201130878 六、發明說明： 【發明所屬之技術領域】 本發明係關於要求難燃性之環氧樹脂組成物的發明， 係有用於作為電子電路基板所用之覆銅積層板製造用之樹 脂組成物或電子零件所用之密封材、成形材、鑄模材、接 著劑、電絕緣塗料等，尤其關於作為覆銅積層板製造用之 樹脂組成物時不僅具有難燃效果，且亦可提供密著性、耐 熱性及对濕性優異之積層板的難燃性含填環氧樹脂組成 物。 【先前技術】 實際利用環氧樹脂之型態係例如有液狀至固形狀、溶 解於溶劑之清漆（varnish)狀等。液狀類型係廣泛利用於鑄 模材料和接著劑用途等，固形類型係利用於密封材和粉體 塗料等。此外，清漆類型係利用於含浸在玻璃基材和碳纖 維等而使用之纖維補強塑膠材料和溶劑型塗料。尤其因其 優異之密著性、電氣特性（絕緣性）而廣泛使用於電氣電子 材料零件。 由於此等電氣電子材料零件係如玻璃環氧積層板或1C 密封材所代表般要求高之難燃性（UL: V-0)，故通常是使用 經鹵化之環氧樹脂。例如，在玻璃環氧積層板中，經難燃 化之FR-4等級者一般係以經溴取代之環氧樹脂作為主原 料成分，並對其調配混合各種環氧樹脂而成之環氧樹脂與 環氧樹脂用硬化劑而使用。 然而，使用此等經鹵化之環氧樹脂，不但成為近年來 4 321863 201130878 會心境問題之-大要因’且在高溫環境下 強烈要求減少南辛之：二期可靠性造成不良影響’因此， 齒辛之I: 使用量、或是希望研發出使用可替代 =合物的難燃劑或其他難燃處方。 p . 7就替代此等齒素之難燃處方的技術而言， 之枯输，種例如使用嶙動m合物等作為添加系難燃劑 1’但此等技術皆導致積層板 之耐熱性和耐水性等之 =，丨會隨著時間而溢出（bleed〇ut)之問題，尤其 使产羞抖層板用途之㈣性會急劇降低。於是，檢討各種 枯二直3 ^與特定之魏合物反應而提升積層板之性能的 技術（專利文獻彳 3 主°然而’此等技術皆就耐熱性而言 為極限，難以提升至其以上之_熱性。-般 、k升耐熱性，係採取多使用曱盼紛搭（1 :〇volac)%氧樹脂等多宫能環氧樹脂之方法 ，但會招致難 =生降，和接著性降低。最近，為了對應無錯焊接，由於 ^提升&溫時之可靠性而要求硬化物之吸水率下降和 低彈f生化等 在專利文獻5中雖藉由使具有萘芳烧基結構 之環氧樹脂與特定之魏合物反應 而同時達成難燃性與耐 ^ &升仁仍招致接著性降低。如此，難以一邊藉由 3 Θ環氧;MJ旨組成物來保持難燃性，—邊提升耐熱性並同 時確保接著性。 [先前技術文獻] [專利文獻] [專利文獻1]日本特開2001-288247號公報 5 321863 201130878 [專利文獻2] [專利文獻3] [專利文獻4] [專利文獻5] [專利文獻6] 日本特開2002-249540號公報 日本特開2001-123049號公報 日本專利第3642403號公報 日本特開2008-214513號公報 日本特開昭61-268691號公報 【發明内容】 (發明欲解決之課題） 本發明欲解決之課題係提供一種耐熱性、耐濕性、難 燃性優異之難燃性含磷環氧樹脂組成物，其係在不使用鹵 素即賦予難燃性之含磷環氧樹脂中，因提高高溫時之可靠 性，而不會招致接著性降低者。 (解決課題之方法） 亦即，本發明之要旨係一種難燃性含磷環氧樹脂組成 物，其係含有含磷環氧樹脂（X)與硬化劑（Y)的難燃性含磷 環氧樹脂組成物，其中，前述含磷環氧樹脂（X)係藉由使含 有80重量％至100重量％之具有萘骨架之2官能環氧樹脂 類的環氧樹脂類（a)、與相對於化學式（1)1莫耳以化學式 (2)0. 06莫耳以下之比率混合的磷化合物類（b)進行反應而 得者，並且，該難燃性含磷環氧樹脂組成物中，相對於全 部環氧樹脂成分之含磷率為〇. 5重量％至未達2. 0重量％。 6 321863 (1)201130878[Technical Field] The present invention relates to a resin composition for producing a flame-retardant epoxy resin composition, and a resin composition for producing a copper-clad laminate used for an electronic circuit board or A sealing material, a molding material, a molding material, an adhesive, an electrical insulating coating, and the like used for an electronic component, in particular, not only have a flame retardant effect as a resin composition for manufacturing a copper clad laminate, but also provide adhesion and heat resistance. The flame retardant inclusion of an epoxy resin composition of a laminate which is excellent in properties and wetness. [Prior Art] The type of epoxy resin actually used is, for example, a liquid to solid shape, a varnish dissolved in a solvent, or the like. The liquid type is widely used for molding materials and adhesives, and the solid type is used for sealing materials and powder coatings. In addition, the varnish type is used for fiber-reinforced plastic materials and solvent-based coatings which are impregnated on glass substrates and carbon fibers. In particular, it is widely used in electrical and electronic materials because of its excellent adhesion and electrical properties (insulation). Halogenated epoxy resins are commonly used because such electrical and electronic material parts are highly flame-retardant (UL: V-0) as represented by glass epoxy laminates or 1C sealants. For example, in a glass epoxy laminate, the flame-retarded FR-4 grade is generally made of a bromine-substituted epoxy resin as a main raw material component, and an epoxy resin obtained by mixing various epoxy resins. It is used together with a hardener for epoxy resins. However, the use of such halogenated epoxy resins has not only become a major cause of concern in recent years 4 321863 201130878, but also strongly requires the reduction of Nanxin in high temperature environments: the second phase of reliability causes adverse effects. Xin Zhi I: The amount of use, or the desire to develop a flame retardant or other flame retardant prescription using an alternative compound. p. 7 In the technique of replacing the flame retardant prescription of these fangs, for example, the use of a turbulent m compound or the like as an additive flame retardant 1', but these techniques lead to heat resistance of the laminate. And water resistance, etc., 丨 will bleed over time (bleed〇ut), especially the use of shyness slabs (4) will be dramatically reduced. Therefore, reviewing various techniques for improving the performance of laminates by reacting with a specific compound (Patent Document 彳3 main) However, these technologies are extreme in terms of heat resistance, and it is difficult to raise them above. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ In recent years, in order to cope with the error-free soldering, it is required to reduce the water absorption rate of the cured product and the low-elasticity of the biochemicals due to the reliability of the temperature rise and the temperature, and the like, in the patent document 5, by having a naphthalene-based structure. Epoxy resin reacts with a specific fare to achieve both flame retardancy and resistance, and the adhesion is still reduced. Thus, it is difficult to maintain flame retardancy by using a 3 Θ epoxy; MJ composition. - [Patent Document 1] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2001-288247 5 321863 201130878 [Patent Document 2] [Patent Document 3] [Patent Document 4] [Patent Document 5] [Patent Document 6] Japanese Special Open 20 Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The problem to be solved is to provide a flame-retardant phosphorus-containing epoxy resin composition excellent in heat resistance, moisture resistance, and flame retardancy, which is improved in a phosphorus-containing epoxy resin which imparts flame retardancy without using a halogen. The reliability at high temperature is not caused by the decrease in adhesion. (Method for solving the problem) That is, the present invention is directed to a flame-retardant phosphorus-containing epoxy resin composition containing a phosphorus-containing epoxy resin ( X) a flame-retardant phosphorus-containing epoxy resin composition with a hardener (Y), wherein the phosphorus-containing epoxy resin (X) is obtained by containing 80% by weight to 100% by weight of a 2-functional group having a naphthalene skeleton The epoxy resin-based epoxy resin (a) is reacted with a phosphorus compound (b) mixed with a chemical formula (1) 1 molar at a ratio of the chemical formula (2) 0.06 mol or less, And, the flame retardant phosphorus-containing epoxy resin composition, phase The phosphorus content of the whole epoxy resin component is 〇. 5 wt% to less than 2.0 wt%. 6 321863 (1) 201130878
