JPH0812744A - Resin composition and prepreg - Google Patents
Resin composition and prepregInfo
- Publication number
- JPH0812744A JPH0812744A JP15189794A JP15189794A JPH0812744A JP H0812744 A JPH0812744 A JP H0812744A JP 15189794 A JP15189794 A JP 15189794A JP 15189794 A JP15189794 A JP 15189794A JP H0812744 A JPH0812744 A JP H0812744A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- resin composition
- prepreg
- resin
- represented
- 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]
【産業上の利用分野】この発明は、各種電子機器に用い
られるプリント配線基板を構成する樹脂組成物およびプ
リプレグに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition and a prepreg constituting a printed wiring board used in various electronic devices.
【０００２】[0002]
【従来の技術】近年、電子機器の高性能化が急速に進む
につれ、プリント配線板は増々高度な特性、機能および
経済性が要求されている。基板材料としてはこれまで、
電気絶縁性、強度、コスト等に優れたガラス繊維とエポ
キシ樹脂の組合せがほとんどを占めてきていたが、最近
の配線の高密度化やチップ実装の進展にともない、ガラ
ス繊維基材では対応できない局面が顕在化し、全芳香族
ポリアミド繊維を基材とする銅張積層板を作る試みが報
告されている（例えば特開昭６０−５２９３７号公報、
特開昭６１−１６０５００号公報、特開昭６２−２６１
１９０号公報、特開昭６２−２７３７９２号公報、特開
昭６２−２７４６８８号公報、特開昭６２−２７４６８
９号公報等）。これらは、低膨張、低誘電率、軽量であ
るといった特徴を生かして、民生用電子機器をはじめ産
業用や軍需用などの用途に検討されている。この銅張積
層板は、エポキシ樹脂等の配合ワニスを全芳香族ポリア
ミド繊維からなる織物や紙、不織布などに含浸乾燥させ
て得られるプリプレグを複数枚積層形成することにより
得られる。2. Description of the Related Art In recent years, as the performance of electronic equipment has rapidly increased, printed wiring boards are required to have more advanced characteristics, functions and economical efficiency. So far as the substrate material,
The combination of glass fiber and epoxy resin, which excel in electrical insulation, strength, and cost, has been dominated, but with the recent increase in wiring density and chip mounting, the situation where glass fiber substrates cannot handle Has been reported, and an attempt to produce a copper-clad laminate using wholly aromatic polyamide fibers as a base material has been reported (for example, JP-A-60-52937,
JP-A-61-160500, JP-A-62-261
190, JP 62-273792, JP 62-274688, and JP 62-27468.
No. 9, etc.). Taking advantage of their characteristics such as low expansion, low dielectric constant, and light weight, these have been investigated for applications such as consumer electronic devices, industrial use, and military use. This copper-clad laminate is obtained by laminating and forming a plurality of prepregs obtained by impregnating and drying a varnish such as an epoxy resin in a woven fabric, paper, a nonwoven fabric or the like made of wholly aromatic polyamide fibers.
【０００３】従来から銅張積層板用エポキシ樹脂組成と
しては、難燃性を得るためのテトラブロムビスフェノー
ルＡとエピクロルヒドリンから得られる臭素化エポキシ
樹脂に耐熱性のオルソクレゾールノボラック型樹脂、硬
化剤としてジシアンジアミドなどを加えたものが多用さ
れてきた。しかし該エポキシ樹脂組成物はピール強度は
良好であるが耐熱性が低く、更に従来のブロム含有率
（エポキシ樹脂組成物の固形分対比約１５〜１８重量
％）のワニス（ＦＲ−４相当）を芳香族ポリアミド繊維
基材に対して含浸させた基板は、難燃性が劣りまた耐湿
ハンダ性も不良である。Conventionally, as an epoxy resin composition for copper-clad laminates, a brominated epoxy resin obtained from tetrabromobisphenol A and epichlorohydrin for obtaining flame retardancy, a heat-resistant orthocresol novolac type resin, and a dicyandiamide as a curing agent are used. Those that have been added have been used frequently. However, the epoxy resin composition has good peel strength but low heat resistance, and a varnish (corresponding to FR-4) having a conventional bromine content (about 15 to 18% by weight relative to the solid content of the epoxy resin composition) is used. A substrate impregnated with an aromatic polyamide fiber base material has inferior flame retardancy and poor moisture solder resistance.
