200837108 九、發明說明 【發明所屬之技術領域】 本發明係關於散熱材料。 【先前技術】 近來’於電子機器領域中，抑制該電子機器溫度上升 之冷卻（散熱）技術逐漸重要。尤其，個人用電腦（PC)中， 即使該容積有減少之趨勢，仍隨著CPU(電腦中央處理器） 之動作頻率增加，發熱量急速持續上升，關於CPU以外 之零件亦有發熱量增加趨勢。 另外，除了此等以外，因爲亦要求靜音化、減低消耗 電力，所以尋求盡可能不依賴風扇空冷之散熱系統。 因爲冷卻技術中「達成經濟之冷卻效果」係最重要的項 目，所以以低成本可達成效率佳之冷卻，進行各種檢討。 作爲散熱材料所要求之特性，可舉例如熱傳導性佳、 價廉、耐久性、耐熱性及耐候性優異、可製作成所需形 狀、輕量、及小型等。作爲傳統之散熱材料，雖提出熱傳 導率高之鋁或銅爲材料之散熱片（Heat sink)(例如參考特 開平〇5 — 074992號公報），使用此等鋁或銅時並不能滿足 輕量化之必要條件。另外，如鋁或銅之金屬材料，因爲於 表面具有光澤，所以亦有放射率低，難以得到因熱輻射之 散熱效果之缺點。爲解決此缺點’例如雖檢討於金屬材料 的表面，施以黑色被覆或將金屬材料表面氧化處理等之後 處理（例如參考特開2005 - 1 5 3 296號公報及特開2000 — 200837108 282292號公報），但處理步驟增加而成爲低成本化之障 礙。 【發明內容】 本發明之目的係提供輕量，具有高放射率，散熱特性 優異之散熱材料。 本發明係關於（1 )含有高熱傳導性材料及樹脂之散熱 材料，於散熱材料中含有50〜95質量％之高熱傳導性材 料爲特徵之散熱材料。 另外’本發明係關於（2)上述高熱傳導性材料係含石 墨爲特徵之上述（1)記載之散熱材料。 另外’本發明係關於（3)上述散熱材料之容積密度爲 1·2〜2.2g/cm3爲特徵之上述（1)或（2)記載之散熱材料。 另外’本發明係關於（4)上述散熱材料於6 0 °C時放射 面之放射率爲〇 · 4 〇以上爲特徵之上述至（3 )中任一項記 載之散熱材料。 另外’本發明係關於（5)上述散熱材料之厚度方向之 熱傳導率爲1〇W/mK以上爲特徵之上述（1)至（4)中任一項 記載之散熱材料。 另外，本發明係關於（6)上述散熱材料之面方向之熱 傳導率爲3〇W/mK以上爲特徵之上述（1)至（5)中任一項記 載之散熱材料。 另外，本發明係關於（7)上述散熱材料係具有散熱片 結構爲特徵之上述⑴至（6)中任—項記載之散熱材料。 200837108 Λ外，本發明係關於（8 )上述散熱片之高度係散熱材 料整體高度之30〜95%爲特徵之上述（7)記載之散熱材 料。 、 另外，本發明係關於（9)上述散熱片之溝部係圓錐 • 狀，圓錐角度爲1〜30。爲特徵之上述（7)或（8)記載之散 熱材料。 另外’本發明係關於（丨0)上述散熱材料整體高度係 • 1mm以上爲特徵之上述（1)至（9)中任—項記載之散熱材 料。 另外’本發明係關於（11)上述散熟材料之比熱係 〇.85J/gK以下爲特徵之上述⑴至（1〇)中任—項記載之散熱 材料。 另外，本發明係關於（12)上述散熱材料面方向之熱膨 脹率係8xl0-6/t：以下爲特徵之上述（1)至（11)中任一項記 載之散熱材料。 • 另外，本發明係關於（13)上述散熱材料之體積固有電 阻係200μΩιη以下爲特徵之上述（1)至（12)中任一項記載 、 之散熱材料。 力外本發明係關於（14)上述散熱材料係ul_ 94規 格，具有V-0之難燃性爲特徵之上述（1)至（13)中任一項 記載之散熱材料。 另外，本發明係關於（15)上述散熱材料散熱面之相反 面具有黏著層爲特徵之上述（1)至（14)中任一項記載之散熱 材料。 200837108 另外，本發明係關於（16)上述黏著層之厚度爲15〇μπ] 以下爲特徵之上述（15)記載之散熱材料。 另外’本發明係關於（17)上述黏著層之熱傳導率爲 0.5W/mK以上爲特徵之上述（15)或（16)記載之散熱材料。 用以實施發明之最佳型態 本發明之散熱材料係含有高熱傳導性材料及樹脂，於 散熱材料中含有50〜95質量％之高熱傳導性材料爲特 徵。上述散熱材料中之高熱傳導性材料之含量係以6〇〜 9 5質量％爲宜，以7 0〜9 5質量％尤佳。上述高熱傳導性 材料之含量未滿5 0質量％時，散熱材料之傳熱特性降 低’不能得到充分的散熱特性。另一方面，上述高熱傳導 性材料之含量超過9 5質量％時，散熱材料之成形性降 低，不能得到所需形狀之散熱材料。 本發明中所使用之高熱傳導性材料並無特別的限制， 作爲散熱材料之熱傳導性塡料係已知物亦可，但熱傳導率 爲10〜100 OW/mK者爲宜。作爲高熱傳導性材料之一例， 可舉例如二氧化矽、石墨、氧化鋁、氫氧化鋁、氮化鋁、 碳化矽、氫氧化鎂等之無機塡料、鋁、銅、銀、金等之金 屬塡料等。此等高熱傳導性材料係可使用1種，亦可組合 2種以上使用。 上述高熱傳導性材料例中，就輕量化及散熱特性上， 以石墨爲宜。作爲石墨，例如使用天然石墨粉末、人造石 墨粉末、將膨脹石墨或膨脹石墨薄片粉碎之膨脹石墨粉末 -8 - 200837108 寺。此寺中係以天然或人造石墨粉末爲宜。此等石墨之形 狀係球狀、塊狀、鱗片、樹枝狀等，雖無特別限制，但平 均粒徑係以5〜50Ομιη爲宜。此等石墨之平均粒徑係可使 用電射繞射式粒度分佈測定裝置而測定。另外，平均粒徑 爲5 0%D之値。 本發明中，藉由混合上述高熱傳導性材料之粉末與樹 脂，可得到輕量，散熱特性優異之散熱材料。另外，石墨 或金屬塡料等之高熱導電性材料係藉由與樹脂混合，將可 防止因粒子脫離而電子機器內部發生短路。 本發明中所使用之樹脂係以熱可塑性樹脂或熱硬化性 樹脂爲宜。作爲熱可塑性樹脂，可舉例如聚乙烯、聚丙 烯、聚甲基戊烯、聚丁烯、結晶性聚丁二烯、聚苯乙烯、 聚丁二烯、苯乙烯丁二烯樹脂、聚氯化乙烯、聚乙酸乙 烯、偏氯乙烯、乙烯.乙酸乙烯共聚物（EVA)、丙烯腈·苯 乙烯共聚物（AS)、丙烯腈·丁二烯·苯乙烯共聚物（ABS)、 離子鍵聚合物、丙烯腈·丙烯酸橡膠·苯乙烯共聚物 (A AS)、氯化聚乙烯·丙烯腈♦苯乙烯共聚物（ACS)、聚甲基 甲基丙烯酸酯、聚甲基丙烯酸酯、聚四氟乙烯、乙烯.聚 四氟乙烯共聚物、聚縮醛（聚甲醛）、聚醯胺、聚碳酸酯、 聚伸苯基醚（polyphenyleneether)、聚對苯二甲酸乙二醇 酯、聚對苯一甲酸丁 一醇酯、聚丙燦酸酯（U聚合物（註冊 商標））、聚苯乙烯、聚醚礪、聚醯亞胺、聚醯胺醯亞胺、 聚伸苯基硫（Polyphenylenesulfide)、聚氧苯甲醯、聚醚醚 酮、聚醚醯亞胺、其他液晶聚酯等。 -9- 200837108 另外，作爲熱硬化性樹脂，可舉例如酚醛樹脂、含有 由開環聚合而聚合之二氫苯幷噁嗪環之熱硬化性樹脂、胺 基樹脂（脲醛樹脂、三聚氰胺樹脂、苯幷胍胺樹脂 (benzoguanamine resin))、不飽和聚酯樹脂、鄰苯二甲酸 二烯丙基酯、醇酸樹脂、環氧樹脂、聚胺基甲酸乙酯樹 脂、矽氧樹脂等。 此等樹脂中，就耐熱性、成形性、與金屬模具之離型 性上，適用酚醛樹脂、含有由開環聚合而聚合之二氫苯幷 噁嗪環之熱硬化性樹脂、環氧樹脂。另外，此等樹脂係可 單獨使用，亦可倂用2種以上。 另外，所謂「含有由開環聚合而聚合之二氫苯幷噁嗪 環之熱硬化性樹脂」係指由具有酚性羥基之化合物、甲醛 類及1級胺所合成之樹脂。此樹脂係由加熱引起開環聚合 反應，形成具有不使揮發份發生之優異特性之交聯結構。 含有下述一般式（I )所示之結構部位（亦即’二氫苯 幷噁嗪環）之樹脂，尤其耐熱性優異，由加成反應而進行 硬化，不發生揮發性產物，因爲形成均勻緻密之樹脂層， 所以爲適合之樹脂。 [化1]200837108 IX. Description of the Invention [Technical Field of the Invention] The present invention relates to a heat dissipating material. [Prior Art] Recently, in the field of electronic equipment, cooling (heat dissipation) technology for suppressing the temperature rise of the electronic machine has become increasingly important. In particular, in a personal computer (PC), even if the volume is reduced, the frequency of the CPU (computer central processing unit) increases, and the amount of heat generation continues to rise rapidly. . In addition, in addition to these, since it is also required to be quiet and to reduce power consumption, a heat dissipation system that does not rely on fan air cooling as much as possible is sought. Since the "cooling effect of the economy" is the most important item in the cooling technology, it is possible to achieve efficient cooling at a low cost and carry out various reviews. The properties required for the heat dissipating material are, for example, excellent in thermal conductivity, low in cost, excellent in durability, heat resistance, and weather resistance, and can be produced into a desired shape, light weight, and small size. As a conventional heat-dissipating material, a heat sink having a high thermal conductivity of aluminum or copper is proposed (for example, Japanese Laid-Open Patent Publication No. Hei-5-074992), and the use of such aluminum or copper does not satisfy the weight reduction. Necessary conditions. Further, a metal material such as aluminum or copper has a low emissivity because of its luster on the surface, and it is difficult to obtain a heat dissipation effect due to heat radiation. In order to solve this disadvantage, for example, it is reviewed on the surface of a metal material, and the black coating is applied or the surface of the metal material is oxidized or the like (for example, refer to Japanese Laid-Open Patent Publication No. Hei. No. 2005-155-296 and No. 2000-200837108 282292 ), but the processing steps have increased and become an obstacle to cost reduction. SUMMARY OF THE INVENTION An object of the present invention is to provide a heat dissipating material which is lightweight, has high emissivity, and is excellent in heat dissipation characteristics. The present invention relates to (1) a heat dissipating material containing a high heat conductive material and a resin, and a heat dissipating material characterized by a high heat conductive material of 50 to 95% by mass in the heat dissipating material. Further, the present invention relates to the heat dissipating material of the above (1), characterized in that the high thermal conductive material is a graphite-containing ink. Further, the present invention relates to the heat dissipating material according to the above (1) or (2), characterized in that the heat dissipating material has a bulk density of 1-2 to 2.2 g/cm3. Further, the present invention relates to a heat dissipating material recorded in any one of the above-mentioned items (3) characterized in that the heat dissipating material has a radiation emissivity of 60 C or more at 60 °C. Further, the present invention relates to the heat dissipating material according to any one of the above (1) to (4), wherein the thermal conductivity of the heat dissipating material in the thickness direction is 1 〇 W/mK or more. Further, the present invention relates to the heat dissipating material described in any one of the above (1) to (5), characterized in that the thermal conductivity of the heat dissipating material in the plane direction is 3 〇 W/mK or more. Further, the present invention relates to the heat dissipating material according to any one of the above (1) to (6), wherein the heat dissipating material is characterized by a fin structure. The present invention relates to the heat dissipating material described in the above (7), characterized in that (8) the heat sink is characterized by a height of 30 to 95% of the overall height of the heat dissipating material. Further, the present invention relates to (9) that the groove portion of the fin is a conical shape, and the taper angle is 