200806765 (1) 九、發明說明 【發明所屬之技術領域】 本發明係有關耐光性底層塗料組成物，使用該底層塗 料組成物之發光半導體裝置的製造方法，及由該方法所得 發光半導體裝置以及使用該底層塗料組成物之發光半導體 裝置。 I 【先前技術】 藉由發光一極體之局亮度、高輸出功率化，構成發光 二極體之封裝材料、密封材料等之材料截至目前爲止，處 於更大之光•熱的負荷。近年來，廣泛使用聚矽氧樹脂之 耐久性高的材料做爲高輸出功率發光二極體（led)之密封 樹脂。惟，爲搭載LED之封裝係由金屬、半導體材料等 複數種材料所成，密封樹脂材料務必具與其各種材料之黏 著信賴性。又LED驅動時之光照射與高溫下有引起底層 φ 塗料層之變色、由LED之光取出效率降低的問題。又， 含高活性化合物之底層塗料，其塗佈處理時間受限，導致 生產作業面產生問題點。爲解決此等問題，目前爲止亦有 有關矽醇縮合觸媒、矽烷偶合劑之組合所成之底層塗料之 • 報告例（專利文獻1、2)，惟對於LED之底層塗料塗佈作 業性，黏著信賴性與耐變色性之三者兼具的底層塗料並未 記載。 [專利文獻1]特開2004-3 39450 [專利文獻2]特開2005-093724 200806765 (2) 【發明內容】 因此，本發明之課題係提供一種具良好的塗佈作業性 ，密封樹脂與基材之黏著信賴性高，對於光照射、加熱具 有高度耐變色性之底層塗料材料。 又，本發明之課題亦提供一種藉由使用此底層塗料組 成物後製造更高性能之發光半導體裝置之方法。 本發明者爲解決該課題，進行精密硏討後結果發現， φ 組合路易斯酸之有機鋁化合物與特定之矽烷偶合劑及有機 溶劑後，可解決上述課題，進而完成本發明。 亦即，做爲解決上述課題之手段，本發明第1係提供 含有（A)下述一般式（1) R1xR2ySi(R3)4-X-Y …（1) (式中，R1及R2代表獨立地氫原子、或具有1個以上反應 φ 性取代基亦可之碳原子數1〜3 0之烷基，R3代表氯原子、 羥基或碳原子數1〜30之非取代或取代之烷氧基或芳氧基 ，X爲1〜2之整數、Y爲0〜1之整數，χ + γ爲1或2之整 數） * 所示之至少1種矽烷化合物及/或此等之部份水解縮合物 (B) 路易斯酸性之有機鋁化合物、以及 (C) 有機溶劑、 所成之底層塗料組成物。 -6 - 200806765 (3) 本發明第2係提供其特徵爲使底層塗料組成物塗佈於 預成型封裝上所裝置之發光半導體元件表面後，乾燥之後 ，形成被覆該發光半導體元件表面之底層塗料組成物層， 於該底層塗料組成物層上適用加成反應硬化型聚矽氧後， 使該元件進行外模成形之樹脂密封。 •使用本發明底層塗料組成物後，可改善底層塗料塗佈 ，乾燥步驟可利用之時間，提昇作業性，可提昇密封樹脂 φ 對於基材之黏著信賴性。且底層塗料組成物之塗佈層由於 具有化學性、物理穩定性，因此即使於元件點燈時所產生 之高溫•光照射條件下其底層塗料層仍具有耐變色性。由 此特定可實現長壽命且信賴性高之發光半導體裝置。 【實施方式】 以下，進行本發明更詳細之說明。 φ [底層塗料組成物] [(A)矽烷偶合劑] 做爲（A)成份使用者係一般式〇): R1xR2YSi(R3)4 x γ …⑴ (式中，R1及R2代表獨立地氫原子、或具有1個以上反應 性取代基亦可之碳原子數U0、較佳爲2〜30、更佳爲 2〜1 5之烷基’ R3代表氯原子、羥基或碳原子數1〜30之非 200806765 (4) 取代或取代之烷氧基或芳氧基，X爲1〜2之整數、Y爲 0〜1之整數，Χ + Υ爲1或2之整數） 所示之至少1種矽烷化合物及/或此等之部份水解縮合物 〇 又，R1、R2不同時爲氫原子（亦即，R1、R2中至少1 方爲具有1個以上之反應性取代基亦可之碳原子數2〜30 之烷基）者宜。 鲁 一般式（1)中，R1與R2之兩者，或其一方爲院基時， 較佳者如：甲基、乙基、丙基、異丙基、丁基等中碳原子 數1〜1 8之烷基例。 R1或R2所示之烷基爲具有1個以上之反應性取代基 亦可。其中反應性取代基之例如··環氧基、氧雜環丁烷基 、丙烯醯氧基、甲基丙烯醯氧基、氫硫基、胺基、氰基、 異氰基之例。 更具體而言，做爲環氧基或具有環氧基之烷基例者如 % :縮水甘油基、沒-環氧丙氧基乙基、α-環氧丙氧基丙基 、/3 -環氧丙氧基丙基、r -環氧丙氧基丙基、^ -環氧丙氧 . 基丁基、卢-環氧丙氧基丁基、r-環氧丙氧基丁基、環 氧丙氧基丁基、（3，4-環氧基環己基）甲基、/3-(3,4-環氧基 環己基）乙基、r-(3,4-環氧基環己基）丙基、（5-(3,4-環氧 基環己基）丁基等例。 做爲氧雜環丁烷基之烷基例者如：（3 -乙基氧雜環丁 烷-3-基）丙基等例。 做爲具有丙烯醯氧基之烷基例者如：丙烯醯氧基甲基 -8- 200806765 (5) 、冷-丙烯醯氧基乙基、石-丙烯醯氧基丙基、r -丙烯醯氧 基丙基等例。 做爲具有甲基丙烯醯氧基之烷基例者如：甲基丙烯醯 氧基甲基、/3 -甲基丙烯醯氧基乙基、Θ -甲基丙烯醯氧基 丙基、r -甲基丙烯醯氧基丙基等例。 - 具有氫硫基之烷基例者如：氫硫基甲基、/3 -氫硫基 乙基、y3-氫硫基丙基、7 -氫硫基丙基等例，具有醯基之 φ 烷基例者如：胺基甲基、/3 -胺基乙基、胺基丙基、r -胺基丙基、ν-(θ -胺基乙基）r -胺基丙基、N_苯基-τ -胺 基丙基等例。 具有醯基之烷基例者如：氰基甲基、氰基乙基、 沒-氰基丙基、r-氰基丙基等例。具有異氰基之取代基例 者如·異氰基甲基、/5-異氰基乙基、異氨基丙基、 異氰基丙基等例。 一般式（1)中113代表氯原子、羥原子或碳原子數1〜3〇 • 之非取代或取代之烷氧基或芳氧基。 做爲碳原子數1〜3 0之非取代或取代之烷氧基例者以 碳原子數爲1〜10、特別是碳原子數丨〜6之低級烷氧基者 宜，如：甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、 異丁氧基、第三-丁氧基、環己氧基等之非取代之烷氧基 、甲氧基甲氧基、甲氧基乙氧基、乙氧基甲氧基、乙氧基 乙氧基等烷氧基取代之烷氧基等例。 做爲碳原子數1〜3 0之非取代或取代之芳氧基例者以 碳原子數6〜18，特別是碳原子數6〜12之具有1個或2個 -9- 200806765 (6) 芳香族環者宜，如：苯基氧基、〇，m ’ p-甲苯基氧基、二 甲基苯基氧基、〇，m，p-乙基苯基氧基、；基氧基、苯基 乙基氧基、萘基氧基、聯苯基氧基、蒽基氧基等例。 [(B)有機鋁化合物] •做爲（B)成份所使用之路易斯酸性之有機鋁化合物考 量做爲本發明底層塗料組成物中矽醇縮合觸媒之作用者， φ 較佳者爲下述一般式（2): R4xA1(OR5)3.x …（2) (式中，X爲0〜3之整數、X爲1〜3時，R4代表獨立地碳原 子數3〇以下（亦即，碳原子數1〜3〇)、較佳者爲1〜15、更 佳者爲1〜1 0之烷氧基、乙醯基、乙醯氧基（亦即丙酮酸酯 基）；R5代表碳原子數1〜1 5之非取代或取代烷基或芳基） φ 所示之有機鋁化合物。代表該有機鋁化合物之一般式（2)中 ’ R5之非取代或取代之烷基或芳基例者如：甲基、乙基、 丙基、異丙基、丁基、異丁基、第三-丁基、環己基等之 理想碳原子數爲1〜1 5、特別佳者爲1〜1 0之烷基例。又以 苯基、氟苯基、沒-萘基、蒽基等理想碳原子數爲6〜18之 芳基爲較佳。 R4之烷氧基及OR5之非取代或取代烷氧基或做爲芳 氧基者與一般式（1)之R3所示例者相同之非取代或取代烷 氧基或非取代或取代芳氧基例。 -10- 200806765 (7) 做爲上述有機鋁化合物之具體-例者如：三（第二-丁氧-基）鋁、三甲氧基鋁、三乙氧基鋁、三丙氧基鋁、三（第二-丙氧基）鋁、三丁氧基鋁、三（第三-丁氧基鋁）、三（環己基 氧基）鋁、乙醯基二甲氧基鋁、乙醯基二乙氧基鋁、乙醯 基二丙氧基鋁、乙醯基雙（第二-丙氧基）鋁、乙醯基二丁氧 基鋁、乙醯基雙（第二-丁氧基）鋁、乙醯基雙（第三-丁氧基 )鋁、乙醯氧基二甲氧基鋁、乙醯氧基二乙氧基鋁、乙醯 φ 氧基二丙氧基鋁、乙醯氧基雙（第二-丙氧基）鋁、乙醯氧基 二丁氧基鋁、乙醯氧基雙（第二-丁氧基）鋁、乙醯氧基雙（ 桌二-丁氧基）錫等例。較佳者爲三（第二-丁氧基）銘。 做爲（B)成份者可單獨使用1種或組合2種以上之路 易斯酸性有機鋁化合物。 本發明組成物中，（A)成份/(B)成份之質量比爲1以下 者宜、（A)成份/(B)成份之質量比爲 1〜0.01，甚至爲 0.8〜0·1、特別是0.7〜0.2將可大幅擴大塗佈作業性、亦即 φ ，由底層塗料塗佈後至結束乾燥之乾燥步驟中可利用時間 之範圍（可使用時間或界限）面更爲理想。 [有機溶劑] 做爲（C)成份所使用之有機溶劑者，可使用公知之各 種有機溶劑，特別爲取得高度效果者可使用如·· η_戊烷、 η-己烷、η-庚烷、異辛烷、環戊烷、環己烷等碳原子數 5〜1 5之烴系溶劑。亦可使用含雜溶劑（亦即含碳、氫以外 之雜原子的溶劑），如：亦可使用乙醇、丙醇、丁·醇、環 -11 - 200806765 (8) 己醇、一***、四氫呋喃、1，4 -二氧陸圜、丙酮、乙酸乙 酯、乙酸丁酯等醇系、醚系、酯系溶劑。另外亦可使用氟 鍵院、氯院醚寺含Μ系溶劑。更理想者可使用苯、甲苯、 二甲苯、卩比陡等碳原子數5〜15之芳香族碳環系溶劑或芳 香族複環系溶劑。 '做爲芳香族碳環系溶劑之理想例者如—般式（3 ): 【化1】200806765 (1) EMBODIMENT OF THE INVENTION [Technical Field] The present invention relates to a light-resistant primer composition, a method for producing a light-emitting semiconductor device using the primer composition, and a light-emitting semiconductor device obtained by the method and use thereof A light-emitting semiconductor device of the primer composition. I. [Prior Art] By the brightness and high output of the light-emitting diode, the materials for the package materials and sealing materials constituting the light-emitting diode have been subjected to a larger light and heat load up to now. In recent years, a highly durable material of polyoxymethylene resin has been widely used as a sealing resin of a high-output light-emitting diode (LED). However, the package for mounting LEDs is made of a variety of materials such as metal and semiconductor materials, and the sealing resin material must have adhesion reliability to various materials. Further, when the LED is driven by light and at a high temperature, there is a problem that the color of the underlying layer φ is changed, and the light extraction efficiency of the LED is lowered. Further, the primer containing a highly active compound has a limited coating treatment time, which causes problems in the production work surface. In order to solve these problems, there have been reports on the primers (Patent Documents 1 and 2) of the primers formed by a combination of a decyl alcohol condensation catalyst and a decane coupling agent, but the coating workability of the primer for the LED is The primers that adhere to both the reliability and the discoloration resistance are not described. [Patent Document 1] JP-A-2004-3 39450 [Patent Document 2] JP-A-2005-093724 200806765 (2) SUMMARY OF THE INVENTION Accordingly, the object of the present invention is to provide a coating workability and a sealing resin and a base. The material has high adhesion and reliability, and it is a primer material which is highly resistant to discoloration by light irradiation and heating. Further, the object of the present invention is to provide a method for producing a higher performance light-emitting semiconductor device by using the primer composition. In order to solve this problem, the inventors of the present invention have found that the above-mentioned problems can be solved by combining φ with an organoaluminum compound of a Lewis acid and a specific decane coupling agent and an organic solvent, and the present invention has been completed. That is, as means for solving the above problems, the first aspect of the present invention provides (A) the following general formula (1) R1xR2ySi(R3)4-XY (1) (wherein R1 and R2 represent independently hydrogen; An atom, or an alkyl group having 1 or more carbon atoms which may have one or more reactive φ substituents, and R3 represents a chlorine atom, a hydroxyl group or an unsubstituted or substituted alkoxy group or a aryl group having 1 to 30 carbon atoms. An oxy group, X is an integer of 1 to 2, Y is an integer of 0 to 1, and χ + γ is an integer of 1 or 2) * at least one decane compound and/or a partially hydrolyzed condensate thereof ( B) Lewis acid organoaluminum compound, and (C) organic solvent, and the resulting primer composition. -6 - 200806765 (3) The second aspect of the present invention provides a primer which is characterized in that a primer composition is applied onto a surface of a light-emitting semiconductor device mounted on a preform package, and after drying, a primer coating the surface of the light-emitting semiconductor device is formed. The composition layer is subjected to an addition reaction-hardening type polyfluorene oxide on the primer composition layer, and the element is subjected to external molding to seal the resin. • After using the primer composition of the present invention, the coating of the primer can be improved, the time of the drying step can be utilized, the workability can be improved, and the adhesion reliability of the sealing resin φ to the substrate can be improved. Further, since the coating layer of the primer composition has chemical and physical stability, the primer layer is resistant to discoloration even under high temperature and light irradiation conditions when the component is lit. In this way, a light-emitting semiconductor device having a long life and high reliability can be realized. [Embodiment] Hereinafter, the present invention will be described in more detail. φ [Base coating composition] [(A) decane coupling agent] As a component of (A), the general formula is: R1xR2YSi(R3)4 x γ (1) (wherein R1 and R2 represent independently hydrogen atoms) Or an alkyl group having a carbon atom number U0, preferably 2 to 30, more preferably 2 to 15 5 having one or more reactive substituents, and a