JPH09291148A - Production of modified polyphenylene oxide, epoxy resin composition containing modified polyphenylene oxioe produced by the process, prepreg made using the composition, and laminate made using the prepreg - Google Patents
Production of modified polyphenylene oxide, epoxy resin composition containing modified polyphenylene oxioe produced by the process, prepreg made using the composition, and laminate made using the prepregInfo
- Publication number
- JPH09291148A JPH09291148A JP8127566A JP12756696A JPH09291148A JP H09291148 A JPH09291148 A JP H09291148A JP 8127566 A JP8127566 A JP 8127566A JP 12756696 A JP12756696 A JP 12756696A JP H09291148 A JPH09291148 A JP H09291148A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- prepreg
- ppo
- polyphenylene oxide
- modified polyphenylene
- 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.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、変成ポリフェニレ
ンオキサイドの製法、この製法による変成ポリフェニレ
ンオキサイドを用いたエポキシ樹脂組成物、この組成物
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、半導体等の電子部品を搭載する回路板に加工
される積層板に有用なものである。TECHNICAL FIELD The present invention relates to a method for producing a modified polyphenylene oxide, an epoxy resin composition using the modified polyphenylene oxide produced by the method, a prepreg using the composition, and a laminated board using the prepreg. It is useful for a laminated board processed into a circuit board on which electronic components such as the above are mounted.
【０００２】[0002]
【従来の技術】エポキシ樹脂、エポキシ樹脂の硬化剤、
及びポリフェニレンオキサイド（以下、ＰＰＯと記す）
の硬化物がガラスクロスと一体となった積層板は、１９
７０年にはすでに知られている。この種のポリフェニレ
ンオキサイド−エポキシ樹脂系の熱硬化型樹脂の硬化物
から成る積層板は、優れた高周波特性、特に、誘電率、
誘電正接の特性を備えている点で、衛星通信波領域で使
用されるＸバンド（１０ＧＨｚ）領域に好適である。2. Description of the Related Art Epoxy resins, epoxy resin curing agents,
And polyphenylene oxide (hereinafter referred to as PPO)
The laminated plate in which the cured product of is integrated with the glass cloth is 19
It is already known in 70 years. A laminated plate made of a cured product of this type of polyphenylene oxide-epoxy resin-based thermosetting resin has excellent high frequency characteristics, particularly, a dielectric constant,
It is suitable for the X band (10 GHz) region used in the satellite communication wave region because it has the characteristic of dielectric loss tangent.
【０００３】ところが、高分子量のＰＰＯは、ガラス転
移温度が高いことに関連して溶融粘度が高ために、この
種のＰＰＯを含有したプリプレグを加熱加圧する成形加
工性が悪い。However, since high molecular weight PPO has a high melt viscosity associated with a high glass transition temperature, it has poor moldability in heating and pressing a prepreg containing this type of PPO.
【０００４】そこで、他の樹脂とのブレンドにより改善
する解決手段が模索されているが、ＰＰＯは相溶性が乏
しく、機械的強度に難点があり、この問題解決のために
相溶化剤として両者のポリマーのグラフト、またはブロ
ックの共重合体の使用が考えられる。これらの共重合体
は無変成のＰＰＯの末端に結合したフェノール性水酸基
を他のポリマー中の官能基と反応させることによって生
成される。これらの他のポリマーで変成したＰＰＯとし
ては、たとえば特公昭５３−１２５５７号公報によって
固有粘度０．６以下のＰＰＯとエピクロルヒドリンを触
媒の存在下で反応させることによって末端をエポキシ化
した変成ＰＰＯを製造する方法、特開平４−２６１４２
６号によって末端をエポキシ化した変成ＰＰＯにポリカ
ルボン酸を反応させることによって末端カルボン酸変成
ＰＰＯを製造する方法、特開平４−８０２３１号公報に
よって末端をエポキシ化した変成ＰＰＯにポリアミン化
合物を反応させることによって末端アミノ化変成ＰＰＯ
を製造する方法が知られている。Therefore, a solution to improve by blending with other resins is being sought, but PPO has poor compatibility and mechanical strength, and in order to solve this problem, PPO is used as a compatibilizer. The use of polymer grafts or block copolymers is contemplated. These copolymers are formed by reacting the terminal phenolic hydroxyl groups of unmodified PPO with functional groups in other polymers. As the PPO modified with these other polymers, for example, modified PPO whose terminal is epoxidized by reacting PPO having an intrinsic viscosity of 0.6 or less with epichlorohydrin in the presence of a catalyst according to JP-B-53-12557 is produced. Method, JP-A-4-26142
No. 6, a method for producing a terminal carboxylic acid-modified PPO by reacting a modified carboxylic acid having an epoxidized end with a polycarboxylic acid, and a modified PPO having an epoxidized terminal by reacting a polyamine compound according to JP-A-4-80231. Terminal aminated modified PPO
There is known a method for manufacturing.
【０００５】これらの製法で得られた変成ＰＰＯは、前
述の如く溶融粘度が高く、その結果積層板の銅箔のピー
リング強度が弱く、プリプレグの層間にメッキが染み込
む現象が起き、また樹脂の含浸性が悪いことに起因する
半田耐熱性が低い問題がある。The modified PPO obtained by these manufacturing methods has a high melt viscosity as described above, and as a result, the peeling strength of the copper foil of the laminated plate is weak, the phenomenon that the plating penetrates between the layers of the prepreg, and the impregnation of the resin occurs. There is a problem that solder heat resistance is low due to poor solderability.
【０００６】[0006]
【発明が解決しようとする課題】本発明は上記の事情に
鑑みてなされたもので、その目的とするところは、金属
箔の引き剥がし強度、半田耐熱性、メッキ染み込み性並
びに高周波特性の指標である誘電率、誘電正接特性に優
れた積層板の製造に有用なエポキシ樹脂組成物を構成す
る変成ポリフェニレンオキサイドの製法、変成ポリフェ
ニレンオキサイドを用いたエポキシ樹脂組成物、この組
成物を用いたプリプレグ、及びこのプリプレグを用いた
積層板を提供するものである。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to measure peeling strength of a metal foil, solder heat resistance, plating penetration, and high frequency characteristics. Certain dielectric constant, a method for producing a modified polyphenylene oxide constituting an epoxy resin composition useful for producing a laminated board having excellent dielectric loss tangent properties, an epoxy resin composition using the modified polyphenylene oxide, a prepreg using this composition, and A laminated board using this prepreg is provided.