1 to 30. The heat-dissipating material described in the above (7) or (8). Further, the present invention relates to a heat dissipating material according to any one of the above (1) to (9), characterized in that the entire heat dissipating material has a height of 1 mm or more. Further, the present invention relates to the heat dissipating material according to any one of the above (1) to (1), characterized in that the specific heat of the above-mentioned bulk material is 85.85J/gK or less. Further, the present invention relates to (12) a heat dissipating material recorded in any one of the above (1) to (11), characterized in that the thermal expansion coefficient in the surface direction of the heat dissipating material is 8x10-6/t. Further, the present invention relates to the heat dissipating material according to any one of the above (1) to (12), wherein the heat dissipation material has a volume specific resistance of 200 μΩ or less. The present invention relates to the heat dissipating material according to any one of the above (1) to (13), wherein the heat dissipating material is ul_94, and has a V-0 flame retardancy. Further, the present invention relates to the heat dissipating material according to any one of the above (1) to (14), wherein the heat dissipating surface of the heat dissipating material has an adhesive layer. Further, the present invention relates to the heat dissipating material according to the above (15), characterized in that the thickness of the adhesive layer is 15 〇μπ] or less. Further, the present invention relates to the heat dissipating material according to the above (15) or (16), characterized in that the thermal conductivity of the adhesive layer is 0.5 W/mK or more. BEST MODE FOR CARRYING OUT THE INVENTION The heat dissipating material of the present invention contains a highly thermally conductive material and a resin, and contains 50 to 95% by mass of a highly thermally conductive material in the heat dissipating material. The content of the high heat conductive material in the heat dissipating material is preferably 6 〇 to 9.5 mass%, more preferably 70 to 9.5 mass%. When the content of the above highly thermally conductive material is less than 50% by mass, the heat transfer characteristics of the heat dissipating material are lowered, and sufficient heat dissipation characteristics cannot be obtained. On the other hand, when the content of the above high thermal conductive material exceeds 95% by mass, the formability of the heat dissipating material is lowered, and a heat dissipating material having a desired shape cannot be obtained. The high thermal conductivity material used in the present invention is not particularly limited, and a heat conductive material as a heat dissipating material may be known, but a thermal conductivity of 10 to 100 OW/mK is preferred. Examples of the highly thermally conductive material include inorganic materials such as cerium oxide, graphite, aluminum oxide, aluminum hydroxide, aluminum nitride, cerium carbide, magnesium hydroxide, and metals such as aluminum, copper, silver, and gold. Dumping, etc. These high thermal conductivity materials may be used alone or in combination of two or more. In the above examples of the high thermal conductivity material, graphite is preferred in terms of weight reduction and heat dissipation characteristics. As the graphite, for example, natural graphite powder, artificial graphite powder, expanded graphite powder pulverized with expanded graphite or expanded graphite flakes -8 - 200837108 Temple. Natural or artificial graphite powder is preferred in this temple. The shape of the graphite is spherical, massive, scale, dendritic, etc., and is not particularly limited, but the average particle diameter is preferably 5 to 50 μm. The average particle diameter of these graphites can be measured by an electric radiation diffraction type particle size distribution measuring apparatus. Further, the average particle diameter is 50% D. In the present invention, by mixing the powder and the resin of the above highly thermally conductive material, a heat-dissipating material which is lightweight and excellent in heat dissipation characteristics can be obtained. Further, the highly thermally conductive material such as graphite or metal tantalum is mixed with the resin to prevent short-circuiting inside the electronic device due to particle detachment. The resin used in the present invention is preferably a thermoplastic resin or a thermosetting resin. Examples of the thermoplastic resin include polyethylene, polypropylene, polymethylpentene, polybutene, crystalline polybutadiene, polystyrene, polybutadiene, styrene butadiene resin, and polychlorination. Ethylene, polyvinyl acetate, vinylidene chloride, ethylene, vinyl acetate copolymer (EVA), acrylonitrile styrene copolymer (AS), acrylonitrile butadiene styrene copolymer (ABS), ionomer , acrylonitrile, acrylic rubber, styrene copolymer (A AS), chlorinated polyethylene, acrylonitrile, styrene copolymer (ACS), polymethyl methacrylate, polymethacrylate, polytetrafluoroethylene , ethylene, polytetrafluoroethylene copolymer, polyacetal (polyoxymethylene), polyamine, polycarbonate, polyphenyleneether, polyethylene terephthalate, polyparaphenylene Butanol ester, polyacrylic acid ester (U polymer (registered trademark)), polystyrene, polyether oxime, polyimide, polyamidoximine, polyphenylenesulfide, polyoxygen Benzoquinone, polyetheretherketone, polyetherimide, other liquid crystal polyesters, and the like. -9-200837108 In addition, examples of the thermosetting resin include a phenol resin, a thermosetting resin containing a dihydrophenyloxazin ring polymerized by ring-opening polymerization, and an amine resin (urea resin, melamine resin, and benzene). A benzoguanamine resin, an unsaturated polyester resin, a diallyl phthalate, an alkyd resin, an epoxy resin, a polyurethane resin, a silicone resin, or the like. Among these resins, a phenol resin, a thermosetting resin containing a dihydrobenzoxazine ring polymerized by ring-opening polymerization, and an epoxy resin are used in terms of heat resistance, moldability, and mold release property. Further, these resins may be used singly or in combination of two or more. In addition, the "thermosetting resin containing a dihydrophenylhydrazine ring polymerized by ring-opening polymerization" means a resin synthesized from a compound having a phenolic hydroxyl group, a formaldehyde, and a primary amine. This resin is subjected to a ring-opening polymerization reaction by heating to form a crosslinked structure having excellent characteristics which do not cause volatiles. A resin containing a structural moiety represented by the following general formula (I) (that is, a 'dihydrophenylhydrazine ring) is excellent in heat resistance, hardened by an addition reaction, and does not generate volatile products because uniform formation occurs. A dense resin layer, so it is a suitable resin. [Chemical 1]
-10- 200837108 作爲含二氫苯幷噁嗪環之熱硬化性樹脂係含有如下述 一般式（A)及一般式（B) [化2]-10- 200837108 The thermosetting resin containing a dihydrophenyl hydrazine ring contains the following general formula (A) and general formula (B) [Chemical 2]
OH (式中’鍵結於芳香環基之氫係除了一個羥基鄰位以 外’亦可爲取代基取代） [化3]OH (wherein the hydrogen bond bonded to the aromatic ring group may be substituted by a substituent other than a hydroxyl group) may also be substituted by a substituent)
