JP2021176684A - Surface protective film - Google Patents
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- JP2021176684A JP2021176684A JP2020082350A JP2020082350A JP2021176684A JP 2021176684 A JP2021176684 A JP 2021176684A JP 2020082350 A JP2020082350 A JP 2020082350A JP 2020082350 A JP2020082350 A JP 2020082350A JP 2021176684 A JP2021176684 A JP 2021176684A
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- density polyethylene
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- 230000001681 protective effect Effects 0.000 title claims abstract description 59
- 239000002028 Biomass Substances 0.000 claims abstract description 103
- 239000010410 layer Substances 0.000 claims abstract description 77
- 229920003023 plastic Polymers 0.000 claims abstract description 57
- 239000004033 plastic Substances 0.000 claims abstract description 57
- -1 polyethylene Polymers 0.000 claims abstract description 41
- 239000004698 Polyethylene Substances 0.000 claims abstract description 33
- 229920000573 polyethylene Polymers 0.000 claims abstract description 33
- 239000012790 adhesive layer Substances 0.000 claims abstract description 24
- 239000003208 petroleum Substances 0.000 abstract description 31
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 5
- 239000001569 carbon dioxide Substances 0.000 abstract description 5
- 230000002411 adverse Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 239000002344 surface layer Substances 0.000 abstract description 2
- 229920001684 low density polyethylene Polymers 0.000 description 24
- 239000004702 low-density polyethylene Substances 0.000 description 24
- 229920001903 high density polyethylene Polymers 0.000 description 20
- 239000004700 high-density polyethylene Substances 0.000 description 20
- 229920000092 linear low density polyethylene Polymers 0.000 description 18
- 239000004707 linear low-density polyethylene Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 239000011342 resin composition Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 240000000111 Saccharum officinarum Species 0.000 description 2
- 235000007201 Saccharum officinarum Nutrition 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 229920000704 biodegradable plastic Polymers 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920006353 Acrylite® Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-NJFSPNSNSA-N Carbon-14 Chemical compound [14C] OKTJSMMVPCPJKN-NJFSPNSNSA-N 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
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- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明はバイオマス由来のポリエチレンを用いた表面保護フィルムに関する。 The present invention relates to a surface protective film using polyethylene derived from biomass.
従来、表面保護フィルムには石油由来のポリエチレン樹脂が多用されてきたが、近年は世界的な地球環境保護強化、並びに原料となる石油の枯渇が懸念されており、石油から精製・重合されるプラスチック原料についてもバイオマス由来のプラスチック原料が注目されつつある。ここでいうバイオマス由来のプラスチックとは、植物であるトウモロコシやサトウキビなどを加工する過程において発生する副生成物を発酵・脱水・重合して製造されるプラスチックである。バイオマス由来のプラスチック製品を焼却する際に排出される二酸化炭素を再び植物であるサトウキビやトウモロコシなどに光合成によって吸収させ結果的に大気中の二酸化炭素増加に影響を与えることのないことは、所謂カーボンニュートラルと呼ばれる。また石油由来のプラスチックからバイオマス由来のプラスチックに転換することにより、石油の枯渇懸念が払拭されることも期待されるため、特許文献１のようにバイオマス由来のプラスチック原料を製造、また特許文献２のようにバイオマス由来のプラスチック原料を加工されることが研究されてきた。 Conventionally, petroleum-derived polyethylene resin has been widely used for surface protection films, but in recent years there are concerns about strengthening global environmental protection and depletion of petroleum, which is a raw material, and plastics that are refined and polymerized from petroleum. As for raw materials, biomass-derived plastic raw materials are attracting attention. The biomass-derived plastic referred to here is a plastic produced by fermenting, dehydrating, and polymerizing by-products generated in the process of processing plants such as corn and sugar cane. It is so-called carbon that carbon dioxide emitted when incinerating biomass-derived plastic products is absorbed again by plants such as sugar cane and corn by photosynthesis and does not affect the increase in carbon dioxide in the atmosphere as a result. Called neutral. Further, by switching from petroleum-derived plastics to biomass-derived plastics, it is expected that concerns about petroleum depletion will be eliminated. Therefore, as in Patent Document 1, biomass-derived plastic raw materials are manufactured, and in Patent Document 2, It has been studied to process biomass-derived plastic raw materials as described above.
本発明の目的は、表面保護フィルムにバイオマス由来のプラスチックを使用することにより、大気中の二酸化炭素増加という悪影響を抑えつつ、石油の枯渇懸念を払拭する表面保護フィルムを提供することにある。 An object of the present invention is to provide a surface protective film that eliminates concerns about oil depletion while suppressing the adverse effect of an increase in carbon dioxide in the atmosphere by using a biomass-derived plastic as the surface protective film.
本発明者は、上記課題を解決するために鋭意研究開発を重ねた結果、少なくとも背面層、中間層及び粘着層を有する表面保護フィルムであって、表面保護フィルム全体においてバイオマスプラスチック度数が８０以上のバイオマス由来ポリエチレンの含有量が３５重量％以上である構成とすることで目的が達成できることを見いだした。 As a result of intensive research and development to solve the above problems, the present inventor is a surface protective film having at least a back layer, an intermediate layer and an adhesive layer, and the biomass plastic frequency of the entire surface protective film is 80 or more. It was found that the purpose can be achieved by setting the content of biomass-derived polyethylene to 35% by weight or more.
本発明によれば、バイオマス由来プラスチックを用いることにより大気中の二酸化炭素量増加を防ぐカーボンニュートラルな表面保護フィルムを提供することができる。また、石油の枯渇に対する懸念に貢献することができる。 According to the present invention, it is possible to provide a carbon-neutral surface protective film that prevents an increase in the amount of carbon dioxide in the atmosphere by using a biomass-derived plastic. It can also contribute to concerns about oil depletion.
