201〇2〇2?lrw 29_ 九、發明說明： 【發明所屬之技術領域】 本發明是有關於一種感光性組成物、其所形成之封合 結構以及封合結構的製造方法。 口 【先前技術】 有機電激發光元件(organic electroluminescent de\dees or polymer electroluminescent devices )有輕薄、自發光、低 消耗功率、不需背光源、無視角限制及高反應速率等優良 特性’已被視為平面顯示器的明日之星。除了顯示哭座 外，由於有機電激發光元件可在輕薄、可 成陣列結構，所以也非常適合應用於照明，一般預估有機 電激發光元件的發光效率提升至1〇〇Lm/w以上，且演色 性高於80以上時，即有機會取代一般照明光源，因此有機 電激發光元件在為未來將扮演非常重要的角色。 罄 卜然，，OLED元件在商品化的過程巾，最令人注意的 是元件壽命_。—般造成〇LED元件騎的是ιτ〇 部份會有接觸不良、均勻性不足、制注人障.礙過大以及 有機層氧化等問題。另—個原_是有機層部份會有結晶 散、電化學性f魏、編卜8撼喧仙 L 等現象。糾，在陰極部份齡發生氧化、剝離 °此外’大氣中的水以及氧氣對於元 牛也疋^ β甚矩’導致元件輝度降低、驅動電壓上升、歸 Spots及短路發生，因此’封裝技術在〇led技術中是極 u W 29307twf.doc/n 201020291 為重要的一環。 ★ OLED S件難方法μ封止鮮㈣賴基材與封 裝盍’以阻絕錢及氧氣。早期qLED元件封裝方法如 Pioneer公司的美國專利第US6819〇42號以及nec公司的 美國專利第6525339號所揭示，均是以金屬封蓋貼附強力 吸水劑後’透過低透濕性環氧樹脂，利用紫外光硬化 板做緊密貼合，達到減緩水氣侵入的效果。後來，Ha_ Menegus #人之美國專利申請第2〇〇7/〇267972號則是以 玻璃封裝蓋取代不鏽鋼蓋，並在封止區域整合導入溶塊壁 (触^)、吸_與封賴。—般μ，封錢的阻絕並 不疋問題，因此封裝的問題即在紫外光封止劑。封止劑必 須選擇本身對水氣及氧氣有極佳之阻絕性 財鱗㈣邮-柳料搭^ 八蚀’然而此類的封止馳為硬脆，並不適 ;究，m材封合。因此’近期多有封止劑的開發與 參 =，_號所提出的-種封止劑，其包= -到到—個％氧樹脂官能基的樹脂；(2)含有0.M0% 一到五個方香環的酚醛樹脂，且在鄰位上 (3)0.1-10%陽離子型光起始劑。 土 【發明内容】 絕水it月提Γ種感光性組成物，其除了具有優異的阻 、 乳氣月匕力之外，還有良好的撓曲性與基材的附著 6 〜TW 29307twf.doc/n 201020291 力，以作為封止劑，用於一般不鏽鋼蓋或玻璃基材的封合， 或用於軟性基材的封合。 曰本發明提出一種感光性組成物，以感光性組成物之總 重篁來计鼻，其包括2〇〜80%的寡分子聚合物、2〜30%之 至少一第二環氧樹脂以及12〜54%之至少一第三環氧樹 月曰而且，感光性組成物還包括：每1〇〇重量份的寡分子 聚合物、第二環氧樹脂以及第三環氧樹脂之重量合中含有 2〜15重1份(phr)的陽離子型起始劑以及2〜的自由 基，起始劑。募分子聚合物的分子量為350〜3000 ,是由 〒環氧樹脂與一不飽和單羧酸改質而成，其分子鏈上 至少有兩個或兩個以上的壓克力官能基。第二環氧樹脂具 有四個或以上的環氧基，且環氧當量為15〇〜5〇〇。第三環 氧=旨’其與該第二魏樹料同，為—觀態環狀脂肪 族環氧樹脂。 ❿ 依照本發明實施例所述，上述之感光性組成物中，寡 为子聚合物的分子量為500〜1〇〇〇。 ，照本發明實施例所述，上述之感光性組成物中第 二=樹脂包括㈣A型環氧樹脂及其衍生物、雙盼f系 月旨3衍生物、酚搭環氧樹脂、蔡系環氧樹脂、脂 肪無衣氧树脂或脂環族環氧樹脂。 齡Λ 2本發明實施例所述’上述之感光性組成物中，雙 為180〜t細旨為㈣伽Α㈣氧樹闕縣當量大約 依照本發明實施例所述，上述之感光性組成物中，不 7 201020291 — -----1W 293 07twf.doc/n 飽和單羧酸包括丙烯酸、曱基丙烯酸、笨乙稀基丙稀酸、 硖喃丙稀酸、巴豆酸（CrotonicAcid)或氰基桂皮酸。 依照本發明實施例所述，上述之感光性組成物中，更 包括填充物。 依照本發明實施例所述’上述之感光性組成物中，填 充物包括二氧化矽、滑石粉、氧化鋁或黏土。 依照本發明實施例所述，上述之感光性組成物中，自 ❿ 由基型起始劑包括安息香、安息香衍生物或苯乙酮衍生物。 依照本發明實施例所述，上述之感光性組成物中，安 息香衍生物包括安息香曱醚、安息香***或安息香正丁 喊；苯乙酮衍生物包括二烷氧基苯乙酮、氣化苯乙酮或2_ 經基-2-曱基-1-丙嗣。 依照本發明實施例所述，上述之感光性組成物中，陽 離子型起始劑包括二芳基碘化合物或三芳基硫化合物。 依照本發明實施例所述，上述之感光性組成物不包含 溶劑。 依照本發明實施例所述，上述之感光性組成物中第 — %氧樹脂包括碳數為3〇〜9〇的固態多官能基環氧樹脂。 依照本發明實施例所述，上述之感光性組成物中，第 二環氧樹脂包括碳數為15〜25的環狀脂肪族環氧樹脂。 依照本發明實施例所述，上述之感光性組成物包括： 30〜40%的募分子聚合物；6〜3G%之第二環氧樹脂；以及 30〜54%之第三環氧樹脂。 201020291 ---------1 w 29307twf.doc/n ❿ ❿ 依照本發明實施例所述，上述之感光性組成物可作為 封止劑或黏著劑 本發明提出一種封合結構，其包括兩基材與封合物， 封合物位於前述兩基材之間，其是由上述之感光性組成物 [由光源照射硬化而成。 依照本發明實施例所述，上述之封合結構中，封合物 填滿上述兩基材之間的間隙或以框膠方式封合上述兩基 材。 一本發明提出一種封合結構的製造方法，包括將上述感 光性組成物置料紐之間，關統，以錢光性組成 物硬化形成封合物。 依照本發明實施例所述’上述之封合結構的製造方法 光源包括紫外光。 依照本發明實施例所述，上述之封合結構的製造方法 紫外光的照度為3〜9 J/cm2。 =士發明實施綱述，上述销合結構的製造方法 务外光的照度為5〜7 J/cm2。 光阻自由基.子型紫外光硬化系統，促使感 封止劑能夠混成(H蝴環氧樹脂的 與壓克力樹脂的柔曲度，使得封止劑除了具有優显的 之外’更有良好的撓曲性與基材的附 ,發明不僅可以用於-般不鏽鋼蓋或玻 离基材的封合’更可以用在軟性基材的封合。 中 中 中 9 201020291 〜ι …29307twf.doc/n 為讓本發明能更明顯易懂，下文特舉實施例，並配合 所附圖式，作詳細說明如下。 【實施方式】 本發明提出一種感光性組成物，其包括寡分子聚合 物、至少一第二環氧樹脂、至少一第三環氧樹脂、陽離子 型起始劑以及自由基型起始劑。 φ 寡分子聚合物是由第一環氧樹脂與不飽和單羧酸改質 而成，其分子鏈上至少有兩個或兩個以上的壓克力官能 基。养分子聚合物具有壓克力官能基，因此能夠提供較佳 的撓曲性。在一實施例中，募分子聚合物的含量為感光性 組成物總重量的20〜80%。在另一實施例中，寡分子聚合 物的含量為感光性組成物總重量的30〜4〇%。第—環氧樹 脂之實例包括雙酚A型環氧樹脂及其衍生物、雙酚F系環 、氧樹脂及其衍生物、酚醛環氧樹脂、萘系環氧樹脂、脂肪 族環氧樹脂或脂環族環氧樹。雙酚A型環氧樹脂為液態雙 盼A型環氧樹脂的環氧當量大約為丨〜。雙驗a型環 氧樹脂例如是Shell Chemical的EPON 828商品，其環氧 虽置為185-210。雙酚F型環氧樹脂例如是DAINIPPON INK &CHEMICALS公司的Epilclon 830S商品，其環氧當 量約171。不飽和單羧酸之實例包括丙烯酸、曱基丙烯酸、 苯乙稀基丙烯酸、硖喃丙烯酸、巴豆酸（Crotonic Acid) 或氰基桂皮酸。在一實施例中，寡分子聚合物的分子量分 子量為350〜3000。在另一實施例中，寡分子聚合物的分 293〇7twf.doc/n 201020291201〇2〇2?lrw 29_ IX. Description of the Invention: [Technical Field] The present invention relates to a photosensitive composition, a sealing structure formed therewith, and a method for producing a sealing structure. [Prior Art] Organic electroluminescent de\dees or polymer electroluminescent devices have excellent characteristics such as light weight, self-luminescence, low power consumption, no backlight, no viewing angle limitation and high reaction rate. The star of tomorrow for the flat panel display. In addition to displaying the crying seat, since the organic electroluminescent element can be light and thin and can be arrayed, it is also very suitable for illumination. Generally, the luminous efficiency of the organic electroluminescent element is estimated to be above 1 〇〇Lm/w. When the color rendering is higher than 80, there is an opportunity to replace the general illumination source, so the organic electroluminescent element will play a very important role for the future.卜 卜然, OLED components in the commercial process towel, the most noteworthy is the component life _. As a result, the LED components are ridden by the fact that some of them may have poor contact, insufficient uniformity, defects in the production of defects, excessive oxidation, and oxidation of the organic layer. Another original _ is the organic layer part of the phenomenon of crystal dispersion, electrochemical f Wei, braided 8 撼喧 L L and so on. Correction, oxidation and stripping occur at the cathode part of the temperature. In addition, 'the water in the atmosphere and the oxygen are also 元^β, which causes the element brightness to decrease, the driving voltage to rise, the Spots and the short circuit to occur, so the package technology is In the 〇led technology is a very u W 29307twf.doc/n 201020291 is an important part. ★ OLED S parts are difficult to seal the fresh (four) Lai substrate and package 盍 ' to block money and oxygen. The early qLED component encapsulation method, as disclosed in U.S. Patent No. 6,819, 430, to Pioneer, and U.S. Patent No. 6,525, 339, to nec, is a low moisture permeable epoxy resin after being attached with a strong water absorbing agent by a metal cap. The UV-cured plate is used