(式中，R1係烴基，鍵結於芳香環基之氫亦可爲取代 基取代） 所示之化學結構單位者，抑制揮發性氣體之效果高， 所以適宜，就耐熱性等上，含有一般式（A)/—般式（B)之 旲耳比爲4/1〜1/9者爲宜。藉由使用材料之比率等而可 將其調整。 另外，於上述一般式（A)及一般式（B)中所示之化學結 -11 - 200837108 構單位中，關於取代基並無特別的限制，可舉例如甲基、 乙基等之烷基等爲宜。另外，一般式（A)中，因爲一個經 基鄰位係進行硬化反應，所以以具有氫爲宜。上述各化學 結構單位之數係1分子中所含一般式（A)之數爲m ’ 一般 式（B)之數爲η時，以m^l、ngl且m + ng 2即可’就硬 f 化物之特性，例如耐熱性等上，數平均係以1 〇 - m + n g 3 爲宜。 φ 上述各化學結構單位係可互相直接鍵結，亦可藉由有 機基鍵結。作爲上述有機基，可舉例如烯烴基、苯二甲基 等爲宜，作爲烯烴基，可舉例如 [化4] —CH2— R2 • 所示之基（但是，R2係表示氫原子、甲基、乙基、丙 基、異丙基、苯基或取代苯基）、碳數爲5〜20個之鏈狀 ' 烷基等。此係可選自作爲原料使用之具有酚性羥基之化合 - 物之種類等。 作爲含二氫苯幷噁嗪環之熱硬化性樹脂之原料之上述 具有酚性羥基之化合物，可舉例如酚醛漆用酚醛樹脂、甲 階酚醛樹脂（resol resin)、苯酚變性二甲苯樹脂、烷基酚 醛樹脂、三聚氰胺酚醛樹脂、聚丁二烯變性酚醛樹脂等之 酚醛樹脂、雙酚化合物（bisphenol)、二酚化合物、三酚化 -12- 200837108 合物、四酚化合物等。 作爲含二氫苯幷噁嗪環之熱硬化性樹脂之原料之甲醛 類’除了甲醛以外，可使用如仲甲醛、六伸甲基四胺之發 生甲醛者等。 作爲含二氫苯幷噁嗪環之熱硬化性樹脂之原料之一級 胺，具體上可舉例如甲胺、乙胺、丙胺、環己胺等之脂肪 族胺、苯胺、取代苯胺等之芳香族胺。就硬化性上，以脂 肪族胺爲宜，就耐熱性上，以芳香族胺爲宜。 各材料係以相對於1莫耳之具有酚性羥基之化合物之 0.2〜0.9莫耳之1級胺、1級胺之2倍莫耳量以上之甲醛 之比，使具有酚性羥基之化合物、甲醛類及1級胺反應， 就所得樹脂之黏著性等方面上係適宜的。 本發明之散熱材料係除了高熱傳導性材料及樹脂之 外，亦可含有樹脂硬化物、硬化促進劑、內部離型劑、滑 劑等之成份。 本發明中，作爲使用上述各材料，製作含二氫苯幷噁 嗪環之熱硬化性樹脂之方法係將具有酚性羥基之化合物及 1級胺之混合物，添加於加熱7 0 °C以上之甲醛類中爲宜， 以70〜1 10°C爲宜，以90〜100°C尤佳，以20〜120分鐘 反應爲宜，之後，以120°C以下之適合溫度，藉由減壓乾 燥而可合成。 含二氫苯幷噁嗪環之熱硬化性樹脂係可取自日立化成 工業（股）製之加成反應型熱硬化樹脂，商品名「HR 1060」。 本發明所使用之酚醛樹脂雖無特別的限定’以使用例 -13- 200837108 如下述一般式（n )所示之甲階酚醛系酚醛樹脂爲 [化5] (II) _ (式ϋ中，a係i以上之整數。） 本1胃明中，就與高熱傳導性材料之混合性上 脂係以粉末狀爲宜，粒徑係以 2〇〇μηι以下 ΙΟΟμηι以下更好。散熱材料係以容積密度 2.2g/cm3 爲宜，以 ι·5 〜2.2g/cm3 尤佳，以 1.7, 更好。容積密度未滿l.2g/cm3時，散熱材料之 爲隔熱層作用之空氣，熱傳導率降低而有散熱材 特性降低之趨勢。另一方面，容積密度超過 # 時’有不能得到輕量散熱材料之趨勢。容積密度 材料之質量除以體積而可測定。 ^ 使本發明之散熱材料之容積密度爲1.2〜2 ， 將充分地混練之材料，以充分的壓力、溫度熱 可。 本發明之散熱材料於6 0 °C時散熱面之放 0 · 4 0以上爲宜，以0.6 0以上尤佳，以〇 · 8 〇以上 射率未滿0·40時，有難以得到因熱輻射之散熱 勢。因放射率之理論的上限値係1 · 〇，本發明之 宜。(In the formula, the R1 hydrocarbon group and the hydrogen bonded to the aromatic ring group may be substituted by a substituent.) The chemical structural unit shown has a high effect of suppressing a volatile gas, and therefore is suitable for heat resistance and the like. The formula (A) / - general formula (B) is preferably in the range of 4/1 to 1/9. It can be adjusted by using the ratio of the materials and the like. Further, in the chemical unit of the above-mentioned general formula (A) and the general formula (B), the substituent is not particularly limited, and examples thereof include an alkyl group such as a methyl group or an ethyl group. It is appropriate. Further, in the general formula (A), since one of the ortho-groups undergoes a hardening reaction, it is preferred to have hydrogen. The number of the above-mentioned chemical structural units is one in which the number of the general formula (A) is m '. When the number of the general formula (B) is η, m^l, ngl, and m + ng 2 can be hard. The characteristics of the compound, such as heat resistance, are preferably 1 〇- m + ng 3 . φ Each of the above chemical structural units may be directly bonded to each other or may be bonded by an organic group. The above-mentioned organic group is preferably an olefin group or a benzene dimethyl group. The olefin group may, for example, be a group represented by [Chem. 4]-CH2-R2. (However, R2 represents a hydrogen atom or a methyl group. , an ethyl group, a propyl group, an isopropyl group, a phenyl group or a substituted phenyl group), a chain-like alkyl group having a carbon number of 5 to 20 or the like. This type may be selected from the group of compounds having a phenolic hydroxyl group used as a raw material, and the like. Examples of the compound having a phenolic hydroxyl group as a raw material of a thermosetting resin containing a dihydrophenyloxazin ring include a phenol resin for a phenolic lacquer, a resol resin, a phenol denatured xylene resin, and an alkane. A phenol resin such as a phenol resin, a melamine phenol resin, a polybutadiene-modified phenol resin, a bisphenol compound, a diphenol compound, a trisylated -12-200837108 compound, a tetraphenol compound or the like. As the formaldehyde of the raw material of the thermosetting resin containing a dihydro benzoxazine ring, in addition to formaldehyde, a formaldehyde such as paraformaldehyde or hexamethylenetetramine can be used. The monoamine which is a raw material of the thermosetting resin containing a dihydro benzoxazine ring may, for example, be an aromatic amine such as methylamine, ethylamine, propylamine or cyclohexylamine, or an aromatic such as aniline or substituted aniline. amine. In terms of hardenability, an aliphatic amine is preferred, and in terms of heat resistance, an aromatic amine is preferred. Each of the materials is a compound having a phenolic hydroxyl group, in a ratio of 0.2 to 0.9 moles of a first amine of a compound having a phenolic hydroxyl group to a formaldehyde of 2 times the molar amount or more of a primary amine. The reaction of formaldehyde and primary amine is suitable in terms of adhesion of the obtained resin. The heat dissipating material of the present invention may contain, in addition to the highly thermally conductive material and the resin, a resin cured product, a hardening accelerator, an internal release agent, a lubricant, and the like. In the present invention, as a method of producing a thermosetting resin containing a dihydrophenyloxazin ring by using each of the above materials, a mixture of a compound having a phenolic hydroxyl group and a primary amine is added to a heating of 70 ° C or higher. It is preferably used in the form of formaldehyde, preferably 70 to 1 10 ° C, preferably 90 to 100 ° C, preferably 20 to 120 minutes, and then dried at a suitable temperature of 120 ° C or less. And can be synthesized. The thermosetting resin containing a dihydro benzoxazine ring can be obtained from an addition reaction type thermosetting resin manufactured by Hitachi Chemical Co., Ltd., trade name "HR 1060". The phenol resin used in the present invention is not particularly limited. In the use example-13-200837108, a resol phenolic phenol resin represented by the following general formula (n) is [Chemical Formula 5] (II) _ a is an integer of i or more.) In the present invention, the mixed fat with the high heat conductive material is preferably a powder, and the particle size is preferably 2 〇〇μηι or less ΙΟΟμηι or less. The heat dissipating material is preferably a bulk density of 2.2 g/cm3, more preferably ι·5 to 2.2 g/cm3, and more preferably 1.7. When the bulk density is less than 1.2 g/cm3, the heat-dissipating material acts as the air of the heat-insulating layer, and the thermal conductivity is lowered and the heat-dissipating material characteristics are lowered. On the other hand, when the bulk density exceeds #, there is a tendency that a lightweight heat-dissipating material cannot be obtained. Bulk Density The mass of a material divided by the volume can be determined. ^ The heat dissipating material of the present invention has a bulk density of 1.2 to 2, and the material to be sufficiently kneaded can be heated at a sufficient pressure and temperature. The heat dissipating material of the present invention is preferably placed at a temperature of 60 ° C at a temperature of 60 ° C or more, preferably 0.60 or more, and when the radiance of 〇 · 8 〇 or more is less than 0·40, it is difficult to obtain heat. Radiation heat dissipation. The upper limit of the theory of emissivity is 1 · 〇, and the present invention is suitable.
