TW202200711A - Thermally conductive silicone composition and cured product of same - Google Patents

Abstract

The present invention is a thermally conductive silicone composition which contains: (A) an organopolysiloxane that has two or more alkenyl groups in each molecule; (B) an organohydrogen polysiloxane that has two or more Si-H groups; (C) a thermally conductive filler that is composed of the following components (C-1) a spherical alumina having an average particle diameter of more than 75 [mu]m but not more than 125 [mu]m, (C-2) a spherical alumina having an average particle diameter of more than 35 [mu]m but not more than 65 [mu]m, (C-3) a spherical alumina having an average particle diameter of more than 5 [mu]m but not more than 25 [mu]m and (C-4) an amorphous alumina having an average particle diameter of more than 0.4 [mu]m but not more than 4 [mu]m; (D) a curing catalyst; (E) an addition reaction control material; (F) one or both of (F-1) an alkoxysilane compound represented by general formula (1) and (F-2) a polysiloxane compound represented by general formula (2); and (G) an organopolysiloxane represented by general formula (3). Consequently, the present invention provides: a thermally conductive silicone composition which has low viscosity and excellent processability, while maintaining insulating properties; and a cured product of this thermally conductive silicone composition. (1): R1 aR2 bSi(OR3)4-a-b.

Description

導熱性矽氧組成物及其硬化物Thermally conductive silicon oxide composition and its hardened product

本發明是有關一種導熱性矽氧組成物及其硬化物，其有用於作為導熱材料。The present invention relates to a thermally conductive silicon oxide composition and its cured product, which are useful as thermally conductive materials.

個人電腦、數位影碟、行動電話等電子機器中所使用的CPU(中央處理器)、驅動IC(積體電路)和記憶體等LSI(大型積體電路)晶片隨著高性能化、高速化、小型化、高積體化，而本身會產生大量的熱，而因該熱而使晶片的溫度上升會造成晶片的運作不良、破壞。因此，已提出用以抑制運作中的晶片的溫度上升的多種散熱方法及用於該方法的散熱構件。LSI (Large Integrated Circuit) chips such as CPU (Central Processing Unit), driver IC (Integrated Circuit), and memory used in electronic devices such as personal computers, digital video discs, and mobile phones have become increasingly high-performance, high-speed, and Due to miniaturization and high integration, a large amount of heat will be generated, and the temperature of the chip will rise due to the heat, which will cause malfunction and damage of the chip. Therefore, various heat dissipation methods for suppressing the temperature rise of the wafer in operation and heat dissipation members used for the methods have been proposed.

先前，在電子機器等中，為了抑制運作中的晶片的溫度上升，而一直是使用一種散熱片，其是使用鋁和銅等導熱率高的金屬板。此散熱片會傳導該晶片產生的熱，並藉由與外部氣體之間的溫度差來將該熱從表面釋放出。Conventionally, in electronic equipment and the like, in order to suppress the temperature rise of the wafer in operation, a heat sink has been used, which is a metal plate with high thermal conductivity such as aluminum and copper. The heat sink conducts the heat generated by the chip and releases the heat from the surface by the temperature difference with the outside air.

為了將從晶片產生的熱效率良好地傳導至散熱片，而必須使散熱片與晶片密合，但由於有各晶片的高度的差異和由組裝加工所產生的公差，故已使具有柔軟性的薄片和膏介於晶片與散熱片之間，而經由此薄片或膏來實現從晶片傳導至散熱片。In order to efficiently conduct the heat generated from the wafer to the heat sink, it is necessary to make the heat sink and the wafer close to each other. However, due to the difference in the height of each wafer and the tolerance caused by the assembly process, a flexible sheet has been used. The paste is interposed between the wafer and the heat sink, and conduction from the wafer to the heat sink is achieved through the wafer or paste.

薄片的處理性較膏更優異，而由導熱性矽氧橡膠等所形成的導熱薄片(導熱性矽氧橡膠薄片)已用於各種領域中。The handleability of the sheet is better than that of a paste, and a thermally conductive sheet (thermally conductive silicone rubber sheet) formed of thermally conductive silicone rubber or the like has been used in various fields.

專利文獻1揭示一種絕緣性組成物，其是在矽氧橡膠等合成橡膠100質量份中調配從氧化鈹、氧化鋁、水合氧化鋁、氧化鎂、氧化鋅之中選出的至少1種以上金屬氧化物100～800質量份而成。Patent Document 1 discloses an insulating composition comprising at least one metal oxide selected from beryllium oxide, aluminum oxide, hydrated aluminum oxide, magnesium oxide, and zinc oxide in 100 parts by mass of synthetic rubber such as silicone rubber. from 100 to 800 parts by mass.

另一方面，由於個人電腦、文書處理器、CD-ROM(唯讀光碟)機等電子機器的高積體化進行，而裝置內的LSI、CPU等積體電路元件的放熱量增加，故先前的冷卻方法有時不充分。特別是，當為行動用的筆記型的個人電腦時，由於機器內部的空間狹小，故無法安裝較大的散熱片和冷卻風扇。並且，此等機器中，由於在印刷基板上搭載有積體電路元件，且基板的材質是使用導熱性不良的玻璃強化環氧樹脂和聚醯亞胺樹脂，故無法像先前這樣經由散熱絕緣薄片來使熱釋放至基板。On the other hand, due to the high integration of electronic equipment such as personal computers, word processors, and CD-ROM (Compact Disk Read Only) players, the heat generation of integrated circuit elements such as LSIs and CPUs in the devices has increased. The cooling method is sometimes insufficient. In particular, in the case of a notebook personal computer for mobile use, a large heat sink and cooling fan cannot be installed due to the small space inside the machine. In addition, in these devices, since integrated circuit elements are mounted on the printed circuit board, and the material of the substrate is glass-reinforced epoxy resin and polyimide resin with poor thermal conductivity, it is impossible to pass the heat dissipation insulating sheet as before. to release heat to the substrate.

於是，使用下述方式：於積體電路元件的附近設置自然冷卻型或強制冷卻型的散熱零件，而將在元件產生的熱傳導至散熱零件。如果以此方式來使元件與散熱零件直接接觸，則熱會因表面的凹凸而傳導惡化，並且即使經由散熱絕緣薄片來安裝，散熱絕緣薄片的柔軟性也稍微不良，故有會因熱膨脹而在元件與基板之間施加應力而破損的疑慮。Then, a method is used in which a natural cooling type or a forced cooling type heat dissipation member is provided near the integrated circuit element, and the heat generated in the element is conducted to the heat dissipation member. If the element is brought into direct contact with the heat-dissipating member in this way, the heat conduction will be deteriorated due to the unevenness of the surface, and even if the heat-dissipating insulating sheet is mounted through the heat-dissipating insulating sheet, the flexibility of the heat-dissipating insulating sheet is slightly poor, so there is a possibility of thermal expansion. Doubt of breakage due to stress applied between components and substrates.

此外，如果要在各電路元件安裝散熱零件，則需要多餘的空間，而會難以進行機器的小型化，故也有時會採用將數個元件與一個散熱零件組合來冷卻的方式。In addition, if a heat dissipation component is to be mounted on each circuit element, an extra space is required, which makes it difficult to reduce the size of the apparatus. Therefore, a method of combining several components with a single heat dissipation part for cooling is sometimes employed.

特別是，筆記型的電腦中所使用的BGA(球柵陣列)型的CPU由於高度較其它元件更低而放熱量更大，故必須充分考慮冷卻方式。In particular, the BGA (Ball Grid Array) type CPU used in the notebook computer has a lower height than other components and generates more heat, so the cooling method must be fully considered.

於是，需要一種低硬度的高導熱性材料，其能夠填埋因每個元件的高度不同而產生的各種間隙。對於這樣的所欲解決的問題，而期望一種導熱性薄片，其導熱性優異且具有柔軟性而能夠對應於各種間隙。Therefore, there is a need for a low-hardness, high-thermal-conductivity material that can fill various gaps created by the difference in height of each element. With regard to such a problem to be solved, a thermally conductive sheet which is excellent in thermal conductivity and has flexibility so as to be able to cope with various gaps is desired.

此時，專利文獻2揭示一種薄片，其是以將金屬氧化物等導熱性材料混入矽氧樹脂中後進行成形而成，且於具有處理時所需的強度的矽氧樹脂層上積層有柔軟而容易變形的矽氧層。此外，專利文獻3揭示一種導熱性複合薄片，其含有導熱性填充材料，且是將ASKER C硬度為5～50的矽氧橡膠層與具有直徑0.3 mm以上的孔的多孔性強化材料層組合而成。專利文獻4揭示一種薄片，其是以導熱性矽氧橡膠來將可撓性的三維網狀體或發泡體的骨架格子表面包覆而成。專利文獻5揭示一種導熱性複合矽氧薄片，其是將具有強化性的薄片或布內藏，且至少其中一面具有黏著性，且ASKER C硬度為5～50且厚度為0.4 mm以下。專利文獻6揭示一種散熱間隔物，其含有加成硬化型液狀矽氧橡膠及導熱性絕緣性陶瓷粉末，且其硬化物的ASKER C硬度為25以下，且熱阻為3.0℃/W以下。At this time, Patent Document 2 discloses a sheet formed by mixing a thermally conductive material such as a metal oxide into a silicone resin and then molding, and laminating a flexible sheet on a silicone resin layer having strength required for handling And easily deformed silicon oxide layer. In addition, Patent Document 3 discloses a thermally conductive composite sheet comprising a thermally conductive filler and obtained by combining a silicone rubber layer having an Asker C hardness of 5 to 50 and a porous reinforcing material layer having pores with a diameter of 0.3 mm or more. become. Patent Document 4 discloses a sheet in which the surface of a skeleton lattice of a flexible three-dimensional network or foam is covered with thermally conductive silicone rubber. Patent Document 5 discloses a thermally conductive composite silicon oxide sheet, which contains a reinforcing sheet or cloth, and at least one side has adhesiveness, and has an ASKER C hardness of 5 to 50 and a thickness of 0.4 mm or less. Patent Document 6 discloses a heat-dissipating spacer comprising addition-hardening liquid silicone rubber and thermally conductive insulating ceramic powder, and the cured product has an ASKER C hardness of 25 or less and a thermal resistance of 3.0° C./W or less.

此等導熱性矽氧硬化物由於經常也要求絕緣性，故在導熱率為0.5～6 W/m・K的範圍內，經常主要是使用氧化鋁來作為導熱性填充材料。一般而言，非晶質的氧化鋁雖提高導熱率的效果較球狀的氧化鋁更高，但有對矽氧的填充性不良、材料黏度會因填充而上升而加工性惡化這樣的缺點。此外，氧化鋁像研磨劑中所使用的這樣莫氏(Mohs)硬度為9而非常硬。因此，使用特別是粒徑為10 μm以上的非晶質氧化鋁的導熱性矽氧組成物如果在製造時施加剪力，則有會將反應鍋的內壁和攪拌翼削去這樣的問題。於是，反應鍋和攪拌翼的成分會混入導熱性矽氧組成物中，而導熱性矽氧組成物及使用其的硬化物的絕緣性會降低。此外，反應鍋及攪拌翼的空隙變寬，而攪拌效率會降低，而即使在相同條件下製造，也無法獲得一定的品質。此外，為了防止此情形，而有必須頻繁更換零件這樣的問題。Since these thermally conductive silica cured products often require insulating properties, alumina is often mainly used as a thermally conductive filler in the range of thermal conductivity of 0.5 to 6 W/m·K. Generally speaking, although amorphous alumina has a higher thermal conductivity improvement effect than spherical alumina, it has disadvantages such as poor filling properties with silicon and oxygen, and material viscosity increases due to filling, thereby deteriorating workability. In addition, alumina is very hard with a Mohs hardness of 9 as used in abrasives. Therefore, when a thermally conductive siloxane composition using amorphous alumina having a particle size of 10 μm or more is applied during production, there is a problem that the inner wall of the reaction pot and the stirring blades are cut off. Then, the components of the reaction pot and the stirring blade are mixed into the thermally conductive silicone composition, and the insulating properties of the thermally conductive silicone composition and the cured product using the same are lowered. In addition, the gap between the reaction pot and the stirring blade is widened, and the stirring efficiency is lowered, and a certain quality cannot be obtained even if it is manufactured under the same conditions. Furthermore, in order to prevent this, there is a problem that parts must be replaced frequently.

