JP2013176861A - 粘着テープ用フィルムおよび粘着テープ - Google Patents
粘着テープ用フィルムおよび粘着テープ Download PDFInfo
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- JP2013176861A JP2013176861A JP2012041172A JP2012041172A JP2013176861A JP 2013176861 A JP2013176861 A JP 2013176861A JP 2012041172 A JP2012041172 A JP 2012041172A JP 2012041172 A JP2012041172 A JP 2012041172A JP 2013176861 A JP2013176861 A JP 2013176861A
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- Prior art keywords
- film
- meth
- pressure
- adhesive tape
- adhesive layer
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Classifications
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Abstract
【解決手段】粘着テープ用フィルムは、プラスチックフィルムの片方の面に非粘着層を備える粘着テープ用フィルムであって、該非粘着層がシリコーンと(メタ)アクリル系ポリマーの混合層であり、該(メタ)アクリル系ポリマーの計算Tgが10℃以上である。
【選択図】図1
Description
プラスチックフィルムの片方の面に非粘着層を備える粘着テープ用フィルムであって、
該非粘着層がシリコーンと(メタ)アクリル系ポリマーの混合層であり、
該(メタ)アクリル系ポリマーの計算Tgが10℃以上である。
本発明の粘着テープ用フィルムは、プラスチックフィルムの片方の面に非粘着層を備える。
プラスチックフィルムは、特に限定するものではなく、任意の適切な樹脂材料を含み得る。このような樹脂材料としては、好ましくは、例えば、ポリ塩化ビニル、ポリオレフィン、ポリエステル、ポリイミド、ポリアミドなどが挙げられ、より好ましくは、ポリ塩化ビニル、ポリオレフィンが挙げられ、さらに好ましくは、ポリ塩化ビニルが挙げられる。ポリ塩化ビニルは応力緩和性に優れるため、特に、LEDダイシングなどの半導体加工に用いる粘着テープに用いることができる粘着テープ用フィルムに好適に用いることができる。
非粘着層は、シリコーンと(メタ)アクリル系ポリマーの混合層である。非粘着層をシリコーンと(メタ)アクリル系ポリマーの混合層とすることにより、非粘着層とプラスチックフィルムとの馴染みが良くなり、本発明の粘着テープ用フィルムおよびそれを含む粘着テープは、延伸等の変形に対する追随性が良好なものとなる。
1/(273+Tg)=Σ(Wi/(273+Tgi))
本発明の粘着テープは、本発明の粘着テープ用フィルムにおける上記プラスチックフィルムの上記非粘着層と反対の面に粘着剤層を備える。
最大伸びは、JIS−K−7127に従って、インストロン型引張試験機(島津製作所製、オートグラフ)によって測定した。具体的には、幅20mm×長さ100mmのサンプルをチャック間距離50mmで設置した後、0.3m/分の引張速度で引っ張りを行い、破断した際の値を測定した。
弾性率は、JIS−K−7127に従って測定した。
(SEMによる観察)
非粘着層断面が観察できるよう加工した後、透過型電子顕微鏡(SEM)で形態観察を行った。
(全反射法による赤外分光測定(ATR−IR)による観察)
赤外分光スペクトルメーター(Perkinermer製、Spectrum One)を用い、全反射測定法を選択し、プローブ光の分析深さを変えるため、2種類の全反射測定用プリズム(ZnSe45°、Ge45°)を用いて、非粘着層のATR−IR測定を行った。
OLYMPUS製の共焦点レーザー顕微鏡「LEXT3000」を使用して、対物レンズ20倍で3Dモードにて測定した。3Dモードの観察範囲の決定は、レンズを上下動させた際にCF画像(共焦点画像)が真っ暗になる位置をそれぞれ観察範囲のTopとBottomに設定することで行った。
