TWI780100B - Thermally conductive resin composition, heat dissipation sheet, heat dissipation member, and manufacturing method thereof - Google Patents
Thermally conductive resin composition, heat dissipation sheet, heat dissipation member, and manufacturing method thereof Download PDFInfo
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- TWI780100B TWI780100B TW107100868A TW107100868A TWI780100B TW I780100 B TWI780100 B TW I780100B TW 107100868 A TW107100868 A TW 107100868A TW 107100868 A TW107100868 A TW 107100868A TW I780100 B TWI780100 B TW I780100B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
Abstract
提供能夠得到具有高熱傳導性和高柔軟性的樹脂成形體的熱傳導性樹脂組成物。 Provided is a thermally conductive resin composition capable of obtaining a resin molded article having high thermal conductivity and high flexibility.
一種熱傳導性樹脂組成物，其包含以下的成分(A)~(D)，以阿斯克C(ASKER C)計，樹脂成形體的硬度成為30以下。(A)包含至少在末端或者側鏈具有乙烯基的有機聚矽氧烷、和至少在末端或者側鏈具有2個以上的H-Si基的有機聚矽氧烷，25℃的黏度為100~2,500mPa．s的二液加成反應型液狀矽酮；(B)至少在末端或者側鏈具有2個以上的乙烯基的高分子量矽酮1~20體積%；(C)烷基烷氧基矽烷0.05~2體積%；(D)無機填料63~85體積%。 A thermally conductive resin composition comprising the following components (A) to (D), wherein the hardness of a resin molded body is 30 or less in terms of Asker C (ASKER C). (A) An organopolysiloxane comprising at least a vinyl group at a terminal or a side chain, and an organopolysiloxane having at least two H-Si groups at a terminal or a side chain, and having a viscosity at 25°C of 100~ 2,500mPa． s two-liquid addition reaction type liquid silicone; (B) 1-20% by volume of high-molecular-weight silicone having at least two or more vinyl groups at the terminal or side chain; (C) alkyl alkoxysilane 0.05 ~2% by volume; (D) 63~85% by volume of inorganic filler.
Description
本發明係關於熱傳導性樹脂組成物、樹脂成形體、散熱片、散熱構件及其製造方法。 The present invention relates to a thermally conductive resin composition, a resin molded body, a heat sink, a heat radiation member, and a manufacturing method thereof.
隨著電子零件的小型化、高輸出化，從那些電子零件產生的每單位面積的熱量變得非常大。其溫度上升，有引起電子零件的壽命降低、運作不良、故障之虞。因此，電子零件的冷卻使用了金屬製的散熱物(heat sink)或框體，為了進一步效率佳地將熱從電子零件傳遞至散熱物或框體等的冷卻部而使用了熱傳導性材料。作為使用此熱傳導性材料的理由，在使電子零件與散熱物等直接接觸的情況下，若細微地觀看，則在其界面有空氣存在而成為熱傳導的障礙。由此，使熱傳導性材料存在於電子零件與散熱物等之間以取代存在於界面的空氣，從而能夠效率佳地傳遞熱。 With miniaturization and higher output of electronic components, the amount of heat per unit area generated from those electronic components becomes very large. The rise in temperature may cause shortening of the life of electronic parts, malfunction, and failure. Therefore, metal heat sinks or frames are used to cool electronic components, and thermally conductive materials are used to more efficiently transfer heat from electronic components to cooling parts such as heat sinks and frames. The reason for using this thermally conductive material is that when an electronic component is brought into direct contact with a radiator or the like, air exists at the interface and becomes an obstacle to heat conduction when viewed finely. In this way, heat can be efficiently transferred by allowing the thermally conductive material to exist between the electronic component and the heat sink instead of the air present at the interface.
作為熱傳導性材料，有將熱傳導性粉末填充於樹脂而成者。作為該樹脂，可舉出：矽酮樹脂、丙烯酸樹脂、環氧樹脂等，從耐熱性、柔軟性的均衡性佳的觀點來看，大多使用矽酮樹脂。 As a heat conductive material, what filled resin with heat conductive powder exists. Examples of the resin include silicone resins, acrylic resins, epoxy resins, and the like, and silicone resins are often used from the viewpoint of a good balance between heat resistance and flexibility.
作為使用矽酮樹脂的熱傳導性材料，有將熱傳導性填充劑填充於矽酮橡膠或者矽酮凝膠的熱傳導 性片、或將熱傳導性填充劑填充於矽酮油的熱傳導性膏體等。膏體係與界面的緊貼比片高，可以薄膜化至熱傳導性填充劑的最大粒徑，因此能夠實現低熱阻。但是，由於是液狀，因此有引起滴落或溢出的缺點。另一方面，與膏體相比，片係作業性優異，此外，能夠壓縮並固定在電子零件與散熱物或者框體之間，如膏體般的滴落或溢出性良好。但是，片係固體且被壓縮使用，故而壓縮應力大，因此會有片的使用成為電子零件故障或框體歪斜的原因之一之虞。 Examples of thermally conductive materials using silicone resin include thermally conductive sheets filled with thermally conductive fillers in silicone rubber or silicone gel, thermally conductive pastes filled with thermally conductive fillers in silicone oil, and the like. The paste system has a higher adhesion to the interface than the sheet, and can be thinned to the maximum particle size of the thermally conductive filler, so low thermal resistance can be achieved. However, since it is liquid, it has a disadvantage of causing dripping or overflowing. On the other hand, compared with the paste, the sheet-based workability is excellent, and in addition, it can be compressed and fixed between the electronic component and the radiator or the frame, and the dripping or spilling like a paste is good. However, since the sheet is solid and used under compression, the compressive stress is large. Therefore, use of the sheet may cause failure of electronic components or distortion of the housing.
因為需要傳遞基板上的發熱體的熱而使其散熱至冷卻框體，因此在專利文獻1及專利文獻2中提出了散熱片。 Patent Document 1 and Patent Document 2 propose heat sinks because the heat from the heat generating body on the substrate needs to be transferred to the cooling frame.
具體而言，專利文獻1的請求項8中記載了一種熱傳導率為5.4W/mK以上且阿斯克C(ASKER C)硬度為60以下的散熱片，其係使用高熱傳導性樹脂組成物而製作出，其中，該高熱傳導性樹脂組成物係使用以體積比計包含60~90vol%的掺合粒子的高熱傳導性樹脂化合物而成形的，該掺合粒子係依以下的掺合而包含：60~80vol%的平均粒徑50~100μm的球狀礬土粒子、5~30vol%的平均粒徑0.5~7μm的球狀礬土粒子、10~35vol%的平均粒徑0.5~7μm的非球狀礬土粒子。 Specifically, Claim 8 of Patent Document 1 describes a heat sink having a thermal conductivity of 5.4 W/mK or higher and an Asker C (ASKER C) hardness of 60 or lower, which is produced using a high thermal conductivity resin composition. wherein, the high thermal conductivity resin composition is molded using a high thermal conductivity resin compound containing 60 to 90 vol% of blended particles in terms of volume ratio, and the blended particles are blended according to the following: 60 ~80vol% of spherical alumina particles with an average particle size of 50~100μm, 5~30vol% of spherical alumina particles with an average particle size of 0.5~7μm, and 10~35vol% of non-spherical alumina particles with an average particle size of 0.5~7μm Alumina particles.
此外，專利文獻2的請求項6中記載了一種熱傳導率為5.0W/mK以上且片硬度為60以下的樹脂成形體，其係以體積比計而在樹脂中包含超過72體積%~80體積%的礬土掺合粒子，其中，該礬土掺合粒子係 粒度分布在超過30μm~100μm、超過5μm~30μm、5μm以下的範圍內分別具有波峰，包含60~85體積%的粒度分布在超過30μm~100μm的範圍內的礬土粒子、5~15體積%的粒度分布在超過5μm~30μm以下的範圍內的礬土粒子、10~25體積%的粒度分布在5μm以下的範圍內的礬土粒子，該粒度分布在超過30μm~100μm的範圍內的礬土粒子為球狀粒子，該粒度分布在30μm以下的範圍內的礬土粒子為非球狀粒子。 In addition, Claim 6 of Patent Document 2 describes a resin molded article having a thermal conductivity of 5.0 W/mK or more and a sheet hardness of 60 or less, which contains more than 72% by volume to 80% by volume in the resin. % of alumina blended particles, wherein the particle size distribution of the alumina blended particles has peaks in the ranges of more than 30 μm to 100 μm, more than 5 μm to 30 μm, and less than 5 μm, including 60 to 85% by volume. Bauxite particles in the range of 30 μm to 100 μm, 5 to 15 volume % of alumina particles in the range of more than 5 μm to less than 30 μm, 10 to 25 volume % of alumina particles in the range of 5 μm or less Particles, the alumina particles with a particle size distribution in the range of more than 30 μm to 100 μm are spherical particles, and the alumina particles with a particle size distribution in the range of 30 μm or less are non-spherical particles.
專利文獻1 日本特開2007-277406號公報 Patent Document 1 Japanese Unexamined Patent Publication No. 2007-277406
專利文獻2 日本特開2009-274929號公報 Patent Document 2 Japanese Patent Application Laid-Open No. 2009-274929
而且，專利文獻1中，實際上，作為片硬度(10mm)低的散熱片，記載了能夠製作阿斯克C硬度為45且熱傳導率為5.4W/mK而礬土填充率為59體積%的散熱片(發明例30)、及阿斯克C硬度為42且熱傳導率為5.3W/mK而礬土填充率為77體積%的散熱片(比較例16)。 In addition, in Patent Document 1, as a heat sink with a low sheet hardness (10 mm), it is described that a heat sink with an Asc C hardness of 45, a thermal conductivity of 5.4 W/mK, and an alumina filling rate of 59% by volume can be produced. sheet (Invention Example 30), and a heat sink having an Asker C hardness of 42, a thermal conductivity of 5.3 W/mK, and an alumina filling rate of 77% by volume (Comparative Example 16).
此外，專利文獻2中，實際上，作為片硬度(2.5mm)低的散熱片，記載了能夠製作阿斯克C硬度為48且熱傳導率為5.2W/mK而礬土填充率為72.5體積%的散熱片(實施例46)、及阿斯克C硬度為39且熱傳導率為 4.6W/mK而礬土填充率為71.4體積%的散熱片(比較例45)。 In addition, in Patent Document 2, it is described that as a heat sink having a low sheet hardness (2.5 mm), it is possible to manufacture a heat sink having an Asc C hardness of 48, a thermal conductivity of 5.2 W/mK, and an alumina filling rate of 72.5% by volume. A heat sink (Example 46), and a heat sink (Comparative Example 45) having an Asker C hardness of 39, a thermal conductivity of 4.6 W/mK, and an alumina filling rate of 71.4% by volume.
目前，有在得到高熱傳導性的散熱片之際在樹脂組成物中高度填充無機填料的情況，但因無機填料的高度填充而損害散熱片的柔軟性。因此，在專利文獻1及專利文獻2中，只能將散熱片的阿斯克C硬度製作到39。儘管如此，現況是這樣的阿斯克C硬度的散熱片依然達不到所要求的柔軟性。 Conventionally, when obtaining a heat sink with high thermal conductivity, an inorganic filler is highly filled in a resin composition, but the flexibility of the heat sink is impaired by the high filling of the inorganic filler. Therefore, in Patent Document 1 and Patent Document 2, the Usk C hardness of the heat sink can only be produced up to 39. However, the current situation is that such heat sinks with Asker C hardness still cannot achieve the required flexibility.