【０００７】[0007]
【課題を解決するための手段】本発明の請求項１乃至請
求項３に係る変性ポリフェニレンオキサイドの製法は、
数平均分子量が１００００〜３００００の高分子量のポ
リフェニレンオキサイドをポリフェノール性化合物とラ
ジカル開始剤の存在下で再分配反応させて得られた数平
均分子量が１０００〜３０００のフェノール変性ポリフ
ェニレンオキサイド、及びエピクロルヒドリンとを反応
させるもので、末端にエポキシ基を導入した低分子量の
変成ポリフェニレンオキサイドが生成する。The method for producing a modified polyphenylene oxide according to claim 1 to claim 3 of the present invention comprises:
A phenol-modified polyphenylene oxide having a number average molecular weight of 1000 to 3000 obtained by redistribution reaction of a high molecular weight polyphenylene oxide having a number average molecular weight of 10,000 to 30,000 in the presence of a polyphenolic compound and a radical initiator, and epichlorohydrin. This is a reaction that produces a low molecular weight modified polyphenylene oxide having an epoxy group introduced at the terminal.
【０００８】本発明の請求項４に係るエポキシ樹脂組成
物は、エポキシ樹脂、請求項１乃至請求項３に係る製法
によって得られた変成ポリフェニレンオキサイド、及び
エポキシ樹脂の硬化剤を必須成分として含有し、金属箔
の引き剥がし強度、半田耐熱性、メッキ染み込み性並び
に高周波特性の指標である誘電率、誘電正接特性に優れ
た積層板の製造に有用なものである。An epoxy resin composition according to claim 4 of the present invention contains an epoxy resin, a modified polyphenylene oxide obtained by the production method according to claims 1 to 3, and a curing agent for the epoxy resin as essential components. It is useful for producing a laminated plate having excellent peeling strength of metal foil, solder heat resistance, plating penetration, and excellent dielectric constant and dielectric loss tangent characteristic of high frequency characteristics.
【０００９】本発明の請求項５に係るプリプレグは、請
求項４のエポキシ樹脂組成物を基材に含浸し、このエポ
キシ樹脂組成物中のエポキシ樹脂とエポキシ変成ポリフ
ェニレンオキサイドがエポキシ樹脂の硬化剤によりＢス
テージに半硬化したもので、金属箔の引き剥がし強度、
半田耐熱性、メッキ染み込み性並びに高周波特性の指標
である誘電率、誘電正接特性に優れた積層板の製造に有
用なものである。A prepreg according to claim 5 of the present invention comprises a base material impregnated with the epoxy resin composition according to claim 4, and the epoxy resin and the epoxy-modified polyphenylene oxide in the epoxy resin composition are treated with a curing agent for the epoxy resin. It is a semi-cured material on the B stage.
It is useful for manufacturing a laminated plate having excellent solder heat resistance, plating penetration, and high dielectric constant and dielectric loss tangent characteristic of high frequency characteristics.
【００１０】本発明の請求項６に係る積層板は、請求項
５のプリプレグを加熱加圧したもので、プリプレグ中の
半硬化したエポキシ樹脂の硬化が完結すると、エポキシ
樹脂の硬化物の架橋構造にポリフェニレンオキサイドが
関与し、その結果、金属箔の引き剥がし強度、半田耐熱
性、メッキ染み込み性並びに高周波特性の指標である誘
電率、誘電正接特性に優れたものである。A laminated plate according to claim 6 of the present invention is obtained by heating and pressing the prepreg according to claim 5, and when the curing of the semi-cured epoxy resin in the prepreg is completed, a crosslinked structure of the cured epoxy resin is obtained. Since polyphenylene oxide is involved in the above, as a result, it is excellent in peeling strength of metal foil, solder heat resistance, plating penetration, and excellent dielectric constant and dielectric loss tangent characteristic which are indicators of high frequency characteristics.
【００１１】以下、本発明の実施形態を詳述する。The embodiments of the present invention will be described in detail below.
【００１２】[0012]
【発明の実施の形態】本発明の製法によって生成される
変成ポリフェニレンオキサイドは、末端にエポキシ基が
導入された変成ＰＰＯである。この変成ＰＰＯは、エポ
キシ樹脂の硬化物の架橋構造に関与するもので、数平均
分子量が１００００乃至３００００の高分子ＰＰＯをフ
ェノール性化合物と高分子ＰＰＯのラジカル開始剤の存
在下で再分配反応させることによって末端にフェノール
性化合物のフェノール性水酸基を有する低分子のフェノ
ール変成ＰＰＯを原料とし、このフェノール変成ＰＰＯ
は数平均分子量が１０００〜３０００に制限される。す
なわち、フェノール変成ＰＰＯの数平均分子量が１００
０未満では積層板の耐熱性が低下し３０００を越える
と、基材に含浸したエポキシ樹脂のＢステージに変成し
た半硬化物の溶融粘度が増大し、その結果積層板の金属
箔の引き剥がし強度、半田耐熱性、メッキ染み込み性の
性能を阻害するからである。BEST MODE FOR CARRYING OUT THE INVENTION The modified polyphenylene oxide produced by the method of the present invention is a modified PPO having an epoxy group introduced at its terminal. This modified PPO is involved in the crosslinked structure of a cured product of an epoxy resin, and causes a redistribution reaction of polymer PPO having a number average molecular weight of 10,000 to 30,000 in the presence of a phenolic compound and a radical initiator of polymer PPO. As a result, a low-molecular-weight phenol-modified PPO having a phenolic hydroxyl group of a phenolic compound at its end is used as a raw material.
Has a number average molecular weight limited to 1000 to 3000. That is, the number average molecular weight of phenol-modified PPO is 100.
If it is less than 0, the heat resistance of the laminate decreases, and if it exceeds 3000, the melt viscosity of the semi-cured product of the epoxy resin impregnated in the base material transformed to the B stage increases, resulting in the peeling strength of the metal foil of the laminate. This is because it hinders the solder heat resistance and the performance of plating penetration.
【００１３】上記の高分子ＰＰＯとしては、代表的な一
例を示すとポリ（２，６−ジメチル−１，４フェニレン
オキサイド）を挙げることができる。このような高分子
ＰＰＯは、たとえばＵＳＰ４，０５９，５６８号の明細
書に開示された合成法により製造することができる。As a typical example of the above-mentioned polymer PPO, poly (2,6-dimethyl-1,4phenylene oxide) can be given. Such polymer PPO can be produced, for example, by the synthetic method disclosed in the specification of USP 4,059,568.