為了解決此問題，而也有僅使用球狀氧化鋁粉的方法，但為了高導熱化，而必須較非晶質氧化鋁更大量填充，而組成物的黏度會上升，而加工性會惡化。此外，由於組成物及該硬化物中的矽氧的存在量會相對地減少，故硬度會上升，而壓縮性會不良。In order to solve this problem, there is also a method of using only spherical alumina powder, but in order to increase thermal conductivity, it is necessary to fill a larger amount than amorphous alumina, and the viscosity of the composition increases and the workability deteriorates. In addition, since the amount of silicon and oxygen in the composition and the cured product is relatively reduced, the hardness is increased, and the compressibility is poor.

此外，為了提高導熱率，而有一種方法，其一般是使用導熱率高的導熱性填充材料、例如氮化鋁和氮化硼等導熱性填充材料，但有成本高且加工也困難這樣的問題。 [先前技術文獻] (專利文獻)In addition, in order to improve the thermal conductivity, there is a method that generally uses a thermally conductive filler with high thermal conductivity, for example, thermally conductive fillers such as aluminum nitride and boron nitride, but there are problems such as high cost and difficult processing. . [Prior Art Literature] (patent literature)

專利文獻1：日本特開昭7-32400號公報 專利文獻2：日本特開平2-196453號公報 專利文獻3：日本特開平7-266356號公報 專利文獻4：日本特開平8-2538707號公報 專利文獻5：日本特開平9-1738號公報 專利文獻6：日本特開平9-296114號公報Patent Document 1: Japanese Patent Laid-Open No. 7-32400 Patent Document 2: Japanese Patent Application Laid-Open No. 2-196453 Patent Document 3: Japanese Patent Application Laid-Open No. 7-266356 Patent Document 4: Japanese Patent Application Laid-Open No. 8-2538707 Patent Document 5: Japanese Patent Application Laid-Open No. 9-1738 Patent Document 6: Japanese Patent Application Laid-Open No. 9-296114

[發明所欲解決的問題] 本發明是鑒於上述原因而完成，目的在於提供一種導熱性矽氧組成物及其硬化物，該組成物一面維持絕緣性一面為低黏度且加工性優異。 [解決問題的技術手段][Problems to be Solved by Invention] The present invention was made in view of the above-mentioned reasons, and an object of the present invention is to provide a thermally conductive silicon oxide composition and a cured product thereof, which have low viscosity and excellent workability while maintaining insulating properties. [Technical means to solve the problem]

為了解決上述所欲解決的問題，本發明中提供一種導熱性矽氧組成物，其特徵在於包含： (A)1分子中具有至少2個烯基的有機聚矽氧烷：100質量份； (B)具有至少2個與矽原子直接鍵結的氫原子的有機氫聚矽氧烷：與矽原子直接鍵結的氫原子的mol數成為源自(A)成分的烯基的mol數的0.1～5.0倍量的量； (C)由下述(C-1)～(C-4)成分所組成的導熱性填充材料：7,200～9,000質量份： (C-1)平均粒徑為超過75 μm且125 μm以下的球狀氧化鋁填料：2,250～4,000質量份； (C-2)平均粒徑為超過35 μm且65 μm以下的球狀氧化鋁填料：900～2,700質量份； (C-3)平均粒徑為超過5 μm且25 μm以下的球狀氧化鋁填料：450～1,500質量份； (C-4)平均粒徑為超過0.4 μm且4 μm以下的非晶質氧化鋁填料：1,600～2,500質量份； (D)鉑族金屬系硬化觸媒：相對於(A)成分以鉑族金屬系元素質量來換算為0.1～2,000 ppm； (E)加成反應控制材料：0.01～1質量份； (F)從由(F-1)下述通式(1)表示的烷氧基矽烷化合物及下述通式(2)表示的分子鏈單末端已被三烷氧基矽烷基所封閉的二甲基聚矽氧烷所組成的群組中選出的至少1種：0.01～300質量份

式(1)中，R¹ 獨立地為碳原子數6～15的烷基，R² 獨立地為未被取代或已被取代的碳原子數1～12的1價烴基，R³ 獨立地為碳原子數1～6的烷基，a為1～3的整數，b為0～2的整數，但是a＋b為1～3的整數；

式(2)中，R⁴ 獨立地為碳原子數1～6的烷基，c為5～100的整數； (G)下述通式(3)表示的23℃時的運動黏度為10～100,000 mm² /s的有機聚矽氧烷：0.1～100質量份

式(3)中，R⁵ 獨立地為碳原子數1～12的不含脂肪族不飽和鍵的1價烴基，d為5～2,000的整數。In order to solve the above-mentioned problems to be solved, the present invention provides a thermally conductive silicone composition, which is characterized by comprising: (A) an organopolysiloxane having at least 2 alkenyl groups in 1 molecule: 100 parts by mass; ( B) Organohydrogenpolysiloxane having at least two hydrogen atoms directly bonded to silicon atoms: The number of moles of hydrogen atoms directly bonded to silicon atoms is 0.1 of the number of moles of alkenyl groups derived from (A) component Amount of to 5.0 times the amount; (C) Thermally conductive filler consisting of the following (C-1) to (C-4) components: 7,200 to 9,000 parts by mass: (C-1) The average particle size exceeds 75 Spherical alumina fillers having an average particle size of more than 35 μm and 65 μm or less: 900 to 2,700 parts by mass; (C-2) 3) Spherical alumina fillers with an average particle size exceeding 5 μm and 25 μm or less: 450 to 1,500 parts by mass; (C-4) Amorphous alumina fillers with an average particle size exceeding 0.4 μm and 4 μm or less: 1,600 to 2,500 parts by mass; (D) Platinum group metal-based hardening catalyst: 0.1 to 2,000 ppm in terms of platinum group metal-based element mass relative to (A) component; (E) Addition reaction control material: 0.01 to 1 Parts by mass; (F) from (F-1) the alkoxysilane compound represented by the following general formula (1) and the molecular chain represented by the following general formula (2) whose single terminal has been replaced by a trialkoxysilane group At least one selected from the group consisting of blocked dimethylpolysiloxanes: 0.01 to 300 parts by mass

In formula (1), R ¹ is independently an alkyl group having 6 to 15 carbon atoms, R ² is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and R ³ is independently For an alkyl group having 1 to 6 carbon atoms, a is an integer of 1 to 3, b is an integer of 0 to 2, but a+b is an integer of 1 to 3;

In formula (2), R ⁴ is independently an alkyl group having 1 to 6 carbon atoms, and c is an integer of 5 to 100; (G) The kinematic viscosity at 23° C. represented by the following general formula (3) is 10 to 10 100,000 mm ² /s organopolysiloxane: 0.1 to 100 parts by mass

In formula (3), R ⁵ is independently a monovalent hydrocarbon group having 1 to 12 carbon atoms that does not contain an aliphatic unsaturated bond, and d is an integer of 5 to 2,000.

如果為這樣的導熱性矽氧組成物，則會具有高導熱性，並且一面維持絕緣性一面為低黏度且加工性優異。Such a thermally conductive silicon oxide composition has high thermal conductivity, has low viscosity while maintaining insulating properties, and is excellent in workability.

此外，本發明中較佳為一種導熱性矽氧組成物，其23℃時的絕對黏度為800 Pa・s以下。In addition, in the present invention, it is preferable to use a thermally conductive silicon oxide composition whose absolute viscosity at 23° C. is 800 Pa·s or less.

如果為這樣的導熱性矽氧組成物，則不會損害成形性。If it is such a thermally conductive silicon-oxygen composition, the formability will not be impaired.

此外，本發明中提供一種導熱性矽氧硬化物，其是使前述導熱性矽氧組成物硬化而成。In addition, the present invention provides a thermally conductive silicon oxide cured product obtained by curing the thermally conductive silicon oxide composition.

如果為這樣的導熱性矽氧硬化物，則導熱性及絕緣性優異，而合適作為一種導熱性樹脂成形體，其是例如設置於電子機器內的放熱零件與散熱零件之間來用於散熱。Such a thermally conductive cured silicone oxide is excellent in thermal conductivity and insulating properties, and is suitable as a thermally conductive resin molded body, which is installed between, for example, a heat radiating part and a heat radiating part in an electronic device for heat dissipation.

此外，本發明中較佳為一種導熱性矽氧硬化物，其導熱率為6.5 W/m・K以上。In addition, in the present invention, it is preferable to use a thermally conductive cured silicon oxide having a thermal conductivity of 6.5 W/m·K or more.

如果為這樣的導熱性矽氧硬化物，則導熱性更優異。If it is such a thermally conductive cured silicon oxide, the thermal conductivity is more excellent.

此外，本發明中較佳為一種導熱性矽氧硬化物，其硬度是以ASKER C硬度計計為60以下。In addition, in the present invention, it is preferable to use a thermally conductive silicon oxide cured product, the hardness of which is 60 or less in ASKER C hardness.

如果為這樣的導熱性矽氧硬化物，則會以沿著被散熱體的形狀的方式變形，而容易在不對被散熱體施加應力的情形下顯示良好的散熱特性。If it is such a thermally conductive cured silicon oxide, it deforms so as to follow the shape of the body to be radiated, and it is easy to exhibit good heat dissipation properties without applying stress to the body to be radiated.

此外，本發明中較佳為一種導熱性矽氧硬化物，其絕緣破壞電壓為10 kV/mm以上。In addition, in the present invention, it is preferable to use a thermally conductive silicon oxide cured product, the dielectric breakdown voltage of which is 10 kV/mm or more.

如果為這樣的導熱性矽氧硬化物，則在使用時容易安定地確保絕緣。If it is such a thermally conductive cured silicon oxide, it is easy to ensure stable insulation at the time of use.

此外，本發明中提供一種導熱性矽氧組成物的製造方法，其至少具有一面將前述(A)、(C)、(F)成分加熱一面攪拌的步驟。Moreover, this invention provides the manufacturing method of the thermally conductive silicon-oxygen composition which has the process of stirring at least the said (A), (C), and (F) components while heating.

如果為這樣的導熱性矽氧組成物的製造方法，則能夠減少在成型後的硬化物表面產生的氣泡。 [功效]According to the manufacturing method of such a thermally conductive silicon oxide composition, the generation of air bubbles on the surface of the cured product after molding can be reduced. [effect]

如上所述，本發明的導熱性矽氧組成物是以特定比例來將平均粒徑為超過0.4 μm且65 μm以下的球狀氧化鋁及非晶質氧化鋁與平均粒徑為超過75 μm且125 μm以下的球狀氧化鋁併用，而大粒徑球狀氧化鋁會彌補粒徑小的球狀氧化鋁的缺點，且粒徑小的球狀氧化鋁會彌補大粒徑球狀氧化鋁的缺點，而能夠提供一種導熱性矽氧硬化物，其壓縮性、絕緣性、導熱性、加工性優異且特別是具有6.5 W/m・K以上的導熱率。As described above, the thermally conductive silicon-oxygen composition of the present invention is a mixture of spherical alumina and amorphous alumina with an average particle size exceeding 0.4 μm and 65 μm or less with an average particle size exceeding 75 μm and Spherical alumina below 125 μm is used together, while the large particle size spherical alumina will make up for the shortcomings of the small particle size spherical alumina, and the small particle size spherical alumina will make up for the large particle size spherical alumina. However, it is possible to provide a thermally conductive cured silicon oxide having excellent compressibility, insulating properties, thermal conductivity, and workability, and particularly having a thermal conductivity of 6.5 W/m·K or more.

