JP2007224102A - Thermal conductive silicone composition, thermal conductive silicone molded article, and its manufacturing method - Google Patents
Thermal conductive silicone composition, thermal conductive silicone molded article, and its manufacturing method Download PDFInfo
- Publication number
- JP2007224102A JP2007224102A JP2006044694A JP2006044694A JP2007224102A JP 2007224102 A JP2007224102 A JP 2007224102A JP 2006044694 A JP2006044694 A JP 2006044694A JP 2006044694 A JP2006044694 A JP 2006044694A JP 2007224102 A JP2007224102 A JP 2007224102A
- Authority
- JP
- Japan
- Prior art keywords
- group
- component
- heat
- conductive silicone
- thermally conductive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
Description
本発明は、電子部品等の放熱のために、発熱性電子部品の熱境界面とヒートシンク又は回路基板等の放熱部材との間に介装する熱伝達材料として有効な熱伝導性シリコーン組成物、熱伝導性シリコーン成形体及びその製造方法に関する。 The present invention is a heat conductive silicone composition effective as a heat transfer material interposed between a heat boundary surface of a heat-generating electronic component and a heat dissipation member such as a heat sink or a circuit board for heat dissipation of the electronic component, The present invention relates to a thermally conductive silicone molded body and a method for producing the same.
電子機器に使用されるＣＰＵ、ドライバＩＣやメモリー等の電子部品は、高性能化・高速化・小型化・高集積化に伴い、それ自身が大量の熱を発生するようになり、その熱によるチップの温度上昇はチップの動作不良、破壊を引き起こす。そのため、動作中の電子部品等の温度上昇を抑制するための多くの放熱方法及びそれに使用する放熱部材が提案されている。 Electronic components such as CPUs, driver ICs, and memories used in electronic devices generate large amounts of heat as they become more sophisticated, faster, smaller, and more integrated. Chip temperature rise causes chip malfunction and destruction. Therefore, many heat dissipating methods and heat dissipating members used for suppressing the temperature rise of electronic parts during operation have been proposed.
従来、電子機器等の発熱部材においては、動作中の部材の温度上昇を抑えるために、アルミニウムや銅等の熱伝導率の高い金属板を用いたヒートシンク等の放熱部材が使用されている。 Conventionally, in a heat generating member such as an electronic device, a heat radiating member such as a heat sink using a metal plate having a high thermal conductivity such as aluminum or copper is used in order to suppress a temperature rise of the member during operation.
ここで、発熱部材から発生する熱を放熱部材に効率よく伝えるために、柔軟性を有するシートを発熱部材と放熱部材との間に介装させ、このシートを介して発熱部材から放熱部材への熱伝導を実現している。 Here, in order to efficiently transmit the heat generated from the heat generating member to the heat radiating member, a flexible sheet is interposed between the heat generating member and the heat radiating member, and the heat generating member is connected to the heat radiating member via this sheet. Realizes heat conduction.
その際、発熱部材及び放熱部材とシートとの密着度を高くすることにより、接触熱抵抗が低くなり放熱の効率は高くなる。このシートの硬度が高い場合、発熱部材及び放熱部材との密着度を上げ接触熱抵抗を低くするためには、シート及び両部材に掛ける応力を高くする必要があり、そうするとこれら両部材に悪影響を及ぼす可能性がある。 At that time, by increasing the adhesion between the heat generating member and the heat radiating member and the sheet, the contact thermal resistance is lowered and the heat radiation efficiency is increased. When the hardness of the sheet is high, it is necessary to increase the stress applied to the sheet and both members in order to increase the adhesion between the heat generating member and the heat radiating member and to reduce the contact thermal resistance. There is a possibility of effect.
シートの硬度を低くすることにより、それほど応力をかけずとも発熱部材及び放熱部材とシートとの密着度を高くすることが可能である。しかしながら、シートの硬度が低くなることにより、取り扱いの際にシートが伸びてしまう、シート表面の粘着性が大きくなり、取り扱いが困難になる等の不具合が指摘されている。 By reducing the hardness of the sheet, it is possible to increase the degree of adhesion between the heat generating member and the heat radiating member and the sheet without applying much stress. However, it has been pointed out that the hardness of the sheet is low, the sheet is stretched during handling, the adhesiveness of the sheet surface is increased, and the handling is difficult.
これらを解決するため、高硬度のシート上に低硬度シートを成形する等の複合化が行われてきた。これにより取り扱い性が良好で、低応力で高い密着度を得ることが可能となった。しかしながら、製造の際の工程が複雑かつ長くなり、シートの収率悪化、コストアップといった問題点があった。 In order to solve these problems, composites such as molding a low hardness sheet on a high hardness sheet have been performed. Thereby, the handleability is good, and it is possible to obtain a high degree of adhesion with low stress. However, the manufacturing process is complicated and long, and there are problems such as deterioration of sheet yield and cost increase.
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。
本発明は、上記事情に鑑みなされたもので、電子部品等の発熱部材（被放熱物）と放熱部材との間に設置されて、密着性及び取り扱い性が良好な熱伝達材料として有効な熱伝導性シリコーン組成物、熱伝導性シリコーン成形体及びその製造方法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 is installed between a heat-generating member (heat-dissipating material) such as an electronic component and a heat-dissipating member, and is effective as a heat transfer material having good adhesion and handling properties. It aims at providing a conductive silicone composition, a heat conductive silicone molding, and its manufacturing method.
本発明者は、上記目的を達成するため鋭意検討した結果、（ａ）１分子中に少なくとも２個のアルケニル基を有するオルガノポリシロキサン、（ｂ）熱伝導性充填剤、（ｃ）ケイ素原子に直接結合した水素原子（Ｓｉ−Ｈ基）を分子中に平均で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）白金族系付加反応触媒、及び（ｅ）アルケニル基が付加可能なケイ素原子に直接結合した水素原子（Ｓｉ−Ｈ基）を分子中に一つ持つ揮発性化合物を含有してなるシリコーン組成物を基材に積層することで、基材に接触する内側表面と外部に露呈、開放された外側表面とを有する未硬化シリコーン体を形成し、これを加熱硬化させるという、いわばワンステップで外側表面部にスキン硬化層が形成され、内側表面部にこのスキン硬化層より硬化程度が低く、低硬度層が形成されたシリコーン伝熱体が得られ、このシリコーン伝熱体が、電子部品等の発熱部材（被放熱物）と放熱部材との間に設置されて、熱伝導性が良好で、密着性及び取り扱い性に優れた熱伝導部材となり得ることを見出し、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 (a) an organopolysiloxane having at least two alkenyl groups in one molecule, (b) a thermally conductive filler, and (c) a silicon atom. An organohydrogenpolysiloxane having two or more directly bonded hydrogen atoms (Si-H groups) on average in the molecule, (d) a platinum group addition reaction catalyst, and (e) a silicon atom to which an alkenyl group can be added. By laminating a silicone composition containing a volatile compound having one directly bonded hydrogen atom (Si-H group) in the molecule to the substrate, it is exposed to the inner surface contacting the substrate and the outside. An uncured silicone body having an open outer surface is formed, and this is cured by heating. In other words, a skin cured layer is formed on the outer surface portion in one step, and this skin cured layer is formed on the inner surface portion. A silicone heat transfer body with a low degree of curing and a low hardness layer is obtained, and this silicone heat transfer body is installed between a heat generating member (heat radiated object) such as an electronic component and a heat radiating member, The present inventors have found that the heat conductive member can be a heat conductive member having good heat conductivity and excellent adhesion and handleability, and has led to the present invention.
