201144347 六、發明說明： [發明所屬之技術領域】 本發明係關於結晶性之環氧樹脂、其製造方法、使用 其之環氧樹脂組成物及硬化物。 【先前技術】 近年’尤其伴隨先端材料領域之進步，追求更高性能 之基質樹脂之開發。例如在半導體封閉領域中，因車載用 半導體之進展而追求局耐熱性、熱分解安定性優異的基質 樹脂。另一方面’因高密度實裝化亦有進展，導向無機塡 料之高充塡率化、亦強烈追求基質樹脂之低黏度化。又， 要求對應嚴苛使用環境用的高溫信賴性之提升、由散熱性 提升的觀點亦要求熱傳導率之提升。 然而，在習知的環氧樹脂尙未有滿足此等要求者。例 如專利文獻1，提案耐熱性、耐濕性優異之萘酚芳烷基型 環氧樹脂，但在耐熱性之點上並不足夠，且黏度高、不適 合於無機塡料的高充塡率化。又，作爲耐熱性優異者，專 利文獻2中揭示使4,4’-二羥基聯苯以P-二甲苯基連結的芳 烷基型之環氧樹脂，但在耐濕性、難燃性有問題。專利文 獻3中，揭示具有使雙酚化合物以聯苯撐基連結的構造之 聯苯基芳烷基型環氧樹脂，但爲不具結晶性之樹脂狀物、 且黏度及軟化點變高在成形性上有問題。 [先前技術文獻] [專利文獻1]特開平1 - 252624號公報 201144347 [專利文獻2]特開平4-255714號公報 [專利文獻3]特開平8-239454號公報 【發明內容】 S此本發明的目的在於提供低黏度性及作爲固體的操 作性優異’且耐熱性、耐濕性、及熱傳導性亦具有優異性 能、可用於暦合、成形、注型、接著等用途之環氧樹脂及 使用其之環氧樹脂組成物及其硬化物。 亦即’本發明係關於下述一般式（丨）所表示、基於 示差掃描熱m分析中之熔點的吸熱波峰溫度在1 〇 〇〜1 5 0 °c 之範圍的具有結晶性之環氧樹脂。 【化1】[Technical Field] The present invention relates to a crystalline epoxy resin, a method for producing the same, an epoxy resin composition using the same, and a cured product. [Prior Art] In recent years, especially in the field of advanced materials, development of a matrix resin having higher performance has been pursued. For example, in the field of semiconductor sealing, a matrix resin excellent in heat resistance and thermal decomposition stability has been pursued due to progress in automotive semiconductors. On the other hand, there has been progress in high-density mounting, which has led to a high filling rate of inorganic materials and a strong pursuit of low viscosity of matrix resins. In addition, it is required to improve the heat conductivity in response to the improvement of high-temperature reliability for use in harsh environments and the improvement in heat dissipation. However, conventional epoxy resins have not met such requirements. For example, Patent Document 1 proposes a naphthol aralkyl type epoxy resin excellent in heat resistance and moisture resistance, but it is not sufficient in heat resistance, and has high viscosity and is not suitable for high charge rate of inorganic materials. . Further, as an excellent heat resistance, Patent Document 2 discloses an aralkyl type epoxy resin in which 4,4'-dihydroxybiphenyl is bonded to P-xylyl, but has moisture resistance and flame retardancy. problem. Patent Document 3 discloses a biphenyl aralkyl type epoxy resin having a structure in which a bisphenol compound is bonded to a biphenylene group, but is a resinous material having no crystallinity, and has a high viscosity and a softening point in forming. There is a problem with sex. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The purpose of the invention is to provide a low-viscosity and excellent workability as a solid, and an excellent performance in heat resistance, moisture resistance, and thermal conductivity, and can be used for bonding, forming, injection molding, and the like. Its epoxy resin composition and its hardened material. That is, the present invention relates to a crystalline epoxy resin having an endothermic peak temperature of from 1 〇〇 to 150 ° C, which is represented by the following general formula (丨), based on the melting point in the differential scanning thermal m analysis. . 【化1】
(但，η之平均値爲0.2〜4.0，G爲環氧丙基）。 又’本發明係關於使4，4 ’ -二羥基聯苯】莫耳與下述― 般式（2 )所表示的聯苯系縮合劑0.1〜〇 . 4莫耳反應成爲下 述一般式（3 )所表示的多元羥基樹脂後，使其與表氯醇 反應而得到之基於示差掃描熱量分析中之熔點的吸熱波峰 溫度在1 00〜1 5 0°C之範圍的具有結晶性之環氧樹脂。 201144347 【化2】 (2) x-ch2-^h0^-ch2-x (但，X爲羥基、鹵素原子或碳數1〜6之烷氧基）。 【化3】(However, the average 値 of η is 0.2 to 4.0, and G is a glycidyl group). Further, the present invention relates to a 4,4 '-dihydroxybiphenyl]mole and a biphenyl condensing agent represented by the following formula (2): 0.1 to 〇. 4 molar reaction becomes the following general formula ( 3) The polyhydroxy resin represented by the reaction, which is obtained by reacting with epichlorohydrin to obtain a crystalline epoxy having an endothermic peak temperature based on the melting point in the differential scanning calorimetric analysis in the range of 100 to 150 ° C Resin. 201144347 (2) x-ch2-^h0^-ch2-x (However, X is a hydroxyl group, a halogen atom or an alkoxy group having 1 to 6 carbon atoms). [化3]
(但，η之平均値爲〇_2〜4.0)。 進一步本發明係關於由環氧樹脂及硬化劑所成的環氧 樹脂組成物中，以作爲環氧樹脂成分含上述環氧樹脂爲特 徵的環氧樹脂組成物、及將其硬化而成的硬化物。 [實施發明之最佳形態] 以下將本發明詳細說明。 本發明的環氧樹脂爲一般式（1 )所表示、重複單元η 之値相異的成分之混合物。在此，η之平均値爲〇 . 2〜4 · 0。 比此小’則結晶性增強，同時熔點變高、操作性降低。比 此大’則結晶性降低’同時黏度變高、成形性降低。由低 黏度性、操作性及成形性之觀點，η = 〇體的含有率以在30 〜60%之範圍者爲佳。本說明書所謂η的平均値係指數平均 201144347 本發明的環氧樹脂具有結晶性、在固體之狀態結晶化 。該結晶固體以昇溫速度1 〇 °c /分鐘測定的基於示差掃描 熱量分析中之熔點的吸熱波峰之溫度爲100〜150t、較佳 爲1 2 0〜1 5 0 °c之範圍者。比此高，則調整環氧樹脂組成物 時與硬化劑之相溶性降低，比此低，則產生環氧樹脂組成 物的結塊等之問題、操作性降低。因環氧樹脂之結晶狀態 ，有可見複數熔點波峰之情形，在此所謂吸熱波峰溫度係 指對應最大波峰者。波峰之吸熱量認爲係表示結晶性程度 者，但通常以樹脂成分換算在20〜8(H/g之範圍。比此小， 則結晶性之程度低、操作性降低。 本發明的環氧樹脂雖可藉由一般式（3)所表示的多 元羥基樹脂與表氯醇反應而得，但在環氧樹脂之發明中， 製造方法不限於此。但，因說明製造方法之發明，使本發 明的環氧樹脂變得易於理解，故由環氧樹脂之原料的多元 羥基樹脂及環氧樹脂之製造方法來說明。 一般式（3 )所表示的多元羥基樹脂爲η之値相異的成 分之混合物，η之平均値爲0.2〜4 · 0。比此小，則結晶性變 強、合成環氧樹脂時對表氯醇之溶解性降低，同時得到的 環氧樹脂之熔點變高、操作性降低。比此大，則結晶性降 低’同時黏度變高 '成形性降低。由低黏度性、操作性及 成形性之觀點，η = 0體的含有率以在3 0〜6 0 %之範圍者爲佳 〇 如此的多元羥基樹脂可藉由4,4’-二羥基聯苯與一般式 (2)所表示的聯苯系縮合劑反應而得。 -8- 201144347 —般式（2)中，X爲羥基、鹵素原子或碳數丨〜6之烷 氧基。具體上，可舉例如4,4，-雙羥基甲基聯苯、4,4，_雙氯 甲基聯苯、4,4，-雙溴甲基聯苯、4,4，_雙甲氧基甲基聯苯、 4,4’-雙乙氧基甲基聯苯。由反應性之觀點，以4,4，_雙經基 甲基聯苯、4,4，-雙氯甲基聯苯爲佳，由離子性雜質降低觀 點以4,4’-雙羥基甲基聯苯' 4,4，_雙甲氧基甲基聯苯爲佳。 反應時的莫耳比相對於4,4，-二羥基聯苯丨莫耳而言， 聯苯系縮合劑必須在1莫耳以下，一般爲〇·〗〜〇 . 5莫耳之範 圍’更較佳爲0_2〜ο.4莫耳之範圍。比此少，則結晶性變 強、合成環氧樹脂時對表氯醇之溶解性降低，同時得到的 環氧樹脂之熔點變局、操作性降低。又，比此多，則樹脂 之結晶性降低’同時軟化點及熔融黏度變高、損及操作作 業性、成形性。 又’縮合劑使用4，4 ’ -雙氯甲基聯苯時，雖亦可在無觸 媒下進行反應’通常本縮合反應於酸性觸媒之存在下進行 。該酸性觸媒，可由周知無機酸、有機酸適宜選擇，例如 鹽酸、硫酸、磷酸等之無機酸、或甲酸、草酸、三氟乙酸 、P-甲苯磺酸、甲磺酸 '三氟甲磺酸等之有機酸、或氯化 鋅、氯化鋁、氯化鐵、三氟化硼等之路易士酸、或固體酸 等。 該反應在〜25〇°C進行1〜20小時。又，反應時，可 使用甲醇、乙醇、丙醇'丁醇、乙二醇、甲基溶纖劑、乙 基溶纖劑等之醇類或苯 '甲苯、氯苯、二氯苯等之芳香族 化合物等作爲溶劑。反應完畢後，因應必要除去溶劑、或 -9 - 201144347 因縮合反應生成之水、醇類。 如此，得到的多元羥基樹脂除可用作環氧樹 以外，亦可作爲環氧樹脂硬化劑使用。又，進一 六次甲四胺等之硬化劑組合，亦可應用作爲酚樹 料。 說明關於一般式（3 )所表示的多元羥基樹 醇之反應的本發明的環氧樹脂之製造方法。該反 知環氧化反應同樣進行。 例如使一般式（3 )所表示的多元羥基樹脂 表氯醇後’在氫氧化鈉、氫氧化鉀等之鹼金屬氫 存在下在50〜150 °C、較佳爲60〜120。(：之範圍進f 時反應之方法。此時的表氯醇的使用量相對於多 脂中羥基1莫耳而言，在0.8〜2莫耳、較佳爲〇.9〃 之範園。反應完畢後將過S表氯醇餾去，使殘留 甲苯 '甲基異丁基酮等之溶劑，過濾、水洗除去 接著藉由使溶劑餾去’可得到前述一般式（1 ) 目的環氧樹脂。進行環氧化反應時，亦可使用四 之觸媒。 本發明的環氧樹脂之純度、尤其水解性氯量 子零件之信賴性提升的觀點以少者爲佳。雖非爲 者’但較佳爲lOOOppm以下、再較佳爲5〇〇ppm以(However, the average η is 〇_2~4.0). Further, the present invention relates to an epoxy resin composition comprising an epoxy resin and a curing agent, an epoxy resin composition characterized by containing the epoxy resin as an epoxy resin component, and hardening by hardening the epoxy resin component. Things. