TWI681034B - 具有可活化吸氣劑材料之黏著劑、其用途及應用方法,及保護有機電子裝置之方法 - Google Patents
具有可活化吸氣劑材料之黏著劑、其用途及應用方法,及保護有機電子裝置之方法 Download PDFInfo
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- TWI681034B TWI681034B TW104135079A TW104135079A TWI681034B TW I681034 B TWI681034 B TW I681034B TW 104135079 A TW104135079 A TW 104135079A TW 104135079 A TW104135079 A TW 104135079A TW I681034 B TWI681034 B TW I681034B
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- adhesive tape
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- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 description 1
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- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
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- FOWDZVNRQHPXDO-UHFFFAOYSA-N propyl hydrogen carbonate Chemical compound CCCOC(O)=O FOWDZVNRQHPXDO-UHFFFAOYSA-N 0.000 description 1
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 1
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- 239000004065 semiconductor Substances 0.000 description 1
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- 150000004756 silanes Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229960004029 silicic acid Drugs 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
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- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
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- 125000001544 thienyl group Chemical group 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
- QLNOVKKVHFRGMA-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical group [CH2]CC[Si](OC)(OC)OC QLNOVKKVHFRGMA-UHFFFAOYSA-N 0.000 description 1
- JQPMDTQDAXRDGS-UHFFFAOYSA-N triphenylalumane Chemical compound C1=CC=CC=C1[Al](C=1C=CC=CC=1)C1=CC=CC=C1 JQPMDTQDAXRDGS-UHFFFAOYSA-N 0.000 description 1
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- 230000008016 vaporization Effects 0.000 description 1
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- 229940102001 zinc bromide Drugs 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
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- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
本發明揭示一種黏著劑,包含吸氣劑材料、及可選擇含有之溶劑,其包含可藉外部刺激活化之吸氣劑材料與滲透物的反應用之觸媒,而可容忍與滲透物(如水分)短暫接觸(尤其是在使用者應用之前)而吸氣劑能力無任何顯著損害。
Description
本發明關於一種黏著劑,其包含吸氣劑材料及可選擇使用之溶劑;一種包含此黏著劑之黏著帶;此黏著劑與此黏著帶之用途;及一種應用該黏著劑或黏著帶之方法。本發明進一步關於一種包含此黏著劑之黏著帶,及此黏著劑之用途。
此種黏著劑為常識。存在於該黏著劑中的吸氣劑材料可捕捉可滲透物質,例如水、氧、低分子量烴、或揮發性有機化合物,其穿透至黏著劑中。此類黏著劑用以例如封包欲防護水之物品。在此情形,該可滲透物質為水。此吸氣劑之用途的特別重要領域為(光)電子裝置。
(光)電子裝置現正比以往更常用於商業產品。此類裝置包含無機或有機電子結構,例如有機、有機金屬、或聚合半導體、或其組合。這些裝置及產品依照所欲用途而為剛性或撓性,現在對撓性裝置之需求增加。此類裝置係例如藉由印刷方法而製造,如凸版印刷、凹版印刷、網版印刷、平版印刷、或「非撞擊印刷」(例
如熱轉印、噴墨印刷、或數位印刷)。然而,許多情形亦使用真空方法,例如化學蒸汽沉積(CVD)、物理蒸汽沉積(PVD)、電漿強化化學或物理沉積(PECVD)方法、濺射、(電漿)蝕刻或汽化,在此情形結構化通常受光罩影響。
已商業化或因其市場潛力而感興趣之(光)電子裝置的實例包括電泳或電致變色組配件或顯示器、讀取或顯示裝置中的有機或聚合發光二極體(OLED或PLED),或者如照明、電致發光燈、發光電化學電池(LEEC)、有機太陽能電池(較佳為染料或聚合物太陽能電池)、無機太陽能電池(較佳為薄膜太陽能電池,尤其是基於矽、鍺、銅、銦、與砷)、鈣鈦礦太陽能電池、有機場效電晶體、有機交換元件、有機光學放大器、有機雷射二極體、有機或無機感應器、或基於有機或無機之RFID轉發器。
封包黏著帶之進一步應用在電池技術領域為已知的,尤其是在撓性微電池及薄膜電池之領域,更特別是包含含鋰陰極、陽極、或電解質者。
因而應了解,在此文件中,有機(光)電子裝置表示包含至少一種電子功能性、至少部分為有機構件-例如有機金屬化合物-或其中電子功能性結構的厚度小於20微米之電子裝置。
在無機及/或有機(光)電子領域中,更特別是有機(光)電子領域,得到合適的(光)電子裝置壽命及功能之技術挑戰被認為是對存在於其中的構件防護滲透物。
滲透物可能為大量低分子量有機或無機化合物,尤其是水蒸氣與氧。
在無機及/或有機(光)電子領域,更特別是使用有機原料材料的情形,有太多(光)電子裝置對水蒸氣與氧為敏感性,水或水蒸氣穿透被許多裝置認定為主要問題。因此,在該電子裝置之壽命期間需要藉封包防護,因為性能會隨使用時間而下降。例如在發光裝置的情形,如電致發光燈(EL燈)或有機發光二級體(OLED),相對於電泳顯示器(EP顯示器)的情形,組分氧化會造成亮度嚴重下降,或者在太陽能電池的情形,效率在非常短的時間嚴重下降。
