JPH1129621A - Phenolic compound, epoxy compound and resin composition containing the same - Google Patents

Phenolic compound, epoxy compound and resin composition containing the same

Info

Publication number
JPH1129621A
JPH1129621A JP18347897A JP18347897A JPH1129621A JP H1129621 A JPH1129621 A JP H1129621A JP 18347897 A JP18347897 A JP 18347897A JP 18347897 A JP18347897 A JP 18347897A JP H1129621 A JPH1129621 A JP H1129621A
Authority
JP
Japan
Prior art keywords
compound
phenyl
epoxy
bis
aminophenoxy
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.)
Pending
Application number
JP18347897A
Other languages
Japanese (ja)
Inventor
Junichi Katagiri
純一 片桐
Akio Takahashi
昭雄 高橋
Akio Nishikawa
昭夫 西川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hitachi Ltd
Original Assignee
Hitachi Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hitachi Ltd filed Critical Hitachi Ltd
Priority to JP18347897A priority Critical patent/JPH1129621A/en
Publication of JPH1129621A publication Critical patent/JPH1129621A/en
Pending legal-status Critical Current

Links

Abstract

PROBLEM TO BE SOLVED: To obtain a new phenolic compound or epoxy compound useful for composite materials excellent in heat resistance and flexibility such as materials for laminates and molding materials for semiconductor sealing use, adhesives, coating materials, etc. SOLUTION: This new phenolic compound is shown by formula I (R1 to R4 are each H, a lower alkyl, etc.;5 and R6 are each H, F, a fluoroalkyl, etc.), and obtained by diazotizing an ether linkage-contg. amine compound of formula II e.g. 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[3-methyl-4-(-4- aminophenoxy)phenyl]propane} followed by thermal decomposition of the resulting diazonium salt in its acidic aqueous solution. This compound exhibits infrared absorption spectra at 1,230 cm<-1> based on the ether linkage and at 3,550-3,200 cm<-1> based on the hydroxyl group.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明の属する技術分野】本発明は、積層板用材料,半
導体封止用成形材料を始めとする複合材料用,接着,塗
料等に有用な、耐熱性,可撓性に優れたエーテル結合を
有するフェノール化合物,エポキシ化合物及び該化合物
を含む樹脂組成物に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ether bond having excellent heat resistance and flexibility, which is useful for materials for laminated boards, molding materials for semiconductor encapsulation and other composite materials, adhesives, paints and the like. The present invention relates to a phenol compound, an epoxy compound and a resin composition containing the compound.

【0002】[0002]

【従来の技術】エポキシ樹脂は作業性及び電気特性,機
械的特性,耐熱性,接着性等の硬化物特性に優れており
電気,電子部品,構造材料,接着剤,塗料等の分野で広
く用いられている。
2. Description of the Related Art Epoxy resins are excellent in workability and cured product properties such as electrical properties, mechanical properties, heat resistance and adhesiveness, and are widely used in the fields of electrics, electronic parts, structural materials, adhesives, and paints. Have been.

【0003】最近の電機機器の小型軽量化や使用環境の
過酷化等に伴って、複合材料には耐熱性,機械的特性等
に、より一層の優れた材料が望まれるようになった。こ
れらの要求に対して、フェノール,エポキシ化合物等を
含有するエポキシ樹脂組成物について種々の提案がなさ
れているが、未だ不十分である。
[0003] With the recent miniaturization of electric appliances and the severer use environment, it has been demanded that composite materials have better heat resistance and mechanical properties. To meet these requirements, various proposals have been made for epoxy resin compositions containing phenol, epoxy compounds and the like, but these are still insufficient.

【0004】[0004]

【発明が解決しようとする課題】本発明は、耐熱性,可
撓性に優れたエーテル結合を有するフェノール化合物,
エポキシ化合物及び該化合物を含有する樹脂組成物とを
提供することにある。
DISCLOSURE OF THE INVENTION The present invention relates to a phenol compound having an ether bond having excellent heat resistance and flexibility,
An object of the present invention is to provide an epoxy compound and a resin composition containing the compound.