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The epoxy resin of the present invention is a mixture of components represented by the general formula (1) and having a repeating unit η. Here, the average η of η is 〇 2 to 4 · 0. When it is smaller than this, the crystallinity is enhanced, and the melting point is increased and the workability is lowered. If it is larger than this, the crystallinity is lowered, and the viscosity is high and the formability is lowered. From the viewpoint of low viscosity, workability, and formability, the content of η = steroid is preferably in the range of 30 to 60%. The average lanthanide index average of η in the present specification is 201144347. The epoxy resin of the present invention has crystallinity and is crystallized in a solid state. The temperature of the endothermic peak based on the melting point in the differential scanning calorimetry of the crystalline solid measured at a temperature rising rate of 1 〇 ° c /min is in the range of 100 to 150 t, preferably 1 2 0 to 150 ° C. When the epoxy resin composition is adjusted, the compatibility with the curing agent is lowered, and if it is lower, the problem of agglomeration of the epoxy resin composition or the like is caused, and workability is lowered. Due to the crystalline state of the epoxy resin, there is a case where a complex melting point peak is seen. Here, the endothermic peak temperature refers to the corresponding maximum peak. The heat absorption of the peak is considered to be a degree of crystallinity, but it is usually in the range of 20 to 8 (H/g in terms of resin content). When the amount is smaller than this, the degree of crystallinity is low and the workability is lowered. Although the resin can be obtained by reacting a polyhydric hydroxy resin represented by the general formula (3) with epichlorohydrin, in the invention of the epoxy resin, the production method is not limited thereto. However, the invention of the production method is described. Since the epoxy resin of the invention is easy to understand, it is explained by a method for producing a polyvalent hydroxy resin and an epoxy resin of a raw material of an epoxy resin. The polyhydric hydroxy resin represented by the general formula (3) is a composition different from η. The mixture has an average enthalpy of η of 0.2 to 4 · 0. When the ratio is smaller, the crystallinity becomes stronger, the solubility of epichlorohydrin decreases when the epoxy resin is synthesized, and the melting point of the obtained epoxy resin becomes high, and the operation is performed. If the viscosity is lower than this, the crystallinity is lowered, and the viscosity is high, and the formability is lowered. From the viewpoint of low viscosity, workability, and formability, the content of η = 0 is in the range of 30 to 60%. The range is the multi-hydroxy tree It can be obtained by reacting 4,4'-dihydroxybiphenyl with a biphenyl condensing agent represented by the general formula (2). -8- 201144347 In the general formula (2), X is a hydroxyl group, a halogen atom or carbon. The alkoxy group of 丨~6. Specifically, for example, 4,4,-bishydroxymethylbiphenyl, 4,4,-dichloromethylbiphenyl, 4,4,-dibromomethylbiphenyl 4,4,_bismethoxymethylbiphenyl, 4,4'-diethoxymethylbiphenyl. From the viewpoint of reactivity, 4,4,-di-bis-methylethylbiphenyl, 4 4,-dichloromethylbiphenyl is preferred, and 4,4'-bishydroxymethylbiphenyl '4,4,_bismethoxymethylbiphenyl is preferred from the viewpoint of reducing ionic impurities. The molar ratio of the molar ratio to the 4,4,-dihydroxybiphenyl oxime must be below 1 mole, generally 〇·〗 〇. 5 mole range 'more preferably It is a range of 0_2 to ο. 4 moles. When the amount is less than this, the crystallinity becomes strong, and the solubility of epichlorohydrin in the synthesis of the epoxy resin is lowered, and the melting point of the obtained epoxy resin is changed and the workability is lowered. More than this, the crystallinity of the resin is lowered' while the softening point and the melt viscosity are changed. And the workability and formability are impaired. When the 4,4 '-dichloromethylbiphenyl is used as the condensing agent, the reaction can be carried out without a catalyst. Usually, the condensation reaction is carried out in the presence of an acidic catalyst. The acidic catalyst can be suitably selected from known inorganic acids and organic acids, such as inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, or formic acid, oxalic acid, trifluoroacetic acid, P-toluenesulfonic acid, methanesulfonic acid 'trifluoroethylene. An organic acid such as sulfonic acid, or a Lewis acid such as zinc chloride, aluminum chloride, iron chloride or boron trifluoride, or a solid acid, etc. The reaction is carried out at 〜25 ° C for 1 to 20 hours. In the reaction, an alcohol such as methanol, ethanol, propanol butanol, ethylene glycol, methyl cellosolve or ethyl cellosolve or aromatics such as benzene 'toluene, chlorobenzene or dichlorobenzene may be used. A compound or the like is used as a solvent. After the completion of the reaction, it is necessary to remove the solvent or the water or alcohol formed by the condensation reaction in -9 - 201144347. Thus, the obtained polyvalent hydroxy resin can be used as an epoxy resin hardener in addition to being used as an epoxy resin. Further, a combination of hardeners such as methyltetramine or the like may be applied as a phenol tree. A method for producing the epoxy resin of the present invention relating to the reaction of the polyhydric hydroxyalcohol represented by the general formula (3) will be described. This anti-epoxidation reaction is also carried out. For example, the polyhydric hydroxy resin represented by the general formula (3) is epichlorohydrin in the presence of an alkali metal hydrogen such as sodium hydroxide or potassium hydroxide at 50 to 150 ° C, preferably 60 to 120. (The method of the reaction in the range of f: The amount of epichlorohydrin used at this time is 0.8 to 2 moles, preferably 〇.9 inches, relative to the hydroxyl group 1 mole in the fat. After the completion of the reaction, the S-epichlorohydrin is distilled off, and the solvent such as toluene 'methyl isobutyl ketone is left, filtered, washed with water, and then distilled off by solvent to obtain the epoxy resin of the above general formula (1). When the epoxidation reaction is carried out, a four-catalyst may be used. The purity of the epoxy resin of the present invention, particularly the reliability of the hydrolyzable chlorinated quantum component, is preferably improved, although it is not preferred. It is below 1000 ppm, and more preferably 5 〇〇 ppm.
