JP3560006B2 - Surface protection film - Google Patents
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- JP3560006B2 JP3560006B2 JP32046895A JP32046895A JP3560006B2 JP 3560006 B2 JP3560006 B2 JP 3560006B2 JP 32046895 A JP32046895 A JP 32046895A JP 32046895 A JP32046895 A JP 32046895A JP 3560006 B2 JP3560006 B2 JP 3560006B2
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Description
【0001】
【発明の属する技術分野】
本発明は、ステンレス板、アルミ板等の金属板、塗装した金属板、合成樹脂板、ガラス板、塩化ビニルラミネート鋼板等の表面保護フイルムに関するものであって、特に、エンボス板、マット板に加工した、表面あるいはヘアーライン加工した表面を保護する表面保護フイルムに関するものである。
【0002】
【従来の技術】
従来から、表面保護フィルムとして、金属板、合成樹脂板、化粧板等の切削加工、運搬・輸送時の表面に傷が付くのを防止するためにポリ塩化ビニル、ポリエチレン、ポリプロピレンなどの基材フィルムあるいは紙の片面にエチレン・酢酸ビニル共重合体、アクリル系樹脂、天然ゴム等を主成分とする粘着層が設けられた表面保護フィルムが多く使用されている。
【0003】
また、金属板、合成樹脂板、化粧板等の片面あるいは両面の表面をヘアライン加工、マット加工、エンボス加工した、表面に凹凸を有する樹脂板に対しては、室温で塑性変形しやすい粘着剤として糊引きといわれる天然ゴム等と粘着付与剤とを溶剤に溶解しバーコート等により基材フィルムに塗布した表面保護フィルムが用いられている。
【0004】
ところで、表面粗さの異なる凹凸を有する表面に対して適度な粘着力を有し、高温に曝されたり、長期にわたって被着されても粘着力の経時変化が生じず、不要時には容易に剥離できて糊残りがなく、基材の破断が起こらない、あるいは、焼却しても塩素ガスを放出しない、あるいは、溶剤を用いない表面保護フィルムが望まれていた。
【0005】
そこで、上記問題点を解決するため、特公昭58−30911号公報、特開昭61−103975号公報にポリオレフィンなどの基材フィルムの片面に、一般式A−B(ここで、Aはスチレン重合体ブロックを示し、Bはブタジエン重合体ブロック、イソプレン重合体ブロック、又はエチレン・ブチレン共重合体ブロックを示す)のブロック共重合体と粘着付与樹脂とを混和した粘着剤層が形成された表面保護フィルムが開示されている。
【0006】
ところが、ブロック共重合体と粘着付与樹脂とからなる粘着剤層を上記表面保護フィルムに貼着すると粘着剤組成中のブロック共重合体の含有量が多いために、貼着後の粘着力がすでに高く、輸送・保管で経時変化した場合、被着体を積み重ねした場合、40℃程度の高温下に放置した場合、さらに粘着力が上昇して剥離しにくい問題があった。
【0007】
それらを改善する方法として、特開平6−240216公報にエチレン−αオレフィン共重合体および/またはプロピレン−αオレフィン共重合体とブロック型スチレン系共重合体と粘着付与樹脂とを主成分とする粘着剤層により、高温に曝されたり、長期に被着されても粘着力の経時的な上昇が起こらない表面保護フィルムが開示されている。
【0008】
しかしながら、この表面保護フィルムは、金属板、合成樹脂板、化粧板等の鏡面板あるいは中心平均粗さの小さい(例えば、1μm未満)、比較的なめらかな表面に対しては、有効であるが、表面をヘアライン加工、マット加工、エンボス加工した凹凸を有する金属板、樹脂板(例えば、中心線平均粗さ(JIS−B0601)Raが1〜3μmのもの)に対しては、粘着しにくい問題があった。
【0009】
【発明が解決しようとする課題】
本発明は、上記の欠点を解決する目的で鋭意検討を行った結果、適度な初期粘着力(100g〜400g/50mm)を有し、高温に曝されたり、長期に被着されても粘着力の経時的な上昇が起こらず、かつ、不要時には容易に剥離できて被着体に糊残りがなく、基材の破断が起こらない表面保護フィルムを提供することを目的とする。
【0010】
【課題を解決するための手段】
この目的に沿う本発明は、ポリオレフィン系樹脂からなる基材フィルムの片面に粘着剤層が形成され、該粘着剤層の主成分がスチレン系ランダム共重合体の水素添加樹脂とエチレン−αオレフィン共重合体エラストマーとからなることを特徴とする表面保護フィルムである。
【0011】
【発明の実施の形態】
