TWI635169B - Thermally conductive composite sheet - Google Patents
Thermally conductive composite sheet Download PDFInfo
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- TWI635169B TWI635169B TW103139558A TW103139558A TWI635169B TW I635169 B TWI635169 B TW I635169B TW 103139558 A TW103139558 A TW 103139558A TW 103139558 A TW103139558 A TW 103139558A TW I635169 B TWI635169 B TW I635169B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F3/00—Plate-like or laminated elements; Assemblies of plate-like or laminated elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/302—Conductive
Abstract
本發明的熱傳導性複合薄片為富有柔軟性、安裝步驟為簡便，係可追隨發熱體之表面形狀者，藉由將此貼附於發熱體，對於發熱體之降溫非常地有效。 The thermally conductive composite sheet of the present invention is flexible and easy to install, and can follow the surface shape of the heating element. By attaching this to the heating element, it is very effective in reducing the temperature of the heating element.
解決課題之手段，本發明的熱傳導性複合薄片，其係於熱傳導層之一面層合熱放射層，並於另一面層合熱傳導性聚矽氧樹脂層而成，其中，前述熱傳導層，係面方向之熱傳導率為200W/mK以上，前述熱放射層，係厚度10μm以上100μm以下，前述熱傳導性聚矽氧樹脂層，係厚度為0.2mm以上，以阿斯克C(Asker C)之硬度為40以下。 Means for solving the problem, the thermally conductive composite sheet of the present invention is formed by laminating a heat radiation layer on one surface of a heat conductive layer and a heat conductive polysiloxane resin layer on the other surface, wherein the heat conductive layer and the surface are The thermal conductivity in the direction is 200 W / mK or more. The thermal radiation layer has a thickness of 10 μm to 100 μm. The thermally conductive silicone layer has a thickness of 0.2 mm or more. The hardness of Asker C is 40. the following.
Description
本發明為關於一熱傳導性複合薄片，其係適合安裝於無法使用散熱體(heat sink)等的冷卻構件的電子機器等。 The present invention relates to a thermally conductive composite sheet, which is suitable for mounting on an electronic device or the like which cannot use a cooling member such as a heat sink.
隨著電視、電腦、通信裝置、產業機器等的電子機器之小型化、薄型化、高性能化，搭載於該等的CPU、驅動IC等的晶片之發熱量增加。晶片之溫度上昇會引起晶片之作動不良、破壞。因此，為了抑制作動中的晶片之溫度上昇，已提案有許多的散熱方法及用於該等散熱方法之散熱構件。已往，在電子機器等中，為了抑制作動中的晶片之溫度上昇，係使用了利用鋁或銅等熱傳導率高的金屬板之散熱體(heat sink)。該散熱體為傳導該晶片所產生的熱量，並藉由與外部空氣的溫度差而將該熱量由表面釋放。 With the miniaturization, thinness, and high performance of electronic devices such as televisions, computers, communication devices, and industrial equipment, the amount of heat generated by chips mounted on such CPUs and driver ICs has increased. An increase in the temperature of a wafer may cause malfunction or damage of the wafer. Therefore, in order to suppress the temperature rise of the active wafer, many heat radiation methods and heat radiation members used for these heat radiation methods have been proposed. In the past, in electronic equipment and the like, in order to suppress the temperature rise of a moving wafer, a heat sink using a metal plate having a high thermal conductivity such as aluminum or copper is used. The heat sink conducts the heat generated by the chip, and releases the heat from the surface through the temperature difference from the outside air.
為了將由晶片所產生的熱量效率良好地傳遞至散熱體，需要使散熱體密接於晶片上，但由於具有各晶片的高度的差異或組裝加工所導致的公差，因而將具有柔 軟性的薄片或導熱膏(grease)設置於晶片與散熱體之間，透過此薄片或導熱膏來實現自晶片往散熱體的熱傳導。 In order to efficiently transfer the heat generated by the wafer to the heat sink, the heat sink needs to be in close contact with the wafer. However, due to the difference in the height of each wafer or the tolerance caused by the assembly process, it will have a flexible A soft sheet or thermal paste is disposed between the chip and the heat sink, and the heat conduction from the chip to the heat sink is achieved through the sheet or the heat paste.
但，如上述般因機器之小型化、薄型化、高性能化所導致的無法搭載散熱體之情形為漸增。例如，以攜帶為假設前提的智慧型手機或數位攝影機；以設置於天花板、或由天花板垂掛為假設前提的LED照明等，由於大小或重量問題而無法使用散熱體，或要求將散熱體除去。基於如此般之情事，已有幾個利用熱放射的散熱對策零件被報告著。 However, as described above, there are increasing cases in which heat sinks cannot be mounted due to the miniaturization, thinning, and high performance of the equipment. For example, a smartphone or a digital video camera with the assumption of carrying; LED lighting with the assumption of being installed on the ceiling or hanging from the ceiling cannot be used due to size or weight issues, or the heat sink must be removed. Based on such circumstances, several heat radiation countermeasure parts using heat radiation have been reported.
〔專利文獻1〕日本特開2006-298703號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2006-298703
〔專利文獻2〕日本特開2004-43612號公報 [Patent Document 2] Japanese Patent Laid-Open No. 2004-43612
〔專利文獻3〕日本特開2013-144747號公報 [Patent Document 3] Japanese Patent Laid-Open No. 2013-144747
〔專利文獻4〕日本特開2004-200199號公報 [Patent Document 4] Japanese Patent Laid-Open No. 2004-200199
已提案有一種散熱方法，其係將紅外線散熱率為高的菫青石(cordierite)粉粒體燒成，並將所得到的陶瓷材料成型，藉由使用作為基板、或使用來取代散熱體，使來自發熱體的熱量以作為輻射熱而散熱(專利文獻 1：日本特開2006-298703號公報)。但，此陶瓷材料之剛性高而難以成型，或安置的發熱零件之表面不為平面而如彎曲般之情形時，則具有無法安置之問題。 A heat dissipation method has been proposed, which consists of firing cordierite powder and granules with a high infrared radiation rate, and molding the obtained ceramic material, and using it as a substrate or instead of a heat sink, The heat from the heating element is dissipated as radiant heat (Patent Literature 1: Japanese Patent Application Laid-Open No. 2006-298703). However, when the ceramic material has high rigidity and is difficult to be molded, or when the surface of the heat-generating component to be placed is not flat and curved, it has a problem that it cannot be placed.
其他方面，已提案有一種散熱手法，其係將硬化性樹脂中為含有熱放射率高的粒子的組成物以適當有機溶劑稀釋(被稱為熱放射塗料)，將其塗布或噴塗於發熱體並使乾燥、硬化，使熱放射層直接層合至發熱體，使來自發熱體的熱量散熱至系外(專利文獻2、3：日本特開2004-43612號公報、日本特開2013-144747號公報)。但，對於發熱體之塗布或噴塗，可舉例如：必須導入用於此之設備；塗布量、噴塗量之管理困難；必須具有使塗料硬化之步驟等，而具有所謂步驟變複雜之缺點。 In other respects, a heat dissipation method has been proposed, which is a method of diluting a composition containing particles with high thermal emissivity in a curable resin with an appropriate organic solvent (called a thermal radiation coating) and coating or spraying it on a heating element Drying and hardening, the heat radiation layer is directly laminated to the heating element, and the heat from the heating element is dissipated outside the system (Patent Documents 2 and 3: Japanese Patent Application Laid-Open No. 2004-43612, Japanese Patent Application Laid-Open No. 2013-144747 Bulletin). However, for the coating or spraying of the heating element, for example: the equipment used for this must be introduced; the management of the coating amount and the spraying amount is difficult; the step of hardening the coating must be provided;
又，已提案有一種熱放射薄片，其係於金屬薄板之一面形成熱放射膜，並於金屬薄板之另一面貼合接著層(專利文獻4：日本特開2004-200199號公報)。但，此接著層之厚度為薄，又，熱傳導率為低。發熱體表面之平滑性為高時雖不成問題，但發熱體表面為粗糙時，或發熱體具有複數且分別的高度為相異時，則無法順利地追隨發熱體表面，又，接著層之熱傳導率為低時，不利於熱量之傳達至熱放射層，而散熱效果會顯著下降。 In addition, a heat radiation sheet has been proposed which forms a heat radiation film on one surface of a metal thin plate and attaches an adhesive layer to the other surface of the metal thin plate (Patent Document 4: Japanese Patent Application Laid-Open No. 2004-200199). However, the thickness of this adhesive layer is thin and the thermal conductivity is low. When the smoothness of the surface of the heating element is high, it is not a problem, but when the surface of the heating element is rough, or when the heating element has a plurality of different heights, the surface of the heating element cannot be smoothly followed, and the heat conduction of the subsequent layer When the rate is low, it is not conducive to the transmission of heat to the heat radiation layer, and the heat dissipation effect will be significantly reduced.
本發明為有鑑於上述情事之發明，以提供富有柔軟性、安裝步驟為簡便，並可追隨發熱體之表面形狀之熱傳導性複合薄片為目的。 The present invention has been made in view of the foregoing circumstances, and aims to provide a thermally conductive composite sheet that is flexible and easy to install, and can follow the surface shape of a heating element.
本發明人們為了達成上述目的經深入研究檢討之結果發現，藉由於面方向之熱傳導率為高的熱傳導層之一面層合厚度為10μm以上100μm以下的熱放射層，並於另一面層合厚度為0.2mm以上，以阿斯克C(Asker C)之硬度為40以下的熱傳導性聚矽氧樹脂層，可得到富有柔軟性、安裝步驟為簡便，並可追隨發熱體之表面形狀之熱傳導性複合薄片，遂而完成本發明。 In order to achieve the above object, the inventors have conducted in-depth research and review. As a result, it is found that one of the thermally conductive layers having a high thermal conductivity in the plane direction is laminated with a heat radiation layer having a thickness of 10 μm or more and 100 μm or less, and is laminated on the other surface with a thickness of Above 0.2mm, a thermally conductive polysiloxane resin layer with an Asker C hardness of 40 or less can obtain a thermally conductive composite sheet with rich flexibility, easy installation steps, and following the surface shape of the heating element Then, the present invention has been completed.
因此，本發明為提供下述熱傳導性複合薄片。 Therefore, the present invention provides the following thermally conductive composite sheet.
