JP2009235265A - Curable silicone rubber composition and photosemiconductor device using the same as sealing material - Google Patents

Curable silicone rubber composition and photosemiconductor device using the same as sealing material Download PDF

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JP2009235265A
JP2009235265A JP2008084142A JP2008084142A JP2009235265A JP 2009235265 A JP2009235265 A JP 2009235265A JP 2008084142 A JP2008084142 A JP 2008084142A JP 2008084142 A JP2008084142 A JP 2008084142A JP 2009235265 A JP2009235265 A JP 2009235265A
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Tsutomu Kashiwagi
努 柏木
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Shin Etsu Chemical Co Ltd
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    • H01L2224/48225—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
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Abstract

<P>PROBLEM TO BE SOLVED: 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. <P>SOLUTION: 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. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

本発明は、支持構造体上に搭載された光半導体チップの被覆ないし封止の材料として有用な付加硬化型の硬化性シリコーンゴム組成物に関し、特に半導体チップに直接に適量適用し、成形、硬化させて透明な被覆を形成するのに適した付加硬化型の硬化性シリコーンゴム組成物に関する。   The present invention relates to an addition-curing type curable silicone rubber composition useful as a material for coating or sealing an optical semiconductor chip mounted on a support structure, and in particular, an appropriate amount is directly applied to a semiconductor chip to be molded and cured. The present invention relates to an addition-curable curable silicone rubber composition suitable for forming a transparent coating.

ＬＥＤ発光装置用レンズは、射出成形等の機械成形よって大量に製造されている。従来はアクリル樹脂、ポリカーボネート樹脂等の熱可塑樹脂を用いて成形されていたが、ＬＥＤ発光装置の高出力化に伴い、熱可塑樹脂では耐熱性、耐変色性が不十分であるとの問題が出てきた。また、最近では鉛フリー半田が多く使用されるようになってきたが、鉛フリー半田は従来の半田に比べ溶融温度が高いため、通常２６０℃以上の高温で光学素子を基板に半田付けする。このような温度で半田付けを行った場合、従来の熱可塑性材料からなるレンズでは変形が起ったり、高温のため黄変する不具合が発生し使用することが出来なくなる。   A large number of lenses for LED light emitting devices are manufactured by mechanical molding such as injection molding. Conventionally, it was molded using thermoplastic resin such as acrylic resin and polycarbonate resin, but with the increase in output of LED light emitting device, there is a problem that thermoplastic resin has insufficient heat resistance and discoloration resistance. It came out. In recent years, lead-free solder has been frequently used. Since lead-free solder has a higher melting temperature than conventional solder, the optical element is usually soldered to the substrate at a high temperature of 260 ° C. or higher. When soldering is performed at such a temperature, a conventional lens made of a thermoplastic material may be deformed, or may be yellowed due to a high temperature and cannot be used.

このような状況からＬＥＤ等のためのレンズ材料にシリコーン樹脂を使用する試みが数多くなされている。例えば、シリコーン樹脂を用いて射出成形等の成形方法で予め製造したレンズを、ＬＥＤチップを搭載したパッケージに装着する方法が提案されている（特許文献１）。しかし、この方法では接着樹脂とインナー樹脂とが必要になる上に作業も煩雑で容易でない。   Under such circumstances, many attempts have been made to use a silicone resin as a lens material for an LED or the like. For example, a method has been proposed in which a lens manufactured in advance by a molding method such as injection molding using silicone resin is mounted on a package on which an LED chip is mounted (Patent Document 1). However, this method requires an adhesive resin and an inner resin and is cumbersome and difficult.

支持構造体上に装着した光半導体チップ上で材料を成形、硬化させる方法として、オーバーモールド法が知られている（特許文献２参照）。この方法は、樹脂の透明性やチクソ性のコントロールが不十分であるという欠点を有する。   As a method for molding and curing a material on an optical semiconductor chip mounted on a support structure, an overmold method is known (see Patent Document 2). This method has a drawback that the transparency and thixotropic control of the resin are insufficient.

そこで、近年、支持構造体上に搭載されたＬＥＤチップ上にシリコーン樹脂を直接適用し、レンズ状に成形する方法が提案されている（特許文献３）。しかし、使用されるシリコーン樹脂のチクソ性が劣るため、これを支持基板上のＬＥＤチップにディスペンサーを用いて直接に適量を適用し、成形・硬化させようとしても流れてしまい、目的の形状を有する成形・硬化物が得られないという問題があった。また、シリコーン樹脂のチクソ性が不十分である結果、これを使用する製造装置も高価なものとならざるを得ないという問題もあった。   Therefore, in recent years, a method has been proposed in which a silicone resin is directly applied to an LED chip mounted on a support structure and molded into a lens shape (Patent Document 3). However, since the thixotropy of the silicone resin used is inferior, the appropriate amount is directly applied to the LED chip on the support substrate using a dispenser, and it flows even if it is molded and cured, so that it has the desired shape. There was a problem that a molded / cured product could not be obtained. Further, as a result of insufficient thixotropy of the silicone resin, there has been a problem that a manufacturing apparatus using the silicone resin has to be expensive.

シリコーン樹脂にヒュームドシリカを添加すればチクソ性を付与できることは知られているが白濁が生じたり得られるチクソ性にロットごとにバラツキがあるため実用的でなかった。   Although it is known that thixotropy can be imparted by adding fumed silica to a silicone resin, it is not practical because of the cloudiness or the thixotropy obtained varies from lot to lot.

特開２００７−２４２２４６JP2007-242246 特開２００６−１４８１４７JP 2006-148147 A 特開２００７−１２３８９１JP 2007-123891 A

そこで、本発明の課題は、支持構造体上に装着したＬＥＤチップにディスペンサーを用いて直接に適量を適用し、成形・硬化させることにより透明性の高いレンズ形状の被覆ないし封止体を形成することができる硬化性シリコーンゴム組成物を提供することにある。   Accordingly, an object of the present invention is to form a highly transparent lens-shaped coating or sealing body by applying an appropriate amount directly to a LED chip mounted on a support structure using a dispenser, and molding and curing the LED chip. An object of the present invention is to provide a curable silicone rubber composition that can be used.

そこで、本発明者らは、オルガノポリシロキサン成分の構成、ヒュームドシリカの屈折率とそれ以外の成分全体の屈折率との関係などを検討することにより、硬化物の透明性と安定したチクソ性を両立したシリコーン樹脂組成物を見出し、上記の課題を解決することができた。   Therefore, the present inventors examined the constitution of the organopolysiloxane component, the relationship between the refractive index of fumed silica and the refractive index of the other components as a whole, and the transparency of the cured product and stable thixotropy. The present inventors have found a silicone resin composition that satisfies both of the above and has solved the above problems.

即ち、本発明は、具体的には、
（Ａ）一分子中に２個以上の脂肪族不飽和結合を有し、本質的に直鎖状であるオルガノポリシロキサン、
（Ｂ）一分子中に２個以上の脂肪族不飽和結合を有し、樹脂構造を有するオルガノポリシロキサン、
（Ｃ）一分子中にケイ素原子結合水素原子を２個以上有するオルガノハイドロジェンポリシロキサン、
（Ｄ）白金族金属系触媒、
（Ｅ）（Ｆ）成分以外のチクソ性付与剤、および
（Ｆ）ヒュームドシリカ
を含有してなり、かつ（Ａ）〜（Ｅ）成分からなる組成物の屈折率が1.42〜1.47であることを特徴とする硬化性シリコーンゴム組成物を提供する。 That is, the present invention specifically includes
(A) an organopolysiloxane having two or more aliphatic unsaturated bonds in one molecule and being essentially linear;
(B) an organopolysiloxane having two or more aliphatic unsaturated bonds in one molecule and having a resin structure;
(C) an organohydrogenpolysiloxane having two or more silicon-bonded hydrogen atoms in one molecule;
(D) a platinum group metal catalyst,
(E) The thixotropic agent other than (F) component and (F) fumed silica are contained, and the refractive index of the composition comprising components (A) to (E) is 1.42 to 1.47. A curable silicone rubber composition is provided.

また、本発明は上記の組成物を硬化してなり、厚さ１ｍｍの層状態で２０℃における波長４５０ｎｍの光の透過率が８０％以上であるシリコーンゴム硬化物を提供する。   In addition, the present invention provides a cured silicone rubber obtained by curing the above composition and having a layer state of 1 mm thickness and a light transmittance of 450 nm at 20 ° C. of light having a wavelength of 450% or more.

