TW201005040A

TW201005040A - Curable silicone rubber composition and photosemiconductor device using the same as sealing material

Info

Publication number: TW201005040A
Application number: TW98109941A
Authority: TW
Inventors: Tsutomu Kashiwagi
Original assignee: Shinetsu Chemical Co
Priority date: 2008-03-27
Filing date: 2009-03-26
Publication date: 2010-02-01
Also published as: KR20090103785A; TWI429714B; KR101495361B1; JP2009235265A; JP5000566B2

Abstract

To provide a curable silicone rubber composition capable of forming a lens-shaped coated or sealed body having high transparency by applying an adequate amount of the composition direct to an LED chip fitted on a supporting structure using a dispenser, by molding the chip and by curing the chip. This curable silicone rubber composition comprises (A) a substantially straight-chain organopolysiloxane having two or more aliphatic unsaturated bonds in one molecule thereof, (B) an organopolysiloxane having a resin structure and having two or more aliphatic unsaturated bonds in one molecule thereof, (C) an organohydrogenpolysiloxane having two or more hydrogen atoms bonded to a silicon atom in one molecule thereof, (D) a platinum group metal-based catalyst, (E) a thixotropy imparting agent other than component (F), and (F) fumed silica, wherein the refractive index of the composition comprising the components (A) to (E) is 1.42 to 1.47, and provided is also a photosemiconductor device using the curable silicone rubber composition as a sealing material.

Description

201005040 六、發明說明：【發明所屬之技術領域】 #發明係關於一種作爲搭載於支持構造體上之光半導體晶片之被覆或封閉材料時，有用之附加硬化型之硬化性聚砂氧橡膠組成物；尤其，係關於一種可直接地適量適用 , 於半導體晶片上’使其成形、硬化，並形成透明被覆之合適的附加硬化型之硬化性聚矽氧橡膠組成物。【先前技術】 LED發光裝置用透鏡，係以射出成形等機械成形之方式而大量製造。傳統上，係使用丙烯基樹脂、聚碳酸酯樹脂等之熱可塑性樹脂而成形，惟伴隨著LED發光裝置之高輸出化’在熱可塑性樹脂上產生了耐熱性、耐變色性不完全之問題。此外，最近雖然多使用無鉛焊錫，惟無鉛焊錫相較於傳統之焊錫而言，其溶融溫度較高之故，一般係 • 於26〇°C以上之高溫將光學元件焊在基板上。如在此種溫度下施加焊錫時，傳統上由熱可塑性材料所成之透鏡就會產生變形，且因高溫之故就會產生變黃之不理想狀況。基於此種狀況，即有許多在用於LED等之透鏡材料 ' 上，使用聚矽氧樹脂之嘗試。舉例而言，有提案使用聚矽氧樹脂以射出成形等之成形方法所預先製造之透鏡，再裝置於搭載有LED晶片之封裝之方法（專利文獻1)。然而，此種方法除需要接著樹脂及內層樹脂外，其操作亦很繁雜而不容易。 -5- 201005040 在裝置於支持構造體上之光半導體晶片上，使材料發生成形、硬化之方法，已知有包覆成形（overmold )法（參照專利文獻1)。此種方法，其有樹脂之透明性或觸變性之控制爲不完全之缺點。因此，近年，有提案在搭載於支持構造體上之LED 晶片上，直接適用聚矽氧樹脂，並使之成形爲透鏡狀之方法（專利文獻3)。然而，由於所使用之聚矽氧樹脂之觸變性不良之故，即使在支持基板上之LED晶片上以分配器直接地適量加以使用，並使之成形、硬化後，亦會流動，從而無法得到具有目的形狀之成形·硬化物之問題。再者，聚矽氧樹脂之觸變性爲不完全之結果，造成使用其等之製造裝置持續維持在高價之問題。如在聚矽氧樹脂上添加燻矽時，已知可賦予其觸變性，惟會產生白濁現象，且所得到之觸變性，會在各批次產生散亂不均的現象，從而並不實用。專利文獻1 :特開2007-242246 專利文獻2 :特開2006-148 147 專利文獻3 :特開2007- 1 23 89 1 【發明內容】發明之揭示發明所欲解決之課題據此，本發明之課題係提供一種硬化性聚矽氧橡膠組成物，其係於裝置在支持構造體上之LED晶片上使用分 -6- 201005040 配器，直接適量地適用於其上，藉由使其成形、硬化，可形成高透明性之透鏡形狀的被覆或封閉體。解決課題之手段由此，本發明者們，藉由檢討有機聚矽氧烷成分之構，成、燻矽之折射率及其以外之成分整體之折射率之關係等，而發現了可兼顧硬化物之透明性及安定之觸變性的聚矽 Φ 氧樹脂組成物，並解決了上述之課題。亦即，本發明，具體而言，係提供一種硬化性聚矽氧橡膠組成物，其特徵爲含有： (A) 在一分子中具有2個以上之脂肪族不飽和鍵，且本質上爲直鏈狀之有機聚矽氧烷， (B) 在一分子中具有2個以上之脂肪族不飽和鍵，且具有樹脂構造之有機聚矽氧烷， (C) 在一分子中具有2個以上之結合於矽原子之氫 φ 原子之有機氫聚矽氧烷， (D) 鉑族金靥系觸媒， (E )除（F )成分以外之觸變性賦予劑，以及 (F)燻矽 ' 所成者，且由（A) ~(E)成分所成之組成物之折射率係 1.42〜1.47 ° 此外，本發明並提供一種聚矽氧橡膠硬化物，其特徵係將上述之組成物加以硬化所成，且在厚度1 mm之層狀態，其20°C下之波長450 nm之光之穿透率爲80%以上者 201005040 該硬化物，舉例而言，可用於在光半導體裝置使用之光半導體晶片之封閉材料上。據此，本發明並進一步提供一種光半導體裝置，其特徵係具有光半導體晶片，以及被覆該光半導體晶片加之將上述之組成物加以硬化所成之聚矽氧橡膠硬化物。發明之效果本發明之組成物由於其觸變性優良之故，舉例而言，可以在裝置於支持構造體上之光半導體晶片上使用分配器，而簡便地適用適量之組成物，其後並藉由使其成形、硬化，就可以安定地形成一種透鏡形狀的被覆體。【實施方式】實施發明之最佳型態 (A)含有脂肪族不飽和鍵之有機聚矽氧烷本發明之基底成分之（A)成分，係在一分子中具有 2個以上之脂肪族不飽和鍵，且本質上爲直鏈狀之有機聚矽氧烷。該有機聚矽氧烷之黏度基於作業性、硬化性等之觀點，一般係以 25°C下爲 10〜1,000,000 mPa · s，尤以 100〜100,000 mPa· s 爲最佳。分子構造在本質上係直鏈狀，並以直鏈狀爲較佳。所謂「本質上係直鏈狀」，係指除將本成分中之兩末端封閉 -8- 201005040 之三有機聚矽氧烷基以外之全部聚矽氧烷單位，主要係以 2官能單位（D單位）（具體而言，係式：Ri2Si〇所示之單位）所構成，惟亦可含有：全部聚矽氧烷單位之3莫耳 %以下’較佳爲2莫耳％以下而形成分枝之3官能單位（τ -單位）（具體而言，係式：VSiO^所示之單位）及4官 . 能單位（Q單位）（具體而言’係式：Si04/2所示之單位 )之至少1種聚矽氧烷單位之意。較佳者，僅兩末端係以 φ 1官能單位（M單位）（具體而言，係式：R^SiOm所示之單位）所構成’而其他之聚矽氧烷單位則全部係由D單位所構成之直鏈狀之二有機聚矽氧烷。在此，R1係取代或非取代之一價烴基。其中，R1之一價烴基，一般係碳原子數1~1〇，最佳係1〜6者，具體而言，有甲基、乙基、丙基、異丙基、丁基、異丁基、tert-丁基、戊基、新戊基、己基、辛基、壬基、癸基等之烷基；環己基；苯基、甲苯基、二甲苯基、 φ 萘基等之芳基、苄基、苯基乙基、苯基丙基等之芳烷基、乙烯基、烯丙基、丙烯基、異丙烯基、丁烯基、戊烯基、己烯基、辛烯基等之鏈烯基；環己烯基；及將此等之烴基之氫原子之一部分或全部以氟、溴、氯等之鹵原子、氰基 ' 等進行取代者，例如氯甲基、氯丙基、溴乙基、三氟丙基等之鹵取代烷基或氰基乙基等。 (A)成分之有機聚矽氧烷，其係於在一分子中具有 2個以上之脂肪族不飽和鍵。脂肪族不飽和鍵，其代表者爲碳原子數2-8，尤其是2〜6之鏈烯基及環烯基，具體而 -9 - 201005040 言，有上述之乙烯基、烯丙基、丙烯基、異丙烯基、丁烯基、戊烯基、己烯基等之鏈烯基、環己烯基等之環烯基。其中，又以乙烯基及烯丙基爲最佳。 (A)成分之有機聚矽氧烷，其較佳之具體例子，有下述一般式（1)所示之在分子鏈兩末端之矽原子各具有至少1個鏈烯基之直鏈狀有機聚矽氧烷，如上所述者，其在25°c下之黏度爲10〜l，〇〇〇,〇〇〇mPa· S。 (1) ❹ 【化1】 R1 R1 R2 R1 1111 H2C=CH-SiO—(SiO)k—(SiO)m-Si-CH=CH2 (式中，R1如前所述，係獨立地爲非取代或取代之一價烴基，R2爲彼此同一或相異之不具有脂肪族不飽和鍵之非取代或取代之一價烴基，k及m係獨立地爲0或正整數，k+m係此有機聚矽氧烷在 25 °C之黏度可成爲 10~l，O00,000 mPa· s 之數）°201005040 VI. Description of the Invention: [Technical Field of the Invention] The invention relates to an additional hardening type curable polyoxyethylene rubber composition which is useful as a coating or sealing material for an optical semiconductor wafer mounted on a support structure. In particular, it relates to a hardenable polyoxyxene rubber composition which is suitable for the right amount and which is suitable for forming, hardening, and forming a transparent coating on a semiconductor wafer. [Prior Art] A lens for an LED light-emitting device is mass-produced by mechanical molding such as injection molding. Conventionally, it has been molded using a thermoplastic resin such as a propylene-based resin or a polycarbonate resin, but the high-output of the LED light-emitting device has caused a problem that heat resistance and discoloration resistance are incomplete in the thermoplastic resin. In addition, although lead-free solders have recently been used, the lead-free solder has a higher melting temperature than conventional solders, and is generally soldered to a substrate at a high temperature of 26 ° C or higher. When solder is applied at such a temperature, the lens which is conventionally formed of a thermoplastic material is deformed, and the yellowing is undesired due to the high temperature. Based on this situation, there are many attempts to use polyoxyxylene resin on lens materials for LEDs and the like. For example, a lens which is preliminarily produced by a molding method such as injection molding using a polysiloxane resin, and a method of mounting a package in which an LED chip is mounted is proposed (Patent Document 1). However, this method is complicated and difficult to handle except for the resin and the inner resin. -5-201005040 A method of forming and hardening a material on a photo-semiconductor wafer mounted on a support structure is known as an overmolding method (see Patent Document 1). In this method, the control of the transparency or thixotropic property of the resin is incomplete. Therefore, in recent years, there has been proposed a method in which a polysiloxane resin is directly applied to an LED wafer mounted on a support structure and formed into a lens shape (Patent Document 3). However, due to the poor thixotropy of the polyoxyxene resin used, even if the dispenser is directly used in an appropriate amount on the LED wafer on the support substrate, and formed and hardened, it will flow, and thus cannot be obtained. There is a problem of forming and hardening the object of the desired shape. Further, the thixotropy of the polyoxyxene resin is incomplete, resulting in a problem that the manufacturing apparatus using the same is continuously maintained at a high price. For example, when the smoked enamel is added to the polyoxyxene resin, it is known that it can impart thixotropy, but white turbidity is generated, and the thixotropy obtained can cause unevenness in each batch, which is not practical. . Patent Document 1: JP-A-2007-242246 Patent Document 2: JP-A-2006-148 147 Patent Document 3: JP-A-2007- 1-23 89 1 SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION According to the present invention, The subject is to provide a curable polyoxyxene rubber composition which is applied to an LED wafer of a support structure on a support wafer by a -6-201005040 adapter, and is directly applied thereto, by forming and hardening it. A coating or a closed body of a lens shape having high transparency can be formed. In order to solve the problem, the inventors of the present invention have found that the relationship between the composition of the organopolyoxane component, the refractive index of the smoked sputum, and the refractive index of the components other than the whole is found. The composition of the above-mentioned problems is solved by the transparency of the substance and the thixotropy of the thixotrope oxy-resin composition. That is, the present invention, in particular, provides a curable polyoxyxene rubber composition characterized by comprising: (A) having two or more aliphatic unsaturated bonds in one molecule, and being substantially straight a chain-like organic polyoxane, (B) an organopolysiloxane having two or more aliphatic unsaturated bonds in one molecule and having a resin structure, (C) having two or more in one molecule An organic hydrogen polyoxane bonded to a hydrogen atom of a ruthenium atom, (D) a platinum group ruthenium catalyst, (E) a thixotropic agent other than the (F) component, and (F) a smoked sputum The refractive index of the composition formed by the components (A) to (E) is 1.42 to 1.47 °. In addition, the present invention provides a cured silicone rubber characterized by hardening the above composition. In the state of a layer having a thickness of 1 mm, the transmittance of light having a wavelength of 450 nm at 20 ° C is 80% or more. 201005040 The cured product, for example, can be used for light used in an optical semiconductor device. On the sealing material of the semiconductor wafer. Accordingly, the present invention further provides an optical semiconductor device characterized by comprising an optical semiconductor wafer, and a cured polyoxyethylene rubber obtained by coating the optical semiconductor wafer and curing the composition. EFFECT OF THE INVENTION The composition of the present invention is excellent in thixotropy. For example, a dispenser can be used on an optical semiconductor wafer mounted on a support structure, and an appropriate amount of the composition can be easily applied, and then borrowed. By forming and hardening it, a lens-shaped covering body can be stably formed. [Embodiment] The best mode for carrying out the invention (A) Organopolyoxyalkylene containing an aliphatic unsaturated bond The component (A) of the base component of the present invention has two or more aliphatic groups in one molecule. A saturated poly bond, and is essentially a linear organopolyoxane. The viscosity of the organopolyoxane is generally from 10 to 1,000,000 mPa·s at 25 ° C, and particularly preferably from 100 to 100,000 mPa·s, from the viewpoints of workability and hardenability. The molecular structure is linear in nature and is preferably linear. The term "linearly intrinsically linear" refers to all polyoxoxane units except for the organic polydecyloxyalkyl group of -8-201005040, which is mainly composed of two functional units (D). The unit (specifically, the unit of the formula: Ri2Si〇) is composed of, but may contain: 3 mol% or less of all polyoxane units, preferably 2 mol% or less, to form branches. 3 functional units (τ - units) (specifically, the formula: VSiO^ shows the unit) and 4 official units (Q units) (specifically, 'system: Si04/2 shown units) At least one polyoxane unit is intended. Preferably, only the two ends are composed of φ 1 functional units (M units) (specifically, the formula: units represented by R^SiOm) and the other polyoxyalkylene units are all D units. A linear diorganopolysiloxane composed of linear. Here, R1 is a substituted or unsubstituted one-valent hydrocarbon group. Wherein, R1 is a monovalent hydrocarbon group, generally having a carbon number of 1 to 1 Torr, and preferably having 1 to 6 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group. An alkyl group such as tert-butyl, pentyl, neopentyl, hexyl, octyl, decyl, fluorenyl or the like; a cyclohexyl group; an aryl group such as a phenyl group, a tolyl group, a xylyl group or a φ naphthyl group; An aryl group such as an aralkyl group, a phenylethyl group or a phenylpropyl group, a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, a pentenyl group, a hexenyl group or an octenyl group. a cyclohexenyl group; and a part or all of a hydrogen atom of such a hydrocarbon group is substituted with a halogen atom such as fluorine, bromine or chlorine, a cyano group or the like, such as chloromethyl, chloropropyl or bromoethyl A halogen-substituted alkyl group or a cyanoethyl group such as a trifluoropropyl group. The organopolyoxane of the component (A) is one having two or more aliphatic unsaturated bonds in one molecule. An aliphatic unsaturated bond, which is represented by an alkenyl group having 2 to 8 carbon atoms, particularly 2 to 6 and a cycloalkenyl group, specifically -9 - 201005040, having the above-mentioned vinyl group, allyl group, and propylene group a cycloalkenyl group such as an alkenyl group such as a group, an isopropenyl group, a butenyl group, a pentenyl group or a hexenyl group; or a cycloalkenyl group; Among them, vinyl and allyl groups are preferred. A preferred example of the organic polyoxane of the component (A) is a linear organopoly group having at least one alkenyl group each having a halogen atom at both ends of the molecular chain represented by the following general formula (1). The oxime, as described above, has a viscosity of 10 to 1, 〇〇〇, 〇〇〇mPa· S at 25 ° C. (1) ❹ [Chemical 1] R1 R1 R2 R1 1111 H2C=CH-SiO-(SiO)k-(SiO)m-Si-CH=CH2 (wherein R1 is independently unsubstituted as described above) Or substituting a monovalent hydrocarbon group, R2 is an unsubstituted or substituted one-valent hydrocarbon group which is the same or different from each other and has no aliphatic unsaturated bond, and k and m are independently 0 or a positive integer, and k+m is organic The viscosity of polyoxyalkylene at 25 °C can be 10~l, O00,000 mPa·s)