[1].一種熱傳導性複合薄片，其係於熱傳導層之一面層合熱放射層，並於另一面層合熱傳導性聚矽氧樹脂層而成，其中，前述熱傳導層，係面方向之熱傳導率為200W/mK以上，前述熱放射層，係厚度10μm以上100μm以下，前述熱傳導性聚矽氧樹脂層，係厚度為0.2mm以上，以阿斯克C(Asker C)之硬度為40以下。 [1]. A thermally conductive composite sheet, which is formed by laminating a heat radiation layer on one side of a heat conductive layer and a heat conductive polysiloxane resin layer on the other side, wherein the aforementioned heat conductive layer is the heat conduction in the plane direction. The rate is 200 W / mK or more. The thermal radiation layer has a thickness of 10 μm to 100 μm. The thermally conductive silicone layer has a thickness of 0.2 mm or more. The hardness of Asker C is 40 or less.
[2].如前述[1]之熱傳導性複合薄片，其中，熱傳導性聚矽氧樹脂層，係含有(a)~(d)成分而成的熱傳導性聚矽氧組成物之硬化物，(a)以下述平均組成式(1)所示並於一分子中具有2個以上鍵結於矽原子之烯基之有機聚矽氧烷：100質量份， RaSiO(4-a)/2 (1)(式中，R獨立為碳原子數1~12之非取代或取代之一價烴基，a為1.8~2.2之正數)；(b)熱傳導性填充劑：200~4,000質量份；(c)一分子中具有2個以上鍵結於矽原子之氫原子之有機氫聚矽氧烷：相對於(a)成分中之烯基，(c)成分中直接鍵結於矽原子之氫原子之莫耳比為0.5~5.0之量；(d)鉑系化合物：以鉑系元素量為(a)成分的0.1~1,000ppm。 [2]. The thermally conductive composite sheet according to the aforementioned [1], wherein the thermally conductive polysiloxane resin layer is a hardened material of a thermally conductive polysiloxane composition containing (a) to (d), ( a) Organic polysiloxane represented by the following average composition formula (1) and having at least two alkenyl groups bonded to silicon atoms in one molecule: 100 parts by mass, R a SiO (4-a) / 2 (1) (In the formula, R is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, a is a positive number of 1.8 to 2.2); (b) a thermally conductive filler: 200 to 4,000 parts by mass; ( c) Organic hydrogen polysiloxanes having more than two hydrogen atoms bonded to silicon atoms in one molecule: Compared to alkenyl groups in (a) component, hydrogen atoms directly bonded to silicon atom in (c) component The molar ratio is from 0.5 to 5.0; (d) Platinum-based compounds: The amount of platinum-based elements is 0.1 to 1,000 ppm of the component (a).
[3].如前述[2]之熱傳導性複合薄片，其中，熱傳導性聚矽氧組成物進而包含(f)聚矽氧樹脂：50~500質量份。 [3]. The thermally conductive composite sheet according to the aforementioned [2], wherein the thermally conductive polysiloxane composition further comprises (f) a polysiloxane resin: 50 to 500 parts by mass.
[4].如前述[3]之熱傳導性複合薄片，其中，聚矽氧樹脂(f)為R1 3SiO1/2單位(R1表示非取代或取代之一價烴基)(M單位)與SiO4/2單位(Q單位)之共聚物，且M單位與Q單位之比(M/Q)以莫耳比為0.5~1.5，不含有脂肪族不飽和基。 [4]. The thermally conductive composite sheet according to the aforementioned [3], wherein the silicone resin (f) is R 1 3 SiO 1/2 units (R 1 represents an unsubstituted or substituted monovalent hydrocarbon group) (M units) It is a copolymer with SiO 4/2 units (Q units), and the ratio of M units to Q units (M / Q) is 0.5 to 1.5 in a molar ratio, and does not contain aliphatic unsaturated groups.
[5].如前述[1]之熱傳導性複合薄片，其中，熱傳導性聚矽氧樹脂層，係含有(b)、(f)、(g)成分而成的熱傳導性聚矽氧組成物之硬化物，(b)熱傳導性填充劑：100~3,000質量份；(f)聚矽氧樹脂：100質量份；(g)有機過氧化物系化合物：以有機過氧化物換算 為0.1~2質量份。 [5]. The thermally conductive composite sheet according to the aforementioned [1], wherein the thermally conductive polysiloxane resin layer is a thermally conductive polysiloxane composition containing components (b), (f), and (g). Hardened material, (b) thermally conductive filler: 100 to 3,000 parts by mass; (f) polysiloxane resin: 100 parts by mass; (g) organic peroxide-based compound: organic peroxide conversion It is 0.1 to 2 parts by mass.
[6].如前述[5]之熱傳導性複合薄片，其中，聚矽氧樹脂(f)為R1 3SiO1/2單位(R1表示非取代或取代之一價烴基)(M單位)與SiO4/2單位(Q單位)之共聚物，且M單位與Q單位之比(M/Q)以莫耳比為0.5~1.5，不含有脂肪族不飽和基。 [6]. The thermally conductive composite sheet according to the aforementioned [5], wherein the polysiloxane resin (f) is R 1 3 SiO 1/2 units (R 1 represents an unsubstituted or substituted monovalent hydrocarbon group) (M units) It is a copolymer with SiO 4/2 units (Q units), and the ratio of M units to Q units (M / Q) is 0.5 to 1.5 in a molar ratio, and does not contain aliphatic unsaturated groups.
[7].如前述[2]~[6]中任一項之熱傳導性複合薄片，其中，(b)熱傳導性填充劑之平均粒徑為0.1~200μm。 [7]. The thermally conductive composite sheet according to any one of [2] to [6] above, wherein (b) the average particle diameter of the thermally conductive filler is 0.1 to 200 μm.
[8].如前述[2]~[6]中任一項之熱傳導性複合薄片，其中，熱傳導性聚矽氧組成物進而包含選自(h-1)及(h-2)成分之表面處理劑，(h-1)：以下述一般式(2)所表示之烷氧基矽烷化合物，R2 mR3 nSi(OR4)4-m-n (2)(式中，R2獨立為碳原子數6~15之烷基，R3獨立為非取代或取代之碳原子數1~8之一價烴基，R4獨立為碳原子數1~6之烷基，m為1~3之整數，n為0、1或2，m+n為1~3之整數)；(h-2)：以下述一般式(3)所表示並將分子鏈單末端以三烷氧基矽烷基封端之二甲基聚矽氧烷，
[9].如前述[1]之熱傳導性複合薄片，其中，熱傳導性聚矽氧樹脂層之熱傳導率為1.4W/mK以上。 [9]. The thermally conductive composite sheet according to the aforementioned [1], wherein the thermal conductivity of the thermally conductive polysiloxane resin layer is 1.4 W / mK or more.
[10].如前述[1]之熱傳導性複合薄片，其中，熱傳導層為鋁箔。 [10]. The thermally conductive composite sheet according to the aforementioned [1], wherein the thermally conductive layer is an aluminum foil.
[11].如前述[1]之熱傳導性複合薄片，其中，熱傳導層為銅箔。 [11]. The thermally conductive composite sheet according to the aforementioned [1], wherein the thermally conductive layer is a copper foil.
[12].如前述[1]之熱傳導性複合薄片，其中，熱放射層之熱放射率為0.80以上。 [12]. The thermally conductive composite sheet according to the aforementioned [1], wherein the thermal emissivity of the thermal radiation layer is 0.80 or more.
[13].如前述[1]之熱傳導性複合薄片，其中，熱放射層係由包含選自陶瓷粉、菫青石粉及黑鉛之粒子之有機樹脂層所成。 [13]. The thermally conductive composite sheet according to the aforementioned [1], wherein the heat radiation layer is made of an organic resin layer containing particles selected from the group consisting of ceramic powder, vermiculite powder, and black lead.
[14].如前述[13]之熱傳導性複合薄片，其中，上述粒子之平均粒徑為0.1~50μm。 [14]. The thermally conductive composite sheet according to the aforementioned [13], wherein the average particle diameter of the particles is 0.1 to 50 μm.
藉由本發明的熱傳導性複合薄片，其係於熱傳導層之一面層合熱放射層，並於另一面層合熱傳導性聚矽氧樹脂層而成，其中，前述熱傳導層，係面方向之熱傳導率為200W/mK以上，前述熱放射層，係厚度10μm以上100μm以下，前述熱傳導性聚矽氧樹脂層，係厚度為0.2mm以上，以阿斯克C(Asker C)之硬度為40以下，可得到富有柔軟性、安裝步驟為簡便，並可追隨發熱體之表面形狀之熱傳導性複合薄片，將此貼附於發熱體，可非 常有效地降低發熱體之溫度。 The heat conductive composite sheet of the present invention is formed by laminating a heat radiation layer on one surface of the heat conductive layer and a heat conductive polysiloxane resin layer on the other surface, wherein the aforementioned heat conductive layer has a thermal conductivity in a plane direction. It is 200 W / mK or more. The thermal radiation layer has a thickness of 10 μm or more and 100 μm or less. The thermally conductive polysiloxane resin layer has a thickness of 0.2 mm or more. The hardness of Asker C is 40 or less. A thermally conductive composite sheet that is rich in flexibility and easy to install, and can follow the surface shape of the heating element. Often effective in reducing the temperature of the heating element.
本發明的熱傳導性複合薄片中，熱傳導層之面方向之熱傳導率為200W/mK以上，較佳為200~2,000W/mK。當熱傳導層之面方向之熱傳導率低時，本發明的熱傳導性複合薄片無法得到充分的熱擴散性。於考慮使用熱放射的散熱對策時，所散熱的熱量會依附於面積及熱放射率。因此，薄片之面積，於安裝上為不成問題之範圍內，以越大者越有利。此時，熱傳導層可有效率地迅速將來自發熱體的熱量予以散熱。不具有熱傳導層時，來自發熱體的熱量不易擴散，因而無法發揮使薄片面積變大之優點。尚，本發明中，熱傳導層之面方向之熱傳導率為藉由熱波(thermo wave)分析儀來測定熱擴散率，可由熱擴散率計算出熱傳導率來進行測定。 In the thermally conductive composite sheet of the present invention, the thermal conductivity in the plane direction of the thermally conductive layer is 200 W / mK or more, and preferably 200 to 2,000 W / mK. When the thermal conductivity in the surface direction of the heat conductive layer is low, the heat conductive composite sheet of the present invention cannot obtain sufficient heat diffusibility. When considering heat radiation countermeasures using thermal radiation, the amount of heat radiated will depend on the area and thermal emissivity. Therefore, the larger the area of the sheet is within the range of no problem in installation, the larger the more advantageous. In this case, the heat-conducting layer can efficiently and quickly dissipate the heat from the heating element. Without a heat-conducting layer, the heat from the heat-generating body is not easily diffused, so that the advantage of increasing the sheet area cannot be exhibited. In the present invention, the thermal conductivity in the plane direction of the thermal conductive layer is measured by a thermal wave analyzer, and the thermal conductivity can be calculated from the thermal diffusivity and measured.
