JP2017024944A - 透明な粘着剤層を有するカバー部材 - Google Patents
透明な粘着剤層を有するカバー部材 Download PDFInfo
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- JP2017024944A JP2017024944A JP2015145222A JP2015145222A JP2017024944A JP 2017024944 A JP2017024944 A JP 2017024944A JP 2015145222 A JP2015145222 A JP 2015145222A JP 2015145222 A JP2015145222 A JP 2015145222A JP 2017024944 A JP2017024944 A JP 2017024944A
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Classifications
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Abstract
Description
面積比は、一辺が10μm〜200μmの方形領域において、該方形領域の全体面積に対する高屈折率材料粒子17の占める面積の割合とし、複数の方形領域について測定を行い、その測定値を平均することにより面積比が求められる。
ガラス製カバーレンズとして、厚さ0.65mmの無アルカリガラス(屈折率1.53)を使用した。図7(a)は、当該カバー部材の構成をカバー部材26として示す。プラスチック製カバーレンズとしては、厚さ0.7mmの表面が硬化処理されたアクリル板(商品名「アクリライト(R) MR200」、三菱レイヨン社製、表面(硬化層)屈折率1.53)を使用した。図7(b)は、当該カバー部材の構成をカバー部材27として示す。図中の各層に記載した数値は、屈折率を表す。以下、同様にその他の図(図7から図11)において各層に記載された数値は、単位の表記がなければ屈折率を表す。
(アクリルオリゴマーの作成)
ジシクロペンタニルアクリレート(DCPMA、メタクリル酸ジシクロペンタニル)60重量部、メチルメタクリレート(MMA、メタクリル酸メチル)40重量部、連鎖移動剤としてのα−チオグリセロール3.5重量部、及び重合溶媒としてのトルエン100重量部を、4つ口フラスコに投入し、これらを窒素雰囲気下において70℃で1時間撹拌した。次に、重合開始剤としての2,2´−アゾビスイソブチロニトリル0.2重量部を4つ口フラスコに投入し、70℃で2時間反応させ、続いて、80℃で2時間反応させた。その後、反応液を130℃温度雰囲気下に投入し、トルエン、連鎖移動剤及び未反応モノマーを乾燥除去させ、固形状のアクリル系ポリマーを得た。このようにして得られたアクリル系ポリマーを「アクリル系ポリマー(A−1)」とした。このアクリル系ポリマー(A−1)の重量平均分子量(Mw)は5.1×103であった。
2−エチルヘキシルアクリレート(2EHA)68重量部、N−ビニル−2−ピロリドン(NVP)14.5重量部、及びヒドロキシエチルアクリレート(HEA)17.5重量部から構成されるモノマー混合物に、光重合開始剤(商品名「イルガキュア184」、BASF社製)0.035重量部、及び光重合開始剤(商品名「イルガキュア651」、BASF社製)0.035重量部を配合した後、このモノマー混合物を窒素雰囲気下で紫外線に曝露して部分的に光重合させることにより、重合率約10重量%の部分重合物(アクリル系ポリマーシロップ)を得た。
2−エチルヘキシルアクリレート(2EHA)28.5重量部、イソステアリルアクリレート(ISTA)28.5重量部、イソボルニルアクリレート22重量部、4−ヒドロキシブチルアクリレート(4HBA)20重量部、2種の光重合開始剤(商品名:イルガキュア184、BASF製)0.05重量部、及び光重合開始剤(商品名:イルガキュア651、BASF製)0.05重量部を配合した後、このモノマー混合物を窒素雰囲気下で紫外線に曝露して部分的に光重合させることにより、重合率約10重量%の部分重合物(アクリル系ポリマーシロップ)を得た。
〈粘着剤A/高屈折率材料のナノ粒子分散液を使用する事例〉
(粘着剤A/ナノ粒子分散液を使用した事例)