【0005】[0005]

【課題を解決するための手段】本発明は、 (1)前記一般式〔I〕(式中、R1〜R4は水素,低級
アルキル基,低級アルコキシ基,ハロゲン,フルオロア
ルキル基のいずれかであり、お互いに同じであっても異
なってもよい。R5,R6は水素,フッ素,低級アルキル
基,フルオロアルキル基のいずれかであり、互いに同じ
であっても異なってもよい。)で表されるフェノール化
合物。
According to the present invention, there is provided a compound represented by the following general formula (I): wherein R 1 to R 4 are any of hydrogen, a lower alkyl group, a lower alkoxy group, a halogen and a fluoroalkyl group. And R 5 and R 6 may be any of hydrogen, fluorine, a lower alkyl group and a fluoroalkyl group, and may be the same or different.) A phenolic compound represented by

【0006】(2)前記一般式〔I〕で表されるフェノ
ール化合物の水酸基をグリシジルエーテル化してなるエ
ポキシ化合物。
(2) An epoxy compound obtained by glycidyl etherification of a hydroxyl group of a phenol compound represented by the above general formula [I].

【0007】(3)上記(1)記載のフェノール化合物
と(2)記載のエポキシ化合物を含有してなるエポキシ
樹脂組成物。
(3) An epoxy resin composition containing the phenol compound described in (1) and the epoxy compound described in (2).

【0008】(4)上記(1)記載のフェノール化合物
とエポキシ化合物を含有してなるエポキシ樹脂組成物。
(4) An epoxy resin composition containing the phenolic compound and the epoxy compound as described in (1) above.

【0009】(5)上記(2)記載のエポキシ化合物と
硬化剤を含有してなるエポキシ樹脂組成物。
(5) An epoxy resin composition comprising the epoxy compound according to (2) and a curing agent.

【0010】[0010]

【発明の実施の形態】本発明において、前記一般式
〔I〕で示されるエーテル結合を有するフェノール化合
物は、一般式〔II〕
BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the phenolic compound having an ether bond represented by the above general formula [I] is a compound represented by the general formula [II]

【0011】[0011]