此外，在製造上述組成物的步驟中，藉由一面加熱一面攪拌，即能夠減少在成型後的硬化物表面產生的氣泡。In addition, in the step of producing the above-mentioned composition, by stirring while heating, the generation of air bubbles on the surface of the cured product after molding can be reduced.

如上所述，先前一直尋求開發一種導熱性矽氧組成物及其硬化物，該組成物具有高導熱性，且一面維持絕緣性一面為低黏度且加工性優異。As described above, it has been sought to develop a thermally conductive silicon oxide composition and a cured product thereof, which have high thermal conductivity, have low viscosity while maintaining insulating properties, and are excellent in processability.

本發明人等為了達成上述目的而致力進行研究後，結果發現下述事實：以特定比例來將平均粒徑為超過0.4 μm且65 μm以下的球狀氧化鋁及非晶質氧化鋁與平均粒徑為超過75 μm且125 μm以下的球狀氧化鋁併用，即能夠解決上述問題。也就是說發現下述事實：調配大量的比表面積小的超過75 μm且125 μm以下的球狀氧化鋁，即能夠有效提高導熱性，且黏度低且加工性優異。The inventors of the present invention, as a result of diligent research to achieve the above-mentioned object, found the fact that spherical alumina and amorphous alumina having an average particle diameter of more than 0.4 μm and 65 μm or less are combined with the average particle size in a specific ratio. The above problems can be solved by using spherical alumina with a diameter exceeding 75 μm and 125 μm or less in combination. That is to say, it was found that the fact that a large amount of spherical alumina having a small specific surface area exceeding 75 μm and 125 μm or less can effectively improve thermal conductivity, has a low viscosity, and is excellent in workability.

此外發現下述事實：藉由將具有65 μm以下的平均粒徑的球狀氧化鋁及非晶質氧化鋁併用，而會提高組成物的流動性而改善加工性；以及由於超過5 μm的粒子是使用球狀氧化鋁，故能夠抑制反應鍋和攪拌翼的磨損，而絕緣性提高。In addition, it was found that by using spherical alumina having an average particle diameter of 65 μm or less and amorphous alumina in combination, the fluidity of the composition is improved and the workability is improved; and that the particles exceed 5 μm. Since spherical alumina is used, the abrasion of the reaction pot and the stirring blade can be suppressed, and the insulation can be improved.

也就是說發現下述事實：大粒徑球狀氧化鋁會彌補粒徑小的球狀氧化鋁的缺點，且粒徑小的球狀氧化鋁及非晶質氧化鋁會彌補大粒徑球狀氧化鋁的缺點，而能夠提供一種導熱性矽氧組成物及其硬化物，其壓縮性、絕緣性、導熱性、加工性優異且特別是具有6.5 W/m・K以上的導熱率，且合適作為一種導熱性樹脂成形體，其是例如設置於電子機器內的放熱零件與散熱零件之間來用於散熱，特別是發現下述事實：能夠提供一種導熱性矽氧組成物及其硬化物，其有用於作為導熱材料，該導熱材料是為了藉由導熱來將電子零件冷卻而使其介於放熱性電子零件的熱邊界面與散熱片或電路基板等散熱構件之間的界面，而完成本發明。That is to say, the following fact was found: the large particle size spherical alumina will make up for the shortcomings of the small particle size spherical alumina, and the small particle size spherical alumina and amorphous alumina will make up for the large particle size spherical alumina In view of the shortcomings of aluminum oxide, it is possible to provide a thermally conductive silicon-oxygen composition and a cured product thereof, which are excellent in compressibility, insulating properties, thermal conductivity, and workability, and particularly have a thermal conductivity of 6.5 W/m·K or more, and are suitable for As a thermally conductive resin molded body, which is installed between, for example, a heat-dissipating part and a heat-dissipating part in an electronic device for heat dissipation, in particular, it was found that a thermally conductive silicone composition and a cured product thereof can be provided, It is useful as a thermally conductive material, which is used to cool the electronic parts by conducting heat so as to be between the thermal boundary surface of the exothermic electronic parts and the interface between the heat dissipation members such as heat sinks or circuit boards, and complete the present invention. invention.

也就是說，本發明為一種導熱性矽氧組成物，其特徵在於包含： (A)1分子中具有至少2個烯基的有機聚矽氧烷：100質量份； (B)具有至少2個與矽原子直接鍵結的氫原子的有機氫聚矽氧烷：與矽原子直接鍵結的氫原子的mol數成為源自(A)成分的烯基的mol數的0.1～5.0倍量的量； (C)由下述(C-1)～(C-4)成分所組成的導熱性填充材料：7,200～9,000質量份： (C-1)平均粒徑為超過75 μm且125 μm以下的球狀氧化鋁填料：2,250～4,000質量份； (C-2)平均粒徑為超過35 μm且65 μm以下的球狀氧化鋁填料：900～2,700質量份； (C-3)平均粒徑為超過5 μm且25 μm以下的球狀氧化鋁填料：450～1,500質量份； (C-4)平均粒徑為超過0.4 μm且4 μm以下的非晶質氧化鋁填料：1,600～2,500質量份； (D)鉑族金屬系硬化觸媒：相對於(A)成分以鉑族金屬系元素質量來換算為0.1～2,000 ppm； (E)加成反應控制材料：0.01～1質量份； (F)從由(F-1)下述通式(1)表示的烷氧基矽烷化合物及下述通式(2)表示的分子鏈單末端已被三烷氧基矽烷基所封閉的二甲基聚矽氧烷所組成的群組中選出的至少1種：0.01～300質量份

式(1)中，R¹ 獨立地為碳原子數6～15的烷基，R² 獨立地為未被取代或已被取代的碳原子數1～12的1價烴基，R³ 獨立地為碳原子數1～6的烷基，a為1～3的整數，b為0～2的整數，但是a＋b為1～3的整數；

式(2)中，R⁴ 獨立地為碳原子數1～6的烷基，c為5～100的整數； (G)下述通式(3)表示的23℃時的運動黏度為10～100,000 mm² /s的有機聚矽氧烷：0.1～100質量份

式(3)中，R⁵ 獨立地為碳原子數1～12的不含脂肪族不飽和鍵的1價烴基，d為5～2,000的整數。That is, the present invention is a thermally conductive silicone composition, characterized by comprising: (A) an organopolysiloxane having at least two alkenyl groups in 1 molecule: 100 parts by mass; (B) having at least two Organohydrogenpolysiloxane with hydrogen atoms directly bonded to silicon atoms: an amount in which the number of moles of hydrogen atoms directly bonded to silicon atoms is 0.1 to 5.0 times the number of moles of alkenyl groups derived from (A) component (C) Thermally conductive filler consisting of the following components (C-1) to (C-4): 7,200 to 9,000 parts by mass: (C-1) Those having an average particle size of more than 75 μm and 125 μm or less Spherical alumina filler: 2,250 to 4,000 parts by mass; (C-2) Spherical alumina filler with an average particle size of more than 35 μm and 65 μm or less: 900 to 2,700 parts by mass; (C-3) Average particle size of Spherical alumina fillers exceeding 5 μm and 25 μm or less: 450-1,500 parts by mass; (C-4) Amorphous alumina fillers having an average particle size exceeding 0.4 μm and 4 μm or less: 1,600-2,500 parts by mass; (D) Platinum group metal-based hardening catalyst: 0.1 to 2,000 ppm in terms of platinum group metal-based element mass relative to (A) component; (E) Addition reaction control material: 0.01 to 1 part by mass; (F) From (F-1) an alkoxysilane compound represented by the following general formula (1) and a dimethyl polymer having a single terminal of the molecular chain represented by the following general formula (2) blocked with a trialkoxysilyl group At least one selected from the group consisting of siloxanes: 0.01 to 300 parts by mass

In formula (1), R ¹ is independently an alkyl group having 6 to 15 carbon atoms, R ² is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and R ³ is independently For an alkyl group having 1 to 6 carbon atoms, a is an integer of 1 to 3, b is an integer of 0 to 2, but a+b is an integer of 1 to 3;

In formula (2), R ⁴ is independently an alkyl group having 1 to 6 carbon atoms, and c is an integer of 5 to 100; (G) The kinematic viscosity at 23° C. represented by the following general formula (3) is 10 to 10 100,000 mm ² /s organopolysiloxane: 0.1 to 100 parts by mass

In formula (3), R ⁵ is independently a monovalent hydrocarbon group having 1 to 12 carbon atoms that does not contain an aliphatic unsaturated bond, and d is an integer of 5 to 2,000.

以下詳細說明本發明，但本發明並不受此等所限定。The present invention will be described in detail below, but the present invention is not limited to these.

本發明的導熱性矽氧組成物含有下述來作為必要成分： (A)含烯基的有機聚矽氧烷； (B)有機氫聚矽氧烷； (C)導熱性填充材料； (D)鉑族金屬系硬化觸媒； (E)加成反應控制材料； (F)表面處理劑； (G)黏度調整劑。 以下說明此等。The thermally conductive silicon-oxygen composition of the present invention contains the following as essential components: (A) alkenyl-containing organopolysiloxanes; (B) organohydrogenpolysiloxanes; (C) thermally conductive filler material; (D) platinum group metal hardening catalyst; (E) an addition reaction control material; (F) surface treatment agent; (G) Viscosity modifier. These are described below.

[(A)含烯基的有機聚矽氧烷] (A)成分也就是含烯基的有機聚矽氧烷為1分子中具有至少2個烯基的有機聚矽氧烷。(A)成分可為1分子中具有2個以上的與矽原子鍵結的烯基的有機聚矽氧烷，且會成為本發明的導熱性矽氧硬化物的主劑。一般而言通常主鏈部分基本上是由二有機矽氧烷單元的重複所構成，其分子結構的一部分可包含分枝狀的結構，並且也可為環狀體，從硬化物的機械強度等物性的觀點來看，較佳為直鏈狀的二有機聚矽氧烷。[(A) Alkenyl group-containing organopolysiloxane] The component (A), that is, the alkenyl group-containing organopolysiloxane is an organopolysiloxane having at least two alkenyl groups in one molecule. The component (A) may be an organopolysiloxane having two or more alkenyl groups bonded to silicon atoms in one molecule, and will be the main ingredient of the thermally conductive silicone cured product of the present invention. Generally speaking, the main chain part is basically composed of repeats of diorganosiloxane units, and part of its molecular structure may contain branched structures, and may also be cyclic bodies, from the mechanical strength of hardened products, etc. From the viewpoint of physical properties, straight-chain diorganopolysiloxane is preferred.

