TWI548713B - 壓敏性黏著劑組成物、壓敏性黏著膜及使用彼製造有機電子裝置之方法 - Google Patents
壓敏性黏著劑組成物、壓敏性黏著膜及使用彼製造有機電子裝置之方法 Download PDFInfo
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- TWI548713B TWI548713B TW103126849A TW103126849A TWI548713B TW I548713 B TWI548713 B TW I548713B TW 103126849 A TW103126849 A TW 103126849A TW 103126849 A TW103126849 A TW 103126849A TW I548713 B TWI548713 B TW I548713B
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- pressure
- sensitive adhesive
- film
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- resin
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C09J123/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C09J123/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/08—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms
- C08F255/10—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms on to butene polymers
-
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Description
本發明係關於壓敏性黏著劑組成物、壓敏性黏著膜以及使用彼製造有機電子裝置之方法。
有機電子裝置(OED)係指包括使用電洞及電子產生電荷交替之有機材料層的裝置，且可包括，例如，光電裝置(photovoltaic device)、整流器、發射器(transmitter)以及有機發光二極體(OLED)。
代表性的OED，為OLED，其相較於常用光源係具有較低耗電及較高反應速度，並形成較薄的顯示裝置或光源。此外，OLED具有極佳的空間利用度，且有望於包括所有種類之可攜式裝置、螢幕、筆記型電腦及TV的各種領域中應用。
擴展OLED之商業化與用途的主要問題為耐久性。OLED所含之有機材料和金屬電極極易因外在因素
如水而氧化，且含有OLED之產品對環境因素非常敏感。因此，對於有機電子裝置如OLED已提出各種用以避免氧氣或水從外在環境透入的方法。
韓國專利申請案第2008-0088606號係提出黏著劑包封組成物及有機電致發光裝置，其因以聚異丁烯(PIB)為基礎的壓敏性黏著劑而加工性差且於高溫及高濕度之可靠性低。
因此，於有機電子裝置，需要研發能確保所需壽命、極佳地避免濕氣透入、在高溫及高濕度下維持可靠性、且具有極佳光學特性之封裝劑。
本發明係關於提供壓敏性黏著劑組成物，其可形成有效避免濕氣或氧氣從外在環境透入有機電子裝置之結構，且具有極佳的機械特性(如操作性(handleability)與加工性)和極佳的透光性(transparency)；壓敏性黏著膜；以及使用彼製造有機電子裝置之方法。
於一態樣中，本發明係提供壓敏性黏著劑組成物。該壓敏性黏著劑組成物可應用於，例如，有機電子裝置如OLED之封裝(encapsulation)或包封(capsulation)。
本文使用之術語“有機電子裝置”係指具有包括於彼此面對之電極對間之使用電洞及電子產生電荷交替
的有機材料層之結構的產品或裝置，且可包括，但不限於，例如，光電裝置(photovoltaic device)、整流器、發射器(transmitter)以及有機發光二極體(OLED)。於一實例中，有機電子裝置可為OLED。
於本發明之一例示性具體實例中，壓敏性黏著劑組成物可包括封裝樹脂、可由活化能射線照射而聚合之多官能性活化能射線-可聚合化合物(multifunctional active energy ray-polymerizable compound)、以及滿足式1之矽烷化合物：
式1中，R1為氫或烷基。R1可為，例如，具有1至4或1至2個碳原子之烷基。此外，式1中，R2及R3係各自獨立地為氫或直鏈、支鏈或環狀烷基，或者R2係與R3連結而形成環狀烷基。舉例而言，R2及R3可各自獨立地為氫或直鏈、支鏈或環狀烷基。此處，直鏈烷基可具有1至10、1至6、或1至4個碳原子，支鏈烷基可具有3至10、3至6、或3至4個碳原子，且環狀烷基可具有3至10、3至8、3至6、或3至4個碳原子。此外，R2可與R3連結而形成具有2至10、3至10、4至9、或4
至8個碳原子之環狀烷基。此外，式1中，R4、R5及R6係各自獨立地為氫、烷基或烷氧基，R4、R5及R6中之至少一者為烷氧基，以及，n為1或以上之整數。具言之，R4、R5及R6係各自獨立地為具有1至10、1至6、1至4、或1至2個碳原子之烷基；或具有1至10、1至8、1至4或1至2個碳原子之烷氧基。此處，R4、R5及R6中之至少一者可為烷氧基，且R4、R5及R6可都為烷氧基，但本發明不以此為限。於一實例中，矽烷化合物並無特別限制，只要其滿足式1，且其可為，例如，3-甲基丙烯醯氧基丙基三甲氧基矽烷(3-methacryloxypropyl trimethoxysilane)、3-甲基丙烯醯氧基丙基三乙氧基矽烷(3-methacryloxy propyl triethoxysilane)、3-丙烯醯氧基丙基三甲氧基矽烷(3-acryloxy propyl trimethoxysilane)、3-丙烯醯氧基丙基三乙氧基矽烷(3-acryloxy propyl triethoxysilane)、3-甲基丙烯醯氧基甲基三乙氧基矽烷(3-methacryloxy methyl triethoxysilane)、3-甲基丙烯醯氧基甲基三甲氧基矽烷(3-methacryloxy methyl trimethoxysilane)、3-丙烯醯氧基丙基甲基二甲氧基矽烷(3-acryloxy propyl methyldimethoxysilane)、甲基丙烯醯氧基甲基甲基二甲氧基矽烷(methacryloxy methyl methyldimethoxysilane)、甲基丙烯醯氧基甲基甲基二乙氧基矽烷(methacryloxy methyl methyldiethoxysilane)、甲基丙烯醯氧基丙基甲基二甲氧基矽烷(methacryloxy propyl methyldimethoxysilane)、甲基丙烯醯氧基丙基甲
