201141915 六、發明說明： 【發明所屬之技術領域】 本發明係有關硬化性樹脂組成物以及使用其所得之發 光裝置。 【先前技術】 發光二極體（LED )等之發光裝置，爲了保護發光二 極體（LED )元件等之發光元件或改變發色，通常係以封 裝材被覆發光元件而構成。且，已知以高折射率材料被覆 發光元件可提高取出光效率。 過去’一般使用環氧樹脂作爲該封裝材之材料。然而 ’包含藍光LED元件或紫外線LED元件作爲發光元件之 LED在發光元件附近的環氧樹脂（封裝材）會因自藍光 LED元件發出之近紫外光或自紫外線LED元件發出之紫外 光而黃化，而有因發光元件之發熱而熱劣化之問題。尤其 ’於電燈等要求高亮度之用途，自藍光LED元件或紫外線 LED元件之發光量較多，容易引起黃化或熱劣化。 據此，作爲於要求高亮度之用途中，亦不會因近紫外 光或紫外光而造成黃化，且難以熱劣化之封裝材，已開發 出例如由二甲基聚矽氧烷所成之矽酮樹脂所構成之封裝材 。然而，該封裝材之問題爲折射率低，難以有效地取出來 自LED元件發出之光。 專利文獻1及2揭示含有具有鍵結於矽原子之烯基之矽 酮樹脂與具有Si-H鍵之有機氫聚矽氧烷之矽酮樹脂組成物 -5- 201141915 。該矽酮樹脂組成物若利用氫矽烷基化反應而交聯則獲得 硬化物。然而，該硬化物有折射率低之問題。 [先前技術文獻] 專利文獻 專利文獻1 :特開2004- 1 86 1 68號公報 專利文獻2 :特開2 0 0 4 - 2 2 1 3 0 8號公報 【發明內容】 [發明欲解決之課題] 本發明係爲解決上述之過去問題而完成者，其目的係 提供一種折射率高、透明性優異、以及耐熱性等亦優異之 硬化性樹脂組成物，以及發光效率優異之發光裝置。 [用以解決課題之手段] 本發明者等人爲達成上述目的而進行積極硏究，發現 若利用含有具有特定構造之矽氧烷系聚合物及氧化銷等金 屬氧化物粒子之硬化性樹脂組成物，則可較好地使用作爲 金屬氧化物粒子之分散性優異、折射率高、透明性優異、 進而耐熱性等亦優異之膜之材料，因而完成本發明。 亦即，本發明係提供以下之[1]〜[8]者。 [1] 一種發光裝置之製造方法，其包含下列步驟： (a )以硬化性樹脂組成物被覆發光元件之步驟，該 硬化性樹脂組成物含有： 201141915 (A)由含有以下述通式（i)表示之化合物之矽烷化 合物獲得之矽氧烷系聚合物， (R1)pSi(X)4-p (1) [通式（1 )中，R 1爲碳數1〜1 2之非水解性有機基，X爲水 解性基，及p爲0〜3之整數]， (B )金屬氧化物粒子，及（C )有機溶劑，且上述（ A) 成分含有矽烷醇基，該矽烷醇基中所含羥基數相對於 前述矽氧烷系聚合物中之矽原子數爲15〜3 00%，且上述（ B) 成分之調配量相對於上述（A)成分100質量份爲 50〜2,000質量份，及 (b )將上述發光元件加熱之步驟。 [2] —種發光裝置，其包含發光元件及形成在該發光元 件表面上之硬化性樹脂組成物之硬化物的硬化膜，該硬化 性樹脂組成物含有：（A)由含有以下述通式（1)表示之 化合物之矽烷化合物獲得之矽氧烷系聚合物， (R1)pSi(X)4-p (1) [通式（1 )中，R1爲碳數1〜12之非水解性有機基，X爲水 解性基，及P爲〇〜3之整數]，及（B )金屬氧化物粒子，且 上述（A)成分含有矽烷醇基，該矽烷醇基中所含羥基數 相對於前述矽氧烷系聚合物中之矽原子數爲15〜300%，上 述（B)成分之調配量相對於上述（A)成分100質量份爲 50〜2,000質量份。 [3] —種硬化性樹脂組成物，其含有（A )由含有以下 述通式（1 )表示之化合物之矽烷化合物獲得之矽氧烷系 201141915 聚合物， (R,)pSi(X)4.p ⑴ [通式（1 )中，R 1爲碳數1〜1 2之非水解性有機基，X爲水 解性基，及p爲0〜3之整數]，（B)金屬氧化物粒子’及（ C)有機溶劑，且上述（A)成分含有矽烷醇基’該矽烷醇 基中所含羥基數相對於前述矽氧烷系聚合物中之矽原子數 爲15〜3 00%，上述（B)成分之調配量相對於上述（A)成 分100質量份爲50~2,000質量份》 [4] 如上述[3]所述之硬化性樹脂組成物，其中上述（A )成分之矽烷醇基中所含羥基數相對於前述矽氧烷系聚合 物中之矽原子數爲3 0〜2 5 0% » [5] 如上述[3]或[4]所述之硬化性樹脂組成物，其中上 述（B )成分之調配量相對於上述（A)成分100質量份爲 100〜1，500質量份。 [6] 如上述[3]至[5]中任一項所述之硬化性樹脂組成物 ，其中上述（B)成分爲數平均一次粒徑爲1〜l〇〇nm之微 粒子。 [7 ]如上述[3 ]至[6 ]中任一項所述之硬化性樹脂組成物 ’其爲發光元件之被覆用。 [8 ] —種硬化性樹脂組成物之製造方法，其特徵爲在（ C)有機溶劑中混合1〇〇質量份之（A)矽氧烷系聚合物及 50〜2,000質量份之（B )金屬氧化物粒子而製造如上述 [3]〜[7]中任一項之硬化性樹脂組成物，該（A )矽氧烷系 聚合物爲由含有以下述通式（1)表示之化合物之矽烷化 -8 - 201141915 合物獲得之矽氧烷系聚合物，且含有矽烷醇基，該矽烷醇 基中所含羥基數相對於該矽氧烷系聚合物中之矽原子數爲 1 5 〜3 0 0 %， (R1)pSi(X)4-P (1) [通式（1 )中，R1爲碳數1~12之非水解性有機基，X爲水 解性基，及p爲0〜3之整數]。 [發明效果] 本發明之硬化性樹脂組成物之折射率高，且透明性、 耐熱性、龜裂耐性及耐光性優異。 本發明之硬化性樹脂組成物適宜作爲用以在發光元件 表面上形成硬化膜之材料。 在發光元件之表面上形成本發明之硬化性樹脂組成物 的硬化物之硬化膜之發光裝置具有高的發光效率。 【實施方式】 針對本發明所用之各成分加以詳細說明。 [(A)成分：由矽烷化合物所得之矽氧烷系聚合物] (A)成分係由含有以下述通式（1)表示之化合物之 矽烷化合物獲得之矽氧烷系聚合物， (R1)pSi(X)4.p ⑴ [通式（1)中，R1爲碳數1~12之非水解性有機基，X爲水 解性基，及p爲0〜3之整數]， 201141915 通式（1 )中以χ表示之水解性基通常係指 且在過量水存在下，在室溫（25 °C)〜100 °C之 加熱，使烷氧基水解生成矽烷醇基之基。再者 可在水解後進一步縮合形成矽烷氧縮合物》201141915 VI. [Technical Field] The present invention relates to a curable resin composition and a light-emitting device obtained using the same. [Prior Art] A light-emitting device such as a light-emitting diode (LED) is generally configured by covering a light-emitting element with a sealing material in order to protect a light-emitting element such as a light-emitting diode (LED) element or to change color. Further, it is known that coating a light-emitting element with a high refractive index material can improve light extraction efficiency. In the past, epoxy resins were generally used as the material of the package. However, an epoxy resin (package) containing an LED with a blue LED element or an ultraviolet LED element as a light-emitting element in the vicinity of the light-emitting element may be yellowed by ultraviolet light emitted from the blue LED element or ultraviolet light emitted from the ultraviolet LED element. There is a problem of thermal deterioration due to heat generation of the light-emitting element. In particular, in applications requiring high brightness such as electric lamps, the amount of light emitted from the blue LED element or the ultraviolet LED element is large, and yellowing or thermal deterioration is likely to occur. Accordingly, as an encapsulant which does not cause yellowing due to near-ultraviolet light or ultraviolet light and which is difficult to thermally deteriorate, it has been developed, for example, from dimethyl polyoxane. A packaging material composed of an anthrone resin. However, the problem of the package is that the refractive index is low, and it is difficult to efficiently extract light emitted from the LED element. Patent Documents 1 and 2 disclose an anthrone resin composition containing an anthracene resin having an alkenyl group bonded to a ruthenium atom and an organohydrogenpolyoxyalkylene having a Si-H bond -5-201141915. The fluorenone resin composition is crosslinked by hydroquinone alkylation reaction to obtain a cured product. However, the cured product has a problem of a low refractive index. [PRIOR ART DOCUMENT PATENT DOCUMENT PATENT DOCUMENT 1: JP-A-2004- 1 86 1 The present invention has been made to solve the above problems, and an object of the present invention is to provide a curable resin composition having high refractive index, excellent transparency, heat resistance, and the like, and a light-emitting device having excellent luminous efficiency. [Means for Solving the Problems] The inventors of the present invention conducted active research to achieve the above object, and found that a curable resin composition containing a metal oxide particle such as a siloxane-based polymer having a specific structure and an oxidation pin is used. In the present invention, the material of the film which is excellent in dispersibility of the metal oxide particles, high in refractive index, excellent in transparency, and excellent in heat resistance can be preferably used. That is, the present invention provides the following [1] to [8]. [1] A method of producing a light-emitting device, comprising the steps of: (a) coating a light-emitting element with a curable resin composition, the curable resin composition comprising: 201141915 (A) containing the following formula (i) ) a naphthenic polymer obtained from a decane compound of the compound, (R1) pSi(X)4-p (1) [In the formula (1), R 1 is a non-hydrolyzable carbon number of 1 to 12. An organic group, X is a hydrolyzable group, and p is an integer of 0 to 3, (B) a metal oxide particle, and (C) an organic solvent, and the above (A) component contains a stanol group, and the stanol group is The number of hydroxyl groups to be contained is 15 to 30,000% based on the number of ruthenium atoms in the azide-based polymer, and the amount of the component (B) is 50 to 2,000 parts by mass based on 100 parts by mass of the component (A). And (b) a step of heating the above-mentioned light-emitting element. [2] A light-emitting device comprising a light-emitting element and a cured film of a cured product of a curable resin composition formed on a surface of the light-emitting element, the curable resin composition comprising: (A) containing a general formula (1) a nonoxyl group-derived polymer obtained from a decane compound of the compound, (R1) pSi(X)4-p (1) [In the formula (1), R1 is a non-hydrolyzable group having a carbon number of 1 to 12 An organic group, X is a hydrolyzable group, and P is an integer of 〇3 to 3, and (B) a metal oxide particle, and the component (A) contains a stanol group, and the number of hydroxyl groups in the stanol group is relative to The number of the ruthenium atoms in the siloxane polymer is 15 to 300%, and the amount of the component (B) is 50 to 2,000 parts by mass based on 100 parts by mass of the component (A). [3] A curable resin composition comprising (A) a pyrithmene 201141915 polymer obtained from a decane compound containing a compound represented by the following formula (1), (R,) pSi(X)4 .p (1) [In the formula (1), R 1 is a non-hydrolyzable organic group having 1 to 12 carbon atoms, X is a hydrolyzable group, and p is an integer of 0 to 3], and (B) a metal oxide particle And (C) an organic solvent, wherein the component (A) contains a stanol group, and the number of hydroxyl groups in the stanol group is 15 to 30,000% based on the number of ruthenium atoms in the siloxane polymer, The amount of the component (B) is 50 to 2,000 parts by mass based on 100 parts by mass of the component (A), and the stil The number of the hydroxyl groups in the group is from 30 to 25% by the number of the ruthenium atoms in the azide-based polymer. [5] The curable resin composition according to the above [3] or [4], The amount of the component (B) to be added is 100 to 1,500 parts by mass based on 100 parts by mass of the component (A). [6] The curable resin composition according to any one of the above [3], wherein