for close fitting to reduce the intrusion of water vapor. Later, the US Patent Application No. 2〇〇7/〇267972 of Ha_ Menegus #人人 replaced the stainless steel cover with a glass-encapsulated cover, and integrated the introduction of the solution wall (touch), suction and sealing in the sealing area. As for the μ, the blocking of the money is not a problem, so the problem of packaging is the UV blocking agent. The sealant must be selected to have excellent resistance to moisture and oxygen. (4) Post-willow material is used to make it eight-etched. However, such a seal is hard and brittle, and it is not suitable. Therefore, there have been many recent developments of blocking agents and the types of blocking agents proposed by _, _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ To a five-part phenolic phenolic resin, and in the ortho position (3) 0.1-10% cationic photoinitiator. Soil [Summary of the Invention] The water-repellent composition of the water-repellent it month, in addition to excellent resistance, milky lunar force, good flexibility and adhesion of the substrate 6 ~ TW 29307twf.doc /n 201020291 Force, used as a sealer for the sealing of general stainless steel covers or glass substrates, or for the sealing of soft substrates. The present invention provides a photosensitive composition comprising a total weight of a photosensitive composition comprising 2 to 80% of an oligo molecular polymer, 2 to 30% of at least a second epoxy resin, and 12 ～54% of at least one third epoxy tree 曰 and the photosensitive composition further comprises: 1 part by weight of the oligo molecular polymer, the second epoxy resin and the third epoxy resin 2 to 15 parts by weight of 1 part (phr) of a cationic initiator and 2 to a free radical, starting agent. The molecular weight of the polymer is 350 to 3000, which is modified from an epoxy resin and an unsaturated monocarboxylic acid, and has at least two or more acrylic functional groups in its molecular chain. The second epoxy resin has four or more epoxy groups and has an epoxy equivalent of 15 Å to 5 Å. The third epoxy group is the same as the second Wei tree material, and is a view-ring cyclic aliphatic epoxy resin. According to the embodiment of the invention, in the photosensitive composition described above, the molecular weight of the oligomeric polymer is 500 to 1 Torr. According to the embodiment of the present invention, the second photosensitive material in the photosensitive composition includes (IV) A-type epoxy resin and its derivative, double-prepared f-based Yue 3 derivative, phenol epoxy resin, and Cai ring Oxygen resin, fat non-oxygen resin or cycloaliphatic epoxy resin. Age Λ 2 In the above-mentioned photosensitive composition, the above-mentioned photosensitive composition, the double is 180~t, the purpose is (4) gamma (tetra) oxoanthene equivalent, according to the embodiment of the present invention, the above photosensitive composition , not 7 201020291 — -----1W 293 07twf.doc/n Saturated monocarboxylic acids include acrylic acid, mercaptoacrylic acid, stupid acid acrylic acid, perylene glycol acid, crotonic acid (CrotonicAcid) or cyano Cinnamon acid. According to an embodiment of the invention, the photosensitive composition described above further comprises a filler. According to the photosensitive composition described above in the embodiment of the invention, the filler comprises cerium oxide, talc, alumina or clay. According to an embodiment of the present invention, in the above photosensitive composition, the pharmaceutically acceptable starter comprises a benzoin, a benzoin derivative or an acetophenone derivative. According to an embodiment of the present invention, in the above photosensitive composition, the benzoin derivative includes benzoin ether, benzoin ethyl ether or benzoin sing; the acetophenone derivative includes dialkoxyacetophenone, gasified phenyl b Ketone or 2-cysyl-2-mercapto-1-propanthene. According to the embodiment of the invention, in the above photosensitive composition, the cationic initiator is a diaryliodonium compound or a triarylsulfide compound. According to an embodiment of the invention, the photosensitive composition described above does not contain a solvent. According to an embodiment of the present invention, the first-half oxy-resin in the photosensitive composition includes a solid polyfunctional epoxy resin having a carbon number of 3 Å to 9 Å. According to the embodiment of the invention, in the photosensitive composition described above, the second epoxy resin comprises a cyclic aliphatic epoxy resin having a carbon number of 15 to 25. According to an embodiment of the invention, the photosensitive composition comprises: 30 to 40% of a molecular polymer; 6 to 3 G% of a second epoxy; and 30 to 54% of a third epoxy resin. 