200948843 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種信賴性優異之可用於半導體封裝、 層合板、散熱基板等電氣·電子零件用絕緣材料之在常溫 下爲固態之操作性優異，且成形時之低黏度性優異之結晶 性改性環氧樹脂，及使用其之環氧樹脂組成物，以及由其 獲得之硬化物。 φ 【先前技術】 過去，二極體、電晶體、積體電路等之電氣、電子零 件或半導體裝置等之封裝方法係採用例如以環氧樹脂或聚 矽氧樹脂等封裝之方法，或使用玻璃、金屬、陶瓷等之氣 密（Hermetic seal)法，但近年來隨著信賴性提高同時可 大量生產且具成本優勢之藉由遞模成形之樹脂封裝已成爲 主流。 © 藉由上述遞模成形之樹脂封裝方法中使用之樹脂組成 物中，一般係使用由以環氧樹脂與作爲硬化劑之酚樹脂作 爲樹脂成分之主要成分之樹脂組成物所構成之封裝材料。 另外，電子零件安裝於印刷電路板之方法，由過去之 插銷方式進展到表面安裝方式。由於表面安裝方式係將封 裝整體加熱至焊錫溫度，因此因熱衝擊使封裝龜裂成爲大 的問題點，但防止封裝龜裂的有力方法有無機充塡材之高 充塡率化。另外，作爲電源裝置等之封裝材料所使用之環 氧樹脂組成物由於相對應於元件釋出之大量熱，而要求無 -5- 200948843 機充塡材之高密度充塡化。 爲了克服上述問題點，因此期望低黏度性優異之環氧 樹脂。至於低黏度環氧樹脂一般雖已通常廣泛使用雙酚A 型環氧樹脂、雙酚F型環氧樹脂等’但該等環氧樹脂中低 黏度者在常溫下爲液態，處理上有困難。再者，該等環氧 樹脂於耐熱性、機械強度、韌性方面並不充分。 由於上述背景，最近有多數提案提及使用在常溫下爲 固態之結晶性環氧樹脂之環氧樹脂組成物。專利文獻1中 © ，提案有以雙酚系環氧樹脂作爲主劑之半導體封裝用環氧 樹脂組成物作爲改良處理之作業性、耐熱性、韌性等者， 但於低吸水性、低黏度性、硬化性方面並不充分。又，專 - 利文獻2中提案有雙酚F型作爲主劑之固態環氧樹脂。雙 酚F型環氧樹脂雖有低黏度性優異之特徵，但有耐熱性、 硬化性之問題。另外，專利文獻3中雖揭示使用帶有氫醌 結構之環氧樹脂之環氧樹脂組成物，但該等爲具有碳數 3〜6之烷基取代基者，由於取代基之立體障礙，使反應性 ❹ 降低，或者因硬化後分子之充塡受阻礙而產生熱傳導率下 降等之問題。又，專利文獻7中雖揭示調配帶有氫醌結構 之環氧樹脂與具有聯苯結構之環氧樹脂所成之環氧樹脂組 成物，但並非將高熱傳導性之呈現當作目標者。專利文獻 7中使用經四甲基取代之環氧樹脂作爲具有聯苯結構之環 氧樹脂，但本發明者依循實驗之結果，發現具有烷基取代 基者會有使熱傳導率下降之問題。 又，已嘗試使用結晶氧化矽、氮化矽、氮化鋁、球狀 -6- 200948843 氧化鋁粉末作爲用以提高熱傳導率之方法（專利文獻4、5 )，但提高無機塡充材料之含有率時，成形時之黏度上升 同時亦使流動性下降，而產生成形性受損之問題。據此， 僅以提高無機塡充材之含有率之方法有其界限。 由上述背景，由基質樹脂本身之高熱傳導率化之方法 亦被檢討，例如，專利文獻6及專利文獻8中提出使用具 有剛直之液晶（mesogenic)基之液晶性樹脂之樹脂組成 〇 物。但，該等具有液晶基之環氧樹脂由於爲具有聯苯結構 、甲亞胺（a ζ 〇 m e t h i n e )結構等之剛直構造之高結晶性之 不具有高熔點之分子量分布之實質上單一之環氧化合物， • 因此作爲環氧樹脂組成物時有作業性不良之缺點。再者， ' 硬化狀態中由於使分子有效的配向，因此有必要導入強力 磁場使之硬化，爲了於工業上廣泛利用故設備上受到相當 大的限制。另外，與無機塡充材之配合系統爲相較於基質 樹脂之熱傳導率，無機塡充材之熱傳導率壓倒性地較大， © 即使提高基質樹脂本身之熱傳導率，現實上是無助於作爲 複合材料之熱傳導率提升，而無法獲得充分之熱傳導率提 ^ 高效果。因此，一般認知爲關於熱傳導性提高之檢討係提 高樹脂之熱傳導性，而與塡料之混合系統之情況，若塡料 充分存在，由於塡料之熱傳導性壓倒性地較高，故即使樹 脂之熱傳導性多少變佳，但效果少。 專利文獻9中揭示對於藉由覆晶（Flip Chip )方式等 安裝有半導體元件之半導體裝置之連接用電極部分的該負 荷有效地分散於封裝之樹脂層並減輕，即使在溫度循環等 200948843 過度嚴苛之環境條件下，亦可確保半導體裝置之導通性之 環氧樹脂組成物，但亦揭示環氧樹脂爲具有第三丁基之氫 棍型環氧樹脂或具有甲基之聯苯型環氧樹脂等。專利文獻 ίο中揭示流動性良好，模具磨耗少，且可獲得具有高熱傳 導性之硬化物之含有球狀方石英之高熱傳導性環氧樹脂組 成物’但達成其之手段爲塡充材之改良，並非改良樹脂者 。專利文獻11中揭示可獲得高塡充有無機塡充材之熱傳 導性優異之成形物之環氧樹脂組成物，但達成其之手段爲 塡充材之改良’而非改良樹脂者。 [專利文獻1]特公平4-7365號 [專利文獻2]特開平6-345850號 [專利文獻3]特開平6-145293號公報 [專利文獻4]特開平11-147936號公報 [專利文獻5]特開2002-309067號公報 [專利文獻6]特開平11_323162號公報 [專利文獻7]特開平6-184272號公報 [專利文獻8]特開平2〇〇4_331811號公報 [專利文獻9]特開2001-207031號公報 [專利文獻10]特開2001-172472號公報 [專利文獻11]特開2001-348488號公報 【發明內容】 [發明欲解決之課題] 據此’本發明之目的在於消除上述問題點，而提供一 -8- 200948843 種在常溫下爲固體之處理性優異且在成形溫度下之低黏度 性優異之改性環氧樹脂，以及使用其與無機塡充材複合化 之情況下可獲得熱傳導率高，且在低熱膨脹性下耐熱性及 耐濕性優異之硬化物之環氧樹脂組成物及其硬化物。 [解決課題之手段] 爲解決上述課題而進行各種檢討之結果，認爲於特定 〇 樹脂之情形，或含有某一定量以上之無機塡充材時，提高 樹脂之熱傳導性係反映於最終硬化物之現象。所以，發現 使具有特定酚性羥基之化合物之混合物與環氧氯丙烷反應 * ，在常溫下具有結晶性、操作性優異且作爲複合材料之熱 傳導率特異地被提升，因而完成本發明。 本發明爲在常溫具有結晶性之改性環氧樹脂，其特徵 爲其係對氫醌1重量份混合有0.1〜10重量份之4,4’-二羥 基聯苯之混合物與環氧氯丙烷反應所得。。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 And a crystalline modified epoxy resin excellent in low viscosity at the time of molding, and an epoxy resin composition using the same, and a cured product obtained therefrom. φ [Prior Art] In the past, a packaging method such as an electric or electronic component or a semiconductor device such as a diode, a transistor, or an integrated circuit was used, for example, by encapsulating epoxy resin or polyoxymethylene resin, or using glass. , Hermetic seal method of metal, ceramics, etc., but in recent years, with the increase in reliability, mass-produced and cost-effective resin packaging by transfer molding has become mainstream. © The resin composition used in the resin encapsulation method of the above-mentioned transfer molding, generally, an encapsulating material composed of a resin composition containing an epoxy resin and a phenol resin as a curing agent as a main component of a resin component is used. In addition, the method of mounting electronic components on a printed circuit board has progressed from the past plugging method to the surface mounting method. Since the surface mounting method heats the entire package to the solder temperature, the package crack is a big problem due to thermal shock, but a powerful method for preventing package cracking is the high filling rate of the inorganic filler. Further, the epoxy resin composition used as the encapsulating material of the power supply device or the like is required to have a high density of the filling material of the machine due to the large amount of heat corresponding to the release of the element. In order to overcome the above problems, an epoxy resin excellent in low viscosity is desired. As for the low-viscosity epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, etc. are generally widely used. However, those having low viscosity in such epoxy resins are liquid at normal temperature, and handling is difficult. Further, these epoxy resins are not sufficient in terms of heat resistance, mechanical strength, and toughness. Due to the above background, most recent proposals have mentioned the use of an epoxy resin composition which is a solid crystalline epoxy resin at normal temperature. In Patent Document 1, we have proposed an epoxy resin composition for semiconductor encapsulation using a bisphenol-based epoxy resin as a main component as an improvement in workability, heat resistance, toughness, etc., but low water absorption and low viscosity. The hardenability is not sufficient. Further, in the patent document 2, a solid epoxy resin having a bisphenol F type as a main component is proposed. Although the bisphenol F type epoxy resin is excellent in low viscosity, it has problems of heat resistance and hardenability. Further, Patent Document 3 discloses an epoxy resin composition using an epoxy resin having a hydroquinone structure, but those having an alkyl group having 3 to 6 carbon atoms are caused by steric hindrance of the substituent. The reactivity ❹ is lowered, or the charge of the molecule is hindered due to the hardening of the molecule, and the thermal conductivity is lowered. Further, Patent Document 7 discloses an epoxy resin composition in which an epoxy resin having a hydroquinone structure and an epoxy resin having a biphenyl structure are blended, but the appearance of high thermal conductivity is not intended. In Patent Document 7, a tetramethyl-substituted epoxy resin is used as the epoxy resin having a biphenyl structure. However, according to the results of experiments, the inventors have found that having an alkyl substituent has a problem of lowering the thermal conductivity. Further, attempts have been made to use crystalline cerium oxide, cerium nitride, aluminum nitride, and spherical -6-200948843 alumina powder as a method for increasing thermal conductivity (Patent Documents 4 and 5), but to improve the content of inorganic ceramium-containing materials. At the time of the rate, the viscosity at the time of molding increases, and the fluidity is also lowered, which causes a problem of impaired formability. Accordingly, there is a limit to the method of increasing the content of the inorganic cerium filler. In view of the above, the method of the high thermal conductivity of the matrix resin itself has been examined. For example, Patent Document 6 and Patent Document 8 propose a resin composition using a liquid crystal resin having a straight-form liquid crystal. However, these epoxy resins having a liquid crystal group are substantially single rings having a high crystallinity and a high melting point molecular weight distribution, which has a biphenyl structure, an anthracene (meth) structure, or the like. Oxygen compounds, • Therefore, they are disadvantageous in workability when used as an epoxy resin