本発明において、基材フィルムを形成するポリオレフィン系樹脂としては、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(LLD−PE)、エチレン−αオレフィン共重合体、エチレン−エチルアクリレート共重合体、エチレン−酢酸ビニル共重合体、エチレン−メチルメタクリレート共重合体、エチレン−nブチルアクリレート共重合体、ポリプロピレンなどを用いることができ、これらのポリオレフィン系樹脂の2種以上の混合物が使用されてもよい。
【0012】
本発明の粘着剤層に使用されるスチレン系ランダム共重合体の水素添加樹脂とは、スチレン系モノマ7〜45重量%、好ましくは7〜35重量%とブタジエン93〜55重量%、好ましくは93〜65重量%との共重合体の水素添加樹脂である。スチレン系モノマ量が7重量%未満になると樹脂としての取扱い性が悪くなり、スチレン系モノマ量が45重量%を超えると樹脂として硬くなる。さらに、共重合体の水素添加率は95%以上、好ましくは97%以上である。また、これらの樹脂には重合法によりブロック型とランダム型があるが、凹凸を有するエンボス板、マット板への粘着性の点でランダム型が好ましい。
【0013】
スチレン系共重合体水素添加樹脂のブロック型タイプとは、スチレンあるいはα−メチルスチレンとブタジエンのブロック共重合体を水素添加したものである。スチレンとブタジエンのブロック共重合体を水素添加したものは通称SEBS(スチレン・エチレン・ブタジエン・スチレン)樹脂と呼ばれる。また、スチレン系共重合体の水素添加樹脂のランダム型タイプとはポリスチレンあるいはα−メチルポリスチレンのブロック(a)とスチレンあるいはα−メチルスチレンとブタジエンのランダム共重合体ブロック(b)、必要に応じてスチレンあるいはα−メチルスチレンとブタジエンのテーパーブロック(c)からなり、これらがブロック的に結合したブロック共重合体のことである。
【0014】
また、スチレン系共重合体水素添加樹脂のランダム型タイプとブロック型タイプとの違いは、ブロック型タイプは、ポリスチレンあるいはα−メチルポリスチレンのブロック(a)に相当する100℃付近のガラス転移温度が検出されるのに対して、ランダム型タイプは、(a)に相当するガラス転移温度が検出されない点にある。
【0015】
本発明の粘着剤層に使用されるエチレン−αオレフィン共重合体エラストマーとは、エチレン含有量が30重量%以上、好ましくは40重量%以上、さらに好ましくは50重量%以上であって、プロピレン、ブテン−1、ヘキセン−1、4−メチルペンテン−1、オクテン−1が共重合された共重合体エラストマー、即ち、非結晶性〜低結晶性の共重合体である。中でもプロピレン、ブテン−1、オクテン−1との共重合体エラストマーの単体や混合物が好ましい。
【0016】
上記エチレン−αオレフィン共重合体エラストマーの添加量は、スチレン系ランダム共重合体の水素添加樹脂に対して、50重量%を超えると凝集力が小さすぎるので、50重量%未満が好ましい。
【0017】
本発明の粘着剤層に使用される粘着付与樹脂とは、スチレン系ランダム共重合体の水素添加樹脂およびエチレン−αオレフィン共重合体エラストマーと選択的に相溶するものが用いられる。例えば、脂肪族炭化水素樹脂、テルペン樹脂、クマロン・インデン樹脂、芳香族炭化水素樹脂、ロジン樹脂などが好適に使用される。スチレン系ランダム共重合体の水素添加樹脂と相溶性が良く、凹凸を有する被着体への粘着性発現の点からは、テルペン樹脂が好ましい。粘着付与樹脂の粘着剤中の添加量は、1重量%未満では凹凸を有する被着体に対して粘着性が発現されず、逆に30重量%を超えると温度・経時変化で粘着力が上昇しやすくなることや被着体への糊残りが生じやすくなることで、1〜30重量%に限定され、より好ましくは、1〜20重量%である。
粘着付与樹脂のガラス転移温度および軟化点は低い方が、分子量が小さく粘着力を付与しやすいが、押出製膜の熱安定性に劣るので、軟化点は100〜140℃の範囲が好ましい。また、表面保護フィルムを被着体に貼着後高温下に放置した場合の粘着力が上昇して剥離しにくい問題では、粘着付与樹脂の粘着剤中の含有量にもよるが、粘着付与樹脂のガラス転移温度に影響しやすく、ガラス転移温度が低い程、粘着力が上昇しやすいので、夏期の外気温への曝露を考慮するとガラス転移温度は50℃以上が好ましく、より好ましくは60℃以上である。
【0018】
温度・経時変化で粘着力が上昇しやすくなることや被着体への糊残りが生じやすくなることの現象については、粘着層に混和した粘着付与樹脂のガラス転移温度が曝露される温度よりも十分高いと問題を生じにくいが、曝露される温度よりも低いガラス転移温度の粘着付与樹脂を混和すると、粘着付与樹脂が粘着剤層の表面に粘性流動しやすく、被着体表面を被覆することが原因と考えられる。この表面保護フィルムを剥離する温度が粘着付与樹脂のガラス転移温度以上である場合は、粘着力が上昇しにくいが、逆に剥離する温度が粘着付与樹脂のガラス転移温度以下である場合は、被着体を被覆した粘着付与樹脂が冷却・固化することで粘着力が上昇しやすく、被着体への糊残りなどの問題が生じやすくなると推測されるが明確でない。