即ち、本発明は下記熱伝導性シリコーン組成物、熱伝導性シリコーン成形体及びその製造方法を提供する。
［１］（ａ）１分子中に少なくとも２個のアルケニル基を有するオルガノポリシロキサン： １００質量部、
（ｂ）熱伝導性充填剤： ３００〜５，０００質量部、
（ｃ）ケイ素原子に直接結合した水素原子を分子中に平均で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： （ａ）成分中のアルケニル基に対する（ｃ）成分中のケイ素原子に直接結合した水素原子がモル比で０．６〜１０．０となる量、
（ｄ）白金族系付加反応触媒： 白金元素の量で０．１〜１，０００ｐｐｍ、
（ｅ）アルケニル基が付加可能なケイ素原子に直接結合した水素原子を分子中に一つ持つ揮発性化合物： （ｃ）成分中のケイ素原子に直接結合した水素原子に対する（ｅ）成分中のケイ素原子に直接結合した水素原子がモル比で０．０１〜２．０に相当する量
を構成成分とし、開放状態で加熱硬化し、開放側表面にスキン層が形成されることを特徴とする熱伝導性シリコーン組成物。
［２］熱伝導性充填剤が、金属、酸化物、窒化物、ケイ化物及び人工ダイヤモンドから選ばれる１種又は２種以上であることを特徴とする上記［１］記載の熱伝導性シリコーン組成物。
［３］上記［１］又は［２］記載の熱伝導性シリコーン組成物を開放状態で加熱硬化させて得られる熱伝導性シリコーン成形体。
［４］上記［１］又は［２］記載の熱伝導性シリコーン組成物を基材に積層して未硬化シリコーン体を形成し、これを開放状態で加熱硬化して外側表面部にスキン硬化層を形成し、上記基材側の内側表面部に上記スキン層より低硬度層が形成されたシリコーン伝熱体を形成することを特徴とする熱伝導性シリコーン成形体の製造方法。
That is, this invention provides the following heat conductive silicone composition, a heat conductive silicone molded object, and its manufacturing method.
[1] (a) Organopolysiloxane having at least two alkenyl groups in one molecule: 100 parts by mass
(B) Thermally conductive filler: 300 to 5,000 parts by mass,
(C) Organohydrogenpolysiloxane having an average of two or more hydrogen atoms directly bonded to silicon atoms in the molecule: (a) Hydrogen atoms directly bonded to silicon atoms in component (c) relative to alkenyl groups in component In an amount of 0.6 to 10.0 in molar ratio,
(D) Platinum group addition reaction catalyst: 0.1 to 1,000 ppm in the amount of platinum element,
(E) Volatile compound having in its molecule one hydrogen atom directly bonded to a silicon atom to which an alkenyl group can be added: (c) Silicon in component (e) with respect to a hydrogen atom directly bonded to a silicon atom in component The heat is characterized in that the hydrogen atoms directly bonded to the atoms have an amount corresponding to a molar ratio of 0.01 to 2.0 as a constituent component and are heat-cured in an open state to form a skin layer on the open-side surface. Conductive silicone composition.
[2] The heat conductive silicone composition according to the above [1], wherein the heat conductive filler is one or more selected from metals, oxides, nitrides, silicides and artificial diamonds. object.
[3] A thermally conductive silicone molded article obtained by heat-curing the thermally conductive silicone composition according to [1] or [2] in an open state.
[4] The thermally conductive silicone composition described in [1] or [2] above is laminated on a base material to form an uncured silicone body, which is heated and cured in an open state to form a skin cured layer on the outer surface portion. And forming a silicone heat transfer body in which a lower hardness layer than the skin layer is formed on the inner surface portion on the base material side.
本発明によれば、電子部品等の発熱部材（被放熱物）と放熱部材との間に設置されて、熱伝導性が良好で、密着性及び取り扱い性に優れた熱伝導部材を容易に提供することができる。 According to the present invention, a heat conductive member that is installed between a heat generating member (heat radiated object) such as an electronic component and a heat radiating member and has good heat conductivity and excellent adhesion and handling is easily provided. can do.
以下、本発明について詳細に説明する。
本発明に用いられる（ａ）成分のオルガノポリシロキサンは１分子中に少なくとも２個のアルケニル基を有するもので、通常は、主鎖部分が基本的にジオルガノシロキサン単位の繰り返しからなるものが好ましい。
The present invention will be described in detail below.
The organopolysiloxane of component (a) used in the present invention has at least two alkenyl groups in one molecule, and it is usually preferred that the main chain portion basically consists of repeating diorganosiloxane units. .
（ａ）成分として具体的には、下記一般式（１）、（２）又は（３）で表されるものが挙げられる。
（式中、Ｘはアルケニル基、Ｒ1は独立に脂肪族不飽和結合を含有しない非置換又は置換の１価炭化水素基であり、ＲはＸ又はＲ1を示し、ａ、ｂ、ｃは０又は正数、ｄは２以上の正数、ｅは０又は正数、ｆは１以上の正数である。）
Specific examples of the component (a) include those represented by the following general formula (1), (2) or (3).
(Wherein X is an alkenyl group, R 1 is an unsubstituted or substituted monovalent hydrocarbon group which does not independently contain an aliphatic unsaturated bond, R represents X or R 1 , and a, b and c are 0 or a positive number, d is a positive number of 2 or more, e is 0 or a positive number, and f is a positive number of 1 or more.)
上記式中、Ｒ1の脂肪族不飽和結合を含有しない非置換又は置換の１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、ヘプチル基、オクチル基、ノニル基、デシル基、ドデシル基などのアルキル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基等のシクロアルキル基、フェニル基、トリル基、キシリル基、ナフチル基、ビフェニリ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、メチルベンジル基等のアラルキル基、並びにこれらの基の炭素原子に結合している水素原子の一部又は全部が、フッ素、塩素、臭素等のハロゲン原子、シアノ基などで置換された基、例えば、クロロメチル基、２−ブロモエチル基、３−クロロプロピル基、３，３，３−トリフルオロプロピル基、クロロフェニル基、フルオロフェニル基、シアノエチル基、３，３，４，４，５，５，６，６，６−ノナフルオロヘキシル基等の炭素原子数が１〜１０、特に炭素原子数が１〜６のものが挙げられ、これらの中でも好ましくは、メチル基、エチル基、プロピル基、クロロメチル基、ブロモエチル基、３，３，３−トリフルオロプロピル基、シアノエチル基等の炭素原子数１〜３の非置換又は置換のアルキル基、及びフェニル基、クロロフェニル基、フルオロフェニル基等の非置換又は置換のフェニル基である。また、Ｒ1は全てが同一であっても、異なっていてもよい。 In the above formula, examples of the unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond represented by R 1 include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert- Butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl and other alkyl groups, cyclopentyl, cyclohexyl, cycloheptyl and other cycloalkyl groups, phenyl, tolyl Group, an aryl group such as a xylyl group, a naphthyl group, a biphenylyl group, an aralkyl group such as a benzyl group, a phenylethyl group, a phenylpropyl group, a methylbenzyl group, and a hydrogen atom bonded to the carbon atom of these groups. Groups in which part or all are substituted with halogen atoms such as fluorine, chlorine, bromine, cyano groups, etc., for example Chloromethyl group, 2-bromoethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, chlorophenyl group, fluorophenyl group, cyanoethyl group, 3,3,4,4,5,5,6, Examples thereof include those having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, such as 6,6-nonafluorohexyl group, and among these, methyl group, ethyl group, propyl group, chloromethyl group are preferable. , Unsubstituted or substituted alkyl groups having 1 to 3 carbon atoms such as bromoethyl group, 3,3,3-trifluoropropyl group, and cyanoethyl group, and unsubstituted or substituted phenyl group, chlorophenyl group, fluorophenyl group, etc. Of the phenyl group. R 1 may all be the same or different.
Ｘはアルケニル基である。分子中のＸが全て同一である必要はない。
アルケニル基としては、例えば、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等の通常、炭素原子数２〜８程度のものが挙げられ、中でもビニル基、アリル基等の低級アルケニル基が好ましく、特にはビニル基が好ましい。
X is an alkenyl group. It is not necessary that all Xs in the molecule are the same.
Examples of the alkenyl group usually include those having about 2 to 8 carbon atoms such as a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, a hexenyl group, and a cyclohexenyl group. Among them, a vinyl group, A lower alkenyl group such as an allyl group is preferred, and a vinyl group is particularly preferred.