此外，R2之不具有脂肪族不飽和鍵之一價烴基，其碳原子數爲1〜1〇，較佳爲1〜6爲理想’例如有與上述R1之具體例子爲相同者’惟不含鏈烯基及環己烯基。 k 及 m，一般係滿足〇$k$2,000，l$mS10,000, 且l$k+mgl〇,〇〇〇之〇或正整數，較佳者係滿足5Sk + mS2,000，且〇‘k/ (k+m) S0.2 之整數。一般式（1)所示之有機聚矽氧烷，其具體而言，例如有下示者。 •10- 201005040 【化2】 c6h5 h2c=ch-s 卜 o- c«3\ c,h5 -Si-〇4—si一( :ch2 C6H5 \CH3/iii CiH5 CH3H2C=CH-Si-〇 C6H5\ CH3 SI-〇4—Si—CH=CH2 0H=CH，八 'CiiHs/n ch=ch2 ❿Further, R2 does not have a monovalent hydrocarbon group of an aliphatic unsaturated bond, and has a carbon number of 1 to 1 Å, preferably 1 to 6 is desirable 'for example, the same as the specific example of the above R1' Alkenyl and cyclohexenyl. k and m, generally satisfy 〇$k$2,000, l$mS10,000, and l$k+mgl〇, 〇〇〇 or positive integer, preferably 5Sk + mS2,000, and 〇'k / (k+m) An integer from S0.2. The organopolyoxane represented by the general formula (1), specifically, for example, is shown below. •10- 201005040 【化2】c6h5 h2c=ch-s 卜o- c«3\ c,h5 -Si-〇4—si one ( :ch2 C6H5 \CH3/iii CiH5 CH3H2C=CH-Si-〇C6H5\ CH3 SI-〇4—Si—CH=CH2 0H=CH, eight 'CiiHs/n ch=ch2 ❿

