JP4934422B2 - Surface protection film - Google Patents
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- JP4934422B2 JP4934422B2 JP2006353708A JP2006353708A JP4934422B2 JP 4934422 B2 JP4934422 B2 JP 4934422B2 JP 2006353708 A JP2006353708 A JP 2006353708A JP 2006353708 A JP2006353708 A JP 2006353708A JP 4934422 B2 JP4934422 B2 JP 4934422B2
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- 239000010410 layer Substances 0.000 claims description 83
- -1 polyethylene Polymers 0.000 claims description 58
- 229920000573 polyethylene Polymers 0.000 claims description 58
- 239000004698 Polyethylene Substances 0.000 claims description 56
- 230000001681 protective effect Effects 0.000 claims description 43
- 238000010828 elution Methods 0.000 claims description 37
- 239000012790 adhesive layer Substances 0.000 claims description 32
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 26
- 239000005977 Ethylene Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 25
- 239000004711 α-olefin Substances 0.000 claims description 22
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 16
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 11
- 238000005259 measurement Methods 0.000 claims description 11
- 229920001903 high density polyethylene Polymers 0.000 claims description 9
- 239000004700 high-density polyethylene Substances 0.000 claims description 9
- 229920001684 low density polyethylene Polymers 0.000 claims description 9
- 239000004702 low-density polyethylene Substances 0.000 claims description 9
- 230000003287 optical effect Effects 0.000 claims description 8
- 239000012968 metallocene catalyst Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 description 38
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 23
- 238000004519 manufacturing process Methods 0.000 description 12
- 239000000853 adhesive Substances 0.000 description 11
- 230000001070 adhesive effect Effects 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 11
- 238000005227 gel permeation chromatography Methods 0.000 description 10
- 239000011342 resin composition Substances 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 8
- 229920013716 polyethylene resin Polymers 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 5
- 238000005194 fractionation Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000010526 radical polymerization reaction Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 229920000092 linear low density polyethylene Polymers 0.000 description 3
- 239000004707 linear low-density polyethylene Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000011990 phillips catalyst Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 238000007613 slurry method Methods 0.000 description 3
- 101710113246 Pectinesterase 3 Proteins 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Landscapes
- Polarising Elements (AREA)
- Laminated Bodies (AREA)
Description
本発明は、部材の表面を保護するために部材表面に貼り合わせて使用する表面保護フィルムに関するものであり、特に、粘着剤を添加しなくても良好な部材表面への粘着性を有し、輸送運搬時のフィルム表面の傷つき性が良好で、部材と貼り合せる際の繰出時にシワが入らず滑らかに繰り出すことができる表面保護フィルムに関するものである。さらに、導光板、偏光板、位相差板、プリズムシート等の光学材料の保護に使用される表面保護フィルムに関するものである。 The present invention relates to a surface protective film that is used by being bonded to the surface of a member in order to protect the surface of the member, and in particular, has good adhesiveness to the surface of a member without adding an adhesive, The present invention relates to a surface protective film that has good scratch resistance on the surface of a film during transportation and transportation, and can be smoothly fed out without wrinkling when it is attached to a member. Furthermore, it is related with the surface protection film used for protection of optical materials, such as a light-guide plate, a polarizing plate, a phase difference plate, and a prism sheet.
アクリル板、ポリカーボネート板などのプラスチック材料やガラス基板などは、液晶テレビ、パソコン、携帯電話、デジタルカメラ等の液晶部等の光学機器部材として幅広く用いられている。それらの部材は、加工時や輸送運搬時等の表面の傷つきや汚れ防止の観点から、表面保護フィルムが貼り付けられ、加工後又は輸送運搬後に係る表面保護フィルムを剥がして使用することが一般的である。 Plastic materials such as acrylic plates and polycarbonate plates, glass substrates, and the like are widely used as optical equipment members such as liquid crystal sections of liquid crystal televisions, personal computers, mobile phones, digital cameras, and the like. For these members, from the viewpoint of preventing scratches and dirt on the surface during processing, transportation and transportation, a surface protection film is affixed, and it is general to use after removing the surface protection film after processing or transportation and transportation. It is.
従来、表面保護フィルムには粘着層にエチレン・酢酸ビニル共重合体が使用されている（例えば、特許文献１〜２参照。）。しかしながら、粘着層にエチレン・酢酸ビニル共重合体を用いたフィルムは、経時で粘着強度が上昇してしまい問題があった。 Conventionally, ethylene / vinyl acetate copolymer is used for the adhesive layer in the surface protective film (for example, refer to Patent Documents 1 and 2). However, a film using an ethylene / vinyl acetate copolymer for the adhesive layer has a problem that the adhesive strength increases with time.
この問題を解決する手段として、粘着強度の経時での上昇を抑えるために、粘着層が、クロス別法によって１００重量％溶出したときの温度が６４℃以下であるエチレン単独あるいはエチレンとα−オレフィンとを構造単位とするポリエチレン系樹脂からなることを特徴とする表面保護フィルムが提案されている（例えば、特許文献３参照。）が、係る粘着層を有する表面保護フィルムは、全般的に粘着強度が強く、部材と貼り合せる際のロール巻状態からの繰り出し時に滑らかに繰り出すことができないという問題があった。
また、粘着層と基材層の複合形態からなり、該粘着層が、密度０．８６０〜０．９２０ｇ／ｃｍ３、融点６０〜１１５℃、示差走査熱量測定によって得た融解曲線が単一ピ−クを示すエチレン−α−オレフィン共重合体に、粘着付与剤を４０ｗｔ％以下の範囲で含有せしめた配合物で構成されていることを特徴とする表面保護フィルムが提案されている（例えば、特許文献４参照。）が、被着体表面に粘着剤が移行し汚染性の点から問題があった。
The adhesive layer is composed of a composite form of an adhesive layer and a base material layer. The adhesive layer has a density of 0.860 to 0.920 g / cm 3 , a melting point of 60 to 115 ° C., and a melting curve obtained by differential scanning calorimetry. A surface protective film characterized in that it is composed of a blend in which a tackifier is contained in a range of 40 wt% or less in an ethylene-α-olefin copolymer exhibiting a-ku has been proposed (for example, However, there is a problem from the viewpoint of contamination due to the transfer of the adhesive to the surface of the adherend.
本発明の目的は、前述した従来の技術の問題点に鑑み、耐傷付き性が良好で、適度な粘着性を有し、部材と貼り合せる際のロール巻状態からの繰り出し性に優れる表面保護フィルムを提供することにある。 The object of the present invention is to provide a surface protective film that has good scratch resistance, moderate tackiness, and excellent roll-out from a rolled state when bonded to a member in view of the above-mentioned problems of the prior art. Is to provide.