3Dモードでの画像取り込み方法は、Step方式で0.2μmピッチにて画像取り込みを行った。
算術平均表面粗さRaの計測は、解析モードの粗さ解析にて任意の場所のRaを計測した。なお、値はn=5の平均値にて求めた。
20mm(タテ)×50mm(ヨコ)のスライドガラスに、粘着テープ用フィルムまたは粘着テープを背面(実施例・比較例において、粘着テープ用フィルムの場合は非粘着層側の面、粘着テープの場合は粘着剤層の反対側の面)が表になるように貼付した。次に、80℃環境下にて、上記テープ貼付スライドガラスと被着体となるスライドガラス(青板縁磨品、サイズ:65mm×165mm×1.35mmt)とを、上記テープ貼付スライドガラスの背面側と上記スライドガラスの非スズ面側を接触させて、15分間放置した後、2kgローラーにて一往復させてスライドガラスと上記テープ貼付スライドガラスの背面を貼り合わせ、80℃環境下にて30分間放置した。放置後、常温まで冷却した後、インストロン式引張試験機(島津製作所製、オートグラフ)で、引張速度0.3m/分において、0°剥離を行った。その時の剥離力(最大値)を測定し、下記の基準によって評価を行った。
○:剥離力5.0N未満。
△:剥離力5.0N以上15.0N未満。
×:剥離力15.0N以上。
JIS−Z−0237を参照し、23℃保存下において、被着体および非粘着層を含む粘着テープ用フィルムまたは粘着テープを1時間以上保持し、その後、非粘着面をSUS430BAに線圧8kg/m、圧着速度0.3m/分で圧着し、30分後の剥離力を、0.3m/分の引張速度、180°ピールで測定した。
◎:0.5N/20mm未満。
○:0.5N/20mm以上、1.0N/20mm未満。
×:1.0N/20mm以上。
粘着テープの粘着剤層面を、同じ粘着テープの粘着剤層と反対側の最外面(背面層)に、線圧8Kg/m、圧着速度0.3m/分で圧着し、圧着後、50℃×48hrで保存した。保存後、引張速度0.3m/分にて、180°ピールの剥離試験によって剥離を行い(JIS−Z−0237準拠)、粘着剤層面と背面層のブロッキング(引き剥がし力)を測定した。
評価は引き剥がし力の測定とともに、引き剥がし時の背面層の脱落、粘着剤層の破壊(凝集破壊、投錨破壊により糊残り)などを確認し、総合評価とした。
評価は下記の基準に従った。
○:引き剥がし力3.0N/20mm未満、目視での脱落、粘着剤層の破壊なし。
×:引き剥がし力3.0N/20mm以上または目視での脱落、粘着剤層の破壊あり。
(投錨性確認試験A)
引張速度0.3m/分〜3m/分によって、粘着テープ用フィルムまたは粘着テープを200%まで延伸し、延伸時および延伸後の、粘着テープ用フィルムまたは粘着テープの粘着剤層と反対側の最外面(背面層)の脱落性を目視にて評価した。
(投錨性確認試験B)
投錨性確認試験Aと同様の延伸を行った後、日東電工(株)製「NO.31B」を背面処理層にして、2Kgローラー(25mm幅)にて、0.3m/分の圧着速度にて一往復させ、その後、23℃×50%RHにて1分間保管し、0.3m/分〜3m/分の剥離速度において90°剥離を行い、背面の脱落性を目視にて評価した。
(評価)
以上の評価を総合的に判断し、下記の基準に従って、投錨性を評価した。
◎:目視で確認できる背面の脱落が、投錨性確認試験Aおよび投錨性確認試験Bともに無かった。
○:目視で確認できる背面の脱落が、投錨性確認試験Aでは無く、投錨性確認試験Bではわずかに確認された(点状に確認)。
×:投錨性確認試験Aにおいて背面の脱落が確認されたか、または、投錨性確認試験Bにおいて背面の脱落が確認された。
重合度P=1050のポリ塩化ビニル100重量部に対してDOP可塑剤(フタル酸ビス(2−エチルヘキシル)、ジェイプラス製)27重量部を含んだ軟質ポリ塩化ビニルフィルムをカレンダー法によって製造した。この軟質ポリ塩化ビニルフィルムの厚みは70μmであり、JIS−K−7127に従って測定される弾性率(MD)が250MPa、JIS−K−7127に従って測定される最大伸び(MD)が400%であった。また、製造直後の表面粗さ(算術平均表面粗さRa)は0.1μmであった。
