JP2012117016A - 粘着剤及び粘着テープ - Google Patents
粘着剤及び粘着テープ Download PDFInfo
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Abstract
【解決手段】 (1)炭素数4〜6の脂肪族アルキル(メタ)アクリレート及び炭素数7〜12の脂肪族アルキル(メタ)アクリレートから選ばれるアクリレートを含むアクリレート混合物、(2)アミド基含有ビニルモノマー、(3)非第3級芳香族アルコールと(メタ)アクリル酸とのエステル、または非第3級脂環式アルコールと(メタ)アクリル酸とのエステル、及び(4)(メタ)アクリル酸からなるモノマー混合物を重合することにより得られるポリマーを含む粘着剤、及びかかる粘着剤を用いた粘着テープ。
【選択図】 なし
Description
モノマー成分(1)炭素数4〜6の脂肪族アルキル(メタ)アクリレート及び炭素数7〜12の脂肪族アルキル(メタ)アクリレートから選ばれるアクリレートを含むアクリレート混合物 46〜60質量部、
モノマー成分(2)アミド基含有ビニルモノマー 22〜36質量部、
モノマー成分(3)非第3級芳香族アルコールと(メタ)アクリル酸とのエステル、または非第3級脂環式アルコールと(メタ)アクリル酸とのエステル 10〜30質量部、及び
モノマー成分(4)(メタ)アクリル酸 0〜3質量部
からなるモノマー混合物100質量部を重合することにより得られるポリマーを含む粘着剤を提供するものである。
炭素数4〜6の脂肪族アルキル(メタ)アクリレート及び炭素数7〜12の脂肪族アルキル(メタ)アクリレートから選ばれるアクリレートを含むアクリレート混合物(モノマー成分(1))、アミド基含有ビニルモノマー(モノマー成分(2))、非第3級芳香族アルコールと(メタ)アクリル酸とのエステル、または非第3級脂環式アルコールと(メタ)アクリル酸とのエステル(モノマー成分(3))、及び(メタ)アクリル酸(モノマー成分(4))からなるモノマー混合物100質量部を重合することにより得られるポリマーを含む粘着剤に関する。
本明細書において、「(メタ)アクリル」とは、「アクリルまたはメタクリル」を意味する。
モノマー
モノマー成分(1)とは、炭素数4〜6の脂肪族アルキル(メタ)アクリレート及び炭素数7〜12の脂肪族アルキル(メタ)アクリレートから選ばれるアクリレートを含むアクリレート混合物をいう。
また、モノマー成分(2)として、N−ビニル環状アミドモノマーを用いる場合、モノマー成分(1)の含有量は、約47〜約60質量部、約47〜約56質量部、または約50〜約56質量部とすることができる。
重合開始剤
本発明の粘着剤には、通常用いられる重合開始剤を適宜選択して用いることができる。
架橋剤
本発明の粘着剤は、さらに通常用いる架橋剤を含んでも良い。例えば、多官能アクリレート、イソシアネート系架橋剤、エポキシ系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、金属キレート系架橋剤、メラミン樹脂系架橋剤、過酸化物系架橋剤などが挙げられる。
架橋剤の添加量は特に限定されないが例えば、前記モノマー混合物を100質量部としたとき約0.01質量部〜約0.5質量部とすることができる。
添加剤
本発明の粘着剤は、さらに可塑剤、フィラー、老化防止剤、接着促進剤(塩素化ポリオレフィンなど)、紫外線吸収剤、顔料等通常用いられる添加剤を使用することができる。
粘着剤の製法
本発明の粘着剤は、前記モノマー混合物、すなわちすなわち前記モノマーの混合物を重合することにより得られるポリマーからなる。
かかるポリマーは、例えば、前記モノマー混合物に、光重合開始剤、また所望により従来公知の添加剤を混合して、窒素ガスでモノマーを十分に置換して酸素を除いた後、紫外線、X線、ガンマ線、または電子線等の放射線を照射して重合することにより得られる。あるいは、まず前記モノマー混合物に、光重合開始剤の一部を加えて、粘度が約1000cps〜約5000cps程度になるように例えば紫外線を照射してプレポリマーを作成し、続いてさらに光重合開始剤を加えて例えば紫外線を照射し重合することにより得られる。
粘着テープ
本発明の粘着テープは、基材層と本発明の粘着剤からなる粘着剤層を含む。基材の片面のみに、または両面に粘着剤層を積層して粘着テープとすることができる。あるいは、基材の片面にあらかじめ粘着剤の層を有する材料のかかる粘着剤の層と反対側の面に、本発明の粘着剤からなる粘着剤層を積層して粘着テープとすることもできる。また所望により、プライマー層など他の機能を有する層を有していても良い。さらに粘着剤層の表面に通常用いられる剥離ライナーを積層してもよい。
構造体
本発明の構造体は、基材層、粘着剤層、及びポリメチルメタクリレートからなる自動車外装部品を含む。特に、基材層、粘着剤層、及びポリメチルメタクリレートがこの順に積層されている構造体が好ましい。
BA :n−ブチルアクリレート(三菱化学(株)社製)