【０００４】これらの欠点を克服するために、まず難燃
性に着目してオルソクレゾールノボラック型エポキシ樹
脂の代わりにブロム化フェノールノボラック型エポキシ
樹脂を用い、次に耐熱性を向上させるためにその配合量
を増大させると、耐熱性の向上はわずかであり同時にピ
ール強度が大幅に低下し、更に耐湿ハンダ性の向上は殆
どない。更に他の耐熱性の骨格を導入したり剛直な核を
数多く導入したり架橋密度を増大したりする方法によ
り、耐熱性だけはかなり向上させることができる。しか
し一方で難燃剤を加えると耐熱性、ピール強度、耐湿ハ
ンダ性等が低下するため、従来より難燃性を強化させつ
つ耐熱性を向上させ、かつピール強度や耐湿ハンダ性を
同時に向上させることは極めて困難であった。In order to overcome these drawbacks, first, focusing on the flame retardancy, a brominated phenol novolac type epoxy resin is used in place of the orthocresol novolac type epoxy resin, and then its blending for improving heat resistance. When the amount is increased, the heat resistance is slightly improved, and at the same time, the peel strength is significantly reduced, and the moisture solder resistance is hardly improved. Further, only the heat resistance can be considerably improved by introducing another heat-resistant skeleton, introducing many rigid nuclei, or increasing the crosslinking density. However, on the other hand, adding a flame retardant lowers heat resistance, peel strength, moisture solder resistance, etc., so it is necessary to improve heat resistance while at the same time enhancing flame resistance, and at the same time improve peel strength and moisture solder resistance. Was extremely difficult.
【０００５】また、硬化剤の方では、耐熱性と耐湿性を
有する硬化剤としてフェノールノボラック樹脂やオルソ
クレゾールノボラック樹脂、メタクレゾールノボラック
樹脂、パラクレゾールノボラック樹脂、レゾルシンノボ
ラック樹脂などのアルキルフェノールノボラック樹脂等
が用いられ、またエポキシ樹脂の硬化促進剤としては、
イミダゾール類またはイミダゾリン類がよく利用されて
いる。イミダゾール類としては、２−メチルイミダゾー
ル、２−エチルイミダゾール、４−メチルイミダゾー
ル、２−エチル−４−メチルイミダゾール、２−ウンデ
シルイミダゾール、１−ベンジル−２−メチルイミダゾ
ール等が、イミダゾリン類としては２−エチル−４−メ
チルイミダゾリン、２−ウンデシルイミダゾリン、２−
メチルイミダゾリン等がある。これらのノボラック樹脂
と硬化促進剤を上記各種のエポキシ樹脂の硬化剤として
使用した場合は、耐熱性および耐湿ハンダ性はかなり向
上するが、ピール強度が著しく低下してしまう。As for the curing agent, as a curing agent having heat resistance and moisture resistance, an alkylphenol novolac resin such as phenol novolac resin, orthocresol novolac resin, meta-cresol novolac resin, para-cresol novolac resin or resorcinol novolac resin is used. Used as a curing accelerator for epoxy resin,
Imidazoles or imidazolines are commonly used. Examples of the imidazoles include 2-methylimidazole, 2-ethylimidazole, 4-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, and the like. 2-Ethyl-4-methylimidazoline, 2-undecylimidazoline, 2-
Examples include methyl imidazoline. When these novolac resins and curing accelerators are used as curing agents for the above various epoxy resins, heat resistance and moisture solder resistance are considerably improved, but the peel strength is significantly reduced.
【０００６】したがってガラス繊維に比べて難燃性が低
くかつ吸水率が高い芳香族ポリアミド繊維を基材とする
基板においては、耐熱性とピール強度を向上させかつ高
度の難燃性や耐湿ハンダ性を付与するために、全く従来
と異なるエポキシ樹脂と硬化システムの開発が必要であ
った。Therefore, in a substrate having an aromatic polyamide fiber as a base material, which has lower flame retardancy and higher water absorption than glass fiber, heat resistance and peel strength are improved, and high flame retardancy and moisture solder resistance are provided. In order to provide the above, it was necessary to develop a completely different epoxy resin and curing system.