(2) (發明之效果） 若使用本發明之環氧樹脂組成物，則獲得難燃性、接 著力、耐熱性、耐濕性皆優異且線膨脹係數低之硬化物。 並可獲得含磷率為0.5重量％至未達2. 〇重量％之難燃性 且高耐熱性與低吸水率之硬化物。 【實施方式】 以下，針對本發明之實施型態而詳細說明。本發明所 使用之環氧樹脂類（a)係含有8〇重量％至剛重量％之具 有萘骨架之2官能環氧樹脂類作為必須成分。 具有萘骨架之2官能環氧樹月旨類可列舉如腦雙τ〇 zx-腿（東都化成股份公㈣，丨，4m環氧樹脂）、 EP0T0HTGZX-171K東都化成股份公司製，2 5_萃二醇㈣ 氧樹脂）等，但不限定於此等，又亦可併用2種以上。 又，2官能環氧樹脂類必須具有蔡骨架。若為不且有 萘骨架之2官能環氧樹脂_無法圖謀提升義性，且合 321863 7 201130878 招致難燃性降低，而無法獲得可在古 在円耐熱用途使用之組成 物。 此外，具有蔡骨架之2官能環盖姓 衣氣樹脂類必須為環氧樹 脂類（a)中之80重量％以上。若夫违如‘ 右禾違80重量％則會急劇降 低接著性，而僅獲得缺乏實用性之組成物。 雖然若使用80重量％以上的具有蔡骨架之2官能環氧 樹脂類’即可充分滿足耐触和接著性，但為了圖謀更進 一步提升難燃性和耐熱性，亦可在未達2〇重量％之範圍含 有具有萘㈣之2官能環氧.樹脂料的縣樹賴，從難 燃性之觀點來看係以脂肪族系環氧樹脂為不佳，從耐熱性 之觀點來看係以平均官能基數目為2.1以上之多官能環氧 樹脂類為佳。 平均官能基數目為2. 1以上之多官能環氧樹脂類可列 舉如酚酚醛（phenol novolac)型環氧樹脂、曱酚驗醛型環 氧樹脂、^•烧基型環氧樹脂等。具體例可列舉如ΕροτΟΗΤΟ YDPN-638(東都化成股份公司製，酚酚醛型環氧樹脂）、 ΕΡ0Τ0ΗΤ0 YDCN-701 ' ΕΡ0Τ0ΗΤ0 YDCN-702 ' ΕΡ0Τ0ΗΤ0 YDCN-703、ΕΡ0Τ0ΗΤ0 YDCN-704(東都化成股份公司製，鄰 曱酚酚醛型環氧樹脂）、ΕΡ0Τ0ΗΤ0 ESN-175C東都化成股份 公司製，冷-萘醇芳烷基型環氧樹脂）、ΕΡ0Τ0ΗΤ0 ESN-475V、EP0T0HT0 ESN-485C東都化成股份公司製，α-萘醇芳烷基型環氧樹脂）、ΕΡ0Τ0ΗΤ0 ESN-375C東都化成股 份公司製’二萘醇芳烷基型環氧樹脂）、ΕΡΡΝ-501Η、 EPPN-502C曰本化藥股份公司製，3官能環氧樹脂）、 8 321863 201130878 nc-3_(日本化藥股份公司製，聯笨芳絲型環氧樹 等，但不限定於此等，又亦可併用2種以上。此等中^(2) (Effects of the Invention) When the epoxy resin composition of the present invention is used, a cured product excellent in flame retardancy, adhesion, heat resistance, and moisture resistance and having a low coefficient of linear expansion is obtained. Further, a cured product having a phosphorus-containing ratio of 0.5% by weight to less than 2.% by weight of flame retardancy and high heat resistance and low water absorption can be obtained. [Embodiment] Hereinafter, the embodiment of the present invention will be described in detail. The epoxy resin (a) used in the present invention contains, as an essential component, a bismuth epoxy resin having a naphthalene skeleton of from 8 to 5% by weight. The bifunctional epoxy tree having a naphthalene skeleton can be exemplified by a brain double τ〇zx-leg (Dongdu Huacheng Co., Ltd. (four), 丨, 4m epoxy resin), EP0T0HTGZX-171K Dongdu Chemical Co., Ltd., 2 5_ The diol (tetra) oxy-resin or the like is not limited thereto, and two or more kinds thereof may be used in combination. Further, the bifunctional epoxy resin must have a Cai skeleton. If it is a 2-functional epoxy resin which does not have a naphthalene skeleton, it cannot be improved, and 321863 7 201130878 causes a decrease in flame retardancy, and it is impossible to obtain a composition which can be used in ancient heat-resistant applications. Further, the 2-functional ring-capped surname resin having a Cai skeleton must be 80% by weight or more of the epoxy resin (a). If he does not violate the 80% by weight of the right-wing, it will drastically reduce the adhesion, and only obtain the composition that lacks practicality. Although 80% by weight or more of a bifunctional epoxy resin having a Cai skeleton can be used to sufficiently satisfy the contact resistance and adhesion, in order to further improve the flame retardancy and heat resistance, it may be less than 2 parts by weight. In the range of %, the county-based bismuth resin containing a naphthalene (tetra) epoxy resin material is not preferred from the viewpoint of flame retardancy, and is based on heat resistance. A polyfunctional epoxy resin having a functional group number of 2.1 or more is preferred. The polyfunctional epoxy resin having an average number of functional groups of 2.1 or more may be exemplified by a phenol novolac type epoxy resin, a nonylphenol type aldehyde type epoxy resin, or a calcined type epoxy resin. Specific examples include ΕροτΟΗΤΟ YDPN-638 (made by Dongdu Chemical Co., Ltd., phenol novolac type epoxy resin), ΕΡ0Τ0ΗΤ0 YDCN-701 'ΕΡ0Τ0ΗΤ0 YDCN-702 'ΕΡ0Τ0ΗΤ0 YDCN-703, ΕΡ0Τ0ΗΤ0 YDCN-704 (made by Dongdu Chemical Co., Ltd.) O-nonphenol phenolic epoxy resin), ΕΡ0Τ0ΗΤ0 ESN-175C Dongdu Chemical Co., Ltd., cold-naphthyl alcohol aralkyl epoxy resin), ΕΡ0Τ0ΗΤ0 ESN-475V, EP0T0HT0 ESN-485C Dongdu Chemical Co., Ltd., α- Naphthyl aralkyl type epoxy resin), ΕΡ0Τ0ΗΤ0 ESN-375C Dongdu Chemical Co., Ltd.'s 'naphthyl alcohol aralkyl type epoxy resin', ΕΡΡΝ-501Η, EPPN-502C 曰本化制药股份有限公司, 3 functional Epoxy resin), 8 321863 201130878 nc-3_ (made by Nippon Kasei Co., Ltd., but not limited to this, but it is also possible to use two or more types together.
以不具有取代基之朌祕㈣氧樹脂或萘醇芳絲 L 樹脂為更佳。 < 在專利文獻1中，雖然揭示由最多含有45重量 有萘骨架之2官能環氧_的環氧樹脂所獲得的含备、 樹脂，但由於其為未達75重量％，而使八1 專利文獻5巾絲赫轉料絲_氧如旨所^ 含磷環氧樹脂，但由於未使用具有萘骨架之2a的 脂類，故即使料錄充分，其接著性卻㈣氣樹 本發明所用之磷化合物類（b)必須為相對於化 所示化合物i莫耳二化學式⑵所示化合物“6子料以) 下之比率'/¾合的鱗化合物類。It is more preferable to use an oxy resin or a naphthol aryl L resin which does not have a substituent. < Patent Document 1 discloses a preparation and a resin obtained from an epoxy resin having a maximum of 45 parts by weight of a bifunctional epoxy group having a naphthalene skeleton, but since it is less than 75% by weight, Patent Document 5 丝丝赫转丝丝_氧如为^ Phosphorus-containing epoxy resin, but since the lipid having the naphthalene skeleton 2a is not used, even if the material is sufficient, the adhesion is (4) gas tree used in the present invention. The phosphorus compound (b) must be a scaly compound having a ratio of '/3' to the compound "6 substrate" represented by the chemical formula (2).
1) (2) 321863 9 2011308781) (2) 321863 9 201130878
Dihydro-9-oxa-10-ph〇wSphaphenanthrene-10-〇xide)與作 為醌類之1，4-萘醌的反應而獲得的磷化合物。 就磷化合物類（b)而言，可將預先合成之化學式（1)所 示化合物與化學式（2)所示化合物混合而使用，亦可在與環 氧樹脂類（a)反應前，使化學式（2)所示化合物與1，4-萘 醌’以相對於化學式（2)所示化合物1莫耳為〇. 94莫耳至 1.00莫耳之1,4-萘醌與進行反應。當在與環氧樹脂類（a) 反應前使化學式（2)所示化合物與1，4-萘醌反應時，相對 於化學式（2)所示化合物1莫耳，若使用丨.〇〇莫耳以上之 1’ 4-萘酿’則所得之含填環氧樹脂（X)中會殘存原料之1，4_ 萘醌’而使硬化物之耐濕性惡化，故較不佳。 當化學式（2)所示化合物超過〇.〇6莫耳時，由於容易 =整s磷率，故對於提升難燃性和降低黏度為有效果，但 多=生1官能之化學式（2)所示化合物與環氧基之反應，降 氏及氧基數目’而導致硬化物之接著性降低和财熱性降低 ^耐濕性降低’使高耐熱料之電絕緣可靠性明顯下降。 ^使用化學式⑵所示化合物時，必須預先製造化學式⑴ 於：：：：。該化合物之製造需要許多步驟，生產性不佳， 中，最終::二益广’在與環氧樹脂類⑹之反應 則所得之含磷成物中的含辦若設為高値， 升，而使與玻“之子量增大’樹脂黏度會過度上 不具利益，改性明㈣化，不僅在工業上成為 惡化，並且積層魏之物性，尤其是焊接耐熱性會 積層板之彈性模數（elasticmc)dulus)亦容易變 321863 10 201130878 高，不適於近年之低彈性化傾向。因此，相對於化學式（U 所示化合物1莫耳’化學式（2)所示化合物之莫耳比為〇 〇6 莫耳以下，較佳為〇. 〇1莫耳至〇. 〇5莫耳。 專利文獻4中，雖揭示由萘二醇型環氧樹脂所獲得之 含踏環氧樹脂，但未考慮到殘存之化學式（2)所示化合物， 於其實施例中由於是以1 : 0. 92莫耳進行反應，故化學式 (2)所示化合物會殘存許多，因而使耐熱性不佳，高耐熱用 途之電絕緣可靠性明顯下降。 當本發明所用之環氧樹脂類（a)與磷化合物類反應 時，亦可使用磷化合物類（b)以外之2官能以上之酚化合物 類。2 g此以上之齡化合物類可列舉如雙齡a、雙紛ς、雙 酚F、萘二醇、聯酚（biphenol)、酚酚醛樹脂、甲酚酚醛 樹脂、乙二醛四酚樹脂、雙酚人酚醛樹脂、酚芳烷基樹脂、 萘醇芳烧基樹脂、聯酚芳烷基樹脂等。尤其是從難燃性之 觀點來看’以萘二醇或聯紛為特佳。使用2官能以上之盼 化合物類之目的’係為了在使環氧樹脂類⑷與填化合物類 ⑹反應時調整㈣率或軟化點或環氧當量，故軌合物類 (b)，、2目此以上之*化合物類的量的比例係依據含鱗環 氧樹脂⑴之含碟率或軟化點或環氧#量而適當變更。、 此外，本發明所用之環氧樹脂類（a)與鱗化合物類（b) 的反應可依公知方法進行，反應溫度為剛。〇至綱。c，更 佳為可在12〇。(：至18()ΐ中於轉下進行。反應時間可進行 環氧當量之測定而決定。該測定可依據服_7236之方法 測定。藉由環氧樹脂類（a)與環氧_旨與雜合物類⑻之 201130878 反應而使環氧當量變大，可依據與理論環氧當 決定反應終點。 較而 又，反應速度慢時，可視需要而使用觸媒以改盖生 性。具體而言，可使用节基二甲基胺等三級胺類、以 甲基銨等四級敍鹽類、三苯基膦、三（2,6一二 膦等膦類、漠化乙基三笨基鱗等鱗發、2_甲基心、2—土) 基-4-甲基咪唑等咪唑類等各種觸媒。 乙 本發明之難燃性含磷環氧樹脂級成物中 f氧樹脂成分之含磷率必須為0. 5重量％至未達..2 〇 匕若未達G. 5重量％則無法賦予充分之難燃性。若里 !量％以上，則會因含嶙環氧樹脂中之鱗成分之馬塑.〇 :硬化物之耐濕性降低，並使高耐熱用途之可靠二顯; 難燃性含财氧樹職錢巾 氣樹脂成分之含嶙率調整為。.5重^=字相對於全部環 的：要性’故相對於含嶙環氧樹脂二2·。重量％ 不含磷之環氧樹脂〇重量份至5〇重 4里份，可調配 份以上時，則必須提高含鱗環氧樹里刀。若調配50重量 損，在此情形下.，難燃性含鱗率以使難燃 ^生會大幅降低。從難燃性之觀組成物之耐 月曰係以脂肪族系環氧 ，不含磷之環氧樹 以平均宫能基數目2為不佳，從耐熱性之觀點來看， 且以前述環氧樹脂環氧樹_為佳， 以上之多宫能環氧樹基數目 3磷之環氧樹脂類 321863 12 201130878 時，若為50重量份以下，即可無損耐敎性 本發明之_性含_氧_組成物4 :、性而獲付 環氧樹脂⑴1G0重量份，該不含碟 =對於含鱗 至25重量份。 