.，上述樹 爲宜’以 爲 1.2〜 -2.2g/cm3 內部含作 ‘料之散熱 2 · 2 g/cm3 :係將散熱 .2 g/cm3， 壓成形即 射率係以 .更好。放 |效果之趨 上限亦未 -14- 200837108 滿 1.0。 散熱材料於6 0 °C時散熱面之放射率係可以例如稱爲 FT — IR法之方法測定。此方法係由ft — IR(傅立葉轉換紅 外線分光光度計）測定黑體爐（任意相異2點之溫度）及測 定試樣（散熱材料）之放射面之分光放射強度，由此等之分 光放射強度與黑體爐之分光放射強度理論値，求出測定試 樣之分光放射率，由此算出積分放射率者，於本發明中稱 此積分放射率爲放射率。另外，因爲放射率係依測定試樣 之溫度（溫度依賴性係依材料而顯示不同行爲），本發明中 使用於60°C之値。 使本發明之散熱材料於6 0 °C時散熱面之放射率爲 〇. 4 0以上係使用粗糙金屬模具成形散熱材料、或使用噴砂 機（Blasting Machine)等，使散熱材料表面粗糙即可。 本發明之散熱材料之厚度方向之熱傳導率係以 10W/mK以上爲宜，以20W/mK以上尤佳，以30W/mK以 上更好。厚度方向之熱傳導率未滿1 OW/mK時，有不能利 用來自散熱面（具有散熱片結構時爲具有散熱片的面）之熱 輻射散發來自熱源的熱之趨勢。另外，本發明之散熱材料 之面方向之熱傳導率係以30W/mK以上爲宜，以50W/mK 以上尤佳，以1〇〇W/mK以上更好。爲得到高散熱特性， 雖然熱傳導率愈高愈好，但上限爲200W/mK，爲得到超 過200W/mK之熱傳導率，因爲必須極端減少樹脂含量， 成形將變得困難。 厚度方向之熱傳導率係藉由例如雷射閃光、氙氣閃光 -15- 200837108 等之半時間法，測定熱擴散率，由雷射閃光、氙氣閃光等 求出之比熱及容積密度的積算出。另外，由溫度傾斜法亦 可直接算出厚度方向之熱傳導率。由半時間法測定係可使 用例如真空理工股份有限公司製之熱定數測定裝置TC -3000型、TC— 7000型、或NETZSCH公司製之 NanoflashLFA447 等。 另外，面方向之熱傳導率係由稱爲層積（lamellar)法 之將試樣細切重疊，製作成面，垂直照射雷射閃光、氣氣 閃光於此面，依據半時間法，與厚度方向之熱傳導率同樣 地操作而算出之方法或將試樣細切重疊，製作成面，對此 面賦予垂直溫度差，由溫度傾斜法而可測定。 使本發明之散熱材料之厚度方向之熱傳導率爲 10W/mK以上係將散熱材料中含有質量比爲50%以上之高 熱傳導性材料之材料，充分混練，以充分的壓力、溫度熱 壓成形即可。使面方向之熱傳導率爲3 0 W/mK以上係與厚 度方向同樣地將散熱材料中含有質量比爲5 0%以上之高熱 傳導性材料之材料’充分混練，以充分的壓力、溫度熱壓 成形即可。 本發明之散熱材料係以比熱爲〇.85j/gK以下爲宜， 以G.80J/gK以下尤佳’以〇.75J/gK以下更好。比熱爲 0.85J/gK以下時’與傳統作爲散熱材料所使用之比熱爲 0.8 8 J/gK之使用銘之散熱材料比較，溫度反應性優異。 使本發明之散熱材料之比熱爲0 8 5J/gK以下係將散 熱材料中含有質量比爲50%以上之高熱傳導性材料之材 -16- 200837108 料，充分混練，以充分的壓力、溫度熱壓成形即可。 本發明之散熱材料之面方向之熱膨脹率係以8χ1(Γ67 t以下爲宜，以7乂10_6/艺以下尤佳，以6xl0-0/t：以下更 . 好。上述熱膨脹率爲8x1 (T6/°C以下時，與傳統作爲散熱 材料所使用之熱膨脹率爲25 xlO·6/°C之使用鋁之散熱材料 比較’加熱時尺寸變化少，不易發生因熱衝擊之破損。 使本發明之散熱材料面方向之熱膨脹率爲8x1 (T6/t： φ 以下係將散熱材料中含有質量比爲50%以上之高熱傳導性 材料之材料，充分混練，以充分的壓力、溫度熱壓成形即 可〇 本發明之散熱材料之體積固有電阻係以200μΩ m以 下爲宜，以150μΩιη以下尤佳，以1〇〇μΩιη以下更好。 上述散熱材料之體積固有電阻若爲200μΩιη以下時，藉 由散熱材料而可接地。 使本發明之散熱材料之體積固有電阻爲200μ Ω m以 • 下係將散熱材料中含有質量比爲50%以上之高熱傳導性材 料之材料，充分混練，以充分的壓力、溫度熱壓成形即 • 可。 ， 本發明之散熱材料係以UL — 94規格，具有V— 0之 難燃性爲宜。本發明品因可作爲電子零件使用，所以於安 全上必須具有難燃性。 本發明之散熱材料爲得到V 一 〇之難燃性係將散熱材 料中含有質量比爲50%以上之高熱傳導性材料之材料，充 分混練’以充分的壓力、溫度熱壓成形即可。 -17- 200837108 爲提高散熱性’本發明之散熱材料係以散熱面側具有 散熱片結構爲宜。在此’散熱片形狀係只要表面積增加而 容易擴散熱之形狀者即可，並無特別的限定，可舉例如細 長狀或圓筒狀等之梳型、圚錐狀等之針型等。散熱片數 量、方向、間隔、配置等係因應用途或適用對象等而適當 設定。 上述散熱片之高度係以散熱材料整體高度之30〜95% 爲宜，以40〜95%尤佳，以50〜95%更好。散熱片高度未 滿散熱材料整體高度之3 0%時，有散熱特性降低之趨勢。 另一方面，散熱片高度超過散熱材料整體高度之95%時， 有散熱片難以成形之趨勢，有散熱材料強度降低之趨勢。 上述散熱片係爲提升散熱效率，散熱片的厚度係由散 熱片的先端部份朝向根部漸增’溝部成圓錐爲宜。圓錐角 度爲1〜30。爲宜，以1〜20。尤佳，以1〜1〇。更好。 上述圓錐角度未滿1°時，有難以自金屬模具離型之趨 勢。另一方面，上述圓錐角度超過30。時，因爲散熱片 根部寬度增大，散熱片間之間距不能變細，所以因散熱面 積減少而有散熱特性降低之趨勢。圓錐形狀之散熱材料例 係如圖1所示。 使本發明之散熱材料之結構如上述所需形狀係由選擇 成形散熱材料時之金屬模具所進行。本發明之散熱材料整 體局度係依用途、搭載部份而異，但使用於電腦、電漿電 視等之電子機器時，就熱容量及散熱材料之面方向傳熱 上’以1mm以上爲宜，以2mm以上尤佳，以3mm以上 -18- 200837108 更好。上述散熱材料整體高度未滿lmm時，熱容量及散 熱材料之面方向傳熱降低，有不能得到有效散熱之趨勢。 另一方面’上述散熱材料整體高度之上限爲i5〇mm程 度’超過此時，將可能難以成形。 關於本發明之散熱材料之製造方法並無特別的限制， 例如將局熱傳導性材料與樹脂之混合物，以捏和機、擂潰 機、漢塞混合機（Henschel Mixer)、行星式攪拌機、輥碾 機等，經由攪拌、混合、混練、壓延等之步驟，將所得之 混合物，例如以射出成形、擠壓成形、加壓成形等之已知 塑膠成形方法，成形成所需形狀而可製作。 爲提局與熱源之黏著性，本發明之散熱材料係以於該 散熱面之相反面具有黏著層爲宜。作爲黏著層之材料係只 要可黏著本發明之散熱材料與CPU等之熱源者即可，並 無特別的限制，例如可使用丙烯酸系黏著材料、橡膠系黏 著材料，聚矽氧烷系黏著材料等之黏著材料，使用於支持 體之兩面具有黏著材料之黏著薄膜，就作業性、低成本化 之觀點上係適宜的。作爲相關黏著薄膜，可舉例如使用作 爲支持體之PET(聚對苯二甲酸乙二醇酯）等之高分子薄膜 或鋁、銅等之金屬箔，於上述支持體之兩面具有黏著材料 之黏著薄膜。黏著層之厚度爲抑制熱阻（Thermal Resistance)，以1 5 0 μm以下爲宜，以1 〇〇 μm以下尤佳， 以5 Ομπι以下更好。上述黏著層厚度超過150 μιη時，熱阻 增加，將有難以有效地傳熱於散熱材料之趨勢。就黏著層 之強度、黏著力上，黏著層厚度之下限値係以5 μιη以上 -19- 200837108 爲宜。另外，因爲散熱材料藉由具有黏著層，抑制熱傳導 率降低’形成散熱材料之黏著層之材料之熱傳導率係以 0.5W/mK以上爲且’以以上尤佳。 本發明之散熱材料係可作爲用以抑制於電腦、電漿電 視等之電子機器中因CPU、電漿電視之熱源等之溫度上升 之散熱裝置使用。 【實施方式】 實施例 以下係藉由實施例具體地說明本發明。 實施例1 將粉碎膨脹石墨薄片化物之膨脹石墨粉碎粉（日立化 成工業股份有限公司製，商品名：HGF — L)及含二氫苯幷 噁嗪環粉末之加成反應型熱硬化性樹脂（日立化成工業股 份有限公司製，商品名：HR 1 060)，以質量比5 5/45粉體 混合，使用熱加壓，以面壓爲30MPa、成形溫度爲200 °C、成形時間爲5分鐘之加壓條件成形，製作具有如圖3 所示形狀之散熱片結構之散熱材料。圖3係表示散熱材料 面方向之形狀之正面圖。 接著，上述所使用之散熱材料之與散熱片相反面之底 面，於厚度爲5μιη之PET薄膜的兩面，貼附具有5μιη之 丙烯酸橡膠黏著材料之厚度爲15 μιη之黏著薄膜（曰立化 成聚合物股份有限公司製，商品名·· Hi — Bon，熱傳導熱 -20- 200837108 爲0.2W/mK)，製作附有黏著層之散熱材料。 由以下方法測定所得散熱材料之容積密度、於6(TC 時放射面之放射率、熱傳導率、比熱、熱膨脹率、及體積 固有電阻。結果如表1所示。 (測定容積密度） 散熱材料之質量除以體積而算出。 (測定放射率） 散熱材料之放射面之放射率係使用日本電子股份有限 公司製之JIR — 5 500型傅立葉轉換紅外線分光光度計及放 射測定裝置JRR - 200，以FT — IR法測定，算出積分放射 率，作爲放射率。 (測定熱傳導率） 熱傳導率係使用真空理工股份有限公司製TC— 7000 型，測定熱擴散率，由比熱及容積密度算出。 (測定比熱） 比熱係藉由使用Perkin-Elmer公司製之DSC— 7型之 DSC(差示掃描熱量計）測定。 (測定熱膨脹率） 熱膨脹率係使用SEIKO股份有限公司製之SS5200型 熱機械分析裝置（TMA)測定。 (測定體積固有電阻） 體積固有電阻係使用 KIKUE ELECTRONICS公司之 MODEL PAB型電流電壓發生器，由4端子法測定。 所得之散熱材料之散熱特性係由下述方法評估。 -21 - 200837108 如圖2所示，放置銅板3於1 〇mm方塊之陶瓷加熱器 2 (坂口電熱股份有限公司製）上’黏貼散熱材料1於銅板3 上，以連接散熱材料1之黏著層。流通一定輸出： 2.5W/cm2(l 50 °C )之電流於陶瓷力卩熱器2，由 Thermo-Logger(安立計器股份有限公司製，製品名：AM— 8 060K) 測定銅板3之中心部份溫度。因難以直接測定陶瓷加熱器 2之溫度降低，所以測定陶瓷加熱器2與散熱材料1間之 銅板3之溫度。測定銅板溫度係進行試驗開始2 0分鐘 後，爲避免周圍環境溫度的影響，定義銅板之溫度T 1與 環境溫度T2之差（T1 一 T2)爲評估溫度。結果如表丨所 示。 實施例2 除了膨脹石墨粉碎粉與加成反應型熱硬化性樹脂之質 量比爲70/3 0以外，與實施例1同樣地操作，製作附有黏 著層之散熱材料，進行相同的評估。結果如表1所示。 實施例3 除了膨脹石墨粉碎粉與加成反應型熱硬化性樹脂之質 量比爲9 0/1 〇以外，與實施例1同樣地操作，製作附有黏 著層之散熱材料，進行相同的評估。結果如表1所示。 實施例4 除了使用天然石墨粉（日本石墨股份有限公司製，商 -22- 200837108 品名：F4 8)以取代膨脹石墨粉碎粉，天然石墨粉與加成反 應型熱硬化性樹脂之質量比爲90/10以外，與實施例〗同 樣地操作，製作散熱材料。接著，塗佈熱傳導性潤滑脂 (Sunhayato股份有限公司製，商品名：SCH— 20，熱傳導 率爲〇.84W/mK)於與散熱材料散熱片相反面之底面，使與 銅板密合。進行與實施例1相同之評估，結果如表1所 示0 實施例5 除了使用人造石墨粉（Timcal公司製，商品名：ks5 -7 5)以取代膨脹石墨粉碎粉，人造石墨粉與加成反應型熱 硬化性樹脂之質量比爲9 0/ 1 〇以外，與實施例1同樣地操 作，製作散熱材料。接著，塗佈熱傳導性潤滑脂 (Sunhayato股份有限公司製，商品名：SCH— 20，熱傳導 率爲〇.84W/mK)於與散熱材料散熱片相反面之底面，使與 • 銅板密合。進行與實施例1相同之評估，結果如表1所 7[\ ° 實施例6 除了使用酚醛樹脂（日立化成工業股份有限公司製， 商品名：HP - 1 90R)以取代加成反應型熱硬化性樹脂，膨 脹石墨粉碎粉與酚醛樹脂之質量比爲90/10以外，與實施 例1同樣地操作’製作散熱材料。接著，塗佈熱傳導性潤 滑脂（Sunhayato股份有限公司製，商品名：scH 一 20，熱 -23- 200837108 傳導率爲0.84W/mK)於與散熱材料散熱片相反面之底面， 使與銅板密合。進行與實施例1相同之評估，結果如表1 所示。 實施例7 除了使用人造石墨粉（Timcal公司製，商品名：ks5 — 7 5)以取代膨脹石墨粉碎粉，使用酚醛樹脂（日立化成工業 股份有限公司製，商品名：HP - 190R)以取代加成反應型 熱硬化性樹脂，人造石墨粉Jkli醛樹脂乙質量比爲90/10 条 以外，與實施例1同樣地操作，製作散熱材料。接著，塗 佈熱傳導性潤滑脂（Sunhayato股份有限公司製，商品名： SCH— 20，熱傳導率爲〇.84W/mK)於與散熱材料散熱片相 反面之底面，使與銅板密合。進行與實施例1相同之評 估，結果如表1所示。 實施例8 除了使用天然石墨粉（日本石墨股份有限公司製，商 品名：F48)以取代膨脹石墨粉碎粉，使用酚醛樹脂.（日立 化成工業股份有限公司製，商品名：HP — 190R)以取代加 成反應型熱硬化性樹脂，天然石墨粉與酚醛樹脂之質量t匕 爲90/10以外，與實施例1同樣地操作，製作散熱材料。 接著，塗佈熱傳導性潤滑脂（Sunhayato股份有限公司製， 商品名：SCH— 20，熱傳導率爲0.84W/mK)於與散熱材料 散熱片相反面之底面，使與銅板密合。進行與實施例1 ；[:目 -24- 200837108 同之評估，結果如表1所示° 比較例1 除了膨脹石墨粉碎粉與加成反應型熱硬化性樹脂之質 量比爲96/4以外，與實施例1同樣地操作時，混合物黏 度上升，不能成形，不能製作散熱材料。 比較例2 除了膨脹石墨粉碎粉與加成反應型熱硬化性樹脂之質 量比爲45/5 5以外，與實施例1同樣地操作，製作附有黏 著層之散熱材料，進行相同評估。結果如表2所示。 比較例3 膨脹石墨粉碎粉與加成反應型熱硬化性樹脂之質量比 爲4 5 / 5 5，如圖4所示之形狀以外，與實施例1同樣地操 作，製作散熱材料。接著，塗佈熱傳導性潤滑脂 (Sunhayato股份有限公司製，商品名：SCH— 20，熱傳導 率爲0.84W/mK)於與散熱材料散熱片相反面之底面，使與 銅板密合。進行與實施例1相同之評估，結果如表2所 不 ° 參考例1The above-mentioned tree is suitable as '1.2 to -2.2g/cm3. The internal content is ‘heat dissipation of the material 2 · 2 g/cm3 : the heat will be dissipated. 