基二乙氧基矽烷(methacryloxy propyl methyldiethoxysilane)、甲基丙烯醯氧基丙基二甲基甲氧基矽烷(methacryloxy propyl dimethylmethoxysilane)或甲基丙烯醯氧基丙基二甲基乙氧基矽烷(methacryloxy propyl dimethylethoxysilane)。矽烷化合物的丙烯醯基可藉由與壓敏性黏著劑組成物之封裝樹脂或活化能射線-可聚合化合物交聯而用以提高介面(interface)壓敏性黏著劑強度。矽烷化合物之含量，相對於100重量份之封裝樹脂，可為，例如，0.1至10、0.5至8、0.8至5、1至5、1至4.5、或1至4重量份。
於一實例中，活化能射線-可聚合化合物可與滿足式1之矽烷化合物形成交聯結構，且該交聯結構可與封裝樹脂形成半-互穿聚合物網絡(semi-interpenetrating polymer network)(半-IPN)。即，壓敏性黏著劑組成物可包括半-IPN。術語"半-IPN"係包括至少一聚合物交聯結構(聚合物網絡)及至少一直鏈或支鏈聚合物，且至少一部分該直鏈或支鏈聚合物係具有穿入該聚合物交聯結構之結構。由於該直鏈或支鏈聚合物理論上可無損化學鍵而與聚合物交聯結構分離，因此半-IPN係與IPN結構不同。
於一例示性具體實例中，交聯結構可為藉由施熱而形成的交聯結構、藉由照射活化能射線而形成的交聯結構、或藉由於室溫老化而形成的交聯結構。此處，微波、紅外(IR)射線、紫外(UV)射線、X射線與γ射線，以及粒子束如α-粒子束、質子束、中子束或電子束，
且慣常為UV射線與電子束，係包括在"活化能射線"類別中。由於引入此半-IPN結構因而可提高壓敏性黏著劑組成物之機械性質如加工性、改善耐濕氣黏著性能(humidity-resistant adhesive performance)、實現透光性，以及實現目前無法達到的高濕氣阻隔性能、和極佳的面板壽命(panel lifetime)。
於一實例中，活化能射線-可聚合化合物可與滿足式1之矽烷化合物形成交聯結構，且封裝樹脂可與活化能射線-可聚合化合物或滿足式1之矽烷化合物形成交聯結構，因而形成互穿聚合物網絡(IPN)結構。此外，術語"IPN結構"係指其中壓敏黏著劑中存在至少兩交聯結構之狀態。於一實例中，IPN結構可指包括至少兩個為交結(intertwining)、糾結(entanglement)或穿入(penetrating)狀態的交聯結構之結。舉例而言，本發明之組成物可包括由封裝樹脂形成之交聯結構(下文中稱為“第一交聯結構”)以及由活化能射線-可聚合化合物與滿足式1之矽烷化合物之反應形成之交聯結構(下文中稱為“第二交聯結構”)，第一和第二交聯結構可為交結(intertwining)狀態或糾結(entanglement)狀態。即，因壓敏性黏著劑組成物包括為交聯狀態之半-IPN或IPN結構，因而可藉由提高壓敏性黏著劑之壓敏性黏著劑強度及避免因濕氣透入而降低之介面壓敏性黏著劑強度以能於嚴苛條件如高溫及高濕度下實現壓敏性黏著劑之極佳耐久性及可靠性。
於本發明之一例示性具體實例中，封裝樹脂之玻璃轉化溫度可為低於0、-10、-30、-50或-60℃。此處，玻璃轉化溫度可指以約1J/cm2或以上之劑量照射UV射線後之玻璃轉化溫度，或者於UV照射後另進行熱固化之後的玻璃轉化溫度。
於一實例中，封裝樹脂可包括苯乙烯系樹脂或彈性體、聚烯烴系樹脂或彈性體、其他彈性體、聚氧伸烷基(polyoxyalkylene)系樹脂或彈性體、聚酯系樹脂或彈性體、聚氯乙烯系樹脂或彈性體、聚碳酸酯系樹脂或彈性體、聚伸苯硫(polyphenylenesulfide)系樹脂或彈性體、聚醯胺系樹脂或彈性體、丙烯酸酯系樹脂或彈性體、環氧(epoxy)系樹脂或彈性體、矽(silicone)系樹脂或彈性體、氟系樹脂或彈性體、或該等之混合物。
此處，苯乙烯系樹脂或彈性體可為，例如，苯乙烯-乙烯-丁二烯-苯乙烯(SEBS)嵌段共聚物、苯乙烯-異戊二烯-苯乙烯(SIS)嵌段共聚物、丙烯腈-丁二烯-苯乙烯(ABS)嵌段共聚物、丙烯腈-苯乙烯-丙烯酸酯(ASA)嵌段共聚物、苯乙烯-丁二烯-苯乙烯(SBS)嵌段共聚物、苯乙烯系均聚物、或該等之混合物。烯烴系樹脂或彈性體可為，例如，高密度聚乙烯(high density polyethylene)系樹脂或彈性體、低密度聚乙烯(low density polyethylene)系樹脂或彈性體、聚丙烯系樹脂或彈性體、或該等之混合物。彈性體可為，例如，酯系熱塑性彈性體、烯烴(olefin)系彈性體、矽(silicone)系彈
性體、丙烯酸系(acrylic)彈性體、或該等之混合物。其中，烯烴系熱塑性彈性體可為聚丁二烯樹脂或彈性體或者聚異丁烯樹脂或彈性體。聚氧伸烷基(polyoxyalkylene)系樹脂或彈性體可為，例如，聚甲醛(polyoxymethylene)系樹脂或彈性體、聚氧乙烯(polyoxyethylene)系樹脂或彈性體、或該等之混合物。聚酯系樹脂或彈性體可為，例如，聚對酞酸乙二酯(polyethylene terephthalate)系樹脂或彈性體、聚對酞酸丁二酯(polybutylene terephthalate)系樹脂或彈性體、或該等之混合物。聚氯乙烯系樹脂或彈性體可為，例如，聚偏二氯乙烯。封裝樹脂可包括烴類(hydrocarbon)混合樹脂，例如，三十六烷或烷烴(paraffin)。聚醯胺系樹脂或彈性體可為，例如，尼龍(nylon)。丙烯酸酯系樹脂或彈性體可為，例如，聚(甲基)丙烯酸丁酯。環氧(epoxy)系樹脂或彈性體可為，例如，雙酚型(如雙酚A型、雙酚F型、雙酚S型)、及其氫化產物；清漆(novolac)型如酚清漆(phenolnovolac)型或甲酚清漆(cresolnovolac)型；含氮環型如三環氧丙基三聚異氰酸酯(triglycidylisocyanurate)型或乙內醯胺(hydantoin)型；脂環(alicyclic)型；脂族型；芳族型如萘型或聯苯型；環氧丙基(glycidyl)型如環氧丙醚(glycidylether)型、環氧丙胺(glycidylarmine)型或環氧丙酯(glycidylester)型；二環型如二環戊二烯型；酯型；醚酯型；或該等之混合物。矽(silicone)系樹脂或彈性體可為，例如，聚二甲基矽氧