魏心為0重量份 本發明之含磷環氧樹脂（χ)之含磷 量％至3.5重量％之範圍内即可，會要；^〇.5重 旦0/W 、…去曰η 重量％至3.〇重 里/為佳，以1.2重以至2 7重量％為更佳 置％至2.3重量％為特佳。含辦若未達G· 會_確保難祕。若超過3. 5 .重量，則樹㈣=會明 顯變南而難以合成，且因樹脂之分子量增大，而對_性 造成不良影響，對於玻璃布之含浸性亦惡化，不僅在工業 上不具利益，所得積層板之物性，尤其是焊接耐熱性會惡 化。.此外，當未使用含磷環氧樹脂（χ)以外之環氣樹脂時二 含磷環氧樹脂（X)之含磷率必須為〇·5重量％至未達2 〇重 量％。 本發明之含磷環氧樹脂（χ)之環氧當量較佳為2〇〇g/eq 至600g/eq，更佳為23〇§/叫至55〇g/eq，特佳為 至500g/eq。當環氧當量未達2〇〇g/eq時，接著性不佳， 當超過600g/eq時’會對耐熱性造成不良影響，故以調整 成 200g/eq 至 6〇〇g/eq 為佳。 本發明之硬化劑（γ)可列舉如以酚酚醛樹脂為代表之 各種多70齡樹脂類或酸酐類、以雙氰胺（dicyandiamide) 為代表之私'類、酿肼（hydrazi de)類、酸性聚酯類等通常使 用之每氧樹脂用硬化劑，此等硬化劑可僅使用1種，亦可 13 321863 201130878 併用2種以上。 本發明之難燃性含磷環氧樹脂組成物可視需要而調酉己 三級胺、四級銨鹽、膦類、咪唑類等硬化促進劑。此外 亦可視需要而調配無機填充劑或是玻璃布、芳綸（afaini0 纖維等補強材、填充材、顏料等。 將使用本發明之難燃性含磷環氧樹脂組成物而獲彳| < 積層板之特性予以評估的結果，可獲得高耐熱性、低％ & 率、且高溫時之可靠性高的硬化物。可知該環氧樹脂l、 物及其硬化物係有用於作為電子電路基板所用之覆麵J積層 板之製造用樹脂組成物或電子零件所用之密封材、成^ 材、鑄模材、接著劑、薄膜材、電絕緣塗料用材料等。 (實施例） 以下，基於合成例、實施例及比較例而具體說明本於 明，但本發明之技術範圍不僅限於實施例。又，合成例 實施例及比較例中之各成分之調配份數只要未特別聲明， 即表示重量份。 又，本發明係使用以下之分析方法。 環氧當量.JIS K-7236記載之方法。亦即，將試料溶解於 氣仿10mL中’分別添加乙酸酐2〇乩、20%之 溴化四乙基銨乙酸溶液1〇mL，使用電位差滴定 裝置並以0.1m〇l/L過氣酸乙酸標準液進行滴 定。 軟化點.JIS K-7234記载之環球法。亦即，將試料予以熔 融脫泡並注入環中，於甘油浴測定。 14 321863 201130878 含碟率：；s肖酸-過氯酸分解法。亦即，將硫酸、硝酸、過氯 酸添加於試料並進行熱分解，使所有磷成為正磷 酸後，於硫酸酸性溶液中使0. 2 5 %飢酸敍溶液及 5%鉬酸敍溶液反應’所產生之碟-鈒鉬酸錯合物 之發色’係測定波長420nm時之吸光度，以校準 曲線求得含磷率。 銅箔剝離強度：JIS C-6481 5. 7記載之方法。亦即，在銅 箔與絕緣板之間，朝直角方向以5〇mm/分鐘 之速度進行剝離而測定。 層間剝離強度：以JIS C-6481 5. 7為準之方法。亦即，在 1片預浸片（prepreg)與其餘3片之間，朝 直角方向以50mm/分鐘之速度進行剝離而 測定。 難燃性·依據 ULQJnderwriters Laboratories)規格、UL94 垂直試驗法而進行測定，以作為同規格之判定基 準之V-0、V-卜V-2、NG(無難燃性）之4水準進行 判定（越為後者，難燃性越差）。 玻璃轉移溫度：TMA法。亦即，使用SII NanoTechnology 股份公司製之TMA/SS120U作為分析裝置， 依據熱機械分析（TMA)以10t/分鐘之升溫 速度進行測定。 線熱膨服係激.TM A、+ 尔默· 1MA 法。亦即，使用 SII NanoTechnology 股份公司製之TMA/SS120U作為分析裝置， 依據熱機械分析（TMA)以1(TC/分鐘之升溫 15 321863 201130878 速度進行測定而求得之從5(TC至150°C之 位移。 吸水率：以JIS C-648]. 5. 13為準之方法。亦即，使用已 裁切為50mmx50m丨η之試驗片，測定於5〇°C之烘箱 中乾燥24小時後之乾燥重量，繼而測定在經調整 為85°C/85%RH之處理槽内保管12〇小時後之重 量，並基於從乾燥重量增加之份量測定吸濕率。 焊接耐熱性：以JIS C-6481 5. 5為準之方法。亦即，使用 已裁切為25mmx25mm之試驗片，將於l〇〇°C 煮沸2小時後之試驗片以n = 5而浸於288°C 之焊浴中20秒，當5片皆未發生膨脹和剝離 時為〇，即使僅有1片發生該等現象時亦為 X 〇 合成例1 在備有攪拌裝置、溫度計、冷卻管、氮氣導入裝置的 4 口玻螭製可分離式燒瓶中’饋入作為化學式（2)所示磷化 合物之HCA(三光股份公司製，含磷率：14. 2重量％)64. 與甲笨150g，一邊於氮氣環境下攪拌，一邊加熱使完全溶 解。然後，一邊注意因反應熱所致之升溫，一邊分次投入 作為醌類之1，4-萘醌（川崎化成工業股份公司製，3%含水 品）45. 9g。此時之1,4-萘醌與HCA之莫耳比為1,4-萘醌/ HCA=〇. 95。加熱反應後，饋入作為具有萘骨架之2官能環 氧樹脂的£?01'0訂0 2)【-1711(東都化成股份公司製，2,5-萘二醇型環氧樹脂，環氧當量：146g/eq)317. lg、以及作 16 321863 201130878 為平均官能基數目為2. 1以上之多官能環氧樹脂的 ΕΡ0Τ0ΗΤ0 YDPN-638(東都化成股份公司製，酿驗搭型環氧 樹脂，環氧當量：176g/eq)74. 4g，一邊導入氮氣一邊進行 攪拌，加熱至13 0 °C並將甲笨去除至系統外。然後，添加 作為觸媒之三苯基膦（北興化學工業股份公司製，製品名： TPP)0.11g’ 一邊使反應溫度保持於16〇。^至165°C—邊反 應4小時，獲得含磷環氧樹脂a。所得之含磷環氧樹脂A 之環氧當量為260g/eq ’含磷率為1. 8重量％ ’軟化點為 73t。 合成例2 在備有攪拌裝置、溫度計、冷卻管、氮氣導入裝置的 4 口玻璃製可分離式燒瓶中，饋入作為化學式（2)所示磷化 合物之HCA(如前述）64.0g與甲苯I50g，一邊於氮氣環境 下授拌’ 一邊加熱使完全溶解。然後，一邊注意因反應熱 所致之升湓，一邊分次投入作為醌類之丨，4-萘醌（如前 述）47. 3g。此時之ι，4-萘醌與HCA之莫耳比為1，4-萘醌 /HCA = 0. 98。加熱反應後，饋入作為具有萘骨架之2官能 環氧樹脂的ΕΡ0Τ0ΗΤ0 ZX-1711(如前述）395. Og，一邊導入 氮氣一邊進行攪拌，加熱至130°C並將甲苯去除至系統外。 *、、:後’添加作為觸媒之二本基鱗（如前述）Q. Hg，.__邊使反 應溫度保持於16(TC至1651 —邊反應4小時，獲得含磷環 氧樹脂β。所得之含磷環氧樹脂B之環氧當量為251g/eq， 含磷率為1. 8重量％，軟化點為76°C。 合成例3 17 321863 201130878 在備有麟裝置、溫度計、冷卻管、氮氣導入裝置的 4 口玻璃製可分離式燒瓶中，饋入作為化學式（2)所示磷化 合物之HCA(如前述）30. 〇g與甲笨7〇g，一邊於氮氣環境下 龄’ -邊加熱使完全溶解。然後，一邊注意因反應熱所 致之升溫，一邊分次投入作為醌類之丨，4_萘醌（如前述） 22. lg。此時之1,4-萘醌與HCA之莫耳比為丨，4_萘醌/HCA =〇· 98。加熱反應後，饋入作為具有萘骨架之2官能環氧 樹脂的ΕΡ0Τ0ΗΤ0 ZX-1711 (如前述）35〇. 〇g與作為平均官能 基數目為2. 1以上之多官能環氧樹脂的Ep〇T〇HT〇 esn_485 (東都化成股份公司製，α—萘醇芳烷基型環氧樹脂，環氧 當量：269g/eq)82. lg，一邊導入氮氣一邊進行攪拌，加熱 至130 C並將曱笨去除至系統外。然後，添加作為觸媒之 二苯基膦（如則述）〇. 〇5g，一邊使反應溫度保持於16〇。〇至 165°C —邊反應4小時，獲得含磷環氧樹脂c。所得之含磷 環氧樹脂C之環氧當量為215g/eq，含磷率為〇.8重量％， 軟化點為66°C。 合成例4 在備有攪拌裝置、溫度計、冷卻管、氮氣導入裝置的 4 口玻璃製可分離式燒瓶中，饋入作為化學式（2)所示磷化 合物之HCA(如前述）75. Og與甲笨i75g，一邊於氮氣環境 下攪拌，一邊加熱使完全溶解。然後，一邊注意因反應熱 所致之升溫，一邊分次投入作為醌類之i，4-萘醌（如前 述）55. 9g。此時之1,4-萘醌與HCA之莫耳比為1，4-萘醌 /HCA=0. 99。加熱反應後，饋入作為具有萘骨架之2官能 18 321863 201130878 環氧樹脂的EP0T0HT0ZX-171K如前述）339. 5g與作為2官 能以上之酚化合物的4, 4,-聯酚（新日鐵化學股份公司势， 羥基當量：93g/eq)18. Og’ 一邊導入氮氣一邊進行擾掉， 加熱至13(TC並將曱苯去除至系統外。然後，添加^為觸 媒之二苯基膦（如前述）〇.15g’ 一邊使反應溫度保持於“ο °〇至165°C —邊反應4小時，獲得含磷環氧樹脂所得之 含磷環氧樹脂D之環氧當量為353g/eq，含鱗率為2 i重 量％，軟化點為l〇〇°C。 合成何' 5 在備有攪拌裝置、溫度計、冷卻管、氮氣導入裝置的 4 口玻璃製可分離式燒瓶中，饋入作為具有萘骨架之2官 能環氧樹脂的ΕΡ0Τ0ΗΤ0 ZX-171K如前述）337.2g、作為平 均官能基數目為2_1以上之多官能環氧樹脂的Ep〇T〇HT〇 ESN-485(如前述）17.7g、作為化學式（1)所示磷化合物之 9,10氫9氧雜-10-(2, 7-二經基萘基）-i〇_磷雜菲_ι〇_ 氧化物（依專利文獻6記載之方法所預先合成者，以下簡稱 f HCA-Nq)159 8g、作為化學式⑵所示璘化合物之脳（如 前t)2. 7§，—邊於氮氣環境下授拌，一邊加熱至130°C。 此時，相對於化學式⑴所示碟化合物 然後，添加作為觸媒之 1基 膦（如刖述）〇. 16g，一 i蠢蚀c + ^ G ^ ^ 使反應溫度保持於16(TC至165Ό ==當時量::：環氧樹η。所得之㈣環氧 化點為靴。 geq’含磷率為2.5重量％ ’軟 321863 19 201130878 合成例6 在備有授拌裝置、溫度計、冷卻管、氮氣導入裝置的 4 口玻螭製可分離式燒瓶中’饋入作為具有萘骨架之2官 能環氧樹脂的EP0T0HTC ZX-1711(如前述）400. 〇g、作為化 學式（1)所示磷化合物之HCA-NQ (如前述）62.〇g、以及作 為2官能以上之酚化合物的4, 4’ ~聯酚（如前述）4〇. 〇g，一 邊於氮氣環境下授拌，一邊加熱至13CTC。此時，不使用 化學式（2)所示磷化合物。然後，添加作為觸媒之三笨基膦 (如前述）0· ig’ 一邊使反應溫度保持於160°C至165。(： 一邊A phosphorus compound obtained by the reaction of Dihydro-9-oxa-10-ph〇wSphaphenanthrene-10-〇xide with 1,4-naphthoquinone as an anthracene. In the case of the phosphorus compound (b), the compound represented by the chemical formula (1) synthesized in advance may be used in combination with the compound represented by the chemical formula (2), or the chemical formula may be used before the reaction with the epoxy resin (a). (2) The compound shown and 1,4-naphthoquinone' are reacted with respect to the compound 1 shown in the formula (2), from 94 mol to 1.00 mol of 1,4-naphthoquinone. When the compound of the formula (2) is reacted with 1,4-naphthoquinone before the reaction with the epoxy resin (a), the compound 1 is not shown in the formula (2), and if 丨.〇〇莫 is used In the case of 1'4-naphthene above the ear, the 1,4-naphthoquinone which remains in the filled epoxy resin (X) is obtained, and the moisture resistance of the cured product is deteriorated, which is not preferable. When the compound of the formula (2) exceeds 〇.〇6 mol, it is effective for improving the flame retardancy and lowering the viscosity because of the easy = s phosphorus ratio, but more than the chemical formula (2) The reaction of the compound with the epoxy group, the number of the lowering and the number of the oxy group, results in a decrease in the adhesion of the cured product and a decrease in the heat resistance. The decrease in the moisture resistance makes the electrical insulation reliability of the high heat resistant material significantly lower. ^ When using the compound of the formula (2), the chemical formula (1) must be prepared in advance at ::::. The preparation of the compound requires a lot of steps, and the productivity is not good. In the end, the final content of the phosphorus-containing product obtained by the reaction with the epoxy resin (6) is set to sorghum and liter. If the amount of resin is increased, the viscosity of the resin will be excessively unprofitable, and the modification will not only deteriorate in the industry, but also the physical properties of the laminated layer, especially the elastic modulus of the laminated board (welding heat resistance). ) dulus) is also easy to change 321863 10 201130878 high, not suitable for the low elasticity tendency in recent years. Therefore, compared with the chemical formula (U shows the compound 1 Moer's formula (2), the molar ratio of the compound is 〇〇6 Mo Below the ear, it is preferably 〇. 