JPH09124806A - Production of prepreg - Google Patents
Production of prepregInfo
- Publication number
- JPH09124806A JPH09124806A JP28308095A JP28308095A JPH09124806A JP H09124806 A JPH09124806 A JP H09124806A JP 28308095 A JP28308095 A JP 28308095A JP 28308095 A JP28308095 A JP 28308095A JP H09124806 A JPH09124806 A JP H09124806A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- polyphenylene ether
- prepreg
- producing
- molecular weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、プリント回路板に
有用な変性エポキシ樹脂が含浸されたプリプレグの製法
に関する。FIELD OF THE INVENTION The present invention relates to a method for producing a prepreg impregnated with a modified epoxy resin useful for a printed circuit board.
【０００２】[0002]
【従来の技術】特に高周波領域で使用されるプリント回
路板には、特性として低誘電率と低誘電正接が求められ
る。ポリフェニレンエーテル（ＰＰＥ）樹脂は、低誘電
率、及び低誘電正接に起因して高周波用途に有用である
が、熱可塑性であり、接着性が低く、溶剤に対して溶解
性が劣る問題がある。これに対して、エポキシ樹脂は、
接着性や溶剤溶解性に優れている反面、誘電率、誘電正
接が比較的高く、高周波用途に使用すると、電送速度と
電送損失の点で好ましくない。2. Description of the Related Art Especially, a printed circuit board used in a high frequency region is required to have a low dielectric constant and a low dielectric loss tangent as characteristics. Polyphenylene ether (PPE) resins are useful for high frequency applications due to their low dielectric constant and low dielectric loss tangent, but they are thermoplastic, have low adhesiveness, and have poor solubility in solvents. On the other hand, epoxy resin is
Although it has excellent adhesiveness and solvent solubility, it has a relatively high dielectric constant and dielectric loss tangent, and is unfavorable from the viewpoint of transmission speed and transmission loss when used in high frequency applications.
【０００３】このように、特性の異なるエポキシ樹脂と
ＰＰＥをエポキシ樹脂の硬化剤とラジカル開始剤の存在
の下で反応させた変性エポキシ樹脂を必須成分としたプ
リプレグを用いて製造した積層板が提供され、高周波領
域で実用化されている。この実用化された積層板の原料
として用いられる変性エポキシ樹脂は、高分子量のＰＰ
Ｅの骨格がラジカル開始剤によって切断されることによ
っ生成した比較的低分子量のポリフェニレンエーテルと
エポキシ樹脂との反応生成物で、具体的には、低分子量
のポリフェニレンエーテルとエポキシ樹脂とポリフェニ
レンエーテルをラジカル化するラジカル開始剤とエポキ
シ樹脂の硬化剤をワニスの状態で、たとえばガラス布、
ガラス不織布、クラフト紙、リンター紙等の基材に含浸
後、加熱乾燥することにより基材中に変性エポキシ樹脂
の半硬化物を生成せしめてプリプレグとし、このプリプ
レグをさらに加熱加圧して積層板として提供される。As described above, there is provided a laminated plate manufactured by using a prepreg containing a modified epoxy resin as an essential component, which is obtained by reacting an epoxy resin and PPE having different characteristics in the presence of a curing agent for the epoxy resin and a radical initiator. It has been put to practical use in the high frequency range. The modified epoxy resin used as a raw material for this practically used laminated plate is a high molecular weight PP.
It is a reaction product of a relatively low molecular weight polyphenylene ether and an epoxy resin, which is generated by cleaving the skeleton of E by a radical initiator, and specifically, a low molecular weight polyphenylene ether, an epoxy resin, and a polyphenylene ether. Radical initiator and epoxy resin curing agent in the form of varnish, for example, glass cloth,
After impregnating a base material such as glass nonwoven fabric, kraft paper, linter paper, etc., it is heated and dried to produce a semi-cured product of the modified epoxy resin in the base material to form a prepreg, and this prepreg is further heated and pressed to form a laminated board. Provided.