OH=CH2 / 〒H3 H2C=CH-Si-〇——{-Si-OOH=CH2 / 〒H3 H2C=CH-Si-〇——{-Si-O

ch»ch2 Si—CH=CH2 c:h=ch2 \ ch3 h \ c6rs /«» ch=ch2 C：H=CH2 / «3 \ ch=ch2 H2C=CH-Si-〇——i-Si-OJ—Si—CH=CH2 CH=CH2 \ /«〇 ch=ch2 h2c=chCh»ch2 Si—CH=CH2 c:h=ch2 \ ch3 h \ c6rs /«» ch=ch2 C:H=CH2 / «3 \ ch=ch2 H2C=CH-Si-〇——i-Si-OJ —Si—CH=CH2 CH=CH2 \ /«〇ch=ch2 h2c=ch

c6h5 Si-CH=CH2 ch=ch2 ❹ 【化3】 ch3 ch3 ch3 CH2=CH-Si〇—(SiO)5-Si-CH=CH2 ch3 ch3 ch3 ch3 ch3 ch3 ot3 CH2=CH-Si〇—(SiO)u—(SiO)5rSi-CH=CH2 c;h3 c6h5 ch3 ch3 (上式中，k及m係如上所示）。 (A)成分之有機聚矽氧烷，其進一步之具體例子有以下所示者。 -11 - 201005040 【化4】 ch3 H2C=HC-Si~〇-CH, CHi H2C=HC-Si-〇- 3C6h5 Si-CH=CH2 ch=ch2 ❹ 【化3】 ch3 ch3 ch3 CH2=CH-Si〇—(SiO)5-Si-CH=CH2 ch3 ch3 ch3 ch3 ch3 ch3 ot3 CH2=CH-Si〇—(SiO U—(SiO)5rSi-CH=CH2 c; h3 c6h5 ch3 ch3 (in the above formula, k and m are as shown above). Further examples of the organopolyoxane of the component (A) are as follows. -11 - 201005040 [Chemical 4] ch3 H2C=HC-Si~〇-CH, CHi H2C=HC-Si-〇- 3

CH ch3 I H2C=HC-Si-0 ch3CH ch3 I H2C=HC-Si-0 ch3

Si一O I ch3 ch3 / ch3 I / I H2C=HC-Si-〇十 Si—O CH3 \ CH3Si-O I ch3 ch3 / ch3 I / I H2C=HC-Si-〇 Ten Si-O CH3 \ CH3

Si一0-4- QH5 /ioSi 0-4- QH5 /io

CeHsCeHs

Si一OSi-O

CH3 I Si—CH=CH, ch3CH3 I Si—CH=CH, ch3

CH3 Si—CH=CH2 I ch3CH3 Si—CH=CH2 I ch3

H2C=HC-Si-〇H2C=HC-Si-〇

(B)具有樹脂構造之有機聚矽氧烷本發明中，具有脂肪族不飽和鍵之有機聚矽氧烷，除 7 (A)成分之本質上爲直鏈狀之有機聚矽氧烷以外，並可使用樹脂構造之有機聚矽氧烷作爲（B)成分而使用。 (B)具有成分之脂肪族不飽和基之樹脂構造之有機聚矽氧烷，其係先進行三次元交聯，而具有三次元網狀構造者。該有機聚矽氧烷，係由R^SiOm單位及Si02單位所成者，惟亦可視情形而進一步含有R】Si03/2單位及 -12- 201005040 R'SiO單位之至少一種亦即，基本上，係由R^SiOm單位及Si02單位所成者，惟在不損及發明目的效果之範圍內，亦可任意地含有R^SiOw單位及/或R^siO單位。較佳者，係由R^SiOm單位及Si02單位所成者。在此，Ri 係相同或相異’而獨立地爲取代或非取代性，較佳爲碳原 .子數1~1〇之一價烴基，已如關於（A)成分之說明所述。又此有機聚矽氧烷，其係以重量平均分子量500~10,000 φ 之範圍爲較佳。 (B)成分之有機聚矽氧烷，其基於「具有樹脂構造」之點’係與（A)成分之本質上爲直鏈狀之有機聚矽氧烷爲相異者。本說明書中，所謂（B)成分之有機聚矽氧烷「具有樹脂構造」，係指該有機聚矽氧烷樹脂中之全矽氧烷單位之5莫耳％以上，較佳爲1 〇莫耳％以上，更佳爲 15〜75莫耳％，最佳則爲25〜50莫耳％，係由Si02單位所成者。此單位係具有將分子之矽氧烷骨架作用成三次元 φ 網狀構造者。具有（B)成分之樹脂構造之有機聚砂氧院，其較佳者，基本係由Si02單位（QB單位）' R\R4pSi〇() 5單位（ MB1單位）及R3qR4rSiOQ.5單位（MB2單位）所成者，並 ' 可以上述比例含有任意地二官能性矽氧烷單位及/或三官能性矽氧烷單位（亦即，有機倍半矽氧烷單位）之有機聚矽氧烷（在此，R3係乙烯基或烯丙基，R4係不含脂肪族不飽和鍵之一價烴基，η爲2或3，p爲0或1，並有n+p =3之關係，q爲〇或i，r爲2或3，並有q+r=3之關 -13- 201005040 係）。此外，R4之不含脂肪族不飽和鍵之取代或非取代之— 價烴基’例如有與上述R2同樣之碳原子數i、"，尤其是 1〜6者》在此’如將QB單位之莫耳數作爲q，MB1單位之莫耳數作爲nu，MB2單位之莫耳數作爲m2時，其係以滿足以下關係式（1)及（2): (HM+mz) / q= 0.3〜3、尤其是 0.7 〜1 (1) 0 m2/q=0.01〜1、尤其是 0.07 〜0.15 ( 2 ) 者爲較佳。此種樹脂構造之有機聚矽氧烷之合成，可將各自單位源之化合物，組合成生成單位所要之比例，而在例如酸之存在下進行共水解。其中，前述QB單位源，例如有矽酸蘇打、烷基矽酸鹽、聚烷基矽酸鹽、四氯化矽等。此外，ΜB 1單位源，例如有下述例示之化合物。參 -14- 201005040 【化5】 h2c:=ch HC=CH2 H2C=CH-Si—〇—Si-CH=CH2 h2c:=ch hc=ch2 CH, CH, H2C=CH-Si—O—Si-CH=CH2 h2c=ch hc=ch2(B) Organic polyoxyalkylene having a resin structure In the present invention, an organic polyoxyalkylene having an aliphatic unsaturated bond, except for the organic polyoxyalkylene which is linear in nature in the 7 (A) component, An organic polyoxyalkylene having a resin structure can be used as the component (B). (B) An organic polyoxyalkylene having a resin structure of a component of an aliphatic unsaturated group which is first subjected to three-dimensional crosslinking and has a three-dimensional network structure. The organopolyoxane is composed of R^SiOm units and SiO 2 units, but may further contain at least one of R]Si03/2 units and -12-201005040 R'SiO units, as the case may be, basically It is composed of R^SiOm unit and SiO2 unit, and may contain R^SiOw unit and/or R^siO unit arbitrarily within the range not impairing the effect of the invention. The better ones are those made up of R^SiOm units and SiO2 units. Here, Ri is the same or different and independently substituted or unsubstituted, preferably a carbon atom. The number of 1 to 1 fluorene hydrocarbon group is as described in the description of the component (A). Further, the organic polyoxane is preferably in the range of a weight average molecular weight of 500 to 10,000 φ. The organopolyoxane of the component (B) is distinguished by the fact that the "having a resin structure" is different from the linear organopolysiloxane of the component (A). In the present specification, the organic polyoxane of the component (B) "having a resin structure" means 5 mol% or more of the total decane unit in the organopolysiloxane resin, preferably 1 〇 mo More than or equal to the ear, more preferably 15 to 75 mol%, and most preferably 25 to 50 mol%, which is formed by the SiO 2 unit. This unit has a structure in which a molecular naphthenic skeleton is formed into a three-dimensional φ network structure. The organic polyxic furnace having the resin structure of the component (B), preferably, is basically composed of SiO 2 units (QB units) 'R\R4pSi〇() 5 units (MB1 units) and R3qR4rSiOQ.5 units (MB2 units) And an organic polyoxane which may contain any difunctional azoxy group unit and/or a trifunctional azide unit (i.e., an organic sesquiterpene unit) in the above ratio (in the above ratio) Thus, R3 is a vinyl or allyl group, R4 is a monovalent hydrocarbon group free of aliphatic unsaturated bonds, η is 2 or 3, p is 0 or 1, and has a relationship of n+p=3, q is 〇 Or i, r is 2 or 3, and there is a q+r=3 level -13 - 201005040 series). Further, the substituted or unsubstituted aliphatic hydrocarbon group of R4 which does not contain an aliphatic unsaturated bond has, for example, the same number of carbon atoms i, ", especially 1 to 6 of the above R2. Here, as in the case of QB unit The number of moles is q, the number of moles of MB1 is nu, and the number of moles of MB2 is m2, which satisfies the following relations (1) and (2): (HM+mz) / q= 0.3 〜3, especially 0.7 〜1 (1) 0 m2 / q = 0.01 〜 1, especially 0.07 〜 0.15 ( 2 ) is preferred. The synthesis of the organopolyoxane of such a resin structure can be carried out by combining the compounds of the respective unit sources into a desired ratio of the production unit, and co-hydrolysis in the presence of, for example, an acid. Here, the QB unit source is, for example, a soda citrate, an alkyl phthalate, a polyalkyl decanoate or ruthenium tetrachloride. Further, the ΜB 1 unit source is, for example, a compound exemplified below.参-14- 201005040 [Chemical 5] h2c:=ch HC=CH2 H2C=CH-Si-〇-Si-CH=CH2 h2c:=ch hc=ch2 CH, CH, H2C=CH-Si—O—Si- CH=CH2 h2c=ch hc=ch2