【００１４】この高分子ＰＰＯの再分配反応に用いられ
るフェノール性化合物としては、ポリフェノールのビス
フェノールＡ、フェノ−ルノボラック、クレゾールノボ
ラック等、フェノール性水酸基を分子内に２個以上有す
る多官能のフェノール類が好ましい。ラジカル開始剤と
しては、ジクミルパーオキサイド、ｔｅｒｔ−ブチルク
ミルパーオキサイド、ジ−ｔｅｒｔ−ブチルパーオキサ
イド、２・５−ジメチル−２・５−ジ−ｔｅｒｔ−ブチ
ルパーオキシヘキシン３、２・５−ジメチル−２・５−
ジ−ｔｅｒｔ−ブチルパーオキシヘキサン、α・α’−
ビス（ｔｅｒｔ−ブチルパーオキシ−ｍ−イソプロピ
ル）ベンゼン〔１・４（または１・３）−ビス（ｔｅｒ
ｔ−ブチルパーオキシイソプロピル）ベンゼンともい
う〕、ベンゾイルパーオキサイド（以下、ＢＰＯと記
す）などの過酸化物を挙げることができる。また、開始
剤として過酸化物ではないが、市販の開始剤である日本
油脂（株）製の商品名「ビスクミル」（１分半減温度３
３０℃）を使用することもできる。Examples of the phenolic compound used in the redistribution reaction of the polymer PPO include polyphenols such as bisphenol A, phenol novolac, and cresol novolac, which are polyfunctional phenols having two or more phenolic hydroxyl groups in the molecule. preferable. Examples of the radical initiator include dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide, 2.5-dimethyl-2,5-di-tert-butylperoxyhexyne 3, 2.5. -Dimethyl-2,5-
Di-tert-butylperoxyhexane, α · α′-
Bis (tert-butylperoxy-m-isopropyl) benzene [1.4 (or 1.3) -bis (ter
Also referred to as t-butylperoxyisopropyl) benzene], and benzoyl peroxide (hereinafter referred to as BPO). In addition, the initiator is not a peroxide, but is a commercially available initiator, trade name “Biscumyl” manufactured by NOF Corporation (1 min half-life temperature 3
30 ° C.) can also be used.
【００１５】ラジカル開始剤の存在下で数平均分子量が
１００００乃至３００００の高分子ＰＰＯとフェノール
性化合物をトルエン、クロロホルム等の溶媒中で反応さ
せると、先ず高分子ＰＰＯがラジカル化され、直鎖が切
断された低分子のＰＰＯが生成する再分配反応が進行
し、この活性化された低分子ＰＰＯとフェノール性化合
物とが反応して末端にフェノール性化合物のフェノール
性水酸基を有する低分子のフェノール変成ＰＰＯが生成
する。When a high molecular weight PPO having a number average molecular weight of 10,000 to 30,000 is reacted with a phenolic compound in a solvent such as toluene or chloroform in the presence of a radical initiator, the high molecular weight PPO is first radicalized to form a linear chain. A redistribution reaction that produces cleaved low molecular weight PPO proceeds, and the activated low molecular weight PPO reacts with a phenolic compound to cause a low molecular weight phenol modification having a phenolic hydroxyl group of the phenolic compound at the terminal. PPO is generated.
【００１６】なお、ベンゾイルパーオキサイドの量は、
ポリフェニレンエーテル１００重量部に対して３〜１０
重量部で、フェノール性化合物の量は３〜２０重量部が
適量である。すなわち、ベンゾイルパーオキサイドなら
びにフェノール性化合物の添加量が過剰になると、再分
配反応が過度に進行し低分子のポリフェニレンオキサイ
ドの数平均分子量が低下し、その結果前述の如く耐熱性
が低下する。また、少な過ぎると再分配反応が進行せず
数平均分子量の低下が起こらない。The amount of benzoyl peroxide is
3 to 10 relative to 100 parts by weight of polyphenylene ether
An appropriate amount of the phenolic compound is 3 to 20 parts by weight. That is, when the addition amount of benzoyl peroxide and the phenolic compound becomes excessive, the redistribution reaction proceeds excessively and the number average molecular weight of the low molecular weight polyphenylene oxide decreases, and as a result, the heat resistance decreases as described above. If it is too small, the redistribution reaction does not proceed and the number average molecular weight does not decrease.
【００１７】再分配反応はトルエン、ベンゼン、キシレ
ン等の芳香族炭化水素系溶媒中で８０〜１２０℃に１０
〜１００分加熱して行う。この再分配反応を通して、末
端にフェノール性化合物のフェノール性水酸基を有する
低分子のフェノール変成ＰＰＯが生成する。The redistribution reaction is carried out at 80 to 120 ° C. in an aromatic hydrocarbon solvent such as toluene, benzene or xylene at a temperature of 10 to 10.
Heat for ~ 100 minutes. Through this redistribution reaction, a low molecular weight phenol-modified PPO having a phenolic hydroxyl group of a phenolic compound at the terminal is produced.
【００１８】次に本発明の変性ポリフェニレンオキサイ
ドを生成する、低分子ＰＰＯから成るフェノール変成Ｐ
ＰＯとエピクロルヒドリンとの反応について説明する。Next, a phenol-modified P comprising low molecular weight PPO, which produces the modified polyphenylene oxide of the present invention.
The reaction between PO and epichlorohydrin will be described.
【００１９】フェノール変成ＰＰＯの末端に導入された
フェノール性水酸基と反応してエポキシ化するエピクロ
ルヒドリンのモル数は、末端のフェノール性水酸基に対
して１倍以上好ましくは２倍以上の割合で使用し、反応
条件は８０〜１２０℃で１〜１０時間が好ましい。この
反応には、水酸化ナトリウム、水酸化カリウム等のアル
カリ金属の水酸化物の水溶液が有効で、エピクロルヒド
リンのエポキシ基に対して１当量以上好ましくは１．２
当量以上特に好ましくは１．５当量以上使用する。この
反応には、前述のＰＰＯの再分配反応の際に用いた溶媒
を引き続き使用してもよく、他の溶媒に切り換えてもよ
い。反応後は、系を冷却しメタノールの如きＰＰＯに対
して貧溶媒に生成物を注ぎ込み沈殿として析出させ、さ
らにこの沈殿物を濾過して分離し、水又はメタノールで
洗浄し、未反応のエピクロルヒドリンや前記の触媒を除
去した後５０〜８０℃で減圧乾燥して、目的とする本発
明の変成ポリフェニレンオキサイドを高い純度で得るこ
とができる。The number of moles of epichlorohydrin, which reacts with the phenolic hydroxyl group introduced at the terminal of the phenol-modified PPO and is epoxidized, is 1 time or more, preferably 2 times or more of the terminal phenolic hydroxyl group. The reaction conditions are preferably 80 to 120 ° C. and 1 to 10 hours. For this reaction, an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is effective, and 1 equivalent or more, preferably 1.2 or more, relative to the epoxy group of epichlorohydrin.
Equivalent amount or more, particularly preferably 1.5 equivalent amount or more. In this reaction, the solvent used in the redistribution reaction of PPO described above may be continuously used or may be switched to another solvent. After the reaction, the system is cooled and the product is poured into a poor solvent for PPO such as methanol to form a precipitate, and the precipitate is filtered and separated, washed with water or methanol, and unreacted epichlorohydrin or After removing the catalyst, the target modified polyphenylene oxide of the present invention can be obtained with high purity by drying under reduced pressure at 50 to 80 ° C.