本発明者は、上記課題を解決するため種々の研究を重ねた結果、外層、中間層、粘着層の順に積層された３層構成のフィルムの外層に特定のポリエチレン又はポリエチレン組成物を、中間層にポリエチレン又はポリエチレン組成物を、粘着層に特定のエチレン・α−オレフィン共重合体を用いた、特定の物性を有する積層フィルムが、耐傷付き性が良好で、適度な粘着性を有し、部材と貼り合せる際のロール巻状態からの繰り出し性に優れる表面保護フィルムになり得ることを見出し、本発明を完成させた。 As a result of repeating various studies to solve the above problems, the present inventor has obtained a specific polyethylene or polyethylene composition on the outer layer of a three-layer film laminated in the order of the outer layer, the intermediate layer, and the adhesive layer. A laminated film having specific properties using polyethylene or a polyethylene composition and a specific ethylene / α-olefin copolymer for the pressure-sensitive adhesive layer has good scratch resistance and has moderate pressure-sensitive adhesive properties. The present invention has been completed by finding that it can be a surface protective film excellent in unwinding property from a roll-wound state when being bonded together.
すなわち、本発明の第１の発明によれば、外層、中間層、粘着層の順に積層された少なくとも３層構成の表面保護フィルムであって、外層は、低密度ポリエチレン９５〜５重量％、高密度ポリエチレン５〜９５重量％を含む、Ｄ硬度が５５以上であるポリエチレン組成物からなり、中間層は、Ｄ硬度が外層より小さい、ポリエチレン又はポリエチレン組成物からなり、粘着層は、メタロセン触媒を用いて製造され、重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）が３．５以下である、密度が０．８７５〜０．９１０ｇ／ｃｍ３、オルトジクロロベンゼンを溶媒とした温度上昇溶出分離（ＴＲＥＦ）測定において、２０℃以下の溶出量が２０重量％以下、６５℃以上の溶出量が０．５重量％以上のエチレン・α−オレフィン共重合体を主成分とする、タテ方向の引張弾性率が４００ＭＰａ以下であることを特徴とする表面保護フィルムが提供される。 That is, according to the first invention of the present invention, it is a surface protective film having at least a three-layer structure in which an outer layer, an intermediate layer, and an adhesive layer are laminated in this order, and the outer layer has a low density polyethylene of 95 to 5% by weight, a high It comprises a polyethylene composition having a density of 5 to 95% by weight, a D hardness of 55 or more, the intermediate layer is made of polyethylene or a polyethylene composition having a D hardness smaller than the outer layer, and the adhesive layer uses a metallocene catalyst. The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / Mn) is 3.5 or less, the density is 0.875 to 0.910 g / cm 3 , and orthodichlorobenzene is used. In the temperature rise elution separation (TREF) measurement using a solvent, the amount of elution at 20 ° C. or less is 20% by weight or less, and the amount of elution at 65 ° C. or more is 0.5% by weight or more. As a main component fin copolymer, longitudinal direction of the tensile modulus surface protective film is provided to equal to or less than 400 MPa.
また、本発明の第２の発明によれば、第１の発明において、導光板、偏光板、位相差板、プリズムシートの光学材料の保護に使用する表面保護フィルムが提供される。 Moreover, according to 2nd invention of this invention, the surface protection film used for protection of the optical material of a light-guide plate, a polarizing plate, a phase difference plate, and a prism sheet in 1st invention is provided.
本発明の保護フィルムは、耐傷付き性が良好で、適度な粘着性を有し、部材と貼り合せる際のロール巻状態からの繰り出し性に優れる。 The protective film of the present invention has good scratch resistance, has moderate tackiness, and is excellent in roll-out property from a rolled state when bonded to a member.
本発明は、Ｄ硬度が５５以上であるポリエチレン又はポリエチレン組成物からなる外層と、ポリエチレン又はポリエチレン組成物からなる中間層と、密度が０．８７５〜０．９１０ｇ／ｃｍ３、オルトジクロロベンゼンを溶媒とした温度上昇溶出分離（ＴＲＥＦ）測定において、２０℃以下の溶出量が２０重量％以下、６５℃以上の溶出量が０．５重量％以上のエチレン・α−オレフィン共重合体を主成分とする粘着層が、外層、中間層、粘着層の順に積層された少なくとも３層構成の積層フィルムであって、該積層フィルムのタテ方向の引張弾性率が４００ＭＰａ以下である表面保護フィルムである。以下、本発明の保護フィルムの各層の構成成分、保護フィルムの特性、製造法について詳細に説明する。 The present invention relates to an outer layer made of polyethylene or a polyethylene composition having a D hardness of 55 or more, an intermediate layer made of polyethylene or a polyethylene composition, a density of 0.875 to 0.910 g / cm 3 , and orthodichlorobenzene as a solvent. In the temperature rise elution separation (TREF) measurement, an ethylene / α-olefin copolymer having an elution amount of 20 ° C. or less at 20% by weight or less and an elution amount at 65 ° C. or more of 0.5% by weight or more is a main component. The pressure-sensitive adhesive layer is a laminated film having at least a three-layer structure in which an outer layer, an intermediate layer, and a pressure-sensitive adhesive layer are laminated in this order, and is a surface protective film whose tensile elastic modulus in the vertical direction is 400 MPa or less. Hereinafter, the component of each layer of the protective film of the present invention, the characteristics of the protective film, and the production method will be described in detail.
１．外層
本発明の表面保護フィルムの外層は、ポリエチレン又はポリエチレン組成物からなる。外層に用いるポリエチレンとしては、高密度ポリエチレン、高圧ラジカル重合法低密度ポリエチレン、直鎖状低密度ポリエチレン等の低密度ポリエチレン等が挙げられる。
高密度ポリエチレンは、一般的にチーグラー触媒、フィリップス触媒、メタロセン触媒等の触媒を使用して、気相法、溶液法、高圧法、スラリー法等のプロセスで、エチレンまたはエチレンと少量のプロピレン、１−ブテン、１−ヘキセン、４−メチル−１−ペンテン、１−オクテン等のα−オレフィンとを（共）重合させて製造される。
高圧ラジカル重合法低密度ポリエチレンは、パーオキサイドなどのラジカル発生剤を重合開始剤として、高圧ラジカル重合法等のプロセスで、エチレン又はエチレンと少量のプロピレン、１−ブテン、１−ヘキセン、４−メチル−１−ペンテン、１−オクテン等のα−オレフィンとを（共）重合させて製造される。
直鎖状低密度ポリエチレンは、一般的にチーグラー触媒、フィリップス触媒、メタロセン触媒等の触媒を使用して、気相法、溶液法、高圧法、スラリー法等のプロセスでエチレンとプロピレン、１−ブテン、１−ヘキセン、４−メチル−１−ペンテン、１−オクテン等のα−オレフィンとを共重合させて製造される。α−オレフィンは単独で使用してもよいが２種類以上を併用して使用してもかまわない。
低密度ポリエチレンは、成形性の点から高圧ラジカル重合法低密度ポリエチレンを使用することが好ましい。
1. Outer layer The outer layer of the surface protective film of the present invention is made of polyethylene or a polyethylene composition. Examples of the polyethylene used for the outer layer include high-density polyethylene, low-pressure polyethylene such as high-pressure radical polymerization low-density polyethylene, and linear low-density polyethylene.
High-density polyethylene generally uses a catalyst such as a Ziegler catalyst, a Phillips catalyst, or a metallocene catalyst, and is a process such as a gas phase method, a solution method, a high-pressure method, or a slurry method. It is produced by (co) polymerizing with α-olefins such as -butene, 1-hexene, 4-methyl-1-pentene, 1-octene.