シリコーン樹脂(KS−723A、信越化学工業製)60重量部、シリコーン樹脂(KS−723B、信越化学工業製)40重量部、アクリル共重合ポリマー(メチルメタクリレート(MMA)/ブチルアクリレート(BA)/ヒドロキシエチルアクリレート(HEA)=90/10/10)50重量部、スズ系触媒(Cat−PS3、信越化学工業製)10重量部を、溶液状態で混合して、混合溶液(1)を得た。混合溶液(1)中のシリコーンと(メタ)アクリル系ポリマーの混合比は、重量比で、シリコーン:(メタ)アクリル系ポリマー=2:1であった。また、アクリル共重合ポリマーの計算Tgは67.8℃、SP値は10.7(cal/cm3)0.5であった。
製造例1で製造した軟質ポリ塩化ビニルフィルムの片方の面に、上記混合溶液(1)を塗布して、厚さ1.0μm、算術平均表面粗さRa=0.5μmの非粘着層を形成させた。
このようにして、粘着テープ用フィルム(1)を得た。
各種評価結果を表1に示した。
また、非粘着層をSEMによって観察すると、図1、図2、図3に示すように、形態観察像の濃淡により、空気界面側とプラスチックフィルム側とで組成が異なっていることが確認でき、シリコーンが(メタ)アクリル系ポリマーよりも多く含まれるシリコーンリッチ相と(メタ)アクリル系ポリマーがシリコーンよりも多く含まれる(メタ)アクリル系ポリマーリッチ相を含んでおり、シリコーンリッチ相と(メタ)アクリル系ポリマーリッチ相とが互いに独立した相分離構造をなしており、シリコーンリッチ相が空気界面側(プラスチックフィルムの反対側)に存在しており、(メタ)アクリル系ポリマーリッチ相がプラスチックフィルム側に存在していることが観察された。
さらに、非粘着層について全反射法による赤外分光測定(ATR−IR)を行ったところ、(メタ)アクリル系ポリマー相中のカルボニル基由来の1725cm−1付近のピークに対するSi−CH3由来の800cm−1付近のピークの吸光度比を測定した結果、ZnSe45°に比べGe45°のプリズムを用いた場合に800cm−1付近のピークが大きくなることがわかった。したがって、基材側に比べ空気界面側でケイ素の含有率が高まることがわかった。
また、非粘着層においてシリコーンリッチ相が空気界面側(プラスチックフィルムの反対側)に存在していることは、FT−IRにおいても確認できた。FT−IRによる測定は、Perkinermer製の「Spectrum One」を用い、分析深さ方向の異なる2種類のプリズム(ZnSe45°、Ge45°)にて空気界面側をATR法で測定した。得られたチャートを確認したところ、非粘着層の(メタ)アクリルポリマー由来のC=Oに帰属する1720cm−1−1730cm−1のピークに対する、Si−CH3由来の800cm−1付近のピークの吸光度比が、分析深さ方向の浅いGe45°のプリズムを用いた場合に大きくなっていることが確認できた。このことから、空気界面側にはシリコーンの濃度がより高くなっていることが証明できた。
これらの観察結果、ならびに、表面自由エネルギー最小化の原理を考慮にいれると、空気界面側にシリコーンリッチ相を有する2層構造が非粘着層に形成されたことがわかった。
実施例1において、製造例1で製造した軟質ポリ塩化ビニルフィルムの片方の面に混合溶液(1)を塗布して、実施例1と同様に行い、厚さ0.7μm、算術平均表面粗さRa=0.1μmの非粘着層を形成させた。
このようにして、粘着テープ用フィルム(2)を得た。
各種評価結果を表1に示した。
ブチルアクリレート(BA)/アクリロニトリル(AN)/アクリル酸(AA)=85/15/2.5(重量比)から構成されるアクリル共重合ポリマー100重量部、メラミン系架橋剤(ブタノール変性メラミンホルムアルデヒド樹脂、「スーパーベッカミンJ−820−60N」、日本ポリウレタン製)10重量部、DOP可塑剤(フタル酸ビス(2−エチルヘキシル)、ジェイプラス製)60重量部からなる粘着剤のトルエン溶液を調製した。
この粘着剤溶液を、実施例1で得られた粘着テープ用フィルム(1)の非粘着層と反対側の面に塗布した後、130℃×90秒で乾燥し、厚み10μmの粘着剤層を軟質ポリ塩化ビニルフィルムの非粘着層と反対側の面に形成した。形成した粘着剤層のSP値は10.5であった。
このようにして、粘着テープ(3)を得た。
各種評価結果を表1に示した。
非粘着層形成用のアクリル共重合ポリマーとして、メチルメタクリレート(MMA)/エチルアクリレート(EA)/ヒドロキシエチルアクリレート(HEA)=90/10/10のアクリル共重合ポリマーを50重量部用いた以外は実施例1と同様に行って粘着テープ用フィルム(4)を得た。この粘着テープ用フィルム(4)を粘着テープ用フィルム(1)に代えて用いた以外は実施例3と同様に行い、粘着テープ(4)を得た。