【００２０】このようにして得られた本発明の変成ポリ
フェニレンオキサイドは、溶融粘度が低く流動性に富
み、ビスフェノ−ルＡ型エポキシ樹脂、ビスフェノ−ル
Ｆ型エポキシ樹脂、ビスフェノ−ルＳ型エポキシ樹脂、
フェノ−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、イソシアヌレート型エポキシ樹
脂、ヒダントイン型エポキシ樹脂、脂環式エポキシ樹
脂、ビフェニル型エポキシ樹脂、及び、多官能エポキシ
樹脂等のエポキシ樹脂にも相溶性に富み、均質なワニス
を構成するエポキシ樹脂組成物を与える。The modified polyphenylene oxide of the present invention thus obtained has a low melt viscosity and a high fluidity, and is a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin. ,
Compatible with phenol novolac type epoxy resin, cresol novolac type epoxy resin, isocyanurate type epoxy resin, hydantoin type epoxy resin, alicyclic epoxy resin, biphenyl type epoxy resin, and polyfunctional epoxy resin. It provides an epoxy resin composition that constitutes a rich, homogeneous varnish.
【００２１】なお、本発明の変成ポリフェニレンオキサ
イドは、ポリアミンやポリカルボン酸化合物を反応させ
て末端アミンＰＰＯや末端カルボン酸ＰＰＯを製造する
原料としても有用である。The modified polyphenylene oxide of the present invention is also useful as a raw material for producing a terminal amine PPO or a terminal carboxylic acid PPO by reacting a polyamine or a polycarboxylic acid compound.
【００２２】次に基材に含浸するワニスの形態で使用さ
れる、本発明のエポキシ樹脂組成物について説明する。
このエポキシ樹脂組成物は、エポキシ樹脂、上記の変成
ポリフェニレンオキサイド、及びエポキシ樹脂の硬化剤
を必須成分として含有して成るもので、上記の変成ポリ
フェニレンオキサイドは末端にエポキシ基を有する樹脂
であるからして、この樹脂とは別に配合される上記エポ
キシ樹脂とともにエポキシ樹脂成分として作用する。こ
こで、エポキシ樹脂組成物の主要成分である上記エポキ
シ樹脂としては、積層板に使用されるエポキシ樹脂であ
れば特に限定されるものではなく、例えば、ビスフェノ
−ルＡ型エポキシ樹脂、ビスフェノ−ルＦ型エポキシ樹
脂、ビスフェノ−ルＳ型エポキシ樹脂、フェノ−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、イソシアヌレート型エポキシ樹脂、ヒダントイ
ン型エポキシ樹脂、脂環式エポキシ樹脂、ビフェニル型
エポキシ樹脂、及び、多官能エポキシ樹脂等が挙げら
れ、これらの単独あるいは混合して使用される。さら
に、これらの樹脂を臭素化した難燃化エポキシ樹脂も使
用することができる。Next, the epoxy resin composition of the present invention used in the form of a varnish for impregnating a substrate will be described.
This epoxy resin composition comprises an epoxy resin, the above modified polyphenylene oxide, and a curing agent for the epoxy resin as essential components, and the above modified polyphenylene oxide is a resin having an epoxy group at the terminal. Then, it acts as an epoxy resin component together with the epoxy resin blended separately from this resin. Here, the above-mentioned epoxy resin which is a main component of the epoxy resin composition is not particularly limited as long as it is an epoxy resin used for a laminated board, and examples thereof include bisphenol A type epoxy resin and bisphenol. F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, isocyanurate type epoxy resin, hydantoin type epoxy resin, alicyclic epoxy resin, biphenyl type epoxy resin, and Examples thereof include polyfunctional epoxy resins, which may be used alone or in combination. Furthermore, flame-retardant epoxy resins obtained by brominated these resins can also be used.
【００２３】これらのエポキシ樹脂の硬化剤としては、
通常使用される第一級、第２級アミン等のアミン系、ビ
スフェノールＡ、ビスフェノールＦ等のポリフェノール
を含むフェノール系、酸無水物系を挙げることができ
る。これらは、単独あるいは複数混合して使用される。As a curing agent for these epoxy resins,
Examples thereof include amine systems such as primary and secondary amines which are usually used, phenol systems including polyphenols such as bisphenol A and bisphenol F, and acid anhydride systems. These are used alone or as a mixture of two or more.
【００２４】また、エポキシ樹脂の硬化反応には、必要
に応じて例えばイミダゾール系の硬化促進剤、その他通
常使用される促進剤が添加される。If necessary, for example, an imidazole-based curing accelerator and other commonly used accelerators are added to the curing reaction of the epoxy resin.
【００２５】ここで、エポキシ樹脂組成物の硬化機構に
ついて言及すると、エポキシ基を導入した変成ＰＰＯは
硬化剤によって主要成分のエポキシ樹脂とも結合する。
したがって、変成ＰＰＯはエポキシ樹脂の架橋構造に架
橋構造に関与することになる。Here, referring to the curing mechanism of the epoxy resin composition, the modified PPO in which an epoxy group is introduced is also bonded to the main component epoxy resin by a curing agent.
Therefore, the modified PPO is involved in the crosslinked structure of the epoxy resin.
【００２６】上記のエポキシ樹脂組成物をワニスの形態
でガラス布、ガラス不織布等に含浸乾燥して得られたプ
リプレグは、金属箔の引き剥がし強度、半田耐熱性、メ
ッキ染み込み性並びに高周波特性の指標である誘電率、
誘電正接特性に優れた積層板を与える。A prepreg obtained by impregnating and drying a glass cloth, a glass non-woven cloth or the like with the above epoxy resin composition in the form of a varnish is an index of peeling strength of metal foil, solder heat resistance, plating penetration and high frequency characteristics. Is the dielectric constant,
A laminate having excellent dielectric loss tangent characteristics is provided.