201020291 ---------1 w 29307twf.doc/n ❿ ❿ In accordance with an embodiment of the present invention, the above photosensitive composition can be used as a sealant or an adhesive. The present invention provides a sealing structure. The substrate and the sealing composition are disposed, and the sealing compound is located between the two substrates, and is formed by curing the above-mentioned photosensitive composition [illuminated by a light source. According to the embodiment of the present invention, in the sealing structure, the sealing compound fills the gap between the two substrates or seals the two substrates by a sealant. A method for manufacturing a sealing structure according to the present invention comprises: arranging the photosensitive composition described above, and curing the composition with a light-sensitive composition. The method of manufacturing the above-described sealing structure according to an embodiment of the present invention includes a source of ultraviolet light. According to the embodiment of the present invention, the manufacturing method of the above sealing structure has an illuminance of ultraviolet light of 3 to 9 J/cm 2 . In the outline of the invention, the illuminance of the above-mentioned pin-and-pin structure is 5 to 7 J/cm 2 . Photoresist free radical. Sub-type UV curing system, which enables the combination of the sealing agent (the softness of the H-resin epoxy resin and the acrylic resin, so that the sealing agent has better than the excellent one) Good flexibility and adhesion to the substrate, the invention can be used not only for the sealing of the stainless steel cover or the glass substrate, but also for the sealing of the soft substrate. 中中中9 201020291 ~ι ...29307twf. The present invention will be described in detail below with reference to the accompanying drawings, in which the present invention is described in detail below. [Embodiment] The present invention provides a photosensitive composition comprising an oligo molecular polymer. At least a second epoxy resin, at least a third epoxy resin, a cationic initiator, and a radical initiator. The φ oligo molecular polymer is modified from the first epoxy resin and the unsaturated monocarboxylic acid. It has at least two or more acrylic functional groups on its molecular chain. The molecular polymer has an acrylic functional group and thus provides better flexibility. In one embodiment, it is raised. The content of the molecular polymer is the total amount of the photosensitive composition In another embodiment, the content of the oligo molecular polymer is 30 to 4% by weight based on the total weight of the photosensitive composition. Examples of the first epoxy resin include bisphenol A type epoxy resin and a derivative thereof, a bisphenol F ring, an oxygen resin and a derivative thereof, a novolac epoxy resin, a naphthalene epoxy resin, an aliphatic epoxy resin or an alicyclic epoxy resin. The bisphenol A epoxy resin is a liquid The epoxy equivalent of the double-presence A type epoxy resin is about 丨~. The double-check type a-type epoxy resin is, for example, a product of Shell Chemical's EPON 828, and the epoxy is set to 185-210. For example, a bisphenol F-type epoxy resin It is a product of Epilclon 830S of DAINIPPON INK & CHEMICALS, which has an epoxy equivalent of about 171. Examples of unsaturated monocarboxylic acids include acrylic acid, mercaptoacrylic acid, styrene acrylic acid, fluorene acrylic acid, Crotonic acid or Cyanocinic acid. In one embodiment, the molecular weight molecular weight of the oligo molecular polymer is from 350 to 3000. In another embodiment, the oligo molecular polymer is divided into 293 〇 7 twf.doc/n 201020291
A / …dTW 子量分子量為500〜1000。寡分子聚合物的分子量過高， 則有黏度太大，難以操作的問題。寡分子聚合物的分子量 過低，則會導致強度不足。募分子聚合物之合成步驟例如 是將第一環氧樹脂與不飽和單缓酸混合後，再加入適當催 化劑’於適當的溫度下進行反應一段時間。在一實施例中， 券分子聚合物之合成步驟為先將液態的雙紛A環氧樹脂與 不飽和單致酸混合後’再加入三苯基填 馨 （Triphenyiphosphine)催化劑’於10(rc下反應Μ小時， 以形成之。 第二環氧樹脂具有四個或以上的環氧基，且其環氧當 量為150〜500。第二環氧樹脂的含量為感光性組成物總重 量的2〜30%。在一實施例中，第二環氧樹脂的含量為感光 性組成物總重量的2〜8%。在另一實施例中，第二環氧樹 脂的含量為感光性組成物總重量的6〜3〇%。第二環氧樹 脂可以是在室溫下呈固態的環氧樹脂。第二環氧樹脂包括 奴數為30〜90的固態多官能基環氧樹脂，例如是酚 9 (N^〇laC)環氧掛脂、鄰甲竣Novolac環氧樹脂、或2_乙基 聚氧乙烯甘油酯環氧樹脂。第二環氧樹脂可以使用aba Geigy 公司的 ECN_1299 商品、SheU Chemical 公司的 SU 8 商〇口、固態雙官能基環氧樹脂例如是三井石化公司的R3〇l 商品、Shell Chemical公司的ΕΡ〇Ν10〇1商品、或南亞公 司的NPES901商品等。 第二環氧樹脂，其與第二環氧樹脂不同，為一種環狀 月曰肪奴％氧樹脂，其在室溫下呈液態。液態的第三環氧樹 11 201020291 ί / TW 29307twf.doc/n 脂可以提供作為感光性組成物的各成分熱溶融的媒介，使 得封裝用感光性組成可不需使用任何的溶劑。在一實施例 中’第三環氧樹脂的含量為12〜48%。在另一實施例中， 第三環氧樹脂的含量為30〜54%。第三環氧樹脂的實例包 括碳數為15〜25的環狀脂肪族環氧樹脂’例如是3,4_環氧 基環己烧竣酸醋(3,4-epoxylcyclohexanecarboxylate)、或脂 環族二環氧化物(Cycloaliphatic diepoxide)。第三環氧樹脂 參 可以使用SART0MER公司的K126商品(3,4-環氧環己烷 甲基環氧環己甲酸甲酯 (3,4-Epoxycyclohexanemethyl-3,4- epoxy- cyclohexane carboxylate))、或 Dow Chemical 公司的 ERL-4221、 ERL4221D、ERL-4221E 等商品。 陽離子型起始劑的含量例如是每100重量份的寡分子 聚合物、第二環氧樹脂以及第三環氧樹脂之重量合中含有 2〜15重量份（以後，以2〜15 phr表示之）。陽離子型起始 劑的實例包括三芳基硫化合物或二芳基碘化合物，例如 ❹ SARTOMER公司的二芳基碘鑌鹽型之陽離子起始劑 CD1012。 自由基型起始劑的含量例如是每100重量份的募分子 聚合物、第二環氧樹脂以及第三環氧樹脂之重量合中含有 2〜15phr重量份（以後，以2〜15 phr表示之）。自由基型 起始劑包括安息香（Benzoin)、安息香衍生物或苯乙酮衍 生物。安息香衍生物的實例包括安息香甲醚、安息香乙_ 或安息香正丁喊。苯乙酮衍生物的實例包括二烧氧基苯乙 12 201020291 —TW 29307twf.doc/n 酮、氣化苯乙酮、2-經基-2-甲基-1-丙_、經基環己基苯 基丙酮（1-hydroxycyclohexyl phenyl ketone(例如 Ciba 公司 之IRGACURE 184商品）或雙(2,4,6-三曱基苯曱基-苯基 氧化膦（bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide (例如Ciba公司的IRGACURE 819商品）。 本發明感光性組成物除了包括寡分子聚合物、至少一 第一環氧樹脂、至少一第三環氧樹脂、陽離子型起始劑以 φ 及自由基型起始劑冬外，還可再添加填充物。填充物包括 二氧化矽、滑石粉、氧化鋁或黏土。填充物的使用可以填 充於分子鏈間的自由體積，除了具有阻擋水氣或是氧氣穿 透路徑的作用之外’並且還可以降低材料的成本。 本發明之感光性組成物可用作為封合材料或黏著層。 在實際應用時’可以先將至少一種第二環氧樹脂與至少一 種第三環氧樹脂在適當的溫度下，例如是l〇〇〜u〇<t下熱 溶融，再將寡分子聚合物、陽離子型起始劑以及自由基型 起始劑加入，之後’照射紫外光以使其聚合硬化。在—實 • 施例中，所使用的紫外光的照度例如是3〜9J/Cm2。在另一 實施例中，所使用的紫外光的照度例如是5〜7 J/cm2。 本發明之感光性組成物可以作為封止劑或黏著層，以 應用於構裝元件的封合或黏著，構裂元件包括光電元件(例 如是LED、0LED、LCD)或是光纖等。圖i和2分別是將 本發明之感光性組成物應用於光電元件作為封合劑的示音 圖。 請參照圖1，基材10上已依序堆疊陽極12、發光層 13 201020291 rwWJVrW 29307twf.doc/n 14以及陰極16。而本發明之感紐組成細用作為封止 d，凡全填滿基材1〇與另一基材20之間的間隙’使其一 者緊密的黏貼。基材1〇與基材2〇例如是硬式基材或^可 撓式基材。硬式基材之材質例如是玻璃、石英、半導體晶 圓如矽晶圓、或半導體合金晶圓如矽化鍺晶圓等。可撓^ 基材之材質例如是塑膠如聚乙烯(PE)、聚對苯二甲酸乙二 酉曰(PET)、聚醯亞胺(pi)等、金屬落(metaif〇ii)或是紙等。 -月參“、、 圖2 ’本發明之感光性組成物用作為封止劑， 其並未完全填滿基材1〇與另一基材20之間的間隙，而僅 是用以框膠方式封合基材1〇與另一基材20。 實施例 寡分子聚合物-I(Oligomer-I)合成： 將EPON 828 (第一環氧樹脂，雙紛A型環氧樹月旨， 環氧當量185-210，Shell Chemical商品）185克、丙烯酸 (Acyrlic acid，分子量 72.06，TCI 商品）79.99 克、熱抑 制劑（2,2’-亞曱基雙（4-曱基-6-叔丁基苯 S^)( 2,2'-methylenebis(4-methyl-6-tert-butylphenol» SHOWA 商品)）0.34克、及催化劑(三苯基膦，Triphenyl phosphine， Lancaster商品）3.93克放入1升反應瓶中，然後將反應瓶 放入油浴槽内，攪拌速度為200rpm，反應溫度在 105°C±5°C，冷凝管溫度設為9°C，總反應時間5〜6小時。 