201002752 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種在信賴性優良之半導體封閉、層合 板、放熱基板等之電氣•電子零件用絕緣材料上有用之環 氧樹脂組成物及使用其之成形物。 【先前技術】 傳統上’關於二極體、電晶體、積體電路等之電氣· 電子零件、或者半導體裝置等之封閉方法上，係採用例如 環氧樹脂或矽樹脂等等之封閉方法；或使用玻璃、金屬、 陶瓷等之氣密密封法，惟近年則以除了要求信賴性提升以 外，還要能大量生產者，亦即具有成本經濟面之優點之轉 注成形所進行之樹脂封閉，成爲了主流。 在以上述轉注成形所進行之樹脂封閉方法而使用之樹 脂組成物中’其一般係使用環氧樹脂，以及硬化劑之苯酚 樹脂作爲樹脂成分之主成分之樹脂組成物，所成之封閉材 料。 現在，基於保護功率設備等元件之目的所使用之環氧 樹脂組成物，由於要對應於元件所釋放之多量之熱之緣故 ，皆塡充了高密度的結晶二氧化矽等無機塡充材料。 進而，在近年，功率設備有以組裝了 1C技術的單一 晶片所構成者或模組化者等，其被希望能進一步提升對於 封閉材料之熱釋放性、熱膨脹性。 對應於此等之要求，爲提升熱傳導率起見，有嘗試使 -5- 201002752 用結晶二氧化矽、氮化矽、氮化鋁、球狀氧化鋁粉末（專 利文獻1、2)，惟如提升無機塡充材料之含有率時，在 成形時黏度上升之同時，其流動率亦會降低，從而產生了 成形性受損之問題。因此，僅提高無機塡充材料之含有率 之方法，有其限制存在。 基於上述背景，有檢討利用基體（matrix )樹脂本身 所進行之高熱傳導效率化之方法，舉例而言，在專利文獻 3及專利文獻4中，有提案使用具有剛直之液晶質（ m e s 〇 g e η )基之液晶性樹脂之樹脂組成物。然而，此等具 有液晶質基之環氧樹脂，係具有聯苯構造、甲亞胺構造等 之剛直構造之高結晶性、高融點之環氧化合物，在作爲環 氧樹脂組成物處理時有其缺點。進一步，爲使其在硬化狀 態下之分子能以良好效率配向起見，必須特別施加強力之 磁場使其硬化等操作，因此在工業上廣泛利用時對於設備 就造成了很大的限制。此外，在與無機塡充劑之配合系中 ，與基體樹脂之熱傳導率相較，無機塡充材料之熱傳導率 遠大的多，而即使將基體樹脂本身之熱傳導率提高，現實 上對於其複合材料之熱傳導率提高者，亦無大的幫助，因 此並不能得到充分的熱傳導率提高之效果。 在專利文獻5中，揭示了 4,4’-二苯甲酮型之環氧樹 脂，惟僅揭示將酸酐作爲硬化劑所得到之硬化物的實施例 ，而其並非表現高熱傳導性之高次構造受控制硬化物。 專利文獻1 :特開平1 1 - 1 4 7 9 3 6號公報 專利文獻2:特開2002-309067號公報 201002752 專利文獻3 :特開平1 1 - 3 2 3 1 6 2號公報 專利文獻4:特開2004-33181】號公報 專利文獻5:特開平2-202512號公報 【發明內容】 發明之揭示 發明所欲解決之課題 據此，本發明之目的，係提供一種能解決上述問題點 ，且其成形性優良，當與無機塡充材料進行複合化時具有 高的熱傳導率，並在低熱膨脹性之下能賦予耐熱性及耐濕 性之硬化物的環氧樹脂組成物，以及使用其之成形物。 解決課題之手段 本發明者們，發現了在特定之環氧樹脂及特定之硬化 劑加以組合時，可得到硬化後，其高次構造受到控制之成 形物，而其高熱傳導性、低熱膨脹性、高耐熱性及高耐濕 性可以特異性地提高，從而完成本發明。 亦即’本發明係關於一種環氧樹脂組成物，其特徵爲 在含有（A)環氧樹脂及（B)硬化劑之環氧樹脂組成物 中，環氧樹脂之50wt%以上係下述一般式（1)所示之 4，4’-二苯甲酮系環氧樹脂，且硬化劑之50 wt %以上係下 述一般式（2)所示之4,4’_二苯甲酮系苯酚性樹脂，並且 環氧樹脂中之環氧基及硬化劑中之官能基之當量比係在 0.8〜1.5之範圍內者， 201002752 【化1】 .0[Technical Field] The present invention relates to an epoxy resin composition and use thereof for an insulating material for electric and electronic parts such as a semiconductor sealing, a laminated board, and a heat radiating substrate which are excellent in reliability. Its shape. [Prior Art] Conventionally, a sealing method such as an epoxy resin or a resin or the like is used for a sealing method of an electric/electronic component such as a diode, a transistor, an integrated circuit, or the like, or a semiconductor device or the like; or The gas-tight sealing method using glass, metal, ceramics, etc., in recent years, in addition to the increase in reliability required, it is also possible to manufacture a large number of producers, that is, a resin-sealed resin which has the advantages of cost-effective surface. Mainstream. In the resin composition used in the resin sealing method by the above-mentioned transfer molding, a resin material which is an epoxy resin and a phenol resin of a curing agent as a main component of a resin component is generally used as a sealing material. Now, an epoxy resin composition used for the purpose of protecting components such as power devices is filled with a high-density inorganic ruthenium material such as crystalline ruthenium dioxide because of the amount of heat released by the element. Further, in recent years, power devices have been formed by a single wafer in which 1C technology is assembled, or a modularizer, and it is desired to further improve the heat release property and thermal expansion property of the sealing material. Corresponding to these requirements, in order to improve the thermal conductivity, there is an attempt to use crystalline cerium oxide, cerium nitride, aluminum nitride, and spherical alumina powder for -5 to 201002752 (Patent Documents 1, 2). When the content of the inorganic filler is increased, the viscosity increases while forming, and the flow rate is also lowered, which causes a problem of impaired formability. Therefore, there is a limitation in the method of merely increasing the content of the inorganic chelating material. Based on the above-mentioned background, there is a method of reviewing the high heat transfer efficiency by the matrix resin itself. For example, in Patent Document 3 and Patent Document 4, it is proposed to use a liquid crystal having a rigidity (mes 〇ge η A resin composition of a liquid crystalline resin. However, these epoxy resins having a liquid crystal group are those having a high crystallinity and a high melting point of a rigid structure such as a biphenyl structure or a methylimine structure, and are treated as an epoxy resin composition. Its shortcomings. Further, in order to align the molecules in the hardened state with good efficiency, it is necessary to particularly apply a strong magnetic field to harden the operation, and the like, and therefore, it is greatly restricted to the equipment when it is widely used in the industry. In addition, in the combination with the inorganic chelating agent, the thermal conductivity of the inorganic chelating material is much larger than that of the matrix resin, and even if the thermal conductivity of the matrix resin itself is increased, the composite material is actually The increase in thermal conductivity does not help much, and therefore does not provide sufficient thermal conductivity enhancement. In Patent Document 5, an epoxy resin of a 4,4'-benzophenone type is disclosed, but only an example of a cured product obtained by using an acid anhydride as a curing agent is disclosed, and it is not a high degree of high thermal conductivity. Construct a controlled hardened material. [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A-2002-309067 No. 201002752 Patent Document 3: Japanese Patent Publication No. Hei No. 1 1 - 3 2 3 1 6 2 Patent Document 4: SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION According to the present invention, it is an object of the present invention to provide a solution to the above problems. An epoxy resin composition which is excellent in moldability, has a high thermal conductivity when compounded with an inorganic chelating material, and imparts a heat-resistant and moisture-resistant cured product under low thermal expansion property, and uses the same. Shaped product. MEANS FOR SOLVING THE PROBLEMS The present inventors have found that when a specific epoxy resin and a specific curing agent are combined, it is possible to obtain a molded product having a high-order structure after curing, and high thermal conductivity and low thermal expansion property. The high heat resistance and high moisture resistance can be specifically increased to complete the present invention. That is, the present invention relates to an epoxy resin composition characterized in that in the epoxy resin composition containing the (A) epoxy resin and the (B) hardener, 50% by weight or more of the epoxy resin is as follows. a 4,4'-benzophenone-based epoxy resin represented by the formula (1), and 50 wt% or more of the curing agent is a 4,4'-benzophenone group represented by the following general formula (2) a phenolic resin, and the equivalent ratio of the epoxy group in the epoxy resin and the functional group in the hardener is in the range of 0.8 to 1.5, 201002752 [Chemical 1] .0