【化2】 Embedded image

【0012】(式中、R1〜R4は水素,低級アルキル
基,低級アルコキシ基,ハロゲン,フルオロアルキル基
のいずれかであり、お互いに同じであっても異なっても
よい。R5,R6は水素,フッ素,低級アルキル基,フル
オロアルキル基のいずれかであり、互いに同じであって
も異なってもよい。)で表されるエーテル結合を有する
アミン化合物、例えば、2,2′−ビス〔4−(4−ア
ミノフェノキシ)フェニル〕プロパン、2,2′−ビス
〔3−メチル−4−(4−アミノフェノキシ)フェニ
ル〕プロパン、2,2′−ビス〔3−クロロ−4−(4
−アミノフェノキシ)フェニル〕プロパン、2,2′−
ビス〔3−ブロモ−4−(4−アミノフェノキシ)フェ
ニル〕プロパン、2,2′−ビス〔3−エチル−4−
(4−アミノフェノキシ)フェニル〕プロパン、2,
2′−ビス〔3−プロピル−4−(4−アミノフェノキ
シ)フェニル〕プロパン、2,2′−ビス〔3−イソプ
ロピル−4−(4−アミノフェノキシ)フェニル〕プロ
パン、2,2′−ビス〔3−ブチル−4−(4−アミノ
フェノキシ)フェニル〕プロパン、2,2′−ビス〔3
−s−ブチル−4−(4−アミノフェノキシ)フェニ
ル〕プロパン、2,2′−ビス〔3−メトキシ−4−
(4−アミノフェノキシ)フェニル〕プロパン、1,
1′−ビス〔4−(4−アミノフェノキシ)フェニル〕
エタン、1,1′−ビス〔3−メチル−4−(4−アミ
ンフェノキシ)フェニル〕エタン、1,1′−ビス〔3
−クロロ−4−(4−アミノフェノキシ)フェニル〕エ
タン、1,1′−ビス〔3−ブロモ−4−(4−アミノ
フェノキシ)フェニル〕エタン、ビス〔4−(4−アミ
ノフェノキシ)フェニル〕メタン、ビス〔3−メチル−
4−(4−アミノフェノキシ)フェニル〕メタン、ビス
〔3−クロロ−4−(4−アミノフェノキシ)フェニ
ル〕メタン、ビス〔3−ブロモ−4−(4−アミノフェ
ノキシ)フェニル〕メタン、1,1,1,3,3,3−
ヘキサフルオロ−2,2−ビス〔4−(4−アミノフェ
ノキシ)フェニル〕プロパン、1,1,1,3,3,3
−ヘキサクロロ−2,2−ビス〔4−(4−アミノフェ
ノキシ)フェニル〕プロパン、3,3−ビス〔4−(4
−アミノフェノキシ)フェニル〕ペンタン、1,1−ビ
ス〔4−(4−アミノフェノキシ)フェニル〕プロパ
ン、1,1,1,3,3,3−ヘキサフルオロ−2,2
−ビス〔3,5−ジメチル−4−(4−アミノフェノキ
シ)フェニル〕プロパン、1,1,1,3,3,3−ヘ
キサフルオロ−2,2−ビス〔3,5−ジブロモ−4−
(4−アミノフェノキシ)フェニル〕プロパン、1,
1,1,3,3,3−ヘキサフルオロ−2,2−ビス
〔3−メチル−4−(4−アミノフェノキシ)フェニ
ル〕プロパンなどの化合物をジアゾ化し、ジアゾニウム
塩を酸性水溶液中で熱分解させる方法で得ることができ
る。
(Wherein, R 1 to R 4 are any of hydrogen, lower alkyl group, lower alkoxy group, halogen and fluoroalkyl group, and may be the same or different from each other. R 5 , R 6 is hydrogen, fluorine, a lower alkyl group or a fluoroalkyl group, which may be the same or different from each other.), For example, an amine compound having an ether bond, such as 2,2'-bis [4- (4-aminophenoxy) phenyl] propane, 2,2'-bis [3-methyl-4- (4-aminophenoxy) phenyl] propane, 2,2'-bis [3-chloro-4- ( 4
-Aminophenoxy) phenyl] propane, 2,2'-
Bis [3-bromo-4- (4-aminophenoxy) phenyl] propane, 2,2'-bis [3-ethyl-4-
(4-aminophenoxy) phenyl] propane, 2,
2'-bis [3-propyl-4- (4-aminophenoxy) phenyl] propane, 2,2'-bis [3-isopropyl-4- (4-aminophenoxy) phenyl] propane, 2,2'-bis [3-butyl-4- (4-aminophenoxy) phenyl] propane, 2,2'-bis [3
-S-butyl-4- (4-aminophenoxy) phenyl] propane, 2,2'-bis [3-methoxy-4-
(4-aminophenoxy) phenyl] propane, 1,
1'-bis [4- (4-aminophenoxy) phenyl]
Ethane, 1,1'-bis [3-methyl-4- (4-aminephenoxy) phenyl] ethane, 1,1'-bis [3
-Chloro-4- (4-aminophenoxy) phenyl] ethane, 1,1'-bis [3-bromo-4- (4-aminophenoxy) phenyl] ethane, bis [4- (4-aminophenoxy) phenyl] Methane, bis [3-methyl-
4- (4-aminophenoxy) phenyl] methane, bis [3-chloro-4- (4-aminophenoxy) phenyl] methane, bis [3-bromo-4- (4-aminophenoxy) phenyl] methane, 1, 1,1,3,3,3-
Hexafluoro-2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,1,1,3,3,3
-Hexachloro-2,2-bis [4- (4-aminophenoxy) phenyl] propane, 3,3-bis [4- (4
-Aminophenoxy) phenyl] pentane, 1,1-bis [4- (4-aminophenoxy) phenyl] propane, 1,1,1,3,3,3-hexafluoro-2,2
-Bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] propane, 1,1,1,3,3,3-hexafluoro-2,2-bis [3,5-dibromo-4-
(4-aminophenoxy) phenyl] propane, 1,
Compounds such as 1,1,3,3,3-hexafluoro-2,2-bis [3-methyl-4- (4-aminophenoxy) phenyl] propane are diazotized, and the diazonium salt is thermally decomposed in an acidic aqueous solution. Can be obtained.

【0013】合成された本発明のエーテル結合を有する
フェノール化合物は、その赤外線吸収(IR)スペクト
ルが1230cm-1にエーテル結合に基づく特性吸収
が、3550〜3200cm-1にヒドロキシル基に基づ
く特性吸収が認められることから、前記一般式〔I〕で
表される化学構造を有するものである。
[0013] phenol compound having an ether bond of the present invention which is synthesized, its infrared (IR) absorption spectrum characteristic absorption based on the ether bond to 1230 cm -1, characteristic absorption based on hydroxyl groups 3550~3200Cm -1 Since it is recognized, it has a chemical structure represented by the general formula [I].