〇1 mol to 〇. 〇5 mol. Patent Document 4 discloses a stepping epoxy resin obtained from a naphthalenediol type epoxy resin, but does not consider the remaining The compound of the formula (2) is reacted in a ratio of 1:0.9 mol in the examples, so that the compound represented by the formula (2) remains a lot, and thus the heat resistance is poor, and the heat resistance is high. Insulation reliability has dropped significantly. When the epoxy resin (a) to be used is reacted with a phosphorus compound, a phenol compound having two or more functional groups other than the phosphorus compound (b) may be used. 2 g of the compound of the above age may be, for example, a double age a. Double bismuth, bisphenol F, naphthalene diol, biphenol, phenolic phenolic resin, cresol novolac resin, glyoxal tetraphenol resin, bisphenol phenolic resin, phenol aralkyl resin, naphthol aromatic A base resin, a phenol aralkyl resin, etc., especially from the viewpoint of flame retardancy, 'preferably with naphthalene diol or a combination. The purpose of using a compound having two or more functional groups is to make an epoxy When the resin (4) is reacted with the compound (6), the (four) rate or the softening point or the epoxy equivalent is adjusted, so the ratio of the amount of the compound of the orbital compound (b), and the above 2 is based on the scaled epoxy resin. (1) The content of the epoxy resin (a) and the scaly compound (b) used in the present invention can be appropriately changed according to the content of the disk or the softening point or the amount of epoxy. The reaction temperature is just 〇至纲.c, more preferably at 12 〇. (: to 18 () ΐ in the middle of the turn. The time can be determined by measuring the epoxy equivalent. The measurement can be determined according to the method of the method of _7236. The epoxy equivalent is obtained by reacting the epoxy resin (a) with the epoxy resin and the 201130878 of the hybrid (8). When it becomes larger, it can be determined according to the theoretical epoxy. When the reaction rate is slow, the catalyst can be used as needed to change the bioavailability. Specifically, a tertiary amine such as a benzyl dimethylamine can be used. Classes, four grades of salt, such as methylammonium, triphenylphosphine, tris (phosphines such as 2,6-diphosphine, desertified ethyl three stupid scales, etc., 2-methyl heart, 2- 5重量%至未未。 The 5% of the phosphorus-containing resin composition of the composition of the present invention达..2 〇匕 If it does not reach G. 5 wt%, it cannot give sufficient flame retardancy. If the amount is more than %, it will be due to the scale of the enamel resin contained in the epoxy resin. 〇: the moisture resistance of the cured product is lowered, and the high heat-resistance is reliable; the flame retardant contains the oxygen tree The content of the resin component of the money towel is adjusted to be. The .5 weight ^= word is relative to all the rings: the nature is relative to the bismuth-containing epoxy resin. Weight % Phosphorus-free epoxy resin 〇 parts by weight to 5 4 4 parts, when the sizing is more than above, the scaly epoxy tree knives must be improved. If 50 weight loss is formulated, in this case, the flame retardant scaly rate will greatly reduce the flame retardancy. From the viewpoint of flame retardancy, the composition is resistant to aliphatic epoxide, and the epoxy-free epoxy tree has a poor average number of gongs of 2, from the viewpoint of heat resistance, and the aforementioned ring Oxygen resin epoxy tree _ is better, the above number of epoxy resin base number 3 phosphorus epoxy resin 321863 12 201130878, if it is 50 parts by weight or less, it can be non-destructive tolerant. _Oxygen_Composition 4: The epoxy resin (1) was added in an amount of 1 G0 by weight, which did not contain a dish = for scaly to 25 parts by weight. Wei Xin is 0 parts by weight of the phosphorus-containing epoxy resin (χ) of the present invention in the range of % to 3.5% by weight of the phosphorus, which may be required; ^ 〇. 5 heavy denier 0 / W, ... to 曰 η weight From 3% to 7% by weight, more preferably from 1.2% by weight to more than 2.3% by weight. If you don't have a G, you will be sure to be secret. If it exceeds 3.5 weight, the tree (4) = will become significantly south and difficult to synthesize, and the molecular weight of the resin will increase, which will adversely affect the _ property, and the impregnation of the glass cloth will also deteriorate, not only in the industry. Benefits, the physical properties of the resulting laminate, especially the weld heat resistance will deteriorate. Further, when the epoxy resin other than the phosphorus-containing epoxy resin (χ) is not used, the phosphorus content of the phosphorus-containing epoxy resin (X) must be from 5% by weight to less than 2% by weight. The epoxy equivalent of the phosphorus-containing epoxy resin of the present invention is preferably from 2 〇〇g/eq to 600 g/eq, more preferably from 23 〇 / to 55 〇 g / eq, particularly preferably up to 500 g / Eq. When the epoxy equivalent is less than 2〇〇g/eq, the adhesion is not good. When it exceeds 600g/eq, it will adversely affect the heat resistance, so it is better to adjust it to 200g/eq to 6〇〇g/eq. . The hardener (γ) of the present invention may be, for example, various 70-year-old resins or acid anhydrides represented by phenol novolac resins, and private catechus and hydrazides represented by dicyandiamide. A curing agent for each oxygen resin which is usually used, such as an acidic polyester, may be used alone or in combination of two or more kinds. The flame-retardant phosphorus-containing epoxy resin composition of the present invention may be used as a hardening accelerator such as a tertiary amine, a quaternary ammonium salt, a phosphine or an imidazole, as needed. In addition, an inorganic filler, glass cloth, aramid (afaini0 fiber, etc., filler, filler, etc.) may be blended as needed. The flame retardant phosphorus-containing epoxy resin composition of the present invention may be used to obtain 彳| < As a result of evaluation of the characteristics of the laminate, a cured product having high heat resistance, low % & ratio, and high reliability at high temperatures can be obtained. It is understood that the epoxy resin, the cured product and the cured product thereof are used as an electronic circuit. A sealing material, a material, a molding material, an adhesive, a film material, a material for an electrical insulating coating material, etc., which are used for the production of a resin J-layer laminate for use in a substrate, or a material for use in an electronic component. (Example) The present invention is not limited to the examples, but the technical scope of the present invention is not limited to the examples. Further, the number of blending components of the components in the synthesis examples and the comparative examples is not particularly indicated. Further, in the present invention, the following analysis method is used: Epoxy equivalent. The method described in JIS K-7236, that is, the sample is dissolved in 10 mL of a gas mixture, and acetic anhydride is added in an amount of 2%, 20%, respectively. 