chlorine atom, a hydroxyl group or a carbon number of 1 to 30. Non-200806765 (4) Substituted or substituted alkoxy or aryloxy, X is an integer from 1 to 2, Y is an integer from 0 to 1, and Χ + Υ is an integer of 1 or 2) at least one decane shown a compound and/or a partial hydrolysis condensate thereof; and R1 and R2 are not hydrogen atoms at the same time (that is, at least one of R1 and R2 is a carbon atom having one or more reactive substituents) 2 to 30 alkyl groups are suitable. In the general formula (1), when both of R1 and R2, or one of them is a hospital base, preferably, the number of carbon atoms in the methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc. is 1~ An alkyl group of 18. The alkyl group represented by R1 or R2 may have one or more reactive substituents. Examples of the reactive substituent are, for example, an epoxy group, an oxetanyl group, an acryloxy group, a methacryloxy group, a thio group, an amine group, a cyano group or an isocyano group. More specifically, as an epoxy group or an alkyl group having an epoxy group, such as %: glycidyl group, non-glycidoxyethyl group, α-glycidoxypropyl group, /3 - Glycidoxypropyl, r-glycidoxypropyl, ^-glycidoxypropyl, butyl-glycidoxybutyl, r-glycidoxybutyl, ring Oxypropoxybutyl, (3,4-epoxycyclohexyl)methyl, /3-(3,4-epoxycyclohexyl)ethyl, r-(3,4-epoxycyclohexyl) Examples of propyl, (5-(3,4-epoxycyclohexyl)butyl, etc. Examples of alkyl groups as oxetane groups such as: (3-ethyloxetane-3) - propyl), etc. Examples of alkyl groups having an acryloxy group such as: acryloxymethyl-8-200806765 (5), cold-acryloxyethyl, stone-propylene oxime Examples of the propyl group, the r-propylene methoxy propyl group, etc., and the alkyl group having a methacryloxy group, such as methacryloxymethyl group, /3-methacryloxy group Examples of hydrazine, hydrazine-methacryloxypropyl, r-methacryloxypropyl, etc. - Examples of alkyl having a thiol group such as: thiol , /3 - thioethyl, y3-hydrothiopropyl, 7- thiopropyl propyl, etc., examples of φ alkyl having a fluorenyl group such as: aminomethyl, /3 -amino B Examples of a group, an aminopropyl group, an r-aminopropyl group, a ν-(θ-aminoethyl)r-aminopropyl group, an N-phenyl-τ-aminopropyl group, and the like. For example, cyanomethyl, cyanoethyl, non-cyanopropyl, r-cyanopropyl, etc. Examples of substituents having an isocyano group such as isocyanomethyl, /5 -Isocyanoethyl, isoaminopropyl, isocyanopropyl, etc. In general formula (1), 113 represents a chlorine atom, a hydroxyl atom or an unsubstituted or substituted alkoxy group having 1 to 3 carbon atoms. Or an alkoxy group as an unsubstituted or substituted alkoxy group having 1 to 30 carbon atoms, preferably having a lower alkoxy group having 1 to 10 carbon atoms, particularly a carbon number of 丨6. Such as: methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, cyclohexyloxy, etc., unsubstituted alkoxy, A Alkoxy groups such as oxymethoxy, methoxyethoxy, ethoxymethoxy, ethoxyethoxy, etc. Examples of the alkoxy group, etc., as an unsubstituted or substituted aryloxy group having 1 to 30 carbon atoms, have 1 or 2 carbon atoms, especially 6 to 12 carbon atoms. -9- 200806765 (6) Aromatic rings, such as: phenyloxy, hydrazine, m 'p-tolyloxy, dimethylphenyloxy, hydrazine, m, p-ethylphenyl Examples of the oxy group, the oxy group, the phenylethyloxy group, the naphthyloxy group, the biphenylyloxy group, the decyloxy group, etc. [(B) Organoaluminum compound] • Used as the component (B) The Lewis acidic organoaluminum compound is considered to be a sterol condensation catalyst in the primer composition of the present invention, and φ is preferably the following general formula (2): R4xA1(OR5)3.x (2) (wherein, X is an integer of 0 to 3, and when X is 1 to 3, R4 represents independently 3 to 3 carbon atoms (that is, 1 to 3 carbon atoms), preferably 1 to 15, More preferably, it is an alkoxy group of 1 to 10, an ethyl oxime group, an ethoxy group (ie, a pyruvate group); and R5 represents an unsubstituted or substituted alkyl or aryl group having 1 to 15 carbon atoms) An organoaluminum compound represented by φ. An alkyl or aryl group which is an unsubstituted or substituted R 5 of the general formula (2) representing the organoaluminum compound, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, The alkyl group having a desirable number of carbon atoms such as tri-butyl