TW201120000A

TW201120000A - Multivalent carboxylic acid composition, curable resin composition, cured article and method for producing multivalent carboxylic acid composition

Info

Publication number: TW201120000A
Application number: TW099120201A
Authority: TW
Inventors: Masataka Nakanishi; Kenichi Kuboki; Naofusa Miyagawa; Yoshihiro Kawada; Chie Sasaki; Shizuka Aoki; Zuikan Suzuki; Masato Yarita; Hiroo Koyanagi
Original assignee: Nippon Kayaku Kk
Priority date: 2009-06-22
Filing date: 2010-06-22
Publication date: 2011-06-16
Also published as: CN102459144A; CN102459144B; CN103787887B; JP5713898B2; CN103787887A; TWI491590B; JPWO2010150524A1; KR101692450B1; KR20120030056A; WO2010150524A1

Abstract

The present invention relates to a multivalent carboxylic acid composition containing a multivalent carboxylic acid represented by the following formula (1), an epoxy resin curing agent composition containing the same, a curable resin composition containing the curing agent composition and an epoxy resin, a cured article thereof, and a novel multivalent carboxylic acid. When the multivalent carboxylic acid and a composition containing the same are used as a curing agent for epoxy resin, evaporation of the curing agent during cure is little, and the obtained cured article has excellent optical properties and thermal durability. (in this formula, R respectively independently represents hydrogen atom, C1-C6 alkyl group or carboxyl group, P represents a divalent cross-linking group defined by the following (a) or (b), (a) A cross-linking group which is a chained-shape alkyl chain having a C6-C10 branched structure, the chained-shape alkyl chain having a C3-C12 straight chain as a main chain, and two to four side chains, and at least one of the side chains is C2-C10. (b) A divalent cross-linking group formed by removing two hydroxyl groups from at least one cross-linked polycyclic diol selected from tricyclodecane dimethanol or pentacyclopentadecane dimethanol, which may have a methyl group on a cyclic ring.

Description

201120000 六、發明說明：【發明所屬之技術領域】本發明係有關特別適用於電氣電子材料紐、多元賴組成細及含有該多錢酸組·^多元氧樹脂之硬化劑的硬化性環氧樹脂組成物。並且乍為環綾酸組成物除了多元叛酸所使用之領域以外，亦可該多元為塗料、接著劑、成形品、半導體、光半導體=作用樹脂、光半導體之黏晶（die bQnd)材料用樹脂材枓，樹脂等之原料，或改質劑、塑化劑、潤滑油原料、= 藥中間產物、塗料用樹脂之原料、或色劑（t〇ner)用樹脂【先前技術】、s、° 多元羧酸具備有高熱安定性、良好之電氣特性、優異之耐藥性以及在形成縮合體時之反應性良好等，可作為^ 聯劑、縮合劑等之優異性能。因此，多元羧酸近年來在^ 為高分子製造原材料上極為顯目並逐漸地廣為使用。而且，已知多元羧酸亦可作為環氧樹脂之硬化劑使用。 3有環氧樹脂之硬化性樹脂組成物在作為耐熱性優異之樹脂，係利用在建築、土木、汽車、飛機等之領域。近年來，特別是在半導體相關領域中充滿著附有相機之行動電話、超薄蜜液晶或電漿電視、輕量之筆記型電腦等的具有成為輕.薄.短.小之關鍵字的高特性之電子機器。對此’在該等半導體相關領域中所使用之材料，特別是在環樹月曰所代表之封裝材料中亦要求有極高之特性。 5 322150 . VB- 201120000 更且，近年來，環氧樹脂在光電相關頜域中之利用受到矚目。特別是隨著近年來之高度資訊化，為了順利地傳送、處理龐大的資訊而開發出改變以往經電氣配線之訊號傳送而以光訊號傳達資訊之技術並加以利用。該等所使用之光波導、藍色LED以及光半導體等光學元件之領域中，對於其中所使用之硬化性樹脂，要求有賦予透明性以及耐久性優異之硬化物。一般而言，在如此之領域中所使用的環氧樹脂之硬化劑可列舉如：酸酐系之化合物。特別是使用由環狀脂肪族烴之多元羧酸所形成的酸酐之硬化物，由於耐光性優異，因此使用該酸針者居多。例如，一般係使用曱基四氫酜酸酐、六氫酞酸酐、四氫酞酸酐等脂環式酸酐。其中，由於操作容易故主要使用常溫為液狀之曱基六氫酞酸酐、甲基四氫酞酸酐等。然而’單獨將上述脂環式酸酐作為硬化劑時，由於該等硬化劑之蒸氣壓高而在硬化時會有部分蒸發，因此，硬化物中並無規定量之羧酸酐（硬化劑）的存在故而引起環氧樹脂組成物之硬化不良的問題、以及因硬化條件而使其特 ^生大1lw改變’而有難以獲得安定且具有目的之性能的硬化物之問題。並且，將硬化物在開放系中大量生產時，該等硬化劑在大氣中揮發並對大氣釋出有害物質而產生環境污染、對人體的不良影響以及生產線之污染等問題。並且，使用以往之硬化劑的硬化物，在密封LED時，特別是在密封SMD(Surface Mount Device)時，由於樹脂 322150 6 201120000 的使用I少’而會有下㈣題：上述之硬化不佳及無法得到安定性能之影響極為顯著、因凹陷的發生等引起配線露出而使咎封不元王、或在焊錫回焊（s〇lder reH〇W)時之龜裂及/或剝離等的發生、或因長期點燈而使品質變差等之問題。另外’類似本發明之多元羧酸的多元羧酸，已知在例如專利文獻4及5等中為乳化劑等用途。 [先前技術文獻] [專利文獻] [專利文獻1]日本特開2003-277473號公報 [專利文獻2]日本特開2008-063333號公報 [專利文獻3]曰本專利2813028號公報 [專利文獻4]曰本專利2915962號公報 [專利文獻5]日本特開平3-26743號公報【發明内容】 [發明所欲解決之課題] 本發明之目的係提供硬化時之硬化劑的揮發少而可達到硬化物安定之目的性能的硬化劑、硬化劑所使用之新穎多元羧酸、含有該多元羧酸或硬化劑組成物之環氧樹脂組成物（硬化性樹脂組成物）、以及該環氧樹脂組成物（硬化性樹脂組成物）之硬化物。因而提供有用之新穎多元羧酸以及含有該多元羧酸之組成物。特別是，目的在提供硬化物之耐熱特性’具體而言，係透光率之維持率、LED中之照度維持率等光學特性優異之硬化性樹脂組成物，因此之多 7 322150 201120000 元羧酸以及含有該多元羧酸之多元羧酸組成物。 [用以解決課題之手段] 本發明者等因鑑於上述實情而專心致志進行檢討之結果，遂而完成本發明。亦即，本發明係有關下述之發明者。 1. 一種含有下述式（1)表示之多元羧酸的多元羧酸組成物，201120000 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a hardenable epoxy resin which is particularly suitable for use in electrical and electronic materials, finely divided compositions, and hardeners containing the polyacid acid group. Composition. Further, the ruthenium phthalic acid composition may be used in addition to the field of multi-dimensional oxic acid, and may be used as a coating, an adhesive, a molded article, a semiconductor, a photo-semiconductor, a functional resin, or a photo-semiconductor die bQnd material. Raw materials such as resin materials, resins, etc., or modifiers, plasticizers, lubricant raw materials, = drug intermediates, raw materials for coating resins, or resins for toners (pre-technical), s, ° The polycarboxylic acid has excellent thermal stability, good electrical properties, excellent chemical resistance, and good reactivity when forming a condensate, and can be used as a coupling agent or a condensing agent. Therefore, polycarboxylic acids have been extremely prominent and widely used in recent years as raw materials for polymer production. Further, it is known that a polyvalent carboxylic acid can also be used as a hardener for an epoxy resin. (3) The curable resin composition having an epoxy resin is used in the fields of construction, civil engineering, automobiles, and airplanes as a resin excellent in heat resistance. In recent years, especially in the field of semiconductors, it is full of camera-equipped mobile phones, ultra-thin honey LCD or plasma TVs, lightweight notebook computers, etc., which have become the key to light, thin, short and small. Characteristic electronic machine. Extremely high properties are also required for the materials used in these semiconductor-related fields, particularly in the packaging materials represented by the ring tree. 5 322150 . VB- 201120000 Moreover, in recent years, the use of epoxy resin in the optoelectronic related jaw domain has attracted attention. In particular, with the recent high level of informationization, in order to smoothly transmit and process huge amounts of information, we have developed and utilized technologies that change the transmission of signals by electrical wiring and transmit information by optical signals. In the field of optical elements such as optical waveguides, blue LEDs, and optical semiconductors, the cured resin used therein is required to have a cured product excellent in transparency and durability. In general, the hardener of the epoxy resin used in such a field may, for example, be an acid anhydride-based compound. In particular, a cured product of an acid anhydride formed of a polyvalent carboxylic acid of a cyclic aliphatic hydrocarbon is used, and since it has excellent light resistance, the acid needle is often used. For example, an alicyclic acid anhydride such as mercaptotetrahydrofurfuric anhydride, hexahydrophthalic anhydride or tetrahydrophthalic anhydride is generally used. Among them, sulfhydryl hexahydrophthalic anhydride or methyltetrahydrophthalic anhydride which is liquid at normal temperature is mainly used because of ease of handling. However, when the above-mentioned alicyclic acid anhydride is used alone as a hardener, since the vapor pressure of the hardeners is high and partial evaporation occurs during hardening, there is no prescribed amount of carboxylic anhydride (hardener) in the cured product. Therefore, there is a problem that the epoxy resin composition is poorly cured, and the curing condition is changed by a large amount of 1 Hz, and there is a problem that it is difficult to obtain a cured product having a desired performance. Further, when the hardened material is mass-produced in an open system, the hardener is volatilized in the atmosphere and releases harmful substances to the atmosphere to cause environmental pollution, adverse effects on the human body, and contamination of the production line. In addition, when the LED is sealed, especially when the SMD (Surface Mount Device) is sealed, the use of the resin 322150 6 201120000 is small, and there is a lower (four) problem: the above hardening is poor. And the effect that the stability performance cannot be obtained is extremely remarkable, and the wiring is exposed due to the occurrence of the dent, and the occurrence of cracks and/or peeling during the solder reflow (s〇lder reH〇W) is caused. Or problems such as poor quality due to long-term lighting. Further, a polyvalent carboxylic acid similar to the polyvalent carboxylic acid of the present invention is known to be used as an emulsifier, for example, in Patent Documents 4 and 5. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2008-063333 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2008-063333 [Patent Document 3] Japanese Patent No. 2813028 (Patent Document 4) [Patent Document 5] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 3-26743. a novel polycarboxylic acid used for a hardening agent and a hardening agent, a epoxy resin composition containing the polycarboxylic acid or hardener composition (curable resin composition), and the epoxy resin composition (hardened resin composition) cured product. Thus, useful novel polycarboxylic acids and compositions containing the polycarboxylic acids are provided. In particular, the purpose is to provide a curable resin composition which is excellent in optical properties such as a heat retention property of a cured product, specifically, a transmittance retention ratio and an illuminance maintenance ratio in an LED. Therefore, it is 7 322150 201120000 carboxylic acid. And a polycarboxylic acid composition containing the polycarboxylic acid. [Means for Solving the Problems] The present inventors completed the present invention by focusing on the results of the review in view of the above facts. That is, the present invention relates to the inventors described below. A polycarboxylic acid composition containing a polyvalent carboxylic acid represented by the following formula (1),

式中，R各自獨立表示氫原子、碳數1至6之烷基或羧基；P表示下述（a)或（b)所定義之2價交聯基： (a) 係屬於具有碳數6至20之分支構造的鏈狀烷基鏈之交聯基，而該鏈狀烷基鏈具有碳數3至12之直鏈的主鏈與2 至4個之侧鏈，且該側鏈之至少1者為碳數2至10、 (b) 係可在環上具有曱基之從選自三環癸烷二曱醇或五環十五烷二曱醇之至少1種的交聯多環二醇中去除2個羥基後之2價交聯基，惟P為（b)時，R表示氫原子以外之基。 2.如上述1記載之多元羧酸組成物，其中，2價交聯基係以（a)所定義之交聯基，且以（a)所定義之交聯基係下述式 (al)表示之2價基的任一者，式（al)= 8 322150 201120000Wherein R each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a carboxyl group; and P represents a divalent crosslinking group as defined in the following (a) or (b): (a) is a carbon number 6 a cross-linking group of a chain alkyl chain of a branched structure of 20, wherein the chain alkyl chain has a linear main chain of 3 to 12 carbon atoms and 2 to 4 side chains, and at least the side chain 1 is a carbon number of 2 to 10, (b) is a crosslinked polycyclic second having at least one selected from the group consisting of tricyclodecanedioxane or pentadecanedioxanol having a mercapto group on the ring. A divalent cross-linking group in which two hydroxyl groups are removed from the alcohol, and when P is (b), R represents a group other than a hydrogen atom. 2. The polycarboxylic acid composition according to the above 1, wherein the divalent crosslinking group is a crosslinking group defined by (a), and the crosslinking group defined by (a) is the following formula (al) Any one of the two valence groups indicated, (al) = 8 322150 201120000

式中，各基之末端的氺記號係表示在*記號處鍵結所鄰接之氧原子。 3. 如上述1或2記載之多元羧酸組成物，其中，（a)之交聯基中之主鏈為碳數3至6之直鏈，側鏈之至少2者為碳數 2至4之烷基。 4. 如上述1至3中任一項記載之多元羧酸組成物，其中，以（a)所定義之交聯基係從2, 4-二乙基-1，5-戊二醇去除2 個羥基後之2價基。 5. 如上述1記載之多元羧酸組成物.，其中，2價之交聯基係（b)所定義之交聯基，且（b)所定義之交聯基係下述式（bl) 表示之2價基的任一者，式（bl):In the formula, the 氺 mark at the end of each group indicates the oxygen atom adjacent to the bond at the * mark. 3. The polycarboxylic acid composition according to the above 1 or 2, wherein the main chain in the crosslinking group (a) is a linear chain having a carbon number of 3 to 6, and at least two of the side chains are a carbon number of 2 to 4. Alkyl group. 4. The polycarboxylic acid composition according to any one of 1 to 3 above, wherein the crosslinking group defined by (a) is removed from 2,4-diethyl-1,5-pentanediol 2 A divalent group after a hydroxyl group. 5. The polycarboxylic acid composition according to the above 1, wherein the cross-linking group defined by the cross-linking group of (2) is (b), and the cross-linking group defined by (b) is the following formula (bl) Any of the two valence groups, formula (bl):

S 9 322150 201120000S 9 322150 201120000

式中，各構造式中存在之複數個R2各自獨立表示氫原子或甲基。 6. 如上述1至5中任一項記載之多元羧酸組成物，其係由 R2均為氫原子之多元羧酸所成者。 7. 如上述1至6中任一項記載之多元羧酸組成物，係包含 50莫耳％以上之式（1)之R為曱基及/或羧基的多元羧酸者。 8. 如上述1至7中任一項記載之多元羧酸組成物，其中，式（1)之R為甲基或羧基。 9. 如上述8記載之多元羧酸組成物，其中，氫原子以外之基為曱基。 10. 如上述1至8中任一項記載之多元羧酸組成物，其中，多元羧酸組成物係包含式（1)所示之多元羧酸的至少1種與可經甲基取代之C4至C?環二、三或四羧酸酐。 11. 如上述10記載之多元羧酸組成物，其中，可經甲基取代之C4至C?環二、三或四羧酸酐係可經曱基取代之環己烷二或三羧酸酐。 12. —種環氧樹脂用硬化劑，係含有式（1)之多元羧酸、或如上述10或11記載之多元羧酸組成物。 13. 如上述12記載之環氧樹脂用硬化劑組成物，其係由： 10 322150 201120000 式⑴之P表示的2價交聯基係以（a)所定義之交聯基且以 U)所定義之交聯基係下述（1)之2價基的多元羧酸、盥選自下述（2)之酸酐所成組群中之至少丨種的酸酐，所成之多元羧酸組成物， , (1)2價基： • 從2,4—二乙基-1，5-戊二醇去除2個羥基後之2價基； (2)酸酐：曱基六氫酞酸酐、以及環己烷-1，2,4-三羧酸一 14.如上述12記載之環氧樹顧硬化難成物，其係由：式⑴之P表示的2價交聯基係以⑻所㈣之交聯基且^ (b)所定義之交聯基係下述⑴之式（Μ)所示的2價義中々任一者的多城酸、與選自下述⑵之酸酐所成組群；^ 少1種的酸酐，所成之多元羧酸組成物， ⑴式（bl):In the formula, a plurality of R2 present in each structural formula each independently represent a hydrogen atom or a methyl group. 6. The polycarboxylic acid composition according to any one of the above 1 to 5, which is obtained from a polyvalent carboxylic acid wherein R2 is a hydrogen atom. 7. The polyhydric carboxylic acid composition according to any one of the above 1 to 6, which is a polyvalent carboxylic acid containing 50 mol% or more of the formula (1) wherein R is a mercapto group and/or a carboxyl group. The polycarboxylic acid composition according to any one of the above 1 to 7, wherein R of the formula (1) is a methyl group or a carboxyl group. 9. The polycarboxylic acid composition according to the above 8, wherein the group other than the hydrogen atom is a mercapto group. The polycarboxylic acid composition according to any one of the above 1 to 8, wherein the polycarboxylic acid composition contains at least one of the polycarboxylic acid represented by the formula (1) and a C4 which may be substituted by a methyl group. To C? ring di-, tri- or tetracarboxylic anhydride. 11. The polycarboxylic acid composition according to the above 10, wherein the C4 to C? ring di, tri or tetracarboxylic anhydride which may be substituted by a methyl group is a cyclohexane di or tricarboxylic anhydride which may be substituted with a mercapto group. A curing agent for an epoxy resin comprising a polyvalent carboxylic acid of the formula (1) or a polyvalent carboxylic acid composition according to the above 10 or 11. 13. The hardener composition for an epoxy resin according to the above 12, which is: 10 322150 201120000 The divalent crosslinked group represented by P of the formula (1) is a cross-linking group defined by (a) and is a U) The crosslinked group is defined as a polyvalent carboxylic acid having a valence group of the following (1), and an anthracene selected from the group consisting of the acid anhydrides of the following (2), and a polyvalent carboxylic acid composition. , (1) Divalent group: • A divalent group obtained by removing two hydroxyl groups from 2,4-diethyl-1,5-pentanediol; (2) Anhydride: mercapto hexahydrophthalic anhydride, and ring Hexane-1,2,4-tricarboxylic acid- 14. The epoxy resin hardening product according to the above 12, which is characterized in that: the divalent crosslinked group represented by P of the formula (1) is (8) (4) The cross-linking group and the cross-linking group defined by (b) are a group of a poly-methane acid of any of the divalent intermediates represented by the following formula (1) and an acid anhydride selected from the group (2) below. ;^ One less acid anhydride, the resulting polycarboxylic acid composition, (1) Formula (bl):

子或各構造式t存在之複數府各自獨立表示氣原 (2)酸酐：甲基六纽_、以及環己 322150 11 201120000 酐。 15. —種硬化性樹脂組成物，係包含如上述丨至7中任一項 δ己载之式（1)的多元羧酸或如上述12至14中任一項記载之硬化劑組成物，與環氧樹脂者。 16. 如上述15記載之硬化性樹脂組成物，其中，環氧樹脂係脂環式環氧樹脂。 Π.如上述16記載之硬化性樹脂組成物，其中，硬化劑組成物係上述13記載之硬化劑組成物。 18.如上述16記載之硬化性樹脂組成物，其中，硬化劑組成物係上述14記載之硬化劑組成物。 19· 一種上述15記載之硬化性樹脂組成物的硬化物。 20.種上述丨兄載之式（1)所示的多元讓酸之製造方法，係使下述（a)或（b)之二元醇與（c)反應者，其中， (a) 係具有碳數6至20之分支構造的鏈狀脂肪族二元醇，而其鏈狀烧基鏈具有碳數3至12之直鏈的主鏈與2至4 個之側鏈，且該側鏈之至少丨者為碳數2至1〇之烷基、或 (b) 係可在環上具有曱基之選自三環癸烷二曱醇或五環十五烧二甲醇之至少1種的交聯多環二醇； (c) 係至少1種選自六氫酞酸酐、曱基六氫敗酸酐以及環己烷-1，2, 4-三羧酸酐所成組群中之至少丨種的酸酐，惟如為（b)時’係至少丨種包含曱基六氫酞酸酐或環己烷一1’2,4-三緩酸酐之任一者的酸酐。 21·如上述20記载之多元羧酸組成物之製造方法’其中，將（a)或（b)之二元醇與（c)之酸酐，以相封於酸酐基1當量 322150 12 201120000 之二元醇的經基當量成為0.001至2當量之比例，在反應溫度40至150°C使其反應。 22. 如上述21記載之多元羧酸組成物之製造方法，其中， (c)之酸酐係六氫酞酸酐及甲基六氫酞酸酐之混合物。 23. 如上述21或22記載之多元羧酸組成物之製造方法，其中，二元醇係2，4_二乙基_1，5_戍二酵或2_乙基_2_丁基 -1，3-丙二醇。 24. 如上述21記載之多元羧酸組成物之製造方法，其係使 2, 4-二乙基-1，5-戊二醇、與六氫酞酸酐及甲基六氫酞酸酐之混合物反應而成。 25. 如上述21記載之多元羧酸組成物之製造方法，其係使無取代之三環癸烷二曱醇或五環十五烷二甲醇、與六氫酞酸酐及甲基六氫酞酸酐之混合物反應而成。 26. —種下述式（1)表示之多元羧酸，式⑴The plural or each of the structural formulas t exist independently to represent the gas (2) acid anhydride: methyl hexa _, and cyclohexene 322150 11 201120000 anhydride. A hardening resin composition comprising the polycarboxylic acid of the formula (1) as set forth in any one of the above-mentioned 丨 to 7 or the hardener composition according to any one of the above 12 to 14 , with epoxy resin. 16. The curable resin composition according to the above 15, wherein the epoxy resin is an alicyclic epoxy resin. The curable resin composition according to the above-mentioned item 16, wherein the hardener composition is the hardener composition described in the above item 13. 18. The curable resin composition according to the above-mentioned item 16, wherein the hardener composition is the hardener composition described in the above 14. 19. A cured product of the curable resin composition according to the above item 15. 20. The method for producing a polybasic acid represented by the above formula (1), wherein the diol of the following (a) or (b) is reacted with (c), wherein (a) a chain aliphatic diol having a branched structure of 6 to 20 carbon atoms, wherein the chain alkyl chain has a linear main chain of 3 to 12 carbon atoms and 2 to 4 side chains, and the side chain At least one of a carbon number of 2 to 1 Å, or (b) at least one selected from the group consisting of tricyclodecane decyl alcohol or penta pentadecane dimethanol having a fluorenyl group on the ring Cross-linked polycyclic diol; (c) at least one selected from the group consisting of hexahydrophthalic anhydride, decyl hexahydroauhydride, and cyclohexane-1,2,4-tricarboxylic anhydride The acid anhydride, if it is (b), is at least an acid anhydride containing any one of mercaptohexahydrophthalic anhydride or cyclohexane-1'2,4-tribasic acid anhydride. The method for producing a polyvalent carboxylic acid composition according to the above 20, wherein the diol of (a) or (b) and the acid anhydride of (c) are phase-sealed to an acid anhydride group of 1 equivalent of 322150 12 201120000 The base equivalent of the diol is 0.001 to 2 equivalents, and the reaction is carried out at a reaction temperature of 40 to 150 °C. 22. The method for producing a polyvalent carboxylic acid composition according to the above 21, wherein the acid anhydride of the (c) is a mixture of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride. 23. The method for producing a polycarboxylic acid composition according to the above 21 or 22, wherein the diol is 2,4-diethyl-1,5-anthracene or 2-ethyl-2-butyl- 1,3-propanediol. 24. The method for producing a polycarboxylic acid composition according to the above 21, which comprises reacting 2,4-diethyl-1,5-pentanediol with a mixture of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride. Made. 25. The method for producing a polycarboxylic acid composition according to the above 21, which is an unsubstituted tricyclodecane decyl alcohol or pentacyclopentadecane dimethanol, hexahydrophthalic anhydride, and methyl hexahydrophthalic anhydride. The mixture is reacted. 26. A polycarboxylic acid represented by the following formula (1), formula (1)

式中，R各自獨立表示氫原子、碳數1至6之烷基或羧基；P表示下述（a)或.（b)所定義之2價交聯基： (a) 係屬於具有碳數6至20之分支構造的鏈狀烷基鏈之交聯基，而該鏈狀烷基鏈具有碳數3至12之直鏈的主鏈與2 至4個之侧鏈，且該側鏈之至少1者為碳數2至10、 (b) 係可在環上具有甲基之從選自三環癸烷二曱醇或五環 •es 13 322150 201120000 十五烷二曱醇之至少1種的交聯多環二醇中去除2個羥基後之2價交聯基，惟P為（b)時，R表示氫原子以外之基。 27. 如上述26記載之多元羧酸，其中，P係以（a)所定義之 2價交聯基，側鏈之至少2者為碳數2至10之交聯基。 28. 如上述27記載之多元羧酸，其中，以（a)所定義之2 價交聯基係從2, 4-二乙基-1，5-戊二醇去除2個羥基後之伸烧基。 29. 如上述26記載之多元羧酸，其中，P係以（b)所定義之 2價交聯基。 30. 如上述26記載之多元羧酸，其中，式（1)中之R係甲基或羧基。 [發明之效果] 本發明之式（1)的多元羧酸或多元羧酸組成物係環氧樹脂之硬化能力優異而可應用作為環氧樹脂之硬化劑。並且調配在環氧樹脂之該多元羧酸或該多元羧酸組成物係使環氧樹脂硬化時一般所採用的溫度範圍中的揮發極少。其結果，達成操作容易並安定硬化物之目的性能。具體上係可得到透明度高且熱耐久性優異之環氧樹脂硬化物。該熱而才久性特別是可列舉如：耐回焊性、透光率之維持率以及 LED在長期點燈下之照度維持率等的光學特性之熱耐久性。【實施方式】本發明之多元羧酸係下述（1)所示之多元羧酸，本發明之多元羧酸，其特徵係：含有下述式（1)所示之多元羧酸 14 322150 201120000 者，Wherein R each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a carboxyl group; and P represents a divalent crosslinking group as defined in the following (a) or (b): (a) is a carbon number a crosslinked group of a chain alkyl chain having a branched structure of 6 to 20, and the chain alkyl chain has a linear main chain of 3 to 12 carbon atoms and 2 to 4 side chains, and the side chain At least one of which has a carbon number of 2 to 10, and (b) is at least one selected from the group consisting of tricyclodecanedioxane or pentacyclic es 13 322150 201120000 pentadecane didecyl alcohol having a methyl group in the ring. In the crosslinked polycyclic diol, a divalent crosslinking group is obtained by removing two hydroxyl groups, and when P is (b), R represents a group other than a hydrogen atom. 27. The polycarboxylic acid according to the above item 26, wherein P is a divalent crosslinking group defined by (a), and at least two of the side chains are a crosslinking group having 2 to 10 carbon atoms. 28. The polycarboxylic acid according to the above 27, wherein the two-valent crosslinking group defined by (a) is obtained by removing two hydroxyl groups from 2,4-diethyl-1,5-pentanediol. base. 29. The polycarboxylic acid according to the above item 26, wherein P is a divalent crosslinking group defined by (b). The polycarboxylic acid according to the above item 26, wherein R in the formula (1) is a methyl group or a carboxyl group. [Effect of the Invention] The polyvalent carboxylic acid or polyvalent carboxylic acid composition epoxy resin of the formula (1) of the present invention is excellent in curing ability and can be used as a curing agent for an epoxy resin. Further, the polyvalent carboxylic acid or the polycarboxylic acid composition in the epoxy resin is emulsified in a temperature range generally used for hardening an epoxy resin. As a result, the purpose of the operation is easy and the purpose of the cured product is stabilized. Specifically, an epoxy resin cured product having high transparency and excellent heat durability can be obtained. In particular, the heat durability of the optical characteristics such as the reflow resistance, the transmittance retention rate, and the illuminance maintenance ratio of the LED under long-term lighting can be cited. [Embodiment] The polyvalent carboxylic acid of the present invention is a polyvalent carboxylic acid represented by the following (1), and the polyvalent carboxylic acid of the present invention is characterized by comprising a polycarboxylic acid represented by the following formula (1): 14 322150 201120000 By,

式中，R各自獨立表示氫原子、碳數1至6之烷基或羧基；P表示下述（a)或（b)所定義之2價交聯基： (a) 係屬於具有碳數6.至20之分支構造的鏈狀烷基鏈之交聯基，而該鏈狀烷基鏈具有碳數3至12之直鏈的主鏈與2 至4個之側鏈，且該側鏈之至少1者為碳數2至10、 (b) 係可在環上具有甲基之從選自三環癸烷二曱醇或五環十五烷二曱醇之至少1種的交聯多環二醇中去除2個羥基後之2價交聯基。更具體而言，本發明之多元羧酸係式（1)所示之至少1 個R為甲基或羧基之化合物，尤其以2個R為曱基或羧基之化合物更佳。本發明之多元羧酸組成物徐至少含有2種以上的上述式（1)所示之化合物，或者，包含至少1種上述式（1)所示之化合物與具有飽和構造的酸酐之組成物，其中，較佳之酸酐係可經甲基取代之c4至〇環二、三或四羧酸酐，以可經曱基取代之C4至c7環二、或三羧酸酐更佳。上述式（1)中，以P表示之交聯基係以上述（a)或（b) 所定義之2價交聯基，對於該等將在以下具體說明。上述（a)所定義之2價交聯基係從具有碳數6至20之分支構造的2價之醇（二元醇）去除羥基後之2價的鏈狀烷Wherein R each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a carboxyl group; and P represents a divalent crosslinking group as defined in the following (a) or (b): (a) is a carbon number 6 a cross-linking group of a chain alkyl chain of a branch structure of 20, wherein the chain-like alkyl chain has a linear main chain of 3 to 12 carbon atoms and 2 to 4 side chains, and the side chain At least one is a carbon number of 2 to 10, and (b) is a crosslinked polycyclic ring having at least one selected from tricyclodecanedioxane or pentadecanedioxanol having a methyl group in the ring. A divalent cross-linking group in which two hydroxyl groups are removed from the diol. More specifically, the polyvalent carboxylic acid of the present invention is a compound in which at least one R represented by the formula (1) is a methyl group or a carboxyl group, and particularly preferably a compound having two R groups as a mercapto group or a carboxyl group. The polycarboxylic acid composition of the present invention contains at least two or more compounds represented by the above formula (1), or a composition comprising at least one compound represented by the above formula (1) and an acid anhydride having a saturated structure. Among them, preferred anhydrides are c4 to anthracene di, tri or tetracarboxylic anhydrides which may be substituted by a methyl group, and more preferably a C4 to c7 ring di or a tricarboxylic acid anhydride which may be substituted with a mercapto group. In the above formula (1), the cross-linking group represented by P is a divalent cross-linking group defined by the above (a) or (b), and the details thereof will be specifically described below. The divalent cross-linking group defined by the above (a) is a divalent chain-like alkane obtained by removing a hydroxyl group from a divalent alcohol (diol) having a branched structure of 6 to 20 carbon atoms.

