TW201220941A - have high refraction rate to provide excellent light emitting efficiency - Google Patents
have high refraction rate to provide excellent light emitting efficiency Download PDFInfo
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- TW201220941A TW201220941A TW100124448A TW100124448A TW201220941A TW 201220941 A TW201220941 A TW 201220941A TW 100124448 A TW100124448 A TW 100124448A TW 100124448 A TW100124448 A TW 100124448A TW 201220941 A TW201220941 A TW 201220941A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/85—Arrangements for extracting light from the devices
- H10K50/858—Arrangements for extracting light from the devices comprising refractive means, e.g. lenses
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/301—Details of OLEDs
- H10K2102/331—Nanoparticles used in non-emissive layers, e.g. in packaging layer
Abstract
Description
201220941 六、發明說明： 【發明所屬之技術領域】 本發明係關於發光元件及作爲構成發光元件之含粒子 層之材料之組成物。 【先前技術】 發光元件具有於透明基板之表面上依序層合透明陽電 極層、發光材料層、及陰電極層之順序層合而成之基本構 成。例如，有機電致發光元件係將來自其陽電極層之電洞 、來自其陰電極層之電子注入由有機材料組成之發光材料 層之內部，且藉由使電洞與電子在發光材料層內部再結合 ，生成激子，利用該激子失活時發出之光（螢光、磷光） 而發光之發光元件。於發光材料層產生之光係i透明基板 側射出至發光元件外部。 專利文獻1中揭示具有使用聚醚楓樹脂、聚醚醯亞胺 樹脂等高折射率樹脂之高折射率層之發光元件。 [先前技術文獻] [專利文獻] [專利文獻1]特開20〇4-296438號公報 【發明內容】 [發明欲解決之課題] 藉由使用專利文獻1中所述之透明導電性基板’可使 -5- 201220941 發光元件發出之光自透明基板側以某種程度效率良好地射 出。然而，藉由發光元件發出之光，會有使聚醚颯樹脂、 聚醚醯亞胺樹脂等高折射率樹脂劣化之問題。 因此本發明之目的係提供一種改善發光效率及耐久性 之發光元件。 [用以解決課題之手段] 本發明人爲解決上述課題而積極檢討之結果，發現若 發光元件具備含有特定成分之含粒子層，則可達成上述目 的，因而完成本發明》 亦即，本發明爲提供以下之[1]〜[7]者。 [1] —種發光元件，其特徵爲具備基板、第一電極、 發光層、第二電極及含粒子層，且以前述基板、前述第一 電極、前述發光層及前述第二電極之順序層合而成，前述 含粒子層係形成於前述第一電極之與形成有前述發光層之 側之相反側及前述第二電極之與形成有前述發光層之側之 相反側之至少一側上，前述含粒子層爲含有下述（A)成 分及（B)成分之形成含粒子層用組成物之硬化物， (A) 自矽氧烷系聚合物、鈦烷氧系聚合物及該等之 共聚物所選出之至少一種聚合物 (B) 金屬氧化物粒子。 [2] 如前述Π]所述之發光元件，其中發光元件爲有機 電致發光元件。 [3] 如前述[1]或[2]所述之發光元件，其係於前述基201220941 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a light-emitting element and a composition of a material containing a particle-containing layer constituting the light-emitting element. [Prior Art] The light-emitting element has a basic structure in which a transparent anode layer, a light-emitting material layer, and a cathode electrode layer are sequentially laminated on the surface of a transparent substrate. For example, an organic electroluminescent element injects electrons from a positive electrode layer thereof, electrons from a negative electrode layer thereof into a layer of a light-emitting material composed of an organic material, and allows holes and electrons to be inside the light-emitting material layer. In combination, an exciton is generated, and a light-emitting element that emits light by using the light (fluorescence, phosphorescence) emitted when the exciton is deactivated is used. The side of the light-emitting i-transparent substrate generated by the luminescent material layer is emitted to the outside of the light-emitting element. Patent Document 1 discloses a light-emitting element having a high refractive index layer of a high refractive index resin such as a polyether maple resin or a polyether fluorene resin. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Unexamined Patent Application Publication No. JP-A No. Hei. The light emitted from the light-emitting element of the -5 - 201220941 is efficiently emitted from the transparent substrate side to some extent. However, the light emitted from the light-emitting element has a problem of deteriorating a high refractive index resin such as a polyether oxime resin or a polyether quinone resin. SUMMARY OF THE INVENTION Accordingly, it is an object of the invention to provide a light-emitting element which improves luminous efficiency and durability. [Means for Solving the Problem] The present inventors have found out that the light-emitting element has a particle-containing layer containing a specific component, and the above object can be attained, and the present invention has been completed. To provide the following [1] ~ [7]. [1] A light-emitting device comprising: a substrate, a first electrode, a light-emitting layer, a second electrode, and a particle-containing layer, wherein the substrate, the first electrode, the light-emitting layer, and the second electrode are sequentially layered The particle-containing layer is formed on at least one side of the first electrode opposite to the side on which the light-emitting layer is formed and on the side opposite to the side of the second electrode on which the light-emitting layer is formed. The particle-containing layer is a cured product containing a composition for a particle-containing layer containing the following components (A) and (B), (A) a self-oxynet-based polymer, a titanium alkoxy polymer, and the like. At least one polymer (B) metal oxide particle selected from the copolymer. [2] The light-emitting element according to the above, wherein the light-emitting element is an organic electroluminescence element. [3] The light-emitting element according to the above [1] or [2], which is based on the aforementioned base
-6- 201220941 板及前述第一電極之間具備前述含粒子層而成。 [4】如前述[1]~[3]中任一項所述之發光元件，其中前 述聚合物爲使由以下述通式（1)所示之化合物與以下述 通式（2)所示之化合物選出之至少一種化合物經縮合而 成之聚合物， (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0~3之整數] (R1)PTi(X)4.p (2) [通式（2)中，R1爲碳數i — u之非水解性有機基，X爲水 解性基，及p爲0〜3之整數]» [5] 如前述[1]〜[4]中任一項所述之發光元件，其中前 述（B)成分之調配量相對於前述（A)成分1〇〇質ΐ份爲 5 0〜2，0 0 0質量份。 [6] 如前述[1]〜[5]中任一項所述之發光元件，其中前 述（Β)成分係數目平均一次粒徑爲1〜lOOnm之微粒子。 [7] —種形成含粒子層用組成物，其係用以形成如前 述[1]〜[6]中任一項所述之發光元件的含粒子層之組成物， 其特徵爲含有下述（A)成分及（B)成分， (A) 自矽氧烷系聚合物、鈦烷氧系聚合物及該等之 共聚物所選出之至少一種共聚物； ^ (B) 金屬氧化物粒子。 [發明效果] 201220941 本發明之發光元件由於具備由特定組成物之硬化物所 組成之含粒子層，且該含粒子層之折射率高，故具有優異 之發光效率。 另外，本發明之發光元件亦具有優異之耐久性，故即 使在嚴格之使用條件下，亦可在長期持續地不降低性能下 使用。 【實施方式】 以下，參照圖式說明本發明之發光元件之各種實施形 態例。 圖1中，發光元件1 〇爲本發明之發光元件之實施形態 例1。發光元件10具有依基板11、第一電極13、發光層15 、第二電極17、及含粒子層18之順序層合而成之構造。第 二電極17爲透射型電極，於發光層15生成之光通過第二電 極17及含粒子層18，發射至發光元件10之外部。 至於基板11可使用於一般發光元件所使用之基板，但 較好爲機械強度、熱安定性、透明性、表面平滑性、操作 容易性及防水性優異之玻璃基板或透明塑膠基板。 第一電極13係藉由使用蒸鍍法或濺鍍法等將形成第一 電極用物質供給於基板11之上面而形成。第一電極13具有 抵接於後述發光層15之第一面，及抵接於基板11之第二面 。形成第一電極用物質可使用透明的傳導性優異之氧化銦 錫（ITO )、氧化銦鋅（IZO )、氧化錫（Sn02 )、氧化 鋅（ZnO)等。或者，若使用鎂（Mg)、鋁（A1)、鋁· 8 -8- 201220941 鋰（Al-Li )、鈣（Ca )、鎂-銦（Mg-In )、鎂- I Ag)等，則可形成第一電極13作爲反射型電極。 發光層15爲利用藉由施加電場而顯示發光現象 而成膜者。至於該種物質，可使用激活氧化鋅ZnS ： ，X爲 Μη、Tb、Cu、Sm 等激活元素）、CaS:Eu、S SrGa2S4:Ce ' CaGa2S4:Ce ' CaS :Pb、BaAl2S4:E\i 等 即使用之無機EL物質，8-羥基喹啉之鋁錯合物、芳 類、蒽單結晶等低分子色素系之有機EL物質，聚 苯基伸乙烯基）、聚[2·甲氧基-5-(2-乙基己氧基 伸苯基伸乙烯基]、聚-(3-烷基噻吩）、聚乙烯基 共軛高分子系之有機EL物質等之自過去即使用之 物質。發光層15之厚度通常爲10〜lOOOnm，較好爲 nm，更好爲50〜200nm。發光層15可藉由蒸鍍或濺 真空成膜製程，或以氯仿等作爲溶劑之塗佈製程形 第二電極17爲電子注入電極的陽極。第二電極 成用金屬列舉爲鋰（Li )、鎂（Mg )、鋁（A1 ) (Al-Li)、鈣（Ca)、鎂-銦（Mg'-In )、鎂-銀（ )等。藉由於薄膜上形成該等金屬，可獲得透射型 另一方面，爲了獲得自元件側取出光之上發射方式 元件，亦可利用ITO、IZO形成透射型電極。 含粒子層18爲含有下述（A)成分及下述（B) 形成含粒子層用組成物之硬化物。 針對本發明中使用之各成分加以詳細說明。 ：(Mg- 之物質 X (但 r S : C e、 自過去 香族胺 (對-伸 )-1,4-咔唑等 有機EL 30〜500 鍍等之1 成。 17之形 、鋁-鋰 Mg-Ag 電極。 之發光 成分之 201220941 [(A)成分；由矽氧烷系聚合物、鈦氧烷系聚合物及 該等之共聚物選出之至少一種聚合物] 由矽氧烷系聚合物、鈦氧烷系聚合物及該等之共聚物 選出之至少一種聚合物可列舉爲例如使由以下述通式 )所示之化合物與以下述通式（2)所示之化合物選出之 至少一種化合物經縮合而成之聚合物， (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0〜3之整數] (R1)pTi(X)4.p (2) [通式（2)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]。 通式（1)及通式（2)中之以X表示之水解性基通常 爲可藉由在無觸媒且過量水存在下，於室溫（25 °C) 〜1 〇 0 °C之溫度範圍內加熱，使烷氧基等水解性基水解生成 矽烷醇基或鈦醇基之基。又，水解性基於水解後再經縮合 形成矽氧烷縮合物或鈦氧烷縮合物。 通式（1 )之附加字p爲0〜3之整數，較好爲〇~2之整數 〇 由矽氧烷系聚合物、鈦氧烷系聚合物及該等之共聚物 選出之至少一種聚合物較好含有矽烷醇基或鈦醇基。該矽 烷醇基或鈦醇基中所含羥基之數相對於聚合物中之矽原子 及鈦原子之數目之總和.，較好爲15~3 00%，更好爲 30〜250%，又更好爲50〜200%。矽烷醇基及鈦醇基中所含 201220941 羥基之數相對於聚合物中之矽原子及鈦原子之數目之總和 在上述範圍內時，可獲得金屬氧化物粒子之分散性優異之 形成含粒子層用組成物，進而可獲得折射率高、透明性、 耐熱性、龜裂耐性及耐光性優異之膜。 矽氧烷系聚合物亦可留下一部份未水解之水解性基。 又，矽氧烷系聚合物亦可爲一部份矽烷醇基或水解性基彼 此縮合而成之部份縮合物。 通式（1)及通式（2)中之有機基R1爲碳數1〜12之非 水解性有機基。有機基R1中之所謂非水解性意指在使水解 性基X水解之條件下，仍可就此安定地存在之性質。 作爲有機基R1列舉爲例如碳數1〜12之烴基、碳數1~12 之鹵化烴基等。有機基R1,可爲直鏈狀、分支狀、環狀或該 等之組合。又，有機基R1亦可具有含有雜原子之構造單位 。該等構造單位可例示爲醚鍵、酯鍵、硫醚鍵等，含有該 等鍵之有機基R1可列舉爲例如氧雜環丁烷基、環氧乙烷基 等具有環氧基之基、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1〜8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、第三丁基等之脂肪族烴基，環 丙基、環丁基、環戊基、環己基等脂環族烴基，苯基、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。 -11 - 201220941 另外，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。 具體而言爲氯甲基、二氯甲基、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、全氟乙基、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、全氟乙基。 通式（1)及通式（2)中之水解性基X列舉爲氫原子 、鹵素原子、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。 說明以通式（1 )表示之水解性矽烷化合物（以下簡 稱爲矽烷化合物）之具體例。 具有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 -12- 201220941 、甲基三甲氧基矽烷、甲基三乙氧基矽烷、甲基三 矽烷、乙基三甲氧基矽烷、乙基三異丙氧基矽烷、 丁氧基矽烷、丁基三甲氧基矽烷、五氟苯基三甲氧 、苯基三甲氧基矽烷、d3-甲基三甲氧基矽烷、九氟 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 烷、二甲基二胺基矽烷、二甲基二乙醯氧基矽烷、 二甲氧基矽烷、二苯基二甲氧基矽烷、二丁基二甲 烷等。 具有一個水解性基之矽烷化合物列舉爲三甲基 、六甲基二矽氮烷、三甲基矽烷、三丁基矽烷、三 氧基矽烷、三丁基乙氧基矽烷等。 說明以通式（2 )表示之水解性鈦化合物（以 簡稱爲駄化合物）之具體例。 具有四個水解性基之鈦化合物列舉爲四氯鈦、 鈦、四乙醯氧基鈦、四甲氧基鈦、四乙氧基鈦、四 鈦、四苯氧基鈦、四苄氧基鈦、三甲氧基鈦、三乙 等。 具有三個水解性基之鈦化合物列舉爲甲基三氯 基三甲氧基鈦、甲基三乙氧基鈦、甲基三丁氧基鈦 三甲氧基鈦、乙基三異丙氧基鈦、乙基三丁氧基鈦 三甲氧基鈦、五氟苯基三甲氧基鈦、苯基三甲氧基 甲基三甲氧基鈦、九氟丁基乙基三甲氧基鈦、三氟 甲氧基鈦等。 丁氧基 乙基三 基矽烷 丁基乙 二氯矽 二甲基 氧基矽 氯矽烷 甲基甲 下有時 四胺基 丁氧基 氧基鈦 鈦、甲 、乙基 、丁基 汰、d3- 甲基三 -13- 201220941 具有兩個水解性基之鈦化合物列舉爲二甲基二氯鈦、 二甲基二胺基鈦、二甲基二乙醯氧基鈦、二甲基二甲氧基 鈦、二苯基二甲氧基鈦、二丁基二甲氧基鈦等。 具有一個水解性基之鈦化合物列舉爲三甲基氯鈦、六 甲基二矽氮烷、三甲基鈦、三丁基鈦、三甲基甲氧基鈦、 三丁基乙氧基鈦等。 針對由（A)成分之矽氧烷系聚合物、鈦氧烷系聚合 物及該等之共聚物選出之至少一種聚合物之分子量加以說 明。該分子量可使用於移動相係使用四氫呋喃之凝膠滲透 層析儀（以下有時簡稱爲GPC )，以聚苯乙烯換算之重量 平均分子量測定。 