<pi2CH3 CH2CH3 H2C=€H-Si—〇—Si-CH=CH2 h2c=ch hc=ch2<pi2CH3 CH2CH3 H2C=€H-Si—〇—Si—CH=CH2 h2c=ch hc=ch2

H2C=CH—Si—〇—Si—C：H=CH2 h2c=ch hc=ch2H2C=CH—Si—〇—Si—C:H=CH2 h2c=ch hc=ch2

H2C=CH--Si—〇—Si—CH=CH2 h2c=ch hc=ch2H2C=CH--Si—〇—Si—CH=CH2 h2c=ch hc=ch2

h2c=ch H2C=CH-Si—Cl H2C：=CH ch3 H2C=CH-Si—Cl h2c=ch 進一步，mB2單位源，例如有下述例示之化合物。 -15- 201005040 【化6】 ch3 ch3H2c=ch H2C=CH-Si-Cl H2C:=CH ch3 H2C=CH-Si—Cl h2c=ch Further, the mB2 unit source is, for example, the compound exemplified below. -15- 201005040 【化6】 ch3 ch3

I II I

H3c—Si—〇—Si-CH3 I I ch3 ch3 CH2CH3 CH2CH3 H2C=CH-Si—0—Si 一 CH=CH2H3c—Si—〇—Si—CH3 I I ch3 ch3 CH2CH3 CH2CH3 H2C=CH-Si—0—Si—CH=CH2

I I ch3 ch3I I ch3 ch3

CH2CH3 CH2CH3 H3C-Si—o—Si-CH3 CHj CH3CH2CH3 CH2CH3 H3C-Si-o-Si-CH3 CHj CH3

H3C—Sji-O—由一 CH3 CH3 CH,H3C—Sji-O—by a CH3 CH3 CH,

H3C—Si—O—Si 一 CH3 ch3 ch3H3C—Si—O—Si—CH3 ch3 ch3

H3C-Si-a ch3 CH,H3C-Si-a ch3 CH,

I H2C=CH-Si-Cl ch3 此種具有（B)成分之樹脂構造之有機聚砂氧院’其係用於調整所得到之硬化物之硬度而配合者，如先前所說明者，以前述（A)成分及（B)成分之合計量而言，—般 -16- 201005040 係0.1〜50質量％之量，較佳係1〜30質量％加以配合。可根據該（B)成分之比例進行調整而調整其硬度。 (C)有機氫聚矽氧烷 (C)成分之有機氫聚矽氧烷係發揮交聯劑之作用者 . ，該成分中之SiH基及（A)成分及（B)成分中之鏈烯基等之脂肪族不飽和基，係藉由加成反應而形成硬化物。 φ 此種有機氫聚矽氧烷，其只要係在一分子中具有結合於矽原子之氫原子（亦即SiH基）2個以上，較佳爲3個以上，最佳爲4〜1，0 0 0個者即可。結合於矽原子之氫原子，其位置並無特別之限制，可爲分子之末端亦可爲非末端。 (C)成分之有機氫聚矽氧烷，其係與（A)成分及（ B)成分進行反應，並作爲交聯劑而作用者，在一分子中平均有2個以上，較佳爲平均3個以上之結合於矽原子之氫原子（以SiH所示之氫甲矽烷基）者爲必要，其一般具有者係3〜1000個，較佳爲3〜500個，最佳爲3〜200個，極佳爲4〜100個左右之結合於矽原子之氫原子爲理想。其分子構造並無特別之限制，傳統上可在加成反應硬化型聚矽氧組成物上作爲交聯劑而使用者皆可，例如有線狀 ' 、環狀、分枝狀、三次元網狀構造（樹脂狀）等各種。在一分子中有2個以上，較佳含有3個以上之結合於矽原子之氫原子，可位於其分子鏈末端及分子鏈非末端之任一者，或位於其二者均可。此種氫原子以外之結合於矽原子之一價原子或取代基，均不含脂肪族不飽和鍵，較佳 -17- 201005040 者係碳原子數1〜10之結合於矽原子之非取代或取代之— 價烴基。該有機氫聚矽氧烷之一分子中之矽原子數（亦即聚合度），其一般爲2〜1 000個，較佳爲3〜300個，最佳則爲4〜150個左右者爲理想，在25°C下之黏度，其一般爲 0.1〜100000 m P a · s，較佳爲0.5〜5000 m P a · s左右之室溫（2 5 °C )下爲液狀者。該有機氫聚矽氧烷，例如可使用下述平均組成式（2 )所示者。 R5bHcSiΟ(4-b-c)/2 ( 2) (式中，R5係不含脂肪族不飽和鍵，其較佳爲碳原子數1〜10之結合於矽原子之非取代或取代之一價烴基，b 爲0.7〜2.1之數，c爲0.001〜1.0之數，且b+c爲0.8〜 3.0之範圍者）。上述式R5所示之不含脂肪族不飽和鍵之非取代或取代之一價烴基，其例如有甲基、乙基、丙基、異丙基、丁基、異丁基、tert-丁基、戊基、新戊基、己基、環己基、辛基、壬基、癸基等烷基、苯基、甲苯基、二甲苯基、萘基等芳基、苄基、苯基乙基、苯基丙基等之芳烷基；將此等之烴基之氫原子之一部分或全部以氟、溴、氯等鹵原子加以取代者，如氯甲基、氯丙基、溴乙基、三氟丙基等。此等之非取代或取代之一價烴基’其又以烷基、芳基爲更佳，並以甲基、苯基爲最佳。此外，較佳者，b爲1.0〜2.0之數，c爲0.01〜1·〇之 201005040 數，且b+c爲1.5〜2·5之範圍者。此種有機氫聚矽氧院’其—般可藉由將R5SiHCi2、 (R5)3SiCl、（R5)2SiCl2、（R5)2SiHCl(R5 係如前述者）之類的氯砂院進行水解’或將經水解所得到之矽氧烷加以平衡化而得到。平均組成式（2)所示之有機氫聚矽氧烷，其具體而言’有1，1，3,3-四甲基二矽氧烷、13,5,7-四甲基環四矽氧 φ 烷、三（氫二甲基甲矽烷氧基）甲基矽烷 '三（氫二甲基甲矽烷氧基）苯基矽烷、甲基氫環聚矽氧烷、甲基氫矽氧烷•二甲基矽氧烷環狀共聚物、兩末端三甲基甲矽烷氧基封閉甲基氫聚矽氧烷、兩末端三甲基甲矽烷氧基封閉二甲基矽氧烷·甲基氫矽氧烷共聚物、兩末端二甲基氫甲矽烷氧基封閉二甲基聚矽氧烷、兩末端二甲基氫甲矽烷氧基封閉二甲基聚矽氧烷•甲基氫矽氧烷共聚物、兩末端三甲基甲矽烷氧基封閉甲基氫矽氧烷·二苯基矽氧烷共聚物、兩 • 末端三甲基甲矽烷氧基封閉甲基氫矽氧烷•二苯基矽氧烷 •二甲基矽氧烷共聚物、兩末端三甲基甲矽烷氧基封閉甲基氫矽氧烷•甲基苯基矽氧烷·二甲基矽氧烷共聚物、兩末端二甲基氫甲矽烷氧基封閉甲基氫矽氧烷•二甲基矽氧 " 烷·二苯基矽氧烷共聚物 '兩末端二甲基氫甲矽烷氧基封閉甲基氫矽氧烷·二甲基矽氧烷•甲基苯基矽氧烷共聚物、由（CH3)2HSi01/2 單位及（CH3)3Si01/2 單位及 Si04/2 單位所成之共聚物、由（CH3)2HSi〇i/2單位及Si〇4,2單位所成之共聚物、由（CH3)2HSi〇i/2 單位及 Si〇4/2 單位及（C6H5)3Si〇i/2 -19- 201005040 單位所成之共聚物等。更具體言之，例如有下述式所示構造之氫有機矽氧烷【化7】I H2C=CH-Si-Cl ch3 such an organic polyoxo chamber having a resin structure of the component (B) is used to adjust the hardness of the obtained cured product, as described above, with the aforementioned The total amount of the component (A) and the component (B) is generally from 0.1 to 50% by mass, preferably from 1 to 30% by mass, based on the total amount of the component (A). The hardness can be adjusted by adjusting the ratio of the component (B). (C) The organohydrogen polyoxyalkylene of the organohydrogen polyoxyalkylene (C) component functions as a crosslinking agent. The SiH group and the (A) component and the olefin in the component (B) in the component The aliphatic unsaturated group such as a group forms a cured product by an addition reaction. φ such an organic hydrogen polyoxyalkylene which has two or more hydrogen atoms (i.e., SiH groups) bonded to a ruthenium atom in one molecule, preferably three or more, and most preferably 4 to 1,0 0 0 can be. The position of the hydrogen atom bonded to the ruthenium atom is not particularly limited, and may be a terminal end of the molecule or a non-terminal end. The organic hydrogen polyoxyalkylene of the component (C) which reacts with the component (A) and the component (B) and acts as a crosslinking agent, and has an average of two or more in one molecule, preferably an average It is necessary to have three or more hydrogen atoms (hydrocarbinyl group represented by SiH) bonded to a halogen atom, and generally have 3 to 1000, preferably 3 to 500, and most preferably 3 to 200. Preferably, it is preferably from about 4 to about 100 hydrogen atoms bonded to a ruthenium atom. The molecular structure thereof is not particularly limited, and conventionally, it can be used as a crosslinking agent on an addition reaction-hardening polyfluorene-oxygen composition, for example, a linear 'ring, a ring, a branch, or a three-dimensional network. Various types of structures (resin-like). There are two or more in one molecule, and preferably three or more hydrogen atoms bonded to the ruthenium atom may be located at either the end of the molecular chain or the non-terminal end of the molecular chain, or both. Any one of such a hydrogen atom bonded to one of the valence atoms or a substituent of the ruthenium atom does not contain an aliphatic unsaturated bond, and preferably -17-201005040 is an unsubstituted or bonded ruthenium atom having a carbon number of 1 to 10. Replace it with a valence hydrocarbon group. The number of ruthenium atoms (that is, the degree of polymerization) in one molecule of the organohydrogen polyoxyalkylene is generally from 2 to 1,000, preferably from 3 to 300, and most preferably from 4 to 150. Desirably, the viscosity at 25 ° C is generally 0.1 to 100,000 m P a · s, preferably 0.5 to 5000 m P a · s or so at room temperature (25 ° C). As the organic hydrogen polyoxyalkylene, for example, those represented by the following average composition formula (2) can be used. R5bHcSiΟ(4-bc)/2 (2) (wherein R5 does not contain an aliphatic unsaturated bond, and is preferably an unsubstituted or substituted one-valent hydrocarbon group having a carbon number of 1 to 10 bonded to a halogen atom, b is a number of 0.7 to 2.1, c is a number of 0.001 to 1.0, and b+c is a range of 0.8 to 3.0). The unsubstituted or substituted monovalent hydrocarbon group represented by the above formula R5 which does not contain an aliphatic unsaturated bond, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tert-butyl group. , pentyl, neopentyl, hexyl, cyclohexyl, octyl, decyl, decyl, etc. alkyl, phenyl, tolyl, xylyl, naphthyl and the like aryl, benzyl, phenylethyl, benzene An aralkyl group such as a propyl group; a part or all of a hydrogen atom of such a hydrocarbon group is substituted with a halogen atom such as fluorine, bromine or chlorine, such as chloromethyl, chloropropyl, bromoethyl or trifluoropropane. Base. These unsubstituted or substituted one-valent hydrocarbon groups are more preferably an alkyl group or an aryl group, and most preferably a methyl group or a phenyl group. Further, preferably, b is a number of 1.0 to 2.0, c is a number of 0.01 to 1 〇 201005040, and b + c is a range of 1.5 to 2.5. Such an organohydrogen polyoxylizer can be hydrolyzed by a chlorine sand plant such as R5SiHCi2, (R5)3SiCl, (R5)2SiCl2, (R5)2SiHCl (R5 is as described above) or The hydroxane obtained by the hydrolysis is obtained by equilibration. An organic hydrogen polyoxyalkylene represented by the formula (2), which specifically has 1,1,3,3-tetramethyldioxane, 13,5,7-tetramethylcyclotetrazepine Oxy φ alkane, tris(hydrodimethylformamoxy)methyl decane 'tris(hydrodimethylformamoxy)phenyl decane, methylhydrocyclopolyoxyalkylene, methylhydroquinone Dimethyl methoxy olefin cyclic copolymer, two-terminal trimethyl methacryloxy blocking methyl hydrogen polyoxy siloxane, two-terminal trimethyl methacryloxy blocking dimethyl methoxy oxane methyl hydrazine Oxyalkane copolymer, two-terminal dimethylhydroformamoxy blocking dimethylpolyoxane, two-terminal dimethylhydroformamoxy blocking dimethylpolydecane, methylhydroquinone copolymer , two-terminal trimethylmethane alkoxy-blocked methylhydroquinone-diphenyl decane copolymer, two terminal trimethylmethane alkoxy-blocked methylhydroquinone • diphenyl fluorene Oxylkane dimethyl methoxide copolymer, two-terminal trimethylmethane alkoxy-blocked methylhydroquinone, methyl phenyl oxane dimethyl methoxide copolymer, two terminal dimethyl Hydrogen矽 alkoxy blocking methyl hydroperoxane • dimethyl oxime " alkane diphenyl decane copolymer 'end two dimethyl hydroformamoxy blocking methyl hydrooxane dimethyl a copolymer of oxime/methylphenyl decane, a copolymer of (CH3)2HSi01/2 units and (CH3)3Si01/2 units and Si04/2 units, from (CH3)2HSi〇i/2 Copolymers of units and Si〇4,2 units, copolymers of (CH3)2HSi〇i/2 units and Si〇4/2 units and (C6H5)3Si〇i/2 -19- 201005040 units Wait. More specifically, for example, a hydroorganooxy oxane having the structure shown by the following formula [Chemical 7]