具體而言，目前若要得到高熱傳導的散熱片，則散熱片的柔軟性惡化，因此有在夾持散熱片時對基板的應力大，所搭載的元件因基板的彎曲而剝離，或對散熱元件施加不合適的力的顧慮。 Specifically, if a heat sink with high thermal conductivity is to be obtained at present, the flexibility of the heat sink is deteriorated. Therefore, when the heat sink is clamped, the stress on the substrate is large, and the mounted components are peeled off due to the bending of the substrate, or the heat dissipation is affected. Concerns about components exerting undue force.
另外，若為了賦予散熱片的柔軟性而抑制無機填料的填充率，則自然有散熱片的熱傳導率下降而無法滿足需要的散熱特性的缺點。 In addition, if the filling rate of the inorganic filler is suppressed in order to impart flexibility to the heat sink, the thermal conductivity of the heat sink naturally decreases and the required heat dissipation characteristics cannot be satisfied.
由此，目前尚無法提供能夠滿足高熱傳導性和高柔軟性兩者的散熱片。 Therefore, it has not been possible to provide a heat sink that satisfies both high thermal conductivity and high flexibility.
即，本發明的主要目的為提供能夠得到具有高熱傳導性和高柔軟性的樹脂成形體的熱傳導性樹脂組成物。 That is, the main object of the present invention is to provide a thermally conductive resin composition capable of obtaining a resin molded article having high thermal conductivity and high flexibility.
因此，本發明人等為了解決上述課題而進行銳意檢討，結果發現到能夠提供可以藉由組合並使用：成分(A)包含具有乙烯基的有機聚矽氧烷、和具有H-Si基的有機聚矽氧烷，具有特定黏度的二液加成型矽 酮；(B)具有乙烯基的高分子量矽酮；及(C)烷基烷氧基矽烷，來得到高度含有無機填料而且具有高熱傳導性和高柔軟性的樹脂成形體的熱傳導性樹脂組成物。於是，本發明人等發現了可以藉由採用下述手段來達成目的。 Therefore, the inventors of the present invention earnestly examined in order to solve the above-mentioned problems, and as a result, found that it is possible to provide an organic polysiloxane containing a vinyl group and an organic polysiloxane having an H-Si group by combining and using the component (A). Polysiloxane, a two-component addition type silicone with a specific viscosity; (B) a high molecular weight silicone with a vinyl group; and (C) an alkylalkoxysilane, to obtain a highly inorganic filler and have high thermal conductivity A thermally conductive resin composition for a highly flexible resin molded product. Then, the inventors of the present invention found that the object can be achieved by adopting the following means.
即，本發明係由以下構成。 That is, the present invention is constituted as follows.
[1]一種熱傳導性樹脂組成物，其包含以下的成分(A)~(D)，以阿斯克C計，樹脂成形體的硬度成為30以下。 [1] A thermally conductive resin composition comprising the following components (A) to (D), wherein the hardness of the resin molded article is 30 or less in terms of Asker C.
(A)包含至少在末端或者側鏈具有乙烯基的有機聚矽氧烷、和至少在末端或者側鏈具有2個以上的H-Si基的有機聚矽氧烷，25℃的黏度為100~2,500mPa．s的二液加成反應型液狀矽酮 (A) An organopolysiloxane comprising at least a vinyl group at a terminal or a side chain, and an organopolysiloxane having at least two H-Si groups at a terminal or a side chain, and having a viscosity at 25°C of 100~ 2,500mPa． s two-liquid addition reaction type liquid silicone
(B)至少在末端或者側鏈具有2個以上的乙烯基的高分子量矽酮1~20體積% (B) 1-20% by volume of high-molecular-weight silicone having at least two vinyl groups at the terminal or side chain
(C)烷基烷氧基矽烷0.05~2體積% (C) Alkylalkoxysilane 0.05~2% by volume
(D)無機填料63~85體積% (D) Inorganic filler 63~85% by volume
[2]如[1]的熱傳導性樹脂組成物，其中前述成分(A)中的至少在末端或者側鏈具有乙烯基的有機聚矽氧烷、和至少在末端或者側鏈具有2個以上的H-Si基的有機聚矽氧烷的比係1：1.5~1.5：1。 [2] The thermally conductive resin composition according to [1], wherein the component (A) includes an organopolysiloxane having a vinyl group at least at a terminal or a side chain, and at least two or more vinyl groups at a terminal or a side chain. The ratio of H-Si based organopolysiloxane is 1:1.5~1.5:1.
[3]如[1]或[2]的熱傳導性樹脂組成物，其中前述無機填料的粒度分布係在平均粒徑10~100μm、1~10μm及小於1μm的範圍內具有極大值或者波峰，平均粒徑10~100μm的無機填料係23~50體積%，平均粒徑1~10μm的無機填料係15~30體積%， 平均粒徑小於1.0μm的無機填料係5~20體積%。 [3] The thermally conductive resin composition according to [1] or [2], wherein the particle size distribution of the inorganic filler has a maximum value or a peak in the range of an average particle diameter of 10 to 100 μm, 1 to 10 μm and less than 1 μm, and the average Inorganic fillers with a particle size of 10-100 μm are 23-50% by volume, inorganic fillers with an average particle size of 1-10μm are 15-30% by volume, and inorganic fillers with an average particle size of less than 1.0μm are 5-20% by volume.
[4]一種樹脂成形體，其由如[1]至[3]中任一項的熱傳導性樹脂組成物構成。 [4] A resin molded article composed of the thermally conductive resin composition according to any one of [1] to [3].
[5]一種散熱片，其使用如[1]至[3]中任一項的熱傳導性樹脂組成物。 [5] A heat sink using the thermally conductive resin composition according to any one of [1] to [3].
[6]一種用於通訊用構件的散熱片或者高熱傳導性散熱構件，其使用如[1]至[3]中任一項的熱傳導性樹脂組成物，熱傳導率為3W/mK以上且阿斯克C硬度為30以下。 [6] A heat sink or high thermal conductivity heat dissipation member for communication components, which uses the thermally conductive resin composition according to any one of [1] to [3], and has a thermal conductivity of 3 W/mK or more and Asker C hardness is 30 or less.
[7]一種如[1]至[3]中任一項的熱傳導性樹脂組成物的製造方法。 [7] A method for producing the thermally conductive resin composition according to any one of [1] to [3].
根據本發明的話，便能夠提供能夠得到具有高熱傳導性和高柔軟性的樹脂成形體的熱傳導性樹脂組成物，此外，能夠提供具有高熱傳導性和高柔軟性的樹脂成形體。 According to the present invention, it is possible to provide a thermally conductive resin composition capable of obtaining a resin molded article having high thermal conductivity and high flexibility, and to provide a resin molded article having high thermal conductivity and high flexibility.
以下，針對供實施本發明用的適合的實施形態進行說明。但是，本發明不限於以下的實施形態，能夠在本發明的範圍內自由地變更。不應依其狹隘地解釋本發明的範圍。 Hereinafter, suitable embodiments for carrying out the present invention will be described. However, the present invention is not limited to the following embodiments, and can be freely changed within the scope of the present invention. The scope of the present invention should not be construed narrowly therefrom.
本發明的樹脂組成物，係包含：成分(A)包含(a1)至少在末端或者側鏈具有乙烯基的有機聚矽氧烷、和(a2)至少在末端或者側鏈具有2個以上的H-Si基的有機聚矽氧烷，25℃的黏度為100~2,500mPa．s的二液加成反應型液狀矽酮；成分(B)具有兩末端乙烯基的高分子量矽酮1~20體積%；成分(C)烷基烷氧基矽烷0.05~2體積%；成分(D)無機填料63~85體積%；以阿斯克C計，樹脂成形體的硬度成為30以下的熱傳導性樹脂組成物。 The resin composition of the present invention comprises: component (A) comprising (a1) an organopolysiloxane having a vinyl group at least at a terminal or a side chain; and (a2) having at least two H at a terminal or a side chain -Si-based organopolysiloxane with a viscosity of 100~2,500mPa at 25°C. Two-liquid addition reaction type liquid silicone of s; component (B) 1-20 volume % of high molecular weight silicone with vinyl groups at both ends; component (C) 0.05-2 volume % of alkyl alkoxysilane; component (D) Inorganic filler 63 to 85% by volume; a thermally conductive resin composition having a hardness of a resin molded body of 30 or less in terms of Asker C.
在本發明的樹脂組成物中，成分(A)中的成分(a1)及成分(a2)、和成分(B)以及成分(C)之四成分進行反應而硬化，從而形成矽酮橡膠。於是，藉由使用成分(A)~(C)，即使樹脂組成物中有63~85體積%這樣高含量的無機填料，也能夠得到高柔軟性的樹脂成形體。 In the resin composition of the present invention, component (a1) and component (a2) in component (A), and four components of component (B) and component (C) are reacted and hardened to form silicone rubber. Therefore, by using the components (A) to (C), even if the resin composition has a high content of 63 to 85% by volume of the inorganic filler, a highly flexible resin molded article can be obtained.
另外，因為能夠高度含有無機填料，因此能夠得到高熱傳導性的樹脂成形體。 In addition, since the inorganic filler can be highly contained, a highly thermally conductive resin molded article can be obtained.
<成分(A)二液加成反應型液狀矽酮> <Component (A) two-component addition reaction type liquid silicone>
本發明的成分(A)二液加成反應型液狀矽酮係包含成分(a1)至少在末端或者側鏈具有乙烯基的有機聚矽氧烷(以下，也稱為「具有乙烯基的有機聚矽氧烷」。)、和成分(a2)至少在末端或者側鏈具有2個以上的H-Si基的有機聚矽氧烷(以下，也稱為「具有H-Si基的有機聚 矽氧烷」。)者。前述成分(A)，理想的是25℃的黏度為100~2,500mPa．s。此外，就適合程度而言，理想的是前述(a1)：前述(a2)的比在1：1.5~1.5：1之間。 Component (A) of the present invention is a two-component addition reaction type liquid silicone containing component (a1) an organopolysiloxane having a vinyl group at least at its terminal or side chain (hereinafter also referred to as "organopolysiloxane having a vinyl group"). Polysiloxane."), and component (a2) organopolysiloxane having at least two H-Si groups at least at the terminal or side chain (hereinafter also referred to as "organopolysiloxane having H-Si groups oxane".) The aforementioned component (A) preferably has a viscosity of 100~2,500mPa at 25°C. s. In addition, it is desirable that the ratio of the aforementioned (a1): the aforementioned (a2) is between 1:1.5 to 1.5:1 in terms of suitability.