本発明の表面保護フィルムは、少なくとも背面層、中間層および粘着層を有し、背面層、中間層、粘着層ならびにその他機能性を持つ層がある場合はそれも含め、表面保護フィルム全体でバイオマスプラスチック度数が８０以上のバイオマス由来ポリエチレンを３５重量％以上含む。尚、バイオマスプラスチック度数とは、プラスチック全体の重量に対するバイオマス由来のプラスチックの占有率であり、バイオマス由来プラスチックにのみ含有される放射性炭素１４の含有量によって計測されるものである。 The surface protective film of the present invention has at least a back layer, an intermediate layer and an adhesive layer, and biomass in the entire surface protective film including the back layer, the intermediate layer, the adhesive layer and other functional layers, if any. Contains 35% by weight or more of biomass-derived polyethylene having a plastic content of 80 or more. The biomass plastic frequency is the occupancy rate of the biomass-derived plastic with respect to the total weight of the plastic, and is measured by the content of radioactive carbon 14 contained only in the biomass-derived plastic.
本発明の表面保護フィルムに用いるバイオマス由来ポリエチレンは、バイオプラスチック度が８０以上かつ、表面保護フィルム全体におけるバイオマス由来ポリエチレンの占有重量が３５重量％以上でないと、所謂カーボンニュートラルの性質を持たなくなってしまう。またバイオマスプラスチック識別表示上、表面保護フィルムにおけるバイオマス由来ポリエチレンの重量が３５重量％以上であることが望ましく、バイオマス由来ポリエチレンの、ロットによるバイオマスプラスチック度数のばらつきを考慮すると４５重量％以上であることが好ましい。またバイオマス由来ポリエチレンの重量が多すぎると、バイオマス由来ポリエチレン起因による不純物が多くなり、表面保護フィルムの表面に析出し、表面保護フィルムを被着体に貼合した際に不純物が転写し、被着体の汚染となってしまうため、好ましくは表面保護フィルムにおけるバイオマス由来ポリエチレンの占有重量は７０重量％未満、より好ましくは６０重量％未満である。 The biomass-derived polyethylene used in the surface protective film of the present invention does not have the so-called carbon-neutral property unless the bioplastic degree is 80 or more and the occupied weight of the biomass-derived polyethylene in the entire surface protective film is 35% by weight or more. .. Further, on the biomass plastic identification label, it is desirable that the weight of the biomass-derived polyethylene in the surface protective film is 35% by weight or more, and it is 45% by weight or more in consideration of the variation in the biomass plastic frequency depending on the lot of the biomass-derived polyethylene. preferable. If the weight of the biomass-derived polyethylene is too large, impurities caused by the biomass-derived polyethylene will increase and precipitate on the surface of the surface protection film, and when the surface protection film is attached to the adherend, the impurities are transferred and adhered. The occupied weight of the biomass-derived polyethylene in the surface protective film is preferably less than 70% by weight, more preferably less than 60% by weight, because it pollutes the body.
本発明の表面保護フィルムは、表面保護フィルム全体でバイオマスプラスチック度数が８０以上のバイオマス由来ポリエチレンを３５重量％以上含まれていれば、背面層、中間層及び粘着層各層毎のバイオマス由来ポリエチレン含有率に制限はないが、中間層の厚みを表面保護フィルム全体に対して６０％以上を占め、かつ中間層の主原料としてバイオマスプラスチック度数が８０以上のバイオマス由来の高密度ポリエチレン、またはバイオマス由来の低密度ポリエチレンを合計５５重量％以上からなる混合樹脂で組成されることが機能上好ましい。 If the surface protective film of the present invention contains 35% by weight or more of biomass-derived polyethylene having a biomass plastic content of 80 or more in the entire surface protective film, the biomass-derived polyethylene content of each of the back layer, the intermediate layer and the adhesive layer is high. Although there is no limitation, the thickness of the intermediate layer occupies 60% or more of the entire surface protective film, and the main raw material of the intermediate layer is high-density polyethylene derived from biomass having a biomass plastic content of 80 or more, or low density derived from biomass. It is functionally preferable that the density polyethylene is composed of a mixed resin having a total content of 55% by weight or more.
本発明の表面保護フィルムに用いられるバイオマス由来ポリエチレンについては、高密度ポリエチレンもしくは低密度ポリエチレン、および直鎖状低密度ポリエチレンのいずれか、あるいはそれらの混合物が好ましく用いられる。高密度ポリエチレンは固さと切れやすさ、低密度ポリエチレンは柔らかさ、直鎖状低密度ポリエチレンは破断のしにくさという特徴を持っており、表面保護フィルムに要求される特性に応じて任意の割合で配合される。また、本発明の表面保護フィルムに用いられるバイオマス由来ポリエチレンは、バイオマスプラスチック度数および重量以外には特に制限は無いが、荷重２．１６kg、温度１９０℃にて測定されるメルトフローレートが１．０以上１０．０以下であることが好ましく、より好ましくは３．０以上８．０以下であることが、表面保護フィルムの製造工程上好ましい。 As the biomass-derived polyethylene used in the surface protective film of the present invention, either high-density polyethylene or low-density polyethylene, linear low-density polyethylene, or a mixture thereof is preferably used. High-density polyethylene is characterized by hardness and ease of cutting, low-density polyethylene is characterized by softness, and linear low-density polyethylene is resistant to breakage. It is mixed with. The biomass-derived polyethylene used in the surface protective film of the present invention is not particularly limited except for the frequency and weight of the biomass plastic, but has a melt flow rate of 1.0 measured at a load of 2.16 kg and a temperature of 190 ° C. It is preferably 10.0 or more, more preferably 3.0 or more and 8.0 or less, in the process of producing the surface protective film.
