201008970 六、發明說明： 【發明所屬之技術領域】 本發明係關於環氧樹脂硬化劑、環氧樹脂組成物、其 硬化物以及光半導體裝置。進一步詳細而言關於可供應著 色少、耐龜裂性及透明性優異之硬化物之環氧樹脂硬化劑 、環氧樹脂組成物、其硬化物以及光半導體裝置。 ® 【先前技術】 一般而言，由酸酐與環氧樹脂所得到之環氧樹脂硬化 物，係廉價並且透明性、電氣絕緣性、耐藥品性、耐濕性 、接著性等優異，一直被使用在電氣絕緣材料、半導體材 料、接著材料、塗料材料等、各式各樣之用途方面。作爲 一個代表性的使用範例，可列舉用於保護發光二極體（ Light-emitting diode:以下略記爲LED)之發光元件之密 封材。近年來，隨著將發出短波長光線的光源與螢光體組 ® 合之白色LED普及，密封材之劣化逐漸被視爲問題。 亦即，白色LED之情況中，由於使用較高能量之光源 ，因此與以往之紅色或綠色之LED相比，會有密封材劣化 而容易著色、LED之壽命變短的問題發生。另外，因爲發 光元件之改良使得小型化及大電流化進展，隨著如此，在 使LED長時間點燈之情況中所產生的熱也變大，因此亦相 同地引起密封材之劣化。 抑制如此的光或熱造成之劣化’在環氧樹脂之更進一 步普及方面，正成爲重要的課題。.作爲解決此事的方法， -5- 201008970 使用脂環式環氧樹脂之環氧樹脂組成物代替容易因爲光或 熱造成劣化的芳香族環氧樹脂被提出（例如參照專利文獻 1、2及 3 )。 另一方面，使用這樣的脂環式環氧樹脂之環氧樹脂組 成物，有所得到之硬化物缺乏強韌性、容易因爲溫度等條 件變化產生龜裂的這種缺點。爲了解決此事而使由環氧樹 脂組成物所得到之硬化物強韌化的方法而言，已知有使用 由各種高分子所構成之改質劑的方法。例如有藉由在環氧 ❹ 樹脂組成物添加聚酯樹脂，不損及硬化物之透明性地使強 韌性提升之方法被提出（例如參照專利文獻4)。 但是一般而言，由於聚酯樹脂在縮合時顏色容易附著 ，因此在上述專利文獻4所記載之發明中，如其實施例所 揭示般，硬化物由黃色顯著地著色成褐色。因此，在例如 上述LED密封材般要求無色透明的用途之中，會有實用上 的問題。 爲了解決如此的問題，而有添加樹枝狀高分子的方法 ® 被提出（例如參照專利文獻5 )。 [先前技術文獻] [專利文獻] 專利文獻1 :特開2000-196151號公報 專利文獻2:特開2003-012896號公報 專利文獻3:特開2003-221 490號公報 專利文獻4:特開2004-1 3 1 553號公報 -6 - 201008970 專利文獻5 ··特開2007-3 1 4740號公報 【發明內容】 [發明所欲解決之課題] 但是，前述添加樹枝狀高分子的方法，由於在混合後 之黏度有變高的傾向，且有硬化物之強度差的傾向，因此 會有使用困難的問題。因此，特別是對於在LED之密封要 ® 求微細的加工或表面平滑性之情況而言並不適合。 本發明係鑑於上述之問題而完成者，提供一種環氧樹 脂硬化劑，可兼顧混合後之低黏度與硬化後之強度，而且 可供應著色少、耐龜裂性及透明性優異之硬化物。另外， 提供低黏度之環氧樹脂組成物、著色少、耐龜裂性及透明 性優異之其硬化物以及光半導體裝置。 [用於解決課題之方法] ® 本發明人等，爲了解決上述課題專心檢討之結果，發 現藉由對多元羧酸酐，添加混合特定之樹枝狀高分子作爲 改質劑之環氧樹脂硬化劑，可容易得到低黏度並且使用容 易的環氧樹脂組成物，另外還有著色少、強度、耐龜裂性 及透明性優異之硬化物，以至於使本發明完成。 本發明係關於以下的[1]〜[15]項。 Π]—種環氧樹脂硬化劑，係含有多元羧酸酐及羥値 5 50 mgKOH/g以下之樹枝狀高分子。 [2]如[1]記載之環氧樹脂硬化劑，其中樹枝狀高分子 201008970 之重量平均分子量係2000以下。 [3] 如[1]或[2]記載之環氧樹脂硬化劑’其中樹枝狀高 分子之黏度係l〇Pa · s ( 25°C )以下。 [4] 如[1]〜[3]之任一者所記載之環氧樹脂硬化劑，其 中多元羧酸酐係以下述通式（1)所表示之化合物， [化1]201008970 VI. [Technical Field] The present invention relates to an epoxy resin hardener, an epoxy resin composition, a cured product thereof, and an optical semiconductor device. More specifically, it relates to an epoxy resin hardener, an epoxy resin composition, a cured product thereof, and an optical semiconductor device which are capable of supplying a cured product excellent in color, crack resistance and transparency. ® [Prior Art] In general, an epoxy resin obtained from an acid anhydride and an epoxy resin is inexpensive, excellent in transparency, electrical insulation, chemical resistance, moisture resistance, adhesion, etc., and has been used. In various applications such as electrical insulating materials, semiconductor materials, bonding materials, coating materials, and the like. As a typical use example, a sealing material for protecting a light-emitting element of a light-emitting diode (hereinafter abbreviated as LED) can be cited. In recent years, with the popularization of white LEDs that emit light sources of short-wavelength light and phosphor groups, deterioration of sealing materials is gradually recognized as a problem. In other words, in the case of a white LED, since a light source of a higher energy is used, there is a problem that the sealing material is deteriorated and the color is easily colored and the life of the LED is shortened compared with the conventional red or green LED. In addition, since the improvement of the light-emitting element is progressing in miniaturization and large current, the heat generated in the case where the LED is turned on for a long time is also increased, so that the deterioration of the sealing material is caused by the same. The suppression of such deterioration by light or heat has become an important issue in the further popularization of epoxy resins. As a method for solving this problem, -5-201008970, an epoxy resin composition using an alicyclic epoxy resin is used instead of an aromatic epoxy resin which is easily deteriorated by light or heat (for example, refer to Patent Documents 1 and 2). 