JPH09111208A - Surface protecting film - Google Patents
Surface protecting filmInfo
- Publication number
- JPH09111208A JPH09111208A JP7265329A JP26532995A JPH09111208A JP H09111208 A JPH09111208 A JP H09111208A JP 7265329 A JP7265329 A JP 7265329A JP 26532995 A JP26532995 A JP 26532995A JP H09111208 A JPH09111208 A JP H09111208A
- Authority
- JP
- Japan
- Prior art keywords
- molecular weight
- average molecular
- temperature
- weight
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 239000011347 resin Substances 0.000 claims abstract description 30
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000005977 Ethylene Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000005194 fractionation Methods 0.000 claims abstract description 17
- 238000010828 elution Methods 0.000 claims abstract description 16
- 239000010410 layer Substances 0.000 claims description 28
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 17
- 230000001681 protective effect Effects 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000002685 polymerization catalyst Substances 0.000 claims description 10
- 229910052723 transition metal Inorganic materials 0.000 claims description 9
- 150000003624 transition metals Chemical class 0.000 claims description 9
- 239000012790 adhesive layer Substances 0.000 claims description 5
- 241000251468 Actinopterygii Species 0.000 abstract description 6
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000000470 constituent Substances 0.000 abstract description 2
- 238000001125 extrusion Methods 0.000 abstract description 2
- 239000004698 Polyethylene Substances 0.000 description 10
- -1 polyethylene Polymers 0.000 description 10
- 229920000573 polyethylene Polymers 0.000 description 10
- 239000000463 material Substances 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- JOLOSPPNXWGZBG-UHFFFAOYSA-N C[Ti]C1C=CC=C1 Chemical compound C[Ti]C1C=CC=C1 JOLOSPPNXWGZBG-UHFFFAOYSA-N 0.000 description 1
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- KZSQACPORPMQSL-UHFFFAOYSA-L [Cl-].[Cl-].[Hf+3].C[SiH](C)C(C(C(C)(C)C)(C)[N-]C1C=CC=C1)C Chemical compound [Cl-].[Cl-].[Hf+3].C[SiH](C)C(C(C(C)(C)C)(C)[N-]C1C=CC=C1)C KZSQACPORPMQSL-UHFFFAOYSA-L 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- JAGHDVYKBYUAFD-UHFFFAOYSA-L cyclopenta-1,3-diene;titanium(4+);dichloride Chemical compound [Cl-].[Cl-].[Ti+4].C1C=CC=[C-]1.C1C=CC=[C-]1 JAGHDVYKBYUAFD-UHFFFAOYSA-L 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- SRKKQWSERFMTOX-UHFFFAOYSA-N cyclopentane;titanium Chemical compound [Ti].[CH]1C=CC=C1 SRKKQWSERFMTOX-UHFFFAOYSA-N 0.000 description 1
- 208000028659 discharge Diseases 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、合成樹脂板などの
表面保護、特に偏光板や位相差板などの液晶表示の構成
部材の表面保護用として好適に使用される表面保護フィ
ルムに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface protective film which is preferably used for surface protection of synthetic resin plates and the like, and particularly for surface protection of components of liquid crystal displays such as polarizing plates and retardation plates.
【０００２】[0002]
【従来の技術】従来、表面保護フィルムとしては、基材
層の片面に溶剤を含む粘着剤組成物を塗布し、加熱・乾
燥して溶剤を除去したタイプ、基材層に熱溶融させた粘
着剤組成物を積層したタイプ、基材層を粘着剤組成物と
ともに熱溶融させて共押出ししたタイプがある。たとえ
ば特開昭５４−１３３５７８号公報においては、特定の
低密度ポリエチレン５０〜９０重量％と、重量平均分子
量／数平均分子量との比が９〜１５の特定の高密度ポリ
エチレン１０〜５０重量％とからなるポリエチレンと、
エチレン−不飽和エステル共重合体からなる接着性樹脂
層とを共押出しした積層フィルムが記載されている。2. Description of the Related Art Conventionally, as a surface protective film, a type in which a pressure-sensitive adhesive composition containing a solvent is applied to one surface of a base material layer, and the solvent is removed by heating and drying, a pressure-sensitive adhesive which is heat-melted to the base material layer. There are a type in which the agent composition is laminated and a type in which the base material layer is heat-melted together with the pressure-sensitive adhesive composition and coextruded. For example, in JP-A-54-133578, a specific low density polyethylene of 50 to 90% by weight and a specific high density polyethylene of 10 to 50% by weight of a weight average molecular weight / number average molecular weight ratio of 9 to 15 are used. Consisting of polyethylene,
