TWI323735B - A silicone compound and application thereof - Google Patents
A silicone compound and application thereof Download PDFInfo
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1323735 九、發明說明: 【發明所屬之技術領域】 本發明係關於一種矽酮化合物及其組合物,其係應用 於電子/光電/光學元件中的基板、接著劑、光波導、鏡片、 保S蔓膜及封裝材料等該組合物硬化後具有良好的透明度、 低線膨脹係數’高硬度和高耐熱性’尤其適用於發光二極 • 體(LED)之封裝。 【先前技術】 為了因應電子/光電/光學產品輕薄短小之需求,目前許 • 多研究投入如何提升該類產品中具对熱性及透光性元件之 技術開發。 以LED封裝材料為例,從實際應用的角度來看,安裝 使用簡單、體積相對較小的大功率led元件必將在大部分 # 照明應用中取代傳統的小功率LED元件,小功率LED組成 鲁&照日月燈具為了達到照明的需要,必須集中許多個LED的 光能以達到照明的設計需求,其缺點是線路複雜,散熱不 易,為了平衡各個LED間的電流電壓關係必需設計複雜的 供電電路,相比之下,大功率LED元件遠大於小功率lED 元件的總合,其供電線路相對簡單,散熱結構完善,物理 特性穩定,因此,大功率LED元件的功率代替小功率led 元件成為半導體照明元件是必然的趨勢。對於大功率led 元件的封裝方法,不能簡單套用傳統小功率_ 裝方法和封裝材料,大耗散功率、大發熱量、高$光效率 5 P02940051TW(本所案號 〇5P〇5 i8) 1323735 =見有的封裝材料、封裝設備和封裝工藝提出了更高的要 環氧件的封裝材料以環氧樹脂為主流, 電氣性質、物理性質,對金屬接著性 但—般常用於大功率led或部分白光led元件 r其遇高熱或uv時容易變黃劣化,影響元件出 ,以财熱性和uv性較佳之石夕酮樹脂取代,但 妹差接紐、⑽脹係數太大、硬度差等缺 •ΓΛ、利號US6,632,892,其中該咖封裝材料組成物 工拿取二t結構為㈣化合物’由於該化合物硬度低,加 仆人物π ·+,且其線膨脹係數大,在溫度產生變化時,該1323735 IX. Description of the Invention: [Technical Field] The present invention relates to an anthrone compound and a composition thereof, which are applied to a substrate, an adhesive, an optical waveguide, a lens, and a security in an electronic/optoelectronic/optical element. The composition such as vine film and encapsulating material has good transparency, low linear expansion coefficient 'high hardness and high heat resistance', and is particularly suitable for the package of light-emitting diodes (LEDs). [Prior Art] In response to the demand for light/small electronic/optoelectronic/optical products, many research efforts have been made to improve the technical development of thermal and transmissive components in such products. Taking LED packaging materials as an example, from the point of view of practical application, high-power LED components with simple installation and relatively small volume will replace traditional low-power LED components in most lighting applications. In order to meet the needs of lighting, it is necessary to concentrate the light energy of many LEDs to meet the design requirements of lighting. The disadvantage is that the wiring is complicated and the heat dissipation is not easy. In order to balance the current-voltage relationship between the LEDs, it is necessary to design a complicated power supply. In contrast, high-power LED components are much larger than the sum of low-power lED components. The power supply circuit is relatively simple, the heat dissipation structure is perfect, and the physical characteristics are stable. Therefore, the power of high-power LED components replaces the low-power LED components into semiconductors. Lighting components are an inevitable trend. For the packaging method of high-power LED components, it is not easy to apply the traditional low-power method and packaging materials, large dissipated power, large heat, high light efficiency 5 P02940051TW (the case number 〇5P〇5 i8) 1323735 = see Some packaging materials, packaging equipment and packaging processes have proposed higher epoxy resin packaging materials with epoxy resin as the mainstream, electrical properties, physical