200911865 九、發明說明： 【發明所屬之技術領域】 本發明係有關一種具有優異之低黏度性，且可提供❹ 性、可撓性、高度伸長性優異之硬化物的新穎環氧樹脂γ 使用其之環氧樹脂組合物、以及其硬化物，該環 曰 有效地用作為以半導體元件為代表之電氣-電子零件等\ 封裝體、被覆材料'積層材料、或複合材料等之 Z適用於印刷電路板、半導體封裝體等電氣電邑 緣材料等等。 'έ 【先前技術】 環氧樹脂以其在工t上廣泛之用途使用至今 求之性能近年更是日兴掸矣而，、被要 曰多。例如，以環氧樹脂為主劑之 樹脂組合物的代表領域為半導體封裝材料，近年， 半導體兀件之集成度的提高，封裝體之尺寸也有大 化、=化的趨勢，而且安褒方式也朝表面安裝化進展， 於此環境下，開發一種對於 是為人所企盼者。 厚科耐熱性更為優異之材料， 卷二:二㈤兩集成化、高密度安裝化的技術動向，代 广利用模具之移送成形封裝，混成 裝、捲帶式封裝、铟脈杣此乃直接封 "十狀陣列封裝、塑膠球狀陣列封F 等之不使用模具而利用 干巧封裝 正方興未艾。然而二:進行封裝及安裝之方式， 之固體材料相較，卻有^液狀材料與用於移送成形 材料在黏度上有其上限=的Μ因為液狀 使用之树脂、硬化劑、填充 130083.doc 200911865 劑等會受到限制所造成。 專利文獻1特開平4-359009號公報 專利文獻2特開2006-188606號公報 專利文獻3特開2005-320477號公報 專利文獻4特開平3-27571 1號公報 為了克服此等問題，業界期待的是作為主劑之環氧樹脂 及硬化劑能低點度化、低吸濕化、高耐熱化。作 環氧樹脂，-般廣為人知的是雙盼A型環氧樹脂、及雙^ ^•衣氧樹月日等等’但其等在低黏度性此_層面卻不夠充 有關低黏度性優異之環氧樹脂E，專利文^中曾提案 一種具有亞甲氧鏈之環氧樹脂E，但其耐熱性、吸 有改良的餘地。專利文獻2中故$亲猫目+及‘化' j文獻2中日&案一種具有二環己基環 優:^駐’但其伸長性卻有改良的餘地。作為可撓性 類、& ’專利文獻3巾曾提案-種碳數為2〜12之二價 醇類之環氧樹脂E輿-僧私+ > 化卻右^ 之焉可挽性樹脂，但其低黏度 <的餘地。專利文獻4令曾提案-種由氫化二聚 —醇化合物之縮水甘油 與劑，但因使用-令‘ 的可撓性賦 的餘地。 —聚—㊣化合物之故，其伸純卻有改良 f發明内容】 疋以，本發明之目的係 性，且可提#_ '、 "―種具有優異之低黏度200911865 IX. Description of the Invention: [Technical Field] The present invention relates to a novel epoxy resin γ having excellent low viscosity and capable of providing a cured product excellent in flexibility, flexibility, and high elongation. The epoxy resin composition and the cured product thereof, the ring is effectively used as an electric-electronic component such as a semiconductor element, a package, a coating material, a laminate material, or a composite material, and the like is applied to a printed circuit. Electrical and electrical materials such as plates and semiconductor packages. 'έ 【Prior Art】 Epoxy resin has been used for a wide range of applications in the industry, and its performance has been in recent years. For example, a representative area of a resin composition mainly composed of an epoxy resin is a semiconductor packaging material. In recent years, the integration degree of a semiconductor element has been increased, and the size of the package has also become larger and smaller, and the ampoule method is also Advance toward surface mounting, in this environment, develop a kind of person who is looking forward to it. The material with better heat resistance of the thick section, Volume 2: Two (5) two integrated, high-density mounting technology trends, the use of mold transfer molding package, hybrid assembly, tape and reel packaging, indium pulse is directly Sealing "Ten-shaped array packaging, plastic spherical array sealing F, etc., without the use of molds, using dry packaging is in the ascendant. However, the method of encapsulation and installation, compared with the solid materials, there are liquid materials and the upper limit of the viscosity of the transfer molding material = Μ because of the liquid resin, hardener, filling 130083. Doc 200911865 Agents will be subject to restrictions. Patent Document 1 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The epoxy resin and the hardener which are the main components can be low-intensity, low in moisture absorption, and high in heat resistance. As epoxy resin, it is widely known that it is a pair of A-type epoxy resin, and a double ^ ^• clothing oxygen tree, etc. 'But its low viscosity is not enough for low viscosity. Epoxy Resin E, an epoxy resin E having a methylene oxide chain has been proposed in the patent document, but it has room for improvement in heat resistance and absorption. In Patent Document 2, there is a room for improvement in extensibility of the Japanese and Japanese versions of the Japanese and Japanese versions of the Japanese and Japanese patents. As a flexible type, & 'Patent Document 3, it has been proposed - an epoxy resin of a divalent alcohol having a carbon number of 2 to 12, E 舆 - 僧 + + > , but its low viscosity < Patent Document 4 has proposed a glycidol and a compound from a hydrogenated dimer-alcohol compound, but there is room for flexibility by using -. - Poly-positive compound, its pure but improved. f Inventive content] 疋, the purpose of the present invention, and can be #_ ', "-- has excellent low viscosity