(1) (惟，η係0〜15之數） 【化2】 (2) (惟’ m係0〜1 5之數） 〇 本發明之環氧樹脂組成物可含有無機塡充材料，其中 無機塡充材料係以含有50〜95wt%者爲較佳。再者，本 發明之環氧樹脂組成物，其係適合作爲半導體封閉用之環 氧樹脂組成物。 再者’本發明係關於一種預浸漬體，其特徵係將上述 環氧樹脂組成物含浸於薄片狀之纖維基材中，並作成半硬 化狀態而成者。 進一步’本發明係關於一種成形物，其特徵係將上述 環氧樹脂組成物加熱成形而得者。該硬化物，係以滿足以 下任一者以上爲較佳，1 )該熱傳導率係4 W/m · K以上 ;2)在示差掃描熱分析中之融點峰部係自150 t至300 〇C 之範圍者；3)在示差掃描熱分析中之樹脂成分換算之吸 -8 - 201002752 熱量係5 J/g以上者。 【實施方式】 實施發明之最佳型態 上述一般式（1)所示之4，4’-二苯甲酮系環氧樹脂（ 亦稱爲二苯甲酮系環氧樹脂），其可藉由使4,4’-二羥基 二苯甲酮與環氧氯丙烷進行反應而製造。該反應亦可與一 般之環氧化反應同樣地進行。舉例而言，可將4,4’-二經 基二苯甲酮溶解於過剩之環氧氯丙烷中，再於氫氧化鈉、 氫氧化鉀等之鹼金屬氫氧化物之存在下，以50〜150°C， 較佳爲60〜100 °C之範圍，使其反應1〜10小時之方法。 此時，鹼金屬氫氧化物之使用量，係相對於4,4’-二羥基 二苯甲酮中之羥基1莫爾，可使用0.8〜1.2莫爾，較佳 爲0.9〜1.0莫爾。環氧氯丙烷，係使用相對於4,4’_二羥 基二苯甲酮中之羥基爲過剩量者，一般而言，相對於 4,4’-二羥基二苯甲酮中之羥基1莫爾，係1.5至15莫爾 。在反應終了後，將過剩之環氧氯丙烷餾去，再將殘留物 溶解於甲苯、甲基異丁酮等之溶劑中，然後過濾、水洗而 除去無機鹽，最後餾去溶劑，即可得到標的之二苯甲酮系 環氧樹脂。 上述一般式（1)中，η係0〜15之數，惟η之値藉 於 。 , 對整 ^一一 一口 相調而 院以例 丙加舉 氯地。 氧易擇 環容選 之以地 用可當 使就適 所’而 時比’ 應爾途 反莫用 成之之 合酮用 在甲適 脂苯所 樹二據 氧基根 環羥可 變 1-1 値 改之 由 4， η -9- 201002752 在追求塡充劑之高塡充率化之半導體封閉之用途上，係以 低黏度下具有結晶性者爲較佳’ η之平均値，則可以在 〇.〇1〜1.0之範圍較佳地進行選擇。如較此更大時，其黏 度會變高，或處理性會降低。 本發明所使用之二苯甲酮系環氧樹脂’其原料可使用 將4，4 ’ -二羥基二苯甲酮與別種之苯酚性化合物加以混合 者’來進行合成。此時之4,4’-二羥基二苯甲酮之混合比 率，係5 〇wt %以上。苯酚性化合物並無特別之限制，惟 一分子中係以具有2個羥基之二官能性者爲較佳。 本發明所使用之環氧樹脂，一般式（1)所示之二苯 甲酮系環氧樹脂，其在環氧樹脂成分中，一般係含有 50wt%以上者，較佳係含有 80wt%以上者，最佳則係含 有90 wt %以上者。該二苯甲酮系環氧樹脂之環氧基當量 ，一般係由160至20,000之範圍，惟較佳之環氧基當量 ，可配合用途而適當地加以選擇。舉例而言，在半導體封 閉之用途上，基於無機塡充劑之高塡充率化及流動性提升 之觀點，係以低黏度者爲佳，且在上述一般式（1)中， 以n=0體爲主成分之環氧基當量，則以160至250之範 圍者爲較佳。此外，在層合板等之用途中，基於賦予薄膜 性、可撓性之觀點，較佳係4 0 0〜2 0，0 0 0之範圍。(1) (However, the number of η is 0 to 15) [2] (2) (Only the number of m-systems 0 to 1 5) The epoxy resin composition of the present invention may contain an inorganic filler, wherein The inorganic filler material is preferably 50 to 95% by weight. Further, the epoxy resin composition of the present invention is suitable as an epoxy resin composition for semiconductor encapsulation. Further, the present invention relates to a prepreg characterized in that the epoxy resin composition is impregnated into a sheet-like fibrous base material and formed into a semi-hardened state. Further, the present invention relates to a molded article characterized by subjecting the above epoxy resin composition to heat molding. The cured product is preferably one or more of the following: 1) the thermal conductivity is 4 W/m·K or more; 2) the melting peak in the differential scanning calorimetry is from 150 t to 300 〇. The range of C; 3) The conversion of the resin component in the differential scanning thermal analysis -8 - 201002752 The heat system is 5 J/g or more. [Embodiment] The 4,4'-benzophenone-based epoxy resin (also referred to as benzophenone-based epoxy resin) represented by the above general formula (1) can be used in the best mode of the invention. It is produced by reacting 4,4'-dihydroxybenzophenone with epichlorohydrin. This reaction can also be carried out in the same manner as the general epoxidation reaction. For example, 4,4'-di-dibenzophenone can be dissolved in excess epichlorohydrin, and in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, 50 A method of reacting for 1 to 10 hours at a temperature of from -150 ° C, preferably from 60 to 100 ° C. In this case, the alkali metal hydroxide is used in an amount of from 0.8 to 1.2 mol, preferably from 0.9 to 1.0 mol, based on the hydroxyl group of the 4,4'-dihydroxybenzophenone. Epichlorohydrin is used in excess of the hydroxyl group in 4,4'-dihydroxybenzophenone. In general, it is relative to the hydroxyl group in 4,4'-dihydroxybenzophenone. Seoul, 1.5 to 15 moles. After the completion of the reaction, the excess epichlorohydrin is distilled off, and the residue is dissolved in a solvent such as toluene or methyl isobutyl ketone, and then filtered, washed with water to remove the inorganic salt, and finally the solvent is distilled off. The standard benzophenone epoxy resin. In the above general formula (1), η is a number of 0 to 15, but η is derived from . , for the whole one-on-one, and the hospital to increase the chlorine. Oxygen is easy to choose, and the choice of the ring can be used to make it suitable for the time and the ratio of the ketone used in the application of the ketone in the benzoic acid benzene. 1 tampering by 4, η -9- 201002752 In the pursuit of high-capacity semiconductor sealing of 塡 , , , 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体 半导体It is preferable to select in the range of 〇.〇1 to 1.0. If it is larger than this, its viscosity will become higher, or the handleability will be lowered. The benzophenone-based epoxy resin used in the present invention can be synthesized by mixing 4,4 '-dihydroxybenzophenone with a phenolic compound of another type. The mixing ratio of 4,4'-dihydroxybenzophenone at this time was 5 〇 wt % or more. The phenolic compound is not particularly limited, and a monofunctional one having two hydroxyl groups is preferred in the sole molecule. The epoxy resin used in the present invention is a benzophenone-based epoxy resin represented by the general formula (1), and the epoxy resin component generally contains 50% by weight or more, preferably 80% by weight or more. The best is 90% or more. The epoxy equivalent of the benzophenone-based epoxy resin is generally in the range of from 160 to 20,000, and preferably the epoxy equivalent is appropriately selected depending on the use. For example, in the case of semiconductor encapsulation, based on the viewpoint of high charge rate and fluidity improvement of inorganic chelating agents, it is preferable to use low viscosity, and in the above general formula (1), n= The epoxy group equivalent of the main component of the 0 body is preferably in the range of 160 to 250. Further, in the use of a laminate or the like, it is preferably in the range of 4 0 0 to 2 0 0 0 0 based on the viewpoint of imparting film properties and flexibility.