作為熱傳導層，可列舉例如石墨薄片、或鋁 箔、銅箔等。石墨薄片的面內熱傳導為非常優異，但彎曲或拉伸為弱，缺乏加工性。又，有石墨粉脫落之虞，且成本高。相較於石墨薄片，鋁箔或銅箔為低成本，由於強度高故合適。 Examples of the heat-conducting layer include graphite flakes and aluminum Foil, copper foil, etc. The graphite sheet has excellent in-plane thermal conduction, but is weak in bending or stretching, and lacks workability. In addition, graphite powder may fall off and the cost is high. Compared with graphite flakes, aluminum foil or copper foil is suitable for low cost and high strength.
熱傳導層之厚度較佳為0.01~0.1mm。又較佳為0.03~0.1mm，更佳為0.03~0.08mm。當熱傳導層之厚度過薄時，熱傳導性複合薄片會變得缺乏剛性，操作變困難。 又，超過0.1mm時，有損作為熱傳導性複合薄片之柔軟性，考量安裝時，有不適合之虞。 The thickness of the heat conductive layer is preferably 0.01 to 0.1 mm. It is more preferably 0.03 to 0.1 mm, and even more preferably 0.03 to 0.08 mm. When the thickness of the heat-conducting layer is too thin, the heat-conducting composite sheet may lack rigidity, making handling difficult. In addition, when it exceeds 0.1 mm, the flexibility as a heat conductive composite sheet is impaired, and there is a possibility that it may be unsuitable when considering mounting.
本發明的熱傳導性複合薄片中，熱放射層之熱放射率較佳為0.80以上，又較佳為0.80~0.99。未滿0.80時，有無法得到充分散熱效果之情形。熱放射層為含有組合氧化矽、氧化鋁、氧化鈦、氮化硼、氮化鋁等的陶瓷粉、或菫青石粉、黑鉛等熱放射率高的粒子中1種類或2種類以上的有機樹脂層，較佳為具備充分的柔軟性，使熱放射率高的粒子分散於有機樹脂中並只要是可確保熱放射率為0.80以上，未特別限定者。又，作為有機樹脂，舉例如丙烯酸樹脂、聚矽氧樹脂、環氧樹脂、胺基甲酸酯樹脂、聚酯樹脂等，但不限定於該等。 In the thermally conductive composite sheet of the present invention, the thermal emissivity of the thermal radiation layer is preferably 0.80 or more, and more preferably 0.80 to 0.99. When it is less than 0.80, a sufficient heat radiation effect may not be obtained. The thermal emissive layer is composed of one or two or more organic particles among ceramic powders containing a combination of silicon oxide, aluminum oxide, titanium oxide, boron nitride, and aluminum nitride, or particles of high thermal emissivity such as ochre powder and black lead The resin layer is preferably not particularly limited as long as it has sufficient flexibility to disperse particles with high thermal emissivity in the organic resin and can ensure a thermal emissivity of 0.80 or more. Examples of the organic resin include, but are not limited to, acrylic resin, silicone resin, epoxy resin, urethane resin, and polyester resin.
尚，本發明中，熱放射層之熱放射率為使用熱放射率測定器(AERD京都電子工業(股)製)所測定之值。 In the present invention, the thermal emissivity of the thermal emissive layer is a value measured using a thermal emissivity measuring device (AERD Kyoto Electronics Industry Co., Ltd.).
熱放射層之厚度為10~100μm，較佳為20~50μm。較10μm薄時，會變得缺乏加工性。又，使成為較100μm厚 時，會變得缺乏柔軟性。 The thickness of the heat radiation layer is 10 to 100 μm, and preferably 20 to 50 μm. When it is thinner than 10 μm, the workability becomes insufficient. And make it thicker than 100 μm As it becomes less flexible.
熱放射層為包含上述粉體的有機樹脂層，使 用於熱放射層的粒子之平均粒徑較佳為0.1~50μm，又較佳為1~10μm。上述粉體可利用球磨機或噴射磨機等的粉碎機，以粉碎的粉末狀態來使用。尚，粒徑為藉由Microtrac粒度分布測定裝置MT3300EX(日機裝(股))所測定之值。又，平均粒徑之基準為體積。 The heat radiation layer is an organic resin layer containing the above powder, so that The average particle diameter of the particles used in the heat emission layer is preferably 0.1 to 50 μm, and more preferably 1 to 10 μm. The powder can be used in a pulverized powder state using a pulverizer such as a ball mill or a jet mill. The particle size is a value measured by a Microtrac particle size distribution measuring device MT3300EX (Nikkiso Co., Ltd.). The standard of the average particle diameter is volume.
粉體之熱放射率較佳為0.80~0.99，又較佳為 0.85~0.99。又，相對於有機樹脂100質量份，上述粒子為40~200質量份，特佳為使用50~150質量份。當調配量少時，有無法得到熱放射性之情形，過多時，有粉體之填充為困難之情形。 The thermal emissivity of the powder is preferably 0.80 ~ 0.99, and more preferably 0.85 ~ 0.99. In addition, the particles are 40 to 200 parts by mass with respect to 100 parts by mass of the organic resin, and it is particularly preferable to use 50 to 150 parts by mass. When the blending amount is small, thermal radioactivity may not be obtained, and when it is too large, powder filling may be difficult.
作為熱放射層，可使用市售者，例子方面， 可列舉Cerac α(Cerac(股)製，熱放射率0.96)、Pelcool(Pelnox(股)製；含粉體之丙烯酸樹脂)等。 As the heat radiation layer, a commercially available one can be used. For example, Examples thereof include Cerac α (Cerac (strand), thermal emissivity 0.96), Pelcool (Pelnox (strand); powder-containing acrylic resin), and the like.
又，使熱放射層予以層合至熱傳導層者，作 為熱放射薄片可使用市售者，例如，將作為熱傳導層的鋁箔與作為熱放射層的熱放射性聚酯樹脂層合以作為熱放射薄片，可列舉Morgen sheet((股)淺利電機製)等。 In addition, the heat radiation layer is laminated to the heat conductive layer, and As the heat radiation sheet, a commercially available one can be used. For example, an aluminum foil as a heat conductive layer and a heat radioactive polyester resin as a heat radiation layer are laminated to be used as the heat radiation sheet. Morgen sheet ((shallow electric mechanism)) Wait.
本發明的熱傳導性複合薄片中，熱傳導性聚矽氧樹脂層之熱傳導率較佳為1.4W/mK以上，又較佳為2.0W/mK以上。當熱傳導性聚矽氧樹脂層之熱傳導率未滿1.4W/Mk 時，有無法將來自發熱體的熱量有效地傳遞至熱傳導層之情形。即，有無法得到充分散熱效果之情形。上限雖然未特別限制，但通常而言為10W/mK以下。此熱傳導率，可藉由將指定量的熱傳導性填充材調配至使用作為聚矽氧樹脂層的聚矽氧組成物中而得到。 In the thermally conductive composite sheet of the present invention, the thermal conductivity of the thermally conductive polysiloxane resin layer is preferably 1.4 W / mK or more, and more preferably 2.0 W / mK or more. When the thermal conductivity of the thermally conductive polysiloxane resin layer is less than 1.4 W / Mk In some cases, the heat from the heating element cannot be efficiently transferred to the heat conductive layer. That is, there may be a case where a sufficient heat radiation effect cannot be obtained. Although the upper limit is not particularly limited, it is generally 10 W / mK or less. This thermal conductivity can be obtained by blending a specified amount of a thermally conductive filler into a silicone composition using a silicone resin layer.
尚，本發明中，熱傳導性聚矽氧樹脂層之熱傳導率之測定為使用熱傳導率計(TPA-501，京都電子工業(股)製之商品名)所測定之值。 In the present invention, the measurement of the thermal conductivity of the thermally-conductive polysiloxane resin layer is a value measured using a thermal conductivity meter (TPA-501, a trade name of Kyoto Electronics Industry Co., Ltd.).
熱傳導性聚矽氧樹脂層之厚度為0.2mm以上。較佳為0.5mm以上，又較佳為1mm以上。由後述的實施例亦可得知般，當熱傳導性聚矽氧樹脂層之厚度越厚者，安裝之際之發熱體之降溫效果越大。此係認為，當熱傳導性聚矽氧樹脂層之厚度為厚時，在將來自發熱體的熱量傳遞至熱放射層之前，可發揮暫時儲存於熱傳導性聚矽氧樹脂層之作用之故。厚度過薄時，將難以得到在傳遞至熱放射層之前之儲存熱量之效果。厚度之上限未特別限制，但就實際使用時之質量之點而言，較佳為15mm以下，特佳為10mm以下，尤佳為5mm以下。 The thickness of the thermally conductive polysiloxane resin layer is 0.2 mm or more. It is preferably 0.5 mm or more, and more preferably 1 mm or more. It can also be seen from the examples described later that when the thickness of the thermally conductive polysiloxane resin layer is thicker, the cooling effect of the heating element at the time of installation is larger. This is considered that when the thickness of the thermally conductive polysiloxane resin layer is thick, it can temporarily store the heat in the thermally conductive polysiloxane resin layer before transferring heat from the heating element to the heat radiation layer. When the thickness is too thin, it is difficult to obtain the effect of storing heat before being transferred to the heat radiation layer. The upper limit of the thickness is not particularly limited, but in terms of quality in actual use, it is preferably 15 mm or less, particularly preferably 10 mm or less, and particularly preferably 5 mm or less.
熱傳導性聚矽氧樹脂層的硬度，以阿斯克C(Asker C)之硬度為40以下，較佳為30以下。當硬度超過40 時，變得缺乏對於發熱體之追隨性，接觸熱阻會增加。 又，對於高度相異的複數發熱體進行安裝之際，無法吸收該高度之差異，散熱特性有降低之可能性。硬度之下限值未特別限制，但就操作性之點而言，較佳為3以上，特佳為5以上。此阿斯克C(Asker C)硬度，可藉由調整聚矽氧組成物(其係使用於後述的熱傳導性聚矽氧樹脂層)中的聚矽氧樹脂含有量、有機氫聚矽氧烷含有量而得到。 The hardness of the thermally conductive polysiloxane resin layer is 40 or less, preferably 30 or less, based on the hardness of Asker C. When hardness exceeds 40 As a result, the followability to the heating element becomes insufficient, and the contact thermal resistance increases. In addition, when a plurality of heating elements having different heights are mounted, the difference in height cannot be absorbed, and there is a possibility that the heat dissipation characteristics are reduced. The lower limit of the hardness is not particularly limited, but in terms of operability, it is preferably 3 or more, and particularly preferably 5 or more. This Asker C hardness can be adjusted by adjusting the polysiloxane content in the polysiloxane composition (which is used in the thermally conductive polysiloxane layer described later) and the content of the organic hydrogen polysiloxane. Get it.
