TW201125838A - Polyhydroxy compound, method for producing the same and epoxy resin composition and cured product thereof - Google Patents

Polyhydroxy compound, method for producing the same and epoxy resin composition and cured product thereof Download PDF

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TW201125838A
TW201125838A TW099128274A TW99128274A TW201125838A TW 201125838 A TW201125838 A TW 201125838A TW 099128274 A TW099128274 A TW 099128274A TW 99128274 A TW99128274 A TW 99128274A TW 201125838 A TW201125838 A TW 201125838A
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group
amine
resin
carbon atoms
epoxy resin
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TW099128274A
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Chinese (zh)
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TWI510454B (en
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Masaki Omura
Masashi Kaji
Kazuhiko Nakahara
Hisashi Yamada
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Nippon Steel Chemical Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/74—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
    • C07D333/18—Radicals substituted by singly bound hetero atoms other than halogen by sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Epoxy Resins (AREA)
  • Indole Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)

Abstract

The invention can provide a polyhydroxy compound containing an amino group or an imide that is applied to a cured agent, a modifier and an intermediate of an epoxy resin composition yielding a cured product excellent in flame retardance, high heat resistance, humidity resistance, and excellent high adhesion between dissimilar materials. More particularly, the polyhydroxy compound containing the amino group can be represented by the following common formula (1) and can be prepared by reacting 0.05 to 1.5 mole of an aromatic amine and an aldehyde with respect to 1 mole of a phenol ring within a phenol. The polyhydroxy compound containing imide group can be produced by reacting the polyhydroxy compound containing the amino group with dicarboxylic acid ahhydride to perform imidization for the amino group. In the formula, X is a direct bonding, -O-, -S-, -SO2-, -CO-, or a divalent hydrocarbon group; and the mean value of m is 0.05 to 1.5.

Description

201125838 六、發明說明： 【發明所屬之技術領域】 本發明有關作爲環氧樹脂的硬化劑、改性劑（ reforming agent)有用的多元羥基化合物，經使用彼等之 環氧樹脂組成物以及其硬化物，而很適合使用爲印刷電路 板、半導體密封（semi-conductor sealing)等的電氣電子 領域的絕緣材料、塗層材料（coating material)以及複合 材料（composite material)等的主材樹脂（base resin) 者。 【先前技術】 環氧樹脂係工業上在廣泛的用途上所使用者，惟其性 能要求（performance requirement)則愈來愈高度化。例 如’在以環氧樹脂作爲主要劑質（principal material)之 樹脂組成物的代表性領域，有半導體密封材料（ semiconductor sealing material )，惟隨著半導體元件的 積體度（integration level )之提升，組件大小（：package size)在朝向大面積化、薄型化之同時，黏著方式（ mounting ways)亦逐漸往表面黏著化（surface m〇unting )發展’因而盼望一種焊劑抗熱性優異的材料之開發。又 最近’隨著車輛裝載用半導體之進展，要求在高溫使用環 境下的可靠性提升’除高的玻璃化溫度點以外，尙希望開 發一種熱分解穩定性高的材料。於電路基板材料方面亦同 樣’從焊劑抗熱性提升之觀點來自，盼望一種除低吸濕性 -5- 201125838 、高抗熱性、高黏附性（high adherence )的提升之外， 尙在高溫使用環境下的分解劣化小的材料之開發。再者最 近，從環境保護之觀點來看，有排除鹵素系阻燃劑之動向 ，而希望開發一種阻燃性更爲優異的環氧樹脂及硬化劑。 鑑於上述背景，有人在硏究種種環氧樹脂及環氧樹脂 硬化劑。作爲環氧樹脂硬化劑的一例，周知有萘系樹脂、 聯苯系樹脂等，雖然在阻燃性提升上有些程度之效果，惟 由於因硬化性不佳之缺點或具有僅由烴所構成之主骨架之 故，未能達成足夠的阻燃性。 另一方面，就環氧樹脂而言，尙未開發能滿足此等要 求者。例如，周知的雙酚型環氧樹脂，係在常溫下爲液狀 者，由於因作業性良好，及與硬化劑、添加劑等的混合容 易之故廣泛在使用，惟卻在抗熱性、抗濕性上有問題。又 ，經改良抗熱性者而言，周知有酚醛清漆型環氧樹脂，惟 在抗濕性、黏著性等方面有問題。再者，主骨架爲僅由烴 所構成之在來的環氧樹脂，則全然不具有阻燃性。 作爲不使用鹵素系阻燃劑之下能提升阻燃性之計策而 言，曾揭示有添加磷酸酯系的阻燃劑之方法。然而，採用 磷酸酯系的阻燃劑之方法，則抗濕性並不足夠。又，在高 溫、多濕的環境下，磷酸酯會引起水解（hydrolysis )， 而有降低作爲絕緣材料之可靠性之問題。作爲不含磷原子 或鹵素原子之下仍能提升阻燃性者，有人硏究按與硬化劑 同樣方式將具有聯苯構造之芳烷基型環氧樹脂應用爲半導 體密封材料之作法。然而，彼等環氧樹脂在阻燃性、抗濕 -6- 201125838 性、或抗熱性之任一項中，性能並不足夠。 又’於專利文獻1、2以及3中，揭示有含胺基之苯酧 樹脂’含醯亞胺基之苯酚樹脂，雖然具有苯酚骨架與醯亞 月女骨架成爲父替共聚物（alternate copolymer)之構造而 抗熱性已獲提升，惟由於軟化點（softening point )及黏 度（v i s c 〇 s i t y )增高，以致有操作處理性大幅度降低之問 題。 再者，專利文獻4及5中，揭示有胺基或馬來醯亞胺基 作爲末端基所取代之苯酚性化合物，惟當進行含胺基之苯 酣化合物之合成時，有需要首先在苯酚化合物及鹼性條件 下使甲醛進行反應以合成二羥甲基化合物，接著，使此與 苯胺類在酸性條件下進行反應等繁雜的合成操作之問題。 再者，當將雙酚化合物作爲起始原料（starting material ) 以進行二羥甲基化合物之合成時，有雙酚化合物中的亞甲 基對羥基成爲鄰位之限制。由此所製得之樹脂，因立體阻 礙（steric hindrance)相當大之故，有成爲脆弱的硬化物 之問題。 [先前技術文獻] [專利文獻] 專利文獻1 :日本專利特開平4·227624號公報 專利文獻2:日本專利特開平7- 1 0970號公報 專利文獻3:日本專利特開平7·3 3 8 5 8號公報 專利文獻4:日本專利408 4 5 97號公報 專利文獻5:日本專利特開2009- 1 6 1 605號公報 201125838 【發明內容】 [發明所欲解決之課題] 本發明之目的在於提供爲環氧樹脂組成物的硬化劑、 改性劑等有用的多元羥基化合物。其他目的在於提供具有 優異的成型性之同時，能賦與抗熱性、阻燃性、低吸濕性 、熱分解穩定性等優異的硬化物之爲電氣•電子部件類的 密封、電路基板材料等、複合材料等有用的環氧樹脂組成 物、以及提供其硬化物。 [用以解決課題之手段] 本發明爲一種含胺基之多元羥基化合物，其特徵爲： 使苯酚類、芳香族胺類以及醛類反應後所得之可以下述一 般式（1 )， 【化1】201125838 VI. Description of the Invention: [Technical Field] The present invention relates to a polyvalent hydroxy compound which is useful as a curing agent and a reforming agent for an epoxy resin, and uses the epoxy resin composition thereof and the hardening thereof. It is very suitable for use as an insulating material such as a printed circuit board, a semi-conductor sealing, an insulating material, a coating material, and a composite material. ) By. [Prior Art] Epoxy resin is industrially used in a wide range of applications, but its performance requirements are becoming more and more advanced. For example, in the representative field of a resin composition using an epoxy resin as a principal material, there is a semiconductor sealing material, but as the integration level of the semiconductor element is increased, The package size is larger and thinner, and the mounting methods are gradually developed to surface m〇unting. Therefore, development of a material excellent in solder heat resistance is desired. Recently, with the progress of semiconductors for vehicle loading, it is required to improve the reliability in a high-temperature use environment. In addition to the high glass transition temperature, it is desired to develop a material having high thermal decomposition stability. In terms of the material of the circuit board, it also comes from the viewpoint of improving the heat resistance of the solder. It is expected that in addition to the low hygroscopicity-5-201125838, the high heat resistance and the high adherence, the high temperature environment is used. Development of materials with low decomposition degradation. In addition, from the viewpoint of environmental protection, there is a tendency to eliminate the halogen-based flame retardant, and it is desired to develop an epoxy resin and a curing agent which are more excellent in flame retardancy. In view of the above background, some people are looking for various epoxy resins and epoxy resin hardeners. As an example of the epoxy resin curing agent, a naphthalene-based resin or a biphenyl-based resin is known, and although it has some effects in improving flame retardancy, it is disadvantageous due to poor hardenability or has a main component composed only of hydrocarbons. Due to the skeleton, sufficient flame retardancy could not be achieved. On the other hand, in the case of epoxy resins, 尙 has not been developed to meet these requirements. For example, a well-known bisphenol type epoxy resin is liquid at room temperature, and is widely used because it is excellent in workability and easy to mix with a curing agent or an additive, but is resistant to heat and humidity. There is a problem with sex. Further, those who have improved heat resistance are known to have a novolac type epoxy resin, but have problems in moisture resistance and adhesion. Further, since the main skeleton is an epoxy resin composed only of a hydrocarbon, it does not have flame retardancy at all. As a countermeasure for improving flame retardancy without using a halogen-based flame retardant, a method of adding a phosphate-based flame retardant has been disclosed. However, the method of using a phosphate-based flame retardant is not sufficient for moisture resistance. Further, in a high-temperature, high-humidity environment, the phosphate ester causes hydrolysis, and there is a problem of lowering the reliability as an insulating material. As a flame retardant which does not contain a phosphorus atom or a halogen atom, it has been considered that a phenylene type epoxy resin having a biphenyl structure is applied as a semiconductor sealing material in the same manner as a hardener. However, in any of the flame retardancy, moisture resistance, heat resistance, or heat resistance, the performance of the epoxy resin is not sufficient. Further, in Patent Documents 1, 2 and 3, a phenol resin containing an amino group-containing benzoquinone resin is disclosed, and a phenol skeleton and a ruthenium skeleton are used as an alternate copolymer. The heat resistance of the structure has been improved, but the softening point and the viscosity (visc 〇sity) are increased, so that the handling property is greatly reduced. Further, in Patent Documents 4 and 5, a phenolic compound in which an amine group or a maleimine group is substituted as a terminal group is disclosed, but when the synthesis of an amino group-containing benzoquinone compound is carried out, it is necessary to firstly use phenol. The compound and the basic conditions allow the reaction of formaldehyde to synthesize a dimethylol compound, followed by a complicated synthesis operation such as reaction with an aniline under acidic conditions. Further, when a bisphenol compound is used as a starting material for the synthesis of a dimethylol compound, the methylene group in the bisphenol compound is restricted to the ortho position. The resin thus obtained has a problem that it becomes a weak and hardened material because the steric hindrance is relatively large. [PRIOR ART DOCUMENT] Patent Document 1: Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document No. 8] Japanese Patent No. 408 4 5 97 Patent Document 5: Japanese Patent Laid-Open No. Publication No. 2009- 1 6 No. 605 No. 201125838 SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] An object of the present invention is to provide It is a useful polyvalent hydroxy compound which is a hardener, a modifier, etc. of an epoxy resin composition. Other objects are to provide a cured product having excellent heat resistance, flame retardancy, low moisture absorption, thermal decomposition stability, etc., which is excellent in moldability, electrical and electronic parts, circuit board materials, and the like. A useful epoxy resin composition such as a composite material, and a cured product thereof. [Means for Solving the Problem] The present invention relates to an amine group-containing polyvalent hydroxy compound, which is characterized in that the phenol, the aromatic amine, and the aldehyde are reacted, and the following general formula (1) can be obtained. 1】

(在此，R!表示氫原子、羥基、碳數1至8的烷氧基或 碳數1至8的烴基，R2至Κ·4表示氫原子或碳數1至8的烴基， X 表示直接鍵結（direct bonding) 、-0·、-S-、-S02-、-CO-或二元的烴基》n爲1至10的數，而m爲0至2的整數， 201125838 惟m的平均爲0.05至1.5)。 表示之含胺基之多元羥基化合物。 又，本發明爲一種含胺基之多亓赖(here, R! represents a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms or a hydrocarbon group having 1 to 8 carbon atoms, and R2 to Κ·4 represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and X represents a direct Direct bonding, -0·, -S-, -S02-, -CO- or binary hydrocarbon group n is a number from 1 to 10, and m is an integer from 0 to 2, 201125838 only average of m It is 0.05 to 1.5). A polyhydroxy compound containing an amine group. Moreover, the present invention is an amine-containing group

Tser収空心夕兀羥基化合物之製造方 表示之苯酚類的 法，其特徵爲：對可以下述一般式（2 具有羥基之苯環!莫耳’使用可以下述—般式（”表示之 芳香族胺類0.05至U莫耳’及可以下述—般式⑷表示 之醛類〇.〇5$1·5莫耳’且依芳香族胺類與醒類的莫耳比爲 0.5至2.0的條件進行反應。A method for producing a phenol according to the manufacturer of a hollow hydroxy compound of Tser, which is characterized in that it can be expressed by the following general formula (2 benzene ring having a hydroxyl group; Moer' can be expressed by the following formula (" The amines are 0.05 to U Mo' and can be represented by the following formula (4): aldehydes 〇 5 1 5 1 5 耳 耳 且 且 且 且 依 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族Carry out the reaction.