【0019】
本発明の粘着剤層のスチレン系ランダム共重合体の水素添加樹脂とエチレン−αオレフィン共重合体エラストマーおよび粘着付与樹脂のそれぞれの添加量は、中心平均粗さの異なる被着体に対して、適宜決定することができる。例えば、中心平均粗さ(Ra)が大きい被着体に対しては、エチレン−αオレフィン共重合体エラストマーの添加量を減量すること、あるいは、粘着付与剤の添加量を増量することで、適度な粘着力(100〜400g/50mm)を有することができる。
【0020】
本発明の表面保護フィルムは、上記粘着剤組成物が前記基材フィルムの片面に積層されたものであり、その積層方法は任意の方法が採用されてよく、例えば、上記粘着剤組成物を溶剤に溶解しバーコート等により基材フィルムに塗布し積層する方法でも良いが、基材フィルムを形成するポリオレフィン系樹脂と粘着剤組成物とを共押出して積層する方法がコストの点からは好ましい。
【0021】
表面保護フィルムを構成する基材のフィルムと粘着剤層の厚みは、用途によって適宜決定されるが、基材フィルムの厚みは、10〜80μm、粘着剤層の厚みは、5〜30μmである。
【0022】
また、粘着剤層に本発明の効果を損なわない範囲で、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(LLD−PE)、エチルアクリレート共重合体、エチレン−酢酸ビニル共重合体、エチレン−メチルメタクリレート共重合体、エチレン−nブチルアクリレート共重合体、ポリプロピレンなどのポリオレフィン系樹脂を1種または2種以上を添加することもできる。また、必要に応じて、軟化剤、紫外線吸収剤、耐熱安定剤、酸化防止剤、耐候安定剤、帯電防止剤、アンチブロッキング剤、スリップ剤、顔料、染料、無機・有機の充填剤など通常樹脂に添加して使用される添加剤と併用することができる。
【0023】
【特性の測定方法および評価基準】
(1)ガラス転移温度
示差走査型熱量計(DSC、SII型セイコー電子工業社製)を用い、サンプル10mgを0℃より5℃/分の昇温速度で昇温していった際にガラス状態からゴム状態への二次転移にともなう比熱変化を測定したチャートから比熱変化の開始点と終了点との中心点を読み取りガラス転移温度とした。
【0024】
(2)粘着力
表面保護フィルムをマット板(中心平均粗さJIS−B0601、Ra=1.0μm)、エンボス板(Ra=2.1μm)の表面に23℃で2kgの圧着ローラを用いて貼付け、23℃×30分、60℃×7日のそれぞれの場合における粘着力をJIS−Z0237に準じ、測定した。
【0025】
(3)被着体表面の汚染性
表面保護フィルムをマット板(中心平均粗さJIS−B0601、Ra=1.0μm)、エンボス板(Ra=2.1μm)の表面に23℃で2kgの圧着ローラを用いて貼付け、23℃×30分、60℃×7日のそれぞれの場合における剥離した後のマット板の汚染性を目視により判定した。全く汚染されていないものを○、汚れが少しみえるが、実用可能なものを△、汚れがみえ、実用不可なものを×として評価した。
【0026】
【実施例】
次に本発明の効果を実施例により説明する。
【0027】
(1)粘着剤組成物の調整
実施例1〜2
粘着層にスチレン系ランダム共重合体の水素添加樹脂として、日本合成ゴム社製“ダイナロン”1320P、エチレン−αオレフィン共重合体エラストマーとして、エチレン−オクテン−1共重合体(ダウケミカル社製“ENGAGE”EG8200)、粘着付与樹脂として、ヤスハラケミカル社製テルペン樹脂“クリアロン”P125を使用し、それぞれの添加量は表1に示すとおりとし、さらに酸化防止剤としてチバガイギ社製“イルガノックス”1010を1.0重量部、紫外線吸収剤としてチバガイギ社製“チヌビン”327を0.5重量部を配合して粘着剤組成物を調製した。
【0028】
比較例1、比較例3〜5
スチレン系ランダム共重合体の水素添加樹脂の替わりに旭化成工業社製“タフテック”H1052以外は実施例1と同様に粘着剤組成物を調整した。
【0029】
比較例2
エチレン−αオレフィン共重合体として、エチレン−1ブテン共重合体(三井石油化学社製“タフマ”A4085)90重量%以外は実施例1と同様に粘着剤組成物を調整した。
【0030】
実施例3〜6、比較例6〜8
粘着付与樹脂として、実施例3、実施例5〜6および比較例8はヤスハラケミカル社製“クリアロン”P125、実施例4は荒川化学社製“アルコン”P115、比較例6はヤスハラケミカル社製“クリアロン”P85を、それぞれ表3に示す添加量で使用し、比較例7は粘着付与樹脂を添加しなかった。また、実施例3〜6ではスチレン系ランダム共重合体の水素添加樹脂とエチレン−αオレフィン共重合体エラストマーとの比率を2/1の組成とし、上記粘着付与樹脂を添加し、酸化防止剤および紫外線吸収剤を実施例1と同様に添加し、粘着剤組成物を調製した。
【0031】
