201241033 六、發明說明： 【發明所屬之技術領域】 本發明是關於具有阻燃性之含磷環氧樹脂及含有該 填之環氧樹脂組成物，以及其硬化物。 【先前技術】 由於環氧樹脂在接著性、财熱性、成形性方面優異， 故廣泛使用在電氣·電子機器的積層板、密封劑、汽車零 件、FRP、運動用品等方面。 尤其，在電氣·電子機器中使用積層板時，為了防止 火災時的燃燒與發煙的控制，而強烈要求對積層板賦於阻 燃性。作為積層板用樹脂的阻燃化方法，以往，係單獨或 組合溴系阻燃劑、氮系阻燃劑與磷系阻燃劑，在前述單獨 或組合的阻燃劑中以併用無機系阻燃助劑之阻燃系統為主 流。但是，近年來，由於環境問題而儘可能地避開溴系阻 燃劑的使用。又，作為添加型構系阻燃劑而使用紅填時， 在安全性上並不足，在使用磷酸系化合物時，會有滲出硬 化物表面之問題。又，使用磷酸酯類時，會有銲錫耐熱性、 耐溶劑性下降的問題。 針對前述問題，在專利文獻1、2中，揭示一種使10-(2, 5-二羥基苯基）-10H-9-氧雜-10-膦菲-10-氧化物（三光 股份有限公司製商品名HCA-HQ)與環氧樹脂類以所定之 莫耳比反應而得的熱硬化性樹脂及組成物。又，在專利文 獻3中，揭示一種具有2個官能以上之環氧基的樹脂與二 苯基氧膦基氫醌反應而製成之含磷環氧樹脂。然而，由如 323897 5 201241033 此之磷化合物與環氧樹脂反應而得的含鱗環氧樹脂，由於 隨著磷含量變高而使分子量變大’故可得到有充分阻燃性 之樹脂清漆的黏度會變高’而有作業性或對玻璃布（glass cloth)等基材之含浸性變差之問題。進一步，含構環氧樹 脂的分子量變大時’由於硬化物的交聯密度降低，故很難 得到高的玻璃轉移溫度。 又，雖在專利文獻4中揭示一種只有含填環氧樹脂 而得不到充分的阻燃性，使磷化合物在含磷環氧樹脂清漆 中溶解並提高磷含量之方法，但在溶劑中必需使用N，N一二 甲基曱醯胺等的高沸點溶劑，而有磷化合物容易析出的問 題。在專利文獻5中，雖揭示將HCA_HQ的平均粒徑1〇//m， 最大粒徑40 的大小藉由微粉碎而分散在樹脂清漆中的 方法，但比起使用高沸點溶劑溶解磷化合物的情形，黏度 將容易變高，如欲降低清漆黏度則有得不到充分之阻燃性 的問題。 [先前技術文獻] (專利文獻） 專利文獻1 :日本專利—3092009 專利文獻2:日本特開平 專利文獻3:曰本特開平5_214〇7〇 專利文獻4:日本特開2〇〇2_24954〇 專利文獻5 :日本特開2〇〇3_〇11269 【發明内容】 [發明欲解決之課題] 323897 6 ⑧ 201241033 本發明之目的是提供-種含•裒氡樹脂，係藉由反應 後在末端殘存酚性羥基使分子量變小，則清漆黏产會低 ‘ ·作業性優異。又，本發明藉由硬化該含鐵環氧樹， * 可以提供硬化性、阻燃性、耐熱性、接著性優異的硬化物。 [解決課題之手段] 即，本發明是 ⑴二種含磷環氧樹脂，其特徵係、：由環氧樹脂類⑸， =具有與環氧樹脂類⑷的環氧基反應之反應性官能 =匕合物類㈦反應而得’其中具有反應性官能基 兔二勿類(b)疋將一般式⑴所示的含磷酚化合物作 成分’並且所得含鱗環氣樹脂的環氧基當量是 在由式1求得之理論環氧當量之_至哪的範圍内。 (1) 〇1~fC%R2201241033 VI. Description of the Invention: [Technical Field] The present invention relates to a phosphorus-containing epoxy resin having flame retardancy and an epoxy resin composition containing the same, and a cured product thereof. [Prior Art] Since epoxy resin is excellent in adhesiveness, heat efficiency, and moldability, it is widely used in laminates, sealants, automobile parts, FRP, sporting goods, etc. of electric and electronic equipment. In particular, when a laminate is used in an electric or electronic device, in order to prevent combustion and smoke control during a fire, it is strongly required to impart a flame retardancy to the laminate. As a flame-retarding method of the resin for laminated sheets, conventionally, a bromine-based flame retardant, a nitrogen-based flame retardant, and a phosphorus-based flame retardant are used alone or in combination, and the inorganic resistance is used in combination with the flame retardant alone or in combination. The flame retardant system of fuel additives is the mainstream. However, in recent years, the use of bromine-based flame retardants has been avoided as much as possible due to environmental problems. Further, when red filler is used as the additive-type flame retardant, it is insufficient in safety, and when a phosphate-based compound is used, there is a problem that the surface of the carbide is oozing out. Moreover, when a phosphate ester is used, there exists a problem that solder heat resistance and solvent resistance fall. In view of the above problems, Patent Documents 1 and 2 disclose that 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphinophen-10-oxide (manufactured by Sanko Co., Ltd.) The product name HCA-HQ) and a thermosetting resin and a composition obtained by reacting an epoxy resin with a predetermined molar ratio. Further, Patent Document 3 discloses a phosphorus-containing epoxy resin produced by reacting a resin having two or more functional epoxy groups with diphenylphosphinylhydroquinone. However, the scaly epoxy resin obtained by reacting a phosphorus compound such as 323897 5 201241033 with an epoxy resin has a molecular weight which becomes larger as the phosphorus content becomes higher, so that a resin varnish having sufficient flame retardancy can be obtained. The viscosity becomes high, and there is a problem of workability or impregnation of a substrate such as glass cloth. Further, when the molecular weight of the structural epoxy resin is increased, the crosslinking density of the cured product is lowered, so that it is difficult to obtain a high glass transition temperature. Further, Patent Document 4 discloses a method of dissolving a phosphorus compound in a phosphorus-containing epoxy resin varnish and increasing the phosphorus content, which does not provide sufficient flame retardancy, and is necessary in a solvent. A high boiling point solvent such as N,N-dimethylamine or the like is used, and there is a problem that the phosphorus compound is easily precipitated. Patent Document 5 discloses a method in which the average particle diameter of HCA_HQ is 1 〇//m, and the maximum particle diameter 40 is dispersed in a resin varnish by fine pulverization, but the phosphorus compound is dissolved by using a high-boiling solvent. In the case, the viscosity will tend to become high, and if the viscosity of the varnish is to be lowered, there is a problem that sufficient flame retardancy is not obtained. [Prior Art Document] (Patent Document) Patent Document 1: Japanese Patent - 3092009 Patent Document 2: Japanese Patent Laid-Open Patent Publication No. 3: 曰本特开平 5_214〇7〇 Patent Document 4: Japanese Patent Publication 2〇〇2_24954〇 Patent Literature 5: Japanese Patent Laid-Open No. 2〇〇3_〇11269 [Summary of the Invention] [Problems to be Solved by the Invention] 323897 6 8 201241033 The object of the present invention is to provide a resin containing phenol which remains at the end after the reaction. If the molecular weight is reduced by the hydroxyl group, the varnish will be low in productivity. Moreover, the present invention can provide a cured product excellent in curability, flame retardancy, heat resistance, and adhesion by curing the iron-containing epoxy tree. [Means for Solving the Problem] The present invention is (1) two kinds of phosphorus-containing epoxy resins, characterized in that: epoxy resin (5), = reactive functional group having an epoxy group reactive with epoxy resin (4) = The compound (7) is obtained by reacting a compound having a reactive functional group (b), a phosphorus-containing phenol compound represented by the general formula (1) as a component, and the epoxy equivalent of the obtained scaly ring-containing resin is Within the range of the theoretical epoxy equivalent of the formula 1 obtained. (1) 〇1~fC%R2
HO- A—〇H Υ式中’ A表示碳原子數6至2()的伸芳基及/或三基 如1) ’ n表示0或卜又，式中1及R2表示碳原子 1至6的基’可以相同也可以相異，也可以與續 原子共同成為環狀。） [數1] 理論環氧基當量(g/eq )= 反應總重量(g) ^Χ^Γ)"…… 323897 201241033 [數2] a_ 禮氧樹脂類（a)之重量（g) A~ ~~類（a)之環氧基當量（g7^y^~.........(2) [數3] R__$有多性官能基的化合物類(b)之) 一-基的化合物類（b)之官能…口；) (2)上述（1)所述之含磷環氧樹脂，係由相對於气 __ 環氧樹脂類⑷的環氧基1當量，與具有^應 基化合物類（b)之反應性官能基0. 1〇卷曰ρ 田1至0. 94當 量之範圍反應所得。 (3 ) —種含鱗環氧樹脂組成物，係相對於含 、3哥將前述（1) (4) 或前述（2)所述之含磷環氧樹脂作為必須成八之八填 環氧樹脂（c)的環氧基1當量，摻配$裒氧樹^硬1劑 的反應性官能基0. 1當量至1. 3當量之範圍^ 一種含磷環氧樹脂硬化物，係使前述（3)所述之含磷 環氧樹脂組成物硬化而成者。 [發明效果] 本發明之含磷環氧樹脂，雖是藉由環氧樹脂類（&)的 環氧基’與一般式（1)所示含磷酚化合物的酚性經基反應而 考于’但並不是與全部之紛性經基反應’而是殘存一部分， 在環氧樹脂中環氧基與酚性羥基為共存。藉由環氧基與酚 性經基共存之事’比全部的紛性經基反應的情形更能得到 分子量變低的環氧樹脂，作成環氧樹脂清漆時的黏度也會 323897 ⑧ 8 201241033 變低。藉由此可以得到提高對玻璃布之含浸性等，且作業 _ 性良好之含磷環氧樹脂。又，評估本環氧樹脂的硬化物物 ·_ 性之時，發現不具有酚性羥基與只具有環氧基之公知的含 *. 磷環氧樹脂相比，可以提高耐熱性及阻燃性等，遂而完成 本發明。 【實施方式】 [實施發明之最佳形態] 以下，詳細說明關於本發明的實施形態。 為了製造本發明之含磷環氧樹脂而使用的環氧樹脂（a) 可以列舉.由 Epotohto YD-128、Epotohto YD-8125(新日 鐵化學股份有限公司製雙酚A型環氧樹脂）、Ep〇t〇ht〇 YDF-170、Epotohto YDF-8170(新日鐵化學股份有限公司製 雙酚F型環氧樹脂）、YSLV-80XY(新日鐵化學股份有限公司 製四曱基雙紛F型環氧樹脂）、Epotohto YDC-1312(氫酿i 型環氧樹脂）、jER YX4000H(三菱化學股份有限公司製聯 苯型環氧樹脂）、Epotohto YDPN-638C新日鐵化學股份有限 公司製紛紛酸清漆型環氧樹脂）、Ep〇t〇hto YDCN-70U新 日鐵化學股份有限公司製甲酚酚醛清漆型環氧樹脂）、 Epotohto ZX-120K新日鐵化學股份有限公司製雙紛苐型 環氧樹脂）、TX-0710(新日鐵化學股份有限公司製雙酚s 型環氧樹脂）、EPICLON EXA-1515C大日本化學工業有限公 司A雙紛S型環氧樹脂）、NC-3000(日本化藥股份有限公 司製聯苯芳烷基酚型環氧樹脂）、Ep〇t〇hto ZX-1355、 Epotohto ZX-1711(新日鐵化學股份有限公司製萘二醇型 323897 9 201241033 環氧樹脂）、Epotohto ESN-155(新日鐵化學股份有限公司 製/3 -萘盼芳烧基型環氧樹脂）、Epotohto ESN-355、 Epotohto ESN-375(新日鐵化學股份有限公司製聯萘盼芳 烧基型環氧樹脂）、Epotohto ESN-475V、Epotohto ESN-485 (新日鐵化學股份有限公司製α-萘酚芳烷基型環氧樹脂）、 ΕΡΡΝ-501Η(日本化藥股份有限公司製三苯基曱燒型環氧 樹脂）、Sumiepoxy ΤΜΗ-574(住友化學股份有限公司製三 苯基曱烧型環氧樹脂）、YSLV-120ΤΕ(新日鐵化學股份有限 公司製雙硫醚型環氧樹脂）、Epotohto ΖΧ-1684(新日鐵化 學股份有限公司製間苯二酚型環氧樹脂）、DENACOL EX - 2 01 (長瀨Chemtex股份有限公司製間苯二酚型環氧樹脂）、 EPICLON HP-7200H(DIC股份有限公司製二環戍二稀型環氧 樹脂）等的多酴樹脂之紛化合物與表鹵醇（epihalohydrin) 所製造之環氧樹脂；由TX-0929、TX-0934、ΤΧ-1〇32(新日 鐵化學股份有限公司製烷二醇型環氧樹脂）等的醇化合物 與表鹵醇所製造之環氧樹脂；由Celloxide 2021CDaieel 化學工業股份有限公司製脂肪族環狀環氧樹脂）、Epotohto YH-434(新日鐵化學股份有限公司製二胺基二苯基曱烧四 環氧丙基胺）等的胺化合物與表齒醇所製造之環氧樹脂；將 jER 630(三菱化學股份有限公司製胺基酚型環氧樹脂）、HO-A—〇H Υ where 'A represents a aryl group having 6 to 2 () and/or a tri-group such as 1) 'n represents 0 or 卜, wherein 1 and R2 represent a carbon atom 1 to The bases of 6 may be the same or different, or may form a ring together with the continuation atom. ) [Number 1] Theoretical Epoxy Equivalent (g/eq) = Total Reaction Weight (g) ^Χ^Γ)"...... 