本發明所g胃水解性氯係指由以下的方法所測定之 ，使試料〇.5g溶於二噁烷3〇mi後，加AlN_K〇H 行30分鐘煮沸迴流後’冷卻至室溫，進一步加入 脂之原料 步藉由與 脂成形材 脂與表氯 應可與周 溶於過11 氧化物的 ί 1〜1 〇小 元羥基樹 I 1 .2莫耳 物溶解於 鈾機鹽， /»、、 \/^t JXDL 所表示的 級銨鹽等 由適用電 特別限定 下。又， 値。亦即 、10ml進 80%丙酮 -10- 201144347 水1 00ml，以0.0 02N-AgNO3水溶液進行電位差滴定所得的 値。 本發明的環氧樹脂組成物中含有環氧樹脂與硬化劑， 作爲環氧樹脂成分含有上述一般式（1 )之環氧樹脂。 本發明的環氧樹脂組成物中，除作爲必須成分使用的 —般式（1 )之環氧樹脂以外，亦可倂用分子中具2個以上 環氧基的一般其他環氧樹脂。例如雙酚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 苯基颯、4,4’-二羥基二苯硫醚' 4,4’-二羥基二苯基酮、芴 雙酚、4,4’-聯酚、3,3’，5,5’-四甲基-4,4’-二羥基聯苯、 2,2’-聯酚、間苯二酚、兒茶酚、t-丁基兒茶酚、t-丁基對 苯二酚、1，2-二羥基萘、1，3-二羥基萘、1,4-二羥基萘、 1,5-二羥基萘、Μ-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 烯两基化物或聚烯丙基化物、烯丙基化雙酚A、烯丙基化 雙酿F、烯丙基化酚酚醛清漆等之2元酚類、或酚酚醛清漆 、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、二甲酚酚醛清漆、聚-P-羥基苯乙烯、 參_(4-羥基苯基）甲烷、〗，1，2,2-肆（4-羥基苯基）乙烷、氟甘 胺醇、焦掊酚、t- 丁基焦掊酚、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、酚芳 院基樹脂、萘酚芳烷基樹脂、二環戊二烯系樹脂等之3元 以上的酚類、或由四溴雙酚A等之鹵素化雙酚類衍生的環 -11 - 201144347 氧丙基醚化物等。此等之環氧樹脂可1種或2種以上混合使 用。 本發明的環氧樹脂組成物，作爲環氧樹脂以含環氧樹 脂成分之50wt%以上之上述般式（1 )之環氧樹脂爲佳。 再較佳爲全環氧樹脂之70wt%以上、更較佳爲80 wt%以上 。使用比例比此少，則作爲環氧樹脂組成物之成形性惡化 ，同時作爲硬化物時的耐熱性、耐濕性、及熱傳導性及耐 回流焊接性等之提升效果小。 作爲本發明的環氧樹脂組成物中之硬化劑，一般可使 用作爲環氧樹脂的硬化劑之所有已知者。例如雙氛胺、多 元酚類 '酸酐類、芳香族及脂肪族胺類等。在要求耐濕性 、耐熱性的電氣•電子零件的封閉領域以多元酚類宜於使 用。將此等具體例示，如下。在本發明的樹脂組成物，可 混合使用此等硬化劑的1種或2種以上。 多元酚類，可舉例如雙酚A、雙酚F、雙酚S、芴雙酚 、4,4、聯酚、2,2’-聯酚、對苯二酚、間苯二酚、萘二醇等 之2元酚類、或參- (4·羥基苯基）甲烷、ι,〗，2,2-肆（4-羥 基苯基）乙烷、酚酚醛清漆、〇·甲酹酚醛清漆、萘酚酚醛 清漆、聚乙烯基酚等所代表之3元以上的酚類、進而酚類 、萘酚類或雙酚A、雙酚F、雙酚S、芴雙酚、4,4’-聯酚、 2，2’-聯酚、對苯二酚、間苯二酚、萘二醇等之2元酚類的 經甲醛、乙醛、苯甲醛、P·羥基苯甲醛、ρ·二甲苯二醇等 縮合劑合成之多元酚性化合物等。又，亦可使用一般式（ 3 )所表示的多元羥基樹脂。 -12· 201144347 酸酐，例如苯二甲酸酐、四氫苯二甲酸酐、甲基四氫 苯二甲酸酐'六氫苯二甲酸酐、甲基六氫苯二甲酸酐、甲 基納迪克酸酐、納迪克酸酐、偏苯三酸酐等。 胺類’有4,4’-二胺基二苯基甲烷、4,4，-二胺基二苯基 丙院、4,4’-二胺基二苯基颯、m·苯二胺、p_二甲苯二胺 等之芳香族胺類、乙烯二胺 '六亞甲二胺、二乙烯三胺、 三乙烯四胺等之脂肪族胺類。 在本發明的樹脂組成物，可將此等硬化劑的1種或2種 以上混合使用。 又’本發明的環氧樹脂組成物中，可適宜搭配聚酯、 聚醯胺、聚亞胺、聚醚、聚苯醚、聚胺基甲酸酯、石油樹 脂、茚香豆酮樹脂、苯氧基樹脂等之寡聚物或高分子化合 物’亦可搭配無機充塡劑、顔料、難燃劑、搖改性賦予劑 、耦合劑、流動性提升劑等之各種添加劑。 進一步本發明的環氧樹脂組成物中，可搭配無機充塡 劑’例如可單獨或併用2種類以上的球狀或破碎狀的熔融 二氧化矽、結晶二氧化矽等之二氧化矽粉末、氧化鋁、锆 '矽酸鈣、碳酸鈣、碳化矽、氮化硼、氧化鈹、氧化銷、 鎂橄欖石、塊滑石、尖晶石、莫來石、二氧化鈦等之粉體 、或使此等球形化的珠粒、鈦酸鉀、碳化矽' 氮化矽、氧 化鋁等之單結晶纖維、玻璃纖維等。上述無機充塡劑中由 線膨脹係數降低觀點以熔融二氧化矽爲佳、由高熱傳導性 之觀點以氧化鋁爲佳。充塡劑形狀由成形時的流動性及模 具摩耗性來看以50%以上爲球形者爲佳，尤其使用球狀熔 -13- 201144347 融二氧化矽粉末爲佳。 無機充塡材的添加量通常相對環氧樹脂組成物而言在 50wt%以上，但較佳爲70wt%以上、更較佳爲80wt%以上。 比此少，則無法充分發揮低吸濕性、低熱膨脹性、高耐熱 性、高熱傳導性之本發明目的效果。此等之效果，係無機 充塡材的添加童愈多愈好，但非因應其體稂分率提升者， 而係由特定添加量開始大幅地提升。另一方面，無機充塡 材的添加比此多，則黏度變高、成形性惡化所以不佳。 本發明的環氧樹脂組成物中，可搭配公知硬化促進劑 。可舉例如胺類、咪唑類、有機膦類、路易士酸等，具體 上如1，8-二氮雜雙環（5,4,0)十一烯-7、1，5-二氮雜-雙環 (4,3,0)壬烯、5、6-二丁基胺基-1，8-二氮雜-雙環（5,4,0)十 一烯-7等之環脒化合物及此等之化合物加成馬來酸酐、苯 醌、重氮苯基甲烷等之具π鍵結的化合物而得的具有分子 內分極之化合物、三乙烯二胺、芣基二甲基胺、三乙醇胺 、二甲基胺基乙醇、參（二甲基胺基甲基）酚等三級胺類 及此等之衍生物、2 -甲基咪唑、2 -苯基咪唑、2 -苯基·4 -甲 基咪唑、2 ·十七基咪唑等咪唑類及此等之衍生物、三丁基 膦、甲基二苯基膦、三苯基膦、二苯基膦、苯基膦等之有 機膦類及此等之膦類加成馬來酸酐、苯驅、重氮苯基甲院 等之具π鍵結的化合物而得之具分子內分極之磷化合物、 四苯基鱗·四苯基硼酸酯 '四苯基鱗•乙基三苯基硼酸酯 、四丁基鐵•四丁基硼酸酯等之四取代鱗.四取代硼酸酯 、2 -乙基-4-甲基咪唑•四苯基硼酸酯、Ν -甲基嗎啉.四苯 -14 - 201144347 基硼酸酯等之四苯基硼鹽及此等之衍生物等。添加量，通 常相對環氧樹脂1 〇 0重量份而言、在〇 · 2〜1 0重量份的範圍 。此等可單獨使用、亦可倂用。 本發明的環氧樹脂組成物中，因應必要使用難燃劑。 如此的難燃劑’可舉例如紅磷、磷氧化合物等之磷系難燃 劑、三嗪衍生物等之氮系難燃劑、偶磷氮衍生物等之磷氮 系難燃劑、金屬氧化物 '金屬水合物、二茂金屬衍生物等 之有機金屬錯合物、硼酸鋅' 錫酸鋅、鉬酸鋅等之鋅化合 物等，其中以金屬水合物爲佳。金屬水合物，可舉例如氫 氧化鋁、氫氧化鎂、氫氧化鈣、氫氧化鎳、氫氧化鈷、氫 氧化鐵、氫氧化錫、氫氧化鋅、氫氧化銅、氫氧化鈦等， 又’亦可使用此等之金屬水合物與氧化鎳、氧化鈷、氧化 鐵、氧化錫、氧化鋅、氧化銅、氧化鈀等之金屬氧化物的 複合化金屬水合物。由對安全性、難燃效果及成形材料的 成形性影響觀點，以氫氧化鎂爲佳。 本發明的環氧樹脂組成物中，除上述以外，因應必要 可使用高級脂肪酸、高級脂肪酸金屬鹽、酯系蠟、聚嫌煙 系蠟等之脫膜劑、碳黑等之著色劑、矽烷系、鈦酸醋系、 鋁酸酯系等之耦合劑、矽酮粉末等之可撓劑、砂酮油或石夕 酮橡膠粉末等之應力緩和劑、菱水鎂鋁石、銻-鉍等之離 子捕集劑等。 又’本發明的環氧樹脂組成物中’由成形時的流動性 改良及與引線架等之基材的密著性提升觀點，可添加熱可 塑性之寡聚物類。熱可塑性之寡聚物類，例如C5系及（^系 -15- 201144347 的石油樹s曰 '苯乙烯樹脂、茚樹脂、茚•苯乙烯共聚合樹 月曰、印•本乙烯.酚共聚合樹脂、茚•香豆酮共聚合樹脂 、茚.本並噻吩共聚合樹脂等。添加量，通常相對環氧樹 月曰1 〇 〇重Μ份而言，在2〜3 〇重量份的範圍。 本發明的環氧樹脂組成物的調製方法，可使用任何可 將各種原材料均一分散混合之手法，但一般方法，可舉例 如使特定搭配量的原材料以混合機等充分混合後，以混合 輕、押出機等進行熔融混練、冷卻、粉碎之方法。 本發明的環氧樹脂組成物尤其適用半導體裝置的封閉 用。 本:發明的硬化物係使上述環氧樹脂組成物熱硬化而得 。爲了使用本發明的環氧樹脂組成物得到硬化物，適用例 如轉注成形、加壓成形、注型成形、射出成形、押出成形 等之方法，但由量產性之觀點以轉注成形爲佳。 【實施方式】 [Κ施例] 以下、以货施例將本發明進一步具體說明。 合成例1 於2〇〇〇ml之4口燒瓶中，加入4,4’ -二羥基聯苯186_0g (卜〇莫耳）、二乙二醇二甲基醚600g，氮氣流下、邊攪 拌邊升溫至150。(：，於二乙二醇二甲基醚260g中滴下溶解 有4,4’-雙氯甲基聯苯75.3g( 0.3莫耳）之溶液後，升溫至 -16- 201144347 1 7 0 °c後進行2小時反應。反應後，滴下至大量純水中後藉 由再沈澱回收，得到淡黃色結晶性之樹脂2 2 0 g。得到樹脂 之〇11當量爲130.8。〇3(：測定中之波峰溫度爲248.5它、伴 隨結晶溶解之吸熱量爲95.5J/g。得到樹脂之GPC圖表如圖 1。GPC測定所求出的一般式（3 )中之各成分比，n = 0爲 3 9.3 3 % ' n=l 爲 22.2 5 %、n = 2 爲 12.19%、n = 3 爲 8.14%、n = 4 爲5.5 8 %、η 2 5爲1 1 . 8 8 %。在此D S C波峰溫度係指使用示 差掃描熱量分析裝置（Seiko Instruments製DSC220 C型 )，以昇溫速度5°C /分鐘測定的値。又，GPC測定，裝置 ；日本 Waters(股）製、515A 型、管柱；TSK-GEL200〇x3 支 及TSK-GEL4000X 1支（皆東曹（股）製）、溶劑；四氫呋喃 、流量；lml/min、溫度；38°C、檢出器；遵循RI之條件 合成例2 除使用將4,4’-二羥基聯苯I67.4g(0.9莫耳）、二乙二 醇二甲基醚540g、4,4’-雙氯甲基聯苯90.4g( 0.36莫耳）溶 於二乙二醇二甲基醚3 20g的溶液以外，與實施例1同樣地 進行反應，得到淡黃色且結晶性之樹脂2 0 5 g。得到樹脂之 OH當量爲139.2。DSC波峰溫度爲242.4°c、GPC測定所求 出的一般式（3)中之各成分比，11 = 0爲31.21%'11=：1爲 21.19%、11 = 2爲13.38%'11 = 3爲1〇.63%、11 = 4爲7.55%、112 5 爲 1 5 . 3 5 %。 -17- 201144347 合成例3 除使用將4,4’-二羥基聯苯l86.0g(l.〇莫耳）、 醇二甲基醚540g、4,4’-雙氯甲基聯苯5〇2g(〇2莫 於二乙二醇二甲基醚32〇g的溶液以外，與實施例1 進行反應，得到淡黃色且結晶性之樹脂1 95g。得到 OH當量爲125.6。DSC波峰溫度爲25 5.4。!：、GPC測 出的一般式（3)中之各成分比，n = 〇爲50.87 %、 2 0.6 7 %、η = 2 爲 1 1 · 5 4 %、η = 3 爲 7 1 1 %、n = 4 爲 3.7 8 % 爲 5 · 8 7 %。 合成例4 除使用將4,4’-二羥基聯苯152.5g ( 0.82莫耳） 二醇二甲基醚500g、4,4’-雙氯甲基聯苯ii2.9g(0. )溶於二乙二醇二甲基醚360g的溶液以外，與實挤 樣地進行反應，得到淡黃色樹脂201 g。得到樹脂: 量爲1 5 0 · 1。G P C測定所求出的一般式（3 )中之各 ’ n = 0 爲 22.03%、n=l 爲 14.65%、n = 2 爲 11.89%、 9.46% ' 11 = 4爲7.36%、11&5爲33.87 0/〇〇 合成例5 除使用將4,4’-二羥基聯苯186.0g( 1.0莫耳）、 醇二甲基醚600g、1,4-雙氯甲基苯52.5g(0.3莫耳 二乙二醇二甲基醚260g的溶液以外，與實施例1同 行反應，得到淡黃色且結晶性之樹脂202。得到樹 二乙二 耳）溶 同樣地 樹脂之 定所求 n= 1爲 、η 2 5 、二乙 45莫耳 δ例1同 匕ΟΗ當 成分比 η = 3爲 二乙二 )溶於 樣地進 !旨之ΟΗ -18- 201144347 當量爲116.3。DSC波峰溫度爲241.7°C、GPC測定所求出的 —般式（3)中，對應交聯部位之聯苯撐基取代爲苯撐基 構造的各成分比，η = 0爲4 0.3 3 %、η = 1爲2 3 · 3 1 %、η = 2爲 1 1.22%、η = 3爲 7.09%、η = 4爲 5.17%、ng 5爲 12.35% ° 合成例6 除取代4,4，-二羥基聯苯（1.0莫耳），使用4,4’-二羥 基二苯基甲烷200.0g(1.0莫耳）外，與合成例1同樣地進 行反應後，經減壓蒸餾將溶劑餾去，得到淡褐色樹脂245 g 。得到樹脂之Ο Η當量爲1 3 7.6。G P C測定所求出的一般式 (3)中4,4’ -二羥基聯苯骨架取代爲4,4，-二羥基二苯基甲 烷的構造中之各成分比，η = 0爲3 6 · 8 9 %、η= 1爲2 0.3 6 %、 η = 2 爲 12.30%、η = 3 爲 9.68%、η = 4 爲 6.58%、ng 5 爲 13.56% 實施例1 使合成例1所得樹脂1 2 0 g溶於表氯醇5 0 9 g、二乙二醇 二甲基醚76.4§，在減壓下（約13 0丁〇1*〇62°〇使48%氫氧化 鈉水溶液76.5 g花費4小時滴下。此期間，生成的水藉由與 表氯醇共沸除去於系統外、餾出的表氯醇則回到系統內。 滴下完畢後，進一步繼續進行1小時反應。之後，使表氯 醇餾去，加入甲基異丁基酮97 1 g後，以水洗除去鹽。之後 ，添加2 4 %氫氧化鈉水溶液1 9.3 g，在8 5 °C進行2小時反應 。反應後，進行過濾、水洗後，使溶劑的甲基異丁基酮減 -19- 201144347 壓餾去’得到環氧樹脂丨4 8 g (環氧樹脂A )。環氧當量爲 183.7、水解性氯爲1 400ppm。得到樹脂之GPC圖表如圖2 。GPC測定所求出的一般式（〗）中之各成分比，n = 〇爲 42.49%、n=l 爲 19.41%、n = 2 爲 12.23%、n = 3 爲 8.50%、n-4 爲4.5 6 %、n g 5爲8 .丨8 %。D S c測定結果如圖3。D S C測定結 果中之波峰溫度爲140.0°C、伴隨結晶熔解之吸熱量爲 36,9J/g。又，毛細管熔點爲Hi.5〜i43.8°C、150°C之熔融 黏度爲51mPa· s。 實施例2 使合成例2所得樹脂122g溶於表氯醇486g、二乙二醇 二甲基醚72.98，減壓下（約1301'〇1^)在62。(：使48%氫氧 化鈉水溶液7 3 · 0 g花費4小時滴下。此期間，生成的水藉由 與表氯醇共沸除去於系統外、餾出的表氯醇則回到系統內 。滴下完畢後，進一步繼_進行1小時反應。之後，使表 氯醇餾去，加入甲基異丁基酮97 0g後，以水洗除去鹽。之 後’添加24%氫氧化鈉水溶液I9.3g，在85°C進行2小時反 應。反應後，進行過濾、水洗後，使溶劑的甲基異丁基酮 減壓餾去’得到環氧樹脂1 46g (環氧樹脂B )。環氧當量 爲1 9 5 . 1、水解性氯爲7 1 5 p p m。D S C測定中之波峰溫度爲 13 5. 1°C、伴隨結晶熔解之吸熱量爲29.8 J/g。毛細管熔點爲 107.8〜140.1°(：、150°(：之熔融黏度爲95111?&.8。0?(：測定 所求出的一般式（1)中之各成分比，n = 〇爲32.25%、n=l 爲18.42%、11 = 2爲12.85%、11 = 3爲9,42%、11 = 4爲6.01%、11 -20- 201144347 2 5爲 16.63%。 實施例3 使合成例3所得樹脂1 1 0 g溶於表氯醇4 8 6 g、二乙二醇 一甲基醚71_5§，減壓下（約1301'〇1>1')在62°〇使48%氫氧 化鈉水溶液7 0 · 8 g花費4小時滴下。此期間，生成的水藉由 與表氯醇共沸除去於系統外、餾出的表氯醇則回到系統內 。滴下完畢後，進一步繼續進行1小時反應。之後，使表 氯醇餾去，加入甲基異丁基酮972g後，以水洗除去鹽。之 後’添加2 4 %氫氧化鈉水溶液1 5.5 g，在8 5。(：進行2小時反 應。反應後，進行過濾、水洗後，使溶劑的甲基異丁基酮 減壓餾去’得到環氧樹脂1 49g (環氧樹脂C )。