TW202248310A - Method for manufacturing thermally conductive sheet - Google Patents

Abstract

A method for manufacturing a thermally conductive sheet according to the present invention comprises: (A) a step for fabricating a primary sheet containing a polymer matrix and an anisotropic filler dispersed in the polymer matrix, the anisotropic filler being oriented in a thickness direction with an end portion of the anisotropic filler exposed on a surface of the primary sheet; (B) a pressing step for compressing the primary sheet in the thickness direction; and (C) a polishing step for polishing the surface of the primary sheet. According to the present invention, it is possible to provide a method for manufacturing a thermally conductive sheet having a thermal resistance value lower than before.

Description

導熱性片之製造方法Manufacturing method of thermally conductive sheet

本發明係關於一種導熱性片之製造方法，例如係關於一種配置於發熱體與散熱體之間而使用之導熱性片之製造方法。The present invention relates to a method of manufacturing a thermally conductive sheet, for example, relates to a method of manufacturing a thermally conductive sheet disposed between a heating element and a radiator.

在電腦、汽車零件、行動電話等電子機器中，為了使由半導體元件、機械零件等發熱體產生之熱進行發散，一般使用散熱片（heat sink）等散熱體。已知出於提高對散熱體之傳熱效率之目的，於發熱體與散熱體之間配置導熱性片。 一般而言，導熱性片配置於電子機器內部時以壓縮之方式使用，故要求其具有高柔軟性。因此，於橡膠或凝膠等柔軟性較高之高分子基質中摻合具有導熱性之填充材，構成導熱性片。又，眾所周知，為提高導熱性片於厚度方向上之導熱性，使碳纖維等具有異向性之填充材於厚度方向上配向（例如，參照專利文獻1、2）。 In electronic devices such as computers, auto parts, and mobile phones, in order to dissipate the heat generated by heating elements such as semiconductor elements and mechanical parts, heat sinks and other heat sinks are generally used. It is known that a thermally conductive sheet is disposed between a heat generating body and a heat sink for the purpose of improving heat transfer efficiency to a heat sink. Generally speaking, when a thermally conductive sheet is arranged inside an electronic device, it is used in a compressed form, so it is required to have high flexibility. Therefore, a thermally conductive filler is mixed with a flexible polymer matrix such as rubber or gel to form a thermally conductive sheet. Also, it is known to align anisotropic fillers such as carbon fibers in the thickness direction in order to improve the thermal conductivity of the thermally conductive sheet in the thickness direction (for example, refer to Patent Documents 1 and 2).

又，除使異向性填充材於厚度方向上配向之方法以外，各種嘗試提高導熱性之方法亦被研究。 專利文獻3揭示了關於如下導熱性片之發明，該導熱性片中，就進一步提高導熱性之觀點而言，使碳纖維等具有異向性之填充材於片表面露出，並且使片表面之峰頂點之算術平均曲率（Spc）在一定數值以下，並揭示該導熱性片可降低熱阻值（即，可提高導熱性）。 專利文獻4記載了一種導熱性片之製造方法，該方法具有由黏合劑樹脂中含有導熱性填料之導熱性樹脂組成物形成成型體片，並對該成型體片進行加壓之步驟。該製造方法中，成型體片中含有黏合劑樹脂之未硬化成分，藉由對該未硬化成分進行加壓，使其於片表面露出。其結果，未硬化成分覆蓋片整個表面，可提高片與發熱體及散熱體之密接性，降低熱阻值。 [先前技術文獻] [專利文獻] Furthermore, in addition to the method of aligning the anisotropic filler in the thickness direction, various methods of attempting to improve thermal conductivity have also been studied. Patent Document 3 discloses an invention related to a thermally conductive sheet in which an anisotropic filler such as carbon fiber is exposed on the surface of the sheet and peaks on the surface of the sheet are exposed from the viewpoint of further improving thermal conductivity. The arithmetic mean curvature (Spc) of the vertex is below a certain value, which indicates that the thermal conductivity sheet can reduce the thermal resistance value (ie, improve the thermal conductivity). Patent Document 4 describes a method for producing a thermally conductive sheet, which includes the steps of forming a molded sheet from a thermally conductive resin composition containing a thermally conductive filler in a binder resin, and pressurizing the molded sheet. In this production method, the uncured component of the binder resin is contained in the molded product sheet, and the uncured component is exposed on the surface of the sheet by pressing. As a result, the uncured component covers the entire surface of the sheet, which improves the adhesion between the sheet, the heating element and the radiator, and reduces the thermal resistance. [Prior Art Literature] [Patent Document]

專利文獻1：日本特開2018-056315號公報 專利文獻2：日本特開2018-014534號公報 專利文獻3：國際公開第2020/067141號 專利文獻4：日本特開2015-029076號公報 Patent Document 1: Japanese Patent Laid-Open No. 2018-056315 Patent Document 2: Japanese Patent Laid-Open No. 2018-014534 Patent Document 3: International Publication No. 2020/067141 Patent Document 4: Japanese Patent Laid-Open No. 2015-029076

[發明所欲解決之課題][Problem to be Solved by the Invention]

在上述藉由未硬化成分覆蓋片整個表面之方法中，未硬化成分含有乙烯基等反應性較高之基，故而亦擔憂因紫外線產生反應或與被黏著體反應，從而產生不良情況。又，擔憂使用過程中，未硬化成分轉移（滲出）至被黏著體。 又，根據上述各專利文獻揭示之發明，可獲得熱阻值相對較低、散熱性良好之導熱性片，然而，近年來，隨著電子機器之高程度化，其發熱量增加，因此要求一種熱阻值較先前低之導熱性片。 In the above-mentioned method of covering the entire surface of the sheet with the uncured component, the uncured component contains a highly reactive group such as a vinyl group, so there is also concern about adverse effects due to the reaction of ultraviolet rays or the reaction with the adherend. In addition, there is a concern that unhardened components may transfer (bleed) to an adherend during use. Also, according to the inventions disclosed in the above-mentioned patent documents, a thermally conductive sheet with relatively low thermal resistance and good heat dissipation can be obtained. However, in recent years, with the advancement of electronic equipment, the amount of heat generated has increased. Therefore, a Thermally conductive sheet with lower thermal resistance than before.

因此，本發明之課題在於提供一種製造熱阻值較先前低之導熱性片之方法。 [解決課題之技術手段] Therefore, an object of the present invention is to provide a method of manufacturing a thermally conductive sheet having a lower thermal resistance than before. [Technical means to solve the problem]

本發明者經過努力研究，結果發現，藉由對含有高分子基質與分散於該高分子基質之異向性填充材之特定初級片實施加壓步驟與研磨步驟兩個步驟，可解決上述課題，從而完成了本發明。 即，本發明提供以下之[1]至[8]。 As a result of diligent research, the present inventors have found that the above-mentioned problems can be solved by performing two steps of pressurization and grinding on a specific primary sheet containing a polymer matrix and an anisotropic filler dispersed in the polymer matrix. The present invention has thus been accomplished. That is, the present invention provides the following [1] to [8].

[1]一種導熱性片之製造方法，其具備：（A）製作初級片之步驟，該初級片含有高分子基質及分散於上述高分子基質之異向性填充材，上述異向性填充材於厚度方向上配向，且上述異向性填充材之端部於表面露出；（B）加壓步驟，其將上述初級片於厚度方向上進行壓縮；及（C）研磨步驟，其研磨上述初級片之表面。 [2]如上述[1]之導熱性片之製造方法，其中，上述加壓步驟中之初級片之厚度變化為3%以上。 [3]如上述[1]或[2]之導熱性片之製造方法，其中，上述異向性填充材含有碳纖維。 [4]如上述[1]至[3]中任一項之導熱性片之製造方法，其中，上述異向性填充材含有碳纖維及鱗片狀碳粉末。 [5]如上述[1]至[4]中任一項之導熱性片之製造方法，其中，上述高分子基質包含有機聚矽氧烷。 [6]如上述[1]至[5]中任一項之導熱性片之製造方法，其中，上述高分子基質包含有機聚矽氧烷及烴系化合物。 [7]如上述[1]至[6]中任一項之導熱性片之製造方法，其中，於（C）研磨步驟之前進行上述（B）加壓步驟。 [8]如上述[1]至[6]中任一項之導熱性片之製造方法，其中，於（C）研磨步驟之後進行上述（B）加壓步驟，上述（B）加壓步驟係使初級片之表面粗糙化之步驟。 [發明之效果] [1] A method of manufacturing a thermally conductive sheet, comprising: (A) a step of producing a primary sheet, the primary sheet comprising a polymer matrix and an anisotropic filler dispersed in the polymer matrix, the anisotropic filler Alignment in the thickness direction, and the end of the above-mentioned anisotropic filler is exposed on the surface; (B) a pressing step, which compresses the above-mentioned primary sheet in the thickness direction; and (C) a grinding step, which grinds the above-mentioned primary sheet The surface of the piece. [2] The method for producing a thermally conductive sheet according to [1] above, wherein the variation in thickness of the primary sheet in the pressing step is 3% or more. [3] The method for producing a thermally conductive sheet according to the above [1] or [2], wherein the anisotropic filler contains carbon fibers. [4] The method for producing a thermally conductive sheet according to any one of [1] to [3] above, wherein the anisotropic filler contains carbon fibers and flaky carbon powder. [5] The method for producing a thermally conductive sheet according to any one of [1] to [4] above, wherein the polymer matrix includes an organopolysiloxane. [6] The method for producing a thermally conductive sheet according to any one of [1] to [5] above, wherein the polymer matrix includes an organopolysiloxane and a hydrocarbon compound. [7] The method for producing a thermally conductive sheet according to any one of [1] to [6] above, wherein the (B) pressurizing step is performed before the (C) grinding step. [8] The method for producing a thermally conductive sheet according to any one of the above [1] to [6], wherein the (B) pressurizing step is performed after the (C) grinding step, and the above (B) pressurizing step is A step of roughening the surface of the primary sheet. [Effect of Invention]

根據本發明，可提供一種製造熱阻值較先前低之導熱性片之方法。According to the present invention, it is possible to provide a method of manufacturing a thermally conductive sheet having a lower thermal resistance than before.

本發明之導熱性片之製造方法具備：（A）製作初級片之步驟，該初級片含有高分子基質及分散於上述高分子基質之異向性填充材，上述異向性填充材於厚度方向上配向，且上述異向性填充材之端部於表面露出；（B）加壓步驟，其將上述初級片於厚度方向上進行壓縮；及（C）研磨步驟，其研磨上述初級片之表面。The manufacturing method of the thermally conductive sheet of the present invention includes: (A) the step of producing a primary sheet, the primary sheet contains a polymer matrix and an anisotropic filler dispersed in the polymer matrix, and the anisotropic filler is in the thickness direction upward alignment, and the end of the above-mentioned anisotropic filler is exposed on the surface; (B) a pressing step, which compresses the above-mentioned primary sheet in the thickness direction; and (C) a grinding step, which grinds the surface of the above-mentioned primary sheet .

根據本發明之製造方法，可製造熱阻值較低之導熱性片。其原因尚不確定，可推斷如下。 認為（B）加壓步驟中，片於厚度方向被壓縮，其結果，使厚度一定程度地減小。因此，片內部之每單位體積之異向性填充材之濃度增加，其結果，易形成導熱通道，熱阻值降低。又，（C）研磨步驟中，藉由研磨，提高片表面之平滑性，其結果，片與被黏著體易密接，因此熱阻值降低。該等（B）加壓步驟及（C）研磨步驟利用互相不同之作用機制發揮降低熱阻值之效果，藉由實施該等兩個步驟，可更有效地降低熱阻值。 According to the manufacturing method of the present invention, a thermally conductive sheet with low thermal resistance can be manufactured. The reason for this is not certain but can be inferred as follows. It is considered that the sheet is compressed in the thickness direction in the (B) pressing step, and as a result, the thickness is reduced to some extent. Therefore, the concentration of the anisotropic filler per unit volume inside the sheet increases, and as a result, heat conduction channels are easily formed, and the thermal resistance decreases. In addition, in the (C) polishing step, the smoothness of the surface of the sheet is improved by polishing, and as a result, the sheet and the adherend tend to be in close contact, so that the thermal resistance value decreases. The (B) pressurizing step and (C) grinding step use different mechanisms to reduce the thermal resistance. By implementing these two steps, the thermal resistance can be reduced more effectively.

再者，本發明中，（B）加壓步驟及（C）研磨步驟之順序並無特別限定。即，可於（C）研磨步驟之前進行（B）加壓步驟，亦可於（C）研磨步驟之後進行（B）加壓步驟。就獲得熱阻值更低之導熱性片之觀點而言，較佳為於（C）研磨步驟之後進行（B）加壓步驟。其原因推斷如下，藉由先進行（C）研磨步驟，使片表面變得平滑，繼而對該平滑表面進行（B）加壓步驟，因此於相同之加壓條件下容易被加壓。 以下將詳細地說明本發明之製造方法之各步驟。 In addition, in this invention, the order of (B) pressurization process and (C) grinding process is not specifically limited. That is, the (B) pressurization step may be performed before the (C) grinding step, or the (B) pressurization step may be performed after the (C) grinding step. From the viewpoint of obtaining a thermally conductive sheet with lower thermal resistance, it is preferable to perform (B) pressurizing step after (C) grinding step. The reason for this is presumed to be as follows. The surface of the sheet is smoothed by first performing the (C) polishing step, and then the smooth surface is subjected to the (B) pressurization step, so it is easy to be pressurized under the same pressurization conditions. Each step of the manufacturing method of the present invention will be described in detail below.

[（A）製作初級片之步驟] 對本步驟製作之初級片進行說明。 [(A) Steps in making primary films] The primary film produced in this step will be described.

＜初級片＞ 初級片含有高分子基質及分散於上述高分子基質之異向性填充材，上述異向性填充材於厚度方向上配向，且上述異向性填充材之端部於表面露出。 ＜Elementary film＞ The primary sheet contains a polymer matrix and an anisotropic filler dispersed in the polymer matrix, the anisotropic filler is aligned in the thickness direction, and the end of the anisotropic filler is exposed on the surface.

參考圖式，對本發明之初級片進行說明。再者，本發明並不限定於圖式之內容。圖1中，代表性示出異向性填充材為纖維材料之情形之例。 本發明之一實施方式之初級片10含有高分子基質14及分散於該高分子基質14之異向性填充材12。異向性填充材12之端部於初級片10之表面10A、10B露出。又，於初級片10之內部，異向性填充材12之長軸於初級片10之厚度方向上配向。如此，藉由於厚度方向上配向之異向性填充材12，容易於厚度方向上形成導熱通道，降低初級片10之熱阻值。為使異向性填充材12配向，可實施後述磁場配向或流動配向等處理。 The primary sheet of the present invention will be described with reference to the drawings. Furthermore, the present invention is not limited to the contents of the drawings. In FIG. 1 , an example in which the anisotropic filler is a fiber material is representatively shown. A primary sheet 10 according to an embodiment of the present invention includes a polymer matrix 14 and an anisotropic filler 12 dispersed in the polymer matrix 14 . The ends of the anisotropic filler 12 are exposed on the surfaces 10A and 10B of the primary sheet 10 . Also, inside the primary sheet 10 , the major axis of the anisotropic filler 12 is aligned in the thickness direction of the primary sheet 10 . In this way, with the anisotropic filler 12 oriented in the thickness direction, it is easy to form a heat conduction channel in the thickness direction, reducing the thermal resistance of the primary sheet 10 . In order to align the anisotropic filler 12, treatment such as magnetic field alignment or flow alignment described later may be performed.

此處，所謂異向性填充材12於初級片10之厚度方向上配向之狀態，係指個數比率超過60%之異向性填充材12之長軸方向處於距離初級片10之厚度方向20°以內之範圍之狀態。此種配向狀態可藉由利用電子顯微鏡觀察沿初級片10之厚度方向之剖面來確認。Here, the so-called state that the anisotropic filler 12 is aligned in the thickness direction of the primary sheet 10 means that the long axis direction of the anisotropic filler 12 whose number ratio exceeds 60% is 20° away from the primary sheet 10 in the thickness direction. The state within the range of °. Such an alignment state can be confirmed by observing a cross section along the thickness direction of the primary sheet 10 with an electron microscope.

如圖1所示，藉由含有非異向性填充材16，初級片之導熱性變得進一步良好。非異向性填充材16之詳情見後述。再者，初級片可如圖2之初級片20所示，不含非異向性填充材16。As shown in FIG. 1 , by including the anisotropic filler 16 , the thermal conductivity of the primary sheet becomes further improved. Details of the anisotropic filler 16 will be described later. Furthermore, the primary sheet can be shown as the primary sheet 20 in FIG. 2 without the anisotropic filler 16 .

（高分子基質） 初級片中使用之高分子基質為彈性體或橡膠等高分子化合物，較佳為使用由如主劑及硬化劑之混合系構成之液狀高分子組成物（硬化性高分子組成物）硬化而形成者。硬化性高分子組成物例如可為由未交聯橡膠及交聯劑構成者，亦可為包含單體、預聚物等及硬化劑等者。又，上述硬化反應可為常溫硬化，亦可為熱硬化。 (polymer matrix) The polymer matrix used in the primary sheet is a polymer compound such as an elastomer or rubber, and it is preferably hardened by using a liquid polymer composition (curable polymer composition) composed of a mixture of a main agent and a hardener. former. The curable polymer composition may be composed of, for example, uncrosslinked rubber and a crosslinking agent, or may include monomers, prepolymers, etc., and a curing agent. In addition, the above-mentioned curing reaction may be room temperature curing or thermal curing.

由硬化性高分子組成物形成之高分子基質較佳為包含有機聚矽氧烷（聚矽氧橡膠），該有機聚矽氧烷較佳為具有交聯結構。形成此種有機聚矽氧烷時，較佳為使用加成反應硬化型聚矽氧，更具體而言，作為硬化性高分子組成物，使用包含含烯基有機聚矽氧烷及有機氫化聚矽氧烷者即可。The polymer matrix formed of the curable polymer composition preferably contains organopolysiloxane (polysiloxane rubber), and the organopolysiloxane preferably has a cross-linked structure. When forming such an organopolysiloxane, it is preferable to use an addition reaction-curable polysiloxane, and more specifically, as a curable polymer composition, a compound containing an alkenyl group-containing organopolysiloxane and an organohydrogenated polysiloxane is used. Siloxane will do.