properties, metal adhesion but generally used for high-power led or partial white light Led element r is prone to yellowing deterioration when it encounters high heat or uv, affecting the component, and is replaced by the lithene resin which is better in heat and uv, but the difference is too large, the expansion coefficient is too large, the hardness is poor, etc. U.S. Patent No. 6,632,892, wherein the coffee encapsulating material composition takes the structure of the two t structures as (4) the compound 'since the hardness of the compound is low, the servant character π ·+, and the coefficient of linear expansion is large, when the temperature changes, The
封二:变化大。曰本專利號JP61_127723,其中該[ED 物之矽酮系化合物之極性和表面能均低,與 间樹脂兩者不相容、混摻不易,且為增加其相 必?先加以改質;因此’為改善上述習知封裝材料 难从:I明開發一種石夕酉同化合物及其組成物,以改善 :統:剩樹脂和環氧樹脂之缺點,且兼具兩者之優點,實 屬必要。 、 【發明内容】 一有鑑於科學技術和生活機能不斷進步,電子、光電及 光學產品具有輕薄短小的需求,因此電子、光電及光學元 件之耐熱性標準持續提升,而光電及光學元件對於在高溫 或UV照射條件下,其透光率也被要求維持一定水準,本發 明之目的在於提供一種矽酮化合物,其係以分子鏈末端或 側鏈含Si-H官能基之石夕_化合物(silic〇ne)為主體結構與 含一個不飽和官能基和二個環氧官能基之異氰尿酸酯^ P02940051TW(本所案號 05P0518) 6 1323735 (isocyanurate)化合物反應,得到具有環氧官能基之石夕酮化合 物,該化合物為無色透明之液體。 σ 本發明之另一目的係提供一種具有光及/或熱硬化特性 之組合物’應用於電子/光電/光學元件中的基板、接著劑、 光波導、鏡片、保護膜及封裝材料等,該組合物硬化後具 有良好的透明度、低線膨脹係數、高硬度和高耐熱性,尤 其適用於發光二極體(LED)之封裝。Seal 2: The change is big.曰Patent No. JP61_127723, wherein the [the ketone-based compound of the ED has low polarity and surface energy, is incompatible with the inter-resin, is not easy to mix, and is necessary to increase it? Firstly, it has been upgraded; therefore, it is difficult to improve the above-mentioned conventional packaging materials: I Ming developed a compound and its composition to improve the defects of the resin and epoxy resin, and both The advantages are really necessary. [Invention] In view of the continuous advancement of science and technology and living functions, the demand for electronic, optoelectronic and optical products is light and thin, so the heat resistance standards of electronic, optoelectronic and optical components continue to increase, while the photoelectric and optical components are at high temperatures. Or under UV irradiation conditions, the light transmittance is also required to maintain a certain level. The object of the present invention is to provide an anthrone compound which is a Siic-containing compound having a Si-H functional group at the end of a molecular chain or a side chain (silic) 〇ne) is a main structure with an unsaturated functional group and two epoxy functional groups of isocyanurate ^ P02940051TW (Our Office No. 05P0518) 6 1323735 (isocyanurate) compound to obtain an epoxy functional group An amine compound which is a colorless, transparent liquid. σ Another object of the present invention is to provide a composition having optical and/or thermosetting properties, a substrate, an adhesive, an optical waveguide, a lens, a protective film, a packaging material, and the like applied to an electronic/optoelectronic/optical element. The composition has good transparency, low coefficient of linear expansion, high hardness and high heat resistance after hardening, and is particularly suitable for packaging of light-emitting diodes (LEDs).