為了達成非常良好的密封而使用專用屏障黏著劑(亦指具有水蒸氣屏障性質之黏著劑)。用以密封(光)電子構件之良好黏著劑對氧,且尤其是水蒸氣,為低滲透力,對裝置具有充分的黏附性,且可完全配合。
屏障作用一般藉由報告氧穿透率(OTR)及水蒸氣穿透率(WVTR)而特徵化。各速率表示在指定的溫度及分壓條件下,可能及進一步測量條件(如空氣相對濕度),按區域及時間計算的氧或水蒸氣通過膜之流量。這些值越小則各材料之封包適合度越佳。所報告的滲透性不單基於WVTR或OTR值,亦始終包括滲透之平均路徑長度的規格,例如材料厚度,或者標準化成為特定路徑長度。
滲透力P為氣體及/或液體滲透通過物體之能力的測度。P值低表示屏障作用良好。滲透力P為在
特定滲透路徑長度、分壓、及溫度的穩態條件下,界定材料與界定滲透性之比值。滲透力P為擴散項D與溶解度項S之積:P=D*S。
溶解度項S主要說明屏障黏著劑對滲透物之親和力。例如在水蒸氣的情形,疏水性材料獲得小的S值。擴散項D為滲透物在屏障材料中的移動力的測度,且與如分子移動力或自由體積之性質直接相關。該情形經常為高交聯或高結晶材料獲得相當低的D值。然而,高結晶材料通常較不透明,且交聯較大導致撓性較低。滲透力P一般隨分子移動力增加而提高,例如當溫度上升或超過玻璃轉移點時。
嘗試增加黏著劑之屏障作用必須考慮滲透物D及S,尤其是關於對水蒸氣與氧之滲透力的影響。除了這些化學性質,亦必須考量對滲透力之物理影響,尤其是平均滲透路徑長度及界面性質(黏著劑之配合特徵,黏附性)。理想的屏障黏著劑具有低的D值及S值,兼具非常良好的基板黏附性。
低溶解度項S單獨通常不足以獲得良好的屏障性質。其一特定典型實例為矽氧烷彈性體。該材料為極疏水性(溶解度項小),但是因圍繞Si-O鍵之自由轉動(擴散項大)而對水蒸氣與氧具有相當小的屏障作用。為了良好的屏障作用,因而溶解度項S與擴散項D之間必須有良好的平衡。
另外已揭述基於氫化程度最大的苯乙烯嵌段共聚物及樹脂之屏障黏著劑(參見DE 10 2008 047 964 A1號專利)。
在此亦報告常用黏著劑系統之滲透值(WVTR)(在37.5℃及90%相對壓力測量)。典型的丙烯酸酯系壓感性黏著劑為100克/平方米日至1,000克/平方米日之間的範圍。因為鏈之高移動力,壓感性聚矽氧黏著劑對水有超過1,000克/平方米日之甚至更高的滲透值。如果使用苯乙烯嵌段共聚物作為彈性體成分,則未氫化或不完全氫化系統獲得50-100克/平方米日之WVTR值,及氫化系統(例如SEBS)獲得小於50克/平方米日之值。純聚(異丁烯)彈性體、或苯乙烯與聚異丁烯之嵌段共聚物獲得小於15克/平方米日之特別低的WVTR值。
一種改良屏障作用之手段仍為使用與穿透物質(稱為可滲透物質,例如水或氧)反應之物質。穿透至(光)電子裝置中的可滲透物質,如氧或水蒸氣,然後被這些物質化學或物理(較佳為化學)結合,因此增加穿透時間(breakthrough time)(「延遲時間」)。該物質在文獻中稱為「吸氣劑」、「捕捉劑」、「乾燥劑」、或「吸收劑」。在以下僅使用術語「吸氣劑」。吸氣劑或吸氣劑材料為可吸收至少一種可滲透物質之材料。
吸氣劑材料為例如鹽,如氯化鈷、氯化鈣、溴化鈣、氯化鋰、溴化鋰、氯化鎂、過氯酸鋇、過氯酸鎂、氯化鋅、溴化鋅、氧化矽(例如矽膠)、硫酸鋁、硫酸鈣、硫酸銅、硫酸鋇、硫酸鎂、硫酸鋰、硫酸鈉、硫酸鈷、硫酸鈦、二硫亞磺酸鈉、碳酸鈉、二亞硫酸鉀、碳酸鉀、碳酸鎂、二氧化鈦、矽藻土、沸石;片狀矽酸鹽,如蒙脫石與膨土;金屬氧化物,如氧化鋇、氧化鈣、
氧化鐵、氧化鎂、氧化鈉、氧化鉀、氧化鍶、氧化鋁(活性鋁氧);及碳奈米管、活性碳、五氧化磷、與矽烷;易氧化金屬,例如鐵、鈣、鈉、與鎂;金屬氫化物,例如氫化鈣、氫化鋇、氫化鍶、氫化鈉、與氫化鋰鋁;氫氧化物,如氫氧化鉀與氫氧化鈉;金屬錯合物,例如乙醯丙酮酸鋁;另外及有機吸收劑,例如聚烯烴共聚物、聚醯胺共聚物、PET共聚酯、單與多羧酸之酐(如乙酸酐、丙酸酐、丁酸酐、或甲基四氫苯二甲酸酐);異氰酸酯或其他基於混成聚合物之吸收劑,其通常結合觸媒(例如鈷)而使用;其他的有機吸收劑,例如微交聯聚丙烯酸、聚乙烯醇、抗壞血酸酯、葡萄糖、五倍子酸、或不飽和脂與油。
依照其功能,吸氣劑材料較佳為以本質上無滲透物材料使用,例如無水形式。其使吸氣劑材料與作為填料之類似材料有所差別。例如氧化矽經常以發煙氧化矽之形式作為填料。然而,如果將此填料照常在周圍條件下儲存,則其從環境吸水且無法再作為工業可利用程度之吸氣劑材料。唯有已被乾燥或保持乾燥之氧化矽可作為吸氣劑材料。然而,亦可使用已以滲透物部分錯合之材料,例如CaSO4*1/2H2O(硫酸鈣半水合物),或定義為通式(SiO2)m*nH2O之化合物的部分水合氧化矽。
如上所述,應了解氧化矽表示通式(SiO2)m*nH2O之化合物。其為由濕化學、熱或熱解法製造的二氧化矽。更特別地,氧化矽中合適的吸氣劑材料為矽膠,例如經鈷化合物(作為水分指示劑)浸漬之矽膠(藍膠),及發煙氧化矽。
應了解,「吸收」表示一種或以上的物質被另一種物質-依照本發明係被吸氣劑材料-佔有的過程。吸氣劑因此亦可稱為「吸收劑」或「吸收試劑」。可滲透物質被吸氣劑材料吸收可例如因吸收或吸附,在此情形,吸附可以化學吸收或物理吸收之形式發生。
應了解,「可滲透物質」表示一種如氣態或液態物質,或者依情形為固態物質,而可穿透至欲保護的黏著劑中,繼而可穿透通過之物質。此類以上指稱的物質在以下稱為「滲透物」。滲透物可來自黏著劑本身或來自環境,例如甚至來自塗有黏著劑之黏著帶的載體材料。低分子量有機化合物,如溶劑殘渣、殘餘單體、油、樹脂成分、塑化劑、及水,經常從黏著劑或黏著帶本身發散。水、揮發性有機化合物(VOC)、低分子量烴、及氧經常從環境發散。
例如水,一種結合穿透水之方式為經由吸附於一般為氧化矽、分子篩、沸石、或硫酸鈉之物理方法。水經烷氧基矽烷、唑啶、異氰酸酯、氧化鋇、五氧化磷、鹼金屬與鹼土金屬氧化物(例如氧化鈣)、金屬鈣或金屬氫氧化物(WO 2004/009720 A2號專利)化學結合。
此種已揭述於黏著劑之吸氣劑主要為無機填料,例如氯化鈣或各種氧化物(參考US 5,304,419 A、EP 2 380 930 A1、或US 6,936,131 A號專利)。
有機吸氣劑亦已揭述於黏著劑,例如EP 2 597 697 A1號專利,其中使用聚合烷氧基矽烷作為吸氣劑。WO 2014/001005 A1號專利提及許多種在黏著劑中
作為吸氣劑之不同矽烷。在大量烷氧基矽烷的選擇中,所屬技術領域者首先選擇易水解的烷氧基矽烷。然而,當該烷氧基為乙氧基時,在將組裝件封包於有機電子設備中的情形獲得特別良好的活性。現已令人驚奇地發現,相較於甲氧基矽烷為較不反應性之乙氧基矽烷極更佳地降低水分滲透,特別是在高溫。其為意料外的,因為甲氧基矽烷之反應性通常比對應的乙氧基矽烷高(參考Wacker product description 6085e/09.13“GENIOSL®”,第11頁,2013年9月(09.13))。
此種黏著劑或由此黏著劑製造的膠帶的情形之困難為最終使用前之儲存及運輸。包含吸氣劑之黏著劑或膠帶在使用前必須以密閉式密封儲存/運輸。吸氣劑吸收穿透的滲透物,尤其是如水分,因此其被耗盡且屏障力降低。其尤其是對在電子設備中的應用非常不利,因為黏著帶通常被沖切成外部牽切機的大小,因此接觸水分。因此,依照牽切機沖切所花費的時間及出現的空氣濕度,膠帶中的水捕捉劑有時被大量消耗,有時為少量消耗。除了吸氣劑功能(即除了作為吸氣劑-且在此情形為吸收水-之能力)降低,黏著劑或黏著帶因此在應用之後所具有吸氣劑能力,即吸收水之能力,不再明確有效。
因此,本發明之一目的為提供一種黏著劑,其容忍與滲透物(如水分)短暫接觸(尤其是在使用者應用之前)而吸氣劑能力無任何顯著損害。
現已令人驚奇地發現,當開頭指定型式的黏著劑包含可藉外部刺激活化之吸氣劑材料與滲透物的反應用之觸媒時,可獲得此種黏著劑。