烷。此外，氟系樹脂或彈性體可為聚三氟乙烯(polytrifluoroethylene)樹脂或彈性體、聚四氟乙烯(polytetrafluoroethylene)樹脂或彈性體、聚氯三氟乙烯(polychlorotrifluoroethylene)樹脂或彈性體、聚六氟丙烯(polyhexafluoropropylene)樹脂或彈性體、聚偏二氟乙烯、聚氟乙烯、聚伸乙基伸丙基氟化物(polyethylenepropylene fluoride)、或該等之混合物。
上列樹脂或彈性體中之一者可接枝至例如順丁烯二酸酐、與上列樹脂或彈性體中之另一者或用於製備該樹脂或彈性體之單體共聚合、或者以非上述樹脂或彈性體之化合物改質。該化合物可為羧基封端的丁二烯-丙烯腈共聚物。
於一實例中，壓敏性黏著劑組成物為封裝樹脂，其可包括烯烴(olefin)系彈性體、矽(silicone)系彈性體、或前述類型之丙烯酸系(acrylic)彈性體，但本發明不以此為限。
具言之，封裝樹脂可為二烯和具有一個碳-碳雙鍵之烯烴系化合物之共聚物。此處，烯烴系化合物可包括異丁烯、丙烯或乙烯，且二烯可為能與烯烴系化合物聚合之單體，例如，1-丁烯、2-丁烯、異戊二烯或丁二烯。即，本發明之封裝樹脂可為，例如，異丁烯單體之均聚物；藉由使異丁烯單體與能與其聚合之單體共聚合而製備之共聚物；或該等之混合物。於一實例中，具有一個碳-碳雙鍵之烯烴系化合物與二烯之共聚物可為丁基橡膠
(butyl rubber)。當如上所述使用特定樹脂時本發明所獲致之濕氣阻隔性令人滿意。此外，本發明可藉由引入上述各種交聯系統而改善耐濕氣性(humidity resistance)和耐熱性(heat resistance)，其係由於常用之異丁烯聚合物雖透濕性(moisture permeability)低但耐熱性低。
於壓敏性黏著劑組成物中，樹脂或彈性體組份之重量平均分子量(Mw)可為使該壓敏性黏著劑組成物可被塑化成膜類型之程度。舉例而言，樹脂或彈性體之重量平均分子量(Mw)可為約100,000至2,000,000、100,000至1,500,000、或100,000至1,000,000。本文使用之術語"重量平均分子量"是指以凝膠穿透層析法(GPC)測得之相對於聚苯乙烯標準品的轉換值。然而，樹脂或彈性體組份並非必具有上述重量平均分子量。舉例而言，當樹脂或彈性體組份的分子量不足以形成膜時，另外的黏合劑樹脂可摻入壓敏性黏著劑組成物中。
如上所述，本發明之壓敏性黏著劑組成物可包括與封裝樹脂之相容性高且能與封裝樹脂形成特定交聯結構的活化能射線-可聚合化合物。
舉例來說，本發明之壓敏性黏著劑組成物可包括可藉由照射活化能射線而與封裝樹脂聚合的多官能性活化能射線-可聚合化合物。活化能射線-可聚合化合物可指，例如，包含至少兩個可藉由照射活化能射線而參與聚合反應之官能基(例如，含有乙烯系不飽和雙鍵(如丙烯醯基或甲基丙烯醯基)之官能基、及如環氧基(epoxy
group)或氧雜環丁烷基(oxetane group)之官能基)的化合物。
作為多官能性活化能射線-可聚合化合物可使用，例如，多官能性丙烯酸酯(MFA)。
此外，可藉由照射活化能射線而聚合之多官能性活化能射線-可聚合化合物係可滿足式2。此外，活化能射線-可聚合化合物之含量，相對於100重量份之封裝樹脂，可為5至30、5至25、8至20、10至18、或12至18重量份。
式2中，R1為氫或具有1至4個碳原子之烷基，n為2或以上之整數，以及X為自具有3至30個碳原子之直鏈、支鏈或環狀烷基衍生之基團。此處，當X為由環狀烷基衍生之基團時，X可為，例如，由具有3至30、6至28、8至22、或12至20個碳原子之環狀烷基衍生之基團。此外，當X為由直鏈烷基衍生之基團時，X可為由具有3至30、6至25、或8至20個碳原子之直鏈烷基衍生之基團。此外，當X為由支鏈烷基衍生之基團時，X可為由具有3至30、5至25、或6至20個碳原子之支
鏈烷基衍生之基團。
本文使用之術語"由烷基衍生之基團"可指由烷基構成之特定化合物的基團。於一實例中，式2中，當n為2，X可為伸烷基。此外，當n為3或以上，烷基的至少兩個氫可從X釋出，且鍵結至式2之(甲基)丙烯醯基。
本文使用之術語"烷基"，除非另有特別定義，係可指具有1至30、1至25、1至20、1至16、1至12、1至8、或1至4個碳原子之烷基。烷基可為直鏈、支鏈、或環狀結構，且可任意地經至少一取代基取代。
本文使用之術語"伸烷基"，除非另有特別定義，係可為具有2至30、2至25、2至20、2至16、2至12、2至10、或2至8個碳原子之伸烷基。伸烷基可為直鏈、支鏈、或環狀結構，且可任意地經至少一取代基取代。
本文使用之術語"烷氧基"，除非另有特別定義，係可為具有1至20、1至16、1至12、1至8、或1至4個碳原子之烷氧基。烷氧基可為直鏈、支鏈、或環狀結構。此外，烷氧基可任意地經至少一取代基取代。
可藉由照射活化能射線而聚合之多官能性活化能射線-可聚合化合物係可為任何滿足式2者而無限制。例如，該化合物可為1,4-丁二醇二(甲基)丙烯酸酯(1,4-butanediol di(meth)acrylate)、1,3-丁二醇二(甲基)丙烯酸酯(1,3-butylene glycol di(meth)acrylate)
、1,6-己二醇二(甲基)丙烯酸酯(1,6-hexanediol di(meth)acrylate)、1,8-辛二醇二(甲基)丙烯酸酯(1,8-octanediol di(meth)acrylate)、1,12-十二烷二醇二(甲基)丙烯酸酯(1,12-dodecanediol di(meth)acrylate)、新戊二醇二(甲基)丙烯酸酯(neopentylglycol di(meth)acrylate)、二(甲基)丙烯酸二環戊酯(dicyclopentanyl di(meth)acrylate)、環己烷-1,4-二甲醇二(甲基)丙烯酸酯(cyclohexane-1,4-dimethanol di(meth)acrylate)、三環癸烷二甲醇二(甲基)丙烯酸酯、二羥甲基二環戊烷二(甲基)丙烯酸酯(dimethylol dicyclopentane di(meth)acrylate)、經新戊二醇改質之三甲基丙烷二(甲基)丙烯酸酯(neopentyl glycol modified trimethylpropane di(meth)acrylate)、金剛烷二(甲基)丙烯酸酯(adamantane di(meth)acrylate)、三羥甲丙烷三(甲基)丙烯酸酯(trimethylolpropane tri(meth)acrylate)或該等之混合物。
