TW201802136A

TW201802136A - Polyhydroxy resin, method for producing same, epoxy resin, epoxy resin composition and cured product of epoxy resin composition

Info

Publication number: TW201802136A
Application number: TW106110365A
Authority: TW
Inventors: 廣田健; 大村昌己
Original assignee: 新日鐵住金化學股份有限公司
Priority date: 2016-03-30
Filing date: 2017-03-28
Publication date: 2018-01-16
Also published as: JP6937744B2; WO2017170703A1; TWI728084B; JPWO2017170703A1

Abstract

Provided are: an epoxy resin composition which is capable of providing a cured product that exhibits high Tg properties and excellent thermal decomposition stability if used for lamination, molding, casting, bonding and the like, while having an excellent effect of reducing chlorine ions in an extraction solution, and which is useful as a sealing material for electrical/electronic components and the like, a circuit board material and a sheet material; and a polyhydroxy resin which serves as a starting material for an epoxy resin that is used for the purpose of obtaining the above-described cured product. A polyhydroxy resin represented by general formula (3), which is characterized in that: a component where n = 0 is from 15% to 30% (inclusive); a high molecular weight component where n = 6 or higher is 30% or less; and the total chlorine amount is 1,000 wt ppm or less. (In the formula, n represents a number of 0-20.).

Description

多價羥基樹脂、其之製造方法、環氧樹脂、環氧樹脂組成物及其之硬化物 Polyvalent hydroxyl resin, method for producing the same, epoxy resin, epoxy resin composition, and hardened product thereof

本發明有關總氯量低的多價羥基樹脂、其之製造方法、使用其之環氧樹脂、環氧樹脂組成物及硬化物。 The present invention relates to a polyvalent hydroxyl resin having a low total chlorine content, a method for producing the same, an epoxy resin using the same, an epoxy resin composition, and a cured product.

環氧樹脂雖可於工業上廣泛用途中使用，但其要求性能逐年高度化。該等中，對於近幾年進行開發之功率裝置，要求裝置之功率密度進一步提高，其結果，期望開發即使動作時之晶片表面溫度達到250℃亦可耐受該溫度之密封材料。 Although epoxy resin can be used in a wide range of industrial applications, its required performance is increasing year by year. Among these, power devices that have been developed in recent years are required to further increase the power density of the devices. As a result, it is desired to develop a sealing material that can withstand the temperature even if the wafer surface temperature during operation reaches 250 ° C.

此等中，專利文獻1中揭示具有聯酚-聯苯基芳烷基構造之環氧樹脂、環氧樹脂組成物及硬化物，且顯示耐熱性、耐濕性及熱傳導性優異。 Among these, Patent Document 1 discloses that an epoxy resin, an epoxy resin composition, and a cured product having a biphenol-biphenylaralkyl structure have excellent heat resistance, moisture resistance, and thermal conductivity.

專利文獻2、3中亦同樣揭示具有聯酚-聯苯基芳烷基構造之環氧樹脂組成物、環氧樹脂硬化物之製造方法及半導體裝置，並顯示獲得耐熱性、熱分解安定性優異之硬化物。 Patent Documents 2 and 3 also disclose an epoxy resin composition having a biphenol-biphenylaralkyl structure, a method for manufacturing an epoxy resin hardened product, and a semiconductor device, and have shown excellent heat resistance and thermal decomposition stability. Of hardened.

然而，專利文獻1~3雖揭示原料使用含氯之化合物所得之多價羥基樹脂或環氧樹脂，但關於其氯量全然未觸及，實際上，由於多價羥基樹脂中殘留之氯量高，故於隨後環氧化所得之環氧樹脂之氯量亦高，而有硬化物之信賴性惡化之課題。且，專利文獻3中，由於所得環氧樹脂之熔融黏度高，故有成形步驟中之作業性低的課題，且由於必須增加n=0成分之去除步驟之操作，故工業上欠佳。 However, although Patent Documents 1 to 3 disclose polyvalent hydroxy resins or epoxy resins obtained by using a chlorine-containing compound as a raw material, the amount of chlorine is completely untouched. In fact, since the amount of chlorine remaining in the polyvalent hydroxy resin is high, Therefore, the amount of chlorine in the epoxy resin obtained after the subsequent epoxidation is also high, and there is a problem that the reliability of the cured product is deteriorated. Further, in Patent Document 3, since the obtained epoxy resin has a high melt viscosity, there is a problem that the workability in the molding step is low, and since an operation of removing the n = 0 component must be added, it is industrially unsatisfactory.

[先前技術文獻] [Prior technical literature]

[專利文獻] [Patent Literature]

[專利文獻1]WO2011/074517號公報 [Patent Document 1] WO2011 / 074517

[專利文獻2]WO2014/065152號公報 [Patent Document 2] WO2014 / 065152

[專利文獻3]WO2015/146606號公報 [Patent Document 3] WO2015 / 146606

本發明之目的係可提供可獲得具有高的耐熱性，且信賴性及成形作業性亦優異之環氧樹脂硬化物的環氧樹脂、及作為用以效率良好地獲得該環氧樹脂之原料有用之多價羥基樹脂及其製造方法。 An object of the present invention is to provide an epoxy resin which can obtain an epoxy resin hardened product having high heat resistance and excellent reliability and molding workability, and is useful as a raw material for efficiently obtaining the epoxy resin. Polyvalent hydroxy resin and its manufacturing method.

且，本發明之另一目的係藉由使用以該多價羥基樹脂作為原料所得之環氧樹脂，而提供於功率裝置密封材等之電氣．電子零件類之密封材料、或電路基板材料、薄片材料中有用之環氧樹脂組成物，及提供其硬化物。 And, another object of the present invention is to provide electric power for sealing materials of power devices by using an epoxy resin obtained by using the polyvalent hydroxy resin as a raw material. Sealing materials for electronic parts, circuit board materials, and sheet materials The epoxy resin composition useful in the material and provides its hardened.

亦即，本發明係一種多價羥基樹脂，其特徵係使以式(1)表示之4,4’-二羥基聯苯與以式(2)表示之作為芳香族交聯劑之4,4’-雙氯甲基聯苯反應而得之以通式(3)表示之多價羥基樹脂，且n=0成分為30%以下15%以上，n=6以上之高分子量成分為30%以下，且總氯量為1000ppm以下，

That is, the present invention is a polyvalent hydroxyl resin characterized in that 4,4'-dihydroxybiphenyl represented by the formula (1) and 4,4 represented by the formula (2) as an aromatic crosslinking agent The polyvalent hydroxy resin represented by the general formula (3) is obtained by the reaction of '-dichloromethyl biphenyl, and the n = 0 component is 30% or less and 15% or more, and the high molecular weight component of n = 6 or more is 30% or less. , And the total chlorine content is below 1000ppm,

其中，n表示0~20之數。 Among them, n represents a number from 0 to 20.

本發明係一種上述多價羥基樹脂之製造方法，其特徵為對於4,4’-二羥基聯苯(1)1莫耳，使用芳香族交聯劑(2)0.3~0.6莫耳，以使固形分濃度成為30~65wt%之方式使用溶劑進行反應。 The present invention relates to a method for producing the above-mentioned polyvalent hydroxy resin, which is characterized in that for 4,4'-dihydroxybiphenyl (1) 1 mole, an aromatic crosslinking agent (2) 0.3 to 0.6 mole is used so that The reaction was performed using a solvent such that the solid content concentration became 30 to 65 wt%.

又，本發明係一種環氧樹脂，其特徵係使上述多價羥基樹脂與表氯醇反應而得。 The present invention is an epoxy resin, which is characterized in that The polyvalent hydroxy resin is obtained by reacting with epichlorohydrin.

進而，本發明係一種環氧樹脂組成物，其特徵係以上述環氧樹脂及硬化劑作為必須成分，及提供一種環氧樹脂硬化物，其特徵係使上述環氧樹脂組成物硬化者。 Furthermore, this invention is an epoxy resin composition characterized by including the said epoxy resin and hardener as an essential component, and providing the epoxy resin hardened | cured material characterized by the said epoxy resin composition being hardened.

依據本發明，儘管使用雙氯甲基聯苯作為原料交聯劑，仍為總氯量經減低之多價羥基樹脂，且藉由以該多價羥基樹脂作為原料與表氯醇反應，而可效率良好地製造低黏度且低氯性之優異環氧樹脂。且，藉由使調配有該環氧樹脂之環氧樹脂組成物加熱硬化，可獲得具有高Tg性以外，萃取水氯離子之減低效果及成形作業性優異之硬化物，而可較好地使用於電氣．電子零件類之密封材料、高放熱薄片、高放熱基板等之電路基板材料等之用途中。 According to the present invention, although dichloromethylbiphenyl is used as a raw material cross-linking agent, it is a polyvalent hydroxyl resin having a reduced total chlorine content, and by using the polyvalent hydroxyl resin as a raw material to react with epichlorohydrin, it is possible to Efficiently manufacture excellent epoxy resin with low viscosity and low chlorine resistance. In addition, by curing the epoxy resin composition formulated with the epoxy resin by heating, a hardened product having a high Tg property, a reduction effect of extracting water and chloride ions, and an excellent molding workability can be obtained, and can be suitably used. Yu Electric. It is used for sealing materials of electronic parts, high exothermic flakes, high exothermic substrates and other circuit substrate materials.

圖1係實施例1所得之多價羥基樹脂A之GPC圖表。 FIG. 1 is a GPC chart of the polyvalent hydroxy resin A obtained in Example 1. FIG.

圖2係比較例1所得之多價羥基樹脂D之GPC圖表。 FIG. 2 is a GPC chart of the polyvalent hydroxy resin D obtained in Comparative Example 1. FIG.