本発明の表面保護フィルムに用いられるバイオマス由来ポリエチレンが、バイオマスプラスチック度数が８０以上、かつ表面保護フィルム全体におけるバイオマス由来ポリエチレンの重量が３５重量％以上であれば、背面層、中間層、あるいは粘着層に用いられる樹脂については特に制限はなく、バイオマス由来プラスチックに限らず従来一般的に使用される樹脂、例えば石油由来の高密度ポリエチレン、プロピレン−エチレンブロック共重合体、エチレン−酢酸ビニル共重合体など、表面保護フィルムに求められる性能を満たす樹脂が好適に使用される。 If the biomass-derived polyethylene used in the surface protective film of the present invention has a biomass plastic frequency of 80 or more and the weight of the biomass-derived polyethylene in the entire surface protective film is 35% by weight or more, the back layer, the intermediate layer, or the adhesive layer The resin used for is not particularly limited, and is not limited to biomass-derived plastics, but resins commonly used in the past, such as high-density polyethylene derived from petroleum, propylene-ethylene block copolymer, ethylene-vinyl acetate copolymer, etc. , A resin that satisfies the performance required for the surface protective film is preferably used.
粘着層に含まれるバイオマス由来ポリエチレンは高密度ポリエチレン、低密度ポリエチレン、直鎖状低密度ポリエチレンのいずれか、もしくはそれらの混合でも良いが、粘着性を持たせるためには樹脂に柔軟性があることが望ましく、そのために低密度ポリエチレンまたは直鎖状低密度ポリエチレンが好適に使用され、特に好ましくは直鎖状低密度ポリエチレンが好適に用いられる。 The biomass-derived polyethylene contained in the adhesive layer may be any of high-density polyethylene, low-density polyethylene, linear low-density polyethylene, or a mixture thereof, but the resin must be flexible in order to have adhesiveness. Therefore, low-density polyethylene or linear low-density polyethylene is preferably used, and particularly preferably linear low-density polyethylene is preferably used.
また、背面層および中間層に含まれるバイオマス由来ポリエチレンについては高密度ポリエチレン、低密度ポリエチレン、直鎖状低密度ポリエチレンのいずれか、もしくはそれらの混合でも良いが、荷重２．１６kg、温度１９０℃にて測定されるメルトフローレートが１．０以上１０．０以下であることが好ましく、より好ましくは３．０以上８．０以下であることが、表面保護フィルムの製造工程上好ましい。また、それらを表面保護フィルムに要求される特性に応じて任意の割合で配合することが可能である。 The biomass-derived polyethylene contained in the back layer and the intermediate layer may be any of high-density polyethylene, low-density polyethylene, linear low-density polyethylene, or a mixture thereof, but at a load of 2.16 kg and a temperature of 190 ° C. The melt flow rate measured in the above is preferably 1.0 or more and 10.0 or less, and more preferably 3.0 or more and 8.0 or less in the process of manufacturing the surface protective film. Further, they can be blended in an arbitrary ratio according to the properties required for the surface protective film.
本発明の表面保護フィルムの背面層には、必要に応じてポリチオフェンなどの導電剤や、表面に印刷を施すための例えばコロナ放電処理、プラズマ処理、火炎処理表面処理が施されていてもよく、また本発明の表面保護フィルムには、必要に応じて中間層に着色剤や紫外線吸収剤、導電剤、粘着層に粘着付与剤などといった別途機能性の持った樹脂をバイオマス由来ポリエチレンの含有重量に影響が出ない範囲で添加されてもよい。さらに
表面保護フィルムのバイオマスプラスチック度数や機能が阻害されない範囲で、背面層のさらに上層や、背面層と中間層の間、また中間層と粘着層の間に、着色層や紫外線吸収層、導電層などといった別途機能性の持った層を積層されてもよい。
If necessary, the back layer of the surface protective film of the present invention may be subjected to a conductive agent such as polythiophene, or, for example, corona discharge treatment, plasma treatment, or flame treatment surface treatment for printing on the surface. Further, in the surface protective film of the present invention, if necessary, a resin having a separate function such as a colorant, an ultraviolet absorber, a conductive agent in the intermediate layer, and a tackifier in the adhesive layer is added to the content weight of the biomass-derived polyethylene. It may be added within a range that does not affect it. Furthermore, as long as the biomass plastic frequency and function of the surface protective film are not impaired, a colored layer, an ultraviolet absorbing layer, and a conductive layer are further above the back layer, between the back layer and the intermediate layer, and between the intermediate layer and the adhesive layer. Layers having separate functionality such as, etc. may be laminated.
以下、具体的な実施例に基づいて、本発明の表面保護フィルムを詳細に説明するが、本発明はこれら実施例に限定されるものではない。なお、以下に示す方法で測定、評価した。なお、背面層、中間層、粘着層それぞれのバイオマス由来ポリエチレン含有量に、それぞれの樹脂のバイオマスプラスチック度数を乗算した数値を表面保護フィルム全体のバイオマスプラスチック度数とする。 Hereinafter, the surface protective film of the present invention will be described in detail based on specific examples, but the present invention is not limited to these examples. It was measured and evaluated by the method shown below. The biomass-derived polyethylene content of each of the back layer, the intermediate layer, and the adhesive layer is multiplied by the biomass plastic frequency of each resin to obtain the biomass plastic frequency of the entire surface protective film.