2 g/cm3, and the press forming rate is better. The effect of the release of the upper limit is not -14- 200837108 full 1.0. The emissivity of the heat dissipating surface of the heat dissipating material at 60 ° C can be measured, for example, by the method of the FT-IR method. In this method, the FT-IR (Fourier Transform Infrared Spectrophotometer) is used to measure the spectroscopic radiation intensity of the black body furnace (the temperature of any two different temperatures) and the radiation surface of the measurement sample (heat dissipating material), and thus the spectroscopic radiation intensity. In the theory of the spectroscopic radiation intensity of the black body furnace, the spectroscopic emissivity of the measurement sample is obtained, and the integrated emissivity is calculated. In the present invention, the integral emissivity is referred to as the emissivity. Further, since the emissivity is based on the temperature of the measurement sample (temperature dependence shows different behavior depending on the material), the present invention is used at 60 °C. The emissivity of the heat dissipating surface of the heat dissipating material of the present invention at 60 ° C is 〇. 40 or more, the heat dissipating material is formed by using a rough metal mold, or a blasting machine or the like is used to roughen the surface of the heat dissipating material. The heat conductivity of the heat dissipating material of the present invention is preferably 10 W/mK or more, more preferably 20 W/mK or more, and still more preferably 30 W/mK or more. When the thermal conductivity in the thickness direction is less than 1 OW/mK, there is a tendency that heat from the heat source can be dissipated from the heat radiation from the heat dissipating surface (the surface having the fins in the fin structure). Further, the heat conductivity of the heat dissipating material of the present invention is preferably 30 W/mK or more, more preferably 50 W/mK or more, and still more preferably 1 W/mK or more. In order to obtain high heat dissipation characteristics, the higher the thermal conductivity, the higher the better, but the upper limit is 200 W/mK. In order to obtain a thermal conductivity exceeding 200 W/mK, the formation becomes difficult because the resin content must be extremely reduced. The thermal conductivity in the thickness direction is calculated by a half-time method such as laser flash or xenon flash -15-200837108, and the thermal diffusivity is calculated from the product of specific heat and bulk density obtained by laser flash, xenon flash, or the like. In addition, the thermal conductivity in the thickness direction can be directly calculated by the temperature tilt method. For the measurement by the half-time method, for example, a heat number measuring device TC-3000 type, a TC-7000 type manufactured by Vacuum Technology Co., Ltd., or a NanoflashLFA447 manufactured by NETZSCH Co., Ltd., or the like can be used. In addition, the thermal conductivity in the plane direction is formed by laminating the samples by a lamellar method to form a surface, which is vertically irradiated with a laser flash and a gas flashing on the surface, according to the half-time method and the thickness direction. The method in which the thermal conductivity is calculated in the same manner or the sample is finely overlapped to form a surface, and a vertical temperature difference is applied to the surface, which can be measured by a temperature tilt method. The heat transfer material of the present invention has a thermal conductivity of 10 W/mK or more in the thickness direction, and a material having a high thermal conductivity material having a mass ratio of 50% or more in the heat dissipating material is sufficiently kneaded, and is formed by hot pressing at a sufficient pressure and temperature. can. The thermal conductivity of the surface direction is 30 W/mK or more, and the material of the high heat conductive material having a mass ratio of 50% or more in the heat dissipating material is sufficiently kneaded in the same manner as the thickness direction, and is sufficiently pressed at a sufficient pressure and temperature. Form it. The heat dissipating material of the present invention preferably has a specific heat of 〇.85j/gK or less, more preferably G.80J/gK or less, or more preferably 〇75J/gK or less. When the specific heat is 0.85 J/gK or less, the temperature reactivity is excellent compared with the conventional heat-dissipating material used as a heat-dissipating material of 0.8 8 J/gK. The specific heat of the heat dissipating material of the present invention is 0 8 5 J/gK or less, and the heat dissipating material contains a material of high thermal conductivity material having a mass ratio of 50% or more, -16-200837108, fully kneaded, with sufficient pressure and temperature heat. Press forming can be. The thermal expansion coefficient of the surface of the heat dissipating material of the present invention is preferably 8χ1 (Γ67 t or less, more preferably 7乂10_6/art or less, and 6xl0-0/t: or less. better. The above thermal expansion rate is 8x1 (T6) When it is at least °C, it is less than the heat-dissipating material of aluminum which is conventionally used as a heat-dissipating material and has a thermal expansion coefficient of 25 x 10 · 6 / ° C. The dimensional change is small during heating, and damage due to thermal shock is less likely to occur. The coefficient of thermal expansion of the surface of the heat dissipating material is 8x1 (T6/t: φ or less). The material containing a high thermal conductivity material having a mass ratio of 50% or more in the heat dissipating material is sufficiently kneaded and can be formed by hot pressing at a sufficient pressure and temperature. The heat capacity of the heat dissipating material of the present invention is preferably 200 μΩ m or less, more preferably 150 μΩηη or less, and even more preferably 1 μμΩηη. When the volume specific resistance of the heat dissipating material is 200 μΩ or less, the heat dissipating material is used. The heat-dissipating material of the present invention has a volume specific resistance of 200 μ Ω m to provide a material having a high thermal conductivity material having a mass ratio of 50% or more in the heat-dissipating material, and is sufficiently kneaded. Fully pressure and temperature hot press forming is possible. The heat dissipating material of the present invention is UL-94, and has a flame retardancy of V-0. The product of the present invention can be used as an electronic component, so it is safe. It is necessary to have a flame retardancy. The heat-dissipating material of the present invention is a material having a high heat-conductive material having a mass ratio of 50% or more in a heat-dissipating material, and is sufficiently kneaded to sufficiently heat and heat. -17- 200837108 In order to improve heat dissipation, the heat dissipating material of the present invention preferably has a fin structure on the side of the heat dissipating surface. Here, the shape of the fin is as long as the surface area is increased and the shape of heat is easily diffused. In particular, for example, a comb type such as an elongated shape or a cylindrical shape, a needle type such as a tapered shape, etc., etc., the number, direction, interval, arrangement, and the like of the heat sink are appropriately set depending on the application or the object to be applied. The height of the heat sink is preferably 30 to 95% of the overall height of the heat dissipating material, preferably 40 to 95%, more preferably 50 to 95%, and the heat sink height is less than 30% of the overall height of the heat dissipating material. On the other hand, when the heat sink height exceeds 95% of the overall height of the heat dissipating material, there is a tendency that the heat sink is difficult to form, and the heat sink material has a tendency to decrease in strength. The heat sink is for improving heat dissipation efficiency and heat dissipation. The thickness of the sheet is gradually increased from the tip end portion of the fin toward the root portion. The groove portion is preferably a cone. The taper angle is 1 to 30. Preferably, it is 1 to 20. More preferably, it is 1 to 1 inch. More