JPH06239966A - Epoxy resin, epoxy resin composition and its cured product - Google Patents
Epoxy resin, epoxy resin composition and its cured productInfo
- Publication number
- JPH06239966A JPH06239966A JP4869693A JP4869693A JPH06239966A JP H06239966 A JPH06239966 A JP H06239966A JP 4869693 A JP4869693 A JP 4869693A JP 4869693 A JP4869693 A JP 4869693A JP H06239966 A JPH06239966 A JP H06239966A
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- JP
- Japan
- Prior art keywords
- epoxy resin
- formula
- parts
- equivalent
- allyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
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- Epoxy Resins (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は耐熱性、耐水性に優れた
硬化物を与えるエポキシ樹脂およびエポキシ樹脂組成物
およびその硬化物に関するものであり、本発明の組成物
は成形材料，注型材料，積層材料，複合材料，塗料，接
着剤，レジストなどの広範囲の用途に極めて有用であ
る。又、本発明のエポキシ樹脂が有するアリル基とシリ
コンオイルのＳｉＨ基とを反応させることにより、ポリ
マーアロイへの応用も可能である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin and an epoxy resin composition which give a cured product excellent in heat resistance and water resistance, and a cured product thereof. The composition of the present invention is a molding material or a casting material. It is extremely useful for a wide range of applications such as laminated materials, composite materials, paints, adhesives, and resists. Further, it can be applied to a polymer alloy by reacting the allyl group of the epoxy resin of the present invention with the SiH group of silicon oil.
【０００２】[0002]
【従来の技術】エポキシ樹脂は種々の硬化剤で硬化させ
ることにより、一般的に機械的性質，耐水性，耐薬品
性，耐熱性，電気的性質などの優れた硬化物となり、接
着剤，塗料，積層板，成形材料，注型材料などの幅広い
分野に利用されている。従来、工業的に最も多く使用さ
れているエポキシ樹脂としてビスフェノ−ルＡにエピク
ロルヒドリンを反応させて得られる液状および固形のビ
スフェノ−ルＡ型エポキシ樹脂がある。その他液状のビ
スフェノ−ルＡ型エポキシ樹脂にテトラブルムビスフェ
ノ−ルＡを反応させて得られる難燃性固形エポキシ樹脂
などが汎用エポキシ樹脂として工業的に使用されてい
る。2. Description of the Related Art Epoxy resins, when cured with various curing agents, generally become cured products having excellent mechanical properties, water resistance, chemical resistance, heat resistance, and electrical properties, and are used as adhesives and paints. It is used in a wide range of fields such as laminates, molding materials, and casting materials. Conventionally, as the most widely used epoxy resin in the industry, there are liquid and solid bisphenol A type epoxy resins obtained by reacting bisphenol A with epichlorohydrin. In addition, a flame-retardant solid epoxy resin obtained by reacting liquid bisphenol A type epoxy resin with Tetrabum bisphenol A is industrially used as a general-purpose epoxy resin.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、前記し
たような汎用エポキシ樹脂は分子量が大きくなるにつれ
て、それを使用して得られる硬化物の吸水性は高くなり
耐熱性は低下するという欠点がある。一方、最近の電子
産業などの目ざましい発達に伴い、これらに使用される
電気絶縁材料などに要求される耐水性及び耐熱性は益々
厳しくなっており、耐水性及び耐熱性に優れたエポキシ
樹脂の出現が待ち望まれている。However, the general-purpose epoxy resin as described above has the drawback that as the molecular weight increases, the water absorbency of the cured product obtained by using it increases and the heat resistance decreases. On the other hand, with the recent remarkable development of the electronics industry and the like, the water resistance and heat resistance required for electric insulating materials used for these have become more and more severe, and the emergence of epoxy resins having excellent water resistance and heat resistance. Is awaited.
【０００４】[0004]
【課題を解決するための手段】本発明者らはこうした実
状に鑑み、耐水性及び耐熱性に優れるエポキシ樹脂を求
めて鋭意研究した結果、後記式（１）で表されるエポキ
シ樹脂がその硬化物に対して耐水性及び耐熱性を付与す
るものであることを見い出して本発明を完成させるに到
った。すなわち本発明は（１）式（１）In view of these circumstances, the present inventors have earnestly studied for an epoxy resin having excellent water resistance and heat resistance, and as a result, the epoxy resin represented by the following formula (1) is cured. The present invention has been completed by finding that it imparts water resistance and heat resistance to an object. That is, the present invention relates to the formula (1) (1)
【０００５】[0005]
【化２】 [Chemical 2]
【０００６】（式中、ｎは平均値を示し正数を表す。Ｒ
は、２個のフェノール性水酸基を有する化合物の水酸基
が除かれた残基を表し、個々のＲはお互いに同一であっ
ても異なっていてもよい。又、個々のＸは、水素原子、
アリル基（ＣＨ2 ＝ＣＨＣＨ2−）、或いはグリシジル
基を表し、個々のＸはお互いに同一であっても異なって
もよいが、Ｘの５％以上はアリル基である。）で表され
るエポキシ樹脂、(In the formula, n represents an average value and represents a positive number. R
Represents a residue obtained by removing a hydroxyl group of a compound having two phenolic hydroxyl groups, and individual Rs may be the same or different from each other. Also, each X is a hydrogen atom,
It represents an allyl group (CH 2 ═CHCH 2 —) or a glycidyl group, and each X may be the same or different from each other, but 5% or more of X is an allyl group. ) Epoxy resin represented by
【０００７】（２）エポキシ樹脂、硬化剤、及び必要に
より硬化促進剤を含有するエポキシ樹脂組成物におい
て、該エポキシ樹脂成分として式（１）のエポキシ樹脂
を含有することを特徴とするエポキシ樹脂組成物、
（３）上記（２）記載のエポキシ樹脂組成物からなる積
層板用エポキシ樹脂組成物、（４）上記（２）又は
（３）記載のエポキシ樹脂組成物の硬化物、に関するも
のである。(2) An epoxy resin composition containing an epoxy resin, a curing agent, and optionally a curing accelerator, which contains the epoxy resin of the formula (1) as the epoxy resin component. object,
(3) An epoxy resin composition for laminated boards, which comprises the epoxy resin composition described in (2) above, and (4) a cured product of the epoxy resin composition described in (2) or (3) above.
