JP2007002234A - Curable silicone rubber composition and semiconductor device - Google Patents

Curable silicone rubber composition and semiconductor device Download PDF

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JP2007002234A
JP2007002234A JP2006142331A JP2006142331A JP2007002234A JP 2007002234 A JP2007002234 A JP 2007002234A JP 2006142331 A JP2006142331 A JP 2006142331A JP 2006142331 A JP2006142331 A JP 2006142331A JP 2007002234 A JP2007002234 A JP 2007002234A
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silicone rubber
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rubber composition
curable silicone
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Tsutomu Kashiwagi
努 柏木
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Shin Etsu Chemical Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48151—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
    • H01L2224/48221—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
    • H01L2224/48245—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 metallic
    • H01L2224/48247—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 metallic connecting the wire to a bond pad of the item
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01019—Potassium [K]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/11—Device type
    • H01L2924/12—Passive devices, e.g. 2 terminal devices
    • H01L2924/1204—Optical Diode
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable silicone rubber composition giving a transparent cured product having sufficient adhesive strength to hardly adhesive materials for various packages composed of a thermoplastic material such as PPA and LCP and to electrodes made of a metal such as Ag, Au, Ni and Pd and provide a semiconductor device encapsulated with the cured material of the composition. <P>SOLUTION: The invention relates to a curable silicone rubber composition containing (A) an organopolysiloxane containing a vinyl group, (B) an organohydrogenpolysiloxane, (C) an aluminum metal-based polymerization catalyst, (D) a platinum group metal-based catalyst and (E) a tackifying component and a semiconductor device encapsulated with the cured material of the composition. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、付加硬化型のシリコーンゴム組成物に関するものであり、特にＰＰＡ（ポリフタル酸アミド樹脂）、液晶ポリマー（ＬＣＰ）等の熱可塑性プラスチック、及び銀、金等の電極貴金属などに接着が良好な硬化性シリコーンゴム組成物、及びその硬化物で封止された半導体装置に関する。   The present invention relates to an addition-curable silicone rubber composition, and particularly has good adhesion to thermoplastics such as PPA (polyphthalamide resin) and liquid crystal polymer (LCP), and electrode noble metals such as silver and gold. The present invention relates to a curable silicone rubber composition and a semiconductor device sealed with the cured product.

シリコーンゴム組成物は、耐候性、耐熱性等の特性や、硬度、伸び等のゴム的性質に優れた硬化物を形成することから種々の用途に使用されている。   Silicone rubber compositions are used in various applications because they form cured products having excellent properties such as weather resistance and heat resistance, and rubber properties such as hardness and elongation.

また、最近、耐熱性の優れた熱可塑性プラスチックとして、ＰＰＡ（ポリフタル酸アミド樹脂）、ＬＣＰ（液晶ポリマー）が各種パッケージの材料として検討されており、またフレーム及び電極としてＡｇ、Ａｕ、Ｎｉ、Ｐｄ等の金属が使われているが、これらは比較的接着が困難である。また、これら材料を用いて形成したパッケージ実装の半田条件は、鉛を含まない高温半田に変更されており、これらの高温ストレスや温度サイクル、高温高湿での保存により、パッケージとシリコーン樹脂の界面で容易に剥離が発生するといった不具合が多数生じている。   Recently, PPA (polyphthalamide resin) and LCP (liquid crystal polymer) have been studied as materials for various packages as thermoplastics having excellent heat resistance, and Ag, Au, Ni, Pd are used as frames and electrodes. Are used, but these are relatively difficult to bond. In addition, the soldering conditions for package mounting using these materials have been changed to high-temperature solder that does not contain lead, and the interface between the package and the silicone resin has been changed by these high-temperature stresses, temperature cycles, and storage at high temperatures and high humidity. Many problems such as easy peeling occur.

一般に、付加硬化型のシリコーンゴム組成物においては、各種シランカップリング剤の添加により接着の向上を図っているが、このような組成物は十分に反応が終了せず、厳しい条件の試験では剥離が発生してしまう。また、激しい反応を起こすと変色したり、透明にならず、光用途等には使用できなかった。   In general, in addition-curing type silicone rubber compositions, adhesion is improved by adding various silane coupling agents. However, such a composition does not sufficiently complete the reaction, and it is peeled off under severe conditions. Will occur. Moreover, when a violent reaction was caused, it was not discolored or transparent, and could not be used for light applications.

なお、本発明に関連する公知文献としては、下記のものがある。
特開２００３−１７４０５９号公報 特開２００２−３３８８３３号公報 In addition, as a well-known document relevant to this invention, there exist the following.
JP 2003-174059 A JP 2002-338833 A

本発明は、上記事情に鑑みなされたもので、接着が困難であるＰＰＡ（ポリフタル酸アミド樹脂）、ＬＣＰ（液晶ポリマー）等の熱可塑性プラスチックからなる各種パッケージの材料や、Ａｇ、Ａｕ、Ｎｉ、Ｐｄ等の金属からなる電極に対しても十分な接着強度を与え、かつ透明性を有する硬化物を与える硬化性シリコーンゴム組成物、及びこの組成物の硬化物により封止された半導体装置を提供することを目的とする。   The present invention has been made in view of the above circumstances, and various packaging materials made of thermoplastic plastics such as PPA (polyphthalamide resin) and LCP (liquid crystal polymer), which are difficult to adhere, Ag, Au, Ni, Provided are a curable silicone rubber composition that gives sufficient adhesive strength to an electrode made of a metal such as Pd, and gives a cured product having transparency, and a semiconductor device sealed with the cured product of this composition The purpose is to do.