the component (B) is a microparticle having a number average primary particle diameter of 1 to 10 nm. [7] The curable resin composition as described in any one of the above [3] to [6], which is used for coating a light-emitting element. [8] A method for producing a curable resin composition, characterized by mixing 1 part by mass of (A) a phthalocyanine-based polymer and 50 to 2,000 parts by mass of (B) in (C) an organic solvent The curable resin composition according to any one of the above [3] to [7], wherein the (A) fluorinated base polymer is a compound containing a compound represented by the following formula (1). The alkylene oxide-derived polymer obtained by the alkylation of -8 - 201141915, and containing a stanol group, the number of hydroxyl groups contained in the stanol group is 15 5 with respect to the number of ruthenium atoms in the siloxane polymer 3 0 0 %, (R1) pSi(X)4-P (1) [In the formula (1), R1 is a non-hydrolyzable organic group having 1 to 12 carbon atoms, X is a hydrolyzable group, and p is 0. An integer of ~3]. [Effect of the Invention] The curable resin composition of the present invention has a high refractive index and is excellent in transparency, heat resistance, crack resistance, and light resistance. The curable resin composition of the present invention is suitably used as a material for forming a cured film on the surface of a light-emitting element. A light-emitting device which forms a cured film of a cured product of the curable resin composition of the present invention on the surface of the light-emitting element has high luminous efficiency. [Embodiment] Each component used in the present invention will be described in detail. [Component (A): a oxane-based polymer obtained from a decane compound] (A) is a siloxane-based polymer obtained from a decane compound containing a compound represented by the following formula (1), (R1) pSi(X)4.p (1) [In the formula (1), R1 is a non-hydrolyzable organic group having 1 to 12 carbon atoms, X is a hydrolyzable group, and p is an integer of 0 to 3], 201141915 Formula ( 1) The hydrolyzable group represented by hydrazine generally means that the alkoxy group is hydrolyzed to form a decyl alcohol group by heating at room temperature (25 ° C) to 100 ° C in the presence of excess water. Further, it can be further condensed after hydrolysis to form a decane oxygen condensate.
通式（1 )中附加字p爲0~3之整數，較好I 〇 矽氧烷系聚合物包含矽烷醇基。該矽烷醇 羥基數相對前述矽氧烷聚合物中之矽原子數爲 較好爲30〜250 %，更好爲50〜200%。矽烷醇基 基數相對於前述矽氧烷聚合物中之矽原子數若 內’則可獲得金屬氧化物之分散性優異之硬化 物，進而可獲得折射率高、透明性、耐熱性、 耐光性優異之膜。 砂氧院系聚合物若爲使至少兩個水解性砂 合者即可。 矽氧烷系聚合物亦可殘留一部分未水解之 且’矽氧烷系聚合物亦可爲一部分之矽烷醇基 彼此縮合之部分縮合物。 通式（1 )中之有機基R1爲非水解性爲碳 水解性有機基。有機基R 1中之非水解性基意指 基X水解之條件下，其本身仍安定存在之性質。 有機基R1列舉爲碳數1~12之烴基、碳數卜 基等。有機基R1可爲直鏈狀、分支狀、環狀或 之組合。且，有機基R1亦可爲含有雜原子之構 可在無觸媒 溫度範圍內 ，水解性基 | 0〜2之整數 基中所含之 〖1 5 〜3 0 0 %， 中所含之羥 在上述範圍 性樹脂組成 龜裂耐性及 烷化合物縮 水解性基。 或水解性基 數1〜1 2之非 在使水解性 1 2之鹵化烴 亦可爲該等 造。該等構 -10- 201141915 造單位可例示爲醚鍵、酯鍵、硫醚鍵等，作爲包含該等鑑 之有機基R1，可舉例有例如具有環氧乙烷基（oxiranyi ) 、氧雜環丁烷基等環氧基之基、具有（甲基）丙烯醯氧基 之基等。 有機基R1中之碳數1〜12之烴基就反應性及所得膜之龜 裂耐性之觀點而言，較好爲碳數之烴基，更好爲碳數 1〜4之烴基。具體而言，可列舉爲甲基、乙基、正丙基、 異丙基、正丁基、異丁基、第三丁基等脂肪族烴基、環丙 基、環丁基、環戊基、環己基等之脂環族烴基、苯蕋、甲 基苯基、乙基苯基、苄基等芳香族烴基，較好爲甲基、乙 基、正丙基、異丙基、第三丁基、苯基、甲基苯基，更好 爲甲基、乙基。 又，有機基R1中經鹵素原子取代之碳數1〜12之烴基列 舉爲氟化烴基、氯化烴基、溴化烴基，較好爲氟化烴基。 該烴基之碳數就反應性及所得膜之龜裂耐性之觀點而言， 較好爲1 ~ 4。 具體而言可列舉爲氯甲基 '二氯甲烷、三氯甲基、氟 甲基、二氟甲基、三氟甲基、2,2,2-三氟乙基、五氟乙基 、全氟正丙基、全氟異丙基、全氟正丁基、全氟異丁基、 全氟第三丁基，較好爲氟甲基、二氟甲基、三氟甲基、 2.2.2- 三氟乙基、五氟乙基、全氟正丙基、全氟異丙基、 全氟第三丁基，更好爲氟甲基、二氟甲基、三氟甲基、 2.2.2- 三氟乙基、五氟乙基。 通式（1 )中之水解性基X列舉爲氫原子、鹵素原子、 -11 - 201141915 碳數1~12之烷氧基、碳數1〜12之鹵化烷氧基、碳數2〜12之 醯氧基、碳數2〜12之鹵化醯氧基等。碳數1〜12之烷氧基之 較佳例列舉爲甲氧基、乙氧基等。鹵素原子之較佳例列舉 爲氟、氯、溴、碘等。醯氧基之較佳例列舉爲乙醯氧基、 丙醯氧基、丁醯氧基等。 茲對以通式（1 )表示之水解性矽烷化合物（有時僅 稱爲矽烷化合物）之具體例加以說明。 作爲含有4個水解性基之矽烷化合物，列舉爲四氯矽 烷、四胺基矽烷、四乙醯氧基矽烷、四甲氧基矽烷、四乙 氧基矽烷、四丁氧基矽烷、四苯氧基矽烷、四苄氧基矽烷 、三甲氧基矽烷、三乙氧基矽烷等。 具有三個水解性基之矽烷化合物列舉爲甲基三氯矽烷 '甲基三甲氧基矽烷、甲基三乙氧基矽烷、甲基三丁氧基 矽烷、乙基三甲氧基矽烷、乙基三異丙氧基矽烷、乙基三 丁氧基矽烷'丁基三甲氧基矽烷、五氟苯基三甲氧基矽烷 、苯基三甲氧基矽烷、d3-甲基三甲氧基矽烷、九氟丁基乙 基三甲氧基矽烷、三氟甲基三甲氧基矽烷等。 具有兩個水解性基之矽烷化合物列舉爲二甲基二氯矽 烷、二甲基二胺基矽烷、二甲基二乙醯氧基矽烷、二甲基 二甲氧基矽烷、二苯基二甲氧基矽烷、二丁基二甲氧基矽 烷等。 具有一個水解性基之矽烷化合物列舉爲三甲基氯矽烷 、六甲基二矽氮烷、三甲基矽烷、三丁基矽烷、三甲基甲 氧基矽烷'三丁基乙氧基矽烷等。 -12- 201141915 針對（A)成分之矽氧烷系聚合物加以說明。該分子 量可使用四氫呋喃爲移動相，利用凝膠滲透層析儀（以下 簡稱爲GPC) ’以聚苯乙烯換算之重量平均分子量測定。 矽氧烷系聚合物之重量平均分子量較好爲500〜 1 00,000 ’更好爲800〜30,000，又更好爲1，〇〇〇〜5,000。該 値未達500時，會有硬化膜形成時之龜裂耐性下降之傾向 。該値超過100,000時，會有（B )成分之金屬氧化物粒子 之分散性降低之傾向。 獲得矽氧烷矽聚合物時之觸媒 獲得矽氧烷系聚合物時之觸媒較好爲由金屬螯合化合 物、酸性化合物、及鹼性化合物所選出之至少一種化合物 ，更好爲酸性化合物。 (d-l )金屬螯合化合物 可作爲觸媒使用之金屬螯合化合物係以下述通式（2 )表示。 RI5eM(OR16)f.e (2) (式中’ R15爲螯合劑，Μ爲金屬原子，R16表示烷基或芳 基，f表示金屬Μ之原子價，e表示1〜f之整數）。 其中，金屬Μ較好爲由ΠΙΒ族金屬（鋁、鎵、銦、鉅 )及IVA族金屬（鈦、鉻、給）選出之至少一種金屬，更 好爲欽、飽、銷。 以R15表示之螯合劑可列舉爲CH3COCH2COCH3、 -13- 201141915 CH3COCH2COOC2H5 等。 以R16表示之烷基或芳基可列舉爲上述通式（1)中R1 所表示之烷基或芳基。 金屬螯合化合物之較佳具體例列舉爲 (CH3(CH3)HCO)4-tTi(CH3COCH2COCH3)t， (CH3(CH3)HCO)4.,Ti(CH3COCH2COOC2H5)t， (C4H90)4-,Ti(CH3C0CH2C0CH3)t， (C4H90)4-tTi(CH3C0CH2C00C2H5)t， (C2H5(CH3)CO)4-tTi(CH3COCH2COCH3)t， (C2H5(CH3)CO)4-tTi(CH3COCH2COOC2H5)t， (CH3(CH3)HCO)4-tZr(CH3COCH2COCH3)t， (CH3(CH3)HCO)4.tZr(CH3COCH2COOC2H5)t， (C4H90)4-tZr(CH3C0CH2C0CH3)t， (C4H90)4.tZr(CH3C0CH2C00C2H5)t， (C2H5(CH3)CO)4-tZr(CH3COCH2COCH3)t， (C2H5(CH3)CO)4.tZr(CH3COCH2COOC2H5)t， (CH3(CH3)HCO)3-tAl(CH3COCH2COCH3)t， (CH3(CH3)HCO)3-tAl(CH3COCH2COOC2H5)t， (C4H90)3.tAl(CH3C0CH2C0CH3)t， (C4H90)3-tAl(CH3C0CH2C00C2H5)t， (C2H5(CH3)CO)3.tAl(CH3COCH2COCH3)t， (C2H5(CH3)CO)3-tAl(CH3COCH2COOC2H5)^。 金屬螯合化合物之量相對於矽烷化合物之合計量100 質量份（換算完全水解縮合物），較好爲0.000 1〜10質量 -14- 201141915 份’更好爲0_001〜5質量份。該量未達〇〇〇〇1質量份，會有 塗膜之塗佈性變差之情況’超過丨〇質量份時，無法控制聚 合物成長，有引起凝膠化之情況。 在金屬蜜合化合物存在下使水解性矽烷化合物水解縮 合時’矽烷化合物之合計量每！莫耳較好使用〇.5〜2〇莫耳 之水，最好使用1〜1 0莫耳之水。水量未達〇 . 5莫耳時，水 解反應無法充分進行，有塗佈性及儲存安定性發生問題之 情況’超過20莫耳時’會有水解及縮合反應中聚合物析出 或發生凝膠化之情況。且，水較好間歇性或連續添加。 (d-2 )酸性化合物 可作爲觸媒使用之酸性化合物可例示爲有機酸或無機 酸，較好爲有機酸。 有機酸可列舉爲例如乙酸、丙酸、丁酸、戊酸、己酸 、庚酸、辛酸、壬酸、癸酸、草酸、馬來酸、甲基丙二酸 、己二酸、癸二酸、沒食子酸、丁酸、苯六甲酸（ Mellitic acid )、花生四烯酸、莽草酸（shikimic acid )、 2 -乙基己酸、油酸、硬脂酸' 亞油酸（linoleic acid)、 亞麻酸（linolenic acid)、水楊酸、苯甲酸、對-胺基苯 甲酸、對-甲苯磺酸、苯磺酸、單氯乙酸、二氯乙酸、三 氯乙酸、三氟乙酸、甲酸、丙二酸、磺酸、苯二甲酸、富 馬酸、檸檬酸、酒石酸、馬來酸酐、富馬酸、衣康酸、琥 珀酸、中康酸、檸康酸、蘋果酸、丙二酸、戊二酸之水解 物、馬來酸酐之水解物、苯二甲酸酐之水解物等。 -15- 201141915 無機酸可列舉爲例如鹽酸、硝酸、硫酸、氫氟酸、磷 酸等。 其中，就水解縮合（水解及其後續之縮合）反應中之 聚合物析出或凝膠化之虞較少觀點而言較好爲有機酸，其 中，更好爲具有羧基之化合物。 具有殘機之化合物中，最好爲乙酸、草酸、馬來酸、 甲酸、丙二酸、苯二甲酸、富馬酸'衣康酸、琥珀酸、中 康酸、檸康酸、蘋果酸、丙二酸、戊二酸、馬來酸酐之水 解物等有機酸。 該等酸性化合物可單獨使用一種或組合兩種以上使用 〇 酸性化合物之量相對於砂院化合物之合計量100質量 份（換算完全水解縮合物），較好爲0 · 〇 0 0〗〜i 0質量份， 更好爲0.001〜5質II份。該量未達〇.〇〇〇1質量份時，會有塗 膜之塗佈性變差之情況’超過1 〇質量份時，會有水解縮合 反應急速進行而引起凝膠化之情況。 在酸性化合物存在下使水解性矽烷化合物水解縮合時 ’矽烷化合物之合計量每1莫耳較好使用〇5〜2〇莫耳之水 ，最好使用1〜10莫耳之水。水量未達〇·5莫耳時，水解反 應無法充分進行，會有塗佈性及儲存安定性發生問題之情 況’超過2〇莫耳時’會有水解縮合反應中之聚合物析出或 發生凝膠化之情況。且，水較好間歇性或連續添加。 (d · 3 )鹼性化合物 -16- 201141915 可作爲觸媒使用之鹼性化合物列舉 醇胺、丙醇胺、丁醇胺、N-甲基甲醇胺 N -丙基甲醇胺、N -丁基甲醇胺、N -甲基 醇胺、N -丙基乙醇胺、n，N -二甲基甲醇 醇胺、N，N-二丙基甲醇胺、N，N_二丁基 甲醇胺、N -乙基二甲醇胺、N -丙基二甲 醇胺、N-(胺基甲基）甲醇胺、N-(胺 N-(胺基甲基）丙醇胺、N-(胺基甲基 甲基胺、甲氧基乙基胺、甲氧基丙基胺 N，N-二甲基胺、n，N-二乙基胺、N，N-二 基胺、三甲基胺、三乙基胺、三丙基胺 化四甲基銨、氫氧化四乙基銨、氫氧化 四丁基銨、四甲基乙二胺、四乙基乙二 、氨 '氫氧化鈉、氫氧化鉀、氫氧化四 乙基銨、氫氧化四正丙基銨、氫氧化四 甲基銨、氯化四甲基銨、溴化四乙基銨 鹼性化合物之量相對於矽烷化合物 計量1莫耳，較好爲0.00001〜10莫耳，] 耳。 [(B )成分：金屬氧化物粒子] 本發明中使用具有高折射率之金屬 具有高折射率之硬化物。該等微粒子只 400nm之光之折射率較好爲1.55以上， 爲例如甲醇胺、乙 、N-乙基甲醇胺' 乙醇胺、N-乙基乙 胺、Ν,Ν-二乙基甲 甲醇胺、Ν-甲基二 醇胺、Ν-丁基二甲 基甲基）乙醇胺、 )丁醇胺、甲氧基 、甲氧基丁基胺、 丙基胺、Ν，Ν-二丁 、三丁基胺、氫氧 四丙基銨、氫氧化 胺、四丙基乙二胺 甲基銨、氫氧化四 正丁基銨、溴化四 〇 中之水解性基之合 ϋ好爲0.00005〜5莫 氧化物粒子以獲得 要是在2 5 °C之波長 更好爲1.60以上， -17- 201141915 最好爲1 .70以上之微粒子則無特別限制，列舉爲例如氧化 鉻、氧化鈦、氧化鋅、氧化鉬、氧化銦、氧化給、氧化錫 、氧化鈮及該等之複合物等金屬氧化物粒子。其中，以氧 化锆（Zr02)之微粒子較佳。 上述氧化鈦只要具有Ti02構造者即無特別限制，列舉 爲例如銳鈦礦型、金紅石型、板鈦礦型。 該等金屬氧化物粒子可單獨使用一種，或組合兩種以 上使用。 (B)成分之金屬氧化物粒子之數平均一次粒徑較好 爲l~100nm，更好爲3〜70nm，最好爲5〜50nm。數平均一次 粒徑在上述範圍內時，可獲得透明性優異之硬化物。 (B)成分之金屬氧化物粒子在與（A)成分及（C) 成分混合前，可爲粉體狀，亦可爲溶劑分散之溶膠。溶劑 係使用例如有機溶劑。有機溶劑列舉爲例如2-丁醇、甲醇 、甲基乙基酮、甲基異丁基酮、環己酮、N-甲基-2-吡咯 烷酮、丙二醇單甲基醚等。 (B)成分之調配量相對於（A)成分100質量份爲 50〜2,000質量份，較好爲100~1，500質量份，更好爲 150〜1，000質量份。該量超過1，000質量份時，會有無法獲 得充分龜裂耐性之虞，該量未達100質量份時，硬化膜（ 組成物之硬化物）之折射率降低，會有發光裝置之發光效 率降低之虞。 再者，（B )成分爲溶劑分散之溶膠時’ （B )成分之 調配量係指不含溶劑之質量。又，（B )成分爲溶劑分散 -18- 201141915 之溶膠時，作爲（B)成分之溶劑之有機溶劑量爲構成（C )成分之有機溶劑之調配量之一部分者。 [(C)成分：有機溶劑] 本發明可藉由調配有機溶劑而提高組成物之儲存安定 性，且可賦予適當之黏度。 有機溶劑列舉爲醚系有機溶劑、酯系有機溶劑、酮系 有機溶劑、烴系有機溶劑、醇系有機溶劑等。作爲有機溶 劑較好使用在大氣壓下（l，〇13hPa)之沸點爲50〜250°C之 範圍內，可使各成分均勻分散之有機溶劑。 該等有機溶劑列舉爲例如脂肪族烴系溶劑、芳香族烴 系溶劑、單醇系溶劑、多元醇系溶劑、酮系溶劑、醚系溶 劑、酯系溶劑、含氮系溶劑、含硫系溶劑等。該等有機溶 劑可單獨使用一種或組合兩種以上使用。 有機溶劑中，就更提高組成物之儲存安定性之觀點而 言，較好爲單醇系溶劑、多元醇系溶劑、及酮系溶劑。該 等溶劑之較佳化合物之例列舉爲丙二醇單甲基醚、乳酸乙 酯、甲基乙基酮、甲基異丁基酮、環己酮、甲基戊基酮、 甲醇、乙醇、2-丁醇等。該等較佳之化合物可單獨使用一 種或組合兩種以上使用。 本發明中，有機溶劑之種類較好考慮組成物之塗佈方 法進行選擇。例如，爲了容易獲得具有均句厚度之硬化膜 (組成物之硬化物）而使用旋轉塗佈法時，有機溶劑較好 使用乙二醇單乙基醚、丙二醇單甲基醚等二醇醚類；乙基 -19- 201141915 溶纖素乙酸酯、丙二醇甲基醚乙酸酯、丙二 酯等乙二醇烷基醚乙酸酯類；乳酸乙酯、2-等酯類；二乙二醇單甲基醚、二乙二醇二甲 醇乙基甲基醚等二乙二醇類；甲基乙基酮、 、2-庚酮、環己酮、甲基戊基酮等酮類； 最佳之有機溶劑爲乙基溶纖素乙酸酯、 醚、丙二醇甲基醚乙酸酯、乳酸乙酯、甲基 異丁基酮、甲基戊基酮等。 (C)成分（有機溶劑）之調配量相對 除外之組成物之成分總量1 0 0質量份，較好： 量份，更好爲100〜1，000質量份。若在前述 ，則可提高組成物之儲存安定性，且賦予適 容易地形成具有均勻厚度之高折射率硬化膜 (c )成分之添加方法並無特別限制， (Α)成分時添加，亦可在調製含有（β )成 添加，亦可在混合（Α)成分與（Β)成分時 [(D )成分：分散劑] 本發明之硬化性樹脂組成物可使用各種 金屬氧化物粒子之分散性。 