TW201536881A - 黏著劑組合物及含彼之偏光板 - Google Patents

黏著劑組合物及含彼之偏光板 Download PDF

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TW201536881A
TW201536881A TW104109826A TW104109826A TW201536881A TW 201536881 A TW201536881 A TW 201536881A TW 104109826 A TW104109826 A TW 104109826A TW 104109826 A TW104109826 A TW 104109826A TW 201536881 A TW201536881 A TW 201536881A
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adhesive composition
weight
acid
polarizing plate
meth
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崔漢永
劉旼根
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東友精細化工有限公司
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Abstract

本發明提供黏著劑組合物，其包含丙烯酸共聚物、交聯劑、矽烷偶合劑及pKa為3或更小之強酸；包含該黏著劑組合物之偏光板及液晶顯示裝置。本發明之黏著劑組合物具有高黏著強度及極佳耐久性。

Description

黏著劑組合物及含彼之偏光板
本發明係關於黏著劑組合物及包含其之偏光板。具體而言，本發明提供具有高黏著強度及極佳耐久性之黏著劑組合物、包含該黏著劑組合物之偏光板及具有該偏光板之液晶顯示裝置。
液晶顯示裝置(LCD)具有包括液晶單元及經由黏著劑層層壓在液晶單元兩側上之偏光板之液晶面板。
用於將偏光板附接至液晶單元之黏著劑應同時滿足耐久性(例如耐熱性、耐熱/濕性、耐熱震性及耐冷性)、重工作性以解決接觸誤差或外源物質之存在、防止由偏光板之收縮應力產生之光漏，及抗靜電特性以防止靜電產生同時移除離型膜來黏著偏光板。在該等特性中，用於達成耐久性及重工作性之黏著劑特徵彼此衝突。因此，尚未完全滿足兩種物理特性。
為提供黏著劑與基板之良好黏著，提出向黏著劑中添加矽烷偶合劑之技術。日本專利申請公開案第(Hei)4-223403號揭示包含具有環氧基之矽烷化合物(例如3-縮水甘油氧基丙基三甲氧基矽烷)之黏著劑組合物。然而，該黏著劑組合物在實際應用中具有不充分的黏著及耐久性。
本發明之目標係提供黏著劑組合物，其包含pKa為3或更小之強酸以具有高黏著強度及極佳耐久性。
本發明之另一目標係提供包括包含黏著劑組合物之黏著劑層之偏光板。
本發明之另一目標係提供在液晶單元之至少一個表面上具有偏光板之液晶顯示裝置。
本發明之一態樣提供黏著劑組合物，其包含丙烯酸共聚物、交聯劑、矽烷偶合劑及pKa為3或更小之強酸。
在本發明之一實施例中，pKa為3或更小之強酸包含草酸或對甲苯磺酸。
本發明之另一態樣提供包括包含黏著劑組合物之黏著劑層之偏光板。
本發明之另一態樣提供在液晶單元之至少一個表面上具有偏光板之液晶顯示裝置。
本發明之黏著劑組合物藉由強酸之作用來增加矽烷偶合劑之活性，由此極大地增強黏著強度且容易提供極佳耐久性。
本發明更詳細闡述於下文中。
本發明之一實施例係關於黏著劑組合物，其包含丙烯酸共聚物、交聯劑、矽烷偶合劑及pKa為3或更小之強酸。
在本發明之一實施例中，丙烯酸共聚物係黏著劑樹脂，其可係 具有C1-12烷基之(甲基)丙烯酸酯單體及具有可交聯官能基之單體的共聚物。如本文所使用，術語「(甲基)丙烯酸酯」係指丙烯酸酯及甲基丙烯酸酯。
具有C1-12烷基之(甲基)丙烯酸酯單體之實例可包括(甲基)丙烯酸正丁基酯、(甲基)丙烯酸2-丁基酯、(甲基)丙烯酸第三丁基酯、(甲基)丙烯酸2-乙基己基酯、(甲基)丙烯酸2-乙基丁基酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸正丙基酯、(甲基)丙烯酸異丙基酯、(甲基)丙烯酸戊基酯、(甲基)丙烯酸正辛基酯、(甲基)丙烯酸異辛基酯、(甲基)丙烯酸正壬基酯、(甲基)丙烯酸異壬基酯、(甲基)丙烯酸癸基酯、(甲基)丙烯酸月桂基酯等。該等單體可單獨使用或以兩者或更多者之組合使用。其中，丙烯酸正丁基酯、丙烯酸2-乙基己基酯及其混合物較佳。
具有C1-12烷基之(甲基)丙烯酸酯單體較佳係以基於100重量%之用於製備丙烯酸共聚物之總單體計為80重量%至99重量%、更佳90重量%至95重量%之量存在。若(甲基)丙烯酸酯單體之量小於80重量%，則黏著強度可能不足。若(甲基)丙烯酸酯單體之量大於99重量%，則可能降低內聚強度。
具有可交聯官能基之單體係用於經由與如下文所述之交聯劑化學鍵結來獲得內聚強度或黏著強度，及其可包括具有羥基之單體、具有羧基之單體、具有醯胺基團之單體、具有三級銨基團之單體等。該等單體可單獨使用或以兩者或更多者之組合使用。
具有羥基之單體之實例可包括(甲基)丙烯酸2-羥基乙基酯、(甲基)丙烯酸2-羥基丙基酯、(甲基)丙烯酸2-羥基丁基酯、(甲基)丙烯酸4-羥基丁基酯、(甲基)丙烯酸6-羥基己基酯、2-羥基乙二醇(甲基)丙烯酸酯、2-羥基丙二醇(甲基)丙烯酸酯、具有C2-4伸烷基之羥基伸烷基二醇(甲基)丙烯酸酯等。其中，(甲基)丙烯酸2-羥基乙基酯較佳。
具有羧基之單體之實例可包括一元酸，例如(甲基)丙烯酸及巴豆酸；二元酸，例如馬來酸、衣康酸及富馬酸及其單烷基酯；3-(甲基)丙烯醯基丙酸；具有C2-3烷基之(甲基)丙烯酸2-羥基烷基酯之琥珀酸酐開環加成物、具有C2-4伸烷基之羥基伸烷基二醇(甲基)丙烯酸酯之琥珀酸酐開環加成物、藉由將琥珀酸酐開環添加至具有C2-3烷基之(甲基)丙烯酸2-羥基烷基酯之己內酯加成物獲得的化合物等。其中，(甲基)丙烯酸較佳。
具有醯胺基團之單體之實例可包括(甲基)丙烯醯胺、N-異丙基丙烯醯胺、N-第三丁基丙烯醯胺等。其中，(甲基)丙烯醯胺較佳。
具有三級胺基團之單體之實例可包括(甲基)丙烯酸N,N-(二甲基胺基)乙基酯、(甲基)丙烯酸N,N-(二乙基胺基)乙基酯、(甲基)丙烯酸N,N-(二甲基胺基)丙基酯等。
具有可交聯官能基之單體較佳係以基於100重量%之用於製備丙烯酸共聚物之總單體計為1重量%至20重量%、更佳1重量%至10重量%之量存在。若具有可交聯官能基之單體之量小於1重量%，則可能降低內聚強度。若具有可交聯官能基之單體之量大於20重量%，則可能減弱黏著強度。
除上述單體外，可進一步含有介於不使黏著強度降格之範圍內、例如10重量%或更小、較佳5重量%或更小之其他單體。
共聚物可使用業內通常已知(但不限於)之整體聚合、溶液聚合、乳化聚合或懸浮聚合等來製備。其中，溶液聚合較佳。此外，可使用業內通常已知之溶劑、聚合起始劑、用於控制分子量之鏈轉移劑等進行聚合。
丙烯酸共聚物可具有50,000至2,000,000、較佳1,000,000至2,000,000之聚苯乙烯轉換量平均分子量，如藉由凝膠滲透層析(GPC)所量測。
在本發明之一實施例中，交聯劑藉由使共聚物交聯用於增強黏著劑之內聚強度。舉例而言，交聯劑可包括(但不限於)異氰酸酯化合物、環氧化合物等。該等化合物可單獨使用或以兩者或更多者之組合使用。
異氰酸酯化合物之實例可包括二異氰酸酯化合物，例如二異氰酸伸甲苯基酯、二甲苯二異氰酸酯、2,4-二苯基甲烷二異氰酸酯、4，4-二苯基甲烷二異氰酸酯、二異氰酸六亞甲基酯、異佛爾酮二異氰酸酯、四甲基二甲苯二異氰酸酯及萘二異氰酸酯；及具有三個官能基之多官能基異氰酸酯化合物，例如藉由使1mol多元醇化合物(例如三羥甲基丙烷)與3mol二異氰酸酯化合物反應獲得之加成物、藉由自縮合3mol二異氰酸酯化合物獲得之異氰尿酸酯、藉由縮合自2mol二異氰酸酯化合物製備之二異氰酸酯脲與1mol二異氰酸酯化合物獲得之雙脲、三苯基甲烷三異氰酸酯及雙三異氰酸亞甲基酯。
環氧化合物之實例可包括乙二醇二縮水甘油醚、二乙二醇二縮水甘油醚、聚乙二醇二縮水甘油醚、丙二醇二縮水甘油醚、三丙二醇二縮水甘油醚、聚丙二醇二縮水甘油醚、新戊二醇二縮水甘油醚、1,6-己二醇二縮水甘油醚、聚四亞甲基二醇二縮水甘油醚、甘油二縮水甘油醚、甘油三縮水甘油醚、二甘油聚縮水甘油醚、聚甘油聚縮水甘油醚、間苯二酚二縮水甘油醚、2,2-二溴新戊二醇二縮水甘油醚、三羥甲基丙烷三縮水甘油醚、異戊四醇聚縮水甘油醚、山梨醇聚縮水甘油醚、己二酸二縮水甘油酯、苯二甲酸二縮水甘油酯、異氰尿酸叁(縮水甘油基)酯、異氰尿酸叁(縮水甘油氧基乙基)酯、1,3-雙(N,N-縮水甘油基胺基甲基)環己烷、N,N,N’,N’-四縮水甘油基-間二甲苯二胺等。
除異氰酸酯化合物及環氧化合物外，三聚氰胺化合物可進一步單獨使用或以兩者或更多者之組合使用。
三聚氰胺化合物之實例可包括六羥甲基三聚氰胺、六甲氧基甲基三聚氰胺、六丁氧基甲基三聚氰胺等。
較佳可含有基於100重量份數之丙烯酸共聚物計為0.1重量份數至15重量份數、更佳0.1重量份數至5重量份數之量的交聯劑。若交聯劑之量小於0.1重量份數，則內聚強度可能因不充分交聯所致而降低，由此導致耐久性減弱，例如提升及損壞切割特性。若交聯劑之量大於15重量份數，則殘餘應力因過度交聯而無法充分鬆弛。
在本發明之一實施例中，矽烷偶合劑用於增強黏著劑與基板之黏著，且其可係含有官能基(例如胺基、環氧基、乙醯乙醯基、聚伸烷基二醇、丙烯酸基團及烷基)之烷氧基矽烷，較佳含有環氧基之矽烷偶合劑。
矽烷偶合劑之特定實例可包括乙烯基氯矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、2-(3,4-環氧基環己基)乙基三甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、3-縮水甘油氧基丙基二乙氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、對苯乙烯基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基甲基三乙氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-三乙氧基矽基-N-(1,3-二甲基亞丁基)丙基胺、N-苯基-3-胺基丙基三甲氧基矽烷、3-氯丙基三甲氧基矽烷、3-巰基丙基甲基二甲氧基矽烷、3-巰基丙基三甲氧基矽烷、雙(三乙氧基矽基丙基)四硫化物、3-異氰酸基丙基三乙氧基矽烷等，較佳基於環氧基之矽烷，例如2-(3,4-環氧基環己基)乙基三甲氧基矽烷、3-縮水 甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、3-縮水甘油氧基丙基二乙氧基矽烷及3-縮水甘油氧基丙基三乙氧基矽烷。該等化合物可單獨使用或以兩者或更多者之組合使用。
矽烷偶合劑較佳係以基於100重量份數之丙烯酸共聚物計為0.01重量份數至2重量份數、更佳0.01重量份數至0.5重量份數之量存在。若矽烷偶合劑之量小於0.01重量份數，則增加黏著強度之效應可能不足以導致耐熱條件下之剝離缺陷。若矽烷偶合劑之量大於2重量份數，則可能減弱增加黏著強度之效應。
在本發明之一實施例中，當考慮到在有機溶劑中之溶解度時，若強酸之pKa為3或更小，則其可係任何酸、較佳pKa為3或更小之有機酸。強酸之特定實例可包括具有拉電子取代基之乙酸衍生物，例如草酸、硝基乙酸及氯乙酸；有機磺酸，例如對甲苯磺酸、苯磺酸、甲磺酸及三氟甲磺酸；及有機磷酸衍生物，例如苯基膦酸。其中，草酸及對甲苯磺酸較佳。
強酸較佳係以基於100重量份數之丙烯酸共聚物計為0.001重量份數至0.1重量份數之量存在。若強酸之量小於0.001重量份數，則增加黏著強度之效應可能不足。若強酸之量大於0.1重量份數，則內聚強度可能因不足凝膠分率而降低。
根據本發明一實施例之黏著劑組合物(若需要)可進一步包含添加劑，例如增黏樹脂、抗氧化劑、整平劑、表面潤滑劑、染料、顏料、消泡劑、填充劑、光穩定劑及抗靜電劑，以控制黏著、內聚、黏度、彈性、玻璃轉變溫度、抗靜電特性等。
本發明之黏著劑組合物可用於附接偏光板與液晶單元之黏著劑及表面保護膜用黏著劑。而且，黏著劑組合物可用於以下用途之黏著劑：保護膜、反射片、多種結構用黏著片、照片用黏著片、車道用黏著片、光學黏著劑產品、電子部件、一般黏著片產品及醫用貼片。
本發明之一實施例係關於包括包含如上文所述之黏著劑組合物之黏著劑層之偏光板。
黏著劑層之厚度可端視其黏著強度而變化，且可較佳介於3μm至100μm、更佳10μm至100μm範圍內。
此一偏光板可應用於典型液晶顯示裝置。具體而言，偏光板可用於製造包括液晶面板之液晶顯示裝置，其中具有黏著劑層之偏光板層壓在液晶單元之至少一側上。
因此，本發明之一實施例係關於在液晶單元之至少一側上具有偏光板之液晶顯示裝置。
進一步藉由以下實例、比較實例及實驗實例來說明本發明，此不應理解為限制本發明之範疇。
製備實例1：丙烯酸共聚物之製備
向配備有冷卻器且經受氮氣流之1L反應器添加由85重量份數之丙烯酸正丁基酯(BA)、7重量份數之丙烯酸甲酯(MA)、5重量份數之丙烯酸2-羥基乙基酯及3重量份數之丙烯酸組成的單體混合物，且然後添加100重量份數之乙酸乙酯(EAc)作為溶劑。然後，用氮氣吹掃1小時以移除氧，隨後將溫度維持在62℃。將混合物均勻攪拌後，向其添加0.07重量份數之偶氮雙異丁腈(AIBN)作為反應起始劑，且使所得混合物反應8小時，以獲得重量平均分子量為約1,000,000之丙烯酸共聚物。
實例1至12及比較實例1至4：黏著劑附接之偏光板之製備
混合表1中所列示之組份以獲得黏著劑組合物(單位：重量份數)。
將由此獲得之黏著劑組合物施加在經矽離型劑塗覆之膜上以使乾燥後之厚度為25μm，且在100℃下乾燥1分鐘以形成黏著劑層。將另一離型膜層壓在其上以獲得黏著片。
在離型膜自上文所製備之黏著片剝離後，將黏著劑層附接至包含TAC保護膜之185μm厚之碘偏光板，以製備黏著劑附接之偏光板。
交聯劑：Coronate-L(TDI/TMP加成物，Nippon Polyurethane Industry)
D110N(二甲苯二異氰酸酯(XDI)之加成物，Mitsui Chemicals公司)
矽烷偶合劑：KBM-403(Shin-Etsu)
KBM-4803(Shin-Etsu)
C-1：草酸(pKa=2.83)
C-2：對甲苯磺酸(pKa<0)
C-3：苯甲酸(pKa=3.77)
C-4：十三烷酸(pKa=4.75)
實驗實例1：黏著強度及耐熱性之評估
使用以下方法量測在實例及比較實例中製備之黏著劑附接之偏光板的物理特性，且結果展示於表2中。
(1)黏著強度
將黏著劑附接之偏光板切割成25mm×100mm之大小。剝離離型膜後，在0.25MPa下將偏光板層壓在玻璃基板上且使其經受50℃、490pa及20分鐘條件下之高壓釜處理，以獲得樣品。
使樣品在25℃、50% RH下靜置24小時，且使用通用測試機(UTM,Instron)藉由以10m/min之剝離速率及180。之剝離角剝離來量測其黏著強度。量測係在25℃、50% RH下實施。
(2)耐熱性
在離型膜自黏著劑附接之偏光板剝離後，將板層壓在玻璃(Corning公司)上，然後進行高壓釜處理。在85℃下靜置300小時後，觀察到出現氣泡或剝離。
<評估標準>
×：至少3個氣泡或剝離
Δ：不大於2個氣泡或剝離
O：無氣泡或剝離
如表2中所展示，本發明之使用強酸之實例1至12之偏光板與僅使用矽烷偶合劑之比較實例1及2之彼等及使用弱酸之比較實例3及4之彼等相比，展現顯著更優異的黏著強度及耐熱性。
儘管已展示且闡述本發明之具體實施例，但彼等熟習此項技術者應理解，本發明並不意欲限於較佳實施例，且彼等熟習此項技術者應明瞭，可在不背離本發明之精神及範疇的情況下作出多種改變及修改。
因此，本發明之範疇係藉由隨附申請專利範圍及其等效內容加以界定。

Claims (8)

  1. 一種黏著劑組合物，其包含丙烯酸共聚物、交聯劑、矽烷偶合劑及pKa為3或更小之強酸。
  2. 如請求項1之黏著劑組合物，其中該矽烷偶合劑係以基於100重量份數之該丙烯酸共聚物計為0.01重量份數至2重量份數之量存在。
  3. 如請求項1之黏著劑組合物，其中該pKa為3或更小之強酸係有機酸。
  4. 如請求項1之黏著劑組合物，其中該pKa為3或更小之強酸係乙酸衍生物、有機磺酸或有機磷酸衍生物。
  5. 如請求項1之黏著劑組合物，其中該pKa為3或更小之強酸係草酸或對甲苯磺酸。
  6. 如請求項1之黏著劑組合物，其中該pKa為3或更小之強酸係以基於100重量份數之該丙烯酸共聚物計為0.001重量份數至0.1重量份數之量存在。
  7. 一種偏光板，其包括包含如請求項1至6中任一項之黏著劑組合物之黏著劑層。
  8. 一種液晶顯示裝置，其在液晶單元之至少一側上具有如請求項7之偏光板。
TW104109826A 2014-03-26 2015-03-26 黏著劑組合物及含彼之偏光板 TW201536881A (zh)

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