201237106 六、發明說明： 【發明所屬之技術領域】 本發明關於硬化性有機聚矽氧烷組成物、光學元件封 止材及光學元件，詳細地關於可形成在高溫、高濕的環境 下保管後之廻焊試驗中，能防止自封裝的剝離或龜裂之硬 化物的硬化性有機聚矽氧烷組成物、由該組成物所成的光 學元件封止材及經由此硬化物所封閉的可靠性優異之光學 元件。 【先前技術】 加成硬化性有機聚矽氧烷組成物係含有含烯基等的脂 肪族不飽和基之有機聚矽氧烷及有機氫聚矽氧烷，藉由氫 矽烷化反應進行硬化而給予硬化物。如此所得之硬化物係 耐熱性、耐寒性、電絕緣性優異，而且因爲透明，而使用 於LED的封止材等之各種光學用途。 光學用途尤其LED的封止材所使用的聚矽氧材料， 係在LED元件的組裝時經過廻焊步驟，故暫時地暴露於 260°C左右的高溫下。因此，要求對於廻焊時的樹脂之龜 裂或自封裝的剝離等具有耐性，即耐廻焊性。 於以往的LED封止材料中，有提案藉由添加各種接 著助劑等，而提高耐廻焊性（日本特開2010-111811號公 報、日本特開2010-109034號公報、日本特開2010-13619 號公報、日本特開2010-13503號公報、日本特開 2007-84766號公報：專利文獻1〜5)。然而，於高溫、 201237106 高濕下保管，使樹脂與反射器吸收水分後進行廻焊的吸濕 廻焊試驗中，即使以往在廻焊試驗沒有問題的樹脂中，也 發生樹脂的龜裂或自封裝的剝離等，而希望其之解決。 [先前技術文獻] [專利文獻] [專利文獻1]日本特開2010-1 1 1 81 1號公報 [專利文獻2]日本特開2010-109034號公報 [專利文獻3]日本特開20 1 0- 1 36 1 9號公報 [專利文獻4]日本特開2010- 1 3 5 03號公報 [專利文獻5]日本特開2007-84766號公報 【發明內容】 [發明所欲解決的問題] 本發明係鑒於上述情事而完成者，目的在於提供可給 予即使在吸濕廻焊試驗中，也不會發生樹脂的龜裂或自封 裝的剝離之硬化物的硬化性有機聚矽氧烷組成物及由該組 成物所成的光學元件封止材，以及經此硬化物所封閉的光 學元件。 [解決問題的手段] 本發明者們爲了達成上述目的，進行專心致力的檢討 ，結果發現藉由在以往的硬化性有機聚矽氧烷組成物中， 添加具有下述所示之特定的酯鍵與烷氧基矽烷基的化合物 -6- 201237106 ，可得到耐吸濕廻焊性優異之聚矽氧硬化物，而達成本發 明。 因此，本發明提供下述的硬化性有機聚矽氧烷組成物 、光學元件封止材及光學元件。 [申請專利範圍第1項] 一種硬化性有機聚矽氧烷組成物，其含有： (A)下述平均組成式（1): R^S i O (4-a)/2 ( 1 ) (式中，R1係彼此相同或異種的非取代或取代的1價烴 基，R1中的至少1個係芳基，全部R1的0.1〜40莫耳％ 係烯基，a係滿足l$a^3之正數） 所示之在1分子中具有至少2個鍵結於矽原子的烯基之有 機聚矽氧烷， (B )下述平均組成式（2 )： R2bHcS ί O (4-b-c)/2 (2) (式中，R2係脂肪族不飽和基以外之彼此相同或異種的 非取代或取代的1價烴基、或烷氧基，b及c係滿足 〇.7Sb$2.1、O.OOlScSl.O、且 0.8Sb+cS3.0 之正數） 所示之有機氫聚矽氧烷， (C) 含有鈾族金屬的氫矽烷化觸媒， (D) 下述通式（3)所示之化合物： 【化1】201237106 VI. [Technical Field] The present invention relates to a curable organopolysiloxane composition, an optical element sealing material, and an optical element, and in detail, after being stored in a high-temperature, high-humidity environment, In the tantalum welding test, the curable organopolysiloxane composition which can prevent the peeling or cracking of the self-package, the optical element sealing material formed from the composition, and the reliable sealing by the cured product Excellent optical components. [Prior Art] The addition-curable organopolyoxane composition contains an organic polyoxyalkylene group containing an aliphatic unsaturated group such as an alkenyl group and an organic hydrogen polyoxyalkylene, which is hardened by a hydroquinonelation reaction. Give hardened material. The cured product thus obtained is excellent in heat resistance, cold resistance, and electrical insulating properties, and is used in various optical applications such as sealing materials for LEDs because of transparency. In particular, the polyoxyxene material used for the sealing material of the LED is subjected to a soldering step at the time of assembly of the LED element, and is temporarily exposed to a high temperature of about 260 °C. Therefore, it is required to have resistance to cracking of the resin at the time of brazing or peeling from the package, that is, soldering resistance. In the conventional LED sealing material, it is proposed to improve the soldering resistance by adding various kinds of bonding aids, etc. (JP-A-2010-111811, JP-A-2010-109034, and JP-A-2010- Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. However, in the moisture absorbing soldering test in which the resin and the reflector absorb moisture after being stored at a high temperature and 201237106, the resin is cracked or caused by resin in the resin which has no problem in the soldering test. The peeling of the package, etc., and hope to solve it. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2010-1109034 [Patent Document 2] JP-A-2010-109034 (Patent Document 3) [Patent Document 4] Japanese Patent Laid-Open Publication No. JP-A-2007-84766 (Patent Document 5) [Problems to be Solved by the Invention] The present invention In view of the above, it is an object of the present invention to provide a curable organopolyoxane composition which can provide a cured product which does not cause cracking of a resin or peeling from a package even in a moisture absorption soldering test. An optical element sealing material formed by the composition, and an optical element sealed by the cured product. [Means for Solving the Problem] In order to achieve the above object, the inventors of the present invention conducted a review of the specific ester bond, and found that a specific ester bond having the following specificity is added to the conventional curable organopolysiloxane composition. The present invention can be attained by the compound-6-201237106 having an alkoxyalkylene group, which is obtained by obtaining a polyfluorene-cured material excellent in moisture absorption and weldability. Accordingly, the present invention provides the following curable organopolyoxane composition, optical element sealing material, and optical element. [Patent Application No. 1] A curable organopolyoxane composition comprising: (A) an average composition formula (1): R^S i O (4-a)/2 ( 1 ) ( In the formula, R1 is an unsubstituted or substituted monovalent hydrocarbon group which is the same or different from each other, and at least one of R1 is an aryl group, and all of R1 is 0.1 to 40 mol% of an alkenyl group, and a is satisfying l$a^3. Positive number) shows an organopolyoxane having at least 2 alkenyl groups bonded to a ruthenium atom in one molecule, (B) the following average composition formula (2): R2bHcS ί O (4-bc)/ 2 (2) (wherein R2 is an unsubstituted or substituted monovalent hydrocarbon group or alkoxy group which is the same or different from each other other than the aliphatic unsaturated group, and b and c systems satisfy 〇.7Sb$2.1, O.O01ScSl. O, and a positive number of 0.8Sb+cS3.0) an organohydrogen polyoxyalkylene, (C) a hydroquinone catalyst containing a uranium metal, (D) a compound represented by the following formula (3) : 【化1】