【０００７】[0007]
【発明が解決しようとする課題】しかしながら、ノート
型パソコンやカメラ一体型ＶＴＲ等、最近の電子機器や
電子部品の小型軽量化の流れの中でプリント板材料は、
薄物多層プリント板が積極的に用いられるようになっ
た。この薄物多層プリント板としての要求に対して従来
の構成では、耐湿耐熱性、寸法安定性および機械的強度
が低いという問題を有していた。すなわち薄物多層プリ
ント板は、その宿命として単位重量当りの表面積が大き
いため吸湿性が高いうえ、ハンダリフローによる熱衝撃
を、さらには機械的強度の低下をまねきやすく、一般の
多層プリント板に比べてハンダ耐熱性、反りや寸法変化
等に極めて不利な状態である。また、全芳香族ポリアミ
ド繊維基材とエポキシ樹脂間の接着力に関して、樹脂組
成面からの充分な検討がなされていないこともプリント
板の機械的強度低下の一要因となっていた。However, in the recent trend toward miniaturization and weight reduction of electronic devices and electronic components such as notebook type personal computers and camera-integrated VTRs, printed circuit board materials are
Thin multilayer printed boards have been actively used. With respect to the demand for this thin multi-layer printed board, the conventional structure has the problems of low humidity heat resistance, dimensional stability, and low mechanical strength. In other words, thin multi-layer printed boards have a large surface area per unit weight as their fate, so they have high hygroscopicity, and are more prone to thermal shock due to solder reflow and also to lower mechanical strength. It is extremely unfavorable to solder heat resistance, warpage and dimensional change. Further, the adhesive strength between the wholly aromatic polyamide fiber base material and the epoxy resin has not been sufficiently studied from the viewpoint of the resin composition, which has also been a factor of lowering the mechanical strength of the printed board.
【０００８】この発明は、かかる従来の問題点を解消す
るもので、エポキシ樹脂系の架橋性改善とその架橋性向
上による樹脂の高ガラス転移温度化と高温度域での弾性
率低下率の減少、および全芳香族ポリアミド繊維基材と
の接着性の向上を達成し、プリント配線基板の耐熱性お
よび機械的特性の向上を図ることのできる樹脂組成物お
よびプリプレグを提供することを目的とするものであ
る。The present invention solves the above problems of the prior art by improving the crosslinkability of an epoxy resin system and raising the glass transition temperature of the resin and reducing the rate of decrease in elastic modulus in the high temperature region by the improvement of the crosslinkability. , And a resin composition and a prepreg capable of achieving improved adhesiveness with a wholly aromatic polyamide fiber base material and improving heat resistance and mechanical properties of a printed wiring board. Is.
【０００９】[0009]
【課題を解決するための手段】請求項１の樹脂組成物
は、エポキシ樹脂系にテトラブロムビスフェノールＡ構
造を含み、硬化促進剤としてビスイミダゾール化合物を
含むことを特徴とする。請求項２の樹脂組成物は、請求
項１の樹脂組成物において、エポキシ樹脂系が３官能エ
ポキシ樹脂を含んでいる。The resin composition according to claim 1 is characterized in that the epoxy resin system contains a tetrabromobisphenol A structure and a bisimidazole compound as a curing accelerator. A resin composition according to a second aspect is the resin composition according to the first aspect, wherein the epoxy resin system includes a trifunctional epoxy resin.
【００１０】請求項３の樹脂組成物は、請求項１の樹脂
組成物において、エポキシ樹脂系が４官能エポキシ樹脂
を含んでいる。請求項４の樹脂組成物は、請求項１の樹
脂組成物において、エポキシ樹脂系が（化１）で表され
るジオキシジフェニルスルホン構造含有エポキシ樹脂を
含んでいる。A third aspect of the resin composition according to the first aspect is that the epoxy resin system contains a tetrafunctional epoxy resin. A resin composition according to a fourth aspect is the resin composition according to the first aspect, wherein the epoxy resin system includes a dioxydiphenylsulfone structure-containing epoxy resin represented by the formula (1).
【００１１】請求項５の樹脂組成物は、請求項１の樹脂
組成物において、エポキシ樹脂系が（化２）で表される
テトラブロムジオキシジフェニルスルホン構造含有エポ
キシ樹脂を含んでいる。請求項６の樹脂組成物は、請求
項１の樹脂組成物において、ビスイミダゾール化合物の
一般式が（化３）で表されるカルボニルジイミダゾール
を含有する。A resin composition according to a fifth aspect is the resin composition according to the first aspect, wherein the epoxy resin system includes a tetrabromodioxydiphenylsulfone structure-containing epoxy resin represented by the formula (2). A resin composition according to a sixth aspect is the resin composition according to the first aspect, which contains carbonyldiimidazole represented by the general formula of the bisimidazole compound.
【００１２】請求項７の樹脂組成物は、請求項１の樹脂
組成物において、ビスイミダゾール化合物の一般式が
（化４）で表される化合物を含有する。請求項８のプリ
プレグは、請求項１，２，３，４，５，６または７の樹
脂組成物を全芳香族ポリアミド繊維基材に含浸させてな
ることを特徴とする。請求項９のプリプレグは、請求項
８のプリプレグにおいて、全芳香族ポリアミド繊維基材
が１５重量％以下のポリメタフェニレンイソフタラミド
を含むポリパラフェニレンテレフタラミド不織布であ
る。A resin composition according to a seventh aspect is the resin composition according to the first aspect, which contains a compound represented by the general formula (Formula 4) of the bisimidazole compound. The prepreg of claim 8 is characterized in that a wholly aromatic polyamide fiber base material is impregnated with the resin composition of claim 1, 2, 3, 4, 5, 6 or 7. A prepreg according to a ninth aspect is the prepreg according to the eighth aspect, which is the polyparaphenylene terephthalamide nonwoven fabric in which the wholly aromatic polyamide fiber base material contains 15% by weight or less of polymetaphenylene isophthalamide.