本発明者は、上記目的を達成するために鋭意検討を重ねた結果、（Ａ）ビニル基含有オルガノポリシロキサン、（Ｂ）オルガノハイドロジェンポリシロキサン、（Ｃ）アルミニウム金属キレート触媒などのアルミニウム金属系重合触媒、（Ｄ）白金族金属系触媒、及び（Ｅ）接着付与成分として、例えばオルガノオキシシリル変性イソシアヌレート化合物及び／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）やエポキシ基含有シランカップリング剤などの公知の接着助剤を含有して成る硬化性シリコーンゴム組成物が、ＰＰＡ、ＬＣＰ等の熱可塑性プラスチックからなる各種パッケージの材料や、Ａｇ、Ａｕ、Ｎｉ、Ｐｄ等の金属からなる電極などの接着が困難である基材に対しても十分な接着強度を有し、透明性に優れた硬化物となり得、この組成物の硬化物により封止された半導体装置は、信頼性に優れることを見出し、本発明をなすに至った。   As a result of intensive studies to achieve the above object, the present inventor has found that (A) vinyl group-containing organopolysiloxane, (B) organohydrogenpolysiloxane, (C) aluminum metal chelate catalyst, etc. Polymerization catalyst, (D) platinum group metal catalyst, and (E) adhesion-imparting component, for example, organooxysilyl-modified isocyanurate compound and / or hydrolysis condensate thereof (organosiloxane-modified isocyanurate compound) or epoxy group-containing silane A curable silicone rubber composition containing a known adhesion aid such as a coupling agent is made of various package materials made of thermoplastic plastics such as PPA and LCP, and metals such as Ag, Au, Ni and Pd. It has sufficient adhesive strength even for substrates that are difficult to bond, such as electrodes. Can become a cured product excellent in sex, semiconductor device encapsulated with a cured product of the composition, it found that excellent reliability, the present invention has been accomplished.

従って、本発明は、
（Ａ）ビニル基含有オルガノポリシロキサン、
（Ｂ）オルガノハイドロジェンポリシロキサン、
（Ｃ）アルミニウム金属系重合触媒、
（Ｄ）白金族金属系触媒、
（Ｅ）接着付与成分
を含有して成ることを特徴とする硬化性シリコーンゴム組成物、及びこの組成物の硬化物で封止した半導体装置を提供する。 Therefore, the present invention
(A) vinyl group-containing organopolysiloxane,
(B) organohydrogenpolysiloxane,
(C) an aluminum metal polymerization catalyst,
(D) a platinum group metal catalyst,
(E) A curable silicone rubber composition comprising an adhesion-imparting component and a semiconductor device sealed with a cured product of the composition.

本発明の硬化性シリコーンゴム組成物は、今まで非常に接着困難であったＡｇ、ＰＰＡ等の基板に対して有効な接着性を付与し、この組成物の硬化物により封止された半導体装置は、厳しい信頼性試験に耐えうる半導体装置となり得る。   The curable silicone rubber composition of the present invention provides effective adhesion to a substrate such as Ag or PPA, which has been very difficult to bond, and is sealed with a cured product of the composition. Can be a semiconductor device that can withstand strict reliability tests.

（Ａ）ビニル基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ビニル基含有オルガノポリシロキサン（Ａ）としては、一分子中に２個以上の、ビニル基、アリル基等の炭素数２〜８、特に２〜６のアルケニル基で代表される脂肪族不飽和結合を有し、粘度が２５℃で１０〜１，０００，０００ｍＰａ・ｓ、特に１００〜１００，０００ｍＰａ・ｓの基本的に直鎖状のオルガノポリシロキサンを用いることが好ましい。この直鎖状オルガノポリシロキサンは、通常主鎖がジオルガノシロキサン単位の繰り返しからなり、分子鎖両末端がトリオルガノシロキシ基で封鎖されたものが一般的であるが、中でも下記一般式（１）で表される分子鎖両末端のケイ素原子上にそれぞれ１〜３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、上記でも述べた通り、２５℃における粘度が１０〜１，０００，０００ｍＰａ・ｓのものが作業性、硬化性などからより望ましいものである。なお、この直鎖状オルガノポリシロキサンは少量の分岐状構造（三官能性シロキサン単位）を分子鎖中に含有するものであってもよい。
ここで、本発明において、粘度は回転粘度計等により測定することができる。 (A) Vinyl group-containing organopolysiloxane As the vinyl group-containing organopolysiloxane (A) which is the base component of the present invention, 2 or more carbon atoms such as vinyl group and allyl group in one molecule are used. In particular, it has an aliphatic unsaturated bond represented by 2 to 6 alkenyl groups and has a viscosity of 10 to 1,000,000 mPa · s, particularly 100 to 100,000 mPa · s at 25 ° C. It is preferable to use the organopolysiloxane. This straight-chain organopolysiloxane usually has a main chain consisting of repeating diorganosiloxane units, and both ends of the molecular chain are blocked with a triorganosiloxy group. Of these, the following general formula (1) A linear organopolysiloxane having 1 to 3 alkenyl groups on the silicon atoms at both ends of the molecular chain, as described above, having a viscosity at 25 ° C. of 10 to 1,000,000 mPa · s is more desirable from the viewpoint of workability and curability. The linear organopolysiloxane may contain a small amount of a branched structure (trifunctional siloxane unit) in the molecular chain.
Here, in the present invention, the viscosity can be measured by a rotational viscometer or the like.

Figure 2007002234
（式中、Ｒ1は互いに同一又は異種の非置換もしくは置換一価炭化水素基、Ｒ2は互いに同一又は異種の脂肪族不飽和結合を有さない非置換もしくは置換一価炭化水素基であり、ｘ，ｙは０又は正の整数であり、ｘ＋ｙはこのオルガノポリシロキサンの２５℃の粘度を１０〜１，０００，０００ｍＰａ・ｓとする数である。）
Figure 2007002234
 Wherein R 1 is the same or different unsubstituted or substituted monovalent hydrocarbon group, and R 2 is the same or different unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond. , X, y is 0 or a positive integer, and x + y is a number that makes the viscosity of this organopolysiloxane at 25 ° C. 10 to 1,000,000 mPa · s.)

ここで、Ｒ1の一価炭化水素基としては、炭素数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、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、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、ヘキセニル基、シクロヘキセニル基、オクテニル基等のアルケニル基や、これらの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。
また、Ｒ2の一価炭化水素基としても、炭素数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、但しアルケニル基は含まない。
ｘ，ｙは、一般的には０＜ｘ＋ｙ≦１０，０００を満足する０又は正の整数であり、好ましくは５≦ｘ＋ｙ≦２，０００で、０＜ｘ／（ｘ＋ｙ）≦０．２を満足する整数である。 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, and an isobutyl group. Group, alkyl group such as tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, decyl group, aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group, benzyl group , Aralkyl groups such as phenylethyl group and phenylpropyl group, alkenyl groups such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, hexenyl group, cyclohexenyl group and octenyl group, and hydrogen atoms of these groups Are substituted with a halogen atom such as fluorine, bromine or chlorine, a cyano group, etc., such as a chloromethyl group, Roropuropiru group, bromoethyl group, and a halogen-substituted alkyl group or cyanoethyl group such trifluoropropyl group.
Further, the monovalent hydrocarbon group for R 2 is preferably one having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, and the same examples as the specific examples for R 1 described above can be exemplified, but an alkenyl group is not included.
x and y are generally 0 or a positive integer satisfying 0 <x + y ≦ 10,000, preferably 5 ≦ x + y ≦ 2,000, and 0 <x / (x + y) ≦ 0.2. A satisfying integer.