High-pressure radical polymerization method Low-density polyethylene uses ethylene or ethylene and a small amount of propylene, 1-butene, 1-hexene, 4-methyl in a process such as a high-pressure radical polymerization method using a radical generator such as peroxide as a polymerization initiator. It is produced by (co) polymerizing α-olefins such as -1-pentene and 1-octene.
Linear low-density polyethylene generally uses a catalyst such as a Ziegler catalyst, a Phillips catalyst, or a metallocene catalyst, and processes such as a gas phase method, a solution method, a high-pressure method, and a slurry method with ethylene and propylene, 1-butene. , 1-hexene, 4-methyl-1-pentene, 1-octene and other α-olefins are copolymerized. The α-olefin may be used alone or in combination of two or more.
The low density polyethylene is preferably a high pressure radical polymerization method low density polyethylene from the viewpoint of moldability.
外層に用いるポリエチレン組成物としては、上記のポリエチレンに添加剤等を配合した樹脂組成物、上記のポリエチレンを二種以上組み合わせた樹脂組成物、上記のポリエチレンに他の熱可塑性樹脂を配合した樹脂組成物やそれらに添加剤等を配合した樹脂組成物などが挙げられる。これらの中でも、ポリエチレンを二種以上組み合わせた樹脂組成物が好ましく、特に、低密度ポリエチレン９５〜５重量％、高密度ポリエチレン５〜９５重量％を含むポリエチレン樹脂組成物が好ましい。 As a polyethylene composition used for the outer layer, a resin composition in which additives are blended with the above polyethylene, a resin composition in which two or more of the above polyethylenes are combined, and a resin composition in which other thermoplastic resins are blended with the above polyethylene And resin compositions in which additives and the like are blended. Among these, the resin composition which combined 2 or more types of polyethylene is preferable, and the polyethylene resin composition containing 95 to 5 weight% of low density polyethylene and 5 to 95 weight% of high density polyethylene is especially preferable.
また、外層に用いられるポリエチレン又はポリエチレン組成物のＤ硬度は、５５以上であり、好ましくは５７以上である。Ｄ硬度が５５未満であると輸送運搬時にフィルム表面に傷がつきやすいために好ましくない。
ここで、Ｄ硬度は、ＪＩＳ Ｋ７２１５に準拠して測定する値である。
Moreover, the D hardness of the polyethylene or polyethylene composition used for the outer layer is 55 or more, preferably 57 or more. A D hardness of less than 55 is not preferred because the film surface is easily damaged during transportation.
Here, the D hardness is a value measured in accordance with JIS K7215.
ポリエチレンのＤ硬度は、ポリエチレン樹脂メーカーやポリエチレン樹脂販売会社作成の商品パンフレットに掲げられているので、それら市販品の中から選択することが可能である。ポリエチレンを二種以上組み合わせた樹脂組成物のＤ硬度は、各ポリエチレンのＤ硬度と組成割合から加成則計算で予測することができる。一般に、Ｄ硬度はポリエチレンの結晶化度に応じて変化すると考えられるので、ポリエチレン樹脂の中では高密度ポリエチレンが高く、密度が小さくなるにつれて低くなる傾向がある。
本発明においては、Ｄ硬度が５５以上を満たす範囲内で、他の性能（透明性、成形性、中間層との層間強度等）を勘案しつつ選ぶことが好ましい。成形加工性の点から高圧ラジカル重合法低密度ポリエチレン５〜９５重量％、高密度ポリエチレン５〜９５％を含む樹脂組成物であることが好ましい。成形性が優れる高圧ラジカル重合法低密度ポリエチレンと高いＤ硬度の高密度ポリエチレンとのブレンドにより、成形性が良好な硬度の高い外層とすることができる。その他の好ましい態様としては、密度が０．９２５ｇ／ｃｍ３以上の直鎖状低密度ポリエチレンが挙げられる。その利点はフィルム強度が強くなることである。
Since the D hardness of polyethylene is listed in a product pamphlet created by a polyethylene resin manufacturer or a polyethylene resin sales company, it can be selected from those commercially available products. The D hardness of a resin composition in which two or more kinds of polyethylene are combined can be predicted by addition rule calculation from the D hardness and composition ratio of each polyethylene. In general, since the D hardness is considered to change according to the crystallinity of polyethylene, high-density polyethylene is high among polyethylene resins, and tends to decrease as the density decreases.
In the present invention, it is preferable to select in consideration of other performances (transparency, moldability, interlayer strength with the intermediate layer, etc.) within a range where D hardness is 55 or more. From the viewpoint of molding processability, a resin composition containing 5 to 95% by weight of low-pressure polyethylene and 5 to 95% of high-density polyethylene is preferable. High-pressure radical polymerization method with excellent moldability By blending low-density polyethylene and high-density polyethylene with high D hardness, it is possible to form an outer layer with good moldability and high hardness. Other preferred embodiments include linear low density polyethylene having a density of 0.925 g / cm 3 or more. The advantage is increased film strength.
２．中間層
本発明の表面保護フィルムの中間層は、ポリエチレン又はポリエチレン組成物からなる。 ポリエチレン又はポリエチレン組成物としては、特に制限がないが、上記外層で用いたポリエチレン又はポリエチレン組成物と同様なものが好ましいが、Ｄ硬度が外層のポリエチレン又はポリエチレン組成物のそれより小さいポリエチレン又はポリエチレン組成物を使用することが好ましく、Ｄ硬度が５２以下であることがより好ましい。Ｄ硬度が外層のポリエチレン又はポリエチレン組成物のそれより小さいことにより、表面硬度と柔軟性のバランスが良好なものになる。
2. Intermediate layer The intermediate layer of the surface protective film of the present invention is made of polyethylene or a polyethylene composition. Although there is no restriction | limiting in particular as polyethylene or a polyethylene composition, Although the thing similar to the polyethylene or polyethylene composition used for the said outer layer is preferable, D hardness is smaller than that of the outer layer polyethylene or polyethylene composition, or a polyethylene or polyethylene composition It is preferable to use a thing, and it is more preferable that D hardness is 52 or less. When the D hardness is smaller than that of the outer layer polyethylene or the polyethylene composition, the balance between surface hardness and flexibility is good.
３．粘着層
本発明の表面保護フィルムの粘着層は、エチレン・α−オレフィン共重合体が主成分として用いられる。
粘着層で用いるエチレン・α−オレフィン共重合体の密度は、０．８７５〜０．９１０ｇ／ｃｍ３、好ましくは０．８８０〜０．９０５ｇ／ｃｍ３である。密度が０．８７５ｇ／ｃｍ３未満であると融点が低いため保管時のブロッキングが大きい。一方、密度が０．９１０ｇ／ｃｍ３より大きいと粘着強度が弱くなるので好ましくない。
ここで、密度は、ＪＩＳ−Ｋ７１１２に準拠して測定する値である。
3. Adhesive layer The adhesive layer of the surface protective film of the present invention contains an ethylene / α-olefin copolymer as a main component.
The density of the ethylene / α-olefin copolymer used in the adhesive layer is 0.875 to 0.910 g / cm 3 , preferably 0.880 to 0.905 g / cm 3 . When the density is less than 0.875 g / cm 3 , the melting point is low, so that blocking during storage is large. On the other hand, if the density is larger than 0.910 g / cm 3 , the adhesive strength becomes weak.