代供耐濕性、可撓性、一 A 的新穎環氧 向度伸長性優異之硬化物 物。㈣H用其之環氧樹腊組合物、以及其硬化 130083.doc 200911865 具體言之，本發明係有關一種下述通式（1):A cured product excellent in moisture resistance, flexibility, and a novel epoxy elongation of one A. (4) Epoxy wax composition for H and hardening thereof 130083.doc 200911865 Specifically, the present invention relates to a general formula (1):
(其中，R丨〜R8表碳數4〜12之烷基，|^〜尺8中至少一 4 不飽和雙鍵，R丨〜Rs之兩個以上可為相同； 、有 双υ至3之Μ 數，G表縮水甘油基） 所示之水解性鹵素量在0.2重量％以下之新賴環氧樹脂。 又，本發明又有關一種包含環氧樹脂及硬化劑之環曰氧樹 脂組合物，其中混配有上述環氧樹脂作為必要成分。 又，本發明又有關-種將上述環氧樹脂組合物硬化而成 之硬化物。 【實施方式】 本發明之環氧樹脂，可藉由令下列通式（2):(wherein R丨~R8 represents an alkyl group having a carbon number of 4 to 12, at least one of 4 unsaturated double bonds in the range of |^~8, and two or more of R丨~Rs may be the same; The number of turns, G-glycidyl group) is a new epoxy resin having a hydrolyzable halogen amount of 0.2% by weight or less. Further, the present invention relates to a cyclic oxime resin composition comprising an epoxy resin and a hardener, wherein the above epoxy resin is compounded as an essential component. Further, the present invention relates to a cured product obtained by hardening the above epoxy resin composition. [Embodiment] The epoxy resin of the present invention can be obtained by the following formula (2):
一個具 (其中’ R丨〜R4表碳數4〜12之烷基，r丨〜&中至，丨、 有不飽和雙鍵’ R广R4之兩個以上可為相同） 所不之二聚二醇化合物與表_醇反應而製得。 130083.doc 200911865 上述二聚二醇化合物，可舉的是將聚脂肪酸（二聚酸）之 羧基還原成羥基而成者。此處，聚脂肪酸係使不飽和脂肪 酸（亞油酸、油酸）之兩個或兩個以上進行分子間反應所獲 得之化合物，其主成分係碳數36之二元酸，屬習知物。 令上述二聚二醇化合物與表_醇反應之反應，可利用與 . 一般之環氧化反應相同之方式進行。例如，可舉的是在將 上述二聚二醇化合物溶解於過量之表画醇中之後，在氫氧 化鈉、氫氧化鉀等鹼金屬氫氧化物之存在下，在4〇〜12(rc Γ 之範圍下反應卜10小時之方法。此時，基於水解性鹵素降 低之觀點’宜在50〜70°C下進行反應。 作為使用之鹼金屬氫氧化物’可舉的是氫氧化鈉、氫氧 化鉀、氫氧化鋰或其等之混合物等，宜以水溶液或固體狀 使用，更好的是一般市售之氫氧化鈉水溶液。 鹼金屬氫氧化物之使用量，相對二聚二醇化合物中之羥 基1莫耳為0.8〜15.0莫耳，宜為〇·9〜2〇莫耳之範圍。若較 其為少，則殘存水解性鹵素之量會增加，若較其為多，則 U 冑氧樹脂合成時之凝膠的量會增加’招致水洗時乳化物之 生成，而且收率也會降低’不令人滿意。 . 又，基於促進反應之目的，可併用相間移動觸媒。作為 冲目間移動觸媒之具體例，可舉的是氣化四甲銨、溴化四丁 錢1化节基三乙敍、氣化甲基三辛録等之四級敍鹽。此 等：鹽可混合兩種以上使用。又，此等相間移動觸媒之使 量相對—聚二醇化合物100重量份為20重量份以下， 宜為〇.5〜10重量份之範圍，更好為卜5重量份之範圍。 130083.doc 200911865 又’表_相對二聚二醇化合物中 量使用，通常相對二聚- &基的&計量係過 本一* 3^化合物中々 耳，係在1·5〜30莫耳， 之备基的合計量】莫 且為2〜I5莫耳，承拉9 耳之範圍。若較其為少 更好疋在2·5〜10莫 增高，若較其為多， 量大增，黏度 舉的是表氯醇、表蛾-作為表鹵醇，可 ^田醇表溴醇、甲基表氯醇、、皇 醇、甲基表蛾醇等等，其中較好的是表氣醇。土表漠 :二應時，可在與環氧基不反應之 的溶媒為：甲苯、二 — 疋玎具體 本、本等之芳香族烴、 酮、甲基乙基酮 '璜p 甲基異丁基 之醇類，-…嗣等之網類，丙醇、丁醇等 之知類—甘醇甲哔寻 醇趟類，乙醚、丁驗、7且 一丁一醇甲醚等之二 喊 乙基丙基喊等之时·缺 烷、四氫咳喃等之月tIS斗. 月曰肪族喊類’二噁 溶媒混合兩種以上估田 亞颯専專’可將此等 裡以上使用。此等溶媒之使 100重量份為200重量 罝相對表豳醇 里伤以下’且為5〜ls〇重詈 更好的是1〇〜_重量份之範圍。 里…圍’ 反應終了後，餾去過|f 中、過，再子k 之表函醇，將殘餘物溶解於溶劑 二t慮再予水洗除去無機鹽，然 二 獲得本發明之環氧樹脂。 m餾去☆劑’可 當水解性齒去旦 素里過多^，基於降低水解性齒素量之觀 ‘·’可在所獲得之環氧樹 ' 量為㈣倍量之……相對殘存之水解性齒素 〈万式添加驗金屬齑惫#% 溫度進行10分鐘2| n士金屬双乳化物，以60〜9(TC之 方法將乃θ 小'之純化反應後’以中和、水洗等之 方法將過1之驗金屬氯氧化物或 130083.doc 200911865 浴媒減塵館去，可獲得本發明之環 本發明之環氧樹腊，係在通中曰° 者，基於低點度性之觀點，n=^( )中/表⑴之整數 50%以上，更好係70%以上。（體）之含有率宜為 又水解性鹵素含量宜為〇 含量在0.2重量⑽上 $/叫下。右水解性齒素 反應會受到阻礙，，果吏用驗性硬化促進劑時，硬化 發生絕緣信賴性之 降低。特別是會 令人滿意。較佳二電氧電子領域之用途方面不 %以下。 疋在〇·!重量％以下，更好的是在_重量 =:一與硬化_形成組合物，可使 劑=::::組::’係，含環氧樹一 上、、/物’其中關於環氧樹脂成分，係混配有 ，所示之環氧樹脂作為其必要成分。 下二：Γ式⑴所示之環氧樹脂作為其必要成分之情況 lj，一般作為環氧樹脂之硬化劑為人所知者均可 4如包括雙氰胺、多價酚類、酸酐類、芳香族及 脂肪族胺類等等。 、 右做具體例示，作為多價盼類，包括例如雙盼A、雙酚 F雙盼S、苟雙盼、4,4,_雙紛、2,2，_雙盼、氫酸 '間苯二 酚、奈—醇等之二價紛類，或是以三♦經基苯基）甲烧、 U，2,2-四（4_羥基苯基）乙烷、酚醛清漆、鄰-甲酚醛清漆、 萘紛搭清漆、聚乙埼基紛等為代表之三價以上之盼類。