（１）引張弾性率
表面保護フィルムを、作成後３日以上、室温２３℃、湿度５０ＲＨ％雰囲気下で保管し、しかる後にＪＩＳ Ｋ７１６１−１：２０１４ プラスチック−引張特性の求め方−に準拠し引張弾性率を測定した。
(1) Tension elastic modulus The surface protective film is stored in an atmosphere of room temperature of 23 ° C. and humidity of 50 RH% for 3 days or more after preparation, and then tensioned in accordance with JIS K7161-1: 2014 Plastic-How to obtain tensile properties. The elastic modulus was measured.
（２）破断強度、破断伸度
表面保護フィルムを、作成後３日以上、室温２３℃、湿度５０ＲＨ％雰囲気下で保管し、しかる後にＪＩＳ Ｋ７１２７：１９９９ プラスチック−引張特性の試験方法−に準拠し破断強度および破断伸度を測定した。
(2) Breaking strength and breaking elongation The surface protective film is stored in an atmosphere of room temperature of 23 ° C. and humidity of 50 RH% for 3 days or more after preparation, and then conforms to JIS K7127: 1999 plastic-test method for tensile properties. The breaking strength and breaking elongation were measured.
（３）ヘイズ
表面保護フィルムを、作成後３日以上、室温２３℃、湿度５０ＲＨ％雰囲気下で保管し、しかる後に（株）村上色彩技術研究所製のヘーズメーターを用いヘイズを測定した。
(3) Haze The surface protective film was stored in an atmosphere of room temperature of 23 ° C. and humidity of 50 RH% for 3 days or more after preparation, and then haze was measured using a haze meter manufactured by Murakami Color Technology Research Institute Co., Ltd.
（４）粘着力
表面保護フィルムを、作成後３日以上、室温２３℃、湿度５０ＲＨ％雰囲気下で保管し、しかる後に厚さ２０ｍｍ・幅５０ｍｍの三菱ケミカル株式会社製「アクリライトＳ」アクリル板に、貼込圧力９，１００Ｎ／ｍ、貼込速度３００ｃｍ／分で貼付した。しかる後に２３℃雰囲気下で２４時間保管後、引張試験機を用い、引張速度３００ｍｍ／分、剥離角度１８０°にて表面保護フィルムを剥離し粘着力を測定した。
(4) Adhesive strength The surface protective film is stored in an atmosphere of room temperature of 23 ° C. and humidity of 50 RH% for 3 days or more after preparation, and then an acrylic plate of "Acrylite S" manufactured by Mitsubishi Chemical Corporation with a thickness of 20 mm and a width of 50 mm. The film was applied at a pasting pressure of 9,100 N / m and a pasting speed of 300 cm / min. After that, after storing for 24 hours in an atmosphere of 23 ° C., the surface protective film was peeled off at a tensile speed of 300 mm / min and a peeling angle of 180 ° using a tensile tester, and the adhesive strength was measured.
（５）汚染
上記（４）の粘着力測定後、暗室にて、アクリル樹脂板表面にスポットライトを当て、被着体表面の汚染状態を肉眼観察し、以下の判定を行った。
○：汚染がない
×：汚染が酷い。
(5) Contamination After measuring the adhesive strength of (4) above, the surface of the acrylic resin plate was spotlighted in a dark room, and the contaminated state of the surface of the adherend was visually observed, and the following judgment was made.
○: No pollution ×: Severe pollution.
＜実施例１＞
バイオマス由来高密度ポリエチレン（Ｂｒａｓｋｅｍ社製、商品名：ＳＨＣ７２６０、バイオマスプラスチック度数９４．０％、密度０．９５９ｇ／ｃｍ3、ＭＦＲ７．２ｇ／１０分）７０重量％と、石油由来低密度ポリエチレン（住友化学製、商品名：ＣＥ３０５９、バイオマスプラスチック度数０％、密度０．９２４ｇ／ｃｍ3、ＭＦＲ５．８ｇ／１０分）３０重量％からなる組成物を中間層とした。中間層の片面に前期中間層に用いたものと同一の石油由来低密度ポリエチレン（ＣＥ３０５９）を、中間層の、背面層が積層される面の反対側に、石油由来直鎖状低密度ポリエチレン（住友化学製造、商品名：ＣＷ３００６、バイオマスプラスチック度数０％、密度０．９２２ｇ／ｃｍ3、ＭＦＲ５．０ｇ／１０分）からなる粘着層を、Ｔダイ型複合製膜機を用い、押出温度２００℃、背面層の厚さが５μｍ、中間層の厚さが３５μｍ、粘着層の厚さが１０μｍ、合計厚みが５０μｍとなるよう共押出し、表面保護フィルムを作成した。
<Example 1>
Biomass-derived high-density polyethylene (manufactured by Braskem, trade name: SHC7260, biomass plastic content 94.0%, density 0.959 g / cm 3 , MFR 7.2 g / 10 minutes) 70% by weight, and petroleum-derived low-density polyethylene (Sumitomo) A composition made of chemicals, trade name: CE3059, biomass plastic content 0%, density 0.924 g / cm 3 , MFR 5.8 g / 10 minutes) 30% by weight was used as an intermediate layer. Petroleum-derived low-density polyethylene (CE3059), which is the same as that used for the early intermediate layer, is placed on one side of the intermediate layer, and petroleum-derived linear low-density polyethylene (CE3059) is placed on the opposite side of the intermediate layer on which the back layer is laminated. Sumitomo Chemical Mfg. Co., Ltd., trade name: CW3006, biomass plastic content 0%, density 0.922 g / cm 3 , MFR 5.0 g / 10 minutes), using a T-die composite film-forming machine, extrusion temperature 200 ° C. A surface protective film was prepared by co-extruding so that the thickness of the back layer was 5 μm, the thickness of the intermediate layer was 35 μm, the thickness of the adhesive layer was 10 μm, and the total thickness was 50 μm.