323897 201241033 [Number 2] a_ Weight of Oxygen Resin (a) (g) A~ ~~ Ethylene equivalent of class (a) (g7^y^~.........(2) [Number 3] R__$ Compounds with polyfunctional groups (b)) The functional group of the one-based compound (b); (2) The phosphorus-containing epoxy resin according to the above (1), which is one equivalent of the epoxy group relative to the gas-based epoxy resin (4). The reaction is carried out in the range of from 1 to 0.94 equivalents of the reactive functional group having a compound of the compound (b). (3) A scaly epoxy resin composition, which is equivalent to the inclusion of the phosphorus-containing epoxy resin described in the above (1) (4) or (2), as an epoxy resin The epoxy group of the resin (c) is 1 equivalent, and the reactive functional group is blended with a solvent of 0.1% equivalent to 1. 3 equivalents. (3) The phosphorus-containing epoxy resin composition is hardened. [Effect of the Invention] The phosphorus-containing epoxy resin of the present invention is reacted by the phenolic radical reaction of the epoxy group of the epoxy resin (&) with the phosphorus-containing phenol compound represented by the general formula (1). In the 'but not all of the reactive groups', but a part of it remains, in the epoxy resin, the epoxy group and the phenolic hydroxyl group coexist. By the fact that the epoxy group and the phenolic base are coexisting, it is possible to obtain an epoxy resin having a lower molecular weight than the case of all the sulfonic acid radical reaction, and the viscosity when the epoxy resin varnish is formed is also 323897 8 8 201241033 low. By this, it is possible to obtain a phosphorus-containing epoxy resin which is improved in impregnation with glass cloth and has good workability. Further, when the cured product of the present epoxy resin was evaluated, it was found that the phenolic hydroxyl group can improve heat resistance and flame retardancy as compared with the known phosphorus-containing epoxy resin having only an epoxy group. Etc., the present invention is completed. [Embodiment] [Best Mode for Carrying Out the Invention] Hereinafter, embodiments of the present invention will be described in detail. The epoxy resin (a) used for producing the phosphorus-containing epoxy resin of the present invention may be exemplified by Epotohto YD-128, Epotohto YD-8125 (Nippon Steel Chemical Co., Ltd. bisphenol A type epoxy resin), Ep〇t〇ht〇YDF-170, Epotohto YDF-8170 (Nippon Steel Chemical Co., Ltd. bisphenol F-type epoxy resin), YSLV-80XY (Nippon Steel Chemical Co., Ltd. made four 曱基双F Epoxy resin), Epotohto YDC-1312 (hydrogenated i-type epoxy resin), jER YX4000H (biphenyl type epoxy resin manufactured by Mitsubishi Chemical Corporation), Epotohto YDPN-638C Nippon Steel Chemical Co., Ltd. Acid varnish type epoxy resin), Ep〇t〇hto YDCN-70U Nippon Steel Chemical Co., Ltd. cresol novolac type epoxy resin), Epotohto ZX-120K Nippon Steel Chemical Co., Ltd. Epoxy resin), TX-0710 (Nippon Steel Chemical Co., Ltd. bisphenol s type epoxy resin), EPICLON EXA-1515C Dainippon Chemical Industry Co., Ltd. A double S-type epoxy resin), NC-3000 ( Nippon Chemicals Co., Ltd. Biphenyl aralkylphenol type epoxy tree ), Ep〇t〇hto ZX-1355, Epotohto ZX-1711 (Nippon Steel Chemical Co., Ltd. naphthalene glycol type 323897 9 201241033 epoxy resin), Epotohto ESN-155 (Nippon Steel Chemical Co., Ltd. / 3 - naphthene aromatic epoxy resin), Epotohto ESN-355, Epotohto ESN-375 (Nippon Steel Chemical Co., Ltd.), Epotohto ESN-475V, Epotohto ESN -485 (α-naphthol aralkyl type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), ΕΡΡΝ-501Η (Triphenyl oxime-type epoxy resin manufactured by Nippon Kayaku Co., Ltd.), Sumiepoxy ΤΜΗ-574 (Sumitomo Chemical Co., Ltd. made triphenyl sulfonated epoxy resin), YSLV-120 ΤΕ (disulfide epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), Epotohto ΖΧ-1684 (Nippon Steel Chemical Co., Ltd. Company made resorcinol type epoxy resin), DENACOL EX - 2 01 (resorcinol type epoxy resin manufactured by Changchun Chemtex Co., Ltd.), EPICLON HP-7200H (dicyclic bismuth diene manufactured by DIC Corporation) Type epoxy resin, etc. Epoxy resin produced by epihalohydrin; alcohol compound and epihalide such as TX-0929, TX-0934, ΤΧ-1〇32 (alkalidiol type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.) Epoxy resin produced by alcohol; aliphatic cyclic epoxy resin manufactured by Celloxide 2021CDaieel Chemical Industry Co., Ltd.), Epotohto YH-434 (diamine diphenyl sulfonium tetraacetate manufactured by Nippon Steel Chemical Co., Ltd.) An epoxy compound such as propylamine) and an epoxy resin produced from epidentate alcohol; jER 630 (aminophenol-based epoxy resin manufactured by Mitsubishi Chemical Corporation),
Epotohto FX- 289B、Epotohto FX-305、TX-0932AC新日鐵 化學股份有限公司製含磷環氧樹脂）等的環氧樹脂與含填 盼化合物等之改質劑反應而得的含磷環氧樹脂、聚胺醋改 質氧樹脂、含有％吐α定酮壤（oxazo 1 i done)環氧樹脂等， 10 323897 ⑧ 201241033 但不侷限於此等。又，此等之環氧樹脂可以單獨使用，也 可以合併2種類以上而使用。 與環氧樹脂類（a)之環氧基反應的反應性官能基的官 能基當量，在酚化合物時是表示羥基當量；在酸酐時是表 示酸針當量；在胺化合物或在填原子有直接鍵結氫的填化 合物等時是表示活性氫當量。 具有反應性官能基的化合物類（b)是將一般式（1)所 示之含磷酚化合物當作必須成分。作為含磷酚化合物的具 體例者，可以列舉：10-(2,5-二羥基苯基）-1011-9-氧雜-10-膦菲-10-氧化物（三光股份有限公司製商品名HCA -HQ)、 10-(1，4-二氧蔡）-10H-9-氧雜-10-鱗菲-10-氧化物（以下 簡稱為HCA-NQ)、二苯基氧膦基氫醌（北興化學工業股份有 限公司製商品名PPQ)、二苯基氧膦基-1，4-二氧萘、1，4-環辛烯氧膦基-1，4-苯基二醇（曰本化學工業股份有限公司 製商品名CPH0-HQ)、1,5-環辛烯氧膦基-1，4-苯基二醇 (曰本化學二業股份有限公司製商品名CPHO-HQ)等之含 磷酚類，但不侷限於此等。又，此等含磷酚化合物也可以 合併2種類以上而使用。 0=F^〇kR2 ⑴Phosphorus-containing epoxy resin obtained by reacting an epoxy resin such as Epotohto FX-289B, Epotohto FX-305, TX-0932AC, Nippon Steel Chemical Co., Ltd., and a modifier containing a compound such as a phosphorus compound Resin, polyamine vinegar modified oxygen resin, epoxy resin containing oxazo 1 i done, etc., 10 323 897 8 201241033 However, it is not limited thereto. Further, these epoxy resins may be used singly or in combination of two or more types. The functional group equivalent of the reactive functional group reactive with the epoxy group of the epoxy resin (a) means a hydroxyl equivalent in the case of a phenol compound; an acid needle equivalent in an acid anhydride; and an amine compound or a direct atom in a filled atom The compound or the like which bonds hydrogen is equivalent to the active hydrogen equivalent. The compound (b) having a reactive functional group is an essential component of the phosphorus-containing phenol compound represented by the general formula (1). Specific examples of the phosphorus-containing phenol compound include 10-(2,5-dihydroxyphenyl)-1011-9-oxa-10-phosphinophen-10-oxide (trade name of Sanko Co., Ltd.) HCA-HQ), 10-(1,4-dioxonate)-10H-9-oxa-10-phenanthrene-10-oxide (hereinafter referred to as HCA-NQ), diphenylphosphinylhydroquinone (trade name PPQ manufactured by Beixing Chemical Industry Co., Ltd.), diphenylphosphinyl-1,4-dioxophthalene, 1,4-cyclooctenephosphinyl-1,4-phenylene glycol (曰本Chemical Industry Co., Ltd., trade name CPH0-HQ), 1,5-cyclooctene phosphinyl-1,4-phenyl diol (product name CPHO-HQ manufactured by Sakamoto Chemical Co., Ltd.), etc. Phosphorus-containing phenols, but are not limited to these. Further, these phosphorus-containing phenol compounds may be used in combination of two or more types. 0=F^〇kR2 (1)