前述成分(a1)係至少在末端或者側鏈中的任一處具有乙烯基的有機聚矽氧烷，可以是直鏈狀構造或者分枝狀構造中的任一者。一般而言，具有乙烯基的有機聚矽氧烷係有機聚矽氧烷的分子內(Si-R)的R部分的一部分成為乙烯基者(例如，參照以下的一般式(a1-1)~(a1-4))。 The aforementioned component (a1) is an organopolysiloxane having a vinyl group at least at any one of a terminal or a side chain, and may have either a linear structure or a branched structure. In general, a part of the R moiety in the molecule (Si-R) of an organopolysiloxane-based organopolysiloxane having a vinyl group becomes a vinyl group (for example, refer to the following general formula (a1-1)~ (a1-4)).
此乙烯基含量，理想的是在成分(a1)中為0.01~15莫耳%，此外，更佳為在成分(a1)中為0.01~5莫耳%。 The vinyl content is preferably 0.01 to 15 mol % in the component (a1), and more preferably 0.01 to 5 mol % in the component (a1).
前述成分(a1)的具有乙烯基的有機聚矽氧烷適合為具有乙烯基的烷基聚矽氧烷。此烷基較佳為碳數1~3(例如，甲基、乙基等)，更佳為甲基。 The vinyl group-containing organopolysiloxane of the aforementioned component (a1) is suitably a vinyl group-containing alkyl polysiloxane. The alkyl group preferably has 1 to 3 carbon atoms (for example, methyl, ethyl, etc.), more preferably methyl.
此外，成分(a1)的具有乙烯基的有機聚矽氧烷較佳為質量平均分子量小於400,000者，更佳為10,000~200,000，再更佳為15,000~200,000。 In addition, the organopolysiloxane having a vinyl group of the component (a1) preferably has a mass average molecular weight of less than 400,000, more preferably 10,000-200,000, and still more preferably 15,000-200,000.
此處，本發明的「乙烯基的含量」係指在將構成成分(a1)的全部單元設為100莫耳%時的含有乙烯基的矽氧烷單元的莫耳%。但是，對於一個含有乙烯基的矽氧烷單元，設為一個乙烯基。 Here, the "content of vinyl group" in the present invention refers to the mole % of the vinyl group-containing siloxane unit when all the units constituting the component (a1) are taken as 100 mole %. However, for a siloxane unit containing a vinyl group, let it be a vinyl group.
利用NMR測定乙烯基含量。具體而言，使用JEOL公司製的ECP-300NMR，將樣品溶解於作為重溶媒(heavy solvent)的氘代氯仿來進行測定。將在將(乙烯基+H-Si 基+Si-甲基)設為100莫耳%的情況下的乙烯基的比例設為乙烯基含量莫耳%。 Vinyl content was determined by NMR. Specifically, the measurement was performed by dissolving a sample in deuterated chloroform as a heavy solvent using ECP-300NMR manufactured by JEOL. Let the ratio of the vinyl group when (vinyl group+H-Si group+Si-methyl group) be 100 mol% be the vinyl group content mol%.
前述成分(a2)係至少在末端或者側鏈中的任一處具有2個以上的H-Si基的有機聚矽氧烷，可以是直鏈狀構造或者分枝狀構造中的任一者。一般而言，具有H-Si基的有機聚矽氧烷係有機聚矽氧烷的分子內(Si-R)的R部分的一部分成為H基者(例如，參照以下的一般式(a2-1)~(a2-4))。 The aforementioned component (a2) is an organopolysiloxane having two or more H-Si groups at least at any one of a terminal or a side chain, and may have either a linear structure or a branched structure. In general, a part of the R moiety in the molecule (Si-R) of an organopolysiloxane-based organopolysiloxane having an H-Si group becomes an H group (for example, refer to the following general formula (a2-1 )~(a2-4)).
此H-Si基含量，理想的是在(a2)中為0.01~15莫耳%，此外，更佳為在成分(a2)中為0.01~5莫耳%。 The H—Si group content is preferably 0.01 to 15 mol% in (a2), and more preferably 0.01 to 5 mol% in component (a2).
前述成分(a2)的有機聚矽氧烷適合為具有H-Si基的烷基聚矽氧烷。此烷基較佳為碳數1~3(例如，甲基、乙基等)，更佳為甲基。 The organopolysiloxane of the aforementioned component (a2) is suitably an alkylpolysiloxane having an H—Si group. The alkyl group preferably has 1 to 3 carbon atoms (for example, methyl, ethyl, etc.), more preferably methyl.
此外，成分(a2)的具有H-Si基的有機聚矽氧烷較佳為質量平均分子量為400,000以下者，更佳為10,000~200,000，再更佳為15,000~200,000。 In addition, the organopolysiloxane having an H-Si group of the component (a2) is preferably one having a mass average molecular weight of 400,000 or less, more preferably 10,000-200,000, and still more preferably 15,000-200,000.
此處，本發明的「H-Si基的含量」係指在將構成成分(a2)的全部單元設為100莫耳%時的含有H-Si基的矽氧烷單元的莫耳%。 Here, the "content of H-Si group" in this invention means the mole% of the H-Si group containing siloxane unit when the whole unit of a constituent component (a2) is taken as 100 mole%.
利用NMR測定H-Si基含量。使用JEOL公司製的ECP-300NMR，將樣品溶解於作為重溶媒的氘代氯仿來進行測定。在將(乙烯基+H-Si基+Si-甲基)設為100莫耳%的情況下將含有的H-Si基的比例設為H-Si基的含量莫耳%。 The H—Si group content was measured by NMR. The measurement was performed by dissolving a sample in deuterated chloroform as a heavy solvent using ECP-300NMR manufactured by JEOL. When (vinyl group+H-Si group+Si-methyl group) is 100 mol %, let the ratio of the H-Si group contained be the content mol% of H-Si group.
前述成分(A)二液加成反應型液狀矽酮係25℃的黏度為100~2,500mPa．s，較佳為100~2,000mPa．s，更佳為350~2,000mPa．s。 The viscosity of the aforementioned component (A) two-component addition reaction type liquid silicone system is 100~2,500mPa at 25°C. s, preferably 100~2,000mPa. s, more preferably 350~2,000mPa. s.
若前述成分(A)的黏度(25℃)小於100mPa．s，則分子量小，因此有硬化後的片變得容易裂開之虞，若超過2,500mPa．s，則有變得很難高度填充無機填料之虞。 If the viscosity (25°C) of the aforementioned component (A) is less than 100mPa. s, the molecular weight is small, so there is a risk that the hardened sheet will easily crack, if it exceeds 2,500mPa. s, it may become difficult to highly fill the inorganic filler.
對於二液加成型矽酮的黏度，使用BROOKFIELD公司製的B型黏度計「RVDVIT」進行測定。錠子使用f桿，能夠使用20rpm的黏度進行測定。 The viscosity of the two-component addition type silicone was measured using a B-type viscometer "RVDVIT" manufactured by Brookfield. The spindle uses an f-rod, and can be measured using a viscosity of 20 rpm.
此外，就前述成分(A)二液加成反應型液狀矽酮來說，前述(a1)具有乙烯基的有機聚矽氧烷和前述(a2)具有H-Si基的有機聚矽氧烷的比係在1：1.5~1.5：1之間，較佳為1：1.4~1.4：1，較佳為1：1~1.4：1，在使柔軟性提升的方面上是適合的。 In addition, in the aforementioned component (A) two-component addition reaction type liquid silicone, the aforementioned (a1) organopolysiloxane having a vinyl group and the aforementioned (a2) organopolysiloxane having an H-Si group The ratio is between 1:1.5~1.5:1, preferably 1:1.4~1.4:1, more preferably 1:1~1.4:1, which is suitable for improving flexibility.
此外，前述成分(A)二液加成反應型液狀矽酮較佳為有機聚矽氧烷之內係熱硬化者，除了主劑的聚有機聚矽氧烷聚合物外，還可以使用硬化劑(交聯性有機聚矽氧烷)。 In addition, the two-component addition reaction liquid silicone of the aforementioned component (A) is preferably an organopolysiloxane internal heat-curing one. agent (crosslinking organopolysiloxane).
構成前述二液加成反應型液狀矽酮的基礎聚合物，較佳為其主鏈中具有有機基(例如，甲基、苯基、三氟丙基等)者。例如，有機聚矽氧烷的重複構造可舉出：二甲基矽氧烷單元、苯基甲基矽氧烷、二苯基矽氧烷單元等。此外，可以使用具有乙烯基、環氧基等的官能基的改性有機聚矽氧烷。 The base polymer constituting the aforementioned two-component addition reaction type liquid silicone is preferably one having an organic group (eg, methyl group, phenyl group, trifluoropropyl group, etc.) in its main chain. For example, examples of the repeating structure of organopolysiloxane include dimethylsiloxane units, phenylmethylsiloxane units, and diphenylsiloxane units. In addition, modified organopolysiloxanes having functional groups such as vinyl groups and epoxy groups can be used.
此外，前述成分(A)二液加成反應型液狀矽酮能夠使用供促進加成反應用的加成反應觸媒。 In addition, an addition reaction catalyst for accelerating the addition reaction can be used for the two-component addition reaction type liquid silicone of the aforementioned component (A).
此外，前述成分(A)二液加成反應型液狀矽酮，若使用滿足上述各種條件的市售製品的話即可。 In addition, as the two-component addition reaction type liquid silicone of the above-mentioned component (A), what is necessary is just to use the commercially available product which satisfies the above-mentioned various conditions.
又，關於成分(a1)的末端或者側鏈的乙烯基，例如，能舉出用以下的一般式(a1-1)及一般式(a1-2)所表示者。此外，關於成分(a1)至少在末端或者側鏈具有乙烯基的有機聚矽氧烷，例如，能舉出用一般式(a1-3)及一般式(a1-4)所表示者。但是，本發明不限於這些一般式(a1-1)~(a1-4)。此外，關於本發明的成分(a1)，例如，能舉出在末端及/或側鏈具有乙烯基的甲基聚矽氧烷等。 Moreover, the terminal or the vinyl group of a side chain of a component (a1) is represented by the following general formula (a1-1) and general formula (a1-2), for example. Moreover, the organopolysiloxane which has a vinyl group at least in the terminal or a side chain of a component (a1) is represented by general formula (a1-3) and general formula (a1-4), for example. However, the present invention is not limited to these general formulas (a1-1) to (a1-4). Moreover, about the component (a1) of this invention, the methylpolysiloxane etc. which have a vinyl group in a terminal and/or a side chain are mentioned, for example.
此外，關於成分(a2)的末端或者側鏈的H-Si基，例如，能舉出以下的一般式(a2-1)及一般式(a2-2)所表示者等。此外，關於成分(a2)至少在末端或者側鏈具有2個以上的H-Si基的有機聚矽氧烷，例如，能舉出以下的一般式(a2-3)及一般式(a2-4)所表示者。但是，本發明不限於這些一般式(a2-1)~(a2-4)。此外，關於本發明的成分(a2)，例如，能舉出在末端及/或側鏈具有2個以上的H-Si基的甲基聚矽氧烷。 Moreover, about the H-Si group of the terminal of a component (a2) or a side chain, the thing represented by following general formula (a2-1) and general formula (a2-2), etc. are mentioned, for example. In addition, as the organopolysiloxane having at least two or more H-Si groups in the terminal or side chain of the component (a2), for example, the following general formula (a2-3) and general formula (a2-4 ) represented by. However, the present invention is not limited to these general formulas (a2-1) to (a2-4). Moreover, about the component (a2) of this invention, the methyl polysiloxane which has 2 or more H-Si groups in a terminal and/or a side chain can be mentioned, for example.