式中、ａ、ｃ、ｅは０又は正数であるが、ａ、ｃ、ｅは１０〜１０，０００の範囲が好ましく、より好ましくは５０〜２，０００の範囲であり、更に好ましくは１００〜１，０００の範囲である。また、ｂは０又は正数であるが、０≦ｂ／（ａ＋ｂ）≦０．５、好ましくは０≦ｂ／（ａ＋ｂ）≦０．２、更に好ましくは０≦ｂ／（ａ＋ｂ）≦０．１である。
式中、ｄは２以上の正数であるが、０＜ｄ／（ｃ＋ｄ）≦０．５であることが好ましく、より好ましくは０＜ｄ／（ｃ＋ｄ）≦０．２であり、更に好ましくは０＜ｄ／（ｃ＋ｄ）≦０．１である。
式中、ｆは１以上の正数であるが、０＜ｆ／（ｅ＋ｆ）≦０．５であることが好ましく、より好ましくは０＜ｆ／（ｅ＋ｆ）≦０．２であり、更に好ましくは０＜ｆ／（ｅ＋ｆ）≦０．１である。
In the formula, a, c and e are 0 or a positive number, but a, c and e are preferably in the range of 10 to 10,000, more preferably in the range of 50 to 2,000, and still more preferably 100. It is in the range of ~ 1,000. Further, b is 0 or a positive number, but 0 ≦ b / (a + b) ≦ 0.5, preferably 0 ≦ b / (a + b) ≦ 0.2, and more preferably 0 ≦ b / (a + b) ≦ 0. .1.
In the formula, d is a positive number of 2 or more, preferably 0 <d / (c + d) ≦ 0.5, more preferably 0 <d / (c + d) ≦ 0.2, and still more preferably. Is 0 <d / (c + d) ≦ 0.1.
In the formula, f is a positive number of 1 or more, preferably 0 <f / (e + f) ≦ 0.5, more preferably 0 <f / (e + f) ≦ 0.2, and still more preferably. 0 <f / (e + f) ≦ 0.1.
このオルガノポリシロキサンは、１種単独で使用しても、複数の異なるものを併用しても構わない。 This organopolysiloxane may be used alone or in combination with a plurality of different ones.
本発明に用いられる（ｂ）成分の熱伝導性充填剤は、非磁性の銅、アルミニウム等の金属、アルミナ、シリカ、マグネシア、ベンガラ、ベリリア、チタニア、ジルコニア等の金属酸化物、窒化アルミニウム、窒化ケイ素、窒化ホウ素等の金属窒化物、人工ダイヤモンドあるいは炭化ケイ素等、一般に熱伝導性充填剤とされる物質を用いることができる。 The heat conductive filler of the component (b) used in the present invention includes non-magnetic metals such as copper and aluminum, metal oxides such as alumina, silica, magnesia, bengara, beryllia, titania and zirconia, aluminum nitride, and nitride. A material generally used as a thermally conductive filler, such as metal nitrides such as silicon and boron nitride, artificial diamond or silicon carbide, can be used.
これら熱伝導性充填剤は、平均粒径が０．１〜１００μｍ、望ましくは０．５〜５０μｍ、更に望ましくは０．５〜３０μｍのものを用いることができる。これら充填剤は１種単独で用いてもよいし、複数種を混合して用いてもよい。また、平均粒径の異なる粒子を２種以上用いることも可能である。 As these heat conductive fillers, those having an average particle diameter of 0.1 to 100 μm, preferably 0.5 to 50 μm, more preferably 0.5 to 30 μm can be used. These fillers may be used individually by 1 type, and may mix and use multiple types. Two or more kinds of particles having different average particle diameters can be used.
熱伝導性充填剤の配合量は、（ａ）成分１００質量部に対して３００〜５，０００質量部、好ましくは５００〜３，０００質量部である。熱伝導性充填剤の配合量が多すぎると、硬化後に所望の軟らかさを得ることが困難になり、そのために必要な密着性を得ることができなくなる。少なすぎると所望の熱伝導性を得ることができない。 The compounding quantity of a heat conductive filler is 300-5,000 mass parts with respect to 100 mass parts of (a) component, Preferably it is 500-3,000 mass parts. When the blending amount of the heat conductive filler is too large, it becomes difficult to obtain a desired softness after curing, and thus it becomes impossible to obtain the necessary adhesion. If the amount is too small, the desired thermal conductivity cannot be obtained.
本発明に用いられる（ｃ）成分であるオルガノハイドロジェンポリシロキサンは分子中にＳｉ−Ｈ基を平均で２個以上有するものであり、好ましくは平均構造式で以下のように表される単一又は混合物である。 The organohydrogenpolysiloxane which is the component (c) used in the present invention has an average of two or more Si—H groups in the molecule, preferably a single unit represented by the following average structural formula: Or a mixture.
（式中、Ｒ2は独立に脂肪族不飽和結合を含有しない非置換又は置換の１価炭化水素基であり、ｐ、ｓは０又は正数、また、ｑは２以上の正数、ｒは１以上の正数である。）
(Wherein R 2 independently represents an unsubstituted or substituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated bond, p and s are 0 or a positive number, q is a positive number of 2 or more, r Is a positive number greater than or equal to 1.)
式（４）〜（６）中、Ｒ2の脂肪族不飽和結合を含有しない非置換又は置換の１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、ヘプチル基、オクチル基、ノニル基、デシル基、ドデシル基などのアルキル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基等のシクロアルキル基、フェニル基、トリル基、キシリル基、ナフチル基、ビフェニリ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、メチルベンジル基等のアラルキル基、並びにこれらの基に炭素原子が結合している水素原子の一部又は全部が、フッ素、塩素、臭素等のハロゲン原子、シアノ基などで置換された基、例えば、クロロメチル基、２−ブロモエチル基、３−クロロプロピル基、３，３，３−トリフルオロプロピル基、クロロフェニル基、フルオロフェニル基、シアノエチル基、３，３，４，４，５，５，６，６，６−ノナフルオロヘキシル基等が挙げられ、代表的なものは炭素原子数が１〜１０、特に炭素原子数が１〜６のものであり、好ましくは、メチル基、エチル基、プロピル基、クロロメチル基、ブロモエチル基、３，３，３−トリフルオロプロピル基、シアノエチル基等の炭素原子数１〜３の非置換又は置換のアルキル基及びフェニル基、クロロフェニル基、フルオロフェニル基等の非置換又は置換のフェニル基である。又、Ｒ2は全てが同一であることを限定するものではない。式（４）〜（６）中のｐは０又は正数であるが、好ましくは０〜１，０００、更に好ましくは１〜１００である。ｑは２以上の正数、好ましくは２〜３０、更に好ましくは２〜１０、ｒは１以上の正数、好ましくは１〜３０、更に好ましくは１〜１０、ｓは０又は正数、好ましくは１〜３０、更に好ましくは１〜１０である。 In the formulas (4) to (6), as the unsubstituted or substituted monovalent hydrocarbon group not containing an aliphatic unsaturated bond of R 2 , for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, Cycloalkyl groups such as isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, etc., cyclopentyl group, cyclohexyl group, cycloheptyl group An aryl group such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group and a biphenylyl group, an aralkyl group such as a benzyl group, a phenylethyl group, a phenylpropyl group and a methylbenzyl group, and a carbon atom bonded to these groups. A group in which some or all of the hydrogen atoms are substituted with halogen atoms such as fluorine, chlorine, bromine, cyano groups, etc. For example, chloromethyl group, 2-bromoethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, chlorophenyl group, fluorophenyl group, cyanoethyl group, 3,3,4,4,5,5, 6,6,6-nonafluorohexyl group and the like can be mentioned, and typical ones are those having 1 to 10 carbon atoms, particularly those having 1 to 6 carbon atoms, preferably a methyl group, an ethyl group, C1-C3 unsubstituted or substituted alkyl groups such as propyl group, chloromethyl group, bromoethyl group, 3,3,3-trifluoropropyl group, cyanoethyl group and the like, phenyl group, chlorophenyl group, fluorophenyl group, etc. An unsubstituted or substituted phenyl group. Also, R 2 is not limited to being all the same. P in the formulas (4) to (6) is 0 or a positive number, preferably 0 to 1,000, and more preferably 1 to 100. q is a positive number of 2 or more, preferably 2 to 30, more preferably 2 to 10, r is a positive number of 1 or more, preferably 1 to 30, more preferably 1 to 10, and s is 0 or a positive number, preferably Is 1-30, more preferably 1-10.