2EHA :2エチルヘキシルアクリレート((株)日本触媒社製)
nnDMA:ジメチルアクリルアミド((株)興人社製)
NVP :n−ビニル−2−ピロリドン((株)日本触媒社製)
NVC :n−ビニル−カプロラクタム(BASF社製)
BzA :ベンジルアクリレート(大阪有機化学工業(株)社製)
CHA :シクロヘキシルアクリレート(大阪有機化学工業(株)社製)
AA :アクリル酸(東亜合成(株)社製)
Irgacure 651:2,2−ジメトキシ−1,2−ジフェニルエタン−1−オン(チバスペシャリティー・ケミカルズ社製)
HDDA:1,6−ヘキサンジオールジアクリレート 共栄社
V−65:2,2’−アゾビス(2,4−ジメチルバレロニトリル)(和光純薬工業(株)社製)
Bis Aziridine:イソフタノイルビス−2−メチルアジリジン
表1〜4に示すモノマー成分(1)〜(4)に、光重合開始剤を上段に記載した量加え、窒素ガスで置換して十分に酸素を除いた後、粘度が約1000cps〜約5000cpsになるよう紫外線を照射しプレポリマーを作成した。その後、下段に記載した量の光重合開始剤、架橋剤を加えシロップ溶液を得た。
得られたシロップ溶液を厚さ50μmの剥離処理PETフィルム(三菱化学社製)に置き、上面より同種のPETフィルムをかぶせて2枚のフィルムではさみながらナイフコート法により塗布した。続いて、300〜400nmの波長の0.5〜7.0mW/cm2の強度の紫外線を6分間照射させることにより硬化させ、粘着剤を作成した。硬化後の厚さは100μmであった。
得られた粘着剤の一方のPETフィルムを剥がし、露出した粘着剤表面にアクリルフォームテープ(住友スリーエム社製GT7108)をラミネートして粘着テープを得た。
耐圧瓶に、2エチルヘキシルアクリレート21部、ブチルアクリレート31部、ベンジルアクリレート20部、n−ビニルピロリドン26部、アクリル酸2部、及び酢酸エチル185.7部を充填した。重合開始剤(和光純薬社製V−65)0.1部を加え、窒素ガス置換(10分間)して酸素を除いた後耐圧瓶を密閉し、50℃の水浴中で20時間重合した。得られたポリマー溶液の固有粘度をキャノン・フェンスケを用いて測定したところ、1.36dl/gであった。
得られたポリマー溶液とイソフタノイルビス−2−メチルアジリジン0.2部(架橋剤)を瓶に充填して混合した。得られた溶液を、シリコン処理した厚さ50μmのPETフィルムにナイフコーターを用いて塗布し、100℃のオーブンで10分間乾燥して厚さ65μmの粘着剤を得た。続いて、露出した粘着剤表面にアクリルフォームテープ(住友スリーエム社製GT7108)をラミネートして粘着テープを得た。
被着体としてポリメチルメタクリレート(PMMA)の板(100mm×25mm×2mm:三菱レイヨン製アクリペット(登録商標)VH000)を用意し、イソプロピルアルコール(IPA)で洗浄した。上記実施例及び比較例で作成した評価用サンプル(テープサイズ:12mm×60mm)を2kgローラー(1往復)にてそれぞれ圧着した後、室温(25℃)にて24時間放置後、引張試験機(テンシロンRTC−1325A型(株)オリエンテック社製)にて180°ピール強度を測定した(25℃、引張速度50mm/分)。結果を表に示した。
測定1で作成したサンプルを、80℃中にて30分〜60分間放置し、引張試験機(テンシロンRTC−1325A型(株)オリエンテック社製)にて180°ピール強度を測定した(80℃、引張速度50mm/分)。結果を表に示した。
測定1で作成したサンプルを、5℃中にて120分間放置し、引張試験機(テンシロンRTC−1325A型(株)オリエンテック社製)にて90°ピール強度を測定した(5℃、引張速度300mm/分)。結果を表に示した。
測定4:ポリメチルメタクリレートに対する高温(80℃)保持力の測定
ポリメチルメタクリレート(PMMA)の板(100mm×25mm×2mm:三菱レイヨン製アクリペット(登録商標)VH000)を用意し、イソプロピルアルコール(IPA)で洗浄した。上記実験例で作成した保持力測定用評価サンプル(テープサイズ:12mm×25mm)の評価側粘着面をPMMA板に、反対側のアクリルフォームテープの面には清浄なSUS−304の板(0.5mm×30mm×60mm)を貼り合わせ、5kgローラー(1往復)を用いて圧着した。得られた試験片を80℃のオーブン中で60分間養生後、500gの錘を2度の角度になるようサンプルの長手方向の一方の端に吊り下げ、錘が落下するまでの保持時間(分)を計測した。繰り返し数は3とし、平均保持時間を表に示した。
Claims (5)
- モノマー成分(1)炭素数4〜6の脂肪族アルキル(メタ)アクリレート及び炭素数7〜12の脂肪族アルキル(メタ)アクリレートから選ばれるアクリレートを含むアクリレート混合物 46〜60質量部
モノマー成分(2)アミド基含有ビニルモノマー 22〜36質量部
モノマー成分(3)非第3級芳香族アルコールと(メタ)アクリル酸とのエステル、または非第3級脂環式アルコールと(メタ)アクリル酸とのエステル 10〜30質量部、及び