此 130083.doc 200911865 外還包括酚類、萘酚類或雙酚A、雙酚F、雙酚s、芴雙 酚、4,4，-雙酚、2,2，_雙酚、氫醌、間苯二酚、萘二醇等之 一價紛類，與甲搭、乙酸、苯链、對-經基苯經、對-間二 甲苯二醇等之縮合劑所合成之多價酚性化合物。 作為酸酐，包括酞酸酐、四氫酞酸酐、甲基四氫酞酸 酐、六氫酞酸酐、曱基六氫酞酸酐、5_雙環庚烯_2,3_二羧 酸針、橋二雙環[2.2」]^稀2,3·^㈣、苯偏三㈣ 等等。 ( 作為胺類，包括、4,4,_二胺基二苯基甲院、4,4, 苯基丙烷、4,4，-二胺基 胺 一苯基石風、間-苯二胺 '對_二甲 苯二胺等之芳香族胺類，乙二胺、己二胺、二乙#三胺、 二乙撐四胺等之月旨肪族胺類。 本發明之樹脂組合物中，可混合使用此等硬化劑之一種 或兩種以上。 人，…之環氧樹脂組合物中，作為環氧 也可混配通式（1)所千士欢πηOne with (where 'R丨~R4 table carbon number 4~12 alkyl, r丨~& middle to, 丨, with unsaturated double bond' R wide R4 two or more can be the same) The polyglycol compound is prepared by reacting with a table-alcohol. 130083.doc 200911865 The above dimer diol compound is exemplified by reduction of a carboxyl group of a poly fatty acid (dimer acid) to a hydroxyl group. Here, the polyamic acid is a compound obtained by performing intermolecular reaction of two or more of unsaturated fatty acids (linoleic acid, oleic acid), and its main component is a dibasic acid having a carbon number of 36, which is a conventional matter. . The reaction of reacting the above dimer diol compound with a surface alcohol can be carried out in the same manner as in the usual epoxidation reaction. For example, after dissolving the above dimer diol compound in an excess of the surface alcohol, in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, at 4 〇 12 (rc Γ) In the range of 10 hours, the reaction is carried out at a temperature of 50 to 70 ° C. The alkali metal hydroxide used may be sodium hydroxide or hydrogen. Potassium oxide, lithium hydroxide or a mixture thereof or the like is preferably used in the form of an aqueous solution or a solid, more preferably a commercially available aqueous sodium hydroxide solution. The amount of the alkali metal hydroxide used in the dimerized diol compound The hydroxyl group 1 molar is 0.8 to 15.0 mol, and is preferably in the range of 〇·9 to 2 〇 mol. If it is less, the amount of residual hydrolyzable halogen increases, and if it is more, U 胄When the amount of the oxygen resin is synthesized, the amount of the gel increases, which leads to the formation of an emulsion at the time of washing, and the yield is also lowered, which is unsatisfactory. Further, based on the purpose of promoting the reaction, the phase-shifting catalyst can be used in combination. Specific examples of moving the catalyst between the eyes, it is possible to mention Four grades of salt, such as tetramethylammonium, brominated tetrabutyl, 1 sulfhydryl, triacetate, gasified methyl trisin, etc. These: salt can be used in combination of two or more. The amount of the medium is relative to 100 parts by weight of the polyglycol compound, preferably 20 parts by weight or less, more preferably 5 parts by weight. 130083.doc 200911865 The dimer diol compound is used in an amount, usually relative to the dimer- & base & metering system, the 々 ear of the compound, is in the range of 1-5 to 30 moles, and the total amount of the base is And it is 2~I5 Moule, and the range of 9 ears is stretched. If it is less than it is better, it will increase in 2·5~10, if it is more, the amount will increase greatly, and the viscosity will be epichlorohydrin. Moth - as an epihalohydrin, can be a table alcohol bromohydrin, methyl epichlorohydrin, emerol, methyl epitheliol, etc., of which the better is the surface gas alcohol. The solvent which can be reacted with the epoxy group is: toluene, di-anthracene, the aromatic hydrocarbon of the present, the ketone, the methyl ethyl ketone '璜p methyl isobutyl alcohol, - ... Such as nets, such as propanol, butanol, etc. - Glycol methyl hydrazine, ether, butyl, 7 and butyl alcohol methyl ether, etc. The moon tIS bucket of alkane, tetrahydrogen cough, etc. The