1 〇mL of tetraethylammonium bromide acetate solution, titrated with a potential difference titration device and 0.1 m〇l / L peracetic acid acetic acid standard solution. Softening point. The global method described in JIS K-7234. The sample was melted and defoamed and injected into a ring and measured in a glycerin bath. 14 321863 201130878 With a disk rate: s xiao acid-perchloric acid decomposition method, that is, sulfuric acid, nitric acid, perchloric acid was added to the sample and heat was applied. Decomposition, after all the phosphorus is made into orthophosphoric acid, in the acidic solution of sulfuric acid, the reaction of 0.2% of the sulphuric acid solution and the 5% molybdate solution The absorbance at a wavelength of 420 nm was measured, and the phosphorus content was determined by a calibration curve. Copper foil peeling strength: A method described in JIS C-6481 5. That is, between the copper foil and the insulating sheet, 5 朝 in a right angle direction. The peeling strength was measured at a speed of mm/min. Interlaminar peeling strength: A method based on JIS C-6481 5. 7. That is, between one prepreg and the remaining three sheets, in a right angle direction The peeling was measured at a speed of 50 mm/min. Flame retardancy according to ULQJnderwriters Laborato The ries) specification and the UL94 vertical test method are used to determine the V level, V-Bu V-2, and NG (non-flammable) level 4 of the same specification. The more the latter, the flame retardancy The worse). Glass transfer temperature: TMA method. Namely, TMA/SS120U manufactured by SII NanoTechnology Co., Ltd. was used as an analysis device, and the measurement was carried out at a heating rate of 10 t/min based on thermomechanical analysis (TMA). Line thermal expansion is stimulated by TM A, + ermer · 1MA method. That is, using TMA/SS120U manufactured by SII NanoTechnology Co., Ltd. as an analytical device, it is determined from thermodynamic analysis (TMA) at a rate of 1 (TC/min of 15 321863 201130878) from 5 (TC to 150 °C). Displacement: Water absorption rate: JIS C-648]. 5. 13 method, that is, using a test piece cut to 50 mm x 50 m 丨η, measured in an oven at 5 ° C for 24 hours. The dry weight was measured, and the weight after storage for 12 hours in a treatment tank adjusted to 85 ° C / 85% RH was measured, and the moisture absorption rate was measured based on the amount of increase from the dry weight. Solder heat resistance: JIS C-6481 5. The method of 5 is the same. That is, using the test piece which has been cut into 25mmx25mm, the test piece which will be boiled at l〇〇 °C for 2 hours is immersed in the solder bath of 288 °C with n = 5 20 In the second, when the five sheets are not expanded and peeled off, it is 〇, even if only one of the sheets occurs, it is X 〇 Synthesis Example 1 In the case of a stirring device, a thermometer, a cooling tube, and a nitrogen introducing device HCA (supplied as a phosphorus compound represented by chemical formula (2) in a separable flask Co., Ltd., phosphorus content: 14.2% by weight) 64. While stirring in a nitrogen atmosphere, it is heated to completely dissolve. Then, pay attention to the temperature rise due to the heat of reaction. 1,4-naphthoquinone (manufactured by Kawasaki Chemical Industry Co., Ltd., 3% hydrated product) 45. 9 g. The molar ratio of 1,4-naphthoquinone to HCA at this time is 1,4-naphthoquinone / HCA=〇. 95. After heating the reaction, it is fed as a 2-functional epoxy resin having a naphthalene skeleton. 0?01'0 Order 0 2) [-1711 (made by Dongdu Chemical Co., Ltd., 2,5-naphthalenediol type) Epoxy resin, epoxy equivalent: 146g/eq) 317. lg, and 16 321863 201130878 ΕΡ0Τ0ΗΤ0 YDPN-638 (manufactured by Dongdu Chemical Co., Ltd.), which is a polyfunctional epoxy resin having an average number of functional groups of 2.1 or more. The test epoxy resin, epoxy equivalent: 176 g / eq) 74. 4g, while introducing nitrogen gas, stirring, heating to 130 ° C and removing the stupid to the outside of the system. Then, adding triphenyl as a catalyst Base phosphine (manufactured by Beixing Chemical Industry Co., Ltd., product name: TPP) 0.11g' while maintaining the reaction temperature at 16 〇. ^ to 165 ° C The reaction was carried out for 4 hours to obtain a phosphorus-containing epoxy resin a. The epoxy equivalent of the obtained phosphorus-containing epoxy resin A was 260 g/eq. The phosphorus-containing ratio was 1.8% by weight. The softening point was 73 t. In a four-piece separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, 64.0 g of HCA (as described above) and toluene I50g of a phosphorus compound represented by the chemical formula (2) were fed while being in a nitrogen atmosphere. Mix underneath while heating to completely dissolve. Then, while taking care of the rise due to the heat of reaction, the 4-naphthoquinone (as described above) 47.3 g was added in several portions as a hydrazine. The molar ratio of iota, 4-naphthoquinone to HCA at this time was 1,4-naphthoquinone /HCA = 0.98. After the reaction was heated, 395. Og, which was a 2-functional epoxy resin having a naphthalene skeleton, was fed, and while stirring, nitrogen gas was introduced while stirring, and the mixture was heated to 130 ° C and the toluene was removed to the outside of the system. *, ,: After adding 'the base squama as a catalyst (as mentioned above) Q. Hg, .__ while maintaining the reaction temperature at 16 (TC to 1651 - side reaction for 4 hours, obtaining phosphorus-containing epoxy resin β The obtained phosphorus-containing epoxy resin B has an epoxy equivalent of 251 g/eq, a phosphorus content of 1.8% by weight, and a softening point of 76 ° C. Synthesis Example 3 17 321863 201130878 In the case of a lining device, a thermometer, and cooling In a four-piece glass separable flask of a tube and a nitrogen gas introduction device, HCA (as described above) which is a phosphorus compound represented by the chemical formula (2) is fed 30. 