由矽氧烷系聚合物、鈦氧烷系聚合物及該等之共聚物 選出之至少一種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 1，000〜5,000。該 値未達500時，有形成硬化膜時之龜裂耐性降低之傾向。 該値超過100,000時，有（B)成分之金屬氧化物粒子之分 散性降低之傾向。 獲得由矽氧院系聚合物、鈦氧院系聚合物及該等之共 聚物選出之至少一種聚合物時之觸媒較好爲由金屬蜜合化 合物、酸性化合物、及鹼性化合物選出之至少一種化合物 ，更好爲酸性化合物。 (d-Ι )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。-6- 201220941 The plate and the first electrode are provided with the particle-containing layer. [4] The light-emitting element according to any one of the above-mentioned [1], wherein the polymer is a compound represented by the following formula (1) and is represented by the following formula (2) a polymer obtained by condensing at least one compound selected from the compound, (R1)PSi(x)4.p (1) [In the formula (1), R1 is a non-hydrolyzable organic group having a carbon number of 1 to 12, X is a hydrolyzable group, and p is an integer of 0 to 3] (R1) PTi(X)4.p (2) [In the formula (2), R1 is a non-hydrolyzable organic group having a carbon number i - u, The light-emitting element according to any one of the above-mentioned [1] to [4] wherein the amount of the component (B) is adjusted relative to the foregoing (A) Component 1 〇〇 ΐ is 50 to 2,0 0 parts by mass. [6] The light-emitting element according to any one of [1] to [5] wherein the (Β) component is a microparticle having a number average primary particle diameter of 1 to 100 nm. [7] A composition for forming a particle-containing layer, which is a composition comprising a particle-containing layer of the light-emitting element according to any one of the above [1] to [6], which is characterized by comprising the following (A) component and (B) component, (A) at least one copolymer selected from the group consisting of a siloxane polymer, a titanium alkoxide polymer, and the like; ^ (B) Metal oxide particles. [Effect of the Invention] 201220941 The light-emitting device of the present invention has a particle-containing layer composed of a cured product of a specific composition, and the particle-containing layer has a high refractive index, so that it has excellent light-emitting efficiency. Further, the light-emitting element of the present invention has excellent durability, and can be used under long-term continuous use without deteriorating performance even under strict use conditions. [Embodiment] Hereinafter, various embodiments of a light-emitting device of the present invention will be described with reference to the drawings. In Fig. 1, a light-emitting element 1 is an embodiment 1 of a light-emitting element of the present invention. The light-emitting element 10 has a structure in which the substrate 11, the first electrode 13, the light-emitting layer 15, the second electrode 17, and the particle-containing layer 18 are laminated in this order. The second electrode 17 is a transmissive electrode, and light generated in the light-emitting layer 15 is emitted to the outside of the light-emitting element 10 through the second electrode 17 and the particle-containing layer 18. The substrate 11 can be used for a substrate used for a general light-emitting element, but is preferably a glass substrate or a transparent plastic substrate excellent in mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and water repellency. The first electrode 13 is formed by supplying a first electrode material to the upper surface of the substrate 11 by a vapor deposition method, a sputtering method, or the like. The first electrode 13 has a first surface that abuts on the light-emitting layer 15 to be described later, and a second surface that abuts against the substrate 11. As the material for the first electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (Sn02), zinc oxide (ZnO) or the like which is excellent in transparent conductivity can be used. Alternatively, if magnesium (Mg), aluminum (A1), aluminum · 8 -8 - 201220941 lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-I Ag, etc. are used, The first electrode 13 can be formed as a reflective electrode. The light-emitting layer 15 is formed by using a light-emitting phenomenon by applying an electric field. As for the substance, activated zinc oxide ZnS : , X is an active element such as Μη, Tb, Cu, Sm, etc., CaS:Eu, S SrGa2S4:Ce ' CaGa2S4:Ce ' CaS :Pb, BaAl2S4:E\i, etc. That is, the inorganic EL material to be used, an organic EL substance of a low molecular weight type such as an aluminum complex of 8-hydroxyquinoline, an aromatic or a quinone single crystal, a polyphenylene vinyl group, and a poly[2.methoxy-5 - (2-ethylhexyloxyphenylene vinylene), poly-(3-alkylthiophene), a polyvinyl conjugated polymer organic EL material, etc., which have been used in the past. The thickness is usually 10 to 100 nm, preferably nm, more preferably 50 to 200 nm. The light-emitting layer 15 can be formed by a vapor deposition or a vacuum deposition film forming process, or a coating process second electrode 17 using chloroform or the like as a solvent. The electron is injected into the anode of the electrode. The second electrode is made of metal as lithium (Li), magnesium (Mg), aluminum (A1) (Al-Li), calcium (Ca), magnesium-indium (Mg'-In), magnesium. - Silver ( ), etc. By means of the formation of such metals on the film, a transmissive type can be obtained. On the other hand, in order to obtain a light-emitting element from the element side, an ITO can also be used. IZO forms a transmissive electrode. The particle-containing layer 18 is a cured product containing the following component (A) and the following (B) to form a composition for a particle-containing layer. Each component used in the present invention will be described in detail. - Substance X (but r S : C e, organic EL 30~500 plating such as aroma amine (p-extension)-1,4-carbazole, etc. 17-shaped, aluminum-lithium Mg- Ag electrode. 201220941 [(A) component; at least one polymer selected from a siloxane polymer, a titanyl polymer, and the like], a siloxane polymer, titanium The at least one polymer selected from the oxyalkylene polymer and the copolymers may, for example, be at least one compound selected from the compounds represented by the following formula () and the compound represented by the following formula (2). Condensed polymer, (R1)pSi(X)4.p (1) [In the formula (1), R1 is a non-hydrolyzable organic group having a carbon number of 1 to 12, X is a hydrolyzable group, and P An integer of 0 to 3] (R1) pTi(X)4.p (2) [In the formula (2), R1 is a non-hydrolyzable organic group having a carbon number of 1 to 12, X is a hydrolyzable group, and P It is an integer from 0 to 3.]. The hydrolyzable group represented by X in the general formula (1) and the general formula (2) is usually at room temperature (25 ° C) to 1 〇 0 ° C in the absence of a catalyst and excess water. Heating in a temperature range causes hydrolysis of a hydrolyzable group such as an alkoxy group to form a stanol group or a titanol group. Further, the hydrolyzability is hydrolyzed and then condensed to form a siloxane condensate or a titanyl condensate. The additional word p of the formula (1) is an integer of 0 to 3, preferably an integer of 〇~2, at least one selected from the group consisting of a decane-based polymer, a titanyl-based polymer, and copolymers thereof. The polymer preferably contains a stanol or titanium alkoxide group. The sum of the number of hydroxyl groups contained in the stanol group or the titanium alcohol group relative to the number of ruthenium atoms and titanium atoms in the polymer is preferably from 15 to 30,000%, more preferably from 30 to 250%, and further Good for 50~200%. When the sum of the number of the hydroxyl groups of 201220941 and the number of the ruthenium atoms and the titanium atoms in the sterol group and the titanol group is within the above range, the particle-forming layer having excellent dispersibility of the metal oxide particles can be obtained. Further, a film having a high refractive index, transparency, heat resistance, crack resistance, and light resistance can be obtained by using the composition. The alkane-based polymer may also leave a portion of the unhydrolyzable hydrolyzable group. Further, the siloxane-based polymer may be a partial condensate obtained by condensing a part of a stanol group or a hydrolyzable group. The organic group R1 in the formula (1) and the formula (2) is a non-hydrolyzable organic group having 1 to 12 carbon atoms. The term "non-hydrolyzable" in the organic group R1 means a property which can be stably present in this state under the condition that the hydrolyzable group X is hydrolyzed. Examples of the organic group R1 include a hydrocarbon group having 1 to 12 carbon atoms and a halogenated hydrocarbon group having 1 to 12 carbon atoms. The organic group R1 may be linear, branched, cyclic or a combination thereof. Further, the organic group R1 may have a structural unit containing a hetero atom. The structural unit may be an ether bond, an ester bond, a thioether bond or the like, and the organic group R1 containing the bond may, for example, be an epoxy group such as an oxetane group or an oxiran group. A group having a (meth)acryloxy group and the like. The hydrocarbon group having 1 to 12 carbon atoms in the organic group R1 is preferably a hydrocarbon group having 1 to 8 carbon atoms, more preferably a hydrocarbon group having 1 to 4 carbon atoms, from the viewpoint of reactivity and crack resistance of the obtained film. Specifically, 'may be an aliphatic hydrocarbon group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or t-butyl, cyclopropyl, cyclobutyl, cyclopentyl An alicyclic hydrocarbon group such as a cyclohexyl group, an aromatic hydrocarbon group such as a phenyl group, 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 exemplified by a fluorinated hydrocarbon group, a chlorinated hydrocarbon group or a brominated hydrocarbon group, 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 is chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, perfluoro N-propyl, perfluoroisopropyl, perfluoro-n-butyl, perfluoroisobutyl, perfluoro-tert-butyl, preferably fluoromethyl, difluoromethyl, trifluoromethyl, 2, 2, 2-trifluoroethyl, perfluoroethyl, perfluoro-n-propyl, perfluoroisopropyl, perfluoro-t-butyl, more preferably fluoromethyl, difluoromethyl, trifluoromethyl, 2, 2,2-Trifluoroethyl, perfluoroethyl. The hydrolyzable group X in the general formula (1) and the general formula (2) is exemplified by a hydrogen atom, a halogen atom, an alkoxy group having 1 to 12 carbon atoms, a halogenated alkoxy group having 1 to 12 carbon atoms, and a carbon number of 2 to 2. 12 anthraceneoxy group, a halogenated fluorenyloxy group having 2 to 12 carbon atoms, and the like. Preferred examples of the alkoxy group having 1 to 12 carbon atoms are methoxy groups, ethoxy groups and the like. Preferred examples of the halogen atom are fluorine, chlorine, bromine, iodine and the like. Preferred examples of the decyloxy group are ethoxycarbonyl, propyloxy, butanoxy and the like. Specific examples of the hydrolyzable decane compound (hereinafter simply referred to as a decane compound) represented by the formula (1) will be described. The decane compound having four hydrolyzable groups is exemplified by tetrachlorodecane, tetraaminodecane, tetraethoxydecane, tetramethoxydecane, tetraethoxydecane, tetrabutoxydecane, tetraphenoxydecane. , tetrabenzyloxydecane, trimethoxydecane, triethoxydecane, and the like. The decane compound having three hydrolyzable groups is exemplified by methyltrichlorodecane-12-201220941, methyltrimethoxydecane, methyltriethoxydecane, methyltrioxane, ethyltrimethoxydecane, ethyl Triisopropoxydecane, butoxydecane, butyltrimethoxydecane, pentafluorophenyltrimethoxy, phenyltrimethoxydecane, d3-methyltrimethoxydecane, nonafluorotrimethoxydecane, Trifluoromethyltrimethoxydecane, and the like. The decane compound having two hydrolyzable groups is exemplified by dimethylalkane, dimethyldiaminodecane, dimethyldiethoxydecane, dimethoxydecane, diphenyldimethoxydecane, and Butyl dimethane and the like. The decane compound having a hydrolyzable group is exemplified by trimethyl, hexamethyldiazepine, trimethylnonane, tributyl decane, trioxy decane, tributyl ethoxy decane, and the like. A specific example of the hydrolyzable titanium compound (abbreviated as an anthracene compound) represented by the formula (2) will be described. The titanium compound having four hydrolyzable groups is exemplified by titanium tetrachloride, titanium, titanium tetraethoxide, titanium tetramethoxide, titanium tetraethoxide, titanium tetrakis, titanium tetraphenoxide, and tetrabenzyloxy titanium. , trimethoxy titanium, triethyl and the like. The titanium compound having three hydrolyzable groups is exemplified by methyltrichlorotrimethoxytitanium, methyltriethoxytitanium, methyltributoxytitaniumtrimethoxytitanium, ethyltriisopropoxytitanium, Ethyl tributoxide titanium trimethoxy titanium, pentafluorophenyl trimethoxy titanium, phenyl trimethoxymethyl trimethoxy titanium, nonafluorobutyl ethyl trimethoxy titanium, trifluoromethoxy titanium Wait. Butoxyethyl trimethyl decyl butyl ethane dichloro hydrazine dimethyl oxy chloro chloro decyl methyl ketone sometimes tetraaminobutoxy oxy titanium titanium, methyl, ethyl, butyl, d3- Methyltris-13-201220941 Titanium compounds having two hydrolyzable groups are exemplified by dimethyldichlorotitanium, dimethyldiaminetitanium, dimethyldiethoxytitanium, dimethyldimethoxy. Titanium, diphenyldimethoxytitanium, dibutyldimethoxytitanium, and the like. The titanium compound having one hydrolyzable group is exemplified by trimethylchlorotitanium, hexamethyldiazolidine, trimethyltitanium, tributyltitanium, trimethylmethoxytitanium, tributylethoxytitanium, or the like. . The molecular weight of at least one polymer selected from the siloxane series polymer of the component (A), the titanyl polymer, and the copolymers will be described. This molecular weight can be measured by a gel permeation chromatography (hereinafter sometimes abbreviated as GPC) for using a mobile phase using tetrahydrofuran in terms of a weight average molecular weight in terms of polystyrene. The weight average molecular weight of at least one polymer selected from the group consisting of a oxoxane polymer, a titanyl polymer, and the like is preferably from 500 to 10,000,000', more preferably from 800 to 30,000, more preferably 1 , 000~5,000. When the enthalpy is less than 500, the crack resistance at the time of forming a cured film tends to be lowered. When the enthalpy exceeds 100,000, the dispersibility of the metal oxide particles of the component (B) tends to decrease. The catalyst obtained by obtaining at least one polymer selected from the group consisting of a polymer of a deuterium system, a titanyl polymer, and a copolymer of the above is preferably at least selected from the group consisting of a metal honey compound, an acidic compound, and a basic compound. A compound, more preferably an acidic compound. (d-Ι) Metal Chelate Compound The metal chelate compound which can be used as a catalyst is represented by the following formula (2).
-14- 201220941 R15eM(OR16)f.e .....( 2 ) (式中，R15表示螯合劑，M表示金屬原子，R16表示 烷基或芳基，f表示金屬Μ之原子價，e表示Ι-f之整數）。 此處，金屬Μ較好爲由IIIB族金屬（鋁、傢、銦、鉈 )及IVA族金屬（鈦、鉻、給）選出之至少一種之金屬， 更好爲鈦、鋁、锆。 以R15表示之螯合劑可列舉爲CH3COCH2COCH3、 CH3COCH2COOC2H5 等。 以R16表示之烷基或芳基可列舉爲上述通式（1 )中之 以R1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-tTi(CH3COCH2COOC2H5)t、 (C4H90)4-tTi(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、 -15- 201220941 (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與鈦化合物（ 以下亦稱爲矽烷化合物等）之合計量100質量份（換算完 全水解縮合物），較好爲0.0001-10質量份，更好爲 0.001〜5質量份。該量未達0.0001質量份時，會有塗膜之塗 佈性差之情況’超過10質量份時，無法控制聚合物成長， 有引起凝膠化之情況。 在金屬螯合化合物存在下使水解性矽烷化合物水解縮 合時’矽烷化合物等之合計量每1莫耳較好使用0.5〜20莫 耳之水，最好使用1~10莫耳之水。水量未達0.5莫耳時， 水解反應無法充分進行，會有塗佈性及儲存安定性產生問 題之情況，超過20莫耳時，會有產生水解或縮合反應中之 聚合物析出或凝膠化之情況。又，水較好間歇性或連續添 加。 該等金屬螯合化合物可單獨使用一種，或組合兩種以 上使用。 (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-14- 201220941 R15eM(OR16)fe ..... ( 2 ) (wherein R15 represents a chelating agent, M represents a metal atom, R16 represents an alkyl group or an aryl group, f represents the valence of a metal ruthenium, and e represents Ι -f integer). Here, the metal ruthenium is preferably a metal selected from the group consisting of Group IIIB metals (aluminum, domestic, indium, bismuth) and Group IVA metals (titanium, chromium, nitrile), more preferably titanium, aluminum or zirconium. The chelating agent represented by R15 may, for example, be CH3COCH2COCH3, CH3COCH2COOC2H5 or the like. The alkyl group or the aryl group represented by R16 may be an alkyl group or an aryl group represented by R1 in the above formula (1). Preferred examples of the metal chelate compound are (CH3(CH3)HCO)4-tTi(CH3COCH2COCH3)t, (CH3(CH3)HCO)4-tTi(CH3COCH2COOC2H5)t, (C4H90)4-tTi(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, -15- 201220941 (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 0.0001 to 10 parts by mass, more preferably 0.001 to 100 parts by mass based on the total amount of the decane compound and the titanium compound (hereinafter also referred to as a decane compound). 5 parts by mass. When the amount is less than 0.0001 part by mass, the coating property may be poor. When the amount exceeds 10 parts by mass, the growth of the polymer may not be controlled, and gelation may occur. When the hydrolyzable decane compound is hydrolyzed and contracted in the presence of a metal chelating compound, the total amount of the decane compound or the like is preferably 0.5 to 20 moles of water per 1 mole, preferably 1 to 10 moles of water. When the amount of water is less than 0.5 mol, the hydrolysis reaction may not proceed sufficiently, and there may be problems in coating properties and storage stability. When the amount exceeds 20 mol, the polymer may be precipitated or gelled in the hydrolysis or condensation reaction. The situation. Also, the water is preferably added intermittently or continuously. These metal chelating compounds may be used alone or in combination of two or more. (d-2) Acidic 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 can be exemplified by, for example, acetic acid, propionic acid, butyric acid, valeric acid, and caproic acid.