該硬化物は例えば光半導体装置に用いられる光半導体チップの封止材料として有用である。   The cured product is useful, for example, as a sealing material for an optical semiconductor chip used in an optical semiconductor device.

そこで、本発明は、さらに、光半導体チップと、該光半導体チップを被覆する、上記組成物を硬化してなるシリコーンゴム硬化物とを有する光半導体装置を提供する。   Therefore, the present invention further provides an optical semiconductor device having an optical semiconductor chip and a cured silicone rubber obtained by curing the above composition and covering the optical semiconductor chip.

本発明の組成物はチクソ性に優れているので、例えば、支持構造体上に装着された光半導体チップにディスペンサーを用いて適量の組成物を簡便に適用することができ、その後成形、硬化させることによりレンズ形状の被覆体を安定的に形成することができる。   Since the composition of the present invention is excellent in thixotropy, for example, an appropriate amount of the composition can be simply applied to the optical semiconductor chip mounted on the support structure using a dispenser, and then molded and cured. Thus, a lens-shaped covering can be stably formed.

−（Ａ）脂肪族不飽和結合含有オルガノポリシロキサン−
本発明のベース成分である（Ａ）成分は、一分子中に２個以上の脂肪族不飽和結合を有し、本質的に直鎖状であるオルガノポリシロキサンである。該オルガノポリシロキサンは粘度が作業性、硬化性などの点から、２５℃で１０〜１，０００，０００ｍＰａ・ｓ、特に１００〜１００，０００ｍＰａ・ｓであることが望ましい。 -(A) Aliphatic unsaturated bond-containing organopolysiloxane-
The component (A), which is the base component of the present invention, is an organopolysiloxane that has two or more aliphatic unsaturated bonds in one molecule and is essentially linear. The organopolysiloxane desirably has a viscosity of 10 to 1,000,000 mPa · s, particularly 100 to 100,000 mPa · s at 25 ° C. from the viewpoint of workability and curability.

分子構造は本質的に直鎖状であり、好ましくは直鎖状である。「本質的に直鎖状である」とは、本成分中の両末端を封鎖するトリオルガノシロキシ基以外の全てのシロキサン単位が主に２官能単位（Ｄ単位）（具体的には、式：R1 ２SiOで表される単位）で構成されるが、全シロキサン単位の３モル％以下、好ましくは２モル％以下で分岐を形成する３官能単位（Ｔ単位）（具体的には、式：R1SiO3/2で表される単位）および４官能単位（Ｑ単位）（具体的には、式：SiO4/2単位で表される単位）の少なくとも１種のシロキサン単位を含有してもよいことを意味する。好ましくは両末端のみが一官能性単位（Ｍ単位）（具体的には、式：R1 3SiO1/2で表される単位）で構成され、その他のシロキサン単位がすべてＤ単位からなる直鎖状のジオルガノポリシロキサンである。ここで、R1は置換もしくは非置換の一価炭化水素基である。 The molecular structure is essentially linear, preferably linear. “Essentially linear” means that all siloxane units other than the triorganosiloxy group blocking both ends in this component are mainly bifunctional units (D units) (specifically, the formula: R units composed of R 1 2 SiO), but a trifunctional unit (T unit) that forms a branch at 3 mol% or less, preferably 2 mol% or less of all siloxane units (specifically, a formula : Units represented by R 1 SiO 3/2 ) and tetrafunctional units (Q units) (specifically, units represented by the formula: SiO 4/2 units) It means you may. Preferably, only both terminals are composed of monofunctional units (M units) (specifically, units represented by the formula: R 1 3 SiO 1/2 ), and other siloxane units are all composed of D units. It is a chain diorganopolysiloxane. Here, R 1 is a substituted or unsubstituted monovalent hydrocarbon group.

ここで、Ｒ1の一価炭化水素基としては、炭素原子数１〜１０、特に１〜６のものが好ましく、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、オクチル基、ノニル基、デシル基等のアルキル基；等のアルキル基；シクロヘキシル基；フェニル基、トリル基、キシリル基、ナフチル基等のアリール基、ベンジル基、フェニルエチル基、フェニルプロピル基等のアラルキル基、ビニル基、アリル基、プロペニル基、イソプロペニル基、ブテニル基、ペンテニル基、ヘキセニル基、オクテニル基等のアルケニル基；シクロヘキセニル基；およびこれらの炭化水素基の水素原子の一部又は全部をフッ素、臭素、塩素等のハロゲン原子、シアノ基等で置換したもの、例えばクロロメチル基、クロロプロピル基、ブロモエチル基、トリフロロプロピル基等のハロゲン置換アルキル基やシアノエチル基等が挙げられる。 Here, the monovalent hydrocarbon group for R 1 is preferably a group having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, and specifically includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, Alkyl group such as isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, octyl group, nonyl group, decyl group; alkyl group; cyclohexyl group; phenyl group, tolyl group, xylyl group, naphthyl group, etc. Aralkyl groups such as aryl group, benzyl group, phenylethyl group and phenylpropyl group, alkenyl groups such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, pentenyl group, hexenyl group and octenyl group; cyclohexenyl And a part or all of the hydrogen atoms of these hydrocarbon groups may be substituted with halogen atoms such as fluorine, bromine and chlorine, Those substituted with amino group or the like, such as chloromethyl group, chloropropyl group, bromoethyl group, and a halogen-substituted alkyl group or cyanoethyl group such trifluoropropyl group.

（Ａ）成分のオルガノポリシロキサンは、一分子中に２個以上の脂肪族不飽和結合を有する。脂肪族不飽和結合としては、炭素原子数２〜８、特に２〜６のアルケニル基およびシクロアルケニル基が代表的であり、具体的には上述のビニル基、アリル基、プロペニル基、イソプロペニル基、ブテニル基、ペンテニル基、ヘキセニル基等のアルケニル基、シクロヘキセニル基等のシクロアルケニル基で例示される。中でも、好ましくはビニル基およびアリル基である。   The organopolysiloxane of component (A) has two or more aliphatic unsaturated bonds in one molecule. Typical examples of the aliphatic unsaturated bond include alkenyl groups and cycloalkenyl groups having 2 to 8 carbon atoms, particularly 2 to 6 carbon atoms. Specifically, the above-described vinyl group, allyl group, propenyl group, and isopropenyl group. And an alkenyl group such as a butenyl group, a pentenyl group and a hexenyl group, and a cycloalkenyl group such as a cyclohexenyl group. Among these, a vinyl group and an allyl group are preferable.

（Ａ）成分のオルガノポリシロキサンの好ましい具体例としては、下記一般式（１）で表される分子鎖両末端のケイ素原子のおのおのに少なくとも１個のアルケニル基を有する直鎖状オルガノポリシロキサンであって、上記でも述べた通り、２５℃における粘度が１０〜１，０００，０００ｍＰａ・ｓのものである。   A preferred specific example of the organopolysiloxane of component (A) is a linear organopolysiloxane having at least one alkenyl group for each silicon atom at both ends of the molecular chain represented by the following general formula (1). As described above, the viscosity at 25 ° C. is 10 to 1,000,000 mPa · s.

Figure 2009235265
Figure 2009235265

（式中、Ｒ1は前記の通り、独立に、非置換又は置換の一価炭化水素基、Ｒ2は互いに同一又は異種の脂肪族不飽和結合を有しない非置換又は置換一価炭化水素基であり、ｋおよびｍは独立に０又は正の整数であってｋ＋ｍがこのオルガノポリシロキサンの２５℃の粘度を１０〜１，０００，０００ｍＰａ・ｓとなる数である。） (Wherein, R 1 is independently an unsubstituted or substituted monovalent hydrocarbon group as described above, and R 2 is an unsubstituted or substituted monovalent hydrocarbon group that does not have the same or different aliphatic unsaturated bond. And k and m are each independently 0 or a positive integer, and k + m is a number at which the viscosity of this organopolysiloxane at 25 ° C. is 10 to 1,000,000 mPa · s.)

また、Ｒ2の脂肪族不飽和結合を有しない一価炭化水素基としても、炭素原子数１〜１０、特に１〜６のものが好ましく、上記Ｒ1の具体例と同様のものが例示できるが、但しアルケニル基およびシクロヘキセニル基は含まない。 Further, even if the monovalent hydrocarbon group with no aliphatic unsaturated bonds R 2, 1 to 10 carbon atoms, particularly preferably having 1 to 6, are the same as specific examples of the R 1 may be exemplified However, an alkenyl group and a cyclohexenyl group are not included.