S 15 322150 201120000 基鏈，係具有在二元醇之2個醇性羥基中夾有烷基鏈的主鏈、以及由該烷基鏈分支後之烷基鏈（稱為侧鏈）的構造。該侧鏈可從構成主鏈之任意的碳原子分支，亦包含例如：從醇性羥基所鍵結之碳原子（主鏈之末端碳原子）分支的情形。如為具有該構造之交聯基者均可，將如此之交聯基的具體例示於下述式（al)。式（al)S 15 322150 201120000 The base chain has a structure in which a main chain having an alkyl chain interposed between two alcoholic hydroxyl groups of a glycol and an alkyl chain (referred to as a side chain) branched from the alkyl chain. The side chain may be branched from any carbon atom constituting the main chain, and includes, for example, a branch of a carbon atom (the carbon atom at the end of the main chain) to which the alcoholic hydroxyl group is bonded. As a crosslinking base having such a structure, a specific example of such a crosslinking group is shown in the following formula (al). Formula (al)

上述式中，以*記號與式（1)中之P的兩側之氧原子鍵結。以上述（a)所定義之伸烧基交聯基係，相對於主鏈伸烷基，如為具有烷基支鏈（側鏈）之構造即可而無特別限制，主鏈之碳數為3以上之主鏈，以具有至少1個烷基側鏈者為佳，並以具有2個以上之烷基側鏈者為特佳。作為較佳者係可列舉如具有碳數3至12之直鏈的主鏈與2至4 個之侧鏈，且該側鏈之至少1者為碳數2至10之交聯基。 16 322150 201120000 此時，以側鏈之至少2者為碳數2至10之交聯基者更佳。上述（b)所定義之交聯基可列舉如下述式（bl)表示之 2價基。式（bl):In the above formula, the * symbol is bonded to the oxygen atoms on both sides of P in the formula (1). The alkylene-crosslinking group defined by the above (a) is not particularly limited as long as it has an alkyl group (side chain) with respect to the main chain alkyl group (the side chain), and the carbon number of the main chain is The main chain of 3 or more is preferably one having at least one alkyl side chain, and particularly preferably having two or more alkyl side chains. Preferred examples thereof include a main chain having a linear chain of 3 to 12 carbon atoms and 2 to 4 side chains, and at least one of the side chains is a crosslinking group having 2 to 10 carbon atoms. 16 322150 201120000 At this time, it is more preferable that at least two of the side chains are crosslinked groups having a carbon number of 2 to 10. The crosslinking group defined in the above (b) is exemplified by a divalent group represented by the following formula (b1). Formula (bl):

式中，各構造式中存在之複數個R2各自獨立表示氫原子或曱基。該等之中，以R2均為氫原子之交聯基為佳。本發明之式（1)所示的多元羧酸組成物係可藉由使對應上述式（1)之P的二元醇化合物、與可經（^至C6烷基（較佳為曱基）或羧基取代之六氫酞酸酐進行加成反應而獲得。本發明之多元羧酸組成物可依下述製法而得。本發明中，對於得到包含上述式（1)所示之多元羧酸的至少2種之多元羧酸組成物的方法，係有將以上述方法而得之單一的式（1)所示之多元羧酸的至少2種進行混合之方法；或在將上述之式（1)所示的多元羧酸進行合成時，作為上述六氫酞酸酐而使用至少2種之混合物或使用2種之上述二元醇，然後進行加成反應之方法。本發明中，對於得到包含上述式（1)所示之多元羧酸的至少1種與可經甲基取代之C4至C7環二、三或四羧酸酐 5-¾ 17 322150 201120000 雙方的多元羧酸組成物之方法，可列舉下述之方法。 (1) 將以上述方法而得之單一的式（1)所示之多元羧酸的觅少1種、與可經甲基取代之（：4至C7環二、針進行混合之方法；或者， β (2) 在將上述之式（1)所示的多元羧酸進行合成時，將作為其中之一的原料使用之可經甲基或羧基取^之六氫酞酸酐過量使用，使反應後之反應液中，作為原料使用之式（1) 所示的多元羧酸與上述酞酸酐為共存方式之方去。式（1)所示之多元羧酸的合成中使用之上述酸酐係可列舉如具有環己烷構造，且在該環己烷環上具有甲基取代或羧基取代、或無取代’並在分子内具有丨個以上（以1 個為佳）鍵結於己炫1 $衣之酸哥基的多元竣酸肝。具體上可列舉如· 1 ’ 2, 4_己嫁*一緩酸~1，2_野、4~••甲基環己炫-1，2_ 二羧酸酐或環己烷-1,2-二羧酸酐等。在得到式（1)所示之多元缓酸的單一化合物時’係可使用上述酸酐之任一種以進行反應。在得到本發明之多元幾酸組成物時，如上所述，係使用該等羧酸之至少2種以進行反應，或者，相對於上述二元醇，將該等羧酸之至少1種使用過量而進行反應，較佳者係在反應結束後成為酸酐含在反應液中之型態者。該等酸酐至少使用2種時，可為任意之2種，惟在本發明中，從光學特性上’係以Ci至Ce烷基（以甲基為佳）或/及羧基取代之六氫酞酸酐為佳，無取代之六氫酿酸酐宜少於50重量％ ’以40重量％以下為佳，以35重量％以下更 18 322150 201120000 佳’又以30重量％以下為特佳。在以下說明書中，％如無特別指定即為重量％之意。酸酐至少使用2種時，經甲基取代或/及羧基取代之六氫酞酸酐在全部酸酐中，以65%以上為佳，以85%以上更佳’以90%以上為特佳。對於式（1)所示之多元羧酸的合成中使用之上述原料的一 το醇刊舉如在交聯基p之^末端附錢基的二元醇。具體上，係在以⑷所定義之交聯基中含有具總碳數6 至20之分支構造的鏈狀烷基鏈之二元醇。更具體言之，在碳數3至12之主鏈的兩末端具有羥基，並在該主鏈上且有2至4個側鏈’且該側鏈之至少i者（以至少2者為佳）為碳數2至1〇之二元醇。文具體兮物係可列舉如在上述式（al)所記载父聯基中，*記號之位置上鍵結有羥基之化合物。作為原料使用之二元醇中，係以至少具有2個側鍵該侧鏈中至少2個為碳數2至4之側鏈的二元醇為佳。在如此骨架中，特佳之二元醇係可列舉如2,4一二乙』 -1，5-戍二醇、2_乙基_2_丁基丙二醇、2_乙約3 己二醇等，特別以2’4二乙約，5_戊二醇為佳。， -式⑴+以上述⑹所定義之交聯基時之交聯多環：In the formula, a plurality of R2 present in each structural formula each independently represent a hydrogen atom or a thiol group. Among these, it is preferred that R2 is a crosslinking group of a hydrogen atom. The polycarboxylic acid composition represented by the formula (1) of the present invention can be obtained by reacting a diol compound corresponding to P of the above formula (1) with a (^ to C6 alkyl group (preferably a thiol group). Or a carboxy-substituted hexahydrophthalic anhydride is obtained by an addition reaction. The polycarboxylic acid composition of the present invention can be obtained by the following method. In the present invention, a polycarboxylic acid represented by the above formula (1) is obtained. A method of mixing at least two kinds of polyvalent carboxylic acid compositions, wherein at least two of the polycarboxylic acids represented by the formula (1) obtained by the above method are mixed; or the above formula (1) When the polycarboxylic acid shown is synthesized, a mixture of at least two kinds of the above-described hexahydrophthalic anhydride or a mixture of two kinds of the above-mentioned diols is used, and then an addition reaction is carried out. In the present invention, A method of arranging at least one polyvalent carboxylic acid represented by the formula (1) and a polyvalent carboxylic acid composition of a C4 to C7 cyclodi, tri or tetracarboxylic anhydride 5 - 5⁄4 17 322 150 201120000 which may be substituted by a methyl group, The following method: (1) The single equation (1) obtained by the above method is shown. a polycarboxylic acid having one hydrazine, a method of mixing with a methyl group (: 4 to C7 ring two, a needle; or, β (2) a polycarboxylic acid represented by the above formula (1) When the synthesis is carried out, the hexahydrophthalic anhydride which can be used as a raw material by a methyl group or a carboxyl group is used in excess, and the polyhydric carboxylic acid represented by the formula (1) used as a raw material in the reaction liquid after the reaction is used. The acid and the above-mentioned phthalic anhydride are in a coexistence manner. The above-mentioned acid anhydride used in the synthesis of the polyvalent carboxylic acid represented by the formula (1) may, for example, have a cyclohexane structure and have a methyl group on the cyclohexane ring. Substituted or carboxy-substituted, or unsubstituted, and having more than one (more preferably one) in the molecule bonded to the poly-citric acid liver of the acid-based G-based group. Specifically, for example, 1 ' 2, 4_ already married * a slow acid ~ 1,2_ wild, 4 ~ • • methylcyclohexan-1, 2_ dicarboxylic anhydride or cyclohexane-1,2-dicarboxylic anhydride, etc. (1) When a single compound of a polybasic acid retardation is shown, any one of the above acid anhydrides can be used to carry out the reaction. The polybasic acid composition of the present invention is obtained. As described above, at least two of the carboxylic acids are used to carry out the reaction, or at least one of the carboxylic acids is used in an excess amount to react with the diol, preferably at the end of the reaction. Then, the type of the acid anhydride is contained in the reaction liquid. When the acid anhydride is used in at least two kinds, it may be any two, but in the present invention, the optical property is 'Ci to Ce alkyl (in the case of A Preferably, the base is preferably or carboxy substituted hexahydrophthalic anhydride, and the unsubstituted hexahydro styrene is preferably less than 50% by weight 'below 40% by weight or less, 35% by weight or less and 18 322150 201120000' Further, it is particularly preferably 30% by weight or less. In the following description, % is meant to be % by weight unless otherwise specified. When at least two kinds of acid anhydrides are used, the hexahydrophthalic anhydride substituted with a methyl group or/and a carboxyl group is preferably 65% or more in all the acid anhydrides, more preferably 85% or more, and particularly preferably 90% or more. The τ octanol of the above-mentioned starting materials used in the synthesis of the polycarboxylic acid represented by the formula (1) is exemplified as a diol having a hydroxyl group at the end of the crosslinking group p. Specifically, it is a diol having a chain alkyl chain having a branched structure of a total carbon number of 6 to 20 in the crosslinking group defined by (4). More specifically, having a hydroxyl group at both ends of the main chain having 3 to 12 carbon atoms, and having 2 to 4 side chains ' on the main chain and at least i of the side chains (preferably at least 2) ) is a glycol having 2 to 1 carbon atoms. Specific examples of the oxime system include a compound in which a hydroxyl group is bonded to a position of a * mark in the parent group described in the above formula (al). The diol used as a raw material is preferably a diol having at least two of the side chains and at least two of the side chains of a side chain having 2 to 4 carbon atoms. Among such skeletons, particularly preferred glycols include, for example, 2,4-diethyl-1,3-propanediol, 2-ethyl-2-butene propylene glycol, 2-ethylidene-3 hexanediol, and the like. In particular, 2'4 diethyl, 5_pentanediol is preferred. , - (1) + cross-linked polycyclic ring when the cross-linking group is defined by the above (6):

转係將三環魏構造、五料五域造作為主要骨㈣一凡醇類，係以下述式（b2)表示。 J 322150 19 £· 201120000The transgenic line is composed of the tricyclic Wei structure and the five-material five-domain structure as the main bone (four), and the alcohol is expressed by the following formula (b2). J 322150 19 £· 201120000

式中，存在之複數個R2各自獨立表示氫原子或甲基。具體上可列舉如三環癸烷二甲醇、甲基三環癸烷二甲醇、五環十五烷二曱醇等。酸酐與二元醇之反應一般為將酸或鹼作為觸媒之加成反應，惟本發明中特別以在無觸媒下之反應為佳。使用觸媒時，可使用之觸媒可列舉例如：鹽酸、硫酸、甲磺酸、三氟甲磺酸、對甲苯磺酸、硝酸、三氟乙酸、三氣乙酸等酸性化合物；氫氧化納、氫氧化鉀、氫氧化飼、氫氧化鎂等金屬氫氧化物；三乙胺、三丙胺、三丁胺等胺化合物；吡啶、二曱胺基吡啶、1，8-二氮雜二環[5. 4. 0] Η—碳-7-烯、_°坐、三°坐、四σ坐等雜環式化合物；氫氧化四甲銨、氫氧化四乙銨、氫氧化四丙銨、氫氧化四丁銨、氫氧化三甲基乙基銨、氫氧化三甲基丙基銨、氫氧化三甲基丁基銨、氫氧化三甲基十六烷基銨、氫氧化三辛基甲基銨、氯化四曱銨 '溴化四曱錄、蛾化四曱銨、乙酸四曱銨、乙酸三辛基曱基銨等四級銨鹽等。該等觸媒可使用1種或將2種以上混合使用。該等之中，以三乙胺、吡啶、二曱胺基吼咬為佳。 20 322150 201120000 觸媒之使用量並無限制，惟依需要而使用相對於原料之總量100重量份為〇.〇〇1至5重量份者為佳。本反應係，以在無溶劑下之反應為佳，惟亦可使用有機溶劑。有機_之❹量，相躲料反應歸之上述酸酐與上述二元醇之總量i份，其重量比為G篇至i份，以〇. 005至〇. 7份為佳，以U05至0.5份（亦即50重量％以了）更佳^機溶狀使用量在相對於上述反應基質i 重量份的重量比超出1份時，因反應之進行變的極為緩慢而不佳。可使用之有機溶劑的具㈣可列舉如己燒、烧、庚院等烧類；甲苯、二甲苯等芳香族烴化合物；^ 乙”同f基異丁_、環戊酮、環己酮等酮類；二***：四氫呋喃、二噚烷等醚類；乙酸乙酯田醋等酿化合物等。 us曰乙酸甲巧虛本反應^即使在2『C左右之溫度中亦可充分地進反應。從反應時間之問題上，反應溫度以3〇至1订以4〇至航更佳’尤以4Q至靴為特佳。為隹’ 無:劑下進行本反應時，因有酸肝的揮發，係以在7二 :r應為佳’⑷。至靴-至就之二: 莫耳下上=述:可元::反應比率，理論上宜為在等述，在作為本發明4:必要而變更。亦即’如下所明的多元麟組錢^^用硬化·成物使用之本發 ⑴之多元銳與上述^為液狀之硬化劑❹的包含式辻黾酐之組成物時’特別是在式（1)之 21 322150 201120000 多元羧酸的合成中使用的酸酐與調配在該多元羧酸組成物中的酸酐為相同時，在製造時，相對於上述二元醇而在過剩之上述酸酐中進行反應，在該酸酐與該二元醇之反應結束之時點，可作為該酸酐與上述式（1)之多元羧酸的混合物 (硬化劑組成物）。使反應時之具體兩者的饋入比率係，以其官能基當量，相對於該酸酐基1當量，以饋入該二元醇使其羥基當量成為0. 001至2當量之比例者為佳，以0. 01至1. 5當量更佳，又以0. 01至1. 1當量最佳。如上述之製造硬化劑組成物時，該二元醇以其羥基當量，一般係在0.01至0.7 當量之範圍内使用，以0. 01至0. 5當量為佳。 - 反應時間亦依反應溫度、觸媒量等而異，然從工業生產之觀點上，由於長時間之反應會消耗極大的能源而不佳。並且，過短之反應時間意指其反應急遽，從安全面而言並不佳。較佳之範圍約為1至48小時，以1至36小時為佳，以1至24小時更佳，又以2至10小時左右為特佳。反應結束後，經使用觸媒時，分別經由中和、水洗、吸附等而進行觸媒之去除，在餾除溶劑後而得到目的之多元羧酸。並且，在無觸媒之反應中，可因應必要而餾除溶劑，進一步在無溶劑、無觸媒時，可直接取出作成製品。最為適合之製造方法係使上述酸酐、上述二元醇於40 至150°C中且在無觸媒、無溶劑之條件下反應，反應結束後，直接將其取出之手法。如此而得的上述式（1)所示之多元羧酸或含有該多元 22 322150 201120000 無色至淡黃色，的樹- I吊’式（1)之交聯基p如為（a)所定義伸燒基時，則呈現無色至淡黃色之_的樹以有側鏈的之交聯基P如為從⑷所定義之交❹環⑴ 基後之2價交聯基時，以及即使為⑷所 :去除經係呈現液=反料，反應生成物㈣況，其形狀1 式（1)之交聯基p如為（b)所定義之交聯均為氫原子之多元羧酸在硬化時可見到著：二取代基 :的光學用途上並不適用。R為甲基或竣基之化:別在嚴 h有如此之著色’可提高其鮮特性。中，以Si上述式⑴之(a)所定義之交聯基的化人物 I。基或縣之化合物者，_提高光學祕t 為甲發:二物的較佳者係宜含有R 凡熳基、或兼具兩者之式（1)的多元如為含有2種以上之鮮元_❹元_ = = f物。至少R非為氫原子的式⑴之多⑽酸⑺為上:將基為佳）或竣基之多元缓酸），L、元土以曱含右π钱ΧΓΠ 1竣酸之總量，以莫耳％以上之組成物為佳。更佳者氫原子的式⑴之多元賊7()莫耳％以上、’、3有/非為耳％以上的多元舰組成物。殘餘取係90莫之多元鲮酸。為氧原子的式（1) 23 S. 322150 201120000 H 的多元緩酸，較佳者係R為氫原 ^卜之基(；更佳者係R為曱基或羧基）的多元缓酸、或含有此多元㈣之本發明的多元致酸組成物，其透明性優異’可使用作為環氣樹脂之硬化劑、塗料、接著劑、成形 -、半導體、光半導體之密封材料用樹脂、光半導體之黏阳材料用樹脂、聚酸胺樹脂、聚醯亞胺樹脂等之原料或改質劑、塑化劑及潤滑油原料、醫藥農藥中間產物、塗料用樹脂之原料、色劑用樹脂。特別在將本發明之多元羧酸組成物作為環氧樹脂的硬化劑使用時.，硬化性能佳，其硬化物之透明度優異。因此，本發明之多元羧酸組成物極適用作為高亮度之白色LED以及其它之光半導體的密封中所使用之環氧樹脂用硬化劑。其次’對於在本發明之多元羧酸組成物中作為液狀硬化劑使用時，含有式（1)之多元缓酸與駿酐的本發明之多元繞酸組成物進行說明。該多元羧酸組成物之較佳者係包含式（丨）之多元叛酸與可經曱基取代的C4至C7環二、三或四綾酸軒，兩者之比例係’相對於式（1)之多元羧酸1重量份，該酸酐之比例為 0. 1至10重量份，以〇· 5至8重量份為佳，以i至8重量份更佳。該多元缓酸組成物係，所含上述酸軒與在製造式（1) 之多元羧酸時所使用的酸酐為相同物質時，則如上所述，在製造式（1)之多元竣酸時，將作為原料使用之酸酐，相對於作為原料使用之二元醇，使反應後殘留的酸針成為上述 322150 24 201120000 範圍之方式，藉由過剩使用所製造而得、、接或作為本發明之多元叛酸組成物使用者為=液以可直該多元紐組祕之其它的製造方法係佳可藉由將上，所得的式⑴之多元魏與上述可”基取代二至& 衣二二或四㈣㈣上述之比例均勻地溶解混合而獲得。 =元㈣㈣财所含料⑴^讀酸可為（ ^或2種以上之複數種。所含的式⑴之多元紐為β 之多元麟係如上所述，以R為甲基或絲之化並且’在含有複數種的式⑴之多元減時，相 = 之總量’式⑴中之基或絲的多元夂3 1以50莫耳％以上為佳，以65莫耳％以上更佳。 r 5 2可^甲基取代之^至^7環二、三或四減針如為西堯上具有2至4個（以2至3個為佳）缓基的多元缓夂=酐’則無特別障礙。具體上可列舉如六纽酸針、 :基六氫峨酐、丁炫讀_、雙環[2,2,丨]庚烧_2,3_ 竣酉夂酐_ f基雙_[2, 2, 3_二缓酸肝、環己烧一，2,4—三羧酸-1，2-酐等。較佳者係可經甲基或羧基取代 =己燒二紐酐（可經甲基或祕取代之六氣駄酸肝）較 /該等之例可列舉如：六氫㈣if、甲基六纽酸酐或 %己烷-1，2,4-三羧酸—1，2-酐等。土在該多元羧酸組成物中，式（1)之多元羧酸所佔的較仏比例，相對於上述酸酐與該多元羧酸之總重，係2〇至 80重量％ ’以30至75重量％更佳。接著，對於本發明之環氧樹脂用硬化劑進行說明。 25 322150 «9 201120000 本發明之環氧樹脂用硬化劑係包含式（1 )之多元緩酸、或含有該多元羧酸與酸酐之硬化劑。式（1)之較佳的多元敌酸可列舉如R為風原子以外之多元叛酸，更佳者係r 為甲基或羧基之多元羧酸，尤其是所有的R為甲基或羧基之多元缓酸。將式（1)之多元羧酸作為環氧樹脂之硬化劑，特別是作為液狀硬化劑使用時，係以混合液狀之酸酐作為液狀之本發明的多元羧酸組成物者為佳。該液狀之組成物可適用為本發明的環氧樹脂用硬化劑組成物。可使用之液狀的酸酐係以該構造中不具有芳香環而具有飽和環構造之酸酐為佳。具體上可為上述本發明之多元紐組成物的各處所列舉之酸針。又，調配比例等亦以同處所說明之範圍為佳。因此’上述包含式（1)之多元羧酸與酸酐的本發明之多元羧酸組成物可直接作為本發明之環氧樹脂用硬化劑組成物使用0 本硬化劑中，亦可同時含有以下所記載之硬化觸媒、添加劑、無機充填材等。 > 士以下係記載有關包含式（1)之多元羧酸或本發明之環氧树舳用硬化劑的本發明之硬化性樹脂組成物。本發明之硬化性樹脂組成物係含有作為必環氧樹脂。茺战刀之在本發明之硬化性樹脂組成物中使用的環氧樹脂 Γ:择如酚醛型環氧樹脂、雙酚A型環氧樹脂、聯苯』環氧樹知、二苯甲烷型環氧樹脂、苯酚芳烷基型環氧樹脂等。 322150 26 201120000 具體上可列舉如雙酶A、雙盼s、硫二盼、 4, 4’-雙酚、2, 2，-雙紛、3 又酚苐萜一酚、基]-“，-二^對笨二^’^/四甲基屮乂-聯苯苯基）曱烧、1，1，2,2-四（4 '蔡二醇 '三（4~經取代之驗、蔡紛、燒基取^賴（盼、炫基等）與甲醛、乙醛、苯甲醞匕基本、一羥基萘對經基苯乙嗣、鄰經基基=、鄰經基苯㈣、 4, 4、二(氣甲基⑷ 戍二烯、吱喃甲駿、 1，Γ-聯苯、1’4-二"田二（曱氧基曱基）_ 之縮聚物以及該等之改質^)·本、^4、二（甲氧基甲基）苯等類、醇類所衍生之縮水甘油二雙:二f:雙紛水甘油胺系環氧樹脂、縮水甘油酿系;=t 縮院（silsesquiQxane)$ μ錢_、倍半石夕氧或者續等之至少2錄、讀樹月曰（在鍵狀、環狀、梯狀， ==='的混合構造之•具有液狀之環：榭g二己烷構造之環氧樹脂)等固形或狀之衣氧树月曰，惟並不限於該等。特別疋將本發明之硬化性樹脂組成物使用在光學用钟環氧樹脂係以腊環式環氧樹脂或/及含有環氧基之石夕氧樹月曰（較佳者係倍半石夕氧炫構造之環氧樹脂）為佳，特別以兩者之併用為佳。 _尤其在脂環式環氧樹脂時，以骨架上具有環氧基環己烷構造之化合物為佳，以具有環己烯構造之化合物經氧化反應而得的環氧樹脂為特佳。該等脂環式環氧樹脂可列舉如可藉由環己烯羧酸與 ti. 322150 27 201120000 醇類之酯化反應或環己烯曱醇與羧酸類之酯化反應 (Tetrahedron vol. 36 ρ. 2409(1980)' Tetrahedron Letter P. 4475(1980)等所記載之手法）、或者環己烯醛之蒂森科反應（Tischenko reaction)(日本特開 2003-170059 號公報、曰本特開2004-262871號公報等所記載之手法）、再有環已烯綾酸酯之酯交換反應（日本特開2〇〇6_〇52187號公報等所記载之手法）而製造的化合物經氧化之物等。醇類如為具有醇性經基之化合物，則無特別限定缺可列舉如乙二醇、丙二醇、13—丙二醇、丨，2_丁二醇、丨，二丁二醇、1，5-戊二醇、i，6乂二醇、環己烷二曱醇丙三醇、三經甲基乙烷、三羥甲基丙烷、三羥甲基丁 ς、2-赵甲基u-丁二醇等三醇類；季戊四醇等等。羧酸類可列舉如丁二酴貝鄰苯二甲酸、間苯二甲：、己=稀:酸、反丁，、並不限於此等。 &、衣己院-舰等，惟盤化舉麻如二己歸酸衍生物與醇體經縮搭反應之縮例如已揭示在反齡之祕化反騎可製造，共彿脫水，-邊進行心之甲本、二曱笨等溶媒，—邊報）；將多元醇溶解於濃鹽（美國專利第2945_號公邊進行反應之方法（日本，一邊徐緩地添加醛類，一介質中使用水之方法（義^昭48'9_號公報）；在反應應介質中使时機溶媒^利第3g9264g號公報）；在反報）；使用固體酸觸媒之方日本特開平7_21_號公在（日本特開2007-230992號公 322150 28 201120000 報）等。從構造之安定性而言，以環狀縮醛構造為佳。可列舉如乙烯基環己烯或檸檬烯、二環戊二烯、三環戊一烯、曱基二環戊二烯、二環己烯、辛二烯等脂環式多 - 元烯烴經氧化之物等。該等環氧樹脂之具體例可列舉如：ERL-4221、 ERL 4299(全部為商品名，均為d〇w chemical公司製造）、 EPOLEAD GT401、EHPE3150、EHPE3150CE(全部為商品名，均為Daicel chemical工業公司製造）以及二環戊二烯二環氧化物等，然並不限於該等（參考文獻：環氧樹脂總論基礎篇I p76-85頁）。該等可單獨使用亦可將2種以上併用。較佳之脂環式環氧樹脂係以可具有甲基之環氧基環己基，例如以-C00-CH2-、-C00-(C3至C8之2價飽和脂肪族基）-COO-、-Clh-COO-(C3至Cs之2價飽和脂肪族基）-C00- 或-CHz-COO-CC3至Cs之2價飽和脂肪族基）-C00-CH2-等交聯基鍵結之2官能環氧樹脂為佳。含有環氧基之石夕酮樹脂係以倍半石夕氧烧構造之環氧樹脂為隹。倍半矽氧烷構造之環氧樹脂係以具有環氧基環己烷構造之有機聚矽氧烷為佳。更佳者係重量平均分子量在1000以上、20, 000以下（以1000以上、1〇, 〇〇〇以下為佳）之含有環氧基的矽酮樹脂’再更佳者係具有環氧基環己烷構造之有機聚矽氧烷。本發明中’特別是經由將具有環氧基環己基之烷氧矽院在原料中使用之溶膠一凝膠反應（So 1 -Ge 1 React i on)而得的化合物。 29 322150 201120000 具體上可列舉如日本特開2004—2566〇9號公報、日本特開2004-346144號公報、國際公開第2〇〇4/〇7215〇號、日本特開2006-8747號公報、國際公開第2〇〇6/〇〇399〇號、。曰本特開2006-104248號公報、國際公開第2〇〇7/1359〇9 號、日本特開2004-10849號公報、日本特開2〇〇4_359933 號公報、國際公開第2005/100445號、日本特開 2008-174640號公報等中記载之具有分布在三度空間中的網眼狀構造之倍半矽氧烷型的有機聚矽氧烷。在倍半矽氧烷構造方面並無特別限定，惟因單純的三度空間之網眼構造的石夕氧烧過硬，因而期待有可緩和硬度之構造。本發明中，特別以1分子中具有石夕酮段與經由溶膠一凝膠反應而得的上述倍切氧賴造之嵌段構造體為佳。如此化合物之製造法可列舉如國際公開第2010/026714號所記載之製造方法以及構造。本發明之硬化性樹脂組成物中，式（i)之多元羧酸（或 T化劑組成物）可與其它之硬化劑併用。併用時，式（1)之夕π羧酸佔全部硬化劑中之比例係以20重量％以上為佳，尤以30重量％以上更佳。可併用在式（1)之多元羧酸中的硬化劑可列舉例如胺系化合物、具有不飽和環構造之酸酐系化合物、醯胺系化口物、酚系化合物、羧酸系化合物等。可使用之硬化劑的具體例可列舉二胺基二笨基代、二伸乙三胺、三伸乙四胺、二胺基二笨基硬、異佛爾_二胺、雙氰胺、經亞麻酸 322150 201120000 之2聚物與乙二胺所合成的聚醯胺樹脂、駄酸肝、偏苯三酸酐、苯均四酸酐、馬來酸酐、四氫酞酸酐、甲基四氫酞酸if、曱基納迪克酸針（Nadic Methyl Anhydride)、納迪 . 克酸酐、六氫酞酸酐、曱基六氫酞酸酐、丁烷四羧酸酐、 • 二環[2’2’1]庚烷3-二羧酸酐、甲基二環[2, 2, 1]庚烷 -2’ 3-二羧酸酐、環己烷_丨，3, 4_三羧酸_3, 4_酐、雙酚a、雙酚F、雙酚S、雙酚第、萜二酚、4, 4,-雙酚、2, 2,-雙酚、 3, 3’，5’ 5’ _四曱基-[1，1，_聯苯基]_4, 4’ _二醇、對苯二酚、間苯二酚、萘二醇、三（4_羥苯基）曱烷、丨，丨，2,2一四 (4-羥苯基）乙烷、酚類（酚、烷基取代之酚、萘酚、烷基取代之萘酚、二羥基笨、二羥基萘等）與甲醛、乙醛、苯甲醛、對爹二基笨甲盤、鄰經基苯甲駿、對經基苯乙酮、鄰經基苯乙=、二環戊二烯、呋喃甲醛、4,4，-二（氣甲基）-1，1，-聯苯、—4,4 _二（甲氧基甲基）-1，1，-聯苯、1,4，-二（氯甲基）苯1，4 ''一（甲氧基甲基）苯等之縮聚物以及該等之改質物，四/臭雙酚A等之鹵化雙酚類；咪唑、三氟化硼_ #胍彳4生物' @與吟類之縮合物等，然並不限於該等該等可單獨使用，亦可使用2種以上。本發明之硬化性樹脂組成物中，硬化劑與環氧樹脂之In the formula, the plurality of R2 present independently represent a hydrogen atom or a methyl group. Specific examples thereof include tricyclodecane dimethanol, methyl tricyclodecane dimethyl alcohol, pentacyclopentadecanedonol, and the like. The reaction of the acid anhydride with the diol is generally an addition reaction using an acid or a base as a catalyst, but in the present invention, it is particularly preferred to carry out the reaction without a catalyst. When a catalyst is used, examples of the catalyst that can be used include acidic compounds such as hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, nitric acid, trifluoroacetic acid, and tri-glycolic acid; a metal hydroxide such as potassium hydroxide, hydrogen hydroxide or magnesium hydroxide; an amine compound such as triethylamine, tripropylamine or tributylamine; pyridine, diammonium pyridine, 1,8-diazabicyclo[5 4. 0] 杂环-carbon-7-ene, _° sitting, three-degree sitting, four-sigma sitting and other heterocyclic compounds; tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, hydrogen hydroxide Butyl ammonium, trimethylethylammonium hydroxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylhexadecyl ammonium hydroxide, trioctylmethylammonium hydroxide, a tetra-ammonium salt such as tetraammonium chloride, tetrabromide, mothium tetraammonium chloride, tetraammonium acetate, trioctyl ammonium thioglycolate or the like. These catalysts may be used alone or in combination of two or more. Among these, it is preferred to use triethylamine, pyridine or diamine. 20 322150 201120000 The amount of catalyst used is not limited, but it is preferably used in an amount of from 1 to 5 parts by weight based on 100 parts by weight of the total amount of the raw materials as needed. This reaction system is preferably a reaction in the absence of a solvent, but an organic solvent may also be used. The amount of organic ,, the phase reaction is determined by the total amount of the above acid anhydride and the above diol, the weight ratio of G to i, 〇. 005 to 〇. 7 is better, U05 to When 0.5 parts by weight (i.e., 50% by weight or more) is used in an amount exceeding 1 part by weight based on the weight of the reaction substrate i, the progress of the reaction becomes extremely slow and unsatisfactory. Examples of the organic solvent that can be used include (4) aromatics such as hexane, roast, and gypsum; aromatic hydrocarbon compounds such as toluene and xylene; and ethyl b-isobutyl ketone, cyclopentanone, cyclohexanone, and the like. Ketones; diethyl ether: ethers such as tetrahydrofuran and dioxane; ethyl acetate vinegar and other brewing compounds, etc. us 曰曰曰巧虚虚本 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ 。。。。 From the reaction time, the reaction temperature is set to 3 〇 to 1 〇 to a better voyage', especially 4Q to the boots. It is especially good for the 隹' no: under the agent, due to the evaporation of sour liver , in the 7 2: r should be better '(4). To the boots - to the second: Moe down = said: can be:: reaction ratio, theoretically should be in the above, in the present invention 4: If necessary, it is changed as follows: 'In particular, the acid anhydride used in the synthesis of the polycarboxylic acid of the formula (1) 21 322150 201120000 is the same as the acid anhydride formulated in the polycarboxylic acid composition. At the time of production, the reaction is carried out in excess of the above-mentioned acid anhydride with respect to the above-mentioned diol, and when the reaction of the acid anhydride and the diol is completed, the acid anhydride and the polycarboxylic acid of the above formula (1) can be used. a mixture (hardener composition). The feed ratio of the specific two at the time of the reaction is, based on the functional group equivalent, 1 equivalent of the anhydride group, to feed the diol to have a hydroxyl equivalent of 0. The ratio of 001 to 2 equivalents is preferably from 0.01 to 1.5 equivalents, and more preferably from 0.01 to 1.1 equivalents. When the hardener composition is produced as described above, the diol is The hydroxyl equivalent weight is generally used in the range of 0.01 to 0.7 equivalents, preferably from 0.01 to 0.5 equivalents. - The reaction time also varies depending on the reaction temperature, the amount of catalyst, etc., from the viewpoint of industrial production. Because long-term reaction will consume a lot of energy, and too short reaction time means that the reaction is impatient, which is not good from the safety surface. The preferred range is about 1 to 48 hours, from 1 to 36 hours is better, 1 to 24 hours is better, and 2 to 10 hours is especially good. After the completion of the reaction, when the catalyst is used, the catalyst is removed by neutralization, water washing, adsorption, or the like, and the desired polycarboxylic acid is obtained by distilling off the solvent, and in the reaction without a catalyst, If necessary, the solvent is distilled off, and when it is solvent-free or catalyst-free, it can be directly taken out as a product. The most suitable production method is to make the above-mentioned acid anhydride and the above-mentioned glycol at 40 to 150 ° C and without catalyst, The reaction is carried out under the condition of no solvent, and the reaction is directly taken out after the completion of the reaction. The polycarboxylic acid represented by the above formula (1) or the tree containing the plural 22 322150 201120000 colorless to pale yellow, I-hang When the cross-linking group p of the formula (1) is a stretching group as defined in (a), the tree exhibiting a colorless to pale yellow color has a cross-linking group P having a side chain as defined in (4). When the fluorene ring (1) is a 2-valent cross-linking group after the base, and even if it is (4): removing the warp-presenting liquid=reverse material, the reaction product (4), the cross-linking group p of the shape 1 (1) is (b) The polycarboxylic acid defined by cross-linking is a hydrogen atom which is visible during hardening: disubstituted : Not available on optical purposes. R is a methyl or sulfhydryl group: do not have such a color in the strict h' to improve its fresh characteristics. In the above, the person I of the cross-linking group defined by the above formula (1) (a) is Si. The compound of the base or the county, _ enhances the optical secret t is a hair loss: the preferred one of the two substances preferably contains R 熳熳, or both of the formula (1), such as two or more Yuan_❹元_ == f. At least R is not a hydrogen atom of the formula (1), the (10) acid (7) is: the base is preferably) or the sulfhydryl group is a polybasic acid, and the L, the meta-soil is the total amount of the π ΧΓΠ ΧΓΠ ΧΓΠ 竣竣The composition of more than % by mole is preferred. More preferably, the multi-ship composition of the hydrogen atom of the formula (1), the multi-thief 7 (), the mol% or more, the ', the 3's/the non-ears % or more. The residue is taken from a 90% polybasic acid. a polybasic acid of the formula (1) 23 S. 322150 201120000 H which is an oxygen atom, preferably a polybasic acid of the hydrogen group (more preferably R is a mercapto group or a carboxyl group), or The polybasic acid composition of the present invention containing the above-mentioned plural (4) is excellent in transparency, and can be used as a curing agent for a cycloolefin resin, a coating material, an adhesive, a molding, a semiconductor, a resin for a sealing material for an optical semiconductor, and an optical semiconductor. A raw material for a viscous material, a polyamic acid resin, a polyimide resin, or the like, a modifier, a plasticizer, a lubricant raw material, a pharmaceutical pesticide intermediate, a resin for a coating resin, and a resin for a toner. In particular, when the polyvalent carboxylic acid composition of the present invention is used as a curing agent for an epoxy resin, it has excellent curing properties and excellent transparency of the cured product. Therefore, the polycarboxylic acid composition of the present invention is extremely suitable as a curing agent for epoxy resins used for sealing high-brightness white LEDs and other optical semiconductors. Next, the multicomponent acid composition of the present invention containing the polybasic acid of the formula (1) and the phthalic anhydride will be described when it is used as a liquid hardener in the polyvalent carboxylic acid composition of the present invention. The preferred composition of the polycarboxylic acid composition comprises a multi-repulsive acid of the formula (丨) and a C4 to C7 ring di-, tri- or tetradecanoic acid substituted by a mercapto group, the ratio of which is 'relative to the formula ( 1) The polycarboxylic acid is 1 part by weight, and the ratio of the acid anhydride is 0.1 to 10 parts by weight, preferably 5 to 8 parts by weight, more preferably 1 to 8 parts by weight. When the polybasic acid-reducing composition contains the same acid as the acid anhydride used in the production of the polycarboxylic acid of the formula (1), as described above, in the case of producing the polybasic acid of the formula (1) The acid anhydride used as a raw material is obtained by using an excess amount of the acid used as a raw material, and the acid needle remaining after the reaction is in the range of 322150 24 201120000, which is produced by excess use, or as the present invention. The user of the multi-repulsive acid composition is a liquid, and the other manufacturing method of the multi-component composition can be obtained by using the above-mentioned multi-dimensions of the formula (1) and the above-mentioned keis-substituted two to & Two or four (four) (four) The above ratio is uniformly dissolved and mixed to obtain. = yuan (four) (four) financial materials (1) ^ reading acid can be (^ or more than two kinds of multiple species. The multi-nucleus of formula (1) is a multi-component of β As described above, R is methyl or silk and 'in the total amount of the formula (1), the total amount of the phase = the base in the formula (1) or the multicomponent 夂 3 1 of the filament is 50 moles. More than % is better, more preferably 65 mol% or more. r 5 2 can be methyl substituted ^ to ^7 ring two, three or four reduction needles, such as two to four (two to three are preferred) on the Xiqiao, the multiple retardation = anhydride 'has no special obstacles. Specifically, for example Hexazone needle, : hexahydrophthalic anhydride, Ding Xuan read _, double ring [2, 2, 丨] heptane _2, 3_ phthalic anhydride _ f bis-[2, 2, 3_ bis-acid Liver, cyclohexanone, 2,4-tricarboxylic acid-1,2-anhydride, etc. It is preferred to be substituted by methyl or carboxyl group = hexanol hexahydro anhydride (six gas which can be substituted by methyl or secret) Examples of the citrate liver/such as: hexahydro (tetra)if, methylhexaic anhydride or % hexane-1,2,4-tricarboxylic acid-1,2-anhydride, etc. In the acid composition, the proportion of the polycarboxylic acid of the formula (1) is preferably from 2 to 80% by weight, based on the total weight of the above acid anhydride and the polycarboxylic acid, of from 30 to 75% by weight. Next, the hardener for epoxy resin of the present invention will be described. 25 322150 «9 201120000 The hardener for epoxy resin of the present invention contains a polybasic acid of the formula (1) or contains a hardening of the polycarboxylic acid and an acid anhydride. The preferred polybasic acid of formula (1) can be exemplified as R as a wind atom. A multi-repulsive acid, preferably a polycarboxylic acid in which r is a methyl group or a carboxyl group, especially all polybasic acid acids in which R is a methyl group or a carboxyl group. The polycarboxylic acid of the formula (1) is used as an epoxy resin. The hardening agent, particularly when used as a liquid hardener, is preferably a mixed liquid anhydride as a liquid polyvalent carboxylic acid composition of the present invention. The liquid composition can be applied to the epoxy of the present invention. A resin composition for a resin. A liquid acid anhydride which can be used is preferably an acid anhydride having a saturated ring structure without an aromatic ring in the structure. Specifically, it can be enumerated in each of the above-described multi-component compositions of the present invention. Acid needles. Also, the proportion of blending is also better than the range indicated in the same place. Therefore, the polyvalent carboxylic acid composition of the present invention containing the polyvalent carboxylic acid of the formula (1) and the acid anhydride can be directly used as the hardener composition for the epoxy resin of the present invention, and may also contain the following Hardened catalysts, additives, inorganic fillers, etc. described. > The following is a description of the curable resin composition of the present invention containing the polyvalent carboxylic acid of the formula (1) or the hardening agent for epoxide of the present invention. The curable resin composition of the present invention contains a reactive epoxy resin. Epoxy resin used in the curable resin composition of the present invention: phenolic epoxy resin, bisphenol A epoxy resin, biphenyl epoxide, diphenylmethane epoxy Resin, phenol aralkyl type epoxy resin, and the like. 322150 26 201120000 Specifically, for example, double enzyme A, double expectation s, thiophene, 4, 4'-bisphenol, 2, 2,-bis, 3, phenolphthalein, base]-", -二^对笨二^'^/Tetramethylhydrazine-biphenylphenyl) 曱, 1,1,2,2-tetra (4 'Caidiol' three (4~ replaced, Cai , burning base to take (Lao, Xuanji, etc.) and formaldehyde, acetaldehyde, benzamidine, monohydroxynaphthalene, p-aminophenylide, ortho-base =, ortho-phenyl (tetra), 4, 4 , a condensation polymer of bis (gas methyl (4) decadiene, sulfonium thiophene, 1, fluorene, biphenyl, 1'4-di " bis(nonyl fluorenyl) _ and the modification of these ), Ben, ^4, bis(methoxymethyl)benzene, etc., and glycidol derived from alcohols: two f: double glacial glycerin amine epoxy resin, glycidol brewing system; = t shrink (silsesquiQxane) $μ钱_, sesquiterate or continuation of at least 2 records, read tree 曰 (in a mixed structure of key, ring, ladder, ===' • with liquid Ring: 环氧树脂g dihexane structure epoxy resin) and other solid or shaped oxy-trees, but not limited to these. The curable resin composition of the invention is used in an optical resin epoxy resin, a wax ring type epoxy resin or/and an epoxy group-containing stone oxyphyllin (preferably, a sesquiterpene oxide structure) Epoxy resin is preferred, especially in combination with both. _ Especially in the case of an alicyclic epoxy resin, a compound having an epoxycyclohexane structure on the skeleton is preferred, and a cyclohexene structure is used. The epoxy resin obtained by the oxidation reaction of the compound is particularly preferred. The alicyclic epoxy resins may, for example, be esterified with cyclohexene carboxylic acid and ti. 322150 27 201120000 alcohol or cyclohexene oxime. Esterification of an alcohol with a carboxylic acid (Tetrahedron vol. 36 ρ. 2409 (1980) 'Tetrahedron Letter P. 4475 (1980), etc.) or a cyclohexene aldehyde (Tischenko reaction) Japanese Patent Publication No. 2003-170059, the method described in JP-A-2004-262871, and the like, and a transesterification reaction of a cyclohexene phthalate (Japanese Patent Publication No. 2〇〇6_〇52187) The compound produced by the method described in the above is oxidized or the like. The compound having an alcoholic trans group is not particularly limited, and examples thereof include ethylene glycol, propylene glycol, 13-propylene glycol, hydrazine, 2-butanediol, hydrazine, dibutylene glycol, and 1,5-pentanediol. a triol such as i,6-decanediol, cyclohexanedialol glycerol, trimethylethaneethane, trimethylolpropane, trimethylolbutanyl, 2-dimethylmethyl-butanediol; Pentaerythritol, etc. Examples of the carboxylic acid include, for example, dioxane phthalic acid, isophthalic acid, hexanyl acid, and anti-butyl, and are not limited thereto. &, Yijiyuan-ship, etc., but the shrinkage of the ruthenium derivative and the alcohol body by the phlegm of the ruthenium has been revealed, for example, in the anti-aging secret anti-riding can be manufactured, a total of dehydration, - While doing the solvent of the heart, the second and the second, and the like, the solvent is dissolved in the concentrated salt (the method of the reaction of the United States Patent No. 2945_ (the Japanese side, slowly adding the aldehyde, a medium) The method of using water in the medium (Izumi No. 48'9__); in the reaction medium, the timing of the solvent is controlled by the No. 3g9264g; in the counter-report; the use of the solid acid catalyst is the Japanese special Kaiping 7_21 _ No. in the public (Japan Special Open 2007-230992, public 322150 28 201120000 report) and so on. From the viewpoint of structural stability, a cyclic acetal structure is preferred. The alicyclic poly-membered olefin such as vinyl cyclohexene or limonene, dicyclopentadiene, tricyclopentene, decyl dicyclopentadiene, dicyclohexene or octadiene may be oxidized. Things and so on. Specific examples of such epoxy resins include ERL-4221 and ERL 4299 (all of which are trade names, all manufactured by d〇w Chemical Co., Ltd.), EPOLEAD GT401, EHPE3150, and EHPE3150CE (all of which are trade names, all of which are Daicel chemical). It is not limited to these (manufactured by Industrial Co., Ltd.) and dicyclopentadiene diepoxide, etc. (Reference: Basic Principles of Epoxy Resin, page I p76-85). These may be used alone or in combination of two or more. Preferred alicyclic epoxy resins are epoxycyclohexyl groups which may have a methyl group, for example, -C00-CH2-, -C00-(a C2 to C8 divalent saturated aliphatic group)-COO-, -Clh -COO-(2-valent saturated aliphatic group of C3 to Cs)-C00- or -CHz-COO-CC3 to Cs 2-valent saturated aliphatic group)-C00-CH2-is cross-linking bonded 2-functional ring Oxygen resin is preferred. The epoxy group-containing linoleic ketone resin is an epoxy resin having a sesquiterpene oxide structure. The epoxy resin having a sesquiterpene oxide structure is preferably an organopolyoxane having an epoxycyclohexane structure. More preferably, the epoxy group-containing fluorenone resin having a weight average molecular weight of 1,000 or more and 20,000 or less (preferably 1000 or more, 1 Å or less) is more preferably an epoxy ring. An organic polyoxane of hexane structure. In the present invention, a compound obtained by a sol-gel reaction (So 1 - Ge 1 React i on) which is used in a raw material of an alkoxy oxime having an epoxycyclohexyl group. 29 322150 201120000, for example, Japanese Patent Laid-Open No. 2004-2566-9, Japanese Patent Laid-Open No. 2004-346144, International Publication No. 2/4/7215, and JP-A-2006-8747. International Publication No. 2〇〇6/〇〇399〇, . Japanese Patent Publication No. 2006-104248, International Publication No. 2/7359/9, Japanese Patent Laid-Open Publication No. 2004-10849, Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. A sesquiterpene-type organopolyoxane having a network structure distributed in a three-dimensional space as described in JP-A-2008-174640. The sesquioxane structure is not particularly limited. However, since the simple three-dimensional space mesh structure is hard to burn, it is expected to have a structure that can alleviate hardness. In the present invention, in particular, the above-mentioned cleavage oxygen-forming block structure obtained by reacting a linaloketone moiety in one molecule with a sol-gel reaction is preferred. The production method and structure of the compound are as described in International Publication No. 2010/026714. In the curable resin composition of the present invention, the polycarboxylic acid (or the chemical composition) of the formula (i) may be used in combination with other hardeners. When used in combination, the ratio of the sulfocarboxylic acid of the formula (1) to the total amount of the hardener is preferably 20% by weight or more, more preferably 30% by weight or more. The curing agent to be used in the polyvalent carboxylic acid of the formula (1) may, for example, be an amine compound, an acid anhydride compound having an unsaturated ring structure, a guanamine compound, a phenol compound or a carboxylic acid compound. Specific examples of the hardener which can be used include diaminodiphenyl, diethylenetriamine, triethylenetetramine, diaminediphenyl, isophorol, diamine, dicyandiamide, and Linoleic acid 322150 201120000 2-mer and polyethylenediamine synthesized polyamine resin, citric acid liver, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrofurfuric acid if, sulfhydryl Nadic Methyl Anhydride, Nadi Acetic Anhydride, Hexahydrophthalic Anhydride, Mercapto Hexahydrophthalic Anhydride, Butane Tetracarboxylic Anhydride, • Bicyclo[2'2'1]heptane 3-Dicarboxyl Anhydride, methylbicyclo[2,2,1]heptane-2' 3-dicarboxylic anhydride, cyclohexane_丨, 3,4_tricarboxylic acid _3, 4-anhydride, bisphenol a, bisphenol F, bisphenol S, bisphenol, stilbene, 4, 4,-bisphenol, 2, 2,-bisphenol, 3, 3', 5' 5' _tetradecyl-[1,1,_ Biphenyl]_4, 4'-diol, hydroquinone, resorcinol, naphthalenediol, tris(4-hydroxyphenyl)decane, anthracene, anthracene, 2,2-14 (4-hydroxyl Phenyl) ethane, phenols (phenols, alkyl-substituted phenols, naphthols, alkyl-substituted naphthols, dihydroxy stupids, dihydroxynaphthalenes, etc.) Aldehyde, acetaldehyde, benzaldehyde, p-terenyl group, o-benzophenone, p-acetophenone, o-phenylphenidate, dicyclopentadiene, furfural, 4,4, - bis(gas methyl)-1,1,-biphenyl,-4,4-bis(methoxymethyl)-1,1,-biphenyl, 1,4,-bis(chloromethyl)benzene a polycondensate of 1,4 ''-mono(methoxymethyl)benzene and the like, and a halogenated bisphenol such as tetras/bisphenol A; imidazole, boron trifluoride _#胍彳4 The condensate of the genus and the hydrazine is not limited to these, and it may be used alone or in combination of two or more. In the curable resin composition of the present invention, a hardener and an epoxy resin