【００２７】このプリプレグは、以下のような方法でつ
くることができる。ワニス中に基材を浸漬するなどし
て、基材にこれらの樹脂ワニスを含浸させ付着させる。
プリプレグの樹脂含有量は、特に限定しないが、３０〜
７０重量％とするのが好ましい。また、含浸時には、樹
脂ワニスを２５〜３５℃に保つと樹脂ワニス中のエポキ
シ樹脂に対する硬化剤の硬化反応を阻止し、基材への含
浸性を高めることができ、積層板の特性を良好にするこ
とができる。樹脂ワニスを含浸後加熱乾燥するに当たっ
ては、８０〜１８０℃の温度が好ましい。その理由は、
この加熱乾燥が不十分であると、プリプレグ表面部分の
みの乾燥に止まり溶媒が内部に残留する為にプリプレグ
の表面と内部との間で樹脂の濃度差に起因する歪が生
じ、プリプレグ表面に微細なクラックが発生する。ま
た、過度に加熱乾燥をすると、プリプレグ表面では乾燥
過程で急激な粘度変化が起こるためにプリプレグ表面に
スジムラや樹脂タレが発生し、金属箔とプリプレグとの
密着性にムラが生じ、その結果金属箔の引き剥がし強
さ、半田耐熱性、誘電特性に大小、強弱のムラが発生す
る。This prepreg can be manufactured by the following method. The resin varnish is impregnated and adhered to the base material by immersing the base material in the varnish.
The resin content of the prepreg is not particularly limited, but is 30 to
It is preferably 70% by weight. Further, at the time of impregnation, if the resin varnish is kept at 25 to 35 ° C., the curing reaction of the curing agent with the epoxy resin in the resin varnish can be prevented, and the impregnation property into the base material can be enhanced, and the characteristics of the laminated plate can be improved. can do. For impregnation with the resin varnish and heating and drying, a temperature of 80 to 180 ° C. is preferable. The reason is,
If this heating and drying is insufficient, only the surface of the prepreg is dried and the solvent remains inside, causing distortion due to the difference in resin concentration between the surface of the prepreg and the inside, resulting in fine prepreg surface. Cracks occur. Further, if it is heated and dried excessively, the viscosity of the prepreg surface changes rapidly during the drying process, causing unevenness or resin sagging on the prepreg surface, resulting in uneven adhesion between the metal foil and the prepreg. Foil peeling strength, solder heat resistance, and dielectric characteristics vary in size and strength.
【００２８】なお、基材としては、ガラスクロス、アラ
ミドクロス、ポリエステルクロス、パルプ紙、リンター
紙等が挙げられる。Examples of the substrate include glass cloth, aramid cloth, polyester cloth, pulp paper and linter paper.
【００２９】次に本発明の積層板について説明する。上
記のプリプレグの数枚と要すれば金属箔を積層して被圧
体とし、この被圧体を加熱加圧して積層板を得る。金属
箔としては、銅箔、アルミニューム箔等が用いられる。
加圧は、金属箔およびシートの接合と、厚みの調整のた
めに行うので、加圧条件は必要に応じて選択することが
できる。また、変成ポリフェニレンオキサイドとエポキ
シ樹脂とこれらののエポキシ樹脂の硬化剤の架橋反応
は、主として硬化剤の反応特性に依存するので、硬化剤
の種類に応じて加熱温度、加熱時間を選ぶ。たとえば、
一般には温度１５０〜３００℃、圧力５０ｋｇ／ｃ
ｍ2 、時間１０〜６０分程度が目安である。Next, the laminated plate of the present invention will be described. Several sheets of the above-mentioned prepreg and, if necessary, metal foils are laminated to form a pressure-receiving body, and the pressure-receiving body is heated and pressed to obtain a laminated plate. As the metal foil, copper foil, aluminum foil or the like is used.
Since the pressure is applied for joining the metal foil and the sheet and adjusting the thickness, the pressure condition can be selected as necessary. Further, the cross-linking reaction between the modified polyphenylene oxide, the epoxy resin, and the curing agent for these epoxy resins depends mainly on the reaction characteristics of the curing agent, and therefore the heating temperature and the heating time are selected according to the type of the curing agent. For example,
Generally, the temperature is 150-300 ° C and the pressure is 50 kg / c.
The standard is m 2 and time of 10 to 60 minutes.
【００３０】このようにして得られた金属箔張り積層板
は、エポキシ樹脂とポリフェニレンオキサイドの特性が
損なわれず、誘電特性等の高周波特性が優れ、しかも半
田耐熱性を左右する耐熱性、接着強度の強弱に起因する
スルホール、パンチング等の加工性、メッキ液の染み込
みの信頼性も優れたものとなる。The metal foil-clad laminate thus obtained does not impair the properties of the epoxy resin and polyphenylene oxide, is excellent in high frequency properties such as dielectric properties, and has excellent heat resistance and adhesive strength that affect solder heat resistance. Workability such as through hole and punching due to strength and weakness, and reliability of impregnation of the plating solution are also excellent.
【００３１】なお、本発明のエポキシ樹脂組成物は、溶
媒を介して樹脂ワニスとし、この樹脂ワニスをガラスク
ロス等の基材に含浸乾燥してプリプレグとしての使用例
に限るものではなく、たとえばキャスチィング法により
基材を含まないシートを作成し、このシートをプリプレ
グに代用することもできる。このキャステング法に依る
ときは、例えばワニスをワニスの溶媒に不溶のポリエス
テルフィルム、ポリイミドフィルムなどの離型シートに
５〜７００μｍの厚みに塗布し、十分に乾燥させると、
ブレンドした樹脂を熱溶融する押出成形によるのと比較
すると比較的低温でより容易にシ−卜を造ることができ
る点で優れている。ワニスをキャステングする前記シー
トは、離型剤で表面処理したシートを用いると剥離が容
易になるので実際的である。The epoxy resin composition of the present invention is not limited to the use example as a prepreg obtained by forming a resin varnish through a solvent and impregnating and drying the resin varnish on a substrate such as glass cloth. For example, casting It is also possible to prepare a sheet containing no base material by the method and substitute this sheet for the prepreg. When using this casting method, for example, a varnish is applied to a release sheet such as a polyester film or a polyimide film insoluble in the solvent of the varnish in a thickness of 5 to 700 μm, and sufficiently dried,
Compared with extrusion molding in which a blended resin is heat-melted, it is excellent in that a seaweed can be easily manufactured at a relatively low temperature. The above-mentioned sheet for casting the varnish is practical because the sheet whose surface is treated with a release agent facilitates peeling.
【００３２】以下、本発明の実施形態を実施例によって
具体的に説明する。The embodiments of the present invention will be specifically described below with reference to examples.
【００３３】[0033]
（実施例１）先ず、数平均分子量Ｍｎ＝２００００の高
分子ＰＰＯ（日本Ｇ．Ｅ．プラスチック（株）製）１０
０重量部（以下、部と記す）、ベンゾイルパーオキサイ
ド６部、及びフェノール性化合物のビスフェノ−ルＡ６
部にトルエン１００部を添加し９０℃にて６０分間攪拌
し、再分配反応させて末端にフェノール性化合物のフェ
ノール性水酸基を有する低分子のフェノール変性ＰＰＯ
の溶液を得た。この溶液をゲル浸透クロマトグラフ（カ
ラム構成：東ソー（株）製 SuperHM-M（１本）＋SuperH
M −H （１本））にて分子量分布を測定した結果、数平
均分子量は２３００であった。(Example 1) First, a polymer PPO having a number average molecular weight Mn of 20000 (manufactured by GE Plastics Japan Ltd.) 10
0 parts by weight (hereinafter referred to as "part"), 6 parts of benzoyl peroxide, and bisphenol A6 of a phenolic compound
To 100 parts of toluene, stirred at 90 ° C. for 60 minutes, and redistributed to cause a low molecular weight phenol-modified PPO having a phenolic hydroxyl group of a phenolic compound at the end.
