JP2007112903A - 粘着剤層およびその製造方法、粘着剤付光学部材、ならびに画像表示装置 - Google Patents
粘着剤層およびその製造方法、粘着剤付光学部材、ならびに画像表示装置 Download PDFInfo
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- JP2007112903A JP2007112903A JP2005305863A JP2005305863A JP2007112903A JP 2007112903 A JP2007112903 A JP 2007112903A JP 2005305863 A JP2005305863 A JP 2005305863A JP 2005305863 A JP2005305863 A JP 2005305863A JP 2007112903 A JP2007112903 A JP 2007112903A
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Abstract
【解決手段】モノマー単位として、一般式CH2=C(R1)COOR2(ただし、R1は水素またはメチル基、R2は炭素数2〜14のアルキル基である)で表される(メタ)アクリル系モノマー50〜98重量%含有する(メタ)アクリル系ポリマーからなる粘着剤組成物を架橋してなる粘着剤層であって、前記(メタ)アクリル系ポリマーのカルボニル基の固体13C−NMRにおけるピーク強度を100とする場合に、前記(メタ)アクリル系ポリマーの末端メチル基の固体13C−NMRにおけるピーク強度が92〜130であることを特徴とする粘着剤層。
【選択図】なし
Description
モノマー単位として、一般式CH2=C(R1)COOR2(ただし、R1は水素またはメチル基、R2は炭素数2〜14のアルキル基である)で表される(メタ)アクリル系モノマー50〜98重量%含有する(メタ)アクリル系ポリマーからなる粘着剤組成物を架橋してなる粘着剤層であって、前記(メタ)アクリル系ポリマーのカルボニル基の固体13C−NMRにおけるピーク強度を100とする場合に、前記(メタ)アクリル系ポリマーの末端メチル基の固体13C−NMRにおけるピーク強度が92〜130であることを特徴とする。
モノマー単位として、一般式CH2=C(R1)COOR2(ただし、R1は水素またはメチル基、R2は炭素数2〜14のアルキル基である)で表される(メタ)アクリル系モノマー50〜98重量%含有する(メタ)アクリル系ポリマーからなる粘着剤組成物を架橋してなる粘着剤層であって、前記(メタ)アクリル系ポリマーのカルボニル基の固体13C−NMRにおけるピーク強度を100とする場合に、前記(メタ)アクリル系ポリマーの末端メチル基の固体13C−NMRにおけるピーク強度が92〜130であることを特徴とする。
得られた(メタ)アクリル系ポリマーの重量平均分子量は、GPC(ゲル・パーミエーション・クロマトグラフィー)により測定した。
・分析装置:東ソー社製、HLC−8120GPC
・データ処理装置:東ソー社製、GPC−8020
・カラム:東ソー社製、G7000HXL−H+GMHXL+GMHXL
・カラムサイズ;各7.8mmφ×30cm(計90cm)
・流量:0.8ml/min
・注入試料濃度:約0.1重量%
・注入量:100μl
・カラム温度:40℃
・溶離液:テトラヒドロフラン
・検出器:示差屈折計(RI)
なお、分子量はポリスチレン換算により算出した。また、分子量10万以下の重量分率(Area%)は、GPC測定結果から上記データ処理装置で算出した。このときモノマー成分は含めなかった。
熱分解処理後の過酸化物分解量は、HPLC(高速液体クロマトグラフィー)により測定した。具体的には、分解処理前後の粘着剤組成物をそれぞれ約0.2gずつ取り出し、酢酸エチル10mlに浸漬し、振とう機で25℃下、120rpmで3時間振とう抽出した後、室温で3日間静置した。次いで、アセトニトリル10ml加えて、25℃下、120rpmで30分振とうし、メンブランフィルター(0.45μm)によりろ過して得られた抽出液約10μlをHPLCに注入して分析し、分解処理前後の過酸化物量の減少を過酸化物分解量とした。