SiR3d(〇R4)(3-d) 0 201237106 (式中’ R3、R4、R5係各自互相相同或異種的非取代或 取代的1價烴基，d爲0、1或2)。 [申請專利範圍2] 如申請專利範圍第1項之硬化性有機聚矽氧烷組成物 ，其中（B)成分係在1分子中具有至少丨個鍵結矽原子 的芳基。 [申請專利範圍3] 如申請專利範圍第1或2項之硬化性有機聚矽氧烷組 成物，其中相對於（A)成分與（B)成分的合計100質 量份而言，（D)成分的添加量爲0.1〜1〇質量份。 [申請專利範圍4] 一種光學元件封止材，其係由如申請專利範圍第1至 3項中任一項之組成物所構成。 [申請專利範圍5 ] —種光學元件，其係經如申請專利範圍第4項之封止 材的硬化物所封閉。 [發明的效果] 本發明的硬化性有機聚矽氧烷組成物之硬化物，由於 對吸濕廻焊的可靠性良好，可使用於光學元件封止材。 【實施方式】 [實施發明的形態] 以下，詳細說明本發明。 -8 - 201237106 [(A )成分] (A)成分係下述平均組成式（1)所示的有機聚矽 氧烷。 R^S 1 O (4-a)/2 ( 1 ) (式中，R1係彼此相同或異種的非取代或取代的1價烴 基，R1中的至少1個係芳基，全部R1的0.1〜40莫耳％ 係烯基，a係滿足l$a$3之正數）。 (A)成分係在1分子中具有至少2個鍵結於矽原子 的烯基，作爲鍵結於此矽原子的烯基，例如可舉出乙烯基 、烯丙基、丁烯基、戊烯基、己烯基、庚烯基等通常碳數 2〜8、較佳2〜4左右者，特佳爲乙烯基。 (A)成分中的烯基之含量，係在鍵結於矽原子的1 價有機基（即，上述平均組成式（1)中，R1所示的非取 代或取代的1價烴基）中，較佳爲0.1〜40莫耳％，特佳 爲0.2〜20莫耳％。 又，（A)成分係在分子中具有至少1個鍵結於砂原 子的芳基。作爲該芳基，可舉出苯基、甲苯基、二甲苯基 、萘基等通常碳數6〜14、較佳6〜10者，特佳爲苯基。 (A)成分中的芳基之含量，係在鍵結於砂原子的1 價有機基（即，上述平均組成式（1 )中，R1所示的非取 代或取代的1價烴基）中，較佳爲至少5莫耳％。在鍵結 於矽原子的1價有機基中，當芳基未達5莫耳％時，經硬 化的被覆保護材之耐熱性或低溫特性變差，會導致熱衝撃 -9 - 201237106 試驗的可靠性之降低，故較佳爲至少5莫耳％ 3 〇莫耳％以上。其上限係沒有特別的規定，但 矽原子的1價有機基中，較佳爲80莫耳％以下 7〇莫耳％以下。 作爲（A)成分的烯基及芳基以外之鍵結於 有機基，例如可舉出甲基、乙基、丙基、丁基、 基、環己基、庚基等的烷基，苄基、苯乙基等的 氯甲基、3-氯丙基、3，3,3-三氟丙基等的鹵化烷 常碳數1〜12、較佳碳數1〜10左右的非取代或 的1價烴基。 又，a係滿足1〜3之正數，本成分的分子 狀或支鏈狀，可爲直鏈狀、支鏈狀中的任一者。 此有機聚矽氧烷爲直鏈狀時之藉由旋轉式黏 定的黏度，從操作性的方面來看，在25 °C較佳 20,00 0m Pa· s，特佳爲 500 〜10,000mPa· s 左右 黏度若過低，則由於容易流動，有發生成形毛邊 性，黏度若過高，則在必要成分混合時所混入的 會發生難以脫除的情況。再者，支鏈狀時係成爲 體，當爲液體時’在25 °C的黏度較佳爲1,000〜 • s左右的範圍。使用固體狀者時，較佳爲倂用 的直鏈狀有機聚矽氧烷，使在25°C的黏度成 2 0，OOOmP a · s 〇 [(B)成分] ，特佳爲 在鍵結於 ，特佳爲 矽原子的 戊基、己 芳烷基， 基等之通 鹵素取代 構造係鏈 度計所測 爲 1 00〜 的範圍。 等的可能 空氣之泡 液體或固 5,000mPa 此與可溶 爲 1 00〜 -10- 201237106 (B )成分係下述平均組成式（2 ) 氧&’與（A)成分進行氫矽烷化加成 進行作用。 R2bHcS i O (4-b-c)/2 (式中’ R2係脂肪族不飽和基以外之 非取代或取代的1價烴基、或烷氧3 〇.7Sb^2.1、〇,〇01 1.0、且 0.8Sb 較佳爲滿足 l.〇gbS2.0、0.01 盍 cSl.O 之正數）。 作爲上述式（2 )中的R2之1價烴 A)成分中的作爲式（1.)中的Rl之脂 的非取代或取代的1價烴基所具體例示 院基等的非取代1價烴基，或此等基的 全部經鹵素原子（例如氯原子、溴原子 氧基的基（例如環氧基、環氧丙基、環 的取代1價烴基等。又，作爲烷氧基， 氧基、丙氧基、丁氧基等，較佳爲甲 較佳爲碳數1〜6的烷基、碳數6〜10 基、苯基。又，作爲該1價烴基的取代 基的基或烷氧基時，可對本發明組成物 性。 於（B)成分中，特佳爲具有鍵結 該芳基較佳爲苯基。 (B)成分中的芳基之含量，係在 所示的有機氫聚矽 反應，作爲交聯劑 (2) 彼此相同或異種的 ，b及c係滿足 + eg 3.0之正數， •且 1.5$b+ c$2.5 基，例如可舉出（ 肪族不飽和基以外 的烷基、芳基、芳 氫原子之一部分或 、氟原子）、含環 氧丙氧基）等取代 可例示甲氧基、乙 氧基、乙氧基。R2 的芳基，更佳爲甲 基，當具有含環氧 的硬化物賦予黏著 於矽原子的芳基。 鍵結於矽原子的1 -11 - 201237106 價有機基（即，上述平均組成式（2 )中，R2所示之脂肪 族不飽和基以外的非取代或取代的1價烴基）中，較佳爲 至少5莫耳％。在鍵結於砂原子的1價有機基中，若含有 5莫耳％以上的芳基，則經硬化的被覆保護材之耐熱性或 低溫特性係更優異，熱衝撃試驗的可靠性亦更優異。因此 ，較佳至少5莫耳％、特佳20莫耳％以上爲芳基。其上 限係沒有特別的規定，但較佳爲8 0莫耳％以下，特佳爲 6〇莫耳％以下。 (B)成分的有機氫聚矽氧烷之分子構造係沒有特別 的限制，例如可使用直鏈狀、環狀、支鏈狀、三次元網狀 構造（樹脂狀）等之以往製造的各種有機氫聚矽氧烷。 前述有機氫聚矽氧烷宜爲在1分子中具有至少2個（ 通常2〜300個左右）的SiH基。當前述有機氫聚矽氧烷 具有直鏈狀構造或支鏈狀構造時’此等SiH基係可位於分 子鏈末端及分子鏈非末端部分中的任一者’也可位於這兩 者。 前述有機氫聚矽氧烷之1分子中的矽原子之數（聚合 度），較佳爲2〜1，000個，尤佳爲2〜200個’更佳爲2 〜1〇〇個左右。再者，前述有機氫聚砍氧烷在25 °C較佳爲 液狀，藉由旋轉式黏度計所測定的在25 °C的黏度較佳爲1 〜l，000mPa· s,更佳爲 1〇 〜100mPa. s 左右。 作爲上述平均組成式（2)所示的有機氫聚砂氧院’ 例如可舉出式：含有至少4個式：R2HSi0所示的有機氫 矽氧烷單位之環狀化合物、式：R23Si0(HR2Si0)eSiR23所 -12- 201237106 示的化合物、式：HR22SiO(HR2SiO)eSiR22H所示的化 、式：HR22SiO(R22SiO)fSiR22H 所示的化合物、 HR22SiO(HR2SiO)e(R22SiO)fSiR22H 所示的化合物等。 式中，R2係如前述，e及f爲至少1。 或者，上述平均組成式（2)所示的有機氫聚矽 亦可含有式：HSiOu所示的矽氧烷單位、與式：R2 所示的矽氧烷單位及/或式：R22HSiO〇.5所示的矽氧 位。再者，該有機氫聚矽氧烷也可含有不含SiH基的 機矽氧烷單位、二有機矽氧烷單位、三有機矽氧烷單 /或Si04/2單位。上述式中的R2係如前述。 作爲（B)成分的有機氫聚矽氧烷之具體例，可 1，1,3,3-四甲基二矽氧烷、1，3,5,7-四甲基環四矽氧烷 (氫二甲基矽烷氧基）甲基矽烷、三（氫二甲基矽烷 )苯基矽烷、甲基氫環聚矽氧烷、甲基氫矽氧烷·二 矽氧烷環狀共聚物、分子鏈兩末端三甲基矽烷氧基封 基氫聚矽氧烷、分子鏈兩末端三甲基矽烷氧基封鎖二 矽氧烷•甲基氫矽氧烷共聚物、分子鏈兩末端三甲基 氧基封鎖二苯基矽氧烷·甲基氫矽氧烷共聚物、分子 末端三甲基矽烷氧基封鎖甲基苯基矽氧烷•甲基氫矽 共聚物、分子鏈兩末端三甲基矽烷氧基封鎖二甲基矽 •甲基氫矽氧烷•甲基苯基矽氧烷共聚物、分子鏈兩 三甲基矽烷氧基封鎖二甲基矽氧烷·甲基氫矽氧烷· 基矽氧烷共聚物、分子鏈兩末端二甲基氫矽烷氧基封 基氫聚矽氧烷、分子鏈兩末端二甲基氫矽烷氧基封鎖 合物 式： 上述 氧烷 HSiO 烷單 單有 位及 舉出 、 三 氧基 甲基 鎖甲 甲基 矽烷 鏈兩 氧烷 氧烷 末端 二苯 鎖甲 二甲 -13- 201237106 基聚矽氧烷、分子鏈兩末端二甲基氫矽烷氧基封 矽氧烷·甲基氫矽氧烷共聚物、分子鏈兩末端二 烷氧基封領二甲基矽氧烷·甲基苯基矽氧烷共聚 鏈兩末端二甲基氫矽烷氧基封鎖二甲基矽氧烷· 氧烷共聚物、分子鏈兩末端二甲基氫矽烷氧基封 基聚矽氧烷、分子鏈兩末端二甲基氫矽烷氧基封 聚矽氧烷、分子鏈兩末端二甲基氫矽烷氧基封鎖 氧烷·甲基氫矽氧烷共聚物，於此等的各例示化 甲基的一部分或全部經乙基、丙基等其它烷基或 的基取代烷基所取代之有機氫聚矽氧烷、式： 所示的矽氧烷單位與式：R22HSiO〇.5所示的矽氧 式：Si02所示的矽氧烷單位所成之有機矽氧烷共 :R22HSiOG.5所示的矽氧烷單位與式：Si〇2所示 單位所成之有機矽氧烷共聚物、式：R2HSiO所 烷單位與式：I^SiCh.s所示的矽氧烷單位及式 所示的矽氧烷單位中的任一者或兩者所成之有機 聚物、及由此等的有機聚矽氧烷之2種以上所成 。上述式中的R2具有與前述同樣的定義》 (B)成分係可單獨1種使用，也可倂用2種 (B)成分的配合量，係在（C)成分的氫: 媒之存在下使本組成物硬化的充分量，通常以相 )成分中的脂肪族不飽和基而言，（B)成分中的 之莫耳比較佳成爲0.2〜5，更佳成爲0·4〜2之 莫耳比若過小或過大，則硬化會不足，有無法滿 鎖二甲基 甲基氫矽 物、分子 二苯基矽 鎖甲基苯 鎖二苯基 二苯基矽 合物中， 含環氧基 RSSiOo.s 烷單位和 聚物、式 的矽氧烷 示的矽氧 :HSiO,.s 矽氧烷共 的混合物 I以上。 砂院化觸 對於（A J SiH 基 量。上述 足硬度、 -14- 201237106 耐熱性、耐龜裂性等之作爲封止材料的特性之情況。 [(C)成分] 作爲（C)成分的鉑族金屬系氫矽烷化觸媒，只要是 促進（A)成分中的矽原子鍵結脂肪族不飽和基與（B) 成分中的SiH基之氫矽烷化加成反應者，則可使用任何的 觸媒。作爲（C)成分，例如可舉出鉑、鈀、铑等的鉑族 金屬，或氯鈾酸、醇改性氯鉑酸、氯鉑酸與烯烴類、乙烯 基矽氧烷或乙炔化合物的配位化合物、四（三苯基膦）鈀 、氯三（三苯基膦）铑等的鉑族金屬化合物，特佳爲鉑化 合物。 (C)成分係可單獨1種使用，也可倂用2種以上。 (C)成分的配合量可爲當作氫矽烷化觸媒的有效量 ，更佳爲相對於（A)成分與（B)成分的合計質量而言 ，以鉑族金屬元素的質量換算爲0.1〜l，000ppm的範圍， 更佳爲1〜500ppm的範圍。 [(D)成分] (D)成分係下述通式（3)所示的具有酯鍵與烷氧 基矽烷基的化合物，藉由添加（D)成分，在吸濕廻焊試 驗中，得到抑制樹脂的龜裂或自封裝的剝離之效果。 作爲（D)成分之具有酯鍵與烷氧基矽烷基的化合物 ，係在1分子中具有至少1個酯鍵與至少1個烷氧基矽烷 基者，爲下述通式（3)所示的化合物》 -15- 201237106 【化2】SiR3d(〇R4)(3-d) 0 201237106 (wherein R3, R4 and R5 are each an unsubstituted or substituted monovalent hydrocarbon group which is the same or different from each other, and d is 0, 1 or 2). [Patent 2] The sclerosing organopolysiloxane composition according to claim 1, wherein the component (B) is an aryl group having at least one bonded ruthenium atom in one molecule. [Application No. 3] The curable organopolysiloxane composition of the first or second aspect of the patent application, wherein the component (D) is 100 parts by mass based on the total of the components (A) and (B) The amount added is 0.1 to 1 part by mass. [Patent 4] An optical element sealing material comprising the composition of any one of claims 1 to 3. [Patent Application No. 5] An optical element which is closed by a cured product of a sealing material as in the fourth application of the patent application. [Effects of the Invention] The cured product of the curable organopolysiloxane composition of the present invention can be used for an optical element sealing material because of its good reliability against moisture absorbing soldering. [Embodiment] [Embodiment of the Invention] Hereinafter, the present invention will be described in detail. -8 - 201237106 [Component (A)] The component (A) is an organopolysiloxane represented by the following average composition formula (1). R^S 1 O (4-a)/2 ( 1 ) (wherein R1 is an unsubstituted or substituted monovalent hydrocarbon group which is the same or different from each other, and at least one of R1 is an aryl group, and all of R1 is 0.1~ 40 mole % is alkenyl, and a is a positive number of l$a$3). The component (A) has at least two alkenyl groups bonded to a ruthenium atom in one molecule, and examples of the alkenyl group bonded to the ruthenium atom include a vinyl group, an allyl group, a butenyl group, and a pentene group. The base, hexenyl, heptenyl or the like usually has a carbon number of from 2 to 8, preferably from 2 to 4, particularly preferably a vinyl group. The content of the alkenyl group in the component (A) is in a monovalent organic group bonded to a ruthenium atom (that is, an unsubstituted or substituted monovalent hydrocarbon group represented by R1 in the above average composition formula (1), It is preferably 0.1 to 40 mol%, particularly preferably 0.2 to 20 mol%. Further, the component (A) has at least one aryl group bonded to the sand atom in the molecule. The aryl group may, for example, be a phenyl group, a tolyl group, a xylyl group or a naphthyl group, and has a usual carbon number of from 6 to 14, preferably from 6 to 10, particularly preferably a phenyl group. The content of the aryl group in the component (A) is in a monovalent organic group