Was obtained. This solution was gel permeation chromatograph (column composition: Tohso Corp. SuperHM-M (1) + SuperH)
The number average molecular weight was 2,300 as a result of measuring the molecular weight distribution with M-H (1).
【００３４】次に、この溶液２１０部にエピクロルヒド
リン８部と水酸化ナトリューム水溶液（５０％）８部を
加えて１００℃で４時間攪拌した後に室温まで冷却しメ
タノール１リットルを加えて末端にエポキシ基を導入し
た変性ＰＰＯを沈殿させた。この沈殿物を濾別し、メタ
ノール１リットルと水１リットルで２回洗浄し、最後に
メタノール１リットルで洗浄し、７０℃で減圧乾燥し、
変成ポリフェニレンオキサイド（変成ＰＰＯ（Ａ））を
精製した。Next, 8 parts of epichlorohydrin and 8 parts of an aqueous solution of sodium hydroxide (50%) were added to 210 parts of this solution, stirred at 100 ° C. for 4 hours, cooled to room temperature, and 1 liter of methanol was added to the end of the epoxy group. The denatured PPO introduced with was precipitated. The precipitate is filtered off, washed twice with 1 liter of methanol and 1 liter of water, finally with 1 liter of methanol and dried under reduced pressure at 70 ° C.,
Modified polyphenylene oxide (modified PPO (A)) was purified.
【００３５】フェノール変成ＰＰＯとエピクロルヒドリ
ンとの反応率は９１％であった。この反応率は、ＰＰＯ
の１．５重量％の四塩化炭素溶液を光路長１０ｍｍの石
英セルを用いて赤外線スペクトルを測定し、反応前後の
フェノール性水酸基の吸光度（３６２２ｃｍ-1）の値に
より求めた。The reaction rate between the phenol-modified PPO and epichlorohydrin was 91%. This reaction rate is
Infrared spectrum of the 1.5 wt% carbon tetrachloride solution was measured using a quartz cell having an optical path length of 10 mm, and the absorbance (3622 cm −1 ) of the phenolic hydroxyl group before and after the reaction was determined.
【００３６】（実施例２乃至実施例３）実施例１で得た
フェノール変成ＰＰＯの溶液を用い、（表１）に示す配
合に基づき実施例１と同一の条件でエピクロルヒドリン
を反応させ、エポキシ基を導入した本発明の変性ポリフ
ェニレンオキサイド（変成ＰＰＯ（Ｂ））、（変成ＰＰ
Ｏ（Ｃ）を得た。(Examples 2 to 3) Using the phenol-modified PPO solution obtained in Example 1, epichlorohydrin was reacted under the same conditions as in Example 1 based on the formulation shown in (Table 1) to give an epoxy group. The modified polyphenylene oxide of the present invention (modified PPO (B)), (modified PP
O (C) was obtained.
【００３７】（実施例４）実施例１で用いた高分子ＰＰ
Ｏ１００部、ベンゾイルパーオキサイド４部、及びフェ
ノール性化合物のビスフェノ−ルＡ４部にトルエン１０
０部を添加し、実施例１と同一の反応条件で再分配反応
させて末端にフェノール性化合物のフェノール性水酸基
を有する低分子のフェノール変性ＰＰＯの溶液を得た。
数平均分子量は２８００であった。Example 4 Polymer PP used in Example 1
Toluene 10 parts to 100 parts of O, 4 parts of benzoyl peroxide, and 4 parts of bisphenol A which is a phenolic compound.
0 part was added and redistribution reaction was carried out under the same reaction conditions as in Example 1 to obtain a solution of a low molecular weight phenol-modified PPO having a phenolic hydroxyl group of a phenolic compound at the end.
The number average molecular weight was 2,800.
【００３８】次に、この溶液２１０部にエピクロルヒド
リン４部と水酸化ナトリューム水溶液（５０％）２４部
を加えて実施例１と同一の条件で反応させて末端にエポ
キシ基を導入した変性ＰＰＯを沈殿させた。この沈殿物
を濾別し、メタノール１リットルと水１リットルで２回
洗浄し、最後にメタノール１リットルで洗浄し、７０℃
で減圧乾燥し、変成ポリフェニレンオキサイド（変成Ｐ
ＰＯ（Ｄ））を精製した。Next, 4 parts of epichlorohydrin and 24 parts of an aqueous solution of sodium hydroxide (50%) were added to 210 parts of this solution and reacted under the same conditions as in Example 1 to precipitate modified PPO having an epoxy group introduced at the end. Let The precipitate is filtered off, washed twice with 1 liter of methanol and 1 liter of water, and finally with 1 liter of methanol at 70 ° C.
And dried under reduced pressure with modified polyphenylene oxide (modified P
PO (D)) was purified.
【００３９】（実施例５）実施例１で用いた高分子ＰＰ
Ｏ１００部、ベンゾイルパーオキサイド１０部、及びフ
ェノール性化合物のビスフェノ−ルＡ１０部にトルエン
１００部を添加し、実施例１と同一の反応条件で再分配
反応させて末端にフェノール性化合物のフェノール性水
酸基を有する低分子のフェノール変性ＰＰＯの溶液を得
た。数平均分子量は１３００であった。Example 5 Polymer PP used in Example 1
To 100 parts of O, 10 parts of benzoyl peroxide, and 10 parts of bisphenol A of phenolic compound, 100 parts of toluene was added, and redistribution reaction was carried out under the same reaction conditions as in Example 1, and phenolic hydroxyl group of phenolic compound was added to the terminal. A solution of low molecular weight phenol-modified PPO having The number average molecular weight was 1,300.
【００４０】次に、この溶液２１０部にエピクロルヒド
リン２４部と水酸化ナトリューム水溶液（５０％）２４
部を加えて実施例１と同一の条件で反応させて末端にエ
ポキシ基を導入した変性ＰＰＯを沈殿させた。この沈殿
物を濾別し、メタノール１リットルと水１リットルで２
回洗浄し、最後にメタノール１リットルで洗浄し、７０
℃で減圧乾燥し、変成ポリフェニレンオキサイド（変成
ＰＰＯ（Ｅ））を精製した。Next, to 210 parts of this solution, 24 parts of epichlorohydrin and 24% aqueous sodium hydroxide solution (50%) were added.