HO-A-OH (式中，A表示碳原子數6至20的伸芳基及/或三基，η 表示0或1。又，式中之匕及R2表示碳原子數1至6的烴 基，可以相同也可以相異，也可以與磷原子共同成為環狀。） 323897 11 201241033 又，此等含磷紛化合物可由9, 10-二氫-9-氧雜-l〇-膦菲-10-氧化物（三光股份有限公司製商品名HCA)或在 二苯基膦等的磷原子有直接鍵結的活性氩基之磷化合物， 與1，4-苯醌或萘醌等之醌類反應而得。關於HCA-HQ 是在日本特開昭60-126293、關於HCA-NQ是在日本特開昭 61-236787、關於 PPQ 是在 zh.Obshch. Khim，42(11)，2415- 2418頁（1972)揭示合成之方法，但不侷限於此等，可以使 用公知習用的方法。 作為前述含磷酚化合物以外的具有反應性官能基的 化合物類（b)者，例如’可以列舉：兒茶酚（catechol)、間 苯二酚（resorcinol)、氫醌等的羥基苯類、聯苯酚類、聯 萘酚類、三酚類、雙酚A、雙酚F、雙酚S、Shonol BRG-555 (昭和電工股份有限公司製酚酚醛清漆樹脂）、甲酚酚醛清 漆樹脂、烧基盼驗路清漆樹脂、芳燒基紛驗酿清漆樹脂、 含三嗪環之酚酚醛清漆樹脂、聯苯基芳烷基酚樹脂、 RESITOP TPM-100(群榮化學工業股份有限公司製三羥基 苯基甲烷型酚醛清漆樹脂）、在芳烷基萘二醇樹脂等的一分 子中有2個以上的酚性羥基之化合物類、在9, 1〇_二氫一9_ 氧雜-10-膦菲-10-氧化物（三光股份有限公司製商品名 HCA)或二苯基膦等的磷原子有直接鍵結的活性氫基之磷化 合物類、己二醯肼、癸二醯肼等酿肼類、咪唑化合物類及 其鹽類、雙氰胺（dicyandiamide)、胺基安息香酸酯類、二 乙二細、二乙四胺、四乙五胺、間苯二曱胺、異佛爾酮二 胺等的脂肪族胺類、二胺基二笨基曱烧、二胺基二苯基颯、 323897 ⑧ 12 201241033 二胺基乙基笨等之芳香族胺類、對苯二甲酸酐、偏苯三酸 酐、均笨四曱酸酐、馬來酸酐、四氫苯二曱酸酐、甲基四 氫苯二甲酸酐、六氫苯二曱酸酐、曱基六氫苯二曱酸酐、 甲基納連克酸SKNadic Methyl Anhydride)等的酸肝等， 此等也可以使用2種以上。此等化合物的使用量，相對於 所使用的環氧樹脂中之環氧基1當量，官能基以使用在0. 5 當量以下之方式為佳，更佳是0. 2當量以下。 本發明的含磷環氧樹脂的環氧基當量，雖然是在式1 所求理論環氧基當量的60%至95%之範圍，但以70°/。至95% 之1¾圍為佳，更佳是75%至90%之範圍。比60%小時，很多 難'容性的含磷酚化合物會殘留，溶劑溶解性會變差。比95% 大時’作為環氧樹脂清漆時的黏度下降效果會變低。 又本發明的含磷環氧樹脂，係相對於式2所示環氧樹 脂類（a)的環氧基1當量，具有反應性官能基之化合物類（b) 的反應性官能基在〇. 10當量至0. 94當量的範圍下反應而 得：，但以0.2當量至0.70當量為佳，更佳是0.2當量至 〇. 虽量。（b)比0. 10當量少時，阻燃性變不足，超過0· 94 虽反應時，得到之含磷環氧樹脂之清漆黏度會變高。 。 得到本發明的含磷環氧樹脂反應之反應溫度是自100 °〇至25(TC，更佳是13〇。(：至18〇t，在1〇〇它以下進行， 則反應會顯著緩慢，在250¾以上進行，為了作成理論環 氧當量的60%至95%之範圍之反應，在控制上會有困難。 又，在得到本發明的含磷環氧樹脂之反應中，玎因應 必而使用促進反應用之反應觸媒。作為可以使角的觸媒 323897 13 201241033 者，可以列舉：三苯基膦、三（2, 5-二甲氧基苯基）膦等膦 類、η-丁基三苯基鱗溴化物、乙基三苯基鱗碟化物等四級 鱗鹽類、2-乙基-4-甲基味吐、2-苯基σ米唾等之味β坐類、四 甲基銨氣化物、四乙基銨溴化物等四級銨鹽類、三乙胺、 苄基二曱基胺等之三級胺類等公知習用的觸媒，但不侷限 於此等。此等觸媒之使用量，相對於酚化合物全量，係以 0.005%至1%的範圍為佳。 環氧樹脂與含磷紛化合物之反應是可以在無溶劑中 進行’也可以在溶劑中進行，在溶劑中進行時，以在非質 子性溶劑中進行為佳’作為非質子性溶劑者，例如可以列 舉：甲苯、二甲苯、甲醇、乙醇、2-丁氧基乙醇、二烧基 醚、乙二醇醚、丙二醇單曱基醚、二卩等烷等。此等的反應 溶劑可以單獨使用’也可以同時使用2種類以上。此等的 反應溶劑之使用量疋以反應物全重量中的50%以下為佳。 又，本發明的含磷環氧樹脂之反應，在調整觸媒量下 可以將該樹脂環氧基當量定在理論環氧基當量的6 〇 %至 95%之範圍，但或δ周整反應溫度，階段性進行反應等，就可 以使用公知習用的製造方法，並不侷限於此等。 本發明的含磷環氧樹脂組成物，雖以前述之含磷環氧 樹脂為必須成分’但可因應需要而含有其它之環氧樹脂、 環氧樹脂硬化劑、硬化促進劑、填充劑等。 曰 在含有前，含填環氧樹脂組成物中可.使用之環氣樹 脂作為必要*分’除了本發明的含魏氧樹脂之外，在 損及物性範圍内’可以使用與在合成本發明的含碟環氣: 323897 14 201241033 脂中使用之環氧樹脂同樣種類的環氧樹脂，但不偈限於此 等。又，此等環氧樹脂也可以合併2種類以上來使用。 作為本發明的含磷環氧樹脂組成物中可使用的環氧 樹脂硬化劑者，可以列舉：兒茶酚、間苯二酚、氫醌等的 羥基苯類、聯萘酚類、聯苯酚類、三酚類、雙酚A、雙酚F、 雙紛s、二羥基苯基曱烷、三羥基笨基乙烷、Sh〇n〇1 brg_555 (昭和電工股份有限公司製酚酚醛清漆樹脂）、曱酚酚醛清 漆樹脂、烷基酚酚醛清漆樹脂、芳烷基酚酚醛清漆樹脂、 含二嗪環酚酚醛清漆樹脂、聯笨基芳烷基酚樹脂、RESIT〇p TPM-100(群榮化學工業股份有限公司製三羥基苯基曱烷 型酚醛清漆樹脂）、在芳烷基萘二醇樹脂等的一分子具中有 2個以上的酚性羥基之化合物、己二醯肼、癸二醢肼等醯 肼類、咪唑化合物類及其鹽類、二氰胺、胺基安息香酸酯 類、二乙三胺、三乙四胺、四乙五胺、間苯二甲胺、異佛 爾酮二胺等脂肪族胺類、二胺基二苯基曱烷、二胺基二苯 基砜、二胺基乙基苯等芳香族胺類、苯二曱酸酐、偏苯三 酸酐、均苯四甲酸酐、馬來酸酐、四氫苯二甲酸酐、曱基 四氫笨二甲酸酐、六氫苯二曱酸酐、曱基六氫苯二甲酸酐、 曱基納迪克酸酐等酸酐類等，亦可併用丨種類以上公知習 用的環氧樹脂硬化劑。環氧樹脂硬化劑的使用量，相對於 作為本發明的含磷環氧樹脂的必須成分之含磷環氧樹脂類 (c)的環氧基1當量，環氧樹脂硬化劑之官能基是以〇1 當量至1.3當量之範圍為佳，更佳是〇 2當量至〇 9當量。 又，在調整流動性或黏度等時，在不損及本發明的含 323897 15 201241033 磷環氧樹脂組成物的物性之範圍 劑。稀釋劑是以反應性稀釋 ’可以使用反應性稀釋 劑。作為反應性稀釋劑者，可以歹，亦可為非反應性稀釋 2-乙基己基縮水甘㈣、苯’丙基縮水甘油缝、 -紛缩水… 甘㈣等單官能、間苯 -紛縮水甘油峻、新戊二醇縮水 + ]丰 水…等二官能、甘油聚二 =6-己二醇二縮 P〇_c咖ether)、三㈣基^水甘油物咖01 水甘油醚等多官能縮水甘油醚類甘作：=: 〇il)等。 基二乙二醇、松油（Pine 又，在本發明的含磷環氧樹脂組成物令，可因應必要 而可以使用硬化促進劑。例如，可以列舉：膦類、四級鱗 鹽類、三級胺類、四級銨鹽類、咪唑化合物類、三氟化硼 錯合物類、3-(3, 4-二氣二苯基）-ι，ι_二甲基脲、一氯 苯基）-1,1-二甲基脲、3-苯基-1,1-二甲基脲等。此等硬化 促進劑是依使用的環氧樹脂、併用的環氧樹脂硬化劑之種 類、成形方法、硬化溫度、要求的特性，相對於環氣樹月t 以重量比是以〇· 01%至20%的範圍為佳，更佳是〇. 1%至J 本發明的含磷環氧樹脂組成物’在不損及特性範圍 下，也可以摻配其它之熱硬化性樹脂、熱塑性樹脂。例如， 可以列舉：酚樹脂、丙烯酸樹脂、石油樹脂、茚樹於、悉 白 豆酿I-節樹脂、苯氧樹脂、聚胺醋、聚醋、聚醯胺、聚醮亞 胺、聚醯胺醯亞胺、聚醚醯亞胺、聚醚砜、聚織、聚醚醚 酮、聚苯硫、聚乙烯曱醛等’但不侷限於此等》 323897 16 201241033 本發明的含碳環氧樹脂組成物，可因應必要而換配無 機填充劑、有機填充劑。作為填充劑者，可以列舉：溶融 二氧化矽、結晶二氧化矽、氧化銘、氡化矽、氫氧化鋁、 滑石、雲母、碳_、、氫氧Μ、碳_、碳酸 鋇、硫酸鋇、氮化删、石炭、碳纖維、破璃纖維、氧化銘纖 維、矽鋁纖維、碳化矽纖維、聚酯纖維、纖維素纖維、芳 香族醯胺纖維等。此等填充劑在樹脂組成物全體重量中是 以1%至70%為佳。 本發明的含填環乳樹脂組成物，可因應需求而復摻配 矽烷偶合劑、抗氧化劑、脫模劑、消泡劑、乳化劑、觸變 劑（thixotropic agent)、潤滑劑、阻燃劑、顏料等之成核 劑。此等添加劑在樹脂組成物全體重量中，以〇. 〇1 %至2〇% 的範圍為佳。 本發明的含磷環氧樹脂組成物，可以藉由與習知的環 氧樹脂組成物同樣的方法來成型、硬化而作成硬化物。成 型方法、硬化方法是可以採用與習知的環氧樹脂組成物同 樣的方法。無需本發明的樹脂組成物的固有方法。 本發明的含磷環氧樹脂組成物，可以採用積層物、成 型物、接著物、塗膜、薄膜等的形態。 本發明是具有阻燃性的含磷環氧樹脂，由於對玻璃布 (glass cloth)等基材之含浸性良好，故作業性優良，並 且’含磷環氧樹脂硬化物的阻燃性或耐熱性、接著性良好， 故判定適用作為在電氣電子零件中使用的密封材、鋼箔積 層板、絕緣塗料、阻燃塗料、複合材、絕緣阻燃接著劑等 323897 17 201241033 的材料。 (實施例） 其次，呈示本發明的實施例，但本發明的範圍並不侷 限於此等實施例。尤其在沒有特別論述時，「份」是表示重 量份。又，分析方法、測定方法是如下所述。 環氧當量：根據JIS K7236。 驗性經基當量：在試料中加入含有4%甲醇的THF，加 入10%氫氧化四丁基銨，使用紫外可見光分光光度計測定 在波長400nm至250nm間之吸光度。藉由同樣之測定方法 求得的檢量曲線，求得酚性羥基作為羥基每當量之試料重 量。 不揮發分：JIS K7235-1986 數量平均分子量：使用凝膠滲透層析分析儀（東曹股 份有限公司製HLC-8220GPC)測定分子量分佈，藉由標準聚 苯乙烯求得之檢量曲線換算。 填含量：在試料中加入硫酸、鹽酸、過氣酸，加熱使 濕式灰化，將全部之磷原子當作正磷酸。在硫酸酸性溶液 中使偏飢酸鹽及銦酸鹽反應，測定生成之填飢铜酸錯合物 在420nm中的吸光度，藉由預先作成的檢量曲線求得磷原 子的含量，以重量％表示。積層板的磷含量是以相對於積層 板的樹脂份之含量表示。 清漆黏度：使用錐板型黏度計（Tokimec公司製>，旋 轉器（rotor)是使用標準錐（1° 34’）在25°C的環境下，以 旋轉數lOrpm測定。 323897 18 ⑧ 201241033 紅外吸收光譜：使用傅葉爾轉換（Fourier transform) 紅外分光光度計（Perkinelmer股份有限公司製Spectum One),藉由錠劑法（KBr)測定。 玻璃轉移溫度：表示在示差掃描熱量測定裝置（sn NanoTechnology 有限公司製 EXSTAR6000 DSC6200)以 10 °C/分鐘的昇溫條件進行測定時的DSC外插值溫度。 燃燒性：根據 UL94(Underwriters Laboratories Inc. 的安全認證規格）。對5支試驗片進行試驗。第1次及第2 次的接觸火焰（5張分別各2次共計10次的接觸火焰）後的 火焰燃燒持續時間的合計時間，以秒表示。 銅箔剝離強度及層間剝離強度：根據JIS C6481。 Τ-288試驗：根據IPC ΤΜ-650在288°C進行試驗。 實施例1 在具備攪拌裝置、溫度計、冷卻管、氮氣導入管的四 口玻璃製可分離燒瓶實驗裝置中，放入雙紛j?型環氧樹脂 (新曰鐵化學股份有限公司製商品名YDF_17〇,環氧基當 量 170 g/eq· )687 份’加入 1〇-(2, 5-二羥基苯基）-i〇H-9- 氧雜-10-磷菲-10-氧化物（三光股份有限公司製商品名 HCA-HQ，融點256°C，碟含量9.6重量％，羥基當量162 g /eq. )314份。在此加入作為觸媒的三笨基膦（以下簡稱 ΤΡΡ)0· 06份於165°C中反應4小時後’加入曱基乙基酮（以 下簡稱MEK)加以稀釋。得到之含鱗環氧樹脂溶液是淡黃色 透明’不揮發分70%，清漆黏度510 mPa. s，實測環氣基當 量301 g/eq. ’羥基當量850 g/eq.，麟含量3. 〇重量％， 323897 19 201241033 數量平均分子量587。又，㈣於環 1當量，具有反應性官能基的化合物 ：氧基 當量’理論環氧基當量是-〜二== 當量’實測環氧基當量之比率是64X。在表t表示= 與放入比率、樹脂之性狀等。 量 實施例2 與實施例1同樣將687份之YDF-17〇、HCA-Hq251份、 酚酚醛 >月漆型樹脂（昭和電工股份有限公司製商品名 Shonol BRG-557，酚性羥基當量 1〇5 g/eq )63 份放二， 加入作為觸媒的TPP 〇. 06份，以與實施例i同樣的方法反 應，反應終止後，以MEK稀釋。得到之含磷環氧樹脂溶液 是淡黃色透明，不揮發分70%，清漆黏度550 mPa.s，實測 環氧基當量365 g/eq.，羥基當量1200 g/eq.，磷含量 2.4重量％，數量平均分子量619。又，相對於環氧樹脂類 (a)之環氧基1當量’具有反應性官能基的化合物類（b)< 官能基是0. 53當量，理論環氧基當量是527g/eq. ’相對 於理論環氧基當量，實測環氧基當量之比率是69%。在表i 表示放入量與放入比率、樹脂之性狀等。 實施例3 在具備攪拌裝置、溫度計、冷卻管、氮氣導入管的四 口玻璃製可分離燒瓶實驗裝置中，放入9, 10_二氫-9-氧雜 -10-膦菲-10-氧化物（三光股份有限公司製商品名HCA ’ 磷含量14. 2重量W209份及1,4-萘醌（川崎化成工業股份 有限公司製水分量3. 4重量«150重量份、甲苯490份， 323897 20 ⑧ 201241033 於饥中 30分鐘後，—面除去系統内的水分一面在 110C反應90分鐘後’除去甲苯得到1〇_(14_二氧萘 10H-9-氧雜-10-膦菲-1〇_氧化物（hca nq)。在此將ydf_17〇 641份，作為觸媒的TPP 〇. 〇9份加入，以與實施例i同樣 之方法反應，反應終止後，以MEK稀釋。得到之含磷環氧 樹脂溶液是深褐色透明’不揮發分7〇%，清漆黏度440 mpa. s，實測環氧基當量409 g/eq.，羥基當量Π50 g/eq.， 磷含量3. 0重量％，數量平均分子量6〇3。又，相對於環氧 樹脂類（a)之環氧基1當量，具有反應性官能基的化合物類 (b)之官能基是〇.5〇當量，理論環氧基當量是538g/eq.， 相對於理論環氧基當量，實測環氧基當量之比率是76%。 在表1表示放入量與放入比率、樹脂之性狀等。 實施例4 與實施例3同樣將HCA 141份、1,4-萘醌101份放入， 其餘用與實施例3同樣之方法反應得到HCA-NQ。在此加入 紛紛酿清漆型環氧樹脂（新日鐵化學股份有限公司製商品 名YDPN-638，環氧基當量175 g/eq. )758份、作為觸媒 的TPP 0· 02份在165°C中反應4. 5小時後，以MEK稀釋。 得到之含磷環氧樹脂溶液是深褐色透明，不揮發分70%， 清漆黏度130〇mpa.s，實測環氧基當量292g/eq.，羥基當 量3600 g/eq.，磷含量2.0重量％，數平均分子量884。 又’相對於環氧樹脂類（a)之環氧基1當量，具有反應性官 能基的化合物類（b)之官能基是〇· 3〇當量，理論環氧基當 量是318g/eq·，相對於理論環氧基當量，實測環氧基當 323897 21 201241033 量之比率疋92%。在表1表示放入量與放入比率、樹脂之 性狀等。 實施例5 與實施例3同樣將HCA 108份、1，4-萘醌80份放入， 其餘用與實施例3同樣之方法反應得到hca-NQ。在此加入 三苯基曱烧型環氧樹脂（日本化藥股份有限公司製商品名 EPPN-501H，環氧基當量167.2 g/eq. )833份、作為觸媒 的TPP0.02份在150。(：中反應6小時後，以丙二醇單甲基 趟（以下簡稱PGM)/MEK混合溶劑稀釋。得到之含磷環氧樹 脂溶液是深褐色透明，不揮發分7〇%，清漆黏度54〇mPa.s， 實測環氧基當量239g/eq.，羥基當量4〇〇〇g/e(j·,碟人 量1.5重量％，數量平均分子量628。又，相對於環 S 類（a)之環氧基1當量，具有反應性官能基的化合樹脂 之官能基是0· 20當量，理論環氧基當量是255g/e _(b) 對於理論環氧基當量，實測環氧基當量之比率是9=，相 表1表示放入量與玫入比率、樹脂之性狀等。 。。在 實施例6 與實施例3同樣將HCA 1〇8份、丨，4_萘靦8〇份 其餘用與實施例3同樣之方法反應得到HCA州Q。在玫入， 一萘酚芳烷基型環氧樹脂（新日鐵化學股份有限公入 品名ESN-375，環氧基當量167g/eq. )833份、A 5製商 的ΤΡΡ 〇·〇2份’在l5(rc中反應6小時後，以^觸媒 混合溶劑稀釋。得到之含磷環氧樹脂溶液是深褐/½¾ 不揮發分70% ’清漆黏度7〇〇mPa.s ,實測環氧基當逯明， 323897 备量239g 22 201241033 /eq•，歸當量棚^.，磷含量U重量％，❹ :均分子量716。又，相對於環氧樹脂類⑷之環氧基i當 置，具有反應性官能基的化合物類⑻之官能基是〇別: 量，理論環氧基當量是254g/eq.，相對於理論環氧^ 量，實測環氧基當量之比率是94%。在表1表示放入量盘 放入比率、樹脂之性狀等。 /、 實施例7 在實施例1得到的含鱗環氧樹脂中以表2所示之固形 份量摻配雙氰胺（DICY，活性氫當量21 g/eq )之硬化促 進劑，得到樹脂組成物。將此溶解到祖中作為樹脂清漆。 將传到之環氧樹脂清漆含浸玻璃布（WEA 116E1〇6S136日東 紡織股份有限公司冑厚度〇· lmm)中，於15『c的熱風循環 烘箱中乾燥10分鐘，得到預浸布。將4片得到之預浸布與 鋼鉍（3EC-1H三井金屬鑛業股份有限公司製厚度35wm) 重疊。於130txl5分鐘+ 170ΐχ70分鐘的溫度條件下進行 2MPa的真空加壓，得到〇. 5mm厚的積層板。在表2表示摻 配比率與積層板之評估結果。 實施例8 與實施例7同樣，使用實施例2得到的含磷環氧樹脂 及DICY ’得到環氧樹脂硬化物。在表2表示摻配比率與積 層板之評估結果。 實施例9 與實施例7同樣，使用實施例3得到的含磷環氧樹脂 及I)ICY ’得到環氧樹脂硬化物。在表2表示摻配比率與積 323897 23 201241033 層板之評估結果。 實施例10 與實施例7同樣，使用實施例3得到的含磷環氣樹 脂、曱酚酚醛清漆型環氧樹脂（新日鐵化學股份有限公司製 商品名YDCN-704 ’環氧基當量209 g/eq.)以及DICY，得 到環氧樹脂硬化物。在表2表示摻配比率與積層板之評估 結果。 實施例11 與實施例7同樣’使用實施例4得到的含磷環氧樹脂 及DICY，得到環氧樹脂硬化物。在表2表示摻配比率與積 層板之評估結果。 實施例12 與實施例7同樣，使用實施例3得到的含磷環氧樹脂 及BRG-557得到預浸布。重疊4片所得到之預浸布與銅箔 (3EC-11I三井金屬鑛業股份有限公司製厚度35ym)。於 130 〇乂15分鐘+ 19〇。(：><80分鐘的溫度條件下進行21^&的真 空加壓’得到0. 5_厚的積層板。在表2表示摻配比率與 積層板之評估結果。 實施例13 與實施例12同樣，使用實施例5得到的含磷環氧樹 脂及BRG-557得到環氧樹脂硬化物。在表2表示摻配比率 與積層板之評估結果。 實施例14 與實化例12同樣，使用實施例6得到的含磷環氧樹 323897 24 201241033 脂及BRG_557得到環氧樹脂硬化物。在表2表示摻配比率 與積層板之評估結果。 比較例1 與實施例1同樣將勝πο 687份、HCA_HQ314份放 入’加入作為觸媒的_.31份，在165t反應2小時後， 以MEK稀釋。得到之含鱗環氧樹脂溶液是淡黃色透明，不 揮“ 70/"月，黏度17〇〇mPa.s，實測環氧基當量彻忌 八Q. L基田垔>10000 g//eq•，碟含量3· 〇重量％，數量 平均刀子里1260。又’相對於環氧樹脂類⑷之環氧基i 當量，具有反應性官能基的化合物類（b)之官能基是〇·48 當量，理論環氧基當量是474g/eq.，相對於理論環氧基 當量，實測環氧基當量之比率是1〇4%。在< 3表示放入量 與放入比率、樹脂之性狀等。 比較例2 與實施例3同樣將HCA 209份、14_蔡酉昆⑽份放入， 其餘用與實施例3同樣之方法反應得到HCA_NQ。在此加入 YDF-ΠΟ 641份，作為觸媒的TPP 〇 36份，用與比較例工 同樣的方法反應，反應終止後，以mek稀釋。得到之含麟 環氧樹脂溶液是深褐色透明，不揮發分70%，清漆黏度 1500inPa.S，實測環氧基當量527g/eq.，羥基當量>1〇〇〇〇 g/eq·，磷含量3.0重量％，數量平均分子量1〇38。又， 相對於環氧樹脂類（a)之環氧基i當量，具有反應性官能基 的化合物類（b)之官能基是〇. 50當量，理論環氧基當量是 538g/eq. ’相對於理論環氧基當量，實測環氧基當量之比 323897 25 201241033 率是98%。在表3表示放入量與放入比率、樹脂之性狀等。 比較例3 與實施例3同樣將HCA 141份、1,4-萘醌1〇1份放入， 其餘用與實施例3同樣之方法反應得到hca-NQ。在此加入 YDPN-638 758份，作為觸媒的TPP0.24份，在165°C中 進行反應時，在反應開始1小時會凝膠化。因此不能進行 積層板評估。 比較例4 與實施例3同樣將HCA 154份、1，4-萘醌77份放入， 其餘用與實施例3同樣之方法反應得到HCA-NQ。在此加入 YDF-170 246 份、YDPN-638 523 份、作為觸媒的 TPP 0. 23 份，在165。(：中反應2小時，以MEK稀釋。得到之含磷環 氧樹脂溶液是深褐色透明，不揮發分，清漆黏度 1500mPa«s’實測環氧基當量311g/eq，羥基當量>1〇〇〇〇 g/eq· ’磷含量2. 2重量°/fl，數量平均分子量822。又，相 對於環氧樹脂類（a)之環氧基1當量，具有反應性官能基的 化合物類（b)之官能基是0.22當量，理論環氧基當量是302 g/eq. ’相對於理論環氧基當量，實測環氧基當量之比率 疋103%。在表3表示放入量與放入比率、樹脂之性狀等。 比較例5 與實施例3同樣將HCA 108份、1,4-萘醌80份放入， 其餘用與實施例3同樣之方法反應得到HCA-NQ。在此加入 EPPN-501H 833份、作為觸媒的TPP 0· 19份，在15(TC中 反應3小時後，以PGM/MEK混合溶劑稀釋。