作爲分散劑可使用例如鋁化合物。鋁化 爲烷氧化鋁、鋁β-二酮酸酯錯合物等。具體 三乙氧基鋁、三（正丙氧基）鋁、三（異丙 (正丁氧基）鋁、三（第二丁氧基）鋁等烷 醇乙基醚乙酸 羥基丙酸乙酯 基醚、二乙二 甲基異丁基酮 內酯等.。 丙二醇單甲基 乙基酮、甲基 於該有機溶劑 爲 50~20,000質 之較佳範圍內 當之黏度，可 〇 例如可在製造 分之分散液時 添加。 分散劑以提高 合物之例列舉 而言可列舉爲 氧基）鋁、三 氧化合物，銘 -20- 201141915 參（甲基乙醯乙酸酯）'鋁參（乙基乙醯乙酸酯）、參（ 乙醯丙酮酸）鋁、鋁單乙醯基丙酮酸酯雙（甲基乙酸酯） 、鋁單乙醯基丙酮酸酯雙（乙基乙酸酯）等之β_二酮酸酯 錯合物。 鋁化合物之市售品可使用AIPD、PADM、AMD、 ASBD、乙氧化鋁、ALCH、ALCH-50F、ALCH-75、ALCH-TR、ALCH-TR-20、鋁螯合物M、鋁螯合物D、鋁螯合物A (W )、表面處理劑 OL-IOOO、ALUGOMER、ALUGOMER 8 00AF、ALUGOMER- 1 000SF (以上爲川硏精密化學公司 製造）等。 分散劑可使用非離子型分散劑。藉由使用非離子型分 散劑，可提高分散性。本發明所使用之非離子型分散劑較 好爲具有聚氧乙烯烷基構造之磷酸酯系非離子型分散劑。 分散劑之調配量並無特別限制，但含有分散劑時，相 對於有機溶劑除外之組成物成分總量1 00質量％爲例如 0.1 ~ 5 質量 ％。 [(E )成分：分散助劑] 本發明之硬化性樹脂組成物可進一步含有分散助劑以 提高分散性。分散助劑可適當使用由乙醯基丙酮、N，N-二 甲基乙醯基乙醯胺等之一種以上。 分散助劑之調配量並無特別限制，但含有分散助劑時 ，相對於有機溶劑除外之組成物成分總量1 00質量％爲例如 -21 - 201141915 [(F )成分：界面活性劑] 以旋轉塗佈將本發明之硬化性樹脂組成物塗佈於基材 等時’就獲得具有均勻厚度之塗膜之觀點而言，較好調配 界面活性劑。本發明中使用之界面活性劑列舉爲矽酮系界 面活性劑、氟系界面活性劑等。其中，以矽酮系界面活性 劑較佳。 矽酮系界面活性劑之例可列舉爲例如SH28PA ( Toray Dow Corning公司製造，二甲基聚矽氧烷聚氧伸烷基共聚 物）、PEINTADO 19、54 ( Toray Dow Corning公司製造， 二甲基聚矽氧烷聚氧伸烷基共聚物）、FM0411 ( SILAPLANE，CHISSO公司製造）、SF842 8 ( Toray Dow Corning公司製造，二甲基聚矽氧烷聚氧伸烷基共聚物（ 側鏈含有OH) ) 、BYKUV3510C日本BYK公司製造，二 甲基聚矽氧烷-聚氧伸烷基共聚物）、DC5 7 ( Toray Dow Corning公司製造，二甲基聚矽氧烷-聚氧伸烷基共聚物） 、DC190 ( Toray Dow C o r n i n g公司製造，二甲基聚砂氧 烷-聚氧伸烷基共聚物）、SILAPLANE FM-4411、FM-4421 、FM-4425 ' FM-771 1、FM- 7 72 1、FM-772 5、FM-0411、 FM-042 1、FM-0425、FM-DA11、FM-DA21、FM-DA26、 FM0711、FM072 1、FM-0725、TM-070 1、TM-070 1 T ( CHISSO公司製造）、UV3 500、UV3510、UV3 53 0 (曰本 BYK 公司製造）、BY1 6-004、SF8428 ( Toray DowThe additional word p in the formula (1) is an integer of 0 to 3, and preferably the I oxime siloxane polymer contains a stanol group. The number of hydroxyl groups of the stanol is preferably from 30 to 250%, more preferably from 50 to 200%, based on the number of ruthenium atoms in the above siloxane polymer. When the number of decyl alcohol groups is within the number of ruthenium atoms in the siloxane polymer, a cured product excellent in dispersibility of the metal oxide can be obtained, and further, a high refractive index, transparency, heat resistance, and light resistance can be obtained. The film. The sand oxide system polymer may be at least two hydrolyzable sands. The oxyalkylene-based polymer may also remain as a part of the condensate which is not hydrolyzed and the oxime-based polymer may be a part of the stanol group condensed with each other. The organic group R1 in the formula (1) is a non-hydrolyzable organic group. The non-hydrolyzable group in the organic group R 1 means a property which is inherently stable under the condition that the group X is hydrolyzed. The organic group R1 is exemplified by a hydrocarbon group having 1 to 12 carbon atoms, a carbon number group or the like. The organic group R1 may be linear, branched, cyclic or a combination thereof. Further, the organic group R1 may be a hydroxyl group-containing hydroxy group contained in an integer group containing a hydrolyzable group | 0 to 2 in a non-catalytic temperature range. In the above range of resins, the crack resistance and the alkyl compound hydrolyzable group are composed. Or a hydrolyzable group of 1 to 1 2 may be a halogenated hydrocarbon having a hydrolyzable property of 12. The isotactic structure is exemplified by an ether bond, an ester bond, a thioether bond, etc., and examples of the organic group R1 containing the above-mentioned are exemplified by having an oxiranyi group and an oxocyclic ring. A group having an epoxy group such as a butylene group or a group having a (meth)acryloxy group. The hydrocarbon group having 1 to 12 carbon atoms in the organic group R1 is preferably a hydrocarbon group having a carbon number, more preferably a hydrocarbon group having 1 to 4 carbon atoms, from the viewpoint of reactivity and crack resistance of the obtained film. Specific examples thereof include aliphatic hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and t-butyl groups, cyclopropyl, cyclobutyl and cyclopentyl groups. An aromatic hydrocarbon group such as an alicyclic hydrocarbon group such as a cyclohexyl group, a phenylhydrazine, a methylphenyl group, an ethylphenyl group or a benzyl group, preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group or a t-butyl group. Phenyl, methylphenyl, more preferably methyl or ethyl. Further, the hydrocarbon group having 1 to 12 carbon atoms which is substituted by a halogen atom in the organic group R1 is a fluorinated hydrocarbon group, a chlorinated hydrocarbon group or a brominated hydrocarbon group, and preferably a fluorinated hydrocarbon group. The carbon number of the hydrocarbon group is preferably from 1 to 4 from the viewpoint of reactivity and crack resistance of the obtained film. Specifically, it may be exemplified by chloromethyl 'methylene chloride, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, and all. Fluorylpropyl, perfluoroisopropyl, perfluoro-n-butyl, perfluoroisobutyl, perfluoro-tert-butyl, preferably fluoromethyl, difluoromethyl, trifluoromethyl, 2.2.2 - trifluoroethyl, pentafluoroethyl, perfluoro-n-propyl, perfluoroisopropyl, perfluoro-tert-butyl, more preferably fluoromethyl, difluoromethyl, trifluoromethyl, 2.2.2 - Trifluoroethyl, pentafluoroethyl. The hydrolyzable group X in the formula (1) is exemplified by a hydrogen atom, a halogen atom, an alkoxy group of -11 - 201141915 having a carbon number of 1 to 12, a halogenated alkoxy group having a carbon number of 1 to 12, and a carbon number of 2 to 12. A decyloxy group, a halogenated fluorenyloxy group having 2 to 12 carbon atoms, and the like. Preferable examples of the alkoxy group having 1 to 12 carbon atoms are a methoxy group, an ethoxy group and the like. Preferred examples of the halogen atom are fluorine, chlorine, bromine, iodine and the like. Preferred examples of the decyloxy group are an ethoxycarbonyl group, a propenyloxy group, a butoxy group and the like. Specific examples of the hydrolyzable decane compound (sometimes referred to simply as a decane compound) represented by the formula (1) will be described. Examples of the decane compound containing four hydrolyzable groups are tetrachlorodecane, tetraaminodecane, tetraethoxydecane, tetramethoxydecane, tetraethoxydecane, tetrabutoxydecane, and tetraphenyloxide. Alkane, tetrabenzyloxydecane, trimethoxydecane, triethoxydecane, and the like. The decane compound having three hydrolyzable groups is exemplified by methyltrichlorodecane 'methyltrimethoxydecane, methyltriethoxydecane, methyltributoxydecane, ethyltrimethoxydecane, ethyltri Isopropoxy decane, ethyl tributoxydecane 'butyl trimethoxy decane, pentafluorophenyl trimethoxy decane, phenyl trimethoxy decane, d3-methyl trimethoxy decane, nonafluoro butyl Ethyltrimethoxydecane, trifluoromethyltrimethoxydecane, and the like. The decane compound having two hydrolyzable groups is exemplified by dimethyldichlorodecane, dimethyldiaminodecane, dimethyldiethoxydecane, dimethyldimethoxydecane, diphenyldimethyl Oxydecane, dibutyl dimethoxydecane, and the like. The decane compound having one hydrolyzable group is exemplified by trimethylchlorodecane, hexamethyldioxane, trimethyldecane, tributyl decane, trimethyl methoxy decane 'tributyl ethoxy decane, and the like. . -12- 201141915 A description will be given of a naphthenic polymer based on the component (A). The molecular weight can be measured by using a gel permeation chromatography (hereinafter abbreviated as GPC) in terms of polystyrene-equivalent weight average molecular weight using tetrahydrofuran as a mobile phase. The weight average molecular weight of the siloxane-based polymer is preferably from 500 to 1,000,000, more preferably from 800 to 30,000, still more preferably from 1, 〇〇〇 to 5,000. When the enthalpy is less than 500, the crack resistance at the time of formation of a cured film tends to decrease. When the enthalpy exceeds 100,000, the dispersibility of the metal oxide particles of the component (B) tends to decrease. When the catalyst for obtaining a decane oxime polymer obtains a siloxane polymer, the catalyst is preferably at least one compound selected from a metal chelating compound, an acidic compound, and a basic compound, more preferably an acidic compound. . (d-1) Metal Chelate Compound The metal chelate compound which can be used as a catalyst is represented by the following formula (2). RI5eM(OR16)f.e (2) (wherein R15 is a chelating agent, ruthenium is a metal atom, R16 represents an alkyl group or an aryl group, f represents a valence of a metal ruthenium, and e represents an integer of 1 to f). Among them, the metal ruthenium is preferably at least one metal selected from