【０００８】本発明によれば、耐熱性、耐水性に優れた
硬化物を得ることができる。本発明のエポキシ樹脂は、
例えば、式（２）According to the present invention, a cured product having excellent heat resistance and water resistance can be obtained. The epoxy resin of the present invention is
For example, equation (2)
【０００９】[0009]
【化３】 [Chemical 3]
【００１０】（式中、ｎ及びＲは前記と同じ意味を表
す。）で表される化合物のアルコール性水酸基をアリル
ハライド（必要により更にエピハロヒドリン）と反応さ
せることにより得ることができる。It can be obtained by reacting the alcoholic hydroxyl group of the compound represented by the formula (wherein n and R have the same meanings as described above) with an allyl halide (and optionally epihalohydrin).
【００１１】より詳細には式（２）で表される化合物の
アルコ−ル性水酸基とアリルハライド（必要により更に
エピハロヒドリン）との反応をジメチルスルホキシドま
たは４級アンモニウム塩または１，３−ジメチル−２−
イミダゾリジノンとアルカリ金属水酸化物の共存下に行
い，アルカリ金属水酸化物の使用量を調節することによ
り式（１）のエポキシ樹脂を得ることができる。More specifically, the reaction of the alcoholic hydroxyl group of the compound represented by the formula (2) with an allyl halide (further, if necessary, epihalohydrin) is carried out by dimethyl sulfoxide or a quaternary ammonium salt or 1,3-dimethyl-2. −
The epoxy resin of the formula (1) can be obtained by adjusting the amount of alkali metal hydroxide used in the presence of imidazolidinone and alkali metal hydroxide.
【００１２】本発明者らの検討によれば、式（２）の化
合物のアルコ−ル性水酸基は一般のアルコ−ル類より反
応性に富んでおり，例えばジメチルスルホキシドまたは
４級アンモニウム塩または１，３−ジメチル−２−イミ
ダゾリジノンとアルカリ金属水酸化物を共存させること
により、驚くべきことに，アルコ−ル性水酸基とアリル
ハライド（必要により更にエピハロヒドリン）との反応
を選択的に行え、さらにアルカリ金属水酸化物の量を調
節することにより式（２）で表される化合物のアルコ−
ル性水酸基を所望の割合にアリル化（必要により更にエ
ポキシ化）できる。According to the studies by the present inventors, the alcoholic hydroxyl group of the compound of the formula (2) is more reactive than general alcohols, for example, dimethyl sulfoxide or quaternary ammonium salt or 1 Surprisingly, by allowing 3,3-dimethyl-2-imidazolidinone and an alkali metal hydroxide to coexist, a reaction between an alcoholic hydroxyl group and an allyl halide (and further epihalohydrin if necessary) can be selectively carried out, Further, by adjusting the amount of the alkali metal hydroxide, the alcohol of the compound represented by the formula (2)
The hydroxyl group can be allylated to a desired ratio (and further epoxidized if necessary).
【００１３】式（２）で表される化合物のアルコ−ル性
水酸基とアリルハライド（必要により更にエピハロヒド
リン）との反応をジメチルスルホキシドまたは４級アン
モニウム塩または１，３−ジメチル−２−イミダゾリジ
ノンとアルカリ金属水酸化物の共存下に行なう際，溶剤
としてアルコ−ル類，芳香族炭化水素類，ケトン類，環
状又は鎖状エ−テル化合物等を併用しても構わない。ま
たジメチルスルホキシド，４級アンモニウム塩，１，３
−ジメチル−２−イミダゾリジノンは単独で用いてもよ
いが、併用しても構わない。The reaction of the alcoholic hydroxyl group of the compound represented by the formula (2) with an allyl halide (further, if necessary, epihalohydrin) is carried out by dimethyl sulfoxide or a quaternary ammonium salt or 1,3-dimethyl-2-imidazolidinone. When it is carried out in the coexistence with the alkali metal hydroxide, alcohols, aromatic hydrocarbons, ketones, cyclic or chain ether compounds and the like may be used together as a solvent. Dimethyl sulfoxide, quaternary ammonium salt, 1,3
-Dimethyl-2-imidazolidinone may be used alone or in combination.
【００１４】ジメチルスルホキシドあるいは１，３−ジ
メチル−２−イミダゾリジノンの使用量は式（２）で表
される化合物に対して５重量％〜３００重量％が好まし
い。式（２）で表される化合物に対して５重量％未満で
あると式（２）で表される化合物の水酸基とアリルハラ
イド，エピハロヒドリンとの反応が遅くなる為長時間の
反応が必要となり好ましくない。式（２）で表される化
合物に対して３００重量％を超えると増量した効果はほ
とんどなくなる一方容積効率も悪くなり好ましくない。The amount of dimethyl sulfoxide or 1,3-dimethyl-2-imidazolidinone used is preferably 5% by weight to 300% by weight based on the compound represented by the formula (2). When the amount is less than 5% by weight based on the compound represented by the formula (2), the reaction between the hydroxyl group of the compound represented by the formula (2) and allyl halide or epihalohydrin is delayed, which requires a long reaction time, which is preferable. Absent. When it exceeds 300% by weight with respect to the compound represented by the formula (2), the effect of increasing the amount is almost eliminated and the volume efficiency is deteriorated, which is not preferable.
【００１５】４級アンモニウム塩としてはテトラメチル
アンモニウムクロライド，テトラメチルアンモニウムブ
ロマイド，トリメチルベンジルアンモニウムクロライド
等が挙げられ、その使用量は式（２）で表される化合物
のアリル化，エポキシ化させたい水酸基１当量に対して
０．３〜５０ｇが好ましい。０．３ｇ未満であると式
（２）で表される化合物の水酸基とアリルハライド或は
エピハロヒドリンとの反応が遅くなり長時間の反応が必
要となり好ましくなく，又，５０ｇを超えると増量した
効果はほとんどなくなる一方コストが高くなり好ましく
ない。Examples of the quaternary ammonium salt include tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride and the like. The amount of the quaternary ammonium salt used is the hydroxyl group to be allylated or epoxidized in the compound represented by the formula (2). 0.3 to 50 g is preferable for 1 equivalent. If the amount is less than 0.3 g, the reaction between the hydroxyl group of the compound represented by the formula (2) and allyl halide or epihalohydrin is delayed and long-time reaction is required, which is not preferable, and if it exceeds 50 g, the effect of increasing the amount is Although it almost disappears, the cost becomes high, which is not preferable.
