JP4529100B2 - Surface protection film - Google Patents
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- JP4529100B2 JP4529100B2 JP2009157738A JP2009157738A JP4529100B2 JP 4529100 B2 JP4529100 B2 JP 4529100B2 JP 2009157738 A JP2009157738 A JP 2009157738A JP 2009157738 A JP2009157738 A JP 2009157738A JP 4529100 B2 JP4529100 B2 JP 4529100B2
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- 230000001681 protective effect Effects 0.000 claims description 88
- 239000011347 resin Substances 0.000 claims description 50
- 229920005989 resin Polymers 0.000 claims description 50
- 239000012790 adhesive layer Substances 0.000 claims description 41
- 239000010410 layer Substances 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 31
- 239000012968 metallocene catalyst Substances 0.000 claims description 27
- -1 polyethylene Polymers 0.000 claims description 23
- 239000002344 surface layer Substances 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 20
- 229920001155 polypropylene Polymers 0.000 claims description 20
- 229920001400 block copolymer Polymers 0.000 claims description 18
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 15
- 150000001336 alkenes Chemical class 0.000 claims description 13
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 13
- 239000005977 Ethylene Substances 0.000 claims description 12
- 229920000098 polyolefin Polymers 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 239000004743 Polypropylene Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 229920001903 high density polyethylene Polymers 0.000 claims description 8
- 239000004700 high-density polyethylene Substances 0.000 claims description 8
- 229920001684 low density polyethylene Polymers 0.000 claims description 8
- 239000004702 low-density polyethylene Substances 0.000 claims description 8
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 description 98
- 239000000853 adhesive Substances 0.000 description 97
- 230000000052 comparative effect Effects 0.000 description 31
- 229920000092 linear low density polyethylene Polymers 0.000 description 29
- 239000004707 linear low-density polyethylene Substances 0.000 description 29
- 238000000034 method Methods 0.000 description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 16
- 230000000903 blocking effect Effects 0.000 description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- 238000011109 contamination Methods 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- 238000001125 extrusion Methods 0.000 description 8
- 229920001384 propylene homopolymer Polymers 0.000 description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000012805 post-processing Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 230000003746 surface roughness Effects 0.000 description 5
- 230000002087 whitening effect Effects 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920001179 medium density polyethylene Polymers 0.000 description 3
- 239000004701 medium-density polyethylene Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- RCJMVGJKROQDCB-UHFFFAOYSA-N 2-methylpenta-1,3-diene Chemical compound CC=CC(C)=C RCJMVGJKROQDCB-UHFFFAOYSA-N 0.000 description 2
- 229920006353 Acrylite® Polymers 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 238000009998 heat setting Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920005606 polypropylene copolymer Polymers 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 238000003856 thermoforming Methods 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- PCCCQOGUVCNYOI-FNORWQNLSA-N (3e)-2,3-dimethylpenta-1,3-diene Chemical compound C\C=C(/C)C(C)=C PCCCQOGUVCNYOI-FNORWQNLSA-N 0.000 description 1
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- UGWOAPBVIGCNOV-UHFFFAOYSA-N 5-ethenyldec-5-ene Chemical compound CCCCC=C(C=C)CCCC UGWOAPBVIGCNOV-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
Description
本発明は、建築資材、電気・電子分野等で用いられる各種樹脂版、ガラス版、金属板等の表面を保護する目的でその表面に貼着して、保管、運搬、後加工の際に被着体を傷付き、汚染等から守る表面保護フィルムに関する。特に、被着体への保護フィルムの貼着時や被着体から保護フィルムを一度剥がし、再度保護フィルムを貼着する際に、粘着面同士の互着が生じても、互着部の剥離後の粘着面に白化、面荒れ等の汚染が極めて少なく、ハンドリング性が良好な表面保護フィルムに関する。 The present invention is applied to the surface of various resin plates, glass plates, metal plates, etc. used in building materials, electrical / electronic fields, etc. for the purpose of protection, storage, transportation and post-processing. The present invention relates to a surface protective film that protects a kimono from scratches and contamination. In particular, when the protective film is adhered to the adherend or when the protective film is peeled off once from the adherend and then the protective film is adhered again, even if adhesion between the adhesive surfaces occurs, peeling of the adhesive portion The present invention relates to a surface protective film having excellent handling properties with less contamination such as whitening and roughening on the subsequent adhesive surface.
表面保護フィルムに対する基本的な要求性能としては、前記した各種被着体に対し、シワや空気を巻き込むことなく一様に貼り付けられる貼着作業性に優れること、被着体の保管、搬送等の間に浮きや剥がれが生じない適度な粘着力を有すること、被着体の保管中の環境変化や後加工による粘着力の経時変化が少なく、容易に剥離可能で剥離後に被着体の表面を汚染することがない等が挙げられる。 The basic required performance for the surface protective film includes excellent adherence workability that can be uniformly applied to the above-mentioned various adherends without involving wrinkles or air, storage of the adherend, transportation, etc. Adhesive strength that does not float or peel between the surfaces of the adherend, environmental changes during storage of the adherend, and changes in the adhesive strength over time due to post-processing are less likely to be easily peeled off and the surface of the adherend after peeling And so on.
従来の表面保護フィルムとしては、ポリ塩化ビニル樹脂、ポリエチレン系樹脂、ポリプロピレン系樹脂等からなるフィルムを基材として、その片面にウレタン系、アクリル系、ゴム系等の粘着剤を塗工したものが知られている。しかしながら、これらの表面保護フィルムは、基材であるフィルムと粘着剤との密着性に劣る場合があったり、粘着剤自体の凝集力の低さが原因で被着体から剥離した際に粘着剤の一部が被着体の表面に残留したりする問題があった。また、フィルムに粘着剤を塗工して製造する表面保護フィルムは、基材であるフィルムの製造工程と粘着剤の塗工工程との最低２工程を必要とするため製造コストが高くなる問題、粘着剤の塗工工程で大量の溶剤を除去する必要があり環境負荷が高くなる問題等があった。 As a conventional surface protection film, a film made of polyvinyl chloride resin, polyethylene resin, polypropylene resin, etc. is used as a base material, and one surface thereof is coated with an adhesive such as urethane, acrylic or rubber. Are known. However, these surface protective films sometimes have poor adhesion between the base film and the pressure sensitive adhesive, or when peeled from the adherend due to the low cohesive strength of the pressure sensitive adhesive itself. There is a problem that a part of the film remains on the surface of the adherend. In addition, the surface protection film produced by applying a pressure-sensitive adhesive to the film requires a minimum of two steps, ie, a film production process and a pressure-sensitive adhesive coating process, which increases the production cost. There is a problem that a large amount of solvent needs to be removed in the pressure-sensitive adhesive coating process, which increases the environmental load.
上記の問題点を改善する方法として共押出積層法により、基材のフィルム層と粘着剤層とを同時に押出、積層した自己粘着型の表面保護フィルムが提案されている。このような表面保護フィルムとしては、例えば、非晶性オレフィン共重合体（ａ）；２０〜８０質量部、結晶性オレフィン系重合体（ｂ）；３〜３０質量部および結晶性オレフィンブロックを有するブロック共重合体（ｃ）；１０〜５０質量部〔（ａ）（ｂ）および（ｃ）の合計で１００質量部とする〕からなる粘着層を有することを特徴とする粘着フィルムが提供されている（例えば、特許文献１参照。）。 As a method for improving the above problems, a self-adhesive surface protective film in which a base film layer and an adhesive layer are simultaneously extruded and laminated by a coextrusion lamination method has been proposed. Examples of such a surface protective film include an amorphous olefin copolymer (a); 20 to 80 parts by mass, a crystalline olefin polymer (b); 3 to 30 parts by mass, and a crystalline olefin block. An adhesive film comprising an adhesive layer comprising a block copolymer (c); 10 to 50 parts by mass (a total of (a), (b) and (c) is 100 parts by mass) is provided. (For example, refer to Patent Document 1).
しかしながら、前記特許文献１で提供された表面保護フィルムをアクリル板等に粘着した場合には、その初期粘着力が高いことに起因して被着体からの剥離が困難になることがあり、また被着体に糊残しが生じたりする等の問題があった。 However, when the surface protective film provided in Patent Document 1 is adhered to an acrylic plate or the like, peeling from the adherend may be difficult due to its high initial adhesive strength. There have been problems such as adhesive residue remaining on the adherend.
更に、実際に使用される現場において、表面保護フィルムを各種被着体に貼着した状態で保管、運搬された後に、被着体から当該保護フィルムを一度剥がし、被着体の表面状態等を検査してから、再度該表面保護フィルムを貼着して後加工等に供される場合がある。この様な使用現場において前記特許文献１で提供された粘着フィルムを用いたとき、粘着面同士が互着すると粘着面同士の接着性が強固であるため、該互着部を剥離しようとすると粘着面に白化、面荒れが生じることがあり、容易に互着部を剥離し、再度被着体に表面保護フィルムを貼着し得るハンドリング性が劣る等の新たな問題が生じている。 Furthermore, in actual use, after the surface protective film is stored and transported in a state of being adhered to various adherends, the protective film is peeled off from the adherend once, and the surface state of the adherend is determined. After the inspection, the surface protective film may be pasted again and used for post-processing. When the pressure-sensitive adhesive film provided in Patent Document 1 is used in such a use site, the adhesiveness between the pressure-sensitive adhesive surfaces is strong when the pressure-sensitive adhesive surfaces adhere to each other. Surfaces may be whitened or roughened, and new problems have arisen such as inferior handling that can easily peel the adherend and re-attach the surface protective film to the adherend.
本発明が解決しようとする課題は、保護フィルム剥離後の被着体表面に、目視確認できる糊残し等の汚染が無く、かつ、ロール状に巻き取った後、再び繰り出して使用する際、基材層と粘着層とが密着して固まりが生ずる、いわゆるブロッキングがなく、表面保護フィルムとして実用的な粘着力を有しながら、粘着面同士の互着が生じても粘着面同士の粘着力が小さく、互着部の剥離後の粘着面に白化、面荒れ等の汚染が極めて少なく、ハンドリング性が良好な表面保護フィルムを提供することである。 The problem to be solved by the present invention is that the surface of the adherend after the protective film is peeled is free from contamination such as glue residue that can be visually confirmed, and after being rolled up and used again, There is no so-called blocking, the material layer and the adhesive layer are in close contact, and there is no so-called blocking. An object of the present invention is to provide a surface protective film which is small and has a very easy handling property with little adhesion such as whitening and surface roughness on the adhesive surface after peeling of the adhesive portions.