ｋおよびｍは、一般的には、０≦ｋ≦２，０００、１≦ｍ≦１０，０００で、かつ、１≦ｋ＋ｍ≦１０，０００を満足する０又は正の整数であり、好ましくは５≦ｋ＋ｍ≦２，０００で、０≦ｋ／（ｋ＋ｍ）≦０．２を満足する整数である。   k and m are generally 0 or a positive integer satisfying 0 ≦ k ≦ 2,000, 1 ≦ m ≦ 10,000, and 1 ≦ k + m ≦ 10,000, preferably 5 ≦ k + m ≦ 2,000 and an integer satisfying 0 ≦ k / (k + m) ≦ 0.2.

一般式（１で表されるオルガノポリシロキサンとして具体的には、下記のものを例示することができる。   Specific examples of the organopolysiloxane represented by the general formula (1) include the following.

Figure 2009235265
Figure 2009235265

Figure 2009235265
Figure 2009235265

（上記式において、ｋおよびｍは上述した通りである。） (In the above formula, k and m are as described above.)

（Ａ）成分のオルガノポリシロキサンをさらに具体的な例は以下の通りである。   Specific examples of the organopolysiloxane (A) are as follows.

Figure 2009235265
Figure 2009235265

−（Ｂ）樹脂構造を有するオルガノポリシロキサン−
本発明では、脂肪族不飽和結合を有するオルガノポリシロキサンとして、（Ａ）成分の本質的に直鎖状であるオルガノポリシロキサンとともに、樹脂構造のオルガノポリシロキサンが（Ｂ）成分として使用される。 -(B) Organopolysiloxane having a resin structure-
In the present invention, as the organopolysiloxane having an aliphatic unsaturated bond, an organopolysiloxane having a resin structure is used as the component (B) together with the organopolysiloxane that is essentially linear as the component (A).

（Ｂ）成分の脂肪族不飽和基を有する樹脂構造のオルガノポリシロキサンは、予め三次元架橋され、三次元網状構造を有する。該オルガノポリシロキサン、R１ 3SiO1/2単位と、SiO2単位とからなるが、さらに場合によりR1SiO3/2単位およびR1 ２SiO単位の少なくとも一種を含んでもよい。即ち、基本的に、R１ 3SiO1/2単位とSiO2単位とからなるが、任意的にR1SiO3/2単位および／またはR1 ２SiO単位を発明の目的効果を損わない範囲で含有してよいものである。好ましくは、R１ 3SiO1/2単位とSiO2単位とからなる。ここで、R1は同じもしくは異なり、独立に、置換または非置換の、好ましくは炭素原子数１〜１０の、一価炭化水素基であり、（Ａ）成分に関して説明したとおりである。またこのオルガノポリシロキサンは、重量平均分子量が５００〜１０，０００の範囲であるものが好適である。 The organopolysiloxane having a resin structure having an aliphatic unsaturated group (B) is three-dimensionally crosslinked in advance and has a three-dimensional network structure. The organopolysiloxane is composed of R 1 3 SiO 1/2 units and SiO 2 units, but may further contain at least one of R 1 SiO 3/2 units and R 1 2 SiO units. That is, it basically comprises R 1 3 SiO 1/2 units and SiO 2 units, but optionally R 1 SiO 3/2 units and / or R 1 2 SiO units do not impair the object effects of the invention. It may be contained in a range. Preferably, it consists of R 1 3 SiO 1/2 units and SiO 2 units. Here, R 1 is the same or different and is independently a substituted or unsubstituted monovalent hydrocarbon group, preferably having 1 to 10 carbon atoms, as described for the component (A). The organopolysiloxane preferably has a weight average molecular weight in the range of 500 to 10,000.

（Ｂ）成分のオルガノポリシロキサンは「樹脂構造を有する」点で（Ａ）成分の本質的に直鎖状であるオルガノポリシロキサンと相違する。本明細書において、（Ｂ）成分のオルガノポリシロキサンが「樹脂構造を有する」とは該オルガノポリシロキサン樹脂中の全シロキサン単位の５モル％以上、好ましくは１０モル％以上、より好ましくは１５〜７５モル％、更に好ましくは２５〜５０モル％が、SiO2単位からなることを意味する。この単位は分子のシロキサン骨格を三次元網状構造にする作用を有する。 The (B) component organopolysiloxane differs from the (A) component essentially linear organopolysiloxane in that it has a “resin structure”. In this specification, the organopolysiloxane of the component (B) is “having a resin structure” means 5 mol% or more, preferably 10 mol% or more, more preferably 15 to 15 mol% of all siloxane units in the organopolysiloxane resin. 75 mol%, more preferably 25 to 50 mol%, means that consist of SiO 2 units. This unit has a function of making the siloxane skeleton of the molecule into a three-dimensional network structure.

（Ｂ）成分の樹脂構造を有するオルガノポリシロキサンとして好ましいものは、ＳｉＯ2単位（ＱＢ単位）、Ｒ3 nＲ4 pＳｉＯ0.5単位（ＭＢ１単位）およびＲ3 qＲ4 rＳｉＯ0.5単位（ＭＢ２単位）から基本的になり、任意的に二官能性シロキサン単位および／または三官能性シロキサン単位（即ち、オルガノシルセスキオキサン単位）を上述の割合で含んでよいオルガノポリシロキサンである（ここで、Ｒ3はビニル基又はアリル基、Ｒ4は脂肪族不飽和結合を含まない一価炭化水素基であり、ｎは２又は３、ｐは０又は１で、ｎ＋ｐ＝３の関係にあり、ｑは０又は１、ｒは２又は３で、ｑ＋ｒ＝３の関係にある。）。 (B) Preferred examples of organopolysiloxane having a resin structure of the components, SiO 2 units (Q B units), R 3 n R 4 p SiO 0.5 units (M B1 unit) and R 3 q R 4 r SiO 0.5 units It is an organopolysiloxane consisting essentially of (MB 2 units) and optionally containing difunctional siloxane units and / or trifunctional siloxane units (ie organosilsesquioxane units) in the above-mentioned proportions. (Where R 3 is a vinyl group or an allyl group, R 4 is a monovalent hydrocarbon group not containing an aliphatic unsaturated bond, n is 2 or 3, p is 0 or 1, and n + p = 3) Q is 0 or 1, r is 2 or 3, and q + r = 3.

なお、Ｒ4の脂肪族不飽和結合を含まない置換または非置換の一価炭化水素基としては、上記Ｒ2と同様の炭素原子数１〜１０、特に１〜６のものが挙げられる。 In addition, examples of the substituted or unsubstituted monovalent hydrocarbon group not containing the aliphatic unsaturated bond of R 4 include those having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, similar to the above R 2 .

ここで、ＱＢ単位のモル数をｑ、ＭＢ１単位のモル数をｍ１、ＭＢ２単位のモル数をｍ２としたときに、次の関係式（イ）および（ロ）：
（ｍ１＋ｍ２）／ｑ＝０．３〜３、特に０．７〜１ （イ）
ｍ２／ｑ＝０．０１〜１、特に０．０７〜０．１５ （ロ）
を満たすことが好ましい。 Here, when the number of moles of Q B units is q, the number of moles of M B1 units is m 1 , and the number of moles of M B2 units is m 2 , the following relational expressions (A) and (B):
(M 1 + m 2 ) /q=0.3-3, especially 0.7-1 (A)
m 2 /q=0.01 to 1, especially 0.07 to 0.15 (b)
It is preferable to satisfy.

このような樹脂構造のオルガノポリシロキサンの合成は、それぞれの単位源となる化合物を、生成単位が所要の割合となるように組み合わせ、例えば酸の存在下で共加水分解を行うことによって容易に行うことができる。   The synthesis of the organopolysiloxane having such a resin structure is easily performed by combining each unit source compound so that the generated units have a required ratio and co-hydrolyzing in the presence of an acid, for example. be able to.

ここで、前記ＱＢ単位源としては、ケイ酸ソーダ、アルキルシリケート、ポリアルキルシリケート、四塩化ケイ素等を例示することができる。 Here, as the Q B unit source, sodium silicate, alkyl silicates, polyalkyl silicates, can be exemplified silicon tetrachloride.

また、ＭＢ１単位源としては、下記の化合物を例示することができる。 Examples of the MB1 unit source include the following compounds.

Figure 2009235265
Figure 2009235265

更に、ＭＢ２単位源としては、下記の化合物を例示することができる。 Further, examples of the MB2 unit source include the following compounds.