【００１６】アリルハライド及びエピハロヒドリンとし
ては、例えば，アリルクロライド，アリルブロマイド，
エピクロロヒドリン，エピブロモヒドリン等が挙げら
れ，これらは，それぞれ，式（２）で表される化合物の
アリル化或はエポキシ化させたい水酸基１当量に対して
当量以上使用すれば良い。しかしながらアリル化或はエ
ポキシ化させたい水酸基１当量に対して２０倍当量を超
えると増量した効果はほとんどなくなる一方容積効率も
悪くなり好ましくない。Examples of allyl halides and epihalohydrins include allyl chloride, allyl bromide,
Examples thereof include epichlorohydrin and epibromohydrin, and these may be used in an equivalent amount or more with respect to one equivalent of the hydroxyl group to be allylated or epoxidized in the compound represented by the formula (2). However, if it exceeds 20 times equivalent to 1 equivalent of hydroxyl group to be allylated or epoxidized, the effect of increasing the amount is almost lost and the volume efficiency is deteriorated, which is not preferable.
【００１７】アルカリ金属水酸化物としては、苛性ソ−
ダ，苛性カリ，水酸化リチウム，水酸化カルシウムなど
が使用できるが苛性ソ−ダが好ましい。アルカリ金属水
酸化物の使用量は式（２）で表される化合物のアリル化
或はエポキシ化させたい水酸基１当量に対して１〜２．
５倍当量使用すれば良い。アルカリ金属水酸化物は固形
でも水溶液でも構わない。また水溶液を使用する場合は
反応中、反応系内の水は常圧下、減圧下において反応系
外に留去しながら反応を行うこともできる。Alkali metal hydroxides include caustic soda.
Although caustic soda, caustic potash, lithium hydroxide, calcium hydroxide and the like can be used, caustic soda is preferred. The amount of the alkali metal hydroxide used is 1 to 2 per 1 equivalent of the hydroxyl group to be allylated or epoxidized in the compound represented by the formula (2).
It is sufficient to use 5 times the equivalent amount. The alkali metal hydroxide may be solid or aqueous solution. When an aqueous solution is used, the reaction can be carried out during the reaction while distilling the water in the reaction system out of the reaction system under normal pressure or reduced pressure.
【００１８】反応温度は２０〜１００℃が好ましい。反
応温度が２０℃未満であると反応が遅くなり長時間の反
応が必要となる。反応温度が１００℃を超えると副反応
が多く起こり好ましくない。The reaction temperature is preferably 20 to 100 ° C. If the reaction temperature is lower than 20 ° C, the reaction becomes slow and a long-time reaction is required. When the reaction temperature exceeds 100 ° C., many side reactions occur, which is not preferable.
【００１９】本発明の式（１）のエポキシ樹脂におい
て，ｎは平均値を示し正数を表わすが好ましい値は０．
１〜１５，特に好ましい値は１〜１０である。又，Ｘの
５％以上はアリル基であるが，Ｘの１０％以上がアリル
基であることが好ましい。又，Ｒとしては，例えば，In the epoxy resin of the formula (1) of the present invention, n represents an average value and represents a positive number, and the preferable value is 0.
1 to 15, particularly preferably 1 to 10. Further, 5% or more of X is an allyl group, but 10% or more of X is preferably an allyl group. Also, as R, for example,
【００２０】[0020]
【化４】 [Chemical 4]
【００２１】等が挙げられる。Ｒは，式（１）で表され
るエポキシ樹脂において，含有される分子毎に同一であ
っても異なっていてもよく，又，同一分子内において
も，複数存在するＲはお互いに同一であっても異なって
いてもよい。And the like. In the epoxy resin represented by the formula (1), R may be the same or different for each contained molecule, and a plurality of Rs present in the same molecule are the same as each other. Or they may be different.
【００２２】以下に，本発明のエポキシ樹脂組成物につ
いて説明する。本発明のエポキシ樹脂は単独で用いても
よく，又，他のエポキシ樹脂と併用してもよい。他のエ
ポキシ樹脂と併用する場合，本発明のエポキシ樹脂は全
エポキシ樹脂中１０重量％以上用いるのが好ましく，特
に２０重量％以上用いるのが好ましい。他のエポキシ樹
脂としては，例えば，ビスフェノールＡ型エポキシ樹
脂，臭素化ビスフェノールＡ型エポキシ樹脂，トリフェ
ニルメタン型エポキシ樹脂，テトラメチルビフェノール
型エポキシ樹脂，フェノールノボラック型エポキシ樹
脂，クレゾールノボラック型エポキシ樹脂等が挙げられ
る。The epoxy resin composition of the present invention will be described below. The epoxy resin of the present invention may be used alone or in combination with another epoxy resin. When used in combination with another epoxy resin, the epoxy resin of the present invention is preferably used in an amount of 10% by weight or more, more preferably 20% by weight or more, based on the total epoxy resin. Examples of other epoxy resins include bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, triphenylmethane type epoxy resin, tetramethylbiphenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin and the like. Can be mentioned.
【００２３】硬化剤としてはアミン系化合物，酸無水物
系化合物，アミド系化合物，フェノ−ル系化合物などが
挙げられ，具体例としては、ジアミノジフェニルメタ
ン，ジエチレントリアミン，トリエチレンテトラミン，
ジアミノジフェニルスルホン，イソホロンジアミン，ジ
シアンジアミド，リノレン酸の２量体とエチレンジアミ
ンとより合成されるポリアミド樹脂，無水フタル酸，無
水トリメリット酸，無水ピロメリット酸，無水マレイン
酸，テトラヒドロ無水フタル酸，メチルテトラヒドロ無
水フタル酸，無水メチルナジック酸，ヘキサヒドロ無水
フタル酸，メチルヘキサヒドロ無水フタル酸，フェノ−
ルノボラック，及びこれらの変性物，イミダゾ−ル，Ｂ
Ｆ3 −アミン錯体，グアニジン誘導体などが挙げられ
る。これらの硬化剤はそれぞれ単独で用いてもよいし、
２種以上組み合わせて用いてもよい。Examples of the curing agent include amine compounds, acid anhydride compounds, amide compounds and phenol compounds. Specific examples include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine,
Polyamide resin synthesized from diaminodiphenylsulfone, isophoronediamine, dicyandiamide, linolenic acid dimer and ethylenediamine, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydro Phthalic anhydride, methyl nadic acid anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, pheno-
Lunovolac and modified products thereof, imidazole, B
Examples thereof include F3 -amine complex and guanidine derivative. These curing agents may be used alone,
You may use it in combination of 2 or more type.
【００２４】これらの硬化剤の使用量は，エポキシ樹脂
のエポキシ基に対して０．７〜１．２当量が好ましい。
エポキシ基に対して，０．７当量に満たない場合、ある
いは１．２当量を超える場合，いずれも硬化が不完全と
なり良好な硬化物性が得られない恐れがある。The amount of these curing agents used is preferably 0.7 to 1.2 equivalents based on the epoxy groups of the epoxy resin.