【０００４】ところが、ポリフェニレンエーテルとエポ
キシ樹脂を溶媒に溶かしたワニスは、含浸性に多少の問
題を残している。すなわち、基材に対して含浸ムラが発
生し、その結果プリプレグ及び積層板にボイドが発生す
る問題がある。ボイドの発生した積層板は、吸湿性が大
きくなって耐ハンダ性が悪化したり、多層プリント回路
板に用いた場合は、スルホールメッキを施した際にボイ
ドに沿ってメッキ液が浸透し、ショートの原因となる。However, the varnish obtained by dissolving the polyphenylene ether and the epoxy resin in the solvent still has some problems in the impregnation property. That is, there is a problem that impregnation is generated in the base material, and as a result, voids are generated in the prepreg and the laminated plate. A laminated board with voids has a high hygroscopicity and deteriorates solder resistance, and when used in a multilayer printed circuit board, the plating solution penetrates along the voids when through-hole plating is applied, causing a short circuit. Cause of.
【０００５】[0005]
【発明が解決しようとする課題】したがって、本発明の
目的は、ポリフェニレンエーテルとエポキシ樹脂との反
応生成物である変性エポキシ樹脂の硬化物から成る積層
板に有用なプリプレグの製法を提供するものであって、
具体的には、低誘電率と低誘電正接を達成した積層板の
製造に有用な、変性エポキシ樹脂を含浸ムラなく含浸し
たプリプレグの製法を提供するものである。Accordingly, an object of the present invention is to provide a method for producing a prepreg useful for a laminate comprising a cured product of a modified epoxy resin which is a reaction product of polyphenylene ether and an epoxy resin. There
Specifically, the present invention provides a method for producing a prepreg in which a modified epoxy resin is uniformly impregnated, which is useful for producing a laminate having a low dielectric constant and a low dielectric loss tangent.
【０００６】[0006]
【発明が解決する手段】本発明に係るプリプレグの製法
によると、エポキシ樹脂、ポリフェニレンエーテル、エ
ポキシ樹脂の硬化剤、及びポリフェニレンエーテルをラ
ジカル化するラジカル開始剤を含有し、上記ポリフェニ
レンエーテルの数平均分子量が１０００〜２０００であ
るエポキシ樹脂ワニスを基材に含浸した後、加熱乾燥し
て上記エポキシ樹脂にポリフェニレンエーテルをラジカ
ル反応させて変性エポキシ樹脂の半硬化物を生成するも
ので、ポリフェニレンエーテルの数平均分子量が１００
０〜２０００に制限すると、ワニスの基材に対する含浸
性が増大すると同時に低誘電率と低誘電正接の特性を有
する積層板の製造に有用なプリプレグを製造することが
できる。すなわち、ポリフェニレンエーテルが１０００
にも達しない極度に低分子量のポリフェニレンエーテル
を用いると誘電率と低誘電正接の特性を積層板に与える
ことが出来ず、２０００を越えると基材に対する含浸性
が阻害され、低誘電率と低誘電正接の特性を積層板に与
えることが出来ないからである。According to the method for producing a prepreg according to the present invention, an epoxy resin, a polyphenylene ether, a curing agent for the epoxy resin, and a radical initiator for radically converting the polyphenylene ether are contained, and the polyphenylene ether has a number average molecular weight. Is impregnated into the base material with an epoxy resin varnish having a viscosity of 1000 to 2000, followed by heating and drying to cause a radical reaction of polyphenylene ether with the epoxy resin to produce a semi-cured product of a modified epoxy resin. Molecular weight 100
When the amount is limited to 0 to 2000, the impregnating property of the varnish with respect to the base material is increased, and at the same time, it is possible to produce a prepreg which is useful for producing a laminate having low dielectric constant and low dielectric loss tangent. That is, polyphenylene ether is 1000
If an extremely low molecular weight polyphenylene ether that does not reach the above level is used, the properties of dielectric constant and low dielectric loss tangent cannot be given to the laminate, and if it exceeds 2000, impregnation to the substrate is impaired and low dielectric constant and low This is because the characteristics of the dielectric loss tangent cannot be given to the laminated plate.