Figure 2009235265
Figure 2009235265

この（Ｂ）成分の樹脂構造を有するオルガノポリシロキサンは、得られる硬化物の硬度を調整するために配合されるものであり、先にも説明した通り、前記（Ａ）成分と（Ｂ）成分の合計量当り、0.1〜50質量％の量で、好ましくは1〜30質量％配合される。該（Ｂ）成分の割合を調整することにより硬さが調整できる。   The organopolysiloxane having the resin structure of the component (B) is blended to adjust the hardness of the resulting cured product, and as described above, the components (A) and (B) The amount is 0.1 to 50% by mass, preferably 1 to 30% by mass based on the total amount. The hardness can be adjusted by adjusting the proportion of the component (B).

−（Ｃ）オルガノハイドロジェンポリシロキサン−
（Ｃ）成分のオルガノハイドロジェンポリシロキサンは架橋剤として作用するものであり、該成分中のＳｉＨ基と（Ａ）成分および（Ｂ）成分中のアルケニル基等の脂肪族不飽和基とが付加反応することにより硬化物を形成するものである。かかるオルガノハイドロジェンポリシロキサンは、一分子中にケイ素原子に結合した水素原子（即ち、ＳｉＨ基）を２個以上、好ましくは３個以上、特に４〜１，０００個有するものであればいずれのものでもよい。ケイ素原子に結合した水素原子の位置は特に制約はなく、分子の末端でも非末端でもよい。 -(C) Organohydrogenpolysiloxane-
Component (C), the organohydrogenpolysiloxane, acts as a crosslinking agent, and the addition of SiH groups in the component and aliphatic unsaturated groups such as alkenyl groups in the components (A) and (B). A cured product is formed by reaction. Such organohydrogenpolysiloxane is any one having 2 or more, preferably 3 or more, particularly 4 to 1,000, hydrogen atoms bonded to silicon atoms in one molecule (that is, SiH group). It may be a thing. The position of the hydrogen atom bonded to the silicon atom is not particularly limited and may be the terminal or non-terminal of the molecule.

（Ｃ）成分のオルガノハイドロジェンポリシロキサンは、（Ａ）成分および（Ｂ）成分と反応し、架橋剤として作用するものであり、一分子中に平均２個以上、好ましくは平均３個以上の珪素原子に結合した水素原子（ＳｉＨで表されるヒドロシリル基）を有する必要があり、通常、３〜１，０００個、好ましくは３〜５００個、より好ましくは３〜２００個、更に好ましくは４〜１００個程度のケイ素原子結合水素原子を有することが望ましい。その分子構造には特に制限はなく、従来付加反応硬化型シリコーン組成物に架橋剤として使用されているいずれも使用することができ、例えば線状、環状、分岐状、三次元網状構造（樹脂状）等各種のものが使用可能である。   The (C) component organohydrogenpolysiloxane reacts with the (A) component and the (B) component to act as a cross-linking agent, and has an average of 2 or more, preferably an average of 3 or more per molecule. It is necessary to have a hydrogen atom (hydrosilyl group represented by SiH) bonded to a silicon atom, and usually 3 to 1,000, preferably 3 to 500, more preferably 3 to 200, and still more preferably 4 It is desirable to have about ˜100 silicon-bonded hydrogen atoms. There are no particular restrictions on the molecular structure, and any of the conventionally used addition reaction curable silicone compositions used as a crosslinking agent can be used. For example, linear, cyclic, branched, and three-dimensional network structures (resinous ) Etc. can be used.

一分子中に２個以上、好ましくは３個以上含有されるケイ素原子結合水素原子は、分子鎖末端および分子鎖非末端のいずれに位置していてもよく、またこの両方に位置するものであってもよい。かかる水素原子以外の、ケイ素原子に結合した一価の原子または置換基はすべて脂肪族不飽和結合を含まない、好ましくは炭素原子数１〜１０の、珪素原子に結合した非置換又は置換の一価炭化水素基である。   The silicon-bonded hydrogen atoms contained in two or more, preferably three or more in one molecule may be located at either the molecular chain terminal or the molecular chain non-terminal, or both. May be. All monovalent atoms or substituents bonded to silicon atoms other than such hydrogen atoms do not contain aliphatic unsaturated bonds, and preferably are unsubstituted or substituted bonded to silicon atoms having 1 to 10 carbon atoms. Is a valent hydrocarbon group.

該オルガノハイドロジェンポリシロキサンの一分子中の珪素原子の数（即ち、重合度）は通常２〜１，０００個、好ましくは３〜３００個、より好ましくは４〜１５０個程度のものが望ましく、２５℃における粘度が、通常、０．１〜１００，０００ｍPa.ｓ、好ましくは、０．５〜５，０００ｍPa.ｓ程度の、室温（２５℃）で液状のものが使用される。   The number of silicon atoms in one molecule of the organohydrogenpolysiloxane (that is, the degree of polymerization) is usually 2 to 1,000, preferably 3 to 300, more preferably about 4 to 150, A liquid having a viscosity at 25 ° C. of usually 0.1 to 100,000 mPa.s, preferably about 0.5 to 5,000 mPa.s, at room temperature (25 ° C.) is used.

このオルガノハイドロジェンポリシロキサンとしては、例えば、下記平均組成式（２）で示されるものが用いられる。   As this organohydrogenpolysiloxane, for example, those represented by the following average composition formula (2) are used.

Ｒ5 bＨcＳｉＯ(4-b-c)/2 （２）
（式中、Ｒ5は、脂肪族不飽和結合を含まない、好ましくは炭素原子数１〜１０の、珪素原子に結合した非置換又は置換の一価炭化水素基であり、ｂは０．７〜２．１の数、ｃは０．００１〜１．０数であって、かつｂ＋ｃが０．８〜３．０の範囲である。） R 5 b H c SiO (4-bc) / 2 (2)
(Wherein R 5 is an unsubstituted or substituted monovalent hydrocarbon group bonded to a silicon atom having no aliphatic unsaturated bond, preferably having 1 to 10 carbon atoms, and b is 0.7 The number of ~ 2.1, c is 0.001 to 1.0, and b + c is in the range of 0.8 to 3.0.)

上記Ｒ5で表される脂肪族不飽和結合を含まない非置換又は置換の一価炭化水素基としては、例えばメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、シクロヘキシル基、オクチル基、ノニル基、デシル基等のアルキル基、フェニル基、トリル基、キシリル基、ナフチル基等のアリール基、ベンジル基、フェニルエチル基、フェニルプロピル基等のアラルキル基、これらの炭化水素基の水素原子の一部又は全部をフッ素、臭素、塩素等のハロゲン原子で置換したもの、例えばクロロメチル基、クロロプロピル基、ブロモエチル基、トリフロロプロピル基等が挙げられる。これらの非置換又は置換の一価炭化水素基の中でも、好ましくはアルキル基、アリール基であり、より好ましくはメチル基、フェニル基である。 Examples of the unsubstituted or substituted monovalent hydrocarbon group not containing an aliphatic unsaturated bond represented by R 5 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and tert-butyl. Group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, alkyl group such as decyl group, aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group, benzyl group, phenylethyl group, Aralkyl groups such as phenylpropyl groups, or those obtained by substituting some or all of the hydrogen atoms of these hydrocarbon groups with halogen atoms such as fluorine, bromine and chlorine, such as chloromethyl groups, chloropropyl groups, bromoethyl groups, trifluoro A propyl group etc. are mentioned. Among these unsubstituted or substituted monovalent hydrocarbon groups, an alkyl group and an aryl group are preferable, and a methyl group and a phenyl group are more preferable.

また、好ましくは、ｂは１．０〜２．０の数、ｃは０．０１〜１．０の数であって、ｂ＋ｃが１．５〜２．５の範囲である。   Preferably, b is a number from 1.0 to 2.0, c is a number from 0.01 to 1.0, and b + c is in a range from 1.5 to 2.5.

このようなオルガノハイドロジェンポリシロキサンは、通常、Ｒ5ＳｉＨＣｌ2、（Ｒ5）3ＳｉＣｌ、（Ｒ5）2ＳｉＣｌ2、（Ｒ5）2ＳｉＨＣｌ（Ｒ5は、前記の通りである）のようなクロロシランを加水分解するか、加水分解して得られたシロキサンを平衡化することにより得ることができる。 Such organohydrogenpolysiloxanes are usually R 5 SiHCl 2 , (R 5 ) 3 SiCl, (R 5 ) 2 SiCl 2 , (R 5 ) 2 SiHCl (R 5 is as described above). Such chlorosilanes can be hydrolyzed or siloxanes obtained by hydrolysis can be equilibrated.