composition. Further, in the hardened state, since the molecules are effectively aligned, it is necessary to introduce a strong magnetic field to harden them, and the apparatus is considerably limited in order to be widely used in the industry. In addition, the system of mixing with the inorganic ruthenium material is superior to the thermal conductivity of the matrix resin, and the thermal conductivity of the inorganic ruthenium filler material is overwhelmingly large. Even if the thermal conductivity of the matrix resin itself is increased, it is actually not helpful. The thermal conductivity of the composite material is increased, and sufficient thermal conductivity is not obtained. Therefore, it is generally recognized that the review of the improvement in thermal conductivity improves the thermal conductivity of the resin, and in the case of a mixed system with the dip, if the dip is sufficiently present, since the thermal conductivity of the dip is overwhelmingly high, even the resin The thermal conductivity is somewhat better, but the effect is small. Patent Document 9 discloses that the load on the connection electrode portion of the semiconductor device in which the semiconductor device is mounted by a flip chip method or the like is effectively dispersed in the resin layer of the package, and is reduced even in a temperature cycle such as 200948843. An epoxy resin composition that ensures the conductivity of a semiconductor device under severe environmental conditions, but also discloses that the epoxy resin is a hydrogen butyl type epoxy resin having a third butyl group or a biphenyl type epoxy group having a methyl group. Resin, etc. In the patent document ίο, it is disclosed that the fluidity is good, the mold wear is small, and a high thermal conductivity epoxy resin composition containing spherical cristobalite having a high thermal conductivity is obtained, but the means for achieving the improvement of the ruthenium filling material is achieved. Not a modified resin. Patent Document 11 discloses an epoxy resin composition which can obtain a molded article having a high thermal conductivity of an inorganic cerium filling material, but the means for achieving this is an improvement of the enamel filler, rather than an improved resin. [Patent Document 1] Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 7] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 10] JP-A-2001-348488 [Patent Document 11] JP-A-2001-348488 SUMMARY OF INVENTION [Problems to be Solved by the Invention] Accordingly, the present invention aims to eliminate the above-mentioned problems. The problem is to provide a modified epoxy resin which is excellent in solidity at room temperature and excellent in low viscosity at the forming temperature, and in the case of using it in combination with an inorganic ruthenium filler material. An epoxy resin composition having a high thermal conductivity and having excellent heat resistance and moisture resistance under low thermal expansion properties and a cured product thereof can be obtained. [Means for Solving the Problem] As a result of various reviews to solve the above problems, it is considered that the thermal conductivity of the resin is reflected in the final cured product in the case of a specific resin or when a certain amount or more of the inorganic cerium is contained. The phenomenon. Therefore, it has been found that a mixture of a compound having a specific phenolic hydroxyl group is reacted with epichlorohydrin*, has crystallinity at normal temperature, is excellent in workability, and is specifically elevated as a heat conductivity of the composite material, and thus the present invention has been completed. The present invention is a modified epoxy resin having crystallinity at normal temperature, characterized in that it is a mixture of 4 to 4 parts by weight of 4,4'-dihydroxybiphenyl and epichlorohydrin mixed with 1 part by weight of hydroquinone. The reaction is obtained.
© 又，本發明爲一種環氧樹脂組成物，其特徵係以（A )環氧樹脂、（B)硬化劑及（C)無機塡充材作爲主成分 所成之環氧樹脂組成物，其中作爲環氧樹脂係使用50wt% 以上之上述改性環氧樹脂。 上述環氧樹脂組成物之較佳樣態如下所示： 1) 無機塡充材之含有率爲80〜96wt%， 2 ) 硬化劑爲酚系硬化劑， 3) 使用50wt%以上之二官能性酚化合物作爲酚系硬 化劑， -9- 200948843 4) 上述二官能性酚化合物係選自氫醌、4,4’-二羥基 聯苯、4,4’-二羥基二苯醚' 1,4-雙（4-羥基苯氧基）苯、 4,4’·二羥基二苯基甲烷、4,4’-二羥基二苯基硫醚、1，5·萘 二酚、2,7·萘二酚及2,6-萘二酚所組成組群之至少一種， 5) 使用50wt%以上之球狀氧化鋁作爲無機塡充材。 再者，本發明爲一種上述之環氧樹脂組成物，其特徵 爲其爲半導體封裝用環氧樹脂組成物。 又，本發明爲一種硬化物，其特徵爲係使上述之環氧 © 樹脂組成物硬化而得，且熱傳導率爲4W/m · K以上。 其中，上述硬化物之差示掃描熱量分析中熔點之峰値 在120°C至280 °C之範圍，或者硬化物之差示掃描熱量分析 ， 中樹脂成分換算之吸熱量爲10 J/g以上。 ' 【實施方式】 本發明之改性環氧樹脂可藉由使氫醌與4,4’-二羥基 聯苯之混合物與環氧氯丙烷反應而製造。該反應可與通常 © 之環氧化反應同樣地進行。本發明之改性環氧樹脂除包含 氫醌之環氧化物與4，4’-二羥基聯苯之環氧化物以外，亦 可爲含有每一分子中具有源自氫醌與4,4’-二羥基聯苯之 單位之環氧化物之混合物。因此，如所悉知由二羥基化合 物與環氧氯丙烷反應獲得之環氧化物除包含聚合度〇之環 氧化物（n = 0聚物）以外，亦包含n=l (二聚物）、n = 2 ( 三聚物）等多聚物。 氫醌與4,4’-二羥基聯苯之混合比例以重量比計爲氫 -10- 200948843 醌/4,4’-二羥基聯苯=〇·ι〜i〇.〇之範圍，但較好爲〇2~5.〇 之範圍。若比該比例小則在4，4 ’ -二羥基聯苯之環氧化合 物之高熔點性之影響下成爲操作性不良者，比該比例大時 則硬化物之耐熱性等特性下降。 例如，舉例爲使氫醌與4，4’-二羥基聯苯之混合物溶 解於相對於該等酚性羥基之莫耳比爲過量之環氧氯丙烷中 之後，在氫氧化鈉、氫氧化鉀等驗金屬氫氧化物存在下， 〇 於50〜150°C，較好在60~100°c之範圍內反應1~10小時之 方法。此時，鹼金屬氫氧化物之使用量相對於氫醌與 4,4’-二羥基聯苯中之羥基1莫耳爲〇.8〜i.2莫耳，較好爲 0.9〜1.0莫耳之範圍。環氧氯丙烷係使用相對於氫醌及 4，4’ -二羥基聯苯中之羥基爲過量，通常相對於氫醌及 4,4’-二羥基聯苯中之羥基丨莫耳爲1.5至15莫耳。反應 結束後，餾除過剩之環氧氯丙烷，且使殘留物溶解於甲苯 、甲基異丁基酮等溶劑中，經過濾、水洗去除無機鹽，接 © 著藉由餾除溶劑，獲得標的之環氧樹脂。 本發明之改性環氧樹脂製造之際可使用除作爲原料之 必要成分之氫醌及4,4’-二羥基聯苯以外進一步混合其他 酚性化合物者。但，該情況下，氫醌及4,4’-二羥基聯苯 之合計量較好爲包含全部酚性化合物之50 wt %以上，較好 爲70wt%以上，更好爲90wt%以上者。 本發明之改性環氧樹脂之環氧當量通常在110至300 之範圍內，但就無機塡充材之高充塡率化及提高流動性之 觀點觀之以低黏度性者較佳，較好爲環氧當量爲1 1 0至 -11 - 200948843 160之範圍者。 本發明之改性環氧樹脂爲在常溫下具有結晶性者。結 晶性之展現可以差示掃描熱量分析作爲伴隨結晶熔解之吸 熱峰加以確認。而且，由於本發明之改性環氧樹脂爲混合 物，因此該情況之吸熱峰一般並非觀察到一個吸熱峰而是 複數個。以差示掃描熱量分析觀察之溶點，於源自由氫醌 及4,4’-二羥基聯苯衍生之改性環氧樹脂之吸收峰，最低 溫度之吸熱峰爲50°C以上，較好爲70°C以上，最高溫度之 © 吸熱峰爲150°C以下，較好爲130°C以下。若低於該溫度則 作爲粉體時會引起結塊等，在常溫下成爲固體使操作性下 降，高於該溫度時會有與硬化劑等之溶解性不良等之問題 。又，較好在150°C下之熔融黏度越低越佳，通常爲O.lPa • s以下，較好爲〇.〇iPa· s以下，更好爲〇.〇〇5Pa. s以 下， 本發明之改性環氧樹脂之純度，尤其是水解性氯量就 提高適用之電子零件信賴性之觀點而言以較少者較佳。雖 © 無特別限制，但較好爲lOOOppm以下，更好爲500pm以 下。又，本發明所謂的水解性氯爲藉由下列方法測定之値 。亦即，將〇.5g試料溶解於30ml之二噁烷中之後，添加 10ml之1N-KOH且沸騰回流30分鐘後，冷卻至室溫，接 著添力口 1〇〇1111含80%丙酮之水，且以〇.〇〇2：^-入吕1^03水溶 液進行電位差滴定獲得之値。 本發明之環氧樹脂組成物係以（A)環氧樹脂、（B ) 硬化劑及（C)無機塡充材作爲主要成分，且作爲環氧樹 -12- 200948843 脂之環氧樹脂成分之5 0wt%以上包含上述改性環氧樹脂。 亦即，全部環氧樹脂之50wt%以上爲上述之改性環氧樹脂 。有利地是，全部環氧樹脂之70wt%以上，更好90wt%以 上爲上述之改性環氧樹脂。改性環氧樹脂之使用比例少於 該等時作成硬化物時之熱傳導率等之提高效果小。 本發明之環氧樹脂組成物中，除作爲本發明之必要成 分使用之上述改性環氧樹脂以外，亦可倂用分子中具有兩 〇 個以上環氧基之一般其它環氧樹脂。列舉之例爲雙酚A、 雙酚F、3,3’，5,5’-四甲基-4,4’-二羥基二苯基甲烷、4,4’-二羥基二苯基楓' 4,4’-二羥基二苯基硫醚、4,4’-二羥基二 苯基酮、芴雙酚、4,4’-二酚、3,3’，5,5’-四甲基-4,4’-二羥 基聯苯、2,2’-二酚、間苯二酚、兒茶酚、第三丁基兒茶酚 、第三丁基氫醌、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' ❹ 2,6-二羥基萘、2,7-二羥基萘、2,8-二羥基萘，上述二羥基 萘之烯丙基化物或聚烯丙基化物、烯丙基化雙酚A、烯丙 基化雙酚F、烯丙基化雙酚酚醛清漆樹脂等2價之酚類， 或者酚酚醛清漆樹脂、雙酚A酚醛清漆樹脂、鄰-甲酚酚 醛清漆樹脂、間-甲酚酚醛清漆樹脂、對-甲酚酚醛清漆樹 脂、二甲酚酚醛清漆樹脂、聚-對-羥基苯乙烯、參-(4-羥 基苯基）甲烷、1，1，2,2-肆（4-羥基苯基）乙烷、氟甘胺醇 、聯苯三酚、第三丁基聯苯三酚 '烯丙基化聯苯三酚、聚 烯丙基化聯苯三酚、1 ,2,4-苯三醇、2,3,4-三羥基二苯甲酮 -13- 200948843 、酚芳烷基樹脂、萘酚芳烷基樹脂、二環戊二烯系樹脂等 3價以上之酌類，或者四溴雙酚a等鹵化雙酚類衍生之縮 水甘油醚化物等。該等環氧樹脂可使用一種或混合兩種以 上使用。 已知作爲一般環氧樹脂硬化劑者均可用作本發明之環 氧樹脂組成物中使用之硬化劑，但較佳之硬化劑爲酚系硬 化劑。酚系硬化劑有酚性化合物，且酚性化合物除作爲單 一化合物之酚化合物以外，亦包含酚樹脂。 ® 酚系硬化劑之具體例舉例爲雙酚A、雙酚F、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、1，3-雙（4-羥基苯氧基）苯、4,4’-二羥基二 苯基硫醚、4,4’-二羥基二苯基酮、4,4’-二羥基二苯基碾、 4,4’-二羥基聯苯、2,2’-二羥基聯苯、10- (2,5-二羥基苯 基）-10H-9-氧雜-10-磷雜菲-10-氧化物、酚酚醛清漆樹脂 、雙酚A酚醛清漆樹脂、鄰-甲酚酚醛清漆樹脂、間-甲酚 酚醛清漆樹脂、對-甲酚酚醛清漆樹脂、二甲酣酚醛清漆 ^ 樹脂、聚-對-羥基苯乙烯、氫醌、間苯二甲酣、兒茶酣、 第三丁基兒茶酚、第三丁基氫醌，氟甘胺醇、聯苯三酣、 第三丁基聯苯三酿、嫌丙基化聯苯三酌、聚嫌丙基化聯苯 三酌、1,2,4-苯三酣、2,3,4-三經基二苯甲酮、1,2-一經基 萘、1,3-二羥基萘、ι，4-二羥基萘、I，5-二羥基萘、丨，6-二 羥基萘' 1，7 -二羥基萘、丨，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、2,7-二經基 萘、2,8-二羥基萘’上述二羥基萘之嫌丙基化物或聚燃丙 -14- 200948843 基化物、烯丙基化雙酚A、烯丙基化雙酚F、烯丙基化雙 酚酚醛清漆樹脂、烯丙基化聯苯三酚等。 