粘着剤層の厚さが250μmであって、該粘着剤層の両面がPET剥離シートで保護されている状態の粘着剤A(粘着剤層の屈折率:1.49)の一方の軽剥離PETシートを剥離した。露出した粘着剤層の表面に、高屈折率粒子を含有する分散液としてのジルコニア粒子(ZrO2、屈折率:2.17、平均一次粒子径:20nm)を含有する塗布用処理液(分散媒:エタノール、粒子濃度:1.2重量%、分散液の透過率:82%、CIKナノテック(株)製)を、屈折率調整区分の厚さが20nm〜200nmになるようにバーコーターRDS No.5で塗布し、110℃の乾燥オーブンで180秒間乾燥させた。次いで、ジルコニア(ZrO2)粒子が分散された粘着剤層表面に、支持体としてPET剥離シート(75μm)を貼り合わせ、屈折率調整区分付粘着剤(A1)を得た。なお、ジルコニア粒子の平均一次粒子径は、TEM観察により計測した。図8(a)は、屈折率調整区分付粘着剤(A1)の構成を示す。
上記の事例と同様にして、下記の粘着剤及び高屈折率材料のナノ粒子分散液を使用して同様に屈折率調整区分付粘着剤(B1)を作製した。使用材料は、粘着剤B(屈折率1.48)、ZrO2 ナノ粒子分散液(分散媒:エタノール、粒径20nm)であった。
なお、検討に使用した粘着剤の特性一覧を下記表に示す。図8(b)は、屈折率調整区分付粘着剤(B1)の構成を示す。
厚さ100μmのシクロオレフィンポリマーフィルム(商品名:「ゼオノアZF16」、面内複屈折率:0.0001、日本ゼオン(株)製)の両面に、直径3μmの複数の粒子(商品名:「SSX105」、積水樹脂(株)製)を、バインダー樹脂(商品名:「ユニディックRS29−120」、DIC社製)100部に対して0.07部添加した塗工液をバーコーターを用いて塗布し、80℃のオーブン下で1分間乾燥後、積算光量各300mJの紫外線(高圧水銀灯)を照射することで両面にアンチブロッキング層を有するフィルムを形成した(以下、COP基材)。次に、COP基材の片面に、屈折率調整剤(商品名:「オプスター KZ6661」、JSR(株)製)をバーコーターにより塗布し、80℃のオーブン下で1分間乾燥後、積算光量各300mJの紫外線(高圧水銀灯)を照射することで、厚さ100nm、屈折率1.65の屈折率調整層を形成した。得られたCOP基材の屈折率調整層の表面に、巻き取り式スパッタ装置において、透明導電層として厚さ23nmのインジウムスズ酸化物層(ITO)を積層した。上記透明導電層上の一部にフォトレジスト膜を形成した後、これを25℃、5重量%の塩酸(塩化水素水溶液)に1分間浸漬して、透明導電層のエッチングを行った。これにより電極配線パターンに相当する透明導電層が存在する部分(パターン部)(図9(a)中のITO32)と、除去された部分(開口部)とが形成された、パターン付透明導電性フィルム(1)を得た。図9(a)に示す積層体31は、パターン付透明導電性フィルム(1)を表す。
厚さ50μmのPETフィルム(商品名:「ルミラー:U40」東レ社製)の片面に直径3μmの複数の粒子(商品名:「SSX105」、積水樹脂(株)製)を、バインダー樹脂(商品名:「ユニディックRS29−120」、DIC社製)100部に対して0.1部添加した塗工液を、バーコーターを用いて塗布し、80℃のオーブン下1分間乾燥後、積算光量各300mJの紫外線(高圧水銀灯)を照射することで片面に膜厚1.5μmのアンチブロッキング層を形成した(以下、PET基材)。次に、先ほど塗工した面とは逆面に、メラミン樹脂:アルキド樹脂:有機シラン縮合物(重量比2:2:1)の熱硬化型樹脂を塗工し、これを硬化させて、膜厚30nm、屈折率1.54の屈折率調整層を形成した。その後、屈折率調整層を有するPET基材を、巻き取り式スパッタ装置に投入し、屈折率調整層1の表面に、透明導電層として厚み23nmのインジウムスズ酸化物層(ITO)を積層した。上記透明導電層上の一部にフォトレジスト膜を形成した後、これを25℃、5重量%の塩酸(塩化水素水溶液)に1分間浸漬して、透明導電層のエッチングを行った。これにより電極配線パターンに相当する透明導電層が存在する部分(パターン部)(図9(b)中ITO36)と、除去された部分(開口部)とが形成された、パターン付透明導電性フィルム(2)を得た。図9(b)に示す積層体35は、パターン付透明導電性フィルム(2)を表す。
(実施例1)