3). On the other hand, the epoxy resin composition of such an alicyclic epoxy resin has a drawback that the obtained cured product lacks toughness and is liable to be cracked due to changes in temperature and the like. In order to solve the problem and to cure the cured product obtained from the epoxy resin composition, a method of using a modifier composed of various polymers is known. For example, a method of adding a polyester resin to an epoxy resin composition and improving the toughness without impairing the transparency of the cured product has been proposed (for example, see Patent Document 4). However, in the invention described in the above Patent Document 4, as described in the above, the cured product is remarkably colored brown in yellow as in the case of the polyester resin. Therefore, there is a practical problem in applications requiring colorless transparency such as the above-described LED sealing material. In order to solve such a problem, a method of adding a dendrimer is proposed (for example, refer to Patent Document 5). [PRIOR ART DOCUMENT] Patent Document 1: JP-A-2000-196151 Patent Document 2: JP-A-2003-012896 Patent Document 3: JP-A-2003-221 490 Patent Document 4: JP-A-2004 -1 3 3 553 -6 - 201008970 Patent Document 5: JP-A-2007-3 1 4740 SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] However, the method of adding a dendrimer is due to The viscosity after mixing tends to be high, and the strength of the cured product tends to be poor, so that it is difficult to use. Therefore, it is not suitable especially for the case where the sealing of the LED is required to be finely processed or surface smooth. The present invention has been made in view of the above problems, and provides an epoxy resin hardener which can achieve both a low viscosity after mixing and a strength after hardening, and can provide a cured product which is less colored, has excellent crack resistance and transparency. Further, it provides a low-viscosity epoxy resin composition, a cured product which is less colored, has excellent crack resistance and transparency, and an optical semiconductor device. [Means for Solving the Problems] The present inventors have found that an epoxy resin curing agent which is a modifier of a specific dendrimer is added to a polycarboxylic acid anhydride in order to solve the above problems. It is easy to obtain an epoxy resin composition which is low in viscosity and easy to use, and also has a hardened material which is less colored, has excellent strength, crack resistance and transparency, so that the present invention is completed. The present invention relates to the following items [1] to [15]. Π] - an epoxy resin hardener, which is a dendrimer containing a polycarboxylic acid anhydride and a oxonium 5 50 mgKOH/g or less. [2] The epoxy resin hardener according to [1], wherein the dendrimer 201008970 has a weight average molecular weight of 2,000 or less. [3] The epoxy resin hardener described in [1] or [2] wherein the dendritic high molecular viscosity is less than or equal to 1 〇Pa · s (25 ° C). [4] The epoxy resin curing agent according to any one of [1] to [3], wherein the polycarboxylic acid anhydride is a compound represented by the following formula (1), [Chemical Formula 1]
(式中，Rl〜R4係各自獨立地表示氫原子或直鏈或分枝狀 之碳數1〜4之烷基，選自之兩個亦可結合而形成環 )° [5] 如[1]〜[4]之任一者所記載之環氧樹脂硬化劑’其 中樹枝狀高分子係聚酯。 [6] 如[I]〜[5]之任一者所記載之環氧樹脂硬化劑’其 中含有相對於多元羧酸酐1〇〇重量份爲1〜60重量份之樹枝 狀高分子。 [7] —種環氧樹脂組成物，係含有環氧樹脂及Π]〜[6] 之任一者所記載之環氧樹脂硬化劑。 [8] —種環氧樹脂組成物’係含有環氧樹脂、多元羧酸 酐及羥値550 mgKOH/g以下之樹枝狀高分子。 [9] 如[8]記載之環氧樹脂組成物’其中樹枝狀高分子 之重量平均分子量係2000以下。 -8 - 201008970 [10]如[8]或[9]記載之環氧樹脂組成物，其中樹枝狀 高分子之黏度係l〇Pa· s(25°C )以下。 [1 1 ]如[8 ]〜[1 0 ]之任一者所記載之環氧樹脂組成物， 其中多元羧酸酐係以下述通式（1)所表示之化合物，(wherein R1 to R4 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and two of them may be bonded to form a ring) [5] such as [1] The epoxy resin hardener described in any one of [4], wherein the dendrimer-based polyester is used. [6] The epoxy resin curing agent described in any one of [I] to [5], wherein the epoxy resin is contained in an amount of 1 to 60 parts by weight based on 1 part by weight of the polycarboxylic acid anhydride. [7] An epoxy resin composition comprising an epoxy resin and an epoxy resin hardener described in any one of [6]. [8] An epoxy resin composition' is a dendrimer containing an epoxy resin, a polycarboxylic acid anhydride, and a oxindole of 550 mgKOH/g or less. [9] The epoxy resin composition according to [8] wherein the dendrimer has a weight average molecular weight of 2,000 or less. -8 - 201008970 [10] The epoxy resin composition according to [8] or [9] wherein the viscosity of the dendrimer is 1 〇Pa·s (25 ° C) or less. [1] The epoxy resin composition according to any one of [8] to [10], wherein the polycarboxylic acid anhydride is a compound represented by the following formula (1),