【００１３】請求項１０のプリプレグは、請求項８のプ
リプレグにおいて、全芳香族ポリアミド繊維基材がコポ
リパラフェニレン・３．４’オキシジフェニレン・テレ
フタラミド不織布である。A prepreg according to a tenth aspect is the prepreg according to the eighth aspect, wherein the wholly aromatic polyamide fiber base material is copolyparaphenylene.3.4'oxydiphenylene.terephthalamide nonwoven fabric.
【００１４】[0014]
【作用】この発明は、エポキシ樹脂系にテトラブロムビ
スフェノールＡ構造物を必須とし、３官能エポキシ樹
脂，４官能エポキシ樹脂およびスルホン含有エポキシ樹
脂のうち少なくとも１つを含み、その硬化促進剤として
ビスイミダゾール化合物を含有する樹脂組成物であり、
さらにこの樹脂組成物を全芳香族ポリアミド繊維基材に
含浸、乾燥して形成したプリプレグである。３官能エポ
キシ樹脂，４官能エポキシ樹脂およびジオキシジフェニ
レンスルホン含有エポキシ樹脂のうち少なくとも１つを
含む組成物に対してビスイミダゾール化合物は、従来の
イミダゾール系と比較してエポキシ基の開環重合反応が
非常に優れているため、少量の添加で大きな硬化性を発
揮させる能力を有する。これより得られた硬化物は架橋
密度が大きく、かつ室温から高温状態での弾性率低下が
少ないほか、全芳香族ポリアミド繊維基材との接合強度
も大きいため、耐熱性や機械的強度等の向上作用があ
る。The present invention requires a tetrabromobisphenol A structure as an essential component in an epoxy resin system and contains at least one of a trifunctional epoxy resin, a tetrafunctional epoxy resin and a sulfone-containing epoxy resin, and bisimidazole as a curing accelerator thereof. A resin composition containing a compound,
Furthermore, it is a prepreg formed by impregnating a wholly aromatic polyamide fiber base material with this resin composition and drying. For a composition containing at least one of a trifunctional epoxy resin, a tetrafunctional epoxy resin, and a dioxydiphenylene sulfone-containing epoxy resin, the bisimidazole compound has a ring-opening polymerization reaction of an epoxy group as compared with a conventional imidazole system. Is very excellent, and has the ability to exert great curability even when added in a small amount. The cured product obtained from this has a large cross-linking density, and has little decrease in elastic modulus from room temperature to a high temperature state, and also has a large bonding strength with the wholly aromatic polyamide fiber base material, so that heat resistance, mechanical strength, etc. Has an improving effect.
【００１５】[0015]
【実施例】以下、この発明の実施例を説明する。この実
施例は、耐熱性、および機械的強度に大きく影響するエ
ポキシ樹脂組成系におけるエポキシ樹脂と硬化促進剤お
よび基材を規定したものである。 （実施例１）まず、下記に示す〜の材料を溶解混合
してワニスを調製する。なお実施例に示している部数
は、全て重量部を示している。 臭素化ビスフェノールＡ型エポキシ樹脂 ３５．０部 （臭素量；２３％，エポキシ等量；２７０） ３官能エポキシ樹脂 ３５．０部 （臭素量；２３％，エポキシ等量；２７０） ノボラック型フェノール樹脂 ３０．０部 （水酸基等量；１２０） （化３）で表されるカルボニルジイミダゾール ０．１部 メチルエチルケトン ６６．６部 つぎに、全芳香族ポリアミド繊維不織布（構造；ポリパ
ラフェニレンテレフタラミド，坪量；７０ｇ／ｍ2 ，厚
さ；０．１５ｍｍ）を基材とし、この基材に、プリプレ
グ状態で含浸樹脂量が５０±１％になるようにワニスを
含浸させ、１４０℃で５分間乾燥し、プリプレグとし
た。このプリプレグの含浸樹脂量は５０重量％、厚みは
０．１５ｍｍであった。しかる後、プリプレグの両面に
厚さ１８μｍの電解銅箔を積層し、熱圧着してプリント
配線基板を形成した。熱圧着は圧力５０ｋｇ／ｃｍ2 、
温度１８０℃で６０分間の条件で行った。Embodiments of the present invention will be described below. This example defines an epoxy resin, a curing accelerator, and a base material in an epoxy resin composition system that greatly affects heat resistance and mechanical strength. (Example 1) First, the following materials (1) to (4) are dissolved and mixed to prepare a varnish. All parts shown in the examples are parts by weight. Brominated bisphenol A type epoxy resin 35.0 parts (bromine amount; 23%, epoxy equivalent amount: 270) Trifunctional epoxy resin 35.0 parts (bromine amount; 23%, epoxy equivalent amount: 270) Novolac type phenol resin 30 0.0 part (hydroxyl