比相對於全％氧樹脂之環氧基工當量係以0·5至U 田里D 1 g月匕之竣酸對i官能之酸肝）為佳，以5至 1: 2田里為特^。相對於環氧基）當量，如未達$當量或超出1. 5田里時’均無法充分地硬化而有無法得到良好的硬化物性之虞慮。 31 322150 201120000 本發明之硬化性樹脂級成物中，亦可與硬化劑一起併用硬化促進劑。可使用之硬化促進劑的具體例玎列舉如· 2-曱基咪σ坐、2-苯基咪哇、十一烧基^米唑、2-十七炫基咪唑、2-苯基-4-曱基咪唑、卜苄基_2_苯基咪唑、1-苄基 -2-甲基咪唑、1-氰基乙基〜2甲基咪唑、i一氰基乙基-2-苯基咪唑、卜氰基9乙基〜2〜十一烷基咪唑、2, 4_二胺基 -6(2’-曱基咪唑（1，））乙基均三嗪、2,4二胺基一6(2，-十一烷基咪唑（1，））乙基均三嗪、2,4_二胺基_6(2，-乙基，4-甲基咪唑（1,))乙基均三嗪、2,4一二胺基一6(2，-甲基咪唑（1，））乙基均三嗪.異氰脲酸加成物、2·甲基咪唑異氰脲酸之2 : 3加成物、2_苯基咪唑異氰脲酸加成物、2-笨基-3, 5-二羥甲基咪唑、2-苯基—4-羥甲基-5-甲基咪唑、卜氰基乙基-2-苯基-3, 5-二氰基乙氧基甲基咪唑之各種咪唑類，以及，該等咪唑類與酞酸、間酞酸、對酞酸、偏苯二酸、均苯四酸、萘二羧酸、馬來酸、草酸等多元羧酸之鹽類，雙氰胺等醯胺類；1，8-二吖雙環（5.4.0)十一烯-7 等二氮雜化合物以及該等之四苯硼酸鹽、酚醛清漆等之鹽類，與上述多元羧酸類或膦酸類之鹽類；溴化四丁銨、溴化十六烷基三曱基銨、溴化三辛基曱基銨、氫氧化十六烷基三甲基銨等之四級銨鹽（以（^至Cm烷基銨鹽為佳）；三笨基膦、三（曱苯曱醯基）膦、溴化四苯基鱗、四笨基鱗四笨基爛酸鹽等膦酸類或鱗化合物；2, 4,6_三胺基曱基紛等盼類；胺加成物；辛酸錫等金屬化合物等；以及將該等硬化促進劑裝入微膠囊之微勝囊型硬化促進劑等。在該等硬 32 322150 201120000 化促進劑中欲使用何種，例如係依透明性、硬化速度、作業條件而得之透明樹脂組成物所要求的特性適當地選擇。本發明中之較佳者可列舉如：鱗化合物（以四級鱗鹽更佳）或四級敍鹽。硬化促進劑相對於環氧樹脂100重量份時，一般係在〇· 001至15重量份之範圍中使用，以〇. 〇丨至5重量份為佳，以0. 05至1重量份更佳。亦可使本發明之硬化性樹脂組成物中含有作為賦予難燃性之成分的含鱗化合物^含雄化合物可為反應型者亦可為添加型者。含磷化合物之具體例可列舉如：磷酸三甲酯、磷酸三乙酯 '磷酸三曱笨酯、磷酸三（苯二曱基）酯、磷酸曱苯酯二苯酯、填酸曱苯酯-2, 6-二（苯二甲基）酯、 1’ 3-伸苯基雙（二（苯二曱基）磷酸酯）、丨，4_伸苯基雙（二 (苯二甲基）磷酸酯）、4,4’ -聯苯（二（苯二甲基）磷酸酯）等磷酸酯類；9, 10-二氫-9-氧雜-10-磷雜菲ίο-氧化物、 10(2, 5-一起苯基）-10H-9-氧雜-10-碟雜菲10-氧化物等膦類；使環氧樹脂與上述磷化氫類之活化氫反應而得的含磷之環氧化合物、紅磷等，惟以磷酸酯類、磷化氫類或含磷之環氧化合物為佳，尤以丨，3_伸苯基雙（二（苯二甲基）碌酸酯）、1，4-伸苯基雙（二（苯二甲基）磷酸酯）、4, 4，-聯苯（二（苯二甲基）磷酸酯）、4, 4，-亞丁基雙（3-甲基-6-第二丁基苯基-二-十三烧基亞填酸酯）或含構之環氧化合物為特佳。含磷之化合物的含量以含磷之化合物/全環氧樹脂=0. 1至0. 6(重量比）為佳。〇. 1以下時，難燃性不充分，It is better than the epoxy group of the all-% oxygen resin to be 0. 5 to U, and the D 1 g of the tannic acid to the i-functional acid liver) is 5 to 1: 2 ^. With respect to the epoxy group equivalent, if it is less than $ eq or exceeds 1.5 liters, it is not sufficiently hardened to have a good hardening property. 31 322150 201120000 The curable resin composition of the present invention may be used together with a curing agent in combination with a curing agent. Specific examples of the hardening accelerator which can be used are exemplified by 2-indolyl sigma, 2-phenyl imidium, eleven alkyl carbazole, 2-heptacyl imidazole, 2-phenyl-4 - mercapto imidazole, benzylidene-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl~2methylimidazole, i-cyanoethyl-2-phenylimidazole, Cyano 9ethyl~2~undecylimidazole, 2,4-diamino-6(2'-nonylimidazolium (1,)) ethyl s-triazine, 2,4 diamine- 6 ( 2,-undecyl imidazole (1,)) ethyl s-triazine, 2,4-diamino -6 (2,-ethyl, 4-methylimidazolium (1,)) ethyl s-triazine 2,4-diamino- 6 (2,-methylimidazolium (1,)) ethyl s-triazine. Isocyanuric acid adduct, 2 · methylimidazole isocyanuric acid 2 : 3 plus Product, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3, 5-dimethylolimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, cyanide Various imidazoles of ethylethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and the imidazoles and citric acid, meta-citric acid, citric acid, phthalic acid, Pyromellitic acid, naphthalene dicarboxylic acid, maleic acid, oxalic acid, etc. a salt of a carboxylic acid, a guanamine such as dicyandiamide; a diazepine compound such as 1,8-dibicyclobicycle (5.4.0) undecen-7; and a salt of such a tetraphenylborate or a novolac. a salt of the above polycarboxylic acid or phosphonic acid; tetrabutylammonium bromide, cetyltrimethylammonium bromide, trioctyldecylammonium bromide, cetyltrimethylammonium hydroxide a quaternary ammonium salt (equivalent to (^ to Cm alkylammonium salt); triphenylphosphine, tris(indolyl)phosphine, tetraphenylphosphonium bromide, tetraphenyl quaternary Phosphonic acid or squama compound such as acid salt; 2, 4, 6-triamino sulfhydryl group; amine adduct; metal compound such as tin octylate; and microhardening of the hardening accelerator The type of the hardening accelerator, etc., which is used in the above-mentioned hard 32 322150 201120000 chemical accelerator, for example, the characteristics required for the transparent resin composition obtained by the transparency, the curing speed, and the working conditions are appropriately selected. Preferred examples of the invention include, for example, a scaly compound (better than a quaternary scale salt) or a quaternary salt. A hardening accelerator relative to the epoxy resin 10 When it is 0 parts by weight, it is generally used in the range of 001 001 to 15 parts by weight, preferably 5 to 5 parts by weight, more preferably 0.05 to 1 part by weight. The spheroidal compound which is a component which imparts flame retardancy is contained in the resin composition, and the male compound may be a reactive type. The specific examples of the phosphorus-containing compound may, for example, be trimethyl phosphate or phosphoric acid. Ethyl ester triammonium phosphate, tris(phenylenediphenyl) phosphate, phenylphenyl diphenyl ester, phenyl phenyl ester-2,6-bis(phenylenedicarboxy) ester, 1' 3- Phenyl bis(bis(phenylenediyl)phosphate), hydrazine, 4_phenylphenylbis(bis(phenyldimethyl)phosphate), 4,4'-biphenyl (bis(phenyldimethyl) Phosphate), etc.; 9,10-dihydro-9-oxa-10-phosphaphenium oxide, 10(2,5-phenylene)-10H-9-oxa-10 - a phosphine such as a phenanthrene 10 -oxide; a phosphorus-containing epoxy compound obtained by reacting an epoxy resin with an activated hydrogen of the above phosphine, a red phosphorus, etc., but a phosphate ester or a phosphine Or a phosphorus-containing epoxy compound is preferred, especially丨, 3_phenylphenylbis(bis(phenyldimethyl) phthalate), 1,4-phenylphenylbis(bis(phenyldimethyl)phosphate), 4, 4,-biphenyl (two (Benzyl) phosphate, 4,4,-butylene bis(3-methyl-6-t-butylphenyl-di-tridecyl yanoate) or an epoxy containing The compound is particularly good. The content of the phosphorus-containing compound is preferably from 0.1 to 0.6 (weight ratio). 〇. 1 or less, the flame retardancy is not sufficient,