作為多官能性活化能射線-可聚合化合物可使用，例如，具有低於1,000之分子量且包括至少兩個官能基的化合物。於此例中，分子量是指重量平均分子量或慣用(conventional)分子量。多官能性活化能射線-可聚合化合物中所含之環狀結構可為碳環結構、雜環結構、單環結構及多環結構中之任一者。
於本發明之一例示性具體實例中，壓敏性黏著劑組成物可進一步包括自由基起始劑，其可引發上述活
化能射線-可聚合化合物的聚合反應。自由基起始劑可為光起始劑(photoinitiator)或熱起始劑(thermal initiator)。可考量固化速率和黃化可能性而適當選擇特定種類的光起始劑。舉例來說，作為光起始劑可使用以苯偶姻(benzoin)、羥基酮(hydroxy ketone)、胺基酮(amino ketone)或膦氧化物(phosphine oxide)為基礎之光起始劑，具體地為，苯偶姻(benzoin)、苯偶姻甲醚(benzoin methylether)、苯偶姻乙醚(benzoin ethylether)、苯偶姻異丙醚(benzoin isopropylether)、苯偶姻正丁醚(benzoin n-butylether)、苯偶姻異丁醚(benzoin isobutylether)、苯乙酮、二甲胺基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基-2-苯基苯乙酮、2-羥基-2-甲基-1-苯基丙-1-酮、1-羥基環己基苯基酮、2-甲基-1-[4-(甲硫基)苯基]-2-N-啉基-丙-1-酮(2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propane-1-one)、4-(2-羥基乙氧基)苯基-2-(羥基-2-丙基)酮、二苯基酮、對-苯基二苯基酮(p-phenylbenzophenone)、4,4’-二乙胺基二苯基酮、二氯二苯基酮、2-甲基蒽醌、2-乙基蒽醌、2-三級丁基蒽醌、2-胺基蒽醌、2-甲基硫代酮(2-methylthioxanthone)、2-乙基硫代酮(2-ethylthioxanthone)、2-氯硫代酮(2-chlorothioxanthone)、2,4-二甲基硫代酮(2,4-dimethylthioxanthone)、2,4-二乙基硫代酮(2,4-diethylthioxanthone)、苄基二甲縮酮(
benzyldimethylketal)、乙醯苯二甲縮酮(acetophenone dimethylketal)、對-二甲胺基苯甲酸酯、寡聚[2-羥基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙酮](oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone])、或2,4,6-三甲基苄醯基-二苯基-氧化膦(2,4,6-trimethylbenzoyl-diphenyl-phosphineoxide)。
自由基起始劑之含量，相對於100重量份之活化能射線-可聚合化合物，可為0.2至20、0.5至18、1至15、或2至13重量份。因此，有效地引發活化能射線-可聚合化合物之反應，且可避免壓敏性黏著劑組成物之物理性質因為固化後殘留的組份而劣化。
於一實例中，壓敏性黏著劑組成物可進一步包括增黏劑。增黏劑可為氫化之環烯烴(hydrogenated cyclic olefin)系聚合物。作為增黏劑可使用，例如，藉由將石油樹脂(petroleum resin)氫化而得之氫化之石油樹脂。氫化之石油樹脂可為部分或完全氫化，且可為此樹脂之混合物。此增黏劑可具有與壓敏性黏著劑組成物之高相容性、極佳之濕氣阻隔性(moisture barrierability)以及小含量之有機揮發性組份。氫化之石油樹脂的具體實例可為氫化之萜烯(terpene)系樹脂、氫化之酯系樹脂、或氫化之二環戊二烯(dicyclopentadiene)系樹脂。增黏劑之重量平均分子量可為約200至5,000。可依所需適當控制增黏劑之含量。舉例而言，可考量壓敏性黏著劑組成物之交聯度(degree of crosslinking)而選擇增黏劑之含
量。根據一實例，增黏劑之含量，相對於100重量份之壓敏性黏著劑組成物的固含量(solid content)，可為5至100、8至95、10至93、或15至90重量份。
需要時，壓敏性黏著劑組成物可進一步包括濕氣吸收劑。術語"濕氣吸收劑"可指能藉由化學反應移除透入下文所述之壓敏性黏著膜之濕氣或蒸氣的材料。當本發明之壓敏性黏著劑組成物包括濕氣吸收劑時，於形成膜時可能未滿足下文所述之透光率，但卻能實現極佳的濕氣阻隔性(moisture barrierability)。具言之，壓敏性黏著劑組成物可形成欲用於封裝有機電子裝置之膜。於此例中，當壓敏性黏著劑組成物不含濕氣吸收劑且展現極佳的透光性時，其可用於封裝頂射型(top-emissive)有機電子裝置，或當壓敏性黏著劑組成物含有濕氣吸收劑且展現極佳的濕氣阻隔性時，其可用於封裝底射型(bottom-emissive)有機電子裝置。然而，本發明並不以此為限。即，當壓敏性黏著劑組成物不含濕氣吸收劑且展現極佳的透光性時，其可用於封裝底射型(bottom-emissive)有機電子裝置。
舉例來說，濕氣吸收劑可存在為均勻地分散於壓敏性黏著劑組成物或下文所述之壓敏性黏著層中。此處，均勻分散狀態可指濕氣吸收劑以相同或實質相同之密度均勻存在於壓敏性黏著劑組成物或壓敏性黏著層之任何部分的狀態。作為此處所用之濕氣吸收劑可使用，例如，金屬氧化物、硫酸鹽或有機金屬氧化物。具言之，硫酸鹽