Was added and reacted under the same conditions as in Example 1 to precipitate a modified PPO having an epoxy group introduced at its end. The precipitate is filtered off and taken up with 1 liter of methanol and 1 liter of water.
Wash twice, and finally with 1 liter of methanol,
The modified polyphenylene oxide (modified PPO (E)) was purified by drying under reduced pressure at ℃.
【００４１】（表１）に実施例１乃至実施例５の変成Ｐ
ＰＯ（Ａ）、（Ｂ）、（Ｃ）、（Ｄ）、（Ｅ）を製造し
たＰＰＯ、エピクロルヒドリン、水酸化ナトリウムの配
合比率を示した。Table 1 shows the modified P of Examples 1 to 5.
The compounding ratios of PPO, epichlorohydrin, and sodium hydroxide for producing PO (A), (B), (C), (D), and (E) are shown.
【００４２】（実施例６〜実施例１０）実施例１乃至実
施例５で得た変成ＰＰＯ（Ａ）、（Ｂ）、（Ｃ）を用い
て （表２）に示した成分の配合割合に従いセパラブル
フラスコに入れ、室温で３０分間攪拌し空冷を行い２５
℃のワニスを得た。このワニスは初期の粘度も小さく、
析出現象もなく保存性に優れていた。２４時間後に樹脂
ワニスを０．１ｍｍのＥガラスクロスに含浸し、１４０
℃で４分間乾燥し、樹脂含有率５３重量％のプリプレグ
を得た。このプリプレグは、（表３）に示す如く、表面
が平滑で樹脂の含浸ムラもなく、このワニスの良好な含
浸性を裏付けるものであった。(Examples 6 to 10) Using the modified PPOs (A), (B) and (C) obtained in Examples 1 to 5, according to the blending ratio of the components shown in (Table 2). Place in a separable flask, stir at room temperature for 30 minutes, and air cool to 25
A varnish of ℃ was obtained. This varnish has a small initial viscosity,
There was no precipitation phenomenon and it was excellent in storage stability. After 24 hours, 0.1 mm of E glass cloth was impregnated with the resin varnish, and 140
It was dried at ℃ for 4 minutes to obtain a prepreg having a resin content of 53% by weight. As shown in (Table 3), this prepreg had a smooth surface and had no resin impregnation unevenness, which confirmed the good impregnation property of this varnish.
【００４３】このプリプレグに対して外観、取扱性、含
浸性について評価した結果を（表３）に示した。The results of evaluating the appearance, handleability and impregnating property of this prepreg are shown in (Table 3).
【００４４】次に、このプリプレグを８枚重ね合わせ、
その両面に１８μｍの銅箔を配置して被圧体とし、１９
０℃で圧力２０ｋｇ／ｃｍ2 で１００分加熱加圧し両面
に銅箔が積層された銅張り積層板を得た。この積層板に
ついて銅箔引き剥し強さ、ＰＣＴ半田耐熱性、誘電率、
及び誘電正接を測定し、測定結果を（表３）に示した。
なお、誘電率、及び誘電正接はＭＩＬに規定する測定条
件によった。Next, 8 pieces of this prepreg are overlapped,
A copper foil of 18 μm is placed on both sides to form a body to be pressed.
It was heated and pressed at 0 ° C. under a pressure of 20 kg / cm 2 for 100 minutes to obtain a copper-clad laminate having copper foil laminated on both sides. About this laminated board, copper foil peeling strength, PCT solder heat resistance, dielectric constant,
And the dielectric loss tangent were measured and the measurement results are shown in (Table 3).
The dielectric constant and the dielectric loss tangent were based on the measurement conditions specified in MIL.
【００４５】[0045]
（比較例１）実施例１の高分子ＰＰＯ１０１部、ベンゾ
イルパーオキサイド１部、及びフェノール性化合物のビ
スフェノ−ルＡ１部にトルエン１００部を添加し９０℃
にて６０分間攪拌し、再分配反応させてフェノール変成
ＰＰＯの溶液を得た。このフェノール変性ＰＰＯの数平
均分子量は１７０００であった。(Comparative Example 1) Toluene 100 parts was added to 101 parts of the polymer PPO of Example 1, 1 part of benzoyl peroxide, and 1 part of bisphenol A of a phenolic compound, and 90 ° C was added.
The mixture was stirred for 60 minutes, and the redistribution reaction was performed to obtain a solution of phenol-modified PPO. The number average molecular weight of this phenol-modified PPO was 17,000.
【００４６】次に、この溶液にエピクロルヒドリン２部
と水酸化ナトリューム水溶液（５０％）２部を加え、実
施例１と同一の反応条件、処理条件で変性ポリフェニレ
ンオキサイド（変成ＰＰＯ（Ｆ）を精製した。反応率は
９２％であった。Next, 2 parts of epichlorohydrin and 2 parts of an aqueous sodium hydroxide solution (50%) were added to this solution, and the modified polyphenylene oxide (modified PPO (F) was purified under the same reaction conditions and treatment conditions as in Example 1. The reaction rate was 92%.
【００４７】（比較例２）実施例１の高分子ＰＰＯ１０
１部、ベンゾイルパーオキサイド３０部、及びフェノー
ル性化合物のビスフェノ−ルＡ３０部にトルエン１００
部を添加し比較例１と同一の条件で再分配反応させてフ
ェノール変成ＰＰＯの溶液を得た。このフェノール変性
ＰＰＯの数平均分子量は７００であった。Comparative Example 2 Polymer PPO10 of Example 1
1 part, 30 parts of benzoyl peroxide, and 30 parts of bisphenol A, which is a phenolic compound, and 100 parts of toluene.
Parts were added and redistribution reaction was carried out under the same conditions as in Comparative Example 1 to obtain a phenol-modified PPO solution. The number average molecular weight of this phenol-modified PPO was 700.
【００４８】次に、この溶液にエピクロルヒドリン２部
と水酸化ナトリューム水溶液（５０％）２部を加え、実
施例１と同一の反応条件、処理条件で変性ポリフェニレ
ンオキサイド（変成ＰＰＯ（Ｇ）を精製した。Next, 2 parts of epichlorohydrin and 2 parts of an aqueous solution of sodium hydroxide (50%) were added to this solution, and the modified polyphenylene oxide (modified PPO (G) was purified under the same reaction conditions and treatment conditions as in Example 1. .
【００４９】（比較例３）実施例１の高分子ＰＰＯ１０
１部、ベンゾイルパーオキサイド２部、及びフェノール
性化合物のビスフェノ−ルＡ２部にトルエン１００部を
添加し比較例１と同一の条件で再分配反応させてフェノ
ール変成ＰＰＯの溶液を得た。このフェノール変性ＰＰ
Ｏの数平均分子量は３４００であった。Comparative Example 3 Polymer PPO10 of Example 1
100 parts of toluene was added to 1 part, 2 parts of benzoyl peroxide, and 2 parts of bisphenol A of the phenolic compound, and redistribution reaction was performed under the same conditions as in Comparative Example 1 to obtain a solution of phenol-modified PPO. This phenol-modified PP
The number average molecular weight of O was 3,400.