硬化劑亦可混合兩種以上之硬化劑而使用。較好之硬 化劑爲硬化劑中含有50wt%以上，較佳70wt%以上之二官 能基之酚化合物者。此時之二官能基酚化合物較好爲選自 4,4’-二羥基聯苯、4,4’·二羥基二苯基醚' 1,4-雙（4-羥基 苯氧基）苯、4,4’-二羥基二苯基甲烷、4,4’·二羥基二苯基 〇 酮、4,4’-二羥基二苯基硫醚、1，5-萘二酚、2,7-萘二酚、 2,6-萘二酚、氫醌及間苯二甲酚之酚化合物。其中，較佳 爲4,4’-二羥基聯苯、4,4’-二羥基二苯基醚或4,4’-二羥基 二苯基甲烷。 本發明之環氧樹脂組成物中使用之硬化劑除上述酚系 硬化劑以外，亦可使用通常已知之硬化劑作爲硬化劑使用 。舉例爲例如胺系硬化劑、酸酐系硬化劑、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。該等硬化劑之調配量只要 考慮所調配之硬化劑種類或所得熱傳導性環氧樹脂之成形 體之物性適當設定即可。 胺系硬化劑之具體例舉例爲脂肪族胺類、聚醚聚胺類 '脂環式胺類、芳香族胺類等。至於脂肪族胺類舉例爲乙 二胺、1,3-二胺基丙烷、1,4-二胺基丙烷、六亞甲基二胺 、2,5 -二甲基六亞甲基二胺、三甲基六亞甲基二胺、二伸 乙基三胺、亞胺基雙丙基胺、雙（六亞甲基）三胺、三伸 乙基四胺、四伸乙基五胺、五伸乙基六胺、N_羥基乙基伸 -15- 200948843 乙二胺、四（羥基乙基）乙二胺等。聚醚聚胺類舉例爲三 乙二醇二胺、四乙二醇二胺、二乙二醇雙（丙基胺）、聚 氧伸丙基二胺、聚氧伸丙基三胺類等。脂環式胺類舉例爲 異佛爾酮二胺、孟烯二胺、N -胺基乙基哌啶、雙（4 -胺 基-3-甲基二環己基）甲烷、雙（胺基甲基）環己烷、3，9-雙（3-胺基丙基）2,4,8,10-四氧雜螺（5,5)十一烷、原冰 片烯二胺等。芳香族胺類舉例爲四氯-對-二甲苯二胺、間-二甲苯二胺、對-二甲苯二胺、間-苯二胺、鄰-苯二胺、 對·苯二胺、2,4-二胺基苯甲醚、2,4-甲苯二胺、2,4-二胺 基二苯基甲烷、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、間-胺基苯酚、間-胺基苄基胺、苄基二甲基胺、2· (二甲胺基甲基）苯酚、三乙醇胺、甲基苄基胺、α-( 間-胺基苯基）乙基胺、a-(對-胺基苯基）乙基胺、二胺 基二乙基二甲基二苯基甲烷、α，α，_雙（4-胺基苯基）-對-異丙基苯等。 酸酐系硬化劑之具體例舉例爲十二碳烯基琥珀酸酐、 聚己二酸酐、聚壬二酸酐、聚癸二酸酐、聚（乙基十八烷 二酸）酐、聚（苯基十六烷二酸）酐、甲基四氫苯二甲酸 酐、甲基六氫苯二甲酸酐、六氫苯二甲酸酐、甲基內次甲 基四氫苯酐、四氫苯二甲酸酐、三烷基四氫苯二甲酸酐、 甲基環己烯二羧酸酐、甲基環己烯四羧酸酐、苯二甲酸酐 '偏苯三酸酐、均苯四酸酐、二苯甲酮四羧酸酐、乙二醇 雙偏苯三酸酯、氯茵酸酐（Het Anhydride )、耐地酸酐（ -16- 200948843 nadic acid anhydride)、甲基耐地酸肝、5-( 2,5-二氧代 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。 環氧樹脂與硬化劑之調配比例較好爲環氧基與硬化劑 中之官能基當量比在0.8〜1.5之範圍。在該範圍外硬化後 亦會殘留未反應之環氧基或硬化劑中之官能基，且由於使 〇 與封裝機能相關之信賴性下降故而不佳。 本發明之無機塡充材對環氧樹脂組成物之添加量相對 於環氧樹脂組成物爲80〜96wt%，較好爲84〜96wt%。若少 於此値則無法充分的發揮本發明目的效果之高熱傳導性、 低熱膨脹性、高耐熱性。該等效果以無機塡充材之添加量 愈多愈好，但並非隨著其體積分率而提升者，而是隨著特 定之添加量而急速提高。該等物性係高分子狀態之高次構 造受到控制之效果者，認爲係由於該高次構造主要於無機 © 塡充材之表面達成，故特定量之無機塡充材成爲有必要者 。另一方面’無機塡充材之添加量若多於此値則黏度升高 ，使成行性變差而不佳。 上述無機塡充材以球形者較佳，且只要是剖面爲橢圓 者亦包含球狀者則無特別限制，但就流動性改善之觀點而 言’最好極度接近真球狀者。據此，容易獲得面心立方構 造或六方稠密構造等之最密充塡構造，且可獲得足夠之充 塡量。非球形時，充塡量增加時會增加塡充材彼此之摩擦 ，使得到達上述上限之前之流動性極度下降且黏度升高， -17- 200948843 使成形性變差故而不佳。 就熱傳導性之觀點而言，無機塡充材中較好使用 50wt%以上之熱傳導率5W/m. K以上者，且適用者爲氧化 鋁、氮化鋁、結晶氧化矽等。該等中最佳者爲球狀氧化鋁 。另外，亦可依據需要倂用與形狀無關之無定型無機塡充 材，例如熔融氧化矽、結晶氧化矽等。 無機塡充材之平均粒徑較好爲3 0 μιη以下。當平均粒 徑大於此値則會損及環氧樹脂組成物之流動性’或者亦使 © 強度降低而不佳。 本發明之環氧樹脂組成物中可調配已知之硬化促進劑 。舉例有例如胺類、咪唑類、有機膦類、路易斯酸等，具 體而言爲1，8-二氮雜雙環（5，4,0)十一烯-7、三乙二胺、 苄基二甲基胺、三乙醇胺、二甲胺基乙醇、參（二甲胺基 甲基）苯酚等三級胺，2-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、2-十七烷基咪唑等咪唑類，三丁基膦、甲基 二苯基隣、三苯基膦、二苯基膦、苯基膦等有機膦類，四 © 苯基鐄.四苯基硼酸鹽、四苯基鳞.乙基三苯基硼酸鹽、 四丁基鱗.四丁基硼酸鹽等四取代之鐵·四取代之硼酸鹽 、2-乙基-4-甲基咪唑.四苯基硼酸鹽、Ν-甲基嗎啉.四苯 基硼酸鹽等四苯基硼鹽等。添加量相對於重量份之環 氧樹脂通常爲0.2〜1〇重量份之範圍。該等可單獨使用亦 可倂用。 上述硬化促進劑之添加量相對於環氧樹脂（調配作爲 難燃劑之含鹵素之環氧樹脂時’包含該等）與硬化劑之合 -18- 200948843 計較好爲0.1~10.0wt%。當未達O.lwt%時，膠凝化時間變 慢使硬化時之剛性下降，導致作業性下降，相反地當超過 lO.Owt%時，成形過程中硬化變得不良，容易發生未充塡 〇 本發明之環氧樹脂組成物中，可使用於環氧樹脂組成 物中一般使用作爲離型劑之蠟。至於蠟可使用例如硬脂酸 、褐煤酸、褐煤酸酯、磷酸酯等。 〇 本發明之環氧樹脂組成物中爲了提高無機塡充材與樹 脂成分之黏著力，因此可使用在環氧樹脂組成物中一般使 用之偶合劑。至於偶合劑可使用例如環氧基矽烷。偶合劑 之添加量相對於環氧樹脂組成物以0.1〜2 · 0 wt %較佳。若未 達0.1 wt%則樹脂與基材之密著變差而使成形性變差，相 反地當超過2.0 wt%時，於連續成形性之成形品會產生污 損。 又本發明之環氧樹脂組成物就成形時之流動性改良以 〇 及與導線架等之基材之密著性提高之觀點而言，可添加熱 可塑性寡聚物類。熱可塑性寡聚物類例示爲C5系及C9系 石油樹脂、苯乙烯樹脂、茚樹脂、茚·苯乙烯共聚合樹脂 、茚·苯乙烯·酚共聚合樹脂、茚·香豆酮共聚合樹脂、 茚·苯并噻吩共聚合樹脂等。添加量相對於100重量份之 環氧樹脂通常爲2~30重量份之範圍。 再者本發明之環氧樹脂組成物可使用適當調配有一般 環氧樹脂組成物中可使用者。例如，可使用磷系難燃劑、 溴化合物或三氧化銻等難燃劑，及碳黑或有機染料等之著 -19- 200948843 色劑等。 本發明之環氧樹脂組成物係以環氧樹脂、硬化劑及無 機塡充材作爲主要成分。塡充材除外之樹脂成分中，環氧 樹脂及硬化劑之調配比例爲50wt%以上’較好爲70wt%以 上，更好爲80wt%以上。又，塡充材除外之樹脂成分意指 硬化後成爲塡充材以外之成分之所有成分。或者，意指硬 化物中之充塡劑之所有成分。 本發明之環氧樹脂組成物係以混練機將環氧樹脂、硬 化劑、無機塡充材及偶合劑以外之其他成分均勻的混合後 ，添加偶合劑，且藉由加熱輥、捏合機等混練製造。該等 成分之調配順序並無特別限制。另外，混練後進行熔融混 練物之粉碎，亦可進行粉末化或顆粒化。 本發明之環氧樹脂組成物尤其適於半導體裝置之封裝 用。 本發明之硬化物係藉由使上述環氧樹脂組成物熱硬化 而獲得。用以使用本發明之環氧樹脂組成物獲得硬化物可 使用例如遞模成形、壓鑄成形、注型成形、射出成形、擠 壓成形等方法，但就量產性之観點而言，以遞模成形較佳 〇 本發明之硬化物就高熱傳導性之觀點而言較好爲具有 結晶性者。硬化物之結晶性之展現係以差示掃描熱量分析 觀測伴隨著結晶之熔解之吸熱峰作爲熔點加以確認。較佳 之熔點爲120 °C至280 °C之範圍’更好爲150 °C至250。(：之 範圍。又’硬化物之較佳熱傳導率爲4W/m . K以上，最 -20- 200948843 好爲6W/m. K以上。 本發明之硬化物之結晶化度以較高者較佳，結晶化程 度可由差示掃描熱量分析之伴隨著結晶熔解之吸熱量予以 評價。較佳之吸熱量爲塡充材除外之樹脂成分之每單位重 量爲10J/g以上。更好爲15J/g以上，最好爲30J/g以上 。若比該値小則作爲環氧樹脂硬化物之熱傳導率提高效果 小。另外，就低膨脹性及提升耐熱性之觀點而言，結晶性 〇 愈高愈好。又，此處所謂的吸熱量係指由差示掃描熱量分 析計，使用精秤約l〇mg之試料，在氮氣流下，升溫速度 1 Ot /分鐘之條件下測定獲得之吸熱量。 本發明之環氧樹脂硬化物可藉由上述成形方法藉加熱 硬化而獲得，但通常成形溫度爲80°C至250°C，但爲了提 升環氧樹脂硬化物之結晶化度，較好在比硬化物之熔點低 之溫度下硬化。較佳之硬化溫度爲1〇〇 °C至200 °C之範圍， 更好爲1 3 0 °C至1 8 0 °C。又，較佳之硬化時間爲3 0秒至1 ❹ 小時，更好爲1分鐘至30分鐘。進一步成形後，藉由後 硬化可進一步提升結晶化度。通常，後硬化溫度爲130°C 至2 5 0 °C，時間爲1小時至2 0小時之範圍，但較好在比差 示掃描熱量分析之吸熱峰溫度低5°C至40°C之溫度下進行 後硬化1小時至2 4小時較佳。 [實施例] 藉由以下列實施例更具體說明本發明。 參考例1 -21 - 200948843 使150.0g氫醌溶解於1260g環氧氯丙烷、i2〇g二乙 二醇二甲基醚中，在60°C下添加22.7g之4 8%氫氧化鈉並 攪拌1小時。隨後’在減壓下（約130托耳）於3小時內 滴加204.5g之48%氫氧化鈉水溶液。其間，產生之水藉 由與環氧氯丙烷共沸而排除於系統之外，餾出之環氧氯丙 烷則回到系統內。滴加結束後’再繼續反應1小時並脫水 後，餾除環氧氯丙烷，且添加600g之甲基異丁基酮後， 進行水洗將鹽去除。隨後，在85 °C下添加20.0g之48 %氫 ❹ 氧化鈉且攪拌1小時’且以2 0 0 m 1溫水水洗。隨後，藉由 分液將水去除後，減壓餾除甲基異丁基酮，獲得278g之 白色結晶狀環氧樹脂。環氧當量爲117，水解性氯爲 310ppm，以毛細管法測得之熔點爲84。(：至101°C，於 120°C之黏度爲1.8mPa. s。所得樹脂之藉由GPC測定求 得之由氫_所得環氧樹脂之各成分比爲n = 0(單體）爲 85.7%，n=l (二聚物）爲 9.1%，n = 2(三聚物）爲 1.6%。 其中，所謂的水解性氯爲將0.5g試料溶解於3 0ml之二噁 ® 烷中之後’添加l〇ml之1N-KOH且沸騰回流30分鐘後， 冷卻至室溫’接著添加1 0 0 m 1含8 0 %丙酮之水所得者，以 0.002N-AgN〇3水溶液進行電位差滴定獲得之値。又所謂 熔點爲藉由毛細管法以2°C /分鐘之升溫速度獲得之値。黏 度係以BROOHFIELD製造之CAP2000H測定，軟化點係 依據JIS K-691 1 ’以環球法測定。另外，GPC測定爲：裝 置：曰本WATERS (股）製造之51 5A型，管柱：TSK-GEL2000x3根及TSK-GEL4000xl根（均爲東曹（股）製 -22- 200948843 造），溶劑：四氫咲喃’流量：Iml/min’溫度·· 38°C ’檢 出器：依據RI之條件。 參考例2 使lOO.Og之4,4’-二羥基聯苯溶解於700g環氧氯丙烷 、105g二乙二醇二甲基醚中，隨後，在減壓下（約130托 耳）及6 0 °C下’於3小時內滴加8 7 · 8 g之4 8 %氫氧化鈉水 n 溶液。其間，產生之水藉由與環氧氯丙烷共沸排除於系統 之外，餾出之環氧氯丙烷則回到系統內。滴加結束後，再 繼續反應1小時並脫水後，冷卻至常溫，經過濾回收析出 物。隨後，以水洗滌析出物去除鹽，再經乾燥獲得1 3 7g 之結晶性粉末狀環氧樹脂。環氧當量爲163，以毛細管法 測得之熔點爲169°C至175°C。所得樹脂之由GPC測定求 得之通式（1)中各成分比爲n = 0爲93.7 %，n=l爲5.9% 實施例1 使50.0g氫醌、lOO.Og之4,4’-二羥基聯苯溶解於 1000g環氧氯丙烷' 150g二乙二醇二甲基醚中，且在6(rc 下添加1 6.5 g之4 8 %氫氧化鈉並攪拌1小時。隨後，在減 壓下（約130托耳）於3小時內滴加148.8g之48 %氫氧 化鈉水溶液。其間，產生之水藉由與環氧氯丙烷共沸排除 於系統之外，餾出之環氧氯丙烷則回到系統內。滴加結束 後’再繼續反應1小時並脫水後，餾除環氧氯丙烷，添加 -23- 200948843 600g之甲基異丁基酮後，進行水洗將鹽去除。隨後，在 85°C下添加13.5g之48%氫氧化鈉且攪拌1小時，以 200ml溫水水洗。隨後，藉由分液將水去除後，減壓餾除 甲基異丁基酮，獲得224g之白色結晶狀改性環氧樹脂（ 環氧樹脂A)。環氧當量爲139，水解性氯爲320ppm，以 毛細管法測得之熔點爲l〇4°C至141t，150°C下之黏度爲 3.4mPa · s。由GPC測定求得之由氫醌所得之環氧樹脂之 n = 0 (單體）爲 23.1%，n=l (二聚物）爲2.2%。又，以 4,4’-二羥基聯苯獲得之環氧樹脂之n = 0(單體）爲67.2% ，n=l (二聚物）爲 4.1 %。 實施例2 使 75.0g氫醌、75.0g之4,4’-二羥基聯苯溶解於 1000g環氧氯丙烷、15 0g二乙二醇二甲基醚中，在60°C下 添加18. lg之48%氫氧化鈉並攪拌1小時。隨後，在減壓 下（約130托耳）於3小時內滴加162.7g之4 8%氫氧化 〇 鈉水溶液。其間，產生之水藉由與環氧氯丙烷共沸排除於 系統之外，餾出之環氧氯丙烷則回到系統內。滴加結束後 ，再繼續反應1小時並脫水後，餾除環氧氯丙烷，添加 5 40g之甲基異丁基酮後，進行水洗將鹽去除。隨後，在 85°C下添加13.5g之48%氫氧化鈉且攪拌1小時，以 2 00ml溫水水洗。隨後，藉由分液將水去除後，減壓餾除 甲基異丁基酮，獲得214g之白色結晶狀改性環氧樹脂（ 環氧樹脂B)。環氧當量爲135，水解性氯爲3 8 0ppm，以 -24- 200948843 毛細管法測得之熔點爲108°C至H9t’150°C下之黏度爲 2.3mPa . s。由GPC測定求得之由氫醌所得環氧樹脂之 n = 0(單體）爲 53.1°/。，n=l (二聚物）爲 34.2%。又，由 4,4’-二羥基聯苯獲得之環氧樹脂之n==0(單體）爲7.2%， n=l (二聚物）爲 4.3%。 實施例3 〇 使125.0g氫醌、25.0g之4,4’-二羥基聯苯溶解於 1200g環氧氯丙烷、180g二乙二醇二甲基醚中，在60。(：下 添加21.2g之4 8%氫氧化鈉並攪拌1小時。隨後，在減壓 下（約130托耳）於3小時內滴加190.6g之48%氫氧化 鈉水溶液。其間’產生之水藉由與環氧氯丙烷共沸排除於 系統之外，餾出之環氧氯丙烷則回到系統內。滴加結束後 ，再繼續反應1小時並脫水後，餾除環氧氯丙烷，添加 560g之甲基異丁基酮後，進行水洗將鹽去除。隨後，在 ® 85°C下添加13_5g之48%氫氧化鈉且攪拌1小時，且以 2 00ml溫水水洗。隨後，藉由分液將水去除後，減壓餾除 甲基異丁基酮’獲得265g之白色結晶狀改性環氧樹脂（ 環氧樹脂C )。環氧當量爲丨24，水解性氯爲3 9〇ppm，以 毛細管法測得之熔點爲8 6 °C至1 0 5 °C，1 5 0 °C下之黏度爲 0.8mPa . s。由GPC測定求得之由氫醌所得之環氧樹脂之 n-0 (單體）爲n=l (二聚物）爲2.2%。又，由 4,4- 一羥基聯本獲得之環氧樹脂之n = 〇(單體）爲I〗」％ ，：η = 1 (二聚物）爲 3 · 0 %。 -25- 200948843 實施例4~8、比較例1〜5 使用實施例1至實施例3之改性環氧樹脂 編號順序稱爲環氧樹脂A、環氧樹脂B、環氧 參考例1之環氧樹脂（環氧樹脂D)、參考例 脂（環氧樹脂E)、雙酚系環氧樹脂（環氧樹 環氧樹脂公司製造之 YX-4000H ;環氧當量1 氧樹脂成分，以酚芳烷基樹脂（硬化劑A :三 之 XL-225-LL; OH 當量 174，軟化點 75°C) 化劑B ) 、4,4’-二羥基二苯基醚（硬化劑C ) ，以三苯基膦作爲硬化促進劑，以球狀氧化鋁 12·2μπι)作爲無機塡充材，調配表1中所示之 以混練機充分混合後，於加熱輥上混練5分鐘 ，經粉碎分別獲得實施例4〜8、比較例1 ~5之 成物。評價使用該環氧樹脂組成物在1 70°C、 件下成形後，在170°C下進行後硬化12小時獲 物性。實施例之結果彙整列於表1，比較例之 2°又’表1及表2中各調配物之數字表示重 比較例5由於成形不良因而無法進行硬化成形 價。 評價方法如下。 C1) 熱傳導率係使用NETZSCH製造之 熱傳導率計’藉由非固定熱線法測定。 (2) 熔點、熔解熱（DSC法）係使用差 (依實施例 樹脂C )、 2之環氧樹 脂F :日本 9 5 )作爲環 井化學製造 、氫醌（硬 作爲硬化劑 (平均粒徑 成分及量， 者予以冷卻 環氧樹脂組 5分鐘之條 得成形物之 結果列於表 量份。又， 物之物性評 LFA447 型 示掃描熱量 200948843 分析裝置（精工儀器製造之DSC 6200型），在升溫速度 l〇°C/分鐘下測定。 (3) 線膨脹係數、玻璃轉移溫度係使用精工儀器（ 股）製造之TMA120C型熱機械測定裝置，在升溫速度 l〇°C/分鐘下測定。 (4 ) 吸水率係成形直徑50mm，厚度3mm之圓盤， 經後硬化後，在8 5 °C '相對濕度8 5 %之條件下吸濕1 0 0小 〇 時後之重量變化率。 [表1] 實施例 4 5 6 7 8 環氧樹脂A 66.5 107.5 87.0 環氧樹脂B 65.5 環氧樹脂C 62.5 硬化劑A 83.5 84.5 87.5 硬化劑B 42.5 硬化劑C 63.0 無機塡充材 1000 1000 1000 1000 1000 硬化促進劑 1.6 1.6 1.6 1.6 1.6 膠凝時間（sec) 33 34 37 45 42 螺線流動度（cm) 101 110 114 130 127 玻璃轉移點（°C) 134 132 131 87 89 熱膨脹係數（ppm，<Tg) 13.0 14.0 14.0 11.0 10.0 熱膨脹係數（ppm，>Tg) 56.0 57.0 60.0 53.0 52.0 熱變形溫度（°C) 144 142 141 167 172 吸水率（wt%,100h) 0.14 0.15 0.14 0.12 0.11 熱傳導率（W/m，K) 4.3 4.2 4.2 5.0 5.2 熔點（°C) . . 166.3 199.5 熔解熱（J/g-樹脂） 0 0 0 15 26 -27- 200948843 [表2] 比較例 1 2 3 4 5 _ 環氧樹脂D 60.0 34.0 33.0 環氧樹脂E 33.0 環氧樹脂F 34.0 79.0 117.0 硬化劑A 90.0 82.0 71.0 84.0 硬化劑B 33.0 無機充塡材 1000 1000 1000 1000 1000 硬化促進劑 1.6 1.6 1.6 1.6 1.6__ 膠凝時間（sec) 44 49 35 48 螺線流動度（cm) 96 93 77 82 玻璃轉移點rc) 118 122 128 89 熱膨脹係數（Ppm，<Tg) 13.0 15.0 21.0 18.0 熱膨脹係數（ppm，>Tg) 74.0 84.0 82.0 75.0 熱變形溫度（°C) 121 124 131 94 吸水率（wt%，100h) 0.24 0.23 0.21 0.23 熱傳導率（W/m-K) 3.5 3.3 3.2 3.3 熔點（°C) _ 熔解熱（J/g-樹脂） 0 0 0 0 [產業上利用之可能性] 本發明之改性環氧樹脂及環氧樹脂組成物可獲得成形 性、信賴性優異且高熱傳導性、低吸水性、低熱膨脹性、 高耐熱性優異之硬化物，可適當應用於作爲半導體封裝、 層合板、放熱基板等之電氣、電子零件用絕緣材$、丨 u料，而發 揮優異之高放熱性及尺寸安定性。 -28-Further, the present invention is an epoxy resin composition characterized by an epoxy resin composition comprising (A) an epoxy resin, (B) a hardener, and (C) an inorganic cerium filler as a main component, wherein 50% by weight or more of the above modified epoxy resin is used as the epoxy resin. The preferred aspects of the above epoxy resin composition are as follows: 1) the content of the inorganic cerium filler is 80 to 96% by weight, 2) the hardener is a phenolic hardener, 3) the use of 50% by weight or more of difunctionality Phenolic compound as phenolic hardener, -9- 200948843 4) The above difunctional phenolic compound is selected from the group consisting of hydroquinone, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether' 1,4 - bis(4-hydroxyphenoxy)benzene, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl sulfide, 1,5-naphthalenediol, 2,7-naphthalene At least one of a group consisting of diphenol and 2,6-naphthalenediol, 5) using 50% by weight or more of spherical alumina as an inorganic ruthenium. Furthermore, the present invention is an epoxy resin composition as described above, which is characterized in that it is an epoxy resin composition for semiconductor encapsulation. Further, the present invention is a cured product obtained by curing the epoxy resin composition described above and having a thermal conductivity of 4 W/m·K or more. Wherein, in the differential scanning calorimetry of the hardened material, the peak value of the melting point is in the range of 120 ° C to 280 ° C, or the differential scanning calorimetry of the cured product, wherein the heat content of the resin component is 10 J/g or more. . [Embodiment] The modified epoxy resin of the present invention can be produced by reacting a mixture of hydroquinone and 4,4'-dihydroxybiphenyl with epichlorohydrin. This reaction can be carried out in the same manner as in the usual epoxidation reaction. The modified epoxy resin of the present invention may contain, in addition to the epoxide of hydroquinone and the epoxide of 4,4'-dihydroxybiphenyl, having a hydroquinone derived from each molecule and 4, 4' a mixture of epoxides of units of dihydroxybiphenyl. Therefore, as is known, the epoxide obtained by the reaction of a dihydroxy compound with epichlorohydrin contains n=l (dimer) in addition to the epoxide (n = 0 polymer) having a degree of polymerization. a polymer such as n = 2 (trimer). The mixing ratio of hydroquinone to 4,4'-dihydroxybiphenyl is in the weight ratio of hydrogen-10-200948843 醌/4,4'-dihydroxybiphenyl=〇·ι~i〇.〇, but Good for 〇 2~5. 〇 range. When the ratio is smaller than this, the workability is poor under the influence of the high melting point of the epoxide of 4,4 ′-dihydroxybiphenyl. When the ratio is larger than this ratio, the heat resistance and the like of the cured product are deteriorated. For example, after dissolving a mixture of hydroquinone and 4,4'-dihydroxybiphenyl in an excess of epichlorohydrin relative to the molar ratio of the phenolic hydroxyl groups, in sodium hydroxide or potassium hydroxide In the presence of a metal hydroxide, the reaction is carried out at 50 to 150 ° C, preferably in the range of 60 to 100 ° C for 1 to 10 hours. At this time, the amount of the alkali metal hydroxide used is 〇.8 to i.2 moles, preferably 0.9 to 1.0 moles, relative to the hydroxyl group of the hydroquinone and the 4,4'-dihydroxybiphenyl. The scope. The epichlorohydrin is used in an excess amount relative to the hydroquinone and the hydroxyl group in the 4,4'-dihydroxybiphenyl, and is usually 1.5 to the hydroquinone in the hydroquinone and the 4,4'-dihydroxybiphenyl. 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 the inorganic salt is removed by filtration and washing with water to obtain a target by distilling off the solvent. Epoxy resin. In the production of the modified epoxy resin of the present invention, other phenolic compounds may be further mixed in addition to hydroquinone and 4,4'-dihydroxybiphenyl which are essential components of the raw material. However, in this case, the total amount of hydroquinone and 4,4'-dihydroxybiphenyl is preferably 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more based on the total phenolic compound. The epoxy equivalent of the modified epoxy resin of the present invention is usually in the range of 110 to 300. However, in view of the high filling rate of the inorganic cerium filling material and the improvement of the fluidity, the low viscosity is preferred. It is preferably in the range of epoxide equivalents from 1 10 to -11 - 200948843 160. The modified epoxy resin of the present invention has crystallinity at normal temperature. The exhibitivity of crystallinity can be confirmed by differential scanning calorimetry as an endothermic peak accompanying crystal melting. Further, since the modified epoxy resin of the present invention is a mixture, the endothermic peak in this case is generally not observed as an endothermic peak but plural. The absorption point observed by differential scanning calorimetry is the absorption peak of the modified epoxy resin derived from the source free hydroquinone and 4,4'-dihydroxybiphenyl, and the endothermic peak of the lowest temperature is 50 ° C or more. When the temperature is 70 ° C or higher, the endothermic peak of the highest temperature is 150 ° C or lower, preferably 130 ° C or lower. If it is lower than this temperature, it will cause agglomeration or the like when it is used as a powder, and it becomes a solid at normal temperature to lower the workability. When it is higher than this temperature, there is a problem that solubility with a curing agent or the like is poor. Further, the melting viscosity at 150 ° C is preferably as low as possible, and is usually O.lPa·s or less, preferably 〇.iPa·s or less, more preferably 〇.〇〇5Pa.s or less, The purity of the modified epoxy resin of the invention, especially the amount of hydrolyzable chlorine, is preferably from the viewpoint of improving the reliability of the applicable electronic component. Although not particularly limited, it is preferably not more than 1,000,000, more preferably less than 500 pm. Further, the hydrolyzable chlorine in the present invention is determined by the following method. That is, after dissolving 〇.5g of the sample in 30 ml of dioxane, 10 ml of 1N-KOH was added and boiled and refluxed for 30 minutes, and then cooled to room temperature, followed by adding a port of 1 1111 containing 80% acetone water. And 〇.