preferably. When the taper angle is less than 1°, there is a tendency that it is difficult to release from the metal mold. On the other hand, when the taper angle exceeds 30, since the width of the fin base is increased, the distance between the fins cannot be thinned, so heat dissipation is caused. The area is reduced and the heat dissipation characteristics are reduced. A conical heat sink material is shown in Figure 1. The structure of the heat dissipating material of the present invention, as described above, is carried out by a metal mold in which a heat dissipating material is selectively formed. The overall temperature of the heat dissipating material of the present invention varies depending on the application and the mounting portion. However, when it is used in an electronic device such as a computer or a plasma TV, heat transfer in the direction of the heat capacity and the heat dissipating material is preferably 1 mm or more. More preferably 2mm or more, more preferably 3mm or more -18-200837108. When the overall height of the heat dissipating material is less than 1 mm, heat transfer in the surface direction of the heat capacity and the heat dissipating material is lowered, and there is a tendency that heat is not effectively dissipated. On the other hand, the upper limit of the overall height of the heat dissipating material is i5 〇 mm degree, which may be difficult to form. The method for producing the heat dissipating material of the present invention is not particularly limited, and for example, a mixture of a heat conductive material and a resin is used as a kneader, a kneading machine, a Henschel Mixer, a planetary mixer, and a roller mill. The obtained mixture can be produced by a known plastic molding method such as injection molding, extrusion molding, press molding, or the like by a step of stirring, mixing, kneading, rolling, or the like, to form a desired shape. In order to improve the adhesion between the heat source and the heat source, the heat dissipating material of the present invention preferably has an adhesive layer on the opposite side of the heat dissipating surface. The material of the adhesive layer is not particularly limited as long as it can adhere to the heat sink of the present invention and a heat source such as a CPU. For example, an acrylic adhesive, a rubber adhesive, a polyoxyalkylene adhesive, or the like can be used. The adhesive material is used for an adhesive film having an adhesive material on both sides of the support, and is suitable from the viewpoint of workability and cost reduction. As the relevant adhesive film, for example, a polymer film such as PET (polyethylene terephthalate) as a support or a metal foil such as aluminum or copper is used, and the adhesive material is adhered to both surfaces of the support. film. The thickness of the adhesive layer is a thermal resistance of less than 150 μm, preferably less than 1 〇〇 μm, and more preferably less than 5 Ομπι. When the thickness of the above adhesive layer exceeds 150 μm, the thermal resistance increases, and there is a tendency that it is difficult to efficiently transfer heat to the heat dissipating material. As for the strength and adhesion of the adhesive layer, the lower limit of the thickness of the adhesive layer is preferably 5 μm or more and -19 to 200837108. Further, since the heat dissipating material has an adhesive layer, the thermal conductivity is suppressed from decreasing. The thermal conductivity of the material forming the adhesive layer of the heat dissipating material is preferably 0.5 W/mK or more and more preferably </ RTI> or more. The heat dissipating material of the present invention can be used as a heat dissipating device for suppressing an increase in temperature of a CPU, a heat source such as a plasma TV, or the like in an electronic device such as a computer or a plasma TV. [Embodiment] Hereinafter, the present invention will be specifically described by way of examples. Example 1 An expanded graphite pulverized powder of pulverized expanded graphite flakes (manufactured by Hitachi Chemical Co., Ltd., trade name: HGF-L) and an addition reaction type thermosetting resin containing dihydrophenyl hydrazine ring powder ( Made by Hitachi Chemical Co., Ltd., trade name: HR 1 060), mixed with a mass ratio of 5 5/45 powder, using hot pressurization, with a surface pressure of 30 MPa, a forming temperature of 200 ° C, and a forming time of 5 minutes. The pressurization conditions were formed to produce a heat dissipating material having a fin structure of the shape shown in Fig. 3. Fig. 3 is a front elevational view showing the shape of the surface of the heat dissipating material. Next, on the bottom surface of the heat-dissipating material used on the opposite side of the heat-dissipating sheet, on both sides of the PET film having a thickness of 5 μm, an adhesive film having a thickness of 15 μm with an acrylic rubber adhesive material of 5 μm is attached (initialized polymer Co., Ltd., the product name · Hi — Bon, heat conduction heat -20- 200837108 is 0.2W/mK), and a heat dissipation material with an adhesive layer is prepared. The bulk density of the obtained heat-dissipating material was measured by the following method at 6 (radiation ratio, thermal conductivity, specific heat, thermal expansion coefficient, and volume specific resistance at TC). The results are shown in Table 1. (Measurement bulk density) Heat-dissipating material The mass is calculated by dividing the volume. (Measurement of emissivity) The emissivity of the radiating surface of the heat dissipating material is JIR-5500 type Fourier transform infrared spectrophotometer and radiation measuring device JRR-200 manufactured by JEOL Ltd. —The IR method is used to calculate the integrated emissivity as the emissivity. (Measurement of thermal conductivity) The thermal conductivity is calculated using the TC-7000 model manufactured by Vacuum Technology Co., Ltd., and the thermal diffusivity is measured and calculated from specific heat and bulk density. (Measurement specific heat) The specific heat was measured by using DSC (differential scanning calorimeter) of DSC-7 manufactured by Perkin-Elmer Co., Ltd. (Measurement of thermal expansion coefficient) The thermal expansion coefficient was a thermal mechanical analysis device (TMA) of SS5200 manufactured by SEIKO Co., Ltd. Measurement (measurement volume inherent resistance) Volume inherent resistance is based on the MODEL PAB type current and voltage of KIKUE ELECTRONICS The generator was measured by the 4-terminal method. The heat dissipation characteristics of the obtained heat-dissipating material were evaluated by the following method. -21 - 200837108 As shown in Fig. 2, the ceramic heater 2 was placed in a 1 〇mm square. Co., Ltd.) on the 'adhesive heat-dissipating material 1 on the copper plate 3 to connect the adhesive layer of the heat-dissipating material 1. The flow has a certain output: 2.5W/cm2 (l 50 °C) current in the ceramic force heater 2, by Thermo -Logger (manufactured by Anritsu Co., Ltd., product name: AM-8 060K) The temperature of the central portion of the copper plate 3 is measured. Since it is difficult to directly measure the temperature drop of the ceramic heater 2, the ceramic heater 2 and the heat dissipating