一般式（1 )所示之二苯甲酮系環氧樹脂，其形態亦 可配合用途而適當地加以選擇。舉例而言，在半導體封閉 之用途上’由於有許多以粉體處理之故，其係以常溫下爲 固體之結晶性者爲較佳’並以融點在8 0 °C以上，且1 5 0 °C -10- 201002752 下之溶融黏度爲0.005至〇·2 Pa· s者爲理想。此外，在 層合板等之用途中，由於有許多係使其溶解於溶劑中而使 用者’因此環氧樹脂之形態並無特別之限制。 本發明所使用之環氧樹脂之純度，尤其是加水分解性 氯量’基於所適用之電子零件之信賴性提升之觀點，係以 較少者爲佳。其雖無特別之限制，惟較佳係i 0 0 〇 ppm以 下’最佳係5 00 ppm以下者。此外，本發明所謂之加水分 解性氯’係指以下述方法所測定者。亦即，將樣品〇. 5 g 溶解於二噁烷30 mi後，加入ιν-ΚΟΗ 10 m卜再以30分 鐘煮沸還流之後，冷卻至室溫，進一步加入8 0 %丙酮水 100 ml，而以〇.〇〇2 N_AgN〇3水溶液進行電位差滴定所得 到之値。 本發明之環氧樹脂組成物中，除本發明使用之必須成 分之一般式（1)所示之二苯甲酮系環氧樹脂以外，亦可 併用在分子中具有2個以上環氧基之其他環氧樹脂。舉例 而言’有雙酣A、4,4，_二羥基二苯基甲烷、3,3，，5,5、四 甲基-4,4’-二經基二苯基甲烷、4,4，_二羥基二苯基楓、 4,4’-二經基二苯基硫化物、芴雙苯酚、4,4，_聯苯、 3,3，5,5’ -四甲基_4,4’-二羥基聯苯、2,2’-聯苯、間苯二酚 、鄰苯二酚、1-丁基鄰苯二酚、t-丁基氫醌、1,2-二羥基 萘、1，3-二羥基萘、丨，4_二羥基萘、I〗·二羥基萘、丨，6-二 羥基萘、丨，7·二羥基萘、1,8-二羥基萘、2,3-二羥基萘、 2,4-二羥基萘、2,5_二羥基萘、2,6_二羥基萘、2,7_二羥基 蔡、2,8 -二羥基萘、上述二羥基萘之烯丙基化合物或聚儲 -11 - 201002752 丙基化合物、烯丙基化雙酚A、烯丙基化雙酚F、烯丙基 化苯酚酚醛清漆等之2價苯酚類、或者苯酣酌醒清漆、雙 酚A酚醛清漆、〇-甲酚酚醛清漆、m-甲酿酣醒清漆、p甲 酚酚醛清漆、二甲苯酚酚醛清漆 '聚-P-羥基苯乙嫌、二· (4·羥基苯基）甲烷、1,1，2,2 -四（4_羥基苯基）乙院、 氟甘氨醇、焦掊酚、t_丁基焦掊酣、烯丙基化焦掊酚、聚 烯丙基化焦桔酚、1，2,4-苯三醇、2,3,4-三羥基二苯甲酮、 苯酚芳烷樹脂、萘酚芳烷樹脂、二環戊二烯系樹脂等之3 價以上之苯酚類，或者四溴雙酚A等之由鹵化雙酚類所 衍生之環氧丙基醚化物等。此等之其他環氧樹脂，可以1 種單獨或2種以上混合使用皆可。 本發明之環氧樹脂組成物，如將一般式（1 )所示之 二苯甲酮系環氧樹脂之環氧樹脂組成物中之配合比例，控 制在環氧樹脂樹脂成分中之5 Owt %以上時，亦可含有別 種之環氧樹脂’惟基於作成硬化物時之熱傳導率提升之觀 點’一官能性之環氧樹脂之合計量’—般係8 0 w t %以上 ，較佳則爲90wt%以上者爲理想。 一本甲酮系環氧樹脂以外之其他環氧樹脂，其最佳之 環氧樹脂，係下述一般式（3)所示之雙酚系環氧樹脂。 【化3】The benzophenone-based epoxy resin represented by the general formula (1) may be appropriately selected depending on the application. For example, in the case of semiconductor encapsulation, 'because there are many powders, it is better to be crystalline at room temperature, and the melting point is above 80 °C, and 15 0 °C -10- 201002752 The melt viscosity is 0.005 to 〇·2 Pa· s is ideal. Further, in the use of a laminate or the like, since many of them are dissolved in a solvent and used by the user, the form of the epoxy resin is not particularly limited. The purity of the epoxy resin used in the present invention, particularly the amount of hydrolyzable chlorine, is preferably based on the improvement of the reliability of the electronic component to be applied. Although it is not particularly limited, it is preferably less than i 00 ppm or less than the optimum of 500 ppm. Further, the term "hydrolyzable chlorine" as used in the present invention means a method measured by the following method. That is, after the sample 〇. 5 g was dissolved in dioxane 30 mi, added ιν-ΚΟΗ 10 m b and then boiled for 30 minutes, then cooled to room temperature, and further added 100 ml of acetone water 100 ml, 〇.〇〇2 N_AgN〇3 aqueous solution was subjected to potentiometric titration. In the epoxy resin composition of the present invention, in addition to the benzophenone-based epoxy resin represented by the general formula (1) which is an essential component used in the present invention, it may be used in combination with two or more epoxy groups in the molecule. Other epoxy resins. For example, 'has a bismuth A, 4, 4, _ dihydroxydiphenylmethane, 3,3,, 5,5, tetramethyl-4,4'-di-diphenyldiphenylmethane, 4,4 , _ dihydroxydiphenyl maple, 4,4'-di-diphenyldiphenyl sulfide, quinone diphenol, 4,4,-biphenyl, 3,3,5,5'-tetramethyl-4, 4'-dihydroxybiphenyl, 2,2'-biphenyl, resorcinol, catechol, 1-butyl catechol, t-butylhydroquinone, 1,2-dihydroxynaphthalene, 1,3-Dihydroxynaphthalene, anthracene, 4-dihydroxynaphthalene, I-dihydroxynaphthalene, anthracene, 6-dihydroxynaphthalene, anthracene, 7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3 -dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxycaline, 2,8-dihydroxynaphthalene, the above dihydroxynaphthalene Allyl compound or poly storage-11 - 201002752 Divalent compound, allylated bisphenol A, allylated bisphenol F, allylated phenol novolac, etc. Varnish, bisphenol A novolac, bismuth-cresol novolac, m-a brewing varnish, p-cresol novolac, xylenol novolac lacquer poly-P-hydroxybenzene, bis (4·hydroxyl) benzene Methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)benzamine, fluoroglycolol, pyrogallol, t_butyl eschar, allylated pyrophenol, polyallyl Carrageenan, 1,2,4-benzenetriol, 2,3,4-trihydroxybenzophenone, phenol aralkyl resin, naphthol aralkyl resin, dicyclopentadiene resin, etc. A phenol such as a phenol or a epoxidized propyl ether derived from a halogenated bisphenol such as tetrabromobisphenol A. These other epoxy resins may be used alone or in combination of two or more. The epoxy resin composition of the present invention, such as the blending ratio of the epoxy resin composition of the benzophenone epoxy resin represented by the general formula (1), is controlled to 5 Owt% in the epoxy resin resin component. In the above, an epoxy resin of another type may be contained. The viewpoint of the improvement of the thermal conductivity when the cured product is formed is 'the total amount of the epoxy resin of the one-functionality', generally 80% by weight or more, preferably 90% by weight. The above are ideal. The epoxy resin which is the best epoxy resin other than the ketone-based epoxy resin is a bisphenol-based epoxy resin represented by the following general formula (3). [化3]
-12- (3) 201002752 (惟’ Rl〜R3爲鹵原子、碳數1〜8之烴基或碳數1〜8 之^氧基’功爲〇〜5之數，X爲單鍵、伸甲基、氧原子 、磺酸基或硫原子。） 上述雙酚系環氧樹脂，可以4,4，-二羥基聯苯、 3,3’，5,5’-四甲基_4,4，·二羥基聯苯、4,4’_二羥基二苯基申 院、3,3’，5,5、四甲基_4,4，_二羥基二苯基甲烷、4,4，_二殘 基一苯基酸、4,4’_二羥基二苯基硫化物做爲原料，再進行 一般的環氧化反應而合成。此等之環氧樹脂，可在原料階 段使用與4,4，_二羥基二苯甲酮之混合物，然後進行合成 。此等之中’又以由 4,4，_二羥基聯苯、4,4，_二羥基二苯 基甲院、4,4’-二羥基二苯基醚所合成之環氧樹脂爲最佳， 其等除了能賦予具有優良處理性之結晶性之環氧樹脂外， 亦能提供優良熱傳導性之成形物。 本發明之環氧樹脂組成物，其必要成分，係使用上述 一般式（2 )所示之二苯甲酮系苯酚性樹脂作爲硬化劑。 在此’上述二苯甲酮系苯酚性樹脂，其較佳係m爲0之 4,4’-二羥基二苯甲酮。 此外’如將本發明之環氧樹脂組成物作爲層合材料用 之預浸漬物加以應用時，在上述一般式（2)中，係以平 均値係m較0爲大之二苯甲酮系苯酚性樹脂爲較佳使用 者。此時之較佳m値係平均値爲1〜1 5，最佳則爲2〜1 5 者。再者’ m數爲增加之二苯甲酮系苯酚性樹脂之製法， 並無特別之限制’惟例如有對於上述一般式（1 )所示之 -13- 201002752 二苯甲酮系環氧樹脂，使與過剩量之4,4’-二羥基二苯甲 酮進行反應之方法。或者，對於4,4’-二羥基二苯甲酮與 4,4，-二羥基二苯甲酮中之羥基1莫爾，藉由使1莫爾以下 之環氧氯丙烷進行反應而合成。 一般式（2 )所示之二苯甲酮系苯酚性樹脂之羥基當 量，一般係100至20,000之範圍，惟亦可與環氧樹脂相 同地，適當之羥基當量可根據用途而適宜地加以選擇。舉 例而言，在半導體封閉之用途上，基於無機塡充劑之高塡 充率化及流動性提升之觀點，其係以低黏度性者爲較佳， 且在上述一般式（2)中，則以m=0體爲主成分之羥基 當量在100至200之範圍者爲較佳。此外，在層合板等之 用途中，基於賦予薄膜性、可撓性之觀點，係以200〜 2 0,0 00之範圍爲較佳。該羥基當量，即使在使用2種類以 上之環氧樹脂時，亦以能滿足此條件者爲較佳，此時，該 羥基當量，可以全重量（g )/羥基（莫爾）而計算得到。 本發明之環氧樹脂組成物所用之硬化劑，除本發明必 要成分之一般式（2)所示之二苯甲酮系苯酚性樹脂以外 ，一般而言，可根據需要將已知之環氧樹脂硬化劑加以組 合，較佳則可選擇具有苯酚性羥基之其他苯酚系硬化劑。 其他苯酚系硬化劑，其具體例子有：雙酚A、雙酚F、 4,4’-二羥基二苯基醚' 1,4-雙（4-羥基苯氧基）苯、1，3-雙（4-羥基苯氧基）苯、4,4’-二羥基二苯基硫化物、4,4，-二羥基二苯基酮、4,4’-二羥基二苯基颯、4,4’-二羥基二 苯基聯苯、2,2’-二羥基聯苯、ι〇-(2,5-二羥基苯基）_ -14- 201002752 10H-9-氧雜-10-磷染菲-i〇-氧化物、苯酚酚醛清漆、雙酚 A酚醛清漆、〇 -甲酚酚醛清漆、m -甲酚酚醛清漆、p -甲酚 酚醛清漆、二甲苯酚酚醛清漆、聚-p_羥基苯乙烯、氫醌 、間苯二酚、鄰苯二酚、t-丁基鄰苯二酚、t-丁基氫醌、 氟甘氨醇、焦掊酚、t-丁基焦桔酚、烯丙基化焦掊酚、聚 烯丙基化焦掊酚' 1,2,4-苯三醇、2,3,4-三羥基二苯甲酮、 1,2-二羥基萘、1,3-二羥基萘、1,4-二羥基萘、1,5-二羥基 萘、1，6-二羥基萘、1,7-二羥基萘、1,8-二羥基萘、2,3-二 羥基萘、2,4-二羥基萘、2,5-二羥基萘、2,6-二羥基萘、 2,7-二羥基萘、2,8-二羥基萘、上述二羥基萘之烯丙基化 合物或聚烯丙基化合物、烯丙基化雙酚A、烯丙基化雙酚 F、烯丙基化苯酚酚醛清漆、烯丙基化焦掊酚等。 本發明之環氧樹脂組成物中，一般式（2 )所示之二 苯甲酮系苯酚性樹脂之配合比例如係硬化劑成分中之 5 〇 wt %以上時，亦可含有別種之苯酚性化合物（樹脂）’ 惟基於作成硬化物時之熱傳導率提升之觀點’其二官能性 之苯酚性化合物（樹脂）之合計量’係以80wt %以上爲 較佳，並以90wt%以上爲最佳。 在二苯甲酮系苯酚性樹脂以外之其他苯酚性化合物（ 樹脂），其最佳者’具體而言例如有：4,4’_二經基聯苯' 4,4，-二羥基二苯基甲烷' 4,4’-二羥基二苯基醚、1，4-雙（ 4-羥基苯氧基）苯、4,4，-二羥基二苯基硫化物、1，5_萘二 醇、2,7 -萘二醇、2，6 -萘二醇。此等二官能性之苯酣性化 合物或苯酚性樹脂之使用量’一般係硬化劑成分中之 -15- 201002752 50wt%以下，惟較佳係20wt%以下者。 本發明之環氧樹脂組成物所使用之硬化劑’除上述苯 酚系硬化劑以外，尙可倂用一般習知作爲硬化劑之其他硬 化劑。例如有：胺系硬化劑、酸酐系硬化劑、苯酚系硬化 劑、聚硫醇系硬化劑、聚胺基醯胺系硬化劑、異氰酸酯系 硬化劑、嵌段異氰酸酯系硬化劑等。此等硬化劑之配合量 ，可考慮所配合之硬化劑之種類或可得到之熱傳導性環氧 樹脂成形體之物性，而適當地加以設定。 胺系硬化劑之具體例子，例如有脂肪族胺類、聚醚聚 胺類、脂環式胺類、芳香族胺類等。脂肪族胺類，例如有 伸乙基二胺、1,3 -二胺基丙院、1,4 -二胺基丙院、六伸甲 基二胺、2,5 -二甲基六伸甲基二胺、三甲基六伸甲基二胺 、二伸乙基三胺基、亞胺基雙丙基胺、雙（六伸甲基）三 胺、三伸乙基四胺、四伸乙基五胺、五伸乙基六胺、N-經 基乙基伸乙基二胺、四（羥基乙基）伸乙基二胺等。聚醚 聚胺類，例如有三乙二醇二胺、四乙二醇二胺、二乙二醇 雙（丙基胺）、聚氧基伸丙基二胺 '聚氧基伸丙基三胺等 。脂環式胺類，例如有異佛爾酮二胺、二環戊二烯二胺、 N-胺基乙基哌嗪、雙（4-胺基-3-甲基二環己基）甲院、 雙（胺基甲基）環己烷、3,9-雙（3-胺基丙基）〇· 四氧雜螺旋（5,5) --垸、原菠烯二胺等。芳香族胺類 ’例如有四氯-p-苯二甲基二胺、ni -苯二甲基二胺、p_苯 —甲基二胺、m -伸苯基二胺、〇 -伸苯基二胺、p_伸苯基二 胺、2,4-二胺基茴香醚、2,4-甲苯二胺、2,4_二胺基二苯 -16- 201002752 基甲烷、4,4’-二胺基二苯基甲烷、4,4’-二胺基-1,2-二苯 基乙烷、2,4-二胺基二苯基颯、4，4’-二胺基二苯基砸、m-胺基苯酚、m-胺基苄基胺、苄基二甲基胺、2-二甲基胺基 甲基苯酣、三乙醇胺、甲基节基胺、a-(m-胺基苯基） 乙基胺' ct-(p -胺基苯基）乙基胺、二胺基二乙基二甲 基二苯基甲烷' 雙（4-胺基苯基）-P-二異丙基苯 等。 