201116615 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種熱傳導組合物，以及利用該組合物所 製得之具有導熱性及柔軟性的軟墊。 【先前技術】 由於電子裝置的性能提昇及電腦速度高速化的結果，積 體電路、電晶體、半導體等電子元件所釋放出的熱量越來 越多’過高的溫度會對電子元件的性能及所搭，配裝置的操 ® 作造成負面影響。為使該等發熱電子元件於適當的溫度下 正常運作’可藉由熱傳導將熱由電子元件移至散熱器，而 散熱器則可利用任何習知之方式冷卻，例如對流或輻射技 術。 然而，一般散熱器與電子元件並不具有良好的表面平整 度，不易達到二表面緊密接合，導致二者相互貼合時存在 空氣間隙’而空氣為熱傳導率極差的傳熱介質，其導熱係 • 數約為0.025 W/m_K，將阻礙熱傳遞的路徑而增加熱阻 (thermal resistance)。通常可利用熱介面材料 interface material)填補散熱器與電子元件間的空氣間隙， 增加接觸面積、減小介面熱阻，從而提昇散熱效果，確保 電子元件之正常運作。熱介面材料之熱阻越低，則由電子 元件傳導至散熱器的熱越多。 大部分熱介面材料的導熱係數亦不高，一般在〇15至 〇.30W/m.K的範圍。為增加熱介面材料的熱傳能力，可添 加熱傳導填充物於聚合物基質中。 140867.doc 201116615 部分熱介面材料為將矽油與熱傳導填充物混合而成的導 熱膏’然而’導熱膏在長期使用時會因矽油受熱而產生溢 油現象。熱介面材料可具有不同的硬度以因應不同的應 用。部分熱介面材料為充填熱傳導填充物之彈性體。曰本 專利案第2004-323603號揭示一種熱塑性彈性體組合物， 其包含軟化劑組合物及氫化或部分氫化之嵌段共聚物，該 軟化劑組合物包含非芳族碳氫橡膠軟化劑、發泡劑及界面 活性劑。然而，彈性體需要較大的扣合壓力以提高散熱效 率，因而導致機械應力的增加。 在某些產品應用中’例如印刷電路板，熱介面材料需要 具有較柔軟的性質以符合不同裝置高度的要求。中華民國 專利公告第129975 1號係關於一種具有柔軟性之導熱性材 料用樹脂組成物，其包含聚合物（1)、液態塑化劑（π)以及 導熱係數為20 W/m.K以上的導熱性填充劑（111)。 【發明内容】 本發明之一目的係提供一種熱傳導組合物，其包含： (a) 聚合物基質； (b) 熱傳導填充物；及 (c) 液態烴油，其具有低於〇<5(：之玻璃轉移溫度（丁呂）。 本毛月另目的係美供一種由前述熱傳導組合物所製得 而具有導熱性及柔軟性的軟墊。 、 【實施方式】 為使本發明之特徵和優點能更明顯易懂，下文特舉本發 明之較佳貫施方式，並配合所附圖式詳細說明如下： 140867.doc 201116615 熱傳導組合物 本發明係關於一種熱傳導組合物，其包含： (a) 聚合物基質； (b) 熱傳導填充物；及 (C)液悲烴油，其具有低於〇。(：之玻璃轉移溫度（Tg)。 聚合物基質 適用於本發明組合物中作為組份（a)之聚合物基質可根據 φ 所需性質（如耐熱性、耐用性及機械強度）而加以選擇，且 其成分及固化方式並無特別限制。聚合物基質可包含熱塑 性或熱固性樹脂（如環氧樹脂及聚胺酯）、橡膠材料（如矽氧 烷及氟碳橡膠）及各種熱塑性彈性體（如聚乙烯 '聚丙烯、 聚苯乙烯、聚曱基丙烯酸甲酯 '聚氯乙烯、尼龍、聚碳酸 酉曰、聚對苯二曱酸乙二醇酯及玻璃纖維）。此聚合物基質 亦可包含未固化材料’並藉由固化反應而產生聚合物基 ^ 本發明熱傳導組合物可捧合一種、二種或二種以上此 φ 等聚合物基質。適用於本發明之聚合物基質較佳為矽氧 烧’其係由於矽氧烷具有優異之耐熱性，且對於電子零件 具有良好的嚙合性及附著性。 本發明組合物中，聚合物基質之含量，以整體組合物總 重量計，係約1重量％至約25重量％，較佳約1重量％至約 1 5重量％。 熱傳導填充物 本發明組合物之組份（b)為熱傳導填充物，其係分散於 組份（a)之聚合物基質中。適用於本發明組合物之熱傳導填 140867.doc 201116615 充物可為無機粉末、金屬氧化物、金屬顆粒或其組合。舉 例言之，前述無機粉末及金屬氧化物可包含但不限於氮化 硼、氮化鋁、氧化鋁、氧化鎂、氧化鈹、氧化鋅、鈦酸 鋇、鑽石、石1 '碳_、碳化鎢或其組合；前述金屬顆 粒可包含但不限於銅'金、鎳、紹、銀、此等金屬之合金 或其組合。 熱傳導填充物於本發明組合物中之含量為本I明領域之 技勢人士可依所需自行調整的。通常，以整體組合物總重 量計，係約30重量％至約％重量％，較佳約6〇重量％至約 90重量％。 為了提高在組合物中的分散性、增加填充量或降低與聚 合物基質之界面阻抗，前述熱傳導填充物可依需要利用石夕 烷處理劑或界面活性劑等來進行表面處理，以改善熱傳導 填充物的表面化性及分散後的流變性質與穩定性。同時， 作為熱傳導填充物的形狀可包含但不限於球形、纖維狀、 鱗片狀、平面狀、粉碎狀、不定形狀等。 具有低於o°c之玻璃轉移溫度的液態烴油 本發明組合物之組份（c)為具有低於之玻璃轉移溫度 的液態烴油。烴油為有機油類，適用於本發明組合物之烴 油為直鏈或支鏈、飽和或不飽和之脂族或芳族烴類化合 物，其玻璃轉移溫度低於〇。(3，較佳為低於-1〇。匚，且於室 溫下以液體之形式存在。適用於本發明之烴油較佳為莲麻 油、石蠟油或由Lubrizol所製造販售之s〇LspERSE 16_。 本發明組合物中，液態烴油之含量，以整體組合物總重 140867.doc 201116615 里计，係約0.01重量％至約2〇重量％，較佳約〇 〇1重量％至 約5重量％。 選用成分 本發明組合物視需要可加入此技術領域具有通常知識者 所热知之添加劑，其例如但不限於阻燃劑、交聯劑、固化 "、 偶& ^丨抗氧化劑、安定劑、乳化劑、抗沉降劑、可 塱d顏料或其混合物。該添加劑總量，以組合物總重量 0 計，係少於1〇重量％。 u本發明組合物可於室溫下藉由混合組份（a)、（b)及（C)而 製侍’較佳之混合溫度為15至50〇C，並可視需要加入上 述添加劑。 熱傳導軟塾 本心明亦關於一種包含前述熱傳導組合物之軟墊，其可 料熱介面材料。本發明軟墊之成型方法可包含但不限於 麗機成形去、到刀法、刮條塗佈機法、壓延加工法、擠壓 籲成形法及鑄模法。本發明軟塾可視情況為片狀、帶狀 '半 球狀、圓錐狀或角錐狀。 本發明熱傳導軟墊可視情況在至少一表面上覆蓋離型 膜，該離型膜可包含但不限於由聚g旨、％乙稀、聚氯乙 烤、聚丙焊、聚醯胺、醋酸纖維素等所製成之積層紙或薄 膜。當本發明軟墊於加工過程中無法穩定地成型時，可視 f月況塗佈於基材之至少—表面上’該基材可為導熱材料、 導電材料或其組合。 圖1所示為本發明熱傳導軟墊之一具體實施例。可作為 140867.doc 201116615 熱介面材料之軟墊丨包含基材丨丨、本發明熱傳導組合物層 12及離型膜13 β 本發明將經由下列實施例進一步加以詳細描述，唯該敘 述僅係用以例示說明本發明，而非對本發明範圍作任何限 制，任何熟悉此項技藝之人士可輕易達成之修飾及改變均 包括於本案說明書揭示内容及所附申請專利範圍之範圍 内。 實施例 實例1至3及比較例1及2 實例1至3及比較例1及2係依據表1十所示之組成及含量 (重量％)所混合製備而成之熱傳導組合物。 表1 (重量％) 實例 比較例 1 2 3 1 2 GUN 751 3.57 3.6 3.6 3.6 3.6 聚合物基質 矽氧烷 AK30000 5.4 5.4 5.4 5.4 5.4 AK1000 7.6 7.6 7.6 7.6 7.6 熱傳導填充物 氧化鋁 76.85 76.82 76.82 77.5 76.82 乾麻油 0.68 液態烴油 石蠟油 SOLSPERSE 16000 0.68 0.68 塑化劑 Santicizer® 141 0.68 交聯劑 VTMO 0.5 0.5 0.5 0.5 0.5 阻燃劑 SR-2816 5.24 5.24 5.24 5.24 5.24 固化劑 C6 0.16 0.16 0.16 0.16 0.16 140867.doc 201116615 熱壓成型 利用橡膠加硫成型機（熱壓成型機）將實例丨至3及比較例 1及2之組合物製成尺寸為315 mm X 3 15 mm X 1 mm之熱傳 導軟塾。熱壓機之模具尺寸為325 mm x 325 mm χ 1 mm， 成型溫度為160至180°C，固化時間為120至250秒。 