If the amount is less than 0.7 equivalent or more than 1.2 equivalent to the epoxy group, the curing may be incomplete and good cured physical properties may not be obtained.
【００２５】また上記硬化剤を用いる際に硬化促進剤を
併用しても差し支えない。硬化促進剤としては例えばイ
ミダゾ−ル類，第３級アミン類，フェノ−ル類，金属化
合物等が挙げられる。さらに、必要に応じて無機または
有機の充填剤等の種々の配合剤を添加することができ
る。硬化促進剤を使用する場合，その使用量はエポキシ
樹脂１００重量部に対して０．１〜５．０重量部が好ま
しい。When using the above-mentioned curing agent, a curing accelerator may be used in combination. Examples of the curing accelerator include imidazoles, tertiary amines, phenols, metal compounds and the like. Furthermore, various compounding agents such as inorganic or organic fillers can be added as required. When a curing accelerator is used, its amount is preferably 0.1 to 5.0 parts by weight with respect to 100 parts by weight of the epoxy resin.
【００２６】本発明のエポキシ樹脂組成物は，エポキシ
樹脂，硬化剤，必要により硬化促進剤や他の各種配合剤
を均一に混合することにより得ることができる。本発明
のエポキシ樹脂組成物から従来知られている方法と同様
の方法で容易にエポキシ樹脂組成物の硬化物を得ること
ができる。例えば，エポキシ樹脂と硬化剤，必要により
硬化促進剤，充填剤，その他の添加剤を必要に応じて押
出機，ニ−ダ，ロ−ル等を用いて均一になるまで充分に
混合してエポキシ樹脂組成物を得、そのエポキシ樹脂組
成物を溶融後注型あるいはトランスファ−成形機などを
用いて成形し、さらに８０〜２００℃に加熱することに
より硬化物を得ることができる。また本発明の樹脂組成
物を溶剤に溶解させ、ガラス繊維，カ−ボン繊維，ポリ
エステル繊維，ポリアミド繊維，アルミナ繊維，紙など
の基材に含浸させ加熱乾燥して得たプリプレグを熱プレ
ス成形して硬化物を得ることもできる。The epoxy resin composition of the present invention can be obtained by uniformly mixing an epoxy resin, a curing agent, and if necessary, a curing accelerator and other various compounding agents. A cured product of the epoxy resin composition can be easily obtained from the epoxy resin composition of the present invention by a method similar to a conventionally known method. For example, an epoxy resin and a curing agent, and if necessary, a curing accelerator, a filler, and other additives are sufficiently mixed using an extruder, a kneader, a roll, etc., as necessary, until an epoxy resin is obtained. A cured product can be obtained by obtaining a resin composition, melting and molding the epoxy resin composition using a casting or transfer molding machine, and then heating at 80 to 200 ° C. Further, the resin composition of the present invention is dissolved in a solvent and impregnated into a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper and the like, and heat-dried to obtain a prepreg by hot press molding. It is also possible to obtain a cured product.
【００２７】本発明のエポキシ樹脂組成物は，耐水性，
耐熱性に優れた硬化物を与え，積層板用，塗料，接着
剤，封止材用等各種用途に使用できる。The epoxy resin composition of the present invention is
It gives a cured product with excellent heat resistance and can be used for various purposes such as laminates, paints, adhesives, and encapsulants.
【００２８】[0028]
【実施例】次に本発明を実施例，比較例により具体的に
説明するが、以下において部は特に断わりのない限りす
べて重量部であるものとする。尚、ガラス転移点，吸水
率及びＮＭＲの測定条件は次の通りである。EXAMPLES The present invention will now be described in detail with reference to Examples and Comparative Examples. In the following, all parts are parts by weight unless otherwise specified. The glass transition point, water absorption rate and NMR measurement conditions are as follows.
【００２９】ガラス転移点 熱機械測定装置（ＴＭＡ）：真空理工 ＴＭ−７０００ 昇温速度：２℃／ｍｉｎ 吸水率測定条件 試験片（硬化物）：直径 ５０ｍｍ 厚さ ３ｍｍ 円盤 １００℃の水中で２０時間煮沸した後の重量増加量（重
量％）Glass transition temperature thermomechanical measuring device (TMA): Vacuum Riko TM-7000 Temperature rising rate: 2 ° C./min Water absorption measuring condition Test piece (cured product): Diameter 50 mm Thickness 3 mm Disc 20 in water at 100 ° C. Weight increase after boiling for an hour (% by weight)
【００３０】ＮＭＲ測定条件 ＮＭＲ：Ｖａｒｉａｎ Ｇｅｍｉｎｉ−３００ 溶媒：ＣＤＣｌ3 温度：２０℃ 周波数領域：４５００．５Ｈｚ 濃度：１５０ｍｇ／ｍｌ パルス間隔：１０．０microsec 積算回数：１６回NMR measurement conditions NMR: Varian Gemini-300 Solvent: CDCl 3 Temperature: 20 ° C. Frequency range: 4500.5 Hz Concentration: 150 mg / ml Pulse interval: 10.0 microsec Number of integrations: 16 times
【００３１】実施例１〜３，比較例１ 式（２）で表される化合物としてＲが式（３）で示され
る残基でありｎが２．２であるビスフェノ−ルＡ型エポ
キシ樹脂（エポミックＲ−３０１、三井石油化学
（株）、エポキシ当量４７９ｇ／ｅｑ）２２０部（アル
コ−ル性水酸基０．５当量）をジメチルスルホキシド４
４０部に溶解させた後、撹拌下４０℃で塩化アリル７
６．５部を添加した。その後３０％ＮａＯＨ水溶液９
４．７部を加え還流下で５０℃に昇温し３時間反応を行
った。反応終了後メチルイソブチルケトン８８０部、水
４４０部を加え２回水洗を行った。油水分離後、油層よ
りメチルイソブチルケトン及びジメチルスルホキシドを
減圧下に蒸留回収し、エポキシ当量５１１ｇ／ｅｑのエ
ポキシ樹脂（１）２１７部を得た。ＮＭＲを用いて、得
られたエポキシ樹脂（１）のアリル基とグリシジル基と
を合わせた総官能基当量を算出すると２８８ｇ／ｅｑと
なった。得られたエポキシ樹脂（１）は，式（１）にお
いてｎ＝２．２，Ｒが式（３）で表される残基，Ｘが水
素原子及びアリル基を示しＸの６９％がアリル基となっ
ているエポキシ樹脂である。Examples 1 to 3, Comparative Example 1 As a compound represented by the formula (2), R is a residue represented by the formula (3) and n is 2.2. Epomic R-301, Mitsui Petrochemical Co., Ltd., epoxy equivalent 479 g / eq, 220 parts (alcoholic hydroxyl group 0.5 equivalent) was added to dimethyl sulfoxide 4.