【0014】本発明のフェノール化合物にエピクロロヒ
ドリンを反応させることにより上記(2)記載のエポキ
シ化合物が得られる。この反応は、従来の公知の方法で
合成することができる。例えば、本発明のフェノール化
合物とエピクロロヒドリンの混合物に水酸化ナトリウム
等のアルカリ金属水酸化物を添加し30〜120℃で
0.5 〜10時間させた後、水洗,加熱減圧下で過剰な
エピクロロヒドリンを除去してエポキシ化合物を得るこ
とができる。
The epoxy compound described in the above (2) can be obtained by reacting epichlorohydrin with the phenol compound of the present invention. This reaction can be synthesized by a conventionally known method. For example, an alkali metal hydroxide such as sodium hydroxide is added to a mixture of the phenol compound of the present invention and epichlorohydrin, and the mixture is allowed to stand at 30 to 120 ° C. for 0.5 to 10 hours, and then washed with water and heated under reduced pressure to obtain an excess. An epoxy compound can be obtained by removing epichlorohydrin.

【0015】合成された本発明のエーテル結合を有する
エポキシ化合物は、その赤外線吸収(IR)スペクトル
が1230cm-1にエーテル結合に基づく特性吸収が、9
50,830cm-1にエポキシ基に基づく特性吸収が認め
られることから、前記一般式〔I〕で表される化学構造
を有するものである。従って、柔軟なエーテル結合と反
応性に優れたエポキシ基を有することにより、優れた耐
熱性,機械的特性を示すものと推定される。
The synthesized epoxy compound having an ether bond of the present invention has an infrared absorption (IR) spectrum at 1230 cm -1 and a characteristic absorption based on the ether bond of 9
Since a characteristic absorption based on an epoxy group is observed at 50,830 cm -1 , the compound has a chemical structure represented by the above general formula [I]. Therefore, it is presumed that it has excellent heat resistance and mechanical properties by having a flexible ether bond and an epoxy group having excellent reactivity.

【0016】本発明のフェノール化合物は(3),(4)
記載のエポキシ樹脂組成物において(2)記載のエポキ
シ化合物及び既に公知のエポキシ化合物の硬化剤として
用いられる。この場合、公知の硬化剤と併用して用いる
ことができる。
The phenol compound of the present invention comprises (3) and (4)
The epoxy resin composition described above is used as a curing agent for the epoxy compound described in (2) and a known epoxy compound. In this case, it can be used in combination with a known curing agent.

【0017】ここで公知のエポキシ化合物とは、ビスフ
ェノールA型エポキシ樹脂,ビスフェノールF型エポキ
シ樹脂,ノボラック型エポキシ樹脂,脂環式エポキシ樹
脂,ビフェニル型エポキシ樹脂,グリシジルエステル型
エポキシ樹脂,グリシジルアミン型エポキシ樹脂等が挙
げられるがこれらに限定されるものではない。これらは
単独で用いてもよく、2種以上用いることもできる。
Here, the known epoxy compounds include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin, alicyclic epoxy resin, biphenyl type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin. Examples include, but are not limited to, resins. These may be used alone or in combination of two or more.

【0018】また、(5)記載のエポキシ樹脂組成物に
おいて(2)記載のエポキシ化合物に公知の硬化剤を用
いる。この硬化剤としては、アミン類,酸無水物,ポリ
アミド樹脂,イミダゾール類,三フッ化ホウ素アミン錯
体,ジシアンジアミド,フェノール樹脂,ポリビニルフ
ェノール等が用いられる。これらは単独で用いてもよ
く、2種以上用いることもできる。また、これらの硬化
剤を用いるに当たって硬化促進剤を併用してもよい。
In the epoxy resin composition described in (5), a known curing agent is used for the epoxy compound described in (2). As the curing agent, amines, acid anhydrides, polyamide resins, imidazoles, boron trifluoride amine complexes, dicyandiamide, phenol resins, polyvinyl phenol, etc. are used. These may be used alone or in combination of two or more. When using these curing agents, a curing accelerator may be used in combination.