＜実施例２＞
実施例１において、中間層の樹脂組成物のうち、バイオマス由来高密度ポリエチレンをバイオマス由来低密度ポリエチレン（Ｂｒａｓｋｅｍ社製、商品名：ＳＰＢ６８１、バイオマスプラスチック度数９５．０％、密度０．９２２ｇ／ｃｍ3、ＭＦＲ３．８ｇ／１０分）に変更した以外は実施例１と同様とし、表面保護フィルムを作成した。
<Example 2>
In Example 1, among the resin compositions of the intermediate layer, the biomass-derived high-density polyethylene was used as the biomass-derived low-density polyethylene (manufactured by Braskem, trade name: SPB681, biomass plastic content 95.0%, density 0.922 g / cm 3). , MFR 3.8 g / 10 minutes), and the same as in Example 1 was used to prepare a surface protective film.
＜実施例３＞
バイオマス由来直鎖状低密度ポリエチレン（Ｂｒａｓｋｅｍ社製、商品名：ＳＬＨ１１８、バイオマスプラスチック度数８４．０％、密度０．９１６ｇ／ｃｍ3、ＭＦＲ１．０ｇ／１０分）からなる組成物を粘着層とし、粘着層の片面にバイオマス由来高密度ポリエチレン（Ｂｒａｓｋｅｍ社製、商品名：ＳＨＣ７２６０、バイオマスプラスチック度数９４．０％、密度０．９５９ｇ／ｃｍ3、ＭＦＲ７．２ｇ／１０分）４０重量％と、石油由来高密度ポリエチレン（日本ポリエチレン製、商品名：ＨＦ５６２、バイオマスプラスチック度数０％、密度０．９６５ｇ／ｃｍ3、ＭＦＲ７．５ｇ／１０分）６０重量％からなる組成物を中間層として積層し、中間層のさらに上に、石油由来低密度ポリエチレン（住友化学製、商品名：ＣＥ３０５９、バイオマスプラスチック度数０％、密度０．９２４ｇ／ｃｍ3、ＭＦＲ５．８ｇ／１０分）からなる組成物を背面層として積層した。その際、Ｔダイ型複合製膜機を用い、押出温度２００℃、背面層の厚さが５μｍ、中間層の厚さが３５μｍ、粘着層の厚さが１０μｍ、合計厚みが５０μｍとなるよう共押出し、表面保護フィルムを作成した。
<Example 3>
A composition composed of biomass-derived linear low-density polyethylene (manufactured by Braskem, trade name: SLH118, biomass plastic content 84.0%, density 0.916 g / cm 3 , MFR 1.0 g / 10 minutes) was used as an adhesive layer. 40% by weight of biomass-derived high-density polyethylene (manufactured by Braskem, trade name: SHC7260, biomass plastic content 94.0%, density 0.959 g / cm 3 , MFR 7.2 g / 10 minutes) on one side of the adhesive layer, derived from petroleum A composition consisting of 60% by weight of high-density polyethylene (manufactured by Nippon Polyethylene, trade name: HF562, biomass plastic content 0%, density 0.965 g / cm 3 , MFR 7.5 g / 10 minutes) was laminated as an intermediate layer, and an intermediate layer was formed. A composition composed of petroleum-derived low-density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., trade name: CE3059, biomass plastic content 0%, density 0.924 g / cm 3 , MFR 5.8 g / 10 minutes) is laminated as a back layer. bottom. At that time, using a T-die type composite film forming machine, the extrusion temperature is 200 ° C., the thickness of the back layer is 5 μm, the thickness of the intermediate layer is 35 μm, the thickness of the adhesive layer is 10 μm, and the total thickness is 50 μm. Extruded to prepare a surface protective film.
＜実施例４＞
実施例３において、中間層の樹脂組成物のうち、バイオマス由来高密度ポリエチレンをバイオマス由来低密度ポリエチレン（Ｂｒａｓｋｅｍ社製、商品名：ＳＰＢ６８１、バイオマスプラスチック度数９５．０％、密度０．９２２ｇ／ｃｍ3、ＭＦＲ３．８ｇ／１０分）に、石油由来高密度ポリエチレンを石油由来低密度ポリエチレン（住友化学製、商品名：ＣＥ３０５９、バイオマスプラスチック度数０％、密度０．９２４ｇ／ｃｍ3、ＭＦＲ５．８ｇ／１０分）に変更した以外は実施例３と同様とし、表面保護フィルムを作成した。
<Example 4>
In Example 3, among the resin compositions of the intermediate layer, the biomass-derived high-density polyethylene was used as the biomass-derived low-density polyethylene (manufactured by Braskem, trade name: SPB681, biomass plastic content 95.0%, density 0.922 g / cm 3). , MFR 3.8g / 10 minutes), petroleum-derived high-density polyethylene, petroleum-derived low-density polyethylene (manufactured by Sumitomo Chemical, trade name: CE3059, biomass plastic content 0%, density 0.924g / cm 3 , MFR 5.8g / 10) A surface protective film was prepared in the same manner as in Example 3 except that it was changed to (1).