アクリル共重合ポリマーの計算Tgは74.3℃、SP値は10.3(cal/cm3)0.5であった。
非粘着層は、厚さ1.0μm、算術平均表面粗さRa=0.5μmであった。
各種評価結果を表1に示した。
非粘着層形成用のアクリル共重合ポリマーとして、メチルメタクリレート(MMA)/シクロヘキシルアクリレート(CHA)/ヒドロキシエチルアクリレート(HEA)=90/10/10のアクリル共重合ポリマーを50重量部用いた以外は実施例1と同様に行って粘着テープ用フィルム(5)を得た。この粘着テープ用フィルム(5)を粘着テープ用フィルム(1)に代えて用いた以外は実施例3と同様に行い、粘着テープ(5)を得た。
アクリル共重合ポリマーの計算Tgは80.0℃、SP値は10.4(cal/cm3)0.5であった。
非粘着層は、厚さ1.0μm、算術平均表面粗さRa=0.5μmであった。
各種評価結果を表1に示した。
非粘着層形成用のアクリル共重合ポリマーとして、メチルメタクリレート(MMA)/ブチルアクリレート(BA)/ヒドロキシエチルアクリレート(HEA)=95/5/15のアクリル共重合ポリマーを50重量部用いた以外は実施例1と同様に行って粘着テープ用フィルム(6)を得た。この粘着テープ用フィルム(6)を粘着テープ用フィルム(1)に代えて用いた以外は実施例3と同様に行い、粘着テープ(6)を得た。
アクリル共重合ポリマーの計算Tgは73.0℃、SP値は10.5(cal/cm3)0.5であった。
非粘着層は、厚さ1.0μm、算術平均表面粗さRa=1.0μmであった。
各種評価結果を表1に示した。
非粘着層形成用のアクリル共重合ポリマーとして、メチルメタクリレート(MMA)/ブチルアクリレート(BA)/ヒドロキシエチルアクリレート(HEA)=80/20/10のアクリル共重合ポリマーを50重量部用いた以外は実施例1と同様に行って粘着テープ用フィルム(7)を得た。この粘着テープ用フィルム(7)を粘着テープ用フィルム(1)に代えて用いた以外は実施例3と同様に行い、粘着テープ(7)を得た。
アクリル共重合ポリマーの計算Tgは48.5℃、SP値は10.1(cal/cm3)0.5であった。
非粘着層は、厚さ1.0μm、算術平均表面粗さRa=0.2μmであった。
各種評価結果を表1に示した。
非粘着層形成用のアクリル共重合ポリマーとして、メチルメタクリレート(MMA)/ブチルアクリレート(BA)/ヒドロキシエチルアクリレート(HEA)=99/1/5のアクリル共重合ポリマーを50重量部用いた以外は実施例1と同様に行って粘着テープ用フィルム(8)を得た。この粘着テープ用フィルム(8)を粘着テープ用フィルム(1)に代えて用いた以外は実施例3と同様に行い、粘着テープ(8)を得た。
アクリル共重合ポリマーの計算Tgは94.3℃、SP値は10.1(cal/cm3)0.5であった。
非粘着層は、厚さ1.0μm、算術平均表面粗さRa=0.5μmであった。
各種評価結果を表1に示した。
実施例5で得られた粘着テープ(5)の粘着剤層側に、剥離ライナーとして、Si処理を施した厚さ38μmのPETライナーを貼付し、粘着テープ(9)を得た。
非粘着層は、厚さ1.0μm、算術平均表面粗さRa=0.5μmであった。
各種評価結果を表1に示した。
非粘着層形成用のアクリル共重合ポリマーとして、メチルメタクリレート(MMA)/ブチルアクリレート(BA)/ヒドロキシエチルアクリレート(HEA)=95/5/10のアクリル共重合ポリマーを50重量部用いた以外は実施例1と同様に行って粘着テープ用フィルム(10)を得た。この粘着テープ用フィルム(10)を粘着テープ用フィルム(1)に代えて用いた以外は実施例3と同様に行い、粘着テープ(10)を得た。
アクリル共重合ポリマーの計算Tgは77.2℃、SP値は10.3(cal/cm3)0.5であった。
非粘着層は、厚さ1.0μm、算術平均表面粗さRa=0.7μmであった。
各種評価結果を表1に示した。
非粘着層形成用のアクリル共重合ポリマーとして、メチルメタクリレート(MMA)/ブチルアクリレート(BA)/ヒドロキシエチルアクリレート(HEA)=70/30/10のアクリル共重合ポリマーを50重量部用いた以外は実施例1と同様に行って粘着テープ用フィルム(11)を得た。この粘着テープ用フィルム(11)を粘着テープ用フィルム(1)に代えて用いた以外は実施例3と同様に行い、粘着テープ(11)を得た。