【0019】さらに、本発明のエポキシ樹脂組成物に
は、その用途に応じてポリエチレンジグリシジルエーテ
ル,フェニルグリシジルエーテル等の稀釈剤,ポリグリ
シジルエーテル,エポキシ変性ポリブタジェン,アクリ
ロニトリル−ポリブタジェンゴム等の可撓性付与剤,シ
ランカップリング剤,離型剤等を適宜使用できる。
Further, the epoxy resin composition of the present invention may contain a diluent such as polyethylene diglycidyl ether and phenyl glycidyl ether, a polyglycidyl ether, epoxy-modified polybutadiene, acrylonitrile-polybutadiene rubber and the like, depending on the use. A flexibilizing agent, a silane coupling agent, a release agent, and the like can be appropriately used.

【0020】本発明のエポキシ樹脂組成物は従来から知
られている方法で容易に硬化物とすることができる。
The epoxy resin composition of the present invention can be easily cured by a conventionally known method.

【0021】例えば、積層板用材料の用途には溶剤とし
てトルエン,キシレン,アセトン,メチルエチルケト
ン、3−メトキシプロパノール,プロピレングリコール
メチルエーテル,プロピレングリコールエチルエーテ
ル,エチレングリコールエチルエーテル,エチレングリ
コールメチルエーテル,エチレングリコールブチルエー
テル,プロピレングリコールメチルエーテルアセテー
ト、3−メチル−3−メトキシブチルアセテート,シク
ロヘキサノン,ジオキサン、N,N′−ジメチルホルム
アミド、N−メチル−2−ピロリドン,ジメチルスルホ
キシド,トリクロロエチレン,トリクロロエタンなどを
用い、上記のフェノール化合物,エポキシ化合物,硬化
剤等を配合したワニスを作製する。
For example, for use as a material for a laminate, toluene, xylene, acetone, methyl ethyl ketone, 3-methoxypropanol, propylene glycol methyl ether, propylene glycol ethyl ether, ethylene glycol ethyl ether, ethylene glycol methyl ether, ethylene glycol are used as solvents. Using butyl ether, propylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl acetate, cyclohexanone, dioxane, N, N'-dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, trichloroethylene, trichloroethane, etc. A varnish containing a phenol compound, an epoxy compound, a curing agent and the like is prepared.

【0022】このワニスを無機繊維としてEガラス,C
ガラス,Aガラス,Sガラス,Dガラス,Qガラス等の
各種ガラスクロス,有機繊維としてアラミド繊維等や不
織布としてアラミド,芳香族ポリエステル等に塗布し、
溶剤除去してプリプレグを作製する。該プリプレグを加
熱プレス機等を用いて、100〜200℃の温度で加圧
加熱硬化して積層板用材料を得る。
This varnish is used as inorganic fiber for E glass, C
Various glass cloths such as glass, A glass, S glass, D glass, and Q glass; aramid fibers and the like as organic fibers; and aramid and aromatic polyester as nonwoven fabrics;
A prepreg is prepared by removing the solvent. The prepreg is heated under pressure at a temperature of 100 to 200 ° C. using a heating press or the like to obtain a laminate material.

【0023】成形材料としての用途には、ジルコン,シ
リカ,アルミナ,水酸化アルミニウム,炭酸カルシウ
ム,クレー,カオリン,タルク,珪砂,溶融石英ガラ
ス,アスベスト,マイカ,各種ウイスカー,カーボンブ
ラック,二硫化モリブデンなどのような充填材,高級脂
肪酸やワックスなどのような離型剤,エポキシシラン,
ビニルシラン,アルコキシチタネート化合物などのカッ
プリング剤が配合される。また必要に応じて含ハロゲン
系化合物,酸化アンチモンやリン系化合物などの難燃性
付与剤,顔料などを用い、ロール等で混練し均一に混合
してペレット状の成形材料を作製する。該材料をトラン
スファー成型機などで100〜200℃の温度で加圧加
熱して硬化物を得ることができる。
For use as a molding material, zircon, silica, alumina, aluminum hydroxide, calcium carbonate, clay, kaolin, talc, silica sand, fused quartz glass, asbestos, mica, various whiskers, carbon black, molybdenum disulfide, etc. Fillers, release agents such as higher fatty acids and waxes, epoxy silanes,
Coupling agents such as vinyl silane and alkoxy titanate compounds are blended. If necessary, a halogen-containing compound, a flame-retardant imparting agent such as antimony oxide or a phosphorus compound, a pigment, and the like are kneaded with a roll or the like and uniformly mixed to prepare a pellet-shaped molding material. The material can be pressurized and heated at a temperature of 100 to 200 ° C. with a transfer molding machine or the like to obtain a cured product.