環氧當量 爲1 8 2.4、水解性氯爲6 7 5 p p m。D S C測定中之波峰溫度爲 1 46.1°C、伴隨結晶熔解之吸熱量爲46.1J/g。毛細管熔點爲 118.2〜147.0°(：、150°〇之熔融黏度爲361^3.8。〇?(：測定 所求出的一般式（1 )中之各成分比，n = 0爲49.16%、n=l 爲 2 0.1 1%、n = 2 爲 10.52%、n = 3 爲 6.5 1%、n = 4 爲 3.9 8%、η g 5 爲 6.6 5 %。 比較例1 使合成例4所得樹脂125g溶於表氯醇462g、二乙二醇 二甲基醚69.3g ’減壓下（約13〇T〇rr )在62。〇使48%氫氧 化鈉水溶液6 9.4 g花費4小時滴下。此期間，生成的水藉由 與表氯醇共沸除去於系統外、餾出的表氯醇則回到系統內 -21 - 201144347 。滴下完畢後，進一步繼續進行1小時反應。之後，使表 氯醇餾去’加入甲基異丁基酮972 g後，以水洗除去鹽。之 後’添加24%氫氧化鈉水溶液19.3g，在85°C進行2小時反 應。反應後，進行過濾、水洗後，使溶劑的甲基異丁基酮 減壓餾去，得到環氧樹脂148g (環氧樹脂D )。環氧當量 爲2 09 _2、水解性氯爲621 ppm。得到樹脂之結晶性低且在 DSC無法確認明確熔點。15〇。(：之熔融黏度爲〇.52Pa · s。 G P C測定所求出的一般式（1 )中之各成分比，n = 〇爲 2 0.7 5 % ' η=1 爲 12.48%、n = 2 爲 10.59%、n = 3 爲 8.57%、n = 4 爲 5.9 9 %、n g 5 爲 3 7 . 1 1 %。 比較例2 使合成例5所得樹脂115g溶於表氯醇549g、二乙二醇 二甲基醚82.4g，減壓下（約l30T〇rr )在62°C使48%氫氧 化鈉水溶液8 2.4 g花費4小時滴下。此期間，生成的水藉由 與表氯醇共沸除去於系統外、餾出的表氯醇則回到系統內 。滴下完畢後，進一步繼續進行1小時反應。之後，使表 氯醇餾去’加入甲基異丁基酮96 6g後，以水洗除去鹽。之 後，加入2 4 %氫氧化鈉水溶液1 9 · 2 g，在8 5 °C進行2小時反 應。反應後’進行過媳、水洗後，使溶劑的甲基異丁基酮 減壓餾去’得到環氧樹脂1 45g (環氧樹脂E )。環氧當量 爲1 73 _0、水解性氯爲490ppm。DSC測定中之波峰溫度爲 133.6°C、伴隨結晶熔解之吸熱量爲47.6J/g。毛細管熔點爲 1 10.0 〜142.0°C、150°C 之熔融黏度爲 42mPa · s。GPC 測定 -22- 201144347 所求出的一般式（1)中之各成分比，n = 〇爲42.92%、π 爲 1 9.6 4 %、η = 2 爲 1 1 . 4 6 %、η = 3 爲 7.6 7 %、η = 4 爲 4 · 9 1 % ' 2 5 爲 1 0.6 4 %。 比較例3 使合成例6所得樹脂120g溶於表氯醇484g、二乙二醇 二甲基醚6 2.9 g，減壓下（約1 3 0 T 〇 r r )在6 2。(：使4 8 %氫氧 化鈉水溶液69.0g花費4小時滴下。此期間，生成的水藉由 與表氯醇共沸除去於系統外、餾出的表氯醇則回到系統內 。滴下完畢後，進一步繼續進行1小時反應。之後’使表 氯醇餾去，加入甲基異丁基酮95 6g後，以水洗除去鹽。之 後，加入2 4 %氫氧化鈉水溶液1 7.6 g，在8 5 °C進行2小時反 應。反應後，進行過濾、水洗後，使溶劑的甲基異丁基酮 減壓餾去，得到淡褐色的非結晶性環氧樹脂1 52.5g (環氧 樹脂F )。環氧當量爲1 9 3 · 5、水解性氯爲4 5 0 p p m。軟化點 爲82t、1 5〇°C之熔融黏度爲68mPa . s。GPC測定所求出的 —般式（1 )中4,4’-二羥基聯苯骨架取代爲4,4，_二羥基二 苯基甲院的構造中之各成分比，n = 〇爲34.54 %、n=l爲 18.65%、11 = 2爲12.34%、11 = 3爲1〇.69%、11 = 4爲8.20%、112 5 爲 1 5.2 2 %。 實施例4〜6、比較例4〜7The gastric hydrolyzable chlorine of the present invention is measured by the following method. After the sample is dissolved in 3 〇mi of dioxane, 5 g of the sample is added, and AlN_K〇H is added for 30 minutes, boiled and refluxed, and then cooled to room temperature, further. Adding the fat raw material step by dissolving the uranium machine salt with the lipid forming material grease and the surface chlorine which can be dissolved in the 11 oxides of the ί1~1 〇 small hydroxy tree I 1.2 molars, /» , \/^t The grade ammonium salt represented by JXDL is specifically limited by the applicable electricity. Also, hehe. That is, 10 ml of 80% acetone -10- 201144347 water 1 00 ml, and the enthalpy obtained by potentiometric titration with 0.0 02 N-AgNO 3 aqueous solution. The epoxy resin composition of the present invention contains an epoxy resin and a curing agent, and the epoxy resin component contains the epoxy resin of the above general formula (1). In the epoxy resin composition of the present invention, in addition to the epoxy resin of the general formula (1) used as an essential component, a general other epoxy resin having two or more epoxy groups in the molecule may be used. For example, bisphenol A, bisphenol F, 3,3',5,5'-tetramethyl-4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylanthracene, 4,4 '-Dihydroxydiphenyl sulfide' 4,4'-dihydroxydiphenyl ketone, bismuth bisphenol, 4,4'-biphenol, 3,3',5,5'-tetramethyl-4,4 '-Dihydroxybiphenyl, 2,2'-biphenol, resorcinol, catechol, t-butylcatechol, t-butyl hydroquinone, 1,2-dihydroxynaphthalene, 1 , 3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, anthracene-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-di Hydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene' 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxynaphthalene, the above dihydroxynaphthalene a phenol or a phenol novolac, a bisphenol A phenol varnish, a phenolic novolac, a allylic bisphenol A, an allylated bisphenol F, an allylated phenol novolak, or the like, 〇-cresol novolac, m-cresol novolac, p_cresol novolac, xylenol novolac, poly-P-hydroxystyrene, ginseng-4-(4-hydroxyphenyl)methane, 〗 1, 2,2-indole (4-hydroxyphenyl)ethane, Glycerol, pyrogallol, t-butyl pyrogallol, allylated pyrogallol 'polyallylated pyrophenol, 1,2,4-benzenetriol' 2,3,4-tri 3 or more phenols such as hydroxybenzophenone, phenolic aryl resin, naphthol aralkyl resin, and dicyclopentadiene resin, or derived from halogenated bisphenols such as tetrabromobisphenol A Ring-11 - 201144347 Oxypropyl propyl etherate and the like. These epoxy resins may be used alone or in combination of two or more. The epoxy resin composition of the present invention is preferably an epoxy resin containing the epoxy resin component of the above formula (1) in an amount of 50% by weight or more. More preferably, it is 70% by weight or more, more preferably 80% by weight or more of the total epoxy resin. When the ratio is less than this, the moldability of the epoxy resin composition is deteriorated, and the effect of improving heat resistance, moisture resistance, thermal conductivity, and reflow resistance as a cured product is small. As the hardener in the epoxy resin composition of the present invention, all known as a hardener for an epoxy resin can be generally used. For example, diamine, polyphenols, anhydrides, aromatic and aliphatic amines. Polyphenols are suitable for use in the field of sealing of electrical and electronic parts requiring moisture resistance and heat resistance. These are specifically exemplified as follows. In the resin composition of the present invention, one or two or more kinds of these curing agents may be used in combination. Examples of the polyhydric phenols include bisphenol A, bisphenol F, bisphenol S, bisphenol, 4, 4, biphenol, 2,2'-biphenol, hydroquinone, resorcin, and naphthalene. a 2-valent phenol such as an alcohol, or a ginseng-(4. hydroxyphenyl)methane, ι, 〗 2, 2-肆 (4-hydroxyphenyl) ethane, a phenol novolac, a bismuth novolak novolac, More than 3 yuan of phenols represented by naphthol novolac, polyvinyl phenol, etc., further phenols, naphthols or bisphenol A, bisphenol F, bisphenol S, bisphenol, 4, 4'-linked Formaldehyde, acetaldehyde, benzaldehyde, P-hydroxybenzaldehyde, ρ·xylene II of phenol, 2,2′-biphenol, hydroquinone, resorcinol, naphthalenediol, etc. A polyphenolic compound synthesized by a condensing agent such as an alcohol. Further, a polyvalent hydroxy resin represented by the general formula (3) can also be used. -12· 201144347 Anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride 'hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, methyl nadic anhydride, Nadickic anhydride, trimellitic anhydride, and the like. The amines are 4,4'-diaminodiphenylmethane, 4,4,-diaminodiphenylpropanoid, 4,4'-diaminodiphenylanthracene, m-phenylenediamine, An aliphatic amine such as p-xylylenediamine or an aliphatic amine such as