作為市售品的二液加成反應型液狀矽酮橡膠，例如，可舉出：Momentive公司製的「X14-B8530」、Toray-Dow Corning公司製的「SE-1885A/B」、信越化學工業公司製的「KE-1283」等，但本發明不限於這些具體的市售製品的範圍。 Examples of commercially available two-component addition reaction liquid silicone rubber include "X14-B8530" manufactured by Momentive, "SE-1885A/B" manufactured by Toray-Dow Corning, and Shin-Etsu Chemical Co., Ltd. "KE-1283" manufactured by Kogyo Co., Ltd., etc., but the present invention is not limited to the range of these specific commercially available products.
前述成分(A)二液加成反應型液狀矽酮的含量適合為10~35體積%，更適合為16~34體積%。成分(A)含量，作為下限值，更佳為12體積%以上，再更佳為18體積%以上。此外，成分(A)的含量，作為上限值，更佳為33體積%以下。前述成分(A)的含量，若組成物中小於10體積%，則有柔軟性受損之虞，若組成物中超過35體積%，則有熱傳導率降低之虞。 The content of the aforementioned component (A) two-component addition reaction type liquid silicone is suitably 10-35% by volume, more suitably 16-34% by volume. The lower limit of the component (A) content is more preferably at least 12% by volume, and still more preferably at least 18% by volume. In addition, the content of the component (A) is more preferably 33% by volume or less as the upper limit. If the content of the aforementioned component (A) is less than 10% by volume in the composition, the flexibility may be impaired, and if it exceeds 35% by volume in the composition, the thermal conductivity may decrease.
此外，本發明中所使用的加成反應型液狀矽酮也能夠與乙醯基醇類、馬來酸酯類等的反應延遲劑、十~數百μm的氣凝膠或矽酮粉末等的增黏劑、耐燃劑、顏料等併用。 In addition, the addition reaction liquid silicone used in the present invention can also be used with reaction retarders such as acetyl alcohols and maleic acid esters, airgel or silicone powder of tens to hundreds of μm, etc. Adhesives, flame retardants, pigments, etc. are used together.
<成分(B)在末端或者側鏈中的任一者具有2個以上的乙烯基的高分子量矽酮> <High-molecular-weight silicone having two or more vinyl groups in either terminal or side chain of component (B)>
本發明的成分(B)在末端或者側鏈中的任一者具有2個以上的乙烯基的高分子量矽酮較佳為質量平均分子量為400,000~900,000。 Component (B) of the present invention preferably has a mass average molecular weight of 400,000 to 900,000 in the high-molecular-weight silicone having two or more vinyl groups in either the terminal or the side chain.
在前述成分(B)中，乙烯基的含量沒有特別的限制，為了使其適合形成與組成物中的各成分的網絡，例如，成分(B)中，較佳為0.01~15莫耳%，更佳為0.05~5莫耳%。 In the aforementioned component (B), the content of the vinyl group is not particularly limited. In order to make it suitable for forming a network with each component in the composition, for example, in component (B), it is preferably 0.01 to 15 mol%, More preferably, it is 0.05-5 mol%.
此處，本發明的「乙烯基的含量」係指在將構成成分(B)的全部單元設為100莫耳%時的含有乙烯基的矽氧烷單元的莫耳%。又，乙烯基含量的測定方法係如下所示。 Here, the "content of vinyl group" in the present invention refers to the mole % of the vinyl group-containing siloxane unit when all the units constituting the component (B) are taken as 100 mole %. In addition, the measuring method of the vinyl content is as follows.
利用NMR測定乙烯基含量。具體而言，使用JEOL公司製的ECP-300NMR，將樣品溶解於作為重溶媒的氘代氯仿來進行測定。將在將(乙烯基+H-Si基+Si-甲基)設為100莫耳%的情況下的乙烯基的比例設為乙烯基含量莫耳%。 Vinyl content was determined by NMR. Specifically, the measurement was performed by dissolving a sample in deuterated chloroform as a heavy solvent using ECP-300NMR manufactured by JEOL. Let the proportion of the vinyl group when (vinyl group+H-Si group+Si-methyl group) be 100 mol% be the vinyl group content mol%.
本發明的成分(B)較佳為具有含有乙烯基的直鏈狀的烷基的矽酮，其為具有直鏈構造和可成為硬化時的交聯點的乙烯基者。適合為用以下的一般式(B)所表示者。 The component (B) of the present invention is preferably a silicone having a linear alkyl group containing a vinyl group, which has a linear structure and a vinyl group that can serve as a crosslinking point during hardening. What is represented by the following general formula (B) is suitable.
前述式(B)中，R1及R2係各自獨立的碳數1~10的取代或者未取代的烷基、烯基、芳基、或者組合它們的烴基，複數個R1及R2當中至少一個以上為乙烯基。複數個R1係彼此獨立者，可以彼此互異，也可以相同。 In the aforementioned formula (B), R 1 and R 2 are independently substituted or unsubstituted alkyl groups, alkenyl groups, aryl groups, or hydrocarbon groups combining them with 1 to 10 carbon atoms, among the plurality of R 1 and R 2 At least one or more is a vinyl group. A plurality of R 1s are independent of each other, and may be different from each other, or may be the same.
作為碳數1~10的烷基，例如，可舉出：甲基、乙基、丙基等，其中，較佳為甲基。 As a C1-C10 alkyl group, a methyl group, an ethyl group, a propyl group etc. are mentioned, for example, Among them, a methyl group is preferable.
作為碳數1~10的烯基，例如，可舉出：乙烯基、烯丙基、丁烯基等，其中，較佳為乙烯基。 Examples of alkenyl groups having 1 to 10 carbon atoms include vinyl groups, allyl groups, and butenyl groups, among which vinyl groups are preferred.
作為碳數1~10的芳基，例如，可舉出苯基等。 As a C1-C10 aryl group, a phenyl group etc. are mentioned, for example.
前述式(B)中，R3係碳數1~8的取代或者未取代的烷基、芳基或者組合它們的烴基。作為碳數1~8的烷基，例如，可舉出：甲基、乙基及丙基等，其中，較佳為甲基。作為碳數1~8的芳基，例如，可舉出苯基等。R3當中較佳為甲基。 In the aforementioned formula (B), R is a substituted or unsubstituted alkyl group, aryl group or a hydrocarbon group combining them with 1 to 8 carbon atoms. As a C1-C8 alkyl group, a methyl group, an ethyl group, a propyl group etc. are mentioned, for example, Among them, a methyl group is preferable. As a C1-8 aryl group, a phenyl group etc. are mentioned, for example. Methyl is preferred among R 3 .
前述式(B)中，複數個R3係彼此獨立者，可以彼此互異，也可以相同。 In the aforementioned formula (B), a plurality of R 3 are independent of each other, and may be different from each other, or may be the same.
前述式(B)中的m及n係構成前述成分(B)的重複單元的數量，m係1000~10000的整數，n係0~1000的整數。m較佳為3000~10000的整數，更佳為3600~8000的整數。n較佳為1~1000的整數，更佳為40~700的整數。 m and n in the aforementioned formula (B) are the number of repeating units constituting the aforementioned component (B), m is an integer of 1,000 to 10,000, and n is an integer of 0 to 1,000. m is preferably an integer of 3,000 to 10,000, more preferably an integer of 3,600 to 8,000. n is preferably an integer of 1 to 1000, more preferably an integer of 40 to 700.
作為前述成分(B)，例如，較佳為具有用以下的一般式(B1)所表示的構造者。在下述一般式(B1)中，R1及R2係各自獨立的甲基或者乙烯基，複數個R1及R2當中，至少一個為乙烯基。 As the aforementioned component (B), for example, one having a structure represented by the following general formula (B1) is preferable. In the following general formula (B1), R 1 and R 2 are independently methyl or vinyl groups, and at least one of the plurality of R 1 and R 2 is a vinyl group.
在下述一般式(B1)中，R1適合為甲基，R2適合為乙烯基。 In the following general formula (B1), R 1 is suitably methyl and R 2 is suitably vinyl.
作為前述成分(B)，能夠使用市售品，可舉出：Momentive公司製的TSE201、Momentive公司製的XE25-511及Momentive公司製的SRH-32等。Momentive公司製的TSE201等係例如用下述式(B1-1)所表示者。 As said component (B), a commercial item can be used, TSE201 by the Momentive company, XE25-511 by the Momentive company, SRH-32 by the Momentive company etc. are mentioned. Momentive's TSE201 etc. are represented by following formula (B1-1), for example.
Momentive公司製的TSE-201(商品名)係乙烯基含量：0.2mol%、質量平均分子量800,000，Momentive公司製的SRH-32(商品名)係乙烯基含量：0.1mol%、質量平均分子量500,000。 Momentive TSE-201 (trade name) has a vinyl content of 0.2 mol % and a mass average molecular weight of 800,000, and Momentive's SRH-32 (trade name) has a vinyl content of 0.1 mol % and a mass average molecular weight of 500,000.
前述成分(B)的含量係組成物中1~20體積%，若為1體積%以下，則成形加工性惡化。前述成分(B)的含量係組成物中，較佳為2~15體積%，更佳為4~10體積%。 The content of the aforementioned component (B) is 1 to 20% by volume in the composition, and if it is 1% by volume or less, formability deteriorates. The content of the aforementioned component (B) is preferably 2-15% by volume, more preferably 4-10% by volume in the composition.
<成分(C)烷基烷氧基矽烷> <Component (C) Alkylalkoxysilane>
本發明的成分(C)烷基烷氧基矽烷沒有特別的限定，可以具有取代基。能夠適宜使用市售品，例如，可 舉出Toray-Dow Corning公司製的Z-6210等。Toray-Dow Corning公司製的Z-6210(商品名)係正癸基三甲氧基矽烷。 The component (C) alkylalkoxysilane of this invention is not specifically limited, It may have a substituent. Commercially available products can be suitably used, for example, Z-6210 manufactured by Toray-Dow Corning Co., Ltd., etc. are mentioned. Z-6210 (trade name) manufactured by Toray-Dow Corning is n-decyltrimethoxysilane.
前述成分(C)的烷基烷氧基矽烷較佳為分子量為100~300者。 The alkylalkoxysilane of the aforementioned component (C) preferably has a molecular weight of 100-300.
前述成分(C)較佳為具有碳數1~18的烷基的烷基烷氧基矽烷。 The aforementioned component (C) is preferably an alkylalkoxysilane having an alkyl group having 1 to 18 carbon atoms.
此外，「烷基烷氧基矽烷」的烷基可以是直鏈狀、分枝狀、環狀中的任一烷基。 In addition, the alkyl group of "alkyl alkoxysilane" may be any one of linear, branched and cyclic.
此外，「烷基烷氧基矽烷」的烷氧基，不管是甲氧基、乙氧基、苯氧基都能使用。 In addition, the alkoxy group of "alkyl alkoxysilane" can be used regardless of methoxy, ethoxy, or phenoxy.
前述成分(C)更佳為用以下的一般式(C)所表示者。 The aforementioned component (C) is more preferably represented by the following general formula (C).