在此黏著劑的情形,當必要時吸氣劑功能可被活化,即尤其是當已塗佈該黏著劑及使物品防護滲透物(例如水蒸氣)時。此黏著劑可被稱為「可切換(switchable)」。其滲透物結合功能,尤其是水結合功能,可藉外部刺激或引發劑「切換」,藉該外部刺激或引發劑將觸媒活化。在該黏著劑之儲存或運輸期間,該觸媒、因此及吸氣劑功能,尚未被活化或開放。吸氣劑若與滲透物(尤其是與水蒸氣)反應亦為不顯著程度,且未被消耗。僅當該黏著劑已被塗佈且事實上使物品防護水蒸氣及防護水蒸氣穿透時,吸氣劑被活化或「開啟」及呈現其功能。
該觸媒改變吸氣劑與滲透物(尤其是與水(蒸氣))的反應之速率常數。在本發明內文中,該改變為速率常數增加至少5倍,較佳為10倍,更佳為至少50倍。
該觸媒可例如為潛在性酸或潛在性鹼,其表示該觸媒在活化後可就酸鹼性質方面而言改變化學環境,因此將速率與環境有關的反應加速。以矽烷為例,例如反應速率對pH之依附性揭述於J.Org.Chem.,第51卷,第20期,1986第3827-3830頁。其他有水的pH依附性反應為例如酐、碳化二亞胺、唑啶酮、酯、或異氰酸酯酯之水解。
此種環境變化而可發生的潛在系統之實例為基於鎓鹽之系統,尤其是鋶與錪,及二茂鐵。
在水的情形,吸氣劑材料在中性或準中性環境中對水之活性最低。應了解,「中性環境」表示相當於在水溶液中pH為7之環境。應了解,「準中性環境」表示相當於在水溶液中pH為6至8之間,較佳為6.5至7.5之間的環境。在中性環境中,此情形之吸氣劑材料對水反應之反應速率最低。該反應速率太低而使得與水(蒸氣)無顯著反應。相反地,如果環境變成酸性或鹼性,則反應速率顯著上升。
所屬技術領域者已知的其他觸媒亦適合本發明。觸媒已備奈米或微米封包尤其為典型的。這些觸媒因破壞該封包而被活化。
存在於本發明黏著劑中的觸媒之量較佳為小於5重量百分比,更佳為小於2重量百分比,且尤其是小於1重量百分比。因此,相當少量即足以達成本發明之效果。
「外部刺激」表示將觸媒活化之外部影響。
特別適合的外部刺激為UV放射線、溫度變化、微波放射線、或可見光,非常偏好UV放射線。簡單地以UV放射線活化為可能的;另一方面,黏著劑不太可能在所欲應用之前偶然對UV放射線曝光,故可避免非蓄意活化。
更佳為該黏著劑包含由至少一種彈性體、及至少一種膠黏樹脂組成的黏著劑基底。特別合適的黏著
劑因此包含黏著劑基底、吸氣劑材料、及可選擇含有之溶劑、及可藉外部刺激之吸氣劑材料與滲透物的反應用之觸媒。
另外,本發明黏著劑較佳為壓感性黏著劑。如此使其使用容易而特別良好,因為該黏著劑甚至在交聯之前已黏附於欲黏結位置。
本發明黏著劑當進一步包含至少一種具有至少一個可硬化基之反應性樹脂時有特別良好的適合度。此黏著劑可被塗佈,但仍先要可變形。其僅在該可硬化基反應之後,黏著劑才硬化及展現其完整黏結作用。
特別適合的可硬化基為環狀醚、乙烯基、丙烯酸酯、甲基丙烯酸酯、羥基、胺基及/或異氰酸酯。該反應性樹脂中亦可有複數個不同的可硬化基。
當該黏著劑包含反應性樹脂時,若對吸氣劑材料與滲透物的反應用之觸媒之刺激同時為該反應性樹脂硬化用之引發劑,則此類系統特別易於處理。尤其是UV放射線特別適合作為該刺激。在此情形,該觸媒為光觸媒。
另一方面,非常適合的黏著劑亦包括不含有任何反應性樹脂者。此類黏著劑不需要額外的硬化步驟,故不必考量任何對此系統中反應性基硬化之要求,且僅顧慮吸氣劑材料以必要方式被活化。
壓感性黏著劑特別適合作為無反應性樹脂之黏著劑。
較佳為該黏著劑為具有黏著劑基底之屏障黏著劑,該基底在有反應性樹脂的情形硬化後具有小於100克/平方米日,較佳為小於50克/平方米日,尤其是小於15克/平方米日之水蒸氣滲透率。
較佳為該黏著劑在刺激觸媒之前具有中性或準中性環境。因此,較佳為該黏著劑不含有任何酸性或鹼性基,尤其是無有機酸、丙烯酸、甲基丙烯酸、胺、醯胺、或其聚合物。
更佳為該吸氣劑材料為至少一種選自由烷氧基矽烷與烷氧基矽氧烷所組成的群組之化合物。這些化合物確保中性環境。烷氧基矽烷與烷氧基矽氧烷較佳為在此可為單體、或具有2至40個重複SiR2基之寡聚物。該化合物可為鏈接或環狀。
應了解,「矽烷」表示通式Ra-Si-X4-a之化合物、或其部分縮合產物。在式中,a為0至3,且較佳為0或1之整數。X為可水解基,例如且偏好鹵素原子,尤其是氯,烷氧基,例如甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、第二丁氧基、或第三丁氧基,或乙醯氧基。所屬技術領域者已知的可水解基之其他實例同樣可用於本發明內文。如果有複數個X取代基,則其可為相同或不同。R為可選擇經取代之烴基團,例如甲基、乙基、正丙基、異丙基、正丁基、第二丁基或第三丁基、戊基與其分枝異構物、己基與其分枝異構物、庚基與其分枝異構物、辛基與其分枝異構物、壬基與其分枝異構物、癸基與其分枝異構物、十一基與其分枝異構
物、十二基與其分枝異構物、十四基與其分枝異構物、十六基與其分枝異構物、十八基與其分枝異構物、或二十基與其分枝異構物。該烴基團可另外含有環狀及/或芳香族成分。其代表性結構為環己基、苯基、與苄基。視情況地,該烴基團R含有例如一種或以上的含雜原子取代基,如胺基、胺基烷基、環氧丙氧基、(甲基)丙烯醯氧基等。如果有複數個R取代基,則其可為相同或不同。
可作為吸氣劑材料之矽烷較佳為選自包含以下的群組: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-胺基丙基二乙氧基甲基矽烷、N-(2-胺基乙基)-3-胺基丙基二甲氧基甲基矽烷、(N-丁基)-3-胺基丙基三甲氧基矽烷、3-(N-乙胺基)-2-甲基丙基三甲氧基矽烷、4-胺基-3,3-二甲基丁基三甲氧基矽烷、4-胺基-3,3-二甲基丁基二甲氧基甲基矽烷、(N-環己基)胺基甲基二甲氧基甲基矽烷、(N-環己基)胺基甲基三甲氧基矽烷、(N-苯基)-3-胺基丙基三甲氧基矽烷、(N-苯基)胺基甲基二甲氧基甲基矽烷、(N-苄基-2-胺基乙基)-3-胺基丙基三甲氧基矽烷、[2-(N-苄基-N-乙烯基胺基)乙基]-3-胺基丙基三甲氧基矽烷鹽酸鹽、[2-(N-苄基-N-乙烯基胺基)乙基]-3-胺基丙基三甲氧基矽烷、貳(3-丙基三乙氧基矽烷基)胺、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三(2-甲氧基乙氧基)矽烷、乙烯基三異丙氧基矽烷、乙烯基二甲氧基甲基矽烷、乙烯基三乙醯氧基矽烷、3-三乙氧基矽烷基丙基琥
珀酸酐、3-環氧丙氧基丙基丙基三甲氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、2-(3,4-環氧基環己基)乙基三乙氧基矽烷、2-(3,4-環氧基環己基)乙基三甲氧基矽烷、2-(3,4-環氧基環己基)乙基甲基二甲氧基矽烷、2-(3,4-環氧基環己基)乙基甲基二乙氧基矽烷、三乙氧基辛基矽烷、三甲氧基辛基矽烷、3-環氧丙氧基丙基二乙氧基甲基矽烷、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三乙氧基矽烷、3-甲基丙烯醯氧基丙基三異丙氧基矽烷、3-甲基丙烯醯氧基丙基二甲氧基甲基矽烷、3-甲基丙烯醯氧基丙基二乙氧基甲基矽烷、3-氯丙基三甲氧基矽烷、3-氯丙基三乙氧基矽烷、3-異氰酸基丙基三甲氧基矽烷、3-異氰酸基丙基三乙氧基矽烷、異氰酸基甲基三甲氧基矽烷、異氰酸基甲基二甲氧基甲基矽烷、參[3-(三甲氧基矽烷基)丙基]異三聚氰酸酯、3-脲基丙基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷、2-羥基-4-(3-三乙氧基矽烷基丙氧基)二苯基酮、4-(3’-氯二甲基矽烷基丙氧基)二苯基酮、3-巰基丙基三甲氧基矽烷、3-巰基丙基二甲氧基甲基矽烷、貳(3-三乙氧基矽烷基丙基)二硫烷、貳(3-三乙氧基矽烷基丙基)四硫烷、貳(三乙氧基矽烷基丙基)多硫烷、與氯化十八碳胺基二甲基三甲氧基矽烷基丙基銨。亦可使用其他的非交聯烷氧基矽烷作為吸氣劑材料。
應了解,本發明內文之矽氧烷表示具有至少二個經氧原子鍵結之SiR2基之化合物。在特別適合本發明之烷氧基矽氧烷中,至少一個R基團為烷氧基。特別
適合本發明之矽氧烷的實例為前段提及之寡聚物或聚合物。
