TW201816070A - Highly thermally conductive composite material - Google Patents

Abstract

Provided is a highly thermally conductive composite material which is excellent in terms of heat resistance and thermal conductivity. The highly thermally conductive composite material is for thermal conduction applications and is obtained by incorporating a thermally conductive filler having a thermal conductivity of 20 W.m-1.K-1 or greater into a resin. The resin is a phenyl-modified polydimethylsiloxane-based hybrid polymer comprising a product of the reaction of the following prepolymers (A) and (B). The prepolymer (A) is a phenyl-modified hybrid prepolymer which comprises a product of condensation of a polydimethylsiloxane having silanol groups at both terminals with a phenyltrialkoxysilane, and the prepolymer (B) is a phenyl-modified hybrid prepolymer which comprises a product of hydrolysis/condensation of a polydimethylsiloxane having trialkoxysilyl groups at both terminals with a phenyltrialkoxysilane and a diphenyldialkoxysilane.

Description

高熱傳導複合材料High thermal conductivity composite material

本發明是關於一種調配了熱傳導性填料而成之熱傳導複合材料。The invention relates to a heat conductive composite material prepared by blending a heat conductive filler.

以藉由熱傳導特性而實行的散熱或熱釋放為目的之複合構件（以下稱為散熱構件），被廣泛使用於以重型電機相關或電器製品等為主的方面。此散熱構件，是由具有高熱傳導性的陶瓷或金屬等填料、和可賦予彈性的耐熱樹脂之複合材料所構成。近年來，由於電子零件的高密度化、高集積化，所要求的熱傳導率變高，運算元件所產生的熱量也變大。又，製品的小型化、薄膜化的要求也高，在尋求絕緣性的用途上，是尋求即便在高使用溫度的環境中亦能穩定並具有高絕緣性。Composite members (hereinafter referred to as heat-dissipating members) whose purpose is to dissipate heat or release heat based on thermal conduction characteristics are widely used in areas such as heavy-duty motors or electrical appliances. This heat radiating member is composed of a composite material such as a ceramic or metal filler having high thermal conductivity, and a heat-resistant resin that can impart elasticity. In recent years, due to the increase in density and integration of electronic components, the required thermal conductivity has increased, and the amount of heat generated by computing elements has also increased. In addition, there is also a high demand for miniaturization and thinning of products, and in applications where insulation is sought, it is sought to be stable and have high insulation even in an environment with a high use temperature.

對於高電絕緣性且高熱傳導的要求，大多是採用高熱傳導性的陶瓷填料。在泛用上是採用氧化鋁，若進一步尋求機能性時則是採用氮化物或氧化鋯系氧化物等。其中，又以氮化鋁（以下稱為AlN）作為高熱傳導性填料而受到矚目。For the requirements of high electrical insulation and high thermal conductivity, ceramic fillers with high thermal conductivity are mostly used. For general use, alumina is used, and if further function is sought, nitride or zirconia-based oxide is used. Among them, aluminum nitride (hereinafter referred to as AlN) has attracted attention as a highly thermally conductive filler.

AlN，作為填料而具有170W‧m^-1 ‧K^-1 的高熱傳導率，其燒結體則作為熱傳導絕緣材料而被廣泛地實用於以車載用途為首的方面。該AlN燒結填料被使用作為對各種樹脂材料的添加劑。對於原本熱傳導率低的樹脂，AlN燒結填料可賦予高熱傳導性，所以藉由將AlN燒結填料和樹脂進行複合化以做成散熱構件，而可在各領域中作為發熱體的冷卻之用而實用化。AlN has a high thermal conductivity of 170W‧m ^-1 ‧K ^-1 as a filler, and its sintered body is widely used as a thermally conductive insulating material for applications including automotive applications. The AlN sintered filler is used as an additive to various resin materials. For resins with low thermal conductivity, AlN sintered fillers can provide high thermal conductivity. Therefore, by combining AlN sintered fillers and resins to form heat-dissipating members, they can be practically used as cooling elements in various fields. Into.

此種散熱構件，其與發熱體之間的密著性備受重視。所以，其尋求能承受來自發熱體的發熱的耐熱性、和能不殘存空氣層而密著於發熱體的低硬度柔軟性。對於此種用途，一般是使用兼具耐熱性和柔軟性的矽氧樹脂。矽氧樹脂具有能在150℃～170℃左右的溫度中連續使用的耐熱性，一般是作為低價格且安全性亦高的彈性材料而為人所熟知。但是，近年來的電源模組等，如前述般地趨向小型化、薄膜化，其被要求的耐熱溫度則逐漸上升。又，近年來受到矚目而加速研究開發的次世代碳化矽（SiC）、氮化鎵（GaN）電源模組等，動作溫度為200℃以上的高溫，則既有的矽氧樹脂等會暴露出硬度上升或揮發成分多等問題。又，矽氧樹脂在高溫下，其電絕緣性的降低亦令人顧慮，所以近年來其在電氣構件中的使用亦逐漸受到顧慮。Such a heat radiating member has attracted much attention to the adhesion between the heat radiating member and the body. Therefore, it is required to have heat resistance capable of withstanding heat generation from the heating element and low hardness and flexibility capable of adhering to the heating element without leaving an air layer. For such applications, a silicone resin having both heat resistance and flexibility is generally used. Silicone resin has heat resistance that can be continuously used at a temperature of about 150 ° C to 170 ° C, and is generally known as an elastic material with low price and high safety. However, in recent years, power modules and the like have been miniaturized and thinned as described above, and the required heat-resistant temperature has gradually increased. In addition, in recent years, the next-generation silicon carbide (SiC), gallium nitride (GaN) power modules, etc., which have received attention and accelerated research and development, have been exposed to existing silicone resins, etc. at operating temperatures above 200 ° C. Problems such as increased hardness or many volatile components. In addition, the reduction in electrical insulation properties of silicone resins at high temperatures is also a cause for concern, so in recent years its use in electrical components has also become a concern.

作為滿足此耐熱性的材料，最近已開發了一種有機-無機混成組成物，其將無機成分導入至矽氧樹脂原料中而提升上述矽氧樹脂的特性。有機-無機混成組成物，是兼具下述特性的材料：有機成分也就是矽氧樹脂的柔軟性、撥水性、脫模性等特性；及，無機成分的耐熱性、黏接性等特性；該有機-無機混成組成物，被提出作為一種具有連續使用溫度200℃以上的高耐熱性和柔軟性且進一步具有高電絕緣性等優異特性的材料（專利文獻1～2）。而且，亦已提出一種材料，是將熱傳導性填料以高濃度導入至有機-無機混成組成物中而成（專利文獻3～5）。 [先前技術文獻] （專利文獻）As a material satisfying this heat resistance, an organic-inorganic hybrid composition has been recently developed which introduces an inorganic component into a silicone resin raw material to improve the characteristics of the silicone resin. Organic-inorganic hybrid composition is a material that has the following characteristics: the organic component, that is, the softness, water repellency, and release properties of the silicone resin; and the heat resistance and adhesion properties of the inorganic component; This organic-inorganic hybrid composition has been proposed as a material having high heat resistance and flexibility at a continuous use temperature of 200 ° C. or higher, and further excellent properties such as high electrical insulation (Patent Documents 1 to 2). In addition, a material has been proposed in which a thermally conductive filler is introduced into an organic-inorganic mixed composition at a high concentration (Patent Documents 3 to 5). [Prior Art Literature] (Patent Literature)

專利文獻1：日本再表2010-090280號公報 專利文獻2：日本特開2016-003317號公報 專利文獻3：日本特開2004-250665號公報 專利文獻4：日本特開2014-210857號公報 專利文獻5：日本特開2015-013927號公報Patent Document 1: Japanese Patent Application Publication No. 2010-090280 Patent Document 2: Japanese Patent Application Publication No. 2016-003317 Patent Document 3: Japanese Patent Application Publication No. 2004-250665 Patent Literature 4: Japanese Patent Application Publication No. 2014-210857 5: Japanese Patent Laid-Open No. 2015-013927

[發明所欲解決之問題] 然而，在高溫下的使用時，維持電絕緣性、高熱傳導性、低硬度柔軟性、黏接性仍然是困難的。[Problems to be Solved by the Invention] However, it is still difficult to maintain electrical insulation, high thermal conductivity, low hardness softness, and adhesion when used at high temperatures.

高耐熱性的熱傳導性材料中，重要的不只是上述般的高溫中的樹脂劣化，亦必須考慮熱傳導性填料的劣化。尤其在作為高熱傳導性填料而著名的填料中，有AlN。AlN的熱傳導率，是廣泛使用的氧化鋁的熱傳導率的5倍左右之高，因此理論上可降低調配量、可降低散熱構件的硬度。但是，已知AlN容易與大氣中的水分反應而發生水解，被分解為氫氧化鋁與氨（AlN＋3H₂ O→Al(OH)₃ ＋NH₃ ）。若AlN受到水解而變成Al(OH)₃ ，則熱傳導性會降低，無法賦予高熱傳導性。此狀態下，尤其是重視耐熱性的熱傳導片等所使用的矽氧樹脂等，沒有阻隔大氣中的水蒸氣之氣體阻障性，作為填料而經複合化之AlN會容易地水解。因此，在氣體阻障性低的樹脂中，會容易發生水解，熱傳導率會經時性地降低。此種填料的變化，會使製品品質顯著降低。Among thermally conductive materials having high heat resistance, it is important not only to deteriorate the resin at high temperatures as described above, but also to consider deterioration of the thermally conductive filler. Among the fillers known as highly thermally conductive fillers are AlN. The thermal conductivity of AlN is about 5 times higher than the thermal conductivity of widely used aluminum oxide. Therefore, in theory, the blending amount can be reduced and the hardness of the heat dissipation member can be reduced. However, it is known that AlN easily reacts with moisture in the atmosphere to undergo hydrolysis, and is decomposed into aluminum hydroxide and ammonia (AlN + 3H ₂ O → Al (OH) ₃ + NH ₃ ). When AlN is hydrolyzed to Al (OH) ₃ , the thermal conductivity is reduced, and high thermal conductivity cannot be provided. In this state, especially silicone resins used for heat-conductive sheets and the like that attach importance to heat resistance do not have gas barrier properties to block water vapor in the atmosphere, and the compounded AlN is easily hydrolyzed as a filler. Therefore, in a resin having a low gas barrier property, hydrolysis tends to occur, and the thermal conductivity decreases with time. Changes in such fillers can significantly reduce product quality.

因此，本發明的目的在於提供一種高熱傳導構件，其耐熱性和熱傳導性優異。本發明的目的進一步在於提供一種熱傳導性構件，其在散熱構件等熱傳導構件中，在200℃以上的高溫環境中不會發生黏接性降低、硬度上升、電絕緣性降低之類的問題。 [解決問題之技術手段]Therefore, an object of the present invention is to provide a highly thermally conductive member that is excellent in heat resistance and thermal conductivity. Another object of the present invention is to provide a thermally conductive member that does not cause problems such as a decrease in adhesion, a rise in hardness, and a decrease in electrical insulation in a high-temperature environment of 200 ° C. or higher in a thermally conductive member such as a heat sink member. [Technical means to solve the problem]

依照本發明而完成的高熱傳導複合材料，其特徵在於：是於樹脂中調配有熱傳導率為20W‧m^-1 ‧K^-1 以上的熱傳導性填料而成之熱傳導用途的複合材料，該樹脂是苯基改質聚二甲基矽氧烷系混成聚合物，其包含下述預聚物（A）和預聚物（B）之反應物： 預聚物（A）是苯基改質混成預聚物，其包含由在兩端具有矽醇基之聚二甲基矽氧烷、和苯基三烷氧基矽烷所形成之縮合反應生成物； 預聚物（B）是苯基改質混成預聚物，其包含由在兩端具有三烷氧矽基（trialkoxysilyl group）之聚二甲基矽氧烷、苯基三烷氧基矽烷及二苯基二烷氧基矽烷所形成之水解縮合反應生成物。The high-heat-conducting composite material completed according to the present invention is characterized in that it is a heat-conducting composite material prepared by disposing a thermally conductive filler having a thermal conductivity of 20W‧m ^-1 ‧K ^-1 or more in a resin. The resin is Phenyl modified polydimethylsiloxane based hybrid polymer, which includes the following prepolymers (A) and reactants of prepolymer (B): The prepolymer (A) is a phenyl modified mixed prepolymer A polymer comprising a condensation reaction product formed of a polydimethylsiloxane having a silanol group at both ends and a phenyltrialkoxysilane; and the prepolymer (B) is a modified phenyl group Prepolymer comprising a hydrolytic condensation formed by polydimethylsiloxanes having trialkoxysilyl groups at both ends, phenyltrialkoxysilane, and diphenyldialkoxysilane Reaction product.

又，在本發明的高熱傳導複合材料中，所採用作為預聚物（A）的原料之前述在兩端具有矽醇基之聚二甲基矽氧烷，較佳是數量平均分子量（Mn）為25000～45000，且分子量分佈指數（Mw／Mn；Mw為重量平均分子量）為1.4以下，而所採用作為預聚物（B）的原料之前述在兩端具有三烷氧矽基之聚二甲基矽氧烷，較佳是數量平均分子量（Mn）為15000～28000，且分子量分佈指數（Mw／Mn；Mw為重量平均分子量）為1.3以下。In the high thermal conductivity composite material of the present invention, the aforementioned polydimethylsiloxane having silanol groups at both ends as a raw material of the prepolymer (A) is preferably a number average molecular weight (Mn). It is 25,000 to 45000, and the molecular weight distribution index (Mw / Mn; Mw is weight average molecular weight) is 1.4 or less, and the aforementioned polydiamine having a trialkoxysilyl group at both ends is used as a raw material of the prepolymer (B) The methylsiloxane preferably has a number average molecular weight (Mn) of 15,000 to 28,000 and a molecular weight distribution index (Mw / Mn; Mw is a weight average molecular weight) of 1.3 or less.

又，本發明的高熱傳導複合材料中，前述熱傳導性填料，較佳是在填料表面具有可進行脫水或脫醇反應之官能基。In the highly thermally conductive composite material of the present invention, it is preferable that the thermally conductive filler has a functional group capable of performing a dehydration or dealcoholization reaction on the surface of the filler.

又，本發明的高熱傳導複合材料中，前述熱傳導性填料的熱傳導率較佳是150W‧m^-1 ‧K^-1 以上。In the highly thermally conductive composite material of the present invention, the thermal conductivity of the thermally conductive filler is preferably 150 W · m ^-1 ‧K ^-1 or more.

又，本發明的高熱傳導複合材料中，前述熱傳導性填料較佳是包含氮化鋁填料。In the highly thermally conductive composite material of the present invention, the thermally conductive filler preferably contains an aluminum nitride filler.

又，本發明的高熱傳導複合材料中，前述熱傳導性填料，較佳是僅添加氮化鋁、或於氮化鋁中添加氧化鋁及氮化硼之中的至少一種而成，且相對於全部的熱傳導性填料而言，平均粒徑20～100μm的氮化鋁填料的比率為25wt%以上，剩餘部分則為平均粒徑小於該氮化鋁填料之填料。In the highly thermally conductive composite material of the present invention, it is preferable that the thermally conductive filler is formed by adding only aluminum nitride or at least one of aluminum oxide and boron nitride to aluminum nitride, and it is relative to all As for the thermally conductive filler, the ratio of the aluminum nitride filler having an average particle diameter of 20 to 100 μm is 25% by weight or more, and the remainder is a filler having an average particle diameter smaller than the aluminum nitride filler.

又，本發明的高熱傳導複合材料中，前述預聚物（A）和前述預聚物（B）之合計質量、與前述熱傳導性填料之合計質量的比，較佳是預聚物：填料＝5：95～30：70。In the highly thermally conductive composite material of the present invention, the ratio of the total mass of the prepolymer (A) and the prepolymer (B) to the total mass of the thermally conductive filler is preferably a prepolymer: filler = 5: 95 to 30: 70.