After dissolving in 40 parts, allyl chloride 7 at 40 ° C. with stirring.
6.5 parts were added. Then 30% NaOH aqueous solution 9
4.7 parts was added and the mixture was heated to 50 ° C. under reflux and reacted for 3 hours. After completion of the reaction, 880 parts of methyl isobutyl ketone and 440 parts of water were added and the mixture was washed twice with water. After separation of the oil and water, methyl isobutyl ketone and dimethyl sulfoxide were distilled and recovered from the oil layer under reduced pressure to obtain 217 parts of epoxy resin (1) having an epoxy equivalent of 511 g / eq. The total functional group equivalent of the obtained epoxy resin (1) including allyl groups and glycidyl groups was calculated by NMR to be 288 g / eq. In the obtained epoxy resin (1), n = 2.2 in the formula (1), R is a residue represented by the formula (3), X is a hydrogen atom and an allyl group, and 69% of X is an allyl group. It is an epoxy resin.
【００３２】また同様の方法で３０％ＮａＯＨ水溶液の
使用量を６７．７部にしてエポキシ当量５０４ｇ／ｅｑ
のエポキシ樹脂（２）２１０部を得た。ＮＭＲを用い
て、得られたエポキシ樹脂（２）のアリル基とグリシジ
ル基とを合わせた総官能基当量を算出すると３１９ｇ／
ｅｑとなった。得られたエポキシ樹脂（２）は，式
（１）においてｎ＝２．２，Ｒが式（３）で表される残
基，Ｘが水素原子及びアリル基を示しＸの５２％がアリ
ル基となっているエポキシ樹脂である。In the same manner, the amount of the 30% NaOH aqueous solution used was 67.7 parts and the epoxy equivalent was 504 g / eq.
To obtain 210 parts of the epoxy resin (2). The total functional group equivalent weight of the obtained epoxy resin (2) including allyl group and glycidyl group was calculated by using NMR to obtain 319 g /
It became eq. In the obtained epoxy resin (2), n = 2.2 in the formula (1), R is a residue represented by the formula (3), X is a hydrogen atom and an allyl group, and 52% of X is an allyl group. It is an epoxy resin.
【００３３】更に同様の方法で３０％ＮａＯＨ水溶液の
使用量を４０．６部にしてエポキシ当量４９６ｇ／ｅｑ
のエポキシ樹脂（３）２０６部を得た。ＮＭＲを用い
て、得られたエポキシ樹脂（３）のアリル基とグリシジ
ル基とを合わせた総官能基当量を算出すると３７２ｇ／
ｅｑとなった。得られたエポキシ樹脂（３）は，式
（１）においてｎ＝２．２，Ｒが式（３）で表される残
基，Ｘが水素原子及びアリル基を示しＸの３０％がアリ
ル基となっているエポキシ樹脂である。Further, in the same manner, the amount of 30% NaOH aqueous solution used was changed to 40.6 parts and the epoxy equivalent was 496 g / eq.
206 parts of epoxy resin (3) was obtained. The total functional group equivalent of the obtained epoxy resin (3) including allyl groups and glycidyl groups was calculated by using NMR, and was found to be 372 g /
It became eq. In the obtained epoxy resin (3), n = 2.2 in the formula (1), R is a residue represented by the formula (3), X is a hydrogen atom and an allyl group, and 30% of X is an allyl group. It is an epoxy resin.
【００３４】また得られたエポキシ樹脂（１）〜
（３）、比較としてエポキシ樹脂エポミックＲ−３０
１、硬化剤としてジアミノジフェニルメタン（ＤＤＭ）
を用い、表−１に示す組成で配合して、７０℃で１５分
ロールで混練し，１５０℃、１８０秒でトランスファー
成形して、その後１６０℃で２時間、更に１８０℃で８
時間硬化せしめて試験片を作成し、ガラス転移点及び吸
水率を測定した。結果を表１に示す。なお表中，各成分
の欄の数値は重量部を示す。The obtained epoxy resins (1) to
(3), for comparison, epoxy resin Epomic R-30
1. Diaminodiphenylmethane (DDM) as a curing agent
The composition shown in Table 1 was used, and the mixture was kneaded with a roll at 70 ° C. for 15 minutes, transfer-molded at 150 ° C. for 180 seconds, then at 160 ° C. for 2 hours, and further at 180 ° C. for 8 hours.
A test piece was prepared by curing for a period of time, and the glass transition point and water absorption were measured. The results are shown in Table 1. In the table, the numerical values in the column of each component indicate parts by weight.
【００３５】 表１ 実 施 例 比較例 １ ２ ３ １ エポキシ樹脂（１） 100 エポキシ樹脂（２） 100 エポキシ樹脂（３） 100 エポミックＲ−３０１ 100 エポキシ当量(g/eq) 511 504 496 479 総官能基当量(g/eq) 288 319 372 479 ＤＤＭ 17 16 13 10 ガラス転移点（℃） 155 147 144 140 吸水率（％） 1.51 1.60 1.67 1.87 Table 1 Actual Example Comparative Example 1 2 3 1 Epoxy resin (1) 100 Epoxy resin (2) 100 Epoxy resin (3) 100 Epomic R-301 100 Epoxy equivalent (g / eq) 511 504 496 479 Total functionality Base equivalent (g / eq) 288 319 372 479 DDM 17 16 13 10 Glass transition point (℃) 155 147 144 140 Water absorption rate (%) 1.51 1.60 1.67 1.87
【００３６】実施例４〜５，比較例２ 実施例１〜３と同様の原料エポミックＲ−３０１を５３
２部用いてエポキシ樹脂（３）の合成の場合と同様の方
法でエポキシ当量が４９４ｇ／ｅｑ、ＮＭＲを用いて算
出されたアリル基とグリシジル基とを合わせた総官能基
当量が３６９ｇ／ｅｑであるエポキシ樹脂５２２部を得
た。得られたエポキシ樹脂２１９部をエピクロルヒドリ
ン６４８部に溶解させた後、テトラメチルアンモニウム
クロライド２．５部を添加し、次いでＮａＯＨを１３．
５部添加し，更に撹拌下４０℃で３時間反応を行った。
反応終了後水３２４部を加え水洗を行った。油水分離
後、油層より過剰の未反応エピクロルヒドリンを減圧下
に蒸留回収し、エポキシ当量３４９ｇ／ｅｑのエポキシ
樹脂（４）２２１部を得た。ＮＭＲを用いてアリル基と
グリシジル基とを合わせた総官能基当量を算出すると２
９１ｇ／ｅｑとなった。得られたエポキシ樹脂（４）
は，式（１）においてｎ＝２．２，Ｒが式（３）で表さ
れる残基，Ｘが水素原子，アリル基及びグリシジル基を
示し，Ｘの３０％がアリル基に，又，Ｘの４５％がグリ
シジル基になっているエポキシ樹脂である。Examples 4 to 5 and Comparative Example 2 The same raw material Epomic R-301 as in Examples 1 to 53 was used.