＜実施例５＞
実施例３において、粘着層の樹脂組成物のうち、バイオマス由来直鎖状低密度ポリエチレンをバイオマス由来低密度ポリエチレン（Ｂｒａｓｋｅｍ社製、商品名：ＳＰＢ６８１、バイオマスプラスチック度数９５．０％、密度０．９２２ｇ／ｃｍ3、ＭＦＲ３．８ｇ／１０分）に変更した以外は実施例３と同様とし、表面保護フィルムを作成した。
<Example 5>
In Example 3, among the resin compositions of the adhesive layer, the biomass-derived linear low-density polyethylene was used as the biomass-derived low-density polyethylene (manufactured by Braskem, trade name: SPB681, biomass plastic content 95.0%, density 0.922 g). A surface protective film was prepared in the same manner as in Example 3 except that it was changed to / cm 3, MFR 3.8 g / 10 minutes).
＜実施例６＞
実施例２において、中間層の樹脂組成物のうち、バイオマス由来低密度ポリエチレンの配合量を５０重量％、石油由来低密度ポリエチレンの配合量を５０重量％に変更した以外は実施例２と同様とし、表面保護フィルムを作成した。
<Example 6>
In Example 2, the same as in Example 2 except that the blending amount of the biomass-derived low-density polyethylene was changed to 50% by weight and the blending amount of the petroleum-derived low-density polyethylene was changed to 50% by weight in the resin composition of the intermediate layer. , Created a surface protection film.
＜実施例７＞
実施例１において、粘着層の樹脂組成物を、石油由来直鎖状低密度ポリエチレンからバイオマス由来直鎖状低密度ポリエチレン（Ｂｒａｓｋｅｍ社製、商品名：ＳＬＨ１１８、バイオマスプラスチック度数８４．０％、密度０．９１６ｇ／ｃｍ3、ＭＦＲ１．０ｇ／１０分）に変更した以外は実施例１と同様とし、表面保護フィルムを作成した。
<Example 7>
In Example 1, the resin composition of the adhesive layer was changed from petroleum-derived linear low-density polyethylene to biomass-derived linear low-density polyethylene (manufactured by Braskem, trade name: SLH118, biomass plastic frequency 84.0%, density 0. A surface protective film was prepared in the same manner as in Example 1 except that it was changed to .916 g / cm 3, MFR 1.0 g / 10 minutes).
＜比較例１＞
実施例１において、中間層の樹脂組成物のうち、バイオマス由来高密度ポリエチレンを
石油由来高密度ポリエチレン（日本ポリエチレン製、商品名：ＨＦ５６２、バイオマスプラスチック度数０％、密度０．９６５ｇ／ｃｍ3、ＭＦＲ７．５ｇ／１０分）に変更した以外は実施例１と同様とし、表面保護フィルムを作成した。
<Comparative example 1>
In Example 1, among the resin compositions of the intermediate layer, the biomass-derived high-density polyethylene was used as petroleum-derived high-density polyethylene (manufactured by Japan Polyethylene, trade name: HF562, biomass plastic content 0%, density 0.965 g / cm 3 , MFR7). A surface protective film was prepared in the same manner as in Example 1 except that it was changed to .5 g / 10 minutes).
＜比較例２＞
実施例２において、中間層の樹脂組成物のうち、バイオマス由来低密度ポリエチレンを
石油由来低密度ポリエチレン（住友化学製、商品名：ＣＥ３０５９、バイオマスプラスチック度数０％、密度０．９２４ｇ／ｃｍ3、ＭＦＲ５．８ｇ／１０分）に変更した以外は実施例２と同様とし、表面保護フィルムを作成した。
<Comparative example 2>
In Example 2, among the resin compositions of the intermediate layer, the biomass-derived low-density polyethylene was used as the petroleum-derived low-density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., trade name: CE3059, biomass plastic content 0%, density 0.924 g / cm 3 , MFR 5). A surface protective film was prepared in the same manner as in Example 2 except that it was changed to (0.8 g / 10 minutes).
＜比較例３＞
石油由来高密度ポリエチレン（日本ポリエチレン製、商品名：ＨＦ５６２、バイオマスプラスチック度数０％、密度０．９６５ｇ／ｃｍ3、ＭＦＲ７．５ｇ／１０分）からなる組成物を中間層とした。中間層の片面に石油由来低密度ポリエチレン（住友化学製、商品名：ＣＥ３０５９、バイオマスプラスチック度数０％、密度０．９２４ｇ／ｃｍ3、ＭＦＲ５．８ｇ／１０分））を、中間層の、背面層が積層される面の反対側に、石油由来直鎖状低密度ポリエチレン（住友化学製造、商品名：ＣＷ３００６、バイオマスプラスチック度数０％、密度０．９２２ｇ／ｃｍ3、ＭＦＲ５．０ｇ／１０分）からなる粘着層を、Ｔダイ型複合製膜機を用い、押出温度２００℃、背面層の厚さが５μｍ、中間層の厚さが３５μｍ、粘着層の厚さが１０μｍ、合計厚みが５０μｍとなるよう共押出し、表面保護フィルムを作成した。
<Comparative example 3>
A composition composed of petroleum-derived high-density polyethylene (manufactured by Japan Polyethylene, trade name: HF562, biomass plastic content 0%, density 0.965 g / cm 3 , MFR 7.5 g / 10 minutes) was used as an intermediate layer. Low-density polyethylene derived from petroleum (manufactured by Sumitomo Chemical, trade name: CE3059, biomass plastic content 0%, density 0.924 g / cm 3 , MFR 5.8 g / 10 minutes) is applied to one side of the intermediate layer, and the back layer of the intermediate layer. From petroleum-derived linear low-density polyethylene (Sumitomo Chemical Manufacturing, trade name: CW3006, biomass plastic content 0%, density 0.922 g / cm 3 , MFR 5.0 g / 10 minutes) on the opposite side of the surface on which Using a T-die type composite film forming machine, the pressure-sensitive adhesive layer has an extrusion temperature of 200 ° C., a back layer thickness of 5 μm, an intermediate layer thickness of 35 μm, an adhesive layer thickness of 10 μm, and a total thickness of 50 μm. A surface protective film was prepared by coextrusion.