為達上述目的,本發明係提供一種矽酮化合物,其化 學式如(I)所示:In order to achieve the above object, the present invention provides an anthrone compound having a chemical formula as shown in (I):
II
fi—0jSi—oj-Si—r5 B R2 m (i);fi—0jSi—oj-Si—r5 B R2 m (i);
其中,m、n係為〇或正整數,但m、n不同時為0;!^、 R2、R3、Κ·4、R5、A及B係獨立為氮、鹵素、未取代之Ci 〜C6之直鏈或具支鏈之烷基、環烷基或烷氧基、以齒素取 代之(^〜(:6之直鏈或具支鏈之烷基、環烷基或烷氧基、未 取代或以齒素取代之芳香基、未取代或以鹵素取代之雜芳 香基或如化學式(H)所示之取代基Wherein m and n are 〇 or a positive integer, but m and n are not 0 at the same time; !^, R2, R3, Κ·4, R5, A and B are independently nitrogen, halogen, and unsubstituted Ci~C6 a straight or branched alkyl, cycloalkyl or alkoxy group, substituted with dentate (^~(: 6 straight or branched alkyl, cycloalkyl or alkoxy, un An aromatic group substituted or substituted with dentate, a heteroaryl group which is unsubstituted or substituted with a halogen or a substituent represented by the formula (H)
其中R6係獨立為氫、鹵素、未取代之(^〜(:6之直鏈或 7 P02940051TW(本所案號 05P0518) 具支鏈之烷基、環烷基或烷氧基、以鹵素取代之(^〜(^之 直鏈或具支鏈之炫基、環炫基或炫氧基、未取代或以鹵素 取代之芳香基、未取代或以齒素取代之雜芳香基; R7係獨立為未取代之c〇〜c6之直鏈或具支鏈之烷基、 環烧基或烧氧基、以_素取代之c〇〜c6之直鏈或具支鏈之 烷基、環烷基或烷氧基、未取代或以鹵素取代之芳香基、 未取代或以鹵素取代之雜芳香基或羧基。 前述化學式(I)之A與B至少一為前述化學式(II)所示之 取代基。 本發明另提供一種具有光及熱硬化特性之組合物,其 係包含:100重量份之前述矽酮化合物;及一反應促發劑。 於本發明之一較佳實施例中,前述具有光及/或熱硬化 特性之組合物可進一步包含0.1〜9900重量份之環氧化合 物。 於本發明之另一較佳實施例中,前述具有光及熱硬化 特性之組合物係可進一步包含一添加劑,其中前述添加劑 為界面活性劑(例如:消泡劑、平坦劑)、染顏料、可塑 劑、熱安定劑、UV安定劑、折射率調控劑、密著賦予 劑、溶劑、化學式(I)以外之環氧樹脂或其混合物。 本發明之一較佳實施例,其中該反應促發劑係為熱硬 化劑,包含胺類化合物、酸類化合物、酚類化合物、醇 類化合物、酸無水物化合物、醯胺化合物、硫醇化合物、 三氟化硼胺複合物、腺酯(urethane)化合物、異氰酸鹽 (isocyanunate)化合物或其混合物。 本發明之另一較佳實施例’其中該反應促發劑係為光 硬化起始劑’其中包含芳香烴基二重氮銨鹽 (aryldiazonium salts)、二芳香烴基碘銨鹽 P02940051TW(本所案號 05P0518) g 1323735 (diaryliodonium salts)、三芳香煙基硫化碟敍鹽(triaryl sulphonium salts)、三芳香烴基鱗酸敍鹽 (triarylphosphonium salts)、三芳香烴基亞砸錢鹽 (triarylselenonium salts)、二烧基苯酿甲基硫化填銨鹽 (dialkylphenacylsulphonium salts)、二炫基-4-經基苯硫 化稱敍鹽(dialkyl-4-hydroxyphenylsulphonium salts)、硫 化填酸酷(sulphonic acid ester)、石夕醇基-铭錯合物、 (silanol-aluminium complexes) 二茂鐵敍鹽 _ (Ferrocenium salts)或其混合物。 1 本發明之另一較佳實施例,其中該反應促發劑係可添 加一觸媒促進反應,其中該觸媒包含胺類化合物、咪唑化 合物(imidazole)、芳香族羥基(aryl) or烷磷(alkyl phosphonium)化合物、四丁基漠化敍(tetrabutyl ammonium bromide) 、 2-甲基-4-咪 唾 (2-methyl-4-imidazole)、三苯(基)膦(triphenyl phosphine)、苯甲基二曱胺(benzyldimethylamine)、三乙 醇胺(triethanolamine)或其混合物。 P 本發明提供一種矽酮化合物及一種具有光及熱硬化特 性之組合物’利用導入ί哀氧基團配製成熱硬化及/或光硬化 組合物,其具有加強硬度、提高玻璃轉化溫度、降低線膨 張係數之優點’並利用導入異氰尿酸g旨類(isocyanurate)基團 大幅提升該組合物之耐熱性及耐候性,相較於習知技術, 本發明之方法係具有較佳之加工性及透光性,有效改善習 知技術之缺失與弊端’其適用於光學/光電產品之應用材料。 【實施方式】 本發明提供一矽酮化合物,及一含該化合物之具熱/光 P02940051TW 体所案號 〇5P〇518) 9 1323735 硬化特性之組合物,該組合物可應用於電子/光電/光學元件 中的基板、接著劑、光波導、鏡片、保護膜、封裝材料等, 尤其適用於發光二極體(led)封裝。此組成物硬化後具有良 好的透明度'低線膨脹係數、高硬度及高耐熱性。前述含 石夕酮化合物之組成物含有:(A)矽酮化合物:該矽酮化合物 係以分子鏈末端或側鏈含Si-H官能基之矽酮化合物 (silicone)為主體結構,與含一個不飽和官能基和二個環氧官 能基之異氰尿酸酯類(iS〇Cyanurate)化合物反應(見下列化學 • 式(m)),藉由不飽和官能基與si-H官能基的反應鍵結後, 1 得到具有環氧官能基之矽酮化合物(見化學式;及反 應促發劑:熱硬化劑,或是光硬化起始劑。Wherein R6 is independently hydrogen, halogen, unsubstituted (^~(:6 straight chain or 7 P02940051TW (Oh. 05P0518) branched alkyl, cycloalkyl or alkoxy, substituted by halogen (^~(^ is a straight or branched chain, cyclohexyl or decyloxy, unsubstituted or halogen-substituted aromatic group, unsubstituted or heteroaryl substituted with dentate; R7 is independently Unsubstituted c〇~c6 linear or branched alkyl, cycloalkyl or alkoxy, linear or branched alkyl, cycloalkyl or An alkoxy group, an unsubstituted or halogen-substituted aryl group, an unsubstituted or halogen-substituted heteroaryl group or a carboxyl group. At least one of A and B of the above formula (I) is a substituent represented by the above formula (II). The present invention further provides a composition having light and heat hardening properties, comprising: 100 parts by weight of the aforementioned anthrone compound; and a reaction triggering agent. In a preferred embodiment of the present invention, the foregoing light and The composition