〇g and a stupid 7 〇g, while under a nitrogen atmosphere '-When it is heated, it is completely dissolved. Then, while paying attention to the temperature rise due to the heat of reaction, it is divided into hydrazines as a quinone, 4_naphthoquinone (as mentioned above) 22. lg. The molar ratio of hydrazine to HCA is 丨, 4_naphthoquinone/HCA = 〇·98. After heating, the ΕΡ0Τ0ΗΤ0 ZX-1711 (as mentioned above) which is a 2-functional epoxy resin having a naphthalene skeleton is fed. 35〇. g and Ep〇T〇HT〇esn_485 as a polyfunctional epoxy resin having an average number of functional groups of 2.1 or more (made by Dongdu Chemical Co., Ltd., α- Alcohol aralkyl type epoxy resin, epoxy equivalent: 269 g/eq) 82. lg, stirred while introducing nitrogen gas, heated to 130 C and removed to the outside of the system. Then, diphenyl as a catalyst was added. The phosphine (as described) 〇 5g, while maintaining the reaction temperature at 16 〇. 〇 to 165 ° C - while reacting for 4 hours, to obtain a phosphorus-containing epoxy resin c. The resulting phosphorus-containing epoxy resin C ring The oxygen equivalent was 215 g/eq, the phosphorus content was 8% by weight, and the softening point was 66 ° C. Synthesis Example 4 A 4-piece glass separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device In the above, the HCA (as described above) of the phosphorus compound represented by the chemical formula (2) is 75. Og and 75 g of the thief i 75 g, and the mixture is heated under a nitrogen atmosphere to be completely dissolved. Then, attention is paid to the heat of reaction. The temperature was raised, and the i,4-naphthoquinone (as described above) was 55. 9 g. The molar ratio of 1,4-naphthoquinone to HCA was 1,4-naphthoquinone/HCA=0. 99. After heating the reaction, feed EP0T0HT0ZX-171K as a 2-functional 18 321863 201130878 epoxy resin with a naphthalene skeleton. 339. 5g and 4, 4,-biphenol which is a phenolic compound having a bifunctional or higher function (Nippon Steel Chemical Co., Ltd., hydroxyl equivalent: 93 g/eq) 18. Og' is disturbed while introducing nitrogen gas, heating To 13 (TC and remove the benzene to the outside of the system. Then, add ^ as the catalyst diphenyl phosphine (as mentioned above) 〇.15g' while maintaining the reaction temperature at "ο ° 〇 to 165 ° C - side reaction After 4 hours, the phosphorus-containing epoxy resin D obtained by obtaining the phosphorus-containing epoxy resin had an epoxy equivalent of 353 g/eq, a scaly ratio of 2 i% by weight, and a softening point of 10 °C. Synthesis of 5' In a 4-piece separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen introduction device, ΕΡ0Τ0ΗΤ0 ZX-171K as a 2-functional epoxy resin having a naphthalene skeleton was fed as described above. 337.2 g, Ep〇T〇HT〇ESN-485 (as described above) as a polyfunctional epoxy resin having an average number of functional groups of 2_1 or more, 17.7 g, and 9,10 hydrogen 9 oxa compound as a phosphorus compound represented by the chemical formula (1) -10-(2,7-di-p-naphthyl)-i〇_phosphaphenanthracene_oxide (pre-synthesized by the method described in Patent Document 6, hereinafter abbreviated as f HCA-Nq) 159 8g, As a hydrazine compound of the formula (2) (as in the previous t) 2. 7 §, - while stirring in a nitrogen atmosphere, it was heated to 130 °C. At this time, with respect to the dish compound represented by the chemical formula (1), a 1-phosphine (as described above) as a catalyst is added. 16 g, an i chopper c + ^ G ^ ^ The reaction temperature is maintained at 16 (TC to 165 Ό). ==At the time::: Epoxy tree η. The obtained (iv) epoxidation point is the shoe. The geq' phosphorus content is 2.5% by weight 'Soft 321863 19 201130878 Synthesis Example 6 With mixing device, thermometer, cooling tube, In a 4-port glass separable flask equipped with a nitrogen gas introduction device, EP0T0HTC ZX-1711 (as described above) is fed as a bifunctional epoxy resin having a naphthalene skeleton 400. 〇g, a phosphorus compound represented by the chemical formula (1) HCA-NQ (as described above) 62. 〇g, and 4, 4'-biphenol (as described above) as a bisphenol or a phenol compound of 4 or more, 4〇. 〇g, while being mixed under a nitrogen atmosphere, heated to 13 CTC. At this time, the phosphorus compound represented by the chemical formula (2) is not used. Then, the tris-phosphine (as described above) of 0·ig' as a catalyst is added while maintaining the reaction temperature at 160 ° C to 165.
反應4小時，獲得含鱗環氧樹脂F。所得之含碟環氧樹脂F 之環氧當量為269g/eq，含磷率為1〇重量％，軟化點為 96〇C。 合成例7 在備有搜拌裝置、溫度計、冷卻管、氮氣導入裝置的 口玻璃製可分離式燒瓶中，饋入作為化學式（2)所示磷化 合物之HCA(如前述）103. 6g與曱笨24〇g 下授拌’一邊加熱使完全溶解。然後， 所致之升溫，一邊分次投入作*贿μ i 240g，一邊於氮氣環境After reacting for 4 hours, a scaly epoxy resin F was obtained. The resulting dish-containing epoxy resin F had an epoxy equivalent of 269 g/eq, a phosphorus content of 1% by weight, and a softening point of 96 °C. 6克和曱 H 如 如 如 如 H H 103 103 103 103 103 103 103 103 103 103 103 103 103 103 103 103 103 103 103 103 103 103 103 103 103 103 103 103 103 103 103 103 103 103 103 103 103 103 103 103 103 103 103 Stupid 24 〇g will be mixed with 'heating to dissolve completely. Then, the temperature is increased, and it is put into a bribe μ i 240g in a nitrogen atmosphere.
C並將曱苯去除至系統外。然後， 邊進行攪拌，加熱至130 添加作為觸媒之三苯基 321863 20 201130878 膦（如前述）0.16g，一邊使反應溫度保持於至i65°C 一邊反應4小時，獲得含鱗環氧樹脂（j。所得之含填環氧 樹脂G之環氧當量為365g/eq ’含罐率為3 〇重量％，軟 化點為ll〇°C。 合成例8 在備有攪拌裝置、溫度計、冷卻管、氮氣導入裝置的 4 口玻璃製可分離式燒瓶中，饋入作為化學式（2)所示填化 合物之HCA(如前述）64.8g與曱苯15〇g，一邊於氮氣環境 下攪拌，一邊加熱使完全溶解。然後，.一邊注意因反應熱 所致之升溫，一邊分次投入作為醌類之丨，4_萘醌（如前述） 44. 5g。此時之ι，4-萘醌與HCA之莫耳比為丨，4-萘醌/HCA = 0.91。加熱反應後，饋入作為具有萘骨架之2官能環氧 樹脂的ΕΡ0Τ0ΗΤ0 ZX-171K如前述）i92.〇g、以及作為2官 能環氧樹脂的ΕΡ0Τ0ΗΤ0 YD-128C東都化成股份公司製，雙 酚A型環氧樹脂，環氧當量：187g/eq)192. 〇g，一邊導入 氮氣—邊進行攪拌，加熱至130。(：並將曱苯去除至系統外。 然後，添加作為觸媒之三苯基膦（如前述）〇. llg，一邊使反 應溫度保持於16(TC至165Ϊ —邊反應4小時，獲得含磷環 氧樹脂H。所得之含磷環氧樹脂H之環氧當量為288g/eq， 含磷率為I 9重量％，軟化點為7〇°c。 合成例9 在備有攪拌裝置、溫度計、冷卻管、氮氣導入裝置的 4 口玻璃製可分離式燒瓶中，饋入作為化學式（2)所示磷化 合物之HCA(如前述）70. Og與甲苯16〇g，一邊於氮氣環境 21 321863 201130878 下授拌’-邊加熱使完全溶解H —邊注意因反應熱 所致之升溫，-邊分次投入作為_之u_萘職（如前述） 46.4g。此時之1,4-萘親與HCA之莫耳比為u—蔡酿/隐 = 0.88。加熱反應後，饋入作為具有萘骨架之2官能環 樹脂的ΕΡ0Τ0ΗΤ0 ZX-1711(如前述）3〇〇g，一邊導入=氣一 邊進行授拌’加熱至130°C並將曱苯去除至系統外。然t， 添加作為觸媒之三苯基膦（如前述）〇. 12g，一邊使反應、田 保持於16忙至165°c -邊反應、4小時，獲得含碟環 i。所得之含磷環氧樹脂ϊ之環氧當量為3〇ι—: 為2. 4重量％，軟化點為96°C。 合成例10 官 以及作 0g，一 不使用 笨基 l9〇°c 在備有授拌裝置、溫度計、冷卻管、氮氣導 4口玻璃製可分離式燒瓶中，饋入作為具有萘骨架x勺 能環氧樹脂的ΕΡ0Τ0ΗΤ0 ZX-1711C如前述）281 〇g、、之 為化學式（1)所示填化合物之HCA-NQ (如前述）2= 〇 邊於氮氣環境下授拌，一邊加熱至13〇。此時 这 化學式（2)所示璘化合物。然後’添加作為觸媒之三〜 至 所得之含碟ja ^ 脂J之環氧當量為608g/eq，含磷率為3 5重曰〇长氧樹 點為14(TC。 ’軟化 實施例1至7及比較例1至4 依據表1所示之調配處方而調配含碟環氧樹 化劑（Y)、其他環氧樹脂、硬化促進劍莖 ” m 、硬 齊丨專。以甲基己基輞溶 (如前述）0. 21g，一邊使反應溫度保持於17〇七 本基膦 邊反應4小時，獲得含磷環氧樹脂j 321863 22 1 201130878 解含鱗環氧樹脂與其他環氧樹脂，並添加作為預先溶解於 乙一醇單甲謎（methyl cellosolve)及二曱基甲醯胺之硬 化劑（Y)的雙氰胺（DICY ’活性氫當量：21. Og/eq)、以及作 為硬化促進劑的2-乙基-4-甲基咪唑（四國化成股份公司 . 製’ 2E4MZ)，以使不揮發份成為50重量％之方式調製樹脂 清漆。然後，使用所得之樹脂清漆，含浸於基材之玻璃布（曰 東紡績股份公司製，WEA 116E 106S 136，厚度lOOym)， 將經含浸之玻璃布於150°C之熱風循環式烘箱乾燥8分 鐘’獲得預浸片。其次’將所得之預浸片4片與銅羯（三井 金屬礦業股份公司製’ 3EC-III，厚度35#111)重疊，以130 °Cxl5分鐘及170°Cx2.0MPax70分鐘之條件進行加熱與加 壓’獲得0.6mm厚之積層板。