A laminated film in which an adhesive resin layer made of an ethylene-unsaturated ester copolymer is coextruded is described.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、上記公
報に記載の積層フィルムにおいては、基材層を形成する
ポリエチレンは分子量分布が広く、つまり分子量の小さ
い低分子量のものと、分子量の大きい高分子量のものと
が混在している。そして、この高分子量のものが、共押
出ししてフイルムを成形する際に、未溶融の微細なかた
まり（以下、フィッシュアイという。）となってフィル
ム中に存在することになる。この結果、積層フィルムを
被保護物に貼付けた後、そのままの状態で段積み保管し
た場合、上記フィッシュアイの存在により、被保護物に
凹みが生じる。したがって、たとえば液晶表示材として
使用される偏光板や位相差板として上記積層フィルムを
使用しようとしても、凹みがあることにより画像に歪み
が生じるので、適用できないという問題があった。However, in the laminated film described in the above publication, the polyethylene forming the base material layer has a wide molecular weight distribution, that is, a low molecular weight polyethylene having a small molecular weight and a high molecular weight polyethylene having a large molecular weight. Things and things are mixed. This high molecular weight substance is present in the film as an unmelted fine lump (hereinafter referred to as fish eye) when the film is formed by coextrusion. As a result, when the laminated films are attached to the object to be protected and then stacked and stored as they are, the presence of the fish eyes causes a dent in the object to be protected. Therefore, even if an attempt is made to use the above-mentioned laminated film as a polarizing plate or a retardation plate used as a liquid crystal display material, the image is distorted due to the dents, which is not applicable.
【０００４】本発明は、上記フィッシュアイが発生せ
ず、偏光板や位相差板などの液晶表示の構成部材の表面
保護用のフィルムとして好適な表面保護フィルムを提供
することを目的とするものである。It is an object of the present invention to provide a surface protective film which does not generate the above fisheyes and is suitable as a film for protecting the surface of a liquid crystal display component such as a polarizing plate or a retardation plate. is there.
【０００５】[0005]
【課題を解決するための手段】請求項１記載の本発明の
表面保護フィルムは、エチレン系樹脂製の基材フィルム
の片面に粘着剤層が形成された表面保護フィルムにおい
て、前記エチレン系樹脂が、クロス分別法によって１０
重量％溶出したときの温度から１００重量％溶出終了し
たときの温度の幅が３０℃以下であり、かつ、重量平均
分子量／数平均分子量の値が１．５〜３．５であるもの
である。The surface protective film of the present invention according to claim 1 is a surface protective film in which an adhesive layer is formed on one surface of a base film made of an ethylene resin, wherein the ethylene resin is , 10 by cross fractionation
The temperature range from the temperature at the time of elution by weight% to the temperature at the end of 100% by weight elution is 30 ° C. or less, and the value of weight average molecular weight / number average molecular weight is 1.5 to 3.5. .
【０００６】また、請求項２記載の本発明の表面保護フ
ィルムは、エチレン系樹脂製の基材フィルムの片面に粘
着剤層が形成された表面保護フィルムにおいて、前記エ
チレン系樹脂が、重合触媒として四価の遷移金属を含む
メタロセン化合物を用いて得られたものである。The surface protective film of the present invention according to claim 2 is a surface protective film in which an adhesive layer is formed on one side of a base film made of an ethylene resin, wherein the ethylene resin serves as a polymerization catalyst. It was obtained using a metallocene compound containing a tetravalent transition metal.
【０００７】さらに、請求項３記載の本発明の表面保護
フィルムは、エチレン系樹脂製の基材フイルムの片面に
粘着剤層が形成された表面保護フィルムにおいて、前記
エチレン系樹脂が、重合触媒として四価の遷移金属を含
むメタロセン化合物を用いて得られたものであり、しか
も、クロス分別法によって１０重量％溶出したときの温
度から１００重量％溶出終了したときの温度の幅が３０
℃以下であり、かつ、重量平均分子量／数平均分子量の
値が１．５〜３．５であるものである。Furthermore, the surface protective film of the present invention according to claim 3 is a surface protective film in which an adhesive layer is formed on one side of a base film made of an ethylene resin, wherein the ethylene resin serves as a polymerization catalyst. It was obtained using a metallocene compound containing a tetravalent transition metal, and the temperature range from the temperature at the time of elution of 10% by weight to the completion of the elution of 100% by weight by the cross fractionation method was 30.