酸酐系硬化劑之具體例子，例如有十二碳烯琥珀酸酐 、聚已二酸酐、聚壬二酸酐、聚癸二酸酐、聚（甲基十八 烷二酸）酐、聚（苯基十六烷二酸）酐、甲基四氫苯二酸 酐、甲基六氫苯二酸酐、六氫苯二酸酐、甲基-5-降冰片 烯-2,3-二羧酸酐、四氫苯二酸酐、三烷基四氫苯二酸酐、 甲基環己烯二羧酸酐、甲基環己烯四羧酸酐、苯二酸酐、 三苯六甲酸酐、均苯四甲酸酐、二苯甲酮四羧酸酐、乙二 醇雙偏苯三酸酯、氯橋酸酐、耐地酸酐、甲基耐地酸酐、 5- ( 2，5-二氧基四氫-3-呋喃基）-3-甲基-3-環己烷-1,2-二 羧酸酐、3,4-二羧基-1，2,3,4-四氫-1-萘琥珀酸二酐、1-甲 基-二羧基-1,2,3,4-四氫-1-萘琥珀酸二酐等。 本發明之環氧樹脂組成物，其環氧樹脂及硬化劑之配 合比率，係環氧基與硬化劑中之官能基之當量比爲0.8〜 1_5的範圍。在此範圍外時，其硬化後亦有未反應之環氧 基或硬化劑中之官能基殘留，且其作爲電氣絕緣材料之信 賴性降低之故而不理想。 本發明之環氧樹脂組成物中，亦可添加無機塡充材料 -17- 201002752 。無機塡充材料之添加量，相對於環氧樹 係 50〜95wt%，惟較佳係 80〜95wt%。 將無法充分地發揮高熱傳導性、低熱膨脹 之效果。此等之效果，係以無機塡充材料 並不會因應其體積分率而提高，反而是從 始而有大幅提升之情形。此等之物性，考 子狀態下之高次構造受控制之效果所導致 次構造主要係於無機塡充材料表面達成之 定量之無機塡充材料。另一方面，如無機 量較此爲多時，其黏度會變高，或成形性 〇 無機塡充材料係以球狀者爲較佳，在 亦包含之情況下，只要是球狀者，並無特 於流動性改善之觀點，其係以儘可能接近 佳。藉此’就能谷易地獲得面心立方構造 等之最密塡充構造，並取得充分之塡充量 形，在將塡充量增加時，塡充劑間之摩擦 達到上述之上限前’其流動性會極度地降 ，且成形性會惡化之故，因此並不理想。 基於熱傳導率提升之觀點，在無機塡 係以使用熱傳導率在5 W/m · K以上之 5 〇 w t %以上者爲較佳，並以使用氧化銘、 氧化矽等爲理想。此等之中最佳者，係球 ’亦可根據需要’而倂用與形狀無關係之 脂組成物，一般 如較此爲少時， 性、高耐熱性等 越多者爲佳，惟 特定之添加量開 慮是因爲在高分 者，而由於此高 故，因此必須特 塡充材料之添加 會惡化而不理想 橫斷面爲橢圓者 別之限制，惟基 於真球狀者爲較 或六方緻密構造 。如非球形之情 會增加，從而在 低，黏度會變高 充材料之中，其 無機塡充材料爲 氮化鋁、結晶二 狀氧化鋁。此外 無定形無機塡充 -18- 201002752 材料，例如溶融二氧化矽、結晶二氧化矽等 無機塡充材料之平均粒徑，係以30 μ 佳。平均粒徑如較此爲大時，環氧樹脂組成 受損，且強度亦會降低之故而不理想。 此外，無機塡充材料，亦可倂用玻璃纖 基材、或纖維狀基材與粒子狀無機塡充材料 纖維狀基材進行複合時，該使用溶劑之清漆 於薄片狀之纖維狀基材，進行乾燥，然後作 浸漬體。如此所作成之預浸漬體，可藉由與 不銹鋼箔等之金屬基材、聚對苯二甲酸乙二 二甲酸丁二醇酯、聚乙烯萘二甲酸酯 '液晶 胺、聚醯亞胺、鐵氟龍等之高分子基材進行 加熱成形，而應用於印刷電路板、放熱基板 本發明之環氧樹脂組成物中，亦可使用 硬化促進劑。舉例而言，有胺類、咪唑類、 易士酸等，具體上’例如1,8-二氮雜雙環 烯-7、三伸乙烯二胺、苄基二甲基胺、三乙 胺基乙醇 '三（二甲基胺基甲基）苯酚等之 基咪唑、2-苯基咪唑、2-苯基_4_甲基咪唑、 嗤等之味哇類 '三丁基鱗、甲基二苯基膦、 苯基膦、苯基膦等之有機膦類、四苯基錢· 、四苯基錢•乙基三苯基硼酸鹽、四丁基錢 鹽等之四取代辚•四取代硼酸鹽、2 -乙基-四苯基硼酸鹽、Ν-甲基嗎啉·四苯基硼酸鹽 m以下者爲較 物之流動性會 維等之纖維狀 者。如使其與 ，例如可含浸 成本發明之預 銅箔、鋁箔、 醇酯、聚對苯 聚合物、聚醯 層合，並使其 等。 傳統上已知之 有機膦類、路 (5,4,0 )十一 醇胺、二甲基 .三級胺、2-甲 2-十七烷基咪 三苯基膦、二 四苯基硼酸鹽 •四丁基硼酸 4 -甲基咪唑· 等之四苯基硼 -19- 201002752 酸鹽等。一般而言’添加量’相對於環氧樹脂100重量份 ，係0.2〜10重量份之範圍。此等可以單獨使用，亦可以 倂用。 上述硬化觸媒之添加量，相對於環氧樹脂（包含作爲 難燃劑之含鹵環氧樹脂）及硬化劑之合計，係以0. 1〜 10·0質量％爲較佳。如未達0.1質量％時，其成形時間會 變長，且因成形時之剛性降低會導致其作業性降低；相反 地，如超過1〇·〇質量％時，在成形過程中會發生硬化， 而容易發生未塡充之情形。 本發明之環氧樹脂組成物中，可使用在環氧樹脂組成 物中一般作爲離型劑使用之蠟。蠟，例如有硬脂酸、二十 八碳酸、二十八碳酸酯、磷酸酯等。 本發明之環氧樹脂組成物中，爲使無機塡充材料與樹 脂成分之接著力能提升起見，可使用在環氧樹脂組成物中 一般使用之偶合劑。偶合劑，例如可使用環氧基矽烷。偶 合劑之添加量，相對於環氧樹脂組成物，係以0.1〜2.0 質量％爲較佳。如未達0.1質量％時，樹脂與基材之配合 會變差，成形性也會變差，相反地，如超過2.0質量％時 ，在連續成形性上會發生成形品污染等情形。 又本發明之環氧樹脂組成物中，基於成形時之流動性 改良及導線架等之與基材之密接性提升之觀點，可添加熱 可塑性之低聚物類。熱可塑性之低聚物類，例如有C5系 及C9系之石油樹脂、苯乙烯樹脂、茚樹脂、茚·苯乙烯 共聚樹脂 '節•苯乙燦·苯酌共聚樹脂、節•香豆酮共聚 -20- 201002752 樹脂、茚·苯倂噻吩共聚樹脂等。添加量，一般相對於環 氧樹脂100重量份，係2〜30重量份之範圍。 進而’本發明之環氧樹脂組成物，可適當地使用一般 在環氧樹脂組成物中可使用者。舉例而言，有磷系難燃劑 、溴化合物或三氧化銻等之難燃劑、以及碳黑或有機染料 等之著色劑等。 本發明之環氧樹脂組成物，可將環氧樹脂、硬化劑、 無機塡充材料、及偶合劑以外之其他成分，藉由混合器進 行均一地混合之後，添加偶合劑，再以加熱滚輥、捏和機 等進行混練而製造。此等成分之配合順序，並無特別之限 制。進一步，亦可於混練後進行溶融混練物之磨碎，而使 其粉末化或錠劑化。本發明之環氧樹脂組成物，係以環氧 樹脂及硬化劑作爲樹脂成分之主成分。其較佳係60 wt % 以上’最佳係80wt%以上，爲環氧樹脂及硬化劑者。 本發明之環氧樹脂組成物，其作爲電氣絕緣材料係有 用，尤其適合在半導體裝置作爲封閉用者。 爲使用本發明之環氧樹脂組成物而製得成形物起見， 例如可適用傳遞成形、加壓成形、注型成形、射出成形、 擠壓成形等方法，惟基於量產性之觀點，係以傳遞成形爲 較佳。在該成形時，可進行加熱，而產生硬化（聚合）。 因此，所得到之成形物因爲係聚合樹脂（熱可塑性或熱硬 化性樹脂）之成形物之故，亦稱爲硬化成形物。從而，在 本說明書所謂之硬化，亦係包含聚合之意，而硬化樹脂係 包含熱可塑性樹脂者。 -21 - 201002752 本發明之成形物，其一般係作成三次元交聯者，惟未 必須要是三次元交聯體，亦可爲由熱可塑性之二次元高分 子所成之成形物。其中，尤其是使二官能性環氧樹脂與二 官能性硬化劑發生反應時，一般可藉由在環氧基之開環反 應所生成之二級羥基進一步與環氧基反應而成爲三次元交 聯體，惟可藉由選擇硬化條件而成爲熱可塑性之二次元高 分子成形體。基於高熱傳導性之觀點，係以成爲結晶性之 成形物爲較佳，惟一般而言，由於三次元交聯體會阻礙結 晶性之故，因此以減少交聯且二次元高分子作爲主體之成 形體爲較佳。成形體之結晶性之表現，可藉由：在示差掃 描熱分析下，伴隨著結晶融解的吸熱峰部，將其作爲融點 ，加以觀測而確認。通常，融點範圍係120°C至320 °C， 較佳係150°C至300°C，最佳係200°C至280°C之範圍。 本發明之成形物之結晶化度，係以越高者爲佳，可由 示差掃描熱分析下，伴隨著結晶之融解的吸熱量，加以評 價。一般而言，吸熱量係扣除塡充材料之樹脂成分的每單 位重量爲5 J/g以上，較佳之吸熱量則爲10】/g以上··更 佳爲20 J/g以上，最佳爲30 J/g以上者。如較此爲小時 ，其作爲環氧樹脂成形物之熱傳導率提升效果就小。此外 ，基於低熱膨脹性及耐熱性提升之觀點，亦以結晶性越高 者爲較佳。此外，在此所謂之吸熱量，係指藉由示差熱分 析計，使用精坪約1 〇 m g之樣品，而在氮氣氣流下以升溫 速度1 〇°c /分之條件加以測定所得到之吸熱量。 本發明之成形物，可藉由以上述成形方法使其加熱成 -22- 201002752 形而得到，惟一般而言，成形溫度係由8 0 °C至2 5 0 t：，且 爲提高其成形物之結晶化度，係以在較成形物之融點爲低 之溫度成形者爲較佳。較佳之成形溫度係l〇(TC至220 °C 之範圍，最佳則係1 5 0 °C至2 0 0 °C者。此外，較佳之成形 時間係3 0秒至1小時，最佳之成形時間係1分至3 〇分。 進一步，在成形後，可藉由後固化，而提升其結晶化度。 通常該後固化溫度係1 3 0 °C至2 5 0 °C，時間則係1小時至 20小時之範圍，惟較佳者，係以在示差熱分析下較吸熱 峰部之溫度低5 °C至4 0 °C之溫度下，以1小時至2 4小時 進行後固化者爲理想。此外，成形物之較佳熱傳導率係4 W/m · K以上，最佳則係6 W/m · K以上者。 實施例 以下，茲依實施例進一步具體說明本發明。 參考例1 將4,4，-二羥基二苯甲酮1 070 g溶解於環氧氯丙烷 65 00 g中’並於60°c減壓下（約130 Torr)，以4小時 將4 8 %氫氧化鈉水溶液8 〇 8 g滴下。其間，所生成之水係 藉由與環氧氯丙烷之共沸而排出系外’所餾出之環氧氯丙 院則回歸系內。滴下結束後，進一步繼續反應1小時脫水 後’餾去環氧氯丙烷，再加入甲基異丁酮3 500 g後，進 行水洗而除去鹽。其後，於8 〇 t：下添加2 0 %氫氧化鈉 1〇〇 g ’攪拌2小時，並以溫水1 00 0 mL進行水洗。然後 -23- 201002752 ，利用分液將水除去’再減壓餾去甲基異丁酮’而製得淡 黃色結晶狀之環氧樹脂1 460 g (環氧樹脂A )。 環氧樹脂A以毛細管法所測得之融點係1 2 8 °C至1 3 1 。(：，而在150°C下之黏度則爲。環氧當量係 1 79，加水分解性氯爲270 ppm ’所得到之樹脂以GPC測 定所求出之一般式（1)下之各成分比’當n=〇時爲91.0 %，而當η = 1時爲8.2 %。在此’所謂加水分解性氯’係 指將樣品〇·5 g溶解於二噁烷30 ml後’加入10 ml之 1 N - Κ Ο Η，煮沸還流3 0分鐘後，冷卻至室溫，進一步再力口 入80%丙酮水100 ml後，對其藉由0.002 N-AgN03水溶 液進行電位差滴定所測定之値。又所謂融點，係指藉由毛 細管法以升溫速度2 °C /分所得到之値。黏度係以BROOK FIELD製，在CAP2000H下測定，而軟化點貝lj根據 JIS K-691 1以環球法加以測定。此外，GPC測定，係根據 :裝置爲日本 waters (股）製 515A型，管柱爲 TSK-GEL2000 X 3管及 T S K - G E L 4 0 0 0 x 1 管（不論何者均爲 TOSOH (股）製），溶劑爲四氫呋喃，流量爲lml/min， 溫度爲3 8 °C，檢測器爲RI，等條件所進行者。 實施例1〜6、比較例1〜5 環氧樹脂成分係使用參考例1之環氧樹脂（環氧樹脂 A) 、4,4’-二羥基二苯基醚之環氧化物（環氧樹脂B:東 都化成製’ YSLV-80DE ’環氧當量174)、或聯苯系環氧 樹脂（環氧樹脂C :日本環氧樹脂製，YX-4000H，環氧 -24- 201002752 當量195 )，而硬化劑則使用4,4’-二羥基二二苯 化劑A ) 、4,4’-二羥基二苯基醚（硬化劑B)、 基二苯基甲烷（硬化劑C) 、4，4’-二羥基二二苯 化劑D )或苯酚酚醛清漆（硬化劑E :群榮化學 4261’ OH當量103，軟化點82°C )。此外，硬 使用三苯基膦，無機塡充材料則使用球狀氧化鋁 徑1 2.2 # m )。配合表1所示之成分，並以混合 混合後’另以加熱滾輥混練約5分鐘後冷卻，再 自得到實施例1〜6、比較例1〜5之環氧樹脂組 用該環氧樹脂組成物，以表1所示條件進行成形 ，而評價其成形物之物性。 整理其結果，並不於表1及表2中。此外， 配合物之數字係重量份。再者，評價則依據以下 (1)熱傳導率：使用NETZSCH製LFA447 率計，利用非定常熱線法進行測定。 (2 )融點、融解熱之測定（DSC法）：使 描熱量分析裝置（精工儀器製DSC6200型）， 速度l〇°C /分加以測定。 (3 )線膨脹係數、玻璃態化溫度：使用精 股）製TMA120C型熱機械測定裝置，再以升溫: /分加以測定。 (4 )吸水率：使直徑5〇 mrn、厚度3 mm 形’在後硬化之後，以8 5 °C、相對濕度8 5 %之 其吸濕1 〇 〇小時後，測其重量變化率。 甲酮（硬 4,4，-二羥 甲酮（硬 製，PSM-化促進劑 (平均粒 器充分地 磨碎而各 成物。使 及後硬化 表中之各 行之。 型熱傳導 用不差掃 再以升溫 工儀器（ 速度1 0 °c 之圓盤成 條件，使 -25- 201002752 [表l] 實施例 1 2 3 4 5 6 環氧樹脂A 94.0 85.5 78.0 94.0 94.5 94.5 環氧樹脂B 8.5 15.5 硬化劑A 56.0 56.0 56.5 51.0 46.5 50.5 硬化劑C 5.0 9.0 硬化劑D 5.0 無機塡充材料A 1350 1350 1350 1350 1350 1350 硬化促進劑 1.6 1.6 1.6 1.6 1.6 1.6 玻璃態化溫度(。。） 