(在此，L表示氫原子、羥基、碳數丨至8的烷氧基或 碳數1至8的烴基，X表示直接鍵結、-〇_、_s_、_s〇2_、_ co -或—兀的烴基》11爲1至1〇的數）。 【化3】 nh2 R2~^~R3 ⑶ (在此’ R2、h表示氫原子或碳數1至8的烴基） 【化4】 (4) R4~CH〇 (在此’ R4表示氫原子或碳數1至8的烴基）。 -9 - 201125838 再者，本發明爲一種含醯亞胺基之多元羥基化， 其特徵爲：使上述含胺基之多元羥基化合物辑^^ z(co)2〇表示之二羧酸酐類進行反應後所得之可以τ _ _ 般式（5)表示之含含醯亞胺基之多元羥基化合物。 【化5】(here, L represents a hydrogen atom, a hydroxyl group, an alkoxy group having a carbon number of 8 to 8 or a hydrocarbon group having 1 to 8 carbon atoms, and X represents a direct bond, -〇_, _s_, _s〇2_, _co- or - The hydrocarbyl group of hydrazine is a number from 1 to 1 Å). [Chemical 3] nh2 R2~^~R3 (3) (here, 'R2, h represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms). (4) R4~CH〇 (wherein R4 represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms). -9 - 201125838 Furthermore, the present invention is a polyhydroxyl group containing a quinone imine group, characterized in that the above-mentioned amino group-containing polyhydroxy compound is synthesized by a dicarboxylic acid anhydride represented by 2(z)(2). The polyhydroxy compound containing a quinone imine group represented by the formula (5) which is obtained by the reaction of τ _ _ can be obtained after the reaction. 【化5】

(在此，Ri至R4、X、η以及m’具有與一般式（j) 同樣意義。Z爲從二羧酸酐類所生成之至少具有2個碳原子 之二元的基）。 又’本發明爲一種含釀亞胺基之多兀經基化合物之製 造方法，其特徵爲：對可以上述一般式（2)表示之苯酚 類中的具有羥基之苯環1莫耳，使用可以上述一般式（3) 表示之芳香族胺類〇_〇5至1.5莫耳，及可以上述一般式（4 )表示之醛類〇·〇5至1.5莫耳，且依芳香族胺類與醛類的莫 耳比爲0 · 5至2.0的條件進行反應藉以製得含胺基之多元羥 基化合物’接著’將此含胺基之多元羥基化合物與可以 Z(CO)2〇 (在此’ Z係至少具有2個碳原子之二元的基）表 示之二羧酸酐類’對胺基1莫耳按酸酐基能成爲K0至1.5莫 耳之比例使用並進行反應。 再者’本發明爲一種環氧樹脂組成物，係由環氧樹脂 201125838 及硬化劑所成之環氧樹脂組成物’其特徵爲：作爲硬化劑 的一部分或全部，使用上述的含醯胺基之多元羥基化合物 或含醯亞胺基之多元羥基化合物。又，本發明爲一種環氧 樹脂硬化物，其特徵爲：使此種環氧樹脂組成物硬化所成 之環氧樹脂硬化物。 [發明之效果] 本發明之含胺基之多元羥基化合物及含醯亞胺基之多 元羥基化合物，係作爲環氧樹脂的硬化劑、改性劑以及環 氧樹脂中間物有用者，如應用爲環氧樹脂組成物之情形， 除具有優異的阻燃性之同時，尙能賦與高抗熱性、抗濕性 以及與異種材料間的高黏附性優異的硬化物，並能很適合 使用於電氣•電子部件類的密封、電路基板材料等用途上 [發明之最佳實施形態] 以下，就本發明內容加以詳細說明。 本發明之含胺基之多元羥基化合物（以下，簡稱含胺 基之樹脂），可以一般式（1)表示。又，本發明之含醯 亞胺之多元羥基化合物（以下，簡稱含醯亞胺基之樹脂） ，可以一般式（5)表示。由於含醯亞胺基之樹脂，可由 使含胺基之樹脂的胺基之醯亞胺化而製得之故，含胺基之 樹脂亦係屬於含醯亞胺之樹脂的中間物。又，含胺基之多 元羥基化合物及含醯亞胺基之多元羥基化合物，在均屬於 -11 - 201125838 多元羥基化合物之處有其共通點之故，將兩者總稱爲本發 明之多元羥基化合物、或含胺基或醯亞胺基之樹脂。 由於本發明之含胺基之多元羥基化合物，可藉由使以 一般式（2)表示之苯酚類與芳香族胺類與醛類反應而製 得之故，首先從製造方法之發明開始說明。 於一般式（2)中，1^爲氫原子、羥基、碳數1至8的 烷氧基或碳數1至8的烴基。如R,爲氫原子或甲基則低黏度 性會優異。又，如爲羥基則抗熱性會優異。再者，如爲苯 基、节基、苯乙烯基或節基（indenyl )則抗濕性、阻燃性 '高黏附性會優異。較佳爲氫原子、碳數1至3的烷氧基或 碳數1至3的烷基。 於一般式（2 )中，X爲直接鍵結、-〇-、-s-、_S〇2_ 、-CO-或二元的烴基。如X爲直接鍵結、-S02-、-CO-，則 抗熱性會優異。又，如X爲亞甲基、亞乙基或亞異丙基， 則溶劑溶解性、低黏度性會優異。再者，如X爲-C Η 2 - φ -CH2-基或-CH2- Φ - φ -CH2-基，貝IJ抗濕性、阻燃性、抗龜裂 性會優異。在此’ Φ表示伸苯基。二元的烴基而言，較佳 爲碳數1至14的烴基，惟更佳爲碳數1至3的伸烷基或者亞 院基或伸茬基（xylylene)。 於一般式（2)中，n爲1至1〇的數。在此，—般式 )的苯酚類，如係由η値不相同的成分之混合物所構成之 苯酚性樹脂之情形’則η爲其平均（數平均）値。再者， 可以一般式（2 )的苯酚性化合物而言，如係以η爲1或2的 整數之雙酚化合物或參酚化合物或平均値η爲1〜2之雙酚 -12- 201125838 化合物或參酚化合物作爲主成分之樹脂，或係以此等化合 物或樹脂作爲主成分者’則低黏度性、溶劑溶解性會優異 。更佳之η，如係整數時則爲i，如係平均値時則爲1至1 5 〇 可以一般式（2)表示之苯酚類而言，有11爲1至1〇的 整數之任一之單一化合物之情形，及2種以上的混合物之 情形’而如係混合物之情形，則可爲具有分子量分佈（ distribution of molecular weight)之樹脂《較佳爲可舉： η爲1之雙酚化合物及具有分子量分佈之多元苯酚系樹脂。 如具體例示時，雙酚化合物而言，可舉：雙酚F、雙 酚Α、4,4’-二羥基二苯基甲烷、4,4’-二羥基二苯基醚、 4,4’-二羥基二苯基颯、4,4’-二羥基二苯基硫化物、4,4，-二經基二苯基酮、茜（fluorene)雙酣、2,2’-聯苯酌（ biphenol) 、4,4’-聯苯酚。又，多元的苯酚性樹脂而言， 可例示：苯酚酚醛清漆、雙酚A酚醛清漆、鄰甲酚酚醛清 漆、苯酚芳烷基樹脂，由苯酚與雙氯甲基聯苯之反應所得 之聯苯型芳烷基樹脂。 於一般式（3)中，R2、R3表示氫原子或碳數1至8的 烴基。如R2、R3爲氫原子或甲基，則低黏度性會優異。再 者，如爲苯基、苄基、苯乙烯基、茚基，則抗濕性、阻燃 性、高黏附性會優異。一般式（3 )的芳香族胺類而言， 具體可舉：苯胺、2-甲基苯胺' 3-甲基苯胺、4-甲基苯胺 、2,4-二甲基苯胺' 2,6_二甲基苯胺、乙基苯胺類、苯基 苯胺類、苄基苯胺類，惟從低黏度性、反應性的觀點來看 -13- 201125838 ，較佳爲苯胺。 於一般式（4)中，R4表示氫原子、碳數1至8的烴基 。一般式（4)的醛類而言，具體可舉：甲醛、乙醛、苄 醛，惟從低黏度性、反應性的觀點來看，較佳爲甲醛。再 者，反應時的醛源而言，可採用：甲醛水、仲甲醛（ paraformaldehyde)、三噚院（trioxane)等。 本發明之含胺基之樹脂，如使含有可以式（2 )表示 之苯酚類與可以式（3)表示之芳香族胺類以及可以式（4 )表示之醛類之反應混合物進行反應，即可加以合成。於 此反應中’主反應將如下方式進行。首先，醛類即優先與 芳香族胺類反應而生成醛類的芳香族胺加成物。接著，該 加成物即與苯酚類進行反應，以生成苯酚類與芳香族胺類 經介由fl女基甲基而結合之脫水縮合物（dehydration condensation product)，接著，該脫水縮合物引起轉移反 應（transfer reaction)後生成苯酚類與芳香族胺類經介由 伸甲基鍵結而反應之本發明之含胺基之多元羥基化合物。 因而’對芳香族胺類，如醛類不足之情形則未反應的芳香 族胺類會殘留’如醛類過剩之情形，則此等即與苯酣類或 所生成之含胺基之樹脂進行反應而高分子量化。 從此等觀點來看’芳香族胺類的使用量，係對苯酸類 中之具有羥基之苯環1莫耳，爲在0.05至1.5莫耳的範圍， 惟較佳爲在0.1至1.0’更佳爲在0.15至1.0莫耳，再佳爲在 0.2至0·9莫耳’特佳爲在〇·4至0.8莫耳的範圍。如較此爲 少時’則抗熱性、阻燃性等的提升效果低，如較此爲多時 -14- 201125838 ，則軟化點升局而操作處理性降低。 醛類的使用量，係對苯酚類中之具有羥基之苯環丨莫 耳，爲在〇·〇5至1.5莫耳的範圍，惟較佳爲在〇1至1〇，更 佳爲在0.15至1_〇莫耳，再佳爲在〇·2至〇.9莫耳，特佳爲在 0.5至2.0莫耳的範圍。又，係對芳香族胺類丨莫耳爲在 0.9至1.1莫耳的範圍，惟較佳爲在〇.8至1.2莫耳，更佳爲 在0 · 9至1 1莫耳的範圍。如較此爲少時，則反應後所殘留 之未反應的芳香族胺類的量會增多，如較此爲多時，則因 苯酚類、或所生成之含胺基之樹脂會與醛類進行反應而高 分子量化之故，高軟化點及高黏度化之結果操作處理性會 降低之同時，亦可能會凝膠化。 醛類’係作爲使苯酚類與芳香族胺類結合之交聯劑而 發揮作用。對苯酚類中的1個苯環，可能會結合m個芳香族 胺類。該反應係一種縮合反應（condensation reaction) ，而會生成水。在此，苯酚類中之具有羥基之苯環，係指 於一般式（2)中，經與羥基結合之苯環之意，而與苯酚 類中之苯環或苯酚環同意義者。 此種反應，可於無觸媒或觸媒之存在下進行。如使用 觸媒時，則作爲觸媒，可從周知之無機酸、有機酸中適當 加以選擇。具體可舉：鹽酸、硫酸、磷酸等無機酸（ mineral acid)、或甲酸、草酸、三氟醋酸、對甲苯磺酸 、二甲基硫酸、二乙基硫酸等有機酸、或氯化鋅、氯化鋁 、氯化鐵、三氟化硼等路易斯酸（Lewis acid )或離子交 換樹脂、活化黏土（activated clay)、氧化砂一氧化銘、 -15- 201125838 沸石（zeolite)等固體酸（solid acid )等。 又，此種反應，係通常在1〇至250°C下進行1至20小時 。較佳的反應溫度爲50至20(TC，較佳的反應時間爲1至1〇 小時。再者，在反應時，可作爲溶劑而使用：甲醇、乙醇 、丙醇、丁醇、乙二醇、甲基賽路蘇（methyl cellosolve )、乙基賽路蘇等醇類，或丙嗣、甲基乙基甲酮、甲基異 丁基甲酮等酮類，二甲基醚、二乙基醚、二異丙基醚、四 氫呋喃、二噚烷（dioxane)等醚類，苯、甲苯、氯苯、二 氯苯等芳香族化合物等。 反應終了後，有時，所製得之含胺基之樹脂中，會殘 留未反應之芳香族胺類及醛類。所殘留之芳香族胺類及醛 類，通常可依減壓蒸餾、水洗或溶劑部分分離法（solvent fractioning)等方法去除於系外。由於在減壓蒸餾時亦會 進行反應之故，溫度及時間（合計）安排在上述範圍爲宜 。含胺基之樹脂中殘留之未反應的芳香族胺類及醛類的量 控制爲少較宜，通常爲5重量％以下、較佳爲3重量％以下 、更佳爲1重量％以下。如所殘留之芳香族胺類及醛類的量 多時，則製作成型物時會揮發，以致降低成型作業性之同 時，可能成爲成型物的空隙（void )之原因。又，成型物 的阻燃性亦會降低。 本發明之含胺基之多元羥基化合物，可以上述一般式 (1 )表示。在此，X、R,以及η係與於一般式（2 )的苯酚 類的說明中之X、L以及η相同者。又，R2、R3係與一般式 (3 )的芳香族胺類的說明中之R2、R3相同者，R4係與於 -16- 201125838 一般式（4)的醛類的說明中之114相同者。 於一般式（1)中，m爲0至2的整數，惟以經與羥基結 合之每1個苯環（苯酚環）的平均計，爲在〇.05至丨.5的範 圍。如作爲含胺基之樹脂觀看時，m的數係就1個苯酚環， 以平均計，爲在0.05至1.5，惟較佳爲在^丨至丨^、更佳爲 在0.15至1.0、再佳爲在0.2至0.9、特佳爲在〇.4至0.8的範 圍。如較此爲少時’則抗熱性、阻燃性等的提升效果小， 如較此爲多時’則軟化點升高之結果操作處理性會降低。 如本發明之含胺基之多元羥基化合物係不具有分子量分佈 而η爲整數之化合物之情形，則一分子中的至少1個m爲1或 2。又，如係η具有分子量分佈而屬於平均値之化合物之情 形’則每一分子之平均的m (—分子中的m的合計的數平 均），爲在0.1至3的範圍。 本發明之含胺基之樹脂的軟化點係以40至160 °C爲宜 ’較佳爲在50至1 20°C、更佳爲在60至1 00°C的範圍。在此 ，軟化點，係依據JIS K-6911的環球法（ring and ball test )所測定之軟化點之意。如較此爲低時，則當將此調配於 環氧樹脂中時，硬化物的抗熱性會降低，如較此爲高時， 則成型時的流動性會降低。再者，如作爲本發明之含醯亞 胺基之樹脂的中間物使用之情形，則所得之含醯亞胺基之 樹脂的軟化點及黏度會增高，以致操作處理性會降低。在 此，含胺基之樹脂及含醯亞胺基之樹脂的軟化點，係藉由 改變一般式（1 )的η或m等而能加以調整者，一般而言， 如改大此等即可增高軟化點。 -17- 201125838 其次，就可以一般式（5)表示之本發明之含醯亞胺 基之樹脂加以說明。於一般式（5 )中，心至R4、X、m以 及η，係與一般式（1)中之說明同樣意義者。 又，於一般式（5 )中，如m的數爲少時，則抗熱性、 阻燃性等的提升效果會減小，如較此爲多時，則軟化點增 高而操作處理性會降低。 Z，係從可以z(co)2o表示之羧酸酐類，去除酸酐基 (co2)o後所生成之二元的基。因而，Z係從二羧酸的無水 物的說明即可瞭解。 較佳的Z而言，可例示：可以CnH2nSCnH2n-2表示之二 元的脂肪族基，可以A表示之二元的1至3環的芳香族環， 可以Ar-Y-Ar表示之二元的芳香族基，可以環C4-6表示之二 元的環烴基，可以雙環（bicycl〇)C6.8表示之二元的雙環烴 基。又，η而言，較佳爲在1至8的範圍。A而言，較佳爲二 元的苯環、萘環 '蒽環或菲（phenanthrene )環。Ar而言 ，較佳爲苯環，而2個Ar可爲不相同。Y而言，較佳爲單鍵 (singlebond) 、0、S、SO、S02、CO 或 CnH2n，n 而言， 較佳爲在1至8的範圍。環C4.6而言，較佳爲二元的C4至C6 的環烷、環烯或環二烯環。可以雙環（：6.8表示之二元的雙 環烴基而言，較佳爲二元的C6_8的雙環烷環。此等烴基、 芳香族環或脂肪族環可具有取代基，而如具有取代基之情 形，較佳的取代基爲碳數1至6的烷基、苯基、碳數1至6的 烷氧基、羥基或鹵素。 又，Z較佳爲選自：碳數2至24的不飽和脂肪族基、不 -18- 201125838 飽和單環式脂肪族基、不飽和縮合多環式脂肪族基經直接 方式或藉由交聯員（member of cross linking)而互相連 結之不飽和非縮合多環式脂肪族基、作爲取代基而具有鏈 狀脂肪族基之單環式芳香族基、作爲取代基而具有鏈狀脂 肪族基之縮合多環式芳香族基、作爲取代基而具有不飽和 單環式脂肪族基及作爲取代基而具有不飽和單環式脂肪族 基之縮合多環式芳香族基所成群之二元的基。 本發明之含醯亞胺基之樹脂，係對本發明之含胺基之 樹脂使二羧酸酐進行反應，即可製得。 在此可使用之二羧酸酐而言，可例舉：馬來酸酐、酞 酸酐、2,3-二苯基酮二羧酸酐、3,4-二苯基酮二羧酸酐、 2,3 -二羧基苯基苯基醚酐、3,4 -二羧基苯基苯基醚、2,3-聯 苯基二羧酸酐、3,4 -聯苯基二羧酸酐、2,3 -二羧酸苯基苯 基颯酐、3,4 -二羧基苯基苯基颯酐、2,3_二羧基苯基苯基 硫化物無水物、3,4-二羧基苯基苯基硫化物無水物、1，2-蔡二羧酸酐、2,3-萘二羧酸酐、1，8_萘二羧酸酐、1,2-蒽二 羧酸酐、2,3-蒽二羧酸酐、1，9·蒽二羧酸酐、環丁烷-1,2-二羧酸酐、環丁烷-1,3 -二羧酸酐、ι，2 -環戊烷二羧酸酐、 1-甲基-1，2-環戊烷二羧酸酐、12-環己烷二羧酸酐、1,3-瓌己烷二羧酸酐、1-環己烯-1，2·二羧酸酐、2-環己烯-1，2-二羧酸酐、3 -環己烯-1,2 -二羧酸酐、4 -環己烯-1，2 -二羧酸 酐、1-環己烯-1，3 -二羧酸酐、3 -環己烯-1，3·二羧酸酐、4_ 環己烯-1，3 -二羧酸酐、1，3-環己二烯- i，2 -二羧酸酐、1，4-瓌己二烯-1,2 -二羧酸酐、2,4 -環己二烯-1,2 -二羧酸酐、 -19- 201125838 2,5-環己二烯-1,2 -二羧酸酐、2,6 -環己二烯- l，2 -二羧酸酐 、3,5 -環己二烯-1，2 -二羧酸酐、環己基琥珀酸酐、5_雙環 [2,2,1]庚烯-2,3-二羧酸酐、雙環[2,2，1]庚烯-2,3_二羧酸酐 、2-雙環[2,2，1]庚烯-2,3-二羧酸酐、2_雙環[2,2,2]辛烯_ 2,3 -二羧酸酐、5 -雙環[2，2,2]辛烯-2,3 -二羧酸酐等。其中 ，較合適的化合物爲馬來酸酐、酞酸酐以及降冰片烯二酸 (nadic acid )酐。如採用馬來酸酐時，則會生成馬來醯 亞胺基’如將此應用之樹脂組成物之情形，由於馬來酿亞 胺基會參與硬化反應之故’可期待大幅度的抗熱性的提升 。又，如採用酞酸酐及降冰片烯二酸酐之情形，則於硬化 物中，可期待抗濕性及抗熱性的提升。 於此製造方法中，首先對含胺基之樹脂使羧酸酐進行 反應後，將此加成物進行加熱脫水閉環（heating， dehydrating，ring closure)，或在酸性觸媒的存在下，進 行既定溶劑中之加熱回流，藉以使其進行脫水縮合（ dehydrating condensation)者。不用觸媒之下進行加熱脫 水閉環之方法，係在常壓或減壓下進行加熱脫水。反應， 通常係在無溶劑下進行者，惟亦可爲反應而使用惰性的溶 劑。此種方法中，上述的羧酸酐的任一種均可使用，惟特 別是不飽和脂肪族羧酸酐以外之羧酸酐很合適。 如採用酸性觸媒以使其脫水閉環之情形，作爲酸性觸 媒，可使用：硫酸、鹽酸、磷酸等無機酸、磷鎢酸、磷鉬 酸等雜多酸（heteropoly-acid)、對甲苯擴酸、甲院擴酸 等有機磺酸、三氯醋酸、三氟醋酸等鹵素化羧酸’氧化砂 -20- 201125838 氧化鋁等固體酸，陽離子型離子交換樹脂等。特別是硫酸 、磷酸、對甲苯磺酸很合適。又，此等酸，可作成與胺的 鹽的形態。此等酸性觸媒，雖因其種類而有所異，惟一般 對二羧酸酐和前述含胺基之樹脂的合計量，按0.1至10重 量％的量使用爲宜。如觸媒量爲少於〇. 1重量％時，則不能 達成所希望的觸媒效果，又即使使用10重量％以上時，仍 然不能獲得一定程度以上之效果，以致不僅不經濟、且殘 留觸媒之去除亦有困難。 進行縮合反應時所用之溶劑而言，可使用：己烷、庚 烷、癸烷、環己烷等脂肪族或脂環族烴，苯、甲苯、茬等 芳香族烴以及其鹵素化物，Ν,Ν-二甲基甲醛、N-甲基吡咯 烷酮、乙腈、Ν，Ν-二甲基乙醯胺、二甲基亞颯、環丁颯（ sulfolane)、茴香醚（anisole)、正丁基醚等含氧或者含 硫極性溶劑。溶劑量，一般爲對前述含胺基之樹脂和羧酸 酐的合計量，在1至20倍，特別是2至10倍的範圍較合適。 反應溫度，一般在80至200 °C，較佳爲150至200 °C。 在加熱回流下進行反應時的反應溫度，雖因所用之溶劑而 有若干不同，惟一般在80至190°C、特別是在1〇〇至16CTC 的範圍較合適。壓力可爲加壓、常壓、減壓的任一種，可 按照所用之溶劑及反應溫度而加以適當選擇。反應時間， 一般爲在〇 . 5至2 0小時，特別是在1至1 5小時的範圍。在此 ，二羧酸酐及含胺基之樹脂的飼給量，係對含胺基之樹脂 成分，將二羧酸酐量作成等量或若干過剩之方式較合適。 一般而言，以莫耳基準計，對含胺基之樹脂中的全胺基， -21 - 按羧 成後 二羧 含醯 80 羧酸 壓下 位， 位的 經醯 計， 上者 亞胺 環氧 的一 脂， 基之 亞胺 基之 201125838 酸酐能成爲1.0至1.5倍之方式飼給即 ，進行反應混合物之洗滌，以去除殘 酸酐之後，餾除溶劑而製得濃縮物。 亞胺之樹脂，係醯亞胺基/羥基的莫： :20，軟化點在60至160°c程度爲宜。 酐的去除，雖因二羧酸酐的沸點而有 於150至25(TC下進行爲宜。 本發明之含醯亞胺之樹脂，係含胺基 在與二羧酸酐進行反應後，一次性所 至少一部分，較佳爲全部已經成爲醯 亞胺化後的胺基的量，較佳爲儘量少 較佳爲5,000g/eq.(當量）以上者，更佳 。在此，如按胺當量能爲5000g/eq.以 化時，則在提升阻燃性、抗熱性上而 又，本發明爲一種環氧樹脂硬化物， 樹脂及硬化劑所成之環氧樹脂組成物 部分或全部，而使用本發明之含胺基 而有下列的2種。 1 )作爲硬化劑的一部分或全部，而 樹脂之組成物。 2 )作爲硬化劑的一部分或全部，而 基之樹脂之組成物。 3 )作爲硬化劑的一部分或全部，而 樹脂及前述含醯亞胺基之樹脂之組成 可。縮合反應完 留觸媒，未反應 如此方式所得之 5比在3 : 97至 在此，未反應二 所不同，惟在減 之樹脂的胺基部 生成之醯胺基部 亞胺基之樹脂。 量者，以胺當量 爲 10,000g/eq.以 上之方式使其醯 言，較爲有利。 其特徵爲：於由 中，作爲硬化劑 或醯亞胺基之樹 調配有前述含胺 調配有前述含醯 調配有前述含胺 物。 -22- 201125838 在上述1 )及2 )的組成物之情形，含胺基或醯亞胺基 之樹脂的調配量（如調配含胺基之樹脂及含醯亞胺基之樹 脂的兩者時，則其合計量），通常係對環氧樹脂1 00重量 份爲在2至200重量份’較佳爲在5至80重量份的範圍。如 較此爲少時’則阻燃性、低吸濕性以及黏附性提升之效果 小’如較此爲多時，則有成型性及硬化物的強度會降低之 問題。 如作爲硬化物的全量而使用本發明之含胺基之樹脂或 含醯亞胺基之樹脂之情形，通常，各調配量，係在考慮樹 脂中的胺基及苯酚性羥基的活性氫（active hydrogen )的 量與環氧樹脂中的環氧基的當量平衡之下加以調配。環氧 樹脂及硬化劑的當量比，通常係在0.2至5.0的範圍，較佳 爲0.5至2.0的範圍。較此爲大或爲小，環氧樹脂組成物的 硬化性均會降低之同時，硬化物的抗熱性、機械強度（ mechanical strength )等會降低。 作爲硬化劑而可倂用本發明之含胺基或醯亞胺基之樹 脂以外的硬化劑。其他的硬化劑的調配量，係含胺基或醯 亞胺基之樹脂的調配量，通常按對環氧樹脂100重量份， 能保持在2至200重量份，較佳爲在5至80重量份的範圍之 範圍內加以決定。如含胺基或醯亞胺基之樹脂的調配量較 此爲少時’則阻燃性、低吸濕性以及黏附性提升之效果小 ’如較此爲多時’則有成型性及硬化物的強度會降低之問 題。 含胺基或醯亞胺基之樹脂以外的硬化劑而言1 一般作 -23- 201125838 爲環氧樹脂的硬化劑所周知者均可使用，而有：雙氰胺、 酸肝類、多兀本酣類、芳香族及脂肪族胺類等。此等之中 ，於半導體密封材料等需要高的電氣絕緣性之領域中，較 佳爲將多元苯酚類作爲硬化劑使用。以下，將表示硬化劑 的具體例。 酸酐硬化劑而言，例如，有：酞酸酐、四氫酞酸酐、 甲基四氫駄酸酐、六氫酞酸酐、甲基六氫醜酸野、甲基海 明酸酐（hymic acid anhydride)、十二碳烯琥珀酸酐、降 冰片稀二酸酐（nadic acid anhydride)、偏苯三甲酸酐等 〇 多元苯酚類而言，例如，有：雙酚A、雙酚F、雙酣S 、蕗雙酚、4,4’-聯苯酚、2，2’-聯苯酚、氫醌、雷瑣辛（ resorcin)、萘二醇等二元的苯酚類，或者，參（4-羥基 苯基）甲烷、1，1，2,2-肆（4-羥基苯基）乙烷、苯酚酚醛清 漆、鄰甲酚酚醛清漆、萘酚酚醛清漆、聚乙烯基苯酚等所 代表之三元以上的苯酚類。再者，有：由苯酚類、萘酚類 、雙酚A'雙酚F、雙酚S'莽雙酚、4,4’聯苯酚、2,2’-聯 苯酚、氫醌、雷瑣辛、萘二醇等二元苯酚類，與甲醛、乙 醛、苄醛、對羥基苄醛、對茬二醇等縮合劑所合成之多元 苯酚性化合物等。又，亦可調配前述之本發明之苯酚樹脂 組成物。 胺類而言，有：4,4’-二胺基二苯基甲烷、4,4’-二胺基 二苯基丙烷、4,4’-二胺基二苯基砸、間伸苯基二胺、對伸 茬基二胺等芳香族胺類，伸乙基二胺、六亞甲基二胺、二 -24- 201125838 伸乙基三胺、三伸乙基四胺等脂肪族胺等。 爲上述組成物，亦可混合此等硬化劑的1種或2種以上 使用。 