〇〇2:^- into the Lu 1 ^ 03 aqueous solution for potential difference titration obtained. The epoxy resin composition of the present invention comprises (A) an epoxy resin, (B) a hardener, and (C) an inorganic ruthenium as a main component, and is used as an epoxy resin component of Epoxy-12-200948843 grease. More than 50% by weight of the above modified epoxy resin is contained. That is, 50% by weight or more of all the epoxy resins are the above-mentioned modified epoxy resins. Advantageously, more than 70% by weight, more preferably more than 90% by weight of the total epoxy resin is the modified epoxy resin described above. The use ratio of the modified epoxy resin is less than that of the heat conductivity at the time of forming the cured product. In the epoxy resin composition of the present invention, in addition to the above-mentioned modified epoxy resin used as an essential component of the present invention, another general epoxy resin having two or more epoxy groups in the molecule may be used. Examples are bisphenol A, bisphenol F, 3,3',5,5'-tetramethyl-4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl maple' 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, bismuth bisphenol, 4,4'-diphenol, 3,3',5,5'-tetramethyl -4,4'-dihydroxybiphenyl, 2,2'-diphenol, resorcinol, catechol, tert-butylcatechol, tert-butylhydroquinone, 1,2-dihydroxynaphthalene , 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2 , 3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene' ❹ 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxynaphthalene, the above two a valent phenol such as an allyl compound or a polyallyl compound of hydroxynaphthalene, an allylated bisphenol A, an allylated bisphenol F, or an allylated bisphenol novolak resin, or a phenol novolac Resin, bisphenol A novolac resin, o-cresol novolac resin, m-cresol novolac resin, p-cresol novolak resin, xylenol novolac resin, poly-p-hydroxystyrene, ginseng- (4- Hydroxyphenyl)methane, 1,1,2,2-indolyl (4-hydroxyphenyl)ethane, fluoroglycolol, biphenyltriol, tert-butyl pyrogallol allylic biphenyl Trisphenol, polyallylated pyrogallol, 1,2,4-benzenetriol, 2,3,4-trihydroxybenzophenone-13- 200948843, phenol aralkyl resin, naphthol aralkyl A trivalent or higher valence of a base resin or a dicyclopentadiene-based resin, or a glycidyl ether derivative derived from a halogenated bisphenol such as tetrabromobisphenol a. These epoxy resins may be used singly or in combination of two or more. It is known that it can be used as a hardener for the epoxy resin composition of the present invention as a general epoxy resin hardener, but a preferred hardener is a phenolic hardener. The phenolic curing agent has a phenolic compound, and the phenolic compound contains a phenol resin in addition to the phenol compound as a single compound. Specific examples of the phenolic hardener are bisphenol A, bisphenol F, 4,4'-dihydroxydiphenylmethane, 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 milling, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10 -phosphaphenanthrene-10-oxide, phenol novolac resin, bisphenol A novolac resin, o-cresol novolac resin, m-cresol novolac resin, p-cresol novolac resin, dimethyl phenol aldehyde Varnish ^ Resin, poly-p-hydroxystyrene, hydroquinone, m-xylylene, catechin, tert-butylcatechol, tert-butylhydroquinone, fluoroglycolol, biphenyl triterpene, Tertiary butyl biphenyl, propylated biphenyl, polypropylated biphenyl, 1,2,4-benzenetriazide, 2,3,4-trisylbiphenyl Ketone, 1,2-monopyridyl, 1,3-dihydroxynaphthalene, iota, 4-dihydroxynaphthalene, I,5-dihydroxynaphthalene, anthracene, 6-dihydroxynaphthalene' 1,7-dihydroxynaphthalene,丨,8·dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dipyridyl, 2 , 8-dihydroxynaphthalene's above-mentioned dihydroxynaphthalene pseudo-propylate or poly-fired C-14-200948843 base, allylated bisphenol A, allylated bisphenol F, allylated bisphenol phenolic Varnish resin, allylated biphenyltriol, and the like. The hardener may also be used by mixing two or more hardeners. A preferred hardener is a phenolic compound containing 50% by weight or more, preferably 70% by weight or more of the difunctional group in the hardener. The difunctional phenol compound at this time is preferably selected from the group consisting of 4,4'-dihydroxybiphenyl and 4,4'-dihydroxydiphenyl ether '1,4-bis(4-hydroxyphenoxy)benzene. 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylfluorenone, 4,4'-dihydroxydiphenyl sulfide, 1,5-naphthalenediol, 2,7- A phenolic compound of naphthalenediol, 2,6-naphthalenediol, hydroquinone, and meta-xylenol. Among them, preferred is 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether or 4,4'-dihydroxydiphenylmethane. The curing agent used in the epoxy resin composition of the present invention may be used as a curing agent in addition to the above-mentioned phenolic curing agent, using a generally known curing agent. For example, an amine-based curing agent, an acid-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, a blocked isocyanate-based curing agent, and the like are exemplified. The amount of the curing agent to be added may be appropriately set in consideration of the type of the curing agent to be blended or the physical properties of the molded body of the obtained thermally conductive epoxy resin. Specific examples of the amine-based curing agent are aliphatic amines, polyether polyamines, alicyclic amines, and aromatic amines. As the aliphatic amines, for example, ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, Trimethylhexamethylenediamine, diethylidene triamine, iminodipropylamine, bis(hexamethylene)triamine, triethylidenetetramine, tetraethylidene pentaamine, five Ethyl hexamine, N-hydroxyethyl extension -15- 200948843 Ethylenediamine, tetrakis(hydroxyethyl)ethylenediamine, and the like. The polyether polyamines are exemplified by triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis (propylamine), polyoxypropylene diamine, polyoxypropylene propyl triamine and the like. Examples of the alicyclic amines are isophorone diamine, mennene diamine, N-aminoethylpiperidine, bis(4-amino-3-methyldicyclohexyl)methane, bis(amine group A) Base) cyclohexane, 3,9-bis(3-aminopropyl) 2,4,8,10-tetraoxaspiro(5,5)undecane, norbornene diamine, and the like. Examples of the aromatic amines are tetrachloro-p-xylenediamine, m-xylylenediamine, p-xylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2, 4-diaminoanisole, 2,4-toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino -1,2-diphenylethane, 2,4-diaminodiphenylphosphonium, 4,4'-diaminodiphenylphosphonium, m-aminophenol, m-aminobenzylamine, Benzyldimethylamine, 2·(dimethylaminomethyl)phenol, triethanolamine, methylbenzylamine, α-(m-aminophenyl)ethylamine, a-(p-aminobenzene) Ethylamine, diaminodiethyldimethylmethane, α,α,_bis(4-aminophenyl)-p-isopropylbenzene, and the like. Specific examples of the acid anhydride-based hardener are, for example, dodecenyl succinic anhydride, polyadipate anhydride, polysebacic anhydride, polysebacic anhydride, poly(ethyl octadecandioic acid) anhydride, poly(phenyl hexadecane) Alkanedioic acid anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methyl endomethylenetetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trioxane Tetrahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, methylcyclohexene