14 29307twf.doc/n 201020291The molecular weight of A / ...dTW is 500~1000. If the molecular weight of the oligo molecular polymer is too high, there is a problem that the viscosity is too large and it is difficult to handle. If the molecular weight of the oligo molecular polymer is too low, the strength will be insufficient. The synthetic step of the molecular polymer is carried out, for example, by mixing the first epoxy resin with an unsaturated mono-acid, and then adding a suitable catalyst to carry out the reaction at a suitable temperature for a certain period of time. In one embodiment, the step of synthesizing the valency molecule polymer is to first mix the liquid bisphenol A epoxy resin with the unsaturated monoacid and then add the triphenyiphosphine catalyst to 10 (rc) The second epoxy resin has four or more epoxy groups and has an epoxy equivalent of 150 to 500. The content of the second epoxy resin is 2~ of the total weight of the photosensitive composition. 30%. In one embodiment, the content of the second epoxy resin is 2 to 8% by weight based on the total weight of the photosensitive composition. In another embodiment, the content of the second epoxy resin is the total weight of the photosensitive composition. 6 to 3 % by weight. The second epoxy resin may be an epoxy resin which is solid at room temperature. The second epoxy resin includes a solid polyfunctional epoxy resin having a slave number of 30 to 90, such as phenol 9 (N^〇laC) epoxy grease, o-benzol Novolac epoxy resin, or 2-ethyl polyoxyethylene glyceride epoxy resin. The second epoxy resin can be used by ABA Geigy's ECN_1299 product, SheU Chemical Company SU 8 〇 、, solid bifunctional epoxy resin such as Mitsui The company's R3〇l product, Shell Chemical's ΕΡ〇Ν10〇1 product, or South Asia's NPES901 product, etc. The second epoxy resin, which is different from the second epoxy resin, is a ring-shaped moon Oxygen resin, which is liquid at room temperature. The liquid third epoxy tree 11 201020291 ί / TW 29307twf.doc/n grease can provide a heat-melting medium for each component of the photosensitive composition, making the photosensitive composition of the package It is not necessary to use any solvent. In one embodiment, the content of the third epoxy resin is 12 to 48%. In another embodiment, the content of the third epoxy resin is 30 to 54%. Examples of the resin include a cyclic aliphatic epoxy resin having a carbon number of 15 to 25, such as 3,4-epoxylcyclohexanecarboxylate, or an alicyclic diepoxide. (Cycloaliphatic diepoxide). The third epoxy resin can be used in the K126 product of SART0MER (3,4-epoxycyclohexanemethyl-3,4-epoxy- Cyclohexane carboxylate)), or EWL-4221 of Dow Chemical Company ERL4221D, ERL-4221E, etc. The content of the cationic initiator is, for example, 2 to 15 parts by weight per 100 parts by weight of the oligo molecular polymer, the second epoxy resin, and the third epoxy resin (hereinafter). , expressed in 2~15 phr). Examples of the cationic initiator include a triarylsulfide compound or a diaryliodonium compound such as a cationic initiator CD1012 of a diaryliodonium salt type of SAR SARTOMER. The content of the radical type initiator is, for example, 2 to 15 phr parts by weight per 100 parts by weight of the molecular polymer, the second epoxy resin, and the third epoxy resin (hereinafter, expressed by 2 to 15 phr) )). Free radical type starters include Benzoin, benzoin derivatives or acetophenone derivatives. Examples of benzoin derivatives include benzoin methyl ether, benzoin B or benzoin. Examples of the acetophenone derivative include dioxyoxyphenylene 12 201020291 - TW 29307twf.doc/n ketone, gasified acetophenone, 2-carbyl-2-methyl-1-propanyl, cyclyl-based 1-hydroxycyclohexyl phenyl ketone (for example, IRGACURE 184 from Ciba) or bis(2,4,6-trimethylbenzoyl)- Phenylphosphineoxide (for example, IMGACURE 819 from Ciba). The photosensitive composition of the present invention comprises, in addition to the oligo molecular polymer, at least a first epoxy resin, at least a third epoxy resin, a cationic initiator, φ and a free radical. The type of starter may be further added to the filler in winter. The filler includes cerium oxide, talc, alumina or clay. The filler can be used to fill the free volume between the molecular chains, in addition to blocking moisture or The effect of the oxygen penetrating path is 'and the cost of the material can also be reduced. The photosensitive composition of the present invention can be used as a sealing material or an adhesive layer. In practical applications, at least one second epoxy resin can be firstly used. a third epoxy tree At a suitable temperature, for example, l〇〇~u〇<t hot melt, then add an oligo molecular polymer, a cationic initiator, and a radical initiator, and then 'irradiate ultraviolet light to make it Polymerization hardening. In the embodiment, the illuminance of the ultraviolet light used is, for example, 3 to 9 J/cm 2. In another embodiment, the illuminance of the ultraviolet light used is, for example, 5 to 7 J/cm 2 . The photosensitive composition of the invention can be used as a sealing agent or an adhesive layer for sealing or adhesion of a component, which comprises a photovoltaic element (for example, LED, OLED, LCD) or an optical fiber, etc. 2 is a sound diagram in which the photosensitive composition of the present invention is applied to a photovoltaic element as a sealing agent. Referring to FIG. 1, the anode 12 and the light-emitting layer 13 are sequentially stacked on the substrate 10. 