RR 44 (R(R 55 )) pp SiXSiX 3-p3-p (C) (C)
前述式(C)中，R4係碳數1~18的直鏈狀或者分枝鏈狀的烷基，R5係氫原子或者碳數1~3的烷基，X係碳數1~12的烷氧基，p係0~2的整數。 In the aforementioned formula (C), R4 is a linear or branched chain alkyl group with 1 to 18 carbons, R5 is a hydrogen atom or an alkyl group with 1 to 3 carbons, and X is an alkyl group with 1 to 12 carbons. The alkoxy group, p is an integer of 0~2.
前述式(C)中，R4的烷基的碳數較佳為1~12，更佳為1~10，再更佳為6~10，再更佳為8~10。R4較佳為甲基、乙基、丙基、丁基、戊基、己基、辛基、2-乙基己基、壬基、癸基、十二烷基、月桂基等。其中，從很難揮發的觀點來看，癸基是有效的。 In the aforementioned formula (C), the carbon number of the alkyl group of R4 is preferably 1-12, more preferably 1-10, more preferably 6-10, and even more preferably 8-10. R 4 is preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, nonyl, decyl, dodecyl, lauryl and the like. Among them, decyl group is effective from the viewpoint of being hard to volatilize.
前述式(C)中，R5較佳為甲基。 In the aforementioned formula (C), R 5 is preferably a methyl group.
前述式(C)中，p較佳為0，因此較佳為「X3」。 In the aforementioned formula (C), p is preferably 0, so it is preferably "X 3 ".
前述式(C)中，X較佳為碳數1~6的烷氧基，例如，較佳為甲氧基、乙氧基、正丙氧基、異丙氧基、苯氧基等。其中，在與填料的親和性方面上，甲氧基是有效的。 In the aforementioned formula (C), X is preferably an alkoxy group having 1 to 6 carbon atoms, for example, preferably a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a phenoxy group, and the like. Among them, the methoxy group is effective in terms of the affinity with the filler.
前述式(C)中，「X3-n」較佳為三甲氧基。 In the aforementioned formula (C), "X 3-n " is preferably trimethoxy.
作為前述烷基烷氧基矽烷，從很難揮發的觀點來看，較佳為正癸基三甲氧基矽烷。 As the above-mentioned alkylalkoxysilane, n-decyltrimethoxysilane is preferable from the viewpoint of being hardly volatile.
本發明的成分(C)的烷基烷氧基矽烷的含量係組成物中0.05~2體積%，較佳為0.1~2體積%。若小於0.05體積%，則填料與矽酮的親和性下降而熱特性變得容易受損，若超過2體積%，則黏度急遽下降而填料變得容易沉澱。 The content of the alkylalkoxysilane in the component (C) of the present invention is 0.05-2% by volume in the composition, preferably 0.1-2% by volume. If it is less than 0.05% by volume, the affinity between the filler and silicone is lowered and the thermal properties are likely to be impaired. If it exceeds 2% by volume, the viscosity drops rapidly and the filler tends to precipitate.
<成分(D)無機填料> <Component (D) Inorganic filler>
本發明的樹脂組成物的熱傳導性填料的含有率，較佳為總體積中的63體積%以上，更佳為65~85體積%，特別理想的是70~85體積%。 The content of the thermally conductive filler in the resin composition of the present invention is preferably at least 63% by volume, more preferably 65 to 85% by volume, and particularly preferably 70 to 85% by volume.
在熱傳導性填料的含有率小於63體積%方面，將樹脂組成物硬化的片的熱傳導性容易變得不充分，因此含量越高越理想。此外，若超過85體積%，則樹脂組成物的流動性變差，小於0.3mm的厚度的樹脂組成物的硬化物的製作容易變得困難，因此理想的是85體積%以下。 When the content of the thermally conductive filler is less than 63% by volume, the thermal conductivity of the sheet cured from the resin composition tends to be insufficient, so the higher the content, the better. Also, if it exceeds 85% by volume, the fluidity of the resin composition will deteriorate, and it will easily become difficult to produce a cured product of the resin composition with a thickness of less than 0.3 mm. Therefore, it is preferably 85% by volume or less.
本發明中所使用的無機填料能舉出：熱傳導性填料的氧化鋁、氧化鎂、氮化硼、氮化鋁、氮化矽、碳化矽、金屬鋁及石墨等。能夠單獨使用它們或者將它們組合2種以上使用。本發明中所使用的無機填料理想的是球狀(球形度適合為0.85以上)。 Examples of the inorganic filler used in the present invention include alumina, magnesia, boron nitride, aluminum nitride, silicon nitride, silicon carbide, metallic aluminum, and graphite as thermally conductive fillers. These can be used individually or in combination of 2 or more types. The inorganic filler used in the present invention is preferably spherical (sphericity is preferably 0.85 or more).
它們當中，氧化鋁表現出高熱傳導性，同時對樹脂的填充性良好，因而是理想的。 Among them, alumina exhibits high thermal conductivity, and at the same time has good filling property to resin, and thus is ideal.
本發明中所使用的氧化鋁較佳為球狀。氧化鋁(以下也稱為「礬土」)可以是用氫氧化鋁粉末的火燄熔射法、拜耳法、銨礬熱分解法、有機鋁水解法、鋁水中放電法、凍結乾燥法等中的任一方法所製造者，從粒徑分布的控制及粒子形狀控制的方面來看，適合為氫氧化鋁粉末的火燄熔射法。 Alumina used in the present invention is preferably spherical. Alumina (hereinafter also referred to as "bauxite") can be produced by flame spraying method using aluminum hydroxide powder, Bayer method, ammonium alum thermal decomposition method, organic aluminum hydrolysis method, aluminum water discharge method, freeze-drying method, etc. Either method is suitable for the flame spraying method of aluminum hydroxide powder from the viewpoint of particle size distribution control and particle shape control.
此外，球狀礬土粉末的結晶構造可以是單晶體、多晶體中的任一者，從高熱傳導性的方面來看，結晶相理想的是α相，此外比重理想的是3.7以上。若比重小於3.7，則存在於粒子內部的空孔和低結晶相的存在比例變多，因此變得很難將熱傳導率提高至2.5W/mK以上。球狀礬土粉末的粒度調整能夠藉由球狀礬土粉末的分級．混合操作來進行。 In addition, the crystal structure of the spherical alumina powder may be any of single crystal and polycrystal. From the viewpoint of high thermal conductivity, the crystal phase is preferably α phase, and the specific gravity is preferably 3.7 or more. If the specific gravity is less than 3.7, the ratio of voids and low-crystalline phases present in the particles increases, making it difficult to increase the thermal conductivity to 2.5 W/mK or more. The particle size of spherical alumina powder can be adjusted by classifying spherical alumina powder. Mixed operations are performed.
在使用球狀礬土粉末的情況下，球形度為0.85以上。在球形度小於0.85方面，流動性降低而填料會在間隔物(spacer)內發生偏析而物性的變異變大。作為球形度為0.85以上的市售品，例如，可舉出：Denka股份有限公司製的球狀礬土DAW70(商品名)、球狀礬土DAW45S(商品名)、球狀礬土DAW05(商品名)、球狀礬土ASFP20(商品名)等。 In the case of using spherical alumina powder, the degree of sphericity is 0.85 or more. When the sphericity is less than 0.85, the fluidity decreases, the filler segregates in the spacer, and the variation in physical properties increases. As commercially available products having a sphericity of 0.85 or more, for example, spherical alumina DAW70 (trade name), spherical alumina DAW45S (trade name), spherical alumina DAW05 (trade name) manufactured by Denka Co., Ltd. name), spherical alumina ASFP20 (trade name), etc.
本發明的無機填料的粒度分布較佳為在平均粒徑10~100μm、1~10μm及小於1μm的範圍內具有極大值或者波峰者。 The particle size distribution of the inorganic filler of the present invention preferably has a maximum value or a peak in the range of an average particle diameter of 10-100 μm, 1-10 μm and less than 1 μm.
前述平均粒徑10~100μm的無機填料係無機填料中，較佳為23體積%以上，更佳為25~50體積%，再更佳為30~48體積%，再更佳為34~47體積%。 Among the above-mentioned inorganic fillers with an average particle size of 10-100 μm, it is preferably more than 23% by volume, more preferably 25-50% by volume, more preferably 30-48% by volume, and even more preferably 34-47% by volume %.
此外，前述平均粒徑1~10μm的無機填料係無機填料中，較佳為15~30體積%，更佳為20~28體積%，再更佳為20~25體積%。 In addition, among the above-mentioned inorganic fillers with an average particle diameter of 1-10 μm, the content is preferably 15-30% by volume, more preferably 20-28% by volume, and even more preferably 20-25% by volume.
此外，前述平均粒徑小於1.0μm的無機填料係無機填料中，較佳為5~20體積%，更佳為10~15體積%，再更佳為11~13體積%。 In addition, among the above-mentioned inorganic fillers with an average particle size of less than 1.0 μm, the content is preferably 5-20% by volume, more preferably 10-15% by volume, and even more preferably 11-13% by volume.
前述無機填料的粒度分布較佳為適宜組合這3個範圍的無機填料。 The particle size distribution of the above-mentioned inorganic filler is preferably an inorganic filler suitable for combining these three ranges.
本發明的無機填料的粒度分布較佳為平均粒徑10~100μm的無機填料為25~50體積%(更適合為34~47體積%)，平均粒徑1~10μm的無機填料為15~30體積%(更適合為20~25體積%)，平均粒徑小於1.0μm的無機填料為5~20體積%(更適合為11~13體積%)。 The particle size distribution of the inorganic filler of the present invention is preferably 25 to 50% by volume (more suitably 34 to 47% by volume) for inorganic fillers with an average particle diameter of 10 to 100 μm, and 15 to 30% for inorganic fillers with an average particle diameter of 1 to 10 μm. % by volume (20~25% by volume is more suitable), and 5~20% by volume (11~13% by volume is more suitable) for inorganic fillers with an average particle size of less than 1.0 μm.
<樹脂組成物的製造方法、樹脂成形體、散熱片等> <Manufacturing method of resin composition, resin molded article, heat sink, etc.>
本發明的高熱傳導性樹脂成形體能夠用公知的製造方法得到。例如，能夠藉由混合前述成分(A)~(D)來得到。 The highly thermally conductive resin molded article of the present invention can be obtained by a known production method. For example, it can obtain by mixing said component (A)-(D).