C. or less, and the value of weight average molecular weight / number average molecular weight is 1.5 to 3.5.
【０００８】（作用）請求項１〜３記載の本発明の表面
保護フィルムは、上述のとおり、粘着剤層が形成される
基材フィルムが特定のエチレン系樹脂製のものであるの
で、樹脂の分子量分布が狭く、フィルム成形時に未溶融
のフィッシュアイが存在せず、このため、表面保護フィ
ルムを被保護物に貼付けて段積み保管しても、被保護物
に凹みが生じることがない。(Function) In the surface protective film of the present invention according to claims 1 to 3, since the base film on which the pressure-sensitive adhesive layer is formed is made of a specific ethylene resin, as described above, The molecular weight distribution is narrow, and unmelted fish eyes do not exist at the time of film formation. Therefore, even if the surface protection film is stuck on the object to be protected and stacked, the object to be protected does not have a dent.
【０００９】[0009]
【発明の実施の形態】本発明において使用される基材フ
ィルムはエチレン系樹脂製のものであり、このエチレン
系樹脂としては、エチレンの単独重合体、あるいはエチ
レンとα−オレフィンとの共重合体を使用することがで
きる。ここで、共重合成分のα−オレフィンとしては、
プロピレン、１−ブテン、１−ペンテン、１−ヘキセ
ン、４−メチル−１−ペンテン、１−ヘプテン、１−オ
クテンなどが挙げられる。BEST MODE FOR CARRYING OUT THE INVENTION The base film used in the present invention is made of an ethylene resin, and the ethylene resin may be a homopolymer of ethylene or a copolymer of ethylene and α-olefin. Can be used. Here, as the α-olefin of the copolymerization component,
Propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene and the like can be mentioned.
【００１０】そして、本発明においては、上記エチレン
系樹脂はつぎの〜のいずれかの条件を満足するもの
である。 クロス分別法によって１０重量％溶出したときの温度
から１００重量％溶出終了したときの温度の幅が３０℃
以下であり、かつ、重量平均分子量／数平均分子量の値
が１．５〜３．５であるもの。 重合触媒として四価の遷移金属を含むメタロセン化合
物を用いて得られたもの。 重合触媒として四価の遷移金属を含むメタロセン化合
物を用いて得られたものであり、しかも、クロス分別法
によって１０重量％溶出したときの温度から１００重量
％溶出終了したときの温度の幅が３０℃以下であり、か
つ、重量平均分子量／数平均分子量の値が１．５〜３．
５であるもの。In the present invention, the ethylene resin satisfies any of the following conditions (1) to (3). The width of the temperature at the time of elution by 10% by weight by the cross fractionation method to the temperature at the end of 100% by weight elution is 30 ° C.
It is the following and the value of weight average molecular weight / number average molecular weight is 1.5 to 3.5. Obtained by using a metallocene compound containing a tetravalent transition metal as a polymerization catalyst. It was obtained by using a metallocene compound containing a tetravalent transition metal as a polymerization catalyst, and the temperature range from the temperature at the time of elution of 10% by weight to the end of the time of 100% by weight dissolution by the cross fractionation method was 30. C. or less, and the value of weight average molecular weight / number average molecular weight is 1.5 to 3.
What is 5.
【００１１】本発明において採用しているクロス分別法
とは以下に示す方法である。まず、エチレン系樹脂を１
４０℃あるいはエチレン系樹脂が完全に溶解する温度の
ｏ−ジクロロベンゼンに溶解し、ついで一定速度で冷却
し、あらかじめ用意しておいた不活性担体の表面に、薄
いポリマー層を結晶性の高い順および分子量の大きい順
に生成させる。つぎに、温度を連続的または段階的に昇
温し、順次溶出した成分の濃度を検出して、組成分布
（結晶性分布）を測定する。これを温度上昇溶離分別
（Ｔｅｍｐｅｒａｔｕｒｅ Ｒｉｓｉｎｇ Ｅｌｕｔｉ
ｏｎ Ｆｒａｃｔｉｏｎａｔｉｏｎ；ＴＲＥＦ）とい
う。同時に、順次溶出した成分を高温型ゲルパーミエー
ションクロマトグラフ（Ｓｉｚｅ Ｅｘｃｌｕｓｉｏｎ
Ｃｈｒｏｍａｔｏｇｒａｐｈ；ＳＥＣ）により分析し
て、分子量と分子量分布を測定する。本発明において
は、上記温度上昇溶離分別部分と高温型ゲルパーミエー
ションクロマトグラフ部分の両者をシステムとして備え
ているクロス分別クロマトグラフ装置（三菱化学社製Ｃ
ＦＣ−Ｔ１５０Ａ型）を用いて、データを測定した。The cross fractionation method used in the present invention is the following method. First, 1 ethylene resin
It is dissolved in o-dichlorobenzene at 40 ° C or a temperature at which the ethylene resin is completely dissolved, and then cooled at a constant rate, and a thin polymer layer is formed on the surface of an inert carrier prepared in advance in order of high crystallinity. And in descending order of molecular weight. Next, the temperature is continuously or stepwise raised, the concentrations of the components that are sequentially eluted are detected, and the composition distribution (crystallinity distribution) is measured. This is the temperature rising elution fractionation (Temperature Rising Eluti
on Fractionation (TREF). At the same time, the components that have been sequentially eluted are analyzed by a high temperature gel permeation chromatograph
Chromatograph; SEC) to determine the molecular weight and molecular weight distribution. In the present invention, a cross fractionation chromatograph device (C manufactured by Mitsubishi Chemical Co., Ltd.) equipped with both the above-mentioned temperature rising elution fractionation part and high temperature type gel permeation chromatograph part as a system.