作為使用於熱傳導性聚矽氧樹脂層的熱傳導 性聚矽氧組成物，具體而言可舉例如熱傳導性聚矽氧組成物(A)或熱傳導性聚矽氧組成物(B)。 Thermal conductivity as a thermally conductive polysiloxane resin layer Specific examples of the polysiloxane composition include a thermally conductive polysiloxane composition (A) or a thermally conductive polysiloxane composition (B).
熱傳導性聚矽氧組成物(A)為含有下述(a)~(d)成分而成，(a)以下述平均組成式(1)所示並於一分子中具有2個以上鍵結於矽原子之烯基之有機聚矽氧烷：100質量份，RaSiO(4-a)/2 (1)(式中，R獨立為碳原子數1~12之非取代或取代之一價烴基，a為1.8~2.2之正數)；(b)熱傳導性填充劑：200~4,000質量份；(c)一分子中具有2個以上鍵結於矽原子之氫原子之有機氫聚矽氧烷：相對於(a)成分中之烯基，(c)成分中直接鍵結於矽原子之氫原子之莫耳比為0.5~5.0之量；(d)鉑系化合物：以鉑系元素量為(a)成分的0.1~ 1,000ppm。 The thermally conductive polysiloxane composition (A) contains the following components (a) to (d), (a) is represented by the following average composition formula (1), and has two or more bonds in one molecule: silicon organopolysiloxane siloxane silicon atoms of alkenyl group: 100 parts by mass, R a SiO (4-a ) / 2 (1) ( wherein, R is independently a non-carbon atoms of 1 to 12, a substituted or unsubstituted monovalent one (Hydrocarbon group, a is a positive number of 1.8 to 2.2); (b) thermally conductive filler: 200 to 4,000 parts by mass; (c) an organic hydrogen polysiloxane having more than two hydrogen atoms bonded to silicon atoms in one molecule : Relative to the alkenyl group in the component (a), the molar ratio of the hydrogen atom directly bonded to the silicon atom in the component (c) is 0.5 to 5.0; (d) the platinum-based compound: the platinum-based element amount is (a) 0.1 to 1,000 ppm of the component.
熱傳導性聚矽氧組成物(B)為含有下述(b)、(f)、(g)成分而成，(b)熱傳導性填充劑：100~3,000質量份；(f)聚矽氧樹脂：100質量份；(g)有機過氧化物系化合物：以有機過氧化物換算為0.1~2質量份。 The thermally conductive polysiloxane composition (B) contains the following components (b), (f), and (g), (b) a thermally conductive filler: 100 to 3,000 parts by mass; (f) a polysiloxane resin : 100 parts by mass; (g) organic peroxide-based compound: 0.1 to 2 parts by mass in terms of organic peroxide.
以下，對於上述熱傳導性聚矽氧組成物(A)之各成分進行說明。 Hereinafter, each component of the said thermally-conductive polysiloxane composition (A) is demonstrated.
(a)成分之含烯基之有機聚矽氧烷，係以下述平均組成式(1)所示並於一分子中具有2個以上鍵結於矽原子之烯基之有機聚矽氧烷，較佳為一分子中具有2~100個鍵結於矽原子之烯基，RaSiO(4-a)/2 (1)(式中，R獨立為碳原子數1~12之非取代或取代之一價烴基，a為1.8~2.2之正數，較佳為1.95~2.05之正數) (a) The alkenyl-containing organopolysiloxane containing the component is an organopolysiloxane represented by the following average composition formula (1) and having at least two alkenyl groups bonded to silicon atoms in one molecule, It is preferably an alkenyl group having 2 to 100 silicon atoms bonded in one molecule, and R a SiO (4-a) / 2 (1) (wherein R is independently an unsubstituted or Substituted monovalent hydrocarbon group, a is a positive number of 1.8 to 2.2, preferably a positive number of 1.95 to 2.05)
(a)成分為加成反應硬化型組成物中的主劑(基質聚合物)。通常而言，主鏈部分基本上以二有機矽氧烷單位之重複所成者為一般，此可於分子構造的一部份包含支鏈狀的構造，又，亦可為環狀體，但就硬化物之機械強度等、物性之點而言，較佳為直鏈狀的二有機聚矽氧烷。 (a) A component is a main agent (matrix polymer) in an addition reaction hardening type composition. Generally speaking, the main chain part is basically formed by the repetition of two organosiloxane units. This may include a branched structure in a part of the molecular structure, and may also be a cyclic body. In terms of mechanical properties such as the mechanical strength of the cured product, a linear diorganopolysiloxane is preferred.
上述式(1)中，R互相為同種或異種的碳原子數1~12，特以1~10之非取代或取代之一價烴基，作為 鍵結於矽原子之烯基以外的官能基，列舉例如：甲基、乙基、丙基、異丙基、丁基、異丁基、tert-丁基、戊基、新戊基、己基、庚基、辛基、壬基、癸基、十二烷基等的烷基、環戊基、環己基、環庚基等的環烷基、苯基、甲苯基、二甲苯基、萘基、聯苯基等的芳基、苄基、苯乙基、苯丙基、甲基苄基等的芳烷基，以及該等基之碳原子所鍵結的氫原子之一部份或全部被氟、氯、溴等的鹵原子、氰基等取代之基，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，代表性為碳原子數1~10，特別代表性為碳原子數1~6者，較佳為甲基、乙基、丙基、氯甲基、溴乙基、3,3,3-三氟丙基、氰乙基等的碳原子數1~3之非取代或取代之烷基及苯基、氯苯基、氟苯基等的非取代或取代之苯基。又，鍵結於矽原子之烯基以外的官能基，可全部為相同或相異。 In the above formula (1), R is the same or different kind of carbon atoms of 1 to 12, and especially a non-substituted or substituted monovalent hydrocarbon group of 1 to 10 is used as Functional groups other than the alkenyl group bonded to the silicon atom include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, Alkyl, such as heptyl, octyl, nonyl, decyl, dodecyl, cycloalkyl, cyclopentyl, cyclohexyl, cycloheptyl, etc., phenyl, tolyl, xylyl, naphthyl, Aryl groups such as biphenyl, benzyl, phenethyl, phenylpropyl, methylbenzyl, etc., and some or all of the hydrogen atoms bonded to the carbon atoms of these groups are fluorine Halogen atom such as chloro, bromine, etc., substituted groups such as cyano, for example: chloromethyl, 2-bromoethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, chlorophenyl, fluorine Phenyl, cyanoethyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, etc., typically 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms Among them, methyl, ethyl, propyl, chloromethyl, bromoethyl, 3,3,3-trifluoropropyl, cyanoethyl and the like having an unsubstituted or substituted carbon number of 1 to 3 are preferred. Alkyl and unsubstituted or substituted phenyl such as phenyl, chlorophenyl, and fluorophenyl. Moreover, all functional groups other than the alkenyl group bonded to a silicon atom may be the same or different.
又，作為烯基，可列舉例如乙烯基、烯丙基、丙烯基、異丙烯基、丁烯基、己烯基、環己烯基等，通常而言為碳原子數2~8左右者，之中，較佳為乙烯基、烯丙基等的低級烯基，特佳為乙烯基。 Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, a hexenyl group, and a cyclohexenyl group. Generally, the number of carbon atoms is about 2 to 8, Among them, lower alkenyl groups such as vinyl and allyl are preferred, and vinyl is particularly preferred.
此有機聚矽氧烷之25℃時之動黏度，通常而 言為10~100,000mm2/s，特佳為500~50,000mm2/s之範圍。當前述動黏度過低時，所得到的組成物之保存安定性有變差之情形，又，過高時，所得到的組成物之伸展性有變差之情形。尚，本發明中，動黏度可藉由奧士瓦黏度計 來測定。 The dynamic viscosity of the organic polysiloxane at 25 ° C is generally in the range of 10 to 100,000 mm 2 / s, and particularly preferably in the range of 500 to 50,000 mm 2 / s. When the aforementioned dynamic viscosity is too low, the storage stability of the obtained composition may be deteriorated, and when it is too high, the extensibility of the obtained composition may be deteriorated. However, in the present invention, the dynamic viscosity can be measured by an Oshwa viscosity meter.
此(a)成分之有機聚矽氧烷，可使用單獨1種，亦可組合動黏度為相異的2種以上使用。 The organopolysiloxane of the component (a) may be used singly or in combination of two or more kinds having different dynamic viscosities.
作為熱傳導性聚矽氧組成物中所填充的熱傳導性填充材，可使用非磁性的銅或鋁等的金屬、氧化鋁、氧化矽、氧化鎂、紅氧化鐵(bengala)、氧化鈹、氧化鈦、氧化鋯、鋅白等的金屬氧化物、氮化鋁、氮化矽、氮化硼等的金屬氮化物、氫氧化鋁、氫氧化鎂等的金屬氫氧化物、人工鑽石或碳化矽等一般被作為熱傳導填充材之物質。熱傳導性填充材可使用單獨1種，或組合2種以上使用。 As the thermally conductive filler filled in the thermally conductive polysiloxane composition, non-magnetic metals such as copper or aluminum, aluminum oxide, silicon oxide, magnesium oxide, red iron oxide (bengala), beryllium oxide, and titanium oxide can be used. , Metal oxides such as zirconia, zinc white, metal nitrides such as aluminum nitride, silicon nitride, boron nitride, metal hydroxides such as aluminum hydroxide, magnesium hydroxide, artificial diamond or silicon carbide, etc. Substances used as heat conductive fillers. The thermally conductive filler can be used alone or in combination of two or more.
熱傳導性填充材之平均粒徑，較佳為0.1~ 200μm，又較佳為0.1~100μm，更較佳為0.5~50μm。此處所述的平均粒徑為藉由Microtrac粒度分布測定裝置MT3300EX(日機裝(股))所測定之值。又，平均粒徑之基準為體積。 The average particle diameter of the thermally conductive filler is preferably 0.1 to 200 μm, more preferably 0.1 to 100 μm, and more preferably 0.5 to 50 μm. The average particle diameter described here is a value measured by a Microtrac particle size distribution measuring device MT3300EX (Nikkiso Co., Ltd.). The standard of the average particle diameter is volume.
作為熱傳導性填充劑之調配量，相對於(a) 成分100質量份，較佳為200~4,000質量份，又較佳為200~3,000質量份。當熱傳導性填充劑之調配量過少時，熱傳導性樹脂層有無法得到充分的熱傳導率之情形，調配量過多時，成形性會惡化，黏著性有降低之情形。 The amount of the thermally conductive filler is relative to (a) The ingredients are 100 parts by mass, preferably 200 to 4,000 parts by mass, and still more preferably 200 to 3,000 parts by mass. When the blending amount of the thermally conductive filler is too small, the thermally conductive resin layer may not be able to obtain sufficient thermal conductivity. When the blending amount is too large, the moldability may be deteriorated and the adhesion may be reduced.