與矽原子鍵結的烯基以外的官能基為未被取代或已被取代的1價烴基，可舉例如：甲基、乙基、丙基、異丙基、丁基、異丁基、三級丁基、戊基、新戊基、己基、庚基、辛基、壬基、癸基、十二烷基等烷基；環戊基、環己基、環庚基等環烷基；苯基、甲苯基、二甲苯基、萘基、聯苯基等芳基；苯甲基、苯乙基、苯丙基、甲基苯甲基等芳烷基；及此等基的碳原子鍵結的氫原子的一部分或全部被氟、氯、溴等鹵素原子、氰基等所取代而成的基、例如氯甲基、2-溴乙基、3-氯丙基、3,3,3-三氟丙基、氯苯基、氟苯基、氰乙基、3,3,4,4,5,5,6,6,6-九氟己基等，代表性之物為碳原子數1～10的基，特別代表性之物為碳原子數1～6的基，較佳為：甲基、乙基、丙基、氯甲基、2-溴乙基、3,3,3-三氟丙基、氰乙基等碳原子數1～3的未被取代或已被取代的烷基；及苯基、氯苯基、氟苯基等未被取代或已被取代的苯基。此外，與矽原子鍵結的烯基以外的官能基並不限定於全部相同。The functional group other than the alkenyl group bonded to the silicon atom is an unsubstituted or substituted monovalent hydrocarbon group, for example: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tributyl tertiary butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl and other alkyl groups; cyclopentyl, cyclohexyl, cycloheptyl and other cycloalkyl groups; phenyl , tolyl, xylyl, naphthyl, biphenyl and other aryl groups; benzyl, phenethyl, phenylpropyl, methyl benzyl and other aralkyl groups; and carbon atoms of these groups bonded A group in which a part or all of hydrogen atoms are substituted with halogen atoms such as fluorine, chlorine, and bromine, and cyano groups, such as chloromethyl, 2-bromoethyl, 3-chloropropyl, 3,3,3-tris Fluoropropyl, chlorophenyl, fluorophenyl, cyanoethyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, etc., the representative ones are 1-10 carbon atoms The group of , especially representative is the group with 1 to 6 carbon atoms, preferably: methyl, ethyl, propyl, chloromethyl, 2-bromoethyl, 3,3,3-trifluoropropyl unsubstituted or substituted alkyl groups with 1 to 3 carbon atoms such as phenyl, cyanoethyl and the like; and unsubstituted or substituted phenyl groups such as phenyl, chlorophenyl and fluorophenyl. In addition, functional groups other than the alkenyl group bonded to the silicon atom are not limited to all the same.

此外，烯基可舉例如：乙烯基、烯丙基、丙烯基、異丙烯基、丁烯基、己烯基、環己烯基等通常碳原子數2～8左右的基，其中較佳為乙烯基、烯丙基等低級烯基，特佳為乙烯基。再者，烯基需要1分子中存在2個以上，為了設為所得的硬化物的柔軟性良好，而較佳是只與分子鏈末端的矽原子鍵結來存在。In addition, the alkenyl group includes, for example, vinyl, allyl, propenyl, isopropenyl, butenyl, hexenyl, cyclohexenyl and other groups having about 2 to 8 carbon atoms. Among them, preferred are Lower alkenyl groups such as vinyl and allyl are particularly preferred. In addition, it is necessary that two or more alkenyl groups exist in one molecule, and in order to make the obtained cured product good in flexibility, it is preferable to exist only by bonding with the silicon atom at the terminal of the molecular chain.

此有機聚矽氧烷的23℃時的運動黏度通常較佳為10～100,000 mm² /s，特佳是在500～50,000 mm² /s的範圍內。如果前述黏度在此範圍內，則所得的組成物的保存安定性良好且伸展性良好。再者，運動黏度為當使用奧氏(Ostwald)黏度計時的值(以下相同)。The kinematic viscosity at 23°C of the organopolysiloxane is generally preferably 10 to 100,000 mm ² /s, particularly preferably 500 to 50,000 mm ² /s. When the said viscosity is in this range, the storage stability of the composition obtained is favorable, and extensibility is favorable. In addition, the kinematic viscosity is a value when using an Ostwald viscometer (the same applies hereinafter).

此(A)成分的有機聚矽氧烷可單獨使用1種、或組合使用黏度不同的2種以上。The organopolysiloxane of the component (A) may be used alone or in combination of two or more having different viscosities.

[(B)有機氫聚矽氧烷] (B)成分也就是有機氫聚矽氧烷為具有至少2個與矽原子直接鍵結的氫原子的有機氫聚矽氧烷。(B)成分可為1分子中具有至少2個以上、較佳為2～100個與矽原子直接鍵結的氫原子(Si－H基)的有機氫聚矽氧烷，且為產生(A)成分的交聯劑的作用的成分。也就是說，(B)成分中的Si－H基與(A)成分中的烯基會藉由會被後述(D)成分的鉑族金屬系硬化觸媒所促進的氫矽烷化反應來進行加成，而獲得具有交聯結構的三維網狀結構。再者，當Si－H基的數目未達2個時不會硬化。[(B) Organohydrogen polysiloxane] The component (B), that is, the organohydrogenpolysiloxane, is an organohydrogenpolysiloxane having at least two hydrogen atoms directly bonded to a silicon atom. The component (B) may be an organohydrogen polysiloxane having at least 2 or more, preferably 2 to 100 hydrogen atoms (Si—H groups) directly bonded to silicon atoms in one molecule, and is used to generate (A) ) component that acts as a crosslinking agent. That is, the Si—H group in the component (B) and the alkenyl group in the component (A) proceed by a hydrosilylation reaction promoted by the platinum group metal-based hardening catalyst of the component (D) described later. Addition to obtain a three-dimensional network structure with a cross-linked structure. Furthermore, when the number of Si—H groups is less than two, hardening is not performed.

有機氫聚矽氧烷是使用下述平均結構式(4)表示之物，但並不限定於此。

式(4)中，R⁶ 獨立地為氫原子或不含脂肪族不飽和鍵的未被取代或已被取代的1價烴基，至少2個、較佳為2～10個為氫原子，e為1以上的整數，較佳為10～200的整數。The organohydrogenpolysiloxane is represented by the following average structural formula (4), but is not limited to this.

In formula (4), R ⁶ is independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group without aliphatic unsaturated bonds, at least 2, preferably 2 to 10 are hydrogen atoms, e is an integer of 1 or more, preferably an integer of 10 to 200.

式(4)中，R⁶ 的氫原子以外的不含脂肪族不飽和鍵的未被取代或已被取代的1價烴基可舉例如：甲基、乙基、丙基、異丙基、丁基、異丁基、三級丁基、戊基、新戊基、己基、庚基、辛基、壬基、癸基、十二烷基等烷基；環戊基、環己基、環庚基等環烷基；苯基、甲苯基、二甲苯基、萘基、聯苯基等芳基；苯甲基、苯乙基、苯丙基、甲基苯甲基等芳烷基；及此等基的碳原子鍵結的氫原子的一部分或全部被氟、氯、溴等鹵素原子、氰基等所取代而成的基、例如氯甲基、2-溴乙基、3-氯丙基、3,3,3-三氟丙基、氯苯基、氟苯基、氰乙基、3,3,4,4,5,5,6,6,6-九氟己基等，代表性之物為碳原子數1～10的基，特別代表性之物為碳原子數1～6的基，較佳為：甲基、乙基、丙基、氯甲基、2-溴乙基、3,3,3-三氟丙基、氰乙基等碳原子數1～3的未被取代或已被取代的烷基；及苯基、氯苯基、氟苯基等未被取代或已被取代的苯基。此外，R⁶ 並不限定全部相同。In formula (4), the unsubstituted or substituted monovalent hydrocarbon group that does not contain aliphatic unsaturated bonds other than the hydrogen atom of R ⁶ includes, for example: methyl, ethyl, propyl, isopropyl, butyl Alkyl, isobutyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl and other alkyl groups; cyclopentyl, cyclohexyl, cycloheptyl Cycloalkyl groups such as phenyl, tolyl, xylyl, naphthyl, biphenyl and other aryl groups; aralkyl groups such as benzyl, phenethyl, phenylpropyl, benzyl, etc.; and the like A group in which a part or all of the hydrogen atoms bonded to the carbon atoms of the group are replaced by halogen atoms such as fluorine, chlorine, and bromine, and cyano groups, such as chloromethyl, 2-bromoethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, chlorophenyl, fluorophenyl, cyanoethyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, etc., representative It is a group with 1 to 10 carbon atoms, and a particularly representative one is a group with 1 to 6 carbon atoms, preferably: methyl, ethyl, propyl, chloromethyl, 2-bromoethyl, 3, Unsubstituted or substituted alkyl groups with 1 to 3 carbon atoms such as 3,3-trifluoropropyl, cyanoethyl, etc.; and unsubstituted or substituted phenyl, chlorophenyl, fluorophenyl, etc. phenyl. In addition, R ⁶ is not necessarily limited to all the same.

e為1以上的整數，較佳為10～200的整數。e is an integer of 1 or more, preferably an integer of 10 to 200.

(B)成分的添加量為與矽原子直接鍵結的氫原子的mol數成為源自(A)成分的烯基的mol數的0.1～5.0倍量的量、也就是源自(B)成分的Si－H基相對於源自(A)成分的烯基1 mol成為0.1～5.0 mol的量，較佳為0.3～2.0 mol的量，更佳為0.5～1.0 mol的量。如果源自(B)成分的Si－H基相對於源自(A)成分的烯基1 mol未達0.1 mol，則有時不會硬化、或硬化物的強度不充分且無法保持成形體的形狀而無法進行處理。此外，如果超過5.0 mol，則硬化物的柔軟性會喪失而硬化物會變脆。The amount of the component (B) added is such that the number of moles of hydrogen atoms directly bonded to the silicon atom is 0.1 to 5.0 times the number of moles of the alkenyl group derived from the component (A), that is, the amount derived from the component (B) The Si—H group is in an amount of 0.1 to 5.0 mol, preferably 0.3 to 2.0 mol, more preferably 0.5 to 1.0 mol, based on 1 mol of the alkenyl group derived from the component (A). If the Si—H group derived from the component (B) is less than 0.1 mol relative to 1 mol of the alkenyl group derived from the component (A), curing may not occur, or the strength of the cured product may be insufficient and the strength of the molded body may not be maintained. shape cannot be processed. Further, if it exceeds 5.0 mol, the flexibility of the hardened product is lost and the hardened product becomes brittle.

[(C)導熱性填充材料] (C)成分也就是導熱性填充材料含有氧化鋁，且是由下述(C-1)～(C-4)成分所組成： (C-1)平均粒徑為超過75 μm且125 μm以下的球狀氧化鋁填料； (C-2)平均粒徑為超過35 μm且65 μm以下的球狀氧化鋁填料； (C-3)平均粒徑為超過5 μm且25 μm以下的球狀氧化鋁填料； (C-4)平均粒徑為超過0.4 μm且4 μm以下的非晶質氧化鋁填料。 再者，本發明中，上述平均粒徑為使用日機裝股份有限公司製的粒度分析計也就是Microtrac MT3300EX來測得的體積基準的累積平均粒徑(中位徑)的值。[(C) Thermally conductive filler] The component (C), that is, the thermally conductive filler, contains alumina, and is composed of the following components (C-1) to (C-4): (C-1) Spherical alumina fillers with an average particle size exceeding 75 μm and below 125 μm; (C-2) Spherical alumina fillers with an average particle size exceeding 35 μm and below 65 μm; (C-3) Spherical alumina fillers with an average particle size exceeding 5 μm and below 25 μm; (C-4) An amorphous alumina filler having an average particle size of more than 0.4 μm and 4 μm or less. In addition, in this invention, the said average particle diameter is the value of the cumulative average particle diameter (median diameter) based on the volume measured using the particle size analyzer made by Nikkiso Co., Ltd., that is, Microtrac MT3300EX.

(C-1)成分的球狀氧化鋁填料能夠將導熱率提高為優異。球狀氧化鋁的平均粒徑為超過75 μm且125 μm以下，較佳為80～120 μm。如果平均粒徑為75 μm以下，則提高導熱性的效果降低，並且組成物的黏度上升，而加工性惡化。此外，如果平均粒徑大於125 μm，則反應鍋和攪拌翼的磨損變顯著，而組成物的絕緣性降低。(C-1)成分的球狀氧化鋁可單獨使用1種、或複合使用2種以上。The spherical alumina filler of the component (C-1) can improve thermal conductivity to be excellent. The average particle diameter of the spherical alumina is more than 75 μm and 125 μm or less, preferably 80 to 120 μm. When the average particle diameter is 75 μm or less, the effect of improving the thermal conductivity decreases, the viscosity of the composition increases, and the processability deteriorates. In addition, when the average particle diameter is larger than 125 μm, the abrasion of the reaction pot and the stirring blade becomes remarkable, and the insulating properties of the composition decrease. The spherical alumina of the component (C-1) may be used alone or in combination of two or more.