moon 曰 族 喊 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' The weight 罝 is relative to the surface sterol, and the following is '5' ls 〇 詈 詈 詈 詈 詈 詈 詈 詈 詈 詈 詈 詈 詈 _ 围 围 围 围 围 围 围 围 围 围 围 围 围 围 围 围 围 围 反应 反应 反应 反应 反应 反应 反应 反应The alcohol of k is dissolved in the solvent and then washed with water to remove the inorganic salt, and the epoxy resin of the present invention is obtained. The m-reduced ☆ agent can be used as a hydrolyzable tooth. Based on the reduction of the amount of hydrolyzable dentate, the amount of the obtained epoxy tree can be (four) times the amount of the remaining hydrolyzed dentate (the type of metal 齑惫#% temperature for 10 minutes) 2| nshi metal double emulsion, with 60~9 (the method of TC will be θ small 'purification reaction' after neutralization, washing, etc. According to the viewpoint of low-pointness, n=^( The integer of the middle/table (1) is 50% or more, more preferably 70% or more. The content of (body) is preferably such that the hydrolyzable halogen content is preferably 〇 at 0.2 weight (10). The right hydrolyzed dentate reaction is hindered, and when the test hardening accelerator is used, the hardening of the insulation is reduced. Especially it will be satisfactory. Preferably, the use in the field of electro-oxidation electronics is not less than 5%.疋在〇·!% by weight or less, more preferably in _weight=: one with hardening_forming composition, enabling agent =:::: group:: 'system, containing epoxy tree, 'The epoxy resin component is blended with the epoxy resin shown as an essential component. The second case: the epoxy resin represented by the formula (1) as an essential component thereof, generally known as a hardener for epoxy resins, such as dicyandiamide, polyvalent phenols, acid anhydrides, Aromatic and aliphatic amines and so on. Specific examples are given to the right, as multi-price expectation, including, for example, double-presence A, bisphenol F, double-desired S, bismuth, 4,4, _ double, 2, 2, _ double-hop, hydrogen acid 'm-benzene Divalents of diphenols, naphthyl alcohols, etc., or trimethyl phthalate), U, 2,2-tetrakis(4-hydroxyphenyl)ethane, novolac, o-cresol Varnishes, naphthalene varnishes, and polyethyl phthalate are representative of the three-price or more. This 130083.doc 200911865 also includes phenols, naphthols or bisphenol A, bisphenol F, bisphenol s, bismuth bisphenol, 4,4,-bisphenol, 2,2, bisphenol, hydroquinone, A polyvalent phenolic compound synthesized from a condensing agent such as resorcinol or naphthalenediol, and a condensing agent such as methyl acetate, acetic acid, benzene chain, p-phenylbenzene, p-m-xylene glycol or the like. . Examples of the acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, decyl hexahydrophthalic anhydride, 5-bicycloheptene-2,3-dicarboxylic acid needle, and bridged bicyclo [ 2.2"]^Thin 2,3·^(4), Benzene 3 (4), etc. (As amines, including, 4,4,-diaminodiphenylmethyl, 4,4, phenylpropane, 4,4,-diaminoamine-phenyl-stone, m-phenylenediamine' An aromatic amine such as xylene diamine, an aliphatic amine such as ethylenediamine, hexamethylenediamine, diethylenetriamine or diethylenetetramine. In the resin composition of the present invention, it can be mixed. One or two or more of these hardeners are used. In the epoxy resin composition of the human, the epoxy resin may be mixed as the epoxy compound of the formula (1).