對於所得之各個積層板，進 行銅箔剝離強度、層間剝離強度、難燃性、破璃轉移溫度、 線熱膨脹係數、吸水率、焊接耐熱性之各物性之試驗。其 結果示於表2。 321863 23 201130878 r—lKl—-i 比較例4 1 100.0 1 1.73 1 o.zo 8 Ο 〇 ΙΟ « 比較例3丨 80.0 1 Ο 1 3.98 1 o.zo § f·— 0.14 S Oh 比較例2| 100.0 1 1 3.65 1 0.25 g 0.10 〇 Ok 比較例1 1 I 100.0 I 2.88 0.30 茬 0. 46 〇 Ο ci 實施例71 100.0 | 3.90 O.ZO 8 ο 〇 ο (D .婼 70.0 1 1 ΑΑ Λ 1 I OU. WJ Z CO 0.20 | 涅 I 0. 03 5 to 實施例5| 80.0 I ί 20* 0 j 3.67 0.30 | 8 0. 01 ιί> οι 實施例4 | 100.0 I 4.88 0. 29 0.02 ο 00 ο 實施例3 66.7 CO CO o 4.09 0.30 〇 0.02 s CM • 實施例2 1 80.0 | i 20.0 ί 4.54 0. 20 | o 0. 02 s 實施例1 1 100.0 I ! 4.04 0. SO 0. 05 ο 00 T— < <〇 S·^ 0D η 〇 /-Ν ♦ □ U) W U1 (D IL <0 σ η Φ X 0) φ /-s ο ί "3 YDPN-638 1 ESN—485 DICY ZE4MZ 听' Αβγ t «ϋαι 縣碱 ^ Ν ^ Ί bAL *ii V S气 要S 媒- J〇tJ ^QtJ ηΒτη η®η Ο 〇 « r-ffi ㊣蛘 ^C-φ1 敦* 組成物中之全部環氧樹脂之含磷率 (重量％) 含磷環氧 樹脂00 其他環氧樹脂 jD 硬化促進劑 i 24 321863 201130878 比較例4| eo oq Ο α> to 2 X 比較例3 CD τρ ΙΟ u> S X 比較例2 G> csl a> ο ζ 5 1— 〇0 CM r— α> X 比較例1 Csl 卜 o ? > ΙΟ u> eg X 實施例7 I Csl esi O) ? > u> CD u> u> u> o 實施例6 <D cu ο σ> <D τ—· 〇> CO CD o in 3 eg ο 00 <D Τ-» s u> o 實施例4 00 ι ΙΑ CD T-* C4 in 寸· o 實施例3 (D 〇· ? > in 卜 s 〇 實施例2 1 00 CD s 1£> o 實施例1 ? > 〇> C0 U) o 銅箔剝離 強度(kN/m) 層間剝離 強度(kN/m) 黎 Μ\\ m 玻璃轉移 溫度0*0 M 举 發d 漤3 |吸水率（％) 1 焊接耐熱性 跑I封 25 321863 201130878 實施例1至實施例5與比較例1至比較例3係使用在 與環氧樹脂（a)反應前先令化學式（2)所示化合物與1，4-萘 醌反應獲得之磷化合物類（b)並進行反應而獲得的含磷環 氧樹脂，實施例6係使用以預先合成之化學式（1)所示化合 物與化學式（2)所示化合物作為磷化合物類（b)而反應成的 含磷環氧樹脂，實施例7與比較例4係使用僅以預先合成 之化學式（1)所示填化合物而反應成的含填環氧樹脂。 比較例1在合成含鱗環氧樹脂時，由於僅使用66重量 %之具有萘骨架之2官能環氧樹脂類，且化學式（1):化學 式（2)之莫耳比為1 : 0.46，亦即使用多量化學式（2)之磷 化合物，故吸水率高達1.2%且耐濕性不佳，焊接耐熱性 亦不佳。此外，雖然多用多官能環氧樹脂，但其玻璃轉移 溫度為1551，耐熱性難謂高。層間剝離強度亦未達 1. OkN/m，而未成為具實用性之積層板。比較例2在合成含 磷環氧樹脂時，由於僅使用50重量％之具有萘骨架之2官 能環氧樹脂類，故即使含磷率未達2重量％仍不具有難燃 性，且耐熱性和耐濕性亦不佳。比較例3在合成含磷環氧 樹脂時，雖使用100重量％之具有萘骨架之2官能環氧樹 脂類，但由於化學式（1):化學式（2)之莫耳比為1 : 0. 14， 亦即使用多量化學式（2)化合物，故層間剝離強度未達 1. OkN/m，且耐熱性亦難謂為高。比較例4在合成含磷環氧 樹脂時，雖使用100重量％之具有萘骨架之2官能環氧樹 脂類，且未使用化學式（2)之磷化合物，但由於含磷率高達 3. 5重量％，故樹脂之軟化點高達140°C，使對於玻璃布之 26 321863 201130878 含浸性惡化，而使層間剝離強度未達1. OkN/m，焊接耐熱 性不佳。 相對於此，以相對於化學式（1)化合物1莫耳使化學式 (2)化合物成為0. 06莫耳以下並使用75重量％以上的具有 萘骨架之2官能環氧樹脂類而合成之含磷環氧樹脂作為必 * 須成分，並且環氧樹脂之含磷率為0. 5重量％至未達2. 0 ^ 重量％的實施例i至7係難燃性、接著力、耐熱性、耐濕 性皆優異。此外，如實施例4和實施例7所示，即使含鱗 率為1重量％以下亦可滿足難燃性，故可獲得耐濕性佳之 積層板。如實施例2、3、5、6所示，亦可併用不含填之環 氧樹脂，可獲得不但耐熱性高且同時接著力、難燃性亦優 異之環氧樹脂組成物。並且，若使用本發明之環氧樹脂組 成物，即獲得線膨脹係數低之積層板。 (產業上之可利用性） 本發明係最適合作為以電子電路基板所用之覆銅積層 板為首之電絕緣材料，亦適合作為電子零件所用之密封 材、成形材、鑄模材、接著劑、薄膜材，且亦有效於作為 電絕緣塗料用材料。 【圖式簡單說明】 無。 【主要元件符號說明】 無。 27 321863C and remove the benzene from the system. Then, while stirring, the mixture was heated to 130 to add 0.16 g of triphenyl 321863 20 201130878 phosphine (as described above) as a catalyst, and the reaction temperature was maintained at i65 ° C for 4 hours to obtain a scaly epoxy resin ( j. The epoxy equivalent of the obtained epoxy resin G is 365 g/eq', the pot content is 3 〇% by weight, and the softening point is ll 〇 ° C. Synthesis Example 8 A stirring device, a thermometer, a cooling tube, and the like are provided. In a four-neck separable flask equipped with a nitrogen gas introduction device, 64.8 g of HCA (as described above) and 15 g of toluene as a compound of the formula (2) were fed, and the mixture was heated while stirring under a nitrogen atmosphere. The solution is completely dissolved. Then, while paying attention to the temperature rise due to the heat of reaction, it is added as a hydrazine, 4_naphthoquinone (as mentioned above) 44. 5g. At this time, ι, 4-naphthoquinone and HCA The molar ratio is 丨, 4-naphthoquinone/HCA = 0.91. After heating, the ΕΡ0Τ0ΗΤ0 ZX-171K as a 2-functional epoxy resin having a naphthalene skeleton is fed as described above) i92.〇g, and as a 2-functional epoxy Resin ΕΡ0Τ0ΗΤ0 YD-128C Dongdu Chemical Co., Ltd., bisphenol A Epoxy resin, epoxy equivalents: 187g / eq) 192 〇g, while introducing a nitrogen gas - edge was stirred and heated to 130. (: The benzene is removed to the outside of the system. Then, triphenylphosphine (as described above) 〇. llg is added as a catalyst, and the reaction temperature is maintained at 16 (TC to 165 Torr) for 4 hours to obtain phosphorus. Epoxy resin H. The obtained phosphorus-containing epoxy resin H had an epoxy equivalent of 288 g/eq, a phosphorus content of I 9 wt%, and a softening point of 7 ° C. Synthesis Example 9 A stirring device, a thermometer, and the like were provided. In a four-port separable flask of a cooling tube and a nitrogen gas introduction device, HCA (as described above) of the phosphorus compound represented by the chemical formula (2) was fed 70. Og and toluene 16 〇g, while in a nitrogen atmosphere 21 321863 201130878 Under the mixing of '- while heating to completely dissolve H - while paying attention to the temperature rise due to the heat of reaction, - side-by-side input as _ u_ naphthalene (as mentioned above) 46.4g. At this time 1,4-naphthalene pro The molar ratio to the HCA is u-Caiyin/Hidden = 0.88. After the heating reaction, the ΕΡ0Τ0ΗΤ0 ZX-1711 (as described above) which is a 2-functional ring resin having a naphthalene skeleton is fed 3 〇〇g while introducing the gas side. The mixture was heated to 130 ° C and the toluene was removed to the outside of the system. However, t was added as a triphenyl group as a catalyst. (as mentioned above) 〇. 12g, while maintaining the reaction, the field is maintained at 16 to 165 ° C - while reacting for 4 hours, the dish containing ring i is obtained. The obtained epoxy equivalent of the phosphorus-containing epoxy resin is 3 〇ι —: 2. 4% by weight, softening point is 96 ° C. Synthesis Example 10 official and 0g, one does not use stupid base l9 〇 ° c in the preparation of mixing device, thermometer, cooling tube, nitrogen gas guide 4 glass In a separable flask, HCA-NQ (as described above) is compounded as a compound having a naphthalene skeleton x scoring epoxy resin, 2810Τ0ΗΤ0 ZX-1711C (as described above) 281 〇g, which is a chemical formula (1) 2= The crucible is mixed under a nitrogen atmosphere and heated to 13 Torr. At this time, the hydrazine compound of the formula (2) is added. Then, 'the addition of the catalyst as the third to the obtained epoxide containing the ja-lip J The equivalent weight is 608 g/eq, the phosphorus content is 35, and the long-oxygen tree point is 14 (TC. 'Softening Examples 1 to 7 and Comparative Examples 1 to 4. According to the formulation shown in Table 1, the dish ring is prepared. Oxygenating agent (Y), other epoxy resin, hardening to promote the sword stalk "m", hard 丨 丨 special. Methyl hexyl hydrazine (as mentioned above) 0. 