爲上述組成物所使用之環氧樹脂而言，可選自1分子 中具有環氧基2個以上者。可例舉：雙酚A、雙酚F、 3,3’，5,5’-四甲基雙酚？、雙酚3、蒔雙酚、2,2’-聯苯酚、 3,3’，5,5’-四甲基-4,4’-二羥基聯苯酚、雷瑣辛、萘二醇類 等二元的苯酚類之環氧化物，參（4-羥基苯基）甲烷、 1，1，2,2-肆（4-羥基苯基）乙烷、苯酚酚醛清漆、鄰甲酚酚 醛清漆等三元以上的苯酚類的環氧化物、二環戊二烯與苯 酚類的共縮合樹脂的環氧化物、由苯酚類與對二氯化伸茬 基等所合成之苯酚芳烷基樹脂類的環氧化物、由苯酚類與 雙氯甲基聯苯等所合成之聯苯芳烷基苯酚樹脂的環氧化物 、由萘酚類與對二氯化伸茬基等所合成之萘酚芳烷基樹脂 類的環氧化物等。此等環氧樹脂可以單獨使用，亦可倂用 2種以上。更佳的環氧樹脂可舉：由3,3’，5,5’ -四甲基-4,4，-二羥基聯苯酚、3,3’，5,5’-四甲基-雙酚F等所得之結晶性環 氧樹脂’由鄰甲酚酚醛清漆等的多官能樹脂所得之環氧樹 脂，由苯酚芳烷基樹脂類、聯苯芳烷基樹脂類所得之環氧 樹脂等在常溫下爲固體狀環氧樹脂。 於本發明之環氧樹脂組成物中，作爲其他改性劑而可 適當調配聚酯、聚醯胺、聚醯亞胺、聚醚、聚胺基甲酸醒 、石油系樹脂、茚樹脂（indene resin)、節•香豆嗣樹脂 (indene · coumarine resin )、苯氧基樹脂等低聚物（ -25- 201125838 oligomer )或高分子化合物。添加量，通常係對環氧樹脂 1〇〇重量份，爲在2至30重量份的範圍。 又’於本發明之環氧樹脂組成物中，可調配：無機塡 充劑、顏料、阻燃劑、觸變性加成劑（thixotropy addition agent)、偶合劑（coupling agout)、流動性改善劑（ fluidity promotor)等添加劑。無機塡充劑而言，可例舉 :球狀或破碎狀的熔融矽石（fused silica )、結晶矽石等 矽石粉末、鋁氧粉末、玻璃粉末、或者雲母（mica)、滑 石（talc )、碳酸鈣、鋁氧、水合鋁氧等，如用爲半導體 密封材料之情形的較佳的調配量爲70重量％以上、更佳爲 8 0重量％以上。 顏料而言，有：有機系或無機系的底質顏料（body pigment)、鱗片狀顏料（flake pigment)等。觸變性加成 劑而言，可舉：矽系、蓖蔴子油（castor oil )系、脂肪族 醯胺蠟（amide wax)、氧化聚乙稀蠘（〇xyp〇lyethylene w a X )、有機膨土（ 〇 r g a n i c b e n t ο n i t e )系等。 再者，爲本發明之環氧樹脂組成物，需要時，可採用 硬化促進劑。舉例時，有：胺類、咪唑類、有機膦類、路 易斯酸類等，具體而言，有：1,8 -二氮雜雙環（5,4,0)十 —碳烯-7、三伸乙基二胺、苄基二甲基胺、三乙醇胺、二 甲基胺基乙醇、參（二甲基胺基甲基）苯酚等三級胺、2-甲基咪唑、2-苯基咪唑、2-乙基-4-甲基咪唑、2-苯基-4-甲 基咪唑、2-十七烷基咪唑等咪唑類，三丁基膦、甲基二苯 基膦、三苯基膦、二苯基膦、苯基膦等有機膦類，四苯基 -26- 201125838 膦·四苯基硼酸酯、四苯基膦.乙基三苯基硼酸酯、四丁 基膦•四丁基硼酸酯等四取代鱗•四取代硼酸醋、2_乙_4_ 甲基咪唑•四苯基硼酸酯、N -甲基嗎啉•四苯基硼酸酯等 四苯基硼鹽等。添加量而言’通常係對環氧樹脂1〇0重量 份，爲在0.2至5重量份的範圍。 再者’需要時’爲本發明之樹脂組成物中，可使用·· 巴西棕櫚蠟（carnauba wax ) 、〇p (油性調和）蠟等脫模 劑、γ -縮水甘油氧丙基三甲氧矽烷等偶合劑、碳黑等著色 劑、三氧化銻等阻燃劑、聚矽氧油等低應力化劑' 硬脂酸 鈣等潤滑劑等。 本發明之環氧樹脂組成物，可在作成經溶解於有機溶 劑中之清漆（varnish )狀態後，含浸（impregnating )於 玻璃布（glass cloth)、聚醯胺（aramide)不織布、液晶 聚合物不織物等聚酯不織物等纖維狀物中後實施溶劑去除 ’以作成半固化片（prepreg )。又有時，如塗佈於銅箔、 不鏽鋼箔、聚醯亞胺薄膜、聚酯薄膜等片材狀物上，即可 作成層合物。 如使本發明之環氧樹脂組成物加熱硬化時，則可作成 本發明之環氧樹脂硬化物，而此種硬化物係在低吸濕性、 高抗熱性、黏附性、阻燃性等方面優異者。此種硬化物， 如將環氧樹脂組成物利用注塑成型（cast moulding)、壓 塑成型（press moulding) ' 傳遞成型（transfer moulding )等方法，加以成型加工即可製得。此時之溫度，通常係 在120至22 0°C的範圍。 -27- 201125838 本發明之含胺基或醯亞胺基之樹脂，如與其他多元苯 酚類混合，亦可作成苯酚樹脂組成物。含胺基或醯亞胺基 之樹脂的含有率，係對其他多元苯酚類1〇〇重量份，爲在2 至200重量份，較佳爲在5至100重量份，更佳爲在10至80 重量份的範圍。如較此爲少時，則低吸濕性、抗熱性、黏 附性以及阻燃性等的改性效果（reforming effect )小，如 較此爲多時，則黏度增高以致成型性降低。 在此所稱之其他多元苯酚類，可使用與原先之作爲環 氧樹脂組成物的硬化劑的例所說明之多元苯酚類同樣者。 上述苯酚樹脂組成物，如與爲六甲基四胺等之苯酚樹 脂成型材料一般所用之硬化劑倂用，則可作爲苯酚樹脂硬 化物。 又’本發明之含胺基或醯亞胺基之樹脂，如對此使鹵 素化院基化合物、鹵素化嫌基化合物 '表鹵化醇（ epihalohydrin )等進行反應’則可將含胺基之樹脂中的胺 基及苯酚性羥基的氫原子的一部分或全部取代爲烷基、烯 基、縮水甘油基等。 【實施方式】 [實施例] 以下，藉由實施例而將本發明內容再具體加以說明。 在此’黏度係採用BROOKFIELD製，CAP2000H、軟 化點係依照JIS K-691 1 ’並依環球法測定者。又，Gpc ( 膠透層析術）測定，係依：裝置；日本歐塔斯（Waters ) -28- 201125838 (股）製、515A 型、管柱（column) ； TSK-GEL 2000x3 支及TSK-GEL 4000X1支（均爲東曹（股）製）、溶劑；四 氫呋喃、流量；1 m 1 /分鐘、溫度：3 8 °C、檢測器；RI (放 射性同位素）之條件，爲檢量線則使用聚苯乙烯標準液。 胺當量（amine equivalent)，係藉由利用0.1M (莫耳） 過氯酸一醋酸溶液之電位差式滴定（potentiomentric differential titration)而求得。又，含胺基之樹脂的經基 當量，係按從依氯化乙醯法（acetyl chloride method)所 求出之羥基和胺基的合計量，減去在胺當量之測定所求出 之胺基量以估計羥基量之方式推算者。 [實施例1 ] 飼給苯胺46.5g(0.5莫耳）、4,4’-二羥基二苯基甲烷 200g(1.0莫耳），在導入氮氣之下加熱爲80 °C，並滴下 37%甲醛水溶液40.5g ( 0.5莫耳）。接著，在攪拌下升溫 至95 °C並回流2小時，再於脫水後升溫至180 °C並反應2小 時。然後，於減壓下在180 °C下去除未反應之苯胺後，製 得含胺基之樹脂2 3 8.5g。所得樹脂之羥基當量爲 1 17.4g/eq. ’ 胺當量爲 626.4g/eq.，軟化點爲 62°C，於 150 °C下之熔化黏度（melt viscosity)爲31mPa· s (兆泊）。 將1H-NMR光譜表示於第1圖’將紅外吸收光譜表示於 第2圖’將FDMS光譜表示於第3圖，將GPC圖表表示於第4 圖。於FDMS光譜中，觀察到在式（1 )中對應於n=1& m = 〇 之m/z = 200、對應於n=l及m = l之m/z = 305、對應於n = 2及 -29 - 201125838 m = l 之 m/z=5l8、對應於 n = 2 及 m = 2 之 m/z = 623、對應於 n = 2 及m = 3之m/z = 728、對應於n = 3及m = 2之m/z = 835、對應於 n = 3 及 m = 3 之 m/z = 940、對應於 n = 3 及 m = 4 之 m/z= 1 045、對應 於 n = 4 及 m = 3 之 m/z=1152、對應於 n = 4 及 m = 4 之 m/z=1258 ' 對應於n = 5及m=3之m/z= 1 3 63、對應於n = 6及m = 2之 m/z=1469之情形。在此，有關FDMS光譜之說明中，式（1 )之m係指1分子中的m的合計之意。 [實施例2] 飼給於實施例1中所得之含胺基之樹脂60g、酞酸酐 14.2g，在導入氮氣之下加熱爲150 °C以使其溶解並反應1 小時。在此當中，因反應所生成之水，則加以去除於系統 外。然後，於減壓下在23 0 °C下去除未反應之酞酸酐，製 得含醯亞胺基之樹脂5 7 . 1 g (樹脂A )。所得樹脂之羥基當 量爲157g/eq.，胺當量爲74950g/eq.，軟化點爲76°C，於 150°C下之熔化黏度爲0.1 ImPa · s。 將1H-NMR光譜表示於第5圖，將紅外吸收光譜表示於 第6圖，將FDMS光譜表示於第7圖，將GPC圖表表示於第8 圖。於FDMS光譜中，觀察到在式（5 )中對應於n=l及m = 0 之m/z = 200、對應於n=l及m = l之m/z = 435、對應於n = 2及 m=l 之 m/z = 647、對應於 n=l 及 m = 2 之 m/z = 670、對應於 n = 2 及m = 3之m/z = 884、對應於n=l及m = 3之m/z = 906、對應於 n = 3 及 m = 2 之 m/z=1095、對應於 n = 2 及 m = 3 之 m/z=1118、對 應於n = 3及m = 3之m/z=1330之情形。 -30- 201125838 [實施例3] 飼給於實施例1中所得之含胺基之樹脂60g、馬來酸酐 9.4 g、甲苯120g，在導入氮氣之下加熱爲11〇 °C並在與甲 苯的共沸以去除水於系統外之下反應2小時。然後，於減 壓下加熱爲180 °C下去除甲苯及未反應之馬來酸酐，製得 含醯亞胺基之樹脂64.3g (樹脂B )。所得樹脂之羥基當量 爲144g/eq.，胺當量爲1 3 8400g/eq.，軟化點爲88.5°C，於 150°(：下之熔化黏度爲〇.44?3.3»將〇?(：圖表，表示於第9 圖0 [實施例4] 飼給苯胺46.5g( 0.5莫耳）、4，4’-二羥基二苯基甲烷 100§(0.5莫耳），在導入氮氣之下加熱爲80乞，.並滴下 37%甲醛水溶液4〇.5g ( 0.5莫耳）。接著，在攪拌下升溫 至9 5 °C並回流2小時，再於脫水後升溫至1 8 0 t並反應2小 時。然後，於減壓下在180 °C下去除未反應之苯胺後，製 得含胺基之樹脂134.6g。所得樹脂之羥基當量爲 122.0g/eq_，胺當量爲 3 86.4g/eq.，軟化點爲 85°C，於 I50 它下之熔化黏度爲0.19mPa· s。將GPC圖表，表示於第10 圖。 [實施例5 ] 飼給實施例4中所得之含胺基之樹脂5 0 g、酞酸酐 -31 - 201125838 19.2g，在導入氮氣之下加熱爲150°C以使其溶解並反應1 小時。在此當中，因反應所生成之水，則加以去除於系統 外。然後，於減壓下在23 0 °C下去除未反應之酞酸酐，製 得含有醯亞胺基之樹脂63.8g (樹脂C )。所得樹脂之羥基 當量爲189§/69.’胺當量爲1103(^4£1.，軟化點爲111.3°〇 ，於150°C下之熔化黏度爲2.3mPa· s。將GPC圖表，表示 於第1 1圖。 [實施例6] 飼給苯胺45.9g( 0.49莫耳）、雙酚A 150g(0.66莫耳 )，在導入氮氣之下加熱爲80 °C，並滴下37 %甲醛水溶液 40.0g( 0.49莫耳）。接著，在攪拌下升溫至95 °C並回流2 小時，再於脫水後升溫至1 8 0 °C並反應2小時。然後，於減 壓下在1 8 0 °C下去除未反應之苯胺後，製得含胺基之樹脂 186.6g。所得樹脂之羥基當量爲132.4g/eq.，胺當量爲 5 1 6 · 2 g/ eq · ’軟化點爲8 8 °C ，於1 5 0 °C下之熔化黏度爲 0.19mPa. s。將GPC圖表，表示於第12圖。 [實施例7] 飼給於實施例6中所得之含胺基之樹脂7 0 g、酞酸酐 20.〗g ’在導入氮氣之下加熱爲150 °C以使其溶解並反應1 小時。在此當中’因反應所生成之水，則加以去除於系統 外。然後’於減壓下在23 0 °C下去除未反應之酞酸酐，製 得含有醯亞胺基之樹脂8 0 · 5 g (樹脂D )。所得樹脂之羥基 -32- 201125838 當量爲200g/eq. ’胺當量爲39630g/eq.，軟化點爲i〇5°C， 於150°C下之熔化黏度爲l_3mPa. s。將GPC圖表，表示於 第13圖。 [實施例8] 飼給苯胺23.7g ( 0.25莫耳）、苯酚芳烷基樹脂（明和 化成製，MEH-7800SS，OH (羥基）當量175，軟化點67°C )20〇8，在導入氮氣之下加熱爲80°(：，並滴下37%甲醛水 溶液20.6g(0_25莫耳）。接著，在攪拌下升溫至95 °C並回 流2小時，再於脫水後升溫至1 80 °C並反應2小時。然後， 在減壓下在180 °C下去除未反應之苯胺後’製得含胺基之 樹脂200g。胺當量爲1060g/eq·。將GPC圖表，表示於第14 圖。 將此含胺基之樹脂作成150 °C之後’飼給酞酸酐25.1 g ，在導入氮氣之下加熱爲1 5 0 °C以使其溶解並反應1小時。 在此當中，因反應所生成之水’則加以去除於系統外。然 後，於減壓下在230 °C下去除未反應之酞酸酐’製得含有 醯亞胺基之樹脂212.7g (樹脂E )。所得樹脂之經基當量 爲217g/eq.，胺基當量爲30540g/eq.’軟化點爲l〇l°C ’於 150°C下之溶化黏度爲2.2Pa · s。將GPC圖表’表示於第15 圖。 [合成例1 (比較）] 飼給苯胺40.0g、苯酚200.0g、37°/。甲醒水溶液41.5g’ -33- 201125838 在導入氮氣之下加熱爲80°C以使其溶解。接著，在攪拌下 升溫至95 °C並回流2小時，再於脫水後升溫至180。(：並反應 2小時。然後’在減壓下在180°C下去除未反應之苯酚、苯 胺後’製得含胺基之樹脂102.0g。所得樹脂之羥基當量爲 145.8g/eq·’ 胺當量爲 242 g/eq.，軟化點爲 61°C，於 150°C 下之熔化黏度爲〇.〇2Pa · s。 飼給所得之含胺基之樹脂102.0g、酞酸酐63.6g，在導 入氮氣之下加熱爲8 0 °C以使其溶解。然後，在攪拌下升溫 至1 5 0 °C並反應1小時。在此當中，因反應所生成之水，則 加以去除於系統外。然後，於減壓下在230 °C下去除未反 應之酞酸酐，製得含有醯亞胺基之樹脂152.lg (樹脂F) 。所得樹脂之羥基當量爲295g/eq·，胺當量爲39750g/eq.， 軟化點爲l〇5°C，於150°C下之熔化黏度爲〇.65Pa· s。 [實施例9至13及比較例1至3] 作爲環氧樹脂成分而使用鄰甲酚酚醛清漆型環氧樹脂 (環氧當量200、軟化點65 °C )，作爲硬化劑而使用於實 施例2、3、5、7、8、合成例1所得含醯亞胺基之樹脂（樹 脂A至F)、苯酚酚醛清漆（樹脂G;群榮化學製、PSM-4261、OH當量103、軟化點82°C )、苯酚芳烷基樹脂（樹 脂H;明和化成製' MEH-7800SS' OH當量175、軟化點67 °C )，將作爲塡充劑之氧化矽（平均粒徑18μηι)，作爲硬 化促進劑之三苯基膦以及表1中所示其他成分，按表1中所 示調配比例進行混練後，製得環氧樹脂組成物。使用該環 -34- 201125838 氧樹脂組成物，在175 °C下成型，並在175 °C下進行後塑化 (ρ 〇 s t c u r e ) 1 2小時，在製得硬化物試片後，供爲各種物 性測定之用。 玻璃化溫度（Tg )及線膨脹係數（CTE )之測定，係 採用熱機械測定裝置（thermomechanical measuring apparatus)，按10 °C/分鐘的升溫速度求出者。又吸水率 ，係作成經使用該環氧樹脂組成物以成型直徑50mm、厚 度3111111的圓盤，在後塑化後於85°(：、85%1^(相對濕度） 下使其吸濕100小時後的重量變化率。抗曲強度（bending strength)及彎曲模數（bending modulus)，係依照 JIS K6911，按 3點彎曲試驗法（three-point bending test)在 常溫下加以測定者。黏合強度（bonding strength)，係於 銅板2片之間，使用壓塑壓型機在！ 75 °C下成型25 mmx 12.5mmx0.5mm的成型物’並在}“^下實施後塑化12小時 後’求出抗張抗剪強度（tensile shearing strength)藉以 評價。阻燃性’係在厚度1 /1 6吋的試片之成型後，依照U L 94V-0規格進行評價，以5支試片時的合計燃燒時間表示者 。將其結果，表示於表1中。 -35- 201125838 表 L比較例3 I § o I 800 CSJ T—· in CO 5 in — § 00 CM 00 ο 0.28 234 比較例2 σ> σ> 800 CNJ in CO L 162 T— cq CM LO CO d 0.31 334 比較例1 ζ s 800 to CO 122 in — σ> co p 0.24 in <〇 實施例13 00 800 OJ in CO 00 q CS| — CM LO 00 Οί CNJ 0.19 寸 實施例12 in JO o 00 CSJ in CO p CM — ci CSJ 0.21 5 實施例11 CO 800 C\J in co CO •r— p T· co — s T~ 二 C\j ^*· 0.21 s 實施例10 CO CO CO 800 CNJ in CO 5 q — CM in ▼—· 00 CM CO 0.23 CM to 實施例9 S co CO o § OJ to co LO <〇 T· q CO — (Ο CM 0.22 00 ss m 祕 酹 樹脂A 樹脂B 樹脂c 樹脂D 樹脂E 樹脂F 樹脂G 樹脂H 氧化矽 m m 担 © 碳黑 棕櫚蠟 Tg (°C) CTE (<Tg,x 10-5) CTE (>Tg,x 10-5) 抗曲強度(MPa) 彎曲模數（GPa) 黏合強度(MPa) 吸水率(wt%) 燃燒時間(sec) -36- 201125838 【圖式簡單說明】 第1圖：含胺基之樹脂之i-NMR (氫原子核磁共振） 光譜。 第2圖：含胺基之樹脂之紅外吸收光譜（infrared absorption spectrum ) ° 第3圖：含胺基之樹脂之FDMS (場解吸質譜測定法） 光譜。 第4圖：含胺基之樹脂之GPC (膠透層析術）圖表。 第5圖：含醯亞胺基之樹脂之1H-NMR光譜。 第6圖：含醯亞胺基之樹脂之紅外吸收光譜。 第7圖：含醯亞胺基之樹脂之FDMS光譜。 第8圖：含醯亞胺基之樹脂之GPC圖表。 第9圖：含醯亞胺基之樹脂之GPC圖表。 第10圖：含胺基之樹脂之GPC圖表。 第11圖：含醯亞胺基之樹脂之GPC圖表。 第12圖··含胺基之樹脂之GPC圖表。 第13圖：含醯亞胺基之樹脂之GPC圖表。 第14圖：含胺基之樹脂之GPC圖表。 第15圖：含醯亞胺基之樹脂之GPC圖表。 5 -37-(here, Ri to R4, X, η and m' have the same meanings as in the general formula (j). Z is a binary group having at least two carbon atoms formed from a dicarboxylic acid anhydride). Further, the present invention relates to a process for producing a polyfluorene-containing compound containing a brewing imine group, which is characterized in that it can be used for a benzene ring having a hydroxyl group in the phenol represented by the above general formula (2). The above general formula (3) represents an aromatic amine 〇 _ 〇 5 to 1. 5 moles, and the aldehydes 〇·〇5 to 1. which can be represented by the above general formula (4). 5 moles, and the molar ratio of aromatic amines to aldehydes is from 0.5 to 2. The condition of 0 is reacted to obtain an amine group-containing polyhydroxy compound 'and then' the amine group-containing polyhydroxy compound can be Z(CO) 2 〇 (where the 'Z system has at least 2 carbon atoms The base of the dicarboxylic anhydride can be referred to as an amine group 1 molar acid anhydride group to K0 to 1. The ratio of 5 moles is used and reacted. Furthermore, the present invention is an epoxy resin composition which is an epoxy resin composition formed by an epoxy resin 201125838 and a hardener. It is characterized in that: as a part or all of the hardener, the above-mentioned amine-containing group is used. A polyhydric hydroxy compound or a polyhydric hydroxy compound containing a quinone imine group. Further, the present invention is an epoxy resin cured product characterized by curing an epoxy resin obtained by curing the epoxy resin composition. [Effects of the Invention] The amine group-containing polyvalent hydroxy compound and the quinone imine group-containing polyvalent hydroxy compound of the present invention are useful as a hardener, a modifier, and an epoxy resin intermediate for an epoxy resin, for example, as an application. In the case of an epoxy resin composition, in addition to excellent flame retardancy, it can impart high heat resistance, moisture resistance, and high adhesion to dissimilar materials, and is suitable for electrical use. • Use of electronic component seals, circuit board materials, and the like [Best Embodiment of the Invention] Hereinafter, the contents of the present invention will be described in detail. The amine group-containing polyvalent hydroxy compound (hereinafter, abbreviated as an amine group-containing resin) of the present invention can be represented by the general formula (1). Further, the quinone imine-containing polyvalent hydroxy compound (hereinafter, abbreviated as a quinone imine group-containing resin) of the present invention can be represented by the general formula (5). Since the quinone imine group-containing resin can be obtained by imidating the amine group of the amine group-containing resin, the amine group-containing resin is also an intermediate of the quinone imine-containing resin. Further, the amino group-containing polyhydric hydroxy compound and the quinone imine group-containing polyhydric hydroxy compound have a common point in the -11 - 201125838 polyhydric hydroxy compound, and the two are collectively referred to as the polyhydric hydroxy compound of the present invention. Or a resin containing an amino group or a quinone imine group. Since the amino group-containing polyvalent hydroxy compound of the present invention can be obtained by reacting a phenol represented by the general formula (2) with an aromatic amine and an aldehyde, it will first be described from the invention of the production method. In the general formula (2), 1 is a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms or a hydrocarbon group having 1 to 8 carbon atoms. If R is a hydrogen atom or a methyl group, the low viscosity is excellent. Further, if it is a hydroxyl group, it is excellent in heat resistance. Further, if it is a phenyl group, a benzyl group, a styryl group or an indenyl group, the moisture resistance and the flame retardancy are excellent. Preferred are a hydrogen atom, an alkoxy group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms. In the general formula (2), X is a direct bond, -〇-, -s-, _S〇2_, -CO- or a binary hydrocarbon group. If X is a direct bond, -S02-, -CO-, the heat resistance will be excellent. Further, when X is a methylene group, an ethylene group or an isopropylidene group, solvent solubility and low viscosity are excellent. Further, if X is -C Η 2 - φ -CH2- group or -CH2- Φ - φ -CH2- group, the shell IJ is excellent in moisture resistance, flame retardancy, and crack resistance. Here, 'Φ denotes a phenylene group. The divalent hydrocarbon group is preferably a hydrocarbon group having 1 to 14 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms or a subfield or xylylene group. In the general formula (2), n is a number from 1 to 1 。. Here, in the case where the phenols of the general formula are phenolic resins composed of a mixture of η値 different components, η is an average (number average) 値. Further, in the case of the phenolic compound of the general formula (2), for example, a bisphenol compound or a phenol compound having an integer of 1 or 2 or a bisphenol-12-201125838 compound having an average 値η of 1 to 2 A resin having a phenol compound as a main component or a compound or a resin as a main component is excellent in low viscosity and solvent solubility. More preferably, η is i if it is an integer, and 1 to 15 if it is an average 値. For a phenol represented by the general formula (2), 11 is an integer of 1 to 1 〇. In the case of a single compound, and in the case of a mixture of two or more kinds, and in the case of a mixture, it may be a resin having a distribution of molecular weight. Preferably, a bisphenol compound having η of 1 and A polyhydric phenolic resin having a molecular weight distribution. As exemplified, the bisphenol compound may be bisphenol F, bisphenol hydrazine, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, 4,4'. -dihydroxydiphenylphosphonium, 4,4'-dihydroxydiphenyl sulfide, 4,4,-di-diphenyldiphenyl ketone, fluorene biguanide, 2,2'-biphenyl ( Biphenol), 4,4'-biphenol. Further, the polyhydric phenol resin may, for example, be a phenol novolak, a bisphenol A novolac, an o-cresol novolac or a phenol aralkyl resin, and a biphenyl obtained by reacting phenol with bischloromethylbiphenyl. Type aralkyl resin. In the general formula (3), R2 and R3 represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. If R2 and R3 are a hydrogen atom or a methyl group, the low viscosity is excellent. Further, if it is a phenyl group, a benzyl group, a styryl group or a fluorenyl group, it is excellent in moisture resistance, flame retardancy, and high adhesion. Specific examples of the aromatic amine of the formula (3) include aniline, 2-methylaniline '3-methylaniline, 4-methylaniline, and 2,4-dimethylaniline' 2,6_ Dimethylaniline, ethylaniline, phenylaniline, benzylaniline, but from the viewpoint of low viscosity and reactivity-13-201125838, preferably aniline. In the general formula (4), R4 represents a hydrogen atom and a hydrocarbon group having 1 to 8 carbon atoms. Specific examples of the aldehyde of the formula (4) include formaldehyde, acetaldehyde and benzaldehyde. From the viewpoint of low viscosity and reactivity, formaldehyde is preferred. Further, as the aldehyde source at the time of the reaction, formaldehyde water, paraformaldehyde, trioxane or the like can be used. The amine group-containing resin of the present invention reacts with a reaction mixture containing a phenol represented by the formula (2) and an aromatic amine represented by the formula (3) and an aldehyde represented by the formula (4), that is, Can be synthesized. In this reaction, the main reaction will proceed as follows. First, an aldehyde is an aromatic amine adduct which reacts preferentially with an aromatic amine to form an aldehyde. Next, the adduct is reacted with a phenol to form a dehydration condensation product in which a phenol and an aromatic amine are bonded via a fl-methyl group, and then the dehydrated condensate causes a transfer. After the transfer reaction, an amine group-containing polyhydroxy compound of the present invention in which a phenol and an aromatic amine are reacted by a methyl group bond is formed. Therefore, 'in the case of an aromatic amine, such as an aldehyde, the unreacted aromatic amine may remain. If the aldehyde is excessive, the benzoquinone or the resulting amine-containing resin may be used. The reaction is high molecular weight. From these viewpoints, the amount of the aromatic amine used is a benzene ring having 1 hydroxy group in the benzoic acid, which is 0. 05 to 1. 5 mole range, but preferably at 0. 1 to 1. 0' is better at 0. 15 to 1. 0 Mo, then better at 0. 2 to 0·9 Moer's special is in 〇·4 to 0. 8 mole range. If it is less than this, the improvement effect of heat resistance, flame retardancy, etc. is low, and if it is more than -14 to 201125838, the softening point is promoted and the handling property is lowered. The amount of the aldehyde used is benzene ring oxime having a hydroxyl group in the phenol, and is in the range of 〇·〇5 to 1. The range of 5 moles, preferably from 1 to 1 〇, more preferably at 0. 15 to 1_〇莫耳, and then better at 〇·2 to 〇. 9 Mo Er, especially good at 0. 5 to 2. 0 mole range. Also, the aromatic amines are in the form of 0. 9 to 1. 1 mole range, but better in 〇. 8 to 1. 2 moles, more preferably in the range of 0 · 9 to 1 1 m. If it is less than this, the amount of unreacted aromatic amine remaining after the reaction increases, and if it is more than this, the phenol or the resulting amine group-containing resin may be combined with the aldehyde. When the reaction is carried out and the polymer is quantified, the high softening point and the high viscosity result are lowered, and the gelation may be caused. The aldehydes function as a crosslinking agent that bonds phenols to aromatic amines. For one benzene ring in the phenol, m aromatic amines may be combined. The reaction is a condensation reaction which produces water. Here, the benzene ring having a hydroxyl group in the phenol is defined by the meaning of the benzene ring bonded to the hydroxyl group in the general formula (2), and the same as the benzene ring or the phenol ring in the phenol. This reaction can be carried out in the absence of a catalyst or a catalyst. When a catalyst is used, it can be appropriately selected from well-known inorganic acids and organic acids as a catalyst. Specific examples include mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, or organic acids such as formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, dimethylsulfuric acid, and diethylsulfuric acid, or zinc chloride or chlorine. Lewis acid or ion exchange resin, activated clay, oxidized sand, -15- 201125838 Zeolite, etc. )Wait. Further, such a reaction is usually carried out at 1 to 20 ° C for 1 to 20 hours. A preferred reaction temperature is 50 to 20 (TC, preferably a reaction time of 1 to 1 hour. Further, in the reaction, it can be used as a solvent: methanol, ethanol, propanol, butanol, ethylene glycol. , methyl cellosolve, ethyl celecoxib and other alcohols, or ketones such as propyl ketone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl ether, diethyl ether, An ether such as diisopropyl ether, tetrahydrofuran or dioxane; an aromatic compound such as benzene, toluene, chlorobenzene or dichlorobenzene; etc. After the completion of the reaction, sometimes the amine-containing resin obtained is obtained. Unreacted aromatic amines and aldehydes remain, and the residual aromatic amines and aldehydes are usually removed by distillation, water washing or solvent fractionation. Since the reaction is carried out during distillation under reduced pressure, the temperature and time (total) are preferably in the above range. The amount of unreacted aromatic amines and aldehydes remaining in the amine group-containing resin is controlled to be less. Preferably, it is usually 5% by weight or less, preferably 3% by weight or less, more preferably When the amount of the aromatic amines and the aldehydes remaining is large, volatilization occurs when the molded article is produced, so that the molding workability is lowered and the voids of the molded product may be caused. The flame retardancy of the molded article is also lowered. The amine group-containing polyvalent hydroxy compound of the present invention can be represented by the above general formula (1). Here, X, R, and η are related to the phenol of the general formula (2). In the description of the class, X, L and η are the same. Further, R2 and R3 are the same as R2 and R3 in the description of the aromatic amine of the general formula (3), and the R4 system is in the general formula of -16-201125838. In the description of the aldehyde of (4), 114 is the same. In the general formula (1), m is an integer of 0 to 2, but based on the average of each benzene ring (phenol ring) bonded to the hydroxyl group, For 〇. 05 to 丨. The scope of 5. When viewed as an amine group-containing resin, the number of m is 1 phenol ring, on average, at 0. 05 to 1. 5, but preferably in ^丨 to 丨^, more preferably in 0. 