較佳為該吸氣劑具有至少一個可硬化基。特別適合的可硬化基為環狀醚、乙烯基、丙烯酸酯、甲基丙烯酸酯、羥基、胺基、或異氰酸酯。
在以烷氧基矽氧烷作為吸氣劑的情形,該烷氧基矽氧烷較佳為每個矽原子具有一個烷氧基與一個可硬化基。該烷氧基可與相鄰的Si-烷氧基相同或不同。相鄰重複單元之可硬化基同樣可為相同或不同。
在以烷氧基矽氧烷作為吸氣劑的情形,該烷氧基矽氧烷具有至少一個乙氧基與至少一種可硬化基,該可硬化基為環狀醚基。特別合適的環狀醚基為環氧基或環氧丙基,及矽烷、2-(3,4-環氧基環己基)乙基三甲氧基矽烷,尤其是2-(3,4-環氧基環己基)乙基三乙氧基矽烷,且特佳為2-(3,4-環氧基環己基)乙基甲基二乙氧基矽烷。
吸氣劑材料之量為至少2重量百分比,較佳為至少3重量百分比,且尤其是至少5重量百分比,則黏著劑帶有特別良好的性質。非常特別有利的黏著劑為其中吸氣劑材料之量為3至15重量百分比,較佳為4至10重量百分比,且尤其是4.5至7重量百分比之範圍。
反應性樹脂在黏著劑中的比例為15至80重量百分比,尤其是20至70重量百分比,且更佳為25至65重量百分比。為了在硬化後獲得良好的使用容易性及彈性黏著劑,較佳的反應性樹脂含量為15至35重量百
分比,尤其是20至30重量百分比。對於更高交聯的黏著劑黏結,反應性樹脂含量較佳為65至80重量百分比。產生特別良好的有關彈性與交聯程度之平衡的反應性樹脂含量為35至65重量百分比。
在一較佳具體實施例中,該反應性樹脂包含環氧基,尤其是脂肪族,且非常特佳為環脂肪族環氧基。適合性非常良好為含有環氧丙基及/或環氧基環己基作為可硬化基之反應性樹脂。
非常特別適合的黏著劑為其中反應性樹脂及烷氧基矽烷或烷氧基矽氧烷具有同類的基(尤其是相同的可硬化基)者。在此情形,反應性樹脂及寡聚烷氧基矽烷或烷氧基矽氧烷可以特別良好的方式彼此聚合及交聯。應了解,「同類的官能性可硬化基」表示化學上彼此非常類似者,例如環大小不同的環狀醚、或其中環脂肪族結構之環大小不同的環氧基醚。
在一較佳具體實施例中,該黏著劑藉陽離子性、熱、或放射線誘發硬化。另外較佳為該黏著劑含有至少一型可交聯成分之陽離子性硬化用光引發劑。
在一特佳具體實施例中,該黏著劑含有反應性樹脂,且將吸氣劑硬化及活化的步驟同時進行,且硬化及活化係以相同的方式誘發。例如反應性脂的交聯反應可藉UV誘發。UV放射線亦會在中性至酸性的環境中產生變化,其例如再度造成吸氣劑活化。平行硬化及活化特別適合,因為在已塗佈黏著劑或黏著帶之後僅需要一個步驟。其同樣僅需要一種裝置,例如UV放射線來源。藉熱誘發進行硬化及吸氣劑活化同樣可行。
壓感性黏著劑指即使是在相當溫和的接觸壓力下仍可持續黏結基板,且在使用後又可從基板脫離而本質上無殘渣之黏著劑。壓感性黏著劑在室溫為永久性壓感性,因此觸摸為充分低的黏度及高膠黏性,使得其即使是在低接觸壓力仍將特定基板的表面潤濕。對應黏著劑之黏結力係基於其黏著性質、及對其內聚性質之再脫離力。可使用的壓感性黏著劑基底包括各種材料。
該聚合物可為一種聚合物、或二種或以上的不同聚合物的混合物。在此情形,該至少一種聚合物尤其可為彈性體或熱塑物。
所使用的彈性體原則上可為壓感性黏著劑產業習用之任何彈性體,例如如Donatas Satas之“Handbook of Pressure Sensitive Adhesive Technology”(Satas & Associates,Warwick 1999)所述。
在本申請案內文中,在化學方面,較佳為所使用的彈性體由至少一種烯烴單體或由聚胺基甲酸酯形成,且為例如基於聚胺基甲酸酯、天然橡膠、合成橡膠(如丁基、(異)丁基、腈、或丁二烯橡膠)、具有由不飽和或部分或完全氫化聚二烯嵌段(聚丁二烯、聚異戊二烯、聚(異)丁烯、其與所屬技術領域者熟知的其他彈性體嵌段的共聚物)形成的彈性體嵌段之苯乙烯嵌段共聚物、聚烯烴、氟聚合物及/或聚矽氧之彈性體。
較佳為該至少一種彈性體由至少一種烯烴單體及/或由至少一種聚胺基甲酸酯形成。更佳為該彈性體為至少一種乙烯基芳香族嵌段共聚物。
如果使用橡膠或合成橡膠、或由其製造的摻合物,作為壓感性黏著劑之基底材料,則天然橡膠原則上可依照所需的純度及黏度程度選自所有可用的品質,例如縐綢、RSS、ADS、TSR、或CV型,且合成橡膠選自由無規共聚合苯乙烯-丁二烯橡膠(SBR)、丁二烯橡膠(BR)、合成聚異戊二烯(IR)、丁基橡膠(IIR)、鹵化丁基橡膠(XIIR)、丙烯酸酯橡膠(ACM)、乙烯-乙酸乙烯酯共聚物(EVA)、或聚胺基甲酸酯及/或其摻合物所組成的群組。
所使用的至少一種聚合物亦可為所屬技術領域者已知的任何種類之熱塑物,例如如教科書J.M.G.Cowie之“Chemie und Physik der synthetischen Polymere”[Chemistry and Physics of Synthetic Polymers](Vieweg,Braunschweig)、及B.Tieke之“Makromolekulare Chemie”[Macromolecular Chemistry](VCH Weinheim,1997)所指定。其中有例如聚(乙烯)、聚(丙烯)、聚(氯乙烯)、聚(苯乙烯)、聚(甲醛)、聚(環氧乙烷)、聚(對苯二甲酸伸乙酯)、聚(碳酸酯)、聚(苯醚)、聚(胺基甲酸酯)、聚(脲)、苯氧樹脂、丙烯腈-丁二烯-苯乙烯(ABS)、聚(醯胺)(PA)、聚(乳酸酯)(PLA)、聚(醚醚酮)(PEEK)、聚(碸)(PSU)、聚(醚碸)(PES)。聚(丙烯酸酯)、聚(甲基丙烯酸酯)、與聚(甲基丙烯酸甲酯)(PMMA)如聚合物同樣可行,但是在本發明內文中不較佳。
可用於矽氧烷水解催化之內涵觸媒尤其是基於鋶、錪、與二茂鐵之系統。鋶系陽離子之實例可參考
US 6,908,722 B1號專利(尤其是第10至21欄)所示的細節。
作為上述陽離子之相對離子的陰離子之實例包括四氟硼酸基、四苯基硼酸基、六氟磷酸基、過氯酸基、四氯鐵酸基、六氟砷酸基、六氟銻酸基、五氟羥基銻酸基、六氯銻酸基、肆五氟苯基硼酸基、肆(五氟甲基苯基)硼酸基、二(三氟甲基磺醯基)醯胺、與甲基化參(三氟甲基磺醯基)。特別是錪系引發劑用之其他可想到的陰離子另外包括氯化物、溴化物、或碘化物,但是偏好引發劑本質上無氯與溴。
更特定而言,可使用的系統包括:˙鋶鹽(參見例如US 4,231,951 A、US 4,256,828 A、US 4,058,401 A、US 4,138,255 A、及US 2010/063221 A1號專利),如三苯基鋶六氟砷酸鹽、三苯基鋶六氟硼酸鹽、三苯基鋶四氟硼酸鹽、三苯基鋶肆(五氟苄基)硼酸鹽、甲基二苯基鋶四氟硼酸鹽、甲基二苯基鋶肆(五氟苄基)硼酸鹽、二甲基苯基鋶六氟磷酸鹽、三苯基鋶六氟磷酸鹽、三苯基鋶六氟銻酸鹽、二苯基萘基鋶六氟砷酸鹽、三甲苯鋶六氟磷酸鹽、大茴香基二苯基鋶六氟銻酸鹽、4-丁氧基苯基二苯基鋶四氟硼酸鹽、4-氯苯基二苯基鋶六氟銻酸鹽、參(4-苯氧基苯基)鋶六氟磷酸鹽、二(4-乙氧基苯基)甲基鋶六氟砷酸鹽、4-乙醯基苯基二苯基鋶四氟硼酸鹽、4-乙醯基苯基二苯基鋶肆(五氟苄基)硼酸鹽、參(4-硫甲氧基苯基)鋶六氟
磷酸鹽、二(甲氧基磺醯基苯基)甲基鋶六氟銻酸鹽、二(甲氧基萘基)甲基鋶四氟硼酸鹽、二(甲氧基萘基)甲基鋶肆(五氟苄基)硼酸鹽、二(羰甲氧基苯基)甲基鋶六氟磷酸鹽、(4-辛氧基苯基)二苯基鋶肆(3,5-貳(三氟甲基)苯基)硼酸鹽、參[4-(4-乙醯基苯基)硫苯基]鋶肆(五氟苯基)硼酸鹽、參(十二基苯基)鋶肆(3,5-貳三氟甲基苯基)硼酸鹽、4-乙醯胺基苯基二苯基鋶四氟硼酸鹽、4-乙醯胺基苯基二苯基鋶肆(五氟苄基)硼酸鹽、二甲基萘基鋶六氟磷酸鹽、三氟甲基二苯基鋶四氟硼酸鹽、三氟甲基二苯基鋶肆(五氟苄基)硼酸鹽、苯基甲基苄基鋶六氟磷酸鹽、5-甲基噻蒽六氟磷酸鹽、10-苯基-9,9-二甲基硫六氟磷酸鹽、10-苯基-9-氧代硫四氟硼酸鹽、10-苯基-9-氧代硫肆(五氟苄基)硼酸鹽、5-甲基-10-氧代硫四氟硼酸鹽、5-甲基-10-氧代硫肆(五氟苄基)硼酸鹽、與5-甲基-10,10-二氧代硫六氟磷酸鹽;˙錪鹽(參見例如US 3,729,313 A、US 3,741,769 A、US 4,250,053 A、US 4,394,403 A、及US 2010/063221 A1號專利),如二苯基錪四氟硼酸鹽、二(4-甲基苯基)錪四氟硼酸鹽、苯基-4-甲基苯基錪四氟硼酸鹽、二(4-氯苯基)錪六氟磷酸鹽、二萘基錪四氟硼酸鹽、二(4-三氟甲基苯基)錪四氟硼酸鹽、二苯基錪六氟磷酸鹽、二(4-甲基苯基)錪六氟磷酸鹽、二苯基錪六氟砷酸鹽、二(4-苯氧基苯基)錪四氟硼酸鹽、苯基-2-噻吩基錪六氟