21g, While maintaining the reaction temperature at 17 〇7-base phosphine for 4 hours, a phosphorus-containing epoxy resin j 321863 22 1 201130878 was obtained to dissolve the squamous epoxy resin and other epoxy resin, and was added as a pre-dissolved in the monomethyl alcohol. The cyanoguanidine (DICY 'active hydrogen equivalent: 21. Og/eq) of the methyl cellosolve and the hardening agent (Y) of dimethyl carbamide, and 2-ethyl-4-methyl as a hardening accelerator The resin varnish was prepared in such a manner that the nonvolatile content was 50% by weight in the form of a product of 2E4MZ. Then, using the obtained resin varnish, glass cloth impregnated with the substrate (WEA 116E 106S 136, thickness 100 μm, manufactured by Daito Machinery Co., Ltd.), and the impregnated glass cloth was dried in a hot air circulating oven at 150 ° C for 8 minutes. 'Get prepreg. Secondly, 'the obtained prepreg 4 pieces were overlapped with copper enamel (3EC-III, thickness 35#111, manufactured by Mitsui Mining Co., Ltd.), and heated and added at 130 °C for 15 minutes and 170 °C for 2.0 MPa for 70 minutes. Press to obtain a 0.6 mm thick laminate. With respect to each of the obtained laminated sheets, tests for various physical properties such as copper foil peeling strength, interlayer peel strength, flame retardancy, glass transition temperature, linear thermal expansion coefficient, water absorption ratio, and solder heat resistance were performed. The results are shown in Table 2. 321863 23 201130878 r—lKl—i Comparative Example 4 1 100.0 1 1.73 1 o.zo 8 Ο 〇ΙΟ « Comparative Example 3丨80.0 1 Ο 1 3.98 1 o.zo § f·- 0.14 S Oh Comparative Example 2| 100.0 1 1 3.65 1 0.25 g 0.10 〇Ok Comparative Example 1 1 I 100.0 I 2.88 0.30 茬0. 46 〇Ο ci Example 71 100.0 | 3.90 O.ZO 8 ο 〇ο (D .婼70.0 1 1 ΑΑ Λ 1 I OU WJ Z CO 0.20 | Nie I 0. 03 5 to Example 5| 80.0 I ί 20* 0 j 3.67 0.30 | 8 0. 01 ιί> οι Example 4 | 100.0 I 4.88 0. 29 0.02 ο 00 ο 3 66.7 CO CO o 4.09 0.30 〇0.02 s CM • Example 2 1 80.0 | i 20.0 ί 4.54 0. 20 | o 0. 02 s Example 1 1 100.0 I ! 4.04 0. SO 0. 05 ο 00 T— < ; <〇S·^ 0D η 〇/-Ν ♦ □ U) W U1 (D IL <0 σ η Φ X 0) φ /-s ο ί "3 YDPN-638 1 ESN-485 DICY ZE4MZ Listen 'Αβγ t «ϋαι县碱^ Ν ^ Ί bAL *ii VS gas to S medium - J〇tJ ^QtJ ηΒτη η®η Ο 〇« r-ffi 正蛘^C-φ1 * Phosphorus content of all epoxy resins in the composition (% by weight) Phosphorus-containing epoxy resin 00 Other epoxy resin jD hardening accelerator i 24 321863 201130878 Comparative Example 4| eo oq Ο α> to 2 X Comparative Example 3 CD τρ ΙΟ u> SX Comparative Example 2 G> csl a> ο ζ 5 1 - 〇 0 CM r - α > X Comparative Example 1 Csl 卜 o ? > ΙΟ u> eg X Example 7 I Csl esi O) ? >u> CD u>u>u> o Example 6 <D cu ο σ><D τ-· 〇> CO CD o in 3 eg ο 00 <D Τ-» s u> o Implementation Example 4 00 ι ΙΑ CD T-* C4 in 寸 · o Example 3 (D 〇· ? > in 卜 〇 〇 Example 2 1 00 CD s 1 £> o Example 1 ? >〇> C0 U) o Copper foil peel strength (kN/m) Interlayer peel strength (kN/m) Li Wei\\ m Glass transfer temperature 0*0 M Lifting d 漤3 | Water absorption rate (%) 1 Welding heat resistance running I 25 321863 201130878 Examples 1 to 5 and Comparative Examples 1 to 3 use phosphorus obtained by reacting a compound of the formula (2) with 1,4-naphthoquinone before reacting with the epoxy resin (a). Compound (b) and proceed In the phosphorus-containing epoxy resin obtained by the reaction, in Example 6, a phosphorus-containing epoxy resin obtained by reacting a compound represented by the chemical formula (1) synthesized in advance with a compound represented by the chemical formula (2) as the phosphorus compound (b) was used. In Example 7 and Comparative Example 4, a filled epoxy resin which was reacted only by filling a compound as shown in the chemical formula (1) synthesized in advance was used. In Comparative Example 1, in the synthesis of the scaly epoxy resin, since only 66% by weight of a 2-functional epoxy resin having a naphthalene skeleton was used, and the molar ratio of the chemical formula (1): Chemical formula (2) was 1:0.46, That is, a large amount of the phosphorus compound of the chemical formula (2) is used, so that the water absorption rate is as high as 1.2%, the moisture resistance is poor, and the solder heat resistance is also poor. Further, although a polyfunctional epoxy resin is often used, the glass transition temperature is 1551, and heat resistance is difficult to be high. The peel strength between layers has not reached 1. OkN/m, and it has not become a practical laminate. In Comparative Example 2, when a phosphorus-containing epoxy resin was synthesized, since only 50% by weight of a bifunctional epoxy resin having a naphthalene skeleton was used, even if the phosphorus content was less than 2% by weight, it was not flame retardant and heat resistance. And moisture resistance is also not good. In Comparative Example 3, when a phosphorus-containing epoxy resin was synthesized, 100% by weight of a bifunctional epoxy resin having a naphthalene skeleton was used, but the molar ratio of the chemical formula (1): the chemical formula (2) was 1:0.4. That is, a large amount of the chemical formula (2) compound is used, so the interlayer peeling strength is less than 1. OkN/m, and the heat resistance is hardly high. The weight of the phosphorus is as high as 3. 5 by weight. The weight of the phosphorus is as high as 3. 5 by weight. %, so the softening point of the resin is as high as 140 ° C, so that the impregnation of the glass cloth 26 321863 201130878 deteriorates, and the interlayer peel strength is less than 1. OkN / m, the solder heat resistance is not good. On the other hand, the phosphorus compound synthesized by using the compound of formula (1) with respect to the compound of formula (1) is 0. 06 mol or less and using 7 wt% or more of a bifunctional epoxy resin having a naphthalene skeleton. The epoxy resin is a necessary component, and the phosphorus content of the epoxy resin is from 0.5% by weight to less than 2.0% by weight. Examples i to 7 are flame retardant, adhesion, heat resistance, and resistance. Excellent wettability. Further, as shown in Example 4 and Example 7, even if the scaly ratio is 1% by weight or less, the flame retardancy can be satisfied, so that a laminate having excellent moisture resistance can be obtained. As shown in Examples 2, 3, 5 and 6, it is also possible to use an epoxy resin composition which does not contain a filled epoxy resin, and which is excellent in heat resistance and excellent in adhesion and flame retardancy. Further, when the epoxy resin composition of the present invention is used, a laminate having a low coefficient of linear expansion is obtained. (Industrial Applicability) The present invention is most suitable as an electrical insulating material including a copper-clad laminate for use in an electronic circuit board, and is also suitable as a sealing material, a molding material, a molding material, an adhesive, and a film for use in electronic components. It is also effective as a material for electrical insulating coatings. [Simple description of the diagram] None. [Main component symbol description] None. 27 321863