-16- 201220941 、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、偏苯三酸、花生四 燒酸、莽草酸（shikimic acid) 、2 -乙基己酸、油酸、硬 脂酸、亞麻酸、亞麻油酸、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、^ 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、號 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。 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）之反應中 ，聚合物之析出或凝膠化少之觀點而言，較好爲有機酸， 其中，更好爲具有羧基之化合物。 具有羧基之化合物中，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。 酸性化合物之量相對於矽烷化合物等之合計量100質 量份（換算完全水解縮合物），較好爲0.0001-10質量份 ，更好爲0.001~5質量份，該量未達0.000 1質量份時，會有 塗膜之塗佈性差之情況，超過10質量份時，會有急遽進行 -17- 201220941 水解縮合反應而引起凝膠化之情況。 在酸性化合物存在下使矽烷化合物等水解縮合時，矽 烷化合物等之合計量每1莫耳較好使用0.5~20莫耳之水， 最好俾用1〜10莫耳之水。水量未達0.5莫耳時，水解反應 無法充分進行，會有塗佈性及儲存安定性產生問題之情況 ’超過20莫耳時，會產生水解縮合反應中之聚合物析出或 凝膠化之情況。又，水較好間歇性或連續添加❶ (d - 3 )鹼性化合物 可作爲觸媒使用之鹼性化合物列舉爲例如甲醇胺、乙 醇胺、丙醇胺、丁醇胺、N-甲基甲醇胺、N-乙基甲醇胺、 N-丙基甲醇胺、N-丁基甲醇胺、N-甲基乙醇胺、N-乙基乙 醇胺、N-丙基乙醇胺、n，N-二甲基甲醇胺、N，N-二乙基甲 醇胺、N，N-二丙基甲醇胺、n，N-二丁基甲醇胺、N-甲基二 甲醇胺、N-乙基二甲醇胺、N-丙基二甲醇胺、N_丁基二甲 醇胺、N-(胺基甲基）甲醇胺、N-(胺基甲基）乙醇胺、 N-(胺基甲基）丙醇胺、N-(胺基甲基）丁醇胺、甲氧基 甲基胺 '甲氧基乙基胺、甲氧基丙基胺、甲氧基丁基胺、 N，N-二甲基胺' N，N-二乙基胺、N，N-二丙基胺、Ν,Ν·二丁 基胺、三甲基胺、三乙基胺、三丙基胺、三丁基胺、氫氧 化四甲基銨 '氫氧化四乙基銨、氫氧化四丙基銨、氫氧化 四丁基銨、四甲基乙二胺、四乙基乙二胺、四丙基乙二胺 、氨、氫氧化鈉 '氫氧化鉀、氫氧化四甲基銨、氫氧化四 乙基銨、氫氧化四正丙基銨、氫氧化四正丁基敍、溴化四 甲基銨、氯化四甲基銨、溴化四乙基銨等。 -18 - 201220941 鹼性化合物之量相對於矽烷化合物等之水解性基之含 量1莫耳’較好爲0_00001~10莫耳，更好爲0.00005〜5莫耳 。該量未達0.0 0001莫耳時，會有無法充分進行水解縮合 之情況，超過10莫耳時，會有所得水解縮合物之儲存安定 性差之情況。 [(B)成分：金屬氧化物粒子] 本發明中’爲了獲得具有高折射率之硬化物，較好使 用具有高折射率之金屬氧化物粒子。該金屬氧化物粒子爲 在25°C下之波長4〇Onm之光折射率較好爲1.55以上，更好 爲1.60以上’最好爲1.70以上之微粒子。該種金屬氧化物 粒子列舉爲例如氧化銷、氧化鈦、氧化鲜、氧化钽、氧化 銦、氧化給、氧化錫、氧化鈮及該等之複合物等之金屬氧 化物粒子。其中，以氧化锆（Zr02 )之微粒子較佳。 上述氧化鈦只要爲具有Ti02構造者即無特別限制，列 舉爲例如銳鈦礦型、金紅石型、板鈦礦型等。 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1〜100nm，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。至於溶 劑可使用例如有機溶劑。有機溶劑列舉爲例如2-丁醇、甲 -19- 201220941 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，較 好爲50〜2,000質量份，更好爲100〜1，500質量份，又更好爲 15 0~1，000質量份。該量未達50質量份時，硬化膜（組成 物之硬化物）之折射率低，會有發光裝置之發光效率低之 虞，該量超過2,000質量份時，會有無法獲得足夠之龜裂 耐性之虞。 又，（B)成分爲溶劑分散之溶膠時，（B)成分之調 配量意指不含溶劑之質量。另外，（B)成分爲溶劑分散 溶膠時，作爲（B)成分之溶劑之有機溶劑之量爲構成（C )成分之有機溶劑之調配量之一部份者。 ^ ( A)成分與（B )成分之合計調配量並無特別限制， 但相對於去除有機溶劑之組成物之成分總量1 00質量％，就 所得含有粒子層之耐熱性之觀點而言，較好爲50〜100質量 %，更好爲70~ 100質量％，又更好爲80〜100質量％，最好爲 9 0〜1 0 0質量％。 [(C)成分：有機溶劑] 本發明中，藉由調配有機溶劑，可提高組成物之儲存 安定性，且賦予適當黏度》 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。有機溶劑在 大氣壓下（1.013hPa)之沸點在50~250°C之範圍內，且較 -20- 201220941 好使用可均勻分散各成分之有機溶劑。 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、多價醇系溶劑、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，就進一步提高組成物之儲存安定性之觀 點而言’較好爲單醇系溶劑、多價醇系溶劑、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。該等較佳化合物可單獨使用 —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 法而選擇。例如爲了容易獲得具有均勻厚度之硬化膜（組 成物之硬化物），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；乙基溶纖 素乙酸酯、丙二醇甲基醚乙酸酯、丙二醇乙基醚乙酸酯等 乙二醇烷基醚乙酸酯類；乳酸乙酯、2-羥基丙酸乙酯等酯 類；二乙二醇單甲基醚、二乙二醇二甲基醚、二乙二醇乙 基甲基醚等二乙二醇類；甲基乙基酮、甲基異丁基酮、2_ 庚酮、環己酮、甲基戊基酮等酮類；γ-丁內酯等。 最佳之有機溶劑爲乙基溶纖素乙酸酯、丙二醇單甲基 醚、丙二醇甲基醚乙酸酯、乳酸乙酯、甲基乙基酮 '甲基 異丁基酮、甲基戊基酮等。 (C)成分（有機溶劑）之調配量相對於去除該有機 -21 - 201220941 溶劑之組成物成分之總量100質量份，較好爲50~20,000質 量份，更好爲100〜1,000質量份。在前述之較佳範圍內時 ，可提高組成物之儲存安定性，且可賦予適當黏度，可容 易地形成具有均勻厚度之高折射率之硬化膜。 (c )成分之添加方法並無特別限制，例如，可在製 造（A)成分時添加，亦可在調製含有（B)成分之分散液 時添加，也可在混合（A)成分與（B)成分時添加。 [(D )成分；分散劑] 本發明之形成含粒子層用組成物可含有各種分散劑以 提高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。鋁化合物之例可列 舉爲€氧化鋁、β-二酮酸鋁錯合物等。具體而言，可列舉 爲三乙氧基鋁、三（正丙氧基）鋁、三（異丙氧基）鋁、 三（正丁氧基）鋁、三（第二丁氧基）鋁等烷氧化物化合 物，參（甲基乙醯基乙酸）鋁、參（乙基乙醯基乙酸）鋁 、三（乙醯基丙酮酸酯）鋁、單乙醯基丙酮酸鋁雙（甲基 乙酸酯）、單乙醯基丙酮酸鋁雙（乙基乙酸酯）等β-二酮 酸酯錯合物等。 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 800AF ' ALUGOMER 1000SF(以上爲川硏精密化學公司製-16- 201220941, heptanoic acid, caprylic acid, citric acid, citric acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, azelaic acid, gallic acid, butyric acid, trimellitic acid, peanut Tetanic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linolenic acid, linoleic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluene Acid, benzenesulfonic acid, monochloroacetic acid 'dichloroacetic acid, ^ chloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, maleic anhydride, Fumar Acid, itaconic acid, benzoic acid, mesaconic acid, citraconic acid, malic acid, malonic acid, hydrolyzate of glutaric acid, hydrolyzate of maleic anhydride, hydrolyzate of phthalic anhydride, and the like. The inorganic acid may, for example, be hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid or the like. Among them, in the reaction of hydrolysis condensation (hydrolysis and subsequent condensation), an organic acid is preferred from the viewpoint of less precipitation or gelation of the polymer, and among them, a compound having a carboxyl group is more preferable. Among the compounds having a carboxyl group, acetic acid, oxalic acid, maleic acid, formic acid, malonic acid 'phthalic acid, fumaric acid, itaconic acid' succinic acid, mesaconic acid, citraconic acid, malic acid, and sodium C are preferred. An organic acid such as a hydrolyzate of diacid, glutaric acid or maleic anhydride. These acidic compounds may be used alone or in combination of two or more. The amount of the acidic compound is preferably 0.0001 to 10 parts by mass, more preferably 0.001 to 5 parts by mass, based on 100 parts by mass of the total amount of the decane compound or the like (in terms of the total hydrolysis condensate), and the amount is less than 0.0001 part by mass. In the case where the coating property of the coating film is poor, when it exceeds 10 parts by mass, there is a case where the -17-201220941 hydrolytic condensation reaction is rapidly performed to cause gelation. When the decane compound or the like is hydrolyzed and condensed in the presence of an acidic compound, the total amount of the decane compound or the like is preferably 0.5 to 20 moles of water per 1 mole, preferably 1 to 10 moles of water. When the amount of water is less than 0.5 mol, the hydrolysis reaction may not proceed sufficiently, and there may be problems in coating properties and storage stability. When the amount exceeds 20 mol, the precipitation or gelation of the polymer in the hydrolysis condensation reaction may occur. . Further, the water is preferably intermittently or continuously added with a ruthenium (d - 3 ) basic compound. The basic compound which can be used as a catalyst is exemplified by, for example, methanolamine, ethanolamine, propanolamine, butanolamine, N-methylmethanolamine. , N-ethylmethanolamine, N-propylmethanolamine, N-butylmethanolamine, N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, n,N-dimethylmethanolamine, N,N-diethylmethanolamine, N,N-dipropylmethanolamine, n,N-dibutylmethanolamine, N-methyldimethanolamine, N-ethyldimethanolamine, N-propyl Dimethanolamine, N-butyldimethanolamine, N-(aminomethyl)methanolamine, N-(aminomethyl)ethanolamine, N-(aminomethyl)propanolamine, N-(amino group Methyl)butanolamine, methoxymethylamine 'methoxyethylamine, methoxypropylamine, methoxybutylamine, N,N-dimethylamine 'N,N-diethyl Base amine, N,N-dipropylamine, hydrazine, hydrazine dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tetramethylammonium hydroxide Tetraethylammonium, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetramethylethylenediamine, tetraethylethylene , tetrapropylethylenediamine, ammonia, sodium hydroxide 'potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetra-n-butyl hydride, bromination Tetramethylammonium, tetramethylammonium chloride, tetraethylammonium bromide, and the like. -18 - 201220941 The amount of the basic compound relative to the hydrolyzable group of the decane compound or the like is 1 mole, preferably 0_00001 to 10 moles, more preferably 0.00005 to 5 moles. When the amount is less than 0.00001 mol, the hydrolysis condensation may not be sufficiently performed. When the amount exceeds 10 mol, the storage stability of the obtained hydrolysis-condensation product may be inferior. [Component (B): Metal oxide particles] In the present invention, in order to obtain a cured product having a high refractive index, metal oxide particles having a high refractive index are preferably used. The metal oxide particles are particles having a refractive index of 4 〇 Onm at 25 ° C of preferably 1.55 or more, more preferably 1.60 or more and most preferably 1.70 or more. Such metal oxide particles are exemplified by metal oxide particles such as an oxidation pin, titanium oxide, oxidized fresh, cerium 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 before being mixed with the components (A) and (C), or may be a solvent-dispersed sol. As the solvent, for example, an organic solvent can be used. The organic solvent is exemplified by, for example, 2-butanol, A-19-201220941 alcohol, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, propylene glycol monomethyl ether and the like. The blending amount of the component (B) is preferably from 50 to 2,000 parts by mass, more preferably from 100 to 1,500 parts by mass, even more preferably from 15 to 1,000 parts by mass, per 100 parts by mass of the component (A). When the amount is less than 50 parts by mass, the refractive index of the cured film (hardened material of the composition) is low, and the luminous efficiency of the light-emitting device is low. When the amount exceeds 2,000 parts by mass, sufficient cracking may not be obtained. The patience. 