bonded to a sand atom (that is, an unsubstituted or substituted monovalent hydrocarbon group represented by R1 in the above average composition formula (1), It is preferably at least 5 mol%. In the monovalent organic group bonded to a ruthenium atom, when the aryl group is less than 5 mol%, the heat resistance or low-temperature characteristics of the hardened coated protective material are deteriorated, which leads to reliable heat test -9 - 201237106 The decrease in properties is preferably at least 5 mol% 3 〇 mol% or more. The upper limit is not particularly limited, but among the monovalent organic groups of the halogen atom, it is preferably 80 mol% or less and 7 mol% or less. Examples of the organic group to be bonded to the organic group other than the alkenyl group and the aryl group as the component (A) include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a group, a cyclohexyl group or a heptyl group, and a benzyl group. a halogenated alkane such as chloromethyl, 3-chloropropyl or 3,3,3-trifluoropropyl, such as phenethyl, usually having an unsubstituted or substituted carbon number of from 1 to 12, preferably from 1 to 10 carbon atoms. Valence hydrocarbon group. Further, a is a positive number of 1 to 3, and the molecular or branched form of the component may be either linear or branched. When the organic polyoxyalkylene is linear, the viscosity by the rotary bonding is preferably 20,00 0 mPa·s at 25 ° C, and particularly preferably 500 to 10,000 mPa from the viewpoint of handling. s If the left and right viscosities are too low, the forming burrs may occur due to easy flow, and if the viscosity is too high, it may be difficult to remove the mixed components when necessary. Further, in the case of a branched chain, it is a body, and when it is a liquid, the viscosity at 25 ° C is preferably in the range of about 1,000 to s. When a solid is used, it is preferably a linear organopolyoxane for use in a viscosity of 25 ° C to 2,0,000 mPa s 〇 [(B) component], particularly preferably at the bonding Further, it is particularly preferably a range of 1 00 〜 which is a halogen-substituted structural ligament meter of a pentyl group, a hexyl aralkyl group or a fluorene atom. Such a possible air bubble liquid or solid 5,000 mPa This is soluble with 1 00~ -10- 201237106 (B) The composition is the following average composition formula (2) Oxygen & ' and (A) component hydrosilylation plus In progress. R2bHcS i O (4-bc)/2 (wherein R2 is an unsubstituted or substituted monovalent hydrocarbon group other than an aliphatic unsaturated group, or an alkoxy 3 〇.7Sb^2.1, 〇, 〇01 1.0, and 0.8 Sb is preferably a positive number satisfying l.〇gbS2.0, 0.01 盍cSl.O). The unsubstituted or substituted monovalent hydrocarbon group which is an unsubstituted or substituted monovalent hydrocarbon group of the R1 in the formula (1.) in the monovalent hydrocarbon A) component of the formula (2) Or all of such a group is a halogen atom (for example, a chlorine atom or a bromine atomicoxy group (for example, an epoxy group, a propylene group, a ring-substituted monovalent hydrocarbon group, etc.), as an alkoxy group, an oxy group, Preferred examples of the propoxy group, the butoxy group and the like are preferably an alkyl group having 1 to 6 carbon atoms, a carbon number of 6 to 10 groups, and a phenyl group. Further, a group or alkoxy group as a substituent of the monovalent hydrocarbon group. In the case of the component (B), it is particularly preferred to have a bond. The aryl group is preferably a phenyl group. The content of the aryl group in the component (B) is the organic hydrogen group shown. The hydrazine reaction is the same as or different from the crosslinking agent (2), and the b and c systems satisfy a positive number of + eg 3.0, and 1.5$b+ c$2.5, for example, an alkyl group other than the aliphatic unsaturated group. A methoxy group, an ethoxy group, an ethoxy group, and an aryl group of R2 may be exemplified by a substituent such as an aryl group, an aromatic hydrogen atom or a fluorine atom, or a glycidoxy group. More preferably, it is a methyl group, and when it has an epoxy-containing hardened substance, it imparts an aryl group bonded to a ruthenium atom. The 1 -11 - 201237106 valence organic group bonded to a ruthenium atom (that is, the above average composition formula (2), R2 In the unsubstituted or substituted monovalent hydrocarbon group other than the aliphatic unsaturated group shown, it is preferably at least 5 mol%. When the monovalent organic group bonded to the sand atom contains 5 mol% or more The aryl group is more excellent in heat resistance or low-temperature property of the hardened coated protective material, and is more excellent in reliability of the hot stamping test. Therefore, it is preferably at least 5 mol%, particularly preferably 20 mol% or more. The upper limit is not particularly limited, but is preferably 80% or less, and particularly preferably 6% by mole or less. The molecular structure of the organic hydrogen polyoxyalkylene of the component (B) is not particularly limited. For example, various organic hydrogen polyoxyalkylenes which have been conventionally produced, such as a linear chain, a cyclic chain, a branched chain, or a three-dimensional network structure (resin type) can be used. The above-mentioned organic hydrogen polyoxyalkylene is preferably in one molecule. Having at least 2 (usually 2 to 300 or so) SiH groups. When the aforementioned organic hydrogen polymerization When the oxane has a linear structure or a branched structure, 'these SiH groups may be located at either the end of the molecular chain and the non-terminal portion of the molecular chain' may also be located in the two. The aforementioned organohydrogen polyoxyalkylene. The number of the ruthenium atoms (degree of polymerization) in one molecule is preferably from 2 to 1,000, particularly preferably from 2 to 200, more preferably from about 2 to about 1. Further, the aforementioned organic hydrogen polymerization The chopped alkane is preferably liquid at 25 ° C, and the viscosity at 25 ° C as measured by a rotary viscometer is preferably from 1 to 1,000 mPa·s, more preferably from about 1 to about 100 mPa·s. The organic hydrogen polyoxo compound represented by the above average composition formula (2) is, for example, a cyclic compound containing at least four organic hydrooxane units represented by the formula: R2HSi0, and a formula: R23Si0 (HR2Si0) a compound represented by the formula: HR22SiO(HR2SiO)eSiR22H, a compound represented by the formula: HR22SiO(R22SiO)fSiR22H, a compound represented by HR22SiO(HR2SiO)e(R22SiO)fSiR22H, or the like. In the formula, R2 is as described above, and e and f are at least 1. Alternatively, the organic hydrogen polyfluorene represented by the above average composition formula (2) may further contain a unit of the formula: Hoxau, a unit of the formula: R2, and/or a formula: R22HSiO〇.5 The oxygen level shown. Further, the organohydrogenpolysiloxane may contain a SiH group-free oxime unit, a diorganooxane unit, a triorganooxane unit or a Si04/2 unit. R2 in the above formula is as described above. Specific examples of the organohydrogenpolyoxane as the component (B) include 1,1,3,3-tetramethyldioxane and 1,3,5,7-tetramethylcyclotetraoxane ( Hydrogen dimethyl decyloxy) methyl decane, tris(hydrodimethyl decane) phenyl decane, methyl hydrogen cyclopolyoxyalkylene, methyl hydroquinone dioxane cyclic copolymer, molecule The two ends of the chain are trimethyldecyloxy-blocking hydrogen polyoxyalkylene, the two-terminal dimethyl decyloxy group at the end of the molecular chain blocks the dioxane/methylhydroquinone copolymer, and the three-terminal oxygen at the end of the molecular chain Blocking of diphenyloxane·methylhydroquinone copolymer, molecular terminal trimethyldecaneoxy blockade methyl phenyl oxane • methylhydroquinone copolymer, molecular chain both ends trimethyl decane Oxygen-blocked dimethyl hydrazine-methylhydroquinone-methylphenyl decane copolymer, molecular chain ditrimethyl decyloxy blockade dimethyl methoxy oxane methyl hydro oxane a siloxane derivative, a dimethylhydroquinolyloxy-hydrogenated alkoxy oxyalkylene at the two ends of the molecular chain, and a dimethylhydroquinolyloxy group at the two-terminal end of the molecular chain: the above oxyalkylene HSiO alkane Single-positioned and exemplified, trioxymethyl-methyl-methyl decane-chain dioxooxane terminal diphenyl-methyl dimethyl-13- 201237106-based polyoxy siloxane, molecular chain both-terminal dimethylhydrohaloalkoxy Base-terminated oxime-methyl hydroquinone copolymer, molecular chain two-terminal dialkoxy-terminated dimethyl methoxy oxane-methyl phenyl methoxy olefin copolymer chain two-terminal dimethylhydroquinoloxy Blocking dimethyloxane oxyalkylene copolymer, molecular chain two-terminal dimethylhydroquinoloxy-blocking polyoxyalkylene, molecular chain two-terminal dimethylhydroquinoloxy alkoxy alkane, molecular chain The two-terminal dimethylhydrohalo alkoxy group blocks the oxyalkylene methylhydroquinoxane copolymer, and some or all of the alkyl groups of the above-exemplified methyl groups are substituted with other alkyl groups or alkyl groups such as ethyl or propyl groups. The organic hydrogen polyoxyalkylene substituted by the formula, the formula: the unit of the oxoxane and the organooxane represented by the formula: R22HSiO〇.5; : an organic oxane copolymer formed by a unit of arsonane represented by R22HSiOG.5 and a unit represented by the formula: Si〇2, and a formula: R2HSiO An alkane unit and an organic polymer of any one or both of a siloxane derivative unit of the formula: I^SiCh.s and a oxoxane unit represented by the formula, and the like Two or more kinds of alkane are formed. R2 in the above formula has the same definition as described above. The component (B) may be used singly or in combination with two types of components (B), in the presence of hydrogen of the component (C): The sufficient amount of the composition to be hardened is usually an aliphatic unsaturated group in the phase component, and the molar component in the component (B) is preferably 0.2 to 5, more preferably 0 to 4 to 2 If the ear ratio is too small or too large, the hardening will be insufficient, and there may be a failure to lock the dimethylmethylhydroquinone, the molecular diphenyl sulfonium methyl phenyl-terphenyl diphenyl phthalate, and the epoxy group. RSSiOo.s alkane units and polymers, a mixture of helium oxides of the formula: HSiO, a mixture of Hs. In the case of the AJ SiH base material, the above-mentioned foot hardness, -14-201237106 heat resistance, crack resistance, and the like as a sealing material. [(C) component] Platinum as the (C) component The group metal-based hydroquinone-catalyzed catalyst may be any one which promotes a hydroquinone-addition reaction of a ruthenium atom-bonded aliphatic unsaturation in the component (A) and a SiH-group in the component (B). The catalyst (C) may, for example, be a platinum group metal such as platinum, palladium or rhodium, or a chloroauric acid, an alcohol-modified chloroplatinic acid, a chloroplatinic acid and an olefin, a vinyl alkane or an acetylene. A complex compound of a compound, a platinum group metal compound such as tetrakis(triphenylphosphine)palladium or chlorotris(triphenylphosphine) ruthenium or the like, particularly preferably a platinum compound. The component (C) may be used alone or in combination. The amount of the component (C) may be an effective amount as a hydroquinone catalyst, and more preferably a platinum group metal with respect to the total mass of the components (A) and (B). The mass of the element is converted into a range of 0.1 to 1,000 ppm, more preferably in the range of 1 to 500 ppm. [(D) component] (D) component is as follows The compound having an ester bond and an alkoxyalkylalkyl group represented by the formula (3), by adding the component (D), has an effect of suppressing cracking of the resin or peeling from the package in the moisture absorption soldering test. The compound having an ester bond and an alkoxyalkyl group in the component (D) is one having at least one ester bond and at least one alkoxyalkyl group in one molecule, and is represented by the following formula (3). Compound -15- 201237106 【化2】