group equivalent; 120) Carbonyldiimidazole represented by Chemical formula 3 0.1 part Methyl ethyl ketone 66.6 parts Next, a wholly aromatic polyamide fiber nonwoven fabric (structure: polyparaphenylene terephthalamide, tsubo) Amount: 70 g / m 2 , thickness: 0.15 mm) is used as a base material, and this base material is impregnated with varnish so that the amount of impregnated resin is 50 ± 1% in a prepreg state, and dried at 140 ° C. for 5 minutes. I made it a prepreg. The amount of impregnated resin in this prepreg was 50% by weight, and the thickness was 0.15 mm. Then, an electrolytic copper foil having a thickness of 18 μm was laminated on both surfaces of the prepreg and thermocompression bonded to form a printed wiring board. The pressure for thermocompression bonding is 50 kg / cm 2 ,
It was performed at a temperature of 180 ° C. for 60 minutes.
【００１６】（実施例２）（実施例１）において用いた
３官能エポキシ樹脂の代わりに、４官能エポキシ樹脂を
用いた以外は（実施例１）と同様にしてワニスを得て、
それを用いてプリプレグおよびプリント配線基板を形成
した。 （実施例３）（実施例１）において用いた３官能エポキ
シ樹脂の代わりに、（化１）で表されるジオキシジフェ
ニルスルホン含有ビスフェノールＡ型エポキシ樹脂を用
いた以外は（実施例１）と同様にしてワニスを得て、そ
れを用いてプリプレグおよびプリント配線基板を形成し
た。Example 2 A varnish was obtained in the same manner as in Example 1 except that a tetrafunctional epoxy resin was used instead of the trifunctional epoxy resin used in Example 1.
Using it, a prepreg and a printed wiring board were formed. (Example 3) [Example 1] except that a dioxydiphenylsulfone-containing bisphenol A type epoxy resin represented by (Chemical Formula 1) was used in place of the trifunctional epoxy resin used in (Example 1). A varnish was obtained in the same manner and used to form a prepreg and a printed wiring board.
【００１７】（実施例４）（実施例１）において用いた
３官能エポキシ樹脂の代わりに、（化２）で表されるテ
トラブロムジオキシジフェニルスルホン含有ビスフェノ
ールＡ型エポキシ樹脂を用いた以外は（実施例１）と同
様にしてワニスを得て、それを用いてプリプレグおよび
プリント配線基板を形成した。(Example 4) In place of the trifunctional epoxy resin used in (Example 1), a tetrabromodioxydiphenylsulfone-containing bisphenol A type epoxy resin represented by Chemical formula 2 was used ( A varnish was obtained in the same manner as in Example 1) and used to form a prepreg and a printed wiring board.
【００１８】（実施例５）（実施例１）において用いた
カルボニルジイミダゾールの代わりに、（化４）で表さ
れる化合物を用いた以外は（実施例１）と同様にしてワ
ニスを得て、それを用いてプリプレグおよびプリント配
線基板を形成した。 （比較例１）（実施例１）において用いた３官能エポキ
シ樹脂の代わりに、２官能エポキシ樹脂を用いた以外は
（実施例１）と同様にしてワニスを得て、それを用いて
プリプレグおよびプリント配線基板を形成した。(Example 5) A varnish was obtained in the same manner as in (Example 1) except that the compound represented by (Chemical Formula 4) was used instead of the carbonyldiimidazole used in (Example 1). A prepreg and a printed wiring board were formed using it. (Comparative Example 1) A varnish was obtained in the same manner as in (Example 1) except that a bifunctional epoxy resin was used in place of the trifunctional epoxy resin used in (Example 1). A printed wiring board was formed.
【００１９】（比較例２）（実施例１）において用いた
カルボニルジイミダゾールの代わりに、２−エチル−４
−メチルイミダゾールを用いた以外は（実施例１）と同
様にしてワニスを得て、それを用いてプリプレグおよび
プリント配線基板を形成した。 （実施例６）（実施例１）において用いたポリパラフェ
ニレンテレフタラミド構造の不織布基材の代わりに、１
５重量％のポリメタフェニレンイソフタラミドを含むポ
リパラフェニレンテレフェタラミド構造の布織布を用い
た以外は（実施例１）と同様にしてプリプレグおよびプ
リント配線基板を形成した。Comparative Example 2 2-Ethyl-4 was used instead of carbonyldiimidazole used in Example 1.