S 33 322150 201120000 ，在〇· 6 Μ上時’惟恐硬化良影響。絕緣特性受到不在本發明之硬化性樹脂組成物巾抗氧化劑。可使用之抗氧化劑可列舉=應所需而添加糸抗氧化劑、磷系抗氧化劑等。抗氧化2抗氣化劑、硫合二種以上使用。相對^减劑可單獨使用或組樹脂成分100重量份，H 之硬化性樹月旨組成物中的 ⑽，較佳為〇.01至0.5重量:用置通吊為°·_至抗氧化劑可列舉如酚系抗氧化劑、护系抗氧化劑等齡季浐氦#豳, Ί、几氧化劑、鱗礼匕齊J寻紛系抗氧化劑之具體例可例示如第三丁基對甲齡、丁基化縣菌㈣、2 :丁6-: 乙酚、硬脂基5—-铉一丁Α , 矛一丁暴對 w U’b 一 '弟二丁基-4-羥基苯基）丙酸酉曰、、辛基-3-(3,5-二-第三丁基+經基苯基）丙酸酉旨、 2, 4-雙（正辛硫基）_6~(4—羥基—3,卜二_第三丁基苯胺）1’3,5 一 # 2,4雙[(辛硫基）甲基]鄰甲盼等單紛類；2,2’ -亞甲基雙（4一曱基_6_第三丁基酚）、2,2, _亞曱基雙（4-乙基-6-第三丁基酚）、4,4，_硫代雙（3一曱基一6_ 第二丁基酚）、4,4 -亞丁基雙（3_甲基_6_第三丁基酚）、二乙二醇-雙[3-(3-第三丁基_5_甲基-4-羥基笨基）丙酸酯]、1,6-己二醇-雙[3-(3,5-二-第三丁基-4-羥基苯基）丙酸酯]、Ν，Ν’ -六亞曱基雙（3, 5-二-第三丁基-4-羥基-氫基肉桂酿胺）、2, 2-硫基-二伸乙基雙[3-(3, 5-二-第三丁基-4-經基笨基）丙酸醋]、3, 5-二-第三丁基-4-經基苄基膦酸酯-二乙酯、3, 9-雙[1，1-二甲基一2一{冷-(3-第三丁基-4- 34 322150 201120000 經基-5-甲基苯基）丙醯氧基}乙基]-2, 4, 8, 10-四氧雜螺 [5, 5]十一烧、雙（3, 5-二-第三丁基-4-羥基苄基磺酸乙酯）妈等雙酚類；1，1，3-三（2-甲基-4-羥基-5-第三丁基苯基）丁院、1，3, 5-三甲基-2, 4, 6-三（3, 5-二-第三丁基-4-經基苄基）苯、四-(亞甲基_3_(3’，5，_二_第三丁基_4，_羥基苯基）丙酸酯）甲烷、雙[3,3，_雙-(4，_羥基-3，_第三丁基本基）丁酸]甘油酯、三-(3, 5-二-第三丁基-4-經基苄基）-異氰脲酸酯、1，3,5-三（3，，5，-二-第三丁基-4，- 羥基苄基）-S-三嗪-2, 4, 6-(1Η，3H，5H)三酮、生育酚等高分子型紛類。硫系抗氧化劑之具體例可例示如二月桂基_3, 3, _硫代一丙酉文S曰、一肉豆蔻基-3,3 -硫代二丙酸酯、二硬脂基 -3,3’ -硫代二丙酸酯等。嶙糸柷乳化劑之具體例可例示如亞磷酸三笨酯、亞磷酸二苯基酯異癸基酯、亞磷酸苯基酯二異癸基酯、三（壬基苯基）亞磷酸酯、二異癸基季戊四醇亞磷酸酯、三（2,4_二"_ 第三丁基苯基）亞磷酸酯、環狀新戊烷四基雙（十八烷基）亞鱗酸自旨、環狀新魏四基二（2,4_二_第三了基笨基)兀亞土破酸醋、環狀新錢四基二（2, 4-二—第三丁基+甲基 =二[2-第三丁基—"基+丨2—(十八心基_ 乙基}本基]風亞磷酸醋等亞磷酸酉旨類；9，1〇—二氫 -1㈣雜菲-10_氧化物、1(K3,5—二—第三丁基+羥基；土 )-9，10-二氫+氧雜鲁碟雜菲鲁氧化物魯癸氧基 _，10-二氫-9-氧雜’―磷雜菲氧化物等氧雜磷雜二 322150 35 201120000 氧化物類等。該等抗氧化劑可各自單獨使用，亦可將2種以上組合併用。特別是在本發明中以磷系之抗氧化劑為佳。本發明之硬化性樹脂組成物中，另可因應所需而添加光安定劑。光安定劑係以受阻胺系之光安定劑為佳，尤以受阻胺類光安定劑（HALS : Hindered Amine Light Stabilizer) 為適合。HALS並無特別限定者，惟代表性者可列舉如：二丁胺·1，3,5-三嗪·Ν，Ν，-雙（2,2,6,6-四甲基一 4一哌啶^ -1，6-六亞甲二胺與^(2,2,6,6_四曱基_4—哌啶基）丁2 胺之縮聚物、琥珀酸二甲基羥基乙基）_4_羥^ -2, 2, 6, 6-四曱基哌啶縮聚物、聚3,3_四曱基$ 基）胺基-1，3, 5-三嗪-2, 4-二基}{(2, 2, 6, 6-四甲基_4一哌啶基）亞胺基}六亞甲基{(2, 2, 6, 6-四曱基-4—哌啶基）亞胺基}]、雙（1，2, 2, 6, 6-五曱基-4-哌咬基）[[3, 5-雙（1 ι_二甲基乙基）-4-羥基苯基]甲基]丁基丙二酸酯、雙（2, & & 6一四曱基-4-哌啶基）癸二酸酯（後述li)、雙2, 2, 6 五甲基-4-哌啶基）癸二酸酯、雙（1_辛氧基_2, 2, 6, 6_四曱基 -4-哌啶基）癸二酸酯、2-(3,5-二-第三丁基〜4_羥基苄基）-2-正丁基丙二酸雙（1，2, 2, 6, 6-五曱基-4-哌啶基）等，HALS可僅使用1種，亦可併用2種以上。本發明之硬化性樹脂組成物中，亦可因應必要而調配黏合劑樹脂。黏合劑樹脂可列舉如：縮丁醛系樹脂、縮醛系樹脂、丙烯酸系樹脂、環氧-尼龍系樹脂、NBR_酚系樹脂、 322150 36 201120000 環氧-NBR系樹脂、聚醯胺系樹脂、聚醯亞胺系樹脂、矽鲖系樹脂等，惟並不限於此等。黏合劑樹脂之調配量以在無損及硬化物之難燃性、耐熱性的範圍為佳，相對於樹骑^ . 分100重量份，一般可因應需要而使用0.05至50重量份， . 以〇. 至20重量份為佳。 . 本發明之硬化性樹脂組成物中，可因應必要而添加無機充填劑。無機充填劑係可列舉如：結晶氧化矽、熔煉^ 化矽、氧化鋁、錯石、矽酸鈣、碳酸鈣、碳化矽、氮化矽、氮化硼、氧化鍅、鎂撖欖石、塊滑石、尖晶石、二氧化敛、滑石等之粉體或該等經球型化之珠粒等，惟不僅限於該等。 2等可單獨❹，亦可併用2種以上。該等無機充填劑之含置係本發明之硬化性樹脂組成物中可使用〇至95重量％之篁。更且，可在本發明之硬化性樹脂組成物中添加矽烷偶合劑、硬脂酸、棕櫚酸、硬脂酸鋅、硬脂酸鈣等脫模劑；碳酸鋅（2-乙基己酸辞、硬脂酸鋅、山茶酸鋅、肉豆謹酸辞）或磷酸酯鋅（辛基磷酸辞、硬脂基磷酸鋅等）等鋅化合物（金屬矣）、界面活性劑、染料、顏料、紫外線吸收劑等各種調配劑、各種熱硬化性樹脂。較佳之硬化性樹脂組成物可列舉如下述之樹脂組成物。 ⑴-種組成物’係包含··相對於硬化性樹脂組成物之總量 3有1(^至90重之環氧龍、相對於該環㈣脂之環氧基1當量，以硬化劑組成物之官能基當量計，含有〇·5至 1· 5當量之硬化性樹脂組成物者。該樹脂組成物更可含有 322150 37 201120000 ίΙΓ氧樹脂100重量份為請至15重量份之比例的進劑。一般以含有該硬化促進劑者為佳。係上二記載之硬化性樹脂組成物’其中’環氡樹脂錢燒（以重γ平"^旨4具有環氧基環己燒構造之有機聚有機聚石夕心二句为子量為1000至2〇,〇〇0左右之環氧基虱烷為佳，以1000至1〇〇〇〇左右者更佳）。脂環式产^述（1)或（ii)記載之硬化性樹脂組成物，其中，物。χ & _日為具有環氧基環己炫構造之脂環式環氧化 =====載甲:化：”了’其中’ -⑽篇-、-C()(wr /、有曱基之壤氧基環己基，例如 -CH2-C〇n-rr 3 C8之2價飽和脂肪族基）-C00-、 (c3至c之之2價飽和脂肪族基）—C(X)_或_CH2-C00~ 宫能環氧樹脂。 CH2-等父聯基鍵_之2 (V)如上述G)至（iv)中任一項吁哉其中，硬化劑係式⑴之多元之硬化性樹脂組成物，载的多元驗組成物。魏或上述1、上述10所記述⑴至(iv)中任-項記載之硬化性樹脂組成 1的劑係含有式⑴之多元驗或上述η所記戰的夕兀竣酸組成物之硬化劑。 =上述⑴至…任-項記载之硬化性樹脂組成 =。其中’魏_成物係上述u所記載之多錄酸組成 322150 38 201120000 (Viii)如上述（〇至（vi)中任一項記載之硬化性樹脂組成物，其中’硬化劑組成物係上述13所記載之硬化劑組成物。 (IX) 如上述（1)至（viii)中任一項記載之硬化性樹脂組成 •物，其中，硬化劑係含有式（1)之多元羧酸者或含有上述 14所記載之硬化劑者。 (X) 如上述（i)至（ix)中任一項記載之硬化性樹脂組成物，其中，該硬化促進劑係鱗化合物（更佳者為四級鱗鹽）或四級錢鹽。 (xi)如上述（i)至（ix)中任一項記載之硬化性樹脂組成物’其中’式（1)之R為甲基或羧基。將本發明之硬化性樹脂組成物使用在光半導體封閉劑時，可因應需要而添加螢光體。螢光體係例如藉由吸收部分由藍色LED元件所發出之藍色光，並發出波長經轉換之黃色光，即具有形成白色光之作用者。預先將螢光體分政在硬化性樹脂組成物中，然後將光半導體進行密封。螢光體並無特別限制，可使用以往習知之螢光體，可例示如稀土類元素之銘酸鹽、硫代沒食子酸鹽、正石夕酸鹽等。更具體上，可列舉如：YAG螢光體、tag螢光體、正矽酸鹽螢光體、硫代沒食子酸鹽螢光體、硫化物螢光體等螢光體，可例不如：YAl〇3:Ce、Y3Al5〇12:Ce、Y4Al2〇9:Ce、Y2〇2S:Eu、 Sr5(P〇4)3ci:Eu、（SrEu)O.Al2〇3等。該螢光體之粒徑係使用在該領域中之習知粒徑者，平均粒徑係以1至250/zm 為佳’以2至50 am更佳。在使用該等螢光體時，其添加里相對於該樹脂成分1〇〇重量份，係以1至80重量份為 S- 39 322150 201120000 佳’以5至60重量份更佳。本發明之硬化性樹脂組成物可藉由將各成分均勻地混合而獲得。本發明之硬化性樹脂組成物以與以往習知之相同方法而可輕易地作成該硬化物。可列舉例如將本發明之環氧樹脂與硬化劑以及因應所需之硬化促進劑、含磷化合物、黏合劑樹脂、無機充填材以及調配劑，依所需而使用擠出機、捏合機、輥等充分地混合至均勻後而得硬化性樹脂組成物’該硬化性樹脂組成物為液狀時，係以灌注 (potting)、鑄造（casting)、浸潰基材、硬化性樹脂組成物流入模型之流鑄，經加熱而硬化之手法；如為固形時，係在溶融後流鑄或使用轉移成型機（transfer machine)等使之成型，再經由加熱而硬化之手法。硬化溫度、時間係在80至20(TC進行2至1〇小時。硬化方法雖可在高溫使之一次固化，惟以逐步地升溫以進行硬化反應者為佳。具體而言，在80至15(rc之間進行初期硬化，然後在100C至20(TC之間進行後硬化。硬化階段以分為2 至8階段而進行昇溫者為佳，以2至4階段更佳。將本發明之硬化性樹脂組成物溶解在甲苯、二甲苯、S 33 322150 201120000, when you are on the 〇·6 ’, fear of hardening good influence. The insulating property is not affected by the curable resin composition of the present invention. The antioxidant which can be used is exemplified by adding an antimony antioxidant, a phosphorus-based antioxidant, or the like as needed. Antioxidant 2 anti-gasifier and sulfur are used in combination of two or more. The relative reducing agent may be used alone or in combination with 100 parts by weight of the resin component, and (10) of the curable composition of H, preferably 〇.01 to 0.5 by weight: by means of a suspension to ° ° to an antioxidant Specific examples of antioxidants such as phenolic antioxidants, antioxidants, and the like may be exemplified by, for example, a third butyl group, a butyl group, and a specific example of an antioxidant. Phytophthora (4), 2: Ding 6-: Ethylphenol, stearyl 5- 铉 Α Α , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ,曰,, octyl-3-(3,5-di-t-butyl+periphenyl)propionic acid, 2,4-bis(n-octylthio)_6~(4-hydroxy-3, Bu-di-tert-butylaniline) 1'3,5-# 2,4 bis[(octylthio)methyl]--------- 2,2'-methylene double (4 曱Base_6_t-butylphenol), 2,2, _indenyl bis(4-ethyl-6-tert-butylphenol), 4,4, _ thiobis (3-indolyl-6_) Second butyl phenol), 4,4-butylene bis(3-methyl-6_t-butylphenol), diethylene glycol-bis[3-(3-t-butyl-5-methyl) -4-hydroxyphenyl)propionate], 1,6-hexyl Alcohol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], hydrazine, Ν'-hexamethylene bis (3, 5-di-t-butyl) -4-hydroxy-hydrogen cinnamylamine), 2, 2-thio-diethylidene bis[3-(3,5-di-t-butyl-4-ylphenyl)propionic acid vinegar] ,3,5-di-t-butyl-4-transbenzylphosphonate-diethyl ester, 3,9-bis[1,1-dimethyl- 2-{cold-(3-third Butyl-4-34 322150 201120000 mercapto-5-methylphenyl)propoxycarbonyl}ethyl]-2, 4, 8, 10-tetraoxaspiro[5, 5] eleven, double ( 3,5-di-t-butyl-4-hydroxybenzylsulfonate ethyl ester) Mom and other bisphenols; 1,1,3-tris(2-methyl-4-hydroxy-5-t-butyl Phenyl) Dingyuan, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-alkylbenzyl)benzene, tetra-(methylene _3_(3',5,_di-t-butyl-4-[,hydroxyphenyl)propionate) methane, bis[3,3,_bis-(4,_hydroxy-3, _ third Basic base) butyrate] glyceride, tris-(3,5-di-t-butyl-4-alkylbenzyl)-isocyanurate, 1,3,5-tris(3,,5, -di-t-butyl-4,-hydroxybenzyl)-S-triazine-2, 4, 6-(1Η,3H,5H High molecular weight such as triketone and tocopherol. Specific examples of the sulfur-based antioxidants include, for example, dilauryl _3, 3, thio-propyl hydrazine, hydrazinyl-3,3-thiodipropionate, distearyl-3 , 3'-thiodipropionate and the like. Specific examples of the hydrazine emulsifier include, for example, triphenyl phosphite, isodecyl phosphite, diisodecyl phenyl phosphite, tris(nonylphenyl) phosphite, Diisodecyl pentaerythritol phosphite, tris(2,4_bis"_t-butylphenyl)phosphite, cyclic neopentyltetraylbis(octadecyl) sulphite环环新魏四基二(2,4_二_三基基基基)兀土土破酸醋,环新钱四基二(2, 4-二-三丁+methyl=二[ 2-tert-butyl-" base + 丨2-(octadecyl-ethyl) ketone] phosphite citrate and other phosphites; 9,1 〇-dihydro-1 (tetra) phenanthrene-10 _oxide, 1 (K3,5-di-t-butyl+hydroxyl; earth)-9,10-dihydrogen+oxaluene dish phenanthrene oxide ruthenium oxy-, 10-dihydro-9 Oxaphosphorus oxide such as oxa-phosphorus oxide 322150 35 201120000 Oxide, etc. These antioxidants may be used singly or in combination of two or more. In particular, phosphorus is used in the present invention. Preferably, the antioxidant is preferred. In the curable resin composition of the present invention, A light stabilizer is added as needed. The light stabilizer is preferably a hindered amine light stabilizer, and particularly a Hinder: A Hindered Amine Light Stabilizer. HALS is not particularly limited. Representative examples include dibutylamine·1,3,5-triazine·Ν, Ν,-bis(2,2,6,6-tetramethyl- 4 piperidinium-1,6- Polycondensate of hexamethylenediamine and ^(2,2,6,6-tetradecyl-4-pyridinyl)butanamine, dimethylhydroxyethyl succinate)_4_hydroxy^-2, 2 , 6, 6-tetramethylpiperidine polycondensate, poly 3,3_tetradecylamino)-1,3,5-triazine-2,4-diyl}{(2, 2, 6 , 6-tetramethyl-4(piperidinyl)imido}hexamethylene {(2, 2, 6, 6-tetradecyl-4-piperidinyl)imido}], double (1 , 2, 2, 6, 6-pentamethyl-4-piperidinyl)[[3, 5-bis(1 ι-dimethylethyl)-4-hydroxyphenyl]methyl]butylpropane Acid ester, bis(2, && 6-tetradecyl-4-piperidyl) sebacate (li), bis 2, 2, 6 pentamethyl-4-piperidinyl) Acid ester, bis(1-octyloxy-2, 2, 6, 6-tetradecyl-4-piperidyl) sebacate, 2-(3,5-di-t-butyl- 4_hydroxybenzyl)-2-n-butylmalonic acid bis(1,2,2,6,6-pentamethyl-4-piperidyl), etc., HALS can be used alone or in combination 2 More than one species. In the curable resin composition of the present invention, a binder resin may be blended as necessary. Examples of the binder resin include butyral resin, acetal resin, acrylic resin, epoxy-nylon resin, NBR phenol resin, 322150 36 201120000 epoxy-NBR resin, and polyamine resin. Polyimine-based resin, fluorene-based resin, etc., but is not limited thereto. The blending amount of the binder resin is preferably in the range of flame retardancy and heat resistance of the non-destructive and hardened material, and is generally used in an amount of 0.05 to 50 parts by weight based on 100 parts by weight of the tree ride. It is preferably up to 20 parts by weight. In the curable resin composition of the present invention, an inorganic filler may be added as necessary. Examples of the inorganic filler include, for example, crystalline cerium oxide, smelting cerium, aluminum oxide, strontium, calcium silicate, calcium carbonate, cerium carbide, cerium nitride, boron nitride, cerium oxide, magnesium sapphire, and blocks. Powders such as talc, spinel, dioxane, talc, or the like, or such spheroidized beads, are not limited thereto. 2 or the like may be used alone or in combination of two or more. The inorganic filler may be used in the curable resin composition of the present invention in an amount of from 〇 to 95% by weight. Further, a mold release agent such as a decane coupling agent, stearic acid, palmitic acid, zinc stearate or calcium stearate may be added to the curable resin composition of the present invention; zinc carbonate (2-ethylhexanoic acid) , zinc stearate, zinc betelate, nutmeg) or zinc compounds such as zinc phosphate (octyl phosphate, zinc stearyl phosphate, etc.), surfactants, dyes, pigments, ultraviolet rays Various preparation agents such as an absorbent, and various thermosetting resins. Preferred examples of the curable resin composition include the following resin compositions. (1) - The composition 'includes ·················································· The functional group equivalent of the material contains a hardening resin composition of 〇 5 to 1.5 equivalents. The resin composition may further contain 322150 37 201120000 ΙΓ 100 parts by weight of oxygen resin, up to 15 parts by weight. Generally, it is preferable to contain the hardening accelerator. The curable resin composition described in the above two is in which the ring-ring resin is burned (by weight gamma flat) and has an epoxy group. The organic polyorganic polylithic eclipse has a sub-quantity of 1000 to 2 〇, and an epoxy decane of about 〇〇0 is preferred, preferably about 1000 to 1 ).) The curable resin composition according to (1) or (ii), wherein the substance is an alicyclic epoxidation having an epoxycyclohexanthene structure ===== armor: "There" '-(10)--, -C() (wr /, a sulfhydryl-based cyclohexyl group, such as a 2-valent saturated aliphatic group of -CH2-C〇n-rr 3 C8)-C00- , (C3 to c of the two-valent saturated aliphatic group) - C (X) _ or _CH2-C00 ~ uterine epoxy resin. CH2- and other parental bond _ 2 (V) as above G) to ( Iv) Any one of the hardening resin compositions of the formula (1), which is a multi-component composition, which is described in any one of the above-mentioned items (1) to (iv). The agent of the curable resin composition 1 contains a sizing agent of the formula (1) or a curing agent of the cerium acid composition of the above-mentioned η. The hardening resin composition of the above (1) to (a) is defined. The hardening resin composition according to any one of the above-mentioned (a), wherein the hardener composition is the above-mentioned 13 The curable resin composition according to any one of the above aspects (1) to (viii), wherein the curing agent contains a polycarboxylic acid of the formula (1) or contains The curable resin composition according to any one of the above-mentioned (i) to (ix), wherein the hardening accelerator is scaly (a) a hardening resin composition as described in any one of the above (i) to (ix), wherein R of the formula (1) When a curable resin composition of the present invention is used in a photo-semiconductor blocking agent, a phosphor may be added as needed. The fluorescent system emits blue light by a blue LED element, for example, by absorbing portions. And emitting a wavelength-converted yellow light, that is, having a function of forming white light. The phosphor is previously divided into a curable resin composition, and then the photo-semiconductor is sealed. The phosphor is not particularly limited, and a conventionally known phosphor can be used, and examples thereof include a rare earth element acid salt, a thiogallate salt, and a oxetane salt. More specifically, examples thereof include a phosphor such as a YAG phosphor, a tag phosphor, a strontium silicate phosphor, a thiogallate phosphor, or a sulfide phosphor. : YAl〇3: Ce, Y3Al5〇12: Ce, Y4Al2〇9: Ce, Y2〇2S: Eu, Sr5(P〇4)3ci: Eu, (SrEu)O.Al2〇3, and the like. The particle size of the phosphor is a conventional particle size used in the art, and the average particle diameter is preferably from 1 to 250 / zm, more preferably from 2 to 50 am. When the phosphors are used, the amount thereof is from 1 to 80 parts by weight, preferably from 1 to 80 parts by weight, more preferably from 5 to 60 parts by weight, based on 1 part by weight to the total of the resin component. The curable resin composition of the present invention can be obtained by uniformly mixing the components. The curable resin composition of the present invention can be easily produced into the cured product in the same manner as conventionally known. For example, an epoxy resin and a hardener of the present invention, and a hardening accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler, and a compounding agent which are required for use, and an extruder, a kneader, and a roll are used as needed. When the curable resin composition is in a liquid state, it is sufficiently mixed and homogenized, and the composition is poured into a model by potting, casting, impregnating the substrate, and curable resin. The method of casting, heating and hardening; if it is solid, it is formed by casting after melting, or by using a transfer machine or the like, and then hardening by heating. The hardening temperature and time are between 80 and 20 (TC is carried out for 2 to 1 hour. Although the hardening method can be cured once at a high temperature, it is preferred to gradually increase the temperature to carry out the hardening reaction. Specifically, at 80 to 15 (The initial hardening is carried out between rc, and then post-hardening is carried out between 100 C and 20 (TC. The hardening stage is preferably carried out by dividing into 2 to 8 stages, preferably 2 to 4 stages. The hardening of the present invention. The resin composition is dissolved in toluene, xylene,