また、比較例6〜8はスチレン系ランダム共重合体の水素添加樹脂の替わりに、旭化成工業社製“タフテック”H1052を使用し、エチレン−αオレフィン共重合体エラストマーとの比率を2/1の組成とし、上記粘着付与樹脂を添加し、酸化防止剤、紫外線吸収剤を実施例1と同様に添加し、粘着剤組成物を調製した。
【0032】
(2)表面保護フィルムの作製
上記粘着剤組成物と基材層用の高密度ポリエチレン(昭和電工社製“ショーフレックス”F6080)/低密度ポリエチレン(住友化学工業社製“スミカセン”L705)=50/50を2層共押出法により押出成形して、基材層の厚みが50μm、粘着層の厚みが10μmとなるように60μm厚みの表面保護フイルムを作製した。
【0033】
得られた表面保護フィルムを中心平均粗さの異なるマット板、エンボス板に貼付け、フイルムの特性を評価した。この結果は表1、表2および表3に示す通りであった。
【0034】
【表1】
表1に見られるように実施例1〜実施例2は凹凸を有する何れの被着体に対しても適度の粘着力を有するものであり、高温(60℃)による経時変化は小さいものであった。また、被着体への貼付・剥離後の被着体表面の汚染は認められなかった。
【0035】
【表2】
これに比べ、表2に見られるように比較例1〜比較例4は被着体表面の汚染は認められないものの凹凸を有する被着体に対しては粘着力は不十分であった。比較例5は粘着力が強すぎ、被着体表面を汚し、また高温の経時変化が大きいものであった。
【0036】
【表3】
また、表3に見られるように実施例3〜実施例6も凹凸を有する何れの被着体に対しても適度の粘着力を有するものであり、60℃による粘着力の経時変化は小さいものであった。
【0037】
これに比べ、比較例6は凹凸を有する何れの被着体に対しても適度の粘着力を有するが、60℃の粘着力が上昇し、経時変化は大きいものであった。また、粘着付与樹脂が無添加の比較例7は粘着力が不十分であった。さらに、粘着付与樹脂の粘着剤中含有量が50%の比較例8は、粘着力が強すぎ、被着体に糊残りが生じた。
【0038】
本発明の表面保護フィルムが、実施例に示す通り凹凸を有するマット板、エンボス板の被着体に対して粘着性能を有し、温度・経時変化で粘着力の上昇がなく、被着体への糊残りがないことで格段に優れていることがわかる。
【0039】
【発明の効果】
本発明で得られた表面保護フイルムは、スチレン系ランダム共重合体の水素添加物とエチレン−αオレフィン共重合体エラストマーと粘着付与樹脂とを主成分とした粘着剤層と基材層とを2層共押出法により、溶融押出したフィルムであって、ヘアライン加工、マット加工、エンボス加工の凹凸を有する金属板・合成樹脂板等の被着体に対して、適度な初期粘着力を有し、高温に曝されたり、長期にわたって、被着されても粘着力の経時的な上昇が起こらず、さらに、剥離の際には容易に剥離できて、被着体に糊残りがなく、基材フィルムを破断することがないものである。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a surface protection film such as a stainless steel plate, a metal plate such as an aluminum plate, a painted metal plate, a synthetic resin plate, a glass plate, a polyvinyl chloride laminated steel plate, etc., and particularly to an embossed plate or a mat plate. The present invention relates to a surface protection film for protecting a surface or a hairline processed surface.
[0002]
[Prior art]
Conventionally, as a surface protection film, a base film of polyvinyl chloride, polyethylene, polypropylene, etc. to prevent cutting of metal plate, synthetic resin plate, decorative plate, etc. Alternatively, a surface protective film in which an adhesive layer mainly composed of an ethylene / vinyl acetate copolymer, an acrylic resin, a natural rubber, or the like is provided on one side of paper is often used.