(C-2)、(C-3)成分的球狀氧化鋁填料會提高組成物的導熱率，並且抑制非晶質氧化鋁與反應鍋和攪拌翼的接觸，而提供抑制磨損的阻障效果。(C-2)成分的平均粒徑為超過35 μm且65 μm以下，較佳為40～60 μm，(C-3)成分的平均粒徑為超過5 μm且25 μm以下，較佳為7～20 μm。如果(C-2)、(C-3)成分的平均粒徑在上述範圍外，則不會顯現上述特性，特別是如果(C-3)成分的平均粒徑為5 μm以下，則阻障效果降低，而由非晶質粒子所造成的反應鍋和攪拌翼的磨損變顯著。(C-2)、(C-3)成分的球狀氧化鋁可單獨使用1種、或複合使用2種以上。The spherical alumina fillers of the components (C-2) and (C-3) increase the thermal conductivity of the composition, suppress the contact of the amorphous alumina with the reaction pot and the stirring blade, and provide a barrier effect of inhibiting wear . The average particle diameter of the component (C-2) is more than 35 μm and 65 μm or less, preferably 40 to 60 μm, and the average particle diameter of the component (C-3) is more than 5 μm and 25 μm or less, preferably 7 ~20 μm. When the average particle size of the components (C-2) and (C-3) is outside the above-mentioned range, the above-mentioned characteristics will not be exhibited, and in particular, if the average particle size of the (C-3) component is 5 μm or less, the barrier will The effect is reduced, and the wear of the reaction pot and the stirring blade caused by the amorphous particles becomes significant. The spherical alumina of the components (C-2) and (C-3) may be used alone or in combination of two or more.

(C-4)成分的非晶質氧化鋁填料雖也會產生提高組成物的導熱率的功能，但其主要功能為組成物的黏度調整、潤滑度提高、填充性提高。(C-4)成分的平均粒徑為超過0.4 μm且4 μm以下，較佳為0.6～3 μm。如果在此範圍外，則不會顯現上述特性。The amorphous alumina filler of the component (C-4) also has the function of improving the thermal conductivity of the composition, but its main function is to adjust the viscosity of the composition, improve the lubricity, and improve the filling property. The average particle diameter of the component (C-4) is more than 0.4 μm and 4 μm or less, preferably 0.6 to 3 μm. If it is outside this range, the above-mentioned characteristics will not be exhibited.

相對於(A)成分100質量份，(C-1)成分的調配量為2,250～4,000質量份，較佳為2,750～3,500質量份。如果過少，則難以提高導熱率，如果過多，則反應鍋和攪拌翼的磨損變顯著，而組成物的絕緣性降低。The compounding quantity of (C-1) component is 2,250-4,000 mass parts with respect to 100 mass parts of (A) components, Preferably it is 2,750-3,500 mass parts. If it is too small, it will become difficult to improve thermal conductivity, and if it is too large, abrasion of a reaction pot and a stirring blade will become remarkable, and the insulating property of a composition will fall.

相對於(A)成分100質量份，(C-2)成分的調配量為900～2,700質量份，較佳為1,350～2,250質量份。如果過少，則難以提高導熱率，如果過多，則組成物的流動性會喪失，而損害成形性。The compounding quantity of (C-2) component is 900-2,700 mass parts with respect to 100 mass parts of (A) components, Preferably it is 1,350-2,250 mass parts. If it is too small, it will be difficult to improve the thermal conductivity, and if it is too large, the fluidity of the composition will be lost, and the formability will be impaired.

相對於(A)成分100質量份，(C-3)成分的調配量為450～1,500質量份，較佳為550～900質量份。如果過少，則難以提高導熱率，如果過多，則組成物的流動性會喪失，而損害成形性。The compounding quantity of (C-3) component is 450-1,500 mass parts with respect to 100 mass parts of (A) components, Preferably it is 550-900 mass parts. If it is too small, it will be difficult to improve the thermal conductivity, and if it is too large, the fluidity of the composition will be lost, and the formability will be impaired.

相對於(A)成分100質量份，(C-4)成分的調配量為1,600～2,500質量份，較佳為1,800～2,250質量份。如果過少，則難以提高導熱率，如果過多，則組成物的流動性會喪失，而損害成形性。The compounding quantity of (C-4) component is 1,600-2,500 mass parts with respect to 100 mass parts of (A) components, Preferably it is 1,800-2,250 mass parts. If it is too small, it will be difficult to improve the thermal conductivity, and if it is too large, the fluidity of the composition will be lost, and the formability will be impaired.

並且，相對於(A)成分100質量份，(C)成分的調配量(也就是上述(C-1)～(C-4)成分的合計調配量)需要為7,200～9,000質量份，較佳為7,500～8,000質量份。當此調配量為未達7,200質量份時，所得的組成物的導熱率惡化。如果調配量超過9,000質量份，則組成物的潤濕性不足，而無法獲得膏狀的均勻的組成物。Moreover, the compounding quantity of (C) component (that is, the total compounding quantity of said (C-1)-(C-4) component) needs to be 7,200-9,000 mass parts with respect to 100 mass parts of (A) components, and it is preferable It is 7,500-8,000 mass parts. When this compounding amount is less than 7,200 parts by mass, the thermal conductivity of the obtained composition deteriorates. When the compounding amount exceeds 9,000 parts by mass, the wettability of the composition is insufficient, and a paste-like uniform composition cannot be obtained.

以上述調配比例來使用(C)成分，即能夠更有利且確實地達成上述本發明的效果。By using the component (C) in the above-mentioned mixing ratio, the effect of the present invention can be achieved more favorably and surely.

[(D)鉑族金屬系硬化觸媒] (D)成分的鉑族金屬系硬化觸媒是用以促進源自(A)成分的烯基與源自(B)成分的Si－H基的加成反應，用於氫矽烷化反應的觸媒可舉例如周知的觸媒。其具體例可舉例如：鉑(包含鉑黑)、銠、鈀等鉑族金屬單體；H₂ PtCl₄ ・nH₂ O、H₂ PtCl₆ ・nH₂ O、NaHPtCl₆ ・nH₂ O、KaHPtCl₆ ・nH₂ O、Na₂ PtCl₆ ・nH₂ O、K₂ PtCl₄ ・nH₂ O、PtCl₄ ・nH₂ O、PtCl₂ 、Na₂ HPtCl₄ ・nH₂ O(但是，式中，n為0～6的整數，較佳為0或6)等氯化鉑、氯鉑酸及氯鉑酸鹽；醇類改質氯鉑酸(參照美國專利第3,220,972號說明書)；氯鉑酸與烯烴的複合物(美國專利第3,159,601號說明書、美國專利第3,159,662號說明書、美國專利第3,775,452號說明書)；使鉑黑、鈀等鉑族金屬載持於氧化鋁、氧化矽、碳等載體而成之物；銠-烯烴複合物、氯參(三苯膦)銠(威爾金森(Wilkinson)觸媒)；氯化鉑、氯鉑酸或氯鉑酸鹽與含乙烯基的矽氧烷、特別是含乙烯基的環狀矽氧烷的複合物等。[(D) Platinum Group Metal-Based Hardening Catalyst] The platinum group metal-based hardening catalyst of (D) component promotes the alkenyl group derived from (A) component and the Si—H group derived from (B) component. For the addition reaction, the catalyst used for the hydrosilylation reaction may, for example, be a known catalyst. Specific examples thereof include platinum group metal monomers such as platinum (including platinum black), rhodium, and palladium; H ₂ PtCl ₄ ·nH ₂ O, H ₂ PtCl ₆ ·nH ₂ O, NaHPtCl ₆ ·nH ₂ O, KaHPtCl ₆・nH ₂ O, Na ₂ PtCl ₆・nH ₂ O, K ₂ PtCl ₄・nH ₂ O, PtCl ₄・nH ₂ O, PtCl ₂ , Na ₂ HPtCl ₄・nH ₂ O (however, in the formula, n is An integer from 0 to 6, preferably 0 or 6) platinum chloride, chloroplatinic acid and chloroplatinate; alcohol-modified chloroplatinic acid (refer to the specification of US Pat. No. 3,220,972); Composite (US Patent No. 3,159,601, US Patent No. 3,159,662, US Patent No. 3,775,452); a product obtained by supporting platinum group metals such as platinum black and palladium on a carrier such as alumina, silicon oxide, and carbon ; rhodium-olefin complexes, chlorosine (triphenylphosphine) rhodium (Wilkinson catalyst); platinum chloride, chloroplatinic acid or chloroplatinate with vinyl-containing siloxanes, especially containing Compounds of vinyl cyclosiloxanes, etc.

(D)成分的使用量是相對於(A)成分的以鉑族金屬元素的質量來換算為0.1～2,000 ppm，較佳為50～1,000 ppm。如果未達0.1 ppm，則作為觸媒的效果低，故較不佳，如果超過2,000 ppm，則經濟上較不佳。The usage-amount of (D)component is 0.1-2,000 ppm with respect to the mass of a platinum group metal element with respect to (A) component, Preferably it is 50-1,000 ppm. If it is less than 0.1 ppm, the effect as a catalyst is low, so it is unfavorable, and if it exceeds 2,000 ppm, it is economically unfavorable.

[(E)反應控制材料] 本發明的導熱性矽氧組成物中，使用加成反應控制材料來作為(E)成分。加成反應控制材料能夠使用一般的加成反應硬化型矽氧組成物中所使用的公知的加成反應控制材料全部。例如：1-乙炔基-1-己醇、3-丁炔-1-醇、乙炔基亞甲基甲醇等乙炔系化合物和各種氮化合物、有機磷化合物、肟(oxime)化合物、有機氯化合物等。[(E) Reaction Control Material] In the thermally conductive silicon-oxygen composition of the present invention, an addition reaction control material is used as the component (E). As the addition reaction control material, all known addition reaction control materials used in general addition reaction curable silicone compositions can be used. For example: acetylene compounds such as 1-ethynyl-1-hexanol, 3-butyn-1-ol, ethynylmethylene methanol, various nitrogen compounds, organophosphorus compounds, oxime compounds, organochlorine compounds, etc. .

當調配(E)成分時，相對於(A)成分100質量份，使用量為0.01～1質量份，特別宜為0.1～0.8質量份左右。如果調配量過多，則有時硬化反應不會進行而損害成形效率。如果調配量過少，則有無法控制硬化反應的疑慮。When (E) component is mix|blended, the usage-amount is 0.01-1 mass part with respect to 100 mass parts of (A) components, Especially about 0.1-0.8 mass part is suitable. If the compounding amount is too large, the hardening reaction may not proceed and the molding efficiency may be impaired. If the blending amount is too small, there is a concern that the hardening reaction cannot be controlled.

[(F)表面處理劑] 本發明的導熱性矽氧組成物中，為了下述目的而調配(F)成分的表面處理劑：在調製組成物時，對(C)成分也就是導熱性填充材料進行疏水化處理，而提高(A)成分也就是有機聚矽氧烷之間的潤濕性，而使(C)成分也就是導熱性填充材料均勻分散在由(A)成分所構成的基質中。該(F)成分為從由下述表示的(F-1)成分及(F-2)成分所組成的群組中選出的至少1種。[(F) Surface treatment agent] In the thermally conductive silicone composition of the present invention, the surface treatment agent of the component (F) is prepared for the purpose of performing a hydrophobization treatment on the component (C), that is, the thermally conductive filler when preparing the composition, so as to improve the The component (A) is wettability between organopolysiloxanes, and the component (C), that is, the thermally conductive filler, is uniformly dispersed in the matrix composed of the component (A). This (F) component is at least 1 sort(s) chosen from the group which consists of (F-1) component and (F-2) component shown below.

(F-1)成分為下述通式(1)表示的烷氧基矽烷化合物。

式(1)中，R¹ 獨立地為碳原子數6～15的烷基，R² 獨立地為未被取代或已被取代的碳原子數1～12的1價烴基，R³ 獨立地為碳原子數1～6的烷基，a為1～3的整數，b為0～2的整數，但是a＋b為1～3的整數。The component (F-1) is an alkoxysilane compound represented by the following general formula (1).