（Ａ）成分として具体的には、下記のものを例示することができる。

Figure 2007002234
（上記式において、ｔはそれぞれ独立に８〜２，０００の整数である。） Specific examples of the component (A) include the following.
Figure 2007002234
 (In the above formula, t is each independently an integer of 8 to 2,000.)

Figure 2007002234
Figure 2007002234

Figure 2007002234
Figure 2007002234

Figure 2007002234
（上記式において、ｘ，ｙは上述した通りである。）
Figure 2007002234
 (In the above formula, x and y are as described above.)

また、本発明においては、レジン構造のオルガノポリシロキサンを上記のオルガノポリシロキサンと併用して使用することができる。このレジン構造（即ち、三次元網状構造）のオルガノポリシロキサンは、ＳｉＯ2単位、Ｒ3 kＲ4 pＳｉＯ0.5単位及びＲ3 qＲ4 rＳｉＯ0.5単位からなるレジン構造のオルガノポリシロキサン（但し、上記式において、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、ｋは２又は３、ｐは０又は１で、ｋ＋ｐ＝３、ｑは０又は１、ｒは２又は３で、ｑ＋ｒ＝３である。）であることが好ましい。なお、Ｒ4の一価炭化水素基としては、上記Ｒ2と同様の炭素数１〜１０、特に１〜６のものが挙げられる。 In the present invention, an organopolysiloxane having a resin structure can be used in combination with the above organopolysiloxane. The organopolysiloxane having this resin structure (that is, a three-dimensional network structure) is an organopolysiloxane having a resin structure consisting of SiO 2 units, R 3 k R 4 p SiO 0.5 units and R 3 q R 4 r SiO 0.5 units (provided that In the above formula, R 3 is a vinyl group or an allyl group, R 4 is a monovalent hydrocarbon group not containing an aliphatic unsaturated bond, k is 2 or 3, p is 0 or 1, and k + p = 3, q is preferably 0 or 1, r is 2 or 3, and q + r = 3). Examples of the monovalent hydrocarbon group for 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、レジン構造のオルガノポリシロキサンは、ＳｉＯ2単位をａ単位、Ｒ3 kＲ4 pＳｉＯ0.5単位をｂ単位、Ｒ3 qＲ4 rＳｉＯ0.5単位をｃ単位とした場合、これら単位割合は、モル比として、
（ｂ＋ｃ）／ａ＝０．３〜３、特に０．７〜１
ｃ／ａ＝０．０１〜１、特に０．０７〜０．１５
であることが好ましく、またこのオルガノポリシロキサンは、ＧＰＣによるポリスチレン換算の重量平均分子量が５００〜１０，０００の範囲であるものが好適である。 Here, organopolysiloxane resin structure, when the SiO 2 unit a unit, R 3 k R 4 p SiO 0.5 units b units, the R 3 q R 4 r SiO 0.5 units and c units, these units ratio Is the molar ratio
(B + c) /a=0.3-3, especially 0.7-1
c / a = 0.01 to 1, especially 0.07 to 0.15
The organopolysiloxane preferably has a polystyrene-reduced weight average molecular weight in the range of 500 to 10,000 by GPC.

なお、このレジン構造のオルガノポリシロキサンは、上記ａ単位、ｂ単位、ｃ単位に加えて、更に、二官能性シロキサン単位や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）を本発明の目的を損なわない範囲で少量含有するものであってもよい。   In addition to the a unit, b unit, and c unit, the resin-structured organopolysiloxane further includes a bifunctional siloxane unit and a trifunctional siloxane unit (that is, an organosilsesquioxane unit). It may be contained in a small amount within a range that does not impair the purpose.

このようなレジン構造のオルガノポリシロキサンは、各単位源となる化合物を、上記モル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合成することができる。   Such an organopolysiloxane having a resin structure can be easily synthesized by combining the compounds serving as the unit sources so as to have the above molar ratio, and performing cohydrolysis in the presence of an acid, for example.

ここで、前記ａ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, examples of the a unit source include sodium silicate, alkyl silicate, polyalkyl silicate, silicon tetrachloride and the like.

また、ｂ単位源としては、下記のものを例示することができる。

Figure 2007002234
Moreover, as a b unit source, the following can be illustrated.
Figure 2007002234

更に、ｃ単位源としては、下記のものを例示することができる。

Figure 2007002234
Further, examples of the c unit source include the following.
Figure 2007002234

上記レジン構造のオルガノポリシロキサンは、硬化物の物理的強度及び表面のタック性を改善するために配合されるものであり、（Ａ）成分中、２０〜７０質量％の量で配合されることが好ましく、より好ましくは３０〜６０質量％の量で配合される。レジン構造のオルガノポリシロキサンの配合量が少なすぎると、上記効果が十分達成されない場合があり、多すぎると、組成物の粘度が著しく高くなったり、硬化物にクラックが発生し易くなる場合がある。   The above-mentioned organopolysiloxane having a resin structure is blended in order to improve the physical strength and surface tackiness of the cured product, and is blended in an amount of 20 to 70% by mass in the component (A). Is more preferable, and more preferably 30 to 60% by mass. If the amount of the resin-structured organopolysiloxane is too small, the above effect may not be sufficiently achieved. If the amount is too large, the viscosity of the composition may be remarkably increased or cracks may easily occur in the cured product. .

（Ｂ）オルガノハイドロジェンポリシロキサン
（Ｂ）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）成分中のビニル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個以上有するものであればいずれのものでもよいが、特に下記平均組成式（２）
Ｈa（Ｒ5）bＳｉＯ(4-a-b)/2 （２）
（式中、Ｒ5は脂肪族不飽和結合を含有しない同一又は異種の非置換もしくは置換の一価炭化水素基であり、ａ及びｂは、０．００１≦ａ＜２、０．７≦ｂ≦２、かつ０．８≦ａ＋ｂ≦３を満たす数である。）
で表され、一分子中にケイ素原子に結合した水素原子（ＳｉＨ基）を少なくとも２個（通常２〜３００個）、好ましくは３個以上（例えば３〜２００個）有するものが好適に用いられる。 (B) Organohydrogenpolysiloxane The (B) component organohydrogenpolysiloxane acts as a crosslinking agent, and the SiH group in the component and the vinyl group in the component (A) undergo an addition reaction. To form a cured product. The organohydrogenpolysiloxane may be any one as long as it has two or more hydrogen atoms (that is, SiH groups) bonded to a silicon atom in one molecule. In particular, the following average composition formula (2)
H a (R 5 ) b SiO (4-ab) / 2 (2)
Wherein R 5 is the same or different unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond, and a and b are 0.001 ≦ a <2, 0.7 ≦ b ≦ 2 and 0.8 ≦ a + b ≦ 3.)
And having at least 2 (usually 2 to 300), preferably 3 or more (for example, 3 to 200) hydrogen atoms bonded to silicon atoms in one molecule is suitably used. .