H3C-Si-CH3 R6H3C-Si-CH3 R6

ΟΟ

Η VH3 CH3Η VH3 CH3

H3C-Si-CH3 CHz O CH 3 όH3C-Si-CH3 CHz O CH 3 ό

I-Si-O—Si—〇—Si—〇—Si—Si-II I I I CH3 O CH3 CH, H3C-S1-CH3I-Si-O-Si-〇-Si-〇-Si-Si-II I I I CH3 O CH3 CH, H3C-S1-CH3

HH

-20- 201005040 【化8】-20- 201005040 【化8】

(上式中，L爲0〜200之整數，Μ爲1〜200之整數，R6爲含有選自環氧基、（甲基）丙烯氧基、烷氧基甲砂烷基之官能基之官能基取代烷基）。此外，（C)成分之有機氫聚矽氧烷之配合量，係上述（A)成分及（B)成分之硬化有效量，尤以其所含之結合於矽原子之氫原子，其相對於（A)成分及（B)成分中 -21 - 201005040 之鏈烯基等之脂肪族不飽和基之合計1莫耳，係以0.8〜 4.0莫耳爲較佳，1·0〜3.0莫耳爲更佳，並以1.〇〜2.0莫耳爲最佳。該（C)成分如過多時’未反應之結合於砂原子之氫原子會大量地殘存於硬化物中，結果會有造成橡膠物性經時變化之原因之虞。 (D)鉑族金屬系觸媒 (D)成分之鉛族金屬系觸媒，係具有能使本發明之組成物發生加成硬化反應之作用。該觸媒，例如有鉑系、鈀系、铑系者，惟基於成本之觀點，例如有鉑、鉑黑、氯化鉑酸等之鉑系物質，如 H2PtCl6 · mH20，K2PtCl6， KHPtCU · mH2〇，K2PtC“，K^PtCU · mH2〇，Pt02 · mH2〇 (m爲正整數）等，或此等與含有烯烴等之烴、醇或乙烯基之有機聚矽氧烷之錯合物等。此等可爲一種單獨或二種以上之組合。 (D)成分之配合量爲有效量即可，一般，係以相對於前述（A)〜（E)成分之合計量，鉑族金屬換算（質量 )時，爲0.1〜1000 ppm，較佳爲0.5〜200 ppm之範圍。 (E )觸變性賦予劑該觸變性賦予劑，係（F)成分之燻矽以外之觸變性賦予劑，其係藉由（F)成分之燻矽所具有的羥基（OH) 與氫鍵結或形成擬似交聯，而使得觸變性得以表現，且其較佳者係於室溫（25t )下呈現液狀者。 -22- 201005040 該觸變性賦予劑，可使用具有：羥基（-OH基）、院氧基、鏈烯基氧基、芳基氧基等之有機氧基等極性基；以及環氧基之任一者，之聚矽氧化合物（有機聚矽氧院）或聚醚等之有機樹脂成分。具體而言，例如有具有下述式所示之結合於矽原子之氫原子與環氧基之有機聚矽氧烷（惟，不含有烷氧基等之極性基者）。該（E)成分，相對於 (A)〜（C)成分之合計100質量份，係添加〇.〇1〜5質量份之範圍。【化9】(In the above formula, L is an integer of 0 to 200, Μ is an integer of 1 to 200, and R6 is a functional group having a functional group selected from the group consisting of an epoxy group, a (meth) propyleneoxy group, and an alkoxymethyl group. Base substituted alkyl). Further, the compounding amount of the organic hydrogen polyoxyalkylene of the component (C) is an effective amount of curing of the above components (A) and (B), particularly a hydrogen atom bonded to a halogen atom, which is relative to (A) component and (B) component - 21 - 201005040 The total number of aliphatic unsaturated groups of alkenyl groups and the like is 1 mole, preferably 0.8 to 4.0 moles, and 1 to 0 to 3.0 moles. Better, and the best is 1.1~2.0 mol. When the component (C) is too large, the unreacted hydrogen atom bonded to the sand atom remains in the hardened material in a large amount, and as a result, the rubber property changes over time. (D) A platinum group metal catalyst (D) component of a lead group metal catalyst has an action of allowing an addition hardening reaction of the composition of the present invention. The catalyst is, for example, a platinum-based, a palladium-based or a lanthanide-based one, but a platinum-based substance such as platinum, platinum black, or chloroplatinic acid, such as H2PtCl6 · mH20, K2PtCl6, KHPtCU · mH2〇, is based on cost. , K2PtC ", K ^ PtCU · mH2 〇, Pt02 · mH2 〇 (m is a positive integer), etc., or such a complex with a hydrocarbon containing an olefin or the like, an alcohol or a vinyl organic polyoxane, etc. The compounding amount of the component (D) may be an effective amount, and generally, in terms of the total amount of the components (A) to (E), the platinum group metal is converted (quality). In the case of 0.1 to 1000 ppm, preferably in the range of 0.5 to 200 ppm. (E) Thixotropy-imparting agent, the thixotropic imparting agent, which is a thixotropic imparting agent other than the smoked component of the component (F) The hydroxyl group (OH) possessed by the smoked component of the component (F) is hydrogen-bonded or formed to be pseudo-crosslinked, so that thixotropy is exhibited, and it is preferably one which exhibits liquidity at room temperature (25t). -22- 201005040 The thixotropy-imparting agent can be used with: a hydroxyl group (-OH group), an alkoxy group, an alkenyloxy group, an aryl group Or a polar group such as an organic oxy group such as a group; and an organic resin component such as a polyfluorene compound (organic polysiloxane) or a polyether, and the like, for example, An organic polyoxyalkylene (hereinafter, a polar group not containing an alkoxy group or the like) bonded to a hydrogen atom of a halogen atom and an epoxy group is shown. The component (E) is relative to (A) to (C). The total amount of the components is 100 parts by mass, and is added in the range of 1 to 5 parts by mass.