作為橡膠，除上述以外，還可使用各種合成橡膠，具體例例如可列舉丙烯酸橡膠、腈橡膠、異戊二烯橡膠、胺酯（urethane）橡膠、乙烯丙烯橡膠、苯乙烯-丁二烯橡膠、丁二烯橡膠、氟橡膠、丁基橡膠等。當使用該等橡膠時，合成橡膠可於初級片中交聯或保持未交聯（即，未硬化）。未交聯之橡膠主要用於流動配向。 又，於交聯（即，硬化）之情形時，如上所述，高分子基質可為由如下硬化性高分子組成物硬化而形成者，該硬化性高分子組成物為由該等合成橡膠形成之未交聯橡膠及交聯劑構成。 又，作為彈性體，亦可使用聚酯系熱塑性彈性體、聚胺酯系熱塑性彈性體等熱塑性彈性體、或由主劑及硬化劑構成之混合系液狀高分子組成物硬化形成之熱硬化型彈性體。例如，可例示由包含具有羥基之高分子及異氰酸酯之高分子組成物硬化而形成之聚胺酯系彈性體。 上述之中，就例如硬化後之高分子基質尤其柔軟、導熱性填充材之填充性良好之觀點而言，高分子基質較佳為有機聚矽氧烷。 As the rubber, various synthetic rubbers other than those mentioned above can be used. Specific examples include acrylic rubber, nitrile rubber, isoprene rubber, urethane rubber, ethylene propylene rubber, styrene-butadiene rubber, Butadiene rubber, fluorine rubber, butyl rubber, etc. When such rubbers are used, the synthetic rubber can be crosslinked in the primary sheet or remain uncrosslinked (ie, not hardened). Uncrosslinked rubber is mainly used for flow alignment. Also, in the case of crosslinking (i.e., hardening), as described above, the polymer matrix may be formed by hardening a curable polymer composition formed of these synthetic rubbers It is composed of uncrosslinked rubber and crosslinking agent. In addition, as the elastomer, thermoplastic elastomers such as polyester-based thermoplastic elastomers and polyurethane-based thermoplastic elastomers, or thermosetting elastic elastomers formed by hardening a mixed liquid polymer composition composed of a main agent and a hardener can also be used. body. For example, a polyurethane-based elastomer cured from a polymer composition containing a polymer having a hydroxyl group and an isocyanate can be exemplified. Among the above, the polymer matrix is preferably an organopolysiloxane from the viewpoint that the polymer matrix after hardening is particularly soft and that the thermally conductive filler has good filling properties.

高分子基質可為由有機聚矽氧烷等高分子化合物單體構成者，更佳為包含有機聚矽氧烷及烴系化合物。 烴系化合物可使用於室溫時為液狀或藉由加熱至一定溫度（例如，高於23℃且80℃以下之溫度）而熔融之化合物。藉由使初級片含有液狀化合物或經加熱而熔融之化合物作為烴系化合物，可提高加熱時之柔軟性。因此，可提高由初級片形成之導熱性片與發熱體及散熱體等之密接性，可降低熱阻值。 The polymer matrix can be composed of polymer monomers such as organopolysiloxane, and more preferably includes organopolysiloxane and hydrocarbon compounds. As the hydrocarbon compound, a compound that is liquid at room temperature or melts by heating to a certain temperature (for example, a temperature higher than 23° C. and lower than 80° C.) can be used. By making the primary sheet contain a liquid compound or a compound melted by heating as a hydrocarbon compound, flexibility during heating can be improved. Therefore, the adhesion between the thermally conductive sheet formed of the primary sheet and the heating element, radiator, etc. can be improved, and the thermal resistance value can be reduced.

就加熱時（例如80℃）可熔融之觀點而言，烴系化合物之熔點較佳為80℃以下，更佳為70℃以下，進而較佳為60℃以下，進而更佳為50℃以下。 烴系化合物較佳為於室溫、1大氣壓時為固體狀。藉由在於室溫時為固體，提高操作性，例如，於室溫附近之溫度進行後述切割加工時，因具有特定之剛性，而可容易地獲得初級片。因此，烴系化合物之熔點較佳為高於常溫（23℃），更佳為30℃以上，進而較佳為35℃以上。再者，烴系化合物之熔點係使用熱重量示差熱分析（TGDTA）以升溫速度1℃/min測得之DTA曲線之吸熱波峰之溫度。又，當烴系化合物為混合物時，熔點係上述溫度範圍中之最大吸熱波峰。 From the viewpoint of being meltable when heated (for example, 80°C), the melting point of the hydrocarbon compound is preferably 80°C or lower, more preferably 70°C or lower, further preferably 60°C or lower, even more preferably 50°C or lower. The hydrocarbon-based compound is preferably solid at room temperature and 1 atmosphere. Since it is solid at room temperature, workability is improved. For example, when cutting processing described later is performed at a temperature near room temperature, primary sheets can be easily obtained due to specific rigidity. Therefore, the melting point of the hydrocarbon compound is preferably higher than normal temperature (23°C), more preferably 30°C or higher, and still more preferably 35°C or higher. Furthermore, the melting point of the hydrocarbon compound is the temperature of the endothermic peak of the DTA curve measured by thermogravimetric differential thermal analysis (TGDTA) at a heating rate of 1°C/min. Also, when the hydrocarbon compound is a mixture, the melting point is the maximum endothermic peak in the above temperature range.

作為烴系化合物之具體例，可列舉液態石蠟、石蠟、凡士林、聚α-烯烴（PAO）、聚乙烯蠟、聚丙烯蠟等。該等之中，就於常溫時之操作性等觀點而言，較佳為石蠟、凡士林、聚α-烯烴（PAO）、聚乙烯蠟、聚丙烯蠟。再者，凡士林係一種半固態烴系化合物，係異烷烴、環烷烴（cycloparaffin）、環烷（naphthene）等多種烴系化合物之混合物。又，作為凡士林，例如可例示日本藥典中所定義之白色凡士林。Specific examples of the hydrocarbon-based compound include liquid paraffin, paraffin, vaseline, polyα-olefin (PAO), polyethylene wax, polypropylene wax, and the like. Among them, paraffin wax, vaseline, polyα-olefin (PAO), polyethylene wax, and polypropylene wax are preferable from the viewpoint of handleability at room temperature. Furthermore, petrolatum is a semi-solid hydrocarbon compound, which is a mixture of various hydrocarbon compounds such as isoalkane, cycloparaffin, and naphthene. Moreover, as petrolatum, white petrolatum defined in the Japanese Pharmacopoeia can be exemplified, for example.

上述之中，聚α-烯烴（PAO）較佳，其中，具有結晶性之晶質聚α-烯烴（CPAO）更佳。聚α-烯烴為α-烯烴之聚合物。α-烯烴之種類並無特別限制，可為直鏈，可具有支鏈，又，可具有環狀結構。聚α-烯烴例如為碳數2～30之α-烯烴之聚合物，較佳為碳數6～20之α-烯烴之聚合物。藉由增加結晶性聚α-烯烴、例如α-烯烴之碳數，可製成側鏈結晶性聚α-烯烴。 聚α-烯烴可為單一α-烯烴之聚合物，亦可為兩種以上α-烯烴之共聚物。 Among the above, polyα-olefin (PAO) is preferred, and among them, crystalline polyα-olefin (CPAO) is more preferred. Polyalphaolefins are polymers of alpha-olefins. The type of α-olefin is not particularly limited, and may have a straight chain, a branched chain, or a cyclic structure. The polyα-olefin is, for example, a polymer of α-olefins having 2 to 30 carbon atoms, preferably a polymer of α-olefins having 6 to 20 carbon atoms. By increasing the carbon number of crystalline polyalpha-olefins, such as alpha-olefins, side-chain crystalline polyalpha-olefins can be produced. Poly α-olefin can be a polymer of a single α-olefin, or a copolymer of two or more α-olefins.

初級片中，相對於有機聚矽氧烷及烴系化合物之總計100質量份，烴系化合物之含量較佳為1～50質量份。 若烴系化合物之含量為1質量份以上，則導熱性片於高溫下具有一定之柔軟性，組裝於發熱體與散熱體之間等時之導熱性易提高。 另一方面，若上述含量為50質量份以下，則導熱性片中含有一定量之有機聚矽氧烷，可使導熱性片之保形性良好。進而，導熱性片易具有適當之回彈性，且與發熱體或散熱體之間不形成空氣層而穩定地組裝，提高可靠性。 就該等觀點而言，烴系化合物之含量更佳為3質量份以上，進而較佳為5質量份以上，進而更佳為8質量份以上，又，更佳為40質量份以下，進而較佳為30質量份以下，進而更佳為25質量份以下。 In the primary sheet, the content of the hydrocarbon-based compound is preferably from 1 to 50 parts by mass relative to 100 parts by mass in total of the organopolysiloxane and the hydrocarbon-based compound. When the content of the hydrocarbon compound is more than 1 part by mass, the thermally conductive sheet has a certain degree of flexibility at high temperature, and the thermal conductivity when assembled between the heating element and the radiator is easy to improve. On the other hand, if the above-mentioned content is less than 50 parts by mass, a certain amount of organopolysiloxane is contained in the thermally conductive sheet, so that the shape retention of the thermally conductive sheet can be improved. Furthermore, the thermally conductive sheet is easy to have appropriate resilience, and can be assembled stably without forming an air layer between the heating element or the heat dissipation element, thereby improving reliability. From these viewpoints, the content of the hydrocarbon-based compound is more preferably at least 3 parts by mass, more preferably at least 5 parts by mass, still more preferably at least 8 parts by mass, still more preferably at most 40 parts by mass, and still more preferably at least 40 parts by mass. Preferably, it is 30 mass parts or less, More preferably, it is 25 mass parts or less.

若以體積基準之填充率（體積填充率）表示高分子基質之含量，則相對於初級片總量，較佳為20～50體積%，更佳為25～45體積%。If the content of the polymer matrix is represented by the volume-based filling rate (volume filling rate), it is preferably 20-50% by volume, more preferably 25-45% by volume relative to the total amount of the primary sheet.

（添加劑） 於高分子基質中，可於不損害初級片及由其形成之導熱性片之功能之範圍內，進而摻合各種添加劑。作為添加劑，例如可列舉選自分散劑、偶合劑、黏著劑、阻燃劑、抗氧化劑、著色劑、防沈澱劑等之至少一種以上。又，當使硬化性高分子組成物如上所述進行交聯、硬化等時，可摻合促進交聯、硬化之交聯促進劑、硬化促進劑等作為添加劑。 (additive) In the polymer matrix, various additives can be blended within the scope of not impairing the functions of the primary sheet and the thermally conductive sheet formed therefrom. As an additive, for example, at least one or more selected from a dispersant, a coupling agent, an adhesive, a flame retardant, an antioxidant, a colorant, an anti-sedimentation agent, and the like can be mentioned. Also, when the curable polymer composition is subjected to crosslinking, hardening, etc. as described above, a crosslinking accelerator, a hardening accelerator, etc. that accelerate crosslinking and hardening may be blended as additives.

（異向性填充材） 高分子基質中所含異向性填充材係形狀上具有異向性之填充材，且為可配向之填充材。異向性填充材較佳為導熱性填充材。作為異向性填充材，較佳為纖維狀填充材（例如碳纖維等纖維材料）、鱗片狀填充材（石墨、石墨烯、氮化硼等鱗片狀材料）等。 (anisotropic filler) The anisotropic filler contained in the polymer matrix is an anisotropic filler in shape and can be aligned. The anisotropic filler is preferably a thermally conductive filler. As the anisotropic filler, fibrous fillers (for example, fiber materials such as carbon fibers), and scaly fillers (flaky materials such as graphite, graphene, and boron nitride), and the like are preferable.

異向性填充材之縱橫比較高，具體而言，縱橫比超過2，縱橫比較佳為5以上。藉由使縱橫比大於2，容易使異向性填充材於厚度方向上配向，易提高初級片及導熱性片之導熱性。 又，縱橫比之上限並無特別限定，但從實用性而言，其上限為100。 再者，所謂縱橫比，係指異向性填充材之長軸方向之長度與短軸方向之長度之比，當異向性填充材為纖維材料時，縱橫比係指纖維長度/纖維直徑，當為鱗片狀材料時，縱橫比係指鱗片狀材料之長軸方向之長度/厚度。 就提高導熱性之觀點而言，異向性填充材較佳為纖維材料。 The aspect ratio of the anisotropic filler is high, specifically, the aspect ratio exceeds 2, and the aspect ratio is preferably 5 or more. By making the aspect ratio greater than 2, it is easy to align the anisotropic filler in the thickness direction, and it is easy to improve the thermal conductivity of the primary sheet and the thermally conductive sheet. In addition, the upper limit of the aspect ratio is not particularly limited, but the upper limit is 100 for practical use. Furthermore, the so-called aspect ratio refers to the ratio of the length of the long axis direction of the anisotropic filler to the length of the short axis direction. When the anisotropic filler is a fiber material, the aspect ratio refers to the fiber length/fiber diameter, In the case of a scaly material, the aspect ratio refers to the length/thickness in the long axis direction of the scaly material. From the viewpoint of improving thermal conductivity, the anisotropic filler is preferably a fiber material.

相對於高分子基質100質量份，初級片中之異向性填充材之含量較佳為30～500質量份，更佳為50～300質量份。又，關於異向性填充材之含量，若以體積基準之填充率（體積填充率）表示，則相對於初級片總量，其較佳為5～60體積%，更佳為8～45體積%。 藉由使異向性填充材之含量為30質量份以上，易提高導熱性，藉由使異向性填充材之含量為300質量份以下，易使後述混合組成物之黏度適當，使異向性填充材之配向性良好。 The content of the anisotropic filler in the primary sheet is preferably from 30 to 500 parts by mass, more preferably from 50 to 300 parts by mass, relative to 100 parts by mass of the polymer matrix. Also, the content of the anisotropic filler is preferably 5 to 60% by volume, more preferably 8 to 45% by volume, relative to the total amount of the primary sheet, in terms of volume-based filling rate (volume filling rate). %. By making the content of the anisotropic filler 30 parts by mass or more, it is easy to improve thermal conductivity, and by making the content of the anisotropic filler 300 parts by mass or less, it is easy to make the viscosity of the mixed composition described later appropriate, and make the anisotropic The orientation of the permanent filler is good.

當異向性填充材為纖維材料時，其平均纖維長度較佳為50～500 μm，更佳為70～350 μm。若使平均纖維長度為50 μm以上，則於初級片內部，異向性填充材彼此適當接觸，確保傳熱路徑。 另一方面，若使平均纖維長度為500 μm以下，則異向性填充材之體積減小，可高度填充於高分子基質中。 When the anisotropic filler is a fiber material, its average fiber length is preferably 50-500 μm, more preferably 70-350 μm. If the average fiber length is 50 μm or more, the anisotropic fillers will be in proper contact with each other inside the primary sheet, thereby securing a heat transfer path. On the other hand, if the average fiber length is 500 μm or less, the volume of the anisotropic filler can be reduced, and it can be highly filled in the polymer matrix.

又，纖維材料之平均纖維長度較佳為短於初級片之厚度。藉由使纖維材料之平均纖維長度短於初級片之厚度，防止纖維材料從初級片之表面超過必要程度地突出。 又，當異向性填充材為鱗片狀材料時，其平均粒徑較佳為10～400 μm，更佳為15～200 μm。又，特佳為15～130 μm。藉由使平均粒徑為10 μm以上，初級片中之異向性填充材彼此容易接觸，確保傳熱路徑。另一方面，若使平均粒徑為400 μm以下，則異向性填充材之體積減小，可將異向性填充材高度填充至高分子基質中。 再者，碳纖維之平均纖維長度或鱗片狀材料之平均粒徑可利用顯微鏡觀察異向性填充材，例如根據纖維長度或長徑算出。更具體而言，例如，可使用電子顯微鏡或光學顯微鏡，測定任意50個異向性填充材之纖維長度或長徑，以其平均值（算術平均值）為平均纖維長度或平均粒徑。 Also, the average fiber length of the fibrous material is preferably shorter than the thickness of the primary sheet. By making the average fiber length of the fibrous material shorter than the thickness of the primary sheet, the fibrous material is prevented from protruding from the surface of the primary sheet more than necessary. Also, when the anisotropic filler is a scaly material, its average particle size is preferably 10-400 μm, more preferably 15-200 μm. Also, particularly preferably, it is 15 to 130 μm. By setting the average particle size to 10 μm or more, the anisotropic fillers in the primary sheet are easily in contact with each other, ensuring a heat transfer path. On the other hand, if the average particle size is 400 μm or less, the volume of the anisotropic filler will be reduced, and the polymer matrix can be highly filled with the anisotropic filler. Furthermore, the average fiber length of the carbon fiber or the average particle size of the scale-like material can be calculated from the fiber length or major diameter by observing the anisotropic filler with a microscope, for example. More specifically, for example, the fiber length or major diameter of arbitrary 50 anisotropic fillers can be measured using an electron microscope or an optical microscope, and the average (arithmetic mean) thereof can be used as the average fiber length or average particle diameter.