ここで、上記式（２）中のＲ5は、脂肪族不飽和結合を含有しない同一又は異種の非置換もしくは置換の炭素数１〜１０、特に炭素数１〜７の一価炭化水素基であることが好ましく、例えば、メチル基等の低級アルキル基、フェニル基等のアリール基など、前述の一般式（１）の置換基Ｒ2で例示したものが挙げられる。また、ａ及びｂは、０．００１≦ａ＜２、０．７≦ｂ≦２、かつ０．８≦ａ＋ｂ≦３を満たす数であり、好ましくは０．０５≦ａ≦１、０．８≦ｂ≦２、かつ１≦ａ＋ｂ≦２．７となる数である。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、分子の末端でも途中でもよい。 Here, R 5 in the above formula (2) is the same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 7 carbon atoms, which does not contain an aliphatic unsaturated bond. Preferably, there may be mentioned, for example, those exemplified for the substituent R 2 in the general formula (1), such as a lower alkyl group such as a methyl group and an aryl group such as a phenyl group. A and b are numbers satisfying 0.001 ≦ a <2, 0.7 ≦ b ≦ 2, and 0.8 ≦ a + b ≦ 3, preferably 0.05 ≦ a ≦ 1, 0.8 ≦ b ≦ 2 and 1 ≦ a + b ≦ 2.7. The position of the hydrogen atom bonded to the silicon atom is not particularly limited, and may be at the end of the molecule or in the middle.

上記オルガノハイドロジェンポリシロキサンとしては、トリス（ジメチルハイドロジェンシロキシ）メチルシラン、トリス（ジメチルハイドロジェンシロキシ）フェニルシラン、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、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、（ＣＨ3）2ＨＳｉＯ1/2単位とＳｉＯ4/2単位とから成る共重合体、（ＣＨ3）2ＨＳｉＯ1/2単位とＳｉＯ4/2単位と（Ｃ6Ｈ5）ＳｉＯ3/2単位とから成る共重合体などが挙げられる。 Examples of the organohydrogenpolysiloxane include tris (dimethylhydrogensiloxy) methylsilane, tris (dimethylhydrogensiloxy) phenylsilane, 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetra. Methylcyclotetrasiloxane, both ends trimethylsiloxy-blocked methylhydrogenpolysiloxane, both ends trimethylsiloxy-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, both ends dimethylhydrogensiloxy-blocked dimethylpolysiloxane, both ends dimethylhydro Gensiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, both ends trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane copolymer , Both terminals blocked with trimethylsiloxy groups methylhydrogensiloxane-diphenylsiloxane-dimethylsiloxane copolymers, copolymers consisting of (CH 3) 2 HSiO 1/2 units and SiO 4/2 units, (CH 3) 2 HSiO Examples thereof include copolymers comprising 1/2 units, SiO 4/2 units, and (C 6 H 5 ) SiO 3/2 units.

また、下記構造で示されるような化合物も使用することができる。

Figure 2007002234
Moreover, a compound as shown by the following structure can also be used.
Figure 2007002234

このオルガノハイドロジェンポリシロキサンの分子構造は、直鎖状、環状、分岐状、三次元網状構造のいずれであってもよいが、一分子中のケイ素原子の数（又は重合度）は３〜１，０００、特に３〜３００程度のものを使用することができる。   The molecular structure of the organohydrogenpolysiloxane may be any of linear, cyclic, branched, and three-dimensional network structures, but the number of silicon atoms in one molecule (or the degree of polymerization) is 3 to 1. , Especially about 3 to 300 can be used.

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.

なお、こ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）成分の硬化有効量であり、特にそのＳｉＨ基が（Ａ）成分中のアルケニル基（例えばビニル基）の合計量当たり０．１〜４．０、特に好ましくは１．０〜３．０、更に好ましくは１．２〜２．８のモル比で使用されることが好ましい。０．１未満では硬化反応が進行せず、シリコーンゴム硬化物を得ることが困難となる場合があり、４．０を超えると、未反応のＳｉＨ基が硬化物中に多量に残存するおそれがあるため、ゴム物性が経時的に変化する原因となる場合が生じる。   In addition, the compounding amount of the organohydrogenpolysiloxane is an effective curing amount of the component (A), and in particular, the SiH group is 0.1 per total amount of alkenyl groups (for example, vinyl groups) in the component (A). It is preferably used in a molar ratio of ˜4.0, particularly preferably 1.0 to 3.0, and more preferably 1.2 to 2.8. If it is less than 0.1, the curing reaction does not proceed, and it may be difficult to obtain a cured silicone rubber. If it exceeds 4.0, a large amount of unreacted SiH groups may remain in the cured product. For this reason, the rubber physical properties may change over time.

（Ｃ）アルミニウム金属系重合触媒
本発明の（Ｃ）成分であるアルミニウム金属系重合触媒は、接着付与成分中のエポキシ基、アルコキシ基等の後述する接着付与成分の官能性基を重合させるものであり、アルミニウム金属系重合触媒として、具体的には、三水酸化アルミニウム、あるいは、アルミニウムアルコラート、アルミニウムアシレート、アルミニウムアシレートの塩、アルミノシロキシ化合物及びアルミニウム金属キレート化合物からなる群から選択される有機アルミニウム化合物が例示されるが、特にアルミニウム金属キレート化合物が好ましい。 (C) Aluminum metal-based polymerization catalyst The aluminum metal-based polymerization catalyst which is the component (C) of the present invention polymerizes the functional groups of the adhesion-imparting component described later such as epoxy group and alkoxy group in the adhesion-imparting component. Yes, as the aluminum metal-based polymerization catalyst, specifically, aluminum trihydroxide, or an organic alcohol selected from the group consisting of aluminum alcoholate, aluminum acylate, aluminum acylate salt, aluminosiloxy compound and aluminum metal chelate compound Although an aluminum compound is illustrated, an aluminum metal chelate compound is particularly preferable.