(上式中，1=0〜100之整數’ m=l〜100之整數，η =1〜100之整數）。 (F)燻矽該成分如上述，係與（Ε)成分之觸變性賦予劑相互作用，而在本發明之組成物中顯示出賦予觸變性之作用。該燻矽，其1次粒子徑係5 nm〜50 nm，且比表面積係10 201005040 〜500 m2/g者爲較佳。該（F)成分之添加量，相對於（A) ~(E)成分之合計1〇〇質量份，一般係1〜30質量份，較佳則係5〜25 質量份者。其他成分(In the above formula, an integer of 1 = 0 to 100' m = an integer of 1 to 100, and an integer of η = 1 to 100). (F) Smoked cockroach This component interacts with the thixotropy imparting agent of the (Ε) component as described above, and exhibits the effect of imparting thixotropy in the composition of the present invention. The smoked cockroach has a primary particle diameter of 5 nm to 50 nm, and a specific surface area of 10 201005040 to 500 m 2 /g is preferred. The amount of the component (F) to be added is usually 1 to 30 parts by mass, preferably 5 to 25 parts by mass, based on 1 part by mass of the total of the components (A) to (E). Other ingredients

本發明之組成物中，除上述（A) ~(F)成分之外，並可根據需要而任意地添加其他成分。舉例而言，有接著助劑、著色劑、螢光體、顏料、樹脂粉體等。接著助劑：爲提高對於本發明組成物之基材之接著性，較佳係添加接著助劑。該接著助劑，例如有一般式（3)所示之有機氧基甲矽烷基變性三聚異氰酸酯化合物及/或其水解縮合物（有機矽氧烷變性三聚異氰酸酯化合物）。【化1 0】In the composition of the present invention, in addition to the above components (A) to (F), other components may be arbitrarily added as needed. For example, there are auxiliaries, colorants, phosphors, pigments, resin powders, and the like. Next, an auxiliary agent is added to improve the adhesion to the substrate of the composition of the present invention. The auxiliaries include, for example, an organic methoxymethyl decyl denatured trimeric isocyanate compound represented by the general formula (3) and/or a hydrolyzed condensate thereof (organic oxirane-modified trimeric isocyanate compound). [化1 0]

I I 7入〆N R7 CI I 7 into 〆N R7 C

(3)(3)

II 〇 [式中，R7係下式（4): 【化1 1】 OR8 -fc:H2)7-〒、OR8 (4) OR8 (其中，R8係氫原子或碳原子數1〜6之一價烴基， -24- 201005040 爲1〜6，尤其是1〜4之整數）。所示之有機基、或含有脂肪族不飽和鍵之一價烴基，惟R7之至少一個係以式（4)所示之有機基]。在一般式（3)中，R7所示之含有脂肪族不飽和鍵之一價烴基，例如有乙烯基、烯丙基、丙烯基、異丙烯基、丁烯基、異丁烯基、戊烯基、己烯基等之碳原子數2〜8, 尤其是2〜6烯基以及環己烯基等。此外，R8所示之碳原子數1〜6之一價烴基，例如有甲基、乙基、丙基、異丙基、丁基、異丁基、tert-丁基、戊基、己基等烷基；環己烯基；乙烯基、烯丙基、丙烯基、異丙烯基、丁烯基、異丁烯基、戊烯基、己烯基等之鏈烯基；環己烯基；苯基等之芳基等之碳原子數1〜8，尤其是1〜6之一價烴基，較佳則爲烷基。上述一般式（3)之有機氧基甲矽烷基變性三聚異氰酸酯化合物，其具體例子有下述式所示之化合物。 -25- 201005040 【化1 2】II 〇 [wherein, R7 is the following formula (4): [Chemical 1 1] OR8 -fc: H2) 7-〒, OR8 (4) OR8 (wherein R8 is a hydrogen atom or one of the carbon atoms 1 to 6 The valence hydrocarbon group, -24-201005040 is 1 to 6, especially an integer of 1 to 4). The organic group shown, or a monovalent hydrocarbon group containing an aliphatic unsaturated bond, wherein at least one of R7 is an organic group represented by the formula (4)]. In the general formula (3), a monovalent hydrocarbon group containing an aliphatic unsaturated bond represented by R7, for example, a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentenyl group, The hexenyl group or the like has 2 to 8 carbon atoms, particularly a 2 to 6 alkenyl group and a cyclohexenyl group. Further, the one-valent hydrocarbon group having 1 to 6 carbon atoms represented by R8 may, for example, be an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group or a hexyl group. a cyclohexenyl group; an alkenyl group such as a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentenyl group, a hexenyl group or the like; a cyclohexenyl group; a phenyl group or the like. The aryl group or the like has 1 to 8 carbon atoms, particularly 1 to 6 monovalent hydrocarbon groups, preferably an alkyl group. The organooxycarbazene-modified trimeric isocyanate compound of the above general formula (3), and a specific example thereof is a compound represented by the following formula. -25- 201005040 【化1 2】

HC CH,HC CH,

?H2 ,Ν, ,OCH, CH2CH2CH2一Si： OCHi h3cc/ h3co、 OCH,?H2 , Ν, , OCH, CH2CH2CH2 - Si: OCHi h3cc / h3co, OCH,

ΗΗ

II

Si——OCH； ch2ch2ch2 i 、c ch2ch2ch2—<II /、〇Ch3 u h3co (CHjO)3SiC3H^ 此外，接之烷氧基以外原子之鏈烯基機矽烷及有機 ,N. C3H(iSi(OCH3)3Si——OCH; ch2ch2ch2 i , c ch2ch2ch2—<II /, 〇Ch3 u h3co (CHjO)3SiC3H^ In addition, an alkenyl group other than an alkoxy group, decane and organic, N. C3H (iSi(OCH3) )3

SC N, 'C3H6Si(OCH3)3 著助劑，例如有：除必須含有結合於矽原子，尙具有結合於矽原子之氫原子、結合於矽、及/或環氧基之有機矽化合物（亦即，有资矽氧烷），其具體例子有下述式所示者。SC N, 'C3H6Si(OCH3)3 auxiliary agent, for example: organic ruthenium compound which has a hydrogen atom bonded to a ruthenium atom and is bonded to ruthenium and/or an epoxy group in addition to a ruthenium atom. That is, a paraoxane is used, and specific examples thereof are as shown in the following formula.

-26- 201005040 【化1 3】 och3-26- 201005040 【化1 3】 och3

och3Och3

H3C-Si-O-Si-O-J—Si-〇- CH3 c2h4 \ CH3 -si—〇H—a—〇- c3H6 \h och2ch-—ch2 -Si-CH3 ch3H3C-Si-O-Si-O-J-Si-〇-CH3 c2h4 \ CH3 -si-〇H-a-〇- c3H6 \h och2ch--ch2 -Si-CH3 ch3