The epoxy equivalent was 494 g / eq in the same manner as in the case of synthesizing the epoxy resin (3) using 2 parts, and the total functional group equivalent calculated by using NMR was a total of 369 g / eq of allyl group and glycidyl group. 522 parts of an epoxy resin were obtained. After 219 parts of the obtained epoxy resin was dissolved in 648 parts of epichlorohydrin, 2.5 parts of tetramethylammonium chloride was added, and then NaOH was added to 13.
5 parts was added, and the reaction was further carried out at 40 ° C. for 3 hours with stirring.
After completion of the reaction, 324 parts of water was added and the mixture was washed with water. After oil-water separation, excess unreacted epichlorohydrin was distilled and collected from the oil layer under reduced pressure to obtain 221 parts of epoxy resin (4) having an epoxy equivalent of 349 g / eq. When the total functional group equivalent of the allyl group and the glycidyl group was calculated using NMR, it was 2
It became 91 g / eq. Obtained epoxy resin (4)
Is n = 2.2 in the formula (1), R is a residue represented by the formula (3), X is a hydrogen atom, an allyl group and a glycidyl group, 30% of X is an allyl group, and An epoxy resin in which 45% of X is a glycidyl group.
【００３７】また同様の方法で９８．５％ＮａＯＨの使
用量を１２．２部としてエポキシ当量３７１ｇ／ｅｑの
エポキシ樹脂（５）２１７部を得た。ＮＭＲを用いてア
リル基とグリシジル基とを合わせた総官能基当量を算出
すると３００ｇ／ｅｑとなった。得られたエポキシ樹脂
（５）は，式（１）においてｎ＝２．２，Ｒが式（３）
で表される残基，Ｘが水素原子，アリル基及びグリシジ
ル基を示し，Ｘの３０％がアリル基であり，又，Ｘの３
５％がグリシジル基であるエポキシ樹脂である。In the same manner, the amount of 98.5% NaOH used was 12.2 parts to obtain 217 parts of epoxy resin (5) having an epoxy equivalent of 371 g / eq. The total functional group equivalent weight of the allyl group and the glycidyl group was calculated by using NMR to obtain 300 g / eq. In the obtained epoxy resin (5), n = 2.2 in the formula (1) and R is the formula (3).
, X represents a hydrogen atom, an allyl group and a glycidyl group, 30% of X is an allyl group, and X of 3
5% is an epoxy resin having a glycidyl group.
【００３８】また得られたエポキシ樹脂（４）〜
（５）、比較としてエポキシ樹脂エポミックＲ−３０
１、硬化剤としてジアミノジフェニルメタン（ＤＤＭ）
を用い、表２に示す組成で配合して、７０℃で１５分ロ
ールで混練し、１５０℃、１８０秒でトランスファー成
形して、その後１６０℃で２時間、更に１８０℃で８時
間硬化せしめて試験片を作成し、ガラス転移点及び吸水
率を測定した。結果を表２に示す。なお，表中，各成分
の欄の数値は重量部を示す。The obtained epoxy resins (4) to
(5), for comparison, epoxy resin Epomic R-30
1. Diaminodiphenylmethane (DDM) as a curing agent
Was blended with the composition shown in Table 2, kneaded with a roll at 70 ° C. for 15 minutes, transfer molded at 150 ° C. for 180 seconds, and then cured at 160 ° C. for 2 hours and further at 180 ° C. for 8 hours. A test piece was prepared and the glass transition point and water absorption were measured. The results are shown in Table 2. In addition, in the table, the numerical value in the column of each component shows a part by weight.
【００３９】 [0039]
【００４０】実施例６〜７，比較例３ 式（２）で表される化合物として，Ｒとして式（３）で
示される残基と式（４）で示される残基の両方が存在
し，ｎが２．６である臭素含有ビスフェノ−ルＡ型エポ
キシ樹脂（エピコート５０４９、油化シェルエポキシ
（株）、エポキシ当量７３５ｇ／ｅｑ、臭素含有量２
６．６重量％）２８１部（アルコ−ル性水酸基０．５当
量）をジメチルスルホキシド５６０部に溶解させた後、
撹拌下４０℃で塩化アリルを７６．５部、３０％ＮａＯ
Ｈ水溶液を８８．０部添加した以外は実施例１と同様に
反応を行い、エポキシ当量７８２ｇ／ｅｑのエポキシ樹
脂（６）２１７部を得た。ＮＭＲを用いて、得られたエ
ポキシ樹脂（６）のアリル基とグリシジル基とを合わせ
た総官能基当量を算出すると４１６ｇ／ｅｑとなった。
得られたエポキシ樹脂（６）は，式（１）においてｎ＝
２．６，Ｒが式（３）で表される残基及び式（４）で表
される残基を示し臭素含有量が２５重量％であり，Ｘが
水素原子及びアリル基を示し，Ｘの６５％がアリル基で
あるエポキシ樹脂である。Examples 6 to 7 and Comparative Example 3 As the compound represented by the formula (2), both a residue represented by the formula (3) and a residue represented by the formula (4) are present as R, Bromine-containing bisphenol A type epoxy resin in which n is 2.6 (Epicoat 5049, Yuka Shell Epoxy Co., Ltd., epoxy equivalent 735 g / eq, bromine content 2)
6.6 parts by weight) 281 parts (0.5 equivalents of alcoholic hydroxyl group) were dissolved in 560 parts of dimethyl sulfoxide,
76.5 parts of allyl chloride, 30% NaO at 40 ° C. with stirring
The reaction was performed in the same manner as in Example 1 except that 88.0 parts of the H aqueous solution was added to obtain 217 parts of an epoxy resin (6) having an epoxy equivalent of 782 g / eq. Using NMR, the total functional group equivalent of the obtained epoxy resin (6), which is a combination of allyl groups and glycidyl groups, was calculated to be 416 g / eq.
The obtained epoxy resin (6) has n =
2.6, R represents a residue represented by the formula (3) and a residue represented by the formula (4), the bromine content is 25% by weight, X represents a hydrogen atom and an allyl group, X 65% of the epoxy resin is an allyl group.