201020291 rwWJVrW 29307twf.doc/n 14 And the cathode 16. The inductive composition of the present invention is used as a sealing d, and the gap between the substrate 1 and the other substrate 20 is completely filled, so that the substrate is closely adhered. The substrate 2 is, for example, a hard substrate or a flexible substrate. Examples of the material of the rigid substrate It is glass, quartz, semiconductor wafers such as germanium wafers, or semiconductor alloy wafers such as germanium wafers, etc. The material of the flexible substrate is, for example, plastic such as polyethylene (PE) or polyethylene terephthalate.曰 (PET), polyimine (pi), etc., metal drop (metaif〇ii) or paper, etc. - Moonlight ",, Figure 2 'The photosensitive composition of the present invention is used as a blocking agent, and The gap between the substrate 1 and the other substrate 20 is not completely filled, but only the substrate 1 and the other substrate 20 are sealed by a sealant. EXAMPLES Oligomeric Polymer-I (Oligomer-I) Synthesis: EPON 828 (first epoxy resin, double-type A-type epoxy resin, epoxy equivalent 185-210, Shell Chemical) 185 g, acrylic acid (Acyrlic acid, molecular weight 72.06, TCI commodity) 79.99 grams, thermal inhibitor (2,2'-hydrazolyl bis(4-mercapto-6-tert-butylbenzene S^) (2,2'-methylenebis (4 -methyl-6-tert-butylphenol»SHOWA ()), 0.34 g, and 3.93 g of catalyst (triphenylphosphine, Triphenyl phosphine, Lancaster) were placed in a 1 liter reaction flask, and then the reaction flask was placed in an oil bath. The stirring speed is 200 rpm, the reaction temperature is 105 ° C ± 5 ° C, the condensation tube temperature is set to 9 ° C, and the total reaction time is 5 to 6 hours. 14 29307twf.doc/n 201020291
t / V\#-/JTW 寡分子聚合物-Il(Oligomer-II)合成： 將Epilclon 830S(第一環氧樹脂，雙酚F型環氧樹脂， 環氧當量約 171，DAINIPPON INK &CHEMICALS 商品） 171克、丙烯酸（分子量72.06，TCI商品）79.99克、熱 抑制劑(2,2'-亞曱基雙(4-甲基-6-叔丁基苯酚），81101八商 品）0.34克及催化劑(三苯基膦，Lancaster商品）3.93克放 入1升反應瓶中’然後將反應瓶放入油浴槽内，攪拌速度 為200rpm’反應溫度在l〇5°C±5°C，冷凝管溫度設為9°C， 總反應時間5〜6小時。 實例1 : 取40克的寡分子聚合物_1、環氧樹脂ECN-1299 (第 二環氧樹脂’鄰甲紛Novolac環氧樹脂，環氧當量 217-244 ’ Ciba Geigy商品）6克、環氧樹脂R301 (第二環 氧樹爿曰’雙盼A型壤乳樹脂，環氧當量450-525，三井石 ❹ 化商品）18克、環氧樹脂K126 (第三環氧樹脂，.3,4-環氧 環己院曱基-3,4-環氧環己曱酸曱酯 (3,4-Epoxycyclohexanemethyl-3,4- epoxy. cyclohexane carboxylate) ’環氧當量131_143，三井石化公司之 SARTOMER商品）36克於反應瓶内，並在9〇。〇油浴中以 機械攪拌混合均勻。接著將油浴降溫至5〇〇c後加入陽離子 起始劑CD1012 (―芳基硪鑌鹽型’ sartqmer商品） 5Phr、自由基起始劑IRGACURE 184 ( “羥基環己基苯基 15 201020291，一一 丙酮（1-Hydroxycyclohexyl phenyl ketone)，Ciba 商品） 1.25phr、自由基起始劑IRGACURE 819 (雙(2,4,6-三甲基 苯甲基-苯基 氧化膦 (Bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide，Ciba 商 品）1.25phr。然後降至室溫後加入滑石粉填充物（粒徑 3-5μιη) 20phr ’並均勻攪拌，接著以三滾筒研磨機研磨二 次。將配方塗佈成厚度約l〇〇Mm之薄膜後，以365nm汞 燈源照射紫外光6J/cm2能量，然後以熱機械分析儀以 10°C/min的升溫速度量測玻璃轉換溫度Tg及熱膨脹係數 (Coefficient of Thermal Expansion);以熱重分析儀(TGA) 量測5%重量損失之溫度；裁切樣品成寬丨公分(cm)長5cm 之試片，然後折曲180。下測試其撓曲度；以M〇c〇n w_3/6〇 水氣滲透儀在40°C相對溼度90%下量測水氣透過速率 (WVTR)。另外，為了職不同紐的拉伸剪切黏接強度 (Tensile-shear Strength Adhesion)，則根據 ASTM 咖⑷似 =法製作試片’並以365nm汞燈源照射紫外光·V能 ® 、里’利用雙枉式拉力機(QC Tecl〇在拉伸速率5mm/min下 測試其對基材的附著力，其結果如表i所示。 實例2〜7 : 依照表1所枕_叹上述實m之方法製備配方 並進行測量’其結果如表1所示。 比較例1 : 16 201020291 w 29307twf.doc/n 取80克养分子聚合物-I、多官能基壓克力單體SR454 (丙乳基化二經甲基丙院二丙稀酸醋（Propoxylated trimethylolpropane triacrylate)，SART0MER 商品）20 克於 反應瓶内’並在50°C油浴中以機械攪拌混合均勻，接著加 入l_25phr自由基起始劑IRGACURE 184、1.25phr自由基 起始劑IRGACURE819。然後降至室溫後加入滑石粉填充 物（粒徑3-5μιη) 20phr，並均勻攪拌，接著以三滾筒研磨 機研磨二次。之後依照實例1之方式測量，其結果如表1 所示。 比較例2 : 取環氧樹脂-I ECN-1299 (第二環氧樹脂，鄰曱酚 Novolac環氧樹脂，環氧當量217-244，CibaGeigy商品） 10克、30克環氧樹脂R3〇l、60克環氧樹脂Km於反應 瓶内，並在90 C油浴中以機械擾摔混合均勻。接著將油浴 降溫至50C後加入5phr陽離子起始劑cdi〇12、125phr • 自由基起始劑IRGACURE 184、l.25phr自由基起始劑 IRGACURE 819。然後降至室溫後加入滑石粉填充物（粒 徑3-5μιη) 20phr，並均勻攪拌，接著以三滾筒研磨機研磨 二次。之後依照實例1之方式測量，其結果如表丨所示。 比較例3 : 取40克养分子聚合物-I、6克環氧樹脂ECN 1299、18 克環氧樹脂R3(H、36克環氧樹月旨Km於反應瓶内，並在 17 29307twf.doc/n 201020291 w _________nw 90 C油浴中以機械攪拌混合均勻。接著將油浴降溫至5〇它 後加入5phr陽離子起始劑CDl〇12、丨25phr自由基起始劑 IRGACURE 184、1.25phr 自由基起始劑 IRGACURE 819， 並均勻授拌，降至室溫後以三滚筒研磨機研磨二次。之後 依照實例1之方式測量，其結果如表丨所示。t / V\#-/JTW Oligomeric Polymer-Il (Oligomer-II) Synthesis: Epilclon 830S (first epoxy resin, bisphenol F epoxy resin, epoxy equivalent of about 171, DAINIPPON INK &CHEMICALS Commodity) 171 g, acrylic acid (molecular weight 72.06, TCI commercial product) 79.99 g, thermal inhibitor (2,2'-fluorenylene bis(4-methyl-6-tert-butylphenol), 81101 eight commercial) 0.34 g and Catalyst (triphenylphosphine, Lancaster) 3.93 g was placed in a 1 liter reaction flask. Then the reaction flask was placed in an oil bath at a stirring speed of 200 rpm. The reaction temperature was at 10 °C ± 5 °C. The temperature was set to 9 ° C and the total reaction time was 5 to 6 hours. Example 1: Take 40 g of oligo molecular polymer _1, epoxy resin ECN-1299 (second epoxy resin 'Neoprene Novolac epoxy resin, epoxy equivalent 217-244 'Ciba Geigy commodity) 6 g, ring Oxygen Resin R301 (Second Epoxy 爿曰 'Double-A type of pre-lact resin, epoxy equivalent 450-525, Mitsui Shisui) 18 grams, epoxy resin K126 (third epoxy resin, .3, 4-, 4-Epoxycyclohexanemethyl-3,4-epoxy cyclohexane carboxylate 'epoxy equivalent 131_143, SARTOMER product of Mitsui Petrochemical Co., Ltd. 36 grams in the reaction bottle and at 9 〇. Mix well with mechanical agitation in the oil bath. Then, the oil bath was cooled to 5 〇〇c, and then a cationic initiator CD1012 ("aryl sulfonium salt type" sartqmer) 5Phr, a radical initiator IRGACURE 184 ("hydroxycyclohexylphenyl 15 201020291, one by one" was added. Acetone (1-Hydroxycyclohexyl phenyl ketone), Ciba product) 1.25 