The data were measured using FC-T150A type).
【００１２】本発明におけるエチレン系樹脂は上記クロ
ス分別法によって１０重量％溶出したときの温度から１
００重量％溶出終了したときの温度の幅が３０℃以下、
好ましくは２８℃以下であるものである。これは上記温
度幅が３０℃を越えると、エチレン系樹脂の中に結晶性
の高い成分と結晶性の低い成分とが同時に存在すること
になり、このため、溶融樹脂粘度にムラが存在し、外観
的に均一なフィルムを得ることができないからである。The ethylene resin in the present invention has a temperature of 1% by weight when it is eluted by 10% by weight by the above cross fractionation method.
The width of the temperature at the end of the dissolution of 00 wt% is 30 ° C or less,
It is preferably 28 ° C or lower. This means that when the temperature range exceeds 30 ° C., a component having high crystallinity and a component having low crystallinity are present at the same time in the ethylene-based resin, so that the viscosity of the molten resin is uneven, This is because a film having a uniform appearance cannot be obtained.
【００１３】また、本発明におけるエチレン系樹脂は上
記条件に加え、重量平均分子量／数平均分子量の値が
１．５〜３．５、好ましくは１．７〜３．０であるもの
である。これは、重量平均分子量／数平均分子量の値が
１．５未満であると、溶融樹脂粘度が高くなって溶融流
動性が悪くなり、押出成形が困難となるからである。一
方、重量平均分子量／数平均分子量の値が３．５を越え
ると、分子量の小さい分子および分子量の大きい分子の
存在比率が高くなり、高分子量分はフイルム成形時に未
溶融のフィッシュアイとなり、被保護物に貼付けた後、
そのままの状態で段積み保管すると、被保護物に凹みを
生じることになるからである。In addition to the above conditions, the ethylene resin in the present invention has a weight average molecular weight / number average molecular weight value of 1.5 to 3.5, preferably 1.7 to 3.0. This is because if the value of the weight average molecular weight / number average molecular weight is less than 1.5, the viscosity of the molten resin becomes high and the melt fluidity deteriorates, making extrusion molding difficult. On the other hand, when the value of the weight average molecular weight / number average molecular weight exceeds 3.5, the abundance ratio of the molecules having a small molecular weight and the molecules having a large molecular weight becomes high, and the high molecular weight component becomes unmelted fish eyes during film forming, After sticking on the protection,
This is because if they are stacked and stored as they are, the object to be protected will have a dent.
【００１４】さらに、本発明におけるエチレン系樹脂
は、四価の遷移金属を含むメタロセン化合物を重合触媒
として用いて得られたものであり、分子量分布が狭く、
しかも、共重合体の場合は、どの分子量成分にも共重合
体成分がほぼ等しい割合で導入されている。ここで四価
の遷移金属を含むメタロセン化合物とは、チタン、ジル
コニウム、ニッケル、パラジウム、ハフニウム、白金な
どの四価の遷移金属に、１個以上のシクロペンタジエニ
ル環またはその類縁体が配位子として存在するものであ
り、シクロペンタジエニルチタニウムトリス（ジメチル
アミド）、メチルシクロペンタジエニルチタニウムトリ
ス（ジメチルアミド）、ビス（シクロペンタジエニル）
チタニウムジクロリド、ジメチルシリルテトラメチルシ
クロペンタジエニル−ｔｅｒｔ−ブチルアミドハフニウ
ムジクロリドなどが挙げられる。なお、このメタロセン
化合物と一緒に、メチルアルミノキサンやホウ素系化合
物を共触媒として併用してもよい。そして、重合方法と
しては、不活性媒体を用いる溶液重合法、実質的に不活
性媒体の存在しない塊状重合法、気相重合法などが利用
できるが、本発明におけるエチレン系樹脂は、これらの
いずれの重合方法で得られたものでもよい。上記メタロ
セン化合物を重合触媒として用いて得られたポリエチレ
ンとしては、ダウ・ケミカル社のＣＧＣＴやエクソン・
ケミカル社のＥＸＡＣＴなどが市販されている。Further, the ethylene resin of the present invention is obtained by using a metallocene compound containing a tetravalent transition metal as a polymerization catalyst, and has a narrow molecular weight distribution,