得到之含鐵學 323897 26 201241033 氧樹脂溶液是深褐色透明，不揮發分70%，清漆黏度 lOOOmPa’s，實測環氧基當量257g/eq.，羥基當量>1〇〇〇〇 g/eq. ’磷含量1. 5重量％，數量平均分子量796。又，相 對於環氧樹脂類（a)之環氧基丨當量，具有反應性官能基的 化合物類（b)之官能基是〇. 2〇當量，理論環氧基當量是255 g/eq.，相對於理論環氧基當量，實測環氧基當量之比率 是101%。在表3表示放入量與放入比率、樹脂之性狀等。 比較例6 與實施例3同樣將HCA 108份、1，4-萘醌80份放入， 其餘用與實施例3同樣之方法反應得到HCA-NQ。在此加入 ESN-375 833份、作為觸媒的TPP 0. 19份，在150°C中反 應6小時後，以PGM/MEK混合溶劑稀釋。得到之含磷環氧 樹脂溶液是深褐色透明，不揮發分7〇%，清漆黏度14〇〇mPa. 3’實測環氧基當量253运/69.，羥基當量>1〇〇〇〇这/叫.， 磷含置1. 5重量％，數量平均分子量892。又，相對於環氧 树月曰類（a)之環氧基1當量，具有反應性官能基的化合物類 (b)之官能基是0.20當量，理論環氧基當量是254 g/ 叫.，相對於理論環氧基當量，實測環氧基當量之比率是 99/«。在表3表示放入量與放入比率、樹脂之性狀等。 比較例7 與實施例7同樣，使用比較例i得到的含碟環氧樹脂 及丨〕ICY得到環氧樹脂硬化物。在表4表轉配比率與積層 板之評估結果。 比較例8 323897 27 201241033 與實施例7同梯，伯田 及DiCYim /吏較例2得到的含磷環氧樹脂 板之評二/。㈣硬化物。在表4表示摻配比率與積層 比較例9 與實施例7同樣，制比較例4得到的含磷環氧樹脂 及DKY得到環氧樹脂硬化物。在表4表示摻配比率與積層 板之評估結果。 比較例10 與實施例U同樣，使用比較例2得_含料氧樹 脂及齡557得到魏樹脂魏物。在表4表祕配比率 與積層板之評估結果。 比較例11 與實施例11同樣，使用比較例5得到的含㈣氧樹 脂及BRG-557 #到環氧樹脂硬化物。在表4表示掺配比率 與積層板之評估結果。 比較例12 與實加例11同樣，使用比較例6得到的含鱗環氧樹 脂及BRG_557得職氧购旨硬化物。麵4表祕配比率 與積層板之評估結果。 323897HO-A-OH (wherein A represents a aryl group and/or a triyl group having 6 to 20 carbon atoms, and η represents 0 or 1. Further, in the formula, R2 represents a hydrocarbon group having 1 to 6 carbon atoms. They may be the same or different, or may form a ring together with a phosphorus atom.) 323897 11 201241033 Further, these phosphorus-containing compounds may be 9, 10-dihydro-9-oxa-l-phosphonium-10 - an oxide (trade name HCA manufactured by Sanko Co., Ltd.) or a phosphorus compound having an active argon group directly bonded to a phosphorus atom such as diphenylphosphine, and an anthracene such as 1,4-benzoquinone or naphthoquinone And got it. About HCA-HQ is in Japan, JP-A-60-126293, HCA-NQ is in Japan, JP-A-61-236787, and PPQ is in zh.Obshch. Khim, 42(11), 2415-2418 (1972) A method of synthesizing is disclosed, but is not limited thereto, and a well-known method can be used. Examples of the compound (b) having a reactive functional group other than the phosphorus-containing phenol compound include, for example, hydroxybenzenes such as catechol, resorcinol, and hydroquinone. Phenols, binaphthols, trisphenols, bisphenol A, bisphenol F, bisphenol S, Shonol BRG-555 (Phenolic novolac resin manufactured by Showa Denko Co., Ltd.), cresol novolac resin, kiln Road inspection varnish resin, aryl-based varnish resin, bisphenol ring-containing phenol novolac resin, biphenyl aralkyl phenol resin, RESITOP TPM-100 (trihydroxyphenyl group manufactured by Qun Rong Chemical Industry Co., Ltd.) a methane type novolac resin), a compound having two or more phenolic hydroxyl groups in one molecule of an aralkyl naphthalenediol resin, etc., in 9,1 〇_dihydro-9-oxa-10-phosphanthene- Phosphorus compounds such as 10-oxide (trade name HCA, manufactured by Sanko Co., Ltd.) or diphenylphosphine, such as phosphorus compounds, which are directly bonded to active hydrogen groups, and arsenic, such as hexamethylene or ruthenium, Imidazole compounds and their salts, dicyandiamide, amine benzoin Aliphatic amines such as acid esters, diethylenediamine, diethylenetetramine, tetraethylenepentamine, isophthalamide, isophorone diamine, diamine-based diphenyl-based, diamine-based Diphenyl hydrazine, 323897 8 12 201241033 Aminoethyl ethyl amides, aromatic amines, terephthalic anhydride, trimellitic anhydride, tetrazoic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyl four An acid liver such as hydroxyphthalic anhydride, hexahydrophthalic anhydride, decyl hexahydrophthalic anhydride or SKNadic Methyl Anhydride may be used. The equivalent of 0.2 equivalents or less, more preferably 0.2 equivalents or less, is preferably used in an amount of 0.5 equivalent or less. The epoxy equivalent of the phosphorus-containing epoxy resin of the present invention is in the range of 60% to 95% of the theoretical epoxy equivalent of the formula 1, but is 70 °/. It is preferably 95% of the circumference, and more preferably 75% to 90%. When it is less than 60%, many difficult-to-capacitance phosphorus-containing phenol compounds remain, and solvent solubility may deteriorate. When it is larger than 95%, the viscosity reduction effect when it is used as an epoxy resin varnish becomes low. Further, the phosphorus-containing epoxy resin of the present invention is one equivalent of the epoxy group of the epoxy resin (a) represented by Formula 2, and the reactive functional group of the compound (b) having a reactive functional group is ruthenium. The reaction is carried out in the range of 10 equivalents to 0.94 equivalents, preferably from 0.2 equivalents to 0.70 equivalents, more preferably from 0.2 equivalents to 〇. (b) When the amount is less than 0.10 equivalent, the flame retardancy becomes insufficient, and when it exceeds 0.94, the varnish viscosity of the obtained phosphorus-containing epoxy resin becomes high. . The reaction temperature for obtaining the phosphorus-containing epoxy resin of the present invention is from 100 ° C to 25 (TC, more preferably 13 Torr. (: to 18 〇t, the reaction is markedly slow after 1 Torr). When it is carried out at 2503⁄4 or more, it is difficult to control in order to form a reaction in the range of 60% to 95% of the theoretical epoxy equivalent. Further, in the reaction for obtaining the phosphorus-containing epoxy resin of the present invention, it is necessary to use it. A reaction catalyst for promoting the reaction. As a catalyst capable of making horns 323897 13 201241033, examples thereof include phosphines such as triphenylphosphine and tris(2,5-dimethoxyphenyl)phosphine, and η-butyl. Four-stage scale salts such as triphenyl sulphate bromide and ethyl triphenyl stellate disc, 2-ethyl-4-methyl sputum, 2-phenyl sigma saliva, etc. Known conventional catalysts such as a quaternary ammonium salt such as a quaternary ammonium salt or a tetraethylammonium bromide, a tertiary amine such as triethylamine or benzyldidecylamine, but are not limited thereto. The amount of the catalyst used is preferably in the range of 0.005% to 1% based on the total amount of the phenol compound. The reaction of the epoxy resin with the phosphorus-containing compound can be insoluble. In the agent, 'may also be carried out in a solvent, and when it is carried out in a solvent, preferably in an aprotic solvent, as an aprotic solvent, for example, toluene, xylene, methanol, ethanol, 2- An alkane such as butanol, dialkyl ether, glycol ether, propylene glycol monodecyl ether or dioxane. These reaction solvents may be used singly or in combination of two or more types. The amount used is preferably 50% or less of the total weight of the reactants. Further, in the reaction of the phosphorus-containing epoxy resin of the present invention, the epoxy equivalent of the resin can be determined in the theoretical epoxy equivalent under the adjustment of the amount of the catalyst. From the range of 6 〇% to 95%, or the reaction temperature of δ weeks, the reaction in stages, etc., it is possible to use a known manufacturing method, and is not limited thereto. The phosphorus-containing epoxy resin composition of the present invention Although the above-mentioned phosphorus-containing epoxy resin is an essential component', other epoxy resins, epoxy resin hardeners, hardening accelerators, fillers, etc. may be contained as needed. Composition The ring gas resin used is as necessary * in addition to the ferulic oxide-containing resin of the present invention, in the range of the physical properties of the damage can be used and used in the synthesis of the ring-containing gas of the present invention: 323897 14 201241033 The same type of epoxy resin as the oxygen resin is not limited thereto. Further, these epoxy resins may be used in combination of two or more types. The epoxy resin which can be used as the phosphorus-containing epoxy resin composition of the present invention. Examples of the hardener include hydroxybenzenes such as catechol, resorcinol and hydroquinone, binaphthols, biphenols, trisphenols, bisphenol A, bisphenol F, double s, and two. Hydroxyphenyl decane, trihydroxyphenyl ethane, Sh〇n〇1 brg_555 (Phenolic novolac resin manufactured by Showa Denko Co., Ltd.), nonylphenol novolak resin, alkylphenol novolac resin, aralkylphenol phenolic aldehyde Varnish resin, diazine ring phenol novolak resin, phenyl aryl phenol resin, RESIT〇p TPM-100 (trihydroxyphenyl decane novolak resin manufactured by Qunrong Chemical Industry Co., Ltd.), in Fang a molecule of alkyl