phr, free radical initiator IRGACURE 819 (bis(2,4,6-trimethylbenzyl-phenylphosphine oxide (Bis(2,4,6) -trimethylbenzoyl)-phenylphosphineoxide, Ciba commodity) 1.25 phr. Then, after cooling to room temperature, add talc filler (particle size 3-5 μιη) 20 phr ' and stir evenly, then grind twice with a three-roll mill. After forming a film having a thickness of about 10 μm, the energy of 6 J/cm 2 of ultraviolet light is irradiated with a 365 nm mercury light source, and then the glass transition temperature Tg and the coefficient of thermal expansion (Coefficient) are measured by a thermomechanical analyzer at a temperature increase rate of 10 ° C/min. Of Thermal Expansion); measuring the temperature of 5% weight loss by thermogravimetric analyzer (TGA); cutting the sample into a test piece of 5 cm in width and (cm) in length, and then bending 180. The degree of deflection is tested under the test; Relative humidity of 40°C with M〇c〇n w_3/6〇 water gas permeation meter The water vapor transmission rate (WVTR) is measured at 90%. In addition, for the Tensile-shear Strength Adhesion, the test piece is made according to the ASTM coffee (4) method and is 365 nm. The mercury source was irradiated with ultraviolet light and V-energy®, and the adhesion of the substrate to the substrate was tested by a double-twist type tensile machine (QC Tecl® at a tensile rate of 5 mm/min. The results are shown in Table i. Example 2 ~7 : Prepare the formula and measure according to the method of Table 1 above. The results are shown in Table 1. Comparative Example 1: 16 201020291 w 29307twf.doc/n Take 80 g of molecular polymer-I , Multifunctional acrylic monomer SR454 (Propoxylated trimethylolpropane triacrylate, SART0MER) 20 grams in the reaction flask 'and in a 50 ° C oil bath Mix well with mechanical agitation, then add 1-25 phr free radical initiator IRGACURE 184, 1.25 phr free radical initiator IRGACURE 819. Then, after cooling to room temperature, add talc filler (particle size 3-5 μιη) 20 phr, and stir evenly. It was then ground twice with a three-roll mill. Then, it was measured in the same manner as in Example 1, and the results are shown in Table 1. Comparative Example 2: Epoxy resin - I ECN-1299 (second epoxy resin, o-nonphenol Novolac epoxy resin, epoxy equivalent 217-244, Ciba Geigy commercial product) 10 g, 30 g epoxy resin R3〇l, 60 g of epoxy resin Km was placed in the reaction flask and uniformly mixed by mechanical disruption in a 90 C oil bath. The oil bath was then cooled to 50 C and 5 phr cationic starter cdi 〇 12, 125 phr • free radical initiator IRGACURE 184, 1.25 phr free radical initiator IRGACURE 819 were added. Then, after dropping to room temperature, 20 phr of a talc filler (particle size 3-5 μm) was added, and the mixture was uniformly stirred, followed by grinding twice with a three-roll mill. Then, it was measured in the same manner as in Example 1, and the results are shown in Table 。. Comparative Example 3: Take 40 grams of molecular polymer - I, 6 grams of epoxy resin ECN 1299, 18 grams of epoxy resin R3 (H, 36 grams of epoxy tree Km in the reaction bottle, and at 17 29307twf.doc /n 201020291 w _________nw 90 C oil bath is mixed with mechanical agitation. Then the oil bath is cooled to 5 〇. Then add 5 phr cationic starter CDl 〇 12, 丨 25 phr free radical initiator IRGACURE 184, 1.25 phr free radical The initiator IRGACURE 819 was uniformly mixed, and after being cooled to room temperature, it was ground twice by a three-roll mill, and then measured in the same manner as in Example 1, and the results are shown in Table 。.
表1 例 1 例 2 例 3 例 4 例 5 例 6 例 7 比 較 例 1 比 較 例 2 比 較 例 3 幕分子 聚合物1(%) 40 50 20 30 60 70 80 80 - 40 環氧樹 10%ECN-1299 脂（％) 30%R301 60 50 80 70 40 30 20 100 60 60%K126 壓見力單體（Acrylate Monomer) (%) • — - - - 20 - - 填充物（phr) 20 20 20 20 20 20 20 20 20 - 自由基型起始劑（phr) 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 - 2.5 陽離子型起始劑（phr) 5 5 5 5 5 5 5 - 5 5 玻璃轉移温度Tgu (°c) 129 123 130 129 120 105 101 60 130 125 熱膨脹係數CTE (<Tg ; pm/°C) 53 55 51 53 60 61 65 110 44 52 5%重量損失之溫度(°C) 330 315 331 330 311 310 301 160 375 325 在玻璃上之拉伸剪切黏接 強度(Kgf/mm2) 102 100 101 110 98 93 95 10 50 90 在聚亞醯胺上之拉伸剪切 黏接強度(KgPmm2) 103 99 90 91 100 105 105 11 30 88 撓曲性（FlexibleAbility) Φ ㊉ Θ Φ Φ 0 Θ Θ X 0 水氣透過速率WVTR (g/m2·天） 4.6 6.0 5.4 6.7 7.1 5.8 7.3 40 8.0 16.6 實例8 : 取40克寡分子聚合物-I、24克環氧樹脂ecN-1299、 36克環氧樹脂K126於反應瓶内’並在9〇。(：油浴中以機械 18 201020291 a. / w^vTW 29307twf.doc/ii 攪拌混合均勻。接著將油浴降溫至5(rc後加入5phr陽離 子起始劑CD1012、1.25phr自由基起始劑iRGACURE 184、1.25phr自由基起始劑irgaCURE 819 ’並均勻擾拌， 降至室溫後以三滾筒研磨機研磨二次。接著將配方塗佈成 厚度約ΙΟΟμπι之薄膜後，以365nm汞燈源照射紫外光 6J7cm2能量，然後以熱機械分析儀以1(rc/min的升溫速度 下里測Tg’裁切樣品成寬1公分(cm)長5cm之試片，然後 折曲180°下測試其撓曲度。另外’根據ASTM D3164 92a ® 方法，製作配方在聚亞酿胺基材上的拉伸剪切黏接強度量 測試片，並以365nm汞燈源照射紫外光6j/cm2能量，利用 雙柱式拉力機(QC Teck)在拉伸速率5mm/min下測試其對 基材的附者力’其結果如表2所示。 實例9〜11 : 依照表2所示之成分與比例以及上述實例8之方法製 備配方並進行測量，其結果如表2所示。 ❹ 比較實例4: 取40克寡分子聚合物-I、30克環氧樹脂ECN-1299、 30克環氧樹脂R301於反應瓶内，並在9CTC油浴中以機械 搜摔合均勻。接者將油洛降溫至5〇C後加入5phr陽離 子起始劑CD1012、1.25phr自由基起始劑IRGAcxjre 184、1.25phr自由基起始劑IRGACURE 819,並均勻攪拌， 降至室溫後以三滚筒研磨機研磨二次。