異向性填充材使用公知之具有導熱性之材料即可，但較佳為具備反磁性，以使其可如後述地進行磁場配向。 作為異向性填充材之具體例，可列舉：碳纖維、或鱗片狀碳粉末所代表之碳系材料；金屬纖維所代表之金屬材料或金屬氧化物；氮化硼或金屬氮化物；金屬碳化物；金屬氫氧化物等。該等之中，碳系材料之比重較小且於高分子基質中之分散性良好，故而較佳，其中，高導熱率之石墨化碳材料更佳。石墨化碳材料因其石墨面於特定方向上對齊而具備反磁性。又，氮化硼等之晶面亦於特定方向上對齊，因此其具備反磁性。 The anisotropic filler may be a known thermally conductive material, but preferably has diamagnetism so that it can perform magnetic field alignment as described later. Specific examples of anisotropic fillers include: carbon-based materials represented by carbon fibers or scaly carbon powders; metal materials or metal oxides represented by metal fibers; boron nitride or metal nitrides; metal carbides substances; metal hydroxides, etc. Among them, carbon-based materials are preferred because they have a small specific gravity and good dispersion in the polymer matrix. Among them, graphitized carbon materials with high thermal conductivity are more preferred. Graphitized carbon materials are diamagnetic because their graphitic faces are aligned in a specific direction. In addition, the crystal planes of boron nitride and the like are also aligned in a specific direction, so they have diamagnetism.

又，異向性填充材並無特別限定，但於具有異向性之方向（即長軸方向）上之導熱率通常為60 W/m・K以上，較佳為400 W/m・K以上。異向性填充材之導熱率之上限並無特別限定，例如可為2000 W/m・K以下。導熱率可由雷射閃光法或根據ASTM D5470之方法進行測定。Also, the anisotropic filler is not particularly limited, but the thermal conductivity in the anisotropic direction (i.e., the long-axis direction) is usually 60 W/m・K or higher, preferably 400 W/m・K or higher . The upper limit of the thermal conductivity of the anisotropic filler is not particularly limited, for example, it may be 2000 W/m·K or less. Thermal conductivity can be measured by a laser flash method or a method according to ASTM D5470.

異向性填充材可單獨使用一種，亦可併用兩種以上。例如，作為異向性填充材，可使用至少兩個具有互不相同之平均粒徑或平均纖維長度之異向性填充材。認為若使用不同尺寸之異向性填充材，則較小之異向性填充材進入到相對較大之異向性填充材之間，藉此可將異向性填充材高密度地填充至高分子基質中，並且提高導熱效率。One type of anisotropic filler may be used alone, or two or more types may be used in combination. For example, as the anisotropic filler, at least two anisotropic fillers having mutually different average particle diameters or average fiber lengths can be used. It is believed that if anisotropic fillers of different sizes are used, the smaller anisotropic fillers will enter between the relatively larger anisotropic fillers, so that the anisotropic fillers can be densely filled into the polymer matrix, and improve thermal conductivity.

上述之中，異向性填充材較佳為含有碳纖維，更佳為含有碳纖維及鱗片狀碳粉末。 用作異向性填充材之碳纖維較佳為石墨化碳纖維。又，作為鱗片狀碳粉末，較佳為鱗片狀石墨粉末。 關於石墨化碳纖維，石墨晶面於纖維軸方向上相連，且其纖維軸方向上具有高導熱率。因此，藉由使其纖維軸方向於特定方向上對齊，可提高特定方向上之導熱率。又，關於鱗片狀石墨粉末，石墨晶面於鱗片面之面內方向上相連，且其面內方向上具有高導熱率。因此，藉由使其鱗片面於特定方向上對齊，可提高特定方向上之導熱率。石墨化碳纖維及鱗片石墨粉末較佳為具有較高之石墨化度。 Among the above, the anisotropic filler preferably contains carbon fibers, and more preferably contains carbon fibers and flaky carbon powder. The carbon fiber used as the anisotropic filler is preferably graphitized carbon fiber. Also, as the flaky carbon powder, flaky graphite powder is preferable. Regarding graphitized carbon fibers, graphite crystal planes are connected in the fiber axis direction, and have high thermal conductivity in the fiber axis direction. Therefore, by aligning the fiber axis directions in a specific direction, the thermal conductivity in the specific direction can be improved. Also, in the flaky graphite powder, graphite crystal planes are connected in the in-plane direction of the flaky plane, and have high thermal conductivity in the in-plane direction. Therefore, by aligning the scale faces in a specific direction, the thermal conductivity in a specific direction can be improved. The graphitized carbon fiber and flake graphite powder preferably have a higher degree of graphitization.

作為上述石墨化碳纖維、鱗片狀石墨粉末等石墨化碳材料，可使用將以下原料石墨化而形成者。例如，可列舉萘等縮合多環烴化合物、PAN（聚丙烯腈）、瀝青等縮合雜環化合物等，尤其較佳為使用石墨化度較高之石墨化中間相瀝青或聚醯亞胺、聚苯并唑（benzazole）。例如，藉由使用中間相瀝青，於後述紡絲步驟中，瀝青因其異向性而於纖維軸方向上被配向，可獲得其纖維軸方向上具有優異之導熱性之石墨化碳纖維。As the graphitized carbon material such as the above-mentioned graphitized carbon fiber and flaky graphite powder, those formed by graphitizing the following raw materials can be used. For example, condensed polycyclic hydrocarbon compounds such as naphthalene, condensed heterocyclic compounds such as PAN (polyacrylonitrile), pitch, etc., etc., especially preferably use a graphitized mesophase pitch with a high degree of graphitization or polyimide, polyimide, etc. Benzazole. For example, by using mesophase pitch, in the spinning step described later, the pitch is oriented in the fiber axis direction due to its anisotropy, and graphitized carbon fibers having excellent thermal conductivity in the fiber axis direction can be obtained.

作為石墨化碳纖維，可使用如下者：對原料依次進行紡絲、不熔化、及碳化各處理，然後粉碎或切割成特定粒徑後進行石墨化所得者；或碳化後進行粉碎或切割，繼而進行石墨化所得者。於石墨化前進行粉碎或切割時，因粉碎而於原表面上露出新表面，於該新表面進行石墨化處理時容易進行縮聚反應、環化反應，因此石墨化度提高，獲得導熱性進一步得到提高之石墨化碳纖維。另一方面，於將經紡絲之碳纖維石墨化後進行粉碎時，由於石墨化後之碳纖維剛硬，因此容易粉碎，能夠以短時間之粉碎獲得纖維長度分佈相對狹窄之碳纖維粉末。As the graphitized carbon fiber, the following can be used: the raw material is sequentially subjected to spinning, non-melting, and carbonization, and then pulverized or cut into a specific particle size, and then graphitized; or carbonized, pulverized or cut, and then Graphite gainers. When pulverizing or cutting before graphitization, a new surface is exposed on the original surface due to pulverization, and polycondensation reaction and cyclization reaction are easy to proceed when graphitizing the new surface, so the degree of graphitization is improved, and the thermal conductivity is further improved. Enhanced graphitized carbon fiber. On the other hand, when the spun carbon fiber is graphitized and then pulverized, since the graphitized carbon fiber is rigid, it is easy to pulverize, and a carbon fiber powder with a relatively narrow fiber length distribution can be obtained by pulverizing in a short time.

（非異向性填充材） 非異向性填充材係與異向性填充材分開包含於初級片之導熱性填充材，該材料與異向性填充材一同賦予初級片導熱性。藉由填充非異向性填充材，於硬化成片之前一階段，抑制黏度上升，使分散性良好。又，異向性填充材之間，例如若纖維長度變大，則填充材之間之接觸面積難以增加，但藉由在其間填入非異向性填充材，可形成傳熱路徑，可獲得導熱率較高之初級片。 非異向性填充材係形狀實質上不具有異向性之填充材，即便於後述磁力線產生之情況下或剪切力作用下等使異向性填充材於特定方向上配向之環境下，非異向性填充材亦不於該特定方向上配向。 (non-anisotropic filler) The non-anisotropic filler is a thermally conductive filler included in the primary sheet separately from the anisotropic filler, and this material together with the anisotropic filler imparts thermal conductivity to the primary sheet. By filling the non-isotropic filler, the viscosity rise is suppressed in the stage before hardening into a sheet, and the dispersibility is good. Also, between anisotropic fillers, for example, if the fiber length becomes longer, it is difficult to increase the contact area between fillers, but by filling them with non-anisotropic fillers, a heat transfer path can be formed, and it is possible to obtain Primary sheet with high thermal conductivity. Non-anisotropic fillers are fillers that are substantially non-anisotropic in shape. Even under conditions where the anisotropic fillers are aligned in a specific direction under the generation of magnetic lines of force described later or under the action of shear force, the non-anisotropic fillers are non-anisotropic. Anisotropic fillers are also not aligned in this particular direction.

非異向性填充材之縱橫比為2以下，較佳為1.5以下。本實施方式中，藉由含有如此縱橫比較低之非異向性填充材，具有導熱性之填充材適當地介置於非異向性填充材之間隙中，可獲得導熱率較高之初級片。又，藉由使縱橫比為2以下，可防止後述混合組成物之黏度上升，進行高度填充。The aspect ratio of the anisotropic filler is 2 or less, preferably 1.5 or less. In this embodiment, by including the anisotropic filler with such a low aspect ratio, the thermally conductive filler is properly interposed in the gap between the anisotropic fillers, and a primary sheet with high thermal conductivity can be obtained. . In addition, by setting the aspect ratio to be 2 or less, it is possible to prevent the viscosity of the mixed composition described later from increasing, and to achieve a high degree of filling.

關於非異向性填充材之具體例，例如可列舉金屬、金屬氧化物、金屬氮化物、金屬氫氧化物、碳材料、金屬以外之氧化物、氮化物、碳化物等。又，非異向性填充材之形狀可列舉球狀、不定形之粉末等。 非異向性填充材中，金屬可列舉鋁、銅、鎳等，金屬氧化物可列舉氧化鋁（alumina）、氧化鎂、氧化鋅等，金屬氮化物可列舉氮化鋁等。作為金屬氫氧化物，可列舉氫氧化鋁。進而，作為碳材料，可列舉球狀石墨等。作為金屬以外之氧化物、氮化物、碳化物，可列舉石英、氮化硼、碳化矽等。 上述之中，非異向性填充材較佳為選自氧化鋁、鋁、氧化鋅、氮化硼、及氮化鋁，尤其就填充性及導熱率之觀點而言，較佳為鋁、氧化鋁，更佳為鋁。 非異向性填充材可單獨使用上述中之一種，亦可併用兩種以上。 Specific examples of the anisotropic filler include metals, metal oxides, metal nitrides, metal hydroxides, carbon materials, oxides other than metals, nitrides, and carbides. Also, examples of the shape of the anisotropic filler include spherical and amorphous powders. Among the anisotropic fillers, examples of metals include aluminum, copper, and nickel, examples of metal oxides include aluminum oxide, magnesium oxide, and zinc oxide, and examples of metal nitrides include aluminum nitride and the like. Aluminum hydroxide is mentioned as a metal hydroxide. Furthermore, spherical graphite etc. are mentioned as a carbon material. Examples of oxides, nitrides, and carbides other than metals include quartz, boron nitride, and silicon carbide. Among the above, the non-anisotropic filler is preferably selected from alumina, aluminum, zinc oxide, boron nitride, and aluminum nitride, especially from the viewpoint of filling property and thermal conductivity, aluminum, oxide Aluminum, more preferably aluminum. As the anisotropic filler, one of the above-mentioned ones may be used alone, or two or more of them may be used in combination.

非異向性填充材之平均粒徑較佳為0.1～50 μm，更佳為0.5～35 μm。又，特佳為1～15 μm。藉由使平均粒徑為50 μm以下，不易產生擾亂異向性填充材之配向等問題。又，藉由使平均粒徑為0.1 μm以上，非異向性填充材之比表面積不會超過必要程度地增大，即使摻合大量非異向性填充材，混合組成物之黏度亦不易上升，容易高程度地填充非異向性填充材。 作為非異向性填充材，例如，可使用至少兩種具有互不相同之平均粒徑之非異向性填充材。 再者，非異向性填充材之平均粒徑可藉由利用電子顯微鏡等觀察來進行測定。更具體而言，例如，可使用電子顯微鏡或光學顯微鏡，測定任意50個非異向性填充材之粒徑，以其平均值（算術平均值）作為平均粒徑。或者，平均粒徑係利用雷射繞射散射法（JIS R1629）測得之粒度分佈之體積平均粒徑。 The average particle size of the anisotropic filler is preferably 0.1-50 μm, more preferably 0.5-35 μm. Moreover, it is particularly preferably 1 to 15 μm. By setting the average particle size to 50 μm or less, problems such as disturbing the alignment of the anisotropic filler are less likely to occur. In addition, by setting the average particle size to 0.1 μm or more, the specific surface area of the anisotropic filler does not increase more than necessary, and even if a large amount of the anisotropic filler is mixed, the viscosity of the mixed composition does not easily increase. , It is easy to fill the anisotropic filler to a high degree. As the anisotropic filler, for example, at least two kinds of anisotropic fillers having mutually different average particle diameters can be used. In addition, the average particle diameter of an anisotropic filler can be measured by observation with an electron microscope etc. More specifically, for example, the particle diameters of arbitrary 50 anisotropic fillers can be measured using an electron microscope or an optical microscope, and the average value (arithmetic mean) thereof can be used as the average particle diameter. Alternatively, the average particle diameter is the volume average particle diameter of the particle size distribution measured by the laser diffraction scattering method (JIS R1629).

相對於高分子基質100質量份，非異向性填充材之含量較佳為150～800質量份之範圍，更佳為200～600質量份之範圍。 若以體積基準之填充率（體積填充率）表示非異向性填充材之含量，則相對於初級片總量，較佳為25～60體積%，更佳為40～55體積%。 藉由使非異向性填充材之含量為150質量份以上，而介存於異向性填充材彼此之間隙中之非異向性填充材之量變得充足，導熱性良好。另一方面，藉由使非異向性填充材之含量為800質量份以下，可獲得導熱性隨含量增加而提高之效果，又，非異向性填充材亦不會阻礙異向性填充材之導熱。進而，藉由使非異向性填充材之含量為200～600質量份之範圍內，初級片之導熱性優異，混合組成物之黏度亦較佳。 The content of the anisotropic filler is preferably in the range of 150-800 parts by mass relative to 100 parts by mass of the polymer matrix, more preferably in the range of 200-600 parts by mass. When the content of the anisotropic filler is represented by volume-based filling rate (volume filling rate), it is preferably 25 to 60 volume %, more preferably 40 to 55 volume %, relative to the total amount of the primary sheet. When the content of the anisotropic filler is 150 parts by mass or more, the amount of the anisotropic filler interposed in the gap between the anisotropic fillers becomes sufficient, and thermal conductivity becomes favorable. On the other hand, by keeping the content of the non-anisotropic filler at 800 parts by mass or less, the effect of increasing the thermal conductivity as the content increases can be obtained, and the non-isotropic filler does not hinder the anisotropic filler. of heat conduction. Furthermore, by setting the content of the anisotropic filler within the range of 200 to 600 parts by mass, the thermal conductivity of the primary sheet is excellent, and the viscosity of the mixed composition is also favorable.

非異向性填充材之體積填充率與異向性填充材之體積填充率之比較佳為2～5，更佳為2～3。藉由使體積填充率之比率範圍為上述範圍內，非異向性填充材可適度地填充於異向性填充材之間，可形成有效之傳熱路徑，因此可提高初級片之導熱性。The ratio of the volume filling rate of the anisotropic filler to that of the anisotropic filler is preferably 2-5, more preferably 2-3. By setting the ratio of the volume filling rate within the above-mentioned range, the non-anisotropic filler can be properly filled between the anisotropic fillers, an effective heat transfer path can be formed, and thus the thermal conductivity of the primary sheet can be improved.

初級片之厚度並無特別限定，根據供導熱性片搭載之電子機器之形狀及用途適當進行變更，例如為0.1～5.0 mm，較佳為0.1～0.3 mm。藉由使初級片之厚度為0.1～0.3 mm，所形成之導熱性片之厚度變薄，成為易導熱之導熱性片。The thickness of the primary sheet is not particularly limited, and can be appropriately changed according to the shape and application of the electronic device on which the thermally conductive sheet is mounted, for example, it is 0.1-5.0 mm, preferably 0.1-0.3 mm. By making the thickness of the primary sheet 0.1 to 0.3 mm, the thickness of the formed thermally conductive sheet becomes thinner, and becomes a thermally conductive sheet that is easy to conduct heat.

＜初級片之製作＞ 初級片並無特別限定，例如，可由包括以下之步驟（A-1）及（A-2）之方法製造。 步驟（A-1）：使異向性填充材沿初級片中之成為厚度方向之一方向上配向，獲得配向成形體之步驟； 步驟（A-2）：將配向成形體切割成片狀，獲得初級片之步驟。 以下，更詳細地說明各步驟。 ＜Preliminary Film Production＞ The primary sheet is not particularly limited, and can be produced, for example, by a method including the following steps (A-1) and (A-2). Step (A-1): a step of aligning the anisotropic filler along one of the thickness directions in the primary sheet to obtain an aligned molded body; Step (A-2): the step of cutting the aligned formed body into sheets to obtain primary sheets. Hereinafter, each step will be described in more detail.

《步驟（A-1）》 步驟（A-1）中，例如，由包含異向性填充材及成為高分子基質之原料之液狀高分子組成物之混合組成物形成配向成形體。混合組成物中可視需要含有非異向性填充材、烴系化合物、後述相溶性物質等。混合組成物較佳為硬化從而形成配向成形體。更具體而言，配向成形體可由磁場配向製造法、流動配向製造法獲得，該等之中，較佳為磁場配向製造法。 "Step (A-1)" In step (A-1), for example, an aligned molded body is formed from a mixed composition including an anisotropic filler and a liquid polymer composition as a raw material of a polymer matrix. The mixed composition may optionally contain an anisotropic filler, a hydrocarbon-based compound, a compatible substance described later, and the like. The mixed composition is preferably hardened to form an aligned shape. More specifically, the aligned molded body can be obtained by a magnetic field alignment manufacturing method and a flow alignment manufacturing method, and among them, a magnetic field alignment manufacturing method is preferable.