()^本發^環氧樹脂料㈣種環氧樹 月日。作為此一情況下之 以上環負美心曰“吏用刀子中具有兩個 土 有一般環氧樹脂。舉例言之，包括雙_ A、雙酚S、苟雙酚、 L祜雙酚 咕 呀4,4_雙紛、2,2’-雙紛、氫酉昆 酚等之二價酚類，式θ_ 門本一 或疋二-(4_羥基苯基）甲烷、 (4-羥基苯基）乙燒、齡太 5 上之紛類，^ 甲㈣清漆等之三價以 上之：類，四漠雙⑽等之幽化 甘油基醚化物等，式g取 1彳了生之縮水 水…類，或是：：：乙二醇或聚丙二醇等醇類之聚縮 氛基二苯基甲院等之聚縮水甘油基胺 130083.doc •12- 200911865 類等，脂環式環氧樹脂等。 a u ^ , 專裒氧樹脂可混合使用一種 ;陶裡u上。若以本絡 ,,^ ^ 之裒氧樹脂作為必要成分之组人 物的情形’與本發明有 ㈣刀之，，且口 * ' -Ψ^ & ^ 式（1)所不環氧樹脂的混配 重该J衣軋树脂在全體φ盔c , Λ 圍。 全體中為5〜100%’宜為60〜1〇。%之範 又，本發明之環氧樹脂組 臂醯舱^ ^ 物中，可適當混配以聚酯、 聚醯胺、聚醯亞胺、聚醚 ^ 笮胺基甲馱酯、石油樹脂、茚 本开呋喃樹脂、苯氧基樹 寻之养聚物或南分子化合物， 也可混配無機填充劑、嚭 . ，；斗、難燃劑、增黏性賦盥劑、偶 合劑、流動性提高劑尊之天“ U偶 可為球肤U & 4之杨劑。作為無機填充劑，例如 了為球狀或破碎狀熔融二氧化 n r. . v . 、々日日一巩化矽等之二氧 化夕粕末、氧化鋁粉末、 择 坂褐杨末、雲母、滑石、碳酸 鈣、氧化鋁或水合氧化鋁等 盔德“躺所 作為顏科，包括有機系或 可舉的有”…I · 為增黏性賦與劑， 麻油系、脂肪族植物油脂肪酸·胺合成 ::乳化聚乙稀蠘、有機蒙脫土系等等。又，因應必要， ^發明^樹脂組合物中’還可使用卡巴蟻、〇ρ蠛等之脫模 齊J γ_縮水甘油氧基丙基=甲負其功ρ»楚 、 甲氣基石夕炫等之偶合劑、碳黑 匕Ah二氧化録等之難燃劑、石夕油等之低應力化 劑、硬脂酸鈣等之滑劑等等。 再者’因應必要，本於明夕括 + 4八”， 尽^月之樹月曰組合物中還可使用周知 之硬化促進劑。其可舉實例為_ 一 貝妁兩—乙撐二胺、三乙撐四胺、 異佛爾酮二胺、Μ -甲婪- … 一甲本-私、二胺基二苯基甲烷等之胺 1 乙基-4-甲基咪唑等之咪唑類，2-甲基 130083.doc -13· 200911865 咪㈣、2-乙基-4-甲基爾等之咪唾琳類"米嗤化合物 之二吖嗪鹽、氰基乙基鹽、氰基乙基笨偏三酸鹽等之各種 鹽類’醋酸辞、醋酸鈉等之金屬系化合物類，氯化四乙錢 荨之四級錄鹽類，醯胺化合物類，三笨膦等之有機麟化合 ，類等等。此等硬化促進劑之混配比例，相對於本發明之 環氧樹脂100質量份為0.01〜5重量份，更好為〇1〜2重量 份。 本發明之環該脂硬化物，可藉由加熱上述環氧樹脂組 合物而獲得。有關獲得硬化物之方法，可適當地使用注 模、，主入、裝瓶、滴製、滴覆、移送成形、壓縮成形等 等’此時之溫度通常為loot〜3〇(TC之範圍。 發明之效果 使用本發明環氧樹脂之環氧樹脂組合物，具有優異之低 黏度性，且將其硬化所得之硬化物具有耐濕性、可撓性、 高度伸長性優異之性能，因此適於高抗蝕塗料、粉體塗 料、PCM塗料、罐塗料等之塗布用途，或是土木-建設用 途，接著用途，電氣絕緣用、半導體晶片假固定劑等之電 氣-電子零件用途，以及以印刷電路板或碳纖維補強塑膠 (CFRP)為首之各種複合材料用途等等，特別適用於印刷電 路板、半導體封裝體等電氣電子領域之絕緣材料等等。 實施例 以下，茲根據實施例及比較例將本發明具體說明，但本 發明之技術範圍不受實施例之限制。又，實施例及比較例 中之各成分之混配份數，如無特別否認，均是指重量份。 130083.doc -14- 200911865 又，性狀值分析係採以下之方法。 (1) 環氧當量係根據Jis Κ_7236測定。 (2) 水解性氯夏，係种取樣本約2 g置於三角燒瓶中，以 二°惡烧溶解後’加入0.1 N-KOH甲醇溶液約25 mi，在70°C 溫水中反應30分鐘後’移至200 ml燒杯中，再加入丙_、 離子交換水及醋酸3 m卜以利用0.01 N_AgN〇3水溶液之滴 定測定之。 (3) 黏度係根據JIS K-7233由單一圓筒旋轉黏度計法測 定。 實施例1 在備有授拌機、溫度計、氮氣吹入管及冷卻管之反應裝 置中，添加PRIP〇L2033(二聚酸之羧基還原至羥基之二聚 一醇化合物，羥基當量27〇 g/eq，優尼克馬日本公司 製）3〇〇份、表氯醇256.9份及甲苯12〇份，予以混合溶解 之。在50。(：下一面攪掉，一面將氣化爷基三乙銨6份加入 後將96 /q氫氧化鉀97.4份以每次隔30分鐘分5次之方式加 入繼之，在5〇C下反應2.5小時之後，加入甲苯3〇〇份， 以過濾除去生成之鹽，以離子交換水270份水洗並分液 後，餾去表氣醇，將其溶解於甲基異丁基酮5〇〇份中。 作後在80 C下攪拌之，並一面添加12 5%氫氧化鈉水 :液96份，進行15小時之純化反應。之後以_份之離子 父換水水洗並分液之。而後再以磷酸中和、水洗之並除去 θ二後，再進行水洗及過濾後，餾去曱基異丁基_庐 得本發明之環氧樹脂A 325份。所獲得之環氧樹脂A ^ 130083.doc 15 200911865 250t下之黏度為200 mPa.s，氧當量為378 g/eq，水解性 氯為0.02%。由GPC測定結果可知，n=〇體為體 及其他成分等為16%。就環氧樹脂A，其紅外線光错圖係 示於圖1 ’ GPC曲線圖係適於圖2。 實施例2及比較例1、2 作為環氧樹脂成分，係採用實施例】所得之環氧樹脂A、 YD-171(一聚酸聚縮水甘油g旨樹脂、環氧當量旦㈣、 25°C下之黏度為740 mPa.s、水解性氣Q51%，東都化成公 司製）、阳-207S(聚丙二醇二縮水甘油喊 '環氧當量η] g/eq、25°C下之黏度為44 mPa.s、水解性氯〇〇5%，東都化 成公司製），作為硬化劑’係採用力卡希德MH7〇〇(甲基六 氫敗酸酐，酸if當量168 g/eq，冑日本理化製），作為硬化 促進劑’係採用希西可林PX_4ET(有機鱗鹽化合物，曰本 化學製），以表i中所示之混配方式，獲得環氧樹脂組合 物。又，表中之數值係指混配時之重量份。 使用此環氧樹脂組合物在10(TC下進行2小時之成形，再 以刚以⑴小時之後硬化’獲得硬化物試驗片之後供 各種物性測定用。結果適於表2中。 又，硬化物性之試驗方法及評估方係如下所干。 ⑴㈣膨脹係數U用熱機械測定裝L以節分 之升溫速度測定，以50°C〜100°C之變位求得。 ⑽”，係採用直徑5。職、厚二之試驗片，在 Μ、職RH之條件下做50小時之吸濕後的重量增加變 化率。 130083.doc •16- 200911865 (3) 離子性雜質量，係將105°C、20小時加壓蒸煮器試驗 後之抽出離子份，以離子色層分析法測定其氣離子、鈉離 子、鉀離子，換算成固形分求得。 (4) 伸長量，係根據JIS K-6251，以啞鈴狀6號形試驗片 測定。 (5) 發黏性，係以指觸硬化物確認發黏之有無。 表1 實施例1 比較例1 比較例2 環氧樹脂A 100 • YD-171 - 100 _ PG-207S - 100 硬化劑 90 90 90 硬化促進劑 0.5 0.5 0.5 表2 實施例2 比較例1 比較例2 線熱膨脹係數(ppm/°C ) 203 206 115 吸水率(°/〇) 0.5 0.3 3.1 離子性雜質量(ppm) 氣離子 納離子 鈣離子 10 0.1以下 0.1以下 600 0.1以下 0.1以下 300 0.2 0.1以下 伸長量(％) 125 48 38 發黏性 無 有 無 比較例1中，使用之環氧樹脂，其水解性氯較0.51 %及 0.2%為多，因此硬化物之氯離子有600 ppm，與實施例相 較多至6 0倍。此一事實顯示電絕緣信賴性不佳。又，伸長 量48%也只有實施例之約一半。又，比較例2中所使用之 130083.doc 17 200911865 裒氧樹月日為不具有不飽和鍵結之脂肪族醇，伸長量低至 π%，只為實施例之約1/3，與實施例相較延伸性並不充 刀再者，比較例2之吸水率高至31%，與實施例比較吸 水性過高因而不佳。 產業上之可利用性 使用本發明之環氧樹脂，其低黏度性優異，且可獲得低 彈Γ且具有高度伸長性之硬化物。因此可製造在-般的使 用祀圍内具有必要之耐熱性，且為低彈性、耐渴性優異之 硬化物，可獲得有對於以半導體元件為代表之電氣-電子 零件等之封裝體、被覆材料、積層材料、或複合材料等有 用之樹脂組合物，技術上之意義重大。 【圖式簡單說明】 圖中之縱軸表透過率，橫 圖中之縱輛表標準聚乙 圖1係環氧樹脂A之IR光譜圖 轴表波長。 