可為硫酸鎂、硫酸鈉或硫酸鎳，有機金屬氧化物可為氧化鋁辛酸鹽(aluminum oxide octylate)。此處，金屬氧化物可為五氧化磷(P2O5)、氧化鋰(Li2O)、氧化鈉(Na2O)、氧化鋇(BaO)、氧化鈣(CaO)或氧化鎂(MgO)，金屬鹽可為硫酸鹽如硫酸鋰(Li2SO4)、硫酸鈉(Na2SO4)、硫酸鈣(CaSO4)、硫酸鎂(MgSO4)、硫酸鈷(CoSO4)、硫酸鎵(Ga2(SO4)3)、硫酸鈦(Ti(SO4)2)或硫酸鎳(NiSO4)；金屬鹵化物，如氯化鈣(CaCl2)、氯化鎂(MgCl2)、氯化鍶(SrCl2)、氯化釔(YCl3)、氯化銅(CuCl2)、氟化銫(CsF)、氟化鉭(TaF5)、氟化鈮(NbF5)、溴化鋰(LiBr)、溴化鈣(CaBr2)、溴化銫(CeBr3)、溴化硒(SeBr4)、溴化釩(VBr3)、溴化鎂(MgBr2)、碘化鋇(BaI2)或碘化鎂(MgI2)；或金屬氯酸鹽，如過氯酸鋇(Ba(ClO4)2)或過氯酸鎂(Mg(ClO4)2)，但本發明不以此為限。作為可含於壓敏性黏著劑組成物中之濕氣吸收劑可使用，上述材料中之一或至少二者。於一實例中，當使用上述材料之至少二者時，濕氣吸收劑可為經煅燒的白雲石。
此濕氣吸收劑可根據其用途而控制於適當尺寸。於一實例中，濕氣吸收劑的平均直徑可控制於約10至15000nm。具有上述平均直徑範圍之濕氣吸收劑因為與濕氣的反應速度不會過高而易於儲存，且可有效地移除濕氣且不會損及欲封裝之元件。
可考量所欲的阻隔特性以適當選擇濕氣吸收
劑之含量而無特別限制。
需要時，壓敏性黏著劑組成物可進一步包括濕氣阻斷劑(moisture blocker)。本文使用之術語"濕氣阻斷劑"可指能阻斷或避免濕氣或蒸氣於膜中移動並與濕氣不具反應性或反應性低的材料。作為濕氣阻斷劑者可使用黏土、滑石、針型矽石(needle-like silica)、平面矽石(planar silica)、多孔矽石(porous silica)、沸石、氧化鈦(titania)及氧化鋯(zirconia)中之一或至少二者。此外，水阻斷劑之表面可經有機改質劑處理以促進有機材料透入。作為此有機改質劑可使用二甲基苄基氫化之牛脂四級銨(dimethyl benzyl hydrogenated tallow quaternary ammonium)、二甲基氫化之牛脂四級銨(dimethyl hydrogenated tallow quaternary ammonium)、甲基牛脂雙-2-羥基乙基四級銨(methyl tallow bis-2-hydroxyethyl quaternary ammonium)、二甲基氫化之牛脂2-乙基己基四級銨(dimethyl hydrogenated tallow 2-ethylhexyl quaternary ammonium)、二甲基去氫化之牛脂四級銨(dimethyl dehydrogenated tallow quaternary ammonium)、或該等之混合物。
可考量所欲阻斷特性以適當選擇濕氣阻斷劑之含量而無特別限制。
除了上述組份以外，壓敏性黏著劑組成物可根據其用途及下文所述之壓敏性黏著膜之製法而含有各種添加劑。舉例來說，壓敏性黏著劑組成物可根據所欲
物理性質而包括適當含量範圍之可固化材料、交聯劑或填料。
於一實例中，本發明之壓敏性黏著劑組成物可具有之方程式1所示之凝膠含量(gel content)為50%或以上。
[方程式1]凝膠含量(wt%)=B/A×100
方程式1中，A是壓敏性黏著劑組成物的質量，B是壓敏性黏著劑組成物於60℃浸於甲苯中24小時且以200網目過濾器(孔尺寸為200μm)過濾後所留之不溶成分的乾質量(dry mass)。
方程式1所示之凝膠含量可為50至99%、50至90%、50至80%、或50至70%。即，於本發明，可藉由凝膠含量決定適當範圍之壓敏性黏著劑組成物的交聯結構及交聯度(degree of crosslinking)以實現具極佳的濕氣阻隔特性、可靠性及光學特性之壓敏性黏著劑組成物。
於另一態樣中，本發明提供壓敏性黏著膜。壓敏性黏著膜可包括壓敏性黏著層。此外，當於25℃及50%相對濕度儲存1小時後之壓敏性黏著層對基板的剝離強度(剝離速度：5mm/sec，剝離角度：180度)為P gf/25mm、且於85℃及85%相對濕度儲存1小時後之壓敏性黏著層對基板的剝離強度(剝離速度：5mm/sec，剝離角度：180度)為Q gf/25mm時，壓敏性黏著膜係滿足方程式2。溫度及濕度條件可為常溫、常濕度。
[方程式2]Q1.3P
此外，於本發明之一例示性具體實例中，於25℃及50%相對濕度儲存1小時後(在交聯結構實現前或後)之壓敏性黏著膜對玻璃基板的剝離強度(剝離速度：5mm/sec，剝離角度：180度)可為1,000gf/吋或以上。剝離強度可使用質地分析儀(texture analyzer)依據ASTM3330來測量。當壓敏性黏著劑組成物之組成或交聯狀況(crosslinking condition)係控制為具此剝離強度時，可提供能實現具極佳耐久性之電子裝置封裝或包封結構的壓敏性黏著膜。
壓敏性黏著膜之壓敏性黏著層可進一步包括上述壓敏性黏著劑組成物或其交聯產物。壓敏性黏著層亦可具有膜或片之形狀。此壓敏性黏著層可用於封裝有機電子元件。
於本發明之一例示性具體實例中，壓敏性黏著層形成為如上述之單層結構，或者可由下文所述之至少兩層所形成。舉例而言，壓敏性黏著層可包括含有上述壓敏性黏著劑組成物或其交聯產物的第一層以及包含壓敏性黏著樹脂或黏著樹脂的第二層。第二層所包含之壓敏性黏著樹脂或黏著樹脂可與上述封裝樹脂相同或不同，且可根據目的由嫻於此技術之人士適當地選擇。當壓敏性黏著層係由至少兩層所形成時，上述壓敏性黏著劑強度或剝離強度可相應於第一層或第二層。此外，第一和第二層可包括
或不包括濕氣吸收劑。
於一實例中，第二層所包含之壓敏性黏著樹脂可包括含有至少一熱可固化官能基(如環氧丙基、異氰酸基(isocyanate group)、羥基、羧基或醯胺基)、或至少一電磁波可固化官能基(如環氧基、環狀醚基、硫基(sulfide group)、縮醛基(acetal group)或內酯基(lactone group))的可固化樹脂，其可經固化而展現黏著特性。此外，此樹脂之特定種類可為，但不限於，丙烯酸樹脂(acryl resin)、聚酯樹脂、異氰酸樹脂(isocyanate resin)或環氧樹脂。