（磁場配向製造法） 磁場配向製造法中，將至少包含硬化後成為高分子基質之液狀高分子組成物及異向性填充材之混合組成物注入模具等之內部後，將其置於磁場中，使異向性填充材沿磁場配向，繼而使高分子組成物硬化，藉此獲得配向成形體。配向成形體較佳為形成為塊狀。 又，於模具內部之與混合組成物接觸之部分可配置有剝離膜。作為剝離膜，例如使用剝離性良好之樹脂膜或單面經剝離劑等剝離處理過之樹脂膜。藉由使用剝離膜，配向成形體容易從模具脫模。 (Magnetic field alignment manufacturing method) In the magnetic field alignment manufacturing method, a mixed composition including at least a liquid polymer composition that becomes a polymer matrix after hardening and an anisotropic filler is injected into a mold, etc., and then placed in a magnetic field to make the anisotropy The filler is aligned along the magnetic field, and then the polymer composition is hardened, thereby obtaining an aligned molded body. The alignment molding is preferably formed in a block shape. In addition, a release film may be disposed on the portion in contact with the mixed composition inside the mold. As the release film, for example, a resin film with good releasability or a resin film that has been subjected to release treatment with a release agent or the like on one side is used. By using a release film, the alignment molded body is easily released from the mold.

磁場配向製造法中，為了進行磁場配向，使用之混合組成物之黏度較佳為10～300 Pa・s。藉由使混合組成物之黏度為10 Pa・s以上，異向性填充材或非異向性填充材不易沈澱。又，藉由使混合組成物之黏度為300 Pa・s以下，流動性變得良好，異向性填充材於磁場中適當地被配向，亦不會產生配向所需時間過長之問題。再者，黏度係指使用旋轉黏度計（布氏黏度計DV-E、主軸SC4-14）於25℃以旋轉速度10 rpm測得之黏度。 然而，當使用不易沈澱之異向性填充材及非異向性填充材，或將其與防沈澱劑等添加劑組合使用時，混合組成物黏度可未達10 Pa・s。 In the magnetic field alignment manufacturing method, in order to perform magnetic field alignment, the viscosity of the mixed composition used is preferably 10-300 Pa·s. By making the viscosity of the mixed composition more than 10 Pa·s, the anisotropic filler or non-anisotropic filler is less likely to settle. In addition, by making the viscosity of the mixed composition below 300 Pa·s, the fluidity becomes good, and the anisotropic filler is properly aligned in the magnetic field, and the problem that the alignment takes too long does not arise. Furthermore, the viscosity refers to the viscosity measured at 25° C. with a rotational speed of 10 rpm using a rotational viscometer (Brookfield viscometer DV-E, spindle SC4-14). However, when anisotropic fillers and non-anisotropic fillers that are not prone to sedimentation are used, or when they are used in combination with additives such as anti-sedimentation agents, the viscosity of the mixed composition may not reach 10 Pa·s.

磁場配向製造法中，作為用於施加磁力線之磁力線產生源，可列舉超導磁鐵、永久磁鐵、電磁鐵等，就可產生高磁通密度之磁場之觀點而言，較佳為超導磁鐵。從該等磁力線產生源產生之磁場之磁通密度較佳為1～30特士拉。若使磁通密度為1特士拉以上，則可使碳材料等構成之上述異向性填充材容易進行配向。又，藉由使磁通密度為30特士拉以下，可實用性地進行製造。 高分子組成物之硬化可藉由加熱而進行，例如，可於50～180℃左右之溫度進行。又，加熱時間例如為10分鐘～3小時左右。 In the magnetic field alignment manufacturing method, examples of the source of magnetic force lines for applying magnetic force lines include superconducting magnets, permanent magnets, electromagnets, etc., and superconducting magnets are preferred from the viewpoint of generating a magnetic field with high magnetic flux density. The magnetic flux density of the magnetic field generated from these magnetic flux generation sources is preferably 1-30 Tesla. When the magnetic flux density is 1 Tesla or more, the above-mentioned anisotropic filler made of a carbon material or the like can be easily aligned. In addition, practical production is possible by setting the magnetic flux density to be 30 Tesla or less. The hardening of the polymer composition can be performed by heating, for example, at a temperature of about 50-180°C. Moreover, heating time is about 10 minutes - 3 hours, for example.

（流動配向製造法） 流動配向製造法中，可對混合組成物施加剪切力，製造面方向上配向有異向性填充材之預備片，積層複數片該預備片，製造積層塊，以該積層塊作為配向成形體。 更具體而言，流動配向製造法中，首先，攪拌混合組成物，製備摻合之固形物均質地分散而成之混合組成物。此處，高分子組成物中使用之高分子化合物可為包含於常溫（23℃）時為液狀之高分子化合物者，亦可為包含於常溫時為固體狀之高分子化合物者。 混合組成物之黏度相對較高，使得其在拉伸成片狀時受到剪切力，具體而言，混合組成物之黏度較佳為3～50 Pa・s。為獲得上述黏度，較佳為於混合組成物中摻合溶劑。 (Flow alignment manufacturing method) In the flow alignment manufacturing method, a shear force can be applied to the mixed composition to manufacture a preparatory sheet with an anisotropic filler aligned in the surface direction, and a plurality of preparatory sheets can be laminated to produce a laminated block, and the laminated block can be used as an alignment molded body . More specifically, in the flow alignment manufacturing method, first, the composition is stirred and mixed to prepare a mixed composition in which the blended solids are uniformly dispersed. Here, the polymer compound used in the polymer composition may be a polymer compound that is liquid at normal temperature (23° C.), or may be a polymer compound that is solid at normal temperature. The viscosity of the mixed composition is relatively high, so that it is subjected to shear force when stretched into a sheet. Specifically, the viscosity of the mixed composition is preferably 3-50 Pa·s. In order to obtain the above-mentioned viscosity, it is preferable to blend a solvent into the mixed composition.

其次，一面對混合組成物施加剪切力，一面使其平坦地延伸，成形為片狀（預備片）。藉由施加剪切力，可使異向性填充材於剪切方向上配向。作為片之成形手段，例如，可藉由棒式塗佈機或刮刀等塗佈用敷料器、或者擠出成形或利用分配器裝置之噴出等，將混合組成物塗佈於基材膜上，繼而，視需要進行乾燥，或使混合組成物半硬化。 若上述分配器裝置所具備之噴出口為例如寬幅形狀，則藉由噴出混合組成物可容易地形成預備片。根據此方法，可於不使用大型設備且鮮少產生邊角材料等之情況下，形成異向性填充材於一個方向進行配向而得之預備片。 預備片之厚度較佳為50～250 μm左右。預備片中，異向性填充材於沿著片之面方向之一個方向上配向。 其次，可將複數片之預備片以配向方向相同之方式重疊積層後，視需要藉由加熱、紫外線照射等使混合組成物硬化，並且藉由熱壓等使預備片互相接著，藉此形成積層塊，以該積層塊作為配向成形體。 Next, while applying a shearing force to the mixed composition, it is stretched flat and shaped into a sheet (preliminary sheet). By applying a shear force, the anisotropic filler can be aligned in the shear direction. As the means for forming the sheet, for example, the mixed composition can be applied to the base film by means of a coating applicator such as a bar coater or a doctor blade, extrusion molding or spraying by a dispenser device, etc. Then, drying is performed as necessary, or the mixed composition is semi-hardened. If the ejection port provided in the above-mentioned dispenser device has a wide shape, for example, the preparation sheet can be easily formed by ejecting the mixed composition. According to this method, it is possible to form a preparatory sheet in which the anisotropic filler is aligned in one direction without using large-scale equipment and rarely generating edge materials. The thickness of the preparation sheet is preferably about 50-250 μm. In the prepared sheet, the anisotropic filler is aligned in one direction along the surface direction of the sheet. Next, a plurality of preparatory sheets can be laminated in such a way that the alignment direction is the same, and if necessary, the mixed composition is hardened by heating, ultraviolet radiation, etc., and the preparatory sheets are bonded to each other by hot pressing, thereby forming a laminate. block, and use the laminated block as an alignment molding.

當步驟（A-1）中使用之混合組成物中含有烴系化合物時，較佳為亦一併含有相溶性物質。相溶性物質係與烴系化合物及液狀高分子組成物相溶或溶解於其中之物質。烴系化合物與高分子組成物之相溶性較低，但藉由使用相溶性物質，烴系化合物可均勻地混合於高分子組成物中。因此，烴系化合物亦可均勻地混合於使高分子組成物硬化而獲得之高分子基質中。When the mixed composition used in the step (A-1) contains a hydrocarbon compound, it is preferable to also contain a compatible substance. Compatible substances are substances that are compatible with or dissolved in hydrocarbon compounds and liquid polymer compositions. The compatibility between the hydrocarbon compound and the polymer composition is low, but by using a compatible substance, the hydrocarbon compound can be uniformly mixed in the polymer composition. Therefore, the hydrocarbon compound can also be uniformly mixed in the polymer matrix obtained by hardening the polymer composition.

（相溶性物質） 相溶性物質可為溶解於烴系化合物中且與液狀高分子組成物相溶之物質。相溶性物質較佳為於常溫（23℃）、1大氣壓時為液狀之物質。如後所述，相溶性物質係例如藉由50～180℃左右之加熱而揮發之成分。相溶性物質於硬化時經加熱而揮發，藉此可增加初級片中之異向性填充材及非異向性填充材之含有比率。又，混合組成物藉由含有相溶性物質而黏度降低。因此，易使異向性填充材之摻合量增多，進而，藉由磁場配向等使異向性填充材容易於特定方向上配向。 (compatible substances) Compatible substances can be dissolved in hydrocarbon compounds and compatible with liquid polymer compositions. Compatible substances are preferably liquid substances at normal temperature (23°C) and 1 atmosphere. As will be described later, the compatible substance is a component that volatilizes by heating at about 50 to 180°C, for example. Compatible substances are volatilized by heating during hardening, thereby increasing the content ratio of the anisotropic filler and non-anisotropic filler in the primary sheet. Also, the viscosity of the mixed composition is reduced by containing compatible substances. Therefore, it is easy to increase the blending amount of the anisotropic filler, and further, it is easy to align the anisotropic filler in a specific direction by magnetic field alignment or the like.

作為相溶性物質，可列舉烷氧基矽烷化合物、烴系溶劑、烷氧基矽氧烷化合物等。由於該等化合物對烴系化合物及液狀高分子組成物具有較高溶解性或相溶性，因此，於混合組成物中，可提高烴系化合物對於高分子組成物之分散性。藉此，烴系化合物亦適當地分散於初級片中，易確保保形性、可靠性、高溫下之柔軟性等。 相溶性物質可單獨使用一種，亦可將兩種以上組合使用。 Examples of compatible substances include alkoxysilane compounds, hydrocarbon-based solvents, alkoxysiloxane compounds, and the like. Because these compounds have high solubility or compatibility with hydrocarbon compounds and liquid polymer compositions, therefore, in the mixed composition, the dispersibility of hydrocarbon compounds for polymer compositions can be improved. Thereby, the hydrocarbon compound is properly dispersed in the primary sheet, and it is easy to ensure shape retention, reliability, flexibility at high temperature, and the like. Compatible substances may be used alone or in combination of two or more.

作為相溶性物質，較佳為使用烷氧基矽烷化合物。藉由使用烷氧基矽烷化合物，未發現由硬化而獲得之導熱性片之表面有氣泡等，外觀良好。 用作相溶性物質之烷氧基矽烷化合物係具有如下結構之化合物，即，矽原子（Si）所具有之4個鍵中，1～3個與烷氧基鍵結，剩餘之鍵與有機取代基鍵結。烷氧基矽烷化合物藉由含有烷氧基及有機取代基，可提高烴系化合物相對於高分子組成物之分散性。 作為烷氧基矽烷化合物所具有之烷氧基，例如可列舉：甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、及己氧基。烷氧基矽烷化合物可以二聚物之形式包含於高分子組成物中。 As a compatible substance, it is preferable to use an alkoxysilane compound. By using an alkoxysilane compound, no bubbles or the like were found on the surface of the thermally conductive sheet obtained by curing, and the appearance was good. The alkoxysilane compound used as a compatible substance is a compound having the following structure, that is, among the 4 bonds of a silicon atom (Si), 1 to 3 are bonded to alkoxy groups, and the remaining bonds are substituted with organic base bond. Alkoxysilane compounds can improve the dispersibility of hydrocarbon compounds relative to polymer compositions by containing alkoxy groups and organic substituents. As an alkoxy group which an alkoxysilane compound has, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group are mentioned, for example. Alkoxysilane compounds can be contained in polymer compositions in the form of dimers.

烷氧基矽烷化合物之中，就易獲取性之觀點而言，較佳為具有甲氧基及乙氧基之至少任一者之烷氧基矽烷化合物。就與高分子組成物及烴系化合物之相溶性、溶解性等觀點而言，烷氧基矽烷化合物中所含烷氧基之數量較佳為2或3，更佳為3。具體而言，烷氧基矽烷化合物較佳為選自三甲氧基矽烷化合物、三乙氧基矽烷化合物、二甲氧基矽烷化合物、二乙氧基矽烷化合物中之至少一種。Among the alkoxysilane compounds, an alkoxysilane compound having at least one of a methoxy group and an ethoxy group is preferable from the viewpoint of availability. The number of alkoxy groups contained in the alkoxysilane compound is preferably 2 or 3, more preferably 3, from the viewpoints of compatibility with polymer compositions and hydrocarbon compounds, and solubility. Specifically, the alkoxysilane compound is preferably at least one selected from trimethoxysilane compounds, triethoxysilane compounds, dimethoxysilane compounds, and diethoxysilane compounds.

作為烷氧基矽烷化合物具有之有機取代基中所含之官能基，例如可列舉：丙烯醯基、烷基、羧基、乙烯基、甲基丙烯基、芳香族基、胺基、異氰酸基、異氰尿酸基、環氧基、羥基、及巰基。此處，當使用鉑觸媒作為高分子組成物之硬化觸媒時，較佳為選擇使用不易影響有機聚矽氧烷之硬化反應之烷氧基矽烷化合物。具體而言，當使用利用了鉑觸媒之加成反應型有機聚矽氧烷時，烷氧基矽烷化合物之有機取代基較佳為不含胺基、異氰酸基、異氰尿酸基、羥基、或巰基。Examples of the functional group contained in the organic substituent of the alkoxysilane compound include: acryl group, alkyl group, carboxyl group, vinyl group, methacryl group, aromatic group, amino group, isocyanate group , isocyanuric acid group, epoxy group, hydroxyl group, and mercapto group. Here, when a platinum catalyst is used as the curing catalyst of the polymer composition, it is preferable to use an alkoxysilane compound that is less likely to affect the curing reaction of the organopolysiloxane. Specifically, when using an addition reaction organopolysiloxane using a platinum catalyst, the organic substituent of the alkoxysilane compound preferably does not contain an amine group, an isocyanate group, an isocyanurate group, Hydroxyl, or mercapto.

就提高烴系化合物於高分子基質中之分散性之觀點而言，烷氧基矽烷化合物較佳為包含具有與矽原子鍵結之烷基之烷基烷氧基矽烷化合物、即，包含具有烷基作為有機取代基之烷氧基矽烷化合物。因此，較佳為二烷基二烷氧基矽烷化合物、烷基三烷氧基矽烷化合物，其中，又以烷基三烷氧基矽烷化合物為較佳。 與矽原子鍵結之烷基之碳數例如可為1～16。又，於三甲氧基矽烷化合物、三乙氧基矽烷化合物等三烷氧基矽烷化合物中，就提高烴系化合物之分散性之觀點而言，上述烷基之碳數較佳為6以上，進而較佳為8以上，又，碳數較佳為12以下，更佳為10以下。 另一方面，於二甲氧基矽烷化合物、三乙氧基矽烷化合物等二烷氧基矽烷化合物中，就提高烴系化合物之分散性之觀點而言，上述烷基之碳數可為1以上，又，碳數較佳為10以下，更佳為6以下，進而較佳為4以下。 From the viewpoint of improving the dispersibility of the hydrocarbon-based compound in the polymer matrix, the alkoxysilane compound is preferably an alkylalkoxysilane compound having an alkyl group bonded to a silicon atom, that is, an alkyl alkoxysilane compound having an alkyl group bonded to a silicon atom. Alkoxysilane compounds with organic substituents. Therefore, dialkyldialkoxysilane compounds and alkyltrialkoxysilane compounds are preferred, and among them, alkyltrialkoxysilane compounds are more preferred. The carbon number of the alkyl group bonded to the silicon atom may be 1-16, for example. Also, in trialkoxysilane compounds such as trimethoxysilane compounds and triethoxysilane compounds, from the viewpoint of improving the dispersibility of hydrocarbon-based compounds, the carbon number of the above-mentioned alkyl group is preferably 6 or more, and further It is preferably at least 8, and the carbon number is preferably at most 12, more preferably at most 10. On the other hand, in dialkoxysilane compounds such as dimethoxysilane compounds and triethoxysilane compounds, from the viewpoint of improving the dispersibility of hydrocarbon-based compounds, the carbon number of the above-mentioned alkyl group may be 1 or more. , and the number of carbon atoms is preferably 10 or less, more preferably 6 or less, further preferably 4 or less.