tetracarboxylic anhydride, phthalic anhydride' trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol double Trimellitic acid ester, Het Anhydride, oxalic anhydride (-16-200948843 nadic acid anhydride), methyl dysfunctional acid liver, 5-(2,5-dioxotetrahydro-3-furan 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. The ratio of the epoxy resin to the hardener is preferably such that the functional group equivalent ratio of the epoxy group to the hardener is in the range of 0.8 to 1.5. The unreacted epoxy group or the functional group in the hardener remains after hardening outside this range, and it is not preferable because the reliability associated with the package function is lowered. The amount of the epoxy resin composition to be added to the epoxy resin composition of the present invention is 80 to 96% by weight, preferably 84 to 96% by weight based on the epoxy resin composition. If it is less than this, the high thermal conductivity, low thermal expansion property, and high heat resistance of the effects of the present invention cannot be sufficiently exerted. These effects are better as the amount of the inorganic cerium filler added, but it is not increased with the volume fraction, but is rapidly increased with the specific addition amount. It is considered that the high-order structure of these physical properties is controlled by the effect of the high-order structure mainly on the surface of the inorganic © cerium filler material, so that a certain amount of the inorganic cerium filler is necessary. On the other hand, if the amount of the inorganic cerium filler added is more than this, the viscosity is increased, which makes the gradation worse. The inorganic ruthenium filler is preferably spherical, and is not particularly limited as long as it has an elliptical cross section and a spherical shape. However, it is preferable that the fluidity is improved to be close to a true spherical shape. According to this, it is easy to obtain the most densely packed structure such as a face-centered cubic structure or a hexagonal dense structure, and a sufficient amount of charge can be obtained. When it is non-spherical, the increase in the amount of charge increases the friction between the ruthenium materials, so that the fluidity before the above upper limit is extremely lowered and the viscosity is increased, and -17-200948843 deteriorates the formability. From the viewpoint of thermal conductivity, it is preferable to use 50% by weight or more of the thermal conductivity of 5 W/m. K or more in the inorganic cerium material, and it is preferably aluminum oxide, aluminum nitride, crystalline cerium oxide or the like. The best of these is spherical alumina. Further, an amorphous inorganic cerium filler which is not related to the shape, such as molten cerium oxide, crystalline cerium oxide or the like, may be used as needed. The average particle diameter of the inorganic cerium filler is preferably 30 μm or less. When the average particle diameter is larger than this, the fluidity of the epoxy resin composition may be impaired or the strength of EPS may be lowered. A known hardening accelerator can be formulated in the epoxy resin composition of the present invention. Examples are, for example, amines, imidazoles, organic phosphines, Lewis acids and the like, in particular 1,8-diazabicyclo(5,4,0)undecene-7, triethylenediamine, benzyldi Tertiary amines such as methylamine, triethanolamine, dimethylaminoethanol, ginseng (dimethylaminomethyl)phenol, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole , imidazoles such as 2-heptadecylimidazole, organic phosphines such as tributylphosphine, methyldiphenyl ortho, triphenylphosphine, diphenylphosphine, phenylphosphine, tetraphenylene.tetraphenyl Tetra-substituted iron tetra-substituted borate, 2-ethyl-4-methylimidazole, such as borate, tetraphenyl sulphate, ethyl triphenyl borate, tetrabutyl sulphate, tetrabutyl borate. Tetraphenylborate such as tetraphenylborate, Ν-methylmorpholine or tetraphenylborate. The amount of addition is usually in the range of 0.2 to 1 part by weight based on parts by weight of the epoxy resin. These can be used alone or in combination. The amount of the hardening accelerator added is preferably from 0.1 to 10.0% by weight based on the combination of the epoxy resin (including the halogen-containing epoxy resin as a flame retardant) and the curing agent -18-200948843. When it is less than 0.1% by weight, the gelation time becomes slow, and the rigidity at the time of hardening is lowered, resulting in a decrease in workability. Conversely, when it exceeds 0.01% by weight, hardening becomes poor during the forming process, and unfilling is liable to occur. 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. As the wax, for example, stearic acid, montanic acid, montanic acid ester, phosphate ester or the like can be used.为了 In order to increase the adhesion between the inorganic enamel and the resin component in the epoxy resin composition of the present invention, 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 wt% with respect to the epoxy resin composition. When the amount is less than 0.1% by weight, the adhesion between the resin and the substrate is deteriorated to deteriorate the moldability, and when it exceeds 2.0 wt%, the molded article having continuous formability is stained. Further, in the epoxy resin composition of the present invention, thermoplasticity oligomers can be added from the viewpoint of improving fluidity during molding and improving adhesion to a substrate such as a lead frame. The thermoplastic oligomers are exemplified by C5-based and C9-based petroleum resins, styrene resins, oxime resins, styrene-styrene copolymer resins, styrene-styrene-phenol copolymer resins, ketone-coumarone copolymer resins, and茚·benzothiophene copolymerized resin, and the like. The amount of addition is usually 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 in a general epoxy resin composition. For example, a phosphorus-based flame retardant, a flammable agent such as a bromine compound or antimony trioxide, and a toner such as carbon black or an organic dye can be used. The epoxy resin composition of the present invention contains an epoxy resin, a hardener and an inorganic ruthenium as main components. In the resin component other than the cerium filler, the blending ratio of the epoxy resin and the curing agent is 50% by weight or more', preferably 70% by weight or more, more preferably 80% by weight or more. Further, the resin component excluding the ruthenium filler means all components which are components other than the ruthenium after hardening. Or, it means all the components of the filling agent in the hard compound. The epoxy resin composition of the present invention is obtained by uniformly mixing an epoxy resin, a curing agent, an inorganic cerium filling material and other components other than a coupling agent in a kneading machine, adding a coupling agent, and kneading by a heating roll, a kneading machine or the like. Manufacturing. The order in which these ingredients are formulated is not particularly limited. Further, after the kneading, the melt kneaded material is pulverized, and powdering or granulation may be carried out. The epoxy resin composition of the present invention is particularly suitable for encapsulation of semiconductor devices. The cured product of the present invention is obtained by thermally hardening the above epoxy resin composition. For obtaining