A varnish was obtained in the same manner as in (Example 1) except that -methylimidazole was used, and the varnish was used to form a prepreg and a printed wiring board. (Example 6) Instead of the non-woven fabric substrate having the polyparaphenylene terephthalamide structure used in (Example 1), 1
A prepreg and a printed wiring board were formed in the same manner as in (Example 1) except that a woven fabric having a polyparaphenylene terephetamide structure containing 5% by weight of polymetaphenylene isophthalamide was used.
【００２０】（実施例７）（実施例１）において用いた
ポリパラフェニレンテレフタラミド構造の不織布基材の
代わりに、コポリパラフェニレン・３．４’オキシジフ
ェニレン・テレフタラミド構造の不織布を用いた以外は
（実施例１）と同様にしてプリプレグおよびプリント配
線基板を形成した。(Example 7) Instead of the polyparaphenylene terephthalamide structure nonwoven fabric substrate used in (Example 1), a copolyparaphenylene.3.4'oxydiphenylene terephthalamide structure nonwoven fabric was used. A prepreg and a printed wiring board were formed in the same manner as in (Example 1) except for the above.
【００２１】以上の実施例および比較例で得られたプリ
ント配線基板に対し、銅箔引き剥し強度、ガラス転移温
度（Ｔｇ）、弾性率、ハンダリフローによる抵抗変化量
の測定を行い、その結果を表１に示す。なお、評価方法
はつぎの（１）〜（４）とした。 （１）ピール強度（ｋｇ／ｃｍ）：ＪＩＳＣ６４８１の
方法で測定した。 （２）ガラス転移温度（Ｔｇ；℃）：銅箔をエッチング
後の基板をレオバイブロンにより測定しＴａｎδのピー
ク値で表した。 （３）弾性率（ｋｇ／ｍｍ2 ）：銅箔をエッチング後の
基板をレオバイブロンにより測定した２０℃と２５０℃
での貯蔵弾性率値で表した。 （４）ハンダリフローによる抵抗変化量（ｍΩ）：５０
０穴の直列配線基板に２６０℃２分のハンダリフローを
１０回施した後、電極間の抵抗を測定し、初期値からの
変化量で表した。The printed wiring boards obtained in the above Examples and Comparative Examples were measured for copper foil peeling strength, glass transition temperature (Tg), elastic modulus, and resistance change due to solder reflow. It shows in Table 1. The evaluation methods were the following (1) to (4). (1) Peel strength (kg / cm): Measured by the method of JIS C6481. (2) Glass transition temperature (Tg; ° C): The substrate after etching the copper foil was measured with rheovibron and expressed as a Tan δ peak value. (3) Modulus of elasticity (kg / mm 2 ): 20 ° C. and 250 ° C. measured by rheovibron on the substrate after etching the copper foil
It was expressed by the storage elastic modulus value. (4) Resistance change due to solder reflow (mΩ): 50
After performing a solder reflow at 260 ° C. for 2 minutes on a 0-hole serial wiring board 10 times, the resistance between the electrodes was measured and expressed as the amount of change from the initial value.
【００２２】[0022]
【表１】 [Table 1]
【００２３】この実施例によれば、エポキシ樹脂系にテ
トラブロムビスフェノールＡ構造物を必須とし、３また
は４官能エポキシ樹脂あるいはスルホン含有エポキシ樹
脂を含み、その硬化促進剤としてビスイミダゾール化合
物を含有する樹脂組成物を、全芳香族ポリアミド繊維基
材に含浸、乾燥してプリプレグを形成し、このプリプレ
グを所要枚数積層し、その表面へ銅箔を重ねて加圧加熱
により一体に成形して銅張積層板とすることにより、次
の効果が得られる。 （イ）リフロー法による半田付け工程時の抵抗変化率が
小さい耐熱性に優れた配線基板を得ることができる。 （ロ）銅箔および全芳香族ポリアミド繊維基材との接着
力が大きい機械的特性の優れた配線基板を得ることがで
きる。According to this example, a resin containing a tetrabromobisphenol A structure as an essential component in an epoxy resin system, a tri- or tetra-functional epoxy resin or a sulfone-containing epoxy resin, and a bisimidazole compound as a curing accelerator therefor is used. The composition is impregnated into a wholly aromatic polyamide fiber base material and dried to form a prepreg. The required number of prepregs are laminated, copper foil is laminated on the surface and integrally molded by pressure heating and copper clad lamination. By using a plate, the following effects can be obtained. (A) It is possible to obtain a wiring board having a small rate of resistance change during the soldering process by the reflow method and having excellent heat resistance. (B) It is possible to obtain a wiring board having a large adhesive force with a copper foil and a wholly aromatic polyamide fiber base material and excellent mechanical properties.