このようなアルミニウム金属キレート化合物からなる触媒としては、市販品を使用することができ、例えば、ＡＣＳ、ケロープＥＢ−２（いずれも、ホープ製薬（株）製商品名）等が挙げられる。   As the catalyst comprising such an aluminum metal chelate compound, a commercially available product can be used, and examples thereof include ACS and Kelope EB-2 (both are trade names manufactured by Hope Pharmaceutical Co., Ltd.).

このアルミニウム金属系重合触媒の配合量は触媒量であり、この触媒量としては（Ａ）成分と（Ｅ）成分との合計に対して０．００５〜１０質量％、より望ましくは０．０５〜２質量％である。０．００５質量％未満では十分な効果が得られない場合があり、１０質量％を超えると、樹脂の硬化特性（硬度、外観等）に影響を及ぼす場合がある。   The compounding amount of the aluminum metal-based polymerization catalyst is a catalyst amount, and the catalyst amount is 0.005 to 10% by mass, more preferably 0.05 to 2% by mass. If the amount is less than 0.005% by mass, sufficient effects may not be obtained. If the amount exceeds 10% by mass, the curing characteristics (hardness, appearance, etc.) of the resin may be affected.

（Ｄ）白金族金属系触媒
本発明に用いられる（Ｄ）成分の白金族金属系触媒は、本発明組成物の付加硬化反応を生じさせるために配合されるものであり、この触媒としては、白金系、パラジウム系、ロジウム系等のものがあるが、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を例示することができ、これらは単独でも、２種以上の組み合わせでも使用することができる。 (D) used in the platinum group metal catalyst present invention component (D) a platinum group metal-based catalysts, which are compounded for inducing addition cure reaction of the present composition, as the catalyst, There are platinum type, palladium type, rhodium type, etc., but from the viewpoint of cost etc., platinum type such as platinum, platinum black, chloroplatinic acid, for example, 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 hydrocarbons such as olefins, alcohol or vinyl A complex with a group-containing organopolysiloxane can be exemplified, and these can be used alone or in combination of two or more.

これらの触媒成分の配合量は、所謂触媒量でよく、通常、前記（Ａ），（Ｂ）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 these catalyst components may be a so-called catalyst amount, and is usually 0.1 to 1,000 ppm in terms of platinum group metal (mass) relative to the total amount of the components (A) and (B), preferably Used in the range of 0.5 to 200 ppm.

（Ｅ）接着付与成分
本発明の組成物には、これを硬化して得られる硬化物の接着性を向上させるため、（Ｅ）成分として接着付与成分を添加配合する。（Ｅ）成分として、具体的には、一分子中にケイ素原子に結合した水素原子（ＳｉＨ基）、ケイ素原子に結合したアルケニル基（例えばＳｉ−ＣＨ＝ＣＨ2基）、アルコキシシリル基（例えばトリメトキシシリル基）、エポキシ基（例えばグリシドキシプロピル基、３，４−エポキシシクロヘキシルエチル基）から選ばれる官能性基を少なくとも２種、好ましくは２又は３種含有する直鎖状又は環状のケイ素原子数４〜５０個、好ましくは４〜２０個程度のオルガノシロキサンオリゴマーが挙げられる。 (E) Adhesion imparting component In order to improve the adhesiveness of the hardened | cured material obtained by hardening | curing this to the composition of this invention, an adhesion imparting component is added and mix | blended as (E) component. (E) as component, specifically one hydrogen atom bonded to a silicon atom in the molecule (SiH group), alkenyl groups bonded to silicon atom (e.g., Si-CH = CH 2 groups), alkoxysilyl groups (e.g. A linear or cyclic group containing at least two, preferably two or three functional groups selected from a trimethoxysilyl group) and an epoxy group (for example, glycidoxypropyl group, 3,4-epoxycyclohexylethyl group) Examples thereof include organosiloxane oligomers having 4 to 50 silicon atoms, preferably about 4 to 20 silicon atoms.

また、これに加えて下記一般式（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及び／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）が好適に使用される。   In addition to this, an organooxysilyl-modified isocyanurate compound represented by the following general formula (3) and / or a hydrolysis condensate thereof (organosiloxane-modified isocyanurate compound) is preferably used.

Figure 2007002234
（式中、Ｒ6は、下記式（４）
Figure 2007002234
 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るが、少なくとも１個は式（４）の有機基であり、Ｒ7は水素原子又は炭素数１〜６の一価炭化水素基、ｓは１〜６、特に１〜４の整数である。）
Figure 2007002234
 (Wherein R 6 represents the following formula (4)
Figure 2007002234
 Or a monovalent hydrocarbon group containing an aliphatic unsaturated bond, at least one of which is an organic group of the formula (4), and R 7 is a hydrogen atom or having 1 to 6 carbon atoms. A monovalent hydrocarbon group, s is an integer of 1-6, especially 1-4. )

この場合、Ｒ6の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、シクロヘキセニル基等の炭素数２〜８、特に２〜６のアルケニル基などが挙げられる。また、Ｒ7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、シクロヘキシル基等のアルキル基、ビニル基、アリル基、プロペニル基、イソプロペニル基等の上記Ｒ6として例示したものと同様のアルケニル基、フェニル基等のアリール基などの炭素数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。 In this case, the monovalent hydrocarbon group containing an aliphatic unsaturated bond represented by R 6 includes a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentenyl group, a hexenyl group, and a cyclohexenyl group. And alkenyl groups having 2 to 8 carbon atoms, particularly 2 to 6 carbon atoms. Examples of the monovalent hydrocarbon group for R 7 include methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, isobutyl groups, tert-butyl groups, pentyl groups, hexyl groups, cyclohexyl groups, and other alkyl groups, vinyl A monovalent hydrocarbon group having 1 to 8 carbon atoms, particularly 1 to 6 carbon atoms such as an alkenyl group and an aryl group such as a phenyl group, which are the same as those exemplified as R 6 such as a group, an allyl group, a propenyl group and an isopropenyl group. And preferably an alkyl group.