In formula (1), R ¹ is independently an alkyl group having 6 to 15 carbon atoms, R ² is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and R ³ is independently In the alkyl group having 1 to 6 carbon atoms, a is an integer of 1 to 3, and b is an integer of 0 to 2, but a+b is an integer of 1 to 3.

上述通式(1)中，R¹ 獨立地為碳原子數6～15的烷基。R¹ 表示的烷基可舉例如：己基、辛基、壬基、癸基、十二烷基、十四烷基等。如果此R¹ 表示的烷基的碳原子數滿足6～15的範圍，則會充分提高(A)成分的潤濕性，而處理性良好，且組成物的低溫特性良好。In the above general formula (1), R ¹ is independently an alkyl group having 6 to 15 carbon atoms. Examples of the alkyl group represented by R ¹ include a hexyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, and a tetradecyl group. When the number of carbon atoms of the alkyl group represented by this R ¹ satisfies the range of 6 to 15, the wettability of the component (A) will be sufficiently improved, the handleability will be good, and the low-temperature characteristics of the composition will be good.

上述通式(1)中，R² 獨立地為未被取代或已被取代的碳原子數1～12的1價烴基。R² 表示的未被取代或已被取代的1價烴基可舉例如：甲基、乙基、丙基、異丙基、丁基、異丁基、三級丁基、戊基、新戊基、己基、庚基、辛基、壬基、癸基、十二烷基等烷基；環戊基、環己基、環庚基等環烷基；苯基、甲苯基、二甲苯基、萘基、聯苯基等芳基；苯甲基、苯乙基、苯丙基、甲基苯甲基等芳烷基；及此等基的碳原子鍵結的氫原子的一部分或全部被氟、氯、溴等鹵素原子、氰基等所取代而成的基、例如氯甲基、2-溴乙基、3-氯丙基、3,3,3-三氟丙基、氯苯基、氟苯基、氰乙基、3,3,4,4,5,5,6,6,6-九氟己基等，代表性之物為碳原子數1～10的基，特別代表性之物為碳原子數1～6的基，較佳為：甲基、乙基、丙基、氯甲基、2-溴乙基、3,3,3-三氟丙基、氰乙基等碳原子數1～3的未被取代或已被取代的烷基；及苯基、氯苯基、氟苯基等未被取代或已被取代的苯基。In the above general formula (1), R ² is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms. The unsubstituted or substituted monovalent hydrocarbon group represented by R ² includes, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, and neopentyl , hexyl, heptyl, octyl, nonyl, decyl, dodecyl and other alkyl groups; cyclopentyl, cyclohexyl, cycloheptyl and other cycloalkyl groups; phenyl, tolyl, xylyl, naphthyl , aryl groups such as biphenyl; aralkyl groups such as benzyl, phenethyl, phenylpropyl, methyl benzyl; and some or all of the hydrogen atoms bonded to the carbon atoms of these groups are fluorine, chlorine , Groups substituted by halogen atoms such as bromine, cyano groups, etc., such as chloromethyl, 2-bromoethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, chlorophenyl, fluorobenzene group, cyanoethyl group, 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, etc., representative ones are groups with 1 to 10 carbon atoms, especially representative ones are carbon atoms Groups having 1 to 6 atoms, preferably methyl, ethyl, propyl, chloromethyl, 2-bromoethyl, 3,3,3-trifluoropropyl, cyanoethyl, etc. having 1 carbon atoms unsubstituted or substituted alkyl groups of ~3; and unsubstituted or substituted phenyl groups such as phenyl, chlorophenyl, and fluorophenyl.

上述通式(1)中，R³ 獨立地為碳原子數1～6的烷基。R³ 可舉例如：甲基、乙基、丙基、丁基、己基等。In the above general formula (1), R ³ is independently an alkyl group having 1 to 6 carbon atoms. For example, R ³ includes methyl, ethyl, propyl, butyl, hexyl and the like.

上述通式(1)中，a為1～3的整數，b為0～2的整數，但是a＋b為1～3的整數。In the above general formula (1), a is an integer of 1 to 3, and b is an integer of 0 to 2, but a+b is an integer of 1 to 3.

(F-2)成分為下述通式(2)表示的分子鏈單末端已被三烷氧基矽烷基所封閉的二甲基聚矽氧烷。

式(2)中，R⁴ 獨立地為碳原子數1～6的烷基，c為5～100、較佳為5～70、特佳為10～50的整數。The component (F-2) is a dimethylpolysiloxane in which a single terminal of the molecular chain represented by the following general formula (2) is blocked with a trialkoxysilyl group.

In formula (2), R ⁴ is independently an alkyl group having 1 to 6 carbon atoms, and c is an integer of 5 to 100, preferably 5 to 70, particularly preferably 10 to 50.

上述通式(2)中，R⁴ 獨立地為碳原子數1～6的烷基。R⁴ 可舉例如甲基。In the above general formula (2), R ⁴ is independently an alkyl group having 1 to 6 carbon atoms. R ⁴ is, for example, methyl.

上述通式(2)中，c為5～100的整數，較佳為5～70的整數，特佳為10～50的整數。In the said general formula (2), c is an integer of 5-100, Preferably it is an integer of 5-70, Especially preferably, it is an integer of 10-50.

(F)成分的表面處理劑可組合調配(F-1)成分及(F-2)成分之中的任一種或兩種。(F) The surface treatment agent of a component can mix|blend either one or two of (F-1) component and (F-2) component in combination.

當調配(F)成分時，相對於(A)成分100質量份，調配量為0.01～300質量份，特佳為0.1～200質量份。如果本成分的比例增加，則有會引發油分離的可能性。如果本成分的比例減少，則作為表面處理劑的效果降低。因此，較佳是在上述範圍內。When (F) component is mix|blended, it is 0.01-300 mass parts with respect to 100 mass parts of (A) components, and it is especially preferable that it is 0.1-200 mass parts. If the ratio of this component increases, there is a possibility that oil separation may occur. When the ratio of this component is reduced, the effect as a surface treatment agent is reduced. Therefore, it is preferable to be in the said range.

[(G)黏度調整劑(有機聚矽氧烷)] 本發明的導熱性矽氧組成物中，為了導熱性矽氧組成物的黏度調整等的特性賦予的目的，而添加下述通式(3)表示的23℃時的運動黏度為10～100,000 mm² /s的有機聚矽氧烷來作為(G)成分。(G)成分可單獨使用1種、或併用2種以上。

式(3)中，R⁵ 獨立地為碳原子數1～12的不含脂肪族不飽和鍵的1價烴基，d為5～2,000的整數。[(G) Viscosity modifier (organopolysiloxane)] To the thermally conductive silicone composition of the present invention, the following general formula ( 3) An organopolysiloxane having a kinematic viscosity at 23°C of 10 to 100,000 mm ² /s is used as the component (G). (G) component can be used individually by 1 type or in combination of 2 or more types.

In formula (3), R ⁵ is independently a monovalent hydrocarbon group having 1 to 12 carbon atoms that does not contain an aliphatic unsaturated bond, and d is an integer of 5 to 2,000.

上述通式(3)中，R⁵ 獨立地為未被取代或已被取代的碳原子數1～12的不含脂肪族不飽和鍵的1價烴基。R⁵ 可舉例如：甲基、乙基、丙基、異丙基、丁基、異丁基、三級丁基、戊基、新戊基、己基、庚基、辛基、壬基、癸基、十二烷基等烷基；環戊基、環己基、環庚基等環烷基；苯基、甲苯基、二甲苯基、萘基、聯苯基等芳基；苯甲基、苯乙基、苯丙基、甲基苯甲基等芳烷基；及此等基的碳原子鍵結的氫原子的一部分或全部被氟、氯、溴等鹵素原子、氰基等所取代而成的基、例如氯甲基、2-溴乙基、3-氯丙基、3,3,3-三氟丙基、氯苯基、氟苯基、氰乙基、3,3,4,4,5,5,6,6,6-九氟己基等，代表性之物為碳原子數1～10的基，特別代表性之物為碳原子數1～6的基，較佳為：甲基、乙基、丙基、氯甲基、2-溴乙基、3,3,3-三氟丙基、氰乙基等碳原子數1～3的未被取代或已被取代的烷基；及苯基、氯苯基、氟苯基等未被取代或已被取代的苯基，特佳為甲基、苯基。In the above-mentioned general formula (3), R ⁵ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms that does not contain an aliphatic unsaturated bond. Examples of R ⁵ include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl alkyl, dodecyl and other alkyl groups; cyclopentyl, cyclohexyl, cycloheptyl and other cycloalkyl groups; phenyl, tolyl, xylyl, naphthyl, biphenyl and other aryl groups; benzyl, benzene and other Aralkyl groups such as ethyl, phenylpropyl, methylbenzyl, etc.; and some or all of the hydrogen atoms bonded to the carbon atoms of these groups are replaced by halogen atoms such as fluorine, chlorine, and bromine, cyano groups, etc. radicals such as chloromethyl, 2-bromoethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, chlorophenyl, fluorophenyl, cyanoethyl, 3,3,4,4 , 5,5,6,6,6-nonafluorohexyl, etc., the representative thing is a group with 1 to 10 carbon atoms, a particularly representative thing is a group with 1 to 6 carbon atoms, preferably: methyl Unsubstituted or substituted alkyl groups with 1 to 3 carbon atoms such as ethyl, ethyl, propyl, chloromethyl, 2-bromoethyl, 3,3,3-trifluoropropyl, cyanoethyl, etc. ; and unsubstituted or substituted phenyl groups such as phenyl, chlorophenyl, and fluorophenyl, particularly preferably methyl and phenyl.

上述通式(3)中，從所要求的黏度的觀點來看，d為5～2,000的整數，較佳為10～1,000的整數。In the above-mentioned general formula (3), from the viewpoint of the required viscosity, d is an integer of 5 to 2,000, preferably an integer of 10 to 1,000.

此外，(G)成分的23℃時的運動黏度為10～100,000 mm² /s，特佳為100～10,000 mm² /s。如果前述運動黏度低於10 mm² /s，則所得的組成物的硬化物容易發生油滲出。如果前述運動黏度大於100,000 mm² /s，則所得的導熱性矽氧組成物的柔軟性容易缺乏。Further, the kinematic viscosity at 23° C. of the component (G) is 10 to 100,000 mm ² /s, particularly preferably 100 to 10,000 mm ² /s. If the aforementioned kinematic viscosity is less than 10 mm ² /s, oil oozing is likely to occur in the hardened product of the obtained composition. When the aforementioned kinematic viscosity exceeds 100,000 mm ² /s, the resulting thermally conductive silicon-oxygen composition tends to lack flexibility.

當在本發明的導熱性矽氧組成物中添加(G)成分時，相對於(A)成分100質量份，為0.1～100質量份，較佳為1～50質量份。如果該添加量在此範圍外，則硬化前的導熱性矽氧組成物難以維持良好的流動性、工作性，並且難以將(C)成分的導熱性填充材料填充在該導熱性矽氧組成物中。When the (G) component is added to the thermally conductive silicon-oxygen composition of the present invention, it is 0.1 to 100 parts by mass, preferably 1 to 50 parts by mass, relative to 100 parts by mass of the (A) component. If the amount of addition is outside this range, it is difficult to maintain good fluidity and workability of the thermally conductive silicon-oxygen composition before curing, and it is difficult to fill the thermally-conductive silicon-oxygen composition with the thermally conductive filler of the component (C). middle.