【０００７】なお、上記エポキシ樹脂の硬化剤として
は、フェノール性化合物が有効であり、ラジカル開始剤
としては、ベンゾイルパーオキサイド等の過酸化物が有
効である。A phenolic compound is effective as a curing agent for the epoxy resin, and a peroxide such as benzoyl peroxide is effective as a radical initiator.
【０００８】[0008]
【発明の実施の形態】以下、この発明の実施形態につい
て、具体的に説明する。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be specifically described below.
【０００９】本発明に係るプリプレグの製法は、エポキ
シ樹脂、ポリフェニレンエーテル、エポキシ樹脂の硬化
剤、ポリフェニレンエーテルのラジカル開始剤を必須成
分として含有するワニスを用いる。ここで、エポキシ樹
脂としては、従来のプリント回路板に適用される化合物
を適用することができ、特に制限はない。例示すれば、
ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型
エポキシ樹脂、ビスフェノールＳ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、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、及びこれら
の多官能エポキシ樹脂などが挙げられ、これらは単独、
または複数混合して使用される。さらには、これらの樹
脂の臭素化した難燃化エポキシ樹脂も使用できる。The prepreg manufacturing method according to the present invention uses a varnish containing an epoxy resin, a polyphenylene ether, a curing agent for the epoxy resin, and a radical initiator for the polyphenylene ether as essential components. Here, as the epoxy resin, a compound applied to a conventional printed circuit board can be applied, and there is no particular limitation. For example,
Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, isocyanurate type epoxy resin, hydantoin type epoxy resin, alicyclic Formula epoxy resins, and these polyfunctional epoxy resins, and the like, these alone,
Alternatively, a plurality of them may be mixed and used. Further, brominated flame-retardant epoxy resins of these resins can also be used.
【００１０】これらのエポキシ樹脂にラジカル反応させ
るポリフェニレンエーテルは、市販されている高分子量
のものを使用する場合には、ポリフェニレンエーテルを
ラジカル化するラジカル開始剤でもってポリフェニレン
エーテルの骨格を切断して低分子化した化合物を使用す
ることが必要である。すなわち、このポリフェニレンエ
ーテルの数平均分子量は、１０００〜２０００に制限さ
れる。すなわち、ポリフェニレンエーテルの低分子が過
度に進行して１０００にも達しない極度に低分子のポリ
フェニレンエーテルを用いると、ポリフェニレンエーテ
ルに起因する低誘電率と低誘電正接の特性を積層板に与
えることが出来ず、２０００を越えると、基材に対する
含浸性が阻害され、低誘電率と低誘電正接の特性を積層
板に与えることが出来ないからである。また、このポリ
フェニレンエーテルはポリスチレン等で変性した化合物
を使用することもできる。As for the polyphenylene ether to be radically reacted with these epoxy resins, when a commercially available high molecular weight one is used, the skeleton of the polyphenylene ether is cleaved by a radical initiator which radicalizes the polyphenylene ether to lower the polyphenylene ether. It is necessary to use molecularized compounds. That is, the number average molecular weight of this polyphenylene ether is limited to 1000 to 2000. That is, when a polyphenylene ether having an extremely low molecular weight of polyphenylene ether is excessively advanced and does not reach 1000, properties of low dielectric constant and low dielectric loss tangent due to the polyphenylene ether can be imparted to the laminate. If it exceeds 2000, the impregnating property with respect to the base material is impaired, and the properties of low dielectric constant and low dielectric loss tangent cannot be given to the laminate. Further, as the polyphenylene ether, a compound modified with polystyrene or the like can be used.
【００１１】エポキシ樹脂の硬化剤としては、エポキシ
樹脂の硬化剤として常用されるアミン系、フェノール
系、酸無水物系が用いられる。As the epoxy resin curing agent, amine-based, phenol-based, or acid anhydride-based compounds commonly used as epoxy resin curing agents are used.