本発明者らは、上記の課題を解決すべく鋭意研究を重ねた結果、表面保護フィルムの粘着層に結晶性オレフィンブロックを有するブロック共重合体とプロピレン系重合体と直鎖状低密度ポリエチレンとの３つの成分を、特定の配合比率で混合した樹脂を主成分として用いると、被着体への低汚染性、耐ブロッキング性、表面保護フィルムとして実用的な粘着力、粘着面同士の互着が生じても容易に剥離し粘着面の白化・面荒れが生じない、ハンドリング性が良好な表面保護フィルムを提供し得ることを見いだし、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that a block copolymer having a crystalline olefin block in the adhesive layer of the surface protective film, a propylene-based polymer, a linear low-density polyethylene, Using as a main component a resin in which these three components are mixed at a specific blending ratio, low contamination to the adherend, blocking resistance, practical adhesive strength as a surface protective film, and adhesion between adhesive surfaces It has been found that a surface protective film having excellent handling properties can be provided which is easily peeled off and does not cause whitening and surface roughness of the adhesive surface, and has completed the present invention.
すなわち、本発明は、基材層（Ａ）と粘着層（Ｂ）とを有する表面保護フィルムであって、該粘着層（Ｂ）が結晶性オレフィンブロックを有するブロック共重合体（Ｂ１）１０〜５０質量％と、プロピレン系重合体（Ｂ２）１０〜５０質量％と、密度が０．８８０〜０．９３８ｇ／ｃｍ３ である直鎖状低密度ポリエチレン（Ｂ３）１０〜７０質量％と、を混合した樹脂混合物を主成分とすることを特徴とする表面保護フィルムを提供するものである。 That is, this invention is a surface protection film which has a base material layer (A) and an adhesion layer (B), Comprising: This block copolymer (B1) 10 to which this adhesion layer (B) has a crystalline olefin block and 50 wt%, a propylene-based polymer (B2) and 10 to 50 mass%, and 10 to 70 wt% linear low density polyethylene (B3) with a density of 0.880~0.938g / cm 3, the A surface protective film comprising a mixed resin mixture as a main component is provided.
本発明の表面保護フィルムは、各種樹脂版、ガラス版、金属板等に貼着された後、高温環境にさらされたりしても、粘着力の経時変化が少なく、かつ、被着体からの浮きや剥がれがなく、被着体に反りを発生させることがない等の耐熱性に優れ、また、剥離後の被着体表面に目視確認できる糊残しが無く、さらに、ロール状に巻き取った後、再び繰り出して使用する際のブロッキングがなく、耐ブロッキング性にも優れる。また、表面保護フィルムとして実用的な粘着力を有しながら、粘着面同士の互着が生じても、粘着面同士の粘着力が小さく、互着部の剥離後の粘着面に白化、面荒れ等の汚染が極めて少ない。したがって、本発明の表面保護フィルムは、各種樹脂版、ガラス版、金属板等の表面を保護するフィルムとして有用である。特に、被着体に貼着後、乾燥、加熱成形、加熱処理等の後加工工程で被着体の表面状態等を確認する工程が含まれる場合や、保護フィルム剥離後に印刷等の二次加工を施される用途等に好適である。 Even if the surface protective film of the present invention is applied to various resin plates, glass plates, metal plates, etc., and then exposed to a high temperature environment, the adhesive force hardly changes over time, and from the adherend. Excellent heat resistance, such as no lifting or peeling, and no warpage of the adherend, and no adhesive residue that can be visually confirmed on the surface of the adherend after peeling. After that, there is no blocking at the time of extending and using again, and it is excellent also in blocking resistance. In addition, the adhesive force between the adhesive surfaces is small even if the adhesive surfaces are adhered to each other while having a practical adhesive strength as a surface protective film, and the adhesive surface after peeling of the adhesive portions is whitened and roughened. There is very little pollution. Therefore, the surface protective film of the present invention is useful as a film for protecting the surface of various resin plates, glass plates, metal plates and the like. In particular, after sticking to the adherend, including post-processing steps such as drying, thermoforming, heat treatment, etc. to check the surface condition of the adherend, or secondary processing such as printing after the protective film is peeled off Suitable for applications where
以下、本発明を詳細に説明する。本発明の表面保護フィルムは、少なくとも基材層と粘着層とを有する共押出積層法により形成した多層フィルムである。尚、本発明において、「主成分とする」とは、各層を形成させるために使用する樹脂、或いは添加剤等を含む樹脂混合物において、本発明で規定する特定の樹脂又は樹脂混合物の、全体質量に対する質量割合が６５質量％以上であることを示すものであり、好ましくは８０質量％以上であることをいうものである。 Hereinafter, the present invention will be described in detail. The surface protective film of the present invention is a multilayer film formed by a coextrusion lamination method having at least a base material layer and an adhesive layer. In the present invention, “main component” means the total mass of the specific resin or resin mixture defined in the present invention in the resin used for forming each layer, or in a resin mixture containing additives. It means that the mass ratio to is 65 mass% or more, preferably 80 mass% or more.
本発明で表面保護フィルムの基材層（Ａ）に用いる樹脂は、特に限定されないが、オレフィン系重合体（Ａ１）を主成分として用いることが好ましく、例えば、プロピレン単独重合体、プロピレン−エチレン共重合体、プロピレンーエチレンーブテン−１共重合体等のプロピレン系重合体、低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン、直鎖状低密度ポリエチレン等のエチレン系重合体等が挙げられる。これらのオレフィン系重合体（Ａ１）は、単独で用いても、２種以上を併用しても良い。これらの中でも、本発明の表面保護フィルムを各種樹脂版、ガラス版、金属板等に貼着された後、乾燥、加熱成型等の後加工に供されて高温環境下にさらされる用途で用いる場合や、ロール状に巻き取られ長期間保管する場合は、結晶性プロピレン系重合体を用いることが好ましく、表面保護フィルムの耐熱性を向上できる点でプロピレン単独重合体を用いることがより好ましい。なお、本願において結晶性とはＤＳＣ（示差走査熱量測定）において９５〜２５０℃の範囲で０．５Ｊ／ｇ以上のピークを有することを言うものである。 The resin used for the substrate layer (A) of the surface protective film in the present invention is not particularly limited, but it is preferable to use the olefin polymer (A1) as a main component, for example, a propylene homopolymer, a propylene-ethylene copolymer. Examples include polymers, propylene polymers such as propylene-ethylene-butene-1 copolymer, and ethylene polymers such as low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene. These olefin polymers (A1) may be used alone or in combination of two or more. Among these, when the surface protective film of the present invention is applied to various resin plates, glass plates, metal plates, etc., and then used for post-processing such as drying and heat molding to be exposed to a high temperature environment. In the case of being rolled up and stored for a long period of time, it is preferable to use a crystalline propylene polymer, and it is more preferable to use a propylene homopolymer in terms of improving the heat resistance of the surface protective film. In addition, in this application, crystallinity means having a peak of 0.5 J / g or more in the range of 95-250 degreeC in DSC (differential scanning calorimetry).
また、上記のプロピレン系重合体は、メルトフローレート（以下、「２３０℃のＭＦＲ」という。；ＪＩＳ Ｋ７２１０：１９９９に準拠して、２３０℃、２１．１８Ｎで測定した値）が０．５〜３０．０ｇ／１０分で、融点が１２０〜１６５℃であるものが好ましく、より好ましくは、２３０℃のＭＦＲが２．０〜１５．０ｇ／１０分で、融点が１２５〜１６２℃のものである。ＭＦＲ及び融点がこの範囲であれば、被着体に貼着された後の乾燥、加熱成形等によって高温環境にさらされてもフィルムの収縮が少ないため、浮きや剥がれがなく、被着体に反りを発生させることもなく、また、積層フィルムの成膜性も向上する。 The propylene polymer has a melt flow rate (hereinafter referred to as “230 ° C. MFR”; a value measured at 230 ° C. and 21.18 N in accordance with JIS K7210: 1999) of 0.5 to Those having a melting point of 120 to 165 ° C. at 30.0 g / 10 minutes are preferred, more preferably those having an MFR of 230 ° C. of 2.0 to 15.0 g / 10 minutes and a melting point of 125 to 162 ° C. is there. If the MFR and the melting point are within this range, the film is less shrunk even if it is exposed to a high temperature environment by drying, heat molding or the like after being attached to the adherend, so that it does not float or peel off. There is no warping, and the film formability of the laminated film is improved.
一方、前記（Ａ１）の中でも、表面保護フィルム剥離後に印刷等の二次加工を施す場合や、被着体に表面保護フィルムが貼着された状態で被着体を切断加工する場合は、低汚染性に優れる点や、表面保護フィルムがきれいに切断し、糸引き、毛羽立ち等の外観不良を生じない切断性を有する点でエチレン系重合体を用いるのが好ましく、更に耐熱性が良好な点で低密度ポリエチレンと高密度ポリエチレンとの混合樹脂を用いることがより好ましい。 On the other hand, among the above (A1), when secondary processing such as printing is performed after the surface protective film is peeled off, or when the adherend is cut with the surface protective film attached to the adherend, the low It is preferable to use an ethylene-based polymer because it has excellent contamination properties, and the surface protective film cuts cleanly, and has cutting properties that do not cause poor appearance such as stringing and fluffing. It is more preferable to use a mixed resin of low density polyethylene and high density polyethylene.