or cyclohexyl is 1 to 15 and particularly preferably 1 to 10. Further, an aryl group having an ideal carbon number of 6 to 18, such as a phenyl group, a fluorophenyl group, a non-naphthyl group or a fluorenyl group, is preferred. An alkoxy group of R4 and an unsubstituted or substituted alkoxy group of OR5 or an aryloxy group which is the same as the one represented by R3 of the general formula (1), an unsubstituted or substituted alkoxy group or an unsubstituted or substituted aryloxy group. example. -10- 200806765 (7) As specific examples of the above organoaluminum compound, such as: tris(t-butoxy-yl)aluminum, trimethoxyaluminum, triethoxyaluminum, tripropoxyaluminum, and tris (Second-propoxy)aluminum, tributoxyaluminum, tris(t-butoxyaluminum), tris(cyclohexyloxy)aluminum, etidinyldimethoxyaluminum, etidyldiethyl Aluminium oxyaluminum, acetamidopropoxy aluminum, acetyl bis(secondary-propoxy) aluminum, acetyl bis-butoxy aluminum, acetyl bis(secondary-butoxy) aluminum, Ethyl bis(tris-butoxy)aluminum, ethoxylated dimethoxyaluminum, ethoxylated diethoxyaluminum, acetamidine φ oxydipropoxyaluminum, acetoxyl double (second-propoxy)aluminum, ethoxylated dibutoxyaluminum, ethoxylated bis(second-butoxy)aluminum, ethoxylated bis(tabledi-butoxy)tin, etc. example. Preferred is tris(second-butoxy). As the component (B), one type or a combination of two or more types of Lewis acid organoaluminum compounds may be used alone. In the composition of the present invention, the mass ratio of the component (A) to the component (B) is preferably 1 or less, and the mass ratio of the component (A) to the component (B) is 1 to 0.01, or even 0.8 to 0.1, particularly When it is 0.7 to 0.2, the coating workability, that is, φ, can be greatly expanded, and the range of usable time (use time or limit) in the drying step from the application of the primer to the end of drying is more preferable. [Organic solvent] As the organic solvent used for the component (C), various known organic solvents can be used, and those having a high effect can be used, such as η·pentane, η-hexane, and η-heptane. A hydrocarbon solvent having 5 to 15 carbon atoms such as isooctane, cyclopentane or cyclohexane. It is also possible to use a solvent containing a hetero-solvent (that is, a solvent containing a hetero atom other than carbon or hydrogen), for example, ethanol, propanol, butanol, cyclo-11 - 200806765 (8) hexanol, monoethyl ether, tetrahydrofuran. An alcohol-based, ether-based or ester-based solvent such as 1,4-dioxane, acetone, ethyl acetate or butyl acetate. In addition, it is also possible to use a fluorine-based solvent or a chlorine-based ether temple containing an oxime-based solvent. More preferably, an aromatic carbocyclic solvent having a carbon number of 5 to 15 such as benzene, toluene, xylene or hydrazine is used, or an aromatic sulfonate-based solvent. 'As an ideal example of an aromatic carbon ring solvent, as in the general formula (3): [Chemical 1]
Rs …（3) 所示之化合物所成之有機溶劑例。 上述式（3)中，做爲R6、R7、R8之取代基例者如：獨 立地氫原子、羥基、碳原子數1〜6之烷基、烷氧基、醯胺 基、胺基、及鹵原子例，其R6、R7、R8特別以氫原子與 院基之組合所成者爲最佳。 上述烷基可爲直鏈狀、支鏈狀或環狀之烷基均可，如 :甲基、乙基、正-丙基、異-丙基、環丙基、正·丁基、 異-丁基、第二-丁基、第三-丁基、環丁基、1-甲基-環丙 基、2-甲基-環丙基、正-戊基、1-甲基-正-丁基、2-甲基-正-丁基、3-甲基-正-丁基、1，1-二甲基-正-丙基、1，2-二 甲基-η-丙基、2，2-二甲基-正-丙基、1-乙基-正-丙基、環 戊基、卜甲基-環丁基、2-甲基-環丁基、3-甲基-環丁基、 1，2-二甲基-環丙基、2，3-二甲基-環丙基、1-乙基-環丙基 -12- 200806765 (9) 、2-乙基-環丙基、正-己基、1-甲基-正-戊基、2-甲基-正-戊基、3-甲基-正-戊基、4-甲基-正·戊基、1，1-二甲基-正-丁基、1，2-二甲基-正-丁基、1，3-二甲基-正-丁基、2，2-二甲基-正-丁基、2，3-二甲基-正-丁基、3，3-二甲基-正-丁基、1-乙基-正-丁基、2-乙基-正-丁基、1，1，2-三甲基-•正-丙基、1，2，2-三甲基-正-丙基、1-乙基-1_甲基-正-丙 基、1-乙基-2-甲基-正-丙基、環己基、1-甲基-環戊基、2-φ 甲基-環戊基、3-甲基-環戊基、1-乙基-環丁基、2-乙基-環 丁基、3-乙基-環丁基、1，2-二甲基環丁基、1，3-二甲基-環丁基、2，2-二甲基-環丁基、2，3-二甲基-環丁基、2，4-二甲基-環丁基、3，3-二甲基-環丁基、1-正-丙基-環丙基 、2-正-丙基-環丙基、1-異-丙基-環丙基、2-異-丙基-環丙 基、1，2，2-三甲基環丙基、1，2，3-三甲基環丙基、2，2, 3-三甲基環丙基、1-乙基-2-甲基環丙基、2-乙基-1-甲基環 丙基、2-乙基-2-甲基環丙基、2-乙基-3-甲基環丙基等例 做爲上述式（3)之烷氧基例者如：甲氧基、乙氧基、 正-丙氧基、異-丙氧基、C-丙氧基、正-丁氧基、異-丁氧 基、第二-丁氧基、第三-丁氧基、C-丁氧基、1-甲基-C-丙 ' 氧基、2-甲基-C-丙氧基、戊氧基、C-戊氧基、己氧基、C- 己氧基等例。 做爲上述（3)之醯胺基例者如：乙醯醯胺（乙醯胺基）、 乙基羰醯胺基、正-丙基羰醯胺基、異-丙基羰醯胺基、正-丁基羰醯胺基等例。 -13- 200806765 (10) 做爲上述式（3)之胺基例者如：胺基、甲基胺基、乙基 胺基、丙基胺基、異丙基胺基、二甲基胺基、二乙基胺基 、二丙基胺基、二異-丙基胺基等例。 做爲上述（3)之鹵原子者如：氟原子、氯原子、溴原子 、碘原子例。 有機溶劑之更具體例者之做爲醇類例者如：甲醇、乙 醇、異丙醇、第三-丁醇、正-丙醇、第二-丁醇、異丁醇、 φ 正-丁醇、2-丁醇、正-己醇、1-戊醇、新戊醇、環戊醇、 環己醇等1價醇類；丙二醇單甲醚、丙二醇單***、丙二 醇單異丙醚、丙二醇單正-丙醚、丙二醇單正-丁醚、丙二 醇單第二-丁醚等之丙二醇單烷醚類；乙二醇單甲醚、乙 三醇單***、乙二醇單正-丙醚、乙二醇單異丙醚、乙二 醇單正-丁醚、乙二醇單第二-丁醚、乙二醇單第三-丁醚、 乙二醇單正-戊醚、乙二醇單正-己醚、2_苯氧基乙醇、 ¥氧基）乙醇等乙二醇單烷醚類；丙二醇單乙酸酯、丙二 φ 醇單丙酸酯、乙二醇單乙酸酯、乙二醇單丙酸酯、二乙= 醇單乙酸酯等具有酯鍵之醇類；乙二醇、丙二醇、二乙二 酉子、己一醇等2價醇類；氟醇、四氫氟醇、1-氯-2-丙醇、 一丙嗣醇、2_氰基乙醇、丙酮氰表氯醇等具羥基以外取代 基之醇類等例。 