於本發明，作為可固化樹脂，可使用芳族或脂族、或直鏈或支鏈環氧樹脂。於本發明之一例示性具體實例中，可使用含有至少二官能基並具有180至1,000g/eq之環氧化物當量(epoxy equivalent)的環氧樹脂。當使用具有上述範圍之環氧化物當量的環氧樹脂時，可有效維持固化產物之特性如黏著性能和玻璃轉化溫度。此環氧樹脂可為下列者中之一者或至少兩者之混合物：甲酚清漆環氧樹脂(cresol novolac epoxy resin)、雙酚A型環氧樹脂(bisphenol A-type epoxy resin)、雙酚A型清漆環氧樹脂(bisphenol A-type novolac epoxy resin)、酚清漆環氧樹脂(phenol novolac epoxy resin)、四官能性環氧樹脂(tetrafunctional epoxy resin)、聯苯型環氧樹脂、三酚甲烷(triphenol methane)型環氧樹脂、經烷基改質之三酚甲烷環氧樹脂、萘型環氧樹脂、二環戊二烯型環氧
樹脂以及經二環戊二烯改質之酚型環氧樹脂。
於本發明之一例示性具體實例中，除了上述樹脂外，第二層可包括另外的組份如上述活化能射線-可聚合化合物、自由基起始劑、增黏劑、濕氣吸收劑、濕氣阻斷劑、分散劑、或矽烷化合物，其可與第一層中者相同或不同。此外，第二層可根據所欲物理性質而包括適當含量範圍之可固化材料、固化劑或填料。
第一及第二層之層合順序並無特別限制，因此第二層可形成於第一層上，或者第一層可形成於第二層上。
於一實例中，壓敏性黏著膜可包含於壓敏性黏著層表面上之阻隔膜。阻隔膜可由本技術領域中常用的任何材料所形成而無限制。例如，此處，阻隔膜可包括基底層、有機底塗層、無機沉積層、和有機頂塗層，且有機頂塗層可以與壓敏性黏著層接觸。
壓敏性黏著膜的於膜之厚度方向量測的水氣穿透率(WVTR)(製成膜厚度為10μm)可為50、40、30、20或10g/m2‧天或以下(於100℉以及100%相對濕度)。藉由控制含有壓敏性黏著劑組成物之壓敏性黏著層的組成及交聯狀態以具有此WVTR，可實現當用於電子裝置的封裝或包封結構時能藉由有效阻斷濕氣或氧氣自外在環境透入而安定地保護元件之封裝或包封結構。WVTR越低，濕氣阻隔性越佳，因此，WVTR的下限可為，但未特別限於，0g/m2‧天。
此外，壓敏性黏著膜可對可見光區具有極佳的透光率。於一實例中，本發明之壓敏性黏著膜之透光率(對可見光區)可為85%或以上。例如，壓敏性黏著膜之透光率(對可見光區)可為85%、87%、或90%或以上。此外，本發明之壓敏性黏著膜可具有低霾度(haze)與極佳透光率。於一實例中，壓敏性黏著膜之霾度可為3%、2%、1%、0.8%、0.5%、或0.3%或以下。即，根據本發明之壓敏性黏著劑組成物可藉由引入特定交聯系統而實現極佳的光學特性以及於高溫與高濕度之可靠性。
壓敏性黏著膜可進一步包括基底膜或離型膜(release film)(下文中可稱為"第一膜")，且壓敏性黏著層可形成於該基底膜或離型膜上。該結構可進一步包括形成於該壓敏性黏著層上之基底膜或離型膜(下文中可稱為"第二膜")。
圖1及2為例示性壓敏性黏著膜之橫截面圖。
如圖1所示，壓敏性黏著膜1可包含形成於基底膜或離型膜12上之壓敏性黏著層11。如圖2所示，另一例示性壓敏性黏著膜2可進一步包含形成於壓敏性黏著層11上之基底膜或離型膜21。雖未示於圖1及2，壓敏性黏著膜亦可具有壓敏性黏著劑組成物而無承載基底如基底膜或離型膜，並因而具有僅含形成為於室溫維持固相或半固相之膜或片之壓敏性黏著層的結構，或者壓敏性黏著層係形成於一基底膜或離型膜之兩面上的結構。
未特別限制第一膜之特定類型。作為第一膜可使用，例如，塑料膜。第一膜可為聚對酞酸乙二酯膜、聚四氟乙烯膜、聚乙烯膜、聚丙烯膜、聚丁烯膜、聚丁二烯膜、氯乙烯共聚物膜、聚胺甲酸酯(polyurethane)膜、乙烯-乙酸乙烯酯膜、乙烯-丙烯共聚物膜、乙烯-丙烯酸乙酯共聚物膜、乙烯-丙烯酸甲酯共聚物膜或聚醯亞胺膜。
當第一膜為離型膜時，可於此塑料膜之一或兩面上進行適當的離型處理(release treatment)。當於離型處理使用離型劑時可使用醇酸(alkyd)系離型劑、矽(silicone)系離型劑、氟系離型劑、氟化酯系離型劑、聚烯烴(polyolefin)系離型劑或蠟系離型劑。考量耐熱性，於上述實例中慣常使用醇酸(alkyd)系離型劑、矽(silicone)系離型劑或氟系離型劑，但本發明不以此為限。
作為第一膜可使用，例如，於基底之頂面或側面上形成氣體阻隔層之塑料膜。此膜可直接構成，例如，用於實現撓性元件之有機電子裝置的基板。
亦未特別限制第二膜之類型。舉例而言，作為第二膜可使用於上列之第一膜的類別中之一者，其可與第一膜相同或不同。
第一膜或第二膜之厚度並無特別限制。於一實例中，第一膜之厚度可為約50至500或100至200μm。於此範圍，製備或製造壓敏性黏著劑或有機電子裝
置之方法可有效地自動化，且可獲致經濟可行性(economic feasibility)上之有利效果。
第二膜之厚度亦無特別限制。舉例而言，第二膜之厚度可為與第一膜者相同、或較小或較大。
壓敏性黏著膜之壓敏性黏著層係包含壓敏性黏著劑組成物，且形成為膜或片。於壓敏性黏著層中，壓敏性黏著劑組成物可為交聯或未交聯狀態。壓敏性黏著層可於室溫為固相或半固相。此壓敏性黏著樹脂可於有機電子元件之封裝結構中形成交聯結構，此將於下文描述。
壓敏性黏著層之厚度並無特別限制，且可考量其用途而適當選擇。舉例而言，壓敏性黏著層之厚度可為約5至200μm。可考量，例如，埋置性(embeddability)(當作為有機電子元件的封裝劑時)、加工性或經濟可行性而控制壓敏性黏著層之厚度。
於另一態樣中，本發明提供製造壓敏性黏著膜之方法。可藉由將壓敏性黏著劑組成物塑化成膜或片而製造例示性壓敏性黏著膜。
於一實例中，該方法可包括將含有壓敏性黏著劑組成物之塗覆液施於為片或膜之基底膜或離型膜，並乾燥該所施之塗覆液。該方法可進一步包括將另外的基底膜或離型膜黏附至乾燥的塗覆液。
含有壓敏性黏著劑組成物之塗覆液可藉由例如將上述各壓敏性黏著劑組成物之組份溶於或分散於適當溶劑而製備。於一實例中，壓敏性黏著劑組成物之製備係
可藉由將濕氣吸收劑、阻斷劑或填料(需要時)溶於或分散於溶劑中，研磨所得產物，並使濕氣吸收劑、阻斷劑或填料與封裝樹脂混合。
用於製備塗覆液之溶劑的種類並無特別限制。但若溶劑的乾燥時間過長或需於高溫乾燥溶劑，在壓敏性黏著膜之可加工性或耐久性上會有些許問題。因此，可使用揮發溫度為為150℃或以下之溶劑。考量到膜之模製性(moldability)，可將少量具上述範圍或以上之揮發溫度的溶劑混合以使用。溶劑可為，但不限於，下列者中之一或至少二者：甲基乙基酮(methylethylketone(MEK))、丙酮、甲苯、二甲基甲醯胺(DMF)，甲賽璐蘇(methyl cellosolve(MCS))、四氫呋喃(THF)、二甲苯以及N-甲基吡咯啶酮(N-methylpyrrolidone(NMP))。