磷酸鹽、3,5-二甲基吡唑基-4-苯基錪六氟磷酸鹽、二苯基錪六氟銻酸鹽、2,2'-二苯基錪四氟硼酸鹽、二(2,4-二氯苯基)錪六氟磷酸鹽、二(4-溴苯基)錪六氟磷酸鹽、二(4-甲氧基苯基)錪六氟磷酸鹽、二(3-羧基苯基)錪六氟磷酸鹽、二(3-甲氧基羰基苯基)錪六氟磷酸鹽、二(3-甲氧基磺醯基苯基)錪六氟磷酸鹽、二(4-乙醯胺基苯基)錪六氟磷酸鹽、二(2-苯并噻吩基)錪六氟磷酸鹽,二芳基錪參三氟甲基磺醯基甲基化物,如二苯基錪六氟銻酸鹽,二芳基錪肆(五氟苯基)硼酸鹽,如二苯基錪肆(五氟苯基)硼酸鹽、(4-正去矽烷氧基苯基)苯基錪六氟銻酸鹽、[4-(2-羥基-正去矽烷氧基)苯基]苯基錪六氟銻酸鹽、[4-(2-羥基-正去矽烷氧基)苯基]苯基錪三氟磺酸鹽、[4-(2-羥基-正四去矽烷氧基)苯基]苯基錪六氟磷酸鹽、[4-(2-羥基-正四去矽烷氧基)苯基]苯基錪肆(五氟苯基)硼酸鹽、貳(4-第三丁基苯基)錪六氟銻酸鹽、貳(4-第三丁基苯基)錪六氟磷酸鹽、貳(4-第三丁基苯基)錪三氟磺酸鹽、貳(4-第三丁基苯基)錪四氟硼酸鹽、貳(十二基苯基)錪六氟銻酸鹽、貳(十二基苯基)錪四氟硼酸鹽、貳(十二基苯基)錪六氟磷酸鹽、貳(十二基苯基)錪三氟甲基磺酸鹽、二(十二基苯基)錪六氟銻酸鹽、二(十二基苯基)錪三氟甲磺酸鹽、二苯基錪重硫酸鹽、4,4’-二氯二苯基錪重硫酸鹽、4,4’-二溴二苯基錪重硫酸鹽、3,3’-二硝基
二苯基錪重硫酸鹽、4,4’-二甲基二苯基錪重硫酸鹽、4,4’-貳(琥珀醯胺基二苯基)錪重硫酸鹽、3-硝基二苯基錪重硫酸鹽、4,4’-二甲氧基二苯基錪重硫酸鹽、貳(十二基苯基)錪肆(五氟苯基)硼酸鹽、(4-辛氧基苯基)苯基錪肆(3,5-貳三氟甲基苯基)硼酸鹽、與(甲苯基異丙苯基)錪肆(五氟苯基)硼酸鹽;及˙二茂鐵鹽(參見例如EP 542 716 B1號專利),如η5-(2,4-環戊二烯-1-基)-[(1,2,3,4,5,6,9)-(1-甲基乙基)苯]鐵。
另外,光潛伏鹼(photolatent base)揭述於J.Studer等人之論文“Photolatent bases:new catalysts for UV-curing of coatings”,其係在Radtech e5:UV & EB Technology Conference 2006(RadTech International,NA,23.-26.April 2006,Lakeside Center at McCormick Place-Chicago,IL)發表。其中提及的光潛伏鹼之實例為苯基乙醛酸酯之銨鹽、二苯甲基銨鹽、N-二苯基酮甲基三-N-烷基銨鹽、胺醯亞胺衍生物、α-銨基二苯基酮鹽、或N-甲基尼非待平(nifedipine)。光潛伏鹼之其他實例可在“Coatings & Inks-Photoinitiators Part 3:What’s New or May Be Coming”(Gordon Bradley,24.01.2007),及在其中引用的美國專利US 6,489,374、US 6,087,070、US 20040242867、與US 20030212164號中發現,例如4-(鄰硝基苯基)二氫吡啶、四級有機硼光引發劑、α-胺基苯乙酮、及α-銨基烯屬烴、亞胺基烯屬烴、或甲脒基烯屬烴
之四或三芳基烷基硼酸酯、及在UV光下釋放DBN(1,5-二氮雜雙環[4.3.0]壬-5-烯)之化合物。
其他的可活化觸媒本質上為所屬技術領域者已知的奈米或微米封包方法,且詳述於Vikas Mittal編輯的“Encapsulation Nanotechnologies”,Wiley。典型釋放機構揭述於其中的10.8.2章。
視情況存在之合適膠黏樹脂為所屬技術領域者已知的膠黏樹脂,例如得自Satas。
特別有利為壓感性黏著劑含有至少一型較佳為至少部分氫化膠黏樹脂,有利為與彈性體成分相容者,或者如果使用由硬及軟嵌段形成的共聚物,則主要為具有軟嵌段(塑化劑樹脂)。
當對應的膠黏樹脂之軟化溫度(藉環球法測量)高於25℃時為有利的。另外,當使用至少一型軟化溫度低於20℃之膠黏樹脂時為另外有利的。如果需要,其可一方面藉此方法微調黏著劑特徵,另一方面微調黏結基板之配合特徵。
對於相當非極性彈性體,用於壓感性黏著劑之樹脂可有利地為基於松脂及松脂衍生物之部分或完全氫化樹脂、二環戊二烯之氫化聚合物、基於C5、C5/C9、或C9單體流之部分、選擇性或完全氫化烴樹脂、基於α-蒎烯及/或β-蒎烯及/或δ-檸檬烯及/或△3-蒈烯之聚萜烯、較佳為純C8與C9芳香族之氫化聚合物。上述膠黏樹脂可單獨或以混合物使用。
其可使用在室溫為固態或液態之樹脂。為了確保高老化及UV安定性,其偏好氫化程度為至少90%,較佳為至少95%之氫化樹脂。
可選擇存在的反應性樹脂,其亦稱為可交聯成分,原則上可為壓感性黏著劑或反應性黏著劑之領域的所屬技術領域者已知的任何反應性組分,且在分子量增加反應中形成巨分子,例如如Gerd Habenicht“Kleben-Grundlagen,Technologien,Anwendungen”[Adhesive Bonding Principles,Technologies,Applications],第6版,Springer,2009所述。其為例如形成環氧化物、聚酯、聚醚、聚胺基甲酸酯或酚樹脂、基於甲酚或酚醛樹脂之聚合物、聚硫化物或丙烯酸系聚合物(丙烯酸系、甲基丙烯酸系)之組分。
該可交聯成分之結構及化學本性並不嚴格,其條件為與彈性體相至少部分互溶,及分子量增加反應可在不導致彈性體相之任何顯著損害及/或瓦解的條件下進行,尤其是關於所使用的溫度、所使用的觸媒型式等。
該反應性樹脂較佳為由環狀醚組成,且適合放射線-化學、視情況及熱交聯,其軟化溫度低於40℃,較佳為低於20℃。
基於環狀醚之反應性樹脂特別是環氧化物,即帶有至少一個環氧乙烷或環氧丙烷基之化合物。其本質可為芳香族,尤其是脂肪族或環脂肪族。
可使用的反應性樹脂可為單官能性、二官能性、三官能性、或四官能性,或者具有更高官能性至多官能性,該官能性係關於環狀醚基。
不打算強加限制,其實例為3,4-環氧基環己基甲基-3’,4’-環氧基環己烷羧酸酯(EEC)與衍生物、二氧化二環戊二烯與衍生物、3-乙基-3-環氧丙烷甲醇與衍生物、二環氧丙基四氫苯二甲酸酯與衍生物、二環氧丙基六氫苯二甲酸酯與衍生物、乙烷1,2-二環氧丙基醚與衍生物、丙烷1,3-二環氧丙基醚與衍生物、丁烷-1,4-二醇二環氧丙基醚與衍生物、高碳烷屬烴1,n-二環氧丙基醚與衍生物、貳[(3,4-環氧基環己基)甲基]己二酸酯與衍生物、二氧化乙烯基環己基與衍生物、環己烷-1,4-二甲醇貳(3,4-環氧基環己烷羧酸酯)與衍生物、二環氧丙基4,5-環氧基四氫苯二甲酸酯與衍生物、貳[1-乙基(3-環氧丙基)甲基)醚與衍生物、季戊四醇四環氧丙基醚與衍生物、雙酚A二環氧丙基醚(DGEBA)、氫化雙酚A二環氧丙基醚、雙酚F二環氧丙基醚、氫化雙酚F二環氧丙基醚、環氧基酚酚醛樹脂、氫化環氧基酚酚醛樹脂、環氧基甲酚酚醛樹脂、氫化環氧基甲酚酚醛樹脂、2-(7-二環;螺[1,3-二氧陸圜-5,3’-[7]二環[4.1.0]庚烷]、1,4-貳((2,3-環氧基丙氧基)甲基)環己烷。
特別適合陽離子性硬化為基於環己基環氧化物之反應性樹脂,例如3,4-環氧基環己基甲基-3’,4’-環氧基環己烷羧酸酯(EEC)與衍生物、及貳[(3,4-環氧基環己基)甲基]己二酸酯與衍生物。
反應性樹脂可以其單聚或二聚形式、三聚形式等,至多及包括其寡聚形式使用。
反應性樹脂彼此、或與其他共反應性化合物(如醇(單官能性或多官能性)或乙烯醚(單官能性或多官能性))的混合物同樣可行。