・装置:東ソー社製、HPL CCPM/UV8000
・カラム:MACHEREY−NAGEL社製、NUCLEOSIL 7C18(4.6mmφ×250mm)
・流量:1ml/min
・カラム圧力:41kg/cm2
・カラム温度:40℃
・溶離液:水/アセトニトリル=30/70
・注入量:10μl
・注入試料濃度:0.01重量%
・検出器:UV検出器(230nm)
各実施例・比較例で作製した粘着剤層をW1g(約0.1g)取り出し、酢酸エチルに室温(約25℃)下で1週間浸漬した。その後、浸漬処理した粘着剤層(不溶分)を酢酸エチル中から取り出し、130℃で2時間乾燥後の重量W2gを測定し、(W2/W1)×100として計算される値をゲル分率(重量%)とした。
固体13C−NMRの測定および各ピーク強度の算出は、下記の条件で行なった。
・装置:Bruker DRX300(300MHz、7.05T)
・ローター径:7mmφ
・MAS Rate:4kHz
・ケミカルシフト値:hexamethylbenzene 17.36ppm(外部標準)
・CP contact Time:0.5ms
・Pulse Delay: 10s
・積算回数:CP/MAS 2000回
また、得られたスペクトルから、174ppm付近のカルボニル炭素のピーク面積を100として、14ppm付近の末端メチル基炭素のピーク面積を算出した。
作製した粘着剤付光学部材(幅:25mm)を、無アルカリガラス板(コーニング社製、1737、厚み:1.2mm)に2Kgのロール1往復にて貼り付け、50℃、0.5MPaの圧力で30分間オートクレーブ処理を行った。その後、23℃×50%RHで3時間保存し、評価用サンプル(a)を得た。
作製した5インチサイズの積層サンプルを無アクリルガラス(コーニング社製、1737、厚み:1.2mm)に貼り付けた後、50℃、0.3Mpaのオートクレーブにて30分間、次いで60℃×95%RHの雰囲気下で500時間保存してから、室温(約25℃)に戻し、評価用サンプルを得た。耐湿試験の評価は目視でおこない、評価基準は以下のとおりである。
・粘着剤付光学部材の浮きや剥がれが生じなかった場合:○
・粘着剤付光学部材の浮きや剥がれがかなり生じた場合:×
〔アクリル系ポリマー(A)〕
攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた4つ口フラスコに、ブチルアクリレート100重量部、6−ヒドロキシヘキシルアクリレート0.6重量部、重合開始剤として2,2’−アゾビスイソブチロニトリル0.1重量部、酢酸エチル200重量部を仕込み、十分に窒素置換した後、窒素気流下で攪拌しながらフラスコ内の液温を55℃に保って20時間重合反応を行い、アクリル系ポリマー(A)溶液を調製した。上記アクリル系ポリマー(A)の重量平均分子量は167万であった。
攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた4つ口フラスコに、ブチルアクリレート100重量部、4−ヒドロキシブチルアクリレート0.5重量部、アクリル酸0.5重量部、重合開始剤として2,2’−アゾビスイソブチロニトリル0.1重量部、酢酸エチル200重量部を仕込み、十分に窒素置換した後、窒素気流下で攪拌しながらフラスコ内の液温を55℃に保って20時間重合反応を行い、アクリル系ポリマー(B)溶液を調製した。上記アクリル系ポリマー(B)の重量平均分子量は177万であった。
攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた4つ口フラスコに、2−エチルヘキシルアクリレート50重量部、ブチルアクリレート50重量部、4−ヒドロキシブチルアクリレート0.3重量部、アクリル酸0.3重量部、重合開始剤として2,2’−アゾビスイソブチロニトリル0.1重量部、酢酸エチル200重量部を仕込み、十分に窒素置換した後、窒素気流下で攪拌しながらフラスコ内の液温を55℃に保って20時間重合反応を行い、アクリル系ポリマー(C)溶液を調製した。上記アクリル系ポリマー(C)の重量平均分子量は145万であった。
攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた4つ口フラスコに、ブチルアクリレート100重量部、2−ヒドロキシエチルアクリレート0.4重量部、重合開始剤として2,2’−アゾビスイソブチロニトリル0.1重量部、酢酸エチル200重量部を仕込み、十分に窒素置換した後、窒素気流下で攪拌しながらフラスコ内の液温を55℃に保って20時間重合反応を行い、アクリル系ポリマー(D)溶液を調製した。上記アクリル系ポリマー(D)の重量平均分子量は170万であった。
(光学部材用粘着剤溶液の調製)
上記アクリル系ポリマー(A)溶液の固形分100重量部に対して、過酸化物としてジベンゾイルパーオキシド(和光純薬社製、1分間半減期:130℃)0.3重量部、およびシランカップリング剤として3−グリシドキシプロピルトリメトキシシラン0.1重量部を配合し、均一に混合撹拌してアクリル系粘着剤溶液(1)を調整した。
上記アクリル系粘着剤溶液(1)を、シリコーン処理を施したポリエチレンテレフタレート(PET)フィルム(東レ社製、厚さ:38μm)の片面に塗布し、130℃で3分間乾燥・架橋をおこない、乾燥後の厚さが25μmの粘着剤層を形成した。ここで、理論計算により算出される過酸化物の分解量は約88重量%であった。なお、粘着剤層のゲル分率は71%であった。また、この粘着剤層を60℃に1ヶ月保存してもゲル分率の増加は観察されなかった。さらに、上記粘着剤層のアクリル系ポリマーの固体13C−NMRにおける各々のピークは、側鎖ブチル基の場合には図2に示すように4本のピークが明確に観察された。
(光学部材用粘着剤溶液の調製)
上記アクリル系ポリマー(B)溶液の固形分100重量部に対して、過酸化物としてジベンゾイルパーオキシド(和光純薬社製、1分間半減期:130℃)0.2重量部、イソシアネート系架橋剤としてヘキサメチレンジイソシアネートのトリメチロールプロパン付加物(三井武田ケミカル社製、D160N)0.1重量部、およびシランカップリング剤として3−グリシドキシプロピルトリエトキシシラン0.1重量部を配合し、均一に混合撹拌してアクリル系粘着剤溶液(2)を調整した。
上記アクリル系粘着剤溶液(2)を、シリコーン処理を施したポリエチレンテレフタレート(PET)フィルム(東レ社製、厚さ:38μm)の片面に塗布し、130℃で3分間乾燥・架橋をおこない、乾燥後の厚さが25μmの粘着剤層を形成した。ここで、理論計算により算出される過酸化物の分解量は約88重量%であった。なお、粘着剤層のゲル分率は78%であった。また、この粘着剤層を60℃に1ヶ月保存してもゲル分率の増加は観察されなかった。
(光学部材用粘着剤溶液の調製)
上記アクリル系ポリマー(C)溶液の固形分100重量部に対して、過酸化物としてジベンゾイルパーオキシド(和光純薬社製、1分間半減期:130℃)0.3重量部、イソシアネート系架橋剤としてヘキサメチレンジイソシアネートのトリメチロールプロパン付加物(三井武田ケミカル社製、D160N)0.05重量部、およびシランカップリング剤として2−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン0.1重量部を配合し、均一に混合撹拌してアクリル系粘着剤溶液(3)を調整した。
上記アクリル系粘着剤溶液(3)を、シリコーン処理を施したポリエチレンテレフタレート(PET)フィルム(東レ社製、厚さ:38μm)の片面に塗布し、130℃で3分間乾燥・架橋をおこない、乾燥後の厚さが25μmの粘着剤層を形成した。ここで、理論計算により算出される過酸化物の分解量は約88重量%であった。なお、粘着剤層のゲル分率は75%であった。また、この粘着剤層を60℃に1ヶ月保存してもゲル分率の増加は観察されなかった。
(光学部材用粘着剤溶液の調製)
上記アクリル系ポリマー(A)溶液の固形分100重量部に対して、イソシアネート系架橋剤としてトリレンジイソシアネートのトリメチロールプロパン付加物(日本ポリウレタン工業社製、コロネートL)0.4重量部、およびシランカップリング剤として3−グリシドキシプロピルトリメトキシシラン0.1重量部を配合し、均一に混合撹拌してアクリル系粘着剤溶液(4)を調整した。
上記アクリル系粘着剤溶液(4)を、シリコーン処理を施したポリエチレンテレフタレート(PET)フィルム(東レ社製、厚さ:38μm)の片面に塗布し、130℃で3分間乾燥・架橋をおこない、乾燥後の厚さが25μmの粘着剤層を形成した。なお、粘着剤層のゲル分率は65%であった。