132 123 121 122 119 131 熱膨脹係數(ppm,<Tg) 8.4 8.6 8.7 8.6 8.7 8.6 熱膨脹係數(ppm，<Tg) 27.9 33.0 34.5 32.4 37.0 29.5 熱變形溫度(TC ) 240 211 203 219 199 231 吸水率(wt%，100h) 0.12 0.14 0.16 0.14 0.15 0.13 熱傳導率(W/nvK) 5.33 4.87 4.43 4.98 4.68 5.29 融點(C ) 226.0 209.0 198.0 211.0 196.0 225.0 融解熱(J/g-樹脂） 53 28 21 33 27 43 -26- 201002752 [表2] 比較例 1 2 3 4 5 6 環氧樹脂A 96.0 96.0 42.5 31.0 環氧樹脂B 51.0 62.0 93.0 環氧樹脂C 97.0 硬化劑A 56.5 57.0 57.0 53.0 硬化劑B 54.0 硬化劑C 54.0 無機塡充材料A 1350 1350 1350 1350 1350 1350 硬化促進劑 1.6 1.6 1.6 1.6 1.6 1.6 玻璃態化溫度fc ) 113 111 112 107 116 119 熱膨脹係數(ppm,<Tg) 10.5 11.4 11.5 12.0 11.4 11.7 熱膨脹係數(ppm，<Tg) 44.7 48.5 46.2 43.8 44.1 46.5 熱變形溫度(°C ) 122 121 117 115 124 126 吸水率(wt%，l〇〇h) 0.27 0.26 0.26 0.27 0.25 0.22 熱傳導率(W/m.K) 3.75 3.56 3.94 3.87 3.74 3.35 融點(°C ) - 融解熱(J/g-樹脂） - - - • _ 產業上可利用性 本發明之環氧樹脂組成物 且爲可賦予高熱傳導性、低吸 性之優良硬化成形物，並適合 、放熱基板等之電氣•電子零 良之高放熱性及尺寸安定性者 ’其成形性、信賴性優良， 水性、低熱膨脹性、高耐熱 應用於半導體封閉、層合板 件用絕緣材料，而可發揮優 -27--12- (3) 201002752 (However, 'Rl~R3 is a halogen atom, a hydrocarbon group having a carbon number of 1 to 8 or an oxy group having a carbon number of 1 to 8 is a number of 〇~5, and X is a single bond and a nail. a base, an oxygen atom, a sulfonic acid group or a sulfur atom.) The above bisphenol epoxy resin may be 4,4,-dihydroxybiphenyl, 3,3',5,5'-tetramethyl-4,4, · Dihydroxybiphenyl, 4,4'-dihydroxydiphenyl, 3,3',5,5, tetramethyl-4,4,-dihydroxydiphenylmethane, 4,4,_2 The residue monophenyl acid and 4,4'-dihydroxydiphenyl sulfide are used as a raw material, and then subjected to a general epoxidation reaction to synthesize. These epoxy resins can be used in the raw material stage in a mixture with 4,4,-dihydroxybenzophenone and then synthesized. Among these, the epoxy resin synthesized by 4,4,-dihydroxybiphenyl, 4,4,-dihydroxydiphenylmethyl and 4,4'-dihydroxydiphenyl ether is the most Preferably, in addition to the epoxy resin which imparts excellent crystallinity, it can also provide a molded article excellent in thermal conductivity. In the epoxy resin composition of the present invention, a benzophenone-based phenol resin represented by the above general formula (2) is used as a curing agent. Here, the above benzophenone-based phenol resin is preferably a 4,4'-dihydroxybenzophenone. Further, when the epoxy resin composition of the present invention is used as a prepreg for a laminate, in the above general formula (2), a benzophenone having an average lanthanum m of 0 is used. Phenolic resins are preferred users. In this case, the average m値 is 1 to 15 5, and the best is 2 to 15. Further, the method of producing a benzophenone-based phenol resin having an increased m number is not particularly limited. For example, there is a benzophenone-based epoxy resin as shown in the above general formula (1)-13-201002752. A method of reacting with an excess amount of 4,4'-dihydroxybenzophenone. Alternatively, 4,4'-dihydroxybenzophenone and hydroxy 1 mole in 4,4,-dihydroxybenzophenone are synthesized by reacting epichlorohydrin of 1 mole or less. The hydroxyl equivalent of the benzophenone-based phenol resin represented by the general formula (2) is generally in the range of 100 to 20,000, but may be appropriately selected according to the use, as well as the epoxy resin. . For example, in the use of semiconductor encapsulation, based on the high enthalpy of the inorganic chelating agent and the improvement of the fluidity, it is preferred to have a low viscosity, and in the above general formula (2), Further, it is preferred that the hydroxyl group equivalent of the m=0 body as a main component is in the range of 100 to 200. Further, in the use of a laminate or the like, it is preferably in the range of 200 to 20, 000 based on the viewpoint of imparting film properties and flexibility. The hydroxyl equivalent is preferably one in which two or more kinds of epoxy resins are used. In this case, the hydroxyl equivalent can be calculated by the total weight (g) / hydroxyl group (mole). The hardener used in the epoxy resin composition of the present invention, in addition to the benzophenone-based phenol resin represented by the general formula (2) of the essential component of the present invention, generally, a known epoxy resin can be used as needed. The hardener is preferably combined with another phenolic hardener having a phenolic hydroxyl group. Other phenolic hardeners, specific examples thereof are: bisphenol A, bisphenol F, 4,4'-dihydroxydiphenyl ether '1,4-bis(4-hydroxyphenoxy)benzene, 1,3- Bis(4-hydroxyphenoxy)benzene, 4,4'-dihydroxydiphenyl sulfide, 4,4,-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl fluorene, 4, 4'-Dihydroxydiphenylbiphenyl, 2,2'-dihydroxybiphenyl, ι〇-(2,5-dihydroxyphenyl)_ -14- 201002752 10H-9-oxa-10-phosphor dyed Phenanthrene-oxide, phenol novolac, bisphenol A novolac, cresol-cresol novolac, m-cresol novolac, p-cresol novolac, xylenol novolac, poly-p-hydroxyl Styrene, hydroquinone, resorcinol, catechol, t-butyl catechol, t-butylhydroquinone, fluoroglycolol, pyrogallol, t-butyl pyrophenol, alkene Propylated pyrophenol, polyallyylated pyrophenol phenol 1,2,4-benzenetriol, 2,3,4-trihydroxybenzophenone, 1,2-dihydroxynaphthalene, 1,3 -dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-di Hydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5- Hydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxynaphthalene, allyl compound of the above dihydroxynaphthalene or polyallyl compound, allylated bisphenol A , allylated bisphenol F, allylated phenol novolac, allylated pyrophenol, and the like. In the epoxy resin composition of the present invention, when the compounding ratio of the benzophenone-based phenol resin represented by the general formula (2) is, for example, 5 〇wt% or more of the hardener component, it may contain other phenolic properties. The compound (resin) is based on the viewpoint of the improvement of the thermal conductivity when the cured product is formed. The total amount of the difunctional phenolic compound (resin) is preferably 80% by weight or more, and preferably 90% by weight or more. . The other phenolic compound (resin) other than the benzophenone-based phenol resin is, for example, specifically: 4,4'-di-diphenylbiphenyl 4,4,-dihydroxydiphenyl Methane '4,4'-dihydroxydiphenyl ether, 1,4-bis(4-hydroxyphenoxy)benzene, 4,4,-dihydroxydiphenyl sulfide, 1,5-naphthenediol 2,7-naphthalenediol, 2,6-naphthalenediol. The amount of the difunctional benzoquinone compound or phenol resin used is generally -15 - 201002752 50 wt% or less of the hardener component, but preferably 20 wt% or less. The curing agent used in the epoxy resin composition of the present invention is other than the above-mentioned phenol-based curing agent, and other hardening agents conventionally known as curing agents can be used. For example, an amine-based curing agent, an acid anhydride-based curing agent, a phenol-based curing agent, a polythiol-based curing agent, a polyamine-based amide-based curing agent, an isocyanate-based curing agent, and a blocked isocyanate-based curing agent may be used. The blending amount of these hardeners can be appropriately set in consideration of the kind of the hardener to be blended or the physical properties of the heat conductive epoxy resin molded body which can be obtained. Specific examples of the amine-based curing agent include aliphatic amines, polyether polyamines, alicyclic amines, and aromatic amines. Aliphatic amines, for example, ethylidene diamine, 1,3 -diaminopropyl, 1,4 -diaminopropyl, hexamethylenediamine, 2,5-dimethylhexamethyl Diamine, trimethylhexamethylenediamine, diethylidene triamine, imidodipropylamine, bis(hexamethylene)triamine, triethylidenetetraamine, tetrazide Pentylamine, pentaerythritol hexamine, N-methylethylethylidene diamine, tetrakis(hydroxyethyl)ethylidene diamine, and the like. The polyether polyamines are, for example, triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis (propylamine), polyoxypropylene diamine 'polyoxypropyl propyl triamine, and the like. Alicyclic amines, for example, isophorone diamine, dicyclopentadienyl diamine, N-aminoethylpiperazine, bis(4-amino-3-methyldicyclohexyl), Bis(aminomethyl)cyclohexane, 3,9-bis(3-aminopropyl)hydrazine·tetraoxaspiro(5,5)-indole, raw spinylene diamine, and the like. The aromatic amines are, for example, tetrachloro-p-phthaldimethyldiamine, ni-benzenedimethyldiamine, p_benzene-methyldiamine, m-phenylenediamine, fluorene-phenylene Diamine, p_phenylenediamine, 2,4-diaminoanisole, 2,4-toluenediamine, 2,4-diaminodiphenyl-16-201002752, methane, 4,4'- Diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 2,4-diaminodiphenylanthracene, 4,4'-diaminodiphenyl砸, m-aminophenol, m-aminobenzylamine, benzyldimethylamine, 2-dimethylaminomethylphenylhydrazine, triethanolamine, methyl benzylamine, a-(m-amine Phenyl) ethylamine ' ct-(p -aminophenyl)ethylamine, diaminodiethyldimethylmethane' bis(4-aminophenyl)-P-diiso Propyl benzene and the like. Specific examples of the acid anhydride-based hardener include, for example, dodecene succinic anhydride, polysuccinic anhydride, polysebacic anhydride, polysebacic anhydride, poly(methyloctadecanedioic acid) anhydride, poly(phenyl hexadecane) Alkanoic acid anhydride, methyltetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, hexahydrophthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, tetrahydrophthalic anhydride , trialkyltetrahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, methylcyclohexene tetracarboxylic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride , ethylene glycol trimellitate, chloro-bromic anhydride, ceric anhydride, methyl benzoic anhydride, 5-(2,5-dioxytetrahydro-3-furanyl)-3-methyl-3 -cyclohexane-1,2-dicarboxylic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 1-methyl-dicarboxy-1,2 , 3,4-tetrahydro-1-naphthalene succinic dianhydride, and the like. In the epoxy resin composition of the present invention, the ratio of the epoxy resin to the hardener is such that the equivalent ratio of the epoxy group to the functional group in the hardener is in the range of 0.8 to 1_5. When it is outside this range, it remains after the hardening of the unreacted epoxy group or the functional group in the hardener, and it is not preferable as the reliability of the electrical insulating material is lowered. In the epoxy resin composition of the present invention, an inorganic chelating material -17-201002752 may also be added. The inorganic filler material is added in an amount of 50 to 95% by weight, preferably 80 to 95% by weight based on the epoxy resin. The effect of high thermal conductivity and low thermal expansion cannot be sufficiently exerted. These effects are based on the fact that the inorganic filling material does not increase in response to its volume fraction, but rather increases from the beginning. These physical properties, the high-order structure under the test state, are controlled by the effect, and the secondary structure is mainly based on the quantitative inorganic filler material achieved on the surface of the inorganic filler material. On the other hand, if the amount of the inorganic material is more than this, the viscosity thereof becomes high, or the formability of the inorganic filler material is preferably spherical, and if it is included, as long as it is spherical, There is no particular point of view on improving liquidity, which is as close as possible. In this way, it is possible to obtain the most dense structure of the face-centered cubic structure, etc., and obtain a sufficient charge shape. When the charge is increased, the friction between the charge reaches the upper limit. The fluidity is extremely lowered, and the formability is deteriorated, which is not preferable. From the viewpoint of the improvement of the thermal conductivity, it is preferable to use a thermal conductivity of 5 W/m·K or more of 5 〇 w t % or more, and it is preferable to use oxidized yttrium, yttrium oxide or the like. Among the best of these, the ball 'can be used as needed' and the fat composition has no relationship with the shape. Generally, if it is less, the more the sex, the high heat resistance, etc., the better, but the specific The added amount is considered because it is in the high score, and because of this high, the addition of the special supplementary material will deteriorate, and the ideal cross section is the ellipse. However, based on the true spherical shape, Hexagonal dense structure. If the non-spherical condition is increased, the inorganic filling material is aluminum nitride or crystalline di-alumina in the low-viscosity material. In addition, the amorphous inorganic yoke -18- 201002752 material, such as molten cerium oxide, crystalline cerium oxide and other inorganic cerium filling materials, the average particle size is preferably 30 μ. If the average particle diameter is larger than this, the epoxy resin composition is impaired and the strength is also lowered, which is not preferable. Further, when the inorganic filler is used, the glass fiber substrate or the fibrous substrate may be compounded with the particulate inorganic filler fibrous substrate, and the solvent varnish may be used in the flaky fibrous substrate. Drying is carried out, followed by impregnation. The prepreg thus formed can be made of a metal substrate such as stainless steel foil, butylene terephthalate, polyethylene naphthalate, liquid crystal amine, polyimine, A polymer substrate such as Teflon is subjected to heat molding, and is applied to a printed circuit board or a heat-releasing substrate. A curing accelerator can also be used in the epoxy resin composition of the present invention. For example, there are amines, imidazoles, ortho-acids, etc., specifically, for example, '1,8-diazabicycloalkenyl-7, tri-extended ethylenediamine, benzyldimethylamine, triethylaminoethanol 'Trimethane, such as tris(dimethylaminomethyl) phenol, 2-phenylimidazole, 2-phenyl-4-methylimidazole, hydrazine, etc. Tetrasubstituted anthracene • tetrasubstituted borate such as an organophosphine such as a phosphine, a phenylphosphine or a phenylphosphine, a tetraphenyl hydrazine, a tetraphenyl hydroxyethyl triphenyl borate or a tetrabutyl hydroxy salt In the case of 2-ethyl-tetraphenylborate or hydrazine-methylmorpholine-tetraphenylborate m, the fluidity of the liquid or the like is comparable. For example, it may be impregnated with the pre-copper foil of the invention, aluminum foil, alcohol ester, polyparaphenylene polymer, polyfluorene, and the like. Organic phosphines, ruthenium (5,4,0) undecylamine, dimethyl.triamine, 2-methyl-2-heptadecylmethylenetriphenylphosphine, ditetraphenylborate • Tetraphenylboron 19-201002752 acid salt such as tetrabutylborate 4-methylimidazole. Generally, the 'addition amount' is in the range of 0.2 to 10 parts by weight