硬度測試 將實例1至3及比較例1及2之組合物所製得的熱傳導軟墊 以Shore 〇〇硬度計測試，其結果以Sh〇re 〇〇表示並顯示於 表2中。 傳導性測試 根據 ASTM (American Society for Testing and Materials) D547〇中所描述之標準測試方法，對實例1及比較例1之組 合物所製得的熱傳導軟墊進行傳導性測試。所得結果顯示 於表2中。 熱穩定性測試 將實例1及比較例1之組合物所製得的熱傳導軟墊切分成 六片’其尺寸為2.54 cm X 5 cm X 0.1 cm，並平鋪於鋁板表 面’然後置於設定為150°C之烘箱中保持分別24小時及兩 週’觀察其重量損失之變化。重量損失率係由如下公式測 得》 (測量前重量-測量後重量）/測量前重量X 1 〇〇% 所仵結果顯示於表2中。 140867.doc 201116615 表2 _比較例 l__3 1 2201116615 VI. Description of the Invention: [Technical Field] The present invention relates to a heat-conductive composition, and a cushion having thermal conductivity and flexibility obtained by using the composition. [Prior Art] As a result of the improvement of the performance of electronic devices and the speed of computer speed, more and more heat is released from electronic components such as integrated circuits, transistors, semiconductors, etc. 'Excessive temperature will affect the performance of electronic components and The operation of the device is negatively affected by the operation of the device. In order for the heat-generating electronic components to function properly at the appropriate temperature, heat can be transferred from the electronic components to the heat sink by thermal conduction, and the heat sink can be cooled by any conventional means, such as convection or radiation techniques. However, in general, the heat sink and the electronic component do not have a good surface flatness, and it is difficult to achieve close contact between the two surfaces, resulting in an air gap when the two are attached to each other, and the air is a heat transfer medium having extremely poor thermal conductivity, and the heat conduction system thereof • The number is approximately 0.025 W/m_K, which will hinder the path of heat transfer and increase thermal resistance. The interface material can be used to fill the air gap between the heat sink and the electronic components, increase the contact area, and reduce the thermal resistance of the interface, thereby improving the heat dissipation effect and ensuring the normal operation of the electronic components. The lower the thermal resistance of the thermal interface material, the more heat is transferred from the electronic component to the heat sink. The thermal conductivity of most thermal interface materials is also not high, typically in the range of 〇15 to 〇.30W/m.K. To increase the heat transfer capability of the thermal interface material, a conductive filler can be added to the polymer matrix. 140867.doc 201116615 Part of the thermal interface material is a thermal paste that mixes eucalyptus oil with a heat conductive filler. However, the thermal grease will cause oil spillage due to the heat of the sputum oil during long-term use. Thermal interface materials can have different hardnesses to accommodate different applications. A portion of the thermal interface material is an elastomer filled with a thermally conductive filler. A thermoplastic elastomer composition comprising a softener composition and a hydrogenated or partially hydrogenated block copolymer comprising a non-aromatic hydrocarbon rubber softener, hair, is disclosed in Japanese Patent Publication No. 2004-323603 Foaming agent and surfactant. However, the elastomer requires a large fastening pressure to increase the heat dissipation efficiency, thus causing an increase in mechanical stress. In some product applications, such as printed circuit boards, thermal interface materials need to have softer properties to meet the height requirements of different devices. The Republic of China