做爲酯系溶劑例者如：甲酸乙酯、甲酸丙酯等之甲酸 醋類’乙酸甲酯、乙酸乙酯、乙酸正-丙酯、乙酸-異柯_ 、乙酸丁醋、乙酸戊酯、乙酸異戊酯等之乙酸酯類；柯酸 甲酉曰丙酸乙酯等之丙酸酯類；乳酸甲酯、乳酸乙酯、乳 -14- 200806765 (11) 酸丁酯等之乳酸酯類；乙醯乙酸甲酯、乙醯乙酸乙酯等之 乙醯乙酸酯類；酪酸酯類；異酪酸酯類；吉草酸酯類；苯 甲酸酯類；草酸酯類；蘋果酸酯類；馬來酸酯類；酒石酸 酯類；檸檬酸酯類；二乙二醇二酯類；碳酸二乙酯、碳酸 乙烯酯、碳酸丙烯酯等之具有碳酸酯鍵化合物；硼酸酯類 :磷酸酯類之例。 做爲醯胺系溶劑例者如：N，N -二甲基甲醯胺、N -甲 φ 基甲醯胺、N，N-二甲基乙醯胺等非環狀醯胺類、N_甲基_ 2-吡咯烷酮等之環狀醯胺類等例。 做爲硝基化合物系溶劑例者如：硝基甲烷、硝基乙烷 、硝基丙基、硝基苯等之烷基取代硝基化合物例。 此等有機溶劑可適用單獨1種、亦可組合2種以上， 由取得特異性底層塗料組成物之高度保存穩定性面視之， 特別以芳香族化合物系溶劑者最佳。 • [發光半導體裝置之製造方法] 本發明發光半導體裝置之製造方法之特徵係含有使該 底層塗料組成物塗佈於預成型封裝上所裝置之發光半導體 元件表面後，乾燥之後，形成被覆該發光半導體元件表面 之底層塗料組成物層，於該底層塗料組成物層上適用加成 反應硬化型聚矽氧樹脂後，使該元件進行外模成形之樹脂 密封。 該製造方法中，於該發光半導體元件表面所形成之底 層塗料組成物層之一般式（1)所示之矽烷化合物中R3之反 -15- 200806765 (12) 應率爲50〜90%、較佳者爲55〜80%、更佳者爲6〇〜75%範 圍狀態下，藉由加成反應硬化型聚矽氧樹脂進行外模成形 樹脂密封者宜。其中，「R3之反應率」係指使存在於該矽 烷化合物之R3之初莫耳數爲A，使反應（水解、及依不同 情況下進一步縮合）後所殘存之未反應R3之莫耳數爲B， 以（1-B/A)xl00(%)示之。另外，使用本發明底層塗料組成 物之前，該反應率爲〇〜4 9 %範圍內者其黏著信賴性及耐變 色性面爲較佳。 預成型封裝多半以如：導引構架、合成樹脂、陶瓷等 各種材料所構成，而藉由使用本發明底層塗料組成物可達 成高度信賴性之黏著。 做爲發光半導體元件例者如：發光二極體、半導體雷 射、有機EL(電致發光）、無機EL等例。 將底層塗料組成物塗佈於被密封部份之方法並無特別 限定，一般常法進行均可，通常藉由定量液體吐出裝置之 底層塗料滴入之方法即可。塗佈後的乾燥可於10〜4 0 °C 下進行，於室溫（15〜30 °C)者宜。 由底層塗料組成物之塗佈至乾燥（結束）爲止之時間爲 15分鐘〜6小時、特別以20分鐘〜3小時之界限（安全係數） 進行者宜，而使用本發明組成物後可充份以此時間的界限 設定塗佈、乾燥條件。更理想者爲3 0分鐘〜1小時。 做爲密封樹脂所使用之加成反應硬化型聚矽氧樹脂亦 未特別受限。 -16- 200806765 (13) [實施例] 以下，藉由實施例進行本發明更詳細之說明’惟本發 明並未受限於此等實施例。以下所載「份」係代表「質量 份」之意。 [實施例1] (1) 底層塗料組成物之調製 φ 氮氣流下99.25份之甲苯中加入0.5份三（第二-丁氧 基）鋁，進行劇烈攪拌5分鐘後溶解之。再於取得溶液中 溶解〇 . 2 5份之3 -環氧丙氧基丙基三甲氧基砂院（信越化學 工業（股份）製、商品名KBM-403)，進行劇烈攪拌5分鐘 後，取得底層塗料組成物。此底層塗料組成物於使用前氮 氣流下以空孔尺寸（過濾細孔）1 μιη之濾器進行過濾。 (2) LED元件之底層塗料處理 • 對於進行裝置於封裝（外模成形封裝）之發光二極體元 件之樹脂密封部位，將（1 )取得之底層塗料組成物利用噴射 . 裝置進行塗佈。持續使含於塗佈之底層塗料組成物中之溶 劑於室溫下分別經由3 0分鐘、1小時及2小時之乾燥後去 除之後，於密封部位形成底層塗料層。 -17 - 200806765 (14) 化學工業製、商品名X-3 5 -3 3 0B)於真空下，脫泡之_同時進 行攪拌。接著將該樹脂溶液藉由噴射裝置後注入LED封 裝塑模框內於6 0 t下處理1小時，再於1 〇 〇 °C處理2 小時，於1 5 0 °C下處理4小時後取得密封之LED。 _ (4)底層塗料組成物之矽烷偶合劑反應度之測定 將本發明之底層塗料組成物塗佈於玻璃皿後，分別於 φ 3 0分鐘、1小時，2小時之條件下乾燥後，取得之硬化物 溶於重氯仿後，藉由過濾去除不溶物。此溶液藉由NMR( 核磁共振光譜）測定後，由積分比求出甲氧基矽烷殘留量 後決定反應度。重覆進行相同實驗3次後，確定其反應度 爲60〜70%之範圍以內。 [比較例1 ] (藉由鈦系底層塗料之塗佈處理） 以鈦系底層塗料（信越化學工業（股份）製、商品名 primer C)取代實施例1所調製之底層塗料組成物使用之外 ，以實施例1之（3)的方法進行密封LED元件。 [評定] 針對實施例1及比較例1取得之密封完成之LED，經 由下述條件使 • LED封裝之污染性 •塗佈乾燥作業之時間界限 -18- 200806765 (15) •對於reflow之耐剝離性、及 •吸濕條件下之LED驅動時之耐變色性 依下述基準進行評定。 表1代表「塗佈乾燥作業之時間界限」與「對於 reflow之耐剝離性」之結果。表2代表「吸濕條侔下之 LED驅動時之耐變色性」之結果。 (1) LED封裝之污染性評定 底層塗料塗佈處理後，藉由實體顯微鏡觀測LED封 裝之表面狀態時之情況分成四階段。 A :底層塗料塗佈•乾燥後之LED封裝表面呈平滑、 且爲透明。 B :底層塗料塗佈•乾燥後之LED封裝表面呈平滑、 且爲不透明。 C :底層塗料塗佈•乾燥後之LED封裝表面呈粗糙、 且爲透明。 D :底層塗料塗佈•乾燥後之L E D封裝表面呈粗糙、 且爲不透明。 (2) 密封樹脂之LED捲裝上之剝離試驗 將樹脂密封於複數個（η = 1〜1 6)之底層塗料塗佈•乾燥 後之L E D封裝，進行硬化反應後，將其維持於8 5 °C、濕 度8 5 %之恒溫恒濕槽中’放置2 4小時。由恒溫恒濕槽取 出後立刻藉由IRreflow裝置於260 °C進行熱履歷（3次輸 -19- 200806765 (16) 送速度：40cm/min)。以實體顯微鏡觀測處理後之LED封 裝狀態，判斷LED封裝與密封樹脂界面之剝離狀態’判 定以下2階段。 A : LED中密封之密封樹脂與LED封裝界面呈密合狀 態。 B : LED中密封之密封樹脂與LED封裝界面呈剝離狀 態。 (3)進行底層塗料處理·密封之LED點燈試驗 使初期呈無色透明之樹脂密封完成之LED於8 5 t、 濕度85%之條件下，進行通電•點燈試驗，分成以下3階 段進行判定最大1 〇〇〇小時爲止之LED著色狀態。 A :幾乎未出現變色。 B :稍有變色。 C :強烈變色。 • [表1]An example of an organic solvent formed by a compound represented by Rs (3). In the above formula (3), as a substituent of R6, R7 and R8, for example, an independently hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group, a decylamino group, an amine group, and In the case of a halogen atom, R6, R7 and R8 are particularly preferably a combination of a hydrogen atom and a hospital base. The above alkyl group may be a linear, branched or cyclic alkyl group, such as methyl, ethyl, n-propyl, iso-propyl, cyclopropyl, n-butyl, iso- Butyl, second-butyl, tert-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl Base, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-η-propyl, 2, 2-Dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1 ,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl-12- 200806765 (9), 2-ethyl-cyclopropyl, n- Hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl- n-Butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl Base-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl- • n-propyl, 1,2,2-three - n-propyl, 1-ethyl-1 -methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2- φ methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl Cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-ring Butyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-iso-propyl-cyclopropyl, 