図10(a)に示す光学部材積層体を作製した。屈折率調整区分付粘着剤(A1)のベース粘着剤A側のPET剥離シートを剥離して、ガラス製カバーレンズ(カバー部材26)の一方の面に貼り合せ、屈折率調整区分がカバーレンズの外側になるように積層された、粘着剤付カバーレンズ(A)を作成した。作成した粘着剤付カバーレンズ(A)の屈折率調整区分側のPET剥離シートを剥離して、パターンを有する透明導電フィルム(1)(積層体31)の透明導電層の上に、該粘着剤付カバーレンズの屈折率調整区分(高屈折率粒子を有する側)と該透明導電層と該基材上の透明導電層の部分と導電層がない部と接触するように積層して作成した。また、屈折率調整区分(高屈折率粒子を有する側)と接触する面とは反対側の面に、反射率測定のために、評価用の黒色のPETフィルム39を貼った。
図10(b)に示す光学部材積層体を作製した。積層する粘着剤を屈折率調整区分付粘着剤(B1)に変更して、ベース粘着剤側のPET剥離シートを剥離して、プラスチック製カバーレンズ(カバー部材27)の一方の面に貼り合せ、屈折率調整区分が該カバーレンズの外側になるように積層された、粘着剤付カバーレンズ(B)を作成した。作成した粘着剤付カバーレンズ(B)の屈折率調整区分側のPET剥離シートを剥離して、パターンを有する透明導電フィルム(2)の透明導電層の上に、該粘着剤付カバーレンズの屈折率調整区分(高屈折率粒子を有する側)と該透明導電層と該基材上の透明導電層の部分と導電層がない部と接触するように積層して作成した。また、屈折率調整区分(高屈折率粒子を有する側)と接触する面とは反対側の面に、反射率測定のために、評価用の黒色のPETフィルム39を貼った。
図11(a)に示す光学部材積層体を作製した。積層する屈折率調整区分付粘着剤(A1)を、屈折率調整層を有さない粘着剤Aに変更して、粘着剤付カバーレンズ(C)を作成した以外は、実施例1と同様に作成した。
図11(b)に示す光学部材積層体を作製した。積層する屈折率調整区分付粘着剤(B1)を、屈折率調整層を有さない粘着剤Bに変更して、粘着剤付カバーレンズ(D)を作成した以外は、実施例2と同様に作成した。
〈アクリル系ポリマーの重量平均分子量(Mw)の測定〉
作製した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。
装置:東ソー社製、HLC−8220GPC
カラム:
サンプルカラム;東ソー社製、TSKguardcolumn Super HZ−H(1本)+TSKgel Super HZM−H(2本)
リファレンスカラム;東ソー社製、TSKgel Super H−RC(1本)
流量:0.6mL/min
注入量:10μL
カラム温度:40℃
溶離液:THF
注入試料濃度:0.2重量%
検出器:示差屈折計
なお、重量平均分子量はポリスチレン換算により算出した。
実施例のそれぞれにおける粘着剤層の高屈折率材料粒子を有する側の表面を、FE−SEMを用いて、加速電圧2kV、観察倍率500倍、2,000倍、5,000倍、及び20,000倍で観察した。図8にその20,000倍写真を示す。高屈折率材料粒子が均一に分散されていることが分かる。
実施例の粘着剤層の高屈折率材料粒子を有する側の表面近傍の断面を、透過型電子顕微鏡(TEM)を用いて、倍率30,000倍で観察した。その結果を図13(a)(b)に示す。図13(a)では、屈折率調整用区分の厚みのほぼ全体にわたって高屈折率材料粒子がほぼ均一に分布しているが、図13(b)の例では、粘着剤層における高屈折率材料粒子の分布が、粘着剤層の表面で最も高く、粘着剤層の厚さ方向に従って減少していく分布を有することが分かる。
実施例及び比較例で得られた粘着層の平均表面屈折率を、分光エリプソメーター(EC−400、JA.Woolam製)を用いてナトリウムD線(589nm)における屈折率を測定した。実施例及び比較例の粘着層では、両面の剥離シートを剥離して、粒子を塗布していない面に黒板を貼り合わせた状態で、粒子が塗布されている面の平均屈折率を測定した。比較例の粘着シートでは、両方の剥離シートを剥離して、一方の面に黒板を貼り合わせた状態で、粘着剤層表面の平均屈折率を測定した。
粘着剤層の深さ方向の断面を調整し、TEM観察を行った。得られたTEM像(直接倍率3000〜30000倍)から屈折率調整区分の厚さの測定を計測した。屈折率調整区分層の厚みは、粘着剤ベース層との調整区分との界面の凸凹の平均値とし、粘着剤ベース層との界面の判別が困難な場合には、表面TEM像を画像処理ソフト(ImageJ)で二値化画像処理し、ナノ粒子の90%が存在する領域の深さを調整区分の厚みとした。