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, 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). ^ The total amount of the components (A) and (B) is not particularly limited, but the total amount of the components of the composition from which the organic solvent is removed is 100% by mass, and the heat resistance of the obtained particle layer is obtained. It is preferably from 50 to 100% by mass, more preferably from 70 to 100% by mass, still more preferably from 80 to 100% by mass, most preferably from 90 to 1.0% by mass. [(C) component: organic solvent] In the present invention, by adjusting an organic solvent, the storage stability of the composition can be improved and an appropriate viscosity can be imparted. The organic solvent is exemplified by an ether-based organic solvent, an ester-based organic solvent, and a ketone-based organic solvent. A solvent, a hydrocarbon-based organic solvent, an alcohol-based organic solvent, or the like. The organic solvent has a boiling point of 50 to 250 ° C at atmospheric pressure (1.013 hPa), and is preferably used to uniformly disperse the organic solvent of each component from -20 to 201220941. Examples of the organic solvent include an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, a monool solvent, a polyvalent alcohol solvent, a ketone solvent, an ether solvent, an ester solvent, a nitrogen-containing solvent, and a sulfur-containing system. Solvents, etc. These organic solvents may be used alone or in combination of two or more. In the organic solvent, the viewpoint of further improving the storage stability of the composition is preferably a monool solvent, a polyvalent alcohol solvent, and a ketone solvent. 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 singly 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 (hardened product of a composition) having a uniform thickness, when a spin coating method is used, a glycol ether such as ethylene glycol monoethyl ether or propylene glycol monomethyl ether is preferably used as the organic solvent; Ethylene glycol alkyl ether acetates such as cellosolve acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate; esters such as ethyl lactate and ethyl 2-hydroxypropionate; Diethylene glycol such as ethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether; methyl ethyl ketone, methyl isobutyl ketone, 2 - heptanone, a ketone such as cyclohexanone or methyl amyl ketone; γ-butyrolactone or the like. The most preferred organic solvents are ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, ethyl lactate, methyl ethyl ketone 'methyl isobutyl ketone, methyl amyl Ketones, etc. The blending amount of the component (C) (organic solvent) is preferably from 50 to 20,000 parts by mass, more preferably from 100 to 1,000 parts by mass, per 100 parts by mass of the total of the constituent components of the organic solvent-removing organic solvent. Within the above preferred range, the storage stability of the composition can be improved, and an appropriate viscosity can be imparted, and a cured film having a high refractive index of a uniform thickness can be easily formed. The method of adding the component (c) is not particularly limited. For example, it may be added during the production of the component (A), or may be added during the preparation of the dispersion containing the component (B), or may be mixed with the component (A) and (B). ) Add ingredients. [(D) component; dispersant] The composition for forming a particle-containing layer of the present invention may contain various dispersants to increase the dispersibility of the metal oxide particles. As the dispersing agent, for example, an aluminum compound can be used. Examples of the aluminum compound may be exemplified by alumina, a β-diketonate complex, and the like. Specific examples thereof include triethoxyaluminum, tri(n-propoxy)aluminum, tris(isopropoxy)aluminum, tri(n-butoxy)aluminum, tris(t-butoxy)aluminum, and the like. Alkoxide compound, ginseng (methyl ethinylacetate) aluminum, ginseng (ethyl ethionylacetate) aluminum, tris(ethyl decyl pyruvate) aluminum, aluminum acetoacetate bis (methyl ethane) A β-diketonate complex such as an acid ester or an aluminum acetoacetate bis(ethyl acetate). Commercially available aluminum compounds can be used AIPD, PADM, AMD, ASBD 'Aluminum oxide, 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 800AF 'ALUGOMER 1000SF (above is Chuanxiong Precision Chemical Co., Ltd.
S -22- 201220941 造）等。 至於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。本發明中使用之非離子型分散 劑較好爲具有聚氧伸乙基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 對於去除有機溶劑之組成物之成分總量1 〇〇質量％，爲例如 0.1〜5質量％。 [(E )成分；分散助劑] 本發明之形成含粒子層用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選出之一種以上。 分散助劑之調配量並無特別限制，但含有分散助劑時 ，相對於去除有機溶劑之組成物之成分總量1 〇〇質量％，爲 例如〇· 1〜5質量％。 [(F )成分；界面活性劑] 藉由旋轉塗佈將本發明之形成含粒子層用組成物塗佈 於基材等上時，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 矽氧系界面活性劑、氟系界面活性劑等。其中，以矽氧系 之界面活性劑較佳。 矽氧系之界面活性劑之例列舉爲例如SH28PA ( Toray -23- 201220941 道康寧公司製造，二甲基聚矽氧烷聚氧伸烷基共聚物）、 PAINTEDO 19、54 (.Toray道康寧公司製造，二甲基聚矽 氧院聚氧伸烷基共聚物）、FM0411 ( SilaPlain，CHISS0 公司製造）、SF8428 ( Toray道康寧公司製造，二甲基聚 矽氧烷聚氧伸烷基共聚物（含有側鏈〇H))、 BYKUV3510 (曰本BYK化學公司製造，二甲基聚矽氧烷-聚氧伸垸基共聚物）、DC57 (T〇ray道康寧•砂氧公司製 造，二甲基聚矽氧烷-聚氧伸烷基共聚物）、DC 190 ( Toray道康寧•矽氧公司製造’二甲基聚矽氧烷-聚氧伸烷 基共聚物）、Silaplain FM-441 1、FM-442 1、FM-4425、 FM-7711、FM-772 1、FM-7725、FM-0411、FM-042 1、FM-042 5 、 FM-DA11 、 FM-DA21 、 FM-DA26 、 FM0711 、 FM0721 ' FM-0725、TM-0701、TM - 0 7 0 1 T ( C ΗIS S Ο 公司 製造）、UV3500、UV3510、UV3530 (日本 ΒΚΥ 化學公司 製造）、ΒΥ1 6-004、SF8428 ( Toray道康寧•矽氧公司製 造）、VPS-1001 (和光純藥製造）等。最佳之例可列舉爲 Silaplain FM-7711、FM-772 1、FM-7 725、FM-0411、FM-0421 、FM-0425、FM0711、FM072 1、FM-0725、VPS-1001 等。另外，具有乙烯性不飽和基之矽氧化合物之市售品可 列舉爲例如TegoRad 2300、2200N ( Tego化學公司製造） 等》 氟系界面活性劑之例列舉爲例如Megafac F-1 14、 F410、F41 1、F450、F493、F494、F443、F444、F445、 F446 、 F470 、 F471 、 F472SF 、 F474 、 F475 、 R30 、 F477 、S -22- 201220941 made) and so on. As the dispersing agent, a nonionic dispersing agent can be used. 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 polyoxyethylidene group structure. The amount of the dispersing agent is not particularly limited. However, when the dispersing agent is contained, it is, for example, 0.1 to 5% by mass based on the total amount of the component of the organic solvent-removing composition. [(E) component; dispersing aid] The composition for forming a particle-containing layer of the present invention may further contain a dispersing aid to improve dispersibility. As the dispersing aid, one or more selected from the group consisting of etidinylacetone, N,N-dimethylethendylacetamide, and the like can be suitably used. The amount of the dispersing aid is not particularly limited. However, when the dispersing aid is contained, the total amount of the component of the composition for removing the organic solvent is, for example, 〇·1 to 5% by mass. [(F) component; surfactant] When the composition for forming a particle-containing layer of the present invention is applied onto a substrate or the like by spin coating, it is preferable to obtain a coating film having a uniform thickness. Interface active agent. The surfactant used in the present invention is exemplified by a ruthenium-based surfactant, a fluorine-based surfactant, and the like. Among them, a surfactant of a ruthenium oxide type is preferred. Examples of the surfactant of the oxime system are, for example, SH28PA (Toray -23-201220941 manufactured by Dow Corning Corporation, dimethyl polyoxyalkylene polyoxyalkylene copolymer), PAINTEDO 19, 54 (manufactured by Toray Dow Corning Corporation, Dimethyl polyoxyl polyoxyalkylene copolymer), FM0411 (SilaPlain, manufactured by CHISS0), SF8428 (manufactured by Toray Dow Corning, dimethyl polyoxyalkylene polyoxyalkylene copolymer (with side chain) 〇H)), BYKUV3510 (manufactured by BYK Chemical Co., Ltd., dimethyl polyoxyalkylene-polyoxyalkylene copolymer), DC57 (manufactured by T〇ray Dow Corning Sand Oxide Co., Ltd., dimethyl polyoxyalkylene) - polyoxyalkylene copolymer), DC 190 (Toray Dow Corning Co., Ltd. manufactures 'dimethyl polyoxyalkylene-polyoxyalkylene copolymer), Silaplain FM-441 1, FM-442 1, FM -4425, FM-7711, FM-772 1, FM-7725, FM-0411, FM-042 1, FM-042 5, FM-DA11, FM-DA21, FM-DA26, FM0711, FM0721 'FM-0725, TM-0701, TM - 0 7 0 1 T (manufactured by C ΗIS S Ο), UV3500, UV3510, UV3530 (manufactured by Nippon Chemical Co., Ltd.), Β Υ1 6-004, SF8428 (manufactured by Toray Dow Corning Co., Ltd.), VPS-1001 (made by Wako Pure Chemical Industries, etc.). The best examples are as Silaplain FM-7711, FM-772 1, FM-7 725, FM-0411, FM-0421, FM-0425, FM0711, FM072 1, FM-0725, VPS-1001, and the like. Further, commercially available products of an epoxy group having an ethylenically unsaturated group include, for example, TegoRad 2300 and 2200N (manufactured by Tego Chemical Co., Ltd.). Examples of the fluorine-based surfactant are, for example, Megafac F-1 14 and F410. F41 1, F450, F493, F494, F443, F444, F445, F446, F470, F471, F472SF, F474, F475, R30, F477,