此外，本發明的高熱傳導性樹脂成形體，係例如可經過原料的混合．成形．加硫步驟來加以製造。就混合而言，可使用輥磨機、捏合機、班布瑞混合機等的混合機。成形方法較佳為刮刀(doctor blade)法，能夠依樹脂的黏度使用擠出法．壓製法．軋光輥法等。加硫溫度理 想的是50~200℃，加熱硬化時間較佳為2~14小時。在小於50℃方面，加硫不充分，若超過200℃，則間隔物的一部分劣化。加硫係使用一般的熱風乾燥機、遠紅外乾燥機、微波乾燥機等進行。能夠依此方式操作而得到熱傳導性樹脂成形體。作為本發明中所使用的樹脂原料，在無損本發明的效果的範圍內，除了上述成分(A)~(C)外，還可以適宜選擇丙烯酸樹脂及環氧樹脂等的樹脂原料。此外，可以以本發明的組成物成為100體積%的方式進行掺合，也可以進一步添加於本發明的組成物100體積%。 In addition, the high thermal conductivity resin molded article of the present invention, for example, can be mixed through raw materials. forming. Sulphurization step to be manufactured. For mixing, a mixer such as a roll mill, a kneader, a Banbury mixer can be used. The forming method is preferably doctor blade method, and extrusion method can be used according to the viscosity of the resin. suppression method. Calender roll method, etc. The ideal vulcanization temperature is 50~200°C, and the heating and hardening time is preferably 2~14 hours. When the temperature is less than 50°C, sulfur addition is insufficient, and when it exceeds 200°C, part of the spacer deteriorates. Sulfur addition is carried out using general hot air dryers, far-infrared dryers, microwave dryers, etc. In this manner, a thermally conductive resin molded article can be obtained. As the resin raw material used in the present invention, in addition to the above-mentioned components (A) to (C), resin raw materials such as acrylic resins and epoxy resins can be appropriately selected within the range that does not impair the effects of the present invention. In addition, it may be blended so that the composition of the present invention becomes 100% by volume, or may be further added to 100% by volume of the composition of the present invention.
由本發明的樹脂組成物所得到的樹脂成形體的厚度為0.3mm~6mm，特別理想的是0.5~5mm。若樹脂成形體的厚度比0.3mm薄，則由熱傳導性填料所造成的表面粗糙度會變大，熱傳導性變差。此外，若超過6mm，則樹脂成形體的硬化物變厚，熱傳導性變差。樹脂成形體的厚度理想的是以樹脂組成物的硬化後的厚度作為基準。 The thickness of the resin molded body obtained from the resin composition of the present invention is 0.3 mm to 6 mm, particularly preferably 0.5 to 5 mm. If the thickness of the resin molded body is thinner than 0.3 mm, the surface roughness due to the thermally conductive filler will increase, resulting in poor thermal conductivity. Moreover, when it exceeds 6 mm, the hardened|cured material of a resin molded object will become thick, and thermal conductivity will deteriorate. The thickness of the resin molded article is preferably based on the thickness of the cured resin composition.
依以上方式，本發明的熱傳導性樹脂組成物係能夠得到具有高熱傳導性和高柔軟性的樹脂成形體的樹脂組成物。 As described above, the thermally conductive resin composition system of the present invention is a resin composition capable of obtaining a resin molded article having high thermal conductivity and high flexibility.
藉由使用本發明的樹脂組成物，能夠提供具有高熱傳導性和高柔軟性的樹脂成形體及散熱片。 By using the resin composition of the present invention, it is possible to provide a resin molded article and a heat sink having high thermal conductivity and high flexibility.
本發明的樹脂成形體係具有高熱傳導性者，可以提供熱傳導率3W/mK以上，甚至5W/mK以上者。 The resin molding system of the present invention has a high thermal conductivity, and can provide a thermal conductivity of 3 W/mK or more, or even 5 W/mK or more.
另外，本發明的樹脂成形體係具有高熱傳導性，而且具有其阿斯克C硬度30以下者。該樹脂成形體的阿斯克C硬度較佳為30以下，更佳為5~30，再更佳為7~15。若阿斯克C硬度比5小，則有處理片之際的作業性(handling)變得困難之虞。 In addition, the resin molding system of the present invention has high thermal conductivity and has an Asker C hardness of 30 or less. The Usk C hardness of the resin molded article is preferably 30 or less, more preferably 5-30, and still more preferably 7-15. When the Asker C hardness is less than 5, there is a possibility that handling when handling a sheet becomes difficult.
此外，本發明的樹脂成形體的壓縮率較佳為25%以上，更佳為30%以上，再更佳為35%以上。 In addition, the compression rate of the resin molded article of the present invention is preferably at least 25%, more preferably at least 30%, and still more preferably at least 35%.
目前的高熱傳導性樹脂成形體，如上所述，可實質製作的阿斯克C硬度係到40左右為止。儘管如此，若阿斯克C硬度超過30，則熱傳導性片本身變硬，與發熱元件的緊貼性受損而熱傳導性變差。然而，藉由使用本發明的樹脂組成物，能夠具有熱傳導率3W/mK以上的高傳導性，同時將阿斯克C硬度設為30以下，因而可以提供新穎的高熱傳導性樹脂成形體。 As mentioned above, the current high thermal conductivity resin molded article can be substantially produced up to about 40 Usk C hardness. Nevertheless, when the Asker C hardness exceeds 30, the thermally conductive sheet itself becomes hard, and the adhesiveness to the heating element is impaired, resulting in poor thermal conductivity. However, by using the resin composition of the present invention, it is possible to have high conductivity with a thermal conductivity of 3 W/mK or higher, and at the same time to set the Usk C hardness to 30 or lower, so that a novel highly thermally conductive resin molded article can be provided.
此外，本發明的樹脂成形體具有高柔軟性，因而可以具有壓縮率高達25%以上的壓縮率。 In addition, the resin molded article of the present invention has high flexibility and thus can have a compressibility as high as 25% or more.
根據本發明的話，便能夠提供具有高熱傳導性和高柔軟性的樹脂成形體及散熱片。另外，根據本發明的話，便能夠提供具有高柔軟性的高熱傳導性部散熱材。另外，能夠適合提供散熱間隔物，該散熱間隔物特別適合作為電子零件用散熱構件。 According to the present invention, it is possible to provide a resin molded article and a heat sink having high thermal conductivity and high flexibility. In addition, according to the present invention, it is possible to provide a high thermal conductivity heat sink having high flexibility. In addition, it is possible to suitably provide a heat dissipation spacer which is particularly suitable as a heat dissipation member for electronic components.
另外，根據本發明的話，則可提供使用了其高熱傳導性散熱構件的行動基地台用途、或蓄電池用途、功率調節器裝置。 In addition, according to the present invention, it is possible to provide a mobile base station use, a storage battery use, or a power conditioner device using the heat dissipation member with high thermal conductivity.
另外，藉由使用本發明的樹脂組成物，能夠提供具有高柔軟性的高熱傳導性部散熱材。本發明適合作為如要求半導體元件的發熱面和散熱鰭等的散熱面的緊貼性的電子零件用散熱構件。本發明的散熱構件，例如，理想的是用作散熱片、散熱間隔物等。 In addition, by using the resin composition of the present invention, it is possible to provide a high thermal conductivity heat sink material having high flexibility. The present invention is suitable as a heat dissipation member for electronic components, for example, in which the heat dissipation surface of a semiconductor element and heat dissipation surfaces such as heat dissipation fins require close adhesion. The heat dissipation member of the present invention is preferably used, for example, as a heat dissipation fin, a heat dissipation spacer, or the like.
另外，藉由使用本發明的樹脂組成物，能夠提供使用了其高熱傳導性散熱構件的無線基地台或行動基地台用途(例如，通訊用、高速通訊用等)、或蓄電池用途、功率調節器裝置等所要求的電子零件。 In addition, by using the resin composition of the present invention, it is possible to provide wireless base stations or mobile base station applications (for example, for communication, high-speed communication, etc.), storage battery applications, and power conditioners using the high thermal conductivity heat dissipation member. Electronic parts required for devices, etc.
此外，本發明的樹脂組成物的散熱構件係高柔軟性且與散熱元件的緊貼性優異，作為電子機器，能夠適用於智慧型手機、平板PC、個人電腦、家庭用遊戲機、電源、汽車、例如無線基地台用途。 In addition, the heat dissipation member of the resin composition of the present invention has high flexibility and excellent adhesion to heat dissipation elements, and can be applied to smart phones, tablet PCs, personal computers, home game machines, power supplies, automobiles, etc. as electronic equipment. , such as wireless base station applications.
無線基地台用途，發熱元件的功率係隨著高速通訊的規格上升而升高，因此必須提高對散熱材所要求的熱傳導率，逐漸變得需要2W/mK以上。現在，開始要求3~5W/mK，若為了使熱傳導性提升而高度填充熱傳導填料，則散熱片變硬，有因基板的翹曲或發熱元件的應力所產生的損傷的可能性。此用途要求高柔軟性散熱材，阿斯克C硬度為30以下，壓縮率要求25%以上。 For wireless base station applications, the power of heating elements increases with the increase in high-speed communication specifications, so it is necessary to increase the thermal conductivity required for heat dissipation materials, and gradually becomes more than 2W/mK. At present, 3~5W/mK is required. If the thermal conductivity filler is highly filled to improve thermal conductivity, the heat sink will become hard, and there is a possibility of damage due to warpage of the substrate or stress of the heating element. This application requires a high flexibility heat dissipation material, the Asker C hardness is below 30, and the compressibility is required to be above 25%.
根據本發明的話，便可以提供無線基地台用途等的用途所使用的電子零件中使用的散熱片或者高熱傳導性散熱構件滿足熱傳導率3W/mK以上且阿斯克C硬度為30以下的條件者。另外，也可以提供滿足熱傳導率3W/mK以上且阿斯克C硬度為30以下及壓縮率25%以上的條件者。 According to the present invention, it is possible to provide a heat sink or a high-thermal-conductivity heat-dissipating member that satisfies the conditions of thermal conductivity of 3 W/mK or more and Asker C hardness of 30 or less. In addition, those satisfying the conditions of thermal conductivity of 3 W/mK or more, Usk C hardness of 30 or less, and compressibility of 25% or more can also be provided.
又，本發明的間隔物係可經過原料的混合．成形．加硫步驟來加以製造。就混合而言，可使用輥磨機、捏合機、班布瑞混合機等的混合機。成形方法較佳為刮刀法，能夠依樹脂組成物的黏度使用擠出法．壓製法．軋光輥法等。加硫溫度理想的是50~200℃。在小於50℃方面，加硫不充分，若超過200℃，則間隔物的一部分劣化。加硫係使用一般的熱風乾燥機、遠紅外乾燥機、微波乾燥機等進行。依此方式操作而得到熱傳導性片。 Also, the spacer system of the present invention can be mixed through raw materials. forming. Sulphurization step to be manufactured. For mixing, a mixer such as a roll mill, a kneader, a Banbury mixer can be used. The forming method is preferably scraper method, and extrusion method can be used according to the viscosity of the resin composition. suppression method. Calender roll method, etc. The ideal vulcanization temperature is 50~200°C. When the temperature is less than 50°C, sulfur addition is insufficient, and when it exceeds 200°C, part of the spacer deteriorates. Sulfur addition is carried out using general hot air dryers, far-infrared dryers, microwave dryers, etc. In this manner, a thermally conductive sheet was obtained.
本發明係適合用於產業用構件等的熱傳導構件者，特別是適合用於安裝時的壓縮應力小的高柔軟性熱傳導性樹脂組成物、熱傳導性樹脂成形體及散熱構件者。 The present invention is suitable for use in thermally conductive members such as industrial members, especially for highly flexible thermally conductive resin compositions, thermally conductive resin molded articles, and heat dissipation members with low compressive stress during mounting.