SiR3d(〇R4)(3-d) ^Y^R5 (3) Ο (式中，R3、R4、R5係各自互相相同或異種的非取代或 取代的1價烴基，d爲0、1或2 )。 作爲上述式（3 )中的R3、R4、R5之非取代或取代的 1價烴基，例如可舉出甲基、乙基、丙基、丁基、戊基、 己基、環己基、庚基等的烷基，苯基、甲苯基、二甲苯基 、萘基等的芳基，氯甲基、3-氯丙基、3，3,3-三氟丙基等 的鹵化烷基等之通常碳數1〜10、較佳碳數1〜6左右的 非取代或鹵素取代的1價烴基。其中，關於R3，從與上 述（A)及（B)成分的混合容易性來看，較佳爲甲基、 乙基，關於R4，從水解的容易性來看，較佳爲甲基、乙 基，關於R5，從與上述（A)及（B)成分的混合容易性 來看，較佳爲碳數1〜10的直鏈或支鏈狀的烷基，更佳爲 甲基、乙基、丙基、2-甲基己基、2-乙基己基等》 (D)成分係可單獨1種使用，也可倂用2種以上。 (D)成分的含量係可爲不發生硬化阻礙或硬化後的 發黏之程度的量，相對於（A)成分與（B)成分的合計 1〇〇質量份而言，較佳爲0.1〜10質量份的範圍，更佳爲 〇·5〜5質量份的範圍。若未達0.1質量份，則有得不到對 吸濕廻焊的效果之虞，若超過1〇質量份，則會有發生硬 化阻礙或硬化後的發黏或滲出等問題之情況。 -16- 201237106 [其它成分] 於本發明的組成物中，除了前述（A)〜（D)成分 以外，在不損害本發明目的之範圍內，亦可摻合其它任意 的成分。作爲其具體例，可舉出以下者。此等其它成分係 可各自單獨1種使用，也可倂用2種以上。 • (A)成分以外之含有脂肪族不飽和基的化合物 在本發明的組成物中，於（A )成分以外，以提高封 止材料與基材的黏著性爲目的，亦可摻合與（B)成分進 行加成反應之含有脂肪族不飽和基的化合物。作爲（A ) 成分以外之如此含有脂肪族不飽和基的化合物，較佳爲參 與硬化物的形成者，可舉出每1分子中具有至少1個脂肪 族不飽和基的（A)成分以外之有機聚矽氧烷。其分子構 造例如可爲直鏈狀、環狀、支鏈狀、三次元網狀等中的任 一者。作爲具體例，可舉出N-烯丙基N’，N”-雙（3-三甲 氧基矽烷基丙基）異三聚氰酸酯、N-烯丙基Ν’，N”-雙（3-三乙氧基矽烷基丙基）異三聚氰酸酯等。 又，可摻合上述有機聚矽氧烷以外之含有脂肪族不飽 和基的有機化合物。作爲該含有脂肪族不飽和基的化合物 之具體例，可舉出丁二烯、由多官能性醇所衍生的二丙烯 酸酯等的單體，聚乙烯、聚丙烯或苯乙烯與其它乙烯性不 飽和化合物（例如丙烯腈或丁二烯）的共聚物等之聚烯烴 ，由丙烯酸、甲基丙烯酸或馬來酸的酯等之官能性取代有 機化合物所衍生的寡聚物或聚合物。（A)成分以外之含 -17- 201237106 有脂肪族不飽和基的化合物係在室溫下可爲液體或固體。 上述（A)成分以外之含有脂肪族不飽和基的化合物 之含量，係可爲不損害本發明目的之程度的量，宜相對於 (A)成分與（B)成分的合計100質量份而言，較佳爲 0.1〜10質量份的範圍，更佳爲0.5〜5質量份的範圍。若 未達0.1質量份，則有得不到對黏著性的提高之效果之虞 ’若超過1 〇質量份，則有發生硬化物的耐熱性降低等問 題之情況。 •加成反應控制劑 爲了確保適用期，可在本發明組成物中摻合加成反應 控制劑。加成反應控制劑只要是對上述（C )成分的氫矽 烷化觸媒具有硬化抑制效果之化合物，則沒有特別的限定 ，可使用習知者。作爲其具體例，可舉出三苯基膦等的含 磷化合物，三丁胺、四甲基伸乙二胺、苯并三唑等的含氮 化合物，含硫化合物物，炔醇類（例如1 -乙炔基環己醇 、3，5-二甲基-1-己炔-3-醇、3-甲基-1-十二炔-3-醇）等的 炔系化合物，含有2個以上的烯基之化合物，氫過氧化物 ，馬來酸衍生物等。 加成反應控制劑的硬化抑制效果之程度，係隨著其加 成反應控制劑的化學構造而不同。因此，對於所使用的各 加成反應控制劑，較佳爲將其添加量調整至最合適量，但 通常相對於（Α)成分與（Β)成分的合計100質量份而 言爲0.000 1〜5質量份左右。藉由添加最合適量的加成反 -18- 201237106 應控制劑，組成物係成爲室溫下長期儲存安定性及加熱硬 化性優異者。 •其它任意成分 爲了抑制硬化物的著色、白濁、氧化降解等之發生， 可在本發明組成物中摻合2,6-二第三丁基-4-甲基苯酚等 習知的抗氧化劑。又，爲了賦予對光降解的抵抗性，亦可 在本發明組成物中摻合受阻胺系安定劑等的光安定劑。再 者，於不對由本發明組成物所得之硬化物的透明性造成影 響的範圍內，爲了提高強度，可在本發明組成物中摻合煙 燻矽石等的無機質塡充劑，視需要亦可在本發明組成物中 摻合染料、顏料、難燃劑等。 [硬化物] 本發明的硬化性有機聚矽氧烷組成物，係可在眾所周 知的硬化條件下藉由眾所周知的硬化方法使硬化。具體地 ，通常藉由以80〜200°C加熱，較佳以100〜160°C加熱， 可使該組成物硬化。加熱時間可爲0.5分鐘〜5小時左右 ，特佳爲1分鐘〜3小時左右，但於要求LED封止用等精 度時，較佳爲加長硬化時間。所得之硬化物的形態係沒有 特別的限制，例如可爲凝膠硬化物、彈性體硬化物及樹脂 硬化物中的任一者。當該硬化物作爲光學元件封止用時， 較佳爲使用無色透明且高折射率（折射率1.54以上，尤 其 1 ·54 〜1.65 )者。 -19- 201237106 [光學元件封止材] 本發明組成物的硬化物係與通常的硬化性有機聚矽氧 烷組成物之硬化物同樣地，耐熱性、耐寒性、電絕緣性優 異，更且耐吸濕廻焊性亦優異。作爲經由本發明的組成物 所成的封止材所封閉的光學元件，例如可舉出LED、半導 體雷射、發光二極體、光電晶體、太陽電池、CCD等。 如此的光學元件係可藉由在該光學元件上塗佈由本發明的 組成物所成的封止材，使所塗佈的封止材在眾所周知的硬 化條件下，藉由眾所周知的硬化方法，具體地如上述進行 硬化，而進行封閉。 [實施例] 以下顯示調製例、實施例及比較例來具體說明本發明 ，惟本發明不受下述的實施例所限制。 再者，於下述之例中，黏度係使用旋轉式黏度計在 •25°C所測定之値。折射率係使用 ATAGO製數位折射計 RX-5000，在25t測定5 8 9nm的折射率，硬度係依據 JIS-K6249進行測定。又，於下述例中，份表示質量份。 又，於下述之例中，表示聚矽氧油或聚矽氧樹脂的平 均組成之記號係表示如以下的單位。又，各聚矽油或各聚 矽氧樹脂的莫耳數表示各成分中所含有的乙烯基或SiH基 之莫耳數。 -20- 201237106SiR3d(〇R4)(3-d) ^Y^R5 (3) Ο (wherein R3, R4 and R5 are each an unsubstituted or substituted monovalent hydrocarbon group which are mutually identical or heterogeneous, and d is 0, 1 or 2 ). Examples of the unsubstituted or substituted monovalent hydrocarbon group of R3, R4 and R5 in the above formula (3) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group and the like. Ordinary carbon such as an alkyl group, an aryl group such as a phenyl group, a tolyl group, a xylyl group or a naphthyl group; a halogenated alkyl group such as a chloromethyl group, a 3-chloropropyl group or a 3,3,3-trifluoropropyl group; An unsubstituted or halogen-substituted monovalent hydrocarbon group having a number of from 1 to 10, preferably from about 1 to about 6 carbon atoms. In particular, R3 is preferably a methyl group or an ethyl group from the viewpoint of ease of mixing with the components (A) and (B), and R4 is preferably a methyl group or a ethyl group from the viewpoint of easiness of hydrolysis. The R5 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a methyl group or an ethyl group, from the viewpoint of ease of mixing with the above components (A) and (B). And propyl, 2-methylhexyl, 2-ethylhexyl, etc. (D) may be used alone or in combination of two or more. The content of the component (D) may be an amount that does not cause hardening or hardening after curing, and is preferably 0.1 to 1 part by mass based on the total of the components (A) and (B). The range of 10 parts by mass is more preferably in the range of 〇 5 to 5 parts by mass. If it is less than 0.1 part by mass, the effect of moisture absorbing soldering may not be obtained, and if it exceeds 1 part by mass, problems such as hardening inhibition or stickiness or bleeding after hardening may occur. -16-201237106 [Other components] In the composition of the present invention, in addition to the above components (A) to (D), other optional components may be blended insofar as the object of the present invention is not impaired. Specific examples thereof include the following. These other components may be used alone or in combination of two or more. • The compound containing an aliphatic unsaturated group other than the component (A) may be blended with (in addition to the component (A) for the purpose of improving the adhesion between the sealing material and the substrate. B) An aliphatic unsaturated group-containing compound in which the component is subjected to an addition reaction. The compound containing an aliphatic unsaturated group other than the component (A) is preferably a component which participates in the formation of a cured product, and is not limited to the component (A) having at least one aliphatic unsaturated group per molecule. Organic polyoxyalkylene. The molecular structure thereof may be, for example, any one of a linear chain, a cyclic chain, a branched chain, and a cubic network. Specific examples thereof include N-allyl N',N"-bis(3-trimethoxydecylpropyl)isophthalocyanate, N-allylΝ', N"-double ( 3-triethoxydecylpropyl)isocyanate or the like. Further, an organic compound containing an aliphatic unsaturated group other than the above organopolysiloxane may be blended. Specific examples of the aliphatic unsaturated group-containing compound include butadiene, a monomer such as a diacrylate derived from a polyfunctional alcohol, and polyethylene, polypropylene or styrene and other ethylenic groups. A polyolefin such as a copolymer of a saturated compound (for example, acrylonitrile or butadiene), an oligomer or a polymer derived by substituting an organic compound such as an ester of acrylic acid, methacrylic acid or maleic acid. In addition to the component (A) -17- 201237106 The compound having an aliphatic unsaturation group may be a liquid or a solid at room temperature. The content of the aliphatic unsaturated group-containing compound other than the component (A) may be an amount that does not impair the object of the present invention, and is preferably 100 parts by mass based on the total of the components (A) and (B). It is preferably in the range of 0.1 to 10 parts by mass, more preferably in the range of 0.5 to 5 parts by mass. If it is less than 0.1 part by mass, the effect of improving the adhesiveness may not be obtained. If it exceeds 1 part by mass, the heat resistance of the cured product may be lowered. • Addition reaction controlling agent In order to secure the pot life, an addition reaction controlling agent may be blended in the composition of the present invention. The addition reaction controlling agent is not particularly limited as long as it has a curing inhibitory effect on the hydroquinone catalyst of the component (C), and a conventional one can be used. Specific examples thereof include a phosphorus-containing compound such as triphenylphosphine, a nitrogen-containing compound such as tributylamine, tetramethylethylenediamine or benzotriazole, a sulfur-containing compound, and an alkynol (for example). An acetylene compound such as 1-acetylcyclohexanol, 3,5-dimethyl-1-hexyn-3-ol or 3-methyl-1-dodecyn-3-ol, which contains two or more Alkenyl compounds, hydroperoxides, maleic acid derivatives and the like. The degree of the hardening inhibitory effect of the addition reaction controlling agent varies depending on the chemical structure of the addition reaction controlling agent. Therefore, it is preferable to adjust the addition amount of each addition reaction control agent to an optimum amount, but it is usually 0.000 1 to 100 parts by mass based on the total of the (Α) component and the (Β) component. 