圖3係實施例2所得之環氧樹脂A之GPC圖表。 FIG. 3 is a GPC chart of the epoxy resin A obtained in Example 2. FIG.

本發明之多價羥基樹脂係通式(3)表示之重複單位n之值不同的成分之混合物，n=0之成分為30%以下15%以上，較好為20%以上，n=6以上之成分為30%以下，較好為10%以上。n=0成分大於30%時，使用使多價羥基樹脂環氧化所得之環氧樹脂而硬化之硬化物中，產生玻璃轉移點(Tg)降低或熱分解安定性降低，小於15%時，使多價羥基樹脂環氧化所得之環氧樹脂熔融黏度變高。另一方面，n=6以上之成分大於30%時，使多價羥基樹脂環氧化所得之環氧樹脂之製造階段中由於大量生成凝膠化物，故有樹脂收率降低之傾向，進而所得之環氧樹脂之高分子量體成分增加，故會使環氧樹脂之熔融黏度變高。n為0~20之數，但較好平均值(數平均)為1.0~5.0。又，本發明之多價羥基樹脂雖主成分為式(3)表示之樹脂，但亦可作為反應上不可避免生成之副成分微量存在多分支之多價羥基樹脂或於末端具有氯或羥基者。 The polyvalent hydroxy resin of the present invention is a mixture of components having different values of the repeating unit n represented by the general formula (3). The component of n = 0 is 30% or less and 15% or more, preferably 20% or more and n = 6 or more. The component is 30% or less, and preferably 10% or more. When the n = 0 component is greater than 30%, the hardened product using epoxy resin obtained by epoxidizing a polyvalent hydroxy resin is used to reduce the glass transition point (Tg) or the thermal decomposition stability. When it is less than 15%, The epoxy resin obtained by the epoxidation of the polyvalent hydroxyl resin has a higher melt viscosity. On the other hand, when the component with n = 6 or more is greater than 30%, the epoxy resin obtained by epoxidizing the polyvalent hydroxy resin has a large amount of gelation during the production stage, so the resin yield tends to decrease, and the obtained The high-molecular-weight body composition of the epoxy resin increases, so that the melt viscosity of the epoxy resin becomes high. n is a number from 0 to 20, but a preferable average value (number average) is 1.0 to 5.0. In addition, although the polyvalent hydroxy resin of the present invention is a resin represented by the formula (3) as a main component, it can also be used as a secondary component unavoidably formed in the reaction. The polyvalent hydroxy resin has a small amount of multi-branches or has chlorine or a hydroxyl group at the end .

且，本發明之多價羥基樹脂於樹脂中含有之總氯量為1000wtppm以下，較好為500ppm以下，更好為350ppm以下。總氯量多於其時，使用使本發明之多價羥基樹脂環氧化所得之環氧樹脂而硬化之硬化物中，無法期待萃取水氯離子之減低效果，且有使玻璃轉移點(Tg)降低或熱分解安定性降低之傾向。又，本發明中所謂總氯係表示樹脂中含有之氯分子之重量比例，係藉由以下方法測定。亦即，將試料1.0g溶解於丁基卡必醇25ml後，添加1N-KOH丙二醇溶液25ml，於230℃以上加熱回流10分鐘後，冷卻至室溫，進而添加80%丙酮水100ml，以0.002N-AgNO₃水溶液進行電位差滴定所得之值。 In addition, the total amount of chlorine contained in the resin of the polyvalent hydroxy resin of the present invention is 1000 wtppm or less, preferably 500 ppm or less, and more preferably 350 ppm or less. When the total amount of chlorine is more than that, the hardened product hardened by using the epoxy resin obtained by epoxidizing the polyvalent hydroxy resin of the present invention can not be expected to reduce the effect of extracting water chloride ions and has a glass transition point (Tg) The tendency to decrease or decrease the stability of thermal decomposition. In the present invention, the term "total chlorine" refers to the weight ratio of chlorine molecules contained in the resin, and is measured by the following method. That is, after dissolving 1.0 g of the sample in 25 ml of butyl carbitol, 25 ml of a 1N-KOH propylene glycol solution was added, and the mixture was heated to reflux at 230 ° C or higher for 10 minutes, and then cooled to room temperature, and then 100 ml of 80% acetone water was added. Potential difference titration of an N-AgNO ₃ aqueous solution.

本發明之多價羥基樹脂係藉由使4,4’-二羥基聯苯與芳香族交聯劑反應而得。作為芳香族交聯劑，基於4,4’-二羥基聯苯之反應性之觀點，4,4’-雙氯甲基聯苯為必須。但，亦可併用作為其他芳香族交聯劑之4,4’-雙羥基甲基聯苯、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，但其於交聯劑全體中之調配量為50wt%以下，較好為30wt%以下。 The polyvalent hydroxy resin of the present invention is obtained by reacting 4,4'-dihydroxybiphenyl with an aromatic crosslinking agent. As an aromatic crosslinking agent, 4,4'-dichloromethylbiphenyl is necessary from the viewpoint of the reactivity of 4,4'-dihydroxybiphenyl. However, 4,4'-bishydroxymethylbiphenyl, 4,4'-bisbromomethylbiphenyl, 4,4'-bismethoxymethylbiphenyl can be used together as other aromatic crosslinking agents. And 4,4'-diethoxymethyl biphenyl, but the blending amount thereof is 50 wt% or less, preferably 30 wt% or less, in the entire crosslinking agent.

作為二官能酚性化合物的4,4’-二羥基聯苯與作為芳香族交聯劑之4,4’-雙氯甲基聯苯之反應中，使用對於芳香族交聯劑過剩量之4,4’-二羥基聯苯。亦即，芳香族交聯劑之使用量對於4,4’-二羥基聯苯1莫耳為0.3~0.6莫耳，較好為0.4~0.5莫耳。芳香族交聯劑之使用量多於0.6莫耳時，所得之多價羥基樹脂中之高分子量體形成較多，故使該多價羥基樹脂環氧化所得之環氧樹脂之製造階段中由於大量生成凝膠化物，故有樹脂收率降低之傾向，進而所得之環氧樹脂之高分子量體成分增加，故會使環氧樹脂之熔融黏度變高。另一方面，芳香族交聯劑之使用量少於0.4莫耳時，由於n=0成分變多，故使用使該多價羥基樹脂環氧化所得之環氧樹脂之硬化物無法展現充分高的Tg性。 In the reaction of 4,4'-dihydroxybiphenyl as a bifunctional phenolic compound and 4,4'-bischloromethylbiphenyl as an aromatic cross-linking agent, 4 of the excess amount of the aromatic cross-linking agent is used. , 4'-dihydroxybiphenyl. That is, the used amount of the aromatic cross-linking agent is 0.3 to 0.6 mol, preferably 0.4 to 0.5 mol, with respect to 1,4'-dihydroxybiphenyl 1 mol. When the amount of the aromatic cross-linking agent is more than 0.6 mol, the high-molecular-weight body in the obtained polyvalent hydroxy resin is formed more, so the epoxy resin obtained by the epoxidation of the polyvalent hydroxy resin has a large amount in the manufacturing stage. The gelation product is formed, so the resin yield tends to decrease, and the high molecular weight body component of the obtained epoxy resin increases, so the melt viscosity of the epoxy resin becomes high. On the other hand, when the amount of the aromatic cross-linking agent is less than 0.4 mol, since the n = 0 component increases, the cured product of the epoxy resin obtained by epoxidizing the polyvalent hydroxy resin cannot exhibit sufficiently high Tg sex.

該反應首先在無觸媒、或在無機酸、有機酸等之酸觸媒存在下進行。有時產生氯甲基與OH基反應而生成醚鍵等之副反應，為了抑制其故在酸性條件進行。即使無觸媒，由於因氯甲基對芳香族環之置換反應而副生氯化氫而成為酸性條件，故酸觸媒並非必須，反而有汙染反應物之虞，但若存在酸觸媒則可自初期即產生期望之反應。作為此種酸觸媒舉例為例如鹽酸、硫酸、磷酸等之礦酸，或甲酸、草酸、三氟乙酸、對-甲苯磺酸等之有機酸，或氯化鋅、氯化鋁、氯化鐵、三氟化硼等之路易士酸，或活性白土、氧化矽-氧化鋁、沸石等之固體酸等。 This reaction is first performed in the absence of a catalyst or in the presence of an acid catalyst such as an inorganic acid, an organic acid, or the like. Sometimes chloromethyl reacts with OH groups and Side reactions such as the formation of ether bonds are carried out under acidic conditions in order to suppress them. Even if there is no catalyst, it is an acidic condition due to the by-produced hydrogen chloride by the substitution reaction of chloromethyl to the aromatic ring. Therefore, the acid catalyst is not necessary and may contaminate the reactants. The desired response is produced early. Examples of such acid catalysts include mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as formic acid, oxalic acid, trifluoroacetic acid, and p-toluenesulfonic acid; or zinc chloride, aluminum chloride, and ferric chloride. Lewis acid, such as boron trifluoride, or solid acid such as activated clay, silica-alumina, zeolite, etc.