(c)成分之有機氫聚矽氧烷，係一分子中具有2個以上鍵結於矽原子之氫原子(即，SiH基)之有機氫聚矽氧烷，較佳為一分子中具有2~100個鍵結於矽原子之氫原子，對於(a)成分而言，(c)成分係作用為交聯劑之成分。即，在後述的(d)成分(鉑系化合物)之存在下，藉由氫化矽烷化反應，(c)成分中的鍵結於矽原子之氫原子會加成於(a)成分中的烯基，而生成一具有三次元網狀構造的交聯硬化物，該三次元網狀構造為具有交聯鍵結。 (c) The organohydrogenpolysiloxane is an organohydrogenpolysiloxane having more than two hydrogen atoms (ie, SiH groups) bonded to silicon atoms in one molecule, preferably 2 in one molecule. ~ 100 hydrogen atoms bonded to a silicon atom. For the component (a), the component (c) functions as a cross-linking component. That is, in the presence of the component (d) (platinum-based compound) described later, the hydrogen atom bonded to the silicon atom in the component (c) is added to the olefin in the component (a) by a hydrosilylation reaction. And a cross-linked hardened body having a three-dimensional network structure is formed, which has a cross-linked bond.
作為(c)成分中的鍵結於矽原子之有機基， 可列舉例如不具有脂肪族不飽和鍵結之非取代或取代之一價烴基等。具體而言，可列舉與在(a)成分說明中作為脂肪族不飽和基以外的鍵結於矽原子之基所示例為相同的非取代或取代之一價烴基，該等之中，就合成容易性及經濟性之觀點而言，較佳為甲基。 As the organic group bonded to the silicon atom in the component (c), Examples thereof include an unsubstituted or substituted monovalent hydrocarbon group which does not have an aliphatic unsaturated bond. Specifically, the same unsubstituted or substituted monovalent hydrocarbon group as that exemplified as the group bonded to a silicon atom other than the aliphatic unsaturated group in the description of the component (a) can be listed. From the viewpoint of easiness and economy, methyl is preferred.
本發明中的(c)成分之有機氫聚矽氧烷之構 造未特別限定，可任意為直鏈狀、支鏈狀及環狀，較佳為直鏈狀。 Structure of organohydrogenpolysiloxane in component (c) in the present invention The structure is not particularly limited, and may be any of linear, branched, and cyclic, and preferably linear.
又，有機氫聚矽氧烷之聚合度(矽原子之數)，較佳為2~100，特佳為2~50。 The polymerization degree (the number of silicon atoms) of the organic hydrogen polysiloxane is preferably 2 to 100, and particularly preferably 2 to 50.
作為(c)成分之有機氫聚矽氧烷之適合的具 體例，舉例如分子鏈兩末端以三甲基矽氧烷基所封端的甲基氫聚矽氧烷、分子鏈兩末端以三甲基矽氧烷基所封端的二甲基矽氧烷‧甲基氫矽氧烷共聚物、分子鏈兩末端以三 甲基矽氧烷基所封端的二甲基矽氧烷‧甲基氫矽氧烷‧甲基苯基矽氧烷共聚物、分子鏈兩末端以二甲基氫矽氧烷基所封端的二甲基聚矽氧烷、分子鏈兩末端以二甲基氫矽氧烷基所封端的二甲基矽氧烷‧甲基氫矽氧烷共聚物、分子鏈兩末端以二甲基氫矽氧烷基所封端的二甲基矽氧烷‧甲基苯基矽氧烷共聚物、分子鏈兩末端以二甲基氫矽氧烷基所封端的甲基苯基聚矽氧烷等。尚，(c)成分之有機氫聚矽氧烷，可使用單獨1種，亦可組合2種以上使用。 Suitable organohydrogenpolysiloxanes as component (c) For example, for example, methylhydropolysiloxane terminated with trimethylsilyl groups at both ends of the molecular chain, and dimethylsiloxane · methyl terminated with trimethylsiloxy groups at both ends of the molecular chain Hydrogen siloxane copolymer Copolymers of dimethylsiloxane, methylhydrosiloxane, and methylphenylsiloxane terminated by methylsiloxyalkyl, and two ends of molecular chain terminated with dimethylhydrosiloxane Methylpolysiloxane, dimethylsiloxane ‧ methylhydrosiloxane copolymer terminated at both ends of the molecular chain with dimethylhydrosiloxane, dimethylhydrosiloxane at both ends of the molecular chain Copolymers of dimethylsiloxane and methylphenylsiloxane terminated by alkyl groups, methylphenylpolysiloxanes terminated by dimethylhydrosilyl at both ends of the molecular chain, and the like. The organohydrogenpolysiloxane of component (c) may be used singly or in combination of two or more kinds.
(c)成分之調配量，相對於(a)成分中之 烯基1莫耳，使(c)成分中之SiH基以成為0.5~5.0莫耳之量為較佳，又較佳以成為0.8~4.0莫耳之量。相對於(a)成分中之烯基1莫耳，當(c)成分中之SiH基之量未滿0.5莫耳時，會產生組成物無法硬化、或硬化物之強度為不足，而無法作為成形體、複合體操作等的問題之情形。另一方面，當使用超過5.0莫耳之量時，硬化物表面之黏著性有變不足之虞。 (c) The amount of the component is relative to the amount of the component (a) The alkenyl group is 1 mole. The SiH group in the component (c) is preferably 0.5 to 5.0 moles, and more preferably 0.8 to 4.0 moles. When the amount of SiH group in component (c) is less than 0.5 mol relative to 1 mol of alkenyl group in component (a), the composition cannot be hardened, or the strength of the hardened material is insufficient, and cannot be used In the case of problems with the operation of shaped bodies and composites. On the other hand, when an amount exceeding 5.0 mol is used, the adhesiveness on the surface of the hardened material may become insufficient.
(d)成分之鉑系化合物，係促進(a)成分中的烯基、與(c)成分中的鍵結於矽原子之氫原子之加成反應，並用來使本發明的組成物轉換成三次元網狀構造的交聯硬化物所調配之觸媒成分。 The platinum-based compound of the component (d) promotes the addition reaction of the alkenyl group in the component (a) and the hydrogen atom bonded to the silicon atom in the component (c), and is used to convert the composition of the present invention into A catalyst component formulated by a three-dimensional network crosslinked cured product.
上述(d)成分，可適當地自使用於一般的氫化矽烷化反應的習知觸媒中選擇使用。作為該具體例，可 列舉例如：鉑(包含鉑黑)、銠、鈀等的鉑族金屬單質；H2PtCl4‧nH2O、H2PtCl6‧nH2O、NaHPtCl6‧nH2O、KHPtCl6‧nH2O、Na2PtCl6‧nH2O、K2PtCl4‧nH2O、PtCl4‧nH2O、PtCl2、Na2HPtCl4‧nH2O(但是式中的n為0~6之整數，較佳為0或6)等的氯化鉑、氯化鉑酸及氯化鉑酸鹽；醇變性氯化鉑酸；氯化鉑酸與烯烴之錯合物；將鉑黑、鈀等的鉑族金屬載持於氧化鋁、氧化矽、碳等之載體者；銠-烯烴錯合物；氯參(三苯基膦)銠(威爾金森(Wilkinson)觸媒)；氯化鉑、氯化鉑酸、氯化鉑酸鹽與含乙烯基之矽氧烷之錯合物等。該等鉑系化合物可使用單獨1種，亦可組合2種以上使用。 The component (d) can be appropriately selected from conventional catalysts used in general hydrosilylation reactions. As this specific example, platinum (including platinum black), rhodium, palladium, and other platinum group metal element; H 2 PtCl 4 ‧nH 2 O, H 2 PtCl 6 ‧nH 2 O, NaHPtCl 6 ‧nH 2 O KHPtCl 6 ‧nH 2 O, Na 2 PtCl 6 ‧nH 2 O, K 2 PtCl 4 ‧nH 2 O, PtCl 4 ‧nH 2 O, PtCl 2 , Na 2 HPtCl 4 ‧nH 2 O (but n in the formula Is an integer from 0 to 6, preferably 0 or 6), such as platinum chloride, platinum chloride, and platinum chloride; alcohol-denatured chloroplatinic acid; a complex of chloroplatinic acid and an olefin; Platinum group metals such as platinum black and palladium supported on alumina, silica, carbon, etc .; rhodium-olefin complexes; chloroshen (triphenylphosphine) rhodium (Wilkinson catalyst) ; Complex of platinum chloride, platinum chloride acid, platinum chloride and vinyl-containing siloxane. These platinum-based compounds may be used singly or in combination of two or more kinds.
上述(d)成分之鉑系化合物之調配量，只要 是用來使組成物硬化為所需的有效量即可，通常而言，以相對於(a)成分的鉑族金屬元素之質量換算為0.1~1,000ppm，較佳為0.5~500ppm。 The compounding amount of the platinum-based compound of the component (d) is as long as It is sufficient to harden the composition to a required effective amount. Generally, it is 0.1 to 1,000 ppm, preferably 0.5 to 500 ppm, in terms of the mass of the platinum group metal element with respect to the component (a).
(e)成分之反應控制劑為視所需而調配之成分，其係用來調整在(d)成分之存在下所進行的(a)成分與(c)成分之加成反應(氫化矽烷化反應)之速度。如此般的(e)成分之反應控制劑，可適當地自使用於一般的加成反應硬化型聚矽氧組成物的習知加成反應控制劑中選擇使用。作為該具體例，舉例如1-乙炔基-1-環己醇、3-丁炔-1-醇、乙炔基亞甲基甲醇等的乙炔化合物、氮化合 物、有機磷化合物、硫化合物、肟化合物、有機氯化合物等。該等加成反應控制劑可使用單獨1種，亦可組合2種以上使用。 The reaction control agent for the component (e) is a component prepared as necessary, and it is used to adjust the addition reaction of the component (a) and the component (c) in the presence of the component (d) (hydrosilylation) Reaction) speed. Such a reaction control agent for the component (e) can be appropriately selected and used from a conventional addition reaction control agent used in a general addition reaction-hardening polysiloxane composition. As this specific example, for example, acetylene compounds such as 1-ethynyl-1-cyclohexanol, 3-butyn-1-ol, ethynylmethylene methanol, etc. Substances, organic phosphorus compounds, sulfur compounds, oxime compounds, organic chlorine compounds, and the like. These addition reaction controlling agents may be used singly or in combination of two or more kinds.
