JPH0812858A - Epoxy resin composition, prepreg using the epoxy resin composition, and laminate board using the prepreg - Google Patents
Epoxy resin composition, prepreg using the epoxy resin composition, and laminate board using the prepregInfo
- Publication number
- JPH0812858A JPH0812858A JP14584294A JP14584294A JPH0812858A JP H0812858 A JPH0812858 A JP H0812858A JP 14584294 A JP14584294 A JP 14584294A JP 14584294 A JP14584294 A JP 14584294A JP H0812858 A JPH0812858 A JP H0812858A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- resin composition
- prepreg
- curing agent
- phosphorus
- 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.)
- Withdrawn
Links
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
Landscapes
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はエポキシ樹脂組成物、こ
のエポキシ樹脂組成物を用いたプリプレグ、及びこのプ
リプレグを用いた積層板に関し、この積層板はコンピュ
ータ、電子機器等のプリント配線板に有用なものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition, a prepreg using the epoxy resin composition, and a laminated board using the prepreg. The laminated board is useful as a printed wiring board for computers, electronic devices and the like. It is something.
【０００２】[0002]
【従来の技術】プリント配線板に有用な難燃性を有する
エポキシ樹脂積層板の材料として用いられるエポキシ樹
脂組成物は、樹脂として臭素化エポキシ樹脂を、硬化剤
として、ジシアンジアミド、又は、その誘導体を、硬化
促進剤としてイミダゾール類を含有したものが知られて
いる。近年の高密度化に伴い、高耐熱性、及び銅マイブ
レーションの生じ難い積層板の要求が高まっている。し
かし、イミダゾール類を含有したエポキシ樹脂組成物で
得られた積層板は、吸湿後の耐熱性及びオーブン耐熱性
や耐銅マイブレーション特性が充分に満足する水準に至
っていないため、耐熱性、耐銅マイブレーション特性の
向上が求められている。2. Description of the Related Art An epoxy resin composition used as a material for a flame-retardant epoxy resin laminate useful for a printed wiring board comprises a brominated epoxy resin as a resin and dicyandiamide or a derivative thereof as a curing agent. Those containing imidazoles as curing accelerators are known. With the recent increase in density, there has been an increasing demand for a laminated plate having high heat resistance and in which copper migration is unlikely to occur. However, the laminate obtained by the epoxy resin composition containing the imidazole, the heat resistance after moisture absorption and the oven heat resistance and the resistance to copper migration are not yet sufficiently satisfied, so that the heat resistance and the copper resistance Improvement of the migration characteristics is required.
【０００３】[0003]
【発明が解決しようとする課題】本発明は上記の事実に
鑑みてなされたもので、その目的とするところは、吸湿
後の耐熱性やオーブン耐熱性に優れ、及び、銅マイブレ
ーションの生じ難い、難燃性を有する積層板、並びにこ
の積層板が得られるエポキシ樹脂組成物、及び、プリプ
レグを提供することにある。SUMMARY OF THE INVENTION The present invention has been made in view of the above facts, and an object thereof is to have excellent heat resistance after moisture absorption and oven heat resistance, and to prevent copper migration from occurring. Another object of the present invention is to provide a flame retardant laminate, an epoxy resin composition from which the laminate can be obtained, and a prepreg.
【０００４】[0004]
【課題を解決するための手段】本発明の請求項１に係る
エポキシ樹脂組成物は、臭素含有量が１５〜３０重量
％である臭素化エポキシ樹脂を５０重量％以上含むエポ
キシ樹脂、アミン硬化剤、及び、リン含有化合物を
含有することを特徴とする。The epoxy resin composition according to claim 1 of the present invention comprises an epoxy resin and an amine curing agent containing 50% by weight or more of a brominated epoxy resin having a bromine content of 15 to 30% by weight. , And a phosphorus-containing compound.
【０００５】本発明の請求項２に係るエポキシ樹脂組成
物は、請求項１記載のエポキシ樹脂組成物において、上
記エポキシ樹脂と、上記アミン硬化剤及びリン含有化合
物の少なくとも１種以上とを混合後に、加熱したことを
特徴とする。An epoxy resin composition according to a second aspect of the present invention is the epoxy resin composition according to the first aspect, after mixing the epoxy resin with at least one of the amine curing agent and the phosphorus-containing compound. , Characterized by being heated.
【０００６】本発明の請求項３に係るエポキシ樹脂組成
物は、請求項２記載のエポキシ樹脂組成物において、上
記加熱が温度６０〜１２０℃、温度６０℃以上が時間３
０〜１５０分の範囲であることを特徴とする。An epoxy resin composition according to a third aspect of the present invention is the epoxy resin composition according to the second aspect, wherein the heating is performed at a temperature of 60 to 120 ° C., and the temperature of 60 ° C. or higher is time 3
It is characterized by being in the range of 0 to 150 minutes.
【０００７】本発明の請求項４に係るエポキシ樹脂組成
物は、請求項１乃至請求項３いずれか記載のエポキシ樹
脂組成物において、上記リン含有化合物として、トリフ
ェニルホスフィン、ジフェニルクレジルホスフィン、ト
リクレジルホスフィン、亜リン酸トリフェニル、亜リン
酸ジフェニルのうち少なくとも１種以上を含有すること
を特徴とする。An epoxy resin composition according to a fourth aspect of the present invention is the epoxy resin composition according to any one of the first to third aspects, wherein the phosphorus-containing compound is triphenylphosphine, diphenylcresylphosphine or triphenylphosphine. It is characterized by containing at least one or more of cresylphosphine, triphenyl phosphite, and diphenyl phosphite.
【０００８】本発明の請求項５に係るエポキシ樹脂組成
物は、請求項１乃至請求項４いずれか記載のエポキシ樹
脂組成物において、上記臭素化エポキシ樹脂が下記
〔１〕の構造式を有するテトラブロムビスフェノールＡ
型エポキシ樹脂であることを特徴とする。An epoxy resin composition according to claim 5 of the present invention is the epoxy resin composition according to any one of claims 1 to 4, wherein the brominated epoxy resin has the following structural formula [1]: Brombisphenol A
Type epoxy resin.
【０００９】[0009]
【化２】 Embedded image
【００１０】本発明の請求項６に係るエポキシ樹脂組成
物は、請求項１乃至請求項５いずれか記載のエポキシ樹
脂組成物において、上記アミン硬化剤がジシアンジアミ
ド、又はジシアンジアミドの誘導体のうち少なくとも１
種以上を含有することを特徴とする。An epoxy resin composition according to a sixth aspect of the present invention is the epoxy resin composition according to any one of the first to fifth aspects, wherein the amine curing agent is at least one of dicyandiamide or a dicyandiamide derivative.
It is characterized by containing at least one species.