ethylenediamine 'hexamethylenediamine, diethylenetriamine or triethylenetetramine. In the resin composition of the present invention, one type or two or more types of these hardening agents may be used in combination. Further, the epoxy resin composition of the present invention can be suitably blended with polyester, polyamine, polyimine, polyether, polyphenylene ether, polyurethane, petroleum resin, coumarinone resin, benzene. The oligomer or polymer compound of an oxy resin or the like may be blended with various additives such as an inorganic filler, a pigment, a flame retardant, a shake modification imparting agent, a coupling agent, and a fluidity enhancer. Further, in the epoxy resin composition of the present invention, an inorganic charging agent can be used, for example, two or more kinds of spherical or crushed cerium oxide powder such as molten cerium oxide or crystalline cerium oxide can be used alone or in combination. Aluminum, zirconium calcium citrate, calcium carbonate, tantalum carbide, boron nitride, cerium oxide, oxidized pin, forsterite, talc, spinel, mullite, titanium dioxide, etc., or such spherical Single crystal fiber such as beads, potassium titanate, niobium carbide 'tantalum nitride, aluminum oxide, or the like, glass fiber, and the like. In the above inorganic filler, it is preferred to use molten cerium oxide for the purpose of lowering the coefficient of linear expansion, and alumina is preferred from the viewpoint of high thermal conductivity. The shape of the filler is preferably 50% or more in terms of fluidity during molding and mold wearability, and it is particularly preferable to use a spherical melt-13-201144347 cerium oxide powder. The amount of the inorganic filler to be added is usually 50% by weight or more, preferably 70% by weight or more, more preferably 80% by weight or more, based on the epoxy resin composition. On the other hand, the effects of the present invention having low hygroscopicity, low thermal expansion property, high heat resistance, and high thermal conductivity cannot be sufficiently exhibited. The effect of these is that the addition of inorganic filling materials is better, but it is not affected by the increase in body weight, but it is greatly increased by the specific addition amount. On the other hand, when the addition of the inorganic filler is more than this, the viscosity is high and the formability is deteriorated, which is not preferable. The epoxy resin composition of the present invention can be blended with a known hardening accelerator. For example, an amine, an imidazole, an organic phosphine, a Lewis acid, etc., specifically, for example, 1,8-diazabicyclo(5,4,0)undecene-7, 1,5-diaza- Bicyclic (4,3,0) terpene, 5,6-dibutylamino-1,8-diaza-bicyclo(5,4,0) undecene-7, etc. a compound having an intramolecular polarization obtained by adding a compound having a π bond such as maleic anhydride, benzoquinone or diazophenylmethane, triethylenediamine, decyldimethylamine, triethanolamine, and Tertiary amines such as methylaminoethanol and ginseng (dimethylaminomethyl)phenol and derivatives thereof, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methyl Imidazoles such as imidazole and 2 ·heptyl imidazole, and derivatives thereof, organic phosphines such as tributylphosphine, methyl diphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine, etc. The phosphine is added to a compound having a π bond such as maleic anhydride, benzene flooding, or diazobenzene, and the phosphorus compound having tetramolecular tetraphenyl borate Tetraphenyl scale • ethyl triphenyl borate, tetrabutyl iron • four Tetrasubstituted sulphate, etc. tetrasubstituted borate, 2-ethyl-4-methylimidazole • tetraphenyl borate, Ν-methylmorpholine. tetraphenyl-14 - 201144347 boronic acid a tetraphenylboron salt such as an ester or the like and the like. The amount of addition is usually in the range of 〇 2 to 10 parts by weight relative to 1 重量 0 parts by weight of the epoxy resin. These can be used alone or in combination. In the epoxy resin composition of the present invention, a flame retardant is used as necessary. Examples of such a flame retardant include a phosphorus-based flame retardant such as red phosphorus or a phosphorus-oxygen compound, a nitrogen-based flame retardant such as a triazine derivative, a phosphorus-nitrogen-based flame retardant such as an azo-phosphorus derivative, or a metal. An organometallic complex such as an oxide 'metal hydrate or a metallocene derivative, a zinc compound such as zinc borate 'zinc stannate or zinc molybdate, and the like, and a metal hydrate is preferred. Examples of the metal hydrate include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, nickel hydroxide, cobalt hydroxide, iron hydroxide, tin hydroxide, zinc hydroxide, copper hydroxide, and titanium hydroxide. A composite metal hydrate of such a metal hydrate with a metal oxide such as nickel oxide, cobalt oxide, iron oxide, tin oxide, zinc oxide, copper oxide or palladium oxide can also be used. Magnesium hydroxide is preferred from the viewpoints of safety, flame retardant effect, and formability of the formed material. In the epoxy resin composition of the present invention, in addition to the above, a high-fat fatty acid, a higher fatty acid metal salt, an ester wax, a release agent such as a polystyrene wax, a coloring agent such as carbon black, a decane system, or the like may be used. a coupling agent such as a titanate-based or an aluminate-based compound, a flexible agent such as an anthrone powder, a stress relieving agent such as a sulphonic acid or a sulphuric acid rubber powder, an ion of a magnesite, a lanthanum-niobium or the like Collecting agent, etc. Further, the epoxy resin composition of the present invention can be added with thermoplastic oligomers from the viewpoints of improvement in fluidity at the time of molding and improvement in adhesion to a substrate such as a lead frame. Thermoplastic oligomers, such as C5 and (1) -15- 201144347, petroleum tree s曰' styrene resin, oxime resin, ytterbium styrene copolymer tree, yttrium, yttrium ethylene, phenol copolymerization Resin, hydrazine-coumarone copolymerization resin, hydrazine thiophene copolymerization resin, etc. The amount of addition is usually in the range of 2 to 3 parts by weight relative to the weight of the epoxy resin. In the method for preparing the epoxy resin composition of the present invention, any method in which various raw materials can be uniformly dispersed and mixed can be used. However, in general, for example, a specific amount of the raw materials may be sufficiently mixed by a mixer or the like, and the mixture may be lightly mixed. A method of