塵成型而可作成本發明之硬化性樹此時之溶劑在本發明之硬化性樹脂 322150 40 201120000 組成物與該溶劑之混合物中，一般係使用10至70重量％之量，以15至70重量％之量為佳。並且，直接將液狀組成物以RTM方式亦可得到含碳纖維之環氧樹脂硬化物。並且，亦可將本發明之硬化性樹脂組成物使用作為薄膜型組成物之改質劑。具體而言，可在B階中提高撓性等的情形下使用。如此之薄獏型樹脂組成物係可將本發明之硬化性樹脂組成物A作為上述硬化性樹脂組成物清漆塗佈在剝離膜上，在加熱下去除溶劑後，藉由進行B階化而得到作為片狀之接著劑。該片狀接著劑可作為多層基板等中之層間絕緣層使用。接著’對於本發明之環氧樹脂組成物作為光半導體之密封材料或黏晶材料使用時進行詳細說明。本發明之環氧樹脂組成物在使用作為高亮度白色led 等之光半導體的密封材料或黏晶材料時，藉由將含有式（J) 之多元羧酸的硬化劑（硬化劑組成物）、與環氧樹脂以外之硬化促進劑、偶合劑材、抗氧化劑、光安定劑等孓添加物充分地混合而調製環氧樹脂組成物以作為密封材料使用，或作為黏晶材料與密封材料雙方使用。混合方法係使用捏合機、三軸輥、多功能攪掉機、行星式攪拌機、均質機、均質分散機、珠磨機等在常溫或加溫中進行混合。高亮度白色LED等之光半導體一般係將使層積在藍寶石、尖晶石、SiC、Si、ZnO 等基板上的 GaAs、GaP、GaAlAs、 GaAsP、AlGa、InP、GaN、InN、AlN、InGaN 等半導體晶片，以接著劑（黏晶材料）黏接在導線架、散熱板或封裝物上而 41 322150 201120000 成。亦有為通過電流而連接金屬線等線之型。為了防止熱或濕氣且為了達到透鏡功能之功用而將該半導體晶片以王: 氧樹脂等密騎料密封。本發明之環氧樹脂組成:係可= 用作為該料材料或黏晶材料。由步驟上，本發明之硬化性樹脂組成物使用在黏晶材料及密封材料雙方上為方便。將半導體晶片以本發明之硬化性樹脂组成物接著在基板之方法係，本發明之環氧樹脂組成物藉由分注器 (Dispenser)、灌注、網版印刷塗佈後，放上半導體晶片並進行加熱硬化’即可使半導體晶片接著。加熱係可使用熱風循環式、紅外線、高頻等方法。加熱條件係以例如80至230X：、1分鐘至24小時左右為佳。以減低加熱硬化時所產生之内部應力為目的，可在8〇至 120°C使預先硬化30分鐘至5小時後，再以12〇至丨8〇七、 30分鐘至1〇小時之條件使其後硬化。密封材料之成型方式係可使用如上所述之在半導體晶片經固定之基板所插人之型框内注人密封材料後進行加熱硬化而成型之;^人方式；預先在模型上注人密封材料，使固疋於基板上之半導體晶片浸潰於此，經力η熱硬化後再由模型脫模之壓縮成型方式等。注入方法可列舉如分注、轉注成型（tanker molding)、射出成型（injecti〇n m〇iding)等。加熱可使用熱風循環式、紅外線以及高頻等之方法。加熱條件係以例如80至23〇。(：、1分鐘至24小時左右為佳。以減低加熱硬化時所產生之内部應力為目的，可 322150 42 201120000 在80至120°C使預先硬化30分鐘至5小時後，盅,、，丹从12〇至180°C、30分鐘至10小時之條件使其後硬化。更且，本發明之硬化性樹脂組成物可使用在環氧樹月旨等之熱硬化性樹脂所使用的一般用途上，具體上可歹,丨汽^ 接著劑、塗料、塗佈劑、成型材料（片、薄膜、PRP等）絕緣材料（包含印刷基板、電線包覆等）、密封材料以外、密封材料、基板用之氰酸酯樹脂組成物、以及作鼻、 Μ丨且齊丨j用硬化劑之丙烯酸酯系樹脂等、對其它樹脂之添加劑等。接著劑除了土木用、建築用、汽車用、一般事務用、醫療用之接著劑以外，可列舉如電子材料用之接著劑。該等中之電子材料用接著劑可列舉如：增層（Build—Up)基板等多層基板之層間接著劑；黏晶劑、底部填充劑（u n d e r f i i i) 等半導體用接著劑；BGA強化用底部填充劑、異方性導電膜（ACF . Anisotropic Conductive Film)、異方性導電膠 (ACP: Anisotropic Conductive Paste)等封裝用接著劑等。密封材料可列舉如電容器、電晶體、二極體、發光二極體、1C、LSI等用之灌注、浸潰、傳遞模塑密封；IC、 LSI類之COB、C0F、TAB等用的所謂灌注密封；覆晶等用之底部充填、QFP、BGA、CSP等之ic封裝類在安裝時之密封（包含強化用底部充填）等。本發明之硬化性樹脂組成物經硬化而得的本發明之硬化物可使用在以光學零件材料為主之各種用途上。光學用材料-般表示使可見光、紅外線、紫外線、χ射線、雷射光等之光通過該材料中之用途所使用之材料。更具體言 322150 43 201120000 之，除了燈型、ςΜη i SMD型等LED用密封材料之外，可列舉儿左坂、硯角修正膜、接著劑、偽等液晶用膜等㈣偏先片保5蔓膜曰曰顯不裝置周邊材料。並為下世代之半面顯示器所期待的彩色PDP(顯㈣）之密封材料、: 反射2、光予修正膜、殼材、前面玻璃之保護膜、前面玻璃1替代材料、接著劑；或為LED顯示裝置中所使用之led 的核塑材、LED之密封材料、前面坡璃之保護膜、前面玻璃之替代材料、接著劑；或為定址液晶（ΡΑΙΧ)顯示器中之基板材料、導光板、稜鏡片、偏向板、相位差板、視角修正膜、接著劑、偏光板保護膜；或為有機EL(電場發光）顯不器中之前面玻璃的保護膜；前面玻璃之替代材料、接著劑；或為場發射顯示器（FED)中之各種薄膜基板、前面玻璃之保護膜、前面玻璃之替代材料、接著劑。在光記錄領域中係VD(影像磁碟;）、cd/CD-ROM、CD-R/RW、 DVD-R/DVD-RAM、M0/MD、PD(相變化光碟）、光卡用之磁碟基板材料、讀取透鏡、保護膜、密封材料、接著劑等。在光學機器領域中係有靜態照相機之透鏡用材料、取景鏡、反光鏡、取景器遮罩、感光體。亦有攝影機之攝影透鏡、取景器。亦有投影電視之投射鏡、保護膜、密封材料、接著劑等。亦有感光機器之透鏡用材料、密封材料、接著劑、薄膜等。在光零件領域中係有光通訊系統中的光切換周邊之纖維材料、逯鏡、波導、元件之密封材料、接著劑等。聚光益周邊之光纖材料、金屬箍、密封材料、接 322150 201120000 著劑等。在光被動元件、光電路元件中係有透鏡、波導、 LED之密封材料、CCD之密封材料、接著劑等。光電積體電路（0EIC)周邊之基板材料、纖維材料、元件之密封材料 • 接著劑等。光纖領域中係有裝飾顯示器用照明/光導等；工 . 業用途之感應器類、顯示/標示類等；或者通訊基礎架= (Telecommunication infrastructure)用以及家庭内之數位機器連接用光纖。半導體積體電路周邊材料中係有 LSI、超LSI材料用之微蝕刻用的阻劑材料。在汽車/運輸機領域中係有汽車用之反光燈、軸承護圈、齒輪部分、^ 蝕層、切換部分、頭燈、引擎内零件、電子零件、各種内外裝品、驅動引擎、煞車油箱、汽車用防錄鋼板、内侧板、内裝材料、保護/結束用線束、燃料管、車燈、玻璃替代品。另有鐵路車輛用複層玻璃。又可為飛機之構造材的細性賦 ^劑、引擎周邊構材、保護/結束用線束、防餘層。在建築領域中係有内裝/加工用材料、電氣遮罩、薄片、玻璃中間膜:玻璃替代品、太陽電池周邊材料。農業用者係有溫室覆蓋用膜。作為下世代之光/電子機能有機材料係有有機 L元件周邊材料、有機光折射元件、.光_光轉換裝置之光增幅元件、光運算元件、有機太陽電池周邊的基板材料、纖維材料、元件之密封材料接著劑等。密封劑係可列舉如電容器、電晶體、二極體、發光二極體、IC、LSI等用之灌注、浸潰、傳遞模塑密封；ic、 LSI類之COB、CQF、TAB等用之灌注密封；覆晶等用之底 #充填、BGA、CSP等之1C封裝類在安裝時之密封（包含強 322150 45 201120000 化用底部充填）等。光學用材料之其它用途係如硬化性樹脂組成物A或硬化性樹脂組成物B所使用之一般用途，可列舉如接著劑、塗料、被覆劑、成型材料（包含片、薄膜' FRp等）、絕緣材料（包含印刷基板、電線包覆等）、密封劑除外，對其它樹脂的添加劑等。接著劑除了土木用、建築用、汽車用、般事務用、醫療用之接著劑之外，另可列舉如電子材料用之接著劑。該等中之電子材料用的接著劑可列舉如增層基板等之多層基板的層間接著劑；黏晶劑、底部填充劑等半導體用接著劑；BGA強化用底部充填劑' 異方性導電膜 (ACF)、異方性導電膠（ACP)等封裝用接著劑等。、 [實施例] 以下，依實施例而更具體地說明本發明，惟下述之 $，如無特別限定，即為重量份。另外，本發明並非限於實施例者。並且，本發明中，凝膠層析（以下稱為「Gpc」）之測定係如下述。管柱為Shodex SYSTEM-21管柱（KF-803L、 KF-802. 5U2支）、KF-802)、連接洗提液為四氫呋喃、流迷為lmL/min.、管柱溫度為4(rc，檢測係在RI(反射率）下進行，標準曲線係使用Shodex製之標準聚笨乙烯。官能基當量係由依GPC所求得之比率而算出，並分別將羧酸、酸酐作為1當量而求得之值。實施例1(多元羧酸組成物A1) 在備有攪拌機、回流冷凝管以及攪拌裝置之燒瓶中，〜邊實施氮氣吹淨（nitrogen purging)，一邊添加甲苯ι〇 322150 46 201120000 份、2’4-二乙基5-戊二醇（協和發酵化學⑻製造；協和二醇PD9)80份、甲基六氫酿酸軒與六氣敗酸針之混合物 (新日本理化（股）製造；Rikacid MH700比率7 : 3，以下 •稱為酸針H1)168份，在1〇〇。(：進行4小時加熱授拌。在此 .時點’經由哪確認原料的消失（1面積％以下）後而結束反 •應。結束反應後，使用旋轉蒸發器，將殘留的溶劑進行德除而得到本發明之多元羧酸組成物（A1)246份。所得為無色固形樹脂，經由GPC之多元羧酸含量為97面積％。並且，羧基與酸酐合併之官能基當量（以下單稱為官能基當量）為 245g/eq·。另外，形狀雖為固形，惟具有些微流動性，在室溫徐緩變形而具有接近半固形之形狀。實施例2(硬化劑組成物B1) 相對於貫施例1所得之多元羧酸組成物（A1)25份，在添加酸酐（Η1) 7 5份使其均勻溶解，得到本發明之硬化劑組成物（Β1)。50°C中之黏度為450mPa.s(£型黏度儀）。實施例3(硬化劑組成物B2) 在備有攪拌機、回流冷凝管以及攪拌裝置之燒瓶中，一邊實施氮氣吹淨，一邊添加2, 4_二乙基5_戊二醇（協和發酵化學（股）製造；協和二醇PD9)2〇份、酸肝（hi)i〇〇份’在60°C進行4小時加熱攪拌。經由gpc確認2, 4-二乙基-1,5-戊二醇為1面積％以下。得到含有本發明之多元羧酸組成物的硬化劑組成物（B2)12〇份。所得之反應生成物為無色液狀樹脂。依GPC之組合比例係：多元竣酸（μ)為 52面積％、曱基六氫酞酸酐與六氫酞酸酐之總量為48面積 47 322150 201120000 %。並且，官能基當量為197g/eq.。50°C中之黏度為 1340niPa.s(25°C 中為 19700mPa.s ; E 型黏度儀）。實施例4、5(硬化性樹脂組成物）硬化劑係分別使用由實施例2及3所得之本發明的硬化劑組成物B1及B2、環氧樹脂係使用3, 4-環氧基環己基甲基-3, 4-環氧基環己基羧酸酯（Dow Chemical公司製造； UVR-6105以下稱為環氧樹脂（EP-1))、硬化促進劑係使用氫氧化十六烷基三曱基銨（東京化成工業（股）製造；25%曱醇溶液，以下稱為C1)，以下述表1所示之調配比例（重量份）進行調配，進行20分鐘之脫泡後，得到本發明之硬化性樹脂組成物。比較例1(比較用硬化性樹脂組成物）在上述實施例4及5中，除了將硬化劑變更為酸酐（H1) 之外’與實施例4及5進行相同步驟，得到比較用之硬化性樹脂組成物。使用所得之硬化性樹脂組成物，以下述所示之要點進行揮發試驗及LED試驗，並將該等之結果示於表1。另外，硬化條件係120°Cx2小時之預備硬化後15(TCx5小時。揮發試驗：實施例4、5及比較例1所得之硬化性樹脂組成物經實施真空脫泡20分鐘後，徐緩地注入以耐熱膠帶作成屏障 (dam)之玻璃基板上鑄型成為30mmx20mmx高度lmm者。鑄型之樹脂重量經正確地測定後，以上述條件使該鑄型物硬化0 48 322150 201120000 將如此進行而得之硬化物重量進行測定，確認硬化時之重量的減少。另外，硬化係實施例4、5及比較例！之任一者在同一烘箱下相同施行。 LED試驗：將實施例4、5及比較例i所得之各硬化性樹脂組成物進行真空脫泡2G分鐘後，個別地充填於量筒中。使用精密吐出裝置，分別將上述者注人並成型於各搭载具有發光波長46恤之發光元件的表面封裝型⑽型3m_)LED。然後，使該專在上述之硬化條件下硬化，得評價項目以及評價基準：用 (a)揮發性·以目視觀察密封後之硬化物表面是否有凹凸並進行評價。表中之評價基準係如下所述。〇：看不出有凹洞。 △:看出些微凹洞。 X :看出多數凹洞（有露出線）。 (b)回焊試驗：將所得之試驗用led在30°C、7〇%X72小時吸濕後，使用高溫觀察裝置（SMT Scope SK、5〇〇〇 ;山陽精工（股）製造），確認在以下之回焊條件下的LED有無龜裂產生。試驗係在n=3進行，以（〇κ數）/(試驗數）進行評價。同時，上述之（0K數）係看不出龜裂產生之合格數。條件係指由25°C以2°C/秒升溫至150。(：，然後在150 °C中維持2分鐘，再以2ΐ/秒升溫至260°C並維持10秒後，以1.3。0 /秒冷卻至室溫者。 322150 49 201120000 表1 B1 ~ B2 TTi - 4 實施例5 比較例1 單位硬化劑組成物 18.7 — 重量份 19.9 重量份硬化劑 HI EP1 ' _ 16.8 重量份環氧樹脂 13.0 13.0 13.0 重量份硬化促進劑 Cl 0. 05 0. 05 0. 05 重量份 -- 揮發試驗(揮發)量 4.6 5.8 13.0 重量％ (a) LE1D試驗（匕） Em 〇卜X 3/3 ------1 3/3 1/3 將實施例4、5與比較例J進行比較時，本發明之硬化性樹脂組成物的揮發量彡，即使在密封㈣時亦不會引發線露出等問題。更且，在回焊時亦看不到龜製的產生。由上述結果可知’藉由將含有本發明之多频酸组成物及酸針之本發明的硬化劑組成物作為硬化劑使用時，即可得到耐揮發性、以及賦予耐_龜裂中之優異硬化物的硬化性樹脂組成物者。實施例6(硬化劑組成物β3) 在備有攪拌機、回流冷凝管以及攪拌裝置之燒瓶中， :==’ 一邊添加2’4一基识二醇(協、今酵化子（奴）製造；協和二醇PD9)12份、酸酐（ηι)73 土、’，4環已境三缓酸_1，2-酐（Η-ΤΜΑη三菱瓦斯化學製造’以下稱為Η2)15份，在6(TC進行4小時加熱攪拌。經 2GPC確認2’4、二乙基―1，5-戊二醇成為1面積％以下後結 322150 50 201120000 得到含有式（1)之多元羧酸及酸酐的本發明之硬化劑組成物（B3) 100份。所得為無色之液狀樹脂。官能基當量為 183g/eq.。50°C 中之黏度為 1010mPa.s。，實施例7(硬化劑組成物B4) 在備有攪拌機、回流冷凝管以及攪拌裝置之燒瓶中， • 一邊實施氮氣吹淨，一邊添加2, 4-二乙基4,5-戊二醇（協和發酵化學（股）製造；協和二醇PD9)2〇份、4_甲基環己烷二羧酸酐（新日本理化（股）製造；Rikacid ΜΗ H3)l〇〇份，在60°(：進行4小時加熱攪拌。經由6?(：確認2,4-二乙美 _1，5_戊二醇為1面積％以下。得到含有式（1)之多元羧酸及酸酐的硬化劑組成物（B4)120份。官能基當量為2〇ig/eq。 5(TC 中之黏度為 1100mPa.s(25t：中為 16200mPa.s; E 型黏度儀）。實施例7a 由硬化劑組成物（B4)50份’使用旋轉蒸發器，將1〇〇至150°C存在過量之甲基六氫酞酸酐去除（由曱基六氣駄酸酐不再流出之時點’在加熱減壓條件下直接流入氮氣分鐘’即可充分地去除酸酐）的情況下，取出本發明之多元羧酸組成物（B4a)25份。形狀為無色之半固形至固形樹脂。所得樹脂之軟化點（依JIS K-7234之基準）為58 9 °C，在150°C中之熔融黏度為0. 08Pa.s。實施例8 (硬化劑組成物B5) 在備有攪拌機、回流冷凝管以及攪拌裝置之燒瓶中，一邊實施氮氣吹淨，一邊添加2, 4-二乙基-1，5-戊二醇（協 51 322150 s- 201120000 和發酵化學（股）製造；協和二醇PD9)12份、酸酐（H3)73 份、酸酐（H2)15份，在60°C進行4小時加熱攪拌。經由 GPC確認2, 4-二乙基-1，5-戊二醇成為1面積％以下。得到含有式（1)之多元缓酸及酸酐的硬化劑組成物（B5)l〇〇份。所得為無色之液狀樹脂。官能基當量為186g/eq.。50 °C中之黏度為1050mPa*s。實施例9(硬化劑組成物B6) 在備有攪拌機、回流冷凝管以及攪拌裝置之燒瓶中，一邊實施氮氣吹淨’一邊添加2, 4-二乙基-1，5-戊二醇（協和發酵化學（股）製造；協和二醇PD9)20份、環己燒二叛酸酐100份’在60°C進行4小時加熱攪拌。經由gpc確認2,4-二乙基-1,5-戊二醇為1面積％以下。得到含有式（1)之多元羧酸及酸酐的硬化劑組成物（B6)120份。官能基當量為 188g/eq.。50°C中之黏度為1200mPa.s(E型黏度儀）。合成例1(比較用硬化劑組成物B7) 在備有攪拌機、回流冷凝管以及攪拌裝置之燒瓶中，一邊實施氮氣吹淨，一邊添加1，4-環己烷二曱醇（新曰本理化製造；SKY-CDM)20份、酸酐（Hl)l〇〇份，在6〇°c進行 4小時加熱檟;拌。得到含有比較例用之多元叛酸及酸肝的硬化劑組成物（B7)120份。官能基當量為171g/eq.。25ΐ 中之點度為18900mPa.s(E型黏度儀）。合成例2(比較用硬化劑組成物β8) 在備有攪拌機、回流冷凝管以及攪拌裝置之燒瓶中，一邊實施氮氣吹淨，一邊添加新戊二醇2〇份、酸酐（ηι)ι〇〇 52 322150 201120000 份，在60°C進行4小時加熱攪拌。得到含有比較例用之多元羧酸及酸酐的硬化劑組成物（B8)12()份。官能基當量為 197g/eq.。25°C中之黏度為238〇〇mPa.s(E型黏度儀）。合成例3(比較用硬化劑組成物B9) 在備有攪拌機、回流冷凝管以及攪拌裝置之燒瓶中，一邊實施氮氣吹淨，一邊添加丨，6_己二醇2〇份、酸酐（hi) 100份’在60°C進行4小時加熱攪拌。得到含有比較例用之多元羧酸及酸酐的硬化劑組成物（B9)12〇份。官能基當量為197g/eq. °25°C中之黏度為15600mPa.s(E型黏度儀）。合成例4(環氧樹脂EP-2) 在反應容器中饋入石-(3, 4-環氧基環己基）乙基三曱氧石夕烧106份、重量平均分子量n〇〇(GPC測定值）之矽醇末端甲基苯基矽酮油234份（矽醇當量850 ;係使用GPC所測定之重量平均分子量之1/2而算出）以及0.5%氫氧化_ (KOH)甲醇溶液18份，將浴溫設定在75Ϊ：而進行升溫。升溫後，使其於回流下反應8小時。接著，追加甲醇305份後，費時60分鐘滴入蒸餾水之曱醇溶液（濃度為5〇重量％)86. 4份，使其於回流下75 °C中反應8小時。反應結束後，以5%之磷酸二氫鈉水溶液中和後，在80°C蒸館回收甲醇約90%。添加曱基異丁酮380 份’並以200份之水進行反覆3次之水洗。其次，藉由使用旋轉蒸發器將有機相在減壓下、100X：中去除溶媒，得至,j 具有矽氣烷構造之環氧樹脂（EP_2)300份。所得化合物之環氧當量為729g/eq、重量平均分子量為2200，外觀為無 322150 53 201120000 色透明者。合成例5(環氧基之原料化合物D-1) 在備有擾拌機、回流冷凝管、擾拌裝置以及 Dean Stark官之燒瓶中，一邊實施氮氣吹淨，一邊添加· 1,4-環己烷二羧酸二甲酯（岩古瓦斯（股）製造；DMCD_p)U{) ‘ 伤。環己烯-4-曱醇314份、四丁氧基鈦〇. 〇7份，一邊以 12〇C1 小時、150°C1 ]、時、17(TC1 小時、190°C12 小時去除經反應所生紅，-邊進行反應。經確認氣相層析 (GC)中，原料峰為1面積％以下後，冷卻至50Ϊ。 $部結束後，添加347份之曱苯使其均勻，然後，將心，液^ 10重量％之氫氧化鈉水溶液80份進行3次清洗、再―財100份/次反覆進行水洗使廢水成為中性為止。在以旋轉蒸發器加熱減壓下，顧除甲苯與未反應之3_環己甲ϋ。得到以雙（3_環己稀基甲基H，4_環己炫二羧酸為主成分之常溫為液狀的化合物（D-l)24〇份。合成例6(環氧樹脂EP-3) 在備有攪拌機、回流冷凝管以及攪拌裝置之燒瓶中，邊實轭氮氣吹淨，一邊添加水π份、ι2—鎢磷酸〇. 95 伤氫一鈉0.78份、三辛基乙酸錄之50%二甲苯溶液 2· 7伤、甲苯180份以及合成例5所得之化合物（d_i)i 18 伤。將此溶液升溫至6(TC，一邊激烈地攪拌，一邊以1小The sclerosing tree which can be used as the sclerosing tree of the present invention is the solvent of the curable resin of the present invention 322150 40 201120000. The mixture of the composition and the solvent is generally used in an amount of 10 to 70% by weight, and 15 to 70% by weight. The amount of % is better. Further, the liquid composition can be directly obtained by RTM to obtain an epoxy resin cured product containing carbon fibers. Further, the curable resin composition of the present invention can also be used as a modifier for a film-type composition. Specifically, it can be used in the case where flexibility or the like is improved in the B-stage. In such a thin resin composition, the curable resin composition A of the present invention can be applied as a curable resin composition varnish to a release film, and after removing the solvent by heating, a B-stage can be obtained. As a sheet-like adhesive. The sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like. Next, the epoxy resin composition of the present invention will be described in detail when it is used as a sealing material or a die-bonding material for a photo-semiconductor. When the epoxy resin composition of the present invention is used as a sealing material or a die-bonding material of a photo-semiconductor such as high-brightness white LED, a curing agent (hardener composition) containing a polyvalent carboxylic acid of the formula (J), The epoxy resin composition is sufficiently mixed with a cerium additive such as a curing accelerator other than an epoxy resin, a coupling agent, an antioxidant, or a light stabilizer to be used as a sealing material, or as both a die-bonding material and a sealing material. . The mixing method is carried out by using a kneader, a triaxial roll, a multi-functional agitating machine, a planetary mixer, a homogenizer, a homogenizer, a bead mill, or the like at normal temperature or under heating. Optical semiconductors such as high-brightness white LEDs are generally GaAs, GaP, GaAlAs, GaAsP, AlGa, InP, GaN, InN, AlN, InGaN, etc. laminated on substrates such as sapphire, spinel, SiC, Si, and ZnO. The semiconductor wafer is bonded to the lead frame, heat sink or package with an adhesive (adhesive material) to 41 322150 201120000. There is also a type in which a metal wire or the like is connected by a current. The semiconductor wafer is sealed with a dense alloy such as an oxygen resin in order to prevent heat or moisture and to achieve the function of the lens function. The epoxy resin composition of the present invention can be used as the material or the die bonding material. In the step, the curable resin composition of the present invention is conveniently used on both the die-bonding material and the sealing material. The semiconductor wafer is coated with the curable resin composition of the present invention and then applied to the substrate. The epoxy resin composition of the present invention is coated by a dispenser, infusion, screen printing, and the semiconductor wafer is placed thereon. The heat curing can be performed to make the semiconductor wafer follow. The heating system can use a method such as hot air circulation type, infrared ray, or high frequency. The heating conditions are, for example, 80 to 230X: preferably 1 minute to 24 hours. For the purpose of reducing the internal stress generated during heat hardening, it can be pre-hardened at 8 〇 to 120 ° C for 30 minutes to 5 hours, and then 12 〇 to 丨 8 〇 7 and 30 minutes to 1 〇 hour. It hardens afterwards. The molding method of the sealing material can be formed by heating and hardening the sealing material in the frame inserted into the substrate of the semiconductor wafer as described above, and then forming the sealing material by pre-applying the model on the model. A semiconductor wafer that is fixed to the substrate is immersed therein, and is subjected to a compression molding method such as mold release by force η. Examples of the injection method include dispensing, tanker molding, and injection molding (injecti〇n m〇iding). For heating, a method such as hot air circulation type, infrared ray, and high frequency can be used. The heating conditions are, for example, 80 to 23 Torr. (:, about 1 minute to 24 hours is preferred. For the purpose of reducing the internal stress generated during heat hardening, 322150 42 201120000 can be pre-hardened for 30 minutes to 5 hours at 80 to 120 ° C, 盅,,, 丹The post-hardening of the curable resin composition of the present invention can be used for the general use of the thermosetting resin such as Epoxy resin, etc., from 12 to 180 ° C for 30 minutes to 10 hours. Specifically, it can be used as a sealing agent, a coating material, a coating agent, a molding material (sheet, film, PRP, etc.), an insulating material (including a printed substrate, a wire coating, etc.), a sealing material, a sealing material, and a substrate. The cyanate resin composition, the acrylate resin used as a curing agent for the nose, the sputum, and the like, the additives to other resins, etc. The following agents are used for civil engineering, construction, automotive, general affairs. Examples of the adhesive for medical use include an adhesive for an electronic material. Examples of the adhesive for an electronic material include an interlayer adhesive of a multilayer substrate such as a build-up substrate; Agent, bottom An adhesive for semiconductors such as a filler (such as underfiii); an underfill for BGA reinforcement, an anisotropic conductive film (ACF. Anisotropic Conductive Film), and an adhesive for encapsulation such as an anisotropic conductive paste (ACP). Examples of the sealing material include perfusion, impregnation, and transfer molding sealing for capacitors, transistors, diodes, light-emitting diodes, 1C, LSI, etc.; so-called perfusion for IC, LSI COB, COF, TAB, etc. Sealing, bottom filling for flip chip, etc., sealing of ic package such as QFP, BGA, CSP, etc. at the time of mounting (including underfill for reinforcement), etc. The present invention is obtained by hardening a curable resin composition of the present invention. The cured product can be used in various applications mainly including optical component materials, and the optical material generally means a material used for the purpose of passing visible light, infrared rays, ultraviolet rays, xenon rays, laser light, etc. through the material. 322150 43 201120000 In addition to the LED sealing materials such as the lamp type and the in i SMD type, the film for the left eye, the corner correction film, the adhesive, the pseudo liquid crystal, etc. (4) The first color film protects the 5 vine film and displays the surrounding materials. It is the color PDP (display (4)) sealing material expected for the next generation of the half-face display,: reflection 2, light correction film, shell material, front glass Protective film, front glass 1 substitute material, adhesive; or led nuclear plastic material used in LED display device, LED sealing material, front glass protective film, front glass substitute material, adhesive; or The substrate material, the light guide plate, the cymbal sheet, the deflecting plate, the phase difference plate, the viewing angle correction film, the adhesive agent, the polarizing plate protective film in the liquid crystal (ΡΑΙΧ) display, or the organic EL (electric field illuminating) display device The protective film of the front glass; the substitute material of the front glass, the adhesive; or various film substrates in the field emission display (FED), the protective film of the front glass, the substitute material of the front glass, and the adhesive. In the field of optical recording, it is VD (image disk;), cd/CD-ROM, CD-R/RW, DVD-R/DVD-RAM, M0/MD, PD (phase-change optical disc), magnetic for optical cards. Disc substrate material, reading lens, protective film, sealing material, adhesive, and the like. In the field of optical machines, there are materials for lenses for still cameras, finder mirrors, mirrors, viewfinder masks, and photoreceptors. There are also camera lenses and viewfinders. There are also projection mirrors for projection TVs, protective films, sealing materials, and adhesives. There are also lens materials, sealing materials, adhesives, films, and the like for photosensitive machines. In the field of optical components, there are optical materials in the optical communication system, fiber optic materials, frog mirrors, waveguides, sealing materials for components, and adhesives. Fiber optic materials, metal hoops, sealing materials, and 322150 201120000 coatings. The light passive element and the optical circuit element are a lens, a waveguide, a sealing material for an LED, a sealing material for a CCD, an adhesive, and the like. Substrate material, fiber material, and sealing material for components around the optoelectronic integrated circuit (0EIC) • Subsequent agents. In the field of optical fibers, there are lighting/light guides for decorative displays, sensors for display applications, display/labeling, etc., or communication bases for telecommunication infrastructure and digital connection machines for digital devices in the home. Among the materials surrounding the semiconductor integrated circuit, there are resist materials for microetching for LSI and super LSI materials. In the field of automobiles/transport machines, there are automotive reflectors, bearing retainers, gear parts, corrosion layers, switching parts, headlights, engine parts, electronic parts, various interior and exterior parts, drive engines, brake tanks, and automobiles. Use anti-recording steel plate, inner side plate, interior material, protection/end harness, fuel pipe, lamp, glass substitute. There is also a laminated glass for railway vehicles. It can also be a fine agent for the structural material of the aircraft, an engine peripheral member, a wire harness for protection/end, and a barrier layer. In the construction field, there are interior/processing materials, electrical masks, sheets, and glass interlayer films: glass substitutes, and solar cell peripheral materials. Agricultural users have membranes for greenhouse covering. As the next generation of light/electronic functional organic materials, there are organic L-component peripheral materials, organic light-refracting elements, optical-amplifying elements, optical arithmetic elements, substrate materials around organic solar cells, fiber materials, and components. The sealing material is an adhesive or the like. Examples of the sealant include perfusion, impregnation, transfer molding and sealing for capacitors, transistors, diodes, light-emitting diodes, ICs, LSIs, etc.; ic, LSI-based COB, CQF, TAB, etc. Sealing; Cladding and other bottoms# Filling, BGA, CSP and other 1C packages are sealed at the time of installation (including strong 322150 45 201120000 for bottom filling). The other use of the optical material is a general use of the curable resin composition A or the curable resin composition B, and examples thereof include an adhesive, a coating material, a coating material, a molding material (including a sheet, a film 'FRp, etc.), Insulation materials (including printed boards, wire coatings, etc.), sealants, additives to other resins, etc. The adhesive agent may be an adhesive for electronic materials, in addition to an adhesive for civil engineering, construction, automotive, general use, and medical use. Examples of the adhesive for the electronic material in the above-mentioned materials include an interlayer adhesive for a multilayer substrate such as a build-up substrate; a semiconductor adhesive for a die bond or an underfill; and a BGA-reinforced underfill agent for an anisotropic conductive film. (ACF), an adhesive for encapsulation such as an anisotropic conductive paste (ACP). [Examples] Hereinafter, the present invention will be specifically described by way of examples, but the following $ is not particularly limited, that is, parts by weight. Further, the invention is not limited to the embodiment. Further, in the present invention, the measurement of gel chromatography (hereinafter referred to as "Gpc") is as follows. The column is Shodex SYSTEM-21 (KF-803L, KF-802. 5U2), KF-802), the eluent is tetrahydrofuran, the flow is 1 mL/min, and the column temperature is 4 (rc, The detection system was carried out under RI (reflectance), and the standard curve was a standard polystyrene produced by Shodex. The functional group equivalent was calculated from the ratio determined by GPC, and the carboxylic acid and the acid anhydride were respectively obtained as one equivalent. Example 1 (Polycarboxylic acid composition A1) In a flask equipped with a stirrer, a reflux condenser, and a stirring device, toluene ι 322150 46 201120000 parts were added while nitrogen purge was performed. 2'4-diethyl 5-pentanediol (manufactured by Kyowa Fermentation Chemicals (8); Condensed Glycol PD9) 80 parts, a mixture of methyl hexahydro sulphate and a hexahydrate acid needle (New Japan Physicochemical Co., Ltd.) ;Rikacid MH700 ratio: 7:3, the following is called acid needle H1) 168 parts, at 1 〇〇. (: 4 hours of heating and mixing. At this point, the point where the material disappears (1 area% or less) After the end of the reaction, the reaction should be completed. After the reaction is completed, the residual solvent is introduced using a rotary evaporator. In addition, 246 parts of the polycarboxylic acid composition (A1) of the present invention were obtained. The obtained colorless solid resin had a polycarboxylic acid content of 97% by area via GPC, and a functional group equivalent of a carboxyl group and an acid anhydride (hereinafter referred to as The functional group equivalent is 245 g/eq·. Further, although the shape is solid, it has a slight fluidity and is slowly deformed at room temperature to have a shape close to a semi-solid shape. Example 2 (hardener composition B1) Relative to 25 parts of the polycarboxylic acid composition (A1) obtained in Example 1 was uniformly dissolved by adding 75 parts of an acid anhydride (Η1) to obtain a hardener composition (Β1) of the present invention. The viscosity at 50 ° C was 450 mPa. .s (£-type viscometer). Example 3 (hardener composition B2) In a flask equipped with a stirrer, a reflux condenser, and a stirring device, while blowing nitrogen gas, 2, 4_diethyl 5 was added. _Pentanediol (Concord Fermentation Chemicals Co., Ltd.; Concord Glycol PD9) 2 parts, sour liver (hi) i〇〇 part 'heated and stirred at 60 ° C for 4 hours. Confirm 2, 4- 2 via gpc Ethyl-1,5-pentanediol is 1% by area or less. A polycarboxylate containing the present invention is obtained. The hardener composition (B2) of the acid composition is 12 parts by weight. The obtained reaction product is a colorless liquid resin. The ratio of the combination of GPC is: 52% by area of decanoic acid (μ), fluorenyl hexahydrophthalic anhydride The total amount with hexahydrophthalic anhydride is 48 area 47 322150 201120000%, and the functional group equivalent is 197 g/eq. The viscosity at 50 ° C is 1340 niPa.s (19700 mPa.s at 25 ° C; E-type viscosity) instrument). Examples 4 and 5 (curable resin composition) The curing agent was obtained by using the curing agent compositions B1 and B2 of the present invention obtained in Examples 2 and 3, respectively, and using 3, 4-epoxycyclohexyl group as the epoxy resin. Methyl-3,4-epoxycyclohexylcarboxylate (manufactured by Dow Chemical Co., Ltd.; UVR-6105 hereinafter referred to as epoxy resin (EP-1)), and hardening accelerator are cetyltrimethyl hydroxide The ammonium amide (manufactured by Tokyo Chemical Industry Co., Ltd.; 25% sterol solution, hereinafter referred to as C1) was prepared by blending ratio (parts by weight) shown in Table 1 below, and after defoaming for 20 minutes, the present invention was obtained. A curable resin composition. Comparative Example 1 (Compacting Curable Resin Composition) In the above Examples 4 and 5, except that the curing agent was changed to the acid anhydride (H1), the same steps as in Examples 4 and 5 were carried out, and the comparative hardening property was obtained. Resin composition. Using the obtained curable resin composition, a volatilization test and an LED test were carried out at the points indicated below, and the results are shown in Table 1. Further, the curing conditions were 15 °C for 5 hours after preliminary hardening at 120 ° C for 2 hours. Volatilization test: The curable resin compositions obtained in Examples 4 and 5 and Comparative Example 1 were vacuum-deaerated for 20 minutes, and then slowly injected. The heat-resistant adhesive tape is used as a dam on a glass substrate to be molded into a size of 30 mm x 20 mm x 1 mm. After the weight of the resin of the mold is correctly measured, the mold is hardened under the above conditions. 0 48 322150 201120000 The weight of the material was measured to confirm the decrease in weight at the time of hardening. Further, either of the curing examples 4 and 5 and the comparative example were carried out in the same oven. LED test: Examples 4, 5 and Comparative Example i Each of the obtained curable resin compositions was subjected to vacuum defoaming for 2 G minutes, and then individually filled in a graduated cylinder. The above-mentioned one was injected and molded into a surface package each having a light-emitting element having an emission wavelength of 46 glasses, using a precision discharge device. Type (10) type 3m_) LED. Then, the evaluation was carried out under the above-mentioned hardening conditions to obtain an evaluation item and evaluation criteria: (a) Volatileness: The surface of the cured product after sealing was visually observed for irregularities and evaluated. The evaluation criteria in the table are as follows. 〇: I can't see a hole. △: I saw some micro-pits. X: I see most of the holes (with lines exposed). (b) Reflow test: The obtained test was absorbed by a led at 30 ° C, 7 ° C for 72 hours, and then confirmed by a high-temperature observation device (SMT Scope SK, 5 〇〇〇; manufactured by Sanyo Seiko Co., Ltd.). The presence or absence of cracking in the LED under the following reflow conditions. The test was carried out at n=3 and evaluated by (〇κ number)/(test number). At the same time, the above (0K number) does not show the number of passes produced by the crack. The condition means that the temperature is raised to 150 at 25 ° C at 2 ° C / sec. (:, then maintained at 150 ° C for 2 minutes, then heated to 260 ° C at 2 ΐ / sec and maintained for 10 seconds, then cooled to room temperature at 1.30 / sec. 322150 49 201120000 Table 1 B1 ~ B2 TTi - 4 Example 5 Comparative Example 1 Unit hardener composition 18.7 - Parts by weight 19.9 parts by weight of hardener HI EP1 '_ 16.8 parts by weight of epoxy resin 13.0 13.0 13.0 parts by weight of hardening accelerator Cl 0. 05 0. 05 0. 05 Parts by weight -- Volatilization test (volatilization) 4.6 5.8 13.0% by weight (a) LE1D test (匕) Em 〇 X X 3/3 ------1 3/3 1/3 Examples 4, 5 and In Comparative Example J, when the amount of volatilization of the curable resin composition of the present invention is 彡, no problem such as exposure of the wire is caused even in the case of sealing (four), and the occurrence of turtles is not observed even during reflow. From the above results, it is understood that when the curing agent composition of the present invention containing the multi-frequency acid composition of the present invention and the acid needle is used as a curing agent, volatility resistance and excellent resistance to cracking can be obtained. The curable resin composition of the cured product. Example 6 (hardener composition β3) In the flask of the mixing machine, reflux condenser and stirring device, :==' Add 2'4-based diol (made by Co., Ltd.), 12 parts, and anhydride (ηι) ) 73 soil, ', 4 ring has been tempered acid _1, 2-anhydride (Η-ΤΜΑη Mitsubishi Gas Chemical Manufacturing 'hereinafter referred to as Η 2) 15 parts, at 6 (TC for 4 hours heating and stirring. Confirmed by 2GPC 2 '4. Diethyl-1,5-pentanediol is 1% by area or less and then 322150 50 201120000 100 parts of the hardener composition (B3) of the present invention containing the polycarboxylic acid of the formula (1) and an acid anhydride are obtained. The obtained colorless liquid resin had a functional group equivalent of 183 g/eq. The viscosity at 50 ° C was 1010 mPa·s. Example 7 (hardener composition B4) was equipped with a stirrer, a reflux condenser, and a stirring device. In the flask, • 2, 4-diethyl 4,5-pentanediol (manufactured by Kyowa Fermentation Chemicals Co., Ltd.; Condensed Glycol PD9) was added to the flask while the nitrogen purge was performed. Hexanedicarboxylic anhydride (manufactured by Nippon Chemical and Chemical Co., Ltd.; Rikacid ΜΗ H3), at 60 ° (: 4 hours heating and stirring. via 6? It is confirmed that 2,4-diethyl-1,5-pentanediol is 1% by area or less. 120 parts of the hardener composition (B4) containing the polycarboxylic acid of the formula (1) and an acid anhydride is obtained. The functional group equivalent is 2 〇ig/eq. 5 (The viscosity in TC is 1100 mPa.s (25t: medium is 16200mPa.s; E-type viscometer). Example 7a From the hardener composition (B4) 50 parts 'The use of a rotary evaporator to remove excess methyl hexahydrophthalic anhydride from 1 Torr to 150 ° C (from the point where the fluorenyl hexahydrophthalic anhydride no longer flows out) In the case where the acid anhydride was sufficiently removed by heating under reduced pressure for a few minutes, 25 parts of the polycarboxylic acid composition (B4a) of the present invention was taken out. The shape is a colorless semi-solid to solid resin. The viscous viscosity of the resin is 0. 08Pa.s. The softening point of the resin is 5.8 °C. Example 8 (hardener composition B5) In a flask equipped with a stirrer, a reflux condenser, and a stirring device, 2, 4-diethyl-1,5-pentanediol was added while purging with nitrogen. 51 322150 s- 201120000 and fermentation chemistry (stock); 12 parts of copolydiol diol PD9), 73 parts of acid anhydride (H3), 15 parts of acid anhydride (H2), heated and stirred at 60 ° C for 4 hours. It was confirmed by GPC that 2,4-diethyl-1,5-pentanediol was 1 area% or less. A hardener composition (B5) containing the polybasic acid of the formula (1) and an acid anhydride was obtained in a portion. The result is a colorless liquid resin. The functional group equivalent weight was 186 g/eq. The viscosity at 50 °C is 1050 mPa*s. Example 9 (hardener composition B6) In a flask equipped with a stirrer, a reflux condenser, and a stirring device, 2,4-diethyl-1,5-pentanediol was added while performing nitrogen purge. Fermentation chemistry (manufacturing); 20 parts of copolydiol diol PD9), 100 parts of cyclohexanone dihydroxanthate' was heated and stirred at 60 ° C for 4 hours. It was confirmed by gpc that 2,4-diethyl-1,5-pentanediol was 1 area% or less. 120 parts of a hardener composition (B6) containing the polyvalent carboxylic acid of the formula (1) and an acid anhydride was obtained. The functional group equivalent was 188 g/eq. The viscosity at 50 ° C is 1200 mPa.s (E-type viscometer). Synthesis Example 1 (Comparative Hardener Composition B7) In a flask equipped with a stirrer, a reflux condenser, and a stirring device, 1,4-cyclohexanedimethanol was added while purging with nitrogen gas. Manufactured; SKY-CDM) 20 parts, an acid anhydride (Hl) 1 part, heated at 6 ° C for 4 hours; mixed. 120 parts of a hardener composition (B7) containing a plurality of polyphenolic acid and acid liver for comparative use were obtained. The functional group equivalent was 171 g/eq. The point in 25ΐ is 18900mPa.s (E-type viscometer). Synthesis Example 2 (Comparative Hardener Composition β8) In a flask equipped with a stirrer, a reflux condenser, and a stirring device, while purging with nitrogen, 2 parts of neopentyl glycol and an acid anhydride (ηι) were added. 52 322150 201120000 parts, heated and stirred at 60 ° C for 4 hours. A 12 part portion of the hardener composition (B8) containing the polycarboxylic acid and the acid anhydride used in the comparative example was obtained. The functional group equivalent was 197 g/eq. The viscosity at 25 ° C is 238 〇〇 mPa.s (E-type viscometer). Synthesis Example 3 (Comparative Hardener Composition B9) In a flask equipped with a stirrer, a reflux condenser, and a stirring device, ruthenium, 6-hexanediol, and an acid anhydride (hi) were added while purging with nitrogen. 100 parts 'heated and stirred at 60 ° C for 4 hours. The hardener composition (B9) containing the polycarboxylic acid and the acid anhydride used in the comparative example was obtained in 12 parts. The functional group weight was 197 g/eq. The viscosity at 25 ° C was 15600 mPa·s (E-type viscometer). Synthesis Example 4 (Epoxy Resin EP-2) 106 parts of stone-(3,4-epoxycyclohexyl)ethyltrioxoxalate was introduced into a reaction vessel, and the weight average molecular weight n〇〇 was measured by GPC. Value) 234 parts of sterol-terminated methyl phenyl fluorenone oil (sterol equivalent 850; calculated using 1/2 of the weight average molecular weight measured by GPC) and 18 parts of 0.5% KOH (KOH) methanol solution The bath temperature was set to 75 Ϊ: and the temperature was raised. After warming up, it was allowed to react under reflux for 8 hours. Next, after adding 305 parts of methanol, 86. 4 parts of a decyl alcohol solution (concentration: 5% by weight) of distilled water was added dropwise thereto over 60 minutes, and the mixture was reacted at 75 ° C for 8 hours under reflux. After completion of the reaction, the mixture was neutralized with a 5% aqueous solution of sodium dihydrogen phosphate, and then methanol was recovered at 80 ° C for about 90%. 380 parts of decyl isobutyl ketone was added and washed with water for 3 times with 200 parts of water. Next, by dissolving the organic phase under reduced pressure at 100X: using a rotary evaporator, it was obtained that 300 parts of epoxy resin (EP_2) having a helium-ane structure was obtained. The obtained compound had an epoxy equivalent of 729 g/eq, a weight average molecular weight of 2,200, and an appearance of no 322150 53 201120000 color transparent. Synthesis Example 5 (Organic Compound D-1 of Epoxy Group) In a flask equipped with a scrambler, a reflux condenser, a scrambler, and a Dean Stark, a nitrogen purge was performed while adding a 1,4-ring. Dimethyl hexanedicarboxylate (manufactured by Iwaswas Co., Ltd.; DMCD_p) U{) 'Injury. 314 parts of cyclohexene-4-nonanol, tetrabutyloxytitanium 〇. 7 parts, one side of 12 〇C1 hour, 150 °C1], hour, 17 (TC1 hour, 190 °C 12 hours to remove the reaction In the gas chromatography (GC), after confirming that the raw material peak was 1 area% or less, it was cooled to 50 Torr. After the end of the portion, 347 parts of benzene was added to make it uniform, and then, the heart was 80 parts of a 10% by weight aqueous sodium hydroxide solution was washed three times, and then washed again with 100 parts/time of water to make the wastewater neutral. Under the heating and decompression by a rotary evaporator, toluene and no 3_cyclohexylmethyl hydrazine was reacted, and 24 parts of a compound (D1) having a bis (3-cyclohexylmethyl)H,4-cyclohexyl dicarboxylic acid as a main component in a liquid state was obtained. 6 (Epoxy resin EP-3) In a flask equipped with a stirrer, a reflux condenser and a stirring device, the yoke was purged with nitrogen while adding π parts of water, ι2 - strontium tungstate phosphate. , trioctyl acetic acid recorded in a 50% xylene solution 2.7 wounds, 180 parts of toluene and the compound (d_i) i obtained in Synthesis Example 5 were injured. The solution was heated to 6 (TC, while stirring vigorously, one small