該反應可在溫度10~250℃，較好100~180℃進行1~30小時，較好3~24小時。反應溫度為100℃以下時，4,4’-雙氯甲基聯苯與4,4’-二羥基聯苯之反應性缺乏而反應耗費時間，而且4,4’-二羥基聯苯析出，使4,4’-雙氯甲基聯苯與4,4’-二羥基聯苯之莫耳比偏離，會生成較多高分子量體。另一方面反應溫度為180℃以上時，有樹脂分解之虞。且，反應時間為3小時以下時，會殘存未反應之4,4’-雙氯甲基聯苯，反應時間為24小時以上時，生產性惡化。 The reaction can be carried out at a temperature of 10 to 250 ° C, preferably 100 to 180 ° C, for 1 to 30 hours, preferably 3 to 24 hours. When the reaction temperature is below 100 ° C, the reactivity of 4,4'-dichloromethylbiphenyl and 4,4'-dihydroxybiphenyl is lacking and the reaction takes time, and 4,4'-dihydroxybiphenyl is precipitated. Deviating the molar ratio of 4,4'-dichloromethylbiphenyl and 4,4'-dihydroxybiphenyl will cause more high molecular weight bodies. On the other hand, when the reaction temperature is 180 ° C or higher, the resin may be decomposed. When the reaction time is 3 hours or less, unreacted 4,4'-bischloromethylbiphenyl remains, and when the reaction time is 24 hours or more, productivity is deteriorated.

本反應中之固形分濃度宜使用溶劑而成為30~65%，較好成為45%~57%。固形分濃度稀於30%時，4,4’-雙氯甲基聯苯與4,4’-二羥基聯苯之反應性缺乏而使反應耗費時間，且由於易殘留未反應之4,4’-雙氯甲基聯苯，故有所得多價羥基樹脂之總氯量易變高之傾向。另一方面，濃於65%時，4,4’-二羥基聯苯大量析出，使4,4’-雙氯甲基聯苯與4,4’-二羥基聯苯之莫耳比大為偏離，故高分子量體之比例會增加。此處所謂固形分濃度係用以製造多價羥基樹脂所使用之全部原料中除了溶劑及觸媒以外之固形分的濃度。 The solid content concentration in this reaction should preferably be 30 to 65% using a solvent, and preferably 45% to 57%. When the solid content concentration is less than 30%, the lack of reactivity between 4,4'-dichloromethylbiphenyl and 4,4'-dihydroxybiphenyl makes the reaction time-consuming, and it is easy to leave unreacted 4,4 '-Dichloromethylbiphenyl, so the total chlorine content of polyvalent hydroxy resins tends to become high. On the other hand, when it is more than 65%, 4,4'-dihydroxybiphenyl precipitates in a large amount, so that the molar ratio of 4,4'-dichloromethylbiphenyl to 4,4'-dihydroxybiphenyl is large. Deviation The proportion of high molecular weight bodies will increase. The so-called solid content concentration refers to the concentration of the solid content of all the raw materials used to produce the polyvalent hydroxy resin except for the solvent and the catalyst.

作為本反應使用之溶劑宜為例如甲醇、乙醇、丙醇、丁醇、乙二醇、甲基溶纖素、乙基溶纖素、二乙二醇二甲醚、三乙二醇二甲醚(triglyme)等之醇類，或苯、甲苯、氯苯、二氯苯等之芳香族化合物，該等中特佳為乙基溶纖素、二乙二醇二甲醚、三乙二醇二甲醚。且，基於環氧化步驟中之生產性之觀點，特佳為二乙二醇二甲醚。反應結束後，所得之多價羥基樹脂亦可藉由減壓餾除、水洗或於弱溶劑中再沉澱等之方法而去除溶劑，但亦可殘留溶劑直接作為環氧化反應之原料。 The solvent used in this reaction is preferably, for example, methanol, ethanol, propanol, butanol, ethylene glycol, methylcellulysin, ethylcellolysin, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether. (triglyme) and other alcohols, or aromatic compounds such as benzene, toluene, chlorobenzene, dichlorobenzene, etc. Among these, ethylcellulysin, diethylene glycol dimethyl ether, and triethylene glycol di Methyl ether. Further, from the viewpoint of productivity in the epoxidation step, diethylene glycol dimethyl ether is particularly preferred. After the reaction, the obtained polyvalent hydroxy resin can also be removed by methods such as distillation under reduced pressure, washing with water, or reprecipitation in a weak solvent, but the residual solvent can also be used directly as a raw material for the epoxidation reaction.

其次，本發明於無觸媒或在酸觸媒存在下之反應結束後，亦可添加氫氧化鈉、氫氧化鉀等之鹼金屬氫氧化物進行反應。藉由該步驟，由於可使未反應氯甲基反應，故可大為減低多價羥基樹脂中之總氯量。且過量之鹼金屬氫氧化物亦可不去除，而直接利用作為多價羥基樹脂環氧化時之鹼觸媒。 Secondly, in the present invention, after the reaction is completed in the absence of a catalyst or in the presence of an acid catalyst, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide may be added for the reaction. With this step, since unreacted chloromethyl group can be reacted, the total amount of chlorine in the polyvalent hydroxy resin can be greatly reduced. Moreover, the excess alkali metal hydroxide can also be used as an alkali catalyst in the epoxidation of the polyvalent hydroxyl resin without removing it.

該反應中，反應溫度為10~200℃，較好為80~150℃，反應時間宜為1~10小時，較好為1~5小時。 In this reaction, the reaction temperature is 10 to 200 ° C, preferably 80 to 150 ° C, and the reaction time is preferably 1 to 10 hours, preferably 1 to 5 hours.

本發明之環氧樹脂可藉由上述多價羥基樹脂與表氯醇反應而製造。該反應可以與通常之環氧化反應同樣進行。舉例為例如將多價羥基樹脂溶解於過量之表氯醇後，在氫氧化鈉、氫氧化鉀等之鹼金屬氫氧化物存在下，於50~150℃，較好60~120℃反應1~10小時之方法。此時，鹼金屬氫氧化物之使用量對於多價羥基化合物中之羥基1莫耳為0.8~1.2莫耳，較好為0.9~1.1莫耳。且表氯醇雖對於多價羥基樹脂中之羥基過量使用，但通常對於多價羥基化合物中之羥基1莫耳為1.5~15莫耳，較好為2~8莫耳。反應結束後，餾除過量表氯醇，將殘留物溶解於甲苯、甲基異丁基酮等之溶劑，經過濾、水洗而去除無機鹽，接著餾除溶劑，而獲得環氧樹脂。 The epoxy resin of the present invention can be produced by reacting the above-mentioned polyvalent hydroxy resin with epichlorohydrin. This reaction can be carried out in the same manner as a usual epoxidation reaction. For example, after dissolving a polyvalent hydroxy resin in an excess of epichlorohydrin, in the presence of an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, etc., A method of reacting at 50 to 150 ° C, preferably 60 to 120 ° C for 1 to 10 hours. At this time, the amount of the alkali metal hydroxide used is 0.8 to 1.2 moles, preferably 0.9 to 1.1 moles, for 1 mole of the hydroxyl group in the polyvalent hydroxyl compound. In addition, although epichlorohydrin is used excessively for the hydroxyl groups in the polyvalent hydroxyl resin, it is generally 1.5 to 15 moles, preferably 2 to 8 moles, for the hydroxyl group of the polyvalent hydroxyl compound. After the reaction, the excess epichlorohydrin was distilled off, and the residue was dissolved in a solvent such as toluene and methyl isobutyl ketone. The inorganic salt was removed by filtration and washing, and then the solvent was distilled off to obtain an epoxy resin.

且，環氧化時，生成之環氧化合物之環氧基開環、縮合，少量副生寡聚合化之環氧化合物時，該環氧化合物即使存在亦無妨。 In addition, during the epoxidation, when the epoxy group of the produced epoxy compound is ring-opened and condensed, and a small amount of the by-product oligomerized epoxy compound is present, the epoxy compound may be present.

本發明之環氧樹脂之純度，尤其是總氯量，基於提高所應用之電子零件之性能之觀點，較少較好。尤其本發明中，使用由總氯量被減低之多價羥基樹脂衍生之環氧樹脂所得之硬化物中，可為高Tg，提高熱分解安定性、熱傳導性，並減低萃取氯離子。該環氧樹脂之總氯量之範圍較好為2000ppm以下，又更好為1500ppm以下，水解性氯之範圍較好為500ppm以下，更好為400ppm以下。 The purity of the epoxy resin of the present invention, especially the total chlorine content, is less and better from the viewpoint of improving the performance of the applied electronic parts. In particular, in the present invention, a hardened product obtained by using an epoxy resin derived from a polyvalent hydroxy resin having a reduced total chlorine content can have a high Tg, improve thermal decomposition stability, thermal conductivity, and reduce extraction of chloride ions. The range of the total chlorine content of the epoxy resin is preferably 2000 ppm or less, more preferably 1500 ppm or less, and the range of hydrolyzable chlorine is preferably 500 ppm or less, more preferably 400 ppm or less.

又，該環氧樹脂之熔融黏度，基於經混合處理之環氧樹脂組成物之均一性之觀點，於150℃下為0.55Pa．s以下，較好為0.40Pa．s以下，更好為0.3Pa．s以下。熔融黏度高於其時，混合處理後之環氧樹脂組成物產生不均一部分，而有硬化性或耐熱性等之物性降低之傾向。 The melt viscosity of the epoxy resin is 0.55 Pa at 150 ° C based on the homogeneity of the mixed epoxy resin composition. s or less, preferably 0.40Pa. s or less, more preferably 0.3Pa. s or less. When the melt viscosity is higher than that, an uneven portion of the epoxy resin composition is generated after the mixing process, and the physical properties such as hardenability and heat resistance are reduced. to.