Moreover, in the case of the copolymer, the copolymer component is introduced into almost any of the molecular weight components in a substantially equal ratio. Here, the metallocene compound containing a tetravalent transition metal refers to a tetravalent transition metal such as titanium, zirconium, nickel, palladium, hafnium, or platinum coordinated with one or more cyclopentadienyl rings or its analogs. Existing as a child, cyclopentadienyl titanium tris (dimethylamide), methylcyclopentadienyl titanium tris (dimethylamide), bis (cyclopentadienyl)
Titanium dichloride, dimethylsilyl tetramethylcyclopentadienyl-tert-butylamide hafnium dichloride and the like can be mentioned. In addition, a methylaluminoxane or a boron-based compound may be used as a cocatalyst together with the metallocene compound. And, as the polymerization method, a solution polymerization method using an inert medium, a bulk polymerization method in which substantially no inert medium is present, a gas phase polymerization method and the like can be used. It may be obtained by the above polymerization method. Examples of polyethylene obtained by using the metallocene compound as a polymerization catalyst include CGCT and Exxon
EXACT manufactured by Chemicals, Inc. is commercially available.
【００１５】上記基材フィルムの厚みは、特に限定され
ないが、２０〜２００μｍ、好ましくは４０〜１００μ
ｍである。The thickness of the substrate film is not particularly limited, but is 20 to 200 μm, preferably 40 to 100 μm.
m.
【００１６】本発明においては、上記基材フィルムの片
面に粘着剤層が形成されているが、この粘着剤として
は、特に限定されず、たとえばゴム系粘着剤、アクリル
系粘着剤などが好適に使用される。特に、エチレン酢酸
ビニル共重合体（ＥＶＡ）、スチレンブタジエンブロッ
ク共重合体（ＳＢＳ）、スチレンイソプレンブロック共
重合体（ＳＩＳ）などを主成分とするものが好ましい。
また、必要に応じて粘着付与樹脂、酸化防止剤、難燃
剤、顔料などを加えてもよい。この粘着剤層を基材フィ
ルムの片面に設ける手段としては、たとえば加熱溶融し
て積層する方法、あるいは両者を加熱溶融させて、Ｔダ
イにより２層共押出しする方法を採用すればよい。粘着
剤層の厚みは５〜４０μｍとするのがよい。In the present invention, a pressure-sensitive adhesive layer is formed on one surface of the base film, but the pressure-sensitive adhesive is not particularly limited, and for example, a rubber-based pressure-sensitive adhesive or an acrylic pressure-sensitive adhesive is suitable. used. In particular, those containing ethylene vinyl acetate copolymer (EVA), styrene butadiene block copolymer (SBS), styrene isoprene block copolymer (SIS), etc. as main components are preferable.
In addition, tackifier resins, antioxidants, flame retardants, pigments and the like may be added if necessary. As a means for providing this pressure-sensitive adhesive layer on one surface of the substrate film, for example, a method of heating and melting and laminating, or a method of heating and melting both and coextruding two layers by a T die may be adopted. The pressure-sensitive adhesive layer preferably has a thickness of 5 to 40 μm.
【００１７】本発明において使用される基材フィルムと
粘着剤層との親和力を向上させるため、基材フィルムの
表面に従来公知のコロナ放電処理、プラズマ放電処理な
どが施されていてもよい。In order to improve the affinity between the base film used in the present invention and the pressure-sensitive adhesive layer, the surface of the base film may be subjected to conventionally known corona discharge treatment, plasma discharge treatment or the like.
【００１８】[0018]
【実施例】以下、本発明の実施例を具体的に説明する
が、本発明はこれらの実施例に限定されるものではな
い。EXAMPLES Examples of the present invention will be specifically described below, but the present invention is not limited to these examples.