【００４１】また同様の方法で３０％ＮａＯＨ水溶液の
使用量を６０．９部にしてエポキシ当量７７０ｇ／ｅｑ
のエポキシ樹脂（７）２０６部を得た。ＮＭＲを用い
て、得られたエポキシ樹脂（７）のアリル基とグリシジ
ル基とを合わせた総官能基当量を算出すると４７６ｇ／
ｅｑとなった。得られたエポキシ樹脂（７）は，式
（１）においてｎ＝２．６，Ｒが式（３）で表される残
基及び式（４）で表される残基を示し臭素含有量が２
５．４重量％であり，Ｘが水素原子及びアリル基を示
し，Ｘの４５％がアリル基であるエポキシ樹脂である。In the same manner, the amount of the 30% NaOH aqueous solution used was 60.9 parts and the epoxy equivalent was 770 g / eq.
206 parts of epoxy resin (7) was obtained. The total functional group equivalent of the obtained epoxy resin (7) including allyl group and glycidyl group was calculated by using NMR to obtain 476 g /
It became eq. The obtained epoxy resin (7) has a bromine content of n = 2.6 in the formula (1), R represents a residue represented by the formula (3) and a residue represented by the formula (4). Two
The epoxy resin is 5.4% by weight, X represents a hydrogen atom and an allyl group, and 45% of X is an allyl group.
【００４２】また得られたエポキシ樹脂（６）〜
（７）、比較としてエポキシ樹脂エピコート５０４９、
硬化剤としてジアミノジフェニルメタン（ＤＤＭ）を用
い、表３に示す組成で配合して、７０℃で１５分ロール
で混練し、１５０℃、１８０秒でトランスファー成形し
て、その後１６０℃で２時間、更に１８０℃で８時間硬
化せしめて試験片を作成し、ガラス転移点及び吸水率を
測定した。結果を表３に示す。なお，表中，各成分の欄
の数値は重量部を示す。The obtained epoxy resins (6) to
(7), for comparison, epoxy resin Epicoat 5049,
Using diaminodiphenylmethane (DDM) as a curing agent, blended with the composition shown in Table 3, kneading with a roll for 15 minutes at 70 ° C., transfer molding at 150 ° C. for 180 seconds, and then at 160 ° C. for 2 hours, and further. A test piece was prepared by curing at 180 ° C. for 8 hours, and the glass transition point and water absorption were measured. The results are shown in Table 3. In addition, in the table, the numerical value in the column of each component shows a part by weight.
【００４３】 [0043]
【００４４】実施例８〜１０，比較例４ 式（２）で表されるエポキシ樹脂としてＲが式（３）で
示される残基であり，ｎが３．２であるビスフェノール
Ａ型エポキシ樹脂（エポミックＲ−３０２，三井石油化
学（株），エポキシ当量６２９ｇ／ｅｑ）３８９部（ア
ルコール性水酸基１．０当量）をジメチルスルホキシド
８００部に溶解させた後，攪拌下３０℃で塩化アリル７
６．５部を添加した。その後の３０％ＮａＯＨ水溶液１
３５部（１．０モル）を加え還流下で５０℃に昇温し３
時間反応を行った。反応終了後メチルイソブチルケトン
１６００部，水８００部を加え２回水洗を行った。油水
分離後，油層よりメチルイソブチルケトン及びジメチル
スルホキシドを減圧下に蒸留回収し，エポキシ当量６９
０ｇ／ｅｑのエポキシ樹脂（８）３７５部を得た。得ら
れたエポキシ樹脂（８）は，式（１）においてｎ＝３．
２，Ｒが式（３）で表される残基，Ｘが水素原子及びア
リル基を示し，Ｘの５０％がアリル基で，ＮＭＲによる
総官能基当量＝３８１ｇ／ｅｑであるエポキシ樹脂であ
る。Examples 8 to 10, Comparative Example 4 As the epoxy resin represented by the formula (2), R is a residue represented by the formula (3) and n is 3.2. Epomic R-302, Mitsui Petrochemical Co., Ltd., epoxy equivalent 629 g / eq, 389 parts (alcoholic hydroxyl group 1.0 equivalent) was dissolved in dimethyl sulfoxide 800 parts, and then allyl chloride 7 was stirred at 30 ° C.
6.5 parts were added. Then 30% NaOH aqueous solution 1
35 parts (1.0 mol) was added and the temperature was raised to 50 ° C. under reflux.
The reaction was carried out over time. After the completion of the reaction, 1600 parts of methyl isobutyl ketone and 800 parts of water were added and washed twice with water. After oil-water separation, methyl isobutyl ketone and dimethyl sulfoxide were distilled and recovered from the oil layer under reduced pressure to obtain an epoxy equivalent of 69
375 parts of 0 g / eq of epoxy resin (8) was obtained. The obtained epoxy resin (8) has n = 3.
2, R is a residue represented by the formula (3), X is a hydrogen atom and an allyl group, 50% of X is an allyl group, and the total functional group equivalent by NMR is 381 g / eq. .
【００４５】また同様の方法で３０％ＮａＯＨ水溶液の
使用量を９４．７部（０．７モル）にしてエポキシ当量
６８２ｇ／ｅｑのエポキシ樹脂（９）３７１部を得た。
得られたエポキシ樹脂（９）は，式（１）においてｎ＝
３．２，Ｒが式（３）で表される残基，Ｘが水素原子及
びアリル基を示し，Ｘの３５％がアアリル基で，ＮＭＲ
による総官能基当量＝４３２ｇ／ｅｑであるエポキシ樹
脂である。In the same manner, the amount of 30% NaOH aqueous solution used was 94.7 parts (0.7 mol) to obtain 371 parts of epoxy resin (9) having an epoxy equivalent of 682 g / eq.
The obtained epoxy resin (9) has n =
3.2, R is a residue represented by the formula (3), X is a hydrogen atom and an allyl group, and 35% of X is an allyl group, and NMR
Is an epoxy resin having a total functional group equivalent of 432 g / eq.
【００４６】更に同様の方法で３０％ＮａＯＨ水溶液の
使用量を５４．１部（０．４モル）にしてエポキシ当量
６７１ｇ／ｅｑのエポキシ樹脂（１０）366 部を得た。
得られたエポキシ樹脂（１０）は，式（１）においてｎ
＝３．２，Ｒが式（３）で表される残基，Ｘが水素原子
及びアリル基を示し，Ｘの２０％がアリル基であり，Ｎ
ＭＲによる総官能基当量＝４９５ｇ／ｅｑのエポキシ樹
脂である。In the same manner, the amount of 30% NaOH aqueous solution used was 54.1 parts (0.4 mol) to obtain 366 parts of epoxy resin (10) having an epoxy equivalent of 671 g / eq.