本發明之環氧樹脂由於與軟化點同時亦顯示熔點，故為n數不同之成分的混合物，且為結晶性環氧樹脂。又，該環氧樹脂之軟化點或熔點，可藉由改變環氧樹脂原料的多價羥基樹脂合成時之聯酚類與交聯劑之莫耳比而容易地調整，但基於抑制環氧樹脂組成物之混合處理時之高熔點成分之溶解殘留所致之物性降低之觀點時，其軟化點或熔點較好為135℃以下，更好為130℃以下。軟化點或熔點高於其時，有硬化性或耐熱性等之物性降低之傾向。且，為了減低軟化點或熔點，必須使熔點高的n=0成分減少，但通常若以減少n=0成分之方式變更聯酚類與交聯劑之莫耳比，則由於分子量增加，而有軟化點或熔點增加之傾向。相對地，本發明之環氧樹脂由於n=0成分少，而且n=6以上之高分子量成分之含量低，故可抑制軟化點或黏度增加，而抑制自使用其之環氧樹脂組成物所得之硬化物之硬化性或耐熱性等之物性降低。亦即，本發明之多價羥基樹脂與表氯醇反應而得之環氧樹脂，於環氧化反應中，由於有樹脂中之羥基彼此鍵結之情況，故有高分子量體些許增加之傾向，但大致事先反映了作為原料的多價羥基樹脂之分子量分佈，而使n=0成分為35%以下，n=6以上之成分為30%以下。惟，原料的多價羥基樹脂之高分子量體過多時，因上述反應而高分子量化之樹脂成為凝膠化物而被去除至系統外，故高分子量體之峰值比例減少，成為n=0成分增加之傾向。又，環氧樹脂中，重複單位n亦為0~20之數，作為平均值(數平均)時亦為1.0~5.0左右。 Since the epoxy resin of the present invention exhibits a melting point at the same time as the softening point, it is a mixture of components having different n numbers and is a crystalline epoxy resin. In addition, the softening point or melting point of this epoxy resin can be easily adjusted by changing the molar ratio of biphenols and crosslinking agents during the synthesis of the polyvalent hydroxy resin of the epoxy resin raw material. From the viewpoint of lowering the physical properties of the high-melting point component due to the dissolution and remaining during the mixing treatment of the composition, the softening point or melting point is preferably 135 ° C or lower, more preferably 130 ° C or lower. When the softening point or melting point is higher than this, physical properties such as hardenability and heat resistance tend to decrease. In addition, in order to reduce the softening point or melting point, it is necessary to reduce the n = 0 component with a high melting point. However, if the mole ratio of biphenols and crosslinkers is generally changed to reduce the n = 0 component, the molecular weight increases, and The softening point or melting point tends to increase. In contrast, since the epoxy resin of the present invention has fewer components n = 0, and the content of high molecular weight components with n = 6 or higher is low, it can suppress an increase in softening point or viscosity, and can be obtained from the epoxy resin composition using the epoxy resin composition. Physical properties such as hardenability and heat resistance of the hardened material are reduced. That is, the epoxy resin obtained by reacting the polyvalent hydroxy resin of the present invention with epichlorohydrin has a tendency that the high molecular weight body increases slightly in the epoxidation reaction because the hydroxy groups in the resin are bonded to each other. However, the molecular weight distribution of the polyvalent hydroxy resin as a raw material is roughly reflected in advance, so that the n = 0 component is 35% or less, and the n = 6 component is 30% or less. However, when the polyvalent hydroxy resin of the raw material has too many high molecular weight bodies, the resin having a high molecular weight due to the above reaction becomes a gel and is removed outside the system, so the peak proportion of the high molecular weight body decreases, and the n = 0 component increases. The tendency. In epoxy resin, the repeating unit n is also It is a number from 0 to 20, and when it is an average value (number average), it is about 1.0 to 5.0.

本發明之環氧樹脂組成物係以上述本發明之環氧樹脂及硬化劑作為必須成分。有利地是以該等及無機填充材作為必須成分。 The epoxy resin composition of this invention contains the said epoxy resin and hardening | curing agent of this invention as an essential component. Advantageously, these and inorganic fillers are used as essential components.

作為本發明之環氧樹脂組成物中調配之硬化劑，於半導體密封材等之要求高電氣絕緣性之領域中，較好使用多價酚類作為硬化劑。以下，顯示硬化劑之具體例。 As the hardener formulated in the epoxy resin composition of the present invention, polyvalent phenols are preferably used as the hardener in fields requiring high electrical insulation properties such as semiconductor sealing materials. Specific examples of the hardener are shown below.

作為多價酚類舉例為例如雙酚A、雙酚F、雙酚S、茀雙酚、氫醌、間苯二酚、兒茶酚、聯酚類、萘二酚類等之2價酚類，進而為以參-(4-羥基苯基)甲烷、1,1,2,2-肆(4-羥基苯基)乙烷、酚酚醛清漆、鄰-甲酚酚醛清漆、萘酚酚醛清漆、二環戊二烯型酚樹脂、酚芳烷基樹脂等為代表之3價以上之酚類，進而為酚類、萘酚類或雙酚A、雙酚F、雙酚S、茀雙酚、4,4’-聯酚、2,2’-聯酚、氫醌、間苯二酚、兒茶酚、萘二酚類等之2價酚類與甲醛、乙醛、苯甲醛、對-羥基苯甲醛、對-二甲苯二醇、對-二甲苯二醇二甲醚、二乙烯基苯、二異丙烯基苯、二甲氧基甲基聯苯類、二乙烯基聯苯、二異丙烯基聯苯類等之交聯劑反應而合成之多價酚性化合物、由酚類與雙氯甲基聯苯等所得之聯苯芳烷基型酚樹脂、由萘酚類與對二甲苯二氯化物等合成之萘酚芳烷基樹脂類等。 Examples of the polyvalent phenols are divalent phenols such as bisphenol A, bisphenol F, bisphenol S, pyrene bisphenol, hydroquinone, resorcinol, catechol, biphenols, naphthalene diphenols, etc. And further to ginseng- (4-hydroxyphenyl) methane, 1,1,2,2- (4-hydroxyphenyl) ethane, phenol novolac, o-cresol novolac, naphthol novolac, Dicyclopentadiene-type phenol resins, phenol aralkyl resins, and the like are representative of trivalent or higher phenols, and further are phenols, naphthols or bisphenol A, bisphenol F, bisphenol S, bisphenol, Bivalent phenols such as 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcinol, catechol, naphthalene, and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxyl Benzaldehyde, p-xylene glycol, p-xylene glycol dimethyl ether, divinylbenzene, diisopropenylbenzene, dimethoxymethylbiphenyls, divinylbiphenyl, diisopropene Polyvalent phenolic compounds synthesized by the reaction of cross-linking agents such as biphenyls, biphenylaralkyl phenol resins obtained from phenols and bischloromethyl biphenyls, etc., from naphthols and p-xylylene Synthesized naphthol aralkyl resins such as chlorides.

且，亦可使用其他硬化劑成分，可使用例如二氰基二醯胺、酸酐類、芳香族及脂肪族胺類等。本發明之環氧樹脂組成物中，可使用該等硬化劑之1種或混合2種以上使用。 Moreover, other hardening | curing agent components can also be used, For example, a dicyandiamide, an acid anhydride, aromatic and aliphatic amine, etc. can be used. this invention In the epoxy resin composition, one type of these curing agents may be used, or two or more types may be used in combination.

硬化劑之調配量係考慮環氧樹脂中之環氧基與硬化劑之官能基(多價酚類時為羥基)之當量平衡而調配。環氧樹脂及硬化劑之當量比，對於環氧基1當量，硬化劑官能基通常為0.2至5.0之範圍，較好為0.5至2.0之範圍，更好為0.8~1.5之範圍。大於其或小於其，均會使環氧樹脂組成物之硬化性降低，且使硬化物之耐熱性、力學強度等降低。 The compounding amount of the hardener is prepared by considering the equivalent balance between the epoxy group in the epoxy resin and the functional group of the hardener (hydroxyl in the case of polyvalent phenols). The equivalent ratio of the epoxy resin and the hardener is generally in the range of 0.2 to 5.0, preferably in the range of 0.5 to 2.0, and more preferably in the range of 0.8 to 1.5. Larger or smaller than this will reduce the hardenability of the epoxy resin composition, and reduce the heat resistance and mechanical strength of the hardened material.

又，該環氧樹脂組成物中，作為環氧樹脂成分，亦可調配藉由使用本發明之多價羥基樹脂而獲得之環氧樹脂以外之他種環氧樹脂。作為該情況之他種環氧樹脂，所有於分子中具有2個以上環氧基之通常環氧樹脂均可使用。若舉例則有雙酚A、雙酚F、雙酚S、茀雙酚、4,4’-聯酚、3,3’,5,5’-四甲基-4,4’-二羥基聯苯、間苯二酚、萘二酚類等之2價酚類之環氧化物、參-(4-羥基苯基)甲烷、1,1,2,2-肆(4-羥基苯基)乙烷、酚酚醛清漆、鄰-甲酚酚醛清漆等為之3價以上之酚類之環氧化物、由二環戊二烯與酚類所得之共縮合樹脂之環氧化物、由甲酚類與甲醛與烷氧基取代之萘類所得之共縮合樹脂之環氧化物、由酚類與對二甲苯二氯化物等所得之酚芳烷基樹脂之環氧化物、由酚類與雙氯甲基聯苯等所得之聯苯芳烷基型酚樹脂之環氧化物、由萘酚類與對二甲苯二氯化物等合成之萘酚芳烷基樹脂類之環氧化物等。該等環氧樹脂可使用1種或混合2種以上使用。而且，環氧樹脂全體中之本發明之環氧樹脂的調配量，宜為5~100wt%，較好為60~100wt%之範圍，他種環氧樹脂之調配量較好為0~40wt%之範圍。 In this epoxy resin composition, as the epoxy resin component, other epoxy resins other than the epoxy resin obtained by using the polyvalent hydroxyl resin of the present invention may be blended. As other epoxy resins in this case, all ordinary epoxy resins having two or more epoxy groups in the molecule can be used. For example, there are bisphenol A, bisphenol F, bisphenol S, bisphenol, 4,4'-biphenol, 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxyl Epoxides of divalent phenols such as benzene, resorcinol, naphthol, etc., p- (4-hydroxyphenyl) methane, 1,1,2,2- (4-hydroxyphenyl) ethyl Alkanes, phenol novolacs, ortho-cresol novolacs are phenolic epoxides of trivalent or higher valence, epoxides of co-condensation resins obtained from dicyclopentadiene and phenols, and cresols from cresols and Epoxides of co-condensation resins obtained from formaldehyde and alkoxy-substituted naphthalenes, epoxides of phenol aralkyl resins obtained from phenols and p-xylene dichloride, etc., from phenols and dichloromethyl Epoxides of biphenylaralkyl phenol resins obtained from biphenyl and the like, naphthol aralkyl resins epoxides synthesized from naphthols and p-xylene dichloride and the like. These epoxy resins can be used in one kind or Use by mixing 2 or more types. In addition, the blending amount of the epoxy resin of the present invention in the whole epoxy resin is preferably in a range of 5 to 100 wt%, preferably 60 to 100 wt%, and the blending amount of other kinds of epoxy resins is preferably 0 to 40 wt%. Range.