Ut21Ut21
(式中’ Ri〜R·4係各自獨立地表示氫原子或直鏈或分枝狀 之碳數1〜4之烷基，選自之兩個亦可結合而形成環 )。 [12] 如[8]〜[11]之任一者所記載之環氧樹脂組成物， 其中樹枝狀高分子係聚酯。 [13] 如[8]〜[12]之任一者所記載之環氧樹脂組成物， 其中含有相對於多元羧酸酐100重量份而言爲丨〜60重量份 之樹枝狀高分子。 [14] 一種硬化物，係使[7]〜[13]之任一者所記載之環 氧樹脂組成物硬化而成。 [15] —種光半導體裝置’係以[14]記載之硬化物密封 光半導體元件而成。 本發明內容，係與在2008年7月29日所申請之特願 2008- 1 94808號，及在2009年5月27日所申請之特願2009- 127596號所記載之主題相關連’該等揭示內容係由於引用 -9- 201008970 而被援用於此。 [發明之效果] 依據本發明，可得到一種環氧樹脂硬化劑，係在混合 後爲低黏度並且使用容易，而且可供給硬化物強度良好的 環氧樹脂組成物，藉此可得到著色少、耐龜裂性及透明性 優異之硬化物。 【實施方式】 以下，對本發明作詳細地說明。 對於本發明所使用之多元羧酸酐並無特別限制，可列 舉例如琥珀酸酐、馬來酸酐、苯二甲酸酐、四氫苯二甲酸 酐、甲基四氫苯二甲酸酐、甲基內亞甲基四氫苯二甲酸酐 、伊康酸酐、焦蜜石酸酐、二苯基酮四羧酸酐等。該等亦 可倂用兩種以上。 爲了使藉由本發明所得到之硬化物爲著色少、耐龜裂 性及透明性優異這樣的效果更加顯著地發揮，多元羧酸酐 係以上述通式（1)所表示之化合物爲佳。 就如此的化合物而言，可列舉例如六氫苯二甲酸酐、 甲基六氫苯二甲酸酐、甲基內亞甲基六氫苯二甲酸酐等。 該等亦可倂用兩種以上。 多元羧酸酐之使用量，係以相對於環氧樹脂中之環氧 基1當量而言酸酐基成爲0.8〜1當量之方式配合者爲佳， 成爲0.9〜1當量之方式配合者爲較佳。酸酐基若爲0.8當量 201008970 以上，則硬化變得充分，成爲沒有硬化物之機械的特性顯 著地降低之虞。另外，酸酐基爲1當量以下之情況中，亦 相同地可避免硬化物之機械的特性之降低。 本發明所使用之樹枝狀高分子係羥値550 mgKOH/g以 下，宜爲羥値400〜500 mgKOH/g。只要爲550 mgKOH/g以 下，即可防止變成高黏度之現象。 另外，因爲高黏度、透明度之降低等問題，因此重量 © 平均分子量係以2000以下爲隹，1 000〜2000爲較佳。 再者，以使用此黏度爲10Pa· s(25°c )之樹枝狀高 分子者爲佳，1〜10Pa . s ( 25°C )爲較佳。 爲了使藉由本發明所得到之樹脂組成物爲低黏度並且 使用容易之效果，以及所得到之硬化物的特徵：著色少、 耐龜裂性等強度及透明性優異這樣的效果更加顯著地發揮 ，樹枝狀高分子係以聚酯爲佳。另外，以在具有至少1個 反應性環氧基或羥基之核附加了 1〜50世代，宜爲1〜10世 ® 代之至少1個二羥基一元羧酸之聚酯爲較佳。 就適合的核而言，可列舉新戊二醇、三羥甲基丙烷、 季戊四醇、2-丁基-2-乙基-1，3-丙烷二醇等醇類、一元羧酸 之縮水甘油基酯、一元醇之縮水甘油醚等環氧化物類等。 就二羥基單羧酸而言，可列舉2,2·雙（羥甲基）丙酸 、2,2-雙（羥甲基）丁酸等。對於本發明所使用之樹枝狀 高分子之製造方法並無特別限制，可適用周知的方法。 在本發明中，樹枝狀高分子，係以相對於多元羧酸酐 100重量份含1〜60重量份爲佳，含10〜5 0重量份爲較佳。 -11 - 201008970 樹枝狀高分子之含量只要爲1重量份以上，則所得到之硬 化物之強韌性充分，成爲沒有耐龜裂性降低之虞。另外， 樹枝狀高分子之含量只要爲60重量份以下，則不會變成高 黏度而使用容易，所得到之硬化物之玻璃轉移溫度也沒有 顯著地降低之虞，實用上爲適合的。 本發明所使用之環氧樹脂並無特別限制，而由耐光性 及耐熱性方面看來，係以脂環式環氧樹脂爲佳。脂環式環 氧樹脂係於1分子中具有脂環式骨架及2個以上之環氧基者 β ，可列舉例如3'，4'-環氧環己基甲基-3,4-環氧環己烷羧酸 酯、雙（3，4-環氧環己基甲基）己二酸酯、二氧化乙烯基 環己烯、氫化雙酚Α二縮水甘油醚等。該等亦可併用兩種 以上。 另外，亦可因應目的使用脂環式環氧樹脂以外之環氧 樹脂。就如此的環氧樹脂而言，可列舉例如藉由雙酚A、 雙酚S等雙酚類與表氯醇之反應所得到之雙酚型環氧樹脂 、藉由苯酚酚醛與表氯醇之反應所得到之苯酚酚醛型環氧 ® 樹脂、藉由多元羧酸與表氯醇之反應所得到之縮水甘油基 酯型環氧樹脂等。該等亦可倂用兩種以上。 該等脂環式環氧樹脂以外之環氧樹脂之使用量，係以 相對於脂環式環氧樹脂1〇〇重量份定爲〇〜80重量份爲佳， 定爲〇〜20重量份爲較佳。脂環式環氧樹脂以外之環氧樹 脂之使用量只要是在80重量份以下，即可防止硬化物之耐 光性及耐熱性降低。 在本發明中，藉由混合多元羧酸酐及樹枝狀高分子， -12- 201008970 可得到目標的環氧樹脂硬化劑，而對於其製造方法並無特 別限制’可適用周知的方法。進一步，藉由混合該環氧樹 脂硬化劑及環氧樹脂，可得到環氧樹脂組成物，而對於其 製造方法並無特別限制，可適用周知的方法。另外，將樹 枝狀高分子與多元羧酸酐分別各自與環氧樹脂混合，亦可 得到環氧樹脂組成物。 本發明中之環氧樹脂組成物可因應目的適當地添加硬 〇 化促進劑。就硬化促進劑而言，可列舉例如2-乙基-4-甲基 咪唑、1-甲基咪唑等咪唑類、苄基二甲基胺、Ν,Ν-二甲基 苯胺等三級胺、四甲基氯化銨、苄基三乙基氯化銨等四級 敍鹽、四正丁基鎸〇,〇-二乙基二硫代磷酸鹽、四丁基鱗苯 并三唑鹽等鳞鹽、辛酸鋅、硬脂酸鋅等金屬鹽、乙醯丙酮 鋅、苯甲醯基丙酮鋅等金屬錯合物等。 在使用硬化促進劑之情況下環氧樹脂組成物中之配合 量，係以定爲〇 . 〇 1〜8重量％爲佳，定爲〇 . 1〜5重量％爲較 β 佳。硬化促進劑之配合量若爲0.01重量％以上，則可得到 充分之效果。另外，硬化促進劑之配合量若爲8重量％以下 ，則可減低所得到之硬化物著色或者耐熱性降低。 對於本發明中之環氧樹脂組成物而言，可在不損及所 得到之硬化物之特性的範圍，因應目的進一步添加各種添 加劑。就添加劑而言，可列舉可撓化劑、熱安定劑、紫外 線吸收劑、難燃劑、帶電防止劑、消泡劑、搖變性賦予劑 、離型劑等。再者’可列舉例如用於使硬化物之耐光性及 耐熱性進一步提升之抗氧化劑；用於控制硬化中之聚合反 -13- 201008970 應之鏈移動劑；用於改良硬化物之機械的物性、接著性、 操作性之充塡劑、可塑劑、低應力化劑、偶合劑、染料、 光散射劑等。 藉由使本發明中之環氧樹脂組成物加熱硬化，可得到 著色少、耐龜裂性及透明性優異之硬化物。對於硬化物之 製造方法並無特別限制，可適用周知的方法。對於加熱硬 化之溫度及時間並未特別受到限定，而以90〜1 80 °C、1〜 12小時爲佳。將環氧樹脂組成物藉由塗佈、灌注、浸漬等 @ 方法設置於LED發光元件等表面上，藉由加熱硬化可密封 LED發光元件等。 本發明之光半導體裝置，係以上述硬化物密封LED發 光元件、光二極體元件等光半導體元件者，爲著色少、耐 龜裂性及透明性優異、進一步耐光性及耐熱性亦優異者。 [實施例] 以下，藉由實施例對本發明進一步具體地作說明。本 ® 發明並非受到該等實施例限制者。 (實施例1 ) 相對於聚酯樹枝狀高分子（羥値4 70 mgKOH/g、重量 平均分子量 1800、黏度 7.6Pa· s (25°C ) 、BOLTORN P- 1000 : Perstorp公司製之商品名）20重量份，加入4-甲基 六氫苯二甲酸酐（HN-7000 :日立化成工業股份有限公司 製/酸酐當量168 (g/eq) ) 116重量份作爲多元羧酸酐，於 -14- 201008970 70 °C加熱並攪拌，使其溶解至成爲均勻的，得到環氧樹脂 硬化劑（I )。 相對於環氧樹脂硬化.劑（I ) 136重量份，加入3，，4'-環 氧環己基甲基-3,4-環氧環己烷羧酸酯（〇£1^〇乂1〇£ 2 021? ;DAICEL.化學工業股份有限公司製之商品名/環氧當量 138 ( g/eq )) 1〇〇重量份作爲環氧樹脂，四正丁基銹〇,〇-二乙基二硫代磷酸鹽（HISHICOLIN PX-4ET:日本化學工 Ο 業股份有限公司製之商品名）1重量份作爲硬化促進劑， 9,10-二氫-9-磷雜-10-氧雜菲-9-氧化物（HCA:三光化學 股份有限公司製）1重量份作爲安定劑，於8(TC加熱並攪 拌，使其溶解至成爲均勻的，得到環氧樹脂組成物（I) 〇 接下來，使環氧樹脂組成物（I)在減壓下充分地脫 泡之後，將一部份平靜地注入至（a)將金饜製夾具置於 中央之金屬製淺皿，將殘餘部分注入至（b)板狀之金屬 ® 模具，分別在1 2 0 °C加熱1小時之後，進一步在1 5 0 °C加熱4 小時，得到兩種硬化物（I)。 (實施例2 ) 除了使用聚酯樹枝狀高分子40重量份代替20重量份以 外，係以與實施例1相同之方式得到環氧樹脂硬化劑（II ) 〇 除了使用環氧樹脂硬化劑（II) 156重量份代替環氧樹 脂硬化劑（I )以外，係以與實施例1相同之方式，得到環 -15- 201008970 氧樹脂組成物（II )。進一步，以與實施例1相同之方式得 到硬化物（II )。 (實施例3 ) 除了使用3-甲基六氫苯二甲酸酐與4-甲基六氫苯二甲 酸酐之混合物（以下稱爲3&4-甲基六氫苯二甲酸酐。