【0024】次に、本発明を具体的な実施例に基づいて
説明する。
Next, the present invention will be described based on specific embodiments.

【0025】(実施例1)2,2′−ビス〔4−(4−
アミノフェノキシ)フェニル〕プロパン20gをエタノ
ール100mlに溶解し、これに熱水200mlと亜硫
酸水素ナトリウム12gを加えた後24時間還流下に加
熱する。冷却後濾過し、濾液にやや過剰の水酸化ナトリ
ウムを加えて、更に0.5 時間穏やかに加熱、再び濾過
し、濾液に氷酢酸100mlを加えて酸性にするとフェ
ノール化合物(a)が得られる。
(Example 1) 2,2'-bis [4- (4-
Aminophenoxy) phenyl] propane (20 g) was dissolved in ethanol (100 ml). To this, 200 ml of hot water and 12 g of sodium bisulfite were added, and the mixture was heated under reflux for 24 hours. After cooling, the mixture was filtered, a slight excess of sodium hydroxide was added to the filtrate, the mixture was gently heated for another 0.5 hour, filtered again, and the filtrate was acidified with 100 ml of glacial acetic acid to obtain the phenol compound (a).

【0026】IRスペクトルを測定した結果、1230
〜1240cm-1にエーテル結合の特性吸収、3500〜
3200cm-1にヒドロキシル基に由来する特性吸収が認
められた。
As a result of measuring the IR spectrum, 1230
Characteristic absorption of ether bond at ~ 1240 cm -1 , 3500
Characteristic absorption derived from the hydroxyl group was observed at 3200 cm -1 .

【0027】(実施例2)1,1′−ビス〔4−(4−
アミノフェノキシ)フェニル〕エタンを用いた他は実施
例1と同様にしてフェノール化合物(b)を得た。
Example 2 1,1'-bis [4- (4-
A phenol compound (b) was obtained in the same manner as in Example 1 except that [aminophenoxy) phenyl] ethane was used.

【0028】IRスペクトルを測定した結果、1230
〜1240cm-1にエーテル結合の特性吸収、3550〜
3200cm-1にヒドロキシル基に由来する特性吸収が認
められた。
As a result of measuring the IR spectrum, 1230
Characteristic absorption of ether bond at ~ 1240 cm -1 , 3550 ~
Characteristic absorption derived from the hydroxyl group was observed at 3200 cm -1 .

【0029】(実施例3)実施例1で得られたフェノー
ル化合物40重量部をエピクロルヒドリン75重量部、
ジメチルスルホキシド40重量部に溶解させた後、水酸
化ナトリウム10重量部添加し、60℃で3時間反応さ
せた。水洗で中性にした後、加熱減圧下で過剰のエピク
ロルヒドリンを除去し、残留物をメチルエチルケトンに
溶解した。さらに、この溶液を60℃に加熱し、水酸化
ナトリウム水溶液を加えて約1時間反応後、水洗,加熱
減圧下で溶剤を除去しエポキシ化合物を得た。得られた
エポキシ化合物のエポキシ当量は275であった。
Example 3 40 parts by weight of the phenol compound obtained in Example 1 were added to 75 parts by weight of epichlorohydrin,
After dissolving in 40 parts by weight of dimethyl sulfoxide, 10 parts by weight of sodium hydroxide was added and reacted at 60 ° C. for 3 hours. After neutralization by washing with water, excess epichlorohydrin was removed under heating and reduced pressure, and the residue was dissolved in methyl ethyl ketone. Further, this solution was heated to 60 ° C., an aqueous sodium hydroxide solution was added thereto, and the mixture was reacted for about 1 hour, washed with water, and heated to remove the solvent under reduced pressure to obtain an epoxy compound. The epoxy equivalent of the obtained epoxy compound was 275.