【００２４】これは、３官能エポキシ樹脂，４官能エポ
キシ樹脂およびジオキシジフェニレンスルホン含有エポ
キシ樹脂のうち少なくとも１つを含む組成物に対してビ
スイミダゾール化合物は、従来のイミダゾール系と比較
してエポキシ基の開環重合反応が非常に優れているた
め、少量の添加で大きな硬化性を発揮させる能力を有す
る。そのため、これより得られた硬化物は架橋密度が大
きく、かつ室温から高温状態での弾性率低下が少ないほ
か、全芳香族ポリアミド繊維基材との接合強度も大きい
ため、耐熱性や機械的強度等の向上作用があることによ
る。This is because the bisimidazole compound is more effective than the conventional imidazole-based compound in the composition containing at least one of a trifunctional epoxy resin, a tetrafunctional epoxy resin and a dioxydiphenylene sulfone-containing epoxy resin. Since the ring-opening polymerization reaction of the group is very excellent, it has the ability to exert great curability even when added in a small amount. Therefore, the cured product obtained from this has a high cross-linking density and little decrease in elastic modulus from room temperature to high temperature, and also has a large bonding strength with the wholly aromatic polyamide fiber base material, resulting in heat resistance and mechanical strength. It is due to the effect of improving
【００２５】なお、テトラブロムビスフェノールＡ構造
物は、加熱により分子内の水酸基と臭素との脱臭素化分
解が生じ、発生した臭化水素による酸素遮蔽効果による
難燃機能を有している。なお、全芳香族ポリアミド繊維
基材として、ポリメタフェニレンイソフタラミドが１５
重量％を超える構成の場合は、吸水性が大きくなり絶縁
性が確保されないため不適当であり、（実施例６）のよ
うに、ポリメタフェニレンイソフタラミドが１５重量％
以下の構成の場合であればよい。The tetrabromobisphenol A structure has a flame-retardant function due to the oxygen shielding effect of hydrogen bromide generated by debromination decomposition of hydroxyl groups in the molecule and bromine by heating. In addition, as a wholly aromatic polyamide fiber base material, polymetaphenylene isophthalamide is 15
In the case of the composition exceeding 5% by weight, the water absorption becomes large and the insulating property cannot be secured, so that it is unsuitable, and as in (Example 6), polymetaphenylene isophthalamide is 15% by weight.
The following configurations may be used.
【００２６】[0026]
【発明の効果】以上のようにこの発明は、エポキシ樹脂
系にテトラブロムビスフェノールＡ構造物を必須とし、
３官能エポキシ樹脂，４官能エポキシ樹脂およびスルホ
ン含有エポキシ樹脂のうち少なくとも１つを含み、その
硬化促進剤としてビスイミダゾール化合物を含有する樹
脂組成物であり、さらにこの樹脂組成物を全芳香族ポリ
アミド繊維基材に含浸、乾燥して形成したプリプレグで
ある。このプリプレグを所要枚数積層し、その表面へ銅
箔を重ねて加圧加熱により一体に成形して銅張積層板と
することにより、次の効果が得られる。 （イ）リフロー法による半田付け工程時の抵抗変化率が
小さい耐熱性に優れた配線基板を得ることができる。 （ロ）銅箔および全芳香族ポリアミド繊維基材との接着
力が大きい機械的特性の優れた配線基板を得ることがで
きる。As described above, according to the present invention, a tetrabromobisphenol A structure is essential in the epoxy resin system,
A resin composition containing at least one of a trifunctional epoxy resin, a tetrafunctional epoxy resin and a sulfone-containing epoxy resin, and containing a bisimidazole compound as a curing accelerator thereof, and further comprising this resin composition as a wholly aromatic polyamide fiber. It is a prepreg formed by impregnating a base material and drying. The following effects can be obtained by laminating a required number of these prepregs, stacking a copper foil on the surface thereof, and integrally molding the prepregs by heating under pressure to form a copper clad laminate. (A) It is possible to obtain a wiring board having a small rate of resistance change during the soldering process by the reflow method and having excellent heat resistance. (B) It is possible to obtain a wiring board having a large adhesive force with a copper foil and a wholly aromatic polyamide fiber base material and excellent mechanical properties.