The obtained epoxy resin (10) has n in the formula (1).
= 3.2, R is a residue represented by the formula (3), X represents a hydrogen atom and an allyl group, and 20% of X is an allyl group, N
It is an epoxy resin having a total functional group equivalent by MR of 495 g / eq.
【００４７】また得られたエポキシ樹脂（８）〜（１
０），比較としてエポキシ樹脂エポミックＲ−３０２，
硬化剤としてＤＤＭを用い，表４に示す組成で配合し
て，７０℃で１５分ロール混練し，１５０℃，１８０秒
でトランスファー成形して，その後１６０℃で２時間，
更に１８０℃で８時間硬化せしめて試験片を作成し，ガ
ラス転移点及び吸水率を測定した。結果を表４に示す。
なお，表中，各成分の欄の数値は重量部を示す。The obtained epoxy resins (8) to (1
0), for comparison, epoxy resin Epomic R-302,
Using DDM as a curing agent, compounding with the composition shown in Table 4, roll kneading at 70 ° C for 15 minutes, transfer molding at 150 ° C for 180 seconds, and then at 160 ° C for 2 hours,
Further, it was cured at 180 ° C. for 8 hours to prepare a test piece, and the glass transition point and water absorption were measured. The results are shown in Table 4.
In addition, in the table, the numerical value in the column of each component shows a part by weight.
【００４８】 表４ 実施例 比較例 ８ ９ １０ ４ エポキシ樹脂（８） 100 エポキシ樹脂（９） 100 エポキシ樹脂（１０） 100 エポミックＲ−３０２ 100 エポキシ当量（g/eq) 690 682 671 629 総官能基当量(g/eq) 381 432 495 629 ＤＤＭ 13 11 10 8 ガラス転移点（℃） 156 152 145 130 吸水率（％） 1.33 1.67 1.84 2.04Table 4 Example Comparative Example 8 9 10 4 Epoxy resin (8) 100 Epoxy resin (9) 100 Epoxy resin (10) 100 Epomic R-302 100 Epoxy equivalent (g / eq) 690 682 671 629 Total functional groups Equivalent (g / eq) 381 432 495 629 DDM 13 11 10 8 Glass transition point (℃) 156 152 145 130 Water absorption rate (%) 1.33 1.67 1.84 2.04
【００４９】[0049]
【発明の効果】本発明のエポキシ樹脂は耐熱性、耐水性
に優れた特性を兼ね備えた硬化物を与えることができ、
成形材料，注型材料，積層材料，塗料，接着剤，レジス
トなどの広範囲の用途に極めて有用である。The epoxy resin of the present invention can provide a cured product having excellent heat resistance and water resistance.
It is extremely useful for a wide range of applications such as molding materials, casting materials, laminated materials, paints, adhesives and resists.
Claims (4)
ェノール性水酸基を有する化合物の水酸基が除かれた残
基を表し、個々のＲはお互いに同一であっても異なって
いてもよい。又、個々のＸは、水素原子、アリル基、或
いはグリシジル基を表し、個々のＸはお互いに同一であ
っても異なっていてもよいが、Ｘの５％以上はアリル基
である。）で表されるエポキシ樹脂。1. A formula (1): (In the formula, n represents an average value and represents a positive number. R represents a residue obtained by removing a hydroxyl group of a compound having two phenolic hydroxyl groups, and each R is the same or different. Further, each X represents a hydrogen atom, an allyl group, or a glycidyl group, and each X may be the same as or different from each other, but 5% or more of X is an allyl group. The epoxy resin represented by.
化促進剤を含有するエポキシ樹脂組成物において、該エ
ポキシ樹脂成分として請求項１記載のエポキシ樹脂を含
有することを特徴とするエポキシ樹脂組成物。2. An epoxy resin composition containing an epoxy resin, a curing agent, and optionally a curing accelerator, wherein the epoxy resin composition according to claim 1 is contained as the epoxy resin component. .
る積層板用エポキシ樹脂組成物。3. An epoxy resin composition for laminates, which comprises the epoxy resin composition according to claim 2.
の硬化物。4. A cured product of the epoxy resin composition according to claim 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04869693A JP3377241B2 (en) | 1993-02-16 | 1993-02-16 | Method for producing epoxy resin, epoxy resin composition and cured product thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04869693A JP3377241B2 (en) | 1993-02-16 | 1993-02-16 | Method for producing epoxy resin, epoxy resin composition and cured product thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06239966A true JPH06239966A (en) | 1994-08-30 |
| JP3377241B2 JP3377241B2 (en) | 2003-02-17 |
Family
ID=12810477
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04869693A Expired - Fee Related JP3377241B2 (en) | 1993-02-16 | 1993-02-16 | Method for producing epoxy resin, epoxy resin composition and cured product thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3377241B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07228580A (en) * | 1993-12-21 | 1995-08-29 | Yuka Shell Epoxy Kk | Modified polyvalent epoxy compound, production of the compound and epoxy resin composition |
| WO2008018364A1 (en) * | 2006-08-07 | 2008-02-14 | Nippon Steel Chemical Co., Ltd. | Prepreg, laminate and printed wiring board |
| JP2010513577A (en) * | 2006-12-14 | 2010-04-30 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン | Adhesive polyurethane adhesive |
| JP5088952B2 (en) * | 2005-05-09 | 2012-12-05 | 日本化薬株式会社 | Epoxy resin, production method thereof and use thereof |
-
1993
- 1993-02-16 JP JP04869693A patent/JP3377241B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07228580A (en) * | 1993-12-21 | 1995-08-29 | Yuka Shell Epoxy Kk | Modified polyvalent epoxy compound, production of the compound and epoxy resin composition |
| JP5088952B2 (en) * | 2005-05-09 | 2012-12-05 | 日本化薬株式会社 | Epoxy resin, production method thereof and use thereof |
| WO2008018364A1 (en) * | 2006-08-07 | 2008-02-14 | Nippon Steel Chemical Co., Ltd. | Prepreg, laminate and printed wiring board |
| JP5234962B2 (en) * | 2006-08-07 | 2013-07-10 | 新日鉄住金化学株式会社 | Prepreg, laminated board and printed wiring board |
| JP2010513577A (en) * | 2006-12-14 | 2010-04-30 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン | Adhesive polyurethane adhesive |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3377241B2 (en) | 2003-02-17 |
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