アクリル共重合ポリマーの計算Tgは31.2℃、SP値は10.4(cal/cm3)0.5であった。
非粘着層は、厚さ1.0μm、算術平均表面粗さRa=0.3μmであった。
各種評価結果を表1に示した。
実施例3において、非粘着層を形成しなかった以外は、実施例3と同様に行い、粘着テープ(C1)を得た。
各種評価結果を表1に示した。
非粘着層形成用のアクリル共重合ポリマーとして、メチルメタクリレート(MMA)/ブチルアクリレート(BA)/ヒドロキシエチルアクリレート(HEA)=55/45/10のアクリル共重合ポリマーを50重量部用いた以外は実施例1と同様に行って粘着テープ用フィルム(C2)を得た。この粘着テープ用フィルム(C2)を粘着テープ用フィルム(1)に代えて用いた以外は実施例3と同様に行い、粘着テープ(C2)を得た。
アクリル共重合ポリマーの計算Tgは8.6℃、SP値は10.4(cal/cm3)0.5であった。
非粘着層は、厚さ1.0μm、算術平均表面粗さRa=0.08μmであった。
各種評価結果を表1に示した。
Claims (16)
- プラスチックフィルムの片方の面に非粘着層を備える粘着テープ用フィルムであって、
該非粘着層がシリコーンと(メタ)アクリル系ポリマーの混合層であり、
該(メタ)アクリル系ポリマーの計算Tgが10℃以上である、
粘着テープ用フィルム。 - 前記非粘着層の算術平均表面粗さRaが0.1μm以上である、請求項1に記載の粘着テープ用フィルム。
- 前記(メタ)アクリル系ポリマーのSP値が9.0(cal/cm3)0.5〜12.0(cal/cm3)0.5である、請求項1または2に記載の粘着テープ用フィルム。
- 前記非粘着層が相分離構造を有する、請求項1から3までのいずれかに記載の粘着テープ用フィルム。
- 前記非粘着層中のシリコーンと(メタ)アクリル系ポリマーの混合比が、重量比で、シリコーン:(メタ)アクリル系ポリマー=1:50〜50:1である、請求項1から4までのいずれかに記載の粘着テープ用フィルム。
- 前記非粘着層の非粘着試験剥離力が1.0N/20mm未満である、請求項1から5までのいずれかに記載の粘着テープ用フィルム。
- 前記非粘着層の厚みが0.01μm〜10μmである、請求項1から6までのいずれかに記載の粘着テープ用フィルム。
- 前記プラスチックフィルムのJIS−K−7127に従って測定される最大伸びが100%以上である、請求項1から7までのいずれかに記載の粘着テープ用フィルム。
- 前記プラスチックフィルムの厚みが20μm〜200μmである、請求項1から8までのいずれかに記載の粘着テープ用フィルム。
- 前記プラスチックフィルムが少なくともポリ塩化ビニルを含む、請求項1から9までのいずれかに記載の粘着テープ用フィルム。
- 請求項1から10までのいずれかに記載の粘着テープ用フィルムにおける前記プラスチックフィルムの前記非粘着層と反対の面に粘着剤層を備える、粘着テープ。
- 前記粘着剤層が少なくとも1種の(メタ)アクリル系ポリマーを含む、請求項11に記載の粘着テープ。
- 前記粘着剤層のSP値が9.0(cal/cm3)0.5〜12.0(cal/cm3)0.5である、請求項11または12に記載の粘着テープ。
- 前記粘着剤層の表面に剥離ライナーを備える、請求項11から13までのいずれかに記載の粘着テープ。
- 半導体加工に用いられる、請求項11から14までのいずれかに記載の粘着テープ。
- LEDダイシング用途に用いられる、請求項11から15までのいずれかに記載の粘着テープ。
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CN201380003304.7A CN103857524B (zh) | 2012-02-28 | 2013-02-08 | 粘合带用薄膜和粘合带 |
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US20140178620A1 (en) | 2014-06-26 |
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Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |