TW201837145A - 高性能光可固化光學清透黏著劑 - Google Patents

高性能光可固化光學清透黏著劑 Download PDF

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Publication number
TW201837145A
TW201837145A TW107106916A TW107106916A TW201837145A TW 201837145 A TW201837145 A TW 201837145A TW 107106916 A TW107106916 A TW 107106916A TW 107106916 A TW107106916 A TW 107106916A TW 201837145 A TW201837145 A TW 201837145A
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Taiwan
Prior art keywords
meth
acrylate
optically
curable adhesive
weight
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TW107106916A
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English (en)
Inventor
蘭虹 劉
大衛 艾倫 柯維姿
劍輝 夏
奧黛莉 安妮 雪曼
湯馬士 保羅 克隆
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美商3M新設資產公司
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Publication of TW201837145A publication Critical patent/TW201837145A/zh

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    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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Abstract

本發明係光學清透可固化黏著劑，其包括聚乙烯醇縮丁醛、聚胺甲酸酯(甲基)丙烯酸酯、及光起始劑。聚乙烯醇縮丁醛具有在約9與約13mPA．s之間的動態黏度和小於約18%的聚乙烯醇重量百分比。聚胺甲酸酯(甲基)丙烯酸酯包括二醇、至少一種二異氰酸酯、及羥基官能(甲基)丙烯酸酯或異氰酸基官能(甲基)丙烯酸酯的反應產物。當光學清透可固化黏著劑置於兩個透明基材之間並製成層壓體時，當固化時，層壓體具有小於約6%的霧度、大於約88%的透射率及大於約98%的光學清透性。當固化時，光學清透可固化黏著劑基於ASTM 3330亦具有至少約100g/cm的剝離黏著力。

Description

高性能光可固化光學清透黏著劑
本發明大致上係關於光學清透黏著劑。具體而言，本發明係關於光可固化光學清透黏著劑。
與傳統的光學清透黏著劑(OCA)膜相比，據信光可固化光學清透黏著劑(PCOCA)可以提供更薄的間隙、更好的厚度控制、減少至無層壓應力、以及更好的對顯示器總成的各種特徵(例如油墨梯級)的適形性。因此，液體光學透明黏著劑(LOCA)在顯示器產業中變得越來越普遍，以填充防護玻璃(cover glass)與銦錫氧化物(ITO)觸控感測器之間、ITO觸控感測器與液晶模組之間、或直接位於防護玻璃與液晶模組之間的氣隙。
顯示器產業目前正朝著液晶模組(LCM)接合方向發展，其中據信低收縮率、低模數材料對於光學性能和LCM接合是必需的。此外，確保OCA不會對LCM的外觀產生有害效應也很重要(例如雲紋(mura)效應、光學缺陷等)，具有高的黏著力，並且在環境條件下(諸如暴露於85℃的溫度或65℃/90% RH的條件下)達一延長時間段係光學可靠的。
目前的LOCA產品主要由丙烯酸單體或基於丙烯酸單體的反應性寡聚物製備。然而，這些產品具有顯著的收縮，這可能對LCM接合有害或需要進一步最佳化。具有可固化功能性的聚丙烯酸酯系寡聚物亦用於LOCA材料以實現高黏著力、低收縮率和低模數LCM接合。然而，為了在環境老化條件下獲得可塗佈黏度和光學可靠性，這些寡聚物通常需要相對高濃度的極性單體(諸如丙烯酸4-羥基丁酯)，其一般需要在85℃及65℃/90% RH下大於800小時的光學穩定性。使用高含量的稀釋劑單體可能直接導致黏著劑在固化時收縮，並可能抵消使用聚丙烯酸酯寡聚物的益處。
在一實施例中，本發明係光學清透可固化黏著劑，其包括聚乙烯醇縮丁醛、聚胺甲酸酯(甲基)丙烯酸酯、及光起始劑。聚乙烯醇縮丁醛具有在約9與約13mPA．s之間的動態黏度和小於約18%的聚乙烯醇重量百分比。聚胺甲酸酯(甲基)丙烯酸酯包括二醇、至少一種二異氰酸酯、及羥基官能(甲基)丙烯酸酯或異氰酸基官能(甲基)丙烯酸酯的反應產物。當光學清透可固化黏著劑置於兩個透明基材之間並製成層壓體時，當固化時，層壓體具有小於約6%的霧度、大於約88%的透射率及大於約98%的光學清透性。當固化時，光學清透可固化黏著劑基於ASTM 3330亦具有至少約100g/cm的剝離黏著力。
在另一實施例中，本發明係一光學清透層壓體，其包括一第一基材、一第二基材及一定位於該第一基材及該第二基材之間的光學清透可固化黏著劑。光學清透可固化黏著劑包括聚乙烯醇縮丁 醛、聚胺甲酸酯(甲基)丙烯酸酯、及光起始劑。聚乙烯醇縮丁醛具有在約9與約13mPA．s之間的動態黏度和小於約18%的聚乙烯醇重量百分比。聚胺甲酸酯(甲基)丙烯酸酯包括二醇、至少一種二異氰酸酯、及羥基官能(甲基)丙烯酸酯或異氰酸基官能(甲基)丙烯酸酯的反應產物。當光學清透可固化黏著劑置於兩個透明基材之間並製成層壓體時，當固化時，層壓體具有小於約6%的霧度、大於約88%的透射率及大於約98%的光學清透性。光學清透可固化黏著劑基於ASTM 3330亦具有至少約100g/cm的剝離黏著力。
本發明係高性能光可固化光學清透黏著劑(PCOCA)構造，PCOCA係具有卓越的光學清透性以及卓越的黏著力的可固化光學清透黏著劑，並可用於，例如在用於將基板接合到玻璃的顯示器總成中。PCOCA材料係由可固化(甲基)丙烯酸及聚胺甲酸酯(或聚脲)系反應性寡聚物的摻合物製備。
本發明之PCOCA包括聚乙烯醇縮丁醛、聚胺甲酸酯(甲基)丙烯酸酯、及光起始劑。在一實施例中，PCOCA包括介於約20重量%與約80重量%之間、特別地介於約30重量%與約60重量%之間、更特別地介於約32重量%與約60重量%之間、且最特別地介於約40重量%與約60重量%之間的聚乙烯醇縮丁醛(不包括光起始劑)及介於約20重量%與約80重量%之間、特別地介於約40重量% 與約70重量%之間、更特別地介於約40重量%與約68重量%之間、且最特別地介於約40重量%與約60重量%之間的聚胺甲酸酯(甲基)丙烯酸酯(不包括光起始劑)。在一實施例中，配方中聚乙烯醇縮丁醛及聚胺甲酸酯(甲基)丙烯酸酯之重量百分比總計100%。在另一實施例中，由於配方中存在添加劑，配方中聚乙烯醇縮丁醛及聚胺甲酸酯(甲基)丙烯酸酯之重量百分比總計小於100%。
在一實施例中，聚乙烯醇縮丁醛具有在約9與約13mPA．s之間的動態黏度(如根據DIN 53015所測量，10%固體在溶液中，在含5%水的乙醇中)和小於約18%的聚乙烯醇重量百分比。具體而言，聚乙烯醇縮丁醛具有介於約14%與約18%之間的聚乙烯醇重量百分比及介於約5%與約8%之間的聚乙酸乙烯酯重量百分比。在一實施例中，聚乙烯醇縮丁醛具有介於約10,000g/mol與約15,000g/mol之間的重量平均分子量。合適的市售可得聚乙烯醇縮丁醛之實例包括但不限於Mowital B14S，可購自Kuraray America,Inc.，位於Houston,TX。
聚胺甲酸酯(甲基)丙烯酸酯係具有一或多個附接至聚胺甲酸酯聚合物上的(甲基)丙烯酸酯基團的聚胺甲酸酯聚合物。聚胺甲酸酯係在許多應用中有用的聚合物，諸如黏著劑。聚胺甲酸酯可由包括含異氰酸基官能基之化合物(諸如聚異氰酸酯(較佳地二異氰酸酯))及具有與異氰酸酯基團反應之官能基之化合物(諸如多醇及/或多胺(較佳地二醇及/或二胺))的起始材料製備。在一些實施例中，聚胺甲酸酯係交替、嵌段的、星形嵌段或鏈段共聚物(或其組合)。 聚胺甲酸酯亦可以含有其他化學部分，諸如烷基、芳基、丙烯酸酯、醚、酯、及碳酸酯基團，以及其混合物。在一實施例中，聚胺甲酸酯(甲基)丙烯酸酯具有介於約2,700g/mol與約63,000g/mol之間的重量平均分子量。
聚胺甲酸酯(甲基)丙烯酸酯在聚合物鏈的一或多個鏈末端和其他位置可具有(甲基)丙烯酸酯官能基。作為一非限制性的實例，(甲基)丙烯酸酯二醇(例如(甲基)丙烯酸2-甘油酯)可用於製造具有丙烯酸酯基團的聚胺甲酸酯(甲基)丙烯酸酯，該等丙烯酸酯基團位於不靠近聚合物鏈末端的位置。在一實施例中，聚胺甲酸酯(甲基)丙烯酸酯在鏈端具有(甲基)丙烯酸酯官能基。
聚胺甲酸酯(甲基)丙烯酸酯可以藉由選擇用於製備他們的起始材料來包含其他官能基(例如醚、酯、及/或碳酸酯官能基)。作為一非限制性的實例，聚(四氫呋喃)可用於製造亦包含醚官能基的聚胺甲酸酯(甲基)丙烯酸酯。特別適合適的聚胺甲酸酯(甲基)丙烯酸酯包含胺甲酸酯、(甲基)丙烯酸酯、及醚官能基。另一特別適合適的聚胺甲酸酯(甲基)丙烯酸酯包含胺甲酸酯、(甲基)丙烯酸酯、及酯官能基。
市售可得合適的聚胺甲酸酯(甲基)丙烯酸酯之實例包括但不限於：CN978、CN981、及CN991，可購自Sartomer Americas，位於Exton,PA。在一實施例中，聚胺甲酸酯(甲基)丙烯酸酯具有介於約1.3與約3.0之間的多分散性。多分散性指數用作聚合物 分子量分布寬度的量度，並且由數量平均分子量：重量平均分子量的比例所界定。多分散性指數越大，聚合物的分子量分布越寬。
本發明之聚胺甲酸酯(甲基)丙烯酸酯包括包含二醇、至少一種二異氰酸酯、及羥基官能(甲基)丙烯酸酯或異氰酸基官能(甲基)丙烯酸酯的反應產物的聚胺甲酸酯(甲基)丙烯酸酯。(甲基)丙烯酸酯被定義為丙烯酸或甲基丙烯酸的酯。二醇和二異氰酸酯可以不同的比例存在，至少部分取決於二醇和二異氰酸酯的分子量以及所得聚胺甲酸酯(甲基)丙烯酸酯的所欲分子量。如聚胺甲酸酯配方之所屬技術領域，可以選擇提供對聚胺甲酸酯(甲基)丙烯酸酯以及對包含聚胺甲酸酯(甲基)丙烯酸酯之黏著劑的可撓性和適形性之二醇。亦可以選擇提供聚胺甲酸酯(甲基)丙烯酸酯與聚乙烯醇縮丁醛或黏著劑配方的其它組分的相容性之二醇。不受理論拘限，認為在聚乙烯醇縮丁醛與聚胺甲酸酯(甲基)丙烯酸酯材料之間的相容性對於在所得黏著劑中獲得所欲的光學性質是必需的。
亦可以選擇提供所得黏著劑所欲的性質(諸如黏著性質和光學性質)之二醇。在一實施例中，基於聚(四氫呋喃)及聚己內酯的二醇適用於本發明黏著劑配方中使用的聚胺甲酸酯(甲基)丙烯酸酯，且基於聚(四氫呋喃)的二醇特別適用於用於本發明黏著劑配方中使用的聚胺甲酸酯(甲基)丙烯酸酯。在一實施例中，二醇可以包括較低分子量的二醇，諸如乙二醇或丁二醇。在一實施例中，二醇係選自具有約1000g/mol或更小的數量平均分子量(Mn)之聚(四氫呋喃)二醇及具有約1000g/mol或更小的數量平均分子量的聚己內酯二醇中的一 者。合適的市售可得具有約1000g/mol的分子量之聚(四氫呋喃)二醇之實例包括但不限於PolyTHF 1000 Polyether，可購自BASF Corp.，位於Florham Park,NJ。
亦可以選擇提供聚胺甲酸酯(甲基)丙烯酸酯及所得黏著劑所欲的性質(諸如黏著性質和光學性質)之二異氰酸酯。在一實施例中，異氰酸酯包括脂族異氰酸酯。特別合適的異氰酸酯包括脂族二異氰酸酯。如所屬技術領域中已知的，脂族異氰酸酯是其中一或多個異氰酸基中的各者藉由化學鍵附接至脂族碳原子之一者。然而，脂族異氰酸酯分子也可以含有不附接至一或多個異氰酸基中的任一者的芳族部分是可接受的。藉由此定義，亞甲基二苯基二異氰酸酯(MDI)及甲苯二異氰酸酯(TDI)不是脂族異氰酸酯，但被認為是芳族異氰酸酯。然而，間四甲伸茬基二異氰酸酯及對四甲伸茬基二異氰酸酯(各別係m-TMXDI及p-TMXDI)被認為是脂族異氰酸酯，即使他們含有芳環(參見以下結構)。當然，其分子結構中不含芳族部分的異氰酸酯(諸如異佛爾酮二異氰酸酯(IPDI))是脂族異氰酸酯。
芳族異氰酸酯
脂族異氰酸酯
合適的二異氰酸酯之實例包括但不限於：2,6-甲苯二異氰酸酯(TDI)、亞甲基二伸環己基-4,4'-二異氰酸酯(H12MDI)、3-異氰酸基甲基-3,5,5-三甲基環己基異氰酸酯(IPDI)、1,6-二異氰酸基己烷(HDI)、四甲基-間-伸茬基二異氰酸酯、2,2,4-及2,4,4-三甲基-1,6-二異氰酸基己烷的混合物(TMXDI)、反-1,4-氫化伸茬基二異氰酸酯(H6XDI)、及其組合。在一實施例中，二異氰酸酯是脂族二異氰酸酯。
本發明之聚胺甲酸酯(甲基)丙烯酸酯亦可包括羥基官能(甲基)丙烯酸酯或異氰酸基官能(甲基)丙烯酸酯。單官能分子亦可以用於製備聚胺甲酸酯。例如，單官能分子(諸如單官能含醇和含異氰酸酯的分子)可用於在聚合物合成期間在聚胺甲酸酯鏈末端或其附近引入官能基。合適的單官能醇包括丙烯酸2-羥乙酯(HEA)和甲基丙烯酸2-羥乙酯(HEMA)。每個醇基團提供多於一個丙烯酸酯的另一單官能醇的實例為二甲基丙烯酸甘油酯，也稱為雙(甲基丙烯醯基氧基)丙醇(1,2-和1,3-形式的混合物)。合適的單官能異氰酸酯包括丙烯酸2-異氰酸基乙酯和甲基丙烯酸2-異氰酸基乙酯。每個異氰酸酯基團提供多於一個丙烯酸酯的另一單官能異氰酸酯的實例為1,1-雙(丙烯醯基氧 基甲基)乙基異氰酸酯，可購自CBC America,Commack,NY。所有這些化合物都可用於合成具有(甲基)丙烯酸酯末端基的聚胺甲酸酯。
合適的聚胺甲酸酯(甲基)丙烯酸酯藉由將單官能醇及雙官能醇與二異氰酸酯組合來製備。在一實施例中，單官能醇係選自HEA、HEMA、及其組合。其他合適的聚胺甲酸酯藉由將單官能異氰酸酯及雙官能異氰酸酯與二醇組合來製備。在一實施例中，單官能異氰酸酯係選自丙烯酸2-異氰酸基乙酯、甲基丙烯酸2-異氰酸基乙酯。在另一實施例中，聚胺甲酸酯(甲基)丙烯酸酯如上文論述藉由將單官能醇與二異氰酸酯組合來製備。適合與二異氰酸酯反應的單官能醇的另一個實例是己內酯延長的(甲基)丙烯酸羥乙酯。市售合適的己內酯延長的(甲基)丙烯酸羥乙酯之實例包括但不限於SR495，可購自Sartomer Americas，位於Exton,PA。
可以使用各種方法來合成聚胺甲酸酯(甲基)丙烯酸酯。起始材料可以藉由所屬技術領域中已知的方法並以所選比例組合以產生具有所欲性質(諸如所選分子量)的聚胺甲酸酯(甲基)丙烯酸酯。所屬技術領域中已知的一種方法係將多官能醇(較佳地二醇)與聚異氰酸酯(較佳地二異氰酸酯)組合以產生聚胺甲酸酯預聚物。聚胺甲酸酯預聚物可以在分子鏈端上具有醇或異氰酸酯官能基，這取決於多元醇對聚異氰酸酯的所選比例。
在其中藉由二醇與二異氰酸酯的反應合成聚胺甲酸酯預聚物的一實施例，選擇二異氰酸酯對二醇的比例以既提供所欲的分子量並產生聚胺甲酸酯預聚物末端的異氰酸酯或羥基末端基。在分子鏈 末端具有異氰酸酯官能基的聚胺甲酸酯預聚物可與單醇反應以產生聚胺甲酸酯，其中末端基由單醇提供。在分子鏈末端具有醇官能基的聚胺甲酸酯預聚物可與單異氰酸酯反應以產生聚胺甲酸酯，其中末端基由單異氰酸酯提供。
在一實施例中，聚胺甲酸酯預聚物與引入(甲基)丙烯酸酯官能基的另一分子反應。選擇甲基(丙烯酸酯)分子以具有與其反應的聚胺甲酸酯預聚物的官能基互補的官能基。例如，對於異氰酸酯封端的聚胺甲酸酯預聚物，選擇亦含有羥基官能基的(甲基)丙烯酸酯分子(例如HEA或HEMA)。替代地，對於烴基封端聚胺甲酸酯預聚物，選擇亦含有異氰酸酯基的(甲基)丙烯酸酯分子(例如丙烯酸2-異氰酸基乙酯或甲基丙烯酸2-異氰酸基乙酯)。這些具有(甲基)丙烯酸酯末端基的聚胺甲酸酯聚合物稱為聚胺甲酸酯(甲基)丙烯酸酯或胺甲酸酯(甲基)丙烯酸酯。
可以選擇聚異氰酸酯及多官能醇以提供所得胺甲酸酯(甲基)丙烯酸酯所欲的性質，諸如熱性質(例如玻璃轉移溫度)，光學性質(例如透射率、霧度和清透性)，在所選溶劑中的溶解度，以及與其他所選聚合物(例如聚(乙烯醇縮丁醛(PVB))的相容性。
聚胺甲酸酯(甲基)丙烯酸酯在聚合物鏈的一或多個鏈末端和其他位置可具有(甲基)丙烯酸酯官能基。作為一非限制性的實例，(甲基)丙烯酸酯二醇(例如(甲基)丙烯酸2-甘油酯)可用於製造具有(甲基)丙烯酸酯基團的聚胺甲酸酯(甲基)丙烯酸酯，該等(甲基)丙烯 酸酯基團位於不靠近聚合物鏈末端的位置。在一較佳實施例中，聚胺甲酸酯(甲基)丙烯酸酯在鏈末端具有(甲基)丙烯酸酯官能基。
聚胺甲酸酯(甲基)丙烯酸酯可以藉由選擇用於製備他們的起始材料來包含其他官能基(例如醚、酯、及/或碳酸酯官能基)。作為一非限制性的實例，聚(四氫呋喃)可用於製造亦包含醚官能基的聚胺甲酸酯(甲基)丙烯酸酯。特別適合適的聚胺甲酸酯(甲基)丙烯酸酯包含胺甲酸酯、(甲基)丙烯酸酯、及醚官能基。另一特別適合適的聚胺甲酸酯(甲基)丙烯酸酯包含胺甲酸酯、(甲基)丙烯酸酯、及酯官能基。
光起始劑係用於固化PCOCA。一般藉由暴露於適當波長及強度之光來活化一或多種起始劑。經常使用UV光。合適的市售可得光起始劑之實例包括但不限於：Darocur 4265及Irgacure 184，兩者皆可購自BASF Corp.，位於Florham Park,NJ。
出於特殊目的可添加至前驅物混合物之其他材料，包括，例如：熱穩定劑、助黏劑、交聯劑、表面改質劑、紫外光穩定劑、抗氧化劑、抗靜電劑、增稠劑、填料、顏料、著色劑、染料、觸變劑、加工助劑、奈米粒子、纖維及其組合。
實務上，高性能光可固化光學清透黏著劑可以定位於第一基材與第二基材之間以形成層壓體。層壓體包括具有至少一主表面的第一基材，具有至少一主表面的第二基材，及定位相鄰於該第一基材及第二基材之該主表面的PCOCA。因此，第一基材及第二基材中 的至少一者是光學清透的，並且可以包括例如光學膜或光學清透基材。
包括PCOCA的層壓體可用於顯示器總成中。顯示器總成可進一步包括另一個基材(例如永久或暫時附接至PCOCA)、另一個黏著劑層、或其組合。如本文中所使用，術語「鄰近(adjacent)」可被用來指稱直接接觸的兩個層或藉由一或多個薄層(例如底漆或硬塗層)分離的兩個層。相鄰的層時常是直接接觸的。此外，還提供了包括定位於兩個基材之間的PCOCA之層壓體，其中該等基材中之至少一者係光學膜。光學膜意圖增強、操縱、控制、維持、傳送、反射、折射、吸收、延遲或以其他方式改變入射到膜表面上的光。層壓體中包括的膜包括具有光學功能的材料種類，例如偏光器、干涉偏光器、反射偏光器、擴散器、彩色光學膜、鏡、百葉光學膜、光控制膜、透明片、增亮膜、防眩和抗反射膜、及類似物。用於所提供之層壓體的膜亦可包括延遲板，諸如四分之一波及半波相位延遲光學元件。其他光學清透膜包括防裂膜(anti-splinter film)及電磁干擾濾波器。
在一些實施例中，所生成的層壓體可以是光學元件或可被用於製備光學元件。本文中使用的術語「光學元件(optical element)」係指具有光學效應或光學應用的物件。光學元件可被用於例如電子顯示器、建築應用、運輸應用、投射應用、光子應用、及圖形應用。適當的光學元件包括但不限於玻璃(glazing)(例如窗和擋風玻璃)、螢幕或顯示器、陰極射線管、及反射器。
例示性的光學清透基材包括但不限於：顯示面板(諸如液晶顯示器、OLED顯示器、觸控面板、電濕潤顯示器或陰極射線管)、窗或玻璃(glazing)、光學組件(諸如反射器、偏光器、繞射光柵、鏡、或覆蓋鏡片(cover lens))、另一種膜(諸如裝飾膜)或另一種光學膜。
光學清透基材的代表性實例包括玻璃及聚合基材，包括那些含有聚碳酸酯、聚酯(例如聚苯二甲酸乙二酯和聚萘二甲酸乙二酯)、聚胺甲酸酯、聚(甲基)丙烯酸酯(例如聚甲基丙烯酸甲酯)、聚乙烯醇、聚烯烴(例如聚乙烯、聚丙烯)、及三乙酸纖維素的聚合基材。典型上，覆蓋鏡片可以由玻璃、聚甲基丙烯酸甲酯、或聚碳酸酯製成。
在其他實施例中，任一基材可以是離型襯墊。可使用任何適合的離型襯墊。例示性離型襯墊包括由紙(例如牛皮紙)或聚合材料(例如，聚烯烴，諸如聚乙烯或聚丙烯、乙烯乙酸乙烯酯、聚胺甲酸酯、聚酯，諸如聚苯二甲酸乙二酯、及類似物)製成之離型襯墊。至少一些離型襯墊係塗佈有一層離型劑，諸如含聚矽氧材料或含氟碳化物材料。例示性離型襯墊包括(但不限於)可以商標名「T-30」及「T-10」購自CP Film(Martinsville,VA)之襯墊，其具有在聚苯二甲酸乙二酯膜上之聚矽氧離型塗層。
可移除離型襯墊以將PCOCA黏著至另一基材(即離型襯墊之移除暴露出黏著劑層之表面，該表面隨後可接合於另一基材表 面)。通常，PCOCA永久接合於此另一基材，然而在一些情況下，黏著可以限於允許對顯示器進行再加工。
本發明之高性能光可固化光學清透黏著劑在使用其之物品的壽命期間保持光學清透性、接合強度、及抗分層性。如本文中所使用，用語「光學清透的(optically clear)」係指當固化時具有以下的材料：小於約6%、特別地小於約4%，更特別地小於約2%的霧度；大於約88%，特別地大於約89%，更特別地大於約90%的光透射率；大於約98%，特別地大於約99%，更特別地大於約99.5%的光學清透性。一般而言，清透性、霧度及透射率是在黏著劑保持在諸如聚(對苯二甲酸乙二酯)(PET)的兩種光學膜之間的結構上測量的。然後對整個結構進行測量，包括黏著劑和基材。可使用例如ASTM-D 1003-92來測定霧度和光透射率兩者。使用例如BYK Gardner haze-gard plus 4725 instrument(Geretsried,Germany)可以進行透射率、霧度和光學清透性的光學測量。BYK儀器使用照明「C」光源並測量該光譜範圍內的所有光線以計算透射率值。霧度是偏離入射光束大於2.5°的透射光的百分比。在角度小於2.5°評估光學清透性。一般而言，PCOCA是視覺上無氣泡的。
本發明之高性能光可固化光學清透黏著劑基於ASTM 3330在固化時亦具有至少約100g/cm，特別地至少約150g/cm，更特別地至少約200g/cm的剝離黏著力。如果PCOCA的剝離黏著力太低，則黏著劑將失效並且可能導致包括他的物品分開(分層)。黏著 劑可能會以多種方式失效。如果黏著劑殘留物殘留在定位相鄰於黏著劑任一側的一個或兩個基材上，則黏著劑失效。
當用於製造裝置時，本發明之PCOCA相對於聚乙烯醇縮丁醛提供了數個優點。PCOCA是可固化的，所以他們在固化之前和之後可以具有明顯不同的性質。聚乙烯醇縮丁醛不會以此方式改變性質，因此表現得更像熱熔融黏著劑。另外，因為他們經固化，所以PCOCA抗流動。已知聚乙烯醇縮丁醛在升高的溫度下流動，諸如黏著劑在製造裝置期間可能暴露。此外，由於他們是組分之混合物，因此可藉由選擇組分和改變組分比例來調整PCOCA的性質以滿足產品需求。這對於新產品的PCOCA的採購，開發和應用提供了優勢，這些產品優於聚乙烯醇縮丁醛本身以及許多現有的光學清透黏著劑。
本發明之層壓體具有下列性質之至少一者：PCOCA在物品使用壽命期間具有光學透射率，PCOCA可以保持物品層之間的充分接合強度，PCOCA可以抵抗或避免分層，且PCOCA可以在使用壽命期間抵抗黏著劑層的起泡。當用於顯示器，層壓體係固化時光學清透且具有以下：小於約6%、特別地小於約4%，更特別地小於約2%的霧度；大於約88%，特別地大於約89%，更特別地大於約90%的光透射率；大於約98%，特別地大於約99%，更特別地大於約99.5%的光學清透性。
本揭露之目的及優點係藉由以下之實例而進一步說明，但不應不當地解讀這些實例中詳述的特定材料及其用量、以及其他條件及細節而限制本發明。
實例
本發明在以下實例中被更具體地描述，該等實例只意圖作為說明，因為在本發明範圍內的許多改變和變化對於所屬技術領域中具有通常知識者而言將是顯而易見的。除非另外註明，否則以下實例中所報導之所有份數、百分比、及比均以重量計。
材料
測試方法 分子量判定
使用習知凝膠滲透層析術(GPC)來特徵化各聚胺甲酸酯(甲基)丙烯酸酯之分子量分布。GPC儀器(得自Waters Corporation(Milford,MA,USA))包括高壓液體層析泵(型號1515HPLC)、自動取樣器(型號717)、UV檢測器(型號2487)、及折射率檢測器(型號2410)。層析儀配備有二個可購自Varian Inc.(Palo Alto,CA,USA)的5微米PLgel MIXED-D管柱。聚合溶液樣本之製備如下：稀釋聚合物溶液或溶解經乾燥之聚合物材料於四氫呋喃(THF)中成0.5百分比(重量/體積)濃度，並通過購自VWR International(West Chester,PA,USA)的0.2微米聚四氟乙烯濾片過濾THF溶液。將所得的樣品注入GPC並以每分鐘1毫升的速率洗提通過保持在35℃的管柱。使用線性最小平方適配分析以聚苯乙烯標準品來校準系統，以建立校準曲線。針對各樣本相對於此標準校準曲線，計算重量平均分子量(Mw)與多分散性指數(重量平均分子量除以數量平均分子量)。分子量分布列於表2中。
發光透射率、清晰度、及霧度
使用BYK Gardner Haze-Gard Plus 4725 instrument(Geretsried,Germany)可以進行透射率、霧度和光學清透性的光學測量。BYK儀器使用照明「C」光源並測量該光譜範圍內的所有光線以計算透射率值。霧度是偏離入射光束大於2.5°的透射光的百分比。在角度小於2.5°評估光學清透性。數值以表4中的透射率百分比(%T)，霧度百分比(%H)和清透性百分比(%C)記述。如果樣本具有至少88%的透射率百分比、不大於6%的霧度百分比，及在捨入後具有至少98%的清透性百分比，則認為該樣本是可接受的。
180°剝離黏著力測試
基於ASTM 3330測試剝離黏著力。使用可購自IMASS,Inc.(Accord,Massachusetts)之IMASS剝離測試儀，使用5kg荷重單元，4秒延遲，20秒測試時間和30.48cm/min剝離速率進行室溫剝離。重複三次測試，並以公克每公分(g/cm)記述平均值。剝離黏著力係列在表3中。如果樣本具有至少約100g/cm的剝離黏著力，則認為該樣本是可接受的。
樣本製備 經電漿底塗的PET
將一卷125微米厚的聚苯二甲酸乙二酯(PET)膜安裝在卷對卷真空處理腔室的退繞輥上，將該膜纏繞在鼓輪電極(drum electrode)，然後固定到鼓輪電極相反側的捲取輥上。退繞及捲取張力維持在3磅(13.3N)。關閉腔室門，且將腔室泵抽至約5×10-4托之基礎壓力。以20標準立方公分/分鐘(sccm)之流率引入六甲基二矽氧烷(HMDS)，並以500sccm的流率提供氧氣。藉由將射頻功率施加至鼓輪以6000瓦之功率開啟電漿，並開始鼓輪旋轉，使得膜以10呎/分鐘之速度運輸。暴露期間的壓力約為8至10毫托。
剝離測試樣本製備
使用具有20密耳間隙的刮刀塗佈機將表3中提供的黏著劑溶液塗佈在經電漿底塗的PET之經底塗表面上。將經塗佈的樣本在70℃下乾燥10分鐘。將樣本從烘箱中取出並藉由手施用SKC T50緊離型襯墊。然後將樣本切成1.3cm寬乘以13cm長。將尺寸為6.35cm乘以17.78cm之浮製玻璃板在層壓前在烘箱中加熱至90℃。然後自樣本移除離型襯墊，並使用手動輥將他們層壓到浮製玻璃的空氣側(非錫)上。然後將層壓的玻片置於90℃的烘箱中5分鐘，然後再次層壓，使用離型襯墊作為輥與樣本之間的界面，以防止在黏著劑滲出的情況下污染輥。然後使用裝備有D燈泡的Light-Hammer 6 UV固化系統(Fusion UV-Systems Inc.,Gaithersburg,MD)，在氮氣氣氛下以100%燈功率在20呎/分鐘的線速度通過4次下操作來固化塗層。
聚胺甲酸酯丙烯酸酯C的製備(16 IPDI 14 PTMO 1000 2 HEA)
向裝備有頂置式攪拌器的三升三頸圓底反應燒瓶中加入99.31g(0.8935當量(eq.),111.15eq Wt)IPDI、480g MEK、386.42g(0.7818eq,492.27eq Wt)PolyTHF 1000(在80℃下在低於20mmHg的壓力下乾燥過夜)及0.25g(相對於總固體為500ppm)DBTDL。將燒瓶置於裝有冷凝器和溫度探測器的油浴中，置於乾燥空氣下並攪拌。最初，反應溫度為28℃、5分鐘時為29.9℃、13分鐘時為31.7℃、23分鐘時為47.9℃、及31分鐘時為53℃。此時加熱油浴使內部溫度達到60℃。在反應開始4小時和15分鐘後，反應等分試樣的FTIR在2265cm-1處顯示出小的異氰酸酯峰。在反應開始4小時20分鐘後，加入14.23g(0.1229eq，10%化學計量過量)的HEA並用20g MEK潤洗以使反應達到50%固體。在反應開始後6小時20分鐘，反應等分試樣的FTIR在2265cm-1處未顯示出異氰酸酯峰。然後反應經428.57g MEK調整至35%固體。認為這些聚胺甲酸酯丙烯酸酯的結構是由二醇與二異氰酸酯反應形成聚胺甲酸酯所形成的線性聚合物，且這些線性聚合物在各末端用丙烯酸羥乙酯封蓋(需要兩個當量，但是使用10%化學計量過量以確保完成轉換)。HEA之化學計量將會是0.1229/1.1或0.1117eq。IPDI之當量數是(0.8935/0.1117)*2、或16當量，且PTMO二醇之當量數是(0.7818/0.1117)*2、或14當量。