平均組成式（２）で表されるオルガノハイドロジェンポリシロキサンとして、具体的には、例えば、１，１，３，３−テトラメチルジシロキサン、１，３,５,７−テトラメチルシクロテトラシロキサン、トリス（ハイドロジェンジメチルシロキシ）メチルシラン、トリス（ハイドロジェンジメチルシロキシ）フェニルシラン、メチルハイドロジェンシクロポリシロキサン、メチルハイドロジェンシロキサン・ジメチルシロキサン環状共重合体、両末端トリメチルシロキシ基封鎖メチルハイドロジェンポリシロキサン、両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体、両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルポリシロキサン、両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体、両末端トリメチルシロキシ基封鎖メチルハイドロジェンシロキサン・ジフェニルシロキサン共重合体、両末端トリメチルシロキシ基封鎖メチルハイドロジェンシロキサン・ジフェニルシロキサン・ジメチルシロキサン共重合体、両末端トリメチルシロキシ基封鎖メチルハイドロジェンシロキサン・メチルフェニルシロキサン・ジメチルシロキサン共重合体、両末端ジメチルハイドロジェンシロキシ基封鎖メチルハイドロジェンシロキサン・ジメチルシロキサン・ジフェニルシロキサン共重合体、両末端ジメチルハイドロジェンシロキシ基封鎖メチルハイドロジェンシロキサン・ジメチルシロキサン・メチルフェニルシロキサン共重合体、（ＣＨ3）2ＨＳｉＯ1/2単位と（ＣＨ3）3ＳｉＯ1/2単位とＳｉＯ4/2単位とからなる共重合体、（ＣＨ3）2ＨＳｉＯ1/2単位とＳｉＯ4/2単位とからなる共重合体、（ＣＨ3）2ＨＳｉＯ1/2単位とＳｉＯ4/2単位と（Ｃ6Ｈ5）3ＳｉＯ1/2単位とからなる共重合体などが挙げられる。 Specific examples of the organohydrogenpolysiloxane represented by the average composition formula (2) include 1,1,3,3-tetramethyldisiloxane and 1,3,5,7-tetramethylcyclotetrasiloxane. , Tris (hydrogendimethylsiloxy) methylsilane, tris (hydrogendimethylsiloxy) phenylsilane, methylhydrogencyclopolysiloxane, methylhydrogensiloxane-dimethylsiloxane cyclic copolymer, trimethylsiloxy group-blocked methylhydrogenpolysiloxane , Both ends trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, both ends dimethylhydrogensiloxy group-blocked dimethylpolysiloxane, both ends dimethylhydrogensiloxy group-blocked dimethyl Siloxane / methylhydrogensiloxane copolymer, trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane copolymer, trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane / dimethylsiloxane copolymer, both ends Trimethylsiloxy group-blocked methylhydrogensiloxane / methylphenylsiloxane / dimethylsiloxane copolymer, both ends dimethylhydrogensiloxy group-blocked methylhydrogensiloxane / dimethylsiloxane / diphenylsiloxane copolymer, both ends dimethylhydrogensiloxy group-blocked methyl Hydrogensiloxane / dimethylsiloxane / methylphenylsiloxane copolymer, (CH 3 ) 2 HSiO 1/2 unit and (CH 3 ) 3 A copolymer composed of SiO 1/2 units and SiO 4/2 units, a copolymer composed of (CH 3 ) 2 HSiO 1/2 units and SiO 4/2 units, (CH 3 ) 2 HSiO 1/2 Examples thereof include copolymers comprising units, SiO 4/2 units, and (C 6 H 5 ) 3 SiO 1/2 units.

さらに具体的には、下記式で表される構造のハイドロジェンオルガノシロキサンが例示できる。   More specifically, hydrogen organosiloxane having a structure represented by the following formula can be exemplified.

Figure 2009235265
Figure 2009235265

Figure 2009235265
Figure 2009235265

（上の式中、Ｌは０〜２００の整数、Ｍは１〜２００の整数、Ｒ6はエポキシ基、（メタ）アクリロキシ基、アルコキシシリル基から選ばれる官能基を含有する官能基置換アルキル基である。） (In the above formula, L is an integer of 0 to 200, M is an integer of 1 to 200, R 6 is a functional group-substituted alkyl group containing a functional group selected from an epoxy group, a (meth) acryloxy group, and an alkoxysilyl group. .)

なお、（Ｃ）成分のオルガノハイドロジェンポリシロキサンの配合量は、上記（Ａ）成分および（Ｂ）成分の硬化有効量であり、特にこれに含まれるケイ素原子結合水素原子が、（Ａ）成分および（Ｂ）成分中のアルケニル基等の脂肪族不飽和基の合計１モル当たり０．８〜４．０モルであることが好ましく、１．０〜３．０モルがより好ましく、１．０〜２．０モルであることがさらに好ましい。該（Ｃ）成分が多すぎると、未反応のケイ素原子結合水素原子が硬化物中に多量に残存する結果、ゴム物性が経時的に変化する原因となる恐れがある。   In addition, the compounding amount of the organohydrogenpolysiloxane of the component (C) is an effective curing amount of the component (A) and the component (B), and the silicon atom-bonded hydrogen atoms contained therein are particularly the component (A). And preferably 0.8 to 4.0 moles, more preferably 1.0 to 3.0 moles per mole of aliphatic unsaturated groups such as alkenyl groups in component (B), More preferably, it is -2.0 mol. If the component (C) is too much, a large amount of unreacted silicon-bonded hydrogen atoms remain in the cured product, which may cause the rubber properties to change over time.

−（Ｄ）白金族金属系触媒−
（Ｄ）成分の白金族金属系触媒は本発明の組成物の付加硬化反応を生じさせる作用を有する。該触媒としては、白金系、パラジウム系、ロジウム系のものがあるが、コスト等の見地から白金、白金黒、塩化白金酸などの白金系のもの、例えば、Ｈ2ＰｔＣｌ6・ｍＨ2Ｏ，Ｋ2ＰｔＣｌ6，ＫＨＰｔＣｌ6・ｍＨ2Ｏ，Ｋ2ＰｔＣｌ4，Ｋ2ＰｔＣｌ4・ｍＨ2Ｏ，ＰｔＯ2・ｍＨ2Ｏ（ｍは、正の整数）等や、これらと、オレフィン等の炭化水素、アルコール又はビニル基含有オルガノポリシロキサンとの錯体等が挙げられる。これらは一種単独でも２種以上を組み合わせても使用することができる。 -(D) Platinum group metal catalyst-
The platinum group metal catalyst of component (D) has the effect of causing an addition curing reaction of the composition of the present invention. Examples of the catalyst include platinum-based, palladium-based, and rhodium-based catalysts. From the viewpoint of cost and the like, platinum-based catalysts such as platinum, platinum black, and chloroplatinic acid such as H 2 PtCl 6 · mH 2 O, K 2 PtCl 6 , KHPtCl 6 · mH 2 O, K 2 PtCl 4 , K 2 PtCl 4 · mH 2 O, PtO 2 · mH 2 O (m is a positive integer), etc., and carbonization of olefins and the like Examples thereof include a complex with hydrogen, alcohol, or vinyl group-containing organopolysiloxane. These can be used singly or in combination of two or more.

（Ｄ）成分の配合量は有効量でよく、通常、前記（Ａ）〜（Ｅ）成分の合計量に対して白金族金属換算（質量）で０．１〜１，０００ｐｐｍ、好ましくは０．５〜２００ｐｐｍの範囲で使用される。   The compounding amount of the component (D) may be an effective amount, and is usually 0.1 to 1,000 ppm, preferably 0.00 in terms of platinum group metal (mass) based on the total amount of the components (A) to (E). Used in the range of 5 to 200 ppm.

−（Ｅ）チクソ性付与剤−
該チクソ性付与剤は（Ｆ）成分のヒュームドシリカ以外のチクソ性付与剤であって、（Ｆ）成分のヒュームドシリカが有する水酸基（OH）と水素結合や擬似架橋を形成することによりチクソ性を発現させるもので、好適には室温（２５℃）において液状のものである。 -(E) thixotropic agent-
The thixotropic agent is a thixotropic agent other than the fumed silica of the component (F), and forms a hydrogen bond or pseudo-crosslinking with the hydroxyl group (OH) of the fumed silica of the component (F). And is preferably liquid at room temperature (25 ° C.).