5 parts by mass or so. By adding an optimum amount of the addition reaction -18-201237106, the composition is excellent in long-term storage stability and heat hardening at room temperature. • Other optional components In order to suppress the occurrence of coloration, white turbidity, oxidative degradation, and the like of the cured product, a conventional antioxidant such as 2,6-di-tert-butyl-4-methylphenol may be blended in the composition of the present invention. Further, in order to impart resistance to photodegradation, a light stabilizer such as a hindered amine-based stabilizer may be blended in the composition of the present invention. Further, in the range which does not affect the transparency of the cured product obtained from the composition of the present invention, in order to improve the strength, an inorganic filler such as smoky quartz may be blended in the composition of the present invention, if necessary. Dyes, pigments, flame retardants, and the like are blended in the composition of the present invention. [Cured product] The curable organic polyoxane composition of the present invention can be cured by a well-known hardening method under well-known curing conditions. Specifically, the composition is usually cured by heating at 80 to 200 ° C, preferably at 100 to 160 ° C. The heating time may be from about 0.5 minutes to about 5 hours, particularly preferably from about 1 minute to about 3 hours, but it is preferably an extended hardening time when accuracy such as LED sealing is required. The form of the obtained cured product is not particularly limited, and may be, for example, any of a gel cured product, an elastomer cured product, and a resin cured product. When the cured product is used as an optical element for sealing, it is preferred to use a colorless transparent and high refractive index (refractive index of 1.54 or more, especially 1 · 54 to 1.65). -19-201237106 [Optical element sealing material] The cured product of the composition of the present invention is excellent in heat resistance, cold resistance, and electrical insulating properties, similarly to the cured product of the usual curable organopolyoxane composition. It is also excellent in moisture absorption and solderability. Examples of the optical element to be blocked by the sealing material formed by the composition of the present invention include an LED, a semiconductor laser, a light-emitting diode, a photoelectric crystal, a solar cell, and a CCD. Such an optical element can be coated with a sealing material made of the composition of the present invention on the optical element, so that the applied sealing material can be formed by a well-known hardening method under well-known hardening conditions. The ground is hardened as described above and closed. [Examples] Hereinafter, the present invention will be specifically described by way of Preparation Examples, Examples and Comparative Examples, but the present invention is not limited by the following examples. Further, in the following examples, the viscosity was measured at 25 ° C using a rotary viscometer. The refractive index was measured by using an ATAGO digital refractometer RX-5000, and the refractive index of 589 nm was measured at 25t, and the hardness was measured in accordance with JIS-K6249. Further, in the following examples, the parts represent parts by mass. Further, in the following examples, the symbols indicating the average composition of the polyoxygenated oil or the polyoxyxylene resin are as follows. Further, the number of moles of each of the polyanthracene oil or each of the polyoxymethylene resins indicates the number of moles of the vinyl group or the SiH group contained in each component. -20- 201237106
Mh : (CHs) zHS i Ο1/2 MVi : (CH2=CH) (CH3) zS i Ο1/2 Μφνί ： (CH2=CH) (CeHs) (CH3) S i 〇1/2 D : (CH3) 2S i Ο2/2 DVi : (CH2=CH) (CHa) S i Ο2/2 D*1* : (C6H5) 2S i Ο2/2 Τφ : (CeHs) S i Ο3/2 [調製例1]鉑觸媒的調製 以鉑含量成爲1.0質量％的方式，用黏度0.7P a· s、 平均組成式：Μνί20190φ9的聚矽氧油來稀釋六氯鈾酸與 sym-四甲基二乙烯基二矽氧烷的反應生成物，而調製本實 施例及比較例所使用的鉑觸媒（觸媒A )。 [調製例2]平均組成式：的聚矽氧樹脂之合成 於10L的燒瓶中，加入水4,380g及二甲苯i，8〇〇g， 以內溫不超過60 °C的方式，於其中滴下三氯苯基矽烷 l，903g、氯二甲基乙烯基矽烷361.5g、二甲苯360g的混 合溶液，然後在60°C〜65 °C繼續攪拌2小時。冷卻至室溫 後，分離水相。用芒硝水洗淨有機相，然後添加氫氧化鉀 4.3g，在130°C〜140°C繼續攪拌12小時。去除700g二甲 苯後，冷卻至50 °C〜60 °C，更添加氯三甲基矽烷21.8g、 醋酸鉀19.9g，在50°C〜60°C繼續攪拌2小時。冷卻至室 溫後，過濾而得到無色透明的平均組成式：之聚 矽氧樹脂的二甲苯溶液（不揮發份約50質量％)。 [調製例3]平均組成式：DV^T%的聚矽氧樹脂之合成 -21 - 201237106 於10L的燒瓶中，加入水4,500g及甲苯l，6〇5g，以 內溫不超過60。(：的方式，於其中滴下三氯苯基矽烷 l，862g、二氯甲基乙烯基矽烷310g、甲苯384g的混合溶 液，然後在60°C〜65 °C繼續攪拌2小時。冷卻至室溫後， 分離水相。用小蘇打水洗淨有機相，然後添加50質量％ 氫氧化鉀水溶液〇.5g，在100°C〜1 l〇°C繼續攪拌2小時。 冷卻至40°C〜45°C後，添加氯三甲基矽烷1.45g、醋酸鉀 5.05g，在40°C〜45°C繼續攪拌2小時。然後，藉由減壓 濃縮以去除甲苯直到不揮發份成爲約50質量％。冷卻至 室溫後，過濾而得到無色透明的平均組成式：之 聚矽氧樹脂的甲苯溶液（不揮發份約50質量％)。 [調製例4]平均組成式：Μφν;20φ3.6的聚矽氧油之合成 於5 00mL的燒瓶中，加入水200g及甲苯1 17g，加溫 至75°C，於其中滴下二氯二苯基矽烷l〇〇g，在80°C繼續 攪拌3小時。冷卻至室溫後，分離水相。以無水硫酸鈉 l〇g將有機相乾燥，過濾而得到二氯二苯基矽烷水解寡聚 物的甲苯溶液。藉由減壓濃縮以去除甲苯，添加混合二甲 基二苯基二乙烯基二矽氧烷30.6g。更添加濃硫酸5.0g， 在50°C/15mmHg的條件下進行5小時縮合反應。添加混 合甲苯100g、10質量％芒硝水l〇〇g後，分離水相。用小 蘇打水洗淨及水洗淨有機相，然後藉由減壓濃縮以去除甲 苯。過濾所得之白濁液體，而得到無色透明且在25 °C的黏 度約2,000mPa · s的平均組成式：Μφνί2ϋφ3.6之聚矽氧油 -22- 201237106 [實施例1] 使平均組成式：Μφνΐ2〇φ3·6的聚矽氧油22份、平均 組成式：的聚矽氧樹脂53份、平均組成式： M'D%的有機氫聚矽氧烷22份及下述式（4 )所示之具 有酯鍵與甲氧基矽烷基的化合物（添加劑A) 1份之混合 物與作爲控制劑的3 -甲基-1-十二炔-3-醇0.0056份及觸媒 A 0.05份進行混合’而得到有機聚矽氧烷組成物。將此組 成物以1 0 0 °C加熱2小時，更以1 5 〇 °C加熱4小時而使硬 化，結果所得之彈性體（A )'的硬度以Shore D計爲27。 再者’表1中顯示吸濕廻焊的試驗結果。 