又，本發明的高熱傳導複合材料中，前述熱傳導性填料是平均粒徑為0.2～10μm的氧化鋁填料，前述預聚物（A）和前述預聚物（B）之合計質量、與前述氧化鋁填料之質量的比，較佳是預聚物：填料＝5：95～30：70。In the highly thermally conductive composite material of the present invention, the thermally conductive filler is an alumina filler having an average particle diameter of 0.2 to 10 μm, the total mass of the prepolymer (A) and the prepolymer (B), and the oxidation. The mass ratio of the aluminum filler is preferably prepolymer: filler = 5:95 to 30:70.

又，本發明的高熱傳導複合材料，較佳是熱傳導率為4.0W‧m^-1 ‧K^-1 以上。The high thermal conductivity composite material of the present invention preferably has a thermal conductivity of 4.0 W‧m ^-1 ‧K ^-1 or more.

又，依照本發明而完成的熱傳導糊劑，包含上述任一種高熱傳導複合材料。另外，熱傳導糊劑亦可僅由上述任一種高熱傳導複合材料所形成。The heat conductive paste prepared according to the present invention includes any one of the above-mentioned high heat conductive composite materials. In addition, the heat conductive paste may be formed of only one of the above-mentioned high heat conductive composite materials.

又，本發明的高熱傳導複合材料，較佳是彈性模數為20MPa以下。The high thermal conductivity composite material of the present invention preferably has an elastic modulus of 20 MPa or less.

又，依照本發明而完成的熱傳導片，包含上述任一種高熱傳導複合材料。另外，熱傳導片亦可僅由上述任一種高熱傳導複合材料所形成。 [發明之功效]The thermally conductive sheet completed according to the present invention includes any of the above-mentioned high thermally conductive composite materials. In addition, the heat conductive sheet may be formed of only one of the above-mentioned high heat conductive composite materials. [Effect of the invention]

藉由此方式，可提供一種高熱傳導構件，其耐熱性和熱傳導性優異。進一步，可提供一種熱傳導性構件，其在散熱構件等熱傳導構件中，在200℃以上的高溫環境中不會發生黏接性降低、硬度上升、電絕緣性降低等問題。In this way, a highly thermally conductive member can be provided, which is excellent in heat resistance and thermal conductivity. Further, it is possible to provide a thermally conductive member that does not cause problems such as a decrease in adhesion, a rise in hardness, and a decrease in electrical insulation in a high-temperature environment of 200 ° C. or higher in a thermally conductive member such as a heat dissipation member.

以下詳細地說明本發明。 ＜在兩端具有矽醇基之聚二甲基矽氧烷（PDMS-1）＞ 具有賦予表面黏著性與柔軟性之功效的苯基改質混成預聚物（A），其PDMS原料是在兩端具有矽醇基之聚二甲基矽氧烷（PDMS-1），較佳是由通式（1）表示者。The present invention will be described in detail below. ＜ Polydimethylsiloxane (PDMS-1) with silanol groups at both ends ＞ The phenyl group is modified and mixed into a prepolymer (A) with the function of giving surface adhesion and softness. The PDMS raw material is Polydimethylsiloxane (PDMS-1) having a silanol group at both ends is preferably represented by the general formula (1).

一般的聚二甲基矽氧烷，具有比較廣的分子量分佈，所以反應時間和反應溫度等也很寬廣。因此，通常難以表現明確的特性。本發明的原料所使用的在兩端具有矽醇基之聚二甲基矽氧烷，較佳是使用烷基鋰作為起始劑，並以活性陰離子聚合等方式製造而成且分子量分佈狹窄而均勻者。以重量平均分子量（Mw）與數量平均分子量（Mn）之比率所算出的分子量分佈指數（Mw／Mn），較佳是採用1.4以下者，進一步較佳是1.3以下者，更佳是1.2以下者，最佳是1.1以下者。在兩端具有矽醇基之聚二甲基矽氧烷，若分子量分佈指數（Mw／Mn）是1.4以下或進一步是1.3以下，則苯基改質反應容易進行，亦無硬化不良之虞。而且，當在將苯基改質混成預聚物（A）與後述的苯基改質混成預聚物（B）混合而獲得之苯基改質聚二甲基矽氧烷系混成預聚物（C）中，添加、混合熱傳導性填料（若為熱傳導片時，進一步使其加熱硬化）而獲得之高熱傳導複合材料，經過長時間亦能維持耐熱性（即便在200℃以上的高溫環境中長期使用，亦不會發生黏接性降低、硬度上升、電絕緣性降低這類的問題）。進一步，在兩端具有矽醇基之聚二甲基矽氧烷，若分子量分佈指數（Mw／Mn）是1.2以下或進一步是1.1以下，則可獲得在200℃以上的高溫中的耐熱維持特性特別優異的高熱傳導複合材料。此分子量分佈指數（Mw／Mn）大於1.4者，低分子成分或高分子成分的比率較高，苯基改質反應難以進行，或是會有硬化時未反應成分變多、硬化不良之虞，在耐熱環境也就是本發明之用途中會有較為不佳的情形。General polydimethylsiloxane has a relatively wide molecular weight distribution, so the reaction time and reaction temperature are also very wide. Therefore, it is often difficult to express clear characteristics. The polydimethylsiloxane having a silanol group at both ends used in the raw material of the present invention is preferably produced by using an alkyl lithium as a starter and produced by living anion polymerization and the like, and has a narrow molecular weight distribution. Uniform. The molecular weight distribution index (Mw / Mn) calculated by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably 1.4 or less, more preferably 1.3 or less, and even more preferably 1.2 or less. The best is below 1.1. If the polydimethylsiloxane having a silanol group at both ends has a molecular weight distribution index (Mw / Mn) of 1.4 or less and further 1.3 or less, the phenyl modification reaction is easy to proceed and there is no risk of poor curing. In addition, a phenyl-modified polydimethylsiloxane system obtained by mixing a phenyl-modified modified prepolymer (A) with a phenyl-modified modified prepolymer (B) described later is mixed into a prepolymer. In (C), the highly thermally conductive composite material obtained by adding and mixing a thermally conductive filler (if it is a thermally conductive sheet and further heat-hardening it) can maintain heat resistance over a long period of time (even in a high temperature environment of 200 ° C or higher) Long-term use will not cause problems such as reduced adhesion, increased hardness, and reduced electrical insulation). Further, if the polydimethylsiloxane having a silanol group at both ends has a molecular weight distribution index (Mw / Mn) of 1.2 or less, or more than 1.1, a heat-resistant maintenance characteristic at a high temperature of 200 ° C or higher can be obtained. Particularly excellent high thermal conductivity composite material. If the molecular weight distribution index (Mw / Mn) is greater than 1.4, the ratio of low-molecular components or high-molecular components is high, and the phenyl modification reaction is difficult to proceed, or there may be more unreacted components during curing and poor curing. In a heat-resistant environment, that is, in the application of the present invention, there may be a relatively poor situation.

進一步，成為苯基改質混成預聚物（A）的原料之聚二甲基矽氧烷（PDMS-1），其數量平均分子量（Mn）較佳是25000～45000。若數量平均分子量（Mn）是25000以上，則可提升高熱傳導複合材料的耐熱性，並且可使其表現出黏著性。又，若數量平均分子量（Mn）是45000以下，則可容易地合成聚二甲基矽氧烷（PDMS-1）及苯基改質混成預聚物（A）。若數量平均分子量（Mn）小於25000，則高熱傳導複合材料的耐熱性降低，並且可能會難以表現黏著性，相反地，若大於45000，則聚二甲基矽氧烷（PDMS-1）及苯基改質混成預聚物（A）的合成變得困難，並且會有所製作而成之預聚物的黏度過高、與熱傳導性填料之間的複合化變得困難之虞。當特別期望耐熱性和柔軟性時，例如當在250℃以上的高溫下使用時等情形，較佳是採用數量平均分子量（Mn）為30000以上的PDMS，若進一步考慮耐熱維持特性、黏著性、黏度、合成之容易性等的均衡，則進一步較佳的數量平均分子量大約為30000～44000。Furthermore, the polydimethylsiloxane (PDMS-1), which is a raw material of the phenyl modification and mixed into the prepolymer (A), preferably has a number average molecular weight (Mn) of 25,000 to 45,000. When the number-average molecular weight (Mn) is 25,000 or more, the heat resistance of the high thermal conductivity composite material can be improved, and the adhesiveness can be exhibited. In addition, if the number average molecular weight (Mn) is 45,000 or less, polydimethylsiloxane (PDMS-1) and phenyl modification can be easily synthesized into a prepolymer (A). If the number average molecular weight (Mn) is less than 25,000, the heat resistance of the high heat conductive composite material is reduced, and it may be difficult to express adhesion. On the contrary, if it is more than 45,000, polydimethylsiloxane (PDMS-1) and benzene It is difficult to synthesize the base modified and mixed into the prepolymer (A), and the prepolymer produced may be too high in viscosity, and it may become difficult to compound with the thermally conductive filler. When heat resistance and flexibility are particularly desired, such as when used at a high temperature of 250 ° C or higher, it is preferable to use PDMS with a number average molecular weight (Mn) of 30,000 or more. If further consideration is given to heat retention characteristics, adhesiveness, For a balance of viscosity, ease of synthesis, and the like, a more preferable number average molecular weight is about 30,000 to 44,000.

作為本發明所採用的在兩端具有矽醇基之聚二甲基矽氧烷，特佳是JNC股份有限公司製造的FM9927（代表值：Mn＝32000，Mw／Mn＝1.09；有批次間差異，Mn＝29000～37000，Mw／Mn＝1.06～1.25）、FM9928（代表值：Mn＝47000，Mw／Mn＝1.11；有批次間差異，Mn＝45000～48000，Mw／Mn＝1.10～1.35）等。關於FM9927、FM9928各自的Mn和Mw／Mn，雖然有大約在上述範圍內的批次間差異，但藉由此範圍內的差異，所獲得之苯基改質混成預聚物（A）、進一步獲得之苯基改質聚二甲基矽氧烷系混成預聚物（C）及高熱傳導複合材料的物性等，不會產生很大的差異。這些原料，為了在使用前去除低沸點成分，所以亦可進行蒸發處理。此情形中，數量平均分子量（Mn）、分子量分佈指數（Mw／Mn）有增加的趨勢。As the polydimethylsiloxane having a silanol group at both ends used in the present invention, particularly preferred is FM9927 (representative value: Mn = 32000, Mw / Mn = 1.09; manufactured by JNC Corporation); Differences, Mn = 29000 ～ 37000, Mw / Mn = 1.06 ～ 1.25), FM9928 (representative values: Mn = 47000, Mw / Mn = 1.11; there are differences between batches, Mn = 45000 ～ 48000, Mw / Mn = 1.10 ～ 1.35) etc. Regarding the respective Mn and Mw / Mn of FM9927 and FM9928, although there are batch-to-batch differences within the above-mentioned range, the phenyl groups obtained are modified and mixed into the prepolymer (A) through the differences in this range. The physical properties of the obtained phenyl-modified polydimethylsiloxane-based prepolymer (C) and the high heat-conducting composite material do not differ greatly. These raw materials may be subjected to evaporation treatment in order to remove low-boiling components before use. In this case, the number average molecular weight (Mn) and molecular weight distribution index (Mw / Mn) tend to increase.

＜在兩端具有三烷氧矽基之聚二甲基矽氧烷（PDMS-2）＞ 表現固體維持性的苯基改質混成預聚物（B），其PDMS原料是在兩端具有三烷氧矽基之聚二甲基矽氧烷（PDMS-2），較佳是由通式（2）表示者。<Polydimethylsiloxane (PDMS-2) with a trialkoxysilyl group at both ends> A phenyl group that exhibits solid retention and is modified into a prepolymer (B). The PDMS raw material is The alkoxysilyl-based polydimethylsiloxane (PDMS-2) is preferably represented by the general formula (2).

此處，R¹ 是碳數為1～3的烷基，選自甲基、乙基、正丙基、異丙基，可全部相同，亦可部分或全部不同。從反應性、安全面及反應控制的觀點而言，R¹ 最佳是乙基。X是氧或碳數為2以下的伸烷基，可相同亦可不同。 Here, R ¹ is an alkyl group having 1 to 3 carbon atoms, and is selected from methyl, ethyl, n-propyl, and isopropyl, and may be all the same or may be partially or completely different. From the viewpoints of reactivity, safety surface, and reaction control, R ^{1 is} preferably an ethyl group. X is oxygen or an alkylene group having a carbon number of 2 or less, and may be the same or different.

藉由在兩端具有三烷氧矽基，會增加聚二甲基矽氧烷與二苯基二烷氧基矽烷或者其部分水解物或縮合物之間的反應部位，而提高所期望的縮合反應速度，該二苯基二烷氧基矽烷或者其部分水解物或縮合物，係因立體障礙以致反應性差。關於此原料，亦與上述在兩端具有矽醇基之聚二甲基矽氧烷同樣，期望其分子量分佈狹窄。分子量分佈狹窄的這種PDMS，同樣可以在活性陰離子聚合的應用下合成。關於在兩端具有三烷氧矽基之聚二甲基矽氧烷，分子量分佈指數（Mw／Mn）較佳是採用1.3以下者，進一步較佳是1.2以下者，更佳是1.1以下者。若在兩端具有三烷氧矽基之聚二甲基矽氧烷的分子量分佈指數（Mw／Mn）是1.3以下，進一步是1.2以下，則苯基改質反應容易進行，亦無硬化不良之虞。而且，當在後述的苯基改質聚二甲基矽氧烷系混成預聚物（C）中，添加、混合熱傳導性填料（若為熱傳導片時進一步使其加熱硬化）而獲得之高熱傳導複合材料，經過長時間亦能維持耐熱性（即便在200℃以上的高溫環境中長期使用，亦不會發生黏接性降低、硬度上升、電絕緣性降低之類的問題）。進一步，在兩端具有三烷氧矽基之聚二甲基矽氧烷，若分子量分佈指數（Mw／Mn）是1.1以下，則可獲得在更進一步的高溫中的耐熱維持特性特別優異的高熱傳導複合材料。此分子量分佈指數（Mw／Mn）若為大於1.3者，則低分子成分或高分子成分的比率較高，苯基改質反應難以進行，或是會有硬化時未反應成分較多、硬化不良之虞。另外，反應時，在兩端具有三烷氧矽基之聚二甲基矽氧烷，其烷氧基亦可部分或全部被水解而生成矽醇基。By having a trialkoxysilyl group at both ends, the reaction site between polydimethylsiloxane and diphenyldialkoxysilane or a partial hydrolysate or condensate thereof is increased, and the desired condensation is increased. The reaction rate is that the diphenyldialkoxysilane or its partial hydrolysate or condensate has poor reactivity due to steric hindrance. This raw material is also expected to have a narrow molecular weight distribution similar to the polydimethylsiloxane having a silanol group at both ends. This kind of PDMS with narrow molecular weight distribution can also be synthesized under the application of living anionic polymerization. Regarding polydimethylsiloxane having a trialkoxysilyl group at both ends, the molecular weight distribution index (Mw / Mn) is preferably 1.3 or less, more preferably 1.2 or less, and even more preferably 1.1 or less. If the molecular weight distribution index (Mw / Mn) of polydimethylsiloxane having a trialkoxysilyl group at both ends is 1.3 or less, and further 1.2 or less, the phenyl modification reaction is easy to proceed, and there is no poor curing. Yu. In addition, a high thermal conductivity obtained by adding and mixing a thermally conductive filler (if a thermally conductive sheet is further heated and hardened) is added to a phenyl-modified polydimethylsiloxane-based prepolymer (C) described later. The composite material can maintain heat resistance over a long period of time (even if it is used for a long time in a high temperature environment above 200 ° C, problems such as reduced adhesion, increased hardness, and decreased electrical insulation) will not occur. Furthermore, if the polydimethylsiloxane having a trialkoxysilyl group at both ends has a molecular weight distribution index (Mw / Mn) of 1.1 or less, it is possible to obtain a particularly high heat-maintaining property at a further high temperature. Thermally conductive composites. If the molecular weight distribution index (Mw / Mn) is greater than 1.3, the ratio of low-molecular components or high-molecular components is high, and the phenyl modification reaction is difficult to proceed, or there may be many unreacted components during curing and poor curing. Fear. In addition, during the reaction, the alkoxy group of the polydimethylsiloxane having a trialkoxysilyl group at both ends may be partially or completely hydrolyzed to form a silanol group.