（ｃ）成分の配合量は、（ａ）成分中のアルケニル基に対する（ｃ）成分中のケイ素原子に直接結合した水素原子のモル比（Ｓｉ−Ｈ／アルケニル基）が０．６〜１０．０となる量であり、好ましくは０．７〜５．０となる量である。０．６未満であると組成物の硬化が不十分となり、１０．０を超えると成形時に発泡してしまう。 The compounding amount of the component (c) is such that the molar ratio of the hydrogen atom directly bonded to the silicon atom in the component (c) to the alkenyl group in the component (a) (Si-H / alkenyl group) is 0.6 to 10. The amount is 0, preferably 0.7 to 5.0. If it is less than 0.6, the composition is insufficiently cured, and if it exceeds 10.0, foaming occurs during molding.
本発明に用いられる（ｄ）成分の白金族系付加反応触媒は、（ａ）成分中のアルケニル基と、（ｃ）成分中のＳｉ−Ｈ基との付加反応を促進するための触媒であり、ヒドロシリル化反応に用いられる触媒として周知の触媒が挙げられる。その具体例としては、例えば、白金（白金黒を含む）、ロジウム、パラジウム等の白金族金属単体、Ｈ2ＰｔＣｌ4・ｎＨ2Ｏ、Ｈ2ＰｔＣｌ6・ｎＨ2Ｏ、ＮａＨＰｔＣｌ6・ｎＨ2Ｏ、ＫＨＰｔＣｌ6・ｎＨ2Ｏ、Ｎａ2ＰｔＣｌ6・ｎＨ2Ｏ、Ｋ2ＰｔＣｌ4・ｎＨ2Ｏ、ＰｔＣｌ4・ｎＨ2Ｏ、ＰｔＣｌ2、Ｎａ2ＨＰｔＣｌ4・ｎＨ2Ｏ（但し、式中、ｎは０〜６の整数であり、好ましくは０又は６である）等の塩化白金、塩化白金酸及び塩化白金酸塩、アルコール変性塩化白金酸（特許文献２参照）、塩化白金酸とオレフィンとのコンプレックス、白金黒、パラジウム等の白金族金属をアルミナ、シリカ、カーボン等の担体に担持させたもの、ロジウム−オレフィンコンプレックス、クロロトリス（トリフェニルフォスフィン）ロジウム（ウィルキンソン触媒）、塩化白金、塩化白金酸又は塩化白金酸塩とビニル基含有シロキサン、特にビニル基含有環状シロキサンとのコンプレックス等が挙げられる。 The platinum group addition reaction catalyst of component (d) used in the present invention is a catalyst for promoting the addition reaction between the alkenyl group in component (a) and the Si—H group in component (c). Examples of the catalyst used in the hydrosilylation reaction include known catalysts. Specific examples thereof include platinum group metals such as platinum (including platinum black), rhodium and palladium, H 2 PtCl 4 · nH 2 O, H 2 PtCl 6 · nH 2 O, NaHPtCl 6 · nH 2 O. , KHPtCl 6 · nH 2 O, Na 2 PtCl 6 · nH 2 O, K 2 PtCl 4 · nH 2 O, PtCl 4 · nH 2 O, PtCl 2 , Na 2 HPtCl 4 · nH 2 O (where, n is an integer of 0 to 6, preferably 0 or 6), such as platinum chloride, chloroplatinic acid and chloroplatinate, alcohol-modified chloroplatinic acid (see Patent Document 2), chloroplatinic acid and olefin Complex, platinum black, platinum group metals such as palladium supported on alumina, silica, carbon, etc., rhodium-olefin complex, chlorotris (triphenylphosphine) lodge (Complex of platinum chloride, chloroplatinic acid or chloroplatinate and vinyl group-containing siloxane, particularly vinyl group-containing cyclic siloxane).
（ｄ）成分の使用量は、所謂触媒量でよく、通常、成分（ａ）に対する白金族金属元素の質量換算で、０．１〜１，０００ｐｐｍ、好ましくは０．５〜５００ｐｐｍ、より好ましくは１．０〜２００ｐｐｍ程度がよい。０．１ｐｐｍ未満では硬化が不十分となり、１，０００ｐｐｍを超えると経済的に不利である。 The amount of component (d) used may be a so-called catalytic amount, and is usually 0.1 to 1,000 ppm, preferably 0.5 to 500 ppm, more preferably in terms of the mass of the platinum group metal element relative to component (a). About 1.0-200 ppm is good. If it is less than 0.1 ppm, curing is insufficient, and if it exceeds 1,000 ppm, it is economically disadvantageous.
（ｅ）成分のアルケニル基が付加可能なケイ素原子に直接結合した水素原子（Ｓｉ−Ｈ基）を分子中に一つ持つ揮発性化合物は、組成物を加熱成形する際に成形物表面から揮発するものであればよいが、シラン化合物、低分子シロキサン化合物から選ばれることが好ましい。また、加熱時の温度（特に１５０℃）で蒸気圧が１．３３ｋＰａ（１０ｍｍＨｇ）以上を示すことが好ましく、更には６．６７ｋＰａ（５０ｍｍＨｇ）以上を示すことが好ましい。 (E) The volatile compound having one hydrogen atom (Si-H group) directly bonded to the silicon atom to which the alkenyl group of the component can be added is volatilized from the surface of the molded product when the composition is thermoformed. However, it is preferably selected from silane compounds and low molecular siloxane compounds. Further, the vapor pressure is preferably 1.33 kPa (10 mmHg) or more at the heating temperature (particularly 150 ° C.), more preferably 6.67 kPa (50 mmHg) or more.
揮発性化合物がシラン又は低分子シロキサンである場合、以下の一般式で示される化合物を用いることができる。 When the volatile compound is silane or low molecular siloxane, a compound represented by the following general formula can be used.
（式中、Ｒ3は脂肪族不飽和結合を含有しない非置換又は置換の１価炭化水素基であり、ｈは０又は正数であり、ｉは０又は正数であり、ｊは２以上の正数である。）
(In the formula, R 3 is an unsubstituted or substituted monovalent hydrocarbon group not containing an aliphatic unsaturated bond, h is 0 or a positive number, i is 0 or a positive number, and j is 2 or more. Is a positive number.)