進而，基於減低硬化物的應力之目的，環氧樹脂組成物中亦可含有交聯彈性體。調配交聯彈性體時，可使硬化物之熱衝擊測試中之封裝龜裂發生顯著減少。 Furthermore, for the purpose of reducing the stress of the cured product, a crosslinked elastomer may be contained in the epoxy resin composition. When the cross-linked elastomer is formulated, encapsulation cracking in the thermal shock test of the hardened material can be significantly reduced.

交聯彈性體之含量，對於環氧樹脂100重量份，宜為3~30重量份之範圍，較好為5~20重量份，更好為5~15重量份。少於其時，無法充分發揮硬化物之應力減低效果。且相反地大於其時，硬化物之Tg變低並且流動性降低而有成形加工性劣化之傾向。 The content of the crosslinked elastomer is preferably in the range of 3 to 30 parts by weight, preferably 5 to 20 parts by weight, and more preferably 5 to 15 parts by weight for 100 parts by weight of the epoxy resin. If less than that, the effect of reducing the stress of the hardened material cannot be fully exhibited. On the other hand, if it is larger than this, the Tg of the hardened material is lowered, and the fluidity is lowered, which tends to deteriorate the formability.

作為交聯彈性體，可使用習知者，但基於提高環氧樹脂之相溶性之觀點，較好使用苯乙烯系橡膠、丙烯酸系橡膠。 As the crosslinked elastomer, a known one can be used, but from the viewpoint of improving the compatibility of epoxy resins, styrene-based rubber and acrylic rubber are preferably used.

調配無機填充材作為必須成分時，作為無機填充材舉例為例如球狀或破碎狀熔融氧化矽、結晶氧化矽等之氧化矽粉末、氧化鋁粉末、玻璃粉末、或雲母、滑石、碳酸鈣、氧化鋁、水合氧化鋁等，使用於半導體封裝材時之較佳調配量，於組成物中為70重量%以上，更好為80重量%以上。無機填充材之形狀並未限制，可使用球狀、破碎狀、扁平狀、纖維狀等，其粒徑或長徑較好為1~1000μm之範圍。成為預浸片時之纖維狀基材之纖維長度較好為10mm以上，其中調配之無機填充材之量較好為10~70重量%之範圍。 When an inorganic filler is prepared as an essential component, examples of the inorganic filler include, for example, spherical or crushed fused silica, crystalline silica, and the like, alumina powder, glass powder, or mica, talc, calcium carbonate, and oxidized silica. Aluminum, hydrated alumina, and the like are preferably used in a semiconductor packaging material in an amount of 70% by weight or more, and more preferably 80% by weight or more. The shape of the inorganic filler is not limited, and a spherical shape, a crushed shape, a flat shape, a fibrous shape, and the like can be used, and the particle diameter or the long diameter is preferably in the range of 1 to 1000 μm. The fiber length of the fibrous substrate when it becomes a prepreg is preferably 10 mm or more, and the amount of the inorganic filler to be blended is preferably in the range of 10 to 70% by weight.

本發明之環氧樹脂組成物中，除上述必須成分以外，可添加其他添加劑。 The epoxy resin composition of the present invention may contain other additives in addition to the above-mentioned essential components.

本發明之環氧樹脂組成物中，亦可適當調配聚酯、聚醯胺、聚醯亞胺、聚醚、聚胺基甲酸酯、石油樹脂、茚樹脂、茚．香豆酮樹脂、苯氧樹脂等之寡聚物或高分子化合物作為其他改質劑等。添加量通常對於環氧樹脂100重量份，為2~30重量份之範圍。 In the epoxy resin composition of the present invention, polyester, polyamidoamine, polyamidoimide, polyether, polyurethane, petroleum resin, indene resin, and indene can also be appropriately blended. Oligomers or polymer compounds such as coumarone resin and phenoxy resin are used as other modifiers. The added amount is usually in the range of 2 to 30 parts by weight based on 100 parts by weight of the epoxy resin.

又，本發明之環氧樹脂組成物中，可調配顏料、難燃劑、搖變性賦予劑、偶合劑、流動性提高劑等之添加劑。 In the epoxy resin composition of the present invention, additives such as a pigment, a flame retardant, a shake modifier, a coupling agent, and a fluidity improver may be blended.

作為顏料有有機系或無機系之體質顏料、鱗片狀顏料等。作為搖變性賦予劑，可舉例矽系、蓖麻油系、脂肪族醯胺蠟、氧化聚乙烯蠟、有機膨潤土系等。 Examples of the pigment include organic or inorganic extender pigments and scaly pigments. Examples of shake modifiers include silicon-based, castor oil-based, aliphatic ammonium wax, oxidized polyethylene wax, and organic bentonite-based.

本發明之環氧樹脂組成物中，可根據需要使用硬化促進劑。若舉例則有胺類、咪唑類、有機膦類、路易士酸類，具體而言，有1,8-二氮雜雙環(5,4,0)十一碳烯-7、三伸乙二胺、苄基二甲基胺、三乙醇胺、二甲胺基乙醇、參(二甲胺基甲基)乙醇等之三級胺、2-甲基咪唑、2-苯基咪唑、2-乙基-4-甲基咪唑、2-苯基-4-甲基咪唑、2-十五烷基咪唑等之咪唑類、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、四苯基鏻．四苯基硼酸鹽、四苯基鏻．乙基三苯基硼酸鹽、四丁基鏻．四丁基硼酸鹽等之四取代鏻．四取代硼酸鹽、2-乙基-4-甲基咪唑．四苯基硼酸鹽、N-甲基嗎啉．四苯基硼酸鹽等之四苯基硼酸鹽等。作為添加量通常對於環氧樹脂100重量份為0.2~5重量份之範圍。 A hardening accelerator can be used in the epoxy resin composition of this invention as needed. Examples include amines, imidazoles, organic phosphines, and Lewis acids. Specifically, there are 1,8-diazabicyclo (5,4,0) undecene-7, and triethylenediamine. Tertiary amines such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, gins (dimethylaminomethyl) ethanol, 2-methylimidazole, 2-phenylimidazole, 2-ethyl- Imidazoles such as 4-methylimidazole, 2-phenyl-4-methylimidazole, 2-pentadecylimidazole, tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine , Organic phosphines such as phenylphosphine, tetraphenylphosphonium. Tetraphenylborate, tetraphenylphosphonium. Ethyltriphenylborate, tetrabutylphosphonium. Tetrabutyl borate and other tetra-substituted hydrazones. Tetra-substituted borate, 2-ethyl-4-methylimidazole. Tetraphenylborate, N-methylmorpholine. Tetraphenylborate Phenylborate, etc. The addition amount is usually in the range of 0.2 to 5 parts by weight based on 100 parts by weight of the epoxy resin.

進而根據需要，於本發明之樹脂組成物中，可使用巴西棕櫚蠟、OP蠟等之脫模劑，γ-縮水甘油氧基丙基三甲氧基矽烷等之偶合劑，碳黑等之著色劑，三氧化銻等之難燃劑，硬脂酸鈣等之滑劑等。 Further, according to need, in the resin composition of the present invention, a release agent such as carnauba wax, OP wax, a coupling agent such as γ-glycidoxypropyltrimethoxysilane, and a coloring agent such as carbon black can be used , Flame retardants such as antimony trioxide, lubricants such as calcium stearate.

本發明之環氧樹脂組成物可作為一部分或全部溶解於有機溶劑之清漆狀態(稱為清漆)有利地使用。含有無機填充材等之溶劑不溶分時，並無必要使其溶解，可設為懸浮狀態，期望儘可能為均一溶液。樹脂組成物中之環氧樹脂期望全部溶解，但由本發明之製法所得之環氧樹脂之溶解性優異，於保存狀態下，不易析出固形分。清漆中之環氧樹脂之一部分成為固形物而分離時，成為其硬化物特性差者。 The epoxy resin composition of the present invention can be advantageously used as a varnish state (referred to as a varnish) partially or entirely dissolved in an organic solvent. When a solvent containing an inorganic filler or the like does not dissolve, it is not necessary to dissolve it, and it may be suspended, and it is desirable to be a uniform solution as much as possible. The epoxy resin in the resin composition is expected to be completely dissolved, but the epoxy resin obtained by the production method of the present invention is excellent in solubility, and it is difficult to precipitate a solid content in a stored state. When a part of the epoxy resin in the varnish becomes a solid and separates, it becomes a person with poor hardened properties.