melt-kneading, cooling, and pulverizing by an extruder or the like. The epoxy resin composition of the present invention is particularly suitable for sealing a semiconductor device. The cured product of the invention is obtained by thermally curing the epoxy resin composition. The epoxy resin composition of the present invention is obtained by a method such as transfer molding, press molding, injection molding, injection molding, extrusion molding, or the like, but is transferred from the viewpoint of mass productivity. [Embodiment] [Examples] Hereinafter, the present invention will be further specifically described by way of a cargo example. Synthesis Example 1 4,4'-dihydroxyl linkage was added to a 4-inch flask of 2 〇〇〇ml. Benzene 186_0g (dimethoprim) and diethylene glycol dimethyl ether (600g) were heated to 150 after stirring under nitrogen flow. (:, 4,4' was dissolved in 260 g of diethylene glycol dimethyl ether. - a solution of 75.3 g (0.3 mol) of dichloromethylbiphenyl, and then heating to -16-201144347 1 70 °c for 2 hours. After the reaction, it is dripped into a large amount of pure water and then recovered by reprecipitation. 2,0 g of a resin having a pale yellow crystallinity was obtained, and 11 equivalents of the resin were obtained as 130.8. 〇3 (: the peak temperature in the measurement was 248.5, and the heat absorption accompanying the dissolution of the crystal was 95.5 J/g. The GPC chart is shown in Fig. 1. The ratio of each component in the general formula (3) obtained by GPC measurement, n = 0 is 3 9.3 3 % ' n = l is 22.2 5 %, n = 2 is 12.19%, n = 3 8.14%, n = 4 is 5.5 8 %, and η 2 5 is 11.8%. The DSC peak temperature refers to the use of differential scanning calorimetry (DSC220 Type C manufactured by Seiko Instruments).値 measured at a heating rate of 5 ° C / min. Also, GPC measurement, device; Japan Waters (stock) system, 515A type, pipe column; TSK-GEL200〇x3 branch and TSK-GEL4000X 1 branch (All Dongcao (shares) )), solvent; tetrahydrofuran, flow rate; lml/min, temperature; 38 ° C, detector; following the conditions of RI Synthesis Example 2 In addition to the use of 4,4'-dihydroxybiphenyl I67.4g (0.9 m ), 540 g of diethylene glycol dimethyl ether, 90.4 g (0.36 mol) of 4,4′-dichloromethylbiphenyl dissolved in diethylene glycol dimethyl ether 3 20 g, and Example 1 The reaction was carried out in the same manner to obtain a pale yellow and crystalline resin (250 g). The OH equivalent of the obtained resin was 139.2. The DSC peak temperature is 242.4 ° C, the ratio of each component in the general formula (3) obtained by GPC measurement, 11 = 0 is 31.21% '11 =: 1 is 21.19%, and 11 = 2 is 13.38% '11 = 3 It is 1〇.63%, 11=4 is 7.55%, and 112 5 is 15.53%. -17- 201144347 Synthesis Example 3 In addition to the use of 4,4'-dihydroxybiphenyl l86.0 g (l. oxime), alcohol dimethyl ether 540 g, 4,4'- bischloromethylbiphenyl 5 〇 2 g (〇2) was reacted with Example 1 except that a solution of 32 g of diethylene glycol dimethyl ether was used to obtain 1 95 g of a pale yellow crystalline resin. The obtained OH equivalent was 125.6. The DSC peak temperature was 25. 5.4.::, the ratio of each component in the general formula (3) measured by GPC, n = 〇 is 50.87 %, 2 0.6 7 %, η = 2 is 1 1 · 5 4 %, and η = 3 is 7 1 1 %, n = 4 is 3.7 8 % is 5 · 8 7 %. Synthesis Example 4 In addition to using 4,4'-dihydroxybiphenyl 152.5 g (0.82 mol) glycol dimethyl ether 500 g, 4, 4' - Dichloromethylbiphenyl ii 2.9 g (0.) was dissolved in a solution of diethylene glycol dimethyl ether (360 g), and reacted with an actual sample to obtain 201 g of a pale yellow resin. 5 0 · 1. Each of 'n = 0 in the general formula (3) obtained by GPC measurement is 22.03%, n = l is 14.65%, n = 2 is 11.89%, 9.46% '11 = 4 is 7.36% , 11 & 5 is 33.87 0 / 〇〇 Synthesis Example 5 In addition to the use of 4,4 '-dihydroxybiphenyl 186.0 g (1.0 mol), A solution of 600 g of dimethyl ether and 52.5 g of 1,4-dichloromethylbenzene (260 mol of 0.3 mol of diethylene glycol dimethyl ether) was reacted with Example 1 to obtain a pale yellow crystalline resin 202. The obtained resin is obtained by dissolving the same resin as n=1, η 2 5 , and diethyl 45 δ δ, and the composition ratio of η = 3 is diethylene). Into the ground! The purpose of the ΟΗ -18- 201144347 equivalent is 116.3. The DSC peak temperature is 241.7 ° C, and the general formula (3) obtained by GPC measurement corresponds to the ratio of each component of the phenylene group substituted with the biphenylene group in the crosslinked portion, and η = 0 is 4 0.3 3 %. η = 1 is 2 3 · 3 1 %, η = 2 is 1.22%, η = 3 is 7.09%, η = 4 is 5.17%, and ng 5 is 12.35%. Synthesis Example 6 In addition to substitution 4, 4, - Dihydroxybiphenyl (1.0 mol), except that 200.0 g (1.0 mol) of 4,4'-dihydroxydiphenylmethane was used, the reaction was carried out in the same manner as in Synthesis Example 1, and the solvent was distilled off under reduced pressure. A pale brown resin of 245 g was obtained. The Ο equivalent of the resin is 1 3 7.6. The ratio of each component in the structure of 4,4'-dihydroxybiphenyl skeleton substituted by 4,4,-dihydroxydiphenylmethane in the general formula (3) obtained by GPC measurement, η = 0 is 3 6 · 8 9 %, η = 1 is 2 0.3 6 %, η = 2 is 12.30%, η = 3 is 9.68%, η = 4 is 6.58%, and ng 5 is 13.56%. Example 1 The resin obtained in Synthesis Example 1 was used. 0 g dissolved in epichlorohydrin 5 0 9 g, diethylene glycol dimethyl ether 76.4 §, under reduced pressure (about 13 0 〇 〇 1 * 〇 62 ° 〇 48% sodium hydroxide aqueous solution 76.5 g cost 4 During this period, the produced water is removed from the system by azeotrope removal with epichlorohydrin, and the distilled epichlorohydrin is returned to the system. After the completion of the dropwise addition, the reaction is further continued for 1 hour. The alcohol was distilled off, 97 1 g of methyl isobutyl ketone was added, and the salt was removed by washing with water. Thereafter, 1 9.3 g of a 24% aqueous sodium hydroxide solution was added, and the reaction was carried out at 85 ° C for 2 hours. After the reaction, filtration was carried out. After washing with water, the methyl isobutyl ketone of the solvent was reduced by -19-201144347 to obtain an epoxy resin 丨 4 8 g (epoxy resin A). The epoxy equivalent was 183.7 and the hydrolyzable chlorine was 1 400 ppm. Get the tree The GPC chart is shown in Fig. 2. The ratio of each component in the general formula (〗) obtained by GPC measurement, n = 〇 is 42.49%, n = l is 19.41%, n = 2 is 12.23%, and n = 3 is 8.50. %, n-4 is 4.5 6 %, ng 5 is 8. 