Here, the density is a value measured according to JIS-K7112.
また、エチレン・α−オレフィン共重合体の温度上昇溶出分離（ＴＲＥＦ）による２０℃以下の溶出量は、２０重量％以下、好ましくは５重量％以下、より好ましくは３重量％以下である。ＴＲＥＦによる溶出量が２０重量％を超えると繰り出し時の剥離強度が大きく滑らかに繰り出せないので好ましくない。
さらに、エチレン・α−オレフィン共重合体の温度上昇溶出分離（ＴＲＥＦ）による６５℃以上の溶出量は、０．５％重量以上、好ましくは２．０重量％以上、より好ましくは５．０重量％以上である。ＴＲＥＦによる６５℃以上の溶出量が０．５重量％以下であると粘着強度が弱くなるので好ましくない。
ここで、ＴＲＥＦによる溶出量の測定は、結晶性分別を行う昇温溶出分別（ＴＲＥＦ）部と分子量分別を行うゲルパーミエーションクロマトグラフィー（ＧＰＣ）部とから成る下記のクロス分別クロマトグラフ（ＣＦＣ）方法による。
まず、ポリマーサンプルを０．５ｍｇ／ｍＬのＢＨＴを含むオルトジクロロベンゼン（ＯＤＣＢ）に１４０℃で完全に溶解した後、この溶液を装置のサンプルループを経て１４０℃に保持されたＴＲＥＦカラム（不活性ガラスビーズ担体が充填されたカラム）に注入し、所定の第１溶出温度まで徐々に冷却しポリマーサンプルを結晶化させる。所定の温度で３０分保持した後、ＯＤＣＢをＴＲＥＦカラムに通液することにより、溶出成分がＧＰＣ部に注入されて分子量分別が行われ、赤外検出器（ＦＯＸＢＯＲＯ社製ＭＩＲＡＮ １Ａ ＩＲ検出器、測定波長３．４２μｍ）によりクロマトグラムが得られる。その間ＴＲＥＦ部では次の溶出温度に昇温され、第１溶出温度のクロマトグラムが得られた後、第２溶出温度での溶出成分がＧＰＣ部に注入される。以下同様の操作を繰り返すことにより、各溶出温度での溶出成分のクロマトグラムが得られる。
測定条件を以下に示す。
装置：ダイヤインスツルメンツ社製ＣＦＣ−Ｔ１０２Ｌ
ＧＰＣカラム：昭和電工社製ＡＤ−８０６ＭＳ（３本を直列に接続）
溶媒：ＯＤＣＢ
サンプル濃度：３ｍｇ／ｍＬ
注入量：０．４ｍＬ
結晶化速度：１℃／分
溶媒流速：１ｍＬ／分
ＧＰＣ測定時間：３４分
ＧＰＣ測定後安定時間：５分
溶出温度：０，５，１０，１５，２０，２５，３０，３５，４０，４５，４９，５２，５５，５８，６１，６４，６７，７０，７３，７６，７９，８２，８５，８８，９１，９４，９７，１００，１０２，１２０，１４０
データ解析：測定によって得られた各溶出温度における溶出成分のクロマトグラムは、装置付属のデータ処理プログラムにより処理され、総和が１００％となるように規格化された溶出量（クロマトグラムの面積に比例）が求められる。さらに、溶出温度に対する積分溶出曲線が計算される。得られた溶出曲線から２０℃以下の溶出量と６５℃以上の溶出量を求める。
Further, the amount of elution at 20 ° C. or less by temperature rising elution separation (TREF) of the ethylene / α-olefin copolymer is 20% by weight or less, preferably 5% by weight or less, more preferably 3% by weight or less. If the amount of elution by TREF exceeds 20% by weight, the peeling strength at the time of feeding is large, and it cannot be smoothly fed out.
Furthermore, the elution amount of 65 ° C. or more by temperature rising elution separation (TREF) of the ethylene / α-olefin copolymer is 0.5% by weight or more, preferably 2.0% by weight or more, more preferably 5.0% by weight. % Or more. If the amount of elution at 65 ° C. or higher by TREF is 0.5% by weight or less, the adhesive strength becomes weak, which is not preferable.
Here, the amount of elution by TREF is measured by the following cross fractionation chromatograph (CFC) comprising a temperature rising elution fractionation (TREF) portion for performing crystalline fractionation and a gel permeation chromatography (GPC) portion for performing molecular weight fractionation. Depending on the method.
First, a polymer sample was completely dissolved in orthodichlorobenzene (ODCB) containing 0.5 mg / mL BHT at 140 ° C., and this solution was passed through a sample loop of the apparatus, and a TREF column (inert) maintained at 140 ° C. The polymer sample is crystallized by slowly cooling to a predetermined first elution temperature. After maintaining at a predetermined temperature for 30 minutes, ODCB is passed through a TREF column, whereby the eluted component is injected into the GPC section to perform molecular weight fractionation. An infrared detector (MIRAN 1A IR detector manufactured by FOXBORO, A chromatogram is obtained with a measuring wavelength of 3.42 μm). Meanwhile, in the TREF part, the temperature is raised to the next elution temperature, and after obtaining the chromatogram of the first elution temperature, the elution component at the second elution temperature is injected into the GPC part. Thereafter, the same operation is repeated to obtain a chromatogram of the eluted components at each elution temperature.
The measurement conditions are shown below.
Equipment: CFC-T102L manufactured by Dia Instruments
GPC column: Showa Denko AD-806MS (3 connected in series)
Solvent: ODCB
Sample concentration: 3 mg / mL
Injection volume: 0.4mL
Crystallization rate: 1 ° C / min Solvent flow rate: 1 mL / min GPC measurement time: 34 minutes Stabilization time after GPC measurement: 5 minutes Elution temperature: 0, 5, 10, 15, 20, 25, 30, 35, 40, 45 49, 52, 55, 58, 61, 64, 67, 70, 73, 76, 79, 82, 85, 88, 91, 94, 97, 100, 102, 120, 140
Data analysis: The chromatograms of the elution components obtained at each elution temperature obtained by measurement are processed by the data processing program attached to the instrument, and the elution amount is standardized so that the total is 100% (proportional to the area of the chromatogram) ) Is required. In addition, an integrated elution curve for the elution temperature is calculated. An elution amount of 20 ° C. or lower and an elution amount of 65 ° C. or higher are determined from the obtained elution curve.