作為含烷基之烷氧基矽烷化合物，例如可列舉：甲基三甲氧基矽烷、二甲基二甲氧基矽烷、二乙基二甲氧基矽烷、三甲基甲氧基矽烷、甲基三乙氧基矽烷、二甲基二乙氧基矽烷、乙基三甲氧基矽烷、正丙基三甲氧基矽烷、二正丙基二甲氧基矽烷、二正丙基二乙氧基矽烷、異丁基三甲氧基矽烷、異丁基三乙氧基矽烷、異丁基三甲氧基矽烷、異丁基三乙氧基矽烷、正己基三甲氧基矽烷、正己基三乙氧基矽烷、甲基環己基二甲氧基矽烷、甲基環己基二乙氧基矽烷、正辛基三甲氧基矽烷、正辛基三乙氧基矽烷、正癸基三甲氧基矽烷、正癸基三乙氧基矽烷等。 含烷基之烷氧基矽烷化合物之中，就改善烴系化合物之分散性之觀點而言，進而較佳為正癸基三甲氧基矽烷、二甲基二甲氧基矽烷、正辛基三乙氧基矽烷，就與烴系化合物之溶解性之觀點而言，進而更佳為正癸基三甲氧基矽烷、正辛基三乙氧基矽烷。 Examples of alkyl group-containing alkoxysilane compounds include: methyltrimethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, trimethylmethoxysilane, methyl Triethoxysilane, dimethyldiethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, Isobutyltrimethoxysilane, isobutyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, methyl Cyclohexyldimethoxysilane, Methylcyclohexyldiethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, n-decyltriethoxysilane base silane, etc. Among the alkyl group-containing alkoxysilane compounds, n-decyltrimethoxysilane, dimethyldimethoxysilane, n-octyltrimethoxysilane, n-octyltrimethoxysilane, and Ethoxysilane is more preferably n-decyltrimethoxysilane and n-octyltriethoxysilane from the viewpoint of solubility with hydrocarbon compounds.

用作相溶性物質之烷氧基矽氧烷化合物具有如下結構，即，含有兩個以上之矽氧烷鍵，且烷氧基與至少一個矽原子鍵結。烷氧基矽氧烷化合物具有如下結構，即，有機取代基與構成矽氧烷鍵之矽原子中之至少一個矽原子鍵結。烷氧基矽氧烷化合物藉由具有烷氧基及有機取代基，可提高烴系化合物之分散性。 作為烷氧基矽氧烷化合物所具有之烷氧基及有機取代基，可列舉上述烷氧基矽烷化合物之說明中所例示者，就提高烴系化合物之分散性之觀點而言，較佳為至少具有烷基。 The alkoxysiloxane compound used as a compatible substance has a structure containing two or more siloxane bonds, and an alkoxy group is bonded to at least one silicon atom. The alkoxysiloxane compound has a structure in which an organic substituent is bonded to at least one silicon atom among silicon atoms constituting a siloxane bond. Alkoxysiloxane compounds can improve the dispersibility of hydrocarbon compounds by having alkoxy groups and organic substituents. The alkoxy groups and organic substituents that the alkoxysiloxane compound has include those exemplified in the description of the above-mentioned alkoxysilane compound. From the viewpoint of improving the dispersibility of the hydrocarbon compound, preferred are have at least an alkyl group.

作為烷氧基矽氧烷化合物，例如可列舉：甲基甲氧基矽氧烷低聚物、甲基苯基甲氧基矽氧烷低聚物、甲基環氧基甲氧基矽氧烷低聚物、甲基巰基甲氧基矽氧烷低聚物、及甲基丙烯醯基甲氧基矽氧烷低聚物等。 烷氧基矽氧烷化合物可使用一種或兩種以上。 Examples of alkoxysiloxane compounds include: methylmethoxysiloxane oligomer, methylphenylmethoxysiloxane oligomer, methylepoxymethoxysiloxane Oligomers, methylmercaptomethoxysiloxane oligomers, and methacrylmethoxysiloxane oligomers, etc. Alkoxysiloxane compounds may be used singly or in combination of two or more.

作為用作相溶性物質之烴系溶劑，可列舉芳香族烴系溶劑。其中，就與硬化性聚矽氧組成物之相溶性之觀點而言，較佳為芳香族烴系溶劑。作為芳香族烴系溶劑，可列舉碳數為6～10左右之芳香族烴系溶劑，例如可列舉：甲苯、二甲苯、對稱三甲苯、乙基苯、丙基苯、丁基苯、第三丁基苯等，較佳為甲苯、二甲苯等。Examples of the hydrocarbon-based solvent used as a compatible substance include aromatic hydrocarbon-based solvents. Among these, aromatic hydrocarbon-based solvents are preferred from the viewpoint of compatibility with the curable polysiloxane composition. Examples of the aromatic hydrocarbon-based solvent include aromatic hydrocarbon-based solvents having about 6 to 10 carbon atoms, such as toluene, xylene, trimethylbenzene, ethylbenzene, propylbenzene, butylbenzene, third Butylbenzene, etc., preferably toluene, xylene, etc.

混合組成物中，相對於高分子組成物與烴系化合物之總計100質量份，相溶性物質之含量較佳為6～60質量份。若相溶性物質之含量為6質量份以上，則可充分提高烴系化合物對於高分子組成物之混合均勻性。又，藉由使相溶性物質之含量為60質量份以下，可獲得與相溶性物質之使用量相稱之效果。就該等觀點而言，相溶性物質之上述含量更佳為10～50質量份，進而較佳為15～45質量份。In the mixed composition, the content of the compatible substance is preferably 6 to 60 parts by mass relative to 100 parts by mass in total of the polymer composition and the hydrocarbon compound. If the content of the compatible substance is more than 6 parts by mass, the uniformity of mixing the hydrocarbon-based compound with the polymer composition can be sufficiently improved. Moreover, the effect commensurate with the usage-amount of a compatible substance can be acquired by making content of a compatible substance into 60 mass parts or less. From these viewpoints, the said content of a compatible material is more preferably 10-50 mass parts, More preferably, it is 15-45 mass parts.

相溶性物質可包含於最終之導熱性片中，又，亦可實施揮發步驟以使最終之導熱性片中不含相溶性物質。於不使相溶性物質揮發之情況下製造之導熱性片有柔軟性過高，失去回復性，導致操作性等變差之虞。另一方面，使相溶性物質完全揮發而製造之導熱性片有柔軟性降低之虞。因此，當以揮發前之配向成形體或初級片中所含之相溶性物質為100質量%時，相溶性物質之揮發量較佳為1～80質量%，更佳為5～50質量%。藉由使相溶性物質之揮發量為上述範圍，容易獲得具有適度柔軟性、且操作性亦良好之導熱性片。 揮發步驟可於實施步驟（A-1），使高分子組成物硬化後實施。具體而言，可於針對配向成形體或後述步驟（A-2）中所得之初級片進行加壓步驟或研磨步驟之前或之後實施。其中，較佳為於步驟（A-2）之後之狀態下實施。其原因在於，初級片為較薄之片狀，此外，無表層，異向性填充材之前端（端部）於初級片表面露出。因此，揮發速度較快，相溶性物質處於被封在初級片內部之狀態下，發泡之可能性小。 揮發量可藉由調整加熱溫度及加熱時間等來調整。可於加熱溫度為例如65～150℃左右之溫度下進行調整。又，加熱時間為例如2～24小時。藉由加熱，使至少一部分相溶性物質揮發。 又，加熱溫度特佳為調整為於2小時加熱時間內使添加之相溶性物質量之1～80%揮發之溫度。藉此，可抑制相溶性物質之急遽揮發，抑制氣泡殘留於片中。 Compatible substances may be included in the final thermally conductive sheet, and a volatilization step may be performed so that the final thermally conductive sheet does not contain compatible substances. The thermally conductive sheet produced without volatilizing the compatible substances may have too high flexibility, lose recovery, and cause poor operability. On the other hand, a thermally conductive sheet produced by completely volatilizing a compatible substance may lower flexibility. Therefore, when the compatible substance contained in the alignment molding or the primary sheet before volatilization is taken as 100% by mass, the volatilization amount of the compatible substance is preferably 1-80% by mass, more preferably 5-50% by mass. By making the volatilization amount of a compatible substance into the said range, it becomes easy to obtain the thermally conductive sheet which has moderate flexibility and is also favorable in handleability. The volatilization step can be carried out after the step (A-1) of hardening the polymer composition. Specifically, it may be performed before or after the pressing step or the grinding step is performed on the aligned molded body or the primary sheet obtained in the step (A-2) described later. Among them, it is preferable to carry out in the state after step (A-2). The reason for this is that the primary sheet is in a thin sheet shape and has no surface layer, and the front end (end) of the anisotropic filler is exposed on the surface of the primary sheet. Therefore, the volatilization speed is fast, and the compatible substance is in the state of being sealed inside the primary sheet, and the possibility of foaming is small. The amount of volatilization can be adjusted by adjusting the heating temperature and heating time. Adjustment can be performed at a heating temperature of, for example, about 65 to 150°C. Moreover, heating time is 2 to 24 hours, for example. By heating, at least a part of the compatible substances are volatilized. In addition, the heating temperature is particularly preferably adjusted to a temperature at which 1 to 80% of the amount of added compatible substances is volatilized within a heating time of 2 hours. Thereby, the rapid volatilization of compatible substances can be suppressed, and air bubbles can be suppressed from remaining in the tablet.

《步驟（A-2）》 步驟（A-2）為切割加工步驟，其係藉由切片等，於與異向性填充材之配向方向垂直之方向，對步驟（A-1）中獲得之配向成形體進行切割，獲得初級片。切片例如可由剪切刀片或雷射等進行。藉由切片等切割，於初級片之作為切割面之各表面，異向性填充材之前端（端部）從高分子基質露出。所露出之異向性填充材大多於厚度方向上配向，並未倒塌。 "Step (A-2)" Step (A-2) is a cutting process step, which is to cut the alignment formed body obtained in step (A-1) in a direction perpendicular to the alignment direction of the anisotropic filler by slicing, etc., to obtain primary piece. Slicing can be performed, for example, by a shear blade or a laser. By cutting by slicing or the like, the front end (end) of the anisotropic filler is exposed from the polymer matrix on each of the cut surfaces of the primary sheet. Most of the exposed anisotropic fillers are aligned in the thickness direction and have not collapsed.

[（B）加壓步驟] （B）加壓步驟係將初級片於厚度方向上壓縮之步驟。藉由實施該加壓步驟，初級片之熱阻值降低。認為其原因在於，片於厚度方向上被壓縮，其結果，厚度一定程度地變薄，因此片內部之每單位體積之異向性填充材之濃度升高，其結果，易形成導熱通道。又，認為藉由進行加壓，表面粗糙度降低，藉此對被黏著體之密接性提高，此亦有助於熱阻值之降低。 [(B) pressurization step] (B) The pressing step is a step of compressing the primary sheet in the thickness direction. By performing this pressurization step, the thermal resistance of the primary sheet decreases. The reason for this is considered to be that the sheet is compressed in the thickness direction, and as a result, the thickness becomes thinner to some extent, so the concentration of the anisotropic filler per unit volume inside the sheet increases, and as a result, heat conduction channels are easily formed. In addition, it is considered that the surface roughness is reduced by applying pressure, thereby improving the adhesion to the adherend, which also contributes to the reduction of the thermal resistance value.

（B）加壓步驟中，初級片之厚度變化較佳為3%以上，更佳為7%以上，進而較佳為10%以上。若初級片之厚度變化為該等下限值以上，則易使所形成之導熱性片之熱阻值降低。 初級片之厚度變化之上限值並無特別限制，例如為40%。 初級片之厚度變化（%）可根據100×[（加壓步驟前之片厚度－加壓步驟後之片厚度）/（加壓步驟前之片厚度）]而求出。 (B) In the pressing step, the change in thickness of the primary sheet is preferably at least 3%, more preferably at least 7%, and still more preferably at least 10%. If the thickness variation of the primary sheet is above the lower limit values, the thermal resistance of the formed thermally conductive sheet tends to decrease. The upper limit of the thickness change of the primary sheet is not particularly limited, for example, it is 40%. The thickness change (%) of the primary sheet can be obtained by 100×[(sheet thickness before pressurization step-sheet thickness after pressurization step)/(sheet thickness before pressurization step)].

（B）加壓步驟中，加壓溫度並無特別限定，例如為10～150℃，較佳為25～70℃，更佳為30～60℃，進而較佳為30～50℃。 再者，加壓溫度可根據初級片之組成適當進行設定，較佳為不會使高分子基質實質上劣化，且促進加壓引起之應變之溫度。 具體而言，當初級片包含烴系化合物時，加壓溫度較佳為25～70℃，更佳為30～60℃。若為此種加壓溫度範圍，則導熱性片之熱阻值容易降低。當初級片包含烴系化合物時，加壓步驟之溫度條件可設定得相對寬廣。 相對於此，當初級片不含烴系化合物時，加壓溫度較佳為25～55℃，更佳為30～50℃。若為此種加壓溫度範圍，則導熱性片之熱阻值容易降低。 (B) In the pressurization step, the pressurization temperature is not particularly limited, but is, for example, 10 to 150°C, preferably 25 to 70°C, more preferably 30 to 60°C, further preferably 30 to 50°C. Furthermore, the pressing temperature can be appropriately set according to the composition of the primary sheet, but it is preferably a temperature that does not substantially deteriorate the polymer matrix and promotes strain caused by pressing. Specifically, when the primary sheet contains a hydrocarbon-based compound, the pressing temperature is preferably from 25 to 70°C, more preferably from 30 to 60°C. In such a pressure temperature range, the thermal resistance of the thermally conductive sheet tends to decrease. When the primary sheet contains a hydrocarbon compound, the temperature condition of the pressurizing step can be set relatively broadly. On the other hand, when the primary sheet does not contain a hydrocarbon compound, the pressing temperature is preferably from 25 to 55°C, more preferably from 30 to 50°C. In such a pressure temperature range, the thermal resistance of the thermally conductive sheet tends to decrease.

（B）加壓步驟中，初級片之壓縮率（加壓時之壓縮率）並無特別限定，例如為5～80%，較佳為10～70%。初級片之壓縮率較佳為根據（B）加壓步驟及（C）研磨步驟之實施順序進行調整。 具體而言，當於（C）研磨步驟之前進行（B）加壓步驟時，（B）加壓步驟中，初級片之壓縮率較佳為20～80%，更佳為30～70%。若為此種壓縮率，則導熱性片之熱阻值容易降低。 又，藉由在（C）研磨步驟之前進行（B）加壓步驟，即使於加壓步驟中表面狀態變差之情形時，亦容易獲得表面平滑之導熱性片。換言之，藉由在（C）研磨步驟之前進行（B）加壓步驟，可抑制最終獲得之導熱性片之表面粗糙度之不均，進而可降低熱阻值之不均。 (B) In the pressing step, the compression rate of the primary sheet (compression rate during pressurization) is not particularly limited, but is, for example, 5 to 80%, preferably 10 to 70%. The compression ratio of the primary sheet is preferably adjusted according to the order of (B) pressing step and (C) grinding step. Specifically, when the (B) pressing step is performed before the (C) grinding step, in the (B) pressing step, the compression ratio of the primary sheet is preferably 20-80%, more preferably 30-70%. With such a compressibility, the thermal resistance of the thermally conductive sheet tends to decrease. Moreover, by performing (B) pressurization process before (C) grinding|polishing process, even when the surface state deteriorates in a pressurization process, it becomes easy to obtain the thermally conductive sheet with a smooth surface. In other words, by performing the (B) pressing step before the (C) grinding step, the unevenness of the surface roughness of the finally obtained thermal conductive sheet can be suppressed, thereby reducing the unevenness of the thermal resistance value.

相對於此，當於（C）研磨步驟之後進行（B）加壓步驟時，（B）加壓步驟中，初級片之壓縮率較佳為5～80%，更佳為10～70%。若為此種壓縮率，則導熱性片之熱阻值易降低。 即，藉由在（C）研磨步驟之後進行（B）加壓步驟，即使於壓縮率較低之情形時，亦容易獲得熱阻值較低之導熱性片。換言之，藉由在（C）研磨步驟之後進行（B）加壓步驟，（B）加壓步驟中之壓縮率可設定於相對寬廣之數值範圍內，提高導熱性片之生產性。 當於（C）研磨步驟之後進行（B）加壓步驟時，（B）加壓步驟易成為使初級片之表面粗糙化之步驟，但即使於此種情形時，亦可獲得熱阻值較低之導熱性片。 再者，加壓步驟中之壓縮率由下式算出。 壓縮率（%）＝100×[（加壓前之片厚度－加壓時之片厚度）/加壓前之片厚度] On the other hand, when the (B) pressing step is performed after the (C) grinding step, the compression ratio of the primary sheet in the (B) pressing step is preferably 5 to 80%, more preferably 10 to 70%. With such a compression rate, the thermal resistance of the thermally conductive sheet tends to decrease. That is, by performing the (B) pressurization step after the (C) grinding step, even when the compressibility is low, it is easy to obtain a thermally conductive sheet with a low thermal resistance value. In other words, by performing the (B) pressing step after the (C) grinding step, the compression rate in the (B) pressing step can be set within a relatively wide range of values, improving the productivity of the thermally conductive sheet. When the (B) pressing step is performed after the (C) grinding step, the (B) pressing step tends to be a step for roughening the surface of the primary sheet, but even in this case, a lower thermal resistance value can be obtained. Low thermal conductivity sheet. In addition, the compression ratio in the pressurization step was calculated from the following formula. Compression ratio (%)=100×[(sheet thickness before pressing - sheet thickness when pressing)/sheet thickness before pressing]

對初級片進行加壓之方法只要為可將片於厚度方向上進行壓縮之方法即可，並無特別限制，例如可列舉將初級片夾於兩片平板之間進行加壓之方法。又，壓縮率可以如下方式進行調整，例如，於兩片平板之間配置間隔件再進行加壓。平板之材質並無特別限定，例如可使用如不鏽鋼、鋁、高碳鋼、預硬鋼般之金屬材料。又，可利用平板直接進行加壓，但於難以剝離初級片之情形時，亦可介存剝離片。The method of pressing the primary sheet is not particularly limited as long as it can compress the sheet in the thickness direction. For example, a method of pressing the primary sheet between two flat plates is mentioned. Also, the compressibility can be adjusted by, for example, placing a spacer between two flat plates and then applying pressure. The material of the flat plate is not particularly limited, for example, metal materials such as stainless steel, aluminum, high carbon steel, and pre-hardened steel can be used. Also, the pressure can be directly applied with a flat plate, but when it is difficult to peel off the primary sheet, the peeling sheet can also be interposed.