該チクソ成分付与剤としては、ヒドロキシ基（−ＯＨ基）、アルコキシ基、アルケニルオキシ基、アリールオキシ基等のオルガノオキシ基等の極性基、並びに、エポキシ基のいずれか一方をもつシリコーン化合物（オルガノポリシロキサン）やポリエーテル等の有機樹脂成分を用いることができる。具体的には、例えば、下記の式で表されるケイ素原子結合水素原子とエポキシ基をもつオルガノポリシロキサン（但し、アルコキシ基等の極性基を含有しないもの）が挙げられる。該（Ｅ）成分は（Ａ）〜（Ｃ）成分の合計１００質量部当り、０．０１〜５質量部の範囲で添加される。   The thixo component-imparting agent includes a silicone compound (organo) having any one of a polar group such as an organooxy group such as a hydroxy group (—OH group), an alkoxy group, an alkenyloxy group, and an aryloxy group, and an epoxy group. Organic resin components such as polysiloxane) and polyether can be used. Specifically, for example, organopolysiloxane having a silicon atom-bonded hydrogen atom represented by the following formula and an epoxy group (however, it does not contain a polar group such as an alkoxy group). The component (E) is added in the range of 0.01 to 5 parts by mass per 100 parts by mass in total of the components (A) to (C).

Figure 2009235265
Figure 2009235265

（上記式中、ｌ＝０〜１００の整数、ｍ＝１〜１００の整数、ｎは１〜１００の整数を示す。） (In the above formula, l is an integer from 0 to 100, m is an integer from 1 to 100, and n is an integer from 1 to 100.)

−（Ｆ）ヒュームドシリカ−
該成分は上述のように（Ｅ）成分のチクソ性付与剤と相互作用して本発明の組成物にチクソ性を付与する作用を示す。該ヒュームドシリカは、１次粒子径が５ｎｍ〜５０ｎｍであり、比表面積が１０〜５００ｍ２／ｇであることが好ましい。 -(F) Fumed silica-
As described above, the component interacts with the thixotropic agent of component (E) and exhibits the effect of imparting thixotropy to the composition of the present invention. The fumed silica preferably has a primary particle size of 5 nm to 50 nm and a specific surface area of 10 to 500 m 2 / g.

該（Ｆ）成分の添加量は（Ａ）〜（Ｅ）成分の合計１００質量部に対して１〜３０質量部、特に５〜２５質量部が好ましい。   The added amount of the component (F) is preferably 1 to 30 parts by mass, particularly 5 to 25 parts by mass with respect to 100 parts by mass in total of the components (A) to (E).

−その他の成分−
本発明の組成物には、上述した（Ａ）〜（Ｆ）成分の他に必要に応じて他の成分を任意的に添加することができる。例えば、接着助剤、着色剤、蛍光体、顔料、樹脂粉体等が挙げられる。 -Other ingredients-
In addition to the components (A) to (F) described above, other components can be optionally added to the composition of the present invention as necessary. For example, an adhesion assistant, a colorant, a phosphor, a pigment, a resin powder, and the like can be given.

・接着助剤：
本発明の組成物の基材に対する接着性を高めるために接着助剤を添加することが好ましい。接着助剤としては、例えば、一般式（３）で示されるオルガノオキシシリル変性イソシアヌレート化合物および／又はその加水分解縮合物（オルガノシロキサン変性イソシアヌレート化合物）が挙げられる。 ・ Adhesion aid:
In order to increase the adhesion of the composition of the present invention to the substrate, it is preferable to add an adhesion assistant. Examples of the adhesion assistant include an organooxysilyl-modified isocyanurate compound represented by the general formula (3) and / or a hydrolysis condensate thereof (organosiloxane-modified isocyanurate compound).

Figure 2009235265
Figure 2009235265

〔式中、Ｒ7は、下記式（４）： [Wherein R 7 represents the following formula (4):

Figure 2009235265
Figure 2009235265

（ここで、Ｒ8は水素原子又は炭素原子数１〜６の一価炭化水素基、ｓは１〜６、特に１〜４の整数である。）
で表される有機基、又は脂肪族不飽和結合を含有する一価炭化水素基であり、但しＲ7の少なくとも１個は式（４）で表される有機基である。〕 (Here, R 8 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and s is an integer of 1 to 6, particularly 1 to 4.)
Or a monovalent hydrocarbon group containing an aliphatic unsaturated bond, provided that at least one of R 7 is an organic group represented by the formula (4). ]

一般式（３）において、Ｒ7で表される脂肪族不飽和結合を含有する一価炭化水素基としては、ビニル基、アリル基、プロペニル基、イソプロペニル基、ブテニル基、イソブテニル基、ペンテニル基、ヘキセニル基等の炭素原子数２〜８、特に２〜６のアルケニル基、およびシクロヘキセニル基等が挙げられる。 In the general formula (3), the monovalent hydrocarbon group containing an aliphatic unsaturated bond represented by R 7 includes a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, and a pentenyl group. And an alkenyl group having 2 to 8 carbon atoms, particularly 2 to 6 carbon atoms, such as a hexenyl group, and a cyclohexenyl group.

また、Ｒ8で表される炭素原子数１〜６の一価炭化水素基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ヘキシル基等のアルキル基；シクロヘキシル基；ビニル基、アリル基、プロペニル基、イソプロペニル基、ブテニル基、イソブテニル基、ペンテニル基、ヘキセニル基等のアルケニル基；シクロヘキセニル基；フェニル基等のアリール基などの炭素原子数１〜８、特に１〜６の一価炭化水素基が挙げられ、好ましくはアルキル基である。 Examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms represented by R 8 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, and hexyl. Alkyl groups such as groups; cyclohexyl groups; alkenyl groups such as vinyl groups, allyl groups, propenyl groups, isopropenyl groups, butenyl groups, isobutenyl groups, pentenyl groups, hexenyl groups; cyclohexenyl groups; aryl groups such as phenyl groups, etc. Examples thereof include monovalent hydrocarbon groups having 1 to 8 carbon atoms, particularly 1 to 6 carbon atoms, and preferably an alkyl group.

上記一般式（３）のオルガノオキシシリル変性イソシアヌレート化合物の具体例として下記の式で表される化合物が挙げられる。   Specific examples of the organooxysilyl-modified isocyanurate compound represented by the general formula (3) include compounds represented by the following formula.

Figure 2009235265
Figure 2009235265

また、接着助剤として、ケイ素原子結合アルコキシ基を必須に含有すると共に、ケイ素原子結合水素原子、ケイ素原子結合アルケニル基、および／またはエポキシ基を有する有機ケイ素化合物（即ち、オルガノシランおよびオルガノポリシロキサン）が挙げられ、具体例として下記の式で表されるものがある。   Further, as an adhesion assistant, an organic silicon compound (ie, organosilane and organopolysiloxane) which essentially contains a silicon atom-bonded alkoxy group and has a silicon atom-bonded hydrogen atom, a silicon atom-bonded alkenyl group, and / or an epoxy group. And specific examples include those represented by the following formula.

Figure 2009235265
Figure 2009235265

（式中、ｍは０〜５０の整数であり、ｎは０〜５０の整数であり、但し、ｍ＋ｎが２〜５０、好ましくは４〜２０を満足する。） (In the formula, m is an integer of 0 to 50, and n is an integer of 0 to 50, provided that m + n satisfies 2 to 50, preferably 4 to 20.)

このような有機ケイ素化合物の内、得られる硬化物の接着性が特に優れている化合物としては、一分子中にケイ素原子結合アルコキシ基と、アルケニル基もしくはケイ素原子結合水素原子（ＳｉＨ基）とを有する有機ケイ素化合物であることが好ましい。   Among these organosilicon compounds, the resulting cured product has a particularly excellent adhesive property, and includes silicon-bonded alkoxy groups and alkenyl groups or silicon-bonded hydrogen atoms (SiH groups) in one molecule. It is preferable that it is an organosilicon compound.

該接着助剤の配合量は、（Ａ）成分、（Ｂ）成分および（Ｃ）成分の合計１００質量部に対して、通常１０質量部以下（即ち、０〜１０質量部）、好ましくは０．０１〜５質量部、より好ましくは０．１〜１質量部程度配合することができる。（Ｆ）成分の配合量が多すぎると硬化物の硬度や表面タック性に悪影響を及ぼすことがある。   The compounding amount of the adhesion assistant is usually 10 parts by mass or less (that is, 0 to 10 parts by mass), preferably 0 with respect to 100 parts by mass in total of the components (A), (B) and (C). .01 to 5 parts by mass, more preferably about 0.1 to 1 part by mass can be blended. If the amount of component (F) is too large, the hardness and surface tackiness of the cured product may be adversely affected.