將塗覆液施於基底膜或離型膜之方法可為，但未特別限於，已知的塗覆法如刮刀塗覆(knife coating)、輥塗(roll coating)、噴塗(spray coating)、凹版式塗覆(gravure coating)、簾塗(curtain coating)、逗號刮刀塗覆(comma coating)或唇模塗覆(lip coating)。
可乾燥所施之塗覆液以揮發溶劑，藉此形成壓敏性黏著層。乾燥可於，例如，70至150℃進行1至10分鐘。可考量所使用之溶劑種類而改變乾燥條件。
乾燥後可於壓敏性黏著層上形成另外的基底膜或離型膜。
於另一態樣中，本發明提供用於封裝有機電子裝置之產品。用於封裝有機電子裝置之產品可包括基板；形成於該基板上之有機電子元件；以及封裝有機電子元件之整個表面例如頂面和側面的壓敏性黏著膜。壓敏性黏著膜可包括含有交聯狀態之壓敏性黏著劑組成物的壓敏性黏著層。用於封裝有機電子裝置之產品可進一步包括形成於壓敏性黏著層之頂面的覆蓋基板。
此處，有機電子元件可為，例如，有機發光元件。
於另一態樣中，本發明提供製造有機電子裝置之方法。用於封裝有機電子裝置之產品可使用例如壓敏性黏著膜而製造。
壓敏性黏著層可形成為在有機電子裝置中展現極佳的濕氣阻隔性及光學性質、有效地固定及承載基板與覆蓋基板之結構的封裝層。
此外，無論有機電子裝置之類型為何(例如，頂射型(top-emissive)或底射型(bottom-emissive)有機電子裝置)，壓敏性黏著層可展現極佳的透光性且可為安定的。
本文使用之術語"封裝層"可指覆蓋有機電子元件之頂面與側面之壓敏性黏著層。
圖3為圖示其中有機電子元件為有機發光元件之例示性有機電子裝置之圖。
舉例而言，製造有機電子裝置係可包括，將
上述壓敏性黏著膜施於其上形成有機電子元件之基板以覆蓋有機電子元件；以及固化該壓敏性黏著膜。
本文使用之術語"固化"可指藉由形成本發明之壓敏性黏著劑組成物使透過加熱或UV照射而具有交聯結構以製備壓敏性黏著劑。
具言之，有機電子元件32之形成係可藉由以如真空沉積或濺鍍之方法於作為基板之玻璃或聚合物膜31上形成透明電極、於透明電極上形成由例如電洞傳輸層、發光層和電子傳輸層構成之發光有機材料層、以及於其上進一步形成電極層。接著，係設置壓敏性黏著膜之壓敏性黏著層以覆蓋歷經上述程序的基板31之有機電子元件32的整個表面。
接著，可藉由使用層壓機(laminator)(並加熱以提供流動性)以將壓敏性黏著層壓至有機電子元件、以及交聯壓敏性黏著層中之樹酯，以形成封裝層。
於一實例中，設置以覆蓋有機電子元件32整個表面之壓敏性黏著層33可事先轉移至覆蓋基板34(如玻璃或聚合物膜)。將壓敏性黏著層轉移至覆蓋基板34，係可在從壓敏性黏著膜剝離第一或第二膜且壓敏性黏著層接觸覆蓋基板34後使用真空壓製機或真空層壓機並加熱而進行。當壓敏性黏著劑包含熱可固化壓敏性黏著樹脂且在此製程期間過度進行固化反應時，封裝層之黏結強度(cohesive strength)或壓敏性黏著劑強度可能會降低。因此，製程溫度可控制為約100℃或以下，且製程時
間可控制為於5分鐘內。
可藉由將已轉移有壓敏性黏著層之覆蓋基板34設置於有機電子元件32上、並進行熱壓程序，以形成封裝層。
封裝層可藉由固化壓敏性黏著層33而形成。舉例來說，可根據可固化壓敏性黏著樹脂之固化方法，於適當加熱室或UV室中進行固化程序。可考量有機電子元件的安定性和壓敏性黏著樹脂的固化性而適當選擇加熱條件或活化能射線照射條件，且為了增加壓製效率，可採取應用熱與壓力之熱壓(autoclaving)。
此處，係描述製造有機電子裝置之方法的一實例，但有機電子裝置可藉不同的方法製造。例如，可藉上述方法製造裝置，但可改變程序之順序或條件。舉例來說，可藉由先將壓敏性黏著層轉移至基板31上之有機電子元件上，而非轉移至覆蓋基板34上，並且在層合覆蓋基板34後實施固化程序，以形成封裝層。
本發明可提供能有效抵擋從外在環境透入有機電子裝置之濕氣或氧氣、並展現於嚴苛條件如高溫及高濕度下之可靠性與極佳光學特性的壓敏性黏著劑組成物，以及，包含彼之壓敏性黏著膜。
1，2‧‧‧壓敏性黏著膜
11‧‧‧壓敏性黏著層
12‧‧‧第一膜
21‧‧‧第二膜
3‧‧‧有機電子裝置
31‧‧‧基板
32‧‧‧有機電子元件
33‧‧‧壓敏性黏著層或封裝層
34‧‧‧覆蓋基板
圖1及2為根據本發明之例示性具體實例之壓敏性黏著膜的橫截面圖；以及圖3為根據本發明之一例示性具體實例之用於封裝有機電子裝置之產品的橫截面圖。
以下參照實施例及比較例詳述本發明，但本發明之範疇並不為以下實施例所限制。
製備塗覆液，其係藉由添加90g的丁基橡膠(Br268，EXXON)作為封裝樹脂、10g的氫化之DCPD系增黏劑(SU-90，Kolon)作為增黏劑、15g的三環癸烷二甲醇二丙烯酸酯(M262，Miwon)作為活化能射線-可聚合化合物、3g的3-甲基丙烯醯氧基丙基三甲氧基矽烷(3-methacryloxypropyl trimethoxysilane)(Sigma Aldrich)作為矽烷化合物、以及0.5g的2,2-二甲氧基-1,2-二苯基乙-1-酮(2,2-dimethoxy-1,2-diphenylethane-1-one)(Irgacure651，Ciba)作為自由基起始劑，並於甲苯將混合物稀釋成固含量(solid content)為約20wt%。
將製得的溶液塗覆在離型(release)PET之離型表面(released surface)，在烘箱中於100℃乾燥15分鐘，以製造含有厚度為20μm之壓敏性黏著層的壓敏性
黏著膜。所製的膜以2J/cm2照射UV射線後量測樣品之物理性質。
以如實施例1所述之相同方法製備壓敏性黏著膜，但使用10g的3-甲基丙烯醯氧基丙基三甲氧基矽烷(3-methacryloxypropyl trimethoxysilane)(Sigma Aldrich)。
以如實施例1所述之相同方法製備壓敏性黏著膜，但不使用3-甲基丙烯醯氧基丙基三甲氧基矽烷(0g)。
以如實施例1所述之相同方法製備壓敏性黏著膜，但使用90g的丙烯酸丁酯及10g的丙烯酸取代實施例1所用之丁基橡膠及氫化之DCPD系增黏劑。
下文中，藉以下方法評估實施例和比較例之物理性質。
實施例或比較例所製之壓敏性黏著膜的寬度係設為1吋，膜係於25°℃及50%相對濕度維持1小時，
之後量測壓敏性黏著膜之壓敏性黏著層對OLED面板(其上無機沉積氮化矽之玻璃)的剝離強度(剝離速度：5mm/sec，剝離角度：180度)。