【００１９】（実施例１）メタロセン化合物を重合触媒
として用いて得られたポリエチレン（商品名「ＥＸＡＣ
Ｔ３０２７」、密度＝０．９００ｇ／ｃｍ3 、重量平均
分子量／数平均分子量＝２．０、エクソン・ケミカル社
製）を基材フイルム層の原料とし、ＥＶＡ（商品名「Ｅ
ＶＡ５４０」、酢酸ビニル含有量＝１０％、ＭＩ＝３、
密度＝０．９２７ｇ／ｃｍ3 、東ソー社製）を粘着剤層
の原料として用い、基材フィルム層の厚みが４０μｍ、
粘着剤層の厚みが２０μｍとなるように、フィードブロ
ック方式によるＴダイによる２層共押出し成形法にて厚
み６０μｍの表面保護フィルムを得た。なお、成形条件
はつぎに示すとおりである。 ・基材フィルム原料の押出機のシリンダー設定温度：１５０℃ ・粘着剤原料の押出機のシリンダー設定温度 ：１５０℃ ・フィードブロック部の設定温度 ：１７０℃ ・金型の設定温度 ：１９０℃ ・Ｔダイのリップクリアランス ：１ｍｍ また、使用したポリエチレンのクロス分別法による測定
結果は表１に示すとおりである。(Example 1) Polyethylene (trade name "EXAC" obtained using a metallocene compound as a polymerization catalyst
T3027 ", density = 0.900 g / cm 3 , weight average molecular weight / number average molecular weight = 2.0, manufactured by Exxon Chemical Co., Ltd., is used as a raw material for the base film layer, and EVA (trade name" E
VA540 ", vinyl acetate content = 10%, MI = 3,
Density = 0.927 g / cm 3 , manufactured by Tosoh Corporation) as a raw material for the pressure-sensitive adhesive layer, and the thickness of the base film layer is 40 μm.
A surface protection film having a thickness of 60 μm was obtained by a two-layer coextrusion molding method using a T die by a feed block method so that the pressure-sensitive adhesive layer had a thickness of 20 μm. The molding conditions are as follows.・ Cylinder setting temperature of extruder for base material film: 150 ° C ・ Cylinder setting temperature of extruder for adhesive material: 150 ° C ・ Feed block part setting temperature: 170 ° C ・ Mold setting temperature: 190 ° C ・ T Die lip clearance: 1 mm Further, the measurement results of the polyethylene used by the cross fractionation method are shown in Table 1.
【００２０】（実施例２）メタロセン化合物を重合触媒
として用いて得られたポリエチレン（商品名「ＥＸＡＣ
Ｔ４０１１」、密度＝０．８８５ｇ／ｃｍ3 、重量平均
分子量／数平均分子量＝２．１、エクソン・ケミカル社
製）を基材フィルム層の原料とし、ＥＶＡ（商品名「Ｅ
ＶＡ５４０」、酢酸ビニル含有量＝１０％、ＭＩ＝３、
密度＝０．９２７ｇ／ｃｍ3 、東ソー社製）を粘着剤層
の原料として用い、基材フィルム層の厚みが４０μｍ、
粘着剤層の厚みが２０μｍとなるように、Ｔダイによる
２層共押出し成形法にて厚み６０μｍの表面保護フィル
ムを得た。なお、成形条件は上記実施例１と同一であ
る。また、使用したポリエチレンのクロス分別法による
測定結果は表１に示すとおりである。(Example 2) Polyethylene (trade name "EXAC" obtained using a metallocene compound as a polymerization catalyst
T4011, "density = 0.885 g / cm 3 , weight average molecular weight / number average molecular weight = 2.1, manufactured by Exxon Chemical Co., Ltd., was used as a raw material for the base film layer, and EVA (trade name" E "
VA540 ", vinyl acetate content = 10%, MI = 3,
Density = 0.927 g / cm 3 , manufactured by Tosoh Corporation) as a raw material for the pressure-sensitive adhesive layer, and the thickness of the base film layer is 40 μm.
A surface protection film having a thickness of 60 μm was obtained by a two-layer coextrusion molding method using a T die so that the pressure-sensitive adhesive layer had a thickness of 20 μm. The molding conditions are the same as in Example 1 above. The measurement results of the polyethylene used by the cross fractionation method are shown in Table 1.
【００２１】（比較例１）三塩化チタン系触媒を用いて
得られた直鎖状低密度ポリエチレン（商品名「１０４４
Ｄ」、密度＝０．９２５ｇ／ｃｍ3 、重量平均分子量／
数平均分子量＝４．０、出光石油化学社製）を基材フィ
ルム層の原料として用いる以外は上記実施例１と同様に
して、Ｔダイによる２層共押出し成形法にて厚み６０μ
ｍの表面保護フィルムを得た。なお、成形条件は上記実
施例１と同一である。また、使用したポリエチレンのク
ロス分別法による測定結果は表１に示すとおりである。(Comparative Example 1) Linear low-density polyethylene (trade name "1044" obtained using a titanium trichloride-based catalyst)
D ", density = 0.925 g / cm 3 , weight average molecular weight /
A number average molecular weight = 4.0, manufactured by Idemitsu Petrochemical Co., Ltd.) was used as a raw material for the base film layer, and the thickness was 60 μm by a two-layer coextrusion method using a T-die in the same manner as in Example 1 above.
m surface protection film was obtained. The molding conditions are the same as in Example 1 above. The measurement results of the polyethylene used by the cross fractionation method are shown in Table 1.