＜比較例４＞
石油由来高密度ポリエチレン（日本ポリエチレン製、商品名：ＨＦ５６２、バイオマスプラスチック度数０％、密度０．９６５ｇ／ｃｍ3、ＭＦＲ７．５ｇ／１０分）６０重量％、石油由来低密度ポリエチレン（住友化学製、商品名：ＣＥ３０５９、バイオマスプラスチック度数０％、密度０．９２４ｇ／ｃｍ3、ＭＦＲ５．８ｇ／１０分）２０重量％、石油由来直鎖状低密度ポリエチレン（住友化学製造、商品名：ＣＷ３００６、バイオマスプラスチック度数０％、密度０．９２２ｇ／ｃｍ3、ＭＦＲ５．０ｇ／１０分）２０重量％およびからなる組成物を中間層とした。中間層の片面に石油由来低低密度ポリエチレン（ＣＥ３０５９）からなる組成物を背面層として積層した。中間層の、背面層が積層される面の反対側に、石油由来直鎖状低密度ポリエチレン（ＣＷ３００６）からなる組成物を粘着層として積層した。その際、Ｔダイ型複合製膜機を用い、押出温度２００℃、背面層の厚さが５μｍ、中間層の厚さが３５μｍ、粘着層の厚さが１０μｍ、合計厚みが５０μｍとなるよう共押出し、表面保護フィルムを作成した。
<Comparative example 4>
Petroleum-derived high-density polyethylene (manufactured by Nippon Polyethylene, trade name: HF562, biomass plastic frequency 0%, density 0.965 g / cm 3 , MFR 7.5 g / 10 minutes) 60% by weight, petroleum-derived low-density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., Product name: CE3059, biomass plastic frequency 0%, density 0.924 g / cm 3 , MFR 5.8 g / 10 minutes) 20% by weight, petroleum-derived linear low-density polyethylene (Sumitomo Chemical Manufacturing, product name: CW3006, biomass plastic) A composition consisting of 0% frequency, 0.922 g / cm 3 density, 5.0 g / 10 min MFR) and 20% by weight was used as an intermediate layer. A composition made of petroleum-derived low-density polyethylene (CE3059) was laminated as a back layer on one side of the intermediate layer. A composition made of petroleum-derived linear low-density polyethylene (CW3006) was laminated as an adhesive layer on the opposite side of the intermediate layer to the surface on which the back surface layer was laminated. At that time, using a T-die type composite film forming machine, the extrusion temperature is 200 ° C., the thickness of the back layer is 5 μm, the thickness of the intermediate layer is 35 μm, the thickness of the adhesive layer is 10 μm, and the total thickness is 50 μm. Extruded to prepare a surface protective film.
＜参考例５＞
バイオマス由来高密度ポリエチレン（Ｂｒａｓｋｅｍ社製、商品名：ＳＨＣ７２６０、バイオマスプラスチック度数９４．０％、密度０．９５９ｇ／ｃｍ3、ＭＦＲ７．２ｇ／１０分）からなる組成物を中間層とした。中間層の片面にバイオマス由来低密度ポリエチレン（Ｂｒａｓｋｅｍ社製、商品名：ＳＰＢ６８１、バイオマスプラスチック度数９５．０％、密度０．９２２ｇ／ｃｍ3、ＭＦＲ３．８ｇ／１０分）からなる組成物を背面層として積層した。中間層の、背面層が積層される面の反対側に、バイオマス由来直鎖状低密度ポリエチレン（Ｂｒａｓｋｅｍ社製、商品名：ＳＬＨ１１８、バイオマスプラスチック度数８４．０％、密度０．９１６ｇ／ｃｍ3、ＭＦＲ１．０ｇ／１０分）からなる組成物を粘着層として積層し、Ｔダイ型複合製膜機を用い、押出温度２００℃、背面層の厚さが５μｍ、中間層の厚さが３５μｍ、粘着層の厚さが１０μｍ、合計厚みが５０μｍとなるよう共押出し、表面保護フィルムを作成した。
<Reference example 5>
A composition composed of biomass-derived high-density polyethylene (manufactured by Braskem, trade name: SHC7260, biomass plastic content 94.0%, density 0.959 g / cm 3 , MFR 7.2 g / 10 minutes) was used as an intermediate layer. A composition composed of biomass-derived low-density polyethylene (manufactured by Braskem, trade name: SPB681, biomass plastic content 95.0%, density 0.922 g / cm 3 , MFR 3.8 g / 10 minutes) is placed on one side of the intermediate layer as a back layer. Laminated as. Biomass-derived linear low-density polyethylene (manufactured by Braskem, trade name: SLH118, biomass plastic frequency 84.0%, density 0.916 g / cm 3 , on the opposite side of the intermediate layer to the surface on which the back layer is laminated, A composition consisting of MFR 1.0 g / 10 min) was laminated as an adhesive layer, and an extrusion temperature of 200 ° C., a back layer thickness of 5 μm, an intermediate layer thickness of 35 μm, and adhesion were used using a T-die composite film forming machine. A surface protective film was prepared by co-extruding so that the layer thickness was 10 μm and the total thickness was 50 μm.