モノマー成分(4)(メタ)アクリル酸 0〜3質量部
からなるモノマー混合物100質量部を重合することにより得られるポリマーを含む粘着剤。 - 前記モノマー混合物において、
前記モノマー成分(1)として、炭素数4〜6の脂肪族アルキル(メタ)アクリレート及び炭素数7〜12の脂肪族アルキル(メタ)アクリレートの配合比(質量比)が3:7〜7:3であるアクリレート混合物 46〜53質量部
前記モノマー成分(2)として、
一般式1:CHR=CH−C(O)−N(R1)R2(式中、Rは水素またはメチル基、R1及びR2は、水素、または炭素数1〜4の直鎖または分岐鎖のアルキル基であって、R1とR2は同時に水素となることはない。)で表されるモノマー 26〜34質量部を含む請求項1に記載の粘着剤。 - 前記モノマー混合物において、
前記モノマー成分(1)として、炭素数4〜6の脂肪族アルキル(メタ)アクリレート及び炭素数7〜12の脂肪族アルキル(メタ)アクリレートの配合比(質量比)が2.5:7.5〜10:0であるアクリレート混合物 47〜60質量部、
前記モノマー成分(2)として、
N−ビニル環状アミドモノマー 22〜36質量部を含む請求項1に記載の粘着剤。 - 基材層、及び請求項1〜3のいずれか一項に記載の粘着剤からなる粘着剤層を含む粘着テープ。
- 基材層、請求項1〜3のいずれか一項に記載の粘着剤からなる粘着剤層、及びポリメチルメタクリレートからなる自動車外装部品を含む構造体。
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PCT/US2011/062870 WO2012075271A1 (en) | 2010-12-03 | 2011-12-01 | Pressure sensitive adhesive and adhesive tape |
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Cited By (6)
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JP2014196447A (ja) * | 2013-03-29 | 2014-10-16 | 株式会社ブリヂストン | 光硬化性粘着剤組成物 |
JP2014196446A (ja) * | 2013-03-29 | 2014-10-16 | 株式会社ブリヂストン | 光硬化性粘着剤組成物 |
JP2015189940A (ja) * | 2014-03-28 | 2015-11-02 | アイカ工業株式会社 | 粘着剤組成物 |
WO2016144659A1 (en) | 2015-03-06 | 2016-09-15 | 3M Innovative Properties Company | Pressure sensitive adhesive and laminate |
JP2017105953A (ja) * | 2015-12-11 | 2017-06-15 | Dic株式会社 | 活性エネルギー線硬化型樹脂組成物及び積層フィルム |
JP2019044026A (ja) * | 2017-08-30 | 2019-03-22 | 綜研化学株式会社 | 粘着剤組成物及び粘着シート |
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US20140370221A1 (en) * | 2013-06-14 | 2014-12-18 | Nitto Denko Corporation | Lightweight two-sided adhesive tape |
US10903435B2 (en) * | 2017-10-18 | 2021-01-26 | Dongwoo Fine-Chem Co., Ltd. | Flexible display device |
KR102188402B1 (ko) | 2018-11-23 | 2020-12-08 | 주식회사 엘엠에스 | 접착시트 및 이를 포함하는 접착소재 |
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JP2017105953A (ja) * | 2015-12-11 | 2017-06-15 | Dic株式会社 | 活性エネルギー線硬化型樹脂組成物及び積層フィルム |
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US9422461B2 (en) | 2016-08-23 |
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WO2012075271A1 (en) | 2012-06-07 |
KR20130141621A (ko) | 2013-12-26 |
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