[0003]
In addition, for resin plates with irregularities on the surface, which have been subjected to hairline processing, matte processing, embossing on one or both surfaces of metal plates, synthetic resin plates, decorative plates, etc., as an adhesive that is easily plastically deformed at room temperature A surface protection film is used in which a natural rubber or the like, which is referred to as a paste, and a tackifier are dissolved in a solvent and applied to a substrate film by a bar coat or the like.
[0004]
By the way, it has an appropriate adhesive strength to a surface having unevenness with different surface roughness, does not change over time even when exposed to high temperatures or applied for a long time, and can be easily peeled off when unnecessary. There has been a demand for a surface protective film that has no adhesive residue, does not break the substrate, does not release chlorine gas even when incinerated, or does not use a solvent.
[0005]
In order to solve the above problem, Japanese Patent Publication No. Sho 58-30911 and Japanese Patent Application Laid-Open No. Sho 61-103975 disclose, on one side of a base film such as polyolefin, a general formula AB (where A is a styrene polymer). B represents a butadiene polymer block, an isoprene polymer block, or an ethylene / butylene copolymer block), and the surface protection has a pressure-sensitive adhesive layer formed by mixing a block copolymer with a tackifying resin. A film is disclosed.
[0006]
However, when the pressure-sensitive adhesive layer composed of a block copolymer and a tackifying resin is adhered to the surface protective film, the adhesion after adhesion is already high because the content of the block copolymer in the adhesive composition is large. However, there is a problem in that the adhesive strength is high, the adhesive strength is further increased, and if the adherends are stacked, or if the adherends are stacked, or left at a high temperature of about 40 ° C., the adhesive strength is further increased and the peeling is difficult.
[0007]
As a method for improving these, JP-A-6-240216 discloses an adhesive comprising an ethylene-α olefin copolymer and / or a propylene-α olefin copolymer, a block-type styrene-based copolymer and a tackifying resin as main components. There is disclosed a surface protective film in which the adhesive layer does not increase in adhesive strength with time even when exposed to a high temperature or applied for a long time by the agent layer.
[0008]
However, this surface protective film is effective for a mirror plate such as a metal plate, a synthetic resin plate, a decorative plate or the like, or a relatively smooth surface having a small center average roughness (for example, less than 1 μm), There is a problem that it is difficult to adhere to a metal plate or a resin plate (for example, having a center line average roughness (JIS-B0601) Ra of 1 to 3 μm) having irregularities whose surface is subjected to hairline processing, mat processing, and emboss processing. there were.
[0009]
[Problems to be solved by the invention]
As a result of intensive studies to solve the above-mentioned drawbacks, the present invention has an appropriate initial adhesive strength (100 g to 400 g / 50 mm), and has an adhesive strength even when exposed to a high temperature or applied for a long time. It is an object of the present invention to provide a surface protective film which does not cause a rise over time, can be easily peeled off when unnecessary, has no adhesive residue on the adherend, and does not break the substrate.
[0010]
[Means for Solving the Problems]
According to the present invention, which meets this object, an adhesive layer is formed on one surface of a base film made of a polyolefin resin, and the main components of the adhesive layer are a hydrogenated resin of a styrene-based random copolymer and an ethylene-α-olefin copolymer. A surface protective film comprising a polymer elastomer .
[0011]
BEST MODE FOR CARRYING OUT THE INVENTION
In the present invention, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene (LLD-PE), ethylene-α-olefin copolymer, ethylene- Ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ethylene-n-butyl acrylate copolymer, polypropylene, etc. can be used, and a mixture of two or more of these polyolefin-based resins can be used. May be used.
[0012]
The hydrogenated resin of the styrene random copolymer used in the pressure-sensitive adhesive layer of the present invention is defined as 7 to 45% by weight, preferably 7 to 35% by weight of styrene type monomer and 93 to 55% by weight, preferably 93% by weight of butadiene. ~ 65% by weight of a copolymer hydrogenated resin. If the amount of the styrene-based monomer is less than 7% by weight, the handleability as a resin becomes poor, and if the amount of the styrene-based monomer exceeds 45% by weight, the resin becomes hard. Further, the hydrogenation rate of the copolymer is 95% or more, preferably 97% or more. These resins are classified into a block type and a random type according to a polymerization method, and a random type is preferred in terms of adhesion to an embossed plate or a mat plate having irregularities.
[0013]
The block type of the styrene copolymer hydrogenated resin is obtained by hydrogenating a block copolymer of styrene or α-methylstyrene and butadiene. A resin obtained by hydrogenating a block copolymer of styrene and butadiene is generally called SEBS (styrene-ethylene-butadiene-styrene) resin. Further, the random type of the hydrogenated resin of the styrene copolymer is defined as a block (a) of polystyrene or α-methylpolystyrene and a random copolymer block (b) of styrene or α-methylstyrene and butadiene, if necessary. Is a block copolymer composed of styrene or α-methylstyrene and butadiene in a taper block (c), and these are block-bonded.