15 to 1. 0, then better at 0. 2 to 0. 9, especially good for you. 4 to 0. The scope of 8. If it is less than this, the effect of improving heat resistance and flame retardancy is small, and if it is more than this, the softening point is increased, and the handling property is lowered. When the amino group-containing polyvalent hydroxy compound of the present invention is a compound having no molecular weight distribution and η is an integer, at least one m in one molecule is 1 or 2. Further, if the η has a molecular weight distribution and the compound which belongs to the average enthalpy, the average m of each molecule (the total number of m in the numerator) is 0. Range of 1 to 3. The amine group-containing resin of the present invention has a softening point of preferably from 40 to 160 ° C, preferably from 50 to 1 20 ° C, more preferably from 60 to 100 ° C. Here, the softening point is based on the softening point measured by the ring and ball test of JIS K-6911. If it is lower than this, when it is blended in an epoxy resin, the heat resistance of the cured product is lowered, and if it is higher, the fluidity at the time of molding is lowered. Further, when it is used as an intermediate of the quinone-imine-based resin of the present invention, the softening point and viscosity of the obtained quinone-imine-based resin are increased, so that handling property is lowered. Here, the softening point of the amine group-containing resin and the quinone imine group-containing resin can be adjusted by changing the η or m of the general formula (1), and generally, if it is changed, Can increase the softening point. -17- 201125838 Next, the quinone imine group-containing resin of the present invention represented by the general formula (5) will be described. In the general formula (5), the core to R4, X, m, and η are the same as those described in the general formula (1). Further, in the general formula (5), when the number of m is small, the effect of improving heat resistance, flame retardancy, and the like is reduced, and if it is more than this, the softening point is increased and the handling property is lowered. . Z is a binary group formed by removing an acid anhydride group (co2) from a carboxylic acid anhydride represented by z(co) 2o. Thus, the Z system can be understood from the description of the anhydrous substance of the dicarboxylic acid. Preferred Z is exemplified by a binary aliphatic group which may be represented by CnH2nSCnH2n-2, a binary 1 to 3 ring aromatic ring which may be represented by A, and a binary represented by Ar-Y-Ar. An aromatic group, which may be a binary hydrocarbon group represented by a ring C4-6, which may be bicyclic (Ccyclyl) C6. 8 represents a binary bicyclic hydrocarbon group. Further, η is preferably in the range of 1 to 8. In the case of A, a divalent benzene ring, a naphthalene ring 'anthracene ring or a phenanthrene ring is preferred. For Ar, a benzene ring is preferred, and two Ar groups may be different. Y is preferably a single bond, 0, S, SO, S02, CO or CnH2n, and n is preferably in the range of 1 to 8. Ring C4. In particular, a binary C4 to C6 cycloalkane, cycloalkenene or cyclodiene ring is preferred. Can be double ring (: 6. The binary bicyclic hydrocarbon group represented by 8 is preferably a binary C6-8 bicycloalkane ring. These hydrocarbon groups, aromatic rings or aliphatic rings may have a substituent, and in the case of having a substituent, preferred substituents are an alkyl group having 1 to 6 carbon atoms, a phenyl group, and an alkoxy group having 1 to 6 carbon atoms. Base, hydroxyl or halogen. Further, Z is preferably selected from the group consisting of: an unsaturated aliphatic group having 2 to 24 carbon atoms, a non--18-201125838 saturated monocyclic aliphatic group, and an unsaturated condensed polycyclic aliphatic group in a direct manner or by An unsaturated non-condensed polycyclic aliphatic group which is linked to each other by a member of cross linking, a monocyclic aromatic group which has a chain aliphatic group as a substituent, and a chain aliphatic group as a substituent a condensed polycyclic aromatic group having a group, an unsaturated monocyclic aliphatic group as a substituent, and a condensed polycyclic aromatic group having an unsaturated monocyclic aliphatic group as a substituent The base of the yuan. The quinone imine group-containing resin of the present invention can be obtained by reacting a dicarboxylic acid anhydride with the amine group-containing resin of the present invention. The dicarboxylic acid anhydride usable herein may, for example, be maleic anhydride, phthalic anhydride, 2,3-diphenyl ketone dicarboxylic anhydride, 3,4-diphenyl ketone dicarboxylic anhydride, 2,3 - Dicarboxyphenyl phenyl ether anhydride, 3,4-dicarboxyphenyl phenyl ether, 2,3-biphenyldicarboxylic anhydride, 3,4-diphenyldicarboxylic anhydride, 2,3-dicarboxylic acid Phenylphenyl phthalic anhydride, 3,4-dicarboxyphenyl phenyl phthalic anhydride, 2,3-dicarboxyphenyl phenyl sulfide anhydrate, 3,4-dicarboxyphenyl phenyl sulfide anhydrate, 1,2-Caidicarboxylic anhydride, 2,3-naphthalene dicarboxylic anhydride, 1,8-naphthalene dicarboxylic anhydride, 1,2-anthracene dicarboxylic anhydride, 2,3-indole dicarboxylic anhydride, 1,9·蒽Dicarboxylic anhydride, cyclobutane-1,2-dicarboxylic anhydride, cyclobutane-1,3-dicarboxylic anhydride, iota, 2-cyclopentane dicarboxylic anhydride, 1-methyl-1,2-cyclopentane Alkanedicarboxylic anhydride, 12-cyclohexanedicarboxylic anhydride, 1,3-decanehexanedicarboxylic anhydride, 1-cyclohexene-1,2·dicarboxylic anhydride, 2-cyclohexene-1,2-di Carboxylic anhydride, 3-cyclohexene-1,2-dicarboxylic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, 1-cyclohexene-1,3-dicarboxylic anhydride, 3-cyclohexene -1,3·dicarboxylic anhydride, 4_cyclohexene-1,3-dicarboxylic anhydride, 1 3-cyclohexadiene-i,2-dicarboxylic anhydride, 1,4-瓌hexadiene-1,2-dicarboxylic anhydride, 2,4-cyclohexadiene-1,2-dicarboxylic anhydride, - 19- 201125838 2,5-cyclohexadiene-1,2-dicarboxylic anhydride, 2,6-cyclohexadiene- l,2-dicarboxylic anhydride, 3,5-cyclohexadiene-1,2 - Dicarboxylic anhydride, cyclohexyl succinic anhydride, 5-bicyclo[2,2,1]heptene-2,3-dicarboxylic anhydride, bicyclo[2,2,1]heptene-2,3-dicarboxylic anhydride, 2 -bicyclo[2,2,1]heptene-2,3-dicarboxylic anhydride, 2_bicyclo[2,2,2]octene-2,3-dicarboxylic anhydride, 5-bicyclo[2,2,2 ] octene-2,3-dicarboxylic anhydride and the like. Among them, more suitable compounds are maleic anhydride, phthalic anhydride, and nordic acid anhydride. When maleic anhydride is used, a maleic imide group is formed, as in the case of the resin composition for this application, since the maleimine group may participate in the hardening reaction, a large heat resistance can be expected. Upgrade. Further, in the case of using decanoic anhydride and norbornene dianhydride, improvement in moisture resistance and heat resistance can be expected in the cured product. In the production method, first, the carboxylic acid anhydride is reacted with the amine group-containing resin, and the addition product is subjected to heating, dehydrating, ring closure, or a predetermined solvent in the presence of an acid catalyst. It is heated and refluxed, whereby it is subjected to dehydrating condensation. The method of heating and dehydrating the closed loop without using a catalyst is carried out by heating and dehydrating under normal pressure or reduced pressure. The reaction is usually carried out in the absence of a solvent, but an inert solvent may also be used for the reaction. In such a method, any of the above carboxylic anhydrides may be used, but a carboxylic anhydride other than an unsaturated aliphatic carboxylic anhydride is particularly suitable. If an acidic catalyst is used to dehydrate the ring, as an acid catalyst, inorganic acid such as sulfuric acid, hydrochloric acid or phosphoric acid, heteropoly-acid such as phosphotungstic acid or phosphomolybdic acid, and p-toluene may be used. Halogenated carboxylic acid such as organic sulfonic acid, trichloroacetic acid or trifluoroacetic acid, such as acid or aquaculture, 'oxidized sand -20-201125838 A solid acid such as alumina, a cationic ion exchange resin, and the like. In particular, sulfuric acid, phosphoric acid, and p-toluenesulfonic acid are suitable. Further, these acids can be formed into a form of a salt with an amine. Although these acidic catalysts vary depending on the type thereof, generally, the total amount of the dicarboxylic anhydride and the above-mentioned amine group-containing resin is 0. An amount of from 1 to 10% by weight is preferably used. If the amount of catalyst is less than 〇.  When the amount is 1% by weight, the desired catalyst effect cannot be achieved, and even if it is used in an amount of 10% by weight or more, the effect of a certain degree or more cannot be obtained, so that it is not only uneconomical but also difficult to remove the residual catalyst. As the solvent to be used in the condensation reaction, an aliphatic or alicyclic hydrocarbon such as hexane, heptane, decane or cyclohexane, an aromatic hydrocarbon such as benzene, toluene or hydrazine, and a halogen compound thereof may be used. Ν-dimethylformaldehyde, N-methylpyrrolidone, acetonitrile, hydrazine, hydrazine-dimethylacetamide, dimethyl hydrazine, sulfolane, anisole, n-butyl ether, etc. Oxygen-containing or sulfur-containing polar solvent. The amount of the solvent is generally in the range of from 1 to 20 times, particularly from 2 to 10 times, in the total amount of the above-mentioned amine group-containing resin and carboxylic anhydride. The reaction temperature is usually from 80 to 200 ° C, preferably from 150 to 200 ° C. The reaction temperature at the time of carrying out the reaction under heating under reflux is somewhat different depending on the solvent to be used, but it is usually suitably in the range of 80 to 190 ° C, particularly 1 to 16 CTC. The pressure may be any of pressurization, normal pressure, and reduced pressure, and may be appropriately selected depending on the solvent to be used and the reaction temperature. Reaction time, usually in 〇.  5 to 20 hours, especially in the range of 1 to 15 hours. Here, the feed amount of the dicarboxylic anhydride and the amine group-containing resin is preferably such that the amount of the dicarboxylic anhydride is equal to or more than the amount of the amine group-containing resin component. In general, based on the molar basis, the total amine group in the amine group-containing resin, -21 - is carboxylated to form the dicarboxylic acid containing 醯80 carboxylic acid, and the position of the above is the imine ring. Oxygen monoester, based on the imine group of 201125838 anhydride can become 1. 