【００１２】ポリフェニレンエーテルをラジカル化する
ラジカル開始剤としては、過酸化物が用いられ、特にベ
ンゾイルパーオキサイド（ＢＰＯ）が好適である。A peroxide is used as a radical initiator for converting polyphenylene ether into a radical, and benzoyl peroxide (BPO) is particularly preferable.
【００１３】本発明のプリプレグの製法は、上記のエポ
キシ樹脂ワニスを基材に含浸した後、加熱乾燥して上記
エポキシ樹脂にポリフェニレンエーテルをラジカル反応
させて変性エポキシ樹脂の半硬化物を生成するものであ
る。この変性エポキシ樹脂とポリフェニレンエーテルと
がラジカル反応して得られる変性エポキシ樹脂は、ポリ
フェニレンエーテルをラジカル化するラジカル開始剤の
存在のもとで得られるもので、加熱乾燥によって基材中
に半硬化の状態で生成する。The method for producing a prepreg of the present invention comprises impregnating a base material with the above-mentioned epoxy resin varnish, followed by heating and drying to cause a radical reaction of the above-mentioned epoxy resin with polyphenylene ether to form a semi-cured product of a modified epoxy resin. Is. The modified epoxy resin obtained by radical reaction of this modified epoxy resin and polyphenylene ether is obtained in the presence of a radical initiator that radicalizes the polyphenylene ether, and is semi-cured in the base material by heating and drying. Generate in the state.
【００１４】ここで、ワニスの調製について説明する。
数平均分子量が１５０００〜２５０００のポリフェニレ
ンエーテルの骨格を切断して数平均分子量が１０００〜
２０００のポリフェニレンエーテルを生成する反応条件
について説明すると、ポリフェニレンエーテル１００重
量部（以下単に部と記す）ＢＰＯは３〜１０部、エポキ
シ樹脂の硬化剤であるフェノール性化合物は３〜２０部
が適当である。このようにして得たポリフェニレンエー
テルを含有する生成物を必須成分のエポキシ樹脂とこの
エポキシ樹脂の硬化剤とともに適量の溶媒に溶解させて
エポキシ樹脂ワニスとする。Here, the preparation of the varnish will be described.
The number average molecular weight is 15,000 to 25,000, and the skeleton of the polyphenylene ether is cut to obtain the number average molecular weight of 1,000 to
Explaining reaction conditions for producing 2000 polyphenylene ether, 100 parts by weight of polyphenylene ether (hereinafter simply referred to as "part") BPO is 3 to 10 parts, and a phenolic compound as a curing agent for epoxy resin is 3 to 20 parts. is there. The product containing the polyphenylene ether thus obtained is dissolved in an appropriate amount of a solvent together with an essential component epoxy resin and a curing agent for the epoxy resin to form an epoxy resin varnish.
【００１５】数平均分子量が１５０００〜２５０００の
ポリフェニレンエーテルを用いて本発明で用いるワニス
の他の調製について説明すると、エポキシ樹脂とポリフ
ェニレンエーテルとエポキシ樹脂の硬化剤とＢＰＯとを
溶剤に溶かして反応させることもできる。この場合、ポ
リフェニレンエーテルを基準にしてエポキシ樹脂、この
エポキシ樹脂の硬化剤としてのビスフェノールＡ、及び
ＢＰＯの配合割合を示すと、ポリフェニレンエーテル１
００部、エポキシ樹脂は１００〜３００部、ビスフェノ
ールＡは３〜２０部、ＢＰＯは３〜１０部が適当であ
る。ポリフェニレンエーテルに対して特にビスフェノー
ルＡ、及びＢＰＯの添加量が多すぎると、プリプレグを
構成する変性エポキシ樹脂の平均分子量が下がりすぎ、
積層板の製造の際にプリプレグからの樹脂の流出量の増
大を招き、また硬化を完結させるための反応時間に長時
間を要することになる。反面、添加量が少なすぎると、
ワニスの粘度低減ができず、基材に対する含浸性に劣
る。なお、ポリフェニレンエーテルの骨格を切断する反
応温度は、８０°〜１２０℃が適温で、反応時間は１０
〜１００分で行うことができる。Another preparation of the varnish used in the present invention will be described using polyphenylene ether having a number average molecular weight of 15,000 to 25,000. Epoxy resin, polyphenylene ether, curing agent for epoxy resin and BPO are dissolved in a solvent and reacted. You can also In this case, the mixing ratio of epoxy resin, bisphenol A as a curing agent for this epoxy resin, and BPO based on polyphenylene ether is polyphenylene ether 1
00 parts, 100 to 300 parts of epoxy resin, 3 to 20 parts of bisphenol A, and 3 to 10 parts of BPO are suitable. If the amount of bisphenol A and BPO added is too large relative to the polyphenylene ether, the average molecular weight of the modified epoxy resin constituting the prepreg becomes too low,
At the time of manufacturing a laminated board, the outflow amount of resin from the prepreg is increased, and a long reaction time is required to complete the curing. On the other hand, if the amount added is too small,
The viscosity of the varnish cannot be reduced, and the impregnation property for the base material is poor. The reaction temperature for cleaving the skeleton of polyphenylene ether is 80 ° to 120 ° C., and the reaction time is 10
It can be done in ~ 100 minutes.