the cured product using the epoxy resin composition of the present invention, methods such as transfer molding, die casting molding, injection molding, injection molding, extrusion molding, and the like can be used, but in terms of mass production, Mold forming is preferred. The cured product of the present invention preferably has crystallinity from the viewpoint of high thermal conductivity. The crystallinity of the cured product was confirmed by differential scanning calorimetry to observe the endothermic peak accompanying the melting of the crystal as the melting point. The preferred melting point is in the range of from 120 ° C to 280 ° C, more preferably from 150 ° C to 250. (: the range. The preferred thermal conductivity of the cured product is 4 W/m. K or more, and most -20-200948843 is preferably 6 W/m. K or more. The crystallization degree of the cured product of the present invention is higher. Preferably, the degree of crystallization can be evaluated by the differential heat of differential scanning calorimetry accompanied by the melting of the crystal. The preferred heat absorption is 10 J/g or more per unit weight of the resin component excluding the cerium filling material, more preferably 15 J/g. In the above, it is preferably 30 J/g or more. When it is smaller than this, the effect of improving the thermal conductivity of the cured epoxy resin is small. Further, from the viewpoint of low expandability and heat resistance, the crystallinity is higher. Further, the term "heat absorption" as used herein refers to a sample obtained by a differential scanning calorimeter using a sample of about 1 〇mg of a fine scale, and a heat absorption rate of 1 Ot / minute under a nitrogen stream. The cured epoxy resin of the invention can be obtained by heat curing by the above-mentioned forming method, but usually the forming temperature is from 80 ° C to 250 ° C, but in order to improve the degree of crystallization of the cured epoxy resin, it is better to harden Hardening at a temperature at which the melting point of the substance is low. The hardening temperature is preferably in the range of from 1 ° C to 200 ° C, more preferably from 130 ° C to 180 ° C. Further, the preferred hardening time is from 30 seconds to 1 hour, more preferably 1 Minutes to 30 minutes. After further forming, the degree of crystallization can be further improved by post-hardening. Usually, the post-hardening temperature is 130 ° C to 250 ° C, and the time is in the range of 1 hour to 20 hours, but preferably Post-hardening is preferably carried out at a temperature lower by 5 ° C to 40 ° C than the endothermic peak temperature of the differential scanning calorimetry for 1 hour to 24 hours. [Examples] The present invention will be more specifically illustrated by the following examples. Reference Example 1 -21 - 200948843 150.0 g of hydroquinone was dissolved in 1260 g of epichlorohydrin, i2 g of diethylene glycol dimethyl ether, and 22.7 g of 48% sodium hydroxide was added and stirred at 60 ° C. 1 hour. Then, under reduced pressure (about 130 Torr), 204.5 g of 48% aqueous sodium hydroxide solution was added dropwise over 3 hours. During this time, the produced water was removed from the system by azeotroping with epichlorohydrin. In addition, the distilled epichlorohydrin is returned to the system. After the completion of the dropwise addition, the reaction is further continued for 1 hour and dehydrated, and the epichlorohydrin is distilled off. After 600 g of methyl isobutyl ketone was added, the salt was removed by washing with water. Subsequently, 20.0 g of 48% hydroquinone sodium oxide was added at 85 ° C and stirred for 1 hour', and washed with 200 ml of warm water. Subsequently, the water was removed by liquid separation, and methyl isobutyl ketone was distilled off under reduced pressure to obtain 278 g of a white crystalline epoxy resin. The epoxy equivalent was 117 and the hydrolyzable chlorine was 310 ppm, which was measured by a capillary method. The melting point is 84. (: to 101 ° C, the viscosity at 120 ° C is 1.8 mPa. s. The obtained resin is determined by GPC. The ratio of the components of the obtained epoxy resin is n = 0 (single The body was 85.7%, n=l (dimer) was 9.1%, and n = 2 (trimer) was 1.6%. Here, the so-called hydrolyzable chlorine is obtained by dissolving 0.5 g of the sample in 30 ml of dioxane®, adding 1 ml of 1N-KOH, boiling and refluxing for 30 minutes, and then cooling to room temperature, followed by adding 100 m. 1 obtained by using water containing 80% acetone, and obtained by potentiometric titration with a 0.002N-AgN〇3 aqueous solution. Further, the melting point is obtained by a capillary method at a temperature elevation rate of 2 ° C /min. The viscosity was measured by CAP2000H manufactured by BROOHFIELD, and the softening point was measured by the ring method according to JIS K-691 1 '. In addition, GPC was measured as: Apparatus: Type 51 5A manufactured by Sakamoto WATERS Co., Ltd., pipe column: TSK-GEL2000x3 root and TSK-GEL4000xl root (made by Tosoh Corporation -22-200948843), solvent: Tetrahydrofuran 'flow: Iml / min 'temperature · · 38 ° C 'detector: according to RI conditions. Reference Example 2 100.Og of 4,4'-dihydroxybiphenyl was dissolved in 700 g of epichlorohydrin, 105 g of diethylene glycol dimethyl ether, followed by under reduced pressure (about 130 Torr) and 6 At 0 °C, 8 7 · 8 g of 4 8 % sodium hydroxide water n solution was added dropwise over 3 hours. In the meantime, the produced water is removed from the system by azeotrope with epichlorohydrin, and the distilled epichlorohydrin is returned to the system. After completion of the dropwise addition, the reaction was further continued for 1 hour and dehydrated, and then cooled to room temperature, and the precipitate was collected by filtration. Subsequently, the precipitate was washed with water to remove the salt, and dried to obtain 137 g of a crystalline powdery epoxy resin. The epoxy equivalent was 163, and the melting point measured by a capillary method was 169 ° C to 175 ° C. The ratio of each component in the formula (1) obtained by GPC measurement of the obtained resin was n = 0 was 93.7%, and n = l was 5.9%. Example 1 50.0 g of hydroquinone, 100 g of 4,4'- Dihydroxybiphenyl was dissolved in 1000 g of epichlorohydrin '150 g of diethylene glycol dimethyl ether, and 1 6.5 g of 48% sodium hydroxide was added at 6 (rc) and stirred for 1 hour. Under the next (about 130 Torr), 148.8 g of a 48% aqueous sodium hydroxide solution was added dropwise over 3 hours. During this time, the produced water was removed from the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was distilled off. Then, after returning to the system, after the completion of the dropwise addition, the reaction was further continued for 1 hour and dehydrated, and then the epichlorohydrin was distilled off, and after adding -23-200948843 600 g of methyl isobutyl ketone, the salt was removed by washing with water. 