material 1 are measured. The temperature of the copper plate 3. The temperature of the copper plate is measured. After the test is started for 20 minutes, in order to avoid the influence of the ambient temperature, the difference between the temperature T 1 of the copper plate and the ambient temperature T2 (T1 to T2) is defined as the evaluation temperature. Example 2 A heat dissipating material with an adhesive layer was produced in the same manner as in Example 1 except that the mass ratio of the expanded graphite pulverized powder to the addition reaction type thermosetting resin was 70/30. The results are shown in Table 1. Example 3 The same procedure as in Example 1 was carried out except that the mass ratio of the expanded graphite pulverized powder to the addition reaction type thermosetting resin was 9 0/1 Torr. The heat dissipation materials of the layers were subjected to the same evaluation. The results are shown in Table 1. Example 4 In place of the expanded graphite pulverized powder, a natural graphite powder (manufactured by Nippon Graphite Co., Ltd., -22-200837108, product name: F4 8) was used. A heat dissipating material was produced in the same manner as in the Example except that the mass ratio of the natural graphite powder to the addition reaction type thermosetting resin was 90/10. Next, a thermally conductive grease (manufactured by Sunhayato Co., Ltd., trade name: SCH-20, thermal conductivity: 84.84 W/mK) was applied to the bottom surface of the surface opposite to the heat sink fin to be in close contact with the copper plate. The same evaluation as in Example 1 was carried out, and the results are shown in Table 1. Example 5 Except that artificial graphite powder (trade name: ks5-7 5 manufactured by Timcal Co., Ltd.) was used instead of expanded graphite pulverized powder, artificial graphite powder and addition. A heat dissipating material was produced in the same manner as in Example 1 except that the mass ratio of the reactive thermosetting resin was 90% to 1 Torr. Next, a thermally conductive grease (manufactured by Sunhayato Co., Ltd., trade name: SCH-20, thermal conductivity: 84.84 W/mK) was applied to the bottom surface of the surface opposite to the heat sink fin, so as to be in close contact with the copper plate. The same evaluation as in Example 1 was carried out, and the results are as shown in Table 1 [\ ° Example 6 except that a phenol resin (manufactured by Hitachi Chemical Co., Ltd., trade name: HP - 1 90R) was used in place of the addition reaction type thermosetting. The heat-dissipating material was produced in the same manner as in Example 1 except that the mass ratio of the expanded resin to the pulverized powder of the expanded graphite and the phenol resin was 90/10. Next, a thermally conductive grease (trade name: scH-20, heat-23-200837108 conductivity: 0.84 W/mK, manufactured by Sunhayato Co., Ltd.) was applied to the bottom surface opposite to the heat sink fin to make it dense with the copper plate. Hehe. The same evaluation as in Example 1 was carried out, and the results are shown in Table 1. Example 7 A phenol resin (manufactured by Hitachi Chemical Co., Ltd., trade name: HP - 190R) was used instead of artificial graphite powder (trade name: ks5 - 75, manufactured by Timcal Co., Ltd.) to replace the expanded graphite pulverized powder. A heat-dissipating material was produced in the same manner as in Example 1 except that the mass ratio of the reaction-type thermosetting resin to the artificial graphite powder Jkli aldehyde resin was 90/10. Next, a thermally conductive grease (manufactured by Sunhayato Co., Ltd., trade name: SCH-20, thermal conductivity: 84.84 W/mK) was applied to the bottom surface opposite to the heat sink fins to adhere to the copper plate. The same evaluation as in Example 1 was carried out, and the results are shown in Table 1. Example 8 In place of the expanded graphite pulverized powder, a natural graphite powder (manufactured by Nippon Graphite Co., Ltd., trade name: F48) was used, and a phenol resin (manufactured by Hitachi Chemical Co., Ltd., trade name: HP - 190R) was used instead. The heat-dissipating material was produced in the same manner as in Example 1 except that the addition-type thermosetting resin was used, and the mass of the natural graphite powder and the phenol resin was 90/10. Next, a thermally conductive grease (manufactured by Sunhayato Co., Ltd., trade name: SCH-20, thermal conductivity: 0.84 W/mK) was applied to the bottom surface of the surface opposite to the heat sink fins to adhere to the copper plate. The evaluation was carried out in the same manner as in Example 1; [:目-24-200837108, and the results are shown in Table 1. Comparative Example 1 except that the mass ratio of the expanded graphite pulverized powder to the addition reaction type thermosetting resin was 96/4. When the operation was carried out in the same manner as in Example 1, the viscosity of the mixture was increased, and it was impossible to form a heat-dissipating material. Comparative Example 2 A heat dissipating material with an adhesive layer was produced in the same manner as in Example 1 except that the mass ratio of the expanded graphite pulverized powder to the addition reaction type thermosetting resin was 45/5 5 , and the same evaluation was carried out. The results are shown in Table 2. Comparative Example 3 A heat dissipating material was produced in the same manner as in Example 1 except that the mass ratio of the expanded graphite pulverized powder to the addition reaction type thermosetting resin was 4 5 / 5 5 as shown in Fig. 4 . Then, a heat conductive grease (manufactured by Sunhayato Co., Ltd., trade name: SCH-20, thermal conductivity: 0.84 W/mK) was applied to the bottom surface of the surface opposite to the heat sink fin to be in close contact with the copper plate. The same evaluation as in Example 1 was carried out, and the results are as shown in Table 2. Reference Example 1
以鋁製作如圖3所示形狀之散熱材料。接著，、塗{布熱 傳導性潤滑脂（Sunhayato股份有限公司製，商品名：SCH -25- 200837108 —20，熱傳導率爲〇.84W/mK)於與散熱材料散熱片相反面 之底面’使與銅板密合。進行與實施例i相同之評估，結 果如表2所示。 參考例2 不使用散熱材料，測定銅板之溫度。亦即，放置銅板 3於10mm方塊之陶瓷加熱器2(坂口電熱股份有限公司製） 上’流通一定輸出：2.5W/cm2(15(TC)之電流於陶瓷加熱 器2，由Thermo-Logger(安立計器股份有限公司製，製品 名：AM — 80 60K)測定銅板3之中心部份溫度。定義銅板 之溫度T1與環境溫度T2之差（T1 一 T2)爲評估溫度。結果 如表2所示。A heat dissipating material having a shape as shown in Fig. 3 was made of aluminum. Next, coating {thermal conductivity grease (manufactured by Sunhayato Co., Ltd., trade name: SCH-25-200837108-20, thermal conductivity: 84.84W/mK) on the bottom surface opposite to the heat sink fin" The copper plate is tight. The same evaluation as in Example i was carried out, and the results are shown in Table 2. Reference Example 2 The temperature of the copper plate was measured without using a heat dissipating material. That is, the copper plate 3 is placed on a 10 mm square ceramic heater 2 (manufactured by Hagi Electric Co., Ltd.) to circulate a certain output: 2.5 W/cm 2 (15 (TC) current to the ceramic heater 2, by Thermo-Logger ( Anritsu Co., Ltd., product name: AM - 80 60K) Determine the temperature of the central part of the copper plate 3. Define the difference between the temperature T1 of the copper plate and the ambient temperature T2 (T1 - T2) as the evaluation temperature. The results are shown in Table 2. .