S -24- 201220941 F478、F479、F48 0SF、F482、F483、F484、F486、F487 、F172D、F178K、F178RM、ESM-1、MCF350SF、BL20、 R08、R61、R90 ( DIC公司製造）。 (F )成分之調配比例相對於去除有機溶劑之組成物 之成分總量100質量％，較好爲0〜10質量％，更好爲0.1〜5 質量％，最好爲0.5〜3質量％。該量超過1〇質量％時，會有 組成物之硬化物折射率下降之虞。 [(G )成分；脫水劑] 本發明之形成含粒子層用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，同時可 進一步提高組成物之儲存安定性。 ^本發明中使用之脫水劑定義爲藉由化學反應將水轉化 成水外之物質之化合物，或者，藉由物理吸附或包接，將 水轉化成不會對輻射線硬化性及儲存安定性帶來影響之物 質之化合物。藉由含有脫水劑，可不損及組成物之耐光性 或耐熱性，且提高儲存安定性與輻射線硬化性之相違背的 兩種特性。其理由被認爲是利用脫水劑有效的吸收自外部 入侵之水，提高組成物之儲存安定性，另一方面在輻射線 硬化反應的縮合反應中，藉由以脫水劑依序吸收生成之水 ，而提高組成物之輻射線硬化性。 [(Η )成分：酸產生劑] 本發明之形成含粒子層用組成物亦可含有酸產生劑。 -25- 201220941 所謂酸產生劑係定義爲可藉由照光或加熱產生酸之化合物 〇 此處所謂照光意指例如紅外線 '可見光、紫外線、及 如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，可藉由照光產生酸之光酸產生劑可列舉爲具有 以通式（3)表示之構造之鎗鹽（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 [MZra + n]-m ( 3) [通式（3)中，陽離子爲鑰陽離子’ w爲s、Se、Te、P、 As、Sb、Bi、0、I、Br、Cl 或-N = N，R2、R3、R4 及 R5 爲 相同或不同之有&基，a、b、c及d分別爲0〜3之整數’（ a + b + c + d) -m爲W之價數等。另外，Μ爲構成鹵化物錯合物 [MXm + n]之中心原子的金屬或類金屬（Metalloid) ’例如Β 、P、As、Sb、Fe、. Sn、Bi、Al、Ca、In、Ti、Zn、Sc、V 、Cr、Mn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正電荷’ n爲M之原子價]»S -24- 201220941 F478, F479, F48 0SF, F482, F483, F484, F486, F487, F172D, F178K, F178RM, ESM-1, MCF350SF, BL20, R08, R61, R90 (manufactured by DIC Corporation). The blending ratio of the component (F) is preferably from 0 to 10% by mass, more preferably from 0.1 to 5% by mass, most preferably from 0.5 to 3% by mass, based on 100% by mass of the total of the components of the composition for removing the organic solvent. When the amount exceeds 1% by mass, the refractive index of the cured product of the composition may decrease. [(G) component; dehydrating agent] The composition for forming a particle-containing layer 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 radiation hardening property and storage stability by physical adsorption or inclusion. a compound that affects the substance. By containing a dehydrating agent, the light resistance or heat resistance of the composition can be prevented, and the two characteristics of the storage stability and the radiation hardenability are deteriorated. The reason is considered to be that the dehydrating agent is effective to absorb water invading from the outside, thereby improving the storage stability of the composition, and on the other hand, in the condensation reaction of the radiation hardening reaction, the generated water is sequentially absorbed by the dehydrating agent. And increase the radiation hardenability of the composition. [(Η) component: acid generator] The composition for forming a particle-containing layer of the present invention may further contain an acid generator. -25- 201220941 The so-called acid generator is defined as a compound which can generate an acid by illumination or heating. Here, the term "illumination" means, for example, infrared light, visible light, ultraviolet light, and, for example, X-rays, electron beams, alpha rays, beta rays, gamma Irradiation of the ionizing radiation of the ray. Further, the photoacid generator which can generate an acid by irradiation can be exemplified by a gun salt (first group compound) having a structure represented by the formula (3) or a sulfonic acid having a structure represented by the formula (4). Derivative (Group 2 compound) ° [R2aR3bR4cR5dW] + m [MZra + n]-m (3) [In the formula (3), the cation is a key cation 'w is s, Se, Te, P, As, Sb , Bi, 0, I, Br, Cl or -N = N, R2, R3, R4 and R5 are the same or different & base, a, b, c and d are each an integer of 0~3' (a + b + c + d) -m is the valence of W, etc. Further, Μ is a metal or a metalloid (Metalloid) constituting a central atom of the halide complex [MXm + n] such as Β, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti , Zn, Sc, V, Cr, Mn or Co. Z is a halogen atom or an aryl group such as F, Cl, Br, and m is a positive charge of the halide complex ion ' n is the valence of M]»
Qs-[S ( =0 ) 2-R6]t ( 4 ) [通式（4)中，Q爲一價或二價有機基’ R6爲碳數卜12之 一價有機基，附加字s爲〇或1，附加字t爲1或2]。 首先，第一群化合物之鑰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 鹽爲芳香族銷鹽，最好爲以下述通式（5)表不之二芳基Qs-[S ( =0 ) 2-R6]t ( 4 ) [In the formula (4), Q is a monovalent or divalent organic group ' R 6 is a carbon number b 12 one-valent organic group, and the additional word s is 〇 or 1, the additional word t is 1 or 2]. First, the key 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 pin salt, preferably a diaryl group represented by the following formula (5).
S -26- 201220941 錤鹽， [R'A^-I'-ArW] [ΥΊ ( 5) [通式（5)中’ R7及R分別爲一價有機基，可相同亦可不 酮，R7及R8之至少一方爲具有碳數4以上之院基，Ar1及 Ar2各爲芳香族基，可相同亦可不同，γ-爲—價陰離子， 爲週期表3族、5族之氟化物陰離子，或由CIO〆、CF3-SO3-選出之陰離子]。 又，例示第二群化合物之以通式（4)表示之磺酸衍 生物之例時，可列舉爲二磺酸類、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、苯甲醯基磺酸酯類、1-氧基-2-羥基-3-丙醇之磺酸酯 類、連苯三酚（pyrogallol )三磺酸酯類、苄基磺酸酯類 。又，以通式（4)表示之磺酸衍生物中，更好爲醯亞胺 磺酸酯類，又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，但以形成含粒子層用組 成物之固體成分總量作爲1〇〇質量份，通常較好爲15質量 份以內之値。該添加量超過1 5質量份時，所得硬化物之耐 光性或耐熱性有下降之傾向。 [(I )成分；其他添加劑] 本發明之形成含粒子層用組成物在不損及本發明之效 果之範圍內，可含有上述以外之各種添加劑。該等添加劑 -27- 201220941 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。 [形成含粒子層用組成物之製造方法] 本發明之形成含粒子層用組成物係藉由混合上述成分 (A)〜（C)及視需要調配之其他任意成分而調製。通常 ’可在成分（C)(有機溶劑）中以特定之比例混合成分 (A)(矽氧烷系聚合物等）及成分（B)(金屬氧化物粒 子）以及任意添加之其他成分，藉此調製形成含粒子層用 組成物。 [硬化膜] 本發明之形成含粒子層用組成物之硬化物之硬化膜之 折射率較好爲1.6以上。該折射率爲1.6以上時，發光裝置 之發光效率高。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50nm〜100 μιη之範圍內。 本發明之發光元件由於具備含粒子層18，故於發光層 15生成之光通過第二電極17進入空氣時，基於補強干涉之 原理，可提高射出至發光元件外部之效率，而可大幅助於 發光元件之發光效率的改善。 圖1中，含粒子層18係以接觸於第二電極I7之一面而 形成者加以圖示，但含粒子層1 8與第二電極1 7之間可視需 要具備多種層。另一方面，圖1中雖未圖示，但在含粒子 層18之上部可進一步具備有用以密封發光元件1〇之習知構S -26- 201220941 錤 salt, [R'A^-I'-ArW] [ΥΊ ( 5) [In the general formula (5), R7 and R are each a monovalent organic group, which may or may not be ketone, R7 and At least one of R8 is a hospital having a carbon number of 4 or more, and each of Ar1 and Ar2 is an aromatic group, which may be the same or different, and γ- is a valent anion, and is a fluoride anion of Groups 3 and 5 of the periodic table, or Anion selected by CIO〆, CF3-SO3-]. Further, examples of the sulfonic acid derivative represented by the formula (4) in the second group of compounds include disulfonic acids, disulfonyldiazomethanes, disulfonyl methanes, and sulfonyl groups. Benzopyridyl methanes, sulfhydryl sulfonates, benzamyl sulfonates, sulfonates of 1-oxy-2-hydroxy-3-propanol, pyrogallol Trisulfonates, benzyl sulfonates. Further, the sulfonic acid derivative represented by the formula (4) is more preferably a quinone imide sulfonate, and more preferably a triflate sulfonate derivative in the quinone sulfinate. 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. However, the total amount of the solid content of the composition for forming a particle-containing layer is usually 1 part by mass, and usually preferably 15 parts by mass or less. When the amount is more than 15 parts by mass, the light resistance or heat resistance of the obtained cured product tends to decrease. [Component (I); Other Additives] The composition for forming a particle-containing layer 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 -27-201220941 are exemplified by a curable compound other than the above components, an antioxidant, an ultraviolet absorber, and the like. [Manufacturing Method of Forming Composition Containing Particle Layer] The composition for forming a particle-containing layer of the present invention is prepared by mixing the above components (A) to (C) and optionally other optional components. In general, the component (A) (a siloxane-based polymer, etc.) and the component (B) (metal oxide particles) and other components added may be mixed in a specific ratio in the component (C) (organic solvent). This modulation forms a composition containing a particle layer. [Cured film] The cured film of the cured product of the composition for forming a particle-containing layer of the present invention preferably has a refractive index of 1.6 or more. When the refractive index is 1.6 or more, the light-emitting device has high luminous efficiency. The film thickness of the cured film is not particularly limited, but may be suitably set within a range of, for example, 50 nm to 100 μm depending on the kind of the light-emitting element. Since the light-emitting element of the present invention includes the particle-containing layer 18, when the light generated by the light-emitting layer 15 enters the air through the second electrode 17, the efficiency of the emission to the outside of the light-emitting element can be improved based on the principle of the reinforcing interference, which can greatly contribute to Improvement in luminous efficiency of the light-emitting element. In Fig. 1, the particle-containing layer 18 is formed by being in contact with one surface of the second electrode I7, but a plurality of layers may be provided between the particle-containing layer 18 and the second electrode 17 as needed. On the other hand, although not shown in Fig. 1, the upper portion of the particle-containing layer 18 may further have a conventional structure for sealing the light-emitting element 1