[0014]
The difference between the random type and the block type of the styrene copolymer hydrogenated resin is that the block type has a glass transition temperature around 100 ° C. corresponding to the block (a) of polystyrene or α-methyl polystyrene. On the other hand, the random type is in that the glass transition temperature corresponding to (a) is not detected.
[0015]
The ethylene-α-olefin copolymer elastomer used in the pressure-sensitive adhesive layer of the present invention is defined as having an ethylene content of 30% by weight or more, preferably 40% by weight or more, more preferably 50% by weight or more , and propylene, A copolymer elastomer obtained by copolymerizing butene-1, hexene-1, 4-methylpentene-1, and octene-1 , that is, a non-crystalline to low-crystalline copolymer . Above all, a simple substance or a mixture of a copolymer elastomer with propylene, butene-1, and octene-1 is preferable.
[0016]
The addition amount of the ethylene-α-olefin copolymer elastomer is preferably less than 50% by weight since the cohesive force is too small when the amount exceeds 50% by weight based on the hydrogenated resin of the styrene-based random copolymer.
[0017]
As the tackifier resin used in the pressure-sensitive adhesive layer of the present invention, a resin which is selectively compatible with a hydrogenated resin of a styrene-based random copolymer and an ethylene-α-olefin copolymer elastomer is used. For example, an aliphatic hydrocarbon resin, a terpene resin, a coumarone-indene resin, an aromatic hydrocarbon resin, a rosin resin, and the like are suitably used. Terpene resins are preferred from the viewpoint of good compatibility with the hydrogenated resin of the styrene-based random copolymer and the development of adhesion to an adherend having irregularities. When the amount of the tackifying resin added to the adhesive is less than 1% by weight, no tackiness is exhibited to the adherend having irregularities, and when it exceeds 30% by weight, the adhesive strength increases due to temperature and aging. The content is limited to 1 to 30% by weight, and more preferably 1 to 20% by weight, because it is easy to perform and adhesive residue is easily generated on the adherend.
The lower the glass transition temperature and the lower the softening point of the tackifying resin, the smaller the molecular weight and the easier the tackiness is to be imparted. However, the thermal stability of the extruded film is poor, so the softening point is preferably in the range of 100 to 140 ° C. In addition, when the surface protective film is left at a high temperature after being adhered to the adherend, the problem that the adhesive strength is increased and the peeling is difficult to be performed depends on the content of the tackifying resin in the adhesive. The glass transition temperature is preferably 50 ° C. or higher, more preferably 60 ° C. or higher in consideration of exposure to outside air temperature in summer, since the lower the glass transition temperature, the easier the adhesive strength is to increase. It is.
[0018]
Regarding the phenomenon that the adhesive strength tends to increase due to changes in temperature and aging and the adhesive residue on the adherend tends to occur, the glass transition temperature of the tackifying resin mixed in the adhesive layer is higher than the temperature at which it is exposed. It is difficult to cause a problem if the temperature is sufficiently high, but if a tackifying resin having a glass transition temperature lower than the exposure temperature is mixed, the tackifying resin tends to viscously flow on the surface of the pressure-sensitive adhesive layer, thereby covering the surface of the adherend. Is considered to be the cause. When the temperature at which the surface protective film is peeled is equal to or higher than the glass transition temperature of the tackifying resin, the adhesive strength is not easily increased. It is presumed that cooling and solidification of the tackifier resin covering the adherend tends to increase the adhesive force, which tends to cause problems such as adhesive residue on the adherend, but it is not clear.
[0019]
The amount of each of the hydrogenated resin and the ethylene-α-olefin copolymer elastomer and the tackifier resin of the styrene random copolymer of the pressure-sensitive adhesive layer of the present invention is different for adherends having different center average roughness. It can be determined appropriately. For example, for an adherend having a large center average roughness (Ra), the amount of the ethylene-α-olefin copolymer elastomer may be reduced, or the amount of the tackifier may be increased. High adhesive strength (100 to 400 g / 50 mm).
[0020]
The surface protective film of the present invention is one in which the above-mentioned pressure-sensitive adhesive composition is laminated on one side of the above-mentioned base film, and the lamination method may be any method. May be applied to a base film by a bar coat or the like and then laminated, but a method of coextruding and laminating a polyolefin resin forming the base film and the pressure-sensitive adhesive composition is preferable from the viewpoint of cost.
[0021]
The thicknesses of the base film and the pressure-sensitive adhesive layer constituting the surface protective film are appropriately determined depending on the application. The thickness of the base film is 10 to 80 μm, and the thickness of the pressure-sensitive adhesive layer is 5 to 30 μm.