the group consisting of lanthanum metals (aluminum, gallium, indium, giant) and Group IVA metals (titanium, chromium, and niobium), and is preferably a chin, a full, and a pin. The chelating agent represented by R15 may, for example, be CH3COCH2COCH3, -13-201141915 CH3COCH2COOC2H5 or the like. The alkyl group or the aryl group represented by R16 is exemplified by the alkyl group or the aryl group represented by R1 in the above formula (1). Preferred specific examples of the metal chelate compound are exemplified by (CH3(CH3)HCO)4-tTi(CH3COCH2COCH3)t, (CH3(CH3)HCO)4., Ti(CH3COCH2COOC2H5)t, (C4H90)4-, Ti( CH3C0CH2C0CH3)t, (C4H90)4-tTi(CH3C0CH2C00C2H5)t, (C2H5(CH3)CO)4-tTi(CH3COCH2COCH3)t, (C2H5(CH3)CO)4-tTi(CH3COCH2COOC2H5)t, (CH3(CH3) HCO) 4-tZr(CH3COCH2COCH3)t, (CH3(CH3)HCO)4.tZr(CH3COCH2COOC2H5)t, (C4H90)4-tZr(CH3C0CH2C0CH3)t, (C4H90)4.tZr(CH3C0CH2C00C2H5)t, (C2H5( CH3)CO)4-tZr(CH3COCH2COCH3)t, (C2H5(CH3)CO)4.tZr(CH3COCH2COOC2H5)t, (CH3(CH3)HCO)3-tAl(CH3COCH2COCH3)t, (CH3(CH3)HCO)3 -tAl(CH3COCH2COOC2H5)t, (C4H90)3.tAl(CH3C0CH2C0CH3)t, (C4H90)3-tAl(CH3C0CH2C00C2H5)t, (C2H5(CH3)CO)3.tAl(CH3COCH2COCH3)t, (C2H5(CH3)CO ) 3-tAl(CH3COCH2COOC2H5)^. The amount of the metal chelate compound is preferably from 0.000 1 to 10 parts by mass to 14 to 201141915 parts, more preferably from 0 to 001 parts by mass, based on 100 parts by mass of the total amount of the decane compound (in terms of the total hydrolysis condensate). When the amount is less than 1 part by mass, the coating property of the coating film may be deteriorated. When the amount exceeds 丨〇 by mass, the growth of the polymer cannot be controlled, and gelation may occur. When the hydrolyzable decane compound is hydrolyzed and contracted in the presence of a metal honey compound, the total amount of the decane compound is each! Moore is better to use 〇.5~2〇莫耳水, it is best to use 1~1 0 mo water. The amount of water does not reach 〇. At 5 mol, the hydrolysis reaction cannot be sufficiently carried out, and there are problems in coating properties and storage stability. When the temperature exceeds 20 m, the polymer may precipitate or gel in the hydrolysis and condensation reaction. The situation. Moreover, the water is preferably added intermittently or continuously. (d-2) Acid compound The acidic compound which can be used as a catalyst can be exemplified by an organic acid or an inorganic acid, preferably an organic acid. The organic acid may, for example, be acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, azelaic acid. , gallic acid, butyric acid, mellitic acid, arachidonic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid linoleic acid , linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, Malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, maleic anhydride, fumaric acid, itaconic acid, succinic acid, mesaconic acid, citraconic acid, malic acid, malonic acid, A hydrolyzate of glutaric acid, a hydrolyzate of maleic anhydride, a hydrolyzate of phthalic anhydride, and the like. -15- 201141915 The inorganic acid may, for example, be hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid or the like. Among them, an organic acid is preferred from the viewpoint of less precipitation or gelation of the polymer in the hydrolysis condensation (hydrolysis and subsequent condensation) reaction, and among them, a compound having a carboxyl group is more preferable. Among the compounds having a residual machine, acetic acid, oxalic acid, maleic acid, formic acid, malonic acid, phthalic acid, fumaric acid' itaconic acid, succinic acid, mesaconic acid, citraconic acid, malic acid, An organic acid such as malonic acid, glutaric acid or a hydrolyzate of maleic anhydride. These acidic compounds may be used singly or in combination of two or more kinds of the hydrazine acidic compound in an amount of 100 parts by mass based on the total amount of the sand compound (in terms of the fully hydrolyzed condensate), preferably 0 · 〇0 0 〗 〖i 0 The parts by mass are more preferably 0.001 to 5 parts by mass. When the amount is less than 1 part by mass, the coating property of the coating film may be deteriorated. When the amount exceeds 1 part by mass, the hydrolysis condensation reaction may rapidly proceed to cause gelation. When the hydrolyzable decane compound is hydrolyzed and condensed in the presence of an acidic compound, the total amount of the decane compound is preferably 5 to 2 Torr of water per 1 mole, preferably 1 to 10 moles of water. When the amount of water is less than 5 moles, the hydrolysis reaction may not proceed sufficiently, and there may be problems in coating properties and storage stability. When the amount exceeds 2 moles, the polymer in the hydrolysis condensation reaction may precipitate or condense. The situation of gelatinization. Moreover, the water is preferably added intermittently or continuously. (d · 3 ) Basic compound-16- 201141915 The basic compound which can be used as a catalyst is exemplified by alkanolamine, propanolamine, butanolamine, N-methylmethanolamine N-propylmethanolamine, N-butyl Methanolamine, N-methylolamine, N-propylethanolamine, n,N-dimethylpropanolamine, N,N-dipropylmethanolamine, N,N-dibutylmethanolamine, N-B Dimethanolamine, N-propyldimethanolamine, N-(aminomethyl)methanolamine, N-(amine N-(aminomethyl)propanolamine, N-(aminomethylmethylamine) , methoxyethylamine, methoxypropylamine N,N-dimethylamine, n,N-diethylamine, N,N-diylamine, trimethylamine, triethylamine, Tripropylammonium tetramethylammonium, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, tetramethylethylenediamine, tetraethylethylenediamine, ammonia's sodium hydroxide, potassium hydroxide, hydrogen hydroxide The amount of ethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetramethylammonium hydroxide, tetramethylammonium chloride, and tetraethylammonium bromide basic compound is 1 mol, preferably 0.00001, based on the decane compound. ~10 mol,] ear. [(B) component: metal oxide particles] The present invention A metal having a high refractive index has a high refractive index hardened material. The refractive index of the fine particles of only 400 nm is preferably 1.55 or more, and is, for example, methanolamine, ethylene, N-ethylmethanolamine, ethanolamine, N- Ethylethylamine, hydrazine, hydrazine-diethylmethanolamine, hydrazine-methyl diol amine, hydrazine-butyldimethylmethyl)ethanolamine, butanolamine, methoxy, methoxybutyl Amine, propylamine, hydrazine, hydrazine-dibutyl, tributylamine, tetrapropylammonium hydroxide, amine hydroxide, tetrapropylethylenediamine methylammonium, tetra-n-butylammonium hydroxide, bromide The combination of the hydrolyzable groups in the crucible is preferably 0.00005 to 5 molybdenum particles to obtain a wavelength of preferably more than 1.60 at a wavelength of 25 ° C, and -17 to 201141915 is preferably a particle of 1.70 or more. The limitation is exemplified by metal oxide particles such as chromium oxide, titanium oxide, zinc oxide, molybdenum oxide, indium oxide, oxidized, tin oxide, cerium oxide, and the like. Among them, fine particles of zirconium oxide (ZrO 2 ) are preferred. The titanium oxide is not particularly limited as long as it has a TiO 2 structure, and examples thereof include an anatase type, a rutile type, and a brookite type. These metal oxide particles may be used singly or in combination of two or more. The number average particle diameter of the metal oxide particles of the component (B) is preferably from 1 to 100 nm, more preferably from 3 to 70 nm, most preferably from 5 to 50 nm. When the number average primary particle diameter is within the above range, a cured product excellent in transparency can be obtained. The metal oxide particles of the component (B) may be in the form of a powder or a solvent-dispersed sol before being mixed with the components (A) and (C). The solvent is, for example, an organic solvent. The organic solvent is exemplified by, for example, 2-butanol, methanol, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, propylene glycol monomethyl ether or the like. The amount of the component (B) is 50 to 2,000 parts by mass, preferably 100 to 1,500 parts by mass, more preferably 150 to 1,000 parts by mass, per 100 parts by mass of the component (A). When the amount is more than 1,000 parts by mass, sufficient crack resistance may not be obtained. When the amount is less than 100 parts by mass, the refractive index of the cured film (hardened material of the composition) is lowered, and the light of the light-emitting device may be emitted. The efficiency is reduced. Further, when the component (B) is a