based on 100 parts by weight of the epoxy resin. These can be used alone or in combination. The mass of the above-mentioned hardening catalyst is preferably 0.1 to 10·0% by mass based on the total amount of the epoxy resin (including the halogen-containing epoxy resin as a flame retardant) and the hardener. If it is less than 0.1% by mass, the molding time becomes long, and the workability is lowered due to the decrease in rigidity during molding. Conversely, if it exceeds 1 〇·〇% by mass, hardening occurs during the forming process. It is prone to unfilled situations. In the epoxy resin composition of the present invention, a wax which is generally used as a release agent in the epoxy resin composition can be used. The wax may, for example, be stearic acid, octadecanoic acid, octadecyl carbonate, phosphate or the like. In the epoxy resin composition of the present invention, in order to enhance the adhesion of the inorganic filler and the resin component, a coupling agent generally used in the epoxy resin composition can be used. As the coupling agent, for example, an epoxy decane can be used. The amount of the coupling agent added is preferably 0.1 to 2.0% by mass based on the epoxy resin composition. When the amount is less than 0.1% by mass, the blending of the resin and the substrate is deteriorated, and the formability is also deteriorated. On the other hand, when it exceeds 2.0% by mass, the molded article may be contaminated in the continuous formability. Further, in the epoxy resin composition of the present invention, thermoplastic oligomers can be added from the viewpoint of improvement in fluidity at the time of molding and improvement in adhesion to a substrate such as a lead frame. Examples of thermoplastic oligomers include, for example, C5 and C9 petroleum resins, styrene resins, oxime resins, styrene-styrene copolymer resins, styrene, benzene, benzene, and styrene copolymers. -20- 201002752 Resin, hydrazine benzoquinone thiophene copolymer resin, etc. The amount of addition is generally in the range of 2 to 30 parts by weight based on 100 parts by weight of the epoxy resin. Further, the epoxy resin composition of the present invention can be suitably used as a general user in an epoxy resin composition. For example, there are a phosphorus-based flame retardant, a flame retardant such as a bromine compound or antimony trioxide, and a coloring agent such as carbon black or an organic dye. In the epoxy resin composition of the present invention, an epoxy resin, a hardener, an inorganic chelating material, and other components other than the coupling agent may be uniformly mixed by a mixer, a coupling agent may be added, and then a heating roller may be used. , kneading machine, etc. are produced by kneading. There is no particular limitation on the order in which these ingredients are combined. Further, the kneaded kneaded material may be ground after kneading to be pulverized or tableted. The epoxy resin composition of the present invention contains an epoxy resin and a curing agent as main components of the resin component. It is preferably 60 wt% or more, preferably 80 wt% or more, and is an epoxy resin and a hardener. The epoxy resin composition of the present invention is useful as an electrical insulating material, and is particularly suitable for use as a sealing device in a semiconductor device. In order to obtain a molded article using the epoxy resin composition of the present invention, for example, transfer molding, press molding, injection molding, injection molding, extrusion molding, and the like can be applied, but based on mass production, Transfer molding is preferred. At the time of the formation, heating can be performed to cause hardening (polymerization). Therefore, the obtained molded product is also referred to as a cured product because it is a molded product of a polymer resin (thermoplastic or thermosetting resin). Therefore, the term "hardening" as used in the specification also means polymerization, and the cured resin contains a thermoplastic resin. -21 - 201002752 The molded article of the present invention is generally formed as a three-dimensional crosslinker, but it is not necessarily a three-dimensional crosslinked body, and may be a molded product of a thermoplastic second molecule. Wherein, in particular, when the difunctional epoxy resin is reacted with the difunctional hardener, the secondary hydroxyl group formed by the ring opening reaction of the epoxy group is further reacted with the epoxy group to become a cubic bond. The joint is a thermoplastic polymer molded body which can be thermoplastic by selecting a curing condition. From the viewpoint of high thermal conductivity, it is preferable to form a crystalline molded product. However, in general, since the three-dimensional crosslinked body hinders crystallinity, the crosslinking is reduced and the secondary polymer is formed as a main body. The body is preferred. The crystallinity of the molded body can be confirmed by observing the endothermic peak of the crystal melting under the differential scanning thermal analysis as a melting point. Generally, the melting point ranges from 120 ° C to 320 ° C, preferably from 150 ° C to 300 ° C, and most preferably from 200 ° C to 280 ° C. The degree of crystallization of the molded article of the present invention is preferably as high as possible, and can be evaluated by the differential heat of melting of the crystal under differential scanning calorimetry. In general, the heat absorption amount is 5 J/g or more per unit weight of the resin component minus the charge material, and preferably the heat absorption amount is 10 μg/g or more, and more preferably 20 J/g or more. 30 J/g or more. If it is smaller than this, it has a small effect of improving the thermal conductivity of the epoxy resin molded article. Further, from the viewpoint of improvement in low thermal expansion property and heat resistance, it is preferred that the crystallinity is higher. In addition, the term "heat absorption" as used herein refers to a sample obtained by using a differential thermal analyzer using a sample of about 1 〇mg of a fine slab and measuring at a temperature increase rate of 1 〇 ° c /min under a nitrogen gas stream. Heat. The molded article of the present invention can be obtained by heating it into the shape of -22-201002752 by the above-described forming method, but in general, the forming temperature is from 80 ° C to 250 ton: and the forming thereof is improved. The degree of crystallization of the substance is preferably formed at a temperature lower than the melting point of the molded article. The preferred forming temperature is l〇 (the range of TC to 220 ° C, preferably 150 ° C to 200 ° C. In addition, the preferred forming time is 30 seconds to 1 hour, the best The forming time is from 1 minute to 3 minutes. Further, after forming, the degree of crystallization can be improved by post-curing. Usually, the post-cure temperature is from 130 ° C to 250 ° C, and the time is The range of 1 hour to 20 hours, but preferably, the post-cure is performed at a temperature lower than the temperature of the endothermic peak at a temperature of 5 ° C to 40 ° C under differential thermal analysis for 1 hour to 24 hours. Further, the preferred thermal conductivity of the molded article is 4 W/m·K or more, and most preferably 6 W/m·K or more. EXAMPLES Hereinafter, the present invention will be further specifically described by way of examples. 