%.

以上詳述したように、この例のポリエチレン系樹脂からなるフィルムＦ１〜Ｆ４は、気相重合法にて得られた直鎖状低密度の植物由来ポリエチレン系樹脂を含む樹脂組成物１からなるものである。また、これらフィルムＦ１〜Ｆ４をシーラントフィルムとし、基材フィルム５と積層させた積層フィルム３とするとともに、包装袋６は、この積層フィルム３からなるものである。   As described in detail above, the films F1 to F4 made of the polyethylene-based resin of this example consist of the resin composition 1 containing the linear low density plant-derived polyethylene-based resin obtained by the gas phase polymerization method It is. Moreover, while making these films F1-F4 into a sealant film and making it the laminated | multilayer film 3 laminated | stacked with the base film 5, the packaging bag 6 consists of this laminated | multilayer film 3. FIG.

なお、この発明は、ポリエチレン系樹脂からなるフィルムおよび、このフィルムで構成された包装袋や容器など、ポリエチレン系樹脂を用いたあらゆる製品に適用することができる。   In addition, this invention is applicable to all products using polyethylene-type resin, such as a film which consists of polyethylene-type resin, and a packaging bag and a container comprised with this film.

１ 樹脂組成物
２ 石油由来ポリエチレン系樹脂
３ 積層フィルム
４ シーラントフィルム
５ 基材フィルム
６ 包装袋
７，８ 側面シート
９ 底面シート
Ｆ１〜Ｆ４ フィルム Reference Signs List 1 resin composition 2 petroleum-derived polyethylene-based resin 3 laminated film 4 sealant film 5 base film 6 packaging bag 7, 8 side sheet 9 bottom sheet F1 to F4 film

Claims (1)

少なくとも基材フィルムと、ポリエチレン系樹脂からなるヒートシール性の包装材用シーラントフィルムであって、
該ヒートシール性フィルムは、植物由来エチレンと石油由来α−オレフィンとの気相重合物である植物由来の直鎖状低密度ポリエチレン系樹脂による単層構成のフィルムからなることを特徴とする包装材用シーラントフィルム。 A heat sealable packaging material sealant film comprising at least a substrate film and a polyethylene resin,
The heat sealable film is a packaging material characterized in that it is a film having a single-layer structure of a plant-derived linear low density polyethylene-based resin which is a vapor-phase polymer of plant-derived ethylene and petroleum-derived α-olefin. Sealant film.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023074754A1 (en) * 2021-10-26 2023-05-04 大日本印刷株式会社 Sealant film

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002361776A (en) * 2001-06-13 2002-12-18 Dainippon Printing Co Ltd Laminated tube container
JP2006117767A (en) * 2004-10-20 2006-05-11 Mitsubishi Chemicals Corp Thermoplastic elastomer
JP2009155516A (en) * 2007-12-27 2009-07-16 Sumitomo Chemical Co Ltd Packaging bag
JP2010162748A (en) * 2009-01-15 2010-07-29 Toppan Cosmo Inc Decorative sheet
JP2010166061A (en) * 2007-10-10 2010-07-29 Epson Toyocom Corp Method of manufacturing electronic device and method of manufacturing electronic module
JP2010222482A (en) * 2009-03-24 2010-10-07 Yamato Esuron Kk Plant-derived biodegradable synthetic resin sheet and container
JP2011506628A (en) * 2007-12-05 2011-03-03 ブラスケム エス．エイ． Integrated process for the production of ethylene-butylene copolymers, ethylene-butylene copolymers and the use of 1-butylene as ethylene and comonomers supplied from renewable natural sources
JP6439779B2 (en) * 2016-12-22 2018-12-19 大日本印刷株式会社 Sealant film for packaging material, laminated film for packaging material, and packaging bag using plant-derived polyethylene

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002361776A (en) * 2001-06-13 2002-12-18 Dainippon Printing Co Ltd Laminated tube container
JP2006117767A (en) * 2004-10-20 2006-05-11 Mitsubishi Chemicals Corp Thermoplastic elastomer
JP2010166061A (en) * 2007-10-10 2010-07-29 Epson Toyocom Corp Method of manufacturing electronic device and method of manufacturing electronic module
JP2011506628A (en) * 2007-12-05 2011-03-03 ブラスケム エス．エイ． Integrated process for the production of ethylene-butylene copolymers, ethylene-butylene copolymers and the use of 1-butylene as ethylene and comonomers supplied from renewable natural sources
JP2009155516A (en) * 2007-12-27 2009-07-16 Sumitomo Chemical Co Ltd Packaging bag
JP2010162748A (en) * 2009-01-15 2010-07-29 Toppan Cosmo Inc Decorative sheet
JP2010222482A (en) * 2009-03-24 2010-10-07 Yamato Esuron Kk Plant-derived biodegradable synthetic resin sheet and container
JP6439779B2 (en) * 2016-12-22 2018-12-19 大日本印刷株式会社 Sealant film for packaging material, laminated film for packaging material, and packaging bag using plant-derived polyethylene

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023074754A1 (en) * 2021-10-26 2023-05-04 大日本印刷株式会社 Sealant film

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