進一步，成為苯基改質混成預聚物（B）的原料之聚二甲基矽氧烷（PDMS-2），其數量平均分子量（Mn）較佳是15000～28000。若數量平均分子量（Mn）是15000以上，則可提升高熱傳導複合材料的耐熱性，並且抑制其收縮，使成形容易。又，若數量平均分子量（Mn）是28000以下，則可提高硬度、抑制黏著性。若數量平均分子量（Mn）小於15000，則高熱傳導複合材料的耐熱性降低，並且其收縮亦增大，有成形變得困難之虞。相反地，若大於28000，則會由於聚合物特有的低硬度化以致苯基改質混成預聚物（B）亦產生黏著性，而有無法控制苯基改質聚二甲基矽氧烷系混成預聚物（C）及高熱傳導複合材料的黏著性之虞。若考慮耐熱維持特性、收縮率、黏著性等，則較佳的數量平均分子量大約是18000～23000。Further, the polydimethylsiloxane (PDMS-2), which is a raw material of the phenyl modification and mixed into the prepolymer (B), preferably has a number average molecular weight (Mn) of 15,000 to 28,000. When the number-average molecular weight (Mn) is 15,000 or more, the heat resistance of the high-thermal-conductivity composite material can be improved, and its shrinkage can be suppressed, so that molding can be facilitated. In addition, if the number average molecular weight (Mn) is 28,000 or less, hardness can be increased and adhesion can be suppressed. When the number-average molecular weight (Mn) is less than 15,000, the heat resistance of the high heat-conductive composite material decreases, and the shrinkage thereof also increases, which may cause difficulty in molding. Conversely, if it is more than 28000, the phenyl modification will be mixed into the prepolymer (B) due to the unique low hardness of the polymer, and the dimethyl modification will not be controlled. There is a concern that the prepolymer (C) and the high thermal conductivity composite material are mixed. In consideration of heat resistance maintenance characteristics, shrinkage, adhesion, and the like, a preferable number average molecular weight is approximately 18,000 to 23,000.

作為本發明所採用的在兩端具有三烷氧矽基之聚二甲基矽氧烷，特佳者可舉出JNC股份有限公司製造的FM8826（代表值：Mn＝20000，Mw／Mn＝1.06；有批次間差異，Mn＝19000～23000，Mw／Mn＝1.06～1.18）等。關於FM8826的Mn和Mw／Mn，雖然有大約在上述範圍內的批次間差異，但藉由此範圍內的差異，所獲得之苯基改質混成預聚物（B）、進一步獲得之苯基改質聚二甲基矽氧烷系混成預聚物（C）及高熱傳導複合材料的物性等，不會產生很大的差異。As the polydimethylsiloxane having a trialkoxysilyl group at both ends used in the present invention, FM8826 (representative value: Mn = 20000, Mw / Mn = 1.06) manufactured by JNC Corporation is particularly preferred. ; There are differences between batches, Mn = 19000 ～ 23000, Mw / Mn = 1.06 ～ 1.18) and so on. Regarding FM8826's Mn and Mw / Mn, although there are batch-to-batch differences within the above range, the phenyl group obtained is modified and mixed into the prepolymer (B), and the benzene group is further obtained. The physical properties of the modified polydimethylsiloxane-based prepolymer (C) and the high-heat-conducting composite material are not significantly different.

＜平均分子量的測定＞ PDMS-1和PDMS-2的分子量，是藉由凝膠滲透層析（GPC法）來測定，將重量平均分子量（Mw）與數量平均分子量（Mn）之比作為分子量分佈指數。採用聚苯乙烯作為標準試料，來測定聚苯乙烯換算分子量。 另外，藉由GPC法進行的聚苯乙烯換算分子量測定，是利用以下的測定條件來進行。 a）測定儀器：SIC Autosampler Model 09 Sugai U-620 COLUMN HEATER Uniflows UF-3005S2B2 b）檢測器：MILLIPORE Waters 410 Differential Refractometer c）管柱：Shodex KF806M ×2根 d）烘箱溫度：40℃ e）溶析液：四氫呋喃（THF）1.0mL/min f）標準試料：聚苯乙烯 g）注入量：100μL h）濃度：0.020g/10mL i）試料製備：將添加有0.2重量%的2,6-二-三級丁基-對苯酚（BHT）而成之THF作為溶劑，在室溫中攪拌溶解。 j）修正：將檢量線測定時與試料測定時的BHT波峰的偏移予以修正，而進行分子量計算。<Measurement of average molecular weight> The molecular weights of PDMS-1 and PDMS-2 were measured by gel permeation chromatography (GPC method), and the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) was used as the molecular weight distribution. index. Polystyrene was used as a standard sample to measure the molecular weight in terms of polystyrene. The polystyrene-equivalent molecular weight measurement by the GPC method was performed under the following measurement conditions. a) Measuring instrument: SIC Autosampler Model 09 Sugai U-620 COLUMN HEATER Uniflows UF-3005S2B2 b) Detector: MILLIPORE Waters 410 Differential Refractometer c) Tube: Shodex KF806M × 2 d) Oven temperature: 40 ° C e) Dissolution Solution: Tetrahydrofuran (THF) 1.0mL / min f) Standard sample: Polystyrene g) Injection volume: 100μL h) Concentration: 0.020g / 10mL i) Sample preparation: 0.2% by weight of 2,6-di- THF made from tertiary butyl-p-phenol (BHT) was used as a solvent, and dissolved at room temperature with stirring. j) Correction: Correct the deviation of the BHT peak during the calibration curve measurement and the sample measurement, and calculate the molecular weight.

＜苯基烷氧基矽烷＞ 本發明中作為進行苯基改質之原料而使用的苯基烷氧基矽烷，是指在分子內具有一個或兩個苯基之烷氧基矽烷，藉由烷氧基的水解而生成矽醇基，藉由脫醇反應或脫水反應而與PDMS或經改質之PDMS縮合。對於烷氧基雖無限制，但一般是採用碳數1～3者，特別期望是甲氧基、乙氧基。<Phenylalkoxysilane> The phenylalkoxysilane used as a raw material for phenyl modification in the present invention refers to an alkoxysilane having one or two phenyl groups in the molecule. Hydrolysis of the oxygen group generates silanol groups, which are condensed with PDMS or modified PDMS through dealcoholization or dehydration reactions. Although the alkoxy group is not limited, those having 1 to 3 carbon atoms are generally used, and a methoxy group and an ethoxy group are particularly desirable.

為了對所製作之預聚物賦予耐熱性，含有苯基而成之烷氧基矽烷類是很重要的。苯基，藉其立體效果，而具有可緩和分子內的熱振動而減低分子骨架的熱劣化的效果。但是，若使分子含有過多苯基，則硬化後的硬度會上升而成為硬的高熱傳導複合材料，所以當在熱傳導片的情形中，必須將導入量予以最適化。又，因為π電子雲的效果以致高電壓下的絕緣性有降低之虞，所以必須將導入量予以最適化。In order to impart heat resistance to the produced prepolymer, alkoxysilanes containing a phenyl group are important. By virtue of its three-dimensional effect, phenyl has the effect of reducing thermal vibration in the molecule and reducing thermal degradation of the molecular skeleton. However, if the molecule contains too many phenyl groups, the hardness after hardening will increase to become a hard, highly heat-conductive composite material. Therefore, in the case of a heat-conductive sheet, the amount of introduction must be optimized. In addition, the effect of the π-electron cloud may reduce the insulation properties at high voltages, so the amount of introduction must be optimized.

在分子內具有一個苯基者為苯基三烷氧基矽烷，從反應性的方面而言，雖然期望採用反應性高的苯基三甲氧基矽烷，但從穩定性或安全面（避免發生甲醇）等方面而言，期望採用具有乙氧基之苯基三乙氧基矽烷。當然，若在排氣環境等方面沒有問題，則亦可採用苯基三甲氧基矽烷。另外，雖然一般未販售、難以取得，但若採用苯基三烷氧基矽烷寡聚物亦可獲得同樣的功效、或更佳的功效。Those with one phenyl group in the molecule are phenyltrialkoxysilanes. In terms of reactivity, although it is desirable to use phenyltrimethoxysilanes with high reactivity, from the perspective of stability or safety (avoid methanol ), Etc., it is desirable to use phenyltriethoxysilane with ethoxy group. Of course, if there is no problem in the exhaust environment, etc., phenyltrimethoxysilane can also be used. In addition, although generally not sold and difficult to obtain, the same or better effects can be obtained by using phenyltrialkoxysilane oligomers.

另一方面，使用於苯基改質混成預聚物（B）的製備中的在分子內具有兩個苯基之二苯基二烷氧基矽烷，一般而言反應性低，相較於二苯基二乙氧基矽烷而言，採用具有甲氧基之二苯基二甲氧基矽烷者因為不易受到由苯基所致之立體障礙的影響，反應性優異，所以較佳。雖然亦可採用二苯基二乙氧基矽烷，但因為立體障礙等原因以致反應性顯著較低，所以儘管在安全性方面有問題尚待解決，仍期望採用反應性較高的二苯基二甲氧基矽烷。另外，雖然一般未販售、難以取得，但若採用二苯基二烷氧基矽烷寡聚物亦可獲得同樣的功效、或更佳的功效。On the other hand, diphenyldialkoxysilane, which has two phenyl groups in the molecule, is used in the preparation of a phenyl modified mixed prepolymer (B). As for phenyldiethoxysilane, it is preferable to use a diphenyldimethoxysilane having a methoxy group because it is not easily affected by a steric obstacle caused by a phenyl group and has excellent reactivity. Although diphenyldiethoxysilane can also be used, the reactivity is significantly lower due to steric hindrance and other reasons. Therefore, although there are still problems to be solved in terms of safety, it is still desirable to use diphenyl diester with higher reactivity. Methoxysilane. In addition, although generally not sold and difficult to obtain, the same or better effects can be obtained by using a diphenyldialkoxysilane oligomer.

本發明中，當合成苯基改質混成預聚物（A）及（B）時，苯基並非取代直接鍵結於PDMS-1及PDMS-2的矽（Si）上之甲基而存在，而是存在於苯基烷氧基矽烷結構中，此點甚為重要。含有苯基之化合物，尤其是矽系化合物，一般而言耐熱性優異，但本發明的苯基改質混成預聚物（A）及（B）不僅具有源自苯基烷氧基矽烷的部分的耐熱性，亦具有抑制源自PDMS的部分也就是主骨架的熱劣化而提升耐熱性的功效，在尋求耐熱維持特性的熱傳導片中，上述苯基改質混成預聚物（A）及（B）的分子結構是必要結構。但是，當苯基位於PDMS-1及PDMS-2的主骨架上時，會牽涉到硬化後的硬度上升，使得作為彈性體的特性明顯受到阻礙。因此，使烷氧基矽烷持有苯基，並鍵結於PDMS也就是主骨架的末端。藉此，可製作一種高熱傳導複合材料，其以最終兼具柔軟性和耐熱性的苯基改質聚二甲基矽氧烷系混成聚合物來作為基質材料。In the present invention, when the phenyl group is modified and mixed into the prepolymers (A) and (B), the phenyl group does not exist instead of the methyl group directly bonded to the silicon (Si) of PDMS-1 and PDMS-2. Instead, it is present in the phenylalkoxysilane structure, which is very important. The compound containing a phenyl group, especially a silicon-based compound, is generally excellent in heat resistance, but the phenyl group modified into the prepolymers (A) and (B) of the present invention has not only a portion derived from a phenylalkoxysilane It also has the effect of suppressing the thermal degradation of the part derived from PDMS, that is, the main skeleton, and improving the heat resistance. In the heat conductive sheet that seeks heat resistance maintenance characteristics, the above phenyl groups are modified and mixed into prepolymers (A) and ( B) The molecular structure is a necessary structure. However, when the phenyl group is located on the main skeleton of PDMS-1 and PDMS-2, the hardness after hardening is increased, and the characteristics as an elastomer are significantly impeded. Therefore, the alkoxysilane is made to have a phenyl group and is bonded to the terminal of PDMS, which is the main skeleton. Thereby, a highly thermally conductive composite material can be produced which uses a phenyl-modified polydimethylsiloxane-based mixed polymer having both flexibility and heat resistance as a matrix material.

＜苯基改質混成預聚物（A）、（B）＞ 苯基改質混成預聚物的製造 本發明中，苯基改質混成預聚物（A）及（B），分別是藉由下述方式而製備：上述PDMS-1與苯基三烷氧基矽烷之間的縮合反應；PDMS-2、苯基三烷氧基矽烷及二苯基二烷氧基矽烷的部分或完全水解縮合反應。縮合反應中，通常是採用有機金屬觸媒、或金屬烷氧化物系觸媒。耐熱環境、尤其是250℃以上的使用環境中，同樣較佳是採用不會發生高熱傳導複合材料之熱劣化的鈦（Ti）系烷氧化物類。其他亦可使用鋯（Zr）系觸媒或鋁系觸媒。<Phenyl modification and mixing into prepolymers (A), (B)> 的 Production of phenyl modification and mixing into prepolymers In the present invention, phenyl modification and mixing into prepolymers (A) and (B), respectively Is prepared by: the condensation reaction between the above PDMS-1 and phenyltrialkoxysilane; PDMS-2, a portion of phenyltrialkoxysilane and diphenyldialkoxysilane Complete hydrolysis condensation reaction. In the condensation reaction, an organic metal catalyst or a metal alkoxide-based catalyst is usually used. It is also preferable to use titanium (Ti) -based alkoxides that do not undergo thermal degradation of the high-heat-conducting composite material in a heat-resistant environment, especially in a use environment above 250 ° C. Others can also use zirconium (Zr) catalysts or aluminum catalysts.

作為上述在兩端具有矽醇基之聚二甲基矽氧烷（PDMS-1）和苯基三烷氧基矽烷的反應中所採用的Ti系（Ti烷氧化物類）觸媒，可舉出下述：鈦酸四（2-乙基己基）酯、四正丁氧基鈦、四異丙氧基鈦、鈦酸二異丙氧基雙（乙基乙醯乙酸酯）、四乙醯丙酮鈦（titanium tetraacetyl acetonate）、二-2-乙基己氧基雙（2-乙基-3-羥基己氧基）鈦、二異丙氧基雙（乙醯丙酮）鈦等。當採用Ti系觸媒時，反應中的溶膠容易著色成黃色或黃褐色。應用於製品時，黃色系容易被作為劣化色而避免，所以其中特佳是使用不易使溶膠顯色的鈦酸四（2-乙基己基）酯。As the Ti-based (Ti alkoxide) catalyst used in the above reaction between polydimethylsiloxane (PDMS-1) having a silanol group at both ends and phenyltrialkoxysilane, there may be mentioned The following are produced: tetra (2-ethylhexyl) titanate, tetra-n-butoxytitanium, tetraisopropoxytitanium, diisopropoxybis (ethylacetamidine acetate) titanate, tetraethyl Titanium tetraacetyl acetonate, di-2-ethylhexyloxy bis (2-ethyl-3-hydroxyhexyloxy) titanium, diisopropoxy bis (ethyl acetone) titanium and the like. When a Ti-based catalyst is used, the sol in the reaction is easily colored yellow or tan. When applied to products, the yellow color is easily avoided as a deteriorated color. Therefore, it is particularly preferable to use tetra (2-ethylhexyl) titanate, which is difficult to make sol color.