0 to 1. The mixture was fed in a manner of 5 times, and the reaction mixture was washed to remove residual acid anhydride, and then the solvent was distilled off to obtain a concentrate. The imine resin, which is a quinone imine group/hydroxy group, has a softening point of about 60 to 160 ° C. The removal of the anhydride is preferably carried out at 150 to 25 (TC) depending on the boiling point of the dicarboxylic anhydride. The quinone imine-containing resin of the present invention is an amine-containing group which reacts with the dicarboxylic anhydride and is disposable. At least a portion, preferably all, has been converted to an imidized amine group, preferably less preferably 5,000 g/eq. (Equivalent) or more, better. Here, the amine equivalent energy is 5000 g/eq. In the case of chemical conversion, the flame retardancy and heat resistance are improved, and the present invention is an epoxy resin cured product, a resin or a hardener, or an epoxy resin composition, and the amine-containing composition of the present invention is used. There are the following two types. 1) A part or all of the hardener, and a composition of the resin. 2) A composition of a resin which is a part or all of a hardener. 3) As a part or the whole of the curing agent, the composition of the resin and the above-mentioned quinone imine group-containing resin may be used. The condensation reaction is completed, and the catalyst is not reacted. The ratio obtained in this manner is different from that of 3:97 to here, and the unreacted two is different, but the resin of the mercapto group imine group formed at the amine group of the resin is reduced. The amount of the amine is 10,000 g/eq. It is more advantageous to make a rumor in the above way. It is characterized in that, in the case of a hardener or a quinone imine group, the aforementioned amine-containing compound is formulated with the above-mentioned hydrazine-containing compound. -22- 201125838 In the case of the compositions of the above 1) and 2), the amount of the amine group-containing or quinone-based resin is adjusted (for example, when both the amine group-containing resin and the quinone imine group-containing resin are blended) And the total amount thereof is usually in the range of 2 to 200 parts by weight, preferably 5 to 80 parts by weight, based on 100 parts by weight of the epoxy resin. If it is less than this, the effect of flame retardancy, low moisture absorption, and adhesion improvement is small. If it is more than this, the moldability and the strength of the cured product may be lowered. When the amine group-containing resin or the quinone imine group-containing resin of the present invention is used as the total amount of the cured product, generally, the respective amounts are determined by considering the amine group in the resin and the active hydrogen of the phenolic hydroxyl group (active) The amount of hydrogen is formulated in equilibrium with the equivalent weight of the epoxy group in the epoxy resin. The equivalent ratio of epoxy resin and hardener is usually 0. 2 to 5. The range of 0 is preferably 0. 5 to 2. The range of 0. If it is larger or smaller, the hardenability of the epoxy resin composition is lowered, and the heat resistance, mechanical strength, and the like of the cured product are lowered. As the curing agent, a curing agent other than the amine group-containing or quinone imine group-containing resin of the present invention can be used. The compounding amount of the other hardener is a compounding amount of the amine group or the quinone group-containing resin, and is usually 2 to 200 parts by weight, preferably 5 to 80 parts by weight, based on 100 parts by weight of the epoxy resin. It is determined within the scope of the scope. If the amount of the resin containing an amine group or a quinone imine group is less than this, the effect of improving the flame retardancy, the low moisture absorption property, and the adhesion property is small, and if it is more than this, the moldability and hardening are obtained. The strength of the object will be reduced. For hardeners other than those containing an amine group or a quinone imine group, 1 is generally used as a hardener for epoxy resins, and is known as dicyandiamide, acid liver, and polysaccharides. Benzos, aromatics and aliphatic amines. Among these, in the field where high electrical insulation properties such as semiconductor sealing materials are required, it is preferred to use a polyhydric phenol as a curing agent. Hereinafter, specific examples of the curing agent will be shown. Examples of the acid anhydride hardener include: phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydro sulphuric acid, hymic acid anhydride, and ten Examples of the polyhydric phenols such as dicarbene succinic anhydride, nadic acid anhydride, and trimellitic anhydride include bisphenol A, bisphenol F, biguanide S, and bismuth bisphenol. a binary phenol such as 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcin, naphthalenediol, or ginseng (4-hydroxyphenyl)methane, 1, A ternary or higher phenol represented by 1,2,2-indole (4-hydroxyphenyl)ethane, a phenol novolak, an o-cresol novolac, a naphthol novolak, a polyvinyl phenol or the like. Furthermore, there are: phenols, naphthols, bisphenol A' bisphenol F, bisphenol S' bisphenol, 4,4' biphenol, 2,2'-biphenol, hydroquinone, resorcin A polyphenolic compound such as a divalent phenol such as naphthalenediol or a condensing agent such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzylaldehyde or p-nonyl glycol. Further, the phenol resin composition of the present invention described above may be blended. In the case of amines, there are: 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylanthracene, meta-phenylene Aromatic amines such as diamines and p-nonyldiamines, such as ethyldiamine, hexamethylenediamine, di-24-201125838 exoethyltriamine, tri-extension ethyltetramine, etc. . One or two or more kinds of these curing agents may be used in combination with the above-mentioned composition. The epoxy resin used for the above composition may be selected from two or more epoxy groups in one molecule. For example, bisphenol A, bisphenol F, 3, 3', 5, 5'-tetramethyl bisphenol? , bisphenol 3, bismuth bisphenol, 2,2'-biphenol, 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenol, resorcin, naphthalenediol, etc. Binary phenolic epoxide, ginseng (4-hydroxyphenyl)methane, 1,1,2,2-indole (4-hydroxyphenyl)ethane, phenol novolac, o-cresol novolac, etc. An epoxide of a phenol or more, an epoxide of a co-condensation resin of a dicyclopentadiene and a phenol, and a ring of a phenol aralkyl resin synthesized from a phenol or a p-dithiomethane group. An oxide, an epoxide of a biphenyl aralkyl phenol resin synthesized from a phenol or a bischloromethylbiphenyl, or a naphthol aralkyl synthesized from a naphthol and a p-dithiomethylene group. Resin-based epoxides, etc. These epoxy resins may be used singly or in combination of two or more. More preferred epoxy resins are: 3,3',5,5'-tetramethyl-4,4,-dihydroxybiphenol, 3,3',5,5'-tetramethyl-bisphenol The crystalline epoxy resin obtained by F or the like is an epoxy resin obtained from a polyfunctional resin such as o-cresol novolac, or an epoxy resin obtained from a phenol aralkyl resin or a biphenyl aralkyl resin at room temperature. The bottom is a solid epoxy resin. In the epoxy resin composition of the present invention, as a further modifier, polyester, polyamine, polyimine, polyether, polyamino acid awake, petroleum resin, enamel resin (indene resin) can be appropriately formulated. ), • 香 co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co co The amount to be added is usually in the range of 2 to 30 parts by weight based on 1 part by weight of the epoxy resin. Further, in the epoxy resin composition of the present invention, it is adjustable: an inorganic chelating agent, a pigment, a flame retardant, a thixotropy addition agent, a coupling agent (coupling agout), a fluidity improving agent ( Additives such as fluidity promotor). Examples of the inorganic chelating agent include spherical or crushed fused silica, vermiculite powder such as crystalline vermiculite, aluminum oxide powder, glass powder, or mica or talc. A preferred blending amount of calcium carbonate, aluminum oxide, hydrated aluminum oxide or the like in the case of using a semiconductor sealing material is 70% by weight or more, more preferably 80% by weight or more. Examples of the pigment include organic or inorganic body pigments, flake pigments, and the like. The thixotropic additive may be a lanthanide, a castor oil, an amide wax, an oxidized polyethylene 〇 (〇xyp〇lyethylene wa X ), or an organic bentonite. ( 〇rganicbent ο nite ) is the same. Further, in the epoxy resin composition of the present invention, a curing accelerator may be used as needed. For example, there are: amines, imidazoles, organic phosphines, Lewis acids, etc., specifically: 1,8-diazabicyclo(5,4,0)decene-carbene-7, three-stretching Tertiary amines such as bisamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, ginseng (dimethylaminomethyl)phenol, 2-methylimidazole, 2-phenylimidazole, 2 -Imidazoles such as ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, tributylphosphine, methyldiphenylphosphine, triphenylphosphine, and Organophosphines such as phenylphosphine and phenylphosphine, tetraphenyl-26- 201125838 phosphine tetraphenyl borate, tetraphenylphosphine. Tetrasubstituted scales such as ethyl triphenyl borate, tetrabutylphosphine and tetrabutyl borate, tetrasubstituted boric acid vinegar, 2_B_4_methylimidazole • tetraphenyl borate, N-methyl A tetraphenylboron salt such as morpholine or tetraphenylborate. In terms of the amount of addition, it is usually 1 part by weight to the epoxy resin, which is 0. A range of 2 to 5 parts by weight. In the resin composition of the present invention, if necessary, a release agent such as carnauba wax or 〇p (oily blend) wax, γ-glycidoxypropyltrimethoxy decane, or the like can be used. A coloring agent such as a coupling agent or carbon black, a flame retardant such as antimony trioxide, a lubricant such as a low stress agent such as polyoxygenated oil, and a lubricant such as calcium stearate. The epoxy resin composition of the present invention can be impregnated on a glass cloth, an aramide nonwoven fabric, or a liquid crystal polymer after being made into a varnish state dissolved in an organic solvent. A polyester such as a woven fabric is not a fibrous material such as a woven fabric, and then solvent removal is performed to form a