HN-550 0E:日立化成工業股份有限公司製/酸酐當量168( g/eq ))116重量份作爲多元羧酸酐以外，係以與實施例1相同 之方式得到環氧樹脂硬化劑（ΠΙ )。 由環氧樹脂硬化劑（ΙΠ )，以與實施例1相同之方式 ，得到環氧樹脂組成物（ΠΙ )。進一步，以與實施例1相 同之方式得到硬化物（ΙΠ )。 (實施例4 ) 除了使用聚酯樹枝狀高分子40重量份代替20重量份以 外，係以與實施例3相同之方式，得到環氧樹脂硬化劑（ IV )。 除了使用環氧樹脂硬化劑（IV ) 156重量份代替環氧 樹脂硬化劑（Ο以外，係以與實施例1相同之方式，得到 環氧樹脂組成物（IV )。進一步，以與實施例1相同之方 式得到硬化物（IV)。 (比較例1 ) 除了使用聚酯樹枝狀高分子（羥値600 mgKOH/g、重 201008970(wherein, Ri to R·4 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and two of them may be bonded to form a ring). [12] The epoxy resin composition according to any one of [8] to [11], wherein the dendrimer-based polyester is used. [13] The epoxy resin composition according to any one of [8] to [12] wherein the epoxy resin composition contains from 丨 to 60 parts by weight based on 100 parts by weight of the polycarboxylic acid anhydride. [14] A cured product obtained by curing the epoxy resin composition described in any one of [7] to [13]. [15] An optical semiconductor device is obtained by sealing an optical semiconductor element with the cured material described in [14]. The content of the present invention is related to the subject matter described in the Japanese Patent Application No. 2008-127808, filed on Jan. 29, 2008, the The disclosure is hereby incorporated by reference to -9-201008970. [Effects of the Invention] According to the present invention, an epoxy resin curing agent can be obtained which has a low viscosity after mixing and is easy to use, and can supply an epoxy resin composition having a good strength of a cured product, whereby less coloring can be obtained. A cured product excellent in crack resistance and transparency. [Embodiment] Hereinafter, the present invention will be described in detail. The polycarboxylic acid anhydride used in the present invention is not particularly limited, and examples thereof include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylene. Base tetrahydrophthalic anhydride, itaconic anhydride, pyrogalic anhydride, diphenyl ketone tetracarboxylic anhydride, and the like. These can also be used in more than two ways. In order to make the cured product obtained by the present invention less effective in coloring, crack resistance and transparency, the polyvalent carboxylic acid anhydride is preferably a compound represented by the above formula (1). Examples of such a compound include hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methylnamethylene hexahydrophthalic anhydride. These may also be used in two or more types. The amount of the polycarboxylic acid anhydride to be used is preferably from 0.8 to 1 equivalent based on 1 equivalent of the epoxy group in the epoxy resin, and is preferably 0.9 to 1 equivalent. When the acid anhydride group is 0.8 equivalent of 201008970 or more, the hardening becomes sufficient, and the mechanical properties of the cured product are remarkably lowered. Further, in the case where the acid anhydride group is 1 equivalent or less, the mechanical properties of the cured product can be prevented from being lowered in the same manner. The dendrimer used in the present invention is a oxindole of 550 mgKOH/g or less, preferably hydroxyindole of 400 to 500 mgKOH/g. As long as it is below 550 mgKOH/g, it can prevent the phenomenon of becoming high viscosity. Further, since the viscosity is high, the transparency is lowered, and the like, the weight average molecular weight is preferably 2,000 or less, and preferably 1,000 to 2,000. Further, it is preferred to use a dendrimer having a viscosity of 10 Pa·s (25 ° C), preferably 1 to 10 Pa s (25 ° C). In order to make the resin composition obtained by the present invention have a low viscosity and an easy-to-use effect, and the characteristics of the obtained cured product, the effect of being excellent in strength and transparency such as less coloring and crack resistance is more remarkable. The dendrimer is preferably polyester. Further, a polyester having at least one dihydroxymonocarboxylic acid of 1 to 50 generations, preferably 1 to 10 atoms, is added to the core having at least one reactive epoxy group or hydroxyl group. Examples of suitable cores include alcohols such as neopentyl glycol, trimethylolpropane, pentaerythritol, 2-butyl-2-ethyl-1,3-propanediol, and