【００１１】本発明の請求項７に係るプリプレグは、請
求項１乃至請求項６いずれか記載のエポキシ樹脂組成物
を用い、このエポキシ樹脂組成物を基材に含浸し、半硬
化した状態にあることを特徴とする。A prepreg according to claim 7 of the present invention uses the epoxy resin composition according to any one of claims 1 to 6, and a base material is impregnated with the epoxy resin composition and is in a semi-cured state. It is characterized by
【００１２】本発明の請求項８に係る積層板は、請求項
７記載のプリプレグを用い、このプリプレグを加熱し、
エポキシ樹脂が完全に硬化した状態にあることを特徴と
する。A laminated board according to claim 8 of the present invention uses the prepreg according to claim 7, and heats the prepreg.
It is characterized in that the epoxy resin is in a completely cured state.
【００１３】以下、本発明を詳細に説明する。本発明の
エポキシ樹脂組成物を構成するエポキシ樹脂として、臭
素含有量が１５〜３０重量％である臭素化エポキシ樹脂
を５０重量％以上含有する。上記臭素化エポキシ樹脂が
５０重量％以上含くむと、得られる積層板に難燃性が付
与される。上記臭素化エポキシ樹脂としては、例えば、
テトラブロムビスフェノールＡ型エポキシ樹脂、ブロム
化フェノールノボラック型エポキシ樹脂、テトラブロム
ビスフェノールＡ変性多官能型エポキシ樹脂等が挙げら
れ、積層板に要求されるガラス転移温度（Ｔｇ）等によ
り適宜選択される。なかでも、前記〔１〕の構造式を有
するテトラブロムビスフェノールＡ型エポキシ樹脂は、
ガラス転移温度（Ｔｇ）１３０〜１５０℃の積層板の作
製に際し、工業的に適している。上記エポキシ樹脂とし
ては、上記臭素化エポキシ樹脂と共に、ビスフェノール
Ａ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、ビスフェノ
ールＡノボラック型エポキシ樹脂、多官能型エポキシ樹
脂、ナフトール型エポキシ樹脂等のエポキシ樹脂を１種
又はそれ以上と併用してもよい。Hereinafter, the present invention will be described in detail. As the epoxy resin constituting the epoxy resin composition of the present invention, 50% by weight or more of a brominated epoxy resin having a bromine content of 15 to 30% by weight is contained. When the brominated epoxy resin is contained in an amount of 50% by weight or more, flame retardancy is imparted to the obtained laminate. The brominated epoxy resin, for example,
Tetrabromobisphenol A type epoxy resin, brominated phenol novolac type epoxy resin, tetrabromobisphenol A modified polyfunctional epoxy resin and the like can be mentioned, which are appropriately selected depending on the glass transition temperature (Tg) required for the laminate. Among them, the tetrabromobisphenol A type epoxy resin having the structural formula [1] is
It is industrially suitable for producing a laminate having a glass transition temperature (Tg) of 130 to 150 ° C. Examples of the epoxy resin include bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, polyfunctional epoxy resin, naphthol type epoxy resin together with the brominated epoxy resin. You may use together an epoxy resin with 1 type (s) or more.
【００１４】本発明のエポキシ樹脂組成物は、上記エポ
キシ樹脂と共に、アミン硬化剤、及び、リン含有化合物
をを含有する。上記アミン硬化剤としては、ジシアンジ
アミド、芳香族ジアミン等のジシアンジアミドの誘導体
等が挙げられる。上記リン含有化合物は硬化促進剤とし
て働くもので、例えば、トリフェニルホスフィン、ジフ
ェニルクレジルホスフィン、トリクレジルホスフィン、
亜リン酸トリフェニル、亜リン酸ジフェニル等が挙げら
れる。上記リン含有化合物を硬化促進剤として用いる
と、得られる積層板の吸湿による劣化を防ぐことがで
き、吸湿後の耐熱性を良好にし、銅マイブレーションの
発生を抑えることができる。上記リン含有化合物の含有
量は限定はしないが、０．２〜１．５ｐｈｒが適する。The epoxy resin composition of the present invention contains an amine curing agent and a phosphorus-containing compound in addition to the above epoxy resin. Examples of the amine curing agent include dicyandiamide, dicyandiamide derivatives such as aromatic diamines, and the like. The phosphorus-containing compound functions as a curing accelerator, and examples thereof include triphenylphosphine, diphenylcresylphosphine, tricresylphosphine,
Examples thereof include triphenyl phosphite and diphenyl phosphite. When the above-mentioned phosphorus-containing compound is used as a curing accelerator, deterioration of the resulting laminate due to moisture absorption can be prevented, heat resistance after moisture absorption can be improved, and copper migration can be suppressed. The content of the phosphorus-containing compound is not limited, but 0.2 to 1.5 phr is suitable.
【００１５】本発明のエポキシ樹脂組成物においては、
上記エポキシ樹脂と、上記アミン硬化剤及びリン含有化
合物の少なくとも１種以上とを混合後に、加熱すること
が好ましい。この加熱により、エポキシ樹脂と硬化剤、
又は、リン含有化合物が均一に混合され、得られる積層
板の耐熱性が良好となる。この加熱条件としては、限定
はしないが、温度６０〜１２０℃、温度６０℃以上が時
間３０〜１５０分の範囲が望ましい。In the epoxy resin composition of the present invention,
It is preferable to heat after mixing the epoxy resin with at least one of the amine curing agent and the phosphorus-containing compound. By this heating, epoxy resin and curing agent,
Alternatively, the phosphorus-containing compound is uniformly mixed, and the heat resistance of the resulting laminate becomes good. The heating condition is not limited, but a temperature of 60 to 120 ° C., a temperature of 60 ° C. or higher, and a time of 30 to 150 minutes are desirable.
【００１６】上述の如くして、本発明のエポキシ樹脂組
成物が得られる。本発明のプリプレグは、上記エポキシ
樹脂組成物を基材に含浸し、半硬化して得られる。上記
基材としては、特に限定するものではないが、ガラス繊
維などの無機材料の方が耐熱性などに優れて好ましい。As described above, the epoxy resin composition of the present invention is obtained. The prepreg of the present invention is obtained by impregnating a base material with the epoxy resin composition and semi-curing it. The base material is not particularly limited, but an inorganic material such as glass fiber is preferable because it is superior in heat resistance.
【００１７】上記プリプレグを１枚又は複数枚重ね、必
要により、外側に銅箔等の金属箔を配し、加熱し、エポ
キシ樹脂を完全に硬化させると、本発明の積層板が得ら
れる。積層板は樹脂が硬化した絶縁層が単層の積層板に
限らず、回路板を内層材とした多層の積層板でもよい。
上記内層材の樹脂は限定しないが、上記エポキシ樹脂組
成物を用いて作製した回路板が、耐熱性、耐銅マイブレ
ーション特性がより向上するので、好ましい。この回路
板を内層材とする場合は、密着性を良好とするため、プ
リント配線板の表面に化学処理を施すとよい。この化学
処理としては、例えば、ブラックオキサイド処理やブラ
ウンオキサイド処理等が挙げられる。A laminate of the present invention is obtained by stacking one or a plurality of the above prepregs and, if necessary, disposing a metal foil such as a copper foil on the outside and heating the epoxy resin to completely cure the epoxy resin. The laminated board is not limited to a laminated board in which the insulating layer in which the resin is cured is a single layer, and may be a laminated board in which a circuit board is an inner layer material.