實施例或比較例所製之壓敏性黏著膜的寬度係設為1吋，膜係於85℃及85%相對濕度維持1小時，之後量測壓敏性黏著膜之壓敏性黏著層對OLED面板(其上無機沉積氮化矽之玻璃)的剝離強度(剝離速度：5mm/sec，剝離角度：180度)。
測量係於常溫、常濕度進行，剝離強度係使用質地分析儀(texture analyzer)依據ASTM3330來測量。
將實施例或比較例所用之樹脂溶於溶劑中以製備樹脂組成物。將樹脂組成物施於厚度為38μm之基底膜(離型聚酯膜，RS-21G，SKC)。接著，組成物於110℃乾燥10分鐘，以形成厚度為100μm之膜型層。之後剝離基底膜，然後於厚度方向測量該膜型層之WVTR，且該層係維持於100℉及100%相對濕度。根據ASTM F1249說明書測量WVTR。
上述所製之壓敏性黏著膜之霾度係根據JIS K7105標準測試方法使用霾度計量測。
實施例或比較例所製之壓敏性黏著膜的寬度係設為1吋，膜係於25℃及50%相對濕度維持1週，之後量測壓敏性黏著膜對離型PET之剝離強度(剝離速度：5mm/sec，剝離角度：180度)。
測量係於常溫、常濕度進行，剝離強度係使用質地分析儀(texture analyzer)依據ASTM3330來測量。
如表1所示，根據本發明之實施例1可藉由避免於高溫及高濕度下因濕氣透入而降低之介面壓敏性黏著劑強度以能於嚴苛條件如高溫及高濕度下實現極佳耐久性及可靠性。相對地，比較例1則顯示於高溫下壓敏性黏著劑強度係降低，且比較例3顯示因濕氣透入而使介面壓敏性黏著劑強度降低。
1‧‧‧壓敏性黏著膜
11‧‧‧壓敏性黏著層
12‧‧‧第一膜
Claims (20)
- 一種壓敏性黏著劑組成物，其包括：封裝樹脂，其包含二烯和具有一個碳-碳雙鍵之烯烴系化合物的共聚物；多官能性活化能射線-可聚合化合物；以及滿足式1之矽烷化合物：
- 如申請專利範圍第1項之組成物，其中，活化能射線-可聚合化合物係與滿足式1之矽烷化合物形成交聯結構，以及，該交聯結構係與封裝樹脂形成半-互穿聚合物網絡(semi-interpenetrating polymer network)。
- 如申請專利範圍第1項之組成物，其中，活化能射線-聚合化合物係與滿足式1之矽烷化合物形成交聯結構，以及，封裝樹脂係與活化能射線-可聚合化合物或滿足式1之矽烷化合物形成交聯結構，以形成互穿聚合物網絡(interpenetrating polymer network)。
- 如申請專利範圍第1項之組成物，其中，活化能射線-可聚合化合物為多官能性丙烯酸酯。
- 如申請專利範圍第1項之組成物，其中，活化能射線-可聚合化合物係滿足式2：
- 如申請專利範圍第1項之組成物，其中，相對於100重量份之封裝樹脂，活化能射線-可聚合化合物之含量為5至30重量份。
- 如申請專利範圍第1項之組成物，其中，相對於100重量份之封裝樹脂，滿足式1之矽烷化合物之含量為0.1至10重量份。
- 如申請專利範圍第1項之組成物，其進一步包括增黏劑。
- 如申請專利範圍第8項之組成物，其中，增黏劑為氫化之環烯烴系聚合物。
- 如申請專利範圍第8項之組成物，其中，相對於100重量份之封裝樹脂，增黏劑之含量為5至100重量份。
- 如申請專利範圍第1項之組成物，其進一步包括自由基起始劑。
- 如申請專利範圍第11項之組成物，其中，相對於100重量份之活化能射線-可聚合化合物，自由基起始劑之含量為0.2至20重量份。
- 一種滿足方程式1之壓敏性黏著膜，其包括：壓敏性黏著層，其中，於25℃及50%相對濕度維持1小時後之壓敏性黏著層對基板的剝離強度(剝離速度：5mm/sec，剝離角度：180度)為P gf/25mm，以及於85℃及85%相對濕度維持1小時後之壓敏性黏著層對基板的剝離強度(剝離速度：5mm/sec，剝離角度：180度)為Q gf/25mm：[方程式1]Q1.3 P。
- 如申請專利範圍第13項之膜，其中，壓敏性黏著層係包含如申請專利範圍第1項之壓敏性黏著劑組成物或其交聯產物。
- 如申請專利範圍第13項之膜，其中，壓敏性黏著層係包含具有如申請專利範圍第1項之壓敏性黏著劑組成物或其交聯產物的第一層以及具有壓敏性黏著樹脂或黏著樹脂的第二層。
- 如申請專利範圍第13項之膜，其製成厚度為100μm時，於厚度方向之水氣穿透率為50g/m2‧天或以下。
- 如申請專利範圍第13項之膜，其對可見光區之透光率為85%或以上。
- 如申請專利範圍第13項之膜，其霾度為3%或以下。
- 一種用於封裝有機電子裝置之產品，其包括：基板；形成於該基板上之有機電子元件；以及如申請專利範圍第13項之壓敏性黏著膜，以封裝該有機電子元件。
- 一種製造有機電子裝置之方法，其包括：將如申請專利範圍第13項之壓敏性黏著膜施於其上形成有機電子元件之基板以覆蓋有機電子元件；以及固化該壓敏性黏著膜。
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| TW103126848A TWI534240B (zh) | 2013-08-05 | 2014-08-05 | 壓敏性黏著劑組成物，壓敏性黏著膜及使用彼製造有機電子裝置之方法 |
| TW103126851A TWI589667B (zh) | 2013-08-05 | 2014-08-05 | 壓敏性黏著膜及使用彼製造有機電子裝置之方法 |
| TW103126847A TWI557964B (zh) | 2013-08-05 | 2014-08-05 | 壓敏性黏著膜及使用彼製造有機電子裝置之方法 |
| TW103126849A TWI548713B (zh) | 2013-08-05 | 2014-08-05 | 壓敏性黏著劑組成物、壓敏性黏著膜及使用彼製造有機電子裝置之方法 |
| TW103126852A TWI586774B (zh) | 2013-08-05 | 2014-08-05 | 壓敏性黏著組成物、壓敏性黏著膜、及使用彼製造有機電子裝置之方法 |
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| TW103126851A TWI589667B (zh) | 2013-08-05 | 2014-08-05 | 壓敏性黏著膜及使用彼製造有機電子裝置之方法 |
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