[其它成分] 本發明的導熱性矽氧組成物中可因應本發明的目的來進一步調配其它成分。例如：氧化鐵、氧化鈰等耐熱性提高劑；氧化矽等黏度調整劑；著色劑；脫模劑等任意成分。[other ingredients] In the thermally conductive silicon-oxygen composition of the present invention, other components can be further formulated in accordance with the purpose of the present invention. For example: heat resistance improvers such as iron oxide and cerium oxide; viscosity modifiers such as silicon oxide; colorants; mold release agents and other arbitrary components.

[導熱性矽氧組成物的製造方法] 本發明的導熱性矽氧組成物能夠藉由下述方式來製造：依據慣用方法來將上述各成分均勻混合。較佳是至少包括一面將(A)、(C)、(F)成分加熱一面攪拌的步驟。如果為這樣的導熱性矽氧組成物的製造方法，則能夠減少在成型後的硬化物表面產生的氣泡。[Manufacturing method of thermally conductive silicon oxide composition] The thermally conductive silicon-oxygen composition of the present invention can be produced by uniformly mixing the above components according to a conventional method. It is preferable to include at least a step of stirring while heating the components (A), (C), and (F). According to the manufacturing method of such a thermally conductive silicon oxide composition, the generation of air bubbles on the surface of the cured product after molding can be reduced.

[組成物的絕對黏度] 本發明的導熱性矽氧組成物的絕對黏度較佳是：23℃時為800 Pa・s以下，更佳為700 Pa・s以下，並且較佳為80 Pa・s以上。如果絕對黏度為800 Pa・s以下，則不會損害成形性。再者，本發明中，此絕對黏度為在23℃時依據使用B型黏度計來測定的絕對黏度的值。[Absolute viscosity of composition] The absolute viscosity of the thermally conductive silicone oxide composition of the present invention is preferably 800 Pa·s or less at 23° C., more preferably 700 Pa·s or less, and preferably 80 Pa·s or more. If the absolute viscosity is 800 Pa·s or less, the formability will not be impaired. In addition, in this invention, this absolute viscosity is the value based on the absolute viscosity measured using a Brookfield viscometer at 23 degreeC.

[導熱性矽氧硬化物的製造方法] 將導熱性矽氧組成物成形的硬化條件與公知的加成反應硬化型矽氧橡膠組成物相同即可，例如即使在常溫也會充分硬化，也可因應需要來加熱。較佳是宜在100～120℃使其加成硬化8～12分鐘。這樣的導熱性矽氧硬化物的導熱性優異。[Manufacturing method of thermally conductive silica cured product] The curing conditions for molding the thermally conductive silicone composition may be the same as those of the known addition reaction curable silicone rubber composition. For example, it is sufficiently cured even at room temperature, and it may be heated as needed. It is preferable to make addition hardening at 100-120 degreeC for 8-12 minutes. Such a thermally conductive cured silicon oxide product is excellent in thermal conductivity.

[成形體的導熱率] 本發明中的成形體(導熱性矽氧硬化物)的導熱率是藉由熱圓盤法來測得的23℃時的測定值為6.5 W/m・K以上，特別是7.0 W/m・K以上，由於越高則越佳，故上限無法決定。能夠設為例如8.0 W/m・K以下。[Thermal conductivity of molded body] The thermal conductivity of the molded body (hardened thermally conductive silicon oxide) in the present invention is 6.5 W/m·K or more, particularly 7.0 W/m·K, as measured at 23° C. by the hot disc method K or more, since the higher the better, the upper limit cannot be determined. For example, it can be set to 8.0 W/m·K or less.

[成形體的絕緣破壞電壓] 本發明中的成形體的絕緣破壞電壓是依據JIS K 6249來測定1 mm厚的成形體的絕緣破壞電壓後的測定值為10 kV/mm以上，較佳為13 kV/mm以上，由於越高則越佳，故上限無法決定，能夠設為例如25 kV/mm以下。當為絕緣破壞電壓為10 kV/mm以上的薄片時，在使用時容易安定地確保絕緣。再者，這樣的絕緣破壞電壓能夠藉由調整填料的種類和純度來調整。[Dielectric breakdown voltage of molded body] The dielectric breakdown voltage of the molded body in the present invention is 10 kV/mm or more, preferably 13 kV/mm or more, after measuring the dielectric breakdown voltage of a 1 mm thick molded body in accordance with JIS K 6249. The better, the upper limit cannot be determined, but it can be set to, for example, 25 kV/mm or less. When it is a sheet with a breakdown voltage of 10 kV/mm or more, it is easy to ensure stable insulation during use. In addition, such a dielectric breakdown voltage can be adjusted by adjusting the kind and purity of a filler.

[成形體的硬度] 本發明中的成形體的硬度較佳是使用ASKER C硬度計來測得的23℃時的測定值為60以下，較佳為40以下，更佳為30以下，並且較佳為5以上。當硬度在此範圍內時，會以沿著被散熱體的形狀的方式變形，而容易在不對被散熱體施加應力的情形下顯示良好的散熱特性。再者，這樣的硬度能夠藉由改變(A)成分與(B)成分的比例來調整交聯密度來調整。 [實施例][Hardness of the formed body] The hardness of the formed body in the present invention is preferably 60 or less, preferably 40 or less, more preferably 30 or less, and preferably 5 or more, as measured at 23° C. using an Asker C hardness tester. When the hardness is within this range, it deforms so as to follow the shape of the body to be radiated, and it is easy to exhibit good heat dissipation properties without applying stress to the body to be radiated. In addition, such hardness can be adjusted by adjusting the crosslinking density by changing the ratio of (A) component and (B) component. [Example]

以下使用實施例及比較例來具體說明本發明，但本發明並不受此等所限定。再者，運動黏度是在23℃時使用奧氏黏度計來進行測定。此外，平均粒徑為使用日機裝股份有限公司製的粒度分析計也就是Microtrac MT3300EX來測得的體積基準的累積平均粒徑(中位徑)的值。Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition, the kinematic viscosity was measured at 23 degreeC using an Ostenso viscometer. In addition, the average particle diameter is the value of the cumulative average particle diameter (median diameter) based on the volume measured using Microtrac MT3300EX, which is a particle size analyzer manufactured by Nikkiso Co., Ltd.

下述實施例及比較例中所使用的(A)～(G)成分是如下所示。Components (A) to (G) used in the following Examples and Comparative Examples are as follows.

(A)成分： 下述式(5)表示的運動黏度為600 mm² /s的有機聚矽氧烷。

式(5)中，X為乙烯基，f為能夠獲得上述黏度的數。(A) Component: An organopolysiloxane having a kinematic viscosity of 600 mm ² /s represented by the following formula (5).

In formula (5), X is a vinyl group, and f is a number that can obtain the above-mentioned viscosity.

(B)成分： 下述式(6)表示的有機氫聚矽氧烷。

式(6)中，g為27，h為3。(B) component: Organohydrogen polysiloxane represented by following formula (6).

In formula (6), g is 27, and h is 3.

(C)成分： 平均粒徑是如下所述的球狀氧化鋁、非晶質氧化鋁。 (C-1)平均粒徑為98.8 μm的球狀氧化鋁 (C-2)平均粒徑為48.7 μm的球狀氧化鋁 (C-3)平均粒徑為16.7 μm的球狀氧化鋁 (C-4)平均粒徑為1.7 μm的非晶質氧化鋁(C) Ingredient: The average particle size is spherical alumina and amorphous alumina as described below. (C-1) Spherical alumina with an average particle size of 98.8 μm (C-2) Spherical alumina with an average particle size of 48.7 μm (C-3) Spherical alumina with an average particle size of 16.7 μm (C-4) Amorphous alumina with an average particle size of 1.7 μm

(D)成分： 5質量％氯鉑酸2-乙基己醇溶液。(D) Ingredient: 5 mass % chloroplatinic acid 2-ethylhexanol solution.

(E)成分： 作為加成反應控制材料的乙炔基亞甲基甲醇。(E) Ingredient: Ethynylmethylene methanol as an addition reaction control material.

(F)成分：(F-2)成分 下述式(7)表示的平均聚合度30的單末端已被三甲氧基矽烷基所封閉的二甲基聚矽氧烷。

(F) Component: (F-2) Component dimethylpolysiloxane having an average degree of polymerization of 30 represented by the following formula (7) and having an average degree of polymerization of 30 at one end blocked by a trimethoxysilyl group.

(G)成分： 作為黏度調整劑的下述式(8)表示的運動黏度為100 mm² /s的二甲基聚矽氧烷。

式(8)中，j為80。(G) Component: A dimethylpolysiloxane having a kinematic viscosity of 100 mm ² /s represented by the following formula (8) as a viscosity modifier.

In formula (8), j is 80.

[實施例1～4、比較例1] 實施例1～4及比較例1中，使用下述表1表示的既定量的上述(A)～(G)成分來以下述方式調製組成物，並使其成形硬化後，依照下述方法來測定或觀察組成物的絕對黏度、硬化物的導熱率、硬度、絕緣破壞電壓、比重、及硬化物表面的氣泡。結果一併記載於表1。[Examples 1 to 4, Comparative Example 1] In Examples 1 to 4 and Comparative Example 1, the compositions were prepared in the following manner using predetermined amounts of the above-mentioned (A) to (G) components shown in Table 1 below, and after forming and curing them, the compositions were prepared according to the following method. Measure or observe the absolute viscosity of the composition, thermal conductivity, hardness, dielectric breakdown voltage, specific gravity, and air bubbles on the surface of the cured product. The results are shown in Table 1 together.

[組成物的調製] 以下述表1的實施例1～4及比較例1表示的既定量來加入(A)、(C)、(F)成分，並使用行星式攪拌機來揉合30分鐘後，實施例1～3及比較例1加熱揉合60分鐘，實施例4在不加熱的情形下揉合60分鐘。充分冷卻後，在其中以下述表1的實施例1～4及比較例1表示的既定量來加入(D)成分及(G)成分，進一步加入有效量的作為用以促進與間隔物之間的脫模的內添脫模劑的信越化學公司製的已被苯基改質的矽氧油也就是KF-54，並揉合30分鐘。 在其中進一步以下述表1的實施例1～4及比較例1表示的既定量來加入(B)、(E)成分，並揉合30分鐘，而獲得組成物。[Preparation of composition] The components (A), (C), and (F) were added in predetermined amounts shown in Examples 1 to 4 and Comparative Example 1 in the following Table 1, and kneaded for 30 minutes using a planetary mixer. Examples 1 to 3 And Comparative Example 1 was heated and kneaded for 60 minutes, and Example 4 was kneaded for 60 minutes without heating. After being sufficiently cooled, components (D) and (G) were added in the predetermined amounts shown in Examples 1 to 4 and Comparative Example 1 in the following Table 1, and an effective amount was further added as an effective amount to promote the space between the two. The release agent of Shin-Etsu Chemical Co., Ltd. has been modified with phenyl-modified silicone oil, that is, KF-54, and kneaded for 30 minutes. Further, the components (B) and (E) were added in predetermined amounts shown in Examples 1 to 4 and Comparative Example 1 in the following Table 1, and kneaded for 30 minutes to obtain a composition.

[成形方法] 使實施例1～4及比較例1中所得的組成物流入60 mm×60 mm×6 mm的模具中，並使用加壓成形機來在120℃成形硬化10分鐘。[forming method] The compositions obtained in Examples 1 to 4 and Comparative Example 1 were poured into a mold of 60 mm×60 mm×6 mm, and molded and hardened at 120° C. for 10 minutes using a press molding machine.

[評估方法] 組成物的絕對黏度： 使用B型黏度計來在23℃環境中測定實施例1～4及比較例1中所得的組成物的絕對黏度。[assessment method] Absolute viscosity of the composition: The absolute viscosity of the compositions obtained in Examples 1 to 4 and Comparative Example 1 was measured in a 23°C environment using a Brookfield viscometer.