Patent Publication No. 129975 1 relates to a resin composition for a flexible thermal conductive material comprising a polymer (1), a liquid plasticizer (π), and a thermal conductivity of 20 W/mK or more. Filler (111). SUMMARY OF THE INVENTION One object of the present invention is to provide a heat transfer composition comprising: (a) a polymer matrix; (b) a thermally conductive filler; and (c) a liquid hydrocarbon oil having a lower than <5 ( The glass transition temperature (Ding Lu). The purpose of the present invention is to provide a cushion which is made of the above heat-conductive composition and has thermal conductivity and flexibility. [Embodiment] In order to make the characteristics of the present invention The advantages are more apparent and the following description of the preferred embodiment of the invention is described in detail below with reference to the accompanying drawings: 140867.doc 201116615 Thermal Conductive Composition The present invention relates to a thermally conductive composition comprising: a polymer matrix; (b) a thermally conductive filler; and (C) a liquid hydrocarbon oil having a glass transition temperature (Tg) lower than that of 〇. The polymer matrix is suitable for use as a component in the composition of the present invention. The polymer matrix of (a) may be selected according to the desired properties of φ (e.g., heat resistance, durability, and mechanical strength), and the composition and curing manner thereof are not particularly limited. The polymer matrix may contain a thermoplastic or thermosetting resin ( Such as epoxy resin and polyurethane), rubber materials (such as decane and fluorocarbon rubber) and various thermoplastic elastomers (such as polyethylene 'polypropylene, polystyrene, polymethyl methacrylate' PVC, nylon, Polycarbonate, polyethylene terephthalate, and glass fiber). The polymer matrix may also contain an uncured material 'and produce a polymer base by a curing reaction. ^ The heat conductive composition of the present invention can be combined One, two or more polymer matrices such as φ. The polymer matrix suitable for use in the present invention is preferably oxy-oxygenated because it has excellent heat resistance and good meshing for electronic parts. Properties and Adhesion. The polymer matrix is present in the compositions of the invention in an amount of from about 1% by weight to about 25% by weight, based on the total weight of the total composition, preferably from about 1% by weight to about 15% by weight. Filler Component (b) of the composition of the present invention is a heat conductive filler which is dispersed in the polymer matrix of component (a). Suitable for heat transfer of the composition of the present invention 140867.doc 201116615 Filling may be inorganic Finally, the metal oxide, the metal particles or a combination thereof. For example, the inorganic powder and the metal oxide may include, but are not limited to, boron nitride, aluminum nitride, aluminum oxide, magnesium oxide, cerium oxide, zinc oxide, and titanic acid.