＜参考例６＞
バイオマス由来高密度ポリエチレン（Ｂｒａｓｋｅｍ社製、商品名：ＳＨＣ７２６０、バイオマスプラスチック度数９４．０％、密度０．９５９ｇ／ｃｍ3、ＭＦＲ７．２ｇ／１０分）６０重量％、バイオマス由来低密度ポリエチレン（Ｂｒａｓｋｅｍ社製、ＳＰＢ６８１、バイオマスプラスチック度数９５．０％、密度０．９２２ｇ／ｃｍ3、ＭＦＲ３．８ｇ／１０分）２０重量％、バイオマス由来低直鎖状密度ポリエチレン（Ｂｒａｓｋｅｍ社製、商品名：ＳＬＨ１１８、バイオマスプラスチック度数８４．０％、密度０．９１６ｇ／ｃｍ3、ＭＦＲ１．０ｇ／１０分）２０重量％およびからなる組成物を中間層とした。中間層の片面にバイオマス由来低密度ポリエチレン（ＳＰＢ６８１）からなる組成物を背面層として積層した。中間層の、背面層が積層される面の反対側に、バイオマス由来直鎖状低密度ポリエチレン（ＳＬＨ１１８）からなる組成物を粘着層として積層した。その際、Ｔダイ型複合製膜機を用い、押出温度２００℃、背面層の厚さが５μｍ、中間層の厚さが３５μｍ、粘着層の厚さが１０μｍ、合計厚みが５０μｍとなるよう共押出し、表面保護フィルムを作成した。
<Reference example 6>
Biomass-derived high-density polyethylene (manufactured by Braskem, trade name: SHC7260, biomass plastic frequency 94.0%, density 0.959 g / cm 3 , MFR 7.2 g / 10 minutes) 60% by weight, biomass-derived low-density polyethylene (Brashke) , SPB681, Bioplastic plastic content 95.0%, Density 0.922g / cm 3 , MFR 3.8g / 10 minutes) 20% by weight, Biomass-derived low linear density polyethylene (manufactured by Braskem, trade name: SLH118, biomass A composition consisting of a plastic content of 84.0%, a density of 0.916 g / cm 3 , MFR 1.0 g / 10 minutes) and 20% by weight was used as an intermediate layer. A composition made of biomass-derived low-density polyethylene (SPB681) was laminated as a back layer on one side of the intermediate layer. A composition made of biomass-derived linear low-density polyethylene (SLH118) was laminated as an adhesive layer on the opposite side of the intermediate layer to the surface on which the back layer was laminated. At that time, using a T-die type composite film forming machine, the extrusion temperature is 200 ° C., the thickness of the back layer is 5 μm, the thickness of the intermediate layer is 35 μm, the thickness of the adhesive layer is 10 μm, and the total thickness is 50 μm. Extruded to prepare a surface protective film.
実施例１〜７、ならびに比較例１〜４、参考例５、６の評価結果を表１に示す。なお、表中のＢ−ＨＤとはバイオマス由来高密度ポリエチレンを、Ｂ―ＬＬとはバイオマス由来直鎖状低密度ポリエチレンを、Ｂ−ＬＤとはバイオマス由来低密度ポリエチレンを、Ｏ−ＨＤとは石油由来高密度ポリエチレンを、Ｏ―ＬＬとは石油由来直鎖状低密度ポリエチレンを、Ｏ−ＬＤとは石油由来低密度ポリエチレンを指す。 Table 1 shows the evaluation results of Examples 1 to 7, Comparative Examples 1 to 4, and Reference Examples 5 and 6. In the table, B-HD is biomass-derived high-density polyethylene, B-LL is biomass-derived linear low-density polyethylene, B-LD is biomass-derived low-density polyethylene, and O-HD is petroleum. Derived high-density polyethylene, O-LL refers to petroleum-derived linear low-density polyethylene, and O-LD refers to petroleum-derived low-density polyethylene.
上記の実施例と比較例の対比によると、引張弾性率・破断強度・破断伸度・ヘイズ・粘着力のいずれも石油由来ポリエチレンのみを使用した表面保護フィルムと、バイオマス由来ポリエチレンのみを使用した、あるいは併用した表面保護フィルムとに大きな差異は発現しない。またバイオマス由来ポリエチレンの全体における占有重量が７０重量％以上の場合においては、被着体に対する汚染が見られる。このように本発明の実施によって、石油由来ポリエチレンのみを用いた表面保護フィルムと遜色のない、かつカーボンニュートラルの性質を併せ持った表面保護フィルムを提供することができる。 According to the comparison between the above Examples and Comparative Examples, a surface protective film using only petroleum-derived polyethylene and only biomass-derived polyethylene were used for all of tensile elastic modulus, breaking strength, breaking elongation, haze, and adhesive strength. Alternatively, there is no significant difference from the surface protective film used in combination. Further, when the total weight of the biomass-derived polyethylene is 70% by weight or more, contamination of the adherend is observed. As described above, by implementing the present invention, it is possible to provide a surface protective film that is comparable to the surface protective film using only petroleum-derived polyethylene and has carbon-neutral properties.
Claims (2)
表面保護フィルム全体においてバイオマスプラスチック度数が８０以上のバイオマス由来ポリエチレン含有量が３５重量％以上である表面保護フィルム。 A surface protective film having at least a back layer, an intermediate layer and an adhesive layer.
A surface protective film having a biomass plastic content of 80 or more and a biomass-derived polyethylene content of 35% by weight or more in the entire surface protective film.
表面保護フィルム全体においてバイオマスプラスチック度数が８０以上のバイオマス由来ポリエチレン含有量が７０重量％未満である請求項１記載の表面保護フィルム。 A surface protective film having at least a back layer, an intermediate layer and an adhesive layer.
The surface protective film according to claim 1, wherein the content of biomass-derived polyethylene having a biomass plastic content of 80 or more is less than 70% by weight in the entire surface protective film.
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