Si(OCH3)3 (式中，m爲0〜50之整數，n爲0〜50之整數，但 m+n滿足2〜50，較佳則滿足4〜20)。此種有機矽化合物之中，所得到之硬化物係接著性特別優良之化合物，例如有在一分子中具有結合於矽原子之烷氧基、鏈烯基或結合於矽原子之氫原子（SiH基）之有機矽化合物爲理想。該接著助劑之配合量，相對於（A)成分、（B)成分 -27- 201005040 及（C)成分之合計100質量份，一般係10質量份以下（亦即0〜10質量份），較佳爲0.01〜5質量份，最佳則爲 0.1〜1質量份左右所配合者。（F)成分之配合量如太多時，可能會對硬化物之硬度或表面黏著性造成不良影響。組成物之調製•使用本發明之聚矽氧橡膠組成物，可將上述各成分混合成所要量，均一地進行混合而調製。此時，可少量添加炔醇等之硬化抑制劑並作成1液型而調製。此外，如要調製2 液型時，因爲將（C)成分及（D)成分配置於同一部分中，可能會有發生脫氫反應之危險，因此爲避免該危險起見必須各別地配置其部分。如此調製之本發明組成物，其係以在厚度1 mm之層狀態下，2(TC之波長波長450 nm之光穿透率在80%以上者爲較佳，並以85%以上者爲最佳。至於穿透率以在厚度 1 mm下求出之理由，係因爲將LED晶片被覆而形成透鏡時之透鏡厚度爲約1 mm之故。本發明之組成物，可根據需要，以例如60〜150°C進行加熱而使其立即硬化。如此所得到之硬化物，其具有高度之透明性且對於封裝材料或金屬基板能接著地非常理想。因此，在將LED裝置於基板並封閉之際，其作爲COB (Chip on Board)用封閉劑極佳。又亦可廣泛地使用於光學二極體、CCD、CMOS等廣泛使用之半導體封裝上。此外，在本發明之聚矽氧橡膠組成物中，將（F)成 -28- 201005040 分之燻矽以外之（A)〜（E)成分均一地進行混和之混合物的折射率，其基於硬化物透明性之觀點，係以與燻矽之折射率相同或彼此近似者爲重要。具體而言，除了燻矽以外’將（A)〜（E)成分均一地進行混和之混合物折射率 ’其必須爲1.42〜1.47之範圍內者。本發明組成物之折射率’其硬化率在硬化後亦爲實質上未改變而相同者。在以本發明之組成物將光半導體晶片加以封閉之光半 φ 導體裝置中，光半導體晶片所裝製之支持構造體，其並無特別之限制’可爲封裝者，亦可爲無封裝之支持基板，例如陶瓷基板、砂基板、玻璃環氧基板、電木（環氧樹脂）基板、金屬基板等。實施例以下茲舉出本發明之實施例具體地說明本發明。在以下之記載中，份係指質量份之意思，又黏度則爲25 t下之 φ 測定値。Me爲甲基，Ph爲苯基，Vi爲乙烯基。實施例1 將：之下式所示之 (a)末端以乙烯基封閉之黏度1 pa 聚矽氧烷（VF) 50份，以及【化1 4】Si(OCH3)3 (wherein m is an integer of 0 to 50, and n is an integer of 0 to 50, but m+n satisfies 2 to 50, preferably 4 to 20). Among such organic ruthenium compounds, the obtained cured product is particularly excellent in adhesion, for example, has an alkoxy group bonded to a ruthenium atom in one molecule, an alkenyl group or a hydrogen atom bonded to a ruthenium atom (SiH) The organic bismuth compound of the group is ideal. The amount of the auxiliary agent is generally 10 parts by mass or less (that is, 0 to 10 parts by mass) based on 100 parts by mass of the total of the components (A) and (B), -27 to 201005040 and (C). It is preferably 0.01 to 5 parts by mass, and most preferably 0.1 to 1 part by mass. If the amount of the component (F) is too large, it may adversely affect the hardness or surface adhesion of the cured product. Modification of the composition and use The polyoxyethylene rubber composition of the present invention can be prepared by mixing the above components into a desired amount and uniformly mixing them. In this case, a hardening inhibitor such as an alkyne alcohol may be added in a small amount to prepare a one-liquid type. In addition, when the two liquid type is to be prepared, since the (C) component and the (D) component are disposed in the same portion, there is a possibility that a dehydrogenation reaction may occur. Therefore, in order to avoid the danger, it is necessary to dispose each of them separately. section. The composition of the present invention thus prepared is preferably in the state of a layer having a thickness of 1 mm, 2 (the wavelength of the wavelength of TC is 450 nm, and the light transmittance is preferably 80% or more, and 85% or more is the most. The reason why the transmittance is obtained at a thickness of 1 mm is that the thickness of the lens when the lens is formed by coating the LED wafer is about 1 mm. The composition of the present invention may be, for example, 60 as needed. Heating at ~150 ° C to immediately cure it. The cured product thus obtained has a high degree of transparency and can be ideally followed for the encapsulating material or the metal substrate. Therefore, when the LED device is mounted on the substrate and closed It is excellent as a blocking agent for COB (Chip on Board), and can also be widely used in semiconductor packages widely used for optical diodes, CCD, CMOS, etc. Further, the polyoxyethylene rubber composition of the present invention (F) is a refractive index of a mixture in which (A) to (E) components are uniformly mixed except for the sputum of -28-201005040, which is based on the transparency of the cured product. It is important that the refractive indices are the same or similar to each other. In addition to the smoked sputum, 'the refractive index of the mixture in which the components (A) to (E) are uniformly mixed' must be in the range of 1.42 to 1.47. The refractive index of the composition of the present invention' In the light semi-φ conductor device in which the optical semiconductor wafer is sealed by the composition of the present invention, the support structure of the optical semiconductor wafer is not particularly limited. 'The package may be a package substrate without a package, such as a ceramic substrate, a sand substrate, a glass epoxy substrate, a bakelite (epoxy resin) substrate, a metal substrate, etc. Examples Hereinafter, the implementation of the present invention will be described. In the following description, the term "parts" means mass parts, and the viscosity is φ measured at 25 t. Me is a methyl group, Ph is a phenyl group, and Vi is a vinyl group. 1 Will: (a) end of the formula (a) with a vinyl-blocked viscosity of 1 pa polyoxyalkylene (VF) 50 parts, and [Chemical 1 4]

-29- 201005040 (CH3)3SiO0 5 單位 42_5 (b)由Si02單位50莫耳。/。、莫耳％及ViMezSiOo.5單位7.5莫耳％所成之樹脂構造之乙烯基甲基矽氧烷（VMQ) 50份、 (C) SiH基量，相對於前述（〇成分及（b)成分中之乙嫌基之合計1莫耳，係成爲1.5莫耳之量之下述式：【化1 5】-29- 201005040 (CH3)3SiO0 5 Units 42_5 (b) 50 mA by SiO 2 unit. /. , Mol% and ViMezSiOo.5 units 7.5 mol% of the resin structure of vinyl methyl oxane (VMQ) 50 parts, (C) SiH basis amount, relative to the above (〇 component and (b) component The total amount of the suspicion of the sinister base is 1 mole, which is the following formula of 1.5 moles: [Chemical 1 5]

所示之有機氫聚矽氧烷4.9份、及 (d)氯化鉑酸之辛基醇變性溶液〇.〇5份（相對於（ a) 、（b) 、（c) 、（d)及後述之（e)之各成分合計，鉑換算（質量）約爲5ppm)， (f)燻矽（產品名稱艾洛吉爾300以六甲基二矽氮烷進行矽烷基化處理）1 2份，充分地進行混合，再以三輥輥碎機加以混練° 在所得到之混練物中，再添加（e )下述之流動控制劑（觸變性賦予劑）〇·5 份、下述之接著賦予成分0.2份，調製成組成物° 流動控制劑（觸變性賦予劑）【化1 6】4.9 parts of the organic hydrogen polyoxyalkylene shown, and (d) an octyl alcohol denaturation solution of platinum chloride acid, 5 parts (relative to (a), (b), (c), (d) and The total amount of each component (e) described later is about 5 ppm in terms of platinum, and (f) 12 parts of smoked sputum (product name Aiguier 300 is decyl-alkylated with hexamethyldioxane). The mixture is thoroughly mixed and kneaded by a three-roller. In the obtained kneaded material, (e) the following flow control agent (thixotropy imparting agent) 〇·5 parts is added, followed by 0.2 parts of the composition, prepared into a composition ° flow control agent (thixotropy imparting agent) [Chemical 16]

201005040 (式中，1爲l〇，m爲8)。接著賦予成分【化1 7】 HC^CH2 %入〆0201005040 (where 1 is l〇 and m is 8). Then give the ingredients [Chemical 1 7] HC^CH2 % into 〆0