（Ｅ）成分の接着付与成分としては、下記式に示される化合物が例示される。

Figure 2007002234
（式中、ｇ，ｈはそれぞれｇ＋ｈが２〜５０、好ましくは４〜２０を満足する正の整数である。） (E) As an adhesion | attachment provision component of a component, the compound shown by a following formula is illustrated.
Figure 2007002234
 (In the formula, g and h are positive integers each satisfying g + h of 2 to 50, preferably 4 to 20.)

Figure 2007002234
Figure 2007002234

Figure 2007002234
Figure 2007002234

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）を有する有機ケイ素化合物である。   Among such organosilicon compounds, compounds having particularly excellent adhesion of the resulting cured product include organic compounds having silicon-bonded alkoxy groups and alkenyl groups or silicon-bonded hydrogen atoms (SiH groups) in one molecule. It is a silicon compound.

本発明において、接着付与成分の配合量は、（Ａ）成分１００質量部に対して、通常１０質量部以下の有効量（例えば、０．０１〜１０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。（Ｅ）成分の配合量が少なすぎると基材に対する接着性に劣るが、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場合がある。   In the present invention, the compounding amount of the adhesion-imparting component is usually an effective amount of 10 parts by mass or less (for example, 0.01 to 10 parts by mass), preferably 0.01 to 5 parts per 100 parts by mass of the component (A). About 0.1 to 1 part by mass, more preferably about 0.1 to 1 part by mass can be blended. If the amount of component (E) is too small, the adhesion to the substrate is poor, but if too large, the hardness and surface tackiness of the cured product may be adversely affected.

本発明の組成物には、上述した（Ａ）〜（Ｅ）成分以外にも、必要に応じて、それ自体公知の各種の添加剤を配合することができる。例えば、ヒュームドシリカ、ヒュームド二酸化チタン等の補強性無機充填剤、炭酸カルシウム、ケイ酸カルシウム、二酸化チタン、酸化第二鉄、カーボンブラック、酸化亜鉛等の非補強性無機充填剤を、本発明の目的を損なわない範囲で適宜配合することができる。   In addition to the components (A) to (E) described above, various additives known per se can be blended with the composition of the present invention as necessary. For example, reinforcing inorganic fillers such as fumed silica and fumed titanium dioxide, non-reinforcing inorganic fillers such as calcium carbonate, calcium silicate, titanium dioxide, ferric oxide, carbon black, and zinc oxide are used in the present invention. It can mix | blend suitably in the range which does not impair the objective.

本発明のシリコーンゴム組成物は、上述した各成分を均一に混合することによって調製されるが、通常は、硬化が進行しないように２液に分けて保存され、使用時に２液を混合して硬化を行う。勿論、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液として用いることもできる。また、２液混合タイプでは（Ｂ）成分と（Ｃ）成分の同一配合は脱水素反応の危険性から避ける必要がある。
なお、得られたシリコーンゴム組成物の回転粘度計により測定した２５℃における粘度は、１００〜１０，０００，０００ｍＰａ・ｓ、特には３００〜５００，０００ｍＰａ・ｓ程度が好ましい。 The silicone rubber composition of the present invention is prepared by uniformly mixing the above-described components. Usually, the silicone rubber composition is stored in two liquids so that curing does not proceed. Curing is performed. Of course, a small amount of a curing inhibitor such as acetylene alcohol can be added and used as one liquid. In the two-component mixed type, it is necessary to avoid the same combination of the component (B) and the component (C) from the risk of dehydrogenation reaction.
In addition, as for the viscosity in 25 degreeC measured with the rotational viscometer of the obtained silicone rubber composition, about 100-10,000,000 mPa * s is preferable especially about 300-500,000 mPa * s.

この組成物は、必要によって加熱することにより直ちに硬化して、高い透明性をもち且つＬＣＰ等のパッケージ材料や金属基板に非常によく接着するため、ＬＥＤ、フォットダイオード、ＣＣＤ、ＣＭＯＳ等の半導体パッケージに汎用用途として広く使用することができる。
なお、硬化条件は特に制限されるものではないが、通常、４０〜２５０℃、好ましくは６０〜２００℃で５分〜１０時間、好ましくは３０分〜６時間程度で硬化することができる。 This composition is cured immediately by heating if necessary, has high transparency, and adheres very well to package materials such as LCP and metal substrates, so that semiconductor packages such as LEDs, photodiodes, CCDs, CMOSs, etc. It can be widely used as a general purpose application.
The curing conditions are not particularly limited, but are usually 40 to 250 ° C., preferably 60 to 200 ° C. for 5 minutes to 10 hours, preferably about 30 minutes to 6 hours.

以下、実施例及び比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。なお、下記の例において、部は質量部を示し、Ｖｉはビニル基を示す。   EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, in the following example, a part shows a mass part and Vi shows a vinyl group.

［実施例１］
下記式（ｉ）

Figure 2007002234
で示されるポリシロキサン（ＶＦ）５０部に、ＳｉＯ2単位５０モル％、（ＣＨ3）3ＳｉＯ0.5単位４２．５モル％及びＶｉ3ＳｉＯ0.5単位７．５モル％からなるレジン構造のビニルメチルシロキサン（ＶＭＱ）５０部、ＳｉＨ基量が前記ＶＦ及びＶＭＱ成分中のビニル基の合計量当り１．５倍モルとなる量の下記式（ｉｉ）
Figure 2007002234
 で示されるオルガノハイドロジェンポリシロキサン、塩化白金酸のオクチルアルコール変性溶液（白金濃度２質量％）０．０５部、アルミニウム金属キレート触媒としてホープ製薬製 ＡＣＳ０．１部、及び下記式
Figure 2007002234
 で示される接着付与成分１部を混合し、シリコーンゴム組成物を調製した。
この組成物を、１５０℃／４時間にて加熱成型して硬化物を形成し、外観を目視にて観察した。また、ＪＩＳ Ｋ ６３０１に準拠して、引張強度、硬度（Ａ型スプリング試験機を用いて測定）及び伸び率を測定した。
更に、下記に示す方法により、ＰＰＡ剪断接着力及び凝集破壊率を測定した。これらの結果を表１に示した。 [Example 1]
Formula (i) below
Figure 2007002234
 And 50 parts by weight of polysiloxane (VF) represented by the following formula: Resin-structure vinylmethyl consisting of 50 mol% of SiO 2 units, 42.5 mol% of (CH 3 ) 3 SiO 0.5 units and 7.5 mol% of Vi 3 SiO 0.5 units 50 parts by weight of siloxane (VMQ), and the amount of SiH group is 1.5 times mol per total amount of vinyl groups in the VF and VMQ components.
Figure 2007002234
 An organohydrogenpolysiloxane represented by the formula: 0.05 part of an octyl alcohol-modified solution of chloroplatinic acid (platinum concentration: 2% by mass); 0.1 part of ACS as an aluminum metal chelate catalyst;
Figure 2007002234
 A silicone rubber composition was prepared by mixing 1 part of an adhesion-imparting component represented by the formula (1).
This composition was heat-molded at 150 ° C. for 4 hours to form a cured product, and the appearance was visually observed. Moreover, based on JISK6301, the tensile strength, hardness (measured using an A-type spring tester), and elongation were measured.
Furthermore, the PPA shear adhesive force and the cohesive failure rate were measured by the method described below. These results are shown in Table 1.