上述(e)成分之調配量會依(d)成分之使 用量而異，因而無法一概定之。只要是對於能將氫化矽烷化反應之進行調整成所希望的反應速度為有效量者即足夠。通常而言，相對於(a)成分之質量，以設為10~50,000ppm左右即可。當(e)成分之調配量過少時，組成物之保存安定性會變得不足，有無法確保充分的可使用時間之情形，相反地，過多時，組成物之硬化性有降低之情形。 The amount of the component (e) above will depend on the component (d). The amount varies, so it cannot be determined in general. It suffices if the amount of the hydrosilylation reaction can be adjusted to a desired reaction rate. Generally, it may be about 10 to 50,000 ppm with respect to the mass of the component (a). When the blending amount of the (e) component is too small, the storage stability of the composition may become insufficient, and a sufficient usable time may not be secured. On the contrary, when it is too large, the hardenability of the composition may be reduced.
(f)成分之聚矽氧樹脂，係具有使硬化後的熱傳導性聚矽氧組成物的硬化物表面賦予黏著性之作用。作為如此般的(f)成分之例，舉例如R1 3SiO1/2單位(M單位)與SiO4/2單位(Q單位)之共聚物，且M單位與Q單位之比(莫耳比)M/Q為0.5~1.5之聚矽氧樹脂，M/Q較佳為0.6~1.4，更佳為0.7~1.3。當上述M/Q為上述範圍時，可得到所希望的黏著力。此時，因應所需亦可包含R1 2SiO2/2單位(D單位)或R1SiO3/2單位(T單位)，但該等D單位及T單位之調配較佳為15莫耳%以下，特佳為10莫耳%以下。 (f) The polysiloxane resin has a function of imparting adhesiveness to the surface of the cured product of the thermally conductive polysiloxane composition after curing. As an example of such a (f) component, for example, a copolymer of R 1 3 SiO 1/2 unit (M unit) and SiO 4/2 unit (Q unit), and the ratio of M unit to Q unit (Mole Ratio) Polysilicone resin with M / Q of 0.5 ~ 1.5, M / Q is preferably 0.6 ~ 1.4, more preferably 0.7 ~ 1.3. When the M / Q is within the above range, a desired adhesive force can be obtained. At this time, R 1 2 SiO 2/2 units (D units) or R 1 SiO 3/2 units (T units) may be included as required, but the deployment of these D units and T units is preferably 15 mol % Or less, particularly preferably 10 mol% or less.
表示上述M單位等的一般式中，R1為非取代 或取代之一價烴基，較佳為不含有脂肪族不飽和鍵結之非取代或取代之一價烴基。作為如此般的R1之例，列舉例如：甲基、乙基、丙基、異丙基、丁基、異丁基、tert-丁基、戊基、新戊基、己基、庚基、辛基、壬基、癸基、十二烷基等的烷基、環戊基、環己基、環庚基等的環烷基、苯基、甲苯基、二甲苯基、萘基、聯苯基等的芳基、苄基、苯乙基、苯丙基、甲基苄基等的芳烷基，以及該等基之碳原子所鍵結的氫原子之一部份或全部被氟、氯、溴等的鹵原子、氰基等取代之基，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的碳原子數為1~12，較佳為碳原子數為1~6者。 In the general formula representing the M unit and the like, R 1 is an unsubstituted or substituted monovalent hydrocarbon group, and is preferably an unsubstituted or substituted monovalent hydrocarbon group which does not contain an aliphatic unsaturated bond. Examples of such R 1 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, and octyl. Alkyl, nonyl, decyl, dodecyl, etc., cyclopentyl, cyclohexyl, cycloheptyl, etc. cycloalkyl, phenyl, tolyl, xylyl, naphthyl, biphenyl, etc. Aryl, benzyl, phenethyl, phenylpropyl, methylbenzyl and other aralkyl groups, and some or all of the hydrogen atoms bonded to the carbon atoms of these groups are fluorine, chlorine, bromine And other halogen atoms, substituted groups such as cyano, for example: chloromethyl, 2-bromoethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, chlorophenyl, fluorophenyl, cyano Ethyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl has 1 to 12 carbon atoms, and preferably 1 to 6 carbon atoms.
作為R1，該等之中較佳為甲基、乙基、丙 基、氯甲基、溴乙基、3,3,3-三氟丙基、氰乙基等的碳原子數1~3之非取代或取代之烷基、及苯基、氯苯基、氟苯基等的非取代或取代之苯基。又，R1可全部為相同或相異。只要是不要求耐溶劑性等的特殊特性之情況下，就成本、該取得容易性、化學安定性、環境負擔等之觀點而言，R1較佳全部為甲基。 As R 1 , among these, methyl, ethyl, propyl, chloromethyl, bromoethyl, 3,3,3-trifluoropropyl, cyanoethyl and the like are preferred. Unsubstituted or substituted alkyl, and unsubstituted or substituted phenyl such as phenyl, chlorophenyl, and fluorophenyl. In addition, all of R 1 may be the same or different. As long as special characteristics such as solvent resistance are not required, from the viewpoints of cost, availability, chemical stability, environmental burden, etc., all of R 1 is preferably methyl.
調配(f)成分時，相對於(a)成分100質量 份，該調配量較佳為50~500質量份，又較佳為60~350質量份，更佳為70~250質量份。當(f)成分之調配量未滿50質量份或超過500質量份時，有無法得到所希望的黏著性之情形。 When formulating (f) component, it is 100 mass relative to (a) component The blending amount is preferably 50 to 500 parts by mass, more preferably 60 to 350 parts by mass, and even more preferably 70 to 250 parts by mass. When the blending amount of the (f) component is less than 50 parts by mass or more than 500 parts by mass, the desired adhesiveness may not be obtained.
尚，(f)成分其本身於室溫下為固體或黏稠的液體，亦能以溶解於溶劑中之狀態來使用。此情形時，對組成物之添加量應以除去溶劑部分之量來決定。 The component (f) itself is a solid or viscous liquid at room temperature, and can be used in a state of being dissolved in a solvent. In this case, the amount of addition to the composition should be determined based on the amount of solvent removed.
接著，對於上述熱傳導性聚矽氧組成物(B)之各成分進行說明。 Next, each component of the said thermally-conductive polysiloxane composition (B) is demonstrated.
作為(b)成分之熱傳導性填充劑，可示例與上述熱傳導性聚矽氧組成物(A)之熱傳導性填充劑為相同者。 Examples of the thermally conductive filler of the component (b) are the same as the thermally conductive filler of the thermally conductive polysiloxane composition (A).
作為熱傳導性填充劑之調配量，相對於後述的(f)成分100質量份，較佳為100~3,000質量份，又較佳為200~2,500質量份。當熱傳導性填充劑之調配量過少時，熱傳導性聚矽氧樹脂層有無法得到充分的熱傳導率之情形，調配量過多時，成形性會惡化，黏著性有降低之情形。 The blending amount of the thermally conductive filler is preferably 100 to 3,000 parts by mass, and more preferably 200 to 2,500 parts by mass with respect to 100 parts by mass of the component (f) described later. When the blending amount of the thermally conductive filler is too small, the thermally conductive polysiloxane resin layer may not be able to obtain sufficient thermal conductivity. When the blending amount is too large, the moldability may be deteriorated and the adhesiveness may be reduced.
作為(f)成分之聚矽氧樹脂，可示例與上述熱傳導性聚矽氧組成物(A)之聚矽氧樹脂為相同者。 The silicone resin as the component (f) may be the same as the silicone resin of the thermally conductive silicone composition (A).
藉由有機過氧化物的聚矽氧組成物的硬化反應，係對於分子鏈末端(單末端或兩末端)及分子鏈非末端之任一方或該雙方，使具有乙烯基等的烯基的直鏈狀有機聚矽氧烷在有機過氧化物系化合物之存在下進行自由基聚合而引 起。作為(g)成分之有機過氧化物系化合物，舉例如二醯基過氧化物、二烷基過氧化物等。有機過氧化物系化合物對於光或熱為弱，而不安定，因而使固體的有機過氧化物系化合物分散於組成物中為困難，故使稀釋於有機溶劑、或使分散於聚矽氧成分之狀態下使用者為多。 The hardening reaction of a polysilicone composition of an organic peroxide is to straighten an alkenyl group having a vinyl group or the like to one or both of a molecular chain end (single end or both ends) and a non-terminal end of the molecular chain. The chain-like organopolysiloxane is radically polymerized in the presence of an organic peroxide-based compound to induce Up. Examples of the organic peroxide-based compound (g) include difluorenyl peroxide and dialkyl peroxide. Organic peroxide compounds are weak to light or heat and are unstable. Therefore, it is difficult to disperse solid organic peroxide compounds in the composition. Therefore, they are diluted in an organic solvent or dispersed in a polysiloxane component. There are many users in this state.
有機過氧化物系化合物之調配量，相對於 (f)聚矽氧樹脂100質量份，以有機過氧化物換算較佳為0.1~2質量份，又較佳為0.1~1.6質量份。當調配量過少時，硬化反應有無法充分進行之情形，過多時，組成物有欠缺安定性之情形。 The compounding amount of organic peroxide compounds is relative to (f) 100 parts by mass of the silicone resin, preferably 0.1 to 2 parts by mass, and more preferably 0.1 to 1.6 parts by mass in terms of organic peroxides. When the blending amount is too small, the curing reaction may not proceed sufficiently, and when it is too large, the composition may lack stability.
構成熱傳導聚矽氧樹脂層的熱傳導性聚矽氧組成物中，因應所需且在不損及本發明的目的之範圍內，可添加上述成分以外的成分。 In the thermally-conductive polysiloxane composition constituting the thermally-conductive polysiloxane resin layer, components other than the above-mentioned components may be added as necessary and within a range that does not impair the object of the present invention.
熱傳導性聚矽氧組成物中，以疏水化處理組 成物調製時的(b)成分之熱傳導性填充劑，來提昇與組成物(A)中的(a)成分之有機聚矽氧烷、或組成物(B)中的(f)成分之聚矽氧樹脂之濕潤性，使該熱傳導性填充劑均勻地分散於由(a)成分或(f)成分所成的基質中為目的，可調配表面處理劑(濕潤劑/wetter)(h)。作為此(h)成分，特佳為下述(h-1)及(h-2)成分。 In a thermally conductive polysilicone composition, The thermally conductive filler of component (b) during the preparation of the product, to enhance the polymerization with the organopolysiloxane of component (a) in the composition (A) or the component (f) in the composition (B) The wettability of the silicone resin allows the thermally conductive filler to be uniformly dispersed in a matrix formed by the component (a) or (f), and a surface treatment agent (wetting agent / wetter) (h) can be blended. As this (h) component, the following (h-1) and (h-2) components are particularly preferable.