prepreg. Further, it may be formed into a laminate by coating on a sheet such as a copper foil, a stainless steel foil, a polyimide film, or a polyester film. When the epoxy resin composition of the present invention is heat-cured, it can be used as an epoxy resin cured product of the invention, and the cured product is low in hygroscopicity, high in heat resistance, adhesion, flame retardancy, and the like. Excellent. Such a cured product can be obtained by molding an epoxy resin composition by means of cast molding, press moulding, transfer molding, or the like. The temperature at this time is usually in the range of 120 to 22 °C. -27- 201125838 The amine- or quinone-based resin of the present invention, if mixed with other polyphenols, can also be used as a phenol resin composition. The content of the amino group-containing or quinone-based resin is from 2 to 200 parts by weight, preferably from 5 to 100 parts by weight, more preferably from 10 to 1 part by weight to the other polyhydric phenols. A range of 80 parts by weight. If it is less than this, the reforming effect such as low moisture absorption, heat resistance, adhesion, and flame retardancy is small, and if it is more than this, the viscosity is increased to deteriorate the moldability. The other polyhydric phenols referred to herein may be the same as the polyhydric phenols described in the examples of the conventional hardeners as the epoxy resin composition. The phenol resin composition can be used as a phenol resin hardener if it is used as a curing agent generally used for a phenol resin molding material such as hexamethyltetramine. Further, the amine-containing or quinone-based resin of the present invention can be an amine-containing resin by reacting a halogenated compound compound, a halogenated stimulating compound 'epihalohydrin, etc. A part or all of the hydrogen atom of the amine group and the phenolic hydroxyl group is substituted with an alkyl group, an alkenyl group, a glycidyl group or the like. [Embodiment] [Examples] Hereinafter, the contents of the present invention will be specifically described by way of examples. Here, the viscosity system is BROOKFIELD, and the CAP2000H and softening points are measured according to JIS K-691 1 ' and determined by the method of the universal method. In addition, Gpc (gel permeation chromatography) is determined by: device; Japan's Waters -28- 201125838 (stock) system, 515A type, column (column); TSK-GEL 2000x3 branch and TSK- GEL 4000X1 (all made by Tosoh Co., Ltd.), solvent; tetrahydrofuran, flow rate; 1 m 1 /min, temperature: 38 °C, detector; RI (radioisotope) conditions, used for the calibration line Polystyrene standard solution. The amine equivalent is obtained by using 0. 1M (mole) obtained by potentiomentic differential titration of perchloric acid-acetic acid solution. Further, the base equivalent of the amine group-containing resin is obtained by subtracting the amine determined by the measurement of the amine equivalent by the total amount of the hydroxyl group and the amine group determined from the acetyl chloride method. The basis amount is estimated by estimating the amount of hydroxyl groups. [Example 1] Feeding aniline 46. 5g (0. 5 mol), 4,4'-dihydroxydiphenylmethane 200 g (1. 0 mole), heated to 80 ° C under the introduction of nitrogen, and dropped 37% formaldehyde aqueous solution 40. 5g ( 0. 5 Moore). Subsequently, the temperature was raised to 95 ° C with stirring and refluxed for 2 hours, and after dehydration, the temperature was raised to 180 ° C and reacted for 2 hours. Then, after removing unreacted aniline at 180 ° C under reduced pressure, an amine group-containing resin 2 3 was obtained. 5g. The hydroxyl equivalent of the obtained resin is 1 17. 4g/eq.  ' The amine equivalent is 626. 4g/eq. The softening point was 62 ° C, and the melt viscosity at 150 ° C was 31 mPa·s (megapoise). The 1H-NMR spectrum is shown in Fig. 1 'The infrared absorption spectrum is shown in Fig. 2'. The FDMS spectrum is shown in Fig. 3, and the GPC chart is shown in Fig. 4. In the FDMS spectrum, it is observed that m/z = 200 corresponding to n = 1 & m = 〇 in equation (1), m/z = 305 corresponding to n = l and m = l, corresponding to n = 2 And -29 - 201125838 m = l m/z = 5l8, m/z = 623 corresponding to n = 2 and m = 2, m/z = 728 corresponding to n = 2 and m = 3, corresponding to n = 3 and m = 2 m/z = 835, m/z = 940 corresponding to n = 3 and m = 3, m/z = 1 045 corresponding to n = 3 and m = 4, corresponding to n = 4 and m = 3 m/z = 1152, corresponding to n = 4 and m = 4, m/z = 1258 ' corresponds to n = 5 and m = 3, m/z = 1 3 63, corresponding to n = 6 and m = 2 m / z = 1469. Here, in the description of the FDMS spectrum, m of the formula (1) means the total of m in one molecule. [Example 2] 60 g of an amine group-containing resin obtained in Example 1 and phthalic anhydride were fed. 2 g, heated to 150 ° C under introduction of nitrogen to dissolve and react for 1 hour. In this case, the water generated by the reaction is removed from the system. Then, the unreacted phthalic anhydride was removed at 23 ° C under reduced pressure to obtain a quinone imine group-containing resin 5 7 .  1 g (resin A). The hydroxyl content of the obtained resin was 157 g/eq. The amine equivalent is 74950g/eq. The softening point is 76 ° C, and the melt viscosity at 150 ° C is 0. 1 ImPa · s. The 1H-NMR spectrum is shown in Fig. 5, the infrared absorption spectrum is shown in Fig. 6, the FDMS spectrum is shown in Fig. 7, and the GPC chart is shown in Fig. 8. In the FDMS spectrum, m/z = 200 corresponding to n = 1 and m = 0 in equation (5), m/z = 435 corresponding to n = 1 and m = l, corresponding to n = 2 is observed. m/z = 647 for m=l, m/z = 670 for n=l and m=2, m/z = 884 for n = 2 and m = 3, corresponding to n=l and m = 3 m/z = 906, m/z = 1095 corresponding to n = 3 and m = 2, m/z = 1118 corresponding to n = 2 and m = 3, corresponding to n = 3 and m = 3 The case of m/z=1330. -30-201125838 [Example 3] 60 g of an amine group-containing resin obtained in Example 1 and maleic anhydride were fed. 4 g, 120 g of toluene, was heated to 11 ° C under introduction of nitrogen and reacted for 2 hours while azeotroping with toluene to remove water outside the system. Then, the toluene and the unreacted maleic anhydride are removed by heating at 180 ° C under reduced pressure to obtain a resin containing a quinone imine group. 3g (resin B). The hydroxyl equivalent of the obtained resin was 144 g/eq. , the amine equivalent is 1 3 8400g / eq. The softening point is 88. 5 ° C, at 150 ° (: the melting viscosity is 〇. 44?3. 3» Will 〇? (: chart, shown in Figure 9 Figure 0 [Example 4] feed to aniline 46. 5g ( 0. 5 moles, 4,4'-dihydroxydiphenylmethane 100§ (0. 5 moles, heated to 80 导入 under the introduction of nitrogen. And drip 37% formaldehyde aqueous solution 4 〇. 5g ( 0. 5 Moore). Subsequently, the temperature was raised to 95 ° C under stirring for 2 hours, and after dehydration, the temperature was raised to 180 ° and the reaction was carried out for 2 hours. Then, after removing unreacted aniline at 180 ° C under reduced pressure, an amine-containing resin 134 is obtained. 6g. The hydroxyl equivalent of the obtained resin was 122. 0g/eq_, amine equivalent is 3 86. 4g/eq. The softening point is 85 ° C, and the melting viscosity under I50 is 0. 19mPa·s. The GPC chart is shown in Figure 10. [Example 5] The amine group-containing resin obtained in Example 4 was supplied with 50 g of phthalic anhydride -31 - 201125838. 2 g was heated to 150 ° C under introduction of nitrogen to dissolve and react for 1 hour. In this case, the water generated by the reaction is removed from the system. Then, the unreacted phthalic anhydride is removed at 23 ° C under reduced pressure to obtain a resin containing a quinone imine group. 8g (resin C). The hydroxyl equivalent of the obtained resin was 189 §/69. 'The amine equivalent is 1103 (^4 £1. The softening point is 111. 3 ° 〇, the melt viscosity at 150 ° C is 2. 3mPa·s. The GPC chart is shown in Figure 11. [Example 6] Feeding aniline 45. 9g (0. 49 moles, bisphenol A 150g (0. 66 mol), heated to 80 ° C under the introduction of nitrogen, and dropped 37% formaldehyde aqueous solution 40. 0g ( 0. 49 moles). Subsequently, the temperature was raised to 95 ° C with stirring and refluxed for 2 hours, and after dehydration, the temperature was raised to 180 ° C and reacted for 2 hours. Then, after removing unreacted aniline at 180 ° C under reduced pressure, an amine-containing resin is obtained. 6g. The hydroxyl equivalent of the obtained resin is 132. 4g/eq. , the amine equivalent is 5 1 6 · 2 g / eq · 'softening point is 8 8 ° C, and the melt viscosity at 150 ° C is 0. 19mPa.  s. The GPC chart is shown in Figure 12. [Example 7] The amine group-containing resin obtained in Example 6 was supplied with 70 g of phthalic anhydride. 〗 〖g was heated to 150 ° C under introduction of nitrogen to dissolve and react for 1 hour. In this case, the water generated by the reaction is removed from the system. Then, unreacted phthalic anhydride was removed under reduced pressure at 23 ° C to obtain a resin containing ruthenium imine group 80 0 · 5 g (resin D). The hydroxy group of the obtained resin -32- 201125838 equivalent is 200g/eq.  'The amine equivalent is 39630 g / eq. The softening point is i〇5°C, and the melting viscosity at 150°C is l_3mPa.  s. The GPC chart is shown in Figure 13. [Example 8] Feeding aniline 23. 7g ( 0. 25 mol), phenol aralkyl resin (manufactured by Minghe Chemical Co., Ltd., MEH-7800SS, OH (hydroxyl) equivalent 175, softening point 67 ° C) 20 〇 8, heated to 80 ° under nitrogen introduction (:, and drip 37% formaldehyde aqueous solution 20. 6g (0_25 mol). Subsequently, the temperature was raised to 95 ° C with stirring and refluxed for 2 hours, and after dehydration, the temperature was raised to 1 80 ° C and reacted for 2 hours. Then, 200 g of an amine group-containing resin was obtained by removing unreacted aniline at 180 ° C under reduced pressure. The amine equivalent was 1060 g/eq·. The GPC chart is shown in Figure 14. After the amine group-containing resin was made into 150 ° C, it was fed to phthalic anhydride 25. 1 g was heated to 150 ° C under introduction of nitrogen to dissolve and react for 1 hour. In this case, the water produced by the reaction is removed from the system. Then, the unreacted phthalic anhydride was removed at 230 ° C under reduced pressure to prepare a resin containing a quinone imine group 212. 7g (resin E). The base equivalent of the obtained resin was 217 g/eq. , the amine equivalent is 30540g / eq. The melting point of the softening point is l〇l ° C ' at 150 ° C is 2. 