更佳為本發明之黏著劑為壓感性黏著劑。如此可使得使用容易性特別良好,因為該黏著劑甚至在交聯前已黏附於欲黏結位置。
壓感性黏著劑指即使是在相當溫和的接觸壓力下仍可持續黏結基板,且在使用後又可從基板脫離而本質上無殘渣之黏著劑。壓感性黏著劑在室溫為永久性壓感性,因此觸摸為充分低的黏度及高膠黏性,使得其即使是在低接觸壓力仍將特定基板的表面潤濕。對應黏著劑之黏結力係基於其黏著性質、及對其內聚性質之再脫離力。可使用的壓感性黏著劑基底包括各種材料。
本發明另外關於一種黏著帶,其一面或二面塗有本發明之黏著劑。此黏著帶亦可為轉印黏著帶。黏著帶可造成特別簡單及精確的黏結,因此特別合適。
最後,本發明關於本發明黏著劑或本發明黏著帶作為密封化合物之用途,尤其是用以封包有機電子設備中的組裝件。如上所述詳述,必須對組件防護水(蒸氣)對有機電子設備極為重要。因為其良好的屏障性質,本發明之黏著劑或黏著帶可產生對應防護。因為高透明性及對欲封包的電子設備之損壞小,如同邊緣封包,本發明之黏著劑及本發明之黏著帶尤其亦適合有機電子設備之全區封包。
最後,本發明關於一種應用黏著劑或具有黏著劑之黏著膠帶,尤其是本發明之黏著劑或黏著膠帶之方法,其步驟包含:- 將該黏著劑或黏著膠帶施加於欲黏結的物品,及- 藉外部刺激將吸氣劑材料活化。
以此方法,黏著劑或黏著膠帶在事實上需要(即當其封包或覆蓋欲保護的物品時)之前不展現屏障作用。僅從此時開始,吸氣劑活化成為水捕捉劑。由於吸氣劑作用未事先活化,故在進行儲存或運輸期間未消耗吸氣劑。
一般表示之「黏著帶」包含在一或二面上具有(壓感性)黏著劑之載體材料。該載體材料包括任何平坦結構,例如二維伸長之膜或膜片、長度伸展且寬度有限之帶、帶片、沖切部分(例如(光)電子裝置之邊緣或邊界之形式)、多層裝置等。對於各種應用,其可將非常多種不同的載體,例如膜、紡織物、非織物、及紙,組合黏著劑。另外,術語「黏著帶」亦包含所謂的「轉印黏著帶」,即無載體之黏著帶。在轉印黏著帶的情形,黏著劑是在塗佈於具有脫離層及/或具有抗黏著性質的撓性襯墊之間塗佈。塗佈固定為首先移除一襯墊,塗佈黏著劑,然後移除第二襯墊的情形。如此可將黏著劑直接用於黏結(光)電子裝置中的兩個表面。
亦可為其中不是二個襯墊,而是單一雙面隔離襯墊之黏著帶。在此情形,將黏著帶腹板上面以雙面隔離襯墊之一面覆蓋,及將下面以雙面隔離襯墊之反面覆蓋。尤其是將包裝或捆包相鄰捲繞。
在本文中,黏著帶用之載體材料較佳為包含聚合物膜、膜複合物、或具有有機及/或無基層之膜或膜複合物。舉例而非限制,此類膜/膜複合物可由任何用以製膜之標準塑膠組成:聚乙烯、聚丙烯-尤其是藉單或雙軸拉伸而製造的延伸聚丙烯(OPP)、環狀烯烴共聚物(COC)、聚氯乙烯(PVC)、聚酯-尤其是聚對苯二甲酸伸乙酯(PET)與聚萘甲酸伸乙酯(PEN)、乙烯-乙烯醇(EVOH)、聚偏二氯乙烯(PVDC)、聚偏二氟乙烯(PVDF)、聚丙烯腈(PAN)、聚碳酸酯(PC)、聚醯胺(PA)、聚醚碸(PES)、或聚醯亞胺(PI)。
聚酯膜之優點為確保熱安定性且引入高溫機械安定性。因此,最佳為本發明襯墊中的載體層由聚酯膜組成,例如雙軸拉伸聚對苯二甲酸伸乙酯。
在一較佳具體實施例中,該載體材料亦包括針對一種或以上的指定滲透物之屏障官能基,尤其是針對水蒸氣與氧。此屏障官能基可由有機或無機材料組成。具有屏障官能基之載體材料揭述於EP 2 078 608 A1號專利。
更佳為該載體材料包含至少一無機屏障層。適合性特別良好的無機屏障層為在低壓下(例如藉蒸發、CVD、PVD、PECVD)或在大氣壓力下(例如藉大氣電漿、反應性電暈放電、或熱解)沉積的金屬,如鋁、銀、金、鎳,尤其是金屬化合物,如金屬氧化物、氮化物、或氫氮化物,例如矽、硼、鋁、鋯、鉿、或碲之氧化物或氮化物,或氧化銦錫(ITO)。同樣合適為已摻有其他元素的上述變異式之層。
在雙面(自黏)黏著帶的情形,所使用的上下層可為種類相同或不同及/或層厚度相同或不同的本發明黏著劑。一面或或二面上的載體可依照先前技術進行前處理,例如達成黏著劑固定之改良。一面或或二面同樣可已提供功能層,例如其功能可為屏障層。壓感性黏著劑層可視情況以脫離紙或脫離膜覆蓋。或者亦可將僅一黏著劑層以雙面隔離襯墊覆蓋。
在一變異式中,在該雙面(自黏)黏著帶中提供本發明之黏著劑作為又一種黏著劑,例如任何對覆蓋基板之黏附性特別良好,或重置力特別良好者。
以轉黏著帶或塗覆在平坦結構上之形式存在的壓感性黏著劑之厚度較佳為1微米至2,000微米之間,進一步較佳為5微米至500微米之間,且更佳為約12微米至250微米之間。
當欲改良對基板之黏附性及/或獲得緩衝效果時,使用50微米至150微米之間的層厚度。
1微米至50微米之間的層厚度減少材料消耗量。然而,亦降低對基板之黏附性。
對於雙面黏著帶,黏著劑為同樣的情形,即個別壓感性黏著劑層之厚度較佳為1微米至2,000微米之間,進一步較佳為5微米至500微米之間,且更佳為約12微米至250微米之間。在雙面黏著帶中,如果除了本發明黏著劑亦使用其他黏著劑,則其厚度大於150微米亦為有利的。
在一或二面上塗有黏著劑之黏著帶通常在製程結束時捲繞成為阿基米德蝸線形式之捆。在雙面黏著帶的情形,為了防止黏著劑彼此接觸,或者在單面黏著帶的情形,為了防止黏著劑黏附於載體,在捲繞前將黏著帶以覆蓋材料(亦稱為隔離材料)覆蓋,其與黏著帶一起捲繞。所屬技術領域者已知此種覆蓋材料之名稱為襯墊或脫離襯墊。除了覆蓋單或雙面黏著帶,亦使用襯墊覆蓋純黏著劑(轉印黏著帶)及黏著帶片(例如標籤)。
本發明之又一主要請求項為關於一種保護配置在基板上的有機電子裝置之方法,其中對電子裝置以該電子裝置至少部分被覆蓋物覆蓋之方式施加覆蓋物,其中該覆蓋物另外黏結基板上及/或電子裝置上的至少部分區域,其中該黏結係藉至少一層黏著劑產生。該黏著劑層尤其是一層黏著帶之形式。
本發明之方法可有利地以首先施加(壓感性)黏著劑層之方式進行,其視情況為包含其他層之雙面黏著帶的組件,及在後續步驟將該覆蓋物施加於基板及/或電子裝置。在一進一步有利步驟中,將該(壓感性)黏著劑層,其視情況為包含其他層之雙面黏著帶的組件,及該覆蓋物一起施加於基板及/或電子裝置。
在本發明之方法中,轉印黏著帶可如此首先黏結基板或電子裝置,或者首先黏結覆蓋物。然而,較佳為首先將轉印黏著帶黏結覆蓋物因為如此可獨立於電子裝置而先製造電子功能單元之一組件,及藉積層附接成為整體。
本發明之方法可藉由將覆蓋物及/或(壓感性)黏著劑層,尤其是轉印黏著帶,完全覆蓋電子裝置之方式有利地進行,因為光散射作用然後影響電子裝置全區。
轉印黏著帶對電子裝置之全區積層另外排除任何有害滲透物可能被封入僅封包邊緣之裝置的氣體空間中的影響,因為無氣體空間。
本發明之方法較佳為以亦將電子裝置附近的基板區域以該覆蓋物完全或部分覆蓋之方式進行,在此情形,黏結用黏著帶可覆蓋電子裝置全區,且較佳為同樣覆蓋電子裝置附近的基板區域,較佳為與覆蓋物相同的區域-或者可施加於部分區域,例如電子裝置附近的框架之形式-較佳為亦被覆蓋物覆蓋的區域-及可選擇另外覆蓋電子裝置的邊緣區域。
本發明進一步提供一種(光)電子裝置,其包含至少一種(光)電子結構、及一層本發明之黏著劑,其中該黏著劑層完全覆蓋該(光)電子結構。
1‧‧‧(光)電子裝置
2‧‧‧基板
3‧‧‧電子結構
4‧‧‧覆蓋物
5‧‧‧黏著劑
6‧‧‧轉印黏著帶
6a‧‧‧轉印黏著帶
6b‧‧‧轉印黏著帶
21‧‧‧玻璃載片
22‧‧‧黏著劑
23‧‧‧鈣層
24‧‧‧玻璃載片
25‧‧‧轉印黏著帶
26‧‧‧PET膜
本發明之進一步細節、特點及優點在以下藉較佳作業例詳細闡明。圖式顯示:第1圖顯示用以測定電子組裝件壽命之鈣測試;第2圖為依照實施例V1之黏著劑(即未添加吸氣劑之黏著劑)之壽命測試時間結果的圖表;第3圖為先前技術之(光)電子裝置的示意圖;第4圖為第一本發明(光)電子裝置的示意圖;及第5圖為第二本發明(光)電子裝置的示意圖。
第3圖顯示先前技術之有機電子裝置1之第一組態。此裝置1具有其上配置電子結構3之基板2。基板2本身為滲透物屏障之形式,因此形成電子結構3之封包部分。在電子結構3上方(在本情形與其分開)配置覆蓋物4,其為屏障形式。