また、上記のエチレン系重合体は、メルトフローレート（以下、「１９０℃のＭＦＲ」という。；ＪＩＳ Ｋ７２１０：１９９９に準拠して、１９０℃、２１．１８Ｎで測定した値）が０．５〜３０．０ｇ／１０分であるものが押出成形が容易となることから好ましく、より好ましくは、１９０℃のＭＦＲが２．０〜１５．０ｇ／１０分のものである。さらにこれらのエチレン系重合体は融点が９０〜１３５℃のものであることが好ましく、より好ましくは、融点が１０５〜１３０℃のものである。融点がこの範囲であれば、被着体に貼着された後の乾燥、加熱成形等によって高温環境に置かれてもフィルムの収縮が少ないため、被着体からの浮きや剥がれ、被着体の反りを抑制することができる。 The ethylene-based polymer has a melt flow rate (hereinafter referred to as “190 ° C. MFR”; a value measured at 190 ° C. and 21.18 N in accordance with JIS K7210: 1999). It is preferable that it is 30.0 g / 10 minutes since extrusion molding becomes easy, and more preferably, 190 ° C. MFR is 2.0 to 15.0 g / 10 minutes. Further, these ethylene polymers preferably have a melting point of 90 to 135 ° C, more preferably a melting point of 105 to 130 ° C. If the melting point is within this range, since the film shrinks less even when placed in a high temperature environment by drying, thermoforming, etc. after being attached to the adherend, the adherend is lifted or peeled off. Can be suppressed.
本発明の表面保護フィルムの粘着層（Ｂ）に用いる結晶性オレフィンブロックを有するブロック共重合体（Ｂ１）は、結晶性ポリオレフィンからなるブロック（Ｉ）と結晶性を有さないその他のブロック（ＩＩ）とを有する共重合体であり、好ましくは、当該その他のブロック（ＩＩ）として共役ジエン系重合体からなるブロックを有するものである。また、該共重合体の構成としては、後述するプロピレン系重合体（Ｂ２）と直鎖状低密度ポリエチレン（Ｂ３）とを組み合わせて粘着層（Ｂ）用樹脂として用いた際に得られる表面保護フィルムの粘着性・糊残り性・ハンドリング性の性能バランスに特に優れる点から、（Ｉ−ＩＩ）ｎ１又は（Ｉ−ＩＩ）ｎ２−（Ｉ）（ｎ１、ｎ２は１以上の整数である。）で表される、ポリマー鎖の少なくとも１つの末端が結晶性オレフィンブロック（Ｉ）からなるものであることが好ましい。 The block copolymer (B1) having a crystalline olefin block used for the pressure-sensitive adhesive layer (B) of the surface protective film of the present invention is composed of a block (I) made of crystalline polyolefin and another block (II) not having crystallinity. The other block (II) preferably has a block composed of a conjugated diene polymer. Moreover, as a structure of this copolymer, the surface protection obtained when the propylene polymer (B2) mentioned later and linear low density polyethylene (B3) are combined and used as resin for adhesion layers (B). (I-II) n1 or (I-II) n2- (I) (n1 and n2 are integers of 1 or more) from the point of being particularly excellent in the performance balance of adhesiveness, adhesive residue and handling properties of the film. It is preferable that at least one terminal of the polymer chain represented by the formula (1) is composed of the crystalline olefin block (I).
この様な結晶性オレフィンブロックを有するブロック共重合体（Ｂ１）としては、例えば、特開平３−１２８９５７号公報や特開平８−２３１７８６号で提供されているものが挙げられる。具体的には、１，２−ビニル結合含有率の低い（例えば２５％以下）ポリブタジエン重合体ブロックと、共役ジエン化合物を主体とする重合体であって１，２−及び３，４−結合含有率が高い（例えば５０％以上）重合体ブロックとからなる共重合体を合成し、これを水素添加することによって該ポリブタジエン部分をポリエチレンと類似の構造とすることで結晶性の重合体ブロックとしたもの等が挙げられる。 Examples of the block copolymer (B1) having such a crystalline olefin block include those provided in JP-A-3-128957 and JP-A-8-231786. Specifically, a polymer mainly composed of a polybutadiene polymer block having a low 1,2-vinyl bond content (for example, 25% or less) and a conjugated diene compound, which contains 1,2- and 3,4-bonds. A copolymer composed of a polymer block having a high rate (for example, 50% or more) is synthesized, and the polybutadiene portion is made to have a structure similar to polyethylene by hydrogenating the copolymer to form a crystalline polymer block. And the like.
前記共役ジエン化合物としては、例えば、１，３−ブタジエン、イソプレン、２，３−ジメチル−１，３−ペンタジエン、２−メチル−１，３−ペンタジエン、１，３−ヘキサジエン、４，５−ジエチル−１，３−オクタジエン、３−ブチル−１，３−オクタジエン、クロロプレン等が挙げられ、工業的入手容易性の観点から、１，３−ブタジエン、イソプレンを用いることが好ましい。この様な結晶性オレフィンブロックを有するブロック共重合体として好ましく用いることができる市販品としては、例えば、結晶性オレフィン−エチレン・ブチレン共重合体−結晶性オレフィンの構成を有するブロック共重合体（以下、ＣＥＢＣと略記する。）ＪＳＲ株式会社製「ダイナロン ６２００Ｐ」等が挙げられる。 Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl. -1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene and the like are mentioned, and 1,3-butadiene and isoprene are preferably used from the viewpoint of industrial availability. As a commercially available product that can be preferably used as a block copolymer having such a crystalline olefin block, for example, a block copolymer having a constitution of crystalline olefin-ethylene / butylene copolymer-crystalline olefin (hereinafter referred to as a block copolymer) , Abbreviated as CEBC.) “Dynalon 6200P” manufactured by JSR Corporation.
本発明の表面保護フィルムの粘着層（Ｂ）に用いるプロピレン系重合体（Ｂ２）は、例えば、プロピレン単独重合体、プロピレン−エチレン共重合体、プロピレン−ブテン−１共重合体、プロピレン−エチレン−ブテン−１共重合体、メタロセン触媒系ポリプロピレン等が挙げられる。これらは単独で用いても、２種以上を併用してもよい。また、これらのプロピレン系重合体（Ｂ２）は、２３０℃のＭＦＲが０．５〜３０．０ｇ／１０分で、融点が１２０〜１６５℃であるものが好ましく、より好ましくは、２３０℃のＭＦＲが２．０〜１５．０ｇ／１０分で、融点が１２５〜１６２℃のものである。２３０℃のＭＦＲ及び融点がこの範囲であれば、被着体に貼着された後の乾燥、加熱成形等によって高温環境にさらされてもフィルムの収縮が少ないため、浮きや剥がれがなく、被着体に反りを発生させることもなく、また、積層フィルムの成膜性も向上する。 Examples of the propylene-based polymer (B2) used for the adhesive layer (B) of the surface protective film of the present invention include a propylene homopolymer, a propylene-ethylene copolymer, a propylene-butene-1 copolymer, and a propylene-ethylene- Examples include butene-1 copolymer and metallocene catalyst-based polypropylene. These may be used alone or in combination of two or more. These propylene polymers (B2) preferably have an MFR of 230 ° C. of 0.5 to 30.0 g / 10 min and a melting point of 120 to 165 ° C., more preferably an MFR of 230 ° C. Is 2.0 to 15.0 g / 10 min and the melting point is 125 to 162 ° C. If the MFR at 230 ° C. and the melting point are within this range, the film shrinks little even when exposed to a high temperature environment by drying, heat molding or the like after being adhered to the adherend, and thus there is no floating or peeling. There is no warping of the adherend, and the film formability of the laminated film is improved.
また、前記粘着層（Ｂ）に用いるプロピレン系重合体（Ｂ２）の中でも、メタロセン触媒系ポリプロピレンが好ましい。メタロセン触媒系ポリプロピレンは、従来のチーグラー・ナッタ系触媒に代え、メタロセン系触媒を用いて重合したポリプロピレンである。このメタロセン系触媒としては、例えば、メタロセン化合物とアルミノキサンとを含むメタロセン均一混合触媒、微粒子状の担体上にメタロセン化合物が担持されたメタロセン担持型触媒等が挙げられる。メタロセン担持型触媒については、特開平５−１５５９３１号公報、特開平８−１０４６９１号公報、特開平８−１５７５１５号公報及び特開平８−２３１６２１号公報等に開示されている。メタロセン触媒系ポリプロピレンは、分子量分布及び組成分布の均一性が高く、低分子量成分の含有量が少ないため、前記プロピレン系重合体（Ｂ２）にメタロセン触媒系ポリプロピレンを用いることで、低分子量成分のブリードによる被着体表面の汚染を防止することができる。また、メタロセン触媒系ポリプロピレンは、プロピレン単独重合体でも、プロピレンと他のα−オレフィンとの共重合体でも良く、プロピレンと他のα−オレフィンとの共重合体の例として、プロピレン−エチレン共重合体が挙げられる。 Among the propylene polymers (B2) used for the adhesive layer (B), metallocene catalyst polypropylene is preferable. The metallocene catalyst polypropylene is a polypropylene polymerized using a metallocene catalyst instead of the conventional Ziegler-Natta catalyst. Examples of the metallocene catalyst include a metallocene homogeneous mixed catalyst containing a metallocene compound and an aluminoxane, a metallocene supported catalyst in which a metallocene compound is supported on a particulate carrier, and the like. The metallocene supported catalyst is disclosed in JP-A-5-155931, JP-A-8-104691, JP-A-8-157515, JP-A-8-231621, and the like. Metallocene catalyst-based polypropylene has high uniformity of molecular weight distribution and composition distribution, and low content of low molecular weight components. Therefore, by using metallocene catalyst polypropylene for the propylene polymer (B2), bleeding of low molecular weight components can be achieved. Contamination of the adherend surface due to can be prevented. The metallocene catalyst-based polypropylene may be a propylene homopolymer or a copolymer of propylene and another α-olefin. As an example of a copolymer of propylene and another α-olefin, a propylene-ethylene copolymer may be used. Coalescence is mentioned.