【0030】(実施例4〜6,比較例1)実施例2,3
で得られたフェノール化合物(b)およびエポキシ化合
物と、エポキシ樹脂(ECN195:住友化学社製),
フェノール樹脂(PN:日本化薬社製),硬化促進剤に
2−ウンデシルイミダゾールを用い表1に示す割合(重
量部)で、それぞれ別個に配合し4種類の配合物を作製
した。これらに、充填剤として石英ガラス粉85重量
%、離型剤としてステアリン酸2重量部、着色剤として
カーボンブラック1重量部を添加した後、混練機で均一
に混合し、かつ150〜170℃で1〜5分間加熱成形
して、硬化物を作製した。表1に各硬化物の特性を示
す。
(Examples 4 to 6, Comparative Example 1) Examples 2 and 3
A phenolic compound (b) and an epoxy compound obtained in the above, and an epoxy resin (ECN195: manufactured by Sumitomo Chemical Co., Ltd.),
A phenol resin (PN: manufactured by Nippon Kayaku Co., Ltd.) and 2-undecylimidazole as a curing accelerator were separately blended in proportions (parts by weight) shown in Table 1 to prepare four kinds of blends. After adding 85% by weight of quartz glass powder as a filler, 2 parts by weight of stearic acid as a release agent, and 1 part by weight of carbon black as a coloring agent, the mixture is uniformly mixed with a kneader, and at 150 to 170 ° C. Heat molding was performed for 1 to 5 minutes to produce a cured product. Table 1 shows the properties of each cured product.

【0031】[0031]

【表1】 [Table 1]

【0032】(実施例7)実施例1,3で得られたフェ
ノール系化合物(a)40重量部とエポキシ化合物70
重量部とビスフェノールA型エポキシ(エピコート10
01:シェル社製)30重量部をメチルエチルケトンに
加熱溶解させ、固形分量40〜50重量%のワニスを得
る。さらに、硬化剤として2−エチル−4−メチルイミ
ダゾール2重量部添加した後、ガラスクロス(厚さ0.
1mm )に含浸塗工し、60〜80℃,10〜20分間
乾燥してプリプレグを得る。次に、該プリプレグを10
枚重ねて圧力30kg/cm2 ,温度130℃で30分間,
170℃で60分間プレスを行い積層板を得た。
(Example 7) 40 parts by weight of the phenolic compound (a) obtained in Examples 1 and 3 and the epoxy compound 70
Parts by weight and bisphenol A type epoxy (Epicoat 10
01: manufactured by Shell Co.) is dissolved in methyl ethyl ketone by heating to obtain a varnish having a solid content of 40 to 50% by weight. Further, after adding 2 parts by weight of 2-ethyl-4-methylimidazole as a curing agent, a glass cloth (having a thickness of 0.5 mm) was added.
1 mm) and dried at 60 to 80 ° C. for 10 to 20 minutes to obtain a prepreg. Next, the prepreg was added to 10
30kg / cm 2 at a temperature of 130 ° C for 30 minutes
Pressing was performed at 170 ° C. for 60 minutes to obtain a laminate.

【0033】エポキシ積層板(MCL−E−67:日立
化成)との比較結果を表2に示す。
Table 2 shows the results of comparison with the epoxy laminate (MCL-E-67: Hitachi Chemical).

【0034】[0034]

【表2】 [Table 2]

【0035】[0035]

【発明の効果】本発明のフェノール化合物及び、または
エポキシ化合物を含有するエポキシ樹脂組成物は優れた
耐熱性,可撓性を有する成形材料,積層板を提供できる
材料として極めて有用である。
The epoxy resin composition containing the phenolic compound and / or the epoxy compound of the present invention is extremely useful as a material capable of providing a molding material and a laminate having excellent heat resistance and flexibility.

Claims (5)

【特許請求の範囲】[Claims] 【請求項1】一般式〔I〕 【化1】 (式中、R1〜R4は水素,低級アルキル基,低級アルコ
キシ基,ハロゲン,フルオロアルキル基のいずれかであ
り、お互いに同じであっても異なってもよい。R5,R6
は水素,フッ素,低級アルキル基,フルオロアルキル基
のいずれかであり、互いに同じであっても異なってもよ
い。)で表されるエーテル結合を有するフェノール化合
物。
1. A compound of the general formula [I] (Wherein, R 1 to R 4 are any of hydrogen, a lower alkyl group, a lower alkoxy group, a halogen, and a fluoroalkyl group, and may be the same or different from each other. R 5 and R 6
Is hydrogen, fluorine, a lower alkyl group or a fluoroalkyl group, which may be the same or different. A phenol compound having an ether bond represented by the formula:
【請求項2】請求項1記載のフェノール化合物の水酸基
をグリシジルエーテル化してなるエポキシ化合物。
2. An epoxy compound obtained by glycidyl etherification of a hydroxyl group of the phenol compound according to claim 1.
【請求項3】(a)請求項1記載のエーテル結合を有す
るフェノール化合物と(b)請求項2記載のエポキシ化
合物とを含むエポキシ樹脂組成物。
3. An epoxy resin composition comprising (a) the phenol compound having an ether bond according to claim 1 and (b) the epoxy compound according to claim 2.
【請求項4】(a)請求項1記載のエーテル結合を有す
るフェノール化合物と(b)エポキシ化合物とを含むエ
ポキシ樹脂組成物。
4. An epoxy resin composition comprising (a) the phenol compound having an ether bond according to claim 1 and (b) an epoxy compound.
【請求項5】(a)請求項2記載のエポキシ化合物と
(b)硬化剤を含有してなるエポキシ樹脂組成物。
5. An epoxy resin composition comprising (a) the epoxy compound according to claim 2 and (b) a curing agent.
JP18347897A 1997-07-09 1997-07-09 Phenolic compound, epoxy compound and resin composition containing the same Pending JPH1129621A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP18347897A JPH1129621A (en) 1997-07-09 1997-07-09 Phenolic compound, epoxy compound and resin composition containing the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP18347897A JPH1129621A (en) 1997-07-09 1997-07-09 Phenolic compound, epoxy compound and resin composition containing the same