以下，針對本發明，藉由試驗例(包含實施例及比較例)詳細地進行說明。又，本發明不限於以下的實施例。 Hereinafter, the present invention will be described in detail using test examples (including examples and comparative examples). In addition, the present invention is not limited to the following examples.
使用下述所示的成分(A)包含(a1：具有乙烯基的有機聚矽氧烷)+(a2：具有H-Si基的有機聚矽氧烷)的二液性的加成反應型矽酮、成分(B)具有乙烯基的高分子量矽酮、成分(C)烷氧基矽烷、成分(D)無機填料，基於表1~4中記載的各試驗例的掺合比及體積%比例進行混合。又，將成分(A)~成分(D)的合計量設為體積100%。 A two-component addition-reaction silicone containing (a1: organopolysiloxane having a vinyl group) + (a2: organopolysiloxane having an H-Si group) is used as the component (A) shown below. Ketone, component (B) high-molecular-weight silicone with a vinyl group, component (C) alkoxysilane, component (D) inorganic filler, based on the blending ratio and volume % ratio of each test example described in Tables 1 to 4 to mix. Moreover, let the total amount of a component (A) - a component (D) be 100% by volume.
使用經混合的樹脂組成物使用刮刀(法)，將片(樹脂成形體)製作成既定的厚度，在110℃下進行加熱硬化8小時。 Using the mixed resin composition, a sheet (resin molded article) was produced to a predetermined thickness using a doctor blade (method), and heat curing was performed at 110° C. for 8 hours.
關於各試驗例的評價結果，顯示於表1~4。 The evaluation results of the respective test examples are shown in Tables 1 to 4.
關於試驗例1~5、試驗例11~20、試驗例28~30，藉由使用成分(A)~(D)，能夠在片的厚度為0.3~6mm的範圍內，得到具有良好的柔軟性的熱傳導性散熱性片。另外，(a1)和成分(a2)的比在1.4：1至1：1.4之間能夠得到具有良好的柔軟性的熱傳導性散熱性片。 Regarding Test Examples 1 to 5, Test Examples 11 to 20, and Test Examples 28 to 30, by using components (A) to (D), it is possible to obtain a sheet having good flexibility within the thickness of the sheet within the range of 0.3 to 6 mm. thermally conductive heat sink. Moreover, the ratio of (a1) and a component (a2) is 1.4:1-1:1.4, and the thermally conductive heat radiation sheet which has favorable flexibility can be obtained.
關於試驗例1~8、試驗例25，藉由含有1~20體積%的成分(B)具有乙烯基的高分子量矽酮，能夠得到具有良好的柔軟性的熱傳導性散熱性片。此外，此時，在無機填料67~85體積%的範圍內，能夠得到具有良好的柔軟性的熱傳導性散熱性片。 Regarding Test Examples 1 to 8 and Test Example 25, by containing 1 to 20% by volume of the high-molecular-weight silicone having a vinyl group as the component (B), a thermally conductive heat dissipation sheet having good flexibility can be obtained. In addition, in this case, in the range of 67 to 85% by volume of the inorganic filler, a thermally conductive heat dissipation sheet having good flexibility can be obtained.
關於試驗例9~10、試驗例19~30，藉由含有0.05~2.0體積%的成分(C)烷氧基矽烷，能夠得到具有良好的柔軟性的熱傳導性散熱性片。另外，(a1)和成分(a2)的比在1.4：1至1：1.4之間能夠得到具有良好的柔軟性的熱傳導性散熱性片。 About Test Examples 9-10 and Test Examples 19-30, the thermally conductive heat radiation sheet which has favorable flexibility can be obtained by containing 0.05-2.0 volume% of component (C) alkoxysilane. Moreover, the ratio of (a1) and a component (a2) is 1.4:1-1:1.4, and the thermally conductive heat radiation sheet which has favorable flexibility can be obtained.
此外，關於試驗例31~34，在不含有成分(C)烷氧基矽烷的情況下，無法得到具有良好的柔軟性的熱傳導性散熱性片。 Moreover, about Test Examples 31-34, when component (C) alkoxysilane was not contained, the thermally conductive heat dissipation sheet which has favorable flexibility could not be obtained.
關於試驗例1~20、試驗例26~30，藉由使用成分(A)二液加成反應型矽酮係黏度350~2,000mPa．sec者，能夠得到具有良好的柔軟性的熱傳導性散熱性片。此時成分(a1)和成分(a2)的比為1.4：1。此外，關於試驗例35~36，在二液加成反應型矽酮的黏度超過3,000mPa．sec的情況下，無法得到具有良好的柔軟性的熱傳導性散熱性片。 Regarding test examples 1~20 and test examples 26~30, by using component (A) two-component addition reaction type silicone series viscosity is 350~2,000mPa. sec, a thermally conductive heat dissipation sheet with good flexibility can be obtained. At this time, the ratio of the component (a1) to the component (a2) was 1.4:1. In addition, regarding Test Examples 35 to 36, the viscosity of the two-liquid addition reaction type silicone exceeds 3,000 mPa. sec, a thermally conductive heat dissipation sheet with good flexibility cannot be obtained.
關於試驗例21~30，在前述無機填料的粒度分布係在平均粒徑10~100μm、1~10μm、小於1μm的範圍內具有極大值或者波峰的情況下，能夠得到具有良好的柔軟性的熱傳導性散熱性片。 Regarding test examples 21 to 30, when the particle size distribution of the above-mentioned inorganic filler has a maximum value or a peak in the range of average particle diameter of 10 to 100 μm, 1 to 10 μm, and less than 1 μm, heat conduction with good flexibility can be obtained. Sexual heat sink.
特別是在在平均粒徑60~100μm、1~10μm及小於1μm的範圍內具有極大值或者波峰的情況下，能夠得到具有特好柔軟性的熱傳導性散熱性片。 In particular, when the average particle size has a maximum value or a peak in the range of 60 to 100 μm, 1 to 10 μm, and less than 1 μm, a thermally conductive heat dissipation sheet having particularly good flexibility can be obtained.
用於製造樹脂組成物的原材料如下。 The raw materials used to manufacture the resin composition are as follows.
＊1)二液加成反應型矽酮(具有乙烯基的有機聚矽氧烷(乙烯基含量0.8mol%)：具有H-Si基的有機聚矽氧烷(H-Si含量1.0mol%)=(a1)1.4：(a2)1)；Momentive公司製的X14-B8530；黏度350mPa．sec；各有機聚矽氧烷的質量平均分子量21,000。 *1) Two-component addition reaction silicone (organopolysiloxane with vinyl group (vinyl content: 0.8 mol%): organopolysiloxane with H-Si group (H-Si content: 1.0 mol%) =(a1)1.4:(a2)1); X14-B8530 manufactured by Momentive; viscosity 350 mPa. sec; the mass average molecular weight of each organopolysiloxane is 21,000.
＊1-2)二液加成反應型矽酮(具有乙烯基的有機聚矽氧烷(乙烯基含量0.8mol%)：具有H-Si基的有機聚矽氧烷(H-Si含量1.0mol%)=(a1)1：(a2)1)；Momentive公司製的X14-B8530；黏度350mPa．sec；各有機聚矽氧烷的質量平均分子量21,000。 *1-2) Two-component addition reaction silicone (organopolysiloxane with vinyl group (vinyl content: 0.8 mol%): organopolysiloxane with H-Si group (H-Si content: 1.0 mol%) %)=(a1)1:(a2)1); X14-B8530 manufactured by Momentive; viscosity 350 mPa. sec; the mass average molecular weight of each organopolysiloxane is 21,000.
＊1-3)二液加成反應型矽酮(具有乙烯基的有機聚矽氧烷(乙烯基含量0.8mol%)：具有H-Si基的有機聚矽氧烷(H-Si含量1.0mol%)=(a1)1：(a2)1.4)；Momentive公司製的X14-B8530；黏度350mPa．sec；各有機聚矽氧烷的質量平均分子量21,000。 *1-3) Two-component addition reaction silicone (organopolysiloxane with vinyl group (vinyl content: 0.8mol%): organopolysiloxane with H-Si group (H-Si content: 1.0mol%) %)=(a1)1:(a2)1.4); X14-B8530 manufactured by Momentive; viscosity 350 mPa. sec; the mass average molecular weight of each organopolysiloxane is 21,000.
＊2)二液加成反應型矽酮(具有乙烯基的有機聚矽氧烷(乙烯基含量0.3mol%)：具有H-Si基的有機聚矽氧烷(H-Si含量0.5mol%)=(a1)1.4：(a2)1)；Toray-Dow Corning公司製的SE-1885；黏度440mPa．sec；各有機聚矽氧烷的質量平均分子量120,000。 *2) Two-component addition reaction silicone (organopolysiloxane with vinyl group (vinyl content: 0.3 mol%): organopolysiloxane with H-Si group (H-Si content: 0.5 mol%) =(a1)1.4:(a2)1); SE-1885 manufactured by Toray-Dow Corning; viscosity 440 mPa. sec; the mass average molecular weight of each organopolysiloxane is 120,000.
＊2-2)二液加成反應型矽酮(具有乙烯基的有機聚矽氧烷(乙烯基含量0.3mol%)：具有H-Si基的有機聚矽氧烷(H-Si含量0.5mol%)=(a1)1：(a2)1)；Toray-Dow Corning公司製的SE-1885；黏度430mPa．sec；各有機聚矽氧烷的質量平均分子量120,000。 *2-2) Two-component addition reaction silicone (organopolysiloxane with vinyl group (vinyl content: 0.3 mol%): organopolysiloxane with H-Si group (H-Si content: 0.5 mol%) %)=(a1)1:(a2)1); SE-1885 manufactured by Toray-Dow Corning; viscosity 430 mPa. sec; the mass average molecular weight of each organopolysiloxane is 120,000.
＊2-3)二液加成反應型矽酮(具有乙烯基的有機聚矽氧烷(乙烯基含量0.3mol%)：具有H-Si基的有機聚矽氧烷(H-Si含量0.5mol%)=1：1.4)；Toray-Dow Corning公司製的SE-1885；黏度420mPa．sec；各有機聚矽氧烷的質量平均分子量120,000。 *2-3) Two-component addition reaction silicone (organopolysiloxane with vinyl group (vinyl content: 0.3 mol%): organopolysiloxane with H-Si group (H-Si content: 0.5 mol%) %)=1:1.4); SE-1885 manufactured by Toray-Dow Corning; viscosity 420 mPa. sec; the mass average molecular weight of each organopolysiloxane is 120,000.
＊2-4)二液加成反應型矽酮(具有乙烯基的有機聚矽氧烷(乙烯基含量0.3mol%)：具有H-Si基的有機聚矽氧烷(H-Si含量0.5mol%)=1：1.6)；Toray-Dow Corning公司製的SE-1885；黏度400mPa．sec；各有機聚矽氧烷的質量平均分子量120,000。 *2-4) Two-component addition reaction silicone (organopolysiloxane with vinyl group (vinyl content: 0.3mol%)): organopolysiloxane with H-Si group (H-Si content: 0.5mol%) %)=1:1.6); SE-1885 manufactured by Toray-Dow Corning; viscosity 400 mPa. sec; the mass average molecular weight of each organopolysiloxane is 120,000.