naphthalenediol resin a compound having two or more phenolic hydroxyl groups, an anthraquinone such as hexamethylene dioxime or anthraquinone, an imidazole compound and a salt thereof, dicyandiamide, an amine benzoate, a diethylenetriamine, and a tris Aliphatic amines such as ethylenetetramine, tetraethylenepentamine, m-xylylenediamine, isophoronediamine, diaminodiphenylnonane, diaminodiphenylsulfone, diaminoethylbenzene Aromatic amines, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, mercaptotetrahydrophthalic anhydride, hexahydrophthalic anhydride, mercaptohexahydrogen An acid anhydride such as phthalic anhydride or quinonedic acid anhydride may be used in combination with a conventionally known epoxy resin curing agent. The epoxy resin hardener is used in an amount of 1 equivalent to the epoxy group of the phosphorus-containing epoxy resin (c) which is an essential component of the phosphorus-containing epoxy resin of the present invention, and the functional group of the epoxy resin hardener is A range of from 1 equivalent to 1.3 equivalents is preferred, and more preferably from 2 equivalents to 9 equivalents. Further, when the fluidity, viscosity, and the like are adjusted, the physical properties of the 323897 15 201241033 phosphorus epoxy resin composition of the present invention are not impaired. The diluent is diluted in a reactive manner. A reactive diluent can be used. As a reactive diluent, it can be used as a non-reactive dilute 2-ethylhexyl glycidyl (tetra), phenyl'propyl glycidol, - condensed water, etc. Monofunctional, m-benzene-glycidol Jun, neopentyl glycol shrinkage + ] abundant water, etc., difunctional, glycerol poly 2 = 6-hexanediol dipyrene P〇_c coffeeether), tris(tetra)yl hydroglycolate coffee 01 glyceryl ether and other multifunctional Glycidyl ethers are used as: =: 〇il). Further, in the phosphorus-containing epoxy resin composition of the present invention, a hardening accelerator may be used as necessary. For example, phosphines, quaternary scale salts, and the like may be mentioned. Amines, quaternary ammonium salts, imidazole compounds, boron trifluoride complexes, 3-(3,4-dioxadiphenyl)-ι, ι-dimethylurea, monochlorophenyl -1,1-dimethylurea, 3-phenyl-1,1-dimethylurea, and the like. These hardening accelerators are based on the type of epoxy resin used, the type of epoxy resin curing agent used, the molding method, the curing temperature, and the required characteristics. The weight ratio is 〇·01% to the ring-tree t The range of 20% is preferably, more preferably 〇. 1% to J. The phosphorus-containing epoxy resin composition of the present invention can be blended with other thermosetting resins and thermoplastic resins without damaging the properties. For example, phenol resin, acrylic resin, petroleum resin, eucalyptus, white bean-flavored I-section resin, phenoxy resin, polyamine vinegar, polyacetate, polyamine, polyimine, polyamine醯imine, polyether oximine, polyether sulfone, poly woven, polyetheretherketone, polyphenylene sulfide, polyvinyl furfural, etc. 'but not limited to this' 323897 16 201241033 The carbon-containing epoxy resin of the present invention The composition may be replaced with an inorganic filler or an organic filler as necessary. Examples of the filler include: molten cerium oxide, crystalline cerium oxide, oxidized cerium, cerium hydride, aluminum hydroxide, talc, mica, carbon _, oxyhydroquinone, carbon _, cesium carbonate, barium sulfate, Nitriding, carbonaceous, carbon fiber, glass fiber, oxidized fiber, strontium aluminum fiber, strontium carbide fiber, polyester fiber, cellulose fiber, aromatic amide fiber, and the like. These fillers are preferably from 1% to 70% by weight based on the total weight of the resin composition. The ring-containing latex resin composition of the invention may be compounded with a decane coupling agent, an antioxidant, a mold release agent, an antifoaming agent, an emulsifier, a thixotropic agent, a lubricant, a flame retardant according to requirements. , nucleating agents such as pigments. These additives are preferably in the range of from 0.1% to 2% by weight based on the total weight of the resin composition. The phosphorus-containing epoxy resin composition of the present invention can be molded and cured in the same manner as a conventional epoxy resin composition to form a cured product. The molding method and the hardening method can be carried out in the same manner as the conventional epoxy resin composition. There is no need for an inherent method of the resin composition of the present invention. The phosphorus-containing epoxy resin composition of the present invention may be in the form of a laminate, a molded article, a binder, a coating film, a film or the like. The present invention is a phosphorus-containing epoxy resin having flame retardancy, and has excellent workability due to good impregnation to a substrate such as glass cloth, and flame retardancy or heat resistance of the cured product of the phosphorus-containing epoxy resin. Since it has good properties and good adhesion, it is judged to be applicable as a material for sealing materials, steel foil laminates, insulating coatings, flame retardant coatings, composite materials, and insulating flame retardant adhesives used in electrical and electronic parts, 323897 17 201241033. (Embodiment) Next, an embodiment of the present invention is presented, but the scope of the present invention is not limited to the embodiments. Especially when there is no special discussion, "parts" means heavy parts. Further, the analysis method and measurement method are as follows. Epoxy equivalent: according to JIS K7236. The tester base equivalent: THF containing 4% methanol was added to the sample, and 10% tetrabutylammonium hydroxide was added thereto, and the absorbance at a wavelength of 400 nm to 250 nm was measured using an ultraviolet-visible spectrophotometer. Using the calibration curve obtained by the same measurement method, the phenolic hydroxyl group was determined as the weight of the equivalent amount of the hydroxyl group. Nonvolatiles: JIS K7235-1986 Number average molecular weight: The molecular weight distribution was measured using a gel permeation chromatography analyzer (HLC-8220GPC manufactured by Tosoh Co., Ltd.), and converted by a calibration curve obtained by standard polystyrene. Filling content: sulfuric acid, hydrochloric acid, and peroxyacid are added to the sample, heated to wet ash, and all phosphorus atoms are regarded as orthophosphoric acid. The erbium salt and the indium salt are reacted in an acidic solution of sulfuric acid, and the absorbance of the formed cucurbit acid complex at 420 nm is measured, and the content of the phosphorus atom is determined by a previously prepared calibration curve. Said. The phosphorus content of the laminate is expressed as the content of the resin component relative to the laminate. Varnish viscosity: A cone-and-plate type viscometer (manufactured by Tokimec Co., Ltd.) was used, and a rotator was measured at a rotation number of 10 rpm using a standard cone (1° 34') at 25 ° C. 323897 18 8 201241033 Infrared Absorption spectrum: Fourier transform method (KBR) was measured using a Fourier transform infrared spectrophotometer (Spectum One manufactured by Perkinelmer Co., Ltd.) Glass transition temperature: expressed in a differential scanning calorimeter (sn NanoTechnology) The DSC extrapolation temperature measured by the EXSTAR6000 DSC6200) at a temperature rise of 10 °C/min. Flammability: Tested on 5 test pieces according to UL94 (Safety Certification Specification of Underwriters Laboratories Inc.) The total time of the flame combustion duration after the second and second contact flames (5 contact flames for each of the total of 10 times) is expressed in seconds. Copper foil peel strength and interlayer peel strength: according to JIS C6481. -288 test: Test was carried out according to IPC ΤΜ-650 at 288 ° C. Example 1 with stirring device, thermometer, cooling tube, nitrogen inlet tube In a four-piece glass separable flask experimental apparatus, a double-type j-type epoxy resin (trade name YDF_17〇 manufactured by Xinyitie Chemical Co., Ltd., epoxy equivalent 170 g/eq·) 687 parts was added to '1' 〇-(2, 5-Dihydroxyphenyl)-i〇H-9-oxa-10-phosphaphenanthrene-10-oxide (trade name HCA-HQ, manufactured by Sanko Co., Ltd., melting point 256°C, dish The content is 9.6 wt%, and the hydroxyl equivalent weight is 162 g / eq.) 314 parts. Here, trisylphosphine (hereinafter referred to as hydrazine) as a catalyst is added, and 0.6 part of the reaction is carried out at 165 ° C for 4 hours, then 'incorporation of thiol B The base ketone (hereinafter referred to as MEK) is diluted. The obtained scaly epoxy resin solution is light yellow transparent 'nonvolatile content 70%, varnish viscosity 510 mPa. s, measured ring gas base equivalent 301 g / eq. 