【００１６】なお、この反応は、これらの化合物の溶解
性を有する、たとえば、トルエン、ベンゼン、キシレン
等の芳香族系炭化水素やトリクロロエタン、テトラクロ
ロエタン、トリクロロエチレン、テトラクロロエチレ
ン、クロロホルム等のハロゲン炭化水素化合物に溶解さ
せて行う液相反応が好ましい。In this reaction, for example, aromatic hydrocarbons such as toluene, benzene, and xylene, and halogenated hydrocarbon compounds such as trichloroethane, tetrachloroethane, trichloroethylene, tetrachloroethylene, and chloroform having solubility of these compounds are used. A liquid phase reaction performed by dissolution is preferable.
【００１７】このプリプレグは、１枚乃至重ねた複数枚
に必要に応じて金属箔を配し、これを加熱加圧して積層
板とされる。This prepreg is provided with a metal foil on one sheet or a plurality of laminated sheets, if necessary, and heated and pressed to form a laminated plate.
【００１８】以下、本発明の実施例と比較例を挙げる。Examples of the present invention and comparative examples will be described below.
【００１９】[0019]
（実施例１）ポリフェニレンエーテル（日本ＧＥプラス
チック社製６４０−１１１）１００、ＢＰＯ５部、ビス
フェノールＡ５部をトルエンに溶かし、９０℃にて６０
分間反応させ、ポリフェニレンエーテルの骨格を切断
し、低分子量のポリフェニレンエーテルとした。生成し
たポリフェニレンエーテルのトルエン溶液を試料として
ゲル浸透クロマトグラフにて分子量分布を測定したとこ
ろ、９０℃で数平均分子量は１４００であった。(Example 1) 100 parts of polyphenylene ether (640-111 manufactured by Japan GE Plastics Co., Ltd.), 5 parts of BPO, and 5 parts of bisphenol A were dissolved in toluene and the mixture was heated at 90 ° C to 60 ° C.
After reacting for minutes, the skeleton of polyphenylene ether was cleaved to obtain a low molecular weight polyphenylene ether. When the molecular weight distribution was measured by gel permeation chromatography using the produced toluene solution of polyphenylene ether as a sample, the number average molecular weight was 1400 at 90 ° C.
【００２０】このトルエン溶液１００部に臭素化ビスフ
ェノールＡ型エポキシ樹脂（東都化成社製ＹＤＢ−５０
０をトルエンに溶かして不揮発分８０重量％（以下単に
％と記す）としたもの）１２５部、ジアミノジフェニー
ルメタン１部、２−エチル−４−メチルイミダゾール１
部を加え、さらにトルエンを添加して全体の不揮発分が
５０％となるようにした。得られた溶液状態にあるワニ
スは透明であった。このワニスをガラスクロス（ＭＩＬ
品番２１１６タイプ）に含浸し、１５０℃で３分加熱乾
燥し、樹脂量５３％のプリプレグを得た。得られたプリ
プレグの表面の樹脂ムラの有無、樹脂流出量（ＪＩＳ
Ｃ６５２１）、ガラスクロスへの樹脂の含浸性を評価し
た。評価結果を表１に示した。Brominated bisphenol A type epoxy resin (YDB-50 manufactured by Tohto Kasei Co., Ltd.) was added to 100 parts of this toluene solution.