丨 8%. The results of DS c measurement are shown in Fig. 3. The peak temperature in the DSC measurement is 140.0 ° C, and the heat absorption with crystal melting is 36, 9 J / g. The melting point of the capillary is Hi.5~i43.8 ° C, and the melt viscosity at 150 ° C is 51 mPa·s. Example 2 122 g of the resin obtained in Synthesis Example 2 was dissolved in epichlorohydrin 486 g, diethylene glycol II. Methyl ether 72.98, under reduced pressure (about 1301'〇1^) at 62. (: 48% sodium hydroxide aqueous solution 7 3 · 0 g took 4 hours to drip. During this period, the generated water by using epichlorohydrin The azeotrope removed from the system and the distilled epichlorohydrin was returned to the system. After the completion of the dropwise addition, the reaction was further carried out for 1 hour. Thereafter, the epichlorohydrin was distilled off, and 97 0 g of methyl isobutyl ketone was added. The salt was removed by washing with water. Then, I9.3 g of a 24% aqueous sodium hydroxide solution was added, and the reaction was carried out at 85 ° C for 2 hours. After the reaction, the mixture was filtered, washed with water, and the solvent was distilled under reduced pressure of methyl isobutyl ketone. ' Obtained epoxy resin 1 46g (epoxy resin B). The epoxy equivalent was 195. 1. The hydrolyzable chlorine was 7 15 ppm. The peak temperature in the DSC measurement was 13 5. 1 ° C, accompanied by crystal melting. The heat absorption is 29.8 J/g. The melting point of the capillary is 107.8 to 140.1 ° (:, 150 ° (the melting viscosity is 9511? & 8.0? (: the ratio of each component in the general formula (1) determined by the measurement, n = 〇 is 32.25 %, n=l is 18.42%, 11=2 is 12.85%, 11=3 is 9,42%, 11=4 is 6.01%, and 11-20-201144347 2 5 is 16.63%. Example 3 Synthesis Example 3 The obtained resin 1 100 g was dissolved in epichlorohydrin 4 8 6 g, diethylene glycol monomethyl ether 71_5 § under reduced pressure (about 1301 '〇1 > 1') at 48 ° 〇 to make 48% sodium hydroxide The aqueous solution of 7 0 · 8 g takes 4 hours to drip. During this period, the produced water is removed from the system by azeotropy with epichlorohydrin and returned to the system. After the completion of the dropwise addition, the water is further continued. After the reaction, the epichlorohydrin was distilled off, and after adding 972 g of methyl isobutyl ketone, the salt was removed by washing with water, and then 15.5 g of a 4 4% aqueous sodium hydroxide solution was added thereto at 85 ° C. (: 2 hours) After the reaction, the mixture was filtered and washed with water, and then the methyl isobutyl ketone of the solvent was distilled off under reduced pressure to obtain 1 49 g of an epoxy resin (epoxy resin C). The epoxy equivalent was 1 8 2.4, and the hydrolyzable chlorine was 6 7 5 ppm. DSC measurement The peak temperature is 146.1 ° C, and the heat absorption with crystal melting is 46.1 J/g. The melting point of the capillary is 118.2 to 147.0 ° (:, 150 ° 〇 melt viscosity is 361 ^ 3.8. 〇? The ratio of each component in the general formula (1) is such that n = 0 is 49.16%, n = l is 2 0.1 1%, n = 2 is 10.52%, n = 3 is 6.5 1%, and n = 4 is 3.9 8 % and η g 5 were 6.65%. Comparative Example 1 125 g of the resin obtained in Synthesis Example 4 was dissolved in epichlorohydrin 462 g and diethylene glycol dimethyl ether 69.3 g under reduced pressure (about 13 〇T〇rr). 62. The 48% sodium hydroxide aqueous solution 6 9.4 g was dropped for 4 hours. During this period, the produced water was removed from the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. - 201144347. After the completion of the dropwise addition, the reaction was further continued for 1 hour. Thereafter, epichlorohydrin was distilled off, and 972 g of methyl isobutyl ketone was added, and the salt was removed by washing with water. Thereafter, a urea aqueous solution of 24% was added to 19.3 g. The reaction was carried out for 2 hours at 85 ° C. After the reaction, the mixture was filtered and washed with water, and then methyl isobutyl ketone of the solvent was evaporated under reduced pressure to give 148 g (e.g. The epoxy equivalent was 2 09 _2 and the hydrolyzable chlorine was 621 ppm. The crystallinity of the obtained resin was low and the melting point could not be confirmed in DSC. 15〇. (The melt viscosity is 〇.52 Pa · s. The ratio of each component in the general formula (1) obtained by GPC measurement, n = 〇 is 2 0.7 5 % ' η = 1 is 12.48%, and n = 2 is 10.59. %, n = 3 was 8.57%, n = 4 was 5.9 9 %, and ng 5 was 37.11%. Comparative Example 2 115 g of the resin obtained in Synthesis Example 5 was dissolved in epichlorohydrin 549 g, diethylene glycol dimethicone 82.4 g of the ether was dropped under reduced pressure (about l30 T rrrr) at 48 ° C for 8 hours in 48% sodium hydroxide aqueous solution. During this period, the formed water was removed by azeotropy with epichlorohydrin in the system. The distilled and distilled epichlorohydrin was returned to the system. After the completion of the dropwise addition, the reaction was further continued for 1 hour. Thereafter, epichlorohydrin was distilled off, and 96 6 g of methyl isobutyl ketone was added, followed by washing with water to remove the salt. Thereafter, 1 2 · 2 g of a 24 % aqueous sodium hydroxide solution was added, and the reaction was carried out at 85 ° C for 2 hours. After the reaction, the mixture was subjected to hydrazine and washed with water, and the methyl isobutyl ketone of the solvent was distilled off under reduced pressure. 1 45 g (epoxy resin E) of epoxy resin was obtained, the epoxy equivalent was 1 73 _0, and the hydrolyzable chlorine was 490 ppm. The peak temperature in the DSC measurement was 133.6 ° C, and the heat absorption accompanying the crystal melting was 47.6 J/g. The melting point of the capillary is 1 10.0 to 142.0 ° C, and the melt viscosity at 150 ° C is 42 mPa · s. The ratio of each component in the general formula (1) obtained by GPC measurement -22-201144347, n = 〇 It is 42.92%, π is 1 9.6 4 %, η = 2 is 11.46%, η = 3 is 7.6 7 %, and η = 4 is 4 · 9 1 % ' 2 5 is 1 0.6 4 %. 3 120 g of the resin obtained in Synthesis Example 6 was dissolved in 484 g of epichlorohydrin and 2.9 g of diethylene glycol dimethyl ether, and under reduced pressure (about 130 Torr) at 6 2 (: 4 8 % hydrogen) 69.0 g of an aqueous sodium hydroxide solution was dropped for 4 hours. During this period, the produced water was removed from the system by azeotropy removal with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After the completion of the dropwise addition, the reaction was further continued for 1 hour. After the reaction, the epichlorohydrin was distilled off, 95 6 g of methyl isobutyl ketone was added, and the salt was removed by washing with water. Thereafter, 1 7.6 g of a 24% aqueous sodium hydroxide solution was added, and the reaction was carried out at 85 ° C for 2 hours. After the reaction, the mixture was filtered and washed with water, and then methyl isobutyl ketone of the solvent was distilled off under reduced pressure to obtain 52.5 g (epoxy resin F) of a pale brown amorphous epoxy resin. The epoxy equivalent was 1 9 . 3 · 5, the hydrolyzable chlorine is 4 50 p p m. The softening point is 82 t, and the melt viscosity of 15 ° C is 68 mPa·s. The ratio of the 4,4'-dihydroxybiphenyl skeleton in the general formula (1) obtained by the GPC measurement to the composition ratio of the 4,4,-dihydroxydiphenyl group was n, and the ratio was 34.54. %, n=l is 18.65%, 11=2 is 12.34%, 11=3 is 1〇.69%, 11=4 is 8.20%, and 112 5 is 15.2 2%. Examples 4 to 6 and Comparative Examples 4 to 7