of the thermosetting property may further comprise from 0.1 to 9900 parts by weight of the epoxy compound. In a preferred embodiment, the composition having optical and thermosetting properties may further comprise an additive, wherein the additive is a surfactant (for example, an antifoaming agent, a flat agent), a dye, a plasticizer, a thermal stabilizer, a UV stabilizer, a refractive index regulator, a adhesion imparting agent, a solvent, an epoxy resin other than the chemical formula (I), or a mixture thereof. A preferred embodiment of the present invention, wherein the reaction accelerator is a thermal hardener, Containing amine compounds, acid compounds, phenolic compounds, alcohol compounds, acid anhydride compounds, guanamine compounds, thiol compounds, boron trifluoride amine complexes, urethane compounds, isocyanurate A compound or a mixture thereof. Another preferred embodiment of the present invention, wherein the reaction triggering agent is a photohardening initiator, which comprises an aromatic hydrocarbon aryldiazonium salt, a diaryl hydrocarbon iodide salt P02940051TW (Our Office No. 05P0518) g 1323735 (diaryliodonium salts), triaryl sulphonium salts, triaryl sulfonate (triarylphosphonium salts), triarylselenonium salts, dialkylphenacylsulphonium salts, disulfo-4-alkylbenzene sulfides (dialkyl-4) -hydroxyphenylsulphonium salts), sulphonic acid esters, silanol-aluminium complexes, ferroceneium salts or mixtures thereof. 1 Another preferred embodiment of the present invention, wherein the reaction stimulating agent is capable of adding a catalyst-promoting reaction, wherein the catalyst comprises an amine compound, an imidazole, an aromatic aryl or an alkane phosphorus. (alkyl phosphonium) compound, tetrabutyl ammonium bromide, 2-methyl-4-imidazole, triphenyl phosphine, benzo Benzyldimethylamine, triethanolamine or a mixture thereof. P The present invention provides an anthrone compound and a composition having photohardening properties, which are formulated into a thermosetting and/or photohardening composition by using a chelating oxygen group, which has enhanced hardness, increased glass transition temperature, The advantage of lowering the coefficient of linear expansion is 'to improve the heat resistance and weather resistance of the composition by introducing an isocyanurate group. The method of the present invention has better processability than the prior art. And light transmission, effectively improving the lack of drawbacks and drawbacks of the prior art 'its application materials for optical / optoelectronic products. [Embodiment] The present invention provides a fluorenone compound, and a composition containing the compound having a hardening property of heat/light P02940051TW, No. 5P〇518) 9 1323735, which can be applied to electronic/photoelectric/ The substrate, the adhesive, the optical waveguide, the lens, the protective film, the encapsulating material and the like in the optical element are particularly suitable for a light emitting diode (LED) package. This composition has good transparency after hardening 'low linear expansion coefficient, high hardness and high heat resistance. The composition containing the above-mentioned alkaloid compound contains: (A) an anthrone compound: the anthrone compound is a main structure having a Si-H functional group-containing ketone compound at the end of the molecular chain or a side chain, and Reaction of an unsaturated functional group with two epoxy functional isocyanurate compounds (see the following chemical formula (m)), by reaction of an unsaturated functional group with a si-H functional group After the knot, 1 obtain an anthrone compound having an epoxy functional group (see chemical formula; and a reaction accelerator: a thermal hardener, or a photohardening initiator).