圖2係環氧樹脂A之GPC曲線圖 烯換算分子量，橫軸表溶出時間 130083.doc -18-() ^ This hair ^ epoxy material (four) kind of epoxy tree. As a result of the above, the above-mentioned ring is beautiful. "There are two kinds of organic epoxy resins in the knife. For example, including double _ A, bisphenol S, bismuth bisphenol, L bis bisphenol 咕Divalent phenols such as 4,4_bis, 2,2'-bis, hydroquinone, etc., θ_Domoto-1 or bis-(4-hydroxyphenyl)methane, (4-hydroxyphenyl) ) B-burning, ageing on the 5th, ^ A (four) varnish and other three or more: class, four desert double (10) and other glycerol etherate, etc., formula g take 1 彳 raw shrink water... Class, or::: Polyglycidylamine such as ethylene glycol or polypropylene glycol, such as polycondensation-based diphenyl group, etc. 130083.doc •12- 200911865 Class, etc., alicyclic epoxy resin, etc. AU ^ , a special type of enamel resin can be used in combination; in the case of Tao Li, if the oxime, ^ ^ oxime resin as a group of essential components of the case 'and the invention has (four) knife, and mouth * '-Ψ^ & ^ The compounding weight of the epoxy resin of the formula (1) is the weight of the J-coating resin in the entire φ helmet c, and the circumference is 5 to 100% of the whole. % of the formula, the epoxy of the present invention In the lipid group, the mixture can be appropriately mixed with polyester, polyamide, polyimine, polyether, decyl methyl phthalate, petroleum resin, sulfonium furan resin, phenoxy tree The polymer or the south molecular compound may also be mixed with an inorganic filler, 嚭., a bucket, a flame retardant, a viscosity-enhancing agent, a coupling agent, and a fluidity improver. U & 4 Yang agent. As the inorganic filler, for example, it is a spherical or crushed molten oxidized nr. v. , 々日日分化矽, etc., cerium oxide powder, alumina powder, 坂 坂 坂, mica, Helmets such as talc, calcium carbonate, alumina or hydrated alumina "Like as a Yankee, including organic or may be"... I · A viscosity-enhancing agent, sesame oil, fatty vegetable oil fatty acid amine Synthesis:: Emulsified polyethylene sulphate, organic montmorillonite and so on. Also, if necessary, ^Inventive^Resin composition can also use Kabba ants, 〇ρ蠛, etc., release J γ-glycidoxypropyl group = A negative ρ» Chu, A gas base stone Xi Xu Such as a coupling agent, a flame retardant such as carbon black 匕Ah dioxide, a low stress agent such as Shixia oil, a slip agent such as calcium stearate, and the like. In addition, 'in view of the need, this is included in the eve of the evening + 4 eight," the moonlight 曰 composition can also be used to know the hardening accelerator. It can be exemplified as _ a shellfish two - ethylene diamine , triethylenetetramine, isophorone diamine, hydrazine-methylhydrazine-...imidazide, such as a mono-, diaminodiphenylmethane, etc., an amine such as ethyl-4-methylimidazole, 2-methyl 130083.doc -13· 200911865 imi (tetra), 2-ethyl-4-methyl er, etc., salicin " rice compound, dioxazine salt, cyanoethyl salt, cyano Various kinds of salts such as tribasic acid salts, metal compounds such as acetic acid, sodium acetate, etc., organic salts of quaternary ammonium chloride, guanamine compounds, triphenylphosphine, etc. The compounding ratio of the hardening accelerator is 0.01 to 5 parts by weight, more preferably 1 to 2 parts by weight, per 100 parts by mass of the epoxy resin of the present invention. The material can be obtained by heating the above epoxy resin composition. For the method of obtaining a cured product, injection molding, main injection, bottling, dripping, dripping, and shifting can be suitably used. Sending, compression molding, etc. 