製備聚胺甲酸酯丙烯酸酯的一般程序
使用上述聚胺甲酸酯丙烯酸酯C的程序，使用如表2所示以克為單位之起始材料重量來合成剩餘的聚胺甲酸酯丙烯酸酯(PUA)。將反應在具有500ppm DBTDL的50%固體的燒瓶或罐(在磁力攪拌下)中進行。所有多醇在使用前在80℃下在真空(<10托)下乾燥至少2小時。在一些情況中，將一些反應物稀釋至35%或33%固體，並且在一些情況下，將反應保持在50%固體(表2中所示)並進一步用於其他配方中。
預示性實例-使用羥基封端的預聚物製備聚胺甲酸酯丙烯酸酯
於裝備有頂置式攪拌器的500mL三頸圓底反應燒瓶中加入27.25g(0.245當量(eq.))的異佛爾酮二異氰酸酯(IPDI)及20g甲基乙基酮(MEK)，置於裝有冷凝器之油浴中，置於乾燥空氣下，並加熱至60℃。於均壓添加漏斗中加入140.1g(0.280eq.)的1,000g/mol聚(四氫呋喃)(PTMO，使用前在80℃下真空(<10托)乾燥至少2小時)及80g MEK並附接至反應燒瓶。於反應燒瓶中加入800微升在MEK中的DBTDL的10%溶液。然後將添加漏斗的內容物在30分鐘內加入到反應燒瓶中，並且在時間結束時，將添加漏斗用5g MEK潤洗，並將30g以上的MEK直接加入到反應混合物中。在反應2小時後，反應混合物通過FTIR在2265cm-1處顯示出小的異氰酸酯峰。在一部分中，將在8.02g MEK中的4.94g(0.0350eq.)的丙烯酸2-異氰酸基乙酯(HEA)從罐中加入到反應中。將該罐用5g然後0.5g MEK潤洗，並將潤洗液加入到反應中。約6小時後，將5g MEK中的0.10g的丙烯酸2-異氰酸基乙酯從罐中加入到反應中。將該罐用10g MEK潤洗，並將潤洗液加入到反應中。使混合物再反應30分鐘。然後藉由將乾空氣吹入反應燒瓶以蒸發一些MEK以將產物混合物調整至50%固體，並隨後將產物混合物裝瓶。
光學測試樣本製備的一般塗佈及固化程序
表3提供用於各實例塗佈之溶液的組成。表1中提供標為PVB欄中的縮寫。表2中描述聚胺甲酸酯丙烯酸酯(PUA)，並以表 2中指示的固體wt%添加，或者，除非另有說明，對於市售可得的聚胺甲酸酯丙烯酸酯(CN964、CN978、CN981、CN991、CN9002、及CN9004)，以MEK中50%固溶體添加。光起始劑溶液是在MEK中10%固體的Irgacure 819。給出PVB與PUA的固體重量比，並且如下計算：實例1含有11.88g的25wt%的Mowital B 14 S溶液，相當於2.97g固體。他亦含有5.94g的50wt%的PUA B溶液，相當於2.97g固體。因此固體總量(不包括Irgacure 819)為2.97g+2.97g或5.94g。除非另有說明，所有溶液均在MEK中調節至30wt%固體，並且給出添加或除去MEK的g(各別為正值或負值)以達到30wt%固體。在實例1中，Irgacure 819的固體為0.1g/g溶液乘以0.59g溶液=0.059g Irgacure 819。實例1的總固體量為5.94g+0.059g、或6.00g。
使用表3中提供的黏著劑溶液，使用具有25密耳間隙的刮刀塗佈器，將各黏著劑溶液塗佈在2密耳經電漿底塗的PET膜之經底塗側上製備測試樣品。將經塗佈的PET膜空氣乾燥約10分鐘，然後置於65℃烘箱中10分鐘。然後將樣本黏貼到預加熱至90℃的不銹鋼板上約90秒，然後將第二片2密耳SSP PET膜在其經底塗側上層壓至塗層。然後使用裝備有D燈泡的Light-Hammer 6 UV固化系統(Fusion UV-Systems Inc.,Gaithersburg,MD)，在氮氣氣氛下以100%燈功率在20呎/分鐘的線速度通過1次下操作來固化PET塗層-PET層壓體。
表4中提供各測試樣品的透射率百分比(%T)、霧度百分比(%H)和清透性百分比(%C)以及所選實例和比較例的黏著力值。如果測試樣品不具有所欲的光學性質，則通常不測試黏著力。認為那些具有至少88%的%T、6%或更小的%H、及至少98%的%C，並且具有100g/cm或更大的黏著性的樣品是本發明的實例。
雖然本發明已參照較佳的實施例加以描述，但所屬技術領域中具有通常知識之工作者應能理解形式及細節可改變而不會偏離本發明的精神及範疇。

Claims (21)