為了亦在側面封包電子結構3,同時另外將覆蓋物4黏結電子裝置1,在基板2上的電子結構3沿週邊附近提供黏著劑5。黏著劑是先黏結基板2或先黏結覆蓋物4,在此不重要。黏著劑5將覆蓋物4黏結基板2。藉適當厚的組態,黏著劑5另外可將覆蓋物4與電子結構3隔開。
黏著劑5為先前技術,即滲透屏障高之黏著劑,其可另外以吸氣劑材料充填至高程度。此組裝件無關黏著劑之透明性。
本情形提供沖切部分形式的轉印黏著帶,其因精密幾何而比本質上施加於全區的轉印黏著帶難以處理。
第4圖顯示本發明(光)電子裝置1之組態。所示同為電子結構3配置於基板2上,且被基板2從下方封包。在該電子結構上方及側面,將本發明黏著劑,例如轉印黏著帶6之形式,配置於全區。電子結構3因此被轉印黏著帶6從上方完全封包。然後將覆蓋物4施加於轉印黏著帶6。轉印黏著帶6為一般形式基於上述本發明之轉印黏著帶,且在作業例詳述者。所示版本之轉印黏著帶僅由一層本發明之黏著劑組成。
與以上組態相反,覆蓋物4不須必定滿足高屏障要求,因為當電子裝置被轉印黏著帶完全覆蓋時,已由黏著劑提供屏障。覆蓋物4可例如僅呈現機械保護功能,但亦可另外提供作為滲透屏障。
第5圖顯示(光)電子裝置1之替代性組態。與以上組態相反,現在提供二轉印黏著帶6a、6b,其在本情形相同,但是亦可不同。第一轉印黏著帶6a被配置於基板2全區。其提供電子結構3且以轉印黏著帶6a固定。然後將由轉印黏著帶6a與電子結構3組成的複合物以又一轉印黏著帶6b完全覆蓋,使得電子結構3被轉印黏著帶6a、6b從所有的側面封包。進而在轉印黏著帶6b上方提供覆蓋物4。
因此,在此組態中,基板2或覆蓋物4均不須必定具有屏障性質。為了進一步限制滲透物至電子結構3之滲透而仍可提供。
尤其是關於第4及5圖應指出,其為示意圖。更特別是該圖形中,且較佳為在各情形,轉印黏著帶之層厚度均勻並不明顯。因此轉移至電子結構時不形成尖銳邊緣,如該圖形所出現的情形;而是以流動性轉移且事實上殘留小的未充滿或充滿氣體區域。然而,如果必要亦可配合基板,尤其是當在低壓下施加時。此外,黏著劑受到不同程度的局部壓縮,故流動方法會在邊緣結構對高度差造成一定程度的補償。所示尺寸未按比例縮放,而是僅為了較佳描述之用。尤其是電子結構本身通常相當平坦(厚度經常小於1微米)。
黏著劑與電子組裝件直接接觸並非強制性。亦可在其間配置其他層,例如以薄層封包電子組裝件或屏障膜。
轉印黏著帶之厚度可包括所有的習用厚度,例如1微米至3,000微米。其偏好25至100微米之間的厚度,因為黏結力及處理性質在此範圍特別有益。又一較佳範圍為3至25微米之厚度,因為在此範圍內,在封包應用中可僅以橫切面積小的黏結線將滲透通過黏結線之物質量保持低程度。
為了製造本發明之轉印黏著帶,將黏著帶載體或襯墊之一面以得自溶液或分散液、或以純形式(例如熔化物)之黏著劑塗覆或印刷,或者藉(共)擠壓製造黏著帶。或者,可將本發明黏著劑層藉積層轉印至載體材料或襯墊而製造。該黏著劑層可藉熱或高能量光束交聯。
較佳為此製造方法在僅有低濃度,或者實際上完全無指定滲透物之環境中進行。一實例可為空氣相對濕度低於30%,較佳為低於15%。
一種用以測定電子組裝件壽命之手段為鈣測試。其示於第1圖。為此目的,將大小為10×10平方毫米之薄鈣層23在低壓下配置於玻璃載片21上,然後在氮氣大氣中儲存。鈣層23之厚度為約100奈米。為了封包鈣層23,使用具有欲測試的黏著劑22之黏著帶(23×23
平方毫米)、及作為載體材料之薄玻璃載片24(35微米,得自Schott)。為了安定化,藉50微米厚的轉印黏著帶25將薄玻璃載片以100微米厚的PET膜26積層,而產生目視為高透明性之丙烯酸酯壓感性黏著劑。將黏著劑22以黏著劑22在所有的側面均超出邊緣6.5毫米(A-A)而覆蓋鈣鏡23之方式塗佈於玻璃載片21。因為玻璃載體24為不透性,故僅測到通過壓感性黏著劑或沿界面之滲透。
此測試係基於鈣與水蒸氣及氧的反應,如例如A.G.Erlat等人之“47th Annual Technical Conference Proceedings-Society of Vacuum Coaters”,2004,第654至659頁,及M.E.Gross等人之“46th Annual Technical Conference Proceedings-Society of Vacuum Coaters”,2003,第89至92頁所述。其涉及監測鈣層之光穿透率,其因轉化成氫氧化鈣與氧化鈣而增加。在所述的測試設定中,其係從邊緣進行,使得鈣鏡之可視區域減小。直到鈣鏡之光吸收率減半的時間稱為壽命。該方法涵蓋鈣鏡從邊緣及經由該區域中點降解之面積減小,及由全區降解所造成的鈣鏡層厚度均勻減小。
所選擇的測量條件為60℃及90%空氣相對濕度。將樣本全區以層厚度為50微米之壓感性黏著劑黏結且無氣泡。鈣鏡降解係經由穿透率測量而監測。穿透時間(延遲時間)係定義為水分覆蓋到達鈣之距離所花費的時間(參考第2圖)。在60℃/90% r.h.獲得此時間之前,鈣鏡穿透率僅有邊際變化,及在85℃/85% r.h.為些微變化。
根據ASTM F-1249進行水蒸氣滲透力(WVTR)之測定。為此目的,將壓感性黏著劑以50微米之層厚度塗佈於高滲透聚碸薄膜(得自Sartorius),其本身對滲透屏障無任何貢獻。水蒸氣滲透力係在37.5℃及90%空氣相對濕度以Mocon OX-Tran 2/21測量儀器測定。
數量平均分子量Mn及重量平均分子量Mw之分子量測定係藉凝膠滲透層析術(GPC)完成。所使用的溶離液為THF(四氫呋喃)且有0.1體積百分比之三氟乙酸。該測量係在25℃完成。所使用的前置管柱為PSS-SDV,5微米,103埃,ID 8.0毫米×50毫米。用於分離所使用的管柱為PSS-SDV,5微米,103及105及106埃,各具ID 8.0毫米×300毫米。樣品濃度為4克/公升;流速為每分鐘1.0毫升。測量係針對聚苯乙烯標準品進行。
MMAP為混合甲基環己烷/苯胺霧點,其係使用修正ASTM C 611法測定。其使用甲基環己烷代替標準測試方法所使用的庚烷。該方法使用比例為1/2/1之樹脂/苯胺/甲基環己烷(5克/10毫升/5毫升),及霧點係將三種成分的加熱透明混合物冷卻,直到恰為完全混濁而測量。
DACP為二丙酮霧點,且係將5克之樹脂、5克之二甲苯、與5克之二丙酮醇的加熱溶液冷卻至溶液變成濁狀時測定。
膠黏樹脂軟化溫度係藉標準方法測定,其已知為環球法且在ASTM E28中標準化。
該樹脂之膠黏樹脂軟化溫度係使用Herzog HRB 754環球測試計測定。首先將樹脂樣本以杵與缽細微地壓碎。將生成粉末引入底座開放的黃銅圓筒(圓筒上部內徑為20毫米,圓筒底座開口直徑為16毫米,圓筒高度為6毫米),及在加熱台上熔化。選擇充填體積使得熔化後的樹脂完全充滿圓筒而不過量。
將生成樣本與圓筒一起置於HRB 754之樣品保持器中。如果膠黏樹脂軟化溫度為50℃至150℃之間,則將平衡浴以甘油充滿。在較低的膠黏樹脂軟化溫度,亦可以水浴作業。測試球具有9.5毫米之直徑且重3.5克。依照HRB 754步驟,將球安置於在平衡浴中的測試樣本上方,且放置在測試樣本上。圓筒基座下方25毫米處為收集板,且其上方2毫米處為遮光器。在測量方法期間,將溫度以5℃/分鐘提高。在膠黏樹脂軟化溫度之溫度範圍,球開始移動通過圓筒基座開口,直到其最終在收集板靜止。在此位置,其被遮光器偵測到且記錄此時之平衡浴溫度。其進行雙重測定。膠黏樹脂軟化溫度為2次個別測量之平均值。
為了製造黏著劑層,藉實驗室散佈儀器將各種黏著劑從溶液塗佈於習知襯墊(矽酮化聚酯膜)及乾燥。乾燥後的黏著劑層厚度為50±5微米。在各情形首先
在室溫乾燥10分鐘,及在實驗室乾燥箱中以120℃乾燥10分鐘。在乾燥之後,將各乾燥黏著劑層立刻在開放面以第二襯墊(脫離力較小的矽酮化聚酯膜)積層。