'The temperature at this time is usually loot~3〇 (the range of TC. The effect of the invention is that the epoxy resin composition of the epoxy resin of the invention has excellent low viscosity and hardens it) Since the obtained cured product has excellent properties of moisture resistance, flexibility, and high elongation, it is suitable for coating applications of high-resistance coatings, powder coatings, PCM coatings, can coatings, etc., or civil-construction applications, and then Applications, electrical and electronic parts for electrical insulation, semiconductor wafer dummy fixatives, and various composite materials such as printed circuit boards or carbon fiber reinforced plastics (CFRP), especially for printed circuit boards and semiconductor packages. Insulating materials and the like in the field of electrical and electronic systems. EXAMPLES Hereinafter, the present invention will be specifically described based on examples and comparative examples, but the technical scope of the present invention is not limited by the examples. Further, each of the examples and comparative examples The number of parts of the ingredients, if not specifically denied, refers to parts by weight. 130083.doc -14- 200911865 Again, the trait value analysis method is as follows: (1) The epoxy equivalent is determined according to Jis Κ_7236. (2) Hydrolyzable chlordia, a sample of about 2 g of the strain is placed in an Erlenmeyer flask, dissolved in 2° smoldering, and then added to a 0.1 N-KOH methanol solution for about 25 mi. After reacting in warm water at 70 ° C for 30 minutes, 'moved into a 200 ml beaker, and then added with C-, ion-exchanged water and acetic acid 3 m to determine by titration with 0.01 N_AgN 3 aqueous solution. (3) Viscosity is based on JIS K -7233 was measured by a single cylinder rotary viscometer method. Example 1 In a reaction apparatus equipped with a mixer, a thermometer, a nitrogen gas injection tube, and a cooling tube, PRIP〇L2033 was added (the carboxyl group of the dimer acid was reduced to the hydroxyl group) A polyhydric alcohol compound, a hydroxyl group equivalent of 27 〇g/eq, manufactured by Ukrainian Japan Co., Ltd., 3 parts by weight, 256.9 parts of epichlorohydrin, and 12 parts of toluene were mixed and dissolved. At 50. (: The next side is stirred up, and after adding 6 parts of gasified stearyl triethylammonium, 97.4 parts of 96 / q potassium hydroxide is added in 5 times every 30 minutes, followed by reaction at 5 ° C. After 2.5 hours, 3 parts of toluene was added, and the resulting salt was removed by filtration, washed with 270 parts of ion-exchanged water and separated, and then epigas alcohol was distilled off and dissolved in methyl isobutyl ketone. After mixing, stir at 80 C, and add 12 5% sodium hydroxide water: 96 parts, and carry out a purification reaction for 15 hours. Then, wash the ionic water with _ part of the ion father and separate the liquid. Then use After neutralizing with phosphoric acid, washing with water and removing θ2, washing with water and filtering, the oxime isobutyl group was distilled off to obtain 325 parts of the epoxy resin A of the present invention. The obtained epoxy resin A ^ 130083.doc 15 200911865 The viscosity at 250t is 200 mPa.s, the oxygen equivalent is 378 g/eq, and the hydrolyzable chlorine is 0.02%. From the GPC measurement, it can be seen that n = steroid is 16% of body and other components. Resin A, its infrared optical error diagram is shown in Figure 1 'GPC plot is suitable for Figure 2. Example 2 and Comparative Examples 1, 2 as epoxy resin The epoxy resin A, YD-171 (polymer polyglycidol g resin, epoxy equivalent denier (four), viscosity at 25 ° C of 740 mPa.s, hydrolyzable gas Q51%) was used in the examples. , Dongdu Chemical Co., Ltd.), Yang-207S (polypropylene glycol diglycidyl squid 'epoxy equivalent η] g/eq, viscosity at 25 ° C is 44 mPa.s, hydrolyzable chloranil 5%, Dongdu Chemical Company System), as a