钡, diamond, stone 1 'carbon _, tungsten carbide or a combination thereof; the foregoing metal particles may include, but are not limited to, copper 'gold, nickel, sulphur, silver, alloys of such metals or combinations thereof. Thermally conductive fillers in the combination of the present invention The content of the present invention can be adjusted as needed by the skilled person in the field. Generally, it is from about 30% by weight to about 3% by weight, preferably about 6% by weight, based on the total weight of the total composition. About 90% by weight. In order to improve the dispersibility in the composition, increase the filling amount or reduce the interfacial resistance with the polymer matrix, the above-mentioned heat-conductive filler may be surface-treated by using an astaxane treatment agent or a surfactant or the like as needed. To improve the surface properties of the heat transfer filler and the rheological properties and stability after dispersion. Meanwhile, the shape as the heat conductive filler may include, but is not limited to, a spherical shape, a fibrous shape, a scale shape, a planar shape, a pulverized shape, an indefinite shape, and the like. Liquid hydrocarbon oil having a glass transition temperature lower than o °c Component (c) of the composition of the present invention is a liquid hydrocarbon oil having a glass transition temperature lower than that. The hydrocarbon oil is an organic oil, and the hydrocarbon oil suitable for use in the composition of the present invention is a linear or branched, saturated or unsaturated aliphatic or aromatic hydrocarbon compound having a glass transition temperature lower than that of hydrazine. (3, preferably less than -1 Torr. 匚, and exists in the form of a liquid at room temperature. The hydrocarbon oil suitable for use in the present invention is preferably lotus oil, paraffin oil or sold by Lubrizol. LspERSE 16_. The liquid hydrocarbon oil content of the composition of the present invention is from about 0.01% by weight to about 2,000% by weight based on the total weight of the whole composition of 140867.doc 201116615, preferably about 〇〇1% by weight to about 5% by weight. Ingredients The composition of the present invention may be added to an additive known to those skilled in the art as needed, such as, but not limited to, flame retardant, crosslinking agent, curing ", even & , stabilizer, emulsifier, anti-settling agent, 塱d pigment or a mixture thereof. The total amount of the additive is less than 1% by weight based on the total weight of the composition. u The composition of the present invention can be at room temperature By mixing the components (a), (b) and (C), the preferred mixing temperature is 15 to 50 〇C, and the above additives may be added as needed. The heat conduction soft 塾 is also related to a heat conduction including the foregoing. A cushion of the composition that can be a thermal interface material. The molding method of the cushion of the present invention may include, but is not limited to, a machine forming, a knife-to-blade method, a bar coater method, a calendering method, an extrusion-molding method, and a molding method. The soft palate of the present invention may be in the form of a sheet. The strip-shaped hemispherical, conical or pyramidal shape. The heat conductive cushion of the present invention may cover at least one surface with a release film, which may include, but is not limited to, polyg, % ethyl, polychlorinated Laminated paper or film made of baking, polypropylene welding, polyamide, cellulose acetate, etc. When the cushion of the present invention cannot be stably formed during processing, it can be applied to at least the substrate at the same time. On the surface, the substrate may be a heat conductive material, a conductive material or a combination thereof. Fig. 1 shows a specific embodiment of the heat conduction cushion of the present invention. It can be used as a cushion for the thermal interface material of 140867.doc 201116615. The