0% dissolved in toluene to a nonvolatile content of 80% by weight (hereinafter simply referred to as%)) 125 parts, diaminodiphenylmethane 1 part, 2-ethyl-4-methylimidazole 1
Parts and then toluene to make the total nonvolatile content 50%. The resulting varnish in solution was transparent. Add this varnish to glass cloth (MIL
(Product No. 2116 type) was impregnated and dried by heating at 150 ° C. for 3 minutes to obtain a prepreg having a resin amount of 53%. Presence or absence of resin unevenness on the surface of the obtained prepreg, resin outflow amount (JIS
C6521), and the impregnation property of the resin into the glass cloth was evaluated. Table 1 shows the evaluation results.
【００２１】さらに、このプリプレグを８枚重ね、さら
にこの上下に１８μ厚の銅箔を配し、ステンレスプレー
トを上下に配して１９０℃で１００分、２０ｋｇ／ｃｍ
2 にて加熱加圧成形し、両面銅張の積層板を得た。この
時の成形後の板厚は０．８１ｍｍであった。この積層板
の誘電率、誘電正接、ＰＣＴ半田耐熱性（１２１℃２気
圧で１００分吸湿させた後に２６０℃の半田槽に浸漬し
た後、ミーズリングの発生の有無を評価）、メッキ液の
浸み込み性（ドリル径０．４ｍｍのスルホールを穿孔し
て、これをメッキ槽に浸漬し、析出した内部深さを測
定）、厚さ方向の断面の樹脂の充填性を表２に示した。Further, eight prepregs were stacked, copper foil having a thickness of 18 μm was further arranged on the upper and lower sides, and stainless steel plates were arranged on the upper and lower sides, and at 190 ° C. for 100 minutes, 20 kg / cm.
Heat-press molding was carried out at 2 to obtain a double-sided copper clad laminate. The plate thickness after molding at this time was 0.81 mm. Dielectric constant, dielectric loss tangent, PCT solder heat resistance of this laminated plate (after absorbing moisture at 121 ° C. and 2 atm for 100 minutes and then immersing it in a solder bath at 260 ° C., and then evaluating the occurrence of measling), immersion of plating solution Table 2 shows the penetration property (a through hole having a drill diameter of 0.4 mm was drilled, and this was dipped in a plating tank to measure the deposited internal depth) and the resin filling property of the cross section in the thickness direction.
【００２２】[0022]
（比較例１）ポリフェニレンエーテル（日本ＧＥプラス
チック社製６４０−１１１）１００、ＢＰＯ１部、ビス
フェノールＡ１部をトルエンに溶かし、９０℃にて６０
分間反応させ、ポリフェニレンエーテルの骨格を切断
し、低分子量のポリフェニレンエーテルとした。生成し
たポリフェニレンエーテルのトルエン溶液をゲル浸透ク
ロマトグラフにて分子量分布を測定したところ、９０℃
で数平均分子量は１７０００であった。このトルエン溶
液１００部に臭素化ビスフェノールＡ型エポキシ樹脂
（東都化成社製ＹＤＢ−５００をトルエンに溶かして不
揮発分８０重量％（以下単に％と記す）としたもの）１
２５部、ジアミノジフェニールメタン１部、２−エチル
−４−メチルイミダゾール１部を加え、さらにトルエン
を添加して全体の不揮発分が５０％となるようにした。
得られたワニスは高粘度のワニス状であった。このた
め、さらにトルエンを加え、不揮発分が４０％になるよ
うにしたところ懸濁した液となった。このワニスをガラ
スクロス（ＭＩＬ品番２１１６タイプ）に含浸し、１５
０℃で３分加熱乾燥し、樹脂量５３％のプリプレグを得
た。得られたプリプレグの表面の樹脂ムラの有無、樹脂
流出量、ガラスクロスへの樹脂の含浸性を評価した。評
価結果を表１に示した。(Comparative Example 1) 100 parts of polyphenylene ether (640-111 manufactured by Nippon GE Plastics Co., Ltd.), BPO, and 1 part of bisphenol A were dissolved in toluene, and the mixture was mixed at 60 ° C at 60 ° C.