(光学部材用粘着剤溶液の調製)
上記アクリル系ポリマー(B)溶液の固形分100重量部に対して、エポキシ系架橋剤として1,3−ビス(N,N−グリシジルアミノメチル)シクロヘキサン(三菱ガス化学社製、TETRAD−C)0.2重量部、およびシランカップリング剤として3−グリシドキシプロピルトリメトキシシラン0.1重量部を配合し、均一に混合撹拌してアクリル系粘着剤溶液(5)を調整した。
上記アクリル系粘着剤溶液(5)を、シリコーン処理を施したポリエチレンテレフタレート(PET)フィルム(東レ社製、厚さ:38μm)の片面に塗布し、130℃で3分間乾燥・架橋をおこない、乾燥後の厚さが25μmの粘着剤層を形成した。なお、粘着剤層のゲル分率は60%であった。
(光学部材用粘着剤溶液の調製)
上記アクリル系ポリマー(D)溶液の固形分100重量部に対して、過酸化物としてジベンゾイルパーオキシド(和光純薬社製、1分間半減期:130℃)0.3重量部、およびシランカップリング剤として3−グリシドキシプロピルトリメトキシシラン0.1重量部を配合し、均一に混合撹拌してアクリル系粘着剤溶液(6)を調整した。
上記アクリル系粘着剤溶液(6)を、シリコーン処理を施したポリエチレンテレフタレート(PET)フィルム(東レ社製、厚さ:38μm)の片面に塗布し、130℃で3分間乾燥・架橋をおこない、乾燥後の厚さが25μmの粘着剤層を形成した。ここで、理論計算により算出される過酸化物の分解量は約88重量%であった。なお、粘着剤層のゲル分率は60%であった。また、この粘着剤層を60℃に1ヶ月保存すると、ゲル分率が15重量%まで低下した。
Claims (12)
- モノマー単位として、一般式CH2=C(R1)COOR2(ただし、R1は水素またはメチル基、R2は炭素数2〜14のアルキル基である)で表される(メタ)アクリル系モノマー50〜98重量%含有する(メタ)アクリル系ポリマーからなる粘着剤組成物を架橋してなる粘着剤層であって、前記(メタ)アクリル系ポリマーのカルボニル基の固体13C−NMRにおけるピーク強度を100とする場合に、前記(メタ)アクリル系ポリマーの末端メチル基の固体13C−NMRにおけるピーク強度が92〜130であることを特徴とする粘着剤層。
- 前記粘着剤組成物が、前記(メタ)アクリル系ポリマー100重量部に対し、さらに過酸化物0.02〜2重量部含有してなる請求項1に記載の粘着剤層。
- 前記粘着剤組成物が、前記(メタ)アクリル系ポリマー100重量部に対し、さらにイソシアネート系架橋剤0.02〜2重量部含有してなる請求項2に記載の粘着剤層。
- 前記粘着剤層のゲル分率が40〜90重量%である請求項1〜3のいずれかに記載の粘着剤層。
- 光学部材用として用いられる請求項1〜4のいずれかに記載の粘着剤層。
- 支持体の片面または両面に、モノマー単位として、一般式CH2=C(R1)COOR2(ただし、R1は水素またはメチル基、R2は炭素数2〜14のアルキル基である)で表される(メタ)アクリル系モノマー50〜98重量%含有する(メタ)アクリル系ポリマーからなる粘着剤組成物からなる層を形成する工程と、前記(メタ)アクリル系ポリマーのカルボニル基の固体13C−NMRにおけるピーク強度を100とする場合に、前記(メタ)アクリル系ポリマーの側鎖の末端メチル基の固体13C−NMRにおけるピーク強度が92〜130となるように前記粘着剤組成物からなる層を架橋処理する工程とを含む粘着剤層の製造方法。
- 前記架橋処理が過酸化物架橋処理である請求項6に記載の粘着剤層の製造方法。
- 前記過酸化物架橋処理が前記過酸化物を50重量%以上分解する処理である請求項7に記載の粘着剤層の製造方法。
- 前記粘着剤層のゲル分率が40〜90重量%である請求項6〜8のいずれかに記載の粘着剤層の製造方法。
- 前記粘着剤層が光学部材用として用いられる請求項6〜9のいずれかに記載の粘着剤層の製造方法。
- 請求項1〜5のいずれかに記載の粘着剤層を光学部材の片面または両面に形成してなることを特徴とする粘着剤付光学部材。
- 請求項11に記載の粘着剤付光学部材を少なくとも1枚用いた画像表示装置。
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