【００２２】（比較例２）三塩化チタン系触媒を用いて
得られた直鎖状低密度ポリエチレン（商品名「４３−
１」、密度＝０．９０５ｇ／ｃｍ3 、重量平均分子量／
数平均分子量＝４．４、出光石油化学社製）を基材フィ
ルム層の原料として用いる以外は上記実施例１と同様に
して、Ｔダイによる２層共押出し成形法にて厚み６０μ
ｍの表面保護フィルムを得た。なお、成形条件は上記実
施例１と同一である。また、使用したポリエチレンのク
ロス分別法による測定結果は表１に示すとおりである。(Comparative Example 2) A linear low-density polyethylene (trade name "43-
1 ", density = 0.905 g / cm 3 , weight average molecular weight /
The number average molecular weight = 4.4, manufactured by Idemitsu Petrochemical Co., Ltd.) was used as a raw material for the base film layer, and the thickness was 60 μm by a two-layer coextrusion molding method using a T-die in the same manner as in Example 1 above.
m surface protection film was obtained. The molding conditions are the same as in Example 1 above. The measurement results of the polyethylene used by the cross fractionation method are shown in Table 1.
【００２３】上述のようにして得られた表面保護フィル
ムを、真夏の倉庫内に段積み保管されることを想定し、
以下に示す測定方法にて、ポリカーボネート板（以下、
ＰＣ板という。）の凹みの数をカウントした。 （測定方法）厚さ２ｍｍ、縦１５０ｍｍ、横１００ｍｍ
のＰＣ板に、表面保護フィルムをラミネーターで貼付
け、１５０ｍｍ×１００ｍｍ当たり５００ｇの加重をか
けて、４０℃の熱風循環式オーブン中に４８時間放置す
る。４８時間後に取り出して常温に自然冷却した後、表
面保護フィルムを剥がし、そのＰＣ板の表面状態を倍率
が２０倍のルーペにて観察し、１５０ｍｍ×１００ｍｍ
当たりの凹みの数をカウントする。その結果は、実施例
１および２ではともに０個であるのに対し、比較例１で
は５５個、比較例２では４３個であった。Assuming that the surface protective film obtained as described above is stacked and stored in a warehouse in midsummer,
In the measurement method shown below, a polycarbonate plate (hereinafter,
It is called a PC board. ) Counted the number of dents. (Measurement method) Thickness 2 mm, length 150 mm, width 100 mm
The surface protection film is attached to the PC plate of No. 2 by a laminator, a weight of 500 g per 150 mm × 100 mm is applied, and the plate is left in a hot air circulation oven at 40 ° C. for 48 hours. After 48 hours, it was taken out and naturally cooled to room temperature, then the surface protection film was peeled off, and the surface condition of the PC board was observed with a magnifying power of 20 times, 150 mm × 100 mm
Count the number of dents per hit. The results were 0 in both Examples 1 and 2, but 55 in Comparative Example 1 and 43 in Comparative Example 2.
【００２４】[0024]
【表１】 （脚注） ＊１：Ｍｗ＝重量平均分子量、Ｍｎ＝数平均分子量 ＊２：Ｔ1 ＝ＳＥＣ分析による全樹脂の１０重量％が溶
出する温度 Ｔ2 ＝ＳＥＣ分析による全樹脂の溶出終了温度[Table 1] (Footnote) * 1: Mw = weight average molecular weight, Mn = number average molecular weight * 2: T 1 = temperature at which 10% by weight of all resins by SEC analysis elutes T 2 = elution end temperature of all resins by SEC analysis
【００２５】[0025]
【発明の効果】請求項１〜３記載の本発明の表面保護フ
ィルムは、上述のとおり、粘着剤層が形成される基材フ
ィルムが特定のエチレン系樹脂製のものであるので、樹
脂の分子量分布が狭く、フィルム成形時に未溶融のフィ
ッシュアイが存在せず、このため、表面保護フィルムを
被保護物に貼付けて段積み保管しても、被保護物に凹み
が生じることがない。したがって、偏光板や位相差板な
どの構成部材の表面保護用のフィルムとして好適なもの
である。As described above, in the surface protective film of the present invention according to claims 1 to 3, the base material film on which the pressure-sensitive adhesive layer is formed is made of a specific ethylene resin, so that the molecular weight of the resin is The distribution is narrow, and unmelted fish eyes do not exist at the time of forming the film. Therefore, even when the surface protection film is stuck on the object to be protected and stacked, the object to be protected does not have a dent. Therefore, it is suitable as a film for surface protection of constituent members such as a polarizing plate and a retardation plate.