本発明の表面保護フィルムの粘着層（Ｂ）に用いる直鎖状低密度ポリエチレン（Ｂ３）は、密度が０．８８０〜０．９３８ｇ／ｃｍ３であるものであり、密度が０．８９８〜０．９２５ｇ／ｃｍ３のものがより好ましい。また、その１９０℃のＭＦＲは、０．５〜３０．０ｇ／１０分であるものが好ましく、２．０〜１５．０ｇ／１０分であるものがより好ましい。直鎖状低密度エチレン（Ｂ３）の密度及び１９０℃のＭＦＲがこの範囲であれば、結晶性オレフィンブロックを有する共重合体（Ｂ１）との相溶性が良好で、積層フィルムの成膜性が向上する。 The linear low-density polyethylene (B3) used for the adhesive layer (B) of the surface protective film of the present invention has a density of 0.880 to 0.938 g / cm 3 and a density of 0.898 to 0. More preferably, 925 g / cm 3 . The 190 ° C. MFR is preferably 0.5 to 30.0 g / 10 min, more preferably 2.0 to 15.0 g / 10 min. If the density of the linear low density ethylene (B3) and the MFR at 190 ° C. are in this range, the compatibility with the copolymer (B1) having a crystalline olefin block is good, and the film formability of the laminated film is good. improves.
本発明の粘着層（Ｂ）は、結晶性オレフィンブロックを有するブロック共重合体（Ｂ１）１０〜５０質量％と、プロピレン系重合体（Ｂ２）１０〜５０質量％と、密度が０．８８０〜０．９３８ｇ／ｃｍ３である直鎖状低密度ポリエチレン（Ｂ３）１０〜７０質量％と、を混合したもの〔各成分の割合は、（Ｂ１）と（Ｂ２）と（Ｂ３）の合計質量を１００質量％としたときの質量割合である〕を主成分とする。成分（Ｂ１）の配合比率が１０質量％未満であると保護フィルムの粘着力が十分でなく、５０質量％を超えると保護フィルムの粘着力が強すぎるため取り扱いが困難になったり、糊残しが発生したりする等の問題がある。また、成分（Ｂ２）の配合比率が１０質量％未満であると粘着面同士の互着が生じた場合に粘着面同士の接着力が強く、互着部を剥離した後の粘着面に白化、面荒れが生じるなどの問題があり、５０質量％を超えると保護フィルムの粘着力が十分でない問題がある。また、成分（Ｂ３）の配合比率が１０質量％未満であると粘着面同士の互着が生じた場合に粘着面同士の接着力が強く、互着部を剥離した後の粘着面に白化、面荒れが生じるなどの問題があり、７０質量％を超えると保護フィルムの粘着力が十分でない問題がある。さらに、成分（Ｂ２）又は成分（Ｂ３）が全く配合されていない場合は、粘着面同士の互着が生じた場合に粘着面同士の接着力が強く、互着部を剥離した後の粘着面に白化、面荒れが生じるなどの問題がある。成分（Ｂ１）と成分（Ｂ２）と成分（Ｂ３）との配合比率を、前記の範囲で調整することで、被着体への低汚染性、耐ブロッキング性、表面保護フィルムとして実用的な粘着力を有しながら、粘着面同士の互着が生じても粘着面同士の粘着力を０．０５〜１．６５Ｎ／２５ｍｍ程度に調整することが容易となり、ハンドリング性が良好な粘着性を有する表面保護フィルムを提供できる。 The adhesive layer (B) of the present invention has a block copolymer (B1) having a crystalline olefin block of 10 to 50% by mass, a propylene polymer (B2) of 10 to 50% by mass, and a density of 0.880 to What mixed 10-70 mass% of linear low density polyethylene (B3) which is 0.938 g / cm < 3 > [The ratio of each component is the total mass of (B1), (B2), and (B3). It is a mass ratio with respect to 100% by mass]. When the blending ratio of the component (B1) is less than 10% by mass, the protective film has insufficient adhesive strength, and when it exceeds 50% by mass, the protective film has excessively strong adhesive strength, making it difficult to handle or leaving adhesive residue. There are problems such as occurrence. In addition, when the mixing ratio of the component (B2) is less than 10% by mass, the adhesion between the adhesion surfaces is strong when the adhesion between the adhesion surfaces occurs, and the adhesion surface after peeling the adhesion portion is whitened. There exists a problem that surface roughness arises, and when it exceeds 50 mass%, there exists a problem that the adhesive force of a protective film is not enough. In addition, when the mixing ratio of the component (B3) is less than 10% by mass, the adhesion between the adhesion surfaces is strong when the adhesion between the adhesion surfaces occurs, and the adhesion surface after peeling the adhesion portion is whitened. There exists a problem that surface roughness arises, and when it exceeds 70 mass%, there exists a problem that the adhesive force of a protective film is not enough. Furthermore, when the component (B2) or the component (B3) is not blended at all, the adhesive force between the adhesive surfaces is strong when the adhesive surfaces adhere to each other, and the adhesive surface after peeling the adhesive portions Have problems such as whitening and surface roughness. By adjusting the blending ratio of the component (B1), the component (B2), and the component (B3) within the above ranges, low adhesion to the adherend, blocking resistance, and practical adhesion as a surface protective film Even if the adhesive surfaces adhere to each other while having strength, it becomes easy to adjust the adhesive force between the adhesive surfaces to about 0.05 to 1.65 N / 25 mm, and the adhesiveness has good handling properties. A surface protective film can be provided.
本発明の粘着層（Ｂ）は、前述した成分（Ｂ１）と成分（Ｂ２）と成分（Ｂ３）とを前記配合比率で用いることを必須とするものである。しかしながら、本発明の効果である、被着体への低汚染性、耐ブロッキング性、表面保護フィルムとして実用的な粘着力、ハンドリング性とを兼備させる手法として、前記成分（Ｂ１）と成分（Ｂ２）とを用いることでも達成可能であることが判っている。この場合は、成分（Ｂ１）と成分（Ｂ２）との使用割合を厳密に管理する必要があり、工業的生産における自由度が狭く、実用的ではない点を鑑みた結果、さらに成分（Ｂ３）を併用することで工業的生産が容易となることを見出した。この結果として、粘着層（Ｂ）には更に本発明の効果を損なわない範囲でその他の樹脂や各種添加剤等を併用した混合物とすることもできるようになった。その他の樹脂類としては、本発明の効果を損なわない範囲で、従来、共押出積層法でフィルムを得る場合に使用される樹脂を用いることが可能であり、特にオレフィン系の各種重合体が使用できる。 In the pressure-sensitive adhesive layer (B) of the present invention, it is essential to use the component (B1), the component (B2), and the component (B3) described above at the blending ratio. However, the component (B1) and the component (B2), which are the effects of the present invention, are the low contamination property to the adherend, the blocking resistance, the practical adhesive strength as a surface protective film, and the handling property. ) And have been found to be achievable. In this case, it is necessary to strictly control the use ratio of the component (B1) and the component (B2), and the degree of freedom in industrial production is narrow and impractical. As a result, the component (B3) It was found that industrial production becomes easy by using together. As a result, the pressure-sensitive adhesive layer (B) can be made into a mixture in which other resins, various additives, and the like are used in combination as long as the effects of the present invention are not impaired. As other resins, as long as the effects of the present invention are not impaired, it is possible to use a resin conventionally used for obtaining a film by a coextrusion lamination method, and particularly, various olefin polymers are used. it can.
本発明の表面保護フィルムは、上記のように基材層（Ａ）と粘着層（Ｂ）との少なくとも２層から構成されるが、さらに基材層（Ａ）の上に表面層（Ｃ）を設けても構わない。表面層（Ｃ）に用いる樹脂としては、特に限定はないが、基材層（Ａ）との親和性が良好である点からオレフィン系重合体を用いることが好ましく、例えば、低密度ポリエチレン、直鎖状低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン、プロピレン単独重合体、プロピレン−エチレン共重合体、プロピレン−ブテン−１共重合体、プロピレン−ブテン−１−エチレン共重合体等が挙げられる。これらの中でも、積層フィルムの成膜性が向上することから低密度ポリエチレン、直鎖状低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン及びプロピレン単独重合体がより好ましい。 The surface protective film of the present invention is composed of at least two layers of the base material layer (A) and the adhesive layer (B) as described above, and further the surface layer (C) on the base material layer (A). May be provided. The resin used for the surface layer (C) is not particularly limited, but it is preferable to use an olefin polymer from the viewpoint of good affinity with the base material layer (A). Examples include linear low density polyethylene, medium density polyethylene, high density polyethylene, propylene homopolymer, propylene-ethylene copolymer, propylene-butene-1 copolymer, propylene-butene-1-ethylene copolymer, and the like. Among these, low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, and propylene homopolymer are more preferable because the film formability of the laminated film is improved.
また、表面層（Ｃ）に用いる樹脂を上記に挙げた樹脂と、プロピレン−エチレンブロック共重合体との混合樹脂を主成分とし、表面層の表面を梨地状に改質してもよい。表面層の表面を梨地状とすることで粘着力を強く設計した際に起こりやすい、ロール状で保管した際のブロッキングを軽減できる。ここでプロピレン−エチレンブロック共重合体は、プロピレンとエチレンとをブロック重合した樹脂であって、表面層（Ｃ）に用いた場合に、該樹脂層の表面が梨地状になるものであればよく、特に限定されない。例えば、ポリプロピレン単独重合体の存在下で、エチレンの重合、又はエチレン及びプロピレンの重合を行って得られるプロピレン−エチレンブロック共重合体等が挙げられる。これらの中でも、表面を梨地状にすることが容易であることから、エチレン由来成分含有率が８〜２０質量％であるプロピレン−エチレンブロック共重合体を用いることが好ましく、エチレン由来成分の含有率が１０〜１５質量％のプロピレン−エチレンブロック共重合体であることが好ましい。また、プロピレン−エチレンブロック共重合体との混合樹脂の２３０℃のＭＦＲは４〜１２ｇ／１０分であることが押出加工しやすい点で好ましく、６〜１０ｇ／１０分であることがより好ましい。密度は０．８９０〜０．９１０ｇ／ｃｍ３であることが好ましく、０．８９５〜０．９０５ｇ／ｃｍ３であることがより好ましい。 Further, the resin used for the surface layer (C) may be mainly composed of a mixed resin of the resins listed above and a propylene-ethylene block copolymer, and the surface of the surface layer may be modified into a satin finish. By making the surface of the surface layer into a satin finish, it is possible to reduce blocking when stored in a roll shape, which is likely to occur when the adhesive strength is designed strongly. Here, the propylene-ethylene block copolymer is a resin obtained by block polymerization of propylene and ethylene as long as the surface of the resin layer becomes satin when used in the surface layer (C). There is no particular limitation. Examples thereof include a propylene-ethylene block copolymer obtained by polymerization of ethylene or ethylene and propylene in the presence of a polypropylene homopolymer. Among these, it is preferable to use a propylene-ethylene block copolymer having an ethylene-derived component content of 8 to 20% by mass because the surface is easy to have a satin finish, and the content of ethylene-derived components Is preferably a propylene-ethylene block copolymer of 10 to 15% by mass. Further, the MFR at 230 ° C. of the mixed resin with the propylene-ethylene block copolymer is preferably 4 to 12 g / 10 minutes from the viewpoint of easy extrusion, and more preferably 6 to 10 g / 10 minutes. Preferably the density is 0.890~0.910g / cm 3, more preferably 0.895~0.905g / cm 3.