導熱率： 使用加壓成型機來在120℃10分鐘的條件下使實施例1～4及比較例1中所得的組成物硬化成6 mm厚的薄片狀後，使用2片該薄片，使用導熱率計(商品名：TPS-2500S，京都電子工業股份有限公司製)來測定該薄片的導熱率。Thermal conductivity: After curing the compositions obtained in Examples 1 to 4 and Comparative Example 1 into sheets having a thickness of 6 mm at 120° C. for 10 minutes using a press molding machine, two sheets of the sheets were used, and a thermal conductivity meter ( Trade name: TPS-2500S, manufactured by Kyoto Electronics Industry Co., Ltd.) to measure the thermal conductivity of the sheet.

硬度： 使實施例1～4及比較例1中所得的組成物與上述同樣地硬化成6 mm厚的薄片狀後，將該薄片重疊2片，並使用ASKER C硬度計來進行測定。hardness: The compositions obtained in Examples 1 to 4 and Comparative Example 1 were cured into sheets having a thickness of 6 mm in the same manner as described above, and then the sheets were stacked on two sheets and measured using an ASKER C hardness tester.

絕緣破壞電壓： 使用加壓成型機來在120℃10分鐘的條件下使實施例1～4及比較例1中所得的組成物硬化成1 mm厚的薄片狀後，依據JIS K 6249來測定絕緣破壞電壓。Dielectric breakdown voltage: After curing the compositions obtained in Examples 1 to 4 and Comparative Example 1 into sheets having a thickness of 1 mm under the condition of 120° C. for 10 minutes using a press molding machine, the dielectric breakdown voltage was measured according to JIS K 6249.

比重： 使用加壓成型機來在120℃10分鐘的條件下使實施例1～4及比較例1中所得的組成物硬化成1 mm厚的薄片狀後，使用水中置換法來測定硬化物的比重。proportion: The compositions obtained in Examples 1 to 4 and Comparative Example 1 were cured into 1 mm-thick sheets at 120° C. for 10 minutes using a press molding machine, and then the specific gravity of the cured products was measured using a water displacement method.

硬化物表面的氣泡： 使用加壓成型機來在120℃10分鐘的條件下使實施例1～4及比較例1中所得的組成物硬化成2 mm厚的薄片狀後，觀察硬化物表面有無氣泡。Air bubbles on hardened surface: The compositions obtained in Examples 1 to 4 and Comparative Example 1 were cured into 2 mm thick sheets using a press molding machine at 120° C. for 10 minutes, and then the presence or absence of air bubbles on the surfaces of the cured products was observed.

[表1]

[Table 1]

如果像比較例1這樣導熱性填充材料的總質量份超過9,000質量份，則組成物的潤濕性不足，而無法獲得膏狀的均勻的組成物。When the total mass part of the thermally conductive filler exceeds 9,000 parts by mass as in Comparative Example 1, the wettability of the composition is insufficient, and a paste-like uniform composition cannot be obtained.

像實施例這樣相對於(A)成分100質量份，(C)成分的調配量在7,200～9,000質量份的範圍內，且(C)成分是由下述(C-1)～(C-4)成分所組成，而組成物的絕緣黏度、硬化物的導熱率、硬度、比重、絕緣破壞電壓皆為良好的結果，特別是在組成物的調製中，實施例1～3在攪拌中進行加熱處理，而在成型後的硬化物的表面無法觀察到氣泡。 (C-1)平均粒徑為超過75 μm且125 μm以下的球狀氧化鋁填料2,250～4,000質量份； (C-2)平均粒徑為超過35 μm且65 μm以下的球狀氧化鋁填料900～2,700質量份； (C-3)平均粒徑為超過5 μm且25 μm以下的球狀氧化鋁填料450～1,500質量份； (C-4)平均粒徑為超過0.4 μm且4 μm以下的非晶質氧化鋁填料1,600～2,500質量份。The compounding amount of (C) component is in the range of 7,200 to 9,000 parts by mass with respect to 100 parts by mass of (A) component as in the examples, and (C) component is composed of the following (C-1) to (C-4 ) components, and the insulating viscosity of the composition, the thermal conductivity of the cured product, hardness, specific gravity, and dielectric breakdown voltage are all good results, especially in the preparation of the composition, Examples 1 to 3 are heated during stirring However, no air bubbles were observed on the surface of the molded cured product. (C-1) 2,250 to 4,000 parts by mass of spherical alumina fillers with an average particle size exceeding 75 μm and 125 μm or less; (C-2) 900 to 2,700 parts by mass of spherical alumina fillers having an average particle size of more than 35 μm and 65 μm or less; (C-3) 450 to 1,500 parts by mass of spherical alumina fillers with an average particle size exceeding 5 μm and 25 μm or less; (C-4) 1,600 to 2,500 parts by mass of the amorphous alumina filler having an average particle diameter of more than 0.4 μm and 4 μm or less.

再者，本發明並不受上述實施形態所限定。上述實施形態只是例示，只要具有與本發明的申請專利範圍中所記載的技術思想實質上相同的構成且產生相同的作用效果，無論是何種，都包含在本發明的技術範圍內。In addition, this invention is not limited to the said embodiment. The above-described embodiment is merely an example, and any form is included in the technical scope of the present invention as long as it has substantially the same configuration and produces the same effect as the technical idea described in the scope of the claims of the present invention.

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Claims (10)

一種導熱性矽氧組成物，其特徵在於包含： (A)1分子中具有至少2個烯基的有機聚矽氧烷：100質量份； (B)具有至少2個與矽原子直接鍵結的氫原子的有機氫聚矽氧烷：與矽原子直接鍵結的氫原子的mol數成為源自(A)成分的烯基的mol數的0.1～5.0倍量的量； (C)由下述(C-1)～(C-4)成分所組成的導熱性填充材料：7,200～9,000質量份： (C-1)平均粒徑為超過75 μm且125 μm以下的球狀氧化鋁填料：2,250～4,000質量份； (C-2)平均粒徑為超過35 μm且65 μm以下的球狀氧化鋁填料：900～2,700質量份； (C-3)平均粒徑為超過5 μm且25 μm以下的球狀氧化鋁填料：450～1,500質量份； (C-4)平均粒徑為超過0.4 μm且4 μm以下的非晶質氧化鋁填料：1,600～2,500質量份； (D)鉑族金屬系硬化觸媒：相對於(A)成分以鉑族金屬系元素質量來換算為0.1～2,000 ppm； (E)加成反應控制材料：0.01～1質量份； (F)從由(F-1)下述通式(1)表示的烷氧基矽烷化合物及下述通式(2)表示的分子鏈單末端已被三烷氧基矽烷基所封閉的二甲基聚矽氧烷所組成的群組中選出的至少1種：0.01～300質量份

式(1)中，R¹ 獨立地為碳原子數6～15的烷基，R² 獨立地為未被取代或已被取代的碳原子數1～12的1價烴基，R³ 獨立地為碳原子數1～6的烷基，a為1～3的整數，b為0～2的整數，但是a＋b為1～3的整數；

式(2)中，R⁴ 獨立地為碳原子數1～6的烷基，c為5～100的整數； (G)下述通式(3)表示的23℃時的運動黏度為10～100,000 mm² /s的有機聚矽氧烷：0.1～100質量份

式(3)中，R⁵ 獨立地為碳原子數1～12的不含脂肪族不飽和鍵的1價烴基，d為5～2,000的整數。A thermally conductive silicon-oxygen composition, characterized by comprising: (A) an organopolysiloxane having at least 2 alkenyl groups in 1 molecule: 100 parts by mass; (B) having at least 2 organic polysiloxanes directly bonded to silicon atoms Organohydrogen polysiloxane of hydrogen atom: the amount in which the number of moles of hydrogen atoms directly bonded to the silicon atom is 0.1 to 5.0 times the number of moles of the alkenyl group derived from the component (A); (C) by the following Thermally conductive fillers composed of components (C-1) to (C-4): 7,200 to 9,000 parts by mass: (C-1) Spherical alumina fillers having an average particle size of more than 75 μm and 125 μm or less: 2,250 ~4,000 parts by mass; (C-2) Spherical alumina fillers with an average particle size of more than 35 μm and 65 μm or less: 900 to 2,700 parts by mass; (C-3) Average particle size of more than 5 μm and 25 μm or less Spherical alumina filler: 450 to 1,500 parts by mass; (C-4) Amorphous alumina filler with an average particle diameter of more than 0.4 μm and 4 μm or less: 1,600 to 2,500 parts by mass; (D) Platinum group metal Hardening catalyst: 0.1 to 2,000 ppm in terms of platinum group metal element mass relative to (A) component; (E) Addition reaction control material: 0.01 to 1 part by mass; (F) From (F-1) A group consisting of an alkoxysilane compound represented by the following general formula (1) and a dimethylpolysiloxane having a single terminal of the molecular chain represented by the following general formula (2) blocked with a trialkoxysilyl group At least 1 type selected from the group: 0.01 to 300 parts by mass

In formula (1), R ¹ is independently an alkyl group having 6 to 15 carbon atoms, R ² is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and R ³ is independently For an alkyl group having 1 to 6 carbon atoms, a is an integer of 1 to 3, b is an integer of 0 to 2, but a+b is an integer of 1 to 3;

In formula (2), R ⁴ is independently an alkyl group having 1 to 6 carbon atoms, and c is an integer of 5 to 100; (G) The kinematic viscosity at 23° C. represented by the following general formula (3) is 10 to 10 100,000 mm ² /s organopolysiloxane: 0.1 to 100 parts by mass

In formula (3), R ⁵ is independently a monovalent hydrocarbon group having 1 to 12 carbon atoms that does not contain an aliphatic unsaturated bond, and d is an integer of 5 to 2,000. 如請求項1所述的導熱性矽氧組成物，其23℃時的絕對黏度為800 Pa・s以下。The thermally conductive silicon-oxygen composition according to claim 1, wherein the absolute viscosity at 23°C is 800 Pa·s or less. 一種導熱性矽氧硬化物，其特徵在於：是使請求項1所述的導熱性矽氧組成物硬化而成。A thermally conductive silicon-oxygen cured product, characterized in that it is obtained by curing the thermally-conductive silicon-oxygen composition according to claim 1. 一種導熱性矽氧硬化物，其特徵在於：是使請求項2所述的導熱性矽氧組成物硬化而成。A thermally conductive silicon-oxygen cured product, characterized in that it is obtained by curing the thermally-conductive silicon-oxygen composition described in claim 2. 如請求項3所述的導熱性矽氧硬化物，其導熱率為6.5 W/m・K以上。The thermally conductive cured silicon oxide according to claim 3, having a thermal conductivity of 6.5 W/m·K or more. 如請求項4所述的導熱性矽氧硬化物，其導熱率為6.5 W/m・K以上。The thermally conductive cured silicon oxide according to claim 4, having a thermal conductivity of 6.5 W/m·K or more. 如請求項3至6中任一項所述的導熱性矽氧硬化物，其硬度是以ASKER C硬度計計為60以下。The thermally conductive silicon oxide cured product according to any one of Claims 3 to 6, which has a hardness of 60 or less in terms of ASKER C hardness. 如請求項3至6中任一項所述的導熱性矽氧硬化物，其絕緣破壞電壓為10 kV/mm以上。The thermally conductive cured silicon oxide according to any one of claims 3 to 6, which has a dielectric breakdown voltage of 10 kV/mm or more. 如請求項7所述的導熱性矽氧硬化物，其絕緣破壞電壓為10 kV/mm以上。The thermally conductive silicon oxide cured product according to claim 7, which has a dielectric breakdown voltage of 10 kV/mm or more. 一種導熱性矽氧組成物的製造方法，其特徵在於：為製造請求項1或2所述的導熱性矽氧組成物的方法，並且至少具有一面將前述(A)、(C)、(F)成分加熱一面攪拌的步驟。A method for producing a thermally conductive silicon-oxygen composition, characterized in that: it is a method for producing the thermally-conductive silicon-oxygen composition according to claim 1 or 2, and has at least one side of the above-mentioned (A), (C), (F) ) the step of stirring the ingredients while heating.