式（７）〜（１０）中、Ｒ3の脂肪族不飽和結合を含有しない非置換又は置換の１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、ヘプチル基、オクチル基、ノニル基、デシル基、ドデシル基などのアルキル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基等のシクロアルキル基、フェニル基、トリル基、キシリル基、ナフチル基、ビフェニリ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、メチルベンジル基等のアラルキル基、並びにこれらの基に炭素原子が結合している水素原子の一部又は全部が、フッ素、塩素、臭素等のハロゲン原子、シアノ基などで置換された基、例えば、クロロメチル基、２−ブロモエチル基、３−クロロプロピル基、３，３，３−トリフルオロプロピル基、クロロフェニル基、フルオロフェニル基、シアノエチル基、３，３，４，４，５，５，６，６，６−ノナフルオロヘキシル基等が挙げられ、代表的なものは炭素原子数が１〜１０、特に炭素原子数が１〜６のものであり、好ましくは、メチル基、エチル基、プロピル基、クロロメチル基、ブロモエチル基、３，３，３−トリフルオロプロピル基、シアノエチル基等の炭素原子数１〜３の非置換又は置換のアルキル基及びフェニル基、クロロフェニル基、フルオロフェニル基等の非置換又は置換のフェニル基である。また、Ｒ3は全てが同一であることを限定するものではない。 In formulas (7) to (10), examples of the unsubstituted or substituted monovalent hydrocarbon group not containing an aliphatic unsaturated bond represented by R 3 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, Cycloalkyl groups such as isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, etc., cyclopentyl group, cyclohexyl group, cycloheptyl group An aryl group such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group and a biphenylyl group, an aralkyl group such as a benzyl group, a phenylethyl group, a phenylpropyl group and a methylbenzyl group, and a carbon atom bonded to these groups. Some or all of the hydrogen atoms are substituted with halogen atoms such as fluorine, chlorine and bromine, cyano groups, etc. For example, chloromethyl group, 2-bromoethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, chlorophenyl group, fluorophenyl group, cyanoethyl group, 3,3,4,4,5,5 , 6,6,6-nonafluorohexyl group and the like, typical ones having 1 to 10 carbon atoms, particularly those having 1 to 6 carbon atoms, preferably methyl group, ethyl group , A propyl group, a chloromethyl group, a bromoethyl group, a 3,3,3-trifluoropropyl group, a cyanoethyl group, etc., an unsubstituted or substituted alkyl group having 1 to 3 carbon atoms and a phenyl group, a chlorophenyl group, a fluorophenyl group Or an unsubstituted or substituted phenyl group. Also, R 3 is not limited to being all the same.
式（８）中のｈは０又は正数であり、好ましくは０又は１、更に好ましくは０であり、式（９）中のｉは０又は正数であり、望ましくは０又は１、更に望ましくは０であり、式（１０）中のｊは１以上の正数であり、望ましくは１〜６、更に望ましくは２〜４である。 H in the formula (8) is 0 or a positive number, preferably 0 or 1, more preferably 0, i in the formula (9) is 0 or a positive number, desirably 0 or 1, It is preferably 0, and j in the formula (10) is a positive number of 1 or more, preferably 1 to 6, and more preferably 2 to 4.
（ｅ）成分の配合量は、（ｃ）成分中のケイ素原子に直接結合した水素原子（Ｓｉ−Ｈ基）に対する（ｅ）成分中のケイ素原子に直接結合した水素原子（Ｓｉ−Ｈ基）がモル比［（ｅ）成分のＳｉ−Ｈ／（ｃ）成分のＳｉ−Ｈ］で０．０１〜２．０に相当する量であり、望ましくは０．０５〜１．０、更に望ましくは０．１〜０．５である。２．０よりも多くなると、加熱しても硬化しなくなり、０．０１未満ではシート全体が硬くなってしまう。 The compounding amount of the component (e) is the hydrogen atom (Si-H group) directly bonded to the silicon atom in the component (e) relative to the hydrogen atom (Si-H group) directly bonded to the silicon atom in the component (c). Is an amount corresponding to a molar ratio [Si-H of component (e) / Si-H of component (c)] of 0.01 to 2.0, preferably 0.05 to 1.0, more preferably 0.1 to 0.5. If it exceeds 2.0, it will not be cured even if heated, and if it is less than 0.01, the entire sheet will become hard.
本発明のシリコーン組成物には、この他に、硬化反応を適当な時間に調整するための制御剤、熱伝導性充填剤の表面処理剤、着色のための顔料・染料、難燃性付与剤、内添離型剤等、機能を向上させるための様々な添加剤を本発明の目的を損なわない範囲で添加することが可能である。 In addition to this, the silicone composition of the present invention includes a control agent for adjusting the curing reaction to an appropriate time, a surface treatment agent for a heat conductive filler, a pigment / dye for coloring, and a flame retardant imparting agent. It is possible to add various additives for improving the function, such as an internal release agent, within a range that does not impair the object of the present invention.
（ａ）〜（ｅ）成分及びその他の任意成分を混練することにより所望のシリコーン組成物を得ることができる。混練には、プラネタリミキサ、品川式万能撹拌機、ミックスマーラー、ニーダー、二本ロール、三本ロール等、粉体と液体とを混練せしめる際に用いられるミキサを用いることができる。 A desired silicone composition can be obtained by kneading the components (a) to (e) and other optional components. For the kneading, a mixer used for kneading powder and liquid, such as a planetary mixer, a Shinagawa universal stirrer, a mix muller, a kneader, a two-roll, a three-roll, can be used.
このようにして得られる本発明の熱伝導性シリコーン組成物は、フィルム等の基材上にコーティングする等して基材に積層し、外側表面が外部に露呈、開放され、空気にさらされている開放状態、内側表面が上記基材に接触していることにより空気に直接触れられていない閉鎖状態にある未硬化シリコーン体を形成する。そして、この状態で加熱することにより、上記（ｅ）成分の揮発性化合物が上記未硬化シリコーン体をその外側表面の開放面から揮発するように拡散し、該外側表面近傍でケイ素原子に直接結合した水素原子（Ｓｉ−Ｈ基）の量が増大して上記（ａ）成分のオルガノポリシロキサンのアルケニル基と速やかにかつ十分量で付加反応が生じて表面が硬化し、硬くなって粘着感が実質的にないか又は少ないスキン硬化層が外表面部に形成される一方、この外表面部より内部、特に上記基材に接触している内表面部は、未硬化乃至半硬化状態で、少なくとも上記外表面部より硬化程度が低く、このため上記スキン硬化層より低硬度で軟らかいゴム状態の緩衝層が形成された、シリコーン伝熱体が得られる。 The heat conductive silicone composition of the present invention thus obtained is laminated on a substrate such as by coating on a substrate such as a film, and the outer surface is exposed to the outside, released, and exposed to air. An uncured silicone body in a closed state in which the inner surface is in contact with the substrate and is not in direct contact with air is formed. Then, by heating in this state, the volatile compound of the component (e) diffuses so that the uncured silicone body volatilizes from the open surface of the outer surface, and directly bonds to silicon atoms in the vicinity of the outer surface. The amount of hydrogen atoms (Si-H groups) increased and an addition reaction with the alkenyl group of the organopolysiloxane of component (a) occurred quickly and in a sufficient amount to cure the surface and become hard and sticky. While the skin hardened layer substantially or little is formed on the outer surface portion, the inner surface from this outer surface portion, particularly the inner surface portion in contact with the substrate is at least uncured or semi-cured, A silicone heat transfer body is obtained in which the degree of cure is lower than that of the outer surface portion, and therefore a rubber-like buffer layer having a lower hardness and softer than the skin cured layer is formed.
ここで、基材として用いられるこのシリコーン伝熱体と剥離可能なフィルムとしては、プラスチックフィルムや金属フィルムが例示されるが、例えば、ＰＥＴ（ポリエチレンテレフタレート）フィルム、フッ素樹脂フィルム、ポリエステルフィルム等のプラスチックフィルムが好ましく、特に未硬化シリコーン体の加熱硬化温度（通常８０〜１６０℃程度）での耐熱性を有するプラスチックフィルムが好ましい。 Here, examples of the film that can be peeled off from the silicone heat transfer material used as the base material include plastic films and metal films. A film is preferable, and a plastic film having heat resistance at a heat curing temperature (usually about 80 to 160 ° C.) of an uncured silicone body is particularly preferable.
この基材（フィルム）は、熱伝導部材の使用時に剥離するが、この使用直前まで熱伝導部材に付着された状態で該部材を取り扱うことができるので、この基材（フィルム）に面するシリコーン伝熱体の内表面部が軟らかかったり、粘着性があったとしても、取り扱い性がよいものである。なお、このフィルム厚さは、１０〜５００μｍ、特に５０〜２００μｍが好ましい。 Although this base material (film) peels off at the time of use of a heat conductive member, since this member can be handled in the state attached to the heat conductive member until just before this use, the silicone which faces this base material (film) Even if the inner surface portion of the heat transfer body is soft or sticky, it is easy to handle. The film thickness is preferably 10 to 500 μm, particularly preferably 50 to 200 μm.