粘着剤層の粒子塗布側の表面を、FE−SEMを用いて、加速電圧2kV、観察倍率500倍、2,000倍、5,000倍で観察した。得られた表面SEM像を画像処理ソフト(ImageJ)で二値化画像処理することで、長辺23μm、短辺18μmの長方形領域における全体面積に対する面積として高屈折率粒子の占める面積比率(%)を求めた。
実施例及び比較例で得られた粘着シートでは、高屈折率材料を塗布した側の剥離シートを剥離して、スライドガラス(商品名:白研磨 No.1、厚さ:0.8〜1.0mm、全光線透過率:92%、ヘイズ:0.2%、松浪硝子工業(株)製)に貼り合わせた。さらに他方の剥離シートを剥離して、ベース粘着剤層/粘着性の屈折率調整用層/スライドガラスの層構成を有する試験片を作製した。また、比較例の粘着シートでは、一方の剥離シートを剥離して、スライドガラス(商品名:白研磨 No.1、厚さ:0.8〜1.0mm、全光線透過率:92%、ヘイズ:0.2%、松浪硝子工業(株)製)に貼り合わせ、さらに他方の剥離シートを剥離して、ベース粘着剤層/スライドガラスの層構成を有する試験片を作製した。上記試験片の可視光領域における全光線透過率、ヘイズ値を、ヘイズメーター(装置名:HM−150、(株)村上色彩研究所製)を用いて測定した。
実施例及び比較例で得られた粘着シートから、長さ100mm、幅25mmのシート片を切り出した。次いで、実施例及び比較例のシート片では、粒子が塗布されていない側の剥離シートを剥離して、PETフィルム(商品名:ルミラー S−10、厚さ:25μm、東レ(株)製)を貼付(裏打ち)した。また、比較例1、2のシート片では、一方の剥離シートを剥離して、PETフィルム(商品名:ルミラー S−10、厚さ:25μm、東レ(株)製)を貼付(裏打ち)した。次に、他方の剥離シートを剥離して、試験板としてのガラス板(商品名:ソーダライムガラス ♯0050、松浪硝子工業(株)製)に、2kgローラー、1往復の圧着条件で圧着し、試験板/粘着剤層/PETフィルムから構成されるサンプルを作製した。得られたサンプルについて、オートクレーブ処理(50℃、0.5MPa、15分)し、その後、23℃、50%R.H.の雰囲気下で30分間放冷した。放冷後、引張試験機(装置名:オートグラフ AG−IS、(株)島津製作所製)を用い、JIS Z0237に準拠して、23℃、50%R.H.の雰囲気下、引張速度300mm/分、剥離角度180°の条件で、試験板から粘着シート(粘着剤層/PETフィルム)を引きはがし、180°引き剥がし接着力(N/25mm)を測定した。また、各実施例、比較例において、高屈折率材料の粒子未塗布の粘着シートを作製し、当該高屈折率材料の粒子未塗布の粘着シートにおいても、上記同様に、180度ピール接着力を測定した。
高屈折率粒子を含有する分散液の透過率は、光電比色計(AC−114、OPTIMA社製)で530nmのフィルターを用いて測定した。分散溶媒単独の透過率を100%として、各実施例、比較例で使用した分散液の透過率(%)を測定した。
実施例及び比較例の光学部材積層体の一方の面を反射率測定面とし、反対側の面に片面粘着付黒色PET(PET75NBPET38、リンテック(株)製)を貼って反射率測定用の試料とした。光学部材積層体の反射率測定面側の反射率(Y値)、及び反射率測定面側の反射色相(L*, a*,b*値:CIE1976)を反射型分光光度計(U4100、(株)日立ハイテクノロジーズ製)により測定した。測定は、透明導電層をエッチングした部分と、エッチングしていない部分の双方の位置で行った。すなわち、透明導電層をエッチングした部分(開口部)の測定は、粘着剤層の屈折率調整区分と光学部材積層体の基材との界面の反射率であり、エッチングしていない部分(パターン部)の測定は、粘着剤層の屈折率調整区分と透明導電層界面の反射率を示す。反射色相についても同様である。
反射抑制率(%)=反射率(%)−粒子がない場合の反射率(%)
色差値ΔE*ab=[(ΔL*)^2+(Δa*)^2+(Δb*)^2]^(1/2)
すなわち、光学部材積層体の反射色差値(ΔE*ab)は、エッチングした部分とエッチングしてない部分の色味の差を示す指標である。