(h-1)：以下述一般式(2)所表示之烷氧 基矽烷化合物，R2 mR3 nSi(OR4)4-m-n (2)(式中，R2獨立為碳原子數6~15之烷基，R3獨立為非取代或取代之碳原子數1~8之一價烴基，R4獨立為碳原子數1~6之烷基，m為1~3之整數，n為0、1或2，m+n為1~3之整數)。 (h-1): an alkoxysilane compound represented by the following general formula (2), R 2 m R 3 n Si (OR 4 ) 4-mn (2) (wherein R 2 is independently the number of carbon atoms 6 to 15 alkyl groups, R 3 is independently an unsubstituted or substituted monovalent hydrocarbon group of 1 to 8 carbon atoms, R 4 is independently an alkyl group of 1 to 6 carbon atoms, m is an integer of 1 to 3, n (0, 1, or 2; m + n is an integer from 1 to 3).
上述一般式(2)中，作為R2所表示的烷基，可列舉例如己基、辛基、壬基、癸基、十二烷基、十四烷基等。如此般地，以R2所表示的烷基之碳原子數只要為6~15之範圍時，由於可充分提昇(b)成分之熱傳導性填充劑之濕潤性，使得操作的作業性變良好，故組成物之低溫特性為良好者。 Examples of the alkyl group represented by R 2 in the general formula (2) include a hexyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, and a tetradecyl group. In this way, when the number of carbon atoms of the alkyl group represented by R 2 is in the range of 6 to 15, the wettability of the thermally conductive filler of the component (b) can be sufficiently improved, and the workability is improved. Therefore, the composition has good low temperature characteristics.
又，作為以上述R3所表示的非取代或取代之一價烴基，可列舉例如：甲基、乙基、丙基、己基、辛基等的烷基；環戊基、環己基等的環烷基；乙烯基、烯丙基等的烯基；苯基、甲苯基等的芳基；2-苯乙基、2-甲基-2-苯乙基等的芳烷基；3,3,3-三氟丙基、2-(九氟丁基)乙基、2-(十七氟辛烷)乙基、p-氯苯基等的鹵化烴基等。本發明中，該等之中以甲基及乙基為特佳。 Examples of the unsubstituted or substituted monovalent hydrocarbon group represented by R 3 include alkyl groups such as methyl, ethyl, propyl, hexyl, and octyl; and rings such as cyclopentyl and cyclohexyl. Alkyl; alkenyl such as vinyl, allyl; aryl such as phenyl and tolyl; aralkyl such as 2-phenethyl and 2-methyl-2-phenethyl; 3,3, Halogenated hydrocarbon groups such as 3-trifluoropropyl, 2- (nonafluorobutyl) ethyl, 2- (heptadecafluorooctane) ethyl, p-chlorophenyl, and the like. In the present invention, methyl and ethyl are particularly preferred.
作為以上述R4所表示的烷基，可列舉例如甲基、乙基、丙基、丁基、戊基、己基等。本發明中，該等之中以甲基及乙基為特佳。 Examples of the alkyl group represented by R 4 include methyl, ethyl, propyl, butyl, pentyl, and hexyl. In the present invention, methyl and ethyl are particularly preferred.
作為上述(h-1)成分之適合的具體例，可列舉如下述者。 Specific suitable examples of the (h-1) component include the following.
C6H13Si(OCH3)3 C 6 H 13 Si (OCH 3 ) 3
C10H21Si(OCH3)3 C 10 H 21 Si (OCH 3 ) 3
C12H25Si(OCH3)3 C 12 H 25 Si (OCH 3 ) 3
C12H25Si(OC2H5)3 C 12 H 25 Si (OC 2 H 5 ) 3
C10H21Si(CH3)(OCH3)2 C 10 H 21 Si (CH 3 ) (OCH 3 ) 2
C10H21Si(C6H5)(OCH3)2 C 10 H 21 Si (C 6 H 5 ) (OCH 3 ) 2
C10H21Si(CH3)(OC2H5)2 C 10 H 21 Si (CH 3 ) (OC 2 H 5 ) 2
C10H21Si(CH=CH2)(OCH3)2 C 10 H 21 Si (CH = CH 2 ) (OCH 3 ) 2
C10H21Si(CH2CH2CF3)(OCH3)2 C 10 H 21 Si (CH 2 CH 2 CF 3 ) (OCH 3 ) 2
上述(h-1)成分，可使用單獨1種，亦可組合2種以上使用。(h-1)成分之調配量，即使是添加超過後述的調配量，亦由於該濕潤效果為有限無法再增大，故不經濟。又，此成分具有揮發性，因而在開放系中放置時，組成物及硬化後的硬化物會緩慢地變硬，故較佳停止於所需最低限度之量。 The (h-1) component may be used alone or in combination of two or more. (h-1) The compounded amount of the component is not economical because the moisturizing effect is limited and cannot be increased even if it is added in excess of the amount to be described later. In addition, since this component is volatile, when the composition is left in an open system, the composition and the hardened material after hardening will gradually harden. Therefore, it is preferable to stop it at the required minimum amount.
(h-2)：以下述一般式(3)所表示並將分子鏈單末端以三烷氧基矽烷基封端之二甲基聚矽氧烷，
作為上述(h-2)成分之適合的具體例，可列 舉如下述者。 Suitable specific examples of the (h-2) component are listed below. Examples are as follows.
尚，(h-2)成分，可使用單獨1種，亦可組 合2種以上使用。此(h-2)成分之調配量，當超過後述的調配量時，所得到的硬化物之耐熱性或耐濕性有下降之傾向。 (H-2) ingredients can be used alone or in groups Use more than 2 types. When the compounding amount of this (h-2) component exceeds the compounding amount mentioned later, the heat resistance or moisture resistance of the hardened | cured material obtained will fall.
本發明中，作為(b)成分之表面處理劑，可 選擇由前述(h-1)成分及(h-2)成分所成之群中所選出之至少1種使用。此情形時，組成物(A)中的全(h)成分之調配量，相對於(a)成分100質量份，較佳為0.01~50質量份，特佳為0.1~30質量份。又，組成物(B)中的全(h)成分之調配量，相對於(f)成分100質量份，較佳為0.01~50質量份，特佳為0.1~30質量份。 In the present invention, as the surface treatment agent of component (b), At least one selected from the group consisting of the (h-1) component and the (h-2) component is selected and used. In this case, the blending amount of all (h) components in the composition (A) is preferably 0.01 to 50 parts by mass, and particularly preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the component (a). The compounding amount of all (h) components in the composition (B) is preferably 0.01 to 50 parts by mass, and particularly preferably 0.1 to 30 parts by mass, with respect to 100 parts by mass of the component (f).
本發明中，作為其他任意成分，亦可添加例 如氟變性聚矽氧界面活性劑、作為著色劑的碳黑、二氧化鈦等。更，以熱傳導性填充劑之抗沈降或補強為目的，亦可適當地添加沈降性氧化矽或燒成氧化矽等的微粉末氧化矽、觸變性提昇劑等。 In the present invention, examples may be added as other optional components. Such as fluorine-denatured polysiloxane surfactant, carbon black as colorant, titanium dioxide and so on. Furthermore, for the purpose of anti-settling or reinforcement of the thermally conductive filler, fine powdered silicon oxide such as settling silica or sintered silica, thixotropy enhancer, etc. may be appropriately added.
熱傳導性聚矽氧組成物，可藉由將上述(a) ~(d)成分、或(b)、(f)、(g)成分、及因應所需的其他成分，依照常法混合並予以調製。 A thermally conductive polysiloxane composition can be obtained by combining the above (a) ~ (d) component, or (b), (f), (g) component, and other components required in accordance with the conventional method are mixed and prepared.
尚，作為熱傳導性聚矽氧組成物之硬化條件，只要與習知的加成反應硬化型聚矽氧橡膠組成物或有機過氧化物硬化型聚矽氧橡膠組成物為相同即可。 The curing conditions of the thermally conductive polysiloxane composition may be the same as the conventional addition reaction-curable polysiloxane composition or the organic peroxide-curable polysiloxane composition.
本發明的熱傳導性複合薄片，係藉由於熱傳導層上層合熱放射層使成為熱放射薄片，再對此熱放射薄片層合熱傳導性聚矽氧樹脂層而得到。於熱傳導層上層合熱放射層之方法，可舉例如塗布法等，但不限定於此方法。又，層合熱傳導性聚矽氧樹脂層之方法，可舉例如貼合法、塗布法、壓製法等，但不限定於該等。 The heat conductive composite sheet of the present invention is obtained by laminating a heat radiation layer on a heat conductive layer to become a heat radiation sheet, and then laminating a heat conductive polysiloxane resin layer on the heat radiation sheet. The method of laminating the heat radiation layer on the heat conductive layer includes, for example, a coating method, but is not limited to this method. The method of laminating the thermally-conductive polysiloxane resin layer includes, for example, a bonding method, a coating method, a pressing method, and the like, but is not limited thereto.
本發明的熱傳導性複合薄片，可有效地使用 於智慧型手機、或數位攝影機等的可攜式的電子終端機、或LED照明等。 The thermally conductive composite sheet of the present invention can be effectively used Portable electronic terminals such as smart phones, digital cameras, and LED lighting.
以下為表示實施例及比較例，以具體地說明本發明，但本發明並不限制於下述實施例。 The following are examples and comparative examples to specifically illustrate the present invention, but the present invention is not limited to the following examples.
於進行實施例及比較例時，熱傳導性複合薄片的成型方法如同下述記載。 In Examples and Comparative Examples, a method for molding the thermally conductive composite sheet is as described below.
鋁箔：厚度50μm，面方向之熱傳導率236W/mK Aluminum foil: thickness 50μm, thermal conductivity in the plane direction 236W / mK
銅箔：厚度30μm，面方向之熱傳導率398W/mK Copper foil: thickness 30μm, surface thermal conductivity 398W / mK
(I-1)：將厚度為50μm的Cerac α(熱放射層：熱放射率0.96，包含平均粒徑5μm的氧化鋁的聚矽氧樹脂，Ceramission(股)製)層合至鋁箔(熱傳導層：厚度50μm)上而成的熱放射薄片。 (I-1): Cerac α (thermal emission layer: thermal emissivity: 0.96, silicone resin containing alumina having an average particle diameter of 5 μm, manufactured by Ceramission (strand)) having a thickness of 50 μm is laminated to an aluminum foil (heat conductive layer) : Heat radiation sheet formed on a thickness of 50 μm).