また、上記未硬化シリコーン体、及びこれを硬化させて得られるシリコーン伝熱体は、シート状であることが好ましく、この場合、このシート体の厚さは、０．１〜１０．０ｍｍ、特に０．３〜５．０ｍｍとすることが、取り扱い性及び伝熱特性の点より好ましい。 The uncured silicone body and the silicone heat transfer body obtained by curing the silicone body are preferably in the form of a sheet. In this case, the thickness of the sheet body is 0.1 to 10.0 mm, in particular It is preferable to set it as 0.3-5.0 mm from the point of a handleability and a heat-transfer characteristic.
なお、上記シリコーン組成物を基材にコーティングする方法としては、コンマコート、グラビアコート、バーコート、ナイフコート等を用いることができる。 In addition, as a method of coating the base material with the silicone composition, comma coating, gravure coating, bar coating, knife coating, or the like can be used.
加熱する手段は、熱風、赤外線照射、マイクロ波等あらゆる加熱手段を用いることができる。成形時の加熱温度は、６０〜２００℃とすることが好ましく、より好ましくは８０〜１６０℃であり、加熱時間は１〜３０分とすることが好ましく、より好ましくは３〜１５分である。加熱温度が高すぎると発泡する場合があり、低すぎると開放側表面の粘着感が強すぎてしまう場合がある。一方、加熱時間が短いと十分な表面硬化が起こらない場合があり、長すぎると経済的に不利となる。 Any heating means such as hot air, infrared irradiation, and microwave can be used as the heating means. The heating temperature during molding is preferably 60 to 200 ° C., more preferably 80 to 160 ° C., and the heating time is preferably 1 to 30 minutes, more preferably 3 to 15 minutes. If the heating temperature is too high, foaming may occur, and if it is too low, the adhesiveness on the open side surface may be too strong. On the other hand, if the heating time is short, sufficient surface hardening may not occur, and if it is too long, it is economically disadvantageous.
なお、上記スキン硬化層の厚さ、硬度、緩衝層の硬度とスキン硬化層との硬度差は、（ａ）成分のアルケニル基量と、（ｃ）、（ｅ）成分のＳｉ−Ｈ基の量、これらＳｉ−Ｈ基量との割合や、加熱温度、時間を選定することにより、コントロールすることができる。 The thickness of the skin cured layer, the hardness, the hardness difference between the buffer layer hardness and the skin cured layer are the amount of the alkenyl group of the component (a) and the Si-H group of the components (c) and (e). It can be controlled by selecting the amount, the ratio of these Si-H groups, the heating temperature, and the time.
このようにして得られる熱伝導部材（上記基材を除去した後のシリコーン伝熱体）は、発熱性電子部品（発熱部材乃至被放熱物）の熱境界面とヒートシンク又は回路基板などの放熱部材との間に介装して用いた場合、被放熱物及び放熱部材に低応力で密着し、熱抵抗も小さくなるため、より良好な放熱特性を示すものである。即ち、一面のスキン層が形成され、強靭さを有しているので、取り扱い性が良好である上、スキン層より内部側、特に内側表面部の緩衝層が軟らかく形成されているので、被放熱物と放熱部材との間に、その変位や段差等にも十分確実に追随し、密着よく配置することができる。特に、軟らかい側が発熱部材に接触し、スキン層のある側が放熱部材に接触するように用いることが好ましい。 The heat conducting member (silicone heat transfer member after removing the base material) thus obtained is composed of a heat boundary surface of a heat-generating electronic component (a heat generating member or a heat radiating object) and a heat radiating member such as a heat sink or a circuit board. When it is used in between, it adheres to the object to be radiated and the heat radiating member with low stress, and the thermal resistance is reduced, so that better heat radiating characteristics are exhibited. In other words, since the skin layer on one side is formed and has toughness, it is easy to handle, and the buffer layer on the inner side, particularly the inner surface part, is softer than the skin layer. Between the object and the heat radiating member, it is possible to follow the displacement, the step, and the like with sufficient certainty and arrange them with good adhesion. In particular, it is preferable that the soft side is in contact with the heat generating member and the side having the skin layer is in contact with the heat radiating member.
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、下記例において、粘度はオストワルド法により測定した２５℃における値を示し、平均粒径はマイクロトラックにより測定した値を示す。また、下記式においてＭｅはメチル基を示す。 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 the following examples, the viscosity indicates a value at 25 ° C. measured by the Ostwald method, and the average particle diameter indicates a value measured by Microtrac. In the following formulae, Me represents a methyl group.
［実施例１］
１０，０００ｍｍ2／ｓの粘度を持ち、両末端にビニル基を持つジメチルオルガノポリシロキサン１００質量部、４μｍの平均粒径をもつアルミナ５００質量部を品川式万能撹拌機に仕込み、６０分間混合せしめた後、塩化白金酸の２−エチル−ヘキサノール溶液（白金量で２質量％）を０．２質量部、エチニルシクロヘキサノールのトルエン溶液（５０質量％）を０．１質量部、ペンタメチルハイドロジェンジシロキサンを０．５質量部、オルガノハイドロジェンポリシロキサン（式１１）を５．０質量部、を順に添加し、各物質の添加後にその都度混合を５分行い、最後に−６５０ｍｍＨｇの減圧条件下で５分間混合せしめて組成物ａを得た。この組成物ａを、ＰＥＴフィルム上に厚さ１．０ｍｍとなるように塗布し、１５０℃の雰囲気下に１０分放置し、シート状に成形し、シートＡを得た。
[Example 1]
100 parts by weight of dimethylorganopolysiloxane having a viscosity of 10,000 mm 2 / s and vinyl groups at both ends and 500 parts by weight of alumina having an average particle diameter of 4 μm are charged into a Shinagawa universal stirrer and mixed for 60 minutes. Then, 0.2 parts by mass of 2-ethyl-hexanol solution of chloroplatinic acid (2% by mass in platinum), 0.1 part by mass of toluene solution of ethynylcyclohexanol (50% by mass), pentamethylhydrogen 0.5 parts by mass of disiloxane and 5.0 parts by mass of organohydrogenpolysiloxane (formula 11) were added in order, and after each addition, mixing was performed for 5 minutes each time, and finally a reduced pressure condition of -650 mmHg. Under mixing for 5 minutes, composition a was obtained. This composition a was applied on a PET film so as to have a thickness of 1.0 mm, and left in an atmosphere at 150 ° C. for 10 minutes to form a sheet, whereby a sheet A was obtained.
［実施例２］
１０，０００ｍｍ2／ｓの粘度を持ち、両末端にビニル基を持つジメチルオルガノポリシロキサン１００質量部、４μｍの平均粒径をもつアルミナ５００質量部を品川式万能撹拌機に仕込み、６０分間混合せしめた後、塩化白金酸の２−エチル−ヘキサノール溶液（白金量で２質量％）を０．２質量部、エチニルシクロヘキサノールのトルエン溶液（５０質量％）を０．１質量部、式（１２）で表されるヘプタメチルハイドロジェントリシロキサンを０．７質量部、オルガノハイドロジェンポリシロキサン（式１１）を５．０質量部、を順に添加し、各物質の添加後にその都度混合を５分行い、最後に−６５０ｍｍＨｇの減圧条件下で５分間混合せしめて組成物ｂを得た。この組成物ｂを、ＰＥＴフィルム上に厚さ１．０ｍｍとなるように塗布し、１５０℃の雰囲気下に１０分放置し、シート状に成形し、シートＢを得た。
[Example 2]
100 parts by weight of dimethylorganopolysiloxane having a viscosity of 10,000 mm 2 / s and vinyl groups at both ends and 500 parts by weight of alumina having an average particle diameter of 4 μm are charged into a Shinagawa universal stirrer and mixed for 60 minutes. After that, 0.2 parts by mass of 2-ethyl-hexanol solution of chloroplatinic acid (2% by mass in platinum), 0.1 part by mass of toluene solution of ethynylcyclohexanol (50% by mass), formula (12) 0.7 parts by mass of heptamethylhydrogentrisiloxane represented by the following, 5.0 parts by mass of organohydrogenpolysiloxane (formula 11) were added in order, and after each addition, mixing was performed for 5 minutes each time, Finally, it was mixed for 5 minutes under a reduced pressure condition of -650 mmHg to obtain a composition b. The composition b was applied on a PET film so as to have a thickness of 1.0 mm, and left in an atmosphere at 150 ° C. for 10 minutes to form a sheet, whereby a sheet B was obtained.