所選擇的共聚物為得自Kaneka之聚苯乙烯嵌段-聚異丁烯嵌段共聚物)。全部聚合物中的苯乙烯比例為20重量百分比。其使用Sibstar 62M。分子量Mw為60,000克/莫耳。聚苯乙烯嵌段之玻璃轉移溫度為100℃,及聚異丁烯嵌段為60℃。所使用的膠黏樹脂為得自Exxon之Escorez 5300(環球法105℃,DACP=71,MMAP=72),其為完全氫化烴樹脂,或Escorez 5600(軟化點100℃),其為氫化烴樹脂。將這些原料、視情況及烷氧基矽烷,溶於甲苯(300克)、丙酮(150克)、與60/95特殊沸點酒精(550克)的混合物,而產生50重量百分比溶液。
繼而將觸媒加入溶液。該觸媒為碳酸伸丙酯中50重量百分比溶液之形式。該光潛伏觸媒之最大吸收在320奈米至360奈米之範圍。
個別實施例V1與V2及K1與K2之確實組成物可在表1中發現。
將樣本引入手套工作箱中。將一些樣品在已接受鈣蒸氣沉積之玻璃基板上以橡膠輥無氣泡而積層。將其以第二PET襯墊覆蓋,且在其上積層一層薄玻璃。將此樣品用於壽命測試。
在觸媒(因此及吸氣劑)活化前後,及已將樣品暴露於水之後,黏著劑之水分滲透測量、及在鈣測試中對水測定的穿透時間的結果示於表2。
比較例V1使用非本發明(即不可切換)之觸媒。該樣品具有一定的延遲時間,其不隨以UV光照射的結果而改變。該吸氣劑為不可切換。在本發明實施例K1的情形,延遲時間顯著變化。在實施例K1中,觸媒(因而吸氣劑)被UV放射線活化之後的延遲時間比活化前高15倍。K2為結合吸氣劑活化及反應性樹脂硬化之實施例。該黏著劑在活化/硬化之前無任何延遲時間。該活化/硬化獲得長延遲時間。
一旦將未活化樣品暴露於濕空氣歷時1日,則非本發明樣品V1顯示吸氣劑已被消耗且已與水反應,故延遲時間降至零。相反地,在本發明樣品K1及K2的情形,未活化吸氣劑在該1日期間不與存在於濕空氣中的水反應。樣品之延遲時間與未暴露於濕空氣之樣品實際上與相同。即使樣品因此暴露於水蒸氣,對其作為吸氣劑之功效仍無任何影響,因為吸氣劑功能未被活化。
比較例V2顯示具有高WVTR之樣品不具有可測量的延遲時間。
1‧‧‧(光)電子裝置
2‧‧‧基板
3‧‧‧電子結構
4‧‧‧覆蓋物
6a‧‧‧轉印黏著帶
6b‧‧‧轉印黏著帶
Claims (31)
- 一種黏著劑,其包含:吸氣劑材料,及可選擇含有之溶劑,其特徵為該黏著劑包含可藉外部刺激活化之該吸氣劑材料與滲透物的反應用之觸媒,其中該黏著劑係具有黏著劑基底之屏障黏著劑,且該黏著劑基底在有反應性樹脂的情形硬化後,具有水蒸氣滲透率小於100克/平方米日。
- 如請求項1之黏著劑,其中該滲透物為水。
- 如請求項1或2之黏著劑,其中該吸氣劑係以至少2重量百分比之量存在。
- 如請求項1或2之黏著劑,其中該觸媒之量小於5重量百分比。
- 如請求項1或2之黏著劑,其中該外部刺激為UV放射線、溫度變化、微波放射線、或可見光。
- 如請求項1或2之黏著劑,其中該可藉外部刺激活化之觸媒為潛在性酸(latent acid)或潛在性鹼(latent base)。
- 如請求項1或2之黏著劑,其中該黏著劑包含由以下組成的黏著劑基底:- 至少一種聚合物,及- 至少一種膠黏樹脂。
- 如請求項7之黏著劑,其中該黏著劑基底進一步包含至少一種具有至少一個可硬化基之反應性樹脂。
- 如請求項1或2之黏著劑,其中該吸氣劑材料為至少一種選自包含乙氧基矽烷的群組之化合物。
- 如請求項9之黏著劑,其中該乙氧基矽烷另外包含至少一個可聚合基。
- 如請求項10之黏著劑,其中該可聚合基可與彼等可選用的反應性樹脂聚合。
- 如請求項1或2之黏著劑,其中該吸氣劑材料為至少一種選自包含非芳香族碳化二亞胺的群組之化合物。
- 如請求項1或2之黏著劑,其中該吸氣劑材料為至少一種選自包含酸及/或鹼可水解酯的群組之化合物。
- 如請求項14之黏著劑,其中該觸媒為潛在性鹼。
- 如請求項1或2之黏著劑,其中該吸氣劑材料為至少一種選自異氰酸酯群組之化合物。
- 如請求項16之黏著劑,其中該觸媒為潛在性鹼。
- 如請求項1或2之黏著劑,其中該吸氣劑材料為至少一種選自酐群組之化合物。
- 如請求項18之黏著劑,其中該觸媒為潛在性酸或潛在性鹼。
- 如請求項8之黏著劑,其中該至少一個可硬化基為至少一種選自環狀醚、乙烯基、丙烯酸酯、甲基丙烯酸酯、羥基、胺基、與異氰酸酯之基。
- 如請求項1或2之黏著劑,其中該黏著劑為壓感性黏著劑。
- 一種黏著帶,其包含如請求項1至21中任一項之黏著劑。
- 一種如請求項1至21中任一項之黏著劑及如請求項22之黏著帶用以將組裝件封包於有機電子設備中之用途。
- 一種應用如請求項1至21中任一項之黏著劑、或如請求項22之黏著帶之方法,其步驟包含:- 將該黏著劑或黏著帶施加於欲黏結物品;- 藉外部刺激將該吸氣劑材料活化。
- 如請求項24之方法,其中該黏著劑包含反應性樹脂,且該外部刺激不僅誘發該吸氣劑材料活化,亦誘發該黏著劑或黏著帶硬化。
- 一種保護配置在基板上的有機電子裝置之方法,其中對電子裝置以該電子裝置至少部分被覆蓋物覆蓋之方式施加覆蓋物,其中該覆蓋物另外黏結基板上及/或電子裝置上的至少部分區域,其中該黏結係藉至少一層如請求項1至21中任一項之黏著劑產生。
- 如請求項26之方法,其中該黏著劑係呈一層黏著帶之形式。
- 如請求項26或27之方法,其中首先施加該黏著劑層,其可選擇性作為包含其他層之雙面黏著帶之構件,及在後續步驟將該覆蓋物施加於該基板及/或該電子裝置。
- 如請求項26或27之方法,其中將該黏著劑層及該覆蓋物一起施加於該基板及/或該電子裝置。
- 如請求項26或27之方法,其中該覆蓋物完全覆蓋該電子裝置。
- 如請求項26或27之方法,其中該電子裝置附近的基板區域亦完全或部分被該覆蓋物覆蓋。
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- 2015-10-15 KR KR1020177013521A patent/KR101994466B1/ko active IP Right Grant
- 2015-10-15 US US15/520,003 patent/US20170327717A1/en not_active Abandoned
- 2015-10-15 WO PCT/EP2015/073898 patent/WO2016066435A1/de active Application Filing
- 2015-10-15 JP JP2017523283A patent/JP6474489B2/ja not_active Expired - Fee Related
- 2015-10-15 EP EP15786881.1A patent/EP3212727A1/de active Pending
- 2015-10-26 TW TW104135079A patent/TWI681034B/zh active
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2019
- 2019-06-03 US US16/429,831 patent/US11390783B2/en active Active
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US20170327717A1 (en) | 2017-11-16 |
TW201634634A (zh) | 2016-10-01 |
EP3212727A1 (de) | 2017-09-06 |
US20190284450A1 (en) | 2019-09-19 |
US11390783B2 (en) | 2022-07-19 |
KR101994466B1 (ko) | 2019-06-28 |
WO2016066435A1 (de) | 2016-05-06 |
KR20170070223A (ko) | 2017-06-21 |
CN107148458A (zh) | 2017-09-08 |
JP6474489B2 (ja) | 2019-02-27 |
JP2017537998A (ja) | 2017-12-21 |
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