The resin of the inner layer material is not limited, but a circuit board produced using the epoxy resin composition is preferable because the heat resistance and the resistance to copper migration are further improved. When this circuit board is used as the inner layer material, the surface of the printed wiring board may be chemically treated to improve the adhesion. Examples of this chemical treatment include black oxide treatment and brown oxide treatment.
【００１８】[0018]
実施例１ エポキシ樹脂として、臭素含有量が２１重量％であるテ
トラブロムビスフェノールＡ型エポキシ樹脂（エポキシ
当量５００、ｍ／ｎ＝０．７０）を８０重量部（以下部
と記す）、クレゾールノボラック型エポキシ樹脂（エポ
キシ当量２１０）を２０部、アミン硬化剤としてジシア
ンジアミドを２．５部、リン含有化合物としてトリフェ
ニルホスフィンを０．７部配合し、攪拌してエポキシ樹
脂組成物Ａを作製した。Example 1 As an epoxy resin, 80 parts by weight of a tetrabromobisphenol A type epoxy resin having a bromine content of 21% by weight (epoxy equivalent: 500, m / n = 0.70) (hereinafter referred to as "part"), a cresol novolac type 20 parts of an epoxy resin (epoxy equivalent 210), 2.5 parts of dicyandiamide as an amine curing agent, and 0.7 parts of triphenylphosphine as a phosphorus-containing compound were mixed and stirred to prepare an epoxy resin composition A.
【００１９】基材として厚さ０．１８ｍｍのガラス布
（旭シュエーベル株式会社製、品名７６２８）を用い、
この基材に上記エポキシ樹脂組成物Ａを含浸し、樹脂が
半硬化したプリプレグＡを得た。このプリプレグＡのエ
ポキシ樹脂組成物の含有量は４５重量％であった。As a base material, a glass cloth having a thickness of 0.18 mm (product name 7628 manufactured by Asahi Schwebel Co., Ltd.) was used.
The epoxy resin composition A was impregnated into this base material to obtain a prepreg A in which the resin was semi-cured. The content of the epoxy resin composition of this prepreg A was 45% by weight.
【００２０】次に上記プリプレグＡを８枚重ね、１８μ
ｍの銅箔を両側に配し、温度１７０℃、圧力３０ｋｇ／
ｃｍ2 で９０分、加熱加圧して、樹脂を完全に硬化させ
て、厚さ１．６ｍｍの積層板を得た。Next, 8 sheets of the above prepreg A were stacked and
m copper foil is placed on both sides, temperature 170 ℃, pressure 30kg /
The resin was completely cured by heating and pressurizing at 90 cm 2 for 90 minutes to obtain a laminated plate having a thickness of 1.6 mm.
【００２１】実施例２ エポキシ樹脂として、実施例１と同様のテトラブロムビ
スフェノールＡ型エポキシ樹脂（エポキシ当量５００）
を８０部、クレゾールノボラック型エポキシ樹脂（エポ
キシ当量２１０）を２０部、アミン硬化剤として芳香族
アミン（アミン価＝６３）を１６．０部、リン含有化合
物としてトリフェニルホスフィンを０．６部配合し、攪
拌してエポキシ樹脂組成物Ｂを作製した。Example 2 As an epoxy resin, the same tetrabromobisphenol A type epoxy resin as in Example 1 (epoxy equivalent 500)
80 parts, cresol novolac type epoxy resin (epoxy equivalent 210) 20 parts, aromatic amine (amine value = 63) 16.0 parts as amine curing agent, triphenylphosphine 0.6 parts as phosphorus-containing compound Then, the mixture was stirred to prepare an epoxy resin composition B.
【００２２】基材として厚さ０．１８ｍｍのガラス布
（旭シュエーベル株式会社製、品名７６２８）を用い、
この基材に上記エポキシ樹脂組成物Ｂを含浸し、樹脂が
半硬化したプリプレグＢを得た。このプリプレグＢのエ
ポキシ樹脂組成物の含有量は４５重量％であった。次に
実施例１と同様にして樹脂を完全に硬化させて、厚さ
１．６ｍｍの積層板を得た。A glass cloth (made by Asahi Schwabel Co., Ltd., product name 7628) having a thickness of 0.18 mm was used as a substrate,
This base material was impregnated with the epoxy resin composition B to obtain a prepreg B in which the resin was semi-cured. The content of the epoxy resin composition in this prepreg B was 45% by weight. Next, the resin was completely cured in the same manner as in Example 1 to obtain a laminated plate having a thickness of 1.6 mm.
【００２３】実施例３ エポキシ樹脂として、実施例１と同様のテトラブロムビ
スフェノールＡ型エポキシ樹脂（エポキシ当量５００）
を１００部、アミン硬化剤としてジシアンジアミドを
１．２部、芳香族アミン（アミン価＝６３）を５．０
部、リン含有化合物としてトリフェニルホスフィンを
０．８部配合し、攪拌してエポキシ樹脂組成物Ｃを作製
した。Example 3 As an epoxy resin, the same tetrabromobisphenol A type epoxy resin as in Example 1 (epoxy equivalent 500)
100 parts, 1.2 parts of dicyandiamide as an amine curing agent, and 5.0 parts of an aromatic amine (amine value = 63).
Parts and 0.8 parts of triphenylphosphine as a phosphorus-containing compound were mixed and stirred to prepare an epoxy resin composition C.
【００２４】基材として厚さ０．１８ｍｍのガラス布
（旭シュエーベル株式会社製、品名７６２８）を用い、
この基材に上記エポキシ樹脂組成物Ｃを含浸し、樹脂が
半硬化したプリプレグＣを得た。このプリプレグＣのエ
ポキシ樹脂組成物の含有量は４５重量％であった。次に
実施例１と同様にして樹脂を完全に硬化させて、厚さ
１．６ｍｍの積層板を得た。As the base material, a glass cloth having a thickness of 0.18 mm (product name 7628 manufactured by Asahi Schwebel Co., Ltd.) was used.
This base material was impregnated with the epoxy resin composition C to obtain a prepreg C in which the resin was semi-cured. The content of the epoxy resin composition of this prepreg C was 45% by weight. Next, the resin was completely cured in the same manner as in Example 1 to obtain a laminated plate having a thickness of 1.6 mm.