［ＰＰＡ剪断接着強さの測定］
図１に示すように、幅２５ｍｍのＰＰＡ（ポリフタル酸アミド樹脂）製の基材片１及び２それぞれの一方の端部を、上記で調製した硬化性組成物からなる厚さ１ｍｍの組成物層３を間に挟んで長さ１０ｍｍにわたって重ね、１５０℃で４時間加熱して組成物層３を硬化させた。このようにして作製した試験体を室温にて１２時間以上放置した後、この試験体の両端４と５を矢印の方向に引っ張り試験機で引っ張ることにより、引っ張り剪断接着強さを測定した。 [Measurement of PPA shear bond strength]
As shown in FIG. 1, a composition layer having a thickness of 1 mm made of the curable composition prepared above at one end of each of base pieces 1 and 2 made of PPA (polyphthalamide resin) having a width of 25 mm. The composition layer 3 was cured by being overlapped over a length of 10 mm with 3 interposed therebetween and heated at 150 ° C. for 4 hours. The test specimen prepared in this manner was allowed to stand at room temperature for 12 hours or more, and then the tensile shear adhesive strength was measured by pulling both ends 4 and 5 of the test specimen in the direction of the arrow with a tensile tester.

［凝集破壊率の測定］
上記剪断接着強さを測定した際の試験体の破断面について、破断面全体の面積に対して凝集破壊（即ち、ＰＰＡとシリコーンゴムが界面剥離せずにシリコーンゴム自体が破断）した部分の面積の比率（百分率）を凝集破壊率として評価した。 [Measurement of cohesive failure rate]
Regarding the fracture surface of the specimen when the shear bond strength was measured, the area of the portion where the cohesive failure (that is, the silicone rubber itself fractured without interfacial peeling between the PPA and the silicone rubber) with respect to the entire fracture surface area The ratio (percentage) of was evaluated as the cohesive failure rate.

また、図２で示されるように、ダミーパッケージ（商標名 アモデル）にシリコーンゴム組成物を封入し、１５０℃／４時間の条件で硬化し、ＭＳＬレベル２に準じて加湿リフロー試験を実施した。
即ち、図２において、６はＰＰＡ（ポリフタル酸アミド樹脂）からなるパッケージ、８はこのパッケージ６内に収容された銀メッキされたリードフレーム、９はチップで、リードフレーム８とチップ９とはワイヤー１０によって接続されており、上記パッケージ６内にシリコーンゴム組成物を封入、硬化して上記チップ９及びワイヤー１０を封止した。 Further, as shown in FIG. 2, a silicone rubber composition was enclosed in a dummy package (trade name: Amodel), cured under conditions of 150 ° C./4 hours, and a humidified reflow test was performed according to MSL level 2.
That is, in FIG. 2, 6 is a package made of PPA (polyphthalamide resin), 8 is a silver-plated lead frame housed in the package 6, 9 is a chip, and the lead frame 8 and the chip 9 are wires. 10, the silicone rubber composition was sealed in the package 6 and cured to seal the chip 9 and the wire 10.

加湿リフロー試験は、ＭＳＬ試験法に準じて６０℃／９０％ＲＨの雰囲気下に１６時間放置して十分に吸湿させた後、２６０℃のＩＲリフロー炉を通して、剥離、クラックの発生を目視にて観察した。これらの結果を表３に示した。   In the humidified reflow test, the sample is left for 16 hours in an atmosphere of 60 ° C./90% RH in accordance with the MSL test method to sufficiently absorb moisture, and then visually observed for peeling and cracking through an IR reflow oven at 260 ° C. Observed. These results are shown in Table 3.

［実施例２］
実施例１で用いたアルミニウム金属キレート触媒ＡＣＳの配合量を０．５部に変えた以外は実施例１と同様に調製し、測定した。結果を表１，３に示した。 [Example 2]
It was prepared and measured in the same manner as in Example 1 except that the amount of the aluminum metal chelate catalyst ACS used in Example 1 was changed to 0.5 part. The results are shown in Tables 1 and 3.

［実施例３］
実施例１で用いたアルミニウム金属キレート触媒をホープ製薬製 ケロープＥＢ−２ ０．５部に変更した以外は実施例１と同様に調製し、測定した。結果を表１，３に示した。 [Example 3]
It was prepared and measured in the same manner as in Example 1 except that the aluminum metal chelate catalyst used in Example 1 was changed to 0.5 part of Hope Pharmaceutical's Kerop EB-2. The results are shown in Tables 1 and 3.

［実施例４］
実施例１で用いた接着付与成分に代えて下記式の接着付与成分０．５部を添加した以外は実施例１と同様に調製し、測定した。結果を表１，３に示した。

Figure 2007002234
[Example 4]
It was prepared and measured in the same manner as in Example 1 except that 0.5 part of the adhesion-imparting component represented by the following formula was added instead of the adhesion-imparting component used in Example 1. The results are shown in Tables 1 and 3.
Figure 2007002234

［実施例５］
実施例１で用いた接着付与成分に代えて下記式の接着付与成分１．０部を添加した以外は実施例１と同様に調製し、測定した。結果を表１，３に示した。

Figure 2007002234
[Example 5]
It prepared and measured similarly to Example 1 except having added 1.0 part of adhesion imparting components of the following formula instead of the adhesion imparting component used in Example 1. The results are shown in Tables 1 and 3.
Figure 2007002234

［比較例１］
アルミニウム金属キレート触媒ＡＣＳを添加しない以外は実施例１と同様に調製し、測定した。結果を表２，３に示した。 [Comparative Example 1]
It was prepared and measured in the same manner as in Example 1 except that the aluminum metal chelate catalyst ACS was not added. The results are shown in Tables 2 and 3.