solvent-dispersed sol, the amount of the component (B) is a mass which does not contain a solvent. Further, when the component (B) is a solvent-dispersed sol of -18 to 201141915, the amount of the organic solvent as the solvent of the component (B) is one of the amounts of the organic solvent constituting the component (C). [(C) component: organic solvent] The present invention can improve the storage stability of the composition by blending an organic solvent, and can impart an appropriate viscosity. The organic solvent is exemplified by an ether-based organic solvent, an ester-based organic solvent, a ketone-based organic solvent, a hydrocarbon-based organic solvent, or an alcohol-based organic solvent. As the organic solvent, an organic solvent in which the components are uniformly dispersed in a range of 50 to 250 ° C at a pressure of atmospheric pressure (1, 〇 13 hPa) is preferably used. Examples of the organic solvent include an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, a monool solvent, a polyol solvent, a ketone solvent, an ether solvent, an ester solvent, a nitrogen-containing solvent, and a sulfur-containing solvent. Wait. These organic solvents may be used alone or in combination of two or more. In the organic solvent, a monool solvent, a polyol solvent, and a ketone solvent are preferred from the viewpoint of further improving the storage stability of the composition. Preferred examples of such solvents are propylene glycol monomethyl ether, ethyl lactate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl amyl ketone, methanol, ethanol, 2- Butanol and the like. These preferred compounds may be used alone or in combination of two or more. In the present invention, the kind of the organic solvent is preferably selected in consideration of the coating method of the composition. For example, in order to easily obtain a cured film having a uniform thickness (a cured product of a composition) and using a spin coating method, a glycol ether such as ethylene glycol monoethyl ether or propylene glycol monomethyl ether is preferably used as the organic solvent. ;ethyl-19- 201141915 Ethyl glycol alkyl ether acetates such as cellosolve acetate, propylene glycol methyl ether acetate, propylene glycol; ethyl lactate, 2-ester esters; diethylene glycol Diethylene glycols such as monomethyl ether, diethylene glycol dimethanol ethyl methyl ether; ketones such as methyl ethyl ketone, 2-heptanone, cyclohexanone, methyl amyl ketone; The organic solvent is ethyl cellosolve acetate, ether, propylene glycol methyl ether acetate, ethyl lactate, methyl isobutyl ketone, methyl amyl ketone or the like. The compounding amount of the component (C) (organic solvent) is preferably 100 parts by mass, more preferably 100 parts by weight to 1,000 parts by mass, based on the total amount of the components of the composition excluding the composition. In the above, the storage stability of the composition can be improved, and the method of adding the high refractive index cured film (c) having a uniform thickness can be easily added, and the method of adding the (Α) component can be added. When the (β) is added and added, and the (Α) component and the (Β) component are mixed [(D) component: dispersant] The curable resin composition of the present invention can use the dispersibility of various metal oxide particles. . As the dispersing agent, for example, an aluminum compound can be used. Aluminization is an alkane alumina, an aluminum β-diketonate complex, and the like. Specific triethoxy aluminum, tri(n-propoxy)aluminum, tris(isopropyl(n-butoxy)aluminum, tris(t-butoxy)aluminum, etc. alkanol ethyl ether acetate hydroxypropionate ethyl ester Ether, diethyl dimethyl isobutyl ketone lactone, etc. propylene glycol monomethyl ethyl ketone, methyl group in the organic solvent is preferably in the range of 50 to 20,000, the viscosity can be, for example, can be manufactured When the dispersion is added, the dispersant may be exemplified by an oxy) aluminum, a trioxane, and the -20-201141915 gin (methyl acetoacetate) 'aluminum ginseng (B) Ethyl acetate, ginseng (acetate pyruvate) aluminum, aluminum monoethyl acetonate bis (methyl acetate), aluminum monoethyl acetonate bis (ethyl acetate) Etc. β-diketonate complex. Commercially available aluminum compounds can be used AIPD, PADM, AMD, ASBD, acetonitrile, ALCH, ALCH-50F, ALCH-75, ALCH-TR, ALCH-TR-20, aluminum chelate M, aluminum chelate D, aluminum chelate A (W), surface treatment agent OL-IOOO, ALUGOMER, ALUGOMER 8 00AF, ALUGOMER- 1 000SF (above is manufactured by Chuanxi Precision Chemical Co., Ltd.) and the like. A nonionic dispersant can be used as the dispersant. Dispersibility can be improved by using a nonionic dispersant. The nonionic dispersing agent used in the present invention is preferably a phosphate-based nonionic dispersing agent having a polyoxyethylene alkyl structure. The amount of the dispersing agent is not particularly limited. However, when the dispersing agent is contained, the total amount of the component components excluding the organic solvent is, for example, 0.1 to 5% by mass. [(E) component: dispersing aid] The curable resin composition of the present invention may further contain a dispersing aid to improve dispersibility. The dispersing aid may be one or more selected from the group consisting of etidylacetone and N,N-dimethylethendylacetamide. The amount of the dispersing aid to be added is not particularly limited, but when the dispersing aid is contained, the total amount of the constituent components other than the organic solvent is 100% by mass, for example, -21,194,419,150 [(F) component: surfactant] When the curable resin composition of the present invention is applied to a substrate or the like by spin coating, it is preferred to prepare a surfactant in terms of obtaining a coating film having a uniform thickness. The surfactant used in the present invention is exemplified by an anthrone-based surfactant, a fluorine-based surfactant, and the like. Among them, an anthrone-based surfactant is preferred. Examples of the anthrone-based surfactants include, for example, SH28PA (manufactured by Toray Dow Corning Co., Ltd., dimethyl polyoxyalkylene polyoxyalkylene copolymer), PEINTADO 19, 54 (manufactured by Toray Dow Corning, dimethyl Polyoxyalkylene polyoxyalkylene copolymer), FM0411 (SILAPLANE, manufactured by CHISSO), SF842 8 (manufactured by Toray Dow Corning, dimethyl polyoxyalkylene polyoxyalkylene copolymer (the side chain contains OH) )), BYKUV3510C manufactured by BYK, Japan, dimethyl polyoxane-polyoxyalkylene copolymer), DC5 7 (manufactured by Toray Dow Corning, dimethyl polyoxyalkylene-polyoxyalkylene copolymer) ), DC190 (manufactured by Toray Dow C orning, dimethyl polyoxaxane-polyoxyalkylene copolymer), SILAPLANE FM-4411, FM-4421, FM-4425 'FM-771 1, FM-7 72 1. FM-772 5, FM-0411, FM-042 1, FM-0425, FM-DA11, FM-DA21, FM-DA26, FM0711, FM072 1, FM-0725, TM-070 1, TM-070 1 T (manufactured by CHISSO), UV3 500, UV3510, UV3 53 0 (manufactured by BY本 BYK), BY1 6-004, SF8428 (Toray Dow
Corning公司製造）、VPS-1001 (和光純藥製造）等。最 -22- 201141915 佳之例可歹丨J 舉爲 SILAPLANE FM-7711、FM-7721、FM-7725、FM-0411、FM-042 1、FM-0425、FM0711、FM072 1 、FM-0725、VPS-1001等。另外，具有乙烯性不飽和基之 矽酮化合物之市售品可列舉爲例如Tego Rad2300、2200N (TEGO化學公司製造）等。 氟系界面活性劑列舉爲例如M e g a fa c F -1 1 4、F 4 1 0、 F411 、 F450、F493、F494、F443、F444、F 44 5 ' F446、 F470 、 F471 、 F472SF 、 F474 、 F475 、 R30 、 F477 、 F478 、 F479 ' F480SF 、 F482 、 F483 、 F484 、 F486 、 F487 、 F172D 、F178K、F178RM、ESM-1、MCF3 50SF、BL20、R08、 R61、R90 ( DIC公司製造）。 (F )成分之調配比例相對於有機溶劑除外之組成物 成分總量100質量％，較好爲0〜10質量％，更好爲0.1-5質 量％，最好爲〇 · 5〜3質量％。該量超過1 0質量％時，會有組 成物之硬化物折射率降低之虞。 [(G )成分：脫水劑] 本發明之硬化性樹脂組成物亦可含有脫水劑。藉由添 加脫水劑，可促進組成物之輻射線硬化反應，同時更提高 組成物之儲存安定性。 本發明中使用之脫水劑定義爲利用化學反應將水轉換 成水以外之物質之化合物，或者藉由物理吸附或包接，將 水轉換成不影響輻射線硬化性及儲存安定性之化合物。藉 由含有脫水劑，可不損及組成物之耐光性或耐熱性，而提 -23- 201141915 高儲存安定性與輻射線硬化性之相反的二種特性。至於其 理由，認爲是利用脫水劑有效吸收自外部侵入之水，而提 高組成物之儲存安定性，另一方面於輻射線硬化反應的縮 合反應中，藉由脫水劑逐次吸收生成之水，而提高組成物 之輻射線硬化性。 [(H)成分：酸產生劑] 本發明之硬化性樹脂組成物亦可含有酸產生劑。所謂 酸產生劑係定義爲可藉由光照射或加熱發生使成分（A ) 聚合之活性種（自由基或酸）之化合物。 此處所謂光照射意指例如紅外線、可見光、紫外線及 X射線、電子束、α射線、β射線、γ射線之電離輻射線之照 射。 另外，可利用光照射產生酸之光酸產生劑可列舉具有 以通式（3)表示之構造之錙鹽（第一群化合物）’或具 有以通式（4)表示之構造之磺酸衍生物（第二群化合物 )° [R2aR3bR4cR5dW]m+[MZm + „]m· (3) [通式（3 )中，陽離子爲鑰離子，W爲S、Se、Te、P、As 、813、8卜0、1、81、（：1或->^>^，112、113、114及115爲相同 或不同之有機基，a、b、c及d分別爲0〜3之整數，（ a + b + c + d) _n爲W之價數等。另外’ Μ爲構成鹵化物錯合物 [MXm + n]之中心原子之金屬或類金屬化物’例如Β、ρ、As 、Sb 、 Fe 、 Sn 、 Bi 、 A1 、 Ca 、 In 、 Ti 、 Zn 、 Sc、 V 、 Cr 、 -24- 201141915 Μη或Co。Z爲例如F、Cl、Br等鹵素原子或芳基，m爲鹵化 物錯合物離子之淨電荷，η爲Μ之原子價]。