heat transfer composition layer 12 and the release film 13 of the present invention are further described in the following examples, which are merely intended to illustrate the invention, and are not intended to limit the scope of the invention. The modifications and variations that can be easily made by those skilled in the art are included in the scope of the disclosure of the present specification and the scope of the appended claims. Examples Examples 1 to 3 and Comparative Examples 1 and 2 Examples 1 to 3 and Comparative Examples 1 and 2 A heat-conducting composition prepared according to the composition and content (% by weight) shown in Table 10. Table 1 (% by weight) Example Comparative Example 1 2 3 1 2 GUN 751 3.57 3.6 3.6 3.6 3.6 Polymer matrix 矽Oxyalkane AK30000 5.4 5.4 5.4 5.4 5.4 AK1000 7.6 7.6 7.6 7.6 7.6 Heat Transfer Filler Alumina 76.85 76.82 76.82 77.5 76.82 Dry sesame oil 0.68 Liquid hydrocarbon oil paraffin oil SOLSPERSE 16000 0.68 0.68 Plasticizer Santicizer® 141 0.68 Crosslinker VTMO 0.5 0.5 0.5 0.5 0.5 Flame Retardant SR-2816 5.24 5.24 5.24 5.24 5.24 Curing Agent C6 0.16 0.16 0.16 0.16 0.16 140867.doc 201116615 Hot Pressing Using a rubber vulcanizing machine (hot press forming machine), examples are given to 3 and Comparative Example 1 and The composition of 2 is made of a heat conductive soft palate having a size of 315 mm X 3 15 mm X 1 mm. The hot press has a die size of 325 mm x 325 mm χ 1 mm, a molding temperature of 160 to 180 ° C, and a curing time of 120 to 250 seconds. Hardness Test The heat conductive cushions prepared in the compositions of Examples 1 to 3 and Comparative Examples 1 and 2 were tested with a Shore 〇〇 hardness tester, and the results are shown by Sh 〇 re 〇〇 and shown in Table 2. Conductivity Test Conductive tests were performed on the thermally conductive cushions prepared in the compositions of Examples 1 and 1 according to the standard test methods described in ASTM (American Society for Testing and Materials) D547. The results obtained are shown in Table 2. Thermal stability test The heat conductive cushions prepared in the compositions of Example 1 and Comparative Example 1 were cut into six pieces 'having a size of 2.54 cm X 5 cm X 0.1 cm and laid flat on the surface of the aluminum plate' and then set to The change in weight loss was observed by keeping the oven at 150 ° C for 24 hours and two weeks, respectively. The weight loss rate was measured by the following formula (pre-measurement weight - post-measurement weight) / pre-measurement weight X 1 〇〇%. The results are shown in Table 2. 140867.doc 201116615 Table 2 _Comparative Example l__3 1 2
Shore 00 35 45 57 75 65 ASTMD5470 (W/m.K) 1.7 1.8 重量損失率 (重量％) 24小時 兩週 0.39 0.79 ------- 0.26 0.41 以下申明專利範圍係用以界定本發明之合理保護範圍。 然應明瞭者，技藝人士基於本發明之揭示所可達成之種種 顯而易見之改良，亦應歸屬本發明合理之保護範圍。 【圖式簡單說明】 圖1代表本發明軟墊之示意圖。 【主要元件符號說明】 I 軟墊 II 基材 12 本發明熱傳導組合物層 13 離型膜 140867.doc -10-Shore 00 35 45 57 75 65 ASTMD5470 (W/mK) 1.7 1.8 Weight loss rate (% by weight) 24 hours two weeks 0.39 0.79 ------- 0.26 0.41 The following patent claims are intended to define the reasonable protection of the present invention. range. It should be understood that the obvious modifications that can be made by those skilled in the art based on the present disclosure are also intended to be within the scope of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a cushion of the present invention. [Description of main component symbols] I Pad II Substrate 12 Thermal conductive composition layer of the present invention 13 Release film 140867.doc -10-