本發明之環氧樹脂組成物有利地是作成使樹脂分溶解於溶劑之狀態的組成物(清漆)後，含浸於玻璃布、芳醯胺不織布、液晶聚合物系之聚酯不織布等之纖維狀的基材後，進行去除溶劑，可成為使環氧樹脂組成物與纖維狀基材複合化之預浸片。且，依據情況可藉由將上述清漆塗佈於銅箔、不鏽鋼箔、聚醯亞胺薄膜、聚酯薄膜等之薄片狀物上作成層合物。又，可藉由層合複數片上述預浸片，亦可藉由層合預浸片與上述薄片狀物，而成為層合物。 The epoxy resin composition of the present invention is advantageously formed into a fiber-like composition (varnish) in which a resin component is dissolved in a solvent, and is impregnated with glass cloth, aramid nonwoven fabric, and a liquid crystal polymer polyester nonwoven fabric. After the substrate is removed, the solvent can be removed to form a prepreg that composites the epoxy resin composition with the fibrous substrate. In addition, depending on the situation, the varnish can be applied to a sheet of copper foil, stainless steel foil, polyimide film, polyester film, or the like to form a laminate. In addition, a plurality of the prepregs may be laminated, or a laminate may be formed by laminating the prepregs and the sheet-like material.

本發明之環氧樹脂組成物若加熱硬化，則可成為環氧樹脂硬化物，該硬化物成為低吸濕性、高耐熱性、密著性、難燃性等方面優異者。該硬化物可藉由注模、壓縮成形、轉模成形等之方法將環氧樹脂組成物成形加工而獲得。此時之溫度通常為120~220℃之範圍。 The epoxy resin composition of the present invention can be cured by heating. It becomes an epoxy resin hardened | cured material which is excellent in low hygroscopicity, high heat resistance, adhesiveness, flame retardance, etc. The cured product can be obtained by molding and processing the epoxy resin composition by methods such as injection molding, compression molding, and rotary molding. The temperature at this time is usually in the range of 120 to 220 ° C.

[實施例] [Example]

多價羥基樹脂、環氧樹脂、環氧樹脂組成物及硬化物之試驗條件如下所示。 The test conditions for the polyvalent hydroxy resin, epoxy resin, epoxy resin composition, and cured product are shown below.

1)羥基(OH)當量 1) Hydroxyl (OH) equivalent

使用電位差滴定裝置，使用1,4-二噁烷為溶劑，以1.5mol/L乙醯氯進行乙醯化，以水使過量之乙醯氯分解，並使用0.5mol/L-氫氧化鉀滴定。 Use a potentiometric titration device, use 1,4-dioxane as a solvent, perform acetylation with 1.5 mol / L acetam chloride, decompose excess acetam chloride with water, and titrate with 0.5 mol / L-potassium hydroxide .

2)環氧當量 2) epoxy equivalent

使用電位差滴定裝置，使用氯仿作為溶劑，添加溴化四乙銨乙酸溶液，以電位差滴定裝置使用0.1mol/L過氯酸-乙酸溶液進行測定。 A potentiometric titration device was used, chloroform was used as a solvent, a tetraethylammonium bromide acetic acid solution was added, and a potentiometric titration device was used for measurement using a 0.1 mol / L perchloric acid-acetic acid solution.

3)軟化點 3) Softening point

使用自動軟化點裝置(明峰公司製，ASP-M4SP)，依據JIS-K-2207以環球法測定。 Using an automatic softening point device (manufactured by Mingfeng Co., Ltd., ASP-M4SP), it was measured by the ring and ball method in accordance with JIS-K-2207.

3)熔點 3) melting point

使用示差掃描熱量分析裝置(SII Nanotechnology股份有限公司製DSC7000X)，以升溫速度5℃/分鐘測定而得之峰值溫度作為熔點。 Using a differential scanning calorimeter (SII Nanotechnology) Co., Ltd. DSC7000X), the melting point is the peak temperature measured at a heating rate of 5 ° C / min.

4)熔融黏度 4) Melt viscosity

使用BROOKFIELD製，CAP2000H型旋轉黏度計，於150℃測定。 It was measured at 150 ° C using a CAP2000H rotary viscometer manufactured by BROOKFIELD.

5)總氯 5) total chlorine

將試料1.0g溶解於丁基卡必醇25ml後，添加1N-KOH丙二醇溶液25ml，於230℃以上加熱回流10分鐘後，冷卻至室溫，進而添加80%丙酮水100ml，以0.002N-AgNO₃水溶液進行電位差滴定而測定。 After dissolving 1.0 g of the sample in 25 ml of butyl carbitol, 25 ml of a 1N-KOH propylene glycol solution was added, and the mixture was heated and refluxed at 230 ° C or higher for 10 minutes, and then cooled to room temperature. Then, 100 ml of 80% acetone water was added, and ₃ aqueous solutions were measured by potentiometric titration.

6)水解性氯 6) Hydrolyzable chlorine

將試料0.5g溶解於二噁烷30ml後，添加1N-KOH甲醇溶液5ml，於100℃煮沸回流30分鐘後，冷卻至室溫，進而添加80%丙酮水100ml，以0.002N-AgNO₃水溶液進行電位差滴定而測定。 After 0.5g sample was dissolved in dioxane 30ml, 5ml of methanol was added 1N-KOH solution was boiled under reflux at 100 deg.] C for 30 minutes and cooled to room temperature, further added 80% aqueous acetone 100ml, carried out in aqueous 0.002N-AgNO ₃ Potential difference was measured by titration.

7)玻璃轉移點(Tg) 7) Glass transition point (Tg)

利用熱機械測定裝置(SII Nanotechnology股份有限公司製EXSTAR6000TMA)，以升溫速度10℃/分鐘之條件求出Tg。 Using a thermomechanical measuring device (EXSTAR6000TMA manufactured by SII Nanotechnology Co., Ltd.), Tg was determined under the condition that the temperature was increased at a rate of 10 ° C / min.

8)萃取氯離子 8) Extraction of chloride ions

於耐壓容器中秤量環氧樹脂硬化物2g與離子交換純水50g後，進行加熱萃取，使用離子層析儀，求出萃取水中之氯離子濃度，算出環氧樹脂硬化物之萃取氯離子濃度。 Weigh 2 g of epoxy resin hardened product and 50 g of ion-exchanged pure water in a pressure-resistant container, and then perform heating extraction. Use an ion chromatograph to determine the chloride ion concentration in the extracted water and calculate the extracted chloride ion concentration of the epoxy resin hardened product .

9)樹脂之分子量分佈 9) Molecular weight distribution of resin

使用GPC測定裝置(TOSOH製，HLC-8220 GPC)，管柱使用TSK防護管柱一根(TOSOH製)、TSKgel 2000H XL(TOSOH製)1根、TSKgel 3000H XL(TOSOH製)1根、TSKgel 4000H XL(TOSOH製)1根，檢測器為RI，溶劑為四氫呋喃，流量1.0ml/min，管柱溫度40℃，進行測定。 Using a GPC measuring device (manufactured by TOSOH, HLC-8220 GPC), a TSK protective column (manufactured by TOSOH), one TSKgel 2000H XL (manufactured by TOSOH), one TSKgel 3000H XL (manufactured by TOSOH), and TSKgel 4000H One XL (manufactured by TOSOH) was used. The detector was RI, the solvent was tetrahydrofuran, the flow rate was 1.0 ml / min, and the column temperature was 40 ° C. for measurement.

以下基於實施例及比較例，具體說明本發明。 Hereinafter, the present invention will be specifically described based on examples and comparative examples.

實施例1 Example 1

於1000ml之4頸燒瓶中，饋入4,4’-二羥基聯苯77.5g(0.4莫耳)、二乙二醇二甲醚119.3g、4,4’-雙氯甲基聯苯41.8g(0.16莫耳)，於氮氣流下邊攪拌邊升溫至160℃反應20小時。接著，添加48%氫氧化鉀溶液2.8g，於130℃反應3小時。該反應中，反應莫耳比為0.40，固形分濃度為50%。 In a 1000 ml 4-necked flask, 77.5 g (0.4 mole) of 4,4'-dihydroxybiphenyl, 119.3 g of diethylene glycol dimethyl ether, and 41.8 g of 4,4'-dichloromethyl biphenyl were fed. (0.16 moles), and the temperature was raised to 160 ° C. with stirring under a nitrogen flow for 20 hours to react. Next, 2.8 g of a 48% potassium hydroxide solution was added and reacted at 130 ° C for 3 hours. In this reaction, the molar ratio of the reaction was 0.40, and the solid content concentration was 50%.

反應後，滴下於大量純水中藉由再沉澱而回收，獲得淺黃色樹脂104g。所得樹脂之OH當量129g/eq。所得樹脂藉由GPC測定求得之通式(1)中n=0成分為28.9%，n=6以上之成分為14.1%。且，總氯為220ppm。 After the reaction, it was dropped into a large amount of pure water and recovered by reprecipitation to obtain 104g of light yellow resin. The OH equivalent of the obtained resin was 129 g / eq. In the obtained resin, the n = 0 component in the general formula (1) determined by GPC measurement was 28.9%, and the n = 6 or more component was 14.1%. The total chlorine was 220 ppm.