鈦烷氧化物類，較佳是相對於在兩端具有矽醇基之聚二甲基矽氧烷1mol而採用0.08～0.2mol的量。若量小於0.08mol，則有無法硬化之虞，而量即使大於0.2mol，效果並無改變。鈦烷氧化物類的添加量，進一步較佳是相對於在兩端具有矽醇基之聚二甲基矽氧烷1mol而採用0.09～0.15mol。The titanyl oxide is preferably used in an amount of 0.08 to 0.2 mol based on 1 mol of polydimethylsiloxane having a silanol group at both ends. If the amount is less than 0.08 mol, there is a possibility that it cannot be hardened, and even if the amount is more than 0.2 mol, the effect is not changed. The addition amount of the titanium alkoxides is more preferably from 0.09 to 0.15 mol based on 1 mol of the polydimethylsiloxane having a silanol group at both ends.

上述在兩端具有三烷氧矽基之聚二甲基矽氧烷（PDMS-2）、苯基三烷氧基矽烷及二苯基二烷氧基矽烷的反應時，亦與上述同樣，較佳是採用鈦烷氧化物類化合物作為觸媒。亦可採用前述有機金屬化合物，但與上述同樣地，當考慮到耐熱用途時，較期望是Ti系觸媒。作為Ti系（Ti烷氧化物類）觸媒，可舉出與上述同樣之物，基於與上述同樣的理由，較佳是使用鈦酸四（2-乙基己基）酯。The above reaction of polydimethylsiloxane (PDMS-2), phenyltrialkoxysilane, and diphenyldialkoxysilane with a trialkoxysilyl group at both ends is the same as above, Preferably, a titanium alkoxide compound is used as a catalyst. The aforementioned organometallic compound may be used, but in the same manner as described above, when a heat-resistant application is considered, a Ti-based catalyst is more desirable. Examples of the Ti-based (Ti alkoxide-based) catalyst include the same as described above. For the same reasons as described above, it is preferable to use tetra (2-ethylhexyl) titanate.

鈦烷氧化物類，較佳是相對於在兩端具有三烷氧矽基之聚二甲基矽氧烷1mol而採用0.08～0.2mol的量。若量小於0.08mol，則有無法硬化之虞，而量即使大於0.2mol，效果並無改變。鈦烷氧化物類的添加量，進一步較佳是相對於在兩端具有三烷氧矽基之聚二甲基矽氧烷1mol而採用0.09～0.15mol。The titanyl oxide is preferably used in an amount of 0.08 to 0.2 mol with respect to 1 mol of polydimethylsiloxane having a trialkoxysilyl group at both ends. If the amount is less than 0.08 mol, there is a possibility that it cannot be hardened, and even if the amount is more than 0.2 mol, the effect is not changed. The addition amount of the titanium alkoxide is more preferably 0.09 to 0.15 mol based on 1 mol of the polydimethylsiloxane having a trialkoxysilyl group at both ends.

進行上述縮合反應時，為了進行PDMS或苯基三乙氧基矽烷、二苯基二烷氧基矽烷等的穩定的水解、脫水、脫醇反應，較期望是設為在反應所使用的容器內充滿惰性氣體而成之氣氛。作為惰性氣體，可舉出氮氣或第18族元素（氦、氖、氬、氪、氙等）也就是稀有氣體類。又，這些氣體亦可混合使用。作為水解的方法，可考慮：滴加適量的水、噴霧、導入水蒸氣等各種方法。所導入的水的量，可考慮所使用之烷氧基矽烷單體的種類所致之反應性的差異，而適當調整。受到水解的上述苯基烷氧基矽烷或二苯基二烷氧基矽烷，其烷氧基會變成矽醇基，藉由在惰性氣體的存在下加熱，部分殘存的烷氧基會與PDMS兩端的矽醇基或烷氧矽基發生縮合反應。例如，分子量分佈指數（Mw／Mn）夠小的PDMS與具有苯基之烷氧基矽烷之間的縮合反應，藉由將反應溫度和惰性氣體氣氛中的水分量維持固定、使其穩定化，而能以相對低溫迅速結束反應。另外，為了使反應較為穩定化，亦期望在合成初期時裝設回流管，使其反應一定時間。When the condensation reaction is performed, it is more desirable to set it in a container used for the reaction in order to perform stable hydrolysis, dehydration, and dealcoholization reaction of PDMS, phenyltriethoxysilane, and diphenyldialkoxysilane. An atmosphere filled with inert gas. Examples of the inert gas include nitrogen or a Group 18 element (helium, neon, argon, krypton, xenon, etc.), which is a rare gas. These gases may be used in combination. As a method of hydrolysis, various methods such as dripping an appropriate amount of water, spraying, and introducing water vapor can be considered. The amount of water to be introduced can be appropriately adjusted in consideration of the difference in reactivity due to the type of the alkoxysilane monomer used. The hydrolyzed phenylalkoxysilane or diphenyldialkoxysilane has an alkoxy group that changes to a silanol group. By heating in the presence of an inert gas, some of the remaining alkoxy groups will react with PDMS. The silanol or alkoxysilyl group at the end undergoes a condensation reaction. For example, a condensation reaction between a PDMS with a sufficiently small molecular weight distribution index (Mw / Mn) and an alkoxysilane having a phenyl group can stabilize and stabilize the reaction temperature and the amount of water in an inert gas atmosphere. The reaction can be ended quickly at relatively low temperatures. In addition, in order to stabilize the reaction, it is also desirable to provide a reflux tube in the initial stage of the synthesis and allow the reaction to react for a certain period of time.

調配比 在兩端具有矽醇基之聚二甲基矽氧烷（PDMS-1）和苯基三烷氧基矽烷（Ph-1）之間的調配比，較佳是相對於（PDMS-1）1mol而言，（Ph-1）為0.5～5mol的莫耳比。若莫耳比在上述範圍，則縮合反應會順利地進行，當（Ph-1）較多時，則有柔軟性受損之虞。相反地，當（Ph-1）較少時，耐熱維持性變差、最終變得難以硬化。調配比進一步較佳是相對於（PDMS-1）1mol而言（Ph-1）為1～4mol的莫耳比。Mixing ratio The blending ratio between polydimethylsiloxane (PDMS-1) and phenyltrialkoxysilane (Ph-1) having silanol groups at both ends is preferably relative to (PDMS -1) For 1 mol, (Ph-1) is a molar ratio of 0.5 to 5 mol. If the molar ratio is in the above range, the condensation reaction proceeds smoothly, and when there is a large amount of (Ph-1), the flexibility may be impaired. Conversely, when (Ph-1) is small, heat resistance maintainability is deteriorated and it becomes difficult to harden finally. The blending ratio is more preferably a molar ratio of (Ph-1) of 1 to 4 mol relative to 1 mol of (PDMS-1).

又，在兩端具有三烷氧矽基之聚二甲基矽氧烷（PDMS-2）、苯基三烷氧基矽烷（Ph-1）及二苯基二烷氧基矽烷（Ph-2）的調配比，較佳是相對於（PDMS-2）1mol而言，（Ph-1）為0.5～3mol、（Ph-2）為0.5～3mol的莫耳比。若莫耳比在上述範圍，則縮合反應會順利地進行，當（Ph-1）和（Ph-2）較多時，則有柔軟性受損之虞。相反地，當（Ph-1）和（Ph-2）較少時，耐熱維持性變差、最終變得難以硬化。調配比進一步較佳是相對於（PDMS-2）1mol而言，（Ph-1）為1～2mol、（Ph-2）為1～2mol的莫耳比。In addition, polydimethylsiloxane (PDMS-2), phenyltrialkoxysilane (Ph-1), and diphenyldialkoxysilane (Ph-2) having trialkoxysilyl groups at both ends. The mixing ratio of) is preferably a molar ratio of (Ph-1) of 0.5 to 3 mol and (Ph-2) of 0.5 to 3 mol with respect to 1 mol of (PDMS-2). If the molar ratio is within the above range, the condensation reaction proceeds smoothly, and when there are many (Ph-1) and (Ph-2), the flexibility may be impaired. Conversely, when (Ph-1) and (Ph-2) are small, the heat resistance maintainability is deteriorated, and eventually it becomes difficult to harden. The blending ratio is more preferably a molar ratio of (Ph-1) of 1 to 2 mol and (Ph-2) of 1 to 2 mol relative to 1 mol of (PDMS-2).

另外，此處所謂的莫耳比，是將聚苯乙烯作為標準物質，將四氫呋喃作為溶析液而藉由凝膠滲透層析（GPC法）來測定PDMS（PDMS-1及PDMS-2）的數量平均分子量（Mn）、苯基三烷氧基矽烷（Ph-1）及二苯基二烷氧基矽烷（Ph-2）的分子量，並基於該些分子量所計算而得之莫耳比。In addition, the so-called molar ratio is measured by gel permeation chromatography (GPC method) using polystyrene as a standard substance and tetrahydrofuran as an eluent, and measuring PDMS (PDMS-1 and PDMS-2). The number average molecular weight (Mn), the molecular weights of phenyltrialkoxysilane (Ph-1) and diphenyldialkoxysilane (Ph-2), and the molar ratios calculated based on these molecular weights.

苯基改質混成預聚物（A）、（B）的製備方法 苯基改質混成預聚物（A）、（B）的製備（合成），是採用裝設有攪拌裝置、溫度計、滴加管線而成之反應容器（有複數個***口之燒瓶）。當較為精密地實施合成時，亦期望附有回流裝置。攪拌裝置方面，有附攪拌葉片之旋轉式攪拌機、磁攪拌器、雙軸行星式攪拌機、超音波清洗裝置等，只要是有助於反應且具有將高黏度液狀原料均勻混合的功效即可，無特別限制。但是，因為附有溫度控制、氣氛控制、成分滴加管線等，所以較期望是旋轉式攪拌機、磁攪拌器等。合成溫度方面，均勻性很重要，當合成容量小的情形中，板式加熱器等簡易方法即足夠，但若是大於5L這樣的量產線，則較期望是加熱套（mantle heater）等保溫性和均質性高的加溫方法。合成溫度是適當地設定於60～100℃之間。當低溫下長時間反應時、或高溫下短時間合成時，則依照原料的種類、調配比率、合成設備等而個別地設定。合成氣氛方面，作為惰性氣體而使用例如氮氣，使所含水分量已維持固定的氮氣充分地充滿於該反應容器內。此時，關於氮氣，較期望採用氮氣製造裝置。氮氣供給方面，當然也可以採用來自氮氣瓶或液態氮的供給，但有時會有長時間進行合成的情形，所以較期望採用供給壓力的變動較少的製造裝置。Method for preparing phenyl modified and mixed into prepolymers (A) and (B)  Preparation of phenyl modified and mixed into prepolymers (A) and (B) (synthesis), equipped with stirring device, thermometer 2. A reaction vessel (flask with a plurality of insertion ports) formed by dripping a line. When the synthesis is performed more precisely, it is also desirable to attach a reflow device. As for the stirring device, there are a rotary stirrer with a stirring blade, a magnetic stirrer, a biaxial planetary stirrer, an ultrasonic cleaning device, etc., as long as it is helpful for the reaction and has the effect of uniformly mixing high-viscosity liquid raw materials, No special restrictions. However, since temperature control, atmosphere control, component dropping lines, and the like are attached, a rotary stirrer, a magnetic stirrer, and the like are more desirable. In terms of synthesis temperature, uniformity is very important. When the synthesis capacity is small, a simple method such as a plate heater is sufficient. However, if it is a production line larger than 5L, it is more desirable to maintain heat retention such as a mantle heater. Heating method with high homogeneity. The synthesis temperature is appropriately set between 60 and 100 ° C. When reacting for a long time at a low temperature or for a short time at a high temperature, they are individually set according to the type of raw materials, the blending ratio, the synthesis equipment, and the like. In the synthesis atmosphere, for example, nitrogen gas is used as an inert gas, and the reaction vessel is sufficiently filled with nitrogen gas having a fixed water content. In this case, it is more desirable to use a nitrogen production apparatus for nitrogen. In terms of nitrogen supply, of course, supply from a nitrogen bottle or liquid nitrogen can also be used, but sometimes the synthesis may be performed for a long time, so it is more desirable to use a manufacturing device with less fluctuation in the supply pressure.

＜苯基改質聚二甲基矽氧烷系混成預聚物（C）＞ 將具有賦予表面黏著性與柔軟性之功效的苯基改質混成預聚物（A）、賦予固體維持性的苯基改質混成預聚物（B），以所期望的比例來混合，藉此可製備黏著性與硬度經控制而成之苯基改質聚二甲基矽氧烷系混成預聚物（C）。混合方法並無限定，較期望是雙軸行星式攪拌機等不易受到外部氣體影響的裝置。所獲得的苯基改質聚二甲基矽氧烷系混成預聚物（C），與熱傳導性填料混合，當成形為片狀時則經由加熱步驟而硬化。作為加熱方法，有送風式、循環式等的電爐、氣氛爐等，並無特別限制。此預聚物（C），具有便於以高濃度分散高熱傳導性填料的黏性、與填料之間的表面適合性。<Phenyl modified polydimethylsiloxane-based mixed prepolymer (C)> A phenyl modified having a function of imparting surface adhesiveness and flexibility is mixed into a prepolymer (A), and a solid retaining property is provided. Phenyl modified and mixed into a prepolymer (B), and mixed in a desired ratio, thereby preparing a phenyl modified polydimethylsiloxane based mixed prepolymer (with adhesiveness and hardness controlled) C). The mixing method is not limited, and it is more desirable to use a device such as a biaxial planetary mixer that is not easily affected by external air. The obtained phenyl-modified polydimethylsiloxane is mixed into a prepolymer (C), mixed with a thermally conductive filler, and hardened through a heating step when formed into a sheet. There are no particular restrictions on the heating method, such as an electric furnace or an atmosphere furnace such as a blower type and a circulation type. This prepolymer (C) has a viscosity suitable for dispersing a highly thermally conductive filler at a high concentration and a surface suitability with the filler.

＜熱傳導性填料＞ 本發明所採用的熱傳導性填料，必須是熱傳導率為20W‧m^-1 ‧K^-1 以上者。熱傳導性填料若為熱傳導率小於20W‧m^-1 ‧K^-1 者，則無法獲得具有所期望的熱傳導性的複合材料。<Thermal Conductive Filler> The thermally conductive filler used in the present invention must have a thermal conductivity of 20 W‧m ^-1 ‧K ^-1 or more. If the thermally conductive filler has a thermal conductivity of less than 20 W‧m ^-1 ‧K ^-1 , a composite material having desired thermal conductivity cannot be obtained.

作為電絕緣性高且熱傳導性高的填料，一般是陶瓷填料。陶瓷填料有：氧化鋁（氧化鋁）、氧化鋅、氧化鎂、氧化鋯等的氧化物陶瓷；氮化硼、氮化鋁等氮化物陶瓷等。這些陶瓷填料，已市售具有各種平均粒徑、及粒度分佈者。一般而言，樹脂的熱傳導率是陶瓷填料的熱傳導率的1/10～1/100，所以為了提高複合材料的熱傳導率，則必須使用熱傳導率高的填料較為有效，同時也必須相對於樹脂而以高濃度來充填填料。As a filler having high electrical insulation and high thermal conductivity, a ceramic filler is generally used. Ceramic fillers include oxide ceramics such as alumina (alumina), zinc oxide, magnesium oxide, and zirconia; nitride ceramics such as boron nitride and aluminum nitride. These ceramic fillers are commercially available with various average particle sizes and particle size distributions. Generally speaking, the thermal conductivity of resin is 1/10 to 1/100 of the thermal conductivity of ceramic fillers. Therefore, in order to improve the thermal conductivity of composite materials, it is necessary to use fillers with high thermal conductivity, which is also effective relative to resin. Fill the filler at a high concentration.