時添加35重量％含過氧化氫之水溶液70份，直接在60°C 攪拌13小時。確認氣相層析中之反應的進行，原料波峰為 1面積％。 54 322150 201120000 接者，以1重量％氫氧化鈉水溶液中和後，添加扣量《代魏财純25㈣行3Q分狀祕後靜置。取出分離為2層之有機層’在此添加活性碳(味之素精細化學；(股）製造；CP1)20份、膨濁土（屻un公司製造Bengel ®20份，在室溫檀拌丨小時後過滤。將所得遽液以水刚份進打3次水洗，並經由有機層顧除甲苯，得到常溫_ 狀之极氧樹脂（EP-3M19份。所得環氧樹脂之環氧當量為 217g/eq.。25 C中之黏度為9200mPa.s(E型黏度儀）。合成例7(環氧樹脂之原料二烯烴化合物d_2) 參照PCT/JP2_/m432，在備有授拌機、回流冷凝官以及攪拌裝置之燒瓶中，一邊實施氮氣吹淨，一邊添加水150份、3-環己烯甲醛55. 1份、雙三羥甲基丙烷62 6 份、濃鹽酸7· 3份，在6(TC進行反應1〇小時。反應結束後，於反應液中添加水1 〇份、3%氫氧化鈉水溶液3〇份，接著，該反應液以磷酸氫鈉中和。在此添加曱基異丁酮份，以水100份進行3次水洗後，藉由餾除溶劑，得到二婦烴化合物（D-2)l〇l份。合成例8(環氧樹脂EP-4) 參照PCT/JP2009/067432 ’在備有攪拌機、回流冷凝管以及攪拌裝置之燒瓶中，一邊實施氮氣吹淨，一邊添加水15份、12-鶴磷酸〇. 47份、鱗酸氫二銅〇· 39份、二辛基乙酸銨之50%二甲苯溶液1.4份、甲笨9〇份以及合成例 7中所得之化合物（D-2)54份。將此溶液升溫至6(rc，一邊激烈地擾摔’ 一邊以1小時添加35重量％含過氧化氣之 322150 55 201120000 水溶液35份，並直接在6(rc攪拌13小時。於氣相層析中確認反應之進行時，原料波峰為丨面積％以下。接著，以1重量％氫氧化鈉水溶液中和後，添加2〇重量％硫代硫酸鈉水溶液12份，攪拌3〇分鐘後靜置。取出分離成2層之有機層，在此添加活性碳（味之素精細化學（股）製造，CP1)10 份、蒙脫石 QQJNIMINE INDUSTRIES(股）製造； Kunipia)10份，在室溫攪拌3小時後過濾。將所得濾液以水100份進行3次水洗，並經由所得之有機層餾除甲苯，得到常溫為液狀之環氧樹脂（EP-4)49份。所得環氧樹脂之環氧當量為262g/eq·。25t中之黏度為230000mPa. s(E塑黏度儀）。實施例10(硬化性樹脂组成物）環氧樹脂係使用合成例4中所得環氧樹脂（EP2)、硬化劑係使用實施例3中所得硬化劑組成物（B2)、硬化促進劑係使用四級鱗鹽（日本化學工業（股）製造；Hishicolin ?又41?以下稱為匚2)、添加劑係使用雙（2,2,6,6-四甲基-4-痕啶基）癸二酸酯（日本汽巴（股）製造；TINUVIN770DF以下稱為L1)以及磷系化合物係使用4,4’ -亞丁基雙（3-曱基 -6-第三丁笨基-二-十三烷基磷酸酯）（ADEKA製造； Adekastab 260以下稱為Ml)，以下述表2所示之調配比例（重量份）進行調配，進行20分鐘之脫泡後，得到本發明之硬化性樹脂組成物。對於所得硬化性樹脂組成物係以後述方法進行適用期（p〇t-iife)試驗。將結果併記於下述表 2 〇 56 322150 201120000 將所得硬化性樹脂組成物徐缓地注入試驗片用模型中成型’以120°Cx3小時之預備硬化後i50〇Cxl小時之條件使該鑄造物硬化而得到各種試驗用之硬化物。對於所得硬化物’將以下之熱耐久性穿透率試驗、LED點燈試驗依下述記載之條件進行評價。並將結果併示於下述表2。適用期將製成之硬化性樹脂組成物置於室溫時的黏度變化，在3小時後與6小時後進行測定。然後，以該黏度上昇率（經時黏度/初期黏度χ1〇〇)(%)進行評價。熱财久性穿透率試驗财熱試驗條件：在l5〇〇c烘箱中放置96小時試驗片尺寸：厚度lmm 評價條件：經分光光度計測定400nm之穿透率。並算出其變化值。 LED點燈試驗將所得硬化性樹脂組成物充填於量筒中並使用精密吐出裝置注入並成型於搭載有中心發光波465ηιη<晶片的外徑5mm立方之表面封裝型led封裝物（内徑4.4mm、外壁回度l.25mm)。將該鎊造物放入加熱爐内，進行12(TC ' 1 小時，再於15(rc、3小時之硬化處理，作成lED封裝物。將LED封裴後，以下述條件使LED點燈後測定照度，結果不於表2。點燈詳細條件發光波長：465nm 57 322150 201120000 預定電流為30mA) 驅動方式：定電流方式、6QmA(發光元件驅動環境：85。(：、85% 驅動時間：200小時、4〇〇小時評價：點燈後之照度維持率比較例2、3、4 或3=Γ"’除了將硬化劑變更為合成例h 二 ===或〜，與實心之各個硬化性樹脂組成物，進行同適=得驗。將結果記載於下述表2。功碑並且，將上述所得比較用之硬化性樹脂組成物，使复進行同與實施例10之硬化，對於所得之硬化物，將以下/、熱耐久性穿遂率試驗、LED點燈試驗依下述記載之條行5平"U。並將結果併記於下述表2。 58 322150 201120000 表2 項目實施例10 比較例2 比較例3 比較例4 樹脂有機聚矽氧烷 EP-2 10.0 10.0 10.0 10.0 B2 2.8 硬化劑硬化劑組成物 B7 2.8 組成 B8 2.8 B9 2.8 硬化 _促進劑四級鱗鹽 C2 0.01 0.01 0.01 0.01 添加劑光安定劑 L1 0.03 0.03 0.03 0. 03 磷系化合物 Ml 0.03 0. 03 1 0.03 0.03 硬化性樹脂組成物適用期黏度上昇率 (3小時） % 120 121 129 122 黏度上昇率 (6小時） % 155 190 202 172 熱耐久性穿透率試驗初期穿透率 (400nm) % 91.4% 91.5% 92. 0% 91.0% 硬化物性維持率(400nm) _照度維持率 (200小時後） % .88.7% 87. 3% 87.9% 88. 6% LED點燈試驗 % 105% 71% 102% 105% 照度維持率 (400小時後） % 99% —-_ - 52% 39¾ 由以上之結果可知，本發明之硬化性樹脂組成物之黏度上昇率低，係具有更長試用期者。並且，相較於使用其它骨架之物㈣瞭使用本發明之多元紐料物的硬化物在作為LED時之照度維持率優異且光學特性亦佳。實施例11、12(硬化性樹脂组成物）環氧樹脂係使用合成例6、8 +所得之環氧樹脂（Ep-3、 EP-4)、硬化劑係使用實施例7中所得之硬化劑組成物 (B4)、硬化促進劑係使用四級鱗鹽（日本化學工業（股）製造；HishicolirT* PX4MP以下稱為⑵、添加劑係使用"雙 (2, 2, 6, 6-四甲基-4-哌啶基）癸二酸酯（日本汽巴（股）f 造；測爾肩以下稱為L1)以及磷系化合物係使用 59 S. 322150 201120000 4’4’ -亞丁基雙（3-甲基-6_第三丁苯基—二_十三烧基嶙酸 SIXADEKA.製造，Adekastab 260以下稱為Ml)，以下述表 3所示之調配比例（重量份）進行調配，進行2〇分鐘之脫泡後’得到本發明之硬化性樹脂組成物。將所得硬化性樹脂組成物徐緩地注入試驗片用模型中成型，以120Cx3小時之預備硬化後15〇«>Cxl小時之條件使該鑄造物硬化而得到各種試驗用之硬化物。對於所得硬化物，將以下之LED點燈試驗依下述記載之條件進行評價。並將結果併示於下述表3。 LED點燈試驗將所付硬化性樹脂組成物充填於量筒中並使用精密 '出装置注人並成型於搭載有中心發光波465nm之晶片的外徑5mm立方之表面封裝型⑽封裝物(内徑“丽、外壁 4 h 25mD〇 °將該缉造物放入加熱爐内，進行12吖、i J時再於150C、3小時之硬化處理作成led封裝物。將LED封裝後，以下迷條件使㈣點燈後測定照度，結果示於表3。點燈詳細條件發光波長：465mn 60mA(發光元件預定電流為3〇mA) 驅動方式：定電流方式驅動環境：85°C、85% 驅動時間：200小時評價：麟200丨時後之照度維持率 322150 60 201120000 表3 項目實施例11 實施例12 組成環氧樹脂 EP-3 21. 7 EP-4 26. 2 硬化劑硬化劑組成物 B4 17. 1 17. 1 硬化促進劑四級鱗鹽 C2 0. 02 0. 02 添加劑光安定劑 L1 0. 04 0.04 磷系化合物 Ml 0. 03 0. 03 tED點燈試驗照度維持率 (200小時後） % 102% 102% 實施例13、14、15(硬化性樹脂組成物） J哀氧樹脂係使用環氧樹脂（EP-i、ep-3)、硬化劑係使用貫施例中所得之硬化劑組成物（B2、B4、B6)、並使用硬化促進劑（C2)，以下述表4所示之調配比例（重量份）進行調配，進行20分鐘之脫泡後，得到本發明之硬化性樹脂組成物。將所知硬化性樹脂組成物徐緩地注入試驗片用模型中成型’以110CX3小時之預備硬化後ι5〇ΐχ1小時之條件使該鑄造物硬化而得到各種試驗用之硬化物。對於所得硬化物’將以下之LED點燈試驗依下述記載之條件進行評價。並將結果併示於下述表4。 LED點燈試驗將所得硬化性樹脂組成物充填於量筒中並使用精密吐出裝置;主人並成型於搭载有中心發光波福⑽之晶片的外徑5丽立方之表面封《型LED封裝物(内徑4·-、外壁高度1. 25mm)。將該鑄拌札化物放入加熱爐内，進行120°C、1While adding 70 parts by weight of 70 parts by weight of an aqueous solution containing hydrogen peroxide, it was stirred at 60 ° C for 13 hours. The progress of the reaction in the gas chromatography was confirmed, and the peak of the raw material was 1 area%. 54 322150 201120000 Receiver, after neutralizing with 1% by weight sodium hydroxide aqueous solution, add deduction "Deputy Wei Caichun 25 (four) line 3Q classification after the secret. The organic layer separated into 2 layers was taken out. Here, 20 parts of activated carbon (Ajinomoto Fine Chemicals; manufactured by CP); and turbid soil (20 parts of Bengel® manufactured by 屻un Co., Ltd.) were mixed at room temperature. After the lapse of the filtration, the obtained mash was washed three times with water, and the toluene was removed from the organic layer to obtain a normal temperature olefinic epoxy resin (EP-3M 19 parts. The epoxy equivalent of the obtained epoxy resin was 217 g). /eq. The viscosity in 25 C is 9200 mPa.s (E-type viscometer). Synthesis Example 7 (diolefin compound d_2 of epoxy resin) Refer to PCT/JP2_/m432, equipped with a mixer, reflux condensation In the flask of the stirring device and the stirring device, 150 parts of water, 55.1 parts of 3-cyclohexene formaldehyde, 62 parts of ditrimethylolpropane, and 7.3 parts of concentrated hydrochloric acid were added to the flask while purging with nitrogen. (TC was reacted for 1 hour. After the completion of the reaction, 1 part of water and 3 parts of 3% aqueous sodium hydroxide solution were added to the reaction liquid, and then the reaction liquid was neutralized with sodium hydrogen phosphate. The butanone fraction was washed three times with 100 parts of water, and then the solvent was distilled off to obtain 10 parts of a dipotassium compound (D-2). Example 8 (Epoxy Resin EP-4) Refer to PCT/JP2009/067432 'In a flask equipped with a stirrer, a reflux condenser, and a stirring device, while purging nitrogen gas, adding 15 parts of water, 12-pyridinium phosphate. 47 parts, 39 parts of dibasinium bismuth hydride, 1.4 parts of a 50% xylene solution of ammonium dioctyl ammonium acetate, 9 parts of a hydrazine, and 54 parts of a compound (D-2) obtained in Synthesis Example 7. The solution was heated to 6 (rc, while violently disturbing) while adding 35 parts by weight of 35 parts by weight of 322150 55 201120000 aqueous solution containing peroxidic gas for 35 hours, and stirring directly at 6 (rc for 13 hours. Confirmed by gas chromatography) When the reaction was carried out, the peak of the raw material was less than or equal to the area of 丨. Next, after neutralizing with a 1% by weight aqueous sodium hydroxide solution, 12 parts of a 2% by weight aqueous sodium thiosulfate solution was added, and the mixture was stirred for 3 minutes, and then allowed to stand. 2 layers of organic layer, add 10 parts of activated carbon (made by Ajinomoto Fine Chemicals Co., Ltd., CP1), montmorillonite QQJNIMINE INDUSTRIES (manufactured by Kunming), 10 parts, stirred at room temperature for 3 hours. Filtration. The obtained filtrate was washed 3 times with 100 parts of water and passed through The organic layer was distilled off toluene to obtain 49 parts of epoxy resin (EP-4) at room temperature. The epoxy equivalent of the obtained epoxy resin was 262 g/eq·. The viscosity in 25 t was 230,000 mPa·s (E plastic Viscosity meter. Example 10 (curable resin composition) Epoxy resin was obtained by using the epoxy resin (EP2) obtained in Synthesis Example 4, and a curing agent using the hardener composition (B2) obtained in Example 3, and hardening promotion. The agent uses a quaternary scale salt (manufactured by Nippon Chemical Industry Co., Ltd.; Hishicolin® 41 hereinafter referred to as 匚2), and the additive system uses bis(2,2,6,6-tetramethyl-4-pyridinyl) ) sebacate (manufactured by Nippon Ciba (stock); TINUVIN 770DF hereinafter referred to as L1) and phosphorus compound using 4,4'-butylidene bis(3-indolyl-6-t-butanyl-di- Tridecyl phosphate (manufactured by Adeka; Adekastab 260 hereinafter referred to as M1), formulated in a blending ratio (parts by weight) shown in Table 2 below, and defoamed for 20 minutes to obtain a curable resin of the present invention. Composition. The obtained curable resin composition was subjected to a pot life (p〇t-iife) test in the following method. The results are shown in Table 2 below. 〇56 322150 201120000 The obtained curable resin composition is slowly injected into the test piece and molded in a mold. The casting is hardened by the condition of i50〇Cxl hours after preliminary hardening at 120 ° C for 3 hours. Various hardened materials for the test were obtained. The following heat durability transmittance test and LED lighting test were evaluated for the obtained cured product in accordance with the conditions described below. The results are shown in Table 2 below. Application period The viscosity of the resulting curable resin composition at room temperature was changed, and it was measured after 3 hours and 6 hours. Then, the viscosity was raised (advanced viscosity / initial viscosity χ 1 〇〇) (%). Thermal long-term penetration rate test Confidence test conditions: 96 hours in a l5〇〇c oven Test piece size: thickness lmm Evaluation conditions: The transmittance of 400 nm was measured by a spectrophotometer. And calculate its change value. In the LED lighting test, the obtained curable resin composition was filled in a graduated cylinder and injected and molded into a surface mount type LED package (having an inner diameter of 4.4 mm, which was provided with a center light-emitting wave 465 ηηη < The outer wall returns 1.25mm). The pound was placed in a heating furnace and subjected to 12 (TC '1 hour, and then hardened at 15 (rc, 3 hours) to prepare a lED package. After the LED was sealed, the LED was turned on after the following conditions were measured. Illumination, the results are not shown in Table 2. Lighting detailed conditions Light-emitting wavelength: 465nm 57 322150 201120000 The predetermined current is 30mA) Drive mode: constant current mode, 6QmA (light-emitting element drive environment: 85. (:, 85% Drive time: 200 hours) 4 hours evaluation: Illumination maintenance rate after lighting comparison Example 2, 3, 4 or 3 = Γ " 'In addition to changing the hardener to the synthesis example h === or ~, with solid each curing resin The composition was subjected to the same test. The results are shown in the following Table 2. The cured resin composition for comparison with the above-mentioned results was subjected to the same hardening as in Example 10, and the resulting hardening was carried out. For the following, the following /, thermal durability penetration test, LED lighting test, according to the following description, line 5 " U. And the results are recorded in Table 2. 58 322150 201120000 Table 2 Item Embodiment 10 Comparative Example 2 Comparative Example 3 Comparative Example 4 Resin Polyoxane EP-2 10.0 10.0 10.0 10.0 B2 2.8 Hardener Hardener Composition B7 2.8 Composition B8 2.8 B9 2.8 Hardening_Accelerator Grade IV Scale Salt C2 0.01 0.01 0.01 0.01 Additive Light stabilizer L1 0.03 0.03 0.03 0. 03 Phosphorus compound Ml 0.03 0. 03 1 0.03 0.03 Curable resin composition Applicable viscosity increase rate (3 hours) % 120 121 129 122 Viscosity increase rate (6 hours) % 155 190 202 172 Thermal durability penetration test Transmittance (400nm) % 91.4% 91.5% 92. 0% 91.0% Hardenability retention (400nm) _ Illuminance maintenance rate (after 200 hours) % .88.7% 87. 3% 87.9% 88. 6% LED lighting Test % 105% 71% 102% 105% Illumination retention rate (after 400 hours) % 99% - - _ - 52% 393⁄4 From the above results, it is understood that the curable resin composition of the present invention has a low viscosity increase rate and has The longer the probation period, and the cured product using the multi-material of the present invention is superior in illuminance maintenance ratio and excellent in optical characteristics as an LED compared to the use of other skeletons (IV). Examples 11 and 12 ( Curable resin composition) For the epoxy resin, the epoxy resin (Ep-3, EP-4) obtained in Synthesis Examples 6 and 8 + and the curing agent were used. The hardener composition (B4) obtained in Example 7 and the hardening accelerator were used. Grade scale salt (manufactured by Japan Chemical Industry Co., Ltd.; Hishicolir T* PX4MP hereinafter referred to as (2), additive system used "bis(2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate ( Japanese Ciba (share) f; Measured below the shoulder called L1) and phosphorus compound used 59 S. 322150 201120000 4'4' - Butylene bis (3-methyl-6_T-butylene) Manufactured by SIXADEKA., Adekastab 260 is hereinafter referred to as Ml), and is blended in the proportions (parts by weight) shown in Table 3 below, and after 2 minutes of defoaming, the hardening of the present invention is obtained. Resin composition. The obtained curable resin composition was slowly poured into a test piece mold, and the cast product was cured under the conditions of 15 C « 3 hours of preliminary hardening at 120 C x 3 hours to obtain various hardened materials for the test. For the obtained cured product, the following LED lighting test was evaluated under the conditions described below. The results are shown in Table 3 below. In the LED lighting test, the hardened resin composition was filled in a graduated cylinder and a surface mount type (10) package (outer diameter) having an outer diameter of 5 mm cube mounted on a wafer having a central light-emitting wave of 465 nm was molded by a precision device. "Li, outer wall 4 h 25mD 〇 ° put the sputum into the heating furnace, and then 12 吖, i J and then 150C, 3 hours of hardening treatment to form a led package. After packaging the LED, the following conditions make (4) The illuminance was measured after lighting, and the results are shown in Table 3. Detailed lighting conditions of the lighting: 465 nm 60 mA (the predetermined current of the illuminating element is 3 mA) Driving mode: constant current mode Driving environment: 85 ° C, 85% Driving time: 200 Hour evaluation: illuminance after 丨200丨 322150 60 201120000 Table 3 Item Example 11 Example 12 Composition Epoxy EP-3 21. 7 EP-4 26. 2 Hardener Hardener Composition B4 17. 1 17. 1 Hardening accelerator quaternary salt C2 0. 02 0. 02 Additive light stabilizer L1 0. 04 0.04 Phosphorus compound Ml 0. 03 0. 03 tED lighting test illuminance maintenance rate (after 200 hours) % 102 % 102% Examples 13, 14, 15 (sclerosing tree Composition) J ethoxylate resin is an epoxy resin (EP-i, ep-3), and a hardener is used as a hardener composition (B2, B4, B6) obtained in the respective examples, and a hardening accelerator is used ( C2) was prepared by blending in a proportion (parts by weight) shown in the following Table 4, and defoaming was carried out for 20 minutes to obtain a curable resin composition of the present invention. The curable resin composition was slowly injected into the test piece. The molded product was hardened by molding in a mold for 1 hour at 110 CX for 3 hours, and various hardened materials for the test were obtained. For the obtained cured product, the following LED lighting test was carried out according to the conditions described below. The evaluation was carried out, and the results are shown in the following Table 4. In the LED lighting test, the obtained curable resin composition was filled in a measuring cylinder and a precision discharge device was used; the master was molded on a wafer equipped with a central luminescent wave (10). The surface of the 5 cubic cube is sealed with a type of LED package (inner diameter 4·-, outer wall height 1.25 mm). The cast compound is placed in a heating furnace at 120 ° C, 1

S 61 322150 201120000 小時，再於15(TC ' 3小時之硬化處理，作成lED封裝物。將LED封裴後，以下述條件使led點燈後測定照度，結果示於表4。點燈洋細條件發光波長：465nm 驅動方式.定電流方式、60mA(發光元件預定電流為30mA) 驅動環境：85ΐ、85% 驅動時間：2〇〇小時評價：點燈200小時後之照度維持率表4 — —_—_ 項目實施例實施例14 實施例15 環氣樹賠 EP-1 ~ΎΓ~~ 6.0 6.0 ---- EP-3 4.0 4.0 4.0 組成硬化劑 B2 11.6 硬化劑組成物 B4 1.8 一硬 B5 11.0 —-- 四級鱗鹽 C2 0.01 0.01 0.01 LED點燈試驗 — 照度維持率 (200小時後） % 72% 78% 70% 實施例16、Π、ι8(硬化性樹脂組成物）環氧樹脂係使用環氧樹脂（EP-；l、ΕΡ-3)、硬化劑係使用酸軒（H1、Η2)實施例中所得之硬化劑組成物（Β3、Β5)、並使用硬化促進劑（C2)，以下述表5所示之調配比例（重量份）進行調配’進行20分鐘之脫泡後，得到本發明之硬化性樹脂組成物。將所得硬化性樹脂組成物徐緩地注入試驗片用模型 62 322150 201120000 中成型，以110 Cx3小時之預備硬化後15(Γ(：χ1小時之條件使該鑄造物硬化而得到各種試驗用之硬化物。對於所得硬化物，將以下之led點燈試驗依下述記載之條件進行評價。並將結果併示於下述表5。 LED點燈試驗將所得硬化性樹脂組成物充填於量筒中並使用精密吐出裝置注入並成型於搭载有中心發光波彳阳⑽之晶片的特5mm立方之表面封裝型LED封裝物(内徑4 4咖、外壁南度1.25mm)。將該矯造物放入加熱爐内，進行12〇ΐ、工小時，再於150C、3小時之硬化處理，作成封裝物。將led封裝後’以下述條件使LED點燈後測定照度，結果示於表4。點燈詳細條件發光波長：465nm 6〇mA(發光元件預定電流為3〇mA) 驅動方式：定電流方式、驅動環境：85°C、85% 驅動時間：200小時 .和小時後之照度維持率比較例5、6(比較用之魏性_纟且成物）上述實施例15、16及17中，除了將硬化㈣或Η2之外，進行相同做法，得到比較用之硬= 脂組成物。並且，同與上述實施例15、16及17 對於所得4個硬化物，㈣於騎_，試驗。並將結果併示於下述表5。助點 322150 63 201120000 表5 項目比較例 5 實施例 16 實施例|比較例 17 η 環氧樹脂 EP-1 6.0 6.0 6.0 10.0S 61 322150 201120000 hours, and then 15 (TC '3 hours hardening treatment, made lED package. After the LED was sealed, the LED was lit and the illuminance was measured under the following conditions. The results are shown in Table 4. Conditional emission wavelength: 465nm Driving mode. Constant current mode, 60mA (lighting element predetermined current is 30mA) Driving environment: 85ΐ, 85% Driving time: 2〇〇hour evaluation: Illumination maintenance rate after lighting for 200 hours Table 4 – ___ Project Example Example 14 Example 15 Cyclone Compensation EP-1 ~ ΎΓ~~ 6.0 6.0 ---- EP-3 4.0 4.0 4.0 Composition Hardener B2 11.6 Hardener Composition B4 1.8 A Hard B5 11.0 —-- Four-stage scale salt C2 0.01 0.01 0.01 LED lighting test — Illuminance maintenance rate (after 200 hours) % 72% 78% 70% Example 16, Π, ι8 (curable resin composition) Epoxy resin The epoxy resin (EP-; l, ΕΡ-3) and the hardener are the hardener compositions (Β3, Β5) obtained in the examples of the acid (H1, Η2), and the hardening accelerator (C2) is used, and the following The blending ratio (parts by weight) shown in Table 5 is adjusted to '20 After the defoaming of the bell, the curable resin composition of the present invention was obtained. The obtained curable resin composition was slowly injected into the test piece and molded in a model 62 322150 201120000, and after preliminary hardening at 110 Cx for 3 hours (Γ(:χ1) The cast product was hardened to obtain various cured products for the test under the conditions of the hour. The obtained LED lighting test was evaluated according to the conditions described below for the obtained cured product, and the results are shown in Table 5 below. In the lighting test, the obtained curable resin composition was filled in a measuring cylinder and injected and molded into a special 5 mm cubic surface-mount type LED package (having an inner diameter of 4 4 coffee) equipped with a central light-emitting wave (10) wafer using a precision discharge device. The outer wall is 1.25mm south. The orthodontic material is placed in a heating furnace, and is subjected to hardening treatment for 12 hours and hours, and then hardened at 150C for 3 hours to form a package. After the LED is packaged, the LED is made under the following conditions. The illuminance was measured after lighting, and the results are shown in Table 4. Lighting conditions: Illumination wavelength: 465 nm 6 〇 mA (predetermined current of the illuminating element is 3 mA) Driving method: constant current mode, driving environment: 85 ° C, 8 5% driving time: 200 hours. and illuminance maintenance rate after hours. Comparative Examples 5 and 6 (comparative use of 魏纟成成成 ) ) 上述上述上述上述上述上述上述上述上述上述上述上述上述上述上述上述上述上述上述上述上述上述上述上述上述上述上述上述上述上述, do the same thing, get the hard = fat composition for comparison. Further, in the same manner as in the above Examples 15, 16 and 17, the obtained four cured products were tested. The results are shown in Table 5 below. POINT 322150 63 201120000 Table 5 Item Comparative Example 5 Example 16 Example | Comparative Example 17 η Epoxy Resin EP-1 6.0 6.0 6.0 10.0

實施例 18 TO EP-3 4.0 4.0 4.0 組成硬化劑酸酐硬化劑組成物 H1 H2 B3 6.9 8.2 13.3 2.0 10. 硬化促進劑 B5 严級鐫鹽照ϋ持率(200 ，ED點燈試驗 --〜L 小時後) % 10.8 0.01 82% 0.01 94% 102% 0.01 12.9ΌΓ 83% 93% 實施例bl(多元羧酸組成物Abl) 在備有授拌機、回流冷凝管以及攪拌裝置之燒瓶中，一邊實施氮氣吹淨，一邊添加曱笨10份、三環癸烷二甲醇 (0XEA製造，TCD-AlcholDM)98份、曱基六氫酞酸酐與六氫酞酸酐之混合物（7 : 3)(新日本理化（股）製造；Rikacid MH700，以下稱為酸酐H1)168份，在8代進行15分鐘、 l〇(TC進行4小時之加熱騎。經由Gpc確認為原料之（面積％以下。結束反應後，使用旋轉蒸發器，將殘留的溶劑進行餘除。得到本發明之多元編^成物⑽；下述式⑶ 之構造式的混合物）施份。所得為無色固形樹脂，軟化點為74 C。炎且，溶融黏度在15代為0. 22Pa.S。依GPC之純度為99面積％。並且，官能基當量為266—·。 322150 64 201120000Example 18 TO EP-3 4.0 4.0 4.0 Composition Hardener anhydride hardener composition H1 H2 B3 6.9 8.2 13.3 2.0 10. Hardening accelerator B5 Strict 镌 salt exposure retention rate (200, ED lighting test - ~ L After the hour) % 10.8 0.01 82% 0.01 94% 102% 0.01 12.9 ΌΓ 83% 93% Example bl (polycarboxylic acid composition Abl) was carried out in a flask equipped with a mixer, a reflux condenser and a stirring device. Nitrogen purged, while adding 10 parts of hydrazine, tricyclodecane dimethanol (manufactured by 0XEA, TCD-AlcholDM) 98 parts, a mixture of decyl hexahydrophthalic anhydride and hexahydrophthalic anhydride (7: 3) (New Japan Physical and Chemical) (manufacturing) (Rikacid MH700, hereinafter referred to as anhydride H1) 168 parts, carried out in 8th generation for 15 minutes, l〇 (TC was heated for 4 hours. It was confirmed as raw material by Gpc (area% or less. After the reaction was terminated, The residual solvent was further removed by using a rotary evaporator to obtain a multicomponent composition (10) of the present invention; a mixture of the structural formula of the following formula (3) was applied. The obtained colorless solid resin had a softening point of 74 C. Further, the melt viscosity is 0.22 Pa.S in the 15th generation. The purity according to GPC is 99 area%. Further, the functional group equivalent weight of 266- ·. 32215064 201 120 000