［比較例１］
１０，０００ｍｍ2／ｓの粘度を持ち、両末端にビニル基を持つジメチルオルガノポリシロキサン１００質量部、４μｍの平均粒径をもつアルミナ５００質量部を品川式万能撹拌機に仕込み、６０分間混合せしめた後、塩化白金酸の２−エチル−ヘキサノール溶液（白金量で２質量％）を０．２質量部、エチニルシクロヘキサノールのトルエン溶液（５０質量％）を０．１質量部、オルガノハイドロジェンポリシロキサン（式１１）を５．０質量部、を順に添加し、各物質の添加後にその都度混合を５分行い、最後に−６５０ｍｍＨｇの減圧条件下で５分間混合せしめて組成物ｃを得た。この組成物ｃを、ＰＥＴフィルム上に厚さ１．０ｍｍとなるように塗布し、１５０℃の雰囲気下に１０分放置し、シート状に成形し、シートＣを得た。
[Comparative Example 1]
100 parts by weight of dimethylorganopolysiloxane having a viscosity of 10,000 mm 2 / s and vinyl groups at both ends and 500 parts by weight of alumina having an average particle diameter of 4 μm are charged into a Shinagawa universal stirrer and mixed for 60 minutes. Then, 0.2 parts by mass of 2-ethyl-hexanol solution of chloroplatinic acid (2% by mass in platinum), 0.1 part by mass of toluene solution of ethynylcyclohexanol (50% by mass), organohydrogenpoly 5.0 parts by mass of siloxane (Formula 11) was added in order, and after each addition, mixing was performed for 5 minutes each time, and finally, mixing was performed for 5 minutes under a reduced pressure of −650 mmHg to obtain a composition c. . This composition c was applied on a PET film so as to have a thickness of 1.0 mm, and left in an atmosphere at 150 ° C. for 10 minutes to form a sheet, whereby a sheet C was obtained.
［比較例２］
１０，０００ｍｍ2／ｓの粘度を持ち、両末端にビニル基を持つジメチルオルガノポリシロキサン１００質量部、４μｍの平均粒径をもつアルミナ５００質量部を品川式万能撹拌機に仕込み、６０分間混合せしめた後、塩化白金酸の２−エチル−ヘキサノール溶液（白金量で２質量％）を０．２質量部、エチニルシクロヘキサノールのトルエン溶液（５０質量％）を０．１質量部、オルガノハイドロジェンポリシロキサン（式１１）を２．０質量部、を順に添加し、各物質の添加後にその都度混合を５分行い、最後に−６５０ｍｍＨｇの減圧条件下で５分間混合せしめて組成物ｄを得た。この組成物ｄを、ＰＥＴフィルム上に厚さ１．０ｍｍとなるように塗布し、１５０℃の雰囲気下に１０分放置し、シート状に成形し、シートＤを得た。
[Comparative Example 2]
100 parts by weight of dimethylorganopolysiloxane having a viscosity of 10,000 mm 2 / s and vinyl groups at both ends and 500 parts by weight of alumina having an average particle diameter of 4 μm are charged into a Shinagawa universal stirrer and mixed for 60 minutes. Then, 0.2 parts by mass of 2-ethyl-hexanol solution of chloroplatinic acid (2% by mass in platinum), 0.1 part by mass of toluene solution of ethynylcyclohexanol (50% by mass), organohydrogenpoly 2.0 parts by mass of siloxane (formula 11) was added in order, and after each addition, mixing was performed for 5 minutes each time, and finally, mixing was performed for 5 minutes under a reduced pressure of −650 mmHg to obtain a composition d. . The composition d was applied on a PET film so as to have a thickness of 1.0 mm, and left in an atmosphere at 150 ° C. for 10 minutes to form a sheet, whereby a sheet D was obtained.
［比較例３］
組成物ｃを、ＰＥＴフィルム上に厚さ０．１０ｍｍとなるように塗布し、１５０℃の雰囲気下に１０分放置し、シート状に成形し、シートＣ’を得た。このシートＣ’上に、組成物ｄを厚さ０．９ｍｍとなるように塗布し、１５０℃の雰囲気下に１０分放置し、シート状に成形し、シートＥを得た。
[Comparative Example 3]
The composition c was applied on a PET film so as to have a thickness of 0.10 mm, left in an atmosphere at 150 ° C. for 10 minutes, and formed into a sheet shape to obtain a sheet C ′. On this sheet C ′, the composition d was applied so as to have a thickness of 0.9 mm, left in an atmosphere at 150 ° C. for 10 minutes, and formed into a sheet shape to obtain a sheet E.
［比較例４］
シートＤの開放側表面にオルガノハイドロジェンポリシロキサン（式１３）を５ｇ／ｍ2塗布し、１５０℃の雰囲気下に１０分放置し、シートＦを得た。
[Comparative Example 4]
5 g / m 2 of organohydrogenpolysiloxane (Formula 13) was applied to the surface of the open side of the sheet D and allowed to stand in an atmosphere at 150 ° C. for 10 minutes to obtain a sheet F.
これら成形したシートＡ〜Ｆの表面の粘着感と取り扱い性を確認した。 The adhesion feeling and the handleability of the surface of these molded sheets A to F were confirmed.
更に、これらシートＡ〜ＦをＴＯ−３Ｐ型トランジスタの形に模したモデルヒーターと、ヒートシンクの間に設置し、２９．４ｋＰａの荷重をかけ、モデルヒーターに２８Ｗの電力を印加した。電力印加開始１０分後のモデルヒーターの温度Ｔ１（℃）とヒートシンクの温度Ｔ２（℃）から以下の計算式により各組成物の熱抵抗を計算した。
熱抵抗＝（Ｔ１−Ｔ２）／２８
Further, these sheets A to F were placed between a model heater imitating the shape of a TO-3P transistor and a heat sink, a load of 29.4 kPa was applied, and 28 W of power was applied to the model heater. From the model heater temperature T1 (° C.) and the heat sink temperature T2 (° C.) 10 minutes after the start of power application, the thermal resistance of each composition was calculated according to the following formula.
Thermal resistance = (T1-T2) / 28
本発明によって、取り扱い性良好、低応力、かつ、熱特性の良好なシートを、１つの成形工程で成形することが可能になった。 According to the present invention, it is possible to form a sheet having good handleability, low stress, and good thermal characteristics in a single forming process.