【化3】Mh : (CHs) zHS i Ο1/2 MVi : (CH2=CH) (CH3) zS i Ο1/2 Μφνί : (CH2=CH) (CeHs) (CH3) S i 〇1/2 D : (CH3) 2S i Ο2/2 DVi : (CH2=CH) (CHa) S i Ο2/2 D*1* : (C6H5) 2S i Ο2/2 Τφ : (CeHs) S i Ο3/2 [Preparation Example 1] Platinum catalyst The preparation was carried out by diluting hexachlorournic acid with sym-tetramethyldivinyldioxane in a manner of a platinum content of 1.0% by mass, using a polypyroxaic acid having a viscosity of 0.7 P a·s and an average composition formula: Μνί20190φ9. The platinum catalyst (catalyst A) used in the examples and the comparative examples was prepared by reacting the products. [Preparation Example 2] The average composition formula: The polyfluorene oxide resin was synthesized in a 10 L flask, and 4,380 g of water and xylene, 8 〇〇g, were added thereto, and the internal temperature was not more than 60 ° C, and three were dropped therein. A mixed solution of chlorophenyl decane 1, 903 g, chlorodimethylvinyl decane 361.5 g, and xylene 360 g was further stirred at 60 ° C to 65 ° C for 2 hours. After cooling to room temperature, the aqueous phase was separated. The organic phase was washed with Glauber's salt water, then 4.3 g of potassium hydroxide was added, and stirring was continued at 130 ° C to 140 ° C for 12 hours. After removing 700 g of xylene, it was cooled to 50 ° C to 60 ° C, and 21.8 g of chlorotrimethylnonane and 19.9 g of potassium acetate were further added, and stirring was continued at 50 ° C to 60 ° C for 2 hours. After cooling to room temperature, it was filtered to obtain a colorless and transparent average composition formula: a xylene solution of a polyoxyl resin (non-volatile content of about 50% by mass). [Preparation Example 3] Synthesis of polyoxymethylene resin having an average composition formula: DV^T% -21 - 201237106 4,500 g of water and 1,5 g of toluene were added to a 10 L flask so that the internal temperature did not exceed 60. (: A method in which a mixed solution of trichlorophenyl decane 1, 862 g, 310 g of dichloromethylvinyl decane, and 384 g of toluene was added thereto, and then stirring was continued at 60 ° C to 65 ° C for 2 hours. After that, the aqueous phase was separated. The organic phase was washed with baking soda water, and then added with 50% by mass aqueous potassium hydroxide solution (5 g), and stirring was continued for 2 hours at 100 ° C to 1 l ° ° C. Cooling to 40 ° C to 45 ° After the ° C, 1.45 g of chlorotrimethyl decane and 5.05 g of potassium acetate were added, and stirring was continued for 2 hours at 40 ° C to 45 ° C. Then, the toluene was removed by concentration under reduced pressure until the nonvolatile content became about 50% by mass. After cooling to room temperature, it was filtered to obtain a colorless and transparent average composition formula: a toluene solution of polyoxymethylene resin (non-volatile content of about 50% by mass) [Modulation Example 4] Average composition formula: Μφν; 20φ3.6 The synthesis of the polyoxygenated oil was carried out in a 500 mL flask, 200 g of water and 17 g of toluene were added, and the mixture was heated to 75 ° C, and dichlorodiphenyl decane was added dropwise thereto, and stirring was continued at 80 ° C for 3 hours. After cooling to room temperature, the aqueous phase is separated. The organic phase is dried over anhydrous sodium sulfate (MgSOG) and filtered to give dichlorodichloride. A toluene solution of a hydrazine hydrolyzed oligomer. The toluene was removed by concentration under reduced pressure, and 30.6 g of dimethyldiphenyldivinyldioxane was added, and 5.0 g of concentrated sulfuric acid was further added at 50 ° C / 15 mmHg. 5 hours of condensation reaction was carried out. After adding 100 g of mixed toluene and 10 g of 10% by weight of Glauber's salt water, the aqueous phase was separated, washed with baking soda water and washed with water, and then concentrated by decompression under reduced pressure. Toluene. The obtained white turbid liquid was filtered to obtain a colorless transparent and an average composition of a viscosity of about 2,000 mPa·s at 25 ° C: Μφνί 2 ϋ 3.6 of polyoxygenated oil-22-201237106 [Example 1] : Μφνΐ2〇φ3·6 of polyoxygenated oil 22 parts, average composition formula: 53 parts of polyfluorene oxide resin, average composition formula: M'D% of organic hydrogen polyoxyalkylene 22 parts and the following formula (4) A mixture of a compound having an ester bond and a methoxyalkylene group (Additive A) shown as a control agent, 0.0056 parts of 3-methyl-1-dodecyn-3-ol as a controlling agent, and a catalyst A of 0.05 parts Mixing 'to obtain an organic polyoxane composition. This composition was heated at 100 ° C for 2 hours, The film was hardened by heating at 15 ° C for 4 hours, and as a result, the hardness of the obtained elastomer (A )' was 27 in Shore D. Further, the test results of the moisture absorbing soldering were shown in Table 1.
[實施例2] 除了代替添加劑A，使用下述式（5 )所示之具有酯 鍵與甲氧基矽烷基的化合物（添加劑B) 1份以外，依照 實施例1來調製組成物。將此有機聚矽氧烷組成物以 1 〇 〇 °C加熱2小時，更以1 5 0 °c加熱4小時而使硬化，結果 所得之彈性體（B )的硬度以Shore D計爲25 »再者，表 1中顯示吸濕廻焊的試驗結果。 -23- 201237106 lit 4][Example 2] A composition was prepared in accordance with Example 1 except that instead of the additive A, a compound (additive B) having an ester bond and a methoxydecyl group represented by the following formula (5) was used. The organic polyoxymethane composition was heated at 1 ° C for 2 hours, and further heated at 150 ° C for 4 hours to be hardened. As a result, the obtained elastomer (B) had a hardness of 25 » in Shore D. Further, the test results of the moisture absorbing soldering are shown in Table 1. -23- 201237106 lit 4]
[比較例1 ] 除了代替添加劑A，使用N-烯丙基N’，N”-雙（3-三 乙氧基矽烷基丙基）異三聚氰酸酯（添加劑C) 1份以外 ’依照實施例1來調製組成物。將此有機聚矽氧烷組成物 以l〇〇°C加熱2小時，更以150°C加熱4小時而使硬化’ 結果所得之彈性體（C )的硬度以Shore D計爲40。再者 ’表1中顯示吸濕廻焊的試驗結果。 [比較例2 ] 除了代替添加劑A，使用3-環氧丙氧基丙基三甲氧基 矽烷（信越化學工業（股）製KB Μ-4 03 ) 1份以外，依照 實施例1來調製組成物。將此有機聚矽氧烷組成物以 1 〇〇°C加熱2小時，更以1 50°C加熱4小時而使硬化，結果 所得之彈性體（D )的硬度以Shore D計爲30。再者，表 1中顯示吸濕廻焊的試驗結果。 [比較例3 ] 除了代替添加劑A，使用3 -甲基丙烯醯氧基丙基三甲 氧基矽烷（信越化學工業（股）製KBM-503) 1份以外， β Μ實施例1來調製組成物。將此有機聚矽氧烷組成物以 -24- 201237106 1 0 0。(3加熱2小時’更以1 5 0 °c加熱4小時而使硬化’結果 所得之彈性體（E)的硬度以Shore D計爲28。再者’表 1中顯示吸濕廻焊的試驗結果。 [實施例3] 使平均組成式：Μφνί2ϋφ3.6的聚矽氧油55.1份、平 均組成式：DV^T%的聚矽氧樹脂45份、平均組成式： 的有機氫聚矽氧烷28.6份及上述式（4)所示之 具有酯鍵與甲氧基矽烷基的化合物（添加劑A) 1份之混 合物與作爲控制劑的3-甲基-卜十二炔-3-醇0.2份及觸媒 A 〇. 3份進行混合，而得到有機聚矽氧烷組成物。將此組 成物以100°C加熱2小時，更以150°C加熱4小時而使硬 化，結果所得之彈性體（F)的硬度以Shore D計爲32。 再者，表2中顯示吸濕廻焊的試驗結果。 [實施例4 ] 除了代替添加劑A，使用上述式（5)所示之具有酯 鍵與甲氧基矽烷基的化合物（添加劑B)丨份以外，依照 實施例3來調製組成物。將此有機聚矽氧烷組成物以 1 〇〇°C加熱2小時’更以1 50t加熱4小時而使硬化，結果 所得之彈性體（G )的硬度以Shore D計爲3 1。再者，表 2中顯示吸濕廻焊的試驗結果。 [比較例4 ] -25- 201237106 除了代替添加劑A，使用N-烯丙基N’，N”-雙（3-三 乙氧基矽烷基丙基）異三聚氰酸酯（添加劑C) 1份以外 ’依照實施例3來調製組成物。將此有機聚矽氧烷組成物 以100°c加熱2小時，更以150°c加熱4小時而使硬化， 結果所得之彈性體（H)的硬度以Shore D計爲50。再者 ’表2中顯示吸濕廻焊的試驗結果。 [比較例5] 除了代替添加劑A，使用3-環氧丙氧基丙基三甲氧基 矽烷（信越化學工業（股）製KBM-4〇3 ) 1份以外，依照 實施例3來調製組成物。將此有機聚矽氧烷組成物以 l〇〇°C加熱2小時，更以150°C加熱4小時而使硬化，結果 所得之彈性體（I)的硬度以Shore D計爲30。