【００２５】実施例４ エポキシ樹脂として、実施例１と同様のテトラブロムビ
スフェノールＡ型エポキシ樹脂（エポキシ当量５００）
を８０部、フェノールノボラック型エポキシ樹脂（エポ
キシ当量２００）を２０部、アミン硬化剤としてジシア
ンジアミドを２．６部、リン含有化合物としてトリフェ
ニルホスフィンを０．５部配合し、攪拌してエポキシ樹
脂組成物Ｄを作製した。Example 4 As an epoxy resin, the same tetrabromobisphenol A type epoxy resin as in Example 1 (epoxy equivalent 500)
80 parts, phenol novolac type epoxy resin (epoxy equivalent 200) 20 parts, dicyandiamide 2.6 parts as an amine curing agent, triphenylphosphine 0.5 parts as a phosphorus-containing compound, and stirred to prepare an epoxy resin composition. The thing D was produced.
【００２６】基材として厚さ０．１８ｍｍのガラス布
（旭シュエーベル株式会社製、品名７６２８）を用い、
この基材に上記エポキシ樹脂組成物Ｄを含浸し、樹脂が
半硬化したプリプレグＤを得た。このプリプレグＤのエ
ポキシ樹脂組成物の含有量は４５重量％であった。次に
実施例１と同様にして樹脂を完全に硬化させて、厚さ
１．６ｍｍの積層板を得た。As a base material, a glass cloth having a thickness of 0.18 mm (product name 7628 manufactured by Asahi Schebel Co., Ltd.) was used.
This base material was impregnated with the epoxy resin composition D to obtain a prepreg D in which the resin was semi-cured. The content of the epoxy resin composition in this prepreg D was 45% by weight. Next, the resin was completely cured in the same manner as in Example 1 to obtain a laminated plate having a thickness of 1.6 mm.
【００２７】実施例５ エポキシ樹脂として、実施例１と同様のテトラブロムビ
スフェノールＡ型エポキシ樹脂（エポキシ当量５００）
を８０部、フェノールノボラック型エポキシ樹脂（エポ
キシ当量２００）を２０部、アミン硬化剤として芳香族
アミン（アミン価＝６３）を１６．０部、リン含有化合
物としてトリフェニルホスフィンを０．２部配合し、攪
拌した後に、８０℃で１００分加熱してエポキシ樹脂組
成物Ｅを作製した。Example 5 As an epoxy resin, the same tetrabromobisphenol A type epoxy resin as in Example 1 (epoxy equivalent 500)
80 parts, 20 parts of a phenol novolac type epoxy resin (epoxy equivalent 200), 16.0 parts of an aromatic amine (amine value = 63) as an amine curing agent, and 0.2 parts of triphenylphosphine as a phosphorus-containing compound. Then, the mixture was stirred and then heated at 80 ° C. for 100 minutes to prepare an epoxy resin composition E.
【００２８】基材として厚さ０．１８ｍｍのガラス布
（旭シュエーベル株式会社製、品名７６２８）を用い、
この基材に上記エポキシ樹脂組成物Ｅを含浸し、樹脂が
半硬化したプリプレグＥを得た。このプリプレグＥのエ
ポキシ樹脂組成物の含有量は４５重量％であった。次に
実施例１と同様にして樹脂を完全に硬化させて、厚さ
１．６ｍｍの積層板を得た。As the base material, a glass cloth having a thickness of 0.18 mm (product name 7628 manufactured by Asahi Schwebel Co., Ltd.) was used.
This base material was impregnated with the epoxy resin composition E to obtain a prepreg E in which the resin was semi-cured. The content of the epoxy resin composition in this prepreg E was 45% by weight. Next, the resin was completely cured in the same manner as in Example 1 to obtain a laminated plate having a thickness of 1.6 mm.
【００２９】実施例６ エポキシ樹脂として、実施例１と同様のテトラブロムビ
スフェノールＡ型エポキシ樹脂（エポキシ当量５００）
を８０部、クレゾールノボラック型エポキシ樹脂（エポ
キシ当量２１０）を２０部、アミン硬化剤としてジシア
ンジアミドを２．５部、リン含有化合物としてトリフェ
ニルホスフィンを０．３部配合し、攪拌した後に、９０
℃で８０分加熱してエポキシ樹脂組成物Ｆを作製した。Example 6 As an epoxy resin, the same tetrabromobisphenol A type epoxy resin as in Example 1 (epoxy equivalent 500)
80 parts, 20 parts of a cresol novolac type epoxy resin (epoxy equivalent 210), 2.5 parts of dicyandiamide as an amine curing agent, and 0.3 parts of triphenylphosphine as a phosphorus-containing compound were mixed, and after stirring, 90
An epoxy resin composition F was prepared by heating at 80 ° C. for 80 minutes.
【００３０】基材として厚さ０．１８ｍｍのガラス布
（旭シュエーベル株式会社製、品名７６２８）を用い、
この基材に上記エポキシ樹脂組成物Ｆを含浸し、樹脂が
半硬化したプリプレグＦを得た。このプリプレグＦのエ
ポキシ樹脂組成物の含有量は４５重量％であった。次に
実施例１と同様にして樹脂を完全に硬化させて、厚さ
１．６ｍｍの積層板を得た。As a base material, a glass cloth having a thickness of 0.18 mm (product name 7628 manufactured by Asahi Schebel Co., Ltd.) was used.
This base material was impregnated with the epoxy resin composition F to obtain a prepreg F in which the resin was semi-cured. The content of the epoxy resin composition in this prepreg F was 45% by weight. Next, the resin was completely cured in the same manner as in Example 1 to obtain a laminated plate having a thickness of 1.6 mm.
【００３１】比較例１ エポキシ樹脂として、実施例１と同様のテトラブロムビ
スフェノールＡ型エポキシ樹脂（エポキシ当量５００）
を８０部、フェノールノボラック型エポキシ樹脂（エポ
キシ当量２００）を２０部、アミン硬化剤としてジシア
ンジアミドを２．６部、硬化促進剤として２エチル４メ
チルイミダゾール（２Ｅ４ＭＺと記す）を０．１部配合
し、攪拌した後に、８０℃で１００分加熱してエポキシ
樹脂組成物Ｇを作製した。Comparative Example 1 As an epoxy resin, the same tetrabromobisphenol A type epoxy resin as in Example 1 (epoxy equivalent 500)
80 parts, 20 parts of a phenol novolac type epoxy resin (epoxy equivalent of 200), 2.6 parts of dicyandiamide as an amine curing agent, and 0.1 parts of 2 ethyl 4 methyl imidazole (denoted as 2E4MZ) as a curing accelerator. After stirring, it was heated at 80 ° C. for 100 minutes to prepare an epoxy resin composition G.
【００３２】基材として厚さ０．１８ｍｍのガラス布
（旭シュエーベル株式会社製、品名７６２８）を用い、
この基材に上記エポキシ樹脂組成物Ｇを含浸し、樹脂が
半硬化したプリプレグＧを得た。このプリプレグＧのエ
ポキシ樹脂組成物の含有量は４５重量％であった。次に
実施例１と同様にして樹脂を完全に硬化させて、厚さ
１．６ｍｍの積層板を得た。As a base material, a glass cloth having a thickness of 0.18 mm (product name 7628 manufactured by Asahi Schwebel Co., Ltd.) was used.