I I ❿ H2c、〆丫 N、MCH2—<〇CH3 g S H3a/ 卿圖1係將裝置於玻璃環氧基板1上之led元件2之光半導體裝置3的斷面示意圖。LED元件2及基板1上之電極4，係以金屬線5連接。將上述所得到之組成物，塗佈使LED元件2成爲被覆狀，使其成形、硬化，並形成凸透鏡狀之透明封閉體6。測定該光半導體裝置之下述特性以評價其信賴性。外觀：所得到之封閉體外觀以肉眼進行觀察，評價其透明性機械特性：將前述組成物，施加以1 50°C、4小時之加熱成型而製得硬化物，再依據JIS K 63 0 1，測定硬度（使用A型彈簧試驗機加以測定）。 -31 - 201005040 加濕回焊試驗：依據MSL水準2進行加濕回焊試驗。亦即，將光半導體裝置（樣品數5)放置於60°C/90%RH之環境下使其充分吸濕之後，再以所定次數（1次約6分鐘）通過2 60 亡之IR回焊爐。藉由目視評價其裂縫、剝離等不良情形之發生次數。爲比較起見，不使硬化之後的光半導體裝置吸濕，並同樣地使之進行IR回焊步驟。光穿透率：將組成物已成形爲厚度1 mm之薄片狀並硬化者，藉由20°C下分光光度計測定其對於波長450 nm之光的光穿透率。亮度：再將10 mA之電流施加於LED上，使LED各5個發光，並藉由大塚電子製之LED光學特性監視器（商品名稱：LP-3400 )測定其亮度。組成物之折射率：除不配合燻矽以外，與上述組成物相同地調製其組成物，並以阿倍折射率計測定該組成物之折射率。組成物之流動性： -32- 201005040 在玻璃基板上利用分配器將組成物1g以半球狀滴下，於25 °C下放置30分鐘後，再以150 °Cx3 0分鐘之條件硬化後，利用游標測定所得到之硬化物之直徑並評價其組成物之流動性（形狀保持性）。實施例2 除將實施例1所使用之（a)成分之添加量改成87.5 φ 份，（b)成分之添加量改成12.5份，實施例1所使用之 (c)成分之有機氫聚矽氧烷之添加量改成2份（相對於 (a) 、（b)成分之乙烯基之合計1莫耳，SiH基量係相當於1.5莫耳）以外，其餘均與實施例1同樣地進行操作，調製其組成物，並進行評價。實施例除將實施例1作爲（a)成分使用之VF，改成下述式 • 所示之乙烯基聚矽氧烷50份以外，其餘均與實施例1同樣地進行操作，調製其組成物，並進行評價。【化1 8】I I ❿ H2c, 〆丫 N, MCH2 - < 〇 CH3 g S H3a / 卿 Fig. 1 is a schematic cross-sectional view of the optical semiconductor device 3 of the led device 2 mounted on the glass epoxy substrate 1. The LED element 2 and the electrode 4 on the substrate 1 are connected by a metal wire 5. The composition obtained above was applied to form a LED element 2 into a coating shape, which was molded and cured to form a transparent lens-like transparent sealing body 6. The following characteristics of the optical semiconductor device were measured to evaluate the reliability. Appearance: The appearance of the obtained closed body was observed with the naked eye, and the transparency mechanical properties were evaluated: The composition was heated and formed at 150 ° C for 4 hours to obtain a cured product, and then according to JIS K 63 0 1 The hardness was measured (measured using a type A spring tester). -31 - 201005040 Humidification reflow test: Humidification and reflow test according to MSL level 2. That is, the optical semiconductor device (sample number 5) was placed in an environment of 60 ° C / 90% RH to sufficiently absorb moisture, and then passed through the IR reflow of 2 60 dead for a predetermined number of times (about 1 minute). furnace. The number of occurrences of defects such as cracks and peeling was evaluated by visual observation. For the sake of comparison, the optical semiconductor device after hardening is not absorbed, and the IR reflow step is similarly performed. Light transmittance: The composition was formed into a sheet having a thickness of 1 mm and hardened, and its light transmittance for light having a wavelength of 450 nm was measured by a spectrophotometer at 20 °C. Brightness: A current of 10 mA was applied to the LED, and five LEDs were emitted, and the brightness was measured by an LED optical characteristic monitor (trade name: LP-3400) manufactured by Otsuka Electronics Co., Ltd. Refractive index of the composition: The composition was prepared in the same manner as the above composition except that the smoke was not blended, and the refractive index of the composition was measured by an Abbie refractometer. Flowability of the composition: -32- 201005040 1 g of the composition was dropped on a glass substrate by a dispenser, placed at 25 ° C for 30 minutes, and then hardened at 150 ° C for 30 minutes, using a cursor The diameter of the obtained cured product was measured and the fluidity (shape retention) of the composition was evaluated. Example 2 In addition to changing the amount of the component (a) used in the first embodiment to 87.5 φ parts, the amount of the component (b) was changed to 12.5 parts, and the organic hydrogen grouping of the component (c) used in Example 1 was used. The addition amount of the decane was changed to 2 parts (1 mol to the total of the vinyl groups of the components (a) and (b), and the amount of the SiH group was 1.5 mol), except for the same as in the first embodiment. The operation was carried out, and the composition was prepared and evaluated. EXAMPLES The composition was prepared in the same manner as in Example 1 except that the VF used in the component (a) of Example 1 was changed to 50 parts of the vinyl polyoxane shown by the following formula: And evaluate. [化1 8]

比較例1 除將實施例1作爲（a)成分使用之VF，改成下述式所示之乙烯基聚矽氧烷50份以外，其餘均與實施例1同 -33- 201005040 樣地進行操作，調製其組成物，並進行評價。【化1 9】Comparative Example 1 The procedure of Example 1 was carried out in the same manner as in Example 1 except that the VF used in the component (a) was changed to 50 parts of the vinyl polyoxyalkylene represented by the following formula. The composition was prepared and evaluated. [化1 9]

比較例2 除不使用實施例1使用之（b)成分，並將（a)成分Comparative Example 2 except that the component (b) used in Example 1 was not used, and the component (a) was used.

之乙嫌基聚砂氧垸50份改成下述式：【化2 0】The 50 pieces of the sputum-based polysilicon oxime are changed into the following formula: [Chemical 2 0]

所示之乙烯基聚矽氧烷100份，進而（C)成分之有機氫聚矽氧烷4.9份，並添加下述式：【化2 1】100 parts of the vinyl polyoxane shown, and further 4.9 parts of the organic hydrogen polyoxyalkylene of the component (C), and the following formula is added: [Chemical 2 1]

所示之氫矽氧烷2.5份以外，其餘均與實施例1同樣地進行操作，調製其組成物，並進行評價。此等之結果示於表1及表2中。 -34- 201005040 [表i] 實施例1 實施例2 實施例3 比較例1 比較例2 SiH/SiVi 1.5 1.5 1.5 1.5 1.5 外觀透明透明透明微濁微濁折射率 1.43 1.43 1.46 1.41 1.51 硬化條件 150°C/4hr 150〇C/4hr 150〇C/4hr 150〇C/4hr 150〇C/4hr 硬度 (型式A) 75 35 40 75 35 樹脂之流動性(mm/lg) 直徑 15.5 15.2 15.2 15.3 16.3 光穿透率 (450nm) 20°C 1mm厚 92 92 96 70 65 [表2]The composition was prepared in the same manner as in Example 1 except that 2.5 parts of the hydroquinone was shown, and the composition was prepared and evaluated. The results of these are shown in Tables 1 and 2. -34- 201005040 [Table i] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 SiH/SiVi 1.5 1.5 1.5 1.5 1.5 Appearance Transparent transparent transparent micro-turbid micro-turbidity refractive index 1.43 1.43 1.46 1.41 1.51 Hardening condition 150° C/4hr 150〇C/4hr 150〇C/4hr 150〇C/4hr 150〇C/4hr Hardness (Type A) 75 35 40 75 35 Resin fluidity (mm/lg) Diameter 15.5 15.2 15.2 15.3 16.3 Light wear Permeability (450nm) 20°C 1mm thickness 92 92 96 70 65 [Table 2]

實施例1 實施例2 實施例3 比較例1 比較例2 哽化之後 0 0 0 0 0 加濕回焊試驗註 260回焊 /1次 0 0 0 0 0 260回焊 /2次 0 0 0 0 0 260回焊 /3次 0 0 0 0 0 260回焊 /4次 0 0 0 0 0 260回焊 /5次 0 0 0 0 0 亮度 mLm 100 96 120 75 80 (註）數字係供試之樣品數5個中之不良發生數 ‘ 「260回焊/η次」係使將IR回焊步驟重複η次（每1 次約6分鐘）之意。 -35- 201005040 【圖式簡單說明】圖1:係將裝置於支持基板之玻璃環氧基板上之led 元件，以本發明之組成物使其硬化而成之透鏡狀硬化物進行封閉之光半導體裝置之縱斷面圖。 · 【主要元件符號說明】 1 :玻璃環氧基板 2 : LED元件 3 :光半導體裝置 4 :電極 5 :金屬線 6 :透明封閉體 -36-Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 After deuteration 0 0 0 0 0 Humidification reflow test Note 260 reflow / 1 time 0 0 0 0 0 260 reflow / 2 times 0 0 0 0 0 260 reflow / 3 times 0 0 0 0 0 260 reflow / 4 times 0 0 0 0 0 260 reflow / 5 times 0 0 0 0 0 brightness mLm 100 96 120 75 80 (Note) Digital test sample The number of defects in the number of 5 '260 reflows/n times' is such that the IR reflow step is repeated n times (about 6 minutes per 1 time). -35- 201005040 [Simplified Schematic] FIG. 1 is a light-emitting semiconductor in which a led device is mounted on a glass epoxy substrate supporting a substrate, and a lenticular cured product obtained by hardening the composition of the present invention is used. A longitudinal section of the device. · [Main component symbol description] 1 : Glass epoxy substrate 2 : LED component 3 : Optical semiconductor device 4 : Electrode 5 : Metal wire 6 : Transparent enclosure -36-

Claims

201005040 七、申請專利範園： 1· 一種硬化性聚矽氧橡膠組成物，其特徵爲含有： (A) 在一分子中具有2個以上之脂肪族不飽和鍵，且本質上爲直鏈狀之有機聚矽氧烷， (B) 在一分子中具有2個以上之脂肪族不飽和鍵，且具有樹脂構造之有機聚矽氧烷， (C) 在一分子中具有2個以上之結合於矽原子之氫 φ 原子之有機氫聚矽氧烷， (D) 鉑族金屬系觸媒， (E )除（F )成分以外之觸變性賦與劑，以及 (F)燻矽所成者，且由（A)〜（E)成分所成之組成物之折射率係 1.42〜1 .47。 2. —種聚矽氧橡膠硬化物，其特徵係將申請專利範圍第1項之組成物加以硬化所成，且在厚度1 mm之層狀態 0，其2〇°(：下之波長45〇11111之光之穿透率爲8〇%以上者。 3. —種光半導體裝置，其特徵係具有光半導體晶片，以及被覆該光半導體晶片之將申請專利範圍第1項之組成物加以硬化所成之聚矽氧橡膠硬化物。 -37-201005040 VII. Application for Patent Park: 1. A sclerosing polyoxymethylene rubber composition characterized by: (A) having two or more aliphatic unsaturated bonds in one molecule, and being substantially linear in nature The organic polyoxane, (B) an organic polyoxyalkylene having two or more aliphatic unsaturated bonds in one molecule and having a resin structure, (C) having two or more bonds in one molecule Hexatom hydrogen φ atomic organic hydrogen polyoxane, (D) platinum group metal catalyst, (E) thixotropic agent other than (F) component, and (F) smoked sputum, Further, the refractive index of the composition of the components (A) to (E) is 1.42 to 1.47. 2. A polyoxygenated rubber hardened article characterized by hardening a composition of the first application of the patent application, and in a layer of thickness 1 mm, 0 其° (: a wavelength of 45 下) The transmittance of light of 11111 is more than 8%. 3. An optical semiconductor device characterized by having an optical semiconductor wafer, and a composition for coating the optical semiconductor wafer to cure the composition of the first aspect of the patent application It is a hardened polyoxyethylene rubber. -37-