再者，表 2中顯示吸濕廻焊的試驗結果。 [比較例6] 除了代替添加劑A，使用3 -甲基丙烯醯氧基丙基三甲 氧基矽烷（信越化學工業（股）製KBM- 5 03 ) 1份以外， 依照實施例3來調製組成物。將此有機聚矽氧烷組成物以 1 00°C加熱2小時，更以1 50°c加熱4小時而使硬化，結果 所得之彈性體（J)的硬度以Shore D計爲33。再者，表 2中顯示吸濕廻焊的試驗結果。 評價方法 -26- 201237106 吸濕廻焊試驗用封裝 作爲吸濕廻焊試驗用的測試封裝，使用未搭載有LED 晶片的如圖1中所示的簡易封裝。此處，1爲殼體，2、3 爲引線電極，4爲封止樹脂（實施例及比較例所得之有機 聚矽氧烷組成物的硬化物）〇前述有機聚矽氧烷組成物的 硬化條件係以1 〇〇°C 2小時，更以1 50°C 4小時。 吸濕廻焊之試驗方法 將所製作的測試封裝10個置入85°C、85%RH的恆溫 恆濕槽中24小時後，通過紅外線廻焊裝置（260°C ) 1次 ，觀察外觀的變化。表1、2中顯示結果。再者，將看到 樹脂的龜裂或自LED封裝的剝離者計算爲NG。 [表1] 實施例1 實施例2 比較例1 比較例2 比較例3 添加劑 A B C KBM-403 KBM-503 NG數/試驗數 0/10 0/10 10/10 10/10 10/10 [表2] 實施例3 實施例4 比較例4 比較例5 比較例ό 添加劑 A B C KBM-403 KBM-503 NG數/試驗數 0/10 0/10 10/10 10/10 10/10 【圖式簡單說明】 圖1係本發明的實施例中之吸濕廻焊試驗用封裝的示 意圖 -27- 201237106 【主要元件符號說明】 1 :殼體 2、3 :引線電極 4 :封止樹脂 -28 -[Comparative Example 1] In place of the additive A, N-allyl N',N"-bis(3-triethoxydecylpropyl)isophthalocyanate (Additive C) was used in addition to 1 part. The composition was prepared in Example 1. The organic polyoxane composition was heated at 10 ° C for 2 hours, and further heated at 150 ° C for 4 hours to harden the resulting elastomer (C) hardness. Shore D is calculated as 40. Further, the test results of the moisture absorbing soldering are shown in Table 1. [Comparative Example 2] In place of the additive A, 3-glycidoxypropyltrimethoxydecane was used (Shin-Etsu Chemical Industry ( The composition was prepared in accordance with Example 1. The organic polydecane composition was heated at 1 ° C for 2 hours and further heated at 150 ° C for 4 hours. When hardened, the hardness of the obtained elastomer (D) was 30 in Shore D. Further, the test results of the moisture absorbing soldering were shown in Table 1. [Comparative Example 3] In place of the additive A, 3-A was used. A propylene methoxy propyl trimethoxy decane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) was used to prepare a composition in the same manner as in Example 1 except for 1 part. The composition of the organopolyoxane is -24-201237106 1 0 0. (3 heating for 2 hours 'heating at 150 ° C for 4 hours to harden" results in the hardness of the elastomer (E) as Shore D It is counted as 28. Further, the test results of the moisture absorbing soldering are shown in Table 1. [Example 3] 55.1 parts of the polysiloxane oil having an average composition formula: Μφνί2ϋφ3.6, and an average composition formula: DV^T% 45 parts of a silicone resin, an average composition formula: 28.6 parts of an organic hydrogen polyoxyalkylene, and a mixture of a compound having an ester bond and a methoxyalkylene group (additive A) represented by the above formula (4) and a control 0.2 parts of 3-methyl-bu-dodecyne-3-ol and 3 parts of catalyst A 进行. were mixed to obtain an organic polyoxoxane composition. The composition was heated at 100 ° C for 2 hours. Further, it was hardened by heating at 150 ° C for 4 hours, and as a result, the hardness of the obtained elastomer (F) was 32 in terms of Shore D. Further, the test results of the moisture absorbing soldering were shown in Table 2. [Example 4] In place of the additive A, in addition to the compound (additive B) having an ester bond and a methoxydecyl group represented by the above formula (5), in accordance with Example 3 The composition was prepared, and the organic polyoxane composition was heated at 1 ° C for 2 hours and further heated at 150 ° for 4 hours to be hardened. As a result, the hardness of the obtained elastomer (G ) was 3 in Shore D. 1. Further, the test results of the moisture absorbing soldering are shown in Table 2. [Comparative Example 4] -25- 201237106 In addition to the additive A, N-allyl N', N"-bis (3-triethoxy) was used. The composition was prepared according to Example 3 except for the alkyl propyl)isomeric cyanurate (Additive C). The organic polyoxymethane composition was heated at 100 ° C for 2 hours and further heated at 150 ° C for 4 hours to be hardened, and the resulting elastomer (H) had a hardness of 50 in Shore D. Furthermore, the results of the test for moisture absorbing soldering are shown in Table 2. [Comparative Example 5] A composition was prepared according to Example 3 except that instead of the additive A, 3-glycidoxypropyltrimethoxydecane (KBM-4〇3 manufactured by Shin-Etsu Chemical Co., Ltd.) was used. . This organic polyoxymethane composition was heated at 1 ° C for 2 hours, and further heated at 150 ° C for 4 hours to be hardened. As a result, the obtained elastomer (I) had a hardness of 30 in Shore D. Further, the test results of the moisture absorbing soldering are shown in Table 2. [Comparative Example 6] A composition was prepared according to Example 3 except that instead of the additive A, 3-methylpropenyloxypropyltrimethoxydecane (KBM-503) manufactured by Shin-Etsu Chemical Co., Ltd. was used. . The organic polydecane composition was heated at 100 ° C for 2 hours, and further heated at 150 ° C for 4 hours to be hardened. As a result, the obtained elastomer (J) had a hardness of 33 in Shore D. Further, the test results of the moisture absorbing soldering are shown in Table 2. Evaluation Method -26- 201237106 Packing for moisture absorption soldering test As a test package for moisture absorption soldering test, a simple package as shown in Fig. 1 in which an LED chip is not mounted is used. Here, 1 is a case, 2 and 3 are lead electrodes, 4 is a sealing resin (a cured product of an organic polyoxane composition obtained in the examples and the comparative examples), and the hardened composition of the above organopolyoxane is used. The conditions are 1 〇〇 ° C for 2 hours and 1 50 ° C for 4 hours. Test method for moisture absorbing soldering: 10 test packages were placed in a constant temperature and humidity chamber at 85 ° C and 85% RH for 24 hours, and then passed through an infrared soldering apparatus (260 ° C) once to observe the appearance. Variety. The results are shown in Tables 1 and 2. Further, it will be seen that cracking of the resin or peeling from the LED package is calculated as NG. [Table 1] Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Additive ABC KBM-403 KBM-503 NG number/test number 0/10 0/10 10/10 10/10 10/10 [Table 2 Example 3 Example 4 Comparative Example 4 Comparative Example 5 Comparative Example 添加剂 Additive ABC KBM-403 KBM-503 NG number/test number 0/10 0/10 10/10 10/10 10/10 [Simple description] BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a package for moisture absorbing soldering test in an embodiment of the present invention -27-201237106 [Description of main components] 1 : Housing 2, 3: Lead electrode 4: sealing resin -28 -