[0022]
In addition, as long as the effects of the present invention are not impaired in the pressure-sensitive adhesive layer, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene (LLD-PE), ethyl acrylate copolymer, ethylene-vinyl acetate One or more polyolefin-based resins such as a copolymer, an ethylene-methyl methacrylate copolymer, an ethylene-n-butyl acrylate copolymer, and polypropylene may be added. In addition, if necessary, ordinary resins such as softening agents, ultraviolet absorbers, heat stabilizers, antioxidants, weather stabilizers, antistatic agents, antiblocking agents, slip agents, pigments, dyes, inorganic and organic fillers Can be used in combination with the additives used.
[0023]
[Measurement method and evaluation criteria for characteristics]
(1) Glass transition temperature Glass state when 10 mg of sample was heated from 0 ° C. at a rate of 5 ° C./min using a differential scanning calorimeter (DSC, type SII, manufactured by Seiko Instruments Inc.). The center point between the starting point and the ending point of the specific heat change was read from a chart in which the specific heat change accompanying the secondary transition from the rubber to the rubber state was read, and the glass transition temperature was used.
[0024]
(2) Adhesive surface protective film is adhered to the surface of a mat plate (center average roughness JIS-B0601, Ra = 1.0 μm) or embossed plate (Ra = 2.1 μm) using a 2 kg pressure roller at 23 ° C. , 23 ° C. × 30 minutes, and 60 ° C. × 7 days, the adhesive strength was measured according to JIS-Z0237.
[0025]
(3) A contaminant surface protective film on the surface of the adherend is pressed against the surface of a mat plate (center average roughness JIS-B0601, Ra = 1.0 μm) or embossed plate (Ra = 2.1 μm) at 2 ° C. by 2 kg. The contamination of the mat plate after peeling in each case of 23 ° C. × 30 minutes and 60 ° C. × 7 days was determined by visual observation. A sample that was not contaminated at all was evaluated as 、, and a slightly dirty one was evaluated, but a practically usable one was evaluated as △, and a dirty one that was not practical was evaluated as ×.
[0026]
【Example】
Next, the effects of the present invention will be described with reference to examples.
[0027]
(1) Preparation of pressure-sensitive adhesive composition Examples 1 and 2
"Dynalon" 1320P manufactured by Nippon Synthetic Rubber Co., Ltd. as a hydrogenated resin of a styrene random copolymer in the adhesive layer, and ethylene-octene-1 copolymer (Engage manufactured by Dow Chemical Company) as an ethylene-α-olefin copolymer elastomer "EG8200), as tackifying resin, Yasuhara Chemical Co., Ltd. terpene resin" Clearon "using P125, each addition amount is set to indicate Sutori in Table 1, further Ciba-Geigy Corp. as an antioxidant" Irganox "1010 1 .0 parts by weight, Ciba-Geigy Corp. "Tinuvin" 327 by blending 0.5 parts by weight of papermaking pressure-sensitive adhesive composition tone as an ultraviolet absorber.
[0028]
Comparative Example 1, Comparative Examples 3 to 5
A pressure-sensitive adhesive composition was prepared in the same manner as in Example 1, except that “Tuftec” H1052 manufactured by Asahi Kasei Kogyo Co., Ltd. was used instead of the hydrogenated resin of the styrene random copolymer.
[0029]
Comparative Example 2
A pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except that the ethylene-α-olefin copolymer was 90% by weight of an ethylene-1 butene copolymer (“TAHMA” A4085 manufactured by Mitsui Petrochemical Co., Ltd.).
[0030]
Examples 3 to 6, Comparative Examples 6 to 8
As the tackifying resin, Example 3 , Examples 5 to 6 and Comparative Example 8 are "Clearon" P125 manufactured by Yashara Chemical Company, Example 4 is "Alcon" P115 manufactured by Arakawa Chemical Company, and Comparative Example 6 is "Clearon" manufactured by Yashara Chemical Company. P85 was used in the addition amounts shown in Table 3, and Comparative Example 7 did not add the tackifier resin. Further, in the embodiment 3-6 the ratio ratio of styrene-based random copolymer hydrogenated resin and ethylene -α-olefin copolymer elastomer as the composition of 2/1, was added the tackifier resin, antioxidant agent and an ultraviolet absorber similarly added in example 1, and the pressure-sensitive adhesive composition was made tone.
[0031]
In Comparative Examples 6 to 8, "Tough Tech" H1052 manufactured by Asahi Kasei Kogyo Co., Ltd. was used in place of the hydrogenated resin of the styrene-based random copolymer, and the ratio with the ethylene-α-olefin copolymer elastomer was 2/1. a composition, the addition of the tackifying resin, an antioxidant, an ultraviolet absorber similarly added in example 1, and the pressure-sensitive adhesive composition was made tone.