接著依照上述實例 19 29307twf.doc/n 201020291 wTable 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 Comparative Example 2 Comparative Example 3 Curtain molecule polymer 1 (%) 40 50 20 30 60 70 80 80 - 40 Epoxy tree 10% ECN- 1299 Grease (%) 30% R301 60 50 80 70 40 30 20 100 60 60% K126 Acrylate Monomer (%) • — - - - 20 - - Filler (phr) 20 20 20 20 20 20 20 20 20 - Free radical initiator (phr) 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 - 2.5 Cationic starter (phr) 5 5 5 5 5 5 5 - 5 5 Glass transfer temperature Tgu (°c) 129 123 130 129 120 105 101 60 130 125 Coefficient of thermal expansion CTE (<Tg; pm/°C) 53 55 51 53 60 61 65 110 44 52 5% weight loss temperature (°C) 330 315 331 330 311 310 301 160 375 325 Tensile shear bond strength on glass (Kgf/mm2) 102 100 101 110 98 93 95 10 50 90 Tensile shear bond strength on polyimide (KgPmm2) 103 99 90 91 100 105 105 11 30 88 FlexibilityAbility Φ X Θ Φ Φ 0 Θ Θ X 0 Water vapor transmission rate WVTR (g/m2·day) 4.6 6.0 5.4 6.7 7.1 5.8 7.3 40 8.0 16.6 8: Forty grams of an oligonucleotide molecule of the polymer -I, 24 grams of Epoxy Resin ecN-1299, 36 grams of Epoxy Resin K126 in a reaction vial 'and 9〇. (:In the oil bath, machine 18 201020291 a. / w^vTW 29307twf.doc/ii Stir well and mix. Then cool the oil bath to 5 (after adding rc 5 cation cationic initiator CD 1012, 1.25 phr free radical initiator iRGACURE) 184, 1.25 phr free radical initiator irgaCURE 819 'and evenly disturbed, and then cooled to room temperature and then ground twice with a three-roll mill. Then the formulation was applied to a film having a thickness of about ΙΟΟμπι, and then irradiated with a 365 nm mercury source. Ultraviolet light 6J7cm2 energy, and then cut the sample into a test piece with a width of 1 cm (cm) and a length of 5 cm with a thermomechanical analyzer at a temperature rise rate of 1 (rc/min), and then test the scratch at 180°. Curvature. In addition, according to the ASTM D3164 92a ® method, a tensile shear bond strength test piece prepared on a poly-anisole substrate was prepared, and the energy of 6j/cm2 was irradiated with a 365 nm mercury light source, using double The column tension machine (QC Teck) tested its adhesion to the substrate at a tensile rate of 5 mm/min. The results are shown in Table 2. Examples 9 to 11: Compositions and ratios according to Table 2 and the above The formulation of Example 8 was prepared and measured, and the results are shown in Table 2. Comparative Example 4: Take 40 g of oligo molecular polymer-I, 30 g of epoxy resin ECN-1299, 30 g of epoxy resin R301 in a reaction flask, and mechanically smash it evenly in a 9 CTC oil bath. After the oil was cooled to 5 ° C, 5 phr cationic initiator CD 1012, 1.25 phr free radical initiator IRGAcxjre 184, 1.25 phr free radical initiator IRGACURE 819 were added and uniformly stirred. Grind twice. Then follow the above example 19 29307twf.doc/n 201020291 w
，i W 8之方法測量，其結果如表2所示。 比較實例5 : 取40克募分子聚合物-I、12克環氧樹脂ECN-1299、 48克環氧樹脂EPON 828 (雙酚A型環氧樹脂，環氧當量 185-210 ’ Shell Chemical商品）於反應瓶内，並在9〇。(：油 浴中以機械攪拌混合均勻。接著將油浴降溫至5〇〇C後加入 5phr陽離子起始劑CD1012、1.25phr自由基起始劑 IRGACURE 184、1.25phr 自由基起始劑 IRGACURE 819， 並均勻攪拌，降至室溫後以三滚筒研磨機研磨二次。接著 依照上述實例8之方法測量，其結果如表2所示。 比較實施例6〜9 : 依照表2所示之成分與比例以及上述比較例4之方法 製備配方並進行測量，其結果如表2所示。 表2 \ 例8 例9 例10 例11 比 較 例 4 比 較 例 5 比 較 例 6 比 較 例 7 比 較 例 8 比 較 例 9 募分子聚合物I (%) 40 40 40 40 40 40 40 40 40 40 環 氧 樹 脂 ECN-1299(%) 24 6 30 12 30 12 24 6 - - K126(%) 36 54 30 48 - - 36 54 R301(%) - - - - 30 36 - 24 - EPON828(%) - - - - 48 - 54 6 自由基型起始劑 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2,5 20 201020291, i W 8 method measurement, the results are shown in Table 2. Comparative Example 5: 40 g of molecular polymer-I, 12 g of epoxy resin ECN-1299, 48 g of epoxy resin EPON 828 (bisphenol A epoxy resin, epoxy equivalent 185-210 'Shell Chemical) In the reaction flask, and at 9 〇. (: The oil bath was uniformly mixed by mechanical stirring. Then the oil bath was cooled to 5 ° C and then 5 phr cationic initiator CD 1012, 1.25 phr radical initiator IRGACURE 184, 1.25 phr free radical initiator IRGACURE 819 were added. The mixture was uniformly stirred, and after being cooled to room temperature, it was ground twice by a three-roll mill. Then, it was measured according to the method of the above Example 8, and the results are shown in Table 2. Comparative Examples 6 to 9: According to the composition shown in Table 2 The formulation and the method of the above Comparative Example 4 were prepared and measured, and the results are shown in Table 2. Table 2 \ Example 8 Example 9 Example 10 Example 11 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Polymer molecule I (%) 40 40 40 40 40 40 40 40 40 40 Epoxy resin ECN-1299 (%) 24 6 30 12 30 12 24 6 - - K126 (%) 36 54 30 48 - - 36 54 R301(%) - - - - 30 36 - 24 - EPON828(%) - - - - 48 - 54 6 Free radical initiator 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2,5 20 201020291
vfW 29307twf.doc/n (phr) 陽離子型起始劑 (phr) 5 5 5 5 5 5 5 5 5 5 玻璃轉移溫度Tg CC) ㊉ 0 Θ 0 Θ Φ 0 0 X X 在聚亞醢胺上之拉 伸剪切黏接強度 (Kgf/mm2) 0 0 0 0 X Θ X Θ 0 0 撓曲性 保良拉· v.nir &I Θ 0 0 ㊉ X X X X 0 0 實例12 : 取40克募分子聚合物、24克環氧樹脂ECN-1299、 36克環氧樹脂K126於反應瓶内，並在90°C油浴中以機械 擾拌混合均勻。接著將油浴降溫至5〇。〇後加入5phr陽離 子起始劑CD1012、1.25phr自由基起始劑irgacure 184、1.25phr自由基起始劑irgACURE 819，並均勻攪拌， 降至室溫後以三滾筒研磨機研磨二次。接著依照上述實例 8之方法測量拉伸剪切黏接強度以及撓曲性，其結果如表3 戶斤示。 實例13 : 取40克寡分子聚合物-Π、6克環氧樹脂ECN-1299、 54克環氧樹脂K126於反應瓶内，並在90。(：油浴中以機械 攪拌混合均勻。接著將油浴降溫至5(rc後加入5phr陽離 子起始劑CD1012、1.25phr自由基起始劑IRGACURE 184 (1- hydroxycyclohexyl phenyl ketone，Ciba 商品）、1 _25phr 自由基起始劑IRGACURE 819，並均勻攪拌，降至室溫後 21 201020291 —.....—IW 29307twf.doc/n 以二滾筒研磨機研磨二次。接著依照上述實例8之方法測 量拉伸剪切黏接強度以及撓曲性，其結果如表3所示。 比較例10 : 取40克寡分子聚合物-II、30克環氧樹脂ecN-1299、 30克壤氧樹脂R301於反應瓶内’並在90°C油浴中以機械 φ 擾拌混合均勻。