Made by Corning, VPS-1001 (made by Wako Pure Chemical Industries, etc.). Most -22- 201141915 Good example can be cited as SILAPLANE FM-7711, FM-7721, FM-7725, FM-0411, FM-042 1, FM-0425, FM0711, FM072 1 , FM-0725, VPS- 1001 and so on. Further, commercially available products of an anthranone compound having an ethylenically unsaturated group may, for example, be Tego Rad 2300 or 2200 N (manufactured by TEGO Chemical Co., Ltd.). Fluorine-based surfactants are exemplified by, for example, Mega fa c F -1 1 4, F 4 1 0, F411, F450, F493, F494, F443, F444, F 44 5 'F446, F470, F471, F472SF, F474, F475 , R30, F477, F478, F479 'F480SF, F482, F483, F484, F486, F487, F172D, F178K, F178RM, ESM-1, MCF3 50SF, BL20, R08, R61, R90 (manufactured by DIC Corporation). The compounding ratio of the component (F) is 100% by mass based on the total amount of the component components excluding the organic solvent, preferably 0 to 10% by mass, more preferably 0.1 to 5% by mass, most preferably 5% to 5% by mass. . When the amount exceeds 10% by mass, the refractive index of the cured product of the composition may decrease. [(G) component: dehydrating agent] The curable resin composition of the present invention may further contain a dehydrating agent. By adding a dehydrating agent, the radiation hardening reaction of the composition can be promoted, and the storage stability of the composition can be further improved. The dehydrating agent used in the present invention is defined as a compound which converts water into a substance other than water by a chemical reaction, or converts water into a compound which does not affect radiation hardenability and storage stability by physical adsorption or inclusion. By containing a dehydrating agent, the light resistance or heat resistance of the composition can be prevented, and the two characteristics of high storage stability and radiation hardenability are raised. As for the reason, it is considered that the dehydrating agent effectively absorbs water invaded from the outside to improve the storage stability of the composition, and on the other hand, in the condensation reaction of the radiation hardening reaction, the generated water is successively absorbed by the dehydrating agent, The radiation hardenability of the composition is improved. [(H) component: acid generator] The curable resin composition of the present invention may further contain an acid generator. The acid generator is defined as a compound which can generate an active species (free radical or acid) which polymerizes the component (A) by light irradiation or heating. The term "light irradiation" as used herein means irradiation of ionizing radiation such as infrared rays, visible light, ultraviolet rays, and X-rays, electron beams, alpha rays, beta rays, and gamma rays. In addition, the photoacid generator which can generate an acid by light irradiation can be exemplified by an onium salt (first group compound) having a structure represented by the formula (3) or a sulfonic acid derivative having a structure represented by the formula (4). (Second group of compounds) ° [R2aR3bR4cR5dW]m+[MZm + „]m· (3) [In the general formula (3), the cation is a key ion, and W is S, Se, Te, P, As, 813, 8卜0,1,81, (:1 or ->^>^, 112, 113, 114 and 115 are the same or different organic groups, and a, b, c and d are each an integer of 0 to 3, ( a + b + c + d) _n is the valence of W, etc. Further 'Μ is a metal or metalloid which constitutes a central atom of the halide complex [MXm + n] such as Β, ρ, As, Sb, Fe, Sn, Bi, A1, Ca, In, Ti, Zn, Sc, V, Cr, -24- 201141915 Μη or Co. Z is a halogen atom or an aryl group such as F, Cl, Br, and m is a halide. The net charge of the complex ion, η is the valence of ruthenium].
Qs-[S( = 0)2-R6]t (4) [通式（4)中，Q爲一價或二價有機基，R6爲碳數1〜I2之 一價有機基，附加字s爲0或1，附加字t爲1或2]。 首先，第一群化合物之鐵鹽爲可藉由接受光而釋出酸 性活性物質之化合物。該等第一群化合物中，更有效之鑰 鹽爲芳香族鐵鹽，最好爲以下述通式（5)表示之二芳基 捵鹽。 [R^Ar'-I^Ar^R^CY·] (5) [通式（5 )中，R7及R8分別爲一價有機基，可相同亦可不 同，R7及R8之至少一方爲具有碳數4以上之烷基，Ar1及 Ar2分別爲芳香族基，可相同亦可不同，Y·爲一價陰離子 ，係由週期表3族、5族之氟化陰離子或CIO，' CF3-S〇T選 出之陰離子]。 又，若例示第二群化合物之以通式（4)表示之磺酸 衍生物之例時，可列舉爲二颯類、二磺醯基重氮甲烷類、 二磺醯基甲烷類、磺醯基苯甲醯基甲烷類、醯亞胺磺酸酯 類、苯偶因磺酸酯類、1-氧基-2·羥基-3-丙醇之磺酸酯類 、鄰苯三酚三磺酸酯類、苄基磺酸酯類。且，以通式（4 )表示之磺酸衍生物中，更好爲醢亞胺磺酸酯類，再更好 爲醯亞胺磺酸酯中之三氟甲基磺酸酯衍生物。 針對光酸產生劑之添加量（含有比例）加以說明。光 酸產生劑之添加量並無特別限制，但以硬化性樹脂組成物 -25- 201141915 之固成分總量作爲1 00質量份，通常較好成爲1 5質量份以 內之値。該添加量超過15質量份時，會有所得硬化物之耐 候性或耐熱性下降之傾向。 [(I )成分：其他添加劑] 本發明之硬化性樹脂組成物在不損及本發明效果之範 圍內，可含有上述以外各種添加劑。該等添加劑列舉爲例 如上述成分以外之硬化性化合物、抗氧化劑、紫外線吸收 劑等。 [硬化性樹脂組成物之製造方法] 本發明之硬化性樹脂組成物可藉由混合上述成分（A )〜（C )、及視需要調配之其他任意成分而調製。通常， 可以特定比例，在（C )有機溶劑中混合成分（A )特定之 矽氧烷系聚合物與成分（B)金屬氧化物粒子及任意添加 之其他成分，藉此調製硬化性樹脂組成物。 [硬化膜] 本發明組成物之硬化物的硬化膜之折射率較好爲1 .6 以上。該折射率在1.6以上時，發光裝置之發光效率變高 〇 硬化膜之膜厚並無特別限制，但依據發光元件之種類 可適宜設定在例如50ηηι~100μιη之範圍內。 -26- 201141915 [用途] 本發明之硬化性樹脂組成物並無特別限制，可使用於 例如發光二極體、半導體雷射、光二極體、光電晶體、電 致發光元件等發光元件、CCD、CMOS影.像感應器等中使 用之光學構件、太陽能電池之抗反射膜等中，較好用於發 光二極體、半導體雷射、光二極體、光電晶體、電致發光 元件等發光元件中。 [發光裝置及其製造方法] 本發明之發光裝置並無特別限制，列舉爲例如發光二 極體、半導體雷射、光二極體、光電晶體、電致發光元件 、CCD、C-MOS、太陽能電池等。 本發明之發光裝置可藉由於發光元件表面上被覆本發 明之硬化性樹脂組成物並經硬化形成硬化膜，接著視需要 以封裝材封裝而製造。 被覆（塗佈）本發明之硬化性樹脂組成物之方法並無 特別限制’考慮發光裝置之形狀等，可自旋轉塗佈、浸漬 塗佈、含浸、噴墨等中適宜選擇。 硬化方法可使用習知方法。具體而言列舉爲在 3 0 ~ 2 5 0 °C下加熱1分鐘〜2 4小時之方法。本發明之硬化性樹 脂組成物含有光酸產生劑時，較好在上述加熱步驟之前進 行光照射。此時之光照射較好以例如1〇〇〜5,000mJ/cm2之 能量照射紫外線。 圖1所示之發光裝置爲包含在發光元件1之表面上形成 -27- 201141915 由本發明之硬化性樹脂組成物所成之硬化膜2，且利用封 裝材5封裝之構造者。圖1中，符號3a、3b表示電極部，4a 、4b表示金屬細線，6表示絕緣基板。 發光裝置爲發光二極體時，可使用利用例如GaAs、 GaAlAs、AlGalnP、GaP、GaAsP、ZnSe、ZnS、GaN、 InGaN等化合物製造之發光二極體元件。且，發光二極體 之發光色並無特別限制，列舉爲例如紅、綠、藍、黃、橙 、黃綠、白等^ 實施例 以下，以實施例更具體說明本發明，但本發明並不受 該等實施例之任何限制。 [(A)成分之調製] [合成例1 ] 於附有攪拌機、回流管之燒瓶中添加甲基三甲氧基矽 烷（45.7g)、四乙氧基矽烷（12.33g)、丙二醇單甲基醚 (19.56g)、及草酸（0.03g)，經攪拌獲得溶液後，將溶 液溫度加熱至60°C。接著，滴加蒸餾水（22.3 8g)，滴加 結束後’在1 0 0 °C下攪拌溶液3小時。接著，減壓下進行濃 縮’且將最終之固成分調整成30質量％，獲得（A)成分 (丙二醇單甲基醚溶液）。將其稱爲「A-1」。 [合成例2] -28 - 201141915 於附有攪拌機、回流管之燒瓶中添加甲基三甲氧基矽 院（17.89g)、苯基三甲氧基砂院（35 8〇g)、四乙氧基 矽烷（3.42g)、丙二醇單甲基醚（24.84g ) '及草酸（ 〇. 〇 3 g ) ’經攪拌獲得溶液後’將溶液溫度加熱至6 〇 t。接 著’滴加蒸餾水（1 8 · 0 2 g ) ’滴加結束後，在1 〇〇 °c下攪拌 溶液3小時。接著’減壓下進行濃縮，且將最終之固成分 調整成30質量％ ’獲得（A)成分（丙二醇單甲基醚溶液 )。將其稱爲「A-2」。 至於「A-3」’係使用日本 Momentive Performance Materials公司製造之 YF-3800。 又’ 「Α-1」~「Α-3」之成分組成等示於表卜 [表1] 單位:質量0/〇 A-1 A-2 甲基三甲氧基矽烷 45.7 17.89 苯基三甲氧基矽烷 35.80 四乙氧基矽烷 12.33 3.42 蒸餾水 22.38 18.02 草酸 0.03 0.03 丙二醇單甲基醚 19.56 24.84 合計 100 100 比率γ(%) 141 182 分子量(Mw) 3100 2300 A-3:比較例(市售品，YF-3800,矽烷醇末端之聚二甲基矽氧烷),Y=4%，Mw=3500 [(A)成分之細烷醇基之定量方法] 使用 BRUKER AVANCE 500 型（Bruker公司製造）， 進行矽氧烷聚合物（水解縮合物）之29Si NMR光譜（ -29 - 201141915 100MHz )之測定（溶劑：氘化苯）。該測定中，各峰歸 屬於表2所示之矽原子（T1-T3及Q1~Q4)。藉由進行波形 分解解析，求得各矽原子之面積比，藉此可定量相對於全 部矽原子數之矽烷醇數（以下亦稱爲「比率Y」）。亦即 ，矽原子T1〜T3及Q1~Q4之面積比分別設爲ST1-ST3及 SQ1-SQ4 >全部矽原子數爲ST1-ST3及SQ1-SQ4之總和（ ST1+ST2+ST3+SQ1+SQ2+SQ3+SQ4) > 比率 X爲以式[Y=( 2xSTl+lxST2+0xST3+3xSQl+2xSQ2+3xSQ3+0xSQ4) /( ST1 + ST2 + ST3 + SQ1+SQ2 + SQ3 + SQ4)]表示。 [表2] 位移(ppm) -45〜 -65 -50〜 -80 -60〜 -85 -75〜 -88 -88〜 -94 -94- -103 -103- -115 矽原子 T1 T2 T3 01 02 03 04 —個矽原子上鍵 結之矽烷醇基數 2個 1個 〇個 3個 2個 1個 〇個 T1 :鍵結有碳原子1個與氧原子3個之矽原子(此處，分別係氧原子中之1個含於砂氧 烷鍵，2個含於矽烷醇基） T2 :鍵結有碳原子1個與氧原子3個之矽原子(此處，分別係氧原子中之2個含於砂氧 烷鍵，1個含於矽烷醇基） T3 :鍵結有碳原子1個與氧原子3個之矽原子(此處，氧原子均含於矽氧烷鍵） Q1 :鍵結有氧原子4個之矽原子(此處，分別係氧原子中之1個含於砂氧烷鍵，3個含於 砂院醇基） Q2 :鍵結有氧原子4個之矽原子(此處，分別係氧原子中之2個含於矽氧院鍵，2個含於 矽烷醇基） Q3 :鍵結有氧原子4個之矽原子(此處，分別係氧原子中之3個含於砂氧院鍵，1個含於 矽烷醇基） Q4 :鍵結有氧原子4個之矽原子(此處，分別係氧原子中之3個含於矽氧烷鍵，1個3^ 矽烷醇基） [組成物之調製]] -30- 201141915 將21.0g作爲（B)成分之氧化銷（一次平均 15nm) 、29.7g(固成分8.9g)之「A-1」、以使有 之總重量成爲7〇g之丙二醇單甲基酸饋入容器中’ 添加粒徑0.1mm之氧化锆珠粒（Nikkat0公司製造） 利用珠粒硏磨，以1 5 0 0 rP m攪拌1 0小時’使氧化鉻 子（（B)成分）分散。 於所得氧化锆微粒子之分散液中添加二甲基 烷-聚氧伸烷基共聚物0· 1 0g，獲得組成物「J-1」。Qs-[S( = 0)2-R6]t (4) [In the formula (4), Q is a monovalent or divalent organic group, and R6 is a one-valent organic group having a carbon number of 1 to I2, and an additional word s Is 0 or 1, the additional word t is 1 or 2]. First, the iron salt of the first group of compounds is a compound which can release an acid active material by receiving light. Among the first group of compounds, the more effective key salt is an aromatic iron salt, and is preferably a diaryl sulfonium salt represented by the following formula (5). [R^Ar'-I^Ar^R^CY·] (5) [In the formula (5), R7 and R8 are each a monovalent organic group, which may be the same or different, and at least one of R7 and R8 has The alkyl group having 4 or more carbon atoms, Ar1 and Ar2 are each an aromatic group, and may be the same or different. Y· is a monovalent anion, which is a fluorinated anion or CIO of Group 3 and Group 5 of the periodic table, 'CF3-S 〇T selected anion]. Further, examples of the sulfonic acid derivative represented by the formula (4) in the second group of compounds are exemplified by dioxins, disulfonyldiazomethanes, disulfonylmethanes, and sulfoniums. Benzobenzhydryl methanes, sulfhydryl sulfonates, benzoin sulfonates, sulfonates of 1-oxy-2.hydroxy-3-propanol, pyrogallol trisulfonic acid Esters, benzyl sulfonates. Further, among the sulfonic acid derivatives