Claims (3)
に粘着剤層が形成された表面保護フィルムにおいて、前
記エチレン系樹脂が、クロス分別法によって１０重量％
溶出したときの温度から１００重量％溶出終了したとき
の温度の幅が３０℃以下であり、かつ、重量平均分子量
／数平均分子量の値が１．５〜３．５であることを特徴
とする表面保護フィルム。1. A surface protective film having an adhesive layer formed on one side of a base film made of an ethylene resin, wherein the ethylene resin is 10% by weight by a cross fractionation method.
The temperature range from the temperature at the time of elution to 100% by weight at the time of completion of elution is 30 ° C. or less, and the value of weight average molecular weight / number average molecular weight is 1.5 to 3.5. Surface protection film.
に粘着剤層が形成された表面保護フィルムにおいて、前
記エチレン系樹脂が、重合触媒として四価の遷移金属を
含むメタロセン化合物を用いて得られたものであること
を特徴とする表面保護フィルム。2. A surface protective film having an adhesive layer formed on one surface of a base film made of an ethylene resin, wherein the ethylene resin is obtained by using a metallocene compound containing a tetravalent transition metal as a polymerization catalyst. A surface protective film, which is characterized in that
に粘着剤層が形成された表面保護フィルムにおいて、前
記エチレン系樹脂が、重合触媒として四価の遷移金属を
含むメタロセン化合物を用いて得られたものであり、し
かも、クロス分別法によって１０重量％溶出したときの
温度から１００重量％溶出終了したときの温度の幅が３
０℃以下であり、かつ、重量平均分子量／数平均分子量
の値が１．５〜３．５であることを特徴とする表面保護
フィルム。3. A surface protective film having a pressure-sensitive adhesive layer formed on one surface of a base film made of an ethylene resin, wherein the ethylene resin is obtained by using a metallocene compound containing a tetravalent transition metal as a polymerization catalyst. In addition, the width of the temperature at the time of elution of 10 wt% by the cross fractionation method to the temperature at the end of 100 wt% elution was 3
A surface protective film having a temperature of 0 ° C. or lower and a weight average molecular weight / number average molecular weight value of 1.5 to 3.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26532995A JP3510719B2 (en) | 1995-10-13 | 1995-10-13 | Surface protection film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26532995A JP3510719B2 (en) | 1995-10-13 | 1995-10-13 | Surface protection film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09111208A true JPH09111208A (en) | 1997-04-28 |
| JP3510719B2 JP3510719B2 (en) | 2004-03-29 |
Family
ID=17415685
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26532995A Expired - Lifetime JP3510719B2 (en) | 1995-10-13 | 1995-10-13 | Surface protection film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3510719B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009274231A (en) * | 2008-05-12 | 2009-11-26 | Japan Polypropylene Corp | Propylene-based surface protective film |
| JP2010042667A (en) * | 2008-07-15 | 2010-02-25 | Japan Polypropylene Corp | Propylene-based surface protective film |
| WO2011129167A1 (en) | 2010-04-13 | 2011-10-20 | 東レフィルム加工株式会社 | Surface protective film |
| JP2015130395A (en) * | 2014-01-07 | 2015-07-16 | 三菱樹脂株式会社 | Substrate film for dicing tape and dicing tape |
| WO2022015094A1 (en) | 2020-07-16 | 2022-01-20 | 주식회사 엘지화학 | Transition metal compound and catalyst composition including same |
-
1995
- 1995-10-13 JP JP26532995A patent/JP3510719B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009274231A (en) * | 2008-05-12 | 2009-11-26 | Japan Polypropylene Corp | Propylene-based surface protective film |
| JP2010042667A (en) * | 2008-07-15 | 2010-02-25 | Japan Polypropylene Corp | Propylene-based surface protective film |
| WO2011129167A1 (en) | 2010-04-13 | 2011-10-20 | 東レフィルム加工株式会社 | Surface protective film |
| JP5761571B2 (en) * | 2010-04-13 | 2015-08-12 | 東レフィルム加工株式会社 | Surface protection film |
| JP2015130395A (en) * | 2014-01-07 | 2015-07-16 | 三菱樹脂株式会社 | Substrate film for dicing tape and dicing tape |
| WO2022015094A1 (en) | 2020-07-16 | 2022-01-20 | 주식회사 엘지화학 | Transition metal compound and catalyst composition including same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3510719B2 (en) | 2004-03-29 |
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