實施例2 Example 2

於實施例1所得之樹脂104g中饋入表氯醇449g並溶解。接著，減壓下於65℃以3小時滴下49%氫氧化鈉水溶液65.8g。該滴下中以分離槽分離回流餾出之水與表氯醇，使表氯醇返回反應容器中，將水排出系統外而反應。反應結束後，餾除表氯醇，溶解於甲苯中。隨後，藉由水洗去除鹽，餾除甲苯，獲得環氧樹脂143g(環氧樹脂A)。所得樹脂之環氧當量為197g/eq，軟化點為126℃，於150℃之熔融黏度為0.27Pa．s，總氯為1020ppm，水解性氯為270ppm。 To 104 g of the resin obtained in Example 1, 449 g of epichlorohydrin was fed and dissolved. Next, 65.8 g of a 49% sodium hydroxide aqueous solution was dropped at 65 ° C. for 3 hours under reduced pressure. In this dropping, the water and epichlorohydrin distilled off under reflux are separated in a separation tank, the epichlorohydrin is returned to the reaction container, and the water is discharged out of the system to react. After the reaction was completed, epichlorohydrin was distilled off and dissolved in toluene. Subsequently, the salt was removed by washing with water, and toluene was distilled off to obtain 143 g of epoxy resin (epoxy resin A). The epoxy equivalent of the obtained resin was 197 g / eq, the softening point was 126 ° C, and the melt viscosity at 150 ° C was 0.27Pa. s, total chlorine was 1020 ppm, and hydrolyzable chlorine was 270 ppm.

實施例3 Example 3

於1000ml之4頸燒瓶中，饋入4,4’-二羥基聯苯77.5g(0.4莫耳)、二乙二醇二甲醚129.8g、4,4’-雙氯甲基聯苯52.3g(0.2莫耳)，於氮氣流下邊攪拌邊升溫至160℃反應20小時。接著，添加48%氫氧化鉀溶液2.8g，於130℃反應3小時。該反應中，反應莫耳比為0.50，固形分濃度為50%。 In a 1000 ml 4-necked flask, 77.5 g (0.4 mole) of 4,4'-dihydroxybiphenyl, 129.8 g of diethylene glycol dimethyl ether, and 52.3 g of 4,4'-dichloromethyl biphenyl were fed. (0.2 mol), and the temperature was raised to 160 ° C while stirring under a nitrogen flow, and the reaction was carried out for 20 hours. Next, 2.8 g of a 48% potassium hydroxide solution was added and reacted at 130 ° C for 3 hours. In this reaction, the molar ratio of the reaction was 0.50, and the solid content concentration was 50%.

反應後，滴下於大量純水中藉由再沉澱而回收，獲得淺黃色樹脂110g。所得樹脂之OH當量138g/eq。所得樹脂藉由GPC測定求得之通式(1)中n=0成分為21.4%，n=6以上之成分為25.6%。且，總氯為310ppm。 After the reaction, the solution was dropped into a large amount of pure water and recovered by reprecipitation to obtain 110 g of a pale yellow resin. The OH equivalent of the obtained resin was 138 g / eq. The resulting tree In the general formula (1) obtained by GPC measurement, the component of n = 0 is 21.4%, and the component of n = 6 or more is 25.6%. The total chlorine was 310 ppm.

實施例4 Example 4

於實施例3所得之樹脂110g中饋入表氯醇447g並溶解。接著，減壓下於65℃以3小時滴下49%氫氧化鈉水溶液65.5g。該滴下中以分離槽分離回流餾出之水與表氯醇，使表氯醇返回反應容器中，將水排出系統外而反應。反應結束後，餾除表氯醇，溶解於甲苯中。隨後，藉由水洗去除鹽，餾除甲苯，獲得環氧樹脂111g(環氧樹脂B)。所得樹脂之環氧當量為208g/eq，軟化點為117℃，於150℃之熔融黏度為0.33Pa．s，總氯為1240ppm，水解性氯為260ppm。 To 110 g of the resin obtained in Example 3, 447 g of epichlorohydrin was fed and dissolved. Next, 65.5 g of a 49% sodium hydroxide aqueous solution was dropped under reduced pressure at 65 ° C. for 3 hours. In this dropping, the water and epichlorohydrin distilled off under reflux are separated in a separation tank, the epichlorohydrin is returned to the reaction container, and the water is discharged out of the system to react. After the reaction was completed, epichlorohydrin was distilled off and dissolved in toluene. Subsequently, the salt was removed by washing with water, and toluene was distilled off to obtain 111 g of epoxy resin (epoxy resin B). The epoxy equivalent of the obtained resin was 208 g / eq, the softening point was 117 ° C, and the melt viscosity at 150 ° C was 0.33Pa. s, total chlorine was 1240 ppm, and hydrolyzable chlorine was 260 ppm.

實施例5 Example 5

於1000ml之4頸燒瓶中，饋入4,4’-二羥基聯苯77.5g(0.4莫耳)、二乙二醇二甲醚90.0g、4,4’-雙氯甲基聯苯41.8g(0.16莫耳)，於氮氣流下邊攪拌邊升溫至160℃反應20小時。接著，添加48%氫氧化鉀溶液2.8g，於130℃反應3小時。該反應中，反應莫耳比為0.40，固形分濃度為57%。 In a 1000 ml 4-necked flask, 77.5 g (0.4 mole) of 4,4'-dihydroxybiphenyl, 90.0 g of diethylene glycol dimethyl ether, and 41.8 g of 4,4'-dichloromethyl biphenyl were fed. (0.16 moles), and the temperature was raised to 160 ° C. with stirring under a nitrogen flow for 20 hours to react. Next, 2.8 g of a 48% potassium hydroxide solution was added and reacted at 130 ° C for 3 hours. In this reaction, the molar ratio of the reaction was 0.40, and the solid content concentration was 57%.

反應後，滴下於大量純水中藉由再沉澱而回收，獲得淺黃色樹脂104g。所得樹脂之OH當量129g/eq。所得樹脂藉由GPC測定求得之通式(1)中n=0成分為29.9%，n=6 以上之成分為22.2%。且，總氯為150ppm。 After the reaction, the solution was dropped into a large amount of pure water and recovered by reprecipitation to obtain 104 g of a pale yellow resin. The OH equivalent of the obtained resin was 129 g / eq. In the obtained resin, the n = 0 component in the general formula (1) obtained by GPC measurement was 29.9%, and n = 6 The above composition is 22.2%. The total chlorine was 150 ppm.

實施例6 Example 6

於實施例5所得之樹脂104g中饋入表氯醇449g並溶解。接著，減壓下於65℃以3小時滴下49%氫氧化鈉水溶液65.8g。該滴下中以分離槽分離回流餾出之水與表氯醇，使表氯醇返回反應容器中，將水排出系統外而反應。反應結束後，餾除表氯醇，溶解於甲苯中。隨後，藉由水洗去除鹽，餾除甲苯，獲得環氧樹脂110g(環氧樹脂C)。所得樹脂之環氧當量為196g/eq，軟化點為131℃，於150℃之熔融黏度為0.13Pa．s，總氯為1110ppm，水解性氯為290ppm。 To 104 g of the resin obtained in Example 5, 449 g of epichlorohydrin was fed and dissolved. Next, 65.8 g of a 49% sodium hydroxide aqueous solution was dropped at 65 ° C. for 3 hours under reduced pressure. In this dropping, the water and epichlorohydrin distilled off under reflux are separated in a separation tank, the epichlorohydrin is returned to the reaction container, and the water is discharged out of the system to react. After the reaction was completed, epichlorohydrin was distilled off and dissolved in toluene. Subsequently, the salt was removed by washing with water, and toluene was distilled off to obtain 110 g of epoxy resin (epoxy resin C). The epoxy equivalent of the obtained resin was 196 g / eq, the softening point was 131 ° C, and the melt viscosity at 150 ° C was 0.13Pa. s, total chlorine was 1110 ppm, and hydrolyzable chlorine was 290 ppm.

比較例1 Comparative Example 1

於1000ml之4頸燒瓶中，饋入4,4’-二羥基聯苯77.5g(0.4莫耳)、二乙二醇二甲醚97.9g、4,4’-雙氯甲基聯苯52.3g(0.2莫耳)，於氮氣流下邊攪拌邊升溫至160℃反應10小時。隨後未添加氫氧化鉀溶液。該反應中，反應莫耳比為0.50，固形分濃度為57%。 In a 1000 ml 4-necked flask, 77.5 g (0.4 mole) of 4,4'-dihydroxybiphenyl, 97.9 g of diethylene glycol dimethyl ether, and 52.3 g of 4,4'-dichloromethyl biphenyl were fed. (0.2 mol), and the temperature was raised to 160 ° C while stirring under a nitrogen flow for 10 hours. No potassium hydroxide solution was subsequently added. In this reaction, the molar ratio of the reaction was 0.50, and the solid content concentration was 57%.

反應後，滴下於大量純水中藉由再沉澱而回收，獲得淺黃色樹脂110g。所得樹脂之OH當量138g/eq。所得樹脂藉由GPC測定求得之通式(1)中n=0成分為21.7%，n=6以上之成分為35.0%。且，總氯為3000ppm。 After the reaction, the solution was dropped into a large amount of pure water and recovered by reprecipitation to obtain 110 g of a pale yellow resin. The OH equivalent of the obtained resin was 138 g / eq. In the obtained resin, the n = 0 component in the general formula (1) determined by GPC measurement was 21.7%, and the n = 6 or more component was 35.0%. The total chlorine was 3000 ppm.

比較例2 Comparative Example 2

於比較例1所得之樹脂110g中饋入表氯醇447g並溶解。接著，減壓下於65℃以3小時滴下49%氫氧化鈉水溶液65.5g。該滴下中以分離槽分離回流餾出之水與表氯醇，使表氯醇返回反應容器中，將水排出系統外而反應。反應結束後，餾除表氯醇，溶解於甲苯中。隨後，藉由水洗去除鹽，餾除甲苯，獲得環氧樹脂95g(環氧樹脂D)。所得樹脂之環氧當量為198g/eq，軟化點為125℃，於150℃之熔融黏度為0.71Pa．s，總氯為2180ppm，水解性氯為790ppm。 To 110 g of the resin obtained in Comparative Example 1, 447 g of epichlorohydrin was fed and dissolved. Next, 65.5 g of a 49% sodium hydroxide aqueous solution was dropped under reduced pressure at 65 ° C. for 3 hours. In this dropping, the water and epichlorohydrin distilled off under reflux are separated in a separation tank, the epichlorohydrin is returned to the reaction container, and the water is discharged out of the system to react. After the reaction was completed, epichlorohydrin was distilled off and dissolved in toluene. Subsequently, the salt was removed by washing with water, and toluene was distilled off to obtain 95 g of an epoxy resin (epoxy resin D). The epoxy equivalent of the obtained resin was 198 g / eq, the softening point was 125 ° C, and the melt viscosity at 150 ° C was 0.71 Pa. s, total chlorine was 2180 ppm, and hydrolyzable chlorine was 790 ppm.