−組成物の調製・使用−
本発明のシリコーンゴム組成物は、上述した各成分を所要量均一に混合することによって調製される。その際に、アセチレンアルコール等の硬化抑制剤を少量添加して１液型として調製することができる。また、２液型として調製する場合は、（Ｃ）成分と（Ｄ）成分とを同一パートに配すると脱水素反応が起こる危険があるので、これを避けるために別々のパートに配する必要がある。 -Preparation and use of the composition-
The silicone rubber composition of the present invention is prepared by uniformly mixing the above-described components in required amounts. At that time, a small amount of a curing inhibitor such as acetylene alcohol can be added to prepare a one-pack type. In addition, when preparing as a two-part type, there is a risk that a dehydrogenation reaction will occur if component (C) and component (D) are placed in the same part, so it is necessary to place them in separate parts to avoid this. is there.

こうして調製した本発明の組成物は厚さ１ｍｍの層状態で２０℃における波長４５０ｎｍの光の透過率が８０％以上であることが好ましく、８５％以上であることがより好ましい。透過率が厚さ１ｍｍで求められる理由は、ＬＥＤチップを被覆してレンズを形成したときのレンズの厚さが約１ｍｍであるからである。   The composition of the present invention thus prepared preferably has a light transmittance at a wavelength of 450 nm at 20 ° C. in a layer state of 1 mm thickness of 80% or more, more preferably 85% or more. The reason why the transmittance is required at a thickness of 1 mm is that when the lens is formed by covering the LED chip, the thickness of the lens is about 1 mm.

本発明の組成物は、必要により、例えば６０〜１５０℃に加熱することにより直ちに硬化させることができる。こうして得られる硬化物は高い透明性をもち且つパッケージ材料や金属基板に非常によく接着する。そのためＬＥＤを基板に装着して封止する際にＣＯＢ（チップオンボード）用封止剤として非常に優れている。またフォットダイオード、ＣＣＤ、ＣＭＯＳ等の汎用の半導体パッケージに広く使用することができる。   If necessary, the composition of the present invention can be cured immediately by heating to, for example, 60 to 150 ° C. The cured product thus obtained has high transparency and adheres very well to packaging materials and metal substrates. Therefore, it is very excellent as a COB (chip on board) sealant when an LED is mounted on a substrate and sealed. Further, it can be widely used for general-purpose semiconductor packages such as a photo diode, a CCD, and a CMOS.

なお、本発明のシリコーンゴム組成物において、（Ｆ）成分のヒュームドシリカ以外の（Ａ）〜（Ｅ）成分を均一に混合した混合物の屈折率は、ヒュームドシリカの屈折率と同一又は互いに近似したものであることが硬化物の透明性の点で重要である。具体的には、ヒュームドシリカを除く（Ａ）〜（Ｅ）成分を均一に混合した混合物の屈折率は1.42〜1.47の範囲内である必要がある。本発明の組成物の屈折率は硬化後も実質的に変わらず同じである。   In the silicone rubber composition of the present invention, the refractive index of the mixture obtained by uniformly mixing the components (A) to (E) other than the fumed silica of the component (F) is the same as or different from the refractive index of the fumed silica. The approximation is important in terms of the transparency of the cured product. Specifically, the refractive index of the mixture obtained by uniformly mixing the components (A) to (E) excluding fumed silica needs to be in the range of 1.42 to 1.47. The refractive index of the composition of the present invention remains substantially the same after curing.

本発明の組成物で光半導体チップを封止した光半導体装置において、光半導体チップが装着される支持構造体は特に限定されずパッケージでもよいし、パッケージレスの支持基板、例えばセラミック基板、シリコン基板、ガラスエポキシ基板、ベークライト（エポキシ樹脂）基板、金属基板等でもよい。   In the optical semiconductor device in which the optical semiconductor chip is sealed with the composition of the present invention, the support structure on which the optical semiconductor chip is mounted is not particularly limited and may be a package, or a packageless support substrate such as a ceramic substrate or a silicon substrate. A glass epoxy substrate, a bakelite (epoxy resin) substrate, a metal substrate or the like may be used.

次に本発明の実施例により本発明を具体的に説明する。以下の記載において、部は質量部を意味し、また粘度は２５℃での測定値を示す。Ｍｅはメチル基を、Ｐｈはフェニル基を、Ｖｉはビニル基をそれぞれ示す。   Next, the present invention will be described specifically by way of examples of the present invention. In the following description, “part” means “part by mass”, and “viscosity” indicates a value measured at 25 ° C. Me represents a methyl group, Ph represents a phenyl group, and Vi represents a vinyl group.

・実施例１
（ａ）末端がビニル基で封鎖された粘度１Ｐａ.ｓの下記式で示されるポリシロキサン（ＶＦ）50部、および、 Example 1
(A) 50 parts of a polysiloxane (VF) represented by the following formula having a viscosity of 1 Pa.s whose ends are blocked with vinyl groups, and

Figure 2009235265
Figure 2009235265

（ｂ）ＳｉＯ2単位５０モル％、（ＣＨ3）3ＳｉＯ0.5単位４２．５モル％およびＶｉMe2ＳｉＯ0.5単位７．５モル％からなる樹脂構造のビニルメチルシロキサン（ＶＭＱ）50部、
（ｃ）ＳｉＨ基量が前記（ａ）成分および（ｂ）成分中のビニル基の合計１モル当り１．５モルとなる量の下記式： (B) 50 parts by weight of vinylmethylsiloxane (VMQ) having a resin structure consisting of 50 mol% of SiO 2 units, 42.5 mol% of (CH 3 ) 3 SiO 0.5 units and 7.5 mol% of ViMe 2 SiO 0.5 units;
(C) The following formula in which the amount of SiH groups is 1.5 moles per mole of vinyl groups in the components (a) and (b):

Figure 2009235265
Figure 2009235265

で示されるオルガノハイドロジェンポリシロキサン4.9部、および
（ｄ）塩化白金酸のオクチルアルコール変性溶液０．０５部（（ａ）、（ｂ）、（ｃ）、（ｄ）、および後述の（ｅ）の各成分の合計に対して白金換算（質量）で約５ppm）に、
（ｆ）ヒュームドシリカ（製品名エロジル300をヘキサメチルジシラザンでシリルカ処理した）12部、
を十分に混合し3本ロールミルにて混練した。 4.9 parts of an organohydrogenpolysiloxane represented by the formula: (d) 0.05 part of an octyl alcohol-modified solution of chloroplatinic acid ((a), (b), (c), (d), and (e) described later) In terms of platinum (mass) of about 5ppm)
(F) 12 parts of fumed silica (product name Erosil 300 treated with hexamethyldisilazane in silylca)
Were sufficiently mixed and kneaded in a three-roll mill.

得られた混練物に、
（ｅ）下記のフローコントロール剤（チクソ性付与剤）0.5部と、下記の接着付与成分0.2部と添加し、組成物を調製した。 In the obtained kneaded product,
(E) 0.5 parts of the following flow control agent (thixotropic agent) and 0.2 parts of the following adhesion-imparting component were added to prepare a composition.

〔フローコントロール剤（チクソ性付与剤）〕     [Flow control agent (thixotropic agent)]

Figure 2009235265
Figure 2009235265

（式中、ｌは１０、ｍは８である。） (Wherein l is 10 and m is 8)

〔接着付与成分〕     (Adhesion imparting component)

Figure 2009235265
Figure 2009235265

図１はガラスエポキシ基板１にＬＥＤ素子２を搭載した光半導体装置３を示す断面図である。ＬＥＤ素子２と基板１上の電極４とはワイヤ５で接続されている。上記で得た組成物を、ＬＥＤ素子２を被覆するように塗布し、成形、硬化させて凸レンズ状の透明封止体６を形成した。この光半導体装置の下記の特性を測定し信頼性を評価した。   FIG. 1 is a sectional view showing an optical semiconductor device 3 in which an LED element 2 is mounted on a glass epoxy substrate 1. The LED element 2 and the electrode 4 on the substrate 1 are connected by a wire 5. The composition obtained above was applied so as to cover the LED element 2, molded and cured to form a convex lens-shaped transparent encapsulant 6. The reliability of the optical semiconductor device was evaluated by measuring the following characteristics.

・・外観：
得られた封止体の外観を肉眼で観察し、透明性を評価した。
・・機械的特性：
前記組成物を、150℃で４時間の加熱成型に供して硬化物を得、JIS K 6301に準拠して、硬度（Ａ型スプリング試験機を用いて測定）を測定した。 ··appearance:
The appearance of the obtained sealed body was observed with the naked eye, and the transparency was evaluated.
..Mechanical characteristics:
The composition was subjected to heat molding at 150 ° C. for 4 hours to obtain a cured product, and the hardness (measured using an A-type spring tester) was measured in accordance with JIS K 6301.