glycidyl groups of monocarboxylic acids. An epoxide such as an ester or a glycidyl ether of a monohydric alcohol. Examples of the dihydroxymonocarboxylic acid include 2,2·bis(hydroxymethyl)propionic acid and 2,2-bis(hydroxymethyl)butyric acid. The method for producing the dendrimer used in the present invention is not particularly limited, and a known method can be applied. In the present invention, the dendrimer is preferably 1 to 60 parts by weight, more preferably 10 to 50 parts by weight, per 100 parts by weight of the polycarboxylic acid anhydride. -11 - 201008970 When the content of the dendrimer is 1 part by weight or more, the obtained toughness of the cured product is sufficient, and the crack resistance is not lowered. In addition, when the content of the dendrimer is 60 parts by weight or less, it is easy to use without high viscosity, and the glass transition temperature of the obtained cured product is not remarkably lowered, which is practically suitable. The epoxy resin used in the present invention is not particularly limited, and from the viewpoint of light resistance and heat resistance, an alicyclic epoxy resin is preferred. The alicyclic epoxy resin is a β having an alicyclic skeleton and two or more epoxy groups in one molecule, and examples thereof include a 3',4'-epoxycyclohexylmethyl-3,4-epoxy ring. Hexane carboxylate, bis(3,4-epoxycyclohexylmethyl)adipate, vinylcyclohexene oxide, hydrogenated bisphenolphthalein diglycidyl ether, and the like. These may also be used in combination of two or more. In addition, an epoxy resin other than the alicyclic epoxy resin may be used depending on the purpose. Examples of such an epoxy resin include a bisphenol type epoxy resin obtained by a reaction of a bisphenol such as bisphenol A or bisphenol S with epichlorohydrin, and a phenol novolac and an epichlorohydrin. A phenol novolak type epoxy resin obtained by the reaction, a glycidyl ester type epoxy resin obtained by a reaction of a polyvalent carboxylic acid and epichlorohydrin, and the like. These may also be used in two or more types. The amount of the epoxy resin other than the alicyclic epoxy resin is preferably 〇 80 parts by weight based on 1 part by weight of the alicyclic epoxy resin, and is preferably 〇 20 parts by weight. Preferably. When the amount of the epoxy resin other than the alicyclic epoxy resin is 80 parts by weight or less, the light resistance and heat resistance of the cured product can be prevented from being lowered. In the present invention, the target epoxy resin hardener can be obtained by mixing a polycarboxylic acid anhydride and a dendrimer, -12-201008970, and the production method is not particularly limited. A well-known method can be applied. Further, an epoxy resin composition can be obtained by mixing the epoxy resin hardener and the epoxy resin, and the production method is not particularly limited, and a known method can be applied. Further, each of the dendrimer and the polycarboxylic acid anhydride is mixed with an epoxy resin to obtain an epoxy resin composition. The epoxy resin composition of the present invention may suitably be added with a hardening accelerator in accordance with the purpose. Examples of the hardening accelerator include imidazoles such as 2-ethyl-4-methylimidazole and 1-methylimidazole, tertiary amines such as benzyldimethylamine, hydrazine and hydrazine-dimethylaniline, and the like. Four-grade salt such as tetramethylammonium chloride or benzyltriethylammonium chloride, tetra-n-butyl fluorene, bismuth-diethyldithiophosphate, tetrabutyl benzotriazole salt, etc. a metal salt such as a salt, a zinc octylate or a zinc stearate; a metal complex such as zinc acetonate or zinc benzopyrolactone. In the case where a hardening accelerator is used, the compounding amount in the epoxy resin composition is determined to be 〇. 