さらに、エチレン・α−オレフィン共重合体の重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）は、３．５以下が好ましく、より好ましくは３．０〜１．５であり、特に好ましくは２．５〜２．０である。Ｍｗ／Ｍｎが３．５を超えると、べた付き性が出てくるおそれがある。
ここで、Ｍｗ／Ｍｎは、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定した重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）で定義されるものである。Ｍｗ／Ｍｎの測定方法は、以下の通りである。
装置：ウオーターズ社製ＧＰＣ １５０Ｃ型
検出器：ＭＩＲＡＮ １Ａ赤外分光光度計（測定波長、３．４２μｍ）
カラム：昭和電工社製ＡＤ８０６Ｍ／Ｓ ３本［カラムの較正は、東ソー製単分散ポリスチレン（Ａ５００，Ａ２５００，Ｆ１，Ｆ２，Ｆ４，Ｆ１０，Ｆ２０，Ｆ４０，Ｆ２８８の各０．５ｍｇ／ｍｌ溶液）の測定を行い、溶出体積と分子量の対数値を２次式で近似した。また、試料の分子量は、ポリスチレンとポリエチレンの粘度式を用いてポリエチレンに換算した。ここでポリスチレンの粘度式の係数は、α＝０．７２３、ｌｏｇＫ＝−３．９６７であり、ポリエチレンは、α＝０．７２３、ｌｏｇＫ＝−３．４０７である。
測定温度：１４０℃
注入量：０．２ｍｌ
濃度：２０ｍｇ／１０ｍＬ
溶媒：オルソジクロロベンゼン
流速：１．０ｍｌ／ｍｉｎ
Furthermore, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the ethylene / α-olefin copolymer is preferably 3.5 or less, more preferably 3.0 to 1. 5, particularly preferably 2.5 to 2.0. If Mw / Mn exceeds 3.5, stickiness may occur.
Here, Mw / Mn is defined by the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC). The measuring method of Mw / Mn is as follows.
Apparatus: Waters GPC 150C type Detector: MIRAN 1A infrared spectrophotometer (measurement wavelength, 3.42 μm)
Column: AD806M / S manufactured by Showa Denko Co., Ltd. (column calibration is performed by Tosoh monodisperse polystyrene (0.5 mg / ml solution of each of A500, A2500, F1, F2, F4, F10, F20, F40, and F288) Measurement was performed, and the logarithm of the elution volume and the molecular weight was approximated by a quadratic equation. The molecular weight of the sample was converted to polyethylene using the viscosity formula of polystyrene and polyethylene. Here, the coefficients of the viscosity formula of polystyrene are α = 0.723 and log K = −3.767, and polyethylene has α = 0.723 and log K = −3.407.
Measurement temperature: 140 ° C
Injection volume: 0.2ml
Concentration: 20 mg / 10 mL
Solvent: Orthodichlorobenzene Flow rate: 1.0 ml / min
本発明の粘着層に用いられるエチレン・α−オレフィン共重合体は、チーグラー触媒、フィリップス触媒、メタロセン触媒等の触媒を使用して気相法、溶液法、高圧法、スラリー法等のプロセスでエチレンとプロピレン、１−ブテン、１−ヘキセン、４−メチル−１−ペンテン、１−オクテン等のα−オレフィンとを共重合させて製造される。この中で特にメタロセン触媒を用いて高圧法、もしくは溶液法で製造されたものが分子量分布、結晶性分布とも狭いため好ましい。 The ethylene / α-olefin copolymer used in the adhesive layer of the present invention is obtained by using a catalyst such as a Ziegler catalyst, a Phillips catalyst, or a metallocene catalyst in a process such as a gas phase method, a solution method, a high pressure method, or a slurry method. And propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and other α-olefins are copolymerized. Among these, those produced by a high pressure method or a solution method using a metallocene catalyst are particularly preferable because both the molecular weight distribution and the crystallinity distribution are narrow.
４．保護フィルム
本発明の表面保護フィルムは、上記各層が、外層、中間層、粘着層の順に積層された少なくとも３層構成を持つ積層フィルムである。外層の役割は主に傷つきの防止であり、中間層の役割は主にフィルムの剛性の低下の抑制であり、粘着層の役割は主に部材との粘着である。
4). Protective film The surface protective film of the present invention is a laminated film having at least three layers in which the above layers are laminated in the order of an outer layer, an intermediate layer, and an adhesive layer. The role of the outer layer is mainly to prevent scratches, the role of the intermediate layer is mainly to suppress a decrease in the rigidity of the film, and the role of the adhesive layer is mainly to stick to the member.
本発明の表面保護フィルムは、外層（Ａ）、中間層（Ｂ）、粘着層（Ｃ）の他に、例えば、層間の接着性を高めるため、外層と中間層との間、中間層と粘着層との間のいずれか一方又は両方に接着層を設けることができる。 In addition to the outer layer (A), the intermediate layer (B), and the adhesive layer (C), the surface protective film of the present invention is, for example, between the outer layer and the intermediate layer, and between the intermediate layer and the adhesive layer in order to improve the adhesion between the layers. An adhesive layer can be provided either or both between the layers.
積層フィルムの厚さは、２０〜１００μｍ、各層の厚さの比率はＡ／Ｂ／Ｃ＝２〜３０μｍ／１６〜９８μｍ／２〜３０μｍである。 The thickness of the laminated film is 20 to 100 μm, and the ratio of the thicknesses of the respective layers is A / B / C = 2 to 30 μm / 16 to 98 μm / 2 to 30 μm.
また、本発明の表面保護フィルムのタテ方向の引張弾性率は、４００ＭＰａ以下であり、好ましくは３００ＭＰａ以下、より好ましくは２００ＭＰａ以下である。フィルムのタテ方向の引張弾性率が４００ＭＰａを超えると粘着強度が低下する。フィルムのタテ引張弾性率の下限には制限はないが、低すぎると繰り出し時にフィルムが伸びてしまう不具合のおそれがあるので１００ＭＰａ程度を下限の目安にするとよい。
ここで、タテ方向の引張弾性率は、ＩＳＯ Ｒ１１８４に準拠してフィルム成形時の引取り方向（タテ方向）の弾性率をフィルム弾性率として求める値である。
Moreover, the tensile modulus in the vertical direction of the surface protective film of the present invention is 400 MPa or less, preferably 300 MPa or less, more preferably 200 MPa or less. When the tensile modulus in the vertical direction of the film exceeds 400 MPa, the adhesive strength decreases. The lower limit of the vertical tensile modulus of the film is not limited, but if it is too low, there is a possibility that the film will elongate when fed out.
Here, the tensile modulus in the vertical direction is a value obtained as the film elastic modulus in the take-up direction (vertical direction) during film formation in accordance with ISO R1184.
積層フィルムのタテ方向の引張弾性率が４００ＭＰａ以下を満たす好ましい態様を述べる。第一の好ましい態様としては、外層にＤ硬度が５５以上であるポリエチレン又はポリエチレン組成物、中間層にＤ硬度が５３以下のポリエチレン又はポリエチレン組成物、粘着層が密度が０．８７５〜０．９１０ｇ／ｃｍ３のエチレン・α−オレフィン共重合体を私用したフィルムが挙げられる。その利点は耐傷つき性、粘着性、繰り出し性が良好である。
ポリエチレン、エチレン・α−オレフィン共重合体の弾性率は、ポリエチレン樹脂メーカーやポリエチレン樹脂販売会社作成の商品パンフレットに掲げられているので、多層フィルムの弾性率はそれらの値や各層の厚さ比率から予測することができる。例えば、外層にＤ硬度５５以上のポリエチレンもしくはポリエチレン組成物を用い、フィルムのタテ引張弾性率は４００ＭＰａ以下とするためには、外層に用いるポリエチレンの密度を中間層に使用するポリエチレンの密度よりも高くする、もしくは外層にブレンドする高密度ポリエチレンの割合を中間層の比率よりも小さくすること、さらに外層の厚みを中間層の厚みより薄くすることにより達成される。さらに、本発明では、弾性率が４００ＭＰａ以下を満たす範囲内で、他の性能（透明性、成形性、各層間の層間強度等）を勘案しつつ選ぶことが好ましい。
A preferred embodiment in which the tensile modulus of the laminated film in the vertical direction satisfies 400 MPa or less will be described. As a first preferred embodiment, the outer layer has a polyethylene or polyethylene composition having a D hardness of 55 or more, the intermediate layer has a polyethylene or polyethylene composition having a D hardness of 53 or less, and the adhesive layer has a density of 0.875 to 0.910 g. / cm 3 of ethylene · alpha-olefin copolymer include films private. The advantages are good scratch resistance, adhesiveness and unwinding property.