'hydroxy equivalent 850 g/eq., lin content 3. 〇 weight%, 323897 19 201241033 number average molecular weight 587. Further, (d) 1 equivalent of ring, compound having reactive functional group: oxy equivalent 'theoretical epoxy equivalent is -2 == Equivalent 'The ratio of the measured epoxy equivalents is 64X. Table t shows the ratio of = to the ratio, the properties of the resin, etc. Example 2 In the same manner as in Example 1, 687 parts of YDF-17〇, HCA-Hq251 parts, phenol novolac, and varnish type resin (trade name Shonol BRG-557, manufactured by Showa Denko Co., Ltd., phenolic hydroxyl equivalent 1 〇 5 g/eq) 63 parts were added, and TPP 〇. 06 parts as a catalyst was added, and the reaction was carried out in the same manner as in Example i, and after the reaction was terminated, it was diluted with MEK. The obtained phosphorus-containing epoxy resin solution is light yellow transparent, non-volatile 70%, varnish viscosity 550 mPa.s, measured epoxy equivalent 365 g/eq., hydroxyl equivalent 1200 g/eq., phosphorus content 2.4% by weight The number average molecular weight is 619. Further, the compound (b) having a reactive functional group with respect to the epoxy group (a) has a functional group of 0.33 equivalent, and the theoretical epoxy equivalent is 527 g/eq. The ratio of the measured epoxy equivalents was 69% with respect to the theoretical epoxy equivalent. Table i shows the amount of insertion and the ratio of the input, the properties of the resin, and the like. Example 3 In a four-port separable flask experimental apparatus equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen introduction tube, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxidation was placed. (product name HCA of Sanko Co., Ltd.) Phosphorus content 14.2 weight W209 parts and 1,4-naphthoquinone (water content of Kawasaki Chemical Industry Co., Ltd. 3.4 weight «150 parts by weight, 490 parts toluene, 323897 20 8 201241033 After 30 minutes of hunger, the surface was removed from the system and the reaction was carried out at 110 C for 90 minutes. 'Toluene was removed to obtain 1〇_(14_dioxophthalene 10H-9-oxa-10-phosphinophen-1 〇_oxide (hca nq). Here, 641 parts of ydf_17〇 were added as TAP 触. 〇 9 parts of the catalyst, and reacted in the same manner as in Example i, and after the reaction was terminated, it was diluted with MEK.重量重量。 Phosphorus epoxy resin solution is a dark brown transparent 'nonvolatiles 7〇%, varnish viscosity 440 mpa. s, measured epoxy equivalent 409 g / eq., hydroxyl equivalent Π 50 g / eq., phosphorus content 3. 0% by weight a number average molecular weight of 6 〇 3. Further, having 1 equivalent of an epoxy group of the epoxy resin (a), having a reactive functional group The functional group of the compound (b) is 〇.5 〇 equivalent, the theoretical epoxy equivalent is 538 g/eq., and the ratio of the measured epoxy equivalent is 76% with respect to the theoretical epoxy equivalent. In the same manner as in Example 3, 141 parts of HCA and 101 parts of 1,4-naphthoquinone were placed in the same manner as in Example 3, and the other reaction was carried out in the same manner as in Example 3 to obtain HCA-. NQ. Here, 758 parts of varnish-type epoxy resin (trade name YDPN-638 manufactured by Nippon Steel Chemical Co., Ltd., epoxy equivalent 175 g/eq.), and TPP 0·02 serving as catalyst are added. After reacting at 165 ° C for 4.5 hours, it was diluted with MEK. The obtained phosphorus-containing epoxy resin solution was dark brown transparent, non-volatile 70%, varnish viscosity 130 〇 mpa.s, measured epoxy equivalent 292 g / eq a hydroxyl equivalent of 3600 g/eq., a phosphorus content of 2.0% by weight, a number average molecular weight of 884. Further, a compound having a reactive functional group (1) with respect to 1 equivalent of the epoxy group of the epoxy resin (a) The functional group is 〇·3〇 equivalent, the theoretical epoxy equivalent is 318g/eq·, and the epoxy equivalent is measured as 32389 relative to the theoretical epoxy equivalent. 7 21 201241033 The ratio of the amount is 疋92%. Table 1 shows the amount of insertion and the ratio of the input, the properties of the resin, etc. Example 5 In the same manner as in Example 3, 108 parts of HCA and 80 parts of 1,4-naphthoquinone were placed. The other reaction was carried out in the same manner as in Example 3 to obtain hca-NQ. Here, a triphenylsulfonium-type epoxy resin (trade name EPPN-501H, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of 167.2 g/eq) was added. .833 parts, 0.02 parts of TPP as a catalyst at 150. (6: After 6 hours of reaction, it was diluted with propylene glycol monomethyl hydrazine (hereinafter referred to as PGM)/MEK mixed solvent. The obtained phosphorus-containing epoxy resin solution was dark brown transparent, non-volatile content 7 %, varnish viscosity 54 〇 mPa .s, measured epoxy equivalent 239 g / eq., hydroxyl equivalent 4 〇〇〇 g / e (j ·, dish 1.5% by weight, number average molecular weight 628. Also, relative to the ring S (a) ring 1 equivalent of the oxy group, the functional group of the compound resin having a reactive functional group is 0.200 equivalent, and the theoretical epoxy equivalent is 255 g/e _(b) For the theoretical epoxy equivalent, the ratio of the measured equivalent of the epoxy group is 9=, phase table 1 shows the ratio of the amount of the addition to the ratio of the rose, the properties of the resin, etc. In the same manner as in the example 3, HCA 1〇8 parts, 丨, 4_naphthoquinone 8 parts are used in the same manner as in the example 3. In the same manner as in Example 3, HCA State Q was obtained. In addition, a naphthol aralkyl type epoxy resin (Nippon Steel Chemical Co., Ltd. ESN-375, epoxy equivalent 167 g/eq.) 833份 、 〇 〇 份 A A A A 在 A 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在It is dark brown/1⁄23⁄4 non-volatile 70% 'varnish viscosity 7〇〇mPa.s, measured epoxy 逯 逯 ,, 323897 reserves 239g 22 201241033 /eq•, equivalent shed ^., phosphorus content U% by weight, ❹ : average molecular weight 716. Further, with respect to the epoxy group of the epoxy resin (4), the functional group of the compound (8) having a reactive functional group is a: amount, and the theoretical epoxy equivalent is 254 g/eq. The ratio of the measured epoxy equivalents was 94% with respect to the theoretical epoxy amount. Table 1 shows the put-in ratio of the dial, the properties of the resin, etc. /, Example 7 The content obtained in Example 1 In the scale epoxy resin, a hardening accelerator of dicyandiamide (DICY, active hydrogen equivalent: 21 g/eq) was blended in a solid amount shown in Table 2 to obtain a resin composition, which was dissolved in the ancestors as a resin varnish. The epoxy resin varnish impregnated with glass cloth (WEA 116E1〇6S136 Ridong Textile Co., Ltd. 