represented by the formula (4), more preferably sulfhydrazine sulfonates, more preferably trifluoromethanesulfonate derivatives of sulfhydrazine sulfonate. The addition amount (content ratio) of the photoacid generator will be described. The amount of the photoacid generator to be added is not particularly limited, but the total amount of the solid content of the curable resin composition -25 to 201141915 is 100 parts by mass, and usually it is preferably within 15 parts by mass. When the amount is more than 15 parts by mass, the weather resistance or heat resistance of the obtained cured product tends to decrease. [Component (I): Other Additives] The curable resin composition of the present invention may contain various additives other than the above insofar as the effects of the present invention are not impaired. These additives are exemplified by curable compounds other than the above components, antioxidants, ultraviolet absorbers, and the like. [Method for Producing Curable Resin Composition] The curable resin composition of the present invention can be prepared by mixing the above components (A) to (C) and optionally other optional components. In general, the component (A) specific azoxyalkylene polymer and the component (B) metal oxide particles and any other components added thereto may be mixed in a specific ratio in a (C) organic solvent, whereby the curable resin composition is prepared. . [Cured film] The cured film of the cured product of the composition of the present invention preferably has a refractive index of 1.6 or more. When the refractive index is 1.6 or more, the luminous efficiency of the light-emitting device is increased. 膜 The film thickness of the cured film is not particularly limited, but may be suitably set within a range of, for example, 50 ηηι to 100 μm depending on the type of the light-emitting element. -26-201141915 [Application] The curable resin composition of the present invention is not particularly limited, and can be used for, for example, a light-emitting element such as a light-emitting diode, a semiconductor laser, a photodiode, a photoelectric crystal, or an electroluminescence element, and a CCD. In an CMOS film, an optical member used in an image sensor, an antireflection film of a solar cell, or the like, it is preferably used in a light-emitting element such as a light-emitting diode, a semiconductor laser, a photodiode, a photoelectric crystal, or an electroluminescence element. . [Light-emitting device and method of manufacturing the same] The light-emitting device of the present invention is not particularly limited, and examples thereof include, for example, a light-emitting diode, a semiconductor laser, a photodiode, a photoelectric crystal, an electroluminescence device, a CCD, a C-MOS, and a solar cell. Wait. The light-emitting device of the present invention can be produced by coating a surface of a light-emitting element with a curable resin composition of the present invention and hardening it to form a cured film, followed by encapsulation with a package as needed. The method of coating (coating) the curable resin composition of the present invention is not particularly limited. It can be suitably selected from spin coating, dip coating, impregnation, ink jet, etc., depending on the shape of the light-emitting device. A conventional method can be used for the hardening method. Specifically, it is a method of heating at 30 to 250 ° C for 1 minute to 24 hours. When the curable resin composition of the present invention contains a photoacid generator, it is preferred to carry out light irradiation before the above heating step. The light irradiation at this time is preferably irradiated with ultraviolet rays at an energy of, for example, 1 〇〇 to 5,000 mJ/cm 2 . The light-emitting device shown in Fig. 1 is a structure including a cured film 2 formed of a curable resin composition of the present invention on the surface of the light-emitting element 1 and formed of a curable resin composition of the present invention, and is packaged by the sealing material 5. In Fig. 1, reference numerals 3a and 3b denote electrode portions, 4a and 4b denote fine metal wires, and 6 denotes an insulating substrate. When the light-emitting device is a light-emitting diode, a light-emitting diode element manufactured using a compound such as GaAs, GaAlAs, AlGalnP, GaP, GaAsP, ZnSe, ZnS, GaN, or InGaN can be used. Further, the luminescent color of the light-emitting diode is not particularly limited, and is exemplified by, for example, red, green, blue, yellow, orange, yellow-green, white, etc. Hereinafter, the present invention will be more specifically described by way of examples, but the present invention It is not subject to any limitation by these embodiments. [Preparation of component (A)] [Synthesis Example 1] Methyltrimethoxydecane (45.7 g), tetraethoxydecane (12.33 g), propylene glycol monomethyl ether were added to a flask equipped with a stirrer and a reflux tube. (19.56 g) and oxalic acid (0.03 g), after stirring to obtain a solution, the solution was heated to 60 °C. Then, distilled water (22.3 g) was added dropwise, and after the completion of the dropwise addition, the solution was stirred at 100 ° C for 3 hours. Subsequently, the concentration was adjusted under reduced pressure, and the final solid content was adjusted to 30% by mass to obtain a component (A) (propylene glycol monomethyl ether solution). Call it "A-1". [Synthesis Example 2] -28 - 201141915 To a flask equipped with a stirrer and a reflux tube, methyltrimethoxy sulfonium (17.89 g), phenyltrimethoxy sand (35 8 g), tetraethoxy group were added. After decane (3.42 g), propylene glycol monomethyl ether (24.84 g) 'and oxalic acid (〇. 〇3 g ) 'after stirring to obtain a solution, the temperature of the solution was heated to 6 〇t. Then, after the dropwise addition of distilled water (1 8 · 0 2 g ) was completed, the solution was stirred at 1 ° C for 3 hours. Then, the concentration was adjusted under reduced pressure, and the final solid content was adjusted to 30% by mass to obtain the component (A) (propylene glycol monomethyl ether solution). Call it "A-2". As for "A-3", the YF-3800 manufactured by Momentive Performance Materials of Japan was used. Further, the composition of 'Α-1' to 'Α-3' is shown in Table [Table 1] Unit: Mass 0/〇A-1 A-2 Methyltrimethoxydecane 45.7 17.89 Phenyltrimethoxy Decane 35.80 Tetraethoxydecane 12.33 3.42 Distilled water 22.38 18.02 Oxalic acid 0.03 0.03 Propylene glycol monomethyl ether 19.56 24.84 Total 100 100 Ratio γ (%) 141 182 Molecular weight (Mw) 3100 2300 A-3: Comparative example (commercial product, YF -3800, polydimethyl methoxy oxane at the end of stanol, Y = 4%, Mw = 3500 [Quantitative method of fine alkanol group of (A) component] BRUKER AVANCE 500 (manufactured by Bruker) Determination of 29Si NMR spectrum (solvent: deuterated benzene) of a decane polymer (hydrolysis condensate) (29 - 201141915 100 MHz). In this measurement, each peak belongs to the ruthenium atoms (T1-T3 and Q1 to Q4) shown in Table 2. By performing waveform decomposition analysis and determining the area ratio of each of the germanium atoms, the number of decanols relative to the total number of germanium atoms (hereinafter also referred to as "ratio Y") can be quantified. That is, the area ratios of the germanium atoms T1 to T3 and Q1 to Q4 are set to ST1-ST3 and SQ1-SQ4 >respectively; the total number of germanium atoms is the sum of ST1-ST3 and SQ1-SQ4 (ST1+ST2+ST3+SQ1+) SQ2+SQ3+SQ4) > The ratio X is expressed by the formula [Y=( 2xSTl+lxST2+0xST3+3xSQl+2xSQ2+3xSQ3+0xSQ4) /(ST1 + ST2 + ST3 + SQ1+SQ2 + SQ3 + SQ4)]. [Table 2] Displacement (ppm) -45~ -65 -50~ -80 -60~ -85 -75~ -88 -88~ -94 -94- -103 -103- -115 Helium Atom T1 T2 T3 01 02 03 04—The number of decyl alcohol groups bonded to a ruthenium atom is two, one, three, two, one, one, T1: one atom with carbon atoms and three atoms with oxygen atoms (here, respectively One of the oxygen atoms is contained in the siloxane bond, and two are contained in the decyl alcohol group. T2: one atom of one carbon atom and three atoms of the oxygen atom are bonded (here, two of the oxygen atoms, respectively) Contains a serotonic bond, one is contained in a stanol group. T3: One atom of a carbon atom and three atoms of an oxygen atom are bonded (here, the oxygen atom is contained in a decane bond) Q1: Bonding There are four atoms of the aerobic atom (here, one of the oxygen atoms is contained in the sand oxide, and the other is contained in the sand-based alcohol base). Q2: four atoms of the oxygen atom are bonded to the atom. Wherein, two of the oxygen atoms are contained in the deuterium bond, and two are contained in the decyl alcohol group. Q3: four atoms of the oxygen atom are bonded to each other (here, three of the oxygen atoms are respectively contained) In the sand-oxygen bond, one is contained in the stanol group. Q4: 4 atoms of the oxygen atom bonded to the oxygen atom ( Here, three of the oxygen atoms are respectively contained in the azide bond, and one of the 3 decyl alcohol groups) [modulation of the composition]] -30- 201141915 21.0 g is used as the oxidation pin of the component (B) "A-1" of an average of 15 nm) and 29.7 g (solid content: 8.9 g), and a propylene glycol monomethyl acid having a total weight of 7 〇g is fed into the container. 'Zirconium oxide beads having a particle diameter of 0.1 mm are added. (manufactured by Nikkat Co., Ltd.) The chromia oxide (component (B)) was dispersed by a bead honing at a stirring time of 1 500 rpm for 10 hours. To the dispersion of the obtained zirconia fine particles, 0. 10 g of a dimethylalkane-polyoxyalkylene copolymer was added to obtain a composition "J-1".