接著將油浴降溫至5〇°c後加入5phr陽離VfW 29307twf.doc/n (phr) Cationic starter (phr) 5 5 5 5 5 5 5 5 5 5 Glass transition temperature Tg CC) Ten 0 Θ 0 Θ Φ 0 0 XX Pull on polyamine Extensive shear bond strength (Kgf/mm2) 0 0 0 0 X Θ X Θ 0 0 Flexibility Paula v.nir & I Θ 0 0 X XXXX 0 0 Example 12: Take 40 grams of molecular polymer 24 g of epoxy resin ECN-1299 and 36 g of epoxy resin K126 were placed in the reaction flask and mixed by mechanical disturbance in a 90 ° C oil bath. The oil bath was then cooled to 5 Torr. After the addition, 5 phr of the cationic initiator CD 1012, 1.25 phr of the radical initiator irgacure 184, 1.25 phr of the radical initiator irgACURE 819 were added, and the mixture was uniformly stirred, and after being cooled to room temperature, it was ground twice by a three-roll mill. Then, the tensile shear bond strength and the flexibility were measured in accordance with the method of the above Example 8, and the results are shown in Table 3. Example 13: 40 grams of oligo molecular polymer - hydrazine, 6 grams of epoxy resin ECN-1299, 54 grams of epoxy resin K126 were taken in a reaction flask at 90. (: Mix well in the oil bath with mechanical stirring. Then cool the oil bath to 5 (after adding rc, add 5 phr cationic initiator CD 1012, 1.25 phr radical initiator IRGACURE 184 (1-hydroxycyclohexyl phenyl ketone, Ciba commodity), 1 _25phr radical initiator IRGACURE 819, and stirred evenly, after cooling to room temperature 21 201020291 —.....—IW 29307twf.doc/n was ground twice with a two-roll mill. Then measured according to the method of Example 8 above. Tensile shear bond strength and flexibility were obtained, and the results are shown in Table 3. Comparative Example 10: 40 g of oligo molecular polymer-II, 30 g of epoxy resin ecN-1299, and 30 g of lytic resin R301 were used. Inside the reaction flask and mix it with mechanical φ in a 90 ° C oil bath. Then cool the oil bath to 5 ° ° C and add 5 phr cation
子起始劑CD1012、1.25phr自由基起始劑IRGACURE 184、l_25phr自由基起始劑IRGACURE819,並均勻攪拌， 降至室溫後以三滚筒研磨機研磨二次。接著依照上述實例 8之方法測量拉伸剪切黏接強度以及撓曲性，其結果如表3 所示。 比較例11 : 取40克寡分子聚合物-II、36克環氧樹脂K126、24 克環氧樹脂R301於反應瓶内，並在9〇°C油浴中以機械授 拌混合均勻。接著將油浴降溫至50。(：後加入5phr陽離子 起始劑CD1012、1.25phr自由基起始劑irgaCURE 184、 1.25phr自由基起始劑，並均勻攪拌，降至室溫後以三滾筒 研磨機研磨二次。接著依照上述實例8之方法測量拉伸剪 切黏接強度以及挽曲性’其結果如表3所示。 22 201020291 W 29307twfdoc/n 表3 \ 例12 例13 比 較 例 10 比 較 例 11 募6 >子聚合物-II (%) 40 40 40 40 環 氧 樹 脂 ECN-1299(°/〇) 24 6 30 - ._ 36 K126(°/〇) 36 54~ R301(%) - 30 24 白i (phr 7基型起始制 ) 2.5 2.5 2.5 2.5 陽離子型起始劑 (phr) 5 5 ^ 5 5 玻璃轉移溫度Tg CC) 0 Θ Θ X 在聚亞醢胺上之拉 伸剪切黏接強度 (Kgf^mm2) Φ Θ X Θ 挽曲性 I 0 0 X Φ Φ:良好；X:破裂(Broken) 由表1、表2、和表3的結果顯示以自由基陽離子型 紫外光硬化S&方，除了可以提供封止劑具有優異的阻絕水 氣能力之外’更有良好的撓曲性、基材附著力盘執性 表現。 ....... 綜令以上所述，本發明之感光性組成物包含陽離子型 起始劑以及自由基型起關，可赌感紐喊物在照光 之後所形成之封裝材料混成環氧樹脂的剛性與具有壓克力 官能基之s分子聚合物的撓曲性’使得所形成的封裝材料 不僅具有優異的阻絕水氣以及氧氣的能力，並且可提供良 好的撓曲性與基材附著力表現。因此，本發明之感光性組 成物不僅以用於—般不鐘鋼蓋或玻璃基材的封合， 以用在可撓性基材的封合。 23 201020291The initiator CD 1012, 1.25 phr radical initiator IRGACURE 184, l_25 phr radical initiator IRGACURE 819, and uniformly stirred, was cooled to room temperature and then ground twice with a three-roll mill. Then, the tensile shear bond strength and the flexibility were measured in accordance with the method of the above Example 8, and the results are shown in Table 3. Comparative Example 11: 40 g of oligo molecular polymer-II, 36 g of epoxy resin K126, and 24 g of epoxy resin R301 were placed in a reaction flask and uniformly mixed by mechanical polymerization in a 9 ° C oil bath. The oil bath was then cooled to 50. (: After adding 5 phr cationic initiator CD 1012, 1.25 phr radical initiator irgaCURE 184, 1.25 phr free radical initiator, and uniformly stirred, and then cooled to room temperature and then ground twice with a three-roll mill. The method of Example 8 measures the tensile shear bond strength and the drawability'. The results are shown in Table 3. 22 201020291 W 29307twfdoc/n Table 3 \ Example 12 Example 13 Comparative Example 10 Comparative Example 11 6 6 > -II (%) 40 40 40 40 Epoxy ECN-1299(°/〇) 24 6 30 - ._ 36 K126(°/〇) 36 54~ R301(%) - 30 24 White i (phr 7 base Type starting system) 2.5 2.5 2.5 2.5 Cationic starter (phr) 5 5 ^ 5 5 Glass transfer temperature Tg CC) 0 Θ Θ X Tensile shear bond strength on polyamidoline (Kgf^mm2 Φ Θ X Θ Flexibility I 0 0 X Φ Φ: Good; X: Broken (Broken) The results of Table 1, Table 2, and Table 3 show that the free radical cationic UV light hardens the S& Providing a sealant with excellent resistance to moisture, 'more good flexibility, substrate adhesion performance. . . . In summary, the photosensitive composition of the present invention comprises a cationic initiator and a radical-type seal, and the encapsulating material formed by the gambling stimuli after the illuminating is mixed into an epoxy. The rigidity of the resin and the flexibility of the s molecule polymer with acrylic functional groups make the formed packaging material not only have excellent resistance to moisture and oxygen, but also provide good flexibility and adhesion to the substrate. Performance. Therefore, the photosensitive composition of the present invention is used not only for sealing of a steel cover or a glass substrate but also for sealing on a flexible substrate. 23 201020291
、初兴润哪，因此 範圍所界定者為 ’然其並非用以限定 識者，在不脫離 許之更動與潤飾，因 【圖式簡單說明】 m 圖1是將本發明之感光性組成物應用於光電元件作盍 響封合劑的示意圖。 午作為 圖2是將本發明之感光性組成物應用於光電元件作為 另一種封合劑的示意圖。 【主要元件符號說明】 10'20 :基材 12 :陽極 14 :發光層 ❹ 16 :陰極 18 :封止劑 24In the beginning, the scope is defined as 'there is not used to limit the sensible, and it does not deviate from the change and retouching of the Xu, because [simplified illustration] m Figure 1 is the application of the photosensitive composition of the present invention A schematic diagram of a photovoltaic element as a squeaking sealant. Fig. 2 is a schematic view showing the application of the photosensitive composition of the present invention to a photovoltaic element as another sealing agent. [Main component symbol description] 10'20: Substrate 12: Anode 14: Light-emitting layer ❹ 16: Cathode 18: Blocking agent 24