  1. 一種光學清透可固化黏著劑，其包含：聚乙烯醇縮丁醛，其具有在約9與約13mPA．s之間的動態黏度並具有小於約18%的聚乙烯醇重量百分比；聚胺甲酸酯(甲基)丙烯酸酯，其包含下列之反應產物：二醇；至少一種二異氰酸酯；及羥基官能(甲基)丙烯酸酯或異氰酸基官能(甲基)丙烯酸酯；及光起始劑；其中當該光學清透可固化黏著劑置於兩個透明基材之間並製成層壓體時，當固化時，該層壓體具有小於約6%的霧度、大於約88%的透射率、及大於約98%的光學清透性，且其中該光學清透可固化黏著劑，當固化時，基於ASTM 3330具有至少約100g/cm的剝離黏著力。
  2. 如請求項1之光學清透可固化黏著劑，其中該二醇係選自具有約1000g/mol或更小的數量平均分子量之聚(四氫呋喃)二醇及具有約1000g/mol或更小的數量平均分子量的聚己內酯二醇中的一者。
  3. 如請求項1之光學清透可固化黏著劑，其中該二異氰酸酯係脂族二異氰酸酯。
  4. 如請求項1之光學清透可固化黏著劑，其中該二異氰酸酯係選自下列之一者：2,6-甲苯二異氰酸酯(TDI)、亞甲基二伸環己基-4,4'-二異氰酸酯(H12MDI)、3-異氰酸基甲基-3,5,5-三甲基環己基異氰酸酯(IPDI)、1,6-二異氰酸基己烷(HDI)、四甲基-間-伸茬 基二異氰酸酯、2,2,4-及2,4,4-三甲基-1,6-二異氰酸基己烷的混合物(TMXDI)、反-1,4-氫化伸茬基二異氰酸酯(H6XDI)、及其組合。
  5. 如請求項1之光學清透可固化黏著劑，其中該聚乙烯醇縮丁醛具有介於約10,000g/mol與約15,000g/mol之間的重量平均分子量。
  6. 如請求項1之光學清透可固化黏著劑，其中該聚胺甲酸酯(甲基)丙烯酸酯具有介於約2,700g/mol與約63,000g/mol之間的重量平均分子量。
  7. 如請求項1之光學清透可固化黏著劑，其中該聚胺甲酸酯(甲基)丙烯酸酯具有介於約1.3與約3.0之間的多分散性。
  8. 如請求項1之光學清透可固化黏著劑，其中該聚乙烯醇縮丁醛具有介於約14%與約18%之間的聚乙烯醇重量百分比。
  9. 如請求項1之光學清透可固化黏著劑，其中該聚乙烯醇縮丁醛具有介於約5%與約8%之間的聚乙酸乙烯酯重量百分比。
  10. 如請求項1之光學清透可固化黏著劑，其中該光學清透可固化黏著劑包含介於約30重量%與約60重量%的聚乙烯醇縮丁醛。
  11. 如請求項1之光學清透可固化黏著劑，其中該光學清透可固化黏著劑包含介於約40重量%與約70重量%的聚胺甲酸酯(甲基)丙烯酸酯。
  12. 如請求項1之光學清透可固化黏著劑，其進一步包含選自下列之至少一種添加劑：熱穩定劑、助黏劑、交聯劑、表面改質劑、紫外光穩定劑、抗氧化劑、抗靜電劑、增稠劑、填料、顏料、著色劑、染料、觸變劑、加工助劑、奈米粒子、纖維及其組合。
  13. 一種光學清透層壓體，其包含： 一第一基材；一第二基材；及一定位於該第一基材及該第二基材之間的光學清透可固化黏著劑，該光學清透可固化黏著劑包含：聚乙烯醇縮丁醛，其具有在約9與約13mPA．s之間的動態黏度並具有小於約18%的聚乙烯醇重量百分比；聚胺甲酸酯(甲基)丙烯酸酯，其包含下列之反應產物：二醇；至少一種二異氰酸酯；及羥基官能(甲基)丙烯酸酯或異氰酸基官能(甲基)丙烯酸酯；及光起始劑；其中當該光學清透可固化黏著劑置於兩個透明基材之間並製成層壓體時，該層壓體具有小於約6%的霧度、大於約88%的透射率、及大於約98%的光學清透性，且其中該光學清透可固化黏著劑基於ASTM 3330具有至少約100g/cm的剝離黏著力。
  14. 如請求項13之光學清透層壓體，其中該二醇係選自具有約1000g/mol或更小的數量平均分子量之聚(四氫呋喃)二醇及具有約1000g/mol或更小的數量平均分子量的聚己內酯二醇中的一者。
  15. 如請求項13之光學清透層壓體，其中該二異氰酸酯係脂族二異氰酸酯。
  16. 如請求項13之光學清透層壓體，其中該聚乙烯醇縮丁醛具有介於約10,000g/mol與約15,000g/mol之間的重量平均分子量。
  17. 如請求項13之光學清透層壓體，其中該聚胺甲酸酯(甲基)丙烯 酸酯具有介於約2,700g/mol與約63,000g/mol之間的重量平均分子量。
  18. 如請求項13之光學清透層壓體，其中該聚乙烯醇縮丁醛具有介於約14%與約18%之間的聚乙烯醇重量百分比。
  19. 如請求項13之光學清透層壓體，其中該聚乙烯醇縮丁醛具有介於約5%與約8%之間的聚乙酸乙烯酯重量百分比。
  20. 如請求項13之光學清透層壓體，其中該光學清透可固化黏著劑包含介於約30重量%與約60重量%的聚乙烯醇縮丁醛。
  21. 如請求項13之光學清透層壓體，其中該光學清透可固化黏著劑包含介於約40重量%與約70重量%的聚胺甲酸酯(甲基)丙烯酸酯。
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