本發明所採用的熱傳導性填料中，較佳是在填料表面具有可進行脫水或脫醇反應之官能基。填料會與本發明所採用的在末端具有矽醇基、或烷氧基、或者兩者兼具之苯基改質聚二甲基矽氧烷系混成預聚物（C）進行反應。藉此，填料表面與樹脂會堅固地緊密黏著，可防止由水分等所致之填料變質。具有聚二甲基矽氧烷骨架之預聚物樹脂，因為具有200℃以上的耐熱性，所以所製作成的散熱構件即便位於200℃以上的高溫度區域中，也會顯示穩定的特性。Among the thermally conductive fillers used in the present invention, it is preferred that the filler surface has a functional group capable of undergoing dehydration or dealcoholization reaction. The filler is reacted with a phenyl-modified polydimethylsiloxane system having a silanol group, an alkoxy group, or both at the terminal used in the present invention to form a prepolymer (C). Thereby, the surface of the filler and the resin will be firmly adhered tightly, and the deterioration of the filler due to moisture and the like can be prevented. Since the prepolymer resin having a polydimethylsiloxane frame has heat resistance of 200 ° C or higher, the produced heat dissipating member exhibits stable characteristics even in a high-temperature region of 200 ° C or higher.

本發明所採用的熱傳導性填料的熱傳導率，較佳是150W‧m^-1 ‧K^-1 以上者。作為熱傳導率為150W‧m^-1 ‧K^-1 以上者，可舉出氮化鋁（AlN）填料。AlN具有氧化鋁的5倍的熱傳導率，所以在相同程度的添加量的情形中，可製作出具有比添加氧化鋁時更高的熱傳導率的熱傳導片（散熱片），相反地，在製作相同熱傳導率的熱傳導片時，以比氧化鋁少的添加量即可實現目標的熱傳導率。進一步，相較於添加量多的情形，填料的添加量少時能提升熱傳導片的柔軟性，所以藉由使用AlN，可製作富有柔軟性的熱傳導片。實際的發熱構件或散熱片，於其表面存在著微小的凹凸，所以若僅單純接觸則熱的傳導不良，但藉由夾持柔軟性高的熱傳導片，則可吸收、緩和表面的凹凸，使密著性上升，藉此可提升熱傳導。亦即，藉由使用AlN填料，可實現熱傳導性優異的熱傳導片。另一方面，AlN填料雖然作為熱傳導性填料而言前景看好，但亦有著容易受到水解的問題。藉由將本發明所採用的苯基改質聚二甲基矽氧烷系混成預聚物（C）作為基質用材料，而可提供一種高熱傳導構件，其可在200℃以上的高溫中使用。The thermal conductivity of the thermally conductive filler used in the present invention is preferably 150W‧m ^-1 ‧K ^-1 or more. Examples of a thermal conductivity of 150 W‧m ^-1 ‧K ^-1 or more include an aluminum nitride (AlN) filler. AlN has 5 times the thermal conductivity of alumina, so with the same amount of addition, a thermally conductive sheet (heat sink) with a higher thermal conductivity than when alumina is added can be produced. On the contrary, the same In the case of a thermally conductive sheet, the target thermal conductivity can be achieved with a smaller amount of addition than alumina. Furthermore, compared with the case where the amount of the filler is increased, the softness of the heat conductive sheet can be improved when the amount of the filler is small. Therefore, by using AlN, a soft heat conductive sheet can be produced. Actual heating members or heat sinks have minute irregularities on their surfaces. Therefore, heat conduction is not good if they are simply contacted. However, by holding a heat conductive sheet with high flexibility, the irregularities on the surface can be absorbed and eased. Increased adhesion improves heat transfer. That is, by using an AlN filler, a thermally conductive sheet excellent in thermal conductivity can be realized. On the other hand, although AlN fillers are promising as thermally conductive fillers, they also have the problem of being susceptible to hydrolysis. By mixing the phenyl-modified polydimethylsiloxane-based prepolymer (C) used in the present invention as a material for the matrix, a highly thermally conductive member can be provided that can be used at a high temperature of 200 ° C or higher .

AlN，有藉由下述方式製造者：藉由還原氮化法或直接氮化法而合成的粒徑1μm左右的粒子；使粒子從數μm成長至二十幾μm的粒子；或者，使用1μm左右的粒子作為一次粒子，使其分散於有機溶劑系或水系溶劑中，並適當添加黏合劑等添加劑而做成漿狀，然後使藉由噴霧乾燥機造粒而成之顆粒在高溫氮氣氣氛中進行燒結所製造者。藉由調整噴霧乾燥機的噴霧條件，而可控制顆粒的粒徑至例如100μm左右，結果可製造持有各種粒度分佈的AlN填料。藉由此種製法所製作的AlN填料的表面，殘存有羥基等官能基。AlN is produced by: particles having a particle size of about 1 μm synthesized by reduction nitridation method or direct nitridation method; particles that grow particles from several μm to more than 20 μm; or using 1 μm The left and right particles are used as primary particles, dispersed in an organic solvent-based or water-based solvent, and appropriately added with additives such as a binder to form a slurry. Then, the particles granulated by a spray dryer are exposed to a high-temperature nitrogen atmosphere. Produced by sintering. By adjusting the spraying conditions of the spray dryer, the particle size of the particles can be controlled to, for example, about 100 μm. As a result, AlN fillers having various particle size distributions can be produced. Functional groups such as hydroxyl groups remain on the surface of the AlN filler produced by this manufacturing method.

為了實現高熱傳導性，必須增加熱傳導性填料的充填量。然而，一般而言，填料的充填濃度若增高，則複合材料會有變硬、加工變難的傾向。從而，為了兼具熱傳導率的提升和加工性，能降低高熱傳導複合材料的硬度之填料的選擇或組合變得很重要。為了獲得所期望的熱傳導性和柔軟性、耐熱（維持）性，較佳是以預聚物：填料的質量比為5：95～30：70的方式來充填，更佳是6：94～25：75，最佳是8：92～20：80。In order to achieve high thermal conductivity, it is necessary to increase the filling amount of the thermally conductive filler. In general, however, if the filler concentration is increased, the composite material tends to be hard and difficult to process. Therefore, in order to have both the improvement of thermal conductivity and the workability, the selection or combination of fillers that can reduce the hardness of the high thermal conductivity composite material becomes important. In order to obtain the desired thermal conductivity, softness, and heat resistance (maintenance), it is preferred to fill it with a prepolymer: filler mass ratio of 5:95 to 30:70, more preferably 6:94 to 25 : 75, preferably 8:92 to 20:80.

基於賦予高熱傳導之目的而調配的填料的種類，可以是單一種也可以是二種以上之混合。所採用的填料的粒徑，同樣可以是單一種也可以是二種以上之混合。例如，在高熱傳導上較優異的AlN填料，是表層具有微細凹凸的球狀粒子，若是單一成分、單一粒徑，則粒子的接觸點較少，若以不同粒徑或形狀的粒子使接觸點增加，則熱傳導率會提升。氮化硼等具有各種粒徑的鱗片狀填料，在密實地充填填料時很有效。又，氧化鋁填料亦市售有各種粒徑者。為了使填料的充填濃度增加，當使用具有單一粒徑分佈的填料時，較佳是使用粒度分佈盡量寬廣者。另一方面，當使用具有不同粒度分佈的二種以上的填料時，其粒徑差，較期望是2倍以上，進一步期望將粒徑差設作8倍以上。然而，粒徑若過小，則凡得瓦力所致之粒子彼此的結合力的影響會變大，填料體積增加、空間無法填滿，結果變得難以進行高濃度充填。從而，包括其他填料的粒徑的平衡性在內，必須選擇、調整於最佳。The type of the filler prepared for the purpose of imparting high heat conduction may be a single type or a mixture of two or more types. The particle size of the filler used may be a single type or a mixture of two or more types. For example, AlN filler, which is superior in high thermal conductivity, is spherical particles with fine unevenness on the surface layer. If it is a single component and a single particle size, there are fewer contact points of the particles. If the particles have different particle sizes or shapes, the contact points are made. As it increases, the thermal conductivity increases. Flaky fillers with various particle sizes, such as boron nitride, are effective when filling fillers densely. In addition, alumina fillers are also commercially available in various particle sizes. In order to increase the filling concentration of the filler, when using a filler having a single particle size distribution, it is preferable to use a particle size distribution as wide as possible. On the other hand, when two or more kinds of fillers having different particle size distributions are used, the particle size difference is more preferably 2 times or more, and it is more desirable to set the particle size difference to 8 times or more. However, if the particle diameter is too small, the influence of the binding force between particles caused by van der Waals will increase, the volume of the filler will increase, and the space will not be filled. As a result, it becomes difficult to perform high-concentration filling. Therefore, it is necessary to select and adjust the balance including the particle size balance of other fillers.

承上，當採用氮化鋁填料時，較佳是設為填料全體的25wt%以上，其平均粒徑較佳是設為20～100μm。氮化鋁填料的平均粒徑，進一步較佳是設為30～90μm。又，作為所併用的填料，較佳是平均粒徑小於該氮化鋁填料之填料。When the aluminum nitride filler is used, it is preferably 25% by weight or more of the entire filler, and the average particle diameter is preferably 20 to 100 μm. The average particle diameter of the aluminum nitride filler is more preferably 30 to 90 μm. As the filler to be used in combination, a filler having an average particle diameter smaller than the aluminum nitride filler is preferred.

又，當單獨以熱傳導率低於氮化鋁的氧化鋁填料來製作高熱傳導複合材料時，必須以較高濃度來充填，所以較佳是平均粒徑為0.2～10μm，進一步較佳是0.3～5μm。In addition, when a high-heat-conducting composite material is produced by using an alumina filler having a thermal conductivity lower than that of aluminum nitride alone, it must be filled at a higher concentration, so the average particle diameter is preferably 0.2 to 10 μm, and more preferably 0.3 to 5μm.

＜熱傳導片的製造＞ 將上述苯基改質聚二甲基矽氧烷系混成預聚物（C）和高熱傳導率填料複合而成之複合物成形為片狀後，可藉由使其加熱、硬化而製作熱傳導片。關於片狀化，可採用加壓延伸裝置，其他亦可使用硫化加壓機或擠型機而成形，複合物的硬度或所需的片材的尺寸，可配合每單位時間所需的製造能力而加以選擇。<Manufacturing of thermally conductive sheet> After the compound obtained by compounding the phenyl-modified polydimethylsiloxane based prepolymer (C) and a high thermal conductivity filler is formed into a sheet, it can be heated by heating And harden to make a heat conductive sheet. Regarding the sheeting, a press stretching device can be used. Others can also be formed by using a vulcanizing press or an extruder. The hardness of the compound or the required sheet size can be matched with the required production capacity per unit time. And choose.

熱傳導性填料的混合、捏揉方面，是依照調配量而採用各種方法。若是相對較低的調配量，捏揉時的負荷較少，則以螺旋槳式的攪拌機、捏揉混合機等較為簡便，但若是調配量多而高負荷的分散，則採用自動研缽、三輥磨機、捏揉機等。陶瓷填料一般而言硬度高於金屬者多，所以當捏揉機的構件是使用一般金屬時，金屬構件會磨損，以致成為雜質而有混入複合材料中之虞。從而，捏揉時與複合材料接觸部分的材質，必須選擇超硬合金或陶瓷等耐磨損性高的材質。特別是在要求電絕緣性時，必須極力避免與具有導電性之金屬製構件的接觸。In terms of mixing and kneading of the thermally conductive filler, various methods are adopted depending on the blending amount. If the blending amount is relatively low and the load during kneading is small, it is easier to use a propeller mixer, kneading mixer, etc., but if the blending amount is large and the load is high, use an automatic mortar and three rolls. Mill, kneader, etc. Ceramic fillers generally have a higher hardness than metals. Therefore, when the components of the kneader are made of general metal, the metal components will wear out, which may become impurities and may be mixed into the composite material. Therefore, it is necessary to select a material which is in contact with the composite material during kneading with a material having high abrasion resistance such as cemented carbide or ceramic. In particular, when electrical insulation is required, it is necessary to avoid contact with conductive metal members as much as possible.

＜高熱傳導複合材料的物性＞ 高熱傳導複合材料的熱傳導率，較佳是即便長時間持續在高溫下使用，仍維持於4.0W‧m^-1 ‧K^-1 以上。若無法維持於4.0W‧m^-1 ‧K^-1 以上，則對於因電子零件的高密度化、集積化以致運算元件發熱的熱量增大情形，將有無法充分因應之虞。為了在高溫下的使用中獲得充分的散熱性，高熱傳導複合材料的熱傳導率，進一步較佳是在高溫下的使用前為5.0W‧m^-1 ‧K^-1 以上。<Physical properties of high thermal conductivity composite material> The thermal conductivity of the high thermal conductivity composite material is preferably maintained at 4.0W‧m ^-1 ‧K ^-1 or more even if it is continuously used at high temperature for a long time. If it cannot be maintained above 4.0W‧m ^-1 ‧K ^-1 , it may not be able to cope with the increase in heat generated by computing elements due to high density and integration of electronic components. In order to obtain sufficient heat dissipation during use at high temperatures, the thermal conductivity of the high thermal conductive composite material is more preferably 5.0W‧m ^-1 ‧K ^-1 or more before use at high temperatures.

又，高熱傳導複合材料的彈性模數，較佳是即便長時間持續在高溫下使用，仍維持於20MPa以下。若無法維持於20MPa以下，則有下述情形之虞：低硬度柔軟性受損、與發熱體之間的密著性不足而使得散熱不充分。若考慮低硬度柔軟性，則彈性模數進一步較佳是17MPa以下。另一方面，若是片材，則彈性模數較佳是1MPa以上，以免拉伸強度變得過低。 [實施例]The elastic modulus of the high thermal conductivity composite material is preferably maintained at 20 MPa or less even if it is continuously used at a high temperature for a long time. If it cannot be maintained below 20 MPa, there is a possibility that the low hardness and flexibility are impaired, and the adhesion to the heating element is insufficient, resulting in insufficient heat dissipation. Considering low hardness and flexibility, the elastic modulus is more preferably 17 MPa or less. On the other hand, in the case of a sheet, the elastic modulus is preferably 1 MPa or more so as not to cause the tensile strength to become too low. [Example]

採用實施例來更具體地說明本發明。另外，若無特別記載，則實施例中的「份」、「%」，均為質量基準（質量份、質量%）。又，本發明不受這些實施例所限定。The present invention will be described more specifically with reference to examples. In addition, unless otherwise stated, "part" and "%" in an Example are a mass basis (mass part, mass%). The present invention is not limited by these examples.

[合成例1] 苯基改質混成預聚物（A）的製備 使氮氣充分地充滿於裝設有攪拌裝置、溫度計、滴加管線而成之反應容器中。此時，作為氮氣，是採用藉由氮氣製造裝置（Japan Unix公司製造的UNX-200）所製造而成者。[Synthesis Example 1] Preparation of phenyl modified and mixed into prepolymer (A)  Nitrogen was sufficiently filled in a reaction vessel equipped with a stirring device, a thermometer, and a dripping line. At this time, as the nitrogen gas, a product manufactured by a nitrogen manufacturing apparatus (UNX-200 manufactured by Japan Unix Corporation) was used.