作爲環氧樹脂成分’使用實施例！〜3之環氧樹脂（環 氧樹脂A〜C )、比較例1〜3之環氧樹脂（環氧樹脂D〜F -23- 201144347 )，作爲硬化劑使用酚酚醛清漆（群榮化學製、PSM-426 1 ;OH當量1 03、軟化點82 °C )。又，作爲硬化促進劑使用 三苯基膦、作爲無機充塡材使用球狀氧化鋁（平均粒徑 1 2.2 μηι )。搭配如表1所示成分，以混合機充分混合後， 將以加熱輥約5分鐘混練者冷卻，粉碎後分別得到實施例4 〜6、比較例4〜7之環氧樹脂組成物。使用該環氧樹脂組 成物，以175°C、5分鐘之條件成形後、在180°C進行12小時 後烘焙得到硬化成形物後，評估其物性。 結果一倂如表1。又，表1中各搭配物的數字爲重量份 。又，評估如下進行。又，因比較例4流動性顯著低、成 形困難，無法評估成形物的物性。 (1 )熱傳導率：使用NETZSCH製LFA447型熱傳導率 計以暫態熱線法測定。 (2 )線膨脹係數、玻璃轉移溫度：使用Seiko Instruments (股）製TMA120C型熱機械測定裝置，以昇溫速 度l〇°C/分鐘測定。 (3 )吸水率：使直徑5 0m m、厚度3 m m之圓盤成形， 後烘焙後、以85°C、相對濕度85%之條件使進行1〇〇小時吸 濕後之重m變化率。 (4 )凝膠時間：在預先加熱至1 75 °C的膠體化試驗機 (曰新科學（股）製）之凹部流入環氧樹脂組成物’使用 PTFE製的攪拌棒以一秒鐘2回轉之速度攪拌，調查到環氧 樹脂組成物硬化爲止所要的膠體化時間。 (5 )螺旋流動：以依據規格（EMM 1-1-66 )的螺旋流 -24- 201144347 動測定用模具使環氧樹脂組成物以螺旋流動的注入壓力（ 150kgf/cm2)、硬化溫度175°C、硬化時間3分鐘之條件成 形後，調查流動長。 [表1] 實施例 1 實施例 2 實施例 3 比較例 4 比較例 5 比較例 6 比較例 7 環氧樹脂A 96.0 環氧樹脂B 98. 0 環氧樹脂c 96.0 環氧樹脂D 100.5 100.5 環氧樹脂E 94. 0 環-氧樹脂F 98.0 硬化劑 54.0 52.0 54.0 49. 5 49. 5 56.0 52.0 無機充塡材 1350 1350 1350 1350 800 1350 1350 硬化促進劑 1.6 1. 6 1. 6 1.6 1.6 1.6 1.6 凝膠時間^sec) 33 32 31 27 28 31 34 螺旋流動(cm) 102 94 86 15 45 89 105 玻璃轉移點(°c) 194 203 187 204 178 147 熱膨脹係數 (ppm,<Tg) 10.0 10.0 10.4 15.4 10.6 11. 1 熱膨脹係數 (ppm,>Tg) 47.0 46. 6 51.2 73. 1 55.3 57.4 吸水率(wt%，100h) 0. 19 0. 17 0. 19 0.24 0. 23 0.22 熱傳導率(W/m-K) 4.50 4. 84 4.47 3.52 3.60 3.53 [產業上的利用性] 本發明的環氧樹脂因係結晶性且具有熔點，作爲固體 的操作性優、且低黏度故成形性亦優，同時應用於環氧樹 月曰過成物時，可得優異的局耐熱性、熱分解安定性 '及高 熱傳導性優異的硬化物，可適用於電氣•電子零件類之封 閉、電路基扳材料等用途。又’由本發明所得環氧樹脂係 -25- 201144347 低黏度性及作爲固體的操作性優異，同時可得到耐熱性、 耐濕性、及熱傳導性亦優異的硬化物，適宜用於印刷配線 板、散熱基板、半導體封閉等之電氣電子領域的絕緣材料 【圖式簡單說明】 [圖1 ]參考例1所得樹脂之G P C圖表。 [圖2]實施例1所得樹脂之GPC圖表。 [圖3 ]苡施例1所得樹脂之D S C圖表。 -26-Use examples as epoxy resin components'! ~3 epoxy resin (epoxy resin A~C), epoxy resin of epoxy resin (Epoxy resin D~F-23-201144347), used as a hardener, phenol novolac (manufactured by Qun Rong Chemical Co., Ltd.) PSM-426 1 ; OH equivalent 1 03, softening point 82 ° C). Further, triphenylphosphine was used as the hardening accelerator, and spherical alumina (having an average particle diameter of 1 2.2 μηι) was used as the inorganic filler. After mixing well with a mixer as shown in Table 1, the mixture was cooled by a heat roller for about 5 minutes, and pulverized to obtain epoxy resin compositions of Examples 4 to 6 and Comparative Examples 4 to 7, respectively. Using this epoxy resin composition, it was molded at 175 ° C for 5 minutes, and then baked at 180 ° C for 12 hours to obtain a cured product, and then the physical properties were evaluated. The results are shown in Table 1. Further, the numbers of the respective objects in Table 1 are parts by weight. Also, the evaluation is performed as follows. Further, in Comparative Example 4, the fluidity was remarkably low and the forming was difficult, and the physical properties of the molded product could not be evaluated. (1) Thermal conductivity: measured by a transient hot line method using a LEMA447 type thermal conductivity meter manufactured by NETZSCH. (2) Linear expansion coefficient and glass transition temperature: The temperature was measured at a temperature increase rate of 10 ° C/min using a Thermo Scientific measuring apparatus manufactured by Seiko Instruments Co., Ltd. (3) Water absorption rate: A disk having a diameter of 50 m and a thickness of 3 m was formed, and after the post-baking, the rate of change in weight m after the adsorption for 1 hour was performed at 85 ° C and a relative humidity of 85%. (4) Gel time: Into the concave portion of the colloidal testing machine (manufactured by Fuxin Scientific Co., Ltd.) which was previously heated to 1 75 ° C, the epoxy resin composition was poured into a 2-minute rotation using a stirring rod made of PTFE. The speed was stirred, and the colloidal time required for the epoxy resin composition to harden was investigated. (5) Spiral flow: Injecting pressure (150kgf/cm2) of the epoxy resin composition in a spiral flow according to the specification (EMM 1-1-66) spiral flow-24- 201144347, and the hardening temperature is 175° C. After the conditions of the hardening time of 3 minutes were formed, the flow length was investigated. [Table 1] Example 1 Example 2 Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Epoxy Resin A 96.0 Epoxy Resin B 98. 0 Epoxy Resin c 96.0 Epoxy Resin D 100.5 100.5 Epoxy Resin E 94. 0 Ring-Oxygen Resin F 98.0 Hardener 54.0 52.0 54.0 49. 5 49. 5 56.0 52.0 Inorganic Filling Material 1350 1350 1350 1350 800 1350 1350 Hardening Accelerator 1.6 1. 6 1. 6 1.6 1.6 1.6 1.6 Condensation Glue time ^sec) 33 32 31 27 28 31 34 Spiral flow (cm) 102 94 86 15 45 89 105 Glass transfer point (°c) 194 203 187 204 178 147 Thermal expansion coefficient (ppm, <Tg) 10.0 10.0 10.4 15.4 10.6 11. 1 Thermal expansion coefficient (ppm, > Tg) 47.0 46. 6 51.2 73. 1 55.3 57.4 Water absorption (wt%, 100h) 0. 19 0. 17 0. 19 0.24 0. 23 0.22 Thermal conductivity (W/ mK) 4.50 4. 84 4.47 3.52 3.60 3.53 [Industrial Applicability] The epoxy resin of the present invention has crystallinity and melting point, and is excellent in workability as a solid, and has low viscosity and thus excellent formability. Excellent heat resistance and thermal decomposition of epoxy resin Of 'high thermal conductivity and excellent cured properties, applicable to electric • use the closed type electronic component, circuit board material or the like pull. Further, the epoxy resin obtained in the present invention is a low-viscosity property and excellent in handleability as a solid, and a cured product excellent in heat resistance, moisture resistance, and thermal conductivity, and is suitable for use in a printed wiring board. Insulating material in the field of electrical and electronic fields such as heat-dissipating substrate and semiconductor sealing [Simplified description of the drawing] [Fig. 1] GPC chart of the resin obtained in Reference Example 1. 2] A GPC chart of the resin obtained in Example 1. [Fig. 3] A D S C chart of the resin obtained in Example 1. -26-