Claims (4)
（ｂ）熱伝導性充填剤： ３００〜５，０００質量部、
（ｃ）ケイ素原子に直接結合した水素原子を分子中に平均で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： （ａ）成分中のアルケニル基に対する（ｃ）成分中のケイ素原子に直接結合した水素原子がモル比で０．６〜１０．０となる量、
（ｄ）白金族系付加反応触媒： 白金元素の量で０．１〜１，０００ｐｐｍ、
（ｅ）アルケニル基が付加可能なケイ素原子に直接結合した水素原子を分子中に一つ持つ揮発性化合物： （ｃ）成分中のケイ素原子に直接結合した水素原子に対する（ｅ）成分中のケイ素原子に直接結合した水素原子がモル比で０．０１〜２．０に相当する量
を構成成分とし、開放状態で加熱硬化し、開放側表面にスキン層が形成されることを特徴とする熱伝導性シリコーン組成物。 (A) Organopolysiloxane having at least two alkenyl groups in one molecule: 100 parts by mass
(B) Thermally conductive filler: 300 to 5,000 parts by mass,
(C) Organohydrogenpolysiloxane having an average of two or more hydrogen atoms directly bonded to silicon atoms in the molecule: (a) Hydrogen atoms directly bonded to silicon atoms in component (c) relative to alkenyl groups in component In an amount of 0.6 to 10.0 in molar ratio,
(D) Platinum group addition reaction catalyst: 0.1 to 1,000 ppm in the amount of platinum element,
(E) Volatile compound having in its molecule one hydrogen atom directly bonded to a silicon atom to which an alkenyl group can be added: (c) Silicon in component (e) with respect to a hydrogen atom directly bonded to a silicon atom in component The heat is characterized in that the hydrogen atoms directly bonded to the atoms have an amount corresponding to a molar ratio of 0.01 to 2.0 as a constituent component and are heat-cured in an open state to form a skin layer on the open-side surface. Conductive silicone composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006044694A JP4803365B2 (en) | 2006-02-22 | 2006-02-22 | Thermally conductive silicone composition, thermally conductive silicone molded article and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006044694A JP4803365B2 (en) | 2006-02-22 | 2006-02-22 | Thermally conductive silicone composition, thermally conductive silicone molded article and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2007224102A true JP2007224102A (en) | 2007-09-06 |
| JP4803365B2 JP4803365B2 (en) | 2011-10-26 |
Family
ID=38546205
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006044694A Expired - Fee Related JP4803365B2 (en) | 2006-02-22 | 2006-02-22 | Thermally conductive silicone composition, thermally conductive silicone molded article and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4803365B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009203373A (en) * | 2008-02-28 | 2009-09-10 | Momentive Performance Materials Inc | Thermoconductive silicone composition |
| JP2009256428A (en) * | 2008-04-15 | 2009-11-05 | Shin Etsu Chem Co Ltd | Heat conductive silicone composition, adhesion structure, and semiconductor device |
| WO2014065143A1 (en) * | 2012-10-22 | 2014-05-01 | Jnc株式会社 | Thermosetting resin composition |
| JP2015214665A (en) * | 2014-05-07 | 2015-12-03 | ビジョン開発株式会社 | Molding structure surface-hardened with addition-curable organopolysiloxane composition and production method thereof |
| JP2022545162A (en) * | 2019-07-26 | 2022-10-26 | ダウ シリコーンズ コーポレーション | Curable organopolysiloxane composition, cured product, and electrical/electronic device |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50124953A (en) * | 1974-03-19 | 1975-10-01 | ||
| JPS6422967A (en) * | 1987-07-17 | 1989-01-25 | Shinetsu Chemical Co | Curable liquid silicone rubber composition |
| JPH0423865A (en) * | 1990-05-17 | 1992-01-28 | Shin Etsu Chem Co Ltd | Adhesive organopolysiloxane composition and method for curing the same and its cured product |
| JP2004168920A (en) * | 2002-11-21 | 2004-06-17 | Dow Corning Toray Silicone Co Ltd | Thermally conductive silicone elastomer composition |
| JP2005206733A (en) * | 2004-01-23 | 2005-08-04 | Shin Etsu Chem Co Ltd | Thermally conductive silicone composition for heat radiation and its use method |
| JP2006182888A (en) * | 2004-12-27 | 2006-07-13 | Shin Etsu Chem Co Ltd | Manufacturing method of heat conductive member and heat dissipating structure |
-
2006
- 2006-02-22 JP JP2006044694A patent/JP4803365B2/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50124953A (en) * | 1974-03-19 | 1975-10-01 | ||
| JPS6422967A (en) * | 1987-07-17 | 1989-01-25 | Shinetsu Chemical Co | Curable liquid silicone rubber composition |
| JPH0423865A (en) * | 1990-05-17 | 1992-01-28 | Shin Etsu Chem Co Ltd | Adhesive organopolysiloxane composition and method for curing the same and its cured product |
| JP2004168920A (en) * | 2002-11-21 | 2004-06-17 | Dow Corning Toray Silicone Co Ltd | Thermally conductive silicone elastomer composition |
| JP2005206733A (en) * | 2004-01-23 | 2005-08-04 | Shin Etsu Chem Co Ltd | Thermally conductive silicone composition for heat radiation and its use method |
| JP2006182888A (en) * | 2004-12-27 | 2006-07-13 | Shin Etsu Chem Co Ltd | Manufacturing method of heat conductive member and heat dissipating structure |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009203373A (en) * | 2008-02-28 | 2009-09-10 | Momentive Performance Materials Inc | Thermoconductive silicone composition |
| JP2009256428A (en) * | 2008-04-15 | 2009-11-05 | Shin Etsu Chem Co Ltd | Heat conductive silicone composition, adhesion structure, and semiconductor device |
| WO2014065143A1 (en) * | 2012-10-22 | 2014-05-01 | Jnc株式会社 | Thermosetting resin composition |
| JPWO2014065143A1 (en) * | 2012-10-22 | 2016-09-08 | Jnc株式会社 | Thermosetting resin composition |
| US9512273B2 (en) | 2012-10-22 | 2016-12-06 | Jnc Corporation | Thermosetting resin composition |
| JP2015214665A (en) * | 2014-05-07 | 2015-12-03 | ビジョン開発株式会社 | Molding structure surface-hardened with addition-curable organopolysiloxane composition and production method thereof |
| JP2022545162A (en) * | 2019-07-26 | 2022-10-26 | ダウ シリコーンズ コーポレーション | Curable organopolysiloxane composition, cured product, and electrical/electronic device |
| JP7411063B2 (en) | 2019-07-26 | 2024-01-10 | ダウ シリコーンズ コーポレーション | Curable organopolysiloxane composition, cured product, and electrical/electronic equipment |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4803365B2 (en) | 2011-10-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5283346B2 (en) | Thermally conductive cured product and method for producing the same | |
| JP5015436B2 (en) | Thermally conductive silicone elastomer, thermal conductive medium and thermally conductive silicone elastomer composition | |
| EP1675174B1 (en) | Preparation of heat transfer member and heat-dissipating structure | |
| JP6032359B2 (en) | Thermally conductive composite sheet and heat dissipation structure | |
| JP6020187B2 (en) | Thermally conductive composite sheet | |
| WO2019098290A1 (en) | Two-step curable thermally conductive silicone composition and method for producing same | |
| JP4144998B2 (en) | Material for heat dissipation | |
| JP6314915B2 (en) | Heat dissipation putty sheet | |
| JP2009203373A (en) | Thermoconductive silicone composition | |
| JP2016082155A (en) | Heat dissipation sheet | |
| JP2020002236A (en) | Heat-conductive silicone composition, heat-conductive silicone sheet, and method of manufacturing the same | |
| JP4803365B2 (en) | Thermally conductive silicone composition, thermally conductive silicone molded article and method for producing the same | |
| JP4463117B2 (en) | Flame-retardant and heat-conductive silicone molded article and method for producing the same | |
| TW200536896A (en) | Composition for heat conductive siloxanes heat release and its using method | |
| US7034073B2 (en) | Heat conductive silicone composition and shaped article | |
| JP7264850B2 (en) | Thermally conductive silicone composition, cured product thereof, and heat dissipation sheet | |
| JP6558301B2 (en) | Thermally conductive composite sheet | |
| JP2016219732A (en) | Thermal conducive composite silicone rubber sheet | |
| JP2008160126A (en) | Cooling structure of electronic component | |
| JP4299324B2 (en) | Thermally conductive silicone composition and thermally conductive silicone molded article | |
| JP5418620B2 (en) | Thermal conduction member | |
| JP2004010691A (en) | Thermally conductive silicone rubber molding | |
| WO2020084868A1 (en) | Thermally conductive silicone composition and cured product thereof | |
| JP2020189929A (en) | Method of producing non-tacky heat-conductive silicone rubber sheet | |
| JP2005035264A (en) | Heat conductive silicone shaped body and its manufacturing process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20080125 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20100921 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100929 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20101119 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20110713 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20110726 |
|
| R150 | Certificate of patent (=grant) or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140819 Year of fee payment: 3 |
|
| LAPS | Cancellation because of no payment of annual fees |