【００５０】次に、この溶液にエピクロルヒドリン２部
と水酸化ナトリューム水溶液（５０％）２部を加え、実
施例１と同一の反応条件、処理条件で変性ポリフェニレ
ンオキサイド（変成ＰＰＯ（Ｈ）を精製した。Next, 2 parts of epichlorohydrin and 2 parts of an aqueous solution of sodium hydroxide (50%) were added to this solution, and the modified polyphenylene oxide (modified PPO (H) was purified under the same reaction conditions and treatment conditions as in Example 1. .
【００５１】（比較例４乃至比較例６）比較例１乃至比
較例３の変成ＰＰＯ（Ｆ）、（Ｇ）、（Ｈ）を用いて、
（表２）に示した成分の配合割合に従い実施例６乃至実
施例１０と同一の条件でワニスを得た。このワニスを実
施例と同一のＥガラスクロスに同一条件で含浸乾燥しプ
リプレグを得た。このプリプレグを用いて実施例と同一
の条件で銅張り積層板を得た。(Comparative Examples 4 to 6) Using the modified PPOs (F), (G) and (H) of Comparative Examples 1 to 3,
Varnishes were obtained under the same conditions as in Examples 6 to 10 according to the blending ratios of the components shown in (Table 2). This varnish was impregnated into the same E glass cloth as in Example under the same conditions and dried to obtain a prepreg. Using this prepreg, a copper-clad laminate was obtained under the same conditions as in the examples.
【００５２】[0052]
【表１】 [Table 1]
【００５３】[0053]
【表２】 [Table 2]
【００５４】[0054]
【表３】 [Table 3]
【００５５】実施例と比較例の樹脂ワニス特性、プリプ
レグ特性、積層板特性を対比すると、銅箔引き剥がし強
さ、半田耐熱性、メッキ染み込み性並びに高周波特性の
指標である誘電率、誘電正接特性に優れていることが明
白で、これは樹脂ワニスの含浸性が高まり、且つ本発明
の変成ポリフェニレンオキサイドがエポキシ樹脂の硬化
物を構成する架橋構造に関与していることによるもので
ある。Comparing the resin varnish characteristics, prepreg characteristics, and laminated board characteristics of the examples and the comparative examples, copper foil peeling strength, solder heat resistance, plating penetration, and dielectric constant and dielectric loss tangent characteristic of high frequency characteristics. It is obvious that the modified polyphenylene oxide of the present invention is involved in the crosslinked structure constituting the cured product of the epoxy resin, because the impregnation property of the resin varnish is enhanced.
【００５６】[0056]
【発明の効果】本発明によると、金属箔の引き剥し強
さ、半田耐熱性、メッキ染み込み性並びに高周波特性の
指標である誘電率、誘電正接特性に優れた積層板を与え
ることができる。According to the present invention, it is possible to provide a laminate having excellent peeling strength of a metal foil, solder heat resistance, plating penetration, and excellent dielectric constant and dielectric loss tangent characteristic of high frequency characteristics.
フロントページの続き (72)発明者 斎藤 英一郎 大阪府門真市大字門真1048番地松下電工株 式会社内Front page continuation (72) Inventor Eiichiro Saito 1048, Kadoma, Kadoma-shi, Osaka Matsushita Electric Works Co., Ltd.
Claims (6)
の高分子量のポリフェニレンオキサイドをポリフェノー
ル性化合物とラジカル開始剤の存在下で再分配反応させ
て得られた数平均分子量が１０００〜３０００のフェノ
ール変成ポリフェニレンオキサイド、及びエピクロルヒ
ドリンとを反応させることを特徴とする末端をエポキシ
化した変成ポリフェニレンオキサイドの製法。1. A compound having a number average molecular weight of 10,000 to 30,000
Reacting a high molecular weight polyphenylene oxide with a polyphenolic compound in the presence of a radical initiator to obtain a phenol-modified polyphenylene oxide having a number average molecular weight of 1000 to 3000, and epichlorohydrin. A method for producing a modified polyphenylene oxide having an epoxidized terminal.
キサイドである請求項１の変成ポリフェニレンオキサイ
ドの製法。2. The method for producing a modified polyphenylene oxide according to claim 1, wherein the radical initiator is benzoyl peroxide.
サイドにエピクロルヒドリンを反応させる際に触媒とし
てアルカリ金属の水酸化物を用いる請求項１又は請求項
２の変成ポリフェニレンオキサイドの製法。3. The method for producing a modified polyphenylene oxide according to claim 1 or 2, wherein an alkali metal hydroxide is used as a catalyst when the phenol-modified polyphenylene oxide is reacted with epichlorohydrin.
いずれかの製法によって得られた変成ポリフェニレンオ
キサイド、及びエポキシ樹脂の硬化剤からなるエポキシ
樹脂組成物。4. Epoxy resin, claim 1 to claim 3.
An epoxy resin composition comprising a modified polyphenylene oxide obtained by any of the production methods and an epoxy resin curing agent.
たプリプレグ。5. A prepreg in which a base material is impregnated with the epoxy resin according to claim 4.
層板。6. A laminated plate obtained by heating and pressing the prepreg of claim 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12756696A JP3248424B2 (en) | 1996-02-29 | 1996-05-23 | Process for producing modified polyphenylene oxide, epoxy resin composition using modified polyphenylene oxide by this process, prepreg using this composition, and laminate using this prepreg |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4304596 | 1996-02-29 | ||
| JP8-43045 | 1996-02-29 | ||
| JP12756696A JP3248424B2 (en) | 1996-02-29 | 1996-05-23 | Process for producing modified polyphenylene oxide, epoxy resin composition using modified polyphenylene oxide by this process, prepreg using this composition, and laminate using this prepreg |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09291148A true JPH09291148A (en) | 1997-11-11 |
| JP3248424B2 JP3248424B2 (en) | 2002-01-21 |
Family
ID=26382791
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12756696A Expired - Lifetime JP3248424B2 (en) | 1996-02-29 | 1996-05-23 | Process for producing modified polyphenylene oxide, epoxy resin composition using modified polyphenylene oxide by this process, prepreg using this composition, and laminate using this prepreg |
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| Country | Link |
|---|---|
| JP (1) | JP3248424B2 (en) |
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| US6589656B2 (en) | 2000-07-26 | 2003-07-08 | Matsushita Electric Works, Ltd. | Epoxy resin composition, prepreg and metal-clad laminate |
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