[0032]
(2) Preparation of surface protective film High-density polyethylene ("Showflex" F6080 manufactured by Showa Denko KK) / low-density polyethylene ("Sumikacene" L705 manufactured by Sumitomo Chemical Co., Ltd.) = 50 for the pressure-sensitive adhesive composition and the substrate layer. / 50 was extruded by a two-layer coextrusion method to prepare a 60 μm-thick surface protective film such that the thickness of the base material layer was 50 μm and the thickness of the adhesive layer was 10 μm.
[0033]
The obtained surface protective film was attached to a mat plate and an emboss plate having different center average roughnesses, and the characteristics of the film were evaluated. The results were as shown in Tables 1, 2 and 3.
[0034]
[Table 1]
As can be seen from Table 1, Examples 1 and 2 have moderate adhesive strength to any adherend having irregularities, and change with time at high temperature (60 ° C.) is small. Was. In addition, no contamination was observed on the surface of the adherend after attaching and detaching to the adherend.
[0035]
[Table 2]
In comparison, as shown in Table 2, Comparative Examples 1 to 4 did not show contamination on the adherend surface, but had insufficient adhesion to the adherend having irregularities. In Comparative Example 5, the adhesive strength was too strong, the surface of the adherend was stained, and the high-temperature change with time was large.
[0036]
[Table 3]
Further, as can be seen from Table 3, Examples 3 to 6 also have moderate adhesive strength to any adherend having irregularities, and the change with time of the adhesive strength at 60 ° C. is small. Met.
[0037]
On the other hand, Comparative Example 6 had a moderate adhesive strength to any adherend having irregularities, but the adhesive strength at 60 ° C. was increased, and the change with time was large. Comparative Example 7 in which no tackifier resin was added had insufficient adhesion. Further, in Comparative Example 8 in which the content of the tackifier resin in the pressure-sensitive adhesive was 50%, the adhesive force was too strong, and adhesive residue was left on the adherend.
[0038]
The surface protective film of the present invention has an adhesive property with respect to an adherend of a mat plate and an embossed plate having irregularities as shown in the examples, and there is no increase in the adhesive force due to temperature and aging, and to the adherend. It can be seen that there is no glue residue, which is much better.
[0039]
【The invention's effect】
The surface protective film obtained by the present invention comprises a pressure-sensitive adhesive layer containing a hydrogenated styrene random copolymer, an ethylene-α-olefin copolymer elastomer and a tackifier resin as a main component, and a base layer. By a layer co-extrusion method, it is a melt-extruded film, and has an appropriate initial adhesive strength to an adherend such as a metal plate or a synthetic resin plate having unevenness of a hairline process, a mat process, and an emboss process, Exposure to high temperatures or long-term application does not cause an increase in adhesive strength over time, and can be easily peeled off, leaving no adhesive residue on the adherend, and a substrate film Is not broken.
Claims (3)
Priority Applications (1)
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JP32046895A JP3560006B2 (en) | 1995-12-08 | 1995-12-08 | Surface protection film |
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JP32046895A JP3560006B2 (en) | 1995-12-08 | 1995-12-08 | Surface protection film |
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JPH09157598A JPH09157598A (en) | 1997-06-17 |
JP3560006B2 true JP3560006B2 (en) | 2004-09-02 |
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Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
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ID21997A (en) | 1997-01-30 | 1999-08-19 | Mitsui Chemicals Inc | HEAT-HOT ADHESIVE COMPOSITION |
JP2002302657A (en) * | 2001-04-05 | 2002-10-18 | Sekisui Chem Co Ltd | Surface protective film for bending of metallic plate |
JP4981270B2 (en) * | 2005-06-03 | 2012-07-18 | 積水化学工業株式会社 | Surface protection film |
JP2007161882A (en) * | 2005-12-14 | 2007-06-28 | Sekisui Chem Co Ltd | Surface-protective film |
CN102471646B (en) * | 2009-07-03 | 2013-09-11 | 三井化学东赛璐株式会社 | Surface protective film |
US20130149525A1 (en) * | 2010-03-31 | 2013-06-13 | Toray Advanced Film Co., Ltd. | Surface protection film |
CN104220548A (en) * | 2012-04-10 | 2014-12-17 | 东洋纺株式会社 | Self-adhesive surface protection film |
JP5989433B2 (en) * | 2012-07-18 | 2016-09-07 | 日東電工株式会社 | Surface protection sheet |
JP5989432B2 (en) * | 2012-07-18 | 2016-09-07 | 日東電工株式会社 | Coating film protection sheet |
JPWO2014054701A1 (en) * | 2012-10-05 | 2016-08-25 | 東洋紡株式会社 | Self-adhesive surface protective film |
CN104685017B (en) * | 2012-10-05 | 2021-08-03 | 东洋纺株式会社 | Self-adhesive surface protective film |
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