1 Dissolve 4,4,-dihydroxybenzophenone 1 070 g in epichlorohydrin 65 00 g 'under reduced pressure at 60 ° C (about 130 Torr), 4 8 % oxidized in 4 hours The sodium aqueous solution was dropped at 8 〇 8 g. During this time, the generated water was discharged into the system by the azeotrope with epichlorohydrin and discharged from the outside of the system. After the reaction was further continued for 1 hour, the epichlorohydrin was distilled off, and after adding 3 500 g of methyl isobutyl ketone, the salt was removed by washing with water. Thereafter, 20% sodium hydroxide 1 was added at 8 〇t: 〇〇g 'stirred for 2 hours, and washed with warm water of 100 mL. Then -23-201002752, remove the water by liquid separation and then distill off methyl isobutyl ketone under reduced pressure to obtain a pale yellow crystal. Epoxy resin 1 460 g (epoxy resin A). The melting point of epoxy resin A measured by capillary method is 1 2 8 ° C to 1 3 1 (:, while the viscosity at 150 ° C is The epoxy equivalent system is 1 79, and the water-decomposable chlorine is 270 ppm. The obtained resin is determined by GPC. The ratio of each component under the general formula (1) is 91.0% when n=〇. When η = 1, it is 8.2%. Here, 'so-called hydrolyzable chlorine' means that after the sample 〇·5 g is dissolved in 30 ml of dioxane, '10 ml of 1 N - Κ Η 加入 is added, and the boil is still flowing for 30 minutes. Thereafter, after cooling to room temperature, and further injecting 100 ml of 80% acetone water, the enthalpy was measured by potentiometric titration with a 0.002 N-AgN03 aqueous solution. It is obtained by a capillary method at a heating rate of 2 ° C / min. The viscosity is measured by BROOK FIELD and measured under CAP2000H, and the softening point is measured by the ring method according to JIS K-691 1. In addition, GPC The measurement is based on: the device is a 515A type manufactured by Japan Waters Co., Ltd., the column is TSK-GEL2000 X 3 tube and TSK-GEL 4 0 0 0 x 1 tube (other than TOSOH (stock)), the solvent is Tetrahydrofuran, flow rate of 1 ml / min, temperature of 38 ° C, detector RI, etc. are carried out. Examples 1 to 6 and Comparative Examples 1 to 5 The epoxy resin component was an epoxy resin (epoxy resin A) of Reference Example 1, and an epoxy compound of 4,4'-dihydroxydiphenyl ether (epoxy resin). B: Dongdu Chemical Co., Ltd. 'YSLV-80DE 'epoxy equivalent 174), or biphenyl epoxy resin (epoxy resin C: Japanese epoxy resin, YX-4000H, epoxy-24-201002752 equivalent 195), and The hardener is 4,4'-dihydroxydiphenylbenzene A), 4,4'-dihydroxydiphenyl ether (hardener B), diphenylmethane (hardener C), 4,4 '-Dihydroxydiphenylation agent D) or phenol novolac (hardener E: Group Chemical 4261' OH equivalent 103, softening point 82 ° C). In addition, triphenylphosphine is used hard, and the inorganic ruthenium material uses a spherical alumina diameter of 1 2.2 # m ). The components shown in Table 1 were mixed, and after mixing and mixing, the mixture was further kneaded by a heating roller for about 5 minutes, and then cooled, and the epoxy resin group of Examples 1 to 6 and Comparative Examples 1 to 5 was used for the epoxy resin group. The composition was molded under the conditions shown in Table 1, and the physical properties of the molded product were evaluated. The results are not summarized in Tables 1 and 2. In addition, the figures of the complex are parts by weight. In addition, the evaluation is based on the following (1) Thermal conductivity: The measurement was carried out by the unsteady hot line method using a LEMA447 rate meter manufactured by NETZSCH. (2) Measurement of melting point and melting heat (DSC method): The heat analysis device (DSC6200 type manufactured by Seiko Instruments Co., Ltd.) was measured at a speed of 10 ° C / min. (3) Linear expansion coefficient and glass transition temperature: A TMA120C type thermomechanical measuring device was prepared using a fine stock, and then measured by heating at a rate of /min. (4) Water absorption rate: a diameter of 5 〇 mrn and a thickness of 3 mm were formed. After the post-hardening, the weight change rate was measured after absorbing moisture for 1 ° 〇 at 85 ° C and a relative humidity of 85 %. Methyl ketone (hard 4,4,- dimethyl ketone (hard, PSM-chemical accelerator (average granules are fully ground and each product is formed. The various types in the post-hardening table are used. The heat transfer is not bad) Sweep and then heat the instrument (speed 10 °C disc condition, make -25- 201002752 [Table l] Example 1 2 3 4 5 6 Epoxy resin A 94.0 85.5 78.0 94.0 94.5 94.5 Epoxy resin B 8.5 15.5 Hardener A 56.0 56.0 56.5 51.0 46.5 50.5 Hardener C 5.0 9.0 Hardener D 5.0 Inorganic Filling Material A 1350 1350 1350 1350 1350 1350 Hardening Accelerator 1.6 1.6 1.6 1.6 1.6 1.6 Glassy Temperature (.) 132 123 121 122 119 131 Thermal expansion coefficient (ppm, <Tg) 8.4 8.6 8.7 8.6 8.7 8.6 Thermal expansion coefficient (ppm, <Tg) 27.9 33.0 34.5 32.4 37.0 29.5 Heat distortion temperature (TC ) 240 211 203 219 199 231 Water absorption (wt% , 100h) 0.12 0.14 0.16 0.14 0.15 0.13 Thermal conductivity (W/nvK) 5.33 4.87 4.43 4.98 4.68 5.29 Melting point (C) 226.0 209.0 198.0 211.0 196.0 225.0 Heat of fusion (J/g-resin) 53 28 21 33 27 43 -26 - 201002752 [Table 2] Comparative Example 1 2 3 4 5 6 Epoxy tree Grease A 96.0 96.0 42.5 31.0 Epoxy Resin B 51.0 62.0 93.0 Epoxy Resin C 97.0 Hardener A 56.5 57.0 57.0 53.0 Hardener B 54.0 Hardener C 54.0 Inorganic Filling Material A 1350 1350 1350 1350 1350 1350 Hardening Accelerator 1.6 1.6 1.6 1.6 1.6 1.6 Glass transition temperature fc ) 113 111 112 107 116 119 Thermal expansion coefficient (ppm, < Tg) 10.5 11.4 11.5 12.0 11.4 11.7 Thermal expansion coefficient (ppm, < Tg) 44.7 48.5 46.2 43.8 44.1 46.5 Heat distortion temperature (° C ) 122 121 117 115 124 126 Water absorption (wt%, l〇〇h) 0.27 0.26 0.26 0.27 0.25 0.22 Thermal conductivity (W/mK) 3.75 3.56 3.94 3.87 3.74 3.35 Melting point (°C) - Heat of fusion (J/ G-resin) - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - Good heat release and dimensional stability are excellent in formability and reliability, and water, low thermal expansion, and high heat resistance are applied to semiconductor sealing and insulating materials for laminated boards. -27-