This base material was impregnated with the epoxy resin composition G to obtain a prepreg G in which the resin was semi-cured. The content of the epoxy resin composition in this prepreg G was 45% by weight. Next, the resin was completely cured in the same manner as in Example 1 to obtain a laminated plate having a thickness of 1.6 mm.
【００３３】比較例２ エポキシ樹脂として、実施例１と同様のテトラブロムビ
スフェノールＡ型エポキシ樹脂（エポキシ当量５００）
を８０部、クレゾールノボラック型エポキシ樹脂（エポ
キシ当量２１０）を２０部、アミン硬化剤として芳香族
アミン（アミン価＝６３）を１６．０部、硬化促進剤と
して２Ｅ４ＭＺを０．１部配合し、攪拌してエポキシ樹
脂組成物Ｈを作製した。Comparative Example 2 As an epoxy resin, the same tetrabromobisphenol A type epoxy resin as in Example 1 (epoxy equivalent 500)
80 parts, 20 parts of a cresol novolac type epoxy resin (epoxy equivalent 210), 16.0 parts of an aromatic amine (amine value = 63) as an amine curing agent, and 0.1 parts of 2E4MZ as a curing accelerator, An epoxy resin composition H was prepared by stirring.
【００３４】基材として厚さ０．１８ｍｍのガラス布
（旭シュエーベル株式会社製、品名７６２８）を用い、
この基材に上記エポキシ樹脂組成物Ｈを含浸し、樹脂が
半硬化したプリプレグＨを得た。このプリプレグＨのエ
ポキシ樹脂組成物の含有量は４５重量％であった。次に
実施例１と同様にして樹脂を完全に硬化させて、厚さ
１．６ｍｍの積層板を得た。As a base material, a glass cloth having a thickness of 0.18 mm (product name 7628 manufactured by Asahi Schebel Co., Ltd.) was used.
This epoxy resin composition H was impregnated into this base material to obtain a prepreg H in which the resin was semi-cured. The content of the epoxy resin composition in this prepreg H was 45% by weight. Next, the resin was completely cured in the same manner as in Example 1 to obtain a laminated plate having a thickness of 1.6 mm.
【００３５】[0035]
【表１】 [Table 1]
【００３６】実施例７ エポキシ樹脂として、臭素含有量が２０重量％であるテ
トラブロムビスフェノールＡ変性３官能型エポキシ樹脂
（エポキシ当量４００）を８５部、ビスフェノールＡ型
エポキシ樹脂（エポキシ当量１８０）を１５部、アミン
硬化剤としてジシアンジアミドを２．２部、リン含有化
合物としてトリフェニルホスフィンを０．５部配合し、
攪拌してエポキシ樹脂組成物Ｊを作製した。Example 7 As an epoxy resin, 85 parts of tetrabromobisphenol A-modified trifunctional epoxy resin (epoxy equivalent 400) having a bromine content of 20% by weight, and 15 parts of bisphenol A type epoxy resin (epoxy equivalent 180) were used. Parts, 2.2 parts of dicyandiamide as an amine curing agent, and 0.5 parts of triphenylphosphine as a phosphorus-containing compound,
The epoxy resin composition J was produced by stirring.
【００３７】基材として厚さ０．１８ｍｍのガラス布
（旭シュエーベル株式会社製、品名７６２８）を用い、
この基材に上記エポキシ樹脂組成物Ｊを含浸し、樹脂が
半硬化したプリプレグＪを得た。このプリプレグＪのエ
ポキシ樹脂組成物の含有量は４５重量％であった。次に
実施例１と同様にして樹脂を完全に硬化させて、厚さ
１．６ｍｍの積層板を得た。As a base material, a glass cloth having a thickness of 0.18 mm (product name 7628 manufactured by Asahi Schwabel Co., Ltd.) was used.
This base material was impregnated with the epoxy resin composition J to obtain a prepreg J in which the resin was semi-cured. The content of the epoxy resin composition of this prepreg J was 45% by weight. Next, the resin was completely cured in the same manner as in Example 1 to obtain a laminated plate having a thickness of 1.6 mm.
【００３８】比較例３ エポキシ樹脂として、実施例７と同様のテトラブロムビ
スフェノールＡ変性３官能型エポキシ樹脂（エポキシ当
量４００）を８５部、ビスフェノールＡ型エポキシ樹脂
（エポキシ当量１８０）を１５部、アミン硬化剤として
ジシアンジアミドを２．２部、硬化促進剤として２メチ
ルイミダゾール（２ＭＺと記す）を０．０７部配合し、
攪拌してエポキシ樹脂組成物Ｋを作製した。Comparative Example 3 As the epoxy resin, 85 parts of the same tetrabromobisphenol A-modified trifunctional epoxy resin (epoxy equivalent of 400) as in Example 7, 15 parts of bisphenol A type epoxy resin (epoxy equivalent of 180), amine 2.2 parts of dicyandiamide as a curing agent and 0.07 part of 2-methylimidazole (referred to as 2MZ) as a curing accelerator were added,
An epoxy resin composition K was prepared by stirring.
【００３９】基材として厚さ０．１８ｍｍのガラス布
（旭シュエーベル株式会社製、品名７６２８）を用い、
この基材に上記エポキシ樹脂組成物Ｋを含浸し、樹脂が
半硬化したプリプレグＫを得た。このプリプレグＫのエ
ポキシ樹脂組成物の含有量は４５重量％であった。次に
実施例１と同様にして樹脂を完全に硬化させて、厚さ
１．６ｍｍの積層板を得た。As the base material, a glass cloth having a thickness of 0.18 mm (product name 7628 manufactured by Asahi Schwebel Co., Ltd.) was used.
This base material was impregnated with the epoxy resin composition K to obtain a prepreg K in which the resin was semi-cured. The content of the epoxy resin composition of this prepreg K was 45% by weight. Next, the resin was completely cured in the same manner as in Example 1 to obtain a laminated plate having a thickness of 1.6 mm.
【００４０】[0040]
【表２】 [Table 2]
【００４１】得られた実施例１〜７、及び比較例１〜３
の積層板の吸湿後の耐熱性、オーブン耐熱性、耐銅マイ
ブレーション特性、及び、難燃性を評価した。The obtained Examples 1 to 7 and Comparative Examples 1 to 3
The heat resistance after moisture absorption, the heat resistance of the oven, the resistance to copper migration, and the flame retardancy of the laminated sheet of No. 1 were evaluated.
【００４２】吸湿後の耐熱性の測定は、銅箔を除去した
サイズ５０×５０ｍｍの試料１０枚を、温度６０℃、相
対湿度９０％で１４４時間保管した後に、温度２６０℃
の半田に３０秒間浸漬した。半田浸漬した後に外観を目
視観察し、ふくれの発生した試料は不合格とした。不合
格の枚数を測定した。The heat resistance after moisture absorption was measured by storing 10 samples of 50 × 50 mm in size, from which the copper foil had been removed, at a temperature of 60 ° C. and a relative humidity of 90% for 144 hours, and then at a temperature of 260 ° C.