After reacting for minutes, the skeleton of polyphenylene ether was cleaved to obtain a low molecular weight polyphenylene ether. The resulting polyphenylene ether solution in toluene was subjected to gel permeation chromatography to measure the molecular weight distribution.
The number average molecular weight was 17,000. Brominated bisphenol A type epoxy resin (YDB-500 manufactured by Tohto Kasei Co., Ltd. was dissolved in toluene to obtain a nonvolatile content of 80% by weight (hereinafter simply referred to as%)) in 100 parts of this toluene solution. 1
25 parts, 1 part of diaminodiphenylmethane and 1 part of 2-ethyl-4-methylimidazole were added, and toluene was further added so that the total nonvolatile content became 50%.
The varnish obtained was in the form of a highly viscous varnish. Therefore, when toluene was further added to adjust the nonvolatile content to 40%, a suspension was obtained. Impregnate this varnish into glass cloth (MIL product number 2116 type),
It was heated and dried at 0 ° C. for 3 minutes to obtain a prepreg having a resin amount of 53%. The presence or absence of resin unevenness on the surface of the obtained prepreg, the resin outflow amount, and the impregnation property of the resin into the glass cloth were evaluated. Table 1 shows the evaluation results.
【００２３】さらに、このプリプレグを８枚重ね、さら
にこの上下に１８μ厚の銅箔を配し、ステンレスプレー
トを上下に配して１９０℃で１００分、２０ｋｇ／ｃｍ
2 にて加熱加圧成形し、両面銅張の積層板を得た。この
時の成形後の板厚は０．９２ｍｍであった。この積層板
の誘電率、誘電正接、ＰＣＴ半田耐熱性（１２１℃２気
圧で１００分吸湿させた後に２６０℃の半田槽に浸漬し
た後、ミーズリングの発生の有無を評価）、メッキ液の
浸み込み性（ドリル径０．４ｍｍのスルホールを穿孔し
て、これをメッキ槽に浸漬し、析出した内部深さを測
定）、厚さ方向の断面の樹脂の充填性を表２に示した。Further, eight of these prepregs were stacked, copper foil having a thickness of 18 μm was further arranged on the upper and lower sides thereof, and stainless plates were arranged on the upper and lower sides, and at 190 ° C. for 100 minutes, 20 kg / cm.
Heat-press molding was carried out at 2 to obtain a double-sided copper clad laminate. The plate thickness after molding at this time was 0.92 mm. Dielectric constant, dielectric loss tangent, PCT solder heat resistance of this laminated plate (after absorbing moisture at 121 ° C. and 2 atm for 100 minutes and then immersing it in a solder bath at 260 ° C., and then evaluating the occurrence of measling), immersion of plating solution Table 2 shows the penetration property (a through hole having a drill diameter of 0.4 mm was drilled, and this was dipped in a plating tank to measure the deposited internal depth) and the resin filling property of the cross section in the thickness direction.
【００２４】[0024]
【表１】 [Table 1]
【００２５】[0025]
【表２】 [Table 2]
【００２６】[0026]
【発明の効果】本発明のプリプレグの製法によると、ポ
リフェニレンエーテルとエポキシ樹脂が反応した変性エ
ポキシ樹脂が含浸ムラなく含浸したプリプレグを製造す
ることができ、高周波用途に必要な低誘電率と低誘電正
接の点で優れた積層板の製造に有用なものである。According to the method of producing a prepreg of the present invention, a prepreg impregnated with a modified epoxy resin obtained by reacting a polyphenylene ether with an epoxy resin can be produced without unevenness, and the low dielectric constant and low dielectric constant required for high frequency applications can be obtained. It is useful for the production of a laminated plate excellent in terms of tangent.