The elastic modulus of polyethylene and ethylene / α-olefin copolymers is listed in product brochures created by polyethylene resin manufacturers and polyethylene resin sales companies, so the elastic modulus of multilayer films is calculated from their values and the thickness ratio of each layer. Can be predicted. For example, in order to use polyethylene or a polyethylene composition having a D hardness of 55 or more for the outer layer and the film to have a vertical tensile modulus of 400 MPa or less, the density of the polyethylene used for the outer layer is higher than the density of the polyethylene used for the intermediate layer. The ratio of the high density polyethylene to be blended with the outer layer is made smaller than the ratio of the intermediate layer, and the thickness of the outer layer is made thinner than the thickness of the intermediate layer. Furthermore, in this invention, it is preferable to select in consideration of other performances (transparency, moldability, interlayer strength between layers, etc.) within a range where the elastic modulus satisfies 400 MPa or less.
５．保護フィルムの製造
本発明の表面保護フィルムの製造方法における各層の形成ないし積層は、合目的的な任意のものであり得る。従来の多層フィルムの成形方法に従って、例えば、各層を予め別々にフィルム状に形成して、その後、それらを接着させて積層する方法、及び押出法によって各層の形成及び積層を同一工程で行う方法等がある。前者の場合において、フィルムの製造は、空冷インフレーション成形、空冷二段冷却インフレーション法、Ｔダイフィルム成形、水冷インフレーション成形法等を採用することができる。また、後者の押出方法としては、押出ラミネート法、ドライラミネート法、サンドイッチラミネート法、共押出し法（接着層を設けない共押出し、接着層を設ける共押出し、接着樹脂を配合する共押出しを含む）等の方法がある。本発明では、いずれの方法によっても各種の多層フィルムを得ることができる。
5. Production of Protective Film Formation or lamination of each layer in the method for producing a surface protective film of the present invention can be any purposeful purpose. In accordance with a conventional method for forming a multilayer film, for example, each layer is formed separately in advance, and then laminated by adhering them, and a method of forming and laminating each layer by the extrusion method in the same process, etc. There is. In the former case, the film can be produced by air-cooled inflation molding, air-cooled two-stage cooling inflation method, T-die film molding, water-cooled inflation molding method or the like. Moreover, as the latter extrusion method, extrusion lamination method, dry lamination method, sandwich lamination method, co-extrusion method (including co-extrusion without providing an adhesive layer, co-extrusion with an adhesive layer, and co-extrusion with an adhesive resin) There are methods. In the present invention, various multilayer films can be obtained by any method.
６．保護フィルムの用途
本発明の表面保護フィルムは、被着体表面に粘着層が接するように貼りあわされ、被着体表面の傷つきや汚れを防止する。表面保護フィルムの使用後は被着体から剥がされる、可剥性表面保護用粘着フィルムとして用いられる。
本発明の表面保護フィルムは、光学材料等の被着体の表面を保護することに用いることが好ましく、特に、導光板、偏光板、位相差板、プリズムシート等の光学材料の保護に使用することが好ましい。
被着体への貼り合わせ方法は、公知のいかなる方法でもよく、例えば被着体とフィルムを二本のロール間を通して貼り合わせるラミネーターによる方法などが挙げられる。このようにして表面保護フィルムの粘着層が被着体表面に貼りあわされた光学材料が得られる。
6). Use of Protective Film The surface protective film of the present invention is attached so that the adhesive layer is in contact with the surface of the adherend, and prevents the adherend surface from being damaged or soiled. After the surface protective film is used, it is peeled off from the adherend and used as a peelable surface protective pressure-sensitive adhesive film.
The surface protective film of the present invention is preferably used for protecting the surface of an adherend such as an optical material, and particularly used for protecting optical materials such as a light guide plate, a polarizing plate, a retardation plate, and a prism sheet. It is preferable.
The bonding method to the adherend may be any known method, for example, a method using a laminator for bonding the adherend and the film through two rolls. Thus, an optical material in which the adhesive layer of the surface protective film is adhered to the surface of the adherend is obtained.
以下に示す実施例によって、本発明を更に具体的に説明するが、本発明は、その要旨を超えない限り、以下の実施例に限定されるものではない。なお、実施例で用いた物性測定・評価方法、材料は以下の通りである。 The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples unless it exceeds the gist. The physical property measurement / evaluation methods and materials used in the examples are as follows.
１．物性の測定と評価方法
（１）ＭＦＲ：ＪＩＳ−Ｋ７２１０に準拠し、１９０℃、２．１６ｋｇ荷重の条件で測定した。
（２）密度：ＪＩＳ−Ｋ７１１２に準拠して測定した。
（３）ＴＲＥＦによる２０℃以下の溶出量、６５℃以上の溶出量：前述の方法で測定した。
（４）Ｍｗ／Ｍｎ：前述の方法で測定した。
（５）フィルム弾性率：ＩＳＯ Ｒ１１８４に準拠してフィルム成形時の引取り方向（タテ方向）の弾性率をフィルム弾性率として求めた。
（６）粘着性：フィルムのタテ方向を長手方向にとり、幅２５ｍｍ、長さ２０ｃｍに切断し、予め４５℃に加温したアクリル樹脂板に貼りつけた。貼りつけたフィルムを温度２３℃湿度５０％の中で１２時間エージングした後、ＪＩＳ Ｚ０２３７に準拠して引張速度３００ｍｍ／分、引きはがし角度１８０℃にて２５ｍｍ幅あたりの粘着強度を測定した。
（７）外層表面硬度：外層に使用している樹脂を温度１６０℃で２ｍｍの厚みのプレスシートを作成しＪＩＳ Ｋ７２１５に準拠しＤ硬度を測定した。外層が樹脂の混合物である場合は予め４０ｍｍφの押出機で１８０℃で溶融混練して均質化した後、評価に使用した。
（８）外層−粘着層間剥離性：通常プロテクトフィルムは、外層と粘着層が接した形で紙管に巻き取られ、繰り出されて製品に接着して使用される。繰り出し性の評価として、成形したフィルムを３インチの紙管に外層と粘着層が接した形で巻き取り、繰り出し機に取り付け２０ｍ／分で繰り出した際にシワ、たるみ等入らずに滑らかに繰り出せるかを目視で確認し、滑らかに繰り出せるものを○、滑らかに繰り出せないものを×とした。
1. Measurement of physical properties and evaluation method (1) MFR: Measured in accordance with JIS-K7210 under conditions of 190 ° C. and 2.16 kg load.
(2) Density: Measured according to JIS-K7112.
(3) Elution amount of 20 ° C. or lower by TREF, elution amount of 65 ° C. or higher: measured by the method described above.