-26- 200837108 表1-26- 200837108 Table 1
實 沲例 1 2 3 4 5 6 7 8 石墨之種類 HGF-L HGF-L HGF-L F48 Ks5-75 HGF-L Ks5-75 F48 樹脂之種類 HR1060 HR1060 HR1060 HR1060 HR1060 HR-190R HR-190R HR-190R 石墨/樹脂 (Si%) 55/45 70/30 90/10 90/10 90/10 90/10 90/10 90/10 容積密度 (g/cm3) 1.6 1.8 1.9 1.9 1.9 1.9 1.9 1.9 放射率 0.59 0.58 0.57 0.60 0.58 0.57 0.58 0.56 厚度方向熱 傳導率 (W/mK) 11 14 22 19 20 22 20 19 面方向熱傳 導率(W/mK) 52 63 115 95 100 105 100 98 比熱(J/gK) 0.83 0.79 0.76 0.77 0.77 0.76 0.77 0.77 熱膨脹率 (/°c ) 7χ ΙΟ'6 6.5x 10-6 6χ ΙΟ-6 6x 10·6 6x 10·6 6x ΙΟ'6 6x 10_6 6x ΙΟ'6 體積固有電 阻(ΜΩ m) 150 60 40 52 50 39 48 53 難燃性 (UL-94) V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 黏著層 有 有 有 無 4tjT Μ /\\\ M j\\\ M /w\ 形狀 圖3 圖3 圖3 圖3 圖3 圖3 圖3 圖3 銅板之溫度 Tl(°c ) 62.3 59.3 58.4 60.2 60.5 59.9 59.9 58.8 環境之溫度 T2(°C ) 23.2 21.8 22.7 24.0 24.1 23.8 23.6 22.4 評觸度 T1-T2 rc ) 39.1 37.5 35.7 36.2 36.4 36.1 36.3 36.4 -27- 200837108 表2 比較例 參考例 1 2 3 1 石墨之種類 HGF- L HGF- L HGF- L / 1 樹脂之種類 HR1060 HR1060 HR1060 石墨/樹脂違量％) 96/4 45/55 45/55 容積密度(g/cm3) 7 1.5 1.5 2.71 放射率 0.56 0.57 0.03 厚度方向熱傳導率(W/mK) 8 9 170 面方向熱傳導率(W/mK) 33 34 170 比熱(J/gK) 0.87 0.86 0.88 熱膨脹率(/。〇 7.5x10-6 7.5x10'6 25xl〇·6 體積固有電阻(Μ Ωπι) 220 210 0.031 難燃性(UL-94) X X V-0 黏著層 有 並 Μ j\ \\ 形狀 圖3 圖4 圖3 銅板之溫度Tl(〇C) 66.7 69.9 61.1 147.5 環境之溫度T2(〇C) 24.4 24.3 21.0 22.5 評估溫度T1-T2CC) 42.3 45.6 40.1 125.0 產業上利用性 本發明之散熱材料係輕量且具有高放射率，散熱特性 優異者。 【圖式簡單說明】 [圖1 ]表示具有圓錐形狀之散熱片結構之散熱材料之 正面圖。 [圖2]表示散熱特性評估試驗方法之槪略圖。 [圖3]表示實施例1〜8、比較例2及參考例1中使用 之散熱材料面方向之形狀之正面圖。 -28- 200837108 [圖4]表示比較例3中使用之散熱材料面方向之形狀 之正面圖。Example 1 2 3 4 5 6 7 8 Type of graphite HGF-L HGF-L HGF-L F48 Ks5-75 HGF-L Ks5-75 F48 Type of resin HR1060 HR1060 HR1060 HR1060 HR1060 HR-190R HR-190R HR- 190R Graphite/Resin (Si%) 55/45 70/30 90/10 90/10 90/10 90/10 90/10 90/10 Bulk Density (g/cm3) 1.6 1.8 1.9 1.9 1.9 1.9 1.9 1.9 Emissivity 0.59 0.58 0.57 0.60 0.58 0.57 0.58 0.56 Thermal conductivity in thickness direction (W/mK) 11 14 22 19 20 22 20 19 Thermal conductivity in the plane direction (W/mK) 52 63 115 95 100 105 100 98 Specific heat (J/gK) 0.83 0.79 0.76 0.77 0.77 0.76 0.77 0.77 Thermal expansion rate (/°c) 7χ ΙΟ'6 6.5x 10-6 6χ ΙΟ-6 6x 10·6 6x 10·6 6x ΙΟ'6 6x 10_6 6x ΙΟ'6 Volume inherent resistance (ΜΩ m) 150 60 40 52 50 39 48 53 Flame retardancy (UL-94) V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 Adhesive layer with or without 4tjT Μ /\\ \ M j\\\ M /w\ Shape Figure 3 Figure 3 Figure 3 Figure 3 Figure 3 Figure 3 Figure 3 Figure 3 Copper plate temperature Tl (°c) 62.3 59.3 58.4 60.2 60.5 59.9 59.9 58.8 Ambient temperature T2 (°C 23.2 21.8 22.7 24.0 24.1 23.8 23.6 22.4 Tactile T1-T2 rc ) 39.1 37.5 35.7 36.2 36.4 36.1 36.3 36.4 -27- 200837108 Table 2 Comparative Example Reference Example 1 2 3 1 Type of graphite HGF- L HGF- L HGF- L / 1 Type of resin HR1060 HR1060 HR1060 Graphite/resin violation %) 96/4 45/55 45 /55 Bulk density (g/cm3) 7 1.5 1.5 2.71 Emissivity 0.56 0.57 0.03 Thermal conductivity in the thickness direction (W/mK) 8 9 170 Thermal conductivity in the plane direction (W/mK) 33 34 170 Specific heat (J/gK) 0.87 0.86 0.88 thermal expansion rate (/. 〇7.5x10-6 7.5x10'6 25xl〇·6 Volume inherent resistance (Μ Ωπι) 220 210 0.031 Flame retardant (UL-94) XX V-0 Adhesive layer with Μ j\ \\ Shape Figure 3 Figure 4 Figure 3 Temperature of copper plate Tl(〇C) 66.7 69.9 61.1 147.5 Temperature of environment T2 (〇C) 24.4 24.3 21.0 22.5 Evaluation temperature T1-T2CC) 42.3 45.6 40.1 125.0 Industrial Applicability The heat dissipating material of the present invention is lightweight and high Excellent in emissivity and heat dissipation characteristics. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] is a front view showing a heat dissipating material having a conical fin structure. Fig. 2 is a schematic diagram showing a test method for evaluating heat dissipation characteristics. Fig. 3 is a front elevational view showing the shapes of the surface of the heat dissipating material used in Examples 1 to 8, Comparative Example 2, and Reference Example 1. -28-200837108 [Fig. 4] A front view showing the shape of the surface of the heat dissipating material used in Comparative Example 3.
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