It was dipped in the solder for 30 seconds. After immersing the solder, the appearance was visually observed, and the sample in which blister was generated was rejected. The number of rejected sheets was measured.
【００４３】オーブン耐熱性はサイズ５０×５０ｍｍの
試料を、所定温度のオーブンに３０分間保持し、ふくれ
が発生しなかった温度で判定した。The oven heat resistance was evaluated by holding a sample of 50 × 50 mm in size in an oven at a predetermined temperature for 30 minutes and at the temperature at which no blistering occurred.
【００４４】耐銅マイブレーション特性は、積層板の片
面側に試験回路を形成した。試験回路として、回路長さ
１００ｍｍ、回路幅１５０μｍ、回路間隔１５０μｍの
櫛型の回路を形成した。測定は、温度１２５℃、相対湿
度８５％雰囲気中で電圧ＤＣ４８Ｖを連続して印加し、
２０００時間まで測定した。絶縁抵抗値が１０5 Ω以下
となるまでの時間で判定した。Regarding the resistance to copper migration, a test circuit was formed on one side of the laminate. As a test circuit, a comb-shaped circuit having a circuit length of 100 mm, a circuit width of 150 μm, and a circuit interval of 150 μm was formed. The measurement was performed by continuously applying a voltage of DC 48 V in an atmosphere of a temperature of 125 ° C. and a relative humidity of 85%.
It was measured up to 2000 hours. It was judged by the time until the insulation resistance value became 10 5 Ω or less.
【００４５】難燃性は、ＵＬの試験方法に基づいて１０
個の消炎時間を測定し、９４Ｖ−０（平均５秒以下、最
大１０秒以下）の基準で合否を判定した。Flame retardance is 10 based on UL test method.
The flame-out time of each piece was measured, and the pass / fail was judged on the basis of 94V-0 (average 5 seconds or less, maximum 10 seconds or less).
【００４６】結果は表３に示すとおり。実施例はいずれ
も難燃性は９４Ｖ−０が合格であり、吸湿後の耐熱性は
ふくれが発生せず、オーブン耐熱性、及び、耐銅マイブ
レーション特性は比較例より優れていた。The results are shown in Table 3. In each of the examples, the flame retardancy was 94V-0, the heat resistance after moisture absorption did not cause blistering, and the oven heat resistance and copper migration resistance were superior to those of the comparative examples.
【００４７】[0047]
【表３】 [Table 3]
【００４８】実施例８ 多層の積層板を次のようにして作製した。内層材とし
て、実施例１と同様のプリプレグＡを４枚重ね、３５μ
ｍの銅箔を両側に配し、温度１７０℃、圧力３０ｋｇ／
ｃｍ2 で６０分、加熱加圧して、樹脂を完全に硬化させ
て、厚さ０．８ｍｍの積層板を得た後に、所定の回路を
形成し内層用回路板を得た。この内層用回路板の表面は
ブラックオキサイド処理を施した。Example 8 A multi-layer laminated plate was prepared as follows. As the inner layer material, 4 sheets of the same prepreg A as in Example 1 were stacked and
m copper foil is placed on both sides, temperature 170 ℃, pressure 30kg /
The resin was completely cured by heating and pressing at 60 cm 2 for 60 minutes to obtain a laminated board having a thickness of 0.8 mm, and then a predetermined circuit was formed to obtain an inner layer circuit board. The surface of this inner layer circuit board was subjected to black oxide treatment.
【００４９】プリプレグａとして、実施例１と同様のエ
ポキシ樹脂組成物Ａを、厚さ０．１ｍｍのガラス布（旭
シュエーベル株式会社製、品名２１６）に含浸し、樹脂
が半硬化させた。このプリプレグａのエポキシ樹脂組成
物の含有量は５５重量％であった。As the prepreg a, the same epoxy resin composition A as in Example 1 was impregnated into a glass cloth having a thickness of 0.1 mm (manufactured by Asahi Schwebel Co., Ltd., product name 216) to semi-cure the resin. The content of the epoxy resin composition in this prepreg a was 55% by weight.
【００５０】上記内層材の上下にこのプリプレグａを３
枚づつ重ね、最外層に１８μｍの銅箔を配し、温度１７
０℃、圧力３０ｋｇ／ｃｍ2 で９０分、加熱加圧して、
樹脂を完全に硬化させて、４層の積層板を得た。Three prepregs a are provided above and below the inner layer material.
Stack the sheets one by one, place 18 μm copper foil on the outermost layer, and
Heat and pressurize at 0 ° C and pressure of 30 kg / cm 2 for 90 minutes,
The resin was completely cured to give a 4-layer laminate.
【００５１】実施例９ 実施例８のプリプレグＡに代わり実施例２に用いたプリ
プレグＢを、且つ、実施例８のエポキシ樹脂組成物Ａに
代わり実施例２に用いたエポキシ樹脂組成物Ｂを用いた
以外は実施例８と同様にして、４層の積層板を得た。Example 9 The prepreg B used in Example 2 was used instead of the prepreg A of Example 8, and the epoxy resin composition B used in Example 2 was used instead of the epoxy resin composition A of Example 8. A four-layer laminated plate was obtained in the same manner as in Example 8 except that the above was added.
【００５２】実施例１０ 実施例８のプリプレグＡに代わり実施例３に用いたプリ
プレグＣを、且つ、実施例８のエポキシ樹脂組成物Ａに
代わり実施例３に用いたエポキシ樹脂組成物Ｃを用いた
以外は実施例８と同様にして、４層の積層板を得た。Example 10 The prepreg C used in Example 3 was used instead of the prepreg A of Example 8, and the epoxy resin composition C used in Example 3 was used instead of the epoxy resin composition A of Example 8. A four-layer laminated plate was obtained in the same manner as in Example 8 except that the above was added.
【００５３】実施例１１ 実施例８のプリプレグＡに代わり実施例４に用いたプリ
プレグＤを、且つ、実施例８のエポキシ樹脂組成物Ａに
代わり実施例４に用いたエポキシ樹脂組成物Ｄを用いた
以外は実施例８と同様にして、４層の積層板を得た。Example 11 The prepreg D used in Example 4 was used in place of the prepreg A in Example 8, and the epoxy resin composition D used in Example 4 was used in place of the epoxy resin composition A in Example 8. A four-layer laminated plate was obtained in the same manner as in Example 8 except that the above was added.
【００５４】実施例１２ 実施例８のプリプレグＡに代わり実施例５に用いたプリ
プレグＥを、且つ、実施例８のエポキシ樹脂組成物Ａに
代わり実施例５に用いたエポキシ樹脂組成物Ｅを用いた
以外は実施例８と同様にして、４層の積層板を得た。Example 12 The prepreg E used in Example 5 was used instead of the prepreg A of Example 8, and the epoxy resin composition E used in Example 5 was used instead of the epoxy resin composition A of Example 8. A four-layer laminated plate was obtained in the same manner as in Example 8 except that the above was added.