(4) Mw / Mn: measured by the method described above.
(5) Film elastic modulus: Based on ISO R1184, the elastic modulus in the take-up direction (vertical direction) during film formation was determined as the film elastic modulus.
(6) Adhesiveness: The lengthwise direction of the film was taken as the longitudinal direction, the film was cut into a width of 25 mm and a length of 20 cm, and attached to an acrylic resin plate heated to 45 ° C. in advance. After the pasted film was aged for 12 hours in a temperature of 23 ° C. and a humidity of 50%, the adhesive strength per 25 mm width was measured at a pulling speed of 300 mm / min and a peeling angle of 180 ° C. according to JIS Z0237.
(7) Outer layer surface hardness: A press sheet having a thickness of 2 mm was prepared at a temperature of 160 ° C. from the resin used in the outer layer, and D hardness was measured in accordance with JIS K7215. When the outer layer was a resin mixture, it was used for evaluation after being melt-kneaded and homogenized at 180 ° C. in advance with a 40 mmφ extruder.
(8) Outer layer-adhesive delamination property: Usually, a protective film is wound around a paper tube in a form in which the outer layer and the adhesive layer are in contact with each other. As an evaluation of unwinding property, the formed film can be rolled up in a form in which the outer layer and the adhesive layer are in contact with a 3-inch paper tube, and when unrolled at 20m / min, it can be unwound smoothly without wrinkles or sagging. These were visually checked, and those that could be smoothly fed were marked with ◯, and those that could not be smoothly fed were marked with X.
２．材料
（１）外層、中間層用ポリエチレン
ＰＥ−１：高圧法低密度ポリエチレン（日本ポリエチレン（株）社製ＬＦ２４０）、ＭＦＲ０．７ｇ／１０分、密度０．９２４ｇ／ｃｍ３、Ｄ硬度５２
ＰＥ−２：高密度ポリエチレン（日本ポリエチレン（株）社製ＨＪ５６０）、ＭＦＲ７ｇ／１０分、密度０．９６４ｇ／ｃｍ３、Ｄ硬度６６
（２）粘着層用エチレン・α−オレフィン共重合体
下記の製造例１〜３で得られた（ＰＥ−３）〜（ＰＥ−５）を用いた。物性を表１に示す。
2. Material (1) Polyethylene for outer layer and intermediate layer PE-1: High pressure method low density polyethylene (LF240 manufactured by Nippon Polyethylene Co., Ltd.), MFR 0.7 g / 10 min, density 0.924 g / cm 3 , D hardness 52
PE-2: High density polyethylene (HJ560 manufactured by Nippon Polyethylene Co., Ltd.), MFR 7 g / 10 min, density 0.964 g / cm 3 , D hardness 66
(2) Ethylene / α-olefin copolymer for adhesive layer (PE-3) to (PE-5) obtained in the following Production Examples 1 to 3 were used. The physical properties are shown in Table 1.
（製造例１）
触媒の調製は、特表平７−５０８５４５号公報に記載された方法で実施した。即ち、錯体ジメチルシリレンビス（４，５，６，７−テトラヒドロインデニル）ハフニウムジメチル２．０ミリモルに、トリペンタフルオロフェニルホウ素を上記錯体に対して等モル加え、トルエンで１０リットルに希釈して触媒溶液を調製した。
（ｉｉ）重合
内容積１．５リットルの撹拌式オートクレーブ型連続反応器を反応器内の圧力１３０ＭＰａに保ち、エチレンと１−ヘキセンとの混合物を１−ヘキセンの組成が５６重量％となるように４０ｋｇ／時の割合で原料ガスを連続的に供給した。また、上記触媒溶液を連続的に供給し、重合温度が１５２℃を維持するようにその供給量を調整した。１時間あたりのポリマー生産量は約２．５ｋｇであった。反応終了後、１−ヘキセン含有量＝１２重量％、ＭＦＲ＝３．３ｇ／１０分、密度＝０．９０５ｇ／ｃｍ３、Ｍｗ／Ｍｎ＝２．３、ＴＲＥＦの２０℃以下の溶出量が０．５重量％であり、ＴＲＥＦの６５℃以上の溶出量が１０．１重量％であるエチレン・１−ヘキセン共重合体（ＰＥ−３）を得た。
(Production Example 1)
The catalyst was prepared by the method described in JP-T-7-508545. That is, 2.0 mol of complex dimethylsilylene bis (4,5,6,7-tetrahydroindenyl) hafnium dimethyl is added in an equimolar amount to the above complex, and diluted to 10 liters with toluene. A catalyst solution was prepared.
(Ii) Polymerization A stirred autoclave type continuous reactor having an internal volume of 1.5 liters is maintained at a pressure of 130 MPa in the reactor so that the composition of ethylene and 1-hexene is 56% by weight of 1-hexene. The raw material gas was continuously supplied at a rate of 40 kg / hour. The catalyst solution was continuously supplied, and the supply amount was adjusted so that the polymerization temperature was maintained at 152 ° C. The polymer production per hour was about 2.5 kg. After completion of the reaction, 1-hexene content = 12% by weight, MFR = 3.3 g / 10 min, density = 0.905 g / cm 3 , Mw / Mn = 2.3, and the amount of elution of TREF at 20 ° C. or less is 0. Thus, an ethylene / 1-hexene copolymer (PE-3) having an elution amount of TREF of 65 ° C. or higher of 10.1% by weight was obtained.
（製造例２）
重合時の１−ヘキセンの組成を６３重量％にし、重合温度を１４４℃に代えた以外は製造例１と同様の製法で触媒調整及び重合を行った。１時間あたりのポリマー生産量は約２．４ｋｇであった。反応終了後、１−ヘキセン含有量＝１５重量％、ＭＦＲ＝３．５ｇ／１０分、密度＝０．８９８ｇ／ｃｍ３、Ｍｗ／Ｍｎ＝２．３であるエチレン・１−ヘキセン共重合体（ＰＥ−４）を得た。
(Production Example 2)
Catalyst preparation and polymerization were carried out in the same manner as in Production Example 1 except that the composition of 1-hexene at the time of polymerization was changed to 63% by weight and the polymerization temperature was changed to 144 ° C. The polymer production per hour was about 2.4 kg. After completion of the reaction, an ethylene / 1-hexene copolymer having a 1-hexene content = 15% by weight, MFR = 3.5 g / 10 minutes, density = 0.898 g / cm 3 , and Mw / Mn = 2.3 ( PE-4) was obtained.
（製造例３）
重合時の１−ヘキセンの組成を７６重量％にし、重合温度を１１６℃に代えた以外は製造例１と同様の製法で触媒調整及び重合を行った。１時間あたりのポリマー生産量は約２．７ｋｇであった。反応終了後、１−ヘキセン含有量＝３０重量％、ＭＦＲ＝２．６ｇ／１０分、密度＝０．８７０ｇ／ｃｍ３、Ｍｗ／Ｍｎ＝２．０であるエチレン・１−ヘキセン共重合体（ＰＥ−５）を得た。
(Production Example 3)
Catalyst preparation and polymerization were carried out in the same manner as in Production Example 1 except that the composition of 1-hexene at the time of polymerization was 76% by weight and the polymerization temperature was changed to 116 ° C. The polymer production per hour was about 2.7 kg. After completion of the reaction, an ethylene / 1-hexene copolymer having 1-hexene content = 30 wt%, MFR = 2.6 g / 10 min, density = 0.870 g / cm 3 , and Mw / Mn = 2.0 ( PE-5) was obtained.