2Pa · s. The GPC chart ' is shown in Figure 15. [Synthesis Example 1 (Comparative)] Feeding aniline 40. 0g, phenol 200. 0g, 37°/. Awakening aqueous solution 41. 5g' -33- 201125838 Heated to 80 ° C under nitrogen to dissolve. Subsequently, the mixture was heated to 95 ° C with stirring and refluxed for 2 hours, and then heated to 180 after dehydration. (: and reacted for 2 hours. Then, after removing unreacted phenol and aniline at 180 ° C under reduced pressure, an amine-containing resin 102 was obtained. 0g. The hydroxyl equivalent of the obtained resin was 145. 8g/eq·’ amine equivalent is 242 g/eq. The softening point is 61 ° C, and the melting viscosity at 150 ° C is 〇. 〇 2Pa · s. Feeding the resulting amine-containing resin 102. 0g, phthalic anhydride 63. 6 g was heated to 80 ° C under nitrogen to dissolve. Then, the temperature was raised to 150 ° C with stirring and reacted for 1 hour. In this case, the water generated by the reaction is removed from the system. Then, the unreacted phthalic anhydride was removed at 230 ° C under reduced pressure to obtain a ruthenium-containing resin 152. Lg (resin F). The obtained resin had a hydroxyl equivalent of 295 g/eq· and an amine equivalent of 39,950 g/eq. The softening point is l〇5°C, and the melting viscosity at 150°C is 〇. 65Pa·s. [Examples 9 to 13 and Comparative Examples 1 to 3] An o-cresol novolac type epoxy resin (epoxy equivalent 200, softening point 65 ° C) was used as an epoxy resin component, and used as a curing agent in Examples 2, 3, 5, 7, 8, the quinone imine group-containing resin (resin A to F) obtained in Synthesis Example 1, phenol novolak (resin G; manufactured by Qunrong Chemical, PSM-4261, OH equivalent 103, softening point) 82 ° C), phenol aralkyl resin (resin H; Minghe Chemical System 'MEH-7800SS' OH equivalent 175, softening point 67 ° C), as a cerium oxide cerium oxide (average particle size 18μηι), as hardening The triphenylphosphine of the accelerator and the other components shown in Table 1 were kneaded at a blending ratio shown in Table 1, and an epoxy resin composition was obtained. Using the ring-34-201125838 oxy-resin composition, molding at 175 °C, and post-plasticizing (ρ 〇stcure) at 175 °C for 12 hours, after the preparation of the cured test piece, for various Physical property measurement. The glass transition temperature (Tg) and the coefficient of linear expansion (CTE) were measured by a thermomechanical measuring apparatus at a temperature elevation rate of 10 °C/min. The water absorption rate is obtained by using the epoxy resin composition to form a disk having a diameter of 50 mm and a thickness of 3111111, and after being plasticized, it is made to absorb moisture at 85° (:, 85% 1 (relative humidity)). The rate of change in weight after hours. The bending strength and the bending modulus are measured at room temperature according to JIS K6911 by a three-point bending test. Adhesive strength (bonding strength), between two sheets of copper, using a compression molding machine to form 25 mmx at 75 °C. 5mmx0. The 5 mm molded product was evaluated by tensile shearing strength after being plasticized for 12 hours. The flame retardancy was measured at a thickness of 1 / 16 吋. After molding, the evaluation was carried out in accordance with the UL 94V-0 specification, and the total burning time at the time of the five test pieces is shown. The results are shown in Table 1. -35- 201125838 Table L Comparative Example 3 I § o I 800 CSJ T—· in CO 5 in — § 00 CM 00 ο 0. 28 234 Comparative Example 2 σ > σ > 800 CNJ in CO L 162 T— cq CM LO CO d 0. 31 334 Comparative Example 1 ζ s 800 to CO 122 in — σ> co p 0. 24 in <〇Example 13 00 800 OJ in CO 00 q CS| — CM LO 00 Οί CNJ 0.19 inch Example 12 in JO o 00 CSJ in CO p CM — ci CSJ 0.21 5 Example 11 CO 800 C\J in co CO •r— p T· co — s T~ 2 C\j ^*· 0.21 s Example 10 CO CO CO 800 CNJ in CO 5 q — CM in ▼—· 00 CM CO 0.23 CM to Example 9 S co CO o § OJ to co LO <〇 T· q CO — (Ο CM 0.22 00 ss m Secret Resin A Resin B Resin c Resin D Resin E Resin F Resin G Resin H Oxide m m Support © Carbon Black Palm Wax Tg (°C) CTE ( <Tg, x 10-5) CTE (>Tg, x 10-5) Flexural strength (MPa) Flexural modulus (GPa) Adhesive strength (MPa) Water absorption (wt%) Burning time (sec) -36 - 201125838 [Simple description of the diagram] Fig. 1: i-NMR (hydrogen nuclear magnetic resonance) spectrum of an amine group-containing resin. Fig. 2: Infrared absorption spectrum of an amine group-containing resin. Fig. 3: FDMS (Field Desorption Mass Spectrometry) spectrum of an amine group-containing resin. Figure 4: GPC (gel permeation chromatography) chart of amine-containing resin. Figure 5: 1H-NMR spectrum of a resin containing a quinone imine group. Figure 6: Infrared absorption spectrum of a resin containing a quinone imine group. Figure 7: FDMS spectrum of a resin containing a quinone imine group. Figure 8: GPC chart of a resin containing a quinone imine group. Figure 9: GPC chart of a resin containing a quinone imine group. Figure 10: GPC chart of amine-containing resin. Figure 11: GPC chart of a resin containing a quinone imine group. Figure 12 - GPC chart of amine-containing resin. Figure 13: GPC chart of a resin containing a quinone imine group. Figure 14: GPC chart of amine-containing resin. Figure 15: GPC chart of a resin containing a quinone imine group. 5 -37-

Claims (1)

201125838 七、申請專利範圍： 1.—種含胺基之多元羥基化合物，其特徵爲：使苯 酚類、芳香族胺類以及醛類反應後所得之可以下述一般式 【化1】201125838 VII. Patent application scope: 1. A polyvalent hydroxy compound containing an amine group, which is characterized in that the following general formula can be obtained by reacting phenols, aromatic amines and aldehydes. (在此’ Ri表示氫原子、羥基、碳數1至8的烷氧基或 碳數1至8的烴基，R2至R4表示氫原子或碳數1至8的烴基， X表不直接鍵結、-〇-、-S-、-S〇2-、-CO -或二元的徑基，η 爲1至10的數，而m爲0至2的整數，惟„!的平均爲0.05至1.5 ) 表示之含胺基之多元羥基化合物。 2. —種含胺基之多元羥基化合物之製造方法，其特 徵爲：對可以下述一般式（2)， 【化2】(wherein ' Ri denotes a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms or a hydrocarbon group having 1 to 8 carbon atoms, and R2 to R4 represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and X represents no direct bonding. , -〇-, -S-, -S〇2-, -CO- or a binary radial basis, η is a number from 1 to 10, and m is an integer from 0 to 2, but the average of „! is 0.05 to 1.5) A polyvalent hydroxy compound containing an amine group. 2. A method for producing a polyvalent hydroxy compound containing an amine group, which is characterized in that the following general formula (2) can be used. (在此’ Ri表示氫原子、羥基、碳數1至8的烷氧基或 •38- 201125838 S Ο 2 -、- 碳數1至8的烴基，X表示直接鍵結、_〇_、_ CO-或二元的烴基，η爲1至1〇的數）， 表示之苯酚類的具有羥基之苯環1莫耳，使用 可以下述一般式（3 )， 【化3】(In this case, 'R' represents a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, or 38-201125838 S Ο 2 -, a hydrocarbon group having 1 to 8 carbon atoms, and X represents a direct bond, _〇_, _ CO- or a binary hydrocarbon group, η is a number of 1 to 1 )), and represents a phenolic benzene ring having 1 hydroxy group, which can be used in the following general formula (3), [Chemical 3] (在此，R·2、R3表示氫原子或碳數1至8的烴基 表示之芳香族胺類0.05至1.5莫耳，及 可以下述一般式（4)， 【化4】 R4-cho (δ. (在此’ R4表示氫原子或碳數1至8的烴基） 表示之醛類0.05至1.5莫耳，且依芳香族胺類與醛 比爲0 · 5至2 · 〇的條件進行反應。 3. —種含醯亞胺基之多元羥基化合物，其 使申請專利範圍第1項之含胺基之多元羥基化合 Z(CO)2〇表示之二羧酸酐類進行反應後所得之可 般式（5)表示之含醯亞胺基之多元羥基化合物， )， 的莫耳 徵爲： 與可以 下述一 -39- 201125838 【化5】(here, R·2 and R3 represent a hydrogen atom or an aromatic amine represented by a hydrocarbon group having 1 to 8 carbon atoms of 0.05 to 1.5 mol, and may be the following general formula (4), [Chemical 4] R4-cho ( δ. (wherein R4 represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms), and the aldehyde is 0.05 to 1.5 mol, and the reaction is carried out under the conditions of an aromatic amine to an aldehyde ratio of 0.5 to 2 · 〇. 3. A polyvalent hydroxy compound containing a quinone imine group, which is obtained by reacting a dicarboxylic acid anhydride represented by an amine group-containing polyhydric hydroxyl group Z(CO)2〇 represented by the first aspect of the patent application. The Mohr sign of the polyvalent hydroxy compound containing a quinone imine group represented by the formula (5) is: and can be as follows -39-201125838 (在此’ R】至R4、X、n以及m，具有與一般式（1) 同樣意義’ Z爲從二羧酸酐類所生成之至少具有2個碳原子 之二元的基）。 4. 一種含醯亞胺基之多元羥基化合物之製造方法， 其特徵爲：對可以下述—般式（2)表示之苯酚類中的具 有經基之苯環1莫耳’使用可以下述一般式（3)表示之芳 香族胺類0.05至1.5莫耳，及可以下述一般式（4)表示之 酸類0.05至1.5莫耳，且依芳香族胺類與醛類的莫耳比爲 0.5至2_0的條件進行反應藉以製得含胺基之多元羥基化合 物’接著’將此含胺基之多元羥基化合物與可以z(co)2o (在此，Z係至少具有2個碳原子之二元的基）表示之二羧 酸酐類’對胺基1莫耳按酸酐基能成爲1.0至1 .5莫耳之比例 使用並進行反應， 【化6】(here, 'R' to R4, X, n and m have the same meaning as the general formula (1). 'Z is a group having at least two carbon atoms which are formed from a dicarboxylic anhydride. A method for producing a polyvalent hydroxy compound containing a quinone imine group, which is characterized in that the benzene ring having a thiol group in the phenol represented by the following formula (2) can be used as follows The aromatic amine represented by the general formula (3) is 0.05 to 1.5 mol, and the acid represented by the following general formula (4) is 0.05 to 1.5 mol, and the molar ratio of the aromatic amine to the aldehyde is 0.5. The reaction is carried out under the conditions of 2_0 to obtain an amine group-containing polyhydroxy compound, and then the amine group-containing polyhydroxy compound can be z(co) 2o (here, the Z system has at least 2 carbon atoms) The base of the dicarboxylic acid anhydride is used to react with an amine group 1 molar at an acid anhydride group ratio of 1.0 to 1.5 moles. (在此，R!表示氫原子、羥基、碳數1至8的烷氧基或 -40- 201125838 碳數1至8的烴基’ X表示直接鍵結、-0-、-S-、-S02-、-CO-或二元的烴基，η爲1至10的數）， 【化7】 r2(here, R! represents a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms or -40 to 201125838 a hydrocarbon group having 1 to 8 carbon atoms 'X represents a direct bond, -0-, -S-, -S02 -, -CO- or a binary hydrocarbon group, η is a number from 1 to 10), [Chemical 7] r2 r3 (3) (在此，R2、R3表示氫原子或碳數1至8的烴基）， 【化8】 CHO (4) (在此，R4表示氫原子或碳數1至8的烴基）。 5 . —種環氧樹脂組成物，係由環氧樹脂及硬化劑所 成之環氧樹脂組成物，其特徵爲：作爲硬化劑的一部分或 全部’使用申請專利範圍第1項或第3項之含醯胺基之多元 經基化合物或含醯亞胺基之多元羥基化合物。 6· 一種環氧樹脂硬化物，其特徵爲：使申請專利範 S胃5項之環氧樹脂組成物硬化所成之環氧樹脂硬化物。 -41 -R3 (3) (here, R2 and R3 represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms), and CHO (4) (here, R4 represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms). 5. An epoxy resin composition, which is an epoxy resin composition composed of an epoxy resin and a hardener, and is characterized in that: part or all of the hardening agent is used as the first or third item of the patent application scope. The hydrazine-containing polybasic compound or the quinone-containing hydroxy compound. 6. An epoxy resin cured product characterized by curing an epoxy resin formed by hardening an epoxy resin composition of a patent application. -41 -
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