2- Isopropyl-cyclopropyl, 1,2,2-trimethylcyclopropyl, 1,2,3-trimethylcyclopropyl, 2,2,3-trimethylcyclopropyl, 1- Ethyl-2-methylcyclopropyl, 2-ethyl-1-methylcyclopropyl, 2-ethyl-2-methylcyclopropyl, 2-ethyl-3-methylcyclopropyl, etc. Examples of the alkoxy group of the above formula (3) are methoxy, ethoxy, n-propoxy, iso-propoxy, C-propoxy, n-butoxy, iso- Butoxy, second-butoxy, tert-butoxy, C-butoxy, 1-methyl-C-propanyloxy, 2-methyl-C-propoxy, pentyloxy , C-pentyloxy, hexyloxy, C-hexyloxy Other cases. As the amidamine group of the above (3), for example, acetamide (acetamidoamine), ethylcarbonylamine, n-propylcarbonylamine, iso-propylcarbonylamine, Examples of n-butylcarbonylamine groups and the like. -13- 200806765 (10) As an amine group of the above formula (3), for example, an amine group, a methylamino group, an ethylamino group, a propylamino group, an isopropylamino group, a dimethylamino group. Examples of diethylamino group, dipropylamino group, diiso-propylamino group and the like. Examples of the halogen atom of the above (3) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. More specific examples of the organic solvent include alcohols such as methanol, ethanol, isopropanol, tri-butanol, n-propanol, di-butanol, isobutanol, φ-butanol, a monovalent alcohol such as 2-butanol, n-hexanol, 1-pentanol, neopentyl alcohol, cyclopentanol or cyclohexanol; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monoisopropyl ether, propylene glycol single positive - propylene glycol monoalkyl ethers such as propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-second-butyl ether; ethylene glycol monomethyl ether, ethoxylated monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene Alcohol monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-di-butyl ether, ethylene glycol mono-tert-butyl ether, ethylene glycol mono-n-pentyl ether, ethylene glycol single positive - Ethylene glycol monoalkyl ethers such as hexyl ether, 2-phenoxyethanol, and oxy)ethanol; propylene glycol monoacetate, propanediol monopropionate, ethylene glycol monoacetate, ethylene glycol An alcohol having an ester bond such as a monopropionate or a diethyl ether; an alcohol monoacetate; a divalent alcohol such as ethylene glycol, propylene glycol, diethylene dichloride or hexanol; a fluoroalcohol, a tetrahydrofluoro alcohol, 1-chloro-2-propanol, 1-propanol, 2-cyanoethanol Substituents other than hydroxy acetone cyanohydrin with epichlorohydrin alcohols, etc. Examples of the group. Examples of the ester solvent include formic acid vinegar such as ethyl formate or propyl formate, methyl acetate, ethyl acetate, n-propyl acetate, acetic acid-isoco-, butyl acetate, and amyl acetate. Acetate such as isoamyl acetate; propionate such as ethyl formazanic acid; methyl lactate, ethyl lactate, milk-14-200806765 (11) lactate such as butyl acrylate Ethyl acetate, such as methyl acetate, ethyl acetate, ethyl acetate; tyrosinates; isotyrosates; oxalic acid esters; benzoic acid esters; oxalates; malate; Acid esters; tartaric acid esters; citrate esters; diethylene glycol diesters; carbonate carbonate compounds such as diethyl carbonate, ethylene carbonate, propylene carbonate, etc.; borate esters: phosphate esters . Examples of the amide-based solvent include N,N-dimethylformamide, N-methyl phthalamide, N,N-dimethylacetamide, and the like, N_ Examples of cyclic guanamines such as methyl-2-pyrrolidone. Examples of the nitro compound-based solvent include an alkyl-substituted nitro compound such as nitromethane, nitroethane, nitropropyl or nitrobenzene. These organic solvents may be used singly or in combination of two or more kinds, and it is preferable to obtain a high stability stability of the specific primer composition, and it is particularly preferable as an aromatic compound solvent. [Manufacturing method of light-emitting semiconductor device] The method for producing a light-emitting semiconductor device according to the present invention is characterized in that the surface of the light-emitting semiconductor device to which the primer composition is applied onto a preform package is dried, and then the light is formed to be coated. The primer layer composition layer on the surface of the semiconductor element is applied to the primer composition layer to apply an addition reaction-hardening type polyoxynoxy resin, and then the element