分別秤量：作為在兩端具有矽醇基之聚二甲基矽氧烷（PDMS-1）之JNC公司製造的FM9927（蒸發處理製品，數量平均分子量Mn＝44000，分子量分佈指數（Mw／Mn）＝1.37）226.2份、苯基三乙氧基矽烷（Ph-1；東京化成工業公司製造，分子量＝240.37）3.4份、及Matsumoto Fine Chemical公司製造的鈦酸四（2-乙基己基）酯（ORGATIX TA-30；分子量＝564.75）0.40份，依照上述記載順序投入至已充分充滿氮氣之反應容器內。以附有磁攪拌器之板式加熱器一邊攪拌一邊加熱，以液溫80℃持續攪拌3小時，而製備苯基改質混成預聚物（A）。在上述反應期間，使氮氣持續流入。Weigh separately: FM9927 (evaporation-treated product, number average molecular weight Mn = 44000, molecular weight distribution index (Mw / Mn)) manufactured by JNC Corporation as polydimethylsiloxane (PDMS-1) with silanol groups at both ends. = 1.37) 226.2 parts, 3.4 parts of phenyltriethoxysilane (Ph-1; manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight = 240.37), and tetra (2-ethylhexyl) titanate manufactured by Matsumoto Fine Chemical ( ORGATIX TA-30; molecular weight = 564.75) 0.40 parts, put into the reaction container that is fully filled with nitrogen in the order described above. A plate heater with a magnetic stirrer was used for heating while stirring, and stirring was continued at a liquid temperature of 80 ° C. for 3 hours to prepare a phenyl group modified into a prepolymer (A). During the above reaction, nitrogen was continuously flowed in.

PDMS-1（FM9927）和Ph-1（苯基三乙氧基矽烷）的莫耳比，是PDMS-1：Ph-1＝1：2.8，PDMS-1（FM9927）和ORGATIX TA-30的莫耳比，是PDMS-1：TA-30＝1：0.14。The mole ratios of PDMS-1 (FM9927) and Ph-1 (phenyltriethoxysilane) are the moles of PDMS-1: Ph-1 = 1: 2.8, PDMS-1 (FM9927) and ORGATIX TA-30. The ear ratio is PDMS-1: TA-30 = 1: 0.14.

[合成例2] 苯基改質混成預聚物（B）的製備 使氮氣充分地充滿於裝設有攪拌裝置、溫度計、滴加管線而成之反應容器中。此時，作為氮氣，是採用藉由氮氣製造裝置（Japan Unix公司製造的UNX-200）所製造而成者。[Synthesis Example 2] Preparation of phenyl modified and mixed into prepolymer (B)  Nitrogen was sufficiently filled in a reaction vessel equipped with a stirring device, a thermometer, and a dripping line. At this time, as the nitrogen gas, a product manufactured by a nitrogen manufacturing apparatus (UNX-200 manufactured by Japan Unix Corporation) was used.

分別秤量：作為在兩端具有三烷氧矽基之聚二甲基矽氧烷（PDMS-2）之JNC公司製造的FM8826（數量平均分子量（Mn）＝20000，分子量分佈指數（Mw／Mn）＝1.06）495.8份、二苯基二甲氧基矽烷（Ph-2；信越化學工業公司製造的KBM-202SS，分子量＝244.36）12.1份、經以乙醇稀釋20倍而成之水與乙醇之混合液(水：乙醇=1：19)35份、苯基三乙氧基矽烷（Ph-1；東京化成工業公司製造，分子量＝240.37）11.9份、及Matsumoto Fine Chemical公司製造的鈦酸四（2-乙基己基）酯（ORGATIX TA-30；分子量＝564.75）1.4份，依照上述記載順序投入至已充分充滿氮氣之反應容器內。以附有磁攪拌器之板式加熱器一邊攪拌一邊加熱，並在液溫80℃持續攪拌10小時，而製備苯基改質混成預聚物（B）。在上述反應期間，使氮氣持續流入。Weigh separately: FM8826 (number average molecular weight (Mn) = 20000, molecular weight distribution index (Mw / Mn)) manufactured by JNC Corporation as polydimethylsiloxane (PDMS-2) with trialkoxysilyl groups at both ends. = 1.06) 495.8 parts, diphenyldimethoxysilane (Ph-2; KBM-202SS, manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight = 244.36) 12.1 parts, water and ethanol mixed with 20-fold dilution with ethanol 35 parts of liquid (water: ethanol = 1: 19), 11.9 parts of phenyltriethoxysilane (Ph-1; manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight = 240.37), and tetrakis (4) titanate manufactured by Matsumoto Fine Chemical -1.4 parts of ethylhexyl) ester (ORGATIX TA-30; molecular weight = 564.75), put into a reaction container that was sufficiently filled with nitrogen in the order described above. A plate heater with a magnetic stirrer was used for heating while stirring, and stirring was continued at a liquid temperature of 80 ° C. for 10 hours to prepare a phenyl group modified into a prepolymer (B). During the above reaction, nitrogen was continuously flowed in.

PDMS-2（FM8826）和Ph-1（苯基三乙氧基矽烷）的莫耳比，是PDMS-2：Ph-1＝1：2，PDMS-2（FM8826）和Ph-2（二苯基二甲氧基矽烷）的莫耳比，是PDMS-2：Ph-2＝1：2，PDMS-2（FM8826）和ORGATIX TA-30的莫耳比，是PDMS-2：TA-30＝1：0.1。The molar ratios of PDMS-2 (FM8826) and Ph-1 (phenyltriethoxysilane) are PDMS-2: Ph-1 = 1: 2, PDMS-2 (FM8826) and Ph-2 (diphenyl) The molar ratio of dimethoxysilane is PDMS-2: Ph-2 = 1: 2, and the molar ratio of PDMS-2 (FM8826) and ORGATIX TA-30 is PDMS-2: TA-30 = 1: 0.1.

[合成例3] 不含苯基之混成預聚物（a）的製備 與合成例1同樣地進行，於已充分充滿氮氣之上述反應容器內，投入：作為在兩端具有矽醇基之聚二甲基矽氧烷之JNC公司製造的FM9927（數量平均分子量（Mn）＝32000，分子量分佈指數（Mw／Mn）＝1.13）477.8份、多摩化學工業股份有限公司製造的Silicate 40（四乙氧基矽烷的直鏈狀4～6聚物的寡聚物；藉由精製，寡聚物純度為90質量%，平均分子量＝745）24.9份，在室溫中攪拌30分鐘。[Synthesis Example 3] 的 Preparation of phenyl-free mixed prepolymer (a)  It was carried out in the same manner as in Synthesis Example 1. In the above reaction vessel which was sufficiently filled with nitrogen, it was charged as having a silanol group at both ends. 477.8 parts of FM9927 (number average molecular weight (Mn) = 32000, molecular weight distribution index (Mw / Mn) = 1.13) manufactured by JNC Corporation of Polydimethylsiloxane, Silicate 40 (four by Tama Chemical Industry Co., Ltd.) An oligomer of a linear 4 to 6-mer of ethoxysilane; the purity of the oligomer was 90% by mass, and the average molecular weight was 24.9 parts, and the mixture was stirred at room temperature for 30 minutes.

繼而投入作為縮合觸媒的二月桂酸二丁基錫0.02份之後，以10℃/分鐘的速度從室溫升溫至100℃，進一步使其在100℃反應1小時。之後自然放涼至室溫，而獲得預聚物（a）。相對於FM9927之Silicate 40的寡聚物純含量的莫耳比是1：2。After adding 0.02 parts of dibutyltin dilaurate as a condensation catalyst, the temperature was raised from room temperature to 100 ° C at a rate of 10 ° C / minute, and the reaction was further performed at 100 ° C for 1 hour. Then, it was left to cool to room temperature, and a prepolymer (a) was obtained. The mole ratio to the pure content of oligomer of Silicate 40 of FM9927 is 1: 2.

苯基改質聚二甲基矽氧烷系混成預聚物（C）的製備 將合成例1所製備的苯基改質混成預聚物（A）、和合成例2所製備的苯基改質混成預聚物（B），以（A）：（B）＝75：25的質量比，在氮氣氣氛下，於室溫中攪拌混合1小時，藉此製備成苯基改質聚二甲基矽氧烷系混成預聚物（C）。Preparation of phenyl modified polydimethylsiloxane based prepolymer (C)  Modified phenyl prepared in Synthesis Example 1 into prepolymer (A) and benzene prepared in Synthesis Example 2 The base modification was mixed into the prepolymer (B), and the mass ratio of (A) :( B) = 75: 25 was stirred and mixed at room temperature under a nitrogen atmosphere for 1 hour, thereby preparing a phenyl modified polymer. Dimethylsiloxane is mixed into a prepolymer (C).

＜實施例1＞ 在裝有苯基改質聚二甲基矽氧烷系混成預聚物（C）23份之聚丙烯製燒杯中，投入平均粒徑為80μm的AlN填料（古河電子股份有限公司製造的FAN-f80）77份，以螺旋槳攪拌機混合10分鐘以使其均勻。將所獲得的複合物，使用陶瓷三輥磨機進一步捏揉10分鐘，再進行回收。將所回收的複合物以聚甲基戊烯樹脂薄膜夾持，並以拉伸輥成形為尺寸約100mm×150mm、厚度0.5mm的片狀。將已成形的片材在熱風循環式乾燥機中以200℃加熱10小時，而獲得橡膠片狀的熱傳導片。〈Example 1〉 In a polypropylene beaker containing 23 parts of a phenyl-modified polydimethylsiloxane-based prepolymer (C), an AlN filler having an average particle diameter of 80 μm was charged (Furukawa Electronics Co., Ltd. 77 parts of FAN-f80 manufactured by the company, mixed with a propeller mixer for 10 minutes to make it uniform. The obtained composite was further kneaded using a ceramic three-roll mill for 10 minutes, and then recovered. The recovered composite was sandwiched by a polymethylpentene resin film, and formed into a sheet shape having a size of about 100 mm × 150 mm and a thickness of 0.5 mm by a stretching roll. The formed sheet was heated at 200 ° C. for 10 hours in a hot-air circulation dryer to obtain a rubber sheet-like heat conductive sheet.

另外，實施例及比較例的各填料的平均粒徑，是採用雷射繞射/散射式粒徑分佈測定裝置（崛場製作所製造的LA-950V2），依循日本工業標準JIS Z 8825來測定。於燒杯中裝入離子交換水50mL、試料0.5g、分散劑（六偏磷酸鈉）0.1g並加以攪拌，再注入至測定裝置中。對試料照射雷射光束，從試料所發出的繞射、散射光的強度分佈圖案來求取平均粒徑。In addition, the average particle diameter of each filler in the examples and comparative examples was measured using a laser diffraction / scattering type particle size distribution measuring device (LA-950V2 manufactured by Horiba, Ltd.) in accordance with Japanese Industrial Standard JIS Z 8825. A beaker was charged with 50 mL of ion-exchanged water, 0.5 g of a sample, and 0.1 g of a dispersant (sodium hexametaphosphate), stirred, and then poured into a measuring device. The sample was irradiated with a laser beam, and the average particle diameter was obtained from the intensity distribution pattern of the diffracted and scattered light emitted from the sample.

＜實施例2～6＞ 將平均粒徑為80μm的AlN填料（古河電子股份有限公司製造的FAN-f80）、和平均粒徑為5.0μm的Al₂ O₃ 填料，以80：20（實施例2）、60：40（實施例3）、30：70（實施例4）的質量比進行混合。又，將平均粒徑為80μm的AlN填料（古河電子股份有限公司製造的FAN-f80）、和平均粒徑為4.0μm的氮化硼(BN)填料，以80：20（實施例5）的質量比進行混合。又，將平均粒徑為30μm的AlN填料（古河電子股份有限公司製造的FAN-f30）、和平均粒徑為5.0μm的Al₂ O₃ 填料，以70：30（實施例6）的質量比進行混合。關於混合，是使用球磨機來混合4分鐘。<Examples 2 to 6> An AlN filler having an average particle diameter of 80 μm (FAN-f80 manufactured by Furukawa Electronics Co., Ltd.) and an Al ₂ O ₃ filler having an average particle diameter of 5.0 μm were used at 80:20 (Example 2), 60:40 (Example 3), 30:70 (Example 4) are mixed at a mass ratio. In addition, an AlN filler (FAN-f80 manufactured by Furukawa Electronics Co., Ltd.) having an average particle diameter of 80 μm and a boron nitride (BN) filler having an average particle diameter of 4.0 μm were prepared in a ratio of 80:20 (Example 5). Mass ratio is mixed. In addition, an AlN filler (FAN-f30 manufactured by Furukawa Electronics Co., Ltd.) having an average particle diameter of 30 μm and an Al ₂ O ₃ filler having an average particle diameter of 5.0 μm were used at a mass ratio of 70:30 (Example 6). Mix. The mixing was performed using a ball mill for 4 minutes.

在分別裝入苯基改質聚二甲基矽氧烷系混成預聚物（C）14份、11份、11份、20份、14份之聚丙烯製燒杯中，將上述預先混合而成之混合填料（實施例2～6）依照上述順序分別投入86份、89份、89份、80份、86份，以螺旋槳攪拌機混合10分鐘以使其分別均勻。將所獲得的複合物，使用陶瓷三輥磨機進一步捏揉10分鐘，再進行回收。將所回收的複合物以聚甲基戊烯樹脂薄膜夾持，並以拉伸輥分別成形為尺寸約100mm×150mm、厚度0.5mm的片狀。將已成形的片材在熱風循環式乾燥機中以200℃加熱10小時，而獲得具有各種組成之橡膠片狀的熱傳導片。14 parts, 11 parts, 11 parts, 20 parts, and 14 parts of polypropylene beakers filled with phenyl-modified polydimethylsiloxane-based mixed prepolymers (C) were prepared by mixing the above in advance. The mixed fillers (Examples 2 to 6) were respectively put in 86 parts, 89 parts, 89 parts, 80 parts, and 86 parts in the above order, and mixed with a propeller mixer for 10 minutes to make them uniform. The obtained composite was further kneaded using a ceramic three-roll mill for 10 minutes, and then recovered. The recovered composite was sandwiched by a polymethylpentene resin film, and each was formed into a sheet shape having a size of about 100 mm × 150 mm and a thickness of 0.5 mm by a stretching roll. The formed sheet was heated at 200 ° C. for 10 hours in a hot-air circulation dryer to obtain a rubber sheet-shaped heat conductive sheet having various compositions.

＜比較例1＞ 將平均粒徑為80μm的AlN填料（古河電子股份有限公司製造的FAN-f80）、和平均粒徑為5.0μm的Al₂ O₃ 填料，以70：30的質量比，藉由與實施例2～6同樣的方法進行混合，而獲得混合填料。在裝入不含苯基之混成預聚物（a）13份之聚丙烯製燒杯中，投入上述預先混合而成之混合填料87份，以螺旋槳攪拌機混合10分鐘以使其均勻。將所獲得的複合物，使用陶瓷三輥磨機進一步捏揉10分鐘，再進行回收。將所回收的複合物以聚甲基戊烯樹脂薄膜夾持，並以拉伸輥分別成形為尺寸約100mm×150mm、厚度0.5mm的片狀。將已成形的片材在熱風循環式乾燥機中以200℃加熱10小時，而獲得橡膠片狀的熱傳導片。<Comparative Example 1> An AlN filler having an average particle diameter of 80 μm (FAN-f80 manufactured by Furukawa Electronics Co., Ltd.) and an Al ₂ O ₃ filler having an average particle diameter of 5.0 μm were used at a mass ratio of 70:30. Mixing was performed by the same method as Examples 2 to 6 to obtain a mixed filler. Into a polypropylene beaker containing 13 parts of the phenyl-free mixed prepolymer (a), 87 parts of the above-mentioned mixed filler was put, and mixed with a propeller mixer for 10 minutes to make uniform. The obtained composite was further kneaded using a ceramic three-roll mill for 10 minutes, and then recovered. The recovered composite was sandwiched by a polymethylpentene resin film, and each was formed into a sheet shape having a size of about 100 mm × 150 mm and a thickness of 0.5 mm by a stretching roll. The formed sheet was heated at 200 ° C. for 10 hours in a hot-air circulation dryer to obtain a rubber sheet-like heat conductive sheet.