フロントページの続き (72)発明者 山本 広志 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 Hiroshi Yamamoto 1048, Kadoma, Kadoma-shi, Osaka Matsushita Electric Works Co., Ltd.
Claims (4)
ル、エポキシ樹脂の硬化剤、及びポリフェニレンエーテ
ルをラジカル化するラジカル開始剤を含有し、上記ポリ
フェニレンエーテルの数平均分子量が１０００〜２００
０であるエポキシ樹脂ワニスを基材に含浸した後、加熱
乾燥して上記エポキシ樹脂にポリフェニレンエーテルを
ラジカル反応させて変性エポキシ樹脂の半硬化物を生成
することを特徴とするプリプレグの製法。1. An epoxy resin, a polyphenylene ether, a curing agent for the epoxy resin, and a radical initiator for radicalizing the polyphenylene ether are contained, and the polyphenylene ether has a number average molecular weight of 1000 to 200.
A method for producing a prepreg, characterized in that a base material is impregnated with an epoxy resin varnish having a value of 0, followed by heating and drying to radically react the epoxy resin with polyphenylene ether to produce a semi-cured product of a modified epoxy resin.
系化合物である請求項１のプリプレグの製法。2. The method for producing a prepreg according to claim 1, wherein the curing agent for the epoxy resin is a phenol compound.
求項１又は請求項２のプリプレグの製法。3. The method for producing a prepreg according to claim 1, wherein the radical initiator is a peroxide.
ドである請求項１乃至請求項３いずれかのプリプレグの
製法。4. The method for producing a prepreg according to claim 1, wherein the peroxide is benzoyl peroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28308095A JPH09124806A (en) | 1995-10-31 | 1995-10-31 | Production of prepreg |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28308095A JPH09124806A (en) | 1995-10-31 | 1995-10-31 | Production of prepreg |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09124806A true JPH09124806A (en) | 1997-05-13 |
Family
ID=17660959
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28308095A Pending JPH09124806A (en) | 1995-10-31 | 1995-10-31 | Production of prepreg |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09124806A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0962495A1 (en) * | 1996-11-12 | 1999-12-08 | General Electric Company | A curable polyphenylene ether-thermosetting resin composition |
| US6051662A (en) * | 1996-11-12 | 2000-04-18 | General Electric Co. | Curable polyphenylene ether-thermosetting resin composition and process |
| EP1176172A1 (en) * | 2000-07-26 | 2002-01-30 | Matsushita Electric Works, Ltd. | Epoxy resin composition, prepreg and metal-clad laminate |
| WO2010109948A1 (en) | 2009-03-26 | 2010-09-30 | パナソニック電工株式会社 | Epoxy resin composition, prepreg, metal foil with resin, resin sheet, laminate and multi-layer board |
-
1995
- 1995-10-31 JP JP28308095A patent/JPH09124806A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0962495A1 (en) * | 1996-11-12 | 1999-12-08 | General Electric Company | A curable polyphenylene ether-thermosetting resin composition |
| US6051662A (en) * | 1996-11-12 | 2000-04-18 | General Electric Co. | Curable polyphenylene ether-thermosetting resin composition and process |
| EP1176172A1 (en) * | 2000-07-26 | 2002-01-30 | Matsushita Electric Works, Ltd. | Epoxy resin composition, prepreg and metal-clad laminate |
| WO2010109948A1 (en) | 2009-03-26 | 2010-09-30 | パナソニック電工株式会社 | Epoxy resin composition, prepreg, metal foil with resin, resin sheet, laminate and multi-layer board |
| US10307990B2 (en) | 2009-03-26 | 2019-06-04 | Panasonic Intellectual Property Management Co., Ltd. | Epoxy resin composition, prepreg, resin-coated metal foil, resin sheet, laminate and multilayer board |
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