＊3)二液加成反應型矽酮(具有乙烯基的有機聚矽氧烷：具有H-Si基的有機聚矽氧烷=(a1)1.4：(a2)1)；信越化學股份有限公司製的KE-1283；黏度2,000mPa．sec。 *3) Two-component addition reaction silicone (organopolysiloxane with vinyl group: organopolysiloxane with H-Si group = (a1)1.4: (a2)1); Shin-Etsu Chemical Co., Ltd. Made KE-1283; viscosity 2,000mPa. sec.
＊4)二液加成反應型矽酮(具有乙烯基的有機聚矽氧烷：具有H-Si基的有機聚矽氧烷)=(a1)1.4：(a2)1；Momentive公司製的二液加成型矽酮TSE-3331K(具有乙烯基的有機聚矽氧烷：具有H-Si基的有機聚矽氧烷=1.4：1)；黏度3,000mPa．sec。 *4) Two-component addition reaction silicone (organopolysiloxane with vinyl group: organopolysiloxane with H-Si group)=(a1)1.4:(a2)1; Liquid addition type silicone TSE-3331K (organopolysiloxane with vinyl group:organopolysiloxane with H-Si group=1.4:1); viscosity 3,000mPa. sec.
＊5)在末端或者側鏈具有乙烯基的高分子量矽酮；Momentive公司製的SRH-32；乙烯基含量：0.1mol%，質量平均分子量500,000。 *5) High-molecular-weight silicone having a vinyl group at the terminal or side chain; SRH-32 manufactured by Momentive; vinyl content: 0.1 mol%, mass average molecular weight: 500,000.
＊6)在末端或者側鏈具有乙烯基的高分子量矽酮；Momentive公司製的TSE-201；乙烯基含量：0.2mol%，質量平均分子量800,000。 *6) High-molecular-weight silicone having a vinyl group at the terminal or side chain; TSE-201 manufactured by Momentive; vinyl content: 0.2 mol%, mass average molecular weight: 800,000.
＊7)烷氧基矽烷；Toray-Dow Corning公司製的Z-6210；正癸基三甲氧基矽烷。 *7) Alkoxysilane; Z-6210 manufactured by Toray-Dow Corning; n-decyltrimethoxysilane.
[成分(D)無機填料] [Component (D) inorganic filler]
無機填料使用下述的氧化鋁。表的無機填料的體積%係使用的各球狀填料及各結晶性礬土的合計量。 As the inorganic filler, the following alumina was used. The volume % of the inorganic filler in the table is the total amount of each spherical filler and each crystalline alumina used.
填料d50：70μm：Denka股份有限公司製的球狀礬土DAW70 Filler d50: 70 μm: spherical alumina DAW70 manufactured by Denka Co., Ltd.
填料d50：45μm：Denka股份有限公司製的球狀礬土DAW45S Filler d50: 45 μm: spherical alumina DAW45S manufactured by Denka Co., Ltd.
填料d50：5μm：Denka股份有限公司製的球狀礬土DAW05 Filler d50: 5 μm: spherical alumina DAW05 manufactured by Denka Co., Ltd.
填料d50：0.3μm：Denka股份有限公司製的球狀礬土ASFP20 Filler d50: 0.3 μm: spherical alumina ASFP20 manufactured by Denka Co., Ltd.
此外，結晶性礬土粉末使用下述者。 In addition, as the crystalline alumina powder, the following ones were used.
D50：3μm：住友化學股份有限公司製的結晶性礬土AA-3 D50: 3 μm: Crystalline alumina AA-3 manufactured by Sumitomo Chemical Co., Ltd.
D50：0.5μm：住友化學股份有限公司製的結晶性礬土AA-05 D50: 0.5 μm: Sumitomo Chemical Co., Ltd. crystalline alumina AA-05
[評價基準] [evaluation criteria]
評價係依以下進行判斷。 The evaluation was judged as follows.
＊熱傳導率小於3W/mK時為不佳，熱傳導率3W/mK以上時為良好，5W/mK以上時為優秀。 ＊When the thermal conductivity is less than 3W/mK, it is poor, when the thermal conductivity is more than 3W/mK, it is good, and when it is more than 5W/mK, it is excellent.
壓縮率小於25%時為不佳，壓縮率25%以上時為良好。 When the compression rate is less than 25%, it is not good, and when the compression rate is more than 25%, it is good.
阿斯克C硬度比30大時為高柔軟性不佳，阿斯克C硬度30以下時為高柔軟性良好，阿斯克C硬度15以下時為高柔軟性優秀。 When the Asker C hardness is greater than 30, the high flexibility is poor, when the Asker C hardness is 30 or less, the high flexibility is good, and when the Asker C hardness is 15 or less, the high flexibility is excellent.
<熱傳導性> <Thermal conductivity>
對於在上述所得到的片，剪裁成TO-3型，測定熱阻。然後，利用下述的(1)式及(2)式算出熱傳導率。 The sheet obtained above was cut into TO-3 type, and the thermal resistance was measured. Then, the thermal conductivity was calculated using the following formulas (1) and (2).
熱傳導率係將剪裁成TO-3型的試料包夾在內建有電晶體的TO-3型銅製加熱器外殼(有效面積6.0cm2)與銅板之間，以壓縮為初期厚度的10%的方式施加荷重而加以固定(set)後，向電晶體施加電力15W並保持5分鐘，用(2)式換算由加熱器外殼和散熱鰭的溫度差(℃)並用以下的(1)式所算出的熱阻(℃/W)。 The thermal conductivity is that the sample cut into TO-3 type is sandwiched between the TO-3 type copper heater shell (effective area 6.0cm 2 ) with a built-in transistor and the copper plate, and the compression is 10% of the initial thickness. After applying a load and fixing it (set), apply a power of 15W to the transistor and keep it for 5 minutes, and use the following formula (1) to convert the temperature difference (°C) between the heater shell and the cooling fin by using the formula (2) The thermal resistance (°C/W).
用「熱阻(℃/W)=(加熱器側溫度(℃)-冷卻側溫度(℃))/電力(W)...(1)」的公式算出。然後，能夠利用「熱傳導率(W/mK)=厚度(m)/(截面積(m2)×熱阻(℃/W))...(2)」的公式算出。 Calculated using the formula "thermal resistance (°C/W) = (heater side temperature (°C) - cooling side temperature (°C))/power (W)...(1)". Then, it can be calculated by the formula of "thermal conductivity (W/mK)=thickness (m)/(cross-sectional area (m 2 )×thermal resistance (°C/W))...(2)".
<阿斯克C硬度> <Ask C Hardness>
本發明中所使用的矽酮樹脂硬化後的硬度能夠用根據25℃的SRIS0101的阿斯克C類型的彈簧式硬度進行測定。阿斯克C硬度能夠用高分子計器股份有限公司製的「阿斯克橡膠硬度計C型」進行測定。矽酮樹脂硬化後的類型C阿斯克C硬度為5~30，理想的是7~15。若類型C硬度比5小，則在處理片之際的作業性變得困難。 The hardness of the silicone resin used in the present invention after curing can be measured by the Asker C type spring hardness according to SRIS0101 at 25°C. The Ascot C hardness can be measured with "Asco Rubber Hardness Tester Type C" manufactured by Polymer Instruments Co., Ltd. Type C after hardening of the silicone resin has an Asc C hardness of 5-30, ideally 7-15. When the Type C hardness is less than 5, workability when handling a sheet becomes difficult.
此外，若超過30，則熱傳導性片本身變硬，與發熱元件的緊貼性受損而熱傳導性變差。 Moreover, when it exceeds 30, the thermally conductive sheet itself becomes hard, the adhesiveness with a heating element is impaired, and thermal conductivity deteriorates.
<壓縮率> <compression ratio>
本發明中所使用的壓縮率係將間隔物打孔成10×10mm後，藉由桌上試驗機(島津製作所製的EZ-LX)，測量在厚度方向上施加0.1MPa的荷重時的壓縮變形量，以壓縮率(%)={壓縮變形量(mm)×100}/原本的厚度(mm) The compressibility used in the present invention is to measure the compression deformation when a load of 0.1 MPa is applied in the thickness direction with a tabletop testing machine (EZ-LX manufactured by Shimadzu Corporation) after the spacer is punched to a size of 10×10 mm. Amount, in terms of compression ratio (%)={compression deformation (mm)×100}/original thickness (mm)
算出壓縮率。 Calculate the compression ratio.
<質量平均分子量> <Mass average molecular weight>
聚有機矽氧烷及矽酮的質量平均分子量設為從凝膠滲透層析分析的結果求出的用聚苯乙烯換算的值。分離係在非水系的多孔性凝膠(聚苯乙烯-二甲基苯共聚物)，使用甲苯作為移動相，檢測係使用微差折射計(RI)。 The mass average molecular weights of polyorganosiloxanes and silicones were values calculated in terms of polystyrene from the results of gel permeation chromatography analysis. The separation system uses a non-aqueous porous gel (polystyrene-dimethylbenzene copolymer), using toluene as the mobile phase, and the detection system uses a differential refractometer (RI).
<平均粒徑、最大粒徑、極大值> <Average particle size, maximum particle size, maximum value>
無機填充材的平均粒徑、最大粒徑及極大值係使用島津製作所製的「雷射繞射式粒度分布測定裝置SALD-200」進行測定。評價樣品係向玻璃燒杯添加50cc 的純水、和測定的無機填充材粉末5g，使用刮勺攪拌，之後用超音波洗淨機進行10分鐘分散處理。使用吸量管，將進行過分散處理的無機填充材的粉末的溶液逐滴添加至裝置的取樣部，等待穩定至可以測定吸光度。依此方式操作，在吸光度變得穩定的時候進行測定。雷射繞射式粒度分布測定裝置係由基於用感測器檢測的粒子的繞射/散射光的光強度分布的資料計算粒度分布。平均粒徑係將相對粒子量(差分%)乘以所測定的粒徑的值，除以相對粒子量的合計(100%)來求出。又，平均粒徑係粒子的平均直徑，能夠以極大值或者波峰值的累積重量平均值D50(或者中位徑)的形式求出。又，D50係出現率達到最大的粒徑。 The average particle size, maximum particle size, and maximum value of the inorganic filler were measured using a "laser diffraction particle size distribution analyzer SALD-200" manufactured by Shimadzu Corporation. The evaluation sample was added to a glass beaker with 50 cc of pure water and 5 g of the inorganic filler powder to be measured, stirred with a spatula, and then dispersed for 10 minutes with an ultrasonic cleaner. Using a pipette, add the solution of the dispersed inorganic filler powder dropwise to the sampling part of the device, and wait until it stabilizes until the absorbance can be measured. Operate in this way, and measure when the absorbance becomes stable. The laser diffraction particle size distribution measuring device calculates the particle size distribution from the data of the light intensity distribution based on the diffracted/scattered light of the particles detected by the sensor. The average particle diameter was obtained by multiplying the relative particle amount (difference %) by the measured particle diameter, and dividing by the total (100%) of the relative particle amount. In addition, the average diameter of particles based on the average particle diameter can be obtained as the cumulative weight average value D 50 (or median diameter) of the maximum value or peak value. Also, the D 50 series is the particle diameter at which the occurrence rate becomes the largest.
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