is subjected to external molding to form a resin seal. In the manufacturing method, in the decane compound represented by the general formula (1) of the primer composition layer formed on the surface of the light-emitting semiconductor device, the inverse ratio of R3 to -15-200806765 (12) is 50 to 90%. In the case where the film is in a range of from 55 to 80%, more preferably from 6 to 75%, it is preferable to carry out an outer molding resin sealing by addition reaction hardening type polyoxyl resin. Here, the "reaction rate of R3" means that the number of moles of unreacted R3 remaining after R3 of R3 present in the decane compound is A, and the reaction (hydrolysis and further condensation is further condensed) is B, shown as (1-B/A)xl00 (%). Further, before the use of the primer composition of the present invention, the reaction reliability is in the range of 〇 to 49%, and the adhesion reliability and the resistance to discoloration are preferred. Most of the preformed packages are composed of various materials such as a guide frame, a synthetic resin, a ceramic, and the like, and a highly reliable adhesive can be obtained by using the primer composition of the present invention. Examples of the light-emitting semiconductor element include a light-emitting diode, a semiconductor laser, an organic EL (electroluminescence), and an inorganic EL. The method of applying the primer composition to the sealed portion is not particularly limited, and it can be carried out by a usual method, and it is usually carried out by quantitatively dropping the primer of the liquid discharge device. Drying after coating can be carried out at 10 to 40 ° C, preferably at room temperature (15 to 30 ° C). The time from the application of the primer composition to the drying (end) is from 15 minutes to 6 hours, particularly from the limit of 20 minutes to 3 hours (safety factor), and the composition of the present invention is sufficient for use. The coating and drying conditions are set at the limit of this time. More ideally, it is 30 minutes to 1 hour. The addition reaction-hardening type polyoxymethylene resin used as the sealing resin is also not particularly limited. [16] [Embodiment] Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to the embodiments. The following "parts" represent the meaning of "quality". [Example 1] (1) Preparation of primer composition φ 0.5 parts of tris(t-butoxy)aluminum was added to 99.25 parts of toluene under a nitrogen stream, and the mixture was vigorously stirred for 5 minutes and then dissolved. Further, 2 parts of 3-glycidoxypropyltrimethoxy sand (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-403) was dissolved in the obtained solution, and vigorously stirred for 5 minutes. Primer composition. This primer composition was filtered with a pore size (filtration pore) of 1 μm under a nitrogen gas stream before use. (2) Primer treatment of LED components • The primer composition obtained in (1) is coated with a device by a device for sealing the resin of the light-emitting diode component mounted on the package (outer mold package). The primer contained in the applied primer composition was continuously dried at room temperature for 30 minutes, 1 hour, and 2 hours, and then a primer layer was formed at the sealing portion. -17 - 200806765 (14) Chemical industry, trade name X-3 5 -3 3 0B) Under vacuum, defoaming _ while stirring. Then, the resin solution is injected into the LED package mold frame by the spraying device and treated at 60 t for 1 hour, then treated at 1 ° C for 2 hours, and treated at 150 ° C for 4 hours to obtain a seal. LED. _ (4) Determination of the reactivity of the decane coupling agent of the primer composition After the primer composition of the present invention is applied to a glass dish, it is dried under conditions of φ 30 minutes, 1 hour, and 2 hours, respectively. After the hardened material was dissolved in heavy chloroform, the insoluble matter was removed by filtration. After the solution was measured by NMR (nuclear magnetic resonance spectroscopy), the residual amount of methoxydecane was determined from the integral ratio, and the degree of reaction was determined. After repeating the same experiment three times, it was confirmed that the degree of reaction was within the range of 60 to 70%. [Comparative Example 1] (Coating treatment by titanium-based