實施例b2(硬化劑組成物Bbl) 相對於實施例bl中所得之多元羧酸組成物（Abl :式 (3)之構造式的混合物）25份，添加酸酐（jji)75份使之均勻溶解而得到本發明之硬化劑組成物（Bbi)。實施例b3(硬化劑組成物Bb2) 在備有擾拌機、回流冷凝管以及擾拌裝置之燒瓶中，一邊實施氮氣吹淨，一邊添加三環癸烧二曱醇2〇份、酸酐 (Hl)100份，在50°C進行4小時之加熱攪拌。經由GPC確認三環癸烷二曱醇為1面積％以下。得到含有本發明之多元羧酸組成物的硬化劑組成物（Bb2)120份。所得為無色之液狀樹脂，依GPC之純度，多元羧酸組成物（Ab2 ;式（3)之構造式的混合物）的構造為43面積％、甲基六氫酞酸酐與六氫酞酸酐之總量為57面積％。並且，官能基當量為199g/eq.。實施例b4、b5(硬化性樹脂組成物）、比較例bl(比較用硬化性樹脂組成物）硬化劑係使用實施例b2、b3中所得本發明之硬化劑組成物（Bbl)、（Bb2)，以及比較例之酸酐（H〗）；環氧樹脂係使用3, 4-環氧基環己基甲基_3, 4-環氧基環己基羧酸酯 (Dow Chemical公司製造；UVR-6105以下稱為環氧樹脂 (EP-1));硬化促進劑係使用氫氧化十六烧基三甲基銨（東 65 322150 201120000 京化成工業（股）製造；25%曱醇溶液，以下稱為ci) ’以下述表1所示之調配比例（重量份）進行調配，進行20分鐘之脫泡後，得到本發明或比較用之硬化性樹脂組成物。使用所得之硬化性樹脂組成物’以下述所示之要點進行揮發試驗、LED密封試驗’並將結果示於表bl。另外，硬化條件係120°Cx2小時之預備硬化後15(rcx5小時。揮發試驗：實施例及比較例中所得之硬化性樹脂組成物經實施真空脫泡20分鐘後，徐緩地注入以耐熱膠帶作成屏障（dam) 之玻璃基板上鎮型成為30πππχ20ιππιχ南度1 mm者。鑄型之樹脂重量經正確地測定後，以上述條件使該鑄型物硬化。將如此進行而得之硬化物重量進行測定，確認硬化時之重量的減少。（實施例、比較例之硬化係在同一烘箱下使同樣地硬化）。 led試驗：將實施例及比較例所得之硬化性樹脂組成物進行真空脫泡20分鐘後充填於量筒中，使用精密吐出裝置，將上述者注入並成型於搭載具有發光波長465mn之發光元件的表面封裝型（SMD型3mn^)LED。然後，使該等在既定之硬化條件下硬化，得到試驗用LED。評價項目： (W揮發性：以目視觀察密封後之硬化物表面是否有凹凸並進行評價。表中之評價基準係如下所述。〇：看不出有凹洞。 322150 66 201120000 △:看出些微凹洞。 X :看出多數凹洞（有露出線）。 (b)回焊試驗：將所得之試驗用LED在30°C、70%x72小時吸濕後，使用高溫觀察裝置（SMT Scope SK-5000 ;山陽精工（股）製造），確認在以下之回焊條件下的LED有無龜裂產生。試驗係在n=3進行，以（0K數）/(試驗數）進行評價。條件係指由25°C以2°C/秒升溫至150°C，然後在150 °C中維持2分鐘，再以2°C/秒升溫至260°C並維持10秒後，以1. 3°C/秒冷卻至室溫者。表bl : 實施例b4 實施例b5 比施例bl 單位硬化劑組成物 Bbl 18.7 重量份 Bb2 19.9 重量份硬化劑 HI 16.8 重量份環氧樹脂 EP-1 13.0 13.0 13.0 重量份硬化促進劑 Cl 0.05 0.05 0.05 重量份揮發試驗(揮發量） 4.6 5.8 13.0 重量％ LED 5式·1¾ (a) 〇〇 X (b) 3/3 3/3 1/3 將實施例b4、b5與比較例b 1進行比較時，本發明之硬化性樹脂組成物的揮發量少，即使在密封LED時亦不會引發鋼線露出等之問題。更且，在回焊時亦可減少龜裂。由上述結果可知，本發明之多元羧酸組成物及含有多元羧酸組成物之硬化劑組成物可賦予耐回焊龜裂中之有效的硬化性樹脂組成物者。 67 322150 201120000 實施例b6(硬化劑組成物Bb3) 在備有攪拌機、回流冷凝管以及攪拌裝置之燒瓶中，一邊實施氮氣吹淨，一邊添加三環癸烷二曱醇20份、曱基六氫酞酸酐（新日本理化（股）製造；RikacidMH，以下稱為酸酐H3)100份，4(TC反應3小時後在7(TC進行1小時之加熱擾拌。經由GPC確認三環癸院二曱醇為1面積％以下。得到含有本發明之多元羧酸組成物的硬化劑組成物 (Bb3)120份。所得為無色之液狀樹脂，依GPC之純度，多元羧酸組成物（Ab2 ;下述式（4))為49面積％、曱基六氫酞酸Sf為51面積％。並且，官能基當量為2〇 1 g/eq.。式⑷：Example b2 (hardener composition Bb1) With respect to 25 parts of the polycarboxylic acid composition (Abl: a mixture of the structural formula of the formula (3)) obtained in Example bl, 75 parts of an acid anhydride (jji) was added to uniformly dissolve it. The hardener composition (Bbi) of the present invention was obtained. Example b3 (hardener composition Bb2) In a flask equipped with a scrambler, a reflux condenser, and a scrambler, nitrogen gas was purged, and tricyclic terbene dinonol was added thereto, and an acid anhydride (Hl) was added. 100 parts, heated and stirred at 50 ° C for 4 hours. It was confirmed by GPC that tricyclodecanedioxanol was 1 area% or less. 120 parts of a hardener composition (Bb2) containing the polycarboxylic acid composition of the present invention was obtained. The obtained colorless liquid resin has a structure of a polyvalent carboxylic acid composition (Ab2; a mixture of the structural formula of the formula (3)) of 43% by area, methyl hexahydrophthalic anhydride and hexahydrophthalic anhydride depending on the purity of GPC. The total amount is 57 area%. Further, the functional group equivalent was 199 g/eq. Examples b4 and b5 (curable resin composition) and Comparative Example bl (comparative curable resin composition) The curing agent was obtained by using the hardener compositions (Bbl) and (Bb2) of the present invention obtained in Examples b2 and b3. And the anhydride (H) of the comparative example; the epoxy resin system uses 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexyl carboxylate (Dow Chemical Co., Ltd.; UVR-6105 or less) It is called epoxy resin (EP-1)); the hardening accelerator is made of hexadecyl trimethylammonium hydroxide (East 65 322150 201120000 Jinghuacheng Industry Co., Ltd.; 25% sterol solution, hereinafter referred to as ci 'The blending ratio (parts by weight) shown in the following Table 1 was adjusted, and after defoaming for 20 minutes, the curable resin composition of the present invention or comparatively obtained was obtained. The obtained curable resin composition was subjected to a volatilization test and an LED sealing test at the points indicated below, and the results are shown in Table bl. Further, the curing conditions were 15 ° after the preliminary hardening at 120 ° C for 2 hours (rcx 5 hours. Volatilization test: The curable resin composition obtained in the examples and the comparative examples was subjected to vacuum defoaming for 20 minutes, and then slowly poured into a heat-resistant tape. The shape of the glass substrate of the barrier (dam) is 30ππππ20ππιχ1 mm. The weight of the resin of the mold is accurately measured, and the mold is hardened under the above conditions. The weight of the cured product thus obtained is measured. The weight loss at the time of hardening was confirmed. (The curing of the examples and the comparative examples was similarly cured in the same oven.) Led test: The curable resin composition obtained in the examples and the comparative examples was subjected to vacuum defoaming for 20 minutes. After that, it is filled in a graduated cylinder, and the above-described one is injected and molded into a surface mount type (SMD type 3 mn^) LED having a light-emitting element having an emission wavelength of 465 nm, and then hardened under the predetermined hardening conditions. , Test LEDs were obtained. Evaluation items: (W Volatile: Visually observe whether there is unevenness on the surface of the cured product after sealing and evaluate it The evaluation criteria in the table are as follows: 〇: No pits are visible. 322150 66 201120000 △: Look at some micro-pits. X: See most holes (with exposed lines). (b) Reflow test : The obtained test LED was absorbed at 30 ° C and 70% x 72 hours, and then a high-temperature observation apparatus (SMT Scope SK-5000; manufactured by Sanyo Seiko Co., Ltd.) was used to confirm whether or not the LED under the following reflow conditions were present. Cracking occurred. The test was carried out at n=3 and evaluated by (0K number) / (test number). Condition means heating from 25 ° C to 2 ° C / sec to 150 ° C, then at 150 ° C After maintaining for 2 minutes, the temperature was raised to 260 ° C at 2 ° C / sec and maintained for 10 seconds, and then cooled to room temperature at 1.3 ° C / sec. Table bl: Example b4 Example b5 than the example bl unit Hardener composition Bbl 18.7 parts by weight Bb2 19.9 parts by weight hardener HI 16.8 parts by weight epoxy resin EP-1 13.0 13.0 13.0 parts by weight hardening accelerator Cl 0.05 0.05 0.05 parts by weight volatilization test (volatilizing amount) 4.6 5.8 13.0% by weight LED 5 Formula·13⁄4 (a) 〇〇X (b) 3/3 3/3 1/3 When comparing Examples b4 and b5 with Comparative Example b 1 The curable resin composition of the present invention has a small amount of volatilization, and does not cause problems such as exposure of the steel wire even when the LED is sealed. Further, cracks can be reduced during reflowing. From the above results, it is understood that the present invention The polyvalent carboxylic acid composition and the hardener composition containing the polyvalent carboxylic acid composition can provide an effective curable resin composition for reflow-resistant cracking. 67 322150 201120000 Example b6 (hardener composition Bb3) In a flask equipped with a stirrer, a reflux condenser, and a stirring device, while blowing nitrogen gas, 20 parts of tricyclodecanedioxan, decyl hexahydrogen was added. 100% of phthalic anhydride (manufactured by Nippon Chemical and Chemical Co., Ltd.; Rikacid MH, hereinafter referred to as anhydride H3), 4 (after 3 hours of TC reaction, 7 (TC was heated for 1 hour). Confirmation of the three-ring broth by GPC The alcohol is 1% by area or less. 120 parts of the hardener composition (Bb3) containing the polycarboxylic acid composition of the present invention is obtained. The obtained colorless liquid resin is a polycarboxylic acid composition (Ab2; The formula (4)) is 49% by area, and the mercapto hexahydroabietic acid Sf is 51% by area. Further, the functional group equivalent is 2〇1 g/eq. Formula (4):

由硬化劑組成物（Bb3)50份，使用旋轉蒸發器，將ι〇〇至150°C存在過量之曱基六氫酞酸酐去除。該去除係，由甲基六氫酞酸酐不再流出之時點而流入氮氣4〇分鐘，並在加熱減壓條件下直接將酸酐充分地去除。其結果係取出本發明之式（1)的多元羧酸（Bb3a)25份。形狀為無色之半固形至固形樹脂。所得樹脂之軟化點（依JIS K-7234之基準）為77 〇 °C ’在150°C中之熔融黏度為〇. 24Pa.s。實施例b7(硬化劑組成物Bb4) 322150 68 201120000 在備有攪拌機、回流冷凝管以及攪拌裝置之燒瓶中，一邊實施氮氣吹淨，一邊添加三環癸燒二甲醇15份、甲基六氫酞酸酐（新日本理化（股）製造；RikacidMH，以下稱為酸酐113)70份、環己烷-1，2,4-三羧酸-1，2-軒（三菱瓦斯化學（股）製造；H-TMAn)15份，40°C反應3小時後在7〇〇c進行1小時之加熱攪拌。經由GPC確認三環癸烷二曱醇為i 面積％以下。得到含有本發明之多元羧酸組成物的硬化劑組成物（Bb4)100份。所得為無色之液狀樹脂，依GPC之純度，多元叛酸組成物（Ab3 ;下述式（5))為37面積％、環己烧 -1，2,4-三缓酸-1,2-酐為11面積％、曱基六氫酞酸肝為52 面積％。並且，官能基當量為171g/eq.。式⑸：From the hardener composition (Bb3) 50 parts, an excess of mercapto hexahydrophthalic anhydride was removed by using a rotary evaporator at 10,000 Torr to 150 °C. This removal system was allowed to flow into the nitrogen gas for 4 minutes from the point where the methylhexahydrophthalic anhydride no longer flowed out, and the acid anhydride was sufficiently removed under heating and reduced pressure. As a result, 25 parts of the polycarboxylic acid (Bb3a) of the formula (1) of the present invention was taken out. The shape is a colorless semi-solid to solid resin. The softening point of the obtained resin (based on JIS K-7234) was 77 〇 ° C ', and the melt viscosity at 150 ° C was Pa 24 Pa·s. Example b7 (hardener composition Bb4) 322150 68 201120000 In a flask equipped with a stirrer, a reflux condenser, and a stirring device, while blowing nitrogen gas, 15 parts of tricycloanthracene dimethanol and methyl hexahydroquinone were added. Anhydride (manufactured by Nippon Chemical and Chemical Co., Ltd.; Rikacid MH, hereinafter referred to as anhydride 113) 70 parts, cyclohexane-1,2,4-tricarboxylic acid-1,2-xuan (manufactured by Mitsubishi Gas Chemical Co., Ltd.; H - TMAn) 15 parts, reacted at 40 ° C for 3 hours and then heated and stirred at 7 ° C for 1 hour. It was confirmed by GPC that tricyclodecanedioxanol was i area% or less. 100 parts of a hardener composition (Bb4) containing the polycarboxylic acid composition of the present invention was obtained. The obtained colorless liquid resin, according to the purity of GPC, the multi-repulsive acid composition (Ab3; the following formula (5)) is 37 area%, cyclohexene-1,2,4-tris-acid-1,2 The anhydride was 11 area%, and the mercapto hexahydroabietic acid liver was 52 area%. Further, the functional group equivalent was 171 g/eq. Equation (5):

實施例b8(硬化劑組成物Bb5) 在備有攪拌機、回流冷凝管以及攪拌裝置之燒瓶中，一邊實施氮氣吹淨，一邊添加實施例6中所得之硬化劍說成物（Bb3)50份、環己烷-1，2, 4-三羧酸-1，2-酐（三菱瓦斯化學（股）製造；H-TMAn-S)5份，在l〇〇°C進行2小時之授拌，得到本發明之硬化劑組成物（Bb5)。所得之組成物為無色之液狀組成物。 69 322150 201120000 實施例b9(硬化劑組成物Bb6) 在備有攪拌機、回流冷凝管以及攪拌裝置之燒瓶中，一邊實施氮氣吹淨，一邊添加五環十五烷二甲醇20份及酸酐（H3)100份，40°C反應3小時後在70°C進行1小時之加熱攪拌。經由GPC確認五環十五烷二曱醇為1面積％以下。得到含有本發明之多元羧酸組成物的硬化劑組成物 (Bb6)110 #。所得為無色之液狀組成物，依GPC之純度，多元羧酸組成物（Ab4 ;下述式（6))為40面積％、甲基六氫酞酸酐為60面積％。並且，官能基當量為201g/eq.。式（6):Example b8 (hardener composition Bb5) In a flask equipped with a stirrer, a reflux condenser, and a stirring device, 50 parts of the hardened sword product (Bb3) obtained in Example 6 was added while purging with nitrogen. 5 parts of cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd.; H-TMAn-S), and mixed at 2 ° C for 2 hours. The hardener composition (Bb5) of the present invention is obtained. The resulting composition was a colorless liquid composition. 69 322150 201120000 Example b9 (hardener composition Bb6) In a flask equipped with a stirrer, a reflux condenser, and a stirring device, while blowing nitrogen gas, 20 parts of pentacyclopentadecanedimethanol and an acid anhydride (H3) were added. 100 parts, reacted at 40 ° C for 3 hours, and then heated and stirred at 70 ° C for 1 hour. It was confirmed by GPC that pentacyclopentadecanedonol was 1 area% or less. A hardener composition (Bb6) 110 # containing the polycarboxylic acid composition of the present invention was obtained. The obtained liquid composition was a colorless liquid, and the polycarboxylic acid composition (Ab4; the following formula (6)) was 40% by area and the methylhexahydrophthalic anhydride was 60% by area based on the purity of GPC. Further, the functional group equivalent was 201 g/eq. Equation (6):

實施例bl0(硬化劑組成物Bb7) 在備有攪拌機、回流冷凝管以及攪拌裝置之燒瓶中，一邊實施氮氣吹淨，一邊添加三環癸烷二曱醇10份及酸酐 (Hl)100份，50°C進行3小時之加熱攪拌（經由GPC確認三環癸烷二甲醇為1面積％以下）。得到含有本發明之多元羧酸組成物的硬化劑組成物（Bb7)l 10份。所得為無色之液狀樹脂，依GPC之純度，多元羧酸組成物（Abl ;下述式（3)) 為27面積％、曱基六氫酞酸酐為73面積％。並且，官能基 70 322150 201120000 當量為185g/eq.。合成例bl (比較用硬化劑組成物Bb8) 在備有攪拌機、回流冷凝管以及攪拌裝置之燒瓶中，一邊實施氮氣吹淨，一邊添加二環癸烧二甲醇20份及六氫酞酸酐（新日本理化（股）製造，Rikacid ΗΗ)1〇〇份，5〇。〇進行3小時之加熱攪拌經由GPC確認三環癸烷二曱醇為1 面積％以下。得到含有比較用之多元羧酸級成物的硬化劑組成物（Bb8)120份。所得硬化劑缸成物為無色之液狀組成物，依GPC之純度，多元羧酸組成物（A5 ;下述式7)為48 面積％、甲基六氫醜酸針為52面積％。並且，官能基當量為 200g/eq.。式⑺：Example bl0 (hardener composition Bb7) In a flask equipped with a stirrer, a reflux condenser, and a stirring device, 10 parts of tricyclodecanedioxan and 100 parts of an acid anhydride (Hl) were added while purging with nitrogen. The mixture was heated and stirred at 50 ° C for 3 hours (it was confirmed by GPC that tricyclodecane dimethanol was 1 area% or less). 10 parts of a hardener composition (Bb7) containing the polycarboxylic acid composition of the present invention was obtained. The obtained colorless liquid resin had a polycarboxylic acid composition (Abl; the following formula (3)) of 27% by area and decyl hexahydrophthalic anhydride of 73% by area based on the purity of GPC. Also, the functional group 70 322150 201120000 equivalent is 185 g/eq. Synthesis Example bl (Comparative Hardener Composition Bb8) In a flask equipped with a stirrer, a reflux condenser, and a stirring device, while blowing nitrogen gas, 20 parts of bicyclodoxime dimethanol and hexahydrophthalic anhydride were added (new Made by Japan Physicochemical Co., Ltd., Rikacid ΗΗ) 1 ,, 5 〇.加热 It was confirmed by GPC that the tricyclodecanedioxanol was 1 area% or less by heating and stirring for 3 hours. 120 parts of a hardener composition (Bb8) containing a comparative polycarboxylic acid composition was obtained. The obtained hardener cylinder was a colorless liquid composition. According to the purity of GPC, the polycarboxylic acid composition (A5; the following formula 7) was 48 area%, and the methylhexahydro acid needle was 52 area%. Further, the functional group equivalent was 200 g/eq. Equation (7):

合成例b2 (比較用硬化劑組成物Bb9) 在備有攪拌機、回流冷凝管以及授拌裝置之燒瓶中，一邊實施氮氣吹淨，一邊添加乙二醇1〇份及酸酐（Ηΐ)ι〇〇份，40°C進行3小時之反應後再於70°C進行1小時之加熱授拌。經由GPC確認為原料之1面積％以下。得到含有比較用之多元羧酸組成物的硬化劑組成物（Bb9)l 10份。所得硬化劑組成物為無色之液狀組成物，依GPC之純度，多元羧酸組成物（Ab6 ;下述式（8))為25面積％、甲基六氫酞酸酐與六氫酞酸酐之總量為75面積％。並且，官能基當量為 322150 201120000 185g/eq.。式（8):Synthesis Example b2 (Comparative Hardener Composition Bb9) In a flask equipped with a stirrer, a reflux condenser, and a mixing device, 1 part of ethylene glycol and an acid anhydride (Ηΐ) were added while purging with nitrogen. The mixture was reacted at 40 ° C for 3 hours and then heated at 70 ° C for 1 hour. It was confirmed by GPC to be 1 area% or less of the raw material. 10 parts of a hardener composition (Bb9) containing a comparative polycarboxylic acid composition was obtained. The obtained hardener composition is a colorless liquid composition, and the polycarboxylic acid composition (Ab6; the following formula (8)) is 25 area%, methylhexahydrophthalic anhydride and hexahydrophthalic anhydride according to the purity of GPC. The total amount is 75 area%. Further, the functional group equivalent is 322150 201120000 185g/eq. Equation (8):

合成例b3(比較用硬化劑組成物Bbl〇) 在備有攪拌機、回流冷凝管以及攪拌裝置之燒瓶中邊實施氮氣吹淨，-邊添加環己燒二甲醇=份及酸酐（Hl)100份，4(TC進行3小時之反應後再於7〇。〇進行工小時之加熱攪拌。經由GPC確認為原料之i面積％以下= 得到含有比較用之多元羧酸組成物的硬化劑組成物 (Bbl0)120份》所得硬化劑組成物為無色之液狀組成物，依GPC之純度，多元羧酸組成物（Ab7 ;下述式8)為53面積％、曱基六氫酞酸酐與六氫酞酸酐之總量為47面積％。並且’ s能基當量為2〇〇g/eq.。式（9):Synthesis Example b3 (Comparative Hardener Composition Bbl〇) Nitrogen purge was carried out in a flask equipped with a stirrer, a reflux condenser, and a stirring device, and cyclohexane dimethanol = part and anhydride (Hl) 100 parts were added. 4 (TC was reacted for 3 hours and then at 7 Torr. Heating and stirring was carried out for a working hour. It was confirmed by GPC that the area of the raw material was i% or less = a hardener composition containing a comparative polycarboxylic acid composition was obtained ( Bbl0) 120 parts of the obtained hardener composition is a colorless liquid composition, according to the purity of GPC, the polycarboxylic acid composition (Ab7; the following formula 8) is 53 area%, mercapto hexahydrophthalic anhydride and hexahydrogen The total amount of phthalic anhydride is 47 area%, and the 's energy base equivalent is 2 〇〇g/eq.. (9):

合成例b4(比較用硬化劑組成物Bbll) 在備有攪拌機、回流冷凝管以及攪拌裝置之燒瓶中，邊只轭氮氣吹淨’一邊添加1，6-己二醇20份及酸酐（H1) 72 322150 201120000 100份’ 40°c進行3小時之反應後再於7〇°c進行1小時之加熱擾拌。經由GPC確認為原料之1面積％以下。得到含有比較用之多元羧酸組成物的硬化劑組成物（Bbl 1)120份。所得為無色之液狀樹脂，依GPC之純度，多元羧酸組成物 (Ab8 ;下述式10)為65面積％、曱基六氫醜酸針與六氫駄酸酐之總量為35面積％。並且，官能基當量為200g/eq.。式（10):Synthesis Example b4 (Comparative Hardener Composition Bb11) In a flask equipped with a stirrer, a reflux condenser, and a stirring device, 20 parts of 1,6-hexanediol and an acid anhydride (H1) were added while yoke was purged with nitrogen. 72 322150 201120000 100 parts '40 ° c for 3 hours of reaction and then 1 hr of heating for 1 hour. It was confirmed by GPC to be 1 area% or less of the raw material. 120 parts of a hardener composition (Bbl 1) containing a comparative polycarboxylic acid composition was obtained. The obtained color is a colorless liquid resin. According to the purity of GPC, the polycarboxylic acid composition (Ab8; the following formula 10) is 65 area%, and the total amount of the mercapto hexahydro sulphur acid needle and the hexahydrophthalic anhydride is 35 area%. . Further, the functional group equivalent was 200 g/eq. Equation (10):

合成例b5 (環氧合成原料二稀烴）在備有攪拌機、回流冷凝管、攪拌裝置以及 Dean-Stark管之燒瓶中，一邊實施氮氣吹淨，一邊添加 1，4-%己烧>一繞酸.172份、3-環己稀-1-甲醇448份、甲苯 600份、對曱苯磺酸4份’以在45Ϊ回流之方式，一邊調整系内之減壓度去除所生成之水，一邊進行12小時之反應。反應結束後，將反應溶液以重量％氫氧化鈉水溶液 120份進行3次清洗，再以水7〇份/次反覆進行水洗使廢水呈現中性為止，以旋轉蒸發器在加熱減壓下，藉由餾除曱苯與未反應之3-環己烯-1-甲醇，可得到常溫為液狀之二烯烴化合物343份。合成例b6(環氧樹脂EP-b2) 在備有攪拌機、回流冷凝管以及攪拌裝置之燒瓶中， 322150 73 201120000 一邊實施氮氣吹淨，〆邊添加水15份、12-鎢磷酸0. 95 份、磷酸氫二鈉〇. 78份、乙酸二牛油烷基二甲基銨2. 7 份（Lion Akzo(股）製造；50重量％己烷溶液、Arquad 2HT acetate)、曱苯180份以及合成例b5中所得二烯烴化合物 118份’再度地攪拌下而作成乳液狀態之液。將此溶液升溫至50°C，一邊激烈地授拌，一邊以1小時添加35重量％含過氧化氫之水溶液70份，直接在50°C攪拌13小時。確認氣相層析中之反應的進行後，原料波峰已消失。接著，以1重量％氫氧化鈉水溶液中和後，添加20重量％硫代硫酸納水溶液25份進行30分鐘之授拌後靜置。取出分離為2層之有機層’在此添加石夕膠（Wako gel;C-30〇)1〇份 '活性碳（N0RIT製造；CAPSUPER)20份、膨潤土（H〇jun 公司製造Bengel SH)20份，在室溫攪拌1小時後過渡。將所得滤液以水10 0份進行3次水洗，並經所得之有機芦餾除甲苯。得到常溫為液狀之以下述式（U)為主成分的環氧樹脂（EP-b2) 119份。所得環氧樹脂之環氧當量為 217g/eq.。式（11):Synthesis Example b5 (epoxy synthetic raw material dilute hydrocarbon) In a flask equipped with a stirrer, a reflux condenser, a stirring device, and a Dean-Stark tube, 1,4-% hexane was added while purging with nitrogen gas. 172 parts of acid, 448 parts of 3-cyclohexene-1-methanol, 600 parts of toluene, and 4 parts of toluenesulfonic acid were adjusted to reduce the degree of pressure in the system to remove water generated by refluxing at 45 Torr. The reaction was carried out for 12 hours. After the completion of the reaction, the reaction solution was washed three times with 120 parts by weight of a sodium hydroxide aqueous solution, and then washed with water 7 times/time to make the wastewater neutral, and then heated under reduced pressure by a rotary evaporator. From the distillation of toluene and unreacted 3-cyclohexene-1-methanol, 343 parts of a diene compound which is liquid at normal temperature can be obtained. Synthesis Example b6 (epoxy resin EP-b2) In a flask equipped with a stirrer, a reflux condenser, and a stirring device, 322150 73 201120000 was purged with nitrogen, and 15 parts of water and 12-tungstophosphoric acid were added. , disodium hydrogen phosphate 〇. 78 parts, acetic acid ditallow alkyl dimethyl ammonium 2. 7 parts (manufactured by Lion Akzo; 50% by weight hexane solution, Arquad 2HT acetate), 180 parts of toluene and synthesis The 118 parts of the diolefin compound obtained in Example b5 was re-stirred to prepare a liquid in an emulsion state. The solution was warmed to 50 ° C, and while vigorously mixing, 70 parts of a 35 wt% aqueous solution containing hydrogen peroxide was added over 1 hour, and the mixture was stirred at 50 ° C for 13 hours. After confirming the progress of the reaction in the gas chromatography, the peak of the raw material has disappeared. Subsequently, after neutralizing with a 1% by weight aqueous sodium hydroxide solution, 25 parts of a 20% by weight aqueous sodium thiosulfate solution was added thereto, and the mixture was allowed to stand for 30 minutes, followed by standing. The organic layer separated into two layers was taken out. Here, Wako gel (C-30 〇) 1 〇 part of activated carbon (manufactured by N0RIT; CAPSUPER) 20 parts, bentonite (Bengel SH manufactured by H〇jun Co., Ltd.) 20 was added. The mixture was stirred at room temperature for 1 hour and then transferred. The filtrate obtained was washed with water three times with 10 parts of water, and toluene was removed by the obtained organic retort. 119 parts of an epoxy resin (EP-b2) containing a compound of the following formula (U) as a liquid at room temperature was obtained. The epoxy equivalent of the obtained epoxy resin was 217 g/eq. Equation (11):

實施例bll、bl2(硬化性樹脂組成物）、比較例b2(比較用硬化性樹脂組成物）硬化劑係使用實施例3、6中所得本發明之硬化劑組 322150 74 201120000 成物（Bb2)、（Bb3)’以及合成例bl中所得之比較用硬化劑組成物（Bb8);環氧樹脂係使用環氧樹脂（Ep_1);以及使用硬化促進劑（C1)，以下述表2所示之調配比例（重量份）進行調配，進行20分鐘之脫泡後，得到本發明或比較用之硬化性樹脂組成物。 LED點燈試驗實施例bll、bl2及比較例2中所得之硬化性樹脂組成物貫施真空脫泡20分鐘後充填於量筒中，使用精密吐出裝置庄入並成型於搭載具有發光波長465nm之發光元件的表面封裝型LED(SMD型5ππηφ ;預定電流為30mA)。然後，以預定之硬化條件使之硬化下得到點燈試驗用LED。點燈試驗係在預定電流30mA的2倍之電流下進行點燈試驗。詳細條件係如下所示。測定項目係使用積分球測定點燈2〇〇小時之前、後的照度，並算出試驗用LED之照度的維持率。結果不於表2。點燈詳細條件發光波長：中心發光波長、465nm 驅動方式：定電流方式、6〇mA(發光元件預定電流為3〇mA) 串聯之3個同時點燈驅動環境：85。(：、85%濕熱機内之點燈評價：點燈200小時之前、後的照度與其照度維持率，以及晶片之著色* (*如目視之評價、點燈試驗為劣化時，則在晶片上著色，由此則有照度急驟地降低之傾向） 75 322150 201120000 表b2Examples b11 and bl2 (curable resin composition) and Comparative Example b2 (comparative curable resin composition) The curing agent was obtained by using the hardener group 322150 74 201120000 (Bb2) of the present invention obtained in Examples 3 and 6. (Bb3)' and the hardener composition (Bb8) for comparison obtained in Synthesis Example bl; epoxy resin (Ep_1) for epoxy resin; and hardening accelerator (C1), which are shown in Table 2 below. The blending ratio (parts by weight) was blended, and after defoaming for 20 minutes, a curable resin composition of the present invention or comparatively obtained was obtained. The LED lighting test examples b11, bl2 and the curable resin composition obtained in Comparative Example 2 were subjected to vacuum defoaming for 20 minutes, filled in a graduated cylinder, and molded and molded on a light emitting wavelength of 465 nm using a precision discharge device. The surface mount type LED of the device (SMD type 5ππηφ; predetermined current is 30 mA). Then, it was hardened under predetermined hardening conditions to obtain an LED for lighting test. The lighting test is performed at a current of twice the predetermined current of 30 mA. The detailed conditions are as follows. In the measurement item, the illuminance before and after lighting for 2 hours was measured using an integrating sphere, and the maintenance ratio of the illuminance of the test LED was calculated. The results are not in Table 2. Detailed lighting conditions Light-emitting wavelength: Center light-emitting wavelength, 465nm Drive mode: Constant current mode, 6〇mA (light-emitting element predetermined current is 3〇mA) Three simultaneous lighting in series Drive environment: 85. (:, 85% damp heat machine lighting evaluation: before and after lighting 200 hours, after the illumination and its illuminance maintenance rate, and the color of the wafer * (* If visual evaluation, lighting test is deterioration, then color on the wafer Thus, there is a tendency for the illuminance to decrease sharply.) 75 322150 201120000 Table b2