＜比較例2＞ 將平均粒徑為80μm的AlN填料（古河電子股份有限公司製造的FAN-f80）、和平均粒徑為5.0μm的Al₂ O₃ 填料，以70：30的質量比，藉由與實施例2～6同樣的方法進行混合，而獲得混合填料。在裝入矽氧樹脂（Momentive Performance Materials Inc.製造的TSE-3033）9份之聚丙烯製燒杯中，投入上述混合填料91份，以螺旋槳攪拌機混合10分鐘以使其均勻。將所獲得的複合物，使用陶瓷三輥磨機進一步捏揉10分鐘，再進行回收。將所回收的複合物以聚甲基戊烯樹脂薄膜夾持，並以拉伸輥成形為尺寸約100mm×150mm、厚度0.5mm的片狀。將已成形的片材在熱風循環式乾燥機中以150℃加熱0.5小時，而獲得橡膠片狀的熱傳導片。<Comparative Example 2> An AlN filler having an average particle diameter of 80 μm (FAN-f80 manufactured by Furukawa Electronics Co., Ltd.) and an Al ₂ O ₃ filler having an average particle diameter of 5.0 μm were used at a mass ratio of 70:30. Mixing was performed by the same method as Examples 2 to 6 to obtain a mixed filler. Into a polypropylene beaker filled with 9 parts of a silicone resin (TSE-3033 manufactured by Momentive Performance Materials Inc.), 91 parts of the above-mentioned mixed filler was charged, and mixed with a propeller mixer for 10 minutes to make uniform. The obtained composite was further kneaded using a ceramic three-roll mill for 10 minutes, and then recovered. The recovered composite was sandwiched by a polymethylpentene resin film, and formed into a sheet shape having a size of about 100 mm × 150 mm and a thickness of 0.5 mm by a stretching roll. The formed sheet was heated at 150 ° C. for 0.5 hour in a hot-air circulation dryer to obtain a rubber sheet-like heat conductive sheet.

＜實施例7～11＞ 將平均粒徑為80μm的AlN填料（古河電子股份有限公司製造的FAN-f80）、和平均粒徑為5.0μm的Al₂ O₃ 填料，以70：30的質量比，藉由與實施例2～6同樣的方法進行混合，而獲得混合填料。將苯基改質聚二甲基矽氧烷系混成預聚物（C）和混合填料，分別以質量比成為6：94（實施例7）、9：91（實施例8）、13：87（實施例9）、30：70（實施例10）、50：50（實施例11）的方式饋入聚丙烯製燒杯中，分別以螺旋槳攪拌機混合10分鐘以使其均勻。將所獲得的複合物，使用陶瓷三輥磨機進一步捏揉10分鐘，再進行回收。將所回收的複合物以聚甲基戊烯樹脂薄膜夾持，並以拉伸輥分別成形為尺寸約100mm×150mm、厚度0.5mm的片狀。將已成形的片材在熱風循環式乾燥機中以200℃加熱10小時，而獲得具有各種組成之橡膠片狀的熱傳導片。<Examples 7 to 11> An AlN filler having an average particle diameter of 80 μm (FAN-f80 manufactured by Furukawa Electronics Co., Ltd.) and an Al ₂ O ₃ filler having an average particle diameter of 5.0 μm were used at a mass ratio of 70:30. A mixed filler was obtained by mixing in the same manner as in Examples 2 to 6. The phenyl-modified polydimethylsiloxane system was mixed into a prepolymer (C) and a mixed filler, and the mass ratios were 6:94 (Example 7), 9:91 (Example 8), and 13:87, respectively. (Example 9), 30:70 (Example 10), 50:50 (Example 11) were fed into polypropylene beakers, and each was mixed with a propeller mixer for 10 minutes to make it uniform. The obtained composite was further kneaded using a ceramic three-roll mill for 10 minutes, and then recovered. The recovered composite was sandwiched by a polymethylpentene resin film, and each was formed into a sheet shape having a size of about 100 mm × 150 mm and a thickness of 0.5 mm by a stretching roll. The formed sheet was heated at 200 ° C. for 10 hours in a hot-air circulation dryer to obtain a rubber sheet-shaped heat conductive sheet having various compositions.

＜實施例12～15＞ 將平均粒徑為5.0μm的Al₂ O₃ 填料、和平均粒徑為0. 3μm的Al₂ O₃ 填料，以70：30的質量比，藉由與實施例2～6同樣的方法進行混合，而獲得混合填料。將苯基改質聚二甲基矽氧烷系混成預聚物（C）和混合填料，分別以質量比成為9：91（實施例12）、10：90（實施例13）、11：89（實施例14）、14：86（實施例15）的方式饋入聚丙烯製燒杯中，分別以螺旋槳攪拌機混合10分鐘以使其均勻。將所獲得的複合物，使用陶瓷三輥磨機進一步捏揉10分鐘，再進行回收。將所回收的複合物以聚甲基戊烯樹脂薄膜夾持，並以拉伸輥分別成形為尺寸約100mm×150mm、厚度0.5mm的片狀。將已成形的片材在熱風循環式乾燥機中以200℃加熱10小時，而獲得具有各種組成之橡膠片狀的熱傳導片。另外，關於實施例15，其未進行成形、加熱而製作成熱傳導糊劑。<Examples 12 to 15> The average particle diameter of 5.0μm Al ₂ O ₃ filler, and an average particle size of Al 0. 3μm ₂ O ₃ filler mass ratio of 70:30, with the embodiment of Example 2 by ～ 6 were mixed in the same manner to obtain a mixed filler. The phenyl-modified polydimethylsiloxane system was mixed into a prepolymer (C) and a mixed filler, and the mass ratios were 9:91 (Example 12), 10:90 (Example 13), and 11:89. (Example 14) and 14:86 (Example 15) were fed into a polypropylene beaker, and each was mixed with a propeller mixer for 10 minutes to make it uniform. The obtained composite was further kneaded using a ceramic three-roll mill for 10 minutes, and then recovered. The recovered composite was sandwiched by a polymethylpentene resin film, and each was formed into a sheet shape having a size of about 100 mm × 150 mm and a thickness of 0.5 mm by a stretching roll. The formed sheet was heated at 200 ° C. for 10 hours in a hot-air circulation dryer to obtain a rubber sheet-shaped heat conductive sheet having various compositions. In addition, Example 15 was prepared as a heat conductive paste without forming and heating.

結果評估方法 關於所製作成的高熱傳導複合材料，在室溫下，進行濕熱試驗(PCT（ Pressure Cooker Test ），於熱壓釜中裝入純水、樣品片，121℃×100%RH：2atm下）200小時之後、或是以200℃保持200小時之後，實施以下的評估。Result evaluation method For the prepared high-heat-conducting composite material, a wet heat test (PCT (Pressure Cooker Test)) was performed at room temperature, and pure water and a sample piece were charged into the autoclave at 121 ° C × 100% RH. : 2atm) After 200 hours, or after 200 hours at 200 ° C, the following evaluations were performed.

（1）熱傳導率 熱傳導率的測定，是使用Mentor Graphics Japan Co.,Ltd.製造的T3ster DynTIM測試儀，依循ASTM D5470測試標準而進行。製作直徑為12.8mm且厚度為0.35mm、0.5mm、0.6mm、0.7mm、0.8mm的試料。對試料施加規定的荷重，從上下（厚度方向）的溫度差和電力來測定熱阻值。從上述5種試料的厚度和熱阻的圖表，將接觸熱阻成分和片材的熱阻成分分離，將片材的熱阻成分以線性近似法求出熱阻值，再從該熱阻值算出熱傳導率。(1) Thermal conductivity The thermal conductivity was measured using a T3ster DynTIM tester manufactured by Mentor Graphics Japan Co., Ltd., in accordance with the ASTM D5470 test standard. A sample having a diameter of 12.8 mm and a thickness of 0.35 mm, 0.5 mm, 0.6 mm, 0.7 mm, and 0.8 mm was prepared. A predetermined load was applied to the sample, and the thermal resistance was measured from the temperature difference between the upper and lower (thickness direction) and power. Separate the contact thermal resistance component from the thermal resistance component of the sheet from the graphs of the thickness and thermal resistance of the five samples, determine the thermal resistance value of the thermal resistance component of the sheet by a linear approximation method, and then from the thermal resistance value Calculate the thermal conductivity.

（2）彈性模數 彈性模數的測定，是使用島津製作所製造的AGS-X 50N試驗機，並依照JIS K 6251測試標準而進行。製作厚度為0.5mm的啞鈴狀7號型的樣品片來作為試驗片。從應變率和應力的圖表中，到上降伏點（upper yield point）為止的斜率，計算出彈性模數。(2) Modulus of Elasticity The modulus of elasticity was measured using an AGS-X 50N tester manufactured by Shimadzu Corporation in accordance with the JIS K 6251 test standard. As a test piece, a dumbbell-shaped sample piece having a thickness of 0.5 mm was prepared. From the graph of strain rate and stress, the slope to the upper yield point is used to calculate the elastic modulus.

（3）拉伸強度 拉伸強度的測定，是使用島津製作所製造的AGS-X 50N試驗機，並依照JIS K 6251測試標準而進行。製作厚度為0.5mm的啞鈴狀7號型的樣品片來作為試驗片。將切斷試驗片時的拉伸力除以試驗片的初期截面積，而計算出拉伸強度。(3) Tensile strength The tensile strength was measured by using an AGS-X 50N tester manufactured by Shimadzu Corporation and in accordance with the JIS K 6251 test standard. As a test piece, a dumbbell-shaped sample piece having a thickness of 0.5 mm was prepared. The tensile strength when the test piece was cut was divided by the initial cross-sectional area of the test piece to calculate the tensile strength.

（4）伸長 伸長的測定，是使用島津製作所製造的AGS-X 50N試驗機，並依照JIS K 6251測試標準而進行。製作厚度為0.5mm的啞鈴狀7號型的樣品片來作為試驗片。將切斷試驗片時的長度減去試驗片初期的長度，再除以試驗片初期的長度，而計算出伸長。(4) Elongation The elongation was measured using an AGS-X 50N tester manufactured by Shimadzu Corporation in accordance with the JIS K 6251 test standard. As a test piece, a dumbbell-shaped sample piece having a thickness of 0.5 mm was prepared. The length at the time of cutting the test piece is subtracted from the initial length of the test piece, and then divided by the initial length of the test piece to calculate the elongation.

評估結果 將評估結果顯示於表1。Evaluation Results The evaluation results are shown in Table 1.

[表1] [Table 1]

如同表1所示，實施例1～6的熱傳導片也就是本發明的高熱傳導複合材料，即便在高溫（高濕）下保持之後，柔軟性、熱傳導性仍優異，拉伸強度、伸長亦顯示適度的值。尤其，藉由組合使用AlN填料、和粒徑小於AlN填料的Al₂ O₃ 填料或BN填料，可獲得熱傳導率更加提高的高熱傳導複合材料。另一方面，採用不含苯基之預聚物而成之比較例1的熱傳導片，從製作完成當下開始即缺乏柔軟性，在高溫（高濕）下保持之後，柔軟性更加受損。又，使用市售矽氧樹脂而成之比較例2的熱傳導片，亦顯示與比較例1的熱傳導片同樣的特性。As shown in Table 1, the thermally conductive sheets of Examples 1 to 6 are the high thermally conductive composite materials of the present invention. Even after being held at high temperature (high humidity), they have excellent flexibility and thermal conductivity, and show tensile strength and elongation. Moderate value. In particular, by using an AlN filler in combination with an Al ₂ O ₃ filler or a BN filler having a particle size smaller than that of the AlN filler, a high thermal conductivity composite material having a further improved thermal conductivity can be obtained. On the other hand, the thermally conductive sheet of Comparative Example 1 using a prepolymer that does not contain a phenyl group lacks flexibility from the moment it is manufactured, and its flexibility is further impaired after it is held under high temperature (high humidity). The heat conductive sheet of Comparative Example 2 using a commercially available silicone resin also exhibited the same characteristics as the heat conductive sheet of Comparative Example 1.

實施例7～10的熱傳導片也就是本發明的高熱傳導複合材料，即便在高溫（高濕）下保持之後，柔軟性、熱傳導性仍優異，拉伸強度、伸長亦顯示適度的值。實施例11的熱傳導片，強度弱，無法測定彈性模數，拉伸強度亦為小於1MPa的低值，但具有可使用作為糊劑材料的特性。The heat-conducting sheets of Examples 7 to 10 are also the high-heat-conducting composite material of the present invention. Even after being held at high temperature (high humidity), the flexibility and heat conductivity are excellent, and the tensile strength and elongation also show moderate values. The heat conductive sheet of Example 11 was weak, and the elastic modulus could not be measured. The tensile strength was also a low value of less than 1 MPa, but it had characteristics that it could be used as a paste material.

實施例12～15的熱傳導片（實施例15：糊劑用）也就是本發明的高熱傳導複合材料，藉由混合使用粒徑不同的2種Al₂ O₃ 填料，即便在高溫下的維持之後，柔軟性、熱傳導性仍優異。The heat-conducting sheets of Examples 12 to 15 (Example 15: for paste) are also the high-heat-conducting composite materials of the present invention. By mixing two kinds of Al ₂ O ₃ fillers with different particle sizes, even after maintaining at high temperature, , Excellent flexibility and thermal conductivity.

以下顯示熱傳導片的其他製造例。 [製造例1] 於已裝入預聚物20份之瑪瑙研缽中，投入平均粒徑為80μm的AlN填料80份，混合10分鐘以使其均勻。將所獲得的複合物，以聚甲基戊烯樹脂薄膜夾持，並以硫化加壓機而成形為尺寸約200mm×200mm、厚度0.5mm的片狀。將已成形的片材在熱風循環式乾燥機中以200℃加熱10小時，而獲得橡膠片狀的熱傳導片。The other manufacturing examples of a heat conductive sheet are shown below. [Manufacturing Example 1] 80 parts of an AlN filler having an average particle diameter of 80 μm was put into an agate mortar in which 20 parts of a prepolymer had been charged, and mixed for 10 minutes to make it uniform. The obtained composite was sandwiched by a polymethylpentene resin film, and formed into a sheet shape having a size of about 200 mm × 200 mm and a thickness of 0.5 mm by a vulcanizing press. The formed sheet was heated at 200 ° C. for 10 hours in a hot-air circulation dryer to obtain a rubber sheet-like heat conductive sheet.

[製造例2] 於已裝入預聚物20份之聚丙烯製燒杯中，投入平均粒徑為80μm的AlN填料80份，混合10分鐘以使其均勻。將所獲得的複合物，使用陶瓷三輥磨機進一步捏揉10分鐘，再進行回收。將所獲得的複合物投入單軸擠型機，而成形為寬100mm、厚度0.5mm、長300mm的片狀。將已成形的片材在熱風循環式乾燥機中以200℃加熱10小時，而獲得橡膠片狀的熱傳導片。[Manufacturing Example 2] Into a polypropylene beaker filled with 20 parts of a prepolymer, 80 parts of an AlN filler having an average particle diameter of 80 μm was charged and mixed for 10 minutes to make uniform. The obtained composite was further kneaded using a ceramic three-roll mill for 10 minutes, and then recovered. The obtained composite was put into a uniaxial extruder and formed into a sheet shape having a width of 100 mm, a thickness of 0.5 mm, and a length of 300 mm. The formed sheet was heated at 200 ° C. for 10 hours in a hot-air circulation dryer to obtain a rubber sheet-like heat conductive sheet.