(ΙΠ) 以下係提供利用本發明之訾 術及特點1本實施例並非詳細說明本發明之技 技藝者,在不畴本發明之精^本發明,任何熟悉此 更動與潤飾。 和範圍内’當可作各種之 實施例 P02940051TW体所案號仍哪 1323735 眚施例一:矽酮化合物1之劁備 將1-丙稀基-3,5-環氧甘油醚異氰尿酸酯、少許pt觸媒、 含Si-H官能基之石夕酮化合物k(Si-H濃度0.694(10 2 mol/g) ’黏度15~20cps)及溶劑甲苯(toluene) ’置於單口反應 瓶中,以110°C迴流反應,持續反應4小時,取樣測FT-IR, 確定Si-H官能基波峰2140cm·1消失,之後減壓濃縮得石夕酮 化合物1,如下列表一所示。 土轉例一:矽酮化合物2之劐備 同實施例一之合成步驟,以先前技藝之丙烯基縮水甘油 醚(Allyl glycidyl ether)加上少許Pt觸媒、含Si-H官能基之 石夕嗣化合物h(Si-H濃度0.694(10 2 mol/g) ’黏度15〜20cps) 及溶劑甲苯,置於單口反應瓶中,以110°c迴流反應,持續 反應4小時’取樣測FT-IR,確定Si-H官能基波峰2140cm-i 消失’之後減壓濃縮得石夕酮化合物2為本發明組合物之實 驗對照組,如下列表一所示。 f施例二:矽酮化合物3之製備 將1-稀丙基-3,5-環氧甘油異氰尿酸g旨、少許pt觸媒、 含Si-H官能基之石夕酮化合物边(Si-H濃度〇.528(10·2 mol/g) ’黏度10〜13cps)及溶劑甲苯,置於單口反應瓶中, 以110°C迴流反應’持續反應4小時,取樣測FT_IR,確定 Si-H官能基波峰2140CHT1消失’之後減壓濃縮得石夕酮化合 物3 ’如下列表一所示。 11 P02940051TW(本所案號 05P0518) 1323735(ΙΠ) The following is a description of the invention and the features of the present invention. The present invention is not intended to be a detailed description of the present invention. And in the range 'When it can be used as a variety of examples P02940051TW body number is still 1323735 眚 Example 1: ketone compound 1 preparation of 1-propanyl-3,5-epoxyglyceryl ether isocyanuric acid Ester, a little pt catalyst, Si-H functional group-containing oxalyl compound k (Si-H concentration 0.694 (10 2 mol/g) 'viscosity 15~20 cps) and solvent toluene (toluene) placed in a single-mouth reaction bottle The reaction was refluxed at 110 ° C for 4 hours, and FT-IR was sampled to confirm that the Si-H functional group peak disappeared at 2140 cm·1, and then concentrated under reduced pressure to obtain the oleanone compound 1, as shown in the following Table 1. Soil rotation example 1: Anthraquinone compound 2 is prepared in the same manner as in the first embodiment, using the prior art Allyl glycidyl ether plus a little Pt catalyst, Si-H functional group嗣Compound h (Si-H concentration 0.694 (10 2 mol / g) 'viscosity 15~20cps) and solvent toluene, placed in a single-mouth reaction flask, reflux reaction at 110 ° C, continuous reaction for 4 hours 'sampling FT-IR It was confirmed that the Si-H functional group peak 2140 cm-i disappeared, and then concentrated under reduced pressure to obtain the oleanone compound 2 as an experimental control group of the composition of the present invention, as shown in the following Table 1. f Example 2: Preparation of anthrone compound 3 1-propyl-3,5-epoxyglyceryl isocyanuric acid g, a little pt catalyst, Si-H functional group-containing oxalate compound side (Si -H concentration 〇.528 (10·2 mol/g) 'viscosity 10~13 cps) and solvent toluene, placed in a single-mouth reaction flask, refluxing at 110 ° C 'continuous reaction for 4 hours, sampling FT_IR, determining Si- The H functional base peak 2140CHT1 disappeared and then concentrated under reduced pressure to give the oxazolone compound 3' as shown in the following Table 1. 11 P02940051TW (Our Office Case 05P0518) 1323735