（実施例１）
外層に（ＰＥ−１）６０重量％と（ＰＥ−２）４０重量％からなるポリエチレン樹脂組成物を用い、中間層に（ＰＥ−１）１００重量％のポリエチレンを用い、粘着層に（ＰＥ−３）のエチレン・α−オレフィン共重合体を１００重量％使用し、外層の押出機４０ｍｍφ、中間層の押出機４０ｍｍφ、粘着層の押出機４０ｍｍφを有する多層インフレーション成形機を使用して成形温度１６０℃で外層厚み１０μｍ、中間層厚み３０μｍ、粘着層厚み１０μｍの多層インフレーションフィルムからなる表面保護フィルムを作成した。得られた、表面保護フィルムの評価結果を表２に示す。
Example 1
A polyethylene resin composition comprising 60% by weight of (PE-1) and 40% by weight of (PE-2) is used for the outer layer, 100% by weight of polyethylene is used for the intermediate layer, and (PE- 3) 100% by weight of the ethylene / α-olefin copolymer was used, and a molding temperature of 160 mm was used using a multilayer inflation molding machine having an outer layer extruder 40 mmφ, an intermediate layer extruder 40 mmφ, and an adhesive layer extruder 40 mmφ. A surface protective film made of a multilayer inflation film having an outer layer thickness of 10 μm, an intermediate layer thickness of 30 μm, and an adhesive layer thickness of 10 μm was prepared at ° C. Table 2 shows the evaluation results of the obtained surface protective film.
（実施例２）
粘着層に（ＰＥ−４）を１００重量％使用する以外は実施例１と同様にして、表面保護フィルムを作成した。得られた、表面保護フィルムの評価結果を表２に示す。
(Example 2)
A surface protective film was prepared in the same manner as in Example 1 except that 100% by weight of (PE-4) was used for the adhesive layer. Table 2 shows the evaluation results of the obtained surface protective film.
（比較例１）
外層に（ＰＥ−１）１００重量％のポリエチレンを使用する以外は実施例１と同様にして、表面保護フィルムを作成した。得られた、表面保護フィルムの評価結果を表２に示す。
(Comparative Example 1)
A surface protective film was prepared in the same manner as in Example 1 except that (PE-1) 100% by weight of polyethylene was used for the outer layer. Table 2 shows the evaluation results of the obtained surface protective film.
（比較例２）
中間層に（ＰＥ−１）６０重量％と（ＰＥ−２）４０重量％からなるポリエチレン樹脂組成物を用いる以外は実施例１と同様にして、表面保護フィルムを作成した。得られた、表面保護フィルムの評価結果を表２に示す。
(Comparative Example 2)
A surface protective film was prepared in the same manner as in Example 1 except that a polyethylene resin composition comprising 60% by weight of (PE-1) and 40% by weight of (PE-2) was used for the intermediate layer. Table 2 shows the evaluation results of the obtained surface protective film.
（比較例３）
粘着層に（ＰＥ−５）１００重量％のエチレン・α−オレフィン共重合体を用いる以外は実施例１と同様にして、表面保護フィルムを作成した。得られた、表面保護フィルムの評価結果を表２に示す。
(Comparative Example 3)
A surface protective film was prepared in the same manner as in Example 1 except that (PE-5) 100 wt% ethylene / α-olefin copolymer was used for the adhesive layer. Table 2 shows the evaluation results of the obtained surface protective film.
表２から明らかなように、本発明の表面保護フィルムは、粘着性及び耐傷つき性が良好でかつ良好な繰り出し性を有するフィルムである（実施例１，２）。一方、外層表面硬度が劣ると傷つき性に劣り（比較例１）、タテ方向フィルム弾性率が高すぎると粘着性が十分でなく（比較例２）、粘着層にＴＲＥＦによる２０℃以下の溶出量の多いエチレン・α−オレフィン共重合体を用いると繰り出し性に劣る（比較例３）。 As is apparent from Table 2, the surface protective film of the present invention is a film having good adhesiveness and scratch resistance and having good payout properties (Examples 1 and 2). On the other hand, if the outer layer surface hardness is inferior, the scratch resistance is inferior (Comparative Example 1), and if the vertical film elastic modulus is too high, the adhesiveness is not sufficient (Comparative Example 2). When an ethylene / α-olefin copolymer having a large amount is used, the drawability is poor (Comparative Example 3).
本発明の表面保護フィルムは、粘着剤を添加しなくても良好な部材表面への粘着性を有し、輸送運搬時のフィルム表面の傷つき性が良好で、部材と貼り合せる際の繰出時にシワが入らず滑らかに繰り出すことができるため、導光板、偏光板、位相差板、プリズムシート等の光学材料の保護に好適に使用することができる。 The surface protective film of the present invention has good adhesiveness to the surface of a member without adding an adhesive, has good scratching properties on the film surface during transportation and transportation, and is wrinkled when being attached to the member. Therefore, it can be used smoothly for protecting optical materials such as a light guide plate, a polarizing plate, a retardation plate, and a prism sheet.
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| JP5028248B2 (en) * | 2007-12-21 | 2012-09-19 | 日本ポリエチレン株式会社 | Surface protection film |
| WO2010016403A1 (en) * | 2008-08-05 | 2010-02-11 | Dic株式会社 | Surface protection film |
| JP4529100B2 (en) * | 2008-08-20 | 2010-08-25 | Ｄｉｃ株式会社 | Surface protection film |
| JP5328557B2 (en) * | 2008-09-26 | 2013-10-30 | 日本ポリエチレン株式会社 | Laminated film for surface protection |
| WO2011034045A1 (en) * | 2009-09-15 | 2011-03-24 | 三井化学東セロ株式会社 | Surface protective film |
| JP5540669B2 (en) * | 2009-11-27 | 2014-07-02 | 日本ゼオン株式会社 | Roll wound body |
| JP6217171B2 (en) * | 2013-06-25 | 2017-10-25 | 大日本印刷株式会社 | Optical film transfer body, optical film, and image display device |
| KR101765300B1 (en) | 2015-06-03 | 2017-08-04 | 공진문 | Film Filling Method Of The Phase Change Material And The Film Manufactured Thereby |
| JP2018171808A (en) * | 2017-03-31 | 2018-11-08 | 三井化学株式会社 | Gas barrier laminate film |
| JP6853738B2 (en) * | 2017-06-13 | 2021-03-31 | 三菱瓦斯化学株式会社 | Polyurethane multilayer film |
| JP7240090B2 (en) * | 2017-10-03 | 2023-03-15 | 日東電工株式会社 | Polarizing plate, image display device, and method for manufacturing polarizing plate |
| JP6470829B1 (en) * | 2017-12-04 | 2019-02-13 | 住友化学株式会社 | Optical laminate and method for producing the same |
| CN112852313A (en) * | 2021-01-15 | 2021-05-28 | 东莞市金恒晟新材料科技有限公司 | Protective film convenient for adhesion |
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