Claims (10)
ノールＡ構造を含み、硬化促進剤としてビスイミダゾー
ル化合物を含むことを特徴とする樹脂組成物。1. A resin composition comprising an epoxy resin system containing a tetrabromobisphenol A structure and a bisimidazole compound as a curing accelerator.
含む請求項１の樹脂組成物。2. The resin composition of claim 1, wherein the epoxy resin system comprises a trifunctional epoxy resin.
含む請求項１の樹脂組成物。3. The resin composition of claim 1, wherein the epoxy resin system comprises a tetrafunctional epoxy resin.
シ樹脂を含む請求項１の樹脂組成物。4. An epoxy resin system is represented by: The resin composition according to claim 1, comprising a dioxydiphenyl sulfone structure-containing epoxy resin represented by
造含有エポキシ樹脂を含む請求項１の樹脂組成物。5. An epoxy resin system is represented by: The resin composition according to claim 1, which comprises an epoxy resin containing a tetrabromodioxydiphenyl sulfone structure represented by:
１の樹脂組成物。6. A bisimidazole compound having the general formula: The resin composition according to claim 1, which contains carbonyldiimidazole represented by:
の樹脂組成物を全芳香族ポリアミド繊維基材に含浸させ
てなることを特徴とするプリプレグ。8. The method of claim 1, 2, 3, 4, 5, 6, or 7.
A prepreg, which is obtained by impregnating a wholly aromatic polyamide fiber base material with the resin composition of.
％以下のポリメタフェニレンイソフタラミドを含むポリ
パラフェニレンテレフタラミド不織布である請求項８の
プリプレグ。9. The prepreg according to claim 8, wherein the wholly aromatic polyamide fiber base material is a polyparaphenylene terephthalamide nonwoven fabric containing 15% by weight or less of polymetaphenylene isophthalamide.
パラフェニレン・３．４’オキシジフェニレン・テレフ
タラミド不織布である請求項８のプリプレグ。10. The prepreg according to claim 8, wherein the wholly aromatic polyamide fiber base material is a copolyparaphenylene / 3.4 ′ oxydiphenylene / terephthalamide nonwoven fabric.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15189794A JP3343443B2 (en) | 1994-07-04 | 1994-07-04 | Resin composition and prepreg |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15189794A JP3343443B2 (en) | 1994-07-04 | 1994-07-04 | Resin composition and prepreg |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0812744A true JPH0812744A (en) | 1996-01-16 |
| JP3343443B2 JP3343443B2 (en) | 2002-11-11 |
Family
ID=15528586
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15189794A Expired - Fee Related JP3343443B2 (en) | 1994-07-04 | 1994-07-04 | Resin composition and prepreg |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3343443B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003342399A (en) * | 2002-05-28 | 2003-12-03 | Matsushita Electric Works Ltd | Prepreg and laminated plate having inner layer circuit obtained by using this prepreg |
| JP2014177525A (en) * | 2013-03-14 | 2014-09-25 | Adeka Corp | Bisimidazole compound, epoxy resin curing agent comprising bisimidazole compound, and one-pack curable epoxy resin composition comprising epoxy resin curing agent |
| JP2015059170A (en) * | 2013-09-18 | 2015-03-30 | 味の素株式会社 | Resin composition |
| WO2017012739A1 (en) * | 2015-07-17 | 2017-01-26 | Siemens Aktiengesellschaft | Solid insulation material, use thereof and the thus produced insulation system |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101389300B1 (en) | 2005-02-14 | 2014-04-25 | 존슨 앤드 존슨 비젼 케어, 인코포레이티드 | A method of producing ophthalmic lenses, an ophthalmic device, and a contact lens |
-
1994
- 1994-07-04 JP JP15189794A patent/JP3343443B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003342399A (en) * | 2002-05-28 | 2003-12-03 | Matsushita Electric Works Ltd | Prepreg and laminated plate having inner layer circuit obtained by using this prepreg |
| JP2014177525A (en) * | 2013-03-14 | 2014-09-25 | Adeka Corp | Bisimidazole compound, epoxy resin curing agent comprising bisimidazole compound, and one-pack curable epoxy resin composition comprising epoxy resin curing agent |
| JP2015059170A (en) * | 2013-09-18 | 2015-03-30 | 味の素株式会社 | Resin composition |
| WO2017012739A1 (en) * | 2015-07-17 | 2017-01-26 | Siemens Aktiengesellschaft | Solid insulation material, use thereof and the thus produced insulation system |
| CN107851481A (en) * | 2015-07-17 | 2018-03-27 | 西门子公司 | Solid insulating material, its purposes and the insulation system being produced from it |
| US10522265B2 (en) | 2015-07-17 | 2019-12-31 | Siemens Aktiengesellschaft | Solid insulation material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3343443B2 (en) | 2002-11-11 |
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