表一.石夕酮化合物合成成分與性質表 8 化合物1 化合物2 化合物3 含SiH官 能基梦網 化合物 矽酮化合物Si-H 濃度 〇.694(10·2 mol/g),黏度 15~20cps 10 10 石夕酮化合物边:Si-H 濃度 0·528(10·2 mol/g),黏度 10~13cps 10 含C=C和 epoxy官能 基之化合 物 1-丙烯基-3,5-環氧甘 油醚異氰尿酸酯 (l-allyl-3,5-diglycid yl- isocyanurate) 19.5 18 丙烯基縮水甘油醚 (Allyl glycidyl ether) - 8.3 - 溶劑 甲笨(toluene) 30 13.3 14 改質後環氧當量值(EEW) 248 244 282 熱劣解溫度 7d(weight loss 5%) 340 254 356 註:熱劣解溫度由熱重分析儀分析(TGA)而得。由20。(:升溫至850t,升 溫速率20°C/min,空氣氣氛中。 比較矽酮化合物1、2和3的熱劣解溫度,矽酮化合物1 和3比矽酮化合物2(對照組)分別提高86°c及102。〇。可知 本發明以1-丙烯基-3,5-環氧甘油醚異氰尿酸酯改質之矽酮 化合物其耐熱性比一般丙烯基縮水甘油醚(allyl glycidyl ether)改質者優良。 實施例三:含石夕酮化合物1之纟a合物 將矽酮化合物1與環氧樹脂:雙酚環氧甘油醚(bisphen〇1A diglycidyl ether) (EPON 828),依不同重量比例 1/1〇、1/5、 12 P02940051TW(本所案號 05P0518) 1323735 1/1、5/1、10Π混合,加上相同當量數的酸酐化合物:甲基 六氫苯酐(methylhexahydrophthalic anhydride,MeHHPA)與 0.1 wt%觸媒:四丁基漠化敍(tetrabutyl ammonium bromide, TBAB)混合均勻,組成成分如表二所示。 實施例四:含石夕酮化合物1之組合物 同實施例三之混合步驟,將矽酮化合物1與環氧樹脂 hydrogenated bisphenol A diglycidyl ether (HBPA) ’ 依不同重 量比例1/10、1/5、1/1、5/1、10/1混合,加上相同當量數 的酸酐化合物:曱基六氫苯酐(MeHHPA)與0.1 wt%觸媒:四 丁基溴化銨(TBAB)混合均勻,組成成分如表二所示。 實施例五:含碎嗣化合物3之組合物 將0·9 g石夕蜗化合物 3、0.1 g環氧樹脂 EpoxyCyclohexylPOSS®(EP0408,Hybrid Plastics)、0.05 g 光起始劑UVI-6976 (Dow Chemical)輿少許溶劑混合均勻, 旋轉塗佈在玻璃上,以UV曝光機曝光500mJ/cm2,接著以 150°C烘烤lhr,測得硬化物之玻璃轉化溫度rg為138°C。 比較例二:含妙酮化合物2之組合物 同上述實施例三之混合步驟,將矽酮化合物2與環氧樹 脂 hydrogenated bisphenol A diglycidyl ether (HBPA),依不 同重量比例1/10、1/5、1/1、5/1、10/1混合,加上相同當 量數的酸酐化合物:甲基六氫苯酐(MeHHPA)與0.1 wt%觸 媒:四丁基溴化銨(TBAB)混合均勻,如表二所示。 表二.組成物成分表 P02940051TW(本所案號 05P0518) 1323735 混合系統 號 實施例三 石夕酮化合物 1 / bisphenol A diglycidyl ether (EPON 828) 實施例四 石夕酿I化合物 1 / hydrogenated bisphenol A diglycidyl ether (HBPA) 比較例二 石夕酮化合物 2 / hydrogenated bisphenol A diglycidyl ether (HBPA) :; f施例六:本發明之石夕酮化合物之物理性質比較 將實施例三、四及比較例二之各混合組合物以120¾, 2小時;150°C ’ 2小時二段加熱硬化後,其硬化物測得硬 度、玻璃轉化溫度(rg)、線膨脹係數(CTE)、透光率結果如 第一圖至第四圖所示。 由第一圖可知組合物配方中,添加矽酮化合物1不會降 低硬度。>5夕酮化合物2添加比例增加時,硬化組成物硬度 則是呈現下降趨勢。 由第二圖可知組合物配方中,添加石夕酮化合物1可以提 汁玻璃轉化溫度,尤其以silicone/epoxy=l:1時效果最佳, 達到135°C。矽酮化合物2之硬化組合物系列,其玻璃轉化 溫度只有7(TC左右。 由第三圖可知組合物配方中,添加矽酮化合物1可維持 極小的線膨脹係數,小於80ppm/°C。石夕酮化合物2添加比 例增加時’硬化組合物線膨脹係數則是呈現大幅增加的趨 勢。 由第四圖可知硬化組合物配方中(實施例三、四中 silicone/ epoxy=l :5),可見光波長(400〜700nm)區域中,透光 率均大於80%以上,因此使用本發明之組合物配方其透明 14 P02940051TW(本所案號 〇5P〇518) 度良好。 物,及一::兮:車父於先前技藝’本發明之-種矽酮化合 其具有較佳:1化合物之具熱/光硬化特性之組合物, 與弊端,使性錢紐’有狀知技術之缺失 使其適用於光學/光電產品之應用材料。 其他實施態樣 太枯if明之實施方法已詳述於前述實施例中,任何孰染 之人士皆可依本發明之說明,在不背離:;·; 申,圍内視需要更動、修飾本發 4 亦包含在本發明之申請專利中。 /、他貫 限定本發以較佳實施例揭露如上,然其並非用以 和A可热悉此技藝者,在不脫離本發明之精神 和乾圍内,當可祚久;丁 圊,更動與潤飾,因此,本發明之保 邊祀圍虽視後附之申請專利範圍所界定者為準。 【圖式簡單說明】 弟圖係為本發明之硬度與silicone/epoxy化合物組成 關係圖。 第一圖係為本發明之玻璃轉化溫度與silicone/epoxy化 合物組成關係圖。 第二圖係為本發明之線膨脹係數與silicone/epoxy化合 物組成關係圖。 第四圖係為本發明之實施例三及四之組合物透光率結 果圖。 【主要元件符號對照說明】 P0294〇051TW(本所案號 Q5P0518) 15Table 1. Synthetic components and properties of the compound. Table 8 Compound 1 Compound 2 Compound 3 SiH-containing compound Mengnet compound anthrone compound Si-H Concentration 〇.694 (10·2 mol/g), viscosity 15~20cps 10 10 oxalate compound side: Si-H concentration 0·528 (10·2 mol/g), viscosity 10~13cps 10 Compound containing C=C and epoxy functional group 1-propenyl-3,5-epoxyglycerol L-allyl-3,5-diglycidyl-isocyanurate 19.5 18 Allyl glycidyl ether - 8.3 - solvent toluene 30 13.3 14 modified epoxy Quantities (EEW) 248 244 282 Thermal loss temperature 7d (weight loss 5%) 340 254 356 Note: The thermal decomposition temperature is obtained by thermogravimetric analysis (TGA). By 20. (: heating up to 850t, heating rate 20 °C / min, in air atmosphere. Comparing the thermal inferior temperature of the fluorenone compounds 1, 2 and 3, the fluorenone compounds 1 and 3 are higher than the fluorenone compound 2 (control group) 86 °c and 102. 