hardener's system using Likasid MH7 〇〇 (methyl hexahydroausteric anhydride, acid if equivalent 168 g / eq, 胄 Japan physicochemical system), as a hardening accelerator 'system using Hexicolin PX_4ET (Organic scale salt compound, manufactured by 曰本化学), the epoxy resin composition is obtained by the compounding method shown in Table i. Further, the numerical values in the table refer to the parts by weight when compounded. The composition was molded at 10 (TC for 2 hours, and then hardened after (1) hours to obtain a cured test piece for various physical properties. The results were suitable for Table 2. Further, test methods and evaluation of hardened physical properties. The system is as follows: (1) (IV) Expansion coefficient U is measured by thermomechanical measurement of the heating rate of the segment It is obtained by a displacement of 50 ° C to 100 ° C. (10)", using a test piece with a diameter of 5 and a thickness of 2, and a weight change rate after 50 hours of moisture absorption under the conditions of Μ and RH. 130083.doc •16- 200911865 (3) Ionic impurity mass, which is obtained by extracting ion fraction after 105 °C and 20-hour pressure cooker test, and determining its gas ion, sodium ion and potassium by ion chromatography. The ion was obtained by conversion into a solid fraction. (4) The amount of elongation was measured in a dumbbell-shaped No. 6 test piece according to JIS K-6251. (5) Viscosity, the presence or absence of stickiness is confirmed by finger touch hardening. Table 1 Example 1 Comparative Example 1 Comparative Example 2 Epoxy Resin A 100 • YD-171 - 100 _ PG-207S - 100 Hardener 90 90 90 Hardening Accelerator 0.5 0.5 0.5 Table 2 Example 2 Comparative Example 1 Comparative Example 2 Linear thermal expansion coefficient (ppm/°C) 203 206 115 Water absorption (°/〇) 0.5 0.3 3.1 Ionic impurity (ppm) Gas ion nano ion Calcium ion 10 0.1 or less 0.1 or less 600 0.1 0.1 or less 0.1 or less 300 0.2 0.1 or less Amount (%) 125 48 38 Viscosity is not the same as in Comparative Example 1, the epoxy resin used has more than 0.51% and 0.2% hydrolyzable chlorine, so the chloride ion of the cured product is 600 ppm, which is in comparison with the examples. More to 60 times. This fact shows that electrical insulation is not reliable. Also, the elongation of 48% is only about half of the embodiment. Further, 130083.doc 17 200911865 used in Comparative Example 2 is an aliphatic alcohol having no unsaturated bond, and the elongation is as low as π%, which is only about 1/3 of the embodiment, and is carried out. In comparison with the extensibility, the water absorption rate of Comparative Example 2 was as high as 31%, and the water absorption was too high as compared with the examples, which was not preferable. Industrial Applicability The epoxy resin of the present invention is excellent in low viscosity and can obtain a cured product having a low elastic modulus and a high elongation property. Therefore, it is possible to produce a cured product having excellent heat resistance in a wide range of use and having excellent elasticity and thirst resistance, and a package or coating for an electric-electronic component such as a semiconductor element can be obtained. A useful resin composition such as a material, a laminate material, or a composite material is technically significant. [Simple diagram of the diagram] The vertical axis table transmittance in the figure, the vertical table standard polyethylene in the horizontal view. Figure 1 is the IR spectrum of the epoxy resin A. Fig. 2 is a GPC curve of epoxy resin A. Molecular weight conversion, horizontal axis dissolution time 130083.doc -18-