胄 thickness l·lmm) was dried in a hot air circulating oven of 15 c for 10 minutes to obtain a prepreg. The prepreg overlaps with the steel shovel (3EC-1H Mitsui Metal Mining Co., Ltd. thickness 35wm) Vacuum pressing at 2 MPa was carried out under the conditions of 130 txl 5 minutes + 170 ΐχ 70 minutes to obtain a laminate having a thickness of 5 mm. The results of the evaluation of the blending ratio and the laminate were shown in Table 2. Example 8 Same as Example 7, The phosphorus-containing epoxy resin obtained in Example 2 and DICY' were used to obtain a cured epoxy resin. Table 2 shows the results of evaluation of the blend ratio and the laminate. Example 9 The same procedure as in Example 7 was carried out using Example 3. Phosphorus-containing epoxy resin and I) ICY 'obtained epoxy hardened material. Table 2 shows the results of the evaluation of the blending ratio and product 323897 23 201241033 laminate. Example 10 In the same manner as in Example 7, the phosphorus-containing gas-containing resin and the indophenol novolak-type epoxy resin obtained in Example 3 (manufactured by Nippon Steel Chemical Co., Ltd., trade name YDCN-704 'epoxy equivalent 209 g) were used. /eq.) and DICY, to obtain an epoxy resin cured product. Table 2 shows the blending ratio and the evaluation results of the laminate. Example 11 In the same manner as in Example 7, the phosphorus-containing epoxy resin obtained in Example 4 and DICY were used to obtain a cured epoxy resin. Table 2 shows the results of the evaluation of the blending ratio and the laminate. Example 12 In the same manner as in Example 7, a phosphorus-containing epoxy resin obtained in Example 3 and BRG-557 were used to obtain a prepreg. Four prepregs and copper foils were obtained (3EC-11I Mitsui Metals Mining Co., Ltd. thickness 35ym). At 130 〇乂 15 minutes + 19 〇. (:><> Vacuum pressurization of 21^& under 80 minutes of temperature conditions to obtain a laminate having a thickness of 0.5 mm. Table 2 shows the results of the evaluation of the blend ratio and the laminate. Example 13 In the same manner as in Example 12, the phosphorus-containing epoxy resin obtained in Example 5 and BRG-557 were used to obtain a cured epoxy resin. Table 2 shows the results of evaluation of the blending ratio and the laminate. Example 14 Same as Example 12 The phosphorus-containing epoxy tree 323897 24 201241033 grease obtained in Example 6 and BRG_557 were used to obtain an epoxy resin cured product. The results of the evaluation of the blending ratio and the laminate were shown in Table 2. Comparative Example 1 The same as Example 1, the same as Example 1. 687 parts, HCA_HQ314 parts were placed in '.31 parts as catalyst, and after 2 hours of reaction at 165t, diluted with MEK. The obtained scaly epoxy resin solution was light yellow transparent, not "70/" , viscosity 17 〇〇 mPa.s, measured epoxy equivalent equivalent of eight Q. L jitian 垔 > 10000 g / / eq •, disc content 3 · 〇 weight%, the average number of knives 1260. Also 'relative to Epoxy group (4) epoxy group i equivalent, compound having reactive functional group (b) The functional group is 〇·48 eq., and the theoretical epoxy equivalent is 474 g/eq., and the ratio of the measured epoxy equivalent is 1〇4% with respect to the theoretical epoxy equivalent. Into the ratio, the properties of the resin, etc. Comparative Example 2 In the same manner as in Example 3, HCA 209 parts and 14_Cai Yukun (10 parts) were placed, and the other reaction was carried out in the same manner as in Example 3 to obtain HCA_NQ. Here, YDF-ΠΟ 641 parts were added. As a catalyst, TPP 〇 36 parts, reacted in the same way as the comparative routine, and after the reaction was terminated, it was diluted with mek. The obtained epoxy resin solution was dark brown transparent, non-volatile 70%, varnish viscosity 1500 inPa .S, measured epoxy equivalent weight 527 g / eq., hydroxyl equivalent weight > 1 〇〇〇〇 g / eq ·, phosphorus content 3.0% by weight, number average molecular weight 1 〇 38. In addition, relative to epoxy resin (a The epoxy group i equivalent, the functional group of the compound having the reactive functional group (b) is 〇. 50 equivalents, and the theoretical epoxy equivalent is 538 g/eq. 'Compared to the theoretical epoxy equivalent, the measured epoxy The base equivalent ratio 323897 25 201241033 rate is 98%. Table 3 shows the amount of insertion and placement ratio The properties of the resin, etc. Comparative Example 3 In the same manner as in Example 3, 141 parts of HCA and 1 part of 1,4-naphthoquinone were placed, and the same reaction was carried out in the same manner as in Example 3 to obtain hca-NQ. YDPN-638 758 parts, 0.24 parts of TPP as a catalyst, gelled at 165 ° C for 1 hour after the start of the reaction. Therefore, the evaluation of the laminate cannot be performed. Comparative Example 4 In the same manner as in Example 3, 154 parts of HCA and 77 parts of 1,4-naphthoquinone were placed, and the same reaction as in Example 3 was carried out to obtain HCA-NQ. Here, 246 parts of YDF-170, 523 parts of YDPN-638, and TPP 0. 23 parts as a catalyst were added at 165. (: 2 hours of reaction, diluted with MEK. The obtained phosphorus-containing epoxy resin solution is dark brown transparent, non-volatile, varnish viscosity 1500 mPa «s' measured epoxy equivalent 311 g / eq, hydroxyl equivalent > 1 〇〇 〇〇g/eq· 'phosphorus content 2.2 deg/fl, number average molecular weight 822. Further, a compound having a reactive functional group with respect to 1 equivalent of the epoxy group of the epoxy resin (a) (b) The functional group is 0.22 equivalents, and the theoretical epoxy equivalent is 302 g/eq. 'The ratio of the measured epoxy equivalents is 疋103% with respect to the theoretical epoxy equivalent. Table 3 shows the loading and placing ratios. The properties of the resin, etc. Comparative Example 5 In the same manner as in Example 3, 108 parts of HCA and 80 parts of 1,4-naphthoquinone were placed, and the other reaction was carried out in the same manner as in Example 3 to obtain HCA-NQ. EPPN- was added thereto. 501H 833 parts, TPP 0·19 parts as a catalyst, diluted in 15 (TC for 3 hours, diluted with PGM/MEK mixed solvent. The obtained iron containing 323897 26 201241033 Oxygen resin solution is dark brown transparent, non-volatile 70%, varnish viscosity lOOOOmPa's, measured epoxy equivalent 257g / eq., hydroxyl equivalent > 1〇〇〇〇 g /eq. 'Phosphorus content 1.5% by weight, number average molecular weight 796. Further, the functional group of the compound (b) having a reactive functional group is equivalent to the epoxy group equivalent of the epoxy group (a) 〇 2 〇 equivalent, the theoretical epoxy equivalent is 255 g / eq., compared to the theoretical epoxy equivalent, the ratio of the measured epoxy equivalent is 101%. Table 3 shows the amount and ratio, resin Comparative Example 6 In the same manner as in Example 3, 108 parts of HCA and 80 parts of 1,4-naphthoquinone were placed, and the other reaction was carried out in the same manner as in Example 3 to obtain HCA-NQ. Here, ESN-375 833 was added. A portion of TPP 0.11 as a catalyst was reacted at 150 ° C for 6 hours, and then diluted with a PGM/MEK mixed solvent to obtain a phosphorus-containing epoxy resin solution which was dark brown transparent and had a nonvolatile content of 7 % by weight. The varnish viscosity is 14 〇〇 mPa. 3' measured epoxy equivalent 253 liters / 69., hydroxyl equivalents > 1 〇〇〇〇 this / called., phosphorus containing 1. 5 wt%, number average molecular weight 892. The functional group of the compound (b) having a reactive functional group is 0.20 equivalent with respect to 1 equivalent of the epoxy group of the epoxy resin cerium (a), theoretical epoxy The equivalent is 254 g/min., and the ratio of the measured epoxy equivalent is 99/« with respect to the theoretical epoxy equivalent. Table 3 shows the amount of loading and the ratio of the input, the properties of the resin, etc. Comparative Example 7 and implementation In the same manner as in Example 7, the epoxy resin containing the epoxy resin and the oxime ICY obtained in Comparative Example i was used to obtain a cured epoxy resin. Table 4 shows the results of the evaluation of the blending ratio and the laminate. Comparative Example 8 323897 27 201241033 In the same manner as in Example 7, the evaluation of the phosphorus-containing epoxy resin sheet obtained by Bertian and DiCYim / 吏 Comparative Example 2. (4) Hardened matter. Table 4 shows the blending ratio and the laminated layer. Comparative Example 9 In the same manner as in Example 7, the phosphorus-containing epoxy resin obtained in Comparative Example 4 and DKY were obtained to obtain a cured epoxy resin. Table 4 shows the results of the evaluation of the blending ratio and the laminate. Comparative Example 10 In the same manner as in Example U, a resin resin was obtained by using the oxygen-containing resin of Comparative Example 2 and the age of 557. Table 4 shows the match ratio and the evaluation results of the laminate. Comparative Example 11 In the same manner as in Example 11, the (tetra)oxygen-containing resin and BRG-557# obtained in Comparative Example 5 were used to obtain an epoxy resin cured product. Table 4 shows the results of the evaluation of the blending ratio and the laminate. Comparative Example 12 In the same manner as in the actual example 11, the scaly epoxy resin obtained in Comparative Example 6 and the BRG_557 were used as the cured product. Face 4 table match ratio and evaluation results of laminates. 323897