primer) The titanium-based primer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name primer C) was used instead of the primer composition prepared in Example 1. The LED element was sealed by the method of (3) of Example 1. [Evaluation] The sealed LEDs obtained in Example 1 and Comparative Example 1 were subjected to the following conditions: • Contamination of the LED package • Time limit for coating and drying operations -18 - 200806765 (15) • Resistance to peeling for reflow The discoloration resistance of the LED driving under the conditions of moisture absorption and the hygroscopic condition was evaluated according to the following criteria. Table 1 represents the results of "time limit of coating drying operation" and "peeling resistance to reflow". Table 2 represents the results of "discoloration resistance when the LED is driven under the moisture absorption strip". (1) Contamination evaluation of LED package After the primer coating treatment, the condition of observing the surface state of the LED package by a stereo microscope is divided into four stages. A: Primer coating • The surface of the LED package after drying is smooth and transparent. B: Primer coating • The surface of the LED package after drying is smooth and opaque. C: Primer coating • The surface of the LED package after drying is rough and transparent. D: Primer coating • The dried surface of the L E D package is rough and opaque. (2) Peeling test on LED package of sealing resin The resin is sealed in a plurality of (n = 1 to 16) primer coating and dried LED packages, and after hardening reaction, it is maintained at 8 5 Place in a constant temperature and humidity chamber at °C and humidity of 85% for 2 hours. Immediately after taking out from the constant temperature and humidity chamber, the heat history was performed at 260 °C by the IRreflow device (3 times -19-200806765 (16) sending speed: 40 cm/min). The LED sealing state after the observation by the stereoscopic microscope and the peeling state of the LED package and the sealing resin interface were judged as the following two stages. A : The sealing resin sealed in the LED is in close contact with the LED package interface. B: The sealing resin sealed in the LED is peeled off from the LED package interface. (3) Conducting the LED lighting test for the primer treatment and sealing. The LED which is initially sealed with a colorless and transparent resin is subjected to the energization and lighting test under the conditions of 8 5 t and 85% humidity, and is divided into the following three stages. LED coloring status up to 1 hour. A: There is almost no discoloration. B: A little discoloration. C: Strong discoloration. • [Table 1]
底層塗料塗佈試驗 實施仿 塗料1 〖!ί 1之底層 巨成物 比較例1之有機 系底層给Μ 乾燥時間（HR) 0.5 1 _2 0.5 1 9 乾燥後之LED封裝污染 狀態 A A A A _ Λ L· A IRreflow後黏著狀態 A A A A —— A -20- 200806765 (17) [表2] 1 000小時通電試驗 LED點燈 時間（HR) 24 100 500 1000 本發明之底層塗料組成物 A A A B 有機鈦系底層塗料（比較例） C c C c 由上述結果顯示，於比較例1所使用之鈦系底層塗料 之長時間塗佈乾燥條件下降低黏著信賴性、短時間之led 點燈下出現變色。另外，使用本發明之底層塗料組成物時 ，對於LED元件其可利用於塗佈乾燥之時間範圍廣、作 業性優異。且，長時間之LED驅中未出現變色，具高度 耐變色性。使用本發明底層塗料組成物時，其塗佈乾燥之 作業性、耐變色性及耐剝離性能面均呈現優異者。Primer coating test implementation of imitation paint 1 〖! ί 1 of the bottom layer of the macrocomposite of the organic layer of the comparative example 1 干燥 drying time (HR) 0.5 1 _2 0.5 1 9 LED package contamination status after drying AAAA _ Λ L· A IRreflow post-adhesion state AAAA - A -20- 200806765 (17) [Table 2] 1 000-hour energization test LED lighting time (HR) 24 100 500 1000 The primer composition of the present invention AAAB organic titanium-based primer ( Comparative Example) C c C c From the above results, it was revealed that the titanium-based primer used in Comparative Example 1 was reduced in adhesion under long-term application drying conditions, and discoloration occurred under a short-time led lighting. Further, when the primer composition of the present invention is used, the LED element can be used in a wide range of coating drying time and is excellent in workability. Moreover, there is no discoloration in the LED drive for a long time, and it is highly resistant to discoloration. When the primer composition of the present invention is used, the workability of coating drying, the discoloration resistance, and the peeling resistance surface are excellent.
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