本発明の表面保護フィルムは、全フィルム厚さが２０〜１２０μｍのものが好ましい。全フィルムの厚さがこの範囲であれば、被着体の保護性、被着体の保管、搬送等の間に浮きや剥がれが生じない粘着特性、及び貼着・剥離等の作業性が良好となる。また、粘着層（Ｂ）の厚さは、３〜３０μｍが好ましく、より好ましくは５〜２５μｍである。粘着層（Ｂ）の厚さがこの範囲であれば、被着体の保管、搬送等の間に浮きや剥がれが生じない粘着特性及び積層フィルムの成膜性が良好となる。さらに、本発明の表面保護フィルムに前記表面層（Ｃ）を設ける場合は、表面層（Ｃ）の厚さは３〜３０μｍが好ましく、より好ましくは５〜２０μｍである。表面層（Ｃ）の厚さがこの範囲であれば、耐熱性及び積層フィルムの成膜性が良好となる。 The surface protective film of the present invention preferably has a total film thickness of 20 to 120 μm. If the thickness of the entire film is within this range, the protection of the adherend, the adhesive property that does not cause floating or peeling during storage or transportation of the adherend, and the workability such as sticking / peeling are good. It becomes. Moreover, 3-30 micrometers is preferable and, as for the thickness of the adhesion layer (B), More preferably, it is 5-25 micrometers. When the thickness of the pressure-sensitive adhesive layer (B) is within this range, the pressure-sensitive adhesive properties that do not float or peel off during storage, transportation, etc. of the adherend and the film formability of the laminated film are improved. Furthermore, when providing the said surface layer (C) in the surface protection film of this invention, 3-30 micrometers is preferable and, as for the thickness of a surface layer (C), More preferably, it is 5-20 micrometers. When the thickness of the surface layer (C) is within this range, the heat resistance and the film formability of the laminated film are good.
本発明の表面保護フィルムの製造方法としては、共押出積層法であれば特に限定されるものではないが、例えば、２台以上の押出機を用いて各樹脂層に用いる樹脂を溶融し、共押出ダイス法、フィードブロック法等の共押出法により溶融状態で積層した後、インフレーション、Ｔ−ダイ・チルロール法等の方法を用いてフィルム状に加工する方法が挙げられる。Ｔ−ダイ・チルロール法の場合、ゴムタッチロールやスチールベルト等とチルロール間で、溶融積層されたフィルムをニップして冷却してもよい。 The method for producing the surface protective film of the present invention is not particularly limited as long as it is a coextrusion lamination method. For example, the resin used for each resin layer is melted by using two or more extruders, Examples include a method of laminating in a molten state by a coextrusion method such as an extrusion die method or a feed block method, and then processing into a film using a method such as inflation or a T-die / chill roll method. In the case of the T-die / chill roll method, the melt-laminated film may be nipped and cooled between a rubber touch roll, a steel belt or the like and the chill roll.
さらに、本発明の表面保護フィルムは、少なくとも１軸方向に延伸されていてもよい。延伸方法としては、縦あるいは横方向の１軸延伸、逐次２軸延伸、同時２軸延伸、あるいはチューブラー法２軸延伸等の種々の方法を採用することができる。また、延伸工程はインラインでもあっても、オフラインであってもよい。１軸延伸の延伸方法としては、近接ロール延伸法でも圧延法でもよい。１軸延伸の延伸倍率としては、縦あるいは横方向に１．１〜８０倍が好ましく、より好ましくは３〜３０倍である。一方、２軸延伸の延伸倍率としては、面積比で１．２〜７０倍が好ましく、より好ましくは縦４〜６倍、横５〜９倍、面積比で２０〜５４倍である。 Furthermore, the surface protective film of the present invention may be stretched in at least one axial direction. As the stretching method, various methods such as longitudinal or lateral uniaxial stretching, sequential biaxial stretching, simultaneous biaxial stretching, or tubular method biaxial stretching can be employed. Further, the stretching process may be inline or offline. As a stretching method for uniaxial stretching, a proximity roll stretching method or a rolling method may be used. The stretching ratio of uniaxial stretching is preferably 1.1 to 80 times, more preferably 3 to 30 times in the longitudinal or lateral direction. On the other hand, the stretching ratio of biaxial stretching is preferably 1.2 to 70 times in terms of area ratio, more preferably 4 to 6 times in length, 5 to 9 times in width, and 20 to 54 times in terms of area ratio.
また、縦あるいは横方向の延伸工程としては、必ずしも１段延伸に限らず、多段延伸であってもよい。特に、逐次２軸延伸における縦１軸ロール延伸、縦１軸圧延延伸等の縦１軸延伸においては、厚み、物性の均一性等の点で多段延伸とすることが好ましい。さらに近接ロール延伸においては、フラット法、クロス法のいずれでも構わないが、幅縮みの低減が図れる多段の近接クロス延伸がより好ましい。延伸温度は、１軸延伸の場合、いずれの延伸方法においても８０〜１６０℃が好ましく、１軸延伸でテンター延伸を使用する場合は、９０〜１６５℃が好ましい。また、より好ましい延伸温度としては、それぞれ１１０〜１５５℃、１２０〜１６０℃である。一方、２軸延伸の場合、いずれの方法においても１軸延伸の場合と同様な延伸温度範囲が好ましい。また、延伸工程前に予熱部、延伸工程後に熱固定部を適宜設けてもよい。この場合、予熱部の温度は６０〜１４０℃、熱固定部の温度は９０〜１６０℃の範囲が好ましい。 In addition, the longitudinal or lateral stretching step is not necessarily limited to one-stage stretching, and may be multi-stage stretching. In particular, in longitudinal uniaxial stretching such as longitudinal uniaxial roll stretching and longitudinal uniaxial rolling stretching in sequential biaxial stretching, it is preferable to perform multistage stretching in view of thickness, uniformity of physical properties, and the like. Further, in the proximity roll stretching, either the flat method or the cross method may be used, but multistage proximity cross stretching that can reduce width shrinkage is more preferable. In the case of uniaxial stretching, the stretching temperature is preferably 80 to 160 ° C in any stretching method, and in the case of using tenter stretching in uniaxial stretching, 90 to 165 ° C is preferable. Moreover, as more preferable extending | stretching temperature, they are 110-155 degreeC and 120-160 degreeC, respectively. On the other hand, in the case of biaxial stretching, the stretching temperature range similar to that in the case of uniaxial stretching is preferable in any method. Moreover, you may provide a pre-heating part before an extending process, and a heat setting part after an extending process suitably. In this case, the temperature of the preheating part is preferably in the range of 60 to 140 ° C, and the temperature of the heat fixing part is preferably in the range of 90 to 160 ° C.
本発明の表面保護フィルムは、少なくとも１軸方向への延伸し、熱固定により構造安定化を図ることで、オレフィン系重合体（Ａ１）を主成分とした基材層（Ａ）の配向結晶化により、さらに耐熱性が向上し、粘着力の経時変化が小さくなるので好ましい。 The surface protective film of the present invention is oriented crystallization of the base material layer (A) mainly composed of the olefin polymer (A1) by stretching in at least one axial direction and stabilizing the structure by heat setting. Is preferable because the heat resistance is further improved and the change with time of the adhesive force is reduced.
また、本発明の効果を損なわない範囲で、滑剤、ブロッキング防止剤、紫外線吸収剤、光安定剤、耐電防止剤、防曇剤等、着色剤等を適宜添加してもよい。これらの添加剤としては、オレフィン系重合体用の各種添加剤を使用することが好ましい。 In addition, a lubricant, an antiblocking agent, an ultraviolet absorber, a light stabilizer, an antistatic agent, an antifogging agent, and the like may be added as appropriate without departing from the effects of the present invention. As these additives, it is preferable to use various additives for olefin polymers.
以下に実施例及び比較例を挙げて、本発明を具体的に説明する。 The present invention will be specifically described below with reference to examples and comparative examples.