[（C）研磨步驟] （C）研磨步驟係研磨初級片之表面之步驟。藉由對表面進行研磨，片表面之表面粗糙度降低，與被黏著體之密接性提高，因此熱阻值容易降低。 [(C) Grinding step] (C) The grinding step is a step of grinding the surface of the primary sheet. By grinding the surface, the surface roughness of the sheet surface is reduced, and the adhesion with the adherend is improved, so the thermal resistance value is easily reduced.

表面之研磨例如可使用研磨紙、研磨膜、研磨布、研磨帶等。作為研磨紙之特性，例如，含有之研磨粒之平均粒徑（D50）較佳為0.1～100 μm，更佳為9～60 μm。藉由使用平均粒徑為0.1 μm以上之研磨紙，異向性填充材可從片表面露出，且可使表面平滑化。具體而言，可使與發熱體等之接觸對象面之接觸點以帶有弧度之方式平滑化。又，藉由使用平均粒徑為100 μm以下之研磨紙，防止導熱性片之表面被劃傷等實用性問題。又，出於與上述相同之理由，例如，研磨紙之研磨粒之粒度較佳為♯120～20000，較佳為♯300～15000，更佳為♯320～4000。For surface polishing, for example, abrasive paper, abrasive film, abrasive cloth, abrasive tape, etc. can be used. As characteristics of the abrasive paper, for example, the average particle diameter (D50) of the abrasive grains contained is preferably 0.1 to 100 μm, more preferably 9 to 60 μm. By using abrasive paper with an average particle diameter of 0.1 μm or more, the anisotropic filler can be exposed from the surface of the sheet and the surface can be smoothed. Specifically, it is possible to smooth the contact point with the contact surface of the heating element or the like in an arcuate manner. In addition, by using abrasive paper with an average particle diameter of 100 μm or less, practical problems such as scratches on the surface of the thermally conductive sheet can be prevented. Also, for the same reason as above, for example, the particle size of the abrasive grains of the abrasive paper is preferably ♯120-20000, more preferably ♯300-15000, more preferably ♯320-4000.

研磨方法可使用如下方法，例如：將研磨紙於同一直線方向上連續抵接於初級片之表面進行研磨，此外，將研磨紙在初級片之表面往返一定距離進行研磨，或將研磨紙在初級片之表面於同一方向上旋轉進行研磨，或將研磨紙於多個方向抵接於初級片之表面進行研磨等。 又，關於研磨程度，例如，可一面觀察表面狀態一面進行研磨，例如於往返研磨之情形時，較佳為往返1～300次，更佳為往返2～200次，進而較佳為往返3～50次，具體而言，較佳為研磨至異向性填充材之突出長度為100 μm以下之程度。進而，更佳為研磨至異向性填充材之突出長度為50 μm以下之程度。 上述研磨較佳為於初級片之雙面進行，但如下情形亦可，即於兩個表面中之僅一個表面進行研磨，並且另一表面不進行研磨，又，即使進行研磨，亦可於上述條件以外之條件下進行研磨。 The grinding method can use the following methods, for example: grind the grinding paper on the surface of the primary sheet continuously in the same linear direction, and grind the grinding paper back and forth on the surface of the primary sheet for a certain distance, or put the grinding paper on the surface of the primary sheet The surface of the sheet is rotated in the same direction for grinding, or abrasive paper is brought into contact with the surface of the primary sheet in multiple directions for grinding, etc. Also, regarding the degree of grinding, for example, the grinding can be performed while observing the surface state. For example, in the case of reciprocating grinding, it is preferably 1 to 300 reciprocating times, more preferably 2 to 200 reciprocating times, and more preferably 3 to 300 reciprocating times. 50 times, specifically, it is preferable to polish until the protruding length of the anisotropic filler becomes 100 μm or less. Furthermore, it is more preferable to grind until the protruding length of the anisotropic filler becomes 50 μm or less. The above-mentioned grinding is preferably performed on both sides of the primary sheet, but it is also possible that only one of the two surfaces is ground and the other surface is not ground, and even if it is ground, it can also be ground on the above-mentioned surface. Grinding is carried out under conditions other than the conditions.

研磨步驟中，較佳為以如下方式進行研磨，即，初級片於研磨步驟前後之厚度變化例如為4～40%，較佳為8～30%。 初級片於研磨步驟前後之厚度變化可由下式求出。 研磨步驟前後之厚度變化（%）＝100×[（研磨步驟前之片厚度－研磨步驟後之片厚度）/（研磨步驟前之片厚度）] In the grinding step, the grinding is preferably performed in such a manner that the thickness change of the primary sheet before and after the grinding step is, for example, 4-40%, preferably 8-30%. The change in thickness of the primary sheet before and after the grinding step can be obtained from the following formula. Change in thickness before and after the grinding step (%) = 100×[(thickness of the sheet before the grinding step-thickness of the sheet after the grinding step)/(thickness of the sheet before the grinding step)]

[導熱性片] 利用包括上述步驟（A）～（C）之方法，可製造熱阻值較低之導熱性片。 [Thermal Conductive Sheet] By using the method comprising the above steps (A) to (C), a thermally conductive sheet with low thermal resistance can be manufactured.

＜算術平均高度（Sa）＞ 導熱性片之表面算術平均高度（Sa）較佳為20 μm以下，更佳為1～15 μm，進而較佳為1～12 μm。藉由將算術平均高度（Sa）調整為上述範圍，片表面具有平滑性，片與發熱體等密接之接觸面積擴大，可降低熱阻值。算術平均高度（Sa）可利用市售之表面性狀測定機進行測定，具體而言，可根據實施例中記載之方法進行測定。 ＜Arithmetic mean height (Sa)＞ The surface arithmetic mean height (Sa) of the thermally conductive sheet is preferably 20 μm or less, more preferably 1-15 μm, further preferably 1-12 μm. By adjusting the arithmetic mean height (Sa) to the above range, the surface of the sheet becomes smooth, and the contact area between the sheet and the heat generating element expands, and the thermal resistance value can be reduced. The arithmetic mean height (Sa) can be measured using a commercially available surface texture measuring machine, specifically, it can be measured according to the method described in the Examples.

為了使算術平均高度（Sa）在上述範圍內，例如，可使用粒度#120～20000之研磨紙中之粒度相對較粗者，適當地設定與粒度相應之研磨次數，對表面進行研磨處理。In order to keep the arithmetic mean height (Sa) within the above range, for example, use abrasive paper with a particle size of #120-20000, which is relatively coarse, and properly set the number of times of grinding corresponding to the particle size to perform grinding treatment on the surface.

＜界面展開面積比（Sdr）＞ 又，導熱性片之表面之界面展開面積比（Sdr）較佳為30以下，更佳為1～20，進而較佳為1～10。藉由將界面展開面積比（Sdr）調整為上述範圍，片表面具有平滑性，片與發熱體等密接之接觸面積擴大，可降低熱阻值。 ＜Interface development area ratio (Sdr)＞ Moreover, the interface expansion area ratio (Sdr) of the surface of a thermally conductive sheet becomes like this. Preferably it is 30 or less, More preferably, it is 1-20, More preferably, it is 1-10. By adjusting the interface expansion area ratio (Sdr) to the above range, the surface of the sheet becomes smooth, and the contact area between the sheet and the heating element, etc. is enlarged, and the thermal resistance value can be reduced.

再者，界面展開面積比（Sdr）係表示定義區域之展開面積（表面積）相對於定義區域之面積（例如1 mm ²）增加了多少之指標，完全平坦之面之展開面積比Sdr為0。界面展開面積比（Sdr）可根據實施例中記載之方法進行測定。 Furthermore, the interface expansion area ratio (Sdr) is an index indicating how much the expansion area (surface area) of the defined area has increased relative to the area of the defined area (eg 1 mm ² ), and the expansion area ratio Sdr of a completely flat surface is 0. The interface developed area ratio (Sdr) can be measured according to the method described in the Examples.

又，為了使界面展開面積比（Sdr）在上述範圍內，例如，可使用粒度#120～20000之研磨紙中之粒度相對較粗者，適當地設定與粒度相應之研磨次數，對表面進行研磨處理。In addition, in order to make the interface expansion area ratio (Sdr) within the above range, for example, use abrasive paper with a particle size of #120-20000, which is relatively coarse, and properly set the number of times of grinding corresponding to the particle size to grind the surface deal with.

＜未硬化成分＞ 導熱性片之表面較佳為處於不存在未硬化成分之狀態。藉此，可防止未硬化成分因紫外線產生反應或與被黏著體反應而引起問題。 未硬化成分係作為形成高分子基質之原料之液狀高分子組成物中所包含之成分，例如，當藉由加成反應硬化型聚矽氧形成作為高分子基質之有機聚矽氧烷時，含烯基有機聚矽氧烷及有機氫化聚矽氧烷相當於未硬化成分。繼而，為了使表面處於不存在未硬化成分之狀態，適當地調整液狀高分子組成物之組成即可，例如，可將含烯基有機聚矽氧烷及有機氫化聚矽氧烷兩者均調整為適當含量，使其等不會過量，以防止其中任一者作為未反應成分大量殘留。 ＜Unhardened component＞ The surface of the thermally conductive sheet is preferably in a state where no unhardened components exist. This prevents unhardened components from reacting with ultraviolet rays or reacting with adherends, causing problems. The unhardened component is a component contained in a liquid polymer composition as a raw material for forming a polymer matrix, for example, when forming an organopolysiloxane as a polymer matrix by addition reaction hardening polysiloxane, Alkenyl-containing organopolysiloxanes and organohydrogenpolysiloxanes correspond to unhardened components. Then, in order to keep the surface in a state where no unhardened components exist, it is sufficient to adjust the composition of the liquid polymer composition appropriately. For example, both an alkenyl-containing organopolysiloxane and an organohydrogenpolysiloxane can be mixed It is adjusted to an appropriate content so that there is no excess of any of them, so that a large amount of any of them remains as an unreacted component.

＜厚度＞ 導熱性片之厚度並無特別限定，根據供導熱性片搭載之電子機器之形狀及用途適當進行變更，例如為0.1～5.0 mm，較佳為0.1～0.3 mm。藉由使導熱性片之厚度為0.1～0.3 mm，導熱性片之厚度變薄，成為易導熱之導熱性片。 ＜Thickness＞ The thickness of the thermally conductive sheet is not particularly limited, and can be appropriately changed according to the shape and application of the electronic device on which the thermally conductive sheet is mounted, for example, it is 0.1-5.0 mm, preferably 0.1-0.3 mm. By making the thickness of the thermally conductive sheet 0.1 to 0.3 mm, the thickness of the thermally conductive sheet becomes thinner and becomes a thermally conductive sheet that conducts heat easily.

[導熱性片之用途] 本發明中製造之導熱性片可配置於電子機器中之發熱體與散熱體之間而較佳地使用。作為發熱體，例如可列舉電子元件等，作為散熱體，例如可列舉散熱片、熱管等。 [實施例] [Applications of thermally conductive sheet] The thermally conductive sheet manufactured in the present invention can be preferably used by being disposed between a heat generating body and a heat sink in an electronic device. As a heating body, an electronic component etc. are mentioned, for example, As a heat dissipation body, a heat radiation fin, a heat pipe, etc. are mentioned, for example. [Example]

以下，根據實施例，更詳細地說明本發明，但本發明並不受該等例任何限定。Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited by these examples.

本實施例中，根據以下方法評價導熱性片之物性。In the present examples, the physical properties of the thermally conductive sheet were evaluated according to the following methods.

[算術平均高度（Sa）、界面展開面積比（Sdr）] 導熱性片之算術平均高度（Sa）及界面展開面積比（Sdr）係以下述方式進行測定。 使用雷射顯微鏡（KEYENCE股份有限公司製造、VK-X150）進行表面性狀解析，根據ISO25178測定導熱性片之算術平均高度（Sa）及界面展開面積比（Sdr）。具體而言，以10倍透鏡倍率，藉由雷射法測定表面積為1000 μm×1000 μm之二維區域之表面輪廓。採用測定同一樣品之三處部位時獲得之平均值作為算術平均高度（Sa）。關於界面展開面積比（Sdr）亦採用相同方式，測定同一樣品之三處部位，以其平均值作為界面展開面積比（Sdr）。 [Arithmetic mean height (Sa), interface area ratio (Sdr)] The arithmetic mean height (Sa) and interface expansion area ratio (Sdr) of the thermally conductive sheet were measured in the following manner. Surface properties were analyzed using a laser microscope (manufactured by KEYENCE Co., Ltd., VK-X150), and the arithmetic mean height (Sa) and interface spread area ratio (Sdr) of the thermally conductive sheet were measured in accordance with ISO25178. Specifically, the surface profile of a two-dimensional region with a surface area of 1000 μm×1000 μm was measured by a laser method at a lens magnification of 10 times. The average value obtained when measuring three parts of the same sample is used as the arithmetic mean height (Sa). Regarding the interface expansion area ratio (Sdr), the same method was used to measure three parts of the same sample, and the average value was used as the interface expansion area ratio (Sdr).

[熱阻值] 熱阻值係使用如圖3所示之熱阻測定機，根據以下所示方法進行測定。 具體而言，將各試樣製成尺寸為30 mm×30 mm×0.2 mmt之試驗片S，用於本試驗。繼而，將各試驗片S貼附於測定面為25.4 mm×25.4 mm、側面由隔熱材料21覆蓋之銅製塊22上，以上方之銅製塊23夾住，用荷重元26施加壓力20 psi（0.138 MPa）之負載。此處，下方之銅製塊22與加熱器24相接。又，上方之銅製塊23由隔熱材料21覆蓋，且與帶風扇之散熱片25連接。其次，使加熱器24發熱，使溫度呈大致穩定狀態，10分鐘後，測定上方之銅製塊23之溫度（θ _j0）、下方之銅製塊22之溫度（θ _j1）、及加熱器之發熱量（Q），根據以下式（1）求出各試樣之熱阻值。再者，關於溫度，以使導熱性片達到80℃之方式調整發熱量。 熱阻值＝（θ _j1－θ _j0）/Q      ・・・式（1） 式（1）中，θ _j1為下方之銅製塊22之溫度，θ _j0為上方之銅製塊23之溫度，Q為發熱量。 [Thermal Resistance] The thermal resistance was measured by the method shown below using the thermal resistance measuring machine shown in Fig. 3 . Specifically, each sample was made into a test piece S with a size of 30 mm×30 mm×0.2 mmt for use in this test. Next, attach each test piece S to a copper block 22 whose measuring surface is 25.4 mm×25.4 mm and whose side is covered by a heat insulating material 21, clamp it with the upper copper block 23, and apply a pressure of 20 psi with a load cell 26 ( 0.138 MPa) load. Here, the lower copper block 22 is in contact with the heater 24 . Also, the upper copper block 23 is covered by a heat insulating material 21 and connected to a cooling fin 25 with a fan. Next, let the heater 24 generate heat to make the temperature approximately stable. After 10 minutes, measure the temperature (θ _j0 ) of the upper copper block 23 , the temperature (θ _j1 ) of the lower copper block 22 , and the calorific value of the heater. (Q), calculate the thermal resistance value of each sample according to the following formula (1). In addition, about temperature, the calorific value was adjusted so that a thermally conductive sheet may become 80 degreeC. Thermal resistance value = (θ _j1 - θ _j0 )/Q ・・・Formula (1) In formula (1), _{θj1 is the temperature of the lower copper block 22, θ j0 is} the temperature of the upper copper block 23, and Q is Calorific value.

[配向率] 利用電子顯微鏡觀察所製作之初級片之剖面，抽取100個異向性填充材，求出100個填充材中，於片之厚度方向上配向之異向性填充材之數量。若有61個（61%）以上配向於厚度方向上，則記為A，若未達60個（60%），則記為B。 再者，將異向性填充材之長軸方向處於距離初級片之厚度方向20°以內之範圍者判斷為處於配向狀態。 [Orientation rate] The cross-section of the prepared primary sheet was observed with an electron microscope, 100 anisotropic fillers were selected, and the number of anisotropic fillers aligned in the thickness direction of the sheet among the 100 fillers was calculated. If 61 (61%) or more are aligned in the thickness direction, it will be set as A, and if it is less than 60 (60%), it will be set as B. Furthermore, the anisotropic filler whose major axis direction is within 20° from the thickness direction of the primary sheet is judged to be in an aligned state.

本實施例中，如下所述，分別準備不含烴系化合物之組成A與包含烴系化合物之組成B作為混合組成物。In this example, as described below, composition A not containing hydrocarbon-based compounds and composition B containing hydrocarbon-based compounds were respectively prepared as mixed compositions.

[混合組成物（組成A）] 根據表1之摻合量，將作為高分子組成物之聚矽氧主劑（含烯基有機聚矽氧烷）、聚矽氧硬化劑（有機氫化聚矽氧烷）、及觸媒（鉑系觸媒）與作為相溶性物質之正癸基三甲氧基矽烷均勻地混合，獲得混合物，根據表1之摻合量於該混合物中混合異向性填充材及非異向性填充材，獲得組成A之混合組成物。 再者，作為異向性填充材，使用鱗片石墨粉末（平均長軸長度130 μm）、石墨化碳纖維1（平均纖維長度77 μm）、及石墨化碳纖維2（平均纖維長度150 μm）。作為非異向性填充材，使用鋁粉末（平均粒徑3 μm）。 [Mixed composition (composition A)] According to the blending amount in Table 1, the polysiloxane main agent (containing alkenyl organopolysiloxane), the polysiloxane hardener (organohydrogenpolysiloxane), and the catalyst (platinum catalyst) and n-decyltrimethoxysilane as a compatible substance are uniformly mixed to obtain a mixture, and an anisotropic filler and an anisotropic filler are mixed in the mixture according to the blending amount in Table 1 to obtain Composition A mixed composition. In addition, as the anisotropic filler, flake graphite powder (average major axis length 130 μm), graphitized carbon fiber 1 (average fiber length 77 μm), and graphitized carbon fiber 2 (average fiber length 150 μm) were used. As an anisotropic filler, aluminum powder (average particle size: 3 μm) was used.