〇. It is known that the ketone compound modified with 1-propenyl-3,5-epoxyglyceryl ether isocyanurate has heat resistance higher than that of general allyl glycidyl ether. The modifier is excellent. Example 3: The oxime compound containing the oleanone compound 1 and the epoxy resin: bisphen 〇 1A diglycidyl ether (EPON 828), Different weight ratios 1/1〇, 1/5, 12 P02940051TW (Our Case No. 05P0518) 1323735 1/1, 5/1, 10Π mixed, plus the same equivalent number of anhydride compounds: methylhexahydrophthalic anhydride , MeHHPA) and 0.1 wt% of the catalyst: tetrabutyl ammonium bromide (TBAB) is uniformly mixed, and the composition is shown in Table 2. Example 4: Composition containing the compound of the linalone 1 Three mixing steps, anthrone compound 1 and epoxy resin hydrogenated bisph Enol A diglycidyl ether (HBPA) 'According to different weight ratios of 1/10, 1/5, 1/1, 5/1, 10/1, plus the same equivalent number of anhydride compounds: mercapto hexahydrophthalic anhydride (MeHHPA) It is uniformly mixed with 0.1 wt% catalyst: tetrabutylammonium bromide (TBAB), and the composition is shown in Table 2. Example 5: The composition containing the mash compound 3 will be 0.9 g of the compound 3. 0.1 g epoxy resin EpoxyCyclohexylPOSS® (EP0408, Hybrid Plastics), 0.05 g photoinitiator UVI-6976 (Dow Chemical), mixed with a small amount of solvent, spin coated on glass, exposed to 500 mJ/cm2 with a UV exposure machine, then After baking at 150 ° C for 1 hr, the glass transition temperature rg of the cured product was measured to be 138 ° C. Comparative Example 2: Mixing procedure of the composition containing the ketone compound 2 and the above Example 3, the fluorenone compound 2 and the ring Oxygenated resin bisphenol A diglycidyl ether (HBPA), mixed in different weight ratios of 1/10, 1/5, 1/1, 5/1, 10/1, plus the same equivalent number of anhydride compounds: methyl hexahydrophthalic anhydride (MeHHPA) is uniformly mixed with 0.1 wt% catalyst: tetrabutylammonium bromide (TBAB), as shown in Table 2. Table 2. Composition Composition Table P02940051TW (Originary Case No. 05P0518) 1323735 Mixing System No. Example Example 3 bisphenol A diglycidyl ether (EPON 828) Example 4: hydrogenated bisphenol A diglycidyl ether (HBPA) Comparative Example 2: hydrogenated bisphenol A diglycidyl ether (HBPA):; f. Example 6: Comparison of physical properties of the compound of the present invention. Each of Examples 3, 4 and Comparative Example 2 The mixed composition was cured by heat treatment at 1203 ° C for 2 hours and 150 ° C for 2 hours. The hardness, glass transition temperature (rg), coefficient of linear expansion (CTE), and light transmittance of the cured product were as shown in the first figure. As shown in the fourth figure. It can