【００５５】実施例１３ 実施例８のプリプレグＡに代わり実施例６に用いたプリ
プレグＦを、且つ、実施例８のエポキシ樹脂組成物Ａに
代わり実施例６に用いたエポキシ樹脂組成物Ｆを用いた
以外は実施例８と同様にして、４層の積層板を得た。Example 13 The prepreg F used in Example 6 was used instead of the prepreg A of Example 8, and the epoxy resin composition F used in Example 6 was used instead of the epoxy resin composition A of Example 8. A four-layer laminated plate was obtained in the same manner as in Example 8 except that the above was added.
【００５６】実施例１４ 実施例８のプリプレグＡに代わり実施例７に用いたプリ
プレグＪを、且つ、実施例８のエポキシ樹脂組成物Ｊに
代わり実施例７に用いたエポキシ樹脂組成物Ｊを用いた
以外は実施例８と同様にして、４層の積層板を得た。Example 14 The prepreg J used in Example 7 was used instead of the prepreg A of Example 8, and the epoxy resin composition J used in Example 7 was used instead of the epoxy resin composition J of Example 8. A four-layer laminated plate was obtained in the same manner as in Example 8 except that the above was added.
【００５７】比較例４ 実施例８のプリプレグＡに代わり比較例１に用いたプリ
プレグＧを、且つ、実施例８のエポキシ樹脂組成物Ａに
代わり比較例１に用いたエポキシ樹脂組成物Ｇを用いた
以外は実施例８と同様にして、４層の積層板を得た。Comparative Example 4 The prepreg G used in Comparative Example 1 was used instead of the prepreg A of Example 8, and the epoxy resin composition G used in Comparative Example 1 was used instead of the epoxy resin composition A of Example 8. A four-layer laminated plate was obtained in the same manner as in Example 8 except that the above was added.
【００５８】比較例５ 実施例８のプリプレグＡに代わり比較例２に用いたプリ
プレグＨを、且つ、実施例８のエポキシ樹脂組成物Ａに
代わり比較例２に用いたエポキシ樹脂組成物Ｈを用いた
以外は実施例８と同様にして、４層の積層板を得た。Comparative Example 5 The prepreg H used in Comparative Example 2 was used instead of the prepreg A of Example 8, and the epoxy resin composition H used in Comparative Example 2 was used instead of the epoxy resin composition A of Example 8. A four-layer laminated plate was obtained in the same manner as in Example 8 except that the above was added.
【００５９】比較例６ 実施例８のプリプレグＡに代わり比較例３に用いたプリ
プレグＫを、且つ、実施例８のエポキシ樹脂組成物Ａに
代わり比較例３に用いたエポキシ樹脂組成物Ｋを用いた
以外は実施例８と同様にして、４層の積層板を得た。Comparative Example 6 The prepreg K used in Comparative Example 3 was used instead of the prepreg A of Example 8, and the epoxy resin composition K used in Comparative Example 3 was used instead of the epoxy resin composition A of Example 8. A four-layer laminated plate was obtained in the same manner as in Example 8 except that the above was added.
【００６０】得られた実施例８〜１４、及び比較例３〜
６の４層の積層板の吸湿後の耐熱性、オーブン耐熱性、
耐銅マイブレーション特性、及び、難燃性を上述と同様
に評価した。The obtained Examples 8 to 14 and Comparative Examples 3 to
Heat resistance after moisture absorption of the four-layer laminate of No. 6, oven heat resistance,
The copper resistance to migration and flame retardancy were evaluated in the same manner as above.
【００６１】なお、吸湿後の耐熱性の測定は、最外層の
銅箔を除去したサイズ５０×５０ｍｍの試料１０枚を用
い、上述と同様の条件で評価した。上記耐銅マイブレー
ション特性は、４層の積層板の最外層の銅箔面の片方に
上述と同様の試験回路を形成した。上記難燃性の試料
は、内層材に回路が形成されていない個所で作製した。The heat resistance after moisture absorption was evaluated under the same conditions as above using 10 samples of 50 × 50 mm in size with the outermost copper foil removed. With respect to the above-mentioned copper migration resistance property, a test circuit similar to that described above was formed on one of the outermost copper foil surfaces of the four-layer laminate. The flame-retardant sample was prepared at a portion where no circuit was formed in the inner layer material.
【００６２】結果は表４に示すとおり。実施例はいずれ
も難燃性は９４Ｖ−０が合格であり、吸湿後の耐熱性は
ふくれが発生せず、オーブン耐熱性、及び、耐銅マイブ
レーション特性は比較例より優れていた。The results are shown in Table 4. In each of the examples, the flame retardancy was 94V-0, the heat resistance after moisture absorption did not cause blistering, and the oven heat resistance and copper migration resistance were superior to those of the comparative examples.
【００６３】[0063]
【表４】 [Table 4]
【００６４】[0064]
【発明の効果】本発明の請求項１乃至請求項６いずれか
記載のエポキシ樹脂組成物は、臭素化エポキシ樹脂を５
０重量％以上含むエポキシ樹脂、アミン硬化剤、及び、
リン含有化合物を含有するので、このエポキシ樹脂組成
物を用いると、難燃性を有すると共に、吸湿後の耐熱性
やオーブン耐熱性に優れ、銅マイブレーションの生じ難
い積層板が得られる。The epoxy resin composition according to any one of claims 1 to 6 of the present invention comprises a brominated epoxy resin 5
Epoxy resin containing 0% by weight or more, amine curing agent, and
Since this epoxy resin composition contains a phosphorus-containing compound, a laminate having flame retardancy, excellent heat resistance after moisture absorption and oven heat resistance, and resistant to copper migration is obtained.
【００６５】また、本発明の請求項２に係るエポキシ樹
脂組成物は、特に、エポキシ樹脂と、上記アミン硬化剤
及びリン含有化合物の少なくとも１種以上とを混合後
に、加熱するので、エポキシ樹脂と硬化剤、又は、リン
含有化合物が均一に混合され、得られる積層板の耐熱性
が良好となる。Further, the epoxy resin composition according to the second aspect of the present invention is particularly suitable because it is heated after mixing the epoxy resin with at least one of the amine curing agent and the phosphorus-containing compound. The curing agent or the phosphorus-containing compound is uniformly mixed, and the heat resistance of the obtained laminated plate becomes good.
【００６６】本発明の請求項７に係るプリプレグは、上
記エポキシ樹脂組成物を用いるので、吸湿後の耐熱性や
オーブン耐熱性に優れ、及び、銅マイブレーションの生
じ難い、難燃性を有する積層板を得ることができる。Since the prepreg according to claim 7 of the present invention uses the above-mentioned epoxy resin composition, it is excellent in heat resistance after moisture absorption and oven heat resistance, and is resistant to copper migration and is a flame-retardant laminate. The board can be obtained.