(I-2)：將厚度為30μm的Cerac α(熱放射層：熱放射率0.96，Ceramission(股)製)層合至銅箔(熱傳導層：厚度30μm)上而成的熱放射薄片。 (I-2): A heat radiation sheet in which Cerac α (thermal emission layer: thermal emissivity 0.96, manufactured by Ceramission (strand)) was laminated on a copper foil (heat conduction layer: 30 μm thick) with a thickness of 30 μm.
(I-3)：Morgen sheet MG01-S((股)淺利電機製；於厚度60μm、熱傳導率230W/mK的鋁箔上，層合厚度30μm、熱放射率0.99的熱放射性聚乙烯樹脂(包含平均粒徑1μm的黑鉛的聚酯樹脂)而成的熱放射薄片)。 (I-3): Morgen sheet MG01-S ((shares) shallow electric mechanism; on a 60 μm thick aluminum foil with a thermal conductivity of 230 W / mK, laminated with a 30 μm thickness and thermal emissivity of 0.99 thermal radioactive polyethylene resin Heat radiation sheet) made of black lead polyester resin) having an average particle diameter of 1 μm).
(II-1)~(II-4)：具有下述表中所示阿斯克C(Asker C)硬度及熱傳導率的熱傳導性聚矽氧樹脂層。 (II-1) to (II-4): Thermally conductive polysiloxane resin layers having Asker C hardness and thermal conductivity shown in the following table.
藉由貼合上述熱放射薄片及上述熱傳導性聚矽氧樹脂層而得到熱傳導性複合薄片。 A heat conductive composite sheet is obtained by bonding the heat radiation sheet and the heat conductive silicone resin layer.
用於對比，亦將下述(II-5)~(II-7)與熱放射薄片貼合使用：(II-5)非熱傳導性的聚矽氧樹脂層(熱傳導率0.16W/mK)；(II-6)熱傳導性聚矽氧雙面膠帶(熱傳導率1.0W/mK)；(II-7)丙烯酸雙面黏著膠 帶。 For comparison, the following (II-5) ~ (II-7) are also used in combination with the heat radiation sheet: (II-5) non-thermal conductive polysiloxane resin layer (thermal conductivity 0.16W / mK); (II-6) Thermally conductive polysiloxane double-sided tape (thermal conductivity 1.0W / mK); (II-7) Acrylic double-sided adhesive band.
構成上述樹脂層(II-1)~(II-7)的組成物(ii-1)~(ii-7)之組成如下述所示。 The composition of the compositions (ii-1) to (ii-7) constituting the resin layers (II-1) to (II-7) is shown below.
以下述式所示之有機聚矽氧烷，
(a-1)黏度：600mm2/s (a-1) Viscosity: 600mm 2 / s
(a-2)黏度：30,000mm2/s (a-2) Viscosity: 30,000mm 2 / s
(b-1)平均粒徑30μm的氫氧化鋁粉 (b-1) Aluminum hydroxide powder with an average particle diameter of 30 μm
(b-2)平均粒徑50μm的氧化鋁粉 (b-2) Alumina powder with an average particle size of 50 μm
(b-3)平均粒徑10μm的氧化鋁粉 (b-3) Alumina powder with an average particle size of 10 μm
以下述式所示之有機氫聚矽氧烷，
5質量%氯化鉑酸2-乙基己醇溶液 5 mass% 2-ethylhexanol chloride platinic acid solution
乙炔基亞甲基甲醇 Ethynylmethylene methanol
僅由Me3SiO0.5單位(M單位)及SiO2單位(Q單位)所成的聚矽氧樹脂(Me為表示甲基，M/Q莫耳比為1.15)之甲苯溶液(不揮發分60質量%，黏度30mm2/s)。 A toluene solution of a polysiloxane resin (Me is a methyl group and M / Q molar ratio is 1.15) made of Me 3 SiO 0.5 units (M units) and SiO 2 units (Q units). Mass%, viscosity 30mm 2 / s).
以下述式所表示(平均聚合度30)，並將單末端以三甲氧基矽烷基封端之二甲基聚矽氧烷。 Dimethyl polysiloxane represented by the following formula (average degree of polymerization: 30) and having a single end terminated with a trimethoxysilyl group.
聚矽氧組成物(ii-5)，包含：(甲)僅由Me3SiO0.5單位(M單位)及SiO2單位(Q單位)所成的聚矽氧樹脂(Me為表示甲基，M/Q莫耳比為1.15)之甲苯溶液(不揮發分60質量%，黏度30mm2/s)、(乙)平均聚合度8,000的以二甲基乙烯基將兩末端密封的二甲基聚矽氧烷、(丙)乙炔基亞甲基甲醇、(丁)式(5)中，q=1、r=40的有機氫聚矽氧烷、(戊)5質量%氯化鉑酸2-乙基己醇溶液、(己)甲苯，以質量比例為(甲)/(乙)/(丙)/(丁)/(戊)/(己)=65/20/0.05/0.15/0.1/14.7之聚矽氧黏著材組成物。 Poly silicon oxide composition (ii-5), comprising :( A) only by Me 3 SiO 0.5 unit (M unit) and SiO 2 units (Q units) formed by silicone poly (Me is a methyl group, M / Q Molar ratio of 1.15) in toluene solution (60% by mass of non-volatile matter, viscosity 30mm 2 / s), (B) dimethylpolysilicone sealed at both ends with dimethylvinyl with an average polymerization degree of 8,000 Oxane, (prop) ethynylmethylene methanol, (but) in formula (5), organohydrogenpolysiloxane of q = 1, r = 40, (pentyl) 5% by mass of chloroplatinic acid 2-ethyl Hexyl alcohol solution and (hexane) toluene, the mass ratio is (A) / (B) / (C) / (D) / (P) / (H)) = 65/20 / 0.05 / 0.15 / 0.1 / 14.7 Composition of polysiloxane adhesive material.
組成物(ii-7)，包含：(庚)2-乙基己基丙烯酸酯、(辛)丙烯酸、(壬)己二醇二丙烯酸酯，以質量比例為(庚)/(辛)/(壬)=97/3/0.03之丙烯酸樹脂組成物。 Composition (ii-7) contains: (heptane) 2-ethylhexyl acrylate, (octyl) acrylic acid, (non) hexanediol diacrylate, and the mass ratio is (heptane) / (octyl) / (nonyl) ) = 97/3 / 0.03 acrylic resin composition.
上述樹脂組成物為使用行星式混合機混練而得到。 The resin composition is obtained by kneading using a planetary mixer.
(ii-1)~(ii-3)：將所得到的組成物流入至氟處理薄膜，以成為指定厚度之方式使用模具，以120℃/10分來進行壓製硬化。 (ii-1) to (ii-3): The obtained composition was fed into a fluorine-treated film, and a mold was used so as to have a predetermined thickness, and press-hardened at 120 ° C / 10 minutes.
(ii-4)~(ii-6)：將所得到的組成物以成為指定厚度之方式塗布至氟處理薄膜上，以80℃/10分使溶劑乾燥並以120℃/10分使硬化。 (ii-4) to (ii-6): The obtained composition was applied to a fluorine-treated film so as to have a predetermined thickness, and the solvent was dried at 80 ° C / 10 minutes and cured at 120 ° C / 10 minutes.
(ii-7)：將所得到的組成物塗布至氟處理薄膜上，以照射中心波長360nm的UV燈來使硬化。 (ii-7): The obtained composition was applied to a fluorine-treated film, and was cured by irradiating a UV lamp with a center wavelength of 360 nm.
將如下述表中所示各種的熱放射薄片及各種的樹脂層貼合來調製複合薄片，並使用下述評估方法來進行評估。 Various heat radiation sheets and various resin layers are laminated as shown in the following table to prepare a composite sheet, and evaluation is performed using the following evaluation method.
對於尺寸30×120mm且厚度為2mm的鋁平板施加15W的電力並加熱，在溫度到達一定(64~66℃)時，將尺寸30×100mm的複合薄片貼附至鋁平板，測定1分後的鋁平板之溫度。尚，測定環境為25±2℃、濕度50%±5%。 Apply 15W of power to an aluminum flat plate with a size of 30 × 120mm and a thickness of 2mm. When the temperature reaches a certain value (64 ~ 66 ° C), attach a composite sheet with a size of 30 × 100mm to the aluminum flat plate. Temperature of aluminum flat plate. The measurement environment is 25 ± 2 ° C, and the humidity is 50% ± 5%.
如實施例1~7所示般，藉由於面內之熱傳導率為200W/mK以上的「熱傳導層」上層合厚度10~100μm、較佳為熱放射率為0.80以上的「熱放射層」而形成熱放射薄片，再於此熱放射薄片的熱傳導層側，以0.2mm以上之厚度層合硬度為阿斯克C(Asker C)40以下、較佳為熱傳導率為1.4W/mK以上的「熱傳導性聚矽氧樹脂層」，可得到熱源之降溫效果。特別是，熱傳導性聚矽氧層之熱傳導率為高，且厚度以越厚者熱源之降溫效果為越高。 As shown in Examples 1 to 7, the "heat radiation layer" having a thickness of 10 to 100 µm and preferably a heat emissivity of 0.80 or more is laminated on the "heat conduction layer" having a thermal conductivity of 200 W / mK or more in the plane. A heat radiation sheet is formed, and on the heat conductive layer side of the heat radiation sheet, a thickness of 0.2 mm or more is laminated with a hardness of "Asker C" 40 or less, preferably a heat conductivity of 1.4 W / mK or more. "Polysilicone resin layer" can get the cooling effect of heat source. In particular, the thermal conductivity of the thermally conductive polysilicon layer is high, and the thicker the thickness, the higher the cooling effect of the heat source.
如比較例1、2所示般，當層合熱傳導率為非 常低的聚矽氧樹脂層至熱放射薄片時，無法將來自熱源的熱量效率良好地傳遞至熱放射層。如比較例3、4所示般，當阿斯克C硬度超過40時，降溫效果會變小。如比較例5所示般，使用丙烯酸製雙面黏著膠帶時，不僅無法將來自熱源的熱量效率良好地傳遞至熱傳導層，由於丙烯酸樹脂相較於聚矽氧樹脂為缺乏耐熱性，故於直接接觸於熱源部位之使用，其長期可靠性為不安定。 As shown in Comparative Examples 1 and 2, when the laminated thermal conductivity is not When the normally low polysiloxane resin layer is applied to the heat radiation sheet, the heat from the heat source cannot be efficiently transmitted to the heat radiation layer. As shown in Comparative Examples 3 and 4, when the Asker C hardness exceeds 40, the cooling effect becomes small. As shown in Comparative Example 5, when an acrylic double-sided adhesive tape is used, not only the heat from the heat source cannot be efficiently transferred to the heat-conducting layer, but the acrylic resin lacks heat resistance compared to the silicone resin, so it is directly When used in contact with heat sources, its long-term reliability is unstable.
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