如同以上，藉由將本發明所採用的苯基改質聚二甲基矽氧烷系混成聚合物作為基材，而可獲得耐熱性及柔軟性優異的高熱傳導複合材料，該苯基改質聚二甲基矽氧烷系混成聚合物包含預聚物（A）和（B）之反應物，該預聚物（A）是苯基改質混成預聚物，包含由在兩端具有矽醇基之聚二甲基矽氧烷和苯基三烷氧基矽烷所形成之縮合反應生成物，該預聚物（B）是苯基改質混成預聚物，包含由在兩端具有三烷氧矽基之聚二甲基矽氧烷、苯基三烷氧基矽烷及二苯基二烷氧基矽烷所形成之水解縮合反應生成物。藉由在上述預聚物分子骨架中導入苯基，且特別是將苯基導入至源自烷氧基矽烷單體的部分而非源自PDMS的部分，而會提升樹脂的耐熱溫度，即便是250℃的耐熱環境亦可使用。As described above, by using the phenyl-modified polydimethylsiloxane-based hybrid polymer used in the present invention as a substrate, a high heat-conductive composite material excellent in heat resistance and flexibility can be obtained. The polydimethylsiloxane-based hybrid polymer includes a reactant of prepolymers (A) and (B). The prepolymer (A) is a phenyl group modified into a prepolymer. Condensation reaction product of alcohol-based polydimethylsiloxane and phenyltrialkoxysilane. The prepolymer (B) is a phenyl group modified by a phenyl group. Hydrolyzed condensation reaction product formed by alkoxysilyl-based polydimethylsiloxane, phenyltrialkoxysilane, and diphenyldialkoxysilane. By introducing a phenyl group into the above-mentioned molecular structure of the prepolymer, and particularly introducing the phenyl group to a portion derived from an alkoxysilane monomer rather than a portion derived from PDMS, the heat resistance temperature of the resin is increased, even if it is It can also be used in a heat-resistant environment at 250 ° C.

上述預聚物（A）和預聚物（B），其具有在末端有羥基或烷氧基或兩者兼具之聚二甲基矽氧烷骨架，藉由與表面具有羥基等活性基團的熱傳導性填料之間的反應，而可製作耐熱性特別優異的熱傳導構件（散熱構件）。亦即，具有在末端有羥基或烷氧基或兩者兼具之聚二甲基矽氧烷骨架而成之預聚物，在硬化時，亦與填料表面發生反應，藉此可提供一種熱傳導構件，其在界面的空氣層少。如此一來，藉由與樹脂層之間的化學反應而像這樣堅固地保護填料表層，藉此可防止因水分或氧所致之劣化。又，若將AlN使用於熱傳導性填料，則可製作較高熱傳導性的熱傳導片等高熱傳導複合材料。The prepolymer (A) and the prepolymer (B) have a polydimethylsiloxane skeleton having a hydroxyl group or an alkoxy group at the terminal, or both, and have active groups such as a hydroxyl group on the surface. Reaction between the thermally conductive fillers, and a thermally conductive member (radiating member) having particularly excellent heat resistance can be produced. That is, a prepolymer having a polydimethylsiloxane skeleton having a hydroxyl group or an alkoxy group at the terminal, or both, also reacts with the surface of the filler when hardened, thereby providing a thermal conduction Component, which has less air layer at the interface. In this way, by chemically reacting with the resin layer, the surface layer of the filler is protected as such, thereby preventing deterioration due to moisture or oxygen. When AlN is used as the thermally conductive filler, a highly thermally conductive composite material such as a thermally conductive sheet having high thermal conductivity can be produced.

如此製作成的高熱傳導複合材料，適合使用作為熱傳導（散熱）片、高熱傳導膏、高熱傳導黏著片、高熱傳導黏著劑，或作為耐熱性、熱傳導性、電絕緣特性優異的材料。在SiC、GaN之類作為次世代電源模組而受到矚目的高溫動作元件的散熱、黏接、密封上，本發明的高熱傳導複合材料尤其可作為有效的材料而使用。The high thermal conductivity composite material thus produced is suitable for use as a thermal conductive (radiating) sheet, a high thermal conductive paste, a high thermal conductive adhesive sheet, a high thermal conductive adhesive, or a material having excellent heat resistance, thermal conductivity, and electrical insulation properties. The high-heat-conducting composite material of the present invention is particularly useful as an effective material for heat dissipation, adhesion, and sealing of high-temperature operating elements that have attracted attention as next-generation power modules.

[變化例] 本發明不受上述有限的實施例所限定，所屬技術領域中具有通常知識者可由申請專利範圍和說明書之記載而瞭解本發明的技術思想，只要不違反本發明的技術思想，則亦可進行變化、刪除及增添。 [產業利用性][Modifications] The present invention is not limited by the above-mentioned limited embodiments. Those with ordinary knowledge in the technical field can understand the technical idea of the present invention by applying for the scope of the patent and the description of the specification. As long as the technical idea of the present invention is not violated, Changes, deletions and additions can also be made. [Industrial availability]

本發明的高熱傳導性材料，是在苯基改質聚二甲基矽氧烷系混成聚合物中調配有熱傳導率為20W‧m^-1 ‧K^-1 以上的熱傳導性填料而成，因其熱傳導性、柔軟性（在高溫下的該些物性的維持度）優異，所以可提供一種散熱構件，其在電子零件、電機零件等的絕緣熱傳導用途上很有用，該苯基改質聚二甲基矽氧烷系混成聚合物包含苯基改質混成預聚物（A）和苯基改質混成預聚物（B）之反應物，該苯基改質混成預聚物（A）包含由在兩端具有矽醇基之聚二甲基矽氧烷、和苯基三烷氧基矽烷所形成之縮合反應生成物，該苯基改質混成預聚物（B）包含由在兩端具有三烷氧矽基之聚二甲基矽氧烷、苯基三烷氧基矽烷及二苯基二烷氧基矽烷所形成之水解縮合反應生成物。尤其作為次世代的SiC、GaN之類的高溫動作電源模組的熱傳導構件而言，具有產業利用性。The highly thermally conductive material of the present invention is prepared by mixing a thermally conductive filler having a thermal conductivity of 20W‧m ^-1 ‧K ^-1 or more in a phenyl-modified polydimethylsiloxane-based mixed polymer. Excellent thermal conductivity and flexibility (maintaining of these physical properties at high temperatures), so it is possible to provide a heat-dissipating member, which is useful for the insulation and heat conduction of electronic parts, motor parts, etc. The phenyl-modified polydimethylene Siloxane-based hybrid polymer contains a reactant of phenyl modification mixed into prepolymer (A) and phenyl modification mixed into prepolymer (B), and the phenyl modification mixed into prepolymer (A) contains Condensation reaction product formed by polydimethylsiloxane having silanol groups at both ends and phenyltrialkoxysilane, and the phenyl group is modified and mixed into a prepolymer (B). Trialkoxysilyl polydimethylsiloxane, phenyltrialkoxysilane and diphenyldialkoxysilane formed by hydrolysis and condensation reaction products. In particular, it is industrially usable as a heat-conducting member of a next-generation high-temperature operating power module such as SiC and GaN.

依循本發明而成之高熱傳導複合材料，具有耐熱性、柔軟性、電絕緣性，進一步可使用作為高熱傳導性彈性體，該高熱傳導性彈性體是使用於200℃以上的溫度區域，且必須有高熱傳導性。尤其可使用於次世代的燃料電池、電源模組、便攜式終端機、電腦、遊戲機等的散熱用途。 【001】 【002】 【003】 【004】 【005】 【006】 【007】 【008】 【009】 【010】 【011】 【012】 【013】 【014】 【015】 【016】 【017】 【018】 【019】 【020】 【021】 【022】 【023】 【024】 【025】 【026】 【027】 【028】 【029】 【030】 【031】 【032】 【033】 【034】 【035】 【036】 【037】 【038】 【039】 【040】 【041】 【042】 【043】 【044】 【045】 【046】 【047】 【048】 【049】 【050】 【051】 【052】 【053】 【054】 【055】 【056】 【057】 【058】 【059】 【060】 【061】 【062】 【063】 【064】 【065】 【066】 【067】 【068】 【069】 【070】 【071】 【072】 【073】 【074】 【075】 【076】 【077】 【078】 【079】 【080】 【081】 【082】 【083】 【084】 【085】 【086】 【087】 【088】 【089】 【090】 【091】 【092】 【093】 【094】 【095】 【096】 【097】 【098】 【099】The high thermal conductivity composite material according to the present invention has heat resistance, flexibility, and electrical insulation, and can be further used as a high thermal conductivity elastomer. The high thermal conductivity elastomer is used in a temperature range of 200 ° C or higher, and must be used. Has high thermal conductivity. In particular, it can be used for heat dissipation of next-generation fuel cells, power modules, portable terminals, computers, and game consoles. [001] [002] [003] [004] [005] [006] [007] [008] [009] [010] [011] [012] [013] [014] [015] [016] [017] ] [018] [019] [020] [021] [022] [023] [024] [025] [026] [027] [028] [029] [030] [031] [032] [033] [033] 034] [035] [036] [037] [038] [039] [040] [041] [042] [043] [044] [045] [046] [047] [048] [049] [050] [051] [052] [053] [054] [055] [056] [057] [058] [059] [060] [061] [062] [063] [064] [065] [066] [067] ] [068] [069] [070] [071] [072] ] [073] [074] [075] [076] [077] [078] [079] [080] [081] [082] [083] [084] [085] [086] [087] [088] [088] 089] [090] [091] [092] [093] [094] [095] [096] [097] [098] [099]

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Claims (12)

一種高熱傳導複合材料，其特徵在於： 是於樹脂中調配有熱傳導率為20W‧m^-1 ‧K^-1 以上的熱傳導性填料而成之熱傳導用途的複合材料，該樹脂是苯基改質聚二甲基矽氧烷系混成聚合物，其包含下述預聚物（A）和預聚物（B）之反應物： 預聚物（A）是苯基改質混成預聚物，其包含由在兩端具有矽醇基之聚二甲基矽氧烷、和苯基三烷氧基矽烷所形成之縮合反應生成物； 預聚物（B）是苯基改質混成預聚物，其包含由在兩端具有三烷氧矽基之聚二甲基矽氧烷、苯基三烷氧基矽烷及二苯基二烷氧基矽烷所形成之水解縮合反應生成物。A high-heat-conducting composite material, characterized in that: the resin is a heat-conducting composite material prepared by disposing a thermally conductive filler having a thermal conductivity of 20W‧m ^-1 ‧K ^-1 or more in a resin, and the resin is a phenyl group modified polymer A dimethylsiloxane-based hybrid polymer containing the following reactants of the prepolymer (A) and the prepolymer (B): The prepolymer (A) is a phenyl modified prepolymer, which contains Condensation reaction product formed by a polydimethylsiloxane having a silanol group at both ends and a phenyltrialkoxysilane; the prepolymer (B) is a phenyl group modified into a prepolymer. Contains a hydrolytic condensation reaction product formed of polydimethylsiloxane, phenyltrialkoxysilane, and diphenyldialkoxysilane having trialkoxysilyl groups at both ends. 如請求項1所述之高熱傳導複合材料，其中，前述在兩端具有矽醇基之聚二甲基矽氧烷，其數量平均分子量（Mn）為25000～45000，且分子量分佈指數（Mw／Mn）為1.4以下，其中Mw為重量平均分子量；前述在兩端具有三烷氧矽基之聚二甲基矽氧烷，其數量平均分子量（Mn）為15000～28000，且分子量分佈指數（Mw／Mn）為1.3以下，其中Mw為重量平均分子量。The high thermal conductivity composite material according to claim 1, wherein the aforementioned polydimethylsiloxane having a silanol group at both ends has a number average molecular weight (Mn) of 25,000 to 45,000, and a molecular weight distribution index (Mw / Mn) is less than 1.4, where Mw is the weight average molecular weight; the aforementioned polydimethylsiloxane having a trialkoxysilyl group at both ends has a number average molecular weight (Mn) of 15,000 to 28,000, and a molecular weight distribution index (Mw / Mn) is 1.3 or less, where Mw is a weight average molecular weight. 如請求項1或請求項2所述之高熱傳導複合材料，其中，前述熱傳導性填料，在填料表面具有可進行脫水或脫醇反應之官能基。The high thermal conductivity composite material according to claim 1 or claim 2, wherein the thermally conductive filler has a functional group capable of performing a dehydration or dealcoholization reaction on the surface of the filler. 如請求項1至請求項3中任一項所述之高熱傳導複合材料，其中，前述熱傳導性填料的熱傳導率是150W‧m^-1 ‧K^-1 以上。The high thermal conductivity composite material according to any one of claim 1 to claim 3, wherein the thermal conductivity of the thermally conductive filler is 150 W‧m ^-1 ‧K ^-1 or more. 如請求項1至請求項4中任一項所述之高熱傳導複合材料，其中，前述熱傳導性填料包含氮化鋁填料。The high thermal conductivity composite material according to any one of claim 1 to claim 4, wherein the thermally conductive filler includes an aluminum nitride filler. 如請求項1至請求項5中任一項所述之高熱傳導複合材料，其中，前述熱傳導性填料，是僅添加氮化鋁、或於氮化鋁中添加氧化鋁和氮化硼之中的至少一種而成，且相對於全部的熱傳導性填料而言，平均粒徑20～100μm的氮化鋁填料的比率為25wt%以上，剩餘部分則為平均粒徑小於該氮化鋁填料之填料。The high thermal conductivity composite material according to any one of claim 1 to claim 5, wherein the thermally conductive filler is one obtained by adding only aluminum nitride or aluminum oxide and boron nitride to aluminum nitride. It is at least one type, and the ratio of the aluminum nitride filler having an average particle diameter of 20 to 100 μm is 25% by weight or more with respect to all the thermally conductive fillers, and the remainder is a filler having an average particle diameter smaller than the aluminum nitride filler. 如請求項1至請求項6中任一項所述之高熱傳導複合材料，其中，前述預聚物（A）和前述預聚物（B）之合計質量、與前述熱傳導性填料之合計質量的比，是預聚物：填料＝5：95～30：70。The high thermal conductivity composite material according to any one of claim 1 to claim 6, wherein the total mass of the prepolymer (A) and the prepolymer (B) and the total mass of the thermally conductive filler The ratio is prepolymer: filler = 5: 95 to 30:70. 如請求項1至請求項3中任一項所述之高熱傳導複合材料，其中，前述熱傳導性填料是平均粒徑為0.2～10μm的氧化鋁填料，前述預聚物（A）和前述預聚物（B）之合計質量、與前述氧化鋁填料之質量的比，是預聚物：填料＝5：95～30：70。The high thermal conductivity composite material according to any one of claim 1 to claim 3, wherein the thermally conductive filler is an alumina filler having an average particle diameter of 0.2 to 10 μm, the prepolymer (A), and the prepolymer The ratio of the total mass of the substance (B) to the mass of the alumina filler is prepolymer: filler = 5: 95 to 30:70. 如請求項1至請求項8中任一項所述之高熱傳導複合材料，其熱傳導率為4.0W‧m^-1 ‧K^-1 以上。The high thermal conductivity composite material according to any one of claim 1 to claim 8, the thermal conductivity is 4.0 W‧m ^-1 ‧K ^-1 or more. 如請求項1至請求項9中任一項所述之高熱傳導複合材料，其彈性模數為20MPa以下。The high thermal conductivity composite material according to any one of claim 1 to claim 9, its elastic modulus is 20 MPa or less. 一種熱傳導片，其包含請求項1至請求項10中任一項所述之高熱傳導複合材料。A heat conductive sheet comprising the high heat conductive composite material according to any one of claim 1 to claim 10. 一種熱傳導糊劑，其包含請求項1至請求項9中任一項所述之高熱傳導複合材料。A thermally conductive paste comprising the high thermally conductive composite material according to any one of claim 1 to claim 9.