（実施例１）
基材層用樹脂として、高密度ポリエチレン（密度：０．９６０ｇ／ｃｍ３、ＭＦＲ（１９０℃、２１．１８Ｎ）：１３ｇ／１０分；以下「ＨＤＰＥ」）と低密度ポリエチレン（密度：０．９０２ｇ／ｃｍ３、ＭＦＲ（１９０℃、２１．１８Ｎ）：４ｇ／１０分；以下「ＬＤＰＥ」）とを質量比で５０／５０になるように混合し、粘着層用樹脂として、結晶性オレフィンブロックを有する結晶性オレフィン−エチレン・ブテン共重合体−結晶性オレフィンブロック共重合体（ＣＥＢＣ；ＪＳＲ株式会社製「ダイナロン６２００Ｐ」）４０質量部とメタロセン触媒系プロピレン−エチレンランダム共重合体（密度：０．９００ｇ／ｃｍ３、ＭＦＲ（２３０℃、２１．１８Ｎ）：７．０ｇ／１０分、エチレン単量体単位の含有率：３．５質量％；以下、「メタロセン触媒系ＣＯＰＰ」）２０質量部及び直鎖状低密度ポリエチレン（密度：０．９２０ｇ／ｃｍ３、ＭＦＲ（１９０℃、２１．１８Ｎ）：３ｇ／１０分；以下「ＬＬＤＰＥ（１）」）４０質量部の混合物を用いて、基材層用押出機（口径５０ｍｍ）及び粘着層用押出機（口径４０ｍｍ）にそれぞれ供給し、共押出法により押出温度２５０℃でＴ−ダイから基材層の厚さが６４μｍ、粘着層の厚さが１６μｍになるように押出し、４０℃の水冷金属冷却ロールで冷却した後、ロールに巻き取り、表面保護フィルムを得た。得られたフィルムは、物理的性質を安定化するため、３５℃の熟成室で４８時間熟成させた。
Example 1
As the resin for the base layer, high density polyethylene (density: 0.960 g / cm 3 , MFR (190 ° C., 21.18 N): 13 g / 10 min; hereinafter referred to as “HDPE”) and low density polyethylene (density: 0.902 g) / Cm 3 , MFR (190 ° C., 21.18 N): 4 g / 10 min; hereinafter referred to as “LDPE”) in a mass ratio of 50/50, and the crystalline olefin block is used as the adhesive layer resin. Crystalline Olefin-Ethylene / Butene Copolymer-Crystalline Olefin Block Copolymer (CEBC; “Dynalon 6200P” manufactured by JSR Corporation) and 40 parts by mass of a metallocene catalyst propylene-ethylene random copolymer (density: 0. 900g / cm 3, MFR (230 ℃, 21.18N): 7.0g / 10 min, the content of the ethylene monomer unit: 3.5% by weight Hereinafter, "metallocene catalyst system COPP") 20 parts by mass of linear low density polyethylene (density: 0.920g / cm 3, MFR ( 190 ℃, 21.18N): 3g / 10 min; hereinafter "LLDPE (1) ") Using 40 parts by mass of the mixture, the mixture was supplied to an extruder for a base layer (caliber 50 mm) and an extruder for an adhesive layer (caliber 40 mm), respectively, and from a T-die at an extrusion temperature of 250 ° C by a coextrusion method. Extrusion was performed so that the thickness of the material layer was 64 μm and the thickness of the adhesive layer was 16 μm, and after cooling with a 40 ° C. water-cooled metal cooling roll, the film was wound on a roll to obtain a surface protective film. The obtained film was aged in a aging room at 35 ° C. for 48 hours in order to stabilize physical properties.
（実施例２）
表面層用樹脂として、ＬＤＰＥとプロピレン−エチレンブロック共重合体とを質量比で９５／５となるように混合し、基材用樹脂として、ＨＤＰＥとＬＤＰＥとを質量比で５０／５０になるように混合して用い、粘着層用樹脂として、ＣＥＢＣとメタロセン触媒系ＣＯＰＰとＬＬＤＰＥ（１）とを質量比で４０／２５／３５の混合物を用いて、表面層用押出機（口径５０ｍｍ）、基材層用押出機（口径５０ｍｍ）及び粘着層用押出機（口径４０ｍｍ）にそれぞれ供給し、共押出法により押出温度２５０℃でＴ−ダイから表面層の厚さが１６μｍ、基材層の厚さが４８μｍ、粘着層の厚さが１６μｍになるように押出した以外は実施例１と同様にして、実施例２の表面保護フィルムを得た。
(Example 2)
As a resin for the surface layer, LDPE and propylene-ethylene block copolymer are mixed so that the mass ratio is 95/5, and as a resin for the substrate, HDPE and LDPE are mixed so that the mass ratio is 50/50. As an adhesive layer resin, a mixture of CEBC, metallocene catalyst system COPP and LLDPE (1) in a mass ratio of 40/25/35 was used. The material layer is supplied to an extruder (50 mm diameter) and an adhesive layer extruder (40 mm diameter), respectively, and the surface layer thickness is 16 μm from the T-die at an extrusion temperature of 250 ° C. by the coextrusion method. The surface protective film of Example 2 was obtained in the same manner as in Example 1 except that extrusion was performed so that the thickness was 48 μm and the thickness of the adhesive layer was 16 μm.
（実施例３）
粘着層用樹脂として、ＣＥＢＣとメタロセン触媒系ＣＯＰＰとＬＬＤＰＥ（１）とを質量比で４０／３０／３０の混合物を用いた以外は実施例２と同様にして実施例３の表面保護フィルムを得た。
(Example 3)
The surface protective film of Example 3 was obtained in the same manner as Example 2 except that a mixture of CEBC, metallocene catalyst system COPP and LLDPE (1) having a mass ratio of 40/30/30 was used as the adhesive layer resin. It was.
（実施例４）
粘着層用樹脂として、ＣＥＢＣとメタロセン触媒系ＣＯＰＰとＬＬＤＰＥ（１）とを質量比で３５／２５／４０の混合物を用いた以外は実施例２と同様にして実施例４の表面保護フィルムを得た。
Example 4
A surface protective film of Example 4 was obtained in the same manner as in Example 2 except that a mixture of CEBC, metallocene catalyst system COPP, and LLDPE (1) having a mass ratio of 35/25/40 was used as the adhesive layer resin. It was.
（実施例５）
粘着層用樹脂として、ＣＥＢＣとメタロセン触媒系ＣＯＰＰと直鎖状低密度ポリエチレン（密度：０．９０２ｇ／ｃｍ３、ＭＦＲ（１９０℃、２１．１８Ｎ）：６ｇ／１０分；以下「ＬＬＤＰＥ（２）」という。）とを質量比で２５／３０／４５の混合物を用いた以外は実施例２と同様にして実施例５の表面保護フィルムを得た。
(Example 5)
As the adhesive layer resin, CEBC, metallocene catalyst COPP and linear low density polyethylene (density: 0.902 g / cm 3 , MFR (190 ° C., 21.18 N): 6 g / 10 min; hereinafter referred to as “LLDPE (2)” The surface protective film of Example 5 was obtained in the same manner as in Example 2 except that a mixture having a mass ratio of 25/30/45 was used.
（実施例６）
粘着層用樹脂として、ＣＥＢＣとメタロセン触媒系ＣＯＰＰとＬＬＤＰＥ（２）とを質量比で２５／２５／５０の混合物を用いた以外は実施例２と同様にして実施例６の表面保護フィルムを得た。
(Example 6)
The surface protective film of Example 6 was obtained in the same manner as in Example 2 except that a mixture of CEBC, metallocene catalyst system COPP, and LLDPE (2) having a mass ratio of 25/25/50 was used as the adhesive layer resin. It was.
（実施例７）
粘着層用樹脂として、ＣＥＢＣとメタロセン触媒系ＣＯＰＰとＬＬＤＰＥ（１）とを質量比で４０／５０／１０の混合物を用いた以外は実施例２と同様にして、実施例７の表面保護フィルムを得た。
(Example 7)
The surface protective film of Example 7 was obtained in the same manner as in Example 2 except that a mixture of CEBC, metallocene catalyst system COPP, and LLDPE (1) having a mass ratio of 40/50/10 was used as the adhesive layer resin. Obtained.
（実施例８）
表面層用樹脂として、プロピレン単独重合体（密度：０．９００ｇ／ｃｍ３ 、ＭＦＲ（２３０℃、２１．１８Ｎ）：８．０ｇ／１０分；以下、「ＨＯＰＰ」という。）とプロピレン−エチレンブロック共重合体とを質量比で９５／５の混合物を用い、基材層にＨＯＰＰを用いた以外は実施例２と同様にして、実施例８の表面保護フィルムを得た。
(Example 8)
As the resin for the surface layer, propylene homopolymer (density: 0.900 g / cm 3 , MFR (230 ° C., 21.18 N): 8.0 g / 10 min; hereinafter referred to as “HOPP”) and propylene-ethylene block. A surface protective film of Example 8 was obtained in the same manner as in Example 2 except that a 95/5 mixture by weight of the copolymer was used and HOPP was used for the base material layer.
（実施例９）
粘着層用樹脂として、ＣＥＢＣとメタロセン触媒系ＣＯＰＰとＬＬＤＰＥ（１）とを質量比で４０／３０／３０の混合物を用いた以外は実施例８と同様にして実施例９の表面保護フィルムを得た。
Example 9
The surface protective film of Example 9 was obtained in the same manner as in Example 8 except that a mixture of CEBC, metallocene catalyst system COPP, and LLDPE (1) having a mass ratio of 40/30/30 was used as the adhesive layer resin. It was.
（実施例１０）
粘着層用樹脂として、ＣＥＢＣとメタロセン触媒系ＣＯＰＰとＬＬＤＰＥ（２）とを質量比で２５／２５／５０の混合物を用いた以外は実施例８と同様にして、実施例１０の表面保護フィルムを得た。
(Example 10)
The surface protective film of Example 10 was obtained in the same manner as Example 8 except that a mixture of CEBC, metallocene catalyst system COPP and LLDPE (2) having a mass ratio of 25/25/50 was used as the adhesive layer resin. Obtained.
（実施例１１）
粘着層用樹脂として、ＣＥＢＣとメタロセン触媒系ＣＯＰＰとＬＬＤＰＥ（１）とを質量比で１５／２０／６５の混合物を用いた以外は実施例２と同様にして実施例１１の表面保護フィルムを得た。
(Example 11)
The surface protective film of Example 11 was obtained in the same manner as in Example 2 except that a mixture of CEBC, metallocene catalyst system COPP, and LLDPE (1) having a mass ratio of 15/20/65 was used as the adhesive layer resin. It was.
（実施例１２）
粘着層用樹脂として、ＣＥＢＣとメタロセン触媒系ＣＯＰＰとＬＬＤＰＥ（１）とを質量比で３０／１０／６０の混合物を用いた以外は実施例２と同様にして実施例１２の表面保護フィルムを得た。
(Example 12)
The surface protective film of Example 12 was obtained in the same manner as in Example 2 except that a mixture of CEBC, metallocene catalyst system COPP, and LLDPE (1) having a mass ratio of 30/10/60 was used as the adhesive layer resin. It was.
（比較例１）
粘着層用樹脂として、ＣＥＢＣとＬＬＤＰＥ（１）とを質量比で３０／７０の混合物を用いた以外は実施例１と同様にして比較例１の表面保護フィルムを得た。
(Comparative Example 1)
A surface protective film of Comparative Example 1 was obtained in the same manner as in Example 1 except that a mixture of CEBC and LLDPE (1) having a mass ratio of 30/70 was used as the adhesive layer resin.