パターン見栄えの評価としては、導電層部と導電層がない部分との反射率差(%)と反射色差値から判定を行った。反射率差(%)が、1.0%以上であれば×とした。反射率差1.0%未満であって、色差値が1.0未満であれば◎、1.0〜3.0未満であれば○、3.0以上であれば△とした。
S1、S2・・・支持体
1・・・光学部材積層体
2・・・第1光学部材
3,13・・・透明な粘着剤層
3a、13a・・・ベース粘着剤区分
3b、13b・・・屈折率調整用区分
4・・・第2光学部材
7・・・透明導電性層
17・・・高屈折率材料粒子
19・・・分散液
20・・・粘着剤ベース材料
21・・・積層体
22、26、27・・・カバー部材
23・・・屈折率調整区分付粘着剤
24・・・透明導電性フィルム
25・・・画像表示装置
31、35・・・積層体
32、36・・・ITO層
33、37・・・屈折率調整層
34・・・COP基材
38・・・PET基材
39・・・評価用黒PET
Claims (13)
- 透明な粘着剤層を有するカバー部材であって、
前記粘着剤層は、一方の主面から厚み方向にわたって透明な粘着剤ベース材料により本質的に形成されるベース粘着剤区分と、該粘着剤層の他方の主面から厚み方向にわたって形成された透明な粘着性の屈折率調整用区分とを含み、前記ベース粘着剤区分は前記カバー部材と接し、前記屈折率調整用区分は前記粘着剤ベース材料の屈折率より高い屈折率を有することを特徴とするカバー部材。 - 請求項1に記載したカバー部材であって、前記カバー部材は、ガラス又は透明樹脂部材であることを特徴とするカバー部材。
- 請求項1又は請求項2に記載したカバー部材であって、前記屈折率調整用区分は、厚みが20nm〜600nmであることを特徴とするカバー部材。
- 請求項1から請求項3までのいずれか1項に記載したカバー部材であって、前記屈折率調整用区分は、前記粘着剤ベース材料と同じ粘着性材料に、該粘着性材料より高い屈折率を有する高屈折率材料の粒子が分散されて該屈折率調整用区分の平均屈折率を高めるように構成されたことを特徴とするカバー部材。
- 請求項4に記載したカバー部材であって、前記高屈折率材料の粒子の屈折率は1.60〜2.74であることを特徴とするカバー部材。
- 請求項4から請求項5までのいずれか1項に記載したカバー部材であって、前記高屈折率材料は、TEM観察による平均一次粒子径が3nm〜100nmであることを特徴とするカバー部材。
- 請求項4から請求項6までのいずれか1項に記載したカバー部材であって、前記高屈折率材料の粒子と前記粘着剤ベース材料の屈折率の差が0.15〜1.34であることを特徴とするカバー部材。
- 請求項4から請求項7までのいずれか1項に記載したカバー部材であって、前記高屈折率材料は、TiO2、ZrO2、CeO2、Al2O3、BaTiO3、Nb2O5、及びSnO2からなる群から選択された1又は複数の化合物であることを特徴とするカバー部材。
- 請求項1から請求項7までのいずれか1項に記載したカバー部材であって、前記屈折率調整用区分は、前記粘着剤ベース材料と同じ粘着性材料に該粘着性材料より高い屈折率を有する粒子、ポリマー又はオリゴマーの形態の有機材料が含まれることによって該屈折率調整用区分の平均屈折率を高めるように構成されたことを特徴とするカバー部材。
- 請求項9に記載したカバー部材であって、前記粘着剤ベース材料の屈折率は1.40〜1.55であり、前記有機材料の屈折率は1.59〜2.04であることを特徴とするカバー部材。
- 請求項1から請求項10までのいずれか1項に記載したカバー部材であって、前記粘着剤層の全光線透過率が80%以上であることを特徴とするカバー部材。
- 請求項4から請求項8までのいずれか1項に記載したカバー部材であって、前記高屈折率材料の粒子は、複数の粒子が凝集した凝集体の形態で存在する部分を含むことを特徴とするカバー部材。
- 請求項4から請求項12までのいずれか1項に記載したカバー部材であって、前記屈折率調整用区分は、前記粘着剤層の厚み方向に、不規則な深さで存在することを特徴とするカバー部材。
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WO2017014090A1 (ja) | 2017-01-26 |
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