Publications (1)

Publication Number Publication Date
JPH1129621A true JPH1129621A (en) 1999-02-02

Family

ID=16136516

Family Applications (1)

Application Number Title Priority Date Filing Date
JP18347897A Pending JPH1129621A (en) 1997-07-09 1997-07-09 Phenolic compound, epoxy compound and resin composition containing the same

Country Status (1)

Country Link
JP (1) JPH1129621A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6835785B2 (en) * 2002-01-28 2004-12-28 Mitsubishi Gas Chemical Company, Inc. Polyphenylene ether oligomer compound, derivatives thereof and use thereof
JP2006045523A (en) * 2004-06-28 2006-02-16 Canon Inc Cationic photopolymerizable epoxy resin composition, fine structure member produced by using the same and method for producing fine structure member
WO2019151400A1 (en) * 2018-01-31 2019-08-08 三菱瓦斯化学株式会社 Compound, resin, composition, method for forming resist pattern, method for forming circuit pattern, and method for purifying resin

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6835785B2 (en) * 2002-01-28 2004-12-28 Mitsubishi Gas Chemical Company, Inc. Polyphenylene ether oligomer compound, derivatives thereof and use thereof
US7276563B2 (en) 2002-01-28 2007-10-02 Mitsubishi Gas Chemical Company, Inc. Polyphenylene ether oligomer compound, derivatives thereof and use thereof
US7393904B2 (en) 2002-01-28 2008-07-01 Mitsubishi Gas Chemical Company, Inc. (Meth)acrylate-terminated polyphenylene ether
US7560518B2 (en) 2002-01-28 2009-07-14 Mitsubishi Gas Chemical Company, Inc. (Meth)acrylated epoxy-terminated polyphenylene ether
US7632912B2 (en) 2002-01-28 2009-12-15 Mitsubishi Gas Chemical Company, Inc. Carboxylic acid-modified bisphenol epoxy di(meth)acrylate
US7786219B2 (en) 2002-01-28 2010-08-31 Mitsubishi Gas Chemical Company, Inc. Cyanate-terminated polyphenylene ether
JP2006045523A (en) * 2004-06-28 2006-02-16 Canon Inc Cationic photopolymerizable epoxy resin composition, fine structure member produced by using the same and method for producing fine structure member
JP4498232B2 (en) * 2004-06-28 2010-07-07 キヤノン株式会社 Photocationic polymerizable epoxy resin composition, method for producing microstructure using the same, and method for producing inkjet head
WO2019151400A1 (en) * 2018-01-31 2019-08-08 三菱瓦斯化学株式会社 Compound, resin, composition, method for forming resist pattern, method for forming circuit pattern, and method for purifying resin
CN111655662A (en) * 2018-01-31 2020-09-11 三菱瓦斯化学株式会社 Compound, resin, composition, resist pattern forming method, circuit pattern forming method, and resin purifying method
JPWO2019151400A1 (en) * 2018-01-31 2021-02-25 三菱瓦斯化学株式会社 Compounds, resins, compositions, resist pattern forming methods, circuit pattern forming methods and resin purification methods
CN111655662B (en) * 2018-01-31 2023-09-26 三菱瓦斯化学株式会社 Compound, resin, composition, resist pattern forming method, circuit pattern forming method, and resin purifying method

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