［比較例２］
アルミニウム金属キレート触媒ＡＣＳを添加しない以外は実施例４と同様に調製し、測定した。結果を表２，３に示した。 [Comparative Example 2]
It was prepared and measured in the same manner as in Example 4 except that the aluminum metal chelate catalyst ACS was not added. The results are shown in Tables 2 and 3.

Figure 2007002234
Figure 2007002234

Figure 2007002234
Figure 2007002234

Figure 2007002234
Figure 2007002234

本発明の実施例における剪断接着強さの測定方法を説明する概略斜視図である。It is a schematic perspective view explaining the measuring method of the shear bond strength in the Example of this invention. 本発明の実施例における加湿リフロー試験に用いたパッケージ形状を説明する概略断面図である。It is a schematic sectional drawing explaining the package shape used for the humidification reflow test in the Example of this invention.

符号の説明Explanation of symbols

１，２ 基材片
３ 組成物（硬化物）層
６ パッケージ
７ 封止材料
８ リードフレーム（銀メッキ）
９ チップ
１０ ワイヤー
1, 2 Substrate piece 3 Composition (cured product) layer 6 Package 7 Sealing material 8 Lead frame (silver plating)
9 Chip 10 Wire

Claims (6)

（Ａ）ビニル基含有オルガノポリシロキサン、
（Ｂ）オルガノハイドロジェンポリシロキサン、
（Ｃ）アルミニウム金属系重合触媒、
（Ｄ）白金族金属系触媒、
（Ｅ）接着付与成分
を含有して成ることを特徴とする硬化性シリコーンゴム組成物。 (A) vinyl group-containing organopolysiloxane,
(B) organohydrogenpolysiloxane,
(C) an aluminum metal polymerization catalyst,
(D) a platinum group metal catalyst,
(E) A curable silicone rubber composition comprising an adhesion-imparting component. （Ａ）成分が、下記一般式（１）
Figure 2007002234
 （式中、Ｒ1は互いに同一又は異種の非置換もしくは置換一価炭化水素基、Ｒ2は互いに同一又は異種の脂肪族不飽和結合を有さない非置換もしくは置換一価炭化水素基であり、ｘ，ｙは０又は正の整数であり、ｘ＋ｙはこのオルガノポリシロキサンの２５℃の粘度を１０〜１，０００，０００ｍＰａ・ｓとする数である。）
で表される一分子中に２個以上の脂肪族不飽和結合を有し、粘度が２５℃で１０〜１，０００，０００ｍＰａ・ｓであるオルガノポリシロキサンと、ＳｉＯ2単位、Ｒ3 kＲ4 pＳｉＯ0.5単位及びＲ3 qＲ4 rＳｉＯ0.5単位からなるレジン構造のオルガノポリシロキサン（但し、上記式において、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、ｋは２又は３、ｐは０又は１で、ｋ＋ｐ＝３、ｑは０又は１、ｒは２又は３で、ｑ＋ｒ＝３である。）とからなり、後者のオルガノポリシロキサンの含有量が、（Ａ）成分中２０〜７０質量％である請求項１記載の硬化性シリコーンゴム組成物。 (A) component is the following general formula (1)
Figure 2007002234
 Wherein R 1 is the same or different unsubstituted or substituted monovalent hydrocarbon group, and R 2 is the same or different unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond. , X, y is 0 or a positive integer, and x + y is a number that makes the viscosity of this organopolysiloxane at 25 ° C. 10 to 1,000,000 mPa · s.)
An organopolysiloxane having two or more aliphatic unsaturated bonds in one molecule represented by the formula, having a viscosity of 10 to 1,000,000 mPa · s at 25 ° C., an SiO 2 unit, and R 3 k R Resin-structured organopolysiloxane composed of 4 p SiO 0.5 unit and R 3 q R 4 r SiO 0.5 unit (in the above formula, R 3 is a vinyl group or an allyl group, and R 4 does not contain an aliphatic unsaturated bond) A monovalent hydrocarbon group, k is 2 or 3, p is 0 or 1, k + p = 3, q is 0 or 1, r is 2 or 3, and q + r = 3). The curable silicone rubber composition according to claim 1, wherein the content of the organopolysiloxane is 20 to 70% by mass in the component (A). （Ｃ）成分のアルミニウム金属系重合触媒が、アルミニウム金属キレート化合物である請求項１又は２記載の硬化性シリコーンゴム組成物。   The curable silicone rubber composition according to claim 1 or 2, wherein the aluminum metal polymerization catalyst of component (C) is an aluminum metal chelate compound. （Ｅ）成分の接着付与成分が、ケイ素原子に結合した水素原子、ケイ素原子に結合したアルケニル基、アルコキシシリル基、及びエポキシ基から選ばれる官能性基を少なくとも２種含有する直鎖状又は環状のケイ素原子数４〜５０個のオルガノシロキサンオリゴマーである請求項１，２又は３記載の硬化性シリコーンゴム組成物。   (E) The adhesion imparting component of the component is linear or cyclic containing at least two functional groups selected from a hydrogen atom bonded to a silicon atom, an alkenyl group bonded to a silicon atom, an alkoxysilyl group, and an epoxy group The curable silicone rubber composition according to claim 1, which is an organosiloxane oligomer having 4 to 50 silicon atoms. （Ｅ）成分の接着付与成分が、下記一般式（３）
Figure 2007002234
 （式中、Ｒ6は、下記式（４）
Figure 2007002234
 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るが、少なくとも１個は式（４）の有機基であり、Ｒ7は水素原子又は炭素数１〜６の一価炭化水素基、ｓは１〜６の整数である。）
で示されるイソシアヌレート化合物及び／又はその加水分解縮合物である請求項１，２又は３記載の硬化性シリコーンゴム組成物。 (E) The adhesion imparting component of the component is represented by the following general formula (3)
Figure 2007002234
 (Wherein R 6 represents the following formula (4)
Figure 2007002234
 Or a monovalent hydrocarbon group containing an aliphatic unsaturated bond, at least one of which is an organic group of the formula (4), and R 7 is a hydrogen atom or having 1 to 6 carbon atoms. A monovalent hydrocarbon group, s is an integer of 1-6. )
The curable silicone rubber composition according to claim 1, 2 or 3, which is an isocyanurate compound and / or a hydrolysis-condensation product thereof. 請求項１乃至５のいずれか１項記載の組成物の硬化物で封止した半導体装置。
A semiconductor device sealed with a cured product of the composition according to claim 1.
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