13.5 g of 48% sodium hydroxide was added at 85 ° C and stirred for 1 hour, and washed with 200 ml of warm water. Then, after the water was removed by liquid separation, methyl isobutyl ketone was distilled off under reduced pressure to obtain 224 g of White crystalline modified epoxy resin (epoxy resin A). The epoxy equivalent is 139, the hydrolyzable chlorine is 320 ppm, and the melting point measured by capillary method is l〇4 ° C to 141 t, 150 ° C. The viscosity is 3.4 mPa · s. The epoxy resin obtained by GPC has n = 0 (monomer) of 23.1% and n = l (dimer) of 2.2%. The epoxy resin obtained from 4'-dihydroxybiphenyl has n = 0 (monomer) of 67.2% and n = l (dimer) of 4.1%. Example 2 75.0 g of hydroquinone, 75.0 g of 4 4'-dihydroxybiphenyl was dissolved in 1000 g of epichlorohydrin, 150 g of diethylene glycol dimethyl ether, and 18. lg of 48% sodium hydroxide was added at 60 ° C and stirred for 1 hour. Under reduced pressure (about 130 Torr), 162.7 g of a 48% aqueous solution of sodium bismuth hydroxide was added dropwise over 3 hours. During this time, the produced water was removed from the system by azeotrope with epichlorohydrin and distilled off. The epichlorohydrin was returned to the system. After the completion of the dropwise addition, the reaction was further continued for 1 hour and dehydrated, then the epichlorohydrin was distilled off, and 5 40 g of methyl isobutyl ketone was added, followed by washing with water to remove the salt. Subsequently, 13.5 g of 48% sodium hydroxide was added at 85 ° C and stirred for 1 hour, and washed with 200 ml of warm water. Subsequently, after the water was removed by liquid separation, methyl isobutyl ketone was distilled off under reduced pressure. Obtained 214g of white crystal Modified epoxy resin (epoxy resin B), epoxy equivalent of 135, hydrolyzable chlorine of 380 ppm, melting point of 108 ° C to H9t '150 ° C measured by capillary method -24-200948843 The viscosity was 2.3 mPa·s. The n = 0 (monomer) of the epoxy resin obtained from hydroquinone obtained by GPC measurement was 53.1 ° /. , n = l (dimer) was 34.2%. Further, the epoxy resin obtained from 4,4'-dihydroxybiphenyl had n = =0 (monomer) of 7.2% and n = 1 (dimer) of 4.3%. Example 3 12 125.0 g of hydroquinone and 25.0 g of 4,4'-dihydroxybiphenyl were dissolved in 1200 g of epichlorohydrin and 180 g of diethylene glycol dimethyl ether at 60. (: Add 21.2 g of 48% sodium hydroxide and stir for 1 hour. Then, under reduced pressure (about 130 Torr), add 190.6 g of 48% aqueous sodium hydroxide solution over 3 hours. The water is removed from the system by azeotrope with epichlorohydrin, and the distilled epichlorohydrin is returned to the system. After the completion of the dropwise addition, the reaction is continued for 1 hour and dehydrated, and then the epichlorohydrin is distilled off. After adding 560 g of methyl isobutyl ketone, the salt was removed by washing with water. Subsequently, 13_5 g of 48% sodium hydroxide was added at 85 ° C and stirred for 1 hour, and washed with 200 ml of warm water. After the water was removed by liquid separation, methyl isobutyl ketone was distilled off under reduced pressure to obtain 265 g of a white crystalline modified epoxy resin (epoxy resin C). The epoxy equivalent was 丨24, and the hydrolyzable chlorine was 3 9 〇. Ppm, the melting point measured by capillary method is from 8 6 ° C to 1 0 5 ° C, and the viscosity at 150 ° C is 0.8 mPa. s. The epoxy resin obtained from hydroquinone obtained by GPC measurement N-0 (monomer) is 2.2% for n=l (dimer). Further, n = 〇 (monomer) of epoxy resin obtained from 4,4-hydroxyl linkage is I〗 〖%, :η = 1 (dimer) was 3 · 0%. -25- 200948843 Examples 4 to 8 and Comparative Examples 1 to 5 The modified epoxy resin numbers of Examples 1 to 3 were referred to as epoxy resin A and ring. Oxygen resin B, epoxy resin epoxy resin D (epoxy resin D), reference resin (epoxy resin E), bisphenol epoxy resin (YX-4000H manufactured by Epoxy resin company; Epoxy equivalent 1 oxy resin component, phenol aralkyl resin (hardener A: XL-225-LL; OH equivalent 174, softening point 75 ° C) agent B), 4,4'-dihydroxy Phenyl ether (hardener C), using triphenylphosphine as a hardening accelerator, spherical alumina 12·2μπι) as an inorganic cerium filling material, blending as shown in Table 1 with a kneading machine, and then heating The mixture was kneaded on a roll for 5 minutes, and the products of Examples 4 to 8 and Comparative Examples 1 to 5 were obtained by pulverization. Evaluation After the epoxy resin composition was molded at 1,700 ° C, it was post-hardened at 170 ° C for 12 hours to obtain physical properties. The results of the examples are shown in Table 1. The numerical values of the respective formulations in Table 2 and Table 2 of Comparative Example show that the comparative example 5 cannot be cured by the molding. The evaluation method is as follows. C1) Thermal conductivity is measured by a non-fixed hot wire method using a thermal conductivity meter manufactured by NETZSCH. (2) Melting point, heat of fusion (DSC method) is poorly used (Resin C according to the example), 2 epoxy resin F: Japan 9 5 ) is manufactured as a ring well chemical, hydroquinone (hard as hardener (average particle size) For the composition and amount, the results of the molded article obtained by cooling the epoxy resin group for 5 minutes are listed in the table. In addition, the physical property evaluation of the product LFA447 indicates the scanning heat 200948843 analytical device (DSC 6200 manufactured by Seiko Instruments). The temperature was measured at a temperature rise rate of 10 ° C / min. (3) The coefficient of linear expansion and the glass transition temperature were measured using a TMA120C type thermomechanical measuring device manufactured by Seiko Instruments Co., Ltd. at a temperature rising rate of 10 ° C / min. (4) The water absorption rate is the weight change rate after forming a disc with a diameter of 50 mm and a thickness of 3 mm, after hardening at a temperature of 85 ° C and a relative humidity of 8 5 %. Table 1] Example 4 5 6 7 8 Epoxy Resin A 66.5 107.5 87.0 Epoxy Resin B 65.5 Epoxy Resin C 62.5 Hardener A 83.5 84.5 87.5 Hardener B 42.5 Hardener C 63.0 Inorganic Filling Material 1000 1000 1000 1000 1000 Hardening accelerator 1.6 1.6 1.6 1.6 1.6 Gel time (sec) 33 34 37 45 42 Helical fluidity (cm) 101 110 114 130 127 Glass transfer point (°C) 134 132 131 87 89 Thermal expansion coefficient (ppm, <Tg) 13.0 14.0 14.0 11.0 10.0 Thermal expansion coefficient (ppm, > Tg) 56.0 57.0 60.0 53.0 52.0 Heat distortion temperature (°C) 144 142 141 167 172 Water absorption (wt%, 100h) 0.14 0.15 0.14 0.12 0.11 Thermal conductivity (W/m, K 4.3 4.2 4.2 5.0 5.2 Melting point (°C) . . 166.3 199.5 Heat of fusion (J/g-resin) 0 0 0 15 26 -27- 200948843 [Table 2] Comparative Example 1 2 3 4 5 _ Epoxy resin D 60.0 34.0 33.0 Epoxy Resin E 33.0 Epoxy Resin F 34.0 79.0 117.0 Hardener A 90.0 82.0 71.0 84.0 Hardener B 33.0 Inorganic Filling Material 1000 1000 1000 1000 1000 Hardening Accelerator 1.6 1.6 1.6 1.6 1.6__ Gel Time (sec) 44 49 35 48 Helical fluidity (cm) 96 93 77 82 Glass transition point rc) 118 122 128 89 Thermal expansion coefficient (Ppm, <Tg) 13.0 15.0 21.0 18.0 Thermal expansion coefficient (ppm, > Tg) 74.0 84.0 82.0 75.0 Heat Deformation temperature (°C) 121 124 131 94 Water absorption rate (wt% , 100h) 0.24 0.23 0.21 0.23 Thermal conductivity (W/mK) 3.5 3.3 3.2 3.3 Melting point (°C) _ Heat of fusion (J/g-resin) 0 0 0 0 [Probability of industrial use] Modification of the present invention The epoxy resin and the epoxy resin composition can obtain a cured product which is excellent in moldability and reliability, and has high thermal conductivity, low water absorbability, low thermal expansion property, and high heat resistance, and can be suitably used as a semiconductor package, a laminate, and a heat release. The insulating material for electrical and electronic parts, such as a substrate, and the 材u material are excellent in heat dissipation and dimensional stability. -28-