2S 201241033 表1 實施例I 實施例2 實施例3 實施例4 實施例5 資施例6 環氧樹脂類(a) YDF-170 重量份 687 687 641 YDPN-638 重*份 758 EPPN-501H 重量份 833 ESN-375 重苷份 833 反應 性官 能基 類(b) 含磷酚化合物 HCA-HQ 重量钤 314 251 含磷酚化合物之調整 HCA 重量扮 209 141 108 106 1,4-萘& 重量份 150 101 80 80 BRG-557 重f扮 63 相對於環氡樹脂類(a)之環氧基1當量，具有 反應性官能基的化合物類（b)之官能基當量 0.48 0.53 0.50 0.30 0.20 0.20 觸媒 TPP 重量份 0.06 ο.οβ 0.09 0.02 0.02 0.02 反應條件 溫度 165 165 165 165 150 150 時問 h 4.0 4.0 4.0 4.5 β.Ο 6.0 環氡基當量 實測值 i/eq. 301 365 409 292 239 239 理論值 g/eq. 474 527 53β 3ia 255 2S4 實測值/理論值 % 64 69 7β 92 94 94 羥基當量 β/eq- 850 1200 1750 3600 4000 4000 含磷量 % 3.0 2.4 3.0 2.0 1.5 1.5 清漆黏度 mPa*s 510 550 440 1300 540 700 數量乎均分子量 587 619 603 884 628 71β 表2 實施例7 實施例8 實施例9 實施例10 實施例11 實施例t2 實施例13 實施例H 主劑 實施例1 重量份 100 實施例2 重量份 too 實施例3 重量份 100 70 ΐ00 實施例4 重量份 100 實施例5 重量份 100 實施例β 重量份 100 YDCN-704 重量扮 30 硬化剖 DICY 重量份 2.1 2.0 2.0 2.9 3.3 BRG-557 重量扮 20 4t 41 硬化劑/主劑 0.31 0.35 0.38 0.65 0.4Θ 0_7β 0.94 0.94 觸媒 2E4MZ phr 0.20 0.15 1.00 0.10 0.00 0.20 0.10 0.05 组成物填含量 重量1 2.9 2.3 2.9 2.3 2.1 2.5 1.1 1.1 玻璃轉移溫度 120 125 128 152 182 116 174 165 阻燃性 UL-94 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 合计時間 sec 30 26 27 39 38 21 48 43 射離強度 銅箔 kN/m 1.9 1.8 .2.0 1.5 1.6 1.8 1.0 1.3 層間 kM/m 2.4 IX 2.0 t.O 0.8 2.0 0.8 0.9 T-288試驗 min >βο >60 >60 >60 >60 >60 >60 >60 29 323897 201241033 表3 比較例2 比较讲3 比較俱4 比较拥5 比较偁β YDM70 重4扮 687 641 240 環氧樹庙類(a) Υ〇ΡΝ-β3Β 史量份 m $23 ΕΡΡΜ-501Η 史量份 633 ESN-375 重量扮 833 反應 含堪盼化合物 HCA-HQ 重量份 314 含填扮化合物之調整 HCA &量'份 20d 141 154 108 108 12. S 铤基 1,4-萘醚 重量份 1S0 101 77 80 80 類(b) | 8RQ-557 重量份 相封ίί 反應 ‘環氧樹脂頰(a)之環咚基1當量 _者&基的化合物類(b)之官基當4 0.4B 0.50 0.30 0.22 0.20 0.20 觸媒 ΤΡΡ 史量份 0.31 0.36 0.24 0,23 0.19 0.19 反應條件 溫度 X 165 165 165 1β5 1$0 150 時間 h 2.0 2,0 t.O 2.0 3.0 3.0 實測值 ϊ/β〇. 493 527 無法測定 311 257 253 環氧基當量 理饴值 */eq. 474 538 31丨 302 255 254 實測伹/理请值 % 104 98 - 103 101 99 羥基當量 β/叫 >10000 >10000 無法測定 >10000 >10000 >10000 含磷量 % 3.0 3.0 無法測定 2.2 1.S 1.5 清漆黏度 mP··* 1700 1500 無法測定 1500 1000 1400 教量乎均分子量 1260 1038 無法測定 822 790 892 表4 比較例7 比較例8 比較例9 比較例ίο 比較供11 比較例12 主谢 比較例1 重量份 100 比較例2 重量份 100 100 比較例4 重量份 100 比較例5 重量份 100 比較例6 重量份 100 硬化« 0ICY t量份 2.1 2.0 3.4 BRQ-557 重量份 20 41 41 硬化劑/主劑 0.50 0.50 0.50 0.98 1.01 0.99 觸媒 2E4MZ phr 0.50 1.00 0.08 0.20 0.13 0.05 组成物磷含量 重量％ 2.9 2.9 2.1 2.5 1·1 1.1 玻璃轉移溫度 115 126 135 108 169 161 性 UL-94 ν-α V-0 V-0 V-0 V-1 Y-1 合計時《 sec 36 38 35 30 73 60 制離試驗 銅箔 kN/m 1.9 2.0 1.6 1.9 1.0 1,3 層問 kN/m 2.5 2·1 1.1 2.1 0.8 0.9 T-288試驗 min 20 24 30 >60 >60 >Β0 如表1之實施例1至實施例6所示，本發明之含磷環 氧樹脂，藉由末端環氧基與末端酚性羥基共存，與先前技 術的比較例1至比較例6相比較，數量平均分子量較低， 環氧樹脂清漆黏度低。因此，對玻璃布有良好的含浸性， 作業性優異。再者，如實施例4所示，在比較例3所示以 先前技術係有合成困難，然在環氧樹脂中只使用多官能環 323897 30 ⑧ 201241033 ==環氧樹脂也可能合成，此之分子量或清漆黏 度並不比以在之含磷環氧樹脂遜色。 ' 如表2的實補7至實施例Η勘，在本發明 .η::中摻配環氧樹脂硬化劑經硬化的環氧樹脂硬化 使用以往的含璘環氧樹脂的情形相比不只玻璃轉 移溫度及耐熱可信賴度高，在阻燃性方面也優良。 [產業上的可能利用] 磷環氧樹脂比以往之含碟環氧樹脂，因為 良好，作業性優良。故對玻璃布等基材之含浸性 删含—氧樹脂硬化物與以往之含填環氧 糾曰相*，玻_移㈣高， 。 【圖式簡單說明】 …r生A接者f生也優艮 Ϊ 21:在實施例3得到之含墙環氧樹脂之GPC圖。 r 實施例3得到之含麟環氧樹脂之1R圖° 【主要疋件符號說明】 無 3238972S 201241033 Table 1 Example I Example 2 Example 3 Example 4 Example 5 Example 6 Epoxy resin (a) YDF-170 parts by weight 687 687 641 YDPN-638 weight * part 758 EPPN-501H parts by weight 833 ESN-375 Residues 833 Reactive functional groups (b) Phosphorus-containing phenol compounds HCA-HQ Weight 钤 314 251 Adjustment of phosphorus-containing phenol compounds HCA Weights 209 141 108 106 1,4-naphthalene & Parts by weight 150 101 80 80 BRG-557 Heavy f dressing 63 1 equivalent of the epoxy group of the cyclic oxime resin (a), the functional group equivalent of the compound (b) having a reactive functional group 0.48 0.53 0.50 0.30 0.20 0.20 Catalyst TPP Parts by weight 0.06 ο.οβ 0.09 0.02 0.02 0.02 Reaction conditions Temperature 165 165 165 165 150 150 Time h 4.0 4.0 4.0 4.5 β.Ο 6.0 Cyclodecyl equivalents measured i/eq. 301 365 409 292 239 239 Theoretical value g/ Eq. 474 527 53β 3ia 255 2S4 measured value/theoretical value % 64 69 7β 92 94 94 hydroxyl equivalent β/eq- 850 1200 1750 3600 4000 4000 Phosphorus content % 3.0 2.4 3.0 2.0 1.5 1.5 Varnish viscosity mPa*s 510 550 440 1300 540 700 Sub-amount 587 619 603 884 628 71β Table 2 Example 7 Example 8 Example 9 Example 10 Example 11 Example t2 Example 13 Example H Main agent Example 1 Parts by weight 100 Example 2 Parts by weight Too Example 3 parts by weight 100 70 ΐ00 Example 4 Parts by weight 100 Example 5 Parts by weight 100 Example β Parts by weight 100 YDCN-704 Weight 30 Hardened DICI 2.19% 2.0 2.9 3.3 BRG-557 Weight 20 4t 41 Hardener /Main agent 0.31 0.35 0.38 0.65 0.4Θ 0_7β 0.94 0.94 Catalyst 2E4MZ phr 0.20 0.15 1.00 0.10 0.00 0.20 0.10 0.05 Composition filling content Weight 1 2.9 2.3 2.9 2.3 2.1 2.5 1.1 1.1 Glass transition temperature 120 125 128 152 182 116 174 165 Resistance Flammability UL-94 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 Total time sec 30 26 27 39 38 21 48 43 Injection strength copper foil kN/m 1.9 1.8 .2.0 1.5 1.6 1.8 1.0 1.3 Inter-layer kM/m 2.4 IX 2.0 tO 0.8 2.0 0.8 0.9 T-288 test min >βο >60 >60 >60 >60 >60 >60 >60 29 323897 201241033 Table 3 Comparative Example 2 ratio Compared with 3, more than 4, more than 5, more 偁β YDM70, heavy 4, 687, 641, 240, epoxy tree temple (a) Υ〇ΡΝ-β3Β, historical quantity m $23 ΕΡΡΜ-501Η historical quantity 633 ESN-375 weight dress 833 Reaction containing compound HCA-HQ parts by weight 314 Adjusted HCA & amount 'parts 20d 141 154 108 108 12. S decyl 1,4-naphthyl ether parts 1S0 101 77 80 80 class (b) 8RQ-557 parts by weight ίί Reaction 'Ethylene epoxy (a) ring 咚 1 equivalent _ 者 & base compound (b) 官 4 4 0.4B 0.50 0.30 0.22 0.20 0.20 Catalyst ΤΡΡ Historical quantity 0.31 0.36 0.24 0,23 0.19 0.19 Reaction temperature X 165 165 165 1β5 1$0 150 Time h 2.0 2,0 tO 2.0 3.0 3.0 Measured value ϊ/β〇. 493 527 Unable to measure 311 257 253 Epoxy equivalent饴 * * / eq. 474 538 31 丨 302 255 254 measured 伹 / value % 104 98 - 103 101 99 hydroxyl equivalent β / called > 10000 > 10000 can not be measured > 10000 > 10000 > 10000 Phosphorus % 3.0 3.0 Cannot be measured 2.2 1.S 1.5 Varnish viscosity mP··* 1700 150 0 Unable to measure 1500 1000 1400 Teaching average molecular weight 1260 1038 Unable to measure 822 790 892 Table 4 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example ίο Comparison for 11 Comparative Example 12 Main Comparison Example 1 Parts by Weight 100 Comparative Example 2 Weight Parts 100 100 Comparative Example 4 Parts by weight 100 Comparative Example 5 Parts by weight 100 Comparative Example 6 Parts by weight 100 Hardening « 0ICY t parts 2.1 2.0 3.4 BRQ-557 Parts by weight 20 41 41 Hardener / main agent 0.50 0.50 0.50 0.98 1.01 0.99 Touch Medium 2E4MZ phr 0.50 1.00 0.08 0.20 0.13 0.05 Composition phosphorus content wt% 2.9 2.9 2.1 2.5 1·1 1.1 Glass transition temperature 115 126 135 108 169 161 UL-94 ν-α V-0 V-0 V-0 V- 1 Y-1 combined time "sec 36 38 35 30 73 60 separation test copper foil kN / m 1.9 2.0 1.6 1.9 1.0 1,3 layer kN / m 2.5 2 · 1 1.1 2.1 0.8 0.9 T-288 test min 20 24 30 > 60 > 60 > Β 0 As shown in Example 1 to Example 6 of Table 1, the phosphorus-containing epoxy resin of the present invention coexists with a terminal phenolic hydroxyl group by a terminal epoxy group, and the prior art Comparison of Comparative Example 1 to Comparative Example 6 Lower average molecular weight, low viscosity epoxy resin varnish. Therefore, it has good impregnation property to glass cloth, and it is excellent in workability. Further, as shown in Example 4, it was difficult to synthesize in the prior art as shown in Comparative Example 3, but only a polyfunctional ring was used in the epoxy resin. 323897 30 8 201241033 == Epoxy resin may also be synthesized. The molecular weight or varnish viscosity is not inferior to that of the phosphorus-containing epoxy resin. As shown in Table 2, from the supplement 7 to the example, in the present invention, η:: blended with an epoxy resin hardener, the hardened epoxy resin is hardened, and the conventional tantalum-containing epoxy resin is used instead of glass. The transfer temperature and heat resistance are high, and the flame retardancy is also excellent. [Industrial use] Phosphorus epoxy resin is superior to conventional epoxy resin, and it is excellent in workability. Therefore, the impregnation property of the substrate such as glass cloth is removed. The cured product of the oxygen-containing resin and the conventional epoxy-containing entangled phase* are glass-shifted (four) high. [Simple description of the drawing] ...r raw A picker f is also excellent Ϊ 21: GPC chart of the wall-containing epoxy resin obtained in Example 3. r 1R diagram of the lining epoxy resin obtained in Example 3 [Description of main components] No 323897