（比較例２）
粘着層用樹脂として、ＣＥＢＣとメタロセン触媒系ＣＯＰＰとＬＬＤＰＥ（１）とを質量比で３０／６０／１０の混合物を用いた以外は実施例２と同様にして比較例２の表面保護フィルムを得た。
(Comparative Example 2)
A surface protective film of Comparative Example 2 was obtained in the same manner as Example 2 except that a mixture of CEBC, metallocene catalyst system COPP and LLDPE (1) having a mass ratio of 30/60/10 was used as the adhesive layer resin. It was.
（比較例３）
粘着層用樹脂として、ＣＥＢＣとＬＬＤＰＥ（２）とを質量比で５／９５の混合物を用いた以外は実施例２と同様にして比較例３の表面保護フィルムを得た。
(Comparative Example 3)
A surface protective film of Comparative Example 3 was obtained in the same manner as Example 2 except that a 5/95 mixture of CEBC and LLDPE (2) was used as the adhesive layer resin.
（比較例４）
粘着層用樹脂として、ＣＥＢＣとメタロセン触媒系ＣＯＰＰと非晶性オレフィン共重合体とを質量比で４０／１０／５０の混合物を用いた以外は実施例２と同様にして比較例４の表面保護フィルムを得た。
(Comparative Example 4)
Surface protection of Comparative Example 4 in the same manner as in Example 2 except that a mixture of CEBC, metallocene catalyst COPP, and amorphous olefin copolymer having a mass ratio of 40/10/50 was used as the adhesive layer resin. A film was obtained.
（比較例５）
粘着層用樹脂として、ＣＥＢＣとＬＬＤＰＥ（１）とを質量比で３０／７０の混合物を用いた以外は実施例８と同様にして比較例５の表面保護フィルムを得た。
(Comparative Example 5)
A surface protective film of Comparative Example 5 was obtained in the same manner as in Example 8 except that a mixture of CEBC and LLDPE (1) having a mass ratio of 30/70 was used as the adhesive layer resin.
（比較例６）
粘着層用樹脂として、ＣＥＢＣとメタロセン触媒系ＣＯＰＰとを質量比で７０／３０の混合物を用いた以外は実施例２と同様にして比較例６の表面保護フィルムを得た。
(Comparative Example 6)
A surface protective film of Comparative Example 6 was obtained in the same manner as in Example 2 except that a mixture of CEBC and metallocene catalyst system COPP having a mass ratio of 70/30 was used as the adhesive layer resin.
（比較例７）
粘着層用樹脂として、ＣＥＢＣとメタロセン触媒系ＣＯＰＰとＬＬＤＰＥ（２）とを質量比で２５／５／７０の混合物を用いた以外は実施例２と同様にして比較例７の表面保護フィルムを得た。
(Comparative Example 7)
A surface protective film of Comparative Example 7 was obtained in the same manner as in Example 2 except that a mixture of CEBC, metallocene catalyst system COPP, and LLDPE (2) having a mass ratio of 25/5/70 was used as the adhesive layer resin. It was.
上記の実施例１〜１２及び比較例１〜７で得られた表面保護フィルムを用いて、以下の測定及び評価を行った。 Using the surface protective films obtained in Examples 1 to 12 and Comparative Examples 1 to 7, the following measurements and evaluations were performed.
（１）粘着面同士の粘着力測定
２３℃、５０％ＲＨの恒温室において、ＪＩＳ Ｚ０２３７：２０００に準拠した方法で、縦１５ｃｍ×巾２５ｍｍからなる２枚の表面保護フィルムの粘着面同士を貼着した。貼着されたフィルムを２３℃恒温室中で３０分間静置した後、引張試験機（株式会社エー・アンド・ディー社製）を用いて、３００ｍｍ／分の速度で１８０°方向に剥離して粘着面同士の接着力を測定した。
(1) Adhesive strength measurement between adhesive surfaces In a thermostatic chamber at 23 ° C. and 50% RH, the adhesive surfaces of two surface protective films each having a length of 15 cm and a width of 25 mm are pasted by a method in accordance with JIS Z0237: 2000. I wore it. After the stuck film was allowed to stand for 30 minutes in a constant temperature room at 23 ° C., it was peeled off in the 180 ° direction at a speed of 300 mm / min using a tensile tester (manufactured by A & D Co., Ltd.). The adhesive force between the adhesive surfaces was measured.
（２）粘着面同士の接着、剥離後の粘着面状態
２３℃、５０％ＲＨの恒温室において、ＪＩＳ Ｚ０２３７：２０００に準拠した方法で、縦１５ｃｍ×巾２５ｍｍからなる２枚の表面保護フィルムの粘着面同士を貼着した。貼着されたフィルムを２３℃恒温室中で３０分間静置した後、高速で手剥がしし、粘着面の状況を目視で確認し、以下の基準で粘着面状態を評価した。
○：粘着面に白化、面荒れがないもの
△：粘着面に白化、もしくは面荒れが生じたが実用使用には耐えられるもの
×：粘着面に白化及び面荒れがみられ、実用には不適であるもの
(2) Adhesion of adhesive surfaces, adhesive surface state after peeling In a temperature-controlled room at 23 ° C. and 50% RH, two surface protective films consisting of 15 cm in length and 25 mm in width by a method according to JIS Z0237: 2000 Adhesive surfaces were stuck together. The stuck film was allowed to stand in a constant temperature room at 23 ° C. for 30 minutes, and then peeled off at high speed. The condition of the adhesive surface was visually confirmed, and the adhesive surface state was evaluated according to the following criteria.
○: The adhesive surface is not whitened or roughened. △: The adhesive surface is whitened or roughened, but it can withstand practical use. ×: The adhesive surface is whitened and roughened. What is
（３）粘着力の測定
２３℃、５０％ＲＨの恒温室において、ＪＩＳ Ｚ０２３７：２０００の粘着力評価方法に準拠して、表面保護フィルムを厚さ２ｍｍのアクリル板（鏡面仕上げ、三菱レイヨン株式会社製「アクリライト」）に貼着した。フィルムが貼着されたアクリル板を２３℃恒温室中で３０分間静置した後、引張試験機（株式会社エー・アンド・ディー社製）を用いて、３００ｍｍ／分の速度で１８０°方向に剥離して初期粘着力を測定した。又、フィルムを貼着したアクリル板を５０℃の乾燥機中に１日静置した後、同様に粘着力を測定した。
(3) Measurement of adhesive strength In a thermostatic chamber at 23 ° C. and 50% RH, the surface protective film was made of an acrylic plate having a thickness of 2 mm (mirror finish, Mitsubishi Rayon Co., Ltd.) according to the adhesive strength evaluation method of JIS Z0237: 2000. “Acrylite”). After leaving the acrylic plate with the film attached in a constant temperature room at 23 ° C. for 30 minutes, using a tensile tester (manufactured by A & D Co., Ltd.) in the direction of 180 ° at a speed of 300 mm / min. It peeled and the initial adhesive force was measured. Moreover, after leaving the acrylic board which stuck the film in a 50 degreeC dryer for one day, adhesive force was measured similarly.
（４）糊残り性の評価
２３℃、５０％ＲＨの恒温室において、ＪＩＳ Ｚ０２３７：２０００に準拠した方法で、表面保護フィルムを縦１５ｃｍ×巾５ｃｍのアクリル板（鏡面仕上げ、三菱レイヨン株式会社製「アクリライト」）の全面に貼着した。フィルムが貼着されたアクリル板を６０℃の乾燥機中で３日間静置後、２３℃恒温室中で１時間冷却した。冷却された試験片から、フィルムを１８０°方向に高速で手剥がしし、アクリル板表面の汚染状況を目視で確認し、以下の基準にて糊残り性の評価を行った。
○：アクリル板表面にくもり、白スジ、異物等の汚れ無し。
△：アクリル板表面にくもり、白スジ、異物等の何れかの汚れがあるが実用使用には耐えられるもの
×：アクリル板表面にくもり、白スジ、異物等のいずれかの汚れが有り、実用には不適であるもの
(4) Evaluation of adhesive residue In a temperature-controlled room at 23 ° C. and 50% RH, the surface protective film was made into a 15 cm long by 5 cm wide acrylic plate (mirror finish, manufactured by Mitsubishi Rayon Co., Ltd.) in accordance with JIS Z0237: 2000. "Acrylite") was attached to the entire surface. The acrylic plate on which the film was adhered was allowed to stand in a dryer at 60 ° C. for 3 days, and then cooled in a constant temperature room at 23 ° C. for 1 hour. From the cooled test piece, the film was peeled off at a high speed in the direction of 180 °, the state of contamination on the acrylic plate surface was visually confirmed, and the adhesive residue was evaluated according to the following criteria.
○: No cloudiness, white streaks, foreign matter, etc. on the acrylic plate surface.
△: Any dirt such as cloudy, white streaks, foreign matter, etc. on the acrylic plate surface, but can withstand practical use ×: Any dirt such as cloudy, white streaks, foreign matter etc. on the acrylic plate surface, practical What is unsuitable for
（５）耐ブロッキング性の評価
得られた表面保護フィルムを、Ａ４のサイズ（縦２９７ｍｍ×横２１０ｍｍ）で切り出した。この際、フィルム成膜時の押し出し方向（ＭＤ方向）とＡ４縦方向が一致するように切り出した。切り出したフィルムを１０枚重ねた後、その上下をＡ４サイズ、厚さ３ｍｍの塩化ビニル製の板で挟み、重さ５ｋｇの錘を載せ、４０℃の乾燥機中で１４日間保管後、２３℃、５０％ＲＨの恒温室内で１時間保管した。次いで、そのフィルムをＭＤ方向に２５ｍｍ幅で切り出し、引張試験機（株式会社エー・アンド・ディー社製）を用いて、３００ｍｍ／分の速度で１８０°方向に剥離してブロッキング力を測定した。得られたブロッキング力から、以下の基準によって耐ブロッキング性を評価した。
○：ブロッキング力が０．８Ｎ／２５ｍｍ未満
×：ブロッキング力が０．８Ｎ／２５ｍｍ以上
(5) Evaluation of blocking resistance The obtained surface protective film was cut out in the size of A4 (length 297 mm x width 210 mm). At this time, the film was cut out so that the extrusion direction (MD direction) during film formation coincided with the A4 vertical direction. After 10 cut out films were stacked, the upper and lower sides were sandwiched between A4 size, 3 mm thick vinyl chloride plates, a weight of 5 kg was placed, stored in a dryer at 40 ° C. for 14 days, then stored at 23 ° C. And stored in a constant temperature room of 50% RH for 1 hour. Next, the film was cut out in a width of 25 mm in the MD direction, and peeled in the direction of 180 ° at a speed of 300 mm / min using a tensile tester (manufactured by A & D Co., Ltd.) to measure the blocking force. From the obtained blocking force, blocking resistance was evaluated according to the following criteria.