另外，除改變表3中所示之成分組成以外，餘: 」般，調製組成物「J-2」、「J-4」、「J-5」、「JIn addition, in addition to changing the composition of the components shown in Table 3, the composition "J-2", "J-4", "J-5", "J" were prepared.
[組成物之調製2 ] 將1 5.9 g作爲（B)成分之氧化銷微粒子（數平 粒徑：15nm) 、1.9g 之 PLADD ED-151 (化合物名 乙烯烷基磷酸酯）、三（第二丁氧基）鋁2.2g'乙 〇.9g、2-丁醇2.3g、甲基乙基酮54.3g饋入容器中， 添加粒徑0.1mm之氧化锆珠粒（Nikkato公司製造） 利用珠粒硏磨，以1 500rpm攪拌10小時，使氧化錆 子（（B)成分）分散。 於所得氧化锆微粒子之分散液7 7.5 g中添加2 2 . 成分6.7g)之「A-1」、二甲基聚矽氧烷-聚氧伸烷 物O.lg，獲得組成物「J-3」。 粒徑： 機溶劑 於其中 3 50g， 之微粒 聚砂氧 均一次 :聚氧 醯丙酮 於其中 300g， 之微粒 4g (固 蕋共聚 -31 - 201141915 [表3] 單位：質量份 J-1 J-2 J-3 J-4 J-5 J-6 A-1 (固成分） 8.9 6.7 23.9 A A-2(固成分） 8.9 29.9 A-3 8.9 B 氧化鉻 21.0 21.0 15.9 21.0 6.0 1-甲氧基-2-丙醇 70.0 70.0 15.7 70.0 70.0 C 2-丁醇 2.3 甲基乙基酮 54.3 甲基異丁基酮 70.0 D PLAAD ED-151 1.9 參(第二丁氧基)鋁 2.2 E 乙醯丙酮 0.9 F 二甲基聚矽氧烷-聚 氧伸烷基共聚物υ 0.1 0.1 0.1 0.1 0.1 0.1 合計 100.0 100.0 100.0 100.0 100.0 100.0 l)Toray Dow Coming公司製 針對前述各組成物「J-l」〜「J-6」，如下述進行評價 〇 〈組成物之特性評價〉 (1 )分散粒徑 針對所得組成物中之微粒子，以堀場製作所製造之動 態光散射式粒徑分布測定裝置測定於2 5 t之體積平均粒徑 。體積平均粒徑未達50nm者作爲「〇」，50nm以上未達 1 OOnm者爲「△」，lOOnm以上者爲「X」。結果示於表4。 〈硬化膜之製作〉 -32- 201141915 將組成物分配在直徑4英吋之熔融石英或矽基板上， 經旋轉塗佈使厚度成爲約1 μηι，在1 20°C加熱1分鐘，及在 200°C加熱60分鐘，製作硬化膜（膜厚：1μη〇 。 〈硬化膜之特性評價〉 針對如上述製作之硬化膜，測定下述特性並評價。結 果示於表4。 (2 )硬化性 以手指觸摸上述獲得之硬化膜表面，沒有發黏者判定 爲「〇」，有發黏者判定爲「X」。 (3 )龜裂耐性 以目視觀察上述獲得之硬化膜外觀，沒有龜裂者判定 爲「〇」，有龜裂者判定爲「Xj 。 (4 )透明性 使用日本分光公司製造之分光光度計，分別測定上述 獲得之硬化膜之波長4 〇 〇 nm之透過率（％ )。透過率爲9 0 % 以上時判定爲「〇」，未達90%時判定爲「X」。 (5 )折射率 使用MET0RIC0N公司製造之稜鏡耦合器，測定在 23°C、波長633nm之折射率。折射率爲1.6以上時判定爲「 -33- 201141915 〇」，未達1.6時判定爲「X」。 (6 )耐熱性[Preparation of Composition 2] 1 5.9 g of oxidized pin microparticles (number of flat particles: 15 nm) of (B) component, 1.9 g of PLADD ED-151 (compound name vinyl alkyl phosphate), and third (second Butyloxy)aluminum 2.2 g 'acetonitrile.9 g, 2-butanol 2.3 g, and methyl ethyl ketone 54.3 g were fed into a container, and zirconia beads having a particle diameter of 0.1 mm (manufactured by Nikkato Co., Ltd.) were used. After honing, the mixture was stirred at 1,500 rpm for 10 hours to disperse the cerium oxide (component (B)). To the 7.5 g of the obtained zirconia fine particle dispersion, 7.5 g of the component "A-1" and dimethyl polyoxyalkylene-polyoxyalkylene oxide O.lg were added to obtain a composition "J- 3". Particle size: The organic solvent is 3 50g, and the particle polyaluminum is once: 300g of polyoxyanthracene, and 4g of microparticles (solid-copolymer -31 - 201141915 [Table 3] Unit: parts by mass J-1 J- 2 J-3 J-4 J-5 J-6 A-1 (solid content) 8.9 6.7 23.9 A A-2 (solid content) 8.9 29.9 A-3 8.9 B Chromium oxide 21.0 21.0 15.9 21.0 6.0 1-methoxy -2-propanol 70.0 70.0 15.7 70.0 70.0 C 2-butanol 2.3 methyl ethyl ketone 54.3 methyl isobutyl ketone 70.0 D PLAAD ED-151 1.9 ginseng (second butoxy) aluminum 2.2 E acetamidine acetone 0.9 F dimethyl polysiloxane-polyoxyalkylene copolymer υ 0.1 0.1 0.1 0.1 0.1 0.1 Total 100.0 100.0 100.0 100.0 100.0 100.0 l) Toray Dow Coming Co., Ltd. for each of the above-mentioned compositions "Jl" ~ "J-6 Evaluation was carried out as follows: <Evaluation of characteristics of the composition> (1) Dispersion particle size The volume average of 25 5 was measured for the fine particles in the obtained composition by a dynamic light scattering type particle size distribution measuring apparatus manufactured by Horiba, Ltd. Particle size. When the volume average particle diameter is less than 50 nm, it is "〇", and those of 50 nm or more and less than 100 nm are "△", and those of 100 nm or more are "X". The results are shown in Table 4. <Preparation of cured film> -32- 201141915 The composition was dispensed on a fused silica or tantalum substrate having a diameter of 4 inches, spin-coated to a thickness of about 1 μm, heated at 1 20 ° C for 1 minute, and at 200 ° After heating at ° C for 60 minutes, a cured film (film thickness: 1 μη〇.) <Evaluation of characteristics of cured film> The following properties were measured and evaluated for the cured film prepared as described above. The results are shown in Table 4. (2) Curability When the finger touched the surface of the cured film obtained as described above, it was judged as "〇" if it was not sticky, and "X" when it was sticky. (3) Crack resistance was observed by visual observation of the appearance of the cured film obtained above, and no crack was judged. For the "〇", the cracker was judged as "Xj. (4) The transparency was measured by using a spectrophotometer manufactured by JASCO Corporation, and the transmittance (%) of the obtained cured film at a wavelength of 4 〇〇 nm was measured. When the rate is 90% or more, it is judged as "〇", and when it is less than 90%, it is judged as "X". (5) Refractive index The refractive index at 23 ° C and a wavelength of 633 nm is measured using a 稜鏡coupler manufactured by MET0RIC0N. When the refractive index is 1.6 or more, it is judged as "- 33- 201141915 〇", when it is less than 1.6, it is judged as "X". (6) Heat resistance
使用烘箱，使上述硬化膜在溫度200 °C進行加熱處理 60分鐘，處理前後之硬化膜之透過率之降低（透過率減少 之比例）未達1 〇 %時判定爲「〇」，超過1 〇 %時判定爲「X (7 )耐光性 使用朝日分光公司製造之光源系統（REX-1 000 )，評 價上述之硬化膜之耐光性。使用該光源系統進行1 0小時之 光照射（輻射照度l.5W/cm2，截除波長405nm以外之光， 試驗溫度23 °C )，以目視觀察試驗前後硬化膜之外觀，未 變化者判定爲「〇」，稍變色者判定爲「△」，黃化者判 定爲「X」。 [^4] 實施例1 實施例2 實施例3 比較例1 比較例2 比較例3 組成物種類 J-1 J-2 J-3 J-4 J-5 J-6 評價 比率Y(%) 141 182 141 4 182 141 分散粒徑 〇. 〇 〇 X 〇 硬化性 〇 〇 〇 X 〇 ------ 〇 龜裂耐性 〇 〇 〇 〇 〇 〇 透明性 〇 〇 〇 〇 ----- 〇 折射率 〇 〇 〇 X X 耐熱性 〇 〇 Δ 〇 〇— 耐光性 〇 〇 〇 - 〇 〇 -34- 201141915 由表4可了解’本發明之組成物之硬化物具有優異之 透明性、高的折射率、高的耐熱性、以及高的耐光性，可 知可期待來自具備LED元件等發光元件之發光裝置之輻射 光之有效利用。 【圖式簡單說明】 圖1爲槪念式顯示本發明之發光裝置之一例之剖面圖 【主要元件符號說明】 1 :發光元件 2 :硬化膜 3 a :電極部 3b :電極部 4a ·金屬細線 4b :金屬細線 5 :封裝材 6 :絕緣基板 -35-The cured film was heat-treated at a temperature of 200 ° C for 60 minutes in an oven, and the decrease in the transmittance of the cured film before and after the treatment (the ratio of the decrease in the transmittance) was less than 1%, and it was judged as "〇", and exceeded 1 〇. When it is determined as "X (7) light resistance, the light source system (REX-1 000) manufactured by Asahi Laser Co., Ltd. is used to evaluate the light resistance of the above-mentioned cured film. The light source system is used to perform light irradiation for 10 hours (irradiation illuminance) .5W/cm2, cut off light with a wavelength other than 405 nm, test temperature: 23 °C), and visually observe the appearance of the cured film before and after the test. If it is not changed, it is judged as "〇", and if it is slightly changed, it is judged as "△", yellowing The person judged to be "X". [^4] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Composition type J-1 J-2 J-3 J-4 J-5 J-6 Evaluation ratio Y (%) 141 182 141 4 182 141 Dispersed particle size 〇〇. 〇〇X 〇 hardening 〇〇〇X 〇------ 〇 crack resistance 〇〇〇〇〇〇 transparency 〇〇〇〇----- 〇 〇 Rate XX heat resistance 〇〇Δ 〇〇 - light resistance 〇〇〇 - 〇〇-34- 201141915 It can be understood from Table 4 that the cured product of the composition of the present invention has excellent transparency, high refractive index, With high heat resistance and high light resistance, it is expected that efficient use of radiation from a light-emitting device including a light-emitting element such as an LED element can be expected. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view showing an example of a light-emitting device of the present invention. [Main component symbol description] 1 : Light-emitting element 2: cured film 3 a : Electrode portion 3b : Electrode portion 4 a · Metal thin wire 4b: metal thin wire 5: packaging material 6: insulating substrate -35-