・・加湿リフロー試験：
ＭＳＬレベル２に準ずる加湿リフロー試験を実施した。即ち、光半導体装置（サンプル数５）を６０℃／９０％ＲＨの雰囲気下に放置して十分吸湿させた後に２６０℃のＩＲリフロー炉に所定回数（１回約６分）通した。クラック、剥離等の不良発生数を目視に評価した。比較のために、硬化直後の光半導体装置を吸湿させずに同様にＩＲリフロー工程に供した。 ..Humidification reflow test:
A humidified reflow test according to MSL level 2 was performed. That is, the optical semiconductor device (number of samples: 5) was left in an atmosphere of 60 ° C./90% RH to sufficiently absorb moisture, and then passed through a 260 ° C. IR reflow furnace a predetermined number of times (about 6 minutes once). The number of defects such as cracks and peeling was visually evaluated. For comparison, the optical semiconductor device immediately after curing was similarly subjected to an IR reflow process without absorbing moisture.

・・光透過率：
組成物を厚さ１ｍｍのシート状に成形、硬化させたものの波長４５０ｎｍの光に対する光透過率を２０℃において分光光度計により測定した。
・・輝度：
またＬＥＤに10mAの電流を印加しＬＥＤ各５個を発光させて大塚電子製ＬＥＤ光学特性モニター（商品名：LP-3400）により輝度を測定した。 ..Light transmittance:
The composition was molded into a 1 mm thick sheet and cured, and the light transmittance with respect to light having a wavelength of 450 nm was measured at 20 ° C. with a spectrophotometer.
··Luminance:
In addition, a current of 10 mA was applied to the LEDs to cause each of the five LEDs to emit light, and the luminance was measured with an LED optical characteristic monitor (trade name: LP-3400) manufactured by Otsuka Electronics.

・・組成物の屈折率：
ヒュームドシリカを配合しない以外は上記組成物と同様にして組成物を調製し、該組成物の屈折率をアッベ屈折率計により測定した。
・・組成物の流動性：
ガラス基板上に組成物１ｇをディスペンサーにより半球状の形状に滴下し、２５℃で３０分間放置後、１５０℃×３０分の条件で硬化した後、得られた硬化物の直径をノギスで測定することにより組成物の流動性（形状保持性）を評価した。 .. Refractive index of composition:
A composition was prepared in the same manner as the above composition except that fumed silica was not blended, and the refractive index of the composition was measured with an Abbe refractometer.
.. Fluidity of the composition:
1 g of the composition is dropped on a glass substrate into a hemispherical shape with a dispenser, left at 25 ° C. for 30 minutes, and cured under conditions of 150 ° C. × 30 minutes, and then the diameter of the resulting cured product is measured with a caliper. Thus, the fluidity (shape retention) of the composition was evaluated.

・実施例２
実施例１で用いた（ａ）成分の添加量を８７．５部に、（ｂ）成分の添加量を１２．５部に変え、実施例１で用いた（ｃ）成分のオルガノハイドロジェンポリシロキサンの添加量を２部（（ａ）、（ｂ）成分のビニル基の合計１モル当りのＳｉＨ基量１．５モルに相当する）に変更した以外は、実施例1と同様にして組成物を調製し、評価した。 Example 2
The amount of component (a) used in Example 1 was changed to 87.5 parts, the amount of component (b) added was changed to 12.5 parts, and the organohydrogen poly of component (c) used in Example 1 was changed. The composition was the same as in Example 1 except that the amount of siloxane added was changed to 2 parts (corresponding to 1.5 mol of SiH groups per 1 mol of total vinyl groups of components (a) and (b)). Articles were prepared and evaluated.

・実施例３
実施例１で（ａ）成分として用いたＶＦの代りに下記式で表されるビニルポリシロキサン50部を使用した以外は、実施例1と同様にして組成物を調製し評価した。 Example 3
A composition was prepared and evaluated in the same manner as in Example 1 except that 50 parts of vinylpolysiloxane represented by the following formula was used instead of VF used as the component (a) in Example 1.

Figure 2009235265
Figure 2009235265

・比較例１
実施例１で（ａ）成分として用いたＶＦの代りに下記式で表されるビニルポリシロキサン50部を添加した以外は、実施例１と同様にして組成物を調製し評価した。 Comparative example 1
A composition was prepared and evaluated in the same manner as in Example 1 except that 50 parts of vinylpolysiloxane represented by the following formula was added instead of VF used as the component (a) in Example 1.

Figure 2009235265
Figure 2009235265

・比較例２
実施例1で用いた（ｂ）成分を使用せず、（ａ）成分のビニルポリシロキサン５０部の代りに下記式： Comparative example 2
The component (b) used in Example 1 was not used, and instead of 50 parts of the vinyl polysiloxane of component (a), the following formula:

Figure 2009235265
Figure 2009235265

で表されるビニルポリシロキサン100部を使用し、さらに（ｃ）成分のオルガノハイドロジェンポリシロキサン4.9部の他に、下記式： In addition to 4.9 parts of component (c) organohydrogenpolysiloxane, the following formula:

Figure 2009235265
Figure 2009235265

で表されるハイドロジェンシロキサン2.5部を添加した以外は、実施例1と同様にして組成物を調製し評価した。 A composition was prepared and evaluated in the same manner as in Example 1 except that 2.5 parts of hydrogen siloxane represented by the formula:

これらの結果を表１および表２に示す。   These results are shown in Tables 1 and 2.

Figure 2009235265
Figure 2009235265

Figure 2009235265
Figure 2009235265

（注）
・数字は供試サンプル数５個中の不良発生数
・「２６０リフロー／ｎ回」はＩＲリフロー工程をｎ回（１回当り約６分）繰り返したことを示す。 (note)
Numbers indicate the number of failures in 5 test samples. “260 reflow / n times” indicates that the IR reflow process was repeated n times (about 6 minutes per time).

支持基板であるガラスエポキシ基板上に装着されたＬＥＤ素子を本発明の組成物を硬化させてなるレンズ状硬化物で封止した光半導体装置の縦断面図を示す。The longitudinal cross-sectional view of the optical semiconductor device which sealed the LED element mounted on the glass epoxy board | substrate which is a support substrate with the lens-shaped hardened | cured material formed by hardening the composition of this invention is shown.

符号の説明Explanation of symbols

１．ガラスエポキシ基板
２．ＬＥＤ素子
６．透明封止体 1. 1. Glass epoxy substrate LED element6. Transparent encapsulant

Claims (3)

（Ａ）一分子中に２個以上の脂肪族不飽和結合を有し、本質的に直鎖状であるオルガノポリシロキサン、
（Ｂ）一分子中に２個以上の脂肪族不飽和結合を有し、樹脂構造を有するオルガノポリシロキサン、
（Ｃ）一分子中にケイ素原子結合水素原子を２個以上有するオルガノハイドロジェンポリシロキサン、
（Ｄ）白金族金属系触媒、
（Ｅ）（Ｆ）成分以外のチクソ性付与剤、および
（Ｆ）ヒュームドシリカ
を含有してなり、かつ（Ａ）〜（Ｅ）成分からなる組成物の屈折率が1.42〜1.47であることを特徴とする硬化性シリコーンゴム組成物。 (A) an organopolysiloxane having two or more aliphatic unsaturated bonds in one molecule and being essentially linear;
(B) an organopolysiloxane having two or more aliphatic unsaturated bonds in one molecule and having a resin structure;
(C) an organohydrogenpolysiloxane having two or more silicon-bonded hydrogen atoms in one molecule;
(D) a platinum group metal catalyst,
(E) The thixotropic agent other than (F) component and (F) fumed silica are contained, and the refractive index of the composition comprising components (A) to (E) is 1.42 to 1.47. A curable silicone rubber composition characterized by the above. 請求項１に記載の組成物を硬化してなり、厚さ１ｍｍの層状態で２０℃における波長４５０ｎｍの光の透過率が８０％以上であることを特徴とするシリコーンゴム硬化物。   A cured silicone rubber obtained by curing the composition according to claim 1 and having a light transmittance of 450 nm at 20 ° C. in a layer state of 1 mm thickness of 80% or more. 光半導体チップと、該光半導体チップを被覆する、請求項１に記載の組成物を硬化してなるシリコーンゴム硬化物とを有する光半導体装置。   An optical semiconductor device comprising: an optical semiconductor chip; and a cured silicone rubber obtained by curing the composition according to claim 1 that covers the optical semiconductor chip.
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