be seen from the first figure that the addition of the anthrone compound 1 does not reduce the hardness in the composition formulation. When the proportion of the addition of the ketone compound 2 is increased, the hardness of the hardened composition tends to decrease. It can be seen from the second figure that the addition of the linaloxone compound 1 can increase the glass transition temperature, especially when the silicone/epoxy=l:1 is used, and the effect is 135 °C. The hardening composition series of the anthrone compound 2 has a glass transition temperature of only about 7 (TC). It can be seen from the third figure that the addition of the anthrone compound 1 maintains a very small coefficient of linear expansion, less than 80 ppm/° C. When the proportion of the addition of the ketone compound 2 is increased, the coefficient of linear expansion of the hardened composition tends to increase greatly. From the fourth figure, it is known that the composition of the hardened composition (silicone/epoxy=l:5 in Examples 3 and 4), visible light In the wavelength (400 to 700 nm) region, the light transmittance is more than 80% or more, so that the composition of the present invention is transparent to 14 P02940051TW (the case number 〇5P〇518). The object, and one::兮: The car father in the prior art 'the present invention - the ketone ketone compound has a better: 1 compound of the composition with thermal / photohardening properties, and the drawbacks, so that the lack of knowledge of the technology Application materials for optical/optoelectronic products. Other implementations are too detailed. The method of implementation has been described in detail in the foregoing embodiments, and any person who is infected can follow the instructions of the present invention without departing from the following: Need for internal vision The present invention is also included in the patent application of the present invention. The present invention is disclosed in the preferred embodiments as described above, but it is not intended to be used in conjunction with A, without departing from the invention. In the spirit and the dry circumference, it can be long-lasting; Ding Wei, change and retouch, therefore, the Bianbianwei of the present invention is subject to the definition of the patent application scope attached. [Simple description of the schema] It is the relationship between the hardness of the invention and the composition of the silicone/epoxy compound. The first figure is the relationship between the glass transition temperature and the composition of the silicone/epoxy compound of the present invention. The second figure is the linear expansion coefficient of the invention and the silicone/epoxy The composition diagram of the compound composition. The fourth figure is the result of the transmittance of the composition of the third and fourth embodiments of the present invention. [Comparative description of the main components and symbols] P0294〇051TW (the case number Q5P0518) 15
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