比較例3 Comparative Example 3

於2000ml之4頸燒瓶中，饋入4,4’-二羥基聯苯186.0g(1.0莫耳)、二乙二醇二甲醚860g、4,4’-雙氯甲基聯苯75.3g(0.3莫耳)，於氮氣流下邊攪拌邊升溫至160℃反應10小時。隨後未添加氫氧化鉀溶液。該反應中，反應莫耳比為0.30，固形分濃度為23%。 In a 2000 ml 4-necked flask, 186.0 g (1.0 mol) of 4,4'-dihydroxybiphenyl, 860 g of diethylene glycol dimethyl ether, and 75.3 g of 4,4'-dichloromethyl biphenyl were fed ( 0.3 mol), and heated to 160 ° C. with stirring under a nitrogen flow for 10 hours. No potassium hydroxide solution was subsequently added. In this reaction, the molar ratio of the reaction was 0.30, and the solid content concentration was 23%.

反應後，滴下於大量純水中藉由再沉澱而回收，獲得淺黃色樹脂220g。所得樹脂之OH當量131g/eq。所得樹脂藉由GPC測定求得之通式(1)中n=0成分為39.3%，n=6以上之成分為7.6%。且，總氯為6080ppm。 After the reaction, it was dropped into a large amount of pure water and recovered by reprecipitation to obtain 220 g of a pale yellow resin. The OH equivalent of the obtained resin was 131 g / eq. In the obtained resin, the n = 0 component in the general formula (1) determined by GPC measurement was 39.3%, and the n = 6 or more component was 7.6%. The total chlorine was 6080 ppm.

比較例4 Comparative Example 4

於比較例3所得之樹脂120g中饋入表氯醇509g並溶解。接著，減壓下於65℃以4小時滴下49%氫氧化鈉水溶液76.5g。該滴下中以分離槽分離回流餾出之水與表氯醇，使表氯醇返回反應容器中，將水排出系統外而反應。反應結束後，餾除表氯醇，溶解於甲苯中。隨後，藉由水洗去除鹽，餾除甲苯，獲得環氧樹脂148g(環氧樹脂E)。所得樹脂之環氧當量為184g/eq，軟化點為139℃，於150℃之熔融黏度為0.05Pa．s，總氯為2960ppm，水解性氯為1400ppm。 To 120 g of the resin obtained in Comparative Example 3, 509 g of epichlorohydrin was fed and dissolved. solution. Next, 76.5 g of a 49% sodium hydroxide aqueous solution was dropped at 65 ° C. for 4 hours under reduced pressure. In this dropping, the water and epichlorohydrin distilled off under reflux are separated in a separation tank, the epichlorohydrin is returned to the reaction container, and the water is discharged out of the system to react. After the reaction was completed, epichlorohydrin was distilled off and dissolved in toluene. Subsequently, the salt was removed by washing with water, and toluene was distilled off to obtain 148 g of an epoxy resin (epoxy resin E). The epoxy equivalent of the obtained resin was 184 g / eq, the softening point was 139 ° C, and the melt viscosity at 150 ° C was 0.05 Pa. s, total chlorine was 2960 ppm, and hydrolyzable chlorine was 1400 ppm.

實施例1、3、5所得之多價羥基樹脂及比較例1所得之多價羥基樹脂之樹脂特性示於表1。 Table 1 shows the resin characteristics of the polyvalent hydroxy resin obtained in Examples 1, 3, and 5 and the polyvalent hydroxy resin obtained in Comparative Example 1.

實施例2、4、6所得之環氧樹脂A~C及比較例2所得之環氧樹脂D之樹脂特性示於表2。 The resin characteristics of the epoxy resins A to C obtained in Examples 2, 4, and 6 and the epoxy resin D obtained in Comparative Example 2 are shown in Table 2.

實施例7~9 Examples 7 to 9

將上述實施例2、4、6所得之環氧樹脂A~C、硬化劑及硬化促進劑以表3所示之調配比例混練，調製環氧樹脂組成物。表中之數值表示調配中之重量份。 The epoxy resins A to C, the hardener, and the hardening accelerator obtained in the above Examples 2, 4, and 6 were kneaded at the mixing ratio shown in Table 3 to prepare an epoxy resin composition. The numerical values in the table represent parts by weight in the formulation.

比較例5、6 Comparative Examples 5, 6

將上述比較例2、4所得之環氧樹脂D、硬化劑及硬化促進劑以表3所示之調配比例混練，調製環氧樹脂組成物。表中之數值表示調配中之重量份。 The epoxy resin D, the hardener, and the hardening accelerator obtained in the above Comparative Examples 2 and 4 were kneaded at the mixing ratio shown in Table 3 to prepare an epoxy resin composition. The numerical values in the table represent parts by weight in the formulation.

其他使用之成分示於以下。 The other components used are shown below.

．硬化劑：三酚甲烷型多價羥基樹脂(TPM-100(群榮化學工業股份有限公司製)，OH當量97.5g/eq，軟化點105℃) ． Hardener: Triphenol methane type multivalent hydroxyl resin (TPM-100 (Qunrong (Made by Chemical Industry Co., Ltd.), OH equivalent 97.5g / eq, softening point 105 ° C)

．硬化促進劑：2-苯基-4,5-二羥基甲基咪唑(製品名：2PHZ-PW，四國化成股份有限公司製) ． Hardening accelerator: 2-phenyl-4,5-dihydroxymethylimidazole (product name: 2PHZ-PW, manufactured by Shikoku Chemical Co., Ltd.)

使用該等環氧樹脂組成物於175℃進行成形，進而於200℃進行後烘烤5小時，獲得硬化物試驗片後，供於物性測定。結果示於表3。 These epoxy resin compositions were molded at 175 ° C, and then post-baked at 200 ° C for 5 hours to obtain a hardened test piece, which was then used for physical property measurement. The results are shown in Table 3.

[產業上之可利用性] [Industrial availability]

依據本發明，可效率良好地製造低黏度且低氯性優異之環氧樹脂，因此藉由使調配該環氧樹脂之環氧樹脂組成物加熱硬化，可獲得具有高Tg性，且萃取水氯離子之減低效果及成形作業性優異之硬化物，而可較好地使用於電氣．電子零件類之密封材料、高放熱薄片、高放熱基板等之電路基板材料等之用途。尤其作為要求性能近幾年逐年高度化之功率裝置用密封材料而有用。 According to the present invention, an epoxy resin having low viscosity and excellent chlorine resistance can be efficiently manufactured. Therefore, by heating and curing the epoxy resin composition prepared by the epoxy resin, high Tg properties can be obtained and water chloride can be extracted. It is a hardened product with excellent ion reduction effect and molding workability, and can be used in electrical applications. It is used for sealing materials of electronic parts, high exothermic flakes, circuit substrate materials such as high exothermic substrates, etc. In particular, it is useful as a sealing material for power devices that has been required to be improved in performance in recent years.

Claims

一種多價羥基樹脂，其特徵係使以式(1)表示之4,4’-二羥基聯苯與以式(2)表示之作為芳香族交聯劑之4,4’-雙氯甲基聯苯反應而得之以通式(3)表示之多價羥基樹脂，且以凝膠滲透層析法測定之面積%計，n=0成分為30%以下15%以上，n=6以上之高分子量成分為30%以下，且總氯量為1000wtppm以下，

其中，n表示0~20之數。 A polyvalent hydroxy resin characterized by using 4,4'-dihydroxybiphenyl represented by formula (1) and 4,4'-dichloromethyl represented by formula (2) as an aromatic crosslinking agent The polyvalent hydroxyl resin represented by the general formula (3) is obtained by biphenyl reaction, and the area% determined by gel permeation chromatography method, n = 0 component is 30% or less and 15% or more, and n = 6 or more The high molecular weight component is 30% or less, and the total chlorine content is 1000wtppm or less.

Among them, n represents a number from 0 to 20.

一種如請求項1之多價羥基樹脂之製造方法，其特徵係對於4,4’-二羥基聯苯(1)1莫耳，使用芳香族交聯劑(2)0.3~0.6莫耳，以使固形分濃度成為30~65wt%之方式使用溶劑進行反應。 A method for producing a polyvalent hydroxy resin as claimed in claim 1, characterized in that for 4,4'-dihydroxybiphenyl (1) 1 mole, using an aromatic crosslinking agent (2) 0.3 to 0.6 mole, The reaction was performed using a solvent so that the solid content concentration was 30 to 65 wt%.

一種環氧樹脂，其特徵係使如請求項1之多價羥基樹脂與表氯醇反應而得。 An epoxy resin characterized by using a polyvalent hydroxyl group as claimed in claim 1 Base resin and epichlorohydrin.

一種環氧樹脂組成物，其特徵係以如請求項3之環氧樹脂及硬化劑作為必須成分。 An epoxy resin composition characterized in that an epoxy resin and a hardener as claimed in claim 3 are required components.

一種環氧樹脂硬化物，其特徵係使如請求項4之環氧樹脂組成物硬化者。 An epoxy resin hardened product characterized by hardening the epoxy resin composition according to claim 4.