〇 1 to 8 wt% is preferably determined to be 〇. 1 to 5 wt% is better than β. When the amount of the hardening accelerator is 0.01% by weight or more, a sufficient effect can be obtained. Further, when the amount of the curing accelerator is 8% by weight or less, the obtained cured product can be reduced in coloration or heat resistance. In the epoxy resin composition of the present invention, various additives can be further added in accordance with the purpose without impairing the properties of the obtained cured product. Examples of the additives include a flexible agent, a heat stabilizer, an ultraviolet absorber, a flame retardant, a charge preventive agent, an antifoaming agent, a shake imparting agent, and a release agent. Further, for example, an antioxidant for further improving light resistance and heat resistance of a cured product; a chain shifting agent for controlling polymerization in the hardening of anti--13-201008970; and a mechanical property for improving hardened materials can be cited. Adhesives, adhesives, plasticizers, low-stressing agents, coupling agents, dyes, light scattering agents, and the like. By heat-hardening the epoxy resin composition of the present invention, it is possible to obtain a cured product which is less colored, has excellent crack resistance and transparency. The method for producing the cured product is not particularly limited, and a well-known method can be applied. The temperature and time for heat hardening are not particularly limited, and it is preferably from 90 to 180 ° C for 1 to 12 hours. The epoxy resin composition is placed on the surface of an LED light-emitting element or the like by coating, pouring, dipping, etc., and the LED light-emitting element or the like can be sealed by heat hardening. In the optical semiconductor device of the present invention, the optical semiconductor device such as the LED light-emitting device or the photodiode device is sealed with the cured material, and the film is excellent in coloring resistance, crack resistance and transparency, and further excellent in light resistance and heat resistance. [Examples] Hereinafter, the present invention will be further specifically described by way of examples. This ® invention is not limited by the examples. (Example 1) Relative to polyester dendrimer (hydroxyxanthene 4 70 mgKOH/g, weight average molecular weight 1800, viscosity 7.6 Pa·s (25 ° C), BOLTORN P-1000: trade name of Perstorp Co., Ltd.) 20 parts by weight, 4-methylhexahydrophthalic anhydride (HN-7000: manufactured by Hitachi Chemical Co., Ltd. / anhydride equivalent 168 (g/eq)) 116 parts by weight as a polycarboxylic acid anhydride, at -14-201008970 The mixture was heated and stirred at 70 ° C to dissolve it to be uniform, and an epoxy resin hardener (I ) was obtained. 3,4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (〇1^〇乂1〇) was added to 136 parts by weight of the epoxy resin hardening agent (I). £ 2 021? ; Trade name made by DAICEL. Chemical Industry Co., Ltd. / epoxy equivalent 138 ( g / eq )) 1 part by weight as epoxy resin, tetra-n-butyl rust, 〇-diethyl 1 part by weight of thiophosphate (HISHICOLIN PX-4ET: trade name manufactured by Nippon Chemical Industry Co., Ltd.) as a hardening accelerator, 9,10-dihydro-9-phospha-10-oxaphenanthrene-9 - 1 part by weight of an oxide (HCA: manufactured by Sanko Chemical Co., Ltd.) as a stabilizer, and dissolved and stirred at 8 (TC) to be homogeneous, and an epoxy resin composition (I) is obtained. After the epoxy resin composition (I) is sufficiently defoamed under reduced pressure, a part is quietly injected into (a) a metal crucible in which the metal crucible is placed in the center, and the residual portion is injected (b) ) The plate-shaped metal ® molds were heated at 1 20 ° C for 1 hour and further heated at 150 ° C for 4 hours to obtain two hardened materials (I). (Example 2) An epoxy resin hardener (II) was obtained in the same manner as in Example 1 except that 40 parts by weight of the polyester dendrimer was used instead of 20 parts by weight. In addition to the epoxy resin hardener (II), 156 parts by weight was used instead of the epoxy resin. In the same manner as in Example 1, except that the resin curing agent (I), a cyclic resin composition (II) of the ring-15-201008970 was obtained. Further, a cured product (II) was obtained in the same manner as in Example 1. Example 3) A mixture of 3-methylhexahydrophthalic anhydride and 4-methylhexahydrophthalic anhydride (hereinafter referred to as 3&4-methylhexahydrophthalic anhydride. HN-550 0E) was