【００６７】本発明の請求項８に係る積層板は、上記プ
リプレグを用いるので、難燃性を有し、吸湿後の耐熱性
やオーブン耐熱性に優れ、及び、銅マイブレーションの
生じ難い。本発明の積層板は、特に、多層のプリント配
線板に有用である。Since the laminated plate according to claim 8 of the present invention uses the prepreg, it has flame retardancy, is excellent in heat resistance after moisture absorption and oven heat resistance, and is unlikely to cause copper migration. The laminated board of the present invention is particularly useful for a multilayer printed wiring board.
Claims (8)
素化エポキシ樹脂を５０重量％以上含むエポキシ樹脂、 アミン硬化剤、及び、 リン含有化合物を含有することを特徴とするエポキシ
樹脂組成物。1. An epoxy resin composition comprising an epoxy resin containing 50% by weight or more of a brominated epoxy resin having a bromine content of 15 to 30% by weight, an amine curing agent, and a phosphorus-containing compound. .
及びリン含有化合物の少なくとも１種以上とを混合後
に、加熱したことを特徴とする請求項１記載のエポキシ
樹脂組成物。2. The epoxy resin composition according to claim 1, wherein the epoxy resin and at least one of the amine curing agent and the phosphorus-containing compound are mixed and then heated.
℃、温度６０℃以上が時間３０〜１５０分の範囲である
ことを特徴とする請求項２記載のエポキシ樹脂組成物。3. The heating according to claim 2 is performed at a temperature of 60 to 120.
The epoxy resin composition according to claim 2, wherein the temperature of 60 ° C or higher is in the range of 30 to 150 minutes.
ルホスフィン、ジフェニルクレジルホスフィン、トリク
レジルホスフィン、亜リン酸トリフェニル、亜リン酸ジ
フェニルのうち少なくとも１種以上を含有することを特
徴とする請求項１乃至請求項３いずれか記載のエポキシ
樹脂組成物。4. The compound containing at least one of triphenylphosphine, diphenylcresylphosphine, tricresylphosphine, triphenylphosphite and diphenylphosphite as the phosphorus-containing compound. The epoxy resin composition according to any one of claims 1 to 3.
構造式を有するテトラブロムビスフェノールＡ型エポキ
シ樹脂であることを特徴とする請求項１乃至請求項４い
ずれか記載のエポキシ樹脂組成物。 【化１】 5. The epoxy resin composition according to any one of claims 1 to 4, wherein the brominated epoxy resin is a tetrabromobisphenol A type epoxy resin having the structural formula [1] below. Embedded image
又はジシアンジアミドの誘導体のうち少なくとも１種以
上を含有することを特徴とする請求項１乃至請求項５い
ずれか記載のエポキシ樹脂組成物。6. The amine curing agent is dicyandiamide,
Alternatively, the epoxy resin composition according to any one of claims 1 to 5, which contains at least one kind of dicyandiamide derivative.
ポキシ樹脂組成物を用い、このエポキシ樹脂組成物を基
材に含浸し、半硬化した状態にあることを特徴とするプ
リプレグ。7. A prepreg characterized by using the epoxy resin composition according to any one of claims 1 to 6 and impregnating a substrate with the epoxy resin composition, and in a semi-cured state.
プリプレグを加熱し、エポキシ樹脂が完全に硬化した状
態にあることを特徴とする積層板。8. A laminate comprising the prepreg according to claim 7, wherein the prepreg is heated to completely cure the epoxy resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14584294A JPH0812858A (en) | 1994-06-28 | 1994-06-28 | Epoxy resin composition, prepreg using the epoxy resin composition, and laminate board using the prepreg |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14584294A JPH0812858A (en) | 1994-06-28 | 1994-06-28 | Epoxy resin composition, prepreg using the epoxy resin composition, and laminate board using the prepreg |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0812858A true JPH0812858A (en) | 1996-01-16 |
Family
ID=15394370
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14584294A Withdrawn JPH0812858A (en) | 1994-06-28 | 1994-06-28 | Epoxy resin composition, prepreg using the epoxy resin composition, and laminate board using the prepreg |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0812858A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004108791A1 (en) * | 2003-06-03 | 2004-12-16 | Matsushita Electric Works, Ltd. | Resin composition for printed wiring board, prepreg, and laminate obtained with the same |
| WO2004110115A1 (en) * | 2003-06-02 | 2004-12-16 | Matsushita Electric Works, Ltd. | Prepreg for printed wiring board and copper-clad laminated board |
| KR100765898B1 (en) * | 2005-11-25 | 2007-10-10 | 마츠시다 덴코 가부시키가이샤 | Resin composition for printed wiring board, prepreg, and laminate obtained with the same |
| US20110132646A1 (en) * | 2009-06-12 | 2011-06-09 | Icl-Ip America Inc. | Flame retardant epoxy resin composition, prepreg and laminate thereof |
| JP2014516111A (en) * | 2011-06-09 | 2014-07-07 | ビーエーエスエフ ソシエタス・ヨーロピア | Production of cured epoxy resins with flame retardant phosphonates. |
| JP2021031523A (en) * | 2019-08-19 | 2021-03-01 | 日本化薬株式会社 | Curable resin composition and cured product of the same |
-
1994
- 1994-06-28 JP JP14584294A patent/JPH0812858A/en not_active Withdrawn
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004110115A1 (en) * | 2003-06-02 | 2004-12-16 | Matsushita Electric Works, Ltd. | Prepreg for printed wiring board and copper-clad laminated board |
| WO2004108791A1 (en) * | 2003-06-03 | 2004-12-16 | Matsushita Electric Works, Ltd. | Resin composition for printed wiring board, prepreg, and laminate obtained with the same |
| CN100424110C (en) * | 2003-06-03 | 2008-10-08 | 松下电工株式会社 | Resin composition for printed wiring board, prepreg, and laminate obtained with the same |
| EP1637554A4 (en) * | 2003-06-03 | 2011-08-24 | Panasonic Elec Works Co Ltd | Resin composition for printed wiring board, prepreg, and laminate obtained with the same |
| US8470938B2 (en) | 2003-06-03 | 2013-06-25 | Matsushita Electric Works, Ltd. | Resin composition for printed wiring board, prepreg, and laminate obtained with the same |
| KR100765898B1 (en) * | 2005-11-25 | 2007-10-10 | 마츠시다 덴코 가부시키가이샤 | Resin composition for printed wiring board, prepreg, and laminate obtained with the same |
| US20110132646A1 (en) * | 2009-06-12 | 2011-06-09 | Icl-Ip America Inc. | Flame retardant epoxy resin composition, prepreg and laminate thereof |
| JP2014516111A (en) * | 2011-06-09 | 2014-07-07 | ビーエーエスエフ ソシエタス・ヨーロピア | Production of cured epoxy resins with flame retardant phosphonates. |
| JP2021031523A (en) * | 2019-08-19 | 2021-03-01 | 日本化薬株式会社 | Curable resin composition and cured product of the same |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20010904 |