○: Blocking force is less than 0.8 N / 25 mm ×: Blocking force is 0.8 N / 25 mm or more
上記で作製した表面保護フィルムの層構成及びこれらの表面保護フィルムを用いて得られた評価結果を表１〜３に示した。なお、実施例１と比較例１については、表面層を設けていないので空欄としている。 Tables 1 to 3 show the layer structure of the surface protective film produced above and the evaluation results obtained using these surface protective films. Note that Example 1 and Comparative Example 1 are left blank because no surface layer is provided.
実施例１〜１１の結果から、本発明の表面保護フィルムは、アクリル板に対する粘着力が適切であり、表面保護フィルムとして実用的な微粘着の粘着力を有することがわかった。また、アクリル板に貼着した後、５０℃で１日間放置しても粘着力の変化量がわずかであり、アクリル板からフィルムを剥離した際に、被着体表面に目視確認できる糊残しが無く、異物等の汚染は認められないことがわかった。さらに、ブロッキングすることなく良好な取り扱いが可能で、粘着面同士を互着させたときの粘着面同士の粘着力が０．０５〜１．６５Ｎ／２５ｍｍ程度の粘着力を有し、互着部を剥離した後の粘着面に白化、面荒れがないか、または実用上問題のないレベルに収まっており、粘着面同士が互着してもハンドリング性が良好な表面保護フィルムであることがわかった。 From the results of Examples 1 to 11, it was found that the surface protective film of the present invention has an appropriate adhesive force to the acrylic plate, and has a practically weak adhesive force as a surface protective film. In addition, after being attached to an acrylic plate, the amount of change in adhesive force is slight even when left at 50 ° C. for 1 day, and when the film is peeled off from the acrylic plate, there is an adhesive residue that can be visually confirmed on the adherend surface. There was no contamination such as foreign matter. Furthermore, good handling is possible without blocking, and the adhesive force between the adhesive surfaces when the adhesive surfaces are attached to each other has an adhesive force of about 0.05 to 1.65 N / 25 mm, It is clear that the adhesive surface after peeling is whitened, rough, or at a level where there is no practical problem, and it is a surface protective film with good handling properties even if the adhesive surfaces adhere to each other It was.
比較例１は、実施例１と基材層は同一であるが、粘着層にＣＥＢＣとＬＬＤＰＥ（１）とを３０／７０の混合物を用い、成分（Ｂ２）を配合していない表面保護フィルムの例である。この比較例１の表面保護フィルムでは、粘着面同士を互着させたときの粘着面同士の粘着力が２．４６Ｎ／２５ｍｍと強く、互着部を剥離した後の粘着面に白化、面荒れがあることがわかった。 Comparative Example 1 is a surface protective film in which the base material layer is the same as in Example 1, but a 30/70 mixture of CEBC and LLDPE (1) is used for the adhesive layer, and the component (B2) is not blended. It is an example. In the surface protective film of Comparative Example 1, the adhesive force between the adhesive surfaces when the adhesive surfaces are adhered to each other is as strong as 2.46 N / 25 mm, and the adhesive surface after peeling the adhesive portion is whitened and roughened. I found out that
比較例２は、実施例２と表面層、基材層は同一であるが、粘着層の成分（Ｂ１）の配合比率が３０質量部と成分（Ｂ３）の配合比率が１０質量部であるのに対し、成分（Ｂ２）の配合比率を上限の５０質量部を超える６０質量部とした表面保護フィルムの例である。この比較例２の表面保護フィルムでは、アクリル板に対する粘着力が、０．０３Ｎ／２５ｍｍ程度しかなく、粘着力が不十分となることがわかった。 In Comparative Example 2, the surface layer and the base material layer are the same as Example 2, but the mixing ratio of the component (B1) of the adhesive layer is 30 parts by mass and the mixing ratio of the component (B3) is 10 parts by mass. On the other hand, it is an example of the surface protection film which made the compounding ratio of the component (B2) 60 mass parts which exceeds 50 mass parts of an upper limit. In the surface protective film of Comparative Example 2, the adhesive strength to the acrylic plate was only about 0.03 N / 25 mm, and it was found that the adhesive strength was insufficient.
比較例３は、実施例２と表面層、基材層は同一であるが、粘着層にＣＥＢＣとＬＬＤＰＥ（２）とを質量比で５／９５の混合物を用い、成分（Ｂ２）を配合していない表面保護フィルムの例である。この比較例３の表面保護フィルムでは、粘着面同士を互着させたときの粘着面同士の粘着力が２．９０Ｎ／２５ｍｍと強く、互着部を剥離した後の粘着面に白化、面荒れがあることがわかった。 In Comparative Example 3, the surface layer and the base material layer are the same as in Example 2, but a mixture of CEBC and LLDPE (2) in a mass ratio of 5/95 is used for the adhesive layer, and the component (B2) is blended. It is an example of the surface protection film which is not. In the surface protective film of Comparative Example 3, the adhesive force between the adhesive surfaces when the adhesive surfaces are adhered to each other is as strong as 2.90 N / 25 mm, and the adhesive surface after peeling the adhered portion is whitened and roughened. I found out that
比較例４は、実施例２と表面層、基材層は同一であるが、粘着層に成分（Ｂ３）に変えて、非晶性オレフィン共重合体を用い、ＣＥＢＣとメタロセン触媒系ＣＯＰＰと非晶性オレフィン共重合体とを４０／１０／５０の混合物を用いた表面保護フィルムである（特許文献１参照。）。この比較例４の表面保護フィルムでは、アクリル板に対する粘着力が、４．００Ｎ／２５ｍｍ程度と強く、粘着面同士を互着させたときの粘着面同士の粘着力が５．４０Ｎ／２５ｍｍと強く、互着部を剥離した後の粘着面に白化、面荒れがあることがわかった。 In Comparative Example 4, the surface layer and the base material layer are the same as in Example 2, but instead of the component (B3) in the adhesive layer, an amorphous olefin copolymer was used, and CEBC, the metallocene catalyst system COPP, It is a surface protection film using a crystalline olefin copolymer and a 40/10/50 mixture (see Patent Document 1). In the surface protective film of Comparative Example 4, the adhesive strength to the acrylic plate is as strong as about 4.00 N / 25 mm, and the adhesive strength between the adhesive surfaces when the adhesive surfaces are attached to each other is as strong as 5.40 N / 25 mm. It was found that the pressure-sensitive adhesive surface after whitening and peeling was peeled off.
比較例５は、実施例８と表面層、基材層は同一であるが、粘着層にＣＥＢＣとＬＬＤＰＥ（１）とを質量比で３０／７０の混合物を用い、成分（Ｂ２）を配合していない表面保護フィルムの例である。この比較例５の表面保護フィルムでは、粘着面同士を互着させたときの粘着面同士の粘着力が２．４０Ｎ／２５ｍｍと強く、互着部を剥離した後の粘着面に白化、面荒れがあることがわかった。 In Comparative Example 5, the surface layer and the base material layer are the same as Example 8, but a mixture of CEBC and LLDPE (1) in a mass ratio of 30/70 is used for the adhesive layer, and the component (B2) is blended. It is an example of the surface protection film which is not. In the surface protective film of Comparative Example 5, the adhesive force between the adhesive surfaces when the adhesive surfaces are attached to each other is as strong as 2.40 N / 25 mm, and the adhesive surface after peeling the attached portion is whitened and roughened. I found out that
比較例６は、実施例２と表面層、基材層は同一であるが、粘着層にＣＥＢＣとメタロセン触媒系ＣＯＰＰとを質量比で７０／３０の混合物を用い、成分（Ｂ３）を配合していない表面保護フィルムの例である。この比較例６の表面保護フィルムでは、粘着面同士を互着させたときの粘着面同士の粘着力が４．８０Ｎ／２５ｍｍと強く、互着部を剥離した後の粘着面に白化、面荒れがあることがわかった。 In Comparative Example 6, the surface layer and the base material layer are the same as in Example 2, but a mixture of CEBC and metallocene catalyst COPP in a mass ratio of 70/30 is used for the adhesive layer, and the component (B3) is blended. It is an example of the surface protection film which is not. In the surface protective film of Comparative Example 6, the adhesive force between the adhesive surfaces when the adhesive surfaces are adhered to each other is as strong as 4.80 N / 25 mm, and the adhesive surface after peeling the adhesive portions is whitened and roughened. I found out that
比較例７は、実施例２と表面層、基材層は同一であるが、粘着層のプロピレン系重合体（Ｂ２）成分の使用割合を５質量％にした表面保護フィルムの例である。この比較例７の表面保護フィルムでは、粘着面同士を互着させたときの粘着面同士の粘着力が２．５０Ｎ／２５ｍｍと強く、互着部を剥離した後の粘着面に白化、面荒れがあることがわかった。 Comparative Example 7 is an example of a surface protective film in which the surface layer and the base material layer are the same as Example 2, but the use ratio of the propylene-based polymer (B2) component in the adhesive layer is 5% by mass. In the surface protective film of Comparative Example 7, the adhesive force between the adhesive surfaces when the adhesive surfaces are adhered to each other is as strong as 2.50 N / 25 mm, and the adhesive surface after peeling the adhesive portions is whitened and roughened. I found out that
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