used. : 116 parts by weight of an acid anhydride equivalent of 168 (g/eq) manufactured by Hitachi Chemical Co., Ltd. As an aromatic carboxylic anhydride, an epoxy resin hardener (ΠΙ) was obtained in the same manner as in Example 1. The hardener (ΙΠ) was obtained in the same manner as in Example 1. Further, a cured product (ΙΠ) was obtained in the same manner as in Example 1. (Example 4) In addition to the use of poly 40 parts by weight of the ester dendrimer instead of 20 parts by weight An epoxy resin hardener (IV) was obtained in the same manner as in Example 3. Except that an epoxy resin hardener (IV) 156 parts by weight was used instead of the epoxy resin hardener (Ο, in addition to Example 1) In the same manner, an epoxy resin composition (IV) was obtained. Further, a cured product (IV) was obtained in the same manner as in Example 1. (Comparative Example 1) In addition to a polyester dendrimer (hydroxyxanthene 600 mgKOH/ g, heavy 201008970
量平均分子量 1800、黏度 32.8Pa· s(25°C ) 、BOLTORN p-500 : Perstorp公司製之商品名）20重量份作爲樹枝狀高 分子以外，係以與實施例1相同之方式，得到環氧樹脂硬 化劑（V )。 由環氧樹脂硬化劑（V )，以與實施例1相同之方式得 到環氧樹脂組成物（V )。進一步，以與實施例1相同之方 式得到硬化物（V )。 β (比較例2 )A weight average molecular weight of 1800, a viscosity of 32.8 Pa·s (25 ° C), and BOLTORN p-500: a product name of Perstorp Co., Ltd., 20 parts by weight, as a dendrimer, was obtained in the same manner as in Example 1. Oxygen resin hardener (V). An epoxy resin composition (V) was obtained in the same manner as in Example 1 from an epoxy resin hardener (V). Further, a cured product (V) was obtained in the same manner as in Example 1. β (Comparative Example 2)
除了使用聚酯樹枝狀高分子40重量份代替20重量份以 外，係以與比較例1相同之方式得到環氧樹脂硬化劑（VI )0 除了使用環氧樹脂硬化劑（VI) 156重量份代替環氧 樹脂硬化劑（I )以外，係以與實施例1相同之方式得到環 氧樹脂組成物（VI )。進一步，以與實施例1相同之方式 ® 得到硬化物（VI)。 (比較例3 ) 除了不使用聚酯樹枝狀高分子，使用4-甲基六氫苯二 甲酸酐1 1 6重量份代替環氧樹脂硬化劑（I )以外，係以與 實施例1相同之方式得到環氧樹脂組成物（VII )。 由環氧樹脂組成物（VII )，以與實施例1相同之方式 得到硬化物（VII)。 對在實施例1〜4及比較例1〜3所得到之環氧樹脂組成 -17- 201008970 物（I )〜（VII )之色相及黏度、硬化物（I)〜（VII ) 之外觀、龜裂、玻璃轉移溫度、彎曲強度及彎曲彈性率進 行評估，將其結果表示於表1、2。於龜裂評估使用各硬化 物之中的（a)，於其他硬化物之評估使用（b)。在表1 、2中之特性評估之方法係如同以下所述。 •色相：以目視與ΑΡΗA標準液作比較。 •黏度：於25 °C，以E型黏度計進行測定。 •外觀：對硬化物（b )藉由目視進行判定。 ® •龜裂：將試樣數2個之硬化物（a)在- 3(TC放置20 小時之後，在室溫（25 t )放置1 0小時，以目視確認龜裂 發生之有無。 〇：沒有龜裂 X:試樣中有一處以上龜裂 •玻璃轉移溫度：由硬化物（b)切出2mmx5mmx5mm 之試樣，藉由機械的熱分析（TMA )進行測定。 測定裝置 SSC-5200 ( SEIKO電子工業股份有限 €> 公司製） 測定條件 荷重20g/每分鐘l〇°C加熱 •彎曲強度：依據JIS (日本工業規格）之規格編號 K7171進行測定。 •彎曲彈性率：依據上述JIS K7171進行測定。 -18- 201008970 [表i] 項目 實施例1 實施例2 實施例3 實施例4 配合 (重量份) 酸酐 4-甲基六氫苯二甲酸酐 116 116 — — 3&4-甲基六氫苯二甲酸酐 — — 116 116 樹灘 高分子 羥値470 mgKOH/g 20 40 20 40 羥値600 mgKOH/g — — — — 環氧樹脂 脂肪族職環氧樹脂 100 100 100 100 評估 配合物 色相(APHA) 10 20 10 20 黏度(Pa · s) 2.3 177 2.4 180 硬化物 外觀 無色透明 無色透明 無色透明 無色透明 龜裂 〇 〇 〇 〇 玻璃轉移溫度(。〇 183 141 185 140 彎曲強度(MPa) 90 100 90 105 彎曲彈性率(MPa) 2600 2700 2800 2800 [表2] 項目 比較例1 比較例2 比較例3 配合 (重量份) 酸酐 4-甲基六氫苯二甲酸酐 116 116 116 3&4-甲基六氫苯二甲酸酐 — — — 樹讎 高分子 羥値470 mgKOH/g — — — 羥値600 mgKOH/g 20 40 — 環氧樹脂 脂肪族環狀環氧樹脂 100 100 100 評估 配合物 色相(APHA) 10 20 10 黏度(Pa · s) 13.5 1000以上 0.05 硬化物 外觀 無色透明 淡黃色透明 淡黃色透明 龜裂 〇 〇 X 玻璃嘟麵。C) 182 140 195 彎曲強度(MPa) 80 105 72 彎曲彈性率(MPa) 2600 2900 2900 如表1、2所表示般，判明了在實施例1〜4所得到之樹 脂組成物，兼顧了低黏度與彎曲強度，另外，硬化物也沒 -19- 201008970 有龜裂，爲無色透明的。相對於此，比較例1係由於樹枝 狀高分子之配合量少，因此爲較低黏度，而彎曲強度差。 比較例2係伴隨樹枝狀高分子之配合量增加，彎曲強度變 高，而黏度變得非常高，再者，硬化物著色成黃色。在比 較例3之硬化物中發生了龜裂，此外彎曲強度也低，硬化 物著色成黃色。 藉由本發明，可得到低黏度並且使用容易的環氧樹脂 組成物，及強度高而著色少、耐龜裂性及透明性優 異之硬 〇 化物。 [產業上之利用之可能性] 依據本發明，可得到在混合後爲低黏度並且使用容易 ’而且可供給硬化物強度良好的環氧樹脂組成物之環氧樹 脂硬化劑，藉此可得到著色少、耐龜裂性及透明性優異之 硬化物。 -20-An epoxy resin hardener (VI) was obtained in the same manner as in Comparative Example 1, except that 40 parts by weight of the polyester dendrimer was used instead of 20 parts by weight, except that 156 parts by weight of the epoxy resin hardener (VI) was used instead. An epoxy resin composition (VI) was obtained in the same manner as in Example 1 except for the epoxy resin hardener (I). Further, in the same manner as in Example 1, ® was obtained as a cured product (VI). (Comparative Example 3) The same procedure as in Example 1 was carried out except that the polyester dendrimer was not used, and 161 parts by weight of 4-methylhexahydrophthalic anhydride was used instead of the epoxy resin hardener (I). The epoxy resin composition (VII) was obtained in the manner. From the epoxy resin