S -28- 201220941 造的密封層等，且可爲多種變形例。 圖2中，發光元件20爲本發明之發光元件之實施形態 例2。 發光元件20具有依序層合基板21、含粒子層28、第一 電極23、發光層25及第二電極27而成之構造。第一電極23 爲透射型電極，於發光層25產生之光透過第一電極23及含 粒子層28，射出至發光元件20之外部。含粒子層28係在第 一電極23之與設置發光層之面相反之面上形成。針對構成 發光元件20之各層的詳細說明與前述相同。由前述矽烷化 合物等縮合而成之聚合物所構成之含粒子層28具有高.的折 射率.，且於發光層25生成之光藉由補強干涉原理有效地射 出至外部，故具有改善之光效率特性。 圖3中，發光元件30爲本發明之發光元件之實施形態 例3。 發光元件30具有依序層合基板31、含粒子層38、第一 電極33、發光層35、第二電極37及含粒子層3 9而成之構造 。第一電極33及第二電極37爲透射型電極，於發光層35產 生之光通過第一電極33及第二電極37後，分別通過含粒子 層38及含粒子層39，射出至發光元件30之外部。針對構成 發光元件30之各層之詳細說明係與前述相同。由前述矽烷 化合物等縮合而成之聚合物所構成之含粒子層38及含粒子 層39具有高的折射率，且於發光層35生成之光藉由補強干 涉原理有效地射出於外部，故可具有改善之光效率特性。 -29- 201220941 [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] 於裝設攪拌機、回流冷凝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’ 加熱該溶液使液溫成爲60°C。接著，滴加蒸餾水（22.38g )，且於滴加結束後，在l〇〇°C攪拌溶液3小時。隨後，於 減壓下進行濃縮，將最終之固體成分調整成3〇質量％ ’獲 得（A)成分（丙二醇單甲基醚溶液）。將此稱爲「A-1」 [合成例2] 於裝設攪拌機、回流冷凝管之燒瓶中添加甲基三甲氧 基矽烷（17.89g)、苯基三甲氧基矽烷（ 3 5.8 0g)、四乙 氧基矽烷（3.42g)、丙二醇單甲基醚（ 24.8 4g)及草酸（ 〇.〇3g )，經攪拌，獲得溶液後，加熱該溶液使液溫成爲 60°C。接著，滴加蒸餾水（18.02g)，且於滴加結束後， 在1 0 0 °C攪拌溶液3小時。隨後，於減壓下進行濃縮，將最 終之固體成分調整成3 0質量％，獲得（A )成分（丙二醇 單甲基醚溶液）。將此稱爲「A-2」。S -28- 201220941 Sealing layer, etc., and can be various modifications. In Fig. 2, a light-emitting element 20 is an embodiment 2 of a light-emitting element of the present invention. The light-emitting element 20 has a structure in which the substrate 21, the particle-containing layer 28, the first electrode 23, the light-emitting layer 25, and the second electrode 27 are laminated in this order. The first electrode 23 is a transmissive electrode, and light generated in the light-emitting layer 25 is transmitted through the first electrode 23 and the particle-containing layer 28, and is emitted to the outside of the light-emitting element 20. The particle-containing layer 28 is formed on the surface of the first electrode 23 opposite to the surface on which the light-emitting layer is provided. The detailed description of each layer constituting the light-emitting element 20 is the same as described above. The particle-containing layer 28 composed of the polymer obtained by condensing the decane compound or the like has a high refractive index. The light generated in the light-emitting layer 25 is efficiently emitted to the outside by the principle of reinforcing interference, so that the light is improved. Efficiency characteristics. In Fig. 3, a light-emitting element 30 is an embodiment 3 of a light-emitting element of the present invention. The light-emitting element 30 has a structure in which the substrate 31, the particle-containing layer 38, the first electrode 33, the light-emitting layer 35, the second electrode 37, and the particle-containing layer 39 are sequentially laminated. The first electrode 33 and the second electrode 37 are transmissive electrodes, and the light generated in the light-emitting layer 35 passes through the first electrode 33 and the second electrode 37, and then passes through the particle-containing layer 38 and the particle-containing layer 39, respectively, and is emitted to the light-emitting element 30. External. The detailed description of each layer constituting the light-emitting element 30 is the same as described above. The particle-containing layer 38 and the particle-containing layer 39 composed of the polymer obtained by condensing the decane compound or the like have a high refractive index, and the light generated in the light-emitting layer 35 is efficiently emitted to the outside by the principle of reinforcing interference. With improved light efficiency characteristics. -29-201220941 [Examples] Hereinafter, the present invention will be more specifically described by examples, but the present invention is not limited by the examples. [Preparation of component (A)] [Synthesis Example 1] Methyltrimethoxydecane (45.7 g), tetraethoxydecane (12.33 g), and propylene glycol monomethyl group were placed in a flask equipped with a stirrer and a reflux condenser. Ether (19.56 g) and oxalic acid (0.03 g) were stirred to obtain a solution. The solution was heated to bring the liquid temperature to 60 °C. Next, distilled water (22.38 g) was added dropwise, and after completion of the dropwise addition, the solution was stirred at 100 ° C for 3 hours. Subsequently, concentration was carried out under reduced pressure, and the final solid content was adjusted to 3% by mass to obtain the component (A) (propylene glycol monomethyl ether solution). This is called "A-1". [Synthesis Example 2] Methyltrimethoxydecane (17.89 g), phenyltrimethoxydecane (35.80 g), and tetra are added to a flask equipped with a stirrer and a reflux condenser. Ethoxy decane (3.42 g), propylene glycol monomethyl ether (24.8 4 g) and oxalic acid (3 g) were stirred to obtain a solution, and the solution was heated to bring the liquid temperature to 60 °C. Next, distilled water (18.02 g) was added dropwise, and after completion of the dropwise addition, the solution was stirred at 100 ° C for 3 hours. Subsequently, the mixture was concentrated under reduced pressure, and the final solid component was adjusted to 30% by mass to obtain the component (A) (propylene glycol monomethyl ether solution). This is called "A-2".
S -30- 201220941 1 A-l」及「Ad」之成分組成等示於表1。 至於「A-3」係使用東亞合成公司製造之OX-SQ ME_ 20 〇 至於「A-4」係使用新中村化學工業公司製造之四經 甲基甲烷三丙烯酸酯。 [表1] 單位：質量％ A-1 A-2 甲基三甲氧基矽烷 45.70 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 分子量（Mw ) 3100 2300 [組成物之調製1 ] 於容器中饋入21.0g之作爲（B )成分之氧化錐（―次 平均粒徑：15nm) 、29.7g (固體成分8.9g)之「A」」、 使有機溶劑之總重量成爲70g之量的丙二醇單甲基醚，於 其中添加粒徑〇.11111!1之氧化鉻珠粒（>^1^&1〇公司製造） 350g，利用珠粒硏磨機，以I500rpm攪拌10小時，使氧化 錯之微粒子（（B)成分）分散。 於所得氧化銷微粒子之分散液中添加0.1 0g之二甲基 聚矽氧烷-聚氧伸烷基共聚物，獲得組成物「J-1」。 另外，除使用表2所示之成分以外，餘與組成物「 -31 - 201220941 」同樣，調製組成物「J-2」、「J-4」、「J-6」。成分組 成等示於表2。 [組成物之調製2] 於容器中饋入15.9g之作爲（B)成分之氧化鉻微粒子 (數平均一次粒徑：15 nm) 、1.9g 之 PLADD ED-151 (化 合物名：聚氧伸乙基烷基磷酸酯）、三（第二丁氧基）鋁 2.2g、乙醯基丙酮0.9g、2-丁醇2_3g、甲基乙基酮54.3g、 丙二醇單甲基醚15.7g，且於其中添加粒徑0.1mm之氧化鉻 珠粒（Nikkato公司製造）300g，利用珠粒硏磨機，以 1 5 00rpm攪拌10小時，使氧化鉻之微粒子（（B)成分）分 散。 於所得含氧化锆微粒子之分散液77.5g中添加22.4g之 「A-1」（固體成分6.7g) 、〇· lg之二甲基聚矽氧烷-聚氧 伸烷基共聚物，獲得組成物「J-3」。成分組成等示於表2 [組成物之調製3 ] 於容器中饋入15.91g之作爲（B)成分之氧化锆微粒 子（數平均一次粒徑：15nm) 、1.91g 之 PLADD ED-151、 三（第二丁氧基）鋁2.20g、乙醯基丙酮0.85g、2-丁醇 2.30g、甲基乙基酮70.00g，於其中添加粒徑0.1mm之氧化 鉻珠粒（Nikkato公司製造）3 5 0g，利用珠粒硏磨機，以 1 500rpm攪拌1〇小時，使氧化锆之微粒子（B )分散。The composition of components of S -30- 201220941 1 A-l" and "Ad" is shown in Table 1. As for "A-3", OX-SQ ME_ 20 manufactured by Toagosei Co., Ltd. is used. As for "A-4", tetramethylmethane triacrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd. is used. [Table 1] Unit: mass% A-1 A-2 methyltrimethoxydecane 45.70 17.89 phenyltrimethoxydecane_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 Molecular Weight (Mw) 3100 2300 [Preparation of Composition 1] 21.0 g of an oxide cone as a component (B) was fed into a vessel ("minor average particle diameter: 15 nm"), 29.7 g (solid content: 8.9 g) "A"", propylene glycol monomethyl ether in an amount of 70 g based on the total weight of the organic solvent, and chrome oxide beads having a particle size of 1111111!1 (>^1^&1〇) Manufactured) 350 g, which was stirred at I500 rpm for 10 hours using a bead honing machine to disperse the oxidized fine particles (component (B)). To the dispersion of the obtained oxidized pin fine particles, 0.10 g of a dimethylpolysiloxane-polyoxyalkylene copolymer was added to obtain a composition "J-1". In addition, the components "J-2", "J-4", and "J-6" were prepared in the same manner as the composition "-31 - 201220941" except for the components shown in Table 2. The grouping is shown in Table 2. [Preparation of Composition 2] 15.9 g of chromium oxide fine particles (number average primary particle diameter: 15 nm) as component (B) and 1.9 g of PLADD ED-151 (Compound name: polyoxygen extension B) were fed into the vessel. Base alkyl phosphate), 2.2 g of tri(secondary butoxy)aluminum, 0.9 g of ethenylacetone, 2 to 3 g of 2-butanol, 54.3 g of methyl ethyl ketone, 15.7 g of propylene glycol monomethyl ether, and 300 g of chrome oxide beads (manufactured by Nikkato Co., Ltd.) having a particle diameter of 0.1 mm was added thereto, and the mixture was stirred at 1,500 rpm for 10 hours using a bead honing machine to disperse fine particles of chromium oxide (component (B)). 27.4 g of "A-1" (solid content: 6.7 g) and 〇· lg of dimethyl polyoxyalkylene-polyoxyalkylene copolymer were added to 77.5 g of the obtained dispersion containing zirconia fine particles to obtain a composition. "J-3". The composition and the composition are shown in Table 2. [Preparation of Composition 3] 15.91 g of zirconia fine particles (number average primary particle diameter: 15 nm) as component (B) and 1.91 g of PLADD ED-151, three were fed into the vessel. 2.20 g of (second butoxy)aluminum, 0.85 g of acetylacetone, 2.30 g of 2-butanol, and 70.00 g of methyl ethyl ketone, and chrome oxide beads having a particle diameter of 0.1 mm (manufactured by Nikkato Co., Ltd.) were added thereto. 305 g was dispersed by a bead honing machine at 1,500 rpm for 1 hour to disperse the zirconia fine particles (B).