實施例 bll 實施例 bl2 比施例b2 環氧樹脂 ~EM 6.6 6.6 6. 6 組成硬化劑 Bb2 10.0 Bb3 10.1 Bb8 10.0 硬化觸媒 ~Cl ~~ 0.03 0.03 0. 03 初期照度(mW) 8210 8280 7940 LED點燈試驗 200小時後之照度（min 6280 6670 5710 照度維持率(％) 76 81 72 晶片的著色〇〇 X 由上述結果而可明瞭，在僅由上述式（1)中之R均為氫原子的化合物所成之多元羧酸組成物所組成的比較用硬化劑組成物（Bb8)中之照度維持率差，相對於可看出晶片的著色，由R中經導入曱基的化合物所成之多元竣酸組成物所組成的本發明之硬化性樹脂組成物，在初期照度以及點燈试驗後之照度優異、對晶片的著色亦少，可賦予可抗劣化之硬化物，並可製造適用於產業用之led。實施例 M3、bl4、bl5、bl6、bl7、比較例 b3、b4、b5 硬化劑係使用實施例6、7、8、9、10中所得的本發明之硬化劑組成物（Bb3)、（Bb4)、（Bb5)、（Bb6)、（Bb7) 以及合成例b2、b3、b4中所得的硬化劑組成物（此9)、 (BblO)、（Bbll);環氧樹脂係使用環氧樹脂（Ep—u、合成例b6中所得的5哀氧樹脂（EP-b2);並使用硬化促進劑（日本合成化學製造，HISHI COL IN PX4MP)，以下述表3所示之調配比例（重量份）進行調配’進行20分鐘之脫泡後，得到本 322150 76 201120000 發明或比較用之硬化性樹脂組成物。 (耐熱試驗）實施例bl3至bl7、比較例b3至b5中所得之硬化性 • 樹脂組成物經實施真空脫泡20分鐘後，徐缓地注入以耐熱谬帶作成障（dam)之玻璃基板上鑄型成為3〇丽x2〇mmx高度 1顏者’以12『Cx3小時之預備硬化後i5〇°cxl小時使該鑄造物硬化而得到厚度lmm之穿透率用試驗片。使用該等之試驗片’由分光光度計測定置於l5〇〇c之烘箱中96小時前後的穿透率（測定波長：4〇〇nm)，算出穿透率之維持率。結果示於表3。表b3 實施例比較例實施例比較例 bl3 bl4 bl5 bl6 h3 b4 bl7 b5 組成環氧樹脂 EP-1 6.6 6.6 6.6 6.6 6.6 6.6 EP-b2 10.9 10.9 硬化劑 Bb3 10.1 Bb4 8.6 Bb5 9.2 Bb6 10.1 Bb7 9.9 Bb9 9.3 BblO 10.0 Bbll 10.0 硬化觸媒 C2 0. 03 0.03 0.03 0. 03 0.03 0. 03 0.05 0. 05 熱耐久試驗 (穿透率之維持率(％)) 74.6 80.1 80.0 75.0 54.6 47.7 64.0 17.8 由上述結果可知，含有本發明之多元羧酸組成物的硬化性樹脂組成物因具有耐熱劣化性且其維持率高，因此可適用在光學用途上。在備有攪拌機、回流冷凝管以及攪拌裝置之燒瓶中’ 322150 201120000 -邊實施氮氣吹淨…邊添加UP環己烧三舰酐（Η ΤΜΑη —菱瓦斯化學（股）製造；取）“9份、甲基六氮欧酸針（新日本理化（股）製造；Rikacid MH H3M03.2 伤、曱基乙基_ 349·9份，-邊擾拌一邊升溫至4rc後，以30。分鐘添加預溫至7〇。〇之三環癸烷二曱醇294·4份，，於40 C擾拌30分鐘、再於耽擾拌4小時。將所得反應液以旋轉蒸發器於剛幻5(rc中去除溶劑，得到本發明之多元羧酸組成物（X)816份。形狀為無色之固形樹脂。官能基當量為272g/eq.。所得樹脂之軟化點（依jIS K-7234之基準）為99.8 °C ’在150°C中之熔融黏度為〇 92pa.s。熔融黏度 150°C中之錐-板（Cone-plate)法中的熔融黏度測定機械：錐-板（ICI)高溫黏度儀 (RESEARCH EQUIPMENT(LONDON) LTD.製造）錐型號：3(測定範圍〇至2.00 pa.s) 以下’以同樣條件進行測定。實施例b 由硬化劑組成物（Bb4)50份，使用旋轉蒸發器，將1〇〇至150°C下存在過量之甲基六氫酞酸酐去除（由甲基六氫酞酸酐不再流出之時點，在加熱減壓條件下直接流入氮氣 40分鐘，即可充分地去除酸酐）的情況下，取出本發明之多元羧酸組成物（x2)24份。形狀為無色之固形樹脂。所得樹脂之軟化點（依JIS K-7234之基準）為72.4 78 322150 201120000 C，在150C中之溶融黏度為0. ·s。實施例c 在備有攪拌機、回流冷凝管以及攪拌裝置之燒瓶中’ ‘ 一邊實施氮氣吹淨，一邊添加1，3, 4-環己烷三羧酸-3,4-^ 酐（H-TMAn三菱瓦斯化學（股）製造；H2)162份、甲基六氫酞酸酐（新日本理化（股）製造；Rikacid ΜΗ H3)787份、曱基乙基酮400份，一邊攪拌一邊升溫至40°C後，以30分鐘添加預溫至70°C之三環癸烷二甲醇540份，於40°C攪拌 30分鐘、再於70¾攪拌4小時。將所得反應液以旋轉蒸發器於100至150°C中去除溶劑，得到本發明之多元羧酸組成物（x3)1489份。形狀為無色之固形樹脂。官能基當量為 271g/eq.。所得樹脂之軟化點（依JIS K-7234之基準）80.6°C，在150°C中之熔融黏度為〇. 43Pa.s。Example b11 Example bl2 Specific Example b2 Epoxy Resin ~ EM 6.6 6.6 6. 6 Composition Hardener Bb2 10.0 Bb3 10.1 Bb8 10.0 Hardening Catalyst ~Cl ~~ 0.03 0.03 0. 03 Initial Illumination (mW) 8210 8280 7940 LED Illumination after 200 hours of lighting test (min 6280 6670 5710 illuminance maintenance rate (%) 76 81 72 The color 〇〇X of the wafer is confirmed by the above results, in which only R in the above formula (1) is a hydrogen atom The comparative illuminant composition (Bb8) composed of the polycarboxylic acid composition formed by the compound has a poor illuminance maintenance ratio, and is formed from a compound in which R is introduced into the thiol group with respect to the coloration of the wafer. The curable resin composition of the present invention which is composed of the polyvalent decanoic acid composition is excellent in illuminance after the initial illuminance and the lighting test, and has less coloration on the wafer, and can provide a cured product which is resistant to deterioration, and can be manufactured and applied. Ll for industrial use. Examples M3, bl4, bl5, bl6, bl7, comparative examples b3, b4, b5 Hardeners The hardener compositions of the present invention obtained in Examples 6, 7, 8, 9, and 10 were used. (Bb3), (Bb4), (B B5), (Bb6), (Bb7), and hardener compositions obtained in Synthesis Examples b2, b3, and b4 (9), (BblO), (Bbll); epoxy resin (Ep-u) , the sulphur oxide resin (EP-b2) obtained in the synthesis example b6; and a compounding ratio (parts by weight) shown in the following Table 3 using a hardening accelerator (manufactured by Nippon Synthetic Chemical Co., Ltd., HISHI COL IN PX4MP) After defoaming for 20 minutes, a curable resin composition of the invention or comparative use of 322150 76 201120000 was obtained. (Heat resistance test) The hardenability and resin compositions obtained in Examples bl3 to bl7 and Comparative Examples b3 to b5 were carried out. After vacuum defoaming for 20 minutes, it is slowly injected into a glass substrate with a heat-resistant enamel band as a dam. The mold becomes 3 brilliant x2 〇mmx height 1 s. '12' Cx3 hours of preliminary hardening i5 〇 °cxl The casting was hardened to obtain a test piece for a transmittance of 1 mm in thickness. The test piece was used to measure the transmittance before and after 96 hours in an oven placed at 15 ° C by a spectrophotometer (measuring wavelength: 4 〇〇nm), the retention rate of the penetration rate was calculated. The results are shown in Table 3. B3 EXAMPLES Comparative Examples Examples Comparative Example bl3 bl4 bl5 bl6 h3 b4 bl7 b5 Composition Epoxy Resin EP-1 6.6 6.6 6.6 6.6 6.6 6.6 EP-b2 10.9 10.9 Hardener Bb3 10.1 Bb4 8.6 Bb5 9.2 Bb6 10.1 Bb7 9.9 Bb9 9.3 BblO 10.0 Bbll 10.0 Hardening catalyst C2 0. 03 0.03 0.03 0. 03 0.03 0. 03 0.05 0. 05 Thermal endurance test (retention rate retention (%)) 74.6 80.1 80.0 75.0 54.6 47.7 64.0 17.8 From the above results, Since the curable resin composition containing the polyvalent carboxylic acid composition of the present invention has heat deterioration resistance and high maintenance ratio, it can be suitably used for optical applications. In a flask equipped with a stirrer, a reflux condenser and a stirring device, ' 322150 201120000 - while purging with nitrogen, add UP ring hexazone to the anhydride (Η — 菱菱菱化学化学 ;); Methyl hexanitroic acid needle (manufactured by Nippon Chemical and Chemical Co., Ltd.; Rikacid MH H3M03.2 wound, mercaptoethyl _ 349·9 parts, - while stirring, the temperature is raised to 4 rc, and the pre-addition is added at 30 minutes. Warm to 7 〇. 294·4 parts of tricyclodecanedioxanol, simmered for 30 minutes at 40 C, and then mixed for 4 hours with sputum. The resulting reaction solution was applied to a rotary evaporator at Vision 5 (rc The solvent was removed to obtain 816 parts of the polycarboxylic acid composition (X) of the present invention, and the shape was a colorless solid resin, and the functional group equivalent was 272 g/eq. The softening point of the obtained resin (based on JIS K-7234) was 99.8 °C 'The melt viscosity at 150 ° C is 〇92 pa.s. Melt viscosity measurement in the cone-plate method at 150 ° C. Machine: Cone-plate (ICI) high temperature viscometer (Manufactured by RESEARCH EQUIPMENT (LONDON) LTD.) Cone type: 3 (measurement range 〇 to 2.00 pa.s) The measurement was carried out. Example b From the hardener composition (Bb4) 50 parts, using a rotary evaporator, an excess of methyl hexahydrophthalic anhydride was removed at 1 to 150 ° C (from methyl hexahydrophthalic anhydride not At the time of re-flowing, when the nitrogen gas was directly infiltrated under heating and depressurization for 40 minutes, the acid anhydride was sufficiently removed, and 24 parts of the polycarboxylic acid composition (x2) of the present invention was taken out. The shape was a colorless solid resin. The softening point of the obtained resin (based on JIS K-7234) was 72.4 78 322150 201120000 C, and the melt viscosity at 150 C was 0. ·s. Example c In a flask equipped with a stirrer, a reflux condenser, and a stirring device ' ' While purging with nitrogen, add 1,3, 4-cyclohexanetricarboxylic acid-3,4- anhydride (H-TMAn Mitsubishi Gas Chemical Co., Ltd.; H2) 162 parts, methyl hexahydrogen 787 parts of phthalic anhydride (manufactured by Nippon Chemical and Chemical Co., Ltd.; Rikacid ΜΗ H3), 400 parts of mercaptoethyl ketone, and the temperature was raised to 40 ° C while stirring, and the tricyclic oxime preheated to 70 ° C was added in 30 minutes. 540 parts of alkane dimethanol, stirred at 40 ° C for 30 minutes, and then stirred at 703⁄4 for 4 hours. The reaction liquid was removed by a rotary evaporator at 100 to 150 ° C to obtain 1489 parts of the polycarboxylic acid composition (x3) of the present invention. The shape was a colorless solid resin, and the functional group equivalent was 271 g/eq. The softening point (according to JIS K-7234) is 80.6 ° C, and the melt viscosity at 150 ° C is 〇 43 Pa.s.

合成例A 在備有攪拌機、回流冷凝管以及攪拌裝置之燒瓶中，一邊實施氮氣吹淨，一邊添加環己烯基曱基環己烯羧酸酯 110份、甲苯140份、12-鎢碟酸1份、鎮酸納1 · 5份、鱗酸氫二鈉I 5份、三辛基乙酸銨50%二曱苯溶液1. 5份，將此溶液升溫至45。(：，以20分鐘添加35重量％含過氧化氫之水溶液110份，然後，維持在45±5。(：中並攪拌I2小時。接著，以1重量％氫氧化鈉水溶液中和後，添加2〇重量/硫代硫酸鈉水溶液25份進行3〇分鐘之攪拌後靜置。取 S' 79 322150 201120000 出分離為2層之有機層，在此添加活性碳（味之素精細化學 (股）製造；CP2)5份、蒙脫石⑽NIMINE industries(股）製造；Kunipia)5份，在室溫下攪拌3小時後過滤。將所得慮液以水100份進行3次水洗，並經由所得之有機層顧除甲苯，得到以3, 4-環氧基環己基曱基_3,4_環氧基環己基缓酸醋為主成分之職樹脂（EP5)111份。所得環氧樹脂之環氧當$為130g/eq.。25。(：中之黏度為211mpa.s(E型黏度儀）。實施例 a、b、c、d、e、f、g、h、i、j、k、l 環氧樹脂係使用環氧樹脂（EP2)、環氧樹脂（Ep5);硬化劑係使用硬化劑組成物（Bb3、Bb4、Bb5、χΐ、χ3)、酸酐 (Η3) ’·硬化促進劑係使用四級鱗鹽（C2);添加劑係使用 (L1)(M1)、光安定劑（ADEKA製造；LA-62以下稱為L2); 磷化合物係使用亞磷酸三烷酯（ADEKA製造；Adekastab 3010以下稱為M2)、烧基磷:睃鋅（King Industries公司製造；XC-9206以下稱為M3) ’以下述表A所示之調配比例（重量份）進行調配，進行20分鐘之脫泡後，得到本發明或比較用之硬化性樹脂組.成物。所得之硬化性樹脂組成物進行以下試驗。將結果併示於下述表A。 (回焊.LED點燈試驗）將實施例及比較例1中所得之硬化性樹脂組成物充填於量筒中，將其使用精密吐出裝置注入並成型於搭載具有中心發光波465nm之晶片的外徑5mm立方之表面封裝型 LED封裝物（内徑4. 4mm、外壁高度1.25mm)。將該鑄造物 80 322150 201120000 放入加熱爐内，進行12Gt、1小時，再於15代、3小時之硬北處理，作成LED封裝物。對所得ίΕΙ)將回焊前後之照度使用爻光元件簡易地進行測定。（在遮光下，將作成之 LED以預定電流30mA之電流使其發光，在受光元件中受光，以在此流動之電流值作為照度之尺度）。測定係對LED剛密封後以及回焊試驗後之照度進行測定，並確認其差異。結果示於表A。另外，回焊試驗係使用高溫觀察裝置，假襞地模擬回焊。裝置、條件係如下述。裝置：高溫觀察裝置（SMT Scope SK-5000 ;山陽精工（股）製造）溫度條件：由25°C以2°C/秒升溫至150°C，然後在150°C 中維持2分鐘，再以2°C/秒升溫至260°C並維持1〇秒後，以1· 3。(：/秒冷卻至室溫。 81 322150 201120000 [表A]Synthesis Example A In a flask equipped with a stirrer, a reflux condenser, and a stirring apparatus, 110 parts of cyclohexenylnonylcyclohexene carboxylate, 140 parts of toluene, and 12-tungsole acid were added while purging with nitrogen. 1 part, 1 part of sodium citrate, 5 parts of disodium hydrogen citrate, 5 parts of trioctyl ammonium acetate 50% diphenylbenzene solution 1. 5 parts, the solution was heated to 45. (:, adding 110 parts by weight of a 35 wt% aqueous solution containing hydrogen peroxide in 20 minutes, and then maintaining it at 45 ± 5. (: and stirring for 1 hour). Next, after neutralizing with a 1% by weight aqueous sodium hydroxide solution, 2 parts by weight / 25 parts of aqueous sodium thiosulfate solution, stirred for 3 minutes, and then allowed to stand. Take S' 79 322150 201120000 and separate into two layers of organic layer, where activated carbon is added (Ajinomoto Fine Chemicals) Manufactured; CP2) 5 parts, montmorillonite (10) NIMINE industries (manufactured by NIMINE industries); 5 parts of Kunipia), stirred at room temperature for 3 hours and then filtered. The resulting solution was washed with water 100 times for 3 times, and organically obtained. In order to remove the toluene, 111 parts of the epoxy resin (EP5) containing 3,4-epoxycyclohexyldecyl _3,4-epoxycyclohexyl sulphuric acid vinegar as the main component was obtained. When $ is 130g/eq.. 25. (: viscosity is 211mpa.s (E-type viscometer). Examples a, b, c, d, e, f, g, h, i, j, k, l Epoxy resin (EP2), epoxy resin (Ep5); hardener used hardener composition (Bb3, Bb4, Bb5, χΐ, χ3), anhydride (Η3) '·The hardening accelerator is a four-grade scale salt (C2); the additive is (L1) (M1), a light stabilizer (made by ADEKA; LA-62 is hereinafter referred to as L2); and the phosphorus compound is a trialkyl phosphite. (made by ADEKA; Adekastab 3010 hereinafter referred to as M2), sulphur-based phosphorus: yttrium zinc (manufactured by King Industries Co., Ltd.; XC-9206 hereinafter referred to as M3), which is formulated by the blending ratio (parts by weight) shown in Table A below. After 20 minutes of defoaming, the curable resin composition of the present invention or the comparative product was obtained. The obtained curable resin composition was subjected to the following test. The results are shown in Table A below. (Reflow soldering. LED lighting Test) The curable resin composition obtained in the examples and the comparative example 1 was filled in a graduated cylinder, and this was injected and molded into a surface mount type LED having an outer diameter of 5 mm cube on which a wafer having a central light emission wave of 465 nm was mounted using a precision discharge device. The package (inner diameter 4. 4mm, outer wall height 1.25mm). The casting 80 322150 201120000 was placed in a heating furnace, 12Gt, 1 hour, and then hard-passed in 15th and 3th hours to form an LED package. For the gain ΕΙ) will be before and after reflow The measurement is easily performed using a calender element. (Under the light-shielding, the LED is made to emit light at a current of a predetermined current of 30 mA, and the light is received by the light-receiving element, and the current value flowing therein is used as a scale of illuminance.) The illuminance of the LED immediately after sealing and after the reflow test was measured, and the difference was confirmed. The results are shown in Table A. In addition, the reflow test uses a high-temperature observation device to simulate reflow soldering. The apparatus and conditions are as follows. Device: High temperature observation device (SMT Scope SK-5000; manufactured by Sanyo Seiko Co., Ltd.) Temperature conditions: from 25 ° C to 2 ° C / sec to 150 ° C, then at 150 ° C for 2 minutes, then The temperature was raised to 260 ° C at 2 ° C / sec and maintained at 1 3 3 after 1 。. (: / sec cool to room temperature. 81 322150 201120000 [Table A]

由以上結果可知，具有本發明之多元缓酸組成物的硬化劑組成物，即使暴露於回焊時之高溫中亦能以高的維持率保持照度，係具有高的光學特性者。 [產業上之可利用性] 本發明之多元羧酸組成物係，環氧樹脂之硬化能力優異而可適用作為環氧樹脂之硬化劑。並且，調配在環氧樹脂之該多元缓酸組成物係，一般使環氧樹脂硬化所採用之溫度域中的揮發極少，可穩定地達到硬化物之目的性能，例如高的透明度以及熱财久性（例如：耐回焊性、之手 322150 82 201120000 期點燈中的照度照度維持率、透光率之維持率等），因此在 LED之密封上極為有用。【圖式簡單說明】 • 益 ' 【主要元件符號說明】無 s· 83 322150From the above results, it is understood that the hardener composition having the polybasic acid-inhibiting composition of the present invention can maintain illuminance at a high maintenance rate even when exposed to a high temperature at the time of reflow, and has high optical characteristics. [Industrial Applicability] The polyvalent carboxylic acid composition of the present invention is excellent in curing ability of an epoxy resin and can be suitably used as a curing agent for an epoxy resin. Moreover, the polybasic acid-inhibiting composition of the epoxy resin is blended, and the volatilization in the temperature domain generally used for hardening the epoxy resin is extremely small, and the purpose of the cured product can be stably achieved, such as high transparency and heat retention. (for example, resistance to reflow, hand illuminance retention rate in 322150 82 201120000 period lighting, maintenance rate of light transmittance, etc.), so it is extremely useful for LED sealing. [Simple description of the diagram] • Benefits [Description of main component symbols] None s· 83 322150

Claims

201120000 七、申請專利範圍： 1. 一種含有下述式（1)表示之多元羧酸的多元羧酸組成物， HO201120000 VII. Patent application scope: 1. A polycarboxylic acid composition containing a polycarboxylic acid represented by the following formula (1), HO

式中，R各自獨立表示氫原子、碳數1至6之烷基或羧基；P表示下述（a)或（b)所定義之2價交聯基： (a)係屬於具有碳數6至2〇之分支構造的鏈狀烷基鏈之乂聯基，而該鏈狀烷基鏈具有碳數3至12之直鏈的主鏈與2至4個之側鏈，且該側鏈之至少丨者為碳數2 至10、 ?)係可在環上具有甲基之從％日一丫㈣環十五烧二甲醇之至少丨種的交聯多環 V八，衣一 —I^云除價交聯基，惟p為⑹時，《表示氫原i 如申請專項料〇讀岐成物，其申 2 f貝交聯基係以（a)所定義八交辟扁聯基，且以（a)所定義之又聯基係下述式（al)表示之2價基的任一者，我之式（al): 322150 84 201120000Wherein R each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a carboxyl group; and P represents a divalent crosslinking group as defined in the following (a) or (b): (a) is a carbon number 6 a linkage of a chain alkyl chain to a branch of 2〇, and the chain alkyl chain has a linear main chain of 3 to 12 carbon atoms and 2 to 4 side chains, and the side chain At least the carbon number is 2 to 10, ?) can have a methyl group on the ring from the day of the day (four) ring of fifteen burnt methanol, at least the cross-linked polycyclic V8, Yiyi-I^ Cloud de-crosslinking cross-linking, but when p is (6), "representing hydrogen source i, if applying for special materials, reading the sputum, its application 2 f shell cross-linking system is defined by (a) eight exchange flat joints, And any one of the two valence groups represented by the following formula (al) defined by (a), my formula (al): 322150 84 201120000

式中，各基之末端的*記號係表示在木記號處鍵結所鄰接之氧原子。 3. 如申請專利範圍第1項所述之多元羧酸組成物，其中， (a)之交聯基中之主鏈為碳數3至6之直鏈，側鏈之至少2者為碳數2至4之烷基。 4. 如申請專利範圍第2項所述之多元羧酸組成物，其中，以（a)所定義之交聯基係從2, 4-二乙基-1, 5-戊二醇去除2個羥基後之2價基。 5. 如申請專利範圍第1項所述之多元羧酸組成物，其中， 2價之交聯基係（b)所定義之交聯基，且（b)所定義之交聯基係下述式（bl)表示之2價基的任一者，式（bl):In the formula, the * mark at the end of each group indicates the oxygen atom adjacent to the bond at the wood mark. 3. The polycarboxylic acid composition according to claim 1, wherein the main chain in the cross-linking group of (a) is a linear chain having 3 to 6 carbon atoms, and at least 2 of the side chains are carbon atoms. 2 to 4 alkyl groups. 4. The polycarboxylic acid composition according to claim 2, wherein the crosslinking group defined by (a) is removed from 2, 4-diethyl-1, 5-pentanediol. A divalent group after a hydroxyl group. 5. The polycarboxylic acid composition according to claim 1, wherein the cross-linking group of the divalent cross-linking group (b) is defined, and the cross-linking group defined by (b) is as follows Any one of the divalent groups represented by the formula (bl), and the formula (bl):

85 322150 201120000 式中，各構造式中存在之複數個R2各自獨立表示氫原子或曱基。 6. 如申請專利範圍第5項所述之多元羧酸組成物’其係由 R2均為氫原子之多元羧酸所構成者。 7. 如申請專利範圍第5項所述之多元羧酸組成物’係包含 5〇莫耳％以上之式（1)之R為甲基及/或羧基的多元羧酸者。 8. 如申請專利範圍第1項所述之多元緩酸組成物’其中’ 式（〇之R為甲基或羧基。 9. 如申請專利範圍第8項所述之多元羧酸組成物，其中，氫原子以外之基為甲基。 10. 如申請專利範圍第1項所述之多元羧酸組成物，其中，夕元幾酸組成物係包含式（1)所示之多元缓酸的至少1 種與可經甲基取代之C4至C?環二、三或四竣酸酐。 11·如申請專利範圍第10項所述之多元羧酸組成物，其中，可經甲基取代之C4至C?環二、三或四緩酸酐係可、經甲基取代之環己烷二或三羧酸酐。 12· —種環氧樹脂用硬化劑，係含有申請專利範圍第1項之式（1)的多tl羧酸、或申請專利範圍第1〇項所述之多元羧酸組成物。 13·如申清專利範圍* 12項所述之環氧樹脂用硬化劑，其係由：式（1)之P表示的2價交聯基係以（a)所定義之交聯基且以（a)所定義之交聯基係下述（1)之2價基的多元 S6 322150 201120000 羧酸、與選自下述（2)之酸酐所成組群中之至少1種的酸酐，所成之多元羧酸組成物， (1) 2價基：從2, 4-二乙基-1，5-戊二醇去除2個羥基後之2價基； (2) 酸酐：甲基六氫酞酸酐、以及環己烷-1，2, 4-三緩酸-1，2-酐。 14.如申請專利範圍第12項所述之環氧樹脂用硬化劑，其係由：式（1)之P表示的2價交聯基係以（b)所定義之交聯基且以（b )所定義之交聯基係下述（1)之式（b 1)所示的 2價基中之任一者的多元羧酸、與選自下述（2)之酸酐所成組群中之至少1種的酸酐，所成之多元羧酸組成物， (1)式（bl):85 322150 201120000 wherein, a plurality of R2 present in each structural formula independently represent a hydrogen atom or a sulfhydryl group. 6. The polycarboxylic acid composition as described in claim 5, which is composed of a polycarboxylic acid wherein R2 is a hydrogen atom. 7. The polycarboxylic acid composition as described in claim 5, wherein the polycarboxylic acid having a methyl group and/or a carboxyl group in which R of the formula (1) is 5 mol% or more is contained. 8. The polybasic acid-reducing composition as described in claim 1, wherein R is a methyl group or a carboxyl group. 9. The polycarboxylic acid composition according to claim 8 of the patent application, wherein The group other than the hydrogen atom is a methyl group. The polycarboxylic acid composition according to claim 1, wherein the oxime acid composition comprises at least the polybasic acid represented by the formula (1). A polycarboxylic acid composition as described in claim 10, wherein the methyl group is substituted by a methyl group, and the C4 to C? ring is substituted with a methyl group. C? ring two, three or four slow acid anhydride, methyl substituted cyclohexane di or tricarboxylic anhydride. 12 · a kind of hardener for epoxy resin, containing the formula 1 (1) And a polycarboxylic acid composition as described in claim 1 of the invention. 13) A hardener for an epoxy resin according to the scope of claim 2, wherein: 1) The divalent cross-linking group represented by P is a cross-linking group defined by (a) and the cross-linking group defined by (a) is a valence group of the following (1) Element S6 322150 201120000 A carboxylic acid, an acid anhydride of at least one selected from the group consisting of the acid anhydrides of the following (2), a polycarboxylic acid composition, (1) a valence group: from 2, 4- Diethyl-1,5-pentanediol is a divalent group after removing two hydroxyl groups; (2) Anhydride: methylhexahydrophthalic anhydride, and cyclohexane-1,2,4-tris-acid-1, A sclerosing agent for an epoxy resin according to claim 12, wherein the divalent crosslinking group represented by P of the formula (1) is crosslinked by the definition of (b) The cross-linking group defined by the formula (b) is a polyvalent carboxylic acid of any one of the divalent groups represented by the following formula (1) (b), and an acid anhydride selected from the following (2) At least one acid anhydride in the group, the polycarboxylic acid composition formed, (1) Formula (bl):

式中，各構造式中存在之複數個R2各自獨立表示氫原子或曱基； (2)酸酐： 87 322150 201120000 甲基六氫酞酸酐、以及環己烷-1，2, 4—三羧酸-1，2- 酐。 15·=種硬化性樹脂組成物，係包含巾請專利第^所，之夕元竣酸組成物或中請專利範圍第U項所述之環氧樹脂用硬化劑，與環氧樹脂者。 16. 如申睛專利範圍第15項所述之硬化性樹脂組成物其中’環氧樹脂係脂環式環氧樹脂。 17. 如申凊專利範圍第16項所述之硬化性樹脂組成物，其中，硬化劑組成物係申請專利範圍第13項所述之環氧樹脂用硬化劑組成物。 18. 如申請專利範圍第16項所述之硬化性樹脂組成物，其中’硬化劑組成物係申請專利範圍第14項所述之環氧樹脂用硬化劑組成物。 19. 一種硬化物，係申請專利範圍第15項所述之硬化性樹脂組成物經硬化而成者。 20. —種申請專利範圍第1項所述之式（1)所示的多元叛酸之製造方法，係使下述（a)或（1))之>元醇與（c)反應者’ (a)係具有碳數6至20之分支構造的鏈狀脂肪族二元醇，而鏈狀烷基鏈具有碳數3矣12之直鍵的主鍵與2至4個之側鏈，且該側鏈之至少1者為％數2 至10之院基、或 ⑻係可在環上具有甲基之選自三環癸炫二甲醇或五環十五烷二甲醇之至少1種的交聯多環一醇’ (c)係至少1種選自六氫㈣酐、甲基六氫紘⑽以及 322150 88 201120000 環己烷-1，2, 4-三羧酸酐所成組群中之至少1種的酸酐，惟如為（b)時，係至少1種包含甲基六氫酞酸酐或環己烷-1,2,4-三羧酸酐之任一者的酸酐。 21. 如申請專利範圍第20項所述之多元羧酸組成物之製造方法，其中，將（a)或（b)之二元醇與（c)之酸酐以相對於酸酐基1當量之二元醇的羥基當量成為0.001至2 當量之比例，在反應溫度40至150°C使其反應。 22. 如申請專利範圍第21項所述之多元羧酸組成物之製造方法，其中，（c)之酸酐係六氫酞酸酐及甲基六氫酞酸酐之混合物。 23. 如申請專利範圍第21項所述之多元羧酸組成物之製造方法，其中，二元醇係2, 4-二乙基-1,5-戊二醇或2-乙基-2-丁基-1, 3-丙二醇。 24. 如申請專利範圍第21項所述之多元羧酸組成物之製造方法，其係使2, 4-二乙基-1，5-戊二醇、與六氫酞酸酐及曱基六氫酞酸酐之混合物反應而成。 25. 如申請專利範圍第21項所述之多元羧酸組成物之製造方法，其係使無取代之三環癸烷二曱醇或五環十五烷二甲醇、與六氫醜酸肝及甲基六氫醜酸針之混合物反應而成。 26. —種下述式（1)表示之多元羧酸，式（1) 89 322150 201120000 ΗWherein a plurality of R2 present in each structural formula independently represent a hydrogen atom or a hydrazine group; (2) an acid anhydride: 87 322150 201120000 methyl hexahydrophthalic anhydride, and cyclohexane-1,2,4-tricarboxylic acid -1,2- Anhydride. 15·=The type of the curable resin composition is a sulphuric acid resin composition as described in the U.S. Patent Application No. U. 16. The curable resin composition according to claim 15, wherein the epoxy resin is an epoxy ring epoxy resin. 17. The curable resin composition according to claim 16, wherein the hardener composition is a hardener composition for an epoxy resin according to claim 13 of the patent application. 18. The curable resin composition according to claim 16, wherein the hardener composition is a hardener composition for an epoxy resin according to claim 14. A cured product obtained by hardening a curable resin composition according to claim 15 of the patent application. 20. The method for producing a multi-repulsive acid represented by the formula (1) described in the first application of the patent application, wherein the following (a) or (1)) > ' (a) is a chain aliphatic diol having a branched structure of 6 to 20 carbon atoms, and the chain alkyl chain has a primary bond of 2 to 12 carbon atoms and 2 to 4 side chains, and At least one of the side chains is a hospital base having a % of 2 to 10, or (8) is a cross-linking of at least one selected from the group consisting of tricyclic fluorene dimethanol or pentacyclopentadecane dimethanol having a methyl group on the ring. The poly-polyol monool (c) is at least one selected from the group consisting of hexahydrotetrahydroanhydride, methylhexahydroindole (10), and 322150 88 201120000 cyclohexane-1,2,4-tricarboxylic anhydride. One type of acid anhydride, if it is (b), is an acid anhydride containing at least one of methylhexahydrophthalic anhydride or cyclohexane-1,2,4-tricarboxylic anhydride. 21. The method for producing a polycarboxylic acid composition according to claim 20, wherein the diol of (a) or (b) and the anhydride of (c) are one equivalent of 1 equivalent to the acid anhydride group. The hydroxyl equivalent of the primary alcohol is in a ratio of 0.001 to 2 equivalents, and is reacted at a reaction temperature of 40 to 150 °C. The method for producing a polycarboxylic acid composition according to claim 21, wherein the acid anhydride of (c) is a mixture of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride. 23. The process for producing a polycarboxylic acid composition according to claim 21, wherein the diol is 2,4-diethyl-1,5-pentanediol or 2-ethyl-2- Butyl-1, 3-propanediol. 24. The method for producing a polycarboxylic acid composition according to claim 21, which comprises 2,4-diethyl-1,5-pentanediol, hexahydrophthalic anhydride and mercaptohexahydrogen A mixture of phthalic anhydride is reacted. 25. The method for producing a polycarboxylic acid composition according to claim 21, which is an unsubstituted tricyclodecane decyl alcohol or pentacyclopentadecane dimethanol, and a hexahydro ugly acid liver and A mixture of methyl hexahydro sulphate needles is reacted. 26. A polycarboxylic acid represented by the following formula (1), formula (1) 89 322150 201120000 Η

RR

^ R各自獨立表示氫原子、碳數1至6之烧基或竣基，P表示下述⑷或⑻所定義之2價交聯基：係f於具有&數6至2G之分支構造的鏈狀炫基鏈之乂聯基’而該鏈狀烷基鏈具有碳數3至12之直鍵的主鏈與2 1 4個之側鏈，且該侧鏈之至少1 者為碳數2至1〇、 (b)係可在環上具有甲基之從選自三環癸院二甲醇或五％十五烷二甲醇之至少1種的交聯多環二醇中去除2個羥基後之2價交聯基，惟p為（b)時，R 表示氫原子以外之基。 27·如申請專利範圍第26項所述之多元羧酸，其中，p係以（a)所定義之2價交聯基，側鏈之至少2者為碳數2 至10之交聯基。 28. 如申請專利範圍第27項所述之多元羧酸，其中，以（a) 所定義之2價交聯基係從2, 4-二乙基-1，5-戊二醇去除 2個羥基後之伸烷基。 29. 如申請專利範圍第26項所述之多元羧酸，其中，p係以（b)所定義之2價交聯基。 3〇.如申請專利範圍第26項所述之多元羧酸，其中，式（1) 中之R係甲基或羧基。 90 322150 201120000 四、指定代表圖：本案無圖式 (一) 本案指定代表圖為：第（）圖。 (二) 本代表圖之元件符號簡單說明：五、本案若有化學式時，請揭示最能顯示發明特徵的化學式： HQ^ R each independently represents a hydrogen atom, a calcining group or a mercapto group having 1 to 6 carbon atoms, and P represents a divalent cross-linking group defined by the following (4) or (8): a group F having a branch structure of & 6 to 2G a chain-like chain of a chain-like chain, and the chain-like alkyl chain has a main chain of 3 to 12 carbon atoms and 2 1 4 side chains, and at least one of the side chains has a carbon number of 2 To (1), after removing two hydroxyl groups from at least one crosslinked polycyclic diol selected from the group consisting of tricyclic casket dimethanol or pentane dimethanol, having a methyl group on the ring A divalent cross-linking group, wherein when p is (b), R represents a group other than a hydrogen atom. The polycarboxylic acid according to claim 26, wherein p is a divalent crosslinking group defined by (a), and at least two of the side chains are a crosslinking group having a carbon number of 2 to 10. 28. The polycarboxylic acid according to claim 27, wherein the divalent crosslinking group defined by (a) is removed from 2,4-diethyl-1,5-pentanediol by two The alkyl group after the hydroxyl group. 29. The polycarboxylic acid of claim 26, wherein p is a divalent crosslinking group as defined in (b). The polycarboxylic acid according to claim 26, wherein R in the formula (1) is a methyl group or a carboxyl group. 90 322150 201120000 IV. Designated representative map: There is no schema in this case (1) The representative representative figure in this case is: (). (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: HQ

⑴ 4 322150(1) 4 322150