composition (VII), a cured product (VII) was obtained in the same manner as in Example 1. The appearance of the hue and viscosity of the epoxy resin composition -17-201008970 (I) to (VII) obtained in Examples 1 to 4 and Comparative Examples 1 to 3, and the appearance of the cured product (I) to (VII), turtle The crack, glass transition temperature, bending strength, and flexural modulus were evaluated, and the results are shown in Tables 1 and 2. (a) of each hardened material was used for crack evaluation, and (b) was used for evaluation of other hardened materials. The methods for evaluating the characteristics in Tables 1 and 2 are as follows. • Hue: Visually compare with ΑΡΗA standard solution. • Viscosity: Measured at 25 ° C with an E-type viscometer. • Appearance: The cured product (b) is judged by visual inspection. ® • Cracking: The cured product (a) of the number of samples (a) was placed at -3 (TC for 20 hours, and allowed to stand at room temperature (25 t) for 10 hours to visually confirm the presence or absence of cracking. No cracking X: One or more cracks in the sample • Glass transition temperature: A sample of 2 mm x 5 mm x 5 mm was cut out from the hardened material (b) and measured by mechanical thermal analysis (TMA). Measuring device SSC-5200 (SEIKO) E-Industry Limited Co., Ltd.) Measurement Conditional Load 20g/min l〇°C Heating • Bending Strength: Measured according to JIS (Japanese Industrial Standard) Specification No. K7171. • Bending Elasticity: According to JIS K7171 above -18- 201008970 [Table i] Project Example 1 Example 2 Example 3 Example 4 Blending (parts by weight) Anhydride 4-methylhexahydrophthalic anhydride 116 116 — 3&4-methyl six Hydroxyphthalic anhydride — 116 116 Tree Beach Polymer Hydroxyl 470 mgKOH/g 20 40 20 40 Hydroxylhydrazine 600 mgKOH/g — — — — Epoxy Resin Aliphatic Epoxy 100 100 100 100 Evaluation of Complex Hue (APHA) 10 20 10 20 Viscosity (Pa · s) 2.3 177 2.4 180 Appearance of hardened colorless transparent colorless transparent colorless transparent colorless transparent cracked glass transition temperature (. 〇183 141 185 140 bending strength (MPa) 90 100 90 105 bending elastic modulus (MPa) 2600 2700 2800 2800 [Table 2] Item Comparative Example 1 Comparative Example 2 Comparative Example 3 Blending (parts by weight) Anhydride 4-methylhexahydrophthalic anhydride 116 116 116 3&4-methylhexahydrophthalic anhydride — — — Tree 雠 polymer Hydroxylhydrazine 470 mgKOH/g — — — Hydroxylhydrazine 600 mgKOH/g 20 40 — Epoxy Resin Aliphatic Epoxy Resin 100 100 100 Evaluation of Complex Hue (APHA) 10 20 10 Viscosity (Pa · s) 13.5 1000 or more 0.05 Appearance of hardened colorless transparent yellowish transparent light yellow transparent cracked 〇〇X glass dough. C) 182 140 195 bending strength (MPa) 80 105 72 bending elastic modulus (MPa) 2600 2900 2900 as shown in Tables 1 and 2. In general, it was found that the resin compositions obtained in Examples 1 to 4 had both low viscosity and bending strength, and the cured product was not cracked by -19-201008970, and was colorless and transparent. On the other hand, in Comparative Example 1, since the blending amount of the dendrimer was small, the viscosity was low and the bending strength was poor. In Comparative Example 2, the blending amount of the dendrimer was increased, the bending strength was increased, and the viscosity was extremely high. Further, the cured product was colored yellow. Cracking occurred in the cured product of Comparative Example 3, and the bending strength was also low, and the hardened material was colored yellow. According to the present invention, it is possible to obtain an epoxy resin composition which is low in viscosity and easy to use, and a hard-cured compound which has high strength, is less colored, has excellent crack resistance and transparency. [Possibility of Industrial Applicability] According to the present invention, an epoxy resin hardener which is low in viscosity after mixing and which is easy to use and which can supply an epoxy resin composition having good strength of a cured product can be obtained, whereby coloring can be obtained. A hardened material that is less resistant to cracking and transparency. -20-