[混合組成物（組成B）] 根據表1之摻合量，於23℃使作為烴系化合物之側鏈結晶性聚α-烯烴（CPAO、熔點（Tm）：42℃）與作為相溶性物質之正癸基三甲氧基矽烷混合，獲得烴系化合物溶解於相溶性物質而成之混合物。將所得混合物與作為高分子組成物之聚矽氧主劑（含烯基有機聚矽氧烷）、聚矽氧硬化劑（有機氫化聚矽氧烷）、及觸媒（鉑系觸媒）均勻地混合後，根據表1之摻合量混合異向性填充材及非異向性填充材，獲得組成B之混合組成物。 再者，作為異向性填充材，使用鱗片石墨粉末（平均長軸長度130 μm）、石墨化碳纖維1（平均纖維長度77 μm）、及石墨化碳纖維2（平均纖維長度150 μm）。作為非異向性填充材，使用鋁粉末（平均粒徑3 μm）。 [Mixed composition (composition B)] According to the blending amount in Table 1, side-chain crystalline polyalphaolefin (CPAO, melting point (Tm): 42°C) as a hydrocarbon compound and n-decyltrimethoxysilane as a compatible substance were mixed at 23°C , to obtain a mixture of hydrocarbon compounds dissolved in compatible substances. Mix the resulting mixture with the polysiloxane main agent (containing alkenyl organopolysiloxane), the polysiloxane hardener (organohydrogenpolysiloxane), and the catalyst (platinum catalyst) as a polymer composition After ground mixing, the anisotropic filler and the non-anisotropic filler were mixed according to the blending amounts in Table 1 to obtain a mixed composition of composition B. In addition, as the anisotropic filler, flake graphite powder (average major axis length 130 μm), graphitized carbon fiber 1 (average fiber length 77 μm), and graphitized carbon fiber 2 (average fiber length 150 μm) were used. As an anisotropic filler, aluminum powder (average particle size: 3 μm) was used.

[表1]    混合組成物之組成 組成A 組成B 高分子組成物 含烯基有機聚矽氧烷及有機氫化聚矽氧烷 質量份 100 100 添加劑 觸媒 0.1 0.1 烴系化合物 CPAO 0 3 非異向性填充材 鋁粉末3 μm（平均粒徑） 243 243 異向性填充材 鱗片石墨粉末1  30 μm（平均長軸長度） 20 20 石墨化碳纖維1  77 μm（平均纖維長度） 140 140 石墨化碳纖維2  150 μm（平均纖維長度） 10 10 相溶性物質 正癸基三甲氧基矽烷 22 22 [Table 1] Composition of Mixed Composition Composition A Composition B polymer composition Alkenyl-containing organopolysiloxanes and organohydrogenpolysiloxanes parts by mass 100 100 additive catalyst 0.1 0.1 Hydrocarbons CPAO 0 3 Anisotropic filler Aluminum powder 3 μm (average particle size) 243 243 Anisotropic filler Flake graphite powder 1 30 μm (average major axis length) 20 20 Graphitized carbon fiber 1 77 μm (average fiber length) 140 140 Graphitized carbon fiber 2 150 μm (average fiber length) 10 10 Compatible substances n-decyltrimethoxysilane twenty two twenty two

（實施例1） 將混合組成物（組成A）注入至厚度設定為充分大於導熱性片之模具中，於厚度方向施加8T之磁場，使異向性填充材於厚度方向上配向後，藉由在80℃加熱60分鐘，使高分子組成物硬化，獲得塊狀配向成形體。 其次，使用剪切刀片，將塊狀配向成形體切成厚度約為0.2 mm之片狀，藉此獲得異向性填充材之端部露出之初級片，進而，藉由在150℃加熱2小時，使一部分之相溶性物質揮發。再者，初級片之厚度之實際測定值以表2之初始厚度示出。 繼而，利用研磨粒之平均粒徑（D50）為20 μm之粗研磨紙A（粒度#800）對初級片之兩個表面進行50次往返研磨，實施研磨步驟。 其後，以如表2所示之加壓溫度及壓縮率實施加壓步驟，獲得導熱性片。加壓步驟係藉由將初級片夾於兩片平板（高碳鋼「S50C」製）之間並進行加壓來實施，於兩片平板之間配置間隔件以調節壓縮率。對所得之導熱性片測定熱阻值，將結果示於下表。 (Example 1) Inject the mixed composition (composition A) into a mold whose thickness is set to be sufficiently larger than that of the thermally conductive sheet, apply a magnetic field of 8T in the thickness direction, and align the anisotropic filler in the thickness direction, then heat at 80°C for 60 Minutes, the polymer composition is hardened to obtain a block-shaped alignment molding. Next, using a shear blade, cut the bulk alignment molding into sheets with a thickness of about 0.2 mm, thereby obtaining a primary sheet with the end of the anisotropic filler exposed, and further, by heating at 150°C for 2 hours , to volatilize part of the compatible substances. In addition, the actual measured value of the thickness of the primary sheet is shown in Table 2 as the initial thickness. Then, the two surfaces of the primary sheet were reciprocally ground 50 times with coarse abrasive paper A (grain size #800) having an average particle diameter (D50) of abrasive grains of 20 μm, and a grinding step was performed. Thereafter, a press step was performed at the press temperature and compression rate shown in Table 2 to obtain a thermally conductive sheet. The pressurization step is carried out by clamping the primary sheet between two flat plates (made of high carbon steel "S50C") and pressurizing, and a spacer is placed between the two flat plates to adjust the compressibility. The thermal resistance of the obtained thermally conductive sheet was measured, and the results are shown in the table below.

（實施例2） 將混合組成物（組成A）注入至厚度設定為充分大於導熱性片之模具中，於厚度方向上施加8T之磁場，使異向性填充材於厚度方向上配向後，藉由在80℃加熱60分鐘，使高分子組成物硬化，獲得塊狀配向成形體。 其次，使用剪切刀片，將塊狀配向成形體切成厚度約為0.2 mm之片狀，藉此獲得異向性填充材之端部露出之初級片，進而，藉由在150℃加熱2小時，使一部分之相溶性物質揮發。 繼而，以如表2所示之加壓溫度及壓縮率實施加壓步驟。加壓步驟係藉由將初級片夾於兩片平板（高碳鋼「S50C」製）之間並進行加壓來實施，於兩片平板之間配置間隔件以調節壓縮率。 其後，利用研磨粒之平均粒徑（D50）為20 μm之粗研磨紙A（粒度#800）對初級片之兩個表面進行50次往返研磨，實施研磨步驟，製造導熱性片。對所得之導熱性片測定熱阻值，將結果示於下表。 (Example 2) Inject the mixed composition (composition A) into a mold whose thickness is set to be sufficiently larger than that of the thermally conductive sheet, and apply a magnetic field of 8T in the thickness direction to align the anisotropic filler in the thickness direction, and then heat it at 80°C After 60 minutes, the polymer composition was hardened to obtain a bulk aligned molded body. Next, using a shear blade, cut the bulk alignment molding into sheets with a thickness of about 0.2 mm, thereby obtaining a primary sheet with the end of the anisotropic filler exposed, and further, by heating at 150°C for 2 hours , to volatilize part of the compatible substances. Then, a pressurization step was carried out at the pressurization temperature and compression ratio shown in Table 2. The pressurization step is carried out by clamping the primary sheet between two flat plates (made of high carbon steel "S50C") and pressurizing, and a spacer is placed between the two flat plates to adjust the compressibility. Thereafter, both surfaces of the primary sheet were ground back and forth 50 times with coarse abrasive paper A (grain size #800) having an average particle diameter (D50) of 20 μm, and the grinding step was performed to manufacture a thermally conductive sheet. The thermal resistance of the obtained thermally conductive sheet was measured, and the results are shown in the table below.

（實施例3、5～8、13～16） 如表2、3所述變更混合組成物之種類以及加壓步驟中之加壓溫度及壓縮率，除此以外，以與實施例1相同之方式製造導熱性片。對所得之導熱性片測定熱阻值，將結果示於下表。 (Examples 3, 5-8, 13-16) A thermally conductive sheet was produced in the same manner as in Example 1, except that the type of the mixed composition and the pressurization temperature and compression ratio in the pressurization step were changed as described in Tables 2 and 3. The thermal resistance of the obtained thermally conductive sheet was measured, and the results are shown in the table below.

（實施例4、9～12、17～20） 如表2～4所述變更混合組成物之種類以及加壓步驟中之加壓溫度及壓縮率，除此以外，以與實施例2相同之方式製造導熱性片。對所得之導熱性片測定熱阻值，將結果示於下表。 (Examples 4, 9-12, 17-20) A thermally conductive sheet was produced in the same manner as in Example 2, except that the type of the mixed composition and the pressurization temperature and compression ratio in the pressurization step were changed as described in Tables 2 to 4. The thermal resistance of the obtained thermally conductive sheet was measured, and the results are shown in the table below.

再者，目視觀察以實施例1～20之方法獲得之導熱性片之表面，其結果，未確認到未硬化成分之存在。In addition, as a result of visual observation of the surface of the thermally conductive sheet obtained by the method of Examples 1-20, the presence of the uncured component was not confirmed.

（比較例1） 將混合組成物（組成A）注入至厚度設定為充分大於導熱性片之模具中，於厚度方向上施加8T之磁場，使異向性填充材於厚度方向上配向後，藉由在80℃加熱60分鐘，使高分子組成物硬化，獲得塊狀配向成形體。 其次，使用剪切刀片，將塊狀配向成形體切成厚度約為0.2 mm之片狀，藉此獲得異向性填充材之端部露出之導熱性片，進而，藉由在150℃加熱2小時，使一部分之相溶性物質揮發。 對所得之導熱性片測定熱阻值，將結果示於下表。 (comparative example 1) Inject the mixed composition (composition A) into a mold whose thickness is set to be sufficiently larger than that of the thermally conductive sheet, and apply a magnetic field of 8T in the thickness direction to align the anisotropic filler in the thickness direction, and then heat it at 80°C After 60 minutes, the polymer composition was hardened to obtain a bulk aligned molded body. Next, use a shearing blade to cut the block-shaped alignment molded body into a sheet with a thickness of about 0.2 mm, thereby obtaining a thermally conductive sheet exposed at the end of the anisotropic filler, and then, by heating at 150°C for 2 Hours, to volatilize part of the compatible substances. The thermal resistance of the obtained thermally conductive sheet was measured, and the results are shown in the table below.

（比較例2） 將混合組成物（組成A）注入至厚度設定為充分大於導熱性片之模具中，於厚度方向上施加8T之磁場，使異向性填充材於厚度方向上配向後，藉由在80℃加熱60分鐘，使高分子組成物硬化，獲得塊狀配向成形體。其次，使用剪切刀片，將塊狀配向成形體切成厚度約為0.2 mm之片狀，藉此獲得異向性填充材之端部露出之導熱性片，進而，藉由在150℃加熱2小時，使一部分之相溶性物質揮發。 其次，以表5所示之加壓溫度及壓縮率實施加壓步驟，獲得導熱性片。加壓步驟係藉由將初級片夾於兩片平板（高碳鋼「S50C」製）之間並進行加壓來實施，於兩片平板之間配置間隔件以調節壓縮率。 (comparative example 2) Inject the mixed composition (composition A) into a mold whose thickness is set to be sufficiently larger than that of the thermally conductive sheet, and apply a magnetic field of 8T in the thickness direction to align the anisotropic filler in the thickness direction, and then heat it at 80°C After 60 minutes, the polymer composition was hardened to obtain a bulk aligned molded body. Next, use a shearing blade to cut the block-shaped alignment molded body into a sheet with a thickness of about 0.2 mm, thereby obtaining a thermally conductive sheet exposed at the end of the anisotropic filler, and then, by heating at 150°C for 2 Hours, to volatilize part of the compatible substances. Next, a press step was performed at the press temperature and compression ratio shown in Table 5 to obtain a thermally conductive sheet. The pressurization step is carried out by clamping the primary sheet between two flat plates (made of high carbon steel "S50C") and pressurizing, and a spacer is placed between the two flat plates to adjust the compressibility.

（比較例3） 將混合組成物（組成A）注入至厚度設定為充分大於導熱性片之模具中，於厚度方向上施加8T之磁場，使異向性填充材於厚度方向上配向後，藉由在80℃加熱60分鐘，使高分子組成物硬化，獲得塊狀配向成形體。 其次，使用剪切刀片，將塊狀配向成形體切成厚度約為0.2 mm之片狀，藉此獲得異向性填充材之端部露出之初級片，進而，藉由在150℃加熱2小時，使一部分之相溶性物質揮發。 繼而，利用研磨粒之平均粒徑（D50）為20 μm之粗研磨紙A（粒度#800）對初級片之兩個表面進行50次往返研磨，實施研磨步驟，獲得導熱性片。對所得之導熱性片測定熱阻值，將結果示於下表。 (comparative example 3) Inject the mixed composition (composition A) into a mold whose thickness is set to be sufficiently larger than that of the thermally conductive sheet, and apply a magnetic field of 8T in the thickness direction to align the anisotropic filler in the thickness direction, and then heat it at 80°C After 60 minutes, the polymer composition was hardened to obtain a bulk aligned molded body. Next, using a shear blade, cut the bulk alignment molding into sheets with a thickness of about 0.2 mm, thereby obtaining a primary sheet with the end of the anisotropic filler exposed, and further, by heating at 150°C for 2 hours , to volatilize part of the compatible substances. Then, use coarse abrasive paper A (grain size #800) with an average particle diameter (D50) of 20 μm to grind the two surfaces of the primary sheet back and forth 50 times, and perform the grinding step to obtain a thermally conductive sheet. The thermal resistance of the obtained thermally conductive sheet was measured, and the results are shown in the table below.

（比較例4） 如表5所述變更混合組成物之種類，除此以外，以與比較例1相同之方式獲得導熱性片。對所得之導熱性片測定熱阻值，將結果示於下表。 (comparative example 4) A thermally conductive sheet was obtained in the same manner as in Comparative Example 1 except that the type of the mixed composition was changed as described in Table 5. The thermal resistance of the obtained thermally conductive sheet was measured, and the results are shown in the table below.

（比較例5） 如表5所述變更混合組成物之種類，除此以外，以與比較例2相同之方式獲得導熱性片。對所得之導熱性片測定熱阻值，將結果示於下表。 (comparative example 5) A thermally conductive sheet was obtained in the same manner as in Comparative Example 2 except that the type of the mixed composition was changed as described in Table 5. The thermal resistance of the obtained thermally conductive sheet was measured, and the results are shown in the table below.

（比較例6） 如表5所述變更混合組成物之種類，除此以外，以與比較例3相同之方式獲得導熱性片。對所得之導熱性片測定熱阻值，將結果示於下表。 (comparative example 6) A thermally conductive sheet was obtained in the same manner as in Comparative Example 3 except that the type of the mixed composition was changed as described in Table 5. The thermal resistance of the obtained thermally conductive sheet was measured, and the results are shown in the table below.

再者，表2～5中，「熱阻之降低率（%）」係指與未實施研磨步驟及加壓步驟之例相比較時之熱阻之降低率（%）。更詳細而言，當使用組成A作為混合組成物時，係指與比較例1之熱阻相比較時之熱阻之降低率（%），當使用組成B作為混合組成物時，係指與比較例4之熱阻相比較時之熱阻之降低率（%）。In addition, in Tables 2-5, "the reduction rate (%) of thermal resistance" means the reduction rate (%) of the thermal resistance when compared with the example which did not perform a grinding process and a pressurization process. More specifically, when composition A is used as the mixed composition, it refers to the reduction rate (%) of thermal resistance when compared with the thermal resistance of Comparative Example 1, and when composition B is used as the mixed composition, it refers to the reduction rate (%) compared with that of Comparative Example 1. The reduction rate (%) of the thermal resistance when comparing the thermal resistance of Comparative Example 4.