S -32- 201220941 於所得氧化鉻微粒子之分散液93.17g中添加5.738之「 八-4」、1.〇8之作爲光聚合起始劑之113(^1^184(8八8?公 司製造）、O.lg之二甲基聚矽氧烷-聚氧伸烷基共聚物，獲 得組成物「J-5」。成分組成等示於表2» [組成物之調製4] 於氮氣流下，將四-正丁氧化鈦42.54g( 125毫莫耳） 及二乙二醇26.53 g ( 25 0毫莫耳）添加於溶劑（正丁醇， 6 0mL )中’並經混合。與該等一起，將離子交換水4 5g ( 250毫莫耳）與聯胺鹽酸鹽〇.〇85g(1.25毫莫耳）添加於溶 劑（正丁醇，1 OOmL )中，並經混合》合倂所得二種混合 溶液’在調整成25 °C之恆溫機內攪拌混合2小時，獲得組 成物「J - 7」。 ° -33- 201220941 【3谳一 Ό 1 29.9 〇 d 100.0 1 »—> 5.73 15.91 m oi 70.0 ON CN 0.85 d ο 100.0 寸 1 h 〇\ 00 21.0 70.0 o 100.0 m 1 Η-ι 卜 VO | 15.9 15.7 m CS 54.3 OS CS CS <> d d 100.0 <N ON 〇〇 21.0 70.0 d 100.0 1 Os 〇〇 21.0 70.0 d 100.0 單位：質量％ A-1 (固體成分） i A-2 (固體成分） A-3 (固體成分） A-4丙烯酸單體 氧化锆 丙二醇單甲基醚 2-丁醇 甲基乙基酮 PLAAD ED-151 三（第二丁氧基）鋁 乙醯基丙酮 二甲基聚矽氧烷-聚氧伸烷基共聚物υ 寸 00 υ V-i 口 Ο CQ b0 kH 合計 < m U P Uh κ 绷鉍#*蜮.>%自01( I 餵饀绶1EIII遯fr糊S-翻a^堋鉍tiHItfA3>^fr沲：寸-v ots-wNcys-xo-h}绷鉍啶^链<055账：e-v s -34- 201220941 [實施例1〜4、比較例1〜3] 針對前述之組成物「1」~「J-7」之各組成物如下列 進行評價》 〈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，利用堀場製作所公司製 造之動態光散射式粒徑分佈測定裝置測定於25 °c之體積平 均粒徑。體積平均粒徑未達50nm者記爲「〇」，50nm以 上未達l〇nm者記爲「△」，lOOnm以上者記爲「X」。結果 示於表3。 〈硬化膜之製作〉 •組成物「j-l」〜「J-5」、「J-7」 將組成物分佈於直徑4英&之熔融石英或矽基板上， 旋轉塗佈成厚度約Ιμηι，且在120°C加熱1分鐘，及在150°C 加熱60分鐘，製作硬化膜（膜厚：Ιμιη)。 •組成物「J-6」 將組成物分佈於直徑4英吋之熔融石英或矽基板上， 旋轉塗佈成厚度約Ιμηι，且在12(TC加熱1分鐘，隨後，使 用接觸式光罩對準曝光機（CONTACT· MASK ALIGNER) ，在大氣中以使曝光量成爲2000mJ/cm2之方式照射紫外線 ，接著，在150 °C加熱60分鐘，製作硬化膜。 〈硬化膜之特性評價〉 測定並評價前述硬化膜之下述特性。結果示於表3。 (2 )硬化性 -35- 201220941 以手指觸摸前述硬化膜表面’無發黏者記爲「〇」， 有發黏者記爲「X」。 (3 )龜裂耐性 以目視觀察前述硬化膜之外觀’無龜裂者記爲「〇」 ，有龜裂者記爲「X」。 (4 )透明性 使用日本分光公司製造之分光光度計’測定前述硬化 膜在波長400nm下之透射率（％ )。透射率爲9 0%以上者記 爲「〇」，未達90%者記爲「X」。 (5 )折射率 使用METRICON公司製造之稜鏡耦光器，測定23°C、 波長633nm下之折射率。折射率爲1·6以上時記爲「〇」’ 未達1.6時記爲「X」。 (6 )耐熱性 使用烘箱，使前述硬化膜在溫度3 00°c加熱處理5分鐘 。處理前後之硬化膜之透射率之降低（透射率之減少比例 )未達10%時記爲「〇」，爲10%以上時記爲「X」。 實施例 1 實施例 2 實施例 3 實施例 4 比較例 1 比較例 2 比較例 3 組成物之麵 J-1 J-2 J-3 J-4 J-5 J-6 J-7 分散粒徑 〇 〇 〇 〇 〇 — — 硬化性 〇 〇 〇 〇 〇 〇 〇 龜裂耐性 〇 〇 〇 〇 〇 〇 X 透明性 〇 〇 〇 〇 〇 〇 〇 折射率 〇 〇 〇 〇1 〇 X 〇 耐熱性 〇 〇 〇 〇 X 〇 〇 -36- 201220941 【圖式簡單說明】 圖1爲槪念性顯示本發明之發光元件之實施形態例1之 剖面圖。 圖2爲槪念性顯示本發明之發光元件之實施形態例2之 剖面圖。 圖3爲槪念性顯示本發明之發光元件之實施形態例3之 剖面圖* 【主要元件符號說明】 10、20、30 :發光元件 1 1 ' 21 ' 3 1 :基板 13、23、33 :第一電極 15、25、35 :發光層 ' 17、27、37:第二電極 1 8、2 8、3 8、3 9 :含粒子層 -37-S-32-201220941 Adding 5.738 of "8-4" and 1.〇8 as a photopolymerization initiator to the 93.17 g of the obtained dispersion of chromium oxide fine particles (^1^184 (manufactured by 8:8?) ), O.lg dimethyl polyoxyalkylene-polyoxyalkylene copolymer, the composition "J-5" is obtained. The composition and the composition are shown in Table 2» [Preparation of the composition 4] under a nitrogen stream, 42.54 g (125 mmol) of tetra-n-butyl titanium oxide and 26.53 g (250 mmol) of diethylene glycol were added to the solvent (n-butanol, 60 mL) and mixed. Adding 4 5g (250 millimolar) of ion-exchanged water and hydrazine hydrochloride 〇.〇85g (1.25 millimolar) to the solvent (n-butanol, 100 mL), and mixing The mixed solution was stirred and mixed in a thermostat adjusted to 25 ° C for 2 hours to obtain a composition "J - 7". ° -33 - 201220941 [3谳一Ό 1 29.9 〇d 100.0 1 »-> 5.73 15.91 m oi 70.0 ON CN 0.85 d ο 100.0 inch 1 h 〇\ 00 21.0 70.0 o 100.0 m 1 Η-ι VO | 15.9 15.7 m CS 54.3 OS CS CS <> dd 100.0 <N ON 〇 〇21.0 70.0 d 100.0 1 Os 〇〇21.0 70.0 d 100.0 Unit: mass % A-1 (solid content) i A-2 (solid content) A-3 (solid content) A-4 acrylic monomer zirconia propylene glycol monomethyl Ethyl ether 2-butanol methyl ethyl ketone PLAAD ED-151 Tris(2-butoxy)aluminum ethionyl dimethyl polyoxane-polyoxyalkylene copolymer υ 00 υ Vi Ο CQ b0 kH total < m UP Uh κ 铋 铋 #*蜮.>% from 01 (I feed E1EIII遁fr paste S-turn a^堋铋tiHItfA3>^fr沲: inch-v ots-wNcys- Xo-h} 铋 铋 ^ chain chain < 055 account: ev s -34 - 201220941 [Examples 1 to 4, Comparative Examples 1 to 3] For the composition of the above-mentioned compositions "1" to "J-7" (Evaluation of the characteristics of the composition) (1) Dispersion particle size The fine particles in the obtained composition were measured at a volume average of 25 ° C by a dynamic light scattering type particle size distribution measuring apparatus manufactured by Horiba, Ltd. Particle size. Those whose volume average particle diameter is less than 50 nm are referred to as "〇", those which are less than 10 nm above 50 nm are referred to as "△", and those of 100 nm or more are referred to as "X". The results are shown in Table 3. <Preparation of cured film> • Compositions "jl" to "J-5" and "J-7" The composition is distributed on a fused silica or tantalum substrate having a diameter of 4 inches & and is spin-coated to a thickness of about Ιμηι. This was heated at 120 ° C for 1 minute and at 150 ° C for 60 minutes to prepare a cured film (film thickness: Ιμιη). • Composition "J-6" The composition was distributed on a 4 inch diameter fused silica or tantalum substrate, spin coated to a thickness of about Ιμηι, and heated at 12 (TC for 1 minute, then using a contact mask pair) The exposure exposure machine (CONTACT·MASK ALIGNER) was irradiated with ultraviolet light so that the exposure amount became 2000 mJ/cm 2 in the atmosphere, and then heated at 150 ° C for 60 minutes to produce a cured film. <Evaluation of characteristics of the cured film> Measurement and evaluation The following characteristics of the cured film are shown in Table 3. (2) Curing property -35 - 201220941 Touching the surface of the cured film with a finger is described as "〇", and sticky person is marked as "X" (3) Crack resistance. The appearance of the cured film was visually observed. The crack-free one was marked as "〇", and the cracked one was recorded as "X". (4) The transparency was measured using a spectrophotometer manufactured by JASCO Corporation. 'The transmittance (%) of the cured film at a wavelength of 400 nm is measured. The transmittance is 90% or more, which is "〇", and the less than 90% is recorded as "X". (5) The refractive index is made by METRICON.稜鏡 稜鏡 ,, measuring the refraction at 23 ° C, wavelength 633 nm When the refractive index is 1.6 or more, it is referred to as "〇". When it is less than 1.6, it is referred to as "X". (6) Heat resistance The oven is heated and treated at a temperature of 300 ° C for 5 minutes in an oven. The decrease in the transmittance of the cured film (the decrease ratio of the transmittance) is "〇" when it is less than 10%, and is "X" when it is 10% or more. Example 1 Example 2 Example 3 Example 4 Comparison Example 1 Comparative Example 2 Comparative Example 3 Surface of the composition J-1 J-2 J-3 J-4 J-5 J-6 J-7 Dispersed particle size 〇〇〇〇〇 - sclerosing 〇〇〇〇〇 〇〇 crack resistance 〇〇〇〇〇〇 X transparency 〇〇〇〇〇〇〇 refractive index 〇〇〇〇 1 〇 X 〇 heat resistance 〇〇〇〇 X 〇〇 -36- 201220941 [Simple diagram] BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing a first embodiment of a light-emitting device of the present invention. Fig. 2 is a cross-sectional view showing a second embodiment of a light-emitting device of the present invention. Section 3 of Embodiment 3 of Light Emitting Element of the Invention [Description of Main Element Symbols] 10, 20, 30: Illumination 1 1 ' 21 ' 3 1 : substrate 13, 23, 33: first electrode 15, 25, 35: light-emitting layer '17, 27, 37: second electrode 18, 28, 38, 3 9 : Particle layer-37-
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