[表2]       實施例 1 實施例 2 實施例 3 實施例 4 實施例 5 實施例 6 實施例 7 實施例 8 混合組成物之組成 A A B B A A A A 實施步驟 研磨 ↓ 加壓 加壓 ↓ 研磨 研磨 ↓ 加壓 加壓 ↓ 研磨 研磨 ↓ 加壓 加壓步驟之條件 加壓溫度（℃） 30 30 30 30 60 30 30 30 加壓時之壓縮率（%） 50 50 50 50 50 10 30 70 研磨步驟之條件 20 μm研磨紙研磨 有 有 有 有 有 有 有 有 初級片之厚度 初始厚度（mm） 0.206 0.206 0.201 0.189 0.205 0.213 0.205 0.204 加壓步驟前後之厚度變化（mm） 0.025 0.037 0.029 0.046 0.024 0.007 0.017 0.026 加壓步驟前後之厚度變化（%） 16% 18% 18% 24% 16% 4% 11% 17% 研磨步驟前後之厚度變化（mm） 0.054 0.031 0.046 0.012 0.051 0.053 0.052 0.051 研磨步驟前後之厚度變化（%） 26% 18% 23% 9% 25% 25% 25% 25% 總行程中之厚度變化（mm） 0.079 0.068 0.075 0.058 0.075 0.060 0.069 0.077 總行程中之厚度變化（%） 42% 36% 41% 33% 40% 29% 36% 42% 初級片之配向率 A A A A A A A A 導熱性片之表面粗糙度 Sa 算術平均高度（μm） 10.2 7.6 8.8 8.0 9.4 12.2 8.5 9.9 Sdr 界面展開面積比 6.5 5.6 5.1 4.4 7.5 6.1 6.1 5.7 熱阻測定結果 （20 psi壓縮） 熱阻（℃·in ²/W） 0.020 0.019 0.019 0.018 0.021 0.021 0.02 0.021 測定時之厚度（mm） 0.149 0.145 0.153 0.123 0.162 0.159 0.162 0.142 測定時之壓縮率（%） 28% 30% 24% 35% 21% 25% 21% 30% 熱阻之降低率（%） 64% 65% 56% 58% 62% 62% 64% 62% [Table 2] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Composition of Mixed Composition A A B B A A A A Implementation steps Grind ↓ Pressurize Pressurize ↓ Grind Grind ↓ Pressurize Pressurize ↓ Grind Grind ↓ Pressurize Conditions of pressurization step Pressurization temperature (°C) 30 30 30 30 60 30 30 30 Compression rate when pressurized (%) 50 50 50 50 50 10 30 70 Conditions of grinding step Grinding with 20 μm abrasive paper have have have have have have have have The thickness of the primary sheet Initial thickness (mm) 0.206 0.206 0.201 0.189 0.205 0.213 0.205 0.204 Thickness change before and after pressing step (mm) 0.025 0.037 0.029 0.046 0.024 0.007 0.017 0.026 Thickness change before and after pressing step (%) 16% 18% 18% twenty four% 16% 4% 11% 17% Thickness change before and after grinding steps (mm) 0.054 0.031 0.046 0.012 0.051 0.053 0.052 0.051 Thickness change before and after grinding step (%) 26% 18% twenty three% 9% 25% 25% 25% 25% Thickness change in total stroke (mm) 0.079 0.068 0.075 0.058 0.075 0.060 0.069 0.077 Thickness change in total stroke (%) 42% 36% 41% 33% 40% 29% 36% 42% Alignment rate of primary film A A A A A A A A Surface Roughness of Thermally Conductive Sheet Sa arithmetic mean height (μm) 10.2 7.6 8.8 8.0 9.4 12.2 8.5 9.9 Sdr interface expanded area ratio 6.5 5.6 5.1 4.4 7.5 6.1 6.1 5.7 Thermal Resistance Measurement Results (20 psi Compression) Thermal resistance (℃·in ² /W) 0.020 0.019 0.019 0.018 0.021 0.021 0.02 0.021 Thickness when measured (mm) 0.149 0.145 0.153 0.123 0.162 0.159 0.162 0.142 Compression rate at the time of measurement (%) 28% 30% twenty four% 35% twenty one% 25% twenty one% 30% Reduction rate of thermal resistance (%) 64% 65% 56% 58% 62% 62% 64% 62%

[表3]       實施例 9 實施例 10 實施例 11 實施例 12 實施例 13 實施例 14 實施例 15 實施例 16 混合組成物之組成 A A A A B B B B 實施步驟 加壓 ↓ 研磨 研磨 ↓ 加壓 加壓步驟之條件 加壓溫度（℃） 60 30 30 30 60 30 30 30 加壓時之壓縮率（%） 50 10 30 70 50 10 30 70 研磨步驟之條件 20 μm研磨紙研磨* 有 有 有 有 有 有 有 有 初級片之厚度 初始厚度（mm） 0.207 0.191 0.204 0.197 0.199 0.201 0.205 0.187 加壓步驟前後之厚度變化（mm） 0.038 0.010 0.030 0.038 0.032 0.013 0.025 0.033 加壓步驟前後之厚度變化（%） 19% 5% 15% 19% 21% 8% 15% 23% 研磨步驟前後之厚度變化（mm） 0.028 0.047 0.032 0.029 0.044 0.042 0.043 0.045 研磨步驟前後之厚度變化（%） 16% 26% 18% 19% 22% 21% 21% 24% 總行程中之厚度變化（mm） 0.066 0.057 0.062 0.067 0.076 0.055 0.068 0.078 總行程中之厚度變化（%） 35% 31% 33% 38% 43% 29% 36% 47% 初級片之配向率 A A A A A A A A 導熱性片之表面粗糙度 Sa 算術平均高度（μm） 10.9 14.0 6.5 7.9 10.1 7.4 5.5 11.5 Sdr 界面展開面積比 5.8 6.6 4.7 5.5 6.5 4.7 4.7 6.3 熱阻測定結果 （20 psi壓縮） 熱阻（℃·in ²/W） 0.024 0.026 0.018 0.019 0.017 0.018 0.017 0.017 測定時之厚度（mm） 0.151 0.129 0.153 0.133 0.137 0.16 0.144 0.137 測定時之壓縮率（%） 27% 32% 25% 32% 31% 20% 30% 27% 熱阻之降低率（%） 56% 53% 67% 65% 60% 58% 60% 60% [table 3] Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Composition of Mixed Composition A A A A B B B B Implementation steps Pressurize ↓ Grind Grind ↓ Pressurize Conditions of pressurization step Pressurization temperature (°C) 60 30 30 30 60 30 30 30 Compression rate when pressurized (%) 50 10 30 70 50 10 30 70 Conditions of grinding step Grinding with 20 μm abrasive paper* have have have have have have have have The thickness of the primary sheet Initial thickness (mm) 0.207 0.191 0.204 0.197 0.199 0.201 0.205 0.187 Thickness change before and after pressing step (mm) 0.038 0.010 0.030 0.038 0.032 0.013 0.025 0.033 Thickness change before and after pressing step (%) 19% 5% 15% 19% twenty one% 8% 15% twenty three% Thickness change before and after grinding steps (mm) 0.028 0.047 0.032 0.029 0.044 0.042 0.043 0.045 Thickness change before and after grinding step (%) 16% 26% 18% 19% twenty two% twenty one% twenty one% twenty four% Thickness change in total stroke (mm) 0.066 0.057 0.062 0.067 0.076 0.055 0.068 0.078 Thickness change in total stroke (%) 35% 31% 33% 38% 43% 29% 36% 47% Alignment rate of primary film A A A A A A A A Surface Roughness of Thermally Conductive Sheet Sa arithmetic mean height (μm) 10.9 14.0 6.5 7.9 10.1 7.4 5.5 11.5 Sdr interface expanded area ratio 5.8 6.6 4.7 5.5 6.5 4.7 4.7 6.3 Thermal Resistance Measurement Results (20 psi Compression) Thermal resistance (℃·in ² /W) 0.024 0.026 0.018 0.019 0.017 0.018 0.017 0.017 Thickness when measured (mm) 0.151 0.129 0.153 0.133 0.137 0.16 0.144 0.137 Compression rate at the time of measurement (%) 27% 32% 25% 32% 31% 20% 30% 27% Reduction rate of thermal resistance (%) 56% 53% 67% 65% 60% 58% 60% 60%

[表4]       實施例 17 實施例 18 實施例 19 實施例 20 混合組成物之組成 B B B B 實施步驟 加壓 ↓ 研磨 加壓步驟之條件 加壓溫度（℃） 60 30 30 30 加壓時之壓縮率（%） 50 10 30 70 研磨步驟之條件 20 μm研磨紙研磨* 有 有 有 有 初級片之厚度 初始厚度（mm） 0.198 0.204 0.216 0.235 加壓步驟前後之厚度變化（mm） 0.048 0.022 0.046 0.059 加壓步驟前後之厚度變化（%） 24% 11% 21% 25% 研磨步驟前後之厚度變化（mm） 0.014 0.038 0.020 0.018 研磨步驟前後之厚度變化（%） 9% 21% 12% 10% 總行程中之厚度變化（mm） 0.062 0.060 0.066 0.076 總行程中之厚度變化（%） 34% 32% 33% 35% 初級片之配向率 A A A A 導熱性片之表面粗糙度 Sa 算術平均高度（μm） 10.5 12.5 8.5 8.7 Sdr 界面展開面積比 6.6 6.9 5.4 5.5 熱阻測定結果 （20 psi壓縮） 熱阻（℃·in ²/W） 0.019 0.020 0.018 0.019 測定時之厚度（mm） 0.128 0.139 0.139 0.166 測定時之壓縮率（%） 35% 32% 36% 29% 熱阻之降低率（%） 56% 53% 58% 56% [Table 4] Example 17 Example 18 Example 19 Example 20 Composition of Mixed Composition B B B B Implementation steps Pressurize ↓ Grind Conditions of pressurization step Pressurization temperature (°C) 60 30 30 30 Compression rate when pressurized (%) 50 10 30 70 Conditions of grinding step Grinding with 20 μm abrasive paper* have have have have The thickness of the primary sheet Initial thickness (mm) 0.198 0.204 0.216 0.235 Thickness change before and after pressing step (mm) 0.048 0.022 0.046 0.059 Thickness change before and after pressing step (%) twenty four% 11% twenty one% 25% Thickness change before and after grinding steps (mm) 0.014 0.038 0.020 0.018 Thickness change before and after grinding step (%) 9% twenty one% 12% 10% Thickness change in total stroke (mm) 0.062 0.060 0.066 0.076 Thickness change in total stroke (%) 34% 32% 33% 35% Alignment rate of primary film A A A A Surface Roughness of Thermally Conductive Sheet Sa arithmetic mean height (μm) 10.5 12.5 8.5 8.7 Sdr interface expanded area ratio 6.6 6.9 5.4 5.5 Thermal Resistance Measurement Results (20 psi Compression) Thermal resistance (℃·in ² /W) 0.019 0.020 0.018 0.019 Thickness when measured (mm) 0.128 0.139 0.139 0.166 Compression rate at the time of measurement (%) 35% 32% 36% 29% Reduction rate of thermal resistance (%) 56% 53% 58% 56%

[表5]       比較例 1 比較例 2 比較例 3 比較例 4 比較例 5 比較例 6 混合組成物之組成 A A A B B B 實施步驟 無 加壓 研磨 無 加壓 研磨 加壓步驟之條件 加壓溫度（℃） - 30 - - 30 - 加壓時之壓縮率（%） - 50 - - 50 - 研磨步驟之條件 20 μm研磨紙研磨* 無 無 有 無 無 有 初級片之厚度 初始厚度（mm） 0.271 0.236 0.192 0.255 0.223 0.210 加壓步驟前後之厚度變化（mm） - 0.035 - - 0.049 - 加壓步驟前後之厚度變化（%） - 15% - - 22% - 研磨步驟前後之厚度變化（mm） - - 0.055 - - 0.045 研磨步驟前後之厚度變化（%） - - 29% - - 21% 總行程中之厚度變化（mm） - 0.035 0.055 - 0.049 0.045 總行程中之厚度變化（%） - 15% 29% - 22% 21% 初級片之配向率 A A A A A A 導熱性片之表面粗糙度 Sa 算術平均高度（μm） 14.8 10.3 12.3 15.8 11.1 10.3 Sdr 界面展開面積比 11.2 11.9 7.3 9.3 15.2 6.4 熱阻測定結果 （20 psi壓縮） 熱阻（℃·in ²/W） 0.055 0.032 0.027 0.043 0.028 0.024 測定時之厚度（mm） 0.177 0.154 0.137 0.138 0.147 0.146 測定時之壓縮率（%） 35% 35% 29% 46% 34% 30% 熱阻之降低率（%） 0% 42% 51% 0% 35% 44% [table 5] Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative Example 5 Comparative example 6 Composition of Mixed Composition A A A B B B Implementation steps none Pressurize grinding none Pressurize grinding Conditions of pressurization step Pressurization temperature (°C) - 30 - - 30 - Compression rate when pressurized (%) - 50 - - 50 - Conditions of grinding step Grinding with 20 μm abrasive paper* none none have none none have The thickness of the primary sheet Initial thickness (mm) 0.271 0.236 0.192 0.255 0.223 0.210 Thickness change before and after pressing step (mm) - 0.035 - - 0.049 - Thickness change before and after pressing step (%) - 15% - - twenty two% - Thickness change before and after grinding steps (mm) - - 0.055 - - 0.045 Thickness change before and after grinding step (%) - - 29% - - twenty one% Thickness change in total stroke (mm) - 0.035 0.055 - 0.049 0.045 Thickness change in total stroke (%) - 15% 29% - twenty two% twenty one% Alignment rate of primary film A A A A A A Surface Roughness of Thermally Conductive Sheet Sa arithmetic mean height (μm) 14.8 10.3 12.3 15.8 11.1 10.3 Sdr interface expanded area ratio 11.2 11.9 7.3 9.3 15.2 6.4 Thermal Resistance Measurement Results (20 psi Compression) Thermal resistance (℃·in ² /W) 0.055 0.032 0.027 0.043 0.028 0.024 Thickness when measured (mm) 0.177 0.154 0.137 0.138 0.147 0.146 Compression rate at the time of measurement (%) 35% 35% 29% 46% 34% 30% Reduction rate of thermal resistance (%) 0% 42% 51% 0% 35% 44%

如實施例1～20所示，得知利用包括加壓步驟及研磨步驟兩者之本發明之製造方法製造出之導熱性片之熱阻值較低。 相對於此，與實施例相比，加壓步驟及研磨步驟均未實施之比較例1及4之導熱性片之熱阻值極高，散熱性差。 又，由比較例2～3、比較例5～6之結果可知，當僅實施加壓步驟及研磨步驟中之任一者時，熱阻值未充分降低。即，可知實施加壓步驟及研磨步驟兩者時，對降低熱阻值較有效。 由實施例6與實施例10之比較以及實施例14與實施例18之比較可知，即使於相同組成、相同加壓條件之情況下，於（C）研磨步驟之後進行（B）加壓步驟時，更易使熱阻值降低。 由實施例5～8與實施例13～16之比較、以及實施例9～12與實施例17～20之比較可知，使用烴系化合物時，更易使熱阻值降低。 As shown in Examples 1 to 20, it was found that the thermal resistance value of the thermally conductive sheet produced by the production method of the present invention including both the pressurizing step and the grinding step was low. On the other hand, compared with the examples, the thermal conductive sheets of Comparative Examples 1 and 4 in which neither the pressurization step nor the grinding step was performed had extremely high thermal resistance and poor heat dissipation. Also, from the results of Comparative Examples 2-3 and Comparative Examples 5-6, it can be seen that when only any one of the pressurization step and the polishing step is performed, the thermal resistance value does not sufficiently decrease. That is, it can be seen that performing both the pressurization step and the grinding step is more effective in reducing the thermal resistance value. From the comparison of Example 6 and Example 10 and the comparison of Example 14 and Example 18, it can be seen that even under the same composition and the same pressurization conditions, when the (B) pressurization step is performed after the (C) grinding step , it is easier to reduce the thermal resistance value. From the comparison between Examples 5-8 and Examples 13-16, and the comparison between Examples 9-12 and Examples 17-20, it can be seen that when hydrocarbon compounds are used, it is easier to reduce the thermal resistance.

10,20:初級片 10A,10B:表面 12:異向性填充材 14:高分子基質 16:非異向性填充材 21:隔熱材料 22:下方之銅製塊 23:上方之銅製塊 24:加熱器 25:散熱片 26:荷重元 S:試驗片 θ _j0:上方之銅製塊之溫度 θ _j1:下方之銅製塊之溫度 10, 20: primary sheet 10A, 10B: surface 12: anisotropic filler 14: polymer matrix 16: non-anisotropic filler 21: heat insulation material 22: copper block below 23: copper block above 24: Heater 25: heat sink 26: load cell S: test piece θ _j0 : temperature of the upper copper block θ _j1 : temperature of the lower copper block

[圖1]係示意性地表示本發明之初級片之一實施方式之剖視圖。 [圖2]係示意性地表示本發明之初級片之另一實施方式之剖視圖。 [圖3]係熱阻測定機之概略圖。 [ Fig. 1 ] is a cross-sectional view schematically showing one embodiment of the primary sheet of the present invention. [ Fig. 2 ] is a cross-sectional view schematically showing another embodiment of the primary sheet of the present invention. [Fig. 3] is a schematic diagram of a thermal resistance measuring machine.

Claims (8)

一種導熱性片之製造方法，其具備： （A）製作初級片之步驟，該初級片含有高分子基質及分散於上述高分子基質之異向性填充材，上述異向性填充材於厚度方向上配向，且上述異向性填充材之端部於表面露出； （B）加壓步驟，其將上述初級片於厚度方向上進行壓縮；及 （C）研磨步驟，其研磨上述初級片之表面。 A method of manufacturing a thermally conductive sheet, comprising: (A) A step of producing a primary sheet comprising a polymer matrix and an anisotropic filler dispersed in the polymer matrix, the anisotropic filler is aligned in the thickness direction, and the anisotropic filler is ends exposed on the surface; (B) a pressing step of compressing the above-mentioned primary sheet in the thickness direction; and (C) A grinding step of grinding the surface of the above-mentioned primary sheet. 如請求項1之導熱性片之製造方法，其中，上述加壓步驟中之初級片之厚度變化為3%以上。The method of manufacturing a thermally conductive sheet according to Claim 1, wherein the thickness variation of the primary sheet in the pressing step is 3% or more. 如請求項1或2之導熱性片之製造方法，其中，上述異向性填充材含有碳纖維。The method of manufacturing a thermally conductive sheet according to claim 1 or 2, wherein the anisotropic filler contains carbon fibers. 如請求項1至3中任一項之導熱性片之製造方法，其中，上述異向性填充材含有碳纖維及鱗片狀碳粉末。The method for producing a thermally conductive sheet according to any one of claims 1 to 3, wherein the anisotropic filler contains carbon fibers and flaky carbon powder. 如請求項1至4中任一項之導熱性片之製造方法，其中，上述高分子基質包含有機聚矽氧烷。The method for producing a thermally conductive sheet according to any one of claims 1 to 4, wherein the polymer matrix includes organopolysiloxane. 如請求項1至5中任一項之導熱性片之製造方法，其中，上述高分子基質包含有機聚矽氧烷及烴系化合物。The method for producing a thermally conductive sheet according to any one of claims 1 to 5, wherein the polymer matrix includes organopolysiloxane and a hydrocarbon compound. 如請求項1至6中任一項之導熱性片之製造方法，其中，於（C）研磨步驟之前進行上述（B）加壓步驟。The method for manufacturing a thermally conductive sheet according to any one of Claims 1 to 6, wherein the (B) pressurizing step is performed before the (C) grinding step. 如請求項1至6中任一項之導熱性片之製造方法，其中，於（C）研磨步驟之後進行上述（B）加壓步驟，上述（B）加壓步驟係使初級片之表面粗糙化之步驟。The method for manufacturing a thermally conductive sheet according to any one of claims 1 to 6, wherein the (B) pressing step is performed after the (C) grinding step, and the (B) pressing step is to roughen the surface of the primary sheet The steps of transformation.

Images